原位退火对碲锌镉晶体第二相夹杂缺陷的影响

采用传统布里奇曼法生长碲锌镉晶体,在配料过程中添加适当过量的Cd,并在晶体生长结束阶段的降温过程中加入晶锭原位退火工艺,晶体的第二相夹杂缺陷得到了有效抑制。根据晶体第二相夹杂缺陷的形成机理,结合热扩散理论和碲锌镉晶体的P-T相图,研究了退火温度对晶体第二相夹杂缺陷密度和粒度（尺寸）的影响,获得了抑制碲锌镉晶体第二相夹杂缺陷的退火条件。利用优化的退火条件制备碲锌镉晶体,晶体第二相夹杂缺陷的尺寸小于10 μm,密度小于250 cm－2。     

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。     

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.     

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。     

PBN坩埚生长碲锌镉单晶的性能与缺陷研究

采用垂直布里奇曼法,利用热解氮化硼(PBN)坩埚生长碲锌镉单晶(CdZnTe),并对晶体进行定向、切割与磨抛制成(111)面碲锌镉晶片。采用傅里叶红外透过光谱仪、红外透射显微镜、金相显微镜、X射线形貌仪、X射线衍射仪和X射线双晶衍射仪等仪器系统地检测和研究了碲锌镉晶体的性能与缺陷。研究发现:相比于石英坩埚,采用PBN坩埚生长的碲锌镉晶体单晶率和出片率均大幅增加,孪晶、小角晶界和位错密度明显减少。     

长波碲镉汞薄膜外延用碲锌镉衬底筛选方法研究

主要报道了用于提高液相外延(Liquid Phase Epitaxy, LPE)长波碲镉汞薄膜质量的碲锌镉衬底筛选方法研究。通过对碲锌镉衬底的锌组分、红外透过率、沉淀/夹杂、位错密度、X射线形貌像和X射线衍射半峰宽等参数进行全面测试以及对外延后碲镉汞薄膜的X射线形貌像和X射线衍射半峰宽进行测试评估,发现目前X射线形貌像和锌组分是影响LPE长波碲镉汞薄膜用碲锌镉衬底的重要参数。结果表明,锌组分处于4.2%～4.8%之间、形貌像衍射强度高且均匀性好是长波碲镉汞薄膜外延用衬底的理想选择。     

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。     

碲锌镉晶体常用腐蚀剂的坑形特性研究

大面积、高质量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，而腐蚀法是常用的揭示碲锌镉晶体缺陷和评价晶体质量的方法之一。对碲锌镉晶体常用的Nakagawa、Everson、EAg1和EAg2四种腐蚀剂在碲锌镉材料（111）晶面上的腐蚀坑坑形进行了研究，结果发现，EAg2腐蚀剂在（111）B面上的腐蚀坑为平底坑，Everson腐蚀剂在 (111)B面上产生的腐蚀坑包括平底坑和带有不同倾斜方向坑底的三角锥形坑，进一步的研究还表明，三角锥形坑并未沿着坑底的倾斜方向向下延伸。实验中也首次观察到了EAg腐蚀剂的黑白平底坑。对常用腐蚀剂的坑形特性研究，将有助于更好地利用腐蚀剂开展碲锌镉材料缺陷研究和晶体质量评价工作。     

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.     

X射线衍射形貌术在碲锌镉晶体中的应用

碲锌镉晶体中存在着各种典型晶体缺陷,X射线衍射形貌术是一种非破坏性地整体研究晶体材料结构完整性、均匀性的有效方法。本文将反射式X射线衍射形貌术应用于碲锌镉晶体质量的评价,研究了入射线狭缝宽度、积分时间、扫描步长等测试参数以及样品表面加工状态对X射线衍射形貌的影响。结果表明入射线狭缝宽度对碲锌镉晶体的X射线衍射成像及晶体质量筛选应用影响很大,积分时间、样品扫描步长等测试参数的选择与入射线狭缝宽度密切相关。     

