Sean C. Andrews

Large-scale synthesis of transition-metal-doped TiO2 nanowires with controllable overpotential.

Practical implementation of one-dimensional semiconductors into devices capable of exploiting their novel properties is often hindered by low product yields, poor material quality, high production cost, or overall lack of synthetic control. Here, we show that a molten-salt flux scheme can be used to synthesize large quantities of high-quality, single-crystalline TiO2 nanowires with controllable dimensions. Furthermore, in situ dopant incorporation of various transition metals allows for the tuning of optical, electrical, and catalytic properties. With this combination of control, robustness, and scalability, the molten-salt flux scheme can provide high-quality TiO2 nanowires to satisfy a broad range of application needs from photovoltaics to photocatalysis.

Atomic layer deposition of platinum catalysts on nanowire surfaces for photoelectrochemical water reduction.

The photocathodic hydrogen evolution reaction (HER) from p-type Si nanowire (NW) arrays was evaluated using platinum deposited by atomic layer deposition (ALD) as a HER cocatalyst. ALD of Pt on the NW surface led to a highly conformal coating of nanoparticles with sizes ranging from 0.5 to 3 nm, allowing for precise control of the Pt loading in deep submonolayer quantities. The catalytic performance was measured using as little as 1 cycle of Pt ALD, which corresponded to a surface mass loading of ∼10 ng/cm(2). The quantitative exploration of the lower limits of Pt cocatalyst loading reported here, and its application to high-surface-area NW photoelectrodes, establish a general approach for minimizing the cost of precious-metal cocatalysts for efficient and affordable solar-to-fuel applications.

Quantifying Surface Roughness Effects on Phonon Transport in Silicon Nanowires

Although it has been qualitatively demonstrated that surface roughness can reduce the thermal conductivity of crystalline Si nanowires (SiNWs), the underlying reasons remain unknown and warrant quantitative studies and analysis. In this work, vapor-liquid-solid (VLS) grown SiNWs were controllably roughened and then thoroughly characterized with transmission electron microscopy to obtain detailed surface profiles. Once the roughness information (root-mean-square, σ, correlation length, L, and power spectra) was extracted from the surface profile of a specific SiNW, the thermal conductivity of the same SiNW was measured. The thermal conductivity correlated well with the power spectra of surface roughness, which varies as a power law in the 1-100 nm length scale range. These results suggest a new realm of phonon scattering from rough interfaces, which restricts phonon transport below the Casimir limit. Insights gained from this study can help develop a more concrete theoretical understanding of phonon-surface roughness interactions as well as aid the design of next generation thermoelectric devices.

Oriented assembly of polyhedral plasmonic nanoparticle clusters.

Shaped colloids can be used as nanoscale building blocks for the construction of composite, functional materials that are completely assembled from the bottom up. Assemblies of noble metal nanostructures have unique optical properties that depend on key structural features requiring precise control of both position and connectivity spanning nanometer to micrometer length scales. Identifying and optimizing structures that strongly couple to light is important for understanding the behavior of surface plasmons in small nanoparticle clusters, and can result in highly sensitive chemical and biochemical sensors using surface-enhanced Raman spectroscopy (SERS). We use experiment and simulation to examine the local surface plasmon resonances of different arrangements of Ag polyhedral clusters. High-resolution transmission electron microscopy shows that monodisperse, atomically smooth Ag polyhedra can self-assemble into uniform interparticle gaps that result in reproducible SERS enhancement factors from assembly to assembly. We introduce a large-scale, gravity-driven assembly method that can generate arbitrary nanoparticle clusters based on the size and shape of a patterned template. These templates enable the systematic examination of different cluster arrangements and provide a means of constructing scalable and reliable SERS sensors.

Cleaved-coupled nanowire lasers

The miniaturization of optoelectronic devices is essential for the continued success of photonic technologies. Nanowires have been identified as potential building blocks that mimic conventional photonic components such as interconnects, waveguides, and optical cavities at the nanoscale. Semiconductor nanowires with high optical gain offer promising solutions for lasers with small footprints and low power consumption. Although much effort has been directed toward controlling their size, shape, and composition, most nanowire lasers currently suffer from emitting at multiple frequencies simultaneously, arising from the longitudinal modes native to simple Fabry–Pérot cavities. Cleaved-coupled cavities, two Fabry–Pérot cavities that are axially coupled through an air gap, are a promising architecture to produce single-frequency emission. The miniaturization of this concept, however, imposes a restriction on the dimensions of the intercavity gaps because severe optical losses are incurred when the cross-sectional dimensions of cavities become comparable to the lasing wavelength. Here we theoretically investigate and experimentally demonstrate spectral manipulation of lasing modes by creating cleaved-coupled cavities in gallium nitride (GaN) nanowires. Lasing operation at a single UV wavelength at room temperature was achieved using nanoscale gaps to create the smallest cleaved-coupled cavities to date. Besides the reduced number of lasing modes, the cleaved-coupled nanowires also operate with a lower threshold gain than that of the individual component nanowires. Good agreement was found between the measured lasing spectra and the predicted spectral modes obtained by simulating optical coupling properties. This agreement between theory and experiment presents design principles to rationally control the lasing modes in cleaved-coupled nanowire lasers.

