In‐situ Observations of Nanoscale Effects in Germanium Nanowire Growth with Ternary Eutectic Alloys

Vapour‐liquid‐solid (VLS) techniques are popular routes for the scalable synthesis of semiconductor nanowires. In this article, in‐situ electron microscopy is used to correlate the equilibrium content of ternary (Au_0.75Ag_0.25–Ge and Au_0.65Ag_0.35–Ge) metastable alloys with the kinetics, thermodynamics and diameter of Ge nanowires grown via a VLS mechanism. The shape and geometry of the heterogeneous interfaces between the liquid eutectic and solid Ge nanowires varies as a function of nanowire diameter and eutectic alloy composition. The behaviour of the faceted heterogeneous liquid–solid interface correlates with the growth kinetics of the nanowires, where the main growth facet at the solid nanowire–liquid catalyst drop contact line lengthens for faster nanowire growth kinetics. Pronounced diameter dependent growth kinetics, as inferred from liquid–solid interfacial behaviour, is apparent for the synthesised nanowires. Direct in‐situ microscopy observations facilitates the comparison between the nanowire growth behaviour from ternary (Au–Ag–Ge) and binary (Au–Ge) eutectic systems.     

Formation of Single Tiers of Bridging Silicon Nanowires for Transistor Applications Using Vapor–Liquid–Solid Growth from Short Silicon‐on‐Insulator Sidewalls

Single tiers of silicon nanowires that bridge the gap between the short sidewalls of silicon‐on‐insulator (SOI) source/drain pads are formed. The formation of a single tier of bridging nanowires is enabled by the attachment of a single tier of Au catalyst nanoparticles to short SOI sidewalls and the subsequent growth of epitaxial nanowires via the vapor–liquid–solid (VLS) process. The growth of unobstructed nanowire material occurs due to the attachment of catalyst nanoparticles on silicon surfaces and the removal of catalyst nanoparticles from the SOI‐buried oxide (BOX). Three‐terminal current–voltage measurements of the structure using the substrate as a planar backgate after VLS nanowire growth reveal transistor behaviour characteristics.     

Surface energy of monolayer formation during nanowire growth by vapor-liquid-solid mechanism

An exact expression for the effective surface energy of monolayer formation during the growth of a two-dimensional isotropic nanowire according to the vapor-liquid-solid (VLS) mechanism is obtained with allowance for faceting of the crystal side surface. Conditions necessary for the stability of a drop at the top of the growing nanowire and for the preferred nucleation at the triple phase line are theoretically analyzed in various geometries of the lateral L-S boundary. The obtained results correct the inaccuracies of the previous solution of an analogous problem and make it possible to calculate the nucleation barriers that determine the probabilities of formation of various crystalline phases in nanowires of III–V semiconductor compounds.     

Internal structure of multiphase zinc-blende wurtzite gallium nitride nanowires

In this paper, the internal structure of novel multiphase gallium nitride nanowires in which multiple zinc-blende and wurtzite crystalline domains grow simultaneously along the entire length of the nanowire is investigated. Orientation relationships within the multiphase nanowires are identified using high-resolution transmission electron microscopy of nanowire cross-sections fabricated with a focused ion beam system. A coherent interface between the zinc-blende and wurtzite phases is identified. A mechanism for catalyst-free vapor-solid multiphase nanowire nucleation and growth is proposed.     

In-situ TEM observation of repeating events of nucleation in epitaxial growth of nano CoSi2 in nanowires of Si

The formation of CoSi and CoSi2 in Si nanowires at 700 and 800 degrees C, respectively, by point contact reactions between nanodots of Co and nanowires of Si have been investigated in situ in a ultrahigh vacuum high-resolution transmission electron microscope. The CoSi2 has undergone an axial epitaxial growth in the Si nanowire and a stepwise growth mode was found. We observed that the stepwise growth occurs repeatedly in the form of an atomic step sweeping across the CoSi2/Si interface. It appears that the growth of a new step or a new silicide layer requires an independent event of nucleation. We are able to resolve the nucleation stage and the growth stage of each layer of the epitaxial growth in video images. In the nucleation stage, the incubation period is measured, which is much longer than the period needed to grow the layer across the silicide/Si interface. So the epitaxial growth consists of a repeating nucleation and a rapid stepwise growth across the epitaxial interface. This is a general behavior of epitaxial growth in nanowires. The axial heterostructure of CoSi2/Si/CoSi2 with sharp epitaxial interfaces has been obtained. A discussion of the kinetics of supply limited and source-limited reaction in nanowire case by point contact reaction is given. The heterostructures are promising as high performance transistors based on intrinsic Si nanowires.     

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。     

Ultrafast growth of single-crystalline Si nanowires

Silicon nanowires (SiNWs) have been catalytically synthesized by heat treatment of Si nanopowder at 980 °C. The SiNWs comprise crystalline Si nanoparticles interconnected with metal catalyst. The formation mechanism of nanowires generally depends on the presence of Fe catalysts in the synthesis process of solid–liquid–solid (SLS). Although gas phase of vapor–liquid–solid (VLS) method can be used to produce various of different nanowire materials, growth model based on the SLS mechanism by heat treatment is more ascendant for providing ultrafast growth of single-crystalline Si nanowires and controlling the diameter of them easily. The growth of single-crystalline SiNWs and morphology were discussed.     

