The effects of Au surface diffusion to formation of Au droplets/clusters and nanowire growth on GaAs substrate using VLS method

Using VLS method with the separated 220 nm thick Au catalyst circles/stripes configurations sputtered onto GaAs substrate surface, this paper investigated the effects of the Au droplets/clusters formation as well as the nanowires growth process inside and outside the Au circles/stripes configurations. The Au surface outward diffusion from the Au layer edge up to several tens of micrometers has strongly dominated. The effects of Au surface diffusion to formation of Au droplets/cluster and to the nanowires growth on GaAs semiconductor substrate in the region outside the Au layers have been shown. The mechanism of the droplets/clusters formation outside the Au layer could explained by the surface cluster diffusion, meanwhile the nanowires have grown simultaneously during the Au outward diffusion. The growth could explain by the diffusion of Ga and As atoms into the diffusing Au droplets/clusters via dissociative mechanism to form nanowire seeds inside for nanowires growth. The Au droplets/clusters formation and nanowires growth on GaAs substrate outside Au layer could be applied for making nanodevices blocks outside the Au layer. Unfortunately if this Au surface diffusion phenomenon is occurring on the GaAs semiconductor containing the Au stripes interconnections in micro/nanocircuits this could also cause the short-circuits phenomenon, even at thin Au layer.     

Surfactant effect of Au on Ga adsorption on GaAs(0001) surface

Basing on the density-functional theory, we have investigated the atomistic and electronic structures of Ga adsorption on GaAs(0001) surface with pre-absorbed Au monolayer for the understanding of the surfactant effect of Au on the growth of GaAs nanowires. The results show that the deposited Au layer enhances significantly the stability of the Ga adatom on substrate compared to the direct adsorption of Ga on GaAs(0001) surface. The reason is that more electrons of the Ga 6p levels are transferred toward surface bands of substrate because of mediation of the Au layer. It is revealed that Au plays a catalyst role to assist the adsorption of Ga on GaAs(0001) surface. These results offer valuable information in the epitaxial growth of semiconductor nanowires.     

Temperature conditions for GaAs nanowire formation by Au-assisted molecular beam epitaxy

Molecular beam epitaxial growth of GaAs nanowires using Au particles as a catalyst was investigated. Prior to the growth during annealing, Au alloyed with Ga coming from the GaAs substrate, and melted. Phase transitions of the resulting particles were observed in?situ by reflection high-energy electron diffraction (RHEED). The temperature domain in which GaAs nanowire growth is possible was determined. The lower limit of this domain (320?°C) is close to the observed catalyst solidification temperature. Below this temperature, the catalyst is buried by GaAs growth. Above the higher limit (620?°C), the catalyst segregates on the surface with no significant nanowire formation. Inside this domain, the influence of growth temperature on the nanowire morphology and crystalline structure was investigated in detail by scanning electron microscopy and transmission electron microscopy. The correlation of the nanowire morphology with the RHEED patterns observed during the growth was established. Wurtzite GaAs was found to be the dominant crystal structure of the wires.     

High-resolution detection of Au catalyst atoms in Si nanowires

The potential for the metal nanocatalyst to contaminate vapour-liquid-solid grown semiconductor nanowires has been a long-standing concern, because the most common catalyst material, Au, is highly detrimental to the performance of minority carrier electronic devices. We have detected single Au atoms in Si nanowires grown using Au nanocatalyst particles in a vapour-liquid-solid process. Using high-angle annular dark-field scanning transmission electron microscopy, Au atoms were observed in higher numbers than expected from a simple extrapolation of the bulk solubility to the low growth temperature. Direct measurements of the minority carrier diffusion length versus nanowire diameter, however, demonstrate that surface recombination controls minority carrier transport in as-grown n-type nanowires; the influence of Au is negligible. These results advance the quantitative correlation of atomic-scale structure with the properties of nanomaterials and can provide essential guidance to the development of nanowire-based device technologies.     

