Interrelation between glass transition and reversible photostructural change in a-As2S3

The optical absorption edge has been observed to make a parallel shift to lower energy in a-As₂S₃ as the glass transition temperature, T_g, increases. The structural difference corresponding to different T_g and reversible photostructural change give the same linear relation between the edge shift and the volume change. The saturated position of the edge after long time illumination or annealing is determined only by the condition of last treatment and is independent of previous history. These results suggest that both structural changes are of the same kind and that in the glass there exists an equilibrium state under illumination, if crystallization is avoided.     

The reversible photostructural change studied by ESR of Mn2+ in As2Se3 films

The reversible photostructural change is studied from a microscopic point of view using ESR of Mn²⁺ doped in As₂Se₃ films. It is observed that the hyperfine structure constant changes reversibly corresponding to the reversible optical absorption edge shift. The result is explained in terms of increasing randomness by photoirradiation.     

Reversible photo-induced volume changes in evaporated As2S3 and As4Se5Ge1 films

Reversible photo-induced volume changes have been observed accompanying reversible optical absorption edge shift produced by successive cycles of band gap illumination and annealing for well-annealed evaporated As₂S₃ and As₄Se₅Ge₁ films. The As₂S₃ film shows an increase in its volume by illumination, while As₄Se₅Ge₁ film shows a decrease. Qualitative discussion has been given in connection with pressure-induced optical constant change.     

Thermally and photo-induced changes in the valence states of vapour-deposited As2S3 films: A comparative photoemission study of As2S3 and As4S4

During thermal annealing or light irradiation, the changes in the valence states of vapour-deposited As₂S₃ and As₄S₄ films were observed by UPS. The experimental results reveal that an as-deposited As₂S₃ film contains considerable numbers of As₄S₄ molecular units, which polymerize or cross link to form a As₂S₃ glassy network on annealing or irradiation.     

ESR in X-irradiated As2O3 glass

X-irradiation of glassy As₂O₃ at 77K or 300K produces an unusually large density (～5×10¹⁸ cm^-3) of paramagnetic centers which are stable at 300K. The average spin-Hamiltonian parameters (g = 1.998, g_⊥ = 1.984, A₆ = 243G, A_⊥ = 114G) indicate that these centers are analogous to those previously observed in As₂Se₃ and As₂S₃ glasses and that they consist of unpaired electrons localized on a non-bonding 4p orbital of an As atom. Unlike the results obtained for As₂Se₃ and As₂S₃, the concommitant holes in As₂O₃ are trapped on Fe²⁺ impurity sites which become Fe³⁺ and not on non-bonding oxygen p orbitals. The radiation induced ESR is also accompanied by a stable optical absorption tail which lies within the band gap and increases exponentially with energy. This absorption can be partially bleached with the application of sub-band-gap light.     

Studies on electrodeposited As2S3 thin films by double exposure holographic interferometry technique

Arsenic trisulphide (As₂S₃) thin films have been deposited onto stainless steel and fluorine doped tin oxide (FTO) coated glass substrates by electrodeposition technique using arsenic trioxide (As₂O₃) and sodium thiosulphate (Na₂S₂O₃) as precursors and ethylene diamine tetracetic acid (EDTA) as a complexing agent. Double exposure holographic interferometry (DEHI) technique was used to determine the thickness and stress of As₂S₃ thin films. It was observed that the thickness of the thin film increases whereas film stress to the substrate decreases with an increase in the deposition time. X-ray diffraction and water contact angle measurements showed polycrystalline and hydrophilic surface respectively. The bandgap energy increases from 1.82 to 2.45 eV with decrease in the film thickness from 2.2148 to 0.9492 μm.     

Reversible photostructural change in melt-quenched GeS2 glass

Reversible photostructural change accompanying optical absorption edge shift has been observed in melt-quenched Ges₂ glass for the first time. Experimentally determined values of photo-expansion and photo-induced optical absorption edge shift are 0.47% and 0.075 eV, respectively. It has been demonstrated that the structural origin for the reversible photostructural change should not be attributed to wrong bonds inherently involved even in the stoichiometric glass compounds     

Photo-synthesis of As3S2 crystal from AsAs2S2 mixture

Existence of As₃S₂ compound which is stable in a certain temperature range higher than room temperature has been confirmed in AsAs₂S₂ system. Photo-synthesis effect of As₃S₂ crystal from As and As₂S₂ mixture, namely light induced conversion from a crystalline state to another crystalline state, has also been investigated.     

Infrared properties of AsχTe1−χ glasses

Infrared reflection and transmission measurements in As_χTe_1?χ glasses (45?×?55) show well-defined Gaussian vibrational absorption peaks. Comparisons with spectra observed in crystalline and glassy As₂S₃ and As₂Se₃ indicate that the local order in As_χTe_1?χ glasses is not like that found in crystalline As₂Te₃, but rather it consists primarily of AsTe₃ pyramids which are probably linked together in a fashion similar to that found in As₂S₃ and As₂Se₃.     

Glass formation in the As2Se3-As2Te3-Sb2Te3 system

Chalcogenide glasses from the As₂Se₃-As₂Te₃-Sb₂Te₃ system were synthesized for the first time. The glass-forming region was determined by X-ray diffraction and electron microscopic analyses.The basic physicochemical parameters such as density (d), microhardness (HV) and temperatures of phase transformations (glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network as well as the elasticity module (E) were calculated. The glass-forming ability was evaluated according to Hruby's criteria (K_G). The correlation between composition and properties of the (As₂Se₃)_x(As₂Te₃)_y(Sb₂Te₃)_z glasses was established and comprehensively discussed.     