New mode of vapor-liquid-solid nanowire growth

We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires.     

Lateral, Ge, nanowire growth on SiO2

Vapor-liquid-solid (VLS) nanowires (NWs) typically grow in [111] directions. Previously, the authors have demonstrated guided Si NW growth, engineering the VLS NWs to grow in a [110] direction against a SiO(2) surface. In this work, the authors demonstrate guided high-quality Ge nanowire growth against a SiO(2) surface in the substrate plane to bridge between two Si mesas. The authors explore the interfaces between a Ge NW and the two Si device-layer mesas and report high-quality, epitaxial interfaces between the Ge NW and both Si mesas.     

Doping GaP Core–Shell Nanowire pn‐Junctions: A Study by Off‐Axis Electron Holography

The doping process in GaP core–shell nanowire pn‐junctions using different precursors is evaluated by mapping the nanowires' electrostatic potential distribution by means of off‐axis electron holography. Three precursors, triethyltin (TESn), ditertiarybutylselenide, and silane are investigated for n‐type doping of nanowire shells; among them, TESn is shown to be the most efficient precursor. Off‐axis electron holography reveals higher electrostatic potentials in the regions of nanowire cores grown by the vapor–liquid–solid (VLS) mechanism (axial growth) than the regions grown parasitically by the vapor–solid (VS) mechanism (radial growth), attributed to different incorporation efficiency between VLS and VS of unintentional p‐type carbon doping originating from the trimethylgallium precursor. This study shows that off‐axis electron holography of doped nanowires is unique in terms of the ability to map the electrostatic potential and thereby the active dopant distribution with high spatial resolution.     

Failure of the vapor-liquid-solid mechanism in Au-assisted MOVPE growth of InAs nanowires

We report the temperature dependence of the Au-assisted growth of InAs nanowires in MOVPE. Extensive studies of the growth of such nanowires have attributed growth to the so-called vapor-liquid-solid (VLS) mechanism, with a liquid Au-In alloy particle. We assert here that growth is instead assisted by a solid particle and does not occur at all when the particle is a liquid. Thus the temperature range of InAs nanowire growth is limited by the melting of the Au-In alloy. Comparison with growth of InAs nanowires in the same system assisted by a layer of SiO(x) is used to support this conclusion.     

Growth of germanium nanowires on silicon(111) substrates by molecular beam epitaxy

Heteroepitaxial growth of Ge nanowires was carried out on Si(111) substrates by MBE. Au seeds were used as precursor for the VLS growth of the nanowires. Even if the Au droplets do not act as catalyst for the dissociation of gas, they are local preferential areas where the energetic barrier of Ge nucleation is lowered compare to the remaining non activated surface. Two sets of Au seeds were used as precursors for the VLS process. The first set have an average diameter of 125 nm and the second of 25 nm. In-situ RHEED monitoring showed a Au wetting layer between these seeds before the nanowires growth as well as at the end of the Ge nanowires growth. It means that the wetting layer acted as a surfactant from the Si(111) surface to the Ge grown layer between the nanowires. Analysis of SEM images brought the fact that the diffusion of gold from the droplets on the surface and the sidewalls of the nanowires via the Ostwald ripening is a key parameter of the growth of the nanowires.     

Controlling the abruptness of axial heterojunctions in III-V nanowires: beyond the reservoir effect

Heterostructure nanowires have many potential applications due to the avoidance of interface defects by lateral strain relaxation. However, most heterostructure semiconductor nanowires suffer from persistent interface compositional grading, normally attributed to the dissolution of growth species in the common alloy seed particles. Although progress has been made for some material systems, most binary material combinations remain problematic due to the interaction of growth species in the alloy. In this work we investigate the formation of interfaces in InAs-GaAs heterostructures experimentally and theoretically and demonstrate a technique to attain substantially sharper interfaces. We show that by pulsing the Ga source during heterojunction formation, In is pushed out before GaAs growth initiates, greatly reducing In carry-over. This procedure will be directly applicable to any nanowire system with finite nonideal solubility of growth species in the alloy seed particle and greatly improve the applicability of these structures in future devices.     

Three-dimensional GaN/AlN nanowire heterostructures by separating nucleation and growth processes

Bottom-up nanostructure assembly has been a central theme of materials synthesis over the past few decades. Semiconductor quantum dots and nanowires provide additional degrees of freedom for charge confinement, strain engineering, and surface sensitivity-properties that are useful to a wide range of solid state optical and electronic technologies. A central challenge is to understand and manipulate nanostructure assembly to reproducibly generate emergent structures with the desired properties. However, progress is hampered due to the interdependence of nucleation and growth phenomena. Here we show that by dynamically adjusting the growth kinetics, it is possible to separate the nucleation and growth processes in spontaneously formed GaN nanowires using a two-step molecular beam epitaxy technique. First, a growth phase diagram for these nanowires is systematically developed, which allows for control of nanowire density over three orders of magnitude. Next, we show that by first nucleating nanowires at a low temperature and then growing them at a higher temperature, height and density can be independently selected while maintaining the target density over long growth times. GaN nanowires prepared using this two-step procedure are overgrown with three-dimensionally layered and topologically complex heterostructures of (GaN/AlN). By adjusting the growth temperature in the second growth step either vertical or coaxial nanowire superlattices can be formed. These results indicate that a two-step method allows access to a variety of kinetics at which nanowire nucleation and adatom mobility are adjustable.     

