Optical absorption edge of As<Subscript>40–<Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>60</Subscript> glassy alloys

The fundamental absorption edge of glassy alloys of an As–Sb–S system was studied in the temperature range 77–300 K. The spectral and thermal behavior of the fundamental absorption edge of As_40–x Sb_xS₆₀ glasses was shown to be described by an exponential function of phonon energy. The temperature and concentration behavior of the optical band gap in the studied glasses was established. The well-known Varshni relationship was used to describe the temperature dependence of the optical band gap.     

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.     

Ellipsometric characterization of PbI2 thin film on glass

The optical properties of polycrystalline lead iodide thin film grown on Corning glass substrate have been investigated by spectroscopic ellipsometry. A structural model is proposed to account for the optical constants of the film and its thickness. The optical properties of the PbI₂ layer were modeled using a modified Cauchy dispersion formula. The optical band gap E_g has been calculated based on the absorption coefficient (α) data above the band edge and from the incident photon energy at the maximum index of refraction. The band gap was also measured directly from the plot of the first derivative of the experimental transmission data with respect to the light wavelength around the transition band edge. The band gap was found to be in the range of 2.385±0.010 eV which agrees with the reported experimental values. Urbach's energy tail was observed in the absorption trend below the band edge and was found to be related to Urbach's energy of 0.08 eV.     

Effect of Bi2O3 content on physical and optical properties of 15Li2O-15K2O-xBi2O3-(65−x) B2O3: 5V2O5 glass system

Multi-component bismuth borate glasses doped with vanadium ions 15Li₂O-15K₂O-xBi₂O₃-(65−x) B₂O₃: 5V₂O_5, (x=3, 5, 7, 10, 12 and 15) have been prepared using conventional melt quench technique. Characterization of the prepared glasses has been done using X-ray diffraction, differential scanning calorimetry and density measurements. The effect of Bi₂O₃ content on the optical properties of the present glass system is studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The origin of the Urbach energy is associated with the phonon-assisted indirect transitions. The density and molar volume studies indicate that Bi₂O₃ in these glasses is acting partly as network modifier and partly as network former. The variations in the optical band gap energies, density and molar volume with Bi₂O₃ content have been discussed in terms of changes in the glass structure. Values of the theoretical optical basicity, average crosslink density and the average electronic polarizability are also reported.     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Disorder driven optical processes in nanocrystalline ZnO

A systematic study on the modification of optical properties in mechanically milled ZnO powder has been reported here. The average grain size of the powder becomes ～20 nm within 4 h of milling. Fluctuations of average grain size have been noticed at the initial stage of milling (within 15 min). Changes in grain morphology with milling have also been noticed in scanning electron micrographs of the samples. Room temperature optical absorption data shows a systematic red shift of absorption band edge (～3.25 eV). The band tail parameter (extracted from the optical absorption just below the band edge) follows a simple exponential relation with the inverse of the average grain size. Significant increase of the band tail parameter has been noticed at low grain size regime. It has been analyzed that high values of band tail parameter is a representative of V_Zn–V_O type divacancy clusters. Room temperature photoluminescence spectra show decrease (except for 120 min milling) of band edge emission intensity with increase of milling time. Subsequent decrease of sub-band edge emission is, however, less prominent. The variation of PL intensity ratio (intensity at band edge peak with that at 2.3 eV) follows simple exponential decrease with the increase of band tail parameter. This indeed shows that band edge emission in ZnO is related with the overall disorder in the system, not grain size induced only.     

Origin of visible-light-induced photocatalytic properties of S-doped anatase TiO2 by first-principles investigation

Electronic structures and optical absorption spectra of S-doped anatase TiO₂ are calculated by means of the first-principles pseudopotential total energy method. Electronic structure analyses demonstrate that isolated S 3p states which appear on the upper edge of the valence band cause the narrowing of the band gap of S-doped TiO₂. These changes of electronic structure exert great influence on the optical responses of S-doped TiO₂. Our results are in line with recent experimental observations that the redshift of optical absorption could be attributed to these isolated S 3p states on the upper edge of the valence band of S-doped TiO₂.     

