Neutron thermodiffractometry study of silver chalcogenide glasses

Silver-containing chalcogenide glasses are of considerable interest for applications in optical and electrical recordings and as solid electrolytes. Therefore, insight in their structural properties is important. A neutron thermodiffraction study of Ag_x(Ge_0.25Se_0.75)_100−x glasses with x = 15 and 25 at.% was carried out. The amorphous samples were heated in situ from room temperature up to 350 °C, while the neutron diffraction spectra were collected every degree. For both glasses the Ag₈GeSe₆ phase appeared first, followed by the crystallization of GeSe₂. The crystallization process for the Ag-rich glass was more complex with the appearance of a non-identified third phase. Rietveld refinement helped us in studying the evolution of the lattice constants of each phase upon heating.     

Infrared conductivity of chalcogenide glasses

The general features of the conductivity spectra of chalcogenide glasses in the frequency range 10⁹ to 10¹³ Hz are briefly reviewed.     

Optical properties of chalcogenide glasses

Over the past two decades chalcogenide glasses have been researched in order to assess their suitability as passive bulk optical component materials for 3–5μm and 8–12μm infrared applications. This research has led to a greater understanding of the physical properties of these materials, and the present paper concentrates on the optical properties and applications of these bulk chalcogenide glasses. The various factors influencing the intrinsic and extrinsic optical loss mechanisms in materials are discussed, numerical data on the basic optical properties of chalcogenide glasses is presented and applications are discussed.     

Time-resolved photoluminescence in chalcogenide glasses

The time resolved spectroscopy of the photoluminescence with pulse-dye-laser excitation supplied the direct evidence of the strong electron-phonon interaction and the distributed localized states at band edges and the important information of mobility edge in chalcogenide glasses. The excitation energy dependence of the time resolved photoluminescence indicated that a-As₂S₃ and a-GeSe₂ at 4.2 K had the mobility gaps of 2.6 eV and 2.25 eV, respectively.     

Dielectric relaxation study of chalcogenide glasses

The paper reports dielectric measurements carried out for a variety of threshold and memory alloys of glassy AsGeTe and SeGeTe at different temperatures (83 to 373 K) and various frequencies (0.2, 0.5, 1.0, 2.6 and 5.0 MHz). It is found that the glassy system of chalcogenides exists in the form of molecular dipoles which remain frozen at low temperatures and, as the temperature is increased, the molecules attain freedom of rotation at temperatures which are sometimes as low as 253 K. All the materials displayed dielectric dispersion in the radio frequency range. Gevers' formula has been used to calculate the dielectric loss (?′') and loss-angle (tan δ) from the measured values of the real part of dielectric constant (?′). The curves: log ?′ versus temperature, ?′ versus log ω, ?″ versus log ω, tan δ versus log ω and tan δ versus temperature, gave a direct evidence of the existence of a Debye-type relaxation having a wide distribution of relaxation times.Cole-Cole diagrams have been used to determine the distribution parameter (α) and the molecular relaxation time (τ). The temperature dependence of α and τ for all the alloys is consistent with the “molecular relaxation mechanism”. The paper also reports accurate values of the static and optical dielectric constants for all the alloys.Eyring's relaxation rate equations have been used to determine the free energy of activation (ΔF), and enthalpy of activation (ΔH) for all the alloys. These results indicate the existence of a stronger intermolecular interaction for SeGeTe alloys. mott's concept of “dangling bonds” has also been used to explain the existence of a stronger intermolecular interaction, and hence a greater density of defect states in case of SeGeTe as compared with AsGeTe alloys.It has been finally concluded that the dielectric behaviour of chalcogenide glasses, in general, can be successfully explained by using the theory of molecular relaxation.     

The structure of some chalcogenide glasses

A study using replica electron microscopy, scanning electron microscopy, electron diffraction, X-ray diffraction, sputter etching and differential thermal analysis of the structural properties of glasses having a range of compositions within the AsTeGeSi quaternary system has shown that phase separation generally occurs in the bulk material. The second phase is dispersed as inclusions in the non-crystalline matrix and is apparently non-crystalline away from the boundary of the glass forming region but is crystalline near to the high Te boundary. The crystalline second phase is probably Te. This quaternary system, AsTeGeSi is often used as source material for the fabrication of devices studied for their monostable electrical switching behaviour and the phase separation observed in these materials needs to be considered in the interpretation of the switching properties and for failure analysis of such devices.     

High-speed transient currents in chalcogenide glasses

High-speed transient currents are often observed in chalcogenige glasses. We explain these effects by invoking the presence of Valence Alternation Pairs (VAPs). After an electric field is applied across the chalcogenide glass, carriers can tunnel directly from the electrodes onto the appropriately charged defect centers. This leads to the appearance of potential barriers near the contacts, resulting in a rapid decay of the current. Such a mechanism cannot occur in materials without a large concentration of negatively correlated defects.     

Non-linear properties of chalcogenide glasses and fibers

High purity chalcogenide glasses were prepared in the series As₂S_(3?x)Se_x where x = 0 to 3. The measured third order non-linearities increase with the value of x, and are up to about 1000 times larger than silica for As₂Se₃ glass. We show that the anharmonic oscillator model, using the normalized photon energy, gives an excellent fit to the data over three orders of magnitude. Single mode optical fibers based on As₂S₃ and As₂Se₃ glasses have been fabricated using the double crucible technique and the Stimulated Brillouin Scattering (SBS) investigated. The threshold intensity for the SBS process was measured and used to estimate the Brillouin gain coefficient. Preliminary results indicate record high values for the figure of merit and theoretical gain, compared to silica, which bodes well for slow-light based applications in chalcogenide fibers.     

