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.     

Examination of the effects of high-density plasmas on the surface of HgCdTe

High-density argon-hydrogen plasmas have been demonstrated to be very effective as etchants of CdTe, CdZnTe, and HgCdTe materials for focal plane array applications. Understanding the physical, chemical, and electrical characteristics of these surfaces is critical in elucidating the mechanisms of processing Hg_1−xCd_xTe. The ways in which these plasmas interact with HgCdTe, such as etch rates and loading, have been studied.^1–11 However, little is known on how these plasmas affect the first few atomic layers of HgCdTe. In this study, the effects of high-density plasmas on the surface of HgCdTe were examined. The combination of argon and hydrogen plasma etch leaves a well-ordered, near-stoichiometric surface determined by both x-ray photoelectron spectroscopy and reflection high-energy electron diffraction (RHEED). Starting with Hg_0.78Cd_0.22Te, we were able to produce surfaces with x=0.4 and a RHEED pattern sharp enough to measure 2×1 reconstruction.     

MBE growth and device processing of MWIR HgCdTe on large area Si substrates

The traditional substrate of choice for HgCdTe material growth has been lattice matched bulk CdZnTe material. However, as larger array sizes are required for future devices, it is evident that current size limitations of bulk substrates will become an issue and therefore large area Si substrates will become a requirement for HgCdTe growth in order to maintain the cost-efficiency of future systems. As a result, traditional substrate mounting methods that use chemical compounds to adhere the substrate to the substrate holder may pose significant technical challenges to the growth and fabrication of HgCdTe on large area Si substrates. For these reasons, non-contact (indium-free) substrate mounting was used to grow mid-wave infrared (MWIR) HgCdTe material on 3″ CdTe/Si substrates. In order to maintain a constant tepilayer temperature during HgCdTe nucleation, reflection high-energy electron diffraction (RHEED) was implemented to develop a substrate temperature ramping profile for HgCdTe nucleation. The layers were characterized ex-situ using Fourier transform infrared (FTIR) and etch pit density measurements to determine structural characteristics. Dislocation densities typically measured in the 9 10⁶ cm⁻² to 1 10⁷ cm⁻² range and showed a strong correlation between ramping profile and Cd composition, indicating the uniqueness of the ramping profiles. Hall and photoconductive decay measurements were used to characterize the electrical properties of the layers. Additionally, both single element and 32 32 photovoltaic devices were fabricated from these layers. A RA value of 1.8 10⁶-cm² measured at −40 mV was obtained for MWIR material, which is comparable to HgCdTe grown on bulk CdZnTe substrates.     

Helium-Plasma-Prepared (111)A HgCdTe and (211)B InSb

Brief low-energy helium plasma exposure of mercury cadmium telluride and indium antimonide results in oxide- and elemental-component-free, nearly stoichiometric surfaces. In these initial experiments, the only remaining residue is a topmost trace layer of carbon similar to that present on wet etched and reduced surfaces. The nature of these surfaces was determined by in situ Auger electron spectroscopy, monochromatic X-ray photoelectron, and ion scattering spectroscopy, and compared with established wet chemical and hydrogen argon plasma preparations.     

Electron cyclotron resonance plasma preparation of CdZnTe (211)B surfaces for HgCdTe molecular beam epitaxy

CdZnTe wafers were inserted into a multi-chamber processing facility without prior preparation, cleaned by exposure to an electron cyclotron resonance Ar/H₂ plasma, and used as substrates for molecular beam epitaxy of HgCdTe. Changes induced in the wafer near-surface region during the cleaning step were monitored using in situ spectroscopic ellipsometry. Ellipsometric data were subsequently modeled to provide the time evolution of the thickness of a native overlayer. Auger electron spectra were consistent with surfaces free of residual contamination and which had the stoichiometry of the underlying bulk. Surface roughness values of 0.4 nm were obtained ex situ using interferometric microscopy. Electron diffraction patterns of plasma prepared wafers heated to 185°C (the temperature required for HgCdTe molecular beam epitaxy) were streaked. Structural and electrical characteristics of epilayers grown on these substrates were found to be comparable to those deposited on wafers prepared using a conventional wet chemical process. This demonstrates an important step in an all-vacuum approach to HgCdTe detector fabrication.     

