碲锌镉晶体合成过程中的放热控制和反应机理研究

碲锌镉(Cadmium Zinc Telluride, CZT)是碲镉汞(Mercury Cadmium Telluride, MCT)红外焦平面器件的重要衬底材料,其合成过程存在强烈的放热现象。因此控制放热是CZT多晶材料合成工艺平稳进行的基本条件。通过改变初始旋转倾角可有效调控合成反应的放热强度和放热速率：大倾角有利于获得缓慢且稳定的工艺过程。基于实验结果和热力学计算分析可知,合成反应经过镉-碲的液-固相反应和液-液相反应两个阶段完成。同时实验结果表明,反应的放热量大小决定了在高温下是否会发生第二次反应。最后对二次反应发生的相关机理进行了分析。     

高温热处理对碲锌镉衬底中Zn组分的影响

随着高性能碲镉汞红外探测器对碲锌镉衬底质量要求的不断提高,研制高质量的碲锌镉衬底材料势在必行。本文采用真空高温热处理温场与源控制的衬底高温热处理工艺,系统地研究了主要热处理参数对碲锌镉衬底中Zn组分的影响,给出了Zn组分控制的热处理经验公式,初步获得了碲锌镉衬底中Zn组分的成分控制和高组分均匀性分布的方法,提高了碲锌镉衬底质量。     

大尺寸碲锌镉基碲镉汞材料分子束外延技术研究

针对高质量、大规模碲镉汞红外焦平面探测器需求的持续增加,本文开展了使用分子束外延方式在50 mm×50 mm(211)B碲锌镉衬底上外延碲镉汞材料技术的研究.通过对碲锌镉衬底改进湿化学腐蚀、碲锌镉衬底预处理、碲锌镉衬底缓冲层生长、碲锌镉基碲镉汞材料工艺开发等方面的研究,开发出了能够稳定获得碲锌镉基碲镉汞材料的工艺.材料...     

碲锌镉衬底的化学机械抛光液研究

作为碲锌镉衬底表面加工的重要工序,化学机械抛光(Chemical Mechanical Polishing, CMP)的加工效果决定了碲锌镉衬底的表面质量和生产效率。抛光液是CMP的关键影响因素之一,直接影响衬底抛光后的表面质量。对碲锌镉衬底CMP工艺使用的抛光液进行了研究,探究了以二氧化硅溶胶和过氧化氢为主体的抛光液体系在不同pH值、不同磨料浓度下对衬底抛光表面质量和去除速率的影响。结果表明,使用改进后的抛光液体系对碲锌镉衬底进行CMP,能够在获得超光滑表面的同时实现高效率加工,为批量化制备高表面质量的碲锌镉衬底奠定了良好基础。     

碲锌镉晶体定向研究

碲锌镉材料是制备高性能碲镉汞红外焦平面探测器不可或缺的衬底材料.液相外延工艺和分子束外延工艺分别需要使用(111)晶面和(211)晶面碲锌镉衬底制备碲镉汞薄膜材料.低偏角、高精度衬底的选取有利于高质量碲镉汞外延层的获得.介绍了孪晶线快速定向法、使用X射线衍射仪(X-Ray Diffractome-ter,XRD)定向法...     

分子束外延用碲锌镉(211)B衬底表面预处理技术

本文主要分析了作为分子束外延碲镉汞的碲锌镉衬底的表面预处理工艺。湿化学处理工艺主要目的是去除衬底表面损伤层,0.5%溴甲醇溶液的腐蚀速率为7 nm/s,但腐蚀的同时会形成表面富Te层和氧化层,氧化层的厚度随溴甲醇的浓度增加而增加;高温热处理工艺主要是消除湿化学腐蚀形成的富Te层和氧化层,340℃的高温处理可去除表面氧化层;也可以直接通过回旋共振等离子体处理衬底表面,形成化学计量比正常的干净表面。     

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.     

