On a.c. conductivity in chalcogenide glasses

A simple model describing doubly occupied defect states in chalcogenide glasses is used to get the power frequency dependence of a.c. conductivity. The temperature dependence of the exponent is found to be linear for not too low temperatures.     

A.c. conductivity and optical absorption in chalcogenide glasses

The energy levels of a simple model describing the doubly occupied defect states in chalcogenide glasses are calculated when strong electron-phonon interaction is supposed. The Kubo formula is used to get a.c. conductivity. The model implies a connection between the power dependence of a.c. conductivity ^s and between the low-energy exponential absorption tail.I would like to thank Dr. E. Majerníková for advice and encouragement throughout this work.     

Ionic conductivity of silver chalcogenide glasses

The dynamic response by electrical spectroscopy of ionically conducting chalcogenide glasses (Ag₂S)_x(GeS₂)_1–x has been studied. The activation energies E_d.c deduced from the Arrhenius plots are temperature dependent. Fitting the curves to log(σ_a.c)=f(log ω) leads to values of characteristic parameters that are dependent both on temperature and frequency. The obtained experimental results are compared with a theoretical model based on the concept of “free volume” fluctuations. A new approch is proposed leading to acceptable hopping distances. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994.     

A.c. conductivity and relaxation in LiCoVO4 ceramics

The LiCoVO₄ compound is synthesized by solution-based chemical method. X-ray diffraction analysis exhibits a single phase nature of the compound with cubic structure. The dielectric constant (ε_r), tangent loss (tanδ) and a.c. conductivity (σ_ac) have been studied as a function of frequency and temperature using complex impedance spectroscopy (CIS) technique. The variation of (ε_r and tanδ) with frequency at studied temperatures shows a dispersive behavior at low frequencies. Frequency dependence of σ_ac at different temperatures obeys Jonscher’s universal power law governed by the relation: σ_ac = σ_dc + Aωⁿ, where n is the frequency exponent in the range of 0 ⩽ n ⩽ 1 and A is a constant that depends upon temperature.     

Switching effect in chalcogenide glasses

A new physical concept of the switching effect in chalcogenide glasses is put forward that differs radically from those proposed earlier. The concept is based on the cluster model of the structure of glass. The mechanism of conduction observed after switching is treated within separate regions as resonant motion of singlet electron pairs over two-level systems formed by adjacent localized states. This concept suggests, as a natural consequence, an electronic (rather than thermal) and threshold character of switching, an increase in the electric current by many orders of magnitude, filamentation of the current, the appearance of memory upon holding for a long time in an electric field, and a typical threshold value of the field strength.     

Non-radiative recombination in chalcogenide glasses

Non-radiative recombination of electron-hole pairs in chalcogenide glasses is described using a mechanism of a strong electron-phonon coupling. Recombination proceeds through a transient bonding rearrangement that creates a defect similar to those giving localized electronic states. Incomplete recombination which leaves the defect in a metastable state explains the reversible photostructural change.     

Dielectric relaxation and ac conductivity of sodium tungsten phosphate glasses

Studies of dielectric relaxation and ac conductivity have been made on three samples of sodium tungsten phosphate glasses over a temperature range of 77–420 K. Complex relative permitivity data have been analyzed using dielectric modulus approach. Conductivity relaxation frequency increases with the increase of temperature. Activation energy for conductivity relaxation has also been evaluated. Measured ac conductivity (σ_m(ω)) has been found to be higher than σ_dc at low temperatures whereas at high temperature σ_m(ω) becomes equal to σ_dc at all frequencies. The ac conductivity obeys the relation σ_ac(ω)=Aω ^S over a considerable range of low temperatures. Values of exponent S are nearly equal to unity at about 78 K and the values decrease non-linearly with the increase of temperature. Values of the number density of states at Fermi level (N(E _F)) have been evaluated at 80 K assuming values of electron wave function decay constant α to be 0.5 (Å)^?1. Values of N(E _F) have the order 10²⁰ which are well within the range suggested for localized states. Present values of N(E _F) are smaller than those for tungsten phosphate glasses.     

