Wensheng Shi

Synthesis of Large Areas of Highly Oriented, Very Long Silicon Nanowires**

Silicon is one of the most important electronic materials. Its nanoscale forms, such as nanocrystals, porous silicon, quantum wells, and nanowires, have stimulated great interest among scientists because of their peculiar physical properties, such as light emission, field emission, and quantum confinement effects. The progress made in the synthesis of silicon nanostructures and nanowires in recent years has attracted considerable attention. Today, large quantities of silicon nanowires can be produced by the laser ablation of metalor SiO2-containing silicon targets, [8] and a few properties, such as electric and thermal conductivity and optical properties, have also been studied. However, the experimental characterization and application of silicon nanowires, for example, the measurement of the elastic properties, the realization of efficient field emission of nanoscale silicon, and the fabrication of nanometer field effect transistors and planar displays, have been hampered so far because of the difficulty in growing oriented silicon nanowires. As a result, the production of highly oriented and very long silicon nanowires is a very important and challenging issue. In this communication, we report the successful synthesis of highly oriented, largescale, and very long silicon nanowires on flat silicon substrates by thermal evaporation of silicon monoxide (SiO). The growth mechanism and optical properties of the oriented silicon nanowires are also discussed. To the best of our knowledge, the synthesis of oriented silicon nanowires has not yet been reported. The equipment used for the present work is similar to that described previously. An alumina tube was mounted inside a tube furnace. The SiO powders (Gooodfellow, 99.95 %) were placed near the middle of the high-temperature zone of the furnace. The polished silicon (100) substrates about 5 mm in width and 50 mm in length were ultrasonically cleaned in acetone, ethanol, and deionized water for 20 min each, dipped in 20 % HF for 20 min, and finally rinsed in deionized water for 20 min before they were placed abreast at one end of the alumina tube. The tube had previously been evacuated to a base pressure of 10 torr by a mechanical pump before the starting materials were heated. The carrier gas of argon mixed with 5 % H2 admitted at the other end of the alumina tube flowed at 50 sccm (standard cubic centimeters per minute) at 400 torr. The temperature of the furnace was increased to 1300 C at 6 C/min and kept at this temperature for 7 h. The temperature of the silicon substrate surface where the oriented silicon nanowires grew was found to be approximately 930 C, which differed from that at the center due to the temperature gradient within the tube. The product was first directly examined by scanning electron microscopy (SEM, Philips XL 30 FEG). Microstructural characterization was carried out in a conventional Philips CM 20 transmission electron microscope (TEM) at 200 kV. The high-resolution transmission electron microscopy (HRTEM) study was performed in a Philips CM200 FEG transmission electron microscope, operated at 200 kV accelerating voltage at room temperature. The chemical compositions of the samples were determined by an energy dispersive X-ray (EDX) spectrometer attached to both the SEM and HRTEM instruments. Raman scattering spectra were measured with a Renishaw micro-Raman spectrometer at room temperature. Excitation was by means of the 514 nm line of an Ar laser, and the Raman signals were measured in a backscattering geometry with a spectral resolution of 1.0 cm. The deposited silicon nanowire product is light yellow in color. SEM images at different magnifications of a typical sample in Figures 1a, 1b, 1c, and 1d clearly show the large area of highly oriented nanowires on the surface of the silicon substrate. The low magnification SEM image (Fig. 1a) shows that the area of highly oriented silicon nanowires is about 2 mm ́ 3 mm and the lengths of individual nanowires are up to 1.5±2 mm. The thickness of the oriented nanowire product was about 10 lm, as estimated from the cross-sectional image (Fig. 1d) of the sample prepared by focused ion beam cutting. The highly oriented array of Si nanowires can also be observed from the cross-sectional image. The EDX results show that the nanowires are composed of silicon and oxygen. No metal was found in the sample. Such results are consistent with our previous theory that silicon nanowire growth is enhanced by silicon oxide instead of a metal particle catalyst. Because of local charging effects, the diameters observed from SEM images appear larger than the actual wire diameters. More information about the morphology of silicon nanowires is given by the following TEM characterization Small pieces of oriented silicon nanowire samples were peeled off from a silicon substrate and mounted on a folding grid for TEM and HRTEM observations. Figure 2 shows the typical morphology of silicon nanowires. As reported previously, these nanowires show a better orientation than those synthesized by laser ablation. Silicon nanowires as observed by TEM are quite clean, with very few particles attached to their surfaces, and are relatively homogeneous. Analysis of a number of nanowires shows that the diameters of these silicon nanowires vary from 18 to 46 nm, and the mean value is about 30 nm. The selected-area electron dif-

Controlled synthesis of oriented single-crystal ZnO nanotube arrays on transparent conductive substrates

Large-scale arrays of highly oriented single-crystal ZnO nanotubes (ZNTs) are successfully fabricated on transparent conductive substrates by a simple method from an aqueous solution at a low temperature (typically 85°C). The tubular morphology of the ZnO nanostructures is formed by a defect-selective chemical etching of the electrodeposited ZnO nanorods. The size of the ZNT arrays is determined by that of ZnO nanorod arrays which can be readily controlled by tuning several electrodeposition parameters. The present method can be employed to prepare ZNT arrays on flexible, conductive substrates, as well as on patterned conductive substrates.

Bulk-quantity GaN nanowires synthesized from hot filament chemical vapor deposition

The bulk-quantity synthesis of single-crystal GaN nanowires has been achieved through a simple method of hot filament chemical vapor deposition without using a nanometer-sized catalyst. The microstructures and optical properties of GaN . nanowires have been studied by electron microscopy and photoluminescence PL measurements at room temperature. The GaN nanowires had diameters of 5-12 nm and lengths of a few micrometers, and were highly pure. They possessed a 4 hexagonal wurtzite structure and had a growth direction perpendicular to the 1101 plane. The PL spectra showed a broad emission peak centered at 420 nm. q 2000 Published by Elsevier Science B.V.

