水热法KTP晶体生长与宏观缺陷研究

本文报道了水热法KTP晶体的生长工艺及晶体生长形态,系统研究了水热法KTP晶体的宏观缺陷,其宏观缺陷主要为添晶、生长脊线、裂隙和包裹体.提出了晶体生长工艺的改进措施,如提高原材料和试剂的纯度、调整籽晶的悬挂方式、减少籽晶的尺寸等,都可以减少晶体的宏观缺陷,提高晶体的质量.//(011)切向的籽晶生长的晶体质量较高,且能很好地应用于激光器件中.     

Growth and properties of KTP crystals from a new flux

High-quality KTiOPO₄ (KTP) crystals were grown by a top seeded solution growth (TSSG) method using K₈P₆O₁₉–BaF₂ as a flux. The volatility of different solvents, such as K₈P₆O₁₉ (K₈), K₈–NaF, K₈–KF, and K₈–BaF₂, was measured. These fluoride additives in K₈ fluxes and their compositional effects on the growth of KTP crystals were studied and discussed. The transmissivity and optical homogeneity of KTP crystals were also measured.     

Investigation of growth kinetics and morphology of sodium fluorosilicate ice‐analogue crystals in solutions and gels

The effect of growth method (solution or gel growth) and growth conditions on the morphology of ice analogue crystals (sodium fluorosilicate) has been studied. Many habits typical for atmospheric ice crystals (hexagonal columns, plates, different types of stars or dendrites) were obtained during experiments. The dependence of growth rate of basal and prism faces of columnar crystals on supersaturation was measured for crystals growing by evaporation of solvent. The experiments establish evaporation rate and growth rate ranges at which appearance of certain types of crystals is most probable. The experiments have also shown that good quality sodium fluorosilicate crystals can be obtained in TMS gel. These crystals were significantly bigger than those obtained in solution. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

单掺Rb+和Cs+的KTP晶体生长及其电导率

采用高温溶液降温法在掺质浓度均为5mol;的KTP-K4溶液中分别生长了单掺Rb+和Cs+的KTP晶体,发现掺质改变了晶体生长习性,在相应生长体系中掺质Rb+和Cs+的分配系数分别为O.646和0.08,掺质KTP晶体的晶胞参数a0和b0比纯KTP晶体者略有增长.通过掺Rb+或Cs+,KTP晶体的c向电导率明显降低,但晶体在350～1100nm范围内的光透过性质未受影响.     

Effects of anions on rapid growth and growth habit of KDP crystals

The synthesis of KDP from its raw material has been found exist in the growth solution. In the crystal growth experiment, significant extension of specific faces was observed at low dopant concentration. At high doping concentration, the growth rate of the whole crystal decreased with no significant habit modification. The inhibiting effects of phosphite and other H-bonding anionic ions on the growth of pyramidal faces are discussed. Rapid growth rate experiments have been carried out with purified material and an averaged growth rate of 18.6mm/day was obtained.     

Ga3+:KTP晶体c向电导率的研究

采用ICP-AES法测定了Ga3+:KTP晶体中掺质Ga3+离子含量,并由此得出Ga3+离子在相应晶体生长体系中的平均分配系数为0.0373;采用静电计和多频测试仪测定并计算出Ga3+:KTP晶体c向的电导率,将其与纯KTP晶体者进行比较.结果发现,Ga3+:KTP晶体c向电导率比纯KTP晶体c向电导率在交流情况下最大降低了两个数量级以上.文中对晶体c向电导率的降低机理进行了探讨.     

KTP晶体的水热法生长及其光学性能的测量

使用水热法成功生长出大尺寸、高质量的KTP晶体,对该晶体的光学性能进行测量分析.由LambDA900分光光度计测量得到的水热法生长KTP晶体的透过率曲线表明晶体具有良好的光透过性能,其透过短波下限与熔盐法生长的KTP晶体基本相当.利用自准直法精确测量水热法生长KTP晶体的折射率,拟合得到30℃下折射率的Sellmeier方程的系数,并计算532nm与1319nm波长对应的主轴折射率,计算值与实验值相吻合.     

