Ag–Ge–Se glasses: a vibrational spectroscopy study

Ag_x(Ge_0.25Se_0.75)_100−x glasses with x varying from 0 to 25 have been shown to exhibit a conductivity threshold around x ~8–10. In this work, the structural changes induced by introduction of Ag in Ge₂₅Se₇₅ glass have been investigated using Raman and infra‐red spectroscopies. In ambient conditions, changes are observed in position, width and intensity for vibrations assigned to Ge–Se bonds, showing that the tetrahedral network is relaxed and gains flexibility as Ag is introduced. High pressure experiments on two glasses containing 5 and 25 at.% Ag confirm that Ag‐rich (25%) glasses clearly exhibit higher compressibility than Ag‐poor (5%) glasses. Copyright © 2013 John Wiley & Sons, Ltd.     

Controlled local filament growth and dissolution in Ag–Ge–Se

Memory cells based on the cation migration and filament formation and rupture in a solid electrolyte have attracted much interest due to low switching voltages and a prospective high scalability. In this study we indirectly visualized the growth and dissolution of the conductive filament in Ag–Ge–Se samples with Ag bottom electrodes by surface analysis with Conductive Atomic Force Microscopy (CAFM). By application of a negative voltage to the inert CAFM tip, conductive filaments were grown on the scanned area and they were dissolved under reversed bias. The local conductivity changes directly corresponded to changes in the topography, i.e. to the filament protrusion and dissolution. Topography changes could be circumvented by limiting the maximum current. By placing the CAFM tip on a random spot on the sample, filaments with a diameter as low as 20 nm were grown by local current–voltage measurements. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the reversibility window in binary As–Se glasses

Physical ageing effects caused by prolonged natural storage are recorded for binary As_xSe_1−x glasses with 0.2x<0.4. Their origin is associated with pure “shrinkage” of under-constrained glass networks. It is shown that only stoichiometric As₂Se₃ composition, which network is formed by a so-called self-organized phase, possesses the ideal non-ageing ability.     

Amorphous-to-crystalline transition in Ge22Se78−x Bi x system

Summary Crystallization kinetics is studied in glassy Ge₂₂Se_78−x Bi _x (0≤x≤10) using isothermal annealing at various temperatures between the glass transition and melting. D.c. conductivity is taken as a parameter to estimate the extent of crystallization (α). The activation energy of crystallization (ΔE) and the order parameter (n) are calculated by fitting the values of α in Avrami’s equations of isothermal transformation. The results indicate that ΔE is highly composition dependent and decreases as the Bi concentration increases.     

Nanoscale intrinsic heterogeneities in Ag-Ge-Se glasses and their correlation with physical properties

Ag-Ge-Se glass forming system is dominated by liquid immiscibility. Glasses in the Se-GeSe₂-Ag₂Se triangle may have different morphologies according to their composition. In this work inhomogeneous morphology is observed in Ag_x(Ge_ySe_1−y)_100−x bulk glasses with y = 0.20, 0.25 at.% fraction. Electron microscopy reveals that the scale of heterogeneity strongly depends on the sample composition. The physical properties of these glasses are also dependent on their composition and can be easily correlated to their morphology. Accordingly, the electric conductivity evolves from semiconducting to ionic conductivity whereas a percolation transition occurs in a narrow Ag concentration range.Mössbauer spectrometry let us to analyse the local order of these intrinsically heterogeneous glasses employing ⁵⁷Fe as a probe.     

Crystallization kinetics and thermal stability in Se85-xTe15Sbx chalcogenide glasses

Crystallization process of Se_85-xTe₁₅Sb_x (x = 2.7, 7.5, 10 and 15 at %) chalcogenide glasses has been studied by using differential scanning calorimetry (DSC) with different heating rates. These glasses are found to have a double glasses transition and overlapped crystalline phases for Se₇₀Te₁₅Sb₁₅ glass while single glasses transition and single crystallization stage for other glasses. Glass transition temperature, T_g, onset crystallization temperature, T_c, and peak crystallization temperature, T_p, are found to be dependent on composition and heating rates. Values of various kinetic parameters such as activation energy of glass transition, E_g, activation energy of crystallization, E_c, Hurby number, H_r, thermal stability, S_p, rate constant, K_p, and Avrami exponent, n, are determined for the present systems. Results indicate that rate of crystallization is dependent on thermal stability and glass-forming ability. Crystallization mechanism occurs in two dimensions for studied compositions. Crystalline phases resulting from DSC and scanning electron microscopy have been identified by using X-ray diffraction.     