Surface structure of (111)A HgCdTe

The surface of (111)A HgCdTe has been studied by reflection high-energy electron diffraction and atomic force microscopy (AFM). The as-grown liquid-phase epitaxy (LPE) surface has bilayer (3.7 ± 0.2 Å) step/terrace structures, macro-steps, and cross-hatch patterns. Macro-steps occur about the $[11\bar 2]$ and are from 10–40 Å in height. AFM and x-ray measurements indicate the as-grown epilayer is ≈0.2° off-cut (random polar angle) from the (111). 〈110〉 cross-hatch lines consistent with bilayer (step height=3.9 ± 0.2 Å) {111} slip dislocation are observed. The native oxide/carbon layer for the as-grown LPE (111)A HgCdTe is ≈8 Å. The experimental results suggest that the as-grown LPE surface approximates an equilibrium vicinal crystal structure. The 0.1% Br:ethylene glycol wet chemically etched surfaces retained the macro-step structure, but numerous small protrusions (10–100 Å height, ≈300 Å diameter) developed. The plasma-etched (111)A HgCdTe surface is crystalline, but exhibits surface disorder and is roughened.     

Use of electron cyclotron resonance plasmas to prepare CdZnTe (211)B substrates for HgCdTe molecular beam epitaxy

Without any additional preparation, Cd_1−yZn_yTe (211)B (y∼3.5%) wafers were cleaned by exposure to an electron cyclotron resonance (ECR) Ar/H₂ plasma and used as substrates for HgCdTe molecular beam epitaxy. Auger electron spectra were taken from as-received wafers, conventionally prepared wafers (bromine: methanol etching, followed by heating to 330–340°C), and wafers prepared under a variety of ECR process conditions. Surfaces of as-received wafers contained ∼1.5 monolayers of contaminants (oxygen, carbon, and chlorine). Conventionally prepared wafers had ∼1/4 monolayer of carbon contamination, as well as excess tellurium and/or excess zinc depending on the heating process used. Auger spectra from plasma-treated CdZnTe wafers showed surfaces free from contamination, with the expected stoichiometry. Stoichiometry and surface cleanliness were insensitive to the duration of plasma exposure (2–20 s) and to changes in radio frequency input power (20–100 W). Reflection high energy electron diffraction patterns were streaked indicating microscopically smooth and ordered surfaces. The smoothness of plasma-etched CdZnTe wafers was further confirmed ex situ using interferometric microscopy. Surface roughness values of ∼0.4 nm were measured. Characteristics of HgCdTe epilayers deposited on wafers prepared with plasma and conventional etching were found to be comparable. For these epilayers, etch pit densities on the order of 10⁵ cm⁻² have been achieved. ECR Ar/H₂ plasma cleaning is now utilized at Night Vision and Electronic Sensors Directorate as the baseline CdZnTe surface preparation technique.     

Surface Structure of Molecular Beam Epitaxy (211)B HgCdTe

The as-grown molecular beam epitaxy (MBE) (211)B HgCdTe surface has variable surface topography, which is primarily dependent on substrate temperature and substrate/epilayer mismatch. Nano-ripple formation and cross-hatch patterning are the predominant structural features observed. Nano-ripples preferentially form parallel to the \( [\bar {1}11] \) and are from 0 Å to 100 Å in height with a wavelength between 0.1 μm and 0.8 μm. Cross-hatch patterns result from slip dislocations in the three {111} planes intersecting the (211) growth surface. The cross-hatch step height is 4 ± 1 Å (limited data set). This indicates that only a bi-layer slip (Hg/Cd + Te) in the {111} slip plane occurs. For the deposition of MBE (211)B HgCdTe/CdTe/Si, the reorientation of multiple nano-ripples coalesced into “packets” forms cross-hatch patterns. The as-grown MBE (211)B CdTe/Si surface is highly variable but displays nano-ripples and no cross-hatch pattern. Three types of defects were observed by atomic force microscopy (AFM): needle, void/hillock, and voids.     

