Optical and thermoelectric characterizations of electroplated n-Bi2(Te0.9Se0.1)3

Bismuth selenotelluride (Bi₂(Te_0.9Se_0.1)₃) films were electrodeposited at constant current density from acidic aqueous solutions with Arabic gum in order to produce thin films for miniaturized thermoelectric devices. X-ray fluorescence spectroscopy determined film compositions. X-ray diffraction pattern shows that the films as deposited are polycrystalline, isostructural to Bi₂Te₃ and covered by crystallites. Mueller-matrix analysis reveals that the electroplated layers are optically like an isotropic medium. Their pseudo-dielectric functions were determined using mid-infrared spectroscopic ellipsometry. Tauc-Lorentz combined with Drude dispersion relations were successfully used. The energy band gap E_g was found to be about 0.15 eV. Moreover, the fundamental absorption edge was described by an indirect optical band-to-band transition. From Seebeck coefficient measurement, films exhibit n-type charge carrier and the value of thermoelectric power is about −40 μV/K.     

Thermoelectric properties of Bi0.9Sb0.1 prepared by high pressure

The Bi_0.9Sb_0.1 powders were prepared by mechanical alloying and then pressed under 6 GPa at different pressing temperatures. X-ray diffraction spectra showed that the single phase was formed. The nanostructure of grain was observed by bright-field imaging. Electrical conductivity, Seebeck coefficient, and thermal conductivity had been investigated in the temperature range of 80-300 K. The absolute Seebeck coefficient value of 120.3 μV/K was measured at 130 K. The figure-of-merit reached a maximum value of 0.90×10⁻³ K⁻¹ at 140 K.     

Temperature dependence of thermoelectric properties of Ni-doped CoSb3

Temperature dependences of the Hall coefficient, Hall mobility and thermoelectric properties of Ni-doped CoSb₃ have been characterized over the temperature range from 20 to 773 K. Ni-doped CoSb₃ is an n-type semiconductor and the conduction type changes from n-type to p-type at around 450 K. The temperature for the transition from n-type to p-type increased with increasing Ni content x. The Seebeck coefficient reaches a maximum value near the transition temperature. The electrical resistivity indicates that Co_1−xNi_xSb₃ is a typical semiconductor when x≤0.03 and a degenerate semiconductor when x>0.03. Thermal conductivity analyses show that the lattice component is predominant at lower temperatures and carrier and bipolar components become large at temperatures higher than the transition temperature. The thermoelectric figure of merit reaches a maximum value close to the transition temperature and the largest value, 4.67×10⁻⁴ K⁻¹ at 600 K, was obtained for x=0.05.     

Synchrotron X-ray study of filled skutterudites CeFe4Sb12 and Ce0.8Fe3CoSb12

In situ synchrotron X-ray diffraction measurements are carried out on filled skutterudites CeFe₄Sb₁₂ and Ce_0.8Fe₃CoSb₁₂ up to 32 and 20 GPa, respectively, at room temperature. No phase transformation was observed for both samples in the pressure range. Fitting the pressure-volume data (up to 10 GPa) to the third-order Birch-Murnaghan equation of state, the bulk modulus B₀ is determined to be 74(4) GPa, with the pressure derivative B′₀=7(2) for CeFe₄Sb₁₂, and B₀=71(2) GPa and B′₀=8(2) for Ce_0.8Fe₃CoSb₁₂. The bulk moduli of filled skutterudites CeFe₄Sb₁₂ and Ce_0.8Fe₃CoSb₁₂ in our study are smaller than those from previous studies on unfilled skutterudite CoSb₃. The P-V curves of the unfilled skutterudite CoSb₃ and filled skutterudites Ce_yFe_4−xCo_xSb₁₂ showed good agreement, indicating that the Ce filling fraction and the replacement of Fe with Co have little effect on their compression behaviors.     

Thermally stimulated current measurements in undoped Ga3InSe4 single crystals

The trap levels in nominally undoped Ga₃InSe₄ crystals were investigated in the temperature range of 10-300 K using the thermally stimulated currents technique. The study of trap levels was accomplished by the measurements of current flowing along the c-axis of the crystal. During the experiments we utilized a constant heating rate of 0.8 K/s. Experimental evidence is found for one hole trapping center in the crystal with activation energy of 62 meV. The analysis of the experimental TSC curve gave reasonable results under the model that assumes slow retrapping. The capture cross-section of the trap was determined as 1.0×10⁻²⁵ cm² with concentration of 1.4×10¹⁷ cm⁻³.     

