FINAL 2015-16 UCSB MRSEC Annual Report

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Materials Research Laboratory at UCSB: An NSF MRSEC NSF DMR 1121053 Annual Report for the Period March 2015 to February 2016

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

TABLE OF CONTENTS

1. EXECUTIVE SUMMARY 1

2. LIST OF CENTER PARTICIPANTS 4

3. LIST OF CENTER COLLABORATORS 8

4. STRATEGIC PLAN 12

5. RESEARCH ACCOMPLISHMENTS 13

6. EDUCATION AND HUMAN RESOURCES 31

7. POSTDOCTORAL MENTORING PLAN 41

8. CENTER DIVERSITY 42

9. KNOWLEDGE TRANSFER TO INDUSTRY AND OTHER SECTORS 43

10. INTERNATIONAL ACTIVITIES 44

11. SHARED EXPERIMENTAL AND COMPUTATIONAL FACILITIES 45

12. ADMINISTRATION AND MANAGEMENT 49

13. PLACEMENTS OF STUDENTS AND POSTDOCTORAL SCHOLARS 50

14. LIST OF MRSEC-SUPPORTED PUBLICATIONS 51

LIST OF MRSEC-SUPPORTED PATENTS 76

15. BIOS OF NEW MRSEC INVESTIGATORS 77

16. MRSEC FACULTY AND STUDENTS HONORS AND AWARDS 78

17. HIGHLIGHTS 80

18. STATEMENT OF UNOBLIGATED FUNDS 81

19. BUDGET 82

20. APPENDICES 91

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

1. EXECUTIVE SUMMARY

1a. Vision and Overview

The vision of the NSF MRSEC at UCSB: The Materials Research Laboratory (MRL) is to serve the greater US and international materials communities as an innovation engine for new materials. We see the MRL as the “holding company” for all materials-research related activities that go on at UCSB. The success of the MRL is built on foundation philosophies – all MRL programs are synergistic, continually evolving and focus on problems and opportunities of a scope and complexity that require the advantages of scale and interdisciplinarity. All MRL activities are designed to enhance and cultivate interdisciplinary activities through shared office and laboratory space, intra-IRG meetings, co-supervision of students by faculty members from different departments and a numerous seminars during the year and the summer. One of the strengths of the MRL management structure is a flexible and responsive approach to new challenges and opportunities in all aspects of the MRSEC program. This is clearly demonstrated in this annual report with a significant collection of ground-breaking results, new programs and success stories. In addition to the IRG and Seed research that is carried out, and that is described in detail in this report, we are also proud of the numerous activities around start-up companies, other industrial collaborations, and the key role that the Shared Experimental Facilities (SEFs) play. In addition, there is the huge impact that the MRL has on Education and Outreach on the UCSB campus. As a single example, the MRL is involved with over 150 undergraduate internships every year (school year and summer), making it the single largest set of such activities on the UCSB campus. The large numbers of graduate students and post-doctoral fellows that participate in the Education and Outreach activities of the MRL (exceeding 100 this past year) is a testament to how the MRL vision has become so ingrained in the UCSB culture. The number is particularly noteworthy because it bespeaks the strong leverage of funding that is involved. Many of these involved students and post-docs are not in fact, supported directly by the MRSEC grant. A crucially important foundation for the MRL is the commitment to Shared Experimental Facilities. Materials research is highly resource intensive, and a single scientific publication today may involve very intensive instrumentation resource inputs; inputs that simply could not be made available to individual PIs. The UCSB MRSEC SEFs are divided into six different facilities, and two partner facilities, handling literally hundreds of users: from the groups of UCSB faculty PIs (from within and outside the MRSEC), research groups from other universities and colleges, from industrial partners, and from local small-scale start-ups. In fact, it would be accurate to say that some of the local start-ups in the energy and materials spaces (many led by former MRSEC students) would be hard-put to operate in the Santa Barbara areas were it not for the MRSEC SEFs. As the MRL seeks to renew itself in the new round of funding, it is a time of reflection and a time for documenting best practices. New IRGs are being formed, new members being recruited, and the leadership is evolving. However, the core vision of being an enabler of materials research and education, and of being inclusive, diverse, collaborative, and forward thinking will remain unchanged.

1b. Center Accomplishments for Current Reporting Period

Points of pride from this past reporting year have been the promotion with tenure of two key MRL junior faculty members: Javier Read de Alaniz who, in addition to research participation, heads up our diversity efforts, and Ania Jayich, who has now agreed to take over as Associate Director during the forthcoming MRSEC competition. Recent honors to MRL faculty include the selection of Susanne Stemmer (IRG-2 co-leader) as a National Security Science and Engineering Fellow. Chris Van de Walle (IRG-2 co-leader) was elected to the National Academy of Engineering, and Craig Hawker and Galen Stucky (IRG-3 affiliate) were both elected to the prestigious National Academy of Inventors. Rachel Segalman (Seed) was elected Fellow of the American Physical Society. Amongst the faculty, finally Professor Art Gossard, who was closely involved in the prior MRSEC as an IRG Co-leader, received the

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

National Medal for Technology and Innovation from President Obama earlier in 2016. Closely aligned with these recognitions is that UCSB’s Graduate Materials Program was ranked No. 2 in the 2016 U.S. News list of American Universities (No. 1 among Public Institutions). The Intellectual Merit contributions of the UCSB MRSEC include another highly productive year, with 65 publications acknowledging the MRSEC grant for direct or partial research support, and another 172 acknowledging the use of MRSEC facilities. The cumulative materials effort at UCSB, in which the MRL plays a central role, can be seen from the impact of these publications which can be measured in many different ways. Over 800 publications have appeared that acknowledge the prior MRSEC grant; these have already attracted over 10,000 citations. The latest (2016) Leiden University citation rankings list UCSB at #4 for Physical Sciences and Engineering, internationally: The MRSEC is a key contributor to the impact. In addition to awards to the senior stakeholders noted above, we are also very proud of our graduate students, post-doctoral fellows and even undergraduate interns. To only list a few: current school- year interns Claire Hebert and Joseph Mann, for example, won NSF Graduate Research Fellowships. They will both attend Stanford in the Fall. Claire also received a DOE Computational Science Graduate Fellowship, and Joseph an NDSEG Fellowship. Amongst MRL graduate students, Maxwell Robb received the 2016 Henkel Award for his Ph.D. work (which was related to IRG-1) and Jason Douglas (IRG-3) will soon start an NRC Post-Doctoral Fellowship at NIST.

Intellectual Merits – Research Highlights

The Center is organized into three IRGs and a dynamic and successful seed program. These IRGs include IRG-1: Bio-Inspired Wet Adhesion which focuses on synthetic materials inspired by the key building blocks of natural marine adhesives – catechol units and coacervate domains – coupled with developing quantitative mechanical tests for understanding these natural systems at unprecedented levels. The grand challenge continues to be a fundamental understanding of adhesion in wet and hostile environments allowing the translation to synthetic systems with high performance. The grand challenge of IRG-2: Correlated Electronics is the development of the scientific foundation of new technologies based on the unique transport properties of complex oxide heterostructures. A detailed understanding of the electrical and optical properties of oxide heterostructures, including the roles of strain, defects, interface polar discontinuities and band alignments, is a major focus of this multi-disciplinary program. IRG-3: Robust Biphasic Materials has focused on bulk thermoelectric and magnetic materials that display interfacial phenomena between the two designer phases that are spontaneously created within the material. The grand challenge in IRG-3 is to develop the necessary degrees of control through appropriate processing, which allows desired microstructures of functional materials to be developed. Finally, multiple seed projects have now been awarded that have allowed new participants to be brought into the MRSEC and address challenging new problems, including developing new, state-of-the-art techniques to probe important questions that enable materials advances. In addition to the three IRGs, the UCSB MRSEC is proud of its Seed Program. This past year, as the funding cycle comes to a close, funding in support of a Super Seed was awarded to Rachel Segalman to allow for the continuation and expansion of her then-current Seed project as noted in the cumulative list presented below.

PI or PIs Title Duration Ania Jayich Nanoscale Scanned Probe Imaging of Charge and 1/1/12 to 6/20/14 Spin at Semiconductor Surfaces and Interfaces Javier Read de Alaniz Atom and Energy Efficient Approach to Polymers 1/1/12 to 6/20/14 with Tunable Reactivity and Properties* Omar Saleh and Active Gels 1/1/12 to 6/20/14 Deborah Fygenson

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

Martin Moskovits and Developing Plasmonic Materials for Energy 3/1/13 to 2/28/15 Galen Stucky Applications Joan-Emma Shea Multiscale Modeling of Polymeric Materials 3/1/13 to 2/28/15 Jon Schuller Multipole Spectroscopy 3/1/13 to 2/28/15 Matt Helgeson Bio-inspired Routes to Structured Biphasic 1/1/14 to 12/31/16 Materials via Colloidal Assembly of Nanoemulsions Rachel Segalman Effect of Nanostructure on Ion Conduction in 1/1/14 to 12/31/16 Polymerized Ionic Liquids (this project is now a Super Seed funding Super Seed) provided 3/1/15 to 2/28/17 Mark Sherwin Terahertz Protonics 1/1/14 to 12/31/16

Names and titles in italics indicate that the funding was still active during this reporting period, and details of the activities are presented later in this report. From the above list, it is seen that all of the supported faculty PIs are from outside of the IRG structures.

Key Accomplishments – Broader Impacts

The Broader Impacts of the UCSB MRSEC include the outcomes of the research, the student and post- doctoral training and the mentoring of the early career faculty, the role played by the shared experimental facilities (SEFs) in supporting materials research and allied disciplines on the UCSB campus, and the many activities of the Education and Outreach Programs. All of these are described in detail in what follows. A number of initiatives and activities associated with Education and Outreach are overseen by the UCSB MRSEC that are supported both by the MRSEC grant and other sources of support, including NSF REU site grants, and by a now-ending NSF IMI grant. While the bulk of the funding goes to the support of undergraduate interns, the goals are to impact all stakeholders, starting from K-12 students and teachers to the general public. Figure 1 on the next page describes the range of Education/Outreach activities directly run by, or overseen by the UCSB MRSEC, that attempts to capture what has been carried out during the reporting period.

Fig. 1. Chart describing the many Education and Outreach activities of the UCSB MRSEC, including partnership activities. The nature of the involved stakeholders is indicated on the left.

The rest of the report describes in detail the activities in the past year and directions for the forthcoming year.

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

2. LIST OF CENTER PARTICIPANTS

i. Receiving Center Support: Leon Balents Physics, Kavli Institute for Theoretical Physics IRG2 Alison Butler Chemistry & Biochemistry IRG1 Michael Chabinyc Materials IRG2 Glenn Fredrickson Chemical Engineering, Materials IRG1 Michael Gordon Chemical Engineering IRG3 Songi Han Chemistry & Biochemistry, Chemical Eng. IRG1 Craig Hawker, Co-Director Materials, Chemistry & Biochemistry IRG1 Matthew Helgeson Chemical Engineering Seed Jacob Israelachvili Chemical Engineering, Materials IRG1 Ania Jayich Physics Seed Carlos Levi Materials, Mechanical Engineering IRG3 Eric McFarland Chemical Engineering Seed Martin Moskovits Chemistry & Biochemistry Seed Dorothy Pak Materials Research Laboratory, Marine Science Education Institute Outreach Chris Palmstrøm Electrical & Computer Engineering, Materials IRG3 Tresa Pollock Materials IRG3 Javier Read de Alaniz Chemistry & Biochemistry Seed Omar Saleh Materials Seed Jon Schuller Electrical & Computer Engineering Seed Rachel Segalman Chemical Engineering, Materials Seed Ram Seshadri, Co-Director Materials, Chemistry & Biochemistry IRG3 Joan-Emma Shea Chemistry & Biochemistry, Physics Seed Mark Sherwin Physics Seed James Speck Materials IRG2 Susanne Stemmer Materials IRG2 Galen Stucky Chemistry & Biochemistry, Materials Seed Megan Valentine Mechanical Engineering IRG1 Chris Van de Walle Materials IRG2 Herbert Waite Molecular, Cellular, & Developmental IRG1 Biology; Chemistry & Biochemistry Stephen Wilson Materials IRG2 Bold - IRG Leader/Co-Leader

ii. Affiliated, Not Receiving Center Support S. James Allen Physics IRG2 A. Bhattacharya Center for Nanoscale Materials-Argonne NL IRG2 Irene J. Beyerlein CMIME-Los Alamos NL IRG3 Claus Eisenbach Chemistry-Stuttgart IRG1 Claudia Felser MPI Dresden IRG3 Deborah Fygenson Physics, BMSE Seed G. Robert Odette Mechanical Engineering, Materials IRG3 Baron Peters Chemical Engineering, Chemistry & IRG3 Biochemistry Matthew Tirrell Molecular Engineering, University of Chicago IRG1 Anton Van der Ven Materials IRG3 4

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

iii. Users of Shared Center Facilities

Kolbe Ahn Marine Science S. James Allen Physics, Institute for Terahertz Institute Science and Technology David Awschalom Physics Kaustav Banerjee Electrical and Computer Engineering Gui Bazan Materials, Chemistry & Biochemistry Matthew Begley Materials, Mechanical Engineering Dan Blumenthal Electrical and Computer Engineering Jim Boles Earth Science Bodo Bookhagen Geography and Earth Science John Bowers Electrical and Computer Engineering Steve Buratto Chemistry & Biochemistry Alison Butler Chemistry & Biochemistry Otger Campas Mechanical Engineering Bradley Cardinale Ecology, Evolution & Marine Biology Michael Chabinyc Materials Oliver Chadwick Geography and Earth Science Anthony Cheetham Materials Science & Metallurgy Irene Chen Chemistry & Biochemistry Brad Chmelka Chemical Engineering Dennis Clegg Molecular, Cellular, and Developmental Biology Andrew Cleland Physics Larry Coldren Electrical and Computer Engineering Frederick Dahlquist Chemistry & Biochemistry Steve DenBaars Electrical and Computer Engineering, Materials Mike Doherty Chemical Engineering Peter Ford Chemistry & Biochemistry Glenn Fredrickson Chemical Engineering, Materials Michael Gordon Chemical Engineering, Materials Art Gossard Electrical & Computer Engineering, Materials Claudia Gottstein Molecular, Cellular & Developmental Biology Beth Gwinn Physics Songi Han Chemistry & Biochemistry Craig Hawker Chemistry & Biochemistry, Materials Trevor Hayton Chemistry & Biochemistry Alan Heeger Physics Matthew Helgeson Chemical Engineering Gretchen Hoffmann Ecology, Evolution & Marine Biology Patricia Holden Bren School for Environmental Science Jacob Israelachvili Chemical Engineering Luc Jaeger Chemistry & Biochemistry Skirmantas Janusonis Psychological and Brain Sciences Ania Jayich Physics Arturo Keller Bren School

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

Jim Kennett Geography, Earth Sciences Jennifer King Geography Todd Kippin Psychological and Brain Sciences Kenneth Kosik Neuroscience Research Institute L. Gary Leal Chemical Engineering Hunter Lenihan Bren School Carlos Levi Materials Dan Little Chemistry & Biochemistry Bruce Lipshutz Chemistry & Biochemistry John Martinis Physics Ben Mazin Physics Eric McFarland Chemical Engineering Robert McMeeking Mechanical Engineering Carl Meinhart Mechanical Engineering John Melack Bren School Gabriel Menard Chemistry & Biochemistry Fredrick Milstein Mechanical Engineering Umesh Mishra Electrical & Computer Engineering Samir Mitragotri Chemical Engineering Craig Montell Molecular, Cellular & Developmental Biology Daniel Morse Molecular, Cellular & Developmental Biology Martin Moskovits Chemistry & Biochemistry Shuji Nakamura Materials Stanley Parsons Chemistry & Biochemistry Pierre Petroff Materials, Electrical & Computer Engineering Philip Pincus Physics, Materials Kevin Plaxco Chemistry & Biochemistry Tresa Pollock Materials Javier Read de Alaniz Chemistry & Biochemistry Norbert Reich Chemistry & Biochemistry Dar Roberts Geography Mark Rodwell Electrical & Computer Engineering Joel Rothman Molecular, Cellular & Developmental Biology Cyrus Safinya Materials Omar Saleh Materials Joshua Schimel Ecology, Evolution & Marine Biology Susannah Scott Chemical Engineering Rachel Segalman Chemical Engineering Ram Seshadri Materials, Chemistry & Biochemistry Jon Schuller Electrical & Computer Engineering Tom Soh Mechanical Engineering, Materials James Speck Materials Todd Squires Chemical Engineering Susanne Stemmer Materials Dmitri Strukov Electrical & Computer Engineering Galen Stucky Chemistry & Biochemistry, Materials Theofanis Theofanous Chemical Engineering, Mechanical Engineering Luke Theogarajan Electrical & Computer Engineering Tom Turner Ecology, Evolution & Marine Biology

UCSB MATERIALS RESEARCH LABORATORY: AN NSF MRSEC 2016 ANNUAL REPORT

Megan Valentine Mechanical Engineering Herb Waite Molecular, Cellular & Developmental Biology David Weld Physics Thomas Weimbs Molecular, Cellular, & Developmental Biology Stephen Wilson Materials Les Wilson Molecular, Cellular & Developmental Biology Fred Wudl Materials, Chemistry & Biochemistry Hillary Young Ecology, Evolution & Marine Biology Armen Zakarian Chemistry & Biochemistry Joseph Zasadzinski Chemical Engineering Frank Zok Materials

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

3. LIST OF CENTER COLLABORATORS

Collaborator Institution e-mail Field of expertise IRG # Shared Facilities Barbara Albert Technische [email protected] Boride Materials Yes Universität, darmstadt.de __ Darmstadt, Germany Audrius Center for Physical Alkauskas Sciences and [email protected] Computational IRG-2 Yes Technology, Materials Lithuania

Xavier Banquy University of Biolubrication Montreal, Canada Xavier.banquy@umontreal IRG-1 No .ca Hugh Brown University of Polymer Mechanics Wollongong, [email protected] IRG-1 Yes Australia Markus Bulters Royal DSM, Polymer Simulation Netherlands [email protected] __ No

Hao Cai Nanyang Tech Applied Chemistry University, [email protected] IRG-1 No Singapore Luis Campos Columbia Polymer Synthesis University [email protected] IRG-1 Yes

Luke Connal University of Polymer Synthesis Melbourne, [email protected]. IRG-1 Yes Australia au Costantino ESPCI Paris Tech, Adhesion, Polymer Creton France [email protected] Mechanics IRG-1 No r X.Y. (“Carl”) Cui University of Computational Sydney, Australia [email protected] Materials IRG-2 No

Eric University of eric.drockenmuller@univ- Polymer Chemistry Drockenmuller Lyon, France lyon1.fr IRG-1 No

Luis Echegoyan University of Chemical Texas, El Paso [email protected] Synthesis, IRG-3 No Materials Chang-Beom University of Functional Oxide Eom Wisconsin [email protected] Thin Films IRG-2 No

Charles Fadley UC Davis Photoemission [email protected] Spectroscopy IRG-2 No u

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Amparo Fuertes Institute for Nitride Materials Materials [email protected] __ Yes Research, Barcelona Spain Maria Diaz University of [email protected] Distributed Garcia Alicante, Spain om Feedback Lasers and Organic __ Yes Semiconductors

Taylor Hughes University of [email protected] Theoretical Physics Illinois, Urbana- IRG-2 No Champaign

DongSoo Hwang Pohang University [email protected] Surface Chemistry of Science and IRG-1 No Technology, Korea

Tatsuhiro Iwama Asahi Kasei [email protected] Polymer Simulation Corporation, Japan kasei.co.jp __ Yes

Kenichi Izumi JSR Corporation, Polymer Simulation Japan [email protected] __ Yes

Debdeep Jena Cornell University Optical [email protected] Spectroscopy IRG-2 No

Yongseok Jho Pohang University Theoretical Physics of Science and [email protected] IRG-1 No Technology, Korea

Mercouri Northwestern m- Hybrid Functional Kanatzidis University [email protected] Materials __ Yes du

Ellina Kesselman Technion, IIT, Biochemistry Israel [email protected]. IRG-1 No ac.il Emmanouil University of Computational Kioupakis Michigan, Ann [email protected] Materials IRG-2 No Arbor Takeshi Kondo Inst. for Solid State Photoemission Physics, Univ. of [email protected] IRG-2 No Tokyo, Japan toyko.ac.jp

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Chanoong Lim Pohang University Polymer Chemistry of Science and [email protected] IRG-1 No Technology, Korea

Bettina Lotsch MPI for Solid State Carbon Materials Research, [email protected] __ Yes Stuttgart, Germany

Nate Lynd University of Polymer Chemistry Texas, Austin [email protected] IRG-1 No

John Lyons Brookhaven Computational National [email protected] Materials IRG-2 No Laboratory Rachel Martin University of [email protected] Chemical Biology/ California Irvine Physical Chemistry IRG-1 No

Egbert Meijer Eindhoven Organic Chemistry University of [email protected] IRG-1 No Technology, The Netherlands Brent Melot University of In-situ X-ray Southern [email protected] Diffraction __ Yes California

Ali Miserez Nanyang Biomaterials, Technological [email protected] Transcriptomics IRG-1 No University, Singapore

Himanshu Mishra KAUST, Saudi Interfacial Science Arabia [email protected] IRG-1 No du.sa Satoru Nakatsuji Inst. for Solid State Crystal Growth Physics, Univ. of [email protected] IRG-2 No Tokyo, Japan

Slavomir Nemsak Univ. of California Photoemission Davis [email protected] Spectroscopy IRG-2 No

Christopher Ober Cornell University Polymer Synthesis [email protected] IRG-1 Yes

Katharine Page Spallation Neutron Neutron Scattering Source, Oak Ridge [email protected] __ Yes National Laboratory

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Luigi Petrone Nanyang Tech Interfacial Science University, Luigi.petrone@brookesbel IRG-1 No Singapore l.com Francois Reniers Universite Libre de Plasma Physics Bruxelles, Belgium [email protected] __ Yes e Patrick Rinke Aalto University, Computational Helsinki, [email protected] Materials IRG-2 No Finland

John Rohanna DOW [email protected] Chemistry SEED Yes

Alfred Schultz DOW [email protected] Chemistry SEED Yes

David Shykind Intel Corporation Polymer Simulation [email protected] __ No

Taylor Sparks University of Utah Databases, Thermal [email protected] Conductivity IRG-3 No Measurements

Catherine Stampf University of Computational Sydney, Australia [email protected] Materials IRG-2 No .au Yeshanyahu Technion, IIT, Self Assembly Talmon Israel [email protected] IRG-1 No

Raymond Tu City University of Polymer Chemistry New York [email protected] IRG-1 Yes

Patrick Theofanis Intel Corporation Polymer Simulation [email protected] __ No m Joel Varley Lawrence Computational Livermore [email protected] Materials IRG-2 No Laboratory Amit Verma Cornell University MBE Growth, [email protected] Device Physics IRG-2 No

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

4. STRATEGIC PLAN

Materials research is inherently interdisciplinary and complex, with advances requiring expert input from across multiple related domains. Materials research is also resource intensive, and unraveling the details of structure and function entails multiple characterization and measurements tools, coupled with high- performance computation. The rationale behind the UCSB MRSEC is to foster a creative and collaborative research and training infrastructure, driving a highly-leveraged portfolio of forefront materials research. The vision of the UCSB MRSEC is to be an inclusive enabler and leader in materials research and education. The stakeholders range from K–12 students, school teachers, undergraduate research interns, graduate student and post-doctoral researchers, faculty investigators, other facility users, start-up and established industry partners, and collaborators in the US and abroad. The UCSB MRSEC will synergistically engage all stakeholders to ensure creative and exciting research outcomes are closely coupled with the mentoring of a diverse group of future leaders in materials research.

The UCSB MRSEC tackles transformative problems in materials research whose solutions require the collaborative input of dedicated teams of interdisciplinary researchers. The Interdisciplinary Research Groups (IRGs) strive to develop innovative approaches to synthesis, characterization/measurement and theory/computation to drive advances across a range of materials classes, with their corresponding functions. Rather than focusing on figures of merit, the emphasis is on fundamental understanding that would have sustained utility and impact beyond the duration of the project, especially through the development of methods and tools. New members associated with forward-looking research directions will be brought into the MRSEC through a competitive Seed Program. Support and growth of the Shared Experimental Facilities of the UCSB MRSEC will be a priority, sustaining academic research as well as aiding job creation in the California Central Coast region.

UCSB MRSEC scientists and education staff are dedicated to improving access to science for diverse groups, and to building a competent work force of scientists and engineers. Our education programs provide undergraduate research opportunities, graduate student and post-doctoral mentoring, meta- professional training, outreach to K-12 students and teachers, and community outreach. The goals of the program are to support teachers in creating innovative K-12 science curricula, to encourage a diverse group of students to learn about and pursue careers in science and engineering, to increase public interest and awareness in science, and to enhance scientist interaction with the public.

