Band anticrossing in highly mismatched group II-VI semiconductor alloys

We have successfully synthesized highly mismatched Cd_1−yMn_yO_xTe_1−x alloys by high-dose implantation of O ions into Cd_1−yMn_yTe crystals. In crystals with y>0.02, incorporation of O causes a large decrease in the bandgap. The bandgap reduction increases with y; the largest value observed is 190 meV in O⁺-implanted Cd_0.38Mn_0.62Te. The results are consistent with the band anticrossing (BAC) model, which predicts that a repulsive interaction between localized states of O located above the conduction-band edge and the extended states of the conduction band causes the bandgap reduction. A best fit of the measured bandgap energies of the O-ion-synthesized Cd_1−yMn_yO_xTe_1−x alloys using the BAC model for y<0.55 suggests an activation efficiency of only ∼5% for implanted O in Cd_1−yMn_yTe.     

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.     

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)     

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.     

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.     

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.     

Surface-barrier structures on single crystals of CdMgMnTe quaternary solid solutions: Creation and properties

Planar melt crystallization is used to grow single crystals of Cd-Mg-Mn-Te quaternary alloys along the pseudobinary sections Cd_{0.75 − x} Mg _x Mn_0.25Te, Cd_{0.75 − x} Mg_0.25Mn _x Te, and Cd_{1 − 2x} Mg _x Mn _x Te. The first photosensitive structures, i.e., In/CdMgMnTe Schottky barriers, are fabricated within each indicated single-crystal section. The spectral dependences of the relative quantum efficiency of photoconversion are measured, and the broadband photosensitivity of the new structures is detected. Based on the spectral dependences of the photosensitivity, the nature of the meson transitions is discussed and the corresponding band gaps are determined. The applicability of grown single crystals of CdMgMnTe quaternary alloys to broadband photoconverters of optical radiations is ascertained.     

Observation of lasing from Cr2+:CdTe and compositional effects in Cr2+-doped II-VI semiconductors

We are engaged in a systematic study of the optical and laser properties of Cr²⁺-doped cadmium chalcogenides. Previously, we demonstrated quasi-continuous wave lasing from Cr²⁺-doped Cd_0.55Mn_0.45Te with slope efficiencies as high as 64% and a laser tuning range from 2,170–3,010 nm. In this paper, we report the first demonstration of lasing from Cr:CdTe at room temperature. Pulsed-laser operation was obtained with a free-running spectrum centered at 2,535 nm. The slope efficiency of the laser was low (∼1%) because of large parasitic losses at the laser wavelength. The spectroscopic properties of Cr:CdTe are favorable for laser applications because of a large emission cross section (∼2.5 × 10⁻¹⁸ cm²) and a high emission-quantum yield (∼88%). In addition, CdTe can easily incorporate Cr ions either through melt growth or diffusion doping. Along with our results on Cr²⁺:CdTe, we report on the optical properties of several other Cr²⁺-doped II-VI semiconductors (ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, Cd_0.9Zn_0.1Te, Cd_0.65Mg_0.35Te, Cd_0.85Mn_0.15Te, and Cd_0.55Mn_0.45Te) and compare them for applications as solid-state laser materials.     

Transition metal doped cadmium manganese telluride: A new material for tunable mid-infrared lasing

Relatively new materials for mid-infrared tunable lasing using chromium-doped Cd_1-xMn_xTe and cobalt-doped Cd_1-xMn_xTe have been developed. Previously, ZnS and ZnSe were used as host materials for chromium to produce mid-infrared (MIR) lasing. Compared to these materials, large diameter CdMnTe is easier to grow (using the Bridgman technique) and can be made more homogeneous. Moreover, the ternary nature of Cd_1-xMn_xTe offers the unique opportunity to optimize the optical properties of the material through variation of chemical composition and lattice parameter. Using Cd_0.55Mn_0.45Te:Cr, we have demonstrated room temperature lasing from 2.1 to 3.0 m, and we have demonstrated quasi-continuous wave (cw) lasing. To our knowledge, the observed tuning range (∼840 nm) of Cr²⁺:Cd_0.55Mn_0.45Te is the largest ever reported from a transition metal ion laser. Furthermore, this is the first time that a room temperature quasi-cw laser operating at 3 m has been demonstrated using this type of material. Also, preliminary work on Cd_0.55Mn_0.45Te:Co indicates its potential for tunable mid-infrared lasing around 3600 nm at cryogenic temperatures. Results from inductively coupled plasma mass spectrometry (ICP-MS), which determine the concentration of dopant that has been incorporated in to the host lattice, will be reported, as will the materials characterization and lasing results. The processing issues for optimizing the laser performance in these material systems will also be discussed.     

