Growth of YCOB single crystals by flux technique and their characterization

Nonlinear optical single crystals of YCOB with good optical quality were grown by the flux technique for the first time. Polycrystalline YCOB samples were synthesized by solid state reaction method. The thermal analysis of the sample was performed with lithium carbonate flux in different weight proportions and the growth temperature was optimised. Single crystals of YCOB with dimensions 3 × 3 × 5 mm³ were obtained by the method of ‘slow‐cooling’. The grown crystals were characterized by XRD, UV‐VIS‐NIR, EDAX, FTIR and etching studies. The powder XRD pattern revealed the formation of YCOB compound. The lattice parameters were identified through single crystal XRD studies. The UV‐VIS‐NIR results showed that the crystal has a sharp cutoff at 220 nm and is nearly 55% transparent over a wide wavelength range enabling applications in the UV region. The EDAX measurement revealed the ‘flux‐free’ crystal formation. The presence of the functional groups belonging to the YCOB crystals was identified by the FTIR results. ‘Hillock‐like’ patterns are observed in the etching studies. The primary emphasis in this study is laid to describe ‘flux technique’ as an alternative method to grow YCOB crystals. The results are presented and discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of axial vibration on Bi12SiO20 crystal growth by vertical Bridgman technique

Bi₁₂SiO₂₀ single crystals have been grown successfully by vertical Bridgman technique. During the crystal growth process, different axial vibration amplitudes of 50 μm, 70 μm and 100 μm were applied with the same vibration frequency of 50 Hz. The effect of different axial vibration amplitudes on quality of the as‐grown Bi₁₂SiO₂₀ single crystals was discussed. The crystals have been characterized by X‐ray rocking curve optical and absorption spectrum. The experimental results reveal that the axial vibration amplitude has a pronounced effect on quality of the as‐grown Bi₁₂SiO₂₀ single crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth of the intermetallic compound Nd2PdSi3

Nd₂PdSi₃ single crystals were grown by a vertical floating zone method with radiation heating at a zone traveling rate of 3 mm/h. The compound exhibits congruent melting behavior at a liquidus temperature of about 1790 °C. The actual crystal composition (35.3 ± 0.5) at.% Nd, (16.2 ± 0.5) at.% Pd, and (48.5 ± 0.5) at.% Si is slightly depleted in Pd and Si with respect to the nominal stoichiometry. Therefore, the gradual accumulation of these elements in the traveling zone led to a decrease of the operating temperature during the growth process. Single crystalline samples exhibit a large anisotropy due to the crystal electric field effect and order ferromagnetically below the Curie temperature T_C = 15.1 K. The [001] orientation was identified as the magnetic easy axis at low temperatures. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth,dielectric and photoconducting studies of tetrathiourea mercury(II) tetrathiocyanato zinc(II) NLO single crystals

A highly efficient nonlinear optical single crystals of tetrathiourea mercury (II) tetrathiocyanato zinc(II), Hg(N₂H₄CS )₄Zn(SCN)₄, (TMTZ) were conveniently grown from mixture solvent of ethanol–water by slow evaporation technique. The grown crystals exhibited needle-shaped morphology. The cell parameters of TMTZ single crystals were determined by single-crystal X-ray diffraction. The grown crystals were subjected to optical characterization by FT-IR, FT-Raman and UV–Vis–NIR techniques. The dielectric study of TMTZ showed low dielectric loss in the high-frequency region. The photoconductivity studies confirm that the TMTZ crystal has negative photoconducting nature.     

Induced growth of Pb0.97La0.02(Zr0.66Sn0.27Ti0.07)O3 antiferroelectric single crystals with a platinum wire

Relaxor antiferroelectric (Pb,La)(Zr,Sn,Ti)O₃ (PLZST) with the composition near the morphotropic phase boundary shows excellent electrical properties. However, the crystal growth of PLZST is limited by the incongruent melting of the materials. Crystal growth of PLZST was induced by a platinum wire in the flux solution with 50 wt% PbO‐PbF₂‐B₂O₃ as a solvent. The obtained PLZST single crystals are optical transparent with light yellow color. The size of the crystals in regular rectangular shape varies from 0.5 mm to 1 mm. The PLZST single crystals exhibit tetragonal phase structure. The element contents of the crystals were measured by inductively coupled plasma atomic emission spectrometry. The results show that the composition of as‐grown crystals is a little bit deviated from the starting composition. The single crystals show two dielectric peaks at 115 °C and 182 °C, corresponding to antiferroelectric‐ferroelectric and ferroelectric‐paraelectric phase transitions. The dielectric data of as‐grown crystals indicate there is typical relaxor behavior near 182 °C. The value of relaxor factor n is 1.49642.     

