Growth of high-purity ZnTe single crystals by the sublimation travelling heater method

A travelling heater method (THM) was developed to grow high-purity ZnTe from the vapor phase. This crystal growth method is called the “sublimation THM”. The temperature of the sublimation interface was set at 815°C and the temperature of the growth interface was varied from 785 to 800°C. The growth rate was 3 mm/day. Under these conditions, it was found that the growth process was mainly due to surface nucleation. Characteristics of the crystals were compared with those of solution-THM and vapor phase epitaxially grown crystals. The free-exciton line at 2.381 eV strongly appears and a doublet structure in neutral- acceptor bound exciton at 2.375 eV is clearly resolved with splitting energy of about 0.7 meV. We thus conclude that the THM from the vapor phase is suitable for preparing ZnTe single crystals which have excellent luminescent properties.     

Phase diagrams for the MOVPE growth of ZnTe and ZnSeTe

The phase diagrams for the MOVPE growth of ZnTe and ZnSeTe have been proposed for the first time, based on the thermodynamic equilibrium established at the solid-vapor interface. The regions for the single condensed phase of ZnTe(s) and of ZnSeTe(s) have been investigated, respectively. Additionally, the growth conditions of appearance for the double condensed phase of ZnTe(s) + Zn(s or ) and ZnTe(s) + Te(s or ) for the ZnTe system, of ZnSeTe(s) + Zn(s or ) and ZnSeTe(s) + Te(s or ) for the ZnSeTe system are discussed.     

Structural characterization of heteroepitaxial films of CdSe and ZnTe

The effects of composition, orientation and temperature of substrate on the structure and morphology of epitaxial CdSe and ZnTe films are analyzed. Single crystal wafers of zinc telluride and zinc selenide oriented along (110) and natural cleaved mica were used as substrates. This paper presents a complex investigation of the growth mechanism and crystal perfection of the films by optical microscopy, X-ray and electron diffraction, and by electron microscopy. The structure of the transient region of the film substrate interface was studied by X-ray microanalyzer and by scanning electron microscope. Cadmium selenide layers grown on mica had hexagonal structure and were oriented in the (0001) plane, those grown on zinc telluride crystals had cubic structure and orientation along (110). Zinc telluride layers were cubic and were oriented parallel the (111) plane when deposited on mica, and parallel to (110) when deposited on zinc selenide substrates. It is shown that the layers grew by a layer mechanism. Epitaxial growth of cubic cadmium selenide layers on zinc telluride single crystals, as well as of ZnTe layers on ZnSe substrates, made it possible to grow heterojunctions with a low density of misfit dislocations at the interface; this gave rise to intensive injection electroluminescence and effective separation of non-equilibrium charge carriers in such structures.     

Studies on the vapour growth of ZnS,ZnSe and ZnTe single crystals

Large, highly perfect single crystals (up to 10 × 10 × 5 mm³) of ZnS, ZnSe and ZnTe have been grown from the vapour phase by dissociative sublimation and chemical transport with iodine. Good quality crystals were obtained when the growth rate was limited by diffusion of the vapours rather than by thermal convection or by reaction rates at the charge and or the growing surface. The presence of an inert gas and defined iodine concentrations increase the growth stability, especially for charges with slight deviations from stoichiometry. Electronmicrographs, X-ray topographs and etching experiments revealed low dislocation densities and relatively large inclusion-free regions.     

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)     

Photo-assisted growth of ZnTe by metalorganic chemical vapour deposition

The metalorganic chemical vapour deposition (MOCVD) photo-assisted growth of ZnTe using a xenon lamp has been performed at atmospheric pressure under hydrogen as a carrier gas. Epitaxial growth was achieved on (100) GaAs, (100) GaSb and (100) ZnTe substrates with diethylzinc (DEZn) and diethyltellurium (DETe) as precursors. We have studied the growth rate as a function of the growth temperature, the partial pressure of precursors, the inlet partial pressure ratio R = VI/II, the light intensity and the energy of the irradiating photons. A growth rate enhancement has been observed for illuminated layers grown on GaAs and ZnTe substrates in comparison with those grown without illumination. We have not observed any measurable enhancement for layers grown onto (100) GaSb. The growth rate as a function of the light intensity increases for intensities higher than 20 mW / cm² and saturates for P > 120 mW / cm². We relate the growth rate enhancement to irradiating photons with an energy higher than the band gap of ZnTe at the growth temperature.     

