Solvent effect on the polytype structure of CdI2 crystals

Single crystal platelets of cadmium iodide have been grown from alcohols: n-propyl, isobutyl and isoamyl and from their aqueous solutions. The structures of 880 crystals has been identified and the effect of solvent on the polytype structure of CdI₂ has been discussed regarding: the stability of the basic structures 2H and 4H, the structure of complex polytypes, the effect of the solvent on the structure of faults, the period of polytypes. Some relations indicating the role of the solvent in the formation of polytype structure of CdI₂ have been found.     

Studies on syntactically coalesced Silicon Carbide polytype structures

The structure of two new silicon carbide polytypes, found in syntactic coalescence with a basic structure 6 H, have been worked out. The structure of polytype 21 H is [(33)₂63] and that of polytype 93R is [(33)₄34]₃. The polytype 93R belongs to the structure series [(33)_n34]₃. One of the (00.1) growth face reveals the growth spiral. The splitting of diffraction spots indicates the existence of a high period polytype in the crystal. This high period polytype have been identified as 558H or 1674R. The growth mechanism have been discussed in the light of above observations.     

4H-SiC晶体表面形貌和多型结构变化研究

利用光学显微镜、显微拉曼光谱仪研究了4H-SiC晶体表面形貌和多型分布.显微镜观察结果显示4H-SiC小面生长螺蜷线呈圆形,沿<11(2-)0>方向容易出现裂缝.裂缝两侧有不同的生长形貌.拉曼光谱结果显示缺陷两侧为不同的晶型,裂缝实际为晶型转化的标志.纵切片观察发现,在4H-SiC和15R-SiC多型交界处产生平行于<11(2-)0>方向裂缝;15R-SiC多型一旦出现,其径向生长方向平行于<11(2-)0>方向,轴向生长方向平行于<000(1-)>方向.     

Melt-Growth of Single Crystals of Cadmium Iodide and Study of Their Polytypsim by X-ray Diffraction

Single crystals of cadmium iodide have been grown from melt using Bridgman-Stockbarger system and their polytypism studied by X-ray diffraction. The initially grown crystals were found to stick to the walls of the ampoule and had black specks of impurity suspended in them. A systematic study has been carried out to determine the effect of degree of vacuum, material of the ampoule and quality of raw material on crystal growth. It has been concluded and later verified using zone-refined material that the observed sticking essentially stems from the presence of impurities in the raw material. From X-ray diffraction it is found that all crystals belong to the most common polytype 4H alone.     

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。     

Zn1−xCdx polytype single crystals with various degree of order

The results of X-ray investigations of the polytype structures formed in solid solutions of Zn_1–xCd_xSe are presented. For compositions of 0.22 < x < 0.35 polytypes 8H, 6H, 4H, and DS (disordered structure) are present. The Zn_1–xCd_xS single crystals of 0 ≦ x ≦ 0 were obtained by Bridgman's method under high protective argon pressure from the melt. The structures are characterised by FARKASZ -JAHNKE statistical parameters π(m,p), and by parameters P_LH of the polytype unit cell formation probability.     

A model for the growth of anomalous polytype structures in vapour grown SiC

A number of polytype structures observed in vapour grown SiC crystals have a unit-cell which is an integral multiple of the unit-cell of the basic 6H, 15R or 4H structure. The growth of such anomalous structures cannot be understood in terms of spiral growth round a single screw dislocation in a basic matrix. However many of these polytype crystals display a single growth spiral on their (0001) face indicating that they have resulted from spiral growth round a single screw dislocation. It is shown that this anomaly can be resolved if the basic matrix is assumed to contain stacking faults near the surface at the time of the origin of the screw dislocation ledge. This possibility, overlooked in the earlier deduction of polytype structures, must be taken into consideration since vapour grown SiC crystals frequently contain a high concentration of random stacking faults, producing continuous streaks on their X-ray diffraction photographs. The most probable fault configurations that can occur in 6H, 15R and 4H structures of SiC have been deduced from a calculation of their stacking fault energy. These fault configurations are then considered to lie at different distances from the surface at the time of the origin of a screw dislocation ledge. Such a faulted ledge gives rise to polytype structures during subsequent spiral growth even if the screw dislocation has an integral Burgers vector. The most probable series of polytype structures that can result from such a faulted matrix model are deduced. It is shown that nearly all the polytype structures of SiC hitherto regarded as anomalous (such as 36H, 54H, 66H, 45R, 90R etc.) are among the expected structures and there is no need to postulate a complicated configuration of cooperating dislocations to account for their growth.     

