Microstructural and optical characterization of CdTe(211)B/ZnTe/Si(211) grown by molecular beam epitaxy

CdTe layers have been grown by molecular beam epitaxy on 3 inch nominal Si(211) under various conditions to study the effect of growth parameters on the structural quality. The microstructure of several samples was investigated by high resolution transmission electron microscopy (HRTEM). The orientation of the CdTe layers was affected strongly by the ZnTe buffer deposition temperature. Both single domain CdTe(133)B and CdTe(211)B were obtained by selective growth of ZnTe buffer layers at different temperatures. We demonstrated that thin ZnTe buffer layers (<2 nm) are sufficient to maintain the (211) orientation. CdTe deposited at ∼300°C grows with its normal lattice parameter from the onset of growth, demonstrating the effective strain accommodation of the buffer layer. The low tilt angle (<1°) between CdTe[211] and Si[211] indicates that high miscut Si(211) substrates are unnecessary. From low temperature photoluminescence, it is shown that Cd-substituted Li is the main residual impurity in the CdTe layer. In addition, deep emission bands are attributed to the presence of As_Te and Ag_Cd acceptors. There is no evidence that copper plays a role in the impurity contamination of the samples.     

High-Quality (211)B CdTe on (211)Si Substrates Using Metalorganic Vapor-Phase Epitaxy

High-quality (211)B CdTe buffer layers are required during Hg_1−x Cd _x Te heteroepitaxy on Si substrates. In this study, direct metalorganic vapor-phase epitaxy (MOVPE) of (211)B CdTe on Si, as well as CdTe on Si using intermediate Ge and ZnTe layers, has been achieved. Tertiary butyl arsine was used as a precursor to enable As surfactant action during CdTe MOVPE on Si. The grown CdTe/Si films display a best x-ray diffraction rocking-curve full-width at half-maximum of 64 arc-s and a best Everson etch pit density of 3 × 10⁵ cm⁻². These values are the best reported for MOVPE-grown (211)B CdTe/Si and match state-of-the-art material grown using molecular-beam epitaxy.     

Cyclic Annealing During Metalorganic Vapor-Phase Epitaxial Growth of (211)B CdTe on (211) Si Substrates

High-quality (211)B CdTe buffer layers on Si substrates are required to enable Hg_1–x Cd _x Te growth and device fabrication on lattice-mismatched Si substrates. Metalorganic vapor-phase epitaxy (MOVPE) of (211)B CdTe on Si substrates using Ge and ZnTe interlayers has been achieved. Cyclic annealing has been used during growth of thick CdTe layers in order to improve crystal quality. The best (211)B CdTe/Si films grown in this study display a low x-ray diffraction (XRD) rocking-curve full-width at half-maximum (FWHM) of 85 arcsec and etch pit density (EPD) of 2 × 10⁶ cm⁻². These values are the best reported for MOVPE-grown (211) CdTe/Si and are comparable to those for state-of-the-art molecular beam epitaxy (MBE)-grown CdTe/Si.     

Microstructural Characterization of CdTe(211)B/ZnTe/Si(211) Heterostructures Grown by Molecular Beam Epitaxy

Transmission electron microscopy and small-probe microanalysis have been used to investigate the microstructure and compositional profiles of CdTe(211)B/ZnTe/Si(211) heterostructures. Thin ZnTe buffer layers and subsequent thick CdTe layers were grown on Si(211) substrates using molecular beam epitaxy. Many {111}-type stacking faults were found to be present throughout the entire ZnTe layer, terminating near the point of initiation of CdTe growth. A rotation angle of about 3.5° was observed between lattice planes of the Si substrate and the final CdTe epilayer. Local lattice parameter measurement and elemental profiles indicated that some intermixing of Zn and Cd had taken place. The average widths of the ZnTe layer and the (Cd,Zn)Te transition region were found to be roughly 6.5 nm and 3.5 nm, respectively.     

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).     

