Bulk growth of near-IR cadmium mercury telluride (CMT)

Cadmium mercury telluride (CMT, Cd_xHg_1–xTe) is still the pre-eminent infrared material, despite the difficulties associated with its production and subsequent processing. By varying the x value, the system can be made to cover all the important infrared (IR) ranges of interest. The two most common regions required are x0.21 and 0.3 for 8–14 and 3–5 m atmospheric transmission windows, that is, long wave, LW, and mid wave, MW, respectively. Recently we have extended the growth process to produce both very long wavelength and near-IR material for various applications. This paper focuses on the work undertaken to produce near-IR material, where higher starting x values are used. Growth takes place in simple 2-zone furnaces with the pure elements contained in thick-walled high-purity silica ampoules. The thick ampoule walls are needed to contain the high (up to 70 atm) mercury vapor pressures within the ampoules. An improved ampoule seal-off procedure was developed to enable us to grow at the higher temperatures (hence higher pressures) needed for these higher x start crystals. The accelerated crucible rotation technique (ACRT) modification to the basic Bridgman process is used to grow the crystals. Here, ampoules are subjected to periodic acceleration/deceleration in their rotation, rather than constant rotation as in the Bridgman process, which stirs the melt during growth and produces flatter solid/liquid interfaces. This, in turn, improves the radial and axial compositional uniformity of the material. An additional advantage of ACRT is that the improved radial compositional uniformity enables larger diameter material to be considered. We are currently growing 20 mm diameter, 200 mm long crystals of 0.5 kg weight with good uniformity of composition. The assessment of the near-IR material has included wavelength mapping of both radially cut slices and axially cut planks. The latter gives useful information on the shape and change in the solid/liquid interface as growth proceeds. Quenching experiments reveal actual solid/liquid interfaces that confirm the findings of the wavelength mapping. Images taken with an IR camera reveal features in slices, for example, cracks, inclusions of second phase and swirl patterns, the origin of the latter is unknown.     

Bulk Bridgman growth of cadmium mercury telluride for IR applications

Cadmium mercury telluride (CMT, CD_xHg_1-xTe) is the pre-eminent infrared material, despite the difficulties associated with the production and subsequent processing of this ternary compound. By varying the x value the material can be made to cover all the important infrared (IR) ranges of interest. The first technique developed was the basic vertical Bridgman process with typical crystal dimensions of 13 mm diameter and 150 mm length. We found it necessary to purify both the mercury and the tellurium on-site before use to obtain the required electrical properties. There is marked segregation of the matrix elements in Bridgman growth that is both a disadvantage and an advantage. Its disadvantage is that the yield of material in terms of composition for the two most common regions required (x=0.21 and 0.3 for 8–14 and 3–5 m atmospheric transmission windows, respectively) is low. The advantage is that both regions of interest are produced in the same crystal. A further advantage is that segregation of impurities also occurs and leads to low background donor levels in Bridgman material. This Bridgman material is used exclusively for photoconductive IR detectors that require n-type material. The main disadvantages of the Bridgman technique are that material is non-uniform in composition in the radial direction, as well as in the growth direction, and there are numerous grain and sub-grain boundaries. An improved process was developed at BAE Systems based on the accelerated crucible rotation technique (ACRT). Here, growth ampoules are subjected to periodic acceleration/deceleration in their rotation, rather than constant rotation as in the Bridgman process. The major effect of this is to stir the melt during growth and produce flatter solid/liquid interfaces. This, in turn, improves the radial and axial compositional uniformity of the material, normally by a factor of at least ten-fold. The only drawback is that the material is now p-type as grown and must be annealed in mercury vapor to convert it to n-type. An additional marked advantage of ACRT is that the improved radial compositional uniformity enables larger diameter material to be considered. We are currently growing 20 mm diameter, 200 mm long crystals of 0.5 kg weight with acceptable uniformity of composition and good electrical properties for current photoconductive detector programs. © 2001 Kluwer Academic Publishers     

在横向磁场中用Bridgman法生长HgCdTe晶体

在横向磁场中用Ｂｒｉｄｇｍａｎ法生长的晶锭其轴向组分分布在中部和尾部具有相同的趋势,在头部有三种类型的分布。磁场通过对固液混合区对流的作用影响溶质的再分布和轴向组分分布。突然施加磁场和中断磁场都引起轴向组分分布的突变。当安瓿绕生长轴匀速旋转时,晶锭的径向组分分布既没有安瓿不旋转时的偏心特征,也没有常规Ｂｒｉｄｇｍａｎ法生长晶体的径向对称性,尾部呈现圆锥状的凸起,可能是旋转生长抑制胞状结构的证据。     