In-situ ellipsometry studies of adsorption of Hg on CdTe(211)B/Si(211) and molecular beam epitaxy growth of HgCdTe(211)B

We study the adsorption of Hg on CdTe(211)B using an 88-wavelength spectroscopic ellipsometer mounted on a commercial, molecular beam epitaxy (MBE) chamber. A detailed analysis of the pseudo-dielectric function shows that Hg is present at the surface both in chemisorbed and physisorbed form. Effective medium models for a mixture of chemisorbed and physisorbed Hg on the microscopically rough CdTe surface could not fit our data. However, a proposed model in which a partial layer of physisorbed Hg sits on top of a partial layer of chemisorbed Hg fits the measured pseudo-dielectric function well and yields precise values for the thicknesses of the chemisorbed and the physisorbed Hg layers. These values change in the expected manner as a function of Hg flux, temperature, and Te coverage. An analysis of the uncertainty in the measured thicknesses is carried out in detail, and a study of the limitations of the ellipsometer used for this study is presented. The effects of these limitations on the precision and accuracy of in-situ data are enumerated.     

Real-time monitoring of the surface stoichiometry during molecular beam epitaxy of cubic GaN on (001) GaAs by RHEED

We study the plasma-assisted molecular beam epitaxy of cubic GaN on GaAs(OOl) substrates by means ofin-situ reflection high-energy electron diffraction. The epilayers are characterized by x-ray diffraction, photoluminescence, and Hall measurements, and it is found that the overall best films are grown under a N/Ga ratio close to one. For anin-situ determination of the N/Ga ratio, the growth kinetics is studied via surface reconstruction transitions. The effective N flux giving rise to growth is measured using the transient behavior of the half-order diffraction streak intensity for various plasma operating conditions.     

分子束外延HgCdTe/CdZnTe(211)B表面缺陷研究

HgCdTe材料的表面缺陷是造成探测器性能下降的主要原因之一。采用聚焦离子束（Focused Ion Beam, FIB）、扫描电子显微镜（Scanning Electron Microscope, SEM）和能量色散X射线光谱仪（Energy Dispersive X-ray Spectrometer, EDX）研究了碲锌镉（CdZnTe)基HgCdTe外延层的表面缺陷。通过分析不同类型缺陷形成的原因,确定缺陷起源于HgCdTe材料生长过程。缺陷的形状与生长条件关系密切。凹坑及火山口状缺陷与Hg缺乏/稍高生长温度、分子束源坩埚中材料形状变化造成的不稳定束流有关。金刚石状缺陷和火山口状/金刚石状复合缺陷的产生与Hg/Te高束流比、低生长温度相关。在5 cm×5 cm大小的CdZnTe(211)B衬底表面上生长出了组分为0.216、厚度约为6.06~7 μm的高质量HgCdTe外延层。同时还建立了缺陷类型与HgCdTe薄膜生长工艺的关系。该研究对于制备高质量HgCdTe/CdZnTe外延层具有参考意义。     

Structural Analysis of CdTe Hetero-epitaxy on (211) Si

X-ray diffraction full-width at half-maximum (XRD FWHM), reflection high-energy electron diffraction (RHEED), and atomic force microscopy (AFM) indicate a mosaic structure for molecular-beam epitaxy (MBE) (211)B CdTe/Si. AFM measurements indicate long, thin, small-angle-disoriented grains for CdTe/Si epilayers. These disoriented grains are ~1 μm in the [] direction and are ~40 nm in the [] direction. The RHEED pattern in the [] direction depicts nearly ideal single-crystal periodicity. The RHEED pattern in the [] direction is indicative of small-angle-disoriented crystalline grains. Scanning electron microscopy (SEM), AFM, and XRD measurements all indicate an approximate factor of 10 increase in the Everson etch pit density (EPD) over standard Nomarski microscopy Everson EPD determination.     

