With this award from the Major Research Instrumentation (MRI) Program that is co-funded by Chemistry, Professor Frank Bright from SUNY Buffalo and colleagues Joseph Gardella, Athos Petrou, Esther Takeuchi and Sarbajit Banerjee will acquire a tip-enhanced Raman spectroscopy (TERS) system. The proposal is aimed at enhancing research training and education at all levels, especially in areas such as (a) nanocrystalline sensor platforms, (b) vanadium dioxide and metal vanadate (MxV2O5, where M = Na, K, Cu, Zn) nanowires, (c) biodegradable repair and delivery constructs, (d) magneto-polarons within single ZnMnTe quantum dots, (e) advanced energy storage materials, (f) nanodiamond-based separations, (g) nanoscopic heterogeneity within antifouling and fouling release film surfaces, (h) hydroxyapatite nucleation and growth, (i) organic nanotubes and periodic nanomaterials, (j) substrate-catalyzed monolayer photolithography and energy-conversion, (k) photo-crystallization within amorphous selenium, (l) development of terahertz technologies based on graphene heterostructures, and (m) flexible hybrid xerogel/Bragg grating platforms for wound sensing and restitution.

Raman spectroscopy is a vibrational spectroscopy technique that serves as a powerful analytical tool to identify sample structures. However, the intensity of normal Raman spectroscopy is not very strong and thus ways to enhance the signal are essential. The tip-enhanced Raman spectroscopy (TERS) method is based on the combination of Raman spectroscopy, surface enhanced Raman scattering (SERS) and atomic force microscopy (AFM). The TERS effect uses a metal-coated AFM tip as an antenna that enhances the Raman signal coming from the sample area in contact with the tip. Because the AFM tip is on the nanometer scale, it is possible to obtain localized enhancement on the same scale. By differentiating the tip enhanced Raman from the normal Raman (tip away from the sample) it is possible to obtain Raman information from areas <100 nm in diameter. The requested TERS system will facilitate the characterization of thin films, nanostructures, and porous surfaces and will serve to train undergraduate and graduate students, as well as postdocs. It will also be used in outreach activities at the K-12 level.

Project Report

This grant application, supported by the NSF MRI program, purchased a state-of-the-art instrument that allows atomic force microscopy (AFM), scanning Kelvin probe microscopy (SKPM), confocal Raman, co-localized AFM/Raman, and tip enhanced Raman scattering (TERS) spectroscopy (single point and mapping) measurements across multiple length scales. The new system has been used to expand the programmatic needs of several NSF-supported researchers in the following research areas: (i) Establish the surface chemistry and electronics with intra-crystal strain and the observed photoluminescence from porous silicon and free-standing silicon nanocrystals being explored for chemical sensing applications (Frank Bright, UB Chemistry); (ii) Hybrid MnAs/GaMnAs/GaAs thin films to determine Mn diffusion chemistry and physics from MnAs into GaAs (Joseph Gardella & Hong Luo, UB Chemistry & Physics); (iii)Develop and understand surface grafting to silicon nanoscrystallites using hydrosilation and silanization for biological delivery and chemical sensing applications (Frank Bright & Javid Rzayev, UB Chemistry and Amitav Sanyal, Bogazici University, Chemistry); (iv) Determine the surface topological, electronic and chemical properties of marine anti-fouling/fouling release films derived from silica-based xerogels that form chemically ambiguous nanodomains (Frank Bright & Michael Detty, UB Chemistry); (v) Topological, electronic, chemical and photoluminescence from single and multilayer MoS2 films formed on sapphire for applications in advanced hydrogen evolution reactions (Hao Zeng, UB Physics); (vi) Characteristics of InN thin films formed on GaN for high high-speed transistor switching applications (Uttam Singisetti, UB Electrical Engineering); (vii) Characteristics of 5-10 nm thick Ge films formed on thin Au films for use as wavelength selective filters (Albert Titus, UB Biomedical Engineering); (viii) Effects of laser beam size and fluence on the lift-off characteristics of graphene-based surfaces for direct matrix-assisted laser desorption ionization mass spectrometry applications (Sarbajit Banerjee & Troy Wood, UB Chemistry); (ix) Quantifying sample sputter volumes and the resulting analytical figures of merits for imaging time-of-flight secondary ion mass spectrometry and inductively coupled plasma mass spectrometry on doped NIST glass standards (Diana Aga & Joseph Gardella, UB Chemistry); (x) Physical dimensions, interfacial electronics, and photophysical properties of fractionated carbon nanodiamond materials for new fluorescent probe development (Frank Bright & Luis Colon, UB Chemistry); and (xi) Mapping photo-induced crystallization in thin Se films (Sarbajit Banerjee & Bernard Weinstein, UB Chemistry & Physics) The new system has also supported interdisciplinary graduate education, undergraduate research efforts, and summer research-based professional development for urban middle and high school teachers and students through the NSF-sponsored Interdisciplinary Science and Engineering Partnership (ISEP) with the Buffalo Public Schools (BPS). The investigators participating in this grant application currently support and mentor over 50 graduate students, postdoctoral fellows, and visiting scientists, they play lead roles in major interdisciplinary student training programs (ISEP), and they have successfully served or are serving as mentors for many women and underrepresented minority students through, for example, the Louis Stokes Alliance for Minority Participation (LSAMP) and the Alliance for Graduate Education and the Professoriate (AGEP). All of the investigators are also very active in undergraduate research through an existing REU site (in Chemistry), the UB Undergraduate Academies, and the S-STEM fellows program amongst other vehicles. The investigators also have substantial K-12 outreach efforts that range from summer workshops, expansion of opportunities at the Buffalo Native American Magnet School to the new UB/BPS ISEP. The PI has also developed interdisciplinary graduate course components as part of their outreach programs.

Agency
National Science Foundation (NSF)
Institute
Division of Chemistry (CHE)
Type
Standard Grant (Standard)
Application #
1126301
Program Officer
Carlos A. Murillo
Project Start
Project End
Budget Start
2011-09-01
Budget End
2014-08-31
Support Year
Fiscal Year
2011
Total Cost
$325,645
Indirect Cost
Name
Suny at Buffalo
Department
Type
DUNS #
City
Buffalo
State
NY
Country
United States
Zip Code
14260