Lpe growth of Hgl−xCdxTe using conventional slider boat and effects of annealing on properties of the epilayers

The epitaxial layers of Hg_1−xCd_xTe (0.17≦×≦0.3) were grown by liquid phase epitaxy on CdTe (111)A substrates using a conventional slider boat in the open tube H₂ flow system. The as-grown layers have hole concentrations in the 10¹⁷− 10¹⁸ cm⁻³ range and Hall mobilities in the 100−500 cm²/Vs range for the x=0.2 layers. The surfaces of the layers are mirror-like and EMPA data of the layers show sharp compositional transition at the interface between the epitaxial layer and the substrate. The effects of annealing in Hg over-pressure on the properties of the as-grown layers were also investigated in the temperature range of 250−400 °C. By annealing at the temperature of 400 °C, a compositional change near the interface is observed. Contrary to this, without apparent compositional change, well-behaved n-type layers are obtained by annealing in the 250−300 °C temperature range. Sequential growth of double heterostructure, Hg_l−xCd_xTe/Hg_l−yCd_yTe on a CdTe (111)A substrate was also demonstrated.     

Defect reduction in Hg1−xCdxTe grown by molecular beam epitaxy on Cd0.96Zn0.04Te(211)B

A study on preparation of Cd_0.96Zn_0.04Te(211)B substrates for growth of Hg_1−xCd_xTe epitaxial layers by molecular beam epitaxy (MBE) was investigated. The objective was to investigate the impact of starting substrate surface quality on surface defects such as voids and hillocks commonly observed on MBE Hg_1−xCd_xTe layers. The results of this study indicate that, when the Cd_0.96Zn_0.04Te(211)B substrates are properly prepared, surface defects on the resulting MBE Hg_1−xCd_xTe films are reduced to minimum (size, ∼0.1 m and density ∼500/cm²) so that these MBE Hg_1−xCd_x Te films have surface quality as good as that of liquid phase epitaxial (LPE) Hg_1−xCd_xTe films currently in production in this laboratory.     

Transient behavior of Hg1−xCdxTe film growth on (111)B CdTe substrates by chemical vapor transport

As part of a systematic investigation of the effects of substrate surfaces on epitaxial growth, the transient behavior of Hg_1−xCd_xTe film growth on (111)B CdTe by chemical vapor transport (CVT) has been studied as a function of growth time under vertical stabilizing (hot end on top) and vertical destabilizing (hot end at bottom) ampoule orientations. The experim ental results show the morphological transition of the Hg_1−xCd_xTe deposition on (111)B CdTe at 545°C from three-dimensional islands to layers within about 0.5 and 0.75 h for the growth under vertical stabilizing and destabilizing conditions, respectively. The combined effects of small convective flow disturbances on the growth morphology and defect formation are measurable. The overall trends of the time dependent growth rates and compositions of the Hg_1−xCd_xTe epitaxial layers under stabilizing and destabilizing conditions are similar. The system atically higher growth rates of the Hg_1−xCd_xTe films by about 10% under vertical destabilizing conditions could be influenced by a small convective contribution to the mass transport. The combined results show that improved Hg_1−xCd_xTe epitaxial layers of low twin density on (111)B CdTe substrates can be obtained by CVT under vertical stabilizing conditions.     

Molecular beam epitaxial growth of HgCdTe on CdZnTe(311)B

A series of n-type, indium-doped Hg_1−xCd_xTe (x∼0.225) layers were grown on Cd_0.96Zn_0.04Te(311)B substrates by molecular beam epitaxy (MBE). The Cd_0.96Zn_0.04Te(311)B substrates (2 cm × 3 cm) were prepared in this laboratory by the horizontal Bridgman method using double-zone-refined 6N source materials. The Hg_1−xCd_xTe(311)B epitaxial films were examined by optical microscopy, defect etching, and Hall measurements. Preliminary results indicate that the n-type Hg_1−xCd_xTe(311)B and Hg_1−xCd_xTe(211)B films (x ∼ 0.225) grown by MBE have comparable morphological, structural, and electrical quality, with the best 77 K Hall mobility being 112,000 cm²/V·sec at carrier concentration of 1.9×10⁺¹⁵ cm⁻³.     

