The influence of melt stirring intensity on the axial impurity distribution in proustite single crystals grown by the Stockbarger method using ACRT

The influence of modulated crucible rotation on the axial distribution of Cu, Mg and Si impurities in proustite single crystals grown by the Stockbarger method using ACRT is studied in a wide range of Taylor numbers (1.9·10⁵ < Ta < 7.12·10⁷). The impurity content in the upper part and in the tail portion of the grown crystals is measured using X‐ray‐phase analysis. Micro and macrostriations are observed in the grown crystals. The wavelengths of impurity content fluctuations have been determined. The microfluctuations of axial impurity content are caused by modulated crucible rotation. The studies have revealed that the ACRT provides an effective removal of impurities from the main part of the grown crystal at high intensity of melt stirring, and consequently, the ACRT can be applied validly to decrease the impurity content during the growing of high‐quality proustite single crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Properties of Undoped InP and GaP Bulk Crystals Prepared by Floating Zone Melting

Undoped GaP and InP crystals which are produced by floating zone melting without a crucible were investigated. The background concentration was 10¹⁵cm⁻³ after several passages of the molten zone. The fundamental residual impurities are carbon and silicon penetrating into the crystals during the crystallization process. After purification, the electron mobility of GaP was 200 cm²/V. s, and for InP – 4000 cm²/Vs. The compensation decreased to 20%. A very effective purification was observed with respect to the carbon atoms, but for silicon this result is observed only after several passages of the molten zone. GaP and InP are basic materials for optoelectronic devices and it is important to investigate the possibility for production of pure bulk crystals. A proper method for this aim is the floating zone melting, where the crucible effect is removed and the influence of residual impurities is observed. In this work the influence of the number of floating zone passages on the electrical and luminescence properties of InP and GAP bulk crystals has been investigated.     

Ein einfaches Verfahren zur Herstellung reiner und dotierter CdF2-Kristalle

The preparation of pure CdF₂ and of CdF₂ crystals by the Bridgman method is described in detail. The aggressivity of the melt requires special precautions concerning the crucible material and the protecting gas. By zone melting the spectroanalytical detection limit of impurities (≈ 1 ppm) is attained. Some remarks on the mechanical, thermal, and chemical properties of the crystals and on their further processing are given.     

Distribution of aluminum and indium impurities in crystals of Ge-Si solid solutions grown from the melt

The problem regarding the distribution of aluminum and indium impurities in bulk crystals of solid solutions with a variable composition Ge_1−x Si _x (0 ≤ x ≤ 0.3) is solved in order to establish regularities of the changes in the segregation coefficients of impurities with variations in the composition of the host lattice in the germanium-silicon system. Aluminum-and indium-doped crystals of Ge_1−x Si _x (0 ≤ x ≤ 0.3) solid solutions with a silicon content decreasing along the crystallization axis are grown by a modified Bridgman method with the use of a silicon seed. The concentration distribution of impurities over the length of the crystals is determined from Hall measurements. It is demonstrated that the experimental data on the concentration distribution of impurities in the crystals are in good agreement with the results obtained from the theory according to which the equilibrium segregation coefficients of impurities vary linearly with a change in the composition of Ge-Si solid solution crystals.

     

温梯法生长CaF2晶体中包裹物的研究

本文对温度梯度法生长的氟化钙(CaF2)晶体中的包裹物进行了研究,用光学显微镜和SEM观察了包裹物的形貌,对晶体中的包裹物和透明部分作了微区EDX成分分析,对包裹物所含的杂质进行了解释,提出了减小或消除包裹物的措施.分析结果表明:包裹物的主要成分是碳和氧,碳来源于石墨坩埚和石墨发热体,而杂质氧则来源于原料中的含氧化合物和生长过程气氛中氧的进入.     

The effect of crucible bottom deformation on the quality of Nd:GGG crystals grown by Czochralski method

In this paper, we report the growth of neodymium doped Gadolinium Gallium Garnet (Nd: GGG) crystal using Czochralski (CZ) method, and study the effects of crucible bottom deformation and thermal insulator thickness on the growth process and crystal quality. Garnet structure and <111> crystallography orientation of the crystal were confirmed by the X‐Ray diffraction (XRD) analysis. Macroscopic defects, residual stresses, quality, and homogeneity of the crystals were investigated by means of parallel plane polariscope and laser fizeau interferometer respectively and the results compared together. Experimental observations show that the crucible bottom deformation from flat to convex, and decreasing the thickness of zirconia insulator under the crucible result in the formation of lateral cores and increasing the crystal inhomogeneity and tensions, leading to the decrease of the crystal quality. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and Properties of YIG Single Crystals

In this paper a summary is given on the reproducible preparation of large, nearly defectless yttrium iron garnet single crystals (YIG) grown in fluxes by slowly cooling with accelerated crucible rotation (ACRT) and local bottom cooling. The surface morphology of the growth faces is discussed with regard to the growth mechanism. By different methods the crystals are characterized regarding their lattice defects (impurities, growth striations, dislocations, inclusions). Ferromagnetic resonance measurements in the X-band at polished, inclusionsfree discs show that the linewidth ΔH of any crystals from different runs are less than 0.45 Oe.     

