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.     

Large improvement in HgCdTe photovoltaic detector performances at LETI

The standard infrared photovoltaic technology developed for HgCdTe by LETI and industrialized by SOFRADIR is based on the very simple approach of planar ion-implanted n-on-p homojunctions. Both the growth by liquid-phase epitaxy of excellent-quality epitaxial layers and the simplicity of the planar ion-implanted process enables state-of-the-art detectors to be achieved with a high technological yield. These detectors present high shunt impedance, good quantum efficiency, and a low l/f noise level. The diodes are diffusion-limited down to temperatures much lower than 77K. Their saturation current is limited by the minority-carrier lifetime in the p-side material. R₀A values around 30 ohm-cm² are routinely obtained for 10.0 μm cutoff wavelength detectors at 77K. In this paper, we show that with a new process we can increase the diode R₀A by more than one order of magnitude. This effect is obtained as a result of an increase of minority-carrier lifetime in the n-on-p homojunction configuration. The maximum R₀A value obtained was 655 ohm-cm² on a 10.0 μm cutoff wavelength detector at 77K. Furthermore, other figures of merit much as quantum efficiency or shunt impedance are slightly improved, and l/f noise is not affected. The data presented in the 40–200K temperature range and 9–13 μm cutoff wavelength range show that this decrease of dark current is kept throughout these temperature wavelength ranges. Therefore, we show that a simple planar ion-implanted homojunction can lead to very large R₀A, close to theoretical limits and comparable to data published for p-on-n heterojunctions.     

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).     

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.     

HgCdTe mid-wavelength IR photovoltaic detectors fabricated using plasma induced junction technology

Preliminary characterization results are presented for mid-wave infrared (MWIR) mercury cadmium telluride n-on-p photodiodes fabricated using a plasma induced type conversion junction formation technology. The diodes have been fabricated on three different vacancy doped p-type epitaxial starting materials, grown by liquid phase epitaxy (LPE) on CdZnTe, LPE on sapphire, and P/p isotype heterojunction material grown by molecular beam epitaxy (MBE) on CdZnTe. All materials had CdTe mole fraction in the active region of the device of ∼0.3. The process uses a H₂/CH₄ plasma generated in a parallel plate reactive ion etching (RIE) system to type convert the p-type material to n-type. The process is different from previously reported type conversion techniques in that it does not require a high temperature anneal, does not expose the junction at the surface to atmosphere after formation, and requires significantly fewer process steps than other planar processes. Homojunction devices fabricated using this process exhibit R₀A values >10⁷ Ω·cm² at 80 K. The R₀A is diffusion limited for temperatures >∼135 K. Results for responsivity, bias dependence of dynamic resistance — junction area product and 1/f noise show that the resulting diodes are comparable to the best planar diodes reported in the literature.     

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.     

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.     

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.     

MBE HgCdTe heterostructure p-on-n planar infrared photodiodes

We recently succeeded in fabricating planar Hg_1−yCd_yTe/Hg_1−xCd_xTe (x<y) heterostructure photodiodes with the p-on-n configuration. Here we discuss early results in detail and present new results on an expanded range of infrared operation. The material used for this demonstration was grown by molecular beam epitaxy on lattice-matched CdZnTe substrates. The p-on-n planar devices consist of an arsenic-doped p-type epilayer (y∼0.28) atop a long wavelength infrared n-type epilayer (x=0.22–0.23). The planar junctions were formed by selective pocket diffusion of arsenic deposited on the surface by ion implantation. Detailed analysis of the current-voltage characteristics of these diodes as a function of temperature shows that they have high performance and that their dark currents are diffusion-limited down to 52K. Low frequency noise measurements at a reverse bias voltage of 50 mV resulted in noise current values (at 1 Hz) as low as 1×10⁻¹⁴ amps/Hz^0.5 at 77K. Average R_oA values greater than 10⁶ Ω-cm² at 40K were obtained for these devices with cut-off wavelength values in the 10.6 to 12 μm range. Seventy percent of these devices have R_oA values greater than 10⁵ Ω-cm² at 40K; further studies are needed to improve device uniformity. These results represent the first demonstration that high performance long wavelength infrared devices operating at 40K can be made using HgCdTe material grown by a vapor phase epitaxy growth technique.     

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。     

Structure investigation on Hg1−xCdxTe liquid phase epitaxial films grown by the meltetch technique

Hg_1−xCd_xTe films were grown by a modified meltetch liquid phase epitaxial (LPE) technique which includes both substrate and epilayer etchback steps. The crystal quality of epilayer has been investigated by means of transmission electron microscopy, scanning electron microscopy, and double crystal x-ray diffraction. It has been found that adequate meltetch of the substrate at the beginning of LPE provides a fresh and flat surface for epitaxial growth, while epilayer meltetch at the end of LPE may prevent spurious melt sticking.     

