Si基大面积碲镉汞分子束外延研究

文章报道了Si基碲镉汞分子束外延(MBE)的最新研究进展。尝试用晶向偏角降低高界面应变能的方法,摸索大失配体系中位错的抑制途径,寻找位错密度与双晶半峰宽的对应关系,基本建立了外延材料晶体质量无损检测评价标准,并对外延工艺进行指导。通过上述研究,15~20μm Si基CdTe复合材料双晶半峰宽最好结果为54arcsec,对应位错密度(EPD)小于2×106/cm2,与相同厚度的GaAs/CdTe(211)双晶水平相当,达到或优于国际最好结果。获得的3 in 10μm Si基HgCdTe材料双晶半峰宽最好结果为51arcsec,目前Si基HgCdTe材料已经初步应用于焦平面中波320×240器件制备。     

Developments in the fabrication and performance of high-quality HgCdTe detectors grown on 4-in. Si substrates

We are continuing to develop our growth and processing capabilities for HgCdTe grown on 4-in. Si substrates by molecular beam epitaxy (MBE). Both short-wave and mid-wave infrared (SWIR and MWIR) double-layer hetero-junctions (DLHJs) have been fabricated. In order to improve the producibility of the material, we have implemented an in-situ growth composition-control system. We have explored dry etching the HgCdTe/Si wafers and seen promising results. No induced damage was observed in these samples. Detector results show that the HgCdTe/Si devices are state-of-the-art, following the diffusion-limited trend line established by other HgCdTe technologies. Focal-plane array (FPA) testing has been performed in order to assess the material over large areas. The FPA configurations range from 128×128 to 1,024×1,024, with unit cells as small as 20 μm. The MWIR responsivity and NEDT values are comparable to those of existing InSb FPAs. Pixel operabilities well in excess of 99% have been measured. We have also explored the role of growth macrodefects on diode performance and related their impact to FPA operability. The SWIR HgCdTe/Si shows similar results to the MWIR material. Short-wave IR FPA, median dark-current values of less than 0.1 e⁻/sec have been achieved.     

MBE growth of HgCdTe on silicon substrates for large-area infrared focal plane arrays: A review of recent progress

We review the rapid progress that has been made during the past three years in the heteroepitaxial growth of HgCdTe infrared detector device structures on Si substrates by molecular-beam epitaxy. The evolution of this technology has enabled the fabrication of high performance, large-area HgCdTe infrared focal-plane arrays on Si substrates. A key element of this heteroepitaxial approach has been development of high quality CdTe buffer layers deposited on Si(112) substrates. We review the solutions developed by several groups to address the difficulties associated with the CdTe/Si(112) heteroepitaxial system, including control of crystallographic orientation and minimization of defects such as twins and threading dislocations. The material quality of HgCdTe/Si and the performance of HgCdTe detector structures grown on CdTe/Si(112) composite substrates is reviewed. Finally, we discuss some of the challenges related to composition uniformity and defect generation encountered with scaling the MBE growth process for HgCdTe to large-area Si substrates.     

Performance of molecular-beam epitaxy-grown midwave infrared HgCdTe detectors on four-inch Si substrates and the impact of defects

We are continuing development of the growth of midwave infrared (MWIR) HgCdTe by molecular-beam epitaxy (MBE) on 4-in. Si substrates and the fabrication of state-of-the-art detectors and focal plane arrays (FPAs). Array formats of up to 2048 × 2048 and unit cells as small as 20 μm have been made. We regularly measure response operability values in excess of 99% on these arrays. These values typically exceed expectations, with the number of outages corresponding to as-grown defect densities four times lower than what we measure. We have investigated this operability discrepancy and now can account for it. Comparisons of measured properties were used to establish trends between defect occurrence and pixel operability. These correlations show that a combination of defect removal and low-impact defects provide the explanation. Having this knowledge will allow for better operability predictions and assist in efforts to reduce defect impact on FPA performance.     

