Coulomb zero bias anomaly for fractal geometry and conductivity of granular systems near the percolation threshold

A granular system slightly below the percolation threshold is a collection of finite metallic clusters, characterized by wide spectrum of sizes, resistances, and charging energies. Electrons hop from cluster to clusters via short insulating “links” of high resistance. At low temperatures all clusters are Coulomb blockaded and the dc-conductivity σ is exponentially suppressed. At lowest T the leading transport mechanism is variable range cotunneling via largest (critical) clusters, leading to the modified Efros-Shklovsky law. At intermediate temperatures the principal suppression of ρ originates from the Coulomb zero bias anomaly occurring, when electron tunnels between adjacent large clusters with large resistances. Such clusters are essentially extended objects and their internal dynamics should be taken into account. In this regime the T-dependence of ρ is stretched exponential with a nontrivial index, expressed through the indices of percolation theory. Due to the fractal structure of large clusters the anomaly is strongly enhanced: it arises not only in low dimensions, but also in d = 3 case.     

Surface electromagnetic waves supported by nano conducting layers with inhomogeneities in the conductivity profile

Conducting interfaces and nano conducting layers can support surface electromagnetic waves. Uniform charge layers of non-zero thickness and their asymptotic behavior toward conducting interfaces of infinitely small thicknesses, where the thin charge layer is modeled via a surface conductivity σ _s , are already studied. Here, the possible effects of inhomogeneity in the conductivity profile of the thin conducting layers are investigated for the first time and a new approximate yet accurate enough analytical formulation for mode extraction in such structures is given. In order to rigorously analyze the structure and justify the proposed approximate formulation, the Galerkin’s method with Legendre polynomial basis functions is applied, i.e. the transverse electric field for the TE polarized surface waves and the transverse magnetic field for the TM polarized surface waves are each expanded in terms of Legendre polynomials and then each eigenmode; subjected to appropriate boundary conditions, is sought in the complete space spanned by Legendre basis functions. The proposed approximate solution is then proved to be accurate. In particular, sinusoidal fluctuations are introduced into formerly uniform conductivity profiles and it is numerically demonstrated that surface electromagnetic waves supported by nano conducting layers are not much sensitive to the very shape of conductivity profiles.     

The σK coupling in the chiral unitary approach and the isoscalar ¯N , ¯A interaction

We evaluate the “σ " exchange contribution to the ˉN → ˉN scattering within a chiral unitary approach. We show that the chiral transition potentials for ππ → Kˉ in the t -channel lead to a “σ " contribution that vanishes in the ˉ forward direction and, hence, would produce a null “σ " exchange contribution to the K^- optical potential in nuclear matter in a simple impulse approximation. This is a consequence of the fact that the leading-order chiral Lagrangian gives an I = 0 ππ → Kˉ amplitude proportional to the squared momentum transfer, q². This finding poses questions on the meaning or the origin of “σ " exchange potentials used in relativistic mean-field approaches to the K^- nuclear self-energy. This elementary “σ ” exchange potential in ˉN → ˉN is compared to the Weinberg-Tomozawa term and is found to be smaller than the present theoretical uncertainties but will be relevant in the future when aiming at fitting increasingly more accurate data.     

Intrinsic tunnelling effects in self-doped La0.89MnO3 single crystals

Transport properties of self-doped La_0.89MnO₃ single crystals with Néel temperature of T_N ≈139 K have been investigated in wide temperature range 10–300 K. Data suggests that current at low temperature is conducted through a strongly temperature-dependent, but almost bias independent channel operating in parallel with a bias controlled but temperature independent channel. The first channel is associated with transport across an insulating antiferromagnetic matrix while the latter one represents tunnel conductivity through intrinsic tunnel junctions appearing due to interruption of conducting percolating paths by phase separated insulating inclusions. Tunnel character of the conductivity manifests itself in nonlinear current-voltage characteristics and appearance of a zero-bias anomaly in the form of a prominent conductance peak in the vicinity of zero bias. Zero bias anomaly and V-shaped characteristics of the differential conductance at high voltages are ascribed to the formation of local magnetic states in the insulating region of the tunneling junction.     

