Electrical activity,mode of incorporation and distribution coefficient of group V elements in Hg1−xCdxTe grown from tellurium rich liquid phase epitxial growth solutions

Hg_1−xCd_xTe films were grown liquid phase epitaxially from tellurium rich solutions containing up to 10 at. % of the group V elements P, As, Sb, and Bi. Chemical analysis of the Te growth solutions and the films was carried out in conjunction with extensive Hall effect measurements on the films subsequent to various annealing treatments under Hg rich and Te rich conditions. Despite the presence of a large concentration of the group V elements in the Te source solution, the maximum concentration of these elements incorporated into the liquid phase epitaxially grown Hg_1-xCd_xTe appears to vary from <10¹⁵cm⁻³ for Bi up to 10¹⁷cm⁻³ for phosphorus and As implying a distribution coefficient varying from <10⁻⁵ for Bi up to 10⁻³ for P at growth temperature of ∼500° C. This low value of the distribution coefficient for group V elements for growths from Te rich solutions contrasts with the moderately high values reported in the literature to date for growth from Hg rich solutions as well as pseudobinary solutions (Bridgman growth). The widely differing distribution coefficients and hence the solubility of the group V elements for Hg rich and Te rich liquid phase epitaxial solutions is explained on the basis that the activity coefficient of the group V elements in Te rich solutions is probably orders of magnitude lower than it is in Hg rich solutions. Finally, the results of the anneals at 200° C under Hg saturated conditions with and without a 500° C Hg saturated preanneal have indicatedn top conversion in many of the films attesting to the amphoteric behavior of the group V elements in LPE grown Hg_1−xCd_xTe(s) similar to the previously reported behavior of P in bulk grown Hg_0.8Cd_0.2Te.     

Lpe growth of Hgl−xCdxTe using conventional slider boat and effects of annealing on properties of the epilayers

The epitaxial layers of Hg_1−xCd_xTe (0.17≦×≦0.3) were grown by liquid phase epitaxy on CdTe (111)A substrates using a conventional slider boat in the open tube H₂ flow system. The as-grown layers have hole concentrations in the 10¹⁷− 10¹⁸ cm⁻³ range and Hall mobilities in the 100−500 cm²/Vs range for the x=0.2 layers. The surfaces of the layers are mirror-like and EMPA data of the layers show sharp compositional transition at the interface between the epitaxial layer and the substrate. The effects of annealing in Hg over-pressure on the properties of the as-grown layers were also investigated in the temperature range of 250−400 °C. By annealing at the temperature of 400 °C, a compositional change near the interface is observed. Contrary to this, without apparent compositional change, well-behaved n-type layers are obtained by annealing in the 250−300 °C temperature range. Sequential growth of double heterostructure, Hg_l−xCd_xTe/Hg_l−yCd_yTe on a CdTe (111)A substrate was also demonstrated.     

Chemical–Mechanical Polishing of CdTe and ZnxCd1?xTe Single Crystals by H2O2(HNO3)–HBr–Organic Solvent Etchant Compositions

Chemical–mechanical polishing of CdTe and Zn _x Cd_1−x Te single-crystal surfaces by bromine-evolving compositions based on aqueous solutions of H₂O₂(HNO₃)–HBr–solvent has been investigated. The dependences of the chemical–mechanical polishing rate on the dilution of the base polishing etchant for various organic components have been determined. The surface condition after such polishing has been investigated using profilometry. The polishing etchant compositions for CdTe and Zn _x Cd_1−x Te single-crystal surfaces and the chemical polishing conditions have been optimized.     

Magneto-optical Studies of Spin Phenomena in CdMnTe Doped with Co and Cr

We investigate the magneto-optical and magnetic properties of two quaternary diluted magnetic semiconductor alloys, Cd_1−x−y Mn _x Cr _y Te and Cd_1−x−y Mn _x Co _y Te, with fixed Mn concentration x ∼ 0.37 and, respectively, with concentrations of Cr in the range 0 < y < 0.07 and Co in the range␣0 < y < 0.009. The introduction of Cr and Co leads to very different behaviors, including the occurrence of ferromagnetic order in the case of Cd_1−x−y Mn _x Cr _y Te. We discuss the possible origins leading to the observed behaviors.     

