Formation and control of defects during molecular beam epitaxial growth of HgCdTe

Void defects were demonstrated to form away from the substrate-epifilm interface during the molecular beam epitaxial growth of mercury cadmium telluride on cadmium zinc telluride substrates. These were smaller in size compared to voids which nucleated at the substrate-epifilm interface, which were also observed. Observations of void nucleation away from the substrate-epifilm interface were related to the respective growth regimes active at the time of the void nucleation. Once nucleated, voids replicated all the way to the surface even if the flux ratios were modified to prevent additional nucleation of voids. For a significant number of films, void defects were observed co-located with hillocks. These voids were usually smaller than 1 μm and appeared almost indistinguishable from unaccompanied simple voids. However, these void-hillock complexes displayed a nest of dislocation etch pits around these defects upon dislocation etching, whereas unaccompanied voids did not. The nests could extend as much as 25 μm from the individual void-hillock complex. The density of dislocations within the nest exceeded 5×10⁶ cm⁻², whereas the dislocation density outside of the nest could decrease to <2×10⁵ cm⁻². The void-hillock complexes formed due to fluctuations in growth parameters. Elimination of these fluctuations drastically decreased the concentrations of these defects.     

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.     

Effect of incident angle in spectral ellipsometry on composition control during molecular beam epitaxial growth of HgCdTe

The effect of incident angle in spectral ellipsometry (SE) on composition control of Hg_1−xCd_xTe grown by molecular beam epitaxy (MBE) was investigated. Although a small uncertainty in the incident angle tends to have a significant impact on the ellipsometric data, and therefore the composition data, it was found that the incident angle uncertainty could be corrected in the SE model calculation, resulting in an “optimized” incident angle that would give the best fit between measured and calculated ellipsometric data. Experimental data supporting this simple corrective or optimization procedure for the incident angle are presented.     

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.     

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.     

Molecular beam epitaxial growth and performance of HgCdTe-based simultaneous-mode two-color detectors

Molecular beam epitaxy was employed for the growth of HgCdTe-based n-p⁺-n device structures on (211)B oriented CdZnTe substrates. The device structures were processed as mesa isolated diodes, and operated as back-to-back diodes for the simultaneous detection of two closely spaced sub-bands in the mid-wave infrared spectrum. The devices were characterized by R₀A values in excess of 5 × 10⁵ Ω cm² at 78K, at f/2 fov and quantum efficiencies greater than 70% in each band. Infrared imagery from a focal plane array with 128 × 128 pixels was acquired simultaneously from each band at temperatures between 77 to 180K, with no observable degradation in the image quality with increase in temperature.     

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.     

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.     

HgCdTe composition determination using spectroscopic ellipsometry during molecular beam epitaxy growth of near-infrared avalanche photodiode device structures

The application of spectroscopic ellipsometry (SE) for real-time composition determination during molecular beam epitaxy (MBE) growth of Hg_1−xCd_xTe alloys with x>0.5 is reported. Techniques previously developed for SE determination of composition in long-wavelength infrared (LWIR) HgCdTe have been successfully extended to near-infrared HgCdTe avalanche photodiode (APD) device structures with x values in the range of 0.6–0.8. Ellipsometric data collected over a spectral range of 1.7–5 eV were used to measure depth profiles of HgCdTe alloy composition through the use of an optical model of the growth surface. The optical model used a dielectric-function database collected through the growth of a set of HgCdTe calibration samples with x ranging from 0.6 to 0.8. The sensitivity of this SE method of composition determination is estimated to be Δx ∼0.0002 at x=0.6, which is sufficiently low to sense composition changes arising from flux variations of less than 0.1%. Errors in composition determination because of Hg-flux variations appear to be inconsequential, while substrate-temperature fluctuations have been observed to alter the derived composition at a rate of −0.0004/°C. By comparing the composition inferred from SE and postgrowth 300 K IR transmission measurements on a set of APD device structures, the run-to-run precision of the Se-derived composition (at x=0.6) is estimated to be ±0.0012, which is equivalent to the precision achieved with the same instrumentation during the growth of mid-wavelength infrared (MWIR) HgCdTe alloys in the same MBE system.     

