Properties of CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> crystals and In/CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> structures

Using the method of planar crystallization from the melt with deviations from the stoichiometric composition, p-CuIn₃Se₅ single crystals are grown. The electrical properties of the homogeneous crystals are studied. It is found that the resistivity of the p-CuIn₃Se₅ crystals depends on the excess Se content in the melt. It is established that the voltaic photosensitivity of the In/CuIn₃Se₅ structures is enhanced with an increasing excess of Se content in the melt. The energy spectrum and the character of interband transitions in the CuIn₃Se₅ crystals are discussed. It is concluded that the CuIn₃Se₅ ternary compound can be used in high efficiency photoelectric converters of solar radiation.     

Electrical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> single crystals and photosensitivity of Al/In<Subscript>2</Subscript>Se<Subscript>3</Subscript> Schottky barriers

In₂Se₃ single crystals ∼40 mm long and 14 mm in diameter were grown by the Bridgman method. The composition of grown single crystals and their crystal structure were determined. The conductivity (σ) and Hall constant (R) of grown single crystals were measured and the first Schottky barriers Al/n-In₂Se₃ were fabricated. Rectification and photovoltaic effect were detected in the new structures. Based on the study of the photosensitivity spectra of Al/n-In₂Se₃ structures, the nature of the interband transitions and band gap of In₂Se₃ crystals were determined. It was concluded that the new structures can be applied to develop broadband photoconverters of optical radiation.     

Optical properties of imperfect In<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Spectra of complete sets of optical functions for α-and β-In₂Se₃ in the range of 0–20 eV were calculated using experimental reflection spectra and the Kramers-Kronig relation. Special features in the spectra of optical functions for both In₂Se₃ phases were analyzed. The spectra of both permittivity and characteristic electron energy losses were decomposed into elementary transverse and longitudinal components using the combined Argand diagrams. The main parameters of the electron transitions for these components were determined. The structure of the components was compared with the structure of the expected spectrum of interband transitions.     

Optical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin films

In₂Se₃ films are produced by ion-beam evaporation at substrate temperatures of 313 and 623 K. As the target, In₂Se₃ single crystals grown by the vertical Bridgman method are used. The composition and structure of the crystals and films are determined by the X-ray spectral analysis and X-ray diffraction techniques, respectively. It is established that the crystals and films crystallize with the formation of a hexagonal structure. The band gap and refractive index of the In₂Se₃ films are determined from the transmittance and reflectance spectra. It is found that, as the substrate temperature is increased, the band gap increases.     

Optical properties of CuIn<Subscript>5</Subscript>Se<Subscript>8</Subscript> single crystals

Single crystals of the CuIn₅Se₈ ternary compound are grown by the Bridgman-Stockbarger method (with the vertical layout of the procedure). The composition and structure of the crystals are determined. The spectra of transmittance and photoluminescence are studied in the temperature range from 10 to 300 K. The transmittance spectra and the photoluminescence spectra are used to determine, correspondingly, the band gap and the energy of donor-acceptor transitions in the CuIn₅Se₈ crystals. The temperature dependences of these parameters are obtained.     

Development and photoelectric properties of In/<Emphasis Type="Italic">p</Emphasis>-Ag<Subscript>3</Subscript>AsS<Subscript>3</Subscript> surface-barrier structures

Homogeneous p-Ag₃AsS₃ bulk single crystals with rhombic structure have been grown by planar crystallization from melts with atomic composition corresponding to this ternary compound. Photosensitive surface-barrier structures based on the interface between the surface of these crystals and thin films of pure indium are fabricated for the first time. The photosensitivity of fabricated structures is studied in natural and linearly polarized light. Photosensitivity spectra of In/p-Ag₃AsS₃ structures are measured for the first time and used to determine the nature and energy of interband transitions in p-Ag₃AsS₃ crystals. The phenomenon of natural photopleochroism is studied for surface-barrier structures grown on oriented p-Ag₃AsS₃ single crystals. It is concluded that Ag₃AsS₃ single crystals can be used in photoconverters of natural and linearly polarized light.     

