Optical spectra and energy band structure of AgAsS2 crystals

Ground and excited states of three exciton series are observed in the region of fundamental absorption edge of AgAsS₂ crystals. The contours of exciton reflection spectra are calculated and the main parameters of excitons and energy bands are determined in the center of Brillouin zone. The optical reflection spectra are investigated at 30 K in E∥c and E⊥c polarizations in AgAsS₂ crystals in the region of 2-6 eV. The optical functions are calculated from the reflection spectra and a scheme of electronic transitions responsible for peculiarities of reflection spectra deep into the absorption band is proposed.     

Interference of ordinary and extraordinary waves in AgAsS2 crystals

The anisotropy of the near-bandgap absorption is investigated in AgAsS₂ crystals. The refraction indices, n^‖ and n^⊥ respectively for the E‖c and E⊥c polarizations as well as the spectral dependence of the refraction indices difference, Δn=n‖−n^⊥ are determined from the interference spectra of AgAsS₂ crystals. A transmission band with four maxima is observed in the transmission spectra of crystals placed between crossed polarizers. The optical parameters n, k, ε₁, and ε₂ for the E‖c and E⊥c polarizations are calculated from the reflection spectra by using the Kramers–Kronig relations.     

Optical studies of (NH4)2SO4 single crystal in the paraelectric phase

Transmittance and absorbance spectra of (NH₄)₂SO₄ single crystals along [010] direction were measured at different temperatures (296, 308, 318, 328 and 348 K) in the paraelectric phase. The absorption coefficient was computed and the analysis of the data revealed the existence of two optical transitions in (NH₄)₂SO₄ single crystals. The direct and indirect band gaps were shifted towards the longer wavelength with increasing temperature. The data on the allowed indirect transition was analyzed and interpreted in terms of two valence bands originated by spin orbit interaction and crystal field splitting. The momenta E_p were calculated as the difference between E_g1, the first valence to conduction band, and E_g2 for the second valence band at different temperatures. The results of extinction coefficient (k), the refractive index (n), and dielectric constants (ε) were also discussed and calculated as a function of wave length (λ). The heat treatment of the crystals proved that the variations of these optical parameters can be consequence of the internal microstructure changes caused by annealing.     

Optical and acoustic properties of TeO2/WO3 glasses with small amount of additive ZrO2

The optical and acoustic properties of tellurite glasses in the system TeO₂/ZrO₂/WO₃ have been investigated. The refractive index at different wavelengths and the optical spectra of the glasses have been measured. From the refractive index and absorption edge studies for prepared glasses, the optical parameter viz; optical band gap (E_opt), Urbach energy, (ΔE), dispersion energy, E_d, and the average oscillator energy, E₀, have been calculated. Sound velocities were measured by pulse echo technique. From these velocities and densities values, various elastic moduli were calculated. The variations in the refractive index, optical energy gap and elastic moduli with WO₃ content have been discussed in terms of the glass structure. Quantitatively, we used the bond compression model for analyzing the room temperature elastic moduli data. By calculating the number of bonds per unit volume, the average stretching force constant, and the average ring size we can extract valuable information about the structure of the present glasses.     

Low-temperature absorption edge and photoluminescence in layered structured Tl2Ga2S3Se single crystals

The absorption edge of undoped Tl₂Ga₂S₃Se crystals have been studied through transmission and reflection measurements in the wavelength range 440–1100 nm and in the temperature range 10–300 K. The absorption edge was observed to shift toward lower energy values with increasing temperature. As a result, the rate of the indirect band gap variation with temperature γ=−2.6×10⁻⁴ eV/K and the absolute zero value of the band gap energy E_gi(0)=2.42 eV were obtained.     

