Interface Vol. 26, No. 4, Winter 2017 by The Electrochemical Society

IN THIS ISSUE

RIC S T C C LE

DA IN T O

Yâ&#x20AC;&#x2122;

DI E

CE OF N A T R

NCE IE

VOL. 26, NO. 4 Winter 2017

ST O ECHN

3 From the President:

Of Gradients, Conflicts, Electronics, and Access

7 Pennington Corner: We Choose to Go to the Moon ...

12 National Harbor, Maryland ECS Meeting Highlights

22 Candidates

for Society Office

49 The Chalkboard:

Fluctuation Analysis

53 The Chalkboard:

Relating Cyclic Voltammetry and Electrochemical Impedance Spectroscopy in a Mass Transport Controlled System

57 Looking at Patent Law 63 Tech Highlights 65 Importance of Dielectric

Science in Todayâ&#x20AC;&#x2122;s Technology

67 Novel Humidity Sensors

Based on Nanoscale Hybrid Dielectric Materials

71 Magnetic Nanoferrites

for RF CMOS: Enabling 5G and Beyond

77 High Dielectric Constant Materials for Nanoscale Devices and Beyond

Call for Nominations for Editor of Interface Deadline: January 5, 2018

ECS (The Electrochemical Society) is seeking to fill the position of editor of The Electrochemical Society Interface. Nominees should have qualities of leadership, technical breadth, time commitment, creativity, motivation, and international reputation. The successful candidate also will have excellent English-language writing and editing skills. The editor serves at the pleasure of the Publications Subcommittee for a four-year term, renewable for a total of eight years. A yearly honorarium is offered by the Society.

VOL. 25, NO.4 Winter 2016

IN THIS ISSUE

3 From the Editor:

“Use What You Need, but Need What You Use”

7 From the President: Leading the Band

8 Pennington Corner:

25 Years at the Corner

Winter 2015

11 Honolulu, Hawaii

VOL. 24, NO.4 Winter 2015

PRiME Meeting Highlights

IN THIS ISSUE

3 From the Editor:

The Fall of the Falling Mercury

7 From the President:

Fast Forward to 2051!

9 Phoenix, Arizona

Meeting Highlights

20 Candidates

for Society Offices

36 ECS Classics–Story of

32 Candidates

the Drop: The Way to the Nobel Prize over the Falling Mercury Droplets

41 Tech Highlights 43 The Impact of

Light Emitting Diodes

45 Impact of Light Emitting Diode Adoption on Rare Earth Element Use in Lighting

51 Polymeric Materials in

Phosphor-Converted LEDs for Lighting Applications

for Society Offices

85 PRiME 2016, Honolulu, HI Call for Papers

56 The Chalkboard: Work

Function in Electrochemistry

59 Tech Highlights

61 The Sensor Division Issue

Fall 2016

Summer 2016

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- V O L . 2 5 , N O . 2 -------------------------Summer 2016 -------------------------------------------------Org --------------------------------------------------anic -------------------------------------------------IN THIS ISSUE -------------------------and ----------------------------------------------------------------------------------- ------------------------------------------------- ------------------------ ---------------------------------------Biolo ---------- ------------------------ ------------------------ ---------------- gica -------------------------------------------------l ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

VOL. 25, NO.3 Fall 2016

3 From the Editor: Industry 4.0

7 From the President:

IN THIS ISSUE

More Transitions: Déjà Vu All Over Again!

3 From the Editor:

San Diego, California ECS Meeting Highlights

Electrochemistry and the Olympics

7 Pennington Corner:

29 Electric Vehicles

Digital Media to Promote the Importance of Our Research

Will Save the World

33 Tech Highlights

35 Electrons as “Agents”

31 Special Section:

PRiME 2016 Honolulu, Hawaii

and “Signals” of Change in Organic Chemistry, Biology, and Beyond

PMS motor

DC/AC inverter battery

Computational Studies on the Structure of Electrogenerated Ion Pairs

50 ECS Classics–Historical Origins of the Rotating Ring-Disk Electrode

63 Tech Highlights

63 Portable Breath Monitoring: A New Frontier in Personalized Health Care

65 Lithium-Ion Batteries—

41 Catalytic Reduction of

The 25th Anniversary of Commercialization

Organic Halides by Electrogenerated Nickel(I) Salen

67 Batteries and a Sustainable

47 Low-Cost Microfluidic

liThium-ion BATTeries The 25Th AnniversAry

Arrays for Protein-Based Cancer Diagnostics Using ECL Detection

53 Anodic Olefin Coupling

Reactions: A Mechanism Driven Approach to the Development of New Synthetic Tools

The 25Th AnniversAry of of CommerCiAlizATion CommerCiAlizATion

INTERFACE

VOL. 25, NO. 3

VOL. 25, NO. 2

roch

emis

try

37 When Ions Meet:

Elect

VOL. 24, NO. 4

INESCENCE

55 Phosphors by Design

e s ig I m p a c t o f ht de Emitting Dio

Th L

Modern Society

71 The Dawn

of Lithium-Ion Batteries

75 Importance of Coulombic

Efficiency Measurements in R&D Efforts to Obtain Long-Lived Li-Ion Batteries

79 The Li-Ion Battery:

25 Years of Exciting and Enriching Experiences

85 Lithium and Lithium-Ion

Batteries: Challenges and Prospects

INTERFACE

69 Ubiquitous Wearable

Electrochemical Sensors

73 Rapid Water Quality

Monitoring for Microbial Contamination

79 Smartphone-Based Sensors

109 National Harbor, Maryland Call for Papers

Spring 2016

VOL. 25, NO.1 Spring 2016

Additive MAnufActuring & electrocheMistry

IN THIS ISSUE

3 From the Editor: Interface @ 25!

7 Pennington Corner:

Evolution … Revolution

33 Special Section:

229th ECS Meeting San Diego, California

54 ECS Classics–Making

the Phone System More Reliable: Battery Research at Bell Labs

59 Tech Highlights

61 Additive Manufacturing and Electrochemistry

63 Additive Manufacturing for Electrochemical (Micro)Fluidic Platforms

69 The Emerging Role of

Electrodeposition in Additive Manufacturing

75 Additive Manufacturing:

Rethinking Battery Design

INTERFACE

VOL. 25, NO. 1

INTERFACE

staff, and the community-at-large. The Interface editor’s duties involve soliciting technical topics and articles from the divisions (one division or special topic is featured in each issue of the magazine), and assisting the division or guest editors in the development of its issue. The editor also encourages contributions from the broad scientific community that are of interest to ECS members. The editor reviews all technical manuscripts and provides editing as needed. In conjunction with the publisher, the editor guides the future path of the publication. The director of publications develops the nontechnical content for the publication, with feedback from the editor. In addition to the IAB, the publisher, and the director of publications, the editor has the assistance of other Society staff in the development and production of each issue. If selected as one of the finalists, the candidate is expected to be available for a Web-based interview with the Publications Subcommittee between the dates of February 26 and March 9, 2018. The new editor is expected to officially begin the The Brain role with an official term starting and Electrochemistry no later than June 1, 2018.

cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion V O L . 2 of 6 , Nthin O . 3 films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, F a dopamine l l 2 0 1 7 , carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, IN THIS ISSUE of thin films, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion Editor: 3 From the dopamine , carbon-fiber dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, Cash for Papers, of neural implants, electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization and “The Usefulness of methodologies, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration Useless Knowledge” Redux cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, 7 Pennington Corner: i n vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion AiME Highof thin films, dopamine, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, with Global Partnerships electrodes, miniaturization of carbon- fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum 26 Special Meeting Section: isolation, calibration neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal232nd ECS Meeting Maryland vivoHarbor, monitoring , methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, inNational , barrier neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants Classics:properties of thin 36 ECS Weston, the Weston Cell, cyclic voltammetry, films, corrosion of thin films, dopamine signal isolation, calibration methodologies, and the neuromodulation Volt , in vivo neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, thin biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion Patent Law films, 39 Looking atof dopamine, carbon-fiber dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, 45 Tech Highlights electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, and 47 The Brainmethodologies, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration Electrochemistry cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, 49 Electrochemistry of thin films, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of a Robust Neural Interface dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber Cyclic Voltammetric 53miniaturization of neural implants, electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, Measurements of methodologies, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration Neurotransmitters cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, cyclic voltammetry, neurotransmitters, dopamine, carbon-fiber electrodes, in vivo monitoring, neurotechnology, neuromodulation, in vivo biosensors, platinum electrodes, miniaturization of neural implants, barrier properties of thin films, corrosion of thin films, dopamine signal isolation, calibration methodologies, Fall 2017 VOL. 26, NO. 3

Interface was established in 1992 to serve as an authoritative 25 Years yet accessible publication for those in the field of solid state and electrochemical science and technology. Published quarterly, this four-color magazine contains technical articles about the latest developments in the field, and presents news and information about and for members of ECS 25 and the community-at-large. The editor’s responsibility is to fulfill the Society’s mission regarding the maintenance and development of its publications. The Society is committed to disseminating research and to advance electrochemical and solid state science and technology. Toward that purpose the Society seeks to maximize the value of Interface to both readers and authors. The editor is required to make editorial decisions consistent with maintaining the integrity of these scholarly publications. The editor works with the Interface Advisory Board (IAB), made up of the ECS publisher and representatives from each division. The IAB helps ensure that the publication contains information that encourages synergistic exchange among the Society membership, divisions, groups, sections, officers,

Those interested should send their qualifications for the position as follows: send a résumé (of no more than two pages), and a cover letter (of no more than two pages), stating why they are interested in the position, their previous experience with publications, and the availability of their time to fulfill the duties of this position. The materials should be sent no later than January 5, 2018, to Mary Yess, chief content officer and publisher, mary.yess@electrochem.org.

The Next Level of Bipotentiostat Design Introducing the PARSTAT 3000A-DX Dual channel potentiostat and hardware synchronized bipotentiostat in one Combine with our rotator, accessories, and software for a complete RRDE analysis solution Compact design featuring two independent potentiostats each with EIS capability as standard A high performance system with Âą30 V polarization/ compliance and Âą2 A current

www.ameteksi.com

BCS-8XX Series Battery Cycling System Now more affordable in a DC-only configuration

Precision HPC < 10 ppm 18 bit ADC

Performance 5 current ranges 2 ms acquisition rate

Modularity Mix & Match modules 150 mA to 15 A (120 A in parallel)

Value Uncompromised performance Optional EIS

www.bio-logic.net US: 865.769.3800 World: +33 476 986 831

FROM THE PRESIDENT Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902, Fax 609.737.2743 www.electrochem.org

Of Gradients, Conflicts, Electronics, and Access “It is all about power. If you have power, you have water. If you have water, you have food. If you have food, you can go to school. If you go to school, you have tools to think. If you have access and tools to think, you can learn those next door are not so different. You can work together to mitigate energy disparates and so reduce conflict. It is all about power.” —ECS satellite OpenCon, October 2017 ECS looks to its future as a forum for research and a conduit for access and communication. Tenets of the scientific method are invariant, but practice of communication and access change. Change is driven by gradients. Without gradients, energy is minimized and the system dies, but if gradients are too steep, the system becomes unstable. History maps conflicts over energy and power. Early wars were over land for food energy. Distribution of natural resources and oil sustain conflicts for thermal energy. Gradients in energy distribution drive change and conflict. Going forward, access to critical materials and information, coupled with the skills and imagination to develop advanced technologies, will mitigate steep gradients in energy distribution. ECS commits to open communications and access that will animate the vision of a global scientific community with information access, tools, and communications that address critical issues such as energy, and so contribute to greater global stability. The path forward couples available hardware with newly developing tools. Portable electronics provide means to mitigate the sharp disparities that drive conflict, through communications and access to information. With electronics, the brain is engaged and informed. Calm comes from availability of information and something to engage. Electronics are the apparatus that enable research through access, measurements, and communications. Once tools of only the few, now ubiquitous electronics allow discovery by thinking researchers worldwide. Add information access and communications, and researchers can work together to find new ideas that mitigate the harsh gradients that drive conflict. Researchers working in concert is the evolving symbiosis of research practice. ECS is a nexus for researchers. Electrochemical and solid state researchers are an impressively hardworking, collegial, and creative group drawn from across the globe. It is a network that seeks science, puzzles, and questions that transcend geography and historical frictions. By expanding fundamental understanding, technologies advance to improve the lot of humans worldwide. ECS was there at the beginning as a forum for advanced technologies (from batteries to semiconductors) and critical fundamentals (thermodynamics to catalysis). Going forward, ECS commits to promote access to knowledge and information, to enable communications, and to build a collegial matrix of researchers who address important challenges. ECS’s Free the Science initiative works to morph gradients in scholarly communications to drive openness in research. Information access and communications are the next step to build a global research community, by mitigation of harsh information gradients. Working toward this future, ECS undertakes experiments at the fringes of what is known about how to advance access. It is clear that the tools are in place to bring change, and the gradients to drive that change are in play. How to harness the gradients to effect worldwide access to information and communications is the question that ECS and like-minded researchers face. ECS is driving the path forward to a future of open collaboration, communication, and information because the gentle gradients of evolution in science practice depend on openness. Think how the gradients that drive change can be focused to build openness and shape a future with less conflict and better science. Because, it’s all about power … .

Johna Leddy ECS President president@electrochem.org https://orcid.org/0000-0001-8373-0452 The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Guest Editor: Durga Misra, dmisra@njit.edu Contributing Editors: Donald Pile, donald.pile@gmail. com; Alice Suroviec, asuroviec@berry.edu Managing Editor: Annie Goedkoop, Annie.Goedkoop@electrochem.org Production Manager: Dinia Agrawala, interface@electrochem.org Advertising Manager: Ashley Moran, Ashley.Moran@electrochem.org Advisory Board: Christopher Johnson (Battery), Masayuki Itagaki (Corrosion), Durga Misra (Dielectric Science and Technology), Philippe Vereecken (Electrodeposition), Jennifer Hite (Electronics and Photonics), A. Manivannan (Energy Technology), Paul Gannon (High Temperature Materials), John Weidner (Industrial Electrochemistry and Electrochemical Engineering), Uwe Happek (Luminescence and Display Materials), Slava Rotkin (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew Hillier (Physical and Analytical Electrochemistry), Nianqiang (Nick) Wu (Sensor) Publisher: Mary Yess, mary.yess@electrochem.org Publications Subcommittee Chair: Christina Bock Society Officers: Johna Leddy, President; Yue Kuo, Senior Vice President; Christina Bock, 2nd Vice President; Stefan De Gendt, 3rd Vice President; James Fenton, Secretary; E. Jennings Taylor, Treasurer; Roque J. Calvo, Executive Director Statements and opinions given in The Electrochemical Society Interface are those of the contributors, and ECS assumes no responsibility for them. Authorization to photocopy any article for internal or personal use beyond the fair use provisions of the Copyright Act of 1976 is granted by The Electrochemical Society to libraries and other users registered with the Copyright Clearance Center (CCC). Copying for other than internal or personal use without express permission of ECS is prohibited. The CCC Code for The Electrochemical Society Interface is 1064-8208/92. Canada Post: Publications Mail Agreement #40612608 Canada Returns to be sent to: Pitney Bowes International, P.O. Box 25542, London, ON N6C 6B2 ISSN : Print: 1064-8208

Online: 1944-8783

The Electrochemical Society Interface is published quarterly by The Electrochemical Society (ECS), at 65 South Main Street, Pennington, NJ 08534-2839 USA. Subscription to members as part of membership service; subscription to nonmembers is available; see the ECS website. Single copies $10.00 to members; $19.00 to nonmembers. © Copyright 2017 by The Electrochemical Society. Periodicals postage paid at Pennington, New Jersey, and at additional mailing offices. POSTMASTER: Send address changes to The Electrochemical Society, 65 South Main Street, Pennington, NJ 08534-2839. The Electrochemical Society is an educational, nonprofit 501(c)(3) organization with more than 8,500 scientists and engineers in over 75 countries worldwide who hold individual membership. Founded in 1902, the Society has a long tradition in advancing the theory and practice of electrochemical and solid state science by dissemination of information through its publications and international meetings. 3 All recycled paper. Printed in USA.

Rapid, High-Current Pulsing & Superior, Low-Impedance EIS Reference 30K Booster Nobody is faster Distortion-free, rapid pulsing for charge and discharge

30 A Pulse on a 5 mOhm cell

Nobody goes lower Up to 30A @ 20V, EIS to 300 kHz

200 nOhm Shorted Lead Curve 20 A rms, 0.9 m cell cable

www.gamry.com

Vol. 26, No. 4 Winter 2017

65 67 71 77

Importance of Dielectric Science in Today’s Technology by Durga Misra Novel Humidity Sensors Based on Nanoscale Hybrid Dielectric Materials by Zhi David Chen Magnetic Nanoferrites for RF CMOS: Enabling 5G and Beyond by Ranajit Sai, S. A. Shivashankar, Masahiro Yamaguchi, and Navakanta Bhat High Dielectric Constant Materials for Nanoscale Devices and Beyond by Hiroshi Iwai, Akira Toriumi, and Durga Misra

the President: 3 From Of Gradients, Conflicts, Electronics, and Access

Corner: 7 Pennington We Choose to Go to the Moon ...

Harbor, Maryland 12 National ECS Meeting Highlights for 22 Candidates Society Offices

26 Society News 41 Free Radicals 46 People News 57 Looking at Patent Law 63 Tech Highlights 82 Section News 84 Awards Program 86 New Members Summer Fellowship 90 ECS Reports 99 Student News

Cover design by Dinia Agrawala. The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

PENNINGTON CORNER

We Choose to Go to the Moon . . .

nited States President John F. Kennedy sent a powerful message to the country in his speech at Rice University in 1962, “We choose to go to the Moon in this decade and do the other things, not because they are easy, but because they are hard; because that goal will serve to organize and measure the best of our energies and skills, because that challenge is one that we are willing to accept, one we are unwilling to postpone, and one we intend to win.” History has shown that it was not necessary to go to the Moon to win Kennedy’s challenge. His primary goal was to elevate U.S. national security during the Cold War when the Soviet Union was advancing as a world power and showing signs of superiority in their space program. The U.S. put a man on the Moon in 1969, but far more important was the spirit of innovation that was created, leading to world-changing new technologies in security, communications, and transportation, which was the true win. Kennedy understood the importance of innovation and risk taking to the success of a nation and his speech permanently implanted this message into the ideal of science and the role it plays in advancing mankind. He continues to stimulate progress because in his words, “there is new knowledge to be gained … and used for the progress of all people.” It is amazing how Kennedy’s influence has prevailed. In a recent ECS podcast with Steven Chu,* the former U.S. Secretary of Energy and 1997 Nobel Prize winner said, “As a scientist, you better be an optimist … half the science I try to do is really shoot for the Moon.” *Steven Chu was the Plenary Lecturer at 232nd ECS Meeting, National Harbor, MD, October 6, 2017.

When the Board approved the Free the Science initiative in 2013, we created an ideal to tackle the new paradigm of open science in scholarly communications and that has driven innovation to incredible new levels at ECS. As a nonprofit publisher, we have seen a rise in article submissions and dissemination through structural changes to the journals and to the role of our editorial board and divisions. We introduced a series of new publication opportunities including focus issues, perspective articles, and critical review articles in the journals. In the coming months, ECS will launch ECSarXiv, an open science preprint server, to provide a new venue for content to be shared and cited in our technical fields. And most importantly, through the Free the Science initiative we have created many open access opportunities for authors, which have led to the open accessibility of 36% of our journal articles in the four years since we began. In driving the Free the Science vision since 2013, ECS has experienced innovation and growth in many other programs and services as well. In the area of meetings, ECS has become more diverse, leading to growth in the number of presentations and attendance. Communications have improved dramatically through the creation of a slew of new vehicles: a new organizational website and the Free the Science website; a new digital media center with podcasts, the ECS Masters videos, lecture series, and oral histories; the Redcat Blog; a weekly eNews; and the ECS Digital Library Weekly Digests. These communications have expanded our community reach by increasing our database to over 30,000 constituents (over 3,000 new records so far in 2017) who regularly engage with ECS. And the most interested constituents in the new open science paradigm are the students whose participation in membership, meetings, and publications have all grown. Institutionally, the Board has approved 35 new student chapters worldwide since 2013.

No one gets to the Moon alone, and ECS has developed many new partnerships with organizations who share in the Free the Science ideals (see below). The support of these partners demonstrates the importance of our version of the Moon shot; and, to increase our impact, we seek to engage more like-minded people and organizations as Free the Science grows. Finally our Moon shot has advanced the ECS mission to disseminate research at an unprecedented pace. Over the past six years, we have seen a dramatic increase in several key metrics including: Journal of The Electrochemical Society citations at 48% and impact factor at 46%, and an incredible 220% increase in downloads from the ECS Digital Library. For Free the Science to be realized, it requires new funding that can come from various sources that we need to grow. Philanthropic giving has been slow to materialize but our Moon shot has doubled the number of ECS donors and opened doors at the Gates Foundation, the Arnold Foundation, the Sloan Foundation, and many others that are part of the Open Research Funders Group. The initiative has also driven improvement in the profitability of our operations resulting in a 32% increase in our net worth in the past six years bringing it to $18M. We still have a long way to go before we land on the Moon and at times I wonder whether we will ever take that “one giant leap for mankind.” But then I consider what ECS has accomplished since embarking on our mission-based initiative to Free the Science, and I am reassured in knowing we already have.

Roque J. Calvo ECS Executive Director http://orcid.org/0000-0002-1746-8668

Partners on the Trajectory to Free the Science ECS collaborates with many organizations and these partnerships have helped us to make great progress with our Free the Science initiatives. COS — ECS is a signatory to the Center for Open Science transparency and openness guidelines. COS is building a cost saving platform for the Society’s digital library along with ECSarXiv, a preprint server, currently in beta testing, that will also allow ECS to explore publishing different types of scholarly outputs. Research4Life — Through R4L, ECS is able to provide free or low-cost access to our digital library to developing countries.

SPARC — The Scholarly Publishing and Academic Resources Coalition has supported ECS since 2013 by providing feedback from the library community as we developed our offering. A SPARC representative serves on our Open Access/Open Science Subcommittee.

OSI — The Open Scholarship Initiative convenes stakeholders from around the world, working to improve the scholarly publishing ecosystem. ECS is gaining recognition for Free the Science and building connections among other OA and open science leaders and funders.

CHORUS — ECS became a signatory in 2014. Once we become a full member, CHORUS will be indispensable in minimizing OA mandate compliance burdens for our authors.

OpenCon — ECS was the first scholarly society to hold a satellite OpenCon, bringing together outstanding speakers aimed at creating a culture of change in how research is shared and disseminated, making scientific progress faster.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

COMPLETE SOLUTIONS FOR ADVANCED ELECTROCATALYSIS RESEARCH

Metrohm Electrochemistry supports high-impact electrocatalyst research for a variety of applications with our high-quality, modular Autolab and DropSens potentiostats/ galvanostats and accessories. Whether you are studying reaction mechanisms, kinetics with Levich or KouteckýLevich analysis, plasmonic or chromophoric systems, bio-functionalized electrodes, or surfaces decorated with other catalytic sites, our electrochemical workstations can be tailored to ﬁt your needs. Expand your research capabilities to include • Ultra-low noise RDE and RRDE to investigate reaction mechanisms and kinetics • Fully-integrated spectroelectrochemistry for time-resolved, in-situ experiments • True analog scans and ultra-fast sampling to measure rapid transients • Electrochemical impedance spectroscopy for advanced modeling and analysis • Functionalized screen-printed electrodes and small-volume ﬂow-cells

For more information, visit: catalysis.metrohmusa.com

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOFC-XV

15th International Symposium on Solid Oxide Fuel Cells

HOLLYWOOD, FLORIDA, USA

Highlights from SOFC-XV

he 15th International Symposium on Solid Oxide Fuel Cells (SOFC-XV) was held in Hollywood, Florida, July 2328, 2017 at the Diplomat Beach Resort. Almost 400 scientists, engineers, and researchers from over 30 countries convened to share results and discuss issues related to solid oxide fuel cells and solid oxide electrolysis cells. The event was sponsored by the ECS High Temperature Materials Division and the SOFC Society of Japan, and organized by Subhash Singhal (Pacific Northwest National Laboratory, U.S.) and Tatsuya Kawada (Tohoku University, Japan). The conference kicked off on Monday with overviews of SOFC programs in the U.S., Japan, and Europe, as well as a look back at almost 30 years of research and development activities presented at the past 14 SOFC symposia in this series. Throughout the week, over 225 oral presentations were given on topics such as SOFC systems, anodes, cathodes, electrolytes, fuels, interconnects/contact materials/ seals, cells and stacks, reversible cells, and modeling. Attendees were also able to view more than 125 posters organized across 3 separate evenings. On Wednesday, there was a special workshop on “Synergistic Use of Solid Oxide Fuel Cells (SOFCs) in Data Centers and Other Embedded Energy Applications” (see sidebar). Throughout the wide range of presentations, there were several main observations from the week. Excellent fundamental research in academia and national institutions is being conducted in an ever-increasing number of countries, with a growing emphasis on international collaboration, especially in Europe. On the technical side, considerable progress is being made in the commercialization of SOFC residential CHP units (~1 kWe), and an increasing amount of work is being conducted on electrolysis and reversible cells. Commercial sales of SOFC-distributed power generation systems continue with units totaling over 250 MW installed or on order. The main positive market drivers for SOFCs are low emissions, fuel flexibility, and high efficiency, even in small-sized systems. Issues that need to be further refined are the cost, performance durability, and overall lifetime. (continued on next page)

The Future of SOFCs: Shared Visions More than 100 attendees of SOFC-XV chose to spend the free afternoon on Wednesday attending a special workshop on the synergistic use of SOFCs in data centers and other embedded energy applications. The workshop was chaired by Stu Adler (University of Washington) and included talks by Sean James (Microsoft), Morgan Andreae (Cummins), Jack Brouwer (University of California-Irvine), and Mark Selby (Ceres Power). Following the talks, the speakers held a panel discussion on the future of SOFCs and other related technologies in distributed power. The following are notable highlights from the panel discussion: • “You had me at 50%.” – Sean James The panelists pointed out many benefits of SOFCs in distributed power that go beyond efficiency and agreed that widespread commercialization of SOFCs is currently limited more by cost and better demonstration of long-term reliability in integrated systems. These aspects are more critical to demand-driven commercialization than further improvements in efficiency and/or power density. • “$1,000/kW” – Morgan Andreae The SOFC community has long understood the importance of reducing capital cost. However, the panel provided some customer perspectives on what would be needed to achieve widespread adoption. For data centers, embedded SOFC systems would need to achieve $2,500/kW to attract significant interest and $1,500/kW for widespread adoption. For light commercial power (e.g., truck auxiliary power units), systems would need to be $1,000–$1,200 kW. These figures represent a tipping point where the technology would become demand driven rather than technology/subsidy driven, as it has been historically. • “I would never consider an SOFC system without a battery in it.” – Jack Brouwer At one point, the panel discussion strayed to the issue of batteries versus fuel cells. The panelists agreed that this is a largely specious issue, as the two technologies do fundamentally different things and work best when combined together in synergistic ways. This is especially true in embedded applications that must handle transient demand and storage on multiple timescales. • “SOFCs are the missing piece.” – Mark Selby An audience member asked if the rapid advancement of sustainable electricity generation and batteries would obviate the need for fuel cells to consume fossil fuels. The panelists pointed out that SOFCs do not just consume fossil fuels—SOFCs and SOECs may play a critical future role in interconverting electrical and chemical energy, allowing long-term storage and recovery of sustainably generated electricity, or CO2-neutral transportation fuels. Our need for fuel cells will only grow as we move away from fossil fuels!

ECS Executive Director Roque Calvo presented Subhash Singhal a plaque featuring the original SOFC program from 1989 to celebrate Singhal’s many years of service.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued from previous page)

The panel discussed their visions on the future of SOFCs and other related technologies in distributed power. From left to right: Jack Brouwer (UC Irvine), Morgan Andreae (Cummins), Sean James (Microsoft), and Mark Selby (Ceres Power).

As has become tradition at all the SOFC symposia, attendees gathered on Wednesday night to relax and unwind during a cocktail hour and banquet featuring local-themed entertainment. During the banquet, special recognition was given to Nguyen Minh, Junichiro Mizusaki, and Subhash Singhal, each of whom have attended all 15 SOFC symposia held throughout the years. In addition, during the plenary session, Singhal was presented with a framed certificate of appreciation containing a copy of the call for papers and program from the very first symposium, which was held back in 1989.

“Subhash Singhal launched this conference in 1989 at the 176th ECS Meeting in Hollywood, Florida, and has guided its planning and development for 30 years,” said ECS Executive Director Roque Calvo. “He has developed the SOFC symposium into the most significant event in the world dedicated to the progress of solid oxide fuels cells. On behalf of ECS, it gives me great pleasure to congratulate him and all the conference organizers on conducting the 15th successful SOFC symposium and to thank Subhash for his leadership and significant contributions to this important field.” ECS thanks all the presenters, session chairs, exhibitors, and volunteers for their support in making SOFC-XV a huge success.

Attendees took a break from the technical sessions to enjoy conversation and cocktails with their friends and colleagues before the evening’s banquet.

During three nights of poster sessions, attendees shared their research with colleagues from around the world.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Photo by National Harbor.

232nd ECS MEETING National Harbor, MD

October 1-5, 2017

Highlights from the 232nd ECS Meeting

early 2,400 people from 54 countries attended the 232nd ECS Meeting in National Harbor, Maryland, October 1-5, 2017. Participants could choose from 49 symposia, over 1,250 oral talks, 644 student presentations, and nearly 570 posters. Plenary Session

ECS President Johna Leddy welcomed attendees to the meeting during Monday evening’s plenary session. In addition to wrapping up the first full day of technical sessions and honoring award winners, Leddy highlighted the 115th anniversary of the establishment of ECS and the Society’s bold move toward complete open access through the Free the Science initiative. “Three years ago ECS committed to the vision of Free the Science, an initiative to sustain ECS publications into the future of scholarly communications,” Leddy said. “ECS is one of the only scientific communities to take such a bold stance, recognizing the problems that exist in the current structure of scholarly publishing. Much like our founders 115 years ago, we are taking the lead and carving out a unique position.”

The ECS Lecture Former U.S. Secretary of Energy and Nobel Laurate Steven Chu delivered this meeting’s ECS Lecture, “The Role of Electrochemistry in our Transition to Sustainable Energy.” Chu’s talk focused on the importance of electrochemistry in the coming decades as the energy landscape continues to evolve. (Read more about Chu’s talk on page 20.)

ECS President Johna Leddy presented the opening remarks at the 232nd ECS Meeting.

OpenCon ECS hosted its first ever satellite OpenCon event during the 232nd ECS Meeting. OpenCon is an international event hosted by the Right to Research Coalition, a student organization of the Scholarly Publishing and Academic Resources Coalition (SPARC). The speakers included Ashely Farley (Bill and Melinda Gates Foundation), Meredith Morovati (Dryad), Brian Nosek (Center for Open Science), Dina Paltoo (National Institutes of Health), Daniel Schwartz (University of Washington Clean Energy Institute), and Nick Shockey (SPARC). (Read more about ECS OpenCon 2017 on page 35 of this issue.)

Steven Chu, corecipient of the 1997 Nobel Prize in Physics, delivered the meeting’s plenary lecture.

Dina Paltoo (right) of the National Institutes of Health answered questions during the OpenCon panel discussion alongside SPARC’s Nick Shockey (left). 12

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

ECS Data Sciences Hack Day Another landmark event at National Harbor was the ECS Data Sciences Hack Day, the Society’s first foray into building an electrochemical data sciences and open-source community from the ground up. “Hack Day is an opportunity to get people together to build software, learn how to program, and eventually build a community of data science at ECS,” said Matt Murbach, University of Washington graduate student and co-organizer of the event. “We’re trying to build a repository for software that people use in their daily lives as electrochemists, except we want it to be open. We want people to contribute to packages that other researchers can use and have the ability to build tools and analysis techniques that are reproducible.” Daniel Schwartz, Boeing-Sutter Professor of Chemical Engineering and director of the Clean Energy Institute at the University of Washington, and David Beck, senior data scientist with the eSciences Institute at the University of Washington also coorganized this event. (Read more about ECS Data Sciences Hack Day on page 36 of this issue.)

Organizer David Beck led a hack session during the ECS Data Sciences Hack Day.

“Energy-Water Nexus” featured a talk by Fernando Miralles-Wilhelm of the Earth Systems Science Interdisciplinary Center.

Michael Wolfson of the National Institutes of Health delivered a talk during “The Brain and Electrochemistry” symposium.

Electrochemical Energy Summit The 7th International ECS Electrochemical Energy Summit took place during the 232nd ECS Meeting. This year’s summit theme was “Human Sustainability – Energy, Water, Food, and Health,” and included three distinct symposia: “Energy-Water Nexus,” “The Brain and Electrochemistry,” and “Sensors for Food Safety, Quality, and Security.” The summit was chaired by Eric Wachsman (University of Maryland) and organized by Bryan Chin (Auburn University), Lili Deligianni (IBM Corporation Research Center), and Christina Bock (National Research Council of Canada). “The Electrochemical Energy Summit is really focused on using electrochemistry to address human sustainability issues,” Wachsman said. “We’re bringing in agencies that support the research that is critical for the members of ECS. This is a unique benefit for the members of the Society to find out about opportunities to fund their research so they can make the developments to address the needs of the human population.” In total, the summit had 116 technical presentations across the three symposia and brought invited speakers from organizations ranging from the National Science Foundation to the U.S. Food and Drug Administration.

Sonny Ramaswamy, director of the National Institute of Food and Agriculture, delivered a talk during the “Sensors for Food Safety, Quality, and Security” symposium.

(continued on next page)

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued from previous page)

Award Highlights Battery Slam The ECS Battery Student Slam symposium made its second appearance at the 232nd ECS Meeting. The symposium was open to students pursing undergraduate or graduate degrees geared toward battery-related research, ranging from battery materials and design to fuel cells and supercapacitors. Each student participating in the symposium delivered a 10-minute presentation about their work followed by 2 minutes of questions and discussion from the audience. The top 3 presentations in the symposium were then recognized with cash prizes and awards as judged by the symposium organizers. First Place: Bo Hu, Utah State University, “Long-Cycling Ferrocene/MV Aqueous Organic Redox Flow Battery (AORFB)” Second Place: Armin Vahid Mohammadi, Auburn University, “Aluminum Intercalation and High Capacity of TwoDimensional (2D) Vanadium Carbide (MXene) Cathode in Rechargeable Aluminum Batteries” Third Place: Mallory Clites, Drexel University, “Chemical Preintercalation of Bilayered Vanadium Oxide for Versatile, High Capacity Electrodes in Ion-Based Batteries”

Ride-and-Learn ECS meeting attendees had the opportunity to see some of the world’s first commercial hydrogen and fuel cells vehicles, as well as hear updates from the U.S. Department of Energy, at the DOE Rideand-Learn event. “There are now three hydrogen fuel cell cars that are commercially available,” said Sunita Satyapal, director of fuel cell technologies at the DOE. “We’re continuing to make progress on both fuel cells and hydrogen production, and it’s pretty historic that we’ve come this far in a relatively short period of time.” The Ride-and-Learn was organized by the DOE’s Fuel Cell Technologies Office in the Office of Energy Efficiency and Renewable Energy. The Fuel Cell Technologies Office has funded early-stage hydrogen and fuel cells research and development, enabling a 60 percent reduction in fuel cell cost, a fourfold increase in fuel cell durability, and an 80 percent cut in the cost of electrolyzers over the past decade.

ECS President Johna Leddy (right) with Philippe Marcus (left) from the National Centre for Scientific Research, winner of the Olin Palladium Award.

The 2017 Olin Palladium Award was presented to Philippe Marcus. Marcus is the director of research at the National Centre for Scientific Research and the head of the research group of physical chemistry of surfaces at the Institut de Recherche de Chimie Paris at Chimie ParisTech in France. His field of research is surface electrochemistry and corrosion science, with emphasis on understanding the relationship between structure and properties of metal surfaces and oxide films at the atomic or nanometric scale. The Olin Palladium Award was established in 1950 to recognize distinguished contributions to the field of electrochemical or corrosion science. The award was founded with the funds from the royalties derived from the sale of Herbert H. Uhlig’s Corrosion Handbook. The handbook was sponsored and largely written by members active in the ECS Corrosion Division. The 2017 Carl Wagner Memorial Award was presented to Eric Wachsman. Wachsman is the director of the Maryland Energy Innovation Institute and the Crentz Centennial Chair in Energy Research, with appointments in both the Department of Materials Science and Engineering and the Department of Chemical Engineering at the University of Maryland. Wachsman is a fellow of

Meeting attendees learned about the technology behind fuel cell vehicles during the DOE Ride-and-Learn event.

ECS President Johna Leddy (left) with Eric Wachsman (right) from the University of Maryland, winner of the Carl Wagner Memorial Award. 14

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

ECS 2017 Class of Fellows—front row (left to right): Robert Huggins, ECS President Johna Leddy, Marca Doeff, and Christina Bock; back row (left to right): Khalil Amine, Christopher Johnson, Rangachary Mukundan, Scott Barnett, and Nianqiang (Nick) Wu. Not pictured: Christian Amatore, Plamen Atanassov, Mario Ferreira, Clare Grey, Joachim Maier, Tae-Yeon Seong, and Yang Shao-Horn.

both ECS and the American Ceramic Society and serves on the ECS Board of Directors. The Carl Wagner Memorial Award was established in 1980 to recognize midcareer achievement, excellence in research areas of interest of the Society, and significant contributions in the teaching or guidance of students or colleagues in education, industry, or government. The award commemorates Carl Wagner, a man of outstanding scientific achievement with important contributions in all areas of the Society’s interest, the Society’s first Olin Palladium Award winner, and a dedicated teacher. The Norman Hackerman Young Author Award for the best paper published by young authors in the 2016 volume of the Journal of The Electrochemical Society for a topic in the field of electrochemical science and technology went to Mark Burgess and Kenneth Hernández-Burgos from the University of Illinois at UrbanaChampaign for their paper “Scanning Electrochemical Microscopy and Hydrodynamic Voltammetry Investigation of Charge Transfer Mechanisms on Redox Active Polymers.” The Bruce Deal and Andy Grove Young Author Award for the best paper published by a young author in the 2016 volume of the ECS Journal of Solid State Science and Technology for a topic in the field of solid state science went to Peng Sun from the University of Michigan for his paper “Toward Practical Non-Contact Optical Strain Sensing Using Single-Walled Carbon Nanotubes.” Yue Kuo, ECS senior vice president, assisted with the introduction of the 2017 Class of Fellows. These members are recognized for contributions to the advancement of science and technology, for leadership in electrochemical and solid state science and technology, and for active participation in the affairs of ECS. Christian Amatore—for outstanding contributions in physical, analytical, and molecular electrochemistry through pioneering ultramicro/nanoelectrodes and bringing new and important concepts to these fields that led to major outcomes in chemistry, catalysis, and neuroscience. Khalil Amine—for outstanding achievement in the field of material sciences, electrochemistry, and, more specifically, energy storage. Plamen Atanassov—for important discoveries, innovation, and leadership in the areas of bioelectrochemistry and materials for electrochemical energy conversion. Scott Barnett—for extensive and outstanding contributions to solid oxide fuel cells and batteries and his valuable service to the Society. Christina Bock—for technical research contributions in the area of synthesis and characterization of electrochemical catalysts for energy conversion and storage, environmental control, and electrolyzer applications for over 25 years.

Marca Doeff—for pioneering work on sodium-ion batteries (especially identification and characterization of novel electrode materials), for characterization of solid electrolyte and Li-ion battery cathode materials using synchrotron techniques, and for continued service to the Society. Mario Ferreira—for contributions to corrosion science and electrochemistry in the service, technology, and education industries. Clare Grey—for distinguished contributions to the fundamental understanding of the behavior of electrode materials for lithium-ion batteries. Robert Huggins—for lifetime contributions to the fundamental understanding of battery materials and solid state ionics. Christopher Johnson—for exceptional contributions to advance the field of electrochemical energy storage and for tireless service to ECS. Joachim Maier—for outstanding contributions to the theory and study of point defects and space charges in ionic solids at surfaces and interfaces, resulting in groundbreaking work in the field of size effects in ionic conductors. Rangachary Mukundan—for unmatched, exemplary service and contributions to the Society and the ECS Sensor Division and for the mentoring of students for over 20 years. Tae-Yeon Seong—for significant contributions to the fields of compound semiconductor materials characterization, processing, and optoelectronic devices. Nianqiang Wu—for advancing the science and engineering of sensors for improvement of health and environmental sustainability and for pioneering contributions to the theory of plasmonic solar energy conversion, materials, and devices to secure new sources of energy. (continued on next page)

Exhibitors Special thanks to all the meeting sponsors and exhibitors who showcased the tools and equipment so critical to scientific research.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued from previous page) The ECS Chapters of Excellence Awards went to the ECS University of Washington Student Chapter and the ECS Munich Student Chapter, which consists of students from the Technical University of Munich and Munich University of Applied Sciences. The Outstanding Student Chapter Award went to the ECS University of Maryland Student Chapter.

ECS University of Washington Student Chapter (left to right): Matt Murbach, Johna Leddy, ECS president, Yanbo Qi, Jerry Chen, and Robert Masse.

There were 12 division and section awards: • Battery Division Technology Award was presented to Yang-Kook Sun of Hanyang University. • Battery Division Technology Award was presented to Jun Liu of Pacific Northwest National Laboratory. • Battery Division Research Award was presented to Ryoji Kanno of Tokyo Institute of Technology. • Battery Division Postdoctoral Associate Research Award, sponsored by MTI Corporation and the Jiang Family Foundation, was presented to Haegyeom Kim of Lawrence Berkeley National Laboratory. • Battery Division Postdoctoral Associate Research Award, sponsored by MTI Corporation and the Jiang Family Foundation, was presented to Kimberly See of the University of Illinois at Urbana-Champaign. • Battery Division Student Research Award was presented to Lin Ma of Dalhousie University. • Corrosion Division H. H. Uhlig Award was presented to Herman Terryn of Vrije Universiteit Brussel. • Corrosion Division Morris Cohen Graduate Student Award was presented to Mohsen Esmaily of Chalmers University of Technology. • Electrodeposition Division Research Award was presented to Stanko Brankovic of the University of Houston. • Electrodeposition Division Early Career Investigator Award was presented to Jiahua Zhu of the University of Akron. • High Temperature Materials Division J. Bruce Wagner, Jr. Award was presented to Cortney Kreller of Los Alamos National Laboratory. • Europe Section Heinz Gerischer Award was presented to Kazuhito Hashimoto of the University of Tokyo. (continued on page 18)

ECS Munich Student Chapter (left to right): Gregor Harzer, chapter secretary, Johna Leddy, ECS president, and Morten Wetjen, chapter treasurer. ECS Battery Division Chair Christopher Johnson (right) presented YangKook Sun (left) with the Battery Division Technology Award.

ECS University of Maryland Student Chapter (left to right): Steven Lacey, past chapter president, Johna Leddy, ECS president, Eric Wachsman, chapter advisor, and Patrick Owen Stanley, current chapter president. 16

ECS Battery Division Chair Christopher Johnson (right) presented Jun Liu (left) with the Battery Division Technology Award. The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Ryoji Kanno, winner of the Battery Division Research Award. ECS Corrosion Division Chair Sannakaisa Virtanen (right) presented Mohsen Esmaily (left) with the Corrosion Division Morris Cohen Graduate Student Award.

From left to right: Xiaoping Jiang of the MTI Corporation presented the Battery Division Postdoctoral Associate Research Award, sponsored by MTI Corporation and the Jiang Family Foundation, to Haegyeom Kim and Kimberly See alongside ECS Battery Division Chair Christopher Johnson.

Past ECS Electrodeposition Division Chair Elizabeth Podlaha-Murphy (right) presented Stanko Brankovic (left) with the Electrodeposition Division Research Award.

Lin Ma, winner of the Battery Division Student Research Award.

Past ECS Electrodeposition Division Chair Elizabeth Podlaha-Murphy (right) presented Jiahua Zhu (left) with the Electrodeposition Division Early Career Investigator Award.

ECS Corrosion Division Chair Sannakaisa Virtanen (right) presented Herman Terryn (left) with the Corrosion Division H. H. Uhlig Award. The Electrochemical Society Interface â&#x20AC;˘ Winter 2017 â&#x20AC;˘ www.electrochem.org

(continued from page 16)

Past ECS High Temperature Materials Division Chair Turgut Gur (right) presented Cortney Kreller (left) with the High Temperature Materials Division J. Bruce Wagner, Jr. Award.

Petr Vanýsek (right) presented Kazuhito Hashimoto (left) with the Europe Section Heinz Gerischer Award.

