EDTA和KCl双掺杂下KDP溶液的稳定性研究

研究了EDTA与KCl不同掺杂浓度和不同过饱和比下KDP溶液的成核过程,测定了不同条件下KDP过饱和溶液的诱导期;根据经典成核理论计算了成核热、动力学参数,并分析了溶液稳定性随掺杂浓度的变化情况。利用化学腐蚀法对KDP晶体(100)面进行了腐蚀,得到了清晰的位错蚀坑,并使用光学显微镜观察了(100)面位错蚀坑的分布特点。结果表明,当过饱和度为4%、掺杂浓度为0.01 mol%EDTA和1 mol%KCl时,不仅KDP过饱和溶液的稳定性比较高,而且位错蚀坑的分布比较均匀、密度小,适合高质量的KDP晶体生长。     

点状籽晶法生长KDP晶体中散射颗粒分布

在不同的溶液pH值条件下进行了点状籽晶法慢速和快速生长KDP晶体实验,发展了观察晶体中散射颗粒分布的激光层析技术,通过图像处理得到了KDP晶体内部(100)面完整的散射颗粒分部图,对不同生长速度、不同pH值条件下点状籽晶法生长的KDP晶体的散射颗粒分部做了对比.利用表面光学投影技术观察了晶体表面宏观形貌,并由此分析了不同生长条件下生长机制对散射颗粒分布的影响.测定了散射颗粒密度不同部位的晶体透过率.     

用提拉法生长的GdCa4O(BO3)3晶体的结构缺陷研究

利用相衬显微镜结合化学腐蚀法,进行了沿 010 方向提拉生长的GdCa4O(BO3)3(GdCOB)晶体中的缺陷观察.发现位错是 010 方向生长的晶体中的重要缺陷.在不同方向的晶体切片上观察了螺位错和刃位错蚀坑,位错塞积,平底蚀坑及尖底蚀坑.位错密度随晶体长度的变化而变化.在晶体的尾部观测到位错密度为103/cm2,而在晶体的初始部位位错密度很低,只有40/cm2.在晶体的X,Z及 401 方向的切片的正反两面观察到的位错蚀坑现象完全不同,可以认为GdCOB晶体为单畴极性晶体,自发极化方向沿z轴方向.     

化学腐蚀法研究Nd:YAG晶体位错

采用化学腐蚀法研究Nd∶YAG晶体位错.研究发现,腐蚀剂、腐蚀温度以及腐蚀时间对位错的显示都有影响.浓磷酸腐蚀剂在220 ℃下腐蚀20 min时,显示的位错最为清晰.蚀坑形状为菱形,经过计算,位错密度大约为10~3 cm~(-2).同一种腐蚀剂在不同的腐蚀时间所形成的位错蚀坑大小和形貌是不同的.同时发现在样品的边缘有位错塞积群.     

近红外半导体材料HgInTe的缺陷腐蚀

研究了HgInTe的腐蚀工艺,探索出一种适合于HgInTe的腐蚀液,并对腐蚀原理做了分析.利用该腐蚀液对HgInTe晶体内部的缺陷种类和分布进行了研究.结果表明,垂直轴向切割的HgInTe晶片腐蚀后的位错蚀坑呈近等腰三角形.在本实验条件下,位错蚀坑密度EPD(etch-pit density)约在105/cm2数量级.HgInTe晶体中的位错墙主要以边重叠和角重叠两种方式排列而成.HgInTe中存在少量由内应力引起的微裂纹.该腐蚀液能有效地显示HgInTe晶体不同晶面的多种缺陷,腐蚀效果较好.     

硫镓银晶体的化学腐蚀研究

采用改进的垂直布里奇曼(Bridgman)法自发成核生长AgGaS2晶体,在生长初期对生长安瓿籽晶袋进行上提回熔,生长出外观完整、无裂纹的大尺寸AgCaS2单晶体.采用XRD对晶体进行分析,获得了(112)、(001)和(101)面的高强度尖锐衍射峰.采用不同配比的腐蚀剂对晶体(101)、(112)及(001)晶面进行化学腐蚀,然后采用金相显微镜和扫描电镜观察,结果显示,(101)晶面蚀坑为清晰的近似三角形的四边形蚀坑,(112)晶面蚀坑为清晰的近似三角锥形,(001)晶面则呈现互相垂直的腐蚀线.初步分析了不同蚀坑的形成原因,计算出(101)和(112)面蚀坑密度约为105/cm2数量级.结果表明,改进方法生长出的大尺寸AgGaS2单晶体结构完整、位错密度低,质量较好.     

