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.     

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 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.     

Far-infrared detector based on HgTe/HgCdTe superlattices

HgTe/Hg_0.05Cd_0.95Te superlattices (SLs) were grown on (112)B oriented Cd_0.96Zn_0.04 Te substrates using molecular beam epitaxy (MBE). The SLs, consisting of 100 periods of 80-Å-thick HgTe wells alternating with 77-Å-thick Hg_0.05Cd_0.95Te barriers, were designed to operate as detectors in the far-infrared (FIR) region. Infrared absorption spectroscopy, high-resolution transmission electron microscopy (TEM), Hall effect measurements, and x-ray diffraction were used to characterize the superlattice layers. A series of annealing experiments were initiated to quantify the temperature-dependent interdiffusion of the HgTe wells and Hg_0.05Cd_0.95Te barriers and consequently their degradation, which shifts the absorption edges of the SLs to higher energies, since a high-temperature ex situ anneal is normally required in order to produce the p-type material required for a photovoltaic detector. Results from infrared absorption spectroscopy, TEM, and Hall effect measurements for the annealed samples are presented. A FIR SLs single-element photoconductive (PC) device was designed and fabricated. Both material characterization and device testing have established the applicability of the HgTe/Hg_0.05Cd_0.95Te SLs for the FIR region.     

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.     

MBE HgCdTe on Alternative Substrates for FPA Applications

Results of first-principles calculations and experiments focusing on molecular beam epitaxy (MBE) growth of HgCdTe on the alternative substrates of GaAs and Si are described. The As passivation on (2 × 1) reconstructed (211) Si and its effects on the surface polarity of ZnTe or CdTe were clarified by examining the bonding configurations of As. The quality of HgCdTe grown on Si was confirmed to be similar to that grown on GaAs. Typical surface defects in HgCdTe and CdTe were classified. Good results for uniformities of full width at half maximum (FWHM) values of x-ray rocking curves, surface defects, and x values of Hg_1−x Cd _x Te were obtained by refining the demanding parameters and possible tradeoffs. The sticking coefficient of As₄ for MBE HgCdTe was determined. The effects of Hg-assisted annealing for As activation were investigated experimentally and theoretically by examining the difference of the formation energy of As_Hg and As_Te. Results of focal-plane arrays (FPAs) fabricated with HgCdTe grown on Si and on GaAs are discussed.     

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.     

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.     

X-ray Diffraction Imaging of Improved Bulk-Grown CdZnTe(211) and Its Comparison with Epitaxially Grown CdTe Buffer Layers on Si and Ge Substrates

Large-area high-quality Hg_1–x Cd _x Te sensing layers for infrared imaging in the 8 μm to 12 μm spectral region are typically grown on bulk Cd_1–x Zn _x Te substrates. Alternatively, epitaxial CdTe grown on Si or Ge has been used as a buffer layer for high-quality epitaxial HgCdTe growth. In this paper, x-ray topographs and rocking-curve full-width at half-maximum (FWHM) data will be presented for recent high-quality bulk CdZnTe grown by the vertical gradient freeze (VGF) method, previous bulk CdZnTe grown by the vertical Bridgman technique, epitaxial CdTe buffer layers on Si and Ge, and a HgCdTe layer epitaxially grown on bulk VGF CdZnTe.     

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.     

The Effects of Microvoid Defects on MWIR HgCdTe-Based Diodes

The effects of microvoid defects on the performance of mid-wavelength infrared (MWIR) HgCdTe-based diodes were examined. Molecular beam epitaxy (MBE) was utilized to deposit indium-doped, Hg_0.68Cd_0.32Te on 2 cm × 3 cm, (211)B-oriented, bulk Cd_0.96Zn_0.04Te substrates. These epilayers generally exhibited state-of-the-art material properties with a notable exception: high and nonuniform microvoid defect densities (mid 10⁴ cm⁻² to low 10⁶ cm⁻²). Diodes were fabricated by ion implantation of arsenic to form planar p–n junctions. Dark current–voltage (I–V) curves were measured and analyzed as a function of operating temperature. There was an inverse correlation between wafer-level microvoid defect density and device operability. On each wafer, devices with the smallest implants exhibited higher operability than devices with larger implants. By removal of pad metal and examination of defects within each implant area, it was found that the presence of one or more microvoids within the junction usually caused tunneling or other high-current mechanisms. Diodes free from microvoids exhibited diffusion-limited behavior down to 150 K, the test set limit.     