Dispersion characteristic of hexagonal and square lattice chalcogenide As2Se3 glass photonic crystal fiber

In this paper, we report a chalcogenide As₂Se₃ glass photonic crystal fiber (PCF) for dispersion compensating application. We have used the improved fully vectorial effective index method (IFVEIM) for comparing the dispersion properties (negative and zero dispersion) and effective area in hexagonal and square lattice of As₂Se₃ glass PCF using different wavelength windows. It has been demonstrated that due to their negative dispersion parameter and negative dispersion slope in wavelength range 1.2-2.5 μm, both lattice structures of As₂Se₃ glass PCFs, with pitch (Λ = 2 μm), can be used as dispersion compensating fibers. Further, design parameters have been obtained to achieve zero dispersion in these fibers. It is also shown that As₂Se₃ glass PCF provides much higher negative dispersion compared to silica PCF of the same structure, in wavelength range 1.25-1.6 μm and hence such PCF have high potential to be used as a dispersion compensating fiber in optical communication systems.     

Femtosecond optical Kerr effect study of Ge10As40S30Se20 film

The results of the femtosecond optical heterodyne detection of optical Kerr effect at 805 nm with the 80 fs ultrafast pulses in amorphous Ge₁₀As₄₀S₃₀Se₂₀ film is reported in this paper. The film shows an optical non-linear response of 200 fs under ultrafast 80 fs-pulse excitation, and the values of real and imaginary parts of non-linear susceptibility χ⁽³⁾ were 9.0×10⁻¹² and −4.0×10⁻¹² esu, respectively. The large third-order non-linearity and ultrafast response are attributed to the ultrafast distortion of the electron orbits surrounding the average positions of the nucleus of Ge, As, S and Se atoms. This Ge₁₀As₄₀S₃₀Se₂₀ chalcogenide glass would be expected as a promising material for optical switching technique.     

Raman spectra and structure of As40−xS60Ix glasses

The Raman spectra of bulk As_40?xS₆₀I_x glasses with 0?x?20 have been studied. The obtained spectra can be successfully explained assuming the structure of these glasses to be composed of As₂S_3.45 polymer network matrix with dissolved AsBr₃ and S₈ molecules.     

Photo-induced changes in the infrared vibrational spectrum of evaporated As2S3

Photo-induced changes in the infrared spectrum of amorphous, evaporated As₂S₃ films are described. The results are interpreted in terms of the photopolymerization of As₄S₄ molecular units and sulfur chains into an As₂S₃ glassy network. The role of photo-induced charged states in the polymerization process is discussed.     

Crystallization kinetics in new Sb14As29Se52Te5 amorphous glass

Differential scanning calorimetry (DSC) under non-isothermal conditions is used to study the crystallization kinetics of Sb₁₄As₂₉Se₅₂Te₅ chalcogenide glass. In addition, two approaches are used to analyze the dependence of glass transition temperature (T_g) on the heating rate (α). One is empirical linear relationship between (T_g) and ln(α). The second approach is the use of straight line vs. 1/T_g for the evaluation of the activation energy for glass transition. The phases at which the alloy crystallizes after the thermal treatment have been identified by using X-ray diffraction. The diffractogram of the transformed material shows the presence of some crystallites of As, Te, AsSb, As₂Se₃, Sb₂Se₃ and AsSe_.5Te_.5 in the residual amorphous matrix.     

Photoelectron spectra of As4S3, P4S3, P4Se3 and As4O6

The He(I) UV photoelectron spectra of As₄S₃, P₄S₃, P₄Se₃ and As₄O₆ are reported in this paper. The spectra of As₄S₃ and the isostructural molecules P₄S₃ and P₄Se₃ comprise seven broad but clearly defined peaks, whilst the spectrum of As₄O₆ consists of six peaks and two shoulders. By comparing the spectra with one another and with the photoelectron spectra of other arsenic and phosphorus compounds, the character and symmetry species of the highest-energy occupied molecular orbitals of the molecules have been assigned.     

Observations of photovoltage in Ag photodoping of amorphous As2S3 films

Photovoltage has been measured during Ag photodoping process in amorphous As₂S₃ films. Concerning the driving force on Ag atoms in the process, a tentative energy band model near Ag-As₂S₃ interface has been proposed.     

Photo- and thermal-diffusions of metals into As2S3 glass

Photo- and thermal-diffusion effects of Ag and Cu into As₂S₃ bulk glass have been studied. It has been clarified that the photo-diffusion process is attributed to a purely optical effect. Some differences in diffusing process between Ag and Cu have been clearly shown both for the photo- and thermal-diffusions.     

Conductivity of the chalcogenide semi-insulator system: As2S3Sb2S3

The conductivities of mixed As₂S₃Sb₂S₃ thin films are discussed. Temperature independent a.c. data are interpreted in terms of a hopping mechanism where correlation effects are important. Excepting As₂S₃, which exhibits extrinsic behaviour, the dielectric constant, a.c. conductivity and d.c. conductivity pre-exponential factor, all scale approximately linearly with composition.     

Electronic structure of As4S5 as a local structural model for amorphous As2S3 film

We have studied the electronic structure of As₄S₅ molecule as a model of the local pyramidal structure in amorphous As₂S₃ film. Emphasis has been put on the analysis of the behaviour of a trapped electron in this model concerning the consequent structural relaxation. It has been found that As₄S₅ species has affinity for an excess electron, and that the attachment of an excess electron promotes the cleavages of specific As-S bonds.