Reduction of CdZnTe substrate defects and relation to epitaxial HgCdTe quality

We have conducted annealing experiments on CdZnTe wafers to restore stoichiometry, eliminate or reduce second-phase (Cd or Te) inclusions, and investigate effects on the quality of epitaxial HgCdTe grown on the thermally treated substrates. Two categories of second phase features were revealed in these materials. Category 1 has a star-like shape with sixfold symmetry (as seen by infrared transmission microscopy) and a central core consisting of cadmium. These stars were observed only in the more stoichiometric materials (having good infrared transmission characteristics). Category 2 consists of triangular, hexagonal, and irregular shaped tellurium inclusions which are present in the off-stoichiometry materials (which exhibit strong IR absorption). Substrates were annealed at temperatures ranging from 500 to 700°C for one to seven days, in vapor derived from elemental Cd or Cd_1-xZn_x alloy (x = 0.005). These anneals were able to eliminate the excess IR absorption and decrease the apparent sizes of both categories of second-phase features. It was found that pinhole-like morphological defects on the surface of a HgCdTe layer grown by liquid phase epitaxy can be caused by Cd and Te inclusions located within the CdZnTe substrate near the interface. Additionally, measurement and spatial mapping of copper concentration by sputter initiated resonance ionization spectroscopy showed 10 to 100 times higher Cu concentration in the inclusions than in the surrounding matrix areas.     

磁光—光致发光分析CdZnTe单晶带边浅杂质能级

通过对Bridgeman方法生长的CdZnTe单晶样品进行光致发光(Photoluminescence,PL)光谱测量,发现CdZnTe样品表面Te沉淀物的存在明显影响能量低于1.5 eV的深能级发光过程.进一步对CdZnTe晶锭的不同位置取样进行低温变磁场光致发光光谱测试,获得高分辨光谱信息.拟合分析结果表明:(1)在不含Te沉淀物的CdZnTe样品内部存在应力分布,并因此导致轻、重空穴带分裂;(2)1.57 eV发光特征源于浅施主杂质与价带间的复合过程.     

室温核辐射CdZnTe像素探测器的研制

采用布里奇曼法生长的CdZnTe(CZT)单晶,制成室温核辐射像素探测器.首先通过红外透过显微(IRTM)成像、电阻率测量以及单元探测器能谱响应测试等手段,综合评定了探测器用CZT晶体的质量,结果表明,晶片富Te相密度为28.43 mm-2且尺寸分布较均匀,电阻率为1010 Ω·cm;电子迁移率寿命积为1.07×10-...     

Development of the high-pressure electro-dynamic gradient crystal-growth technology for semi-insulating CdZnTe growth for radiation detector applications

The high-pressure electro-dynamic gradient (HP-EDG) crystal-growth technology has been recently developed and introduced at eV PRODUCTS to grow large-volume, semi-insulating (SI) CdZnTe single crystals for room-temperature x-ray and gamma-ray detector applications. The new HP growth technology significantly improves the downstream CdZnTe device-fabrication yield compared to earlier versions of the HP crystal-growth technology because of the improved structural and charge-transport properties of the CdZnTe ingots. The new state-of-the-art, HP-EDG crystal-growth systems offer exceptional flexibility and thermal and mechanical stability and allow the growth of high-purity CdZnTe ingots. The flexibility of the multi-zone heater system allows the dynamic control of heat flow to optimize the growth-interface shape during crystallization. This flexibility combined with an advanced control system, improved system diagnostics, and realistic heat-transport modeling provides an excellent platform for continuing process development. Initial results on large-diameter (140 mm), SI Cd_1−xZn_xTe (x=0.1) ingots grown in low temperature gradients with the HP-EDG technique show reduced defect density and complete elimination of ingot cracking. The increased single-crystal yield combined with the improved charge transport allows the fabrication of large-volume, high-sensitivity, high energy-resolution detector devices at increased yield. The CdZnTe ingots grown to date produced large-volume crystals (≥1cm³) with electron mobility-lifetime product (μτ_e) in the (3–7) × 10⁻³ cm²/V range. The lower-than-desired charge-transport uniformity of the HP-EDG CdZnTe ingots is associated with the high density of Te inclusions formed in the ingots during crystallization. The latest process-development efforts show a reduction in the Te-inclusion density, an increase of the charge-transport uniformity, and improved energy resolution of the large-volume detectors fabricated from these crystals.     