A study of polycrystalline Cd(Zn,Mn)Te/Cds films and interfaces

Polycrystalline films of Cd_1-x Zn _x Te (x = 0–0.4) and Cd_1-x Mn _x Te (x = 0–0.25) were grown by MBE and MOCVD, respectively, on CdS/SnO₂/glass substrates to investigate their feasibility for solar cell applications. The compositional uniformity and interface quality of the films were analyzed by x-ray diffraction, surface photovoltage, and Auger depth profile measurements to establish a correlation between growth conditions and lattice constant, atomic concentration, and bandgap of the ternary films. MBE-grown polycrystalline Cd_1-x Zn _x Te films showed a linear dependence between Zn/(Cd + Zn) beam flux ratio, Zn concentration in the film, and the bandgap. Polycrystalline Cd_1-x Zn _x Te films grown at 300° C showed good compositional uniformity in contrast to compositionally non-uniform Cd_1-x Mn _x Te films grown by MOCVD in the temperature range of 420–450° C. The MBE-grown Cd_1-x Zn _x Te interface also showed significantly less interdiffusion compared to the MOCVD-grown Cd_1-x Mn _x Te/CdS interface, where preferential exchange between Cd from the CdS layer and Mn from the Cd_1-x Mn _x Te film was observed. The compositional uniformity of MOCVD-grown polycrystalline Cd_1-x Mn _x Te films grown on CdS/SnO₂/glass substrates was found to be a strong function of the growth conditions as well as the Mn source.     

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.     

Planar p-on-n HgCdTe FPAs by Arsenic Ion Implantation

This paper reviews recent developments in the characterization of planar p-on-n photodiodes fabricated from long- and mid-wavelength Hg_1−x Cd _x Te at␣the Electronics and Information Technology Laboratory (LETI). The Hg_1−x Cd _x Te epitaxial layers were grown by both liquid-phase and molecular-beam epitaxy. Planar p-on-n photodiodes were fabricated by arsenic implantation into an indium-doped Hg_1−x Cd _x Te base layer. Electro-optical characterization on these p-on-n photodiodes showed low leakage currents (shunt resistance > 10 GΩ) and mean R ₀ A values comparable to the state of the art, i.e., equal to 5000 Ω cm² at λ _c = 9.3 μm (λ _c: cutoff wavelength). Results of focal-plane arrays operating in both the long-wavelength infrared (IR) and middle-wavelength IR bands are reported, with noise equivalent delta temperature and responsivity values at λ _c = 9.3 μm in excess of 99.64%. These results demonstrate the viability and technological maturity of both material growth and device processing.     

A Scanning Probe Microscopy Study of Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te

The effects of several ex vacuo methods used in the surface preparation of Cd_1−x Zn _x Te (CZT) have been studied using noncontact atomic force microscopy, scanning tunneling microscopy, and scanning tunneling spectroscopy. Preparation techniques include mechanical lapping, hydroplane bromine-methanol polishing, and in vacuo annealing. The morphology, electrical homogeneity, and local density of states (LDOS) have been studied for each preparation method. Impurities and oxides quickly form on the surface after each preparation method. Annealing in ultrahigh vacuum causes the surface electronic structure to become inhomogeneous whilst the LDOS suggests a compositional change from an oxide surface to p-type CZT.     

Characterization of MOCVD-grown CdMnTe films by infrared spectroscopy

Single crystal Cd_1−x Mn _x Te (x=0.10–0.30) films have been grown by metalorganic vapor deposition (MOCVD) on (111) GaAs substrates with and without CdTe buffer layers, at substrate temperatures of 380° to 450° C. Infrared phonon spectra reveal that the films grown at 420° C substrate temperature have reasonable Mn concentration (>10%) and are of good quality in agreement with Raman measurements. Spectral analysis also gives values for Mn concentration that agrees with photoluminescence measurements, and determines film thickness.     

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.     

Melt growth and stoichiometry control of (Cd1−xZnx)1+yTe single crystals

Growth of (Cd_1−xZn_x)_1+yTe(CZT) single crystals is tried by a modified Bridgman method using a reservoir chamber containing Cd and Zn metals with a fixed mole ratio. The aim of this method is to obtain the single crystals with controlled deviation y from stoichiometry and homogeneous target composition x. A suitable growth condition was examined experimentally and the effectiveness of this method for controlling the deviation y from stoichiometry and the composition x is confirmed.     

Tellurium-rich growth and laser fabrication of lead-tin-telluride (Pb1−xSnxTe: 0.06<x<0.08)

Single crystals of Pb_1−x Sn_x Te (0.06<x<0.08) have been grown by using an ingot-nucleation technique from a Te-rich source. The as-grown crystals have a p-type carrier concentration around 10¹⁹ cm⁻³ and dislocation density as low as 10³ cm⁻². Diode lasers fabricated from these crystals have contact resistances of 2×10⁻⁵ Ω-cm² and a single-mode single-ended output power of 750 μW at heat sink temperatures around 15 K.     

