Initial stages of SiC crystal growth by PVT method

Initial stages of SiC crystal growth by Physical Vapor Transport method were investigated. The following features were observed: (a) many nucleation crystallization centres appeared on the seed surface during the initial stage of the growth, (b) at the same places many separate flat faces generated on the crystallization front, (c) the number of facets was dependent on the shape of the crystallization front and decreased during growth, (d) appearance of many facets lead to decrease of structural quality of crystals due to degradation of regions where crystallization steps from independent centres met. The results revealed that the optimal crystallization front should be slightly convex, which permits the growth of crystals with single nucleation centre and evolution of single facet on the crystallization front. The subjects of study were the shape and the morphology of growth interface. Defects in the crystallization fronts and wafers cut from the crystals were studied by optical microscopy, atomic force microscopy (AFM) combined with KOH etching and X‐ray diffraction. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stacking faults in semi‐polar 6H‐SiC single crystals

6H‐SiC single crystals have been successfully grown on (1015) plane seed by sublimation method. High density stacking faults (SFs) were observed by transmission synchrotron radiation X‐ray topography. Based on the invisibility criteria of stacking faults, the displacement vectors of most SFs were determined to be the type of 1/6[1120]. Laser scanning confocal microscopy (LSCM) was used to observe the etching morphology of (0115) wafer. The etching steps of SFs were found and their density decreased from 3.6×10³ cm^‐1 to 2.0×10² cm^‐1 along the <0001> projection direction. The inclination angles of the SFs etching step plane to (10‐15) plane were measured by line scanning of LSCM. It was found that the inclination angles decreased from 20° to 10° along the <0001> projection direction. Different etching characteristics of SFs along radial direction of 6H‐SiC (1015) wafer should be attributed to different displacement vectors and different stacking fault energies for these stacking faults. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

碳化硅单晶生长用高纯碳化硅粉体的研究进展

碳化硅(SiC)以其宽带隙、高临界击穿场强、高热导率、高载流子饱和迁移率等优点,被认为是目前较具发展前景的半导体材料之一.近年来,物理气相传输(PVT)法在制备大尺寸、高质量SiC单晶衬底方面取得了重大突破,进一步推动了SiC在高压、高频、高温电子器件领域的应用.SiC粉体是PVT法生长SiC单晶的原料,其纯度会直接影...     

Growth of AlN single crystals on 6H‐SiC (0001) substrates with AlN MOCVD buffer layer

6H‐SiC (0001) deposited 300 nm thick AlN film by MOCVD was used as the substrate to grow AlN crystals by the physical vapour transport (PVT) method. It was confirmed that c‐axis oriented AlN films were grown and this material had a 3D growth mode. The root mean square (RMS) value for the film was measured to be 2.17 nm. Nucleation and further growth of AlN on so prepared substrate was investigated. Colorless and transparent AlN crystal with 1 mm thick and 40 mm in diameter was obtained after 4 h growth on this substrate. The transparent AlN showed strong (0001) texture XRD patterns, only the (0002) reflection was observed in symmetric θ‐2θ scans. The full width at half maximum for a (0002) X‐ray rocking curve was less than 0.1° indicating good crystalline quality. Anisotropic etchings in molten KOH shows that the growth (0001) plane exposed to the AlN source predominately has an aluminum polarity, no N‐polar inversion domains were observed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transport property measurements in tungsten sulphoselenide single crystals grown by a CVT technique

The transport properties of ternary mixed WS_xSe_2‐x single crystals have been studied by measuring the thermo power, electrical conductivities and Hall parameters in a small temperature range 303‐423 K. The electrical conductivity was highest for selenium rich WSe₂ and lowest for sulphur rich WS₂ crystals. All the crystals showed semiconducting behaviour from the temperature dependence of ‘ρ’, ‘R_H’ and ‘S’. The Hall coefficients showed that the samples are p‐type conducting. The temperature dependence of resistivity, Hall coefficients, carrier concentration showed that all of them are thermally activated. The values of activation energies, pre‐exponential factors and the scattering parameters have been determined. The dominant scattering mechanism for the charge carriers has been explained. The relation between the TEP and the concentration of charge carriers and electrical conductivity was studied. The effective masses of holes and the effective density of states have been determined. These parameters show an increase with increase in sulphur content. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