Phase transition characteristics of Ge–Sb–Te pseudobinary alloys in laser irradiation measurement

Optical switching and structural transformation of GeTe–Sb₂Te₃ pseudobinary alloys, Ge₂Sb₂Te₅, Ge₁Sb₂Te₄, and Ge₁Sb₄Te₇, were studied for data storage application. As-deposited Ge₂Sb₂Te₅, Ge₁Sb₂Te₄, and Ge₁Sb₄Te₇ thin films were amorphous and they crystallized to FCC and HCP upon heat treatment. Crystallization was accelerated by increasing the proportion of Sb₂Te₃ rather than GeTe in Ge–Sb–Te compounds; this was observed by reflectivity changes under nanosecond laser irradiation in static tester. The different crystallization kinetics according to composition might be affected by the structural incompatibility of GeTe under the ‘Umbrella Flip’ theory.     

Glass-forming liquids,anomalous liquids,and polyamorphism in liquids and biopolymers

Summary Glass formation in nature and materials science is reviewed and the recent recognition of polymorphism within the glassy state, polyamorphism, is discussed. The process by which the glassy state originates during the continuous cooling or viscous slowdown process, is examined and the three canonical characteristics of relaxing liquids are correlated through the fragility. The conversion of strong liquids to fragile liquids by pressure-induced coordination number increases is discussed, and then it is shown that for the same type of system it is possible to have the same conversion accomplished via a first-order transition within the liquid state. The systems in which this can happen are of the same type which exhibit polyamorphism, and the whole phenomenology can be accounted for by a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The concept of complex amorphous systems which can lose a significant number of degrees of freedom through weak first-order transitions is then used to discuss the relation between native and denatured hydrated proteins, since the latter have much in common with plasticized chain polymer systems. Finally, we close the circle by taking a short-time-scale phenomenon given much attention by protein physicists,viz., the onset of an anomaly in the Debye-Waller factor with increasing temperature, and showing that for a wide variety of liquids, including computer-simulated strong and fragile ionic liquids, this phenomenon is closely correlated with the experimental glass transition temperature. This implies that the latter owes its origin to the onset of strong anharmonicity in certain components of the vibrational density of states (evidently related to the boson peak) which then permits the system to gain access to its configurational degrees of freedom. The more anharmonic these vibrational components, the closer to the Kauzmann temperature will commence the exploration of configuration space and, for a given configurational microstate degeneracy, the more fragile the liquid will be. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

The optical,structural and thermal optimizations of Ge-As-Se-S-Te glasses

The optical, structural and thermal optimizations of Ge₃₃As₁₂Se₅₅ glass were the aim of this study. In this regards, Ge₃₃As₁₂Se₄₅M₁₀ (M = Se, Te, S and S_0.5Te_0.5) glasses were synthesized by conventional melt quenching technique in quartz ampule. The prepared samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The fundamental absorption edge for prepared samples was also analyzed in terms of the theory proposed by Davis and Mott. The addition of S and Te elements to melting batch has deleterious effects on optical properties of Ge₃₃As₁₂Se₅₅ glass. Mg and Al can act as gettering elements for reduction of the intensity of oxide absorption bands from FTIR spectra (without any effects on optical properties of Ge₃₃As₁₂Se₅₅ glass). The precipitation of GeSe phase, during crystallization process, has negligible effects on optical properties of Ge₃₃As₁₂Se₅₅ glass.     

Evidence of large-angle reorientation in supercooledo-terphenyl

Summary We study the reorientation process of a paramagnetic radical dissolved in supercooledo-terphenyl around and belowT _g via the Electron Spin Resonance spectroscopy. The experimental results are at variance with the hypothesis of diffusive reorientation of the radical. Instead, the ESR lineshapes are fairly well reproduced by assuming that the radical reorientates via large angular jumps with a width Δϕ=80° _−5° ^+10° . The results are compared with previous²H NMR studies. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Study on the structure dependent ultrafast third-order optical nonlinearity of GeS2–In2S3 chalcogenide glasses

The results of the femtosecond time-resolved optical Kerr at 820 nm in GeS₂–In₂S₃ chalcogenide glasses indicate that the response time in GeS₂–In₂S₃ glasses is subpicosecond, which is predominantly due to the distortion of the electron cloud. The value of χ⁽³⁾ in 0.95GeS₂–0.05In₂S₃ glass is also as large as 2.7 × 10⁻¹³ esu, and it reduces with the addition of In₂S₃, which may be ascribed to the microstructure evolution of GeS₂–In₂S₃ glasses. It is deduced that the intrinsic [Ge(In)S₄] tetrahedral structure units that possess the high hyperpolarizability may do great contribution to the enhancement of third-order optical nonlinearity while [S₃Ge–GeS₃] ethane-like molecular units make no considerable contribution to that in femtosecond time scale. These GeS₂–In₂S₃ and GeS₂–In₂S₃-based chalcogenide glasses would be expected to be the promising materials for all-optical switching devices.     

