Redox control of thermopower and figure of merit in phase-coherent molecular wires

We demonstrate how redox control of intra-molecular quantum interference in phase-coherent molecular wires can be used to enhance the thermopower (Seebeck coefficient) S and thermoelectric figure of merit ZT of single molecules attached to nanogap electrodes. Using first principles theory, we study the thermoelectric properties of a family of nine molecules, which consist of dithiol-terminated oligo (phenylene-ethynylenes) (OPEs) containing various central units. Uniquely, one molecule of this family possesses a conjugated acene-based central backbone attached via triple bonds to terminal sulfur atoms bound to gold electrodes and incorporates a fully conjugated hydroquinonecentral unit. We demonstrate that both S and the electronic contribution Z el T to the figure of merit ZT can be dramatically enhanced by oxidizing the hydroquinone to yield a second molecule, which possesses a cross-conjugated anthraquinone central unit. This enhancement originates from the conversion of the pi-conjugation in the former to cross-conjugation in the latter, which promotes the appearance of a sharp anti-resonance at the Fermi energy. Comparison with thermoelectric properties of the remaining seven conjugated molecules demonstrates that such large values of S and Z el T are unprecedented. We also evaluate the phonon contribution to the thermal conductance, which allows us to compute the full figure of merit ZT = Z el T/(1 + κ p/κ el), where κ p is the phonon contribution to the thermal conductance and κ el is the electronic contribution. For unstructured gold electrodes, κ p/κ el Gt⃒ 1 and therefore strategies to reduce κ p are needed to realize the highest possible figure of merit.

Transport properties of strongly correlated metals: A dynamical mean-field approach

The temperature dependence of the transport properties of the metallic phase of a frustrated Hubbard model on the hypercubic lattice at half-filling is calculated. Dynamical mean-held theory, which maps the Hubbard model onto a single impurity,Anderson model that is solved self-consistently, and becomes exact in the limit of large dimensionality, is used. As the temperature increases there is a smooth crossover from coherent Fermi liquid excitations at low temperatures to incoherent excitations at high temperatures. This crossover leads to a nonmonotonic temperature dependence for the resistance, thermopower, and Hall coefficient, unlike in conventional metals. The resistance smoothly increases from a quadratic temperature dependence at low temperatures to large values which can exceed the Mott-Ioffe-Regel value ha/e(2) (where a is a lattice constant) associated with mean free paths less than a lattice constant. Further signatures of the thermal destruction of quasiparticle excitations are a peak in the thermopower and the absence of a Drude peak in the optical conductivity. The results presented here are relevant to a wide range of strongly correlated metals, including transition metal oxides, strontium ruthenates, and organic metals.

Electrical transport properties of CuS single crystals

Electrical resistivity, transverse magnetoresistance and thermoelectric power measurements were performed on CuS high quality single crystals in the range 1.2-300 K and under fields of up to 16 T. The zero field resistivity data are well described below 55 K by a quasi-2D model, consistent with a carrier confinement at lower temperatures, before the transition to the superconducting state. The transverse magnetoresistance develops mainly below 30 K and attains values as large as 470% for a 16 T field at 5 K, this behaviour being ascribed to a band effect mechanism, with a possible magnetic field induced DOS change at the Fermi level. The transverse magnetoresistance shows no signs of saturation, following a power law with field Delta rho/rho(0) proportional to H(1.4), suggesting the existence of open orbits for carriers at the Fermi surface. The thermoelectric power shows an unusual temperature dependence, probably as a result of the complex band structure of CuS.

Preparation and characterisation of certain II-VI, I-III-VI2 semiconductor thin films and transparent conducting oxides

There is an increasing demand for renewable energies due to the limited availability of fossil and nuclear fuels and due to growing environmental problems. Photovoltaic (PV) energy conversion has the potential to contribute significantly to the electrical energy generation in the future. Currently, the cost for photovoltaic systems is one of the main obstacles preventing production and application on a large scale. The photovoltaic research is now focused on the development of materials that will allow mass production without compromising on the conversion efficiencies. Among important selection criteria of PV material and in particular for thin films, are a suitable band gap, high absorption coefficient and reproducible deposition processes capable of large-volume and low cost production. The chalcopyrite semiconductor thin films such as Copper indium selenide and Copper indium sulphide are the materials that are being intensively investigated for lowering the cost of solar cells. Conversion efficiencies of 19 % have been reported for laboratory scale solar cell based on CuInSe2 and its alloys. The main objective of this thesis work is to optimise the growth conditions of materials suitable for the fabrication of solar cell, employing cost effective techniques. A typical heterojunction thin film solar cell consists of an absorber layer, buffer layer and transparent conducting contacts. The most appropriate techniques have been used for depositing these different layers, viz; chemical bath deposition for the window layer, flash evaporation and two-stage process for the absorber layer, and RF magnetron sputtering for the transparent conducting layer. Low cost experimental setups were fabricated for selenisation and sulphurisation experiments, and the magnetron gun for the RF sputtering was indigenously fabricated. The films thus grown were characterised using different tools. A powder X-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive X-ray analysis (EDX) and scanning electron microscopy i (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UV-Vis-NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using the two probe and four probe electrical measurements. Nature of conductivity of the films was determined by thermoprobe and thermopower measurements. The deposition conditions and the process parameters were optimised based on these characterisations.

