CNSE 2013 Faculty Research Report

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2013 CNSE Faculty Research Report

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2013 FACULTY RESEARCH REPORT www.sunycnse.com

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CNSE Senior Vice President and Chief Executive Officer; Vice President and Special Advisor to the President, University-wide Economic Innovation and Outreach; Professor of Nanoscience Alain E. Kaloyeros, Ph.D. CNSE Executive Vice President of Innovation and Technology; CNSE Vice President for Research Michael Liehr, Ph.D. SUNY College of Nanoscale Science and Engineering 257 Fuller Road Albany, New York 12203 www.sunycnse.com The CNSE 2013 Annual Faculty Report is also available on the web at: http://www.sunycnse.com/LeadingEdgeResearchandDevelopment.aspx Report Compiled and Edited by Steve Ference | Kristin Haacker Design by Kristin Haacker Photography by Melissa Renzi © 2014

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TABLE OF CONTENTS The Nanoscience Constellation Ion Beam Laboratory ............................................................................................................................. 7 Hassaram Bakhru, Ph.D., Distinguished Service Professor and Head, Nanoscience Constellation Mengbing Huang, Ph.D., Associate Professor of Nanoscience Characterization, Metrology, and Physics of Nanoscale Materials and Structures .................................................................................................... 13 Alain Diebold, Ph.D., Empire Innovation Professor of Nanoscale Science; Executive Director, Center for Nanoscale Metrology; Executive Director, NC3 Defects and Microstructural Engineering ............................................................................................ 19 Kathleen Dunn, Ph.D., Associate Professor of Nanoscience Schottky Barrier Height Measurement Utilizing Ballistic Electron Emission Microscopy .............................................................................................. 23 Vincent Labella, Ph.D., Associate Professor of Nanoscience Compound Semiconductor Research .................................................................................................. 24 Serge Oktyabrsky, Ph.D., Professor of Nanoscience Nanoscale Characterization and Metrology ........................................................................................ 32 Bradley Thiel, Ph.D., Professor of Nanoscience The Nanoengineering Constellation Plasmonics-Based Chemical Sensors ................................................................................................. 35 Michael Carpenter, Ph.D., Associate Professor of Nanoengineering Lithography ............................................................................................................................................ 38 Gregory Denbeaux, Ph.D., Associate Professor of Nanoengineering PROGRAM: NICE-IP (NSF PFI) .............................................................................................................. 41 Harry Efstathiadis, Ph.D., Associate Professor of Nanoengineering Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY

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TABLE OF CONTENTS Physics of Nanometer-Scale Structures .............................................................................................. 43 Timothy Groves, Ph.D., Interim Vice President of Academic Affairs; Empire Innovation Professor of Nanoscale Science; Director, Center for Nanolithography Development; Associate Head of the Nanoengineering Constellation Photovoltaics ......................................................................................................................................... 49 Harry Efstathiadis, Ph.D., Associate Professor of Nanoengineering Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY PROGRAM: U.S. Photovoltaic Manufacturing Consortium ............................................................... 54 Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY Makoto Hirayama, Ph.D., CNSE Vice President for Asian and Pacific Rim Strategic Alliances; Professor of Nanoengineering Timothy Groves, Ph.D., Interim Vice President of Academic Affairs; Empire Innovation Professor of Nanoscale Science; Director, Center for Nanolithography Development; Associate Head of the Nanoengineering Constellation Alain Diebold, Ph.D., Empire Innovation Professor of Nanoscale Science; Executive Director, Center for Nanoscale Metrology; Executive Director, NC3 James Lloyd, Ph.D., Senior Research Scientist, Professor Harry Efstathiadis, Ph.D., Associate Professor of Nanoengineering PROGRAM: ASPIRE (NSF AIR) ............................................................................................................. 60 John Hartley, Ph.D., Professor and Head, Nanoengineering Constellation; Director, Advanced Lithography Center Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY Supercapacitors ..................................................................................................................................... 62 Manisha Rane-Fondacaro, Ph.D., Instructor Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY

