Jason K. Kawasaki

Synthesis of platinum dendrites and nanowires via directed electrochemical nanowire assembly.

Directed electrochemical nanowire assembly is a promising high growth rate technique for synthesizing electrically connected nanowires and dendrites at desired locations. Here we demonstrate the directed growth and morphological control of edge-supported platinum nanostructures by applying an alternating electric field across a chloroplatinic acid solution. The dendrite structure is characterized with respect to the driving frequency, amplitude, offset, and salt concentration and is well-explained by classical models. Control over the tip diameter, side branch spacing, and amplitude is demonstrated, opening the door to novel device architectures for sensing and catalytic applications.

Influence of Surface Adsorption on the Oxygen Evolution Reaction on IrO2(110)

A catalyst functions by stabilizing reaction intermediates, usually through surface adsorption. In the oxygen evolution reaction (OER), surface oxygen adsorption plays an indispensable role in the electrocatalysis. The relationship between the adsorption energetics and OER kinetics, however, has not yet been experimentally measured. Herein we report an experimental relationship between the adsorption of surface oxygen and the kinetics of the OER on IrO2(110) epitaxially grown on a TiO2(110) single crystal. The high quality of the IrO2 film grown using molecular-beam epitaxy affords the ability to extract the surface oxygen adsorption and its impact on the OER. By examining a series of electrolytes, we find that the adsorption energy changes linearly with pH, which we attribute to the electrified interfacial water. We support this hypothesis by showing that an electrolyte salt modification can lead to an adsorption energy shift. The dependence of the adsorption energy on pH has implications for the OER kinetics, but it is not the only factor; the dependence of the OER electrocatalysis on pH stipulates two OER mechanisms, one operating in acidic solution and another operating in alkaline solution. Our work points to the subtle adsorption-kinetics relationship in the OER and highlights the importance of the interfacial electrified interaction in electrocatalyst design.

Oxygen evolution reaction electrocatalysis on SrIrO3 grown using molecular beam epitaxy

Electrochemical generation of oxygen via the oxygen evolution reaction (OER) is a key enabling step for many air-breathing electrochemical energy storage devices. IrO2 (Ir4+: 5d5) ranks among the most active known OER catalysts. However, it is unclear how the environment of the Ir4+ oxygen-coordination octahedra affects the OER electrocatalysis. Herein, we present the OER kinetics on a single-crystal, epitaxial SrIrO3(100)p perovskite oxide synthesized using molecular-beam epitaxy on a DyScO3(110) substrate. We find that by switching the host structure of the Ir4+ oxygen-coordination octahedra from corner- and edge-sharing rutile (IrO2) to purely corner-sharing perovskite (SrIrO3), the OER activity increases by more than an order of magnitude. We explain our finding with the correlated, semimetal electronic structure of SrIrO3; our density functional theory calculations reveal that the adsorption energetics on SrIrO3 depends sensitively on the electron–electron interaction, whereas for IrO2, it depends rather weakly. This finding suggests the importance of correlations on the OER and the design of future transition metal oxide electrocatalysts.

Local density of states and interface effects in semimetallic ErAs nanoparticles embedded in GaAs.

The atomic and electronic structures of ErAs nanoparticles embedded within a GaAs matrix are examined via cross-sectional scanning tunneling microscopy and spectroscopy (XSTM/XSTS). The local density of states (LDOS) exhibits a finite minimum at the Fermi level demonstrating that the nanoparticles remain semimetallic despite the predictions of previous models of quantum confinement in ErAs. We also use XSTS to measure changes in the LDOS across the ErAs/GaAs interface and propose that the interface atomic structure results in electronic states that prevent the opening of a band gap.