General Student Poster Session

Winners of the General Student Poster Session—front row (left to right): Sungyup Jung, Mariko Kadowaki, ECS President Johna Leddy, and Yubin Liu; back row (left to right): Hiroki Shiikuma, Oliver Harris, Travis Omasta, Abubakar Khaleed, and Saad Intikhab.

There were 95 submissions to the General Student Poster Session. The winners were: First Place – Electrochemical: Saad Intikhab, Drexel University, “Understanding the pH Dependence of the Reversible Hydrogen Reaction through Modified Low Index Pt Single Crystals” Second Place – Electrochemical: Sungyup Jung, The City College of New York, “Effects of Reaction Conditions on Electroreduction of Biomass-Derived Furfural and Its Side Reactions in Acidic Electrolyte” Third Place – Electrochemical: Travis Omasta, University of Connecticut, “Methanol Production – A Key Intermediate in the Electrochemical Interconversion of Organics to Chemicals and Fuels” First Place – Solid State: Yubin Liu, Kanagawa University, “Synthesis of Water-Resistant Thin TiOx Layer-Coated High18

Capacity LiNiaCobAl1-a-bO2 (a > 0.85) Cathode and Its Stable Charge/Discharge Cycle Cathode Performance to Apply a WaterBased Hybrid Polymer Binder to Li-Ion Batteries” Second Place – Solid State: Abubakar Khaleed, University of Pretoria, South Africa, “Solvothermal Preparation of Microspherical Flowerlike Ni(OH)2/Graphene Oxide Electrode for Electrochemical Capacitor Application” Honorable Mentions: Hiroki Shiikuma, Tokyo University of Science, “Dependence of Crystal Structure and Electronic Structures, Dielectric and Piezoelectric Properties on Composition for (K, Na)NbO3-(Bi, Na)TiO3;” Oliver Harris, Drexel University, “Understanding Capacity Fade Mechanisms in High-Voltage Lithium-Ion Batteries;” Mariko Kadowaki, Tohoku University, “Real-Time Microelectrochemical Observation of Very Early Stage of Pitting on Carbon Steel in Chloride Solution.” (continued on page 20) The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Scenes from the Meeting

The Electrochemical Society Interface â&#x20AC;˘ Winter 2017 â&#x20AC;˘ www.electrochem.org

(continued from page 18)

ECS Lecture with Steven Chu

Steven Chu gave the ECS Lecture at the 232nd ECS Meeting.

The ECS Lecture during the 232nd ECS Meeting in National Harbor, Maryland was delivered by Steven Chu. Chu is currently the William R. Kenan, Jr., Professor of Physics and Professor of Molecular & Cellular Physiology at Stanford. Previously, he served as U.S. Secretary of Energy under President Obama and was the corecipient of the 1997 Nobel Prize in Physics for his contribution to laser cooling and atom trapping. Chu’s ECS Lecture, “The Role of Electrochemistry in Our Transition to Sustainable Energy,” focused on the risks society is facing due to changing climate, the evolving energy landscape, and the role of electrochemistry in providing critical technological advances. During his lecture, Chu outlined the risks that modern society faces, which demand technological innovation to provide solutions. Namely, Chu stated that the changing climate poses significant risks to the global community. According to Chu, the Earth has warmed by an alarming one degree Celsius since 1975. “One degree Celsius does not sound like a lot, but just a couple of degrees warmer would make a dramatic difference,” Chu said. “If the Earth does warm by two degrees Celsius, Boston will be underwater.” Greenhouse gas emissions, such as carbon dioxide, have been linked to rising global temperatures. However, Chu believes that reducing carbon emissions alone will not solve this global crisis, citing that carbon dioxide could circulate in the atmosphere for up to 30,000 years. Because of this, much of the carbon dioxide emitted into the atmosphere will continue to pose a threat long after talks of capping emissions are finalized. In order to stay below the global two degrees Celsius temperature rise, Chu reported that the United Nations drew a red line at 2,900 billion tons of total cumulative emissions. However, he states that simply capping emissions will not address the underlying issue. “At the rate we’re going, even if we cap carbon emissions so there is no longer any increase in carbon or other greenhouse gasses,” Chu said, “we’ll go over that red line in 20 years.” The answer to addressing many of these issues, for Chu, is to change the energy landscape. Chu stated that, as the technologies to find and extract oil and gas become more efficient, more focus must be placed on innovative technological advances in renewables to not only offer a clean, efficient alternative, but also an economically competitive one. In addition, Chu believes the shift away from fossil fuels and toward renewable solutions will require a culture shift.

“We transitioned from the Stone Age to the Middle Ages, and nowadays when we look at stones on the ground we don’t shake our heads and say, ‘stranded assets,’” Chu said. “And so we need to get to a time and place where you don’t look at the oil and natural gas in the ground and say, ‘stranded assets.’ You say, ‘We’ve gone on to better things.’” Referencing a 2016 analysis by Lazard, “Leveled Cost of Energy Analysis 10.0,” Chu stated that the current landscape of renewable energy is optimistic. The unsubsidized cost of wind energy was shown to be between 32 and 62 dollars per megawatt hour, or three to six cents per kilowatt hour. Similarly, solar prices have continued to drop, falling by a factor of four within the last five years at 46 to 61 dollars per megawatt hour. According to Chu, continuing advances in the field will allow these prices to drop even further, making renewable energy technologies even more economically competitive. “There’s every expectation that, within a decade or less,” Chu said, “the cost could decline to two cents a kilowatt hour.” One of the keys to the advancement of renewable energy sources, Chu noted, lies in battery technology and other forms of energy storage. Chu discussed how, in the past few years, battery technology has advanced exponentially to open the door for electric vehicles (EVs) and beyond. “When the first EVs started to come out around 2006, they were at a very, very high cost. It was around $1,200 to $1,500 to develop a battery for an EV,” Chu said. “Then that price plummeted. Nowadays, it’s around $250 to $300 to manufacture an EV battery.” Chu noted that, while the EV industry continues to grow, it isn’t because EV prices are declining at an accelerated rate, like those of solar. Instead, he believes a rising awareness of environmental pollution to be the main driver behind the upsurge of EVs. But the impact of batteries expands far beyond EVs, and even beyond lithium-ion batteries, according to Chu. As battery paradigms continue to shift, Chu believes that younger technologies, such as lithium-silicon or lithium-metal batteries, will begin to overcome technological barriers as researchers continue work at a fundamental level. The interconnectivity of research efforts in the field, paired with the technology’s real world, practical applications, led Chu to his overall position that electrochemistry has immense potential to solve pressing global issues, specifically focused on the changing energy landscape. For Chu, one of the most promising ventures is carbon dioxide capture and reuse. He and his research partners are currently working on ways to split carbon dioxide, creating hydrogen as a usable product. From there, hydrocarbons can be developed, paving the way for the future of distributed large-scale energy and EV technologies alike. “We want to take cheap, clean energy, turn it into a chemical fuel, stick it in a tank, and then ship it. At that point, paired with the capture of CO2, we can being to really phase out fossil fuels,” Chu said. “I see electrochemistry at the heart of all of this.”

The audience during Chu’s lecture. 20

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

232nd ECS MEETING

1,259

495

Posters Thirty-Six

Total Presentations

Keynote Talks

644

Two Hundred SixTy-eigHT

Total Student Presentations

Student Posters

Six Hundred Fifty-Six Battery & Energy Storage Talks

ThIRTy

Energy/ Water Talks

335 PEFC Talks

53 Brain Talks

Division/Section Awards

Best Presentation Awards

TWO

Society Awards OpenCon

376

AWARDS

Invited Talks Student Oral Presentations

2,371

SEvEN Talks

Total Awards

Z01

Oral Talks

FourtyNine Symposia

566

TOTAL COUNTRIES

LARgEST SymPOSIA

STUDENT PRESENTATIONS

ALL PRESENTATIONS

National Harbor, MD

general Student Posters

FIFTy-FOUR

Number of Countries Represented

ThIRTyThREE Food Safety Sensor Talks

ELECTROChEmICAL ENERgy SUmmIT The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

116 TOTAL TALks

CANDIDAT NDIDATES ES FOR FOR SOCIE SOCIETTY Y OFFICE OFFICE CA The following are biographical sketches and candidacy statements of the nominated candidates for the annual election of ECS officers. The office not affected by this election is that of the Secretary.

Candidate for President

Candidates for Vice President

Yue Kuo is a Dow Professor in chemical engineering with a joint appointment in electrical engineering and materials science and engineering at Texas A&M University. He holds a Doctor of Engineering Science degree from Columbia University. Before joining Texas A&M University, he worked in the IBM T. J. Watson Research Center and Data General Semiconductor Division in Silicon Valley, where he conducted pioneering work on large area thin film transistor (TFT) technology, MOSFETs, reliability, Cu interconnects, high-k gate dielectric, nonvolatile memories, and a novel type of SSI-LED. In addition to his papers and inventions, his two-volume TFT books are widely used in universities and industry. His organizational honors include fellow of The Electrochemical Society, the ECS Gordon E. Moore Medal, and recognition by the ECS Electronics and Photonics Division. Kuo was an associate editor of the Journal of The Electrochemical Society and Electrochemical and Solid-State Letters (2003-2012) and a technical editor of the ECS Journal of Solid State Science and Technology and ECS Solid State Letters (2012-2015). In addition to his ample service with the ECS Electronics and Photonics Division, Kuo taught short courses, organized and chaired conferences, and continues to actively promote ECS overseas.

E. Jennings Taylor is chief technical officer and intellectual property director of Faraday Technology Inc., an electrochemical engineering company he founded in 1991. His vision was to explore pulse and pulse reverse electrolytic principles and shift the focus of electrochemical process technologies from chemical control, often involving hazardous electrolytes, to electric field control with robust, environmentally benign electrolytes. He has over 200 technical papers and about 45 U.S. and foreign patents. Taylor was recognized by the National Association of Surface Finishers for contributions to the field of pulse/pulse reverse surface finishing with the 2008 Blum Scientific Achievement Award and for contributions to the development of an environmentally friendly functional chromium plating process with the 2013 Presidential Green Chemistry Challenge Award. He is a fellow of The Electrochemical Society and the National Association of Surface Finishers. Taylor has a BA in chemistry from Wittenberg University and an MS and PhD in materials science from the University of Virginia. He obtained an MA in technology strategy and policy from Boston University and is admitted to the U.S. Patent & Trademark Office bar. Before founding Faraday Technology Inc., Taylor worked at International Nickel, Giner Inc., and Physical Sciences Inc. He has served on many National Science Foundation advisory committees and nonprofit boards, including Engineers on Deck, promoting STEM training for teachers and students. During his 38 years as an ECS member, Taylor chaired the ECS Boston Section and the Development and Sponsorship Committees and served as secretary and treasurer of the ECS Industrial Electrochemistry and Electrochemical Engineering Division. He currently serves as treasurer of ECS and cochair of the Free the Science Advisory Board. Taylor is active in organizing symposia directed towards pulse reverse electrolytic processes, electrochemical innovation, and the Bill and Melinda Gates water initiative. He presented an ECS tutorial titled “Intellectual Property for Electrochemical Scientists, Engineers, and Technologists” and coauthors a series of articles related to patent law in Interface.

Statement of Candidacy

ECS has been a premium professional society in electrochemistry and solid state science and technology for 115 years with a glorious history. During that period, we have made an extraordinary impact in academia and industry through publications, conferences, continuing education, and professional activities. ECS is an open society that owes its success to the extensive involvement of all members, including students. In order to remain vibrant and relevant to the rapid changes in science and technology, ECS has to continue its high level of service to members. Therefore, ECS offers open access publications and active member recruitment from academia, industry, and relevant government entities. ECS needs to continuously provide maximum benefits to its members, such as free high-quality publications, opportunities for professional connections and exposure, and international experience through paper presentations, committee service, symposium organization, and recognition through its honors and awards program. (continued on next page)

I am deeply honored to be nominated for the position of vice president of ECS. I understand and accept both the stewardship

Eric Wachsman is the director of the Maryland Energy Innovation Institute and the Crentz Centennial Chair in Energy Research with appointments in both the Materials Science and Chemical Engineering Departments at the University of Maryland. Prior to his time at the University of Maryland, he was the Rhines Chair Professor in materials science at the University of Florida and a senior scientist at SRI International. He received a PhD in materials science from Stanford University in 1990 and MS and BS degrees in chemical engineering from Stanford and the University of California at Berkeley, respectively. His research is focused on solid ion-conducting materials and electrocatalysts, including the development of solid oxide fuel cells and electrolysis cells, solid state batteries, ion-transport membranes, and solid state gas sensors; he has over 250 publications and 20 patents. He is a fellow of The Electrochemical Society (2008) and the American Ceramic Society (2012) and a member of the World Academy of Ceramics (2017). He is the recipient of the 2017 Carl Wagner Memorial Award (ECS), the 2014 Sir William Grove Award (International Association for Hydrogen Energy), the 2014 Pfeil Award (Institute of Materials, Minerals and Mining), the 2012 Fuel Cell Seminar Award, and the 2012 High Temperature Materials Division Outstanding Achievement Award (ECS). Wachsman joined ECS as a graduate student in 1989 and quickly became an active volunteer, chairing and serving on 10 committees, organizing 16 symposia, including the Gates Foundation-sponsored “Energy-Water Nexus” symposium, and chairing the ECS High Temperature Materials Division in 2006. He currently chairs the Interdisciplinary Science and Technology Subcommittee and the ECS National Capital Section. He also serves on the ECS Board of Directors, the Technical Affairs Committee, and the Symposium Planning Subcommittee. He has contributed to the next generation of electrochemists, having graduated 31 PhD and 28 MS students, supervised 22 postdocs and research scientists, and mentored several junior faculty, three of whom have gone on to receive ECS awards. His involvement with students includes founding and serving as faculty advisor for ECS student chapters at both the University of Florida and the University of Maryland. The ECS Maryland

(continued on next page)

(continued on page 24)

Statement of Candidacy

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Candidates for Treasurer Gessie Brisard received her PhD in 1990 from the Université de Sherbrooke. Upon completion of postdoctoral studies at Lawrence Berkeley National Laboratory, she joined her alma mater as an assistant professor in the Chemistry Department and became a full professor in 2004. She also served as vice dean of academia of the faculty of science from 2007 to 2010. Her knowledge and expertise on electrochemistry in nonaqueous solvents of the interfacial behavior of nonaqueous electrolytes, with application to lithium batteries and metal deposition in nonconventional media, have led to successful collaborations with the Institut de Recherche d’Hydro-Quebec and Alcan, the Canadian mining company and aluminum giant. Brisard became a student member of ECS in 1989; this move prepared her immediately for volunteer activity as a symposium organizer. She has since planned numerous symposia, both for the ECS Canada Section and for ECS biannual meetings. She has an extensive committee participation profile in the areas of governance, meetings, and publications, having served on the Council of Sections, the Society Meeting Committee, and Interface Advisory Board, for example. Brisard was a member of the ECS Board of Directors twice as the ECS Physical and Analytical Electrochemistry Division chair and led the ECS Canada Section to be recognized with the Gwendolyn B. Wood Section Excellence Award. She is currently a member of the Ways and Means Committee and is featured on ECS trading card 84.

Statement of Candidacy

I am deeply touched and delighted to be considered for the ECS treasurer position. Since my early graduate school days and throughout my professional life, I have been involved and attached to the Society; it has been, and still is, a worthwhile experience. For almost three decades now, I have witnessed Society efforts to support and encourage member activities (including those on the student level), sponsor highprofile research dissemination, sustain an excellent level in our scientific publications, and achieve constant innovation in our meetings—all this in a mission to promote and advance the various fields of electrochemistry and solid state science and technology. A healthy financial situation provided for the resulting success. As treasurer and member of the ECS Executive Committee, I will ensure that ECS remains financially viable and able to extend the best member benefits, guide students who hold the Society’s future, and ensure relevance through initiatives such as Free (continued on next page)

Yue Kuo

Boryann Liaw is manager of the Energy Storage and Advanced Vehicles Department at Idaho National Laboratory. The department operates the stateof-the-art Battery Test Center, the Non- dest r uct ive Battery Evaluation Laboratory, and the Electric Vehicle Infrastructure Laboratory. Its researchers conduct reliability, safety, and failure analyses of energy storage systems, advanced vehicles, and charging infrastructure and equipment. Before joining Idaho National Laboratory, Liaw was a specialist and tenured faculty member at the Hawaii Natural Energy Institute of the University of Hawaii at Manoa. There, he focused on advanced power source systems for vehicle and energy storage applications. Liaw received his bachelor’s degree in chemistry from National Tsinghua University in Taiwan, his master’s degree in chemistry from the University of Georgia, and his doctorate in materials science and engineering from Stanford University. He conducted his postdoctoral fellowship research at the Max Planck Institute for Solid State Research in Stuttgart, Germany. For the past three decades, Liaw has been involved in R&D projects related to electric and hybrid vehicle evaluation and advanced battery diagnostics and prognostics. His major research activities comprise laboratory and real-life battery and vehicle testing, data collection and analysis, battery modeling and simulation, battery performance and life prediction, battery rapid charging technology development, and battery diagnoses and prognoses. Liaw has coauthored more than 150 technical papers, 7 book chapters, and 8 patents and patent applications. He is a fellow of The Electrochemical Society and has served as chair of the ECS Battery Division, as an associate editor of the Journal of The Electrochemical Society, as a member of multiple editorial boards, and as a member of the ECS Meetings Subcommittee.

Statement of Candidacy

The Electrochemical Society is significantly transforming its publication practices under the grand vision of Free the Science. Stewardship of the board, the officers, and the membership body are all critical at this stage of transformation. The sustainability of ECS journals, ECS’s respective research communities, and the Society itself requires strong support from its members and volunteer leadership. I am interested in serving in a capacity that can provide such support and assist in this important transformation. As treasurer, I welcome the chance to seek and embrace

(continued from previous page)

As president, I will maintain and advance our society’s reputation. In addition to smoothly and successfully achieving the goal of the Free the Science initiative, I will enhance ECS’s global impact in our key program areas. E. Jennings Taylor (continued from previous page)

and fiduciary responsibilities associated with being a member of the ECS Executive Committee and the office of vice president. Electrochemical and solid state science and engineering play critically important roles in energy, water, environment, and manufacturing. The ECS membership has the breadth and depth to conceive innovative solutions to technical challenges in these areas based on its diversity and the networking and information sharing enabled by our meetings and publications. Moving forward, we must maintain our meetings’ quality and the integrity of our publications, increase the opportunities and platforms for information sharing, and continue to provide meaningful engagement of our diverse membership as well as our younger members, who are the future of ECS. Open access is the wave of the future, and its benefits include increased downloads and citations of articles relative to those available by subscription. Open access is aligned with our mission to cultivate and disseminate electrochemical and solid state knowledge to our stakeholders and the wider scientific community, and it will increase excitement and involvement in ECS. Our subscriptionbased revenue model is challenged by this move. As an entrepreneur, I believe that residing in every challenge is an opportunity to define a new and better future. We have laid considerable groundwork to transition to revenues based on a variety of sources, including gifts, investments, and minimal article processing charges, as well as cost savings in our publications and other areas. I am encouraged by our competitive position as the low-cost producer of high-quality publications. Creative solutions to the challenges faced by ECS can only be defined by input from our membership. I am committed to listening to the ideas of members and ECS staff and to increasing participation in our committees. I have been a member of ECS for nearly 40 years, and the Society has had a profound impact on my career. I believe that my entrepreneurial experience will provide a useful perspective regarding ECS governance and financial and strategic issues. I am passionate about innovation, the advancement of electrochemical and solid state science, and student education. If elected, I will diligently perform my duties as a board member and tirelessly support our strategic direction.

(continued on next page)

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued from previous page) Eric Wachsman (continued from page 22)

Student Chapter won the Outstanding Student Chapter Award in 2013 and 2017 and the Chapter of Excellence Award in 2014, 2015, and 2016.

Statement of Candidacy

I have been an active member of ECS on both division and society levels and am proud to have served multiple terms on the ECS Board of Directors. My involvement has given me an understanding of the Society’s operations, successes, and the future challenges. Importantly, it has also provided me with an understanding of ECS’s role in supporting its members, the advancement of science, and our contributions to society at large. We live in a rapidly changing world with major societal issues, such as the limited availability of affordable and sustainable energy, clean water and air, food, and healthcare. The solutions to these issues are at the nexus of science and technology and are becoming more electrochemical in nature. As such, developing symposia that address these grand challenges has

been the focus of my efforts as chair of the Interdisciplinary Science and Technology Subcommittee. As a scientific society, ECS also faces challenges of declining membership and publication revenues, and many of our members face challenges in obtaining adequate research funding. Therefore, if elected vice president, my goals would be to continue to expand ECS’s participation in addressing major societal issues, but also to provide the best possible benefits to our members. We as a scientific society need to not only Free the Science, but also partner with our sister societies to stand up for science. We are not policy makers, but we should make every effort to ensure that policy makers base their decisions on the best available science. Moreover, we should invite more policy makers and funding agency representatives to ECS meetings to provide an opportunity for dialogue as well as an opportunity for our members to learn of new funding opportunities and trends. We need to continue to increase the impact and maintain the high quality of ECS publications while also giving greater free access as a membership benefit. Finally, our student members are the future of our society, and every effort must be made for them to decide, as I did nearly 30 years ago, to make ECS their scientific home.

Gessie Brisard (continued from previous page)

the Science. ECS’s international reputation provides stable ground to continue to attract generous sponsors and encourage donors, individual and industrial, to contribute to Society activities. I pledge to work with you, my fellow members of the Society, and our volunteer leadership to further establish the best financial course and secure the future of the organization. ECS has been driven by committed individuals for the last 115 years, and as treasurer, it will be my honor to continue this tradition. Boryann Liaw (continued from previous page)

new revenue-generating opportunities that will complement the current changes. I believe the fiscal health and strength of ECS is key to its future success and sustainability. It is my hope that, by serving as treasurer, I will be able to contribute a humble effort to benefit the Society in this transition.

PLUS Join the movement! Upgrade to ECS Plus and receive:

Access to all of ECS’s top-ranking, peer-reviewed journal content and more in the ECS Digitial Library.

FREE open access publishing in ECS journals through UNLIMITED article credits for authors from subscribing institutions.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

The best answers come out of the blue...

Special Meeting Section l NATIONAL HARBOR, MD

Battery Testers

High Current Boosters

Potentiostats

Accessories

Full range of E-Chem products available at:

www.bio-logic.net

The Electrochemical Society Interface • Fall 2017 • www.electrochem.org

SOCIE T Y NE WS Focus on Focus Issues … ECS publishes focus issues of the Journal of The Electrochemical Society (JES) and the ECS Journal of Solid State Science and Technology (JSS) that highlight scientific and technological areas of current interest and future promise. These issues are handled by a prestigious group of ECS technical editors and guest editors, and all submissions undergo the same rigorous peer review as papers in the regular issues. Beginning in 2017, all focus issue papers are open access at no cost to the authors. ECS is waiving the Article Processing Charge for all authors of focus issue papers as part of the Society’s ongoing Free the Science initiative.

Current and Upcoming Focus Issues The following focus issues are currently in production with many papers already published in the ECS Digital Library (http://ecsdl.org). • • • • •

JSS Focus Issue on GaN-Based Electronics for Power, RF, and Rad-Hard Applications JSS Focus Issue on Visible and Infrared Phosphor Research and Applications JES Focus Issue on Lithium Sulfur Batteries, Materials, Mechanisms, Modeling, and Applications JES Focus Issue on Processes at the Semiconductor Solution Interface JES Focus Issue on Proton Exchange Membrane Fuel Cell Durability

The following focus issues are open for submissions. Manuscripts may be submitted at http://ecsjournals.msubmit.net. • JES Focus Issue on Ubiquitious Sensors and Systems for IoT • JSS Focus Issue on Semiconductor-Based Sensors for Application to Vapors, Chemicals, Biological Species, and Medical Diagnosis The following focus issue is in the planning stages. Look for the call for papers to come out soon. • JES Focus Issue on the Brain and Electrochemistry, in Honor of Mark Wightman and Christian Amatore

For more info visit:

www.electrochem.org/focus

ORCID ID TO BECOME A REQUIREMENT Why make this requirement? ORCID facilitates recognition, discovery, connectivity, and trust within the highly mobile global research infrastructure. It enables publishers to provide more efficient and accessible service while ensuring that researchers’ work is accurately attributed and conveniently documented. As a leading, nonprofit scientific publisher, ECS is in a singular position to expand ORCID usage and enhance the connectedness of researchers worldwide. By promoting the use of ORCID, ECS helps advance the movement toward greater openness, discoverability, and accessibility across the fast-moving, digitally oriented global research community. 26

As of January 1, 2018, ECS will require all corresponding authors to have an ORCID iD in order to submit to the Journal of The Electrochemical Society or the ECS Journal of Solid State Science and Technology. ORCID iDs will be published in accepted articles and included in articles’ metadata to improve content discoverability and citation. ECS has published numerous blog posts about ORCID and its benefits (www.electrochem.org/redcat-blog/tag/orcid), but here’s the rundown. Your ORCID iD will: • distinguish you from other researchers • ensure your research and activities are properly attributed • connect you with your contributions and affiliations • improve recognition and discoverability • reduce the need for repetitive form-filling • generate an easily accessible digital CV • integrate with many institutions, funders, and publishers • persist throughout your lifetime

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

Q&A with Associate Editor Stephen Maldonado Stephen Maldonado is an associate professor at the University of Michigan, where he leads a research group that focuses on the study of heterogeneous charge transfer processes relevant to the fields of electronics, chemical sensing, and energy conversion/storage technologies. He was recently reappointed as an associate editor for the Journal of The Electrochemical Society (JES) in the area of physical and analytical electrochemistry, electrocatalysis, and photoelectrochemistry. When did you become an ECS associate editor? What made you pursue an editorial role with ECS? I started my time as an ECS associate editor in 2014. I pursued the opportunity for two different reasons. The minor reason was that I was genuinely curious about the “sausagemaking” process of accepting/rejecting a paper. That is, as an author, I had prepared and submitted plenty of papers, but I had little idea about the other side of it. I had reviewed plenty of papers, too, but how those reviews factored into the final fate of the submissions was a mystery. The major reason, though, was that electrochemistry has remained a principal aspect of my adult life. I got into science because, at a fundamental level, I thought electrochemistry was cool. Accordingly, my interests were aligned with ECS at the start, and this has been a major influence on my professional development. After getting tenure, I felt the time was right to give back to this community. So, when I was asked to consider the position, I jumped at the chance. What separates ECS journals from others in the field? I love the fact that ECS is moving to a true open access model. The Free the Science initiative exactly represents what sets ECS apart from other publishers. We are a Society that cares about publicizing and maintaining our discipline. Publication by ECS is not profit driven; it’s science driven.

How important is the peer review process to the integrity of scholarly publishing? Essential. Without peer review, there is no value in scientific reporting. Vetting and reviewing are essential to legitimize the findings. It doesn’t mean that the interpretations are right or that a given study is without flaw, but it does mean that the work has passed some basic level of scrutiny. Without peer review, the distinction between objective findings and subjective messaging becomes indistinguishable. How could opening access to research help bolster innovation? A personal scientific motivation of mine is to enable the realization of semiconductor technologies with the simplest infrastructure possible. Open access is complementary to that concept. If as many people as possible have access and can contribute to the scientific literature, then the probability of idea advancement increases. What role does electrochemistry have in solving some of society’s most pressing issues? My personal belief is that simplifying the requirements for manufacturing existing and future technologies is impactful. For example, an electrochemical process that yields highquality silicon directly from raw silica has the potential to revolutionize the energy and electronic industries. Doing that would go a long way toward making sure everyone on this planet has access to cheap electricity and basic technology. What has enabled JES to continuously publish since 1902? What do you think has been the journal’s key to success? Scientists! At the end of the day, the fate of JES and any other journal is dictated by scientists performing quality research and the value society places on their work. The long history of JES and the continued interest in its topics are testaments to the role electrochemistry plays in modern society. As long as society finds value in electrochemical technologies, JES will be successful. Stephen Maldonado may be reached at smald@umich.edu.

In the

• The spring 2018 issue of Interface will be a special issue focused on the theme of Solar Hydrogen. Guest edited by John Weidner, the issue will feature the following technical articles (titles are tentative): “H2@Scale: Energy System-Side Benefits of Increased H2 Implementation,” by Brian Pivovar; “Thermochemical Cycles for Solar-Hydrogen Production,” by John Weidner, John Staser, Max Gorensek, and Claudio Corgnale; “Solar Photovoltaics,” by Vaidyanathan (Ravi) Subramanian; and an as yet untitled article by Winston V. Schoenfeld and Kristopher Davis. • E. J. Taylor and Maria Inman will again write about intellectual property and patent issues as part of the continuing series of excellent and informative articles by these authors.

issue of

• ECS Spring 2018 Meeting in Seattle. The spring issue will feature a special section on the upcoming ECS meeting, which looks to be one of the largest spring meetings ever held. Anticipate over 2,500 presentations at the meeting. The speaker delivering the ECS Lecture will be Miguel A. Nicolelis, the founder of Duke Univesity’s Center for Neuroengineering. Early-bird deadline for meeting registration and hotel reservations is April 9, 2018. • Tech Highlights continues to provide readers with free access to some of the most interesting papers published in the ECS journals. • Don’t miss the next edition of Websites of Note, Interface’s regular look at interesting websites.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

Q&A with Associate Editor Minhua Shao Minhua Shao is an associate professor at the Hong Kong University of Science and Technology, where he leads a research group pursuing work in advanced material and electrochemical energy technologies. Shao’s current work focuses on electrocatalysis, fuel cells, lithium-ion batteries, lithium-air batteries, carbon dioxide reduction, and water splitting. Shao was recently named an associate editor of the Journal of The Electrochemical Society (JES) in the area of fuel cells, electrolyzers, and energy conversion. What do you hope to accomplish in your new role as JES associate editor? As an associate editor, I hope to accelerate the manuscripthandling process by identifying suitable reviewers and making fair decisions. I also hope to promote the journal at conferences and among peers, attracting high-quality manuscripts. How has scholarly publishing evolved throughout your career? Scholarly publishing has changed significantly in the past two decades. Now researchers have many more choices on which journals to publish their results. The adoption of the socalled impact factor in assessing the quality of journals/papers has misled the scientific community. More seriously, there is a trend that scholarly publishing is more of a business than a platform for sharing research results.

Fergus Reappointed ECST Editor Jeffrey W. Fergus has recently been reappointed editor of ECS Transactions (ECST) for a threeyear period. After receiving his PhD from the University of Pennsylvania and a postdoctoral appointment from the University of Notre Dame, Fergus joined the faculty at Auburn University, where he is currently a professor of materials engineering and the associate dean for program assessment and graduate studies in the Samuel Ginn College of Engineering. Fergus has demonstrated a great capacity for leadership within the Society. In addition to organizing symposia, serving on multiple committees, and establishing the Auburn University Student Chapter, he has served as the chair of the ECS High Temperature Materials Division, the Education Committee, and the ECS Georgia Section. The editor of ECST since 2013, Fergus is enthusiastic to extend the publication’s reach in bold new directions. “One important goal will be to transition ECST to best complement implementation of ECSarXiv and promote the dissemination of research results among the electrochemical and solid state science community,” Fergus says. ECSarXiv, the Society’s forthcoming preprint server, developed in partnership with the Center for Open Science, will be launched in 2018. “The nature of scientific publishing is changing,” Fergus says. “I look forward to adapting ECST policies and procedures to align with these changes.”

Why is the peer review process so important in scholarly publishing? Peer review is an irreplaceable process in scholarly publishing. It minimizes the possibility of reporting wrong results, misinterpretations, and unsupported claims. It is also a powerful tool to control the quality of a journal. How has open access impacted scholarly communications? More and more new scientific journals choose open access by charging publishing fees instead of subscription fees to cover the publishing cost. This new publication model certainly has attracted a considerable amount of manuscripts for various reasons. Even some traditional journals offer an open access option. In my view, open access will be the future of scientific publishing. Why should authors publish in ECS journals? ECS journals have gained their reputations since the establishment of The Electrochemical Society in 1902. A lot of major breakthroughs in electrochemistry and electrochemical engineering were first reported in ECS journals. When I started my graduate studies in corrosion at Xiamen University back in the early 2000s, the first thing we did every month was go to the library and check out the new issue of JES. For more than 100 years, ECS journals have maintained an editorial board containing responsible experts who have assured the high quality of publications. Minhua Shao may be reached at kemshao@ust.hk.

Associate Editor Scott Lillard Reappointed Scott Lillard has recently been reappointed as an associate editor of the Journal of The Electrochemical Society (JES) for a three-year period. He specializes in the corrosion science and technology topical interest area. Lillard is the Professor & Carboline Endowed Chair in Corrosion at the University of Akron, where he played an instrumental role in establishing the university’s corrosion engineering program, the first program in the nation to offer a baccalaureate degree in the field. Lillard was first appointed to the JES Editorial Board in 2015. Read more about his work, goals, and passion for exceptional customer service in the peer review process in the fall 2015 issue of Interface.

Jeff Fergus may be reached at jwfergus@eng.auburn.edu.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

Division News High Temperature Materials Division At the 232nd ECS Meeting in National Harbor, the ECS High Temperature Materials Division celebrated the scientific accomplishments of several of its members recognized by their peers. These celebrations included the presentation of ECS’s prestigious Carl Wagner Memorial Award to Eric Wachsman of the University of Maryland, the induction of Scott Barnett of Northwestern University, and Joachim Maier of Max Planck Institute in Stuttgart, Germany as ECS fellows, and the presentation of the J. Bruce Wagner, Jr. Young Investigator Award of the ECS High Temperature Materials Division to Cortney Kreller of Los Alamos National Laboratory. Wachsman and Kreller both presented their award talks at the “Ionic and Mixed Conduction Ceramics 11” symposium in National Harbor. (See photographs of the award winners in the “Meeting Highlights” section of this issue of Interface.)

Also, the ECS High Temperature Materials Division recently instated the Subhash Singhal Award, which will be given every two years to a qualified researcher recognized for her/his impactful contributions in the general areas of solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs). The award was established to recognize Singhal’s long-lasting contributions to the science and technology of solid oxide fuel cells as well as the great success and longevity of the SOFC symposia series that he initiated nearly three decades ago, for which he served as organizer and cochair throughout the years since.

Dielectric Science and Technology Division The Dielectric Science and Technology Division Thomas D. Callinan Award was established in 1967 to encourage excellence in dielectric investigations, to encourage the preparation of high-quality science and technology papers and patents, and to recognize outstanding contributions to the field of dielectric science and technology. For the purpose of this award, dielectric science and technology is defined as that area of knowledge which deals with the physics and chemistry of dielectric materials as well as the mechanisms and operation of devices in which electrical energy can be stored or insulated in electrical or electronic equipment. The 2017 award recipient was Hiroshi Iwai from Tokyo Institute of Technology. He received the award for his contributions to the thinning of the gate dielectrics for MOSFETs until 0.4 nm EOT. Iwai was acknowledged at the division business meeting on Sunday, May 28, 2017 at the spring ECS meeting in New Orleans. Yaw Obeng, chair of the division, presented him with the award plaque and check for $1,500. On Monday, May 29, 2017, Iwai presented his award lecture, “Dielectrics for MOS Integrated Circuits.” The ECS Dielectric Science and Technology Division sponsored the symposium on “Semiconductors, Dielectrics, and Metals for Nanoelectronics 15: In Memory of Samares Kar” at the 232nd ECS Meeting in National Harbor, Maryland, October 1-5, 2017. Kar, who was a founding coorganizer of the symposium on “Physics and Technology of High-k Gate Dielectrics” held in 2002, passed away in January 2017. His obituary was published in the spring 2017 issue of Interface. To commemorate Kar, the symposium’s organizers invited all the past invited speakers of the symposium, and an overwhelming response was received. Many of the speakers who presented at the first symposium of this series at the 202nd ECS Meeting in Salt Lake City in 2002 were present. A group picture was taken at the beginning of the symposium with some of the participants at National Harbor.

From left to right: Past ECS Dielectric Science and Technology Division Chair Durga Misra, 2017 Dielectric Science and Technology Thomas D. Callinan Award winner Hiroshi Iwai, and current ECS Dielectric Science and Technology Division Chair Yaw Obeng.

Past invited speakers gathered at the symposium on “Semiconductors, Dielectrics, and Metals for Nanoelectronics 15: In Memory of Samares Kar” at the 232nd ECS Meeting in National Harbor—back row (left to right): Dmitriy Marinskiy, Gennadi Bersuker, Dolf Landeer, Yaw Obeng, Robert Wallace, Paul Hurley, Sushant Sonde, and Navakanta Bhat; front row (left to right): Stefan De Gendt, Zia Karim, Durga Misra, Hiroshi Iwai, unidentified, and Susanne Hoffmann-Eifert.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

ECS Division Contacts High Temperature Materials

Battery

Christopher Johnson, Chair Argonne National Laboratory johnsoncs@cmt.anl.gov • 630.252.4787 (US) Marca Doeff, Vice Chair Shirley Meng, Secretary Brett Lucht, Treasurer Doron Aurbach, Journals Editorial Board Representative Corrosion

Sannakaisa Virtanen, Chair Friedrich-Alexander-Universität Erlangen-Nürnberg virtanen@ww.uni-erlangen.de • +49 09131/85-27577 (DE) Masayuki Itagaki, Vice Chair James Nöel, Secretary/Treasurer Gerald Frankel, Journals Editorial Board Representative Dielectric Science and Technology

Yaw Obeng, Chair National Institute of Standards and Technology yaw.obeng@nist.gov • 301.975.8093 (US) Vimal Chaitanya, Vice Chair Peter Mascher, Secretary Uroš Cvelbar, Treasurer Stefan De Gendt, Journals Editorial Board Representative Electrodeposition

Stanko Brankovic, Chair University of Houston srbrankovic@uh.edu • 713.743.4409 (US) Philippe Vereecken, Vice Chair Natasa Vasiljevic, Secretary Luca Magagnin, Treasurer Charles Hussey, Journals Editorial Board Representative Electronics and Photonics

Colm O’Dwyer, Chair University College Cork c.odwyer@ucc.ie • +353 863.958373 (IE) Junichi Murota, Vice Chair Robert Lynch, 2nd Vice Chair Soohwan Jang, Secretary Yu-Lin Wang, Treasurer Fan Ren, Journals Editorial Board Representative Energy Technology

Andy Herring, Chair Colorado School of Mines aherring@mines.edu • 303.384.2082 (US) Vaidyanathan Subramanian, Vice Chair William Mustain, Secretary Katherine Ayers, Treasurer Thomas Fuller, Journals Editorial Board Representative

Greg Jackson, Chair Colorado School of Mines gsjackso@mines.edu • 303.273.3609 (US) Paul Gannon, Sr. Vice Chair Sean Bishop, Jr. Vice Chair Cortney Kreller, Secretary/Treasurer Raymond Gorte, Journals Editorial Board Representative

Industrial Electrochemistry and Electrochemical Engineering

Douglas Riemer, Chair Hutchinson Technology Inc. riemerdp@hotmail.com • 952.442.9781 (US) John Staser, Vice Chair Shrisudersan (Sudha) Jayaraman, Secretary/Treasurer Venkat Subramanian, Journals Editorial Board Representative Luminescence and Display Materials

Mikhail Brik, Chair University of Tartu brik@fi.tartu.ee • + 372 737.4751 (EE) Jakoah Brgoch, Vice Chair Rong-Jun Xie, Secretary/Treasurer Kailash Mishra, Journals Editorial Board Representative Nanocarbons

Slava Rotkin Pennsylvania State University rotkin@psu.edu • 814.863.3087 (US) Hiroshi Imahori, Vice Chair Olga Boltalina, Secretary R. Bruce Weisman, Treasurer Francis D’Souza, Journals Editorial Board Representative Organic and Biological Electrochemistry

Graham Cheek, Chair United States Naval Academy cheek@usna.edu • 410.293.6625 (US) Diane Smith, Vice Chair Sadagopan Krishnan, Secretary/Treasurer Janine Mauzeroll, Journals Editorial Board Representative Physical and Analytical Electrochemistry

Alice Suroviec Berry College asuroviec@berry.edu • 706.238.5869 (US) Petr Vanýsek, Vice Chair Andrew Hillier, Secretary Stephen Paddison, Treasurer David Cliffel, Journals Editorial Board Representative Sensor

Nianqiang (Nick) Wu, Chair West Virginia University nick.wu@mail.wvu.edu • 304.293.3111 (US) Ajit Khosla, Vice Chair Jessica Koehne, Secretary Larry Nagahara, Treasurer Rangachary Mukundan, Journals Editorial Board Representative 30

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

New Division Officers New officers for the fall 2017 – fall 2019 terms have been elected for the following divisions:

Electrodeposition Division

Chair Stanko Brankovic, University of Houston Vice Chair Philippe Vereecken, IMEC and Katholieke Universiteit Leuven Secretary Natasa Vasiljevic, University of Bristol Treasurer Luca Magagnin, Politecnico di Milano Members-at-Large Rohan Akolkar, Case Western Reserve University Antoine Allanore, Massachusetts Institute of Technology Andreas Bund, Technische Universität Ilmenau Toshiyuki Nohira, Kyoto University

High Temperature Materials Division

Chair Greg Jackson, Colorado School of Mines Vice Chair Paul Gannon, Montana State University Bozeman Jr. Vice Chair Sean Bishop, Redox Power Systems Secretary/Treasurer Cortney Kreller, Los Alamos National Laboratory Members-at-Large Stuart Adler, University of Washington Ainara Aguadero, Imperial College London Mark Allendorf, Sandia National Laboratories Fanglin Chen, University of South Carolina Zhe Cheng, Florida International University Koichi Eguchi, Kyoto University Jeffrey Fergus, Auburn University Fernando Garzon, University of New Mexico Srikanth Gopalan, Boston University Ellen Ivers-Tiffee, Karlsruhe Institute of Technology Tatsuya Kawada, Tohoku University

Xingbo Liu, West Virginia University Torsten Markus, Mannheim University of Applied Sciences Nguyen Minh, University of California San Diego Mogens Mogensen, Technical University of Denmark Jason Nicholas, Michigan State University Elizabeth Opila, University of Virginia Nicola Perry, Kyusha University Sandrine Ricote, Colorado School of Mines Emily Ryan, Boston University Subhash Singhal, Pacific Northwest National Laboratory Enrico Traversa, University of Electronic Science and Technology of China Harry Tuller, Massachusetts Institute of Technology Anil Virkar, University of Utah Eric Wachsman, University of Maryland Werner Weppner, Christian-Albrechts-Universität zu Kiel Shu Yamaguchi, University of Tokyo Bilge Yildiz, Massachusetts Institute of Technology Xiao-Dong Zhou, University of Louisiana at Lafayette

Luminescence and Display Materials Division

Chair Mikhail Brik, University of Tartu Vice Chair Jakoah Brgoch, University of Houston Secretary/Treasurer Rong-Jun Xie, National Institute for Materials Science Library Members-at-Large Tetsuhiko Isobe, Keio University Ru-Shi Liu, National Taiwan University Joanna McKittrick, University of California San Diego Kazuyoshi Ogasawara, Kwansei Gakuin University Alan Piquette, Osram Sylvania Dirk Poelman, Universiteit Ghent Alok Srivastava, General Electric Global Research Eugeniusz Zych, Uniwersytet Wroclawski

ECS Collections of Interface Articles Visit the ECS Digital Library (DL) now to access recently created collections of articles from the following recurring columns in Interface: • From the Editor • From the President • Pennington Corner

• ECS Classics • Currents • The Chalkboard

• Websites of Note • Tech Highlights

More collections will be created and more articles will be added as new issues are published and more back issues are put online.

http://interface.ecsdl.org/cgi/collection

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

Advancement News Members Find Special Ways to Support ECS For the past two years, ECS has stepped up its fundraising ambitions to support Free the Science, ECS’s initiative to move toward a future that embraces open science to further advance research in our fields. This is a long-term vision for transformative change in the traditional models of communicating scholarly research and a response to the inevitable changes taking place in the publishing industry. This new reality has stimulated some longtime ECS members to get creative with their philanthropy. This year it all started with a group in the ECS Corrosion Division who wanted to honor the late Hugh Isaacs. Donors came together to create a collection of Isaacs’s work in the Journal of The Electrochemical Society (JES) in the ECS Digital Library. Anchored by a gift from Isaacs’s widow, Sheila, the support put all 45 JES papers in the collection. Sheila joined her late husband’s colleagues for a celebration in his honor in National Harbor in October. At the 231st ECS Meeting in New Orleans, Shimshon Gottesfeld reconnected with many of his old colleagues and attended the special luncheon for fellows and leaders. There he learned about why ECS was pursuing Free the Science and how important it was to more widely share knowledge. With four papers on ECS’s “Top 50 Most Cited List,” Gottesfeld decided to give back the grant he received to be a symposium speaker to support ECS’s efforts.