Broadening participation of all stakeholders at the UCSB MRSEC has the highest priority. UCSB’s Hispanic Serving Institution status (since 2015) provides a powerful framework and context for our efforts towards greater diversity within the Center. Significant gains have been achieved in the proportion of women and URM participants during the past reporting period, including among undergraduate researchers, graduate students, post-doctoral fellows, and Center faculty members. Going forward, we continue to work on and consolidate these gains, and will pay specific attention to increasing URM students at the graduate and post-doctoral levels, contributing to strengthening the pipeline of URM members in the Professoriate. Our continuing PREM relationships with UT El Paso and Jackson State have provided a roadmap for building appropriate alliances, in addition to providing us with valuable inputs on recruitment and retention that inform our interactions with other partner institutions.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

5. RESEARCH ACCOMPLISHMENTS AND PLANS

IRG 1: Bio-Inspired Wet Adhesion

Herbert Waite MCDB/Chemistry Biomimetic Materials, IRG Co-leader Songi Han Chemistry/ChemE Spectroscopy of Soft Matter, IRG Co-leader Megan Valentine MechE Mechanics, IRG Co-leader Alison Butler Chemistry Coordination Chemistry Glenn Fredrickson ChemE/Materials Soft Condensed Matter Theory/Simulation

Craig Hawker Chemistry/Materials Polymer Synthesis

Matthew Helgeson ChemE Complex Fluid/Soft Matter Structure Jacob Israelachvili ChemE/Materials Surface Physics Joan-Emma Shea ChemE/Physics Protein Structure Simulation

5 Post-Doctoral Associates and 8 Students (heavily leveraged with external fellowships) Post-Doctoral Researchers: Emma Filippidi (female), Ilia Kaminker, Zachary Levine, Wei Wei (female), Qiang Zhao. Graduate Students: Thomas Cristiani, Neil Dolinski, Jeff Gopez, Aimal Khankel, Kaila Mattson (Chem- NSF fellowship, female), Greg Maier, Matthew Menyo, Dusty Rose Miller (female), Alex Schrader, Vasisht Shastry, Menaka Wilhelm (female), William Wonderly Contributing Postdocs, Students, Visitors: Dan DeMartini, Katherine Stone (female), Michael Rapp (NSF Fellow), Matthew Gebbie, Daniel Klinger, Brett Fors, Maxwell Robb, Justin Poelma, Frank Leibfarth, Timothy Keller (Chem); Affiliated Undergraduates: John Errico, R. Sheil, Daniel Spokoyny, Brenden McMorrow, Noah Rubin. Affiliates (not supported): Claus Eisenbach (Stuttgart), Matthew Tirrell (Chicago)

Overview: A fundamental challenge in materials science is engineering durable adhesive bonds for wet, salt-encrusted, corroded and fouled surfaces. In 2010, we proposed to overcome this challenge by investigating the adhesion of mussels and sandcastle worms at multiple length and time scales and in sufficient detail to implement emerging design concepts into synthetic platforms. There was tremendous progress in 2015-2016. The progress will be summarized as 1) interfacial and cohesive adhesive chemistry involving Dopa (3, 4-dihydroxyphenylalanine) and catechol-containing natural and synthetic polymers, 2) coacervation, or the fluid-fluid phase separation of polyelectrolytes; 3) adhesive microarchitecture and the control of polyelectrolyte phase behavior, and 4) reduction to practice. The first three themes now have substantial experimental as well as theoretical bases and are interconnected as follows: marine organisms deposit their adhesive secretions on surfaces as coacervated fluids phase-separated from bulk water and spread over target surfaces, thereby presenting adhesive motifs such as Dopa for binding. Finally, the fluids undergo additional phase changes, e.g., inversion and precipitation, to become intricately structured and mechanically robust solid adhesives.

Interfacial Adhesion Chemistry: The adhesive role of the catecholic amino acid, Dopa, in mussel protein sequences has been called “pivotal”, but is poorly understood. A recent report in Science (DOI:10.1126/science.aab0556) by trainees in the Butler, Waite, Israelachvili collaboration has dramatically changed this. They showed that both the catechol of Dopa and lysine were required for interfacial adhesion under saline conditions. The charged ∑-amine of lysine evidently dislodges hydrated K+ ions sitting on mica thereby enabling the catechol to coordinate the underlying alumina sites. These results are the first to contest the notion that Dopa is sufficient for adhesion to all surfaces. A second major insight has to do with whether and how mussel proteins remove surface water from minerals. Waite, Israelachvili collaborating with Ali Miserez at Nanyang Tech (Adv. Func. Mat., DOI: 10.1002/adfm.201600210) used attenuated total reflectance FTIR to prove that surface dehydration 13

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

and coordinative binding between titania surfaces and catechol in mussel mimetic peptides is not observed in the Tyr-containing homologs. Thus, only Dopa dehydrates the surfaces. Dehydration is nicely monitored by the negative absorbance associated with bending and stretching modes in adsorbed water (figure 2). As the peptide film thickness increased, interactions between catechols switched to noncoordinative modes. On hydroxyapatite surfaces, there was no coordination, but adsorption was still strong and dehydration complete. Other studies by students of the Israelachvili-Waite collaboration have shown that non-Dopa containing mussel peptide sequences such as (AKPSYPPTYK)n in MFP-1 and (GYKGKYYGKGKKYYYK)n in MFP-5 exhibit remarkable adhesion when tested in the surface forces apparatus (Adv. Func. Mat., DOI: 10.1002/adfm.201502256). This has been attributed to pi- cation interactions between K and Y in the peptides. Fig. 2. Adsorption and interfacial Changes in cohesion triggered by Fe3+ addition, however, chemistry of synthetic mussel peptide are only observed in those peptide sequences with Dopa sequences on titania and hydroxyapatite as only those can form Fe3+ tris-catecholate coordinated surfaces were investigated by ATR-FTIR. cross-links (Biomacromol., DOI: 10.1021/bm501893y). The negative absorbances at water H2O bending frequencies are the first to measure Given the increasing demand for wet adhesives surface dehydration. in the past few decades (e.g. for dental and medical transplants, coronary artery coatings, cell encapsulants, etc.) and the growing database correlating Dopa chemistry with adhesion, the ability to model catechol-facilitated adhesion to surfaces has become paramount for the smart synthesis and optimization of novel underwater adhesives. During the past funding cycle, trainees in the Shea-Waite-Israelachvili collaboration performed combined experimental and theoretical studies of the adhesion of a mussel adhesive protein-inspired catechol-containing peptide to

Fig. 3. Simulation of mussel-inspired structure in bulk solution (left), on CH3-terminated SAMs, and on OH-hydrophilic SAMs (right). Note that the plane of the Dopa ring (green) is parallel and normal, respectively, to the nonpolar and polar surfaces.

organic thin films. Experiments and simulations both showed significant differences in peptide adsorption on CH3-terminated (hydrophobic) and OH-terminated (hydrophilic) self-assembled monolayers (SAMs), with adsorption strongest on hydrophobic SAMs due to orientationally specific interactions with Dopa (catechol) residues (figure 3). This study thus represents a first “toolbox” for predicting structure-property relationships of next-generation underwater glues on different surfaces.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Coacervation: Mussel and sandcastle worm adhesive peptides are deposited on underwater surfaces as dense fluid-fluid phase separated liquids known as coacervates and either involve the mixing of 2- component oppositely charged polyelectrolytes (sandcastle worms) or single component polyampholytes (mussels). IRG-1 members, particularly Han, Waite, Israelachvili and Fredrickson, have been active in studying both the experimental and theoretical aspects of coacervation. A collaboration between DongSoo Hwang and Songi Han is investigating a microphase-separated complex coacervate fluid generated by mixing a recombinant mussel foot protein-1 (MFP-1) as the polycation and hyaluronic acid (HA) as the polyanion. The exceptionally low interfacial tension of complex coacervates, phase-separated from a biphasic fluid, represents a unique and highly sought-after materials property that would enable novel applications from superior coatings to wet adhesion. Despite extensive studies and broad interest, the molecular and structural bases for Fig. 4. Water-filled bicontinuous nanostructured coacervates with the unique properties of complex low cohesion energies give rise to low interfacial tension (work in coacervates are unclear. A progress, Han, SI). O atoms in water are red. stoichiometric mixture of MFP-1 and HA was macroscopically phase-separated into a dense complex coacervate and a dilute supernatant phase to enable separate characterization of the two fluid phases. Surprisingly, despite a 104-fold difference in density, the diffusivity of water in the coacervate and supernatant phases was found to be indistinguishable (Hwang, Han, et al, ACS Nano, in review). The presence of unbound, bulk-like water in the dense fluid is reconciled with a water population that is only weakly perturbed by the polyelectrolyte interface and network. This hypothesis was experimentally validated by cryo-TEM. The macroscopically phase-separated dense complex coacervate phase was observed to consist of a bicontinuous and biphasic nanostructured network (figure 4), in which one of the phases was confirmed to be water and the other, polyelectrolyte complexes, by staining techniques. We conclude that the weak cohesion energy between water-water and water- polyelectrolytes manifests itself in a bicontinuous network and is responsible for the exceptionally low interfacial energy of this complex fluid phase with respect to virtually any surfaces within an aqueous medium. As measured by a significantly stronger retardation of water diffusivity, the increasing cohesion energy of the dense fluid upon addition of polyethylene glycol strongly suggests that the bicontinuous network structure and interfacial energy are inversely coupled. That is, as the interfacial energy of the dense complex coacervate phase (as measured by the pendant drop method in water) increases, the bicontinuous network structure breaks up. Han, Waite, and Israelachvili are now combining these insights to measure the viscosity of the discontinuous phase of coacervated samples. This work also leverages the microrheology expertise of Valentine, who has recently developed magnetic tweezers devices that allow direct measurement of the viscosity of microliter volumes of soft samples (Rev. Sci. Instr., DOI: 10.1063/1.4921553). It is now established that at least one adhesive protein, MFP-3s, is self-coacervating and that the coacervated form is significantly more efficiently and permanently adsorbed on titania and hydroxyapatite surfaces than noncoacervated aqueous solute (Adv. Func. Mat., DOI: 10.1002/adfm.201600210). Based on reports that coacervates have reduced viscosity and interfacial energy, trainees in the Waite, Israelachvili, Miserez collaboration tested the ability of single coacervates to infiltrate into scaffolds like chitin. The His-, Tyr-rich protein from squid forms self coacervates with reductions in interfacial energy and viscosity that enable it to infiltrate chitin (Nat. Chem. Biol., DOI: 10.1038/nchembio.1833). Given the growing interest in double networks and the difficulty of infiltrating one network into another, these results should spur new thinking about fabrication methods.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Fredrickson and coworkers have applied analytical methods and field-theoretic simulations (FTS) to elucidate the relationship between conventional complex coacervation of a mixture of cationic and anionic polymers in aqueous solution and self-coacervation of one- component polyampholytes. To this end, they have constructed a minimal statistical field theory model of a symmetric coacervate system comprised of two oppositely charged flexible homopolymers of equal lengths N and equal (but opposite in sign) uniform charge densities σ. The solvent is treated implicitly and there are two types of interactions in the system: long-range Coulomb interactions Fig. 5. The phase diagram for two-phase mediated by the solvent dielectric constant ε and short- complex coacervation of a neutral blend of range (potential of mean force) repulsions between polymer polyanions and polycations (solid, blue) segments reflecting the solvent quality and modeled by an and one-component polyampholytes of the same total molecular weight (solid, red) excluded volume parameter u. The phase diagram for this constructed using an approximate analytic model, including the important two-phase region of one-loop perturbation theory. The region of complex coacervation, has been elaborated using a mixed-phase instability (spinodal) is combination of approximate one-loop analytical theory and marked by the dashed lines. C is a exact FTS simulations (figure 5). A contrasting symmetric dimensionless polymer concentration, and E is a dimensionless measure of the polyampholyte model has been constructed by joining electrostatic interaction strength. polyanions and polycations pairwise at one end to form a one-component solution of diblock polyampholytes, each of chain length 2N and no net charge. Similar one-loop and FTS simulations of this model reveal self-coacervation behavior strikingly similar to the conventional two-component case. Fredrickson argues that this near-isomorphism of self-coacervation to conventional coacervation is a consequence of polycations and polyanions pairing to compensate charge even at extremely dilute concentrations prior to entering the two-phase coacervate envelope.

Microarchitecture and mechanics: To understand the impact of these molecular and structural features on adhesion strength and mechanics, the Valentine group studies the mechanics and dynamics of mussel plaque detachment using a custom-built load frame with imaging capabilities. With Waite, Valentine found that the mussel holdfast shape and its ability to dissipate energy substantially improves the plaque tenacity (Soft Matter, DOI:10.1039/C5SM01072A). To understand the structural origins of this enhancement, Valentine, Waite and Helgeson showed with neutron scattering and electron microscopy that such plaques contain porous, hierarchical meshworks (J. Roy. Soc. Interface, DOI: 10.1098/rsif.2015.0614). Valentine and Waite are now extending this work to explore the effects of cyclic loading on mechanics and structures, with a focus on understanding the possible mechanisms of toughening and reversibility after loading. The studies have also been broadened to include more mussel diversity species to attempt to link differences in the natural environment (i.e. average wave power) to adaptations in plaque structure and strength. To continue to translate these advances into synthetic materials with desirable properties, including tunable porosity, stiffness gradients, and controlled shape as well as surface adhesion, a crosscutting collaboration of Valentine, Waite, Israelachvili, Hawker, Eisenbach and Helgeson is working to introduce thiol-ene and catechol functionalities in structured polymer networks. A new collaboration with Prof. Costantino Creton at ESPCI-ParisTech has also been initiated to study the effects of fiber-reinforcement in dynamically-bonded gels, inspired by the mussel.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

A recent capstone study was conducted to determine whether what we’ve learned about catechols, coacervating polyelectrolytes and microstructure could be integrated into a single process (as it is in the mussel or sandcastle worm). In other words, can we take a polyelectrolyte functionalized with catechol, induce it to undergo coacervation underwater, phase invert into a structured fluid and finally precipitate it to a porous adhesive polymer? All of these were achieved and reported in Nature Materials (DOI: 10.1038/NMAT4539). Complex coacervation of a polycation with a catechol- functionalized polyanion was mediated by a DMSO to water solvent exchange. Polyelectrolyte coacervation led to phase Fig. 6. The porous microstructure of an separation, closely followed by phase-inversion and adhesive made by solvent exchange precipitation. Precipitated structures resembled mussel plaques from amine-quaternized chitin and with multiple length scales of porous structure (figure 6). catechol-functionalized polyacrylate. Catechol density in the polyanion was correlated with favoring Scale bar is 200 nm. tighter pore structures. The fact that we can now make a porous wet adhesive and vary its porosity will spur experiments to test the models relating adhesive fracture energy and porosity in actual mussel plaques.

Reductions of concepts to practice: Starting from cheap, bioavailable building blocks such as eugenol, synthetic strategies for the introduction of catechol units into a variety of materials have been developed by Hawker, Waite and Israelachvili and demonstrated to have significant utility for enhancing material properties. An efficient, high-yield route to catechol- functionalized polyethers based on thiol-ene chemistry allows the number and position of the catechol units to be tuned. For example, triblock copolymers having two end blocks with catechol-anchoring groups and a looping poly(ethylene oxide) (PEO) midblock were prepared and shown to be effective for high lubrication and low cell adhesion (ACS Nano, DOI: 10.1021/acsnano.5b06066). Catechol units could also Fig. 7. Bio-inspired catechol building blocks bind to an array of metal oxide surfaces leading be introduced into self-assembled monolayers with the to novel, reformable coatings. Applications reversible nature of catechol binding allowing range from friction/wettability control to adhesive (Nat. Comm., DOI: 10.1038/ncomms9663) biomolecular sensing and antifouling. and removable and recoverable coatings to be prepared on a variety of oxide surfaces (ACS Appl. Mater. Int., DOI: 10.1021/acsami.5b06910) (figure 7), as well as metal-coordinating hydrogels (ACS Macro Lett., DOI: 10.1021/acsmacrolett.5b00664). These reductions to practice represent a promising platform for the development of specialized high-performance, industrial coatings.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

IRG 2: Correlated Electronics

Susanne Stemmer, Materials Oxide Film Growth, IRG Co-leader Chris Van de Walle, Materials DFT Theory, IRG Co-leader Jim Allen, Physics Optical and Electrical Transport Leon Balents, Physics/KITP Many Body Theory Michael Chabinyc, Materials Electrolyte Gating Jim Speck, Materials Oxide Semiconductors Stephen Wilson, Materials Synthesis, Transport

Supported Post-Docs: Stephen Kaun, Honggyu Kim, Jianpeng Liu, Timo Schumann Graduate Students: Lars Bjaalie, Anne Glaudell, Santosh Raghavan, Michael Swift, Wennie Wang, Jack Zhang Affiliates: Anderson Janotti, Xiang Chen, Rebecca Daily, Thomas Hogan, Hartwin Peelaers

Overview: IRG-2: Correlated Electronics is focused on the unique properties of complex oxide heterostructures including the roles of strain, defects, interface polar discontinuities and band alignments; tailoring of the electrical and optical properties of complex oxides through dimensionality, strong correlations, heterostructuring and by field effect; and exploration of the potential of oxides for next- generation technologies. Highlights over the past year include a closely coupled experimental/theoretical study of small polarons in complex oxides, resolving longstanding questions about doping of the Mott state in spin-orbit coupled Mott insulators, and a new model of magnetism at Mott/band insulator interfaces.

Correlated Oxide Heterostructures: In a previous IRG-2 report, we reported on experimental studies that used Sr(Ti,Zr)O3/SrTiO3 heterostructures to modulation-dope SrTiO3 and obtain a two-dimensional electron gas (2DEG) at the interface (Appl. Phys. Lett., DOI: 10.1063/1.4819203). In this project period, the Van de Walle group investigated structural and electronic properties of these materials using hybrid density functional calculations. It was found that the lattice parameter closely follows Vegard’s law. The band gap, which determines the band offsets with SrTiO3 and as such is crucial for the modulation-doping experiments, on the Fig. 8. Magnetic phases at Mott/band other hand, shows a large bowing and is highly sensitive to insulator interfaces. The study is based the Ti distribution. For the 50/50 alloy, it was found that upon a bilayer Hubbard model at U = 1 arranging the Ti and Zr atoms into a 1×1 SZO/STO with a potential difference between the superlattice along the [001] direction leads to a band gap two layers (vertical axis). The close to that of pure STO, and a highly dispersive single band horizontal axis is the carrier density in at the conduction-band minimum. Such short-period the 2DEG, relative to half filling. SZO/STO superlattices could therefore be exploited to improve carrier mobility compared to bulk STO (Phys. Rev. B, DOI: 10.1103/PhysRevB.92.085201). A focus of the oxide heterostructure work in IRG-2 is GdTiO3, which is a prototypical Mott 1 insulator with a Ti 3d electron configuration. GdTiO3 has attracted a lot of attention due to the formation of a high-density two-dimensional electron gas when interfaced with SrTiO3, discovered by the Stemmer group. In this project period, the Van de Walle group contributed to the interpretation of photoemission experiments of this 2DEG (Appl. Phys. Lett., DOI: 10.1063/1.4936936). Experiments (Stemmer group) observe magnetism in the 2DEG at the GdTiO3/SrTiO3 interfaces. Balents showed that the interplay of a high density two-dimensional electron gas and localized electrons in a neighboring Mott insulator leads to kinetic magnetism unique to the Mott/band insulator interface [arXiv:1509.02860], see figure 8.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

In addition to magnetism, the 2DEG at these interfaces shows other unique transport properties. In particular, the resistivity as a function of temperature (T) shows a wide range where is behaves as T2, which has commonly been attributed to Fermi liquid behavior, and is observed in a wide range of correlated materials. In the present project period Stemmer and Balents showed (Sci. Rep., DOI: 10.1038/srep20865) that scattering rate in both 2DEGs and bulks STO is independent of the carrier density. This is contrary to Fermi liquid theory. The results indicate that the applicability of Fermi liquid theory should be questioned for a much broader range of correlated materials and point to the need for a unified theory. Accurate information about the Mott-Hubbard gap in GdTiO3 is essential for the design and analysis of heterostructures. Using hybrid functional calculations, the Van de Walle group determined a value of the Mott-Hubbard gap of close to 2 eV, much larger than had been previously assumed. This value was confirmed in photoluminescence measurements on samples grown by the Stemmer group (Phys. Rev. B, DOI: 10.1103/PhysRevB.92.085111). The Van de Walle group has also performed a comprehensive study of native point defects and impurities in GdTiO3, finding that Fig. 9. Atomic structure for a these systematically introduce small hole polarons and thus explaining carbon substitutional the experimental observation of p-type hopping conductivity in impurity on an oxygen site in nominally undoped material (see figure 9). They also analyzed how GdTiO3, resulting in the the defect-induced polarons impact optical properties and can act as formation of a small hole traps in devices. The work has been selected as an Editor’s polaron on a Ti atom bound Suggestion in the journal Phys. Rev. B (in press). The onset in optical to the carbon. conductivity spectra in rare-earth titanates, typically around 0.5 eV, has commonly been attributed to a transition from the lower to the upper Hubbard band. An intra-IRG-2 collaboration of the Stemmer, Allen, and Van de Walle groups has now established that the absorption is actually due to excitations of small hole polarons. High-quality GdTiO3 samples were grown with molecular beam epitaxy (MBE) by the Stemmer group, and intentionally doped with Sr acceptors. Optical conductivity measurements by the Allen group established that the strength of optical absorption correlates with the amount of Sr doping. First-principles calculations by the Van de Walle group showed that holes in GdTiO3 self-localize in the form of small polarons: the hole becomes trapped on a single Ti site, accompanied by a lattice distortion. Infrared light causes the polarons to be excited out of their self- trapping potential well via a hopping process, and the calculated absorption agrees with the measured curves. The conclusion that this feature in the optical conductivity spectra is caused by small polarons and not by excitations across the Mott-Hubbard gap likely applies to other rare-earth titanates as well. Future theoretical work will include further investigations of band alignments, and effects of strain and pressure on electronic structure and polarons.

Electrostatic Doping of Mott Materials: In addition to the modulation-doped structures described above, which aim at low-density 2DEGs, a focus of IRG-2 is on the electrostatic modulation of very large carrier densities typical of Mott materials. In particular, the modulation of the carrier concentration in correlated materials can potentially drive metal-to-insulator transitions (MITs) if sufficiently high carrier densities can be induced. The Chabinyc group uses ionic liquids (ILs) which are molten salts of bulky organic cations and anions, to attempt to gate both crystalline and amorphous thin films of oxides. A key question in this work was the determination of whether the effects observed were due to electrochemical effects, i.e., modification of the material under investigation, or due to simple electrostatic effects at the IL-oxide interface. Through examination of thin films of NdNiO3, Chabinyc and Stemmer found that the changes in the MIT were found to be driven mainly by electrochemical effects (Appl. Phys. Lett., DOI: 10.1063/1.4915269). Chabinyc and Waite (IRG-1) discovered that electrochemical changes at the surface of solution-processed ZnO could be controlled by addition of redox-active molecules to the IL (Adv. Mater., DOI: 10.1002/adma.201500556). These additives bind to the surface of ZnO in a similar

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

manner to the biomimetic materials studied in IRG-1 and form a solid-electrolyte interfacial layer upon operation of IL-gated devices. The recognition of the reaction chemistry of complex oxides at interfaces with ILs suggests that we can gain control of these materials using electrochemical means. The Van de Walle group and the Chabinyc group are currently working on approaches to study doping of WO3. Furthermore, Wilson and Chabinyc are currently examining the reactivity of single crystals of Sr2IrO4 and Sr3Ir2O7 under electrochemical cycling in ILs to modify their hole and electron concentration.

Spin-Orbit Mott Materials: In addition to electrostatic gating of the MIT relatively “simple”

Mott insulators such as NdNiO3, IRG-2 also focuses on controlling the MIT in another class of Mott materials, the spin-orbit Mott materials. In these materials, the Wilson group, with theoretical support by Balents, is working on understanding their response to doping. One of the goals is to understand the mechanism through which the spin- Fig. 10. Electronic phase diagram showing the orbit Mott state collapses, to search for the collapse of long-range order in electron-doped appearance of nearby competing electronic states, Sr2IrO4. (Phys. Rev. B, DOI: and to understand the influence of nearby 10.1103/PhysRevB.92.075125). instabilities on the resulting phase behaviors. Electron doping was investigated in two prototypical spin- orbit Mott systems, Sr3Ir2O7 and Sr2IrO4. In Sr2IrO4, the Wilson group used La-substitution to weaken the antiferromagnetic ground state and destabilize long-range order into short-range correlations (Phys. Rev. B, DOI: 10.1103/PhysRevB.92.075125) (figure 10). At the upper limit of La-solubility within the lattice, a weak insulating state persists with short-range order spin order in a nanoscale phase separated state. This low-temperature spin state was discovered to freeze into a glass-like state whose onset temperature evolves with electron doping. A key finding of this work was that the Mott state persists up to the doping limit in this system—suggesting that new doping mechanisms must be employed to search for new emergent states beyond the edge of the spin-orbit Mott state’s stability in this material.

Fig. 11. Crystal structure of Sr3Ir2O7 showing a Fig. 12. Relationships between length of b-axis of subtle monoclinic distortion coherently grown ®-(AlxGa1-x)2O3 bc and Al composition x. Error bars show ±2⌠.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

A second accomplishment of the Wilson group in the reporting period was the completion of a study of the electronic phase diagram of La-doped Sr3Ir2O7 (Phys. Rev. Lett., DOI: 10.1103/PhysRevLett.114.257203). The weaker spin-orbit Mott state in this bilayer system can be completely destabilized via electron substitution. The transition into a global metallic regime is accompanied by the appearance of an additional order parameter; one manifested by a subtle structural distortion below a critical temperature (TS). The microscopic origin of this distortion (i.e., structurally or electronically driven) is still under investigation; however as the initial step in exploring this question, the intrinsic structure of the parent Sr3Ir2O7 was explored (Phys. Rev. B, under review; arXiv:1603.07390) (figure 11). In a collaboration between the Van de Walle and Wilson groups, a long-standing mystery regarding the inherent structure of this bilayer compound was resolved. Specifically, they uncovered a subtle monoclinic distortion in the otherwise presumed orthorhombic lattice of Sr3Ir2O7. This study also solved the enigmatic origin of weak ferromagnetism in bulk magnetization measurements of this compound. Going forward, this now provides the basis for more fully understanding the mechanism and symmetry breaking associated with the doping driven TS transition.

Science of Oxide Molecular Beam Epitaxy: Synthesizing oxide thin films with low defect concentrations using oxide molecular beam epitaxy (MBE) remains a major focus of IRG-2. The Speck group, working on MBE of β-Ga2O3 and its heterostructures, have developed a new x-ray characterization method to estimate the composition of MBE β-(AlxGa1-x)2O3 coherently grown on β- Ga2O3 (010). For this purpose, stress-strain relationship in the monoclinic system was used along with elastic stiffness tensor of ®-Ga2O3 obtained from first-principles calculations by Van de Walle. Compositions estimated by XRD were then confirmed by atom probe tomography (APT). As shown in figure 12, the estimated composition for two different samples are in good agreement with the actual number measured by APT.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

IRG 3: Robust Biphasic Materials

Tresa Pollock Materials Characterization, IRG Co-leader Ram Seshadri Chem./Materials Synthesis and Modeling, IRG Co-leader Michael Gordon Chem.E Synthesis Carlos Levi Materials/Mech.E Characterization Chris Palmstrøm ECE/Materials MBE Growth Anton Van der Ven Materials Theory

Supported post-docs: Nisha Verma (50 %). Graduate students: Malinda Buffon (NSF-GRF), Elizabeth Decolvenaere, Jason Douglas (NSF-GRF), Michael Gaultois (Fulbright/NSERC, Graduated in 2015), Emily Levin, Andrew Pebley, Anthony Rice. Undergraduate students: Demetrious Lloyd, Francesca Long (University of Wisconsin, Summer 2015), Shahryar Mooraj, Kai Schwennicke, Natalie White (Jackson State, Summer 2015). Affiliates (not supported): Baron Peters (Chem.E/Chemistry), Galen Stucky (Chem./Materials).

