Chain-forming zintl antimonides as novel thermoelectric materials

Zintl phases, a subset of intermetallic compounds characterized by covalently-bonded "sub-structures," surrounded by highly electropositive cations, exhibit precisely the characteristics desired for thermoelectric applications. The requirement that Zintl compounds satisfy the valence of anions through the formation of covalent substructures leads to many unique, complex crystal structures. Such complexity often leads to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical modes in the phonon dispersion. To date, excellent thermoelectric properties have been demonstrated in several Zintl compounds. However, compared with the large number of known Zintl phases, very few have been investigated as thermoelectric materials.

From this pool of uninvestigated compounds, we selected a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked MSb₄ tetrahedra, where $M$ is a triel element. The compounds discussed in this thesis (A₅M₂Sb₆ and A₃MSb₃, where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related "chain-forming" structure types. This thesis describes the thermoelectric characterization and optimization of these phases, and explores the influence of their chemistry and structure on the thermal and electronic transport properties. Due to their large unit cells, each compound exhibits exceptionally low lattice thermal conductivity (0.4 - 0.6 W/mK at 1000 K), approaching the predicted glassy minimum at high temperatures. A combination of Density Functional calculations and classical transport models were used to explain the experimentally observed electronic transport properties of each compound. Consistent with the Zintl electron counting formalism, A₅M₂Sb₆ and A₃MSb₃ phases were found to have filled valence bands and exhibit intrinsic electronic properties. Doping with divalent transition metals (Zn²⁺ and Mn²⁺) on the M³⁺ site, or Na¹⁺ on the A³⁺ site allowed for rational control of the carrier concentration and a transition towards degenerate semiconducting behavior. In optimally-doped samples, promising peak zT values between 0.4 and 0.9 were obtained, highlighting the value of continued investigations of complex Zintl phases.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Coulomb blockade double-dot Aharonov-Bohm interferometer: Harmonic decomposition of the interference pattern

For the solid-state double-dot interferometer, the phase shifted interference pattern induced by the interplay of inter-dot Coulomb correlation and multiple reflections is analyzed by harmonic decomposition. Unexpected result is uncovered, and is discussed in connection with the which-path detection and electron loss. (C) 2009 Elsevier B.V. All rights reserved.

Shubnikov de Haas oscillations of a two-dimensional electron gas in a modulation-doped Zn0.80Cd0.20Se/ZnS0.06Se0.94 single quantum well

The magnetotransport properties of the two-dimensional (2D) electron gas confined in a modulation-doped Zn0.80Cd0.20Se/ZnS0.06Se0.94 single quantum well structure were studied at temperatures down to 0.35 K in magnetic fields up to 7.5 T. Well resolved 2D Shubnikovde Haas (SdH) oscillations were observed, although the conductivity of the sample in the as grown state was dominated by a bulk parallel conduction layer. After removing most of the parallel conduction layer by wet chemical etching the amplitude and number of SdH oscillations increased. From the temperature dependence of the amplitude the effective mass of the electrons was estimated as 0.17 m(0). Copyright (C) 1996 Published by Elsevier Science Ltd

Morphological study on water-borne conducting polyaniline-poly(ethylene oxide) blends

Conducting polyaniline-poly(ethylene oxide) blends were prepared from their aqueous solutions. The blends displayed an electrical conductivity percolation threshold as low as 1.83 wt % of polyaniline loading. As demonstrated by scanning electron microscopy, polarized optical microscopy, and wide-angle X-ray diffraction studies, the conducting polyaniline took a fibrillar morphology in the blend, and it existed only in the amorphous phase of poly(ethylene oxide). A three-phase model combining morphological factors instead of a two-phase model was proposed to explain the low-conductivity percolation threshold.

