碲锌镉晶体第二相夹杂物特性研究

高质量的碲锌镉单晶是制备碲镉汞红外焦平面器件的理想衬底材料,然而目前碲锌镉材料中的第二相夹杂物严重制约着晶体的质量.根据红外透射形貌的描述和表征,碲锌镉晶体的常见夹杂物被分成了五类,并在此基础上讨论了各自的形成机制,A、B和C类夹杂物与化学配比及其变化密切相关,而D和E类夹杂物与源材料中或者在生长工艺控制过程中氧含量相关.进一步的研究表明大尺寸、高密度的Te夹杂物将会严重降低红外透过率,同时腐蚀坑密集分布在与Cd夹杂对应的六重对称线上,该结果揭示了第二相夹杂物会产生其他缺陷的增殖,但夹杂物引起的应力影响区域是局限的.     

Cd饱和气氛退火对碲锌镉晶体导电类型转变界面的影响

在富Te生长条件下,通过垂直布里奇曼法制备的部分碲锌镉晶体内存在导电类型转变界面。采用富Te液相外延技术在含有导电类型转变界面的碲锌镉衬底上生长碲镉汞薄膜,制成的红外焦平面探测器响应图上存在明显的响应不均匀分界面。碲锌镉晶体的导电类型转变由缺陷类型的不同引起,为消除碲锌镉衬底的导电类型转变界面,提升碲镉汞红外焦平面的成像质量,对含有导电类型转变界面的碲锌镉晶体进行了Cd饱和气氛退火实验,研究了时间和温度等退火条件对晶体导电类型转变界面的影响,探讨了Cd间隙和Cd空位缺陷的形成机制,为晶体生长过程中的Cd空位缺陷抑制提出了解决思路。     

碲锌镉晶体中夹杂问题的实验研究

采用红外透射显微镜检测和研究了热解氮化硼(PBN)坩埚生长碲锌镉晶体(CdZnTe)中的缺陷—夹杂,并对夹杂的影响因素进行了分析。研究发现:不同原料的化学配比、自由空间体积、饱和蒸汽压、晶体生长温场对晶体中夹杂的种类、形状、密度和尺寸都存在着影响,通过一系列工艺的改进可以获得夹杂合格的碲锌镉晶体。     

CdZnTe衬底的退火改性技术研究北大核心CSCD

针对高性能碲镉汞红外探测器对碲锌镉(CdZnTe)衬底质量需求的不断提升,采用高温-真空退火方式,对碲锌镉衬底进行退火改性研究。结果发现:碲锌镉衬底的红外透过率得到明显地改善,在红外波段(2.5~25μm)均达到60%以上;晶片中的第二相夹杂得到极大地改善,可实现无大于1μm的第二相夹杂,即可实现红外显微镜下夹杂不可见;Zn组分分布均匀性得到极大地改善,通过退火分压的调节,可实现衬底中Zn组分可调和Zn值的组分均匀分布,其中Zn组分可控制在0.044~0.051范围内,成分标准偏差可控制在0.001以下,衬底的组分可控和均匀分布为大面阵碲镉汞红外探测器的质量提升奠定了坚实的材料基础。     

Cd1-xZnxTe晶体中由本征缺陷引起的导电类型转变界面研究

在富Te生长条件下,采用垂直布里奇曼法（vertical Bridgman method, VB）生长的部分碲锌镉（Cd_1-xZn_xTe, CZT）晶体内存在导电类型转变界面。为深入探讨碲锌镉晶体导电类型转变界面形成的原因,结合晶体导电类型和红外光谱透过率的测试结果与第一性原理的理论计算进行分析,结果表明,碲锌镉晶体内的导电类型转变界面是晶体生长过程中形成的Cd空位（V_Cd）缺陷与Cd间隙（Cd_i）缺陷导致的。在富Te条件的生长过程中,Cd空位缺陷易于形成,碲锌镉晶体材料中含有大量的Cd空位缺陷,材料的导电型为p型。在晶体生长结束阶段的降温过程中,Cd原子会扩散至碲锌镉晶体中,促进了Cd间隙缺陷的形成,在碲锌镉晶体材料中形成Cd间隙缺陷,导致晶体材料的导电性转变为n型。     