High-pressure structural changes in chalcogenide glasses

The pressure dependence of the first sharp diffraction peak has been studied for GeS₂ and As₂S₃ glasses. The shift of the peak position induced by hydrostatic compression is closely related to the macroscopic compressibility. The shift in glassy GeS₂ quantitatively corresponds to the change in the interlayer distance of the crystalline specimen under pressure. These observations indicate that the glasses consist of distorted layer molecules held together with van der Waals forces.     

Stretched exponential relaxation and dispersive conductivity behavior in lithium bismuth silicate glasses

Glasses having compositions xLi₂O∙(85 − x)Bi₂O₃∙15SiO₂ (x = 35, 40, and 45 mol%) were prepared by normal melt quenching technique. Electrical relaxation and conductivity in these glasses were studied using impedance spectroscopy in the frequency range from 20 Hz to 1 MHz and in the temperature range from 453 to 603 K. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency were extracted from the impedance spectra. The dc conductivity increases with increase in Li₂O content providing modified glass structure and large number of mobile lithium ions. Similar values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome the same energy barrier while conducting and relaxing. The non-exponential character of relaxation processes increases with decrease in stretched exponential parameter ‘β’ as the composition parameter ‘x’ increases. The observed conductivity spectra follow a power law with exponent ‘s’ which increases regularly with frequency and approaches unity at higher frequencies. Nearly constant losses (NCL) characterize this linearly dependent region of the conductivity spectra. A deviation from the ‘master curve’ for various isotherms of conductivity spectra was also observed in the high-frequency region and at low temperatures, which supports the existence of different dynamic processes like NCL in addition to the ion hopping processes in the investigated glass system.     

Ion conductivity and dielectric relaxation behavior in FIC silver based phospho-molybdate glasses

Electrical conductivity and dielectric relaxation studies of silver ion-conducting glasses have been prepared using xAg₂SO₄-15Ag₂O-(90-x)(90P₂O₅-10MoO₃) glass system over a temperature range of 298–353 K and frequencies of 10 Hz to 10 MHz. DC conductivities exhibit Arrhenius behavior over the entire temperature range with a single activation barrier. The ac conductivity behavior of these glasses has been analyzed using single power law; conductivity increases linearly in logarithmic scale with Ag₂SO₄ concentration. The power law exponent (s) decreases, while stretched exponent (β) is insensitive to increase of temperature. Scaling behavior has also been carried out using the reduced plots of conductivity and frequency, which suggest that ion transport mechanism remains unaffected at all temperatures and compositions.     

Evidence of distributed interstitialcy-like relaxation of the shear modulus due to structural relaxation of metallic glasses

The interstitialcy theory is used to calculate the kinetics of shear modulus relaxation induced by structural relaxation of metallic glasses. A continuous distribution of activation energies is shown to be a salient feature of the relaxation. High precision in situ contactless electromagnetic acoustic-transformation shear modulus (600- kHz) measurements performed on a Zr-based bulk metallic glass are found to strongly support the approach under consideration. It is revealed that the activation energy spectra derived from isothermal and isochronal shear modulus measurements are in good agreement with each other. It is concluded that the increase of the shear modulus during structural relaxation can be understood as a decrease of the concentration of structural defects similar to dumbbell interstitials in simple crystalline metals.     