A comparative study on the electronic and optical properties of Sb<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin film

The thin film of Sb₂Se₃ was deposited by thermal evaporation method and the film was annealed in N₂ flow in a three zone furnace at a temperature of 290°С for 30 min. The structural properties were characterized by scanning electron microscopy (SEM), transmission electron microscopy (ТЕМ), X-ray diffraction (XRD) and Raman spectroscopy, respectively. It is seen that the as-deposited film is amorphous and the annealed film is polycrystalline in nature. The surface of Sb₂Se₃ film is oxidized with a thickness of 1.15 nm investigated by X-ray photolecetron spectroscopy (XPS) measurement. Spectroscopic ellipsometry (SE) and UV–vis spectroscopy measurements were carried out to study the optical properties of Sb₂Se₃ film. In addition, the first principles calculations were applied to study the electronic and optical properties of Sb₂Se₃. From the theoretical calculation it is seen that Sb₂Se₃ is intrinsically an indirect band gap semiconductor. Importantly, the experimental band gap is in good agreement with the theoretical band gap. Furthermore, the experimental values of n, k, ε₁, and ε₂ are much closer to the theoretical results. However, the obtained large dielectric constants and refractive index values suggest that exciton binding energy in Sb₂Se₃ should be relatively small and an antireflective coating is recommended to enhance the light absorption of Sb₂Se₃ for thin film solar cells application.     

Thermoelectric Properties of Spark Plasma-Sintered In<Subscript>4</Subscript>Se<Subscript>3</Subscript>-In<Subscript>4</Subscript>Te<Subscript>3</Subscript>

We report the thermoelectric properties of spark plasma-sintered In₄Se₃-In₄Te₃ materials. For comparison, pure In₄Se₃ and In₄Se₃ (80 wt.%)/In₄Te₃ (20 wt.%) mixture samples were prepared. In₄Se₃ and In₄Te₃ powders were synthesized by a conventional melting process in evacuated quartz ampoules, and a spark plasma method was used for the sintering of the pure In₄Se₃ and mixture samples. Thermoelectric and structural characterizations were carried out, and the mixing effect of In₄Se₃ and In₄Te₃ on the thermoelectric properties was investigated.     

Optical Study of Filled Tetrahedral Compounds Li<Subscript>3</Subscript>AlN<Subscript>2</Subscript> and Li<Subscript>3</Subscript>GaN<Subscript>2</Subscript>

A detailed analysis of the optical properties of filled tetrahedral semiconductors Li₃AlN₂ and Li₃GaN₂ has been performed, using the full potential linearized augmented plane wave method within the density functional theory. The real and imaginary parts of the dielectric function ε(ω), the optical absorption coefficient I(ω), the reflectivity R(ω), and the electron energy loss function are calculated within the random phase approximation. The interband transitions responsible for the structures in the spectra are specified. Looking at optical matrix element, we note that the major peaks are dominated by transition from metal s, N 2p states to N 2p, Ga 3d states. The theoretical calculated optical properties and electron energy loss spectrum yield a static dielectric constant of 5.34 and a plasmon energy of 19.47 eV for Li₃GaN₂. In the Li₃AlN₂ compound, the static dielectric constant decreases to 4.75 and yields a plasmon energy of 18.5 eV. The effect of spin–orbit coupling on the optical properties is also investigated and found to be quite small, especially in the low-energy region. In order to check the reliability of our calculations, analogous results obtained for Be₃N₂ in the same structure [space group Ia3(206)] are included in this work.     

Study of single crystals of the CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> ternary compound

Single crystals of the CuIn₃Se₅ ternary compound are grown from the melt by the Bridgman-Stockbarger method. The composition, structure, and electrical properties of the crystals are studied. From the transmittance spectra in the region of the optical absorption edge, the band gap is determined in the temperature range from 10 to 300 K. Using the dilatometry method, the relative elongation is measured for crystals oriented parallel and orthogonal to their principal axis, and the coefficients of thermal expansion are calculated.     

Electronic and Optical Modeling of Solar Cell Compounds CuGaSe<Subscript>2</Subscript> and CuInSe<Subscript>2</Subscript>

We present dielectric-function-related optical properties such as absorption coefficient, refractive index, and reflectivity of the semiconducting chalcopyrites CuGaSe₂ and CuInSe₂. The optical properties were calculated in the framework of density functional theory (DFT) using linear combination of atomic orbitals (LCAO) and full-potential linearized augmented plane wave (FP-LAPW) methods. The calculated spectral dependence of complex dielectric functions is interpreted in terms of interband transitions within energy bands of both chalcopyrites; for example, the lowest energy peak in the e₂ (w) \varepsilon_{2} (\omega ) spectra for CuGaSe₂ corresponds to interband transitions from Ga/Se-4p → Ga-4s while that for CuInSe₂ emerges as due to transition between Se-4p → In-5s bands. The calculated dielectric constant, e₁ (0) \varepsilon_{1} (0) , for CuInSe₂ is higher than that of CuGaSe₂. The electronic structure of both compounds is reasonably interpreted by the LCAO (DFT) method. The optical properties computed using the FP-LAPW model (with scissor correction) are close to the spectroscopic ellipsometry data available in the literature.     