Exciton spectra, valence band splitting, and energy band structure of CuGaXIn1−XS2 and CuGaXIn1−XSe2 crystals

Exciton spectra are studied in CuGa_XIn_1−XS₂ solid solutions by means of photoreflectivity and wavelength modulation spectroscopy at liquid nitrogen temperature. The exciton parameters, dielectric constants, and free carrier effective masses are deduced from experimental spectra by calculations in the framework of a model taking into account the spatial dispersion and the presence of a dead-layer. The crystal field and spin orbit valence band splitting is calculated as a function of X taking into account the energy position of excitonic lines. The energy band structure of CuGa_XIn_1−XS₂ and CuGa_XIn_1−XSe₂ compounds is derived from optical spectra at photon energies higher than the fundamental band gap. The energies of optical transitions are tabulated for X values from 0 to 1.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

Dielectric modelling of the transmittance spectra of thin As20S80 films

As₂₀S₈₀ thin films with different thicknesses (49.4-763.1 nm) were deposited on glass substrates using a thermal evaporation technique. Spectrophotometric measurements of the films' transmittance were taken in the wavelength range of 190-2500 nm. The transmission spectra were simulated with a computer model based on dielectric modelling to determine the optical constants and thicknesses of the films. The O'Leary-Johnson-Lim (OJL) models implemented in the commercial software programme SCOUT were used. Thicknesses obtained by the simulated method were correlated to the results obtained from a surface profiler technique. Optical parameters, such as the refractive index n, the absorption coefficient k, the optical band gap E_g, the high-frequency dielectric constant ε_∞, the Urbach energy E_U, the single-oscillator energy and the dispersion energy, were determined. The results indicated that the thickness effect can be separated into two distinct groups for films of thicknesses either less than or greater than 312 nm.     

Reflection and vibrational spectra of SbSCl0.1I0.9 crystals in the ferroelectric phase-transition region

SbSCl_0.1I_0.9 crystals were grown from the vapor phase and reflection spectra were recorded using a Fourier-transform IR spectrometer. The optical parameters and optical functions along the c axis were calculated using an improved Kramers–Kronig technique with two confining spectral limits. The reflection spectra were analyzed using the oscillator parameter fitting technique for comparison of results. The vibrational frequencies ω_L and ω_T were evaluated. The ferroelectric phase-transition temperature was estimated as 330 K for SbSCl_0.1I_0.9 from experimental reflection measurements and theoretical investigation of the potential energy of Sb atoms for B_1u soft normal modes of SbSI and SbSCl_0.1I_0.9 crystals.     

Exciton and phonon spectra of acoustooptic Tl3AsS3 crystals

The λ-modulated exciton reflection spectra of Tl₃AsS₃ crystals are investigated at 8 and 77 K, in which the ground (n=1) and excited (n=2, 3) exciton states are revealed. Taking into account the spatial dispersion, the shapes of λ-modulated reflection spectra of the n=1 line are calculated and the basic parameters of excitons and bands are determined (the translational and reduced masses of excitons and the effective masses of electrons and light and heavy holes). The one-phonon reflection spectra are studied in the region from 50 to 500 cm^?1 in polarizations E ∥ c and E ⊥ c. The shapes of one-phonon reflection spectra are calculated and the parameters of vibrational modes E and A ₂ are determined.     

First principles study of electronic structure and optical properties of LiMTe2 (M=Al, Ga, In) crystals

The results of first principles calculations of the electronic band structure, density of states and frequency dependent dielectric functions of LiAlTe₂, LiGaTe₂ and LiInTe₂ chalcopyrite crystals are reported. The calculations have been carried out within the density functional theory using norm-conserving pseudopotentials and a plane-wave basis. The peculiarities of the imaginary part ε₂(ω) of the complex permittivity are discussed and interpreted on the basis of the obtained band spectra. Our calculations show that the Ga-containing compound is characterized by the largest optical anisotropy compared to Al- and In-containing compounds and, therefore, is the most promising candidate for nonlinear optical applications among considered crystals.     

