多余碳源的析出形式与宝石级金刚石单晶生长

温度梯度法生长宝石级金刚石单晶过程中,当籽晶无法完全吸收由高温端扩散下来的碳源时,多余碳源的不同析出形式(再结晶石墨或者自发核)对晶体生长速度有明显的影响。当大量多余碳源以再结晶石墨形式析出时,和以金刚石自发核形式析出不同,晶体的生长速度受到较为明显的抑制作用。例如,以NiMnCo触媒为例,随着合成温度的提高,当多余碳源不再以金刚石自发核形式析出,而是以大量片状再结晶石墨形式围绕在晶体周围时,晶体的生长速度从相对低温时的约3.0mg/h降到较高温度时的1.0mg/h;此外,随着合成压力由5.5GPa降到5.2GPa,晶体生长速度由3.0mg/h降到1.0mg/h,多余碳源析出形式也由金刚石自发核变化为再结晶石墨。     

快速生长大尺寸KDP单晶

用传统降温法生长了大尺寸KDP单晶,生长速度一般在1～2 mm/d,周期长,风险大.本文采用"点籽晶"快速生长法多次成功生长出了200 mm级的大尺寸KDP单晶,晶体生长速度达到20 mm/d,晶体生长正常.同时,摇摆曲线表明快速生长的晶体有着很好的结构完整性.     

优质立方六面体金刚石大单晶的生长研究

高温高压静压触媒法合成的金刚石单晶,往往呈现六八面体形貌,因为立方六面体单晶{100}面的生长区间相对较小.本研究利用高温高压温度梯度法,自制Fe-Ni合金触媒,通过对合成组装和工艺进行合理调整后,控制晶体在相对低温适合{100}面生长区域内生长,得到的晶体均呈现完整立方六面体形貌;同时为抑制包裹体和其他杂质的进入,人为的提高晶体的径向平铺生长速度,抑制其轴向生长速度.以在33 h内合成的优质立方六面体晶体为例,晶体最大方向尺寸达到7.3 mm,重1.2克拉,其径向生长速度达到0.22 mm/h,轴向生长速度仅为0.08 mm/h,增重速度为7.3 mg/h.     

β-Zn3BPO7晶体的提拉法生长研究

采用提拉法生长β-Zn3BPO7(简称ZBP)晶体.研究了生长工艺,用[210]方向的籽晶,获得了尺寸为35mm×20mm×10mm的单晶,该晶体无色透明,不开裂,呈现发育完好的{001}板面.通过设计特殊的温场以及在生长结束后采用适当的热条件有效地抑制了相变的发生.生长过程中靠近液面的温度梯度为30～60℃/cm,晶体转速为15～25r/min,提拉速度不大于1mm/h.ZBP晶体有宽的透光范围,它的紫外吸收边为240nm.ZBP晶体不潮解,其莫氏硬度为5Mohs.     

BaBPO5晶体的生长研究

本文采用顶部籽晶高温溶液法,以BPO4-NaF为助熔剂,生长了BaBPO5单晶.生长参数:液面以下温度梯度为1.5℃/cm,液面上温度梯度为10℃/cm,晶体旋转速度30r/min,降温速率0.5-1℃/d,可获得尺寸为30mm×20mm×15mm的BaBPO5单晶.测定了所获单晶及其挥发物的X射线粉末衍射图谱,讨论了助熔剂对BaBPO5晶体生长的影响和该晶体的物化性能.     

点籽晶法快速生长中等口径KDP单晶及其性能表征

本文使用德国MERCK公司生产的KDP原料和自行研制的晶体快速生长装置,采用"点籽晶"快速生长法成功生长出了150 mm级中等口径的KDP单晶,晶体生长速度达到20 mm/d.晶体生长过程中,生长溶液稳定,没有杂晶出现,生长的晶体完好且透明.X射线粉末衍射和摇摆曲线分析表明晶体有着较好的结构完整性;同时,测试了晶体的透过光谱和光损伤阈值,发现快速生长的晶体有着较好的光学性能.     

在NiMnCo-Cu-C体系中生长宝石级金刚石单晶

利用温度梯度法在NiMnCo-Cu-C体系、于5.5 GPa、1250℃条件下进行了宝石级金刚石单晶的生长研究,结果发现,Cu片在触媒中的放置位置和其在金属触媒中所占体积分数对宝石级金刚石单晶的生长具有明显影响.当Cu片放置在碳源和触媒之间时,将不会有充足的碳源扩散到籽晶上,晶体无法生长;但放在触媒中其他位置,体积分数适当时,不会对晶体生长有明显影响.随着Cu体积分数增加,优质晶体生长将变得困难,当体积分数在20;时,晶体有生长,但晶体内部跟表面明显存在由于包裹体存在造成的生长坑洞;当体积分数在40;左右时,晶体将不再生长.不过当Cu在触媒中的体积分数适当时,会降低碳源在触媒中的输运,从而对抑制自发核生长起到一定的作用.     