碲锌镉单晶体的(110)面蚀坑形貌观察

本文报道了一种能够在室温下择优腐蚀碲锌镉(CZT)单晶体(110)晶面的腐蚀液配方,并对富Cd生长的CZT晶体蚀坑形貌进行了扫描电镜观察.结果表明晶体(110)面腐蚀坑形状为三角形,并初步对蚀坑的成因进行了分析,估算出CZT(110)面蚀坑密度约为103～105/cm2数量级.这说明富Cd原料的改进布里奇曼法可以生长出低蚀坑密度的CZT单晶体.     

KDP晶体“二维平动法”生长及其品质分析

首先测量了KDP溶液的亚稳区,并据此开展“点籽晶”KDP晶体快速生长实验.在实验中采用两种晶体运动方法-“二维平动法”和“旋转法”来生长晶体,分别得到尺寸为55 mm×55 mm×48 mm和60 mm×60 mm×45 mm的晶体.将两种运动方式生长的晶体通过透过光谱,锥光干涉图以及化学腐蚀方式进行质量对比.结果表明,两种方式生长的晶体透过光谱没有太大区别,都具有较高的透过率,但“二维平动法”生长的晶体具有较好光学均匀性,位错密度明显降低.说明“二维平动法”生长晶体的方式能够减少晶体内部缺陷,提高晶体质量.     

2μm波段激光晶体Tm:YAP的生长缺陷

采用提拉法沿a、b、c轴方向生长了Tm:YAP晶体,研究了该晶体的几种常见缺陷.通过化学腐蚀,利用光学显微镜观察了Tm:YAP晶体主要晶面的位错腐蚀坑形貌,发现在沿b轴生长晶体的(010)面上存在位错蚀坑密度不同的区域,对其成因进行了分析.借助偏光显微镜研究了晶体中的孪晶及消光现象,分析了成因并提出了消除措施.用He-Ne激光对晶体内的散射颗粒分布进行了研究,在扫描电镜(SEM)下观察到形状不规则的散射颗粒夹杂.上述研究结果对获得优质Tm:YAP晶体具有重要意义.     

L-精氨酸掺杂下ZTS溶液的稳定性研究

研究了L-精氨酸掺杂下硫脲硫酸锌(ZTS)溶液中的成核过程,测量了在不同掺杂浓度下ZTS溶液的亚稳区和诱导期.结果表明:随掺杂浓度的增加,溶液的亚稳区变宽,诱导期增大;根据经典成核理论计算了晶体的成核热、动力学参数,分析了溶液稳定性与掺杂浓度的关系,即随着L-精氨酸掺杂浓度的增加,溶液的稳定性得到明显提高.利用化学腐蚀法对ZTS晶体(100)面进行了腐蚀,并用光学显微镜对腐蚀面进行观察,得到了清晰的位错蚀坑.当L-精氨酸掺杂浓度为1.5mol;时,ZTS晶体(100)面位错蚀坑密度最小,适合高光学质量晶体的生长.     

KDP single crystal growth via three‐dimensional motion growth method

A novel system for rapid crystal growth, namely three‐dimensional motion growth method (“3D MGM”) was proposed. Using this system, a potassium dihydrogen phosphate (KDP) seed was grown to a single crystal with a final size of 50×55×85 mm³. The KDP crystal was characterized by Raman spectroscopy, UV‐vis‐NIR spectroscopy, extinction ratio, laser damage threshold, and etching studies. Raman spectrum shows KDP crystal grown by “3D MGM” maintains good crystallinity as that grown by rotating‐crystal method (“RCM”). The “3D MGM” grown KDP crystal has much better transmittance, higher extinction ratio, higher damage threshold and less dislocation density, compared to “RCM” grown crystal.     

Characterization of KDP crystal grown from solution with low pH value

Solubility curves of KDP (KH₂PO₄) in solutions with different pH values were measured. It was found that the solubility of KDP crystal increased with the reduction pH value of solution. Transparent KDP crystal was grown from solution with 1.5 pH by point seed. Chemical etching experiments revealed that pyramid sector of the crystal displayed more growth defects. Growth defects, such as growth striation and inclusion, were analyzed by white‐beam synchrotron radiation X‐ray topography. The reasons for the formation of these growth defects were discussed. Transmittance spectra test of both prismatic sector and pyramidal sector was performed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

硅酸钇晶体的生长、腐蚀形貌和光谱性能研究

本文采用中频感应提拉法成功生长了未掺杂的Y2SiO5(YSO)晶体,经过定向、切割、抛光后得到样品.经过腐蚀后,利用大视场显微镜和扫描电镜在样品表面上观察到了菱形和四边形的位错蚀坑、小角晶界和包裹物等缺陷;测试了经过氢气、空气退火前后,辐照前后YSO晶体的透过谱,结果表明:YSO晶体的吸收边大约在202nm,氢气退火后在200～300nm波段透过率增加,空气退火后透过率显著降低;辐照后,氢气退火的样品在200～500nm波段透过率显著降低.     