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.     

Periodically twinned nanowires and polytypic nanobelts of ZnS: The role of mass diffusion in vapor-liquid-solid growth

There are two mass diffusion processes regarding the vapor-liquid-solid (VLS) growth of nanostructures: one is inside the catalyst droplet toward the liquid-solid interface; the other is along the side surface planes of the growing nanostructures. In this letter, microscale, modulated mass diffusion scenarios are exhibited through the synthesis of two types of ZnS nanostructures in an Au-catalyzed VLS process: periodically twinned nanowires originated from periodical fluctuation between diffusion rate inside the catalytic droplet and the growth rate on the liquid-solid interface; the formation of asymmetrically polytypic nanobelts is related to one certain side surface bounded by high surface-energy plane, which serves as a preferential diffusion direction of reactant adatoms. The results may have important impact on the understanding of the physical and chemical process of the VLS mechanism. These longitudinally and latitudinally tunable crystalline structures enrich the family of one-dimensional nano-building blocks, and may find potential applications in nanotechnology.     

Epitaxial growth of silicon nanowires using an aluminium catalyst

Silicon nanowires have been identified as important components for future electronic and sensor nanodevices. So far gold has dominated as the catalyst for growing Si nanowires via the vapour-liquid-solid (VLS) mechanism. Unfortunately, gold traps electrons and holes in Si and poses a serious contamination problem for Si complementary metal oxide semiconductor (CMOS) processing. Although there are some reports on the use of non-gold catalysts for Si nanowire growth, either the growth requires high temperatures and/or the catalysts are not compatible with CMOS requirements. From a technological standpoint, a much more attractive catalyst material would be aluminium, as it is a standard metal in Si process lines. Here we report for the first time the epitaxial growth of Al-catalysed Si nanowires and suggest that growth proceeds via a vapour-solid-solid (VSS) rather than a VLS mechanism. It is also found that the tapering of the nanowires can be strongly reduced by lowering the growth temperature.     

The influences of technological conditions and Au cluster islands on morphology of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires grown by VLS method on GaAs substrate

The synthesis of semiconductor nanowires is more and more interested to the applications for building blocks of the innovative nano-sized devices and circuits, but the research and fabrication of these nanowires are also holding a number of difficulties and challenges. Among many different kinds of semiconductor nanowires, Ga₂O₃ is increasingly grown for many promising applications in nano-device production, namely nanowire LED and Laser. So far there are many synthesizing methods of semiconductor nanowires, among them the vapor–liquid–solid (VLS) method is simple, cheap and popular. However, when we use the VLS method for nanowire growth, various technological problems exist. This paper aims at investigating some influences of the growth technological conditions and Au metal catalyst on the morphology of Ga₂O₃ nanowire grown by VLS on GaAs substrate. The main considering factors include the different growing temperatures and times, the effects of Au diffusion, Au droplets formation, Au cluster islands formation, and gas volume of the growing tube/ampoule at the 10⁻¹ torr low air pressure. The obtained experimental results regarding the structural properties of nanowires under these effects investigated by scanning electron microscopy, field emission scanning electron microscopy, high angle annular dark field and bright field, scanning transmission electron microscopy, energy-dispersive X-ray techniques, and focus ion beam are presented and discussed.     

Controlling heterojunction abruptness in VLS-grown semiconductor nanowires via in situ catalyst alloying

For advanced device applications, increasing the compositional abruptness of axial heterostructured and modulation doped nanowires is critical for optimizing performance. For nanowires grown from metal catalysts, the transition region width is dictated by the solute solubility within the catalyst. For example, as a result of the relatively high solubility of Si and Ge in liquid Au for vapor-liquid-solid (VLS) grown nanowires, the transition region width between an axial Si-Ge heterojunction is typically on the order of the nanowire diameter. When the solute solubility in the catalyst is lowered, the heterojunction width can be made sharper. Here we show for the first time the systematic increase in interface sharpness between axial Ge-Si heterojunction nanowires grown by the VLS growth method using a Au-Ga alloy catalyst. Through in situ tailoring of the catalyst composition using trimethylgallium, the Ge-Si heterojunction width is systematically controlled by tuning the semiconductor solubility within a metal Au-Ga alloy catalyst. The present approach of alloying to control solute solubilities in the liquid catalyst may be extended to increasing the sharpness of axial dopant profiles, for example, in Si-Ge pn-heterojunction nanowires which is important for such applications as nanowire tunnel field effect transistors or in Si pn-junction nanowires.