Growth of CuInS2 single crystals from Sb2S3 and Bi2S3 solutions

The phase diagrams of the CuInS₂‐Sb₂S₃ and CuInS₂‐Bi₂S₃ systems were investigated using X‐ray powder diffraction and differential thermal analysis. Based on these results, the compositions for the growth of the CuInS₂ single crystals from CuInS₂‐Sb₂S₃ and CuInS₂‐Bi₂S₃ melts were selected and Bridgman crystal growth process was performed. The investigation of the obtained single crystals using X‐ray powder diffraction and optical absorption spectra indicates that the incorporation of the solvent atoms into the crystal lattice is absent. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

用数学模型计算生长大尺寸光学晶体加热系统结构 第2部分—在φ4 00mmCaF_2晶体生长中计算辐射-传导热交换的方法和结果(英文)

大尺寸氟化物晶体的生长是基于对晶体炉热交换的实验研究和计算结果 ,在晶体生长过程的不同阶段解决了复杂结构生长容器的边界条件和温场的二维计算任务。我们在这里给出了晶体生长过程中温场设置和转变的具体数据。所有的计算都是根据晶体、熔体 ,容器材料的光学特性与光谱和温度的关系以及它们的热物理值与温度的关系做出的。这些结果包括了迄今有关氟化物晶体生长系统和过程的最精确的数据 ,可用于生长技术工艺的发展以及晶体生长炉和容器的设计。     

Growth and characterization of 4‐Aminopyridinium‐4‐nitro phenolate single crystals

Organic optical material 4‐Aminopyridinium‐4‐nitro phenolate (4AP4NP) has been synthesized, and single crystals of size 20 x 14 x 6 mm³ have been grown from acetone solvent at room temperature by solvent evaporation technique. The grown crystals have been characterized by X‐ray diffraction to determine the cell parameters, and by FT‐IR technique to confirm the formation of the expected compound. The crystal belongs to monoclinic crystal system with space group P2₁/a.The structural perfection of the grown crystals has been analyzed by high‐resolution X‐ray diffraction (HRXRD) rocking curve measurements. The thermal stability of the compound has been determined by TG‐DTA curves. The transmittance of 4AP4NP has been used to determine the refractive index n; the extinction coefficient K and both the real ε_r and imaginary ε_i components of the dielectric constant as functions of photon energy. The optical band gap of 4AP4NP is 2.4 eV. The dielectric and mechanical behavior of the specimen was also studied. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

用数学模型计算生长大尺寸光学晶体加热系统结构第2部分-在Ф400mm CaF2晶体生长中计算辐射-传导热交换的方法和结果

大尺寸氟化物晶体的生长是基于对晶体炉热交换的实验研究和计算结果,在晶体生长过程的不同阶段解决了复杂结构生长容器的边界条件和温场的二维计算任务.我们在这里给出了晶体生长过程中温场设置和转变的具体数据.所有的计算都是根据晶体、熔体,容器材料的光学特性与光谱和温度的关系以及它们的热物理值与温度的关系做出的.这些结果包括了迄今有关氟化物晶体生长系统和过程的最精确的数据,可用于生长技术工艺的发展以及晶体生长炉和容器的设计.     

大尺寸电阻加热式碳化硅晶体生长热场设计与优化

大尺寸低缺陷碳化硅(SiC)单晶体是功率器件和射频(RF)器件的重要基础材料,物理气相传输(physical vapor transport, PVT)法是目前生长大尺寸SiC单晶体的主要方法。获得大尺寸高品质晶体的核心是通过调节组分、温度、压力实现气相组分在晶体生长界面均匀定向结晶,同时尽可能减小晶体的热应力。本文对电阻加热式8英寸(1英寸=2.54 cm)碳化硅大尺寸晶体生长系统展开热场设计研究。首先建立描述碳化硅原料受热分解热质输运及其多孔结构演变、系统热输运的物理和数学模型,进而使用数值模拟方法研究加热器位置、加热器功率和辐射孔径对温度分布的影响及其规律,并优化热场结构。数值模拟结果显示,通过优化散热孔形状、保温棉的结构等设计参数,电阻加热式大尺寸晶体生长系统在晶锭厚度变化、多孔介质原料消耗的情况下均能达到较低的晶体横向温度梯度和较高的纵向温度梯度。     

