Geometry-tailored freestanding epitaxial Pd, AuPd, and Au nanoplates driven by surface interactions.

Freestanding epitaxial metal nanoplates can be utilized as advanced three-dimensional platforms for various novel applications. Here we report the vapor-phase epitaxial growth of freestanding Pd, AuPd, and Au nanoplates on an a-cut sapphire substrate as well as the comprehensive study of their growth mechanisms and geometry tailoring. All as-grown Pd, AuPd, and Au nanoplates possess twin-free single crystallinity as well as are aligned three-dimensionally on the substrate with the same orientation. Interestingly, depending on their composition, they have the following three distinct geometries: trapezoid (Pd), hexagon (AuPd), or rhombus (Au). By analyzing the correlation of the geometry and orientation of the as-synthesized nanostructures, we reveal that all the nanoplates grow from square pyramidal seed crystals. The interfacial lattice mismatch between the bottom plane of the square pyramidal seeds and a-cut sapphire substrate increases in the following order: Pd < AuPd < Au. Consequently, the length of the interface between the bottom of the nanoplate and the substrate decreases in the following order: Pd > AuPd > Au; this leads to the resulting geometries of the synthesized nanoplates. Such a fundamental understanding of the growth mechanism would aid the growth of epitaxial metal nanostructures with the desired geometry, which is very attractive for building macroscale functional nanoarchitectures.

Epitaxially aligned submillimeter-scale silver nanoplates grown by simple vapor transport.

Epitaxially aligned large silver (Ag) nanoplate arrays with ultraclean surfaces are very attractive for novel plasmonic applications. Although solution-phase methods have been extensively employed to synthesize Ag nanoplates, these cannot be used to grow epitaxial large Ag nanoplates on substrates. Here we report a vapor-phase synthetic strategy to epitaxially grow submillimeter-scale Ag nanoplates on a variety of substrates. By simply transporting Ag vapor to the substrates at an optimal temperature (820 °C), we synthesize ∼100 µm-sized Ag nanoplates with atomically clean surfaces, which are three-dimensionally aligned on the substrates. We demonstrate that both the type of supported seed and their interfacial lattice matching with the substrates determine the epitaxial growth habit of the nanoplates, directing their crystallinity, shape, and orientation. (i) On r-cut sapphire substrates, twinned pentagonal nanoplates grow vertically from twinned triangular seeds through a seed → nanoplate process. (ii) On m-cut sapphire substrates, twinned trapezoidal Ag nanoplates grow slantingly from twinned decahedral seeds through a seed → NW → nanoplate process. (iii) Interestingly, twin-free single-crystalline trapezoidal Ag nanoplates grow from twin-free square pyramidal seeds on STO (001) substrates through a seed → NW → nanoplate process. The epitaxially aligned Ag nanoplate arrays could serve as a new platform for two-dimensional (2D) guiding of surface plasmons as well as for hierarchical 3D plasmonic nanoarchitecturing.

Quantum Electronic Transport of Topological Surface States in ß-Ag2Se Nanowire.

Single-crystalline ß-Ag2Se nanostructures, a new class of 3D topological insulators (TIs), were synthesized using the chemical vapor transport method. The topological surface states were verified by measuring electronic transport properties including the weak antilocalization effect, Aharonov-Bohm oscillations, and Shubnikov-de Haas oscillations. First-principles band calculations revealed that the band inversion in ß-Ag2Se is caused by strong spin-orbit coupling and Ag-Se bonding hybridization. These investigations provide evidence of nontrivial surface state about ß-Ag2Se TIs that have anisotropic Dirac cones.

Composition-selective fabrication of ordered intermetallic Au-Cu nanowires and their application to nano-size electrochemical glucose detection.

Bimetallic nanostructures can provide distinct and improved physicochemical properties by the coupling effect of the two metal components, making them promising materials for a variety of applications. Herein, we report composition-selective fabrication of ordered intermetallic Au-Cu nanowires (NWs) by two-step chemical vapor transport method and their application to nano-electrocatalytic glucose detection. Ordered intermetallic Au3Cu and AuCu3 NWs are topotaxially fabricated by supplying Cu-containing chemicals to pre-synthesized single-crystalline Au NW arrays. The composition of fabricated Au-Cu NWs can be selected by changing the concentration of Cu-containing species. Interestingly, Au3Cu NW electrodes show unique electrocatalytic activity for glucose oxidation, allowing us to detect glucose without interference from ascorbic acid. Such interference-free detection of glucose is attributed to the synergistic effect, induced by incorporation of Cu in Au. We anticipate that Au3Cu NWs could show possibility as efficient nano-size electrochemical glucose sensors and the present fabrication method can be employed to fabricate valuable ordered intermetallic nanostructures.

Epitaxially aligned cuprous oxide nanowires for all-oxide, single-wire solar cells.

As a p-type semiconducting oxide that can absorb visible light, cuprous oxide (Cu2O) is an attractive material for solar energy conversion. This work introduces a high-temperature, vapor-phase synthesis that produces faceted Cu2O nanowires that grow epitaxially along the surface of a lattice-matched, single-crystal MgO substrate. Individual wires were then fabricated into single-wire, all-oxide diodes and solar cells using low-temperature atomic layer deposition (ALD) of TiO2 and ZnO films to form the heterojunction. The performance of devices made from pristine Cu2O wires and chlorine-exposed Cu2O wires was investigated under one-sun and laser illumination. These faceted wires allow the fabrication of well-controlled heterojunctions that can be used to investigate the interfacial properties of all-oxide solar cells.

Truncated tetrahedron seed crystals initiating stereoaligned growth of FeSi nanowires.

We have synthesized epitaxially grown freestanding FeSi nanowires (NWs) on an m-Al(2)O(3) substrate by using a catalyst-free chemical vapor transport method. FeSi NW growth is initiated from FeSi nanocrystals, formed on a substrate in a characteristic shape with a specific orientation. Cross-section TEM analysis of seed crystals reveals the crystallographic structure and hidden geometry of the seeds. Close correlation of geometrical shapes and orientations of the observed nanocrystals with those of as-grown NWs indicates that directional growth of NWs is initiated from the epitaxially formed seed crystals. The diameter of NWs can be controlled by adjusting the composition of Si in a Si/C mixture. The epitaxial growth method for FeSi NWs via seed crystals could be employed to heteroepitaxial growth of other compound NWs.

Diffusion-driven crystal structure transformation: synthesis of Heusler alloy Fe3Si nanowires.

We report fabrication of Heusler alloy Fe(3)Si nanowires by a diffusion-driven crystal structure transformation method from paramagnetic FeSi nanowires. Magnetic measurements of the Fe(3)Si nanowire ensemble show high-temperature ferromagnetic properties with T(c) >> 370 K. This methodology is also successfully applied to Co(2)Si nanowires in order to obtain metal-rich nanowires (Co) as another evidence of the structural transformation process. Our newly developed nanowire crystal transformation method would be valuable as a general method to fabricate metal-rich silicide nanowires that are otherwise difficult to synthesize.