Te基远红外硫系玻璃光纤的制备及性能分析

随着光学技术由可见向中、远红外等长波长领域的发展,可透远红外的玻璃光纤研究成为近年来光学领域的发展热点之一.传统含Se的Te基硫系光纤无法工作于12μm以上的远红外.本文研究了新型GeTe-AgI硫系玻璃体系的提纯制备,利用挤压技术,制备了阶跃型GeTe-AgI远红外光纤,其光学损耗为:15.6 dB/m@10.6μm,整体低于24 dB/m@8—15μm.在实验过程中,首先采用传统的熔融-淬冷法和蒸馏纯化工艺制备了GeTe-AgI高纯玻璃样品.利用差示扫描量热仪、红外椭偏仪、红外光谱仪等测试了玻璃的物理性质和红外透过性能,分析了提纯工艺、AgI原料纯度对玻璃形成以及透过的影响,最后采用分步挤压法制备了芯包结构光纤.实验结果表明:蒸馏提纯和AgI原料纯度对玻璃的透过性能有着决定性的影响,同时Te含量的增加影响了玻璃的抗析晶能力,但新型挤压制备工艺和有效提纯技术共同保障了较低损耗Te基光纤的制备,所获得的GeTe-AgI光纤具有远红外宽谱应用的潜能(工作波段5.5—15μm)并且绿色环保,可以满足CO_2激光的能量传输和远红外传感应用.     

Linear optical characterization of chalcogenide glasses

A simple experimental method is used to obtain the evolution of both the refractive index and the linear absorption coefficient as a function of the optical wavelength in the near infrared range (from 900 up to 1700 nm with 10 nm resolution). Several chalcogenide glasses (As₂S₃, As₂Se₃, GeSe₄) are tested and the corresponding Cauchy coefficients are determined. Comparison of our results shows a good agreement with values available in the literature at some wavelength. Application of this method is used to estimate Cauchy coefficients of Ge₁₀As₁₀Se₈₀ for the first time to our best knowledge.     

Rayleigh-Brillouin scattering in chalcogenide glasses of the Ge-As-S system

Rayleigh-Brillouin scattering in chalcogenide glasses of the Ge-As-S system was investigated for the (As₂S₃)_100?x (GeS₂)_x (x=0–100) series. The longitudinal hypersonic velocities, adiabatic elasto-optical constants (p ₁₂)_ad at frequencies of about 15 GHz, and Landau–Placzek ratios (R _LP) were determined.     

低损耗Ge-As-Se-Te硫系玻璃远红外光纤的性能分析

中、远红外光学领域的发展,离不开低损耗光波导材料的发展,因此近年来远红外低损耗光纤一直是光学领域的热点之一.本论文在国内首次报道了一种基于挤压法的低损耗远红外光纤制备技术,获得了具有完整结构的远红外光纤,其损耗为:0.46 d B/m@8.7μm,1.31 d B/m@10.6μm,整体低于1 dB/m@7.2—10.3μm.在实验过程中,首先采用传统的熔融淬冷法和蒸馏纯化工艺制备了Ge-As-Se-Te玻璃样品.利用X射线衍射仪和热膨胀仪等测试了玻璃的结构和物理性质,分析了Ge对玻璃热学性质的影响;利用分光光度计、红外光谱仪等研究了玻璃的光谱性质;综合比较了还原剂铝、镁的除氧效果.最后采用挤压法制备了芯包结构光纤.实验结果表明:镁的除氧效果佳,新型挤压制备工艺和有效提纯技术共同推进了硫系光纤损耗的降低,所获得的Ge-As-Se-Te光纤具有远红外广谱应用的潜能(其透光波长接近12μm).     

Photoinduced stable second-harmonic generation in chalcogenide glasses

We report on photoinduced second-harmonic generation (SHG) in chalcogenide glasses. Fundamental and second-harmonic waves from a nanosecond pulsed Nd:YAG laser were used to induce second-order nonlinearity in chalcogenide glasses. The magnitude of SHG in 20G?20A?60S glass was 10(4) larger than that of tellurite glass with a composition of 15Nb(2)O (5) 85TeO(2) (mol.%). Moreover, no apparent decay of photoinduced SHG in 20G?20A?60S glass was observed after optical poling at room temperature. We suggest that the large and stable value of chi((2)) is due to the induced defect structures and large chi((3)) of the chalcogenide glasses.