Kinetic effects in InP nanowire growth and stacking fault formation: the role of interface roughening

InP nanowire polytypic growth was thoroughly studied using electron microscopy techniques as a function of the In precursor flow. The dominant InP crystal structure is wurtzite, and growth parameters determine the density of stacking faults (SF) and zinc blende segments along the nanowires (NWs). Our results show that SF formation in InP NWs cannot be univocally attributed to the droplet supersaturation, if we assume this variable to be proportional to the ex situ In atomic concentration at the catalyst particle. An imbalance between this concentration and the axial growth rate was detected for growth conditions associated with larger SF densities along the NWs, suggesting a different route of precursor incorporation at the triple phase line in that case. The formation of SFs can be further enhanced by varying the In supply during growth and is suppressed for small diameter NWs grown under the same conditions. We attribute the observed behaviors to kinetically driven roughening of the semiconductor/metal interface. The consequent deformation of the triple phase line increases the probability of a phase change at the growth interface in an effort to reach local minima of system interface and surface energy.     

Direct observation of a noncatalytic growth regime for GaAs nanowires

We identify a new noncatalytic growth regime for molecular beam epitaxially grown GaAs nanowires (NWs) that may provide a route toward axial heterostructures with discrete material boundaries and atomically sharp doping profiles. Upon increase of the As/Ga flux ratio, the growth mode of self-induced GaAs NWs on SiO(2)-masked Si(111) is found to exhibit a surprising discontinuous transition in morphology and aspect ratio. For effective As/Ga ratios <1, in situ reflection high-energy electron diffraction measurements reveal clear NW growth delay due to formation of liquid Ga droplets since the growth proceeds via the vapor-liquid-solid mechanism. In contrast, for effective As/Ga ratios >1 an immediate onset of NW growth is observed indicating a transition to droplet-free, facet-driven selective area growth with low vertical growth rates. Distinctly different microstructures, facet formation and either the presence or absence of Ga droplets at the apex of NWs, are further elucidated by transmission electron microscopy. The results show that the growth mode transition is caused by an abrupt change from As- to Ga-limited conditions at the (111)-oriented NW growth front, allowing precise tuning of the dominant growth mode.     

Three-dimensional morphology of GaP-GaAs nanowires revealed by transmission electron microscopy tomography

We have investigated the morphology of heterostructured GaP-GaAs nanowires grown by metal-organic vapor-phase epitaxy as a function of growth temperature and V/III precursor ratio. The study of heterostructured nanowires with transmission electron microscopy tomography allowed the three-dimensional morphology to be resolved, and discrimination between the effect of axial (core) and radial (shell) growth on the morphology. A temperature- and precursor-dependent structure diagram for the GaP nanowire core morphology and the evolution of the different types of side facets during GaAs and GaP shell growth were constituted.     

Control of GaAs nanowire morphology and crystal structure

The morphology and crystal structure of Au-seeded GaAs nanowires (NWs) grown by molecular beam epitaxy were investigated as a function of the temperature, V/III flux ratio, and Ga flux. Low and intermediate growth temperatures of 400 and 500?°C resulted in a strongly tapered morphology, with stacking faults occurring at an average rate of 0.1?nm(-1). NWs with uniform diameter and the occurrence of crystal defects reduced by more than an order of magnitude were achieved at 600?°C, a V/III flux ratio of 2.3, and a Ga impingement rate on the surface of 0.07?nm?s(-1). Comparison of nanowire densities on the various post-growth surfaces suggests a possible incubation time between the moment the Ga shutter is opened and when nanowire growth is initiated. Increasing the flux ratio favored uniform sidewall growth, making the process suitable for the fabrication of core-shell structures.     

Growth of Ge-Si nanowire heterostructures via chemical vapor deposition

The growth of Ge-Si and Ge-Si nanowire (NW) heterostructures was demonstrated via chemical vapor deposition. Due to the influence of interface energy, differing topographies of the heterostructures were observed. On initially grown Ge NWs, numerous Si NW branches were grown near the tip due to Au migration. However, on initially grown Si NWs, high-density Ge nanodots were 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.     