Ferromagnetism in diluted Pb1 ? x ? y Ge x Cr y Te magnetic semiconductors

Magnetic properties of Pb_{1 − x − y} Ge _x Cr _y Te alloys (x = 0.02–0.20, y = 0.01–0.08) were studied. It was detected that the magnetic susceptibility of alloys consists of two contributions: the paramagnetic Curie-Weiss part (the temperature region is T < 50 K) caused, probably, by the Cr³⁺ ion paramagnetism, and the high-temperature ferromagnetic part (T < 300 K). The dependences of the concentration of magnetic centers on the composition of the matrix were obtained from the paramagnetic and ferromagnetic contributions. It was shown that a decrease in the concentration of paramagnetic centers can be, at least qualitatively, explained by the transformation of the electronic structure as the germanium concentration increases. A phenomenological model was suggested, which explains the behavior of magnetic properties as the chromium content increases, and possible mechanisms of ferromagnetic ordering in studied alloys are discussed. Original Russian Text ? E.P. Skipetrov, M.G. Mikheev, F.A. Pakpour, L.A. Skipetrova, N.A. Pichugin, E.I. Slyn’ko, V.E. Slyn’ko, 2009, published in Fizika i Tekhnika Poluprovodnikov, 2009, Vol. 43, No. 3, pp. 316–323.     

Vanadium-Doped Cadmium Manganese Telluride (Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te) Crystals as X- and Gamma-Ray Detectors

CdMnTe offers several potential advantages over CdZnTe as a room- temperature gamma-ray detector, but many drawbacks in its growth process impede the production of large, defect-free single crystals with high electrical resistivity and high electron lifetimes. Here, we report our findings of the defects in several vanadium-doped as-grown as well as annealed Cd_1−x Mn _x Te crystals, using etch pit techniques. We carefully selected single crystals from the raw wafer to fabricate and test as a gamma-ray detector. We describe the quality of the processed Cd_1−x Mn _x Te surfaces, and compare them with similarly treated CdZnTe crystals. We discuss the characterization experiments aimed at clarifying the electrical properties of fabricated detectors, and evaluate their performance as gamma-ray spectrometers.     

Effect of Hydrogen Free Radicals on Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te

The effects of atomic hydrogen (H) and Br/methanol etching on Hg_1−x Cd _x Te films were investigated using x-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Exposure of an as-received Hg_1−x Cd _x Te sample to H + H₂ resulted in H-induced TeO₂ reduction. The oxide reduction was first order with respect to H + H₂ exposure. Exposure to H + H₂ after etching the Hg_1−x Cd _x Te film in a Br/methanol solution induced Hg and C depletion. Hg and C removal was also observed after completely reducing the TeO₂ on the as-received sample. The removal process was hindered by the formation of a Cd-rich overlayer on both etched and unetched surfaces.     

Transport and Thermoelectric Properties of the Ca1?xSrxRu1?yMnyO3 System

The magnetic, transport, and thermoelectric properties of Ca_1−x Sr _x Ru_1−y Mn _y O₃ have been investigated. Ferromagnetism with relatively high T _C (>200 K) was introduced by Mn doping. In particular, ferromagnetism appeared in the Ca_0.5Sr_0.5Ru_1−y Mn _y O₃ system at y > 0.2. The maximum T _C (=270 K) was recorded for a specimen of Ca_0.5Sr_0.5Ru_0.4Mn_0.6O₃. The ferromagnetism seems to be due to the mixed-valence states of Mn³⁺, Mn⁴⁺, Ru⁴⁺, and Ru⁵⁺ ions. The metallic character of Ru-rich specimens was suppressed by Mn substitution, and the system was transformed into a semiconductor at relatively low Mn content near y = 0.1. Specimens with higher Mn content (y > 0.8) had large thermoelectric power (50 μV K⁻¹ to 130 μV K⁻¹ at 280 K) accompanied by relatively low resistivity (0.03 Ω cm to 1 Ω cm). The Ca_0.5Sr_0.5Ru_1−y Mn _y O₃ system seems to have good potential as a thermoelectric material for use above 300 K.     