Overview: The goal of IRG-3: Robust Biphasic Materials is driven by the grand challenge of building new materials with unique properties through the development of biphasic inorganic “hard” materials. Major objectives include elucidating a fundamental understanding of the novel properties arising from the presence and interaction of two phases; developing synthetic strategies that allow these materials to be fabricated in sufficient quantities, greatly expanding their availability and interest; and designing the structural parameters required for robust operation in harsh engineering environments. The current focus of IRG-3 is divided across two applications: thermoelectrics (described first) and magnetic materials (described next). Additionally, modeling and theoretical descriptions of these materials are an active area of development, both as an integrated approach throughout the IRG-3, and as a dedicated area of research (described last).

Research Progress:

Over the past year, IRG-3 has expanded the investigation of biphasic thermoelectric compounds to explore the impact of introducing a full-Heusler secondary phase to a half-Heusler matrix on systems other than that of TiNiSn/TiNi2Sn. This was achieved by introducing precipitates of a semi-coherent NbCo2Sn Heusler phase to half-Heusler NbCoSn through the addition of Co. A series of NbCo1+xSn samples prepared using arc-melting were characterized using electron microscopy, neutron diffraction, and X-ray diffraction studies, and, as shown in the left panel of figure 13, these studies indicated the successful formation of a biphasic material. Neutron diffraction further revealed that annealing has an important role to play in determining antisite ordering of these materials. Electrical and thermal transport measurements were used to understand property evolution; thermal conductivity measurements are highlighted in the right panel of figure 13. It was determined that the observed antisite disorder improves thermoelectric performance through the reduction of thermal conductivity, and, similar to the more widely studied TiNi1+xSn system, the addition of excess Co to NbCoSn phase displays an improvement in thermoelectric performance through a decrease in thermal conductivity. Promising work on biphasic Heusler intermetallics for thermoelectric applications has led to investigations into other functional Heusler materials. Certain types of intermetallic Heusler compounds are known to exhibit various magnetic orderings, which can be controlled by small changes of their chemistry. This is of particular interest to IRG-3 because it is possible to study the interplay of competing magnetic behaviors just by chemical substitution. This past year, IRG-3 researchers have explored the chemical space between antiferromagnetic (AFM) MnRu2Sn and ferromagnetic (FM) FeRu2Sn, characterizing materials of varying Mn:Fe ratios, Mn1- xFexRu2Sn. Our results (figure 14) show that at intermediate compositions, the magnetic hardness (coercivity) of the material is greatly increased, exceeding 1 kOe at Mn0.5Fe0.5Ru2Sn. Neutron diffraction

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

is used to characterize the structure and chemistry of the materials. Though there is no indication of a chemical phase separation—into MnRu2Sn and FeRu2Sn—at intermediate compositions, the appearance of new diffraction peaks at 15 K indicates the coexistence of AFM and FM phases in Mn0.5Fe0.5Ru2Sn. Transmission electron microscopy (TEM) is also being utilized for microstructural characterization.

Fig. 13. Left: Powder synchrotron X-ray diffraction results for unannealed NbCo1+xSn, x = 0.00 through 0.20 (indicated) samples. Indexed peaks from the refined lattice constants for the half-Heusler (hH) and Heusler (H) phases are shown in the top two panels. (220) peaks are shown in detail on the panel to the right, where the evolution of the H phase can be observed with increasing x. Right: Thermal conductivity for x = 0.00 and x = 0.15 samples as (a) a function of temperature and (b) as a function of x at 800 K. An samples were treated to an additional annealing step compared to AP specimens. It is observed that both the absence of the annealing step and the inclusion of the secondary H phase reduces thermal conductivity.

Fig. 14. Left: Time-of-flight neutron diffraction of Mn0.5Fe0.5Ru2Sn converted to an equivalent CuKα 2θ for display. At 15 K, below the Néel temperature, antiferromagnetic ordering in the material causes magnetic scattering peaks to appear, not present at room temperature. Right: Magnetization vs. applied field loops for Mn1–xFexRu2Sn.

Additionally, future plans in this direction for IRG-3 call for looking at magnetic exchange in bulk Mn2NiSn/MnNi2Sn systems prepared by microwave synthesis and arc melting. The full Heusler MnNi2Sn is ferromagnetic with a Curie temperature near room temperature, and the off-stoichiometric compositions are known to display a giant inverse magnetocaloric effect. The high Curie temperature of MnNi2Sn allows for easy observation of the effects of structuring on magnetic properties. While Mn-Mn interactions are antiferromagnetic, the Mn2NiSn has a large degree of antisite disorder, leading to potentially interesting effects. This system will be used to characterize magnetic hardening of soft

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

ferromagnets. Electron microscopy and neutron diffraction will allow for the examination of microstructure and magnetic structure, while the SQUID magnetometer MPMS will be used for magnetic properties measurement such as characterizing exchange bias in these systems.

Fig. 15. Left: Measured sheet resistance of different semiconducting half-Heusler structures. Structures containing both layers show values much lower than pure layers. Heusler layers in these samples are 25nm thick. Right: XRD of the (002)/(004) peaks of CoTiSb1-x films. Two components exist in films with compositions expected to have two phases and are nearly at the same position.

Previously, IRG-3 has used molecular beam epitaxy (MBE), Ni1+xTiSn films to determine the presence of two strained, but not perfectly coherent, phases, captured in figure 15. CoTiSb, a wider band gap semiconductor, has been successfully grown with MBE before, however no full-Heusler phase is predicted to be stable in the Co-Ti-Sb system. Instead, a second phase may be added by growing Sb deficient samples to precipitate out a B2 phase, CoTi. Both pure phases have been successfully grown, and in between compositions potentially show two phases with very similar lattice parameters, suggesting a more coherent interface than in Ni1+xTiSn. Attempts have also been made to integrate NiTiSn and CoTiSb, resulting in heterostructures much more conductive than either constituent layer. Using in-situ X-ray photoelectron spectroscopy, the valence band-offset between the layers was measured to be ~0.1 eV, resulting in a type-I structure (given predicted band gaps). Work is underway to determine the exact cause of this transport behavior.

Fig. 16. (a) Schematic of microplasma-deposition system, (b) picture of Argon microplasma jet operated at 14 Torr, (c) SEM images of cross-sectional and plan views of a NiFe2O4/NiO film o deposited using microplasmas at 175 C, and (d) hysteresis loops for the NiFe2O4/NiO film after o annealing at 500 C for 4 hours in air, where HC is the coercivity and HEB is the horizontal loop shift due to exchange bias.

IRG-3 researchers have continued to develop and utilize flow-stabilized microplasmas (see figure 16) for synthesis of biphasic NiFe2O4 (ferrimagnet) and NiO (antiferromagnet) nanogranular films

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

which exhibit exchange bias, an interesting magnetic phenomena not present in the isolated constituent magnetic phases. The unique operating characteristics innate to microplasmas, namely non-equilibrium plasma operation, relatively high pressures, and large gas throughputs, are conducive to the formation of clusters and nanoparticles in the gas phase. The direct line of site of the microplasma can be leveraged to spray deposit these nanosized gas phase building blocks on any surface to form nanostructured thin films. Figure 16(c) shows the plan and cross sectional view of a biphasic NiFe2O4/NiO film deposited with o microplasmas at a substrate temperature of 175 C. The ability to form NiFe2O4 at relatively low temperatures is an intriguing result, as it highlights the ability of microplasmas to open up chemical pathways that are absent in more traditional synthesis techniques (e.g., co-precipitation, precursor decomposition and thermal methods), which require much higher temperatures to yield spinel NiFe2O4. Magnetization as a function of applied field was measured at 5 K for this film after annealing at 500 oC for 4 hours in air, as shown in figure 16(d). The zero field cooled hysteresis loop (open squares; film was cooled from 300 K to 5 K in no applied magnetic field before M-H measurement) is perfectly symmetric about the origin, showing no sign of exchange bias (i.e., horizontal shift of the hysteresis loop). Conversely, the hysteresis loop measured after field cooling (closed squares; film was cooled from 300 K to 5 K in a 20 kOe applied field before M-H measurement) clearly shows the presence of the exchange bias effect manifested as the horizontal shift of the hysteresis loop (~700 Oe). Additionally, the coercivity (HC) of the hysteresis loop (i.e., half the width of the loop) increased after field cooling. The fundamental nature of this magnetic coupling was investigated using systematic post deposition heat treatments and temperature dependent magnetization measurements, and was found to stem from coupling between the NiFe2O4 nanograins and a very thin amorphous spin glass phase at the interface. Moreover, exchange bias was not witnessed in this film at room temperature, but a coercivity (HC) of 1050 Oe was measured and is the highest reported HC for the NiFe2O4/NiO system at room temperature.

Fig. 17. (a) Formation energies of ground states and selected configurations using both the original (blue) and recovered (orange) Hamiltonians for the three systems examined. In all cases the ground states are exactly recovered, and the energies are accurate to within a small scaling factor. (b) Original (left) and recovered (right) phase diagrams for the three systems examined, scaled by the nearest-neighbor coupling constant (VNN). Color corresponds to ln(HeatCapacity/VNN), such that sudden changes in color highlight phase transitions.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

In addition to the synthesis and characterization projects, IRG-3 has been exploring new approaches for uniting theory/simulations with experiments. Our previous study of the Co-Pt binary revealed massive shortcomings in the predictive power of density functional theory (DFT), with respect to late 3d-5d binaries. Unfortunately, the cluster expansion formalism to-date relies on the availability of high-purity phase formation energies, usually found using ab-initio methods such as DFT. IRG-3 researchers have developed a new method for elucidating the relevant clusters and their coupling constants from high-temperature, disordered phases. Considering cluster expansion Hamiltonians through the lens of entropy maximization yields a polynomial-time algorithm for cluster selection, while thermodynamic calculations yield an intrinsic link between an observable (atomic correlations) and the unobservable cluster coupling constants. Using this approach, the thermodynamic ground states, as well as the full phase diagram, can be determined with only a few measurements on a quenched sample. The new methodology has been tested on three candidate systems, and recovered results nearly identical to our input values (figure 17). In the future, IRG-3 will apply our method to experimental measurements and develop the first experiments-driven cluster expansion Hamiltonian.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Seed Project: Multipole Spectroscopy

Participants: Jon Schuller (PI), Tanya Das (graduate student), Tomer Lewi (Post-doctoral fellow)

Our ability to understand and manipulate materials with light is limited to “visible” properties and excitations. Many “forbidden” excitations do not couple to light and are “invisible” to our optical measurements and manipulations. These “dark” states can exist at the molecular/atomic level as well as at the mesoscale in engineered nanomaterials. In this SEED program we recently showed that engineered light beams couple to nanoparticle resonances that were previously thought to be invisible. Our investigations focus on spherical nanoparticles. With MRSEC support, we fabricate spherical nanoparticles out of a variety of materials, in this case silicon, using high power femtosecond lasers. The laser is focused onto the surface of the semiconductor. The laser light is absorbed, ejecting molten material from the surface that subsequently adopts a spherical shape as it cools. These silicon nanoparticles support a diversity of interesting optical resonances. For instance, with a conventional linearly or circularly polarized light beam we may couple to the “bright” mode shown in figure 18, on the left. This particular resonance exhibits a 4-fold symmetric radiation pattern. To the right in figure 18 is the radiation pattern of a “dark” mode that cannot be accessed with conventional light sources but can be observed by other experimental techniques that employ electron beams. We recently showed that such dark modes are not in fact invisible, but can be excited by suitably engineered light beams.

Fig. 18. Radiation patterns of optical resonances in a spherical silicon nanoparticle. The bright mode on the left can be accessed with conventional light sources. The dark mode on the right is typically thought to be invisible. We have shown that one can couple to this mode with suitably engineered light beams.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Seed Project: Bio-Inspired Routes to Structured Biphasic Materials via Colloidal Assembly of Nanoemulsions

Participants: Matthew Helgeson (PI); Tuan Nguyen (Ph.D. student)

The goal of this project is to investigate the bio-mimetic

colloidal assembly of thermoresponsive nanoemulsions into biphasic structures, and to use these structures as soft liquid templates for hierarchically porous materials. In the previous reporting period, we developed a mechanistic understanding by which the template structure – a hierarchical colloidal gel network possessing a phase separated superstructure – forms through elastically-driven spinodal decomposition and comes to arrest through macroscopic gelation. The work has appeared in Soft Matter (DOI:10.1039/C5SM00851D). We further developed protocols by which the arrested nanoemulsion assemblies can be used to template polymer hydrogels with enhanced porosity and mechanical properties. If this colloidal assembly and templating process is to be used to template a range of materials, then a key control variable of assembly process is its kinetics, i.e. the time scale for formation and arrest of the droplet superstructure. For material templating, this time scale must be fast relative to the rates of material reaction chemistry performed within them. In the current reporting period, we therefore examined our ability to control the kinetics of the colloidal structuring using control parameters for their thermal processing, i.e. the rate and depth of quenching into the spinodal region of the colloidal phase diagram [figure 19(a)]. Using a combination of microscopy and rheometry, we found that the macroscopic gel point (i.e. when G’ = G” in a kinetic gelation

experiment) was closely associated with the time scale for Fig. 19. (a) Colloidal phase diagram for arrest of the assembled structure. We then used rheological thermoresponsive nanoemulsions. Line measurements to parametrically study, for a range of depicts characterstic thermal quenches to colloidal volume fraction ⎞, how this characteristic time various depths. (b) Rheo-kinetics of scale depends on the depth and rate of quenching to a final gelation at various applied temperature temperature in the spinodal boundary [figure 19(b)]. We quenches. Black circles indicate the gel find that the gel time varies by several orders of magnitude point. (c) Representative variation of the depending on the quenching conditions, scales gel time on (c) quench rate and (d) logarithmically with the quench rate [figure 19(c)], and quench depth relative to the spinodal scales exponentially with the quench depth [figure 19(d)]). These results give insight into the fundamental boundary for ⎞ = 0.33. thermodynamic driving forces for gelation and arrest, as well as design rules for tuning the kinetics of nanodroplet assembly.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Super Seed Project: Polymerized Ionic Liquids: Tuning Functionality via Ionic Liquid Chemistry

Participants: Rachel A. Segalman (PI), Gabriel E. Sanoja (Graduate Student), Christopher M. Evans (Post-doctoral Fellow), Matthew E. Helgeson (Collaborator) Polymerized ionic liquids (PILs) are novel materials with properties dictated by the chemistry of the cation and anion comprising the ionic liquid moieties. As such, they constitute a powerful platform for functional materials that respond to external stimuli such as electric and magnetic fields. PILs promise the processability and tunability characteristic of polymers, but with functionalities ranging from multi-valent ion conductivity, mixed ion/electron conductivity, and magnetism. PILs based on carbon-linked imidazole moieties are promising proton- conducting membranes for electrochemical devices operating in anhydrous and aqueous conditions. We have investigated block copolymers block based on poly(styrene-block-ionic liquids) (PS-b-PIL) because each block can be separately designed to provide complementary mechanical and ion transport properties. The block Fig. 19. PILs have the Fig. 20. Paramagnetic PIL copolymers self-assemble into lamellar ability to conduct block copolymer. The ionic nanostructures with domain spacing multivalent ions. These aggregates within the PIL ranging from 10 to 70 nm which confines conducting materials are domain introduce sufficient the ions to the PIL domain. Depending on all formed from a structural anisotropy to the block copolymer composition, the poly(imidazole) overcome thermal motion and anhydrous conductivity can be tuned to be derivative complexed induce magnetization in the higher than that of the corresponding PIL with the appropriate presence of a magnet. homopolymer which is an example of the TFSI-based salt. role of confinement on engineering bulk material properties (Macromolecules, DOI: 10.1021/acs.macromol.5b02202). When hydrated, the block copolymers show a substantially lower water uptake than Nafion, making the materials promising for water electrolysis devices. Ion-conducting polymers have been traditionally designed for solid-state electrolytes in lithium batteries or proton-conducting membranes for fuel cells and water electrolysis devices. However, the well- known complexation between metal cations and neutral imidazole units on a polymer backbone is advantageous for the design of novel materials that conduct multivalent ions. Upon addition of various salts containing bis(trifluoromethane sulfonyl)imide (TFSI-) anion, the imidazole complexes with the metal cation leading to salt dissociation and conductivity (figure 20). In addition to conductivity, these PILs also exhibit excellent mechanical properties due to the formation of ionic crosslinks. The results demonstrated herein illustrate design rules for the development of novel materials with tunable conductivity and modulus. PILs have historically been envisioned as conducting polymers. The design of materials based on PILs with novel functionality requires incorporation of ions with properties beyond ionic conductivity, high dielectric constant, thermal and – electrochemical stability. We have recently synthesized a PIL based on paramagnetic FeCl4 anion. This material responds to an external magnetic field of 0.55 T generated by a neodymium magnet (figure 21). The paramagnetic nature of this polymer is intriguing for patterning applications such as lithography, and photonic crystals, as it can be aligned under relatively low magnetic fields compared to their liquid crystalline diamagnetic counterparts.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Seed Project: Terahertz Protonics

Participants: Mark Sherwin (PI)

During the reporting period, we have worked on three topics with MRSEC SEED funding. 1. Water-Based THz Absorber: Current commercially available THz absorbers offering more than 20 dB return loss are bulky, made of proprietary materials, and intrinsically broadband. This 240 GHz absorber consists of a precisely machined thin layer of PMMA (plexiglas) placed over a small volume of water. By diluting the water with glycerol, the effective refractive index of the back medium may be adjusted finely to maximize return loss. The resonant frequency of the absorber is tuned with the PMMA thickness. Reflectometry measurements of the absorber with a vector network analyzer (VNA)-based terahertz spectrometer show a peak return loss of over 47 dB at 240 GHz and an overall peak return loss between 230 and 250 GHz of over 60 dB. Preliminary calculations suggest that such absorbers can be designed to be effective over much of the sub-THz band. In addition, the absorber is highly sensitive to the refractive index of the back medium, suggesting this type of absorber can be used to track minute changes in the dielectric properties of aqueous solutions. (See: M.L.P. Bailey, A.T. Pierce, A.J. Simon, D.T. Edwards, G.J. Ramian, N.I. Agladze, M.S. Sherwin, “Narrow-band water-based absorber with high return loss for terahertz spectroscopy,” IEEE Transactions on THz Science Technology, DOI: 10.1109/TTHZ.2015.2477609). The two principal authors who contributed equally to this paper--Andrew Pierce and Mary Lou Bailey-- were both undergraduates. Andrew is now pursuing a Ph.D. in Physics at Harvard in the group of Amir Yacoby. Mary Lou is pursuing a Ph.D. in Applied Physics at Yale, and won a 2016 NSF Graduate Research Fellowship. 2. Optically-Detected THz Harmonic Generation from Electronic Materials: (Graduate student researcher Darren Valovcin (Physics, advisor Sherwin) and Mihir Pendharkar (Materials, advisor Palmstrøm). The nonlinear properties of electronic materials at THz frequencies are increasingly important to understand as high-frequency electronics extends well-above 100 GHz. The UCSB FELs are a powerful source for such experiments. However, the existing state of the art makes it challenging to detect and analyze harmonics directly in the THz frequency range. With funds from the Seed, we have begun studies aimed at optically-detecting harmonics generated by intense THz pulses. The idea is to place a material that generates harmonics directly in contact with a nonlinear crystal that can, when illuminated with a near-IR laser, upconvert the harmonics into the near-IR, where they are much easier to detect. Calculations have been performed indicating this is a promising approach, and a heavily-doped GaAs layer has been grown on a 110 GaAs substrate that is suitable for upconversion. Preliminary upconversion experiments have been performed. 3. 240 GHz FEL-Powered Pulsed EPR of the Kölsch Radical: (Physics Graduate student researcher Blake Wilson (Sherwin and Han) and Prof. Fred Wudl). Magnetic resonance is usually performed in the limit of very small magnetic polarization. However, in samples with high concentrations of spins at high magnetic fields, the magnetization of the sample can significantly influence the spin dynamics. We have measured the frequency of the free-induction decay of single crystals of the Kölsch radical after powerful pulses of 240 GHz radiation from the UCSB mm-wave free-electron laser. The Kölsch radical is a Heisenberg antiferromagnet with a Néel temperature of 1.6 K. We find that the frequency of the free- induction decay depends on the tip angle of the spins, even at room temperature. The magnitude of the shift depends on the geometry of the sample. The shift arises from the interaction of the spins in the sample with the demagnetization field, which changes with tip angle. The dependence of this effect on geometry opens up the possibility to study the transfer of coherence from the long-wavelength collective mode that is directly excited by the THz radiation to the internal degrees of freedom of various types of paramagnetic materials.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

6. EDUCATION AND HUMAN RESOURCES

(a) Current Activities

MRL education staff and researchers are dedicated to improving access to science for diverse groups and to building a competent work force of scientists and engineers. Our education programs provide undergraduate research opportunities, graduate student training, outreach to K-12 students and teachers, and community outreach.

MRL UNDERGRADUATE RESEARCH PROGRAMS

MRL Education Programs currently run five undergraduate research intern programs including Research Interns in Science and Engineering (RISE), UCSB PREM with Jackson State University, UCSB PREM with University of Texas at El Paso, California Alliance for Minority Participation (CAMP) and Cooperative International Science and Engineering Internships (CISEI). CAMP, CISEI, and PREM leverage funding from other NSF awards and are not described in detail here. CAMP and CISEI students and project titles are listed on our website at http://www.mrl.ucsb.edu/education/undergraduate-opportunities. PREM is run concurrently with the RISE program and student projects are included with RISE.

Research Interns in Science and Engineering (RISE) and PREM

The MRL RISE program supports laboratory research experiences for undergraduate students in science and engineering. This program has two major components, a summer program and a school-year program. In both components students are placed in research laboratories and assigned a personal mentor, usually a graduate student or postdoctoral researcher. Students also participate in weekly RISE group meetings, practice giving oral presentations on their research, and produce final written and oral reports. Students in the summer program also attend a weekly seminar series and career building workshops, including research ethics training and laboratory safety training. All interns participate in a final Summer Undergraduate Research Colloquium (poster session) with undergraduates on campus from many different summer research programs in the sciences, social sciences, and humanities.

Summer RISE ran from June 15 to August 21, 2015. 21 students participated fully in the RISE program, of which 10 were funded partially or wholly by the MRSEC (2 on the REU Site grant). In addition to center funding, RISE also leveraged funding from the UCSB College of Engineering, the UCSB/JSU PREM and the UCSB/UTEP PREM. Students were recruited nationally and selected with a particular focus on women, underrepresented minority students, first-generation college goers, and students from non-Ph.D. granting and other non-UCSB colleges and universities. The participating interns came from 12 different colleges and universities. In this cycle we supported 41 UCSB undergraduate research interns through the school-year RISE program. Interns were included on numerous refereed publications in this cycle (listed below). RISE research project information can be found at: http://www.mrl.ucsb.edu/education/undergrad/flam.

Demographics for the summer RISE program are provided below: Summer RISE Interns 2014 (includes PREM) No. of Interns Percent of Total Total 21 Female 12 57% Under-rep. minority 10 48% 1st generation college 7 33% Non Ph.D.-granting Institutions 4 19% Non-UCSB students 16 76%

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Undergraduate Career Development Programs

As part of our continued effort to provide career development and support for undergraduates at UCSB, we have initiated a variety of professional development seminars and workshops that we present throughout the year:

Activity Terms # Participants Peer Study Group Spring, Fall, Winter 94 Applying for Internships Winter 12 Graduate Student Panel and Workshop Summer, Fall 65 Applying for the NSF GRF Fall >60 LinkedIn Workshop Summer 50 Figures for Presentations Workshop Summer 50 Research Ethics Workshop Summer 50 Poster Presentation Workshop Summer 50 Writing an Abstract Workshop Summer 50 Oral Presentation Workshop Summer 50

MRL TEACHER PROGRAMS

Research Experience for Teachers (RET)

The RET program is modeled on undergraduate research programs and serves local secondary science teachers. Summer 2015 marked the program’s seventeenth year. Teacher participants work in a research laboratory with a mentor for six weeks. They attend weekly group meetings where they share details of their research through structured presentations. They also attend the weekly summer seminars and do a final oral presentation on their projects, an event to which their mentors are also invited. Unlike the undergraduate programs, the RET program is a two-year commitment. During the school year after the research experience, program staff meet with the teachers at least twice to guide them in considering how some aspect of their research experiences might be integrated into their instructional programs. During a second summer, the teachers return to UCSB for four weeks in order to design lessons or units reflecting this instructional integration. They then test their lessons during the subsequent school year. The culminating event for the RET teachers is an annual March workshop where they present their projects to secondary teachers from the two-county area. This workshop has also been an effective mechanism for recruiting new teachers for the next summer’s cohort. Teachers are recruited from middle and high schools in Santa Barbara, Ventura and Los Angeles Counties. Preference is given to teachers from low-performing schools and those without prior research experience. 2015 Outcomes During Summer 2015, four RET I teachers were funded by the MRL to pursue research projects. Two teachers developed lesson plans under RET II and will present them at the March 11, 2016 MRL Secondary Curriculum Workshop. Over 70 local science teachers are registered to attend. All RET lesson plans and curriculum materials are available online on the MRL website (http://www.mrl.ucsb.edu/RET). As of 2016, 65 curriculum projects are archived. A 2008 survey of RET alumni indicates that 80% of the projects are still in use, indicating a lasting impact on teaching methods.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

INFORMAL K-12 EDUCATION

UCSB ScienceLine

ScienceLine is an internet-based question and answer service that connects MRL researchers with K-12 schools. Students and teachers submit questions online and receive a response from one or more scientific researchers within a week. All the questions and responses are entered into a searchable online archive, which itself is a useful curriculum supplement for science teachers. An outgrowth of ScienceLine includes video interviews, answers and presentations, and YouTube-style videos on topics in Materials Science (http://www.mrl.ucsb.edu/education/resources-teachers). In 2015 we received 656 questions bringing the total archived questions and answers to 5308. ScienceLine is designed to primarily serve local schools and teachers; in 2015 students from over 120 different California schools submitted questions. Overall, questions were received from almost 600 different schools, both US and international (not all users specify their school). In 2015, 69 UCSB scientists, including faculty, postdocs, graduate students, undergraduates and alumni participated by answering questions. 19 of the participating scientists were from the UCSB MRSEC.