Another group of friends got together this year to create the Glenn E. Stoner Collection in the ECS Digital Library. It all came about when Pat Moran and E. J. Taylor were talking about the importance of the Free the Science initiative to the future of ECS. Moran is a professor at the U.S. Naval Academy and a member of the Free the Science Advisory Board, and Taylor is the ECS treasurer and cochair of the Free the Science Advisory Board. Moran suggested establishing the Stoner Collection in the ECS Digital Library in honor of their graduate advisor, Glenn E. Stoner. Spearheaded by a cohort of former classmates from the University of Virginia (UVA), including Paul Natishan and UVA professor Rob Kelly, the team began calling friends and companies that were influenced by the teaching and work of Stoner. They received a great response, raising almost $25,000 to not only create the collection in the digital library but to also provide free access (i.e., freeing the science) to Stoner’s papers. To announce the collection, a surprise party was planned at the National Harbor meeting, generously supported by the Center for Electrochemical Science and Engineering at the University of Virginia under the codirection of professors John Scully and Rob Kelly. Stoner, the recipient of the 2000 Henry B. Linford Award for Distinguished Teaching, clearly had a profound impact on the lives

From left to right: Mary Ryan, Martin Kendig, Patrik Schmuki, Sheila Isaacs, Gerald Frankel, Lucy Oblonsky, Sannakaisa Virtanen, and Anthony Aldykiewicz.

From left to right: E. J. Taylor, Glenn Stoner, Pat Moran, Rob Kelly, and Paul Natishan at the 232nd ECS Meeting in National Harbor.

From left to right: Marcia Gottesfeld, Shimshon Gottesfeld, and ECS Director of Development Karla Cosgriff at the 232nd ECS Meeting in National Harbor.

From left to right: Brian, Glenn, and Marlene Stoner at the 232nd ECS Meeting in National Harbor.

(continued on next page)

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS (continued from previous page) of many academic, government, and industry leaders, as 36 people attended the event. “I’m really pleased with the creation of the Glenn E. Stoner Collection,” said Taylor. “Not only are we honoring our great friend and mentor, Glenn, but we’re providing important support to Free the Science. After so many years of involvement with ECS, it was great to see our community pull together for this special project. We enticed many people to come to the event who haven’t been to an ECS meeting in years, and they were reinvigorated by the content and breadth of our meeting. Truly a win-win for everyone involved.” Making a gift to honor a mentor was also the motivation behind another gift pledged for a Leadership Collection in the ECS Digital Library. The anonymous donor is supporting Free the Science by establishing a collection in JES to honor Distinguished University Professor Chung-Chiun Liu of Case Western Reserve University. Forgoing a stipend in order to support Free the Science was also the impetus for several gifts made recently by K. M. Abraham. Abraham has turned back royalty checks from his editing work on Lithium Batteries: Advanced Technologies and Applications. These gifts, in addition to the establishment of the K. M. Abraham Travel Grant Award, make Abraham one of ECS’s most ardent and generous supporters. ECS is grateful for the creative commitment that all of these donors have demonstrated. If you would like more information on how you can establish collections or mobilize your colleagues to take on a project that will help secure ECS’s future, please contact the ECS Development Department at 609.737.1902 ext. 122 or development@electrochem.org.

From left to right: Pankaj Alabonia (North Carolina A&T State University), K. M. Abraham, and Jiefu Yin (Stony Brook University).

The Glenn E. Stoner Collection in the Journal of The Electrochemical Society was created in 2017 with generous gifts from Susan and John Beatty Bio-Logic USA Charles Boyer Rudolph and Catherine Buchheit Donna and George Cahen Edward Colvin Rebecca and Craig Davidson Bill and Karen Eggers Gerald and June Frankel Richard and Margaret Gangloff Robert Glass Jeffrey Glass Joel Hansen Derek Johnson Robert and Heather Kelly Angela and Pat Moran Terry and Paul Natishan Jeffrey Poirier Kelly and David Reichert Scribner Associates Pat and Louie Scribner Hazel and John Scully Stephen Sharp Stephen Smith Gery and Margaret Stafford Jennings and Barbara Taylor University of Virginia’s Center for Electrochemical Science and Engineering As part of ECS’s mission to Free the Science, articles in the Stoner Collection are now freely accessible to anyone using the ECS Digital Library.

How to Give to ECS There are many ways to give to ECS and we hope you will consider one of these ideas: • Donate $115 to ECS in honor of our 115th Anniversary • Make a gift of stock to ECS by contacting development@electrochem.org • Give a gift at checkout time when you’re registering for your next ECS meeting

Visit

• Donate your stipend, royalties, or speaker fees to ECS • Make a small recurring gift each month • Make a planned gift by leaving a bequest in your will, transferring life insurance, or making an IRA charitable rollover. All planned gifts are recognized through the Carl Hering Legacy Circle

www.electrochem.org and click the red DONATE button to begin. Contact development@electrochem.org

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

Free the Science News ECS OpenCon 2017: Exploring Ideas for Next Generation Research As part of its efforts to socialize the Free the Science initiative, ECS hosted its first ever satellite OpenCon event on October 1, 2017 during the 232nd ECS Meeting in National Harbor, Maryland. This landmark event marked ECS’s first large community effort aimed at creating a culture of change in how research is designed, shared, discussed, and disseminated, with the ultimate goal of making science more open and stimulating faster progress. OpenCon is an international event hosted by the Right to Research Coalition, a student organization of the Scholarly Publishing and Academic Resources Coalition (SPARC). OpenCon provides a platform for researchers to learn about open access and open science, develop critical skills, and catalyze action toward a more open system for sharing the world’s information. This event featured leading vocal advocates in the open science movement, examining the intersection of advances in research infrastructure, the researcher experience, funder mandates and policies, as well as the global shift that is happening in traditional scholarly communications. “This ECS OpenCon is a really important first for the global OpenCon community. It’s the first OpenCon satellite event hosted by a scholarly society, and that’s a huge deal,” said Nick Shockey, SPARC director of programs and engagement and ECS OpenCon speaker. “The research that ECS members do has a very real world impact, and making that work openly available will hopefully accelerate the research and innovation.” Ashley Farley, open access program associate at the Bill and Melinda Gates Foundation, kicked off the program with her keynote talk, “The Importance of Open Science in a Changing Scholarly Communications Paradigm.” “Open science is about opening up the entire practice of science itself, kind of front-loading the process instead of waiting until we get to research results and then making sure they are open and available,” Farley said. “It’s building that openness from the beginning and having an environment that fosters collaboration, so you have open notebooks and open data. It promotes equity among scientists and really supports collaboration.” E. J. Taylor, cochair of the ECS Free the Science Advisory Board and Society treasurer, gave the audience an overview of Free the Science. “Free the Science is truly a mission-based initiative that will help ECS maintain its independence as a nonprofit scientific society, run by scientists and engineers for scientists and engineers,” Taylor said. “I am personally excited that ECS is in the position to be a real leader in our field but also a trailblazer in research communication.

With your voice behind us, we can free the science and ultimately accelerate progress.” Other speakers included Brian Nosek of the Center for Open Science on open science, Meredith Morovati of Dryad on open data, Dina Paltoo of the National Institutes of Health on open and government, and Daniel Schwartz of the University of Washington on open and academia. The event concluded with the panel discussion “Changing Culture: How are the Different Constituencies Represented at this OpenCon Going to Move the Needle on How Science is Communicated?” You can watch full coverage of ECS’s OpenCon at www.youtube. com/ECS1902.

Ashley Farley delivered the keynote talk during ECS’s OpenCon.

From left to right: Daniel Schwartz, Meredith Morovati, and Brian Nosek during the panel discussion.

IRA Charitable Rollover Opportunity for U.S. Taxpayers

From left to right: Daniel Schwartz (University of Washington), Nick Shockey (SPARC), Dina Paltoo (National Institutes of Health), Ashley Farley (Bill and Melinda Gates Foundation), Brian Nosek (Center for Open Science), Meredith Morovati (Dryad), and ECS Executive Director Roque Calvo.

If you’re a U.S. taxpayer and 70.5 years or older, you can take advantage of the IRA Charitable Rollover provision by the end of the year. This means that if you have not yet met your required minimum distributions from your IRA, you can transfer money directly to ECS as a philanthropic gift. Although the gift will not generate an income tax charitable deduction, it will be free from income tax, making it a clear tax win for most donors. For more information, please contact development@electrochem.org or 609.737.1902 ext. 122.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS Successful First ECS Data Sciences Hack Day

DATA

SCIENCES

HACK

DAY OCTOBER 4, 2017

The ECS Data Sciences Hack Day held in National Harbor was the Society’s first foray into building a data sciences and open source community for electrochemistry and solid state science from the ground up. Dataset sharing and open source software have transformed many big data areas such as astronomy, particle physics, synchrotron science, protein and genomic sciences, as well as computational sciences. There is a fast-growing demand for turning big data into actionable information. Data science is concerned with four very relatively specific areas: visualization, data management, statistics, and machine learning. Data science tools and approaches also have the potential to transform bench science like electrochemistry. There is a critical need to build a community of data scientists in our field with people who can grow a library of shared experimental and computational datasets and who develop and adapt open source software tools.

NATIONAL HARBOR, MD

The day-long program was run by Daniel Schwartz, David Beck, and Matthew Murbach. Schwartz is the Boeing-Sutter Professor of Chemical Engineering and director of the Clean Energy Institute at the University of Washington; he brings electrochemistry and modeling expertise to the team. Beck is a senior data scientist with the eSciences Institute at the University of Washington and leads regular hackathons; he is associate director of the NSF Data Intensive Research Enabling CleanTech PhD training program. Murbach is president of the ECS University of Washington Student Chapter and an advanced data sciences PhD trainee; he has been leading the student section software development sessions on the University of Washington campus and has practical experience coaching electrochemistry scientists and engineers in software development. These three spoke passionately about data sciences in an ECS podcast (www.electrochem.org/redcat-blog/open-science-ecs). David Beck noted that science is not “artisanal”; it’s about scientists working in teams. “Having software be open, having data be open, really enables that team effort and allows checks and balances and assurances of reproducibility,” Beck said. Matt Murbach added, “I think it’s going to be grad students pushing their advisors to think about: ‘Let’s publish this data set with this manuscript.’ ‘Let’s publish our software on GitHub.’ And I think that can start to be the cultural change that comes from the excitement of my peers.” The 30 participants in the hack day traveled from around the globe and represented varying stages of careers in both academic and industry roles. The day-long event was kicked off with a short series of informational sessions covering some of the essential tools in any data scientist’s toolbox. During lunch, participants pitched their ideas for projects, and teams for the afternoon session organically formed

Daniel Schwartz

Matthew Murbach

David Beck

around common interests. The remaining time during the afternoon was reserved as open hacking time for working on the project ideas. Good progress was made by teams working on a wide variety of projects, including: • open source software for the analysis of X-ray Photoelectron Spectroscopy (XPS) spectra • writing genetic algorithms to search for molecular structures with RDKit • using machine learning to predict battery degradation • building tools for easily accessing and analyzing open battery prognostics data • open standards for metadata and the sharing of experimental electrochemical data In addition to the projects and scientific discussions, the professional connections made during and after the hack day are vital for laying the groundwork of a growing community of electrochemical data scientists. Outputs from the hack day are organized on an OSF project page (DOI: 10.17605/OSF.IO/Z4XKN), providing a persistent source for information and a lasting legacy of the inaugural event. Schwartz pointed out that funders, like the National Science Foundation, have changed what they are looking for in the supporting materials for a grant. He explained that, in 2013, “they went from, ‘give us your five most significant publications and your five most relevant publications,’ to ‘give us your five most significant research products.’” So the outputs from data science activities, like the hack day, will also provide participants valuable additions to their résumés. As with many experimental programs, this one could not have happened without the support of sponsors. The sponsors of the first ECS Data Sciences Hack Day—the University of Washington Clean Energy Institute, the University of Washington eScience Institute, and the U.S. Army Research Office—provided funding for many of the participants to travel to the event. Not only was the hack day an achievement in and of itself, but it marks the start of ECS maintaining and openly disseminating highquality curated data, software, and other data science tools that will help push forward the open science vision of ECS’s Free the Science initiative. The success in National Harbor has everyone excited for the next opportunity at the ECS meeting in Seattle, Washington in spring 2018. Be sure to sign up for the ECS weekly newsletter (www.electrochem. org/enews) to learn more about opportunities for contributing project ideas and submitting your application for the next ECS Data Sciences Hack Day.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS Next Generation Electrochemistry (NGenE) Launched The second installment of Next Generation Electrochemistry end of the week, NGenE participants summarized their project in a (NGenE), a weeklong summer research workshop on the frontiers of presentation to their peers and the faculty, who acted as reviewers. electrochemistry, took place at the University of Illinois at Chicago The lively discussions and stimulating atmosphere of the workshop from June 26-30, 2017. During NGenE 2017, 37 advanced graduate produced many creative and engaging proposals. students and postdocs and 9 world-renowned experts gathered Looking forward to 2018, the organizing team continues to seek to discuss research frontiers in the study and understanding of input from the community to shape the critical features of the program electrochemical interfaces. Lectures by NGenE faculty provided with a focus on the fundamental aspects of electrochemical science. a high-level overview of the current body of knowledge while The team can be reached at uic.ngene@gmail.com. highlighting critical gaps that need to be overcome in order for transformative advances to be made. The lectures subsequently This notice was prepared by NGenE Director Jordi Cabana. charted possible paths forward involving innovative approaches. The lectures were complemented with demonstrations of cutting-edge tools, such as the university’s in situ electron microscopy, and visits to large-scale user facilities at Argonne National Laboratory. ECS was one of the sponsors of this event. NGenE is centered on its participants, who are encouraged to lead discussions of the contents of each lecture and challenge existing notions. During the week, the participants also conducted a project in a team of four or five. Their task consisted of identifying an innovative, fundamental question within one of two broad topics of interest in electrochemical interfaces. They subsequently developed a research plan to answer this question using the most contemporary methods, inspired by their existing knowledge as well as the new understandings they developed during the summer workshop. NGenE faculty provided mentoring during hour-long sessions of project discussion. At the Attendees of NGenE 2017, a summer research workshop held at the University of Illinois at Chicago.

The ECC-Opto-Std Our allrounder for in-situ visualization of electrode processes

Flexible optical three-electrode test cell Suitable for both sandwich and side-by-side electrode arrangements Available for light microscopy, Raman spectroscopy as well as XRD The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Watch our in-situ test videos on el-cell.com/support/videos

SOCIE T Y NE WS

Institutional Member News Join ECS as an Institutional Member 89% of institutional members have a positive impression of the ECS Institutional Membership Program. Does your organization send multiple staff to the ECS biannual meetings? Or do you know colleagues at your organization that also have an individual ECS membership? The Institutional Membership Program (IMP) may benefit your organization through membership, meeting registrations, advertising, exhibiting, subscriptions to the ECS Digital Library, and more. Check out the Institutional Membership Program to see what works for your organization:

www.electrochem.org/institutional-membership Reach out to our Director of Membership Services, Shannon Reed, with any questions:

Benefits SatisfactionofofInstitutional Institutional Members Beneﬁts Satisfaction Members

SATISFIED 33%

VERY SATISFIED 22%

MORE THAN SATISFIED 45%

Shannon.Reed@electrochem.org

2017 Doron Aurbach 2015 Henry White Nominations Due: April 15, 2018 38

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS ECS Sponsors XXI SIBEE Hosted biennially since 1978, the Simpósio Brasileiro de Eletroquímica e Eletroanalítica (SIBEE) is a distinguished national forum for the discussion and advancement of electrochemistry, electroanalysis, and methods of data dissemination. ECS sponsored the XXI SIBEE, which was held in Natal, Rio Grande do Norte, Brazil, April 17-21, 2017. Featuring lectures, short courses, oral presentations, and posters, the XXI SIBEE connected preeminent scientists across the disciplines of academia, industry, and applied research. Six members of the ECS South Brazil Student Chapter attended the symposium. ECS provided awards to the four student researchers with the best presentations: Pedro Henrique Moura Leal (Federal University of Rio de Janeiro) received the first place oral presentation award for his presentation “Numerical Analysis of the Effect of Homogeneous Reactions in the Current of the Rotating Disc Electrode.” The award consists of complimentary registration to one ECS meeting, complimentary one-year ECS membership, and the winner’s choice of one issue of ECS Transactions. Leal obtained his bachelor’s degree in materials engineering from the Federal University of São Carlos in 2012. In 2013, he earned his master’s degree in metallurgical and materials engineering from the Federal University of Rio de Janeiro. He is currently a PhD student in the metallurgical and materials engineering program of the Alberto Luiz Coimbra Institute for Graduate Studies and Research Engineering at the Federal University of Rio de Janeiro. He works at the Laboratory of Non-Destructive Testing, Corrosion and Welding under the supervision of Oscar Rosa Mattos. Filipe Soares Da Cruz (Federal University of Jequitinhonha and Mucuri Valleys) received the second place oral presentation award

for his presentation “Electrochemical Biosensor for Determination of Uric Acid in Urine Samples by FIA.” The award consists of complimentary registration to one ECS meeting and complimentary one-year ECS membership. Da Cruz graduated as a bachelor of science and technology in chemical engineering from the Federal University of Jequitinhonha and Mucuri Valleys. He holds a master’s degree in chemistry from the Federal University of Jequitinhonha and Mucuri Valleys, where his advisor is Lucas Franco Ferreira. There, Da Cruz works in the Group of Electrochemistry and Applied Nanotechnology. Marílya Palmeira Galdino Da Silva (Federal University of Alagoas) received the first place poster presentation award for her presentation “Employment of PAMAM Dendrimer as an Encapsulating Agent in the Electrochemical Study of a Bioactive Nitroderivative.” The award consists of complimentary registration to one ECS meeting and complimentary one-year ECS membership. Da Silva earned her MS in biochemistry and biotechnology from the Federal University of Alagoas, where she is a PhD student and a member of the research group of the Laboratory of Electrochemistry and Microsystems of Analysis under the direction of Fabiane Caxico de Abreu Galdino. Thais Tasso Guaraldo (University of São Paulo) received the second place poster presentation award for her presentation “Development of Electrochemical Sensors Based on Black Carbon for Determination of Trimethoprim.” The award consists of complimentary one-year ECS membership. Guaraldo received her BS in chemistry from São Paulo State University in 2007. She obtained her MS in 2010 and her PhD in 2014, both in analytical chemistry and from the Institute of Chemistry at São Paulo State University. She is a postdoctoral researcher at the São Carlos Institute of Chemistry at the University of São Paulo.

Upcoming ECS Sponsored Meetings In addition to the ECS biannual meetings and ECS satellite conferences, ECS, its divisions, and sections, sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a partial list of upcoming sponsored meetings. Please visit the ECS website (www.electrochem.org/upcoming-meetings/) for a list of all sponsored meetings.

Silver/Silver Chloride Reference Electrode

2017

• Fuel Cell Seminar & Energy Exposition; Long Beach, CA, USA; November 7-9, 2017; www.fuelcellseminar.com/ • European Fuel Cells Technology & Applications Piero Lunghi Conference (EFC17); Naples, Italy; December 12-15, 2017; www.europeanfuelcell.it

Stable Reference 0.047 Volts vs. SCE Widely used

2018

Non-toxic

• 69th Meeting of the International Society of Electrochemistry; Bologna, Italy; September 2-7, 2018; www.annual69.ise-online.org/; Joint Symposium: “Theory: From Understanding to Optimization and Prediction” To learn more about what an ECS sponsorship could do for your meeting, including information on publishing proceeding volumes for sponsored meetings, or to request an ECS sponsorship of your technical event, please contact ecs@electrochem.org.

Custom glass available Always in stock. Made in USA.

www.koslow.com “Fine electrochemical probes since 1966”

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE T Y NE WS

websites of note by Alice H. Suroviec

Corrosion Technology Laboratory

• The Corrosion Technology Laboratory at the NASA Kennedy Space Center is a network of capabilities—people, equipment, and facilities—that provide technical innovations and engineering services in all areas of corrosion for NASA and external customers. The Corrosion Technology Laboratory is part of the Applied Technology Division of NASA, and any project involving corrosion may utilize this fully staffed and equipped corrosion laboratory as a resource. This site provides fundamentals of corrosion and corrosion control information as well as resources for further information. www.corrosion.ksc.nasa.gov/corr_fundamentals.htm

How Electrochemiluminescence Works

• This video tutorial presents an introduction to electrochemiluminescence (ECL). This overview covers all the topics needed to have a basic understanding of ECL. www.youtu.be/PHbcvBGfzMM

Chemtutor

• This website provides chemistry tutoring for high school and college students. Chemtutor begins with the fundamentals and provides expert help with the most difficult phases of understanding of chemistry. www.chemtutor.com

About the Author

Alice Suroviec is an associate professor of bioanalytical chemistry and chair of the department of chemistry and biochemistry at Berry College. She earned a BS in chemistry from Allegheny College in 2000. She received her PhD from Virginia Tech in 2005 under the direction of Mark R. Anderson. Her research focuses on enzymatically modified electrodes for use as biosensors. She is currently the chair of the ECS Physical and Analytical Electrochemistry Division and an associate editor for the Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry topical interest area in the Journal of The Electrochemical Society. She can be reached at: asuroviec@berry.edu.

ECS Electrochemistry

KNOWLEDGE BASE One site. Thousands of resources. 4 Over 1,000 electrochemical definitions 4 Dozens of articles by leading experts 4 Links to over 1,000 electrochemical websites 4 Over 3,000 books and proceedings volumes listed

http://knowledge.electrochem.org

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

s far as I can rememthat there is no shame in I am taking the opportunity of this invited article to share some ber, I have always admitting that one does personal thoughts about the way academic science education has been interested in not know. They also developed during my life. It seems clear that, if the thrust that allowed understanding the helped me recognize that our scientific world to bloom stems from humanity’s insatiable thirst whys of what I was some of my questions for knowledge and art, the means allocated by society to materialize observing—the mysteries deserved a rational it, as we know it, are more deeply intertwined with the market and with which I have been answer, while others economy than I had previously thought. Paradigms that shaped our confronted. I was constantwere puerile fantasies. It academic world have changed gradually, hence almost imperceptibly, ly interrogating my parents is enough to consult the but not necessarily in the interest of the future of science. to get explanations. Today, internet or YouTube to [Ed. Note: The opinions expressed in this article are those of the I know that some of the realize that most of our author and not Interface nor The Electrochemical Society. Interface questions I asked were, citizens today cannot welcomes feedback on this article.] in fact, scientific ones: so clearly discriminate “Why can clouds flying between rational and in the sky suddenly decide correct information, and to burst open and release unfounded and eccentric rain?” “How can huge sand alternative facts. dunes1 travel over half a Even if it was fully mile during a single night beyond my awareness, while keeping the same my parents’ use of shape?” While others were experimental models to just puerile thoughts, I address questions taught felt just as concerned with me one of the important knowing the answers. qualities and great powers I was the first son of of science. Indeed, from an immigrant family from teaching purposes to Sicily, and the first Frenchcreative research, scientists born in my family. My constantly rely on the parents were caring and, as exceptional ability of the I could discern only later, human mind to distill the not financially wealthy, important features of one but incredibly rich in terms complex phenomenon and of the care they provided. cast them into a real or They always tried to imaginary3 contraption (a answer my questions. The model). These features can trivial ones were easy for then be transposed back them, but the more serious into the initial phenomenon ones were challenging. to better understand its Indeed, even though both causes or nature.4 Art and of them were extremely this primeval desire to smart, they had to stop interrogate nature in order school after completing to rationalize it are, in the elementary level. my view, two distinctive They always did their traits of humanity. Lay best to provide me with people, like my parents, a logical answer, either often unknowingly using rational arguments, proceed along the same or most often, by relying lines, but are generally on experimental analogies. stalled at the level of When they could not intuitive conclusions, answer, they never evaded lacking the scientific and my questions. Instead, they mathematical skills to natural laws that my questions involved. said, “You are right to ask this question, progress further. Conversely, their experimental analogies but we don’t know the answer. It’s even In truth, the modern scientific era did and models were generally correct and possible that, so far, nobody knows the not only pass to us its thirst for scientific captured, at least in part, the essence answer.” They never replied, “You are too understanding; far more importantly, it of the real phenomena that I wanted to young to understand,” which is the best gave us methods to satiate this thirst with understand. way to discourage kids from trying to find rigor. We are supposed to be introduced I did not know back then, however, that meaning in their surrounding world. to these methods in school, under the my parents’ attitude had been essential in I learned later that their answers, though guidance of teachers and professors. This starting me on the path toward science. adequate for me at the time and logically was precisely the role of school in my Not only did they encourage my pleasure correct, were often wrong, simply because time. Teachers and professors did not try of finding things out,2 but they taught me they did not have the chance to learn the

The Red Queen and the Russian Dolls by Christian Amatore

(continued on next page)

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Amatore

they imagined would boundaries that set me “Not only did they contribute to our welfare. on the path that guided to imprint facts in our memories without encourage my pleasure The only difference was me toward academic anchoring them to the explanations that our 2 of finding things out, but that the explorers of Earth, science. Indeed, my 5 brains required; these explanations often like their contemporaries, they taught me that there trajectory naturally prohad to be oversimplified, but they conveyed generally knew what along this path general sense and reasoning without is no shame in admitting gressed these nuggets were before and led me to start a significant distortion. For example, in that one does not know.” thesis under the attentive their journeys began. elementary school, we had books on leçons Explorers of science guidance of Jean-Michel de choses (i.e., lessons about natural things). obeyed their devouring Savéant and during a Each lesson was built like a Sherlock Holmes passions and often needed to persuade postdoctoral stay with the late Jay K. Kochi. novel, starting with a somewhat mysterious their contemporaries about the importance These times marked my beginnings in the story, assembling a patchwork of seemingly and reality of their nuggets. Think about world of Russian dolls, to whose spirit unrelated observations, and progressively Pasteur and microbes, or Marie Curie and I have remained faithful. I believe these solving the puzzle with the aid of proper radioactivity. Furthermore, we could easily experiences, from elementary school to hints, up until the point when a single logical understand that their creative longing never my undergraduate years, were not singular conclusion could be reached. From each stopped during their lives: finding out one among my age group, except maybe for lesson we derived a bring home message, thing would simply expose another one the good fortune of having parents such as which summarized the scientific point or whose existence was unsuspected up until mine and the luck of being taught by many points that we had just come to understand. the previous enigma was solved. In other good teachers and professors. Actually, Retrospectively, I think these leçons de words, this was telling us that creative unbeknownst to me at the time, I belong to choses provided a better introduction to science is like art. Both proceed like an one of the very few generations to which science and creative scientific research than infinite series of Russian dolls: no one can our societies decided to entrust the pursuit one can find in most schoolbooks today, and predict if a new doll will be discovered of their future. Indeed, my age group grew even in most college textbooks. inside before the outer doll is cracked open.6 during the thirty glorious years (the years following the rapid reconstruction of Europe and Japan after World War II) that led to an almost exponential economic growth in developed countries. On the other hand, on each side of the Iron Curtain, our societies were involved in the Cold War. These factors stimulated open scientific research and technology. Indeed, competition among national economics and prestige, political displays of the value of opposing economic and social systems, and trying to keep the lead in the race for new weapons9 could not proceed without more and more scientists and engineers involved on each side. Detecting the best seed scientists in any nook of a country and training them to ensure that, whatever their social origin, they would be able to fully reveal their talents, was a duty of school and a mission assigned to schoolteachers and professors. This has been going on in almost all developed countries for the same reasons. Today, one prefers to euphemistically cover this crude reality under more noble Illustration by John Tenniel of Alice and the Red Queen running to keep in place, from Lewis Carroll’s veils. Speaking about the promotion of Through the Looking Glass. egalitarian education and social elevators has become the usual and politically correct way to describe this mechanism. However, One is even more baffled when trying Along with these leçons de choses, our this is no more correct than speaking to predict any industrial application of schoolbooks offered passages from reputed about installing social elevators during the newly exposed knowledge.7 This is where French writers, and texts relating the feats Industrial Revolution, which dragged people academic research differs from engineering. and life episodes of famous and impressive from the countryside to the cities to serve the The usual distinction between fundamental persons. They were not only telling us machines.10 The only difference is that, then, and applied research is clearly wrong, since their achievements, but also casting these in most countries, the middle and upper there is as much applied research in the sofigures amid the doubts and struggles they classes were numerous enough to easily called fundamentals as there is fundamental experienced while they worked to change provide the required numbers of scientists research in the applied. The real distinction the world. I can see, in retrospect, that these and engineers, who were so essential in is between open research lectures demonstrated contributing to the increasing success of the (the never-ending Rusthat explorers of science “I have used my own Industrial Revolution. A few exceptions have sian dolls) and research were no different from experiences to report on existed, for sure, but they were generally finalized toward an Columbus, Marco Polo, due to improbable happenstances, like that already identified and or Livingstone. All of how these initial years of of Humphry Davy being impressed by the selected target.8 them were people who my life bred boundaries crisp intelligence of the young Michael Until now, I have used lived within their epochs, that set me on the path Faraday. Huge amounts of money were my own experiences to but were exploring new injected into education with the expectation report on how these initial worlds, expecting to that guided me toward that the returns would exceed the initial years of my life bred bring back nuggets that academic science.” (continued from previous page)

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

cost and lead to future networks as it started at strongly prioritize high educational aspects “Today almost all commercial and political CERN before becoming as opposed to research. Clearly, the Red academic researchers the internet, which Queen’s race does not seem to be ending dominance. This worked beyond most optimistic would become so central soon in the academic scientific world. have to compete expectations, generating to the development of To drive the nail deeper, most scientific on priority targets a near exponential growth new forms of economy? publishers have entered into a strong of economies. Or, closer to our field, competitive struggle driven mostly by generally imposed As any realistic and on more modest financial interest. To win their own Red from above.” economist should have grounds, would Bard’s Queen’s race, they need to compete in predicted, this economic or Savéant’s research attracting, as before, the best papers from rise was bound to meet a plateau. The first on the 32 different mechanisms of electrothe best authors. Unfortunately, best no evidence of this materialized in the middle hydrodimerization be appealing to agencies longer has the same meaning as it had during of the 1970s when the first oil crisis struck nowadays? the Russian dolls’ heyday. Now, best is the whole Occidental world. This rapidly This situation resulted in focusing measured in terms of journal impact factors amplified when Japan, and then Korea, funding on what seemed appealing. (JIFs) and h-indexes. However, the very entered with remarkable dynamism into the Unfortunately, today almost all academic definition of JIFs14 dictates that research science- and high technology-based world researchers have to compete on priority that can be rapidly cited, possibly by public economy, accompanied by China, and with targets generally imposed from above, and media, is most welcome.15 It is evident that India joining the process. The problem is not often based on short-term oriented fancies. most of the fully seminal research cannot at all with the globalization of the economy, Forced into participation, we have no choice contribute to good JIFs. Indeed, even if but rather with the fact that this somewhat but to embark, like Alice, in a sort of Red reading such a paper would stimulate many broke down the dream-cash machine Queen’s race, having to run fast constantly academic scientists to immediately follow that had been continuously powering the only to remain in the same spot.13 suit, the timescale needed for obtaining the development of the science- and technologyFortunately, the private dream-cash grant required to perform their own research based growth of traditional Occidental machine shows visible in this new direction, economies.11 Indeed, this growth could signs of recovery, carry it out, and get it “Most scientific happen only because lay people believed stimulated by the published generally publishers have that it would work. They were spontaneously vision and impulses of exceeds the two year willing to provide the money required to billionaires, and based on duration imposed entered into a strong gap make it work. In this respect, it is important models tested in Silicon by the JIF. Hence, competitive struggle publication of fully to recognize that this input was much larger Valley. For example, than what any government could inject using space conquest seems unexpected results is no driven mostly by taxes.12 While this faith was progressively to be leaving the public longer the most favored financial interest.” disintegrating, the number of scientists was domain to become a by JIF-driven journals.16 reaching unprecedented records, having reality in the hands of Such business-driven grown continuously during the heyday of entrepreneurs like the founder of Tesla concurrence among scientific journals can economic expansion to contribute to either Motors, and is attracting huge resources only increase the Red Queen’s speed in her the growth of companies or academia. from giants like Google, followed by race and lead to the complete extinction of Evidently, the conjunction between a less venture capital. Regrettably, at the same the Russian dolls research model. Is this efficient dream-cash machine and a large time, the main preoccupation of scientific what we really want? Will it be beneficial to number of scientists necessarily decreased universities and institutions seems to be our society? the mean research funds per capita. In an improving their rankings in the Shanghai or © The Electrochemical Society. attempt to derail this process and re-attract Times classifications, suggesting that they DOI: 10.1149/2.F01174if. private investments, the public agencies (continued on next page) of many countries decided that access to government funds required justifying shortterm financial returns. The imbecility of such politically correct directives is all the more evident when one notices that the technology-based wealth of our societies is deeply-rooted in unpredicted outcomes Christian Amatore, emeritus director of research at the of previous open research performed by Centre National de la Recherche Scientifique, is a former curiosity-driven scientists who thought and student of the Ecole Normale Supérieure. He is a full member acted in their own ways, following their of the French Academy of Sciences, the Chinese Academy of educated guesses. The outcome of open Sciences, the Academia Europaea, and the Third World research cannot be predicted—and certainly Academy of Sciences. He is an honorary fellow of the Royal cannot be directed—based on short-term Society of Chemistry and the Chemical Society of China, an returns. Rules governing finalized research honorary member of the Chemical Society of Israel, and a simply do not apply to open research. By fellow of The Electrochemical Society; he is also a fellow and definition, most open research cannot boast past president of the International Society of Electrochemistry. predictable short-term applications with He has been knighted in the orders of the Legion of Honor, of which to justify access to taxpayers’ money. National Merit, and of Academic Palms. He has published over 485 primary research For example, if we did not know now that articles with more than 21,700 citations and an h-rating of 74. His research interests it would lead to transistors and computer are extremely broad, ranging from chemistry and catalysis to biology, but are all chips, or Moore’s law on the growth of based on innovative applications of electrochemistry. With Mark Wightman, he was electronics, what governmental or private one of the leading pioneers of the microelectrodes and ultramicroelectrodes that now agency would fund today a research project dominate the world of analytical electrochemistry. He may be reached at on the purification of silicon, and then on christian.amatore@ens.fr. methods precisely designed to mess up with such extra pure silicon? Who would support any research today on packet-switched

About the Author

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Amatore

(continued from previous page)

Notes 1. At the time my family was living in Laghouat, a city located in Algeria (at the time, Algeria was not a colony; it was part of France as Corsica is today) at the north border of the Sahara— hence my concern with moving sand dunes rather than with stable hills or mountains, which I discovered only later in my life. 2. I could not resist in borrowing this marvelous expression from Richard Feynman’s eponymous book title. 3. So-called thought experiments are usually attributed to Einstein. Yet, if it is true that Einstein often used this argumentative method, he did not invent it. In fact, this existed even before Euclidean mathematics, being named δεικνυµι (i.e., “I show”) in ancient Greek. To the best of my knowledge, this was the most ancient method of establishing a proof—or of disproving a previous rationale through providing a paradox, as Einstein loved to do—by casting emphasis on a purely conceptual argument rather than on an experimental contrivance. 4. For example, we have all been taught that Galileo was deeply concerned with the role of the sun in the solar system, but we are also taught that he spent huge amounts of time in understanding the laws governing pendulum oscillations. For a long time, I did not understood how he could put aside his insatiable desire to prove that Copernicus was right to find time to investigate some comparatively inconsequential problem. If I had been smarter, I would have understood that Galileo had remarked that the projection of a mobile object circulating along a circular trajectory on one of its diameters corresponds to a linear oscillation (i.e., precisely the sinusoidal movement displayed by a pendulum at short angles). Galileo was not gifted in mathematics, so designing an experimental model was his approach to the problem. Reducing the mechanics of Earth travelling around the sun down to a pendulum oscillating on his desk is, in my view, incredible proof of his genius and profound prescience of how science would construct itself and proceed after him. 5. At least it was like that in France, with most of the teachers and professors who educated my classmates and me. They were adamant, whether in natural sciences or the French language, about teaching us methods to aid in understanding. In some respects, I can now appreciate that for them, knowing— though necessary—was somewhat

subordinate to understanding. They knew that what is memorized generally evaporates quickly, unless it is deeply anchored in clear, logical roots. Wise sub-Saharan African and Chinese adages from time immemorial perfectly illustrate this view (e.g., in modern English, “Give a man a fish, and you feed him for a day; teach a man to fish, and you feed him for a lifetime”). It is disheartening to see how this stands in such contrast with teaching principles enforced in most schools of Occidental countries since the 1980s. Moreover, notwithstanding the known failure of these methods in the U.S., they have been readily spreading to Europe (except for Finland, which has reverted to the previous ones). Does this mean that the past panem et circenses strategy is resurfacing as the way of governing nations? 6. For example, compare to Picasso elaborating his quintessence of a bull through exploring so many avenues, often returning back to an abandoned train of thought to pursue it in a different direction. I chose Picasso and his bulls series because he archived all his paintings and drawings, thus providing a prodigious documentation that is often freely accessible. However, this process is common to most creators in art or science. Consider, for example, this quote by Faraday: “I am no poet, but if you think for yourselves, as I proceed, the facts will form a poem in your minds” (cited by Bence Jones in The Life and Letters of Faraday (1870), Vol. 2, p. 403). 7. I cannot resist quoting the famous Faraday answer to William Gladstone, then British Chancellor of the Exchequer, who had been so impressed to observe that a field getting out of a magnet bar was strong enough to organize iron fillings into a clear pattern, though one could not feel it or smell it with the human senses. The prime minister asked Faraday what application this prodigious discovery will bring. Faraday answered, “Today, I really cannot foresee any practical value of electricity, but, sir, I am sure that one day you will tax it.” This was only 30 years before the invention of the first alternators and electrical engines. Today, except for photovoltaic conversion, all electricity consumed on Earth is produced by Faraday’s alternators. 8. Consider, for example, the Wright Brothers or Gustave Eiffel as opposed to Thomas Edison or Steve Jobs. The first two made fundamental scientific discoveries that began important progress, while the second two found a market for applications based on improved, but already existing knowledge.

9. Remember how Sputnik’s beeps generated a wave of panic in the U.S. government during the fall of 1957? This led to the expeditious creation of DARPA out of scratch, over the course of just four months, to avoid any future technological or scientific surprises by expanding the frontiers of science and technology through collaboration between academics, industries, and U.S. government partners. 10. Note that, except in France where this was a consequence of the installation of full democracy, the decision to develop schools on a large scale also correlates with the rise of Industrial Revolution. Indeed, a farmhand could gain all required knowledge and practice from his or her parents or neighbors and did not need many writing and calculating skills. Conversely, a factory worker needed such skills to run the machines he or she operated. 11. Spreading global wealth across all nations would certainly benefit humanity as a whole, if traditional market views adapt to this novel norm. In this respect, we have to hope that sub-Saharan Africa will soon join this movement. 12. Though I concentrate here on scientific and technological developments, the same occurred already at the time of the great expeditions across the world to corroborate trade routes for spice and silk. Then, chartered companies such as the Dutch East India Company or the eponymous British ones were literally selling dreams in the form of bonds, whose value was paid back with high interest through the return of a few ships loaded with spices and other highpriced merchandise. Faith in the system and a sufficient percentage of success was enough to generate an accelerated growth. Our recent scientific and technological developments have been more or less powered by the same faith in rising economics. Literally speaking, Sony was telling an exact truth with the slogan “You Dreamed of It, Sony Did It,” except that the two its referred to two different things. 13. To Alice, who wondered why they had to constantly be running, the Red Queen answered, “Here, you see, it takes all the running you can do, to keep in the same place. If you want to get somewhere else, you must run at least twice as fast as that!” (Lewis Carroll’s Through the Looking-Glass). 14. The JIF of a journal is the number of citations received in one year by articles published in that journal during the two preceding years, divided by the total number of articles it published during same the two preceding years. Hence, publishing novel papers that are not expected to bring many

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

citations during the next two years lowers a JIF, even if this paper may open a blooming field a few years after. Note that my own h-index and mean citation rate demonstrate that I am not accusing these circumstances for selfish reasons like Aesop’s famous fox. Yet, though this is not evident from glancing rapidly at Web of Science or Google Scholar statistics, most of my seminal works, the very ones that contributed to building my scientific reputation, received almost no citations for several years after their publication (i.e., before many others implemented

them). A good example is given by microelectrodes, a field which I pioneered with Mark Wightman (Pons and Fleischmann were doing the same on their side), but could not bloom until the National Science Foundation decided to stimulate grant proposals on this topic. 15. This is perfectly obvious with top journals, for which the decision to send a submission to review or reject it without any reviewing is made based on quick assessment of the contribution’s potential for boosting the journal’s JIFs and stimulating the interest of public

media. We have reached a point where catchphrases and the brittleness of a title are more valuable than the paper’s content. 16. A good example is afforded by Binnig and Rohrer’s seminal discovery, which was published in 1982 in Helvetica Physica Acta (whose mean JIF was approximately 0.5 from 1992 to 2001), but was soon awarded the 1986 Nobel Prize for the invention of the scanning tunneling microscope. See: G. Binnig and H. Rohrer, Helv. Phys. Acta, 55, 726, (1982).

RL HERING A C

A C Y CIR C L

The Carl Hering Legacy Circle The Hering Legacy Circle recognizes individuals who have participated in any of ECS’s planned giving programs, including IRA charitable rollover gifts, bequests, life income arrangements, and other deferred gifts. ECS thanks the following members of the Carl Hering Legacy Circle, whose generous gifts will benefit the Society in perpetuity: K. M. Abraham

George R. Gillooly

Keith E. Johnson

Masayuki Dokiya

Stan Hancock

Mary M. Loonam

Robert P. Frankenthal

Carl Hering

Edward G. Weston

W. Jean Horkans

Carl Hering was one of the founding members of ECS. President of the Society from 1906-1907, he served continuously on the Society’s Board of Directors until his death on May 10, 1926. Dr. Hering not only left a legacy of commitment to the Society, but, through a bequest to ECS, he also left a financial legacy. His planned gift continues to support the Society to this day, and for this reason we have created this planned giving circle in his honor.

To learn more about becoming a member of the Carl Hering Legacy Circle, please contact Karla Cosgriff, development director. 609.737.1902 ext. 122 | Karla.Cosgriff@electrochem.org

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

SOCIE PEOPLE T Y NE WS

In Memoriam memoriam Harry Sello (1921 – 2017)

Sello was a semiconductor materials research chemist and pioneer of the semiconductor industry in Silicon Valley. He joined ECS in 1958, was an emeritus member, and a member of the Electronics and Photonics Division as well as the San Francisco Section. He passed away in Palo Alto, California on April 4, 2017. His outgoing personality and ability to explain complex technical matters in simple language influenced generations of engineers, scientists, and curious members of the public across the world. Sello was born in born in 1921 in Chernihiv near Kiev, Ukraine, which at that time was part of Russia. As Jews who had served in the Czarist army his parents fled with their son to the U.S. in 1923. They settled in Chicago where his mother worked as a nurse and his father delivered milk. They encouraged his interest in reading and music. Sympathetic teachers mentored him in math and chemistry. On graduating from the University of Illinois with a BS in chemistry in 1942, Sello enrolled in graduate school at the University of Missouri. After service in the U.S. Navy in the Asia-Pacific theater, he earned MA and PhD degrees in physical chemistry and joined the Shell Oil Development Company in Emeryville, California, as a research chemist in 1948. Sello joined the Shockley Semiconductor Laboratory in Mountain View in 1957. After a couple of years working on silicon device structures under Nobel Prize winner William Shockley, he joined his mentors, Robert Noyce and Gordon Moore, at their start-up company Fairchild Semiconductor. Here he worked with the team that developed the planar process and the first monolithic silicon integrated circuits (ICs). During his time at Shell, Sello had conducted chemistry demonstrations on TV funded by the Ford Foundation and recorded by WGBH. With this experience he narrated a video for Fairchild on applications for ICs that was seen by 2 million viewers across the country. From his 20 years of fundraising as an auctioneer for KQED Channel 9, his face was also familiar to audiences around the Bay Area. In the 1970s, Sello’s international expertise found him involved in a variety of high-level sales, technology licensing, and manufacturing projects. He negotiated agreements with state-owned and private companies, including those in Austria, China, Hungary, and Russia. At age 91, Sello trained as a docent at the Computer History Museum in Mountain View where he enjoyed regaling young audiences with inside stories of the history of the technological revolution that he had lived. arry

Contributed by David A. Laws, Semiconductor Curator, Computer History Museum.

