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.     

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.     

Substitutional-interstitial silver diffusion and drift in bulk (cadmium,mercury) telluride: Results and mechanistic implications

The diffusion and electromigration of Ag in crystals of Cd_xHg_1-xTe is studied, as a function of original doping level and of the concentration of mercury. In materials with x = 0.55-0.8, Ag dopes p-type, when diffusing in at <125°C. This should be contrasted to what is found in n-CdTe, where in-diffusion of Ag at 200°C increases the net donor density, leaving the material n-type. Our results show that the higher is the mercury content or the hole concentration in Cd_xHg_1-xTe (x = 0.55-0.8), the faster Ag will diffuse in these materials. We explain our results, building on earlier suggestions made for Hg-rich materials, by assuming that silver diffuses by way of a substitutional-interstitial mechanism; i.e., it is present as two species with opposite charge, one of which dominates and is practically immobile, while the minority species diffuses rapidly. These forms equilibrate, at room temperature, within a few seconds, something that can be understood by postulating silver-mercury complex formation. If both forms of silver are bound to mercury, then this hypothesis explains the strong influence of mercury content on the diffusion behavior.     

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.     

Study of CdSSe:V and CdMnTe:V photorefractive effect

A large photorefractive effect was measured in CdS_0.8Se_0.2:V and Cd_0.55Mn_0.45Te:V ternary crystals which shows promise for many device applications such as optical signal processing and optical limiting. In this study, we compared the results obtained from two-wave mixing experiments with Cd_0.55Mn_0.45Te:V and CdS_0.8Se_0.2:V crystals at the 633 nm wavelength. As the signal to pump beam ratio was varied from 10⁻¹ to 10⁻⁴, Cd_0.55MN_0.45Te:V and CdS_0.8Se_0.2:V showed a maximum photorefractive gain of 0.17 and 0.20 cm⁻¹, respectively. The grating formation time of both the crystals were measured to be in the milli-second range at an incident intensity of 200 mW/cm².     

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.     

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.     

Large area depositon of Cd1-xZnxTe on GaAs and Si substrates by metalorganic chemical vapor deposition

Results of large-area (up to 1000 cm²/run) Cd_1-xZn_xTe heteroepitaxy on both GaAs and GaAs/Si substrates by metalorganic chemical vapor deposition (MOCVD) are presented. Cd_1-xZn_xTe (x = 0-0.1) films exhibited specular surface morphology, 1% thickness uniformity (standard deviation), and compositional uniformity (Δx) of ±0.002 over 100 mm diam substrates. For selected substrate orientations and deposition conditions, the only planar defects exhibited by (lll)B Cd_1-xZn_xTe/GaAs/Si films were lamella twins parallel to the CdTe/GaAs interface; these do not propagate through either the Cd_1-xZn_xTe layer or subsequently deposited liquid phase epitaxy (LPE) HgCdTe layer(s). Background Ga and As-impurity levels for Cd_1-xZn_xTe on GaAs/Si substrates were below the secondary ion mass spectroscopy detection limit. Preliminary results of HgCdTe liquid phase epitaxy using a Te-rich melt on Si-based substrates resulted in x-ray rocking curve linewidths as narrow as 72 arc-sec and etch-pit densities in the range 1 to 3 x 10⁶ cm².     

Slider LPE of Hg1-xCdxTe using mercury pressure controlled growth solutions

Homogeneous, nearly perfect single crystals of Hg_1-xCd_xTe are extremely difficult to prepare due primarily to the high vapor pressure of mercury. However, epitaxially grown Hg_1-xCd_xTe layers have a high potential for yielding material of a substantially higher quality. Using a new, open-tube, horizontal slider-type liquid phase epitaxial (LPE) growth technique, in which mercury pressure controlled growth solutions are used, a high degree of growth solution compositional control has been demonstrated. LPE layers of Hg_1-xCd_xTe have been grown on CdTe substrates and their high quality has been confirmed by optical, transport and electron microprobe measurements. Layer thicknesses are uniform and have been varied from 5 to 40 μ by changing the degree of supercooling or the growth time. An electron carrier concentration as low as 8.6 × 10¹⁵/cm³ and electron Hall mobilities up to 2.8 × 105 cm²/V-sec at 77K have been measured on in situ annealed samples. This work was sponsored by the Department of the Air Force and the U.S. Army Research Office.     

