Equivalent electric circuit analyses of ionic thermocurrent in sodium-doped CaF2 crystals

The characteristics of high-temperature ionic thermocurrent (HT ITC) in CaF₂ doped with different sodium concentrations were studied by the Teflon-insulated electrode ITC method. It was shown that, with increasing sodium concentration, the HT ITC band moved toward a Na⁺-F_V dipole band with a peak at 162 K. The results of analyses of the HT ITC spectra using an equivalent electric circuit proved that the activation energy of space charge migration related to HT ITC was also strongly dependent on the doped sodium concentrations if varied from 0.94 to 0.46 eV with increasing sodium concentration in our ITC study. In addition, the broadening of the Na⁺-F_V dipole band was observed in 3 nominal mole% NaF-doped CaF₂, which was accompanied by a considerable decrease of the activation energy from 0.46 to 0.29 eV without showing marked temperature shifts of the peak ITC bands.     

Nonlinear optical characterization of phosphate glasses based on ZnO using the Z-scan technique

The nonlinear optical properties of a phosphate vitreous system [(ZnO)_x-(MgO)_30-x-(P₂ O₅)₇₀], where x=8, 10, 15, 18, and 20 mol% synthesized through the melt-quenching technique have been investigated by using the Z-scan technique. In the experiment, a continuous-wave laser with a wavelength of 405 nm was utilized to determine the sign and value of the nonlinear refractive (NLR) index and the absorption coefficient with closed and opened apertures of the Z-scan setup. The NLR index was found to increase with the ZnO concentration in the glass samples by an order of 10^-10 cm²·W^-1. The real and imaginary parts of the third-order nonlinear susceptibility were calculated by referring to the NLR index (n₂) and absorption coefficient (β) of the samples. The value of the third-order nonlinear susceptibility was presented by nonlinear refractive or absorptive behavior of phosphate glasses for proper utilization in nonlinear optical devices. Based on the measurement, the positive sign of the NLR index shows a self-focusing phenomenon. The figures of merit for each sample were calculated to judge the potential of phosphate glasses for application in optical switching.     

Electrochromism by polarization of semiconducting ionic materials

Electrochromic effects are observed by employing a single mixed ionic and electronic conducting layer in-between two transparent electronic leads. Besides the simplicity of the arrangement, the advantage is the displacement of ions only within one phase rather than across phase boundaries as required by conventional devices. The applied voltage controls the compositions at the two interfaces according to Nernst's law independent of ions being majority or minority charge carriers. Appropriate materials are intrinsic conductors in the unpolarized transparent state which become n-type and p-type conducting at the negative and positive electrode side, respectively. Several materials have been investigated, such as lithiated tungsten oxide and lithium/tantalum co-doped tungsten oxide. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 September 1994.     

A model for the occurrence and analysis of ionic thermocurrent spectrum involving different orders of kinetics

Ionic thermocurrent (ITC) spectrum is much similar to a thermoluminescence (TL) glow curve involving monomolecular kinetics. It has already been reported that different orders of kinetics are involved in TL processes, which depend specifically on the extent of recombination and simultaneous retrapping. It is found that the involvement of different orders of kinetics in ITC spectrum depends on the experimental conditions of polarization and rate of rapid cooling. Consequently, order of kinetics involved in the ITC spectrum does not represent any specific feature of the system under investigation. An equation is developed which explains the occurrence of ITC spectrum involving any order of kinetics. Dielectric relaxation parameters, order of kinetics and approximate number of dipoles per unit volume are evaluated conveniently and easily following the proposed model.     

Migration polarization in dielectrics and semiconductors

It is shown that during migration polarization the relaxation time is governed by the carrier lifetime in the bound state, by the thickness of the layer through which the migration occurs, and by the drift velocity. An equation is found for ion migration by generalizing the equation for ion-relaxation polarization. Experimental data found by the Ioffe method on the ion mobility in Al₂O₃ are reported and compared with the mobilities obtained by the method of this paper, on the basis of the equation for the relaxation time. Migration polarization must be taken into account in analyzing the mechanism for the excess noise and certain cases of current oscillations in semiconductors, dielectric loss of a relaxation nature, relaxation phenomena in film-type active devices, etc.     

Dielectric relaxation in vanadium phosphate glasses

An asymmetric distribution of relaxation times has been inferred from an increase in the Cole-Cole distribution parameter α with increasing values of ωτ in 62% v₂O₅–38% P₂O₂ glass. The conventional Debye type relaxation loss peaks in the frequency range 10²–10⁵ Hz are observed in this sample above 85°K. The extrapolated values of dielectric constant and relaxation time below 100°K seem unexpectedly large while the high temperature extrapolated values of ?' are close to ?_∞ as expected. Probably the conventional dielectric loss peaks are observed only above a critical temperature at which the carriers gain sufficient energy to be excited to the conduction band edge. Below this temperature hopping of carriers within kT of the Fermi level may dominate and conventional Debye type dielectric loss peaks may lose their significance as envisaged in the models of frequency dependent ac conductivity.     

Silver ionic conductivity enhancement by network former mixed in oxide-based glasses

Glasses in the binary system xAg₂P₂O₆ − (1 − x)Ag₂Te₂O₅ have been prepared for 0 x 1. For each composition only one glass transition temperature is observed in the temperature range of 180–220 °C. All glasses appear homogeneous considering their optical and electrical properties. Nevertheless, in SEM observations, some glass compositions appear to be heterogeneous after decoration following short nitric acid etching. For each composition, conductivity data obtained in the temperature range of 25–200 °C using impedance techniques obey an Arrhenius relationship with a composition independent pre-exponential term. Variation of the conductivity activation energy with x induces correlative variations of isothermal conductivity curves leading to an increase of the ionic conductivity of about one order of magnitude compared with linearity at 25 °C. This behaviour is discussed with respect to the thermodynamic properties of the glassy solutions.     