Low-temperature thermoelectric properties of Bi85Sb15−xNbx alloys prepared by high-press sintering

The nanocrystalline materials with the general formula Bi₈₅Sb_15−xNb_x (x=0, 0.5, 1, 2, 3) were prepared by mechanical alloying and subsequent high-pressure sintering. Their transport properties involving electrical conductivity, Seebeck coefficient and thermal conductivity have been investigated in the temperature range of 80-300 K. The absolute value of Seebeck coefficient of Bi₈₅Sb₁₃Nb₂ reaches a maximum of 161 μV/K at 105 K, which is 69% larger than that of Bi₈₅Sb₁₅ at the same temperature. The power factor and figure-of-merit are 4.45×10⁻³ WK⁻²m⁻¹ at 220 K and 1.79×10⁻³ K⁻¹ at 196 K, respectively. These results suggest that thermoelectric properties of Bi₈₅Sb₁₅ based material can be improved by Nb doping.     

Admittance spectroscopy of polycrystalline and epitaxially grown CuGaSe2

Using either single crystalline, epitaxially grown p-type CuGaSe₂ (CGSe) films in Schottky diodes or polycrystalline p-CuGaSe₂/n-CdS single-junction solar cells, we employed thermal admittance spectroscopy (TAS) to gain insight into the electronic transport mechanisms of CGSe. In both types of devices, the capacitance decreases about 50% to its geometrical value in a frequency dependent step between 250 and 150 K. For the Schottky diodes, this capacitance step reflects the response of the shallowest acceptors whose energy level is located 150 meV above the valence band. In the solar cells, a comparable response occurs but is superposed by carrier freeze-out outside the space-charge region.     

Structural,thermal and electrical properties of the semiconductor system Ag(1−x)CuxInSe2

This paper presents a study of bulk samples synthesized of the Ag_1−xCu_xInSe₂ semiconductor system. Structural, thermal and electrical properties, as a function of the nominal composition (Cu content) x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 were studied. The influence of x on parameters such as melting temperature, solid phase transition temperature, lattice parameters, bond lengths, crystallite size t (coherent domain), electrical resistivity, electrical mobility and majority carrier concentration was analyzed. The electrical parameters are analyzed at room temperature. In general, it is observed that the properties of the Ag_1−xCu_xInSe₂ system for x≤0.4 are dominated by n-AgInSe₂, while for x>0.4, these are in the domain of p-CuInSe₂. The crystallite size t in the whole composition range (x) is of the order of the nanoparticles. Secondary phases (CuSe, Ag₂Se and InSe) in small proportion were identified by XRD and DTA.     

Band-gap grading in Cu(In,Ga)Se2 solar cells

The quaternary system Cu(In,Ga)Se₂ (CIGS) allows the band gap of the semiconductor to be adjusted over a range of 1.04-1.67 eV. Using a non-uniform Ga/In ratio throughout the film thickness, additional fields can be built into p-type CIGS-based solar cells, and some researchers have asserted that these fields can enhance performance. The experimental evidence that grading improves device performance, however, has not been compelling, mostly because the addition of Ga itself improves device performance and hence a consistent separation of the grading benefit has not always been achieved. Numerical modeling tools are used in this contribution to show that (1) there can be a beneficial effect of grading, (2) in standard thickness CIGS cells the benefit is smaller than commonly believed, (3) there is also the strong possibility of reduced rather than of increased device performance, and (4) thin-absorber cells derive more substantial benefit.     

Glass formation in the As2Se3-As2Te3-Sb2Te3 system

Chalcogenide glasses from the As₂Se₃-As₂Te₃-Sb₂Te₃ system were synthesized for the first time. The glass-forming region was determined by X-ray diffraction and electron microscopic analyses.The basic physicochemical parameters such as density (d), microhardness (HV) and temperatures of phase transformations (glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network as well as the elasticity module (E) were calculated. The glass-forming ability was evaluated according to Hruby's criteria (K_G). The correlation between composition and properties of the (As₂Se₃)_x(As₂Te₃)_y(Sb₂Te₃)_z glasses was established and comprehensively discussed.     

Superconductivity and non-metallicity induced by doping the topological insulators Bi2Se3 and Bi2Te3

We show that by Ca doping the Bi₂Se₃ topological insulator, the Fermi level can be fine tuned to fall inside the band gap and therefore suppresses the bulk conductivity. Non-metallic Bi₂Se₃ crystals are obtained. On the other hand, the Bi₂Se₃ topological insulator can also be induced to become a bulk superconductor, with T_c∼3.8 K, by copper intercalation in the van der Waals gaps between the Bi₂Se₃ layers. Likewise, an as-grown crystal of metallic Bi₂Te₃ can be turned into a non-metallic crystal by slight variation in the Te content. The Bi₂Te₃ topological insulator shows small amounts of superconductivity with T_c∼5.5 K when reacted with Pd to form materials of the type Pd_zBi₂Te₃.     

