Electrical properties of (PbS)0.59TiS2 crystals at high pressure up to 20 GPa

The electrical resistance ρ and thermopower S of the (PbS)_0.59TiS₂ single-crystal compound with mismatched layers and the TiS₂ crystals have been investigated at room temperature in high-pressure chambers with synthetic diamond dies. The decrease in ρ and |S| observed in (PbS)_0.59TiS₂ under the pressure P≈2 GPa is associated with the structural transformation of PbS from the cubic phase into the orthorhombic phase. The jumps of ρ and |S| are presumably caused by the increase in the electron concentration in the TiS₂ layers. For P≥4 GPa, at which the gap is absent in the electronic spectrum of TiS₂, a decrease in ρ(P) is observed for the (PbS)_0.59TiS₂ samples.     

High‐temperature thermoelectric properties of Cu2In4Te7

Cu₂Ga₄Te₇ has recently been reported to have a relatively high thermoelectric (TE) figure of merit (ZT). However, the TE properties of Cu₂In₄Te₇, which has the same defect zinc‐blende structure as Cu₂Ga₄Te₇, have been hardly investigated. Here, we demonstrate that Cu₂In₄Te₇ has relatively high ZT values that are similar to those of Cu₂Ga₄Te₇. High‐density polycrystalline bulk samples of Cu₂In₄Te₇ were prepared and their electrical resistivity (?), Seebeck coefficient (S), and thermal conductivity (κ) were measured. Cu₂In₄Te₇ has a maximum ZT of 0.3 at 700 K, with ?, S, and κ values of 62.1 × 10^–5 Ω m, 394 μV K^–1, and 0.61 W m^–1 K^–1, respectively. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of pressure and anionic substitution on the electrical properties of HgTeS crystals

The resistivity ρ and the Hall constant R for the HgTe_1?x S_x (0.04≤x≤0.6) crystals have been investigated in the temperature range 4.2–350 K in the magnetic fields B up to 14 T. The pressure dependences of the resistivity ρ have been measured at the pressures P as high as 1 GPa at temperature T=77–300 K and magnetic field B=0–2 T. It is found that the samples with x≤0.20 exhibit a decreasing dependence ρ(T) typical of zero-gap semiconductors, whereas the samples with x≥0.27 show the dependence ρ(T) characteristic of semimetals. For the semiconducting crystals with x≈0.20 and x≈0.14, the temperature coefficient of ρ(T) changes sign at T=265 and T>300 K, respectively. Under a pressure of ≈1 GPa, the temperature of the sign inversion decreases by ≈30 K. An increase in the magnetic field B and a rise in the temperature T lead to a change in the sign of the Hall constant R for the semiconducting samples, but do not affect the electronic sign of R for the semimetallic samples. The behavior of R and ρ correlates with the thermoemf data obtained at the quasi-hydro-static pressure P up to 3 GPa. It is demonstrated that the substitution of sulfur atoms for tellurium atoms brings about an increase in the concentration of electrons and a decrease in their mobility. The transition to the wide-gap semiconductor phase is observed at P>1–1.5 GPa. The conclusion is drawn that the semimetallic crystals HgTe_1?x S_x with x≥0.27 and HgSe are similar in properties.     

Thermoelectric power and phase transition of polycrystalline As2Te3 under pressure

The pressure dependence of the thermoelectric power of monoclinic As₂Te₃ is measured up to 10 GPa using a Mao-Bell diamond anvil cell. The thermoelectric power never reaches an absolute value greater than the ambient pressure value of 242 μV/K. Evidence of a phase transition is present between 6 and 8 GPa where the thermoelectric power reaches an absolute value of 225 μV/K after passing through a minimum of S≈75 μV/K. X-ray diffraction experiments confirm that the resulting structure is β-As₂Te₃, which is isostructural with Bi₂Te₃ and Sb₂Te₃.     

