Geometrical aspects of solid solution separation by evaporation‐condensation driven in a closed system by a small temperature difference

Evaporation‐condensation driven in a closed system by a small temperature difference has demonstrated its ability to deliver semiconducting IV‐VI and II‐VI solid solution crystals of highest compositional uniformity. Geometrical aspects of solution component distribution emerging in the crystals grown in the near equilibrium evaporation/condensation systems are considered in this paper. The conclusion is drawn that no increase in the range of compositional variations with increase in the crystal size is to be anticipated. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Self-selecting vapour growth of bulk crystals – Principles and applicability

A method of self-selecting vapour growth (SSVG) for bulk binary and multernary crystals of semiconducting materials is reviewed comprehensively for the first time. Although it has been developed over three decades, the method is less well known – even though it is physically distinct from the more widely used ‘Piper–Polich’ and ‘Markov–Davydov’ vapour transport bulk growth methods. The means by which growth takes place on a polycrystalline source to form a crystal free from the walls is described. Modelling and empirical observations have been used to establish the characteristics of the almost isothermal temperature fields that drive the transport in SSVG. It is demonstrated that precise control of thermal radiation is a fundamental requirement for tailoring the temperature distribution—a fact that has been used well in the design of horizontal tube furnace growth rigs. Achievements in the growth of useful PbS, PbSe, PbTe, CdTe and ZnTe compound crystals are described. The SSVG method has proved to be particularly well suited to the growth of solid solutions, and the results of growth experiments, and of compositional and structural analysis, are presented for Pb(Se,S), (Pb,Sn)Se, (Pb,Sn)Te, (Pb,Ge)Te, Cd(Te,Se), Cd(Te,S) and (Cd,Zn)Te. The excellent compositional uniformity delivered is attributed to entropy driven mixing in the low thermal gradients present in SSVG.

To date, most SSVG has been done at the <50 g level for research or small scale production use. Prospects for scaling up the growth are considered, there being no barriers identified in principle. However, there is a limitation in that the shape of the grown crystals is not accurately controlled at present. To overcome this, and to offer an alternative method of scaling up, the use of vertical tube systems is explored. A significant additional advantage of the vertical configuration is that it allows for continuous recycling of the source/crystal mass so as to continuously self-refine the increasingly uniform – and crystalline – product. Achievements to date in growing II–VI and IV–VI crystals are described for prototype vertical SSVG systems. Finally, future prospects for the SSVG method in terms of further developments to the method, and the specific materials that will benefit from it are highlighted.     

Comparison of thermodynamic and kinetic models of single‐layer crystal–mother‐phase interface

Simple analytical kinetic model of single‐layer crystal–mother‐phase interface is proposed, which provides results that can be compared directly with thermodynamic Jackson model. Both models are based on zeroth order approximation known from lattice‐gas models, in which solid and fluid growth units are treated as mixed randomly in the interface layer. It is shown that the kinetic and thermodynamic approaches can lead to very similar predictions about growth mechanism. The parameters characterising growth conditions, obtained from these models, are significantly different from those obtained from Monte Carlo simulations applied to study stable states of single‐layer interface. Monte Carlo calculations describe crystal growth in detail and their results can predict characteristic parameters for real experiment. Observed differences seem to be strongly influenced by the use of zeroth order approximation. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Kinetic block model of crystal–mother‐phase interface with preferential clustering ‐ single layer case

A new single‐layer kinetic block model of crystal growth is proposed, which takes into account preference for bonds between blocks of the same type over mixed‐type bonds. The obtained parameters describing stable growth conditions were compared with other theoretical models (such as thermodynamic Jackson model and the earlier proposed kinetic model based on zeroth order approximation) which assume that new growth units are attached in a completely random way. Additionally, the results were compared with Monte Carlo simulations. The proposed model produced results which matched the simulation results much better than the other theoretical models. The new model can be used for studying crystal growth both from solution and from vapour. Calculations based on this model show that the number of created mixed‐type bonds depends on the temperature and is lower from its estimation obtained with the use of the zeroth order (Bragg‐Williams) approximation.     