碲锌镉晶体Cd源控制生长技术研究

针对碲锌镉(CdZnTe)晶体中二次相缺陷问题,Cd源控制生长技术是更为有效的缺陷抑制技术。本文结合模拟仿真与实际测温调温,对比了VB法以及VGF法下Cd源处温度的可控性。在实现Cd源处温度控制基础上研究了不同Cd源处温度控制条件对晶体二次相缺陷尺寸及分布的影响。VB法中,Cd源处控制温度快速下降,晶体尾端出现三角形Te夹杂缺陷。VGF法中,在Cd源控制温度达到820～790℃范围内时,虽然晶体头部中心部分二次相缺陷问题改善效果一般,但晶体边缘及尾部二次相缺陷问题能够得到了极大改善。     

碲硒锌镉单晶体的垂直布里奇曼法生长与性能研究

碲锌镉(CdZnTe)是目前最重要的室温半导体核辐射探测器材料。而在CdZnTe晶格中以Se替位部分Te得到碲硒锌镉(CdZnTeSe),将使得晶格中离子键的成分增加,从而提高晶体的硬度,降低Cd空位和Te夹杂物缺陷浓度,提升材料质量。为了获得适宜于核辐射探测器制备的CdZnTeSe晶体,研究了富Te条件下CdZnTeSe晶体的垂直布里奇曼法生长,成功制备出直径为21 mm、长度超过70 mm的Cd_0.9Zn_0.1Te_0.97Se_0.03单晶锭。所得Cd_0.9Zn_0.1Te_0.97Se_0.03晶体的(110)面X射线衍射摇摆半峰宽达到0.104°,而Te夹杂相的尺寸小于5μm,表明晶体具有良好结晶性。Cd_0.9Zn_0.1Te_0.97Se_0.03晶锭尾部的能带隙和红外透过率均低于晶锭的头部和中部,这可归因于Cd_0.9<...     

昆明物理研究所大面积水平推舟液相外延碲镉汞薄膜技术进展

报道了近年来昆明物理研究所在富碲水平推舟液相外延碲镉汞外延薄膜制备技术方面的进展。2019年以来,突破了?120 mm碲锌镉晶体定向生长技术,使碲锌镉衬底沉积相和夹杂相密度≤5×103 cm－2,位错腐蚀坑密度（EPD）≤4.0×104 cm－2,?120 mm（111）晶圆衬底的Zn组份分布极差≤0.36%。基于碲锌镉衬底技术的进步,液相外延碲镉汞薄膜的最大生长尺寸达到了70 mm×75 mm,薄膜位错腐蚀坑密度均值为5×104 cm－2,X射线双晶回摆曲线半峰宽（DCRC-FWHM）≤35 arcsec,部分可控制到25 arcsec以下;50 mm×60 mm尺寸长波碲镉汞薄膜的厚度极差≤±1.25 μm,室温截止波长极差≤±0.1 μm,中波碲镉汞薄膜相应指标分别为≤±1 μm、≤±0.05 μm。材料技术的进展促进了制冷型碲镉汞探测器产能提升和成本的降低,也支撑了高性能长波/甚长波探测器、高工作温度（HOT）探测器以及2048×2048、4096×4096等甚高分辨率高性能探测器的研制。     

碲锌镉晶片退火的显微Raman光谱分析

测量了4块不同退火条件处理碲锌镉晶片的显微Raman光谱,观察到了与碲锌镉材料及材料中Te沉积晶格振动相对应的Raman散射峰,发现了位于327cm^-1／332cm^-1的新峰。通过对碲锌镉晶片进行退火处理,有效的消除了Te沉积,比较碲锌镉晶片退火前后的显微Raman光谱,指出327cm^-1／332cm^-1散射峰只可能由来源于类CdTe或类ZnTe的二级声子散射引起,与碲锌镉材料中的Te沉积无关。     

碲锌镉晶体中微观缺陷分析

碲锌镉晶体(CdZnTe)是一种性能优异的红外焦平面探测器衬底材料,其质量的优劣将直接影响外延层的结构与性能,而晶体中的微观缺陷常常是影响衬底材料质量的主要因素之一。本文采用红外透射显微镜、金相显微镜、X射线形貌仪、扫描电镜、白光干涉仪等仪器系统地检测和研究了碲锌镉晶体中存在的微观缺陷。研究发现碲锌镉晶体样品中主要存在层错、孪晶界和包裹物等微观缺陷,结合晶体缺陷理论详细地分析了碲锌镉晶体中微观缺陷的形成机制。     