Electrical properties and compositional distributions of CVT and PVT grown Hg1−xCdxTe epilayers

Epitaxial layers of Hg_1−xCd_x Te were grown on CdTe substrates by the chemical vapor transport technique using Hgl₂ as a transport agent. The epilayers were of nearly uniform composition both laterally and to a depth of about one-half of the layer thickness. By comparison, the composition varied continuously throughout the depth of the layer for epilayers grown by the physical vapor transport technique. Layers were grown both p- and n-type with carrier concentrations on the order of 10¹⁷ cm⁻³. Low-temperature annealing was used to convert the p-type layers into n-type. The room-temperature carrier mobilities of as-grown and converted n-type layers ranged from 10³ to 10⁴ cm²/V-s depending on the composition and are comparable to previous literature values for undoped Hg_1−xCd_xTe crystals.     

Transient behavior of Hg1−xCdxTe films deposited on (100) CdTe substrates by chemical vapor transport

The growth history of Hg_1−xCd_xTe films deposited on (100) CdTe substrates by chemical vapor transport (CVT) has been studied, for the first time, by using a transient growth technique. The observed morphological evolution of Hg_1−xCd_xTe films deposited at 545°C shows a transition behavior from three-dimensional (3D) islands to two-dimensional (2D) layer growth. The experimental results indicate that the so-called critical time needed for the above morphological transition is about lh under present experimental conditions. Based on the chemical bonding properties of Hg_1−xCd_xTe, and on the behavior of the morphological transition, the Stranski-Krastanov growth mode is suggested for the epitaxial growth system. The time dependence of the growth thickness, of the growth rate (R₁₀₀) along the [100] direction, and of the surface composition all reveal a transient behavior. These are related to the nature of the Hg_1-xCd_xTe/ (100)CdTe heterojunction and to the surface reactions. Comparison of the growth rates and of the total mass deposited as a function of time shows the relationship between epitaxial growth and mass flux of the Hg_1−xCd_xTe-HgI₂ chemical vapor transport system.     

High-Quality (211)B CdTe on (211)Si Substrates Using Metalorganic Vapor-Phase Epitaxy

High-quality (211)B CdTe buffer layers are required during Hg_1−x Cd _x Te heteroepitaxy on Si substrates. In this study, direct metalorganic vapor-phase epitaxy (MOVPE) of (211)B CdTe on Si, as well as CdTe on Si using intermediate Ge and ZnTe layers, has been achieved. Tertiary butyl arsine was used as a precursor to enable As surfactant action during CdTe MOVPE on Si. The grown CdTe/Si films display a best x-ray diffraction rocking-curve full-width at half-maximum of 64 arc-s and a best Everson etch pit density of 3 × 10⁵ cm⁻². These values are the best reported for MOVPE-grown (211)B CdTe/Si and match state-of-the-art material grown using molecular-beam epitaxy.     

Spectroscopic ellipsometry for monitoring and control of molecular beam epitaxially grown HgCdTe heterostructures

A systematic study of the effect of measurement perturbation on in situ monitoring of the composition of molecular beam epitaxially (MBE) grown Hg_1−xCd_xTe using spectroscopic ellipsometry was carried out. Of the five variables investigated, which included angle of incidence, wavelength of the light beam, modulator rotation, analyzer rotation, and modulator amplitude, the angle of incidence and the modulator rotation had the strongest effect on the in situ Hg_1−xCd_xTe composition monitoring process. A wobble-free sample manipulator was installed to reduce the impact of these two variables. With these improvements, the spectroscopic ellipsometer is now routinely used to monitor Hg _1−xCd_xTe compositions during MBE growth of heterostructures and is a useful tool in diagnosing growth-related problems. Examples are included for both application areas, that include the control of the interface between Hg_1−xCd_xTe layers of different compositions, i.e. device engineering.     