Formation and electrical interfacing of nanocrystal-molecule nanostructures

The objective of this thesis work is to develop methods for forming and interfacing nanocrystal-molecule nanostructures in order to explore their electrical transport properties in various controlled environments. This work demonstrates the potential of nanocrystal assemblies for laterally contacting molecules for electronic transport measurements. We first propose a phenomenological model based on rate equations for the formation of hybrid nanocrystal-molecule (respectively: 20 nm – 1.2 nm) nanostructures in solution. We then concentrate on nanocrystals (~ 60 nm) assembled between nano-gaps (~ 40 nm) as a contacting strategy for the measurement of electronic transport properties of thiophene-terminated conjugated molecules (1.5 nm long) in a two-terminal configuration, under vacuum conditions. Similar devices were also probed with a three-terminal configuration using thiophene-terminated oxidation-reduction active molecules (1.8 nm long) in liquid medium for the demonstration of the electrolytic gating technique. The experimental and modelling work presented in this thesis project brings into light physical and chemical processes taking place at the extremely narrow (~1 nm separation) and curved interface between two nanocrystals or one nanocrystal and a grain of a metallic electrode. The formation of molecular bridges at this kind of interface necessitates molecules to diffuse from a large liquid reservoir into the region in the first place. Molecular bonding must occur to the surface for both molecular ends: this is a low yield statistical process in itself as it depends on orientation of surfaces, on steric hindrance at the surface and on binding energies. On the other hand, the experimental work also touched the importance of the competition between potentially immiscible liquids in systems such that (organo-)metallic molecules solvated by organic solvent in water and organic solvent in contact with hydrated citrate stabilised nanocrystals dispersed in solutions or assembled between electrodes from both experimental and simulations point of view.

Spatially-resolved mapping of history-dependent coupled electrochemical and electronical behaviors of electroresistive NiO

Bias-induced oxygen ion dynamics underpins a broad spectrum of electroresistive and memristive phenomena in oxide materials. Although widely studied by device-level and local voltage-current spectroscopies, the relationship between electroresistive phenomena, local electrochemical behaviors, and microstructures remains elusive. Here, the interplay between history-dependent electronic transport and electrochemical phenomena in a NiO single crystalline thin film with a number of well-defined defect types is explored on the nanometer scale using an atomic force microscopy-based technique. A variety of electrochemically-active regions were observed and spatially resolved relationship between the electronic and electrochemical phenomena was revealed. The regions with pronounced electroresistive activity were further correlated with defects identified by scanning transmission electron microscopy. Using fully coupled mechanical-electrochemical modeling, we illustrate that the spatial distribution of strain plays an important role in electrochemical and electroresistive phenomena. These studies illustrate an approach for simultaneous mapping of the electronic and ionic transport on a single defective structure level such as dislocations or interfaces, and pave the way for creating libraries of defect-specific electrochemical responses.

Nonconservative current-driven dynamics: beyond the nanoscale

Long metallic nanowires combine crucial factors for nonconservative current-driven atomic motion. These systems have degenerate vibrational frequencies, clustered about a Kohn anomaly in the dispersion relation, that can couple under current to form nonequilibrium modes of motion growing exponentially in time. Such motion is made possible by nonconservative current-induced forces on atoms, and we refer to it generically as the waterwheel effect. Here the connection between the waterwheel effect and the stimulated directional emission of phonons propagating along the electron flow is discussed in an intuitive manner. Nonadiabatic molecular dynamics show that waterwheel modes self-regulate by reducing the current and by populating modes in nearby frequency, leading to a dynamical steady state in which nonconservative forces are counter-balanced by the electronic friction. The waterwheel effect can be described by an appropriate effective nonequilibrium dynamical response matrix. We show that the current-induced parts of this matrix in metallic systems are long-ranged, especially at low bias. This nonlocality is essential for the characterisation of nonconservative atomic dynamics under current beyond the nanoscale.

Materiais à base de óxidos com estrutura do tipo perovskite e compósitos como ânodos de PCES

This work was focused on the analysis of transport, thermomechanical and electrochemical properties of a series of perovskite-like oxide materials and composites for potential applications as anodes of intermediate-temperature solid oxide fuel cells (SOFCs) with lanthanum gallate and silicate solid electrolytes. The primary attention was centered on A(Mn,Nb)O3-δ (A = Sr, Ca) and (La,Sr)(Mn,Ti)O3-based systems, lanthanum chromite substituted with acceptor-type and variable-valence cations, and various Ni-containing cermets. Emphasis was given to phase stability of the materials, their crystal structure, microstructure of porous electrode layers and dense ceramics, electronic conductivity, Seebeck coefficient, oxygen permeability, thermal and chemical induced expansion, and anodic overpotentials of the electrodes deposited onto (La,Sr)(Ga,Mg)O3- and La10(Si,Al)6O27- based electrolyte membranes. In selected cases, roles of oxygen diffusivity, states of the transition metal cations relevant for the electronic transport, catalytically active additives and doped ceria protective interlayers introduced in the model electrochemical cells were assessed. The correlations between transport properties of the electrode materials and electrochemical behavior of porous electrodes showed that the principal factors governing anode performance include, in particular, electronic conduction of the anode compositions and cation interdiffusion between the electrodes and solid electrolytes. The latter is critically important for the silicatebased electrolyte membranes, leading to substantially worse anode properties compared to the electrochemical cells with lanthanum gallate solid electrolyte. The results made it possible to select several anode compositions exhibiting lower area-specific electrode resistivity compared to known analogues, such as (La,Sr)(Cr,Mn)O3-δ.

