工业晶体生长

本文考察了一些典型的晶体材料及其工业生长技术,如提拉法生长硅单晶,水热法生长水晶,VGF法生长GaAs,下降法生长锗酸铋,壳熔法生长锆石等,探讨了工业晶体生长的特点和发展方向.     

新型非线性光学晶体BaAlBO3F2的生长及组分挥发的研究

采用高温熔液法生长BaAlBO3F2晶体(简称BABF)时,组分挥发严重.本文分析了晶体生长前后的组分中相关元素的重量损失,发现易挥发的物质可能是硼的氧化物和氟化物;X射线衍射分析确定挥发物中还含有少量的NaCl.通过改变助熔剂与熔质的配比,明显降低了晶体的生长温度,减少了组分挥发,优化了晶体生长条件,得到24mm×20mm×6mm尺寸的晶体.     

新型非线性光学晶体BaAIBO3F2的生长及组分挥发的研究

采用高温熔液法生长BaAlBO3F2晶体(简称BABF)时,组分挥发严重.本文分析了晶体生长前后的组分中相关元素的重量损失,发现易挥发的物质可能是硼的氧化物和氟化物;X射线衍射分析确定挥发物中还含有少量的NaCl.通过改变助熔剂与熔质的配比,明显降低了晶体的生长温度,减少了组分挥发,优化了晶体生长条件,得到24mm×20mm×6mm尺寸的晶体.     

高温氧化物晶体生长过程中流体效应的实验研究及理论分析

流体效应是影响晶体生长传热、传质过程和晶体完整性的主要因素,了解其机理将有利于生长优质晶体.我们在空间晶体生长实时观察装置上,利用20μm的碳酸钠作示踪粒子,首次在高温氧化物熔液内同时观察到了表面张力和重力对流效应,并利用测量的结果计算了熔液内表面张力对流和重力对流的速度场.实验结果表明:近坩埚壁处,主要以表面张力对流起主导作用,而在熔液区域内,重力对流效应显著.     

典型非线性光学晶体生长方法综述

非线性光学晶体具有多种生长方法,每种方法都有其独特的优势和适用的晶体,通过了解典型非线性光学晶体生长方法的特点,可以确定采用哪种方法获得高质量的晶体,达到预期的目的.本文主要对典型非线性光学晶体生长方法进行相关介绍,如水热法生长KTP晶体、水溶液法生长KDP晶体、有机溶液法生长DAST晶体、高温溶液法生长BBO、LBO、KBBF等晶体、泡生法生长CBO晶体、提拉法生长LiNbO3晶体、布里奇曼法生长CdSiP2、ZnGeP2、BaGa4 Se7等晶体,阐述典型非线性光学晶体的原料、溶液配制、温度压力的控制等实验制备条件,展示所生长出的晶体样品.通过对上述方法总结,为今后的晶体生长方法选取提供借鉴.     

溶剂熔区移动法制备Cd0.9Zn0.1Te晶体及性能研究

用溶剂熔区移动法制备了掺In的Cd0.9Zn01Te晶体,晶体生长温度800℃,温度梯度为20℃/cm,生长速度0.4 mm/h.测试了晶体的Te夹杂情况、红外透过率图谱、Ⅰ～Ⅴ特性曲线和PICTS特性,并以1115℃下用VB法生长的掺In的Cd0.9Zn0.1Te晶体做为参照,对比了两者性能.结果表明,溶剂熔区移动法制备的晶体Te夹杂的密度和体积百分比比VB法晶片低,但是Te夹杂的尺寸要比VB法晶体大;溶剂熔区移动法晶体的红外透过率比VB法晶体高;溶剂熔区移动法晶体电阻率比VB法晶体高了一个数量级;PICTS测试发现,溶剂熔区移动法晶体内主要的缺陷密度低于VB法晶体.     