Direct growth of CdZnTe/Si substrates for large-area HgCdTe infrared focal plane arrays

Direct epitaxial growth of high-quality 100lCdZnTe on 3 inch diameter vicinal {100}Si substrates has been achieved using molecular beam epitaxy (MBE); a ZnTe initial layer was used to maintain the {100} Si substrate orientation. The properties of these substrates and associated HgCdTe layers grown by liquid phase epitaxy (LPE) and subsequently processed long wavelength infrared (LWIR) detectors were compared directly with our related efforts using CdZnTe/ GaAs/Si substrates grown by metalorganic chemical vapor deposition (MOCVD). The MBE-grown CdZnTe layers are highly specular and have both excellent thickness and compositional uniformity. The x-ray full-width at half-maximum (FWHM) of the MBE-grown CdZnTe/Si increases with composition, which is a characteristic of CdZnTe grown by vapor phase epitaxy, and is essentially equivalent to our results obtained on CdZnTe/GaAs/Si. As we have previously observed, the x-ray FWHM of LPE-grown HgCdTe decreases, particularly for CdZnTe compositions near the lattice matching condition to HgCdTe; so far the best value we have achieved is 54 arc-s. Using these MBE-grown substrates, we have fabricated the first high-performance LWIR HgCdTe detectors and 256 x 256 arrays using substrates consisting of CdZnTe grown directly on Si without the use of an intermediate GaAs buffer layer. We find first that there is no significant difference between arrays fabricated on either CdZnTe/Si or CdZnTe/GaAs/Si and second that the results on these Si-based substrates are comparable with results on bulk CdZnTe substrates at 78K. Further improvements in detector performance on Si-based substrates require a decrease in the dislocation density.     

MBE growth of HgCdTe on silicon substrates for large format MWIR focal plane arrays

HgCdTe p-on-n double layer heterojunctions (DLHJs) for mid-wave infrared (MWIR) detector applications have been grown on 100 mm (4 inch) diameter (211) silicon substrates by molecular beam epitaxy (MBE). The structural quality of these films is excellent, as demonstrated by x-ray rocking curves with full widths at half maximum (FWHMs) of 80–100 arcsec, and etch pit densities from 1 10⁶ to 7 10⁶ cm⁻². Morphological defect densities for these layers are generally less than 1000 cm⁻². Improving Hg flux coverage of the wafer during growth can reduce void defects near the edges of the wafers. Improved tellurium source designs have resulted in better temporal flux stability and a reduction of the center to edge x-value variation from 9% to only 2%. Photovoltaic MWIR detectors have been fabricated from some of these 100mm wafers, and the devices show performance at 140 K which is comparable to other MWIR detectors grown on bulk CdZnTe substrates by MBE and by liquid phase epitaxy.     

HgCdTe/Si materials for long wavelength infrared detectors

The heteroepitaxial growth of HgCdTe on large-area Si substrates is an enabling technology leading to the production of low-cost, large-format infrared focal plane arrays (FPAs). This approach will allow HgCdTe FPA technology to be scaled beyond the limitations of bulk CdZnTe substrates. We have already achieved excellent mid-wavelength infrared (MWIR) and short wavelength infrared (SWIR) detector and FPA results using HgCdTe grown on 4-in. Si substrates using molecular beam epitaxy (MBE), and this work was focused on extending these results into the long wavelength infrared (LWIR) spectral regime. A series of nine p-on-n LWIR HgCdTe double-layer heterojunction (DLHJ) detector structures were grown on 4-in. Si substrates. The HgCdTe composition uniformity was very good over the entire 4-in. wafer with a typical maximum nonuniformity of 2.2% at the very edge of the wafer; run-to-run composition reproducibility, realized with real-time feedback control using spectroscopic ellipsometry, was also very good. Both secondary ion mass spectrometry (SIMS) and Hall-effect measurements showed well-behaved doping and majority carrier properties, respectively. Preliminary detector results were promising for this initial work and good broad-band spectral response was demonstrated; 61% quantum efficiency was measured, which is very good compared to a maximum allowed value of 70% for a non-antireflection-coated Si surface. The R₀A products for HgCdTe/Si detectors in the 9.6-μm and 12-μm cutoff range were at least one order of magnitude below typical results for detectors fabricated on bulk CdZnTe substrates. This lower performance was attributed to an elevated dislocation density, which is in the mid-10⁶ cm⁻² range. The dislocation density in HgCdTe/Si needs to be reduced to <10⁶ cm⁻² to make high-performance LWIR detectors, and multiple approaches are being tried across the infrared community to achieve this result because the technological payoff is significant.     

