Infrared and Raman Spectra of ZnIn2Se4

Infrared reflectivity and Raman spectra of polycrystalline ZnIn₂Se₄ revealed a total number of seven structures due to optical vibrational modes. Based on a comparison with previous measurements on other A^IIB₂^IIIC₄^VI compounds a symmetry assignment of the modes is proposed.     

Infrared lattice vibrations of CdIn2Se4

Infrared reflectivity spectra of CdIn₂Se₄ single crystals are measured at room temperature in the wavenumber range from 180 to 4000 cm⁻¹ for the polarization directions E ⟂ c and E ‖[112]. The spectra reveal two vibrational modes with nearly the same frequencies for both polarization directions. The frequencies of the modes with highest energy compare well with the corresponding mode frequencies in ZnIn₂Se₄, CuInSe₂ and AgInSe₂. It is concluded that these modes are sphalerite-like in nature and that their frequencies are essentially determined by the properties of the In Se bond.     

Far Infrared and Raman Optical Study of CdInGaS4, CdIn2S4, HgInGaS4 and CdIn2S2Se2 Crystals

Raman and infrared reflectivity spectra of CdInGaS₄, CdIn₂G₄, HgInGaS₄, and CdIn₂S₂Se₂ crystals have been investigated. The fiindamental phonon parameters, the limiting dielectric constants ϵ₀ and ϵ∞ and the reflectivity spectrum contours have been calculated using classical dispersion relations.     

Effects of Group III Cation Substitution in the Raman Spectra of Some Defective Chalcopyrites

We report on the Raman spectra of CdIn₂Se₄ and ZnIn₂Se₄ obtained in a transparency region. These spectra have a disordered-like appearance at high frequencies. A comparison is made with the Raman and IR spectra of the similar compounds CdGa₂Se₄ and ZnGa₂Se₄. The overall vibrational behaviour is mainly determined by the anion and a correspondence may be observed between the frequencies of some high energy polar modes. A strong non-polar breathing mode is observed at nearly the same frequency in all these compounds. The observed similarities between the spectra are discussed within the frame of the existing simplified models.     

Infrared Absorption Spectra of CdIn2Te4

Transmittance and reflectance spectra of CdIn₂Te₄ are measured in the wavenumber range from 200 to 4000 cm^–1. In the range from 200 to 400 cm^–1 the spectra are governed by two-phonon combination mode absorptions. In the wavenumber range above 400 cm^–1 absorption coefficients below 1 cm^–1 and a constant reflectivity of about 0.21 are found.     

Infrared reflectivity of ZnIn2Te4

Infrared reflectivity spectra of ZnIn₂Te₄ single crystals are measured at room temperature in the wavenumber range from 170 to 4000 cm⁻¹. The spectra reveal a single vibrational mode the frequency of which compares well with the frequencies of the high-energy infrared active modes in HgIn₂Te₄, CuInTe₂ and AgInTe₂. It is concluded that these modes are sphalerite-like in nature and that they are essentially determined by the properties of the In—Te bond.     

Heat capacity of LiInS2, LiInSe2 and LiInTe2 between 200 and 550 K

The molar heat capacity at constant pressure of LiInS₂, LiInSe₂ and LiInTe₂ was measured in the temperature range from about 200 K to 550 K. An analysis of the experimental data showed that the anharmonic contribution to the heat capacity can be described by a polynomial of fourth order in the temperature. A comparison of the results for the LiInC₂^VI compounds with those for the AgB^IIIC₂^VI and A^IIB^IVC₂^V chalcopyrite compounds showed that the lattice anharmonicity effects are essentially influenced by the specific nature of the Li C^VI bond.     

Thermodynamic feasibility study for chemical vapour deposition of some ternary crystals using iodine and hydrogen iodide

Thermodynamic feasibility of transition metal dichalcogenide (TMDC) single crystals of Cu Al S₂, Cu Al Se₂, Cu Al Te₂, Cu Ga S₂, Cu Ga Se₂, Cu Ga Te₂, Cu In S₂, Cu In Se₂, Cu In Te₂, Ag Ga S₂, Ag Ga Se₂, Ag Ga Te₂, Ag In Se₂, Ag In Te₂, using iodine and hydrogen iodide as transporting agents has been reported in this paper. Results give range of temperature for the iodide transport and prevention of starting material formation (elemental transport) in the growth zone. From the range of temperature for the growth of crystals, selected source zone and growth zone temperatures with a differential of 100 °C are also listed. Referring the data listed in the tables can grow good quality crystals. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron diffraction RDF analysis of amorphous As2Se3,AAs2Se2Te,As2SeTe2 and As2Te3 films

