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.     

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.     

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.     

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.     

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.     

Uniform Cr<Superscript>2+</Superscript> doping of physical vapor transport grown CdS<Subscript>x</Subscript>Se<Subscript>1−x</Subscript> crystals

The Cr²⁺ doped CdS_0.8Se_0.2 crystals were grown by the vertical, self-seeded, physical vapor transport (PVT) technique. Good quality, crack- and inclusion-free single crystals were grown with an average Cr²⁺ concentration of 5 × 10¹⁸ cm⁻³. Different source-to-tip distances were used to improve the segregation coefficient (Cr_crystal/Cr_source) of the grown crystals. It was observed that lowering the source-to-tip distance increases the segregation coefficient dramatically. With a 2-cm source-to-tip distance, good quality crystals were grown with uniform Cr²⁺ concentration throughout the ingot. The segregation coefficient was found to be ∼0.85. The composition of the crystals was also found to be fairly uniform along the length and across the diameter.     

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.     

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.     

Bulk growth of Hg0.8Cd0.2Te single crystals by a combined CVT-seeding technique

The growth of high quality Hg_0.8Cd_0.2Te bulk single crystals by CVT, combined with an in-situ seeding technique, is reported here for the first time. For this purpose, a temperature difference of 590° → 540° C with a gradient of 40°-50° C/cm at the solid-vapor interface, and about 0.1 atm of HgI₂ as a transport agent, were employed. The bulk crystals have the expected stoichiometry and compositional homogeneity. Etch pit densities of 10⁴-10⁵ cm⁻² on the (111) face and hitherto unreported etch pits on the (100) face were observed in this work. Possible origins of the sub-grain structure are discussed.     

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 and properties of Hg1-x Cdx Te epitaxial layers

The growth of epitaxial layers of mercury-cadmium-telluride (Hg_1-xCd_xTe) with relatively low x (0.2-0.3) from Te-rich solutions in an open tube sliding system is studied. The development of a semiclosed slider system with unique features permits the growth of low x material at atmospheric pressure. The quality of the films is improved by the use of Cd_1-yZ_yTe and Hg_1-xCd_xTe substrates instead of CdTe. The substrate effects and the growth procedure are discussed and a solidus line at a relatively low temperature is reported. The asgrown epitaxial layers are p-type with hole concentration of the order of 1·10¹⁷ cm⁻³, hole mobility of about 300 cm²·V⁻¹ sec⁻¹ and excess minority carrier life-time of 3 nsec, at 77 K.     

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.     

Component Overpressure Growth and Characterization of High-Resistivity CdTe Crystals for Radiation Detectors

Spectrometer-grade CdTe single crystals with resistivities higher than 10⁹ Ω cm have been grown by the modified Bridgman method using zone-refined precursor materials (Cd and Te) under a Cd overpressure. The grown CdTe crystals had good charge-transport properties (μτ _e = 2 × 10⁻³ cm² V⁻¹, μτ _h = 8 × 10⁻⁵ cm² V⁻¹) and significantly reduced Te precipitates compared with crystals grown without Cd overpressure. The crystal growth conditions for the Bridgman system were optimized by computer modeling and simulation, using modified MASTRAPP program, and applied to crystal diameters of 14 mm (0.55′′), 38 mm (1.5′′), and 76 mm (3′′). Details of the CdTe crystal growth operation, structural, electrical, and optical characterization measurements, detector fabrication, and testing using ²⁴¹Am (60 keV) and ¹³⁷Cs (662 keV) sources are presented.     

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.     

The direct determination of the vacancy concentration andP-T phase diagram of Hg0.8Cd0.2Te and Hg0.6Cd0.4Te by dynamic mass-loss measurements

A modified mass-loss measurement technique is employed, for the direct,in- situ determination of the metal vacancy formation in (Hg_1x2212;itxCd _x )_1−y Te _y (s) withx = 0.2 and 0.4. Forx = 0.2, the metal vacancy concentrations are determined between 336 and 660° C for three different compositions(y) within the homogeneity region and range from 2.4 to6.8 x 10¹⁹cm₋₃. The enthalpy of formation of a singly-ionized metal vacancy is derived to be between 0.17 and 0.45 eV depending upon the deviation from stoichiometry (compositiony). Forx= 0.4, three samples of different y-values give the metal vacancy concentrations from 1.9 to 5.5 x 10¹⁹cm⁻³ between 316 and 649° C, and the enthalpy of vacancy formation between 0.25 and 0.40 eV. Compared to the recent data on HgTe(s), these experimental results show a slight but significant decrease in the enthalpy of vacancy formation from HgTe to Hg_0.8Cd_0.2Te, which supports theoretical predictions of the bond weakening effect of Cd for the latter alloy system. Based on the simultaneously determined equilibrium Hg partial pressures within the homogeneity range, the vacancy concentration-partial pressure isotherms are constructed. The Hg partial pressures are also measured along the three-phase boundaries of the solid solutions of bothx = 0.2 and 0.4, and these are in close agreement with published data obtained by optical absorption measurements.     

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.     

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.     

N-Type Hg1−xCdxTe: Undoped x = 0.3 LPE material for sprite IR detectors

The requirement for two color Sprite detectors, with elements sensitive in the ranges 3-5 μn (MW) and 8-14 μn (LW) at 77K, is met using Hg_1−xCd_xTe elements of composition x = 0.3 and x = 0.2, respectively. The need for low defect levels for increased performance indicates the use of liquid phase epitaxy (LPE). While LW material is fairly well characterized, the growth and conversion to n-type of MW LPE has proved more difficult. Reported work shows limited data and limited success in converting MW LPE to n-type, and this primarily in donor-doped material. This paper describes the growth, annealing to n-type and characterization of Hg_0.7Cd_0.3Te. High n-type conversion yields were obtained, with low donor levels (mid-10¹³ to mid-10¹⁴ cm⁻³), high mobility (>10⁴ cm² (Vs)⁻¹) and long minority carrier lifetime (>10 us).     

Infrared transmission spectra of Cd<Subscript>1−x</Subscript>Zn<Subscript>x</Subscript>Te (x = 0.04) crystals

Three indicators (T₁₀₀₀, T₅₀₀₀, and T₁₀₀₀/T₅₀₀₀) are used to appraise the infrared (IR) transmission spectra for Cd_1−xZn_xTe (CZT) slices. By comparing the values of these three indicators, four typical types of IR spectra are characterized for CZT crystals. The CZT crystals possessing the four types of IR spectra are different in microstructures, especially the densities and sizes of Te precipitates, the free carrier concentrations, and the resistivities. Mechanisms for the elimination of tiny and dense Te precipitates are given by analyzing the variation of the IR transmittance in the range of 500–5000 cm⁻¹ during the annealing process.     

Study of the vibrational states of CdTe and CdHgTe lattices under conditions of the adsorption of ammonia and carbon dioxide

A comparative analysis of the Raman spectra of CdTe and C_d0.2Hg_0.8Te crystals stored in air, ammonia NH₃, and carbon dioxide CO₂ is performed. It is established that the chemical adsorption of gases causes deformation of the surface of the semiconductors, the signal shape of recombination luminescence varies and hidden vibrational modes of acoustic and optical phonons appear. The variation in the spectrum of lattice vibrations confirms the occurrence of the inverse absorption piezoelectric effect in A ^X B^{8 ? X} materials, particularly CdTe and Cd_0.2Hg_0.8Te.