Superionic conductors with tysonite structure: evidence for a distribution of motional correlation times from19F-NMR data

¹⁹F NMR spectroscopy was used to analyze the onset of the fluorine mobility in monocrystalline LaF₃. The method is sensitive to ionic exchange with correlation times in the range of 10⁻⁶ - 10⁻³s. For the temperature range between 240 K and 400 K the motion is restricted mainly to the sites in the F₁ sublattice and characterized by a strongly heterogeneous behavior which can be well described by a broad distribution of correlation times. The distribution of the correlation times and its variation with temperature reflects the potential energy landscape in the superionic state. The changes in the center position and width of the distribution with temperature differ from an Arrhenius law behavior. Ionic mobility on the microscopical scale, therefore, can not be considered a simple thermally activated process. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Temperature-dependent nepheloxetic shift of the 5 D 0→7 F 0 luminescence line of a Eu3+ ion in a superionic Na5Y(:Eu)Si4O12 single crystal

A decrease in the wavelength of the ⁵ D ₀→⁷ F ₀ luminescence line of a Eu³⁺ ion in a single crystal of the superionic conductor Na₅Y(:Eu)Si₄O₁₂ is observed as a consequence of raising the temperature. The effect is interpreted as the result of a change in the distribution of mobile Na⁺ cations in the second coordination sphere of the luminescing rare-earth ion. Fiz. Tverd. Tela (St. Petersburg) 39, 1997–2000 (November 1997)     

Dufour effect in superionic copper selenide

The Dufour effect has been observed in the superionic conductor copper selenide, Cu_2−x Se. This effect is the opposite of the Soret thermal diffusion effect which was previously only observed in gaseous and liquid systems. Fiz. Tverd. Tela (St. Petersburg) 40, 242–244 (February 1998)     

Structure and Ionic Conductivity of Halocomplexes of Main Group Metallic Elements Studied by NMR and NQR

Li₃InBr₆ undergoes phase transition to a lithium superionic conductor at T _tr = 314 K (σ = 5.0 × 10⁻⁴ S cm⁻¹ at 330 K). The Rietveld analysis and the DSC measurement suggested that the positional disorder is introduced at the cationic sites above T _tr. The X-ray powder diffraction pattern at the superionic phase changes gradually with temperature and finally shows a simple powder pattern at 420 K which is quite similar to that of LiBr. This rock salt structure contains intrinsic vacancies because one In³⁺ and two vacancies substitute for three Li⁺. ⁷Li and ¹¹⁵In NMR support the rapid diffusion of the Li⁺ and the introduction of the In³⁺ into the rock salt structure. On the other hand, the ionic conductivity for Na₃InCl₆ was 10⁻⁵ S cm⁻¹ even at 500 K. Conduction path for the sodium ions could be proposed by means of the Rietveld analysis and the NMR experiment using a single crystal.     

Mechanism for the influence of the geometric parameters on the electrical characteristics of Penning ion sources

A steady-state Penning ion source is studied experimentally. Depending on the geometric parameter l _a (the anode length to diameter ratio) and pressure, maxima are observed in the discharge current and in the ion beam current extracted from an aperture at the center of the cathode. It is shown that at pressures of the order of 10⁻⁴ Torr, two maxima appear in these currents: one, for short discharge gaps with l _a =1–1.5, corresponds to a diverging ion beam, and the other, for longer anodes with l _a =4–5, to a collimated ion beam. At pressures of the order of 10⁻⁵ Torr, only one maximum appears in these currents, for short anodes l _a =2–3 with a diverging ion beam. A physical explanation is proposed for these findings. Zh. Tekh. Fiz. 68, 29–32 (September 1998)     

Effect of carbon ion bombardment and surface oxidation on the twinning rate of single-crystal bismuth

A study is made of the change in the dependences of the normal velocity of twinning boundaries on the magnitude of shear stresses in the twinning plane v _n =v _n (τ) in bismuth crystals owing to ion-cluster doping and oxidation of the irradiated surface. Irradiation was by 25 keV carbonions at a dose of 10¹⁷ ion/cm². Twinning of the crystals took place under pulsed loading conditions with pulse durations of 10⁻⁵−10⁻⁴ s and stress amplitudes of (0.2–2.0)×10³ g/mm³. Carbon ion bombardment of single-crystal bismuth causes a shift in the v _n =v _n (τ) curve toward lower stresses. An oxide film slows down the motion of twinning dislocations. Zh. Tekh. Fiz. 69, 130–131 (May 1999)     

