Influence of growth temperature on the selective area MOVPE of InAs nanowires on GaAs (1 1 1) B using N2 carrier gas

The influence of temperature on selective area (SA) InAs nanowire growth was investigated for metal-organic vapor phase epitaxy (MOVPE) using N₂ as the carrier gas and (1 1 1) B GaAs substrates. In contrast to the growth temperature range – below 600 °C – reported for hydrogen ambient, the optimal growth temperature between 650 and 700 °C was 100 K higher than the optimal ones for H₂ carrier gas. At these temperatures, nanowires with aspect ratios of about 80 and a symmetric hexagonal shape were obtained. The results found are attributed to the physical and chemical properties of the carrier gas.     

Effect of arsenic species on the kinetics of GaAs nanowires growth by molecular beam epitaxy

GaAs nanowires (NWs) are grown on GaAs (1 1 1) B substrates in a molecular beam epitaxy system, by Au-assisted vapor–liquid–solid growth. We compare the characteristics of NWs elaborated with As₂ or As₄ molecules. In a wide range of growth temperatures, As₄ leads to growth rates twice faster than As₂. The shape of the NWs also depends on the arsenic species: with As₄, regular rods can be obtained, while pencil-like shape results from growth with As₂. From the analysis of the incoming fluxes, which contributes to the NWs formation, we conclude that the diffusion length of Ga adatoms along the NW sidewalls is smaller under As₂ flux as compared to that under As₄ flux. It follows that As₂ flux is favourable to the formation of radial heterostructures, whereas As₄ flux is preferable to maintain pure axial growth.     

Growth of hexagonal and cubic InN nanowires using MOCVD with different growth temperatures

We have performed a detailed investigation of the metal-organic chemical vapor deposition (MOCVD) growth and characterization of InN nanowires formed on Si(1 1 1) substrates under nitrogen rich conditions. The growth of InN nanowires has been demonstrated by using an ion beam sputtered (∼10 nm) Au seeding layer prior to the initiation of growth. We tried to vary the growth temperature and pressure in order to obtain an optimum growth condition for InN nanowires. The InN nanowires were grown on the Au+In solid solution droplets caused by annealing in a nitrogen ambient at 700 °C. By applying this technique, we have achieved the formation of InN nanowires that are relatively free of dislocations and stacking faults. Scanning electron microscopy (SEM) showed wires with diameters of 90–200 nm and lengths varying between 3 and 5 μm. Hexagonal and cubic structure is verified by high resolution X-ray diffraction (HR-XRD) spectrum. Raman measurements show that these wurtzite InN nanowires have sharp peaks E₂ (high) at 491 cm⁻¹ and A₁ (LO) at 591 cm⁻¹.     

Influence of substrate temperature on the shape of GaAs nanowires grown by Au-assisted MOVPE

GaAs nanowires (NWs) are grown on the GaAs(1 1 1)B substrates by the Au-assisted metal–organic vapor phase epitaxy (MOVPE). The NW shape is found to be strongly dependent on the substrate temperature during the growth. With increase in the growth temperature, the NW shape modifies from prismatic to conical. The observed temperature behavior is studied within the frame of a theoretical model. It is shown that the key process responsible for the lateral growth is the decomposition of MOVPE precursors at the NW sidewalls and the substrate. Theoretical results are in a good agreement with experimental findings and can be used for the numerical estimates of some important growth parameters as well as for the controlled fabrication of NWs with the desired shape.     

Droplet epitaxy of zinc-blende GaN quantum dots

Zinc-blende GaN quantum dots were grown on 3C-AlN(0 0 1) by a vapor–liquid–solid process in a molecular beam epitaxy system. We were able to control the density of the quantum dots in a range of 5×10⁸–5×10¹² cm⁻². Photoluminescence spectroscopy confirmed the optical activity of the GaN quantum dots in a range of 10¹¹–5×10¹² cm⁻². The data obtained give an insight to the condensation mechanism of the vapor–liquid–solid process in general, because the GaN quantum dots condense in metastable zinc-blende crystal structure supplied by the substrate, and not in the wurtzite crystal structure expected from free condensation in the droplet.     

Growth and process modeling studies of nickel-catalyzed metalorganic chemical vapor deposition of GaN nanowires

A combination of experimental and computational fluid dynamics-based reactor modeling studies were utilized to study the effects of process conditions on GaN nanowire growth by metalorganic chemical vapor deposition (MOCVD) in an isothermal tube reactor. The GaN nanowires were synthesized on (0 0 0 1) sapphire substrates using nickel thin films as a catalyst. GaN nanowire growth was observed over a furnace temperature range of 800–900 °C at V/III ratios ranging from 33 to 67 and was found to be strongly dependent on the position of the substrate relative to the group III inlet tube. The modeling studies revealed that nanowire growth consistently occurred in a region in the reactor where the GaN thin-film deposition rate was reduced and the gas phase consisted primarily of intermediate species produced by the reaction and decomposition of trimethylgallium–ammonia adduct compounds. The GaN nanowires exhibited a predominant [1 1 2¯ 0] growth direction. Photoluminescence measurements revealed an increase in the GaN near-band edge emission intensity and a reduction in the deep-level yellow luminescence with increasing growth temperature and V/III ratio.     

