Sound Velocity Anomaly at the Mott Transition: Application to Organic Conductors and V2O3

Close to the Mott transition, lattice degrees of freedom react to the softening of electron degrees of freedom. This results in a change of lattice spacing, a diverging compressibility, and a critical anomaly of the sound velocity. These effects are investigated within a simple model, in the framework of dynamical mean-field theory. The results compare favorably to recent experiments on the layered organic-conductor kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Cl. We predict that effects of a similar magnitude are expected for V2O3, despite the much larger value of the elastic modulus of this material.

Strain-responsive polyurethane/PEDOT:PSS elastomeric composite fibers with high electrical conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain-sensing applications. The preparation of homogenous composite formulations from polyurethane (PU) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet-spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re-arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented. Conducting elastomeric fibers based on a composite of polyurethane (PU) and PEDOT:PSS, produced by a wet-spinning method, have high electrical conductivity and stretchability. These fibers can sense large strains by changes in resistance. The PU/PEDOT:PSS fiber is optimized to achieve the best strain sensing. PU/PEDOT:PSS fibers can be produced on a large scale and integrated into conventional textiles by weaving or knitting. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polaronic ferromagnetism in conducting polymers

Ferromagnetic behavior at room temperature is reported in metal-free-conducting polymer samples of poly(3-methylthiophene) doped with ClO 4 -. Magnetic moments associated with spin 1/2 positive polarons are possibly interacting through a Dzialoshinski-Moriya anisotropic superexchange via the dopant anions, giving rise to weak ferromagnetism. © 2001 Elsevier Science B.V. All rights reserved.

Low-temperature structural effects in the (TMTSF)2PF6 and AsF6 Bechgaard salts

We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF) 2PF6 and (TMTSF)2AsF6 (TMTSF: tetramethyl-tetraselenafulvalene). The 4 K neutron-scattering structure refinement of the fully deuterated (TMTSF)2PF6-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)2PF6-H12 salt previously determined at the same temperature. Surprisingly, it is found that deuteration corresponds to the application of a negative pressure of 5×102 MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF 6 and AsF6 salts. Two different thermal behaviors have been distinguished. Small Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies θE = 8.3 K and θE = 6.7 K for the PF6-D12 and AsF6-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large Bragg-angle measurements evidence an unexpected structural change around 55 K, which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)2PF6 is dominated by the librational motion of the PF6 units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: θE ≈ 50 K and θE = 76 K for the PF6-D12 and PF6-H12 salts, respectively. © 2013 American Physical Society.

Magic-angle effects in the interlayer magnetoresistance of quasi-one-dimensional metals due to interchain incoherence

The dependence of the magnetoresistance of quasi-one-dimensional metals on the direction of the magnetic field show dips when the field is tilted at the so-called magic angles determined by the structural dimensions of the materials. There is currently no accepted explanation for these magic-angle effects. We present a possible explanation. Our model is based on the assumption that, the intralayer transport in the second most conducting direction has a small contribution from incoherent electrons. This incoherence is modeled by a small uncertainty in momentum perpendicular to the most conducting (chain) direction. Our model predicts the magic angles seen in interlayer transport measurements for different orientations of the field. We compare our results to predictions by other models and to experiment.

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

Individual grain boundary properties and overall performance of metal-organic-deposition coated conductors

We have investigated single grain boundaries (GBs) isolated in coated conductors produced by Metal-Organic Deposition (MOD). When a magnetic field is swept in the film plane, an angle-dependent crossover from boundary to grain limited critical current density Jc is found. In the force-free orientation, even at fields as high as 8 T, the GBs still limit Jc. We deduce that this effect is a direct consequence of GB meandering. We have employed these single GB results to explain the dependence of Jc of polycrystalline tracks on their width: in-plane measurements become flatter as the tracks are narrowed down. This result is consistent with the stronger GB limitation at field configurations close to force-free found from the isolated boundaries. Our study shows that for certain geometries even at high fields the effect of GBs cannot be neglected.

Insight into local structure and molecular dynamics in organic solid-state ionic conductors

Elucidating the rate and geometry of molecular dynamics is particularly important for unravelling ion-conduction mechanisms in electrochemical materials. The local molecular motions in the plastic crystal 1-ethyl-1-methylpyrrolidinium tetrafluoroborate ([C2 mpyr][BF4 ]) are studied by a combination of quantum chemical calculations and advanced solid-state nuclear magnetic resonance spectroscopy. For the first time, a restricted puckering motion with a small fluctuation angle of 25° in the pyrrolidinium ring has been observed, even in the low-temperature phase (-45 °C). This local molecular motion is deemed to be particularly important for the material to maintain its plasticity, and hence, its ion mobility at low temperatures.

Electrical characteristics of lateral heterostructure organic field-effect bipolar transistors

We describe and discuss the unique electrical characteristics of an organic field-effect transistor in which the active layer consists of a type II lateral heterojunction located approximately midway between the source and drain. The two active semiconductors on either side of the junction transport only one carrier type each, with the other becoming trapped, which leads to devices that operate in only the steady state when there is balanced electron and hole injections from the drain and source. We describe the unique transfer characteristics of such devices in two material systems.

