Vinayak P. Dravid

Northwest University, Evanston, Illinois, United States

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Publications (421)1806.4 Total impact

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    ABSTRACT: Graphene-based nanocomposites have been synthesized and tested as electrode materials for high power lithium-ion batteries. In the synthesis of such nanocomposites, graphene is generally introduced by either thermally or chemically reduced graphite oxide (GO), which has poorer electric conductivity and crystallinity than mechanically exfoliated graphene. Here, we prepare few-layer graphene sheet (FLGS) with high electric conductivity, by sonicating expanded graphite in DMF solvent, and develop a simple one-pot hydrothermal method to fabricate monodispersed and ultrasmall Co3O4 nanocubes (about 4 nm in size) on the FLGS. This composite, consisting of homogeneously assembled and high crystalline Co3O4 nanocubes on the FLGS, has shown higher capacity and much better cycling stability than counterparts synthesized using GO as a precursor. The products in different synthesis stages have been characterized by TEM, FTIR and XPS to investigate the nanocube growth mechanism. We find that Co(OH)2 initially grew homogeneously on the graphene surface, then gradually oxidized to form Co3O4 nanoparticle seeds, and finally converted to Co3O4 nanocubes with caboxylated anion as surfactant. This work explores the mechanism of nanocrystal growth and its impact on electrochemical properties to provide further insights into the development of nanostructured electrode materials for high power energy storage.
    Journal of Power Sources 01/2015; 274:816-822. · 5.26 Impact Factor
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    ABSTRACT: SnTe is an intriguing alternative to its sister compound PbTe in thermoelectric energy conversion because of their electronic and structural similarity; however, it is challenging to optimize its thermoelectric performance to the level of PbTe because of the difficulties in decreasing its intrinsically large hole population and high thermal conductivity arising from the tin vacancies. We demonstrate here that by alloying some AgBiTe2 in SnTe, thus forming AgSnxBiTex+2 compositions the hole concentration can be duly decreased because of the high efficiency of Bi as an electron donor. The lattice thermal conductivity is also decreased due to the strong scattering of phonons (by point defect scattering as well as Ag-rich nanostructures) to achieve a value of 0.7 W m−1 K−1 at 750 K. As a result, a high thermoelectric figure ZT of merit of 1.1 at 775 K is achieved by chemical composition optimization (×15), making lead free SnTe–AgBiTe2 a promising thermoelectric material.
    J. Mater. Chem. A. 11/2014;
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    ABSTRACT: The influence of hierarchical TiO2 inclusions on electrical and thermal transport properties has been investigated in the Ba-filled skutterudite compound Ba0.3Co4Sb12 synthesized by ball milling followed by hot pressing. The hierarchical TiO2 with morphology of nanocrystallite aggregates were prepared using a carbon sphere-templated method. It was found that TiO2 inclusions strongly enhance the Seebeck coefficient while they weakly degrade the electric conductivity. In addition, TiO2 inclusions significantly reduce the lattice thermal conductivity through all-scale length phonon scattering due to these hierarchically-structured TiO2 particle inclusions. ZT values up to 1.2 were obtained for Ba0.3Co4Sb12 with the optimal amount and dispersion of TiO2 inclusions. These observations demonstrate an exciting scientific opportunity to raise the figure-of-merit of filled skutterudites via hierarchical dispersion.
    J. Mater. Chem. A. 10/2014;
  • Langli Luo, Jinsong Wu, Junming Xu, Vinayak P Dravid
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    ABSTRACT: Electrode materials based on conversion reactions with lithium ions have shown much higher energy density than those based on intercalation reactions. Here, nanocubes of a typical metal oxide (Co3O4) were grown on few-layer graphene, and their electrochemical lithiation and delithiation were investigated at atomic resolution by in situ transmission electron microscopy to reveal the mechanism of the reversible conversion reaction. During lithiation, a lithium-inserted Co3O4 phase and a phase consisting of nanosized Co-Li-O clusters are identified as the intermediate products prior to the subsequent formation of Li2O crystals. In delithiation, the reduced metal nanoparticles form a network and breakdown into even smaller clusters that act as catalysts to prompt reduction of Li2O, and CoO nanoparticles are identified as the product of the deconversion reaction. Such direct real-space, real-time atomic-scale observations shed light on the phenomena and mechanisms in reaction-based electrochemical energy conversion and provide impetus for further development in electrochemical charge storage devices.