Ultrahigh electrical conductivity in solution-sheared polymeric transparent films

Significance Many applications, including solar cells and touch screens, require coatings that are both optically transparent and electrically conductive. Most device structures use indium tin oxide to serve as this transparent conductor (TC), even though it accounts for a disproportionally large amount of device cost. Alternatives, such as polymer-based materials, may not only provide additional cost benefits, but may also allow for added functionality, such as flexibility. In this paper, we examine conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) deposited by solution shearing as a TC film. Morphological and chemical changes caused by solution shearing deposition lead to record-high conductivities and overall excellent TC performance. With consumer electronics transitioning toward flexible products, there is a growing need for high-performance, mechanically robust, and inexpensive transparent conductors (TCs) for optoelectronic device integration. Herein, we report the scalable fabrication of highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films via solution shearing. Specific control over deposition conditions allows for tunable phase separation and preferential PEDOT backbone alignment, resulting in record-high electrical conductivities of 4,600 ± 100 S/cm while maintaining high optical transparency. High-performance solution-sheared TC PEDOT:PSS films were used as patterned electrodes in capacitive touch sensors and organic photovoltaics to demonstrate practical viability in optoelectronic applications.

Atomic-level control of the thermoelectric properties in polytypoid nanowires

Thermoelectric materials have generated interest as a means of increasing the efficiency of power generation through the scavenging of waste heat. Materials containing nanometer-sized structural and compositional features can exhibit enhanced thermoelectric performance due to the decoupling of certain electrical and thermal properties, but the extent to which these features can be controlled is often limited. Here we report a simple synthesis of M2O3(ZnO)n (M = In, Ga, Fe) nanowires with controllable polytypoid structures, where the nanostructured features are tuned by adjusting the amount of metal precursor. After the introduction of nanometer-scale features (individual atomic layers and alloying), thermal and electrical measurements on single In2-xGaxO3(ZnO)n nanowires reveal a simultaneous improvement in all contributing factors to the thermoelectric figure of merit, indicating successful modification of the nanowire transport properties.

Simultaneous Thermoelectric Property Measurement and Incoherent Phonon Transport in Holey Silicon

Block copolymer patterned holey silicon (HS) was successfully integrated into a microdevice for simultaneous measurements of Seebeck coefficient, electrical conductivity, and thermal conductivity of the same HS microribbon. These fully integrated HS microdevices provided excellent platforms for the systematic investigation of thermoelectric transport properties tailored by the dimensions of the periodic hole array, that is, neck and pitch size, and the doping concentrations. Specifically, thermoelectric transport properties of HS with a neck size in the range of 16-34 nm and a fixed pitch size of 60 nm were characterized, and a clear neck size dependency was shown in the doping range of 3.1 × 10(18) to 6.5 × 10(19) cm(-3). At 300 K, thermal conductivity as low as 1.8 ± 0.2 W/mK was found in HS with a neck size of 16 nm, while optimized zT values were shown in HS with a neck size of 24 nm. The controllable effects of holey array dimensions and doping concentrations on HS thermoelectric performance could aid in improving the understanding of the phonon scattering process in a holey structure and also in facilitating the development of silicon-based thermoelectric devices.

The Effects of Cross-Linking in a Supramolecular Binder on Cycle Life in Silicon Microparticle Anodes

Self-healing supramolecular binder was previously found to enhance the cycling stability of micron-sized silicon particles used as the active material in lithium-ion battery anodes. In this study, we systematically control the density of cross-linking junctions in a modified supramolecular polymer binder in order to better understand how viscoelastic materials properties affect cycling stability. We found that binders with relaxation times on the order of 0.1 s gave the best cycling stability with 80% capacity maintained for over 175 cycles using large silicon particles (∼0.9 um). We attributed this to an improved balance between the viscoelastic stress relaxation in the binder and the stiffness needed to maintain mechanical integrity of the electrode. The more cross-linked binder showed markedly worse performance confirming the need for liquid-like flow in order for our self-healing polymer electrode concept to be effective.

Electron delocalization and charge mobility as a function of reduction in a metal–organic framework

Conductive metal–organic frameworks are an emerging class of three-dimensional architectures with degrees of modularity, synthetic flexibility and structural predictability that are unprecedented in other porous materials. However, engendering long-range charge delocalization and establishing synthetic strategies that are broadly applicable to the diverse range of structures encountered for this class of materials remain challenging. Here, we report the synthesis of KxFe2(BDP)3 (0 ≤ x ≤ 2; BDP2− = 1,4-benzenedipyrazolate), which exhibits full charge delocalization within the parent framework and charge mobilities comparable to technologically relevant polymers and ceramics. Through a battery of spectroscopic methods, computational techniques and single-microcrystal field-effect transistor measurements, we demonstrate that fractional reduction of Fe2(BDP)3 results in a metal–organic framework that displays a nearly 10,000-fold enhancement in conductivity along a single crystallographic axis. The attainment of such properties in a KxFe2(BDP)3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.A conducting metal–organic framework with charge delocalization by reductive potassium insertion is demonstrated. Integration into a field-effect transistor shows similar mobilities to semiconductors, with a mobility estimated to be at least 0.84 cm2 V–1 s–1.