Structure of chalcogenide glasses by neutron diffraction

The purpose of this work is to study the change in the structure of the Ge–Se network upon doping with Ag. We report here a neutron diffraction study on two glasses of the system Ag_x(Ge_0.25Se_0.75)_100−x with different silver contents (x = 15 and 25 at.%) and for two different temperatures (10 and 300 K). The total structure factor S(Q) for the two samples has been measured by neutron diffraction using the two-axis diffractometer dedicated to structural studies of amorphous materials, D4, at the Institut Laue Langevin. We have derived the corresponding radial distribution functions for each sample and each temperature, which gives us an insight about the composition and temperature dependence of the correlation distances and coordination numbers in the short-range. Our results are compatible with the presence of both GeSe_4/2 tetrahedra and Se–Se bonds. The Ag atoms are linked to Se in a triangular environment. Numerical simulations allowing the identification of the main peaks in the total pair correlation functions have complemented the neutron diffraction measurements.     

Infrared absorption of some high-purity chalcogenide glasses

New compouning techniques were devised to prepare high-purity Ge₂₈Sb₁₂Se₆₀ (TI 1173)and Ge₃₃As₁₂Se₅₅ TI 20). The methods were based on the combination of the reactant purification and compounding steps. The goal of the program was to establish the absorption limit for the glasses and to lower the absorption at 10.6 μm. At the present purity level, the GeSbSe glass is found to have an absorption level of about 0.01 cm^?1 at 10.6 μm while the absorption level for the GeAsSe glass is 0.05 cm^?1. Underlying causes for the limits are discussed along with the possibilities for improvement.     

The thermal conductivity of some chalcogenide glasses

The temperature-dependent thermal conductivities of several chalcogenide glasses were determined above 300 K. At 300 K, the thermal conductivity for most of these glasses is about 3 mW/cm · deg.     

Low frequency Raman scattering in chalcogenide glasses

Low frequency Raman spectra of chalcogenide glasses are analyzed in terms of matrix element effects and modes of a layered structure. The spectra of GeSe₂ at low temperature shows no peaks which can be assigned to layer modes. The reduced spectra indicates that the density of states exhibits nearly ω² dependence for ω < 60 cm^?1, and the coupling constant approaches ω² dependence at frequencies less than 20 cm^?1.     

Photoluminescence dynamics in chalcogenide glasses and crystals

Time-resolved photoluminescence studies reveal distinct differences between the recombination processes in a chalcogenide glass and in its crystalline counterpart. Here the three luminescence bands of a-As₂S₃ are interpreted in terms of the recombination of an excition, a self-trapped exciton and a pair of electron- and hole-like small polarons. The two luminescence bands observed in the crystal are attributed to the recombination of two types of excitons composed respectively of a hole bound to a self-trapped electron, and a hole which is induced to self-trap in the presence of a self-trapped electron.     

Self refractive non-linearities in chalcogenide based glasses

We report third order non-linear absorption and refraction measurements at 1.20 and 1.52 μm on selected gallium-Lanthanum sulfide-based glasses (Ga:La:S) showing negligible non-linear absorption and a refractive non-linearity close to one hundred times that of SiO₂. Their potential use in telecommunication as base materials for all-optical switching practical devices is evaluated resulting in large figures of merit. The addition of a glass modifier to the Ga:La:S matrix has improved thermal and optical properties, resulting in ease of fibre drawing. The non-linear optical response of this new variant of the Ga:La:S family is studied.     

Microstructural modification of chalcogenide glasses by femtosecond laser

With the irradiation by femtosecond (fs) laser with high repetition rate, GeS₂ micro/nano-crystalline formation and microstructural modification occurred in pseudo-binary GeS₂–In₂S₃ glass, while almost no similar change was observed in GeS₂ glass. The addition of In₂S₃ is beneficial for the precipitation of GeS₂ micro/nano-crystals. It is expected that functional micro/nano-crystals can be controllably prepared in chalcogenide glasses by fs laser irradiation through glass composition design.     

Temperature dependence of dielectric losses in chalcogenide glasses

The frequency (2 × 10⁴?2 × 10⁷ Hz) and temperature (250–600 K) dependence of the imaginary part of the permittivity, ?′', of As₂Se₃ and Tl₂SnSe_8.61 is explained within a theoretical model. The dielectric premittivities of these compounds are correctly explained by means of a model of a hopping process over a potential barrier between localized sites.We have found that the glassy system of chalcogenide can exist in the form of dipoles. The theory shows, in agreement with the experimental results, that ?′' = Aω^m, where m is a function of temperature.     

Field effect in small filaments of chalcogenide glasses

A field effect has been measured in a semiconducting chalcogenide glass, of composition Te₂AsSi. The sample was in the form of a fine filament, encapsulated within a rod of insulating glass, with the bias field applied radially. The effect is small, and the change in conductivity increases more slowly with field at high fields than at low fields. The results are explained in terms of a model with a uniform density of bulk states near the Fermi energy and a sharp surface level just below the Fermi energy. There is a depletion layer at the surface at zero bias, hence the surface barrier with no external field varied with each sample.