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.     

Enhancement of the 2DEG density in AlGaAs/InGaAs/GaAs P-HEMTs structures grown by MBE on (311)A and (111)A GaAs substrates

The pseudomorphic high electron mobility transistor (P-HEMT) structure materials Al_0.33Ga_0.7As/In_0.1Ga_0.9As/GaAs have been grown by molecular beam epitaxy (MBE) on (311)A and (111)A GaAs substrates. The epitaxy of strain heterostructure on high index GaAs substrate has led to new growth phenomena, material properties and device applications. The photoluminescence (PL) spectra of the structures have been measured at low temperature. The dominant emission in the PL spectra is due to the recombination from the first electron (e1) subband to the first heavy-hole (hh1) subband (E₁₁: e1–hh1). This feature (E₁₁) is a relatively broad peak and has a typical asymmetric line shape. The transformation of the PL spectra in the close vicinity of the Fermi edge (E_F) under different excitation densities gives strong evidence for the Fermi Edge Singularity (FES) existence. The density of the quasi-two-dimensional electron gas (2DEG) determined by PL study (n_s^PL), is in sufficient agreement with the values found from Hall measurements n_s^Hall at 77 K. The results prove an increase of the electron density in sample grown on GaAs (111)A and (311)A rather than in equivalent sample grown on (001) GaAs substrate. This effect is in good agreement with our theoretical prediction, which is based on a self-consistent solution of the coupled Schrödinger and Poisson equations.     

Gallium nitride nanowires doped with magnesium

GaN nanowires doped with Mg have been synthesized on Si (111) substrate through ammoniating Ga₂O₃ films doped with Mg under flowing ammonia atmosphere. The Mg-doped GaN nanowires were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscopy (HRTEM) and photoluminescence (PL). The results demonstrate that the nanowires were single crystalline with hexagonal wurzite structure. The diameters of the nanowires ranged 20-30 nm and the lengths were about hundreds of micrometers. The intense PL peak at 359 nm showed a blueshift from the bulk band gap emission, attributed to Burstein-Moss effect. The growth mechanism of the crystalline GaN nanowires is discussed briefly.     

Strain accommodation in Ga-assisted GaAs nanowires grown on silicon (111)

We study the mechanism of lattice parameter accommodation and the structure of GaAs nanowires (NWs) grown on Si(111) substrates using the Ga-assisted growth mode in molecular beam epitaxy. These nanowires grow preferentially in the zincblende structure, but contain inclusions of wurtzite at the base. By means of grazing incidence x-ray diffraction and high-resolution transmission electron microscopy of the NW-substrate interface, we show that the lattice mismatch between the NW and the substrate is released immediately after the beginning of NW growth through the inclusion of misfit dislocations, and no pseudomorphic growth is obtained for NW diameters down to 10 nm. NWs with a diameter above 100 nm exhibit a rough interface towards the substrate, preventing complete plastic relaxation. Consequently, these NWs exhibit a residual compressive strain at their bottom. In contrast, NWs with a diameter of 50 nm and below are completely relaxed because the interface is smooth.     

Observation of hole accumulation in Ge/Si core/shell nanowires using off-axis electron holography

Hole accumulation in Ge/Si core/shell nanowires (NWs) has been observed and quantified using off-axis electron holography and other electron microscopy techniques. The epitaxial [110]-oriented Ge/Si core/shell NWs were grown on Si (111) substrates by chemical vapor deposition through the vapor-liquid-solid growth mechanism. High-angle annular-dark-field scanning transmission electron microscopy images and off-axis electron holograms were obtained from specific NWs. The excess phase shifts measured by electron holography across the NWs indicated the presence of holes inside the Ge cores. Calculations based on a simplified coaxial cylindrical model gave hole densities of (0.4 ± 0.2) /nm(3) in the core regions.     

Optical properties of GaN epilayers grown on Si (111) and Si (001) substrates

We report the observation of bright photoluminescence (PL) emission from two types of GaN epilayers grown by molecular beam epitaxy (MBE). Wurtzite phase GaN/Si (111) epilayers are grown by gas source MBE process, whereas cubic phase GaN epilayers are grown on (001) Si covered by thin SiC film in the process of Si annealing in propane prior to the GaN growth. PL emissions are identified based on the results of detailed PL and time-resolved PL investigations. For the wurtzite phase GaN we observe an efficient up in the energy transfer from bound to free excitons. This process is explained by a large difference in the PL decay times for two types (free and bound (donor, acceptor)) of excitonic PL emissions. For cubic phase GaN we confirm recent suggestion that acceptors have smaller thermal ionization energies than those in the wurtzite phase GaN.     