CdZnTe中富碲沉积相缺陷引起的液相外延HgCdTe薄膜表面缺陷

为了研究液相外延碲镉汞薄膜表面缺陷形成机制,采用光刻工艺结合化学腐蚀方法在碲锌镉衬底表面实现了网格化,研究了碲锌镉近表面富碲沉积相与外延薄膜表面缺陷的关系.结果表明:衬底近表面富碲沉积相会导致碲镉汞薄膜表面孔洞、类针形凹陷坑缺陷以及三角形凹陷坑聚集区;在液相外延过程中,高温碲镉汞熔液与CdZnTe衬底间的回熔作用可以减少与富碲沉积相相关的表面缺陷,薄膜表面缺陷与衬底表面富碲沉积相的匹配度与回熔深度负相关;回熔过程以及富碲沉积相形态、深度影响HgCdTe薄膜表面缺陷形态和分布.     

碲锌镉晶体表面磨抛方法研究

碲锌镉是一种性能优异的Ⅱ-Ⅵ族化合物半导体材料。随锌含量不同,其禁带宽度可连续调节,是用于制备红外探测器的碲镉汞材料的优良衬底。介绍了多种碲锌镉晶体的磨抛方法,包括手工研磨、机械抛光、化学抛光和机械化学抛光。借助多种表征技术和改良手段,碲锌镉晶体的表面加工取得了显著进步。     

碲锌镉衬底晶面极性对水平液相外延碲镉汞薄膜的影响

研究了碲锌镉衬底（111）晶面的不同极性对水平推舟液相外延生长碲镉汞薄膜的影响。实验结果显示,（111）A面碲锌镉衬底水平液相外延生长碲镉汞薄膜材料组分和厚度均与常规（111）B面碲锌镉衬底碲镉汞薄膜材料相当;碲镉汞母液在采用（111）A面、（111）B面衬底进行液相外延生长的碲镉汞薄膜上接触角分别为（50±2）°和（30±2）°,结合微观模型分析确认碲镉汞母液在碲镉汞薄膜（111）A面存在更大的表面张力;观察并讨论了（111）A面碲镉汞与（111）B面碲镉汞薄膜材料表面微观形貌的差别;实验获得的（111）A面碲镉汞薄膜XRD半峰宽为33.1arcsec。首次报道了（111）晶面选择对母液残留的影响,研究结果表明,采用（111）A面碲锌镉衬底进行碲镉汞水平推舟液相外延生长,能够在不降低晶体质量的情况下,大幅减小薄膜表面母液残留。     

CdZnTe材料的表面钝化新工艺

研究了一种新的钝化CdZnTe(CZT)器件表面的工艺，即先采用KOHKCl溶液对CZT表面进行处理，再用NH4F/H2O2溶液对其进行表面氧化的二步法钝化工艺．并借助俄歇电子能谱（AES）、微电流测试仪等手段对其表面钝化层的质量进行了鉴别，同时与KOH KCl和NH4F/H2O2两种工艺进行了比较．AES能谱分析表明，采用二步法工艺钝化，既可获得化学计量比较好的CZT表面，又可在表面形成一层起保护作用的氧化层．I-V特性曲线显示，两步法钝化后CZT器件的漏电流与KOH KCl和NH4F/H2O2钝化相比都有一定程度的下降．说明文中提出的新工艺在CZT器件制备方面具有良好的应用前景．     

Material properties of large-volume cadmium zinc telluride crystals and their relationship to nuclear detector performance