PVT法生长4H-SiC晶体及多型夹杂缺陷研究进展

作为第三代半导体材料的典型代表,碳化硅因具备宽的带隙、高的热导率、高的击穿电场以及大的电子迁移速率等性能优势,被认为是制作高温、高频、高功率以及高压器件的理想材料之一,可有效突破传统硅基功率半导体器件的物理极限,并被誉为带动“新能源革命”的绿色能源器件。作为制造功率器件的核心材料,碳化硅单晶衬底的生长是关键,尤其是单一4H-SiC晶型制备。各晶型体结构之间有着良好的结晶学相容性和接近的形成自由能,导致所生长的碳化硅晶体容易形成多型夹杂缺陷并严重影响器件性能。为此,本文首先概述了物理气相传输(PVT)法制备碳化硅晶体的基本原理、生长过程以及存在的问题,然后针对多型夹杂缺陷的产生给出了可能的诱导因素并对相关机理进行解释,进一步介绍了常见的碳化硅晶型结构鉴别方式,最后对碳化硅晶体研究作出展望。     

Twins in CdMnTe single crystals grown by Bridgman method

Cd_1‐xMn_xTe (x =0.2, CdMnTe) crystal was grown by the vertical Bridgman method, which exhibits a pure zincblende structure in the whole ingot. The major defect, twins, which is fatal to CdMnTe crystal, was analyzed with scanning electron microscopy (SEM), X‐ray energy disperse spectroscopy (XEDS) and optic microscopy on the chemical etching surface. The twins observed in the as‐grown ingot are mainly lamellar ones, which lie on the {111} faces from the first‐to‐freeze region of the ingot and run parallel to the growth axis of the ingot. Coherent twins with {115}_t‐{111}_h orientations when indexed with respect to both the twin and host orientations, are often found to be terminated by {110}_t‐{114}_h lateral twins. Te inclusions with about 20 μm in width are observed to preferentially decorate the lamellar twin boundaries. The origin of the twins, relating to the growth twin and the phase transformation twin, is also discussed in this paper. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of L‐ascorbic acid single crystals grown from solution with different solvents

Single crystals of L‐ascorbic acid, popularly known as vitamin‐C, were grown from solutions with different solvents and solvent combinations by low temperature solution growth methods. The suitability of different solvents and solvent combinations such as acetone, ethanol, methanol, isopropyl alcohol, water, water + acetone (1:1), water + ethanol (3:1), water + isopropyl alcohol (3:1) and isopropyl alcohol + methanol (1:1) for crystal growth of L‐ascorbic acid was found out by assessing the solubility and crystallization behaviours. Solubility of L‐ascorbic acid in selected solvents and solvent combinations in a range of temperatures was determined by gravimetric method. Solution prepared with water, water + acetone (1:1), water + ethanol (3:1) and water + isopropyl alcohol (3:1) were yielded crystals with tabular, columnar and prismatic habits and their morphologies were evaluated by goniometry. Grown single crystals were characterized with various instrumental techniques such as powder X‐ray diffraction, Fourier infrared spectroscopy, optical transmittance study, differential scanning calorimetry and second harmonic generation studies. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The stress birefringence images of low angle grain boundaries in 6H‐SiC single crystals

Low angle grain boundaries, also referred to as domain walls, is one of the major structural defects in c‐axis physical vapor transport (PVT) grown hexagonal Silicon Carbide. To investigate the nature of the low angle boundaries, polarized optical microscope was used. The low angle boundary gives bright stress birefringence images under polarizing optical microscope. Periodic extinction of the stress birefringence images occurs when the (0001)‐face SiC is rotated under polarizing optical microscope. The micro‐structure of the low angle boundary is proposed. Using dislocation elastic theory, it is theoretically confirmed that the domains consist of uniform pure edge dislocations with Burgers vectors perpendicular to the dislocation arrays. The simulation results coincide with the experimental observations.     

