The overriding obstacle to mass production of hydrogen from water as the premium fuel for powering our planet is the frustratingly slow kinetics of the oxygen evolution reaction (OER). Additionally, inadequate understanding of the key barriers of the OER is a hindrance to insightful design of advanced OER catalysts. This study presents ultrathin amorphous high‐surface area nickel boride (NixB) nanosheets as a low‐cost, very efficient and stable catalyst for the OER for electrochemical water splitting. The catalyst affords 10 mA cm−2 at 0.38 V overpotential during OER in 1.0 m KOH, reducing to only 0.28 V at 20 mA cm−2 when supported on nickel foam, which ranks it among the best reported nonprecious catalysts for oxygen evolution. Operando X‐ray absorption fine‐structure spectroscopy measurements reveal prevalence of NiOOH, as well as Ni‐B under OER conditions, owing to a Ni‐B core@nickel oxyhydroxide shell (Ni‐B@NiOxH) structure, and increase in disorder of the NiOxH layer, thus revealing important insight into the transient states of the catalyst during oxygen evolution.
Aberration corrected scanning transmission electron microscopy (STEM) with high angle annular dark field (HAADF) imaging and the newly developed annular bright field (ABF) imaging are used to define a new guideline for the polarity determination of semiconductor nanowires (NWs) from binary compounds in two extreme cases: (i) when the dumbbell is formed with atoms of similar mass (GaAs) and (ii) in the case where one of the atoms is extremely light (N or O: ZnO and GaN/AlN). The theoretical fundaments of these procedures allow us to overcome the main challenge in the identification of dumbbell polarity. It resides in the separation and identification of the constituent atoms in the dumbbells. The proposed experimental via opens new routes for the fine characterization of nanostructures, e.g., in electronic and optoelectronic fields, where the polarity is crucial for the understanding of their physical properties (optical and electronic) as well as their growth mechanisms.
The exciton-phonon coupling in high-quality cubic phase zinc telluride (ZnTe) nanorods (NRs) is investigated by resonant micro-Raman spectroscopy near the direct bandgap of ZnTe. The scattering cross section of longitudinal optical (LO) phonon is enhanced significantly in the resonant process, where the enhancement factor of LO modes is much higher than that of the transverse optical (TO) modes, indicating a dominant Fröhlich electron-phonon interaction mechanism. Up to fifth-order LO phonons are observed by resonant Raman scattering at room temperature. The Huang-Rhys factor of individual NRs-and thus the exciton-LO coupling strengths-is evaluated, showing increasing with the NR diameter. Surface optical (SO) phonon and its high-order overtones are observed between nLO and (n − 1)LO + TO for the first time, whose positions are consistent with a dielectric continuum model. Strong acoustic phonon-exciton coupling induces a high-frequency shoulder above each nLO peaks with two maxima located around 14 cm −1 and 32 cm −1 , which are assigned to transverse acoustic and longitudinal acoustic phonons, respectively. The resonant multiphonon scattering process involving acoustic and LO phonons is discussed based on an exciton-intermediated cascade model, where a scattering sequence of acoustic phonon followed by LO phonons is favorable. These results advance the understanding of electron-phonon coupling and exciton scattering in quasi-one-dimensional systems, especially in the scarcely documented ZnTe compound, facilitating the development and optimization of NR-based optoelectronic devices.
Combination of mismatched materials in semiconductor nanowire heterostructures offers a freedom of bandstructure engineering that is impossible in standard planar epitaxy. Nevertheless, the presence of strain and structural defects directly control the optoelectronic properties of these nanomaterials. Understanding with atomic accuracy how mismatched heterostructures release or accommodate strain, therefore, is highly desirable. By using atomic resolution high angle annular dark field scanning transmission electron microscopy combined with geometrical phase analyses and computer simulations, we are able to establish the relaxation mechanisms (including both elastic and plastic deformations) to release the mismatch strain in axial nanowire heterostructures. Formation of misfit dislocations, diffusion of atomic species, polarity transfer, and induced structural transformations are studied with atomic resolution at the intermediate ternary interfaces. Two nanowire heterostructure systems with promising applications (InAs/InSb and GaAs/GaSb) have been selected as key examples.
In this work the position-controlled growth of GaN nanowires (NWs) on diamond by means of molecular beam epitaxy is investigated. In terms of growth, diamond can be seen as a model substrate, providing information of systematic relevance also for other substrates. Thin Ti masks are structured by electron beam lithography which allows the fabrication of perfectly homogeneous GaN NW arrays with different diameters and distances. While the wurtzite NWs are found to be Ga-polar, N-polar nucleation leads to the formation of tripod structures with a zinc-blende core which can be efficiently suppressed above a substrate temperature of 870 °C. A variation of the III/V flux ratio reveals that both axial and radial growth rates are N-limited despite the globally N-rich growth conditions, which is explained by the different diffusion behavior of Ga and N atoms. Furthermore, it is shown that the hole arrangement has no effect on the selectivity but can be used to force a transition from nanowire to nanotube growth by employing a highly competitive growth regime.
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