The growth of HgI2 crystals

The paper presents a system for αHgI₂ crystal growth by the temperature oscillation method. The system has a capability of crystal growing at an excess I₂ or Hg vapour pressure. Optimum conditions for producing crystals up to 2 cm³ by volume have been established. The crystals grown at an excess I₂ vapour pressure have higher resistivity and higher drift electron and hole mobilities — μ_e = 120 cm² V⁻¹ s⁻¹ and μ_h = 6 cm² V⁻¹ s⁻¹, respectively.     

Study of surface morphology of vapour-grown HgI2 platelets

Fresh and old as-grown {001} surfaces of α-HgI₂ platelets were studied by optical microscopy. The presence of growth hillocks and the high value of the surface entropy factor are proofs of the spiral growth of platelets. In air surfaces became gradually dull. Consequently, the final micromorphology of HgI₂ is the result of both growth (primary) and post-growth (secondary) processes. For the revelation of defects a new, reliable etchant was used.     

Crystal growth of β-Phthalocyanines from the vapour phase in closed ampoules

An influence of temperature gradient, inert gas pressure and pulling rate on the growth parameters of β-phthalocyanine single crystals grown in the closed ampoules is investigated. The morphology and structure — sensitive properties of β-CuPc crystals grown under different conditions are compared.     

Complexes in the vapour phase and their implications for vapour growth

The significance of polymeric molecules (Cu₃Cl₃, Pt₆Cl₁₂, Ag₃I₃) for chemical transport and the direction of transport in temperature gradients is described. A survey of the large number of dimeric chloride molecules discovered so far, and the corresponding enthalpies of dimerization, is given. 1 : 1 Heterocomplexes such as LiCsCl₂, NaAlCl₄, KThCl₅, CdPbCl₄, AIUCl₈, ThUCl₈, and their enthalpies of reaction for the formation of such complexes from the dimers of the components (e.g., Na₂Cl₂ + Al₂Cl₆ or Th₂Cl₈ + U₂Cl₈) are reported. The stability of larger heterocomplexes (e.g., MeAl₂Cl₈, MeAl₃Cl₁₂, CoGa₂Cl₈, Tl₂ThCl₆) is also reported. The deposition of crystals of compounds, such as CuCl₂, CrCl₂,HgCr₂Se₄, Pd₂A l, by means of gas complexes as reactants, is described.     

Interplay of activation and diffusion in crystal growth from the vapour phase

Recent theories of gas transport in crystal growth by dissociative sublimation are extended to include activated adsorption of either or both species at the growing interface. The regions of diffusion-limited and activation-limited growth are delineated, and an important and extensive region of intermediate control shown to exist.     

Study of the evaporation mechanism in silicon carbide crystals growth from vapour phase

Investigation of the thermal etching (evaporation) of the source material in the process of silicon carbide crystal growth from the vapour phase by the sublimation method has been carried out. It has been established that silicon carbide etching in the temperature interval (2200–2600) °C takes place with the formation of whiskers of evaporation. The mechanism of their formation has been examined and the character of the whisker distribution in the charge of the source silicon carbide has been studied.     

碘化汞(α-HgI2)晶体生长及其性能表征

利用垂直两温区透明油浴炉,采用升华法成功生长了α-HgI2单晶体.通过对比不同生长阶段晶体生长界面,观察到HgI2晶体在气相生长中存在界面形貌转变.晶体生长初期的生长面呈棱面,然后逐渐转变为圆滑界面.利用XRD、透射光谱以及I-V测试对所生长晶体的性能进行了表征.XRD结果表明所生长的晶体为单相的α-HgI2晶体,晶体的生长方向为[001].紫外-可见-近红外透过光谱分析发现,HgI2晶体的截至波长为580 nm,对应的禁带宽度为2.12 eV,近红外区内透过率约为45;.由于空穴的俘获及陷阱能级作用,在2307.5 nm和1731.4 nm处产生了两个明显的吸收峰.所生长的α-HgI2晶体电阻率约为1011Ω·cm,满足制作核辐射探测器的要求.     

The impact of pressure and temperature on growth rate and layer uniformity in the sublimation growth of AlN crystals

To effectively design a large furnace for producing large-size AlN crystals, a fully coupled compressible flow solver was developed to study the sublimation and mass transport processes in AlN crystal growth. Compressible effect, buoyancy effects, flow coupling between aluminum gas and nitrogen gas, and Stefan effect are included. Two sets of experimental data were used to validate the present solver. Simulation results showed that the distributions of Al and N₂ partial pressures are opposite along the axial direction due to constant total pressure and Stefan effect, with the Al and nitrogen partial pressures being highest at the source and seed crystals positions, respectively. The distributions of species inside the growth chamber are obviously two-dimensional, which can curve a flat crystal surface. Simulation results also showed that AlN crystal growth rate can be increased by reducing total pressure or by increasing seed temperature or by increasing source-seed temperature difference. High nitrogen pressure causes decrease in growth rate, but it is beneficial for obtaining uniform growth rate in the radial direction. Results of simulation also showed that there is an optimized temperature difference (40 °C) in the present furnace for obtaining good homogeneity of growth rate.     

Crystal growth from the vapour phase: Confrontation of theory with experiment

Starting with the BCF theory recent crystal growth models based on computer simulations are discussed. These models are confronted with experiments for growth from the vapour concerning rates of growth and the direct observations of step patterns, growth spirals and etch pits.     

