Evaluation of Zn uniformity in CdZnTe substrates

The radial uniformity of Zn concentration in 4 in. CdZnTe crystals was improved by keeping uniform temperature distribution in the VGF furnace. The maximum temperature difference at the outside of crucible in radial direction was reduced to less than 1. The size of voids observed outside of the crystals became small and the distribution has become well-uniformed. To evaluate the Zn uniformity, a new NIR (Near Infrared) instrument was developed using the diode array type spectrometer. The NIR spectra were analyzed by C.D. Maxey et al.’s method. The Zn concentration in 4 in. CdZnTe substrates grown by modified furnace was more uniform than that of the conventional substrates.     

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。     

高温退火处理提高半绝缘VGF-GaAs单晶的电学性能

垂直梯度凝固法(VGF)生长的低位错半绝缘（SI) GaAs单晶存在电阻率和迁移率低、电学补偿度小、均匀性差等问题. 在3种不同温度条件下,对VGF-SI-GaAs晶片进行了加As压的闭管退火处理. 结果表明,经过1160℃/12h的高温退火处理后,VGF-SI-GaAs单晶的电阻率、迁移率和均匀性均得到了显著提高. 利用Hall、热激电流谱（TSC) 、红外吸收法分别测试分析了原生和退火VGF-SI-GaAs单晶样品的电学性质、深能级缺陷、EL2浓度和C浓度,并与常规液封直拉法（LEC) SI-GaAs单晶样品进行了比较. 原生VGF-SI-GaAs单晶中的EL2浓度明显低于LEC-SI-GaAs单晶,经过退火处理后其EL2浓度显著增加,电学补偿增强,而且能级较浅的一些缺陷的浓度降低,因而有效提高了其电学性能.     

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。     

X-ray Diffraction Imaging of Improved Bulk-Grown CdZnTe(211) and Its Comparison with Epitaxially Grown CdTe Buffer Layers on Si and Ge Substrates

Large-area high-quality Hg_1–x Cd _x Te sensing layers for infrared imaging in the 8 μm to 12 μm spectral region are typically grown on bulk Cd_1–x Zn _x Te substrates. Alternatively, epitaxial CdTe grown on Si or Ge has been used as a buffer layer for high-quality epitaxial HgCdTe growth. In this paper, x-ray topographs and rocking-curve full-width at half-maximum (FWHM) data will be presented for recent high-quality bulk CdZnTe grown by the vertical gradient freeze (VGF) method, previous bulk CdZnTe grown by the vertical Bridgman technique, epitaxial CdTe buffer layers on Si and Ge, and a HgCdTe layer epitaxially grown on bulk VGF CdZnTe.     

The oscillations in ESR spectra of Hg0.76Cd0.24Te implanted by Ag+ at the X and Q-bands

The objects of the investigation were uniformly Ag+ doped Hg0.76Cd0.24Te mercury chalcogenide monocrystals obtained by ion implantation with subsequent thermal annealing over 20 days.After implantation and annealing the conductivity was inverted from n-type with carrier concentration of 1016 cm-3 to p-type with carrier concentration of ≈ 3.9 × 1015 cm-3.The investigations of microwave absorption derivative (Dp/Dh) showed the existence of strong oscillations in the magnetic field for Ag:Hg0.76Cd0.24Te in the temperature range 4.2-12 K.The concentration and effective mass of charge carrier were determined from oscillation period and temperature dependency of oscillation amplitude.We suppose that this phenomenon is similar to the de Haas-van Alphen effect in weakly correlated electron system with imperfect nesting vector.     

Uniformity and reproducibility studies of low-pressure-grown Cd<Subscript>0.90</Subscript>Zn<Subscript>0.10</Subscript>Te crystalline materials for radiation detectors

A large number of room-temperature detectors have been produced from CdZnTe crystals grown with 10% Zn and 1.5% excess tellurium by the low-pressure, vertical-Bridgman technique. Radiation spectra obtained by these crystals using a ²⁴¹Am source reveal the characteristic 59.5-keV line as well as the six low-energy peaks, which include the Cd and Te escape peaks. Similarly, ⁵⁷Co spectra obtained also show a very well-defined 122-keV peak with a 3:1 peak-to-valley ratio. Seven CdZnTe crystals have been grown for reproducibility studies. Four of these crystals have resistivities over 1E9 Ω-cm. Considering that the indiumdoping level is on the order of 2E15 cm⁻³, the reproducibility is excellent. The theoretical basis of the high-resistivity phenomenon in CdZnTe is discussed in reference to a previous paper. The uniformity of these 6-in.-long CdZnTe crystals is studied, and various measurements are carried out, both laterally and vertically, along the boule. It is determined that, in general, roughly a 3.5-in. section near the middle of the 6-in. boule has sufficient resistivity for producing radiation detectors. This nonuniformity along the vertical direction is caused mostly by the composition change of Cd, Zn, Te, and In-doping level in the growth melt caused by differences in the segregation coefficients of these elements. Although, variations in resistivity are seen across some of the wafer slices, most show very good uniformity with high breakdown voltage. Some of the variations are attributed to the different grains within the boule. Similar results are seen in the measured radiation spectra obtain on 4 mm × 4 mm × 2 mm samples from different locations across the wafer, where some samples show well-resolved secondary peaks, while others display only the primary spectral lines.     