STGR Model and Relation between Growth Rate and Polytypism

Effect of crystal growth rate on polytypism has been explained using STGR model. It has been suggested that during the process of growth, polytypes are formed from a suitable combination of basic units in accordance with the rate of growth. At a slower rate the most probable polytype is predicted to be different from the one at faster rate.     

On the Structural and Electronic Characteristics of Titanium Sulphide (Tis1.7) Crystals

TiS_1.7 crystals have been grown by vapour transport technique employing a two-zone furnace with the temperatures of reaction and growth zone maintained at 1073 K and 973 K, respectively. We have measured the variation of electrical conductivity (s̀) with temperature (T) of TiS_1.7 single crystals. It has been found that the conductivity increases at temperatures T > 433 K, which provides convincing evidence that the TiS_1.7 crystal is a semiconductor. Another electronic characteristic of TiS_1.7 crystals observed in the present investigation is the occurrence of voltage controlled negative resistance (VCNR) at a field of 32.1 V cm^-1 to 35.7 V cm^-1. All the polytypes of TiS_1.7 were found to exhibit VCNR nearly at the same field which indicates that the VCNR is polytype independent property. The occurrence of VCNR has been explained on the intervally transfer of electrons in the conduction band.     

New schemes for recording electron diffraction patterns of hexagonal and monoclinic crystals

Some new schemes for recording electron diffraction patterns of hexagonal crystals rotating around the axes lying in the (hk0) plane of the reciprocal lattice and monoclinic crystals rotating around the a and b axes of the direct lattice and the a* axis of the reciprocal lattice have been developed. Formulas for interpreting electron diffraction patterns are reported. The electron diffraction patterns obtained based on these schemes were used to solve the 2H and 3R polytypes of CdInGaS₄ crystals and the 3R polytype of Zn_1.5In₃Se₆ crystal with the parameters a = 4.046 and c = 59.292 Å, sp. gr. R3m.     

Effect of an External Magnetic Field on Polytypism of CdI2 Crystals Grown from Solutions

The effect of growth conditions on the polytypic structure of crystals of CdI₂ was analyzed for crystallization from solutions. Three solvents were used: H₂O, 3 H₂O + 1 C₂H₅OH and 1 H₂O + 1.C₂H₅OH. Crystals were grown at two temperatures: 5 and 25°C with low and high growth rates; an external magnetic field of about 0.25 tesla was used. The effect of the above three parameters on the formation of the basic polytypes 2H and 4H and on the ordering of faults in disordered structures and polytype cells was studied by X-ray analysis of crystal surfaces. Some distinct relations between the polytypic structure of crystals of CdI₂ and the magnetic field were found.     

Propagation behavior of threading dislocations during physical vapor transport growth of silicon carbide (SiC) single crystals

The dislocation formation and propagation processes in physical vapor transport (PVT) grown 4H silicon carbide (4H–SiC) single crystals have been investigated using defect selective etching and transmission electron microscopy (TEM). It was found that while the growth initiation process generally increased the density of threading dislocations in the grown crystal, for certain areas of the crystal, threading dislocations were terminated at the growth initiation. Foreign polytype inclusions also introduced a high density of dislocations at the polytype boundary. In the polytype-transformed areas of the crystal, almost no medium size hexagonal etch pits due to threading screw dislocations were observed, indicating that the foreign polytype inclusions had ceased the propagation of threading screw dislocations. Based on these results, we argued the formation and propagation of the threading dislocations in PVT grown SiC crystals, and proposed the dislocation conversion process as a plausible cause of the density reduction of threading dislocations during the PVT growth of SiC single crystals.     

Entropy Contribution and Stacking Fault Energy of CdI2 Polytypes

The CdI₂ material when is grown by using the different techniques under a same growth conditions shows a rich character in crystallization with several phases (polytypes). The exhibition of these polytypes has been explained here by following the Gibb's phase rule. Therefore, an effort has also been made to calculate the stacking fault energy of these polytypes.     