Material parameters for thermoelectric performance

The thermoelectric performance of a thermoelement is ideally defined in terms of the so-called figure-of-meritZ = α²σ/λ, where α,σ and λ refer respectively to the Seebeck coefficient, electrical conductivity and thermal conductivity of the thermoelement material. However, there are other parameters which are fairly good indicators of a material’s thermoelectric ‘worth’. A simple yet useful performance indicator is possible with only two parameters — energy gap and lattice thermal conductivity. This indicator can outline all potentially useful thermoelectric materials. Thermal conductivity in place of lattice thermal conductivity can provide some additional information about the temperature range of operation. Yet another performance indicator may be based on the slope of α vs. ln σ plots. α plotted against ln σ shows a linear relationship in a simplified model, but shows a variation with temperature and carrier concentration. Assuming that such a relationship is true for a narrow range of temperature and carrier concentration, one can calculate the slope m of α vs. ln σ plots against temperature and carrier concentrations. A comparison between the variation ofZT and slopem suggests that such plots may be useful to identify potential thermoelectric materials.     

Ion transport and solid state battery studies on a new silver molybdate superionic glass system: x[0.75AgI: 0.25AgCl]: (1-x)[Ag2O: MoO3]

Preparation, material characterization, ion transport and battery discharge characteristic studies are reported for a new silver molybdate glass system: x[0.75AgI: 0.25AgCl]: (1-x)[Ag₂O: MoO₃], where 0<x<1 in molar weight fraction. The traditional host AgI has been replaced by an alternate compound: “a quenched [0.75AgI: 0.25 AgCl] mixed system/solid solution”. Electrical conductivity (σ), ionic mobility (μ) and mobile ion concentration (n) measurements were carried out as a function of “x”. The composition: 0.8[0.75AgI: 0.25AgCl]: 0.2[Ag₂O: MoO₃] exhibited the highest conductivity (∼ 6×10⁻³ S·cm⁻¹) at room temperature and has been referred to as ‘optimum conducting composition (OCC)’. The compositional variation of “μ” and “n” revealed that the enhancement in the room temperature conductivity of OCC is predominantly due to the increase in mobile ion concentration. The XRD and DSC analysis on OCC indicated the formation of glassy phase with partial presence of unreacted polycrystalline phase of the host salt. The temperature dependence of various ionic transport parameters viz. “σ”, “μ”, “n” and ionic transference number (t_ion) were carried out on the OCC and the results have been discussed on the basis of theoretical models suggested for superionic glasses. In addition to this, solid state batteries were fabricated using OCC as electrolyte and discharge characteristics were studied under varying load conditions.     

Correlation between work hardening and stress relaxation in polycrystalline nickel

Stress-relaxation rates at a constant strain in A-grade nickel polycrystals has been reported to depend in a peculiar manner on the initial stress levelσ ₀ at which relaxation is allowed to start. For large grains (D>75μm),s varies withσ ₀ linearly over the entire stress strain curve. For small grains (D<75μm),s-σ ₀ curve undergoes a change in its slope at a critical value of plastic strainɛ, which decreases as grain size increases. The observation referred to are found to correlate well with the work-hardening behaviour of the nickel polycrystals.     

Electrical properties,equivalent circuit,and dielectric relaxation studies on [(C<Subscript>3</Subscript>H<Subscript>7</Subscript>)<Subscript>4</Subscript>N]<Subscript>2</Subscript>Cd<Subscript>2</Subscript>Cl<Subscript>6</Subscript> polycrystalline

The Ac electrical conductivity and the dielectric relaxation properties of the [(C₃H₇)₄N]₂Cd₂Cl₆ polycrystalline sample have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 209 Hz–5 MHz and 361–418 K, respectively. The purpose is to make a difference between the electrical and dielectric properties of the polycrystalline sample and single crystal. Besides, a detailed analysis of the impedance spectrum suggests that the electrical properties of the material are strongly temperature-dependent. Plots of (Z" versus Z') are well fitted to an equivalent circuit model consisting of a series combination of grains and grains boundary elements. Moreover, the temperature dependence of the electrical conductivity in the different phases follows the Arrhenius law and the frequency dependence of σ (ω) follows the Jonscher’s universal dynamic law. Furthermore, the modulus plots can be characterized by full width at half height or in terms of a nonexperiential decay function φ(t) = exp(t/t)^β. Finally, the imaginary part of the permittivity constant is analyzed with the Cole–Cole formalism.     