Control of Ga doping level in β-FeSi2 using Sn–Ga solvent

We have grown n- and p-type β-FeSi₂ single crystals by the temperature gradient solution growth method using Sn–Ga solvent. The conduction type and the carrier density of the crystals were controlled by the Ga composition in the Sn–Ga solvent. The conduction type was changed from n- to p-type between the Ga composition of 10.2 and 18.5 at% in the solvent. Depending on the Ga composition in the solvent, the carrier density of n- and p-type crystals was changed from 1.5×10¹⁷ to 3×10¹⁷ cm⁻³ and 4×10¹⁷ to 2×10¹⁹ cm⁻³, respectively. The activation energies of n-type crystals were 0.09–0.11 eV while that of p-type crystals were 0.02–0.03 eV.     

HgCdTe组分异质结的生长与表征

采用富碲水平推舟液相外延生长方式,在(111)晶向的碲锌镉衬底上生长了双层组分异质HgCdTe外延薄膜,并对生长后的薄膜质量进行了评价.使用染色法和红外透射光谱数值拟合的方法,对两层薄膜的厚度进行了表征,并建立了一个双层薄膜纵向组分分布模型;对材料的电学参数进行测量的结果显示,双层异质液相外延样品中长波层的载流子迁移率较之单层液相外延样品略高,原因可能是中波覆盖层对长波外延层起到了钝化作用.     

Development of inclusion-free CdZnTe substrates from crystals grown by the vertical-gradient freeze method

With the aim of fabrication of (111) and (211) CdZnTe inclusion-free substrates for molecular-beam epitaxy (MBE) and liquid-phase epitaxy (LPE) growth of mercury cadmium telluride (MCT), we focused on fundamental research of the process of crystallization and cooling to room temperature. Based on the study of inclusion formation in dependence of Cd overpressure above the melt, an optimized process of crystal solidification was established. A key result of this study is the position of the Cd pressure, where inclusion-free crystals were fabricated without post-growth annealing. The crystals with a diameter of 100 mm and a height 40–50 mm were fabricated by the vertical-gradient freeze method (VGFM). The resulting ingots exhibit very good crystallographic quality, with a single-crystalline part filling 60–80% of the crystal volume. Substrates with orientation (111) and (211) and dimensions up to 4 × 4 cm were fabricated.     

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.     

脉冲激光双光束沉积掺Mg的GaN薄膜的研究

采用脉冲激光双光束沉积系统在Si(111)衬底上生长了掺Mg的GaN薄膜和未掺杂GaN薄膜。利用X射线衍射(XRD)、原子力显微镜(AFM)、室温范德堡霍尔测量及光致发光(PL)光谱对两类薄膜进行对比分析，结果显示，所生长的GaN薄膜均为六方纤锌矿晶体结构，掺Mg可细化所生长的GaN薄膜晶粒。随着掺Mg量的增加，GaN薄膜无需后处理即可由”型导电转化为p型导电，GaN薄膜的光学性能随p型载流子浓度增大而提高；然而掺Mg却导致GaN薄膜结晶质量下降，掺镁量过大的GaN薄膜中p型载流子浓度反而减少，光致发光中黄发射峰增强较大。研究表明通过优化脉冲激光双光束沉积参数无需任何后处理可直接获得高空穴载流子浓度的p型GaN薄膜。     

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。     

Study of contacts to CdZnTe radiation detectors

This study characterizes, for the first time, contacts to CdZnTe radiation detectors by measuring the dark noise spectra as a function of the applied bias. The noise currents are correlated with the dc dark current-voltage characteristics of CdZnTe x-ray and gamma-ray detectors. In order to identify and separate the role of the contacts in the overall performance, the measured noise phenomena is correlated with detector configuration and contact design as well as the growth method of the CdZnTe crystals, contact technology, and passivation. Several contact technologies (electroless gold, and a number of evaporated metallic contacts including gold, indium, zinc, titanium, aluminum, and platinum contacts) are compared. Contacts to CdZnTe crystals grown by high pressure Bridgman are compared with contacts to CdZnTe crystals grown by modified Bridgman. Contacts of resistive detectors as well as of Schottky detectors are reported. Large area symmetric contacts are compared with small area pixelized contacts. The role of the metallization used for contacts, the role of surface effects and passivation, and the role of contact design are discussed.     