Direct growth of CdZnTe/Si substrates for large-area HgCdTe infrared focal plane arrays

Direct epitaxial growth of high-quality 100lCdZnTe on 3 inch diameter vicinal {100}Si substrates has been achieved using molecular beam epitaxy (MBE); a ZnTe initial layer was used to maintain the {100} Si substrate orientation. The properties of these substrates and associated HgCdTe layers grown by liquid phase epitaxy (LPE) and subsequently processed long wavelength infrared (LWIR) detectors were compared directly with our related efforts using CdZnTe/ GaAs/Si substrates grown by metalorganic chemical vapor deposition (MOCVD). The MBE-grown CdZnTe layers are highly specular and have both excellent thickness and compositional uniformity. The x-ray full-width at half-maximum (FWHM) of the MBE-grown CdZnTe/Si increases with composition, which is a characteristic of CdZnTe grown by vapor phase epitaxy, and is essentially equivalent to our results obtained on CdZnTe/GaAs/Si. As we have previously observed, the x-ray FWHM of LPE-grown HgCdTe decreases, particularly for CdZnTe compositions near the lattice matching condition to HgCdTe; so far the best value we have achieved is 54 arc-s. Using these MBE-grown substrates, we have fabricated the first high-performance LWIR HgCdTe detectors and 256 x 256 arrays using substrates consisting of CdZnTe grown directly on Si without the use of an intermediate GaAs buffer layer. We find first that there is no significant difference between arrays fabricated on either CdZnTe/Si or CdZnTe/GaAs/Si and second that the results on these Si-based substrates are comparable with results on bulk CdZnTe substrates at 78K. Further improvements in detector performance on Si-based substrates require a decrease in the dislocation density.     

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.     

Cooling process optimization to control Te inclusions for improving CdZnTe detector performance

Investigation of Te inclusion distribution in CdZnTe crystals treated by the cooling process at different rates indicated that cool slowly at 10–20 K/h caused the emergence of lower concentration but larger size Te inclusions, with a high level total volume fraction, decreasing the IR transmittance. When cooled fast, the dimension of Te inclusions reduced and the concentration increased, even the faster cooling rate, the higher the concentration; moreover the IR transmittance improved. The measurement of energy spectrum demonstrated that Te inclusions of large size or high concentration induced by slow or too fast cooling rate respectively degenerate spectroscopy performance. Cooling at 40–50 K/h presented an optimized process, which retained a certain amount but small size Te inclusions and kept a low total volume fraction, expressing better energy resolution.     

CZT晶体用化学机械抛光液的制备及其性能研究

化学机械抛光工艺是碲锌镉(Cadmium Zinc Telluride,CZT)晶体表面处理的关键技术之一.其中,化学机械抛光液是影响晶片表面质量的重要因素.目前用于CZT晶片的抛光液主要是依靠进口的碱性抛光液,这严重制约了我国CZT晶体研究的发展.采用硅溶胶和次氯酸钠(NaClO)溶液作为主要原料,制备了碱性化学机械抛光液.然后采用该抛光液对CZT晶片表面进行了化学机械抛光,并对抛光表面进行了表征.实验结果表明,抛光后晶片表面的粗糙度小于2 nm,因此采用硅溶胶-次氯酸钠碱性抛光液可制备出高质量的CZT抛光表面.     

Electron microscopy of surface-crater defects on HgCdTe/CdZnTe(211)B epilayers grown by molecular-beam epitaxy

Surface-void defects observed in Hg_1−xCd_xTe (x ∼ 0.2–0.4) alloys grown by molecular-beam epitaxy (MBE) have been investigated using scanning and high-resolution transmission-electron microscopy (HRTEM) as well as atomic force microscopy (AFM). These surface craters, which have been attributed to Hg-deficient growth conditions, were found to originate primarily within the HgCdTe epilayer, rather than at the CdZnTe substrate, and they were associated with the local development of polycrystalline morphology. High-resolution observations established the occurrence of finely spaced HgCdTe/Te intergrowths with semicoherent and incoherent grain boundaries, as well as small HgCdTe inclusions embedded within the Te grains. This study is the first time that high-resolution electron microscopy has been used to investigate this type of defect.