Monocrystalline Cd0.2Zn0.8Te solid solution obtained by self‐selecting vapour growth

Cd_0.2Zn_0.8Te monocrystals with the sizes of about 15 mm have been produced by self‐selecting vapour growth (SSVG). High degree of structural perfection of monocrystalline Cd_0.2Zn_0.8Te was achieved. Excellent compositional uniformity was observed as well. To our knowledge, no comparable results are reported for this solid solution. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vapour‐phase growth,purification and large‐area deposition of ZnO tetrapod nanostructures

Large‐yield zinc oxide (ZnO) nanosized tetrapods have been obtained by a standard vapour‐phase growth technique to which a few modifications have been added, such as the separation of the Zn source evaporation region from the Zn oxidation region inside the reactor setup. This modification allows to keep the growth conditions constant and continuous for a long time, thus favouring the obtainment of large amounts of ZnO tetrapod nanostructures. As some contaminations usually occur due to metallic Zn particles and/or different ZnO nanostructures, including not completely reacted ZnO_1‐x solid phases, they can be removed by a three‐step “purification” procedure as described in the article. Further to that, a deposition method from suitable liquid suspensions is also reported, which allows to produce homogeneous distributions of ZnO tetrapods on large substrate areas. The proposed procedures are expected to be particularly appropriate for a large production of samples for device use. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vapour phase epitaxy of II–VI compounds: A review

This paper is mainly concerned with a critical review of the present situation in the field of vapour phase epitaxy of II–VI compounds. LPE-methods have been less successful. Single-crystal films have been grown by vacuum deposition, sublimation, chemical transport and chemical vapour deposition (including metalorganic-hydride processes). Remarkable results h have been obtained with the close-spaced technique and the chemical vapour deposition methods. The following topics from the point of view of the most suitable operating conditions for epitaxy will be discussed: preparation of substrates and source materials, chemical equilibria and material transport, supersaturation in the growth zone and growth temperature. The compounds ZnS, ZnSe, ZnTe exhibit systematic connections for the material transport, orientation dependence of growth rates and the crystal structures. Considerable interest is shown in the epitaxy of II–VI compounds, because of interesting properties with regard to opto-electronic applications, as in electro-optic information storage devices, light emitting diodes and electroluminescent displays.     

Growth of Zn‐doped Germanium under Microgravity

The doping of germanium with zinc from a remote, temperature‐stabilized source was studied under microgravity. A nominally undoped Ge‐crystal was grown by the Gradient‐Freeze technique with the melt surface being in permanent contact with a gaseous atmosphere of zinc. The dopant and carrier concentrations in the solidified Germanium were measured by SIMS, Hall and resistance measurements and compared with the results of a terrestrial reference experiment as well as with concentration profiles calculated on the basis of the thermodynamics of the growth system. The results prove the possibility of vapour phase doping under microgravity. Moreover, the Zn‐concentration at the initial phase boundary even agrees well with the equilibrium value, strongly indicating a nearly homogeneous distribution of the dopant within the melt before the crystallization.     

Atomic‐scale study of vapour growth morphology of crystalline urea

The role of surface relaxation on habit controlling energetics and growth morphology are investigated within the framework of Burton‐Cabrera‐Frank (BCF) and Hartman‐Perdok (HP) models. The habit controlling energetics has been calculated using first principles method. The growth morphology obtained using BCF theory shows that the structural relaxation has considerable effect on growth morphology. The relaxed growth morphology obtained using BCF model match with the experimental result from vapour phase. On the other hand the shape obtained using HP model does not correspond with the experimental shape. Observed polar growth morphology of urea crystal has been discussed particularly in the context of different atomic environments of (111) and (111) faces. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the Iso‐Diameter Growth of β ‐BaB2O4 (BBO) Crystals by Flux Pulling Method

The iso‐diameter growth of β ‐BaB₂O₄ (BBO) crystals by the flux pulling method have been studied based on the phase equilibrium diagram in the BaB₂O₄‐Na₂O pseudo‐binary system and from the interface stability. The mathematical expressions for the cooling rate in the growth of the crystals with constant diameter under stable growth conditions are derived, the experimental phenomena such as diameter contraction and difficulty to grow a lengthy crystal by the flux pulling method are explained, the prerequisite for iso‐diameter BBO crystal growth from the flux is suggested; a new continuous charging flux pulling method is introduced to grow large‐sized high quality crystals with a relative high growth rate.     