Factors affecting the formation of misoriented domains in 6H‐SiC single crystals grown by PVT method

Misoriented domains (MDs) are common defects in 6H‐SiC single crystals. We performed an experimental study on the formation of MDs in 2‐inch 6H‐SiC single crystals. Micro‐Raman spectroscopy revealed that the polytype of MDs was mainly 4H‐SiC. By changing growth conditions, it was found that the MDs' formation was closely related to growth rate and the position of highest temperature relative to growth interface. When the growth rate of ingots was relatively high the MDs were more likely to form. Furthermore, the nearer growth interface the position of highest temperature was, the larger the size of the MDs. Based on our experimental findings we suggested that the MDs' formation and the polytype switching from 6H‐ to 4H‐SiC were due to too large axial and/or radial temperature gradients.The results would be helpful to improve the quality of SiC single crystals grown by PVT technique. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of an External Electric Field on Polytypic Growth of CdI2 Crystals from Solutions

The effect of an external steady electric field on polytypic growth of CdI₂ crystals was investigated. Crystals were grown at four temperatures: 5, 25, 35, and 50°C with the use of four solvents: H₂O, C₂H₅OH, 3 H₂O + 1 C₂H₅OH and 1 H₂O + 1 C₂H₅OH. The electric field of the intensity 500 to 2500 V/cm was oriented in two directions: perpendicular or parallel to the c-axis of hexagonal plates of CdI₂ crystals. The analysis of the effect of the field on polytypism of CdI₂ was based on the analysis of the structure of about 800 crystals grown in the presence of electric field and of about 1000 crystals grown in neutral conditions. It was established that the weak electric field used for crystallization of CdI₂ does not influence noticeably the relative stability of basic polytypes (2H, 4H) and of complex polytypic structures (ordered and disordered). The electric field may influence the structure of CdI₂ crystals in two ways: (i) the polytypes formed in the presence of the field have on average two times larger cells than the polytypes formed in neutral conditions, (ii) the polytypes formed in neutral conditions have usually hexagonal cells; only 6 to 30% of polytypes are of rhombohedral type. When the electric field was used the percentage of rhombohedral polytypes increased to about 65%.     

Study of the influence of the rare-earth elements on the properties of lead iodide

Lead iodide (PbI₂) shows excellent electronic properties for detection of ionizing radiation. We report the introduction of rare-earth elements and other elements as admixtures during synthesis to study their influence on the quality of single crystals. Synthesized material as well as single crystals have been characterized by measurements of electrical resistivity and low-temperature photo luminescence and index of refraction. The structural quality with respect to polytypes was analysed by electron back scatter diffraction. Makyoh topography was applied for surface studies.     

Growth surface topography of kaolinite-group minerals and their simulation based on the regular sequence of enantiomorphic layers

The regularities of manifestation of polytypism in a number of kaolinite-group minerals (kaolinite, dickite, halloysite, and nacrite) have been investigated by transmission electron microscopy and vacuum decoration. Growth patterns of elementary layers with a thickness of 7 Å, individual for each polytype, were observed on (001) faces of microcrystals. Specific features of the growth patterns of polytypes have been revealed by comparing them with simulated patterns constructed based on a packing of regularly alternating right- and left-handed (enantiomorphic) kaolinite layers. The new approach to the consideration of the polytypism of kaolinite minerals is substantiated by the absence of symmetry elements in the 7-Å-thick layer, which determines their structure; the formation of enantiomorphic forms of kaolinite; the presence of grazing-reflection planes in the growth patterns; and the structure of polytypes with a two-layer period. Packing of enantiomorphic layers may yield eight structures, two of which correspond to the right- and left-handed forms of kaolinite, one is for dickite, two are for halloysite, and three are for nacrite. It is shown that the simulated and real growth patterns of these minerals are in good correspondence.     

On the occurrence of polytypism in single crystal CdTe thin films

Cadmium telluride thin films have been found to exhibit polytypism. The polytypes are formed when the as grown amorphous CdTe thin films undergo amorphous to crystalline transformation. The transformed single crystal regions correspond to different polytypes. Besides the well known zinc blende type 3 C cubic phase and less often found wurtzite type 2 H phase, four new polytypes (5 H, 6 H, 6 R and 15 R) the only ones known to-date have been found in the present investigation. In addition to the new polytypes, a new structural variant has also been found. This has the same ‘c’ parameter as that of the 2 H phase but has its ‘a’ lattice parameter as ‘a₀ \documentclass{article}\pagestyle{empty}\begin{document}$ a_{\rm o} \sqrt {3} $\end{document}’ (a₀ being the common lattice parameter of the polytypes). A feasible mechanism making the formation of polytypes intelligible has been suggested.