熔盐法和水热法KTP晶体的晶胞参数及拉曼光谱特征

利用X射线衍射和显微激光拉曼光谱研究熔盐法自发结晶的KTP晶体、顶部籽晶熔盐法KTP晶体和水热法KTP晶体的晶胞参数和拉曼光谱特征,分析和比较不同方法生长的KTP晶体的晶体结构与化学键特征峰.研究表明:KTP晶体的晶胞参数与晶体生长方法有关,熔盐法自发结晶的KTP晶体生长过程中降温速率较快,晶胞体积相对较小;熔盐法和水热法KTP晶体中部分拉曼特征峰的位置因生长方法不同呈现一定的差异,水热法KTP晶体在782 cm-1、744 cm-1和515 cm-1处出现的特征峰可视为水热法KTP晶体的标志峰,借此可将其与熔盐法晶体相区分.     

空间高温氧化物晶体生长过程中流体效应的数字模拟研究

数字模拟方法可以模拟实际晶体生长过程,了解晶体生长参数的变化对晶体生长的影响.本文利用数字模拟的方法,在本实验室建立的空间二维实时观察装置中,对高温Li2B4O7熔液中生长KNbO3晶体的流体效应及温场进行了数字模拟研究,结果表明,在地面生长,熔液内部存在复杂的双涡流动模式,重力对熔液中的速度场和温场的分布产生强烈的作用,而在空间,当重力水平达到一定程度时,可以使熔液中的流动模式简单化,从而降低流动效应对传热、传质造成的不稳定性和不均匀性,有利于提高晶体生长的质量.同时通过对空间搭载实验与地面实验结果进行对比分析,与数字模拟分析的结果一致,随着重力水平的下降,熔液中的速度场,温场分布朝着稳态生长的方向发展,表面张力对流是形成均匀胞状晶体结构的主要因素.     

正钒酸钙晶体的生长及退火的研究

本文报道了Ca3(VO4)2晶体的生长,指出了由于局部区域温度过高引起原料分解产生气泡,光加热浮动熔区法不适合于生长这种晶体.采用了Czochralski法在合适的温场、提拉速度为3mm/h、转速10～20r/min等工艺条件下成功地长出了φ24×38mm的晶体.通过适当的温度梯度和退火条件解决了晶体生长和加工过程中的炸裂问题.     

泡生法蓝宝石单晶不同生长阶段的数值模拟研究

针对泡生法蓝宝石单晶生长的不同生长阶段的温场、流场和固液界面形状进行数值模拟研究.并分析了加热器相对坩埚的轴向位置和不同生长速率对蓝宝石单晶生长的影响.结果表明:在蓝宝石单晶生长中,在靠近坩埚壁面和固液界面的熔体内,等温线密,温度梯度较大;在靠近坩埚底部的熔体内,等温线稀疏,温度梯度较小.随着晶体高度的增加,熔体对流由放肩阶段的两个涡胞变成等径阶段的一个涡胞,熔体平均温度有小幅度下降;加热器相对坩埚的轴向位置对晶体生长炉内温场和固液界面形状影响很大,随着加热器位置上移,晶体内平均温度升高,温度梯度减小;熔体内平均温度降低,温度梯度增大.同时固液界面凸度增大.随着晶体生长速率增大,固液界面凸度增大,界面更加凸向熔体.     

溶剂蒸汽退火辅助微距升华法制备C8-BTBT单晶

有机半导体单晶由于具有内部长程有序的分子排列结构、缺陷及晶界少等优点,表现出优异的光电性能,是实现有机半导体器件实用化的一种重要材料。目前,研究者们已经发展出多种可应用于有机单晶的生长方法,其中,微距升华法是一种可以在大气环境下采用蒸镀的方式制备有机微/纳单晶的方法。然而,当将这种方法应用于C8-BTBT时发现,由于分子的熔点较低,蒸镀得到的是分子直接从液态凝固为无定形/多晶的结构。在本工作中,通过使用溶剂蒸汽退火的方式对其进行后处理,成功地将这种无定形/多晶结构转化为分立的单晶。为了表征所得到的晶体形貌和结构,分别使用光学显微镜、X射线衍射和原子力显微镜等仪器对其进行了表征,发现所制备的晶体结构具备单晶的典型特征。     

