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...     

碲锌镉衬底上中长双色红外碲镉汞分子束外延生长研究

报道了使用分子束外延(Molecular beam epitaxy,MBE)技术,在(211)B碲镉汞(CdZnTe,CZT)衬底上生长中长波双色碲镉汞(HgCdTe,MCT)薄膜材料,生长温度为180℃,研究了双色碲镉汞薄膜材料衬底脱氧技术、分子束外延薄膜生长温度与缓冲层生长等关键技术,实现了中长波双色碲镉汞薄膜生长,外延薄膜采用相差显微镜、扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)、二次离子质谱仪(SIMS)及X射线衍射仪(XRD)对薄膜的表面缺陷、厚度、组分及其均匀性、薄膜纵向组分以及晶体质量进行了表征,表面缺陷数量低于600 cm~(-2),组分(300 K测试)和厚度均匀性分别为(35)x≤0.001、(35)d≤0.9μm,X-Ray双晶衍射摇摆曲线FWHM=65 arcsec,得到了质量较高的中长波双色碲镉汞薄膜材料。     

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...     

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.     

分子束外延用碲锌镉(211)B衬底湿化学预处理技术研究

主要分析了不同溴甲醇溶液腐蚀方法对分子束外延用碲锌镉(211)B衬底表面粗糙度及反射式高能电子衍射(RHEED)图样的影响。实验发现化学抛光后未使用溴甲醇腐蚀的CZT(211)B衬底虽然表面粗糙度较小(小于1.0 nm),但表面RHEED衍射图样无任何衍射点或者条纹;采用0.05%溴体积比的溴甲醇溶液腐蚀CZT(211)B衬底时,即使腐蚀极短的时间,衬底表面粗糙度也达到2.0 nm以上,且表面存在高密度的柱状物,衬底表面RHEED图样呈圆点状或条纹较粗且存在亮点;采用0.01%溴体积比的溴甲醇溶液腐蚀CZT(211)B衬底,表面粗糙度可控制在1.0 nm左右,同时RHEED图样为特征的CZT(211)B晶面短条纹衍射图样,条纹清晰,同时多片衬底重复实验结果一致。同时在其上分子束外延的未优化的中波碲镉汞材料半峰宽为(49.1±5.9)arcsec,组分为0.3083±0.0003,厚度为6.54±0.019 μm。     

软脆碲锌镉衬底的新型化学抛光技术研究

碲锌镉(CdZnTe)是液相外延碲镉汞(HgCdTe)薄膜的最佳衬底材料。获得高质量的CdZnTe衬底表面对于提升红外探测器的性能有着十分重大的意义。针对CdZnTe表面加工技术进行了研究,开发出一种新的化学抛光技术,使得抛光后的CdZnTe表面粗糙度Ra可达0.3 nm。     

中国电科11所碲镉汞薄膜材料制备技术进展

碲镉汞材料具有响应速度快、量子效率高、带隙连续可调等优点,广泛应用于红外探测领域,本文报道了近年来中国电科11所在碲镉汞薄膜材料制备方面的技术进展。在碲锌镉衬底材料制备方面,已突破135mm碲锌镉晶体生长技术,碲锌镉衬底平均位错腐蚀坑密度(EPD) <1×104cm-2,具备了80mm×80mm规格碲锌镉衬底的批量生产能力。在液相外延碲镉汞薄膜制备方面,富碲水平液相外延碲镉汞薄膜平均位错腐蚀坑密度EPD<4×104cm-2,具备80mm×80mm规格碲镉汞薄膜的制备能力;富汞垂直液相外延实现高质量双层异质结碲镉汞薄膜材料批量化制备,该种材料的半峰宽(FWHM)控制在(20～40)arcsec范围内,碲镉汞薄膜厚度极差≤±06μm。在分子束外延碲镉汞薄膜方面,实现了6 in硅基碲镉汞材料制备,组分标准偏差≤00015,表面宏观缺陷密度≤100cm-2;碲锌镉基碲镉汞材料已具备50mm×50mm制备能力,组分标准偏差为0002,厚度标准偏差为0047μm。从探测器验证结果来看,基于富碲水平液相外延碲镉汞薄膜实现了1 k×1 k、2 k×2 k等规格红外焦平面探测器的工程化制备;采用双层异质结碲镉汞薄膜实现了高温工作、长波及甚长波探测器的制备;使用分子束外延制备的碲镉汞薄膜实现了27 k×27 k、54 k×54 k、8 k×8 k等规格红外焦平面探测器研制,在宇航领域有巨大的应用潜力。     

