低阻值In掺杂CdZnTe晶体的退火改性

以Cd_(1-y)Zn_y合金作退火源,对采用改进的垂直布里奇曼法(MVB)生长的In掺杂的Cd_(0.9)Zn_(0.1)Te晶片进行退火改性.结果表明:与退火前相比,退火后晶片的成分均匀性提高,Cd、Zn和Te三种元素的含量更接近理想的化学计量比,平均红外透过率由12;提高到59;,电阻率从3.5×10~6 Ω·cm提高到5.7×10~9 Ω·cm,且在PL谱中出现了代表晶体质量的(D~0,X)发光峰.在合适的条件下对低阻值In掺杂的CdZnTe晶体进行退火改性可较好的提高晶体的性能.     

Te溶剂-Bridgman法Cd0.9Mn0.1Te晶体生长习性研究

采用Te溶剂-Bridgman法生长了尺寸为φ30 mm× 60 mm的Cd0.9Mn0.1Te:In晶锭,通过淬火得到了生长界面形貌.测试了晶片在近红外波段的透过率和电阻;采用化学腐蚀的方法观察了晶片中位错,Te夹杂和孪晶界;采用光学显微镜和红外成像显微镜观察了生长界面处附近的形貌.测试结果表明,晶锭中部结晶质量较好的晶片红外透过率达到60％,电阻率达到2.828×1011Ω · cm.位错密度在106 cm-2数量级,Te夹杂密度为1.9×104 cm-2,同时孪晶密度明显低于Bridgman法生长的晶锭.生长界面宏观形貌平整,呈现微凹界面.但由于淬火过程的快速生长,界面微观形貌发生变化,呈现不规则界面,并在界面附近形成富Te相的包裹.     

移动加热器法生长CdMnTe和CdZnTe晶体的性能研究

采用移动加热器法生长铟惨杂浓度为5×1017 atoms/cm3的Cd0.9Mn0.1Te (CMT)和Cd0.9Zn0.1Te (CZT)单晶.生长得到的CMT晶体和CZT晶体电阻率范围为4.5×109 ～ 6.2×1010 Ω·cm.CMT晶体的成分均匀性要优于CZT晶体,拟合得到CMT和CZT晶体中Mn和Zn的分凝系数分别为0.95和1.23.富Te区在两种晶体生长过程中都具有显著的提纯作用,In惨杂的浓度范围均在6.4 ～ 14.4 ppm范围内.红外透射显微镜观察到三角形和六边形为主的Te夹杂的尺寸5 ～24 μm,浓度为105 cm-3.除最后结晶区之外,沿晶体生长方向Te夹杂的尺寸逐渐减小而浓度逐渐增大.制备的CMT和CZT探测器对59.5 keV241Am放射源均有能谱响应,能量分辨率分别为23.2;和24.6;.     

磷锗锌晶体的热处理研究

采用改进垂直布里奇曼法生长出的磷锗锌(ZnGeP2,ZGP)晶体中存在各种缺陷,导致其红外透过率较低,刚生长的晶体不能直接用于制备红外非线性光学器件.分别采用真空、同成分粉末包裹和真空-同成分粉末包裹的复合退火工艺对生长的ZGP晶体进行了退火热处理研究.应用傅立叶红外光谱仪(FTIR)、高阻仪(HRM)、X射线能谱仪(EDS)等对退火前后的晶体性能和成分进行了测试分析.结果表明,三种方法退火后晶体的红外透过率和电阻率都得到改善,其中复合退火工艺的改善效果最为显著,晶体红外透过率由41;提高到60;,电阻率由2.5×108 Ω·cm提高到7.2 ×108 Ω·cm,晶体成分接近ZGP理想化学配比,退火后晶体的光学和电学性能得到显著改善,可用于ZGP-OPO器件制作.     

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.     

溶剂熔区移动法制备Cd0.9Zn0.1Te晶体及性能研究

用溶剂熔区移动法制备了掺In的Cd0.9Zn01Te晶体,晶体生长温度800℃,温度梯度为20℃/cm,生长速度0.4 mm/h.测试了晶体的Te夹杂情况、红外透过率图谱、Ⅰ～Ⅴ特性曲线和PICTS特性,并以1115℃下用VB法生长的掺In的Cd0.9Zn0.1Te晶体做为参照,对比了两者性能.结果表明,溶剂熔区移动法制备的晶体Te夹杂的密度和体积百分比比VB法晶片低,但是Te夹杂的尺寸要比VB法晶体大;溶剂熔区移动法晶体的红外透过率比VB法晶体高;溶剂熔区移动法晶体电阻率比VB法晶体高了一个数量级;PICTS测试发现,溶剂熔区移动法晶体内主要的缺陷密度低于VB法晶体.     

