Bulk GaN single crystals: growth conditions by flux method

Hexagonal GaN platelet crystals with a size of 1–4 mm have been grown by a Li-based flux method. The influence of growth conditions such as the molar ratio of starting materials, temperature, pressure, the position of Li₃N in the crucible on the growth of GaN single crystals was studied. The quality of GaN single crystal was checked by optical microscope and X-ray rocking curve.     

AlN bulk single crystal growth on 6H-SiC substrates by sublimation method

Large and thick AlN bulk single crystals up to 43 mm in diameter and 10 mm in thickness have been successfully grown on 6H-SiC (0 0 0 1) substrates by the sublimation method using a TaC crucible. Raman spectrum indicates that the polytype of the grown AlN single crystals is a Wurtzite-2H type structure, and the crystals do not include any impurity phases. The quality at the top of the crystal improves as crystal thickness increases along the 〈0 0 0 1〉 direction during growth: a low etch pit density (7×10⁴ cm⁻²) and a small full width at half maximum for a 0002 X-ray rocking curve (58 arcsec) have been achieved at a thickness of ∼8 mm. The possible mechanism behind the improvement in the AlN crystal quality is also discussed.     

Growth behaviour of bulk GaN single crystals grown with various flux ratios using solvent‐thermal method

Bulk GaN single crystals were grown using a solvent‐thermal method. They were grown for 200 h at 600 °C and 800 °C using 8 MPa of N₂ gas and 1–3 mm sized pyramid GaN single crystals. Pure Na, NaN₃ and Ca were used as the flux. The mole fraction of the [flux]/([flux] + [Ga]) was 0.30–0.67. The growth behavior differed according to the flux ratio. The quality of the bulk GaN single crystals was improved by increasing the flux ratio. The bulk GaN single crystals formed by spontaneous nucleation were deposited on the BN crucible wall and bottom during the first step of synthesis. The wurtzite structure of the GaN grown single crystal was confirmed by x‐ray diffration. The chemical composition was analyzed by electron probe microanalysis. The quality and optical properties of the GaN single crystal were examined by Raman spectroscopy and photoluminesence analysis. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influences of supersaturation on LPE growth of GaN single crystals using the Na flux method

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.     

基于钠助熔剂法的GaN单晶生长研究进展

宽禁带氮化镓(GaN)材料以其独特的性质和应用前景成为国内外研究的热点，高质量GaN单晶衬底的制备是获得性能优异的光电子器件和功率器件的基础。钠助熔剂法生长条件温和，易获得高质量、大尺寸的GaN单晶，是一种具有广阔商业化前景的GaN单晶生长方法。钠助熔剂法自20世纪90年代末期被发明以来，经过20多年的发展，钠助熔剂法生长的晶体在尺寸与质量上都取得了长足的进步。本文从晶体生长原理和关键工艺(籽晶选择、温度梯度以及添加剂)等方面综述了钠助熔剂法生长GaN单晶研究进展，并对其面临的挑战和未来发展趋势进行了展望。     

Growth of high-purity ZnTe single crystals by the sublimation travelling heater method

A travelling heater method (THM) was developed to grow high-purity ZnTe from the vapor phase. This crystal growth method is called the “sublimation THM”. The temperature of the sublimation interface was set at 815°C and the temperature of the growth interface was varied from 785 to 800°C. The growth rate was 3 mm/day. Under these conditions, it was found that the growth process was mainly due to surface nucleation. Characteristics of the crystals were compared with those of solution-THM and vapor phase epitaxially grown crystals. The free-exciton line at 2.381 eV strongly appears and a doublet structure in neutral- acceptor bound exciton at 2.375 eV is clearly resolved with splitting energy of about 0.7 meV. We thus conclude that the THM from the vapor phase is suitable for preparing ZnTe single crystals which have excellent luminescent properties.     

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.     

沿[1-100]方向升华法生长6H-SiC单晶

本文采用升华法沿着垂直于c轴方向的[1-100]方向生长6H-SiC单晶.利用光学显微镜对晶体表面及腐蚀后的晶片进行观察,发现沿[1-100]方向生长出的单晶与传统方法沿[0001]方向生长单晶有很多的不同之处,多型对于籽晶的继承性非常强,但是在生长过程中多型夹杂不会发生,该方法生长的晶体中没有发现螺位错(微管)缺陷.     