Ga and In incorporation rates in Ga1−xInxAs growth by chemical beam epitaxy

GaAs, InAs and Ga_1?xIn_xAs layers were grown by chemical beam epitaxy (CBE) using triethylgallium, trimethylindium and tertiarybutylarsine as precursors for Ga, In and As, respectively. The growth rate during the homoepitaxial growth of GaAs and InAs, deduced from the frequency of reflection high-energy electron diffraction intensity oscillations, was used to calibrate the incorporation rates for the III elements. The In content of the Ga_1?xIn_xAs layers was measured by Rutherford backscattering spectrometry and compared with the value predicted from the above calibration data; while the measured In mole fraction is close to the predicted value for the samples grown for low In to Ga flux ratios (x<0.2), the In incorporation is enhanced for larger values of this ratio. The results obtained on layers grown at different substrate temperatures show that In mole fraction is almost constant at growth temperatures in the range 400–500 °C, but a strong dependence on the substrate temperature has been found outside this range. The above results, not observed for samples grown by solid source molecular beam epitaxy, indicate that some interaction between Ga and In precursors at the sample surface could take place during the growth by CBE.     

Growth of undoped and Zn-doped GaN nanowires

Undoped and Zn-doped GaN nanowires were synthesized by chemical vapor deposition (CVD), and the effects of substrates, catalysts and precursors were studied. A high density of GaN nanowires was obtained. The diameter of GaN nanowires ranged from 20 nm to several hundreds of nm, and their length was about several tens of μm. The growth mechanism of GaN nanowires was discussed using a vapor–liquid–solid (VLS) model. Furthermore, room-temperature cathodoluminescence spectra of undoped and Zn-doped GaN nanowires showed emission peaks at 364 and 420 nm, respectively.     

Ordered arrays of high-quality single-crystalline α-Si3N4 nanowires: Synthesis,properties and applications

Ordered arrays of high-quality single-crystalline α-Si₃N₄ nanowires (NWs) have been synthesized via thermal evaporation and detailed characteristics of the NWs have been analyzed by employing scanning electron microscope (SEM) along with energy dispersive spectroscopy (EDS), high-resolution transmission electron microscope (HRTEM), X-ray diffraction (XRD), X-ray photospectroscopy (XPS), infrared (IR), photoluminescence (PL) and in situ I–V measurements by STM/TEM holder. The microscopic results revealed that the NWs having diameter in the range of ~30–100 nm and length in microns. Furthermore, the NWs are found to be single crystalline grown along [0 0 1] direction. The elemental composition and valence states of elements are analyzed by EDS and XPS. The room temperature PL spectra exhibit a broad range visible emission band. The electron transport property of a single NW illustrates the symmetric I–V curve of a semiconductor. The possible growth mechanism is also briefly discussed.     

A simple method to synthesize α-Si3N4, β-SiC and SiO2 nanowires by carbothermal route

α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are synthesized via the direct current arc discharge method with a mixture of silicon, activated carbon and silicon dioxide as the precursor. The α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are about 50–200 nm in stem diameter and 10–100 μm in length. α-Si₃N₄ nanowires and β-SiC nanowires consist of a solid single-crystalline core along the [0 0 1] and [1 1 1] directions, respectively, wrapped within an amorphous SiO_x layer. The direct current arc plasma-assisted self-catalytic vapor–solid and/or vapor–liquid–solid (VLS) growth processes are proposed as the growth mechanism of the nanowires.     

Impurity induced periodic mesostructures in Sb-doped SnO2 nanowires

Impurity doping on semiconductor nanowires formed via vapor–liquid–solid (VLS) mechanism has been investigated with the intention being to control the transport properties. Here we demonstrate that an addition of excess impurity dopants induces a mesostructure of long range periodic arched-shape in Sb-doped SnO₂ nanowires. The microstructural and composition analysis demonstrated the importance of the presence of impurities at the growth interface during VLS growth rather than the dopant incorporation into nanowires, indicating kinetically induced mechanisms.     

