Growth of straight InAs-on-GaAs nanowire heterostructures

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.     

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.     

In Situ Grown Epitaxial Heterojunction Exhibits High‐Performance Electrocatalytic Water Splitting

Electrocatalytic performance can be enhanced by engineering a purposely designed nanoheterojunction and fine‐tuning the interface electronic structure. Herein a new approach of developing atomic epitaxial in‐growth in Co‐Ni₃N nanowires array is devised, where a nanoconfinement effect is reinforced at the interface. The Co‐Ni₃N heterostructure array is formed by thermal annealing NiCo₂O₄ precursor nanowires under an optimized condition, during which the nanowire morphology is retained. The epitaxial in‐growth structure of Co‐Ni₃N at nanometer scale facilitates the electron transfer between the two different domains at the epitaxial interface, leading to a significant enhancement in catalytic activities for both hydrogen and oxygen evolution reactions (10 and 16 times higher in the respective turn‐over frequency compared to Ni₃N‐alone nanorods). The interface transfer effect is verified by electronic binding energy shift and density functional theory (DFT) calculations. This nanoconfinement effect occurring during in situ atomic epitaxial in‐growth of the two compatible materials shows an effective pathway toward high‐performance electrocatalysis and energy storages.     

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.     

生长温度对InAs/GaAs横向异质结构纳米线形貌及晶体结构的影响

低维半导体材料因其超常的物理性能而受到了广泛关注和研究。本文采用金属有机物化学气相沉积（MOCVD）技术,利用金作催化剂制备了InAs/GaAs横向异质结构纳米线,并讨论了不同生长温度情况下InAs横向异质材料对纳米线形貌及晶体结构的影响。提高InAs材料的生长温度,可以有效地抑制纳米线的纵向生长,使其实现横向异质结构的生长。在异质结构纳米线横向生长时发生了侧面晶面旋转的现象,这是纳米线表面重构后侧面趋向能量更低的晶面的结果。本文的研究工作为推动微纳技术的发展提供了相应的理论基础和科学依据。      

Vertically Aligned GaAs Nanowires on Graphite and Few-Layer Graphene: Generic Model and Epitaxial Growth

By utilizing the reduced contact area of nanowires, we show that epitaxial growth of a broad range of semiconductors on graphene can in principle be achieved. A generic atomic model is presented which describes the epitaxial growth configurations applicable to all conventional semiconductor materials. The model is experimentally verified by demonstrating the growth of vertically aligned GaAs nanowires on graphite and few-layer graphene by the self-catalyzed vapor-liquid-solid technique using molecular beam epitaxy. A two-temperature growth strategy was used to increase the nanowire density. Due to the self-catalyzed growth technique used, the nanowires were found to have a regular hexagonal cross-sectional shape, and are uniform in length and diameter. Electron microscopy studies reveal an epitaxial relationship of the grown nanowires with the underlying graphitic substrates. Two relative orientations of the nanowire side-facets were observed, which is well explained by the proposed atomic model. A prototype of a single GaAs nanowire photodetector demonstrates a high-quality material. With GaAs being a model system, as well as a very useful material for various optoelectronic applications, we anticipate this particular GaAs nanowire/graphene hybrid to be promising for flexible and low-cost solar cells.     

The influence of surface oxide on the growth of metal/semiconductor nanowires

We report the critical effects of oxide on the growth of nanostructures through silicide formation. Under an in situ ultrahigh vacuum transmission electron microscope, it is observed from the conversion of Si nanowires into the metallic PtSi grains epitaxially through controlled reactions between lithographically defined Pt pads and Si nanowires. With oxide, instead of contact area, single crystal PtSi grains start forming either near the center between two adjacent pads or from the ends of Si nanowires, resulting in the heterostructure formation of Si/PtSi/Si. Without oxide, transformation from Si into PtSi begins at the contact area between them, resulting in the heterostructure formation of PtSi/Si/PtSi. The nanowire heterostructures have an atomically sharp interface with epitaxial relationships of Si(20-2)//PtSi(10-1) and Si[111]//PtSi[111]. Additionally, it has been observed that the existence of oxide significantly affects not only the growth position but also the growth behavior and the growth rate by two orders of magnitude. Molecular dynamics simulations have been performed to support our experimental results and the proposed growth mechanisms. In addition to fundamental science, the significance of the study matters for future processing techniques in nanotechnology and related applications as well.     

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.     

Epitaxial growth of InP nanowires on germanium

The growth of III-V semiconductors on silicon would allow the integration of their superior (opto-)electronic properties with silicon technology. But fundamental issues such as lattice and thermal expansion mismatch and the formation of antiphase domains have prevented the epitaxial integration of III-V with group IV semiconductors. Here we demonstrate the principle of epitaxial growth of III-V nanowires on a group IV substrate. We have grown InP nanowires on germanium substrates by a vapour-liquid-solid method. Although the crystal lattice mismatch is large (3.7%), the as-grown wires are monocrystalline and virtually free of dislocations. X-ray diffraction unambiguously demonstrates the heteroepitaxial growth of the nanowires. In addition, we show that a low-resistance electrical contact can be obtained between the wires and the substrate.     