The material showing the greatest promise today for production of large-volume gamma-ray spectrometers operable at room temperature is cadmium zinc telluride (CZT). Unfortunately, because of deficiencies in the quality of the present material, high-resolution CZT spectrometers have thus far been limited to relatively small dimensions, which makes them inefficient at detecting high photon energies and ineffective for weak radiation signals except in near proximity. To exploit CZT fully, it will be necessary to make substantial improvements in the material quality. Improving the material involves advances in the crystallinity, purity, carrier lifetimes, and control of the electrical compensation mechanism. A more detailed understanding of the underlying material problems limiting the performance of CZT gamma-ray detectors is required; otherwise, problems with supply, delivery times, and unit cost of large-volume (>5 cm³ active volume) CZT spectrometers are expected to continue. A variety of analytical and numerical techniques have been employed to quantify crystallinity, strain, impurities, compositional and stoichiometric variations, bulk and surface defect states, carrier mobilities and lifetimes, electric field distributions, and surface passivation. Data from these measurements were correlated with spatial maps of the gamma-ray and alpha particle spectroscopic response, and feedback on the effectiveness of crystal growth and detector fabrication procedures has been generated. The results of several of these analytical techniques will be presented in this paper.     

Effect of Colloidal Silver on Optical Transmittance Characteristics of Bulk Cadmium Zinc Telluride Crystals

Colloidal silver is observed to affect the transmittance of p-type Cd_1−y Zn _y Te (CZT) single-crystal substrate material at room temperature. The optical transmittance spectra have been analyzed in the near-infrared (NIR) and mid-infrared (MIR) regions. The transmittance characteristics of CZT showed significant reduction in absorption due to split-off valance band transitions in the NIR region and intervalence band absorption in the MIR region upon coating CZT substrates with silver paste. This reduction in absorption has been explained to be due to the compensation of the acceptor defects (native and foreign). Silver atoms incorporated from the silver coating help in compensation of these defects. A similar effect on transmittance characteristics of mercury cadmium telluride (MCT) epilayers grown on CZT substrates after coating silver paste on the CZT substrate side was also observed. An improvement in the transmittance of CZT substrates after the application of silver paste was observed. A similar improvement in transmittance is usually achieved by annealing the substrates in a Cd/Zn atmosphere. The results are explained by considering the formation of neutral complexes of acceptors (cadmium vacancies) and the interstitial silver. This study also points to the important conclusion that silver paste on CZT should be applied with caution for measurement purposes since it diffuses even at room temperature and modifies the optical characteristics.     

Surface passivation of cadmium zinc telluride radiation detectors by potassium hydroxide solution

The spectral resolution of cadmium zinc telluride (CZT) room temperature nuclear radiation detectors is often limited by the presence of conducting surface species that increase the surface leakage current. Surface passivation plays an important role in reducing this surface leakage current and thereby decreasing the noise of the detectors and improving the spectral energy resolution. Chemical etching with a Br-MeOH solution leaves CZT surfaces rich in Te and is considered as one of the primary causes of the increased surface leakage current. Previous studies have shown that hydrogen peroxide (H₂O₂) forms oxides of tellurium on the CZT surface and thus acts as a good passivating agent. In this study we will present results on the use of potassium hydroxide (KOH) as an alternative passivating agent. The KOH aqueous solution leaves a more stoichiometric (evaluated from the trends in the surface Cd:Te ratio) and smoother CZT surface. The passivation effects of KOH solution on the surface of the CZT have been characterized by current-voltage measurements for different KOH concentrations and etching times for both parallel strip electrodes as well as a metal-semiconductor-metal configuration. The surface chemical composition and its morphology were studied by scanning x-ray photoelectron spectroscopy and atomic force microscopy. The comparison and demonstration of improvements in the spectral resolution of the CZT detectors (based on ²⁴¹Am spectra) with and without the KOH treatment are presented.     