Molecular beam epitaxial growth and performance of integrated two-color HgCdTe detectors operating in the mid-wave infrared band

The first report of molecular beam epitaxial growth and performance of HgCdTe two-color detectors for the simultaneous detection of radiation at 4.1 and 4.5 μm is presented. In-situ doped devices with the n-p-n architecture were grown by molecular beam epitaxy on (211)B CdZnTe substrates. Representative structures exhibited x-ray rocking curves with full width at half-maxima of 40–60 arcs. The typical near surface etch pit density in these structures were 4−7 × 10⁶ cm⁻². The devices were processed as mesa diodes and electrical contacts were made to the two n-type layers and the p-type layer to facilitate simultaneous operation of the two p-n junctions. The spectral response characteristics of the devices were characterized by sharp turn-on and turn-off for both bands, with R₀A values >5 × 10⁵ ωcm² at 77K. The detectors exhibited quantum efficiencies >70% in both bands.     

High performance SWIR HgCdTe detector arrays

Short wave infrared (SWIR) devices have been fabricated using Rockwell’s double layer planar heterostructure (DLPH) architecture with arsenic-ion implanted junctions. Molecular beam epitaxially grown HgCdTe/CdZnTe multilayer structures allowed the thin, tailored device geometries (typical active layer thickness was ∼3.5 μm and cap layer thickness was ∼0.4 μm) to be grown. A planar-mesa geometry that preserved the passivation advantages of the DLPH structure with enhanced optical collection improved the performance. Test detectors showed Band 7 detectors performing near the radiative limit (∼3-5X below theory). Band 5 detector performance was ∼4-50X lower than radiative limited performance, apparently due to Shockley-Hall-Read recombination. We have fabricated SWIR HgCdTe 256 × 12 × 2 arrays of 45 um × 45 μm detector on 45 μm × 60 μm centers and with cutoff wavelength which allows coverage of the Landsat Band 5 (1.5−1.75 μm) and Landsat Band 7 (2.08−2.35 μm) spectral regions. The hybridizable arrays have four subarrays, each having a different detector architecture. One of the Band 7 hybrids has demonstrated performance approaching the radiative theoretical limit for temperatures from 250 to 295K, consistent with test results. D* performance at 250K of the best subarray was high, with an operability of ∼99% at 10¹² cm Hz^1/2/W at a few mV bias. We have observed 1/f noise below 8E-17 AHz ^1/2 at 1 Hz. Also for Band 7 test structures, Ge thin film diffractive microlenses fabricated directly on the back side of the CdZnTe substrate showed the ability to increase the effective collection area of small (nominally <20 μm μm) planar-mesa diodes to the microlens size of 48 urn. Using microlenses allows array performance to exceed 1-D theory up to a factor of 5.     

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。     

Molecular beam epitaxy growth of HgCdTe on Ge for third-generation infrared detectors

The Leti-Lir has studied II–VI compounds for infrared (IR) detection for more than 20 years. The need to reduce the production cost of IR focal plane arrays (FPAs) sparked the development of heteroepitaxy on large-area substrates. Germanium has been chosen as the heterosubstrate for the third generation of IR detectors. First, we report on the progress achieved in HgCdTe growth on 3-in. and 4-in. (211)B CdTe/Ge. Then, we discuss the choice of a new machine for larger size and better homogeneity. Finally, we present the latest results on third-generation IR multicolor and megapixel devices. First-time results regarding a middle wavelength infrared (MWIR) dual-band FPA, with a reduced pitch of 25 μm, and a MWIR 1,280×1,024 FPA will be shown. Both detectors are based on molecular beam epitaxy (MBE)-grown HgCdTe on Ge. The results shown validate the choice of Ge as the substrate for third-generation detectors.     

