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.     

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.     

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.     

Recent developments of high-complexity HgCdTe focal plane arrays at leti infrared laboratory

In this article, we present recent developments of the research in France at LETI infrared laboratory in the field of complex third-generation HgCdTe IRCMOS focal plane arrays (FPAs). We illustrate this with three prototypes of FPAs made at LETI, which have involved some technological improvements from the standard process today in production at Sofradir. We present, using molecular-beam epitaxy (MBE) growth, a 128 × 128 dual-band infrared (photodetector)-complementary metal oxide semiconductor (IRCMOS) with a pitch of 50 μm operating within 2–5 μm. Using the more conventional liquid-phase epitaxy (LPE) growth, we show a new generation of high-performance long linear arrays (1500 × 2; pitch, 30 μm) operating in medium-wavelength infrared (MWIR) or long-wavelength infrared (LWIR) bands based on a modular architecture of butted HgCdTe detection circuit and SiCMOS multiplexers. Finally, we present for the first time a megapixel (1000 × 1000) FPA with a pitch of 15 μm operating in the MWIR band that exhibits a very high performance and pixel operability.     

Status of the MBE technology at leti LIR for the manufacturing of HgCdTe focal plane arrays

This paper presents recent developments that have been made in Leti Infrared Laboratory in the field of molecular beam epitaxy (MBE) growth and fabrication of medium wavelength and long wavelength infrared (MWIR and LWIR) HgCdTe devices. The techniques that lead to growth temperature and flux control are presented. Run to run composition reproducibility is investigated on runs of more than 15 consecutively grown layers. Etch pit density in the low 10⁵ cm⁻² and void density lower than 10³ cm⁻² are obtained routinely on CdZnTe substrates. The samples exhibit low n-type carrier concentration in the 10¹⁴ to 10¹⁵ cm⁻³ range and mobility in excess of 10⁵ cm²/Vs at 77 K for epilayers with 9.5 μm cut-off wavelength. LWIR diodes, fabricated with an-on-p homojunction process present dynamic resistance area products which reach values of 8 10³ Ωcm² for a biased voltage of −50 mV and a cutoff wavelength of 9.5 μm at 77 K. A 320 × 240 plane array with a 30 μm pitch operating at 77 K in the MWIR range has been developed using HgCdTe and CdTe layers MBE grown on a Germanium substrate. Mean NEDT value of 8.8 mK together with an operability of 99.94% is obtained. We fabricated MWIR two-color detectors by the superposition of layers of HgCdTe with different compositions and a mixed MESA and planar technology. These detectors are spatially coherent and can be independently addressed. Current voltage curves of 60 × 60 μm² photodiodes have breakdown voltage exceeding 800 mV for each diode. The cutoff wavelength at 77 K is 3.1 μm for the MWIR-1 and 5 μm for the MWIR-2.     

Surface structure of plasma-etched (211)B HgCdTe

The surface of (211)B HgCdTe has been studied by reflection high-energy electron diffraction (RHEED) and atomic force microscopy (AFM). RHEED analysis of the as-grown Hg-rich molecular beam epitaxy (MBE) (211)B HgCdTe suggests the surface reconstructs by additional Hg incorporation. The plasma-etched (211)B HgCdTe surface is crystalline but stepped and facetted. RHEED analysis indicates asymmetric pyramids (base dimensions ≈0.5×1.1 nm) are formed to minimize surface Hg concentration. The AFM examination of plasma-etched (211)B HgCdTe reveals oriented mesoscopic features.     

HgCdTe focal plane arrays for dual-color mid- and long-wavelength infrared detection

Raytheon Vision Systems (RVS, Goleta, CA) in collaboration with HRL Laboratories (Malibu, CA) is contributing to the maturation and manufacturing readiness of third-generation, dual-color, HgCdTe infrared staring focal plane arrays (FPAs). This paper will highlight data from the routine growth and fabrication of 256×256 30-μm unit-cell staring FPAs that provide dual-color detection in the mid-wavelength infrared (MWIR) and long wavelength infrared (LWIR) spectral regions. The FPAs configured for MWIR/MWIR, MWIR/LWIR, and LWIR/LWIR detection are used for target identification, signature recognition, and clutter rejection in a wide variety of space and ground-based applications. Optimized triple-layer heterojunction (TLHJ) device designs and molecular beam epitaxy (MBE) growth using in-situ controls has contributed to individual bands in all dual-color FPA configurations exhibiting high operability (>99%) and both performance and FPA functionality comparable to state-of-the-art, single-color technology. The measured spectral cross talk from out-of-band radiation for either band is also typically less than 10%. An FPA architecture based on a single-mesa, single-indium bump, and sequential-mode operation leverages current single-color processes in production while also providing compatibility with existing second-generation technologies.     