It’s a Material World

In spring 2006 the MRL introduced a set of hands-on exhibits of new materials designed for presentation to K-6 students and their families in an informal setting. In 2015, we presented It’s a Material World at Family Science Nights at sixteen local elementary to over 2000 students and their families. It’s a Material World was presented by 68 MRL graduate student, postdoc and faculty volunteers.

Build your Own Buckyball Workshops

In 2007 MRL Co-Director Ram Seshadri and Education Director Dorothy Pak received a Faculty Outreach Grant to update and extend our popular presentation centered on a Carbon-60 molecular model kit. MRL Education Staff and graduate students regularly present a Carbon-60 molecular model kit designed to teach K-12 students about nanoscience, chemical bonding and the relationship between structure and properties in materials. In 2015 we presented the activity to over 200 middle and high school students, assisted by 30 graduate student, post doc and faculty volunteers.

Solar Car Workshops

In 2011 MRL Co-Director Ram Seshadri and Education Director Dorothy Pak received a FOG grant to develop a new hands-on workshop on alternative energy and photovoltaics. 288 middle and high school students and their families participated in the workshop, assisted by 29 graduate student, post doc and faculty volunteers. In particular, we partner with the UCSB Office of Education Partnerships to present the workshop to students from UCSB partner schools with high minority enrollments and low college- going rates, including the Kern County Migrant Education program and the MESA Science and Technology Day, which brings over 1000 underrepresented minority middle school students to campus in February. We also partnered with Johns Hopkins University’s Center for Talented Youth to bring the solar car workshop to 75 students and their parents at a day-long science workshop at UCSB.

Art and Energy

In 2015, MRL Co-Director Ram Seshadri, Education Director Dotti Pak and UCSB Art Professor Kim Yasuda received a grant from the UC Academic Senate Pearl Chase Foundation to present interdisciplinary energy and art curriculum to local 4th grade students using neighborhood maps and drawable circuits to create a light installation. The art/science activity focuses on spatial awareness and 33

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

the fourth grade energy curriculum. In February 2016 we presented the new curriculum to 60 4th graders at Isla Vista Elementary School. The students also participated in Prof. Robert Tai’s (U. Va.) NSF PRIME project to assess student engagement through activity-based programs.

LISTS OF EDUCATION PROGRAM REU AND RET PROJECTS MARCH 2015-FEBRUARY 2016

RISE (includes UTEP and JSU PREM and REU site) Summer 2015

Michael A. Abramovitch, University of California, Santa Barbara, Mentor: Maksymilian Nowak; PI: Matthew E. Helgeson, “Designing poly(Ethylene-Glycol) diacrylate hydrogels with controlled pH- responsive swelling.”

Omar Barreda, University of Texas at El Paso, Mentor: Hayden Evans; PI: Ram Seshadri, “Preparation and characterization of hybrid perovskite related structures.”

Paige Chardavoyne, Williams College, Mentor: Dave Fisher; PI: Javier Read de Alaniz, “Formation of carbon-nitrogen bonds through radical processes.”

Chelsea Chaves, Jackson State University, Mentor: Tracy Chuong; PI: Galen Stucky, “Surface-enhanced Raman spectroscopy based false-free biomolecular assay.”

Madeline Dippel, University of California, Santa Barbara, Mentors: Jason Van Sluytman, Wesley Jackson; PI: Carlos Levi, “Development of molten silicate resistant overlayer for rare-earth tantalate thermal barrier coatings.”

Ivan Gastelum, University of Texas at El Paso, Mentors: Yair Kaufman, Sandy Chen, Nans Viel; PI: Jacob Israelachvili, “Wettability of silica: Effect of contamination.”

Marisa E. Gliege, Washington State University, Mentors: Paula Malo de Molina, Juntae Kim; PI: Matthew E. Helgeson, “Self-assembly of nanodroplets using stimuli responsive polymers.”

Christian Gomez, University of California, Santa Barbara, Mentor: Emily Davidson; PI: Rachel Segalman, “Strategy for the chain alignment of poly(3-(2’-ethyl)hexylthiophene) (P3EHT) and its effect on charge transport.”

Gabrielle Hammersley, University of California, Santa Barbara, Mentor: Andrey Samoshin; PI: Javier Read de Alaniz, “Radical tryptamine dimerization through nitroso linker.”

Griselda Hernandez, University of Texas, El Paso, Mentor: Les Burnett; PI: Javier Read de Alaniz, “Nitroso mediated radical coupling reaction for the introduction of amines into organic molecules.”

Mikaela Kosich, Harvey Mudd, Mentor: Elizabeth A. Pedrick; PI: Trevor W. Hayton, “Toward synthesis 2+ of novel uranyl ([UO2] ) hydride complexes.”

Chia-In Jane Lin, University of California, Santa Barbara, Mentor: Robert Pantazes; PI: Patrick Daugherty, “Opening our eyes: Using patient antibodies as biomarkers to detect narcolepsy.”

Chloe Lins, University of South Carolina, Mentor: Santosh Raghavan; PI: Susanne Stemmer, “MBE- grown single phase perovskites.”

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Francesca Long, University of Wisconsin-Madison, Mentor: Jason Douglas; PI: Ram Seshadri, “Improving efficiency in half-Heusler thermoelectrics by lowering thermal conductivity.”

Gabriel A. Lopez, University of Texas, El Paso, Mentors: Erin Perry, John Labram; PI: Michael Chabinyc, “Thin film growth of methylammonium lead thiocynite iodine via spin-casting.”

Miles Markmann, California Polytechnic State University, San Luis Obispo, Mentor: Revital Kaminker; PI: Craig J. Hawker, “Evolution of peptoid monomers.”

Eric Rappeport, Oberlin College, Mentor: Christopher Freeze; PI: Susanne Stemmer, “Optimization of sputtered platinum substrate growth for a barium-strontium-titanate capacitor.”

Alex Selimov, University of Central Florida, Mentor: Victoria Miller; PI: Tresa Pollock, “Characterization of intermetallic particles in magnesium-zinc alloys.”

Alexia Thomas, Jackson State University, Mentor: Jake Berenbeim; PI: Mattanjah de Vries, “Laser mass spectrometry analysis of wine trace markers in archeological vessels.”

Natalie White, Jackson State University, Mentor: Malinda Buffon; PI: Ram Seshadri, “Exploration of TiFe2Sn1–xSbx for thermoelectric applications.”

Chris Zollner, Cornell University, Mentor: Thomas Hogan; PI: Stephen Wilson, “Solid-state synthesis of Nd2Ir2O7 and investigation of novel ground states.”

RISE School Year Participants Spring 2015, Fall 2015 and Winter 2016

Michael Abramovitch, UCSB, Mentor: Max Nowak; PI: Matt Helgeson, “Designing poly(ethylene glycol) diacrylate nano-hydrogels with controlled pH-responsive swelling.”

Samuel Alcantar, UCSB, Mentor: Jose Navarrete; PI: Martin Moskovits, “Developing conductive NiO thin film transistors for catalytic applications.”

Grant Antalek, UCSB, Mentor: Emmanouela Filippidi; PI: Herbert Waite, “Imaging mussel plague formation.”

Adam Arce, UCSB, Mentor and PI: Chen Ji, “Systemic investigation of the relations among source parameters for earthquakes at intermediate depths.”

Bryan Argueta, UCSB, Mentor: Eileen Hamilton; PI: Eduardo Orias, “Investigating chromosome rearrangements facilitated by transcription induced DNA breaks in Tetrahymena thermophile.”

Talia Barth, UCSB, Mentor: David Poerschke; PI: Carlos Levi, “Dynamics of reactions between thermal barrier coatings and silicate melts.”

Michonne Behin, UCSB, Mentor: James Broadway; PI: Jonathan Schooler, “Electroencephalogram (EEG) of intelligence and mind-wandering.”

Rohit Bhatt, UCSB, Mentor: Vinu Krishnan; PI: Samir Mitrogotri, “Addition of CD33 antibody onto nanocrystals via conjugation chemistry.”

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Colton Bracken, UCSB, Mentor: Rob Levenson; PI: Dan Morse, “Characterizing the assembly of reflectin proteins, the drivers of tunable biophotonics.”

Robert Casper, UCSB, Mentor: Justin Iveland; PI: Jim Speck, “Method of treatment to reduce surface contamination of p-Type gallium nitride semiconductors for negative electron affinity photocathodes.”

Amanda Chron, UCSB, Mentor: Dean Morales; PI: Norbert Reich, “Spatially and temporally controlled Cre-Lox genomic editing.”

Daniel Chu, UCSB, Mentor and PI: Irene Chen, “The microbial metagenome of wound ulcers.”

Deborah Clayton-Warwick, UCSB, Mentor: Lourdes Velazquez; PI: Deborah Fygenson, “Use of nunchuck nanostructures for dynamic DSDNA bend angle measurements by fluorescence microscopy.”

Andrew Dawson, UCSB, Mentor: Ches Upham; PI: Horia Metiu, “Halogen mediated oxidative dehydrogenation to make polyethylene into carbon fiber.”

Joshua De Oliveira, UCSB, Mentor: Stefano Menegatti; PI: Samir Mitragotri, “Development of a novel multi-drug conjugate with synergistic anti-cancer activity.”

Abel Fernandez, UCSB, Mentor: Chandra McCauley; PI: Carlos Levi, “Investigation of the tantala-yttria binary phase diagram.”

Christian Gomez, UCSB, Mentor: Emily Davidson; PI: Rachel Segalman, “Strategy for the chain alignment of poly(3-(2’-ethyl)hexylthiophene) (P3EHT) and its effect on charge transport.”

Austin Graham, UCSB, Mentor: Joel Bozekowski; PI: Patrick Daugherty, “Antibody repertoire analysis in bipolar disorder.”

Gabrielle Hammersley, UCSB, Mentor: Andrey Samoshin; PI: Javier de Alaniz, “Synthesis of hindered amines: Copper-mediated radical addition of nitoros compounds.”

Adolfo Hernandez, UCSB, Mentor: Dana Morton; PI: Armand Kuris, “Diverse parasites of the senorita wrasse (Oxyjulis californica) in the Santa Barbara kelp forests.”

Laura Hernandez, UCSB, Mentor: Bruce Braaten; PI: David Low, “Hunt for genes regulated by contact- dependent growth inhibition systems.”

Andy Hsueh, UCSB, Mentor: Kaila Mattson; PI: Craig Hawker, “Light mediated polymer chain end removal.”

Stephanie Landeros, UCSB, Mentor: Geoff Lewis; PI: Stephen Fisher, “Effects of human retinal progenitor cells of glial and immune cell reactivity in the RCS rat.”

Chia-In Jane Lin, UCSB, Mentor: Robert Pantazes; PI: Patrick Daugherty, “In vitro directed evolution of narcolepsy-specific peptide motifs improve patient sensitivity and specificity.”

Joseph Mann, UCSB, Mentor: Nicholas Treat; PI: Craig Hawker, “Novel catalyst design for light mediated ATRP.”

Marine Minasyan, UCSB, Mentor: Ramsey Majzoub; PI: Cyrus Safinya, “Lipid synthesis.” 36

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Bridget Naughton, UCSB, Mentor and PI: Norbert Reich, “The evolutionary lineage and mechanism of processing of bacteriophage T4 DNA-(N6-adenine)-methyltransferase.”

Thomas Nguyen, UCSB, Mentor and PI: Irene Chen, “Aptamer effects on aggregation kinetics of recombinant human α-syn.”

Christopher Nyambura, UCSB, Mentor: Arash Nowbahar; PI: Todd Squires, “SDS with multivarient cations in water.”

Nicholas Parker, UCSB, Mentor: Brian Evanko; PI: Galen Stucky, “Electrode processing for high energy density supercapacitors.”

Navaneet Ramabadran, UCSB, Mentor Arash Nowbahar; PI: Todd Squires, “A proposal to study and visualize the dynamics of Langmuir lunch surfactant monolayer mixing.”

Christopher Reetz, UCSB, Mentor and PI: Ania Jayich, “Magnetic sensing utilizing nitrogen vacancy centers in diamond.”

David Arias Roldan, UCSB, Mentor: Lourdes Velazquez; PI: Deborah Fygenson, “Quantification of DNA origami purity and concentration within solution.”

Monica Romelczyk, UCSB, Mentor: Brian Evanko; PI: Martin Moskovits, “Redox-enhanced electrochemical capacitors.”

Antonia Sowunmi, UCSB, Mentor: Sara Weinstein; PI: Armand Kuris, “Low temperature tolerance of Ascaris suum eggs.”

Blake Toro, UCSB, Mentor: Caitlan Fong; PI: Armand Kuris, “Relative sizes of parasitic castrator, Ortunion conformis, and its shore crab host.”

Anthony Tran, UCSB, Mentor: Megan Chui; PI: Peter Ford, “Changing the selectivity of CuPMO via co- catalyst.”

Vishaal Varahamurthy, UCSB, Mentor: Daniel Becerra; PI: Steven DenBaars, “Optimization of metal contacts on n-GaN.”

Jessica Wong, UCSB, Mentor; Amrita Banerjee; PI: Samir Mitragotri, “Engineering the shape of anaoparticles for improved oral drug delivery and transport.”

Anna Wu, UCSB, Mentor: Chirag Gupta; PI: Pradeep Sen, “High voltage epitaxial characterization.”

Daniel Yur, UCSB, Mentor: Susanna Seppala; PI: Michelle O’Malley, “Characterization of anaerobic gut fungal membrane proteins by heterologous production in Saccharomyces cerevisiae.”

RET 1 & 2 2015

Lauren Galvin, Santa Barbara High School, Mentor: Victoria Steffe; Faculty Supervisor: Cyrus Safinya, “Optimizing a lipid nanocarrier for efficient loading and delivery of a hydrophobic drug: Paclitaxel.”

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Adam Gamboa, Channel Islands High School, Mentor: Daniel Hirche; Faculty Supervisor: Mike Gordon, “Vanadium nanoparticle catalysis.”

Teresa Leza, Villanova Preparatory School, “Proteins: Making bio-inspired connections.”

Jonathon McCabe, Channel Islands High School, “The power of water: How moving water affects our physical world.”

Zachary Moore, Laguna Blanca School, Mentor: Arash Nowbahar, Faculty Supervisor: Todd Squires, “Interfacial polymerization for water treatment membranes.”

Rano Sidhu, Rio Mesa High School, Mentor: Tracy Chuong, Faculty Supervisor: Galen Stucky, “SERS based false-free biomolecular assay.”

(b) Evaluation and Impact of Education and Outreach Activities

Education program staff members are committed to evaluating our programs to assess their impact and effectiveness. Formative assessment is conducted as part of each program, in the form of participant surveys, interviews, and collection of demographic data. In January 2010 the UCSB MRL was selected to participate in Cohort 2 of the CORE (Cornell Office of Research on Evaluation) Netway evaluation project. As part of this project, Education Director Dorothy Pak and Coordinator Julie Standish have been trained in the use of the Netway software, participated in three intensive evaluation training workshops, and developed a comprehensive evaluation plan for the ScienceLine program. We have also been active in promoting cross-site assessment of MRSEC Education programs, including adoption of the URSSA evaluation instrument for our REU programs, long-term involvement in RETNetwork evaluation and support of Prof. Robert Tai’s (University of Virginia) NSF PRIME grant to develop instruments for cross-site assessment of informal science programs. Data was collected from the pilot Art and Energy program at Isla Vista Elementary using Tai’s instrument and will be included in his dataset.

Undergraduate Publications (undergraduate in bold)

J. Areephong, K.M. Mattson, N.J. Treat, S.O. Poelma, J.W. Kramer, H.A. Sprafke, A.A. Latimer, J.R. de Alaniz, C.J. Hawker, “Triazine-mediated controlled radical polymerization: new unimolecular initiators,” Polymer Chem. 7 (2016) 370-374.

M.L.P. Bailey, A.T. Pierce, A.J. Simon, D.T. Edwards, G.J. Ramian, N.I. Agladze, M.S. Sherwin, “Narrow-band water-based absorber with high return loss for terahertz spectroscopy,” IEEE Trans. on Terahertz Sci. and Tech. 5 (2015) 961-966.

S.L. Fronk, C.K. Mai, M. Ford, R.P. Noland, G.C. Bazan, “End-group-mediated aggregation of poly(3- hexylthiophene),” Macromolecules 48 (2015) 6224-6232.

J.K. Harada, L. Balhorn, J. Hazi, M.C. Kemei, R. Seshadri, “Magnetodielectric coupling in the ilmenites MTiO3 (M = Co, Ni),” Phys. Rev. B 93 (2016) 104404(1–6).

A.J. Lehner, D.H. Fabini, H.A. Evans, C.A. Hebert, S.R. Smock, J. Hu, H.B. Wang, J.W. Zwanziger, M.L. Chabinyc, R. Seshadri, “Crystal and electronic structures of complex bismuth iodides A3Bi2I9 (A = K, Rb, Cs) related to perovskite: Aiding the rational design of photovoltaics,” Chem. Mater. 27 (2015) 7137-7148.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

A.Pavlova, C.Y. Cheng, M. Kinnebrew, J. Lew, F.W. Dahlquist, S. Han, “Protein structural and surface water rearrangement constitute major events in the earliest aggregation stages of tau,” Proc. of the National Academy of Sciences USA 113 (2016) E127-E136.

K.A. See, S. Hug, K. Schwinghammer, M.A. Lumley, Y.H. Zheng, J.M. Nolt, G.D. Stucky, F. Wudl, B.V. Lotsch, R. Seshadri, “Lithium charge storage mechanisms of cross-linked triazine networks and their porous carbon derivatives,” Chem. Mater. 27 (2015) 3821-3829.

Intern Presentations at National Meetings

Sebastian Arias – SASE National Conference, Houston, TX, October 8-10, 2015.

Stephanie Landeros, “Effects of human retinal progenitor cells on glial and immune cell reactivity in the RCS rat,” SACNAS conference, Washington DC, October 29-31, 2015. Poster won the Association for Research in Vision and Ophthalmology (ARVO)/SACNAS Eye and Vision Award

Ricardo Vidrio, “Growth of novel two dimensional transition metal dichalcogenides,” SACNAS conference, Washington DC, October 29-31, 2015.

Maribel Lopez, “Effects of double infections on parasitic flatworm reproductive castes,” SACNAS conference, Washington DC, October 29-31, 2015.

Antonia Sowunmi, “Low temperature tolerance of ascaris suum eggs,” SACNAS conference, Washington DC, October 29-31, 2015.

Adolfo Hernandez, “Diverse parasites of the senorita wrasse (Oxyjulis californica) in the Santa Barbara kelp forests,” Western Society of Naturalists, Sacramento, CA, November 5-8, 2015.

Michael Abramovitch, “Designing poly(ethylene glycol) diacrylate hydrogels with controlled pH- responsive swelling,” AIChE Annual Student Conference in Salt Lake City, November 6-9, 2015. Poster won second place in the "Materials Engineering and Sciences VII" category of the Undergraduate Student Poster Competition

Sean Garner, AIChE Annual Student Conference in Salt Lake City, November 6-9, 2015.

Juan Camilo Castillo, SHPE Conference, Baltimore, MD, November 11-15, 2015.

Lorena Covarrubius, SHPE Conference, Baltimore, MD, November 11-15, 2015.

Jesus Vega, SHPE Conference, Baltimore, MD, November 11-15, 2015.

Uriel Ramos, SHPE Conference, Baltimore, MD, November 11-15, 2015.

Leslie Lopez, SHPE Conference, Baltimore, MD, November 11-15, 2015.

Nilufar Karimi, SHPE Conference, Baltimore, MD, November 11-15, 2015.

Samuel Alcantar, “Electrical characterization of ultra-thin conductive oxide films,” STEM National Conference, Pittsburg, PA, November 13-15, 2015.

Raudel Covarrubius, STEM National Conference, Pittsburgh, PA, November 13-15, 2015. 39

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Gabrielle Hammersley, “Synthesis of hindered amines: Copper-mediated radical addition of nitroso compounds,” Southern California Conference on Undergraduate Research, Harvey Mudd, College, Pomona, CA, November 21, 2015.

Thomas Nguyen, “Aptamer effects on aggregation kinetics of recombinant human α-synuclein,” Southern California Conference on Undergraduate Research, Harvey Mudd College, Pomona, CA, November 21, 2015.

Maribel Lopez, “Effects of double infections on parasitic flatworm reproductive castes,” The Wildlife Society Conference, Pomona, CA, February 22-26, 2016.

Monica Romelczyk, ARPA-E Energy Innovation Summit, Washington DC, February 29-March 2, 2016.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

7. POSTDOCTORAL MENTORING PLAN

The post-doctoral mentoring plan originally presented in the proposal has been evolved and refined. We have continued both stand-alone and partnered programs to guide post-doctoral researchers beyond their research in reaching their career goals, including for careers ranging from traditional ones in academia to founding start-up companies, of jobs in National Laboratories and established industry. We note that the activities and programs are not restricted to post-doctoral fellows and often times graduate students and campus visitors also profit from these. In the past year, we have continued to provide funds for every MRL-supported post-doctoral fellow to attend at least one major national conference (ACS/APS/MRS/Gordon Research Conference) every year, and in some cases, support for international conferences or workshops as well. The MRL also engages closely with post-doctoral scholars with respect to seminars speakers, faculty candidates and other visitors to campus, encouraging them to host meals, and even invite speakers of their choice. In addition, time is allocated in the schedule for each seminar visitor to the MRL to meet with a group of MRL post-doctoral scholars. By closely interacting with the speakers, the post-doctoral fellows are able to maximize their interactions with these world-class scientists, gaining additional insights into professional development and future contacts for their independent careers. Since the speakers are not only from academia and National Labs but also from industry and start-up companies, the exposure is to all kinds of careers. The annual Materials Research Outreach Program (described separately in Section 9) and the MRL-supported New Venture Competition run by UCSB’s Technology Management Program play a major role in the informal career-preparation of post-doctoral fellows. To complement these less-formal mentoring opportunities, numerous short (typically one to two hour) career-building workshops have been sponsored by the MRL and led by experts on campus and MRL faculty. For example, in March 2016 MRL sponsored a hands-on workshop designed for post-docs and graduate students on creating an effective CV and cover letter for industry, led by Dr. Leslie Edwards, UCSB Director of Corporate Business Development. A gratifying outcome of the workshops has been the large numbers of non-MRL attendees, who usually learn of the workshops by word of mouth, or through the UCSB Graduate Division. The student organization Graduate Students for Diversity in Science (described in Section 8) plays an important role in the organization and advertising of these activities. For instance, GSDS co-sponsored over 10 career talks this past year as part of the Professional Development Career Talks Series and included invited guest speakers with careers in industry, academia, and entrepreneurs. In May 2015, GSDS co-sponsored and helped plan the UCSB Beyond Academia Conference, a two-day campus-wide event to increase awareness of non-academic career options aimed at post-docs and graduate students in STEM and humanities fields. The impact that these workshops and career activities have across the campus would allow us to say that the MRL is the epicenter on the UCSB campus for mentoring post-doctoral fellows in meta-professional (“soft”) skills.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

8. CENTER DIVERSITY

In committing to bring the participation of women and under-represented minorities at all levels to genuinely reflect the population, the MRL’s diversity program is purposeful, intentional and evidence- based. We recognize the need to be adaptable to the rapidly changing demographic, while maintaining a strong commitment to training, educating, and mentoring the future scientific workforce. To accomplish this in both the short and long terms, we have continued to focus on and improve our flagship programs, while also leveraging resources to broaden our outreach activities. Strategic plan and metrics: Hispanic students now comprise 27% of the undergraduate student population at UCSB, which enabled UCSB to be designated for the first time as a Hispanic Serving Institution (HSI). UCSB is the first Association of American Universities (AAU) to reach this status and we are very proud of this achievement. Although this has been a campus-wide effort, the MRL plays a key role in the support and retention of underrepresented minority students that helped UCSB reach this important milestone. For example, a major focus of our K-12 efforts involve a predominantly Chicano/Latino population. For this group of students, which represents 67% of the students in Santa Barbara, our diversity aims include providing class modules and training for teachers. With targeted outreach through ScienceLine and in-school demonstrations, we serve more than 2600 students per/year. At the undergraduate level, the MRL partners with Jackson State University and the University of Texas, El Paso through the PREM program and maintains informal partnerships with California State Universities and Women’s colleges. In addition, the MRL coordinates the California Alliance for Minority Participation (CAMP) program at UCSB. Taken together, the MRL supports a community of diverse undergraduates through professional development activities including MRL study halls, career- building workshops, graduate student panels, financial support for the GREs and graduate school application fees. At the graduate student level, the MRL has continued to strengthen its commitment to diversity through a number of programs. This includes the Graduate Students for Diversity in Science (GSDS) program. GSDS members continue their collaboration/partnership/relationship with UCLA’s Organization for Cultural Diversity in Chemistry and UMass Amherst’s new diversity chapter to share best practices and diversity programs, and support ways to expand the presence of graduate student-led diversity groups at other universities. In addition, GSDS members organized several quarterly diversity talks as part of the DOW Foundation-supported Distinguished Lecture Series and included invited guests from academia and national laboratories. As part of their outreach efforts to the larger community, GSDS members led a hands-on material science workshop this past February as part of the MESA Science and Technology Day which brings 700+ underrepresented youth from surrounding counties to campus each year to support scientific literacy and encourage students to attend college. At the faculty level, a strong commitment to broaden our outreach efforts were achieved through faculty-led symposiums and diversity activities. As one example, Shea and Read de Alaniz led an innovative 1-day program with local soccer youth clubs aimed at converting athletic talent into academic success. Our commitment to assume leadership for a number of existing programs aimed at broadening participation at UCSB, and the development of new programs provides a strong foundation for achieving our diversity goal of full participation.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

9. KNOWLEDGE TRANSFER TO INDUSTRY AND OTHER SECTORS

This past year has seen the UCSB continuing its tradition of collaborating closely with industry, and inspiring and supporting a number of high-tech start-up companies in the local (California Central Coast) region to thrive. As in past years, the UCSB MRSEC recognizes that it can play a huge role in training the many excellent graduate students and post-doctoral fellows for industrial positions while also exposing them to an international environment and collaborations. In addition, the MRSEC is a well-spring of job creation. The collaborative spirit and the emphasis on lasting infrastructure-building has led to the continued support of two major industry-academia partnerships thriving under the MRSEC umbrella: The Mitsubishi Chemical Center for Advanced Materials (MC-CAM) and the Dow Materials Institute (DowMI). Together these centers contribute over $3,000,000 in funding and support over 30 graduate student and post-doctoral scholars. In addition, the Complex Fluids Design Consortium (CFDC) brings together UCSB researchers and select faculty from other institutions with industry and national laboratory researchers interested in the computational design of soft materials and complex fluids. The CFDC, which had its annual meeting in February 2016 (just following the MROP described below), is setting the stage for two other consortia: on Soft Matter Interfaces, and on Materials for Advanced Ion Transport, that will have their inaugural meetings in September 2017, and that will seek to, in the manner of the CFDC, bring together researchers from UCSB and National Laboratories, with industrial partners.