Growth of Zn3As2 on GaAs by liquid phase epitaxy and their characterization

Zn₃As₂ epitaxial layers were grown on GaAs (1 0 0) substrates by liquid phase epitaxy (LPE) using Ga as the solvent. Zinc mole fraction in the growth melt was varied from 1.07×10^?2 to 6×10^?2. X-ray diffraction spectrum exhibits a sharp peak at 43.3° characteristic of Zn₃As₂ crystalline layer. The peak intensity increases with increase in zinc mole fraction in the growth melt. The compositions of the as-grown Zn₃As₂ layers were confirmed by energy dispersive X-ray (EDX) analysis. Surface morphology was studied using scanning electron microscopy (SEM) and the thickness of the epilayers was also determined. The Hall measurements at 300 K indicate that Zn₃As₂ epilayers are unintentionally p-doped. With an increase of zinc mole fraction in the growth melt, carrier concentration increases and carrier mobility decreases. Infrared optical absorption spectroscopy showed a sharp absorption edge at 1.0 eV corresponding to the reported band gap of Zn₃As₂.     

Hydrothermal synthesis of Bi2Te3 nanowires through the solid-state interdiffusion of Bi and Te atoms on the surface of Te nanowires

Polycrystalline Bi₂Te₃ nanowires were prepared by a hydrothermal method that involved inducing the nucleation of Bi atoms reduced from BiCl₃ on the surface of Te nanowires, which served as sacrificial templates. A Bi–Te alloy is formed by the interdiffusion of Bi and Te atoms at the boundary between the two metals. The Bi₂Te₃ nanowires synthesized in this study had a length of 3–5 μm, which is the same length as that of the Te nanowires, and a diameter of 300–500 nm, which is greater than that of the Te nanowires. The experimental results indicated that volume expansion of the Bi₂Te₃ nanowires was a result of the interdiffusion of Bi and Te atoms when Bi was alloyed on the surface of the Te nanowires. The morphologies of Bi₂Te₃ are strongly dependent on the reaction conditions such as the temperature and the type and concentration of the reducing agent. The morphologies, crystalline structure and physical properties of the product were analyzed by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS).     

Fabrication and characterization of GaAs quantum well buried in AlGaAs/GaAs heterostructure nanowires

We developed a growth method for forming a GaAs quantum well contained in an AlGaAs/GaAs heterostructure nanowire using selective-area metal organic vapor phase epitaxy. To find the optimum growth condition of AlGaAs nanowires, we changed the growth temperature between 800 and 850 °C and found that best uniformity of the shape and the size was obtained near 800 °C but lateral growth of AlGaAs became larger, which resulted in a wide GaAs quantum well grown on the top (1 1 1)B facet of the AlGaAs nanowire. To form the GaAs quantum well with a reduced lateral size atop the AlGaAs nanowire, a GaAs core nanowire about 100 nm in diameter was grown before the AlGaAs growth, which reduced the lateral size of AlGaAs to roughly half compared with that without the GaAs core. Photoluminescence measurement at 4.2 K indicated spectral peaks of the GaAs quantum wells about 60 meV higher than the acceptor-related recombination emission peak of GaAs near 1.5 eV. The photoluminescence peak energy showed a blue shift of about 15 meV, from 1.546 to 1.560 eV, as the growth time of the GaAs quantum well was decreased from 8 to 3 s. Transmission electron microscopy and energy dispersive X-ray analysis of an AlGaAs/GaAs heterostructure nanowire indicated a GaAs quantum well with a thickness of 5−20 nm buried along the 〈1 1 1〉 direction between the AlGaAs shells, showing a successful fabrication of the GaAs quantum well.     

Liquid phase epitaxy (LPE) of GaN on c- and r-faces of AlN substrates

We present the optical properties of MBE-grown GaAs–AlGaAs core–shell nanowires (NWs) grown on anodized-aluminum-oxide (AAO) patterned-Si (1 1 1) substrate using photoluminescence and Raman scattering spectroscopy. The GaAs NWs were grown via the vapor–liquid–solid method with Au-nanoparticles as catalysts. Enhancement in emission of at least an order of magnitude was observed from the GaAs–AlGaAs core–shell NWs as compared to the bare GaAs NWs grown under similar conditions, which is an indication of improved radiative efficiency. The improvement in radiative efficiency is due to the passivating effect of the AlGaAs shell. Variation in bandgap emission energy as a function of temperature was analyzed using the semi-empirical Bose–Einstein model. Results show that the free exciton energy of the GaAs core–shell agrees well with the known emission energy of zinc blende (ZB) bulk GaAs. Further analysis on the linear slope of the temperature dependence curve of photoluminescence emission energy at low temperatures shows that there is no difference between core–shell nanowires and bulk GaAs, strongly indicating that the grown NWs are indeed predominantly ZB in structure. The Raman modes show downshift and asymmetrical broadening, which are characteristic features of NWs. The downshift is attributed to lattice defects rather than the confinement or shape effect.     