Impedance field and transition from thermal to shot noise in Cd1-xZnxTe semi-insulating Ohmic detectors

Within a drift-diffusion model we investigate the role of the self-consistent electric field in determining the impedance field of a macroscopic Ohmic (linear) resistor made by a compensated semi-insulating semiconductor at arbitrary values of the applied voltage. The presence of long-range Coulomb correlations is found to be responsible for a reshaping of the spatial profile of the impedance field. This reshaping gives a null contribution to the macroscopic impedance but modifies essentially the transition from thermal to shot noise of a macroscopic linear resistor. Theoretical calculations explain a set of noise experiments carried out in semi-insulating CdZnTe detectors.

Magnetoresistance at artificial interfaces in the itinerant SrRuO3 ferromagnet

The magnetoresistance across interfaces in the itinerant ferromagnetic oxide SrRuO3 have been studied. To define appropriately the interfaces, epitaxial thin films have been grown on bicrystalline and laser-patterned SrTiO3 substrates. Comparison is made with results obtained on similar experiments using the double-exchange ferromagnetic oxide La2/3Sr1/3MnO3. It is found that in SrRuO3, interfaces induce a substantial negative magnetoresistance, although no traces of the low-field spin tunneling magnetoresistance are found. We discuss these results on the basis of the distinct degree of spin polarization in ruthenates and manganites and the different nature of the surface magnetic layer formed at interfaces.

Magnetic field effect on quantum corrections to the low-temperature conductivity in mettalic perovskite oxides

The transport and magnetotransport properties of the metallic and ferromagnetic SrRuO3 (SRO) and the metallic and paramagnetic LaNiO3 (LNO) epitaxial thin films have been investigated in fields up to 55 T at temperatures down to 1.8 K . At low temperatures both samples display a well-defined resistivity minimum. We argue that this behavior is due to the increasing relevance of quantum corrections to the conductivity (QCC) as temperature is lowered; this effect being particularly relevant in these oxides due to their short mean free path. However, it is not straightforward to discriminate between contributions of weak localization and renormalization of electron-electron interactions to the QCC through temperature dependence alone. We have taken advantage of the distinct effect of a magnetic field on both mechanisms to demonstrate that in ferromagnetic SRO the weak-localization contribution is suppressed by the large internal field leaving only renormalized electron-electron interactions, whereas in the nonmagnetic LNO thin films the weak-localization term is relevant.

Ab Initio Calculations of Structural Evolution and Conductance of Benzene-1,4-dithiol on Gold Leads

By performing at) initio density functional theory (DFT) calculations and electronic transport simulations based on the OFT nonequilibrium Green`s functions method we investigate how the conformational changes of a benzene-1,4-dithiol molecule bonded to gold affect the molecular transport as the electrodes are separated from each other. In particular we consider the full evolution of the stretching process until the Junction breaking point and compare results obtained with a standard semilocal exchange and correlation functional to those computed with a self-interaction corrected method. We conclude that the inclusion of self-interaction corrections is fundamental for describing both the molecule conductance and its stability against conformational fluctuations.

Effects of a quantum measurement on the electric conductivity : Application to graphene

We generalize the standard linear-response (Kubo) theory to obtain the conductivity of a system that is subject to a quantum measurement of the current. Our approach can be used to specifically elucidate how back-action inherent to quantum measurements affects electronic transport. To illustrate the utility of our general formalism, we calculate the frequency-dependent conductivity of graphene and discuss the effect of measurement-induced decoherence on its value in the dc limit. We are able to resolve an ambiguity related to the parametric dependence of the minimal conductivity.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.