In Memoriam memoriam Milton M. Silver (1923-2017), member since 1970, Industrial Electrochemistry and Electrochemical Engineering Division. Charles W. Struck (1928-2016), member since 1974, Luminescence and Display Materials Division. Israel Rubinstein — At press time, Interface learned about the death of Israel Rubinstein. There will be a full-length notice of his passing in the spring 2018 issue of the magazine.

Connect Share Discover ecsblog.org TheElectrochemicalSociety @ECSorg Find out what’s trending in the field and interact with a like-minded community through the ECS social media pages.

ECS Redcat Blog The blog was established to keep members and nonmembers alike informed on the latest scientific research and innovations pertaining to electrochemistry and solid state science and technology. With a constant flow of information, blog visitors are able to stay on the cutting-edge of science and interface with a like-minded community.

www.electrochem.org/redcat-blog

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Discover Your Community

Your ECS membership defines you as a leader in your field – as someone who believes in: • Disseminating scientific research in the most accessible ways • Advancing the science by bridging the gaps between academia, industry, and government

• Mentoring young people through networking and providing quality training and education • Honoring our heroes of the past, recognizing colleagues changing our lives now, and seeking those who are designing the future of our field

“I just like to disseminate my results. To share what I’ve done with others and help grow the field. That’s why I’m a member.” – Researcher and 12-year ECS member

MEMBERSHIP BENEFITS The ECS Member Article Pack—$3,500 VALUE—100 free downloads from all ECS journals giving you access to full-text articles in the ECS Digital Library, including the top publications in solid state and electrochemical science and technology: w Journal of The Electrochemical Society w ECS Journal of Solid State Science and Technology w ECS Electrochemistry Letters w ECS Solid State Letters w ECS Transactions w Electrochemical and Solid-State Letters

Open Access Article Credit—$800 VALUE—receive a complimentary article processing waiver to publish a paper in an ECS journal as Open Access.

Discounts each time you attend an ECS biannual meeting, meet colleagues and mentors face-to-face and participate in top-level symposia and networking get-togethers.

Free subscription to Interface, the quarterly magazine of record for the Society, delivered to your door, filled with the latest developments in the field and news and information for and about ECS members.

Exclusive access to the ECS Member Directory providing contact information for colleagues around the world.

Discounts on ECS products and services, including the ECS Monograph Series published by John Wiley & Sons.

Recognition for your achievements through ECS’s robust honors and awards program.

Plus, you will be notified immediately as new member benefits, discounts, and opportunities are added!

Admission to ongoing educational programs— allowing you to attend comprehensive one-day courses at exceptional member savings.

ro c

DA ECS he Y m .o ! rg

Questions about membership? Contact customerservice@electrochem.org l 609.737.1902, ext. 100

Jo T in e O

ECS MEMBERS Receive a Discount! Visit us at www.electrochem.org

Electrochemical Impedance Spectroscopy 2nd Edition

Mark E. Orazem, Bernard Tribollet This book provides the fundamentals needed to apply impedance spectroscopy to a broad range of applications with emphasis on obtaining physically meaningful insights from measurements. The second edition provides expanded treatment of the influence of mass transport, time-constant dispersion, kinetics, and constant-phase elements. The new edition improves on the clarity of some of the chapters, more than doubling the number of examples. It has more in-depth treatment of background material needed to understand impedance spectroscopy, including electrochemistry, complex variables, and differential equations. This title includes expanded treatment of the influence of mass transport and kinetics, and reflects recent advances in the understanding of frequency dispersion and interpretation of constantphase elements.

ISBN: 978-1-118-52739-9 Cloth | May 2017 | 768pp $135.00 | €129.60 | £108.00

About the Authors Mark E. Orazem is a Professor of Chemical Engineering at the University of Florida. He organized the 6th International Symposium on Electrochemical Impedence Spectroscopy and teaches a short course on impedance spectroscopy for The Electrochemical Society.

Visit us at www.ecsdl.org to see more titles and for your membership discount.

262611

Bernard Tribollet is the Director of Research at the Centre National de la Recherche Scientifique and Associate Director of the Laboratoire Interfaces et Systémes Electrochemique at Pierre and Marie Curie University. Dr. Tribollet instructs an annual short course on impedance spectroscopy.

Fluctuation Analysis by Ryan M. West

Electrochemical Information from Electrical Impedance

n electrochemical measurements, where electrical parameters are the very essence of scientific inquiry, resistance, and in extension impedance, can provide very valuable information. This has been recognized and exploited in measurements of electrochemical impedance spectroscopy (EIS), in particular in more recent years, when instruments or instrumental modules capable of this method became readily available. However, there is another method that allows obtaining electrical impedance: fluctuation analysis. Unlike EIS, which requires external perturbation of the system, fluctuation analysis relies entirely on the electrical signal originating in the random, thermally-driven fluctuations of the system. While both methods provide some identical information, they have also their unique capabilities. The merits of fluctuation analysis, the less familiar of the two methods, will be briefly outlined in this tutorial.

Sources of Noise Much time and energy is spent minimizing noise in electrochemical measurements. This is for good reason since the majority of noise encountered in the lab is from external sources—the 50 or 60 Hz hum of the line power, low frequency flicker noise of electronics, even the imperceptible vibrations of the benchtops may result in frustrating fluctuations in our measurements. This noise is of no analytical use and only acts to obscure information. But hidden beneath these nuisances is a more fundamental noise whose origin is the incessant, random, and rapid motions of the very molecules being studied. These fluctuations are thermally driven and unavoidable—they are a fundamental consequence of the inherent graininess of matter itself. In electrochemical systems and solid-state devices these fluctuations manifest themselves as current, voltage, conductivity, and work function noise. The measurement and analysis of this noise is the domain of fluctuation analysis.

Extracting Information from Noise It should come as no surprise that there exist precise relationships between these ever-present stochastic molecular events and deterministic macroscopic properties. Fluctuation analysis utilizes these relationships to recover information from the noise. With adequate electromagnetic shielding and low-noise pre-amplification, the fluctuations of the system under study can be isolated, measured, and analyzed. In essence, the fluctuations of a signal around its average value are due to the system’s “response” to thermally-driven perturbations. This idea is formally expressed by the FluctuationDissipation Theorem (F-D), which provides the theoretical and mathematical foundations upon which fluctuation analysis is based. There is no need for us to dive into the details of F-D here, but we should bear in mind that its consequences are fundamentally linked to our understanding of dynamic equilibrium. For example, the Einstein–Smoluchowski relationship describing Brownian motion is a direct manifestation of F-D. In fact, any system that demonstrates dynamic equilibrium of any kind will have measureable properties that fluctuate in time.1

Fluctuation analysis is most commonly carried out in the frequency domain by computing the power spectral density (PSD) of the noise. The PSD is a measure of the variance of a stationary fluctuating signal as a function of frequency. A stationary signal is simply one whose macroscopic properties don’t change in time. Essentially, the PSD is a deconvolution of the fluctuating signal into its frequency components, much like a prism filters light into its component wavelengths. A slowly fluctuating signal will have a large PSD at lower frequencies, whereas a signal with faster fluctuations will have a large PSD at higher frequencies. The shape and magnitude of the PSD provides the information in fluctuation analysis (Fig. 1).

Statistical Origin of Fluctuation Analysis Consider a simple isomerization reaction in which the forward and backward rate constants are both equal to 0.5 s-1 AsB The rate constant is the probability that species A will become B (or vice versa) per second. Note that this says nothing about the time scale of each isomerization event, which is assumed to be very small compared to the lifetimes of the species. This is a subtle but important point: the reaction itself may occur very quickly, but it is the lifetime of the particles as described by the rate constant that is probed by noise measurements. Now imagine two particles, one A and one B. On average, one of these particles will react each second. It’s important to keep in mind the statistical nature of the rate constant, i.e., there’s a chance that no reaction will occur or that more than one reaction will. But, most likely just one reaction will occur. Now increase the number of molecules to 1023. Again, on average, half the molecules will flip every second. There is a possibility that the flipping A’s and B’s cancel out, but not entirely, which is why the average is emphasized. This intrinsic variance, i.e., randomness, is a fundamental property of all chemical systems. Now let us monitor the number of A particles. In order to do so, we assume we can freeze time at specific intervals and count all the A particles. The time interval we choose will affect the variance in our count. To make this clear, let’s choose a time interval of 1/1000th of a second. Initially all particles are in some arbitrary state and the rate constant tells us that about 1/2000th of the 1023 particles will flip in this time interval, which means that the number of A particles will not change very much on average. In terms of the PSD, 1/1000th of a second corresponds to 1000 Hz, and at this frequency the signal does not have enough time to fluctuate much, therefore the variance is small. Now let’s restart the clock and freeze the system after every 0.1 s. On this time scale, many more of the particles will flip, 1/20th of all the molecules on average. Of course this implies that the signal is noisier at 10 Hz. Now, let’s freeze after every 1.0 s. Half of the molecules will flip during this interval and the system becomes even noisier. Now, if we freeze every 10 seconds, all the particles flip about 5 times and the system has many chances to become uncorrelated: at long time intervals, corresponding to small frequencies, the system completely forgets its initial conditions and the PSD reaches its maximum value. The analysis here can be extended to processes with more complex mechanisms, including redox reactions at electrode surfaces, transport across membranes, and the movement of charge carriers in electronic materials. Analysis of the PSD provides information about the mechanism and kinetics of spontaneous processes occurring in the system, without need to perturb the system at all.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued on next page)

West

Electrochemical interfaces are particularly well-suited for fluctuation analysis. At the equilibrium potential, there exists an exchange current, thus providing a way of monitoring the reactions in time. Electrochemical noise analysis can be illustrated by first considering the thermal noise across a resistor. The voltage across a resistor at equilibrium will fluctuate around zero, and if the resistor and leads are properly shielded, this noise is caused by the random motions of charge carriers within the resistor. The PSD of these thermal fluctuations is independent of frequency, and therefore known as white noise (Fig. 2). This noise exists in all conducting materials, no matter the nature or mechanism of conductivity, and no matter the material itself. In 1926, J. B. Johnson was the first to measure this noise, now known as the Johnson noise.2 The magnitude of the PSD is given by the Nyquist equation:

Given an equivalent circuit for an interface, the PSD of the voltage fluctuations can be determined by taking into account the resistor’s inherent thermal noise (see Eq. 1). Remember, Johnson noise doesn’t depend on the material properties of the resistor—in this case the resistor is simply part of a model describing an interface. In this equivalent circuit, the Johnson noise has a physically meaningful interpretation: it represents the stochastic nature of the charge transfer process. The double-layer capacitance has the effect of filtering this white noise so that the PSD is flat at low frequencies but after a certain “corner” frequency decreases as ƒ-2 (Fig. 2), resulting in a Lorentzian spectral shape. By simply measuring the voltage fluctuations across the electrochemical interface and plotting the PSD, the values of the charge-transfer resistance and double-layer capacitance can be determined. Beyond redox couples at metallic electrodes, measurements of Johnson noise at electrode interfaces have been successfully extended to the study of biological membranes,2 ionselective interfaces,3 liquid-liquid interfaces,5 nanopores,6 and corrosion analysis.7 In general, this method can be extended to any interface experiencing an exchange current at equilibrium. Of course, this same information could be obtained by EIS. The key difference is that during an EIS experiment a roughly 10 mV sinusoidal perturbation must be applied, but during the noise measurement the system has not been perturbed at all: the system is at true thermodynamic equilibrium. A practical difference between the fluctuation analysis and EIS is in the required equipment. A spectrum analyzer and perturbation signal source, or a potentiostat with built-in EIS functionality, is needed for EIS. On the other hand, the fluctuation analysis requires proper electromagnetic shielding (i.e., a Faraday cage), low noise amplification, and an analog-to-digital converter with a sampling rate high enough to capture the dynamics in the system being studied. More recently, noise analysis has become common enough (particularly in corrosion studies) that it is included in the functionality of some potentiostats.

SV = 4kTR

Current Fluctuations—Shot Noise

(continued from previous page)

Fig. 1. Shown on the left is a signal relaxing to equilibrium in time, with the fluctuations around the equilibrium value shown in the inset. On the right, a PSD of the fluctuating signal is shown. Note that the PSD is usually depicted on a log-log scale.

Potential Fluctuations—Thermal Noise

(1)

Here, k is Boltzmann’s constant, T is temperature, and R is the resistance. For example, for a one megaohm resistor at room temperature the Johnson noise is ~100 nV. (RMS value assuming a bandwidth of 1 Hz.) Notice that Johnson noise does not depend on the material properties of the conductor or any current flowing; it’s simply proportional to the temperature and resistance. While the Johnson noise of a resistor might not seem immediately relevant to an electrochemist, recall that an electrochemical interface can be modelled by an equivalent circuit. For the simple case of a metallic electrode in contact with a reversible redox couple, at equilibrium, a parallel RC circuit is an adequate and physically insightful model, which is regularly invoked to interpret EIS data.3,4 The resistance represents the charge-transfer resistance, which is related to the exchange current, i0, by

RCT =

RT nFi0

(2)

where R is the gas constant, T is the temperature, n is the number of electrons transferred per reaction, and F is Faraday’s constant. The capacitance in the RC circuit represents the double-layer capacitance.

In addition to Johnson noise, additional fluctuations are present when current flows, i.e., when the system is pushed out of equilibrium. This so-called shot noise in electrochemical and solid state devices is a consequence of the discrete nature of the charge carriers and the charge-transfer events. Much like thermal noise, the PSD is independent of the properties of the material and identity of the charge carrier. The root-mean square of the shot noise scales as the square-root of the average current leading to negligible noise at currents typically observed at microelectrodes. But as electrochemical devices continue shrinking to the nanoscale, shot noise may become more important.8 Shot noise resulting from single nanoparticle collisions at ultramicroelectrodes has recently been observed.9 Shot noise is also substantial at single molecular junctions.8 In general, both thermal noise and shot noise are unavoidable in solid state and electrochemical systems—they form the baseline noise present in any measurement. For nanoscale systems, out of equilibrium, analysis of the shot noise can provide valuable information about the system under study, information that is typically averaged out during macroscopic measurements.

Fig. 2. PSDs of the three types of noise commonly encountered in fluctuations analysis.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Conductivity Fluctuations—Excess Noise Excess noise, also known as flicker noise, describes any noise above thermal and shot noise. Under most experimental conditions it is the dominant source of fluctuations, particularly for solid-state devices. It has been measured extensively in the study of electronically conducting materials, corrosion phenomenon, and ion channels, which display this excess noise at low frequencies10,11 In solid-state materials, the flicker noise is generally attributed to fluctuations in the conductivity via either spontaneous fluctuations in mobility of charge carriers and/or number of charge carriers.12 The PSD has a characteristic 1/ƒα shape, where ƒ is the frequency and α ≈ 1 (Fig. 2). Unlike thermal and shot noise, the spectral characteristics depend on the material properties and charge-transfer mechanisms. Therefore, the measurement and analysis of excess noise, so-called flicker noise spectroscopy, can provide detailed information about the properties of the system under study. Flicker noise spectroscopy continues to be a valuable tool for understanding conduction mechanisms in devices and has been extended to the study of devices incorporating state-ofthe-art materials such as graphene13 and organic semiconductors.14

Work Function Fluctuations Work function is a measure of the energy required to move an electron from the bulk of an electronically conducting phase to the vacuum level. Work function fluctuations, like conductivity fluctuations, provide unique information about the dynamics of the charge carriers in conducting films at equilibrium.15 A fieldeffect transistor with a gate electrode composed of the material under study provides a unique platform for the measurement of work function fluctuations. Conducting polymers, e.g., polyaniline, generate noise above the thermal noise, shot noise, and excess noise of the field-effect transistor. This noise is found to have a stretched Lorentzian shape due to the broad distribution of time constants found in these disordered materials. Work function fluctuations also display limited spatial correlations in these films. A useful analogy can be made to local concentration fluctuations in an electrolyte solution—macroscopically the solution has a mean conductivity and ionic strength, but in any small volume element these properties fluctuate and the fluctuations in two different volume elements are not fluctuating “in sync.” These findings can also be rationalized by considering the disorder of conducting polymer films, which leads to the absence of extended electronic states and the presence of localized charge carriers. These observations have important consequences for gas sensing applications and other device applications utilizing disordered organic semiconductors, in particular when the interfaces between organic semiconductors and other conductors or insulators play a key role in device operation. The work function fluctuation analysis provides a unique tool for the study of these materials.

About the Author Ryan West is a professor at the University of San Francisco, in San Francisco, CA, where he teaches analytical and physical chemistry. He received his undergraduate and graduate education at the Georgia Institute of Technology, Atlanta, GA. His research interests include fluctuation analysis of conducting polymers and chemical sensing. He may be reached at rmwest2@usfca.edu. https://orcid.org/0000-0002-4739-3513

References 1. G. Feher and M. Weissman, Proc. Natl. Acad. Sci. U.S.A., 70, 3 (1973). 2. L. J. DeFelice, Introduction to membrane noise, Springer Science & Business Media (2012). 3. A. Haemmerli, J. Janata and J. J. Brophy, J. Electrochem. Soc., 129, 10 (1982). 4. A. Bezegh and J. Janata, J. Electrochem. Soc., 133, 10 (1986). 5. V. Mareček, M. Grätzl and J. Janata, J. Electroanal. Chem. Interfacial Electrochem., 296, 2 (1990). 6. C. Wen, S. Zeng, K. Arstila, T. Sajavaara, Y. Zhu, Z. Zhang and S. Zhang, ACS Sensors., 2, 2 (2017). 7. Z. K. Li, J. M. Reijn and J. Janata, J. Electrochem. Soc., 132, 3 (1985). 8. D. Djukic and J. M. Van Ruitenbeek, Nano Lett., 6, 4 (2006). 9. X. Xiao and A. J. Bard, J. Am. Chem. Soc., 129, 31 (2007). 10. P. Dutta and P. M. Horn, Rev. Mod. Phys., 53, 3 (1981). 11. S. Kogan, Electronic noise and fluctuations in solids, Cambridge University Press (2008). 12. A. K. Raychaudhuri, Curr. Opin. Solid State Mater. Sci., 6, 1 (2002). 13. A. A. Balandin, Nat. Nanotechnol., 8, 8 (2013). 14. C. Bonavolonta, C. Albonetti, M. Barra and M. Valentino, J. Appl. Phys., 110, 9 (2011). 15. R. M. West, M. Josowicz and J. Janata, Phys. Chem. Chem. Phys., 15, 20 (2013).

Conclusions Fluctuation analysis is a broad term used to describe any technique in which a system’s intrinsic noise is used to obtain information. In the field of electrochemistry, fluctuation analysis can be applied to measurements of potential, current, conductivity, and work function on a variety of liquid and solid-state systems. While it’s true that there is some overlap with the EIS (e.g., both methods can be used to determine charge-transfer resistance and double-layer capacitance), the fluctuation analysis can be carried out at true thermodynamic equilibrium, without any external perturbation. Additionally, fluctuation analysis can provide unique and complementary information to other techniques when applied to systems out of equilibrium (e.g., corrosion) or applied in situations where an equivalent perturbation would be hard or impossible to impose (e.g., conductivity and work function fluctuations). As electrochemical and solid-state devices continue to shrink, along with the signals they generate, fluctuation analysis has the potential to become an increasingly convenient and informative tool in the electrochemist’s bag. © The Electrochemical Society. DOI: 10.1149/2.F02174if.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

coming soon

a free preprint service for electrochemistry and solid state science and technology

Visit www.electrochem.org/ecsarxiv to learn more!

Questions? Contact ecsarxiv@electrochem.org. 52

The Electrochemical Society Interface â&#x20AC;˘ Winter 2017 â&#x20AC;˘ www.electrochem.org

Relating Cyclic Voltammetry and Electrochemical Impedance Spectroscopy in a Mass Transport Controlled System by Robert M. Mayall and Viola I. Birss

yclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) have become two of the most ubiquitous techniques in electrochemistry over the past few decades. While there have been many excellent reviews, textbooks, and introductory papers written regarding CV, the jump that most students undertake from CV to EIS has much less supporting literature to draw on. This is especially true in the cases of reversible mass transport controlled systems where the Warburg impedance may become a predominant feature. Thus, we have developed a logical framework with which to demonstrate the interweaving concepts found in both CV and EIS in a reversible mass transport controlled system such that it may be used as an effective teaching tool for those aspiring to apply both techniques in the study of electrochemical systems.

Relevant Background Information Before relating CV and EIS in a mass transport controlled system (specifically under diffusion control), it is important to review these techniques in a simple manner. More detailed descriptions of these techniques can be found in Ref. 1-5. Diffusion control in electrochemistry occurs when the rate determining step in a given electrochemical reaction is the diffusion of a reactant from the bulk of the electrolyte solution to the electrode surface, or vice versa. When this is observed over the full potential range under investigation, this is referred to as “reversible electrochemistry”. Under these conditions, the Nernst equation applies at all potentials, using the instantaneous surface concentration of the reactants and products. The exponential relationship between current and overpotential, derived by Butler

and Volmer, is valid for processes controlled by reaction kinetics (“irreversible electrochemistry”) and is not observed in reversible electrochemistry. Detailed discussions of irreversible Butler-Volmer electrochemistry can be found in Ref. 6. All examples given here are for three-electrode experiments. We will utilize the term CV when describing an experiment in which the potential of a working electrode (WE) is swept from an initial potential, E1, to a potential limit, E2, at a constant rate, υ, before being swept back to E1. The resultant current is plotted as a function of the potential applied at the working electrode vs. the reference electrode (RE), giving a voltammogram, such as the one shown in Fig. 1a for a quiescent solution. For an aqueous system with a soluble reactant/ product, a typical voltage range would cover several hundred millivolts at scan rates typically between 1 mV∙s-1 and 1 V∙s-1. In contrast to CV, EIS experiments involve much smaller amplitude potential perturbations to the WE than in normal CV, with a sinusoidal potential wave applied vs. the RE. This waveform is applied around a certain potential, Eapp, sometimes called the dc bias, with the AC voltage applied around Eapp, from an initial frequency, fi, to a final frequency, ff. In many experiments, Eapp is the open circuit (or equilibrium) potential of the WE in the solution under investigation, although some EIS studies may involve polarization of the WE to a different dc bias potential during an EIS experiment. Typical frequencies used in an EIS experiment range from millihertz to megahertz, with applied AC amplitudes typically of <20 mV at low temperature conditions (<100 °C). Figure 1 demonstrates the typical results that would be obtained from both a CV (Fig. 1a) and EIS (Fig. 1b) experiment, performed in a quiescent solution containing a soluble redox couple, Fe(CN)63-/4-, at an inert electrode (Au). The CV shows both an anodic and cathodic peak, centered at the formal potential (ca. 0.195 V vs Ag/AgCl in this (continued on next page)

Fig. 1. (a) Cyclic voltammogram for 1 mM Fe(CN)63-/4- in a 0.2 M sodium phosphate solution. A scan rate of 250 mV∙s-1 was used between 0 and 0.4 V vs a Ag/ AgCl reference electrode. (b) Nyquist representation of the impedance spectra obtained from the system studied in panel a. The applied 10 mV AC wave was swept from 1 MHz to 10 mHz around the open circuit potential (equal to the E0′, 0.195 V vs Ag/AgCl, in this experiment). A Pt mesh counter electrode and a polished Au disk working electrode with a geometric area of 0.3 cm2 was used. A calculated fit to the Randles circuit, a classical equivalent circuit for a mass transport controlled system, is shown by the red dashed line, which is separated into the higher frequency electrode charge transfer processes, represented as an arc, and the lower frequency Warburg impedance, seen as the line at 45°. The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Mayall and Birss

(continued from previous page)

Fig. 2. (a) Schematic representation of concentration profiles present near the WE/solution interface in a quiescent system during the application of a high frequency AC perturbation. (b) Schematic representation of concentration profiles present in a quiescent system during the application of a low frequency AC perturbation. Both representations are for a system with an equal mix of the Ox and Red forms (1 mM each) of the redox couple in the bulk solution.

work) of the redox couple in 0.2 M pH 7 sodium phosphate buffer. After the peaks, there is a characteristic t1/2 drop-off in the current that is typical of quiescent mass transport controlled system. The peak currents depend on the square root of the sweep rate, and the anodic/cathodic peak separation either does not change with sweep rate (“reversible mass transport controlled electrochemistry”) or becomes larger as the sweep rate increases (“quasi-reversible” or “irreversible” electrochemistry, where Butler-Volmer kinetics begin to dominate at low overpotentials6 and diffusion is rate limiting at higher overpotentials, giving the CV peaks). Figure 1b shows a distinctive Nyquist plot (in-phase impedance on the x axis and out-of-phase impedance on the y axis), obtained at the formal potential (0.195 V vs Ag/AgCl), i.e., the equilibrium potential, showing three main features. At the high frequency end of the spectrum, there is an offset from the origin of the plot due to the solution (series) resistance between the WE and RE, followed by an arc (semi-circle). This arc arises from the response to the resistance of charge transfer (RCT) and a parallel capacitive element (double layer) associated with the Fe(CN)63-/4- electron transfer reaction across the electrode/solution interface. As the frequency is lowered further in the quiescent EIS experiment, a third feature, the straight line at a 45 degree angle above the X-axis, becomes dominant. This is referred to as the Warburg impedance and is related to the growing depletion zone of reactants proximal to the electrode surface during the experiment. A calculated arc and modelled Warburg impedance are overlaid on the raw data for comparison purposes.

The Nernst Equation and Concentration Gradients in Quiescent Experiments It is important to note that the EIS experiment, which involves gathering data over a wide range of applied frequencies, can reveal both kinetic (RCT) and mass transport (Warburg) controlled 54

electrochemistry simultaneously. For a CV experiment to reveal similar information from the same electrochemical system, the scan rate would need to be varied over multiple orders of magnitude. Thus, a simple view of impedance spectroscopy is that each tested frequency in the EIS experiment represents a unique CV scan rate for the same system. It is well documented in the literature that faster scan rates will produce electrochemically irreversible CVs that are dominated by kinetic control, whereas slower scan rates exhibit reversible, mass transport controlled voltammograms (such as seen in Fig. 1a). These fast scan rates, where kinetic control (Butler-Volmer) is dominant, are represented by the high frequency portion of the Nyquist plot (Fig. 1b), whereas the mass-transport controlled, reversible CVs are represented by the low frequency process. The reason for the emergence of mass transport control at low frequencies (i.e., at slower scan rates) stems from the generation of a new equilibrium of oxidized (Ox) and reduced (Red) forms of the redox couple at the electrode surface, as governed by the Nernst Equation (Eq. 1). This equation holds true for any reversible mass transport controlled electrochemical process. It states that, at any given applied E, the surface activity of Ox and Red will fixed by E, and that, at the formal potential for the system (E0′), the activity of Oxsurf and Redsurf at the surface will be equal. E = E 0′ +

 Oxsurf 2.3RT log   Red nF surf 

  

(1)

In the case explored in Fig. 1, where the concentrations of Fe(CN)63- and Fe(CN)64- were equal in the bulk solution and the EIS experiment was performed at the formal potential of the redox couple (equal to the open circuit potential), we can examine the Warburg impedance in terms of concentration gradients near the electrode surface. At high frequencies, the AC potential perturbation changes rapidly, generating minimal changes to the surface concentration of The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

the two forms of the redox couple. As such, there is essentially no dependence of the electrochemical reaction rate on the transport of either species to the electrode surface. This is depicted schematically in Fig. 2a. In contrast, the surface concentrations of the two forms of the redox couple are significantly altered when a sufficiently low frequency AC perturbation is applied as enough time has passed to deplete the reactant proximal to the electrode. In this case, the concentrations of the two forms reach a steady-state at the electrode surface, with the local environment being depleted of the reactant, while the product concentration has built-up. This is depicted in Fig. 2b. An alternate way to envision the effect that a sufficiently low frequency AC potential would have on the concentration gradient is to imagine an extreme example where each point in the AC wave could be treated as a constant DC potential. Here, the electrode would reach a steady-state surface concentration of the two forms of the redox couple and then deplete the local environment of reactant at a rate of t1/2 until bulk electrolysis (complete conversion of one redox species to its other form in the solution bulk) is achieved, as governed by the Cottrell equation (Eq. 2).

nFAc 0 D πt

(2)

The Effects of Solution Convection on Cyclic Voltammetry and Impedance Spectroscopy The system described above raises the question of how one might alter or minimize the effects of diffusion control during an EIS experiment. The introduction of convection to the system, typically through the use of a rotating disk electrode (RDE), is a

common method to form an unstirred layer of fixed thickness close to the electrode, while the bulk concentrations remain constant. A CV of a convected solution, still showing reversible diffusion controlled electrochemistry, is shown in Fig. 3a. In the impedance spectrum of this type of system, the high frequency process remains unchanged, as this represents the kinetics of the Fe(CN)63-/4- couple at the electrode rather than mass transport control (Fig. 3b). However, at low frequencies the Warburg term begins to deviate from the 45 degree response seen in an quiescent system. At the high frequency end of the Warburg process in the Nyquist plot, during the transition from the kinetically controlled process, the introduction of convection does not significantly alter the impedance response. At these frequencies, the reactant proximal to the electrode surface is being depleted and the product is building up, as seen in quiescent solutions. When this depleted zone extends into solution and reaches the boundary of the unstirred layer and the solution bulk, controlled by the convection rate, the impedance spectrum deviates from that of the quiescent one. Fig. 3c depicts the concentration gradients present near the WE surface under these convected conditions. The effect of convection becomes pronounced at low frequencies when the concentration gradients reach a constant value, as dictated by the WE rotation rate. Here, the spectrum deviates from the 45 degree line typical of the Warburg impedance to form a second arc, sometimes referred to as a bounded Warburg arc, which reflects the diffusion boundary created by the convection. This is because the current is now completely dependent upon the diffusion of reactants to the electrode surface at these frequencies and there is no further change in this diffusion rate once the concentration gradient has reached the mass transport boundary. Thus, no matter how much lower the applied AC frequency is, the overall impedance will not increase further as the system has reached a steady-state.

Fig. 3. (a) Cyclic voltammogram for 1 mM Fe(CN)63-/4- in 0.2 M sodium phosphate with (100 mV∙s-1, 1000 RPM) and without (250 mV∙s-1) convection, with these sweep rates selected to bring the quiescent CV into a similar current range as the convected CV. (b) Nyquist representation of the impedance spectra obtained from the system studied in panel a. The applied 10 mV AC wave was swept from 1 MHz to 10 mHz around the open circuit potential (equal to the E0′, 0.195 V vs Ag/AgCl, in this experiment). A Pt mesh counter electrode and a polished Au disk working electrode with a geometric area of 0.3 cm2 was used. (c) Schematic representation of the concentration gradients present in a convected system during the application of a low frequency AC perturbation. The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Mayall and Birss

(continued from previous page)

Concluding Remarks Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are two powerful techniques that explore different aspects of an electrochemical system. A CV experiment reveals the response of a system at a defined scan rate (frequency) over a certain potential range, while an EIS experiment explores the response over multiple frequencies at a defined working electrode potential. When mass transport is rate limiting, the EIS response can manifest itself in various ways, depending upon whether the electrochemical reaction is fast or slow and if the solution is convected or not. Importantly, there is a lack of understanding regarding how to translate between CV and EIS results for the same system, with the purpose of this Chalkboard contribution being to help add clarity to this issue. It is also shown that the combination of these two techniques can provide more information to an experimenter than either can alone. © The Electrochemical Society. DOI: 10.1149/2.F03174if.

Acknowledgments The authors thank the Natural Sciences and Engineering Research Council of Canada (NSERC) for the overall support of this work, and the Alberta Innovates and Vanier Scholarship programs for the support of RMM. We also acknowledge useful discussions with Johna Leddy, Petr Vanýsek, Anne Co, and Keryn Lian on this subject.

About the Authors Robert Mayall is a Vanier Scholar in the third year of his PhD program in electrochemistry under the supervision of Viola Birss in the Department of Chemistry at the University of Calgary. He has a BHSc. in biomedical sciences and has been involved in research projects ranging from genetically engineering microbes for environmental remediation to the study of nanoparticles trapped at liquid/liquid interfaces, with his PhD work focussed on the development of novel electrochemical biosensors for the rapid detection of biological weapons. Outside of his research at the University of Calgary, Mayall is also a co-founder of FREDsense Technologies, a biotechnology company utilizing electrochemistry and synthetic biology to engineer portable sensors capable of rapidly detecting toxins in the field. He may be reached at rmmayall@ucalgary.ca.

Viola Birss is a professor of chemistry and a Tier I Canada Research Chair in Fuel Cells and Related Energy Systems at the University of Calgary, also having been the co-founder and leader of the Western Canada Fuel Cell Initiative and the Solid Oxide Fuel Cells Canada (SOFCC) Network. She is currently the scientific director of the Calgary Advanced Energy Storage and Conversion Research Technology group in Calgary, while also leading a research group of ca. 20 students/PDFs. Birss has made seminal contributions to the understanding of hydrous oxide surface films, the development of electrocatalysts and support materials for high temperature (SOFC) and low temperature fuel cells, electrolysis cells and supercapacitors, as well as in the investigation of nanostructurally ordered nanomaterials and electrochemical pathogen sensors. She may be reached at birss@ucalgary.ca.

References 1. M. E. Orazem and Tribollet, Electrochemical Impedance Spectroscopy, John Wiley & Sons, Hoboken, New Jersey (2008). 2. A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, pp 368-416, John Wiley & Sons, New York (2001). 3. C. M. A. Brett and A. M. Oliveira Brett, Electrochemistry: Principles, Methods and Applications, pp. 224-251, Oxford University Press, Oxford (2005). 4. G. A. Mabbott, “An Introduction to Cyclic Voltammetry,” J. Chem. Educ., 60, 697 (1983). 5. P. T. Kissinger, and W. R. Heineman, “Cyclic Voltammetry,” J. Chem. Educ., 60, 702 (1983). 6. A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, pp. 1-86, John Wiley & Sons, New York (2001).

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Looking at Patent Law: Opportunity Prospecting by Analysis of Analogous Patent Art by E. Jennings Taylor and Maria Inman

n this article we discuss the use of patent citation analysis to identify additional technology applications and potential collaborators or licensees for the patented technology. U.S. law stipulates1 that:

“[Patents] shall have the attributes of personal property.ˮ

As we noted in a previous article2 in Interface, the analogy between real property and intellectual property (patents) can provide helpful perspective. Of particular relevance to patent citation analysis is the analogy between the deed of real property and the claims of a patent. The deed defines the boundaries of ownership by the owner of the real property. The patent claims define the boundaries of ownership by the assignee of the patent. Recall, inventors are generally obligated to assign patent rights to their employer.3 In the case of real property, modern surveying methods lead to precise determination of the boundaries of the real property described in the deed. In the case of a patent, the courts have recognized that language can be imprecise:4 “The nature of language makes it impossible to capture the essence of a thing in a patent application [claim].” Consequently, the intellectual property “boundaries” defined by the claims are often referred to as the “metes and bounds” of the patent. The “metes and bounds” description is derived from an early system of defining the boundaries of real property, where the boundaries are described by the local geography of the parcel of land and are therefore somewhat imprecise. Related to our discussion of opportunity prospecting, when a prospective buyer initiates the purchase of a parcel of land, a search is conducted by a title company to ensure there are no previous owners or legal encumbrances on the real property. During this search, the title company identifies previous owners, current owners, and neighboring properties. Analogously, when an inventor files a patent application, an examination of the prior art is conducted by the U.S. Patent & Trademark Office (USPTO) to ensure there are no previous owners

of all or part of the claimed invention upon which the pending patent application would “trespass.” If prior art is identified that impacts the patentability of a patent application, then the inventor may limit the claims of her/his patent application in order to overcome said prior art. In addition, during the prior art search, the patent examiner identifies background or “neighboring” prior art patents, published patent applications and other publications. Consequently, inventors have the opportunity to become aware of a rich landscape of prior art during examination of their patent applications. Similarly, after a patent application is published and/or subsequently issues, it becomes part of the prior art landscape. Consequently, once a Faraday patent issues, we find it valuable to review the prior art landscape of “backward” citations cited during the examination of the patent application. Additionally, we continue to monitor U.S. Patent & Trademark Office actions to identify “forward” citations where Faraday patents are referenced as prior art against subsequent patent applications. These forward or “referenced by” citations provide the basis for opportunity prospecting by analysis of this analogous prior art. Herein we provide an actual case study illustrating the use of patent citation analysis to identify additional technology applications and potential collaborators or licensees for one of Faraday’s patented technologies. To begin the case study, we provide a brief background of Faraday Technology Inc. as perspective. Our perspective is based on over 25 years of experience at Faraday Technology Inc., a research, development, and engineering company, that was founded in 1991 to conceive, develop, and commercialize novel electrochemical technologies based on pulse current/pulse reverse current (PC/PRC) electrolytic principles. Excellent reviews on PC/PRC plating are available in the seminal work edited by

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued on next page)

Taylor and Inman

(continued from previous page)

Puippe5 and more recently updated.6 Our unique approach to PC/ PRC plating AND surface finishing are summarized as well7,8 and illustrated in the company vision: “To develop robust and environmentally friendly electrochemical deposition and surface finishing processes based on simple electrolytes enabled by pulse/pulse reverse electric fields.” The company’s mission is to conceive and commercialize electrochemical processes based on the PC/PRC technology platform. To support these activities, funding is obtained through the U.S. Small Business Innovative Research (SBIR) and Small Business Technology Transfer (STTR) programs. These programs consist of a Phase I feasibility demonstration activity followed by a Phase II technology development and validation activity. Once the Phase II development activity has been completed, commercialization of the technology for private sector use or transition of the technology for government use comes from private sector or non-SBIR government funding, respectively. Critically, while the SBIR/STTR programs represent a highly competitive source of technology demonstration and validation funding, these programs allow the small business to retain assignment of the inventions “conceived or first actually reduced to practice” with said funds.9 We first demonstrated the effectiveness of PC/PRC surface finishing of automotive planetary gears by replacing a DC electrochemical deburring process based on ethylene glycol with a PC process using a low concentration aqueous salt solution.10 Building on the deburring results, we obtained Phase I and II SBIR funding from the National Science Foundation to demonstrate the ability to use PRC to electropolish nickel alloy coupons in low concentration aqueous salt solution.11 This work provided the basis for two patents assigned to Faraday.

Subsequently, we were approached by an engineer from a manufacturer of stainless steel valves for the semiconductor industry. The manufacturer employed conventional DC electropolishing as the final step for surface finishing of their stainless steel valves, fittings and tubular products. The conventional electropolishing process was based on the well-established viscous salt film paradigm12 and used a chilled electrolyte solution consisting of concentrated sulfuric/ phosphoric acid as well as proprietary additives that may have included fluoride species. Under a stage-gated research-for-hire activity, we demonstrated the ability to electropolish their stainless steel coupons using PRC in conjunction with a low concentration aqueous salt electrolyte. We subsequently demonstrated and validated the PRC electropolishing process on actual stainless steel products using an α-scale manufacturing apparatus in Faraday’s prototyping facility. For competitive reasons, the manufacturing company wanted to retain exclusive rights to the subject technology and we negotiated a “fieldof-use” license consistent with Faraday’s business model.13 The fieldof-use license was defined as follows: 1. Market – semiconductor 2. Product – valves and fittings 3. Material – stainless steel The license was based on two patents (Fig. 1) covering the subject PRC electropolishing technology.14,15 As noted above, we continuously monitor our issued patents to review backward prior art citations and identify forward prior art citations. Specifically, we define them as follows: 1. Backward prior art citations: Prior art cited by Faraday inventors and/or the USPTO examiner during the prosecution of the Faraday patent application, 2. Forward prior art citations: Citations of the Faraday patent as prior art by the inventors and/or the USPTO examiner during the prosecution of subsequent patent applications.

Field-of-Use (FoU) License • Market – Semiconductor • Product – Valves & Fittings • Material – Stainless Steel Fig. 1. Faraday patent nos. 6,402,931 and 6,558,231 licensed to valve manufacturer. 58

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Backward Citations (8)

Fig. 2. Google patent search results for Faraday patent no. 6,558,231.

These citations are easily tracked using the USPTO website16 or “Google patents.”17 In Fig. 2, we illustrate the search results for U.S. patent no. 6,558,231 (referred to below as the ‘231 patent) using Google Patents accessed on September 12, 2017. From the first page, we see that there were eight (8) background or prior art “patent citations” duringFigure the prosecution of the ‘231 number does 3. Forward Citations for patent. FaradayThis Patent No. 6,558,231 not change as a function of the date the Google Patents database is accessed. In addition, we see that there are twenty-nine (29) forward

Boston Scientific

Fig. 3. Forward citations for Faraday patent no. 6,558,231.

or “referenced by” citations as of the date the Google Patent database was accessed. Clearly, these forward citations can change with time as subsequent patent applications issue. For our trivia readers, U.S. patents always issue on a Tuesday. By selecting the “Referenced by” hyperlink, we are taken to the Google patent page with the 29 forward prior art patent citations shown in part in Fig. 3. This page provides the citing patent or patent application number, filing date, publication date, assignee, and title of the patent/patent application. For the prior art highlighted with an asterisk (*), the ‘231 patent was cited as prior art by the USPTO examiner during prosecution of the citing patent. For the prior art without a highlight, the ‘231 patent was cited as prior art by the applicant during prosecution of the citing patent. Upon scanning the list of forward citation prior art, we observe a number of Faraday patents/patent applications and patents/patent applications generally related to electrochemical machining or electrochemical polishing. Of particular interest for this case study is patent no. 7,153,411 (referred to below as the ‘411 patent) assigned to Boston Scientific Scimed, Inc. The highlighted “*” associated with the ‘411 patent indicates that the USPTO examiner cited the ‘231

patent during prosecution. By selecting the “US7153411” hyperlink, a Google patent page displaying the ‘411 patent appears. We downloaded the complete patent by Forward selecting the “Download PDF” hyperlink. Citations (29) By reviewing the claims,18 we determined that the ‘411 patent was directed towards the method or process statutory class. As illustrated in Fig. 4, the cover page of the ‘411 patent indicates that the method is an electropolishing method. Additionally, as illustrated in Fig. 4, Fig. 3/Fig. 2 of the ‘411 patent indicates that the electropolishing method is directed towards medical stents using pulse reverse waveforms. Finally, by review of the claims, we noted that many of the dependent claims were directed towards strong acid electrolytes with additions of chelating agents. This approach is in contrast to Faraday’s approach to development of PC/PRC electrochemical processes based on simple aqueous electrolytes. To summarize, based on this straightforward and simple preliminary analysis, we identified a potential new application, of which we were not previously aware, for Faraday’s PC/PRC process development activities. A more detailed understanding of the prior art citation of Faraday’s ‘231 patent application may be obtained by reviewing the file history of the prosecution of the ‘411 patent at the USPTO Patent Application Information Retrieval (PAIR) website portal.19 In Fig. 5, we illustrate the various documents within the “Image File Wrapper” for the ‘411 patent. These documents represent the correspondences between the USPTO examiner and the patent applicant during the prosecution of the subject patent application. These correspondences include the examiner’s prior art search, the examiner non-final and final rejection office actions, the applicant’s responses to non-final/ final rejections, applicant’s amendments to claims, issue notification and so forth. Our review of the prosecution history of the ‘411 patent application indicates that Faraday’s ‘231 patent was used to support an “obviousness” (35 USC §103) rejection of the claims directed towards pulse reverse electropolishing.18 The ‘411 patent applicant modified their claims to include limitations to the pulse reverse electropolishing method, which then allowed the patent to issue. As discussed earlier, there still could be “freedom to operate” issues associated with the ‘411 patent.2 With this analysis of analogous patent art, we identified a new opportunity for our platform PC/PRC technology directed towards electropolishing of medical stents in simple aqueous electrolytes enabled by our pulse reverse current approach. We successfully pursued funding from the National Institutes of Health (NIH) SBIR program and were awarded Phase I and Phase II projects. With this funding, we demonstrated the feasibility of electropolishing medical stent materials (nickel-titanium) in simple aqueous electrolytes.20 Subsequently, we worked with a supplier of nickel-titanium wire for stent applications to demonstrate and validate the pulse reverse electropolishing process in an α-scale reel-to-reel electropolishing apparatus consisting of 300 and 5,000 foot wire spools.21 These activities led to a license of the same two patents licensed to the semiconductor valve manufacturer but for a different “field-of-use” defined as follows: 1. Market – medical 2. Product – wire based stents and shape sets 3. Material – nickel-titanium alloys

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued on next page) 59

Taylor and Inman

(continued from previous page)

Figure 4. Boston Scientific Patent No. 7,153,411 Citing Faraday Patent No. 6,558,231

Pulse Reverse Current Electropolishing Medical Stent

Fig. 4. Boston Scientific patent no. 7,153,411 citing Faraday patent no. 6,558,231.