Experimental and computational study of the passage of an electron beam through the curvilinear element of the Drakon stellarator system in a tenuous plasma

Results are presented from the first stage of studies on the passage of an electron beam with energy 100–500 eV in a magnetic field of 300–700 Oe through the curvilinear solenoid of the KRéL unit, the latter being a prototype of the closing segment of the Drakon stellarator system, in the plasma-beam discharge regime. The ion density at the end of the curvilinear part of the chamber, n _i ≈8×10⁸–10¹⁰ cm⁻³, the electron temperature T _e ≈4–15 eV, and the positions at which the beam hits the target for different distances from it to the electron source are determined experimentally. The motion of the electron beam is computationally modeled with allowance for the space charge created by the beam and the secondary plasma. From a comparison of the experimentally measured trajectories and trajectories calculated for different values of the space charge, we have obtained an estimate for the unneutralized ion density of the order of 5×10⁷ cm⁻³. Zh. Tekh. Fiz. 69, 22–26 (February 1999)     

Sodium superionic conductor sputter-deposited coatings

Thin sodium superionic conductor (Nasicon) coatings are deposited on rotating substrates by co-sputtering in the reactive mode of a Zr-Si and a Na₃PO₄ target. The influence of the discharge current and of the target-to-substrate distance is investigated owing to the targeted Na₃Zr₂Si₂PO₁₂ stoichiometry. A thermo-structural analysis shows that the amorphous as-deposited coating of convenient composition crystallises around 700 °C in the monoclinic structure. Electrical measurements performed at room temperature after various annealing treatments indicate a ionic conductivity of about 2·10⁻³ S·cm⁻¹, consistent with that of bulk Nasicon. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Superionic conductivity of the heterovalent solid solutions R 1−x M x F 3−x (R=REE, M=Ca, Ba) with tysonite-type structure

The fluorine-ion conductivity of anion-deficient solid solutions R _1−x Ca_xF_3−x and R _1−x Ba_xF_3−x having the tysonite (LaF₃) structure was investigated by the impedance spectroscopy method. R _1−x Ca_xF_3−x (R=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho) and R _1−x Ba_xF_3−x (R=La, Pr, Nd) single crystals were grown from the melt by the Bridgman-Stockbarger method. The electrophysical measurements were performed in the frequency range 5−5×10⁵ and temperature range 300–700 K. The temperature dependences of the electrical conductivity for the crystals studied is determined by the migration of fluorine anions along various structural positions. It is shown that, from the standpoint of increasing the conductivity of tysonite matrices RF₃ (R=La, Pr, Nd), doping by CaF₂ and BaF₂ is less promising than SrF₂. Fiz. Tverd. Tela (St. Petersburg) 41, 638–640 (April 1999)     

New approach to treating the energetics of activation processes in the lattice of superionic conductors with intrinsic structural disorder

Using LaF₃-type superionic trifluorides as an example, it is shown that the intrinsic thermal structural disorder not affecting the symmetry of the lattice is embodied in light inelastic scattering spectra. Tools for analyzing the Arrhenius-like temperature dependence of the activation energy of disordering in the superionic conductor lattice are discussed. It is found that activation energy ΔEa found from the temperature dependence of the Raman line width is many times lower than energy Ea responsible for LaF₃ lattice disordering.     

Polymer–ion–clay interaction based model for ion conduction in intercalation-type polymer nanocomposite

A series of polymer nanocomposite films based on intercalation of (PAN)₈LiCF₃SO₃ into the nanometric clay channels of an organomodified clay has been prepared using the standard solution-casting technique. The role of organoclay concentration on polymer–ion interaction, ion–ion interaction, and ion–clay interaction in clay-based nanocomposite films has been analyzed using Fourier transform infrared (FTIR) analysis. Substantial ion dissociation is observed even at a very low clay loading (1–2 wt.%) in the nanocomposites. FTIR results suggest the presence of both uncoordinated CF₃SO₃ ⁻ (free-anions) and ion pairs in the nanocomposite evidenced by changes in CF₃SO₃ ⁻ symmetry from C3ν to Cs and marked asymmetry in the profile of degenerate δ_d(CF₃ ⁻) mode. The experimental results suggest a direct correlation of clay-assisted ion dissociation process with variation in conductivity (σ _dc) and glass transition temperature (T _g) as a function of clay concentration. A model has been proposed to explain the observed correlation on the basis of polymer–ion–clay interaction. The proposed scheme of ion transport mechanism appears to be consistent with the experimental observation.     

