Observation of phase separation in Hg1−xCdxTe solid solutions by low incident angle x-ray diffraction

The low incident angle (surface analysis) and the conventional wide angle (bulk analysis) x-ray diffraction techniques were employed to investigate the existence of a miscibility gap in the Hg_1−xCd_xTe system. Samples of initial composition Hg_0.46Cd_0.54Te were annealed at 140 and 400°C, respectively, for four weeks. The diffraction planes (531) and (642) have been selected for the x-ray diffraction analysis. The results of this work provide the first, direct experimental evidence for the existence of a miscibility gap at lower temperature in the Hg_1−xCd_xTe system. The phase separation occurs primarily in a thin surface layer at 140°C and is reversible after annealing at 530°C. The compositions of the two compounds at the tie-line at 140°C are Hg_0.22Cd_0.78Te and Hg_0.63Cd_0.37Te.     

Physico-chemical properties of Ga and In dopants during liquid phase epitaxy of CdxHg1−xTe

This work deals with the study by means of radioactive tracers and autoradiography, as well as measuring of galvanomagnetic properties, of Ga and In doping of epitaxial Cd_xHg_1−xTe layers during their crystallization from a Te-rich melt. Ga and In were introduced in the form of Ga⁷² and In¹¹⁴ master alloys with Te. The effective distribution coefficients of Ga and In during the crystallization of the Cd_xHg_1−xTe solid solutions with x=0.20 to 0.23 were determined by cooling the Te-base melt to 515–470°C. Depending on the concentration of the dopants and the time-temperature conditions of Cd_xHg_1−xTe growth, these ratios for Ga and In were 1.5–2.0 and 1.0–1.5, respectively. The electrical activity of Ga and In was determined after annealing of the Cd_xHg_1−xTe layers in saturated Hg vapor at 270–300°C. In doping of the epitaxial layers to (3–8)×10¹⁴ cm⁻³ with subsequent annealing in saturated Hg vapor at ∼270°C increases the carrier lifetime approximately by a factor of two as compared with the undoped material annealed under the same conditions.     

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.     

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.     

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.     

Growth method,composition, and defect structure dependence of mercury diffusion in CdxHg1–xTe

Mercury radiotracer diffusion results are presented, in the range 254 to 452°C, for bulk and epitaxial Cd_xHg_1–xTe, and we believe this to be the first report for metalorganic vapor phase epitaxy (MOVPE) grown Cd_xHg_1–xTe. For all growth types studied, with compositions of x_Cd=0.2±0.04, the variation of the lattice diffusion coefficient, D_Hg, with temperature, under saturated mercury partial pressure, obeyed the equation: D_Hg=3×10⁻³ exp(−1.2 eV/kT) cm² s⁻¹. It was found to have a strong composition dependence but was insensitive to changes of substrate material or crystal orientation. Autoradiography was used to show that mercury also exploited defect structure to diffuse rapidly from the surface. Dislocation diffusion analysis is used to model defect tails in MOVPE Cd_xHg_1–xTe profiles.     

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.     

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 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.     

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.     

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.     

Observation of prevalence of quasi-equilibrium in the MBE growth of Hg1−xCdxTe

MBE growth of Hg_1−xCd_xTe has been carried out at 185°C. Parameters of growth have systematically varied. The resulting compositional changes and the electrical characteristics have been explained on the basis of the prevalence of quasi-equilibrium at the growth temperature.     

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.     

Influence of Cadmium Composition on CH4–H2-Based Inductively Coupled Plasma Etching of Hg1?xCdxTe

In this paper, inductively coupled plasma etching of Hg_1−x Cd _x Te in CH₄–H₂-based chemistry is studied. This work is focused on the effects of substrate temperature, ion energy, and alloy composition on etch rate and surface composition. A strong influence of substrate temperature is shown. The etch rate is multiplied by more than a factor of 3 when the temperature is increased from 5°C to 35°C. A purely physical Cd removal mechanism is ruled out using x-ray photoelectron spectroscopy data from samples etched at different temperatures. Under the conditions of very low ion energy, an etching mechanism limited by the supply of active species from the plasma predicts an Hg_1−x Cd _x Te etch rate evolution that fits very well with our data.     