碲镉汞材料提纯研究

杂质是影响碲镉汞器件性能的重要因素之一。对于碲锌镉衬底晶体和窄禁带碲镉汞材料来说,杂质的影响更加显著。主要论述了碲镉汞材料中常见的杂质类型以及杂质在材料中的作用,并分析了影响器件性能的主要杂质。采用辉光放电质谱法(Glow Discharge Mass Spectrometry, GDMS)测试了材料中的杂质含量,同时通过改进的区熔工艺降低了碲锌镉衬底及液相外延生长的碲镉汞薄膜材料中的杂质含量,提高了碲镉汞薄膜的电学性能,从而满足高性能碲镉汞红外探测器的制备要求。     

3英寸Si基碲镉汞分子束外延工艺研究

随着红外焦平面阵列规模的扩大,由于尺寸和成本的限制,传统晶格匹配的碲锌镉衬底逐渐成为碲镉汞红外焦平面探测器发展的瓶颈,大尺寸、低成本硅基碲镉汞材料应运而生。本文采用分子束外延工艺生长获得了3 in Si基中波碲镉汞薄膜材料,通过采用金相显微镜、傅里叶红外光谱仪、双晶X射线衍射仪、湿化学腐蚀位错密度(EPD)法、Hall测试系统等检测手段对Si基中波碲镉汞分子束外延薄膜材料进行表面、光学、结构和电学性能表征,并采用标准平面器件工艺制备中波640×512焦平面探测阵列进行材料验证,结果表明该材料性能与国际先进水平相当。     

液相外延碲镉汞贯穿型缺陷研究

液相外延碲镉汞材料的贯穿型缺陷会在后续器件制备中导致多个盲元的形成。采用共聚焦显微镜对该类缺陷的深度进行了表征,并对缺陷底部的成分进行了测试。使用聚焦离子束(Focused Ion Beam, FIB)将缺陷挖开后对其进行观察。对于贯穿型缺陷较多的碲锌镉衬底外延生长碲镉汞薄膜,统计后发现碲镉汞表面的贯穿型缺陷与衬底缺陷存在一定的对应关系,因此推测液相外延贯穿型缺陷起源于碲锌镉衬底缺陷。     

MBE Growth of HgCdTe on Large-Area Si and CdZnTe Wafers for SWIR,MWIR and LWIR Detection

Molecular beam epitaxy (MBE) growth of HgCdTe on large-size Si (211) and CdZnTe (211)B substrates is critical to meet the demands of extremely uniform and highly functional third-generation infrared (IR) focal-panel arrays (FPAs). We have described here the importance of wafer maps of HgCdTe thickness, composition, and the macrodefects across the wafer not only to qualify material properties against design specifications but also to diagnose and classify the MBE-growth-related issues on large-area wafers. The paper presents HgCdTe growth with exceptionally uniform composition and thickness and record low macrodefect density on large Si wafers up to 6-in in diameter for the detection of short-wave (SW), mid-wave (MW), and long-wave (LW) IR radiation. We have also proposed a cost-effective approach to use the growth of HgCdTe on low-cost Si substrates to isolate the growth- and substrate-related problems that one occasionally comes across with the CdZnTe substrates and tune the growth parameters such as growth rate, cutoff wavelength (λ _cutoff) and doping parameters before proceeding with the growth on costly large-area CdZnTe substrates. In this way, we demonstrated HgCdTe growth on large CdZnTe substrates of size 7 cm × 7 cm with excellent uniformity and low macrodefect density. Received December 7, 2007; accepted February 25, 2008     

Recent Progress in MBE Growth of CdTe and HgCdTe on (211)B GaAs Substrates

Alternate substrates for molecular beam epitaxy growth of HgCdTe including Si, Ge, and GaAs have been under development for more than a decade. MBE growth of HgCdTe on GaAs substrates was pioneered by Teledyne Imaging Sensors (TIS) in the 1980s. However, recent improvements in the layer crystal quality including improvements in both the CdTe buffer layer and the HgCdTe layer growth have resulted in GaAs emerging as a strong candidate for replacement of bulk CdZnTe substrates for certain infrared imaging applications. In this paper the current state of the art in CdTe and HgCdTe MBE growth on (211)B GaAs and (211) Si at TIS is reviewed. Recent improvements in the CdTe buffer layer quality (double crystal rocking curve full-width at half-maximum?≈?30?arcsec) with HgCdTe dislocation densities of ≤10⁶?cm^?2 are discussed and comparisons are made with historical HgCdTe on bulk CdZnTe and alternate substrate data at TIS. Material properties including the HgCdTe majority carrier mobility and dislocation density are presented as a function of the CdTe buffer layer quality.     

