Lateral uniformity in HgCdTe layers grown by molecular beam epitaxy

The fabrication of high-quality focal plane arrays from HgCdTe layers grown by molecular beam epitaxy (MBE) requires a high degree of lateral uniformity in material properties such as the alloy composition, doping concentration, and defect density. While it is well known that MBE source flux nonuniformity can lead to radial compositional variation for rotating substrates, we have also found that composition can be affected significantly by lateral variations in substrate temperature during growth. In diagnostic experiments, we systematically varied the substrate temperature during MBE and quantified the dependence of HgCdTe alloy composition on substrate temperature. Based on these results, we developed a methodology to quickly and nondestructively characterize MBE-grown layers using postgrowth spatial mapping of the cutoff wavelength from the Fourier transform infrared (FTIR) transmission at 300 K, and we were able to obtain a quantitative relationship between the measured spatial variations in cutoff and the substrate temperature lateral distribution during growth. We refined this methodology by more directly inferring the substrate temperature distribution from secondary ion mass spectroscopy (SIMS) measurements of the As concentration across a wafer, using the fact that the As incorporation rate in MBE-grown p-type layers is highly sensitive to substrate temperature. Combining this multiple-point SIMS analysis with FTIR spatial mapping, we demonstrate how the relative contributions from flux nonuniformity and temperature variations on the lateral composition uniformity can be separated. This capability to accurately map the lateral variations in the substrate temperature has been valuable in optimizing the mounting and bonding of large substrates for MBE growth, and can also be valuable for other aspects of MBE process development.     

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.     

碲镉汞材料中Hg空位、Au、As掺杂的研究进展

碲镉汞材料是制造红外探测器的基础,高性能红外探测器对碲镉汞材料的要求越来越高。为了提升器件性能,必须提高碲镉汞材料的电学性能。而掺杂是一个很好的选择。碲镉汞材料掺杂可以分为n型和p型两种。对于n型掺杂来说,In是一种理想的掺杂剂,其掺杂研究目前已比较成熟。相对而言,p型掺杂研究还不是那么深入。Hg空位、Au、As掺杂均为碲镉汞材料中常见的p型掺杂手段。通过分析和总结近些年的部分相关文献,介绍了碲镉汞材料中Hg空位、Au、As掺杂的研究进展。     

Molecular beam epitaxy growth of high-quality arsenic-doped HgCdTe

We have initiated a joint effort to better elucidate the fundamental mechanisms underlying As-doping in molecular beam epitaxy (MBE)-grown HgCdTe. We have greatly increased the As incorporation rate by using an As cracker cell. With a cracker temperature of 700°C, As incorporation as high as 4×10²⁰ cm⁻³ has been achieved by using an As-reservoir temperature of only 175°C. This allows the growth of highly doped layers with high quality as measured by low dislocation density. Annealing experiments show higher As-activation efficiency with higher anneal temperatures for longer time and higher Hg overpressures. Data are presented for layers with a wide range of doping levels and for layer composition from 0.2 to 0.6.     

Suppression of strain-induced cross-hatch on molecular beam epitaxy (211)B HgCdTe

Because the performance of HgCdTe-based photodiodes can be significantly degraded by the presence of dislocations, we have systematically investigated and suppressed lattice-mismatch-induced cross-hatch formation and the associated generation of dislocations in (211)B HgCdTe/CdZnTe. A series of HgCdTe epilayers were deposited simultaneously on pairs of substrates with differing ZnTe mole fractions. Epilayers’ CdTe mole fraction and substrates’ ZnTe mole fractions were measured using optical-transmission spectra. Lattice mismatch and residual strain were estimated from room-temperature, x-ray diffraction, and double-crystal rocking-curve measurements (DCRC). It was found that cross-hatch patterns were suppressed in epilayers deposited on nearly lattice-matched substrates (|Δa/a_sub|<0.02%). Such epilayers exhibited excellent crystalline quality as revealed by defect-decoration etching (etch-pit density (EPD)<10⁵ cm⁻²) and x-ray diffraction (full-width at half-maximum (FWHM) ∼10 arcsec). In addition to determining the upper limits of lattice mismatch needed to eliminate cross-hatch, we investigated the use of reticulated substrates as a means to suppress cross-hatch. We found that growth on reticulated mesa structures (<100 μm) with edges parallel to [01-1] resulted in epilayers with substantially reduced cross-hatch-line densities despite large lattice mismatch (Δa/a_sub <0.04%). The use of reticulated substrates could suppress cross-hatch because of lateral-alloy variation in large substrates and complex multistack epilayers (e.g., multicolor detectors).     

