129I-Mössbauer study of diffusion effects in the superionic conductor Ag3SI

The superionic conductor Ag₃SI was studied by¹²⁹I-Mössbauer spectroscopy in the rhombohedral γ-phase and in the cubic β-phase at temperatures between 4.2 K and 180 K. In the low-temperature γ-phase, one observes well below the γ-β phase transition at 157 K a motional-narrowing-like decrease of the electric-quadrupole interaction, roughly linear with temperature, which points to a diffusional motion of the Ag⁺ ions already in the γ-phase. Diffusional effects are also reflected by anomalous decrease of thef-factor in the same temperature region, which originates from a restricted short-range diffusional displacement of the iodide ions induced by the hopping Ag⁺ ions.     

Ionic conductivity enhancement during pre-crystallization in amorphous lithium ionic conductor Li2B2O4

It is found from the temperature dependence of the ionic conductivity of amorphous Li₂B₂O₄ that the ion transport process is rather complicated. At temperature below T_k (≈310°C), the ionic conductivity obeys an Arrhenius relation. Above the crystallization temperature T_c (≈410°C) ion transport is dominated by the process in the crystalline state. In between the ionic conductivity is anomalously enhanced. In this pre-crystallization range two distinguishable steps with a transition temperature at T_p (≈380°C) can be identified. At temperature between T_k and T_p, the conductivity increase is due to the redistribution of free volume. For temperature between T_p and T_c the specimen contains a small amount of crystallites but the crystallinity is less than 5%. The ⁷Li NMR spectra show that the line shape of partially crystallized amorphous material is quite similar to that of LiCl containing DSPP but in this case the second-phase particles are crystallites of the parent material.     

Molecular dynamics simulation of the superionic conductor BaF2

Molecular dynamics simulations of the BaF₂ fluoride crystal were carried out over a wide range of temperatures in order to study structural and transport characteristics in the low-temperature, the high-temperature superionic, and the molten state. The experimental temperature dependence of the lattice constant was taken into account. A sharp change in total energy of the system in the vicinity of T=1200 K indicates a phase transition to the high-temperature state with a transition energy U=(18.8±0.2) kJ/mol which is close to the value of the latent heat Q=18.36 kJ/mol obtained experimentally at 1275 K. Calculation of the radial distribution functions g(r) shows that in the high-temperature superionic state the F^– sublattice is already disordered while the Ba²⁺ sublattice stays regularly ordered, which keeps the crystal in the solid state. In the low-temperature state both sublattices are regularly ordered, and in the molten state both sublattices are disordered. The calculated diffusion constants of F^– in the superionic state is about 10^–9m²/s which is a typical value for superionic conductors. The temperature dependence of the diffusion constant obeys the Arrhenius equation. Higher statistical moments of the trajectories are used to characterise the type of ion movement.     

Pb2MnF6: Antiferromagnet and superionic conductor

Measurements of the EPR linewidth versus temperature indicate Pb₂MnF₆ is an antiferromagnet with T_N = 30 ± 1 K. The disappearance of the low-field NMR lines at T_N confirms these results. The coalescence of the ¹⁹F NMR lines above 500 K show the anion conductivity to be comparable to PbF₂.     

Modulation and incommensurability in a superionic conductor

The structure factor S(q) is calculated for the Frenkel-Kontorova model at high temperatures. Application to the 1-d ionic conductor K-Hollandite gives an explanation of diffuse X-ray scattering in terms of a modulation phenomenon. The positions of the diffuse sheets are predicted precisely from the stoichiometric composition. It is confirmed thereby that the mobile K⁺ ions behave like a chain with spacing b = 1/n where n is the concentration. The disorder is characterized as short-range crystalline order of wavelength b, competing with and modulated by the framework potential with a different period a.     

Local ionic motion in the superionic conductor Li3N

Anisotropic dielectric behavior of the superionic conductor lithium nitride (Li₃N) is reported for low temperature where the dc ionic conductivity can be neglected (T<17oK). For E ⊥ c the static dielectric constant followed a Langevin-Debye (ε ∝ 1/T) type law from 170 to 80K which changed to a temperature independent value below 40K. Debye relaxations were measured between 10 and 50K in the frequency range 10Hz to 1MHz. The observed properties are discussed in terms of a locally restricted ionic motion in shallow potentials. Different types of potentials are considered and an overdamped oscillator model is proposed.     

Ionic plasma oscillations in superionic conductors

Some superionic conductors behave as if their charge was carried by nearly free charged particles. If this is the case, these free particles should undergo plasma oscillations. The plasma oscillations may already have been observed in superionic AgI and CuI. Similar oscillations might also be observable in ionic liquids such as melted AgI.     

Microwave electrophysical properties of superionic crystals Ag2HgI4

The paper concerns itself with the investigation results of temperature dependencies of electric conduction and dielectric properties of Ag₂Hgl₄ crystals in the frequency range of 10⁷–7,8·10¹⁰ Hz. The obtained data have shown that in α-phase at T=326 K, the electric conductivity σ is proportional v^0,28 in the frequency range of 10⁷–10⁹ Hz and σ is proporti onal v^0,5 in the range of (1,1–78)·10⁹ Hz. The dependence σ(v) in the range of (1,1–78)·10⁹ Hz may be conditioned by the jumping mechanism of the conductivity and low frequency oscillations of the crystal lattice. It is believed, tha in the σ-phase of Ag₂Hgl₄ a condition of the existence of the ionic polaron is satisfied. The activation energy of the polaron is ΔE_p=0,09 eV.     