In summary, we presented a case study for opportunity prospecting by analysis of analogous patent art (Fig. 6). The approach uses forward or “referenced” by patent citation analysis to identify examiner or applicant prior art citations of the patent of interest during the prosecution of subsequent patent applications. The prior art citation analysis was illustrated using the Google patent search but is also easily conducted using the USPTO patent Boolean search function. While the case study was based on the experience at Faraday Technology Inc., an electrochemical research, development and engineering company with an electrochemical platform technology, we believe the approach would be valuable for other businesses, universities and federal laboratories. More specifically, we suggest that electrochemical scientists, engineers and technologists consider the patent literature in addition to their review of the technical literature. © The Electrochemical Society. DOI: 10.1149/2.F04174if.

About the Authors E. Jennings Taylor is the founder of Faraday Technology, Inc., a small business focused on developing innovative electrochemical processes and technologies based on pulse and pulse reverse electrolytic principles. Jennings leads Faraday’s patent and commercialization strategy and has negotiated numerous via field of use licenses as well as patent sales. In addition to technical publications and presentations, Jennings is an inventor on forty patents. Jennings is admitted to practice before the United States Patent & Trademark Office (USPTO) in patent cases as a patent agent (Registration No. 53,676) and is a 60

member of the American Intellectual Property Law Association (AIPLA). Jennings has been a member of the ECS for thirty-eight years and is a fellow of the ECS and currently serves as treasurer. He may be reached at jenningstaylor@faradaytechnology.com. http://orcid.org/0000-0002-3410-0267

Maria Inman is the research director of Faraday Technology, Inc. where she serves as principal investigator on numerous project development activities and manages the companies pulse and pulse reverse research project portfolio. In addition to technical publications and presentations, Maria is competent in patent drafting and patent drawing preparation and is an inventor on seven patents. Maria is a member of ASTM and has been a member of the ECS for twenty-one years. Maria serves the ECS as a member of numerous committees. She may be reached at mariainman@faradaytechnology.com. http://orcid.org/0000-0003-2560-8410

References 1. 35 U.S.C. §261 Ownership; assignment. 2. E. Jennings Taylor and Maria Inman, “Looking at Patent Law: Why Are Patents Often Referred to as Intellectual Property?” Electrochem. Soc. Interface, 26(1), 41 (2017). 3. E. Jennings Taylor and Maria Inman “Looking at Patent Law: Why Is the Word ‘Right’ Mentioned Only Once in the Constitution of the United States?” Electrochem. Soc. Interface, 26(2), 45 (2017). The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Figure 5. Image File Wrapper for Boston Scientific Patent No. 7,153,411

Allowance

Amendment Rejection of Claims

Fig. 5. Image file wrapper for Boston Scientific patent no. 7,153,411.

Commercial project to develop PC electrochemical deburring of carbon steel planetary gears in aqueous salt solution

NSF SBIR funds to demonstrate PRC electropolishing of passive alloys in low concentration aqueous salt solution (SBIR funding enabled IP rights to be retained)

Commercial project to develop PRC electropolishing of semiconductor valves in low concentration aqueous salt solution

NIH SBIR funds to demonstrate PRC electropolishing of Nickel-Titanium (Nitinol) stents in dilute acid solution

Commercial project to develop PRC electropolishing of Nickel-Titanium (Nitinol) stents and shape sets in dilute acid solution

Figure 6. Case Study of Opportunity Prospecting.

‘411 broad claims for PRC Electropolishing rejected based on ‘231 patent

Faraday Patent 6,558,231 Faraday Patent 6,402,931

Licensing deal for PRC electropolishing of stainless steel valves

Citation analysis identified new opportunity!

Licensing deal for PRC electropolishing of Nitinol stents and shape sets

Boston Scientific Patent Application with broad claims around PRC Electropolishing

Boston Scientific Patent issued with limited claims around PRC Electropolishing

4. Festo Corp. v. Shoketsu Kinzoku Kogyo Kabushiki Co., 535 U.S. 722 (2002). 5. J. C. Puippe and F. Leaman, Theory and Practice of Pulse Plating, AESF, Orlando, Florida (1986). 6. W. E. G. Hansel and S. Roy, Pulse Plating, Leuze Verlag KG, Germany (2012). 7. E. J. Taylor, “Adventures in pulse/pulse reverse electrolytic processes: explorations and applications in surface finishing,” J. Appl. Sur. Fin., 3(4), 178 (2008). 8. E. J. Taylor, M. E. Inman, H. M. Garich, H. A. McCrabb, S. T. Snyder, and T. D. Hall, “Breaking the Chemical Paradigm in Electrochemical Engineering: Case Studies and Lessons Learned from Plating to Polishing,” Advances in Electrochemical Science & Engineering; Electrochemical Engineering: The Path from Discovery to Product, Volume XVIII to be published (2018). 9. 35 U.S.C. 201 (1980) Definitions, Bayh-Dole Public Law 96-517, December 12, 1980. 10. E. J. Taylor and M. Inman, “Electrochemical Surface Finishing,” Electrochem. Soc. Interface, 23(3), 51 (2014). 11. J. J. Sun, J. J. Sun, L. E. Gebhart, R. P. Renz, E. J. Taylor, and M. E. Inman, “The application of CM-ECM technology to metal surface finishing” in Proceedings North American Manufacturing Research Institution of the Society of Manufacturing Engineers, MR00-209 NAMRC XXVIII May 24-26, Lexington, KY (2000). 12. P. A. Jacquet, “On the anodic behavior of copper in aqueous solutions of orthophosphoric acid” Trans. Electrochem. Soc., 69(1), 629 (1936). 13. E. J. Taylor and P. Miller, “Innovation case studies at an R&D company…alignment of technology, intellectual property and financial matters,” Les Nouvelles XXXVI (No. 2), June (2001). 14. C. Zhou, E. J. Taylor, J. J. Sun, L. E. Gebhart, and R. P. Renz, “Electrochemical machining method using modulated reverse electric fields,” U.S. Patent No. 6,402,931, issued June 11, 2002. 15. E. J. Taylor, “Sequential electromachining and electropolishing and the like using modulated electric fields,” U.S. Patent No. 6,558,231, issued May 6, 2003. 16. http://patft.uspto.gov/netahtml/PTO/search-adv. htm, last accessed: Oct. 2017. 17. https://www.google.com/?tbm=pts&hl=en, last accessed: Oct. 2017. 18. E. Jennings Taylor and Maria Inman, “Looking at Patent Law: Patentable Inventions, Conditions for Receiving a Patent, and Claims,” Electrochem. Soc. Interface, 26(3), 44 (2017). 19. https://portal.uspto.gov/pair/PublicPair, last accessed: Oct. 2017. 20. E. J. Taylor, M. E. Inman, T. D. Hall, and B. Kagajwala, “Electropolishing of Passive Materials in HF-Free Low Viscosity Aqueous Electrolytes,” ECS Trans., 45(8), 13 (2013). 21. H. Garich, T. Hall, S. Lucatero, S. Snyder, M. Inman, E. J. Taylor, and L. Kay, “Electrochemical Polishing of Nitinol and Other Medical Alloys in Aqueous Electrolytes Using Pulse/Pulse Reverse Electric Fields,” Paper 1248 presented at The Electrochemical Society Meeting, Chicago, IL, May 24-28, 2015.

Fig. 6. Case study of opportunity prospecting.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Discoveries need discoverability. The electrochemical and solid state community is making key discoveries in the areas of renewable energy, clean water, food safety, medical technology, and more. Such important discoveries need maximum discoverability. ECS Author Choice Open Access gives you the opportunity to make your research freely available to anyone with an internet connection. Find out more about how you can keep your copyright, reach more readers, and help save the world!

www.electrochem.org/OA

T ECH HIGHLIGH T S Mechanical Pre-Lithiation of Silicon Anodes for Lithium Ion Batteries Low Initial Coulombic Efficiency (ICE) continues to be a significant issue for the practical use of alloying materials, such as Si and Ge, as anodes and particularly for their implementation in full Li-ion cells. It is imperative to develop methods to improve ICE to mitigate issues associated with the consumption of electrolyte and the loss of Li during initial cycling. Several methods to improve ICE have been examined, including studying the effects of active material particle size and the use of various electrolyte additives such as vinylene carbonate. The prelithiation of anode materials has also been investigated using two different approaches—electrochemical and mechanical prelithiation. Researchers from the University of Tottori have reported on the formation of a crystalline Li-Si alloy phase via a mechanical alloying (MA) method. Appropriate mechanical prelithiation of the Si anode samples was shown to improve Coulombic efficiency, compared to pure Si samples. Additionally, the Li1.00Si electrode, fabricated using the MA method, exhibited 1.5 times longer cycle life compared to a pure Si electrode when cycled with a specific current of 3.0 A g-1. The evaluation of mechanically prelithiated, easy-to-produce anode materials offers valuable insight for future investigations to further improve ICE. From: Y. Domi, H. Usui, et al., J. Electrochem. Soc., 164, A1651 (2017).

Faraday Cage-Type Electrochemiluminescence Biosensor Based on Multi-Functionalized Graphene Oxide for Ultrasensitive Detection of MicroRNA-21 Detection and analysis of microRNAs have recently been of great interest due to their association with cancer and other diseases. Among the key challenges in developing analytical methods for a microRNA assay is their low concentration. Researchers from Ningbo University in China just reported an ultrasensitive electrochemiluminescence (ECL) microRNA-21 sensor, termed as a Faraday cage-type ECL, that pushed the detection limit down to 0.3 fM. Compared with a conventional sandwich type ECL assay, this new system operates the same way: an immobilized capture unit on the electrode surface captures the signaling unit and the target in the solution phase. The uniqueness of this new method, however, is the structure of the signaling unit. The authors used graphene oxide (GO) as the carrier on which multiple single signal DNA strands and multiple luminol molecules were covalently attached. The resulting GO bearing a net structure could hybridize along with the microRNA-21 to the capture DNA on the electrode surface to form a cage-like structure. Because of the high electronic

conductivity and the high surface area of the GO, the cage essentially formed part of the electrode and multiple luminol molecules could participate in the ECL reaction to enhance the signal significantly. From: J. Lu, L. Wu, Y. Hu, et al., J. Electrochem. Soc., 164, B421 (2017).

An Optimized Trivalent Chromium Conversion Coating Process for AA2024-T351 Alloy Chromate conversion coatings have been the industry standard for the corrosion protection of aluminum alloys for decades. However, recent regulations are significantly reducing their commercial availability due to the toxicity and carcinogenic nature of hexavalent chromium. Trivalent chromium conversion (TCC) coating processes are an alternative technology being pursued as a viable alternative to chromate, and a number of TCC coatings are now commercially available. A particularly challenging application for TCC coatings are highstrength, Cu-bearing alloys, such as AA2024. The Cu-rich particles that strengthen these materials are electrochemically active, and promote the formation of defects in applied TCC coatings, reducing their efficacy. In this paper, a specialized acidic deoxidizing treatment to remove surface-incident Cubearing precipitates combined with a warm water post-treatment was explored. A posttreatment 2 minutes in length in 40 °C deionized water significantly improved the corrosion protectiveness of TCC coatings. However, as the deposition time of the TCC coating was increased, numerous cracks formed in the coating—typically adjacent to intermetallic particles—degrading performance. From: J. Qi, L. Gao, Y. Li, et al., J. Electrochem. Soc., 164, C390 (2017).

Transfer Printing of Micron-Size Graphene for Photonic Integrated Circuits and Devices The growth of high-quality films is important for the increased utilization of graphene in a large variety of possible applications, particularly those involving photonics. Growth techniques such as chemical vapour deposition (CVD) can be used to form these high quality films; however, this direct growth technique is not compatible with many substrates on which integrated photonic devices are typically, built where site selectivity for the graphene is of high importance. There is a drive for improved high-throughput, cost-effective and scalable methods for the site-specific transfer of pre-grown graphene films. Currently, home-built transfer tools are used, which rely on the handling skills of an operator for effective use. A method for the transfer printing of CVD-grown micronsized graphene from one substrate to another using a commercially available automated

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

tool has been developed by a group based in Ghent University, Belgium. Raman spectroscopy and electrical conductivity analysis of the transferred graphene show comparable characteristics to the initial CVD film material subsequent to transfer without the reliance on user handling skills. This technique demonstrates both the high level of reliability and scalability possible for high quality graphene film transfer using a commercially available automated apparatus.

From: L. A. Shiramin, A. Bazin, S. Verstuyft, et al., ECS J. Solid State Sci. Technol., 6, P435 (2017).

A Portable Device for Personal Health Care Portable medical devices for personal health care, home care, and mobile diagnoses by medical professionals complement benchtop point-of-care instruments used in hospitals, urgent care centers, and other medical facilities. Researchers at National Cheng Kung University and National Tsing Hua University in Taiwan recently reported the design, development, fabrication, and prototyping of a transistor-based device for measurement of the C-reactive protein (CRP). The level of this protein is known to increase in blood when there is inflammation in the body, and can also be used to evaluate the risk of a person developing coronary artery disease. Many researchers believe proper treatment of people with elevated CRP will lessen their risk of heart attack or stroke. In this ECS Editors’ Choice article, the authors describe a simple, elegant process for embedding a miniaturized AlGaN/GaN high electron mobility transistor (HEMT) in a plastic-based package. CRP aptamer was immobilized on the surface of the HEMT gate electrode, and a microfluidic capillary channel was incorporated into the device to flow test solutions in/out of the package. Measurement of the drain current of the packaged HEMT sensor was demonstrated to be a sensitive measurement signal for CRP in clinical blood sera, with a detection limit below 1 mg/L. From: P.-C. Chen, Y.-W. Chen, I. Sarangadharan, et al., ECS J. Solid State Sci. Technol., 6, Q71 (2017).

Tech Highlights was prepared by David Enos and Mike Kelly of Sandia National Laboratories, Colm Glynn and David McNulty of University College Cork, Ireland, Zenghe Liu of Verily Life Science, and Donald Pile of Rolled-Ribbon Battery Company. Each article highlighted here is available free online. Go to the online version of Tech Highlights in each issue of Interface, and click on the article summary to take you to the full-text version of the article.

Future ECS Meetings Seattle, WA

Cancun, Mexico

USA 2018 233rd ECS Meeting

AiMES 2018

May 13-17, 2018

September 30-October 4, 2018

Seattle Sheraton and Washington State Convention Center

Moon Palace Resort

Dallas, TX

USA 2019

Atlanta, GA

USA 2019

235th ECS Meeting

236th ECS Meeting

Sheraton Dallas

Hilton Atlanta

May 26-May 31, 2019

October 13-17, 2019

www.electrochem.org/meetings

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Importance of Dielectric Science in Today’s Technology by Durga Misra

he explosive progress of information technology and 5th generation communication technology enables the introduction of the Internet of Things, where the network of physical objects—devices, vehicles, and buildings embedded with sensors, electronics, software, and network connectivity—permits these physical objects to collect and exchange data. The use of dielectric materials in sensors for a multitude of applications such as self-driving cars has made the dielectric science and technology research even more significant than before. More than seventy years ago, in 1945, it all started with establishing the Electric Insulation Division in ECS to offer an interdisciplinary forum to discuss the science of the materials used for electrical insulation in power transmission. With the advancement of technology, when integrated circuits became popular, the division became the Dielectrics and Insulation Division in 1965. In 1990, it became the Dielectric Science and Technology Division due to extensive growth in electronic manufacturing technology. Today, the division still provides a strong interdisciplinary research environment. Recently, the division’s focus has related to new dielectric devices with applications in sensor technology, devices for new communication technologies, and new materials and processes for nanoelectronics manufacturing. In the earlier days, the division mostly considered topics like electrophysics, electrical properties of plastics, wet electrolytic capacitors, wires and cables, inorganic and organic dielectrics, liquid dielectrics, high temperature insulation, prefabricated circuitry, and chemical aspects of printed wiring. Thirty years ago, the focus was on anodic oxide dielectrics for electrolytic capacitors, silicon nitride, and silicon oxide thin insulating films for electronic applications, plasma processing, chemical vapor deposition, multilevel metallization, diamond and diamond-like carbon films, corrosion and reliability of electronic materials and devices, III-V nitride materials and devices, and rapid thermal processing of dielectrics. Subsequently, with the introduction of new materials and processing technologies the focus of Dielectric Science and Technology Division has changed to post-CMOS devices and dielectrics in nanosystems. The division stimulates and disseminates fundamental research on present and future dielectric materials and their synthesis, characterization, processing, fabrication, manufacturing, and reliability through its symposia and short courses. In this issue of Interface we have focused on some of the current topics that are an integral part of current and future technologies. The first article in this issue, by Chen, reviews the nanoscale hybrid dielectric materials used in humidity sensors. These sensors use a porous α-Al2O3(sapphire)/SiO2 hybrid dielectric capacitive structure. When the humidity level in the environment changes, it results in a change of the dielectric constant of the porous dielectric material because of absorption of water molecules. This leads to a change of the capacitance and impedance of the sensors. This α-alumina(sapphire)/silicon dioxide hybrid dielectric humidity sensor exhibits long-term stability, fast response, and durability at extremely high/low humidity levels. This dielectric sensor finds its way to many applications starting from household appliances, automobiles, health care equipment, to agricultural applications.

In the second article, by Sai, et al., the authors discuss magnetic nanoferrites for radio frequency CMOS technology, where the functional materials, especially magnetic oxides such as ferrites, are used in higher frequency integrated devices for the 5th generation communication systems. A low-temperature CMOS-compatible deposition of ferrite films and its integration as a deposition method into the semiconductor processing technology is definitely required for the success of new devices. Since the hexagonal ferrites and their stoichiometric derivatives can be used as suitable magnetic materials in the frequency bands ranging from a few GHz to several hundreds of GHz, extensive research to attain industry-scale reliability and control over material properties is required for the deposition of these hexaferrite films. The article suggests that microwave-irradiation assisted solution-based nonequilibrium spinel ferrite deposition technique offers promise towards CMOS-compatible and scalable ferrite film deposition. For characterization, highly sensitive permeability measurement systems need to be developed. Magnetic nanoferrites bring an interdisciplinary approach by combining the wisdom of RF engineers, semiconductor technologists, material scientists, physicists, and chemists. The third article, by Iwai, et al., provides an overview of high dielectric constant materials for nanoscale devices and their possible future applications. A historical perspective is provided by outlining the development of these materials over the last twenty years. Some new understanding of these materials that can have new applications in future nanoscale devices are discussed. The reliability aspect of these materials used in advanced devices is also addressed. Even though some of the technologies have matured, new science finds novel applications for these materials. A symposium on physics and technology of high-k gate dielectrics, started in 2002, completed its 15th edition at the 232nd meeting of the ECS in National Harbor in 2017. The fifteen volumes of the symposium proceedings represent a unique collection of research publications on the high-k gate stacks, high mobility channel semiconductors, gate electrode metals, and the related topics. © The Electrochemical Society. DOI: 10.1149/2.F06174if.

About the Guest Editor Durga Misra is a professor in the electrical and computer engineering department at the New Jersey Institute of Technology, Newark, NJ. He received an MS (1985) and a PhD (1988) in electrical engineering from University of Waterloo, Waterloo, Canada. He is a past chair of the Dielectric Science and Technology Division of ECS. He is a fellow of ECS and a senior member of the Institute of Electrical and Electronics Engineers. He received the Thomas D. Callinan Award from the DS&T Division and also the winner of the Electronic and Photonic Division Award. His research interests are in the areas of nanoelectronic/optoelectronic devices and circuits especially in the area of high-k gate dielectrics and its reliability. He has published over 250 papers in journals and conferences and edited and co-edited more than 40 proceeding volumes and ECS Transactions. He may be reached at dmisra@njit.edu. https://orcid.org/0000-0001-6844-6058

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

BATT ERY E LE

SILICO N

PLA SMA

CTRO LYTE S

COMPA TIBLE

NAN O

ECS S ER MEMB IVE RECE FF 20% O

SCIE

NCE

Issues from the 232nd ECS Meeting Now Available! Browse all available titles: www.electrochem.org/ecst

Forthcoming Publications:

• 18th International Conference on Advanced Batteries, Accumulators and Fuel Cells (ABAF 2017) – Brno, Czech Republic (September 10-13, 2017) • 6th International Conference on Electrophoretic Deposition – Gyeongju, South Korea (October 1-6, 2017)

• Fuel Cell Seminar & Energy Exposition 2017 – Long Beach, CA (November 7-9, 2017)

• XXXII National Congress of the Mexican Electrochemistry Society (SMEQ) 2017 – Guanajuato, Mexico (June 5-8, 2017) Email ecst@electrochem.org for more information. 66

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Novel Humidity Sensors Based on Nanoscale Hybrid Dielectric Materials by Zhi David Chen

umidity sensors are extensively used in industrial processing and environmental control.1,2 For manufacturing of highly sophisticated integrated circuits in the semiconductor industry, humidity or moisture levels are constantly monitored in wafer processing.3 There are many household applications for humidity sensors, such as intelligent control of the living environment in buildings and houses, cooking control for microwave ovens, and intelligent control of laundry.1 In the automobile industry, humidity sensors are used in rear-window defoggers and motor assembly lines. The lithium-ion batteries used in electrical automobiles are manufactured at low humidity levels, which are monitored and controlled by highly-sensitive humidity sensors, called dew point meters. In the medical field, humidity sensors are used in respiratory equipment, sterilizers, incubators, pharmaceutical processing, and biological products. In agriculture, humidity sensors are used for green-house air-conditioning, plantation protection (dew prevention), soil moisture monitoring, and cereal storage. In the general industrial framework, humidity sensors are used for humidity control in chemical gas purification, dryers, ovens, film desiccation, paper and textile production, and food processing.1

Humidity/Moisture Measurement Units Based on measurement techniques, the most commonly used units for humidity measurement are relative humidity (RH), dew point/ frost point (DP/FP) and parts per million (PPM).2 Relative humidity is the ratio of the partial pressure of water vapor present in a gas to its saturation vapor pressure at a given temperature. The RH measurement is expressed as a percentage, which is a relative value because the saturation vapor pressure increases with temperature. Parts per million represents water vapor content by volume fraction (PPMv) or by weight (PPMw) if multiplied by the ratio of the molecular weight of water to that of air. PPMv is an absolute measurement. Dew point is the temperature (above 0 °C) at which the water vapor in a gas condenses to liquid water. Frost point is the temperature (below 0 °C) at which the vapor condenses to ice. DP/FP is a function of the pressure of the gas but is independent of temperature and is therefore defined as an absolute humidity measurement. Figure 1 shows the correlation among relative humidity, parts per million by volume, and the dew point/frost point. RH measurement covers the higher humidity range, PPMv covers the lower humidity range, and the dew point/frost point covers the entire humidity range. To simplify the terminology, dew point/frost point is usually called simply “dew point.” In daily life, relative humidity is typically used for ease of understanding. For trace moisture measurements, it would be better to use dew point or PPMv, because it tells us the absolute amount of water vapor in a gas or air.

to produce relative humidity sensors because high sensitivity is not required. However, for dew point sensors, extremely high sensitivity is required so that they are able to detect trace moisture levels below 0.5 PPMv or −80 °C DP (see Fig. 1). In addition, dew point sensors can be used for both low humidity and high humidity measurements because of their high sensitivity, but RH sensors cannot be used for low humidity measurement due to their low sensitivity. Currently dew point (moisture) sensors on the market include ceramic sensors, polymer sensors, aluminum oxide film sensors, and chilled-mirror hygrometers.1,2 All sensors on the market have some advantages and drawbacks. The chilled-mirror dew point hygrometers have very high precision, and thus are used as the standard for calibration of other sensors. But they have very high cost.1,3 Ceramic sensors show very good stability (no drift), but respond very slowly with a response time of 5 minutes for a 63% step change from low humidity to high humidity. Polymer sensors with the sensor-heating technology respond very fast either from dry to wet or from wet to dry. But they do not have a wide measurement range. The mainstream polymer sensors have low sensitivity with the measurement range down to only −60 °C DP. Because of polymer’s elastic property, polymer sensors cannot withstand high pressure. In addition, polymer sensors have some drift and hence need calibration every two years. Aluminum oxide film sensors are based on amorphous or γ-Al2O3 obtained by anodization. For simplicity, the amorphous/γ-Al2O3 based sensors are called γ-Al2O3 sensors. Aluminum oxide (γ-Al2O3) sensors have extremely high humidity sensitivity with the measurement range down to -110 °C DP or 1.3 parts per billion by volume fraction. Their temperature coefficient is also very small. However, γ-Al2O3 sensors exhibit long-term drift when exposed to higher moisture levels because the γ-Al2O3 phase is unstable and reacts with moisture to form boehmite (γ-Al2O3.H2O), leading to long-term drift.3-10 Our group has also fabricated γ-Al2O3 dew point sensors, which exhibited very large drift (see Fig. 2). Between tests, the sensor was placed on the desk in the laboratory, which exposed it to a humidity level of ~20 – 30%. It is clear that the γ-Al2O3 sensor had large drift when exposed to moisture. The drift was much faster initially and the drift rate was lowered after a few days. Commercial γ-Al2O3 dew point sensors are usually aged for three months before release to the market, but still require frequent calibration (6 months) and storage in dry environment.11 They cannot be exposed to air, which is inconvenient to users. (continued on next page)

The Pros and Cons of Humidity/ Dew Point Sensors on the Market Humidity sensors are divided into two categories: (1) Relative humidity sensors for high humidity measurement; and, (2) Moisture or dew point sensors for low humidity measurement. Most humidity sensors on the market are relative humidity sensors, including ceramic, semiconductor, and polymer humidity sensors.1,3 It is relatively easier

Fig. 1. Correlation among humidity units: dew/frost point, parts per million by volume fraction (PPMv), and relative humidity.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Chen

(continued from previous page)

formed on a conductive substrate. A nanoscale humidity-sensing film (<10 nm) is deposited conformally on the inner surfaces of the pores using atomic layer deposition. A thin metal film (<50 nm) is deposited as the top electrode. The conductive substrate is used as the bottom electrode.

α-Alumina(Sapphire)/Silicon Dioxide Hybrid Dielectric Sensors

Fig. 2. Capacitance vs.dew point of an γ-Al2O3 moisture sensor. Large drift after exposure to air (20 – 30% RH) for two weeks.

Novel Hybrid Dielectric Sensing Materials Most humidity sensors are capacitive structures where porous humidity-sensing materials are used as dielectric materials. When the humidity level in the environment changes, the amount of water molecules adsorbed in the inner surfaces of pores changes, resulting in change of the dielectric constant of the porous dielectric material. This leads to change of the capacitance and hence the impedance of the sensors. A material considered as a humidity-sensing material for capacitive sensors must have the following properties: (1) dielectric, (2) porous, and (3) humidity-sensing. However, there are many humidity-sensing materials that are not porous. Using the following hybrid dielectric material scheme, non-porous humidity-sensing materials, if deposited by atomic layer deposition, can be converted into porous humiditysensing dielectric materials. In this article, I present novel humidity sensors based on hybrid dielectric materials as shown in Fig. 3.12,13 A porous dielectric material, which may not be humidity sensing, is

It is well known that α-Al2O3 is synthetic sapphire, which is extremely stable. A porous α-Al2O3 film serves as the porous dielectric material. Among various other dielectric materials, SiO2 is the most stable and has been used in silicon-based integrated circuits for several decades. In addition, SiO2 is also highly humidity-sensitive because it is hydrophilic. SiO2 is used as the nanoscale humidity-sensing film here. The schematic hybrid dielectric sensor structure is shown in Fig. 3.12,13 To form wire bonding for the sensor electrodes on conductive substrates, the sensor electrode structure is described in detail in a US patent.14 Porous α-Al2O3 (sapphire) films were formed on aluminum substrates by anodic spark deposition.15-19 Then, conformal SiO2 thin films of ~3 – 10 nm were deposited on the surface, pore walls, and pore bases of the porous α-Al2O3 films by atomic layer deposition (ALD). Because SiO2 growth is controlled at the atomic scale, very uniform and conform SiO2 thin films can be obtained. SiO2 thin films deposited at the pore bases also serve as insulators. Without them, the α-Al2O3 sensors would fail due to short-circuiting. The entire sensor structure consists of α-Al2O3 and SiO2, where SiO2 serves as the humiditysensing material. Without amorphous/γ-Al2O3, the α-Al2O3(sapphire)/ SiO2 hybrid dielectric sensors are highly stable when interacting with water molecules. A conducting film, e.g., platinum, gold, Ti, TiN, TiO2, and their combinations, is deposited on the top of the porous structure, to serve as the top electrode. The aluminum substrate serves as the bottom electrode. Atomic layer deposition was used to obtain atomic layer control of the thin film growth as this technique is based on sequential self-limiting surface reactions. Because of the self-limiting effect and monolayerby-monolayer deposition, the molecules cannot accumulate at the pore entrance and uniform films can be deposited on the entire inner walls of the high-aspect-ratio pores.20-24 Because water molecules can diffuse through SiO2, the presence of a stable porous dielectric material that is not reactive with water molecules, such as α-Al2O3, is of critical importance. The α-Al2O3(sapphire)/SiO2 hybrid dielectric sensor showed very stable performance as shown in Fig. 4. The sensor was tested at varying dew points, generated by a humidity generator through mixture of dry N2 and water vapor. Between tests, the sensor was left exposed to a humidity level of ~40 – 50% RH, with no special care taken to control the exposure. From Fig. 4, it is seen clearly that no drift occurred for the sensor exposed to air (40 – 50% RH) for 40 days except for small random variations. For comparison, a γ-Al2O3based moisture sensor exhibited large drift after exposure to air for only 13 days (see Fig. 2). The sensitivity of the α-Al2O3/SiO2 moisture sensor in the range from −70 °C DP to −80 °C DP is ~1.8 pf/°C DP, which is sufficient for dew point measurements.

Performance of α-Alumina(Sapphire)/ Silicon Dioxide Dew Point Meters

Fig. 3. Novel schematic α-Al2O3/SiO2 hybrid dielectric sensor structure: Conformal SiO2 film deposited on the inner surface of pores of α-Al2O3 structures by atomic layer deposition. (US Patent 9,285,334 and Chinese Patent 201410246545.) 68

α-Al2O3(sapphire) is a thermodynamically stable phase. In combination with SiO2, hybrid dielectric sensors do not exhibit any long-term drift, do not require recalibration, and can be stored anywhere, as shown earlier. The unique pore structure of the α-Al2O3 sensors allows them to respond very quickly to changes in humidity levels. The respond speed of α-Al2O3(sapphire)/SiO2 sensors is the fastest among dew point sensors that do not use sensor-heating technology. As an example of α-Al2O3(sapphire)/SiO2 hybrid dielectric sensors, ASPT SRP-100 portable dew point meters and ASPT T80/T100 dew point transmitters are being manufactured and marketed by Advanced Semiconductor Processing Technology (ASPT). Table I shows, as an The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Table I. Technical data of ASPT T80, T100, and SRP-100. Technical Specifications Dew Point Range

−80 to +20 °C dew point (T80, SRP100) −100 to +20 °C dew point (T100)

Output Signal

4 to 20 mA

Accuracy

±2 °C dew point

Response Time—63% [90%] step change @ 3000 sccm

15 s [45 s] (Step: −60 °C to −20 °C) 1 min [3 min] (Step: −20 °C to −60 °C)

Operating Temperature

0 to +50 °C −30 to +50 °C (extended version)

Repeatability

0.5 °C dew point

Supply Voltage

8 V to 28 V DC

Operating Pressure

5 MPa 15 MPa (extended version)

Summary Fig. 4. Capacitance versus dew point of an α-Al2O3/SiO2 hybrid dielectric moisture sensor. No drift after exposure to air (40 – 50%RH) for 40 days.

example, the technical data of ASPT T80 and T100 transmitters and SRP-100 portable meters. Performance of various dew point sensors available on the market are compared with ASPT sensors as shown in Table II. The Vaisala polymer sensor using sensor-heating technology has the fastest response. The response speed of the ASPT sensor without sensor-heating ranks the second after the Vaisala polymer sensor. The Michell ceramic sensor has the slowest response (5 min for 63% step change from dry to wet). The measurement of response times for both ASPT sensors and Vaisala DMT 152 was carried out in our company lab by a 63% dew point step from −60 °C to −20 °C (dry to wet) and from −20 °C to −60 °C (wet to dry). The response times of Michell Easidew, GE Panametrics, and Xentaur Cosa LPDT were measured by Xentaur company.25 The accuracy of all sensors are close to each other. Regarding the measurement range, the GE γ-Al2O3 dew point sensor has the widest range and Vaisala polymer sensor has the narrowest measurement range. For long-term stability, only the ASPT sensor and the Michell sensor remain stable without recalibration.

A novel α-alumina(sapphire)/silicon dioxide humidity sensor using the hybrid dielectric material technique has been described. The hybrid dielectric material consists of an insulating porous dielectric material and a nanoscale humidity-sensing film deposited conformally on the inner surfaces of the pores using atomic layer deposition. These sensors exhibit long-term stability, fast response, and durability at extremely high/low humidity levels. © The Electrochemical Society. DOI: 10.1149/2.F07174if.

Acknowledgments The author is grateful to his graduate and postdoctoral students in assistance in experiments, including Ibrahim Yucedag, Mengmei Liu, Riasad Badhan, and Bojie Chen. He is thankful to engineers of Advanced Semiconductor Processing Technology (ASPT) in both USA and China in assistance in research and development of the dew point sensor product, including Lei Han, Neha Nehru, Jingbo Tong, Fangdong Huang, Yunju Huo, and Tian Huang. He is also thankful to financial support from Kentucky Science and Engineering Foundation, USA, Chengdu High-Tech Zone Entrepreneur Award, and Chengdu City Talent Program, Chengdu, Sichuan, China. (continued on next page)

Table II Performance comparison of various dew point sensors Response Time (63% dew point step change @ 3000 sccm)

Measurement Range (dew point)

Accuracy (dew point)

Vaisala DMT 152 (Polymer)

−80 °C – −20 °C

±2 °C (<−40 °C) ±3 °C (>−40 °C)

−60 °C to −20 °C: 9 s* −20 °C to −60 °C: 42 s*

Every 2 years

Michell Easidew (Ceramic)

−100 °C – +20 °C

±2 °C

−60 °C to −40 °C: 5 min −40 °C to −60 °C: 15 min

GE Panametrics (γ-Al2O3)

−110 °C – +20 °C

±2 °C (>−65 °C) ±3 °C (<−65 °C)

−60 °C to −40 °C: 1 min 17 s −40 °C to −60 °C: 8 min 20 s

Every 0.5 year

Xentaur Cosa LPDT (γ-Al2O3)

−100 °C – +20 °C

±3 °C

−60 °C to −40 °C: 1 min 17 s −40 °C to −60 °C: 2 min 30 s

Every 0.5 year

Retronic LDP-1 (N/A)

−70 °C – +85 °C

±2 °C (>−50 °C) ±3 °C (<−50 °C)

Dry to wet: 13 s Wet to dry: 10 min

Every 2 years

ASPT T100 (α-Al2O3/SiO2)

−100 °C – +20 °C

±2 °C

−60 °C to −20 °C: 15 s −20 °C to −60 °C: 60 s

Dew Point Sensors

Recalibration

*The sensor-heating technology is used. The response time data for Vaisala and ASPT sensors are from our tests, and those for GE, Michell, and Xentaur sensors are from Xentaur tests25 except for Retronic LDP-1, which are from its data sheet.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Chen

(continued from previous page)

About the Author Zhi David Chen is a professor of electrical and computer engineering at the University of Kentucky, visiting professor at the University of Electronic Science and Technology of China, and co-founder and chief scientist of Advanced Semiconductor Processing Technology (ASPT) in the U.S. and China. He received his BS degree in 1984 and MS degree in 1987 in optoelectronic engineering from the University of Electronic Science and Technology of China, Chengdu, Sichuan, China. He obtained his PhD degree in electrical engineering from the University of Illinois at Urbana-Champaign in 1999. He has published about 100 papers in refereed journals and over 60 conference presentations with many high-impact papers. He pioneered the synthesis of titanium oxide nanotubes using anodic oxidation. He received numerous awards including National Expert of China Thousand Talent Program (2012), U.S. National Science Foundation CAREER Award (2001), the Second Prize Paper Award of Industrial Automation and Control Committee at the 27th Annual Conference of IEEE Industry Application Society (1992), and Chinese National Invention Award (the 3rd Prize, 1995). He currently serves as a member-at-large of the ECS Dielectric Science and Technology Division, and is a member of the ECS Transactions Editorial Advisory Board. He may be reached at zhi.chen@uky.edu. https://orcid.org/0000-0002-4451-5626

References 1. E. Traversa, “Ceramic Sensors for Humidity Detection: the State-of-the-Art and Future Developments,” Sens. Actuators B, 23, 135 (1995). 2. Z. Chen and C. Lu, “Humidity Sensors: A Review of Materials and Mechanisms,” Sensor Letters, 3, 274 (2005). 3. M. G. Kovac, D. Chleck, and P. Goodman, “A New Moisture Sensor for In-Situ Monitoring of Sealed Packages,” Solid State Technol., 21, 35 (1978). 4. R. K. Nahar and V. K. Khanna, “A Study of Capacitance and Resistance Characteristics of an A12O3 Humidity Sensor,” Int. J. Electron., 52, 557 (1982). 5. R. K. Nahar, V. K. Khanna, and W. S. Khokle, “On the Origin of the Humidity-Sensitive Electrical Properties of Porous Aluminium Oxide,” J. Phys. D: Appl. Phys., 17, 2087 (1984). 6. R. K. Nahar, “Physical Understanding of Moisture Induced Degradation of Nanoporous Aluminum Oxide Thin Films,” J. Vac. Sci. Technol. B, 20, 382 (2002) 7. I. Emmer, Z. Hajek, and P. Repa, “Surface Adsorption of Water Vapor on Hydrated Layers of A12O3,” Surf. Sci., 162, 303 (1985). 8. S. Hasegawa, “Performance Characteristics of a Thin Film Aluminum Oxide Humidity Sensor,” 30th Electronic Comp. Conf., IEEE, San Francisco, CA, 1980.

9. J. C. Harding, Jr., “Overcoming Limitations Inherent to Aluminum Oxide Humidity Sensors,” Proc. 1985 Int. Symp. on Moisture and Humidity, Washington, DC, 1985. 10. K. Suzuki, K. Koyama, T. Inuzuka, and Y. Nabeta, “Alumina Thin Film Humidity Sensor, Controlling of Humidity and Aging,” in Proc. 3rd Sensor Symp., IEEE of Japan, Tokyo, Japan, 1983. 11. “System I hygrometer and options,” Operating and Service Manual, Panametrics Ltd. Shannon, Ireland, 1982. (Currently GE Panametrics Inc.) 12. Z. Chen, “Hybrid Dielectric Moisture Sensors,” US Patent No. 9,285,334 (2016). 13. Z. Chen, “Dew Point Sensors and Their Manufacturing Method,” Chinese Patent No. 201410246545 (2016). 14. Z. Chen and I. Yucedag, “Moisture Sensors on Conductive Substrates,” US Patent No. 8,739,623 (2014). 15. G. P. Wirtz and S. D. Brown, “Anodic Spark Deposition of Ceramic Coatings,” Proceedings of Conference on Coatings and Bimetallics for Aggressive Environments, American Society for Metals, Metals Park, OH, 197 (1985). 16. K. A. Koshkarian and W. M. Kriven, “Investigation of a CeramicMetal Interface Prepared by Anodic Spark Deposition,” J. Phys. Colloq., 49, C5 (1988). 17. S. D. Brown, K. J. Kuna, and T. B. Van, “Anodic Spark Deposition from Aqueous Solutions of NaAlO2 and Na2SiO3,” J. Am. Ceram. Soc., 54, 384 (1971). 18. T. B. Van, S. D. Brown, and G. P. Wirtz, “Mechanism of Anodic Spark Deposition,” Am. Ceram. Bull., 56, 563 (1977). 19. S. Tajima, M. Soda, T. Mori, and N. Baba, “Properties and Mechanism of Formation of α-Alumina (Corundum) Film by Anodic Oxidation of Aluminium in Bisulphate Melts,” Electrochim. Acta, 1, 205 (1959). 20. Steven M. George, “Atomic Layer Deposition: An Overview,” Chem. Rev., 110, 111 (2010). 21. D. Hiller, R. Zierold, J. Bachmann, M. Alexe, Y. Yang, J. W. Gerlach, A. Stesmans, M. Jivanescu, U. Müller, J. Vogt, H. Hilmer, P. Löper, M. Künle, F. Munnik, K. Nielsch, and M. Zacharias, “Low temperature silicon dioxide by thermal atomic layer deposition: Investigation of material properties,” J. Appl. Phys,. 107, 064314 (2010). 22. J. Bachmann, R. Zierold, Y. T. Chong, R. Hauert, C. Sturm, R.diger Schmidt-Grund, B. Rheinlnder, M. Grundmann, U. Gosele, and K. Nielsch, “A Practical, Self-Catalytic, Atomic Layer Deposition of Silicon Dioxide,” Angew. Chem. Int. Ed., 47, 6177 (2008). 23. F. Hirose, Y. Kinoshita, S.Shibuya,Y. Narita, H. Miya, K.Hirahara, Y. Kimura, and M. Niwano, “Low-temperatureatomic-layer-deposition of SiO2 with Tris(dimethylamino)silane (TDMAS) and Ozone using Temperature Controlled Water Vapor Treatment,” ECS Trans., 19(2), 417 (2009). 24. L. Han and Z. Chen, “High-Quality Thin SiO2 Films Grown by Atomic Layer Deposition Using Tris(dimethylamino)silane (TDMAS) and Ozone”, ECS J. Solid State Sci. Technol., 2, N228 (2013). 25. Xentaur Corporation document “Xentaur XTR-100 HyperThin-Film Al2O3 Sensor vs. Conventional and Ceramic Al2O3 Moisture Probes” (2011).

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Magnetic Nanoferrites for RF CMOS: Enabling 5G and Beyond by Ranajit Sai, S. A. Shivashankar, Masahiro Yamaguchi, and Navakanta Bhat

Emergence of 5G

rom connected thermostats to self-driving vehicles, advanced connectivity is transforming our lives while saving energy and reducing pollution, thus making living more sustainable. This is the hallmark of the Internet of things (IoT). But the full extent of IoT possibilities is yet to be realized. One of the key foundational technologies that will serve as the core architecture for future capabilities is 5G—the 5th generation telecommunication systems. Unlike its predecessors, 5G is going to be a new heterogeneous ecosystem that includes integration of 4G, Wi-Fi, millimeter waves, and other wireless access technologies, utilizing bandwidths from various frequency bands ranging from <4 GHz to 100 GHz.1 Different usage scenarios demand different capabilities that can be attained in different frequency bands. As per the International Telecommunication Union (ITU), three main usage scenarios are envisaged to expand and support a diverse array of applications for International Mobile Telecommunications (IMT) 2020 and beyond, namely: 1) enhanced mobile broadband; 2) massive machine-type communications; and 3) ultra-reliable and low latency communications (as illustrated in Fig. 1), along with the key performance indicators (KPIs) associated with them.2 The taming of this spectrum is considered essential to achieving the 5G vision of a truly connected world.

RF CMOS: Requirements and Key Challenges

due to a crucial passive component—the inductor. Inductors are widely used in RF integrated circuits. They are essential components of low-noise amplifiers (LNA), power amplifiers (PA), oscillators, filters, etc. But, often, they are the largest components in the circuit, costing more than 50% of chip-area. Apart from “chip real estate,” their large footprint results in a large parasitic capacitance at high frequencies which, in turn, degrades the quality factor and reduces the self-resonance frequency. The need of the hour is to obtain an inductor with high inductance density and high quality factor in the aforesaid frequency bands. Various attempts have been made to enhance the quality factor of integrated inductors on silicon by optimizing coil design, controlling substrate losses, using patterned ground shields, etc., with significant success.5,6 However, it is understood that, to keep up with the technology scaling, on-chip inductors may not be practical to use beyond 10 GHz.5 Distributed passive elements like transmission lines are suggested for the use at frequencies ≫10 GHz. But the length of such distributed elements can be prohibitive for their integration on-chip below 30 GHz. Integration of ferromagnetic and high-ε materials has thus become essential for frequencies of 10-30 GHz—some of the key frequency bands for 5G applications. Therefore, to continue with the miniaturization of RFICs and to move towards SoC solutions, on-chip integration of magnetic materials is necessary and that can pave way for high performance on-chip inductors for the frequency bands above 10 GHz, and thus can fulfill the promise of SoC and IoT. Magnetic materials have played a significant role in achieving efficient high frequency devices since the middle of the last century. Changing requirements over the years have sparked innovation in materials science and processing technology. At present, the requirement is to

The focus of this article is mainly on two of the proposed frequency bands, centered around 6 GHz and 28 GHz, which are designated for connected vehicles and indoor hotspot applications, respectively. Demanding KPIs of various applications call for innovation in radio frequency integrated circuit (RFIC) design. For example, for the connected vehicles in urban grids and highways, high mobility (>300 km/h), high reliability and low latency (≤1 ms) are essential. Lower latency can be achieved by bringing circuit components in a mixed-signal chip closer to one another. However, the physical proximity of the electromagnetic (EM) noise aggressor, viz., digital components, and the victim, viz., analog components, at such high frequencies may lead to serious electromagnetic interference which, in turn, may degrade the reliability of the devices and the systems.3,4 This is of serious concern in designing the RF CMOS circuit layout that uses all frequency bands related to 5G. Therefore, to continue miniaturization of radio frequency integrated circuits while maintaining high reliability, either a novel circuit design approach should be adopted or an on-chip EM noise suppressor must be used. Besides electromagnetic compatibility issues, progress in bringing analog, digital, and RF circuits on one chip—commonly known as system-on-chip (SoC)—is hindered greatly Fig. 1. Proposed key performance indicators of upcoming 5G technology. The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued on next page)

Sai, et al.