Synthesis,growth, morphology of the semiorganic nonlinear optical crystal L‐glutamic acid hydrochloride and its structural,thermal and SHG characterizations

One of the halide derivatives of L ‐glutamic acid which was identified as a semiorganic nonlinear optical material, L ‐glutamic acid hydrochloride [HOOC(CH₂)₂CH(NH₂)COOH.HCl], was grown as bulk single crystal and its significant properties were characterized. The stoichiometric title compound was synthesized and the solubility of its recrystallized form in DD water was determined in the temperature range 30–80 °C by gravimetric method. Structural confirmation was carried out by powder X ‐ray diffraction study through lattice parameter verification. Optical quality smaller dimension single crystals were grown from aqueous solution by self nucleation through slow evaporation of solvent method and a large dimension single crystal was grown by slow cooling method with reversible seed rotation technique. Morphological importances of different growth facets of the as grown crystals were studied through optical goniometry. Unit cell structure of the grown crystal was refined by single crystal X ‐ray diffraction analysis, functional groups present in the crystal responsible for various modes of vibrations were confirmed by FTIR spectroscopy analysis, thermal stability of the grown crytal was analysed by TG/DTA and DSC and second harmonic generation (SHG) of a fundamental Nd:YAG laser beam by Kurtz technique. Results indicate that the grown crystal is in stoichiometric composition and has significant improvement in its thermal and SHG properties when compared to pure L ‐glutamic acid polymorphs.     

Study on rapid growth of KH2PO4 and its characterization

Large size crystals of KH₂PO₄ (KDP) were grown by adopting rapid growth technique from point seeds in a 1500‐liter crystallizer which is used to grow KDP crystals by conventional method. The grown KDP crystal size can reach to 310 × 310 × 320 mm³ and the average growth rate was 8mm/day. The optic properties of the rapidly grown KDP crystals were characterized comparing with the KDP crystals grown by the traditional temperature reduction method. We found it that the optical quality of the KDP crystals we grown rapidly are not significantly different from those of KDP crystals grown by traditional method. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of Mg/Er co‐doping on the principal laser parameters of LiNbO3 crystals

Mg: Er: LiNbO₃ crystals were grown by the Czochralski technique with various concentrations of MgO = 2 mol%, 4 mol%, 6 mol% and the fixed concentration of Er₂O₃= 1 mol% in the melt, and the 8 mol%Mg: 1 mol%Er: LiNbO₃ crystal was fabricated by the Czochralski technique with special technology process. The crystals were treated by polarization, reduction and oxidation. The segregation coefficients of Mg²⁺ and Er³⁺ in Mg: Er: LiNbO₃ crystals were measured by X‐ray fluorescence spectrograph, as well as the crystal's defect structure and optical properties were analyzed by the UV‐Vis, IR and fluorescent spectroscopy. The pump wavelength and the surge wavelength were determined. Using m‐line method tested optical damage resistance of those crystals, the results show that photodamage threshold of Mg: Er: LiNbO₃ crystals are higher than that of Er: LiNbO₃ crystal, and the oxidation treat could enhance the photodamage resistant ability of crystals while the reduction treat could depress the ability. The optical damage resistance of 8 mol%Mg: 1 mol%Er: LiNbO₃ crystal was the strongest among the samples, which was two orders magnitude higher than that of 1 mol%Er: LiNbO₃ crystal. The dependence of the optical properties on defect structure of Mg: Er: LiNbO₃ crystals was discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Czochralski Method ‐ where we are 90 years after Jan Czochralski’s invention

The Czochralski method, i.e. pulling a crystal from the melt, became the most important technology for the production of large semiconductor (Si, GaAs, InP, GaP …) and optical crystals (oxides, CaF₂ …). The present status is achieved by a profound analysis of the mechanisms of heat and species transport which are relevant for the stability of the Czochralski growth process and the performance of the growing crystal. It was clearly demonstrated in the last few years that modeling by numerical simulation is an indispensable tool to analyze the Czochralski process and to understand the governing mechanisms. The contribution presents examples of this kind of modeling the Czochralski technique in correlation with experimental investigations in order to illustrate the present status of understanding relevant processing phenomena. Furthermore, it is shown what problems need still to be solved in the future in order to further improve the yield and quality of Czochralski‐grown crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> and Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> crystals by the low-thermal gradient Czochralski technique

Bi₁₂SiO₂₀ crystals have been grown for the first time by the low-thermal gradient Czochralski technique in the 〈111〉 and 〈110〉 directions. The conditions for reproducible crystal growth with a high-quality polyhedral faceted front are found. The systematic features of shaping Bi₁₂SiO₂₀ and Bi₁₂GeO₂₀ crystals, grown by the low-thermal gradient Czochralski technique, are compared. The defect formation in these crystals is studied and their optical homogeneity is analyzed by interferometry.     