Correlation of CdZnTe(211)B substrate surface morphology and HgCdTe(211)B epilayer defects

We present results on the surface morphology and recombination lifetimes of molecular-beam epitaxy (MBE)-grown HgCdTe (211)B epilayers and correlate them with the roughness of the CdZnTe substrate surfaces. The substrate surface quality was monitored by in-situ spectroscopic ellipsometry (SE) and reflection high-energy electron diffraction (RHEED). The SE roughness of the substrate was measured after oxide desorption in the growth chamber. The RHEED patterns collected show a strong correlation with the SE roughness. This proves that SE is a valuable CdZnTe prescreening tool. We also found a correlation between the substrate roughness and the epilayer morphologies. They are characterized by a high density of thin elongated defects, “needle defects,” which appear on most samples regardless of growth conditions. The HgCdTe epilayers grown on these substrates were characterized by temperature-dependent, photoconductive decay-lifetime data. Fits to the data indicate the presence of mid-gap recombination centers, which were not removed by 250°C/24-h annealing under a Hg-rich atmosphere. These centers are believed to originate from bulk defects rather than Hg vacancies. We show that Te annealing and CdTe growth on the CdZnTe substrates smooth the surface and lower substantially the density of needle defects. Additionally, a variety of interfacial layers were also introduced to reduce the defect density and improve the overall quality of the epilayer, even in the presence of less than perfect substrates. Both the perfection of the substrate surface and that of its crystalline structure are essential for the growth of high-quality material. Thus, CdZnTe surface polishing procedures and growth techniques are crucial issues.     

Status of MBE technology for the flexible manufacturing of HgCdTe focal plane arrays

A robust process has been developed for the reproducible growth of in-situ doped Hg_1−xCd_xTe:As alloys by molecular beam epitaxy. Net hole concentrations in excess of 5 x 10¹⁷ cm⁻³, with peak mobilities >200 cm2/Vs were measured in Hg_0.74Cd_0.26Te:As films. The p-type layers were twin-free and consistently exhibit narrow x-ray rocking curves (<40 arc sec). The reproducible growth of small lots of p-on-n LWIR detector structures has been established. For a typical lot consisting of 13 layers, the average x-value of the n-type base layer was 0.226 with a standard deviation of 0.003. The lateral compositional uniformity across a 2.5 cm × 2.5 cm wafer was × = +- 0.0006. High performance p-on-n LWIR diodes were fabricated that exhibited R_oA_o values (0-fov at 78K) as large as 350 Q cm2 at 10.4 μm.     

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.     

Molecular-beam epitaxial growth of HgCdTe infrared focal-plane arrays on silicon substrates for midwave infrared applications

Molecular beam epitaxy has been employed to deposit HgCdTe infrared detector structures on Si(112) substrates with performance at 125K that is equivalent to detectors grown on conventional CdZnTe substrates. The detector structures are grown on Si via CdTe(112)B buffer layers, whose structural properties include x-ray rocking curve full width at half maximum of 63 arc-sec and near-surface etch pit density of 3–5 × 10⁵ cm⁻² for 9 μm thick CdTe films. HgCdTe p⁺-on-n device structures were grown by molecular beam epitaxy (MBE) on both bulk CdZnTe and Si with 125K cutoff wavelengths ranging from 3.5 to 5 μm. External quantum efficiencies of 70%, limited only by reflection loss at the uncoated Si-vacuum interface, were achieved for detectors on Si. The current-voltage (I-V) characteristics of MBE-grown detectors on CdZnTe and Si were found to be equivalent, with reverse breakdown voltages well in excess of 700 mV. The temperature dependences of the I-V characteristics of MBE-grown diodes on CdZnTe and Si were found to be essentially identical and in agreement with a diffusion-limited current model for temperatures down to 110K. The performance of MBE-grown diodes on Si is also equivalent to that of typical liquid phase epitaxy-grown devices on CdZnTe with R₀A products in the 10⁶–10⁷ Θ-cm² range for 3.6 μm cutoff at 125K and R₀A products in the 10⁴–10⁵ Θ-cm² range for 4.7 μm cutoff at 125K.     

Inductively coupled plasma etching for large format HgCdTe focal plane array fabrication

Inductively coupled plasma (ICP) using hydrogen-based gas chemistry has been developed to meet requirements for deep HgCdTe mesa etching and shallow CdTe passivation etching in large format HgCdTe infrared focal plane array (FPA) fabrication. Large format 2048×2048, 20-μm unit-cell short wavelength infrared (SWIR) and 2560×512, 25-μm unit-cell midwavelength infrared (MWIR) double-layer heterojunction (DLHJ) p-on-n HgCdTe FPAs fabricated using ICP processing exhibit >99% pixel operability. The HgCdTe FPAs are grown by molecular beam epitaxy (MBE) on Si substrates with suitable buffer layers. Midwavelength infrared detectors fabricated from 4-in. MBE-grown HgCdTe/Si substrates using ICP for mesa delineation and CdTe passivation etching demonstrate measured spectral characteristics, RoA product, and quantum efficiency comparable to detectors fabricated using wet chemical processes. Mechanical samples prepared to examine physical characteristics of ICP reveal plasma with high energy and low ion angle distribution, which is necessary for fine definition, high-aspect ratio mesa etching with accurate replication of photolithographic mask dimensions.     

