High quality GaN film overgrown on GaN nanorods array template by HVPE

The high density vertically aligned GaN nanorods array was fabricated by thermal evaporation of GaN powder with the assistance of HCl gas. The GaN nanorods array was used as template for GaN film growth by hydride vapor phase epitaxy (HVPE). The full width at half maximum values (FWHM) of high-resolution X-ray diffraction (HRXRD) rocking curves for the GaN film with GaN nanorods array template are 247 arc sec (002 reflection) and 308 arc sec (102 reflection), while those for the GaN film without GaN nanorods array template are 292 and 369 arc sec, respectively. This result indicates a significant reduction of dislocation density in the overgrown GaN film with GaN nanorods array template. Photoluminescence spectra measurements reveal the compressive strain relaxation and an improvement in the quality of the overgrown GaN film with GaN nanorods array template as compared to the regrown GaN film without GaN nanorods array template, which is consistent with the trend observed by HRXRD.     

Growth behavior of GaN nanoneedles with changing HCl/NH3 flow ratio

We grew one-dimensional GaN nanoneedles on AlN/Si(111) substrates at HCl/NH₃ gas-flow ratios of 1/20, 1/30, and 1/50 using the hydride vapor-phase epitaxy (HVPE) method. Field emission-scanning electron microscopy (FE-SEM) images of GaN nanoneedles show that the vertical growth rate of GaN nanoneedles increases with increasing gas-flow ratio, but there is little growth in the lateral direction. X-ray diffraction patterns indicate that GaN nanoneedles grew with c-axes oriented perpendicular to the substrate. The room-temperature PL spectrum of GaN nanoneedles was detected at 3.237 eV of near-band-edge transitions.     

Hydride vapour phase epitaxy growth and characterisation of GaN layers

A vertical hydride vapour phase epitaxial reactor was applied for the growth of GaN layers on (0001) sapphire. In this paper, the growth parameters and the results of optical investigations are reported. It is seen that the layers grown at high temperature have better crystallographic properties than those grown at 600–800°C, although the latter show a smoother surface. The absorption spectra exhibited a tail from the absorption edge down to about 1 eV that may be fitted by the Lukovsky model considering the presence of a level at about 1.2 eV from the conduction band. The cathodoluminescence spectra show three main emissions: the yellow band, a blue band (BB) centred at 2.8 eV and the near band edge recombination. The BB is mostly originated close to the layer/substrate interface and practically extinguished at the layer surface. It is seen that when the intensity of the BB increases that of the fundamental recombination decreases and vice versa.     

氢化气相外延氮化镓生长中气氛的作用研究

报告了氢化物气相外延技术中，在载气氮气氛中加入氢气对材料表面形貌及材料性质的影响。实验发现生长气氛中氛的存在会显著改进材料的质量，这种作用被归之于氢气氛下氮气在气相中的反应下降以及生长表面较低的氮的活动能力。     

In-situ X-ray studies of organometallic vapor phase epitaxy growth

In this paper we present an overview of the use of X-ray measurements to determine the atomic mechanisms of organometallic vapor phase epitaxy (OMVPE). Detailed information about OMVPE processes has been difficult to obtain because of the high pressure, chemically reactive environment present during growth. X-ray scattering measurements using very intense synchrotron X-ray sources have been uniquely productive in determining the structure of surfaces during OMVPE growth. For example, surface smoothness, step ordering, growth modes, growth rates and surface reconstructions have been determined. In addition, X-ray spectroscopy measurements have revealed much about the complicated gas phase behavior in the OMVPE reactor. From these scattering and spectroscopy measurements, a more complete model of OMVPE growth is being developed.     

An intercalated hybrid of polyacrylamide/layered double hydroxide prepared via in situ intercalative polymerization

A new intercalated hybrid of polyacrylamide (PAM)/layered double hydroxide (LDH) prepared via in situ intercalative polymerization procedure is reported. LDH with counterion ion of nitrate or dodecyl sulfate anion was employed for comparison. The obtained PAM/LDH hybrid was characterized by X-ray diffraction, infrared spectra, differential scanning microcalorimetry and X-ray photoelectron spectrum. The results reveal that the LDH modified with dodecyl sulfate anion can be used to obtain an intercalated hybrid, whereas PAM polymer chains can not enter the interlayer space of LDH with nitrate anion as counterion ion.     

