Spectroscopic ellipsometry for monitoring and control of molecular beam epitaxially grown HgCdTe heterostructures

A systematic study of the effect of measurement perturbation on in situ monitoring of the composition of molecular beam epitaxially (MBE) grown Hg_1−xCd_xTe using spectroscopic ellipsometry was carried out. Of the five variables investigated, which included angle of incidence, wavelength of the light beam, modulator rotation, analyzer rotation, and modulator amplitude, the angle of incidence and the modulator rotation had the strongest effect on the in situ Hg_1−xCd_xTe composition monitoring process. A wobble-free sample manipulator was installed to reduce the impact of these two variables. With these improvements, the spectroscopic ellipsometer is now routinely used to monitor Hg _1−xCd_xTe compositions during MBE growth of heterostructures and is a useful tool in diagnosing growth-related problems. Examples are included for both application areas, that include the control of the interface between Hg_1−xCd_xTe layers of different compositions, i.e. device engineering.     

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.     

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.     

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.     

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.     

Transient behavior of Hg1−xCdxTe film growth on 3° off-(100) CdTe substrates by chemical vapor transport

The effects of substrate misorientation on Hg_1−xCd_xTe films, deposited on 3° off-(100) CdTe substrates by chemical vapor transport (CVT), have been studied for the first time using a transient growth technique. The morphological evolution of Hg_1−xCd_xTe films deposited on the vicinal CdTe substrates at 545°C shows a transition from three-dimensional islands to two-dimensional layer growth. The time and thickness required for the above morphological transition is about 0.75 h and 7 μm, respectively, under present experimental conditions. The pronounced long-range-terrace surface morphology of the Hg_1−xCd_xTe films illustrates the strong effects of the misorientation of the CdTe substrates and of the growth kinetics on the CVT growth of this hetero-epitaxial system. The transient behavior of the surface morphology, of the surface composition, and of the growth rate all reveal the influences of the 3° misorientation of the (100) CdTe substrates on the Hg_1−xCd_xTe epitaxy. The experimental mass flux results of the Hg_1−xCd_xTe-HgI₂ CVT system under transient and steady-state conditions can be related to the surface kinetics and to the thermodynamic properties of the system. The combined results show that the interface kinetics are not fixed in the transient regime and that they are coupled to the vapor mass transport.     

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.     

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.     

Physico-chemical properties of Ga and In dopants during liquid phase epitaxy of CdxHg1−xTe

This work deals with the study by means of radioactive tracers and autoradiography, as well as measuring of galvanomagnetic properties, of Ga and In doping of epitaxial Cd_xHg_1−xTe layers during their crystallization from a Te-rich melt. Ga and In were introduced in the form of Ga⁷² and In¹¹⁴ master alloys with Te. The effective distribution coefficients of Ga and In during the crystallization of the Cd_xHg_1−xTe solid solutions with x=0.20 to 0.23 were determined by cooling the Te-base melt to 515–470°C. Depending on the concentration of the dopants and the time-temperature conditions of Cd_xHg_1−xTe growth, these ratios for Ga and In were 1.5–2.0 and 1.0–1.5, respectively. The electrical activity of Ga and In was determined after annealing of the Cd_xHg_1−xTe layers in saturated Hg vapor at 270–300°C. In doping of the epitaxial layers to (3–8)×10¹⁴ cm⁻³ with subsequent annealing in saturated Hg vapor at ∼270°C increases the carrier lifetime approximately by a factor of two as compared with the undoped material annealed under the same conditions.     

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.     

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.     

Experimental determination of tie-lines in the Hg-Cd-Te system

Starting with powdered Hg_1−xCd_xTe, several tie-lines at 500 and 560°C were established using an energy dispersive spectrometer on a scanning electron microscope for the quantitative analysis. After holding at 500 or 560°C for time periods based upon the powder size and the published interdiffusion constant, then water quenching to room temperature, the primary grains were found to be uniform in composition and covered with a 5-6 μ layer of HgTe or low x Hg_1−xCd_xTe. The primary grain and overall compositions establish directions for tie-lines that are in good agreement with published experimental and theoreti-cal results.     

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.     

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.     

HgCdTe heteroepitaxy on three-inch (112) CdZnTe/Si: Ellipsometric control of substrate temperature

The technique of spectroscopic ellipsometry (SE) has been utilized to monitor in real-time and precisely control the surface temperature of Hg_1−xCd_xTe during molecular beam epitaxy. Due to the temperature dependence of the Hg sticking coefficient under Hg-deficient growth conditions, the near-surface composition of an epilayer is extremely sensitive to surface temperature. SE data were acquired in real time and modeled using a previously established library of dielectric functions of Hg_1−xCd_xTe as a function of composition. Utilizing SE-generated compositional profiles as a guide, substrate heating power was adjusted in such a way as to minimize composition transients. To demonstrate the effectiveness of the technique, we have used SE to control the temperature of HgCdTe epilayer surfaces during deposition on three-inch (211)CdZnTe/ZnTe/Si composite substrates mounted on indium free holders.     

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.     

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.     

Planar p-on-n HgCdTe FPAs by Arsenic Ion Implantation

This paper reviews recent developments in the characterization of planar p-on-n photodiodes fabricated from long- and mid-wavelength Hg_1−x Cd _x Te at␣the Electronics and Information Technology Laboratory (LETI). The Hg_1−x Cd _x Te epitaxial layers were grown by both liquid-phase and molecular-beam epitaxy. Planar p-on-n photodiodes were fabricated by arsenic implantation into an indium-doped Hg_1−x Cd _x Te base layer. Electro-optical characterization on these p-on-n photodiodes showed low leakage currents (shunt resistance > 10 GΩ) and mean R ₀ A values comparable to the state of the art, i.e., equal to 5000 Ω cm² at λ _c = 9.3 μm (λ _c: cutoff wavelength). Results of focal-plane arrays operating in both the long-wavelength infrared (IR) and middle-wavelength IR bands are reported, with noise equivalent delta temperature and responsivity values at λ _c = 9.3 μm in excess of 99.64%. These results demonstrate the viability and technological maturity of both material growth and device processing.     

Transport phenomena in n-MnxHg1−x Te/Cd0.96Zn0.04Te epitaxial films

The results of an experimental study of samples of Mn_xHg_1−x Te films grown by liquid-phase epitaxy on a Cd_0.96Zn_0.04Te substrate are presented. It shows that, as a result of the diffusion of cadmium from the substrate, a Cd_xMn_yHg_1−x−y Te film with a variable band-gap layer is formed close to the 〈epitaxial-film〉-substrate interface. The appearance of this variable band gap is revealed by the transport phenomena. The temperature dependence of the band gap E _g (T) is determined in a linear approximation on T from the results of a theoretical analysis of the temperature dependences of the free-carrier concentration and mobility. It is shown that averaging the semiempirical dependences for the ternary compounds with the extreme compositions, using the virtual-crystal approximation, can produce large errors when determining E _g (T) in a specific semiconductor. Fiz. Tekh. Poluprovodn. 31, 268–272 (March 1997)     

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.