Growth of Lattice-Matched ZnTeSe Alloys on (100) and (211)B GaSb

A key issue with the current HgCdTe/Si system is the high dislocation density due to the large mismatch between HgCdTe and Si. An alternative system that has superior lattice matching is HgCdSe/GaSb. A buffer layer to mitigate issues with direct nucleation of HgCdSe on GaSb is ZnTe_1?x Se _x . We have performed preliminary studies into the growth of lattice-matched ZnTe_1?x Se _x on both (100) and (211)B GaSb. The effects of substrate orientation, substrate temperature, and growth conditions on the morphology and crystallography of ZnTe_0.99Se_0.01 alloys were investigated. The lattice-matching condition yielded minimum root-mean-square (rms) roughness of 1.1?nm, x-ray rocking curve full-width at half-maximum (FWHM) value of ~29?arcsec, and density of nonradiative defects of mid-10⁵?cm^?2 as measured by imaging photoluminescence.     

分子束外延CdTe（211）B／Si复合衬底材料

报道了用MBE的方法，在3英寸Si衬底上制备ZnTe／CdTe（211）B复合衬底材料的初步研究结果，该研究结果将能够直接应用于大面积Si基HgCdTe IRFPA材料的生长．经过Si（211）衬底低温表面处理、ZnTe低温成核、高温退火、高温ZnTe、CdTe层的生长研究，用MBE方法成功地获得了3英寸Si基ZnTe／CdTe（211）B复合衬底材料．CdTe厚度大于10μm，XRD FWHM平均值为120arc sec，最好达到100arc sec，无（133）孪晶和其他多晶晶向．     

Investigation of MBE-Growth of Mid-Wave Infrared Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se

Undoped mid-wave infrared Hg_1?xCd_xSe epitaxial layers have been grown to a nominal thickness of 8–14 μm on GaSb (211)B substrates by molecular beam epitaxy (MBE) using constant beam equivalent pressure ratios. The effects of growth temperature from 70°C to 120°C on epilayer quality and its electronic parameters has been examined using x-ray diffraction (XRD) rocking curves, atomic force microscopy, Nomarski optical imaging, photoconductive decay measurements, and variable magnetic field Hall effect analysis. For samples grown at 70°C, the measured values of XRD rocking curve full width at half maximum (FWHM) (116 arcsec), root mean square (RMS) surface roughness (2.7 nm), electron mobility (6.6?×?10⁴ cm² V^?1 s^?1 at 130 K), minority carrier lifetime (～?2 μs at 130 K), and background n-type doping (～?3?×?10¹⁶ cm^?3 at 130 K), indicate device-grade material quality that is significantly superior to that previously published in the open literature. All of these parameters were found to degrade monotonically with increasing growth temperature, although a reasonably wide growth window exists from 70°C to 90°C, within which good quality HgCdSe can be grown via MBE.     

Microstructure of Heteroepitaxial ZnTe Grown on GaAs(211)B by Molecular Beam Epitaxy

ZnTe was grown on GaAs(211)B by molecular beam epitaxy (MBE). Structural properties and strain relaxation at the ZnTe/GaAs(211)B interface were investigated by high resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM). Application of digital image processing involving a filtered inverse fast Fourier transformation revealed an array of misfit dislocations at the interface and allowed strain relaxation to be estimated. Only one twin defect was observed in the HRTEM images, and details of this twin defect were investigated by STEM.     

Lattice Relaxation and Dislocation Reduction in MBE CdTe(211)B/Ge(211)

We have used x-ray diffraction to assess the thickness dependence of strain in molecular-beam epitaxial (MBE) CdTe(211)/Ge(211). For 25-nm-thick layers, we find tensile stress of 100 MPa and in-plane strain of ~1.5 × 10⁻³. This stress relaxes during growth and becomes zero beyond 1 μm. We use the Dunn and Koch formula to estimate the threading dislocation density from the full-width at half-maximum of the (224) rocking curve. We then estimate the annihilation radius of MBE-grown CdTe(211)B/Ge(211) to be ~10 nm. Our layers have etch pit densities between 5 × 10⁷ cm⁻² and 5 × 10⁶ cm⁻² for a thickness of 10 μm. The lowest densities were obtained by periodic annealing epitaxy. We discuss mechanisms for the saturation of the dislocation density.     