Fast magnetic relaxation, studied by microwave absorption in neutron-irradiated YBa2Cu3O7−x ceramic

A contactless microwave method is used to measure the fast magnetic relaxation of granular ceramic samples of YBa₂Cu₃O_7−x irradiated by neutrons with fluences of 10¹⁶–10¹⁹ cm⁻². An experimental study of the time dependence of the relaxation of high-frequency (rf) absorption (f=100 MHz) after the action of an external magnetic field pulse has shown the magnetic relaxation times τ ₀ to be in the time interval of 0.5–150 ms. The rf-absorption mechanism is discussed in terms of an intergranular system with a thermally activated flux of vortices and their diffusion in the granular medium. Fiz. Tverd. Tela (St. Petersburg) 39, 977–981 (June 1997)     

Optical properties of the ternary compound Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se:Co

We present the results of experimental studies of the optical properties of cobalt-doped Cd _x H_1−x Se (x = 0.18) single crystals with cobalt ion concentrations of NCo = 5·10¹⁸, 5·10¹⁹, and 1·10²⁰ cm⁻³ at T = 90 K and 300 K. The composition (x = 0.18) of the Cd _x Hg_1−x Se solid solution was selected so that the hypothetical resonance level is found on the bottom of the conduction band. We show that the cobalt ions in the mercury selenide can form a resonance donor level only for cobalt concentrations N_Co < 5·10¹⁸ cm⁻³. For N_Co ∼ 5·10¹⁸ cm⁻³, the cobalt ions substitute for mercury atoms, forming a solid solution and leading to an increase in the bandgap width and a change in the physical properties. The solubility of cobalt in the HgSe lattice can be greater than 5%–10%. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 73–77, January–February, 2007.     

Magnetic and electrical properties of Mg1−x CuxO solid solutions and magnetic shielding in Cu-Mg1−x CuxO structures

Mg_1−x Cu_xO solid solutions having an NaCl structure with 0⩽x⩽0.20 are synthesized and Cu-Mg_1−x Cu_xO structures are prepared for superconductivity studies. The magnetic susceptibility χ, electron paramagnetic resonance (EPR), and electrical conductivity of the solid solutions are studied at temperatures of 5–550 K. It is shown that χ ⁻¹(T) obeys the Curie-Weiss law with a paramagnetic Curie temperature Θ close to zero and an effective magnetic moment μ _eff=1.9 μ _B, close to the 1.73 μ _B of a Cu²⁺ ion with spin S=1/2. The width ΔH of the EPR line depends weakly on temperature and increases as x is raised. The volume narrowing of the EPR linewidth ΔH is used to estimate the exchange interaction parameter, 3×10⁻⁴ eV. The g-factor is close to 2 and is temperature independent. The electrical conductivity of Mg_1−x Cu_xO at T=300 K is ≈10⁻¹¹–10⁻¹² Ω⁻¹ cm⁻¹ for x=0 and increases to 10⁻⁵–10⁻⁶ Ω⁻¹ cm⁻¹ for x=0.15–0.20. The conductivity is p-type. Magnetic shielding is observed in Cu-Mg_1−x Cu_xO structures with x=0.15 and 0.20. The possible connection of this phenomenon with interference superconductivity in the contact layer of the structure is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 293–296 (February 1999)     

Nature of conduction via impurities in uncompensated silicon

The static conductivity σ(E) and photoconductivity (PC) at radiation frequencies ħω=10 and 15 meV in Si doped with shallow impurities (density N=10¹⁶−6×10¹⁶ cm⁻³, ionization energy ε₁≃45 meV) with compensation K=10⁻⁴−10⁻⁵ in electric fields E=10–250 V/cm are measured at liquid-helium temperatures T. Special measures are taken to prevent the high-frequency part of the background radiation (ħω>16 meV) from striking the sample. It is found that the conductivity σ(E) is due to carrier motion along the D ⁻ band, which is filled with carriers under the influence of the field E. In fields E<E _q (E _q ≃100–200 V/cm) the carrier motion consists of hops along localized D ⁻ states in a 10–15 meV energy band below the bottom of the free band (energy ε=ε₁); for E>E _q carriers drift along localized D ⁻ states with energy ε∞ε₁−10 meV. An explanation is proposed for the threshold behavior of the field dependence of the photo-and static conductivities. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 4, 232–236 (25 August 1997)     