Critical thickness in the HgCdTe/CdZnTe system

We present an analysis of the critical thickness of Hg_1−xCd_xTe on Cd_1−yZn_yTe substrates as a function of x and y and show that a very tight control of the substrate composition is needed to produce dislocation-free epi-layers. Hg_1−xCd_xTe layers on relaxed underlayers of different compositions of Hg are also examined.     

Vapor phase equilibria in the Cd1−xZnxTe alloy system

Cd_1−xZn_xTe compounds of different compositions have been prepared at temperatures ranging from 400 to 1000°C by annealing elemental Te in sealed quartz ampoules, in an atmosphere comprising vapors of Cd and Zn whose partial pressures were varied by varying the composition of the binary Cd_1−yZn_y alloys which provided the Cd and Zn vapors in these annealing experiments. The chemical compositions of the resulting Cd_1−xZn_xTe compounds have been analyzed using electron probe microanalytical techniques. Results indicate that presence of a 0.5%Zn along with Cd in a closed or semi-closed system may prove to be beneficial in preventing decomposition and/or formation of a metal/non metal phase during annealing of Cd_0.96Zn_0.04 Te substrates. Using the thermodynamic data in the literature for the binary Cd_1−yZn_y alloys and with the assumption that the activities of the Cd and Zn components are weakly dependent on temperature, the partial pressures of Cd and Zn in equilibrium with the Cd_1−xZn_xTe compounds at various temperatures have been evaluated.     

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.     

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.     

MBE growth and characterization of in situ arsenic doped HgCdTe

We report the results of in situ arsenic doping by molecular beam epitaxy using an elemental arsenic source. Single Hg_1−xCd_xTe layers of x ∼0.3 were grown at a lower growth temperature of 175°C to increase the arsenic incorporation into the layers. Layers grown at 175°C have shown typical etch pit densities of 2E6 with achievable densities as low as 7E4cm⁻². Void defect densities can routinely be achieved at levels below 1000 cm⁻². Double crystal x-ray diffraction rocking curves exhibit typical full width at half-maximum values of 23 arcsec indicating high structural quality. Arsenic incorporation into the HgCdTe layers was confirmed using secondary ion mass spectrometry. Isothermal annealing of HgCdTe:As layers at temperatures of either 436 or 300°C results in activation of the arsenic at concentrations ranging from 2E16 to 2E18 cm⁻³. Theoretical fits to variable temperature Hall measurements indicate that layers are not compensated, with near 100% activation after isothermal anneals at 436 or 300°C. Arsenic activation energies and 77K minority carrier lifetime measurements are consistent with published literature values. SIMS analyses of annealed arsenic doping profiles confirm a low arsenic diffusion coefficient.     

Annealing studies of undoped Hg1−xMnx Te bulk crystals at high temperatures

The effect of high temperature annealing treatments in varying mercury atmospheres on Hg_1−xMn_xTe crystals with long wavelength infrared/very long wavelength infrared cut off wavelengths has been studied. The undoped Hg_1−xMn_xTe crystals were grown using the traveling heater method with a tellurium solvent zone, and composition was verified by infrared transmission measurements. The crystals were subjected to annealing temperatures of 500 and 550°C under mercury pressures varying from Hg-rich conditions to Te-rich conditions. The samples were either air cooled or water cooled to room temperature. Hall effect measurements were carried out at 77K at magnetic fields varying from 500 Gauss to 10 kGauss. The hole concentration in the annealed crystals was found to be roughly inversely proportional to the partial pressure of Hg indicating that the material is essentially intrinsic at the anneal temperature. A defect model and a relationship between the mass action constants for the native acceptor defects of HgMnTe are presented.