大尺寸金红石(TiO2)单晶体生长条件的实验研究

采用高纯(99.995;)、超细的金红石(TiO2)粉末为起始原料,用燃熔法制备了尺寸为30mm×50mm的金红石(TiO2)单晶体.讨论了生长气氛、生长速度、温度梯度在晶体生长中的作用,对比了晶体在空气中与在氧气中退火的结果,测定了晶体试样的摇摆曲线和透过率,并与商用晶体的透过率进行了比较.实验表明:生长气氛中的氧分压大于液固界面(即生长界面)处熔体的氧离解压是生长完整晶体的必要条件;在此条件下,能否生长为大尺寸晶体则取决于炉膛的轴向温度梯度;晶体在退火过程中可消除热应力,但退火更重要的作用是通过氧化反应消除氧空位,在氧气氛中退火,可明显缩短退火时间;所制备的晶体完整性较好,透过率与商用晶体基本一致.     

钛酸锶单晶体生长工艺研究

使用数控焰熔法晶体生长炉生长钛酸锶单晶体,研究了气体参数、生长速度和退火工艺参数对晶体生长的影响.在氢氧比为2.5,等径生长速度保持在10 mm·h-1,生长出了直径26 mm、等径长度20 mm、总长40 mm的钛酸锶单晶体,然后经过1550℃ ×72 h+1000℃ ×20 h+600℃ ×24 h的退火,消除钛酸锶单晶体的热应力和氧空位,得到完整的高品质的单晶体.偏光显微镜测试表明,晶体具有很好的完整性.     

提拉法生长高质量氟化镁单晶

设计了适合提拉法生长氟化镁单晶体的温场,采用提拉法成功生长出了直径100 mm的高质量氟化镁单晶.晶体内无气泡等宏观缺陷、无开裂;通过精密退火处理后,晶体透过率达到95;,平均应力双折射小于0.5 nm/cm.上述结果表明采用提拉法可以生长高质量的氟化镁单晶.     

SrTiO3单晶体生长过程中的溢流问题

本文以氯化锶和氯化钛为原料,采用控制水解法制备SrTiO3原料粉末,使用焰熔法生长了SrTiO3单晶体.晶体生长参数为:原料粉末粒度为-200+250目,炉膛气氛的氢氧比H/O为6.00,生长速度为12mm/h,获得了直径30mm,长60mm的单晶.晶体生长过程中,晶体顶部熔体的溢流是妨碍获得大尺寸完整晶体的一个最主要的问题.本文详细讨论了SrTiO3单晶体生长过程中的溢流的成因和解决办法.     

ZnGeP2单晶生长温场研究

根据ZnGeP2(ZGP)晶体的生长特性,自行设计组装了三段式独立控温生长炉,优化了温场分布.采用改进的垂直布里奇曼法成功生长出外观完整、无裂纹的ZGP单晶体,尺寸达15 mm×35 mm.对晶体进行解理实验和X射线衍射分析,发现ZGP晶体易沿(101)面解理,其回摆峰尖锐无劈裂.对未经退火处理的晶片进行红外透过率测试,在2～12 μm波段内红外透过率达45;以上.研究结果表明所设计的温场适合于ZGP单晶生长,生长出的ZGP晶体完整性好、质量较高.     

退火处理对CdZnTe晶体光电性能的影响

研究了生长态CdZnTe晶体在经历了不同温度和时间的Cd/Zn和Te气氛退火后,其光电性能的变化规律.研究表明,在Cd/Zn气氛下退火180 h后,CdZnTe晶体中直径在5μm以上的Te夹杂的密度减小了1个数量级,晶体的体电阻率由1010 Ω·cm减小至～107 Ω· cm.同时发现,Cd/Zn源区的温度决定了退火后晶体在500～4000cm-1范围内红外透过率曲线的平直状态,这可能与晶体中的Cd间隙缺陷浓度相关,而与晶体中的载流子浓度和夹杂/沉淀相状态无关.在Te气氛下退火时,发现晶体的红外透过率的平直状态与晶体电阻率的对数lg(ρ)呈近似线性关系,同样可归因于退火过程中Cd间隙缺陷的浓度变化.     