Si基CdTe/HgCdTe分子束外延材料的位错抑制

基于GaAs/Si材料中位错的运动反应理论,修正获得CdTe/Si和HgCdTe/Si外延材料中的位错运动反应模型.采用快速退火方法对Si基HgCdTe外延材料进行位错抑制实验研究,实验结果与理论曲线基本吻合,从理论角度解释了不同高温热处理条件对材料体内位错的抑制作用.对于厚度为4～10μnn的CdTe/Si进行500...     

Improving material characteristics and reproducibility of MBE HgCdTe

This paper describes our progress to improve the material quality, reproducibility, and flexibility of molecular beam epitaxial (MBE) growth of HgCdTe. Data, statistics, and yields according to defined screen criteria are presented for n-type layer carrier concentration and mobility, void defect density, and dislocation density for more than 100 layers. Minority carrier lifetime data are also presented. Continued improvements in impurity reductiont have allowed us to achieve, for the first time, reproducible, low n-type carrier concentration in the mid-10¹⁴ cnr⁻³ range with high electron mobility. Data are presented that show that low dislocation density films are obtained for growth on CdZnTe substrates with a wide range of Zn concentration. Results are presented from a nine-growth run first pass success demonstration run to further assess material quality reproducibility and flexibility of wavelength band tuning. These results demonstrate the promising potential of MBE growth for flexible manufacturing of HgCdTe for infrared focal plane arrays.     

MBE Growth of HgCdTe on Large-Area Si and CdZnTe Wafers for SWIR,MWIR and LWIR Detection

Molecular beam epitaxy (MBE) growth of HgCdTe on large-size Si (211) and CdZnTe (211)B substrates is critical to meet the demands of extremely uniform and highly functional third-generation infrared (IR) focal-panel arrays (FPAs). We have described here the importance of wafer maps of HgCdTe thickness, composition, and the macrodefects across the wafer not only to qualify material properties against design specifications but also to diagnose and classify the MBE-growth-related issues on large-area wafers. The paper presents HgCdTe growth with exceptionally uniform composition and thickness and record low macrodefect density on large Si wafers up to 6-in in diameter for the detection of short-wave (SW), mid-wave (MW), and long-wave (LW) IR radiation. We have also proposed a cost-effective approach to use the growth of HgCdTe on low-cost Si substrates to isolate the growth- and substrate-related problems that one occasionally comes across with the CdZnTe substrates and tune the growth parameters such as growth rate, cutoff wavelength (λ _cutoff) and doping parameters before proceeding with the growth on costly large-area CdZnTe substrates. In this way, we demonstrated HgCdTe growth on large CdZnTe substrates of size 7 cm × 7 cm with excellent uniformity and low macrodefect density. Received December 7, 2007; accepted February 25, 2008     

Initial evaluation of a valved Te source for MBE growth of HgCdTe

Initial results using a valved Te source for molecular beam epitaxial growth of Hg_1−xCd_xTe are described. Unlike the case for a conventional Knudsen effusion cell where the flux is controlled primarily by temperature, flux from the valved source is controlled primarily by a variable orifice capable of good closure so that the cell temperature can be fixed at the operating temperature. Operating characteristics of the source are described, and include being able to nearly instantaneously change the flux magnitude at will. Using the source for HgCdTe growth has resulted in promising composition reproducibility improvement in initial growth runs.     