Kinetical study of the nonstoichiometric vapour growth process in the system ZnSe:I2

We have studied the growth of ZnSe crystals by chemical transport in a closed system in nonstoichiometric conditions, and we have deduced that the interface kinetics is the phenomenon limiting the growth process. The effect on the growth process of the deviation from stoichiometry of the II‐VI compound was investigated using a mathematical model that involves indirect data computed from directly obtained experimental values. The experimental crystallization rate was compared with the maximum value of the transport flux calculated using the Arizumi‐Nishinaga model. The influence of the stoichiometry of the source material and of the variations in the growth parameters (supercooling, geometrical dimension, specific loading of the ampoule and iodine concentration) on the ZnSe crystal growth process has also been studied. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gaseous control of vapour concentration in crystal synthesis from the vapour phase

The gaseous control in the crystal synthesis from the initial components is discussed. The dependences of the vapour concentrations in the growth region on inert gas flows have been calculated. It is shown that the use of additional inert gas flows conducted directly to the entries into the reaction zone makes it possible to change the vapour concentrations in the growth region rapidly and independently one from another, and these concentrations are linear with the main transport gas flows.     

Numerical study of radial temperature distribution in the AlN sublimation growth system

A large radial temperature gradient in the AlN sublimation growth system would lead to non‐uniform growth rate along the radial direction and introduce thermal stress in the as grown crystal. In this paper, we have numerically studied the radial thermal uniformity in the crucible of a AlN sublimation growth system. The temperature difference on the source top surface is insignificant while the radial temperature gradient on the lid surface is too large to be neglected. The simulation results showed that the crucible material with a large thermal conductivity is beneficial to obtain a uniform temperature distribution on the lid surface. Moreover, it was found that the temperature gradient on the lid surface decreases with increased lid thickness and decreased top window size.     

Plasma enhanced growth of GaN single crystalline layers from Ga vapour

We present an alternative approach to grow thick GaN single crystalline layers from Ga vapour, transported by an N₂ carrier gas flow, and from nitrogen, excited very near the substrate by 2.45 GHz microwaves at pressure in the 200–800 mbar range. Crystal growth requires high stability of process parameters, especially of plasma operation. A major challenge arose from temperature dependent changes in cavity resonance. Optical emission spectroscopy (OES) was used for plasma characterization while the grown layers were characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD).     

Growth of hollow Bi2Se2S crystals from vapour

Hollow crystals of Bi₂Se₂S have been grown from vapour. Crystals show open lateral surface and the length of the crystals is 6 to 7 mm. An explanation is given for the growth mechanism of the hollow crystals.     

HgO-HI-H2O体系中碘化汞(HgI2)结晶形貌研究

通过氧化汞(HgO)在氢碘酸(HI)溶液中反应实验,研究了HgO-HI-H2O生长体系中反应物浓度的变化对最终HgI2结晶形貌的影响.采用岛津UV-2550紫外可见分光光度计分析了反应体系中离子及配合物的种类;采用LEICA-DM2500P偏光显微镜观察了结晶物质的的宏观生长形貌;利用盒计数法定量表征了HgI2结晶物在衬底表面的覆盖度.结果表明,体系中存在[HgI3]-和[HgI4]2-两种配合物;随着生长体系浓度(HgI2析出速率)的变化,HgI2出现了两种结晶形貌.分析认为,高溶质浓度体系容易形成四方形晶粒,生长形貌主要受晶体结构因素影响;低浓度体系容易形成密枝晶,其形貌主要受分子扩散动力学因素控制.     

Crystal structure of the growth surface of silicon carbide obtained by sublimation

Structural study of polycrystalline silicon carbide obtained by sublimation performed via X-ray luminescence and X-ray diffraction analysis. It is shown that chemical vapor deposition of silicon carbide results in the formation of grains with the (00.1), (01.1), and (12.3) crystallographic planes parallel to the growth surface. The grains with the (00.1) growth planes are characterized by perfect structure and by red luminescence. Domains with yellow luminescence have a mosaic structure with the (01.1) and (12.3) growth planes.     

Nucleation of AlN on SiC substrates by seeded sublimation growth

The nucleation of aluminum nitride (AlN) on silicon carbide (SiC) seed by sublimation growth was investigated. Silicon-face, 8 off-axis 4H-SiC (0 0 0 1) and on-axis 6H-SiC (0 0 0 1) were employed as seeds. Initial growth for 15 min and extended growth for 2 h suggested that 1850 °C was the optimum temperature of AlN crystal growth: on an 8 off-axis substrate, AlN grew laterally forming a continuous layer with regular “step” features; on the on-axis substrate, AlN grew vertically as well as laterally, generating an epilayer with hexagonal sub-grains of different sizes. The layer's c-lattice constant was larger than pure AlN, which was caused by the compression of the AlN film and impurities (Si, C) incorporation. Polarity sensitive and defect selective etchings were performed to examine the surface polarity and dislocation density. All the samples had an Al-polar surface and no N-polar inversion domains were observed. Threading dislocations were present regardless of the substrate misorientation. Basal plane dislocations (BPDs) were revealed only on the AlN films on the 8 off-axis substrates. The total dislocation density was in the order of when the film was 20– thick.     

Effect of electrical field on growth of gallium arsenide layers from vapour phase

The effect of electrical fields on the growth rate and morphology of gallium arsenide layers in the GaAs AsCl₃ H₂ system is investigated. The fields both parallel and perpendicular to the substrate surface are used. It is found that application of the parallel field results n increase of growth rate of (111)A face but does not change that of 2° (001). The morphology of layers grown in such a field is better than that grown without any. The application of perpendicular field results in decrease of growth rate for both crystallographic orientations, the layer morphology worthening. In both cases the effect is greater when the substrate has a negative potential. Possible mechanisms of the field influence on the growth rates of gallium arsenide layers are discussed such as: supersaturation decrease because of nucleation in vapour phase and the change in the rates of surface processes.