Cd0.9Mn0.1Te晶体生长及其缺陷分析

采用Bridgman法和ACRT-B法生长了两根Cd0.9Mn0.1Te晶锭(简称CMT-B和CMT-A).采用光学金相显微镜和扫描电镜研究了这两种方法生长的晶体中出现的各种缺陷,并分析了其形成机理.采用JEOL-733电子探针测定了两根晶锭中Mn的分布.对比CMT-B和CMT-A两根晶锭,发现ACRT所产生的对流可提高Cd0.9Mn0.1Te晶体的结晶质量.     

Cd0.96Zn0.04Te单晶生长及晶体成分偏析

采用常规Ｂｒｉｄｇｍａｎ法和ＡＣＲＴ－Ｂ法进行Ｃｄ０．９６Ｚｎ０．０４Ｔｅ晶体生长实验。结果表明：ＡＣＲＴ产生的强迫对流在很大程度上消除了侧壁形核，有利于获得大的晶体；ＡＣＲＴ的加入提高了有效分凝系数ｋｅｆｆ，使其向平衡分凝系数ｋｅｑ趋近，导致轴向的偏析增大。     

ACRT—B法晶体生长过程的传质模型

基于对ＡＣＲＴ－Ｂ法晶体生长对时流及传质特性的认识，提出了ＡＣＲＴ－Ｂ法晶体生长过程的一维传质模型。得到了包括初始过渡区、稳态区及终端过渡区轴向成分分布的解析解。定量计算结果表明，与传统Ｂｒｉｄｇｍａｎ法相比，在生长参数不变的条件下，运用ＡＣＲＴ会失去部分轴向面分均匀区。在保护ＡＣＲＴ提高结晶及径向成分均匀性的前提下，适当提高生长速度，选择尽可能小的坩埚最大转速△ωｍａｘ或选用长径比更大的坩埚，是     

Crystal growth of rare-earth-doped ternary potassium lead chloride single crystals by the Bridgman method

High optical quality pure and rare-earth-doped ternary-potassium-lead-chloride (KPb₂Cl₅) single crystals have been grown using the Bridgman technique in a two-zone transparent vertical furnace. Combining the chlorination of the melt, to eliminate oxygen impurities, with a horizontal zone-refining, followed by the Bridgman growth itself using sealed silica ampoules, we successfully grew non-moisture-sensitive crystals of a high optical quality. The moisture content in the raw materials determines the quality of the resulting crystals.     

Some recent advances in bulk growth of mercury cadmium telluride crystals

The inherent metallurgical problems associated with the HgTe/CdTe pseudobinary alloy system render the standard crystal growth processes inapplicable to the preparation of mercury cadmium telluride crystals for infrared detector applications. A variety of rather nonconventional techniques have been developed to overcome these problems. Two such techniques, viz. asymmetrical Bridgman and horizontal casting for solid-state recrystallization, developed at Solid State Physics Laboratory for the bulk growth of mercury cadmium telluride crystals are reviewed in this communication. Due to the poor thermal conductivity of mercury cadmium telluride melts and solids, and the use of thick-walled quartz ampuoles, it is extremely difficult to obtain a flat solid-liquid interface during Bridgman growth of this material. The technique of asymmetrical Bridgman has been successful in overcoming this problem to a great extent. Solid-state recrystallization has been widely accepted as one of the most successful techniques for obtaining large quantities of acceptable-quality mercury cadmium telluride crystals for infrared detector applications. This is a two-step process—the melt is first quenched to obtain a good cast, which is then subjected to a grain-growth annealing. The horizontal casting procedure developed for solid state recrystallization growth has been successful in improving the overall quality and yield of bulk mercury cadmium telluride crystals.     