不同气氛下YAl3(BO3)4晶体的生长和激光性能研究

分别在有氧气氛(空气)和还原气氛(氢气/氩气混合气)下生长了YAl3(BO3)4(YAB)晶体,并研究了不同生长条件下生长的YAB晶体的透过和266nm激光的输出性能.结果表明,还原气氛下生长的YAB晶体能够消除266 nm附近的吸收,但是晶体的266 nm输出性能并未得到提高.分析推测了可能的原因,并对下一步工作提出可行性的建议.     

红外非线性光学晶体CdSe生长与性能表征

采用垂直无籽晶气相法(VUVG)生长出尺寸达26 mm×45 mm的CdSe单晶体,对CdSe晶体的稳态气相生长速率进行了深入讨论.采用气相升华法提纯后的CdSe多晶原料的X射线粉末衍射谱与PDF卡片值(65-3436)吻合,生长出的单晶体{100}和(110)面XRD衍射峰尖锐,无杂峰,且{100}面出现3级衍射峰.晶锭密度为5.74 g/cm3,与理论计算值接近.退火处理后的晶片在1000～7000 cm-1 红外波段范围内透过率达到70;.采用VUVG法生长的CdSe单晶体,结晶性能好、结构致密、尺寸大和红外透过率高,可用于制备红外非线性光学器件.     

CdWO4闪烁晶体的生长及其光学性能的研究

本工作生长出了φ57mm×45mm的大尺寸CdWO4单晶,并报道了该晶体的最佳生长工艺.对CdWO4原料的一次烧结物、生长炉壁的挥发物进行了XRD谱的测试分析,结果表明一次烧结可以得到基本成相的多晶料;生长原料CdO较WO3更易挥发.同时,测试了CdWO4晶体的一些光学性能,初步探讨了该晶体的发光特性,分析表明氧退火有利于提高晶体的透过率,这可能是由氧退火使氧空位减少所致.此外,该晶体的本征发光主要是由蓝、绿光所组成的.     

高能电子辐照和退火对磷锗锌晶体红外光学性质的影响

对采用改进的垂直布里奇曼法生长出的磷锗锌(ZnGeP2)单晶体样品,在300 K,10 MeV高能电子束下进行辐照实验,测试辐照前后其红外透过率.同时,对样品进行同成分粉末包裹退火处理,对比两种工艺对磷锗锌晶体红外透过率的影响.实验结果表明,退火和高能电子辐照都能对磷锗锌晶体的红外光学性质产生影响,提高其红外透过率.在本文的实验条件下,退火工艺对磷锗锌晶体红外透过率的提高更为明显.     

同质外延生长ZnO单晶结构及光电性能的研究

本文报道了同质外延生长氧化锌(ZnO)单晶在高温氧气气氛退火前后的结构及光电特性。利用化学气相输运(CVT)法生长了红棕色的ZnO单晶,且进行高温氧气气氛退火处理后的ZnO单晶呈现无色透明状。通过X射线衍射仪(XRD)、X射线光电子能谱(XPS)、能谱仪(EDS)和拉曼(Raman)光谱测试分析了高温氧气气氛退火前后的ZnO单晶结构,讨论了退火对单晶内部缺陷类型及结构的影响。XRD测试表明ZnO单晶的生长方向为(002)方向。退火前后ZnO单晶的ω摇摆曲线半高宽分别为59″和31″,表明退火后单晶内缺陷显著减少;XPS和EDS能谱分析了退火前后ZnO单晶的成分和元素价态,结果表明高温氧气气氛处理后单晶内Zn和O元素含量比更接近理论值;通过Raman光谱分析了高温氧气气氛处理前后ZnO单晶的不同拉曼振动模式;通过紫外光谱数据分析,得到了退火前后ZnO单晶的光学禁带宽度分别为3.05 eV和3.2 eV;最后,通过Hall测试分析了高温氧气气氛退火处理前后ZnO单晶的电学性能参数,并深入讨论了退火前后ZnO单晶的低温电输运特性。     

气体湍流对泡生法生长蓝宝石单晶温场的影响

本文采用专业晶体生长模拟软件CrysVUn对泡生法生长大尺寸蓝宝石单晶进行了计算机模拟.分析了气体压力对泡生法生长蓝宝石单晶的温场、气体速度场的影响.结果发现在气压P≥105Pa时,特别是在引晶初期,容易出现籽晶根部熔化,这在实验中得到了很好的验证,并提出了三种解决方案.     

