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.     

Automated compositional control of Hg1−xCdxTe during MBE, using in situ spectroscopic ellipsometry

The implementation of a feedback control system for maintaining a desired compositional value in Hg_1−xCd_xTe epilayers is reported. An 88-wavelength ellipsometer monitored the Cd content (x) of a Hg_1−xCd_xTe film during molecular beam epitaxy, and deviations from a pre-determined set-point were automatically corrected via adjustments in the CdTe effusion cell temperature. The accuracy of this system (Δx∼0.002) was confirmed by Fourier transform infrared transmission measurements made ex situ on the epilayers.     

Real-time control of HgCdTe growth by organometallic vapor phase epitaxy using spectroscopic ellipsometry

The use of spectroscopic ellipsometry for monitoring the vapor phase epitaxial growth of mercury cadmium telluride (Hg_1−xCd_xTe) in real-time is demonstrated. The ellipsometer is used to perform system identification of the chemical vapor deposition reactor used for the growth of CdTe and to measure the response of the reactor to different growth conditions. The dynamic behavior of the reactor is also studied by evaluating the gas transport delay. The optical constants of Hg_1−xCd_xTe are determined at the growth temperature for different compositions.In-situ real-time composition control is performed during the growth of Hg_1−xCd_xTe. The required target compositions are attained by the ellipsometer and appropriate corrections are also made by the controller when a noise input in the form of a temperature variation is introduced.     

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.     

Optical and Structural Properties of CdTe Grown by Molecular Beam Epitaxy at Low Temperature for Resonant-Cavity-Enhanced HgCdTe Detectors

Investigation into resonant-cavity-enhanced (RCE) HgCdTe detectors has revealed a discrepancy in the refractive index of the CdTe layers grown by molecular beam epitaxy (MBE) for the detectors, compared with the reported value for crystalline CdTe. The refractive index of the CdTe grown for RCE detectors was measured using ellipsometry and matches that of CdTe with an inclusion of approximately 10% voids. X-ray measurements confirm that the sample is crystalline and strained to match the lattice spacing of the underlying Hg_(1−x)Cd_(x)Te, while electron diffraction patterns observed during growth indicate that the CdTe layers exhibit some three-dimensional structure. Secondary ion mass spectroscopy results further indicate that there is enhanced interdiffusion at the interface between Hg_(1−x)Cd_(x)Te and CdTe when the Hg_(1−x)Cd_(x)Te is grown on CdTe, suggesting that the defects are nucleated within the CdTe layers.     

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     

Effect of incident angle in spectral ellipsometry on composition control during molecular beam epitaxial growth of HgCdTe

The effect of incident angle in spectral ellipsometry (SE) on composition control of Hg_1−xCd_xTe grown by molecular beam epitaxy (MBE) was investigated. Although a small uncertainty in the incident angle tends to have a significant impact on the ellipsometric data, and therefore the composition data, it was found that the incident angle uncertainty could be corrected in the SE model calculation, resulting in an “optimized” incident angle that would give the best fit between measured and calculated ellipsometric data. Experimental data supporting this simple corrective or optimization procedure for the incident angle are presented.     

Development of Molecular Beam Epitaxially Grown Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te for High-Density Vertically-Integrated Photodiode-Based Focal Plane Arrays

Hg_1−x Cd _x Te samples of x ~ 0.3 (in the midwave infrared, or MWIR, spectral band) were prepared by molecular beam epitaxy (MBE) for fabrication into 30-μm-pitch, 256 × 256, front-side-illuminated, high-density vertically-integrated photodiode (HDVIP) focal plane arrays (FPAs). These MBE Hg_1−x Cd _x Te samples were grown on CdZnTe(211) substrates prepared in this laboratory; they were ~10-μm thick and were doped with indium to ~5 × 10¹⁴ cm⁻³. Standard HDVIP process flow was employed for array fabrication. Excellent array performance data were obtained from these MWIR arrays with MBE HgCdTe material. The noise-equivalent differential flux (NEΔΦ) operability of the best array is 99.76%, comparable to the best array obtained from liquid-phase epitaxy (LPE) material prepared in this laboratory.     

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.     