Optical properties of Tl2In2Se3S layered single crystals

The optical properties of Tl₂In₂Se₃S layered single crystals have been analyzed using transmission and reflection measurements in the wavelength region between 500 and 1100 nm. The optical indirect transitions with a band gap energy of 1.96 eV and direct transitions with a band gap energy of 2.16 eV were determined from analysis of absorption data at room temperature. Dispersion of the refractive index is discussed in terms of the Wemple–DiDomenico single-effective-oscillator model. The refractive index dispersion parameters – oscillator energy, dispersion energy, oscillator strength and zero-frequency refractive index – were found to be 4.67 eV, 45.35 eV, 1.38 × 10¹⁴ m ^{? 2} and 3.27, respectively. Transmission measurements were also performed in the temperature range 10–300 K. As a result of temperature-dependent transmission measurements, the rate of change in the indirect band gap with temperature, i.e. γ = ?5.6 × 10^?4 eV/K, and the absolute zero value of the band gap energy, E _gi(0) = 2.09 eV, were obtained.     

Influence of composition on electrical and optical properties of new chalcogenide thin films from Ge-Se-Tl system

Bulk Ge₂₀Se_80−xTl_x (x ranging from 0 to 15 at%) chalcogenide glasses were prepared by conventional melt quenching technique. Thin films of these compositions were prepared by thermal evaporation, on glass and Si wafer substrates at a base pressure of 10⁻⁶ Torr. X-ray diffraction studies were performed to investigate the structure of the thin films. The absence of any sharp peaks in the X-ray diffractogram confirms that the films are amorphous in nature. The optical constants (absorption coefficient, optical band gap, extinction coefficient and refractive index) of Ge₂₀Se_80−xTl_x thin films are determined by absorption and reflectance measurements in a wavelength range of 400-900 nm. In order to determine the optical gap, the absorption spectra of films with different Tl contents were analyzed. The absorption data revealed the existence of allowed indirect transitions. The optical band gap showed a sharp decrease from 2.06 to 1.79 eV as the Tl content increased from 0% to 15%. It has been found that the values of absorption coefficient and refractive index increase while the extinction coefficient decreases with increase in Tl content in the Ge-Se system. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. DC electrical conductivity of Ge₂₀Se_80−xTl_x thin films was carried out in a temperature range 293-393 K. The electrical activation energy of these films was determined by investigating the temperature dependence of dc conductivity. A decrease in the electrical activation energy from 0.91 to 0.55 eV was observed as the Tl content was increased up to 15 at% in Ge₂₀Se_80−xTl_x system. On the basis of pre-exponential factor, it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges.     

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.     

Photoinduced absorption edge shift of As20Se60Tl20 films

As₂₀Se₆₀Tl₂₀ bulk material was prepared firstly then thermal evaporation method was used to prepare As₂₀Se₆₀Tl₂₀ films. Illumination effect at room temperature for the mentioned films has been studied within the homogeneous glass-forming region. The prepared film samples were amorphous, this is depicted by X-ray chart. Optical properties have been studied using spectrophotometric measurements. The absorption edge was shifted to shorter wavelengths due to light exposure or photobleaching effect. It was found that the extinction coefficient and the optical band gap have opposite character after illumination.     

Optical band gap studies and estimation of two photon absorption coefficient in alkali bismuth borate glasses

The optical absorption spectra of the glasses with composition xBi₂O₃·(30???x)R₂O·70B₂O₃ (R?Li, Na, K) and xBi₂O₃·(70???x)B₂O₃·30Li₂O (0?≤?x?≤?20) have been recorded in the wavelength range 350–650?nm. The glass samples were prepared by the normal melt–quench technique. The fundamental absorption edge for all the series of glasses is analyzed using the theory of Davis and Mott. The position of absorption edges and the values of optical band gap are dependent on the mol% of Bi₂O₃. The absorption in these glasses is associated with indirect transitions. The values of Urbach's energy and band tailing parameters are reported. The two photon absorption coefficient, β, in these glasses has also been estimated from the optical band gap and its value ranges from 1.3 to 11.6?cm/GW. The relationship between β and glass composition has also been discussed in terms of the electronic structure of the glass system.     

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.     

Photoacoustic saturation spectra of some semiconducting group IV-A transition metal dichalcogenides

Photoacoustic saturation spectra in some semiconductors as HfSe₂, ZrS₂ and HfS₂ have been measured at energies above the fundamental absorption edge, where the photoacoustic signal is independent of the optical coefficient and the dips detected in the photoacoustic spectra may be ascribed to optical reflection effects inherent to the band structure. The comparison between our experimental data and those obtained by means of conventional and modulatory spectroscopic techniques proves that such method is a useful tool in order to determine the electronic structure of photoacoustically active semiconductors.     

