Progress in CdZnTe substrate producibility and critical drivers of IRFPA yield originating with CdZnTe substrates

With the goal of maximizing the yield of infrared focal plane arrays (IRFPAs), Santa Barbara Research Center’s (SBRC) Infrared Materials Producibility Program (IRMP) has focused on assessing and improving the quality, yield, and throughput of CdZnTe substrates. A baseline detector lot was fabricated to identify the critical drivers of IRFPA yield coming from the substrates and to evaluate the quality and yield of the current vendor base for CdZnTe substrates. Substrate induced defects and impurities that can potentially affect device performance and operability were carefully mapped out in detail on 44 × 67 mm² size substrates, received from IRMP substrate vendors as well as SBRC. This paper will report on the correlations found between this substrate characterization data base and the IRFPA level defect distributions. Key results from these correlation studies are: (1) extended defects found on the substrates with the Nakagawa etch correlated well with responsivity reduction in the final IRFPA; (2) cross-hatch patterns that were evident in the responsivity map correlated well with similar features seen by x-ray topography on LPE double layers; and (3) a possible correlation of device performance (leakage current at 78K) with copper and lithium impurities in the substrate. Recent initiatives toward improving the quality and yield of the substrate growth process have focused on improving purity in the pre-growth charge preparation, modification of growth parameters to reduce defects and scaling up of the vertical Bridgman growth process from its current 67 mm diameter boule size to 92 mm diameter boules. Promising initial results from the large diameter boule growth process will be shown. The 92 mm diameter CdZnTe boule (6 kg charge) shows two predominant single crystal grains encompassing 75% of boule volume. Defect characterization of boules grown under baseline and modified conditions is discussed.     

Distribution of the high resistivity region in CdZnTe and its effects on gamma-ray detector performance

The effect of the location of the high resistivity region on gamma-ray detector performance within the crystal boule is investigated for 10% zinc with 1.5% excess Te. By varying the indium-doping concentration in several CdZnTe boules, the region of high resistivity is seen to move along the vertical length of the crystal. The variation of the zinc concentration within the crystal boule is compared with the location of the high resistivity region along the length of the crystals. The concentration of zinc is extracted from Fourier transform infrared (FTIR) measurements, and the segregation coefficient is calculated using data obtained from the CdZnTe crystals. The zinc distribution is plotted in terms of the location along the crystal length in order to correlate the concentration with detector performance. Radiation spectra obtained from the 122-KeV gamma rays using a ⁵⁷Co source reveal a strong dependence between detector performance and the relative location of the high resistivity region within the crystal. Initial results suggest that there are three semi-distinct regions along the length of the boule that give very different characteristics, where it can be said that the best detector performance is in the middle region with a 6% resolution of the 122-KeV peak, which is quite good for test detectors without a guard ring such as these. It is determined that this middle region has a zinc concentration of ∼9–11%, which varies slightly from the original concentration of 10%. The differences in the performance characteristics are discussed, and defect distribution within the crystal as the main source of the variation is suggested. Also, based on the results, it is believed that the role of indium is essentially to compensate for the vacancies in the crystal and, therefore, is secondary to the crystalline properties and impurities within the boule. Overall, it is believed that crystalline defects and inclusions play a greater role in determining the performance characteristics of CdZnTe radiation detectors.     

Uniformity and reproducibility studies of low-pressure-grown Cd<Subscript>0.90</Subscript>Zn<Subscript>0.10</Subscript>Te crystalline materials for radiation detectors