Catalyst incorporation at defects during nanowire growth

Scanning and transmission electron microscopy was used to correlate the structure of planar defects with the prevalence of Au catalyst atom incorporation in Si nanowires. Site-specific high-resolution imaging along orthogonal zone axes, enabled by advances in focused ion beam cross sectioning, reveals substantial incorporation of catalyst atoms at grain boundaries in <110> oriented nanowires. In contrast, (111) stacking faults that generate new polytypes in <112> oriented nanowires do not show preferential catalyst incorporation. Tomographic reconstruction of the catalyst-nanowire interface is used to suggest criteria for the stability of planar defects that trap impurity atoms in catalyst-mediated nanowires.     

On the formation of voids, etched holes, and GaO particles configuration during the nanowires growth by VLS method on GaAs substrate

The nanowires grown on GaAs semiconductor substrate play very important roles in nanoelectronics, optoelectronics, and sensors. The nanowires can be produced by many methods among the existing methods of nanowires growth on GaAs semiconductor, the vapor–liquid–solid (VLS) method appears to be simple, low cost, and popular. However, this method in practice requires further investigations concerning the growth mechanisms, size effects, and the role of Au catalyst metal diffusion, as well as the effect of technological conditions. Several undesired phenomena, which strongly influence the morphologies, features, and applications of the grown nanowires, can occur as the result of using thick Au catalyst layers, high growth temperatures, and/or small vapor volume in the closed ampoule. This paper aims to examine simultaneous formation of voids, etched holes, and GaO particles along with the nanowires grown by VLS method on GaAs substrate. As the result, typical technological conditions for the nanowires growth with better characterizations are proposed.     

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.     

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.     

Morphology- and orientation-controlled gallium arsenide nanowires on silicon substrates

GaAs nanowires were epitaxially grown on Si(001) and Si(111) substrates by using Au-catalyzed vapor-liquid-solid (VLS) growth in a solid source molecular beam epitaxy system. Scanning electron microscopy analysis revealed that almost all the GaAs nanowires were grown along <111> directions on both Si substrates for growth conditions investigated. The GaAs nanowires had a very uniform diameter along the growth direction. X-ray diffraction data and transmission electron microscopy analysis revealed that the GaAs<111> nanowires had a mixed crystal structure of the hexagonal wurtzite and the cubic zinc-blende. Current-voltage characteristics of junctions formed by the epitaxially grown GaAs nanowires and the Si substrate were investigated by using a current-sensing atomic force microscopy.     

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.     

Effects of gold diffusion on n-type doping of GaAs nanowires

The deposition of n-GaAs shells is explored as a method of n-type doping in GaAs nanowires grown by the Au-mediated metal-organic chemical vapor deposition. Core-shell GaAs/n-GaAs nanowires exhibit an unintended rectifying behavior that is attributed to the Au diffusion during the shell deposition based on studies using energy dispersive X-ray spectroscopy, current-voltage, capacitance-voltage, and Kelvin probe force measurements. Removing the gold prior to n-type shell deposition results in the realization of n-type GaAs nanowires without rectification. We directly correlate the presence of gold impurities to nanowire electrical properties and provide an insight into the role of seed particles on the properties of nanowires and nanowire heterostructures.     

Growth of GaAs Nanowires on Si Substrates Using a Molecular Beam Epitaxy

Au-catalyzed GaAs nanowires were grown on Si substrates by vapor-liquid-solid growth method using a molecular beam epitaxy (MBE). The MBE growth could produce controlled crystalline orientation and uniform diameter along the wire axis of the GaAs nanowires by adjusting growth conditions including growth temperature and V/III flux ratio. Growths of GaAslang001rang as well as GaAslang111rang nanowires were observed by transmission electron microscopy and scanning electron microscopy. Epitaxially grown GaAslang111rang nanowires on a Si(111) substrate were verified through x-ray diffraction out-of-plane 2thetas/omega-scans. A strong room-temperature photoluminescence (PL) was observed from the epitaxially grown GaAslang111rang nanowires on a Si(100) substrate. Results of low-temperature (10 K) PL measurements and current-sensing atomic force microscopy indicated that the GaAs nanowires on a Si substrate were unintentionally doped with Si     