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TABLE OF CONTENTS III-Nitride based Optoelectronics Materials and Devices ................................................................... 65 Fatemeh (Shadi) Shahedipour-Sandvik, Ph.D., Associate Professor of Nanoengineering Nano-Inspired Device Research ........................................................................................................... 71 Bin Yu, Ph.D., Professor of Nanoengineering The Nanoeconomics Constellation PROGRAM: eNTEL ................................................................................................................................. 77 Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY Laura Schultz, Ph.D., Assistant Professor of Nanoeconomics PROGRAM: iCLEAN, CNSE’s Energy and Nanotechnology Incubator ................................................................................................................... 79 Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY Laura Schultz, Ph.D., Assistant Professor of Nanoeconomics INITIATIVE: New York Business Plan Competition ............................................................................. 81 Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY Laura Schultz, Ph.D., Assistant Professor of Nanoeconomics INITIATIVE: Tech Valley Innovation Pipeline ....................................................................................... 83 Pradeep Haldar, Ph.D., CNSE Vice President of Entrepreneurship Innovation and Clean Energy Programs; Head, Nanoeconomics Constellation; Professor; Director, E2TAC; Executive Director, NENY Laura Schultz, Ph.D., Assistant Professor of Nanoeconomics 85 The Economics of Emerging Technologies: Understanding Investment and Commercialization ........................................................................... Laura Schultz, Ph.D., Assistant Professor of Nanoeconomics

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TABLE OF CONTENTS The Nanobioscience Constellation Sensors, Components, and Mitigators of Stress and Damage Signaling .............................................................................................................. 89 Thomas Begley, Ph.D., Associate Professor of Nanobioscience; Associate Vice President and Director of the Systems Toxicology Laboratory Occupational and Environmental Health and Safety of Engineered Nanomaterials ................................................................................................... 94 Sara Brenner, M.D., M.P.H., Assistant Vice President for NanoHealth Initiatives; Assistant Professor of Nanobioscience Nanobiotechnology, Biosensors & Bioinspired Devices ................................................................... 102 Nathaniel Cady, Ph.D., Associate Professor of Nanobioscience Wafer Processing and Nanobioscience Research ............................................................................. 108 James Castracane, Ph.D., Professor and Head, Nanobioscience Constellation Cellular and Molecular Mechanisms of Cancer Metastasis ............................................................... 114 Nadine Hempel, Ph.D., Assistant Professor of Nanobioscience Nanobioscience and the Role of Oxidants .......................................................................................... 118 J. Andres Melendez, Ph.D., Professor and Associate Head, Nanobioscience Constellation Self-Assembly Platforms: Nanomachines and 3D Tissue Engineering ........................................................................................ 125 Janet Paluh, Ph.D., Associate Professor of Nanobioscience Mammalian and Microbial Cell Bioprocessing ................................................................................... 131 Susan Sharfstein, Ph.D., Associate Professor of Nanobioscience RNA-Based Nanotechnology ................................................................................................................ 136 Scott Tenenbaum, Ph.D., Associate Professor of Nanobioscience Calcium Signaling in Vascular Diseases ............................................................................................. 140 Mohamed Trebak, Ph.D., Associate Professor of Nanobioscience