TEM,chemical etching and FTIR characterization of ZnTe grown by physical vapor transport

ZnTe ingots were obtained by the physical transport method, using an in‐house designed and built tubular furnace. The growth of ZnTe subsequently to the growth of a seed of this material allowed obtaining an ingot formed by only one large and single crystalline grain. TEM was used for the characterization of the as‐grown ZnTe single crystal ingots and commercial single‐crystalline wafers of the same material but grown by a higher temperature and more expensive technique, the Bridgman method. Both materials show very good crystalline microstructure, although some stacking faults were found in the commercial one. The infrared transmittance spectra of both materials were measured by FTIR and some differences, most likely due to differences in raw materials and growth methods, were found. The effectiveness and convenience of several chemical etchants to obtain the dislocation density and the minimal misorientation between adjacent subgrains in the as‐grown ZnTe wafers were checked. It has been found as the most advantageous the chemical solution that does not produce over‐etching. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low-temperature growth of epitaxial layers of ZnSe1−xTex solid solutions

The layers of ZnSe_1−xTe_x (0 < x < 1.0) solid solutions have been grown by liquid-phase epitaxy in a closed tube at 620–680 °C. Zinc chloride served as a solvent. ZnTe and ZnSe crystals were used as sources and substrates with orienting surfaces (110) and (111) for ZnSe and (110) for ZnTe. The composition of the grown layer was specified by the relative content of the ZnSe and the ZnTe in the solution and was controlled by X-ray analysis. The position of the exciton bands in the photoluminescence spectra of ZnSe_1−xTe_x over the interval 0.3 < x < 1.0 is in agreement with the free exciton energies calculated for these compositions. Relatively low-ohmic (of about 10² Ω cm) epitaxial layers of ZnSe_1−xTe_x solid solutions were grown.     

Growth of cadmium zinc telluride by liquid phase electroepitaxy

This study was undertaken to examine the feasibility of growing CdZnTe by liquid phase electroepitaxy. Based on our successful LPEE system of GaInAs, a new crucible to grow CdZnTe was developed. The development presented numerous difficulties. The physical properties of CdZnTe make this material very difficult to grow. All components of the system were investigated. Electromigration of the solute across the solution carries species towards the growth interface. In liquid Cd‐Zn‐Te, the CdTe and ZnTe species remain associated, contrary to the GaInAs system. Experiments showed that LPEE growth of CdZnTe is possible and the electromigration mechanism functions well in the CdZnTe solution. Despite this, other problems remained with the new LPEE system. The preparation of the solution proved difficult without pressurizing the LPEE crucible. Control of the reaction required the use of pre‐compounded CdTe and ZnTe. Proper control of the solution saturation is imperative to ensure minimal dissolution of the seed prior to growth initiation and a reasonable growth rate during growth. The solution remained an issue during the duration of growth due to the high vapor pressures of the constituents. Tellurium evaporation during growth could lower solution volume until electrical contact across the solution is broken. Careful preparation of appropriate solution volume was imperative for successful growth. In LPEE, a uniform electric current passage across the growth interface is necessary for uniform and stable growth interface. This requires the design of a uniform contact zone between the bottom graphite electrode and the seed crystal. The contact zone issue was not adequately resolved in this study. However, a number of successful growth runs were achieved despite the electrical contact problems. Results show that the LPEE of growth CdZnTe is feasible. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of ZnTe layers on (111) GaAs substrates by metalorganic vapor phase epitaxy

ZnTe layers were grown on (111) GaAs substrates by metalorganic vapor phase epitaxy using dimethylzinc and diethyltelluride as the source materials. X-ray diffraction analysis revealed that epitaxial ZnTe layers can be obtained on (111) GaAs substrates. X-ray rocking curves, Raman spectroscopy, and photoluminescence measurements showed that the crystal quality of ZnTe layers depends on the substrate temperature during the growth. A high-crystalline quality (111) ZnTe heteroepitaxial layer with strong near-band-edge emission at 550 nm was obtained at a substrate temperature of 440 °C.     

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.     

Growth and Characterisation of (CuInTe2)1‐x(2 ZnTe)x Solid Solution Single Crystals

The crystal structure as well as the optical properties in the band gap region of (CuInTe₂)_1‐x(2 ZnTe)_x solid solution single crystals grown by directional freezing have been studied. The lattice constants exhibit a linear dependence on crystal composition. The chalcopyrite‐sphalerite phase transition was observed between x = 0.3 and x = 0.4°. The variation of the band gap with respect to crystal composition can be described by a quadratic expression.     

Growth of lanthanum heptamolybdate crystals by gel technique

The growth of single crystals of lanthanum heptamolybdate is achieved by allowing controlled diffusion of La ions through silica gel using the system La(NO₃)₃ MoO₃ NH₄OH HNO₃–Na₂SiO₃. The reaction mechanism leading to the growth is reported. Mechanism of crystallization of La heptamolybdate is discussed. Formation of Liesegang rings consisting of La heptamolybdate crystals in the system is reported. It is observed that concentration programming and seeded growth enhances the size of crystals. The crystals grown in the system are single crystal platelets exhibiting squarish or octagonal facets. Some crystals exhibit a spherulitic morphology.     

