Defect Investigations in CdTe Crystals by RXT,SCL, and EBIC(V) Techniques

The paper covers results of investigations on the defect structure of CdTe crystals. Several techniques have been involved, namely RXT supplied with CL-IR, EBIC(V), and SACP using Electron Probe Micro-Analyzer (EPMA): EBIC(V) measurements were performed on Schottky diodes with CdTe-Au contacts. It has to be emphasized that microscopic images at small magnification (45 ×) had successfully been obtained which were next correlated with X-ray topographs. The observed due to grain boundaries, twins, “as grown” dislocations as well as those introduced either during high-temperature plastic deformation or by pyramidal diamond indenter are discussed.     

Phase-field simulations of Te-precipitate morphology and evolution kinetics in Te-rich CdTe crystals

Te precipitates are one of principal defects that form during cooling of melt-grown CdTe or CZT crystals when grown Te-rich. Many factors such as the kinetic properties of intrinsic point defects (vacancy, interstitial, and antisite defects); stresses associated with the lattice mismatch between precipitate and matrix; temperature gradients and extended defects (dislocations, twin and grain boundaries); non-stoichiometric composition; thermal treatment history all affect the formation and growth/dissolution of Te precipitates in CdTe. A good understanding of these effects on Te precipitate evolution kinetics is technically important in order to optimize material processing and obtain high-quality crystals. This research develops a phase-field model capable of investigating the evolution of coherent Te precipitates in a Te-rich CdTe crystal undergoing cooling from the melt. Cd vacancies and Te interstitials are assumed to be the dominant diffusing species in the system, which is in two-phase equilibrium (matrix CdTe and liquid Te inclusion) at high temperatures and three-phase equilibrium (matrix CdTe, Te precipitate, and void) at low temperatures. Using available thermodynamic and kinetic data from experimental phase diagrams and thermodynamic calculations, the effects of Te interstitial and Cd vacancy mobility, cooling rates and stresses on Te precipitate, and void evolution kinetics are investigated.     

Numerical optimization of thermal field in CdTe crystal growth by travelling heater method

Cadmium telluride (CdTe) and his compounds play a leading role in X‐ray and γ‐ray detector technology. One of the most used methods for growing these crystals is the travelling heater method (THM). The ingots obtained by using this technique show excellent composition uniformity, but the structural quality is affected by the presence of large grains which appear because of large curvatures of the solid‐liquid interface during the solidification process. This numerical work investigate the thermal field and melt convection in CdTe processing by THM in order to elucidate the mechanism of growing these crystals. The influence of the furnace geometry on the interface shape and temperature gradient in liquid is analyzed for samples with small (1 cm) and large (5 cm) diameters. The computations include flow effects on thermal field in the melted zone. The thermal conditions are optimized for THM growth of CdTe crystals at high solidification temperatures. A new multi‐zone furnace configuration for growing crystals of large diameter and flattened interface is proposed in this work.     

Dislocations in CdTe

Two different etchants were developed to get boat- and triangular type etch pits on CdTe crystals. The subboundaries are shown to be symmetrical tilt boundaries. Dislocation density and microhardness measurements were made on three CdTe crystals grown by Bridgman, Travelling heater and vapour phase technique and were correlated.     

Growth and defect studies of CdTe particles

The paper reports the epitaxial growth of cadmium telluride (CdTe) particles by thermal deposition on cleaved planes of (001)NaCl and (001)KBr. Using high resolution transmission electron microscopy and electron diffraction it was shown that CdTe particles could have different orientation and phase (cubic or hexagonal) depending on the substrate temperature. Their most common defects are twins and stacking faults.     

Self-assembled tin-doped ZnO nanowire and nanoplate structures grown by thermal treatment of ZnS powder

Sintering of a ZnS–SnO₂ mixture under argon flow leads to the growth of columnar nanoplate arrays as well as arrays of nanowires, nanorods and nanoplates with six-fold symmetry. The six-fold nanoplate structures correspond to a more advanced stage of growth than the nanowire structures. Cathodoluminescence (CL) in the scanning electron microscope (SEM) shows that the structures contain Sn, but the amount of this element is normally under the detection limit of X-ray energy-dispersive spectroscopy (EDS). The formation of branches in the hierarchical structures depends on the presence of Sn and on defects in the mixture powder.     

Boron oxide encapsulated Bridgman growth of high-purity high-resistivity cadmium telluride crystals

High-purity semi-insulating CdTe crystals have been successfully grown by encapsulated (B₂O₃) Bridgman technique. The procedure strongly limits component losses allowing the achievement of stoichiometry control material and keeps a low level of impurity contamination as shown by mass spectroscopy analysis data. When strictly stoichiometry-controlled and high-purity polycrystalline source material has been used, high-resistivity crystals have been obtained without any intentional doping. EPD values in the range of 1–3×10⁴ cm⁻² have been observed in a wide region of the crystals. Luminescence spectroscopy confirms the purity and good structural quality of the material. The proposed method avoids the technical problems posed by the High Pressure Bridgman technique and fits the requirements for CdTe/CdZnTe crystals large-scale production.     

