Tevye Kuykendall

Photoelectrochemical Water Splitting Using Dense and Aligned TiO2 Nanorod Arrays

Dense and aligned TiO2 nanorod arrays are fabricated using oblique-angle deposition on indium tin oxide (ITO) conducting substrates. The TiO2 nanorods are measured to be 800-1100 nm in length and 45-400 nm in width with an anatase crystal phase. Coverage of the ITO is extremely high with 25 x 10(6) mm(-2) of the TiO2 nanorods. The first use of these dense TiO2 nanorod arrays as working electrodes in photoelectrochemical (PEC) cells used for the generation of hydrogen by water splitting is demonstrated. A number of experimental techniques including UV/Vis absorption spectroscopy, X-ray diffraction, high-resolution scanning electron microscopy, energy-dispersive X-ray spectroscopy, and photoelectrochemistry are used to characterize their structural, optical, and electronic properties. Both UV/Vis and incident-photon-to-current-efficiency measurements show their photoresponse in the visible is limited but with a marked increase around approximately 400 nm. Mott-Schottky measurements give a flat-band potential (V(FB)) of +0.20 V, a carrier density of 4.5 x 10(17) cm(-3), and a space-charge layer of 99 nm. Overall water splitting is observed with an applied overpotential at 1.0 V (versus Ag/AgCl) with a photo-to-hydrogen efficiency of 0.1%. The results suggest that these dense and aligned one-dimensional TiO2 nanostructures are promising for hydrogen generation from water splitting based on PEC cells.

Multilayer nanoassembly of Sn-nanopillar arrays sandwiched between graphene layers for high-capacity lithium storage

Sn nanopillar arrays embedded between graphene sheets were assembled using a conventional film deposition and annealing process. The as-formed three-dimensional (3D) multilayered nanostructure was directly used as an anode material for rechargeable lithium-ion batteries without adding any polymer binder and carbon black. Electrochemical measurements showed very high reversible capacity and excellent cycling performance at a current density as high as 5 A g−1. These results demonstrated that nanocomposite materials with highly functional 1D and 2D components can be synthesized by employing conventional top-down manufacturing methods and self-assembly principles.

Electrostatics of nanowire transistors with triangular cross sections

The electrostatic properties of nanowire field effect transistors with triangular cross sections were investigated. The Poisson equation was solved for these structures; furthermore, two properties of the nanowire field effect transistors, the gate capacitance and current versus gate voltage, were calculated. The simulation results yielded the type, mobility, and concentration of the carriers, as well as the Ohmic contact resistance of the wire transistor. We examined how wire capacitance depends on various parameters: wire diameter, gate oxide thickness, charge density, and shape. It is shown that the capacitance of a triangular nanowire is less than that of a cylindrical nanowire of the same size, which could be significant in structures with thin gate oxides. The simulation results were compared with the previously reported experimental data on GaN nanowires.

Probing carrier lifetimes in photovoltaic materials using subsurface two-photon microscopy.

Accurately measuring the bulk minority carrier lifetime is one of the greatest challenges in evaluating photoactive materials used in photovoltaic cells. One-photon time-resolved photoluminescence decay measurements are commonly used to measure lifetimes of direct bandgap materials. However, because the incident photons have energies higher than the bandgap of the semiconductor, most carriers are generated close to the surface, where surface defects cause inaccurate lifetime measurements. Here we show that two-photon absorption permits sub-surface optical excitation, which allows us to decouple surface and bulk recombination processes even in unpassivated samples. Thus with two-photon microscopy we probe the bulk minority carrier lifetime of photovoltaic semiconductors. We demonstrate how the traditional one-photon technique can underestimate the bulk lifetime in a CdTe crystal by 10× and show that two-photon excitation more accurately measures the bulk lifetime. Finally, we generate multi-dimensional spatial maps of optoelectronic properties in the bulk of these materials using two-photon excitation.

Nanofluidic transport through isolated carbon nanotube channels: Advances, controversies, and challenges

Owing to their simple chemistry and structure, controllable geometry, and a plethora of unusual yet exciting transport properties, carbon nanotubes (CNTs) have emerged as exceptional channels for fundamental nanofluidic studies, as well as building blocks for future fluidic devices that can outperform current technology in many applications. Leveraging the unique fluidic properties of CNTs in advanced systems requires a full understanding of their physical origin. Recent advancements in nanofabrication technology enable nanofluidic devices to be built with a single, nanometer-wide CNT as a fluidic pathway. These novel platforms with isolated CNT nanochannels offer distinct advantages for establishing quantitative structure-transport correlations in comparison with membranes containing many CNT pores. In addition, they are promising components for single-molecule sensors as well as for building nanotube-based circuits wherein fluidics and electronics can be coupled. With such advanced device architecture, molecular and ionic transport can be manipulated with vastly enhanced control for applications in sensing, separation, detection, and therapeutic delivery. Recent achievements in fabricating isolated-CNT nanofluidic platforms are highlighted, along with the most-significant findings each platform enables for water, ion, and molecular transport. The implications of these findings and remaining open questions on the exceptional fluidic properties of CNTs are also discussed.