Evidence of free carrier concentration gradient along the c-axis for undoped GaN single crystals

Results of measurements of infrared reflectivity and micro-Raman scattering on the undoped GaN high pressure grown single crystals are reported. These crystals have usually a high electron concentration due to unintentional doping by oxygen. We show, by the shift of the plasma edge (infrared reflectivity measurements), that the free electron concentration is always higher on the (0 0 0  )N face of the GaN single crystal than on the (0 0 0 1)Ga face. In order to determine the profile of the free carrier concentration, we performed transverse micro-Raman scattering measurements along the (0 0 0 1) c-axis of the crystal with spatial resolution of 1 μm. Micro-Raman experiments give a quantitative information on the free carrier concentration via the longitudinal optical phonon–plasmon (LPP) coupling modes. Thus, by studying the behavior of the LPP mode along the c-axis, we found the presence of a gradient of free electrons. We suppose that this gradient of electrons is due to the gradient of the main electron donor, in undoped GaN single crystals, i.e. oxygen impurity. We propose a growth model which explains qualitatively the incorporation of oxygen during the growth of GaN crystal under high pressure of nitrogen.     

Floating zone growth and characterization of ruby single crystals

Large, high optical quality single crystals of ruby have been grown successfully by the floating zone method under air atmosphere. The size of the grown crystal is typically 60‐70 mm in length and 7‐8 mm in diameter. The obtained crystals were red and did not have any macroscopic defects such as cracks and inclusions. Grown crystals were characterized by powder X‐ray diffraction (XRD) methods, polarized optical microscopy, scanning electron microscopy (SEM). The absorption and fluorescence spectra were measured at room temperature and the dielectric constant measurements of ruby crystals were also presented. Defects occurring in single crystals of ruby during crystal growth by floating zone method are described, and their correlation with the growth parameters is discussed. The origin and control of these defects in grown crystals were studied and the optimum method was proposed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CdSe单晶体的生长及其特性研究

本文报道了用改进的垂直气相法(多级提纯垂直气相法)生长富Cd的CdSe单晶体,并对晶体的性能进行了观测,其电阻率为107Ωcm量级,电子陷阱浓度为108cm-3量级,第一次报道了(110)面的腐蚀形貌。结果表明：采用这种方法制备CdSe单晶,设备简单,易于操作,在提纯和生长过程中不需要转移原料,有利于减少晶体中的杂质含量,降低位错密度,改善晶体的电学性能。多级提纯垂直气相法是一种有前途的CdSe单晶体生长的新方法。     

Bulk growth of gallium nitride: challenges and difficulties

The present status of the GaN bulk growth by High Pressure Solution (HPS) method and combination of HPS and Hydride Vapor Phase Epitaxy (HVPE) methods is reviewed. Up to now the spontaneous high pressure solution growth of GaN results in crystals having habit of hexagonal platelets of surface area of 3 cm² or needles with length up to 1 cm. Recently, the platelets and needles have been used as seeds for the HVPE growth. On the other hand, the LPE technique under pressure with pressure‐grown GaN (hp‐GaN), GaN/sapphire template, patterned GaN/sapphire template and free standing HVPE GaN as seeds has been examined and developed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ammonothermal epitaxy of wurtzite GaN using an NH4I mineralizer

Purely wurtzite phase needle crystals and epitaxial layers of GaN were grown by the ammonothermal method using an NH₄I mineralizer. The inclusion of zincblende phase GaN was effectively eliminated by increasing the growth temperature higher than 500 °C. Accordingly, an approximately 20-μm-thick GaN epitaxial layer was achieved on the Ga-polar face of a c-plane GaN seed wafer at 520 °C. Although the characteristic deep state emission band dominated the room temperature photoluminescence spectrum, the near-band-edge emission of GaN was observed for both the needle crystals and the epitaxial layers. These results encourage one to grow better quality GaN crystals at a high growth rate under high-temperature growth conditions.     