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.     

Mechanism of self-assembled growth of ordered GaAs nanowire arrays by metalorganic vapor phase epitaxy on GaAs vicinal substrates

We report the self-catalyzed growth of GaAs nanowire arrays by metalorganic vapor phase epitaxy (MOVPE) on GaAs vicinal substrates. The effect of substrate misorientation on the nanowire growth and the influence of growth parameters such as temperature and input V/III ratio have been studied in detail. Variation in the nanowire growth mechanism and consequential changes in the nanowire growth morphology were observed. A VLS growth mechanism with negligible effect of the vicinal surface gave rise to randomly distributed droplet-terminated GaAs nanowires at 400?°C and multiprong root-grown GaAs nanowire clusters at 500?°C with low V/III ratio. The substrate misorientation effect was dominant at 500?°C with higher V/III ratio, in which case the combined effect of the vicinal surface and the self-catalyzed Ga droplets assisted the realization of self-assembled and crystallographically oriented epitaxial nanowire arrays through the vapor-solid mechanism.     

Synthesis of single-crystalline Zn metal nanowires utilizing cold-wall physical vapor deposition

Zinc metal nanowires (NWs) of two different morphologies have been synthesized in a cold-wall physical vapor deposition (CWPVD) chamber at high vacuum conditions and growth temperatures of 150 degrees C. Substrates initially seeded by gold or platinum crystals show NWs of wool-like and/or unidirectional morphologies. Transmission electron microscopy (TEM) studies revealed that the rodlike NWs consist of single-crystalline Zn covered with a thin native oxide. NWs of wool-like morphology are suppressed using platinum as the seed metal. NW growth proceeds via vapor-solid (VS) kinetics without any catalyst particles on the wire tips. The highest observed growth rates exceed the Zn deposition rate by factors up to 860, indicating the dominant role of surface diffusion of Zn adatoms, also along the NWs. The surface diffusion length of Zn adatoms on the NW side facet is determined to be 39 mum. Direct impingement of precursor atoms on the NW tip is not significant for the growth process.     

Hyperbranched lead selenide nanowire networks

Lead chalcogenide nanostructures are good potential candidates for applications in multiexciton solar cells, infrared photodetectors, and electroluminescence devices. Here we report the synthesis and electrical measurements of hyperbranched PbSe nanowire networks. Hyperbranched PbSe nanowire networks are synthesized via a vapor-liquid-solid (VLS) mechanism. The branching is induced by continuously feeding the PbSe reactant with the vapor of a low-melting-point metal catalyst including In, Ga, and Bi. The branches show very regular orientation relationships: either perpendicular or parallel to each other. The diameter of the individual NWs depends on the size of the catalyst droplets, which can be controlled by the catalyst vapor pressure. Significantly, the hyperbranched networks can be grown epitaxially on NaCl, a low-cost substrate for future device array applications. Electrical measurements across branched NWs show the evolution of charge carrier transport with distance and degree of branching.     

Lateral self-aligned p-type In2O3 nanowire arrays epitaxially grown on Si substrates

Lateral orientated growth of In2O3 nanowire (NW) and nanorod (NR) arrays has been achieved by a vapor transport and condensation method on (001) and (111) surfaces of Si substrates. The single crystalline In2O3 NWs and NRs were grown along [211] in parallel to the Si +/-[110] and lying in the substrate plane. The electrical measurements show that the In2O3 NWs are p-type semiconductor. By N+ doping, the resistivity of the In2O3 NWs has been tuned. The lateral self-aligned In2O3 NW and NR arrays on Si can offer some unique advantages for fabricating parallel nanodevices that can be integrated directly with silicon technology.     

Diameter-dependent composition of vapor-liquid-solid grown Si(1-x)Ge(x) nanowires

Diameter-dependent compositions of Si(1-x)Ge(x) nanowires grown by a vapor-liquid-solid mechanism using SiH(4) and GeH(4) precursors are studied by transmission electron microscopy and X-ray energy dispersive spectroscopy. For the growth conditions studied, the Ge concentration in Si(1-x)Ge(x) nanowires shows a strong dependence on nanowire diameter, with the Ge concentration decreasing with decreasing nanowire diameter below approximately 50 nm. The size-dependent nature of Ge concentration in Si(1-x)Ge(x) NWs is strongly suggestive of Gibbs-Thomson effects and highlights another important phenomenon in nanowire growth.     

