Light and heat induced interdiffusion in Sb/As2S3 nano-multilayered film

The light and heat induced changes in the optical band gap of Sb/As₂S₃ nanomultilayered chalcogenide film has been studied. Even though the changes in optical bandgap are attributed to the light and heat induced interdiffusion, the diffusional intermixing between the layers is rather different with light and heat. The observed difference in the light and heat induced interdiffusion is due to unequal diffusion coefficients of light and heat predicted by thermal spike model.     

Stimulated interdiffusion and optical recording in Sb/As2S3 nanomultilayers

The role of the compositional modulation at nano-scale dimensions (2–10 nm) in the enhancement of optical recording parameters in nanomultilayers, which contain Sb as active, optical absorbing and diffusing layers and As₂S₃ as barrier (matrix) layers was investigated. Comparison was made with single homogeneous layers made of ternary (As₂S3)_xSb_1−x glasses and co-deposited from Sb and As₂S₃. It was shown that essential increase of the recording efficiency, sensitivity of the bleaching process, broadening of its spectral range occurs due to the stimulated interdiffusion of adjacent components in Sb/As₂S₃ nanomultilayers with optimized Sb layer thickness.     

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.     

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.     

Optical properties of thin films of system (As2Se3)80−x(As2Te3)x(SnTe)20 prepared by PLD

Thin amorphous films from system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ were prepared by pulsed laser deposition (PLD) from their bulk glasses and their optical properties were studied by spectral ellipsometry. Spectral dependencies of refractive index, absorption and extinction coefficient and optical gap (1.41–1.66 eV for (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 20 resp. x = 0) were calculated from optical tansmittance, from ellipsometric data by Tauc method. High values of refractive index n₀ (2.49–2.60) and of non-linear χ⁽³⁾ coefficient of index of refraction (4.9–7.5 × 10⁻¹² esu for the glass (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 0 resp. x = 20) made studied thin films of system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ promising candidates for application in optics and optoelectronics.     

Surface pattern recording in amorphous chalcogenide layers

Investigations of light-induced volume expansion and surface pattern recording in amorphous chalcogenide layers and nano-layered structures (NLS) were extended to direct electron-beam recording on Se/As₂S₃ and Sb/As₂S₃ NLS. Light as well as e-beam induced bleaching occurs in all NLS, while volume expansion occurs only in chalcogenide–chalcogenide NLS and in homogeneous Se or As₂S₃ layers. Comparison of these two phenomena revealed the possible role of purely electronic and thermal processes in the interdiffusion and relief formation. The latter is supposed to be connected with radiation-induced defect creation, free volume increase under the increased fluidity conditions as well as with the possible additional influence of electrostatic forces and stress.     

Two-photon absorption in binary Bi2O3–B2O3 glass at 532 nm

Measurements of two-photon absorption (TPA) coefficients β at 532 nm in binary Bi₂O₃:B₂O₃ glasses are reported. The β obtained ranges from 12.9 to 16.4 cm/GW with the larger value observed in higher Bi₂O₃ glass. The relationship between β and glass composition is discussed in terms of the electronic structure of glasses: β can be scaled with optical band gap.     

Bulk and impurity infrared absorption in 0.5 As2Se30.5 GeSe2 glass

A study of infrared absorption in the 250–4000 cm^?1 region has been carried out for 0.5 As₂Se₃0.5 GeSe₂ glasses quantitatively doped with oxide impurity. The frequencies of the intrinsic 2- and 3-phonon absorption bands at 490 and 690 cm^?1 correspond well to those predicted from combinations of the high frequency bands in the first order IR and Raman spectra of As₂Se₃ and GeSe₂ glasses.Glasses doped with As₂O₃ exhibit the same oxide impurity absorptionbands as those doped with GeO₂. Unlike As₂Se₃ glass, at impurity concentrations up to 1000 ppm As₂O₃, 0.5 As₂Se₃0.5 GeSe₂ glass exhibits only one major oxide impurity species, characterized by absorption bands at 780 and 1260 cm^?1 and due to oxygen bonded to network Ge. The observation of a much weaker network AsO vibration band at 670 cm^?1 confirms that oxygen bonds preferentially to Ge in this glass. The same minor oxide species appears to determine excess IR absorption at the CO₂ laser wavelength of 10.6 μm in both As₂Se₃ and 0.5 As₂Se₃ 0.5 GeSe₂ glasses. The frequencies and intensities of absorption bands due to hydrogen impurities are also quite comparable for these two materials.     