(continued from previous page)

obtain a suitable, integrated magnetic film on Si-CMOS chip. So, for clarity, the discussion henceforth will be confined to such an on-chip integrated magnetic film and its two applicationsâ&#x20AC;&#x201D;as an inductor core and as an EM noise suppressor. A suitably chosen integrated film can serve both the purposesâ&#x20AC;&#x201D; tackling electromagnetic compatibility issues and enhancing the performance of on-chip passives. It is, however, to be noted that the governing principle of the suppression of electromagnetic interference using a magnetic film is different from the principle behind the enhancement of inductance of a coil with a magnetic core, even though both are related to the permeability of the magnetic medium. When subjected to a high frequency magnetic field (several kHz

or higher), the permeability of a magnetic material can be expressed as a complex quantity (ÂľÂ =Â Âľâ&#x20AC;˛Â â&#x2C6;&#x2019;Â jÂľâ&#x20AC;ł), considering that the magnetic dipoles of the material exhibit a delayed response that results in a loss. In general, Âľâ&#x20AC;˛ represents the ability of the material to confine magnetic flux, while the Âľâ&#x20AC;ł describes magnetic losses. Âľâ&#x20AC;˛ assumes a constant value at lower frequencies and begins to drop below zero beyond a cut-off frequency, known as the ferromagnetic resonance frequency (fFMR), and has a direct influence on the inductance of a coil having the said material as the core. On the other hand, the driving idea of noise suppressors is the remediation of RF magnetic field, which is the strongest near the interconnects, by placing nearby a material that has large Âľâ&#x20AC;ł at that RF frequency. The frequency dispersion of complex permeability of a magnetic material (amorphous ferromagnetic CoZrNb thin film, chosen as an example) is shown schematically in Fig. 2, highlighting the usage scenarios of the same as either an inductor core or an EM noise suppressor. Every magnetic film typically exhibits similar characteristicsâ&#x20AC;&#x201D;high Âľâ&#x20AC;˛ at low frequency and the highest Âľâ&#x20AC;ł at fFMR. Magnetic materials are characterized by these three parametersâ&#x20AC;&#x201D;Âľâ&#x20AC;˛, Âľâ&#x20AC;ł, and fFMR. Therefore, a given material can be utilized as an EM noise suppressor if the noise frequency is close to the fFMR, whereas the same material can be used as inductor core at a frequency range well below fFMR where the loss component is negligible. In other words, for a given frequency of application, a single material cannot serve both the purposes simultaneously.

Why Ferrites? Ferromagnetic metal-alloy-based materials are very popular and are being used extensively both as EM noise suppressors and inductor core, especially in the frequency bands below 2Â GHz.7-Â 13 However, owing to their low electrical resistivity, eddy current losses are extremely high in the GHz range. Furthermore, with the ferromagnetic resonance frequency below 5Â GHz in most of them, they can neither be used as inductor core nor as EM noise suppressor in the frequency band in between between 5 GHz and ~30 GHz. Ferromagnetic resonance frequency depends on the magnetic anisotropy present in the material and can be expressed as follows, assuming spherical particles: Îł f FMR = Ha 2Ď&#x20AC;

Fig. 2. (a) Schematic drawing of frequency dispersion of complex permeability, highlighting the appropriate frequency ranges for inductor and noise-suppressor applications. Amorphous CoZrNb thin film is chosen as an example (Ref. Yamaguchi, et al.,13). (b) Magnetic hysteresis curve of the same film. 72

where đ?&#x203A;ž is the gyromagnetic constant and Ha is the effective magnetic anisotropy field, which is the sum of magnetocrystalline anisotropy, shape anisotropy, stress anisotropy. Being amorphous in nature, metal-alloy-based ferromagnetic films possess no magnetocrystalline anisotropy, and thus, exhibits very low anisotropy and FMR frequency. As a result, the focus is now on magnetic oxides, such as spinel ferrites, hexaferrites, and garnets as alternative to ferromagnetic metal-alloys to succeed in the above-specified frequency bandâ&#x20AC;&#x201D;in the realm of 5G.14-17 Ferrite materials are unique because they belong to the family of insulating oxides that are magneticâ&#x20AC;&#x201D;possessing moderate permeability, very high magnetic anisotropy, moderate-to-high permittivity, and low losses up to a few tens of GHz. Spinel ferrites (structural formula: AB2O4, such as NiFe2O4, Fe3O4, MnxZn1.xFe2O4, etc.) and garnets (structural formula: A3B5O12, such as Y3Fe5O12, Y3GaxFe5-xO12, etc.) have cubic crystal structure with close-packed oxygen lattices, whereas the hexaferrites can exist with several hexagonal close-packed structural variations, such as M, Y, W, X, Z, U, in which the metal and oxygen stoichiometry are different.14-17 The possibility of innumerable combinations of metal substitution in them allows fine-tuning of their properties as per requirement. However, the real technological challenge is to deposit thin films of such complex oxides on the Si-CMOS chip. Unlike amorphous metal-alloy films, ferrites and garnets should be well-crystallised to exhibit their magnetic characteristics. High-temperature annealing is often necessary to achieve desired crystalline quality.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2017 â&#x20AC;˘ www.electrochem.org

CMOS Integration of Ferrite Film: Issues and Solutions

Given that magnetic films are typically integrated at the back-end of CMOS fabrication steps, use of processing temperature above 400 °C is untenable, as it makes the whole device fabrication process CMOS-incompatible.18,19 On the other hand, a low-temperature process often leads to inadequately crystallised ferrite films, resulting in inferior magnetic properties and weak adherence, thus limiting their practical usefulness. Printing/pasting a composite layer of pre-processed ferrite powder in a polymer matrix can certainly be a low-temperature CMOS-compatible process.20,21 But, the effective permeability of the composite layer can become untenable due to the presence of polymer material. Therefore, the focus should be on a continuous, dense ferrite film to obtain the best result. In a nutshell, the challenge is to obtain on silicon chips, below 400 °C, a well-adhering ferrite film, having the FMR frequency in the range 5 ~ 30 GHz. Among ferrites, hexaferrites possess high magnetocrystalline anisotropy and thus exhibit FMR at frequencies ranging from a few GHz to several tens of GHz, making them perfectly suited for applications in the desired frequency band. However, the formation of hexagonal ferrites requires annealing above 1000 °C, making them inapt for on-chip integration.17 Development of a low-temperature hexaferrite deposition method can offer invaluable freedom in choosing appropriate magnetic materials for appropriate applications. Despite having a little lower magnetocrystalline anisotropy than hexaferrites, spinel ferrites can be deposited at a temperature compatible with CMOS processing by various soft-chemical deposition routes, such as spin-spraying,22-24 microemulsion technique,25,26 sonochemical method,27 and microwave solvothermal technique28-30 to name a few, in addition to physical routes like pulsed laser deposition (PLD)31 and alternating target laser ablation deposition (ATLAD).32 Among low-temperature spinel ferrite deposition processes, the spin spraying technique provides well-crystallized ferrite layers at sub-100 °C.22-24 However, the formation of ferrite demands sequential spraying of reaction- and oxidizing-solutions, both of which may corrode exposed Cu-wirings of on-chip circuit elements, such as inductors or transmission lines. Furthermore, a substrate pretreatment is advised to achieve required adherence.24 On the other hand, despite the capability of depositing an epitaxial quality film at low-temperature, methods like pulsed laser deposition (PLD) and alternating target laser ablation deposition (ATLAD) are limited to being valuable research tools because of low deposition rates and small substrate size.15 Due to their symmetric cubic crystal structure, spinel ferrites possess moderate magnetocrystalline anisotropies that result in ferromagnetic resonance at frequencies below 10 GHz. Therefore, pushing the fFMR of the spinel ferrites towards 30 GHz has become an added challenge.

in ferrites is mediated by lattice oxygen which resides between two cations—known as superexchange.33 The strength of such superexchange depends on three factors—distance, direction, and the superexchange interaction angle. It is, therefore, easy to surmise that substitution of a lattice cation by a foreign cation of different size and electronegativity would alter the crystal symmetry and, consequently, the magnetic characteristics of ferrites.14,34 Crystal symmetry can be broken by inducing oxygen vacancies, too. Zuo, et al.,31 and Yang, et al.,32 revealed that oxygen partial pressure-mediated far-from-equilibrium distribution of cations in Mn- and Cu-ferrite film systems, deposited by PLD and ATLAD respectively, increases magnetic anisotropy from ~20 Oe to >1000 Oe, thus extending the applicability of spinel ferrites to a higher frequency than is normally associated with them. Now the question is: can we induce a far-from-equilibrium distribution of cation and/or break in crystal symmetry through a soft-chemical method? A rapid synthesis of nanocrystalline ferrite could be the answer. In this context, microwave-assisted deposition technique (MADT)—a rapid, sub-200 °C, and “far-from-equilibrium” solutionbased film deposition method, wherein the precursors decompose and react to form the desired composition under the influence of microwave irradiation—has established itself as an excellent choice for depositing nanocrystalline spinel ferrite films on silicon chips.35-38 An example of the zinc ferrite thin film deposition process steps along with the description of the microwave reactor is schematically shown in Fig. 3. It is to be noted that the formation of oxide nanocrystals and their characteristics depend largely on the reaction mechanism, which is governed by microwave dielectric heating. Therefore, the choice of precursor material and solvent system is extremely important to attain the desired result. There are some excellent review articles28-30,39-41 which discuss microwave-assisted synthesis of oxide nanoparticles in great depth. Furthermore, zinc ferrite nanocrystallites prepared by microwaveassisted synthesis display an unusually high degree of inversion, with ~50% of the lattice zinc atoms out of their equilibrium positions in the crystal structure.42 Such a high degree of crystallographic inversion can alter the crystal symmetry as well as the spin structure, and may thereby induce a higher anisotropy and an enhanced fFMR as a consequence. Although it is in its infancy, this approach can be an excellent way to modulate ferromagnetic resonance frequency of spinel ferrites via the soft-chemical route. (continued on next page)

Tailoring FMR: A Low-Temperature Non-Equilibrium Approach The origin of magnetism in ferrites is the exchange energy between spins of neighboring metallic ions that are aligned antiparallel to each other in their lowest energy configuration. As the distance between two metal ions is too large in ferrites to support a direct Fig. 3. (a) Processing steps for zinc ferrite thin film deposition by microwave-assisted deposition technique exchange, unlike in most magnetic (MADT); (b) Schematic cross-section view of the microwave-reactor used for MADT; (c) A photograph of that metals, the exchange interaction bench-top deposition system. The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Sai, et al.

(continued from previous page)

On-Chip Ferrite-Core Inductors and Noise-Suppressors A recent article described the deposition of a partially inverted zinc ferrite film with excellent soft magnetic characteristics, i.e., saturation magnetization of ~130 emu/cc and coercivity of ~120 Oe directly on a Si-CMOS integrated circuit by MADT.38 The CMOS compatibility of the deposition process was also demonstrated by comparing the ID-VD and ID-VG characteristics of a MOSFET before and after exposing it to microwave-assisted processing. In addition to producing a strongly adherent, uniform, and nonporous film, the said deposition technique offers conformal coating on any exposed surface of irregular geometric shape. In a separate article, such a conformal coating on screw-shaped silica-based micro-propellers was demonstrated.43 A wide variety of thicknesses were obtained, ranging from a few hundred nm to several tens of microns.44 The partially inverted zinc ferrite composite thin film, deposited by MADT, showed FMR frequency above 30 GHz, with negligible FMR loss below 15 GHz. Therefore, this film exhibits perfect characteristics to be used as inductor core in the frequency range up to 15 GHz and as an EM noise suppressor around 30 GHz. Up to 20 % enhancement of inductance was reported with a film 1 µm in thickness—making it the best on-chip ferrite-core inductor with the highest inductance density (750 nH/mm2) at 5 GHz. Furthermore, 13% enhancement in inductance density and 25% enhancement in the quality factor was demonstrated at 10 GHz, staking claim to be

Fig. 5. State-of-the-art of ferrite-core inductors operating at GHz frequency, highlighting the results with zinc ferrite composite film deposited by MADT.

the highest-density (450 nH/mm2) inductor at that frequency.37,38 The quality factor of these inductors could not be enhanced much by depositing the ferrite film only on top of the inductor coil. Moreover, it is proven theoretically that inductance can be increased only by 100% by depositing a magnetic film on just on one side of the coil.7 To harness the best effect of magnetic film, a complete magnetic path, i.e., complete encapsulation of the coil is necessary. By utilizing the ability of MADT to deposit ferrite film conformally, three-sides of the on-chip coil are covered by zinc ferrite thin film in a single step. The resulting coil structure is demonstrated both schematically and with SEM images in Fig. 4. An enhancement of Q-factor by 78% is achieved, as shown in Fig. 4e. It is to be noted that the magnetic path is, nevertheless, not closed. A very large increase of inductance and inductance density can be achieved if the coil can be fabricated on a ferrite layer instead of the interlayer dielectric. There is a serious dearth of on-chip ferrite-core inductors now. Most of the ongoing research is still in the sphere of the research laboratory. There is rapidly growing interest in taking such inductors to the market by the year 2020 to meet the demands of 5G systems. In Fig. 5, the reported ferrite-core inductors are compared with the microwave-deposited ferrite-core on-chip inductors. The superiority of the microwave deposition approach is evident as it forms a bridge between the best of two aspects—high quality coil fabrication by IC technology and positive effect of the ferrite-core. The electromagnetic noise suppression effectiveness of the ferrite film can be shown by depositing the film on a coplanar waveguide, followed by measuring the power loss ratio in the film.13 As mentioned before, it has been demonstrated that 400 nm-thick films of partially inverted zinc ferrite exhibit FMR frequency around 30 GHz.38 Therefore, the film can be suitable for EM noise suppression in the frequency band ~30 GHz. In Fig. 6, the ratio of loss power to input power to an on-chip CPW structure, coated with partially inverted zinc ferrite, is demonstrated. It is found that up to 20% of EM noise power can be dissipated by the ferrite film. This is well below the requirement of the industry at present. However, this has been the first and only demonstration of EM noise suppression at 30 GHz by an on-chip ferrite film.

Closing Remarks and Outlook

Fig. 4. Ferrite-coated on-chip inductor and its measurements; schematic drawing of inductor coil on a Si-CMOS chip (a) with passivation removed from 3-sides of the coil, and (b) with zinc ferrite thin (250 nm) film coated conformally; (c) and (d) show the SEM images of the coil before and after ferrite coating; (e) Measured inductance and Q-factor of the on-chip inductance with ferrite film deposited only on top (in red) and surrounding 3-sides of the coil (in green). 74

The technological shift towards higher frequency for the looming 5G systems brings countless challenges, thus providing boundless opportunities to innovate, so as to meet the demanding specifications of high frequency integrated circuits. Innovation is essential at all levels, from circuit design to device fabrication to system packaging. The role of functional materials, especially magnetic oxides such as ferrites, are going to be the most critical ever for integrated devices. Development of CMOS-compatible low-temperature deposition of ferrite films and the integration of such a deposition method into the The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

professor. His area of research includes the study of high frequency properties of ferrites and hexaferrites, development of on-chip ferritecore inductors for gigahertz applications, and the integration of ferrite films at the back end of the Si-CMOS processing. He is also actively involved in the development of hexaferrite-based electromagnetic noise suppression sheets usable in several tens of gigahertz. He may be reached at ranajit@ecei.tohoku.ac.jp. https://orcid.org/0000-0002-3563-2257

Fig. 6. Demonstration of EM noise suppression at ~30 GHz, achieved by partially inverted zinc ferrite composite thin film deposited by MADT (Sai, et al., article under review).

semiconductor processing technology is the immediate necessity. Being the most suitable magnetic material in the frequency bands ranging from a few GHz to several hundreds of GHz, hexagonal ferrites and their stoichiometric derivatives hold the key to the realization of the full potential of high frequency magnetics in the years to come. Therefore, a serious effort is necessary to deposit hexaferrite films in a CMOS-compatible way. Microwave-irradiationassisted, solution-based, non-equilibrium spinel ferrite deposition technique offers an excellent approach towards CMOS-compatible and scalable ferrite film deposition. However, it is still in its infancy and demands extensive research to attain industry-scale reliability and control over material properties. Besides nanoferrite film deposition, accurate measurement of magnetic characteristics at several tens of GHz is also extremely challenging. Development of permeability measurement systems with high sensitivity is also imperative. Above all, an interdisciplinary approach combining the wisdom of RF engineers, semiconductor technologists, material scientists, physicist, and chemists together is the way forward. © The Electrochemical Society. DOI: 10.1149/2.F08174if.

Acknowledgments The authors acknowledge funding support from the Ministry of Electronics and Information Technology and the Department of Science and Technology, Government of India. The authors also acknowledge the support received from The Ministry of Internal Affairs and Communications (MIC), Government of Japan, for the project Development of Technical Examination Services Concerning Frequency Crowding, and Japan Society for the Promotion of Science for granting a DST-JSPS joint bilateral research project.

About the Authors Ranajit Sai received his PhD in nanoengineering for integrated systems from the Indian Institute of Science in Bengaluru, India in 2014, where he has designed and developed a low-temperature CMOS-compatible ferrite film deposition technique. After his graduation, Sai joined Tohoku University in Sendai, Japan, where he had worked for New Industry Creation Hatchery Center (NICHe) as a post-doctoral researcher for six months before serving the department of electrical engineering as an assistant professor from April 2014 to March 2017. Since April 2017 he is affiliated to NICHe as an assistant

S. A. Shivashankar received his PhD in chemical physics from Purdue University, USA, in 1980. He then worked at the IBM Watson Research Center, New York, as a research staff member, first in the physical sciences division and later in the materials laboratory. He joined the faculty of the Materials Research Centre, Indian Institute of Science (IISc), Bengaluru, India, in 1980 and became a member of the “founding faculty” of the Centre for Nano Science and Engineering (CeNSE) when it was established at IISc in 2010. Since retiring from formal service in 2012, he has been serving at CeNSE in a full-time emeritus capacity. His current research interests are in the development of chemical precursors for the synthesis nanomaterials and nanostructures, including nanostructured thin films, for different applications. He is also an adjunct professor at the Poornaprajna Institute of Scientific Research, Bengaluru. He may be reached at shivu@iisc.ac.in. Masahiro Yamaguchi received his BSc, MSc, and PhD degrees in electrical engineering from Tohoku University, Japan in 1979, 1981 and 1984, respectively. In 1984, he joined the department of electrical engineering, Tohoku University as an assistant professor. In 1990, Yamaguchi became an associate professor at the Research Institute of Electrical Communication, Tohoku University. During October-December 1995, he joined the department of electrical and computer engineering, University of Wisconsin-Madison, USA, as a visiting associate professor. Since 2003, he works for the department of electrical engineering, faculty of engineering, Tohoku University as a full professor. His interests cover high frequency magnetic materials and applications, and EMC. He is currently the chair of the Technical Committee on Magnetics, IEE of Japan, chair of the IEEE EMC Society Sendai Chapter, and the secretary/treasurer of the IEEE Magnetics Society. He may be reached at yamaguti@ecei.tohoku.ac.jp. https://orcid.org/0000-0002-3601-7619 Navakanta Bhat received his PhD in electrical engineering from Stanford University in 1996. Then he worked at Motorola’s Advanced Products R&D Lab in Austin, TX until 1999. He is currently a professor at the Indian Institute of Science (IISc), Bangalore. His current research is on nanoelectronics and sensors. He has more than 200 publications and 20 patents. He was instrumental in creating the National Nanofabrication Centre (NNfC) at IISc, benchmarked against the best university facilities in the world. He is the recipient of IBM Faculty award and Outstanding Research Investigator award (Govt. of India). He is a fellow of INAE. He was the editor of IEEE Transactions on Electron Devices during 2013-2016. He is the member of the National Innovation Council in Nanoelectronics. He is the founder and promoter of a startup called “PathShodh Healthcare,” which builds point-of-care diagnostics for diabetes and its complications. He may be reached at navakant@iisc.ac.in. https://orcid.org/0000-0002-5356-5166

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

(continued on next page)

Sai, et al.

(continued from previous page)

References 1. Recommendation ITU-R M.2083. IMT Vision – “Framework and Overall Objectives of the Future Development of IMT for 2020 and Beyond,” ITU-R M.20, (2015). 2. A. Afzali-Kusha, M. Nagata, N. K. Verghese, and D. J. Allstot, “Substrate Noise Coupling in SoC Design: Modeling, Avoidance, and Validation,” Proc. IEEE, 94, 2109 (2006). 3. T. Sudo, H. Sasaki, N. Masuda, and J. L. Drewniak, “Electromagnetic Interference (EMI) of System-on-Package (SOP),” IEEE Trans. Adv. Packag., 27, 304 (2004). 4. J. N. Burghartz, and B. Rejaei, “On the Design of RF Spiral Inductors on Silicon,” IEEE Trans. Electron Devices, 50, 718 (2003). 5. A. M. Niknejad, and R. G. Meyer, “Analysis, Design, and Optimization of Spiral Inductors and Transformers for Si RF ICs,” IEEE J. Solid-State Circuits, 33, 1470 (1998). 6. D. S. Gardner, et al., “Review of On-Chip Inductor Structures With Magnetic Films,” IEEE Trans. Magn., 45, 4760 (2009). 7. D. S. Gardner, et al., “Integrated On-Chip Inductors With Magnetic Films,” IEEE Trans. Magn., 43, 2615 (2007). 8. M. Vroubel, Y. Zhuang, B. Rejaei, and J. N. Burghartz, “Integrated Tunable Magnetic RF Inductor,” IEEE Electron Device Lett., 25, 787 (2004). 9. W. Xu, et al., “Sub-100 μm Scale On-Chip Inductors with CoZrTa for GHz Applications,” J. Appl. Phys., 109, 07A316 (2011). 10. S. X. Wang, “Fabrication and Analysis of High-Performance Integrated Solenoid Inductor with Magnetic Core,” IEEE Trans. Magn., 44, 4089 (2008). 11. M. Yamaguchi, S. Arakawa, H. Ohzeki, Y. Hayashi, and K. I. Arai, “Characteristics and Analysis of a Thin Film Inductor with Closed Magnetic Circuit Structure,” IEEE Trans. Magn., 28, 3015 (1992). 12. M. Yamaguchi, et al., “Ferromagnetic Thin Film Noise Suppressor Integrated to On-Chip Transmission Lines,” IEEE Trans. Magn., 46, 2450 (2010). 13. V. G. Harris, “Modern Microwave Ferrites,” IEEE Trans. Magn., 48, 1075 (2012). 14. V. G. Harris, et al., “Recent Advances in Processing and Applications of Microwave Ferrites,” J. Magn. Magn. Mater., 321, 2035 (2009). 15. R. Valenzuela, “Novel Applications of Ferrites,” Phys. Res. Int., 2012, 1 (2012). 16. R. C. Pullar, “Hexagonal Ferrites: A Review of the Synthesis, Properties and Applications of Hexaferrite Ceramics,” Prog. Mater. Sci., 57, 1191 (2012). 17. O. Brand, “Microsensor Integration Into Systems-on-Chip,” Proc. IEEE, 94, 1160 (2006). 18. S. Sedky, A. Witvrouw, H. Bender, and K. Baert, “Experimental Determination of the Maximum Post-Process Annealing Temperature for Standard CMOS Wafers,” IEEE Trans. Electron Devices, 48, 377 (2001). 19. Z. Ni, et al., “Design and Analysis of Vertical NanoparticlesMagnetic-Cored Inductors for RF ICs,” IEEE Trans. Electron Devices, 60, 1427 (2013). 20. C. Yang, et al., “On-Chip Soft-Ferrite-Integrated Inductors for RFIC,” in TRANSDUCERS 2009 - 2009 International SolidState Sensors, Actuators and Microsystems Conference 785 (IEEE, 2009). doi:10.1109/SENSOR.2009.5285666 21. O. Obi, et al., “Spin-Spray Deposited NiZn-Ferrite Films Exhibiting μrʹ > 50 at GHz Range,” J. Appl. Phys., 109, 07E527 (2011). 22. A. K. Subramani, et al., “Spinel Ferrite Films by a Novel Solution Process for High Frequency Applications,” Mater. Chem. Phys., 123, 16 (2010).

23. K. Kondo, et al., “Ferrite Thin Film, Method of Manufacturing the Same and Electromangetic Noise Suppressor Using the Same”, US Patent 7648774 B2 24. D. Mathew and R. Juang, “An Overview of the Structure and Magnetism of Spinel Ferrite Nanoparticles and Their Synthesis in Microemulsions,” Chem. Eng. J., 129, 51 (2007). 25. J. Wang, P. F. Chong, S. C. Ng, and L. M. Gan, “Microemulsion Processing of Manganese Zinc Ferrites,” Mater. Lett., 30, 217 (1997). 26. M. Sivakumar, et al., “Fabrication of Zinc Ferrite Nanocrystals by Sonochemical Emulsification and Evaporation: Observation of Magnetization and Its Relaxation at Low Temperature,” J. Phys. Chem. B, 110, 15234 (2006). 27. M. Baghbanzadeh, L. Carbone, P. D. Cozzoli, and C. O. Kappe, “Microwave-Assisted Synthesis of Colloidal Inorganic Nanocrystals,” Angew. Chem. Int. Ed. Engl., 50, 11312 (2011). 28. I. Bilecka and M. Niederberger, “Microwave Chemistry for Inorganic Nanomaterials Synthesis,” Nanoscale, 2, 1358 (2010). 29. N. Pinna and M. Niederberger, “Surfactant‐Free Nonaqueous Synthesis of Metal Oxide Nanostructures,” Angew. Chemie Int. Ed., 47, 5292 (2008). 30. X. Zuo, et al., “Large Induced Magnetic Anisotropy in Manganese Spinel Ferrite Films,” Appl. Phys. Lett., 87, 1 (2005). 31. A. Yang, Z. Chen, S. M. Islam, C. Vittoria, and V. G. Harris, “Cation Engineering of Cu-Ferrite Films Deposited by Alternating Target Laser Ablation Deposition,” J. Appl. Phys., 103, 10 (2008). 32. R. Weisz, “Interatomic Distances and Ferromagnetism in Spinels,” Phys. Rev., 84, 379 (1951). 33. M. A. Willard, L. K. Kurihara, E. E. Carpenter, S. Calvin, and V. G. Harris, “Chemically Prepared Magnetic Nanoparticles,” Int. Mater. Rev., 49, 125 (2004). 34. I. Bilecka, M. Kubli, E. Amstad, and M. Niederberger, “Simultaneous Formation of Ferrite Nanocrystals and Deposition of Thin Films via a Microwave-Assisted Nonaqueous Sol–Gel Process,” J. Sol-Gel Sci. Technol., 57, 313 (2010). 35. B. Reeja-Jayan, et al., “Microwave-Assisted Low-Temperature Growth of Thin Films in Solution,” Sci. Rep., 2, 1003 (2012). 36. R. Sai, K. J. Vinoy, N. Bhat, and S. A. Shivashankar, “CMOSCompatible and Scalable Deposition of Nanocrystalline Zinc Ferrite Thin Film to Improve Inductance Density of Integrated RF Inductor,” IEEE Trans. Magn., 49, 4323 (2013). 37. R. Sai, S. D. Kulkarni, M. Yamaguchi, N. Bhat, and S. A. Shivashankar, “Integrated X-Band Inductor with a Nanoferrite Film Core,” IEEE Magn. Lett., 8, 1 (2017). 38. L. Carbone and P. D. Cozzoli, “Colloidal Heterostructured Nanocrystals: Synthesis and Growth Mechanisms,” Nano Today, 5, 449 (2010). 39. M. Nuchter, B. Ondruschka, W. Bonrath, and A. Gum, “Microwave Assisted Synthesis? A Critical Technology Overview,” Green Chem., 6, 128 (2004). 40. C. Gabriel, S. Gabriel, E. H. Grant, B. S. J. Halstead, and D. M. P. Mingos, “Dielectric Parameters Relevant to Microwave Dielectric Heating,” Chem. Soc. Rev., 27, 213 (1998). 41. R. Sai, et al., “Controlled Inversion and Surface Disorder in Zinc Ferrite Nanocrystallites and Their Effects on Magnetic Properties,” RSC Adv., 5, 10267 (2015). 42. P. L. Venugopalan, et al., “Conformal Cytocompatible Ferrite Coatings Facilitate the Realization of a Nanovoyager in Human Blood. Nano Lett., 14, 1968 (2014). 43. R. Sai, S. D. Kulkarni, K. J. Vinoy, N. Bhat, and S. A. Shivashankar, “Low-Thermal-Budget Solution Processing of Thin Films of Zinc Ferrite and Other Complex Oxides. MRS Proc., 1400, mrsf11-1400-s06-20 (2012).

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

High Dielectric Constant Materials for Nanoscale Devices and Beyond by Hiroshi Iwai, Akira Toriumi, and Durga Misra

he feature size of a metal oxide semiconductor field effect transistor (MOSFET), the driving force behind the silicon microchips, has approached the 10 nm range and below. The gate dielectric, being the critical constraint, has evolved significantly with the introduction of high dielectric constant (high‑k) materials with metal gates1 and requires constant quality improvements to maintain the proper functioning of the transistors and memory devices in the sub 10nm technology node. Many new devices such as nanowire devices, Ge, III-V semiconductors, graphene, 2D-semiconductor channel replacement devices, and tunnel FETs are emerging for the extension of complementary metal oxide semiconductor (CMOS) technology.2 Some of the most promising devices for beyond-CMOS technology that might replace silicon transistors include spin-FET, negative gatecapacitance FET and all-spin logic devices. All these devices will use high‑k materials at some point or the other. In 2005 an article was published in Interface3 prior to integration of high‑k dielectrcs into CMOS technology for commercial production. It was predicted that high‑k dielectric materials would be part of mainstream technologies. Even though many of the materials problems have been solved and many technologies have matured in the interim, many other challenges have also emerged. In this article, we provide a historical perspective of high‑k dielectric development and discuss new understanding, applications and reliability aspects of high‑k gate dielectrics for current and future nanoscale devices.

History of High‑k Gate Insulator Development Although successful operation of the MOSFET was achieved using a SiO2 gate insulator in 1959,4 the SiO2 gate film had problems of high defect density and a large amount of impurities,5 which caused significant yield and reliability issues in the1960s. Several insulators, such as Si3N4,6 Al2O3,6 and even ZrO27,8 were investigated to solve the problems. For example, it was found that Si3N4 and Al2O3 had the merit of better surface protection from contamination or impurity diffusion. However, the interfacial and bulk trap densities of these films were very high. These films were later used in nonvolatile memory structures such as MNOS (Metal Nitride Oxide Semiconductor)6,9 and MAOS (Metal Alminum Oxide Semiconductor).6,10 Meanwhile, Ta2O5 and Al2O3 were used to replace the SiO2 capacitor in DRAM (Dynamic Rendom Access Memory).11,12 Since the huge merits of the miniaturization or scaling13 of MOSFETs were recognized in early 1970s, the thickness of the SiO2 gate films has been continuously decreased. However, in the past, it was predicted that the limit of the gate SiO2 thinning would be 3 nm because of the onset of the direct-tunneling gate leakage current.14 It was demonstrated later, in 1994, that a small gate length transistor could still function well by using a 1.5 nm thick SiO2 gate insulator.15 The direct-tunneling gate leakage current of the small channel gate area was still sufficiently negligible so as not to affect the Id‑Vd characteristics. Thus, SiO2 film with a small concentration of nitrogen16 with thickness less than 3 nm has been used for LSIs since then. However, the total gate leakage current at a chip level became an issue when the gate oxide thickness approached 1.0 nm. To suppress the direct-tunneling gate leakage current, replacing the SiO2 with a high-dielectric constant (or high‑k) insulator was recognized as a solution. It was expected that similar magnitude of Id‑Vd characteristics with suppression of the gate leakage current could be obtained using a physically-thick high‑k gate film.

Thus, it had been vaguely proposed that such sub-3 nm thick gate insulators would be necessary for sub-100 nm gate length generations. However, the development of high‑k gate insulators for MOSFETs had not been seriously undertaken, because it was not known at all if such small (sub-100 nm) gate length MOSFETs could operate successfully, and also, because alternative dielectric films at that time were found to have a much poorer interface. Therefore, the exploration of some high‑k materials such as Si3N4, TiO2, Ta2O3 and Y2O38,17,18 did not start seriously until the mid-1990s. In the early1990s, the operation of the MOSFETs of gate length down to 25 nm was confirmed by performing Monte Carlo simulations.19 It was predicted that for a MOSFET with a gate length below 50 nm, the gate insulator materials should be high permittivity or high‑k,19 in general, as shown in Fig. 1. Although the operation of 40 nm gate length transistors was verified by experiments in 199320 it was still based on the SiO2 gate insulator as high‑k technology was not available at that time. Subsequently, sub-50 nm gate length MOSFETs were integrated in the scope of the industry, and the search for alternate gate dielectric materials applicable for future sub-50 nm gate length CMOS-LSIs became a challenge.21 Eventually, ZrO2 and HfO2, having similar characteristics, were considered as the most promising candidates because of the suitable dielectric constant, band offset values between the silicon and the dielectric, as well as thermal stability during the fabrication process. In the 1999 International Electron Devices Meeting (IEDM), MOSFETs with ZrO2 or HfO2 as gate insulators were reported for the first time by several groups.22‑24 Later, it was found that HfO2 had a better thermal stability than ZrO2. However, there were still a number of issues, such as thermal stability, mobility degradation, threshold voltage control issue, and Fermi-level pinning, that needed to be resolved. Then, HfO2 high‑k gate insulators with interfacial SiO2 film were introduced into 45 nm CMOS technology in 2007.1,25 In the latest 14‑10nm CMOS technology, HfO2-based oxide is still used but the interfacial SiO2 layer has been removed to lower the EOT down to the sub-nanometer range.26,27 Figure 2 summarizes the issues in high‑k/ metal gate stack technologies. The issues have been solved for use for each generation of the scaling. (continued on next page)

Fig.1. Suggested scaling methodology on the gate oxide thickness.19

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Iwai, et al.

(continued from previous page)

New Understanding and Applications of High‑k Dielectrics HfO2 has been used in advanced CMOS technology since 2007.1 High‑k dielectrics keep the scaling equivalently, because the gate capacitance can be scaled down without physically reducing the oxide thickness. In the early stage of high‑k research, high‑k gate FET formation processes such as gate first or gate last processes have been intensively investigated. A number of challenges have arisen upon introducing high‑k gate stacks. The direct HfO2/Si interface was always worse than SiO2/Si interface, and, as a resultant, the interface carrier mobility was degraded considerably. In addition to the enhanced Coulomb scattering due to the interface states and/or bulk trapped charges, a new type of scattering mechanism, remote phonon scattering, Fig. 2. Issues in high‑k/metal gate stacks. was proposed.28 Interlayer SiO2 was introduced to the dielectric constant in HfO2 was actually demonstrated through the improve the interface quality by avoiding direct contact with Si. This stabilization of the cubic or tetragonal phase. The key factor was the remains a fascinating topic from the device physics viewpoint. structural phase transformation by doping another metal-oxide onto Meanwhile, the FET threshold voltage in high‑k gate stacks was HfO2. The typical example was Y2O3-doped HfO2.34 In fact, it had different from that in SiO2/Si. This was elegantly characterized been well recognized in the ceramics community for a long time that by considering the dipole formation at the high‑k/SiO2 interface.29 Y2O3 doping could induce the oxygen vacancy in ZrO2 to maintain Figure 3 shows the experimental evidence of the high‑k/SiO2 the charge neutrality and more symmetric phase such as cubic or interface dipole. By taking account of the interface dipole, the tetragonal than monoclinic.35 threshold voltage should be described as follows: Recently, ferroelectric HfO2 was reported as shown in Fig. 4.36 2εε 0 qN A (2φF ) Vth = Φ MS + Φ dipole + 2φF + We, very unfortunately, could not notice that HfO2 ferroelectricity Cox emerged upon doping with other oxides, though we had carried out

+ + + + + +

Si SiO2 HfLaO Metal

C/Cmax

the same type of experiments as described above. An interesting in which Φdipole is not included in SiO2/Si gate stacks. This is point in the ferroelectric HfO2 is that the ferroelectric orthorhombic interesting because an electric dipole is formed at insulator/insulator phase is not in the conventional phase diagram. Very recently, we interfaces, and the dipole direction and magnitude are high‑k-material found that ferroelectric HfO2 can also be made by anion doping into dependent. Although the dipole formation mechanism is still under HfO2. The key is how to realize the non-centrosymmetric phase HfO2 debate, our simple model that the dipole may be generated from the structure. The ferroelectric orthorhombic phase might lie between oxygen atom concentration difference at the interface can explain the monoclinic and tetragonal phases as a metastable state.37 This most experimental results.30 In addition, the interlayer SiO2 between fact has made it more difficult to recognize such unexpected but the high‑k film and Si should considerably increase EOT (equivalent advantageous functionality easily. In case of ferroelectric HfO2, oxide thickness) in the ultra-thin EOT region. So, it was considered a couple of nanometers thick ferroelectric film is viable and its whether the interlayer could be scavenged by optimizing the PDA application is promising. conditions of gate stacks.31 This interlayer SiO2 scavenging process New semiconductor substrates such as III-V, Ge and 2D materials 32 was also interesting to study both practically and kinetically. In are now under investigation. In fact, the interface of high‑k films particular, the Si kinetics in SiO2 was mysterious in the scavenging with such substrates are quite different from that formed with Si. In process. We found that the scavenging was very sensitive to the case of Ge, for example, most of the studies have been interested substrate, which strongly suggested Si out diffusion from SiO2 to in exploring interlayer GeO2 on Ge by mimicking the SiO2/Si case, HfO2 due to the Si chemical potential gradient in the gate stack. The dielectric constant of HfO2 is ~18, Au Au and higher-k dielectrics will obviously be 1.0 La20% La60% needed sooner or later to enhance the FET SiO0.8 SiO2 performance. It is technically important to Metal 2 p-Si p-Si decide whether a new higher-k material 0.6 Au should be searched for or whether HfO2 Au La20% should be further used. We have been La20% La60% 0.4 - - - - - interested in the structural phase control La60% La20% dipole of HfO2 to enhance the dielectric constant, SiO 2 SiO2 0.2 p-Si because 1st-principles calculation p-Si Au predict that high temperature phases of La60% 0.0 HfO2 such as cubic or tetragonal phases La20% -3 -2 -1 0 1 2 SiO have a higher-k than the amorphous or 2 p-Si Vg(V) monoclinic phases.33 The monoclinic phase, however, is thermodynamically stable at Si processing temperatures, so usually cubic- or tetragonal-phase Fig. 3. C-V characteristics in (HfO2-La2O3)/SiO2/p-Si capacitors with various combinations of two high‑k Fig. 3(or Hf-concentration) of a Hf-La-O film in contact with HfO2 should be intrinsically unavailable. layers. VFB is determined by the La-concentration SiO . This fact suggests that the dipole layer is controlled by the La concentration of a Hf-La-O film on. SiO2. 2 Nevertheless, significant enhancement of The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Al-doped HfO2

Fig. 4. P-E characteristics in Al-doped HfO2. A clear ferroelectric property is shown in 4.8 mol% Al-doped HfO2.36 (Reprinted from T. S. Böscke, et al., Appl. Phys. Lett. 99, 102903 (2011), with Fig.the4permission of AIP Publishing.)

but it was demonstrated recently that neither GeO2 nor HfO2 were appropriate for the Ge substrate.38 When the substrate is changed from Si, the interface reaction kinetics should be considered from the fundamental viewpoint. Thus, we have to identify both appropriate interlayer and high‑k films on Ge.39

Reliability Issues in High‑k Dielectrics Reliability of high‑k gate stacks has been a serious issue over several generations in the context of integrating high‑k materials and its variations. Understanding the charge trapping behavior in the dielectric and at the interface has been the trend to evaluate its reliability. Furthermore, the gate stack’s response to electrical stress,40-42 especially the bias temperature instability (BTI), is another critical issue for threshold voltage shift (ΔVT) in nanoscale devices. Self-heating in FinFETs further adds to the problem of BTI.43 The other vital issue of reliability of high‑k gate stacks is related to stressinduced dielectric breakdown. Studies of breakdown characteristics of high‑k gate stacks are made complicated by the fact that the potential drop/electric field across interfacial and high‑k layers are different due to the differences in the values of the dielectric constant and thickness.44-46 Once the EOT goes down below 0.7 nm for silicon devices, and when germanium is introduced as the channel material, the reliability problem can be exacerbated. High‑k gate dielectrics are known to have a much larger preexisting intrinsic trap density compared to silicon dioxide. These traps, responsible for electron/hole trapping, can be classified into three groups47 according to their locations within the bulk high‑k bandgap as shown in Fig. 5. Group A defect levels lie above the Si conduction band edge, ECSi remains empty under “zero bias,” i.e., zero electric field and thermal equilibrium conditions. However, under “non-zero” gate bias such states facilitate the tunneling of electrons from ECSi/gate through the thin interfacial layer (IL). Thus, they serve as the electron traps. Once the bias is removed, very fast (within μs) de-trapping to the substrate/gate occurs from these states. Hence, these shallow levels give rise to fast transient trapping of electrons, which is mostly responsible for hysteresis and mobility degradation. Group B defects lie within the Si bandgap range. Under “zero bias” conditions, carriers trapped in these deep states de-trap slowly to the substrate, depending on the physical distance from the substrate, and the activation energy w.r.t. to ECSi, which gives rise to slow transient trapping. ΔVT due to trapping at these deep levels is the most critical reliability factor for the high‑k dielectrics. Electrons trapped at levels below EVSi (Group C) give rise to fixed oxide charges.

Since the introduction of HfO2 in mainstream technology1 its reliability has been extensively studied under different stress conditions.48,49 However, the negative bias temperature instability (NBTI) for p-channel MOSFETs and positive bias temperature instability (PBTI) for n-channel MOSFETs remain as serious degradation mechanisms when device temperature is increased.1 Interface state defect generation triggered by Si-H bond breaking at the interface is a point of major concern. One of the widely-used NBTI models is based on reaction-diffusion (R-D) theory, which basically focuses on time dependent net increase in the number of interface defects taking place during electrical stress at elevated temperatures. PBTI has become a concern for high‑k devices even though it was not a serious concern for Si/SiO2 devices. Recent evidence of self-heating in FinFETs has also become a growing concern.44 Since the thermal resistance of these devices has increased from that of planar to bulk FinFET and into SOI FinFET, it is expected to increase even further in future devices like gate-all-around transistors. The impact of selfheating further enhances the NBTI or PBTI degradation process in these devices.50 High‑k gate stacks are usually represented by a multi-layer structure that includes a high‑k dielectric and a thin interfacial layer. Each of these layers, in turn, is affected by interlayer material interactions, in particular, a metal electrode may affect composition of the gate dielectric and a high‑k film may change the stoichiometry of the underlying interfacial layer.46 Stress-induced degradation of the dielectric stack can originate from defect generation in both the high‑k layer and in the interfacial layer, in which degradation is expected to be controlled by different mechanisms. The investigation of breakdown characteristics suggests that the breakdown of the gate stack is typically triggered by defect generation in the thin SiO2 interfacial layer. Several intermediate treatments during the atomic layer deposition (ALD) process of Hf-based high‑k dielectrics have been tried recently to enhance the quality of dielectrics and to downscale the EOT.51 Zr incorporation in HfO2 along with intermediate treatment like plasma exposure or plasma oxidation seems to be promising. The time dependent dielectric breakdown (TDDB) characteristics suggest that the time to breakdown of Hf1-xZrxO2 on silicon increases with increasing Zr percentage when the dielectric is exposed to alternate inert plasma during cyclic ALD deposition. On the other hand, when Ge devices (p-Ge/Al2O3/ZrO2/TiN) were subjected to TDDB, a rapid degradation of TDDB characteristics was observed when a low-k GeO2 interfacial layer was formed during processing. Unlike SiO2, GeO2 seems to degrade easily. But when a comparatively thinner GeOx interfacial layer is formed because of process control, better TDDB characteristics were observed (Fig. 6).52,53 More reliability work is, therefore, necessary for high‑k on Ge and other III-V and 2D materials to integrate these materials into mainstream commercial technologies. (continued on next page)

High-? CB High-κ

IL CB

CB SiSiCB

E High-k C

E Si C

High-k V

Si VB High-? VB High-κ

IL VB

Fig. 5. Defect levels within the bulk high‑k in the context of MOS energy Fig. 5 band diagram: shallow traps (A), deep traps (B) and fixed oxide charge (C).