原位As掺杂p型碲镉汞薄膜的制备研究

非本征p 型掺杂碲镉汞材料可以有效克服少子寿命偏低等问题,提高长波和甚长波红外焦平面器件的性能。本文重点阐述了As 掺杂实现p型掺杂的基础性原理,以及其制备方法,为p-on-n碲镉汞材料器件研究提供依据。     

InSb分子束外延原位掺杂技术研究

对InSb分子束外延薄膜的本征掺杂、N型掺杂以及P型掺杂进行了研究,其中分别以Be作P 型以及以Si、Te作N 型的掺杂剂。实验采用半绝缘的GaAs衬底作为InSb分子束外延用衬底,通过采用低温生长缓冲层技术降低大失配应力,获得高质量InSb外延膜。实验样品采用霍尔测试以及SIMS测试掺杂浓度和迁移率分析掺杂规律、掺杂元素偏聚和激活规律的影响因素。     

Mode of arsenic incorporation in HgCdTe grown by MBE

The results of arsenic incorporation in HgCdTe layers grown by molecular beam epitaxy (MBE) are reported. Obtained results indicate that arsenic was successfully incorporated as acceptors in MBE-HgCdTe layers after a low temperature anneal. Secondary ion mass spectrometry and Hall effect measurements confirm that arsenic is incorporated with an activation yield of up to 100%. This work confirms that arsenic can be used as an effective dopant of MBE-HgCdTe after a low temperature annealing under Hg-saturated conditions.     

Precise arsenic doping of HgCdTe by MBE and effects on compositional interdiffusion

Characterization data are presented for arsenic-doped Hg_1−xCd_xTe epilayers, grown on CdZnTe substrates by molecular beam epitaxy. Arsenic incorporation is influenced both by the cracker-cell bulk temperature (As flux) and by the substrate surface temperature. An Arrhenius-type equation can be used to fit the As incorporation data, yielding characteristic energies of 1.54 and 6.61 eV for the As cell and HgCdTe surface temperatures, respectively, independent of alloy fraction. This relation allows significantly improved predictability and control in the As doping concentration. The effect of growth temperature on As incorporation is demonstrated using a multilayer test structure with composition stepped in a sequence, with x=0.6, 0.45, 0.3, 0.2, of n-type material, followed by the reverse sequence of As-doped material, with the As cell temperature held constant. Secondary ion mass spectroscopy profiles of this layer again indicate the strong As incorporation dependence on growth temperature. Composition profiles for as-grown and annealed pieces of the multilayer sample show greater interdiffusion for the As-doped region as compared to the undoped region, which is attributed to the Fermi-level enhancement effect.     

碲镉汞As掺杂技术研究

对于MBE原位掺杂,HgCdTe的N型掺杂比较容易,而P型掺杂相对来说难度比较大。作为掺杂杂质的As表现出两性掺杂行为,在富Te的条件下生长,As有很大的几率进入到阳离子位置处。而As必须进入Te位才能参与导电,表现为P型。因此,采取了多种方法,现已获得10^16-10^18坤cm^-3掺杂水平的P型材料。在成功实现As的掺杂后,研究人员对激活退火做了一些研究。研究发现,需要在汞压下经过高温退火,As原子才能占据Te位成为受主杂质。对As在碲镉汞中的扩散系数也进行了研究。     

