HgCdTe Research at FFI: Molecular Beam Epitaxy Growth and Characterization

This paper presents results from recent work on molecular beam epitaxy growth of HgCdTe at the Norwegian Defence Research Establishment (FFI), including studies of material properties and fabrication of photodiodes and nanostructures. Systematic studies of defect morphology in HgTe and Hg_1−x Cd _x Te have revealed that there is a minimum in the area covered by defects just below the onset of Te precipitation. The shape and density of microvoids in HgTe can be used to determine the deviation from the optimal growth temperature. This can be further related to the optimal growth temperature of Hg_1−x Cd _x Te with any Cd mole fraction by thermodynamic calculations. A mechanism for the formation of microvoids and needles has been presented. Photoluminescence (PL) has been used to study layers without doping and with Hg vacancy, Ag, and In doping. Planar photodiodes with high dynamic resistance and good quantum efficiency were fabricated by ion-milling vacancy-doped mid-wave and long-wave infrared layers. Quantum wells (QWs) with good crystallinity and high PL light output have been grown. Surface patterning has been found to enhance light emission from HgCdTe thin-film and QW samples by ∼30%. Single-crystal HgTe and segmented HgTe/Te nanowires have been grown, and the resistivity of the nanowires has been measured by conductive atomic force microscopy (AFM), where the AFM tip has been used as a mobile electrode.     

HgCdZnTe quaternary materials for lattice-matched two-color detectors

As the number of bands and the complexity of HgCdTe multicolor structures increases, it is desirable to minimize the lattice mismatch at growth interfaces within the device structure in order to reduce or eliminate mismatch dislocations at these interfaces and potential threading dislocations that can degrade device performance. To achieve this we are investigating the use of Hg_1−x−yCd_xZn_yTe quaternary alloys which have an independently tunable lattice constant and bandgap. Lattice matching in Hg_1−x−yCd_xZn_yTe structures can be achieved using small additions of Zn (y<0.015) to HgCdTe ternary alloys. We have investigated some of the basic properties of Hg_1−x−yCd_xZn_yTe materials with x≈0.31 and 0≤y≤0.015. The quaternary layers were grown on (112)CdZnTe substrates using MBE and the amount of Zn in the layers was determined from calibrated SIMS measurements. As expected, the lattice constant decreased and the bandgap increased as Zn was added to HgCdTe to form Hg_1−x−yCd_xZn_yTe. Hall-effect results for both n-type (In) and p-type (As) Hg_1−x−yCd_xZn_yTe layers were very similar to HgCdTe control samples. We have also utilized x-ray rocking curve measurements with (246) asymmetric reflections as a novel sensitive technique to determine the correct amount of Zn needed to achieve lattice matching at an interface. MWIR/LWIR n-p-n two-color triple-layer heterojunction structures were grown to evaluate the effects of minimizing the lattice mismatch between the widest bandgap p-type collector layer, using Hg_1−x−yCd_xZn_yTe, and the HgCdTe MWIR and LWIR collector layers and compared to structures that did not incorporate the quaternary. Sequential mode two-color detectors were fabricated using a 256 × 256, 30 μm unit cell design. There were several interesting findings. Macro defects predominantly affected the LWIR band (Band 2) operability and had little effect on the MWIR band (Band 1). The incorporation of Hg_1−x−yCd_xZn_yTe p-type collector layers had little effect on MWIR detector performance, but overall the LWIR performance was generally better. These initial detector results indicate that the use of Hg_1−x−yCd_xZn_yTe alloys in multicolor detector structures are potentially promising and should be pursued further.     

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.     

Flexibility of p–n Junction Formation from SWIR to LWIR Using MBE-Grown Hg(1–x)CdxTe on Si Substrates

In this paper, we show the versatility of using molecular-beam epitaxy (MBE) for the growth of the mercury cadmium telluride (HgCdTe) system. Abrupt composition profiles, changes in doping levels or switching doping types are easily performed. It is shown that high-quality material is achieved with Hg_(1–x)Cd _x Te grown by MBE from a cadmium mole fraction of x = 0.15 to x = 0.72. Doping elements incorporation as low as 10¹⁵ cm⁻³ for both n-type and p-type material as well as high incorporation levels >10¹⁸ cm⁻³ for both carrier types were achieved. X-ray curves, secondary-ion mass spectrometry (SIMS) data, Hall data, the influence of doping incorporation with cadmium content and growth rate, etch pit density (EPD), composition uniformity determined from Fourier-transform infrared (FTIR) transmission spectro- scopy, and surface defect maps from low to high x values are presented to illustrate the versatility and quality of HgCdTe material grown by MBE. All data presented in this work are from layers grown on silicon (112) substrate.     

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.     

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.     

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.     

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.     

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.     

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.     

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     

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.     

Effect of Hydrogen Free Radicals on Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te

The effects of atomic hydrogen (H) and Br/methanol etching on Hg_1−x Cd _x Te films were investigated using x-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Exposure of an as-received Hg_1−x Cd _x Te sample to H + H₂ resulted in H-induced TeO₂ reduction. The oxide reduction was first order with respect to H + H₂ exposure. Exposure to H + H₂ after etching the Hg_1−x Cd _x Te film in a Br/methanol solution induced Hg and C depletion. Hg and C removal was also observed after completely reducing the TeO₂ on the as-received sample. The removal process was hindered by the formation of a Cd-rich overlayer on both etched and unetched surfaces.     

Electrical properties and compositional distributions of CVT and PVT grown Hg1−xCdxTe epilayers

Epitaxial layers of Hg_1−xCd_x Te were grown on CdTe substrates by the chemical vapor transport technique using Hgl₂ as a transport agent. The epilayers were of nearly uniform composition both laterally and to a depth of about one-half of the layer thickness. By comparison, the composition varied continuously throughout the depth of the layer for epilayers grown by the physical vapor transport technique. Layers were grown both p- and n-type with carrier concentrations on the order of 10¹⁷ cm⁻³. Low-temperature annealing was used to convert the p-type layers into n-type. The room-temperature carrier mobilities of as-grown and converted n-type layers ranged from 10³ to 10⁴ cm²/V-s depending on the composition and are comparable to previous literature values for undoped Hg_1−xCd_xTe crystals.     

An Initial Investigation of Nitrogen Doping of Wide-Bandgap HgCdTe During Molecular-Beam Epitaxy Using Ar/N Plasmas

An initial investigation of the use of atomic nitrogen for controlled p-type doping of wide-bandgap Hg_0.3Cd_0.7Te (x = 0.7) is reported. Mixtures of argon and nitrogen, ranging in nitrogen concentration from 0.1% to 100%, have been utilized to demonstrate well-controlled nitrogen incorporation in the 10¹⁶ cm⁻³ to 10²⁰ cm⁻³ range using total gas flow rates of 0.3 sccm to 4.0 sccm and radiofrequency (RF) powers of 100 W to 400 W. Nitrogen doping exhibits several desirable attributes including abrupt turn-on and turn-off and minimal sensitivity to variations in growth temperature and HgCdTe composition, with no negative effects on HgCdTe dislocation density and morphology. Preliminary electrical measurements indicate primarily n-type behavior in the 10¹⁴ cm⁻³ to 10¹⁵ cm⁻³ range in as-grown x = 0.7 HgCdTe and CdTe films doped with nitrogen at 10¹⁸ cm⁻³ to 10²⁰ cm⁻³ concentrations, while ZnTe films have exhibited p-type electrical activity with hole concentrations approaching 10²⁰ cm⁻³.     

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.     

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.     

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.     

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.     

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.