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Iwai, et al.

(continued from previous page)

Fig. 6. Statistical (Weibull) distribution of TDDB breakdown characteristics of a p‑Ge/Al2O3/ZrO2/TiN gate stack. Fig. 6

Summary High‑k gate dielectrics has become part of the mainstream CMOS technology, including advanced FinFET devices. We have discussed the historical evolution of this high‑k gate dielectric through scientific and technological challenges over many decades until it was introduced into 45 nm CMOS technology in 2007 by replacing SiO2. Interface and dipole issues were somewhat resolved through scientific understanding and technological innovation. Thanks to the step coverage advantage of atomic layer deposition process, high‑k was easily migrated to FinFET technology. Reliability of devices with high‑k was a significant problem in the beginning but over time it has been improved significantly. Use of high‑k on new semiconductor substrates such as III-V, Ge and 2D materials is currently being investigated but faces many challenges. Recent discovery of ferroelectric properties of HfO2 makes it viable for more potential applications. © The Electrochemical Society. DOI: 10.1149/2.F09174if.

About the Authors Hiroshi Iwai is the professor emeritus at the Tokyo Institute of Technology, and vice dean and distinguished chair professor of National Chiao Tung University in Taiwan. After receiving BE and PhD degrees from the University of Tokyo, he worked at Toshiba Corporation for 26 years and then Tokyo Institute of Technology for 18 years. Iwai is highly recognized for his significant contributions for the development of dielectric films. Those contributions include the introduction of BPSG film reflow to integrated circuits, finding plasma induced damage on gate insulator, prevention of boron penetration of gate oxide by RTN gate SiO2, and the introduction of 1.5 nm tunneling gate oxide to CMOS. Additionally, Iwai is the chair of the ECS Japan Section. He is the winner of Thomas Callinan Award from the Dielectric Science and Technology Division of ECS and has served as an organizer of many ECS symposia and has been a member of various Society committees. Iwai co-authored over 1,000 international and 500 domestic papers in journals and conferences. He may be reached at iwai.h.aa@m.titech.ac.jp.

Akira Toriumi is a professor of Materials Engineering at The University of Tokyo, Japan. He received the B.S. degree in physics, the M.S. and Ph.D. degrees in applied physics from The University of Tokyo. He joined Research and Development Center of Toshiba Corporation and then he moved to The University of Tokyo. His current research interests include materials science and device physics of high-k dielectrics for both silicon and germanium FETs, and materials science and applications of functional oxides. He has authored more than 400 refereed journal/conference publications, and a couple of book chapters. He is a fellow of the Japan Society of Applied Physics and a fellow of the Institute of Electrical and Electronics Engineers. He may be reached at toriumi@ material.t.u-tokyo.ac.jp. Durga Misra is a professor in the Helen and John C. Hartmann Department of Electrical and Computer Engineering, New Jersey Institute of Technology, Newark, USA. His current research interests are in the areas of nanoelectronic/ optoelectronic devices and circuits; especially in the area of nanometer CMOS gate stacks and device reliability. He is a fellow of The Electrochemical Society. He received the Thomas Collinan Award from the Dielectric Science and Technology Division of ECS. He is also the winner of the Electronic and Photonic Division Award from ECS. He edited and co-edited more than 45 books and conference proceedings in his field of research. He has published more than 250 technical articles in peer reviewed journals and in international conference proceedings. He received the MS and PhD degrees in electrical engineering from the University of Waterloo, Waterloo, ON, Canada. He may be reached at dmisra@njit.edu. https://orcid.org/0000-0001-6844-6058

References 1. M. T. Bohr, R. S. Chau, T. Ghani, and K. Mistry, IEEE Spectrum, 44(10), 29 (2007). 2. R. M. Wallace, ECS Trans., 80(1), 17, (2017). 3. D. Misra, H. Iwai, and H. Wong, Electrochem. Soc. Interface, 14(2), 30, (2005). 4. D. Kahng and M. Atalla, Paper presented at the IRE-AIEE Solid-State Device Research Conference, Pittsburgh, PA (1960). 5. E. H. Snow, et al., J. Appl. Phys., 36, 1664 (1965). 6. Y. Nishi and H. Iizuka, in Silicon Integrated Circuits, Part A, Suppl. 2A, D. Kahng Editor, Academic Press, New York (1981). 7. T. Sugano, H. Sakaki, and K. Hoh, Suppl. J. Japan Soc. Appl., 39, 192 (1970). 8. G. D. Wilk, R. M. Wallace, and J. M. Anthony, J. Appl. Phys., 89, 5243 (2001). 9. H. C. Pao and M. O’Connell, Appl. Phys. Lett., 12, 260 (1968). 10. N. J. Chou and P. J. Tsang, Metall. Trans., 2, 659 (1971). 11. K. Kim, et al., in Guide to State-of-the Art Electron Devices, J. N. Burghaltz Editor, John Wiley & Sons (2013). 12. S. K. Park, SEMATECH Symp. Korea, 27 (2011). 13. R. H. Dennard, et al., IEEE J. Solid-State Circuits, 9, 256 (1974). 14. B. Honestain and S. C. Mead, Solid-State Electron., 15, 819 (1972). 15. H. S. Momose, M. Ono, T. Yoshitomi, T. Ohguro, S. Nakamura, M. Saito, and H. Iwai, et al., IEEE Int. Electron. Devices Meet., 593 (1994). 16. T. Morimoto, H. S. Momose, Y. Ozawa, K. Yamabe, and H. Iwai, IEEE Int. Electron. Devices Meet., 429 (1990). 17. H. Iwai, et al., in Physics and Technology of High-κ Dielectrics I, S. Kar, et al., Editors, The Electrochemical Society Proceedings Series, PV 2002-28, p. 27, Pennington, NJ (2002).

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

18. H. Wong and H. Iwai, Microelectron. Eng., 83, 1867 (2006). 19. C. Fiegna, H. Iwai, T. Wada, T. Saito, E. Sangiorgi, and B. Ricc`o, in Symposium on VLSI Technology, p. 33, IEEE (1993). 20. M. Ono, M. Saito, T. Yoshitomi, C. Fiegna, T. Ohguro, and H. Iwai, IEEE Int. Electron. Devices Meet., 119 (1993). 21. K. Hubbard and D. Schlom, J. Mater. Res., 11, 2757 (1996). 22. B. H. Lee, et al., IEEE Int. Electron. Devices Meet., 133 (1999). 23. W. J. Qi, et al., IEEE Int. Electron. Devices Meet., 145 (1999). 24. Y. Ma, et al., IEEE Int. Electron. Devices Meet., 149 (1999). 25. K. Mistry, et al., IEEE Int. Electron. Devices Meet., 247 (2007). 26. S. Natarajan, et al., IEEE Int. Electron. Devices Meet., 71 (2014). 27. T. Ando, et al., IEEE Int. Electron. Devices Meet., 423 (2009). 28. M. Fischetti, et al., J. Appl. Phys. 90, 4587 (2001). 29. Y. Yamamoto, et al., Jpn. J. Appl. Phys., 46, 7251 (2007). 30. K. Kita, K. Kyuno and A. Toriumi, Appl. Phys. Lett., 86, 102906 (2005). 31. T. Ando, Materials, 5, 478 (2012). 32. X. Li, et al., Appl. Phys. Lett., 105, 182902 (2014). 33. X. Zhao and D. Vanderbuild, Phys. Rev. B, 65, 233106 (2002). 34. K. Kita and A. Toriumi, Appl. Phys. Lett., 94, 132902 (2009). 35. I-W. Chen and Y-H. Chiao, Acta Metall., 33, 1827 (1985). 36. T. S. Bӧscke, et al., Appl. Phys. Lett. 99, 102903 (2011). 37. L. Xu et al., J. Appl. Phys. 122, 1234104 (2017). 38. C. Lu, et al., IEEE Int. Electron. Devices Meet. Tech. Dig., 370 (2015). 39. A. Toriumi and T. Nishimura, Jpn. J. Appl. Phys., 57, 010101(2018), published online October 30, 2017, http:// iopscience.iop.org/article/10.7567/JJAP.57.010101. 40. J. Robertson, Solid State Electron., 49(3), 283 (2005). 41. M. Houssa, S. De Gendt, G. Groeseneken, and M. M. Heyns, J. Electrochem. Soc., 151, F288 (2004). 42. A. Kerber, and P. Srinivasan, IEEE Electron. Dev. Lett., 35, 431 (2014). 43. P. Paliwoda, Z. Chbili, A. Kerber, A. Gondal, and D. Misra, Paper presented at the IEEE International Integrated Reliability Workshop, IEEE (2017). 44. R. I. Hegde, D. H. Triyoso, S. B. Samavedam, and B. E. White, J. Appl. Phys., 101, 074113-1 (2007). 45. N. Rahim and D. Misra, J. Electrochem. Soc., 155, G194 (2008). 46. G. Bersuker, N. Chowdhury, C. Young, D. Heh, D. Misra, and R. Choi, in Proceedings of the IEEE Reliability Physics Symposium, p. 49, IEEE (2007). 47. N. A. Chowdhury and D. Misra, J. Electrochem. Soc., 154, G30 (2007). 48. M. Cho, B. Kaczer, T. Kauerauf, L. A. Ragnarsson, and G. Groeseneken, IEEE Electron. Dev. Lett., 34, 593 (2013). 49. A. Kerber and E. Cartier, IEEE Trans. Dev. Mater. Rel., 9, 147 (2009). 50. C. Prasad, et al., Proceedings of the IEEE Reliability Physics Symposium (IRPS), 5D.1.1 (2013). 51. M. N. Bhuyian, D. Misra, K. Tapily, R. Clark, S. Consiglio, C. Wajda, G. Nakamura, and G. Leusink, ECS J. Solid State Sci. Technol., 3, N83 (2014). 52. Y. M. Ding, D. Misra, K. Tapily, R. D. Clark, S. Consiglio, C. S. Wajda, and G. J. Leusink, IEEE Trans. Dev. Mater. Rel., 17, 349 (2017). 53. P. Shao, M. N. Bhuyian, Y. M. Ding and D. Misra, ECS Trans., 80(1), 71 (2017).

THE ELECTROCHEMICAL SOCIETY

MONOGRAPH SERIES

The following volumes are sponsored by ECS, and published by John Wiley & Sons, Inc. Order your copy from the ECS Online Store today! Electrochemical Impedance Spectroscopy (2nd Edition) By Mark E. Orazem and Bernard Tribollet (2017) 768 pages, ISBN 978-1-118-52739-9 Atmospheric Corrosion (2nd Edition) By C. Leygraf, I. Odnevall Wallinder, J. Tidblad, and T. Graedel (2016) 400 pages, ISBN 978-1-118-76227-1 Molecular Modeling of Corrosion Processes: Scientific Development and Engineering Applications Edited by C. D. Taylor and P. Marcus (2015) 272 pages, ISBN 978-1-118-26615-1 Electrochemical Power Sources: Batteries, Fuel Cells, and Supercapacitors By V. S. Bagotsky, A. M. Skundin, and Y. M. Volfkovich (2015) 400 pages, ISBN 978-1-118-46023-8 Modern Electroplating (5th Edition) Edited by M. Schlesinger and M. Paunovic (2014) 736 pages, ISBN 978-0-470-16778-6 Lithium Batteries: Advanced Technologies and Applications Edited by B. Scrosati, K. M. Abraham, W. A. van Schalkwijk, and J. Hassoun (2013) 392 pages, ISBN 978-1-118-18365-6 Fuel Cells: Problems and Solutions (2nd Edition) By V. S. Bagotsky (2012) 406 pages, ISBN 978-1-118-08756-5 Uhlig’s Corrosion Handbook (3rd Edition) Edited by R. Winston Revie (2011) 1,296 pages, ISBN 978-0-470-08032-0 Fundamentals of Electrochemical Deposition (2nd Edition) By M. Paunovic and M. Schlesinger (2006) 373 pages, ISBN 978-0-471-71221-3 Fundamentals of Electrochemistry (2nd Edition) Edited by V. S. Bagotsky (2005) 752 pages, ISBN 978-0-471-70058-6 Electrochemical Systems (3rd Edition) By J. Newman and K. E. Thomas-Alyea (2004) 672 pages, ISBN 978-0-471-47756-3

ECS Members will receive a discount. See the ECS website for prices.

Visit the ECS Online Store The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

T ECH SEC TION HIGHLIGH NE WS TS Singapore Section The ECS Singapore Section worked with Cambridge University to offer an Electrochemical Technique course from June 21 to June 22, 2017 at the Campus for Research Excellence and Technological Enterprise (CREATE) in Singapore. The course was hosted by the Cambridge Centre for Carbon Reduction in Chemical Technology (C4T) at CREATE. The course was attended by local industrialists and researchers from Singapore, the United Kingdom, and China, as well as C4T researchers. The course was also supported by kind sponsorship from Metrohm. The objective of the course was to provide lectures, seminars, and hands-on experiments for industrialists and scientists who use or wish to use analytical electrochemical methods for their research

or industrial applications. The course strongly emphasized the use of small group teaching methods endorsed by Cambridge University and CREATE collaborators to train participants in the use of stateof-the-art electrochemical techniques. The question and answer periods, which followed each session of the program, were key elements of the course. Delegates were able to explore the complex concepts introduced in the lectures with the course’s director and tutors to maximize the learning experience. All delegates were given the opportunity to gain firsthand experience in operating the latest electrochemical analysis equipment and software. Working in small groups, the delegates carried out a series of experimental and analytical measurements to support and enhance the material covered within the lectures.

Twin Cities Section The ECS Twin Cities Section held its local, one-day Electrochemistry Symposium on April 7, 2017 at the 3M Customer Innovation Center. The section organized the symposium with support from ECS and 3M. Six electrochemistry experts from the FDA, academia, and industry gave technical talks covering various topics of interest in electrochemistry: • Johna Leddy, ECS president, University of Iowa, “Electrochemically Silent Films on Electrodes - Means and Methods.” • Bob R. Powell, GM technical fellow and manager, “LithiumIon Batteries: Foundational for Automotive Electrification.” • Michael Root, Boston Scientific fellow, “Assessing the Performance and Reliability of Implantable Medical Device Batteries.” • Pavel Takmakov, FDA, “Chemistry of Robust Neural Interfaces.” • Philippe Buhlmann, University of Minnesota, “Reference Electrodes Are the Easy Part. Really?” • Brandon Bartling, 3M product development specialist, “Redox Flow Batteries – Fun with Pumps and Electrons.” The symposium also included a student poster session. Seven graduate students from the University of Minnesota and the University of Wisconsin-Madison presented their work. PhD candidate Jinbo Hu, from the Department of Chemistry at the University of Minnesota, won the Outstanding Poster Award for his work “A Disposable Planar PaperBased Potentiometric Ion-Sensing.” About 80 electrochemistry enthusiasts attended the symposium. During lunch hours, all attendees were given a free tour of the 3M Customer Innovation Center.

Twin Cities Section officials with the winner of the student poster session (from left to right): Vincent Chevrier, Jinbo Hu, and Peter Zhang.

Twin Cities Section officials and symposium speakers (from left to right): Peter Zhang, Johna Leddy, Vincent Chevrier, Phi Buhlmann, Ben Wilson, Pasha Takmakov, Michael Root, Brandon Bartling, and Hui Ye. 82

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

ORCID

T ECH SEC TION HIGHLIGH NE WS TS

Connecting Research and Researchers

DIstInguIsh yOuRself In thRee easy steps: What is ORCID?

1 2 3

RegIsteR for an ORCID iD COnneCt your iD to your work use yOuR iD in grants, publications, datasets, and more Register today at orcid.org

The Electrochemical Society Interface â&#x20AC;˘ Winter 2017 â&#x20AC;˘ www.electrochem.org

ORCID is a registry of unique identifiers for researchers and scholars that is open, non-proprietary, transparent, mobile, and community-based. ORCID provides a persistent digital identifiers that distinguishes you from every other contributor and supports automated linkages among all your professional activities.

Join ORCID today and become part of the solution.

AWARDS NE W MEMBERS PROGRAM

Awards, Fellowships, Grants ECS distinguishes outstanding technical achievements in electrochemistry, solid state science and technology, and recognizes exceptional service to the Society through the Honors & Awards Program. Recognition opportunities exist in the following categories: Society Awards, Division Awards, Student Awards, and Section Awards. ECS recognizes that today’s emerging scientists are the next generation of leaders in our field and offer competitive Fellowships and Grants to allow students and young professionals to make discoveries and shape our science long into the future.

See highlights below and visit www.electrochem.org for further information.

Society Awards Fellow of The Electrochemical Society was established in 1989 as the Society’s highest honor in recognition of advanced individual technological contributions in the field of electrochemistry and solid state science and technology, and active ECS membership. The award consists of an appropriately worded scroll and lapel pin. Materials are due by February 1, 2018. The Allen J. Bard Award was established in 2013 to recognize distinguished contributions to electrochemical science and exceptionally creative experimental or theoretical studies that have opened new directions in electroanalytical chemistry or electrocatalysis. The award consists of a plaque, a

$7,500 prize, complimentary meeting registration for award recipient and companion, a dinner held in recipient’s honor during the designated meeting, and life membership. Materials are due by April 15, 2018. The Gordon E. Moore Medal was established in 1971 for distinguished contributions to the field of solid state science and technology. The award consists of a silver medal, a plaque, a $7,500 prize, complimentary meeting registration for award recipient and companion, a dinner held in recipient’s honor during the designated meeting, and life membership. Materials are due by April 15, 2018.

Division Awards The Corrosion Division Herbert H. Uhlig Award was established in 1972 to recognize excellence in corrosion research and outstanding technical contributions to the field of corrosion science and technology. The award consists of a scroll, a $1,500 prize, and possible travel assistance. Materials are due by December 15, 2017. The High Temperature Materials Division Outstanding Achievement Award was established in 1984 to recognize excellence in high temperature materials research and outstanding technical contributions to the field of high temperature materials science. The award consists of a scroll, a $1,000 prize, and possible travel assistance. Materials are due by January 1, 2018.

The Luminescence and Display Materials Divisions Centennial Outstanding Achievement Award was established in 2002 to encourage excellence in luminescence and display materials research and outstanding contributions to the field of luminescence and display materials science. The award consists of a scroll and a $1,000 prize. Materials are due by January 1, 2018. The Battery Division Research Award was established in 1958 to recognize excellence in battery and fuel cell research, and encourage publication in ECS outlets. The award recognizes outstanding contributions to the science of primary and secondary cells, batteries and fuel cells. The award consists of a certificate and the sum of $2,000. Materials are due by March 15, 2018.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

AWARDS NE W AWA MEMBERS PROGRAM RDS The Battery Division Technology Award was established in 1993 to encourage the development of battery and fuel cell technology, and to recognize significant achievements in this area. The award is given to those individuals who have made outstanding contributions to the technology of primary and secondary cells, batteries, and/or fuel cells. The award consists of a certificate and the sum of $2,000. Materials are due by March 15, 2018. The Battery Division Postdoctoral Associate Research Award, sponsored by MTI Corporation and the Jiang Family Foundation, was established in 2016 to encourage excellence among postdoctoral researchers in battery and fuel cell research. The award consists of a framed scroll, a $2,000 prize, and complimentary meeting registration at the designated meeting. Two awards will be granted each year. Materials are due by March 15, 2018.

The Electrodeposition Division Research Award recognizes outstanding research contributions to the field of electrodeposition and encourages the publication of high quality papers in this field in the Journal of The Electrochemical Society (JES). The award shall be based on recent outstanding achievement in, or contribution to, the field of electrodeposition and will be given to an author or co-author of a paper that must have appeared in JES or another ECS publication. The award consists of a certificate and the sum of $2,000. Materials are due by April 1, 2018. The Electrodeposition Division Early Career Investigator Award recognizes an outstanding young researcher in the field of electrochemical deposition science and technology. Early recognition of highly qualified scientists is intended to enhance the scientist stature and encourage especially promising researchers to remain active in the field. The award consists of a certificate and the sum of $1,000. Materials are due by April 1, 2018.

Student Awards The Corrosion Division Morris Cohen Graduate Student Award was established in 1991 to recognize and reward outstanding graduate research in the field of corrosion science and/or engineering. The award consists of a certificate and a $1,000 prize. The award, for outstanding Masters or PhD work, is open to graduate students who have successfully completed all the requirements for their degrees as testified to by the student’s advisor, within a period of two years prior to the nomination submission deadline. Materials are due by December 15, 2017.

The Battery Division Student Research Award recognizes promising young engineers and scientists in the field of electrochemical power sources. The award is intended to encourage the recipients to initiate or continue careers in the field. Eligible candidates must be enrolled in a college or university at the time of the nomination deadline. The award consists of a certificate and the sum of $1,000. Materials are due by March 15, 2018.

ECS FELLOWS 2018 Call for Nominations Deadline: February 1, 2018

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

NE W MEMBERS ECS is proud to announce the following new members for July, August, and September 2017.

Members

Thomas Allison, Gaithersburg, MD, USA Osemudiamen Amedu, Bochum, NW, Germany Ryo Arimura, Kadoma-shi, Osaka, Japan Claudia Backes, Heidelberg, BW, Germany Saifullah Badar, Moriguchi, Osaka, Japan Seongmin Bak, Upton, NY, USA Bhaskar Bandarapu, Villach, K, Austria Sara Barron, Braintree, MA, USA Senthilkumar Baskar, Bangalore, KA, India Derek Bassett, Cedar Park, TX, USA Thomas Beck, Cincinnati, OH, USA Mahbuba Begum, Little Rock, AR, USA Hamdi Ben Yahia, Doha, Qatar Erik Berg, Villigen PSI, Switzerland Navakanta Bhat, Bangalore, KA, India Emilie Bodoin, Yonkers, NY, USA Vincent Bouchiat, Grenoble, France Avram Buchbinder, Des Plaines, IL, USA Monica Burriel, Grenoble, France Max Cadeddu, Voghera, Italy James Cahoon, Chapel Hill, NC, USA Silvia Cere, Mar del Plata, Argentina Karen Chan, Menlo Park, CA, USA Halle Cheeseman, Lake City, FL, USA Dejun Chen, Arlington, VA, USA Shuru Chen, Richland, WA, USA Kangguo Cheng, Albany, NY, USA Lei Cheng, Lemont, IL, USA Lili Cheng, Rexford, NY, USA EunAe Cho, Daejeon, South Korea Younjin Cho, Suwon, Gyeonggi, South Korea Taekjib Choi, Seoul, South Korea Ali Cirpan, Ankara, Ankara, Turkey Joel Coffel, Coralville, IA, USA Stuart Cogan, Richardson, TX, USA David Cook, Southampton, Hampshire, United Kingdom Ethan Crumlin, Berkeley, CA, USA Fabio Di Fonzo, Milano, Italy Zhijia Du, Oak Ridge, TN, USA Sebastian Eberhardt, Surrey, BC, Canada John Ekerdt, Austin, TX, USA Abdel El kharbachi, Kjeller, Norway Ramez Elgammal, Knoxville, TN, USA Zhu Feng, NingDe, China Ross Fontenot, Falls Church, VA, USA Gregory Forcherio, Adelphi, MD, USA David French, Edinburgh, United Kingdom Rei Furukawa, Tokyo, Tokyo, Japan Aldo Gago, Stuttgart, BW, Germany Lijun Gao, Suzhou, China Ercolano Giorgio, Montpellier, France Andrea Gomez Sanchez, Villa Maria, Argentina Edward Gonzales, Longmont, CO, USA Detlev Gruetzmacher, Jülich, NW, Germany Yvonne Grunder, Liverpool, EN, United Kingdom Ivana Hasa, Berkeley, CA, USA Kei Hasegawa, Meguro-ku, Tokyo, Japan

John Hennessy, Pasadena, CA, USA Jeanette Henry, Longmont, CO, USA Sally Ann Henry, Boise, ID, USA Matthew Hider, Portland, OR, USA Bing Hsieh, South San Francisco, CA, USA Botao HUANG, Cambridge, MA, USA Henry Huang, Maple Ridge, BC, Canada Yiqing Huang, Hayward, CA, USA Karim Huet, Paris, France Muhammad Hussain, Austin, TX, USA Kiwook Hwang, Suwon-si, South Korea Rajeswari Janarthanan, Solon, OH, USA Jong Yeob Jeon, Troy, NY, USA Kentaro Kaneko, Kyoto City, Kyoto, Japan Hideyuki Kanematsu, Sakai, Osaka, Japan Ranjith Karuparambil Ramachandran, Ghent, Belgium Satender Kataria, Aachen, NW, Germany Mark Kawaguchi, San Carlos, CA, USA Yohannes Kiros, Stockholm, Sweden Tatsumi Kitahara, Fukuoka, Japan Randolph Knarr, Voorheesville, NY, USA Seung Hyeon Ko, Daejeon, South Korea Siddharth Komini Babu, Los Alamos, NM, USA Hiroki Kondo, Woodridge, IL, USA Sergey Krachkovskiy, Hamilton, ON, Canada Patrick Kung, Tuscaloosa, AL, USA Yoshiyuki Kuroda, Yokohama, Kanagawa, Japan Tim La Valle, Annapolis, MD, USA Rakesh Lal, Isla Vista, CA, USA Shashi Lalvani, West Chester, OH, USA Benjamin T. H. Lee, Taoyuan City, Taiwan Hyowon Lee, West Lafayette, IN, USA Rung-Chuan Lee, Berkeley, CA, USA Sunghwan Lee, Waco, TX, USA Chao Lei, Newton, MA, USA Xu Lei, Tokyo, Tokyo, Japan Xuelei Liang, Beijing, China Jinsub Lim, Gwangju, South Korea Krista Limmer, Charlestown, MD, USA Danni Lin, Kearny, NJ, USA Chanyuan Liu, Tualatin, OR, USA Tong Liu, Wuhan, Hubei, China Zengcai Liu, Boca Raton, FL, USA Xiaowei Ma, Halifax, NS, Canada Joseph Manser, Washington, DC, USA Hiroshi Marumoto, Hillsboro, OR, USA Scott Mauger, Golden, CO, USA Yuto Miyahara, Kyoto City, Kyoto, Japan Dai Mochizuki, Ueda, Nagano, Japan Harold Monbouquette, Santa Monica, CA, USA Daisuke Mori, Tsu, Mie, Japan Subhadeep Mukherjee, Woodbridge, VA, USA Richard Murray, Palatine, IL, USA Hiroki Nagashima, Nakagami-gun, Okinawa, Japan Shrikant Nagpure, Idaho Falls, ID, USA Jun Nakamura, Chofu, Tokyo, Japan Hiroto Nakaya, State College, PA, USA

Rajalakshmi Natarajan, Chennai, TN, India Chilan Ngo, Lakewood, CO, USA Christopher Nicholas, Des Plaines, IL, USA Chaojiang Niu, Richland, WA, USA Jinwoo Park, Buffalo, NY, USA Sam Pearn-Rowe, Perth, Western Australia, Australia Anastasia Permyakova, Villigen, AG, Switzerland Ahmad Pesaran, Lakewood, CO, USA Emanuele Piciollo, Montevarchi, Italy Alfred Piggott, Novi, MI, USA Satyananda Kishore Pilli, Solon, OH, USA Branko Popov, Columbia, SC, USA Carole Read, Washington, DC, USA Takuya Saeki, Yokohama, Kanagawa, Japan Jean-Yves Sanchez, Leganes, MAD, Spain Ivana Savic, Cork, Ireland Rolf Schuster, Karlsruhe, Germany Neeraj Sharma, Sydney, New South Wales, Australia Steven Shatas, Santa Clara, CA, USA John Shen, Chicago, IL, USA Shyh-Chiang Shen, Atlanta, GA, USA Yixiang Shi, Beijing, China Kevin Sivula, Lausanne, VD, Switzerland Sushant Sonde, Westmont, IL, USA Zhen Song, Corning, NY, USA Jozsef Speder, Hanau-Wolfgang, HE, Germany Erik Spoerke, Albuquerque, NM, USA Bing Sun, Villigen, Switzerland Yujie Sun, Logan, UT, USA Joseph Sunstrom, Trinity, AL, USA Takafumi Tanehira, Hiroshima-shi, Hiroshima, Japan Tanvir Tanim, Idaho Falls, ID, USA Tokuyuki Teraji, Tsukuba, Ibaraki, Japan Herman Terryn, Brussels, Belgium Maria Eugenia Toimil Molares, Darmstadt, HE, Germany Kyohei Tsutano, Sagamihara, Kanagawa, Japan Kazuhide Ueno, Yokohama, Kanagawa, Japan Hiroaki Umeda, Otsu, Shiga, Japan Oomman Varghese, Houston, TX, USA B. Jill Venton, Charlottesville, VA, USA Jingjing Wang, Livingston, NJ, USA Hiroyuki Watabe, Yokohama-shi, Kanagawa, Japan John Watkins, Pittsburgh, PA, USA Natascha Weidler, Darmstadt, HE, Germany Andrew Weng, Palo Alto, CA, USA Jack Whalen, Pasadena, CA, USA Quinton Williams, Washington, DC, USA Jingjie Wu, Mason, OH, USA Jun Xu, Beijing, China Kaoru Yaegashi, Sunnyvale, CA, USA Cheng-Hsien Yang, Taoyuan, Taiwan, Taiwan Ruidong Yang, Ann Arbor, MI, USA Koffi Yao, Willowbrook, IL, USA Kunio Yube, Katsushika-ku, Tokyo, Japan

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

NE W MEMBERS Alexander Zestos, Washington, DC, USA Siyuan Zhang, Germantown, MD, USA Hongping Zhao, Columbus, OH, USA Huajun Zhou, Fayetteville, AR, USA Eugeniusz Zych, Wroclaw, Poland

Student Members

Mehrdad Abbasi Gharacheh, Athens, OH, USA Charles Abbey, Rolla, MO, USA Zeeshan Ahmad, Pittsburgh, PA, USA Burak Aktekin, Uppsala, Sweden Bryan Alamani, Houston, TX, USA Noora Al-Qahtani, London, United Kingdom Rusul Al-Rubaay, Leicester, Leicestershire, United Kingdom Abdulsattar Alsaedi, Iowa City, IA, USA Randall Archer, San Marcos, TX, USA Maalavan Arivu, Rolla, MO, USA Christopher Arnold, Atlanta, GA, USA Milad Azami Ghadkolai, Central, SC, USA Ugljesa Babic, Villigen, AG, Switzerland Pavan Badami, Tempe, AZ, USA Meisam Bahari, Provo, UT, USA Qiang Bai, College Park, MD, USA David Bazak, Hamilton, ON, Canada Shawn Benson, Lawrence, KS, USA Sarah Berlinger, Berkeley, CA, USA Nico Bevilacqua, Ulm, BW, Germany Yousuf Bootwala, Pittsburgh, PA, USA David Borth, Springboro, OH, USA Rene Bottcher, Ilmenau, TH, Germany Jonathan Braaten, Pittsburgh, PA, USA Borja Cantero-Tubilla, Ithaca, NY, USA Sara Cantonwine, Columbus, OH, USA Austin Carver, Greenwood, SC, USA Nicholas Casco, Bolton, MA, USA Mathilde Cazot, Jarville, France Gi Chang, Changwon-si, Gyeongsangnamdo, South Korea Swarnendu Chatterjee, Philadelphia, PA, USA Po-An Chen, Tainan City, Taiwan, Taiwan Qingzhi Chen, Rolla, MO, USA Ti Chen, Yokohama-shi, Kanagawa, Japan Tina Chen, Berkeley, CA, USA Shan-Ju Chiang, Chicago, IL, USA Seonghun Cho, Daejeon, South Korea Hyejeong Choi, La Mesa, CA, USA Paul Choi, Pittsburgh, PA, USA Anamika Chowdhury, Berkeley, CA, USA Salih Cihangir, Leicester, Leicestershire, United Kingdom Kameron Conforti, Cambridge, MA, USA Kathrine Curtin, Latrobe, PA, USA Michael D’Ambrose, Brooklyn, NY, USA Kevin Dankyi, Olathe, KS, USA Michael Daugherty, Oak Ridge, TN, USA Brian Day, Pittsburgh, PA, USA Abhas Deva, West Lafayette, IN, USA Andrew Dillon, Philadelphia, PA, USA Marm Dixit, Nashville, TN, USA Anna Dorfi, New York, NY, USA Hossein Dormohammadi, Corvallis, OR, USA

Mohamed Doumbia, Silver Spring, MD, USA Paul Dourte, Sparks, NV, USA Eduard Dumitrescu, Potsdam, NY, USA Alexandra Easley, Bryan, TX, USA Fabian Ebert, Garching, BY, Germany Gumaa ElNagar, Berlin, BE, Germany Robert Emmett, Central, SC, USA Mary Ensch, Haslett, MI, USA Busra Ergul, Little Rock, AR, USA Ahmad Fallatah, Ames, IA, USA Filippo Farina, Montpellier, France Lucas Flagg, Seattle, WA, USA Hui-Chun Fu, Jeddah, Saudi Arabia Zan Gao, Charlottesville, VA, USA Rohan Gokhale, Albuquerque, NM, USA Chen Gong, College Park, MD, USA Elena Gorbachuk, Kazan, Russia Emily Gould, Edinburgh, United Kingdom Katharine Greco, Cambridge, MA, USA Mitchell Groenenboom, Pittsburgh, PA, USA Devanshi Gupta, Charlottesville, VA, USA Meelis Harmas, Tartu, Estonia Oliver Harris, Phila, PA, USA Cheng He, Chicago, IL, USA Yufang He, Rolla, MO, USA Burkhard Hecker, Oldenburg, NI, Germany Stephan Hildebrand, Dublin 14, Ireland Shoko Hirano, Inazawa, Aichi, Japan Michael Hoehlinger, Erlangen, BY, Germany Zachary Hood, Atlanta, GA, USA Andrew Horvath, Iowa City, IA, USA Gregory Houchins, Pittsburgh, PA, USA Bo Hu, Logan, UT, USA Garrett Huang, Atlanta, GA, USA Noriyuki Ida, Sendai, Miyagi, Japan Yuta Iida, Meguro-ku, Tokyo, Japan Saad Intikhab, Philadelphia, PA, USA Kohei Ishikawa, Nagoya, Aichi, Japan Ankur Jadhav, New York, NY, USA Badrinath Jagannath, Richardson, TX, USA Prithi Jayaraj, Coimbatore, TN, India Han Jiang, Central, SC, USA Jisu Jiang, Atlanta, GA, USA Kim Jung Hwan, Seoul, South Korea Jihun Kang, Cheonan, South Korea Jinkyeong Kang, Cheonan, South Korea Jukyoung Kang, Cheonan-si, South Korea Khawla Kasar, Leicester, Leicestershire, United Kingdom Matthew Kavanaugh, Leawood, KS, USA Wisawat Keaswejjareansuk, Worcester, MA, USA Meagan Kelso, Rolla, MO, USA Abubakar Khaleed, Pretoria, South Africa Hyenki Kim, Uijeongbu, Gyeonggi-do, South Korea Hyunki Kim, Seoul, South Korea Nam Kim, Bel Air, MD, USA Yoolhee Kim, La Habra, CA, USA Elisabeth Kolp, Munchen, BY, Germany Felicia Konopka, Austin, TX, USA Jonathan Koonce, Iowa City, IA, USA Lisa Krayer, College Park, MD, USA

Dilip Krishnamurthy, Pittsburgh, PA, USA Gregory Kubacki, Charleston, SC, USA Rajan Kumar, Berkeley, CA, USA Karun Kumar Rao, Houston, TX, USA Arpan Kundu, West Lafayette, IN, USA Nobuaki Kunikata, Kobe, Hyogo, Japan Li-Ming Kuo, Taipei City, Taiwan, Taiwan Narendra Kurra, Philadelphia, PA, USA Tian Lan, Ames, IA, USA Andrew Lee, Pittsburgh, PA, USA Hyojae Lee, Tokyo, Japan Keonhag Lee, Toronto, ON, Canada Seon-Hwa Lee, Seoul, South Korea Sophia Lee, Philadelphia, PA, USA Wenjie Li, Madison, WI, USA Yawei Li, Philadelphia, PA, USA Chun-Ho Lin, Thuwal, Saudi Arabia Shuhao Liu, Cleveland Heights, OH, USA Teng Liu, State College, PA, USA Joshua Lochala, Alma, AR, USA Joseph Lopata, Columbia, SC, USA Xu Lu, Auburn, AL, USA Yizhou Lu, College Park, MD, USA Javier Luna, Iowa City, IA, USA Xubo Luo, Knoxville, TN, USA Fazlollah Madani Sani, Athens, OH, USA Shaimaa Maher, Cleveland, OH, USA Manas Mandal, Edmonton, AB, Canada Mrinmay Mandal, Atlanta, GA, USA Hosoda Mankichi, Tokyo, Tokyo, Japan Tatsuya Matsuhira, Meguro-ku, Tokyo, Japan Haruyuki Matsuyama, Chofu, Tokyo, Japan Joshua McEnaney, East Palo Alto, CA, USA Sirak Mekonen, Silver Spring, MD, USA Davide Menga, Garching, BY, Germany Tristan Myers, Lawrence, KS, USA Jeanne N’Diaye, Toronto, ON, Canada Chen Hon Nee, Petaling Jaya, Minh Ngo, Houston, TX, USA Ramsay Nuwayhid, College Park, MD, USA Ryan Ohagan, Trumbull, CT, USA Kehinde Olubanjo, Fayetteville, AR, USA Justin Osborne, Ashburn, VA, USA Stefan Oswald, Munich, BY, Germany Alessandro Palmieri, Willimantic, CT, USA Qin Pang, Corvallis, OR, USA Hyunsu Park, West Lafayette, IN, USA Richard Park, Cambridge, MA, USA Sobana Perumaram Rangarajan, West Lafayette, IN, USA Gayatri Phadke, Storrs, CT, USA Michelle Pierre, Miami, FL, USA Daniel Pocci, Beachwood, OH, USA Ramtej Popuri, Potsdam, NY, USA Diankai Qiu, Juelich, NW, Germany Shuren Qu, Houston, TX, USA Swetha Ramani, Tampa, FL, USA Yaoyu Ren, College Park, MD, USA Morteza Rezaei Talarposhti, Albuquerque, NM, USA Aaron Roy, Albuquerque, NM, USA Patrick Rutto, Youngstown, OH, USA HoonHee Ryu, Seoul, South Korea (continued on next page)

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

NE W MEMBERS (continued from previous page)

Soojy Ryu, Daejeon, South Korea Emily Sahadeo, College Park, MD, USA Oleg Sapunkov, Pittsburgh, PA, USA Tsubasa Sato, Sendai, Miyagi, Japan Brandon Sattarin, Lawrence, KS, USA Apurv Saxena, Rolla, MO, USA Pieter Schiettecatte, Oost-Vlaanderen, Gent, Belgium Ewelina Seta, Warsaw, Poland Ahmed Shamso, London, United Kingdom Junsung Shin, Seoul, South Korea Mehrnaz Shirazi, Houston, TX, USA Jingyu Si, Shorewood, WI, USA Sneh Sinha, Storrs, CT, USA Ellen Synnove Skilbred, Trondheim, Norway Farjana Sonia, Mumbai, MH, India

Lynza Sprowl, Corvallis, OR, USA Shashank Sripad, Pittsburgh, PA, USA Michael Strebl, Erlangen, BY, Germany Revathi Sukesan, Hsinchu, Taiwan, Taiwan Vaidish Sumaria, Pittsburgh, PA, USA Wilaiwan Supap, Muang, Thailand Kazuma Suzuki, Tokyo, Japan Nagaraju Sykam, Bangalore, KA, India Ewelina Szaniawska, Warsaw, Poland Ricky Tjandra, Kitchener, ON, Canada Anusree Unnikrishnan, Chennai, TN, India Anna Wadas, Warsaw, Poland Han Wang, Pittsburgh, PA, USA Haotian Wang, College Park, MD, USA Junnan Wang, Coralville, IA, USA Lianqin Wang, Guildford, United Kingdom Zach Weinrich, Gainesville, FL, USA John Weiss, Columbia, SC, USA Lien-Chun Weng, Albany, CA, USA

Matthias Werheid, Oldenburg, NI, Germany Patrick West, Philadelphia, PA, USA Andrew Wong, Toronto, ON, Canada Jacob Wrubel, Storrs, CT, USA Jeffrey Xu, New York, NY, USA Hao Yang, Columbus, OH, USA Sharah Yasharahla, Forestville, MD, USA Grace Yee, San Francisco, CA, USA Jiefu Yin, Stony Brook, NY, USA Yuanfang Ying, San Marcos, TX, USA Jaesik Yoon, Auburn, AL, USA Tae-Yeon Yu, Seoul, South Korea Christine Adelle Yuson, Klong Luang, Thailand Sarah Zaccarine, Golden, CO, USA Yunya Zhang, Charlottesville, VA, USA Yizhou Zhu, College Park, MD, USA Ya Zhuo, Houston, TX, USA

Benefits of ECS Student Membership Annual Student Membership Dues Are Only $30

w Open Access Article Credit Publish a paper in an ECS journal as open access and avoid the article processing charge w Student Grants and Awards Student awards and support for travel available from ECS divisions w Student Poster Sessions Present papers and participate in student poster sessions at ECS meetings w ECS Member Article Pack 100 full-text downloads from the Journal of The Electrochemical Society, ECS Electrochemistry Letters, ECS Journal of Solid State Science and Technology, ECS Solid State Letters, Electrochemical and Solid-State Letters, and ECS Transactions w Interface Receive the quarterly members' magazine with topical issues, news, and events w Discounts on ECS Meetings Valuable discounts to attend ECS spring and fall meetings w Discounts on ECS Transactions, Monographs, and Proceedings Volumes ECS publications are a valuable resource for students

www.electrochem.org/student-center The Electrochemical Society

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

T ST ECH UDENT HIGHLIGH NE WS TS

ECS STUDENT PROGRAMS

Awarded Student Membership Summer Fellowships

ECS Divisions offer Awarded Student Memberships to qualified full-time students. To be eligible, students must be in their final two years of an undergraduate program or enrolled in a graduate program in science, engineering, or education (with a science or engineering degree). Postdoctoral researchers are not eligible. Memberships include generous meeting discounts, an article pack with access to the ECS Digital Library, a subscription to Interface, and much more.

uApply www.electrochem.org/student-center

The ECS Summer Fellowships were established in 1928 to assist students during the summer months.

Travel Grants Several of the Society’s divisions and sections offer Travel Grants to students, postdoctoral researchers, and young professionals presenting papers at ECS meetings. Please be sure to review travel grant requirements for each division and sections. In order to apply for a travel grant, formal abstract submission is required for the respective meeting you wish to attend.

uQuestions customerservice@electrochem.org

uApply www.electrochem.org/travel-grants

uDeadline Renewable yearly

uQuestions travelgrant@electrochem.org

Please visit the ECS website for complete rules and nomination requirements.

uApply www.electrochem.org/fellowships uQuestions awards@electrochem.org uDeadline January 15

uNote Applicants must reapply each year The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

The Electrochemical Society Interface • Spring 2017 • www.electrochem.org

2017 ECS Summer Fellowship Summary Reports 2017 Summer Fellowship Committee

Summer Fellowships Each year ECS gives up to five Summer Fellowships to assist students in continuing their graduate work during the summer months in a field of interest to the Society. Congratulations to the four Summer Fellowship Recipients for 2017. The Society thanks the Summer Fellowship Committee for their work in reviewing the applications and selecting four excellent recipients.