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)     

Incorporation of hafnium (IV) into KTP framework from phosphate‐fluoride fluxes

Solid solutions KTi_1‐XHf_XOPO₄ (х = 0.008 – 0.107) possessing the KTiOPO₄ structure, have been synthesized in molten system K₂O‐P₂O₅‐TiO₂‐HfF₄. The crystal growth experiment of Hf‐doped KTP crystal has been reported. The X‐ray powder diffraction data and chemical analysis are also presented. It has been shown that KTiOPO₄ crystal structure slightly changes when Hf incorporates into the framework. Transmission/absorption spectra of KTi_0.974Hf_0.026OPO₄ crystals have been recorded. The incorporation of Hf ions shifts the optical absorption edge in the UV‐visible spectrum towards the long‐wavelength region with absorption near 387 nm.     

不同温度下KTP晶体的声表面波特性研究

针对KTP晶体的压电特性,利用克里斯托弗方程计算了20 ～ 140℃温度范围内Z切型传播角度为0～180°的声表面波速度、机电耦合系数、能流角.结果表明,在20℃,能流角为0°,传播角为90°的情况下,机电耦合系数最高达0.675;,是石英晶体的3倍左右;在140℃,能流角为0°,传播角为90°的情况下,机电耦合系数达到0.60;,约为石英晶体的2倍.     

溶液法生长氘化磷酸二氢铵(DADP)晶体及其性能研究

使用优级纯的NH4H2PO4(含量＞99.5;)和重水(纯度＞99.5;)为原料,在重水中经过三次氘化重结晶,获得含氘量＞95;的结晶原料.上述DADP晶体作为原料配成1000ml的饱和溶液,用降温转动法生长出22mm×23mm×78mm尺寸的透明大晶体,并且测定其晶体结构、透过光谱和激光损伤阈值.从数据分析来看在最重要的光谱应用波段(1.06μm附近)DADP晶体综合性能是很优越的,这使得DADP有利于作为电光晶体材料和制作高频高灵敏度的电光器件.     

Bridgman growth and properties of potassium lithium niobate single crystals

Transparent KLN crystals 10mm in diameter and 25 to 45mm in length have been grown by the modified vertical Bridgman technique from different melts in the range of 3035mol% K₂O, 1723mol% Li₂O and 4350mol% Nb₂O₅. The growth conditions are a growth rate of less than 0.25 mm/hr, temperature gradient in solid-liquid interface of 23 °C/mm and growth direction of <110>. As-grown KLN crystals have tetragonal tungsten bronze structure. Most of the as-grown crystals do not crack when cooling through the paraelectric/ferroelectric phase transition. 180° domain structures are observed after the KLN crystal was etched in boiling 2HNO₃:Hf. Dielectric properties and transmission spectrum of the as-grown KLN crystals are measured.     

Morphological evolution of selenium micro‐crystals

A simple solution phase approach using dimethyl formamide (DMF) as solvent is utilized to obtain selenium (Se) microcrystals. Different morphological modifications of the products result from varied reaction environments. Solvothermal treatment of Se with DMF in an autoclave at 170°C yields rod‐like, and feather‐shaped microcrystalline structures while reduction of selenium dioxaide (SeO₂) by DMF generates microspheres at 30°C and 80°C, rods admixed with spherical particles at 120°C and predominantly micro rods at 150°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Yb0.140Gd0.813La0.047VO4晶体的生长、光谱和激光损伤阈值

采用Czochralski方法生长出了Yb0.140Gd0.813La0.047VO4晶体,并测试了Yb3+与La3+在GdVO4晶体中的有效分凝系数.实验结果表明,掺入La3+可在一定程度上提高晶体的激光损伤阈值和晶体生长过程中的稳定性.此外,La3+的引入还有利于减缓高浓度Yb3+掺杂晶体中的荧光捕获效应和浓度猝灭效应的激光损伤阈值.Yb3+在该晶体中具有很宽的吸收半峰宽和荧光半峰宽,分别为26nm和47nm,具有较大的吸收截面和发射截面,分别为2.26×10-20cm2和0.96×10-20cm2,因此该晶体有望用作可调谐激光晶体和飞秒激光晶体.     