The elastic behaviour of tetrahedral materials with vacant sites

As part of a study of defect tetrahedral structure compounds, the elastic constants of single crystal specimens of Hg₃Ga₂□Te₆ and HgIn₂□Te₄ have been measured between 77 K and room temperature using the pulse superposition technique. These compounds are included in the series HgTe, Hg₅In₂□Te₈, Hg₃In₂□Te₆ and HgIn₂□Te₄ and HgTe, Hg₅Ga₂□Te₈, Hg₃Ga₂□Te₆ where there is a progressive increase in the concentration of vacant sites. While the other compounds studied are cubic, HgIn₂□Te₄ has a tetragonal structure with a $\text{c}\text{a}$ ratio of 2.0. The components of the elastic stiffness tensor of this material at 77 K are (in units of 10¹¹ dyne cm^?2) C₁₁ = 4.31 C₁₂ = 2.54 C₄₄ = 2.14 C₃₃ = 4.47 C₁₃ = 2.18 C₆₆ = 2.41. In a cubic material C₁₁ = C₃₃, C₄₄ = C₆₆ and C₁₂ = C₁₃: the elastic behaviour of this tetragonal compound closely resembles that of a cubic material, as might be anticipated from its structure. This similarity is further illustrated by reference to the symmetry of phase velocity and Young's modulus surfaces. Examination of the elastic constants and reduced elastic constants of these compounds shows a regular trend, the elastic stiffness decreases as the number of vacant sites increases. There is an approximately linear relationship between the reduced bulk modulus and the number of sited vacancies.     

Nanomechanical characterizations of InGaN thin films

In_xGa_1−xN thin films with In concentration ranging from 25 to 34 at.% were deposited on sapphire substrate by metal-organic chemical vapor deposition (MOCVD). Crystalline structure and surface morphology of the deposited films were studied by using X-ray diffraction (XRD) and atomic force microscopy (AFM). Hardness, Young's modulus and creep resistance were measured using a nanoindenter. Among the deposited films, In_0.25Ga_0.75N film exhibits a larger grain size and a higher surface roughness. Results indicate that hardness decreases slightly with increasing In concentration in the In_xGa_1−xN films ranged from 16.6 ± 1.1 to 16.1 ± 0.7 GPa and, Young's modulus for the In_0.25Ga_0.75N, In_0.3Ga_0.7N and In_0.34Ga_0.66N films are 375.8 ± 23.1, 322.4 ± 13.5 and 373.9 ± 28.6 GPa, respectively. In addition, the time-dependent nanoindentation creep experiments are presented in this article.     

Electrical and optical properties of single crystal In2Te3 and Ga2Te3

Electrical conductivity and thermopower measurements are reported for the defect semiconductors p-In₂Te₃ and n-Ga₂Te₃. The hole mobility μ_p in the former varied as Tⁿwheren=+5.98 forT<350 K and n=-4.13 forT>350 K showing a maximum of 210 cm²V^-1 sec^-1 at 350 K. Electron mobility in n-Ga₂Te₃ also went through a maximum at 320 K. The optical band-gaps for both were found to be direct, with values of 1.01 and 1.08 eV for In₂Te₃ and Ga₂Te₃ respectively at 300 K. Pronounced effects of annealing on TEP and optical absorption gave evidence of defect ordering at low temperatures followed by defect creation at T>350 K.     

High-pressure thermoelectric characteristics of Bi2Te3 semiconductor with different charge carrier densities

The measurements of the absolute values of the thermopower and of the relative electrical resistance have been performed for n type Bi₂Te₃ under hydrostatic pressure up to 9 GPa at room temperature. Under pressures exceeding 5 GPa and up to the phase transition (at 7 GPa), the samples with the charge carrier density below 10^?19 cm^?3 exhibit an anomalous growth of the thermopower. For the purest sample (n = 10^?18 cm^?3), the thermopower is as high as +150 μV/K. The pressure dependence of the electrical resistance for n-Bi₂Te₃ does not exhibit any anomalies up to the pressure corresponding to the phase transition (7 GPa). Thus, the state with the giant thermoelectric efficiency is found in Bi2Te3 under pressure before the phase transition.     