紊流模型模拟分析旋转对提拉大直径单晶硅的影响

本文采用紊流模型对提拉大直径单晶硅时,对晶体旋转、坩埚旋转及二者共同作用三种情况下,熔体内的流线、等温线、氧的浓度分布、紊流粘性系数、紊动能等作了数值模拟,发现晶体的旋转能提高氧的径向均匀性,紊流粘性系数和紊动能随着坩埚转速的提高先增加后下降.晶体坩埚同时旋转时并不能有效降低紊流粘性系数,但能使子午面上的流动受到抑制,等温线更为平坦,有利于晶体生长.     

稀释磁性半导体Cd0.9Mn0.1Te晶体的退火改性

运用缺陷化学原理近似计算了Cd0.9Mn0.1Te晶体的点缺陷浓度,得到了晶体成分与理想化学计量比偏离最小时的退火条件.利用该退火条件,指导了Cd0.9Mn0.1Te晶体的两温区退火实验,并分析了退火对晶片性能的影响.结果表明:在973 K,Cd气氛下对Cd0.9Mn0.1Te晶片退火140 h后,晶片(111)面的X射线回摆曲线的FWHM值由退火前的168.8' 降至108',红外透过率由退火前48;提升到64;,接近晶体的理论透过率,电阻率也由退火前的2.643×105 Ω·cm提高到4.49×106 Ω·cm.由此可见,对生长态的Cd0.9Mn0.1Te晶体进行退火实验能提高晶体的结晶质量,补偿晶体的Cd空位点缺陷,使晶体成分接近理想的化学计量比.     

氧分压对化学气相沉积法合成ZnO纳米结构形貌的影响

本文利用化学气相沉积(CVD)法在镀有Au(10 nm)膜的单晶Si(100)上制备了ZnO薄膜,并研究了不同的氧分压对ZnO形貌的影响.借助扫描电镜(SEM)、X射线衍射仪(XRD)和透射电子显微镜(TEM)对样品的形貌、结晶质量和晶体生长取向进行了表征.结果表明:当O2分压较小的时候,O2只能与Zn团簇的某些界面发生反应并逐渐结晶生成层状的ZnO微米团簇.当 O2分压较大的时候,ZnO通过二次生长形成由微米柱阵列和表面无序纳米线构成的分层复合结构,并且表面纳米线的密度随着氧分压的增加而增加.高分辨透射电镜(HRTEM)和选取电子衍射(SAED)分析表明,单根纳米线是沿[001]方向生长的ZnO单晶.     

Effects of CaO addition on growth of YVO4 single crystals

YVO₄ single crystals doped with CaO are grown by the floating zone method in nitrogen atmosphere. The crystal is colorless and transparent after annealing in oxygen atmosphere. The effects of CaO addition are discussed. The Ca²⁺ ions can substitute for Y³⁺ at Y-sites in the YVO₄ structure to form oxygen vacancies via which oxide ions can easily diffuse and, consequently, yield transparent crystals.     

移动加热器法生长碲锌镉晶体的组分输运与界面形貌研究

移动加热器法(THM)生长碲锌镉晶体时,界面稳定性对晶体生长的质量有很大影响。本文基于多物理场有限元仿真软件Comsol建立了THM生长碲锌镉晶体的数值模拟模型,讨论了Te边界层与组分过冷区之间的关系,对不同生长阶段的物理场、Te边界层与组分过冷区进行仿真研究,最后讨论了微重力对物理场分布的影响,并对比了微重力与正常重力下的生长界面形貌。模拟结果表明,Te边界层与组分过冷区的分布趋势是一致的,在不同生长阶段,流场中次生涡旋的位置会发生移动,从而导致生长界面的形貌随着生长的进行发生变化,同时微重力条件下形成的生长界面形貌最有利于单晶生长。因此,在晶体生长的中前期,对次生涡旋位置的控制和对组分过冷的削弱,是THM生长高质量晶体的有效方案。     

Study of melt dynamics in crystal growth of Pb1−xSnxTe by the inverted Bridgman method