    ACS Nano 10/2014; · 12.03 Impact Factor
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    ABSTRACT: Alzheimer disease (AD), the most prevalent type of dementia, has been associated with the accumulation of amyloid β oligomers (AβOs) in the central nervous system. AβOs vary widely in size, ranging from dimers to larger than 100 kDa. Evidence indicates that not all oligomers are toxic, and there is yet no consensus on the size of the actual toxic oligomer. Here we used NU4, a conformation-dependent anti-AβO monoclonal antibody, to investigate size and shape of a toxic AβO assembly. By using size-exclusion chromatography and immuno-based detection we isolated an AßO-NU4 complex amenable for biochemical and morphological studies. The apparent molecular mass of the NU4-targeted oligomer was 80 kDa. AFM imaging of the AβO-NU4 complex showed a size distribution centered at 5.37 nm, an increment of 1.5 nm compared to the size of AβOs (3.85 nm). This increment was compatible with the size of NU4 (1.3 nm), suggesting a 1:1 oligomer to NU4 ratio. NU4-reactive oligomers extracted from AD human brain concentrated in a molecular mass range similar to that found for in vitro-prepared oligomers, supporting the relevance of the species herein studied. These results represent an important step towards understanding the connection between AβO size and toxicity.
    ACS Chemical Neuroscience 10/2014; · 3.87 Impact Factor
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    ABSTRACT: We report several synergistic effects in Hg alloying of SnTe to enhance the power factor and overall figure of merit ZT. Hg alloying decreases the energy separation between the two valence bands, leading to pronounced band convergence that improves the Seebeck coefficient. Hg alloying of SnTe also significantly enlarges the band gap thereby effectively suppressing the bipolar diffusion. Collectively, this results in high ZT of 1.35 at 910 K for 2% Bi-doped SnTe with 3%HgTe. The solubility limit of Hg in SnTe is less than 3 mol%, and above this level we observe HgTe precipitates in the SnTe matrix, typically trapped at grain boundary triple junctions. The strong point defect scattering of phonons caused by Hg alloying coupled with mesoscale scattering via grain boundaries contributes to a great reduction of lattice thermal conductivity. The multiple synergistic roles that Hg plays in regulating the electron and phonon transport in SnTe provide important new insights into continued optimization of SnTe-based and related materials.
    Energy & Environmental Science 10/2014; · 11.65 Impact Factor
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    ABSTRACT: A novel, apertureless, cantilever-free pen array can be used for dual scanning photochemical and molecular printing. Serial writing with light is enabled by combining self-focusing pyramidal pens with an opaque backing between pens. The elastomeric pens also afford force-tuned illumination and simultaneous delivery of materials and optical energy. These attributes make the technique a promising candidate for maskless high-resolution photopatterning and combinatorial chemistry.
    Small 10/2014; · 7.82 Impact Factor
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    ABSTRACT: The palate of two-dimensional materials has expanded beyond graphene in recent years to include the chalcogenides among other systems. However, there is a considerable paucity of methods for controlled synthesis of mono- and/or few-layer two-dimensional materials with desirable quality, reproducibility and generality. Here we show a facile top-down synthesis approach for ultra-thin layers of 2D materials down to monolayer. Our method is based on controlled evaporative thinning of initially large sheets, as deposited by vapor mass-transport. Rather than optimizing conditions for monolayer deposition, our approach makes use of selective evaporation of thick sheets to control the eventual thickness, down to a monolayer, a process which appears to be self-stopping. As a result, 2D sheets with high yield, high reproducibility and excellent quality can be generated, with large (>10 µm) and thin (~1-2 nm) dimensions. Evaporative thinning promises to greatly reduce the difficulty involved in isolating large, mono- and few-layers of 2D materials for subsequent studies.