Growth morphology of crystals from kinetic and geometric perspective

The growth morphology of crystals is analysed from macroscopic point of view and the recent developments in this field are surveyed. In particular, it is shown that, for specific geometry characterized by interfacial angles a given face can increase in size for a very wide range of relative growth rates and need not be the slow‐growing face. Even growing faster than the neighbouring faces, such a face can increase in its size. However, there are other faces with other specific geometry, which can decrease the size growing more slowly than one of the neighbouring faces. If the growth time is sufficiently long, such a face may disappear and not be represented in the final crystal morphology. In the present survey the concepts given earlier [5] are extended. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and properties of dyed KDP crystals

Potassium dihydrogen phosphate (KDP) crystals doped with xylenol orange (XO) and methylthymol blue (MTB) are grown from aqueous solutions by the method of solvent evaporation at room temperature under the conditions of natural convection and by the method of temperature lowering. Studied is the influence of the mother solution acidity on the character of the crystal coloration. The color and coloration intensity of the grown crystals are shown to strongly depend on the solution's pH. It is revealed that the crystal habit changes in the presence of organic dyes. The optical transmission spectra and the luminescence spectra of KDP:XO solutions and of the grown crystals are measured. The effect of thermal treatment and UV‐irradiation on the coloration stability of the crystals is studied. It is found that the laser damage threshold in the prismatic impurity rich colored sectors of KDP:XO is the same as that in the prismatic sectors of pure KDP crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A novel way of modifying the thermal gradient in Vertical Bridgman‐Stockbarger Technique and studies on its effect on the growth of benzophenone single crystals

In order to grow benzophenone single crystal, an organic nonlinear optical material, a cost‐effective Vertical Bridgman‐Stockbarger system has been designed and fabricated by employing a two‐zone, transparent furnace made out of immiscible liquids. Transparent, optical quality benzophenone single crystals were successfully grown as a result of a suitable thermal gradient achieved by means of introducing an intermediate liquid in between the two immiscible liquids. The effect of change in the volume of the intermediate liquid thereby the thermal gradient on the growth parameters was analyzed. The quality of the grown single crystal was justified using X‐ray powder diffraction analysis, FTIR, TG‐DTA and optical transmission studies. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of cooling rate on size,quality and morphology of KTiOPO4 (KTP) crystals grown by different nucleation techniques

KTP crystals have been grown by two nucleation techniques namely spontaneous nucleation in flux medium and nucleation on Pt rod using K₆P₄O₁₃ flux.10 °C/h, 7 °C/h, 0.8 °C/h, 0.4 °C/h and 0.2 °C/h cooling rates were applied for spontaneous nucleation and crystals up to 15 × 7 × 4 mm³ in size were grown. 1 °C/h and 0.8 °C/h cooling rates were also used for nucleation on Pt rod and crystals up to 8 × 6 × 3 mm³ in size were grown. The effect of cooling rate on size, morphology and optical quality of grown crystals by both techniques were studied. For nucleation on Pt rod upper and lower rotation rates limits and an optimum rotation rate were distinguished for each cooling rate. Quality of the grown crystals by both techniques was characterized by optical transmission analysis.     

Numerical simulation of the LEC-growth of GaAs crystals with account of high-pressure gas convection

The influence of the inert gas pressure on the growth of 4 GaAs crystals by the liquid encapsulated Czochralski method (LEC) process is studied for a range of the Ar gas pressure up to 10 bar by using our finite-volume computer code STHAMAS. Up to the pressure of 0.6 bar we are considering laminar convection. For the pressure range from 5 to 10 bar we are using the buoyancy extended standard k-ε turbulence model with wall functions to simulate the gas flow. The numerical results show that the Argon gas pressure has a strong influence on the consumption of heater power in qualitative agreement with our experimental results. The convex curvature of the growth interface and the maximum thermal stress (von Mises criterion) are found to increase with increasing gas pressure both in the laminar and turbulent evaluations.