Experiments with crystal growth of Pb_1−xSn_xTe by the inverted Bridgman method confirm the flow transition in the melt through succeeding stages of unsteady (turbulent) convection, periodically unsteady convection, one-vortex steady motion, two-vortex motion and in the end, lack of any detectable convection — in the range of Rayleigh numbers and ratios of melt height to ampoule diameter given by Müller et al. [J. Crystal Growth 70 (1984) 78]. Additionally, quasi-steady axially asymmetric flow between the first two stages has been observed. Its direction is opposite to the direction of the vortex formed in the subsequent stage of crystal growth. The two-vortex flow, beginning when the melt height equals the ampoule radius, is unsteady and periodically changes the liquid-solid interface shape.     

Mechanism for generating interstitial atoms by thermal stress during silicon crystal growth

It has been known that, in growing silicon from melts, vacancies (Vs) predominantly exist in crystals obtained by high-rate growth, while interstitial atoms (Is) predominantly exist in crystals obtained by low-rate growth. To reveal the cause, the temperature distributions in growing crystal surfaces were measured. From this result, it was presumed that the high-rate growth causes a small temperature gradient between the growth interface and the interior of the crystal; in contrast, the low-rate growth causes a large temperature gradient between the growth interface and the interior of the crystal. However, this presumption is opposite to the commonly-accepted notion in melt growth. In order to experimentally demonstrate that the low-rate growth increases the temperature gradient and consequently generates Is, crystals were filled with vacancies by the high-rate growth, and then the pulling was stopped as the extreme condition of the low-rate growth. Nevertheless, the crystals continued to grow spontaneously after the pulling was stopped. Hence, simultaneously with the pulling-stop, the temperature of the melts was increased to melt the spontaneously grown portions, so that the diameters were restored to sizes at the moment of pulling-stop. Then, the crystals were cooled as the cooling time elapsed, and the temperature gradient in the crystals was increased. By using X-ray topographs before and after oxygen precipitation in combination with a minority carrier lifetime distribution, a time-dependent change in the defect type distribution was successfully observed in a three-dimensional manner from the growth interface to the low-temperature portion where the cooling progressed. This result revealed that Vs are uniformly introduced in a grown crystal regardless of the pulling rate as long as the growth continues, and the Vs agglomerate as a void and remain in the crystal, unless recombined with Is. On the other hand, Is are generated only in a region where the temperature gradient is large by low-rate growth. In particular, the generation starts near the peripheral portion in the vicinity of the solid–liquid interface. First, the generated Is are recombined with Vs introduced into the growth interface, so that a recombination region is always formed which is regarded as substantially defect free. Excessively generated Is after the recombination agglomerate and form a dislocation loop region. Unlike conventional Voronkov's diffusion model, Is hardly diffuse over a long distance. Is are generated by re-heating after growth.[In a steady state, the crystal growth rate is synonymous with the pulling rate. Meanwhile, when an atypical operation is performed, the pulling rate is specifically used.]This review on point defects formation intends to contribute further silicon crystals development, because electronic devices are aimed to have finer structures, and there is a demand for more perfect crystals with controlled point defects.     

Optimization of control parameters of cadmium zinc telluride Bridgman single crystal growth

The temperature gradient within a furnace chamber and the crucible pull rate are the key control parameters for cadmium zinc telluride Bridgman single crystal growth. Their effects on the heat and mass transfer in front of the solid‐liquid interface and the solute segregation in the grown crystal were investigated with numerical modeling. With an increase of the temperature gradient, the convection intensity in the melt in front of the solid‐liquid interface increases almost proportionally to the temperature gradient. The interface concavity decreases rapidly at faster crucible pull rates, while it increases at slow pull rates. Moreover, the solute concentration gradient in the melt in front of the solid‐liquid interface decreases significantly, as does the radial solute segregation in the grown crystal. In general, a decrease of the pull rate leads to a strong decrease of the concavity of the solid‐liquid interface and of the radial solute segregation in the grown crystal, while the axial solute segregation in the grown crystal increases slightly. A combination of a low crucible pull rate with a medium temperature gradient within the furnace chamber will make the radial solute segregation of the grown crystal vanish. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)