Anodically Induced Chemical Etching of GaAs Wafers for a GaAs Nanowire-Based Flexible Terahertz Wave Emitter.

A generic top-down approach for the preparation of extended arrays of high-aspect ratio GaAs nanowires (NWs) with different crystallographic orientations (i.e., [100] or [111]) and morphologies (i.e., porous, nonporous, tapered, or awl-like NWs) is reported. The method is based on the anodically induced chemical etching (AICE) of GaAs wafers in an oxidant-free aqueous HF solution at room temperature by using a patterned metal mesh and allows us to overcome the drawbacks of conventional metal-assisted chemical etching (MACE) processes. Local oxidative dissolution of GaAs in contact with a metal is achieved by externally injecting holes (h+) into the valence band (VB) of GaAs through the metal mesh. It is found that injection of holes (h+) through direct GaAs contact, rather than the metal mesh, does not yield uniform nanowires but porosify GaAs wafers due to the high cell potential. On the basis of experiments and numerical simulation for the spatial distribution of an electric field, a phenomenological model that explains the formation of GaAs NWs and their porosification behaviors is proposed. GaAs NWs exhibit excellent terahertz (THz) wave emission properties, which vary with either the length or the shape of the nanowires. By taking advantage of controlled porosification and easy transfer of GaAs NWs to foreign substrates, a flexible THz wave emitter is realized.

Template-Free Electrochemical Growth of Ni-Decorated ZnO Nanorod Array: Application to an Anode of Lithium Ion Battery.

ZnO nanorods (NRs) decorated with Ni nanoparticles were synthesized using a template-free electrochemical deposition in an ultra-dilute aqueous electrolyte and a subsequent galvanic reaction. The electrochemical properties of the ZnO NRs as an anode material for rechargeable Li-ion batteries were evaluated for different binder morphologies (film and close-packed spherical particles) of polyvinylidene fluoride (PVDF). Results showed that the close-packed spherical PVDF simultaneously improved electrochemical capacity and cyclability because the free-volume between the spherical PVDF helped to accommodate the volume change in the anode caused by the Li ions discharge and charge processes. Furthermore, the Ni nanoparticles decorated on the surface of ZnO NRs enhanced the electrical conductivity of the ZnO NR anode, which enabled faster electronic and ionic transport at the interface between the electrolyte and the electrode, resulting in improved electrochemical capacity. The free-volume formed by the close-packed spherical PVDF, and the decoration of metal nanoparticles are expected to provide insight on the simultaneous improvement of electrochemical capacity and cyclability in other metal oxide anode nanostructures.

Electrochemical properties of Sn-decorated SnO nanobranches as an anode of Li-ion battery.

Sn-based oxide materials as an anode of lithium ion batteries (LIBs) suffer from the unavoidable mechanical stress originated from huge volume changes during lithiation/delithiation reactions. We synthesized the hierarchical SnO nanobranches (NBs) decorated with Sn nanoparticles on Cu current collector using a vapor transport method. The Sn-decorated SnO NBs as an anode of LIB showed good electrochemical performance with high reversible capacity retention of as high as 502 mAh/g and rate capability of 455 mAh/g at a current density of 2.0 A/g after 50 cycles. Through the morphological and crystal structure analyses after the charge and discharge processes, it was found that the morphology of Sn-decorated SnO NBs was transformed to nanoporous layered-structure, composed of Sn and lithium oxide, during the repeated lithiation/delithiation reactions. The free-volume of Sn-decorated SnO NBs and nanoporous layered-structure effectively accommodate the huge volume changes and enhance the electrochemical cyclability by facilitating the diffusion of Li-ions.

Electrochemical flow-based solution-solid growth of the Cu2O nanorod array: potential application to lithium ion batteries.

The catalyzed solution-liquid-solid (SLS) growth has been well developed to synthesize semiconductor nanowires with controlled diameters. The SLS growth occurs in the longitudinal direction of nanowires, due to the directional anisotropy driven by the metal catalysts where chemical precursors are introduced. In the present study, we report a selective, template-free, and environmentally-friendly electrochemical flow-based solution-solid (electrochemical flow-SS) growth of the Cu2O nanorod array. The anisotropy for directional growth without any catalysts is generated by the electrical field in a flowing electrolyte of ultra-dilute CuSO4. The filamentary anisotropy originates from electric field enhancement on pyramidal nanocrystals in the electrolyte of low ionic conductivity (13 µS cm(-1)). The Cu2O and Cu nanorods are able to be selectively synthesized by controlling the electrolyte pH and oxygen dissolution into the electrolyte. The synthesized Cu2O nanorod array shows excellent electrochemical properties as an anode material for lithium-ion batteries; the specific capacities increase from 323 to 1206 mA h g(-1) during 500 cycles. The capacity enhancement is due to the phase transformation from Cu2O to CuO, nano-restructuring of nanorods into fragmented nanoparticles, and the progressive generation of an electroactive polymeric gel-like layer on the surface of the nanoparticles. The electrochemical flow-SS growth of Cu2O nanorods is expected to contribute to further development of other functional nanorods.

Effects of ZnO nanowire length on surface-assisted laser desorption/ionization of small molecules.

The effects of nanowire (NW) length on surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) of small molecules were investigated using ZnO NWs of 50 nm diameter with a broad range of lengths ranging from 25 to 1600 nm. Characterization of the ZnO NWs revealed that the length was the only parameter that varied in this study, while other properties of the NWs remained essentially the same as the bulk properties. Experiments on SALDI efficiency exhibited that the SALDI processes on NWs have a certain length window. In the present case of ZnO NWs, the SALDI efficiency was found to be enhanced on the nanowires of 250 nm length, corresponding to an aspect ratio of 5. The roles of NW length in the SALDI processes were discussed from the viewpoint of efficient energy-transfer media as well as physical obstacles screening laser irradiation and preventing the escape of nascent ions from NW surfaces. The existence of the length window may provide valuable insight for tailoring new nanostructures for efficient SALDI of small molecules.