Benefits of current percolation in superconducting coated conductors

The critical currents of coated conductors fabricated by metal-organic deposition (MOD) on rolling-assisted biaxially textured substrates (RABiTS) and by pulsed laser deposition (PLD) on ion-beam assisted deposition (IBAD) templates have been measured as a function of magnetic field orientation and compared to films grown on single crystal substrates. By varying the orientation of magnetic field applied in the plane of the film, we are able to determine the extent to which current flow in each type of conductor is percolative. Standard MOD/RABiTS conductors have also been compared to samples whose grain boundaries have been doped by diffusing Ca from an overlayer. We find that undoped MOD/RABiTS tapes have a less anisotropic in-plane field dependence than PLD/IBAD tapes and that the uniformity of critical current as a function of in-plane field angle is greater for MOD/RABiTS samples doped with Ca. (C) 2005 American Institute of Physics.

Studies On The Electrical Properties Of Some Crystalline Organic Compounds And Conducting Polymers

Solid electrolytes for applications like chemical sensing, energy storage, and conversion have been actively investigated and developed since the early sixties. Although of immense potential, solid state protonic conductors have been ignored in comparison with the great interest that has been shown to other ionic conductors like lithium and silver ion conductors. The non-availability of good, stable protonic conductors could be partly the reason for this situation. Although organic solids are better known for their electrical insulating character, ionic conductors of organic origin constitute a recent addition to the class of ionic conductors. However, detailed studies (N1 such conductors are scarce. Also the last decade has witnessed an unprecedented boom in research on organic "conducting polymers". These newly devised materials show conductivity spanning from insulator to metallic regimes, which can be manipulated by appropriate chemical treatment. They find applications in devices ranging from rechargeable batteries to "smart windows". This thesis mainly deals with the synthesis and investigations on the electrical properties of (i) certain organbc protonic conductors derived from ethylenediamine and (ii) substituted polyanilines

Preparació de nous catalitzadors basats en complexos de Ru i Pd, i el seu ancorament a polímers conductors per a la fabricació de materials multifuncionals

Aquesta tesi doctoral es basa en l'estudi de l'aplicació en catàlisi de dos tipus de complexos organometallics basats en dos metalls de tansició diferents. Concretament s'estudien complexos macrocíclics triolefínics de pal·ladi(0) com a catalitzadors per a les reaccions de Suzuki i Heck, i oxocomplexos carbènics de ruteni(II) com a espècies catalítiques en oxidacions de compostos orgànics. En el cas dels complexos de ruteni s'ha vist que en augmentar el nombre de lligands carbènics en l'esfera de coordinació del metall s'aconseguiex afavorir els processos bielectrònics, obtenint-se catalitzadors més actius i més selectius. En un segon pas, els dos tipus de catalitzadors homogenis s'han immobilitzat sobre la superfície d'un elèctrode mitjançant l'estratègia d'electropolimerització del grup pirrol. Els elèctodes modificats resultants s'han aplicat com a catalitzadors heterogenis. En ambdós casos els catalitzadors heterogenis han mostrat una activitat equiparable o superior a la del sistema homogeni corresponent. Finalment, s'ha assajat una reacció de catàlisi tàndem en què els dos catalitzadors (immobilitzats sobre el mateix elèctrode) actuen en cooperació. S'ha aconseguit realitzar dues transformacions consecutives d'un substat orgànic.

Structural studies of ambient temperature plastic crystal ion conductors

A number of novel organic ionic compounds based on the pyrrolidinium cation are described which have been found to be ion conductors in their solid states around room temperature. The properties of the compounds are consistent with their exhibiting plastic crystal phases. In order to understand some of the molecular origins of the plastic crystal behaviour and the ion conductivity that it promotes, a number of related compounds based on the imidazolium and ammonium cations are also described which have structural elements in common with the pyrrolidinium cation, but which do not show the plastic behaviour. It is found therefore that the nature of the cation is quite critical to the development of this behaviour. The alkyl methyl pyrrolidinium cation is found to produce plastic crystal phases when the alkyl chains are short, thereby preserving the ability of the cation to rotate with minimal steric hindrance. The ammonium and imidazolium cations of comparable size and structure are less able to produce these plastic phases, in many cases because the low temperature phase proceeds to melt rather than forming a stable rotator phase.

Organic ionic plastic crystals : recent advances

Investigations into the synthesis and utilisation of organic ionic plastic crystals have made significant progress in recent years, driven by a continued need for high conductivity solid state electrolytes for a range of electrochemical devices. There are a number of different aspects to research in this area; fundamental studies, utilising a wide range of analytical techniques, of both pure and doped plastic crystals, and the development of plastic crystal-based materials as electrolytes in, for example, lithium ion batteries. Progress in these areas is highlighted and the development of new organic ionic plastic crystals, including a new class of proton conductors, is discussed.