HgCdZnTe quaternary materials for lattice-matched two-color detectors

As the number of bands and the complexity of HgCdTe multicolor structures increases, it is desirable to minimize the lattice mismatch at growth interfaces within the device structure in order to reduce or eliminate mismatch dislocations at these interfaces and potential threading dislocations that can degrade device performance. To achieve this we are investigating the use of Hg_1−x−yCd_xZn_yTe quaternary alloys which have an independently tunable lattice constant and bandgap. Lattice matching in Hg_1−x−yCd_xZn_yTe structures can be achieved using small additions of Zn (y<0.015) to HgCdTe ternary alloys. We have investigated some of the basic properties of Hg_1−x−yCd_xZn_yTe materials with x≈0.31 and 0≤y≤0.015. The quaternary layers were grown on (112)CdZnTe substrates using MBE and the amount of Zn in the layers was determined from calibrated SIMS measurements. As expected, the lattice constant decreased and the bandgap increased as Zn was added to HgCdTe to form Hg_1−x−yCd_xZn_yTe. Hall-effect results for both n-type (In) and p-type (As) Hg_1−x−yCd_xZn_yTe layers were very similar to HgCdTe control samples. We have also utilized x-ray rocking curve measurements with (246) asymmetric reflections as a novel sensitive technique to determine the correct amount of Zn needed to achieve lattice matching at an interface. MWIR/LWIR n-p-n two-color triple-layer heterojunction structures were grown to evaluate the effects of minimizing the lattice mismatch between the widest bandgap p-type collector layer, using Hg_1−x−yCd_xZn_yTe, and the HgCdTe MWIR and LWIR collector layers and compared to structures that did not incorporate the quaternary. Sequential mode two-color detectors were fabricated using a 256 × 256, 30 μm unit cell design. There were several interesting findings. Macro defects predominantly affected the LWIR band (Band 2) operability and had little effect on the MWIR band (Band 1). The incorporation of Hg_1−x−yCd_xZn_yTe p-type collector layers had little effect on MWIR detector performance, but overall the LWIR performance was generally better. These initial detector results indicate that the use of Hg_1−x−yCd_xZn_yTe alloys in multicolor detector structures are potentially promising and should be pursued further.     

Crystal defects and interdiffusion behavior of Hg1−xCdxTe/(100)CdTe epitaxial layers grown by chemical vapor transport

Crystal defects of chemical vapor transport grown Hg_1−xCd_xTe on (100) CdTe structures have been investigated using chemical etching, wavelength-dispersive spectroscopy, x-ray rocking curve, and scanning electron microscopy methods The results indicate that the origin and spatial distribution of the misfit dislocations can be attributed to both the lattice parameter misfit and the inevitable interdiffusion occurring between the substrate and the epitaxial layer. It is proposed that the interdiffusion of Hg along the [100] direction is enhanced by dislocation channels and other defect cores along or near this direction owing to defects on the initial surface of the CdTe substrate. The results indicate that the subgrain boundaries in Hg_1−xCd_xTe are caused by slight misorientation of the lattices and polygonization of the defects during epitaxial layer growth, and by the propagation of the subgrain boundaries existing in the CdTe substrate.     

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.     

Automated compositional control of Hg1−xCdxTe during MBE, using in situ spectroscopic ellipsometry

The implementation of a feedback control system for maintaining a desired compositional value in Hg_1−xCd_xTe epilayers is reported. An 88-wavelength ellipsometer monitored the Cd content (x) of a Hg_1−xCd_xTe film during molecular beam epitaxy, and deviations from a pre-determined set-point were automatically corrected via adjustments in the CdTe effusion cell temperature. The accuracy of this system (Δx∼0.002) was confirmed by Fourier transform infrared transmission measurements made ex situ on the epilayers.     

