Metal organic vapour phase epitaxy of MgO films grown on c-plane Sapphire

Metal organic vapour phase epitaxy (MOVPE) has been used to epitaxially grow MgO films on c-plane sapphire substrates. Bismethylcyclopentadienyl magnesium (MCP₂Mg) and nitrous oxide (N₂O) were used as the magnesium and the oxygen source, respectively, with nitrogen (N₂) as the carrier gas. The dependence of the growth rate on the partial pressure of magnesium and on the growth temperature was investigated. The growth rate increases with the magnesium partial pressure. The morphological and structural properties of MgO films were investigated using atomic force microscopy and X-ray diffraction. The structural properties are strongly dependent on the growth temperature in the range 400–800 °C. (1 1 1)-oriented MgO layers are observed at growth temperatures above 600 °C whereas no diffraction peak is found at lower growth temperatures. The atomic force microscopy (AFM) images reveal a smooth surface morphology.     

Growth of ZnO crystal by self-flux method using Zn solvent

Zinc oxide (ZnO) single crystal was grown, for the first time, by the self-flux method using a high-purity zinc solvent saturated with oxygen. ZnO crystals were successfully grown in the solvent by moving a growing crystal slowly, at about 17 mm/day along a temperature gradient (1.5 °C/mm) in a furnace, from 1050 to 500 °C. Hexagonal single crystals 1–3 mm in length and 0.5–1 mm in thickness were obtained. Energy-dispersive X-ray diffraction, secondary ion mass spectrometry, and photoluminescence confirmed that the purity and crystallinity of the ZnO crystals grown in this work were high.     

Growth of high-quality ZnO single crystals by seeded CVT using the newly designed ampoule

The high-quality ZnO single crystals were grown by seeded chemical vapor transport (CVT) in a newly designed ampoule using carbon as a transport agent. The well-faceted crystal of about 5×5×5 mm³ can be grown reproducibly. Secondary ion mass spectroscopy (SIMS) analysis, X-ray rocking curve (XRC) and photoluminescence (PL) measurements demonstrate that the grown single crystal is of high purity and high crystallinity.     

Initial transient in Zn-doped InSb grown in microgravity

Three Zn-doped InSb crystals were directionally solidified under microgravity conditions at the International Space Station (ISS) Alpha. The distribution of the Zn was measured using SIMS. A short diffusion-controlled transient, typical for systems with k >1 was demonstrated. Static pressure of ∼4000 N/m² was imposed on the melt, to prevent bubble formation and de-wetting. Still, partial de-wetting has occurred in one experiment, and apparently has disturbed the diffusive transport of Zn in the melt.     

Preparation of single-crystalline ZnO films on ZnO-buffered a-plane sapphire by chemical bath deposition

High-quality zinc oxide (ZnO) films were successfully grown on ZnO-buffered a-plane sapphire (Al₂O₃ (1 1 2¯ 0)) substrates by controlling temperature for lateral growth using chemical bath deposition (CBD) at a low temperature of 60 °C. X-ray diffraction analysis and transmission electron microscopy micrographs showed that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. Rocking curves (ω-scans) of the (0 0 0 2) reflections showed a narrow peak with full width at half maximum value of 0.50° for the ZnO film. A reciprocal space map indicated that the lattice parameters of the ZnO film (a=0.3250 nm and c=0.5207 nm) were very close to those of the wurtzite-type ZnO. The ZnO film on the ZnO-buffered Al₂O₃ (1 1 2¯ 0) substrate exhibited n-type conduction, with a carrier concentration of 1.9×10¹⁹ cm⁻³ and high carrier mobility of 22.6 cm² V⁻¹ s⁻¹.     

