Epitaxial insertion of gold silicide nanodisks during the growth of silicon nanowires

Nanodisk-shaped, single-crystal gold silicide heterojunctions were inserted into silicon nanowires during vapor-liquid-solid growth using Au as a catalyst within a specific range of chlorine-to-hydrogen atomic ratio. The mechanism of nanodisk formation has been investigated by changing the source gas ratio of SiCl4 to H2. We report that an over-supply of silicon into the Au-Si liquid alloy leads to highly supersaturated solution and enhances the precipitation of Au in the silicon nanowires due to the formation of unstable phases within the liquid alloy. It is shown that the gold precipitates embedded in the silicon nanowires consisted of a metastable gold silicide. Interestingly, faceting of gold silicide was observed at the Au/Si interfaces, and silicon nanowires were epitaxially grown on the top of the nanodisk by vapor-liquid-solid growth. High resolution transmission electron microscopy confirmed that gold silicide nanodisks are epitaxially connected to the silicon nanowires in the direction of growth direction. These gold silicide nanodisks would be useful as nanosized electrical junctions for future applications in nanowire interconnections.     

Size effect on Ge nanowires growth kinetics by the vapor-liquid-solid mechanism

Germanium nanowires were grown on germanium (111) substrate by ultra high vacuum chemical vapor deposition, via the vapor-liquid-solid growth mechanism, using digermane as gaseous precursor and gold as catalyst. The results show that the nanowire length depends on the diameter catalyst, the smaller the nanowire radius, the slower the nanowires grow.In order to fit the experimental data, we have used a simple model based on the Gibbs-Thomson effect and adapted to our growth conditions. This model was found to perfectly account for the catalyst size dependence of the experimental growth kinetics of germanium nanowires from digermane. From that, a critical radius of 6 nm was derived.     

Taper-free and kinked germanium nanowires grown on silicon via purging and the two-temperature process

We investigate the growth procedures for achieving taper-free and kinked germanium nanowires epitaxially grown on silicon substrates by chemical vapor deposition. Singly and multiply kinked germanium nanowires consisting of <111> segments were formed by employing a reactant gas purging process. Unlike non-epitaxial kinked nanowires, a two-temperature process is necessary to maintain the taper-free nature of segments in our kinked germanium nanowires on silicon. As an application, nanobridges formed between (111) side walls of V-grooved (100) silicon substrates have been demonstrated.     

Stranski-Krastanow growth of germanium on silicon nanowires

There have been extensive studies of germanium (Ge) grown on planar silicon (Si) substrates by the Stranski-Krastanow (S-K) mechanism. In this study, we present S-K growth of Ge on Si nanowires. The Si nanowires were grown at 500 degrees C by a vapor-liquid-solid (VLS) method, using silane (SiH4) as the gaseous precursor. By switching the gas source from SiH4 to germane (GeH4) during the growth and maintaining the growth conditions, epitaxial Ge islands deposited on the outer surface of the initially formed Si nanowires. Transmission electron microscopy (TEM), scanning TEM, and energy-dispersive X-ray spectroscopy techniques were utilized to identify the thin wetting layer and the three-dimensional Ge islands formed around the Si core nanowires. Cross-sectional TEM verified the surface faceting of the Si core nanowires as well as the Ge islands.     

Toward local growth of individual nanowires on three-dimensional microstructures by using a minimally invasive catalyst templating method

We present a novel minimally invasive postprocessing method for catalyst templating based on focused charged particle beam structuring, which enables a localized vapor-liquid-solid (VLS) growth of individual nanowires on prefabricated three-dimensional micro- and nanostructures. Gas-assisted focused electron beam induced deposition (FEBID) was used to deposit a SiO(x) surface layer of about 10 × 10 μm(2) on top of a silicon atomic force microscopy cantilever. Gallium focused ion beam (FIB) milling was used to make a hole through the SiO(x) layer into the underlying silicon. The hole was locally filled with a gold catalyst via FEBID using either Me(2)Au(tfac) or Me(2)Au(acac) as precursor. Subsequent chemical vapor deposition (CVD)-induced VLS growth using a mixture of SiH(4) and Ar resulted in individual high quality crystalline nanowires. The process, its yield, and the resulting angular distribution/crystal orientation of the silicon nanowires are discussed. The presented combined FIB/FEBID/CVD-VLS process is currently the only proven method that enables the growth of individual monocrystalline Si nanowires on prestructured substrates and devices.     

Temperature-dependent growth of germanium oxide and silicon oxide based nanostructures, aligned silicon oxide nanowire assemblies, and silicon oxide microtubes

We demonstrate the temperature-dependent growth of germanium oxide and silicon oxide based composite nanostructures (multiple nanojunctions of Ge nanowires and SiO(x) nanowires, Ge-filled SiO(2) nanotubes, Ge/SiO(2) coaxial nanocables, and a variety of interesting micrometer-sized structures), aligned SiO(x) nanowire assemblies, and SiO(x) microtubes. The structures were characterized by SEM, TEM, energy-dispersive X-ray spectroscopy, and electron diffraction. The combination of laser ablation of a germanium target and thermal evaoporation of silicon monoxide powders resulted in the formation of Ge and SiO(x) species in a carrier gas; the nano/micro-sized structures grow by either a Ge-catalyzed vapor-liquid-solid or a Ge-nanowire-templated vapor-solid process.     