Gas source molecular beam epitaxy of ZnSe and ZnSe:N

The use of gas source molecular beam epitaxy, using hydrogen selenide and elemental Zn as source materials, has resulted in the growth of high quality ZnSe on closely lattice-matched GaAs and (In,Ga)P. The undoped ZnSe epilayers are comparable in quality to material grown by molecular beam epitaxy, as indicated by narrow double-crystal x-ray diffraction rocking curves and intense photoluminescence dominated by a single donor-bound near-bandedge excitonic feature. Nitrogen species, derived from a radio frequency plasma source, are successfully used as acceptor impurities for ZnSe; photoluminescence spectra confirm the incorporation of nitrogen by the presence of the expected donor-to-acceptor pair recombination. Atomic concentrations of nitrogen as high as 5 x 10¹⁸ cm^-3, are measured by secondary ion mass spectroscopy. Thus far, capacitance-voltage measurements indicate net acceptor concentrations (N_A -N_D) of approximately 10¹⁷ cm^-3.     

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.     

Precise control of HgCdTe growth conditions for molecular beam epitaxy

A Hg_1-xCd_xTe growth method is presented for molecular beam epitaxy, which precisely controls growth conditions to routinely obtain device quality epilayers at a certain specific composition. This method corrects the fluctuation in composition x for run-to-run growth by feedback from the x value for the former growth to the fluxes from CdTe and Te cells. We achieved standard deviation Δx/ x of 3.3% for 13 samples grown consecutively. A substrate temperature drop was found during growth, which considerably degrades the crystal quality of epilayers. In this method, this drop is greatly diminished by covering the holder surface with a heavily doped Si wafer. Finally, etch pit density of 4 x 10⁴ cm-² and full width at half-maximum of 12 arc-s for the x-ray double-crystal rocking curve were obtained as the best values.     

Modeling of arsenic activation in HgCdTe

We present a theoretical examination of the behavior of arsenic atoms in Hg_1−xCd_xTe for x=0.3, focusing on the thermodynamic conditions that most closely mimic molecular beam epitaxial growth and subsequent annealing steps. We show that, for molecular beam epitaxial growth where tellurium-saturated conditions apply, arsenic incorporates onto the cation sublattice and becomes inactive. A significant fraction of these arsenic atoms are bound to mercury vacancies. We also propose a model of the activation, which involves transfer of the arsenic from the cation to the anion sublattice. The model suggests that activation anneals must be done at high enough temperatures to surmount an activation barrier, and that the phase field from tellurium- to mercury-rich conditions should be traversed slowly enough so that the cation vacancies are not filled before the site transfer can be completed.     

HgCdTe molecular beam epitaxy technology: A focus on material properties

HgCdTe MBE technology is becoming a mature growth technology for flexible manufacturing of short-wave, medium-wave, long-wave, and very long-wave infrared focal plane arrays. The main reason that this technology is getting more mature for device applications is the progress made in controlling the dopants (both n-type and p-type in-situ) and the success in lowering the defect density to less than 2 x 10⁵/cm² in the base layer. In this paper, we will discuss the unique approach that we have developed for growing As-doped HgCdTe alloys with cadmium arsenide compound. Material properties including composition, crystallinity, dopant activation, minority carrier lifetime, and morphology are also discussed. In addition, we have fabricated several infrared focal plane arrays using device quality double layers and the device results are approaching that of the state-of-the-art liquid phase epitaxy technology.     

Activation of arsenic as an acceptor in Hg1−xCdxTe under equilibrium conditions

Arsenic is an amphoteric impurity in Hg_1−xCd_xTe. Under tellurium-rich conditions, it tends to occupy metal-sublattice sites and act as a donor; while under mercury-rich conditions, it tends to occupy the tellurium sublattice and act as an acceptor. In this process, mercury from the ambient, first, displaces an arsenic atom (donor) occupying a metal-sublattice site. This arsenic atom, in turn, displaces a tellurium atom, taking residence on the tellurium sublattice (acceptor). A second mercury atom combines with this excess tellurium atom at a surface or other crystalline discontinuity. A quantitative knowledge of the equilibrium reaction is important both to understand point defects and doping in HgCdTe. An investigation of this equilibrium under selected mercury pressures spanning the entire range from the tellurium-saturated phase limit to the mercury-saturated phase limit reveals that a majority of the arsenic remains on the sites in the tellurium sublattice even under tellurium-saturated conditions for arsenic concentrations less than 2×10¹⁶ cm⁻³. With increasing mercury pressure, the relative population of the arsenic atoms on sites in the tellurium sublattice monotonically increases, reaching 100% for the mercury-saturated limit.     