Preparation of zeolite T membranes by microwave-assisted in situ nucleation and secondary growth

Zeolite T membranes were firstly prepared on the α-Al₂O₃ tubes by microwave-assisted in situ nucleation and secondary growth. The obtained membranes were characterized by XRD, SEM, single gas permeation, and pervaporation (PV). In the PV dehydration of ethanol and 2-propanol, the as-synthesized membranes displayed high separation performance. For the 90 wt.% alcohol/water mixtures at 338 K, the water flux reached 1.23 kg m^− 2 h^− 1 for the dehydration of ethanol and 1.52 kg m^− 2 h^− 1 for the dehydration of 2-propanol; both separation factors were higher than 10, 000.     

Polarity conversion of hydride vapor phase epitaxy growing GaN via growth interruption modulation

GaN films were deposited by hydride vapor phase epitaxy with and without adopting growth interruption modulation (GIM). The surface morphologies of these samples were observed by atomic force microscopy. After chemical etching, the surface morphology of GaN film grown directly on sapphire changed greatly and turned out to be N-polarity, which could be changed into Ga-polarity when growing via interruption modulation. Photoluminescence spectra showed that optical property of Ga-polar film was better than that of N-polar film. High resolution X-ray diffraction revealed the high crystalline quality GaN film grown by using the GIM method. The polarity conversion was the result of surface reconstruction when adopting GIM method.     

Organometallic vapor phase epitaxy (OMVPE)

Organometallic vapor phase epitaxy (OMVPE) has emerged in this past decade as a flexible and powerful epitaxial materials synthesis technology for a wide range of compound–semiconductor materials and devices. Despite its capabilities and rapidly growing importance, OMVPE is far from being well understood: it is exceedingly complex, involving the chemically reacting flow of mixtures of organometallic, hydride and carrier-gas precursors. Recently, however, OMVPE technologies based on high-speed rotating disk reactors (RDRs) have become increasingly common. As fluid flow in these reactors is typically cylindrically symmetric and laminar, its effect on the overall epitaxial growth process is beginning to be unraveled through quantitative computer models. In addition, over the past several years, a combination of well-controlled surface science and RDR-based growth-rate measurements has led to a richer understanding of some of the critical gas and surface chemistry mechanisms underlying OMVPE. As a consequence, it is becoming increasingly possible to develop a quantitative and physically based understanding of OMVPE in particular chemical systems. In this article, we review this understanding for the important specific case of AlGaAs OMVPE in an RDR under conditions used for growing typical device heterostructures. Our goal is to use typical growth conditions as a starting point for a discussion of fundamental physical and chemical phenomena, beginning with the fluid flow through an RDR and ending with the chemical reactions on the surface. By focusing on one particularly important yet relatively simple specific case, this review differs from more comprehensive previous reviews. Viewed as a case study, though, it complements these previous reviews by illustrating the wide diversity of research that is related to OMVPE. It can also serve as a good starting point for the development and transfer of insights into other more complex cases, such as: OMVPE of materials families containing Sb, P or N species, of other devices types, and in other more complex reactor geometries.     

The influence of reactor pressure on qualities of GaN layers grown by hydride vapor phase epitaxy

Influence of reactor pressure on the quality of GaN layers grown by hydride vapor phase epitaxy (HVPE) has been studied. With the reactor pressure decreasing from 7 to 5 × 10⁴ Pa, improvements in structural, optical, and electrical properties of the GaN films have been observed.An investigation of the surface morphology of the GaN films reveals that the improvements arise from the change of the growth mode from an island-like mode at high pressures to a step-flow one at low pressures. These results clearly indicate that the reactor pressure, similar to the growth temperature, is one of the important parameters to control the qualities of HVPE-GaN epilayers.     

FAU-type zeolite membranes synthesized by microwave assisted in situ crystallization

FAU-type zeolite membranes were prepared by an “in situ aging-microwave synthesis” (AM) method using a clear solution with the molar composition of 70Na₂O: 1Al₂O₃: 20SiO₂: 2000H₂O. After two-stage AM synthesis, a defect-free FAU zeolite layer consisted of uniform zeolite crystals was formed on the support surface. The Si/Al ratio was ca. 1.5. The single-gas permeation and single-liquid vapor permeation properties of the as-synthesized zeolite membranes were investigated. The permselectivity of H₂ and N₂ was as high as 4.25 for FAU-type zeolite membranes. Pervaporation measurements were carried out for the dehydration of ethanol and isopropanol aqueous solutions. FAU-type zeolite membranes displayed relatively high permeation flux and water-selectivity.     