激光控制反应合成的实验研究

本文把表面工程领域两种先进技术——燃烧合成涂层技术和激光表面熔覆技术结合起来进行研究,旨在使这两种表面处理技术优势互补,获得一种新的表面处理技术——激光控制反应合成表面熔覆技术。在结合实验的基础上,研究了在铝热自蔓延反应2Al+Fe_2O_3=2Fe+Al_2O_3的反应物中添加合适的稀释剂,使此体系无法自蔓延,再通过激光能量的输入来诱发和控制反应合成,从而实现在钢板表面的激光陶瓷熔覆。     

Laser ablation sampling for induction coupled plasma source quadrupole mass spectrometry of Cd-Zn-Te materials

A method to measure the elemental composition of both major and minor species that is spatially resolved along and below the surface of Cd-Zn-Te (CZT) crystal specimens is described. This method uses laser ablation sampling (LAS) for material introduction into an inductively coupled plasma (ICP) source quadrupole mass spectrometer (QMS) system for subsequent elemental analysis. Mass spectra are acquired at discrete locations on the surface of each CZT specimen, mounted inside a LAS cell. This cell allows argon sweep gas to transport the ablation products into the ICP-QMS for analysis. Since three component movement of the CZT specimen surface relative to the LAS site is possible under computer control, elemental analysis at specific locations on the surface can be obtained. Additional mass spectra are obtained by repetitive LAS at progressively deeper locations beneath the surface at a fixed position, and at difference sites of interest anywhere on the surface of the CZT specimen. These spectra are analyzed to obtain the relative ionic abundances of all detectable isotopes of the major (CZT matrix) and the minor (trace) elements. From these data, the ensemble atom mass concentrations are calculated for each LAS procedure. The relative mass fraction of each element specie within a particular LAS data set is then determined by calculating the ratio of its abundance to the whole ensemble mass in that sample.     

碲锌镉籽晶定向熔接技术研究

应用CdZnTe晶体作为衬底材料时,其晶向非常关键。CdZnTe晶体籽晶引晶定向生长技术能够有效提高晶体利用率。但是,受碲锌镉晶体生长方法限制,CdZnTe籽晶引晶技术成功率并不高。本文即通过一系列实验研究了籽晶熔接过程升温方式以及籽晶晶向对碲锌镉籽晶熔接成功率的影响,并确定了升温方式是籽晶熔接的关键工艺所在。后续籽晶引晶生长晶向能否持续与籽晶选择晶向有关。通过显著提升初始熔体过热度可以促进<111>籽晶引晶晶向的保持。     

Analysis of CZT crystals and detectors grown in russia and the ukraine by high-pressure bridgman methods

Sandia National Laboratories (SNL) is leading an effort to evaluate vertical high pressure Bridgman (VHPB) Cd_1−xZn_xTe (CZT) crystals grown in the former Soviet Union (FSU) (Ukraine and Russia), in order to study the parameters limiting the crystal quality and the radiation detector performance. The stoichiometry of the CZT crystals, with 0.04<x<0.25, has been determined by methods such as proton-induced x-ray emission (PIXE), x-ray diffraction (XRD), microprobe analysis and laser ablation ICP mass spectroscopy (LA-ICP/MS). Other methods such as triaxial double crystal x-ray diffraction (TADXRD), infrared transmission spectroscopy (IR), atomic force microscopy (AFM), thermoelectric emission spectroscopy (TEES) and laser induced transient charge technique (TCT) were also used to evaluate the material properties. We have measured the zinc distribution in a CZT ingot along the axial direction and also its homogeneity. The (Cd+Zn)/Te average ratio measured on the Ukraine crystals was 1.2, compared to the ratio of 0.9–1.06 on the Russian ingots. The IR transmission showed highly decorated grain boundaries with precipitates and hollow bubbles. Microprobe elemental analysis and LA-ICP/MS showed carbon precipitates in the CZT bulk and carbon deposits along grain boundaries. The higher concentration of impurities and the imperfect crystallinity lead to shorter electron and hole lifetimes in the range of 0.5–2 and 0.1 μs, respectively, compared to 3–20 and 1–7 μs measured on U.S. spectrometer grade CZT detectors. These results are consistent with the lower resistivity and worse crystalline perfection of these crystals, compared to U.S.-grown CZT. However, recently grown CZT from FSU exhibited better detector performance and good response to alpha particles.