Transient regimes in the growth of large-diameter crystals

The behaviour of crystallization rate and interface position under the change of Czochralski growth system parameters is theoretically and experimentally investigated for the case of large diameter crystals growth. It is shown that the large value of crystal diameter leads to the inertia and nonmonotonic character of system relaxation after the perturbation. The possibility of hesitative nonstability is discussed. The transient regimes in the growth of 30 cm diameter KCl single crystals are investigated experimentally. The behaviour of crystallization rate differs from the case of small diameter crystals and corresponds to the results of theoretical analysis.     

In situ measurement of the thermal and photo-assisted MOVPE of ZnTe using laser reflectometry

In situ laser reflectometry has been used to study the growth kinetics of ZnTe under pyrolytic and photo-assisted conditions from diisopropyltellurium (DIPTe) and dimethylzinc.triethylamine (DMZn.TEN). The growth rate of ZnTe was monitored as a function of VI:II ratio, temperature and laser power density. From the results a model for the growth involving the surface decomposition of DIPTe via a bimolecular reaction with methyl radicals homolytically released from the decomposition of DMZn.TEN is proposed. The activation energy under pyrolytic conditions in the low temperature regime for a 1:1 VI:II ratio was found to be 27.6 kcal/mol and under photo-assisted conditions this activation energy was seen to be lowered to 21.9 kcal/mol. The growth kinetics are explained in terms of two competitive processes. The decomposition of DMZn on the surface will be enhanced with increasing substrate temperature; however, the desorption rate of DIPTe will also be enhanced. The competitive nature of these two processes is seen to be particularly pronounced under laser illumination at high power densities, where a growth rate of 13 a.u./s was observed at 360°C, laser power density 67 mW/cm², whereas at 380°C for a similar power density the growth rate was seen to be reduced to 10.5 a.u./s.     

Enhancement of the Automatic Diameter Control System for the Czochralski Growth of Nd:GdVO4 Crystals

The automatic diameter control system was enhanced for the growth of Nd-doped GdVO₄ single crystals by the Czochralski method. It was estimated that excessive amount of feedback in the control system is the effective way to improve the shape of rare-earth vanadate single crystals. The spectral analysis for crystal weight and generator power signals was carried out in real time during growth process for determination of oscillations in the control system.     

Correlation of fundamental photoreflectance spectra with surface quality of bulk ZnTe semiconductor grown from Te solution

Large size ZnTe single crystals were grown from Te‐solution with the vertical Bridgman method. The fundamental photoreflectance (PR) spectra of bulk ZnTe crystal subjected to a successive sequence of surface treatments, i.e., mechanical and chemical polishing, and passivation, have been measured over the wavelength range 200–600 nm at room temperature (RT) for the first time. The shape, relative intensity and evolution of the distinct E₀, E₁, E₁+∆₁ and E₂ transitions during each stage of wafer processing were investigated. It was found that, those distinct transitions vary with varying crystal surface quality. The intensity of the reflectance peaks is large with sharp peak profile when the surface has good crystalline quality. However, E₀ peak can be easily eliminated by a small amount of structural damages on the wafer surface. The dispersion tendency of the E₁ and E₁+∆₁ peaks suggesting the wafer surface is widespread covered by structural damages. The reflection peaks’ intensity were all reduced after passivated with H₂O₂ solution. E₂ peak intensity is more easily to be reduced during passivation.     

Enhanced Automatic Diameter Control System of Czochralski-grown Crystals

The automatic diameter control system with two ways of the crystal diameter determination is described. The correction of temperature oscillations during the growth process is applied in the describing system. Also, it allows to estimate the crystal quality already during the growth process. The control system is intended for the growth of crystals with different physical properties.     

Cover Picture: Cryst. Res. Technol. 8/2010

The cover picture shows a ZnTe ingot grown by physical transport using a seed crystal in the conical part of the quartz ampoule. Twins along the axis of the ZnTe ingot seem to be a frequent defect in the physical transport method. (see pages 817–824).     

Growth of calcium carbonate in polyacrylamide hydrogel: Investigation of the influence of polymer content

The growth of calcium carbonate crystals has attracted growing attention as a model system for biomineralisation processes. Organic molecules and gelatinous matrices are known to play an essential role in the formation of hard tissues. For the investigation of the function of specific influence factors, a model experiment is necessary. Several hydrogels were previously tested as growth matrices for calcium carbonate.

For laboratory experiments, a double diffusion set-up for the growth of crystals in gels was established earlier. Calcium carbonate crystals were grown in polyacrylamide hydrogels.

Here the influence of the polymer content in the hydrogels on the crystallisation behaviour is reported. Time-resolved and spatially resolved crystallisation experiments were conducted. The collected calcium carbonate precipitates were analysed by light microscopy, scanning electron microscopy and X-ray diffraction.

The morphology of the developing crystals was found to be dependent on the polymer content of the hydrogels.