Preparation and characterizations of bulk GaN crystals

The growth conditions and mechanism of hexagonal GaN platelet crystals by Li flux were studied. The experimental results confirmed that these crystals crystallized from Li–Ga–N liquid phase. Photoluminescence (PL) spectra and Raman scattering spectrum of the crystals were obtained, which show that GaN crystals obtained by this method possess good crystalline quality.     

Growth and optical absorption studies on potassium dihydrogen phosphate single crystals

Growth of bulk nonlinear optical (NLO) single crystals gained new significance with the advent of solid‐state laser sources for opto‐electronic applications. An optically transparent crystal of potassium dihydrogen phosphate (KDP) has been grown from aqueous solution along (001) plane with the aid of modified growth assembly of Sankaranarayanan‐Ramasamy (SR) Method. The evaporation rate was controlled and single crystals of 5 mm diameter and 60 mm length with a growth rate 5 mm per day have been grown successfully. The improved transparency of grown crystal was investigated using DRS UV transmittance spectral analysis and the presence of functional groups in the grown crystal is confirmed using FTIR analysis. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single-crystal growth of sulphospinel CuIr2S4 from Bi solution

Single crystals of a sulphospinel CuIr₂S₄ have been grown from bismuth solution by a slow cooling method for the first time. The grown crystals have a maximum edge of about 1 mm in size and a mirror-like shining surface. Optimum growth conditions are fairly strict. The specific weight of starting materials for the crystal growth is found to be 0.30 g of CuIr₂S₄ and 10.0 g of Bi in order to obtain good quality crystals. The starting and finishing temperatures for the slow cooling step in the temperature control are 1000 and 500°C. The pertinent cooling rate is 2°C/h. Since the volume of bismuth itself expands in the transition from liquid phase to solid phase, a simple method of separation of the grown crystals from the liquid solution will be proposed for avoiding the mechanical damages to the grown crystals. The single crystals have the normal-spinel structure of the lattice constant a=9.849 Å at room temperature. A step-like anomaly in the susceptibility of the single crystals, corresponding to the metal–insulator transition in the resistivity, occurs much sharply than in the powder specimen.     

Recent achievements in AMMONO-bulk method

In this paper we present progress made recently in the development of the growth of truly bulk GaN crystals by the ammonothermal method in basic environment. High quality 2-in c-plane GaN seeds are shown. Non-polar wafers can also be cut out from thick GaN crystals grown by ammonothermal method. Perfect crystallinity manifests in very narrow peaks in X-ray rocking curves (the full width at half maximum equals about 15 arcsec). GaN epilayers deposited on these substrates exhibit intrinsic narrow exciton lines, which are very sensitive to the optical selection rules typical for hexagonal symmetry, proving the truly non-polar character of such AMMONO-GaN substrates. Other challenges like homogenous insulating properties or high p-type conductivity have been also accomplished by means of ammonothermal method. Semi-insulating crystals of resistivity up to 10¹¹ Ω cm and p-type conductivity within hole concentration up to 10¹⁸ cm⁻³ are already available in diameters up to 1.5-in.     

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.     

改进的升华法制备氮化铝单晶体

采用改进的升华法在氮气环境下制备氮化铝单晶体.通过优化实验条件制备出了六角形的高质量的氮化铝单晶体.实验发现,在坩埚的不同区域得到的氮化铝晶体的大小和形态有所不同.讨论了温度梯度对氮化铝晶体尺寸大小和形态的影响.     

Studies on the vapour growth of ZnS,ZnSe and ZnTe single crystals

Large, highly perfect single crystals (up to 10 × 10 × 5 mm³) of ZnS, ZnSe and ZnTe have been grown from the vapour phase by dissociative sublimation and chemical transport with iodine. Good quality crystals were obtained when the growth rate was limited by diffusion of the vapours rather than by thermal convection or by reaction rates at the charge and or the growing surface. The presence of an inert gas and defined iodine concentrations increase the growth stability, especially for charges with slight deviations from stoichiometry. Electronmicrographs, X-ray topographs and etching experiments revealed low dislocation densities and relatively large inclusion-free regions.