On the Urbach rule in non-crystalline solids

A comparative analysis of temperature behavior of optical absorption edge is performed for non-crystalline materials where the Urbach behavior is observed (SiO₂), with deviations from the Urbach behavior (20PbO · 80SiO₂) and with a mixed behavior (As₂S₃). For glassy As₂S₃, the Urbach behavior of the absorption edge in a limited temperature range is explained from the point of view of two components of structural disordering - static and dynamic. A parallel red shift of the absorption edge in As₂S₃ and, consequently, the temperature-independent Urbach energy at T < 300 K, are related to the lack of medium-range order in the atomic arrangement in the presence of short-range order.     

Structural, electrical, and optical properties of As2S3-Cu6PS5I nanocomposites

As₂S₃-Cu₆PS₅I nanocomposites are prepared by incorporation of nanocrystals of Cu₆PS₅I superionic conductor in As₂S₃ glass matrix. Their structural studies by scanning electronic microscopy are performed and the electrical conductivity of the nanocomposites is investigated. The temperature dependence of the nanocomposite optical absorption edge is studied; a non-Urbach behaviour of the absorption edge is revealed. Influence of different types of disordering on the optical absorption edge is studied.     

Temperature Dependence of the Absorption Spectra and Optical Parameters in TGS and Cu2+-Doped TGS Crystals

The effect of temperature on the optical absorption spectra and optical parameters is investigated for pure TGS and TGS doped with Cu²⁺ ions. Absorption measurements cover the range from room temperature to about 355 K in the energy range 3-5.5 eV. The temperature dependence of the band gap E_g(T) reveals an anomaly at the phase transition temperature for both pure and Cu²⁺-doped TGS crystals. In the region of the absorption edge the absorption coefficient is found to display Urbach-rule behaviour. The characteristic Urbach parameters are determined and their temperature dependence is investigated.     

Urbach rule in photoelectron emission from surface states of low-sized silica

Spectral and temperature dependences of photoelectron emission from surface (interface) states of SiO₂ films and nanocompacts in the near UV region were studied. They were interpreted in terms of ‘frozen phonons’ conception and modified three-stage electron emission model. The electron emission analog of optical Urbach rule for low-sized silica was proposed. Optical absorption stage was recognized as the dominant phase of electron emission process. The structure and energy parameters of studied samples were obtained. It was revealed that thin and thick SiO₂ films have similar structure parameters while their effective potential barriers differ because of different electron transport conditions. High value of static structural disorder in compacted SiO₂ nanopowders is attributed to peculiarities of their ultradispersed structure.     

Influence of temperature on the microcrystalline structure of thermally evaporated Sb2S3 thin films

Thin films of antimony trisulfide (Sb₂S₃) were prepared by thermal evaporation under vacuum (p=5×10^–5 torr) on glass substrates maintained at various temperatures between 293 K and 523 K. Their microstructural properties have obtained by transmission electron microscopy (TEM). The electron diffraction analysis showed the occurrence of amorphous to polycrystalline transition in the films deposited at higher temperature of substrates (523 K). The polycrystalline thin films were found to have an orthorhombic structure. The interplanar distances and unit‐cell parameters were determined by high‐resolution transmission electron microscopy (HRTEM) and compared with the standard values for Sb₂S₃. The surface morphology of Sb₂S₃ thin films was investigated by scanning electron microscopy (SEM). The optical transmission spectra at normal incidence of Sb₂S₃ thin films have been measured in the spectral range of 400–1400 nm. The analysis of the absorption spectra revealed indirect energy gaps, characterizing of amorphous films, while the polycrystalline films exhibited direct energy gap. From the photon energy dependence of absorption coefficient, the optical band gap energy, E_g, were calculated for each thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of reversible photostructural change on the polarization of photoluminescence in chalcogenide glasses

Optical absorption edge in annealed As₂S₃ films shifts to lower energy after band-gap illumination. In these photodarkened films, polarization memory of photoluminescence was found to increase. In the case of illumination with linearly polarized light, anisotropy is induced in the absorption edge. The polarization memory was larger for larger shift of absorption edge. In contrast with this trend, the memory was smaller in As-rich films, the absorption edge of which was located at lower energy. It is considered that the optical anisotropy of the luminescence centers increases accompanying the reversible photostructural change.     

Distribution of electronic states in amorphous Cd-As thin films on the basis of optical measurements

Transmission and fundamental reflectivity studies, completed on amorphous Cd-As thin films, allowed us to obtain parameters describing the fundamental absorption edge, i.e. the optical pseudogap E_G^opt, Urbach energy E_U and exponential edge parameter E_T. All these data, together with the results of earlier transport measurements, have been utilized in developing simple models of electronic structure (distribution of electronic states) for amorphous Cd-As thin films of various compositions.     

