Characterization of compensation and trapping in CdTe and CdZnTe: Recent advances

Results on the properties of the known impurities, Ge, Sn, V and Bi, and the lattice imperfections, V_Cd and Te_Cd are summarized. We discuss their role in compensation, and in buffering the variations in shallow electronic levels in the grown ingot. We demonstrate that (∼2÷3 kT) variations of the Fermi energy increases carrier trapping to the deep levels. Trapping is manifest in a photoconductivity signal that can be studied by photoconductivity methods, thus allowing to monitor the spectroscopic‐grade material before fabricating the detectors. Our approach could be important in preventing the after‐glow effect and polarization. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Generation of VGaTeAsVAs Complexes in Tellurium-doped n-type GaAs by Low-temperature Annealing

It is shown that low-temperature annealing (T= 425 to 625 °C, t ⩾ 0.5 h) of tellurium-doped n-type GaAs crystals (n₀ = 2 × 10¹⁸ cm⁻³) leads to a generation of V_GaTe_AsV_As complexes as a result of a diffusion of arsenic vacancies to V_GaTe_As complexes or arsenic and gallium vacancies to isolated tellurium atoms. The observed regularities of generation of V_GaTe_AsV_As complexes as the annealing temperature and the annealing time are varied are well explained by the proposed model of diffusion-limited formation of V_GaTe_AsV_As complexes.     

Compensation Mechanism in Vanadium and Gallium Doped CdTe and (Cd,Zn)Te

Vanadium and gallium doped CdTe crystals were grown from the vapour phase (modified Markov method) and (Cd_0.9Zn_0.1)Te: V from the melt (vertical Bridgman). The crystals were characterized by photoinduced current transient spectroscopy (PICTS), photoluminescence (PL) and time dependent charge measurements (TDCM). Transitions from different charge states (V²⁺/V³⁺) of the vanadium donor have been observed in the V-doped crystals by PICTS. A shallow donor level (dE = 0.068 eV) and the Ga A-center have been identified by PICTS and PL measurements in CdTe:Ga. In case of V-doping high resistivity is achieved all over the crystal while Ga-doping results in a high resistivity region only in the middle of the crystal. Calculation of the resistivity by means of a compensation model shows that for both dopants an additional not observed deep donor has to be assumed in order to describe the resistivity distributions.     

Investigation of the nature of point defects in in Te-doped gallium antimonide

Precision lattice constant and density measurements held on gallium antimonide single crystals grown from stoichiometric melts showed that doping of such crystals with Te lead to the intensification of Ga-supersaturated solid solution decomposition process with initial Frenkel defect (Ga_i + V_Ga) production. It is supposed that Te_sb — simple donors form complexes with V_Ga which are believed to be acceptors. Doping of GaSb with Te up to the levels above 2 · 10¹⁸ cm⁻³ leads to partial decomposition of GaSb(Te) solid solution supersaturated with Te.     

Spherulitic crystallization of β‐In2Te3 by physical vapour deposition

Different morphologies of indium telluride (In₂Te₃) including novel spherulites were crystallized using the physical vapour deposition (PVD) method, by varying the difference in the growth and source zone temperature (ΔT) of a dual zone horizontal furnace assembled indigenously. Whiskers and kinked needles of In₂Te₃were grown at ΔT = 250 K and 300 K respectively, maintaining the growth zone at 500 °C. At high supersaturation (Δ T = 400 K), spherulitic crystals were obtained. The stoichiometric composition of these crystals has been confirmed using energy dispersive analysis by x‐rays (EDAX). The structure of β‐In₂Te₃ spherulitic crystals is identified as zinc blende with lattice parameter a = 6.159 Å, from x‐ray diffraction (XRD) studies. The scanning electron microscope (SEM) images revealed the radial structure of the grown spherulites. The growth mechanism for the spherulitic crystallization of β‐In₂Te₃ crystals has been discussed based on the theoretical models. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhancement of thermoelectric efficiency in vapor deposited Sb2Te3 and Sb1.8In0.2Te3 crystals

Pure and indium doped antimony telluride (Sb₂Te₃) crystals find applications in high performance room temperature thermoelectric devices. Owing to the meagre physical properties exhibited on the cleavage faces of melt grown samples, an attempt was made to explore the thermoelectric parameters of p‐type crystals grown by the physical vapor deposition (PVD) method. The crystal structure of the grown platelets (9 mm× 8 mm× 2 mm) was identified as rhombohedral by x‐ray powder diffraction method. The energy dispersive analysis confirmed the elemental composition of the crystals. The electron microscopic and scanning probe image studies revealed that the crystals were grown by layer growth mechanism with low surface roughness. At room temperature (300 K), the values of Seebeck coefficient S (⊥ c) and power factor were observed to be higher for Sb_1.8In_0.2Te₃ crystals (155 μVK⁻¹, 2.669 × 10⁻³ W/mK²) than those of pure ones. Upon doping, the thermal conductivity κ (⊥ c) was decreased by 37.14% and thus thermoelectric efficiency was improved. The increased figure of merit, Z = 1.23 × 10⁻³ K⁻¹ for vapour grown Sb_1.8In_0.2Te₃ platelets indicates that it could be used as a potential thermoelectric candidate.     