TEM analysis of the container effect of Au‐based catalyst droplets during vapour‐liquid‐solid growth of axial ZnTe/CdTe nanowires

Axial heterostructure nanowires (NWs) of ZnTe/CdTe were grown by vapour‐liquid‐solid growth realized in a molecular beam epitaxial chamber. By alternative supply of Zn or Cd and constant Te the heterostructure was generated. The liquid phase is provided by a Au‐based eutectic droplet which stays at the tip of the NW during the entire growth. For structural and chemical characterization by TEM the NWs were harvested from the substrate and transferred to a holey carbon film. The NWs exhibit an expansion of the diameter correlated with the interface region between ZnTe and CdTe. Idiomorphic growth of the CdTe is evident from electron diffraction experiments. The growth rate of CdTe appears to be smaller compared to that of ZnTe at the same temperature. Both, quantitative high‐resolution TEM and energy dispersive X‐ray spectroscopy line scans reveal a smeared ZnTe/CdTe interface along about 200 nm. The smearing is due to both, the liquid catalyst which buffers the supply of Cd instead of Zn at the liquid/solid interface and to the strain which is induced by the lattice mismatch. It forces the system to consume the remnant Zn for the NW growth in favour of Cd. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and magneto‐optical characteristics of cerium‐doped terbium gallium garnet by the floating zone method

Cerium‐doped terbium gallium garnet single crystal having a large Verdet constant was grown by floating zone (FZ) method, which was suitable for the use in optical devices. The lattice parameters and the X‐ray rocking curve measurement of the crystal was determined by X‐ray diffraction analysis. The Verdet constant of the crystal (B = 0.55 T) at the wavelength of 632.8 nm was −165.8 rad m⁻¹ T⁻¹ at room temperature, 23.7% larger than that of pure TGG (−134.0 rad m⁻¹ T⁻¹). The performance of the high optical quality and excellent magneto‐optical properties of the crystal shows the great potential of using this new method to meet the increasing demand of VI‐NIR Faraday rotators.     

Rapid crystal growth without inherent supersaturation induced by nanoscale fluid flows?

Crystal growth is a process that only takes place under non‐equilibrium conditions and a necessary prerequisite is that the crystal is exposed to a phase that is supersaturated in the material the crystal is composed of, be it a solution, a vapour or a supercooled melt. In industrial mass crystallization the growth rate for a population of crystals (in suspension growth processes [1]) rarely exceeds mean linear velocities of 10^‐7 ms^‐1. Here we present a mass crystallization process which is accompanied by rapid crystal growth several orders of magnitude faster and into a region of solution that is without inherent supersaturation. The material investigated is a solid hydrate that exhibits a solution mediated phase transition to its anhydrous form in the presence of methanol [2]. The phase transition is initiated simply by placing an amount of hydrate crystals into the solvent and is characterized by the rapid emergence of needle‐shaped crystals. The needles emanate from the crystal faces of the hydrate crystals and grow into the solution, which is nominally free of the substance to be crystallized. The high growth rate of the crystals, which of the order of up to 10^‐4 ms^‐1 is surprising. Although rapid needle growth has been observed before [3‐9], to date a satisfactory explanation for needles growing under the abovementioned conditions is still outstanding. Based upon the topology of the crystals we propose a tentative mechanism for this phenomenon capable of explaining the unusually rapid growth and highlight those questions that need addressing in order to verify this mechanism. X‐ray powder diffraction is used to characterize the crystal phase of the needles; confocal fluorescence microscopy reveals that the needles are hollow. The width of these needles is between 0.5 and 5 μm, their length appears to be limited only by the amount of hydrate available for their formation. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In‐situ measurements of mass transport rate in vapour growth of hexamethylenetetramine crystal layers

This paper refers to the implementation of a remote optical imaging system suitable for in‐situ mass transport rate measurements in the growth of crystalline layers when grown in closed cylindrical ampoules by a physical vapour transport (PVT) technique. By means of this system, the measurements are carried out by taking photographs, at regular time intervals, of the source material volume as it reduces itself because of mass transfer. After storing the photographs, in real time, in a PC, a suitable software allows to estimate the mass transport rate during the growth process. The authors report here on the detailed setting up of such system when aimed at measuring the growth rate, as it varies with time, of hexamethylenetetramine (HMT, urotropine) crystal layers. A presentation and discussion of the results of these measurements have previously been reported. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of 4‐(2‐hydroxyphenylamino)‐pent‐3‐en‐2‐one single crystals

4‐(2‐hydroxyphenylamino)‐pent‐3‐en‐2‐one (HPAP) was synthesized and single crystals were grown by the solution growth technique using methanol as a solvent. The crystals having orthorhombic symmetry were characterized by single crystal XRD, FTIR spectroscopy, NMR spectroscopy, TGA, DSC and dielectric studies. Very less variation in the value of dielectric constant is found for different frequencies of applied field. The crystals were exhibiting positive photoconductivity and poor NLO responses. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Numerical Simulation of Temperature and Flow Field in the Melt for the Vapour‐pressure‐ controlled Czochralski Growth of GaAs

