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)     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Evaluation of Mn Uniformity in CdMnTe Crystal Grown by the Vertical Bridgman Method

Cd_1−x Mn _x Te is a typical diluted magnetic semiconductor, as well as substrate for the epitaxial growth of Hg_1−x Cd _x Te. In this paper, the homogeneity of a Cd_1−x Mn _x Te (x = 0.2) single-crystal ingot grown by the vertical Bridgman method was studied. The crystal structure and quality of the as-grown ingot were evaluated. Near-infrared (NIR) transmission spectroscopy was adopted to develop a simple optical determination of the Mn concentration in the as-grown ingot. A correlation equation between cut-off wavelength λ _co from NIR transmission spectra and Mn concentration by inductively coupled plasma atomic emission spectrometry (ICP-AES) was established. Using this equation, we investigated the Mn concentration distribution in both the axial and radial directions of the ingot. It was found that the segregation coefficient of Mn in the axial direction of the ingot was 0.95, which is close to unity. The Mn concentration variation in the wafers from the middle part of the ingot was 0.001 mole fraction. All these results proved that homogeneous Cd_0.8Mn_0.2Te crystals can be grown from the vertical Bridgman method.     

Far infrared characterization of Hg1-xCdxTe and related electronic materials

Far infrared (10 to 250 cm⁻¹) reflection and transmission spectroscopy is used to characterize the free-carrier and alloy properties of the leading infrared detector material Hg_1-xCd_xTe and the substrate materials CdTe and CdZnTe. The data yield values for carrier concentration and mobility, the compositional parameter x and film thickness which generally agree with other determinations. The advantages of this contactless nondestructive technique are described. Applications to the newly proposed infrared detector material Hg_1-xMn_xTe are briefly reviewed.     

Temperature dependence of the optical properties of Hg1−xCdxTe

The alloy composition of Hg_1−xCd_xTe should be controlled during growth, so that the desired band gap and the lattice-matched layer may be obtained. In-situ spectroscopic ellipsometry, now commercially available, enables one to acquire spectral data during growth. If one knows the optical dielectric function as a function of alloy composition and temperature, the technique can be fully used to monitor and control temperature, the thickness, and the alloy composition. For this purpose, we first obtained temperature dependent spectral data of Hg_1−xCd_xTe by spectroscopic ellipsometry (SE). The spectral data of Hg_1−xCd_xTe with x = 1,0.235, and 0.344 were obtained from room temperature to 800Kin the photon energy range from 1.3 to 6 eV. The spectral data revealed distinctive critical point structures at E₀, E₀+Δ₀, E₁, E₁+Δ₁, E₂(X), and E₂(Σ). Critical point energies decreased and linewidths increased monotonically as temperature increased. The model for the optical dielectric function enabled (i) the critical point parameters to be determined accurately, and (ii) the spectral data to be expressed as a function of temperature within and outside the experimental range.     

Growth of HgTe Quantum Wells for IR to THz Detectors

We zone-engineered HgCdTe/HgTe/HgCdTe quantum wells (QWs) using the molecular-beam epitaxy (MBE) method with in situ high-precision ellipsometric control of composition and thickness. The variations of ellipsometric parameters in the ψ–Δ plane were represented by smooth broken curves during HgTe QW growth with abrupt composition changes. The form of the spiral fragments and their extensions from fracture to fracture revealed the growing layer composition and its thickness. Single and multiple (up to 30) Cd _x Hg_1−x Te/HgTe/Cd _x Hg_1−x Te QWs with abrupt changes of composition were grown reproducibly on (013) GaAs substrates. HgTe thickness was in the range of 16 nm to 22 nm, with the central portion of Cd _x Hg_1−x Te spacers doped by In to a concentration of 10¹⁴ cm⁻³ to 10¹⁷ cm⁻³. Based on this research, high-quality (013)-grown HgTe QW structures can be used for all-electric detection of radiation ellipticity in a wide spectral range, from far-infrared (terahertz radiation) to mid-infrared wavelengths. Detection was demonstrated for various low-power continuous-wave (CW) lasers and high-power THz pulsed laser systems.     

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.     

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.     

HgCdTe heteroepitaxy on three-inch (112) CdZnTe/Si: Ellipsometric control of substrate temperature

The technique of spectroscopic ellipsometry (SE) has been utilized to monitor in real-time and precisely control the surface temperature of Hg_1−xCd_xTe during molecular beam epitaxy. Due to the temperature dependence of the Hg sticking coefficient under Hg-deficient growth conditions, the near-surface composition of an epilayer is extremely sensitive to surface temperature. SE data were acquired in real time and modeled using a previously established library of dielectric functions of Hg_1−xCd_xTe as a function of composition. Utilizing SE-generated compositional profiles as a guide, substrate heating power was adjusted in such a way as to minimize composition transients. To demonstrate the effectiveness of the technique, we have used SE to control the temperature of HgCdTe epilayer surfaces during deposition on three-inch (211)CdZnTe/ZnTe/Si composite substrates mounted on indium free holders.     

Supercooling studies and LPE growth of Hg1−xCdxTe from Te-Rich solutions

Hg_1-xCd_xTe liquid phase epitaxial (LPE) layers were grown from well-stirred large (100 g) Te-rich Hg-Cd-Te solutions by the dipping method. Supercooling below the liquidus temperature in Te-rich solutions was studied by differential thermal analysis (DTA) and film growth results. Although supercooling of 20 to more than 100° C was routinely measured in small (2 g) sample melts, supercooling in larger melts (>100 g) was erratic and smaller. Factors affecting the degree of supercooling were identified and a Hg-reflux was found to be a major cause of erratic melt behavior. The LPE reactor was modified to correct the Hg-reflux action and a visual technique was developed for in situ determination of the liquidus temperature. A limited amount of supercooling was found in the melt after reactor modification but it was difficult to maintain for extended durations before spontaneous nucleation occurred. Consequently, programmed cooling rather than isothermal LPE was employed to grow many of the films reported here. Hg_1−xCd_xTe epitaxial layers ofx = 0.2 to 0.25 were grown on (111)B oriented CdTe substrates by cooling the melts only 1–2° C below the previously measured crystallization temperature. The small amount of cooling minimized composition variation with film thickness. Excellent surface morphology was obtained when slow cooling rates of 0.02–0.05° C/ min were used. Cooling rates greater than 0.2° C/min created rough, pitted surface. Precise substrate orientation was important in reducing surface terracing. Composition and thickness uniformities of the epitaxial films were excellent as a result of substrate rotation. Run-to-run reproducibility of film composition was ±0.01 inx. Hall measurements showed carrier concentrations in the range 2–20 × 10¹⁴ cm⁻³ with photoconductive lifetimes of 0.5–3.0 dms forx = 0.20 to 0.25.     

Solid solution InxGa1−x AsySbzP1−y−z : A new material for infrared optoelectronics. I. Thermodynamic analysis of the conditions for obtaining solid solutions, isoperiodic to InAs and GaSb substrates, by liquid-phase epitaxy

The diagrams of melt-solid solution (fusibility curves) and solid solution (I)-solid solution (II) (surfaces of spinodal decomposition of solid solutions) phase equilibria in the five-component system In-Ga-As-Sb-P (the solid solutions are isoperiodic to the GaSb and InAs substrates) are calculated. The concentration ranges of the isovalent substitution solid solutions In_xGa_1−x As_ySb_zP_1−y−z , which are accessible for synthesis by liquid-phase epitaxy, are calculated. Fiz. Tekh. Poluprovodn. 31, 410–415 (April 1997)     

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.