Growth of Nd:Sr3Ga2Ge4O14 crystals by a modified Bridgman method

Bridgman growth of Nd:SGG (Sr₃Ga₂Ge₄O₁₄) crystals has been investigated for the first time. Pt crucible of ∅︁25mm×250mm with a seed well of ∅︁10mm×80 mm is used, and seed is SGG crystal of ∅︁10mm×50mm grown by Bridgman method in advance. The growth parameters are optimized as the furnace temperature is set to 1450∼1500°C, temperature gradient in the crystal‐melt interface is less than 25 K/cm and growth rate is less than 0.5mm/h. The Nd:SGG crystals with 25mm in diameter and 60mm in length are grown successfully from 1.5 to 8at% Nd³⁺ doped stoichiometric Sr₃Ga₂Ge₄O₁₄ melt. The distribution coefficient and concentration of Nd³⁺ in Nd:SGG crystals are obviously higher than those of Nd:YAG crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Irradiation plus annealing-induced 1.20 eV emission band in p-type GaAs

The effect of 2.2 MeV electron irradiation and subsequent annealings on the luminescence of tellurium-compensated p-type GaAs crystals is studied and analyzed. A comparatively strong emission band peaked at hv_m near 1.20 eV (induced by radiative electron recombination in Te_AsV_Ga pairs) appears in irradiated annealed (at T ≧ 250 °C) compensated p-type GaAs. The data obtained testify about the following: a) electron irradiation of GaAs creates stable (at T ≦ 200 °C) defects not only in the arsenic sublattice of GaAs, but in its gallium sublattice too; b) radiation plus annealing (r.p.a.)-induced Te_AsV_Ga pairs are characterized by a rather high (compared to that for grown-in Te_As V_Ga pairs) probability of electron radiative transitions in them. The electrical characterization of the r.p. a.-induced 1.20 eV radiative centres (Te_AsV_Ga pairs) is given.     

Top‐seeded growth,optical properties and theoretical studies of noncentrosymmetric Te2V2O9

A single crystal of Te₂V₂O₉ with dimensions of 15×15×5 mm³ has been grown by the top‐seeded growth method. Infrared and transmission spectra indicate the transmission cutoff wavelength of Te₂V₂O₉ crystal is about 620 nm in visible region and 6.2 μm in infrared region. In addition, band structure and density of states calculations of Te₂V₂O₉ were carried out using the total‐energy code CASTEP based on density functional theory. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal diffusivity measurements on As-Te-Ga glasses by photo-thermal deflection technique: Composition dependence and topological thresholds

The thermal diffusivity (α) of As₂₀Te_80−xGa_x glasses (7.5 ? x ? 18.5) has been measured using photo-thermal deflection (PTD) technique. It is found that the thermal diffusivity is comparatively lower for As₂₀Te_80−xGa_x glasses, which is consistent with the memory type of electrical switching exhibited by these samples. Further, the thermal diffusivity of As₂₀Te_80−xGa_x glasses is found to increase with the incorporation of gallium initially (for x ? 9), which is consistent with the metallicity of the additive. This increase in α results in a maximum at the composition x = 9; beyond x = 9, a decrease is seen in α leading to a minimum at the composition x = 15. The observed composition dependence of thermal diffusivity of As₂₀Te_80−xGa_x glasses has been found to be similar to that of Al₂₀As_xTe_100−x glasses, based on which it is proposed that As₂₀Te_80−xGa_x glasses exhibit an extended stiffness transition with compositions x = 9 and x = 15 being its onset and completion, respectively. Also, the composition x = 17.5 at which a second maximum is seen in the thermal diffusivity has been identified to be the chemical threshold (CT) of the As₂₀Te_80−xGa_x glassy system, as at CT, the glass is configurationally closest to the crystalline state and the scattering of the diffusing thermal waves is minimal for the chemically ordered phase.     