Medium range order and optical properties of As2S3 glass

Low frequency Raman scattering and optical absorption edge were measured for As₂S₃ glasses quenched at temperature in the supercooling region of the glasses. It was found that both the Raman spectrum and the optical absorption edge shift to the lower energy side with the rise of the quenching temperature. The effects were interpreted in terms of the order of the arrangements of the layer-like clusters, which become more random as the quenching temperature goes higher.     

Photo and thermal induced effects on (As2S3)0.85Sb0.15 amorphous thin films

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As₂S₃)_0.85Sb_0.15 thin films were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier Transform Infrared spectrometry, X-ray Photoelectron Spectroscopy and Raman Spectroscopy. Photodarkening or photobleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities. The photodarkening in the as-prepared film was seen at low temperature (4.2 K).     

Optical investigations on the existence of phase transition in ZnO:Li thin films prepared by DC sputtering method

We investigated the effect of temperature on the absorption spectra of Zn_0.8Li_0.2O thin films (ZnO:Li), deposited at 573 K, in the wavelength range 190‐800 nm. The films were deposited on sapphire, MgO or quartz substrates by DC sputtering method. The results show a shift of the optical energy gap (E_g), with direct allowed transition type near the fundamental edge, to lower wavelengths as the temperature increases. The temperature rate of E_g changes considerably showing an anomaly around 320 K depending on type of substrate. The founded results indicated that replacement of Zn ions with Li ions induces a ferroelectric phase in the ZnO wurtzite‐type semiconductor. The exponential dependence of the absorption coefficient on the incident photon energy suggests the validity of the Urbach rule. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray photoelectron spectroscopic studies on Se/As2S3 and Sb/As2S3 nanomultilayered film

Photoinduced diffusion in Se/As₂S₃ and Sb/As₂S₃ nanomultilayered thin films are studied by X-ray photoelectron spectroscopy (XPS). The XPS measurements show the atomic movements during photoinduced diffusion in Se/As₂S₃ and Sb/As₂S₃ nanomultilayered film. The analysis of experimental data describes the nature of light induced changes in different structural units.     

Glass formation, physico-chemical properties, and structure of glasses based on Ga2S3-GeS2-Sb2S3 system

We prepared sulfide glasses based on a Ga₂S₃-GeS₂-Sb₂S₃ system and investigated the compositional dependences of their physico-chemical properties and structure. Additivities were observed for density and refractive index; i.e., these properties were presented by the summation of the contribution from each component. With the increase of Sb₂S₃ content, the density, refractive index, and thermal expansion coefficient increased while the glass transition and softening temperatures decreased, and the short-wavelength absorption edge shifted to the longer wavelength side. These variations are expected from the incorporation of a heavy element (Sb) into the glasses. On the other hand, the replacement of GeS₂ by Ga₂S₃ increased the density and refractive index, and shifted the short-wavelength absorption edge to the longer wavelength side. These variations were explained by the increase of the number densities of the cations with the replacement and the formation of metal-metal bonds. The latter was confirmed from the Raman spectra. We also investigated the effects of Ag₂S incorporation on the optical properties. The incorporation of Ag₂S increased the density and refractive index whereas the position of the short-wavelength absorption edge varied little. These results show the possibility of fabricating an optical waveguide by Ag incorporation into the glasses.     

Structure of pulsed-laser deposited arsenic-rich As–S amorphous thin films,and effect of light and temperature

Thin amorphous films from As–S system (∼As₅₀S₅₀) were prepared by the pulsed laser deposition technique. Light- and thermally-induced changes of structure of studied films have been investigated using Raman scattering spectroscopy results and interpreted in terms of chemical reactions and/or phase transitions between individual structural units. The irradiation of as-deposited thin films causes light-induced reactions, in which As₄S₃, α- and β-As₄S₄, and pararealgar/χ-As₄S₄ molecules are formed. Thermal-annealing of exposed thin films leads to the formation of β-As₄S₄ molecules.     

Optical studies of aromatic polyazomethine thin films

Optical transmission and fundamental reflectivity spectra of aromatic polyazomethine thin films, obtained by vacuum evaporation via the polycondensation process have been investigated in the wide spectral range 0.49–6.2 eV. As initial monomers, terephaldehyde (TPA) and one of four different amines, i.e. paraphenylene-diamine (PPDA), 7,2-diamino-fluorene, 1,1′-biphenyl-3,3′,4,4′-tetramine and 3-amino-4-(1-naphthyldiazenyl)phenylamine (fat brown RR) have been used, respectively. Amorphous character of these films was confirmed by the results of X-ray diffraction and AFM investigations. Absorption coefficient of the films has been obtained and the edge of absorption seems to be similar to the absorption edge typical for amorphous semiconductors, what allowed to obtain the Urbach energy and E_T parameter. The energy gaps of the films, following the Tauc relation, are found to change from 2.05 to 2.4 eV, depending on the length of conjugated part of the polymer chain. Absorption bands above the absorption edge, observed for different polyazomethine films are connected with their chemical structure and possible electronic transitions.     

