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.     

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.     

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.     

Vibrational properties of As2S3 glass

Vibrational densities of states and infrared and Raman spectra have been calculated for a structural model of As₂S₃ glass. The calculations are based on simple semi-empirical forms for interatomic potentials, electric dipole moment and Raman polarizability. The bands of the calculated spectra agree well with those of the observed infrared and Raman spectra of As₂S₃ glass in intensity and position, although a small concentration of the wrong SS bonds remains in the structural model and causes an additional peak in the higher frequency region. The calculated depolarization ratio of the Raman spectra is consistent with the observed one.     

Raman spectrum of vitreous As2S3

The spontaneous Stokes and anti-Stokes Raman spectrum of vitreous As₂S₃ is reported. The spectrum was recorded with both HeNe and Ar ion laser excitation lines in the transmission and reflection modes respectively. Spectra were recorded at various temperatures between 20°K and 465°K, the softening temperature of As₂S₃ glass. It is shown conclusively that the quasicontinous scattering observed at low wave number shifts (< 100 cm⁻¹) is real in agreement with the theory of Shuker and Gammon and not an arbitrary background as previously reported. An approximate density of vibrational states is deduced from the polarized Raman spectra.     

Plasma etching of As2S3 films for optical waveguides

Chalcogenide glasses are good candidate materials for ultra-fast non-linear optic devices. In this work, we present the photolithographic process and the plasma etching of arsenic tri-sulphide (As₂S₃) film. The films were deposited on thermally oxidized silicon substrates by ultra-fast pulsed laser deposition. To protect As₂S₃ film from photo-resist developer, thin resist layer ∼100-200 nm was remained on the UV exposed area by controlling resist development time. After removing the protective layer in oxygen plasma, As₂S₃ waveguides were patterned in inductively coupled plasma reactive ion etching (ICP-RIE) system using CF₄-O₂ gas mixture. We investigated the etch rate and the etch selectivity to photo-resist of As₂S₃ as a function of bias power, induction power, operating pressure, and gas flow rate ratio of CF₄ and O₂. The film is mainly etched by the chemical reaction with fluorine radicals. The content of oxygen in the plasma determines the etched sidewall profiles and nearly vertical profile was obtained at high oxygen content plasma.     

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.     

Ac conductivity of Ag-doped bulk,glassy As2S3

Measurements of the electrical conductivity of Ag-doped bulk As₂S₃ glasses have been made as functions of temperature, pressure, frequency and Ag doping level. A Debye-like loss peak was observed near 10⁴ Hz. The frequency of the loss peak is dependent on temperature, pressure and doping level, but these dependences are different from those of the dc conductivity. The ac loss is attributed to the Maxwell-Wagner losses characteristic of inhomogeneous materials. The materials are presumed to be inhomogeneous mixtures of As₂S₃ and Ag₂S. We have also searched unsuccessfully for ac conductance in several bulk chalcogenide glasses.     

Effect of hydrostatic pressure on the elastic moduli of As2S3 and As2Se3 glasses at 195 and 296 K

Velocities of 30 MHz longitudinal and shear ultrasonic waves have been measured in As₂S₃ and As₂Se₃ glasses as a function of hydrostatic pressure up to 1.5 kbar at 195 K and 3 kbar at 296 K. The elastic stiffness moduli are found to have relatively large, positive, pressure dependences which are about the same at both temperatures for both glasses. This behavior is attributed to the weakness of bonding between layers comprised of AsS₃ and AsS₃ pyramids.Inspection of data for a variety of glasses reveals a correlation between the value of C_L/3C_T and whether the elastic moduli are increased or decreased by pressure. (C_L is the longitudinal modulus and C_T the shear modulus.)Using the pressure dependences of the elastic moduli obtained in the present work, it is found that volume change is responsible for most of the temperature dependences of the moduli. In addition elastic gammas are obtained which are consistent with thermal Grüneisen gammas at 12 K. The pressure dependence of the volume of As₂S₃ glass at 296 K is calculated using the present results in the Murnagham equation. Agreement with volumetric data of Weir is obtained.     