Excitation intensity and temperature‐dependent photoluminescence and optical absorption in Tl4Ga3InSe8 layered crystals

Photoluminescence (PL) spectra of Tl₄Ga₃InSe₈ layered crystals grown by Bridgman method have been studied in the wavelength region of 600‐750 nm and in the temperature range of 17‐68 K. A broad PL band centered at 652 nm (1.90 eV) was observed at T = 17 K. Variations of emission band has been studied as a function of excitation laser intensity in the 0.13 to 55.73 mW cm^‐2 range. Radiative transitions from donor level located at 0.19 eV below the bottom of conduction band to shallow acceptor level located at 0.03 eV above the top of the valence band were suggested to be responsible for the observed PL band. From X‐ray powder diffraction and optical absorption study, the parameters of monoclinic unit cell and the energy of indirect band gap were determined, respectively. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave hydrothermal synthesis and photocatalytic properties of ZnWO4 nanorods

Cd²⁺‐doped ZnWO₄ nanorods have been synthesized at 200 °C with microwave hydrothermal method, using Zn(NO₃)₂·6H₂O, Na₂WO₄·2H₂O and CdCl₂ as raw materials. The effects of Cd²⁺ doping contents on the structure and morphology of the product were studied. The results show that Cd²⁺ doping into the crystal lattice of ZnWO₄ nanopowder makes the powder orientationally grow along (010), (110) and (200) crystal planes to form the nanorods. The bigger Cd²⁺ doping contents are, the more obviously ZnWO₄ nanorods grow. Meanwhile, the nanopowder is gradually transformed from monoclinic phase into the orthogonal phase. As the charge transference medium between the interfaces, Cd²⁺ restrains the combination of holes and electrons. After doped, the photocatalytic properties of ZnWO₄ nanorods are increased. When Cd²⁺ doping content is 20%, the Cd²⁺‐doped ZnWO₄ nanorods showed the highest degradation rate up to 98% in 2 h.     

Thermoelectrical properties of In1‐xGaxAs and InAs crystals irradiated with fast electrons

The thermoelectric power in In_1‐xGa_xAs (x = 0,01;0,04) solid solutions and InAs crystals irradiated with fast electrons by the energy of 6 MeV and dose of 10¹⁶‐ 2 x 10¹⁷ el/cm^‐2 on the interval 80‐400 K have been investigated. It is revealed that in the all crystals the value of the thermoelectric power is decreased under irradiation that resulted from the growth of the free electron concentration to form radiation induced defects of the donor type. It has been determined that in the initial InAs after irradiation, the charge carriers scatter on optical phonons and in In_1‐xGa_xAs solid solutions they do on optical phonons and ionized impurities. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Czochralski growth and characterization of Dy: La3Ga5.5Nb0.5O14 single crystals

Dysprosium (Dy) doped La₃Ga_5.5Nb_0.5O₁₄ single crystals were grown by the traditional Czochralski method along z‐axis. The structure of the crystal has been studied by X‐ray powder diffraction method, and the unit‐cell parameters are calculated to be a=8.22070 Å, c=5.12533 Å and V=299.965 ų. The segregation coefficient of Dy³⁺ in La₃Ga_5.5Nb_0.5O₁₄ crystal was measured by X‐ray fluorescence analysis. For 1 mol% doping level in the melt, the distribution coefficient of Dy³⁺ was determined to be 0.341 wt%. Specific heat, thermal expansion and transmission spectrum of Dy: La₃Ga_5.5Nb_0.5O₁₄ single crystals have been measured. The fluorescence spectra of Dy³⁺: La₃Ga_5.5Nb_0.5O₁₄ crystals were measured at room temperature, and there were four emission transitions occurring at 479, 576, 662 and 754 nm, respectively. The fluorescent lifetimes measurement results show 1.0% Dy: La₃Ga_5.5Nb_0.5O₁₄ possesses shorter fluorescence decay time (303.4 μs) than does 1.0%Dy:LGS (436.12 μs). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single‐crystal growth and characterization of mullite‐type orthorhombic Bi2M4O9 (M = Al3+, Ga3+, Fe3+)

Pure and homogeneous single crystals of orthorhombic mullite‐type Bi₂M₄O₉ (M = Al³⁺, Ga³⁺, Fe³⁺), and a mixed Bi₂Fe_1.7Ga_2.3O₉ crystal from an equimolar Ga/Fe composition were grown by the top seeded solution growth (TSSG) method. All these compounds melt incongruently in the range of about 800 and 1100 °C. In case of bismuth gallate and ferrate inclusion‐free crystals with dimensions up to several cubic centimeters can be grown. Limited solubility in Bi₂O₃ and the high steepness of the liquidus curve are the reasons for getting only small imperfect bismuth aluminate crystals. In contrast to ceramic materials preparation reported in literature, divalent calcium and strontium could not be incorporated into the mullite‐type structure during the melt growth process. Several fundamental physical properties like heat capacity, thermal expansion, heat conductivity, elastic constants, high‐pressure behavior and oxygen diffusivity were determined by different research groups using single‐crystalline samples from the as‐grown materials. Furthermore, the refractive indices of Bi₂Ga₄O₉ were measured in the range of 0.430 and 0.700 μm. Such as many other bismuth containing compounds the refractive indices of Bi₂Ga₄O₉ are larger than 2, and Bi₂Ga₄O₉ is an optic biaxial positive crystal. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The field effect in amorphous chalcogenides: An investigation of localized states and electronic transport

