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.     

pH值对KDP晶体位错结构的影响

在一定的过饱和度下,分别用点状和片状籽晶在不同pH值溶液中生长出了KDP晶体.利用化学腐蚀法对KDP晶体的不同晶面进行了腐蚀,得到了清晰的位错蚀坑.应用光学显微镜对位错蚀坑的分布特点和密度做了观察分析,发现很多位错蚀坑成线状排布.pH值对KDP晶体位错密度有较大影响,低pH值条件下生长出的晶体位错密度较大.测试了KDP晶体样本的透过率,结果表明位错密度对KDP晶体的透过率没有明显的影响.     

提拉法Ti:LiAlO2晶体的生长、缺陷及N2退火研究

本文采用提拉法成功地生长了钛掺杂浓度为0.1%原子分数的LiAlO2单晶体,借助光学显微镜,结合化学腐蚀法,对Ti:LiAlO2晶体(100)面空气退火前后的缺陷特征进行了研究,用AFM观测了(100)面晶片在不同温度下流动N2气氛退火过的表面形貌。结果表明:Ti:LiAlO2晶体(100)面的位错腐蚀坑是底面为平行四边形的锥形坑,位错密度约为5.0×104cm-2,900℃空气退火后晶片表面的位错腐蚀坑变大;N2退火能显著影响晶片的表面形貌,当退火温度为900℃时,晶片的均方根粗糙度(RMS)达到最低值。     

激光晶体位错蚀坑的SEM研究

利用扫描电镜(SEM)及能谱(EDS)技术研究激光晶体缺陷,给出了经腐蚀过后Nd: YAG晶体表面位错蚀坑的清晰图片和元素分布定量信息,同时进行了对比实验,并对实验结果进行了分析.结果表明:Nd: YAG晶体位错腐蚀坑呈三角锥状,腐蚀坑杂质元素分布较多,主要元素含量偏离晶体完整区成份;位错腐蚀坑稀疏区与密堆区元素分布及含量不同.并讨论了位错成因.     

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.     

Nd,Y:SrF2激光晶体的位错缺陷表征及分布研究

氟化物激光晶体Nd, Y∶SrF₂(NYSF)具有热导率高、发射光谱宽、发射截面适中等特点，在高功率激光技术领域具有重要应用。激光晶体中的位错是反映其晶格完整性的一类重要的微观晶体缺陷，对晶体材料的力学、光学性能具有重要影响。本文采用坩埚下降法制备了NYSF激光晶体，分析了腐蚀实验条件对位错蚀坑形貌的影响，获得了化学腐蚀法研究NYSF晶体位错缺陷的最佳腐蚀工艺，即浓度为4 mol/L的盐酸溶液作为腐蚀液，腐蚀温度为60℃、腐蚀时间为9～12 min;表征了位错腐蚀坑形态的演变过程，探讨了晶格原子排列对位错蚀坑形态的影响；利用化学腐蚀方法表征了位错缺陷在晶体中的分布规律，即轴向分布为从放肩到尾部先减少后增加，径向分布为从中心到边缘逐步增加；分析了晶体生长条件对位错缺陷形成的影响，提出了位错密度随坩埚下降速率的提高而升高的可能原因。     

重掺杂P型SiC的熔融KOH刻蚀行为研究

本文采用熔融KOH刻蚀方法详细研究了液相法生长的重掺杂P型6H-SiC晶体中的位错情况,探究了时间、温度变化对液相法生长的重掺杂P型6H-SiC晶片表面刻蚀的影响。当提高腐蚀时间或腐蚀温度时,晶片表面的腐蚀坑尺寸均表现出不同程度的增加,过高的温度及长时间刻蚀均导致过腐蚀现象的发生。根据不同腐蚀条件下腐蚀坑的形貌与分布,确定出刻蚀重掺杂P型6H-SiC晶片的最佳工艺参数。利用晶片在不同温度下的腐蚀速率变化关系及阿伦尼乌斯公式计算出晶体的反应活化能为10.59 kcal/mol。最后,对穿透型螺位错(TSD)和穿透型刃位错(TED)的形貌、尺寸和内部结构进行了详细的表征和分析,结果表明P型6H-SiC晶体中腐蚀坑的倾角与腐蚀时间无关。     

r面白宝石单晶的温梯法生长及缺陷研究

本文描述使用温梯法(TGT)生长(1102)方向的白宝石单晶,应用X射线双晶摇摆曲线(XRC)测定了晶体内部的完整性,再利用KOH熔体腐蚀出样品的r面(1102)上的位错蚀坑,借助扫描电子显微镜(SEM)进行观察,发现r面白宝石的位错腐蚀坑呈等腰三角形,并且有台阶状结构,并分析了位错的成因.     

