Michael F. Toney

University of California, Santa Barbara, Santa Barbara, California, United States

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Publications (364)1811.22 Total impact

  • Adam P Hitchcock, Michael F Toney
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    ABSTRACT: Current and future capabilities of X-ray spectromicroscopy are discussed based on coherence-limited imaging methods which will benefit from the dramatic increase in brightness expected from a diffraction-limited storage ring (DLSR). The methods discussed include advanced coherent diffraction techniques and nanoprobe-based real-space imaging using Fresnel zone plates or other diffractive optics whose performance is affected by the degree of coherence. The capabilities of current systems, improvements which can be expected, and some of the important scientific themes which will be impacted are described, with focus on energy materials applications. Potential performance improvements of these techniques based on anticipated DLSR performance are estimated. Several examples of energy sciences research problems which are out of reach of current instrumentation, but which might be solved with the enhanced DLSR performance, are discussed.
    Journal of Synchrotron Radiation 09/2014; 21(Pt 5):1019-1030. · 2.19 Impact Factor
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    ABSTRACT: The nucleating agent DMDBS is used to modulate the crystallization of solution-processed small molecule donor molecules in bulk heterojunction organic photovoltaic (BHJ OPV) devices. This control over donor molecule crystallization leads to a reduction in optimized thermal annealing times as well as smaller donor molecule crystallites, and therefore more efficient devices, when using an excessive amount of solvent additive. We therefore demonstrate the use of nucleating agents as a powerful and versatile processing strategy for solution-processed, small molecule BHJ OPVs.
    J. Mater. Chem. A. 08/2014;
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    ABSTRACT: To design an inexpensive, non-toxic, practical replacement to the internal combustion engine, significant advances in battery technology are required. Germanium anodes offer more than four times larger capacity than presently used graphite anodes. Yet large volume changes during operation severely limit their lifetime. To understand the origin, dynamics, and failure mechanisms of these and other electrode materials, it is essential to image batteries under operating conditions. Using transmission X-ray microscopy the morphology and electron density changes in Ge anode particles are tracked during operation. We observe significant size dependence on the cycling characteristics of Ge particles. Only Ge particles with diameters larger than a few microns display cracks during cycling. Small Ge particles experience volume expansion and cracking before their larger counterparts, but rapidly lose electrical contact. With in situ nanotomography, we demonstrate unambiguously for the first time the fracturing of alloying anode materials into completely unconnected pieces. Moreover, we show that the density changes due to lithiation are consistent with partial transformation into a Li15Ge4-like phase. Our results demonstrate the significant value in linking electrochemical performance studies with morphological evolution to understand failure mechanisms and encourage more systematic searches for a viable high capacity anode material.
    Energy & Environmental Science 07/2014; 7(8). · 11.65 Impact Factor
  • Linda Y. Lim, Nian Liu, Yi Cui, Michael F. Toney
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    ABSTRACT: Lithium-ion batteries using germanium as the anode material are attracting attention because of their high-capacity, higher conductivity, and lithium-ion diffusivity relative to silicon. Despite recent studies on Ge electrode reactions, there is still limited understanding of the reaction mechanisms governing crystalline Ge and the transformations into intermediate amorphous phases that form during the electrochemical charge and discharge process. In this work, we carry out in operando X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) studies on Ge anodes during the initial cycles to better understand these processes. These two probes track both crystalline (XRD) and amorphous (XAS) phase transformations with potential, which allows detailed information on the Ge anode to be obtained. We find that crystalline Ge lithiates inhomogeneously, first forming amorphous Li9Ge4 during the beginning stage of lithiation, followed by the conversion of the remaining crystalline Ge to amorphous Ge. The lithiation of amorphous Ge then forms amorphous LixGe, which are then further lithiated to form crystalline Li15Ge4. During delithiation, crystalline Li15Ge4 transforms directly into a heterogeneous mix of amorphous LixGe, which eventually form amorphous Ge, and interestingly, no amorphous Li9Ge4 are detected. Both our in operando XRD and XAS results present new insights into the reaction mechanism of Ge as anodes in LIBs, and demonstrate the importance of correlating electrochemical results with in operando studies.
    Chemistry of Materials. 06/2014; 26(12):3739–3746.
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    ABSTRACT: Benzo[1,2-b:4,5-b']difuran-thieno[3,4-c]pyrrole-4,6-dione (PBDFTPD) polymers prepared by microwave-assisted synthesis can achieve power conversion efficiencies (PCEs) >7% in BHJ solar cells with phenyl-C61/71-butyric acid methyl ester (PCBM). In "as-cast" PBDFTPD-based devices solution-processed without a small-molecule additive, high PCEs can be obtained in spite of the weak propensity of the polymers to self-assemble and form π-aggregates in thin films.
    Advanced Materials 05/2014; · 14.83 Impact Factor
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    ABSTRACT: In this work, crystallization kinetics and aggregate growth of poly(3-ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X-ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time-dependent, field-effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter-aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.
    Advanced Functional Materials 04/2014; · 10.44 Impact Factor
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    ABSTRACT: Investigations on the impact of interfacial modification on organic optoelectronic device performance often attribute the improved device performance to the optoelectronic properties of the modifier. A critical assumption of such conclusions is that the organic active layer deposited on top of the modified surface (interface) remains unaltered. Here the validity of this assumption is investigated by examining the impact of substrate surface properties on the morphology of poly(3-hexylthiophene):1-(3-methoxycarbonyl)-propyl-1-phenyl-[6,6]C61 (P3HT:PCBM) bulk-heterojunction (BHJ). A set of four nickel oxide and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTL) with contrasting surface properties and performance in organic photovoltaic (OPV) devices is studied. Differences in vertical composition variation and structural morphologies are observed across the samples, but only in the near-interface region of <∼20 nm. Near-interface differences in morphology are most closely correlated with surface polarity and surface roughness of the HTL. Surface polarity is more influenced by surface composition than surface roughness and crystal structure. These findings corroborate the previously mentioned conclusions that the differences in device performance observed in solar cells employing these HTLs are dominated by the electronic properties of the HTL/organic photoactive active layer interface and not by unintentional alteration in the BHJ active layer morphology.