Fig. 21. Goleta, California; the environs of UCSB Fig. 22. Milo, a start-up for sensing blood alcohol (marked by an arrow) manifests an unusually through the skin, and led by Materials graduate large entrepreneurial impact, despite its small size. student Bob Lansdorp (far left, with Netz Arroyo, From J. Guzman and S. Stern, “Where is Silicon Daniel Imberman, and Evan Strenk) were the big Valley? Forecasting and mapping entrepreneurial winners at the 16th annual New Venture quality,” Science, DOI: 10.1126/science.aaa0201 Competition that the UCSB MRSEC co-sponsors. Milo have already won NIH funding for their product. The UCSB MRSEC has continued its showcase activity for industry: The Materials Research Outreach Program (MROP). The two-day event was held in February, and attended by a number of industry (including local start-up) participants. Typical of our attempts to synergize various aspects of the MRSEC, the 2016 MROP was also attended by our faculty and students from our PREM partner institutions, Jackson State and the University of Texas at El Paso. Students from the latter institution also presented posters. Finally, the UCSB MRSEC tradition of creating and supporting start-ups and encouraging entrepreneurship and job creation in the Californa Central Coast region continues (figure 21). UCSB’s Technology Management Program runs the New Venture Competition every year, with partial support from the UCSB MRSEC and the Dow Materials Institute, and MRSEC students are frequently amongst the winners. This year was no exception, with Bob Lansdorp (figure 22), a graduate student of Omar Saleh, leading the winning entry.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

10. INTERNATIONAL ACTIVITIES

The UCSB MRSEC continues its engagement with a broad international community with interactions at every stake-holder level, starting with undergraduate internships (the CISEI and now FLAM REU programs), short graduate student and post-doctoral exchanges, scientific collaborations between faculty, and workshops with international partners. This past year, under the aegis of the Cooperative International Science and Engineering Internships (CISEI) Program, undergraduate interns were welcomed to the MRSEC from abroad, and MRSEC undergraduates themselves traveled to numerous foreign destinations to carry out research in the following universities: Chalmers, Fudan, Oxford, Saarbruecken, Trinity College, Dublin, and TU Eindhoven. CISEI students have displayed a very high propensity to go on to graduate (Ph.D.) programs and to win graduate fellowships such as the NSF GRF. Some examples from this past year have been Claire Hébert (UCSB Physics, CISE internship at Oxford) and Joseph Mann (UCSB Chemistry, CISEI internship at TU Eindhoven). Both Claire and Joseph have won NSF Graduate Research Fellowships and will start graduate school at Stanford in the Fall of 2016. CISEI fellowships are supported by the ICMR but the research, student training components, and the staffing are all under the control of the MRSEC. Since the ICMR (and NSF-IMI) has now come to an end, the new program that will serve the same role is an NSF REU site called FLAM, for Future Leaders in Advanced Materials. Two strong, key partners with whom workshops were run on the UCSB campus this year were Chalmers University in Gothenberg, Sweden, and the Korea Advanced Institute of Science and Technology (KAIST). The UCSB-Chalmers Workshop illustrates an example of a partnership that extends all the way from undergraduate exchanges to faculty visits (figure 23). Workshops with Chalmers have been held annually for the past 5 years, alternating between the two locations. The workshop with KAIST (figure 24) included participants from the Korea Atomic Energy Institute (KAERI) whose HANARO reactor source is currently being refurbished. It is anticipated that post-refurbishment, it will be available for use by all researchers from all three IRGs.

Fig. 23. Picture taken during the 2016 Materials and Fig. 24. Participants at the workshop: Neutrons for Processes for Energy and Chemical Conversion: 5th Advanced Materials: 2016 KAERI-KAIST-UCSB UCSB-Chalmers Workshop on Materials, University Workshop at UCSB. of California, Santa Barbara, with Chalmers and UCSB participants, including graduate students. Third from right is Caroline Jansson, who was an summer undergraduate intern in 2012 and is now in the Ph.D. program at Chalmers.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

11. SHARED EXPERIMENTAL AND COMPUTATIONAL FACILITIES

The Shared Experimental/Computational Facilities continue to be a KEY focus of the UCSB MRSEC, offering state-of-the-art materials instrumentation to a wide network of university and industry partners. Maintained and operated by highly qualified technical staff, these facilities continue to offer world-class instrumentation to users locally, nationally, and internationally for the advancement of materials science. In the past year, the MRSEC has specifically supported the expansion of the Materials Research Lab into over 2000 sq ft of additional lab space as the facility for low temperature materials characterization. This facility will house several new pieces of sophisticated instrumentation to add to our current capabilities. Specifically, both the Polymer and TEMPO facilities will benefit through the addition of a new liquid chromatography mass spectrometer (LCMS), high performance liquid chromatograph (HPLC) and a Dynacool 9 Tesla physical property measurement system (PPMS). This instrument will be cryogen-free, and represents one more step in our facilities efforts to decrease our reliance on scarce resources. These instruments will join complementary analytical techniques in near proximity to improve user accessibility. The new research space has been uniquely designed to increase our facilities’ engagement with the greater UCSB community. The exterior is primarily made of glass, thereby allowing passersby an intimate view of the inter-workings of a scientific research lab. Undergraduates will be both intrigued and inspired to gain exposure beyond the classroom and it is our hope to encourage the pursuit of the sciences, and potentially graduate studies, in offering such valuable exposure. An overview of all of the shared experimental facilities is provided below:

Facility Facility Technical Directors and Users Recharged Director Staff Hours (past year) Computation* Frank Brown Dr. Paul Weakliem 319 na Nathan Rogers Energy Michael Dr. Jeff Gerbec 20 na Chabinyc Dr. Rachel Behrens Microscopy Tresa Pollock Dr. Tom Mates 271 8,233 Dr. Stephan Kraemer Mark Cornish Polymer Craig Hawker Dr. Rachel Behrens 122 4,487 Spectroscopy Songi Han Dr. Jerry Hu 176 15,156 Jaya Nolt Shamon Walker TEMPO** Ram Seshadri Dr. Amanda Strom 170 11,933 Terahertz*** Mark Sherwin Dr. David Enyeart 23 1,101 X-Ray Cyrus Safinya Dr. Youli Li 216 7,643 Miguel Zepeda Philip Kohl Totals 1,026 40,320 * Partnered with the California NanoSystems Institute under the rubric Center for Scientific Computing ** TEMPO = Thermal Electronic/Elemental Magnetic Porosity, and Optical *** Partner facility run by the Institute for Terahertz Science and Technology

The technical capabilities of the Shared/Experimental Facilities have also significantly expanded to meet the needs of our wide user base. The Computational facilities added new servers to increase their server capacity by 75%. In addition to the aforementioned additions, the Microscopy facility installed an impressive nuclear magnetic resonance (NMR) spectrometer, the sensitivity of which will significantly expand the range of materials capable of testing while decreasing sample run time. Three other

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

instruments of note were also added; the Microscopy facility acquired a new scanning electron microscope (SEM), the TEMPO facility updated its thermogravimetric analyzer (TGA), and the X-ray facility obtained a new detector for macromolecular crystallography. The separate facilities reports follow.

Computation: The MRL’s Computational facility continues to be collocated and operated synergistically with the California NanoSystems Institute (CNSI) in the Center for Scientific Computing (CSC) (Directors: Prof. Frank Brown, Dr. Paul Weakliem, Nathan Rogers). The CSC serves over 300 users affiliated with over 30 research groups with additional short-term users from several computational courses. All of the CSC users are affiliated with UCSB. In the past year, to meet the growing needs of specialized GPU computations and leveraging supplemental funding from the Mitsubishi Chemical Center for Advanced Materials, the MRL purchased servers housing 12 NVIDIA K80 GPUs, thereby increasing GPU calculation throughput by 75%. IRG-1 will benefit from the additional GPU power for simulating complex co-acerbation of polyelectrolytes. Funding from CNSI allowed the CSC to purchase 9 Xeon Phi co-processors, adding another computational tool to HPC. Through the past year, all CSC cluster users have utilized more than 23 million hours of aggregate CPU time. Researchers associated with MRL professors Balents, Fredrickson, Pollock, Seshadri, Van de Walle, and Van der Ven are particularly heavy users of CSC resources, accounting for more than 13.5 million hours of aggregate CPU time. In October 2015, the CSC hosted the 2nd Southern California Simulations in Science Conference with over 100 participants from UCSB and 7 regional universities. The conference featured speakers from industry and Lawrence Berkeley National Lab, and focused on the use of computer simulations in industrial research and how students can best prepare for scientific computation in industry. In addition, the CSC continued its broad campus outreach by hosting workshops on XSEDE and SDSC resources available to researchers, and workshops and webinars on parallel programming and scripting. MRL computational facility manager, Nathan Rogers, along with Dr. Paul Weakliem of CNSI, are working with UCSB’s Office of Research on developing an alliance across all University of California campuses to provide an advanced cyber infrastructure for the sharing of resources and knowledge across all 10 UC campuses. Initial work culminated in the lighting up of the Pacific Research Platform at UCSB for 100GB/s connection capabilities to the other UCs.

Energy: The Energy Facility (Director: Prof. Michael Chabinyc; Lab Managers: Dr. Jeff Gerbec, Dr. Rachel Behrens) continues to expand and develop its capabilities for current and future users. We have acquired a new double wide inert atmosphere glove box for materials processing in the Energy Facility. The glove box includes a spin coater and basic processing equipment for novel solution processable semiconducting materials such as organic metal halides. The equipment provides us with a way to process these materials without cross-contamination of materials used in existing battery or organic semiconductor equipment. The Energy Facility currently serves 3 groups in 2 departments with approximately 800 overall usage hours. With our increasing capacities and uses, we are in-kind transitioning to a recharge platform. This will allow us to capture value from the use of our equipment to support its continued operation and future development.

The Microscopy and Microanalysis Facility: (Director: Prof. Tresa Pollock; Lab Managers: Mark Cornish, Dr. Stephan Kraemer, Dr. Tom Mates) This facility provides a range of advanced methods for the analysis of both hard and soft materials. Over the last reporting period, this facility increased its user- base by approximately 14%. Notable acquisitions this year include the purchase of two new state-of-the- art low vacuum SEM instruments. Both contain next-generation features such as a navigation system that drastically improves the site-specific analysis, as well as stage biasing with concomitant improvements in imaging of non-conducting samples. The first SEM, Nova Nano 650, is replacing an existing SEM, XL40, as part of an ongoing rejuvenation process of the electron microscope systems that will intensify in the coming years. At the end of this year it will be fully equipped with EBSD, EDX and CL. The second

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

SEM, FEI Teneo, will be primarily used by two new faculty members for extensive in-situ analysis. Nevertheless, in the spirit of our shared facilities, it will be also available to the public for certain applications. It is expected that, in particular, a new STEM detection system will be under great demand. It is noted that 3D imaging capabilities for the TEM, enabled by previous purchases (see report 2015), take traction and attracted the attention of other UCSB departments such as the Bren School and the Neuroscience Research Institute. Following the commitment to be open to the greater research community, the facility is used by students from partner institutions such as CNSI at UCLA, as well as CalPoly San Luis Obispo.

Polymer: The Polymer Characterization Facility (Director: Prof. Craig Hawker; Lab Manager: Dr. Rachel Behrens) continues to focus on streamlining current processes to optimize efficiency, reproducibility, and accuracy to serve its almost 200 trained internal and external users. Currently, the Polymer Facility serves 24 UCSB research groups in 10 departments and 18 off-campus users from both academia and industry. In the past year, the Polymer Characterization Facility has worked with 6 new industrial and 3 new academic contacts and had the pleasure of continuing to work with 2 previously- associated companies and 2 universities. In addition, the paperwork has been executed for a 5-year collaborative effort between the Polymer Facility and Dr. Maureen Dreher, a Biomedical Engineer at the Food and Drug Administration (FDA) directed towards characterization of the degradation process for cardiovascular stents fabricated from fully absorbable polymers. During the past year, a number of laboratory additions and modifications have been implemented to improve the ease of sample runs and instrument maintenance. With the installation of smaller bore columns on the GPCs, solvent usage was reduced, while the number of samples analyzed during the year increased by 15%. Recent additions to the Polymer Characterization Facility include an Agilent 1200 HPLC and a new Waters UPLC/ToF mass spectrometer. These instruments will be housed in newly-completed laboratory space that will greatly expand the MRSEC shared equipment footprint at UCSB.

Spectroscopy: In the current reporting period, the Spectroscopy Facility (Director: Prof. Songi Han; Lab Manager: Dr. Jerry Hu) acquired and successfully installed a cutting-edge, magic angle spinning (MAS) dynamic nuclear polarization (DNP) NMR spectrometer. This new NMR now works in conjugation with the existing Bruker AVANCE HD solid-state 400MHz WB spectrometer equipped with a built-in field sweep coil (now in use for two years). The core part of the MAS DNP instrumentation was purchased with a successful NSF MRI proposal granted to PIs Profs. Brad Chmelka, Songi Han, Craig Hawker and Dr. Jerry Hu. The complete MAS DNP-NMR system boasts a NMR sensitivity enhancement of up to 300 folds which translates into as much as 90,000 times savings for NMR experiments. This stunning sensitivity enhancement opens new avenues for NMR to a variety of applications that were deemed either inaccessible or infeasible to traditional NMR characterization techniques. The MAS DNP-NMR instrument will most visibly impact the characterization of functional materials, with applications ranging from catalysis, drug delivery, separation and purification devices, and of particular emphases on the elucidation of materials surfaces and interfaces, opening up broad and new characterization opportunities. To make room for the installation of the DNP-NMR system and to sustain the future development and growth of the Spectroscopy facility, the unshielded 500MHz SB magnet of over 20 years of age used with a Bruker DMX 500MHz solution NMR system was replaced with an ultra-shielded and newer magnet. The near zero stray field of the shielded magnet permits the efficient use of our facility space, but also improves overall user safety. It even accommodates users carrying magnetic field-sensitive devices such as pacemakers and metal implants, such that they may access the instrument safely.

TEMPO: The TEMPO (Thermal Electronic/Elemental Magnetic Porosity Optical) facility (Director: Prof. Ram Seshadri; Lab Manager: Dr. Amanda Strom) is a shared facility with over 170 on-campus users from more than 51 different groups and 15 different departments or organizations. We also serve 28 off-campus active users from academia and local industry in addition to accepting samples from external users for analysis by TEMPO staff. The 2015-16 year has been one of expansion for the MRL and, in 47

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

particular, the TEMPO facility with the addition of dedicated space for low-temperature instrumentation. With this addition, the MRL maximized its space-utilization, converting an unused outdoor patio into functional, shared research facility space. The first instrument to be housed in the new space is an entirely cryogen-free Physical Property Measurement System (PPMS), the DynaCool 9 Tesla system. This is an upgrade of our current instrumentation, which has the same capabilities but required cryogens for cooling to the minimum temperature at 2 K. This is in keeping with our goal for the TEMPO to be entirely cryogen-free as costs and maintenance using cryogen systems is prohibitive. In addition to the new Dynacool PPMS, TEMPO also upgraded our thermal analysis capabilities with the purchase of a refurbished Discovery TGA. With this acquisition we have increased our analytical capabilities including High-Resolution TGA, Curie temperature and advanced method programing features. The Discovery TGA can be used in tandem with the Discovery Mass Spectrometer for Evolved Gas Analysis for the identification of thermal decomposition products. This model further improves TEMPO operations by improving user ease in setting samples through a robotic auto-sampling feature.

Terahertz: The Terahertz Facility (Director: Prof. Mark Sherwin; Lab Managers: Dr. Nikolay Agladze and David Enyart), a partner facility of the MRL run by the Institute for Terahertz Science and Technology, provides unique and state-of-the-art experimental capabilities in the THz spectral range, known previously as a THz gap because of the lack of sufficiently powerful and accessible sources of radiation. With advances in solid state THz sources, femtosecond laser generation and detection of THz radiation, this region is now undergoing a tremendous surge of both research and number of promising applications. All these techniques are represented in the Facility. But what makes this Facility truly one- of-a-kind are THz free electron lasers (FEL) driven by the 6 MV electrostatic accelerator. A major upgrade of FELs was performed in the previous years and now peak THz power (up to 70 kW) is available to users. Thanks to the upgrades, the FEL powered 240 GHz EPR instrument is now fully operational with record low spin flipping times. In the past year this setup was upgraded with installation of the new high-speed digitizer with sampling rates up to 12.5 GS/s. A new custom LabVIEW software was written, enabling a wide range of pulsed EPR experiments performed with unprecedented power and time resolution at 240 GHz.

X-Ray: During the current period, the X-Ray Facility (Director: Prof. Cyrus Safinya; Lab Manager: Dr. Youli Li) served a total of 216 active users with 7445 recharge hours (84% internal, 16% external). This facility operates both commercial and custom developed x-ray diffractometers used by this user base. To further its customized capabilities, in the 2015/2016 time period the facility acquired a next generation solid-state detector (Eiger R 1M from Dectris) to complete the custom-built SAXS/WAXS instrument. This mega-pixel area detector with single photon sensitivity is expected to dramatically enhance the data quality of the instrument for low scattering samples.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

12. ADMINISTRATION AND MANAGEMENT

As we gear up for competing for renewal on the 2016/2017 timeframe, the UCSB MRSEC has been reorganizing, with new leadership. While PI Craig Hawker remains closely involved in the running of the current grant, the management structure, since early 2016, now has Ram Seshadri as Director and Ania Jayich as Associate Director. Partly in acknowledgement of how critical the Shared Experimental Facilities are, Hawker will continue to play a key role as Facilities Coordinator, also remaining the lead on the MRFN Program. Other changes include the creation of a new Education/Outreach Advisory Board, comprising Education/Outreach partners and experts on the UCSB campus, and some members of the local community including award-winning school teacher Marilyn Garza. Professor Paul Leonardi of the UCSB Technology Management Program is also a member of this board, helping to integrate and place some of our undergraduate interns into local start-up companies.

Organization, leadership, and reporting and advising structure. The 8-member strong External Advisory Board has been reconstituted with mostly new members. The Education/Outreach Advisory Board has been newly constituted with members from UCSB and local schools. GSDS is a student-run organization with a focus on expanding diversity, that also serves as the student body advising the UCSB MRSEC leadership.

The student-led organization Graduate Students for Diversity in Science plays the dual role of being the student advisory body to the MRSEC. Glenn Fredrickson directs the Mitsubishi Chemicals Center for Advanced Materials which is one of the key industrial partnerships under the UCSB MRSEC umbrella. He has now taken on the role of coordinating industrial outreach. The External Advisory Board has also been almost completely reconstituted as a result of numerous conflicts arising this current MRSEC competition year. The new board members, all of whom have already played a key role in helping advance the MRSEC, are listed below: Professor Nitash Balsara, [UC Berkeley/LBNL], Professor Luis Echegoyen, [UT El Paso] (retained from the old board), Professor Dan Frisbie, [Minnesota], Dr. Michelle Johannes [Naval Research Lab], Professor Ka Yee Lee, [Chicago], Professor Heather Maynard, [UCLA], Professor Stuart Rowan, [Case Western], and Professor Patrick Woodward, [Ohio State].

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

13. PLACEMENTS: STUDENTS & POSTDOCTORAL SCHOLARS

Graduate Student Placements 2015/16

Cain, Tyler Ph.D. Carbonics, Inc., Los Angeles, CA Carilli, Michael Ph.D. Air Force Research Laboratory, Edwards, CA Gaultois, Michael Ph.D. Marie-Curie Postdoc, University of Cambridge Glaudell, Anne* Ph.D. UCSB Postdoc, Chemistry & Biochemistry Dept. Kelley, Sara Nownes* Ph.D. Sr. Scientist, Genia Technologies, Santa Clara, CA Kudela, Damien Ph.D. CEO, Cayuga Biotech, Santa Barbara, CA Lee, Woo-ram Ph.D. Postdoc, University of Michigan Liu, Deyu Ph.D. Postdoc, University of Illinois Luo, Yingdong Ph.D. Oak Ridge National Laboratory, TN Menyo, Matt Ph.D. Carbon3D, San Francisco, CA Miller, Dusty Rose* Ph.D. Postdoc, Vanderbilt University Medical School, TN Paradiso, Sean Ph.D. Citrine Informatics, Redwood City, CA Patel, Sahil Ph.D. Headway Technologies, Inc, Milpitas, CA

Postdoctoral Scholar Placements 2015/16

Areephong, Jetsuda * University of New Brunswick, Canada Cheng, Chiyuan Colgate Research Gonzalez, Federico Lora** Bristol Myers Squibb Jun, Young-Si Chonnam National University, S. Korea Kim, Bongkeun Samsung Research Center, Korea Lee, Dong Woog Asst. Professor, UNIST, Korea Lehner, Anna* Karlsruhe Institute of Technology, Germany Schmidt, Bernard Max Planck Institute, Golm, Germany Shi, Weichao Harvard University, Cambridge MA Tateishi, YuiChi JSR Tokyo, Japan Youngblood, Brian** Lecturer, Dept. of Physics, UCSB * Female ** Underrepresented Minority

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

14. LIST OF MRSEC-SUPPORTED PUBLICATIONS

2015-2016 MRL PUBLICATIONS [237]

IRG-1 [27]

(a) Primary MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [13]

1. D.J. Audus, G.H. Fredrickson, “Field-based simulations of nanostructured polyelectrolyte gels,” in Materials for Energy Infrastructure, Ed. W. Udomkichdecha, A. Mononukul, T. Böllinghaus, J. Lexow. Singapore: Springer, pp. 1-9 (2016). ISBN: 978-981-287-724-6 DOI: 10.1007/978-981-287-724-6

2. X. Banquy, D.W. Lee, K. Kristiansen, M.A. Gebbie, J.N. Israelachvili, “Interaction forces between supported lipid bilayers in the presence of PEGylated polymers,” Biomacromolecules 17 (2016) 88-97. DOI: 10.1021/acs.biomac.5b01216

3. K.W. Desmond, N.A. Zacchia, J.H. Waite, M.T. Valentine, “Dynamics of mussel plaque detachment,” Soft Matter 11 (2015) 6832-6839. DOI: 10.1039/C5SM01072A

4. E. Filippidi, D.G. DeMartini, P. Malo de Molina, E.W. Danner, J. Kim, M.E. Helgeson, J.H. Waite, M.T. Valentine, “The microscopic network structure of mussel (Mytilus) adhesive plaques,” J. R. Soc. Interface 12 (2015) 1-10. DOI: 10.1098/rsif.2015.0827

5. W.R. Gutekunst, C.J. Hawker, “A general approach to sequence-controlled polymers using macrocyclic ring opening metathesis polymerization,” J. Am. Chem. Soc. 137 (2015) 8038-8041. DOI: 10.1021/jacs.5b04940

6. K. Kempe, R.A. Wylie, M.D. Dimitriou, H. Tran, R. Hoogenboom, U.S. Schubert, C.J. Hawker, L.M. Campos, L.A. Connal, “Preparation of non-spherical particles from amphiphilic block copolymers,” J. Polym. Sci. A: Polym. Chem. 54 (2016) 750-757. DOI: 10.1002/pola.27927

7. G.P. Maier, M.V. Rapp, J.H. Waite, J.N. Israelachvili, A. Butler, “Adaptive synergy between catechol and lysine promotes wet adhesion by surface salt displacement,” Science 349 (2015) 628- 632. DOI: 10.1126/science.aab0556

8. K.M. Mattson, A.A. Latimer, A.J. McGrath, N.A. Lynd, P. Lundberg, Z.M. Hudson, C.J. Hawker, “A facile synthesis of catechol-functionalized poly(ethylene oxide) block and random copolymers,” J. Polym. Sci. A: Polym. Chem. 53 (2015) 2685-2692. DOI: 10.1002/pola.27749

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

9. M.S. Menyo, C.J. Hawker, J.H. Waite, “Rate-dependent stiffness and recovery in interpenetrating network hydrogels through sacrificial metal coordination bonds,” ACS Macro Lett. 4 (2015) 1200-1204. DOI: 10.1021/acsmacrolett.5b00664

10. D. Montarnal, N. Delbosc, C. Chamignon, M.A. Virolleaud, Y. Luo, C.J. Hawker, E. Drockenmuller, J. Bernard, “Highly ordered nanoporous films from supramolecular diblock copolymers with hydrogen-bonding junctions,” Angew. Chem. Int. Ed. 54 (2015) 11117-11121. DOI: 10.1002/anie.201504838

11. T. Murakami, B.V.K.J. Schmidt, H.R. Brown, C.J. Hawker, “One-pot ‘click’ fabrication of slide- ring gels,” Macromolecules 48 (2015) 7774-7781. DOI: 10.1021/acs.macromol.5b01713

12. A.M. Schrader, S.H. Donaldson, Jr., J. Song, C.-Y. Cheng, D.W. Lee, S. Han, J.N. Israelachvili, “Correlating steric hydration forces with water dynamics through surface force and diffusion NMR measurements in a lipid–DMSO–H2O system,” PNAS 112 (2015) 10708-10713. DOI: 10.1073/pnas.1512325112