Growth mode control and micro-Raman characterization of triangular GaN nanowires in a vapor phase epitaxy process

The synthesis of single-crystalline GaN nanowires on c-Al₂O₃ substrates using a vapor phase epitaxy process was studied. The GaN nanowires synthesized at a high NH₃ gas flow rate and thus with a sufficient supply of the N source grew via the vapor-solid mechanism, while those synthesized at a low NH₃ gas flow rate grew via the vapor-liquid-solid mechanism. The internal stress between the nanowires and the substrate was investigated using micro-Raman spectroscopy. The X-ray diffraction indicated that the triangular GaN nanowires have a single-crystalline hexagonal structure.     

Epitaxial growth of Cr2O3 thin film on Al2O3 (0001) substrate by radio frequency magnetron sputtering combined with rapid-thermal annealing

We prepared epitaxially grown Cr₂O₃ thin films on Al₂O₃ (0001) substrate by using radio frequency magnetron sputtering at room temperature followed by a rapid-thermal annealing process. It is shown that the phase and the crystallinity of as-grown samples depend on the flow ratios of the working gas (Ar/O₂). X-ray diffraction (XRD) results show that oxygen-rich CrO₃ phase having preferred orientation is formed when sputter-grown at room temperature under the working gas (Ar/O₂) flow ratios of 9:1 and 7:3. XRD Φ-scanning results exhibit that annealing causes the oxygen-rich CrO₃ phase to transform into epitaxial Cr₂O₃ phase, which is confirmed by X-ray photoemission spectroscopy. The samples grown at the gas flow ratio of 9:1 exhibit very smooth surfaces with root mean square roughness of 0.1-0.3 nm.     

Silicon surface passivation by hot-wire CVD Si thin films studied by in situ surface spectroscopy

Silicon thin films can provide an excellent surface passivation of crystalline silicon (c-Si) which is of importance for high efficiency heterojunction solar cells or diffused emitter solar cells with well-passivated rear surfaces. Hot-wire chemical vapor deposition (hot-wire CVD) is an attractive method to synthesize Si thin films for these applications as the method is ion-bombardment free yielding good quality films over a wide range of deposition rates. The properties of the interface between hot-wire CVD Si thin films and H-terminated c-Si substrates have been studied during film growth by three complementary in situ techniques. Spectroscopic ellipsometry has been used to determine the optical properties and thickness of the films, whereas information on the H-bonding modes and H-depth profile has been obtained by attenuated total reflection infrared spectroscopy. Second-harmonic generation (SHG), a nonlinear optical technique sensitive to surface and interface states, has been used to probe two-photon resonances related to modified Si-Si bonds at the interface. By correlating the observations with ex situ lifetime spectroscopy experiments the growth and surface passivation mechanism of the Si films are discussed.     

Annealing effect on cadmium in situ doping of chemical bath deposited PbS thin films

This paper describes the effect of annealing on PbS and Cd-doped PbS thin films prepared by chemical bath deposition at different bath temperatures (T_b). The X-ray diffraction (XRD), optical absorption, scanning electron microscopy, and energy dispersive X-ray (EDX) analyses have been performed to explore the properties of PbS and PbCdS films. From the XRD measurements, the particle size (D) of as-deposited PbS and PbCdS films is estimated to be 22 (27) and 12 (9) nm, respectively, for a T_b of 75 (85) °C. A reduction in D was noticed upon annealing the films at 200 °C, irrespective of the T_b and the doping. The optical band gap energy (E_g) of as-deposited PbS films grown at different T_b is found to be in the range of 1.22-1.42 eV. Doping of PbS with Cd and annealing have led to increase in E_g up to 2.61 (2.66) eV. Optical studies revealed prominent blue shifts in the E_g of as-deposited and annealed films due to quantum confinement effect. The addition of Cd into PbS was confirmed by EDX analysis.     