Heteroepitaxial growth of vertical GaAs nanowires on Si(111) substrates by metal-organic chemical vapor deposition

Epitaxial growth of vertical GaAs nanowires on Si(111) substrates is demonstrated by metal-organic chemical vapor deposition via a vapor-liquid-solid growth mechanism. Systematic experiments indicate that substrate pretreatment, pregrowth alloying temperature, and growth temperature are all crucial to vertical epitaxial growth. Nanowire growth rate and morphology can be well controlled by the growth temperature, the metal-organic precursor molar fraction, and the molar V/III ratio. The as-grown GaAs nanowires have a predominantly zinc-blende crystal structure along a <111> direction. Crystallographic {111} stacking faults found perpendicular to the growth axis could be almost eliminated via growth at high V/III ratio and low temperature. Single nanowire field effect transistors based on unintentionally doped GaAs nanowires were fabricated and found to display a strong effect of surface states on their transport properties.     

Tunable light emission from quantum-confined excitons in TiSi2-catalyzed silicon nanowires

Visible and near-infrared photoluminescence (PL) at room temperature is reported from Si nanowires (NWs) grown by chemical vapor deposition from TiSi2 catalyst sites. NWs grown with average diameter of 20 nm were etched and oxidized to thin and passivate the wires. The PL emission blue shifted continuously with decreasing nanowire diameter. Slowed oxidation was observed for small nanowire diameters and provides a high degree of control over the emission wavelength. Transmission electron microscopy, PL, and time-resolved PL data are fully consistent with quantum confinement of charge carriers in the Si nanowire core being the source of luminescence. These light emitting nanowires could find application in future CMOS-compatible photonic devices.     

Selective area growth of GaN nanowires using metalorganic chemical vapor deposition on nano-patterned Si(111) formed by the etching of nano-sized Au droplets

We report on the selective area growth of GaN nanowires (NWs) on nano-patterned Si(111) substrates by metalorganic chemical vapor deposition. The nano-patterns were fabricated by the oxidation of Si followed by the etching process of Au nano-droplets. The size of formed nano-pattern on Si(111) substrate was corresponding to the size of Au nano-droplet, and the diameter of GaN NWs grown was similar to the diameter of fabricated nano-pattern. The interesting phenomenon of using the nano-patterned Si(111) substrates is the formation of very clear substrate surface even after the growth of GaN NWs. However, in the case of GaN NWs grown using Au nano-droplets, there was several nanoparticles including GaN bulk grains on the Si(111) substrates. The smooth surface morphology of nano-patterned Si(111) substrates was attributed to the presence of SiO₂ layer which prevents the formation of unnecessary GaN particles during the GaN NW growth. Therefore, we believe that nano-patterning method of Si(111) which was obtained by the oxidation of Si(111) substrate and subsequent Au etching process can be utilized to grow high-quality GaN NWs and its related nano-device applications.     

General control of transition-metal-doped GaN nanowire growth: toward understanding the mechanism of dopant incorporation

We report the first synthesis and characterization of cobalt- and chromium-doped GaN nanowires (NWs), and compare them to manganese-doped GaN NWs. Samples were synthesized by chemical vapor deposition method, using cobalt(II) chloride and chromium(III) chloride as dopant precursors. For all three impurity dopants hexagonal, triangular, and rectangular NWs were observed. The fraction of NWs having a particular morphology depends on the initial concentration of the dopant precursors. While all three dopant ions have the identical effect on GaN NW growth and faceting, Co and Cr are incorporated at much lower concentrations than Mn. These findings suggest that the doping mechanism involves binding of the transition-metal intermediates to specific NW facets, inhibiting their growth and causing a change in the NW morphology. We discuss the doping concentrations of Mn, Co, and Cr in terms of differences in their crystal-field stabilization energies (DeltaCFSE) in their gas-phase intermediates and in substitutionally doped GaN NWs. Using iron(III) chloride and cobalt(II) acetate as dopant precursors we show that the doping concentration dependence on DeltaCFSE allows for the prediction of achievable doping concentrations for different dopant ions in GaN NWs, and for a rational choice of a suitable dopant-ion precursor. This work further demonstrates a general and rational control of GaN NW growth using transition-metal impurities.     