The structure and optical properties of silicon nanowires prepared by inductively coupled plasma chemical vapor deposition

Silicon nanowires were prepared by vapor-liquid-solid (VLS) mechanism at a growth temperature as low as 380 °C in an inductively coupled plasma chemical vapor deposition system. The nanowires consist of crystalline core surrounded by a thick amorphous silicon shell. An increase in plasma power produces dense and long nanowires with thick amorphous shell, accompanied with a thick uncatalyzed amorphous silicon film on the silicon substrate. Small catalyst nanoparticles are easier activated by plasma to grow the dense and thin nanowires in comparison with the large-size nanoparticles. Moreover, an enhanced optical absorption is achieved due to the strong light trapping and anti-reflection effects in the thin and tapered silicon nanowires with high density.     

Synthesis of silicon carbide nanowires by solid phase source chemical vapor deposition

In this paper, we report a simple approach to synthesize silicon carbide (SiC) nanowires by solid phase source chemical vapor deposition (CVD) at relatively low temperatures. 3C-SiC nanowires covered by an amorphous shell were obtained on a thin film which was first deposited on silicon substrates, and the nanowires are 20–80 nm in diameter and several μm in length, with a growth direction of [200]. The growth of the nanowires agrees well on vapor-liquid-solid (VLS) process and the film deposited on the substrates plays an important role in the formation of nanowires.     

Composition and local strain mapping in Au-catalyzed axial Si/Ge nanowires

For most applications, heterostructures in nanowires (NWs) with lattice mismatched materials are required and promise certain advantages thanks to lateral strain relaxation. The formation of Si/Ge axial heterojunctions is a challenging task to obtain straight, defect free and extended NWs. And the control of the interface will determine the future device properties. This paper reports the growth and analysis of NWs consisting of an axial Si/Ge heterostructure grown by a vapor-liquid-solid process. The composition gradient and the strain distribution at the heterointerface were measured by advanced quantitative electron microscopy methods with a resolution at the nanometer scale. The transition from pure Ge to pure Si shows an exponential slope with a transition width of 21?nm for a NW diameter of 31?nm. Although diffuse, the heterointerface makes possible strain engineering along the axis of the NW. The interface is dislocation-free and a tensile out-of-plane strain is noticeable in the Ge section of the NW, indicating a lattice accommodation. Experimental results were compared to finite element calculations.     

Controlled growth of Si nanowire arrays for device integration

Silicon nanowires were synthesized, in a controlled manner, for their practical integration into devices. Gold colloids were used for nanowire synthesis by the vapor-liquid-solid growth mechanism. Using SiCl4 as the precursor gas in a chemical vapor deposition system, nanowire arrays were grown vertically aligned with respect to the substrate. By manipulating the colloid deposition on the substrate, highly controlled growth of aligned silicon nanowires was achieved. Nanowire arrays were synthesized with narrow size distributions dictated by the seeding colloids and with average diameters down to 39 nm. The density of wire growth was successfully varied from approximately 0.1-1.8 wires/microm2. Patterned deposition of the colloids led to confinement of the vertical nanowire growth to selected regions. In addition, Si nanowires were grown directly into microchannels to demonstrate the flexibility of the deposition technique. By controlling various aspects of nanowire growth, these methods will enable their efficient and economical incorporation into devices.     

硅纳米线的制备与生长机理

硅纳米线是一种新型的一维半导体光电材料.本文较系统地介绍了硅纳米线在制备技术、生长机理方面的研究现状与最新进展,主要就激光烧蚀法、化学气相沉积法、热气相沉积法及溶液法等制备方法和基于气-液-固机理的生长机理、氧化物辅助生长机理及固-液-固生长机理等作了较为详尽的论述.     

Silicon nanowire synthesis by a vapor-liquid-solid approach

Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.     

钨晶须/纳米线的制备工艺原理及最新研究进展

综述了钨晶须/纳米线几种典型的制备方法及其最新研究进展,如气相沉积法、金属催化诱导法、电化学蚀刻法、模板法等,介绍了气-固、气-液-固和气-固-固生长机制及模型,分析了钨晶须/纳米线在研究和应用中存在的主要问题,指出钨晶须/纳米线生长过程中的影响因素、生长模型建立及钨晶须/纳米线的形貌、组成和产率综合调控是未来重要的研究方向.     