High-Performance LWIR MBE-Grown HgCdTe/Si Focal Plane Arrays

We have been actively pursuing the development of long-wavelength infrared (LWIR) HgCdTe grown by molecular beam epitaxy (MBE) on large-area silicon substrates. The current effort is focused on extending HgCdTe/Si technology to longer wavelengths and lower temperatures. The use of Si versus bulk CdZnTe substrates is being pursued due to the inherent advantages of Si, which include available wafer sizes (as large as 300 mm), lower cost (both for the substrates and number of die per wafer), compatibility with semiconductor processing equipment, and the match of the coefficient of thermal expansion with silicon read-out integrated circuit (ROIC). Raytheon has already demonstrated low-defect, high-quality MBE-grown HgCdTe/Si as large as 150 mm in diameter. The focal plane arrays (FPAs) presented in this paper were grown on 100 mm diameter (211)Si substrates in a Riber Epineat system. The basic device structure is an MBE-grown p-on-n heterojunction device. Growth begins with a CdTe/ZnTe buffer layer followed by the HgCdTe active device layers; the entire growth process is performed in␣situ to maintain clean interfaces between the various layers. In this experiment the cutoff wavelengths were varied from 10.0 μm to 10.7 μm at 78 K. Detectors with >50% quantum efficiency and R ₀ A ∼1000 Ohms cm² were obtained, with 256 × 256, 30 μm focal plane arrays from these detectors demonstrating response operabilities >99%. Work supported by the Missile Defense Agency (MDA) through CACI Technologies, Inc. subcontract no. 601-05-0088, NVESD technical task order no. TTO-01, prime contract no. DAAB07-03-D-C214, (delivery order no. 0016)     

MBE growth and device processing of MWIR HgCdTe on large area Si substrates

The traditional substrate of choice for HgCdTe material growth has been lattice matched bulk CdZnTe material. However, as larger array sizes are required for future devices, it is evident that current size limitations of bulk substrates will become an issue and therefore large area Si substrates will become a requirement for HgCdTe growth in order to maintain the cost-efficiency of future systems. As a result, traditional substrate mounting methods that use chemical compounds to adhere the substrate to the substrate holder may pose significant technical challenges to the growth and fabrication of HgCdTe on large area Si substrates. For these reasons, non-contact (indium-free) substrate mounting was used to grow mid-wave infrared (MWIR) HgCdTe material on 3″ CdTe/Si substrates. In order to maintain a constant tepilayer temperature during HgCdTe nucleation, reflection high-energy electron diffraction (RHEED) was implemented to develop a substrate temperature ramping profile for HgCdTe nucleation. The layers were characterized ex-situ using Fourier transform infrared (FTIR) and etch pit density measurements to determine structural characteristics. Dislocation densities typically measured in the 9 10⁶ cm⁻² to 1 10⁷ cm⁻² range and showed a strong correlation between ramping profile and Cd composition, indicating the uniqueness of the ramping profiles. Hall and photoconductive decay measurements were used to characterize the electrical properties of the layers. Additionally, both single element and 32 32 photovoltaic devices were fabricated from these layers. A RA value of 1.8 10⁶-cm² measured at −40 mV was obtained for MWIR material, which is comparable to HgCdTe grown on bulk CdZnTe substrates.     