Energy formation of antisite defects in doped Sb2Te3 and Bi2Te3 crystals

The free carrier concentration of the Sb_2−xIn_xTe₃, Bi_2−xIn_xTe₃ and Bi₂Te_3−xS_x crystals has been determined from the values of the Hall constants and the free carrier concentration of the Sb_2−xTl_xTe₃ has been calculated from the plasma resonance frequency; with increasing value of x, the hole concentration decreases. As the incorporation of the elements In, Tl and S into the lattice Sb₂Te₃ or Bi₂Te₃, respectively, gives rise to the uncharged defects In^x_Sb, Tl^x_Sb, In^x_Bi and S^x_Te, the x causes the decrease of the antisite defects concentration. The proven effect is explained in the following way: the antisite defects can be created only in crystals whose atoms are bound by weakly polarized bonds. The incorporation of In, Tl and S atoms into the crystal lattice of Sb₂Te₃ or Bi₂Te₃ increases the bond polarity, the ionicity of ternary crystals increases. This unfavorably affects the increase of antisite defects whose concentration decreases. The change of the bond polarity is considered from the changes discovered in the formation energy of antisite defects of the above mentioned ternary crystals.     

Electron spin resonance and luminescence in Ga2−xEuxS3 single crystals

In present work electron spin resonance (ESR) and luminescence have been studied in Ga_2−xEu_xS₃ single crystals. The ESR and photoluminescence (PL) spectra of Ga_2−xEu_xS₃ were observed and the intensity of these spectra has increased linearly with the Eu concentrations in the samples. At the low temperature of 3.8 K in Ga_2−xEu_xS₃ single crystals, when the magnetic field has been applied as the perpendicular to the direction of [110], the hyperfine structure of ESR spectra has been observed. The exchange interaction of Eu²⁺ atoms in Ga_2−xEu_xS₃ single crystals have been determined as, g=4.2. The PL spectrum of pure Ga₂S₃ single crystals was recorded at 4.2 K and consisted of a narrow high-energy band at 2.53–2.38 eV and a low-energy band at 2.14–1.59 eV. Ga_2−xEu_xS₃ resulted in complete quenching of the impurity luminescence bands gave rise to a green europium band (2.38–2.14 eV) in the luminescence spectrum. Crystals of Ga_2−xEu_xS₃ emitted bright green electroluminescence (EL) spectrum when they excited with static and alternating electric fields at 77 K. We have also determined the field and frequency dependences of the EL.     

Thermoelectric properties of n-Bi2Te3 − x − y Se x S y solid solutions under high pressure

The thermoelectric properties of n-Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions with atomic substitutions in the tellurium sublattice (x = 0.27, 0.3, y = 0, and x = y = 0.09) have been studied under a pressure to 8 GPa. It has been found that the Seebeck coefficient and the resistance decrease with increasing P, and power factor χ increases in all compositions and becomes maximal at pressures of 2–4 GPa. It has been shown that the power factor χ, which is proportional to the product of the effective mass of the density of states m/m m/m ₀ and the charge carrier mobility μ₀ in the form (m/m ₀)^3/2μ₀, increases with increasing pressure mainly due to the increase in the mobility and also depends on the solid solution composition. In the composition with substitution Te → Se + S (x = y = 0.09), the peculiarity of the dependence of m/m ₀ on P in the pressure range corresponding to maximal values of the power factor can be explained by the existence of an electronic topological transition. The increase in the power factor under pressure in n-type Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions combined with similar data for p-type Bi_{2 ? x} Sb _x Te₃ solid solutions obtained earlier, including the estimations of possible changes in the thermal conductivity with increasing pressure, give grounds to design thermoelements with improved value of the thermoelectric figure-of-merit, which can be 50–70% at pressures of 2–4 GPa.     

Optical activity of γ<Subscript>1</Subscript>-(Ga<Subscript>x</Subscript>In<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>Se<Subscript>3</Subscript> crystals

The optical activity of uniaxial γ₁-(Ga_xIn_1?x )₂Se₃ crystals (x=0.1, 0.2, 0.3, 0.4) is studied at T=295 and 77 K in the spectral range 0.5–0.8 πm. It is found that the cationic substitution In → Ga leads to a nonlinear increase in the specific rotation of the plane of polarization ρ and the component g ₃₃ of the gyration tensor. It is shown that the gyrotropy of the crystals studied is determined by high-energy transitions whose energy exceeds the energy of the edge transitions and that the gyrotropy observed has a molecular origin.     