Fabrication and photoelectric properties of oxide/CuIn<Subscript>5</Subscript>Se<Subscript>8</Subscript> heterojunctions

Single crystals of the n-CuIn₅Se₈ compound of hexagonal modification have been grown by direct crystallization from melt. On the basis of the experimental study of its thermal interaction with air oxygen, a method for fabricating new oxide/n-CuIn₅Se₈ heterojunctions is proposed. Electrical and photoelectric properties of the structures obtained have been investigated. It is shown that the interaction of n-CuIn₅Se₈ of hexagonal modification with air oxygen makes it possible to obtain heterojunctions with high photosensitivity. The new technology can be used in the design of broadband optical radiation converters based on n-CuIn₅Se₈ crystals.     

Electrical properties of FeIn<Subscript>2</Subscript>Se<Subscript>4</Subscript> single crystals

The temperature dependence of electrical conductivity and current-voltage characteristics of FeIn₂Se₄ single crystals were studied. It is shown that the current in the nonlinear range of the current-voltage characteristic is caused by the field effect. The activation energy of charge carriers, the concentration of traps, and the shape of a potential well in the region of a trap are determined.     

Photoluminescence and composition of amorphous As<Subscript>2</Subscript>Se<Subscript>3</Subscript> films modified with Er(<Emphasis Type="Italic">thd</Emphasis>)<Subscript>3</Subscript> complex compound

The photoluminescence and composition of amorphous As₂Se₃ films modified with an Er(thd)₃ complex compound have been studied. A band centered at 1.54 μm, characteristic of photoluminescence from Er embedded in amorphous matrices, has been revealed at room temperature. The composition of thin amorphous As₂Se₃ films modified with an Er(thd)₃ complex compound has been examined by methods of nuclear microanalysis: Rutherford backscattering and nuclear resonant reactions. Dependences of the concentrations of Er ions, oxygen, and carbon on the growth conditions of the films are obtained. It is shown that the Er concentration in a thin film varies nonlinearly as the relative concentration of the starting complex compound increases. In addition, the increase in the Er content of a film is accompanied by a simultaneous rise in the content of such light elements as oxygen and carbon. Comparative analysis of the nuclear microanalysis data and IR spectra demonstrates that, in modification of As₂Se₃ with the Er(thd)₃ complex compound by the given method, the nearest environment of Er in the complex compound is partly preserved.     

Specific thermoelectric properties of lightly doped Bi<Subscript>2</Subscript>(TeSe)<Subscript>3</Subscript> solid solutions

Electrical and thermoelectric properties of a lightly doped n-Bi₂Te_2.7Se_0.3 solid solution have been studied in the temperature range 77–300 K. The results are compared with data for the compound PbTe_0.9Se_0.1 with a similar magnitude of the Seebeck coefficient S at 84 K. Along with lower thermal conductivity, Bi₂Te_2.7Se_0.3 has a higher electrical conductivity σ and a much weaker temperature dependence. As a result, the power coefficient S ²σ in optimal samples begins to decrease only when the density of minority carriers becomes significant. In this case, |S| considerably exceeds the standard value of 200 μV/K. The reduction of the electron density reduces the thermoelectric figure of merit Z at its maximum and slightly lowers the temperature of the maximum; therefore, the expected effect on the average value of Z in the range 77–300 K is absent. Similar behavior is observed in Bi₂Te_2.88Se_0.12, although the effect is less pronounced. The experimental results are discussed taking into account possible changes in the dominant scattering mechanisms, carrier density, and electron energy spectrum. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 38, No. 7, 2004, pp. 811–815. Original Russian Text Copyright ? 2004 by Konstantinov, Prokof’eva, Ravich, Fedorov, Kompaniets.     