Oxygen pressure dependent VO2 crystal film preparation and the interfacial epitaxial growth study

High quality VO₂ crystal films have been prepared on sapphire substrates by pulsed laser deposition method and the effects of oxygen pressure on the crystal phase structure are investigated. Results indicate that the phases and microstructures of VO₂ films are strongly sensitive to oxygen pressure. High oxygen pressure tends to form coarse B-VO₂ nanocrystals while low pressure favors a flat M1-VO₂ film epitaxial growth. X-ray diffraction φ-scan patterns confirm the [020] epitaxial growth orientation of the M1-VO₂ film and the in-plane lattice epitaxial relationship at the interface is also examined. Raman spectra indicate that M1-VO₂ phase has much stronger Raman scattering modes than B-VO₂, and the clear phonon modes further confirm the idea stoichiometry of VO₂ crystal film. Infrared transmittance spectra as the function of temperature are recorded and the results show that M1-VO₂ crystal films undergo a distinct infrared transmittance variation across metal insulator transition boundary, while B-VO₂ exhibits negligible thermochromic switching properties in the temperature range concerned. The pronounced phase transition behavior of the M1-VO₂ crystal film makes it a promising candidate for optical filter/switch and smart window applications in the future.     

The origin of wing tilt for uncoalesced GaN grown on maskless grooved sapphire fabricated by wet chemical etching

In this paper, wing tilt was detected by high resolution X-ray rocking curve for uncoalesced GaN epilayer grown on maskless periodically grooved sapphire fabricated by wet chemical etching. Stress distribution was characterized by the frequency shift in micro-Raman spectroscopy measurement. It shows inhomogeneous stress distribution between the mesa and wing region, which is in agreement with the finite-element analysis simulations. Meanwhile, the wing tilt calculated by finite-element analysis agrees well with the rocking curve result. The results show that the different relaxation of stress causes inhomogeneous displacements between the mesa and wing region is the main reason of wing tilt formation.     

Formation of thin β-FeSi2 template layer for the epitaxial growth of thick film on Si (111) substrate

For the epitaxial growth of thick β-FeSi₂ films, we fabricated ultrathin β-FeSi₂ template layers (thinner than 20 nm) on Si (111) substrates with different methods. Surface morphology and crystallinity of the template layers were found to be dependent on the surface conditions of the substrate and the fabrication method. It was revealed that to form a smooth and continuous template, a hydrogen-terminated surface was better than that covered with a several-nanometer oxide layer. Using this surface, continuous (110)/(101)-oriented epitaxial template was obtained by depositing 6-nm iron at 400 °C and subsequent in situ annealing at 600 °C in MBE chamber, namely, a reaction deposition epitaxy (RDE) method. Co-deposition of iron and silicon with atomic ratio of Fe/Si=1/2 allowed the forming of template layers at further low temperature. Co-deposited template layers exhibited better crystallinity and morphology than those prepared by RDE. By using the optimized template layer, we succeeded in growing high-quality thick β-FeSi₂ films on Si (111) substrates with sharp β-FeSi₂/Si interface.     

Nanocone SiGe antireflective thin films fabricated by ultrahigh-vacuum chemical vapor deposition with in situ annealing

In this study, we fabricated nanocone-presenting SiGe antireflection layers using only ultrahigh-vacuum chemical vapor deposition. In situ thermal annealing was adopted to cause SiGe clustering, yielding a characteristic nanocone array on the SiGe surface. Atomic force microscopy indicated that the SiGe nanocones had uniform height and distribution. Spectrophotometric measurements revealed that annealing at 900 °C yielded SiGe thin films possessing superior antireflective properties relative to those of the as-grown SiGe sample. We attribute this decrease in reflectance to the presence of the nanostructured cones. Prior to heat treatment, the mean reflectance of ultraviolet rays (wavelength < 400 nm) of the SiGe thin film was ca. 61.7%; it reduced significantly to less than 28.5% when the SiGe thin film was annealed at 900 °C. Thus, the drop in reflectance of the SiGe thin film after thermal treatment exceeded 33%.     

In-situ reflection high-energy electron diffraction study of epitaxial growth of Cu on NaCl (100) under oblique angle vapor deposition

Epitaxial growth of copper on annealed NaCl(100) surface was carried out using thermal evaporation at an oblique angle of incidence (75 ± 5)° with respect to the substrate normal. The substrate was kept at a temperature of (150 ± 5)°C. The crystalline structure of the Cu film was studied in situ by reflection high energy electron diffraction at various deposition times. We observed that the film grows through nucleation of epitaxial islands followed by coalescence and then flattening of the film. The chevron shaped diffraction patterns formed by the refraction effect of electrons were used to identify the crystal facets. With longer deposition times, instead of columnar structures, a continuous epitaxial film was formed despite the oblique angle incidence of the vapor. The morphology of the final film was characterized ex situ by atomic force microscopy and shows L-shaped pores asymmetric with respect to the vapor incident direction.