A new method of enlarging the cross-section of KDP using ADP crystals as seed

A new method of enlarging the cross-section of KDP crystals using an easily enlarged ADP crystal as seed for a KDP crystal, has been investigated. The growth characteristics of the ADP seeds (Z-plate, cap, and parallelly spliced seeds) at KDP supersaturation have been observed. Chemical etching was used to characterize the grown crystals, and chemical analysis to determine the composition of both the region of the seed and the grown crystal. The mechanism of this kind of growth is discussed. In conclusion this growing method should be qualified for enlarging the cross-section of KDP crystals.     

SiC籽晶表面状态对晶体质量的影响

为了研究表面状态对晶体质量的影响,本文分别采用腐蚀后抛光与未抛光的晶片作为籽晶,利用金相显微镜对所得晶体进行了显微观察,结果表明:经过腐蚀后抛光的籽晶生长出的晶体质量高于未抛光籽晶所得晶体;生长前端的位错尺寸以及数量小于未抛光籽晶,说明抛光去除了部分表面浅的缺陷腐蚀坑,同时减小深腐蚀坑的尺寸,使得籽晶生长表面的缺陷密度和尺寸大大降低,有助于减少后期生长的晶体中的缺陷密度,提高结晶质量.     

Improvement of growth habit and optical properties of rapidly grown KDP crystal by adding diethylene triamine pentacetate acid in growth solution

By altering the concentration of a new additive ‐ diethylene triamine pentacetate acid (DTPA) in the growth solution, a series of KDP crystals were obtained by the “point seed” rapid growth method. The growth rates up to about 20 mm/day. Effects of DTPA on the growth habit and optical properties of these as‐grown KDP crystals were investigated. The results reveal that, with the increase of DTPA concentration in growth solution, the contents of impurity metal ions incorporated into crystal and aspect ratio of crystal morphology were both decreased gradually, while the UV transmittance of crystal was enhanced continually. In the presence of moderate concentration of DTPA (100–200 ppm), the solution stability was increased and optical properties of crystal (including optical homogeneity, light scattering and laser damage threshold) were all improved. However excessive doping (>500 ppm) has opposite effects. The impact mechanism was also analyzed combining with the structure of KDP crystal and chemical characteristics of DTPA molecular.     

TEM,chemical etching and FTIR characterization of ZnTe grown by physical vapor transport

ZnTe ingots were obtained by the physical transport method, using an in‐house designed and built tubular furnace. The growth of ZnTe subsequently to the growth of a seed of this material allowed obtaining an ingot formed by only one large and single crystalline grain. TEM was used for the characterization of the as‐grown ZnTe single crystal ingots and commercial single‐crystalline wafers of the same material but grown by a higher temperature and more expensive technique, the Bridgman method. Both materials show very good crystalline microstructure, although some stacking faults were found in the commercial one. The infrared transmittance spectra of both materials were measured by FTIR and some differences, most likely due to differences in raw materials and growth methods, were found. The effectiveness and convenience of several chemical etchants to obtain the dislocation density and the minimal misorientation between adjacent subgrains in the as‐grown ZnTe wafers were checked. It has been found as the most advantageous the chemical solution that does not produce over‐etching. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rapid Z-plate seed regeneration of large size KDP crystal from solution

Regeneration process of a 330×330×20 mm³ Z-plate seed is carried out in a 1.5 metric tonnage volume crystallizer that placed in a water bath of temperature fluctuation less than ±0.02 °C within 10 days. The surface of the whole crystal was restored by the formation of a box-like structure filled with growth solution, and then the transparent layer of perfect tetragonal KDP crystal without inclusions, crack and milky regions just like those produced by traditional slow cooling technique can be grown from solution. After the regeneration, the height of KDP crystal is merely 0.5 times the side of plate seed. We found it that the optical transmission and laser damage threshold of the KDP crystals we grown are not significantly different from those of KDP crystals grown by traditional method.     

Propagation behavior of threading dislocations during physical vapor transport growth of silicon carbide (SiC) single crystals

The dislocation formation and propagation processes in physical vapor transport (PVT) grown 4H silicon carbide (4H–SiC) single crystals have been investigated using defect selective etching and transmission electron microscopy (TEM). It was found that while the growth initiation process generally increased the density of threading dislocations in the grown crystal, for certain areas of the crystal, threading dislocations were terminated at the growth initiation. Foreign polytype inclusions also introduced a high density of dislocations at the polytype boundary. In the polytype-transformed areas of the crystal, almost no medium size hexagonal etch pits due to threading screw dislocations were observed, indicating that the foreign polytype inclusions had ceased the propagation of threading screw dislocations. Based on these results, we argued the formation and propagation of the threading dislocations in PVT grown SiC crystals, and proposed the dislocation conversion process as a plausible cause of the density reduction of threading dislocations during the PVT growth of SiC single crystals.