    ACS Nano 09/2014; · 12.03 Impact Factor
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    ABSTRACT: Ultrathin transition metal dichalcogenides (TMDCs) of Mo and W show great potential for digital electronics and optoelectronic applications. Whereas early studies were limited to mechanically exfoliated flakes, the large-area synthesis of 2D TMDCs has now been realized by chemical vapor deposition (CVD) based on a sulfurization reaction. The optoelectronic properties of CVD grown monolayer MoS2 have been intensively investigated, but the influence of stoichiometry on the electrical and optical properties has been largely overlooked. Here we systematically vary the stoichiometry of monolayer MoS2 during CVD via controlled sulfurization and investigate the associated changes in photoluminescence and electrical properties. X-ray photoelectron spectroscopy is employed to measure relative variations in stoichiometry and the persistence of MoOx species. As MoS2-δ is reduced (increasing δ), the field-effect mobility of monolayer transistors increases while the photoluminescence yield becomes non-uniform. Devices fabricated from monolayers with the lowest sulfur content have negligible hysteresis and a threshold voltage of ~0 V. We conclude that the electrical and optical properties of monolayer MoS2 crystals can be tuned via stoichiometry engineering to meet the requirements of various applications.
    ACS Nano 09/2014; · 12.03 Impact Factor
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    ABSTRACT: SnTe is a potentially attractive thermoelectric because it is the lead-free rock-salt analogue of PbTe. However, SnTe is a poor thermoelectric material because of its high hole concentration arising from inherent Sn vacancies in the lattice and its very high electrical and thermal conductivity. In this study, we demonstrate that SnTe-based materials can be controlled to become excellent thermoelectrics for power generation via the successful application of several key concepts that obviate the well-known disadvantages of SnTe. First, we show that Sn self-compensation can effectively reduce the Sn vacancies and decrease the hole carrier density. For example, a 3 mol % self-compensation of Sn results in a 50% improvement in the figure of merit ZT. In addition, we reveal that Cd, nominally isoelectronic with Sn, favorably impacts the electronic band structure by (a) diminishing the energy separation between the light-hole and heavy-hole valence bands in the material, leading to an enhanced Seebeck coefficient, and (b) enlarging the energy band gap. Thus, alloying with Cd atoms enables a form of valence band engineering that improves the high-temperature thermoelectric performance, where p-type samples of SnCd0.03Te exhibit ZT values of ∼0.96 at 823 K, a 60% improvement over the Cd-free sample. Finally, we introduce endotaxial CdS or ZnS nanoscale precipitates that reduce the lattice thermal conductivity of SnCd0.03Te with no effect on the power factor. We report that SnCd0.03Te that are endotaxially nanostructured with CdS and ZnS have a maximum ZTs of ∼1.3 and ∼1.1 at 873 K, respectively. Therefore, SnTe-based materials could be ideal alternatives for p-type lead chalcogenides for high temperature thermoelectric power generation.
    Journal of the American Chemical Society 05/2014; · 10.68 Impact Factor
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    ABSTRACT: The thermoelectric effect enables direct and reversible conversion between thermal and electrical energy, and provides a viable route for power generation from waste heat. The efficiency of thermoelectric materials is dictated by the dimensionless figure of merit, ZT (where Z is the figure of merit and T is absolute temperature), which governs the Carnot efficiency for heat conversion. Enhancements above the generally high threshold value of 2.5 have important implications for commercial deployment, especially for compounds free of Pb and Te. Here we report an unprecedented ZT of 2.6 ± 0.3 at 923 K, realized in SnSe single crystals measured along the b axis of the room-temperature orthorhombic unit cell. This material also shows a high ZT of 2.3 ± 0.3 along the c axis but a significantly reduced ZT of 0.8 ± 0.2 along the a axis. We attribute the remarkably high ZT along the b axis to the intrinsically ultralow lattice thermal conductivity in SnSe. The layered structure of SnSe derives from a distorted rock-salt structure, and features anomalously high Grüneisen parameters, which reflect the anharmonic and anisotropic bonding. We attribute the exceptionally low lattice thermal conductivity (0.23 ± 0.03 W m(-1) K(-1) at 973 K) in SnSe to the anharmonicity. These findings highlight alternative strategies to nanostructuring for achieving high thermoelectric performance.