Intrinsic and impurity infrared absorption in As2Se3 glass

A quantitative study of infrared absorption in the 250–4000 cm^?1 region of As₂Se₃ glasses doped with small amounts of As₂O₃ or purified by various procedures has been carried out with particular attention to absorption in the wavelength regions of the CO₂ and CO lasers. The dependence of the relative intensities of the oxide impurity bands in the 650–1340 cm^?1 region on the total amount of As₂O₃ added to the glass indicates the existence of three distinct oxide-impurity species. A number of higher-frequency impurity bands which are due to the presence of hydrogen in the glass and whose intensities are highly dependent on the glass-melting conditions have been observed and classified. Intrinsic multiphonon absorption in the 400–1100 cm^?1 region has been interpreted in terms of combination and overtone bands of the two highest-frequency fundamental vibrational modes. Absorption coefficients of As₂Se₃ glass in the 920–1090 cm^?1 CO₂ laser region are limited by intrinsic multiphonon absorption to values of around 10^?2 cm^?1. The lowest absorption coefficients measured in the 1700–2000 cm^?1 CO laser region were around 2 × 10^?3 cm^?1 and may contain contributions from hydrogen-impurity bands.     

Photoluminescence and optical absorption in glassy AsxSe1−x

The photoluminescence and optical absorption spectra in glassy As_xSe_1−x with 0.08 ? x ? 0.40 are essentially independent of x. The PL spectra peak at approximately half the optical gap and the exponential slopes of the optical absorption edges are all approximately 75 meV. For x > 0.4, the PL peaks shift to higher energies, the widths of the PL spectra increase, and there is a strong component to the optical absorption well below the optical gap. Comparisons with ESR experiments in the As_xS_1−x system suggest the possibility of two PL peaks. The second PL peak and the optical absorption below the optical band gap for x > 0.4 are attributed to the presence of As-As bonds.     

Electrical and optical properties of Sn10Sb20−xBixSe70 (0 x 8) glassy films

Chalcogenide glasses are interesting materials due to their infrared transmitting properties and photo-induced effects exhibited by them. Thin films of the glasses Sn₁₀Sb_20−xBi_xSe₇₀ (0 x 8) prepared by melt quenching technique were evaporated in a vacuum better than 10⁻⁵ mbar. Optical transmission spectra of all the deposited films were obtained in a range 400–2500 nm. The optical band gap and the absorption coefficient were calculated from the transmission data and refractive index was calculated using the swanepoel method. The optical band gap initially increases with increase in Bi content (for x = 2) and then decreases sharply for higher Bi concentrations. The refractive index as well as absorption coefficient decrease with increase in wavelength. The dark activation energy initially increases with increase in Bi content and then decreases with further addition.     

The kinetics of photodissolution of Ag in amorphous As2S3 films

A new technique, measurement of the electrical resistance change of the Ag layer, is developed to study the kinetics of photodissolution of Ag in amorphous As₂S₃. It is shown that the photodissolution rate is proportional to the light intensity absorbed in the As₂S₃ at the As₂S₃Ag interface, but photoelectrons ejected from the Ag into the As₂S₃ also contribute. The process is shown to be two-stage. Firstly a critical “radiation damage” dose must be accumulated in the As₂S₃. Secondly, the Ag atom is photon-assisted across the As₂S₃Ag interface activation barrier.     

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.     

Durability of an As2S3 chalcogenide glass: Optical properties and dissolution kinetics

The durability of a As₂S₃ chalcogenide glass composition was studied in de-ionized water at different temperatures (60-90 °C) for different periods of time, up to 120 days. The evolutions of the chemical composition and the pH of the solutions as well as the optical transmission of bulk samples, in the 2-10 μm region, were measured as a function of corrosion time. Atomic force microscopy and optical microscopy were used to investigate the roughness of corroded surfaces and the evolution of surface defects. The water corrosion of As₂S₃ glass was found to follow a congruent dissolution mechanism, a possible glass-water reaction mechanism was proposed. The optical transmission of the glass was found to be affected by the corrosion. The optical loss increased from 4 to 21% with corrosion time, this variation was attributed to the texturation of the surface by the reaction of corrosion. Moreover, the experimental results show that high temperature value enhances the corrosion reaction: an activation energy of 103 ± 2 kJ/mol was computed from experimental measurements.     