Structural, elastic constants, hardness, and optical properties of pyrite-type dinitrides (CN2, SiN2, GeN2)

The crystal structures, band structures, elastic constants, hardness, and optical properties of pyrite-type dinitrides (CN₂, SiN₂, and GeN₂) are obtained from the density functional theory using the plane-wave pseudopotential (PWP) method within the local density and generalized gradient approximations. The formation enthalpies for AN₂ (A=C, Si, and Ge) compounds suggest the three structures that are stable. The calculated band structures show the indirect gaps (Γ−R) in CN₂, SiN₂, and GeN₂. The intrinsic hardnesses of AN₂ (A=C, Si, and Ge ) compounds are calculated. Our results show that the cubic CN₂ and SiN₂ are superhard materials. Furthermore, we studied the optical properties such as the complex dielectric function and the electron energy loss spectra.     

Optical constants of Cu(In0.7Ga0.3)5Se8 and Cu(In0.4Ga0.6)5Se8 crystals

Variable angle spectroscopic ellipsometry has been applied to characterize the optical constants of bulk Cu(In_0.7Ga_0.3)₅Se₈ and Cu(In_0.4Ga_0.6)₅Se₈ crystals grown by the Bridgman method. The spectra were measured at room temperature over the energy range 0.8-4.4 eV. Adachi’s model was used to calculate the dielectric functions as well as the spectral dependence of complex refractive index, absorption coefficient, and normal-incidence reflectivity. The calculated data are in good agreement with the experimental ones over the entire range of photon energies. The parameters such as strength, threshold energy, and broadening, corresponding to the E₀, E_1A, and E_1B interband transitions, have been determined using the simulated annealing algorithm.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

First-principles calculations of structural, electronic, optical and elastic properties of magnesite MgCO3 and calcite CaCO3

Detailed ab initio calculations of the structural, electronic, optical and elastic properties of two crystals - magnesite (MgCO₃) and calcite (CaCO₃) - are reported in the present paper. Both compounds are important natural minerals, playing an important role in the carbon dioxide cycling. The optimized crystal structures, band gaps, density of states diagrams, elastic constants, optical absorption spectra and refractive indexes dependence on the wavelength all have been calculated and compared, when available, with literature data. Both crystals are indirect band compounds, with calculated band gaps of 5.08 eV for MgCO₃ and 5.023 eV for CaCO₃. Both values are underestimated by approximately 1.0 eV with respect to the experimental data. Although both crystals have the same structure, substitution of Mg by Ca ions leads to certain differences, which manifest themselves in noticeable change in the electronic bands profiles and widths, shape of the calculated absorption spectra, and values of the elastic constants. Response of both crystals to the applied hydrostatic pressure was analyzed in the pressure range of phase stability, variations of the lattice parameters and characteristic interionic distances were considered. The obtained dependencies of lattice constants and calculated band gap on pressure can be used for prediction of properties of these two hosts at elevated pressures that occur in the Earth's mantle.     

The study of below and above band-edge imperfection states in In2S3 solar energy materials

β-In₂S₃ is a nontoxic buffer layer material usually used in a thin-film solar cell due to a lot of vacancies and surface states naturally existing in the crystal to assist in photoelectric conversion. Transition metal (TM)-incorporated β-In₂S₃ has also been proposed to increase conversion efficiency in In₂S₃ since multi-photons absorption by intermediate band (IB) would happen in the sulfide. In this paper, single crystals of undoped and Nb-doped β-In₂S₃ have been grown by the chemical vapor transport (CVT) method using ICl₃ as a transport agent. Optical properties of the imperfection states of the crystals are probed by thermoreflectance (TR), photoconductivity (PC), photoluminescence (PL), surface photoconductive response (SPR), optical absorption and photo–voltage–current (photo V–I) measurements. The TR and optical-absorption measurements confirmed that the undoped and Nb-doped β-In₂S₃ are direct semiconductors with energy gap of 1.935 eV for undoped β-In₂S₃, 1.923 eV for β-In₂S₃:Nb_0.005, and 1.901 eV for β-In₂S₃:Nb_0.01. For undoped β-In₂S₃, PC and PL measurements are used to characterize defect transitions below band gap. The above band-edge transitions of undoped β-In₂S₃ have also been evaluated using PL, PC, and SPR measurements. For the evaluation of Nb-doped β-In₂S₃, an intermediate band with energy of ∼0.4 eV below the conduction band edge has been detected in the TR measurements in both β-In₂S₃:Nb_0.005 and β-In₂S₃:Nb_0.01. The photo V–I measurements also verified that the photoelectric-conversion efficiency would be enhanced in the β-In₂S₃ with higher niobium content. Based on the experimental analyses, the optical behavior of the defects, surface states, and IB (formed by Nb) in the In₂S₃ crystals is thus explored.     