Compositional dependences of average positron lifetime in binary As-S/Se glasses

Compositional dependence of average positron lifetime is studied systematically in typical representatives of binary As-S and As-Se glasses. This dependence is shown to be in opposite with molar volume evolution. The origin of this anomaly is discussed in terms of bond free solid angle concept applied to different types of structurally-intrinsic nanovoids in a glass.     

Composition and electric field effects on the transport properties of Bi doped chalcogenide glasses thin films

The temperature dependence of the DC electrical conductivity σ_DC was measured in the temperature range from 300–500 K. It was found that there are double activation energies, E_σ, for Ge₂₀Se_80−xBi_x (x=0, 2.5 and 5 at%) films, while there is single activation energy for Ge₂₀Se_72.5Bi_7.5. when incorporation of Bi=7.5 at%, the pre-exponential value σ₀ decreases by about six order of magnitude, the activation energy in the extended states E_σ decreases from 0.96 to 0.09 eV. Also the effect of applied electric field was studied and observed that, activation energy in high temperature region increases with increasing electric field; this behavior can be understood assuming that the contribution to the conductivity activation process is due to conduction in the extended states and also due to hopping in the localized states. With the increasing electric field, as former process, which is having high activation energy, becomes more predominant due to the dumping of the carriers in the extended states, the effective activation energy of the system increases, in spite of the fact that the activation energy of the extended states conduction may remain constant. Finally, the electrical data suggests that the addition of bismuth produces localized states near the conduction band edge so that the electrical transport is due to hopping of electrons after being excited into localized states at the conduction band edge.     

Thermal characterization of Se85−xSb15Snx (10≤x≤13) chalcogenide glasses

Results of crystallization kinetics, viscosity, specific heat, thermal stability, and glass forming ability of Se_85−xSb₁₅Sn_x (x=10, 11, 12.5, and 13) chalcogenide glasses, using differential scanning calorimeter (DSC), under non-isothermal condition have been reported and discussed. The variation of the peak temperature of crystallization T_p with the heating rate β has been used to investigate the growth kinetics using Kissinger, Takhor, and Augis-Bennet models. The activation energy of crystallization E_c has been found to increase with Sn content and the crystal growth occurs in one dimension. The increasing trend of E_c is interpreted in terms of enhancement of the degree of cross-linking due to the formation of SnSe_4/2 structural units of energies higher than that of Se-Se and Se-Sb bond energies. The viscosity η against 1/T curves has also been drawn and indicated that the atoms of ternary Se-Sb-Sn glasses required more energy, with the addition of Sn, to complete the transformation from amorphous to crystalline state. The demand for thermal stability has been ensured through the calculations of the enthalpy released ΔH_c during the crystallization process and S-parameter, while the obtained values of the reduced glass transition temperature T_rg and Hurby number H_R have been used to estimate the glass forming ability (GFA). Results reveal that, both thermal stability and GFA enhanced with increasing Sn content and the studied samples were prepared from strong glass-forming liquids. The obtained values for the specific heat difference ΔC_p, between the equilibrium liquid and the glass, have been found to decrease with increasing Sn content and are in support of the results of thermal stability and GFA.     

Observation of phase separation in some Se-Te-Sn chalcogenide glasses

Differential scanning calorimeter (DSC) and X-ray diffraction (XRD) techniques were employed here to investigate the glass transition behavior and crystallization kinetics of Se_80−x Te₂₀Sn_x (x=0.0, 2.5 and 5) alloys, which were prepared by the conventional melt quenching method. Two exothermic peaks have been observed in the DSC scans for the samples that contain Sn. Three crystalline phases (Se_7.68Te_0.32, SnSe and SnTe) were classified after heat treating the Se_77.5 Te₂₀Sn_2.5 glass at temperature corresponding to the second crystallization peaks for 3 h. All the characteristic temperatures such as glass transition temperature (T_g), crystallization temperature (T_c) and crystallization peak temperatures (T_p) were found to depend on both the heating rate and the composition. This dependence has been used to deduce the activation energy of the glass transition (E_g), the activation energy of crystallization (E_c), the Avrami exponent (n), thermal stability and the fragility index (F_i).     