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.     

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.     

In situ sensors for monitoring and control in molecular beam epitaxial growth of Hg1−xCdxTe

The current status of the implementation and refinement of two wafer state sensors forin situ monitoring and control during molecular beam epitaxial (MBE) growth of Hg_1−xCd_xTe will be reported. First a rapid scan spectral ellipsometer has been developed and employed for precisely measuring compositions of Hg_1−xCd_xTe alloys during growth. MBE films in the composition range x = 0.20 to 0.30 have been grown andin situ spectra taken at the growth temperature (180°C) and at room temperature. The MBE films were treated as single layers without the need to invoke any surface film (due to surface roughness, oxide, or of any different composition) as required for exsitu data. The least squares fit over the whole spectral range was used as a measure of the precision. The film composition was also determinedex situ by wavelength dispersive analysis of x-rays and by Fourier transform infrared (FTIR) spectrometry after verifying that there was no lateral variation. A precision of better than ±0.0015 has so far been demonstrated usingin situ spectral ellipsometry for Cd composition or CdTe mole fraction, x, measurements. This compares with ±0.003 for single wavelength ellipsometry. The composition of Hg_1−xCd_xTe films were also monitored during growth. A spectral pyrometer based on a FTIR spectrometer has also been developed for substrate temperature measurements during growth. The spectral pyrometer measures both the emission and reflectance to give the emissivity of a growing sample over a range of wavelengths spanning the peak of the grey body emission. From the reflectivity measurements, the thickness (in excess of 1 μm) of the growing film is also determined from the interference fringes. The spectral ellipsometer is only capable of measuring thicknesses up to C.a 5000°A (i.e. optically thin). Excellent agreement is obtained between thein situ (at growth temperature) andex situ (at room temperature) thickness measurements. The small discrepancy can be explained by the refractive index of Hg_1−xCd_xTe being 5% higher at the growth temperature than at room temperature. The combination ofin situ sensors now provides a means of continuously monitoring the composition and thickness of the growing Hg_1−xCd_xTe film.     

Transient behavior of Hg1−xCdxTe film growth on (111)B CdTe substrates by chemical vapor transport

As part of a systematic investigation of the effects of substrate surfaces on epitaxial growth, the transient behavior of Hg_1−xCd_xTe film growth on (111)B CdTe by chemical vapor transport (CVT) has been studied as a function of growth time under vertical stabilizing (hot end on top) and vertical destabilizing (hot end at bottom) ampoule orientations. The experim ental results show the morphological transition of the Hg_1−xCd_xTe deposition on (111)B CdTe at 545°C from three-dimensional islands to layers within about 0.5 and 0.75 h for the growth under vertical stabilizing and destabilizing conditions, respectively. The combined effects of small convective flow disturbances on the growth morphology and defect formation are measurable. The overall trends of the time dependent growth rates and compositions of the Hg_1−xCd_xTe epitaxial layers under stabilizing and destabilizing conditions are similar. The system atically higher growth rates of the Hg_1−xCd_xTe films by about 10% under vertical destabilizing conditions could be influenced by a small convective contribution to the mass transport. The combined results show that improved Hg_1−xCd_xTe epitaxial layers of low twin density on (111)B CdTe substrates can be obtained by CVT under vertical stabilizing conditions.     