(211)-Oriented Domain Formation During Growth of ZnTe on m-Plane Sapphire by MBE

ZnTe epilayers have been grown on 2°-tilted m-plane $\left( {10\overline{1} 0} \right)$ sapphire substrates by molecular beam epitaxy. Pole figure imaging was used to study the domain distribution within the layer, and the pole figures of 111, 220, 004, and 422 ZnTe and $30\overline{3} 0$ sapphire were measured. Computer simulation was used to analyze the symmetry of the diffraction patterns seen in the pole figure images. Stereographic projections were also compared with the pole figures of 422 and 211 ZnTe, confirming that single-domain (211)-oriented ZnTe epilayers had been grown on the 2°-tilted m-plane sapphire substrates. Although differences in crystal structure and lattice mismatch were severe in these heterostructures, precise control of the substrate surface’s lattice arrangement would result in the formation of high-quality epitaxial layers.     

Dislocation arrangements in gaas/ga1−xlnxas multilayers grown on (001), (111) and (112) substrates

GaAs/Ga_1−xIn_xAs strained layer superlattices with well-widths of 7 nm, barrier widths of 14 nm and periods of 10 to 30 have been examined by transmission electron microscopy in plan view and in cross-section for (001), (111) and (112) substrates. Individual layers are below the critical thickness while the overall SLS's are above the critical thickness for dislocation generation. (001) substrates give rise to square grids of 60° dislocations lying parallel to 〈110〉 directions with inclined 1/2 〈101〉 Burgers vectors, resulting from dislocation motion on 8 slip systems. (111) substrates give triangular networks of 60° dislocations lying parallel to 〈110〉 directions resulting from motion on 6 slip systems. (112) substrates have two sets of primary dislocations lying along (132) directions, along with secondary 60° dislocations lying along [110]. Long Lomer-Cottrell dislocations with Burgers vectors lying parallel to the substrate/SLS interface are occasionally observed for (001) substrates, while short segments are observed for (112) substrates; these are formed by reaction between conjugate dislocations. These dislocations arrangements are discussed in terms of the resolved shear stresses resulting from epitaxy for the various substrates orientations. Dislocation densities are much less than those required for complete strain relief. This is analyzed in terms of the reduction in the stress acting on dislocations from partial strain relief, along with a friction stress due to a combination of the Peierls stress and solution hardening from the In substitution. A friction stress ∼10^-3μ is required to explain the observed dislocation densities (μ, is the shear modulus).     

The Surface Kinetics of MBE-Grown CdTe (211)B During In Situ Cyclic Annealing

The surface kinetics of CdTe (211)B grown by molecular beam epitaxy (MBE) is investigated using spectroscopic ellipsometry (SE) during in situ cyclic annealing. A method of measuring sublimation rates from high-index surfaces without use of reflection high-energy electron diffraction is presented. The effect of Te₂ overpressure on the activation energy of sublimation for the CdTe (211)B surface is reported. The sensitivity of SE to surface temperature and film thickness was leveraged to monitor sublimation rates of CdTe stabilized by a Te₂ overpressure. The sublimation activation energy was found to increase from 0.45 eV to 2.94 eV under the Te₂ beam pressure regime investigated.     

Surface Structure of Molecular Beam Epitaxy (211)B HgCdTe

The as-grown molecular beam epitaxy (MBE) (211)B HgCdTe surface has variable surface topography, which is primarily dependent on substrate temperature and substrate/epilayer mismatch. Nano-ripple formation and cross-hatch patterning are the predominant structural features observed. Nano-ripples preferentially form parallel to the \( [\bar {1}11] \) and are from 0 Å to 100 Å in height with a wavelength between 0.1 μm and 0.8 μm. Cross-hatch patterns result from slip dislocations in the three {111} planes intersecting the (211) growth surface. The cross-hatch step height is 4 ± 1 Å (limited data set). This indicates that only a bi-layer slip (Hg/Cd + Te) in the {111} slip plane occurs. For the deposition of MBE (211)B HgCdTe/CdTe/Si, the reorientation of multiple nano-ripples coalesced into “packets” forms cross-hatch patterns. The as-grown MBE (211)B CdTe/Si surface is highly variable but displays nano-ripples and no cross-hatch pattern. Three types of defects were observed by atomic force microscopy (AFM): needle, void/hillock, and voids.     