Rapid growth of α-LiIO3 crystal

A fundamental possibility of significantly increasing the growth rate of α-LiIO₃ crystals without the formation of visible defects in them is demonstrated. The corresponding equipment is designed and a technique for obtaining intermediate-size samples is developed. The crystals grown with an average rate of up to 4 mm/days along the Z axis are of high enough quality to be used as materials of optical elements for laser frequency doubling. α-LiIO₃ crystals have been grown both in an open volume via natural faceting and in a rectangular habit, where growth occurs basically through the pyramid (101) face. It is shown that that amount of limiting impurities in the raw material used can be reduced and that the applicability of this material for rapid growth can be verified.     

Effect of different metal ions on structural,thermal, spectroscopic and optical properties of ATCC and ATMC single crystals

A novel metal‐organic coordination complex nonlinear optical crystals, tri‐allylthiourea cadmium chloride [(CdCl₂(AT)₃] and tri‐allylthiourea mercury chloride [(HgCl₂(AT)₃] abbreviated as ATCC, ATMC (AT is Allylthiourea i.e.,CH₂=CHCH₂NHCSNH₂) has been synthesized and grown as single crystals. It was synthesized in deionised water and further recrystallized to improve its purity. Single crystals of the allylthiourea co‐ordination complex nonlinear optical crystals tri allylthiourea cadmium chloride (ATCC) with dimensions of 14x14x10 mm³ and tri allylthiourea mercury chloride (ATMC) with dimensions of 15x15x12 mm³ were grown successfully from aqueous solution by solvent evaporation as well as by temperature lowering method. It exhibits powder SHG efficiencies higher than that of a well known organic NLO crystal Urea. The solubility of the as grown crystals was estimated from the aqueous solution and the effect of different metal ions on the grown crystals, structural, thermal, spectral and optical properties were analyzed. XRD studies the reveals the same structure of both materials. Influence of the different central metal (Cd and Hg) atoms, changing the thermal properties of the materials when NLO complexes formed with the common ligand allylthiourea. The metal co‐ordination was confirmed form the spectroscopic analysis. From the UV transmittance studies, red shift was from the transparency cut‐off wavelengths. The value is 285nm for ATCC is and is 335nm ATMC, Non‐linear an optical study confirms the suitabilities of the as grown crystals for the non linear optical applications. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of indium intercalation on various properties of MoSe2 single crystals

Indium intercalated MoSe₂ single crystals i.e. In_xMoSe₂ (0 ≤ x ≤ 1) are grown by direct vapour transport technique. These crystals are structurally characterized by X‐ray diffraction, by determining their lattice parameters ‘a’ and ‘c’ and X‐ray density. The Hall effect and thermoelectric power measurements shows that In_xMoSe₂ (0 ≤ x ≤ 1) are p‐type in nature. The direct and indirect band gap measurements are also undertaken on these semiconducting materials. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bulk GaN single crystals: growth conditions by flux method

Hexagonal GaN platelet crystals with a size of 1–4 mm have been grown by a Li-based flux method. The influence of growth conditions such as the molar ratio of starting materials, temperature, pressure, the position of Li₃N in the crucible on the growth of GaN single crystals was studied. The quality of GaN single crystal was checked by optical microscope and X-ray rocking curve.     

Structural and optical investigations on Mn doped Li2B4O7 crystals

Lithium tetraborate crystals have great demand due to its non‐critical phase matching at 90°. Transparent and good optical quality single crystals of undoped and Mn doped Li₂B₄O₇ were grown by Czochralski technique in air atmosphere. The crystalline phase was determined by X‐ray diffraction. Doping of Mn in the grown crystals was confirmed by energy dispersive analysis of X‐rays (EDAX) technique. Transmission spectra show that the crystal is transparent in the visible region. Birefringence interferograms were recorded to qualitatively analyse the optical homogeneity of the grown crystals and to quantify the birefringence of the samples in desired crystal direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)