Photosensitivity of ZnO/CdS/Cu(In,Ga)Se<Subscript>2</Subscript>/Mo thin-film solar cells fabricated on various substrates

The results of measuring the first spectra of relative quantum efficiency for photoconversion in thin-film ZnO/CdS/Cu(In,Ga)Se₂/Mo solar cells fabricated on rigid (glass) and flexible (polyimide) substrates are reported. The character of interband transitions has been studied and the values of the band gap for direct and indirect transitions in thin Cu(In,Ga)Se₂ films are determined. It is found that a shift of the maximal photosensitivity for the obtained solar cells to shorter wavelengths is observed as rigid substrates are replaced by flexible ones. It is concluded that thin-film Cu(In,Ga)Se₂ structures can be used as broad-band photoconverters of solar radiation.     

Effects of Cooling Rate on Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Bi<Subscript>2</Subscript>(Se<Subscript>0.4</Subscript>Te<Subscript>0.6</Subscript>)<Subscript>3</Subscript> Compounds

A series of Bi₂(Se_0.4Te_0.6)₃ compounds were synthesized by a rapid route of melt spinning (MS) combined with a subsequent spark plasma sintering (SPS) process. Measurements of the Seebeck coefficient, electrical conductivity, and thermal conductivity were performed over the temperature range from 300 K to 520 K. The measurement results showed that the cooling rate of melt spinning had a significant impact on the transport properties of electrons and phonons, effectively enhancing the thermoelectric properties of the compounds. The maximum ZT value reached 0.93 at 460 K for the sample prepared with the highest cooling rate, and infrared spectrum measurement results showed that the compound with lower tellurium content, Bi₂(Se_0.4Te_0.6)₃, possesses a larger optical forbidden gap (E _g) compared with the traditional n-type zone-melted material with formula Bi₂(Se_0.07Te_0.93)₃. Our work provides a new approach to develop low-tellurium-bearing Bi₂Te₃-based compounds with good thermoelectric performance.     

Ab Initio Calculations of Phonon Dispersion in ZnGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>

In the context of density functional theory, the phonon density of states and phonon dispersion are calculated for ZnGa₂Se₄. The temperature dependence of the heat capacity of ZnGa₂Se₄ in the temperature range 5–400 K is obtained. The calculated frequencies and symmetries of phonon modes in the center of the Brillouin zone are in good agreement with experimental data obtained by Raman spectroscopy and infrared spectroscopy.     

Effect of Vacancy Distribution on the Thermal Conductivity of Ga<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Our group has focused attention on Ga₂Te₃ as a natural nanostructured thermoelectric material. Ga₂Te₃ has basically a zincblende structure, but one-third of the Ga sites are structural vacancies due to the valence mismatch between Ga and Te. It has been confirmed that (1) vacancies in Ga₂Te₃ exist as two-dimensional (2D) vacancy planes, and (2) Ga₂Te₃ exhibits an unexpectedly low thermal conductivity (κ), most likely due to highly effective phonon scattering by the 2D vacancy planes. However, the effect of the size and periodicity of the 2D vacancy planes on κ has been unclear. In addition, it has also been unclear whether only the 2D vacancy planes reduce κ or if point-type vacancies can also reduce κ. In the present study, we tried to prepare Ga₂Te₃ and Ga₂Se₃ with various vacancy distributions by controlling annealing conditions. The atomic structures of the samples were characterized by means of transmission electron microscopy, and κ was evaluated from the thermal diffusivity measured by the laser flash method. The effects of vacancy distributions on κ of Ga₂Te₃ and Ga₂Se₃ are discussed.     

Room-temperature photoluminescence of Ga<Subscript>0.96</Subscript>In<Subscript>0.04</Subscript>As<Subscript>0.11</Subscript>Sb<Subscript>0.89</Subscript> lattice matched to InAs

Photoluminescence (PL) has been observed at room temperature from a Ga_0.96In_0.04As_0.11Sb_0.89 quaternary solid solution for the first time. High-quality epitaxial layers of n-type (Te-doped) Ga_0.96In_0.04As_0.11Sb_0.89 with low In content were grown by liquid phase epitaxy (LPE) lattice-matched to InAs(100) substrates from a Ga-rich melt. The PL properties of the material were investigated over a wide temperature range, and the principal radiative transitions were identified. In the temperature range <150 K, donor-acceptor recombination involving the first and second ionization state of native antisite defects was the dominant radiative-recombination process, whereas interband recombination was found to dominate at room temperature.