Transient behavior of Hg1−xCdxTe film growth on 3° off-(100) CdTe substrates by chemical vapor transport

The effects of substrate misorientation on Hg_1−xCd_xTe films, deposited on 3° off-(100) CdTe substrates by chemical vapor transport (CVT), have been studied for the first time using a transient growth technique. The morphological evolution of Hg_1−xCd_xTe films deposited on the vicinal CdTe substrates at 545°C shows a transition from three-dimensional islands to two-dimensional layer growth. The time and thickness required for the above morphological transition is about 0.75 h and 7 μm, respectively, under present experimental conditions. The pronounced long-range-terrace surface morphology of the Hg_1−xCd_xTe films illustrates the strong effects of the misorientation of the CdTe substrates and of the growth kinetics on the CVT growth of this hetero-epitaxial system. The transient behavior of the surface morphology, of the surface composition, and of the growth rate all reveal the influences of the 3° misorientation of the (100) CdTe substrates on the Hg_1−xCd_xTe epitaxy. The experimental mass flux results of the Hg_1−xCd_xTe-HgI₂ CVT system under transient and steady-state conditions can be related to the surface kinetics and to the thermodynamic properties of the system. The combined results show that the interface kinetics are not fixed in the transient regime and that they are coupled to the vapor mass transport.     

Transport phenomena in n-MnxHg1−x Te/Cd0.96Zn0.04Te epitaxial films

The results of an experimental study of samples of Mn_xHg_1−x Te films grown by liquid-phase epitaxy on a Cd_0.96Zn_0.04Te substrate are presented. It shows that, as a result of the diffusion of cadmium from the substrate, a Cd_xMn_yHg_1−x−y Te film with a variable band-gap layer is formed close to the 〈epitaxial-film〉-substrate interface. The appearance of this variable band gap is revealed by the transport phenomena. The temperature dependence of the band gap E _g (T) is determined in a linear approximation on T from the results of a theoretical analysis of the temperature dependences of the free-carrier concentration and mobility. It is shown that averaging the semiempirical dependences for the ternary compounds with the extreme compositions, using the virtual-crystal approximation, can produce large errors when determining E _g (T) in a specific semiconductor. Fiz. Tekh. Poluprovodn. 31, 268–272 (March 1997)     

Magnetoluminescence properties of Hg1−xCdxTe epitaxial layers and superlattice structures grown by metalorganic molecular beam epitaxy

We present a study of the electro-optical properties ofHg _1- xCd_xTe epitaxial layers and Hg_1-x Cd_xTe/CdTe (0.28 < x < 0.30) superlattice structures by x-ray diffraction, lateral transport and photo- and magneto-luminescence measurements. Systematic studies of the excitation intensity and magnetic field dependence of the photoluminescence revealed direct evidence of an excitonic contribution to the observed luminescence in Hg_{1- x}Cd_xTe epitaxial layers. Similar investigations of the superlattice structures indicated that excitonic corrections were required to adequately fit the luminescence data. Optical gains of 80 cm⁻¹ were obtained for an excitation intensity of 100 kW/cm² indicating suitable electro-optical properties for making efficient mid-infrared laser diodes.     

Real-time control of HgCdTe growth by organometallic vapor phase epitaxy using spectroscopic ellipsometry

The use of spectroscopic ellipsometry for monitoring the vapor phase epitaxial growth of mercury cadmium telluride (Hg_1−xCd_xTe) in real-time is demonstrated. The ellipsometer is used to perform system identification of the chemical vapor deposition reactor used for the growth of CdTe and to measure the response of the reactor to different growth conditions. The dynamic behavior of the reactor is also studied by evaluating the gas transport delay. The optical constants of Hg_1−xCd_xTe are determined at the growth temperature for different compositions.In-situ real-time composition control is performed during the growth of Hg_1−xCd_xTe. The required target compositions are attained by the ellipsometer and appropriate corrections are also made by the controller when a noise input in the form of a temperature variation is introduced.     

Chemical–Mechanical Polishing of CdTe and ZnxCd1?xTe Single Crystals by H2O2(HNO3)–HBr–Organic Solvent Etchant Compositions

Chemical–mechanical polishing of CdTe and Zn _x Cd_1−x Te single-crystal surfaces by bromine-evolving compositions based on aqueous solutions of H₂O₂(HNO₃)–HBr–solvent has been investigated. The dependences of the chemical–mechanical polishing rate on the dilution of the base polishing etchant for various organic components have been determined. The surface condition after such polishing has been investigated using profilometry. The polishing etchant compositions for CdTe and Zn _x Cd_1−x Te single-crystal surfaces and the chemical polishing conditions have been optimized.     