Au stabilization and coverage of sawtooth facets on Si nanowires grown by vapor-liquid-solid epitaxy

Si nanowires grown in UHV by Au-catalyzed vapor-liquid-solid epitaxy are known to exhibit sidewalls with {112}-type orientation that show faceting. To understand the origin of the faceting, Au induced faceting on Si(112) surfaces was studied in situ by spot-profile-analyzing low-energy electron diffraction. With increasing Au coverage at 750 degrees C, the Si(112) surface undergoes various morphological transformations until, at a critical Au coverage of about 3.1 x 10 (14) atoms/cm (2), a phase consisting of large (111) and (113) facets forms, similar in structure to the nanowire sidewalls. This phase is stable at larger Au coverages in equilibrium with Au droplets. We suggest that Si nanowire surfaces exhibit this structure, and we derive the Au coverage on the two types of facets.     

Point defect configurations of supersaturated Au atoms inside Si nanowires

Aberration-corrected scanning transmission electron microscopy (STEM) is used to reveal individual Au atom configurations inside Si nanowires grown by Au-catalyzed vapor-liquid-solid (VLS) molecular beam epitaxy (MBE). We identify a substitutional and three distinct interstitial configurations, one of which has not been previously identified. We confirm the stability of the observed point defect configurations by density functional theory (DFT) calculations. The observed number densities of the various configurations are in accord with their calculated formation energies. The concentration of Au atoms is larger than the solubility limit, but the effect may be caused by the STEM beam.     

Catalytic role of gold nanoparticle in GaAs nanowire growth: a density functional theory study

The energetics of Ga, As, and GaAs species on the Au(111) surface (employed as a model for Au nanoparticles) is investigated by means of density functional calculations. Apart from formation of the compound Au(7)Ga(2), Ga is found to form a surface alloy with gold with comparable ΔH ~ -0.5 eV for both processes. Dissociative adsorption of As(2) is found to be exothermic by more than 2 eV on both clean Au(111) and AuGa surface alloys. The As-Ga species formed by reaction of As with the surface alloy is sufficiently stable to cover the surface of an Au particle in vacuo in contact with a GaAs substrate. The results of the calculations are interpreted in the context of Au-catalyzed growth of GaAs nanowires. We argue that arsenic is supplied to the growth zone of the nanowire mainly by impingement of molecules on the gold particle and identify a regime of temperatures and As(2) partial pressures suitable for Au-catalyzed nanowire growth in molecular beam epitaxy.     

Growth and characterization of GaAs nanowires on carbon nanotube composite films: toward flexible nanodevices

Poly(ethylene imine) functionalized carbon nanotube thin films, prepared using the vacuum filtration method, were decorated with Au nanoparticles by in situ reduction of HAuCl4 under mild conditions. These Au nanoparticles were subsequently employed for the growth of GaAs nanowires (NWs) by the vapor-liquid-solid process in a gas source molecular beam epitaxy system. The process resulted in the dense growth of GaAs NWs across the entire surface of the single-walled nanotube (SWNT) films. The NWs, which were orientated in a variety of angles with respect to the SWNT films, ranged in diameter between 20 to 200 nm, with heights up to 2.5 microm. Transmission electron microscopy analysis of the NW-SWNT interface indicated that NW growth was initiated upon the surface of the nanotube composite films. Photoluminescence characterization of a single NW specimen showed high optical quality. Rectifying asymmetric current-voltage behavior was observed from contacted NW ensembles and attributed to the core-shell pn-junction within the NWs. Potential applications of such novel hybrid architectures include flexible solar cells, displays, and sensors.     