The growth of GaAs and InAs dots on etched mesas: The effect of substrate temperature on mesa profile and surface morphology on dot distribution

The molecular beam epitaxy (MBE) growth of GaAs and InAs quantum dots on etched mesas has been studied using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The [0 1 1]-oriented mesas are etched into (1 0 0) GaAs substrates, exposing (5 3 3)B sidewall facets. At a substrate temperature of 610 °C a top (1 0 0) plane is seen to evolve on a ridge mesa structure. Alternatively, if the overgrowth is carried out at 630 °C no such facet is seen, and the top ridge remains unchanged during GaAs growth. By controlling the mesa shape, either ordered lines of dots can be grown or the dot density can be varied from <5×10⁸ cm⁻² to >1×10¹¹ cm⁻² on the same substrate in pre-defined regions. The dot distribution observed on the mesa sidewalls and top is discussed in terms of net migration of adatoms from different facets, underlying step density, step height and surface curvature of the mesa top.     

Fabrication of UV detectors based on ZnO nanowires using silicon microchannel

Aligned ZnO nanowires were grown by metal organic chemical vapor deposition on patterned silicon substrate. The shape of nanostructures was greatly influenced by the micropatterned surface. The aspect ratio, packing fraction and the number density of nanowires on top surface are around 10, 0.8 and 10⁷ per mm², respectively, whereas the values are 20, 0.3 and 5×10⁷ per mm², respectively, towards the bottom of the cavity. XRD patterns suggest that the nanostructures have good crystallinity. High-resolution transmission electron microscopy confirmed the single-crystalline growth of the ZnO nanowires along the [0 0 0 1] direction. Photosensitivity of the nanowires, grown on both top and bottom surface of the microchannel, was observed. However, the nanowires grown on bottom surface have shown better UV response with base line recovery at dark condition.     

Influence of growth temperature on growth of InGaAs nanowires in selective-area metal–organic vapor-phase epitaxy

Indium-rich InGaAs nanowires were grown on an InP (111)B substrate by catalyst-free selective-area metal–organic vapor phase epitaxy, and the growth-temperature dependence of growth rate and composition was studied. In particular, nanowire growth rate rapidly decreases as growth temperature increases. This tendency is opposite (for a similar temperature range) to that found in a previous study on selective-area growth of gallium-rich InGaAs nanowires. This difference between indium-rich and gallium-rich nanowires suggests that the influence of growth temperature on the growth of InGaAs nanowires is dependent on the group-III supply ratio. On the basis of previous experimental observations in InAs and GaAs nanowires, temperature dependence of nanowire growth rate and its dependence on group-III supply ratio are predicted. A guideline to determine the optimum growth conditions of InGaAs nanowires is also discussed.     

The influence of indium on the growth of GaN from solution under high pressure

The influence of significant fraction (10–50 mole%) indium in liquid gallium on GaN crystallization from a ternary Ga–In–N solution was analyzed. Crystallization experiments of GaN on GaN-sapphire templates from Ga–In solutions, at 1350–1450 °C, with prior to the growth seed wetting at 1500 °C, and 1.0 GPa N₂ pressure, without solid GaN source showed faster growth of GaN on the seed (by a factor of 1.5–2) than using pure gallium solvent. Nevertheless the new grown crystals were morphologically unstable. The instability was reduced by decrease of the wetting temperature down to 1100 °C or by omitting the wetting procedure entirely, which indicated that GaN dissolves much faster in Ga–In melt than in pure Ga and that the unstable growth was caused most likely by complete dissolution of GaN template before the growth. It was observed that the crystals grown on bulk GaN substrates did not show morphological instability observed for GaN-sapphire templates. The influence of indium on thermodynamic and thermal properties of the investigated system is discussed.     

Novel route to scalable synthesis of II–VI semiconductor nanowires: Catalyst-assisted vacuum thermal evaporation

Vacuum thermal evaporation, a conventional film fabricating technique, has been explored to synthesize II–VI semiconductor nanowires based on a catalyst-assisted vapor–liquid–solid (VLS) process. Low melting-point metals, such as bismuth and tin, can be used as catalysts by co-evaporating with desired semiconductor materials. As proof of the concept, CdTe, CdS, ZnSe and ZnS single crystalline nanowires have been successfully synthesized on a large scale by this method. The growth mechanism involved in the method has been discussed. Morphological, structural and optical properties of as-synthesized nanowires were characterized, revealing the high quality of the nanowires. The results indicate that the method presented here is a novel and general route to mass production of II–VI semiconductor nanowires, which can be possibly scaled up for industrial application at low cost, and extended to other material systems.