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.     

Salting-out precipitation of potassium dihydrogen phosphate (KDP). I. Precipitation mechanism

The precipitation of KDP produced by salting-out with aqueous solutions with different contents of ethanol, 1-propanol and 2-propanol have been studied at 30°C. Induction periods were determined as function of the solution initial supersaturation by a visual procedure. From the experimental results it was possible to conclude that the formation of the new solid phase is controlled by primary nucleation followed by normal growth. The interfacial surface tension of KDP in different solvents was also obtained.     

Dual action of Impurities in Crystal Growth from Solutions

A dual action of impurities becomes evidently in growth kinetic of prismatic faces of KDP. At higher supersaturation two-dimensional nucleation mechanism due to impurities prevails. At smaller supersaturation the blocking effect of the steps created by the dislocation mechanism of growth become efficient. The limit of the “dead” growth zone depending on the impurity's concentration and the solution pH is a result of this last effect and agrees with the Cabrera-Vermilyea mechanism.     

In situ AFM investigation of 2D nucleation on the (100) face of KDP

Surface morphology of the (100) face of potassium dihydrogen phosphate (KDP) crystals which were grown at different supersaturations at 25 °C was investigated by in situ atomic force microscopy (AFM). Various AFM images of 2D nucleation under different growth conditions were presented. It is found that the growth of KDP is controlled by polynuclear nucleation mechanism at the high supersaturation. With reduction of the supersaturation, the growth velocity of 2D nuclei becomes very slow and shows typical anisotropy. It is found that the process of coalescence of 2D nuclei does not lead to defect. The experiments show that the growth mechanism for KDP at 25 °C changes between step flow and 2D nucleation in the supersaturation range of 4.5‐5%. The triangular nuclei which are close to equilateral triangle are observed in the experiment at the supersaturation σ = 6% for the first time, showing typical anisotropic growth. Through observing the dissolution of 2D nuclei, the dissolving process can be regarded as the reverse process of growth. We also find that the microcrystals landing on the surface at σ = 9% would grow and coalesce with each other and there is no observable defect in the coalescence. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fe3+对KDP晶体生长影响的研究

金属离子对KDP晶体的影响是多方面的.本文采用不同的过饱和度,在不同的Fe3+掺杂浓度的生长溶液中生长KDP晶体,定量地研究了Fe3+对KDP晶体生长的影响.实验发现,无论是在高过饱和度还是在低过饱和度下生长KDP晶体,在一定的浓度范围内,Fe3+的掺入既可以增加生长溶液的稳定性,又可以有效抑制晶体柱面的扩展,而且晶体基本不楔化,同时,对晶体光学性能的影响也不大.     

The combined effects of supersaturation and Ba2+ on the batch cooling crystallization of potassium dihydrogen phosphate

The combined effects of supersaturation and Ba²⁺ on potassium dihydrogen phosphate (KDP) were investigated in batch cooling suspension crystallization. Growth size, morphology, and impurity Ba²⁺ adsorbed in the KDP crystals were measured with changing Ba²⁺ concentration and supersaturation. Significant changes in shapes and volume of the grown crystals have been observed. The results further confirmed that the size and shape of crystals were greatly determined by supersaturation. Ba²⁺ ions significantly modified the growth habit of KDP crystals. The concentration of Ba²⁺ ions adsorbed in the crystals increases with the increasing Ba²⁺ ions in the solutions and supersaturation. The foggy phenomena caused by the addition of Ba to the KDP solution were also described. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of pH value on the growth morphology of KH2PO4 crystal grown in defined crystallographic direction