Real-time monitoring of the surface stoichiometry during molecular beam epitaxy of cubic GaN on (001) GaAs by RHEED

We study the plasma-assisted molecular beam epitaxy of cubic GaN on GaAs(OOl) substrates by means ofin-situ reflection high-energy electron diffraction. The epilayers are characterized by x-ray diffraction, photoluminescence, and Hall measurements, and it is found that the overall best films are grown under a N/Ga ratio close to one. For anin-situ determination of the N/Ga ratio, the growth kinetics is studied via surface reconstruction transitions. The effective N flux giving rise to growth is measured using the transient behavior of the half-order diffraction streak intensity for various plasma operating conditions.     

Heteroepitaxy of HgCdTe(112) infrared detector structures on Si(112) substrates by molecular-beam epitaxy

High-quality, single-crystal epitaxial films of CdTe(112)B and HgCdTe(112)B have been grown directly on Si(112) substrates without the need for GaAs interfacial layers. The CdTe and HgCdTe films have been characterized with optical microscopy, x-ray diffraction, wet chemical defect etching, and secondary ion mass spectrometry. HgCdTe/Si infrared detectors have also been fabricated and tested. The CdTe(112)B films are highly specular, twin-free, and have x-ray rocking curves as narrow as 72 arc-sec and near-surface etch pit density (EPD) of 2 × 10⁶ cm⁻² for 8 μm thick films. HgCdTe(112)B films deposited on Si substrates have x-ray rocking curve FWHM as low as 76 arc-sec and EPD of 3-22 × 10⁶ cm⁻². These MBE-grown epitaxial structures have been used to fabricate the first high-performance HgCdTe IR detectors grown directly on Si without use of an intermediate GaAs buffer layer. HgCdTe/Si infrared detectors have been fabricated with 40% quantum efficiency and R₀A = 1.64 × 10⁴ Ωm₂ (0 FOV) for devices with 7.8 μm cutoff wavelength at 78Kto demonstrate the capability of MBE for growth of large-area HgCdTe arrays on Si.     

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.     

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.     

Molecular-beam epitaxial growth of CdSe<Subscript>x</Subscript>Te<Subscript>1−x</Subscript> on Si(211)

We report on the first successful growth of the ternary-alloy CdSe_xTe_1−x(211) on 3-in. Si(211) substrates using molecular-beam epitaxy (MBE). The growth of CdSeTe was performed using a compound CdTe effusion source and an elemental Se effusion source. The alloy composition (x) of the CdSe_xTe_1−x ternary compound was controlled through the Se:CdTe flux ratios. Our results indicated that the crystalline quality of CdSeTe decreases as the alloy composition increases, which is possibly due to an alloy-disordering effect. A similar trend was observed for the CdZnTe ternary-alloy system. However, the alloy-disordering effect in CdSeTe was found to be less severe than that in CdZnTe. We have carried out the growth of CdSeTe on Si at different temperatures. An optimized growth window was established for CdSeTe on Si(211) to achieve high-crystalline-quality CdSeTe/Si layers with 4% Se. The as-grown layers exhibited excellent surface morphology, low surface-defect density (less than 500 cm⁻²), and low x-ray full width at half maximum (FWHM) values near 100 arcsec. Additionally, the CdSeTe/Si layer exhibited excellent lateral uniformity and the best etched-pit density (EPD) value on a 4% CdSeTe, measured to be as low as 1.4 × 10⁵ cm⁻².     

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.     

分子束外延InAs量子点的RHEED实时原位分析

介绍了利用反射式高能电子衍射(RHEED)方法在自组装InAs量子点制备过程中进行结构分析的理论研究与实验工作的最新进展。从反射式高能电子衍射在InAs量子点临界转变状态测定、量子点表面取向、量子点应力分布测定、量子点形核长大动力学过程研究等方面的应用,可以看出RHEED在InAs量子点形成过程中对多种结构特征的原位分析具有突出优势。反射式高能电子衍射仪作为分子束外延系统中的标准配置,已成为一种对InAs量子点微观结构进行分析的简易而理想的分析测试工具。随着反射式高能电子衍射以及衍射理论的进一步发展,必将促进InAs量子点结构的精确表征水平的提高,进而实现更加理想结构的InAs量子点的制备及其应用。     

Kinetic process of nitridation on the α-sapphire surface

我们结合分子动力学模拟和动态蒙特卡洛方法,建立了蓝宝石表面的氮化模拟模型,依此揭示了氮化和过度氮化的过程和原理。通过MBE生长和同位RHEED表征,我们亦观察和分析了不同条件下的α面蓝宝石的氮化情况。结合模拟和实验,我们了解了氮化机制,并且圈定了合适的氮化范围。