Anomalous anisotropic deformations of As2S3 flakes induced by linearly-polarized bandgap illumination

Semi-free As₂S₃ flakes undergo visible-scale anisotropic deformations when exposed to linearly-polarized bandgap illumination. We investigate the behavior and also those in amorphous Se, GeS₂, AgAsS₂, and crystalline As₂S₃. These results suggest that the deformation occurs through photo-induced birefringence, photo-induced fluidity, and optical force.     

Preparation of mixed arsenic/antimony chalcogenide glasses and some optical and thermo-physical properties

The preparation of mixed glasses of As₂S_3−xSe_x (x = 0–3) and (1 − y) · As₂S₃y · Sb₂S₃ (y = 0–1) has been carried out by an in situ pouring technique. X-ray diffraction (XRD) was used to confirm the glassy nature of the materials and monitor devitrification. Visible-IR transmission, photoluminescence, refractive index and micro-Raman were measured as a function of composition. Microhardness (MH) and thermal expansion coefficient (TEC) were also measured. Raman peaks in As₂S₃ and As₂Se₃ were observed around 338 cm⁻¹ and 230 cm⁻¹, respectively in this first composition series in which S was replaced by Se. When As was replaced by Sb, in the case of second composition series, the As₂S₃ related Raman peak became broader and shifted to lower wave number, reflecting some structural change/devitrification. MH increased (1.31–1.50 GPa) with Se and Sb content while the TEC was found to decrease (2.5–1.4 × 10⁻⁵/K). The progressive increase in the content of either Se or Sb in As₂S₃ is anticipated to modify bond lengths and bond angles. The combined effect of these structural modifications would change the local structure of the glass forming a more rigid glass network thereby increasing the hardness and decreasing TEC.     

Compositional dependence of the optical properties of amorphous Sb2Se3−xSx thin films

Thin films of Sb₂Se_3−xS_x solid solutions (x = 0, 1, 2, and 3) were deposited by thermal evaporation of presynthesized materials on glass substrates held at room temperature. The films compositions were confirmed by using energy dispersive analysis of X-rays (EDAX). X-ray diffraction studies revealed that all the as-deposited films as well as those annealed at T_a < 423 K have amorphous phase. The optical constants (n, k) and the thickness (t) of the films were determined from optical transmittance data, in the spectral range 500-2500 nm, using the Swanepoel method. The dispersion parameters were determined from the analysis of the refractive index. An analysis of the optical absorption spectra revealed an Urbach’s tail in the low absorption region, while in the high absorption region an indirect band gap characterizes the films with different compositions. It was found that the optical band gap energy increases quadratically as the S content increases.     

Urbach absorption edge and disordering processes in As2S3 thin films

The temperature studies of transmission spectra for as-deposited and annealed amorphous As₂S₃ thin films are carried out. The optical absorption spectra in the range of their exponential behaviour are analysed, and the dispersion dependences of refractive index as well as their temperature variation are investigated. The Urbach behaviour of optical absorption edge is revealed, the Urbach absorption edge parameters are determined, and their temperature dependences are studied. The effect of different type of disordering on the optical absorption processes in As₂S₃ thin films is studied. A comparative analysis of Urbach absorption edge parameters of As₂S₃ bulk glasses and thin films is performed.     

A photoelectric study on the interface between metallic silver and vitreous As2S3

The electrostatic potential at the AgAs₂S₃ interface was investigated. In the dark, cells of a structure, Ag/As₂S₃/Al behaved like and an electrochemical battery. When light fell onto the cells, short-circuit currents were observed, but their appearancesvaried much, depending on the excitation wavelength and the material of the illuminated electrode. At wavelengths longer than the absorption edge of As₂S₃ glass, photocurrents were characteristic of the polarization current and little influenced by the external field. A model for explaining these findings was proposed on an assumption of an interface reaation between silver and vitreous As₂S₃ in the dark. The interfacial reaction was supposed to accompany a charge separation leading to formation of a potential barrier at the interface.     

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.