KH₂PO₄ single crystals were grown in aqueous solution at different pH values by using “point seeds” with a defined crystallographic direction at 59 degree to the Z axis. Atomic Force Microscope (AFM) was applied to observe the surface morphology of (100) face. It was found that at the same supersaturation, the larger steps appeared at the lower pH value before appearance of 2D nucleus. We found that 2D nucleus was occurred at σ ≤ 0.04 when pH value is <2.8. The occurrence of 2D nucleus was caused by the decreasing step‐edge free energy with the decreasing of pH value in the growth solution. In this paper, we observed the morphologies of (100) faces of KDP crystals which grew in solutions with different pH values. 2D nucleuses appeared on the terrace of growth steps when pH value down to 2.8 and 3.2 at supersaturation of 0.04, while pH value down to 2.4, only 2D nucleation control the growth. Therefore, the pH value can change the growth mechanism of KDP crystals.     

不同pH值下磷酸二氢铵(ADP)溶液成核过程研究

利用全程摄像的方法测定了不同情况下ADP过饱和溶液的诱导期,研究了不同pH值、不同温度的ADP过饱和溶液的成核过程,讨论了pH值、温度和过饱和度S等因素对诱导期的影响.结果表明:改变pH值后,在同一过饱和度下,溶液的稳定性在不同温度间差异较小,更利于晶体在较高的温度下稳定快速的生长;改变pH值后,溶液在整个过饱和度范围内更趋向于均匀成核.根据经典均匀成核理论,针对ADP溶液均匀成核的状况计算出了不同pH值和温度下的固-液界面张力、临界成核功等成核参数,并从上述参数的相互比较中得到了改变pH值后溶液稳定性变强的微观原因.最后通过对表面熵因子的计算,确定了ADP晶体的微观生长机制为连续生长模式.     

Synergy of organic dyes for KDP crystal growth

Single potassium dihydrogen phosphate (KDP) crystals were grown in a supersaturated solution containing an organic dye (sunset yellow FCF, brilliant blue FCF, and sky blue). The growth rate, morphology, and impurity dye distribution of faces, (100) and (101) in a KDP crystal were measured as dye concentration and the supersatutation of KDP were changed. Complete expressions for the effect of dye on all aspects of the growth of KDP crystals were discussed. The growth rates of (100) and (101) faces were well correlated by the empirical equation, and resulted in good estimation of the morphology. The distribution of dye in a KDP crystal was represented by the distribution model containing the minimum growth rate for coloring. The growth rate equation and distribution equation were expressed by functions of the supersaturation and dye concentration, and they could effectively provide the operational conditions with coloring the KDP crystal. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of emulsion types on nucleation kinetics and growth habit in the cooling crystallization

Experiments on unseeded batch cooling crystallization were made to investigate the influence of emulsion [solution in non‐solvent (S/NS) emulsion and non‐solvent in solution (NS/S) emulsion] on crystal size and growth habit of various materials such as hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine, ammonium sulfate, potassium dihydrogen phosphate (KDP), and γ‐glycine. Size of crystals obtained from the S/NS emulsions was found to be significantly larger than that obtained from the NS/S emulsions. Those results were explained by broad induction time distribution of nucleation in the isolated solution droplets and subsequent seeding effect by free movement of early‐induced crystals by vigorous agitation. As a result, the population density of crystals was shown to be smaller in the S/NS emulsions than that in the NS/S emulsions. In the S/NS emulsions, desupersaturation rate should be slow and high supersaturation is subsequently generated during crystal growth stage. Therefore, it may be concluded that crystal morphology of the materials with supersaturation dependent growth habit, such as ammonium sulfate, KDP and γ‐glycine, can be controlled by selection of emulsion type.     

Distribution of metallic ions in a single KDP crystal grown from aqueous solution

A single KDP (potassium dihydrogen phosphate) crystal was grown in a supersaturated solution containing a metallic ion (Al³⁺, Fe³⁺, or Cr³⁺). The growth rate, morphology, and distribution of the metallic ions into the KDP crystal were measured as the ionic concentration and supersaturation in the solution changed. It was found that in the KDP crystal, Al³⁺ and Fe³⁺ were greatly concentrated, but Cr³⁺ was diluted. Complete expressions for the effect of metallic ions on all aspects of the growth of KDP crystal were suggested. The growth rates of (100) and (101) faces were well correlated by the empirical equation and resulted in good estimation of morphology. The distribution of metallic ions into KDP crystal was also correlated by the distribution model. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)