Strain Determination in Quasi-Lattice-Matched LWIR HgCdTe/CdZnTe Layers

We take advantage of the zinc distribution of (211)B CdZnTe substrates to probe the lattice-mismatch-induced stress in long-wave infrared HgCdTe layers grown by molecular beam epitaxy. High-resolution x-ray diffraction is used to accurately determine the strain-free lattice parameters of both CdZnTe and HgCdTe, together with the in-plane components of the stress tensor. By using several wafers, the stress evolution is derived over a broad range of lattice mismatch. In particular, stress relaxation is evidenced for mismatch greater than 0.02% and 0.04% for tensile and compressively strained HgCdTe, respectively. In-plane strain anisotropy, expected for the (211) orientation, is only evidenced for the compressive configuration. Strain relaxation is correlated with substrate curvature and rocking-curve peak broadening, providing indirect evidence for plastic relaxation.     

Si/CdTe复合衬底HgCdTe液相外延材料的生长与性能分析

通过改进推舟液相外延技术,成功地在(211)晶向Si/CdTe复合衬底上进行了HgCdTe液相外延生长,获得了表面光亮的HgCdTe外延薄膜.测试结果表明,(211)Si/CdTe复合衬底液相外延HgCdTe材料组分及厚度的均匀性与常规(111)CdZnTe衬底HgCdTe外延材料相当;位错腐蚀坑平均密度为(5～8)×105 cm-2,比相同衬底上分子束外延材料的平均位错密度要低一个数量级;晶体的双晶半峰宽达到70″左右.研究结果表明,在发展需要低位错密度的大面积长波HgCdTe外延材料制备技术方面,Si/CdTe复合衬底HgCdTe液相外延技术可发挥重要的作用.     

碲锌镉缓冲层液相外延技术的研究

文章报道了采用液相外延方法，在碲锌镉衬底上进行碲锌镉薄膜缓冲层生长的情况，并且采用X光双晶衍射仪、X光形貌仪、红外傅里叶光谱仪、二次离子质谱仪等手段对碲锌镉薄膜进行了表征，碲锌镉薄膜具有较好地组分及均匀性，晶体结构质量也较好。采用碲锌镉缓冲结构生长了碲镉汞液相外延片，其碲锌镉与碲镉汞薄膜界面附近的杂质得到了有效的控制。     

碲锌镉缓冲层液相外延技术的研究

文章报道了采用液相外延方法，在碲锌镉衬底上进行碲锌镉薄膜缓冲层生长的情况，并且采用X光双晶衍射仪、X光形貌仪、红外傅里叶光谱仪、二次离子质谱仪等手段对碲锌镉薄膜进行了表征，碲锌镉薄膜具有较好地组分及均匀性，晶体结构质量也较好。采用碲锌镉缓冲结构生长了碲镉汞液相外延片，其碲锌镉与碲镉汞薄膜界面附近的杂质得到了有效的控制。     

异质衬底外延碲镉汞薄膜位错抑制技术进展

分子束外延碲镉汞技术是制备第三代红外焦平面探测器的重要手段,基于异质衬底的碲镉汞材料具有尺寸大、成本低、与常规半导体设备兼容等优点,是目前低成本高性能红外探测器发展中的研究重点。对异质衬底上碲镉汞薄膜位错密度随厚度的变化规律进行了建模计算,结果显示ρ~1/h模型与实验结果吻合度好,异质衬底上原生碲镉汞薄膜受位错反应半径制约,其位错密度无法降低至5×10 6 cm-2以下,难以满足长波、甚长波器件的应用需求。为了有效降低异质外延的碲镉汞材料位错密度,近年来出现了循环退火、位错阻挡和台面位错吸除等位错抑制技术,本文介绍了各技术的原理及进展,分析了后续发展趋势及重点。循环退火和位错阻挡技术突破难度大,发展潜力小,难以将碲镉汞位错密度控制在5×105 cm-2以内。台面位错吸除技术目前已经显示出了巨大的发展潜力和价值,后续与芯片工艺融合后,有望大幅促进低成本长波、中长波、甚长波器件的发展。     

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.