CdSiP2单晶退火研究

以高纯(6N) Cd、Si、P单质为原料,采用双温区气相输运法和改进的垂直布里奇曼法合成生长出等径尺寸为φ17 mm×65 mm的CdSiP2单晶锭,经切割抛光得到CdSiP2晶片.将样品分别置于真空、镉气氛、磷气氛和在同成分粉末包裹中进行了退火试验.采用X射线能量色散谱仪(EDS)和傅里叶红外分光光度计(FTIR)对退火前后的晶片组分及红外透过谱进行了测试分析.结果表明:四种氛围退火前后样品的组分变化不大,原子比接近理想的化学计量比;镉气氛下退火对晶片的红外透过率改善较为显著,在1600 ～ 4500 cm-1范围内的红外透过率由46;～52;提高到51; ～57;,接近CdSiP2晶体红外透过率的理论值.     

溶剂熔区移动法生长In∶Cd0.9Zn0.1Te晶体的性能研究

采用溶剂熔区移动法生长出掺In的Cd0.9Zn0.1Te晶体.测试了晶体轴向Zn含量分布,并对晶体的头部和中部进行了Te夹杂相、红外透过率、I-V特性曲线和PL谱图的对比测试.结果表明:头部晶体的Zn含量、红外透过率和电阻率均大于中部;而头部晶体的Te夹杂尺寸、杂质和缺陷含量均小于中部.     

富Te条件下CdTe晶体中的点缺陷研究

基于缺陷化学理论,考虑到富Te的CdTe晶体中可能存在的点缺陷,建立了在Te气氛下退火时,热力学平衡态晶体中的点缺陷模型,其中包括Cd间隙(Cdi)、Cd空位(VCd)、Te间隙(Tei)和Te反位(TeCd).利用质量作用定律和伪化学平衡方程计算了富Te情况下本征CdTe晶体中的点缺陷浓度和费米能级.计算结果系统的揭示了点缺陷浓度、费米能级、Te压以及退火温度之间的关系,发现只有TeCd浓度足够大时才能对费米能级产生钉扎作用.     

Te溶剂Bridgman法CdMnTe晶体核辐射探测器的制备和表征

碲锰镉(CdMnTe)作为性能优异的室温核辐射探测器材料,可用于环境监测和工业无损检测领域。本文中采用Te溶剂Bridgman法生长In掺杂Cd_0.9Mn_0.1Te晶体,制备成10 mm×10 mm×2 mm大小的室温单平面探测器,研究了该探测器对²⁴¹Am@59.5 keV γ射线源的能谱响应。通过表征红外透过率、电阻率以及探测器能谱响应等参数,综合评定了探测器用CdMnTe晶体的质量、电学和探测器性能。结果表明,晶片的红外透过率均在55%以上,最好可达到60%。采用湿法钝化,100 V偏压下的漏电流由钝化前的9.48 nA降为钝化后的7.90 nA,钝化后的电阻率为2.832×10¹⁰ Ω·cm。在-400 V反向偏压下,CdMnTe探测器对²⁴¹Am@59.5 keV γ射线源的能量分辨率在钝化前后分别为13.53%和12.51%,钝化后的电子迁移率寿命积为1.049×10^-3 cm²/V。研究了探测器的能量分辨率随电压的变化特性,当偏压≤400 V时,探测器的能量分辨率主要由载流子的收集效率决定,而当偏压>400 V时,能量分辨率由漏电流决定。本文研究结果表明,Te溶剂Bridgman法生长的CdMnTe晶体质量较好,电阻率和电子迁移率寿命积满足探测器制备需求。     

氩气退火时间对Fe(Se,Te)薄膜的性能影响研究

作为一种铁基超导薄膜,Fe(Se,Te)薄膜具有晶体结构简单、所包含的元素较少、易于合成的特点,不仅有利于超导机理研究而且有着潜在的技术应用价值。本文通过磁控溅射在温度为320 ℃的CaF₂单晶衬底上制备了Fe(Se,Te)薄膜,并在氩气氛围下进行了退火处理。研究了退火时间对Fe(Se,Te)薄膜的晶体结构、微观形貌、成分组成以及电输运特性的影响。结果表明:Fe(Se,Te)薄膜的结晶性较好,退火有助于消除薄膜样品中的FeSe相,薄膜的晶格常数c对退火不敏感,退火后薄膜晶粒尺寸变大;Fe(Se,Te)薄膜成分与靶材的名义组分存在一定的偏差,退火时间越长,Fe(Se,Te)薄膜表面的颗粒越密集;Fe(Se,Te)薄膜的电阻随温度升高而减小,呈现出半导体特性,退火3 h后电阻明显增大。     

Melt growth and post‐grown annealing of semiinsulating (CdZn)Te by vertical gradient freeze method

We present results of development of CdZnTe semi‐insulating crystals prepared by Vertical Gradient Freeze method in a 4‐zone furnace. We applied the way of growth of the crystal from the top when the first crystallization seed is created on the surface of the melt. The typical height of the crystals is 5 cm. Resistivity and photoconductivity profiles measured along the growth axis by contactless method are compared and their mutual correlation is explained based on a model of relative shift of the Fermi level and the midgap level present in the material. The influence of the Fermi level on electron trapping and recombination is summarized. We present here results of a two‐step annealing method aimed at reduction of Te inclusions while keeping the resistivity high. We employed CdTe:Cl VGF grown samples to eliminate Te inclusions observed in as grown crystals by two‐step post grown annealing in Cd and Te atmosphere and present a model of the processes leading to high resistivity material after annealing.     