Uniform low defect density molecular beam epitaxial HgCdTe

This paper describes recent advances in MBE HgCdTe technology. A new 3 inch production molecular beam epitaxy (MBE) system, Riber Model 32P, was installed at Rockwell in 1994. The growth technology developed over the years at Rockwell using the Riber 2300 R&D system was transferred to the 32P system in less than six months. This short period of technology transfer attests to our understanding of the MBE HgCdTe growth dynamics and the key growth parameters. Device quality material is being grown routinely in this new system. Further advances have been made to achieve better growth control. One of the biggest challenges in the growth of MBE HgCdTe is the day-to-day control of the substrate surface temperature at nucleation and during growth. This paper describes techniques that have led to growth temperature reproducibility within + - 1°C, and a variation in temperature during substrate rotation within 0.5°C. The rotation of the substrate during growth has improved the uniformity of the grown layers. The measured uniformity data on composition for a typical 3 cm × 3 cm MBE HgCdTe/CdZnTe shows the average and standard deviation values of 0.229 and 0.0006, respectively. Similarly, the average and standard deviation for the layer thickness are 7.5 and 0.06 μm, respectively. P-on-n LWIR test structure photodiodes fabricated using material grown by the new system and using rotation during growth have resulted in high-performance (R₀)A, quantum efficiency) devices at 77 and 40K. In addition, 128 × 28 focal plane arrays with excellent performance and operability have been demonstrated.     

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.     

Molecular-beam epitaxial growth and high-temperature performance of HgCdTe midwave infrared detectors

Results are reported on the molecular-beam epitaxial (MBE) growth and electrical performance of HgCdTe midwave-infrared (MWIR) detector structures. These devices are designed for operation in the 140–160 K temperature range with cutoff wavelengths ranging from 3.4–3.8 μm at 140 K. Epitaxial structures, grown at 185°C on (211)B-oriented CdZnTe substrates, consisting of either conventional two-layer P-n configurations or three-layer P-n-N configurations, were designed to examine the impact of device performance on variation of the n-type base layer (absorber) thickness and the inclusion or omission of an underlying wide-bandgap buffer layer. Devices were grown with absorber thicknesses of 3 μm, 5 μm, and 7 μm to examine the tradeoff between the spectral response characteristic and the reverse-bias electrical performance. In addition, 5-μm-thick, wide-bandgap HgCdTe buffer layers, whose CdTe mole fraction was approximately 0.1 larger than the absorber layer, were introduced into several device structures to study the effect of isolating the device absorbing layer from the substrate/growth initiation interface. The MBE-grown epitaxial wafers were processed into passivated, mesa-type, discrete device structures and diode mini arrays, which were tested for temperature-dependent R₀A product, quantum efficiency, spectral response, and the I-V characteristic at temperatures close to 140 K. External quantum efficiencies of 75–79% were obtained with lateral optical-collection lengths of 7 μm. Analysis of the temperature dependence of the diode R₀A product indicates that the device impedance is limited by the diffusion current at temperatures above 140 K with typical R₀A values of 2×10⁶ Ω cm² for a detector cutoff of 3.8 μm at 140 K. An alloy composition anomaly at the absorbing-layer/buffer-layer interface is believed to limit the observed R₀A products to values approximately one order of magnitude below the theoretical limit projected for radiatively limited carrier lifetime. Device electrical performance was observed to be improved through incorporation of a wide-bandgap buffer layer and through reduction of the absorbing layer thickness. An optimum spectral response characteristic was observed for device structures with 5-μm-thick absorbing layers.     

3英寸Si基碲镉汞分子束外延工艺研究

随着红外焦平面阵列规模的扩大,由于尺寸和成本的限制,传统晶格匹配的碲锌镉衬底逐渐成为碲镉汞红外焦平面探测器发展的瓶颈,大尺寸、低成本硅基碲镉汞材料应运而生。本文采用分子束外延工艺生长获得了3 in Si基中波碲镉汞薄膜材料,通过采用金相显微镜、傅里叶红外光谱仪、双晶X射线衍射仪、湿化学腐蚀位错密度(EPD)法、Hall测试系统等检测手段对Si基中波碲镉汞分子束外延薄膜材料进行表面、光学、结构和电学性能表征,并采用标准平面器件工艺制备中波640×512焦平面探测阵列进行材料验证,结果表明该材料性能与国际先进水平相当。     

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.     

Molecular beam epitaxy HgCdTe growth-induced void defects and their effect on infrared photodiodes

We have carried out a study and identified that MBE HgCdTe growth-induced void defects are detrimental to long wavelength infrared photodiode performance. These defects were induced during nucleation by having surface growth conditions deficient in Hg. Precise control and reproducibility of the CdZnTe surface temperature and beam fluxes are required to minimize such defects. Device quality material with void defect concentration values in the low 10² cm² range were demonstrated.     

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.