Epitaxial integration of nanowires in microsystems by local micrometer-scale vapor-phase epitaxy

Free-standing epitaxially grown nanowires provide a controlled growth system and an optimal interface to the underlying substrate for advanced optical, electrical, and mechanical nanowire device connections. Nanowires can be grown by vapor-phase epitaxy (VPE) methods such as chemical vapor deposition (CVD) or metal organic VPE (MOVPE). However, VPE of semiconducting nanowires is not compatible with several microfabrication processes due to the high synthesis temperatures and issues such as cross-contamination interfering with the intended microsystem or the VPE process. By selectively heating a small microfabricated heater, growth of nanowires can be achieved locally without heating the entire microsystem, thereby reducing the compatibility problems. The first demonstration of epitaxial growth of silicon nanowires by this method is presented and shows that the microsystem can be used for rapid optimization of VPE conditions. The important issue of the cross-contamination of other parts of the microsystem caused by the local growth of nanowires is also investigated by growth of GaN near previously grown silicon nanowires. The design of the cantilever heaters makes it possible to study the grown nanowires with a transmission electron microscope without sample preparation.     

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.     

ZnO nanostructures grown on epitaxial GaN

Presented is the growth of zinc oxide nanorod/nanowire arrays on gallium nitride epitaxial layers. A hierarchical zinc oxide morphology comprising of different scale zinc oxide nanostructures was observed. The first tier of the surface comprised of typical zinc oxide nanorods, with most bridging to adjacent nanorods. While the second tier comprised of smaller zinc oxide nanowires approximately 30 nm in width often growing atop the aforementioned bridges. Samples were analysed via scanning electron microscopy, as well as, cross-sectional and high resolution transmission electron microscopy to elucidate the detailed growth and structural elements of the heterostructure.     

Manipulation of Crawling Growth for the Formation of Sub-millimeter Long ZnO Nanowalls

Vapor-phase growth of ZnO nanowires based on gold catalyst is usually accompanied with lateral crawling growth on the substrate surface. We present results from our systematic experiments where the growth temperature and catalyst size are controlled. The data corroborate that it is possible to obtain clean vertical nanowire arrays while avoiding the crawling growth. 0% the other hand, crawling growth can be manipulated to obtain root-interconnected nanowire arrays, which could be useful for certain applications. Our results also imply that the previously suggested growth mechanism for the wire-on-wall hybridstructure might be incorrect. Finally, we show the formation of sub-millimeter long, straight ZnO nanowalls by combining a gold-catalyzed epitaxial growth of vertical nanowires and their mergence due to a confined crawling growth. These unconventional nanostructures might have unique electric or optical transport properties.     

Metal Oxide Nanostructures from Simple Metal-oxygen Reaction in Air

Metal oxide nanostructures （CuO, Co3O4, ZnO and α-Fe2O3） have been successfully fabricated by a simple and efficient method： heating the appropriate metals in air at low temperatures ranging from 200 to 400℃. The chemical composition, morphology and crystallinity of the nanostructures have been characterized by micro-Raman spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Two mechanisms： vapor-solid and surface diffusion play dominant roles in the growth of metal oxide nanostructures starting with low melting point metals （Zn and Cu） and high melting point metals （Fe and Co）, respectively. With sharp ends and large aspect ratio, the metal oxide nanostructures exhibit impressive field-induced electron emission properties, indicating their potentials as future electron source and displays. The water wettability and anti-wettability properties of iron oxide nanoflakes were also discussed in this work.     

Control of GaP and GaAs nanowire morphology through particle and substrate chemical modification

We demonstrate two very different morphologies for GaP and GaAs nanowires grown by Au-assisted MOVPE on Si(111) substrates: rodlike wires and tapered wires with sharp tips. We show that the morphology is related to the stability of the particles at the wire tips during growth, and we propose that the mechanism of this effect is diffusion of Au away from the tip. Diffusion occurs, leading to tapered wires, only if there is a clean Si surface to act as a reservoir for the Au. Furthermore, the presence of indium in the particles, even at background levels from previous growth runs, inhibits the migration of Au. These results demonstrate a dramatic example of the sensitivity of wire morphology to substrate and particle chemistry, which could provide an important tool to tune nanowire morphology through particle alloying or surface treatment.     