Ion dynamics and sublattice melting in the superionic conductor PbF2

The F¹⁹ relaxation rates in PbF₂ exhibit anamolous changes as the temperature is increased into the superionic phase. These changes confirm the concept of a continuous melting of the fluorine sublattice and show that the fluorine motion in the superionic phase is highly correlated.     

Microstructure of Ag2S–As2S3 glasses

Field effect-scanning electron microscopy (FE-SEM) and electric force microscopy (EFM) measurements were carried out on bulk Ag₂S–As₂S₃ glasses with silver concentrations 1.2, 4 and 9.8 at.%. While the first glass was found to be homogeneous, the presence of chemical contrasts and electrical heterogeneousness throughout the other two samples indicated that the glasses were phase separated. Moreover, it appeared that, while silver-rich nodules of 200–350 nm were embedded in a silver-poor connecting phase in the glass containing 4 at.% Ag, it was the opposite that occurred in the glass containing 9.8 at.% Ag. Such an inversion explained the large difference of 4–5 orders of magnitude in the conductivity of the two glasses.     

Ionic conductivity and chemical diffusion in LixCu2−xSe superionic alloys

Results of studies on the ionic conductivity and chemical diffusion coefficients of stoichiometric Li_xCu_2−xSe (0<x<0.20) ternary alloys in the temperature range 350–405 °C are presented. It is observed that in the stoichiometric copper selenide the substitution of part of copper by lithium leads to a strong change for the deterioration of ionic transport conditions.     

Intracellular potential relief and size effects in the lattice of a LaF3 superionic conductor

The potential relief in the lattice of a LaF₃ crystal is calculated by quantum-mechanical methods for clusters containing from 24 to 1200 ions. For the dielectric phase, formation energy E _a for defects of the vacancy-interstitial fluorine ion type and potential barrier E _d preventing the motion of fluorine ions are found to grow from minimal values E _a = 0.12 eV and E _d = 0.22 eV for a cluster of 24 ions to maximal values E _a = 0.16 eV and E _d = 0.26 eV for clusters of 576 and 1200 ions. The values of E _a and E _d obtained in quasi-mechanical calculations are in good agreement with those obtained from Raman and quasi-elastic light scattering data.     

Far-infrared absorption of the superionic conductor Li3N. temperature and isotope effects

The far-infrared absorption spectrum (20–250cm^–1) of the superionic conductor Li₃N —with⁶Li- and⁷Li-isotopes in the starting material—has been measured for different polarizations and temperatures (4–150 K). TheE c spectrum yields two lines near 80 and 140 cm^–1, which are not observed forE c. From the isotopic frequency ratio ( ₆/ ₇1.07) and from the comparison to lattice dynamics it is concluded that these lines are due to resonant modes, weakly coupled to the lattice. Measurements of the isotope effects on the dielectric properties (10 Hz to 1 MHz) establish that the local diffusive type motion in shallow potentials and the low lying resonant modes originate from the same defect system (including Li-ions in non-regular positions).     

Resistive switching in the devices of Ag/amorphous Ag30Ge17Se53 films/Pt

Electric switching and memory effects were observed on devices composed of an Ag₃₀Ge₁₇Se₅₃(AGS) film sandwiched between Ag and Pt electrodes. The amorphous AGS films were prepared by the pulsed-laser deposition method and the lateral size of devices was scaled down to 1 μm by the focused ion beam nanofabrication technique.     

Temperature dependences of phonon and mobile-ion spectra in superionic conductor CuBr

The temperature dependence of far-infrared reflectivity spectra in sintered CuBr has been measured from 18 to 570 K. Phonon and mobile-ion parameters are evaluated by the fitting procedure with the factored form of the dispersion relation. A strong fourth order anharmonicity is assigned. Estimated values of optical dielectric constant and optical ionic mobility μ_op decrease with increasing temperature within a limited temperature region. For μ_op value, the effects of mobile ion scattering by optical phonons and of the expansion of interionic distance are discussed with respect to the phonon damping constant and the ionic character of the interionic force.     

Photo-induced dynamical changes in amorphous As2S3 films

Optical properties of amorphous As₂S₃ films, which have been illuminated well by bandgap light in advance, can be changed dynamically by exposing to less-bandgap light. This dynamical change has been studied in connection with its plausible relation to the reversible photo-induced change. It has been found that these changes have intimate connections with each other, and can be explained by a certain configurational diagram in a coherent fashion.     

Anisotropic conductivity in a channel-structured superionic conductor: Li2Ti3O7

From measurements on single crystals of Li₂Ti₃O₇, the conductivity is determined to be predominately ionic with an anisotropy of $\text{σ}{}_{\mathrm{b}}\text{σ}{}_{\mathrm{a}}\text{≈4}$ and $\text{σ}{}_{\mathrm{c}}\text{σ}{}_{\mathrm{b}}\text{≈7}$. This anisotropy is significant but is not sufficient to classify this channel-structured ramsdellite material as a one-dimensional conductor. A conduction path through the ramsdellite crystal structure consistent with the determined anisotropy is presented.