一种采用光学比较测角仪测量碲化镉晶体平行度的方法

对碲化镉晶体进行了光学加工,利用两台测量精度为1″的光学比较测角仪和一块平行度优于1″的平行平晶测量了其平行度,并且和光学加工过程中采用激光平面干涉仪测得的氟化钙陪片的平行度进行了比较,分析了这种测量方法的误差来源及大小.结果表明:采用此方法测得的碲化镉晶体的平行度和采用激光平面干涉仪测得的陪片的平行度相差不超过3″;此方法的误差主要来自于光学比较测角仪的测量误差和平行平晶的平行度误差,总误差最大不超过5″,能够满足碲化镉晶体平行度测试的精度要求.     

Compensation Mechanism in Vanadium and Gallium Doped CdTe and (Cd,Zn)Te

Vanadium and gallium doped CdTe crystals were grown from the vapour phase (modified Markov method) and (Cd_0.9Zn_0.1)Te: V from the melt (vertical Bridgman). The crystals were characterized by photoinduced current transient spectroscopy (PICTS), photoluminescence (PL) and time dependent charge measurements (TDCM). Transitions from different charge states (V²⁺/V³⁺) of the vanadium donor have been observed in the V-doped crystals by PICTS. A shallow donor level (dE = 0.068 eV) and the Ga A-center have been identified by PICTS and PL measurements in CdTe:Ga. In case of V-doping high resistivity is achieved all over the crystal while Ga-doping results in a high resistivity region only in the middle of the crystal. Calculation of the resistivity by means of a compensation model shows that for both dopants an additional not observed deep donor has to be assumed in order to describe the resistivity distributions.     

Dewetted growth of CdTe in microgravity (STS‐95)

Two CdTe crystals had been grown in microgravity during the STS‐95 mission. The growth configuration was dedicated to obtain dewetting of the crystals and to achieve high quality material. Background for the performed experiments was based on the theory of the dewetting and previous experience. The after flight characterization of the crystals has demonstrated existance of the dewetting areas of the crystals and their improved quality regarding the earth grown reference sample. The samples had been characterized by EDAX, Synchrotron X‐ray topography, Photoluminescence and Optical and IR microscopy. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of cluster defects of variable composition on the optical and radiative characteristics of oxide crystals

It is shown that oxide crystals contain cluster defects of variable composition, which cause absorption of light in the transparency region of crystals. The model based on the presence of cluster defects in oxide crystals explains well the experimental data on the thermal and radiative coloring of these crystals. It is noted that cluster defects accumulate oxygen in oxide crystals. These defects are responsible also for the photochromic effect in them. Application of the noted model made it possible to fabricate lead tungstate scintillators at North Crystals Company for the ALICE project (CERN) with almost 100% reproducibility of their operating characteristics.     

水热法KTP晶体生长与宏观缺陷研究

本文报道了水热法KTP晶体的生长工艺及晶体生长形态,系统研究了水热法KTP晶体的宏观缺陷,其宏观缺陷主要为添晶、生长脊线、裂隙和包裹体.提出了晶体生长工艺的改进措施,如提高原材料和试剂的纯度、调整籽晶的悬挂方式、减少籽晶的尺寸等,都可以减少晶体的宏观缺陷,提高晶体的质量.//(011)切向的籽晶生长的晶体质量较高,且能很好地应用于激光器件中.     

Topography and goniometry of very perfect crystals

In order to characterise very perfect crystals such as Si which do not show any visible defects in conventional X-ray diffraction topography, the following topics are reviewed. (1) Intensity distribution of Pendellösung fringes in section topographs. (2) The tails of rocking curves. (3) Borrmann anomalous transmission. (4) Decoration of the defects. (5) Diffuse scattering. The experiments reviewed here indicate that the currently available good crystals are not regarded as ideally perfect crystals. The deviations from ideal perfection in (1), (2) and (3) are due to weak deformation of the crystal matrix surrounding the invisible defects whereas (5) gives us direct information about the atomic structure of the defects.     

Specific features of the growth of A II B VI films on (0001)Al2O3 substrates

The structure and orientation of CdTe and ZnO films on sapphire have been investigated for different techniques of pregrowth substrate treatment. Polycrystalline CdTe films are found to grow of substrates unannealed or annealed in vacuum at a residual pressure P < 0.13 Pa. Epitaxial CdTe films with the sphalerite cubic structure, oriented parallel to the substrate by the (111) plane, grow on substrates annealed in air at a temperature of 1000°C or more and having a system of smooth terraces and steps on the surface. For ZnO films with a wurtzite hexagonal structure obtained by magnetron sputtering, a similar correlation between the structural quality and the regime of treatment of sapphire substrates is observed. It is shown that thermal annealing of (0001) sapphire plates in air is the optimal way of substrate preparation for growing epitaxial ZnO films with the base orientation. The obtained epitaxial CdTe films contain a certain amount of structural defects (mosaicity and twins), while the epitaixal ZnO films treated in the same way are close to perfect.     