Catalyst-directed crystallographic orientation control of GaN nanowire growth.

In this work, we demonstrate that catalyst composition can be used to direct the crystallographic growth axis of GaN nanowires. By adjusting the ratio of gold to nickel in a bimetallic catalyst, we achieved selective growth of dense, uniform nanowire arrays along two nonpolar directions. A gold-rich catalyst resulted in single-crystalline nanowire growth along the ⟨11̅00⟩ or m axis, whereas a nickel-rich catalyst resulted in nanowire growth along the ⟨112̅0⟩ or a axis. The same growth control was demonstrated on two different epitaxial substrates. Using proper conditions, many of the nanowires were observed to switch direction midgrowth, resulting in monolithic single-crystal structures with segments of two distinct orientations. Cathodoluminescence spectra revealed significant differences in the optical properties of these nanowire segments, which we attribute to the electronic structures of their semipolar {112̅2} or {11̅01} sidewalls.

Gallium Nitride Nanowires and Heterostructures: Toward Color‐Tunable and White‐Light Sources

Gallium-nitride-based light-emitting diodes have enabled the commercialization of efficient solid-state lighting devices. Nonplanar nanomaterial architectures, such as nanowires and nanowire-based heterostructures, have the potential to significantly improve the performance of light-emitting devices through defect reduction, strain relaxation, and increased junction area. In addition, relaxation of internal strain caused by indium incorporation will facilitate pushing the emission wavelength into the red. This could eliminate inefficient phosphor conversion and enable color-tunable emission or white-light emission by combining blue, green, and red sources. Utilizing the waveguiding modes of the individual nanowires will further enhance light emission, and the properties of photonic structures formed by nanowire arrays can be implemented to improve light extraction. Recent advances in synthetic methods leading to better control over GaN and InGaN nanowire synthesis are described along with new concept devices leading to efficient white-light emission.

Growth of GaN@InGaN Core-Shell and Au-GaN Hybrid Nanostructures for Energy Applications

We demonstrated a method to control the bandgap energy of GaN nanowires by forming GaN@InGaN core-shell hybrid structures using metal organic chemical vapor deposition (MOCVD). Furthermore, we show the growth of Au nanoparticles on the surface of GaN nanowires in solution at room temperature. The work shown here is a first step toward engineering properties that are crucial for the rational design and synthesis of a new class of photocatalytic materials. The hybrid structures were characterized by various techniques, including photoluminescence (PL), energy dispersive x-ray spectroscopy (EDS), transmission and scanning electron microscopy (TEM and SEM), and x-ray diffraction (XRD).

Gain and Raman line-broadening with graphene coated diamond-shape nano-antennas

Using Surface Enhanced Raman Scattering (SERS), we report on intensity-dependent broadening in graphene-deposited broad-band antennas. The antenna gain curve includes both the incident frequency and some of the scattered mode frequencies. By comparing antennas with various gaps and types (bow-tie vs. diamond-shape antennas) we make the case that the line broadening did not originate from strain, thermal or surface potential. Strain, if present, further shifts and broadens those Raman lines that are included within the antenna gain curve.

Tarnishing Silver Metal into Mithrene

Silver metal exposed to the atmosphere corrodes and becomes tarnished as a result of oxidation and precipitation of the metal as an insoluble salt. Tarnish has so poor a reputation that the word itself connotes corruption and disrespectability; however, tarnishing is a facile synthetic approach for preparing thin metal-sulfide films on silver or copper metal that might be exploited to prepare more elaborate materials with desirable optoelectronic properties. In this work, we prepare luminescent semiconducting thin films of mithrene, a metal-organic chalcogenolate assembly, by replacing the tarnish-causing atmospheric sulfur source with diphenyl diselenide. Mithrene, or silver benzeneselenolate [AgSePh]∞, is a crystalline solid that contains both an organic supramolecular phase and a two-dimensional inorganic coordination polymer phase. This compound gradually accumulates as the sole product of silver metal corrosion. The chemical reaction is carried out on metallic silver thin films and yields crystalline films with thicknesses ranging from 5 to 100 nm. We use the large-area films (>6 cm2) afforded by this method to measure the optical properties of this compound. The mild-temperature, wafer-scale processing of hybrid chalcogenolate thin films may prove useful in the application of hybrid organic-inorganic materials in semiconductor devices and hierarchical architectures.