Enhancement of the light emissions from zinc oxide films by controlling the post-treatment ambient

Highly-oriented zinc oxide (ZnO) films were grown on quartz glass substrates by radio frequency magnetron sputtering method. The temperature dependence of the photoluminescence spectra of the ZnO films annealed in argon, argon mixed with 5% hydrogen (H2/Ar) and oxygen ambient, respectively, was investigated from −190 to 600 °C. Results shown that UV light emission was greatly enhanced by annealing the as-grown ZnO film in H2/Ar ambient. Meanwhile, strong visible light emission was observed from the ZnO film annealed in oxygen ambient, and intense emissions in both UV and visible region were obtained from the ZnO films annealed in argon ambient. The UV emission from the ZnO films showed a high thermal stability that can be clearly observed up to 400 °C. The effect of the annealing ambient and the photoluminescence temperature dependence are discussed with the relations to the structural defects.

High-performance surface-enhanced Raman scattering sensors based on Ag nanoparticles-coated Si nanowire arrays for quantitative detection of pesticides

A surface-enhanced Raman scattering (SERS) sensor made of Ag nanoparticles-coated Si nanowire (SiNW) arrays was fabricated for the quantitative detection of Carbaryl (an important nitrogen pesticide). H-terminated SiNWs were capable of reducing silver ions, leading to uniform deposition of silver nanoparticles on SiNW arrays. Such wire arrays exhibited a superior detection sensitivity of 10−17 M Rodamine 6G with high reproducibility. The sensor also enabled high sensitivity, reproducibility, and stability detection of Carbaryl. Significantly, the linear relation between the logarithmic concentrations and Raman peak intensities provided quantitative detection of Carbaryl.

Using Si and Ge Nanostructures as Substrates for Surface-Enhanced Raman Scattering Based on Photoinduced Charge Transfer Mechanism

The possibility of utilizing the Si and Ge nanostructures to promote surface-enhanced Raman scattering (SERS) is discussed. The vibronic coupling of the conduction band and valence band states of Si or Ge with the excited and ground states of the target molecule during the charge transfer (CT) process could enhance the molecular polarizability tensor. Using H-terminated silicon nanowire (H-SiNW) and germanium nanotube (H-GeNT) arrays as substrates, significant Raman enhancement of the standard probes, Rodamine 6G (R6G), dye (Bu(4)N)(2)[Ru(dcbpyH)(2)-(NCS)(2)] (N719), and 4-aminothiophenol (PATP), are demonstrated. The abundant hydrogen atoms terminated on the surface of SiNW and GeNT arrays play a critical role in promoting efficient CT and enable the SERS effect.

Oxide-assisted growth and optical characterization of gallium-arsenide nanowires

This letter reports the synthesis and optical characterization of GaAs nanowires obtained by oxide-assisted laser ablation of a mixture of GaAs and Ga2O3. The GaAs nanowires have lengths up to tens of micrometers and diameters in the range of 10–120 nm, with an average of 60 nm. The nanowires have a thin oxide layer covering a crystalline GaAs core with a [111] growth direction. Raman scattering and photoluminescence (PL) characterizations of GaAs nanowires reveal that the spectral peaks significantly shifted and broadened from those of bulk GaAs material. The changes in these spectra are mainly attributed to impurities, defects, and residual stress in the GaAs nanowires.

Microstructures of gallium nitride nanowires synthesized by oxide-assisted method

Abstract Gallium nitride (GaN) nanowires were synthesized using the recently developed oxide-assisted method by laser ablating a target of GaN mixed with gallium oxide (Ga 2 O 3 ). Transmission electron microscopic characterization showed that GaN nanowires were smooth and straight with a core-sheath structure of 80 nm in average diameter and tens of micrometers in length. Both hexagonal and cubic structured GaN nanowires were produced. The growth mechanism was discussed.

Synthesis and microstructure of gallium phosphide nanowires

Gallium phosphide (GaP) nanowires of 22 nm in diameter and hundreds micrometers in length were synthesized by laser ablation of a powder mixture of GaP and gallium oxide (Ga2O3). The morphology and microstructure of GaP nanowires were investigated by transmission electron microscopy. Twins and stacking faults were observed on {111} planes of the GaP nanowires with special morphologies, and the formation of these defects was discussed. The growth of the GaP nanowires can be described by an oxide-assisted mechanism involving several oxidation-reduction reactions. The successful synthesis of GaP nanowires without any metallic impurities is beneficial for further exploration of their fundamental properties and applications.

Influence of excitation density on photoluminescence of zinc oxide with different morphologies and dimensions

Photoluminescence from zinc oxide (ZnO) nanoparticles, nanorods, microparticles, and single crystals was measured under various conditions of ultraviolet excitation. Near-band-gap and deep-level emissions were observed from all samples. The intensities of both emissions from each ZnO sample exhibited a different nonlinear dependence on the excitation density. These differences could be interpreted by the variation of the light scattering and the specific surface areas of the ZnO morphologies. The intensity ratio of the near-band-gap emission to the deep-level emission from the ZnO samples strongly depended on the density of the excitation light. Our results indicated that the intensity ratio of two emissions depends on the sample type (such as the dimension, specific surface area, etc.), as well as the experimental conditions (such as excitation density, radiation area, etc.). Therefore, this ratio could not be simply employed to unequivocally evaluate the quality of the ZnO.