Catalytic action of gold and copper crystals in the growth of carbon nanotubes

Multi-wall carbon nanotubes are grown in a chemical vapor deposition process by using bulk gold and copper substrates as catalysts. Nanotube growth starts from a nanometer-sized roughness on the metal surfaces and occurs in a mechanism where the catalyst particle is either at the tip (Au) or root (Cu) of the growing nanotube. Whereas Au leads to nanotubes with good structural perfection, nanotubes grown from Cu show a higher density of defects. High-resolution transmission electron microscopy shows the bonding between Au and carbon at the metal-nanotube interface whereas no bonds between Cu and carbon occur. Highly mobile Au or Cu atoms adsorb at the growing edge of a carbon nanotube from where diffusion along the nanotube wall can lead to the formation of Au or Cu nanowires inside the central hollow of carbon nanotubes.     

Growth of GaInAs/AlInAs heterostructure nanowires for long-wavelength photon emission

We investigated the growth of GaInAs/AlInAs heterostructure nanowires on InP(111)B and Si(111) substrates in a metalorganic vapor phase epitaxy reactor. Au colloids were used to deposit Au catalysts 20 and 40 nm in diameter on the substrate surfaces. We obtained vertical GaInAs and AlInAs nanowires on InP(111)B surfaces. The GaInAs nanowires capped with GaAs/AlInAs layers show room-temperature photoluminescence. The peak exhibits a blue-shift when the Ga content in the core GaInAs nanowire is increased. For the GaInAs/AlInAs heterostructure growth, it is possible to change the Ga content sharply but Al also exists in the GaInAs layer regions. We also found that the ratios of Ga and Al contents to In content tend to increase and the axial growth rate to decrease along the nanowire toward the top. We were also able to make vertical GaInAs nanowires on Si(111) surfaces after a short growth of GaP and InP.     

Gold nanowires fabricated by immersion plating

The growth mechanism of oriented Au nanowires fabricated by immersion plating was investigated. Both n-type crystal Si (c-Si) and amorphous Si (a-Si) with an electron-beam (E-beam) patterned resist nanotrench were immersed into the plating bath HAuCl(4)/HF. For the Au nanowires fabricated on c-Si, voids, nanograins, and clusters were observed at various plating conditions, time and temperature. The voids were often found in the center of the Au nanowires due to there being fewer nucleation sites on the c-Si surface. However, Au can easily nucleate on the surface of a-Si and form continuous Au nanowires with grain sizes about 10-50?nm. The resistivities of Au nanowires with width 105?nm fabricated on a-Si are about 4.4-6.5?μΩ?cm. After annealing at 200?°C for 30?min in N(2) ambient, the resistivities are lowered to about 3.0-3.9?μΩ?cm, measured in an atomic force microscope (AFM) in contact mode. The grain size of Au is in the range of ～50-100?nm. A scanning electron microscope (SEM) examination and grazing incident x-ray diffraction (GIXRD) analysis were also carried out to study the morphology and crystalline structure of the Au nanowires.     

Photovoltaic properties of GaAsP core-shell nanowires on Si(001) substrate

We report on the growth and electro-optical studies of photovoltaic properties of GaAsP nanowires. Low density GaAsP nanowires were grown by Au assisted MOVPE on Si(001) substrates using a two step procedure to form a radial p-n junction. The STEM analyses show that the nanowires have cubic structure with the alloy composition GaAs?.??P?.?? in the nanowire core and GaAs?.??P?.?? in the shell. The nanowire ensembles were processed in the form of sub-millimeter size mesas. The photovoltaic properties were characterized by optical beam induced current (OBIC) and electronic beam induced current (EBIC) maps. Both OBIC and EBIC maps show that the photovoltage is generated by the nanowires; however, a strong signal variation from wire to wire is observed. Only one out of six connected nanowires produce a measurable signal. These strong fluctuations can be tentatively explained by the variation of the resistance of the nanowire-to-substrate connection, which is highly sensitive to the quality of the Si-GaAsP interface. This study demonstrates the importance of the spatially resolved charge collection microscopy techniques for the diagnosis of failures in nanowire photovoltaic devices.