Infrared radiation properties of methane at elevated temperatures

The spectral absorptivity of the v₃ and v₄ fundamental and the v₁ + v₄ combination bands of methane have been measured at low resolution for temperatures between 290 and 850 K. Spectral mean (narrow-band) parameters for the fundamental bands have been correlated from the Elsasser model, while total band absorptance data for all three bands have been correlated using the Edwards exponential wide band model. A total emissivity chart has been developed, based on the wide band absorption models.     

The shift of the optical absorption edge in an antiferromagnetic semiconductor

Thes-f model with spinS=7/2 has been used to study the temperature dependence of the optical absorption edge of an antiferromagnetic semiconductor. Two possible antiferromagnetic structures are considered: anAB two-sublattice model and an eight-subllattice model (MnO structure). For theAB two-sublattice model the density of states has been calculated as a function of temperature. A blue shift of the absorption edge of about 0.057 eV is obtained betweenT=T _N andT=0 K for this structure (using the parameters for EuTe). The dependence of the blue shift on the bandwidth and the band filling has been studied. For small values of the band filling the blue shift is practically unchanged.In the case of eight-sublattice structure the lowest single-particle energy (the bottom of the conduction band edge) has been observed as a function of temperature. Using the parameter set suitable for EuTe, it is concluded that the eight-sublattice structure does not show any shift of the optical absorption edge when the temperature is varied.     

Anomalies in the optical properties of nanocrystalline copper oxides CuO and Cu2O near the fundamental absorption edge

A 0.1–0.15-eV displacement of the fundamental absorption edge in the optical absorption spectra of nanocrystalline oxide n-CuO (relative to the position of the fundamental absorption edge in the spectra of CuO single crystals) towards lower energies (red shift) is observed against the background of strong blurring. Nanocrystalline n-Cu₂O exhibits a displacement of the fundamental absorption edge towards higher energies (blue shift) by approximately 0.35 eV. The size of crystallites in n-CuO and n-Cu₂O ranges from 10 to 90 nm. The blue shift of the fundamental absorption edge of n-Cu₂O is typical of classical wide-gap semiconductors and can be explained by size quantization upon a change in the particle size. The anomalous red shift of the fundamental absorption edge of the strongly correlated nanocrystalline oxide n-CuO can be attributed to the highly defective structure of n-CuO, anomalies in the electronic structure of strongly correlated compounds based on 3d metals, and their tendency to electronic phase separation with the formation of metal-like inclusions.     

Physical,optical and electrical properties of calcium bismuth borate glasses

The variation in physical, optical and electrical properties has been investigated as a function of Bi₂O₃ content in 20CaO?·?xBi₂O₃?·?(80???x)B₂O₃ (0?≤?x?≤?60, in mol%) glasses. The samples were prepared by normal melt-quenching process, and the optical absorption and reflection spectra were recorded in the wavelength range of 400–950 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The optical band gap, E _g, for indirect allowed and indirect forbidden transitions has been determined from the available theories and its value lies between 1.80–2.37 eV and 1.08–2.19 eV, respectively. The theoretical fitting of the optical absorption indicates that the present glass system behaves as an indirect gap semiconductor. The origin of the Urbach energy, ΔE, has been associated with the phonon-assisted indirect transitions. The refractive index and optical dielectric constant have been evaluated from the reflection spectra. The density and molar volume are found to depend on the molar concentration of Bi₂O₃. The values of DC electrical conductivity have been measured from 373 to 623 K and the activation energy has been calculated. Theoretical optical basicity has been reported as a function of the Bi₂O₃ content. The variations have been discussed in terms of structural changes.     

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.     

Tunability of electronic and optical properties of the Ba–Zr–S system via dimensional reduction

Transition metal sulfide perovskites offer lower band gaps and greater tunability than oxides, along with other desirable properties for applications. Here, we explore dimensional reduction as a tuning strategy using the Ruddlesden–Popper phases in the Ba–Zr–S system as a model. The three-dimensional perovskite BaZrS₃ is a direct gap semiconductor, with a band gap of 1.5 eV suitable for solar photovoltaic application. However, the three known members of the Ruddlesden–Popper series, are all indirect gap materials, and additionally have lower fundamental band gaps. This is accompanied in the case of Ba₂ZrS₄ by a band structure that is more favorable for carrier transport for oriented samples. The layered Ruddlesden–Popper compounds show significantly anisotropic optical properties, as may be expected. The optical spectra show tails at low energy, which may complicate experimental characterization of these materials.