High‐quality LaCoO3 single crystal grown by optical floating zone method and its electromagnetic properties

A LaCoO₃ single crystal with 4 mm in diameter and 30 mm in length has been grown by optical floating zone method. The as‐grown crystal is highly crystalline with the rhombohedral perovskite structure (R3c) and grows parallel to the (121) direction. The room temperature resistivity of the as‐grown crystal is 0.12 Ω·cm and the insulator‐metal transition occurs around 500 K. The coercivity and the remanence of the as‐grown crystal are 5 Oe and 6.61×10^–5 μ_B/f.u. at 5 K, respectively. In 1000 Oe under zero‐field cooling, the magnetic susceptibility of the as‐grown crystal shows an upturn in a Curie tail fashion below 35 K, and appears a wave crest over the interval 55 K≤T≤90 K. In addition, a slope change of 1/χ(T) at about 12 K is observed in 50000 Oe under zero‐field cooling. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of AgGa1‐xInxSe2 single crystals grown by Bridgman method

High‐pure and single‐phase AgGa_1‐xIn_xSe₂ (x=0.2) polycrystalline was synthesized by the mechanical and temperature oscillation method. Adopting the modified Bridgman method an integral AgGa_1‐xIn_xSe₂ single crystal with diameter of 14 mm and length of 35 mm has been obtained at the rate of 6 mm/day. It was found that there is a new cleavage face which was (101), and observed the four order X‐ray spectrum of the {101} faces. By the method of DSC analysis the melting and freezing points of the AgGa_1‐xIn_xSe₂ (x=0.2) single crystal were about 828°C and 790°C. The transmission spectra of the AgGa_1‐xIn_xSe₂ (x=0.2) sample of 5×6×2 mm³ were obtained by means of UV and IR spectrophotometer. The limiting frequency was 774.316nm and the band gap was 1.6eV. It can be found in the infrared spectrum that the infrared transmission was above 60% from 4000cm^‐1 to 600cm^‐1. The value of α in 5.3µm and 10.6µm were 0.022cm^‐1 and 0.1cm^‐1 respectively. All results showed that the crystal was of good quality. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diamagnetic and photoabsorption characterisation of gel‐grown cadmium oxalate single crystals

Perfect single crystals of cadmium oxalate trihydrate have been grown using the slow and controlled reaction between Cd⁺² and (C₂O₄)^‐2 ions in agar‐agar gel, resulting in the formation of insoluble product Cd(COO)₂.3H₂O. The optimum growth parameters have been determined. The variation of magnetic moment of the grown crystals under an applied static magnetic field is studied and the material is found to be diamagnetic. The polarizability is found sensitive to optical band gap. An empirical relation between magnetic susceptibility and electronic polarizability has been established. Optical absorption spectra of the sample recorded in the range 200‐2500 nm reveal transitions involving absorption and emission of phonons. The detailed study supports the existence of allowed direct and indirect allowed gaps in the material. The direct allowed transition prevails in the region of relatively higher photon energy. Some feeble disorder in the crystal is conceived to be present. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Work‐hardening characteristics of Zn‐Ti alloy single crystals

Shear stress – shear strain curves of 0.14 at.%Ti alloyed Zn single crystals were measured in compression at different temperatures and shear strain rates. The work‐hardening coefficient for basal slip increases with decreasing temperature and increasing shear strain rate. The work‐hardening characteristics are compared with those reported for Zn single crystals with different constituents and purities. It is discussed with respect to the interaction of dislocations with dislocations, vacancies, vacancy agglomerates and solute atoms. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

大尺寸电阻加热式碳化硅晶体生长热场设计与优化

大尺寸低缺陷碳化硅(SiC)单晶体是功率器件和射频(RF)器件的重要基础材料,物理气相传输(physical vapor transport, PVT)法是目前生长大尺寸SiC单晶体的主要方法。获得大尺寸高品质晶体的核心是通过调节组分、温度、压力实现气相组分在晶体生长界面均匀定向结晶,同时尽可能减小晶体的热应力。本文对电阻加热式8英寸(1英寸=2.54 cm)碳化硅大尺寸晶体生长系统展开热场设计研究。首先建立描述碳化硅原料受热分解热质输运及其多孔结构演变、系统热输运的物理和数学模型,进而使用数值模拟方法研究加热器位置、加热器功率和辐射孔径对温度分布的影响及其规律,并优化热场结构。数值模拟结果显示,通过优化散热孔形状、保温棉的结构等设计参数,电阻加热式大尺寸晶体生长系统在晶锭厚度变化、多孔介质原料消耗的情况下均能达到较低的晶体横向温度梯度和较高的纵向温度梯度。     