The influence of the melt flow on the temperature field and interface during the vapour‐pressure‐controlled growth of GaAs was studied numerically with the commercial general‐purpose program FIDAP^TM. The thermal boundary conditions for the domain of seed, crystal, boron oxide and crucible were taken from a global calculation for an equipment used at the IKZ to grow 6″ crystals. Due to the large melt volume the buoyancy forces become rather strong and have to be counteracted by reasonable rotation rates. Preliminary results have been obtained for iso‐ and counter‐rotation showing that the flow field exhibits structures on small scales. High rotation rates are needed to counteract the buoyancy flow efficiently and to achieve a smooth flat interface. Even if the the flow structure is not resolved in detail, the interface shape can be deduced form the calculations.     

MOVPE of II–VI materials

The development of II–VI MOVPE is reviewed, contrasting the narrow bandgap materials with the wide bandgap. Common issues are the need to grow the layers at lower temperatures than their III–V cousins in order to avoid point defects. This means that II–VI MOVPE occurs in a surface kinetic regime for precursor decomposition and has stimulated a lot of research on alternative precursors. The narrow bandgap II–VI growers have settled on dimethyl cadmium (DMCd) combined with diisopropyl telluride (DIPTe) and a liquid Hg source but wide bandgap growers are split between pyrolytic and photo-assisted growth. Recent progress in p-type doping has enabled the demonstration of some new devices, including two colour infrared detectors and the first MOVPE grown green emitting laser structure. The common theme appears to be hydrogen passivation of the Group V dopant and some novel precursor solutions to this problem are discussed.     

The Characteristics of the Mixed Crystals of the KNO3‐NH4NO3‐H2O System at 298 K

The equilibrium studies of the KNO₃‐NH₄NO₃‐H₂O system at 298 K have been conducted. The isotherm of solubility and the curve of distribution have been mathematically described. The parameters of the crystal lattice and the enthalpy of crystallization of the [K_x(NH₄)_1‐x]NO₃ solid solutions as a function of their composition have been presented. The structure of salts KNO₃�xNH₄NO₃ with different x values have been solved and refined.     

Structural studies of crystalline oligosaccharides VI: Crystal structure and conformation of benzyl‐4,6‐O‐benzylidene‐3‐O‐benzoyl‐β‐D‐galactoside

Monsaccharides are the building blocks of polysaccharides and hence are the simplest sugar molecules to study the conformation and molecular structures of sugars. Benzyl‐4,6‐O‐benzylidene‐3‐O‐benzoyl‐β‐D‐galactoside is a key intermediate in the synthesis of polysaccharides. Crystal structural investigation of the title compound was undertaken to establish their chemical structure as well as to study their solid state conformation. Crystals of the title compound, obtained from water/methanol, are orthorhombic, space group P2₁2₁2₁, with cell dimensions a=11.290 (4), b=9.941 (1), c= 21.442(2)Å, V= 2406ų, Z=4, D_obs= 1.42 gm/cm³, D_calc=1.423 g/cm³, 2886 reflections were collected on a CAD‐4 diffractometer. The structure was solved by direct methods and refined to a final reliability index of 4.7%. The galactoside sugar has the chair conformation with C2' and C5' deviating from the mean plane of the other atoms of the sugar. The 4,6‐O‐benzylidene ring also has a chair conformation with the benzoyl group proximal to O6'. The crystal structure is stabilized by O‐H…O hydrogen bonds involving O2' as donor and three C‐H…O hydrogen bond interactions. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Debye temperature and melting point of II‐VI and III‐V semiconductors

In this paper, simple relations are proposed for the calculation of Debye temperature θ_D and melting point T_mof II‐VI and III‐V zincblende semiconductors. Six relations are proposed to calculate the value of θ_D. Out of these six relations, two are based on plasmon energy data and the others on molecular weight, melting point, ionicity and energy gap. Three simple relations are proposed to calculate the value of T_m. They are based on plasmon energy, molecular weight and ionicity of the semiconductors. The average percentage deviation of all nine equations was calculated. In all cases, except one, it was estimated between 3.34 to 17.42 % for θ_D and between 2.37 to 10.45 % for T_m. However, in earlier correlations, it was reported between 10.59 to 33.38% for θ_D and 6.96 to 14.95% for T_m. The lower percentage deviation shows a significant improvement over the empirical relations proposed by earlier workers. The calculated values of θ_D and T_m from all equations are in good agreement with the available experimental values and the values reported by different workers. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)