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It is my pleasure to present the SUNY College of Nanoscale Science and Engineering’s (CNSE) 2013 Faculty Research Report, showcasing the capabilities of CNSE’s world-class innovation ecosystem that is driving the rapid growth of New York’s nanotechnology-based economy under the vision of Governor Andrew M. Cuomo. The mission of CNSE is to serve as an intellectually vibrant powerhouse for research and education in the nanotechnology disciplines, from theoretical principles to practical applications, and this mission is exemplified by the leading-edge work which is conducted by faculty at CNSE’s unparalleled Albany NanoTech Complex. This critical research enables a world in which ultra-fast and secure data is more accessible than ever; novel approaches to healthcare offer improved detection, treatment, and prevention of diseases; clean energy applications show the ability to power the technologies people rely on with less impact to the environment; and so many other nanoscale science-based advances promise to enhance our daily lives. With its unique publicly led, public-private partnership model providing access to 300 mm and 450 mm wafer processing capabilities, CNSE is a model for driving next-generation research. Moreover, CNSE is also able to quickly and efficiently integrate these discoveries into advanced manufacturing processes, providing a true “lab to fab” capability that accelerates innovation while controlling costs amid an increasingly complex research and development environment. The 2013 Faculty Research Report highlights the key areas of CNSE’s educational and research efforts: » » » » Nanoscience refers to the observation, identification, description, discovery, experimental investigation, and theoretical interpretation of nanoscale phenomena. Nanoengineering is the application of nanoscience principles to practical ends, such as the design, manufacture, and operation of efficient and functional structures, machines, processes, and systems on the atomic scale. Nanoeconomics is the formulation, study, and analysis of the economic and business principles underlying the development and deployment of nanoscale know-how, products, and systems Nanobioscience refers to the application of nanoscale scientific concepts and principles to the study of biological and biomedical structures and systems. Nanobioscience also encompasses CNSE’s NanoHealth initiative, which is aimed at developing novel nanotechnology applications in nanomedicine, including nanotoxicology and environmental and public health. Thank you for the opportunity to share CNSE’s exciting research. Michael Liehr CNSE Executive Vice President of Innovation and Technology; Vice President for Research

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NANOSCIENCE Nanoscience refers to the observation, identification, description, discovery, experimental investigation, and theoretical interpretation of nanoscale phenomena. www.sunycnse.com

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The Nanoscience Constellation Ion Beam Laboratory (H. Bakhru and M. Huang) Scope: Ion beam characterization (RBS, NRA, PIXE, High-Res RBS, microbeam) and fabrication (ion implantation) Goals: Fabrication and characterization of nanoscale and microscale devices and structures for electronic, photonic, and spintronic applications Cooperative activities through CNSE with their corporate sponsors: • • • • The Ion Beam Laboratory (IBL) has supplied CNSE with materials analyses and ion implanted standards for STC-MEMS related programs. IBL also provides Implanted Standards to the CNSE Metrology group. IBL provides Analysis to IBM, SEMATECH, and the G450C group. IBL has set up a chamber for 450 mm full wafer analysis. This chamber is being used by G450C group for RBS Analysis on full wafers. 2013 Accomplishments TOPIC 1: Scalable fabrication of high purity diamond nanocrystals with long-spincoherence nitrogen vacancy centers The combination of long spin coherence time and nanoscale size has made nitrogen vacancy (NV) centers in nanodiamonds important to be investigated for quantum information and sensing applications. Currently available high-pressure hightemperature (HPHT) nanodiamonds have a high concentration of paramagnetic impurities that limit their spin coherence time to the order of microseconds, less than 1% of that observed in bulk diamond. Figure 1: Process Schematic. a, Bulk diamond is masked by sputter-coated AuPd. b, O2 inductively coupled plasma etches the diamond with the AuPd as a mask. c, As the etch continues, the AuPd is completely removed. d, The diamond is implanted with nitrogen, annealed, and chemically treated to form NV centers. e, The CVD nanodiamonds are mechanically removed from bulk, and f, transferred onto glass coverslips for confocal microscopy 7

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The Nanoscience Constellation In this work, we used a porous metal mask and a reactive ion etching process to fabricate nanocrystals from high-purity chemical vapor deposition (CVD) diamond. We showed that NV centers in these CVD nanodiamonds possess record spin coherence times in excess of 200 µs, enabling magnetic field sensitivities of 290 nT Hz -1/2 with the spatial resolution characteristic of a 50 nm diameter probe.   Figure 2: Scanning Electron Micrographs. a, AuPd mask. b, Side-view and c, top-view of nanocrystals attached to bulk diamond. d, Nanocrystals separated from bulk and transferred onto a silicon substrate. M.E.Trusheim, L.Li, A.Laraoui, E.H.Chen, O.Gaathon, H.Bakhru, T.Schröder, C.A.Meriles, and D.Englund, “Scalable Fabrication of High Purity Diamond Nanocrystals with Long-Spin-Coherence Nitrogen Vacancy Centers,” Nanoletters 2014 8