Simplified version of calculation of the composition distribution along a single crystal of a binary solid solution obtained by pulling from a feeding melt

The possibility of obtaining single crystals of binary solid solutions exhibiting strong segregation upon crystallization by pulling from a feeding melt with the use of a crucible shaped as a truncated cone and a feeding ingot of complex shape is shown. The composition distribution along the crystal length is found by solving the continuity equation for the second component flux under certain initial and boundary conditions. It is shown that single crystals can be obtained in which the second-component concentration in the stationary mode exceeds the corresponding value in the feeding ingot. The method developed is applied to Ge-Si solid solutions.     

Control of oxygen contamination during the growth of optical calcium fluoride and calcium strontium fluoride crystals

The progress, current state, and prognosis for CaF₂ as an optical material with wide applicability are reviewed by outlining the basic issues: technology, demand, supply, and metrology. To achieve perfect quality for all application grades of CaF₂ grown using a natural fluorite, investigations of the effect of PbF₂ and ZnF₂ scavengers for removal of oxygen contaminants from the starting material, representing chemically purified fluorspar, either granular or as dense precursors is reported. The chemical and crystal-chemical reactions occurring during the crystallization due to the presence of oxygen contaminants, scavengers, and rare-earth impurities are discussed based on data for the composition of the residual atmosphere in the reactor chamber. The water vapors have been shown to have a major impact in deteriorating the optical properties of the grown crystals. The use of precursors, together with 0.1n% ZnF₂ additive, is shown to be highly recommendable for the production of ultraviolet and vacuum ultraviolet grades of CaF₂ and Ca_1−xSr_xF₂ crystals. For visible and infrared grades PbF₂ appears to be a better additive than ZnF₂. The technique for growth of Ca_1−xSr_xF₂ in an argon flow with a 5 nines inlet purity has proved to be suitable for producing high-quality crystals, whose optical properties satisfy the demands of micro-photolithography provided that precise control over the total pressure inside the crucible is implemented.     

Investigations of impurity striations in potassium bichromate crystals

Impurity striations in potassium bichromate crystals (KBC, lopezite) formed during crystal growth from aqueous solution were revealed by chemical etching and analyzed. Striations were revealed as etch grooves, as rows of dislocation etch pits and as rows of flat‐bottomed etch pits. Various types and groups of striations have been visualized. Some striations were due to lateral segregation of impurities caused by convection flow of the mother solution, other were formed during growth stoppages whereas induced striations were generated by changes in hydrodynamical conditions. Growth rates changes resulted in zonal distribution of impurities, formation of planar lattice strain, rows of clusters of point defects and rows of dislocations. Generation of striations with different intensities in various sectors is a proof of the selective capture of impurities. Ratios of growth rates of various faces of KBC crystals growing in forced and free convection regimes were determined by induced striations. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Radial and axial impurity distribution in high-purity germanium crystals

To grow high purity germanium (HPGe) crystals in an underground environment for ultra-low background experiments is being studied. In the present work, HPGe crystals along 〈100〉 direction have been grown by the Czochralski method. In order to investigate the distribution of the impurities as a function of length for a grown crystal, i.e. the axial direction, we fabricated a system to measure the resistivity along the axial direction at both room temperature and liquid nitrogen temperature. The distribution of the impurities along the radial direction was measured with a Hall Effect System. The results show that the carrier concentration in some crystals grown in a hydrogen atmosphere has an impurity level of about 10¹⁰/cm³, which meets the requirements of detector-grade crystals.     

Compositional variation in 0.65 PbMg2/3Nb1/3O3 ‐0.35 PbTiO3 single crystals grown by high temperature solution growth technique

Single crystals of lead magnesium niobate titanate, 0.65 PbMg_2/3Nb_1/3O₃ (PMN) ‐0.35PbTiO₃ (PT) were grown using flux method near morphotropic phase boundary (MPB) composition. The crystals grown at the centre of the platinum crucible were found to PT deficient compared to those grown near the walls of the crucibles. A variation of ∼3.8 mol% in PT concentration was found in the crystals grown at the wall and at the centre of the crucible. The difference in the chemical composition of crystals grown at the centre and the near the wall of the crucible was observed by X‐ray diffraction, EDXRF, dielectric and thermal measurements. The presence of PT rich and deficient crystals is explained in terms of the segregation coefficient of PT in PMN. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Domain structures and etching morphologies of lithium niobate crystals with different Li contents grown by TSSG and double crucible Czochralski method