Synthesis,conversion and comparison of the photocatalytic and electrochemical properties of ZnSe·N2H4 and ZnSe microrods

Novel ZnSe·N₂H₄ complex microrods with ∼2 μm in length and 100∼200 nm in diameter were successfully prepared by the solvothermal method at 110°C for 10 h, employing ZnAc₂·2H₂O and Se powders as the reactants, N₂H₄·H₂O as the reductant and medium. Experiments showed that the as‐obtained complex could be further converted into pure hexagonal ZnSe in an ethanol medium at 180 °C for 10 h, and the morphology hardly changed. The as‐prepared products were characterized by X‐ray powder diffraction (XRD), Energy dispersive spectrum (EDS), IR spectrum, Thermogravimetric (TG) analysis and Field emission scanning electron microscopy (SEM). Also, their photocatalytic degradation and electrochemical property were compared. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Floating-zone growth of large high-quality CoAl2O4 single crystals

We report the first successful floating-zone growth of high-quality CoAl₂O₄ single crystals with volume up to 1 cm³ free from inclusions and sub-grains. The neutron rocking curves of the CoAl₂O₄ crystal have the width of about 0.30 degree proving the excellent quality of the grown samples. X-ray synchrotron experiments show that crystals have spinel structure with the lattice constant a₀=8.09853(1) Å. Magnetization measurements give the effective magnetic moment μ_eff=4.63 μ_B per Co⁺² ion in a good agreement with previous measurements on ceramic samples.     

Bulk GaN crystals grown by HVPE

We succeeded in preparing very thick c-plane bulk gallium nitride (GaN) crystals grown by hydride vapor phase epitaxy. Growth of the bulk GaN crystals was performed on templates with 3 μm GaN layer grown by metal organic chemical vapor deposition on (0 0 0 1) sapphire substrates. Colorless freestanding bulk GaN crystals were obtained through self-separation processes. The crystal's diameter and thickness were about 52 and 5.8 mm, respectively. No surface pits were observed within an area of 46 mm diameter of the bulk GaN crystal. The dislocation density decreased with growth direction (from N-face side to Ga-face side) and ranged from 5.1×10⁶ cm⁻² near the N-face surface to 1.2×10⁶ cm⁻² near the Ga-face. A major impurity was Si, and other impurities (O, C, Cl, H, Fe, Ni and Cr) were near or below the detection limits by SIMS measurements.     

Strain-reduced GaN thick-film grown by hydride vapor phase epitaxy utilizing dot air-bridged structure

A 300 μm GaN thick-film, in diameter 1.5 in, was demonstrated without any crack by hydride vapor phase epitaxy (HVPE) growth. The technique used in relaxing the residual stress caused by differences of thermal expansion coefficients (TEC) and lattice constants between GaN and sapphire substrate to prevent GaN film from crack is called a dot air-bridged structure. After the laser lift-off process, 300-μm-thick freestanding GaN wafer, in diameter 1.5 in, could be fabricated. The compressive stress in the dot air-bridged structure was measured by micro-Raman spectroscopy with the E₂(high) phonon mode. The compressive stress could be reduced to as small as 0.04 GPa, which could prevent the crack during the epitaxial process for GaN growth by HVPE. It is important to obtain a large-area crack-free GaN thick-film, which can be used for fabricating freestanding GaN wafer.     

Synthesis,characterization and optical properties of ZnO nanoparticles with controlled size and morphology

Zinc oxide monodispersed nanoparticles were synthesized using a modified polyol process without any requirement to use a catalyst or calcination step at high temperature. The morphology and the size of the resulting oxide particles were adjusted by using several synthesis parameters (temperature, alkaline ratio, hydrolysis ratio, etc.). The increasing of the alkaline ratio results in a great change of the elaborated particles morphology that evolved from irregular and anisotropic forms (conical, nanorod-like and elliptical) to spherical one. A growth mechanism of these particles was proposed on the basis of zincite crystal structure and the morphology evolution as a function of the synthesis parameters. The photoluminescence spectra show UV-excitonic and visible emission bands. The strongest intensity of the visible emission was observed in nanorod-like particles, which implies an increased fraction of oxygen vacancies in this sample. The rod-like particles with 1 μm length show the dominant UV-emission, which evidences their improved stoichiometry.     