生长气氛和速度在金红石(TiO2)单晶体生长中的作用研究

本文研究了生长气氛和生长速度在焰熔法金红石单晶体生长中的作用,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.研究表明:金红石单晶体的生长受炉膛气氛、生长界面温度和生长速度的影响;炉膛气氛决定晶体能否形成,是关键因素;炉膛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前提条件;晶体在退火过程中消除热应力,但更重要的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.在所优化的实验条件下制备的晶体,完整性较好,透过率为70～72;,与商用晶体的透过率基本一致.     

Er3+:NaY(Wo.9Moo.1O4)2晶体的生长及光谱性能

采用提拉法(CZ法),生长出质量良好的Er3+:NaY(W0.9Mo0.1O4)2晶体.通过X射线粉末衍射,红外光谱分析,并与NaY(WO4)2相比较,得到Er3+:NaY(W0.9Mo0.1O4)2晶体的结构与NYW类似,仍为四方晶系的白钨矿结构,I4(1)/α空间群.测定了晶体的实际组成,得到晶体中各元素均按理论值进行掺杂,计算了掺杂离子的分凝系数约为1.15.在光谱性质上,测试了晶体的吸收光谱,及晶体在50～1000cm-1波数范围内的拉曼光谱,并计算了各吸收峰的半峰宽及吸收系数A.     

Crystallization Control of Molten Ba(B0.9Al0.1)2O4 from Supercooled Pendant Drop

Crystallization process of molten Ba(B_0.9Al_0.1)₂O₄ from supercooled pendant drop was investigated on a viewpoint of a supercooling and a solid phase formation. Molten pendant drop was crystallized by a rod touching at an crystallization temperature under an adequate degree of supercooling. Three kinds of rods were used. Each rod was made of Pt, hBN and graphite which had different wettability to the molten drop. There were three kinds of phases on a solid Ba(B_0.9Al_0.1)₂O₄, such as a high temperature crystal phase, a low temperature crystal phase and a glass phase. All phases could be formed by the present method.     

‘Star‐like’ defects in Cd‐annealed CdZnTe crystals—an experimental study of their origin and formation mechanism

We conducted low‐temperature annealing experiments at temperatures slightly above and below the melting point of Te to clarify the effects of the state of Te inclusions (solid or liquid) upon the formation of ‘star‐like’ defects in Cd‐annealed CdZnTe (CZT). We also carried out post‐growth annealing experiments with and without using Cd vapor to clarify the mechanism of formation of such defects. We demonstrated that these ‘star‐like’ defects are due to the reaction between in‐diffused Cd atoms and the molten Te inclusions, but we found no observable ‘one‐to‐one’ correlation between ‘star‐like’ defects and Te inclusions. The non‐uniform distribution of Te inclusions in the CZT matrix could account for this phenomenon since the punching distance of the dislocations depends on the volume fraction of inclusions within the matrix.     

Investigation of Bimetallic Thiocyanates belonging to ABTC Structure Type: ZnCd(SCN)4 and AHg(SCN)4 (A = Zn,Cd, Mn ) as Nonlinear Optical Crystal Materials

Bimetallic thiocyanate complexes crystal materials belonging to ABTC structure type: ZnCd(SCN)₄ and AHg(SCN)₄ (A = Zn, Cd, Mn ) which are potentially useful in second harmonic generation (SHG) have been prepared. Their structural, optical and physicochemical properties are characterized by infrared spectroscopy, X‐ray powder diffraction, vis/UV/NIR spectroscopy, SHG measurements and thermal analysis. The states of crystal growth solutions are discussed in this article. The crystals belong to tetragonal system with the space group I‐4 and exhibit SHG efficiencies over one order of magnitude higher than that of Urea. Their transparency cutoffs lie in the UV region, and they possess good physicochemical stabilities.     

Growth Mechanism in Atomic Layer Epitaxy (I) Re-evaporation of Cd and Te from CdTe(111) Surfaces Monitored by Auger Electron Spectroscopy

The mechanism of atomic layer epitaxy (ALE) of cadmium telluride has been studied. Auger electron spectroscopy is used to measure the isothermal re-evaporation rates of elemental Cd and Te deposits on the (111)A and (111)B surfaces of CdTe substrates. The results include an observation that the sticking coefficients of Cd and Te are smaller than unity at the growth temperatures typical of CdTe ALE. After desorption the substrates are left partially covered: 35% by a Cd overlayer on the (111)B surface and 72% by Te on the (111)A surface. The re-evaporation rates of Cd and Te experience a drastic change near the substrate-deposit interface. These rates appear two orders of magnitude smaller than those of bulk-like amorphous Cd and Te solids. The activation energies for reevaporation of the near-interface layer region are estimated to be: 1.5 eV for Te on the (111)A face, 1.0 eV for Te on (111)B and 0.5 eV for Cd on (111)B. It has also been shown that AES can be used to identify the polarity of the CdTe(111) surfaces. The relative difference in peak-to-peak intensity ratios of Cd MNN to Te MNN for (111)A and (111)B is (11 ± 2)%.