A study of polycrystalline Cd(Zn,Mn)Te/Cds films and interfaces

Polycrystalline films of Cd_1-x Zn _x Te (x = 0–0.4) and Cd_1-x Mn _x Te (x = 0–0.25) were grown by MBE and MOCVD, respectively, on CdS/SnO₂/glass substrates to investigate their feasibility for solar cell applications. The compositional uniformity and interface quality of the films were analyzed by x-ray diffraction, surface photovoltage, and Auger depth profile measurements to establish a correlation between growth conditions and lattice constant, atomic concentration, and bandgap of the ternary films. MBE-grown polycrystalline Cd_1-x Zn _x Te films showed a linear dependence between Zn/(Cd + Zn) beam flux ratio, Zn concentration in the film, and the bandgap. Polycrystalline Cd_1-x Zn _x Te films grown at 300° C showed good compositional uniformity in contrast to compositionally non-uniform Cd_1-x Mn _x Te films grown by MOCVD in the temperature range of 420–450° C. The MBE-grown Cd_1-x Zn _x Te interface also showed significantly less interdiffusion compared to the MOCVD-grown Cd_1-x Mn _x Te/CdS interface, where preferential exchange between Cd from the CdS layer and Mn from the Cd_1-x Mn _x Te film was observed. The compositional uniformity of MOCVD-grown polycrystalline Cd_1-x Mn _x Te films grown on CdS/SnO₂/glass substrates was found to be a strong function of the growth conditions as well as the Mn source.     

Thermoelectric Characteristics in MBE-Grown HgCdTe-Based Superlattices

We present a study on the thermoelectric properties of n-type Hg_0.75Cd_0.25 Te/Hg_0.7Cd_0.3Te superlattices (SLs). This material system was chosen because HgCdTe is the primary material used in high-performance infrared imaging applications. HgCdTe-based devices can be directly grown on Hg_1−x Cd _x Te/Hg_1−y Cd _y Te SL coolers using advanced growth methods such as molecular-beam epitaxy (MBE), making the monolithic integration of infrared sensors and thermoelectric elements possible. Also, the thermoelectric figure of merit ZT for Hg_0.75Cd_0.25Te/Hg_0.7Cd_0.3Te SLs is predicted to reach values of 2.09, more than two times greater than that achieved in the best thermoelectric devices based on bulk Bi₂Te₃. This large ZT is due to the unique and superior electrical and thermal properties of the HgCdTe system, which has not yet been experimentally explored in any great depth as a thermoelectric material. We used a Riber 32P MBE system equipped with a Hg valved cell, reflection high-energy electron diffraction, infrared pyrometer and in situ spectroscopic ellipsometry to grow the thermoelectric structures. MBE was chosen as a growth technique since it allows for the lowest growth temperature compared with other methods, which limits interdiffusion at the interfaces, thereby allowing for a precise control over electrical and thermal properties. Thermal devices were fabricated using standard photolithography and etching techniques. Thermal properties were evaluated using a differential technique. A thermal conductivity of 0.82 ± 0.07 W/m K and a Seebeck coefficient of 811 ± 150 μV/K were measured. Using a measured value of 0.017 Ω cm for the resistivity, an upper bound ZT of 1.4 is estimated. An erratum to this article can be found at     

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.     

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.     

Distinctive features of the far-infrared reflection spectra of the semimagnetic semiconductors Hg1−x MnxTe1−y Sey

Reflection spectra of single crystals of Hg_1−x Mn_xTe_1−y Se_y (0.01<x<0.14, y=0.01) in the far-infrared range (10–600 cm⁻¹) are investigated at 300 and 77 K. A series of new phonon modes is observed, in addition to the longitudinal and transverse modes corresponding to the ternary compounds. Fiz. Tekh. Poluprovodn. 32, 546–548 (May 1998)     

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.     

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.