Bulk single-crystal growth of ternary AlxGa1−xN from solution in gallium under high pressure

We have successfully grown bulk, single crystals of Al_xGa_1−xN with the Al content x ranging from 0.5 to 0.9. Samples were grown from Ga melt under high nitrogen pressure (up to 10 kbar) and at high temperature (up to 1800 °C) using a gas pressure system. The homogeneity and Al content of the crystals were investigated by X-ray diffraction and laser ablation mass spectrometry. On the basis of the high-pressure experiments, the corresponding pressure–temperature (p–T) phase diagram of Al–Ga–N was derived. The bandgap of the material was determined by the femtosecond two-photon absorption autocorrelation method and is equal to 5.81±0.01 eV for the Al_0.86Ga_0.14N crystals.     

Study of Te inclusions in CdMnTe crystals for nuclear detector applications

The concentration, size and spatial distribution of Te inclusions in the bulk of CdMnTe crystals mined from two batches of ingots were studied. An isolated planar layer decorated with Te inclusions was identified in CdMnTe crystals from the second ingot. The internal electric field of a CMT crystal was probed by infrared (IR) imaging employing Pockels electro-optic effect. The effect of an isolated plane of Te inclusions on the internal electric-field distribution within the CdMnTe crystal was studied. Space charge accumulation around the plane of Te inclusions was observed, which was found to be higher when the detector was reverse-biased. The effects of the plane of Te inclusions on the electric-field distribution within the CdMnTe crystal, and the quality of CdMnTe crystals for nuclear detector applications are discussed.     

Properties of Ge-doped,high-quality bulk GaN crystals fabricated by hydride vapor phase epitaxy

We investigated the properties of Ge-doped, high-quality bulk GaN crystals with Ge concentrations up to 2.4×10¹⁹ cm⁻³. The Ge-doped crystals were fabricated by hydride vapor phase epitaxy with GeCl₄ as the dopant source. Cathodoluminescence imaging revealed no increase in the dislocation density at even the highest Ge concentration, with values as low as 3.4×10⁶ cm⁻². The carrier concentration, as determined by Hall measurement, was almost identical to the combined concentration of Ge and unintentionally incorporated Si. The electron mobilities were 260 and 146 cm² V⁻¹ s⁻¹ for n=3.3×10¹⁸ and 3.35×10¹⁹ cm⁻³, respectively; these values are markedly larger than those reported in the past for Ge-doped GaN thin films. The optical absorption coefficient was quite small below the band gap energy; it slightly increased with increase in Ge concentration. Thermal conductivity, estimated by the laser-flash method, was virtually independent of Ge concentration, maintaining an excellent value around 2.0 W cm⁻¹ K⁻¹. Thermal expansion coefficients along the a- and m-axes were approximately constant at 5.0×10⁻⁶ K⁻¹ in the measured doping concentration range.     

Morphology and photoluminescence properties of ZnO nanostructures fabricated with different given time of Ar

ZnO nanostructures were grown on Au‐coated Si (100) substrates by carbonthermal reduction method with the help of Ar at the beginning of growth. The structural and optical properties of ZnO nanostructures strongly depended on the supply time of Ar. When the given time of Ar gas current was 90s, sample was ZnO nanowires with hexagonal morphology. The Raman spectroscopy revealed the low level of oxygen vacancies and Zn interstitials in samples. Room temperature photoluminescence (PL) spectra exhibited the intensity of green emission increased on the condition of rich oxygen (decrease given time of Ar) and the nanowire had strongest intensity of UV emission compared with other nanostructures. Green emission is ascribed to the electron transition from the bottom of the conduction band to the antisite defect O_Zn level. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of calcium lithium tantalum gallium garnet single crystal

A new disordered garnet single crystal, calcium lithium tantalum gallium garnet (CLTGG) was grown by the Czochralski method. The lattice parameter of the crystal has been determined to be a=12.508±0.001 Å by X-ray powder diffraction (XRPD). The melting point of CLTGG was measured to be 1548 °C. The crystal possesses a wide transmission range from the ultraviolet to infrared, which is advantageous for applications as a laser host material. The refractive indices were also measured by the V-prism method.     