声光晶体TeO2的生长及缺陷研究

本文研究了直接ＴeO２晶体中的主要晶体缺陷形成机理,讨论分析了Ｔ eO2单晶生长的工艺参数对晶体缺陷的影响,结果表明：晶体裂缝的主要与温度梯度有关,温度梯度大于２０－２５℃/cm及出现界面翻转时,易造成晶全的开裂,位错密度增加,晶体中的包裹体主要为气态包裹全,它的形成主要与籽晶的转速和晶体的提拉速率有关,转速１５－１８r/min,拉速０.55mm/h,固液界面微凹,可以减少晶体中的气态包裹体,晶体台阶由晶体生长过程中温度和生长速度的引起伏引起,当台阶间距较宽时,易形成包裹体。     

Nb∶KTiOPO4晶体的生长和倍频性能

通过研究晶体生长工艺参数对Nb∶KTiOPO4(Nb∶KTP)晶体生长的影响,用熔盐顶部籽晶法获得尺寸为55mm×25mm×5mm的Nb∶KTP透明单晶.研究中发现熔体的温度梯度、籽晶和降温速率将严重影响Nb∶KTP晶体的生长.Nb离子的引入不利于Nb∶KTP晶体的生长,尤其是造成晶体易开裂,且沿a轴方向生长速度非常缓慢.同时,Nb的引入大大改变Nb∶KTP晶体的倍频性能.掺杂Nb浓度的摩尔分数为13;时,Nb∶KTP晶体的倍频的Ⅱ型相位匹配的截止波长缩短至937nm,且有效产生469nm倍频蓝光;掺杂Nb浓度的摩尔分数为3;时,Nb∶KTP晶体对Nd∶YAG的1.0642μm激光倍频的最佳相位匹配角为θ=88.32°,()=0°,非常接近90°非临界相位匹配方向.     

优质DKDP晶体的点状籽晶生长及其表征研究

本文在研究DKDP溶液稳定性的基础上,采用Z切点状籽晶(5mm×5mm×3mm)生长了多块DKDP晶体,在250ml和1000ml生长瓶中分别获得了在[100]和[001]向生长速度可达到3mm/d和4.5 mm/d的点状籽晶生长优质DKDP晶体的生长条件.通过等离子体发射光谱(ICP)和紫外可见光谱分析发现DKDP晶体柱面的金属离子含量比锥面高,柱面的紫外可见吸收比锥面大.性能测试结果表明,点状籽晶全方位生长的DKDP晶体的激光损伤阈值约为5GW/cm2、半波电压约为4kV、动态消光比约为1600∶1,发现与传统方法生长晶体的性能没有明显的差别.     

气相生长氮化铝单晶的新方法

通过在钨坩埚盖开小孔的方法改变氮化铝结晶衬底上的温度场分布,在开孔处形成局部低温区;由于孔的几何尺寸的限制和氮化铝晶体生长的各向异性,开孔处的氮化铝晶体单晶化;随后,开孔处的单晶起籽晶的作用,逐渐长成较大尺寸、较高质量的氮化铝单晶.目前用该方法已经制备出直径大于2mm的氮化铝单晶体.     

基于钠助熔剂法的GaN单晶生长研究进展

宽禁带氮化镓(GaN)材料以其独特的性质和应用前景成为国内外研究的热点，高质量GaN单晶衬底的制备是获得性能优异的光电子器件和功率器件的基础。钠助熔剂法生长条件温和，易获得高质量、大尺寸的GaN单晶，是一种具有广阔商业化前景的GaN单晶生长方法。钠助熔剂法自20世纪90年代末期被发明以来，经过20多年的发展，钠助熔剂法生长的晶体在尺寸与质量上都取得了长足的进步。本文从晶体生长原理和关键工艺(籽晶选择、温度梯度以及添加剂)等方面综述了钠助熔剂法生长GaN单晶研究进展，并对其面临的挑战和未来发展趋势进行了展望。     

The solid state controlled growth of sulphides and selenides of Ag and Cu using crystal rotation