一种链珠状SiO2纳米线的制备及分析

实验通过硅粉和氯化钙盐高温处理, 以熔融CaCl₂高温下产生的蒸气作为特殊的蒸发载体, 在1300℃条件下通过热蒸发法在石墨基板表面获得了具有草坪状排列的特殊形状的纳米线。系列测试分析表明, 该纳米线的直径为50~400 nm, 长度约为几个微米, 且为面心立方结构。另外, 系统分析显示传统的纳米线生长模型如气-液-固(VLS)生长机制不能很好地解释该二氧化硅纳米线在石墨纸上的生长过程, 本文提出的一种增强的气-液-固生长机制, 可以很好地解释上述纳米线的生长过程。     

Control of the crystal structure of InAs nanowires by tuning contributions of adatom diffusion

The dependence of crystal structure on contributions of adatom diffusion (ADD) and precursor direct impingement (DIM) was investigated for vapor-liquid-solid growth of InAs nanowires (NWs). The ADD contributions from the sidewalls and substrate surface can be changed by using GaAs NWs of different length as the basis for growing InAs NWs. We found that pure zinc-blende structure is favored when DIM contributions dominate. Moreover, without changing the NW diameter or growth parameters (such as temperature or V/III ratio), a transition from zinc-blende to wurtzite structure can be realized by increasing the ADD contributions. A nucleation model is proposed in which ADD and DIM contributions play different roles in determining the location and phase of the nucleus.     

Synthesis of aligned arrays of “Microropes” of silica nanowires by gas-jet electron beam plasma chemical vapor deposition method

For the first time, aligned arrays of bundles (“microropes”) of silica nanowires were synthesized from a monosilane-hydrogen mixture by gas-jet electron beam plasma chemical vapor deposition method. The synthesis was performed on single-crystal silicon substrates coated by micron-sized particles of stannic catalyst. A bundle (“microrope”) of silica nanowires each of which is about 15 nm in diameter grows from a catalyst particle. It seems that the synthesis proceeds by the vapor-liquid-solid mechanism, and several nanowires grow synchronously from the surface of one catalyst particle. The “microrope” growth rate was about 25 nm/s at a synthesis temperature of 400°C. A possible growth model was proposed to explain these results.     

Phase selection enabled formation of abrupt axial heterojunctions in branched oxide nanowires

Rational synthesis of nanowires via the vapor-liquid-solid (VLS) mechanism with compositional and structural controls is vitally important for fabricating functional nanodevices from bottom up. Here, we show that branched indium tin oxide nanowires can be in situ seeded in vapor transport growth using tailored Au-Cu alloys as catalyst. Furthermore, we demonstrate that VLS synthesis gives unprecedented freedom to navigate the ternary In-Sn-O phase diagram, and a rare and bulk-unstable cubic phase can be selectively stabilized in nanowires. The stabilized cubic fluorite phase possesses an unusual almost equimolar concentration of In and Sn, forming a defect-free epitaxial interface with the conventional bixbyite phase of tin-doped indium oxide that is the most employed transparent conducting oxide. This rational methodology of selecting phases and making abrupt axial heterojunctions in nanowires presents advantages over the conventional synthesis routes, promising novel composition-modulated nanomaterials.     

Control of lateral dimension in metal-catalyzed germanium nanowire growth: usage of carbon sheath

We report on the catalytic growth of thin carbon sheathed single crystal germanium nanowires (GeNWs), which can solve the obstacles that have disturbed a wide range of applications of GeNWs. Single crystal Ge NW core and amorphous carbon sheath are simultaneously grown via vapor-liquid-solid (VLS) process. The carbon sheath completely blocks unintentional vapor deposition on NW surface, thus ensuring highly uniform diameter, dopant distribution, and electrical conductivity along the entire NW length. Furthermore, the sheath not only inhibits metal diffusion but also improves the chemical stability of GeNWs at even high temperatures.     

Ultrafast electron and hole dynamics in germanium nanowires

We present the first ultrafast time-resolved optical measurements, to the best of our knowledge, on ensembles of germanium nanowires. Vertically aligned germanium nanowires with mean diameters of 18 and 30 nm are grown on (111) silicon substrates through chemical vapor deposition. We optically inject electron-hole pairs into the nanowires and exploit the indirect band structure of germanium to separately probe electron and hole dynamics with femtosecond time resolution. We find that the lifetime of both electrons and holes decreases with decreasing nanowire diameter, demonstrating that surface effects dominate carrier relaxation in semiconductor nanowires.     

Smooth germanium nanowires prepared by a hydrothermal deposition process

Smooth germanium nanowires were prepared using Ge and GeO₂ as the starting materials and Cu sheet as the substrate by a simple hydrothermal deposition process. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterizations show that the germanium nanowires are smooth and straight with uniform diameter of about 150 nm in average and tens of micrometers in length. X-ray diffraction (XRD) and Raman spectrum of the germanium nanowires display that the germanium nanowires are mainly composed of cubic diamond phase. PL spectrum shows a strong blue light emission at 441 nm. The growth mechanism is also discussed.