Fine structure in the absorption edge spectrum of NbS2Y2 (Y = Cl,Br, I)

High resolution absorption spectra of single crystals of NbS₂Y₂ (Y = Cl, Br, I), obtained at temperatures between 4.2 and 300 K revealed extensive fine structure in the absorption edge. This structure has been analysed and interpreted in terms of allowed indirect interband transitions, involving phonons corresponding to SS and NbS vibrations, followed by forbidden and by allowed direct transitions. From the shape of the absorption curve associated with the phonon branches of the indirect transitions a binding energy of 23 cm^? for indirect excitons is obtained. A binding energy of 28 cm^? for direct excitons is deduced from the exciton lines observed at the long-wavelength side of the direct transitions. A detailed interpretation of the optical transitions is given in terms of a molecular orbital diagram for the Nb₂S₄ clusters, present in these crystals.     

The aΔg→XΣg magnetic dipole transition of S2

Emission spectra of the 0-0 band of the a¹Δ_g→X³Σ⁻_g magnetic dipole transition of S₂ have been observed in the near-infrared spectral region near 4400 cm⁻¹. The S₂ molecules were generated in a fast-flow system by passing S_x or S₂Cl₂ vapor in Ar carrier gas through a microwave discharge and were excited by electronic-to-electronic energy transfer from metastable singlet oxygen O₂(a¹Δ_g). Medium-resolution spectra of the b¹Σ⁺_g→X³Σ⁻_g and a¹Δ_g→X³Σ⁻_g transitions of S₂ were measured with a Fourier-transform spectrometer. By comparing the bandshape of the 0-0 band of the a→X system with a computer simulation calculated with literature data of the rotational constants of the X and a states, the origin of the 0-0 band was determined to be ν₀=4394.25±0.2 cm⁻¹.     

Infrared reflection and optical absorption studies on SmAsO4

Polarized infrared reflection spectra from flux-grown SmAsO₄ crystals were obtained in the frequency region 100–1200 cm^-1. The observed bands were assigned and compared with those of Raman and infrared spectra. The static dielectric constants, 9.03 and 9.10, for A_2u and E_u, respectively were determined using the Lyddane-Sachs-Teller (LST) relation. Optical absorption measurements suggest that a suitably high dosage of X-ray irradiation increases the background absorption, indicating an increase in the energy band gap in the lower wavelength region.     

Optical characterization of CuIn5S8 crystals by ellipsometry measurements

Optical properties of CuIn₅S₈ crystals grown by Bridgman method were investigated by ellipsometry measurements. Spectral dependence of optical parameters; real and imaginary parts of the pseudodielectric function, pseudorefractive index, pseudoextinction coefficient, reflectivity and absorption coefficients were obtained from the analysis of ellipsometry experiments performed in the 1.2–6.2 eV spectral region. Analysis of spectral dependence of the absorption coefficient revealed the existence of direct band gap transitions with energy 1.53 eV. Wemple–DiDomenico and Spitzer–Fan models were used to find the oscillator energy, dispersion energy, zero-frequency refractive index and high-frequency dielectric constant values. Structural properties of the CuIn₅S₈ crystals were investigated using X-ray diffraction and energy dispersive spectroscopy analysis.