Growth,thermal and optical properties of a new nonlinear optical crystal: ZnBi2B2O7

Single crystals of ZnBi₂B₂O₇ (ZBBO) have been successfully grown by the top-seeded growth method from a high-temperature melt. The crystal was colorless and transparent with size of 15×10×5 mm³. The orientation of ZBBO crystal has been discussed. The melting point, molar enthalpy of fusion, and molar entropy of fusion of the crystal were determined to be 964.02 K, 110680.36 J mol⁻¹, and 113.92 J K⁻¹ mol⁻¹, respectively. The transparency range of the crystal extends from 370 to 2100 nm.     

Synthesis and ammonia sensing property of Ag3CuS2 nanocages obtained from Cu7S4 18-facet hollow nanopolyhedra

Ag₃CuS₂ nanocages were successfully fabricated for the first time via a convenient ion-exchange route by Ag⁺ reacting with Cu₇S₄ 18-facet hollow nanopolyhedra. The average size and shell thickness of Ag₃CuS₂ nanocages were around 400 and 30 nm, respectively. Room-temperature response of Ag₃CuS₂ nanocages to ammonia was investigated by photoluminescence-type sensor. Sensing results suggested that these hollow-structured Ag₃CuS₂ exhibited better performances including higher sensitivity, shorter response and recovery time than their rod-shape counterparts. A possible hole trapping mechanism was proposed.     

Surface-diffusion induced growth of ZnO nanowires

The growth rate of ZnO nanowires grown epitaxially on GaN/sapphire substrates is studied. An inverse proportional relation between diameter and length of the nanowires is observed, i.e., nanowires with smaller diameters grow faster than larger ones. This unexpected result is attributed to surface diffusion of ZnO admolecules along the sidewalls of the nanowires. In addition, the unique c-axis growth of ZnO nanowires, which does not require a catalytic particle at the tip of the growing nanowires is discussed by taking into account polarity, surface free energy, and ionicity. Activation energies of the nanowire growth are determined as well.     

Selective area metal-organic vapor-phase epitaxy of InN,GaN and InGaN covering whole composition range

To investigate mask effects on InGaN selective area metal-organic vapor-phase epitaxy (SA-MOVPE), in-plane thickness profiles of InGaN were investigated with various indium contents covering between InN and GaN. A numerical simulation employing vapor-phase diffusion (VPD) model was also carried out for the quantitative analysis of VPD effect. At the growth temperatures of 650 and 700 °C, the indium content in the vapor phase and that in the solid phase exhibited almost linear relationship, suggesting that the growth of InGaN can be approximated as the superposition of the growth of InN and GaN. The effective vapor-phase diffusion length D/k_s of GaN was much smaller than InN. The profile of the InGaN growth rate in the selective area became more gradual as the solid indium content increased, and the trend seems to be the linear interpolation between the profiles of GaN and InN. However, as the indium content increases, deposition selectivity between mask and crystal surface become degenerated, and the VPD effect was almost canceled when the solid indium content exceeds 0.5. Although further improvement on the growth conditions is necessary to improve selectivity, basic information for the design of the SA-MOVPE of InGaN has been obtained, which will contribute to InGaN-based monolithically integrated multi-wavelength devices.     

Carbon reduction and antimony incorporation in InGaAsSb films grown by metalorganic molecular beam epitaxy using tris-dimethylaminoantimony

InGaAsSb layers nearly lattice-matched to InP were grown by metalorganic molecular beam epitaxy using tris-dimethylaminoantimony (TDMASb). Secondary-ion mass spectroscopy measurements revealed that TDMASb is useful not only as an Sb source but also as an additive that reduces the incorporation of C into the film from group-III metalorganic sources. In the room-temperature photoluminescence spectrum, the incorporation of Sb into InGaAs shifted the peak wavelength from 1.66 to 1.75 μm and, simultaneously, the peak intensity of InGaAsSb became more than twice that of InGaAs.