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The Nanoscience Constellation TOPIC 2: Fabrication and analysis of embedded nickel nanoparticles in silicon for spintronic applications   Hydrogen and nickel implantations were done at different doses and the nanocavity layer formed by subsequent annealing contains cavities decorated by the nickel atoms. The implantations were done on the Extrion 400KV implanter. The RBS analysis (Dynamitron 4MeV implanter) shows that more nickel can be trapped by increasing the Hydrogen dose. The particles were found to be magnetic with a blocking temperature of about 360K, rendering them ferromagnetic at room temperature in the presence of a magnetic field. The lower density of defects (as seen from RBS) can make these structures good candidates to demonstrate spintronic devices. Moment (emu) vs Field (Oe) 4.00E-06 3.00E-06 2.00E-06 Moment 1.00E-06 -2000 0.00E+00 -1000 0 -1.00E-06 -2.00E-06 -3.00E-06 -4.00E-06 Field 1000 2000 Voltage  vs  Current   2.5   2   1.5   Voltage   1   0.5   0   -­‐0.00002   -­‐0.00001   0   0.00001   0.00002   -­‐0.5   Current   (a) RBS plot showing peak due to nanocavity layer, (b) M vs H showing ferromagnetic-like behavior for different H doses, (c) TEM image showing nanocavity layer, (d) V vs I for control sample showing magnetoresistance 9

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The Nanoscience Constellation TOPIC 3: Understanding defect mechanism in laser-annealed ultra-shallow junctions using Ion channeling analysis. Defect mechanisms in LASER annealing has been characterized using a combination of ion channeling and electrical characterization. The comprehensive analysis of the ion channeling spectra shows that the defect is a mixture of different BIC’s. For LASER annealing the defects are a smaller cluster and could be predominantly B2I clusters. In the case of spike annealing, the defects are big clusters that could be predominantly B4I2-. The defect dissolution rate was highly dependent on LASER temperature. Based upon this understanding, a combination of anneal was suggested and verified to make abrupt junctions. Vanamurthy, L.H., Huang, M., Bakhru, H., Furukawa, T., Berliner, N., Herman, J., Zhu, Z., Ronsheim, P., Doris, B., “Subnanometer-resolution depth profiling of boron atoms and lattice defects in silicon ultrashallow junctions by ion beam techniques.” Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films Volume 31, Issue 3, May 2013, 031403. 10

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The Nanoscience Constellation TOPIC 4: Optical confinement and mode selection in single-crystal fibers through hydrogen ion implantation induced nanoscale void structures The group has developed an innovative approach to fabricating optical claddings/barriers within single-crystal sapphire fibers or wafers, enabling strong optical confinement within sapphire crystals even at 1700 °C. The approach relies on ion implantation to generate nanoscale structures within the material, and it will open up many novel opportunities in optical sensing under harsh-environment conditions. See the news report in Laser Focus World, entitled “OPTICAL FIBER SENSING: Improved sapphire fibers raise prospects for harsh-environment-sensing.” (http://www.laserfocusworld.com/articles/print/volume-48/issue-08/world-news/opticalfiber-sensing-improved-sapphire-fibers-raise-prospects-for-harsh-environmentsensing.html) Other activities include investigation of visible and infrared light emission from silicon oxycarbide and erbium oxide thin films, characterization of optical properties in metal nanoparticle embedded Si, and the study of interactions between ion-implanted dopant atoms and point defects in ZnO crystals. Publications 2013-2014 Vanamurthy, L.H., Huang, M., Bakhru, H., Furukawa, T., Berliner, N., Herman, J., Zhu, Z., Ronsheim, P., Doris, B., “Subnanometer-resolution depth profiling of boron atoms and lattice defects in silicon ultrashallow junctions by ion beam techniques.” Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films Volume 31, Issue 3, May 2013, 031403. Huang, H.-C., Dadap, J.-I., Gaathon, O., Herman, I.P., Osgood, R.M., Bakhru, S., Bakhru H., “A microRaman spectroscopic investigation of He+-irradiation damage in LiNbO3.” Optical Materials Express Volume 3, Issue 2, 2013, Pages 126-142. Bishop, S.M., Briggs, B.D., Rice, P.Z., Capulong, J.O., Bakhru, H., Cady, N.C., “Ion implantation synthesis and conduction of tantalum oxide resistive memory layers.” Journal of Vacuum Science and Technology B: Microelectronics and Nanometer Structures Volume 31, Issue 1, January 2013, 012203. 11