Supersmooth and modified surface of sapphire crystals: Formation,characterization, and applications in nanotechnologies

The results of studying the state of the surface of sapphire crystals by a complex of methods in different stages of crystal treatment are considered by an example of preparing sapphire substrates with a supersmooth surface. The possibility of purposefully forming regular micro- and nanoreliefs and thin transition layers using thermal and thermochemical impacts are considered. The advantages of sapphire substrates with a modified surface for forming heteroepitaxial CdTe and ZnO semiconductor films and ordered ensembles of gold nanoparticles are described. The results of the experiments on the application of crystalline sapphire as a material for X-ray optical elements are reported. These elements include total external reflection mirrors and substrates for multilayer mirrors, output windows for synchrotron radiation, and monochromators working in the reflection geometry in X-ray spectrometers. In the latter case, the problems of the defect structure of bulk crystals sapphire and the choice of a method for growing sapphire crystals of the highest structural quality are considered.     

Melt Growth of CdTe Crystals and Transmission Electron Microscopic Investigations of their Grain Boundaries

Transmission electron microscopy investigations are carried out on CdTe crystals grown in quartz ampoules in a temperature region (1020–1091 °C) near to the melting point of 1092 °C, by travelling heater method in quasi-closed and in sealed (at 0.135 Pa) volume, and by the Bridgman method from nearly stoichiometric melts. An original method for preparation of CdTe thin foil is reported. Two types of grain boundaries are observed: high-angle misoriented grain boundaries (more than ten degrees misorientation between adjacent grains) and low-angle misoriented grain boundaries (less than one degree misorientation between adjacent sub-grain). Both dislocations with Burgers vector b = a/6 〈112〉 and b = a/2 〈110〉 are present.     

X-Ray Diffraction Studies on Point Defects in II–VI Compounds

The point defect concentration in Te-rich CdTe and Hg_1-xCd_xTe annealed at various temperatures has been estimated from precision lattice parameters using a simple continuum inclusion model and compared with densities of electrically charged defects determined by high-temperature Hall and conductivity measurements. The nonstoichiometry is realized by cation vacancies. Dependent on the CdTe content, the ratio of total to charged defect concentrations varies between about unity for HgTe-rich composition and 75 for CdTe. Therefore, it is necessary to distinct between “electrical” and “chemical” stability regions.     

Photoacoustic Spectroscopy of Defect States in Etched and Air-annealed CuInSe2 Single Crystals

Photoacoustic spectra of cleaved, polished and etched, and air-annealed n-type CuInSe₂ single crystals are measured at different frequencies between 30 and 312 Hz. The spectra related to the bulk of the crystals exhibit five structures due to defects that are also present in p-type crystals. Polishing and etching as well as subsequent air annealing at 100, 200 and 300 °C reveal rather complex changes of the defect equilibrium in the near-surface region of the crystals which include both relative concentration changes of existing defects and creation of new defects. The results for polished and etched crystals correspond to trends expected from etching induced local modifications of the composition and structure as revealed by electron spectroscopies and ion channeling. Air annealing is found to affect all existing defects and to create up to five new defects which cannot be explained in terms of the related point defect model proposed by CAHEN and NOUFI.     

Vacancy defects in bulk ammonothermal GaN crystals

We have applied positron annihilation spectroscopy to study in-grown vacancy defects in bulk GaN crystals grown by the ammonothermal method. We observe a high concentration of Ga vacancy related defects in n-type samples in spite of the low growth temperature, suggesting that oxygen impurities promote the formation of vacancies also through other mechanisms than a mere reduction of thermodynamical formation enthalpy. On the other hand, no positron trapping at vacancy defects is observed in Mg-doped p-type samples, as expected when the Fermi level is close to the valence band and intrinsic defects are dominantly positively charged. Annealing of the samples at temperatures well above the growth temperature is found to change significantly the defect structure of the material.     

Melt growth and post‐grown annealing of semiinsulating (CdZn)Te by vertical gradient freeze method

We present results of development of CdZnTe semi‐insulating crystals prepared by Vertical Gradient Freeze method in a 4‐zone furnace. We applied the way of growth of the crystal from the top when the first crystallization seed is created on the surface of the melt. The typical height of the crystals is 5 cm. Resistivity and photoconductivity profiles measured along the growth axis by contactless method are compared and their mutual correlation is explained based on a model of relative shift of the Fermi level and the midgap level present in the material. The influence of the Fermi level on electron trapping and recombination is summarized. We present here results of a two‐step annealing method aimed at reduction of Te inclusions while keeping the resistivity high. We employed CdTe:Cl VGF grown samples to eliminate Te inclusions observed in as grown crystals by two‐step post grown annealing in Cd and Te atmosphere and present a model of the processes leading to high resistivity material after annealing.