Effects of a-Si:H resist vacuum-lithography processing on HgCdTe

A vacuum-compatible process for carrying out lithography on Hg_1−xCd_xTe and CdTe films was previously demonstrated. It was shown that hydrogenated amorphous silicon (a-Si:H) could be used as a dry resist by projecting a pattern onto its surface using excimer laser irradiation and then developing that pattern by hydrogen plasma etching. Pattern transfer to an underlying Hg_1−xCd_xTe film was then carried out via Ar/H₂ plasma etching in an electron cyclotron resonance (ECR) reactor. Despite the successful demonstration of pattern transfer, the possibility of inducing harmful effects in the Hg_1−xCd_xTe film due to this vacuum lithography procedure had not been explored. Here we present structural and surface compositional analyses of Hg_1−xCd_xTe films at key stages of the a-Si:H vacuum lithography procedure. X-ray diffraction double crystal rocking curves taken before and after a-Si:H deposition and after development etching were identical, indicating that bulk structural changes in the Hg_1−xCd_xTe film are not induced by these processes. Cross-section transmission electron microscopy studies show that laser-induced heating in the 350 nm thick a-Si:H overlayer is not sufficient to cause structural damage in the underlying Hg_1−xCd_xTe surface. In vacuo surface analysis via Auger electron spectroscopy and ion scattering spectroscopy suggest that the hydrogen plasma development process produces Hg-deficient surfaces but does not introduce C contamination. However, after ECR plasma etching into the Hg_1−xCd_xTe film, the measured x value is much closer to that of the bulk.     

Electrical activity,mode of incorporation and distribution coefficient of group V elements in Hg1−xCdxTe grown from tellurium rich liquid phase epitxial growth solutions

Hg_1−xCd_xTe films were grown liquid phase epitaxially from tellurium rich solutions containing up to 10 at. % of the group V elements P, As, Sb, and Bi. Chemical analysis of the Te growth solutions and the films was carried out in conjunction with extensive Hall effect measurements on the films subsequent to various annealing treatments under Hg rich and Te rich conditions. Despite the presence of a large concentration of the group V elements in the Te source solution, the maximum concentration of these elements incorporated into the liquid phase epitaxially grown Hg_1-xCd_xTe appears to vary from <10¹⁵cm⁻³ for Bi up to 10¹⁷cm⁻³ for phosphorus and As implying a distribution coefficient varying from <10⁻⁵ for Bi up to 10⁻³ for P at growth temperature of ∼500° C. This low value of the distribution coefficient for group V elements for growths from Te rich solutions contrasts with the moderately high values reported in the literature to date for growth from Hg rich solutions as well as pseudobinary solutions (Bridgman growth). The widely differing distribution coefficients and hence the solubility of the group V elements for Hg rich and Te rich liquid phase epitaxial solutions is explained on the basis that the activity coefficient of the group V elements in Te rich solutions is probably orders of magnitude lower than it is in Hg rich solutions. Finally, the results of the anneals at 200° C under Hg saturated conditions with and without a 500° C Hg saturated preanneal have indicatedn top conversion in many of the films attesting to the amphoteric behavior of the group V elements in LPE grown Hg_1−xCd_xTe(s) similar to the previously reported behavior of P in bulk grown Hg_0.8Cd_0.2Te.     

Cyclic Annealing During Metalorganic Vapor-Phase Epitaxial Growth of (211)B CdTe on (211) Si Substrates

High-quality (211)B CdTe buffer layers on Si substrates are required to enable Hg_1–x Cd _x Te growth and device fabrication on lattice-mismatched Si substrates. Metalorganic vapor-phase epitaxy (MOVPE) of (211)B CdTe on Si substrates using Ge and ZnTe interlayers has been achieved. Cyclic annealing has been used during growth of thick CdTe layers in order to improve crystal quality. The best (211)B CdTe/Si films grown in this study display a low x-ray diffraction (XRD) rocking-curve full-width at half-maximum (FWHM) of 85 arcsec and etch pit density (EPD) of 2 × 10⁶ cm⁻². These values are the best reported for MOVPE-grown (211) CdTe/Si and are comparable to those for state-of-the-art molecular beam epitaxy (MBE)-grown CdTe/Si.