Electrical properties and deep levels spectra of bulk SiC crystals grown by hybrid physical–chemical vapor transport method

Concentrations of nitrogen shallow donors, boron shallow acceptors, charge carriers, and electron traps were measured as a function of position along the growth axis in a series of undoped 6H–SiC boules grown by sublimation method with and without addition of hydrogen to the growth atmosphere. Elemental analysis by secondary ion mass spectrometry and measurements of electrical properties indicate that the addition of hydrogen suppresses nitrogen incorporation and formation of all electron traps. Concentration of boron is not affected by hydrogen presence. The addition of hydrogen to the growth ambient improves the uniformity of nitrogen incorporation and deep trap distribution along the growth axis. The results are interpreted as due to increased carbon transport and corresponding shift of crystal stoichiometry toward carbon-rich side of the SiC existence range.     

Stage B work‐hardening of magnesium single crystals

The change in microstructure during tensile deformation of magnesium single crystals by basal slip was studied with electron backscatter diffraction in the scanning electron microscope. Two samples were plastically deformed up to shear strains of 0.37 and 1.28 belonging to work‐hardening stages A and B, respectively. The results show that the local misorientations resulting from rotations around the <10 0> axis strongly increase the work‐hardening coefficient in stage B. The mechanism of work‐hardening in stage B is discussed with respect to subgrain formation. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Precipitation of intermetallic phase in Zn‐Ti alloy single crystals

Pure and 0.14 at.%Ti alloyed Zn single crystals have been grown by the Bridgman technique. The alloyed crystal exhibits a sheet‐like precipitation structure parallel to the basal plane of the hexagonal solid solution Zn‐Ti matrix. The tetragonal precipitates are intermetallic compounds of Zn₁₆Ti composition. They are needle‐shaped with the needle axis peferentially aligned along the <a> axis. The approximate orientation relationship between precipitate and matrix is (0001)<11$\bar 2$ 0>_Matrix||(010)[001]_Zn16Ti. To study the influence of alloying on the mechanical properties, the critical resolved shear stress for basal slip has been measured in compression at different temperatures and strain rates. It is shown that the critical resolved shear stress can be very well explained by theories of solid solution and precipitation hardening. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Layered crystals of apo‐ and holoferritin grown by alternating crystallization

We report on the use of alternating crystallization for deposition of layers of different (though closely related) proteins in a single crystal. Investigations were carried out with the unique protein couple consisting of two forms of ferritin, apoferritin and holoferritin from horse spleen, which, despite being of quite different molecular masses, still possess identical organic shells. Crystals of both proteins were used as substrates for subsequent contiguous growth of the partner protein in perfect alignment. We observed continuous growth of combined (onion‐like) single crystals; artificial structures of biological macromolecules can be designed in this way. The homoepitaxial layered growth shows in an unambiguous way that protein crystallization depends only on the surface protein conformation and amino‐acid composition, but not on the internal molecule structure. The limitations of protein crystal growth for designing layered structures of biological macromolecules were revealed by growing of heterogeneous protein crystals onto pre‐existing protein crystalline substrates. Tetragonal crystals of hen egg‐white lysozyme were grown onto cubic apoferritin crystals used as substrates. It was observed that the lysozyme crystals were not lattice‐matched to the ‘host’ apoferritin crystals; this led to mere aggregates of different crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

8英寸导电型4H-SiC单晶的生长

采用物理气相传输(PVT)法扩径获得了8英寸(1英寸=2.54 cm)4H-SiC籽晶,用于8英寸导电型4H-SiC晶体生长,并加工出厚度520 μm的8英寸4H-SiC衬底。使用拉曼光谱、全自动显微镜面扫描、非接触电阻率测试仪面扫描和高分辨X射线衍射仪对衬底的晶型、微管、电阻率和结晶质量进行了表征。衬底颜色均一并结合拉曼光谱表明衬底4H-SiC晶型面积比例为100%;衬底微管密度小于0.3 cm^-2;衬底电阻率范围20~23 mΩ·cm,平均值为22 mΩ·cm;(004)面高分辨X射线摇摆曲线半峰全宽为32.7″,表明衬底良好的结晶质量。