Correlation of CdZnTe(211)B substrate surface morphology and HgCdTe(211)B epilayer defects

We present results on the surface morphology and recombination lifetimes of molecular-beam epitaxy (MBE)-grown HgCdTe (211)B epilayers and correlate them with the roughness of the CdZnTe substrate surfaces. The substrate surface quality was monitored by in-situ spectroscopic ellipsometry (SE) and reflection high-energy electron diffraction (RHEED). The SE roughness of the substrate was measured after oxide desorption in the growth chamber. The RHEED patterns collected show a strong correlation with the SE roughness. This proves that SE is a valuable CdZnTe prescreening tool. We also found a correlation between the substrate roughness and the epilayer morphologies. They are characterized by a high density of thin elongated defects, “needle defects,” which appear on most samples regardless of growth conditions. The HgCdTe epilayers grown on these substrates were characterized by temperature-dependent, photoconductive decay-lifetime data. Fits to the data indicate the presence of mid-gap recombination centers, which were not removed by 250°C/24-h annealing under a Hg-rich atmosphere. These centers are believed to originate from bulk defects rather than Hg vacancies. We show that Te annealing and CdTe growth on the CdZnTe substrates smooth the surface and lower substantially the density of needle defects. Additionally, a variety of interfacial layers were also introduced to reduce the defect density and improve the overall quality of the epilayer, even in the presence of less than perfect substrates. Both the perfection of the substrate surface and that of its crystalline structure are essential for the growth of high-quality material. Thus, CdZnTe surface polishing procedures and growth techniques are crucial issues.     

CdZnTe photodiode arrays for medical imaging

In this paper, we report on the design, fabrication, and performance of the first CdZnTe Schottky photodiode arrays for radiation detection. High pressure Bridgman-grown CdZnTe substrates with bulk resistivities in the range 10⁸ to 10¹⁰ ohm-cm were used. CdZnTe Schottky photodiodes were formed with In and Ti/Au contacts. Diode arrays with pixel sizes from 1000 × 1000 (im to 100 × 100 urn were fabricated. The diode’s I-V characteristics exhibited low leakage current and high bulk resistivity; leakage current decreased as diode pixel size was reduced. Response of these detector arrays to high energy photons was uniform and their energy resolution improved with smaller pixel size.     

Recent progress in CdZnTe crystals

CdZnTe crystals were grown by vertical gradient freezing (VGF) method with a Cd reservoir for controlling the Cd pressure under conditions such that the crystals are in equilibrium with a Cd vapor corresponding to the minimum deviation from stoichiometry. The precipitate size became smaller by a post growth annealing method in the VGF furnace after the crystal growth without using wafer annealing. The size became less than 2 μm. Precipitate-free crystals were also grown by controlling the cooling method. In addition, the carrier concentration of p-type CdZnTe crystals was reduced using polycrystals grown in pBN boats. We have found that the carrier concentration of p-type ingots is dependent on Na and Li impurity concentrations.     

Improved morphology and crystalline quality of MBE CdZnTe/Si

We report on continuing efforts to develop a reproducible process for molecular beam epitaxy of CdZnTe on three-inch, (211) Si wafers. Through a systematic study of growth parameters, we have significantly improved the crystalline quality and have reduced the density of typical surface defects. Lower substrate growth temperatures (∼250–280°C) and higher CdZnTe growth rates improved the surface morphology of the epilayers by reducing the density of triangular surface defects. Cyclic thermal annealing was found to reduce the dislocation density. Epilayers were characterized using Nomarski microscopy, scanning electron microscopy, x-ray diffraction, defect-decoration etching, and by their use as substrates for HgCdTe epitaxy.     

Influence of Cd-rich Annealing on Defects in Te-rich CdZnTe Materials

The influence of Cd-rich annealing at temperatures of 440–900 °C on the defect properties of Te-rich CdZnTe materials was studied. Cd-rich annealing at temperatures above the melting point of Te was confirmed to effectively reduce the size of Te-rich inclusions in the materials. However, dislocation multiplication occurred in the regions near Te-rich inclusions. Etch pit clusters were observed on the surfaces of annealed materials etched with Everson etchant. The etch pit clusters were much larger than the as-grown Te-rich inclusions. The dependence of the cluster size on that of the Te-rich inclusions and the annealing conditions was investigated. The density of etch pits in the normal region increased when the annealing temperature exceeded 750 °C. The mechanisms of the evolution of the Te-rich inclusions and the formation of new defects during the Cd-rich annealing are discussed.     