Transient behavior of Hg1−xCdxTe films deposited on (100) CdTe substrates by chemical vapor transport

The growth history of Hg_1−xCd_xTe films deposited on (100) CdTe substrates by chemical vapor transport (CVT) has been studied, for the first time, by using a transient growth technique. The observed morphological evolution of Hg_1−xCd_xTe films deposited at 545°C shows a transition behavior from three-dimensional (3D) islands to two-dimensional (2D) layer growth. The experimental results indicate that the so-called critical time needed for the above morphological transition is about lh under present experimental conditions. Based on the chemical bonding properties of Hg_1−xCd_xTe, and on the behavior of the morphological transition, the Stranski-Krastanov growth mode is suggested for the epitaxial growth system. The time dependence of the growth thickness, of the growth rate (R₁₀₀) along the [100] direction, and of the surface composition all reveal a transient behavior. These are related to the nature of the Hg_1-xCd_xTe/ (100)CdTe heterojunction and to the surface reactions. Comparison of the growth rates and of the total mass deposited as a function of time shows the relationship between epitaxial growth and mass flux of the Hg_1−xCd_xTe-HgI₂ chemical vapor transport system.     

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.     

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.     

Effect of successive implantation of Ag+(Cu+) and Xe+ ions on the recombination properties of CdxHg1−x Te crystals

The effect of successive double implantation of Ag⁺(Cu⁺) and Xe⁺ ions on the recombination properties of Cd_xHg_1−x Te (0.2<x<0.3) crystals has been investigated. It is shown that after implantation of ions of one chemical element, followed by diffusion thermal annealing at temperatures below 150–200 K, recombination through local levels lying 30±5 meV below the conduction band bottom dominates. Successive double implantation of Ag⁺(Cu⁺) and Xe⁺ ions followed by diffusion thermal annealing changes the course of the temperature dependence of the lifetime of the nonequilibrium charge carriers. It was determined that for Cd_xHg_1−x Te crystals with x⋍0.20–0.25 in the temperature interval 700–200 K the lifetime of the nonequilibrium charge carriers is low (τ<0.15 μs) and does not depend on the temperature. For Cd_xHg_1−x Te crystals with x⋍0.3 recombination of nonequilibrium charge carriers occurs through two types of levels: in the temperature range 140–200 K — deep levels E _t1⋍E _c −51 meV and at lower temperatures (77–140 K) — through shallower levels E _t2⋍E _c −(16±2) meV. Fiz. Tekh. Poluprovodn. 31, 786–789 (July 1997)     

Observation of phase separation in Hg1−xCdxTe solid solutions by low incident angle x-ray diffraction

The low incident angle (surface analysis) and the conventional wide angle (bulk analysis) x-ray diffraction techniques were employed to investigate the existence of a miscibility gap in the Hg_1−xCd_xTe system. Samples of initial composition Hg_0.46Cd_0.54Te were annealed at 140 and 400°C, respectively, for four weeks. The diffraction planes (531) and (642) have been selected for the x-ray diffraction analysis. The results of this work provide the first, direct experimental evidence for the existence of a miscibility gap at lower temperature in the Hg_1−xCd_xTe system. The phase separation occurs primarily in a thin surface layer at 140°C and is reversible after annealing at 530°C. The compositions of the two compounds at the tie-line at 140°C are Hg_0.22Cd_0.78Te and Hg_0.63Cd_0.37Te.     

Planar n-on-p ion milled mid-wavelength and long-wavelength infrared diodes on molecular beam epitaxy vacancy-doped CdHgTe on CdZnTe

Planar mid-wavelength infrared (MWIR) and long-wavelength infrared (LWIR) photodiodes were fabricated by ion milling molecular beam epitaxy (MBE) Cd_xHg_1−xTe (CMT) layers with and without compositional grading in the layer. Linear arrays with 32 and 64 diodes, as well as test diodes of varying size, were fabricated. Good quantum efficiencies were measured, and MWIR diodes, with cutoff wavelength λ_CO=4.5 μm, had zero-bias resistance-area values (R₀A) in excess of 1×10⁷ Ωcm², whereas LWIR diodes with λ_CO=8.9−9.3 μm had R₀A=3×10² Ωcm² at 77 K. Comparison between a limited number of layers indicates that in layers with a gradient the RA values are a factor of ∼10 larger, and possibly more uniform, than in layers without a gradient.     

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.     

Electrical properties of HgCdTe epilayers doped with silver using an AgNO3 solution

We employed AgNO₃ solutions for doping Ag in liquid phase epitaxy (LPE) grown Hg_0.78Cd_0.22Te epilayers and found that the minority carrier lifetimes became longer so that the diode properties improved. After annealing LPE grown Hg(1-x)Cd(x)Te layers (x=0.22) in Hg atmosphere, the epilayers were immersed in an AgNO₃ solution at room temperature. The typical carrier concentrations of holes was 3 × 10¹⁶ cm⁻³ at 77K. These values were almost the same as for the nondoped wafers. Also, its acceptor level was 3 to 4 meV. This shows that the Ag was activated. The doped crystals have lifetimes several times longer than those of the nondoped crystals. Numerical fitting showed the lifetime was limited mostly by the Auger 7 process. The Shockley-Read-Hall recombination process was not effective. To examine the Ag-doped wafer, we fabricated photodiodes using standard planar technology. The diodes have an average zero-bias resistance of several MΩ and a shunt resistance of about 1 GΩ for a 10 μm cutoff wavelength at 78K. These values are about four times higher than those of nondoped diodes. The photo current is also two times higher at the same pixel size. This shows that the quantum efficiency is increased. The extension of the lifetime contributes to the high resistance and the high quantum efficiency of the photodiode.