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.     

Monolithically integrated HgCdTe focal plane arrays

The cost and performance of hybrid HgCdTe infrared (IR) focal plane arrays are constrained by the necessity of fabricating the detector arrays on a CdZnTe substrate. These substrates are expensive, fragile, available only in small rectangular formats, and are not a good thermal expansion match to the silicon readout integrated circuit. We discuss in this paper an IR sensor technology based on monolithically integrated IR focal plane arrays that could replace the conventional hybrid focal plane array technology. We have investigated the critical issues related to the growth of HgCdTe on Si read-out integrated circuits and the fabrication of monolithic focal plane arrays: (1) the design of Si read-out integrated circuits and focal plane array layouts; (2) the low-temperature cleaning of Si(001) wafers; (3) the growth of CdTe and HgCdTe layers on read-out integrated circuits; (4) diode creation, delineation, electrical, and interconnection; and (4) demonstration of high yield photovoltaic operation without limitation from earlier preprocessing such as substrate cleaning, molecular beam epitaxy (MBE) growth, and device fabrication. Crystallographic, optical, and electrical properties of the grown layers will be presented. Electrical properties for diodes fabricated on misoriented Si and readout integrated circuit (ROIC) substrates will be discussed. The fabrication of arrays with demonstrated I–V properties show that monolithic integration of HgCdTe-based IR focal plane arrays on Si read-out integrated circuits is feasible and could be implemented in the third generation of IR systems.     

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。     

P-Type doping with arsenic in (211)B HgCdTe grown by MBE

Arsenic incorporation and doping in HgCdTe layers grown by molecular beam epitaxy (MBE) were examined in this paper. Arsenic incorporation into MBE-HgCdTe was carried out in two different ways: (1)ex-situ arsenic ion-implantation on indium-doped n-type HgCdTe layers, and (2) through a new approach called arsenic planar doping. We report onex-situ arsenic diffusion on indiumdoped MBE-HgCdTe layers at 450°C. In the investigated layers, arsenic redistribution occurs with a multi-component character. We obtained a diffusion coefficient of D_As = (1-3) × 10⁻¹³ cm²/s at 450°C. Results of differential Hall and fabricated p-n junctions suggest that during high temperature annealing, arsenic preferentially substitutes into Te sublattices and acts as acceptor impurities. In the second case, arsenic has been successfully incorporated during the MBE growth as an acceptor in the planar doping approach. Withoutex-situ annealing, as-grown layers show up to 50% activation of arsenic during the growth. These results are very promising forin-situ fabrication of infrared devices using HgCdTe material.     

Suppression of strain-induced cross-hatch on molecular beam epitaxy (211)B HgCdTe

Because the performance of HgCdTe-based photodiodes can be significantly degraded by the presence of dislocations, we have systematically investigated and suppressed lattice-mismatch-induced cross-hatch formation and the associated generation of dislocations in (211)B HgCdTe/CdZnTe. A series of HgCdTe epilayers were deposited simultaneously on pairs of substrates with differing ZnTe mole fractions. Epilayers’ CdTe mole fraction and substrates’ ZnTe mole fractions were measured using optical-transmission spectra. Lattice mismatch and residual strain were estimated from room-temperature, x-ray diffraction, and double-crystal rocking-curve measurements (DCRC). It was found that cross-hatch patterns were suppressed in epilayers deposited on nearly lattice-matched substrates (|Δa/a_sub|<0.02%). Such epilayers exhibited excellent crystalline quality as revealed by defect-decoration etching (etch-pit density (EPD)<10⁵ cm⁻²) and x-ray diffraction (full-width at half-maximum (FWHM) ∼10 arcsec). In addition to determining the upper limits of lattice mismatch needed to eliminate cross-hatch, we investigated the use of reticulated substrates as a means to suppress cross-hatch. We found that growth on reticulated mesa structures (<100 μm) with edges parallel to [01-1] resulted in epilayers with substantially reduced cross-hatch-line densities despite large lattice mismatch (Δa/a_sub <0.04%). The use of reticulated substrates could suppress cross-hatch because of lateral-alloy variation in large substrates and complex multistack epilayers (e.g., multicolor detectors).     