Morphology, structure and photocatalytic performance of ZnIn2S4 synthesized via a solvothermal/hydrothermal route in different solvents

Hexagonal ZnIn₂S₄ photocatalysts with different morphology and crystallinity (micro-structures) were prepared in aqueous-, methanol- and ethylene glycol-mediated conditions via a solvothermal/hydrothermal method. The aqueous- and methanol-mediated ZnIn₂S₄ presented to be Flowering-Cherry-like microsphere, while the ethylene glycol-mediated ZnIn₂S₄ presented to be micro-cluster. In comparison with two other products, aqueous-mediated ZnIn₂S₄ possessed the best crystallinity (micro-structure), which resulted in the highest photocatalytic activity for hydrogen evolution under visible-light irradiation. Additionally, aqueous-mediated ZnIn₂S₄ was found to be more stable than the other two ZnIn₂S₄ photocatalysts while undergoing the photocatalytic process. During the photocatalytic reaction, the average rates for hydrogen production over aqueous-, methanol- and ethylene glycol-mediated ZnIn₂S₄ were determined to be 27.3, 12.4 and 9.1 μmol h^-1, respectively, in the present photocatalytic systems.     

The effects of elements doping on transport and thermoelectric properties of Sr3Ti2O7

The Ruddlesden–Popper (RP) phase compounds (Sr_0.95R_0.05)₃Ti₂O₇ (R=Er, Y, Dy, Gd, Eu, Sm, Nd and La) were prepared, and their transport and thermoelectric properties were investigated. The results indicate that high-T electrical resistivity ρ (300 K<T<1000 K) increases monotonically with temperature and basically has a relation ρ∝T^M, with M varying from 0.91 to 1.92 at temperatures T>~650 K, suggesting acoustic phonon scattering is dominant. At low temperatures (5 K<T<300 K), ρ for (Sr_0.95R_0.05)₃Ti₂O₇ (R=Nd and La) decreases monotonously with decreasing temperature, whereas ρ for (Sr_0.95R_0.05)₃Ti₂O₇ (R=Er, Y, Dy, Gd, Eu and Sm) decreases first, and then increases instead as T decreases to a critical temperature T_c. Moreover, electrical conductivity σ∝T^1/2 holds at lower temperatures, indicating that the electron–electron interaction caused by the presence of disorder dominates the transport process at the low temperatures. Besides, experiments show that at T<~400 K the lattice thermal conductivity of the doped compounds basically decreases with increase of the atomic mass of dopants. Generally, the figure of merit (ZT) at 1000 K increases first, and then decreases with the increase of the dopants' ionic radius, and the largest ZT is achieved in (Sr_0.95Gd_0.05)₃Ti₂O₇ mainly owing to its lower lattice thermal conductivity.     

Resistance anomaly and structural disorder in NiSi2 under high pressure

Results of X-ray diffraction, electrical resistance, thermoelectric power measurements and electronic band structure calculations on NiSi₂ under high pressure are reported. The thermoelectric power (TEP) changes sign near 0.5 GPa (from +30 to −20 μV/K). As the pressure is increased, the value of TEP increases further in magnitude and near 7 GPa it becomes −50 μV/K. The pressure vs. resistance curve measured up to 30 GPa using diamond anvil (DAC)-based technique exhibits a broad hump near 12 GPa and exhibits hysteresis on pressure release. The ADXRD patterns up to 42 GPa show a gradual irreversible loss of long-range order in NiSi₂ with the diffraction lines progressively broadening under pressure. The FWHM of the diffraction lines show a rapid increase in the half-widths close to 0.5 GPa and also near 12 GPa. The computed band structure at a compression (without any disorder) corresponding to 12 GPa, exhibits an electronic topological transition (ETT). The rapid increase in disorder above 12 GPa implies that the ETT may be facilitating the structural disorder. It is suggested that the pressure drives the material through a region of entropic and energetic barriers and induces disorder in the material.     

High pressure X-ray diffraction study of ReS2

The high-pressure behavior of rhenium disulfide (ReS₂) has been investigated to 51.0 GPa by in situ synchrotron X-ray diffraction in a diamond anvil cell at room temperature. The results demonstrate that the ReS₂ triclinic phase is stable up to 11.3 GPa, at which pressure the ReS₂ transforms to a new high-pressure phase, which is tentatively identified with a hexagonal lattice in space group P6?m2. The high-pressure phase is stable up to the highest pressure in this study (51.0 GPa) and not quenchable upon decompression to ambient pressure. The compressibility of the triclinic phase exhibits anisotropy, meaning that it is more compressive along interlayer directions than intralayer directions, which demonstrates the properties of the weak interlayer van der Waals interactions and the strong intralayer covalent bonds. The largest change in the unit cell angles with increasing pressures is the increase of β, which indicates a rotation of the sulfur atoms around the rhenium atoms during the compression. Fitting the experimental data of the triclinic phase to the third-order Birch-Murnaghan EOS yields a bulk modulus of K_OT=23±4 GPa with its pressure derivative K_OT′= 29±8, and the second-order yields K_OT=49±3 GPa.     