Growth and characterization of Bi2Sr2Ca1Cu2O8+x single crystals

High-quality single crystals are well suited to the investigation of some intrinsic material properties. A modified Bridgman method using a sharp temperature gradient (～300°C/cm) was used to grow Bi₂Sr₂Ca₁Cu₂O_8+x single crystals. Although the samples were contained in alumina ampoules, no aluminium contamination of the samples was detected. Blade-shaped crystals up to ～7–8 mm length and 3–4 mm width could be grown by this method, although extraction from the matrix was difficult. Electron diffraction patterns of the [001] zone axis revealed a high degree of crystallinity. The narrowness of the superconducting transition temperature, as determined by ac susceptibility, also suggests the existence of well-formed crystalline domains. In order to determine the relative orientation of the crystalline domains, electron channeling patterns were recorded from several consecutive growth steps from a fracture surface. The poor contrast of these and Kikuchi patterns suggests the presence of a stacking structure. The results showed a [100] growth direction and (001) cleavage plane. Reversible oxygen loss at the peritectic decomposition temperature of 863°C was observed. Knoop indentation measurements showed that the crystals were quite soft, having a microhardness of 0.44 GPa.     

Composition Distribution in the MnxCd1-xIn2Te4 Ingot Grown by ACRT-B Method

MnxCd1-xIn2Te4 (x=0.1) ingot was successfully grown by the modified Bridgman technique, which applied the accelerated crucible rotation technique (ACRT) in Bridgman process, or briefly ACRT-B. The growth interface profile shape and the composition distribution in the MnxCd1-xIn2Te4 (x=0.1) ingot were analyzed. Even though the stoichiometric composition was synthesized in the original ingot, the composition has been redistributed during the ACRT-B growth process. Mn and Cd contents decrease while In increases along the longitudinal axis. The partition ratios of solutes Mn, Cd and In at the growth interface are evaluated by a mathematical method based on the experimental data, which are found to be 1.286, 1.926 and 0.729 in α phase growth process, and 1.120, 1.055 and 0.985 in β phase growth process, respectively. In the radial direction,Mn and Cd contents increase while In decreases with the distance from the centerline of the ingot.     

Growth of lead sulfide single crystals by the bridgman method

Large crackfree crystals could be grown by the Bridgman technique using graphite ampoules. Their metallurgical properties are typical for Bridgman crystals. However, a high content of carbon is incorporated into the crystals using this method. The variation of the carrier concentration along the length of the crystal could be deduced from the phase diagram.     

An X-ray topographic assessment of cadmium mercury telluride

This paper describes an X-ray topographic (Berg-Barrett) assessment of cadmium mercury telluride grown by the Bridgman and cast-recrystallize-anneal (CRA) methods. Reflection topographs reveal that the Bridgman material studied consists of large numbers of small grains (0.05 to 0.6 mm) with misorientations from 1 to 9 minutes per grain. In contrast, the CRA material studied had only a few grain boundaries and features consistent with a strained lattice, possibly caused by compositional variations.     

Growth of undoped and Te doped InSb crystals by vertical directional solidification technique

We have successfully grown high mobility undoped and Te doped InSb crystals of size 10–12 mm dia. and 60 mm length under inert argon atmosphere in closed quartz ampoules, by vertical directional solidification (VDS) technique. The crystals showed predominantly (220) orientation along the growth axis. The surface defects, such as voids were reduced drastically by selecting proper lowering rate, rotational speed and cone angle of the ampoule. The high mobility and quality crystals were obtained with the ampoule conical angle less than 20°, lowering rate 5mm/h, and rotational speed 10 rpm.     

Investigation of potential and compositional fluctuations in CuGa3Se5 crystals using photoluminescence spectroscopy

We studied the photoluminescence (PL) properties of the ordered defect compound CuGa₃Se₅. Different single crystals were grown by the vertical Bridgman method and by the solid phase crystallization method. Their crystal structure and cell parameters were determined by X-ray diffraction. The PL spectra were recorded at T = 10-300 K. Also, laser power dependences were studied. We found an asymmetric PL band at 1.76 eV. PL band shifts towards higher energies with increasing laser power. The shape and properties of this band assure the presence of potential and compositional fluctuations. The influence of both fluctuations on the PL properties of CuGa₃Se₅ is studied and the radiative recombination processes are explained.     