Full-wafer spatial mapping of macrodefects on HgCdTe epitaxial wafers grown by MBE

We have constructed an optical microscopy system to automatically locate, count, and determine the size of polycrystalline “void” defects on epitaxial layers of HgCdTe grown on CdZnTe or Si substrates. Void macrodefects are readily imaged because their polycrystalline surface is rough, and consequently they scatter light out of the image under specular reflection imaging conditions. Using a computer-controlled stage to move the wafer, a succession of individual, contiguous bright-field images is recorded over the entire wafer. Each image is analyzed by software to locate and characterize all the light-scattering objects present in the frame. Several different representations of the spatial distribution and size of defects are generated, and these can be presented either as false-color density maps or dot-location maps. In addition, various types of statistics on the defect population and size distributions are also available. These data not only convey overall information on the quality of a given wafer, and as such are quite useful for screening to determine which wafers are suitable for array fabrication, but they also allow inferences to be made concerning the origin or root cause of different classes of defects. Several examples are presented to illustrate the use of full-wafer defect mapping to identify macrodefect problems in HgCdTe growth on CdZnTe that can arise from substrate temperature lateral nonuniformity, nonmatched source flux angular distributions, substrate contamination, and intrinsic substrate imperfections.     

VSWIR to VLWIR MBE grown HgCdTe material and detectors for remote sensing applications

The molecular beam epitaxy (MBE) growth technology is inherently flexible in its ability to change the Hg_1−xCd_xTe material’s bandgap within a growth run and from growth run to growth run. This bandgap engineering flexibility permits tailoring the device architecture to the various specific requirements. Material with active layer x values ranging from ∼0.198 to 0.570 have been grown and processed into detectors. This wide range in x values is perfectly suited for remote sensing applications, specifically the National Polar Orbiting Environmental Satellite System (NPOESS) program that requires imaging in a multitude of infrared spectral bands, ranging from the 1.58 to 1.64 μm VSWIR (very short wave infrared) band to the 11.5 to 12.5 μm LWIR (longwave infrared) band and beyond. These diverse spectral bands require high performance detectors, operating at two temperatures; detectors for the VSWIR band operate near room temperature while the SWIR, MWIR (mid wave infra red), LWIR and VLWIR (very long wave infrared) detectors operate near 100K, because of constraints imposed by the cooler for the NPOESS program. This paper uses material parameters to calculate theoretical detector performance for a range of x values. This theoretical detector performance is compared with median measured detector optical and electrical data. Measured detector optical and electrical data, combined with noise model estimates of ROIC performance are used to calculate signal to noise ratio (SNR), for each spectral band. The SNR are compared with respect to the meteorological NPOESS system derived focal plane. The derived system focal plane requirements for NPOESS are met in all the spectral bands.     

MBE growth and characterization of in situ arsenic doped HgCdTe

We report the results of in situ arsenic doping by molecular beam epitaxy using an elemental arsenic source. Single Hg_1−xCd_xTe layers of x ∼0.3 were grown at a lower growth temperature of 175°C to increase the arsenic incorporation into the layers. Layers grown at 175°C have shown typical etch pit densities of 2E6 with achievable densities as low as 7E4cm⁻². Void defect densities can routinely be achieved at levels below 1000 cm⁻². Double crystal x-ray diffraction rocking curves exhibit typical full width at half-maximum values of 23 arcsec indicating high structural quality. Arsenic incorporation into the HgCdTe layers was confirmed using secondary ion mass spectrometry. Isothermal annealing of HgCdTe:As layers at temperatures of either 436 or 300°C results in activation of the arsenic at concentrations ranging from 2E16 to 2E18 cm⁻³. Theoretical fits to variable temperature Hall measurements indicate that layers are not compensated, with near 100% activation after isothermal anneals at 436 or 300°C. Arsenic activation energies and 77K minority carrier lifetime measurements are consistent with published literature values. SIMS analyses of annealed arsenic doping profiles confirm a low arsenic diffusion coefficient.     

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.     