CdZnTe衬底对碲镉汞气相外延表面形貌的影响

利用气相外延技术在CdZnTe衬底上生长Hg1-xCdxTe薄膜材料,通过在不同晶向、不同极性、不同晶向偏离角度CdZnTe衬底上的外延结果发现,CdZnTe衬底对外延形貌的影响非常大。(111)面衬底上外延形貌明显优于(211)面衬底的外延形貌。对于同是<111>CdZnTe晶向的衬底,(111)Cd面CdZnTe衬底上的外延形貌明显优于(111)Te面。对于(111)Cd面CdZnTe衬底,当晶向偏离角度不同时,其外延形貌也有差异,晶向偏离角越小表面形貌越好。     

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.     

用VGF法生长6英寸锗单晶中籽晶熔接工艺研究

采用垂直梯度凝固(VGF)法生长单晶时,其温度梯度较低,生长速率较小,目前已成为生长大直径、低位错密度晶体的主流技术之一.在VGF法生长单晶的过程中,籽晶的熔接工艺直接影响着单晶生长的成败.研究了拉速器速度、保温时间及石英棉用量对6英寸(1英寸=2.54 cm)锗单晶VGF生长中籽晶熔接的影响,并确定了最佳的籽晶熔接工艺.研究结果发现,当拉速器速度为3～4 mm/h、保温时间为75～100 min、石英棉用量为15～20 9时,实现了对籽晶熔接工艺的精准控制,熔接长度为12～22 mm,位错密度小于500 cm-2,有效地降低了生产成本,提高了生产效率和单晶率.     

Au/Cd复合电极沉积方法对其与(111)面CdZnTe衬底接触性能的影响

CdZnTe晶片是HgCdTe外延薄膜的理想衬底。为了优化CdZnTe衬底的电学接触性能,作者基于真空蒸发法和磁控溅射法分别在p型导电性CdZnTe晶片(111)B (富碲面)制备Au/Cd复合电极。通过接触粘附试验,研究了复合电极的制备方法对电极与衬底之间的粘附性;利用卢瑟福背散射光谱法（RBS）比较了不同沉积方法下样品的元素深度分布;采用电流-电压(I-V)测试比较了两种制备工艺对Au/Cd复合电极与CdZnTe衬底欧姆接触特性的影响,从而确定了最佳复合电极的制备工艺。     

Investigation of HgCdTe p-n device structures grown by liquid-phase epitaxy

The microstructure of p-n device structures grown by liquid-phase epitaxy (LPE) on CdZnTe substrates has been evaluated using transmission electron microscopy (TEM). The devices consisted of thick (∼21-μm) n-type layers and thin (∼1.6-μm) p-type layers, with final CdTe (∼0.5 μm) passivation layers. Initial observations revealed small defects, both within the n-type layer (doped with 8×10¹⁴/cm³ of In) and also within the p-type layer but at a much reduced level. These defects were not visible, however, in cross-sectional samples prepared by ion milling with the sample held at liquid nitrogen temperature. Only isolated growth defects were observed in samples having low indium doping levels (2×10¹⁴/cm³). The CdTe passivation layers were generally columnar and polycrystalline, and interfaces with the p-type HgCdTe layers were uneven. No obvious structural changes were apparent in the region of the CdTe/HgCdTe interfaces as a result of annealing at 250°C.     

VGF法生长的低位错掺Si-GaAs单晶的缺陷和性质

研究了垂直梯度凝固法（VGF法）生长的掺Si低阻GaAs单晶材料的晶格缺陷和性质,并将VGF法和LEC法生长的非掺半绝缘GaAs单晶进行了比较. 利用A-B腐蚀显微方法比较了两种材料中的微沉积缺陷,对其形成原因进行了分析. 利用荧光光谱研究了掺Si-GaAs单晶中Si原子和B原子的占位情况和复合体缺陷. Hall测量结果表明,掺Si低阻VGF-GaAs单晶中存在很强的Si自补偿效应,造成掺杂效率降低. VGF-GaAs单晶生长过程中高的Si掺杂浓度造成晶体中产生大量杂质沉积,而杂质B的存在加重了这种现象. 对降低缺陷密度,提高掺杂效率的途径进行了分析.