The annealing of Cd1−xZnxTe in CdZn vapors

As-grown CdZnTe usually contains defects, such as twins, subgrain boundaries, dislocations, and Te precipitates. It is always important to anneal CdZnTe slices in Cd vapor to eliminate these defects, especially Te precipitates. The exchange of Zn atoms between the slices and the vapor plays an important role during the annealing process. In this paper, the effects of Zn partial pressure on the properties of the annealed slices are studied carefully by measuring the concentration profiles, the infrared (IR) transmission spectra, and the x-ray rocking curves. It was found that a surface layer with different compositions and possibly different structure from the bulk crystal formed during the annealing of CdZnTe samples in the saturated Zn vapor. The accumulation of excess Te in the surface layer helps to increase the IR permeability of the bulk crystal greatly. To improve the crystallization quality, a lower Zn-pressure annealing should be used following the high Zn-pressure annealing. The diffusion of Zn in the bulk crystal has also been analyzed at the temperatures of 700°C and 500°C. Calculations determined that D_Zn (700°C)=4.02 × 10⁻¹² cm²s⁻¹ and D_Zn (500°C)=1.22 × 10⁻¹³ cm²s⁻¹.     

碲锌镉晶体的X射线衍射形貌与腐蚀形貌

碲锌镉晶体中存在着各种典型晶体缺陷,其缺陷研究一直倍受关注,X射线衍射形貌术是一种非破坏性地研究晶体材料结构完整性、均匀性的有效方法.采用反射式X射线衍射形貌术对碲锌镉衬底的质量进行了研究,并将衬底的X射线衍射形貌与Everson腐蚀形貌进行了对比分析,碲锌镉衬底的X射线衍射形貌主要有六种特征类型,分别对应不同的晶体结构或缺陷,包括均匀结构、镶嵌结构、孪晶、小角晶界、夹杂、表面划伤,对上述特征类型进行了详细的分析.目前,衬底的X射线衍射形貌主要以均匀结构类型为主,划伤和镶嵌结构缺陷基本已消除,存在的晶体缺陷主要以小角晶界为主.通过对比分析碲锌镉衬底和液相外延碲镉汞薄膜的X射线衍射形貌,发现小角晶界等晶体结构缺陷会延伸到外延层上,碲锌镉衬底质量会直接影响碲镉汞外延层的质量,晶体结构完整的衬底是制备高质量碲镉汞外延材料的基础.     

Pseudobinary phase diagram and existence regions for PbS1−xSex

The pseudobinary phase diagram of the PbS_1−xSe_x system has been re-determined by using thermal analysis to measure the liquidus temperatures and electron microprobe analysis of the first-to-freeze portions of Bridgman-grown ingots to establish the solidus points. The minimum in the liquidus occurs at x = 0.73 and 1076° C. The separation between our solidus and liquidus curves is considerably less than Simpson reports. For PbS_1=xSe_x alloys with 0. 35 ≼ x≼ 0.41, the existence region between 300 and 800° C has been determined by means of Hall coefficient measurements at 77K on Bridgman-grown crystals that were either Pb-saturated or chalcogen-saturated by isothermal annealing and then quenched. Both the Pb-rich and chalcogen-rich solidus lines are retrograde, and the existence region is nearly symmetrical about the stoichiometric composition. New data for the retrograde S-rich solidus of PbS have also been obtained. This work was sponsored by the Department of the Air Force.     

HgCdTe液相外延薄膜表面缺陷的控制

研究了HgCdTe液相外延薄膜表面两类宏观缺陷的形成原因.研究表明,大部分表面凹陷点(void)缺陷的形成是由衬底的蜡沾污所引入的,而表面凸起点(hill-like)是由衬底边缘脱落的CdZnTe微颗粒造成的,通过控制外延生长前的衬底处理过程,可以抑制这两类缺陷,从而生长出零(宏观)缺陷密度的优质HgCdTe外延薄膜.     

空间微重力汽相生长CdZnTe的研究进展

微重力条件下汽相生长CdZnTe晶体可以克服浮力对流,实现“无接触”生长,获得厚度均匀、结构完整、纯度高的材料.本文综述了国内外空间汽相生长CdZnTe晶体的研究进展.