Minority carrier lifetime in indium-doped HgCdTe(211)B epitaxial layers grown by molecular beam epitaxy

We have studied the minority-carrier lifetime on intentionally indium-doped (211)B molecular beam epitaxially grown Hg_1-xCd_xTe epilayers down to 80K with x ≈ 23.0% ± 2.0%. Measured lifetimes were explained by an Auger-limited band-to-band recombination process in this material even in the extrinsic temperature region. Layers show excellent electron mobilities as high as ≈2 x 10⁵ cm²v^-1s^-1 at low temperatures. When the layers are compensated with Hg vacancies, results show that the Schockley-Read recombination process becomes important in addition to the band-to-band processes. From the values of τ_n0 and τ_p0 of one sample, the obtained defect level is acceptor-like and is somewhat related to the Hg vacancies.     

Si基短波碲镉汞材料分子束外延生长研究

报道了在中波工艺基础上,Si 基碲镉汞分子束外延短波工艺的最新研究进展,通过温度标定、使用反射式高能电子衍射、高温计的在线测量和现有的中波 Si 基碲镉汞温度控制曲线建立及优化了 Si 基碲镉汞短波材料的生长温度控制曲线;获得的 Si 基短波 HgCdTe 材料表面光亮、均匀,表面缺陷密度小于3000 cm －2;基于此技术成功制备出了 Si 基短／中波双色材料。     

Heteroepitaxy of HgCdTe (211)B on Ge substrates by molecular beam epitaxy for infrared detectors

Epitaxial growth of (211)B CdTe/HgCdTe has been achieved on two inch germanium (Ge) by molecular beam epitaxy (MBE). Germanium was chosen as an alternative substrate to circumvent the weaknesses of CdZnTe wafers. The ease of surface preparation makes Ge an attractive candidate among many other alternative substrates. Best MBE CdTe growth results were obtained on (211) Ge surfaces which were exposed to arsenic and zinc fluxes prior to the MBE growth. This surface preparation enabled CdTe growth with B-face crystallographic polarity necessary for the HgCdTe growth. This process was reproducible, and produced a smooth and mirror-like surface morphology. The best value of the {422} x-ray double diffraction full width at half maximum measured from the HgCdTe layer was 68 arc-s. We present the 486 point maps of FWHM statistical values obtained from CdTe/Ge and HgCdTe/CdTe/Ge. High resolution microscopy electron transmission and secondary ion mass spectroscopy characterization results are also presented in this paper. High-performance middle wavelength infrared HgCdTe 32-element photodiode linear arrays, using the standard LETI/LIR planar n-on-p ion implanted technology, were fabricated on CdTe/Ge substrates. At 78K, photodiodes exhibited very high R₀A figure of merit higher than 10⁶ Ωcm⁻² for a cutoff wavelength of 4.8 μm. Excess low frequency noise was not observed below 150K.     

P-Type doping with arsenic in (211)B HgCdTe grown by MBE

Arsenic incorporation and doping in HgCdTe layers grown by molecular beam epitaxy (MBE) were examined in this paper. Arsenic incorporation into MBE-HgCdTe was carried out in two different ways: (1)ex-situ arsenic ion-implantation on indium-doped n-type HgCdTe layers, and (2) through a new approach called arsenic planar doping. We report onex-situ arsenic diffusion on indiumdoped MBE-HgCdTe layers at 450°C. In the investigated layers, arsenic redistribution occurs with a multi-component character. We obtained a diffusion coefficient of D_As = (1-3) × 10⁻¹³ cm²/s at 450°C. Results of differential Hall and fabricated p-n junctions suggest that during high temperature annealing, arsenic preferentially substitutes into Te sublattices and acts as acceptor impurities. In the second case, arsenic has been successfully incorporated during the MBE growth as an acceptor in the planar doping approach. Withoutex-situ annealing, as-grown layers show up to 50% activation of arsenic during the growth. These results are very promising forin-situ fabrication of infrared devices using HgCdTe material.