Quasi-one dimensional electrical conductivity and thermoelectric power studies on a discotic liquid crystal

We have studied the electrical conductivity of well aligned samples of hexahexylthiotriphenylene (HHTT) in the pure as well as doped states. The dopant used was a small concentration (0.62 mole %) of the electron acceptor trinitrofluorenone (TNF). In the columnar phases, doping causes the AC(1 kHz) conductivity along the columnar axis (σ _‖) to increase by a factor of 10⁷ or more relative to that in undoped samples; σ _‖ attains a value of 10⁻²S/m, which was the maximum measurable limit of our experimental set up. On the other hand, in the isotropic phase doping makes hardly any difference to the conductivity. The frequency dependence of the conductivity has been investigated. The DC conductivity of doped samples exhibits an enormous anisotropy, σ _‖/σ _⊥ ≥ 10¹⁰, which is 7 orders higher than that reported for any liquid crystalline system, and, to our knowledge, the largest observed in an organic conductor. We also report the first thermoelectric power studies on these ‘molecular wires’. The sign of the thermoelectric power is in conformity with the expected nature of the charge carriers, namely, holes.     

Electrical properties of nickel-doped arsenic trisulphide

Results of temperature and frequency dependent a.c. conductivity of pure and nickel-doped a-As₂S₃ are reported. The a.c. conductivity of pure As₂S₃ obeys a well-known relationship: σ_ac ∝ω ^s. Frequency exponents is found to decrease with increasing temperature. Correlated barrier hopping (CBH) model successfully explains the entire behaviour of a.c. conductivity with respect to temperature and frequency for pure As₂S₃. But a different behaviour of a.c. conductivity has been observed for the nickel doped As₂S₃. At higher temperatures, distinct peaks have been observed in the plots of temperature dependence of a.c. conductivity. The frequency dependent behaviour of a.c. conductivity (σ_ac ∝ω ^s) for nickeldoped As₂S₃ is similar to pure As₂S₃ at lower temperatures. But at higher temperatures, ln σ_ac vs lnf curves have been found to deviate from linearity. Such a behaviour has been explained by assuming that nickel doping gives rise to some neutral defect states (D ^0′) in the band gap. Single polaron hopping is expected to occur between theseD ^0‘ andD ⁺ states. Furthermore, allD ⁺,D ^0′ pairs are assumed to be equivalent, having a fixed relaxation time at a given temperature. The contribution of this relaxation to a.c. conductivity is found to be responsible for the observed peak in the plots of temperature dependence of a.c. conductivity for nickel-doped As₂S₃. The entire behaviour of a.c. conductivity with respect to temperature and frequency has been explained by using CBH and “simple pair” models. Theoretical results obtained by using these models, have been found to be in agreement with the experimental results.     

Analysis of infrared reflectivity of conducting polymers: example of camphor-sulphonic-acid-doped polyaniline

The reflectivity spectrum of a polyaniline CSA-doped in presence of m-cresol has been measured over the wide wavenumber range of 15- 9 000 cm ^-1 (0.002-1.1 eV) at room temperature. Experimental data compare well with similar experiments performed by another group. The conductivity spectrum of this conducting polymer has been deduced from the reflectivity spectrum by means of two methods, Kramers-Kronig transformation and best fit of an “extended Drude” model to the reflectivity spectrum. Whereas the deviation from Drude behavior was interpreted in terms of Anderson localization or by inhomogeneous disorder by other groups, it is shown here that a different model developed for conducting oxides that also exhibit non-Drude behavior, applies very well to this example of conducting polymer. Received 11 February 1999 and Received in final form 26 April 1999     

Frequency dependent magnetoconductivity and conductivity study in Ni-dispersed silica nano-composite produced by sol-gel technique

The low frequency (20 Hz to 1 MHz) ac conductivity and magnetoconductivity behaviour of ceramic nanocomposite (Ni-SiO₂) at low temperature down to 77 K are reported. The frequency dependent conductivity followed the power law, σ(ω) ∝ ω ^s . The fractional exponent s is a function of temperature and was found to increase with increasing temperature. This type of variation may be attributed to small polaron hopping. A peak present in the loss tangent indicates the presence of a Debye relaxation process. The magnetoconductivity of the samples is positive, which strongly depends on frequency. A firm theoretical explanation of frequency dependent magnetoconductivity is still lacking.     