The mechanism of crystal growth in glass forming systems

A critical survey on experimental results on the mode of growth in simple glass forming melts is given, attention being mainly concentrated to data obtained at small undercoolings. Dissolution rates, change of interfacial conditions at constant undercooling as well as detailed structural determinations are considered as experimental evidences, complementary to a thorough analysis of growth-temperature dependences. For network glass formers (SiO₂, GeO₂, P₂O₅, Na₂B₄O₇) with melt structures, similar to those of the corresponding crystals, the normal mode of growth is typical. For a number of simple glass forming substances in which the crystallization is connected with a process of molecular reconstruction (NaPO₃, LiPO₃), spiral growth could be proved. Dislocation-free crystals of high entropy of melting glass forming substances (Na₂S₂O₃ · 5 H₂O, thymol) are obtained after prolonged annealing and growth in thin bored capillaries. Two-dimensional growth is verified for the resulting perfect crystals.     

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 magnetic garnet single crystals from high temperature solution

A review is given to show the development of growth techniques for single crystals for the incongruently melting yttrium iron garnet. As a result of this world-wide development a technique is described in some detail which allows well controlled nucleation and growth using a high temperature solution.     

Role of non-stoichiometry in the cracking of oxide crystals

The cracking and stoichiometric deviations frequently observed in crystals of mixed oxides have generally been perceived to be unrelated phenomena. The present study pertains to the cracking in Czochralski grown crystals of three different materials, viz. CdWO₄, PbWO₄ and ZnWO₄. The results obtained on the single-crystal growth as well as on the thermal stability of melts of these materials and of their constituent oxides demonstrate, for the first time, that stoichiometric deviations manifest as cracks in the crystals. An important outcome of this investigation is that materials exhibiting a small degree of super-cooling with stable melting and solidification temperatures should be less prone to cracking.     

Melting temperatures of NaClO3-NaBrO3 mixed crystals

The melting points of mixed crystals of sodium chlorate and sodium bromate have been determined. The variation of melting point with composition is non-linear with negative deviations from linearity. This negative deviation from linearity is attributed to a possible increase in the vacancy concentration in mixed crystals as compared to the pure end crystals.     

Growth of single crystals of quasicrystalline phases

To study the mechanical and physical properties of quasicrystals, single-crystal samples of large size (several centimeters) are necessary. However, obtainment of such single crystals meets a number of difficulties related to the peritectic character of melting of quasicrystalline compounds, high volatility and oxidizability of the initial components, low growth rate in aperiodic directions, and metastability of the most quasicrystalline structures. In this study, criteria for stable growth of quasicrystalline phases have been determined. The growth mechanisms of icosahedral and decahedral single crystals are described and experimental techniques of single-crystal growth are reviewed.     

Experimental Study of Interface Inversion of Tb3ScxAl5‐xO12 Single Crystals Grown by the Czochralski Method

Thermal conditions and rotation rate were examined experimentally for obtaining a flat interface growth of high melting‐point oxide (Tb₃Sc_xAl_5‐xO₁₂ ‐ TSAG) by the Czochralski method. The critical crystal rotation rate can be significantly reduced, of about twice at low and very low temperature gradients comparing to medium temperature gradients in the melt and surroundings of the crystal. The interface shape of TSAG crystals is not very sensitive on crystal rotation rate at small rotations and becomes very sensitive at higher rotations, when the interface transition takes place. The range of crystal rotation rates during the interface transition from convex to concave decreases with a decrease of temperature gradients. At low temperature gradients interface inversion crystals takes place in very narrow range of rotation rates, which does not allow one to growth such crystals with the flat interface. Even changing crystal rotation rate during the growth process in a suitable manner did not prevent the interface inversion from convex to concave and thus did not allow to obtain and maintain the flat interface.