    Advanced Energy Materials 03/2014; · 14.39 Impact Factor
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    ABSTRACT: Using non-chlorinated solvents for polymer device fabrication is highly desirable to avoid the negative environmental and health effects of chlorinated solvents. Here, a non-chlorinated mixed solvent system, composed by a mixture of tetrahydronaphthalene and p­-xylene, is described for processing a high mobility donor-acceptor fused thiophene-diketopyrrolopyrrole copolymer (PTDPPTFT4) in thin film transistors. The effects of the use of a mixed solvent system on the device performance, e.g., charge transport, morphology, and molecular packing, are investigated. p-Xylene is chosen to promote polymer aggregation in solution, while a higher boiling point solvent, tetrahydronaphthalene, is used to allow a longer evaporation time and better solubility, which further facilitates morphological tuning. By optimizing the ratio of the two solvents, the charge transport characteristics of the polymer semiconductor device are observed to significantly improve for polymer devices deposited by spin coating and solution shearing. Average charge carrier mobilities of 3.13 cm2 V−1 s−1 and a maximum value as high as 3.94 cm2 V−1 s−1 are obtained by solution shearing. The combination of non-chlorinated mixed solvents and the solution shearing film deposition provide a practical and environmentally-friendly approach to achieve high performance polymer transistor devices.
    Advanced Functional Materials 03/2014; · 10.44 Impact Factor
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    ABSTRACT: The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how M n and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD). Low M n PBDTTPD devices have exceedingly large fullerene-rich domains, which cause extensive charge-carrier recombination. Increasing the M n of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene-rich domains and this effect is linked to the dependency of PBDTTPD solubility on M n. Due to its poor solubility high M n PBDTTPD quickly forms a fibrillar polymer network during spin-casting and this network acts as a template that prevents large-scale phase separation. Furthermore, processing low M n PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene-rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells.
    Advanced Energy Materials 03/2014; · 14.39 Impact Factor
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    ABSTRACT: Self-doping of cations on the tetrahedral and octahedral sites in spinel oxides creates “anti-site” defects, which results in functional optical, electronic, magnetic, and other materials properties. Previously, we divded the III–II spinel family into four doping types (DTs) based on first-principle calculations in order to understand their electrical behavior. Here, we present experimental evidence on two prototype spinels for each major doping type (DT1 and DT4) that test the first principles calculations. For the DT-1 Ga2ZnO4 spinel, we show that the anti-site defects in a stoichiometric film are equal in concentration and compenstate each other, whereas, for nonstoichiometric Cr2MnO4, a representative DT-4 spinel, excess Mn on the tetrahedral sites becomes electrically inactive as the Mn species switch from (III) to (II). The agreement between experiment and theory validates the Doping Rules distilled from the theoretical framework and significantly enhances our understanding of the defect chemistry of spinel oxides.
    Chemistry of Materials 02/2014; 26(5):1867. · 8.24 Impact Factor
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    ABSTRACT: A regioregular (RR) donor–acceptor conjugated copolymer based on cyclopenta[2,1-b:3,4-b′]dithiophene (CDT) and pyridal[2,1,3]thiadiazole (PT) structural units was prepared by using polymerization reactions involving reactants specifically designed to avoid random orientation of the asymmetric PT heterocycle along the copolymer backbone. Compared to its regioirregular (RI) counterpart, the RR polymer exhibits a 2 orders of magnitude increase in hole mobility from 0.005 to 0.6 cm2 V–1 s–1. To probe the reason for this difference in mobility, we examined the crystalline structure and its orientation in thin films of both copolymers as a function of depth via grazing incidence wide-angle X-ray scattering (GIWAXS). In the RI film, the π–π stacking direction of the crystallites is mainly perpendicular to the substrate normal (edge-on orientation) while in the RR film the crystallites adopt a mixed π–π stacking orientation in the center of the film as well as near the interface between the polymer and the dielectric layer. These results demonstrate that control of backbone regularity is another important design criterion to consider in the synthesis and optimization of new conjugated copolymers with asymmetric structural units.
    Macromolecules 02/2014; 47(4):1403–1410. · 5.93 Impact Factor
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    ABSTRACT: The driving forces and processes associated with the development of phase separation upon thermal annealing are investigated in solution-processed small molecule bulk heterojunction (BHJ) organic solar cells utilizing a diketopyrrolopyrrole-based donor molecule and a fullerene acceptor (PCBM). In-situ thermal annealing X-ray scattering is used to monitor the development of thin film crystallization and phase separation and reveals that the development of blend phase separation strongly correlates with the nucleation of donor crystallites. Additionally, these morphological changes lead to dramatic increases in blend electron mobility and solar cell figures of merit. These results indicate that donor crystallization is the driving force for blend phase separation. It is hypothesized that donor crystallization from an as-cast homogeneous donor:acceptor blend simultaneously produces donor-rich domains, consisting largely of donor crystallites, and acceptor-rich domains, formed from previously mixed regions of the film that have been enriched with acceptor during donor crystallization. Control of donor crystallization in solution-processed small molecule BHJ solar cells employing PCBM is thus emphasized as an important strategy for the engineering of the nanoscale phase separated, bicontinuous morphology necessary for the fabrication of efficient BHJ photovoltaic devices.
    Advanced Functional Materials 02/2014; · 10.44 Impact Factor