Preparation and characterization of co-doped (Ce0.80La0.15Al0.05O1.90) and multiple-doped (Ce0.80Sm0.10Gd0.05Al0.05O1.90 and Ce0.80Gd0.10Sm0.05Al0.05O1.90) ceria

Attempts have been made to synthesize a few compositions Ce_0.80La_0.15Al_0.05O_1.90, Ce_0.80Sm_0.10Gd_0.05Al_0.05O_1.90, and Ce_0.80Gd_0.10Sm_0.05Al_0.05O_1.90 by citrate–nitrate auto-combustion method. The aim of the present investigation was to study the effect of co-doping and multiple doping on the ionic conductivity of CeO₂ for its use as solid electrolyte in intermediate temperature solid oxide fuel cells. XRD patterns showed that all the samples have fluorite-type crystal structure similar to undoped ceria. Microstructures of thermally etched samples have been studied by scanning electron microscopy. Contributions of grains σ _g and grain boundaries σ _gb to the total conductivity σ _T, have been determined using impedance analysis. Impedance measurements were made in the frequency range 1 Hz–1 MHz and temperature range 250–500 °C. Our experimental results show that multiple doping is more effective than co-doping for improving the oxide ion conductivity of ceria in the materials investigated in the present study.     

Kinetic demixing and grain boundary conductivity of yttria-doped zirconia part I - experimental observations

This work is directed towards a comprehensive study on the role of the microstructure and local chemistry of grain boundaries on the ionic conductivity of yttria (9 mol%)-stabilized zirconia and YSZ-alumina composites. It has been performed on samples prepared from two batches of YSZ powders containing ≈1.0 or 1.6 wt% SiO₂. Electrical conductivity measurements show that the grain boundary conductivity (σ_gb) increases with the sintering temperature and the cooling rate at the end of sintering or when the amount of Si in the ceramic decreases. Alumina additions lead to a decrease in σ_gb of the samples containing 1.0 wt% SiO₂, while σ_gb passes through a maximum in the highly silicon contaminated materials. These results coupled with TEM X-ray microanalysis, which have shown important gradients of the concentration ratio Al/Si in the grains, near the second phase, and in the glassy precipitates, suggest a competitive effect between the insulating alumina particles and the strong interaction of Al₂O₃ for SiO₂, removing it from grain boundary localities. On the other hand, XPS analyses show that Si and Y segregate near the interfaces. Analysis of these results suggests a kinetic demixing process and allow us to explain the beneficial effect of a faster cooling rate at the end of sintering by the lower amount of Si rejected in grain-boundary localities. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Structural and dielectric studies of lead-free ceramics: Na1/2Y1/2TiO3

The polycrystalline samples of Na_1/2Y_1/2TiO₃ were prepared by the mixed-oxide method. A preliminary X-ray structural analysis was shown to exhibit the formation of a single-phase compound with an orthorhombic structure. Microstructural analysis by scanning electron microscopy (SEM) exhibits well defined grains distributed uniformly through out the sample suggesting the compactness and homogeneity of the sample. Detailed studies of dielectric properties of Na_1/2Y_1/2TiO₃ in a wide frequency range (102–106 Hz) at different temperatures (31–500°C) show a dielectric anomaly at 105°C, which may be related to a ferroelectricparaelectric phase transition as suggested by hysteresis loop at room temperature. An ac conductivity (σ _ac) of the material is mainly governed by the polaron hopping mechanism, which is also influenced by both frequency and temperature. The activation energy was obtained from the plot of temperature with a.c. conductivity.      

Quantum chemical study of electronic and dynamic properties of metal and mixed non-stoichiometric clusters

The aim of this contribution is to show that quantum chemistry has suitable tools to extract the specific properties of small metallic and mixed non-stoichiometric clusters which cannot be obtained by extrapolation from the bulk properties to the atom. For this purpose, first the main features of the methods used for the calculations of the ground and excited states of clusters valid at zero temperature (T=0) will be sketched and the factors determining accuracy of results will be pointed out. The structural and optical response properties of cationic Na _n ⁺ clusters as a function of size will be presented and compared with experimental data. The series of non-stoichiometric alkali-halide clusters containing single and multiple excess electrons will serve as prototypes to study a possible “metal-insulator transition” and “segregation into metallic and ionic parts” in finite systems. Second, an outline of ab initio molecular dynamics methods based on gradient corrected density functional approach with gaussian basis used for determination of temperature dependent ground state properties will be presented. Different temperature behavior of distinct type of structures will be illustrated on an example of Li ₉ ⁺ cluster. Presented by V. Bonačić-Koutecky at the International Conference on “Atomic Nuclei and Metallic Clusters”, Prague, September 1–5, 1997. This work has been supported by the Deutsche Forschungsgemeinschaft (SFB 337, Energy transfer in molecular aggregates) and the Consiglio Nationale delle Ricerche (CNR, Rome).     