A large number of room-temperature detectors have been produced from CdZnTe crystals grown with 10% Zn and 1.5% excess tellurium by the low-pressure, vertical-Bridgman technique. Radiation spectra obtained by these crystals using a ²⁴¹Am source reveal the characteristic 59.5-keV line as well as the six low-energy peaks, which include the Cd and Te escape peaks. Similarly, ⁵⁷Co spectra obtained also show a very well-defined 122-keV peak with a 3:1 peak-to-valley ratio. Seven CdZnTe crystals have been grown for reproducibility studies. Four of these crystals have resistivities over 1E9 Ω-cm. Considering that the indiumdoping level is on the order of 2E15 cm⁻³, the reproducibility is excellent. The theoretical basis of the high-resistivity phenomenon in CdZnTe is discussed in reference to a previous paper. The uniformity of these 6-in.-long CdZnTe crystals is studied, and various measurements are carried out, both laterally and vertically, along the boule. It is determined that, in general, roughly a 3.5-in. section near the middle of the 6-in. boule has sufficient resistivity for producing radiation detectors. This nonuniformity along the vertical direction is caused mostly by the composition change of Cd, Zn, Te, and In-doping level in the growth melt caused by differences in the segregation coefficients of these elements. Although, variations in resistivity are seen across some of the wafer slices, most show very good uniformity with high breakdown voltage. Some of the variations are attributed to the different grains within the boule. Similar results are seen in the measured radiation spectra obtain on 4 mm × 4 mm × 2 mm samples from different locations across the wafer, where some samples show well-resolved secondary peaks, while others display only the primary spectral lines.     

Resonance lonization spectroscopy for quantitative and sensitive surface and bulk measurements of impurities in II-VI materials

We have applied resonance ionization spectroscopy for the first time on II-VI materials, Cd, Te, CdZnTe, and HgCdTe for the measurement of trace impurities. It is an analytical technique with extremely high sensitivity, selectivity, dynamic range, and quantitation accuracy. The technique provides virtual freedom from matrix effects and minimizes isobaric and other mass interferences, known to be the shortcomings in secondary ion mass spectroscopy and other mass spectroscopic measurements. Quantitative analysis of Cu in bulk CdZnTe boules has shown Cu concentration in the range low 10¹⁴ to low 10¹⁵ cm^-3 with an average copper content in four different boules near 2 x 10¹⁴ cm^-3. High Cu concentration (1-2 x 10¹⁷ cm^-3) measured in some HgCdTe epitaxial layers correlated with lower Hall mobility in the layer, and in one case the intentionally In-doped, n-type HgCdTe layer turned p-type.     

CdZnTe substrate producibility and its impact on IRFPA yield

The need for cost effective production of HgCdTe infrared detectors and focal plane assemblies has led to increased attention to the availability of high quality large-area CdZnTe substrates. Reasonable yield of large-area substrates (≥4 cm×6 cm format) is necessary for fabrication of focal plane assemblies (FPAs) now in production, and for future infrared (IR) detectors which are growing in size and complexity. Raytheon’s infrared materials producibility (IRMP) program has addressed this issue, after identifying critical drivers of FPA yield coming from substrates, and targeted certain improvements in substrate process steps for highest impact on large-area substrate yield. Three specific areas of improvements in the substrate process were addressed: (1) compounding of a large 6 kg charge of CdTe; (2) vertical Bridgman growth of 92 mm diameter CdZnTe boules in both quartz and pyrolytic boron nitride (PBN) crucibles; and (3) optimized Cd overpressure control during growth and cool-down of the boule. It was shown that the Cd overpressure and the cooling schedule had the strongest effects on defect populations. The resulting improvements include a 33% increase in wafer yield per unit starting weight, an estimated 50% reduction in substrate cost per cm², better morphology of epitaxial HgCdTe layers, and improved yield of satisfactory IR detectors. The criteria for selecting substrates have also improved as a result of this work. In addition, photovoltaic detectors were fabricated on wafers from a variety of sources, and tested. Results compare favorably with those on baseline (earlier process) substrates.     

The growth of low dislocation density Sr1−x,Bax Nb2O6 crystals

The dislocation structures of both pure and Nd doped strontium barium niobate crystals, grown by the Czochralski method, were studied using an etch pit technique. It was determined that dislocations in the boule were being propagated from the seed and were confined to the center of the crystal. Typical dislocation density was 5x10⁴ cm⁻². Through the careful control of growth parameters and use of seed material cut from the dislocation free outer portion of a crystal, it was possible to grow crystals with very low dislocation densities, 1x10² cm⁻², and on occasion dislocation free crystals.     