Structural Characterization of Integrated II–VI and III–V Heterostructures for Solar Cell Applications

We report on the microstructural characterization of monolithically integrated II–VI and III–V heterostructures that are being developed for possible solar cell applications. Observations by transmission electron microscopy have shown that the growth of lattice-matched ZnTe layers on GaSb(100) substrates resulted in very high quality interfaces and very few structural defects. We then investigated short-period superlattices (SSLs) of CdSe and CdTe digital alloys grown using ZnTe buffer layers on GaSb substrates. The effect of rapid thermal annealing was also studied. High-resolution electron micrographs showed that the CdSe-CdTe SSL had very high quality for approximately 25–50 periods closest to the substrate but that considerable stacking faults and microtwins were visible in layers near the top surface of the sample. For comparison purposes, CdSe layers grown on InAs(100) substrates, again using ZnTe as a buffer layer, were also characterized. The quality of the CdSe layer was not as good as that observed in the SSL sample, possibly because of the larger lattice mismatch between the materials.     

Dislocation profiles in HgCdTe(100) on GaAs(100) grown by metalorganic chemical vapor deposition

We studied dislocation etch pit density (EPD) profiles in HgCdTe(lOO) layers grown on GaAs(lOO) by metalorganic chemical vapor deposition. Dislocation profiles in HgCdTe(lll)B and HgCdTe(lOO) layers differ as follows: Misfit dislocations in HgCdTe(lll)B layers are concentrated near the HgCdTe/CdTe interfaces because of slip planes parallel to the interfaces. Away from the HgCdTe/CdTe interface, the HgCdTe(111)B dislocation density remains almost constant. In HgCdTe(lOO) layers, however, the dislocations propagate monotonically to the surface and the dislocation density decreases gradually as dislocations are incorporated with increasing HgCdTe(lOO) layer thicknesses. The dislocation reduction was small in HgCdTe(lOO) layers more than 10 μm from the HgCdTe/CdTe interface. The CdTe(lOO) buffer thickness and dislocation density were similarly related. Since dislocations glide to accommodate the lattice distortion and this movement increases the probability of dislocation incorporation, incorporation proceeds in limited regions from each interface where the lattice distortion and strain are sufficient. We obtained the minimum EPD in HgCdTe(100) of 1 to 3 x 10⁶ cm^-2 by growing both the epitaxial layers more than 8 μm thick.     

The influence of supercooling on the liquid phase epitaxial growth of inas1−xsbx on (100) GASB substrates

The growth by liquid-phase epitaxy of InAs_1−x Sb _x (x = 0.08-0.16) on GaSb was accomplished by using melts of constant arsenic concentration x _As ^L = 0.014. The study of the influence of the degree of supercooling ΔT on the crystal growth was investigated. The strong tendency of the In-As-Sb liquid to dissolve the GaSb substrate was resolved by using high ΔT (20-30° C) for layers having a positive lattice-mismatch Δa/a more than 1.5 x 10⁻³. As positive lattice-mismatch becomes smaller, a larger supersaturation is required to control the substrate dissolution. But owing to the bulk nucleation which restricts the supercooling ΔT at values near 30° C, the growth of epitaxial layers with small lattice-mismatch (until - 5 × 10⁻⁴) was achieved only from time to time. It was observed that an increase of ΔT increases the concentration of antimony in the epilayers and hence leads to the lattice-mismatch. The dislocation etch pit density was found to be only dependent on the lattice-mismatch. The thickness of the grown layers is proportional to ΔT xt ^1/2 with a factorK = 0.025 μm . °C⁻² . s^−1/2     

Study of Surface Treatments on InAs/GaSb Superlattice LWIR Detectors

We report on the comparison of mesa sidewall profiles of InAs/GaSb strained-layer superlattice (SLS) detector structures (λ _{50% cutoff} ≈ 14 μm at V _bias = 0 V and T = 30 K) obtained after (a) a conventional BCl₃-based inductively coupled plasma etch, (b) a chemical etch (H₂O₂:HCl:H₂O, 1:1:4), and (c) a combination of both etches. We found that the smoothest sidewall profile with reasonable undercut (~5 μm) was obtained after chemical etch only. The chemical etch was optimized primarily using an n-type GaSb substrate. During this process, numerous chemical etchants were examined. GaSb n-type substrates were chosen for this study in preference over InAs substrates due to their high chemical reactivity and the complicated composition of the native oxide. In addition, SLS detectors are usually grown on GaSb substrates and, after hybridization of the focal-plane array to the readout integrated circuit, the GaSb substrate is etched away using a combination of wet and dry etching techniques. We found that H₂O₂:HCl:H₂O (1:1:4) etching solution provided the smoothest etched surface of GaSb, with a root-mean-square roughness of 1.59 nm.     