High pressure electrical resistivity studies on Ga-Te glasses

Abstract

Bulk, semiconducting Ga_xTe_100-x (17 ≤ x ≤ 25) glasses are prepared by the meltingh quenching method and electrical resistivity measurements are carried out at high pressures up to 8 GPa and low temperatures down to 77 K in a Bridgman anvil system. It is found that all the Ga_xTe_100-x, glasses exhibit metallization under pressure, with a continuous decrease in electrical resistivity and activation energy for conduction. Further, the high pressure metallic phases of Ga_xTe_100-x samples are found to be crystalline.     

Unstable equilibrium and radiation defects in solids

A new type of point defect in solids genetically related with Frenkel's pairs which appears when there exists the instability zone of pair vacancy (v) - interstitial atom (i). It is shown that, at large instability zones typical of ‘loose’ crystalline structures, equilibrium concentration of unstable pairs i-v may exceed the concentration of usual Frenkel's pairs. In the example of the semiconducting crystals In₂Te₃ and Ga₂Te₃ having loose structure it is experimentally demonstrated that equilibrium point defects cannot be preserved by specimen quenching and that irradiation by large doses of high-energy particles does not result in stable radiation defects formation.     

Dynamic shift of the phase-transition temperature in (Sn1−x In(2/3)x)2P2S6 crystals with incommensurate phase

The dielectric properties of ferroelectric (Sn_1?x In_(2/3)x )₂P₂S₆ crystals were studied in the region of incommensurate phase transitions occurring upon fast cooling and heating (0.2–11 K/min). The dynamic phase-transition shift observed in these materials was examined.     

Effect of post annealing on the characteristics of In2S3 buffer layer grown by chemical bath deposition on a CIGS substrate

In₂S₃ as an alternative Cd-free buffer in Cu(In,Ga)Se₂ (CIGS) solar cells was deposited on CIGS substrate by a chemical bath deposition and characterized after post annealing to optimize film properties for CIGS solar cells. A uniform and pinhole-free In₂S₃ film was deposited on a CIGS substrate by H₂O₂ treatment prior to chemical bath deposition. The In₂S₃ layer was an amorphous state due to the co-existence of In–S, In–O, and In–OH bonds. Annealing at 200 °C induced copper diffusion from CIGS into In₂S₃ layer and lowered the band gap from 3.3 to 1.9 eV, leading to phase change from amorphous state to crystalline state. The conduction band alignment at the In₂S₃/CIGS interface can be controlled by the post annealing. The shunt current through In₂S₃ film was prevented down to the thickness of 30 nm and a 1.15 eV shallow defect was eliminated by the annealing. The results indicated that post annealing in air is a critical to fabricate CIGS solar cells with a sub-30 nm CBD-In₂S₃ buffer layer.     

Inversion of conductivity type in Bi2Te3−xSx crystals

Transport parameters and optical properties of Bi₂Te_3?xS_x single-crystals with x=0–0.18 were studied. With increasing sulphur content the concentration of free current carriers decreases up to x=0.12, due to the interaction of S^x_Te defects with antisite defects Bi^′_Te, and then the p-type conductivity changes to the n-type. The optical gap of Bi₂Te_3?xS_x crystals increases with increasing S content. The obtained results led to the preparation of Bi₂Te₃-Bi₂Te_3?xS_xp–n junction by the heat treatment of p-type Bi₂Te₃ in S vapours.     