    Nature 04/2014; 508(7496):373-7. · 38.60 Impact Factor
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    ABSTRACT: We report the development of thermo-responsive magnetic hydrogels based on poly(N-isopropylacrylamide) encapsulation of Fe3O4 magnetic nanostructures (MNS). In particular, we examined the effects of hydrogels encapsulated with poly-ethylene glycol (PEG) and polyhedral oligomeric silsesquioxane (POSS) surface modified Fe3O4 MNS on magnetic resonance (MR) T2 (transverse spin relaxation) contrast enhancement and associated delivery efficacy of absorbed therapeutic cargo. The microstructural characterization reveal the regular spherical shape and size (~200 nm) of the hydrogels with elevated hydrophilic to hydrophobic transition temperature (~ 40 °C) characterized by LCST (lower critical solution temperature) due to the presence of encapsulated MNS. The hydrogel-MNS (HGMNS) system encapsulated with PEG functionalized Fe3O4 of 12 nm size (HGMNS-PEG-12) exhibited relaxivity rate (r2) of 173 mM(-1)s(-1) compared to 129 mM(-1)s(-1) obtained for hydrogel-MNS system encapsulated with POSS functionalized Fe3O4 (HGMNS-POSS-12) of the same size. Further studies with HGMNS-PEG-12 with absorbed drug doxorubicin (DOX) reveals approximately two-fold enhance in release during 1 h RF (radio-frequency) field exposure followed by 24 h incubation at 37 °C. Quantitatively it is 2.1 µg mg(-1) (DOX/HGMNS) DOX release with RF exposure while only 0.9 µg mg(-1) release without RF exposure for the same period of incubation. Such enhanced release of therapeutic cargo is attributed to micro-environmental heating in the surroundings of MNS as well as magneto-mechanical vibrations under high frequency RF inside hydrogels. Similarly, RF-induced in-vitro localized drug delivery studies with HeLa cell lines for HGMNS-PEG-12 resulted in more than 80 % cell death with RF field exposures for 1 h. We therefore believe that magnetic hydrogel system has in vivo theranostic potential given high MR contrast enhancement from encapsulated MNS and RF-induced localized therapeutic delivery in one nanoconstruct.
    ACS Applied Materials & Interfaces 04/2014; · 5.90 Impact Factor
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    ABSTRACT: We report the temperature-dependent Raman spectra of single- and few-layer MoSe2 and WSe2 in the range 77-700 K. We observed linear variation in the peak positions and widths of the bands arising from contributions of anharmonicity and thermal expansion. After characterization using atomic force microscopy and high-resolution transmission electron microscopy, the temperature coefficients of the Raman modes were determined. Interestingly, the temperature coefficient of the A(2) 2u mode is larger than that of the A1g mode, the latter being much smaller than the corresponding temperature coefficients of the same mode in single-layer MoS2 and of the G band of graphene. The temperature coefficients of the two modes in single-layer MoSe2 are larger than those of the same modes in single-layer WSe2 . We have estimated thermal expansion coefficients and temperature dependence of the vibrational frequencies of MoS2 and MoSe2 within a quasi-harmonic approximation, with inputs from first-principles calculations based on density functional theory. We show that the contrasting temperature dependence of the Raman-active mode A1g in MoS2 and MoSe2 arises essentially from the difference in their strain-phonon coupling.