The temperature dependence of the field effect response permits an unambiguous determination of the identity of those states responsible for electrostatic screening in the amorphous chalcogenides. We observe (1) in As₂Te₃, field effect screening by localized states at the Fermi level at low temperatures (～ 10¹⁹ cm^?3 eV^?1) and by mobile charge carriers (～ 10¹⁸ cm^?3 at 300 K) at high temperatures, and a transition from p-type to two-carrier (primarily n-type) conductivity as the temperature is raised above ～320 K; (2) in As₂SeTe₂, screening by mobile charge carriers (～ 10¹⁸ cm^?3 at 300 K) with strongly type conductivity; (3) in As₂Se₂Te, screening by localized states at the Fermi level (～ 10¹⁹ cm^?3 eV^?1) with strongly p-type conductivity; and (4) in Sb₂Te₃, a very high density of localized states at the Fermi level (～ 2 × 10²⁰ cm^?3 eV^?1) with both electron and hole contributions to the conductivity. Correlation with thermoelectric power results suggests that the p-type conductivity in As₂Te₃ is due to near-equal contributions from two processes: hopping in localized states plus extended state conduction. Aging and annealing behavior is described with the aid of a “chaotic potential model” that appears to be able to account for large changes in mobile carrier density that leave the conductivity unaltered.     

Crystal growth and investigation of CuAlxGa1−xTe2 solid solutions

Alloys of the CuGaTe₂‐CuAlTe₂ system have been synthesized by the one‐temperature method and homogenized by annealing. It was established for the first time by X‐ray and DTA methods that a continuous row of solid solutions is formed in the system. Large block crystals of CuAl_xGa_1−xTe₂ solid solutions have been grown by the Bridgman method (horizontal version). Measurements of density, microhardness and thermal expansion have been carried out on the grown crystals. It has been established, that the density and thermal expansion coefficients are changed linearly with composition, microhardness has a maximum at x = 0.6. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of randomness on the ESR hyperfine structure of Cd+

The ESR spectra of the 5s¹ state of Cd⁺, induced with gamma-ray irradiation, were measured for polycrystalline CaO, β-Ca(PO₃)₂ and glassy Ca(PO₃)₂ matrices. It has been found out that one of the hyperfine absorptions due to the magnetic nuclei (¹¹¹Cd and ¹¹³Cd) reflects very senstively the structural fluctuation around the center in terms of pronounced line broadening. Such a feature was explained reasonably well by introducing the distribution of the hyperfine coupling constant. It was emphasized that Cd²⁺, the precursor of Cd⁺, is a very suitable probe to study the local randomness around Ca²⁺ in solids.     

Neutron Diffraction Investigation of Langanite Crystals

The upper and lower parts of a single crystal with a nominal composition La₃Ga_5.5Nb_0.5O₁₄grown by the Czochralski method (Ir crucible, 99%Ar + 1%O₂, growth direction) have been studied by neutron diffraction for the first time. The compositions of the upper and lower parts are found to differ ((La_2.935(2)□_0.065)(Ga_0.450Nb_0.550(3))Ga₃(Ga_1.965(4) □_0.035)(O_13.90(1) □_0.10) and (La_2.940(1) □_0.060)(Ga_0.590Nb_0.410(2))Ga₅(O_13.82(1) □_0.18), respectively), and microtwin formation was observed in the upper part, with two unit cells related by the translation 1/2Z. Based on a comparison of the refined crystal composition and optical transmission spectra, the absorption bands at 30 000, 24 500, and 20 500 cm_-1 were assigned to divacancies (2 V _La^', 3 V _O^..), oxygen vacancies, and color centers, respectively. A relationship between the crystal color and oxygen content is established.     

Structural and Electrical Characterization of Ag3Ga5Te9 and Ag3In5Se9 Crystals

X-ray powder diffraction studies revealed that Ag₃Ga₅Te₉ and Ag₃In₅Se₉ crystallize in orthorhombic and tetragonal systems, respectively. The temperature dependent conductivity and Hall effect measurements have been carried out between 65—480 K. Ag₃Ga₅Te₉ exhibits p-type conduction with a room temperature conductivity of 4.3 × 10^—4 (Ω · cm)^—1 and mobility less than 1 cm²/V · s. Ag₃In₅Se₉ was identified to be n-type with room temperature conductivity 7.2 × 10^—5 (Ω · cm)^—1 and mobility 20 cm²/V · s. From temperature dependence of the conductivity three different impurity ionization energies were obtained for both compounds. The anomalous behavior observed in the temperature dependence of mobility was attributed to the different features of the microstructure.