Vertical bridgman techniques to homogenize zinc composition of CdZnTe substrates

In order to improve the Zn homogeneity along the axial direction of CdZnTe boule, we have employed a modified Bridgman technique using a (Cd, Zn) alloy source in communication with the melt, whose temperature has been gradually changed from 800 to 840°C during growth. Electron probe microanalysis (EPMA) measurements of Zn composition in the boule shows an excellent homogeneity of Zn along the axis of the CdZnTe boule compared with results in a boule grown by using a fixed source temperature. We have performed a numerical simulation to obtain the approximate temperatures of additional heating and cooling needed to improve the radial Zn homogeneity. CdZnTe boule has been grown by seeded vertical Bridgman furnace with two zones of heater and cooler. Ultraviolet/visible spectroscopic measurements of Zn composition over the length of the boule indicate that the radial distribution of Zn composition is very homogeneous in the body region of the boule, where the radial variation of Zn composition is ±0.0005.     

Growth and characterization of large Nd,Cr:GSGG crystals forhigh-average-power slab lasers

Nd,Cr:GSGG crystal boules up to 13 cm in diameter and 20.5 cm long have been grown by the Czochralski method. Several problems with Nd,Cr:GSGG growth were identified, and solved separately but not all at once; these problems included spiral boule growth, 1-μm absorption loss, iridium on the melt surface, iridium inclusions, boule cracking, dislocation, and fine scattering (smoke). In the grown crystals parameters relevant to their eventual use as gain elements for large slab lasers were measured including optical homogeneity, birefringence, absorption loss at 1 μm, scattering loss, and iridium inclusions. The optical homogeneity of the boules is good, except for a radial gradient in refractive index of about 10^-5 cm^-1. The birefringence is low (<3 nm/cm) in slabs cut from the boules. Scattering losses in the boules range from 0.01 to 0.08 cm^-1. This absorption has been reduced to <0.0025 cm^-1 in small samples using reducing heat treatments, but appropriate treatment conditions for full-scale slabs have yet to be determined     

The annealing of Cd1−xZnxTe in CdZn vapors

As-grown CdZnTe usually contains defects, such as twins, subgrain boundaries, dislocations, and Te precipitates. It is always important to anneal CdZnTe slices in Cd vapor to eliminate these defects, especially Te precipitates. The exchange of Zn atoms between the slices and the vapor plays an important role during the annealing process. In this paper, the effects of Zn partial pressure on the properties of the annealed slices are studied carefully by measuring the concentration profiles, the infrared (IR) transmission spectra, and the x-ray rocking curves. It was found that a surface layer with different compositions and possibly different structure from the bulk crystal formed during the annealing of CdZnTe samples in the saturated Zn vapor. The accumulation of excess Te in the surface layer helps to increase the IR permeability of the bulk crystal greatly. To improve the crystallization quality, a lower Zn-pressure annealing should be used following the high Zn-pressure annealing. The diffusion of Zn in the bulk crystal has also been analyzed at the temperatures of 700°C and 500°C. Calculations determined that D_Zn (700°C)=4.02 × 10⁻¹² cm²s⁻¹ and D_Zn (500°C)=1.22 × 10⁻¹³ cm²s⁻¹.     

Advancements in THM-Grown CdZnTe for Use as Substrates for HgCdTe

The focus of this work is to evaluate the suitability and substrate potential of Cd_0.9Zn_0.1Te and Cd_0.96Zn_0.04Te crystals grown by the traveling heater method (THM). THM-grown Cd_0.9Zn_0.1Te crystals used for gamma spectroscopy have shown very good spectral performance owing partly to the very low concentration of Te inclusions and precipitates. Inspection in the infrared (IR) of annealed THM-grown CdZnTe wafers reveals no inclusions >3 μm, and Fourier-transform infrared measurements show IR transmission values in excess of 60%. Wafer etch pit density values are typically less than 4 × 10^?4 pits/cm², and double-crystal x-ray rocking-curve measurements show full-width at half-maximum values approaching 40 arcsec. 〈211〉 wafers have been produced with off orientation within 0.3°. (111)-Oriented, seeded THM growth runs have the ability to provide 10 60 mm × 60 mm × 2 mm wafers from a 75-mm-diameter boule or 20 90 mm × 90 mm × 2 mm wafers from a 100-mm-diameter boule.