The local order in amorphous films of As₂Se₃, As₂Se₂Te, As₂SeTe₂, and As₂Te₃ has been examined by scanning electron diffraction with direct recording of the intensity of the elastically scattered electrons. The radial distribution functions indicate that there is a systematic increase in mean nearest neighbor distance as the Te concentration is increased, butthe mean coordination number increases slightly around 2.4. Pair function calculation of models shows that the 3-aand 2-fold coordinations of arsenic and chalcogens are retained in these glasses and the interatomic distances are close to those predicted from the Pauling covalent atomic radii of the constituent atomic species. The short range order appears to be similar in amorphous and crystalline As₂Se₃, but different in the case of As₂Te₃ as found by previous workers on bulk materials.     

Direct measurement of isothermal compressibility of amorphous semiconductors

The isothermal compressibilities of the chalcogenide glasses Te₁₅Ge₃As₂, Te₁₅Ge₂As₃ and As₂Se₃ have been measured to 5 kbar by direct measurement of the change in sample length using a differential transformer placed inside the hydrostatic pressure vessel. Calibration data was obtained from the measurement of the compressibilities of alkali halide single crystals. For Te₁₅Ge₃As₂, the isothermal compressibility was found to be 6.00 × 10^?12 ? 0.7 × 10^?22P cm²/dyne; for Te₁₅Ge₂As₃, 5.58 × 10^?12 + 0.3 × 10^?22P cm²/dyne; for As₂Se₃, 6.30 × 10^?12 ? 0.8 × 10^?22P cm²/dyne where P is the pressure in dynes/cm². Errors are near 5%.     

Lattice Vibrations and Interatomic Forces in AIIB2IIIC4VI Defect-Chalcopyrite Compounds (I) Keating Model Considerations

The lattice vibrations of the A^IIB^III₂C^VI₄ semiconductors with defect-chalcopyrite structure are treated in a simplified version of the Keating model considering only interaction with nearest neighbours and assuming that all anions occupy their ideal lattice sites. It is found that in this model the frequencies of the nonpolar and polar modes with highest energy are determined by the properties of the B^III–C^VI sublattice alone. The frequencies of all the other optical modes depend not only on the A^II–C^VI and B^III–C^VI interactions but are also influenced by the presence of the ordered array of vacancies. The results obtained are compared with previous model considerations.     

Interatomic force constants in AIIBIVCV2 chalcopyrite compounds

Force constants of the A^II C^V and B^IV C^V bonds in the A^IIB^IVC^V₂ compounds with chalcopyrite structure are estimated from experimental lattice vibration data using a simplified version of the Keating model. It is shown that the force constants depend exponentially on the bond length. The parameters of this relation are practically the same as those found for the A^IV A^IV, A^III B^V and A^II B^VI bonds in the elemental semiconductors and binary compounds and for the B^III C^VI bond in the A^IB^IIIC^VI₂ semiconductors.     

Infrared studies of Se-based polynary chalcogenide glasses (II): YxZxSe100−2x (Y = Ge,As; Z = As,Te)

The infrared (IR) absorption spectra for Y_xZ_xSe_100?2x glasses (Y = Ge, As;Z = As, Te), x = 2.5 and 5.0 are measured in the wavenumber region 700-60 cm^?1 at room temperature. These IR spectra are explained by comparing with the IR spectra already reported for the binary glasses such as Ge–Se, As–Se and Se–Te. In Ge_xAs_xSe_100-2x glasses (x ? 5.0), the main spectral features as well explained by both the spectra of Ge_xSe_100?x and As_xSe_100?x glasses. Main structural units in these glasses are considered to be GeSe₄ tetrahedra and AsSe₃ pyramids, and Se₈ rings and Se_n chains which are the units in pure glassy Se. In Ge_xTe_xSe_100?2x glasses (x ? 5.0) and IR band which cannot be explained by either the spectra of Ge_xSe_100?x or Se_100?xTe_x glasses appears at 210 cm^?1. This band is considered to be due to Ge–Te bonds. The IR spectra of As_xTe_x Se_100?2x glasses (x ? 5.0) are well explained by both the spectra of As_xSe_100?x and Se_100?xTe_x glasses. It is concluded that As and Te atoms combine with Se atoms in the forms of AsE₃ pyramids and Se₅Te₃ mixed rings, respectively.     