13. W. Shi, Y. Tateishi, W. Li, C.J. Hawker, G.H. Fredrickson, E.J. Kramer, “Producing small domain features using miktoarm block copolymers with large interaction parameters,” ACS Macro Lett. 4 (2015) 1287-1292. DOI: 10.1021/acsmacrolett.5b00712

(b) Partial MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [14]

14. B.K. Ahn, S. Das, R. Linstadt, Y. Kaufman, N.R. Martinez Rodriguez, R. Mirshafian, E. Kesselman, Y. Talmon, B.H. Lipshutz, J.N. Israelachvili, J.H. Waite, “High-performance mussel-inspired adhesives of reduced complexity,” Nature Commun. 6 (2015) 8663. DOI: 10.1038/ncomms9663

15. J. Areephong, K.M. Mattson, N.J. Treat, S.O. Poelma, J.W. Kramer, H.A. Sprafke, A.A. Latimer, J. Read de Alaniz, C.J. Hawker, “Triazine-mediated controlled radical polymerization: New unimolecular initiators,” Polym. Chem. 7 (2016) 370-374. DOI: 10.1039/c5py01563d

16. N.V. Handa, A.V. Serrano, M.J. Robb, C.J. Hawker, “Exploring the synthesis and impact of end- functional poly(3-hexylthiophene),” J. Polym. Sci. A: Polym. Chem. 53 (2015) 831-841. DOI: 10.1002/pola.27522

17. K.L. Killops, C.G. Rodriguez, P. Lundberg, C.J. Hawker, N.A. Lynd, “A synthetic strategy for the preparation of sub-100 nm functional polymer particles of uniform diameter,” Polym. Chem. 6 (2015) 1431-1435. DOI: 10.1039/C4PY01703J

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

18. A.J. McGrath, W. Shi, C.G. Rodriguez, E.J. Kramer, C.J. Hawker, N.A. Lynd, “Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers,” Polym. Chem. 6 (2015) 1465-1473. DOI: 10.1039/C4PY01503G

19. D.R. Miller, S. Das, K.-Y. Huang, S. Han, J.N. Israelachvili, J.H. Waite, “Mussel coating protein- derived complex coacervates mitigate frictional surface damage,” ACS Biomater. Sci. Eng. 1 (2015) 1121-1128. DOI: 10.1021/acsbiomaterials.5b00252

20. D.R. Miller, J.E. Spahn, J.H. Waite, “The staying power of adhesion-associated antioxidant activity in Mytilus californianus,” J. R. Soc. Interface 12 (2015) 20150614. DOI: 10.1098/rsif.2015.0614

21. C.W. Pester, J.E. Poelma, B. Narupai, S.N. Patel, G.M. Su, T.E. Mates, Y. Luo, C.K. Ober, C.J. Hawker, E.J. Kramer, “Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization,” J. Polym. Sci. A: Polym. Chem. 54 (2016) 253-262. DOI: 10.1002/pola.27748

22. B.V.K.J. Schmidt, J. Elbert, D. Scheid, C.J. Hawker, D. Klinger, M. Gallei, “Metallopolymer- based shape anisotropic nanoparticles,” ACS Macro Lett. 4 (2015) 731-735. DOI: 10.1021/acsmacrolett.5b00350

23. S. Seo, S. Das, P.J. Zalicki, R. Mirshafian, C.D. Eisenbach, J.N. Israelachvili, J.H. Waite, B.K. Ahn, “Microphase behavior and enhanced wet-cohesion of synthetic copolyampholytes inspired by a mussel foot protein,” J. Am. Chem. Soc. 137 (2015) 9214-9217. DOI: 10.1021/jacs.5b03827

24. W.C. Shi, A.J. McGrath, Y.L. Li, N.A. Lynd, C.J. Hawker, G.H. Fredrickson, E.J. Kramer, “Cooperative and sequential phase transitions in it-poly(propylene oxide)-b-poly(ethylene oxide)- b-it-poly(propylene oxide) triblock copolymers,” Macromolecules 48 (2015) 3069-3079. DOI: 10.1021/acs.macromol.5b00326

25. Y. Tan, S. Hoon, P.A. Guerette, W. Wei, A. Ghadban, C. Hao, A. Miserez, J.H. Waite, “Infiltration of chitin by protein coacervates defines the squid beak mechanical gradient,” Nature Chem. Biol. 11 488-495 (2015). DOI: 10.1038/nchembio.1833

26. N.A. Zacchia, M.T. Valentine, “Design and optimization of arrays of neodymium iron boron- based magnets for magnetic tweezers applications,” Rev. of Sci. Instrum. 86 (2015) 053704. DOI: 10.1063/1.4921553

27. Y. Zhang, P. Lundberg, M. Diether, C. Porsch, C. Janson, N.A. Lynd, C. Ducani, M. Malkoch, E. Malmström, C.J. Hawker, A.M. Nyström, “Histamine-functionalized copolymer micelles as a drug delivery system in 2D and 3D models of breast cancer,” J. Mater. Chem. B 3 (2015) 2472- 2486. DOI: 10.1039/C4TB02051K

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

IRG-2 [20]

(a) Primary MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [10]

28. L. Bjaalie, D.G. Ouellette, P. Moetakef, T.A. Cain, A. Janotti, B. Himmetoglu, S.J. Allen, S. Stemmer, C.G. Van de Walle, “Small hole polarons in rare-earth titanates,” Appl. Phys. Lett. 106 (2015) 232103. DOI: 10.1063/1.4922316

29. S. Bubel, A.J. Hauser, A.M. Glaudell, T.E. Mates, S. Stemmer, M.L. Chabinyc, “The electrochemical impact on electrostatic modulation of the metal-insulator transition in nickelates,” Appl. Phys. Lett. 106 (2015) 122102. DOI: 10.1063/1.4915269

30. S. Bubel, M.S. Menyo, T.E. Mates, J.H. Waite, M.L. Chabinyc, “Schmitt trigger using a self- healing ionic liquid gated transistor,” Adv. Mater. 27 (2015) 3331-3335. DOI: 10.1002/adma.201500556

31. T. Hogan, Z. Yamani, D. Walkup, X. Chen, R. Dally, T.Z. Ward, M.P.M. Dean, J. Hill, Z. Islam, V. Madhavan, S.D. Wilson, “First-order melting of a weak spin-orbit Mott insulator into a correlated metal,” Phys. Rev. Lett. 114 (2015) 257203. DOI: 10.1103/PhysRevLett.114.257203

32. S.W. Kaun, F. Wu, J.S. Speck, “β-(AlxGa1−x)2O3/Ga2O3 (010) heterostructures grown on β- Ga2O3 (010) substrates by plasma-assisted molecular beam epitaxy,” J. Vac. Sci. Tech. A 33 (2015) 041508. DOI: 10.1116/1.4922340

33. P.M. McBride, A. Janotti, C.E. Dreyer, B. Himmetoglu, C.G. Van de Walle, “Effects of biaxial

stress and layer thickness on octahedral tilts in LaNiO3,” Appl. Phys. Lett. 107 (2015) 261901. DOI: 10.1063/1.4939002

34. E. Mikheev, S. Raghavan, J.Y. Zhang, P.B. Marshall, A.P. Kajdos,

L. Balents, S. Stemmer, “Carrier density independent scattering rate in SrTiO3-based electron liquids,” Sci. Rep. 6 (2016) 20865. DOI: 10.1038/srep20865

35. S. Nemšák, G. Conti, G.K. Palsson, C. Conlon, S. Cho, J.E. Rault, J. Avila, M.-C. Asensio, C.A. Jackson, P. Moetakef, A. Janotti, L. Bjaalie, B. Himmetoglu, C.G. Van de Walle, L. Balents, C.M. Schneider, S. Stemmer, C.S. Fadley, “Observation by resonant angle- resolved photoemission of a critical thickness for 2-dimensional electron gas formation in

SrTiO3 embedded in GdTiO3,” Appl. Phys. Lett. 107 (2015) 231602. DOI: 10.1063/1.4936936

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

36. L. Weston, A. Janotti, X.Y. Cui, B. Himmetoglu, C. Stampfl, C.G. Van de Walle, “Structural and

electronic properties of SrZrO3 and Sr(Ti,Zr)O3 alloys,” Phys. Rev. B 92 (2015) 085201. DOI: 10.1103/PhysRevB.92.085201

37. C.-H. Yee, L. Balents, “Phase separation in doped Mott insulators,” Phys. Rev. X 5 (2015) 021007. DOI: 10.1103/PhysRevX.5.021007

(b) Partial MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [10]

38. S.J. Allen, A.J. Hauser, E. Mikheev, J.Y. Zhang, N.E. Moreno, J. Son, D.G. Ouellette, J. Kally, A. Kozhanov, L. Balents, S. Stemmer, “Gaps and pseudogaps in perovskite rare earth nickelates,” APL Mater. 3 (2015) 062503. DOI: 10.1063/1.4907771

39. L. Bjaalie, A. Verma, B. Himmetoglu, A. Janotti, S. Raghavan, V. Protasenko, E.H. Steenbergen,

D. Jena, S. Stemmer, C.G. Van de Walle, “Determination of the Mott-Hubbard gap in GdTiO3,” Phys. Rev. B 92 (2015) 085111. DOI: 10.1103/PhysRevB.92.085111

40. T.H. Hsieh, H. Ishizuka, L. Balents, T.L. Hughes, “Bulk topological proximity effect,” Phys. Rev. Lett. 116 (2016) 086802. DOI: 10.1103/PhysRevLett.116.086802

41. T. Kondo, M. Nakayama, R. Chen, J.J. Ishikawa, E.-G. Moon, T. Yamamoto, Y. Ota, W. Malaeb, H. Kanai, Y. Nakashima, Y. Ishida, R. Yoshida, H. Yamamoto, M. Matsunami, S. Kimura, N. Inami, K. Ono, H. Kumigashira, S. Nakatsuji, L. Balents, S. Shin, “Quadratic Fermi node in a 3D strongly correlated semimetal,” Nature Commun. 6 (2015) 10042. DOI: 10.1038/ncomms10042

42. D. Lee, H. Lu, Y. Gu, S.-Y. Choi, S.-D. Li, S. Ryu, T.R. Paudel, K. Song, E. Mikheev, S. Lee, S. Stemmer, D.A. Tenne, S.H. Oh, E.Y. Tsymbal, X. Wu, L.-Q. Chen, A. Gruverman, C.B. Eom, “Emergence of room-temperature ferroelectricity at reduced dimensions,” Science 349 (2015) 1314-1317. DOI: 10.1126/science.aaa6442

43. E. Mikheev, J. Hwang, A.P. Kajdos, A.J. Hauser, S. Stemmer, “Tailoring resistive switching in

Pt/SrTiO3 junctions by stoichiometry control,” Sci. Rep. 5 (2015) 11079. DOI: 10.1038/srep11079

44. H. Peelaers, D. Steiauf, J.B. Varley, A. Janotti, C.G. Van de Walle, “(InxGa1-x)2O3 alloys for transparent electronics,” Phys. Rev. B 92 (2015) 085206. DOI: 10.1103/PhysRevB.92.085206

45. S. Raghavan, T. Schumann, H. Kim, J.Y. Zhang, T.A. Cain, S. Stemmer, “High-mobility

BaSnO3 grown by oxide molecular beam epitaxy,” APL Mater. 4 (2016) 016106. DOI: 10.1063/1.4939657

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

46. S. Raghavan, J.Y. Zhang, S. Stemmer, “Two-dimensional electron liquid at the (111)

SmTiO3/SrTiO3 interface,” Appl. Phys. Lett. 106 (2015) 132104. DOI: 10.1063/1.4916963

47. J.Y. Zhang, J. Hwang, B.J. Isaac, S. Stemmer, “Variable-angle high-angle annular dark-field imaging: Application to three-dimensional dopant atom profiling,” Sci. Rep. 5 (2015) 12419. DOI: 10.1038/srep12419

IRG-3 [5]

(a) Primary MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [5]

48. L. Decolvenaere, M.J. Gordon, A. Van der Ven, “Testing predictions from density functional

theory at finite temperatures: ß2-like ground states in Co-Pt,” Phys. Rev. B 92 (2015) 085119. DOI: 10.1103/PhysRevB.92.085119

49. K.A. Denault, J. Brgoch, S.D. Kloß, M.W. Gaultois, J. Siewenie, K. Page, R. Seshadri, “Average and local structure, Debye temperature, and structural rigidity in some oxide compounds related to phosphor hosts,” ACS Appl. Mater. Interfaces 7 (2015) 7264-7272. DOI: 10.1021/acsami.5b00445

50. J.E. Douglas, M.P. Echlin, W.C. Lenthe, R. Seshadri, T.M. Pollock, “Three-dimensional multimodal imaging and analysis of biphasic microstructure in a Ti-Ni-Sn thermoelectric material,” APL Mater. 3 (2015) 096107. DOI: 10.1063/1.4931764

51. M.W. Gaultois, J.E. Douglas, T.D. Sparks, R. Seshadri, “Single-step preparation and consolidation of reduced early-transition-metal oxide/metal n-type thermoelectric composites,” AIP Adv. 5 (2015) 097144. DOI: 10.1063/1.4931161

52. T.D. Sparks, M.W. Gaultois, A. Oliynyk, J. Brgoch, B. Meredig, “Data mining our way to the next generation of thermoelectrics,” Scr. Mater. 111 (2016) 10-15. DOI: 10.1016/j.scriptamat.2015.04.026

SEED [13]

(a) Primary MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [8]

53. T. Das, P.P. Iyer, R.A. DeCrescent, J.A. Schuller, “Beam engineering for selective and enhanced coupling to multipolar resonances,” Phys. Rev. B 92 (2015) 241110. DOI: 10.1103/PhysRevB.92.241110

54. C.M. Evans, G.E. Sanoja, B.C. Popere, R.A. Segalman, “Anhydrous proton transport in polymerized ionic liquid block copolymers: Roles of block length, ionic content, and

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

confinement,” Macromolecules 49 (2016) 395-404. DOI: 10.1021/acs.macromol.5b02202

55. Y. Gao, J. Kim, M.E. Helgeson, “Microdynamics and arrest of coarsening during spinodal decomposition in colloidal gels,” Soft Matter 11 (2015) 6360-6370. (Cover article) DOI: 10.1039/C5SM00851D

56. H.H. Kristoffersen, J.-E. Shea, H. Metiu, “Catechol and HCl adsorption on TiO2(110) in vacuum and at the water–TiO2 interface,” J. Phys. Chem. Lett. 6 (2015) 2277-2281. DOI: 10.1021/acs.jpclett.5b00958

57. Z.A. Levine, S.A. Fischer, J.-E. Shea, J. Pfaendtner, “Trp-cage folding on organic surfaces,” J. Phys. Chem. B 119 (2015) 10417-10425. DOI: 10.1021/acs.jpcb.5b04213

58. Z.A. Levine, L. Larini, N.E. LaPointe, S.C. Feinstein, J.-E. Shea, “Regulation and aggregation of intrinsically disordered peptides,” PNAS 112 (2015) 2758-2763. DOI: 10.1073/pnas.1418155112

59. E.K. Peter, I.V. Pivkin, J.-E. Shea, “A kMC-MD method with generalized move-sets for the simulation of folding of α-helical and β-stranded peptides,” J. Chem. Phys. 142 (2015) 144903. DOI: 10.1063/1.4915919

60. G.H. Zerze, R.G. Mullen, Z.A. Levine, J.-E. Shea, J. Mittal, “To what extent does surface hydrophobicity dictate peptide folding and stability near surfaces?” Langmuir 31 (2015) 12223- 12230. DOI: 10.1021/acs.langmuir.5b03814

(b) Partial MRSEC Support that Acknowledge the MRSEC Award DMR-1121053 [5]

61. E.H. Discekici, C.W. Pester, N.J. Treat, J. Lawrence, K.M. Mattson, B. Narupai, E.P. Toumayan, Y. Luo, A.J. McGrath, P.G. Clark, J. Read de Alaniz, C.J. Hawker, “Simple benchtop approach to polymer brush nanostructures using visible-light-mediated metal-free atom transfer radical polymerization,” ACS Macro Lett. 5 (2016) 258-262. DOI: 10.1021/acsmacrolett.6b00004

62. E.H. Discekici, N.J. Treat, S.O. Poelma, K.M. Mattson, Z.M. Hudson, Y.D. Luo, C.J. Hawker, J. Read de Alaniz, “A highly reducing metal-free photoredox catalyst: Design and application in radical dehalogenations,” Chem. Commun. 51 (2015) 11705-11708. DOI: 10.1039/c5cc04677g

63. S. Mubeen, J. Lee, D. Liu, G.D. Stucky, M. Moskovits, “Panchromatic photoproduction of H2 with surface plasmons,” Nano Lett. 15 (2015) 2132-2136. DOI: 10.1021/acs.nanolett.5b00111

64. C.-Y. Park, D.R. Jacobson, D.T. Nguyen, S. Willardson, O.A. Saleh, “A thin permeable- membrane device for single-molecule manipulation,” Rev. Sci. Instrum. 87 (2016) 014301.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

DOI: 10.1063/1.4939197

65. O.A. Saleh, “Perspective: Single polymer mechanics across the force regimes,” J. Chem. Phys. 142 (2015) 194902. DOI: 10.1063/1.4921348

SHARED FACILITIES [172]

66. V. Agarwal, H. Metiu, “Energy of oxygen-vacancy formation on oxide surfaces: Role of the spatial distribution,” J. Phys. Chem. C 120 (2016) 2320-2323. DOI: 10.1021/acs.jpcc.5b12054

67. V. Agarwal, H. Metiu, “Hydrogen abstraction energies and ammonia binding to BEA, ZSM-5, and α-quartz doped with Al, Sc, B, or Ga,” J. Phys. Chem. C 119 (2015) 16106-16114. DOI: 10.1021/acs.jpcc.5b04171

68. E. Ahmadi, F. Wu, H. Li, S.W. Kaun, M. Tahhan, K. Hestroffer, S. Keller, J.S. Speck, U.K. Mishra, “N-face GaN/AlN/GaN/InAlN and GaN/AlN/AlGaN/GaN/InAlN high-electron- mobility transistor structures grown by plasma-assisted molecular beam epitaxy on vicinal substrates,” Semi. Sci. Tech. 30 (2015) 055012. DOI: 10.1088/0268-1242/30/5/055012

69. N.E.C. de Almeida, T.D. Do, M. Tro, N.E. LaPointe, S.C. Feinstein, J.-E. Shea, M.T. Bowers, “Opposing effects of cucurbit[7]uril and 1,2,3,4,6-penta---O---galloyl- β---D---glucopyranose on

amyloid β25−35 assembly,” ACS Chem. Neurosci. 7 (2016) 218-226. DOI: 10.1021/acschemneuro.5b00280

70. K. Aoyagi, M. Zakrewsky, S. Mitragotri, “Formulating propranolol as an amorphous melt affords reduced skin irritation potential for transdermal drug delivery,” Technology 03 (2015) 214-238. DOI: 10.1142/S2339547815500107

71. I. Barel, N.O. Reich, F.L.H. Brown, “Extracting enzyme processivity from kinetic assays,” J. Chem. Phys. 143 (2015) 224115. DOI: 10.1063/1.4937155

72. A. Birkel, N.A. DeCino, C. Cozzan, A.A. Mikhailovsky, B.-C. Hong, R. Seshadri, “A single- 2+ 3+ 2+ phase full-color phosphor based on Ba3MgSi2O8 co-activated with Eu , Tb , and Mn ,” Solid State Sciences 48 (2015) 82-89. DOI: 10.1016/j.solidstatesciences.2015.07.005

73. J. Botana, X. Wang, C. Hou, D. Yan, H. Lin, Y. Ma, M.-S. Miao, “Mercury under pressure acts as a transition metal: Calculated from first principles,” Angew. Chem. Int’l. Ed. 54 (2015) 9280- 9283. DOI: 10.1002/anie.201503870

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

74. D.A. Browne, B. Mazumder, Y.-R. Wu, J.S. Speck, “Electron transport in unipolar InGaN/GaN

multiple quantum well structures grown by NH3 molecular beam epitaxy,” J. Appl. Phys. 117 (2015) 185703. DOI: 10.1063/1.4919750

75. N.A. Butakov, J.A. Schuller, “Hybrid optical antennas with photonic resistors,” Optics Express 23 (2015) 29698-29707. DOI: 10.1364/OE.23.029698

76. M. Cantore, N. Pfaff, R.M. Farrell, J.S. Speck, S. Nakamura, S.P. DenBaars, “High luminous flux from single crystal phosphor-converted laser-based white lighting system,” Optics Express 24 (2016) A215-A221. DOI: 10.1364/OE.24.00A215

77. M.F. Carilli, K.T. Delaney, G.H. Fredrickson, “Truncation-based energy weighting string method for efficiently resolving small energy barriers,” J. Chem. Phys. 143 (2015) 054105. DOI: 10.1063/1.4927580

78. S.P. Carmichael, M.S. Shell, “Entropic (de)stabilization of surface-bound peptides conjugated with polymers,” J. Chem. Phys. 143 (2015) 243103. DOI: 10.1063/1.4929592

79. C.L. Carpenter, K.T. Delaney, N. Laachi, G.H. Fredrickson, “Directed self-assembly of diblock copolymers in cylindrical confinement: Effect of under-filling and air-polymer interactions on configurations,” Proc. SPIE 9423, Alternative Lithographic Technologies VII (2015) 94231Z-1. DOI: 10.1117/12.2085639

80. I.T. Carroll, R.M. Nisbet, “Departures from neutrality induced by niche and relative fitness differences,” Theoretical Ecology 8 (2015) 449-465. DOI: 10.1007/s12080-015-0261-0

81. D. Chang, M.-H. Chen, A. Van der Ven, “Factors contributing to path hysteresis of displacement and conversion reactions in Li ion batteries,” Chem. Mater. 27 (2015) 7593-7600. DOI: 10.1021/acs.chemmater.5b02356

82. H. Chen, L. Zhang, “A desulfonylative approach in oxidative gold catalysis: Regiospecific access to donor-substituted acyl gold carbenes,” Angew. Chem. Int’l. Ed. 54 (2015) 11775-11779. DOI: 10.1002/anie.201504511

83. M.-H. Chen, A. Emly, A. Van der Ven, “Anharmonicity and phase stability of antiperovskite Li3 OCl,” Phys. Rev. B 91 (2015) 214306. DOI: 10.1103/PhysRevB.91.214306

84. M.-H. Chen, B. Puchala, A. Van der Ven, “High-temperature stability of δ’-ZrO,” CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 51 (2015) 292-298. DOI: 10.1016/j.calphad.2015.10.010

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

85. C.-Y. Cheng, J. Song, J. Pas, L.H.H. Meijer, S. Han, “DMSO induces dehydration near lipid membrane surfaces,” Biophys. J. 109 (2015) 330-339. DOI: 10.1016/j.bpj.2015.06.011

86. S. Chrétien, H. Metiu, “Hydrogen dissociative adsorption on lanthana: Polaron formation and the role of acid-base interactions,” J. Phys. Chem. C 119 (2015) 19876-19882. DOI: 10.1021/acs.jpcc.5b05310

87. R.R. Collino, T.R. Ray, R.C. Fleming, C.H. Sasaki, H. Haj-Hariri, M.R. Begley, “Acoustic field controlled patterning and assembly of anisotropic particles,” Extreme Mechanics Letters 5 (2015) 37-46. DOI: 10.1016/j.eml.2015.09.003

88. J.R. Conway, A.L. Beaulieu, N.L. Beaulieu, S.J. Mazer, A.A. Keller, “Environmental stresses increase photosynthetic disruption by metal oxide nanomaterials in a soil-grown plant,” ACS Nano 9 (2015) 11737-11749. DOI: 10.1021/acsnano.5b03091

89. S. Das, N.R. Martinez Rodriguez, W. Wei, J.H. Waite, J.N. Israelachvili, “Peptide length and dopa determine iron-mediated cohesion of mussel foot proteins,” Adv. Func. Mater. 25 (2015) 5840-5847. DOI: 10.1002/adfm.201502256

90. E.C. Davidson, B.S. Beckingham, V. Ho, R.A. Segalman, “Confined crystallization in lamellae forming poly(3-(2’-ethyl)hexylthiophene) (P3EHT) block copolymers,” J. Poly. Sci. B: Poly. Phys. 54 (2016) 205-215. DOI: 10.1002/polb.23904

91. Z. Deng, L. Zhang, D. Franklin, F.T. Chong, “Herniated hash tables: Exploiting multi-level phase change memory for in-place data expansion,” in MEMSYS ’15 Proceedings of the 2015 Int’l. Symposium on Memory Systems. New York, NY: ACM, pp. 247-257 (2015). ISBN: 978-1- 4503-3604-8 DOI: 10.1145/2818950.2818981

92. K. Ding, A. Corma, J.A. Maciá-Agulló, J.G. Hu, S. Krämer, P.C. Stair, G.D. Stucky, “Constructing hierarchical porous zeolites via kinetic regulation,” J. Am. Chem. Soc. 137 (2015) 11238-11241. DOI: 10.1021/jacs.5b06791

93. T.D. Do, A. Chamas, X. Zheng, A. Barnes, D. Chang, T. Veldstra, H. Takhar, N. Dressler, B. Trapp, K. Miller, A. McMahon, S.C. Meredith, J.-E. Shea, K. Lazar Cantrell, M.T. Bowers, “Elucidation of the aggregation pathways of helix−turn−helix peptides: Stabilization at the turn region is critical for fibril formation,” Biochemistry 54 (2015) 4050-4062. DOI: 10.1021/acs.biochem.5b00414

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

94. T.D. Do, N.E. LaPointe, R. Nelson, P. Krotee, E.Y. Hayden, B. Ulrich, S. Quan, S.C. Feinstein, D.B. Teplow, D. Eisenberg, J.-E. Shea, M.T. Bowers, “Amyloid β---protein C---terminal fragments: Formation of cylindrins and β---barrels,” J. Am. Chem. Soc. 138 (2016) 549-557. DOI: 10.1021/jacs.5b09536