    ChemPhysChem 04/2014; · 3.35 Impact Factor
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    ABSTRACT: The incorporation of nanostructured carbon has been recently reported as an effective approach to improve the cycling stability when Si is used as high-capacity anodes for the next generation Li-ion battery. However, the mechanism of such notable improvement remains unclear. Herein, we report in-situ transmission electron microscopy (TEM) studies to directly observe the dynamic electrochemical lithiation/delithiation processes of crumpled graphene-encapsulated Si nanoparticles to understand their physical and chemical transformations. Unexpectedly, in the first lithiation process, crystalline Si nanoparticles undergo an isotropic to anisotropic transition, which is not observed in pure crystalline and amorphous Si nanoparticles. Such a surprising phenomenon arises from the uniformly distributed localized voltage around the Si nanoparticles due to the highly conductive graphene sheets. It is observed that the intimate contact between graphene and Si is maintained during volume expansion/contraction. Electrochemical sintering process where small Si nanoparticles react and merge together to form large agglomerates following spikes in localized electric current is another problem for batteries. In-situ TEM shows that graphene sheets help maintain the capacity even in the course of electrochemical sintering. Such in-situ TEM observations provide valuable phenomenological insights into electrochemical phenomena, which may help optimize the configuration for further improved performance.
    Scientific Reports 03/2014; 4:3863. · 5.08 Impact Factor
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    ABSTRACT: Lead chalcogenide thermoelectric systems have been shown to reach record high figure of merit values via modification of the band structure to increase the power factor or via nanostructuring to reduce the thermal conductivity. Recently, (PbTe)1-x(PbSe)x was reported to reach high power factors via a delayed onset of interband crossing. Conversely, the (PbTe)1-x(PbS)x was reported to achieve low thermal conductivities arising from extensive nanostructuring. Here we report the thermoelectric properties of the pseudoternary 2% Na-doped (PbTe)1-2x(PbSe)x(PbS)x system. The (PbTe)1-2x(PbSe)x(PbS)x system is an excellent platform to study phase competition between entropically driven atomic mixing (solid solution behavior) and enthalpy-driven phase separation. We observe that the thermoelectric properties of the PbTe-PbSe-PbS 2% Na doped are superior to those of 2% Na-doped PbTe-PbSe and PbTe-PbS, respectively, achieving a ZT ≈2.0 at 800 K. The material exhibits an increased the power factor by virtue of valence band modification combined with a very reduced lattice thermal conductivity deriving from alloy scattering and point defects. The presence of sulfide ions in the rock-salt structure alters the band structure and creates a plateau in the electrical conductivity and thermopower from 600 to 800 K giving a power factor of 27 μW/cmK(2). The very low total thermal conductivity values of 1.1 W/m·K of the x = 0.07 composition is accounted for essentially by phonon scattering from solid solution defects rather than the assistance of endotaxial nanostructures.
    Journal of the American Chemical Society 02/2014; · 10.68 Impact Factor
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    ABSTRACT: We examine the thermodynamics of phase separation and ordering in the ternary CaxPb1-xS and SrxPb1-xS systems by density-functional theory combined with a cluster expansion and Monte Carlo simulations. Similar to most other ternary III-V or IV-VI semiconductor alloys, we find that bulk phase separation is thermodynamically preferred for PbS-CaS. However, we predict the surprising existence of stable, ordered ternary compounds in the PbS-SrS system. These phases are previously unreported ordered rocksalt-based compounds: SrPb3S4, SrPbS2 and Sr3PbS4. The stability of these predicted ordered phases are confirmed by transmission electron microscopy observations and band gap measurements. We believe this work paves the way for a combined theory-experiment approach to decipher complex phase relations in multicomponent chalcogenide systems.
    Journal of the American Chemical Society 01/2014; · 10.68 Impact Factor
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    ABSTRACT: Increasing the conversion efficiency of thermoelectric materials is a key scientific driver behind a worldwide effort to enable heat to electricity power generation at competitive cost. Here we report an increased performance for antimony-doped lead selenide with a thermoelectric figure of merit of ~1.5 at 800 K. This is in sharp contrast to bismuth doped lead selenide, which reaches a figure of merit of <1. Substituting antimony or bismuth for lead achieves maximum power factors between ~23-27 μW cm(-1) K(-2) at temperatures above 400 K. The addition of small amounts (~0.25 mol%) of antimony generates extensive nanoscale precipitates, whereas comparable amounts of bismuth results in very few or no precipitates. The antimony-rich precipitates are endotaxial in lead selenide, and appear remarkably effective in reducing the lattice thermal conductivity. The corresponding bismuth-containing samples exhibit smaller reduction in lattice thermal conductivity.