A Raman study of lithium fluoride containing fast ionic conducting glasses

The role of fluorine in the structure of fluoro-borate fast ionic conducting glasses has been studied by Raman spectroscopy. It is shown that addition of LiF results in important structural changes, compared to binary glasses with the same O/B ratio. The Raman results are consistent with the participation of fluorine in the network. Careful control of the O/B ratio is required in order to detect the alkali fluoride-induced structural changes by Raman spectroscopy.     

Mesopore size dependence of the ionic diffusivity in alumina based composite lithium ionic conductors

Ordered-mesoporous Al₂O₃ was synthesized by a sol–gel method using neutral copolymer surfactants as structure-directing agents. The pore size was controlled over the 3–15 nm range by the use of various surfactants. Composites composed of the synthesized mesoporous Al₂O₃ and a lithium ion conductor (LiI) were prepared. The maximum dc electrical conductivity, 2.6 × 10^− 4 S cm^− 1 at 298 K, was observed for 50 LiI·50 Al₂O₃ composite with 4.2 nm average mesopore size, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which conductivity increased with decreasing pore size, except for samples with a pore size of 2.8 nm. The lithium ion diffusion coefficient determined by the ⁷Li pulsed field gradient nuclear magnetic resonance (PFG-NMR) showed excellent agreement with the measured conductivity calculated by the Nernst-Einstein equation. On the other hand, lithium migration activation energies obtained by quasielastic neutron scattering (QENS) and ⁷Li NMR spin-lattice relaxation time (T₁) were considerably smaller than those obtained from electrical conductivity and PFG-NMR. This could be explained by the ion migration mechanism in heterogeneous composites and a possible enhancement of conductivity in mesoscopically confined spaces.     

Diffusion and ionic conductivity in sodium beta alumina

Measurements of sodium tracer diffusion (D_t) and ionic conductivity (σ) have been made on the same single crystals of sodium beta-alumina of composition 1.23 Na₂0.11 Al₂O₃. The σ- measurements were made over the temperature 390–660 K using reversible (liquid sodium) electrodes. A fit to the conductivity data gives $\text{σT = 2470}\text{exp}\text{(?0.142}\text{eV}\text{kT}\text{)Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{K}$. The D_t, measurements employed two techniques, i.e. nondestructive profiling over the temperature range 210–750 K and cation exchange over the temperature range 505–970 K. The results of the two techniques were in close agreement and can be expressed as $\text{D = 2.12 ×10}{}^{\mathrm{?4}}\text{exp}\text{(?0.169}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}{}^{\mathrm{?1}}$ for T>520K and $\text{D = 2.45 × 10}{}^{\mathrm{?4}}\text{exp}\text{(?0.164}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}\text{470}\text{K}$. The “transition” region between 470 and 520 K is not observed in the conductivity measurements. Silver cation exchange was used to determine the number of mobile sodium ions. A comparison of D_t and σ data yielded a Haven ratio that is temperature dependent, ranging in value from 0.45 at 870 K to 0.35 at 370 K.     

Laser beam induced optical aberrations in phosphate and fluoride phosphate glasses

Designing pulsed laser amplifiers requires detailed knowledge about beam distortions at the amplifying medium. Time resolved experiments have been performed on fluoride phosphate and pure phosphate glass in order to study optical aberrations induced by pump beam irradiation. By means of a probe beam tunable in wavelength, it was possible to discriminate between thermally induced variations of the optical path and beam narrowing effects due to the radial gain distribution. The experimental results were analyzed theoretically regarding Fresnel diffraction. A quite different response was found for the two types of glass despite their similar nominative properties. PACS 42.60.Jf; 42.60.By; 42.15.Fr     

Time dependence of the polarization of the luminescence in chalcogenide glasses

Time dependence of the polarization of the luminescence with polarized exciting light and its temperature dependence were observed in chalcogenide glasses. The experimental data can be analyzed with a model based on localized excitons in a fluctuating potential due to random structure of the glasses.     

Surface layers in ionic crystals: Theoretical treatment illustrated by single crystal alumina

The local thermodynamic equilibrium method has been used to derive theoretical expressions for the surface potential and the potential profile in the space charge region of an ionic crystal with metal contacts and containing variable valence impurities, which is in a gaseous ambient containing one of its constituents. This has been illustrated by using acceptor-doped alumina in equilibrium with an atmosphere containing oxygen. We have incorporated the effects of metal electrodes, and have interpreted the defect and impurity chemical potentials in terms of the band diagram energy levels, neither of which has previously been done in this context. Analysis of the resultant expressions under special conditions, shows that the space charge layer properties depend on the oxygen partial pressure, as well as on the temperature. A rich variety is predicted in the sign and magnitude of surface potential variation with these ambient conditions. Such a variety is implied in the results of dielectric measurements by ourselves and others. The surface potential also depends on the detailed electronic structure of the crystal with its defects and the contacts. The application of local thermodynamic equilibrium allows a certain freedom in eliminating some of the system parameters in favour of others. The physical meaning of this is discussed qualitatively. The overall analysis should, therefore, facilitate interpretation of dielectric measurements in terms of electronic structure.     

Calculation of ionic conductivity activation energies in ionic oxide glasses from spectroscopic data

Activation energies for ionic conduction in inorganic oxide glasses are related to cation-motion vibrational band frequencies from the far infrared spectra of the glasses, and the calculated and observed values are compared.