High-precision measurements of the compressibility and the electrical resistivity of bulk <Emphasis Type="Italic">g</Emphasis>-As<Subscript>2</Subscript>Te<Subscript>3</Subscript> glasses at a hydrostatic pressure up to 8.5 GPa

High-precision studies of the volume and the electrical resistivity of g-As₂Te₃ glasses at a high hydrostatic pressure up to 8.5 GPa at room temperature are performed. The glasses exhibit elastic behavior in compression only at a pressure up to 1 GPa, and a diffuse structural transformation and inelastic density relaxation (logarithmic in time) begin at higher pressures. When the pressure increases further, the relaxation rate passes through a sharp maximum at 2.5 GPa, which is accompanied by softening the relaxing bulk modulus, and then decreases, being noticeable up to the maximum pressure. When pressure is relieved, an unusual inflection point is observed in the baric dependence of the bulk modulus near 4 GPa. The polyamorphic transformation is only partly reversible and the residual densification after pressure release is 2%. In compression, the electrical resistivity of the g-As₂Te₃ glasses decreases exponentially with increasing pressure (at a pressure up to 2 GPa); then, it decreases faster by almost three orders of magnitude in the pressure range 2–3.5 GPa. At a pressure of 5 GPa, the electrical resistivity reaches 10^–3 Ω cm, which is characteristic of a metallic state; this resistivity continues to decrease with increasing pressure and reaches 1.7 × 10^–4 Ω cm at 8.1 GPa. The reverse metal–semiconductor transition occurs at a pressure of 3 GPa when pressure is relieved. When the pressure is decreased to atmospheric pressure, the electrical resistivity of the glasses is below the initial pressure by two–three orders of magnitude. Under normal conditions, both the volume and the electrical resistivity relax to quasi-equilibrium values in several months. Comparative structural and Raman spectroscopy investigations demonstrate that the glasses subjected to high pressure have the maximum chemical order. The glasses with a higher order have a lower electrical resistivity. The polyamorphism in the As₂Te₃ glasses is caused by both structural changes and chemical ordering. The g-As₂Te₃ compound is the first example of glasses, where the reversible metallization under pressure has been studied under hydrostatic conditions.     

Tunable growth of (GaxIn1−x)2O3 nanowires by water vapor

The tunable growth of In-doped Ga₂O₃ (Ga₂O₃:In) and Ga-doped In₂O₃ (In₂O₃:Ga) nanowires (NWs) on Au-coated Si substrates was achieved by modulating the amount of water vapor in flowing Ar at 700–750 °C via carbothermal reduction of Ga₂O₃/In₂O₃ powders with a fixed weight ratio. In Ar, only the Ga₂O₃:In NWs were grown, while in wet Ar the In₂O₃:Ga NWs were synthesized instead. The Ga concentration in In₂O₃ NWs decreased with the increment of water vapor in flowing Ar. The growth of both Ga₂O₃:In and In₂O₃:Ga NWs followed the vapor–liquid–solid process. The In and Ga doping induced a redshift and a blueshift in the optical bandgaps of Ga₂O₃ NWs and In₂O₃ NWs, respectively. The growth mechanisms and optical properties of Ga₂O₃:In and In₂O₃:Ga NWs were discussed.     

Pressure experiment determination of the direct-indirect transition in the quarternary In1−xGaxP1−zAsz

Spontaneous and laser emission from In_1-xGa_xP_1-zAs_z double heterojunction diodes near the direct-indirect crossover (E_Γ = E_X, x ≡ x_c, z ≡ z_c) are studied at 77°K as a function of hydrostatic pressure up to 6 kbar. The pressure coefficients of the spontaneous emission peaks and of the laser modes are ～- 10.5 × 10^-6 eV/bar which is characteristics of the Γ band edge in III–V semiconductors. Laser threshold current is found to rise rapidly as pressure is applied owing to the decreasing Γ-X separation and the resultant carrier transfer to the X minima. Experimental lower limits for the direct-indirect crossover at three points in the In_1-xGa_xP_1-zAs_z quaternary system are determined. These three points and the established crossover in GaAs_1-yP_y (y_c ≈ 0.46, 77°K) give for the quaternary crossover (77°K) x_c ? 0.52z_c = 0.72. and the value x_c ≈ 0.72 for the limiting case of In_1-xGa_xP. Band edge bowing effects along the direct-indirect crossover in the In_1-xGa_xP_1-zAs_z system are discussed. The highest energy laser (77°K) for this quaternary system is estimated from pressure measurements to be ～ 2.155 eV (5752 Å).