HgCdTe/CdTe/Si infrared photodetectors grown by MBE for near-room temperature operation

Conventional HgCdTe infrared detectors need significant cooling in order to reduce noise and leakage currents resulting from thermal generation and recombination processes. Although the need for cooling has long been thought to be fundamental and inevitable, it has been recently suggested that Auger recombination and generation rates can be reduced by using the phenomena of exclusion and extraction to produce nonequilibrium carrier distributions. The devices with Auger suppressed operation requires precise control over the composition, and donor and acceptor doping. The successful development of the molecular beam epitaxy (MBE) growth technique for multi-layer HgCdTe makes it possible to grow these device structures. Theoretical calculations suggest that the p n+ layer sequence is preferable for near-room temperature operation due to longer minority carrier lifetime in lightly doped p-HgCdTe absorber layers. However, because the low doping required for absorption and nonequilibrium operation is easier to achieve in n-type materials, and because Shockley-Read centers should be minimized in order to obtain the benefits of Auger suppression, we have focused on p⁺ n structures. Planar photodiodes were formed on CdTe/Si (211) composite substrates by As implantation followed by a three step annealing sequence. Three inch diameter Si substrates were employed since they are of high quality, low cost, and available in large areas. Due to this development, large area focal plane arrays (FPAs) operated at room temperature are possible in the near future. The structures were characterized by FTIR, x-ray diffraction, temperature dependent Hall measurements, minority carrier lifetimes by photoconductive decay, and in-situ ellipsometry. To study the relative influence of bulk and surface effects, devices with active areas from 1.6 10⁻⁵ cm² to 10⁻³ cm² were fabricated. The smaller area devices show better performance in terms of reverse bias characteristics indicating that the bulk quality could be further improved. At 80 K, the zero bias leakage current for a 40 m 40 m diode with 3.2 m cutoff wavelength is 1 pA, the R₀A product is 1.1 10⁴-cm² and the breakdown voltage is in excess of 500 mV. The device shows a responsivity of 1.3 10⁷ V/W and a 80 K detectivity of 1.9 10¹¹ cm-Hz^1/2/W. At 200 K, the zero bias leakage current is 5 nA and the R₀A product 2.03-cm², while the breakdown voltage decreases to 40 mV.     

Arsenic incorporation during MBE growth of HgCdTe

We discuss the equilibrium model of the amphoteric behavior of arsenic in HgCdTe and its applicability to material grown by molecular beam epitaxy. Suggestions are made on how to achieve active incorporation by manipulating the surface orientation, or by using precursors that provide steric hindrance.     

Progress in the Molecular Beam Epitaxy of HgCdTe on Large-Area Si and CdZnTe Substrates

This paper presents the progress in the molecular beam epitaxy (MBE) growth of HgCdTe on large-area Si and CdZnTe substrates at Raytheon Vision Systems. We report a very high-quality HgCdTe growth, for the first time, on an 8 cm × 8 cm CdZnTe substrate. This paper also describes the excellent HgCdTe growth repeatability on multiple 7 cm × 7 cm CdZnTe substrates. In order to study the percentage wafer area yield and its consistency from run to run, small lots of dual-band long-wave infrared/long-wave infrared triple-layer heterojunction (TLHJ) layers on 5 cm × 5 cm CdZnTe substrates and single-color double-layer heterojunction (DLHJ) layers on 6-inch Si substrates were grown and tested for cutoff wavelength uniformity and micro- and macrovoid defect density and uniformity. The results show that the entire lot of 12 DLHJ-HgCdTe layers on 6-inch Si wafers meet the testing criterion of cutoff wavelength within the range 4.76 ± 0.1 μm at 130 K and micro- and macrovoid defect density of ≤50 cm⁻² and 5 cm⁻², respectively. Likewise, five out of six dual-band TLHJ-HgCdTe layers on 5 cm × 5 cm CdZnTe substrates meet the testing criterion of cutoff wavelength within the range 6.3 ± 0.1 μm at 300 K and micro- and macrovoid defect density of ≤2000 cm⁻² and 500 cm⁻², respectively, on the entire wafer area. Overall we have found that scaling our HgCdTe MBE process to a 10-inch MBE system has provided significant benefits in terms of both wafer uniformity and quality.