Evolution in surface morphology of epitaxial graphene layers on SiC induced by controlled structural strain

The evolution in the surface morphology of epitaxial graphene films and 6H-SiC(0001) substrates is studied by electron channeling contrast imaging. Whereas film thickness is determined by growth temperature only, increasing growth times at constant temperature affects both internal stress and film morphology. Annealing times in excess of 8–10 min lead to an increase in the mean square roughness of SiC step edges to which graphene films are pinned, resulting in compressively stressed films at room temperature. Shorter annealing times produce minimal changes in the morphology of the terrace edges and result in nearly stress-free films upon cooling to room temperature.

Growth and transport properties of epitaxial lattice matched half Heusler CoTiSb/InAlAs/InP(001) heterostructures

We demonstrate the integration of the lattice matched single crystal epitaxial Half Heusler compound CoTiSb with In0.52Al0.48As/InP(001) heterostructures using molecular beam epitaxy. CoTiSb belongs to the subset of Half Heusler compounds that is expected to be semiconducting, despite being composed entirely of metallic constituents. The lattice matching and epitaxial alignment of the CoTiSb films were confirmed by reflection high energy electron diffraction and X-ray diffraction. Temperature dependent transport measurements indicate semiconducting-like behavior, with a room temperature Hall mobility of 530 cm2/Vs and background Hall carrier density of 9.0 × 1017 cm−3, which is comparable to n-Si with similar carrier density. Below 100 K, the films show a large negative magnetoresistance, and possible origins of this negative magnetoresistance are discussed.

Surface and electronic structure of epitaxial PtLuSb (001) thin films

The surface and electronic structure of single crystal thin films of PtLuSb (001) grown by molecular beam epitaxy were studied. Scanning tunneling spectroscopy (STS), photoemission spectroscopy, and temperature dependent Hall measurements of PtLuSb thin films are consistent with a zero-gap semiconductor or semi-metal. STS and photoemission measurements show a decrease in density of states approaching the Fermi level for both valence and conduction bands as well as a slight shift of the Fermi level position into the valence band. Temperature dependent Hall measurements also corroborate the Fermi level position by measurement of p-type carriers.

Epitaxial growth and surface studies of the Half Heusler compound NiTiSn (001)

The Half Heuslers are currently an attractive family of compounds for high temperature thermoelectrics research, and recently, there has been renewed interest since some of these compounds are proposed to be topological insulators. NiTiSn belongs to the family of 18 valence electron Half Heuslers that are predicted to be semiconducting, despite being composed entirely of metallic elements. The growth of the Half Heusler compound NiTiSn by molecular beam epitaxy is demonstrated. The NiTiSn films are epitaxial and single crystalline as observed by reflection high-energy electron diffraction and x-ray diffraction. Temperature dependent transport measurements suggest the films may be semiconducting, but with a high background carrier density indicative of a high density of electrically active defect states. Methods of protecting the sample surface for synchrotron-based photoemission measurements are explored. These methods may be applied to the study of surface electronic structure in unconventional materials.

Martensite transformation of epitaxial Ni-Ti films

The structure and phase transformations of thin Ni–Ti shape memory alloy films grown by molecular beam epitaxy are investigated for compositions from 43 to 56 at. % Ti. Despite the substrate constraint, temperature dependent x-ray diffraction and resistivity measurements reveal reversible, martensitic phase transformations. The results suggest that these occur by an in-plane shear which does not disturb the lattice coherence at interfaces.

Cross-sectional scanning tunneling microscopy and spectroscopy of semimetallic ErAs nanostructures embedded in GaAs

The growth and atomic/electronic structure of molecular beam epitaxy-grown ErAs nanoparticles and nanorods embedded within a GaAs matrix are examined for the first time via cross-sectional scanning tunneling microscopy and spectroscopy. Cross sections enable the interrogation of the internal structure and are well suited for studying embedded nanostructures. The early stages of embedded ErAs nanostructure growth are examined via these techniques and compared with previous cross-sectional transmission electron microscopy work. Tunneling spectroscopy I(V) for both ErAs nanoparticles and nanorods was also performed, demonstrating that both nanostructures are semimetallic