Bimolecular relaxation kinetics observed in radiation-optical properties of Ge–As(Sb)–S glasses

Numerical parameters of decaying bimolecular relaxation kinetics are analysed for radiation-optical properties of chalcogenide glasses within ternary stoichiometric As₂S₃–GeS₂ and Sb₂S₃–GeS₂ as well as non-stoichiometric As₂S₃–Ge₂S₃ systems in dependence on their composition. It is shown, that the observed compositional dependences of bimolecular relaxation parameters have a monotonic character in the glasses of both stoichiometric systems, while the anomalous extremum-like behavior is observed in the vicinity of average coordination number close to 2.7 in non-stoichiometric glasses.     

Influence of thermoannealing on crystallinity and optical properties of Sb2S3 thin films

Sb₂S₃ thin films are obtained by evaporating of Sb₂S₃ powder onto glass substrates maintained at room temperature under pressure of 2×10^‐5 torr. The composition of the thin films was determined by energy dispersive analysis of X‐ray (EDAX). The effect of thermal annealing in vacuum on the structural properties was studied using X‐ray diffraction (XRD) technique and scanning electron microscopy (SEM). The as‐deposition films were amorphous, while the annealed films have an orthorhombic polycrystalline structure. The optical constants of as‐deposited and annealed Sb₂S₃ thin films were obtained from the analysis of the experimental recorded transmission spectral data over the wavelength range 400‐1400 nm. The transmittance analysis allowed the determination of refractive index as function of wavelength. It was found that the refractive dispersion data obeyed the single oscillator model, from which the dispersion parameters (oscillator energy, E₀, dispersion energy, E_d) were determined. The static refractive index n(0), static dielectric constant, ε_∞, and optical band gap energy, E_g, were also calculated using the values of dispersion parameters. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical Properties of Bi2Se3‐xAsx Single Crystals

Bi₂Se_3‐xAs_x single crystals with the As content of c_As = 0 to 2.0x10¹⁹ atoms/cm³ prepared from the elements of 5N purity by means of a modified Bridgman method were characterized by measurements of infrared reflectance and transmittance. Values of the plasma resonance frequency omega_p, optical relaxation time tau, and high‐frequency permittivity were determined by fitting the Drude‐Zener formulas to the reflectance spectra. It was found that the substitution of As atoms for Se atoms in the Bi₂Se₃ crystal lattice leads to a decrease in the omega_p values. This effect is accounted for by a model of point defects in the crystal lattice of Bi₂Se_3‐xAs_x. The dependences of the absorption coefficient K on the energy of incident photons were determined from the transmittance spectra. The optical width of the energy gap is found to decrease with increasing As content. The values of the exponent b from the relation of K ∼ lamda^b for the long‐wavelength absorption edge range within the interval 2.0 to 2.3, i.e. the dominant scattering mechanism of free current carriers in Bi₂Se_3‐xAs_x crystals is the scattering by acoustic phonons.     

Spectrometric and ellipsometric studies of (1 − x)TiO2 · xLn2O3 (Ln = Nd, Sm, Gd, Er, Yb) thin films

Spectrometric and ellipsometric studies of (1 − x)TiO₂ · xLn₂O₃ (Ln = Nd, Sm, Gd, Er, Yb; x = 0.33, 0.5) thin films at room temperature were performed. The obtained dispersion dependences of refractive indices are successfully described by the optical-refractometric relation. The dependence of optical pseudogap and refractive indices on composition and molar mass of the films is investigated. The influence of compositional disordering on the energy width of the exponential absorption edge is studied.     

Preparation and optical properties of AgGaS2 nanofilms

In this paper, AgGaS₂ nanofilms have been prepared by a two‐step process involving the successive ionic layer absorption and reaction (SILAR) and annealing method. Using AgNO₃, GaCl₃ and Na₂S₂O₃ as reaction sources, the mixture films were firstly deposited on quartz glass substrates at room temperature, and then annealed in Ar environment at 200–500 °C for 4 h, respectively. The effects of annealing temperature on structural and optical properties were investigated by XRD, UV‐Vis, EDS and photoluminescence (PL) spectra. It was revealed in XRD results that α‐Ag₉GaS₆ was contained in the samples annealed at 200 °C, and this phase was decreased with increase of the annealing temperatures. When the sample was annealed at above 400 °C, the chalcopyrite AgGaS₂ nanofilm was obtained. The preferred orientation was exhibited along the (112) plane. It was shown in atomic force microscopy (AFM) results that the grain sizes in AgGaS₂ nanofilms were 18‐24 nm and the thin films were smooth and strongly adherent to the substrates. When the annealing temperature was higher than 400 °C, it is an optimum condition to improve the structural and optical properties of the AgGaS₂ thin films. The room temperature PL spectra of AgGaS₂ nanofilms showed prominent band edge emission at 2.72 eV. Based on all results mentioned above, it can be concluded that the SILAR‐annealing method is preferable to preparing high‐quality AgGaS₂ nanofilms. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)