Gas-cluster ion-beam smoothing of chemo-mechanical-polish processed GaSb(100) substrates

Gas-cluster ion-beam (GCIB) processing of surfaces provides individual atoms within an accelerated gas cluster (∼1,500 atoms per cluster), an energy approximately equal to the individual bond energy of the target surface atoms. The gas-cluster beam is thus capable of providing smoothing and etching of the extreme surface of numerous semiconductors, metals, insulators, and magnetic materials. For semiconductor material systems, the gas-cluster processing effect on the surface and subsurface material is of critical interest for device and circuitry application integrity. In the case of III–V GaSb, chemo-mechanical or touch polishing is the final step in the semiconductor-wafer manufacturing process, often leaving scratches of various depths or damage on the polished surface. In this paper, we report the GCIB etching and smoothing of chemical-mechanical polished GaSb(100) wafers. Using a dual-energy, dual gas-cluster source process, ∼100 nm of material was removed from a GaSb(100) surface. Atomic-force microscopy (AFM) imaging and power spectral-density (PSD) analysis shows significant decrease in the post-GCIB root-mean-square (Rms) roughness and peak-to-valley measurements for the material systems. X-ray rocking-curve analysis has shown a 24-arcsec reduction in the full-width at half-maximum (FWHM) of the (111) x-ray diffraction peak of GaSb. High-resolution transmission-electron microscopy (HRTEM) shows the crystallinity of the subsurface of the pre- and post-GCIB surfaces to be consistent, following the 1 × 10¹⁶ ions/cm² total-fluence processes, with dislocation density for both pre- and post-GCIB cases below the HRTEM resolution limit. X-ray photoelectron spectroscopy (XPS) indicates a strong Ga 3p electron binding-energy intensity for gallium-oxide formation on the GaSb surface with the use of an oxygen GCIB process. Analysis of the Ga 3p electron binding-energy peaks in the XPS data in conjunction with HRTEM indicates a higher Ga or GaSb content in the near-surface layer (less stoichiometric-oxide presence) with use of a CF₄/O₂ GCIB process. The same peak analysis indicates that the surface gallium-oxide state is nearly unchanged, except in thickness, with the use of an O₂-GCIB second step. The material results suggest that GCIB provides a viable method of chemo-mechanical polish (CMP) damage removal on group III–V material for further device processing.     

Effects of Thickness and Annealing on Optoelectronic Properties of Electrodeposited ZnS Thin Films for Photonic Device Applications

Thin layers of ZnS with thicknesses of 400 nm, 500 nm, and 700 nm have been electrodeposited on glass/fluorine-doped tin oxide substrates using a simple two-electrode setup under similar conditions. Structural characterization of the layers using x-ray diffraction (XRD) measurements showed that they were amorphous. The results of optical characterization carried out in the wavelength range of 315 nm to 800 nm using spectrophotometry revealed that the optical properties of the layers are strongly influenced by the film thickness as well as annealing conditions. The values of the refractive index, extinction coefficient, absorption coefficient, and dielectric constant obtained from normal-incidence transmittance spectra were generally lower after annealing, showing also the influence of postdeposition annealing on the deposited ZnS layers. Electrical characterization of the layers, using direct-current current–voltage measurement under dark conditions at room temperature, shows that the resistivity of the as-deposited and annealed layers is in the range of 1.4 × 10⁴ Ω cm to 2.5 × 10⁴ Ω cm and 2.5 × 10⁴ Ω cm to 3.1 × 10⁴ Ω cm, respectively. The results suggest that the optoelectronic properties can be tuned for particular applications by adjusting the thickness of the layers appropriately.