Growth of lead molybdate crystals by vertical Bridgman method

The growth of PbMoO₄ crystals by the modified Bridgman method has been reported in this paper. The feed material with strict stoichiometric composition is desirable for the Bridgman growth of the crystals. The continuous composition change of the melts during growth can be avoided because the volatilization of melts is limited by sealed platinum crucibles. By means of the optimum growth parameters such as the growth rate of < 1.2 mm/h and the temperature gradient of 20 ∼ 40°C/cm across the solid-liquid interface under the furnace temperature of 1140 ∼ 1200°C, large size crystals with high optical uniformity were grown successfully. The distribution of Pb and Mo concentration along the growth axis was measured by X-ray fluorescence analysis. The single crystallinity of the grown sample was evaluated by the double-crystal X-ray rocking curve. The transmission spectra were measured in the range of 300–800 nm at room temperature.     

Experimental setup for rapid crystallization using favoured chemical potential and hydrodynamic conditions

The rapid crystallization of KH₂PO₄ (KDP) from solution is demonstrated at a rate up to ≈ 7.5 mm/day along [100] and 22 mm/day along [001] in a crystallizer of 5 l capacity, using accelerated crucible rotation technique (ACRT) and simulated platform geometry for controlling the hydrodynamic conditions. On an experimental basis we have grown the crystals up to 40 · 43 · 66 mm3 size in about 3 days. Comparative analysis of the main structural and optical properties of crystals grown by conventional and rapid crystallization technique, is discussed.     

垂直布里奇曼法CdZnTe晶体生长过程的数值分析

模拟计算了半导体材料CdZnTe布里奇曼法单晶体生长过程，分析了熔体的过热温度、坩埚侧面强化换热以及坩埚加速旋转(ACRT)等因素对结晶界面的形态和晶体组分偏析的影响。结果表明：当熔体的过热温度减小时，熔体中自然对流的强度显著降低，固液界面的凹陷深度有所增加，晶体的轴向等浓度区显著加长，而晶体组分的径向偏析明显增大，坩埚的侧面强化换热增加了自然对流强度，也增大了固液界面的凹陷，但是对溶质成分的偏析影响较小，坩埚加速旋转引起的强迫对流强度远大于自然对流，显著增大了固液界面的凹陷，使熔体中的溶质分布成为均一的浓度场，显著减小了晶体组分的径向偏析，增加了晶体组分的轴向偏析。     

Facetting and optical perfection in Czochralski grown garnets and ruby

Studies of ruby (Al₂O₃/Cr³⁺) and rare-earth aluminium garnet single crystals, in particular the mixed garnets formed between Y₃Al₅O₁₂ (YAG) and Dy₃Al₅O₁₂ (DyAG), have shown that the formation of facets on the solid/liquid interface, which give rise to a strained central core within the crystals, is dependent upon the shape of the solid/liquid interface. Development of the strained and facetted core can be prevented by modifying the growth conditions to produce a flat solid/liquid interface and as a result the optical perfection of the crystals is greatly improved. Certain crystals, e.g. DyAG, grow naturally with aflat interface, and in the present work this has been shown to be due to the optical absorption characteristics of this material. In other materials, e.g. YAG and ruby, the interface shape can be controlled by the rate at which the growing crystal is rotated. The changes in temperature gradient produced in a YAG melt by changes of crystal rotation rate have been measured, and their effect upon crystal perfection is described.     

Electrical properties of Se1−xTex crystals

Single crystals of Se_1?xTe_x (with x varying from 0.1 to 0.9) were successfully grown by the Bridgman method. D.C. Hall effect and temperature dependence of π of these crystals were measured. π at 300°K is found to decrease and the carrier concentration to increase approximately exponentially with x. The temperature dependence of π shows that the conduction is thermally activated. At low temperature (< 300 °K) extrinsic conduction is dominant with the value of the activation energy decreasing from 0.065 to 0.006 eV as x increases from 0.1 to 0.9. At higher temperature, intrinsic conduction is observed for alloys with x = 0.4, 0.5, 0.6 and 0.8 yielding the values of intrinsic band gaps (E_g). The values of E_g are found to decrease with x.     

Chemical vapour transport of transition metal oxides (III) crystal growth of Ti1−xRuxO2 and doped TiO2

Single crystals of the system Ti_1?xRu_xO₂ have been prepared by chemical vapour transport in closed ampoules using halide transport agents. The crystals are single phased for x ≦ 0.02 and 0.98 ≦ x. In the intermediate range a highly ordered two phased system is found. The pure RuO₂ crystals are substantially larger than any grown by open sysem chemical vapour transport. Single crystals of TiO₂ doped with other impurities have also been prepared.