Growth,structure, and some transport properties of topological insulators based on bismuth chalcogenide single crystals

Single crystals of topological insulators—bismuth chalcogenides Bi₂Te₃, Bi_{2 ? x} Sn _x Te₃, Bi₂Se₃, and Bi_{2 ? x} Cu _x Se₃ with different charge-carrier densities—are grown by the modified Bridgman method. Their composition and structure are investigated and temperature dependences of the electric resistance and magnetic field dependences of the Hall voltage are obtained.     

Bond Ionicities and Structural Trends in Some LiBIIIC Compounds

The individual and average bond ionicities of LiAlO₂, LiGaO₂, LiInS₂, LiInSe₂ and LiInTe₂ are evaluated from spectroscopic data. It is found that in these compounds the Li C^VI bond is essentially ionic in nature. It is shown that the structural properties of the compounds can be understood in terms of the average bond parameters.     

Ab initio calculation of vibrational frequencies of GexSe1−x glass

We have used the density functional theory to make the models of Ge_xSe_1?x glass for which the energy is a minimum. The clusters, Ge₂Se₂, Ge₂Se₃, Ge₃Se, Ge₃Se₂, Ge₄Se, GeSe₃, GeSe₄, chain mode zig-zag Ge₄Se₃, corner sharing GeSe₄, and edge sharing Ge₂Se₆, have been made successfully and their vibrational spectra have been calculated from the first principles. We are able to optimize the bond distances as well as the bond angles. The calculated values of the frequencies of vibrations of the various clusters have been compared with those obtained from the experimental Raman spectra of actual glasses, Ge_xSe_1?x(0 < x < 0.3). The local concentration, x within 0.25 nm is nonuniform in the amorphous material. When the same cluster occurs in two stable configurations, low frequency vibrations of frequency, ν < 100 cm^?1, are found. The corner sharing GeSe₄ has low frequency modes at 54 cm^?1 and 93 cm^?1 whereas these modes disappear in the pyramidal configuration. The low frequency modes are therefore associated with the breaking of C₄ symmetry of the pyramidal configuration. The computed vibrational frequencies of clusters Ge₃, Ge₄Se₃, Ge₂Se₃, GeSe₃ and Ge₃Se₂ are actually present in the Raman spectra of the glass, Ge_xSe_1?x(0 < x < 0.3).     

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.     

Chemical shifts of the K-absorption discontinuities of germanium and selenium in some amorphous systems

In the present investigation the chemical shifts of the K-absorption discontinuities of germanium and selenium have been studied in their amorphous chemical compounds Ge₁₀Se₉₀, Ge₃₀Se₇₀, Ge₁₀Se₈₀Te₁₀ and Ge_33.3Se₄₀Te_26.7 using a 1 m Cauchois type bent crystal (mica) X-ray spectrograph. A graph of the chemical shift ΔE in binary compounds against the effective charge q on the absorbing atoms has been plotted. This plot is helpful in determining the effective charges in ternary compounds in which they cannot be calculated theoretically.     

Role of Te valence on phases crystallized in K2O–Nb2O5–TeO2 glasses

Differences in crystalline phases between glass-ceramics and sintered ceramics in the K₂O–Nb₂O₅–TeO₂ system have been examined, particularly to obtain information on the role of Te valence on crystallization behaviors of TeO₂-based glasses. In glasses or glass-ceramics, the valence of Te⁴⁺ is retained even during heat-treatment up to around 600°C, leading to the formation of crystalline phases containing Te⁴⁺, e.g., the face-centered cubic crystalline phase. In a powder sintering method, Te⁴⁺ is easily oxidized to Te⁶⁺ during sintering at around 600°C in air and compounds such as KNbTeO₆ in which Te⁶⁺ is present are formed.     

Thermal expansion in CuAlTe2 compound

The lattice parameters a and c as well as the axial thermal expansion coefficients α ⟂ and α ∥ in the CuAlTe₂ chalcopyrite-type compound are determined as a function of temperature in the range from 80 to 650 K by a X-ray diffractometry technique. The data obtained are used to evaluate the axial ratio c/a, the tetragonal distortion δ = 2 — c/a, the interatomic distances for Cu Te and Al Te bonds and their temperature coefficients. It is found that the thermal expansion behaviour of CuAlTe₂ is similar to that of other CuB^IIIC^VI₂ compounds in having a relatively small expansivity along the c-axis and a large one in the perpendicular direction. When comparing the results for a series of the CuB^IIIC^VI₂ compounds (B Al, Ga, In; C S, Se, Te) it is shown that the correlations between the thermal expansion coefficients α ⟂, α ∥, α_m, dδ/dT and the tetragonal distortion δ, as well as the molar mass of the compound take place.