Relaxation processes in conductivity of Cd1 − x Mn x Te crystals (0.02 < x < 0.55)

The results of studying the temperature dependences of resistivity and the Hall coefficient in crystals of Cd_{1 ? x} Mn _x Te alloys (0.02 < x < 0.55) are used to gain insight into the conductivity relaxation processes observed in the temperature range 200–420 K in Cd_{1 ? x} Mn _x Te crystals with the manganese content x > 0.06. An anomalous isothermal variation in the hole concentration by an amount from half to three orders of magnitude occurs in these crystals. It is shown that relaxation of resistivity in the crystals under consideration can be provided by quasi-chemical reactions with involvement of uncontrolled Cu impurity and defects of CdTe crystal structure.     

Optical band gap of Cd1−x MnxTe and Zn1−x MnxTe semiconductors

The dependence of the optical band gap for Zn_1?x Mn_xTe and Cd_1?x Mn_xTe semiconductor compounds was investigated by the methods of cathodoluminescence and optical reflection. It was found that, for Zn_1?x Mn_xTe compounds in the region x?0.2, the band gap is additionally broadened by a magnitude of about 0.08 eV, which is related to the high density of interstitial-type defects in single crystals. For x?0.3, the probability of the existence of these defects decreases substantially, which is related to the distortion of tetrahedra of the crystal lattice of Zn_1?x Mn_xTe by Mn atoms, which are incorporated into each tetrahedron.     

Single crystal growth of Hg1-xCdxTe

It has been found that single crystals of Hg_1-xCd_xTe with volumes of about 3 cm³ can be obtained using a new method for crystal growth. Experimental details of the new technique as applied to Hg_1-xCd_xTe are discussed. Single crystal growth mechanisms are proposed which involve crystallization from a two-phase mixture followed by recrystallization of the solid. Evidence for the unusually high quality material is obtained from electron-beam microprobe analyses, electrical properties, and magneto-optical spectra. This work was sponsored by the Department of the Air Force.     

The temperature-composition phase diagram and the miscibility gap of Hg1-xCdxTe solid solutions by dynamic mass-loss measurements

The dynamic mass-loss technique has been employed to measure Hg partial pressures over Te-saturated Hg_1-xCd_xTe solid solutions with x = 0.40, 0.54, and 0.70 in the 10^-1 to 10^-4 atm range. The relative chemical potentials of HgTe in Hg_1-xCd_xTe solid solutions have been calculated using the measured Hg partial pressures at temperatures below 413°C, and fitted into an analytical expression. A Gibbs-Duhem integration yielded the relative chemical potentials of CdTe. By combining the relative chemical potentials of the binary components HgTe and CdTe, an expression for the Gibbs free energy of mixing was derived. The binodal (miscibility gap) and spinodal curves of the Hg_1-xCd_xTe solid solutions have been established with the critical temperature and composition of 221°C and Hg_0.40Cd_0.60Te.     

Lead-europium-selenide-telluride grown by molecular beam epitaxy

The band gap of lead-europium-telluride (Pb_1-x Eu_xTe) was determined from room temperature optical absorption measurements and increases as dEg/dx = 3.5 eV for x ≤ 0.044. Eu atoms bond strongly to a PbTe surface during MBE growth and have a small diffusion coefficient (<1 x 10⁻¹⁶ cm /sec at 370°C). The lattice constant of Pb_1-x, Eu_x Te is a nonlinear function of composition, and lattice-matched growth of Pb_1-x Eu_x Se_y Te_1-y, on PbTe is demonstrated. Preliminary studies of the electrical properties of Pb_1-x Eu_x Te indicate compensation of n-type (Bi) and p-type (Tl) dopants. These results indicate that Pb_1-x Eu_x Se_y Te_1-y, may be useful for obtaining diode lasers which emit at wavelengths shorter than those available from Pb_1-x, Sn_x Te.     