The elastic behavior of dense C3N4 under high pressure: First-principles calculations

We have carried a detailed theoretical study on the geometry, density of states, elastic properties, sound velocities and Debye temperature of α-, β-, c- and p-C₃N₄ compounds under a maximum of pressure up to 100 GPa by using first principles calculations. The optimized lattice constants under zero pressure and zero temperature agreed well with the previous experimental and theoretical results. The band gaps of the four types of dense C₃N₄ were widened gradually with the increase of pressure. The calculated Poisson’s ratio γ and B/G values suggest α-, c- and p-C₃N₄ are brittle materials under 0–100 GPa, whereas β-C₃N₄ will become a ductile material as external pressure reaches 57 GPa. We found that the Debye temperature of the four dense C₃N₄ gradually reduces in the order of c-C₃N₄>p-C₃N₄>α-C₃N₄>β-C₃N₄ at 0 GPa and 0 K. However, the Debye temperature of c-C₃N₄ was lower than p-C₃N₄ when external pressure exceeds 6.3 GPa. It may hint that the results could be served as a valuable prediction for further experiments.     

Electronic structure of a thermoelectric material: CsBi4Te6

We have calculated the electronic structure of CsBi₄Te₆ by means of first-principles self-consistent total-energy calculations within the local-density approximation using the full-potential linear-muffin-tin-orbital method. From our calculated electronic structure we have calculated the frequency dependent dielectric function. Our calculations shows that CsBi₄Te₆ a semiconductor with a band gap of 0.3 eV. The calculated dielectric function is very anisotropic. Our calculated density of state support the recent experiment of Chung et al. [Science 287 (2000) 1024] that CsBi₄Te₆ is a high performance thermoelectric material for low temperature applications.     

Effect of annealing temperature on the optical and electrical properties of amorphous As45.2Te46.6In8.2 thin films

The optical absorption of the As-prepared and annealed As_45.2Te_46.6In_8.2 thin films are studied. Films annealed at temperatures higher than 453 K show a decrease in the optical energy gap (E_o). The value of E_o increases from 1.9 to 2.43 eV with increasing thickness of the As-prepared films from 60 to 140 nm. The effect of thickness on high frequency dielectric constant (?_∞) and carrier concentration (N) is also studied. The crystalline structures of the As_45.2Te_46.6In_8.2 thin films resulting from heat treatment of the As-prepared film at different elevated temperatures is studied by X-ray diffraction. An amorphous-crystalline transformation is observed after annealing at temperatures higher than 453 K. The electrical conductivity at low temperatures is found due to the electrons transport by hopping among the localized states near the Fermi level. With annealing the films at temperatures higher than 473 K (the crystallization onset temperature) for 1 h, the electrical conductivity increases and the activation energy decreases, which can be attributed to the amorphous-crystalline transformations.     

Third-order nonlinear optical properties of Bi2S3 and Sb2S3 nanorods studied by the Z-scan technique

Bismuth sulfide (Bi₂S₃) and antimony sulfide (Sb₂S₃) nanorods were synthesized by hydrothermal method. The products were characterized by UV-vis spectrophotometer, X-ray powder diffraction (XRD) and transmission electron microscope (TEM). Bi₂S₃ and Sb₂S₃ nanorods were measured by Z-scan technique to investigate the third-order nonlinear optical (NLO) properties. The result of NLO measurements shows that the Bi₂S₃ and Sb₂S₃ nanorods have the behaviors of the third-order NLO properties of both NLO absorption and NLO refraction with self-focusing effects. The third-order NLO coefficient χ⁽³⁾ of the Bi₂S₃ and Sb₂S₃ nanorods are 6.25×10⁻¹¹ esu and 4.55×10⁻¹¹ esu, respectively. The Sb₂S₃ and Bi₂S₃ nanorods with large third-order NLO coefficient are promising materials for applications in optical devices.     

Electrical properties of TlGaTe2 single crystals under hydrostatic pressure

The effect of hydrostatic pressure (up to 0.82 GPa) on the electric properties of chain TlGaTe₂ single crystals has been investigated in the temperature range 77-296 K. It has been shown that pressure leads to a considerable increase of conductivity (σ_⊥) across the chains of TlGaTe₂ single crystals. Parameters of localized states in the band gap of TlGaTe₂ single crystal according to the low-temperature electrical measurements were obtained at various pressures.