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    ABSTRACT: Organic semiconductors with higher carrier mobility and better transparency have been actively pursued for numerous applications, such as flat-panel display backplane and sensor arrays. The carrier mobility is an important figure of merit and is sensitively influenced by the crystallinity and the molecular arrangement in a crystal lattice. Here we describe the growth of a highly aligned meta-stable structure of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) from a blended solution of C8-BTBT and polystyrene by using a novel off-centre spin-coating method. Combined with a vertical phase separation of the blend, the highly aligned, meta-stable C8-BTBT films provide a significantly increased thin film transistor hole mobility up to 43 cm(2) Vs(-1) (25 cm(2) Vs(-1) on average), which is the highest value reported to date for all organic molecules. The resulting transistors show high transparency of >90% over the visible spectrum, indicating their potential for transparent, high-performance organic electronics.
    Nature Communications 01/2014; 5:3005. · 10.74 Impact Factor
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    ABSTRACT: Most optimized donor-acceptor (D-A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than ∼80% of incident photons with energies above the polymer's band gap. If the thickness of these devices could be increased without sacrificing internal quantum efficiency, the device power conversion efficiency (PCE) could be significantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b′]dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) with 7.3% PCE and find that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge-carrier recombination and limit device quantum efficiency. These findings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum efficiency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells.
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    ABSTRACT: New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.
    Nature Communications 01/2014; 5:3007. · 10.74 Impact Factor
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    ABSTRACT: In this work, the impact of cation disorder on the electrical properties of biaxially textured Co2ZnO4 and Co2NiO4 thin films grown by pulsed laser deposition are investigated using a combination of experiment and theory. Resonant elastic X‐ray diffraction along with conductivity measurements both before and after post‐deposition annealing show that Co2ZnO4 and Co2NiO4 exhibit opposite changes of the conductivity with cation disorder, which can be traced back to their different ground‐state atomic structures, being normal and inverse spinel, respectively. Electronic structure calculations identify a self‐doping mechanism as the origin of conductivity. A novel thermodynamic model describes the non‐equilibrium cation disorder in terms of an effective temperature. This work offers a way of controlling the conductivity in spinels in a quantitative manner by controlling the cation disorder and a new design principle whereby non‐equilibrium growth can be used to create beneficial disorder. A combination of experiment and theory quantifies the dependence of the conductivity in Co2ZnO4 and Co2NiO4 on the cation disorder. A self‐doping mechanism is identified as the origin of conductivity and a thermodynamic model is used to describe the non‐equilibrium cation disorder in terms of an effective temperature. The conductivity in spinels can be controlled by manipulating the cation disorder.
    Advanced Functional Materials 01/2014; 24(5). · 10.44 Impact Factor
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    ABSTRACT: The introduction of processing additives is widely used to increase power conversion efficiencies in organic solar cells. Michael F. Toney, Jeremy R. Niskala and co-workers show on page 300 how additives change the polymer conformation in the casting solution leading to a more-intermixed phase-segregated network structure of the organic solar-cell active layer. This results in a five-fold enhancement in efficiency.
    Advanced Materials 01/2014; 26(2):299. · 14.83 Impact Factor
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    ABSTRACT: Charge-carrier transport in thin-film organic field-effect transistors takes place within the first (few) molecular layer(s) of the active organic material in contact with the gate dielectric. Here, we use atomistic molecular dynamics simulations to evaluate how interactions with bare amorphous silica surfaces that vary in terms of surface potential influence the molecular packing and dynamics of a monolayer pentacene film. The results indicate that the long axis of the pentacene molecules have a non-negligible tilt-angle away from the surface normal. Grazing-incidence X-ray diffraction patterns for these models are calculated, and we discuss notable differences in the shapes of the Bragg rods as a function of the molecular packing, also in relation to previously published experimental reports. Intermolecular electronic couplings (transfer integrals) evaluated for the monolayers show marked differences compared to bulk crystal calculations, a result that points to the importance of fully considering the molecular packing environment in charge-carrier mobility models for organic electronic materials.
    ACS Nano 12/2013; · 12.03 Impact Factor
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    ABSTRACT: Sensors based on organic thin-film transistors (OTFTs) are of considerable interest for chemical and biological detection applications, and the development of highly sensitive, chemically specific, low-cost sensors operating in aqueous environments will have a profound impact. However, the behavior of the dielectric and semiconducting thin films in OFTF-based sensors during underwater operation is not well understood. Here we investigate OTFT-based sensor materials, specifically a polymer dielectric film of cross-linked poly(4-vinylphenol) (x-PVP), used in OTFTs operating in aqueous environments. We show that immersing x-PVP thin films in a 90:10 water–methanol (model analyte) solution causes swelling of nearly 30% and a corresponding 300% increase in the film dielectric constant. Hence, to quantify the charge-transport behavior of organic molecules within aqueous environments, this drastic change in the capacitance must be accounted for in sensor material design.
    Chemistry of Materials. 12/2013; 25(24):5018–5022.
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    ABSTRACT: Efficient charge carrier transport in organic field-effect transistors (OFETs) requires thin films that display long-range order and π-π packing that is both tight and oriented in-plane with the substrate. Some polymers have achieved high field-effect mobility with such solid-state properties; however, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm2/V⋅s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm2/V⋅s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably tighter, and align with a greater preference for in-plane π-π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when non-solvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π-π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials.
    Journal of the American Chemical Society 12/2013; · 10.68 Impact Factor