95. C.E. Dreyer, A. Janotti, C.G. Van de Walle, “Brittle fracture toughnesses of GaN and AlN from first-principles surface-energy calculations,” Appl. Phys. Lett. 106 (2015) 212103. DOI: 10.1063/1.4921855

96. N.D. Eisenmenger, K.T. Delaney, V. Ganesan, G.H. Fredrickson, M.L. Chabinyc, “Energy transfer directly to bilayer interfaces to improve exciton collection in organic photovoltaics,” J. Phys. Chem. C 119 (2015) 19011-19021. DOI: 10.1021/acs.jpcc.5b05749

97. N.A. Eschmann, T.D. Do, N.E. LaPointe, J.-E. Shea, S.C. Feinstein, M.T. Bowers, S. Han, “Tau aggregation propensity engrained in its solution state,” J. Phys. Chem. B 119 (2015) 14421- 14432. DOI: 10.1021/acs.jpcb.5b08092

98. D.H. Fabini, T. Hogan, H.A. Evans, C.C. Stoumpos, M.G. Kanatzidis, R. Seshadri, “Dielectric and thermodynamic signatures of low-temperature glassy dynamics in the hybrid perovskites

CH3NH3PbI3 and HC(NH2)2PbI3,” J. Phys. Chem. Lett. 7 (2016) 376-381. DOI: 10.1021/acs.jpclett.5b02821

99. N. Fechler, N.P. Zussblatt, R. Rothe, R. Schlögl, M.-G. Willinger, B.F. Chmelka, M. Antonietti, “Eutectic syntheses of graphitic carbon with high pyrazinic nitrogen content,” Adv. Mater. 28 (2016) 1287-1294. DOI: 10.1002/adma.201501503

100. M.N. Fireman, D.A. Browne, B. Mazumder, J.S. Speck, U.K. Mishra, “Demonstration of

isotype GaN/AlN/GaN heterobarrier diodes by NH3-molecular beam epitaxy,” Appl. Phys. Lett. 106 (2015) 202106. DOI: 10.1063/1.4921633

101. M.N. Fireman, D.A. Browne, U.K. Mishra, J.S. Speck, “Isotype InGaN/GaN heterobarrier diodes by ammonia molecular beam epitaxy,” J. Appl. Phys. 119 (2016) 055709. DOI: 10.1063/1.4941323

102. C. Fleischmann, J. Gopez, P. Lundberg, H. Ritter, K.L. Killops, C.J. Hawker, D. Klinger, “A robust platform for functional microgels via thiol-ene chemistry with reactive polyether-based nanoparticles,” Polym. Chem. 6 (2015) 2029-2037. DOI: 10.1039/C4PY01766H

103. J.M. Franck, Y. Ding, K. Stone, P.Z. Qin, S. Han, “Anomalously rapid hydration water diffusion dynamics near DNA surfaces,” J. Am. Chem. Soc. 137 (2015) 12013-12023. DOI: 10.1021/jacs.5b05813

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

104. S.L. Fronk, C.-K. Mai, M. Ford, R.P. Noland, G.C. Bazan, “End-group-mediated aggregation of poly(3-hexylthiophene),” Macromolecules 48 (2015) 6224-6232. DOI: 10.1021/acs.macromol.5b00986

105. P. Ganguly, T.D. Do, L. Larini, N.E. LaPointe, A.J. Sercel, M.F. Shade, S.C. Feinstein, M.T. Bowers, J.-E. Shea, “Tau assembly: The dominant role of PHF6 (VQIVYK) in microtubule binding region repeat R3,” J. Phys. Chem. B 119 (2015) 4582-4593. DOI: 10.1021/acs.jpcb.5b00175

106. E.S. Garcia, C.L. Tague, “Subsurface storage capacity influences climate–evapotranspiration interactions in three western United States catchments,” Hydrol. Earth Syst. Sci. 19 (2015) 4845- 4858. DOI: 10.5194/hess-19-4845-2015

107. V.V. Ginzburg, J.D. Weinhold, P.D. Hustad, P. Trefonas, B. Kim, N. Laachi, G.H. Fredrickson, “Field-theoretic simulations and self-consistent field theory (SCFT) for studying block copolymer directed self-assembly,” in Directed Self-Assembly of Block Copolymers for Nano- Manufacturing, Eds. R. Grohheid and P. Nealey. Cambridge, UK: Woodhead Publishing, Elsevier, pp. 67-95 (2015). ISBN: 978-0-08-100250-6 DOI: 10.1016/B978-0-08-100250-6.00004-3

108. L. Gordon, A. Janotti, C.G. Van de Walle, “Defects as qubits in 3C− and 4H−SiC,” Phys. Rev. B 92 (2015) 045208. DOI: 10.1103/PhysRevB.92.045208

109. L. Gordon, J.B. Varley, J.L. Lyons, A. Janotti, C.G. Van de Walle, “Sulfur doping of AlN and AlGaN for improved n-type conductivity,” Physica Status Solidi (RRL) - Rapid Research Lett. 9 (2015) 462-465. DOI: 10.1002/pssr.201510165

110. N.J. Hartmann, G. Wu, T.W. Hayton, “Synthesis of a ‘masked’ terminal nickel(II) sulfide by reductive deprotection and its reaction with nitrous oxide,” Angew. Chem. Int’l. Ed. 54 (2015) 14956-14959. DOI: 10.1002/anie.201508232

111. B.F. Hartmeier, M.A. Brady, N.D. Treat, M.J. Robb, T.E. Mates, A. Hexemer, C. Wang, C.J. Hawker, E.J. Kramer, M.L. Chabinyc, “Significance of miscibility in multidonor bulk heterojunction solar cells,” J. Polym. Sci. B: Polym. Phys. 54 (2016) 237-246. DOI: 10.1002/polb.23907

112. A.J. Hauser, E. Mikheev, N.E. Moreno, J. Hwang, J.Y. Zhang, S. Stemmer, “Correlation

between stoichiometry, strain, and metal-insulator transitions of NdNiO3 films,” Appl. Phys. Lett. 106 (2015) 092104. DOI: 10.1063/1.4914002

113. B. Himmetoglu, A. Janotti, “Transport properties of KTaO3 from first-principles,” J. Phys.: Condens. Matter 28 (2016) 065502.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

DOI: 10.1088/0953-8984/28/6/065502

114. K. Hofmann, N. Kalyon, C. Kapfenberger, L. Lamontagne, S. Zarrini, R. Berger, R. Seshadri,

B. Albert, “Metastable Ni7B3: A new paramagnetic boride from solution chemistry, its crystal structure and magnetic properties,” Inorg. Chem. 54 (2015) 10873-10877. DOI: 10.1021/acs.inorgchem.5b01929

115. C.C. Holland, E.A. Gamble, F.W. Zok, V.S. Deshpande, R.M. McMeeking, “Effect of design on the performance of steel–alumina bilayers and trilayers subject to ballistic impact,” Mechan. of Mater. 91 (2015) 241-251. DOI: 10.1016/j.mechmat.2015.05.002 [

116. N. Hu, C.-K. Mai, G.H. Fredrickson, G.C. Bazan, “One-pot synthesis of semicrystalline/amorphous multiblock copolymers via divinyl-terminated telechelic polyolefins,” Chem. Comm. 52 (2016) 2237-2240. DOI: 10.1039/C5CC09200K

117. C.-Y. Huang, X. Bao, Z. Ye, S. Lee, H. Chiang, H. Li, V. Chobpattana, B. Thibeault, W. Mitchell, S. Stemmer, A. Gossard, E. Sanchez, M. Rodwell, “Ultrathin InAs-channel MOSFETs on Si substrates,” IEEE Proceedings of 2015 International Symposium on VLSI Technology, Systems and Application (VLSI-TSA), pages 1-2, held in Hsinchu, Taiwan on 27-29 April 2015. DOI: 10.1109/VLSI-TSA.2015.7117566

118. Y. Huang, A.A. Keller, “EDTA functionalized magnetic nanoparticle sorbents for cadmium and lead contaminated water treatment,” Water Research 80 (2015) 159-168. DOI: 10.1016/j.watres.2015.05.011

119. S. Hussain, M. Kinnebrew, N.S. Schonenbach, E. Aye, S. Han, “Functional consequences of the oligomeric assembly of proteorhodopsin,” J. Molec. Biol. 427 (2015) 1278-1290. DOI: 10.1016/j.jmb.2015.01.004

120. T. Iwama, N. Laachi, K.T. Delaney, G.H. Fredrickson, “Field-theoretic simulations of directed self-assembly for contact multiplication,” J. Photopolymer Sci. & Tech. 28 (2015) 689. DOI: 10.2494/photopolymer.28.689

121. P.P. Iyer, N.A. Butakov, J.A. Schuller, “Reconfigurable semiconductor phased-array metasurfaces,” ACS Photonics 2 (2015)1077-1084. DOI: 10.1021/acsphotonics.5b00132

122. K. Izumi, B. Kim, N. Laachi, K.T. Delaney, M. Carilli, G.H. Fredrickson, “Barriers to defect melting in chemo-epitaxial directed self-assembly of lamellar-forming diblock copolymer/homopolymer blends,” Proc. SPIE 9423, Alternative Lithographic Technologies VII (2015) 94232C. DOI: 10.1117/12.2085685

123. R.W. Jackson, E.M. Zaleski, D.L. Poerschke, B.T. Hazel, M.R. Begley, C.G. Levi, “Interaction of molten silicates with thermal barrier coatings under temperature gradients,” Acta Mater. 89

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

(2015) 396-407. DOI: 10.1016/j.actamat.2015.01.038

124. D.J. Jorgensen, M.S. Titus, T.M. Pollock, “Femtosecond laser ablation and nanoparticle formation in intermetallic NiAl,” Appl. Surface Sci. 353 (2015) 700-707. DOI: 10.1016/j.apsusc.2015.06.155

125. I.Kaminker, R. Barnes, S. Han, “Overhauser dynamic nuclear polarization studies on local water dynamics,” in Methods in Enzymology: Electron Paramagnetic Resonance Investigations of Biological Systems by Using Spin Labels, Spin Probes, and Intrinsic Metal Ions, Part B, Eds. P. Qin, K. Warncke, Vol. 564, Elsevier, pp. 457-483 (2015). ISBN: 978-0-12-802835-3 DOI: 10.1016/bs.mie.2015.06.040

126. T. Kang, X. Banquy, J. Heo, C. Lim, N.A. Lynd, P. Lundberg, D.X. Oh, H.-K. Lee, Y.-K. Hong, D.S. Hwang, J.H. Waite, J.N. Israelachvili, C.J. Hawker, “Mussel-inspired anchoring of polymer loops that provide superior surface lubrication and antifouling properties,” ACS Nano 10 (2016) 930-937. DOI: 10.1021/acsnano.5b06066

127. T. Kang, D.X. Oh, J. Heo, H.-K. Lee, S. Choy, C.J. Hawker, D.S. Hwang, “Formation, removal, and reformation of surface coatings on various metal oxide surfaces inspired by mussel adhesives,” ACS Appl. Mater. Interfaces 7 (2015) 24656-24662. DOI: 10.1021/acsami.5b06910

128. S.W. Kaun, B. Mazumder, M.N. Fireman, E.C.H. Kyle, U.K Mishra, J.S. Speck, “Pure AlN layers in metal-polar AlGaN/AlN/GaN and AlN/GaN heterostructures grown by low- temperature ammonia-based molecular beam epitaxy,” Semi. Sci. Tech. 30 (2015) 055010. DOI: 10.1088/0268-1242/30/5/055010

129. E. Kioupakis, D. Steiauf, P. Rinke, K.T. Delaney, C.G. Van de Walle, “First-principles calculations of indirect Auger recombination in nitride semiconductors,” Phys. Rev. B 92 (2015) 035207. DOI: 10.1103/PhysRevB.92.035207

130. A. Knappschneider, C. Litterscheid, J. Brgoch, N.C. George, S. Henke, A.K. Cheetham, J.G. Hu,

R. Seshadri, B. Albert, “Manganese tetraboride, MnB4: High-temperature crystal structure, p–n transition, 55Mn NMR spectroscopy, solid solutions, and mechanical properties,” Chem. Eur. J. 21 (2015) 8177-8181. DOI: 10.1002/chem.201406631

131. S.J. Kowsz, C.D. Pynn, S.H. Oh, R.M. Farrell, J.S. Speck, S.P. DenBaars, S. Nakamura, “Demonstration of phosphor-free polarized white light emission from monolithically integrated semipolar InGaN quantum wells,” Appl. Phys. Lett. 107 (2015) 101104. DOI: 10.1063/1.4930304

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

132. K. Krishnaswamy, L. Bjaalie, B. Himmetoglu, A. Janotti, L. Gordon, C.G. Van de Walle,

“BaSnO3 as a channel material in perovskite oxide heterostructures,” Appl. Phys. Lett. 108 (2016) 083501. DOI: 10.1063/1.4942366

133. K. Krishnaswamy, C.E. Dreyer, A. Janotti, C.G. Van de Walle, “First-principles study of

surface charging in LaAlO3/SrTiO3 heterostructures,” Phys. Rev. B 92 (2015) 085420. DOI: 10.1103/PhysRevB.92.085420

134. H.H. Kristoffersen, H. Metiu, “Molten LiCl layer supported on MgO: Its possible role in enhancing the oxidative dehydrogenation of ethane,” J. Phys. Chem. C 119 (2015) 8681-8691. DOI: 10.1021/jp5128628

135. H.H. Kristoffersen, H. Metiu, “Reconstruction of low-index 〈-V2O5 surfaces,” J. Phys. Chem. C 119 (2015) 10500-10506. DOI: 10.1021/acs.jpcc.5b02383

136. H.H. Kristoffersen, H. Metiu, “Structure of V2O5•nH2O xerogels,” J. Phys. Chem. C 120 (2016) 3986-3992. DOI: 10.1021/acs.jpcc.5b12418

137. D. Kudela, S.A. Smith, A. May-Masnou, G.B. Braun, A. Pallaoro, C.K. Nguyen, T.T. Chuong, S. Nownes, R. Allen, N.R. Parker, H.H. Rashidi, J.H. Morrissey, G.D. Stucky, “Clotting activity of polyphosphate-functionalized silica nanoparticles,” Angew. Chem. Int. Ed. 54 (2015) 4018-4022. DOI: 10.1002/anie.201409639

138. S. Kumar, M. Chen, A.C. Anselmo, J.A. Muraski, S. Mitragotri, “Enhanced epidermal localization of topically applied steroids using SPACE™ peptide,” Drug Delivery and Translational Research 5 (2015) 523-530. DOI: 10.1007/s13346-015-0232-4

139. L.Y. Kuritzky, D.J. Myers, J. Nedy, K.M. Kelchner, S. Nakamura, S.P. DenBaars, C. Weisbuch, J.S. Speck, “Electroluminescence characteristics of blue InGaN quantum wells on m-plane GaN ‘double miscut’ substrates,” Appl. Phys. Express 8 (2015) 061002. DOI: 10.7567/APEX.8.061002

140. E.C.H. Kyle, S.W. Kaun, E.C. Young, J.S. Speck, “Increased p-type conductivity through use of an indium surfactant in the growth of Mg-doped GaN,” Appl. Phys. Lett. 106 (2015) 222103. DOI: 10.1063/1.4922216

141. N. Laachi, T. Iwama, K.T. Delaney, D. Shykind, C.J. Weinheimer, G.H. Fredrickson, “Directed self-assembly of linear arrays of block copolymer cylinders,” J. Polym. Sci. B: Polym. Phys. 53 (2015) 317. DOI: 10.1002/polb.23630

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

142. J.G. Labram, D.H. Fabini, E.E. Perry, A.J. Lehner, H. Wang, A.M. Glaudell, G. Wu, H. Evans, D. Buck, R. Cotta, L. Echegoyen, F. Wudl, R. Seshadri, M.L. Chabinyc, “Temperature- dependent polarization in field-effect transport and photovoltaic measurements of methylammonium lead iodide,” J. Phys. Chem. Lett. 6 (2015) 3565-3571. DOI: 10.1021/acs.jpclett.5b01669

143. B.H. Lee, G.C. Bazan, A.J. Heeger, “Doping-induced carrier density modulation in polymer field- effect transistors,” Adv. Mater. 28 (2016) 57-62. DOI: 10.1002/adma.201504307

144. B.H. Lee, B.B.Y. Hsu, S.N. Patel, J. Labram, C. Luo, G.C. Bazan, A.J. Heeger, “Flexible organic transistors with controlled nanomorphology,” Nano Lett. 16 (2016) 314-319. DOI: 10.1021/acs.nanolett.5b03868

145. D.G. Lee, P.R. Roehrdanz, M. Feraud, J. Ervin, T. Anumol, A. Jia, M. Park, C. Tamez, E.W. Morelius, J.L. Gardea-Torresdey, J. Izbicki, J.C. Means, S.A. Snyder, P.A. Holden, “Wastewater compounds in urban shallow groundwater wells correspond to exfiltration probabilities of nearby sewers,” Water Research 85 (2015) 467-475. DOI: 10.1016/j.watres.2015.08.048

146. W. Lee, Y.-S. Jun, J. Park, G.D. Stucky, “Crystalline poly(triazine imide) based g-CN as an efficient electrocatalyst for counter electrodes of dye-sensitized solar cells using a triiodide/iodide redox electrolyte,” J. Mater. Chem. A 3 (2015) 24232-24236. DOI: 10.1039/C5TA08650G

147. A.J. Lehner, D.H. Fabini, H.A. Evans, C.-A. Hébert, S.R. Smock, J. Hu, H. Wang, J.W. Zwanziger, M.L. Chabinyc, R. Seshadri, “Crystal and electronic structures of complex

bismuth iodides A3Bi2l9 (A = K, Rb, Cs) related to perovskite: Aiding the rational design of photovoltaics,” Chem. Mater. 27 (2015) 7137-7148. DOI: 10.1021/acs.chemmater.5b03147

148. A.J. Lehner, H. Wang, D.H. Fabini, C.D. Liman, C.-A. Hébert, E.E. Perry, M. Wang, G.C. Bazan, M.L. Chabinyc, R. Seshadri, “Electronic structure and photovoltaic application of

Bil3,” Appl. Phys. Lett. 107 (2015) 131109. DOI: 10.1063/1.4932129

149. J.T. Leonard, D.A. Cohen, B.P. Yonkee, R.M. Farrell, S.P. DenBaars, J.S. Speck, S. Nakamura, “Smooth e-beam-deposited tin-doped indium oxide for III-nitride vertical-cavity surface- emitting laser intracavity contacts,” J. of Appl. Phys. 118 (2015) 145304. DOI: 10.1063/1.4931883

150. J.T. Leonard, D.A. Cohen, B.P. Yonkee, R.M. Farrell, T. Margalith, S. Lee, S.P. DenBaars, J.S. Speck, S. Nakamura, “Nonpolar III-nitride vertical-cavity surface-emitting lasers incorporating an ion implanted aperture,” Appl. Phys. Lett. 107 (2015) 011102. DOI: 10.1063/1.4926365

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

151. J.T. Leonard, B.P. Yonkee, D.A. Cohen, L. Megalini, S. Lee, J.S. Speck, S.P. DenBaars, S. Nakamura, “Nonpolar III-nitride vertical-cavity surface-emitting laser with a photoelectrochemically etched air-gap aperture,” Appl. Phys. Lett. 108 (2016) 031111. DOI: 10.1063/1.4940380

152. J.T. Leonard, E.C. Young, B.P. Yonkee, D.A. Cohen, T. Margalith, S.P. DenBaars, J.S. Speck, S. Nakamura, “Demonstration of a III-nitride vertical-cavity surface-emitting laser with a III- nitride tunnel junction intracavity contact,” Appl. Phys. Lett. 107 (2015) 091105. DOI: 10.1063/1.4929944

153. R. Levenson, C. Bracken, N. Bush, D.E. Morse, “Cyclable condensation and hierarchical assembly of metastable reflectin proteins, the drivers of tunable biophotonics,” J. of Biol. Chem. 291 (2016) 4058-4068. DOI: 10.1074/jbc.M115.686014

154. T. Lewi, P.P. Iyer, N.A. Butakov, A.A. Mikhailovsky, J.A. Schuller, “Widely tunable infrared antennas using free carrier refraction,” Nano Lett. 15 (2015) 8188-8193. DOI: 10.1021/acs.nanolett.5b03679

155. H. Li, S. Keller, S.H. Chan, J. Lu, S.P. DenBaars, U.K. Mishra, “Unintentional gallium incorporation in AlN and its impact on the electrical properties of GaN/AlN and GaN/AlN/AlGaN heterostructures,” Semicond. Sci. Technol. 30 (2015) 055015. DOI: 10.1088/0268-1242/30/5/055015

156. W. Li, C.H. Hinton, S.S. Lee, J. Wu, J.D. Fortner, “Surface engineering superparamagnetic nanoparticles for aqueous applications: Design and characterization of tailored organic bilayers,” Environ. Sci.: Nano 3 (2016) 85-93. DOI: 10.1039/c5en00089k

157. W. Li, D. Ruth, J.D. Gunton, J.M. Rickman, “Selective encapsulation by Janus particles,” J. Chem. Phys. 142 (2015) 244705. DOI: 10.1063/1.4922781

158. H.-X. Lin, L. Chen, D.-Y. Liu, Z.-C. Lei, Y. Wang, X.-S. Zheng, B. Ren, Z.-X. Xie, G.D. Stucky, Z.-Q. Tian, “Constructing two-dimensional nanoparticle arrays on layered materials inspired by atomic epitaxial growth,” J. Am. Chem. Soc. 137 (2015) 2828-2831. DOI: 10.1021/ja5128538

159. D.-Y. Liu, X. Peng, B. Wu, X. Zheng, T.T. Chuong, J. Li, S. Sun, G.D. Stucky, “Uniform concave polystyrene-carbon core-shell nanospheres by a swelling induced buckling process,” J. Am. Chem. Soc. 137 (2015) 9772-9775. DOI: 10.1021/jacs.5b05027

160. J. Liu, N. Laachi, K.T. Delaney, G.H. Fredrickson, “Advantages and limitations of density functional theory in block copolymer directed self-assembly,” Proc. SPIE Alternative Lithographic Technologies VII 9423 (2015) 94231I-1. DOI: 10.1117/12.2085666

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

161. W. Liu, D. Sarkar, J. Kang, W. Cao, K. Banerjee, “Impact of contact on the operation and

performance of back-gated monolayer MoS2 field-effect-transistors,” ACS Nano 9 (2015) 7904- 7912. DOI: 10.1021/nn506512j

162. X. Liu, C.M. Jackson, F. Wu, B. Mazumder, R. Yeluri, J. Kim, S. Keller, A.R. Arehart, S.A. Ringel, J.S. Speck, U.K. Mishra, “Electrical and structural characterizations of crystallized

Al2O3/GaN interfaces formed by in situ metalorganic chemical vapor deposition,” J. Appl. Phys. 119 (2016) 015303. DOI: 10.1063/1.4939157

163. Y. Luo, D. Montarnal, S. Kirn, W. Shi, K.P. Barteau, C.W. Pester, P.D. Hustad, M.D. Christianson, G.H. Fredrickson, E.J. Kramer, C.J. Hawker, “Poly(dimethylsiloxane-b- methyl methacrylate): A promising candidate for sub-10 nm patterning,” Macromolecules 48 (2015) 3422-3430. DOI: 10.1021/acs.macromol.5b00518

164. Y. Luo, D. Montarnal, N.J. Treat, P.D. Hustad, M.D. Christianson, E.J. Kramer, G.H. Fredrickson, C.J. Hawker, “Enhanced block copolymer phase separation using click chemistry and ionic junctions,” ACS Macro Lett. 4 (2015) 1332-1336. DOI: 10.1021/acsmacrolett.5b00767

165. J.L. Lyons, A. Alkauskas, A. Janotti, C.G. Van de Walle, “First-principles theory of acceptors in nitride semiconductors,” Physica Status Solidi (b) 252 (2015) 900-908. DOI: 10.1002/pssb.201552062

166. J.L. Lyons, K. Krishnaswamy, L. Gordon, A. Janotti, C.G. Van de Walle, “Identification of microscopic hole-trapping mechanisms in nitride semiconductors,” IEEE Electron Device Lett. 37 (2016) 154-156. DOI: 10.1109/LED.2015.2509068

167. J.L. Lyons, C.G. Van de Walle, “Surprising stability of neutral interstitial hydrogen in diamond and cubic BN,” J. Phys.: Condens. Matter 28 (2016) 06LT01. DOI: 10.1088/0953-8984/28/6/06LT01

168. B.M. McSkimming, C. Chaix, J.S. Speck “High active nitrogen flux growth of GaN by plasma assisted molecular beam epitaxy,” J. Vac. Sci. Tech. A 33 (2015) 05E128. DOI: 10.1116/1.4928415

169. C.-K. Mai, T. Arai, X. Liu, S.L. Fronk, G.M. Su, R.A. Segalman, M.L. Chabinyc, G.C. Bazan, “Electrical properties of doped conjugated polyelectrolytes with modulated density of the ionic functionalities,” Chem. Comm. 51 (2015) 17607-17610. DOI: 10.1039/c5cc06690e

170. C.-K. Mai, B. Russ, S.L. Fronk, N. Hu, M.B. Chan-Park, J.J. Urban, R.A. Segalman, M.L. Chabinyc, G.C. Bazan, “Varying the ionic functionalities of conjugated polyelectrolytes

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

leads to both p- and n-type carbon nanotube composites for flexible thermoelectrics,” Energy Environ. Sci. 8 (2015) 2341-2346. DOI: 10.1039/c5ee00938c

171. R.N. Majzoub, K.K. Ewert, E.L. Jacovetty, B. Carragher, C.S. Potter, Y. Li, C.R. Safinya, “Patterned threadlike micelles and DNA-tethered nanoparticles: A structural study of PEGylated cationic liposome–DNA assemblies,” Langmuir 31 (2015) 7073-7083. DOI: 10.1021/acs.langmuir.5b00993

172. P. Malo de Molina, S. Lad, M.E. Helgeson, “Heterogeneity and its influence on the properties of di-functional poly(ethylene glycol) hydrogels: Structure and mechanics,” Macromolecules 48 (2015) 5402-5411. DOI: 10.1021/acs.macromol.5b01115