Ten-inch molecular beam epitaxy production system for HgCdTe growth

Growth of Hg_1−xCd_xTe by molecular beam epitaxy (MBE) has been under development since the early 1980s at Rockwell Scientific Company (RSC), formerly the Rockwell Science Center; and we have shown that high-performance and highly reproducible MBE HgCdTe double heterostructure planar p-on-n devices can be produced with high throughput for various single- and multiplecolor infrared applications. In this paper, we present data on Hg_1−xCd_xTe epitaxial layers grown in a ten-inch production MBE system. For growth of HgCdTe, standard effusion cells containing CdTe and Te were used, in addition to a Hg source. The system is equipped with reflection high energy electron diffraction (RHEED) and spectral ellipsometry in addition to other fully automated electrical and optical monitoring systems. The HgCdTe heterostructures grown in our large ten-inch Riber 49 MBE system have outstanding structural characteristics with etch-pit densities (EPDs) in the low 10⁴ cm⁻² range, Hall carrier concentration in low 10¹⁴ cm⁻³, and void density <1000 cm². The epilayers were grown on near lattice-matched (211)B Cd_0.96Zn_0.04Te substrates. High-performance mid wavelength infrared (MWIR) devices were fabricated with R₀A values of 7.2×10⁶ Ω-cm² at 110 K, and the quantum efficiency without an antireflection coating was 71.5% for cutoff wavelength of 5.21 μm at 37 K. For short wavelength infrared (SWIR) devices, an R₀A value of 9.4×10⁵ Ω-cm² at 200 K was obtained and quantum efficiency without an antireflection coating was 64% for cutoff wavelength of 2.61 μm at 37 K. These R₀A values are comparable to our trend line values in this temperature range.     

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.     

Effects of a-Si:H resist vacuum-lithography processing on HgCdTe

A vacuum-compatible process for carrying out lithography on Hg_1−xCd_xTe and CdTe films was previously demonstrated. It was shown that hydrogenated amorphous silicon (a-Si:H) could be used as a dry resist by projecting a pattern onto its surface using excimer laser irradiation and then developing that pattern by hydrogen plasma etching. Pattern transfer to an underlying Hg_1−xCd_xTe film was then carried out via Ar/H₂ plasma etching in an electron cyclotron resonance (ECR) reactor. Despite the successful demonstration of pattern transfer, the possibility of inducing harmful effects in the Hg_1−xCd_xTe film due to this vacuum lithography procedure had not been explored. Here we present structural and surface compositional analyses of Hg_1−xCd_xTe films at key stages of the a-Si:H vacuum lithography procedure. X-ray diffraction double crystal rocking curves taken before and after a-Si:H deposition and after development etching were identical, indicating that bulk structural changes in the Hg_1−xCd_xTe film are not induced by these processes. Cross-section transmission electron microscopy studies show that laser-induced heating in the 350 nm thick a-Si:H overlayer is not sufficient to cause structural damage in the underlying Hg_1−xCd_xTe surface. In vacuo surface analysis via Auger electron spectroscopy and ion scattering spectroscopy suggest that the hydrogen plasma development process produces Hg-deficient surfaces but does not introduce C contamination. However, after ECR plasma etching into the Hg_1−xCd_xTe film, the measured x value is much closer to that of the bulk.     

Near-bandgap infrared absorption properties of HgCdTe

We report temperature-dependent absorption measurements from 300 K to 4.2 K for molecular beam epitaxy (MBE)-grown Hg_1−xCd_xTe samples with different alloy compositions. The infrared absorption coefficients near the energy gap were obtained using an interference matrix method. Photoconductive spectra were simultaneously measured at the same points on the samples to precisely determine the energy gaps. The Urbach tail energies are extracted from the absorption coefficients, and their temperature dependence is analyzed using a theoretical model. The contribution from static disorder, including structural and alloy disorder, is found to be much larger than the phonon-related dynamic disorder.     

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.     

Observation of prevalence of quasi-equilibrium in the MBE growth of Hg1−xCdxTe

MBE growth of Hg_1−xCd_xTe has been carried out at 185°C. Parameters of growth have systematically varied. The resulting compositional changes and the electrical characteristics have been explained on the basis of the prevalence of quasi-equilibrium at the growth temperature.     

Origin of void defects in Hg1−xCdxTe grown by molecular beam epitaxy

Characterization of defects in Hg_1−xCd_xTe compound semiconductor is essential to reduce intrinsic and the growth-induced extended defects which adversely affect the performance of devices fabricated in this material system. It is shown here that particulates at the substrate surface act as sites where void defects nucleate during Hg_1−xCd_xTe epitaxial growth by molecular beam epitaxy. In this study, we have investigated the effect of substrate surface preparation on formation of void defects and established a one-to-one correlation. A wafer cleaning procedure was developed to reduce the density of such defects to values below 200 cm⁻². Focal plane arrays fabricated on low void density materials grown using this new substrate etching and cleaning procedure were found to have pixel operability above 98.0%.