Thermally stimulated depolarization of glassy As2S3

Decay of dark polarization in glassy As₂S₃ is investigated by thermostimulated depolarization (TSD). An attempt is made to analyse the observed maximum at about 360 K. To get more insight into the TSD phenomena, dc conductivity measurements at corresponding temperature are also presented. It is not possible at present to identify the trapped species responsible for the non-uniform polarization, despite finding that identical traps are active in both surface and bulk trapping.     

Structure and bonding in the mixed chalcogenide system As2SxSe3−x

⁷⁵As Nuclear Quadrupole Resonance (NQR) lineshape measurements for the amorphous mixed chalcogenide system As₂S_xSe_3?x are reported. The line-shapes are asymmetric and approximately 8 MHz in width (full width at half maximum). The peak resonance frequency is observed to increase approximately linearly with x. The NQR results indicate the presence of mixed As₂(S, Se)₃ pyramidal structural units and are thus not consistent with models that predict the occurrence of anion subsite segregation. NQR measurements performed on crystalline As₂SSe₂ lend support to the structural model proposed for the glasses.     

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.     

Structural study of (As2S3)0.6(GeS2)0.4 glass

(As₂S₃)_0.6(GeS₂)_0.4 glass in non-irradiated and γ-irradiated states has been studied by using high-energy synchrotron X-ray diffraction, extended X-ray absorption fine structure spectroscopy, and positron annihilation lifetime spectroscopy. The experimental results are explained by the local changes around As and Ge atoms upon irradiation. These changes are suggested to involve chemical bonds distortion, formation of defective bonds with wrong coordination, rotation of structural units and appearance of additional free volume in the glass network.     

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.     

Electron diffraction RDF analysis of amorphous As2Se3,AAs2Se2Te,As2SeTe2 and As2Te3 films

The local order in amorphous films of As₂Se₃, As₂Se₂Te, As₂SeTe₂, and As₂Te₃ has been examined by scanning electron diffraction with direct recording of the intensity of the elastically scattered electrons. The radial distribution functions indicate that there is a systematic increase in mean nearest neighbor distance as the Te concentration is increased, butthe mean coordination number increases slightly around 2.4. Pair function calculation of models shows that the 3-aand 2-fold coordinations of arsenic and chalcogens are retained in these glasses and the interatomic distances are close to those predicted from the Pauling covalent atomic radii of the constituent atomic species. The short range order appears to be similar in amorphous and crystalline As₂Se₃, but different in the case of As₂Te₃ as found by previous workers on bulk materials.     

Raman scattering of the mixed chalcogenide glass system As2SxSe3-x

Polarized room temperature Raman spectra of glassy As₂S_xSe_3-x for 0≦×≦3 have been measured. Spectra for crystalline As₂S₁Se₂ are reported. The polarization and intensity dependence upon composition are consistent with mixed pyramids of composition As₂S_nSe_3-n and preclude phase separation in the glassy system.     

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.     

Detailed study of the photodarkening process in amorphous As2S3

The photodarkening process in amorphous As₂S₃ was measured and analyzed in detail as a function of illumination time and incident photon flux. Three main results were obtained: (1) the degree of photodarkening approaches a saturation value with time in a simple exponential decay; (2) the saturation value increases with increasing incident photon flux; (3) independent of the incident photon flux, the number of photons required for the saturation is about 10²³/cm³.Detailed analyses based on a simple first-order rate equation show that a rate constant of the photodarkening increases superlinearly with respect to incident photon flux. This means that the reciprocity law between the illumination time and the incident photon flux does not hold in the photodarkening.Photo-modulation of excited electronic states is proposed here in order to interpret the nonlinear relationship between the rate constant and the incident photon flux.