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.     

Electron microscopy of surface-crater defects on HgCdTe/CdZnTe(211)B epilayers grown by molecular-beam epitaxy

Surface-void defects observed in Hg_1−xCd_xTe (x ∼ 0.2–0.4) alloys grown by molecular-beam epitaxy (MBE) have been investigated using scanning and high-resolution transmission-electron microscopy (HRTEM) as well as atomic force microscopy (AFM). These surface craters, which have been attributed to Hg-deficient growth conditions, were found to originate primarily within the HgCdTe epilayer, rather than at the CdZnTe substrate, and they were associated with the local development of polycrystalline morphology. High-resolution observations established the occurrence of finely spaced HgCdTe/Te intergrowths with semicoherent and incoherent grain boundaries, as well as small HgCdTe inclusions embedded within the Te grains. This study is the first time that high-resolution electron microscopy has been used to investigate this type of defect.     

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.     

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.     

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.     

Molecular beam epitaxial HgCdTe material characteristics and device performance: Reproducibility status

Extensive material, device, and focal plane array (FPA) reproducibility data are presented to demonstrate significant advances made in the molecular beam epitaxial (MBE) HgCdTe technology. Excellent control of the composition, growth rate, layer thickness, doping concentration, dislocation density, and transport characteristics has been demonstrated. A change in the bandgap is readily achieved by adjusting the beam fluxes, demonstrating the flexibility of MBE in responding to the needs of infrared detection applications in various spectral bands. High performance of photodiodes fabricated on MBE HgCdTe layers reflects on the overall quality of the grown material. The photodiodes were planar p-on-n junctions fabricated by As ion-implantation into indium doped, n-type, in situ grown double layer heterostructures. At 77K, diodes fabricated on MBE Hg_1−xCd_xTe with x ≈ 0.30 (λ_co ≈ 5.6 μm), x ≈ 0.26 (λ_co ≈ 7 μm), x ≈ 0.23 (λ_co ≈ 10 μm) show R₀A products in excess of 1 x 10⁶ ohm-cm², 7 x 10⁵ ohm-cm², and 3 x 10² ohm-cm², respectively. These devices also show high quantum efficiency. As a means to assess the uniformity of the MBE HgCdTe material, two-dimensional 64 x 64 and 128 x 128 mosaic detector arrays were hybridized to Si multiplexers. These focal plane arrays show an operability as high as 97% at 77K for the x ≈ 0.23 spectral band and 93% at 77K for the x ≈ 0.26 spectral band. The operability is limited partly by the density of void-type defects that are present in the MBE grown layers and are easily identified under an optical microscope.     

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.     

Determination of cut-off wavelength and composition distribution in Hg1-xCdxTe

The determination of cut-off wavelength, λ _co, and composition distribution for Hg_1-xCd_xTe has been discussed in this paper. A shift of the cut-off wavelength was found from the photo-response calculation for the HgCdTe devices with the same energy gap E_g but different thickness d. An expression of λ _co(x,T,d) has been derived from the half-maximum photo-response curve calculation. The composition uniformity has been determined from the room-temperature transmission fitting procedure. The composition real space distribution is suggested to be determined by the combination of absorption edge phenomenon and thermal imaging technique.     

Synthesis and Characterization of <Emphasis Type="Italic">p</Emphasis>-Type Pb<Subscript>0.5</Subscript>Sn<Subscript>0.5</Subscript>Te Thermoelectric Power Generation Elements by Mechanical Alloying

A mechanical alloying (MA) process to transform elemental powders into solid Pb_0.5Sn_0.5Te with thermoelectric functionality comparable to melt-alloyed material is described. The room-temperature doping level and mobility as well as temperature-dependent electrical conductivity, Seebeck coefficient, and thermal conductivity are reported. Estimated values of lattice thermal conductivity (0.7 W m⁻¹ K⁻¹) are lower than some reports of functional melt-alloyed PbSnTe-based material, providing evidence that MA can engender the combination of properties resulting in highly functional thermoelectric material. Though doping level and Sn composition have not been optimized, this material exhibits a ZT value >0.5 at 550 K.