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.     

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.     

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.     

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.     

Molecular beam epitaxy of CdTe and Hg1-xCdxTe ON GaAs (100)

Using the molecular beam epitaxial (MBE) technique, CdTe and Hg_1-xCd_xTe have been grown on Cr-doped GaAs (100) sub-strates. A single effusion cell charged with polycrystal-line CdTe is used for the growth of CdTe films. The CdTe films grown at 200 °C with a growth rate of ~ 2 μm/hr show both streaked and “Kikuchi” patterns, indicating single crystalline CdTe films are smoothly grown on the GaAs sub-strates. A sharp emission peak is observed at near band-edge (7865 Å, 1.577 eV) in the photoluminescence spectrum at 77 K. For the growth of Hg_1-xCd_xTe films, separate sources of HgTe, Cd and Te are used. Hg_0.6Cd_0.4Te films are grown at 50 °C with a growth rate of 1.7 μm/hr. The surfaces are mirror-smooth and the interfaces between the films and the substrates are very flat and smooth. As-grown Hg_0.6Cd_0.4Te films are p-type and converted into n-type by annealing in Hg pressure. Carrier concentration and Hall mobility of an annealed Hg_0.6Cd_0.4Te film are 1 × 10¹⁷ cm^?3 and 1000 cm²/V-sec at 77 K, respectively.     

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.     

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.     

Thermodynamic stability of bulk and epitaxial CdHgTe,ZnHgTe, and MnHgTe alloys

The thermodynamic stability of Cd_1?xHg_xTe, Mn_xHg_1?xTe, and Zn_xHg_1?xTe alloys is studied. Calculations performed in the context of the δ lattice-parameter model indicate that CdHgTe and ZnHgTe alloys are stable over the entire range of compositions at typical growth temperatures. At the same time, a miscibility gap is found in Mn_xHg_1?xTe at 0.33 < x < 1 at T = 950 K, which is consistent with the known experimental data. It is shown that the biaxial strains observed in Mn_xHg_1?xTe/CdTe and Mn_xHg_1?xTe/Cd_0.96Zn_0.04Te thin epitaxial films lead to a narrowing of the miscibility gap and to insignificant lowering of critical temperatures.     

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。     

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.     

Accurate Simulation of Temperature-Dependent Dark Current in HgCdTe Infrared Detectors Assisted by Analytical Modeling

Resistance–voltage curves of n ⁺-on-p Hg_1−x Cd _x Te infrared photodiodes were measured in the temperature range of 60 K to 120 K. Characteristics obtained experimentally were fitted by an improved simultaneous-mode nonlinear fitting process. Based on the extracted parameters, an efficient numerical sim- ulation approach has been developed by inserting trap-assisted and band-to-band tunneling models into continuity equations as generation–recombination processes. Simulated dark-current characteristics were found to be in good agreement with the experimental data, demonstrating the validity of the nonlinear fitting process. Our work presents an efficient method for dark-current simulations over a wide range of temperatures and bias voltages, which is important for investigating mechanisms of carrier transport across the HgCdTe junction.     

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.     

Minority carrier lifetime in indium-doped HgCdTe(211)B epitaxial layers grown by molecular beam epitaxy

We have studied the minority-carrier lifetime on intentionally indium-doped (211)B molecular beam epitaxially grown Hg_1-xCd_xTe epilayers down to 80K with x ≈ 23.0% ± 2.0%. Measured lifetimes were explained by an Auger-limited band-to-band recombination process in this material even in the extrinsic temperature region. Layers show excellent electron mobilities as high as ≈2 x 10⁵ cm²v^-1s^-1 at low temperatures. When the layers are compensated with Hg vacancies, results show that the Schockley-Read recombination process becomes important in addition to the band-to-band processes. From the values of τ_n0 and τ_p0 of one sample, the obtained defect level is acceptor-like and is somewhat related to the Hg vacancies.     

Room temperature characterization of Hg1-xCdxTe P-on-n heterostructure photodiodes

Measurements of 77K R_oA and 300K reverse bias dynamic impedance (R_dA) products at one volt reverse bias has been carried out to assess the degree of correlation of this figure of merit. Planar P-on-n heterostructures were grown on near lattice-matched CdZnTe substrates with Hg_1-xCd_xTe (0.20< x <0.30) by molecular beam epitaxy. These devices were passivated with CdTe and doped with indium and arsenic as n- and p-type dopants, respectively. Current-voltage characteristic of these devices exhibit thermally generated dark currents at small and modest reverse bias. We have observed that R_oA values of these long wavelength infrared P-on-n heterostructure photodiodes at 77K correlate with room temperature R_dA values. Diode arrays with high room temperature R_dA values at one volt reverse bias also have high R_oA values at 77K. Similarly, low R_dA values at room temperature indicate poor performance at 77K where deviation from diffusion current occurs at reverse bias of 0.2 to 1 volt at room temperature. The results presented here, for a small samples of devices, demonstrate that room temperature measurements of current-voltage characteristics to evaluate Hg_1-xCd_xTe (0.22< x <0.28) diode performance and array uniformity at lower temperatures can be used. This provides an acceptable criteria for further study at lower temperatures.     

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).     

Growth by CVT and characterization of Hg1-xCdxTe epitaxial layers

Single crystal epitaxial layers of Hg_1-x Cd _x Te were grown on CdTe substrates employing the chemical vapor transport technique. Different growth temperatures, substrate orientations, and various pressures of Hgl₂ as a transport agent were used while the source materials had a fixed composition ofx = 0.2. The epilayers are of nearly uniform composition to a depth of about one-half of the layer thickness. Chemical etching of the as-grown epilayers revealed low etch pit densities in the range of 10³–10⁴ cm⁻². Rectangle-shaped etch pits are observed for the first time on the (100) oriented epilayers of this material. The growth temperature and Hgl₂ pressure used for the growth experiments have significant effects on the layer morphology and composition.     

Effects of growth conditions on the composition of CVT and PVT grown Hg1-x Cd x Te epitaxial layers

Single crystal epitaxial layers of Hg_1-x Cd _x Te were grown on CdTe substrates employing the chemical and physical vapor transport techniques. Different growth temperatures and various pressures of HgI₂ as a transport agent were used while the source materials had compositions of eitherx = 0.4 orx = 0.6. The epilayers are of nearly uniform composition to a depth of about one-half of the layer thickness. The Hgl₂ pressure and the growth temperature used for the growth experiments have significant effects on the layer composition. The desired epilayer composition ofx = 0.2 can be achieved with either source compositions by properly adjusting the HgI₂ pressure and the growth temperature.     

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.