Photoluminescence study of GaAs thin films and nanowires grown on Si(111)

Mg-doped GaAs nanowires have been grown by molecular beam epitaxy on a partially Au-coated Si(111) substrate by the vapor–liquid–solid mechanism. Outside the coated areas, a thin film of GaAs was grown epitaxially at the same time. The optical properties in both parts of the sample were investigated by photoluminescence spectroscopy, as a function of temperature. A structured emission in the range ～1.25–1.55 eV was observed at 10 K and the resemblances in both cases were identified. The radiative transitions are discussed with relevance to known defect centers in the GaAs thin films and to their possible relation with the zinc-blende and wurtzite phases in the nanowires. The presence of both crystalline phases in the nanowires was confirmed by μ-Raman spectroscopy.     

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.     

Bidirectional growth of indium phosphide nanowires

We present a bidirectional growth mode of InP nanowires grown by selective-area metalorganic vapor-phase epitaxy (SA-MOVPE). We studied the effect of the supply ratio of DEZn ([DEZn]) on InP grown structure morphology and crystal structures during the SA-MOVPE. Two growth regimes were observed in the investigated range of the [DEZn] on an InP(111)B substrate. At low [DEZn], grown structures formed tripod structures featuring three nanowires branched toward the [111]A directions. At high [DEZn], we obtained hexagonal pillar-type structures vertically grown on the (111)B substrate. These results show that the growth direction changes from [111]A to [111]B as [DEZn] is increased. We propose a growth mechanism based on the correlation between the incident facet of rotational twins and the shapes of the grown structures. Our results bring us one step closer to controlling the direction of nanowires on a Si substrate that has a nonpolar nature. They can also be applied to the development of InP nanowire devices.     

Ultra-sharp pointed tip Si nanowires produced by very high frequency plasma enhanced chemical vapor deposition via VLS mechanism

Needle-like silicon nanowires have been grown using gold colloid as the catalyst and silane (SiH₄) as the precursor by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). Si nanowires produced by this method were unique with sharpness below 3 nm. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction technique (XRD) confirmed the single crystalline growth of the Si nanowires with (111) crystalline structure. Raman spectroscopy also has revealed the presence of crystalline Si in the grown Si nanowire body. In this research, presence of a gold nanoparticle on tip of the nanowires proved vapor–liquid–solid growth mechanism.     

MBE法生长ZnO纳米线阵列的结构和光学性能

在氧等离子体辅助的MBE系统中, 以1 nm厚的Au薄膜为催化剂, 基于气?液?固(VLS)机制实现了低温ZnO纳米线阵列在Si(111)衬底表面的生长. 通过场发射扫描电子显微镜(FE-SEM)可以观察到, ZnO纳米线阵列垂直生长在衬底上, 直径为20~30 nm. X射线衍射(XRD)和高分辨透射电镜(HRTEM)结果表明: ZnO纳米线为六方纤锌矿结构, 具有沿c轴方向的择优取向. 光致发光(PL)谱显示在380 nm附近有强烈ZnO本征发射峰, 475~650 nm可见光区域有较强的缺陷导致的发射峰.     

Growth characteristics of GaAs nanowires obtained by selective area metal-organic vapour-phase epitaxy

GaAs nanowires were selectively grown by metal-organic vapour-phase epitaxy within a SiO(2) mask window pattern fabricated on a GaAs(111)B substrate surface. The nanowires were 100-3000?nm in height and 50-300?nm in diameter. The height decreased as the mask window diameter was increased or the growth temperature was increased from 700 to 800?°C. The dependence of the nanowire height on the mask window diameter was compared with a calculation, which indicated that the height was inversely proportional to the mask window diameter. This suggests that the migration of growth species on the nanowire side surface plays a major role. Tetrahedral GaAs grew at an early stage of nanowire growth but became hexagonal as the growth process continued. The calculated change in Gibbs free energy for nucleation growth of the crystals indicated that tetrahedra were energetically more favourable than hexagons. Transmission and scanning electron microscopy analyses of a GaAs nanowire showed that many twins developed along the [Formula: see text] B direction, suggesting that twins had something to do with the evolution of the nanowire shape from tetrahedron to hexagon.     