173. N.R. Martinez Rodriguez, S. Das, Y. Kaufman, J.N. Israelachvili, J.H. Waite, “Interfacial pH during mussel adhesive plaque formation,” Biofouling: The J. Bioadhesion and Biofilm Research 31 (2015) 221-227. DOI: 10.1080/08927014.2015.1026337

174. F.A. Medrano, R.L. Church, “A parallel computing framework for finding the supported solutions to a biobjective network optimization problem,” J. Multi-Crit. Decis. Anal. 22 (2015) 244-259. DOI: 10.1002/mcda.1541

175. L. Megalini, D.L. Becerra, R.M. Farrell, A. Pourhashemi, J.S. Speck, S. Nakamura,

S.P. DenBaars, D.A. Cohen, “Continuous-wave operation of a (20-2-1) InGaN laser diode with a photoelectrochemically etched current aperture,” Appl. Phys. Express 8 (2015) 042701. DOI: 10.7567/APEX.8.042701

176. L. Megalini, L.Y. Kuritzky, J.T. Leonard, R. Shenoy, K. Rose, S. Nakamura, J.S. Speck, D.A. Cohen, S.P. DenBaars “Selective and controllable lateral photoelectrochemical etching of nonpolar and semipolar InGaN/GaN multiple quantum well active regions,” Appl. Phys. Express 8 (2015) 066502. DOI: 10.7567/APEX.8.066502

177. A. Melker, B.P. Fors, C.J. Hawker, J.E. Poelma, “Continuous flow synthesis of poly(methyl methacrylate) via a light-mediated controlled radical polymerization,” J. Polym. Sci. A: Polym. Chem. 53 (2015) 2693-2698. DOI: 10.1002/pola.27765

178. R.J. Messinger, T.G. Marks, S.S. Gleiman, F. Milstein, B.F. Chmelka, “Molecular origins of macroscopic mechanical properties of elastomeric organosiloxane foams,” Macromolecules 48 (2015) 4835-4849. DOI: 10.1021/acs.macromol.5b00532

179. M.-S. Miao, X.-L. Wang, J. Brgoch, F. Spera, M.G. Jackson, G. Kresse, H.-Q. Lin, “Anionic chemistry of noble gases: Formation of Mg–NG (NG = Xe, Kr, Ar) compounds under pressure,” 69

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

J. Am. Chem. Soc. 137 (2015) 14122-14128. DOI: 10.1021/jacs.5b08162

180. E. Mikheev, C.R. Freeze, B.J. Isaac, T.A. Cain, S. Stemmer, “Separation of transport lifetimes

in SrTiO3-based two-dimensional electron liquids,” Phys. Rev. B 91 (2015) 165125. DOI: 10.1103/PhysRevB.91.165125

181. E. Mikheev, A.J. Hauser, B. Himmetoglu, N.E. Moreno, A. Janotti, C.G. Van de Walle, S. Stemmer, “Tuning bad metal and non-Fermi liquid behavior in a Mott material: Rare earth nickelate thin films,” Sci. Adv. 1 (2015) e1500797. DOI: 10.1126/sciadv.1500797

182. E. Mikheev, S. Raghavan, S. Stemmer, “Dielectric response of metal/SrTiO3/two-dimensional electron liquid heterostructures,” Appl. Phys. Lett. 107 (2015) 072905. DOI: 10.1063/1.4928751

183. D. Morton, S. Mortezaei, S. Yemenicioglu, M.J. Isaacman, I.C. Nova, J.H. Gundlach, L. Theogarajan, “Tailored polymeric membranes for Mycobacterium smegmatis porin A (MspA) based biosensors,” J. Mater. Chem. B 3 (2015) 5080. DOI: 10.1039/c5tb00383k

184. S. Mubeen, Y.-S. Jun, J. Lee, E.W. McFarland, “Solid suspension flow batteries using earth abundant materials,” ACS Appl. Mater. Interfaces 8 (2016) 1759-1765. DOI: 10.1021/acsami.5b09515

185. R.G. Mullen, J.-E. Shea, B. Peters, “Easy transition path sampling methods: Flexible-length aimless shooting and permutation shooting,” J. Chem. Theory Comput. 11 (2015) 2421-2428. DOI: 10.1021/acs.jctc.5b00032

186. H.R. Naughton, M.A. Alexandrou, T.H. Oakley, B.J. Cardinale, “Phylogenetic distance does not predict competition in green algal communities,” Ecosphere 6 (2015) 1-19. DOI: 10.1890/ES14-00502.1

187. J.G. Nedy, N.G. Young, K.M. Kelchner, Y. Hu, R.M. Farrell, S. Nakamura, S.P. DenBaars, C. Weisbuch, J.S. Speck, “Low damage dry etch for III-nitride light emitters,” Semi. Sci. Tech. 30 (2015) 085019. DOI: 10.1088/0268-1242/30/8/085019

188. T.-A.D. Nguyen, Z.R. Jones, B.R. Goldsmith, W.R. Buratto, G. Wu, S.L. Scott, T.W. Hayton,

“A Cu25 nanocluster with partial Cu(0) character,” J. Am. Chem. Soc. 137 (2015) 13319-13324. DOI: 10.1021/jacs.5b07574

189. H. Ohtaki, F. Deplace, G.D. Vo, A.M. LaPointe, F. Shimizu, T. Sugano, E.J. Kramer, G.H. Fredrickson, G.W. Coates, “Allyl-terminated polypropylene macromonomers: A route to polyolefin elastomers with excellent elastic behavior,” Macromolecules 48 (2015) 7489. DOI: 10.1021/acs.macromol.5b01975

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

190. S.J. Patel, J.A. Logan, S.D. Harrington, B.D. Schultz, C.J. Palmstrøm, “Surface reconstructions and transport of epitaxial PtLuSb (001) thin films grown by MBE,” J. Cryst. Growth 436 (2016) 145-149. DOI: 10.1016/j.jcrysgro.2015.12.003

191. S.N. Patel, G.M. Su, C. Luo, M. Wang, L.A. Perez, D.A. Fischer, D. Prendergast, G.C. Bazan, A.J. Heeger, M.L. Chabinyc, E.J. Kramer, “NEXAFS spectroscopy reveals the molecular orientation in blade-coated pyridal[2,1,3]thiadiazole-containing conjugated polymer thin films,” Macromolecules 48 (2015) 6606-6616. DOI: 10.1021/acs.macromol.5b01647

192. J.S. Paustian, C.D. Angulo, R. Nery-Azevedo, N. Shi, A.I. Abdel-Fattah, T.M. Squires, “Direct measurements of colloidal solvophoresis under imposed solvent and solute gradients,” Langmuir 31 (2015) 4402-4410. DOI: 10.1021/acs.langmuir.5b00300

193. A. Pavlova, C.-Y. Cheng, M. Kinnebrew, J. Lew, F.W. Dahlquist, S. Han, “Protein structural and surface water rearrangement constitute major events in the earliest aggregation stages of tau,” PNAS 113 (2016) E127-E136. DOI: 10.1073/pnas.1504415113

194. H. Peelaers, E. Kioupakis, C.G. Van de Walle, “Free-carrier absorption in transparent

conducting oxides: Phonon and impurity scattering in SnO2,” Phys. Rev. B 92 (2015) 235201. DOI: 10.1103/PhysRevB.92.235201

195. H. Peelaers, K. Krishnaswamy, L. Gordon, D. Steiauf, A. Sarwe, A. Janotti, C.G. Van de Walle, “Impact of electric-field dependent dielectric constants on two-dimensional electron gases in complex oxides,” Appl. Phys. Lett. 107 (2015) 183505. DOI: 10.1063/1.4935222

196. H. Peelaers, C.G. Van de Walle, “Brillouin zone and band structure of β-Ga2O3,” Phys. Status Solidi B 252 (2015) 828-832. DOI: 10.1002/pssb.201451551

197. N.D. Petsev, L.G. Leal, M.S. Shell, “Multiscale simulation of ideal mixtures using smoothed dissipative particle dynamics,” J. Chem. Phys. 144 (2016) 084115. DOI: 10.1063/1.4942499

198. S. Pimputkar, S. Suihkonen, M. Imade, Y. Mori, J.S. Speck, S. Nakamura, “Free electron concentration dependent sub-bandgap optical absorption characterization of bulk GaN crystals,” J. Cryst. Growth 432 (2015) 49-53. DOI: 10.1016/j.jcrysgro.2015.09.016

199. D.L. Poerschke, G.G.E. Seward, C.G. Levi, “Inﬂuence of Yb:Hf ratio on ytterbium hafnate/molten silicate (CMAS) reactivity,” J. Am. Ceram. Soc. 99 (2016) 651-659. DOI: 10.1111/jace.13964

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

200. B.C. Popere, B. Russ, A.T. Heitsch, P. Trefonas, R.A. Segalman, “Large-area, nanometer-scale discrete doping of semiconductors via block copolymer self-assembly,” Adv. Mater. Interfaces 2 (2015) 1500421. DOI: 10.1002/admi.201500421

201. A. Pourhashemi, R.M. Farrell, D.A. Cohen, J.S. Speck, S.P. DenBaars, S. Nakamura, “High- power blue laser diodes with indium tin oxide cladding on semipolar (2021) GaN substrates,” Appl. Phys. Lett. 106 (2015) 111105. DOI: 10.1063/1.4915324

202. J.W. Pro, R.K. Lim, L.R. Petzold, M. Utz, M.R. Begley, “GPU-based simulations of fracture in idealized brick and mortar composites,” J. Mech. Phys. Sol. 80 (2015) 68-85. DOI: 10.1016/j.jmps.2015.03.011

203. J.W. Pro, R.K. Lim, L.R. Petzold, M. Utz, M.R. Begley, “The impact of stochastic microstructures on the macroscopic fracture properties of brick and mortar composites,” Extreme Mechanics Lett. 5 (2015) 1-9. DOI: 10.1016/j.eml.2015.09.001

204. M.G. Ramírez, J.P. Jahnke, M.J.N. Junk, J.M. Villalvilla, P.G. Boj, J.A. Quintana, E.M. Calzado, B.F. Chmelka, M.A. Díaz-García, “Improved amplified spontaneous emission of dye-doped functionalized mesostructured silica waveguide films,” Adv. Optical Mater. 3 (2015) 1454-1461. DOI: 10.1002/adom.201500297

205. R.K. Rhein, P.C. Dodge, M.-H. Chen, M.S. Titus, T.M. Pollock, A. Van der Ven, “Role of

vibrational and configurational excitations in stabilizing the L12 structure in Co-rich Co-Al-W alloys,” Phys. Rev. B 92 (2015) 174117. DOI: 10.1103/PhysRevB.92.174117

+ 206. A.Y. Rogachev, M.---S. Miao, G. Merino, R. Hoffmann, “Molecular CsF5 and CsF2 ,” Angewandte Chemie Int’l. Ed. 54 (2015) 8275-8278. DOI: 10.1002/ange.201500402

207. M.N. Rossol, V.P. Rajan, F.W. Zok, “Effects of weave architecture on mechanical response of 2D ceramic composites,” Composites Part A: Appl. Sci. and Manufac. 74 (2015) 141-152. DOI: 10.1016/j.compositesa.2015.04.003

208. R.P. Sangodkar, B.J. Smith, D. Gajan, A.J. Rossini, L.R. Roberts, G.P. Funkhouser, A. Lesage, L. Emsley, B.F. Chmelka, “Influences of dilute organic adsorbates on the hydration of low- surface-area silicates,” J. Am. Chem. Soc. 137 (2015) 8096-8112. DOI: 10.1021/jacs.5b00622

209. D. Sarkar, X. Xie, W. Liu, W. Cao, J. Kang, Y. Gong, S. Kraemer, P.M. Ajayan, K. Banerjee, “A subthermionic tunnel field-effect transistor with an atomically thin channel,” Nature 526 (2015) 91.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

DOI: 10.1038/nature15387

210. M. Seal, N. Singh, E.W. McFarland, J. Baltrusaitis, “Electrochemically deposited Sb and In doped tin sulfide (SnS) photoelectrodes,” J. Phys. Chem. C 119 (2015) 6471-6480. DOI: 10.1021/jp512927y

211. K.A. See, S. Hug, K. Schwinghammer, M.A. Lumley, Y. Zheng, J.M. Nolt, G.D. Stucky, F. Wudl, B.V. Lotsch, R. Seshadri, “Lithium charge storage mechanisms of cross-linked triazine networks and their porous carbon derivatives,” Chem. Mater. 27 (2015) 3821-3829. DOI: 10.1021/acs.chemmater.5b00772

212. M.-J. Sher, N.M. Mangan, M.J. Smith, Y.-T. Lin, S. Marbach, T.M. Schneider, S. Gradečak,

M.P. Brenner, E. Mazur, “Femtosecond-laser hyperdoping silicon in an SF6 atmosphere: Dopant incorporation mechanism,” J. Appl. Phys. 117 (2015) 125301. DOI: 10.1063/1.4914520

213. J.B. Sherman, C.-Y. Chiu, R. Fagenson, G. Wu, C.J. Hawker, M.L. Chabinyc, “Suppressing crystallization in solution-processed thin films of organic semiconductors,” MRS Commun. 5 (2015) 447-452. DOI: 10.1557/mrc.2015.60

214. J.B. Sherman, K. Moncino, T. Baruah, G. Wu, S.R. Parkin, B. Purushothaman, R. Zope, J. Anthony, M.L. Chabinyc, “Crystalline alloys of organic donors and acceptors based on TIPS- pentacene,” J. Phys. Chem. C 119 (2015) 20823-20832. DOI: 10.1021/acs.jpcc.5b06363

215. W. Shi, G.H. Fredrickson, E.J. Kramer, C. Ntaras, A. Avgeropoulos, Q. Demassieux, C. Creton, ”Mechanics of an asymmetric hard−soft lamellar nanomaterial,” ACS Nano 10 (2016) 2054-2062. DOI: 10.1021/acsnano.5b06215

216. W. Shi, A.L. Hamilton, K.T. Delaney, G.H. Fredrickson, E.J. Kramer, C. Ntaras, A. Avgeropoulos, N.A. Lynd, “Creating extremely asymmetric lamellar structures via fluctuation-assisted unbinding of miktoarm star block copolymer alloys,” J. Am. Chem. Soc. Comm. 137 (2015) 6160-6163. DOI: 10.1021/jacs.5b02881

217. W. Shi, A.L. Hamilton, K.T. Delaney, G.H. Fredrickson, E.J. Kramer, C. Ntaras, A. Avgeropoulos, N.A. Lynd, Q. Demassieux, C. Creton, “Aperiodic `bricks and mortar’ mesophase: A new equilibrium state of soft matter and application as a stiff thermoplastic elastomer,” Macromolecules 48 (2015) 5378. [Cover Article]. DOI: 10.1021/acs.macromol.5b01210

218. W. Shi, W. Li, K.T. Delaney, G.H. Fredrickson, E.J. Kramer, C. Ntaras, A. Avgeropoulos, N.A. Lynd, “Morphology re-entry in asymmetric PS-PI-PS’ triblock copolymer and PS homopolymer blends,” J. Polym. Sci. B: Polym. Phys. 54 (2016) 169-179. DOI: 10.1002/polb.23811

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

219. B. Shojaei, A. McFadden, J. Shabani, B.D. Schultz, C.J. Palmstrøm, “Studies of scattering mechanisms in gate tunable InAs/(Al,Ga)Sb two dimensional electron gases,” Appl. Phys. Lett. 106 (2015) 222101. DOI: 10.1063/1.4921970

220. B. Shojaei, P.J.J. O'Malley, J. Shabani, P. Roushan, B.D. Schultz, R.M. Lutchyn, C. Nayak, J.M. Martinis, C.J. Palmstrøm, “Demonstration of gate control of spin splitting in a high- mobility InAs/AlSb two-dimensional electron gas,” Phys. Rev. B 93 (2016) 075302. DOI: 10.1103/PhysRevB.93.075302

221. S.D. Springer, A. Butler, “Magnetic susceptibility of Mn(III) complexes of hydroxamate siderophores,” J. Inorg. Biochem. 148 (2015) 22-26. DOI: 10.1016/j.jinorgbio.2015.04.015

222. G.M. Su, E. Lim, E.J. Kramer, M.L. Chabinyc, “Phase separated morphology of ferroelectric– semiconductor polymer blends probed by synchrotron X-ray methods,” Macromolecules 48 (2015) 5861-5867. DOI: 10.1021/acs.macromol.5b01354

223. M.S. Titus, M.P. Echlin, P. Gumbsch, T.M. Pollock, “Dislocation injection in strontium titanate by femtosecond laser pulses,” J. Appl. Phys. 118 (2015) 075901. DOI: 10.1063/1.4928772

224. F.M. Toma, F. Puntoriero, T.V. Pho, M. La Rosa, Y.-S. Jun, B.J. Tremolet de Villers, J. Pavlovich, G.D. Stucky, S. Campagna, F. Wudl, “Polyimide dendrimers containing multiple electron donor-acceptor units and their unique photophysical properties,” Angew. Chem. Int. Ed. 54 (2015) 6775-6779. DOI: 10.1002/anie.201501298

225. J.S. Van Sluytman, S. Krämer, V.K. Tolpygo, CG. Levi, “Microstructure evolution of ZrO2–

YbTaO4 thermal barrier coatings,” Acta Mater. 96 (2015) 133-142. DOI: 10.1016/j.actamat.2015.06.007

226. C.X. Wang, A. Braendle, M.S. Menyo, C.W. Pester, E.E. Perl, I. Arias, C.J. Hawker, D. Klinger, “Catechol-based layer-by-layer assembly of composite coatings: A versatile platform to hierarchical nano-materials,” Soft Matter 11 (2015) 6173-6178. DOI: 10.1039/c5sm01374g

227. X. Wang, J.L. Brosmer, A. Thevenon, P.L. Diaconescu, “Highly active yttrium catalysts for the ring-opening polymerization of ε-caprolactone and δ-valerolactone,” Organometallics 34 (2015) 4700-4706. DOI: 10.1021/acs.organomet.5b00442

228. M.Q. Wilber, J. Kitzes, J. Harte, “Scale collapse and the emergence of the power law species– area relationship,” Global Ecology and Biogeography 24 (2015) 883-895. DOI: 10.1111/geb.12309

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

229. B. Wu, D. Liu, S. Mubeen, T.T. Chuong, M. Moskovits, G.D. Stucky, “Anisotropic growth of

TiO2 onto gold nanorods for plasmon-enhanced hydrogen production from water reduction,” J. Am. Chem. Soc. 138 (2016) 1114-1117. DOI: 10.1021/jacs.5b11341

230. B.P. Yonkee, R.M. Farrell, J.T. Leonard, S.P. DenBaars, J.S. Speck, S. Nakamura, “Demonstration of low resistance ohmic contacts to p-type (20-21) GaN,” Semi. Sci. Tech. 30 (2015) 075007. DOI: 10.1088/0268-1242/30/7/075007

231. E.C. Young, B.P. Yonkee, F. Wu, S.H. Oh, S.P. DenBaars, S. Nakamura, J.S. Speck, “Hybrid tunnel junction contacts to III–nitride light-emitting diodes,” Appl. Phys. Express. 9 (2016) 022102. DOI: 10.7567/APEX.9.022102

232. N.G. Young, R.M. Farrell, S. Oh, M. Cantore, F. Wu, S. Nakamura, S.P. DenBaars, C. Weisbuch, J.S. Speck, “Polarization field screening in thick (0001) InGaN/GaN single quantum well light-emitting diodes,” Appl. Phys. Lett. 108 (2016) 061105. DOI: 10.1063/1.4941815

233. E.M. Zaleski, C. Ensslen, C.G. Levi, “Melting and crystallization of silicate systems relevant to thermal barrier coating damage,” J. Am. Ceram. Soc. 98 (2015) 1642-1649. DOI: 10.1111/jace.13478

234. E. Zamanidoost, F.M. Bayat, D. Strukov, I. Kataeva, “Manhattan rule training for memristive crossbar circuit pattern classifiers,” 2015 IEEE 9th International Symposium on Intelligent Signal Processing (WISP), pages 1-6, 15-17 May 2015 in Siena, Italy. DOI: 10.1109/WISP.2015.7139171

235. H. Zeng, D. Liu, Y. Zhang, K.A. See, Y.-S. Jun, G. Wu, J.A. Gerbec, X. Ji, G.D. Stucky,

“Nanostructured Mn-doped V2O5 cathode material fabricated from layered vanadium jarosite,” Chem. Mater. 27 (2015) 73317336. DOI: 10.1021/acs.chemmater.5b02840

236. Y. Zheng, M.-S. Miao, G. Dantelle, N.D. Eisenmenger, G. Wu, I. Yavuz, M.L. Chabinyc, K.N. Houk, F. Wudl, “A solid-state effect responsible for an organic quintet state at room temperature and ambient pressure,” Adv. Mater. 27 (2015) 1718-1723. DOI: 10.1002/adma.201405093

237. N.E.R. Zimmermann, B. Vorselaars, D. Quigley, B. Peters, “Nucleation of NaCl from aqueous solution: Critical sizes, ion-attachment kinetics, and rates,” J. Am. Chem. Soc. 137 (2015) 13352- 13361. DOI: 10.1021/jacs.5b08098

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

MRSEC-SUPPORTED PATENTS

2015-2016 MRL PATENTS

(a) Patents granted during the current period

“Organic electronic devices prepared using decomposable polymer additives” C.J. Hawker, M. Chabinyc, S-Y. Ku, C. Liman, S. Aramaki, H. Wang, T. Niinomi U.S. Patent 9,260,443 (February 16, 2016)

“Spatial and temporal control of brush formation on surfaces” C.J. Hawker, B.P. Fors, J.E. Poelma U.S. Patent 9,081,283 (July 14, 2015)

“Polyphosphate-functionalized inorganic nanoparticles as hemostatic compositions and methods of use” D. Kudela, G.D. Stucky, A. May-Masnou, G.B. Braun, J.H. Morrissey, S.A. Smith U.S. Patent 9,186,417 (November 17, 2015)

“Compositions for controlled assembly and improved ordering of silicon-containing block copolymers” D. Montarnal, C.J. Hawker, E.J. Kramer, G.H. Fredrickson U.S. Patent 9,158,200 (October 13, 2015)

“High energy capacitors boosted by both catholyte and anolyte” G.D. Stucky, X. Ji U.S. Patent 9,196,425 (November 24, 2015)

(b) Patent applications (excluding provisional applications) during the current period

None

“Doping preferences in conjugated polyelectrolyte /single-walled carbon nanotube composites” G. Bazan, C.-K. Mai U.S. Patent Application 62/213,782 (September 3, 2015)

“Mussel-inspired under-water adhesives/coatings from renewable resources” J.H. Waite, B.K. Ahn, C.J. Hawker, J. Heo, T. Kang U.S. Patent Application 14/908,956 (January 29, 2016)

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

15. BIOS OF NEW SENIOR INVESTIGATORS

No new investigators were added to the UCSB MRSEC in the past year.

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

16. MRSEC FACULTY HONORS/AWARDS 2015-16

Fredrickson, Glenn Re-Appointed Chief Technology Officer, Managing Corporate Executive Officer, Member of the Board, Mitsubishi Chemical Holdings Corporation, Tokyo, Japan, 2015 Amundson Lecturer, University of Minnesota, 2016

Han, Songi: Friedrich Wilhelm Bessel Prize, Alexander von Humboldt Foundation, 2015

Hawker, Craig: Elected Member of the National Academy of Inventors, 2015 Elected as Fellow: American Association for the Advancement of Science (AAAS), 2015 Dow Lecturer, Northwestern University, 2015 Sproull Lecturer, Cornell University, 2015 Purves Lecturer, McGill University, 2015 The Grandpierre Lecturer, Columbia University 2015 Eli Lilly Distinguished Lecturer, Colorado State University, 2015 Pettit Lecturer, University of Texas, Austin

Helgeson, Matthew: 2015 Department of Energy Early Career Award

Israelachvili, Jacob: Plenary Lecturer, 5th International Conference on Colloids and Interfaces, Amsterdam, the Netherlands, 2015 Plenary Lecturer, International Tribology Conference, Tokyo, Japan, 2015

Palmstrøm, Christopher: Molecular Beam Epitaxy (MBE) Innovator Award, 2015 National Security Science and Engineering Faculty Fellow, Dept of Defence, 2015

Read de Alaniz, Javier: 2015-16 Harold J. Plous Award, UC Santa Barbara

Schuller, Jon: MRSEC supported publication, “Beam Engineering for Selective and Enhanced Coupling to Multipole Resonances” chosen as an Editor’s Selection by Physical Review B (PRB)

Segalman, Rachel: Elected Fellow of the American Physical Society, 2015

Squires, Todd: Elected Fellow of the American Physical Society, 2015

Stemmer, Susanne: Elected Fellow of the Microscopy Society of America, 2015

Stucky, Galen: Elected Fellow of the National Academy of Inventors, 2015

Materials Research Laboratory at UCSB: An NSF MRSEC 2016 Annual Report

Valentine, Megan: 2015 Fulbright Scholar Award

Van de Walle: Elected to the National Academy for Engineering (NAE), 2015

Graduate Student Awards:

Buffon, Mandi: 2015 Best Poster Award, Pacifichem Conference, Honolulu HI

Butala, Megan: 2015 Best Poster Award, Pacifichem Conference, Honolulu HI

Gebbie, Matthew: Selected from a world-class pool of Ph.D. student to be UCSB’s representative (1 of 25 selected by the NSF from the USA) at the “General Lindau Meeting of Nobel Laureates” a once-in-a- lifetime opportunity. The meeting took place on 28 June-3 July, 2015 in Lindau, Germany.

Isaac, Brandon: 2015 NSF Graduate Research Fellowship

Marshall, Patrick: 2015 Best Poster Award, SPICE Workshop on Bad Metal Behavior in Mott Systems

Myers, Brian: 2015 IBM PhD Fellowship Award

Patterson, Anastasia: 2015 Best Poster Award, Edward J. Kramer Symposium, Santa Barbara, CA 2015

Steffes, Victoria: 2015 NSF Graduate Research Fellowship

Thomas, Elayne: 2015 Best Poster Award, Materials Research Outreach Program, Santa Barbara, CA 2016

Wonder, Emily: 2015 NSF Graduate Research Fellowship

Undergraduate Awards:

Mann, Joseph: MRL RISE undergraduate intern was awarded the Goldwater Scholarship, April 2015