Luminescent properties of Dy-doped and Dy–Tmco-doped phosphate glasses

Phosphate glasses doped with Dy³⁺ ions and co-doped with Dy³⁺–Tm³⁺ ions are successfully prepared in the present work. Their photoluminescence properties have been studied by absorption, excitation and emission spectra. A combination of blue and yellow emissions has emerged in the glasses, which allows the observation of white light when the glasses are excited by the ultraviolet light. The emission intensity of Dy³⁺ is influenced by the system ionicity, while the intensity ratio of yellow to blue emissions from Dy³⁺ can be tuned by varying both the concentration of Tm³⁺ ion and the glass matrix composition.     

Preparation and properties of Ce-doped Na–Gd phosphate glasses

Rare earth-doped sodium–gadolinium phosphate glasses with increased luminescence efficiency are promising materials for the detection of neutrons, γ- and X-rays. Their main advantages are low cost, high radioluminescence light output, high quality and chemical durability. The glasses were prepared by a rapid quenching technique in air. The radioluminescence intensity maximum was achieved for a Ce concentration of 3 mol% and that of Gd around 30%. Glass transition temperatures were above 300°C for the tested samples and this guarantees that the glass can be utilised in a sufficiently broad temperature range. The glass-forming ability of this glass system is high. However, until now high-quality glass has been only prepared with a Gd concentration of 40 mol% in the starting batch. The glasses containing at least 30 mol% Gd were moisture resistant, while those with lower Gd concentrations were slightly hygroscopic.     

Photoinduced changes in optical properties of Ga-Sb-Ge-Se glasses

The kinetics of photoinduced effects on Ga₅Sb₁₀Ge₂₅Se₆₀ thin film exposed to continuous wave laser radiations are studied as a function of exposure time and laser intensity. The transmission and reflection spectra of thin films before and after exposure are investigated. The optical band gap and the refractive index are derived from the above spectra. Generalized Miller's rule and linear refractive index are used to find the nonlinear susceptibility and nonlinear refractive index of the thin films. The studies show a red shift in the band gap with increase in exposure time and laser power which is attributed to the photoinduced darkening in the films.     

The influence of indium on the structural modification of the amorphous Ge–In–Se system

The effect of both the chemical composition and the nature of the chemical bonding of amorphous alloyed samples of Ge_xIn_ySe_100−x−y prepared under vacuum with x=20, 4y15 on the efficiency of the structural modification Δφ is analysed using a simple consideration based on the coordination number Z, and the number of topological constraints N_co. The previously obtained parameters have been used for the determination of the number of continuous deformation (i.e. zero-frequency modes f ), and for the estimation of the cohesive energies of these glasses, assuming simple additivity of bond energies. A trial has been made to correlate the results of this paper with the previously published data of glass transition temperature T_g, activation energy ₀ and the shift of the K-absorption edge (ΔE_K) of the composition of vacuum prepared Ge_xIn_ySe_100−x−y. It was found that there is a correlation between the lone-pair electrons and the stability of the vitreous state. According to the criterion of Liang, the above correlation has been interpreted in terms of Δφ.     

Mechanism of electron beam poled SHG in 0.95GeS2·0.05In2S3 chalcogenide glasses

Utilizing the Maker fringe method, SHG was observed in the 0.95GeS₂·0.05In₂S₃ chalcogenide glass irradiated by the electron beam and the intensity of SH increases with the enhancement of beam current from 15 to 25 nA. According to Raman spectra of the as-prepared and the irradiated one, no distinct micro-structural transformation was found. In this work, the built-in charge model was founded to interpret the poling mechanism of electron beam irradiation, the emission of the secondary electrons and Auger electrons results in the formation of positive region and the absorbed electrons form negative region. The positive region was situated near the poling surface, and the negative region was much deeper than the positive region. Between the two opposite charged regions, a strong space-charge electrostatic field, E_dc, is created, which leads to the nonzero χ⁽²⁾ in the 0.95GeS₂·0.05In₂S₃ glass. The emission of backscattered electrons does no contribution to the formation of E_dc.