Publication Stats

4k Citations
1,811.22 Total Impact Points

Institutions

  • 2010–2013
    • University of California, Santa Barbara
      • Materials Research Laboratory
      Santa Barbara, California, United States
    • Princeton University
      • Department of Chemical and Biological Engineering
      Princeton, NJ, United States
  • 2009–2013
    • Victoria University of Wellington
      • • MacDiarmid Institute for Advanced Materials and Nanotechnology
      • • School of Chemical and Physical Sciences
      Wellington, Wellington, New Zealand
    • MacDiarmid Institute for Advanced Materials and Nanotechnology
      Wellington, Wellington, New Zealand
    • Callaghan Innovation
      Lower Hutt City, Wellington, New Zealand
  • 2008–2013
    • Stanford University
      • • Department of Chemical Engineering
      • • Department of Materials Science and Engineering
      Palo Alto, CA, United States
    • CSU Mentor
      Long Beach, California, United States
  • 2012
    • Imperial College London
      Londinium, England, United Kingdom
  • 2010–2012
    • Columbia University
      • • Department of Chemistry
      • • Columbia Center for Electron Transport in Molecular Nanostructures (NSEC)
      New York City, NY, United States
  • 2011
    • Carnegie Mellon University
      • Department of Materials Science and Engineering
      Pittsburgh, Pennsylvania, United States
  • 2009–2011
    • National Institute of Standards and Technology
      • Polymers Division
      Gaithersburg, MD, United States
  • 2008–2010
    • University of California, Berkeley
      • Department of Mechanical Engineering
      Berkeley, MO, United States
  • 2007–2008
    • University of Houston
      • Department of Chemical & Biomolecular Engineering
      Houston, TX, United States
    • Palo Alto Research Center
      Palo Alto, California, United States
  • 2005
    • Los Alamos National Laboratory
      • Materials Science and Technology Division
      Los Alamos, NM, United States
  • 2004
    • University of Minnesota Duluth
      Duluth, Minnesota, United States
    • University of Minnesota Twin Cities
      • Department of Chemical Engineering and Materials Science
      Minneapolis, MN, United States
  • 1998
    • University of Wales
      Cardiff, Wales, United Kingdom
  • 1991
    • University of Washington Seattle
      • Department of Physics
      Seattle, Washington, United States