Stoichiometric lithium niobate single crystals with different Li contents have been grown both by the top‐seeded solution growth (TSSG) method from potassium containing flux and by the double crucible Czochralski (DC Cz) method. Spectroscopic properties (e.g. the UV absorption edge, Raman linewidth) and the Curie temperature measurement have been used for the characterization of the crystal composition. The double crucible Czochralski method is found to be suitable for mass production of stoichiometric LiNbO₃ with Li content larger than 49.7 mol% and homogeneity of 0.03 mol%. The domain structures and etching morphologies on negative and positive c‐surface were also investigated by chemical etching method. A new domain structure of three‐fold symmetric sectors were observed in near‐stoichiometric LiNbO₃ grown by TSSG method. The straight line arrangement hillocks on negative c‐surface and the net‐like arrangement etch lines were observed and explained by stress etching mechanism. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of rhodium incorporation in KTiOPO4 single crystals grown from self‐flux

The presence of an impurity like rhodium in the platinum crucible used for the growth of KTiOPO₄ (KTP) single crystals can have severe consequences in the performance of devices made from these crystals. In the present study the effect of rhodium incorporation has been investigated. Rhodium‐incorporated KTP crystals have a lower ionic conductivity (1.3 × 10^–7 S/cm at 100 kHz) than pure KTP crystals (3.5 × 10^–6 S/cm at 100 kHz) along the c‐axis. And the optical absorption in the green‐wavelength regime leads to a detrimental effect on their SHG performance. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of Nd:Sr3Ga2Ge4O14 crystals by a modified Bridgman method

Bridgman growth of Nd:SGG (Sr₃Ga₂Ge₄O₁₄) crystals has been investigated for the first time. Pt crucible of ∅︁25mm×250mm with a seed well of ∅︁10mm×80 mm is used, and seed is SGG crystal of ∅︁10mm×50mm grown by Bridgman method in advance. The growth parameters are optimized as the furnace temperature is set to 1450∼1500°C, temperature gradient in the crystal‐melt interface is less than 25 K/cm and growth rate is less than 0.5mm/h. The Nd:SGG crystals with 25mm in diameter and 60mm in length are grown successfully from 1.5 to 8at% Nd³⁺ doped stoichiometric Sr₃Ga₂Ge₄O₁₄ melt. The distribution coefficient and concentration of Nd³⁺ in Nd:SGG crystals are obviously higher than those of Nd:YAG crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Improvement of Superconductivity in PbxBi2-xSr2CaCu2Oy

In this paper we present the results of recent studies on the improvement of superconductivity in Pb_xBi_2-xSr₂CaCu₂O_y single crystals by preventing impurities incorporation, employing ZrO₂ crucible for crystal growth and post annealing the as-grown crystals in vacuum or argon. It is realized that the superconductivity of as-grown crystals is improved.     

Investigation of the thermal conditions during silicon carbide crystal growth

In the present work an analysis of the thermal conditions during silicon carbide crystal growth from the vapour phase by the sublimation method is carried out. On the basis of the obtained results from the calculation of the temperature distribution along the length of the growing crystal it was drawn a conclusion that in order to decrease the density of dislocations in the growing crystals it is necessary to decrease the temperature gradients in the crucible for growing.     

Influence of reaction between silica crucible and graphite susceptor on impurities of multicrystalline silicon in a unidirectional solidification furnace

The influence of silica crucible reaction with graphite susceptor on carbon and oxygen impurities in multicrystalline silicon was studied by global numerical simulations. Results showed that the crucible reaction has a marked effect on carbon and oxygen impurities in the crystal. When the activity of carbon on the surface of the graphite susceptor increases, both oxygen and carbon impurities in the melt increase rapidly. Therefore, the production of high-purity multicrystalline silicon requires setting a free space between the silica crucible and the graphite susceptor or depositing a layer of SiC film on the surface of susceptor to prevent reaction between them.     

Nitride bonded silicon nitride as a reusable crucible material for directional solidification of silicon

Nitride bonded silicon nitride (NBSN) has the potential of a reusable crucible material for directional solidification of silicon. This is demonstrated in this work by reusing a NBSN crucible six times for the directional solidification of undoped multicrystalline (mc) silicon ingots. The progress of the ingot contamination at subsequent use of the NBSN crucible was studied systematically. Minority carrier lifetime, electrical resistivity as well as impurity content were analyzed after each solidification run. The results were compared to those obtained from ingots which were crystallized by using identical directional solidification process parameters in standard fused silica crucibles with silicon nitride coating. The impurity content of the ingots can be clearly correlated to the impurity content of the NBSN crucible. The main impurity is the acceptor B. Its concentration in the ingots decreases from about 10¹⁷ atoms/cm³ to 10¹⁶ atoms/cm³ with continued reuse. The contamination mechanism is most likely due to outdiffusion from the crucible wall into the Si melt.     

The effect of crucible movement in Bridgman-Stockbarger technique

The effect of the crucible movement on the growth of large size alkali halide crystals effected in a ceramic crucible by B-S technique is investigated. From the studies carried out it follows that the crucible movement adversely affects the thermal conditions in the furnace resulting in a defective growth. To circumvent the problems faced suitable modification of the conventional B-S technique yielding good crystals is suggested.