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The Nanoscience Constellation Gaathon, O., Hodges, J.S., Chen, E.H., Li, L., Bakhru, S., Bakhru, H., Englund, D., Osgood Jr., R.M., “Planar fabrication of arrays of ion-exfoliated single-crystal-diamond membranes with nitrogen-vacancy color centers.” Optical Materials Volume 35, Issue 3, January 2013, Pages 361-365. William Spratt, Mengbing Huang, Thomas Murray and Hua Xia, “Optical mode confinement and selection in single-crystal sapphire fibers by formation of nanometer scale cavities with hydrogen ion implantation.” accepted for publication in Journal of Applied Physics. Sebastian Naczas, Faisal Yaqoob, and Mengbing Huang, “Effects of surface oxide layer on nanocavity formation and silver gettering in hydrogen ion implanted silicon.” Journal of Applied Physics 114, 023502 (2013). Y. Deshko, Mengbing Huang, and A. A. Gorokhovsky, “Conversion efficiency of implanted ions by confocal micro-luminescence mapping.” Journal of Luminescence 133, 61 (2013). Mengbing Huang and William Spratt, “Optical barriers, waveguides, and methods for fabricating barriers and waveguides for use in harsh environments.” US Patent application #13/608,118 12

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The Nanoscience Constellation Characterization, Metrology, and Physics of Nanoscale Materials and Structures (Diebold Group) Scope: The Diebold group works in all areas of characterization and metrology. Through collaboration with CNSE partners, measurement is used to advance R&D into new materials and structures. Examples of research topics and areas include lithography, transistor, and interconnect metrology for silicon IC R&D and manufacturing. The group also works on non-silicon IC materials such as III-V’s and PV. Measurement methods frequently used by the group include spectroscopic ellipsometry, photoluminescence, second harmonic generation, high resolution X-ray diffraction, X-ray reflectivity, transmission electron microscopy, X-ray photoelectron spectroscopy, and ion beam analysis. Goals: Advance new measurement methods for all areas of semiconductor technology (Si, III-V, and PV) from the Lab to the FAB 2013 Accomplishments TOPIC 1: Mueller Matrix Spectroscopic Ellipsometry-based Scatterometry for critical dimension measurement of Si and SiGe/Si fins Scatterometry is used for the characterization and control of critical dimensions (CD) during patterning. This effort studies the application of Mueller Matrix Spectroscopic Ellipsometry (SE) (16 element) Scatterometry (MMSE) to obtain measurement of the feature shape and dimensions of a series of 1D, 2D symmetric and asymmetric grating structures fabricated using e-beam lithography. The advantage of MMSE over traditional SE Scatterometry is the ability of MMSE to measure samples that have anisotropic optical properties and depolarize light. Now that this capability has been established, Fin structures are being characterized. This work is done in collaboration with and funded by Nanometrics, Inc. and the Semiconductor Research Corporation. We also acknowledge close collaboration with GlobalFoundries. Future work will include application of MMSE to Directed Self Assembly of block co-polymer structures. In addition to proving the importance of using 16 Mueller Matrix element scatterometry, this research demonstrated a new analysis method known as anisotropy coefficients. These coefficients are calculated from the MMSE elements across the wavelength range of the ellipsometer. The linear, 45°, and circular anisotropy coefficients showed how pitch walking affects the MMSE data above 500 nm and that the optical anisotropy of the complex refractive index of the materials affects data below 500 nm wavelength. This information is critical to understanding how to improve scatterometry modeling. 13

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