Colossal thermoelectric power in Gd-Sr manganites

Manganites belonging to the series Gd1−xSrxMnO3 (x=0.3, 0.4 and 0.5) were prepared by wet solid-state reaction and their thermoelectric power was evaluated. Thermoelectric power measurements revealed a peak value at ∼40 K. All the samples exhibited a colossal thermopower at ∼40K and in that Gd0.5Sr0.5MnO3 exhibited a maximum value of ∼35mV/K, which is the largest reported for these class of materials at this temperature. Temperaturedependent magnetisation measurements showed that the samples exhibit a phase transition from paramagnetic to spin-glass–like state at these temperatures. Plausible mechanisms responsible for the observed colossal thermoelectric power in Gd-Sr manganites are discussed

Thermoelectric transport properties through a T-shaped single quantum dot

We study the thermopower, thermal conductance, electric conductance and the thermoelectric figure of merit for a gate-defined T-shaped single quantum dot (QD). The QD is solved in the limit of strong Coulombian repulsion U -> infinity, inside the dot, and the quantum wire is modeled on a tight-binding linear chain. We employ the X-boson approach for the Anderson impurity model to describe the localized level within the quantum dot. Our results are in qualitative agreement with recent experimental reports and other theoretical researches for the case of a quantum dot embedded into a conduction channel, employing analogies between the two systems. The results for the thermopower sign as a function of the gate voltage (associated with the quantum dot energy) are in agreement with a recent experimental result obtained for a suspended quantum dot. The thermoelectric figure of merit times temperature results indicates that, at low temperatures and in the crossover between the intermediate valence and Kondo regimes, the system might have practical applicability in the development of thermoelectric devices. (c) 2010 Elsevier B.V. All rights reserved.

Ecological efficiency in thermoelectric power plants

This work evaluates the environmental impact resulting from the natural gas and diesel combustion in thermoelectric power plants that utilize the combined cycle technology (CC), as regarding to Brazilian conditions according to Thermopower Priority Plan JPP). In the regions where there are not natural gas the option has been the utilization of diesel and consequentily there are more emission of pollutants. The ecological efficiency concept, which evaluates by and large the environmental impact, caused by CO2, SO2, NOx and particulate matter (PM) emissions. The combustion gases of the thermoelectric power plants working with natural gas (less pollutant) and diesel (more pollutant) cause problems to the environment, for their components harm the human being life, animals and directly the plants. The resulting pollution from natural gas and diesel combustion is analyzed, considering separately the CO2, SO2, NO2 and particulate matter gas emission and comparing them with the in use international standards regarding the air quality. It can be concluded that it is possible to calculate thermoelectric power plant quantitative and qualitative environment factor, and on the ecological standpoint, for plant with total power of 41441 kW, being 27 170 kW for the gas turbine and 14271 kW for the steam turbine. The natural gas used as fuel is better than the diesel, presenting ecological efficiency of 0.944 versus 0.914 for the latter, considering a thermal efficiency of 54% for the combined cycle. (c) 2006 Elsevier Ltd. All rights reserved.

Thermoelectric effects in quantum dots

We report a numerical renormalization-group study of the thermoelectric effect in the single-electron transistor (SET) and side-coupled geometries. As expected, the computed thermal conductance and thermopower curves show signatures of the Kondo effect and of Fano interference. The thermopower curves are also affected by particle-hole asymmetry. © 2009 Elsevier B.V. All rights reserved.

Spin-dependent beating patterns in thermoelectric properties: Filtering the carriers of the heat flux in a Kondo adatom system

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The best thermoelectric.

What electronic structure provides the largest figure of merit for thermoelectric materials? To answer that question, we write the electrical conductivity, thermopower, and thermal conductivity as integrals of a single function, the transport distribution. Then we derive the mathematical function for the transport distribution, which gives the largest figure of merit. A delta-shaped transport distribution is found to maximize the thermoelectric properties. This result indicates that a narrow distribution of the energy of the electrons participating in the transport process is needed for maximum thermoelectric efficiency. Some possible realizations of this idea are discussed.

VO: a strongly correlated metal close to a Mott-Hubbard transition

Here, we present experimental and computational evidences to support that rocksalt cubic VO is a strongly correlated metal with non-Fermi-liquid thermodynamics and an unusually strong spin-lattice coupling. An unexpected change of sign of metallic thermopower with composition is tentatively ascribed to the presence of a pseudogap in the density of states. These properties are discussed as signatures of the proximity to a magnetic quantum phase transition. The results are summarized in an electronic phase diagram for the 3d monoxides, which resembles that of other strongly correlated systems. The structural and electronic simplicity of 3d monoxides makes them ideal candidates to progress in the understanding of highly correlated electron systems.

Coherence of polaronic transport in layered metals

Layered systems show anisotropic transport properties. The interlayer conductivity shows a general temperature dependence for a wide class of materials. This can be understood if conduction occurs in two different channels activated at different temperatures. We show that the characteristic temperature dependence can be explained using a polaron model for the transport. The results show an intuitive interpretation in terms of coherent and incoherent quasi-particles within the layers. Further, we extract results for the magnetoresistance, thermopower, spectral function and optical conductivity for the model and discuss application to experiments.

Thermal and electrical currents in nanoscale electronic interferometers

We theoretically study thermal transport in an electronic interferometer comprising a parallel circuit of two quantum dots, each of which has a tunable single electronic state which are connected to two leads at different temperature. As a result of quantum interference, the heat current through one of the dots is in the opposite direction to the temperature gradient. An excess heat current flows through the other dot. Although locally, heat flows from cold to hot, globally the second law of thermodynamics is not violated because the entropy current associated with heat transfer through the whole device is still positive. The temperature gradient also induces a circulating electrical current, which makes the interferometer magnetically polarized.