Surface Morphology and Defect Formation Mechanisms for HgCdTe (211)B Grown by Molecular Beam Epitaxy

The surface morphology and crystallinity of HgCdTe films grown by molecular beam epitaxy (MBE) on both CdZnTe and CdTe/Si (211)B substrates were characterized using atomic force microscopy (AFM), as well as scanning (SEM) and transmission (TEM) electron microscopy. Crosshatch patterns and sandy-beach-like morphologies were commonly found on MBE (211) HgCdTe epilayers grown on both CdZnTe and CdTe/Si substrates. The patterns were oriented along the , , and directions, which were associated with the intersection between the (211) growth plane and each of the eight equivalent HgCdTe slip planes. This was caused by strain-driven operation of slip in these systems with relative large Schmid factor, and was accompanied by dislocation formation as well as surface strain relief. Surface crater defects were associated with relatively high growth temperature and/or low Hg flux, whereas microtwins were associated with relatively low growth temperature and/or high Hg flux. AFM and electron microscopy were used to reveal the formation mechanisms of these defects. HgCdTe/HgCdTe superlattices with layer composition differences of less than 2% were grown by MBE on CdZnTe substrates in order to clarify the formation mechanisms of void defects. The micrographs directly revealed the spiral nature of growth, hence demonstrating that the formation of void defects could be associated with the Burton, Cabrera, and Frank (BCF) growth mode. Void defects, including microvoids and craters, were caused by screw defect clusters, which could be triggered by Te precipitates, impurities, dust, other contamination or flakes. Needle defects originated from screw defect clusters linearly aligned along the directions with opposite Burgers vector directions. They were visible in HgCdTe epilayers grown on interfacial superlattices. Hillocks were generated owing to twin growth of void or needle defects on (111) planes due to low growth temperature and the corresponding insufficient Hg movement on the growth surface. Therefore, in addition to nucleation and growth of HgCdTe in the normal two-dimensional layer growth mode, the BCF growth mode played an important role and should be taken into account during investigation of HgCdTe MBE growth mechanisms.     

Shear deformation and strain relaxation in HgCdTe on (211) CdZnTe

Shear strain is present in Hg_0.68Cd_0.32Te epitaxial layers grown by molecular beam epitaxy on (211)-oriented Cd_1−yZn_yTe substrates. Differences in the substrate zinc composition led to lattice mismatch between the epitaxial layer and the substrate. The shear strain induced by the mismatch was measured using reciprocal space maps in the symmetric (422) and asymmetric (511) and (333) reflections. In addition, strain relaxation through the formation of misfit dislocations was confirmed using double crystal x-ray topography. Both the shear strain and the misfit dislocation density increased with increasing mismatch between the epitaxial layer and the substrate. Lattice-matched layers were free of misfit dislocations and exhibited triple axis diffraction rocking curve widths of approximately 6 arcsec. The combination of a thick epitaxial layer, a low index substrate, and the potential for lattice mismatch indicates that both shear strains and misfit dislocations must be considered in the structural analysis of HgCdTe/CdZnTe heterostructures.     

分子束外延InAs量子点的RHEED实时原位分析

介绍了利用反射式高能电子衍射(RHEED)方法在自组装InAs量子点制备过程中进行结构分析的理论研究与实验工作的最新进展。从反射式高能电子衍射在InAs量子点临界转变状态测定、量子点表面取向、量子点应力分布测定、量子点形核长大动力学过程研究等方面的应用,可以看出RHEED在InAs量子点形成过程中对多种结构特征的原位分析具有突出优势。反射式高能电子衍射仪作为分子束外延系统中的标准配置,已成为一种对InAs量子点微观结构进行分析的简易而理想的分析测试工具。随着反射式高能电子衍射以及衍射理论的进一步发展,必将促进InAs量子点结构的精确表征水平的提高,进而实现更加理想结构的InAs量子点的制备及其应用。