Vimal Chaitanya, Chair New Mexico State University

Peter Mascher McMaster University

Kalpathy B. Sundaram University of Central Florida

David S. Hall Dalhousie University

The 2017 Edward G. Weston Summer Research Fellowship – Summary Report Mapping Nanoscale Ion Transport by Lushan Zhou

ransport of ions at small length scales plays critical roles in almost all physical and biophysical processes.1‑4 Investigation of local ion transport properties requires tools for direct visualization of spatially distributed ions at interfaces. Scanning ion conductance microscopy (SICM),5 a scanned nanoscale pipette, allows high resolution non-contact topography imaging of samples bathed in electrolyte and therefore is well-suited for nanoscale ion transport studies. The basic operation for SICM relies on nanopipette ion current – probe-surface distance (Dps) relationship, which is used for probe feedback control. Recently we have described potentiometricSICM (P‑SICM) for resolving heterogeneous conductive pathways within nanopore membranes as well as living epithelial cell sheets.6-8 Briefly, a dual-barrel nanopipette is used as probe (Fig. 1) where the pipette electrode (PE) in one barrel measures ion current for feedback control and topography mapping. After obtaining a topographical image, the pipette is manually positioned to individual points, and the transmembrane potential (VTM) is swept via three bulk electrodes to drive ion flow across the membrane while local potential deflections are recorded with SICM feedback disabled. Such “fixed-position” measurements were done because VTM can interfere with pipette ion current and hence the feedback control. P‑SICM has shown promise in capturing nanoscale transport quantitatively, however, further applications are limited, primarily by the low data acquisition rate in the fixedposition approach. Our specific goal is to advance P‑SICM instrumentation to allow simultaneous topography and local transport recording and generate a spatially-resolved conductance map of a sample. Figure 1a illustrates the scanning protocol.9 Sample and electrode setup are the same as described above, the key difference is that the probe pauses at each pixel during the scan to allow conductance

(a)

(b)

(c)

Fig. 1. (a) Schematic of P‑SICM scanning with cell monolayers. A dual-barrel nanopipette is used as scanning probe. Pipette electrode (PE) in one barrel measures ion current for distance feedback control and potential electrode (UE) in the second barrel records local potential deflections for calculating apparent local conductance. Three bulk electrodes: reference and counter electrode (RE, CE) in top chamber of perfusion cell and working electrode (WE) in the bottom chamber are used to apply transmembrane potentials (VTM) with home-built electrode control module. The scan traces (red) illustrate that pipette “pauses” at two probe-surface distances for each pixel and VTM is ramped during each pause to allow local electrochemical measurement. (b) Representative STEM (left) image of a dual barrel nanopipette side view and SEM image (left inset) of nanopipette end-on view showing the septum between two barrels. SEM images (right) of the nanopore membrane used in c. Average pore diameter was determined to be 272 nm. (c) Simultaneously generated topographical (left) and apparent local conductance (right) images with nanoporous membrane in 0.1 M KCl.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Acknowledgments

(a)

(b)

The Electrochemical Society is gratefully acknowledged for the Edward G. Weston Summer Fellowship. I would like to thank Prof. Lane Baker for his guidance and support, the IU Electronic and Mechanical Instrument Services for building parts used in the study and also my collaborator, Prof. Jianghui Hou in Washington University Medical School.

About the Author Lushan Zhou is currently in the process of completing her doctorate under the supervision of Prof. Lane Baker at Indiana University – Bloomington, Department of Chemistry. She may be reached at luszhou@indiana.edu. https://orcid.org/0000-0002-5427-3552

References 1. Fig. 2. Simultaneously recorded topographical (left) and apparent local conductance (right) maps of live-cell monolayer – Madin Darby Canine Kidney strain II (MDCKII) epithelial cells – in physiological buffer. Cell junctions (spaces between neighboring cells) and cell bodies are clearly resolved in topography image and heterogeneous local conductance was mapped with P-SICM. Scale bar: 5 µm.

measurements. Specifically, the probe approaches surface from a far distance until a set-point is reached, to record topography. A short pause (typically 0.2 s) immediately follows and bypasses the SICM feedback control while turning on the VTM sweep (+/−50‑100 mV, 5 Hz) to allow recording of local potential deflections (ΔVclose). At the end of the pause, VTM is turned off and feedback control resumes to retract the probe far above sample surface. A second pause is applied for “background” measurement (ΔVfar), before the probe translates laterally to the next point. Real-time calculation of the apparent local conductance (G) at each pixel is done with:  ∆Vclose − ∆V far  G =   ∆z ⋅ ρ ⋅ VTM 

The method was first validated with a nanoporous membrane (average pore diameter 272 nm, Fig. 1b) in 0.1 M KCl solution, and the conductance image (Fig. 1c) clearly resolved four pores—transport pathways within sample—which matched well with the topography. Ion transport heterogeneity in living an epithelial cell monolayer (Fig. 2) was also mapped in physiological buffer. Both trans- and paracellular pathways were distinguished, along with visualization of conductance distribution along individual cell junctions, which was not possible with previous methods. Ultimately, we believe the new scan protocol can extend to essentially all local electrochemical measurements and lead to various topography-electrochemical imaging methods.

where Δz and ρ represent probe vertical travel and solution resistivity, respectively. By repeating this process for every pixel, a conductance map of the scanned area is generated.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

2. 3. 4. 5. 6. 7.

8. 9.

H. Zhang and P. K. Shen, Chem. Soc. Rev., 41, 2382 (2012). C. Duan and A. Majumdar, Nat Nano, 5, 848 (2010). X. Hou, W. Guo, and L. Jiang, Chem. Soc. Rev., 40, 2385 (2011). S. Tsukita and M. J. Furuse, Cell Biol., 149, 13 (2000). P. K. Hansma, B. Drake, O. Marti, S. Gould, and C. Prater, Science, 243, 641 (1989). C.-C. Chen, Y. Zhou, C. A. Morris, J. Hou, and L. A. Baker, Anal. Chem., 85, 3621 (2013). Y. Gong, V. Renigunta, Y. Zhou, A. Sunq, J. Wang, J. Yang, A. Renigunta, L. A. Baker, and J. Hou, Mol. Biol. Cell, 26, 4333 (2015). L. Zhou, Y. Gong, A. Sunq, J. Hou, and L. A. Baker, Anal. Chem., 88, 9630 (2016). L. Zhou, Y. Gong, J. Hou, and L. A. Baker, Submitted (2017).

The 2017 Joseph W. Richards Summer Research Fellowship – Summary Report Graphene Intercalation: A Pathway Toward Stabilizing New Two-Dimensional Crystals

ide bandgap group-III nitrides, such as GaN, are integrated in multiple applications including laser-diodes and light-emitting-diodes,1,2 to power electronics and photovoltaics. However, for this materials system to potentially compete with silicon technology, it is imperative to implement GaN in a breath of new applications that may not be easily accessible solely using silicon. These emerging technologies may include tunnel junctions for ultra-low voltage and steep-switching applications,3 single photon emitters and polarization driven topological insulators for quantum transport.4,5 To accomplish this, we developed an alternative growth scheme to realize a two-dimensional (2D) form of GaN, utilizing the mechanism of adatom intercalation from the vapor phase in a metalorganic chemical vapor

by Zakaria Y. Al Balushi deposition (MOCVD) growth environment into the interfacial region of graphene grown epitaxially on SiC. This synthesis process, referred to as Migration Enhanced Encapsulated Growth (MEEG),6 establishes an entirely new platform to realize 2D forms of conventional bulk semiconductors that may frame next-generation technology. As outlined in Fig. 1a, the growth scheme of 2D GaN begins with the delivery of trimethylgallium (TMGa) precursor to the surface of the graphene. Gallium intercalates between graphene and SiC via defects within the graphene lattice. Subsequently, by introducing other intercalants, like atomic nitrogen from NH3, transformation of the intercalated gallium to GaN can occur. It was demonstrated that 2D GaN exhibits unique structural and optical properties from that of bulk material, most notable an

increase in the bandgap energy from 3.4 eV to ~5.0 eV due quantum-confinement. This growth process has the potential of being extended to other material systems beyond nitrides, providing an avenue for new 2D materials exploration. However, an in-depth analysis of the electrical properties of these 2D monolayers has not been achieved due to the small domain size of the 2D monolayers. To further studies on understanding the effect of the quantum-confined 2D structure of GaN on the carrier mobility, we sought out to significantly, improve the domain size and coverage of the 2D GaN (Fig. 1b and c). This was achieved by optimizing the MEEG scheme used for 2D GaN synthesis. In this work, we investigated the impact of the molar concentration of gallium and intercalation temperature on the growth process. In addition, the effect of the

Fig. 1. (a) Top, an illustration of the Migration Enhance Encapsulated Growth (MEEG) process to stabilize a wide-bandgap two-dimensional (2D) form of GaN. MEEG is facilitated by defects in the graphene lattice that act as pathways for intercalation. When the gallium and nitrogen adatoms meet at the graphene/ SiC interface, they chemically react to form 2D GaN; (a) bottom, a scanning transmission electron micrograph (STEM) of a cross-section specimen of the graphene/2D GaN/SiC heterostructure. Overlayed is a simulated annular bright-field scanning transmission electron micrograph to highlight the position of the gallium and nitrogen atomic columns. (b-c) scanning electron micrographs (SEMs) showing an improvement in the domain size of 2D GaN before (b) and after (c) further optimization studies of the growth parameters. The regions of bright contrast in the SEMs are the graphene encapsulated regions of 2D GaN, while the regions of dark contrast are the graphene layers on SiC. 92

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

number of graphene layers and the impact of defects in graphene on the intercalation efficiency of gallium were also investigated. The increase in the concentration of gallium and/or temperature during MEEG generally enhanced parasitic deposition on the surface of graphene, rather than intercalation through the graphene lattice. However, decreasing the number of the graphene layers to one monolayer led to significant improvement on both the domain size and coverage of 2D GaN. In summary, monolayer graphene produced on SiC, with prior intentional introduction of defects into the graphene lattice using a short oxygen plasma exposure process, yielded nearly complete coverage of 2D GaN across the surface of the sample (Fig. 1c). The results of these studies will allow for future transport measurements of the 2D monolayers. © The Electrochemical Society. DOI: 10.1149/2.F11174if.

Acknowledgments The author gratefully acknowledges the ECS Joseph W. Richards Summer Fellowship for funding support and would like to give special thanks to Brian Bersch for assisting in sample preparation and

characterization, as well as Prof. Joan M. Redwing and Prof. Joshua A. Robinson for feedback in planning experiments. The author acknowledges Northrop Grumman and the National Science Foundation under grant number DMR-1420620 (Penn State MRSEC - Center for Nanoscale Science) for providing additional financial support. Any opinions, ﬁndings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reﬂect the views of the National Science Foundation.

References 1. S. Nakamura, T. Mukai, and M. Senoh, Appl. Phys. Lett., 64, 1687 (1994). 2. N. Shuji, S. Masayuki, N. Shin-ichi, I. Naruhito, Y. Takao, M. Toshio, K. Hiroyuki, and S. Yasunobu, Jpn. J. Appl. Phys., 35, L74 (1996). 3. J. Simon, Z. Zhang, K. Goodman, H. Xing, T. Kosel, P. Fay, and D. Jena, Phys. Rev. Lett., 103, 026801 (2009). 4. S. Kako, C. Santori, K. Hoshino, S. Gotzinger, Y. Yamamoto, and Y. Arakawa, Nat. Mater., 5, 887 (2006). 5. M. S. Miao, Q. Yan, C. G. Van de Walle, W. K. Lou, L. L. Li, and K. Chang, Phys. Rev. Lett., 109, 186803 (2012). 6. Z. Y. Al Balushi, K. Wang, R. K. Ghosh, R. A. Vila, S. M. Eichfeld, J. D. Caldwell, X. Qin, Y.-C. Lin, P. A. DeSario, G. Stone, S. Subramanian, D. F. Paul, R. M. Wallace, S. Datta, J. M. Redwing, and J. A. Robinson, Nat. Mater., 15, 1166 (2016).

About the Author Zakaria Y. Al Balushi received his PhD in materials science and engineering in August 2017 at The Pennsylvania State University under the supervision of Prof. Joan M. Redwing and Prof. Joshua A. Robinson. He is currently a Resnick Prize Postdoctoral Fellow in applied physics and materials science at the California Institute of Technology (Caltech). He may be reached at albalushi@caltech.edu. https://orcid.org/0000-0003-2870-7887

Your article. Online. FAST! More than 132,000 articles in all areas of electrochemistry and solid state science and technology from the only nonprofit publisher in its field.

www.ecsdl.org

www.electrochem.org

If you haven’t visited the ECS Digital Library recently, please do so today!

Not an ECS member yet? Start taking advantage of member benefits right now!

Leading the world in electrochemistry and solid state science and technology for more than 115 years

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

The 2017 F. M. Becket Summer Research Fellowship – Summary Report FeNi2Se4-(Black)TiO2 Nanocomposite: A Bifunctional Catalyst for Photoelectrocatalytic Water Splitting

by Siddesh Umapathi

he demand for clean and sustainable energy source is one of the top priorities across the globe and hydrogen is one of the most potential candidates that can substantially address this demand. Generation of hydrogen and oxygen through catalyst-aided water splitting is one of the prime routes facilitating the hydrogen fuel economy. This technology also has immense applications in metal air batteries, PEM fuel cells and solar to fuel energy production, and has been one of the critical topics studied in recent times.1,2 State of art oxygen evolution reaction (OER)

and hydrogen evolution reaction (HER) catalysts are mostly comprised of precious metals and it is the need of the hour to replace them with earth abundant elements. Several new catalyst systems based on Ni, Fe, Co in the form of oxides and (oxy) hydroxides has been reported in the recent past.3,4 More recently there has been a great deal of interest on phosphides, sulfides and especially selenides, which have shown unprecedented catalytic activity compared to the oxides and oxyhydroxides.5 Herein, we have explored a new approach of combining transition metal selenide

based electrocatalysts such as FeNi2Se4 with black TiO2 for overall photoelectrocatalytic water splitting. Black TiO2 (black)TiO2 has recently been of increased interest due to its smaller bandgap caused by the oxygen defects in the TiO2 structure which leads to increased conductivity of the material.6 Moreover, (black)TiO2 can absorb wavelengths of light at or approaching the visible region, thus enhancing the range for photoelectrochemical studies. The electrocatalyst, FeNi2Se4 on the other hand, has shown remarkable acitivity, better than previously reported Ni and Fe based

Fig. 1. (a) PXRD pattern of FeNi2Se4-(black)TiO2 hybrid catalyst, along with reference FeNi2Se4 (PDF # 04-006-5240) and TiO2 (PDF # 00002-0387) confirming the presence of FeNi2Se4 nanoparticles and (black)TiO2. (b) TEM images of FeNi2Se4 decorated on (black)TiO2. (c) Schematic layer by layer assembly of the hybrid catalyst for photoelectrocatalytic application.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Fig. 2. (a) iR corrected polarization curves of FeNi2Se4-(black)TiO2 hybrid catalyst with a loading of 0.55 mg cm-2 drop-casted on CFP substrate, measured in N2 saturated 1.0 M KOH solution at a scan rate of 10 mV s-1. Inset shows chronoamperometric study for 15 hours. (b) LSVs measured for FeNi2Se4-(black)TiO2 in N2 saturated 1.0 M KOH solution at a scan rate of 10 mV s-1in the cathodic scan depicting active HER. Inset shows the HER stability for 6 hours.

electrocatalysts. Hence we have synthesized FeNi2Se4-(black)TiO2 nanocomposite by combining the ternary selenide with (black) TiO2. Such a hybrid nanocomposite is expected to increase the overall conductivity, number of catalytically active sites and electrochemically active surface area due to synergistic effects.7 FeNi2Se4-(black)TiO2 was synthesized by in situ hydrothermal synthesis. Here, stoichiometric amounts of Fe, Ni, and Se precursors were added to the as synthesized (black)TiO2 which was formed by heat treatment under hydrogen gas. A typical synthesis protocol can be written as:

current density of 10 mA cm-2 (Fig. 2a). The stability of the catalyst for continuous oxygen evolution was carried out through chronoamperometric measurements (j vs. t) for 12 hours (Fig. 2a, inset), at an applied potential of 1.43 V vs. RHE, where the catalyst achieved a current density of 10 mA cm-2. The stability of the catalyst was further confirmed through LSV studies which showed that the catalyst has similar onset potential and overpotential at 10 mA cm-2. HER polarization curves (j vs. E) are shown in Fig. 2b, where FeNi2Se4-(black) TiO2 required an overpotential of 280 mV to

FeSO4.7H2O + SeO2 + NiCl2.6H2O + (black)TiO2 → FeNi2Se4 – (black)TiO2 Figure 1a shows the powder X-ray diffraction (pxrd) pattern of as-synthesized hybrid catalyst, wherein the pxrd pattern matched very well with FeNi2Se4 and TiO2 standard patterns (PDF # 04-006-5240 and PDF # 00-002-0387, respectively) confirming the presence of FeNi2Se4 and TiO2 in the composite, and indicating the high degree of crystallinity and purity of the product. Transmission electron microscopy (TEM) confirmed the formation of FeNi2Se4-(black)TiO2 nanostructures (Fig. 1b). The nanoparticles were agglomerated because of their high surface energy, leading to irregular morphology of FeNi2Se4 with an average particle size of 10 – 15 nm and it was decorated on (black)TiO2 particles that were mostly spherical with an average size of ∼100 nm. Linear sweep voltammetry (LSV) measurements were conducted in N2 saturated 1M KOH solution. The FeNi2Se4(black)TiO2 catalyst showed an onset potential of 1.40 V vs. RHE and a small overpotential of 200 mV to achieve the

achieve 10 mA cm-2. However, if the relative ratio between the FeNi2Se4 and (black)TiO2 is increased so that there is an increase in the selenide sites which are active for HER, it is possible to decrease the overpotential. It is always advantageous if the catalyst is active both in the presence of applied potential or solar radiation. Hence, we are performing a layer by layer assembly of FeNi2Se4-(black)TiO2 catalysts (Fig. 1c) for photoelectrochemical devices and the results will be communicated in a separate report. In summary, we have synthesized FeNi2Se4-(black)TiO2 hybrid catalyst for complete photoelectrocatalytic water splitting. The catalyst composite shows overpotentials of 200 mV and 280 mV for OER and HER respectively to achieve a current density of 10 mA cm-2. The chronoamperometric studies shows the catalyst is stable over a long period of time and retains the performance after extended exposure to harsh conditions. © The Electrochemical Society. DOI: 10.1149/2.F12174if.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Acknowledgments I would like to thank The Electrochemical Society for the 2017 F.M. Becket Summer Fellowship and my advisor Prof. Manashi Nath for her guidance and support in conducting research. I would like to thank Dr. Jahangir Masud for helpful discussions and conducting TEM experiments.

About the Author Siddesh Umapathi currently is in the third year of his doctorate at Missouri University of Science and Technolgy in the Department of Chemistry under the supervision of Prof. Manashi Nath. He may be reached at supn6@mst.edu.

References 1. N. S. Lewis and D. G. Nocera, Proc. Natl Acad. Sci, 103, 15729 (2006). 2. M. Winter and R. J. Brodd, Chem. Rev., 104, 4245 (2004). 3. Y. Gorlin, C. J. Chung, J. D. Benck, D. Nordlund, L. Seitz, T. C. Weng, D. Sokaras, B. M. Clemens, and T. F. Jaramillo, J. Am. Chem. Soc., 136, 4920 (2014). 4. T. Hamann, Science, 345, 1566 (2014). 5. A. T. Swesi, J. M. Masud and M. Nath, Energy Environ. Sci., 9, 1771 (2016). 6. A. Byeon, M. Boota, M. Beidaghi, K. V. Aken,, J. W. Lee, and Y. Gogotsi, Electrochem. Commun., 60, 199 (2015). 7. J. Hensel, G. Wang, Y. Li, and J. Z. Zhang, Nano Lett, 10(2), 478 (2010).

The 2017 H. H. Uhlig Summer Research Fellowship – Summary Report Design of New Electrode Materials for Na-Ion Batteries from the Alluaudite Minerals

o empower an increasingly diverse range of energy-intensive applications, electrochemical energy storage in general and Li-ion batteries (LIB) in particular have become key players. But now they are at a critical juncture due to limited lithium resources, which has rekindled a growing interest in Na-ion batteries (NIB) for mass storage applications. This viability of NIB has led to an intensive exploration of wide range of “cathode materials.” In this regard, several strategies can be pursued like high-throughput materials computation to design new materials with “magic phase composition” having both high voltage and high capacity, but success here is still limited. Another interesting way, which we pursued, is to browse through well-known minerals to spot families of materials having attractive structural features for ion transport. One such family is alluaudites with the general formula: Na2M2(XO4)3 (M = 3d metals; X = S, P etc.).1-5 A recent report by Barpanda, et al., unveiled the extraordinary electrochemical activity of Na2Fe2(SO4)3 alluaudites benchmarking the highest ever Fe3+/Fe2+ redox potential (ca. 3.8 V vs. Na+/Na0).2 With this as the basis, we framed our investigation to explore/ design new electrode materials from this alluaudite family.

by Debasmita Dwibedi The motivation was: (i) to design new alluaudite electrodes with low cost and easily scalable synthesis; (ii) to investigate their structural features and ion migration pathways; and (iii) to tune their electrochemical activity, thereby establishing the synthesis-structure-property correlation of alluaudites. In this pursuit, at first, we explored some unconventional solvothermal routes: (i) ionothermal;4 (ii) spray drying; and (iii) Pechini synthesis. Their unique attributes with reported synthesis are highlighted in Table I. Indeed, these solvothermal routes fulfil the demand of designing efficient electrodes economically. As we know from the inductive effect principle, in polyanionic cathodes (M-XOnm-), the ionic bonding nature of M can be tuned depending on the nature of XO bonding. If X is more electronegative, it forms a stronger bond with O, thereby making the M-O bond more ionic. Further in the ionic M-O bond, the lower repulsion between bonding and anti-bonding orbitals places the orbital far from the Fermi level, thereby yielding a higher redox voltage. Employing this, we extended our search for high-voltage cathodes to isostructural analogues and discovered two novel alluaudites: 4.4 V Na2.44Mn1.78(SO4)3 and 5 V Na2.37Co1.83(SO4)3.4,5 Further, with

different Pauling electronegativity values, changing X should follow a general voltage trend of Mo < V < P < S. In this series, we started with the high-throughput synthesis and structural analysis of the phosphate alluaudite framework. For the first time, we successfully synthesized phosphate alluaudite NaFe2Mn(PO4)3 by solution combustion synthesis at 600 °C that exhibited 3.0 V redox potential and 75% of the theoretical capacity with good cycling stability. The redox potential tunability with sulphate and phosphate alluaudite is in accordance with inductive effect principle, as shown in Fig. 1. This work, starting with various energysavvy synthesis routes to discovery of new sulphate alluaudites and tuning the redox activity of phosphate alluaudites, attests the richness of alluaudites as potential sodium insertion hosts. © The Electrochemical Society. DOI: 10.1149/2.F13174if.

Acknowledgments The author is grateful to The Electrochemical Society for the Herbert H. Uhlig Summer Fellowship and to Dr. Prabeer Barpanda for his constant motivation and guidance.

Fig. 1. Inductive effect demonstrating the tunability of redox potential in sulphate and phosphate alluaudites.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Table I. Highlights of various synthesis of Na2Fe2(SO4)3 alluaudites. Employed Synthesis

Morphology

Reported Solid-state Synthesis2

Time

Temperature

12 h mill + 24 h annealing

350 °C

Looking for

Electrochemistry* 100 mAh/g Capacity** 3.8 V Potential

Section News

Agglomerated Ionothermal Route3

30 h Annealing in air ambience

300 °C

80 mAh/g Capacity 3.7 V Potential

6 h Annealing

350 °C

75 mAh/g Capacity 3.7 V Potential

6 h Annealing

200 °C

70 mAh/g Capacity 3.7 V Potential

Bean shaped Spray drying Route

4 µm

We welcome the opportunity to share with our membership, the scientific advances and activity news from your Section.

Spherical Pechini Synthesis Porous *Cycling at C/20. **Theoretical capacity.

About the Author

References

Debasmita Dwibedi is currently a fourth year PhD student in the group of Dr. Prabeer Barpanda at Faraday Materials Laboratory, Materials Research Center, Indian Institute of Science (IISc), Bangalore, India. Her research interests include the synthesis, characterization and electrochemistry of high voltage cathode materials for rechargeable sodium battery application. Dwibedi performed the reported work at IISc during summer 2017. She may be reached at debasmitad@iisc.ac.in. https://orcid.org/0000-0003-2366-1429

1. K. Trad, D. Carlier, L. Croguennec, A. Wattiaux, M. B. Amara, and C. Delmas, Chem. Mater., 22, 5554 (2010). 2. P. Barpanda, G. Oyama, S. Nishimura, S. C. Chung, and A. Yamada, Nature Commun., 5, 4358 (2014). 3. D. Dwibedi, C. D. Ling, R. B. Araujo, S. Chakraborty, S. Duraisamy, N. Munichandraiah, R. Ahuja, and P. Barpanda, ACS Appl. Mater. Interfaces, 8, 6982 (2016). 4. D. Dwibedi, R. B. Araujo, S. Chakraborty, P. P. Shanbogh, N. G. Sundaram, R. Ahuja, and P. Barpanda, J. Mater. Chem. A., 3, 18564 (2015). 5. D. Dwibedi, R. Gond, A. Dayamani, R. B. Araujo, S. Chakraborty, R. Ahuja, and P. Barpanda, Dalton Trans., 46, 55 (2017).

Send your news to: ecs@electrochem.org

Visit www.electrochem.org

Look Out !

We want to hear from you! Students are an important part of the ECS family and the future of the electrochemistry and solid state science community . . .

• What’s going on in your Student Chapter? • What’s the chatter among your colleagues?

• What’s the word on research projects and papers? • Who’s due congratulations for winning an award?

Send your news and a few good pictures to interface@electrochem.org. We’ll spread the word around the Society. Plus, your Student Chapter may also be featured in an upcoming issue of Interface!

electrochem.org/student-center The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

easy steps.

Here!

Ren

AUTOM

Renew in

SHIp ER

M E M C I b T A

s i al

1 2

In your active membership, click Enroll Now and follow steps for setup.

Select My Memberships from the My Account Links menu.

QUESTIONS: Contact customerservice@electrochem.org. 98

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

T ST ECH UDENT HIGHLIGH NE WS TS

Student Chapter News Aalborg University Student Chapter On September 6, 2017, the ECS Aalborg University Student Chapter hosted a fuel cells-oriented event. Invited speaker Pierpaolo Polverino, a research fellow in energy convention systems in the Department of Industrial Engineering at the University of Salerno, Italy, gave a lecture about the design and application of conventional and advanced modelbased diagnostic algorithms related to fuel cells. Afterward, Søren J. Andreasen, who was previously an associate professor at Aalborg University and is currently a senior system engineer at SerEnergy, took the participants on an excursion into SerEnergy. Based in Aalborg, Denmark, SerEnergy is a leading developer and manufacturer of efficient, low-emission methanol fuel cell solutions. Inside, students were shown how fuel cells are manufactured and used in commercial applications. The day was filled with discussion among students and researchers about various aspects of fuel cell technology.

Members of the ECS Aalborg University Student Chapter with their invited speaker (left to right): Xin Gao, Lajos Török, Samuel Simon Araya, Vaclav Knap, chapter president, Steffen Henrik Frensch, chapter treasurer, Sobi Thomas, Pierpaolo Polverino, invited speaker, Xiaoti Cui, Shahid Ali, Fan Zhou, and Debanand Singdeo.

Belgium Student Chapter On the May 23, 2017, 15 members of the ECS Belgium Student Chapter visited the ON Semiconductor facility in Oudenaarde, Belgium. With over 30,000 employees worldwide, ON Semiconductor is a global company engaged in various in industries—automotive, communication, computing, consumer and industrial electronics, and more. The site in Oudenaarde is both a manufacturing plant and a design center; this made it an ideal location for the students’ visit. ON Semiconductor staff directed the students’ tour. First, the students learned about ON Semiconductor as a company, from its position in the global market to how the plant in Oudenaarde operates. Next, Peter Moens gave them a more technical introduction to the R&D performed at ON Semiconductor. Several young researchers guided the students to points of interest throughout the manufacturing plant while fielding their questions. At the end of the tour, the students were challenged with a team-building exercise—the so-called marshmallow challenge—which taught

them the complexity of working under high pressure and the value of making quick decisions as a team. The chapter thanks ON Semiconductor Belgium for hosting and coordinating the visit.

Members of the ECS Belgium Student Chapter during their visit to the ON Semiconductor facility in Oudenaarde, Belgium.

Advertisers Index Ametek.................................................. 1 Bio-Logic........................................ 2, 25 El-Cell..................................................37

Gamry................................................... 4 Koslow..................................................39 Metrohm................................................ 8 Pine........................................................ 6

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Scribner................................................31 Wiley................................................... 48 Zahner-elektrik GmbH & Co KG......11

T ST ECH UDENT HIGHLIGH NE WS TS British Columbia Student Chapter On August 4, 2017, the ECS British Columbia Student Chapter hosted its 6th Annual Young Electrochemists Symposium at the University of British Columbia (UBC) in Vancouver. This fullday event was held in the Chemical and Biological Engineering Department building and was attended by both graduate and undergraduate students, as well as academic faculty and industrial researchers. The event featured several interesting talks that covered a wide range of electrochemical topics—from the electrochemical detection of small molecules to the exchange membranes of fuel cells and electrolyzers. The invited speakers came from both academia—UBC and Simon Fraser University (SFU)—and industry; they included David Wilkinson (UBC), Hogan Yu (SFU), Loren Kaake (SFU), Dustin Banham (Ballard Power Systems), Benjamin Britton (Ionomr), and Saad Dara (Mangrove Water Technologies). In addition, students participated in a three-minute thesis pitch and poster competition.

The organizers recognized the student award recipients for their outstanding research and presentations: Audrey Taylor (SFU, 1st place, $150), Bryan Kung (UBC, 2nd place, $100), and Amelia Hohenadel (SFU, 3rd place, $50). The ECS British Columbia Student Chapter is thankful to the speakers, students, and sponsors (ECS, Gamble Technologies, the SFU Graduate Chemistry Caucus, SFU Graduate Student Society, and the UBC Chemical and Biological Engineering Department) who made this event possible. The chapter looks forward to hosting future events that provide platforms for students, industry professionals, and faculty working locally in the field of electrochemistry to showcase their research, engage in thought-provoking discussion, and build future collaborations.

Case Western Reserve University Student Chapter The ECS Case Western Reserve University Student Chapter finished out the 2016-2017 academic year by hosting a series of educational and professional development seminars. In one such seminar, Founder and CTO of Faraday Technology and ECS Treasurer E. J. Taylor discussed “Electropolishing of Niobium Superconducting Radio Frequency Cavities in Low-Viscosity, WaterBased Electrolytes: A Paradigm Shift from the Viscous Salt Film Model.” The student chapter also held a career panel during which its members were able to discuss career opportunities, challenges, and strategies with electrochemical scientists in various stages of their careers. Vice President of Blue Spark Technologies Frank Feddrix, Case Western Reserve University Distinguished Professor Robert Savinell, and Postdoctoral Appointee of Argonne National Laboratory Krista Hawthorne were all present to share their knowledge and paths to success. Finally, six chapter members conducted teaching demonstrations during the annual Yeager Center Workshop on Electrochemical Measurements at the Ernest B. Yeager Center for Electrochemical Sciences. The chapter is continuing to expand its seminar series and educational offerings during the current academic year.

From left to right: Krista Hawthorn, Frank Feddrix, and Robert Savinell discussed career opportunities and strategies for success during the student chapter’s career panel.

100

E. J. Taylor engaged in a seminar talk at Case Western Reserve University.

Dai Shen, chapter treasurer, lectured on cyclic voltammetry during the Yeager Center Workshop on Electrochemical Measurements.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

T ST ECH UDENT HIGHLIGH NE WS TS Munich Student Chapter On July 20, 2017, the ECS Munich Student Chapter hosted its first ECS panel discussion titled “Fuel Cells vs. Batteries – The Future of Electromobility” in the faculty club at the Institute for Advanced Studies at the Technical University of Munich (TUM). Peter Lamp (BMW), Werner Tillmetz (ZSW Ulm), Kevin Gallagher (Robert Bosch GmbH), and Thomas Schaefer (BeeZero, Linde) accepted invitations to promote an interdisciplinary dialogue about electromobility and discuss opportunities and challenges arising from different energy storage technologies. Thanks to them, approximately 100 participants from industry and energy research-affiliated institutes at the universities in Munich and Ulm experienced an insightful and enjoyable afternoon. After a warm welcome and brief introduction of the ECS Munich Student Chapter by event hosts Christoph Simon and Rui Fang, Hubert Gasteiger (TUM) paved the way for a fruitful discussion by concisely reviewing the state of the art for lithium-ion battery and fuel From left to right: Thomas Schaefer (BeeZero, Linde), Christoph Simon cell cars while pointing out current challenges in cost and the supply (ECS Munich Student Chapter), Werner Tillmetz (ZSW Ulm), Kevin of electricity, hydrogen, and raw materials. In the opening statements Gallagher (Robert Borsch GmbH), Peter Lamp (BMW), and Rui Fang that followed, the panelists shared their individual perspectives on (ECS Munich Student Chapter) engaged in the panel discussion at the electromobility, which they supported with visuals. Lamp illustrated Institute for Advanced Studies at the Technical University of Munich. how electromobility is only one aspect of the disruptive change that Tillmetz explained that, although it may seem that batterymobility is going through, but that electrification is a marathon, powered vehicles have a head start, it is impossible to predict which not a sprint. He complemented his presentation with a short movie technology will be more successful in the long run, as the way we about the driving experience in a battery-electric vehicle. Tillmetz use cars will change dramatically in the years to come. Therefore, a demonstrated the potential of a hydrogen economy against the key goal for Schaefer is to raise public awareness and increase the backdrop of global trends in electromobility. Gallagher pointed out visibility of fuel cell cars. All panelists agreed, nevertheless, that both that, although batteries have penetrated the market for automotive technologies should be supported. applications to a higher degree than fuel cells, the development of “We should all fight together towards zero-emission mobility,” a recharging infrastructure will prove crucial for both technologies. Lamp said. Schaefer introduced BeeZero, the world’s first hydrogen-powered “We’re on the transition,” Gallagher concluded. “It’s occurring car-sharing service, and explained why fuel cell cars are perfect for before our eyes.” weekend trips. After a Q&A session, there was time left for participants to During the 90 minutes that followed, a lively discussion ensued network and pursue further discussion with the panelists. amongst the panelists on the different aspects of energy storage The ECS Munich Student Chapter thanks all of the supporters of technologies and their impacts upon the automotive industry. The this event; in particular, the chapter thanks the four panelists for their discussion was moderated by Simon and Fang. Lamp and Gallagher time and commitment, as well as BMW, Umicore, and BioLogic for expressed confidence that the driving-range limitations of today’s their financial support. battery-powered vehicles will be overcome by technological advances. “If you can only buy one car,” Tillmetz advised attendees, “buy a fuel cell car.” Another key point of the discussion was the recharging and refueling infrastructure, which must develop simultaneously with the vehicles. “Infrastructure for fuel cell cars is a henegg problem,” Schaefer explained, “and we need external forces to break it.” Both he and Lamp emphasized the importance of end user feedback. “In the end, the customer experience will be the same for a battery or a fuel cell car, except for the refueling,” Lamp said. For Gallagher, smart use is key when it comes to the efficient charging of battery vehicles; he proposed that digitalization and connectivity could produce solutions that have yet to be conceived. Attendees at the event hosted by the ECS Munich Student Chapter conversed and networked after the panel discussion concluded.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

101

T ST ECH UDENT HIGHLIGH NE WS TS Ohio University Student Chapter The ECS Ohio University Student Chapter has been active since May 2011 and has sustained its goal of keeping students educated and informed of the latest trends in the fields of electrochemistry and solid state science and technology. Gerardine Botte, Ohio University Distinguished Professor, director of the Center for Electrochemical Engineering Research, and ECS fellow, has served as the chapter’s advisor since its founding. Botte has pushed the chapter toward great success, motivating students to learn and grow through seminars and research and to pass that knowledge on to others through outreach and education. The current chapter officers are Bertrand Neyhouse (president), Ashwin Ramanujam (vice president), Behnaz Jafari (treasurer), and Melina Ghahremani (secretary). The officers organize events, tours, and speakers that help educate members and recruit new students. Distinguished Professor Mark Orazem, University of Florida, was the guest of the chapter in academic year 2016-2017. Orazem delivered a seminar on impedance spectroscopy and its applications for sensor development. The seminar was opened to graduate and

undergraduate students, faculty, and research staff. Attendees took the opportunity to discuss with Orazem the use of electrochemical engineering in industrial applications. On May 30, 2017, during the 231st ECS Meeting in New Orleans, Louisiana, the chapter organized and facilitated the Industrial Electrochemistry and Electrochemical Engineering Division’s 16th outreach program. The event was held at Cabrini High School’s summer STEM Camp for a group of 15 students and their teachers, Ann Smart and Lisa Dubos. The facilitators included Botte, John Staser, and Madhivanan Muthuvel from Ohio University, Le Zhang and Verada Menon Palakkal from Christopher Arges’s group at Louisiana State University, and Santosh Vijapur from Faraday Technology, Inc. The outreach program gives elementary, middle, and high school students hands-on experience in electrochemical energy conversion and technology. It also provides an opportunity for ECS students to mentor young students and support science education in schools around the country.

ECS Ohio University Student Chapter members with Mark Orazem (eighth from the left) from the University of Florida.

Oklahoma Student Chapter The ECS Oklahoma Student Chapter participated in National Lab Day 2017, which was held at Oklahoma State University (OSU) in Stillwater on May 16, 2017. This annual event was organized by Julie Angle of the OSU College of Education in conjunction with the Colleges of Arts and Sciences, Human Sciences, Engineering, Architecture & Technology, and Agricultural Sciences & Natural Resources. Approximately 15 teachers and 105 high school students from across Oklahoma participated in the event. OSU researchers provided engaging hands-on demonstrations of modern scientific experiments to motivate the students to consider pursuing STEM majors.

102

Members of the ECS Oklahoma Student Chapter provided demonstrations on “Electroanalysis of Vitamin-C in a Droplet of Fruit Juice.” The student groups were also given a short training on volumetric titrations. The student chapter presenters were Charuksha Walgama, Gayan Premaratne, Jinesh Niroula, and Asantha Dharmaratne from the Chemistry Department’s Krishnan Research Group. National Lab Day is designed to inform teachers and students of the quality research taking place on the OSU campus, as well as the plethora of opportunities available to students interested in pursuing a STEM major.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

T ST ECH UDENT HIGHLIGH NE WS TS University of Arkansas Student Chapter The ECS University of Arkansas Student Chapter hosted Rajendra Singh from Clemson University from April 11-12, 2017. Chapter officers arranged tours of the Engineering Research Center and the Institute for Nanoscience and Engineering for the D. Houser Banks Professor of Electrical and Computer Engineering. Singh met with faculty in physics, chemistry, and engineering before giving a seminar titled “Nearly Free and Sustainable Electric Power for Mankind.” The chapter worked with student chapters of the American Chemical Society and the IEEE Power Electronics Society to advertise the seminar. The seminar room filled with more than 50 attendees from different departments of the university interested in gaining insight into the future cost of energy and the transformative opportunities enabled by research in photovoltaics. Singh’s many honors include ECS’s 1998 Thomas D. Callinan Award, the J. F. Gibbons Award from the 11th IEEE International Conference on Advanced Thermal Processing of Semiconductors in 2003, and acknowledgement by U.S. President Barack Obama as a White House Champion of Change for his leadership in advancing solar deployment.

Rajendra Singh in front of the seminar audience at the University of Arkansas.

University of Illinois at Chicago Student Chapter On September 6, 2017, the ECS University of Illinois at Chicago Student Chapter held its inaugural event in the university’s Chemical Engineering Building. The event brought together over 40 student chapter members, guest graduate students, and faculty from the university’s Departments of Chemical Engineering, Mechanical Engineering, and Chemistry. The chapter commenced the event with a luncheon that enabled its members to reunite after a summer spent in their individual laboratories. The lunch session provided the chapter an excellent opportunity to meet and recruit new members. The lunch was followed by a presentation given by guest speaker Alan Zdunek from the University of Illinois at Chicago. Zdunek is a clinical assistant professor and the chair of the university’s student chapter. Zdunek spoke about the history and ethos of ECS internationally and in the Chicago region. He also presented work on the electrochemical analysis of copper plating on microchips, which was conducted throughout his many years working in industry in the U.S. and internationally. The presentation provided insight into the superior capabilities of electrochemical impedance spectroscopy and the diverse range of systems it can examine. The talk demonstrated that the advancement of transistors and microchips has relied heavily upon the development of electrochemical technology.

The student chapter is grateful for Zdunek’s time and presentation; it hopes to welcome him back for future events. The chapter would also like to thank all the students and faculty that attended the inaugural event.

Members of the ECS University of Illinois at Chicago Student Chapter with their guest speaker (left to right): Pedram Abbasi, chapter treasurer, Sanjay Behura, chapter vice president, Alan Zdunek, guest speaker, Rumki Bose, chapter secretary, and Samuel Plunkett, chapter president.

University of Virginia Student Chapter The ECS University of Virginia Student Chapter held an interest session to recruit new members last summer. Toward the end of the meeting, a new set of officers was elected for the 2017-2018 school year. The student chapter remains committed, above all else, to promoting a positive learning environment. Aside from the chapter’s local activities, some members of the chapter attended and participated in the 68th Annual Meeting of the International Society of Electrochemistry, which was held in Providence, Rhode Island from August 27 to September 1, 2017. There, Chao Gilbert Liu, current president of the student chapter, received an award for the best poster presentation. The chapter members that attended were able to meet and network with students from other universities.

Members of the ECS University of Virginia Student Chapter mingled with students from other universities at the 68th Annual Meeting of the International Society of Electrochemistry.

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

103

your

FrEE

iDEAs Publish with ECs!  Authoritative & Comprehensive  Rigorous Peer Review  Fast Turn-Around  Visibility & Discoverability  Editors’ Choice Recognition  Long-Term, High Impact  Author Choice Open Access  Awards for Young Authors

Find out what publishing with ECS can do for you.

www.electrochem.org/whypublish 104

The Electrochemical Society Interface • Winter 2017 • www.electrochem.org

Get your subscription today! More than 132,000 articles and abstracts in all areas of electrochemistry and solid state science and technology from one of the leading nonprofit publishers in the field.

Rigorous peer review. Continuous publication. High impact research.

Flexible subscription options are available to academic and corporate libraries and other institutions. Advertising opportunities available. Contact sponsorship@electrochem.org for more information.

Visit www.ecsdl.org for more information.

ECS Institutional Members The Electrochemical Society values the support of our institutional members. Institutional members help ECS support scientific education, sustainability, and innovation. Through ongoing partnership, ECS will continue to lead as the advocate, guardian, and facilitator of electrochemical and solid state science and technology. (Number in parentheses indicates years of membership)

Benefits of Membership Discounts on: • • • •

Advertising in print and online Meeting registrations Exhibits and sponsorships Access to ECS Digital Library

Benefactor Industrie De Nora S.p.A. (34) Pine Research Instrumentation (11) Saft Batteries, Specialty Batteries Group (35) Scribner Associates, Inc. (21) Zahner-elektrik GmbH & Co KG (1)

AMETEK-Scientific Instruments (36) Bio-Logic USA/Bio-Logic SAS (9) Duracell (60) Gamry Instruments (10) Gelest, Inc. (8) Hydro-Québec (10)

Patron 3M (29) EL-CELL GmbH (3) Energizer (72) Faraday Technology, Inc. (11)

IBM Corporation (60) Lawrence Berkeley National Laboratory (13) Panasonic Corporation, AIS Company (23) Toyota Research Institute of North America (9)

Sponsoring Axiall Corporation (22) BASi (2) Central Electrochemical Research Institute (24) DLR-Institut für Vernetzte Energiesysteme e.V. Ford Motor Company (3) GS-Yuasa International Ltd. (37) Honda R&D Co., Ltd. (10) IMERYS Graphite & Carbon (30) Medtronic Inc. (37)

Molecular Rebar Design (1) Nissan Motor Co., Ltd. (10) Permascand AB (14) Technic Inc. (21) Teledyne Energy Systems, Inc. (18) The Electrosynthesis Company, Inc. (21) Tianjin Lishen Battery Joint-Stock Co., Ltd. (3) Toyota Central R&D Labs., Inc. (37) ZSW (13)

Sustaining General Motors Corporation (65) Giner, Inc./GES (31) International Lead Association (38) Kanto Chemical Co., Inc. (5) Karlsruhe Institute of Technology (1) Leclanche SA (32)

Los Alamos National Laboratory (9) MTI Corporation (1) Occidental Chemical Corp. (75) Sandia National Laboratories (41) SanDisk (3) Targray (1)

Please help us continue the vital work of ECS by joining as an institutional member today. To join or discuss institutional membership options please contact Shannon Reed, director of membership services at 609.737.1902 ext. 107 or Shannon.Reed@electrochem.org.

10/30/2017