Ac electrical parameters of Al-ZnPc-Al organic semiconducting films

The ac electrical parameters of thermally evaporated zinc phthalocyanine, ZnPc, semiconducting thin films was measured in the temperature range of 180–390 K and frequency between 0.1 and 20 kHz. Aluminum electrode contacts were utilized to sandwich the organic ZnPc semiconducting films. Capacitance and loss tangent decreased rapidly with frequency at high temperatures, but at lower temperatures a weak variation is observed. An equivalent circuit model assuming ohmic contacts could qualitatively and successfully explains capacitance and loss tangent behavior. The ac conductivity showed strong dependence on both temperature and frequency depending on the relevant temperature and frequency range under consideration. Ac conductivity σ (ω) is found to vary with ω, as ω ^s with the index s ≤ 1.35 suggesting a dominant hopping conduction process at low temperatures (< 250 K) and high frequency. The conductivity of some samples did not increase monotonically with temperature. This behavior was attributed to oxygen exhaustion of the sample as its temperature is increased. The ac conductivity behavior at low temperatures of ZnPc films could be described well by Elliott model assuming hopping of charge carriers between localized sites.     

Dielectric spectra of LiTFSI-doped chitosan/PEO blends

Solid-polymer-blend electrolyte consisting of chitosan and polyethylene oxide (PEO) in a 1:1 weight ratio and doped with lithium trifluoromethanesulfonimide (LiTFSI) salt was prepared by solution cast technique. The highest conducting film with conductivity value of 1.40 × 10^-6 S cm⁻¹ at room temperature consists of 30 wt% LiTFSI. The temperature dependence for the highest conducting film obeyed Arrhenius relationship. From loss tangent–frequency plots at different temperatures, the frequency f _max at which the plot is a maximum was obtained. From this, ln f _max vs 10³/T was plotted. The activation energy value obtained from the log σ vs 10³/T plot and ln f _max vs 10³/T plot is about the same, suggesting that the processes of conductivity and relaxation for the charge carriers are the same. This paper was presented at the International Conference on Solid State Science and Technology 2006, Kuala Terengganu, Malaysia, Sept. 4–6, 2006.     

Glassy effects in the swelling/collapse dynamics of homogeneous polymers

We investigate, using numerical simulations and analytical arguments, a simple one-dimensional model for the swelling or the collapse of a closed polymer chain of size N, representing the dynamical evolution of a polymer in a Θ-solvent that is rapidly changed into a good solvent (swelling) or a bad solvent (collapse). In the case of swelling, the density profile for intermediate times is parabolic and expands in space as t ^1/3, as predicted by a Flory-like continuum theory. The dynamics slows down after a time ∝N ² when the chain becomes stretched, and the polymer gets stuck in metastable “zig-zag” configurations, from which it escapes through thermal activation. The size of the polymer in the final stages is found to grow as . In the case of collapse, the chain very quickly (after a time of order unity) breaks up into clusters of monomers (“pearls”). The evolution of the chain then proceeds through a slow growth of the size of these metastable clusters, again evolving as the logarithm of time. We enumerate the total number of metastable states as a function of the extension of the chain, and deduce from this computation that the radius of the chain should decrease as 1/ln(ln t). We compute the total number of metastable states with a given value of the energy, and find that the complexity is non-zero for arbitrary low energies. We also obtain the distribution of cluster sizes, that we compare to simple “cut-in-two” coalescence models. Finally, we determine the aging properties of the dynamical structure. The subaging behaviour that we find is attributed to the tail of the distribution at small cluster sizes, corresponding to anomalously “fast” clusters (as compared to the average). We argue that this mechanism for subaging might hold in other slowly coarsening systems. Received 23 October 2000     

Theory of the oscillatory dependence of the conductivity of two-component dielectric composites at room temperatures

It is predicted that at room temperatures a hopping mechanism of charge transfer plays a very important role and leads to temperature oscillations of the conductivity σ(T) of a dielectric composite. The dependence of the conductivity σ(ω) on the frequency of an alternating electric field is calculated. The relation obtained can be used to determine, first, the electron relaxation times and, second, and more importantly, the frequency of electron tunneling through the dielectric matrix from measurements of the conductivity in various frequency ranges. Zh. Tekh. Fiz. 69, 31–34 (March 1999)