Temperature dependence of the optical properties of Hg1−xCdxTe

The alloy composition of Hg_1−xCd_xTe should be controlled during growth, so that the desired band gap and the lattice-matched layer may be obtained. In-situ spectroscopic ellipsometry, now commercially available, enables one to acquire spectral data during growth. If one knows the optical dielectric function as a function of alloy composition and temperature, the technique can be fully used to monitor and control temperature, the thickness, and the alloy composition. For this purpose, we first obtained temperature dependent spectral data of Hg_1−xCd_xTe by spectroscopic ellipsometry (SE). The spectral data of Hg_1−xCd_xTe with x = 1,0.235, and 0.344 were obtained from room temperature to 800Kin the photon energy range from 1.3 to 6 eV. The spectral data revealed distinctive critical point structures at E₀, E₀+Δ₀, E₁, E₁+Δ₁, E₂(X), and E₂(Σ). Critical point energies decreased and linewidths increased monotonically as temperature increased. The model for the optical dielectric function enabled (i) the critical point parameters to be determined accurately, and (ii) the spectral data to be expressed as a function of temperature within and outside the experimental range.     

Open-tube vapor transport epitaxy of Hg1−xCdxTe

A novel set-up for horizontal open-tube vapor transport epitaxy of Hg_1−xCd_xTe films is described. Mirror-like Hg_1−xCd_xTe epitaxial layers with thicknesses up to 40 Μm were grown and characterized. The growth temperature ranged from 380 to 550‡C, with growth rates of the order of 0.5–7 Μm per hour. The concentration depth profiles and the optical and electrical properties of relatively uniform films with x≈0.3–0.4 are reported. The process kinetics are studied. A simple model which takes into account the reactions occurring at the boundaries of the epitaxial layer and the interdiffusion in the epilayer is presented and discussed. The model fits the experimentally observed characteristics of the epitaxial growth process. A constant growth rate leading to a linear dependence of film thickness upon deposition time y–y_i=k_s t is derived. The reaction rate constant k is given by k_s=k_oe^−Ea^/kT with k_o=0.18 cm-sec⁻¹and the energy of activation E_a=1.12 eV.     

Variable temperature hall effect on p-Hg1−xCdxTe grown on CdTe and sapphire substrates by liquid phase epitaxy

Variable temperature Hall effect measurements have been made down to 9–10K on p-type Hg_1−xCd_xTe grown by liquid phase epitaxy on both CdTe and sapphire substrates. Carrier freeze-out was usually observed throughout the measured temperature range. For most samples, the hole mobility was well-behaved and exhibited a maximum at ˜ 35K. Values of acceptor ionization energy E_A and donor concentration N_D were estimated from the data, using a model assuming significant compensation, which provided a good fit to the low temperature data. In addition, values of N_D were also estimated from an analysis of the low temperature mobility using the hole effective mass as a parameter to provide reasonable agreement between the N_D values calculated from the Hall coefficient and mobility data. The measured carrier concentration is a result of close compensation between stoichiometric acceptors and donors, with N_D usually in the low-10¹⁷ cm⁻³ range. Average values of E_A for as-grown, undoped x = 0.32 layers on CdTe and sapphire substrates are 7.4 and 6.6 meV, respectively. An activation energy of 0.84 meV was determined for a Cu-doped x = 0.32 layer that was annealed in Hg vapor to reduce the number of Hg vacancies. The average E_A for undoped Hg-annealed x = 0.22 layers on CdTe substrates is 2.35 meV. Layers with x = 0.32 grown on sapphire substrates have average carrier concentrations of 2.92 (σ = 0.54) × 10¹⁶ cm⁻³, compared with 4.64 (θ = 1.26) × 10¹⁶ cm⁻³ for the same composition layers grown on CdTe substrates.     

Analysis of CZT crystals and detectors grown in russia and the ukraine by high-pressure bridgman methods

Sandia National Laboratories (SNL) is leading an effort to evaluate vertical high pressure Bridgman (VHPB) Cd_1−xZn_xTe (CZT) crystals grown in the former Soviet Union (FSU) (Ukraine and Russia), in order to study the parameters limiting the crystal quality and the radiation detector performance. The stoichiometry of the CZT crystals, with 0.04<x<0.25, has been determined by methods such as proton-induced x-ray emission (PIXE), x-ray diffraction (XRD), microprobe analysis and laser ablation ICP mass spectroscopy (LA-ICP/MS). Other methods such as triaxial double crystal x-ray diffraction (TADXRD), infrared transmission spectroscopy (IR), atomic force microscopy (AFM), thermoelectric emission spectroscopy (TEES) and laser induced transient charge technique (TCT) were also used to evaluate the material properties. We have measured the zinc distribution in a CZT ingot along the axial direction and also its homogeneity. The (Cd+Zn)/Te average ratio measured on the Ukraine crystals was 1.2, compared to the ratio of 0.9–1.06 on the Russian ingots. The IR transmission showed highly decorated grain boundaries with precipitates and hollow bubbles. Microprobe elemental analysis and LA-ICP/MS showed carbon precipitates in the CZT bulk and carbon deposits along grain boundaries. The higher concentration of impurities and the imperfect crystallinity lead to shorter electron and hole lifetimes in the range of 0.5–2 and 0.1 μs, respectively, compared to 3–20 and 1–7 μs measured on U.S. spectrometer grade CZT detectors. These results are consistent with the lower resistivity and worse crystalline perfection of these crystals, compared to U.S.-grown CZT. However, recently grown CZT from FSU exhibited better detector performance and good response to alpha particles.     

