Transport properties of nonhomogeneous segregated composites

In conductor-insulator composites in which the conducting particles are dispersed in an insulating continuous matrix the electrical connectedness is established by interparticle quantum tunneling. A recent formulation of the transport problem in these kinds of composites treats each conducting particle as electrically connected to all others via tunneling conductances to form a global tunneling network. Here, we extend this approach to nonhomogeneous composites with a segregated distribution of the conducting phase. We consider a model of segregation in which large random insulating spherical inclusions forbid small conducting particles to occupy homogeneously the volume of the composite, and allow tunneling between all pairs of the conducting objects. By solving numerically the corresponding tunneling resistor network, we show that the composite conductivity σ is enhanced by segregation and that it may remain relatively large also for very small values of the conducting filler concentration. We interpret this behavior by a segregation-induced reduction of the interparticle distances, which is confirmed by a critical path approximation applied to the segregated network. Furthermore, we identify an approximate but accurate scaling relation permitting us to express the conductivity of a segregated systems in terms of the interparticle distances of a corresponding homogeneous system, and which provides an explicit formula for σ which we apply to experimental data on segregated RuO2-cermet composites.

Study of novel electronic conductors

Neven Barisic

This thesis presents the results of a concerted effort to understand the complex array of physical properties exhibited by the BaVS3 family of materials. As a 3d1 system, BaVS3 displays a unique collection of correlation-driven phenomena, including a metal-insulator transition driven by spin-density waves and or charge-density waves as well as a pressure-dependent crossover between the non-Fermi-liquid and Fermi-liquid behaviors. In an attempt to better understand these and many other properties, we have undertaken a systematic experimental study of BaVS3 and related compounds. The primary measurements carried out were those of the transport properties, resistivity and thermoelectric power (TEP). Through the construction of specialized measuring apparatuses, we were able to measure simultaneously these transport properties under conditions of variable temperature (from 2 to 600 K), pressure (up to 3 GPa) and magnetic field (up to 12 T). At ambient pressure and in the range of 250 to 600K, BaVS3 shows nearly isotropic but poor metallic behavior with linear temperature dependences of resistivity and TEP and a Curie-like magnetic susceptibility. The nearly isotropic conductivity contrasts with the 1D 2kF fluctuations observed by lowering the temperature below 250 K (at which the first Jahn-Teller structural phase transition occurs) deep in the metallic phase. The fluctuations reveal the 1D aspects of the electronic character, originating from the chain like structure of the material. The salient feature of BaVS3 at ambient pressure is the second order metal-to-insulator (MI) transition at TMI = 69 K, accompanied by the tetramerization (doubling of the 2V unit cell in the chain direction). In addition to the transport measurements, the strong changes in the electrical and magnetic properties of the system around TMI were followed by magnetic susceptibility, angle-resolved photoelectron spectroscopy and frequency-dependent conductivity. By increasing the pressure, the three-dimensionality of BaVS3 is enhanced and the MI phase transition is suppressed to lower temperatures. TEP and magneto TEP measurements in this pressure range revealed the existence of polarons and of spin fluctuations in the metallic phase. The latter can be identified as precursors to the MI transition. Around 1.8 GPa, where TMI ~15 K, the system enters a strongly fluctuating regime, highly sensitive to the magnetic field, the amplitude and the frequency of the measuring current and to a further increase of the pressure. Closely related to these features, the phase boundary collapses and a hysteretic behavior appears in the transport properties and their magnetic-field-dependent counterparts. At a critical pressure of ~2 GPa, a non-Fermi liquid (NFL) state arises (with n~1.5 in the Tn resistivity law between 1 and 15 K) in relation to the proximate Quantum Critical Point. The p-H-T phase diagram of BaVS3 in this region has been explored in some detail with particular emphasis placed upon the relevance of the spin degrees of freedom (on the insulator side) and the role of quantum fluctuations above the critical pressure. Finally, as the pressure is increased further, the conventional Fermi-liquid exponent of n = 2 is obtained. In order to delve further into the subtleties of the MI transition and the NFL behavior, a comparative study was carried out on the sister compounds Bax-1SrxVS3 and BaVS3 and on sulfur-deficient BaVS3. From this study it became apparent that the imposed chemical substitution manifests itself as an additional effective pressure. The inherent disorder of these samples was observed to affect the NFL behavior by reducing the exponent n towards a value of 1, while the apparent ferromagnetic order below 15 K was seemingly independent of pressure. All the observed features are consistent with a relatively simple two-band tight-binding, vanadium-based, model consisting of a wide quasi one-dimensional band hybridized with a rather isotropic narrow band. Within this context, it is concluded that the MI transition is controlled by the Coulomb-interacting electrons of the wide quasi one-dimensional band. Based on this model a new description of the NFL regime has been proposed.

EPFL2005

Solution of the tunneling-percolation problem in the nanocomposite regime

Gianluca Ambrosetti, Claudio Grimaldi, Thomas Maeder, Peter Ryser

We noted that the tunneling-percolation framework is quite well understood at the extreme cases of percolation-like and hopping-like behaviors but that the intermediate regime has not been previously discussed, in spite of its relevance to the intensively studied electrical properties of nanocomposites. Following that we study here the conductivity of dispersions of particle fillers inside an insulating matrix by taking into account explicitly the filler particle shapes and the inter-particle electron tunneling process. We show that the main features of the filler dependencies of the nanocomposite conductivity can be reproduced without introducing any a priori imposed cut-off in the inter-particle conductances, as usually done in the percolation-like interpretation of these systems. Furthermore, we demonstrate that our numerical results are fully reproduced by the critical path method, which is generalized here in order to include the particle filler shapes. By exploiting this method, we provide simple analytical formulas for the composite conductivity valid for many regimes of interest. The validity of our formulation is assessed by reinterpreting existing experimental results on nanotube, nanofiber, nanosheet and nanosphere composites and by extracting the characteristic tunneling decay length, which is found to be within the expected range of its values. These results are concluded then to be not only useful for the understanding of the intermediate regime but also for tailoring the electrical properties of nanocomposites.

2010

Tunneling and percolation transport regimes in segregated composites

Claudio Grimaldi, Biagio Nigro, Peter Ryser

We consider the problem of electron transport in segregated conductor-insulator composites in which the conducting particles are connected to all others via tunneling conductances, thus forming a global tunneling-connected resistor network. Segregation is induced by the presence of large insulating particles, which forbid the much smaller conducting fillers from occupying uniformly the three-dimensional volume of the composite. By considering both colloidal-like and granular-like dispersions of the conducting phase, modeled respectively by dispersions in the continuum and in the lattice, we evaluate by Monte Carlo simulations the effect of segregation on the composite conductivity sigma, and show that an effective-medium theory applied to the tunneling network reproduces accurately the Monte Carlo results. The theory clarifies that the main effect of segregation in the continuum is that of reducing the mean interparticle distances, leading to a strong enhancement of the conductivity. In the lattice-segregation case the conductivity enhancement is instead given by the lowering of the percolation thresholds for first and beyond-first nearest neighbors. Our results generalize to segregated composites the tunneling-based description of both the percolation and hopping regimes introduced previously for homogeneous disordered systems.

2012

Study of novel electronic conductors

Neven Barisic

EPFL2005