    Nature Communications 01/2014; 5:3640. · 10.74 Impact Factor
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    ABSTRACT: Here we report the synthesis, characterization and application of a multifunctional surface functionalized GdF3:Nd3+ nanophosphor that exhibits efficient near infrared (NIR) fluorescence as well as magnetic properties, which can be utilized for bimodal imaging in medical applications. The nanoparticles are small with an average size of 5 nm and form stable colloids that last for several weeks without settling, enabling the use for several biomedical and photonic applications. Their excellent NIR properties, such as nearly 11 % quantum yield of the 1064 nm emission, make them ideal contrast agents and biomarkers for in vitro and in vivo NIR optical bioimaging. The nanophosphors which were coated with poly(maleic anhydride- alt-1-octadicene) (PMAO) were implemented in cellular imaging and show no significant cellular toxicity for concentrations up to 200 μg ml-1. Furthermore, the incorporation of Gd into the nanocrystalline structure supplies exceptional magnetic properties, making them ideal for use as magnetic resonance imaging (MRI) contrast agents. The utility of these NIR emitting nanoparticles in infrared bioimaging and as contrast agent in magnetic resonance imaging was demonstrated by confocal imaging, magnetic resonance and tissue experiments.
    Journal of Materials Chemistry 08/2013; · 6.63 Impact Factor
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    ABSTRACT: The multicatalytic ubiquitin-proteasome system (UPS) carries out proteolysis in a highly orchestrated way and regulates a large number of cellular processes. Deregulation of the UPS in many disorders has been documented. In some cases, e.g. carcinogenesis, elevated proteasome activity has been implicated in disease development, while the etiology of other diseases, e.g. neurodegeneration, includes decreased UPS activity. Therefore, agents that alter proteasome activity could suppress as well as enhance a multitude of diseases. Metal oxide nanoparticles, often developed as diagnostic tools, have not previously been tested as modulators of proteasome activity. Here, several types of metal oxide nanoparticles were found to adsorb to the proteasome and show variable preferential binding for particular proteasome subunits with several peptide binding "hotspots" possible. These interactions depend on the size, charge, and concentration of the nanoparticles and affect proteasome activity in a time-dependent manner. Should metal oxide nanoparticles increase proteasome activity in cells, as they do in vitro, unintended effects related to changes in proteasome function can be expected.
    ACS Nano 08/2013; · 12.03 Impact Factor

Publication Stats

4k Citations
1,806.40 Total Impact Points

Institutions

  • 1994–2014
    • Northwest University
      Evanston, Illinois, United States
  • 1970–2014
    • Northwestern University
      • • Department of Materials Science and Engineering
      • • Department of Biomedical Engineering
      • • Department of Chemistry
      • • Department of Radiation Oncology
      Evanston, Illinois, United States
  • 2013
    • University of Pune
      • Department of Physics
      Pune, State of Maharashtra, India
  • 2011–2012
    • Institute of Microbial Technology
      Chandigarh, Chandīgarh, India
    • Indian Institute of Technology Bombay
      • Department of Physics
      Mumbai, State of Maharashtra, India
    • Kenyon College
      • Department of Physics
      Gambier, Ohio, United States
  • 2008–2010
    • Argonne National Laboratory
      • Division of Materials Science
      Lemont, Illinois, United States
    • Oak Ridge National Laboratory
      • Biosciences Division
      Oak Ridge, FL, United States
  • 1988–2005
    • Lehigh University
      • Department of Materials Science and Engineering
      Bethlehem, PA, United States
  • 1999
    • University of Illinois at Chicago
      • Department of Physics
      Chicago, IL, United States
  • 1998
    • Korea Research Institute of Chemical Technology
      • Division of Advanced Material
      Daiden, Daejeon, South Korea
    • San Jose State University
      San Jose, California, United States
  • 1997
    • Brown University
      • Department of Physics
      Providence, RI, United States
  • 1995
    • University of Illinois, Urbana-Champaign
      • Department of Materials Science and Engineering
      Urbana, Illinois, United States