Electrodeposition and characterization of CdSe semiconducting nanowires

In this paper, we present our work on the electrodeposited CdSe semiconducting nanowires. Using a low cost and low temperature approach by electrochemistry, CdSe nanowires were successfully grown using polycarbonate template. Depending on the host pore dimension of the substrate, wire diameter can be varied from 400 nm down to 30 nm and wire length from a few microns to tens microns. The as-deposited nanowires exhibit predominantly metastable zinc blende (ZB) structure but after the heat treatment they become wurtzite (W) structure. A combination of different characterization techniques, such as X-ray diffraction, SEM, TEM-HRTEM and EDXS, was used to investigate the growth morphology, crystalline structure and defects in the nanowires. The luminescent properties of CdSe nanowires have also been studied by means of photoluminescence.     

Single crystalline PtSi nanowires, PtSi/Si/PtSi nanowire heterostructures, and nanodevices

We report the formation of PtSi nanowires, PtSi/Si/PtSi nanowire heterostructures, and nanodevices from such heterostructures. Scanning electron microscopy studies show that silicon nanowires can be converted into PtSi nanowires through controlled reactions between lithographically defined platinum pads and silicon nanowires. High-resolution transmission electron microscopy studies show that PtSi/Si/PtSi heterostructure has an atomically sharp interface with epitaxial relationships of Si[110]//PtSi[010] and Si(111)//PtSi(101). Electrical measurements show that the pure PtSi nanowires have low resistivities approximately 28.6 microOmega.cm and high breakdown current densities>1x10(8) A/cm2. Furthermore, using single crystal PtSi/Si/PtSi nanowire heterostructures with atomically sharp interfaces, we have fabricated high-performance nanoscale field-effect transistors from intrinsic silicon nanowires, in which the source and drain contacts are defined by the metallic PtSi nanowire regions, and the gate length is defined by the Si nanowire region. Electrical measurements show nearly perfect p-channel enhancement mode transistor behavior with a normalized transconductance of 0.3 mS/microm, field-effect hole mobility of 168 cm2/V.s, and on/off ratio>10(7), demonstrating the best performing device from intrinsic silicon nanowires.     

Fabrication of vertical ZnO nanowires on silicon (100) with epitaxial ZnO buffer layer

Vertical ZnO nanowires were successfully grown on epitaxial ZnO (002) buffer layer/Si (100) substrate. The nanowire growth process was controlled by surface morphology and orientation of the epitaxial ZnO buffer layer, which was deposited by radio-frequency (rf) sputtering. The copper catalyzed the vapor-liquid-solid growth of ZnO nanowires with diameter of approximately 30 nm and length of approximately 5.0 microm. The perfect wurtzite epitaxial structure (HCP structure) of the ZnO (0002) nanowires synthesized on ZnO (002) buffer layer/Si (100) substrate results in excellent optical characteristics such as strong UV emission at 380 nm with potential use in nano-optical and nano-electronic devices.     

Simultaneous growth mechanisms for Cu-seeded InP nanowires

We report on epitaxial growth of InP nanowires (NWs) from Cu seed particles by metal-organic vapor phase epitaxy (MOVPE). Vertically-aligned straight nanowires can be achieved in a limited temperature range between 340 °C and 370 °C as reported earlier. In this paper we present the effect of the V/III ratio on nanowire morphology, growth rate, and particle configuration at a growth temperature of 350 °C. Two regimes can be observed in the investigated range of molar fractions. At high V/III ratios nanowires grow from a solid Cu₂In particle. At low V/III ratios, nanowire growth from two particle types occurs simultaneously: Growth from solid Cu₂In particles, and significantly faster growth from In-rich particles. We discuss a possible growth mechanism relying on a dynamic interplay between vapor-liquid-solid (VLS) and vapor-solid-solid (VSS) growth. Our results bring us one step closer to the replacement of Au as seed particle material as well as towards a deeper understanding of particle-assisted nanowire growth.      

The role of substrate surface alteration in the fabrication of vertically aligned CdTe nanowires

Previously we have described the deposition of vertically aligned wurtzite CdTe nanowires derived from an unusual catalytically driven growth mode. This growth mode could only proceed when the surface of the substrate was corrupted with an alcohol layer, although the role of the corruption was not fully understood. Here, we present a study detailing the remarkable role that this substrate surface alteration plays in the development of CdTe nanowires; it dramatically improves the size uniformity and largely eliminates lateral growth. These effects are demonstrated to arise from the altered surface's ability to limit Ostwald ripening of the catalytic seed material and by providing a surface unable to promote the epitaxial relationship needed to sustain a lateral growth mode. The axial growth of the CdTe nanowires is found to be exclusively driven through the direct impingement of adatoms onto the catalytic seeds leading to a self-limiting wire height associated with the sublimation of material from the sidewall facets. The work presented furthers the development of the mechanisms needed to promote high quality substrate-based vertically aligned CdTe nanowires. With our present understanding of the growth mechanism being a combination of selective area epitaxy and a catalytically driven vapour-liquid-solid growth mode, these results also raise the intriguing possibility of employing this growth mode in other material systems in an effort to produce superior nanowires.