An improved crystal growth method for ionic-electronic mixed conductors, such as the high temperature cubic modifications of Ag₂X and Cu₂X (where X = S or Se), is presented. Ag or Cu atoms are mobile in these compounds. If the respective sulphur or selenium vapour pressure was sufficiently high at the growth surface, the growth rate was limited by the solid state chemical diffusion of Ag or Cu atoms which was controlled by the rate of the injection of the metal atoms into the compounds. The crystals were grown in a silica ampoule, held in a vertical two zone furnace and rotated at 1 rpm about the vertical axis to achieve a uniform axial temperature distribution. Nearly cylindrical single crystals of size about 3–10 mm diameter, 10–35 mm long were grown by this method.     

Temperature field design,process analysis and control of SAPMAC method for the growth of large size sapphire crystals

In this paper, the relationship between quality of sapphire crystal and growing parameters of SAPMAC (Sapphire growth technique with micro‐pulling and shoulder‐expanding at cooled center) method was discussed. Optimized temperature distribution and technique control were proposed by theoretical analysis, numerical simulation computation and experimental validation to obtain large size sapphire crystals. For a‐axis crystallized direction, with 1.0‐5.0mm/h growth velocity and 10‐30K/h temperature decreasing speed, large sapphire single crystal (∅︁240mm×210mm, 27.5kg) having high optical quality was successfully grown. The absorption spectrum of standard samples was measured as well. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

热丝化学气相法生长单晶金刚石颗粒的衬底温度场仿真及实验研究

本文使用金刚石磨料作为晶种颗粒,通过热丝化学气相法生长出单晶金刚石颗粒,并且建立三维的有限元模型,利用有限元仿真分析了生长过程中影响金刚石磨料生长速率以及沉积质量的各种因素,如热丝的排列方式,衬底的温度场,以及晶种的分布方式.通过固定在热丝CVD反应腔里的热电偶测量了实际的衬底温度分布,从而验证了仿真结果的正确性.另外,通过改变仿真模型优化了沉积单晶金刚石颗粒的工艺参数,获得适应于合成单晶金刚石颗粒的新技术,为化学气相沉积合成单晶金刚石颗粒奠定了基础,也为高温高压金刚石磨料品级的改进与提高提供了新途径.     

Floating zone growth and characterization of ruby single crystals

Large, high optical quality single crystals of ruby have been grown successfully by the floating zone method under air atmosphere. The size of the grown crystal is typically 60‐70 mm in length and 7‐8 mm in diameter. The obtained crystals were red and did not have any macroscopic defects such as cracks and inclusions. Grown crystals were characterized by powder X‐ray diffraction (XRD) methods, polarized optical microscopy, scanning electron microscopy (SEM). The absorption and fluorescence spectra were measured at room temperature and the dielectric constant measurements of ruby crystals were also presented. Defects occurring in single crystals of ruby during crystal growth by floating zone method are described, and their correlation with the growth parameters is discussed. The origin and control of these defects in grown crystals were studied and the optimum method was proposed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Seed loading effects on the mean crystal size of acetylsalicylic acid in a continuous‐flow crystallization device

This study investigates the effects of seed loading on the mean crystal size of the model substance, acetylsalicylic acid, crystallized from ethanol in a continuously seeded tubular crystallizer. A hot, highly concentrated ethanolic acetylsalicylic acid solution was mixed with an acetylsalicylic acid‐ethanol seed suspension. Subsequent cooling of the slurry in the tubing promoted supersaturation and hence crystal growth. The tubular shape of the 15 m‐long crystallizer with an inner diameter of 2 mm enabled narrow residence time distributions of the crystals in the pipe and excellent temperature control in the radial direction and along the tubing. Crystals entering the crystallizer had both identical growth conditions in each section and about the same time for crystal growth. Narrow crystal size distributions were achieved with decreasing differences in the volume‐mean‐diameter sizes of the seed and product crystals as seed loadings increased. Decreasing the seed size had a similar effect as increasing the seed loading, since in that case the same amount of seed mass resulted in more individual seed particles. Altering the arrangement of the coiled crystallizer with respect to spatial directions (horizontal, vertical) did not lead to a significantly different outcome. All experiments produced considerably larger product crystals in comparison to the seeds despite relatively short crystallization times of less than 3 min. Moreover, product mass gains of a few hundred percent at a g/min‐scale were achieved. Similarities in product crystal samples taken at different times at the outlet of the crystallizer showed that steady‐state conditions were rapidly reached in the continuous flow crystallization device. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)