Field dependence of spin-lattice relaxation of Nd3+ ions in Y3Al5O12 crystals

Our studies involve measuring spin-lattice relaxation times for Nd³⁺ ions in yttrium-aluminum garnets over the temperature range 4–50 K at 9.25 and 36.4 GHz for different orientations of the external magnetic field in relation to the crystallographic axes. The temperature dependence of the relaxation rate is described by T ₁ ⁻¹ =AT ⁿ+b exp(−Δ/kT), where n varies from sample to sample, with n=1 for “perfect” samples (i.e., with the longest relaxation times). Here Δ is approximately 130 cm⁻¹, which is the energy of the excited Kramers doublet of the neodymium ion closest to the ground state, and this makes it possible to interpret the second term in T ₁ ⁻¹ as the contribution of two-stage relaxation proceeding through the intermediate level Δ. A strong field dependence of these processes has been discovered: when the frequency was increased fourfold, the relaxation rate increased by a factor of 10. The effect is a specific manifestation of the degeneracy of the excited level, breaking of the symmetry of the crystalline field due to lattice defects, and the prevalence of deformations of a certain type in the spin-lattice interaction. Zh. éksp. Teor. Fiz. 111, 332–343 (January 1997)     

Doppler spectroscopy of a beam in the channel of a H− ion source

It is shown that high-accuracy contact-free measurements of the divergence and emittance of an accelerated H⁻ ion beam at the exit from the source can in principle be performed by passive Doppler spectroscopy of a beam of excited hydrogen atoms produced by neutralization of the ions with excitation on the residual gas in the source channel. The intensity of the H_α-line radiation detected by the Doppler system is calculated, taking into account the principal processes leading to the excitation and deexcitation of the 3s, 3p, and 3d levels of the hydrogen atoms in the beam, for residual gas densities of the order of 10⁻⁴–10⁻⁵ Torr in the source channel. The computed H_α-line intensity was confirmed experimentally, making it possible to perform photoelectronic detection of the spectral contour of the line in the current mode rather than the photon-counting mode. Zh. Tekh. Fiz. 68, 15–18 (June 1998)     

Effect of mixed glass formers on the crystallization kinetics in AgI–Ag<Subscript>2</Subscript>O–V<Subscript>2</Subscript>O<Subscript>5</Subscript>–MoO<Subscript>3</Subscript> glassy superionic system

The crystallization and glass transition kinetics using differential scanning calorimetry (DSC) in 50AgI–33.33Ag₂O–16.67[(V₂O₅)_1−x –(MoO₃) _x ] superionic glassy system is discussed. Thermal stability of glass, studied using various criteria, does not vary significantly with glass former variation. However, the activation energies for structural relaxation (E _s) at glass transition temperature and crystallization (E _c) obtained using Moynihan and Kissinger, Matusita-Sakka formulations found to exhibit interesting trends with MoO₃ substitution in the glass matrix. It is noticed that the electrical conductivity (σ)–temperature (T) cycles obtained at a typical heating rate of 1 °C/min do exhibit significant thermal events. The conductivity after first heating cycle at room temperature is found to be increasing with MoO₃ content and maximum for x = 0.3 (~10⁻³ Ω⁻¹ cm⁻¹ at 30 °C) which is comparable to that of the host 50AgI–33.33Ag₂O–16.67V₂O₅ glassy system. The parameters obtained from σ–T plots and DSC scans do complement each other in a particular range of composition.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Measurement of ionic conductivity of poly (<Emphasis Type="Italic">N</Emphasis>-vinylimidazole) and its fluoroborate salt in solid state

The conductivity of poly(N-vinylimidazole) (PVIM) and its fluoroborate salt (PVIM–HBF₄) are reported here. N-vinylimidazole is polymerized by free radical method and PVIM–HBF₄ is prepared by acidification of PVIM with HBF₄. The polyelectrolyte so formed has been characterized by infrared, hydrogen-1 nuclear magnetic resonance, thermogravimetric analyzer, and differential scanning calorimetry. Frequency and temperature dependence of AC conductivity has been studied to learn about the electrical conduction behavior in the materials. The electrical conductivity of the new material is found to be in the range of 10⁻⁵ to 10⁻⁶ S cm⁻¹.There is about 10²- to 10³-fold increase in conductivity of the polyelectrolyte. The material is shown to be a predominantly ionic conductor with t _ion ≈ 0.88. Apparent activation energies are found to be 0.397 and 0.250 eV for the polymer and the polyelectrolyte, respectively.