Photovoltaic effect and carrier transport mechanisms in Hg1-Mnxtdiodes

Hg_1-xMn_xTe semiconducting semimagnetic alloy has been examined in the context of its possible applications in infrared detectors. For analysis of detector properties the intrinsic carrier concentration has been calculated as a function of temperature and crystal composition. The starting material was In-doped Hg_1-xMn_xTe grown by the modified Bridgman method. The as-grown crystals with manganese content of 12-19% were p-type with carrier concentration and mobility of 100 cm²/ Vs at 77 K. An-type layer was formed on the surface by the annealing process in saturated Hg-vapour at 270-320° for 2 hrs. Capacitance-voltage curves have C^-3 dependence on applied voltage indicating that the junction is linearly graded. From standard electrical measurements and spectral characteristics the main detector parameters were determined and compared to those of Hg_1-xCd_xTe devices. The influence of material properties on detector parameters was analyzed. In order to estimate the carrier transport mechanisms, differential resistivities and current-voltage curves were measured over a wide range of temperaturesi.e. 25 to 300 K. From the temperature dependence of the R₀A product, it was established that at high temperatures (150-300 K) the carrier transport is dominated by a recombination-generation mechanism. In low temperature region the excess current at forward bias is probably attributed to carrier tunneling via energy states distributed randomly within the forbidden gap. At reverse bias the leakage surface or volume currents dominate in the carrier transport.     

Transient behavior of Hg1−xCdxTe film growth on (111)B CdTe substrates by chemical vapor transport

As part of a systematic investigation of the effects of substrate surfaces on epitaxial growth, the transient behavior of Hg_1−xCd_xTe film growth on (111)B CdTe by chemical vapor transport (CVT) has been studied as a function of growth time under vertical stabilizing (hot end on top) and vertical destabilizing (hot end at bottom) ampoule orientations. The experim ental results show the morphological transition of the Hg_1−xCd_xTe deposition on (111)B CdTe at 545°C from three-dimensional islands to layers within about 0.5 and 0.75 h for the growth under vertical stabilizing and destabilizing conditions, respectively. The combined effects of small convective flow disturbances on the growth morphology and defect formation are measurable. The overall trends of the time dependent growth rates and compositions of the Hg_1−xCd_xTe epitaxial layers under stabilizing and destabilizing conditions are similar. The system atically higher growth rates of the Hg_1−xCd_xTe films by about 10% under vertical destabilizing conditions could be influenced by a small convective contribution to the mass transport. The combined results show that improved Hg_1−xCd_xTe epitaxial layers of low twin density on (111)B CdTe substrates can be obtained by CVT under vertical stabilizing conditions.     

Surface-barrier structures on single crystals of CdMgMnTe quaternary solid solutions: Creation and properties

Planar melt crystallization is used to grow single crystals of Cd-Mg-Mn-Te quaternary alloys along the pseudobinary sections Cd_{0.75 − x} Mg _x Mn_0.25Te, Cd_{0.75 − x} Mg_0.25Mn _x Te, and Cd_{1 − 2x} Mg _x Mn _x Te. The first photosensitive structures, i.e., In/CdMgMnTe Schottky barriers, are fabricated within each indicated single-crystal section. The spectral dependences of the relative quantum efficiency of photoconversion are measured, and the broadband photosensitivity of the new structures is detected. Based on the spectral dependences of the photosensitivity, the nature of the meson transitions is discussed and the corresponding band gaps are determined. The applicability of grown single crystals of CdMgMnTe quaternary alloys to broadband photoconverters of optical radiations is ascertained.     

Vanadium-Doped Cadmium Manganese Telluride (Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te) Crystals as X- and Gamma-Ray Detectors

CdMnTe offers several potential advantages over CdZnTe as a room- temperature gamma-ray detector, but many drawbacks in its growth process impede the production of large, defect-free single crystals with high electrical resistivity and high electron lifetimes. Here, we report our findings of the defects in several vanadium-doped as-grown as well as annealed Cd_1−x Mn _x Te crystals, using etch pit techniques. We carefully selected single crystals from the raw wafer to fabricate and test as a gamma-ray detector. We describe the quality of the processed Cd_1−x Mn _x Te surfaces, and compare them with similarly treated CdZnTe crystals. We discuss the characterization experiments aimed at clarifying the electrical properties of fabricated detectors, and evaluate their performance as gamma-ray spectrometers.