Michael F. Toney

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

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Publications (384)1952.78 Total impact

  • Source
    Chemistry of Materials 12/2014; · 8.24 Impact Factor
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    ABSTRACT: The crystallization and electrical characterization of the semiconducting polymer poly(3-hexylthiophene) (P3HT) on a single layer graphene sheet is reported. Grazing incidence X-ray diffraction revealed that P3HT crystallizes with a mixture of face-on and edge-on lamellar orientations on graphene compared to mainly edge-on on a silicon substrate. Moreover, whereas ultrathin (10 nm) P3HT films form well oriented face-on and edge-on lamellae, thicker (50 nm) films form a mosaic of lamellae oriented at different angles from the graphene substrate. This mosaic of crystallites with π–π stacking oriented homogeneously at various angles inside the film favors the creation of a continuous pathway of interconnected crystallites, and results in a strong enhancement in vertical charge transport and charge carrier mobility in the thicker P3HT film. These results provide a better understanding of polythiophene crystallization on graphene, and should help the design of more efficient graphene based organic devices by control of the crystallinity of the semiconducting film.
    Advanced Functional Materials 11/2014; · 10.44 Impact Factor
  • Elyse Coletta, Michael F. Toney, Curtis W. Frank
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    ABSTRACT: Current fuel cell technology demands improvements for widespread use, and novel polymer materials may be able to achieve the necessary enhancements. This work inspects the composition, structure, and properties of poly(ethylene glycol) (PEG)–aromatic polyimide systems aimed at polymer electrolyte membrane applications, as PEG is a known ion conductor and aromatic polyimides are quite stable. Liquid electrolytes were incorporated into the polymers through soaking to achieve ionic conductivity. By varying polyimide and liquid electrolyte, the polymers were analyzed for their structure and conductivity. Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry, small-angle X-ray scattering, electrochemical impedance spectroscopy, and cyclic voltammetry were used as characterization tools. Electrolyte identity impacts liquid uptake and conductivity. Polyimide identity can influence the size and variability of the doped polymer structure, which ultimately can change conductivity by up to 28%, with the maximum conductivity being 102 mS/cm at 80°C and 70% RH. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41675.
    Journal of Applied Polymer Science 11/2014; · 1.40 Impact Factor
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    ABSTRACT: ZnO nanotubes were prepared by selective dissolution of electrodeposited nanorods. The effect of solution pH, rod morphology and chloride ion concentration on the dissolution mechanism were studied. The selective etching was rationalized in terms of the surface energy of the different ZnO crystal faces and reactant diffusion. The nanorod diameter and chloride concentration are the most influential parameters on the dissolution mechanism because they control homogenous dissolution or selective etching of the (110) and (002) surfaces. Bulk solution pH only has an effect on the rate of dissolution. By accurate control of the dissolution process, the nanomorphology can be tailored and the formation of rods with a thin diameter (10-20 nm), cavity or ultra-thin-walled tubes (2-5 nm) can be achieved.
    Langmuir : the ACS journal of surfaces and colloids. 10/2014;
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    ABSTRACT: Alkyl substituents appended to the π-conjugated main chain account for the solution-processability and film-forming properties of most π-conjugated polymers for organic electronic device applications, including field-effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device performance. However, the factors that determine polymer crystallite orientation in thin-films, implying preferential backbone orientation relative to the device substrate, are a matter of some debate, and these structural changes remain difficult to anticipate. In this report, we show how systematic changes in the side-chain pattern of poly(benzo[1,2-b:4,5-b']dithiophene-alt-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers can (i) influence the propensity of the polymer to order in the π-stacking direction, and (ii) direct the preferential orientation of the polymer crystallites in thin films (e.g., "face-on" vs. "edge-on"). Oriented crystallites, specifically crystallites that are well ordered in the π-stacking direction, are believed to be a key contributor to improved thin-film device performance in both FETs and BHJ solar cells.
    ACS Applied Materials & Interfaces 10/2014; · 5.90 Impact Factor
  • 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

Publication Stats

4k Citations
1,952.78 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
  • 2006
    • Soongsil University
      • Department of Chemical and Environmental Engineering
      Sŏul, Seoul, South Korea
  • 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