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.     

High yield of self-catalyzed GaAs nanowire arrays grown on silicon via gallium droplet positioning

We report and detail a method to achieve growth of vertical self-catalyzed GaAs nanowires directly on Si(111) with a near-perfect vertical yield, using electron-beam-defined arrays of holes in a dielectric layer and molecular beam epitaxy. In our conditions, GaAs nanowires are grown along a vapor-liquid-solid mechanism, using in?situ self-forming Ga droplets. The focus of this paper is to understand the role of the substrate preparation and of the pre-growth conditioning. Without changing temperature or the V/III ratio, the yield of vertical nanowires is increased incrementally up to 95%. The possibility to achieve very dense arrays, with center-to-center inter-wire distances less than 100?nm, is demonstrated.     

Effect of thermal annealing on the structural and optical properties of CdTe (111)/GaAs (100) heterostructures

Reflection high-energy electron diffraction (RHEED), double-crystal X-ray rocking curve (DCRC), and photoluminescence (PL) measurements were performed to investigate the effect of thermal annealing on the structural and the optical properties of CdTe (111) epilayers grown on GaAs (100) substrates by molecular beam epitaxy (MBE) at low temperature. The results of the RHEED patterns showed that the oxidized layer on the GaAs substrate was removed in a Te atmosphere, and that the 20-Å CdTe layer was grown by three-dimensional process. When the rapid thermal annealing (RTA) was performed at 500°C for 14 s, the FWHM of the DCRC for the CdTe layer had the smallest value. After the RTA process, the luminescence intensity of the exciton remarkably increased, and the peak at 1.476 eV was dominant. As the RTA temperature increased, the luminescence intensity of the exciton peak related to neutral acceptors (A°, X) increased. The temperature dependence of the spectra showed that the (A°, X) peak originated from the recombination of the excitons bound in high-density defects. The excitation power intensity dependence of the PL spectra showed that the peaks of the transitions due to donor-acceptor pairs shifted to larger energies. These results indicate that the structural and the optical properties of the CdTe epilayers grown on GaAs (100) are improved by RTA, and that the RTA process is very useful for the growth of Hg_xCd_1−xTe on CdTe/GaAs heterostructures.     

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.     

Gold nanocluster distribution on faceted and kinked Si nanowires

Si nanowires were grown on (111) substrates by ultra high vacuum chemical vapor deposition using the Au-catalyzed vapor-liquid-solid (VLS) technique. Depending on the growth temperature, the nanowires can be straight in the <111> direction or kinked towards <112>. We present a transmission electron microscopy investigation of the <112> Si nanowires. Results exhibit the relationship between the morphology of nanowires and the distribution of gold on sidewalls bounding the nanowires. The distribution of Au nanoclusters is used as a probe to investigate the growth mechanisms of the VLS process. Our observations are consistent with the model of nucleation and step flow related to the oscillatory behavior of the catalyst droplet.     

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.     

Abnormal optical behaviour of InAsSb quantum dots grown on GaAs substrate by molecular beam epitaxy

InAs(Sb) quantum dots (QDs) samples were grown on GaAs (001) substrate by Molecular Beam Epitaxy (MBE). The structural characterization by Atomic Force Microscopy (AFM) of samples shows that InAsSb islands size increases strongly with antimony incorporation in InAs/GaAs QDs and decreases with reducing the growth temperature from 520 °C to 490 °C. Abnormal optical behaviour was observed in room temperature (RT) photoluminescence (PL) spectra of samples grown at high temperature (520 °C). Temperature dependent PL study was investigated and reveals an anomalous evolution of emission peak energy (EPE) of InAsSb islands, well-known as “S-inverted curve” and attributed to the release of confined carriers from the InAsSb QDs ground states to the InAsSb wetting layer (WL) states. With only decreasing the growth temperature, the S-inverted shape was suppressed indicating a fulfilled 3D-confinement of carriers in the InAsSb/GaAs QD sample.     

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.