Controlled synthesis of germanium nanowires and nanotubes with variable morphologies and sizes

We report on the controlled growth of germanium (Ge) nanostructures in the form of both nanowire (NW) and nanotube (NT) with ultrahigh aspect ratios and variable diameters. The nanostructures are grown inside a porous anodic aluminum oxide (AAO) template by low-temperature chemical vapor deposition (CVD) assisted by an electrodeposited metal nanorod catalyst. Depending on the choice of catalytic metals (Au, Ni, Cu, Co) and germane (GeH(4)) concentration during CVD, either Ge NWs or NTs can be synthesized at low growth temperatures (310-370 °C). Furthermore, Ge NWs and NTs with two or more branches can be grown from the same stem while using AAO with branched channels as templates. Transmission electron microscopy studies show that NWs are single crystalline and that branches grow epitaxially from the stem of NWs with a crystalline direction independent of diameter. As-grown NTs are amorphous but can crystallize via postannealing at 400 °C in Ar/H(2) atmosphere, with a wall thickness controllable between 6 and 18 nm in the CVD process. The yield and quality of the NTs are critically dependent on the choice of the catalyst, where Ni appears the best choice for Ge NT growth among Ni, Cu, Co, and Au. The synthesis of structurally uniform and morphologically versatile Ge nanostructures may open up new opportunities for integrated Ge-nanostructure-based nanocircuits, nanodevices, and nanosystems.     

Influence of nanowire density on the shape and optical properties of ternary InGaAs nanowires

We have synthesized ternary InGaAs nanowires on (111)B GaAs surfaces by metal-organic chemical vapor deposition. Au colloidal nanoparticles were employed to catalyze nanowire growth. We observed the strong influence of nanowire density on nanowire height, tapering, and base shape specific to the nanowires with high In composition. This dependency was attributed to the large difference of diffusion length on (111)B surfaces between In and Ga reaction species, with In being the more mobile species. Energy dispersive X-ray spectroscopy analysis together with high-resolution electron microscopy study of individual InGaAs nanowires shows large In/Ga compositional variation along the nanowire supporting the present diffusion model. Photoluminescence spectra exhibit a red shift with decreasing nanowire density due to the higher degree of In incorporation in more sparsely distributed InGaAs nanowires.     

Sulfur passivation and contact methods for GaAs nanowire solar cells

The effect of sulfur passivation on core-shell p-n junction GaAs nanowire (NW) solar cells has been investigated. Devices of two types were investigated, consisting of indium tin oxide contact dots or opaque Au finger electrodes. Lateral carrier transport from the NWs to the contact fingers was achieved via a p-doped GaAs surface conduction layer. NWs between the opaque contact fingers had sidewall surfaces exposed for passivation by sulfur. The relative cell efficiency increased by 19% upon passivation. The contribution of the thin film grown between the NWs to the total cell efficiency was estimated by removing the NWs using a sonication procedure. Mechanisms of carrier transport and photovoltaic effects are discussed on the basis of spatially resolved laser scanning measurements.     

Synthesis of high crystallinity ZnO nanowire array on polymer substrate and flexible fiber-based sensor

Well aligned ZnO nanowire (NW) arrays are grown on Kevlar fiber and Kapton film via the chemical vapor deposition (CVD) method. These NWs have better crystallinity than those synthesized through the low-temperature hydrothermal method. The average length and diameter of ZnO NWs grown on Kevlar fiber can be controlled from 0.5 to 2.76 μm and 30 to 300 nm, respectively. A flexible ultraviolet (UV) sensor based on Kevlar fiber/ZnO NWs hybrid structure is made to detect UV illumination quantificationally.