Passivation of Hg1-xCdxTe by photochemical native oxidation: Quantitative analysis of oxide composition

The composition of photochemically grown native oxides on Hg_1-xCd_xTe (x = 0.3) has been analyzed and depth profiled using x-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy. The oxide films were grown in either N₂O or O₂ ambients, and differences in the oxidation process were examined by varying the time and temperature of oxide growth. Under all growth conditions, oxides grown in an O₂ ambient exhibited a higher Hg concentration in the bulk oxide region when compared to N₂O grown oxides. The Hg/Te ratio of all the oxides was found to be less than the starting Hg_1-xCd_xTe substrates and, in some cases, this may be leading to an accumulation of Hg in the oxide/Hg_1-xCd_xTe interface region. For growths at higher temperatures (∼75°C), the excess Hg was seen to move from the oxide/Hg_1-xCd_xTe interface region to the oxide surface. In O₂ ambients, the Hg accumulated at the surface of the oxide whereas for growths in N₂O, it was lost to the ambient. Previous results on photochemical oxidation of Hg_1-xCd_xTe show an inverse relationship between oxide growth rate and temperature. Evidence obtained in this study from oxide compositions, depth profiles and annealing at higher temperatures, suggest that this relationship between oxide growth rate and temperature is primarily due to temperature induced differences in the oxidizing ambient, and not the result of a change in the film growth mechanism due to changing diffusion characteristics with temperature.     

Compositional dependence of infrared phonon parameters for Hg1-xCdxTe

The full set of Lorentzian oscillator parameters describing the two-mode phonon behavior in Hg_1-x-jCd_xTe is reported. A new analysis of reflectivity spectra combined with existing results gives the most accurate available values for the CdTe-like and HgTe-like transverse optical frequency, strength and (for the first time) damping constant vs CdTe fractionx at room, liquid nitrogen and liquid helium temperatures. Polynomial fits vsx for each parameter are provided for use in characterizing Hg_1-xCd_xTe and the HgTe-CdTe superlattice.     

碲镉汞红外探测器性能调控技术研究

对影响Hg_1-xCd_xTe红外探测器性能的不同调控技术——包括材料调控(组分及温度、掺杂浓度、压强及应力等对材料性能的调控)、器件结构调控(n-on-p、p-on-n、p-i-n、n-B-n等器件结构的调控)和工艺调控(各种工艺调控对材料制备和器件制备等的影响)等——进行了简单介绍,以合理调控器件性能、有效降低器件暗电流、提高器件工作温度等,从而促进Hg_1-xCd_xTe红外探测器在降低成本、减小功耗、提高可靠性等方面的发展。     

Multi-Mode behavior of optical phonons in II-VI ternary and quaternary alloys

Zone-center optical phonons of tetrahedrally coordinatedII-VI semiconductor ternary (AB_1-xC_x) and quaternary (AB_1-x-yC_xD_y) alloys display a variety of distinct multi-mode behavior patterns. A brief review of the modified random element isodisplacement model, which can satisfactorily account for the composition dependence of the frequencies of the zone-center optical phonons, is presented; in this model, one uses the macroscopic parameters of the binary end members and their LO-TO phonon frequencies. When a constituent is present in extreme dilution in a binary (or in a ternary), e.g., C in AB (or in AB_1-y D_y), one sees either a local or a gap mode associated with it. For higher concentrations, one can see two (three) LO-TO phonon pairs for the ternary (quaternary) in the first order Raman spectrum or in the infra-red deduced from an analysis of the reststrahlen bands, when the masses of B and C differ significantly but are lighter than that of A. We illustrate these features in the Raman spectra of Cd_1-xMg_xTe and Cd_1-x-y Mg_xMn_yTe. Also shown are the infra-red spectra of the local mode of Mg²⁺ and Mn²⁺ in Cd Te, where their isotopic nature is clearly manifested.     

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.