Thermoelectric properties of high-entropy rare-earth cobaltates

High-entropy concept introduced with a promising paradigm to obtain exotic physical properties has motivated us to explore the thermoelectric properties of Sr-substituted high-entropy rare-earth cobaltates i.e., (LaNdPrSmEu)$_{1-x}$Sr$_x$CoO3 (0 \leq x \leq 0.10). The structural analysis of the samples synthesized using the standard solid-state route, confirms the orthorhombic structure with the Pbnm space group. The Seebeck coefficient and electrical resistivity decrease with rising Sr concentration as well as with an increase in temperature. The multiple A-site ions in high-entropy rare-earth cobaltates result in an improved Seebeck coefficient ({\alpha}) compared to La$_{0.95}$Sr$_{0.05}$CoO$_3$, associated with a decrease in the Co-O-Co bond angle, which further enhances the power factor. The random distribution of cations at the rare-earth site results in a significant lowering of phonon thermal conductivity. As a result, a maximum figure of merit (zT) of 0.23 is obtained at 350K for (LaNdPrSmEu)$_{0.95}$Sr$_{0.05}$CoO$_3$, which is one of the highest values of zT reported at this temperature for oxide materials. This study shows promise to decouple thermoelectric parameters using the high-entropy concept in several materials.Comment: 5 pages, 3 Figure

Novel entropy-stabilized fluorite oxides with multifunctional properties

Development of new high-entropy oxides having configurational entropy dominating the phase stability has become a hot topic since the discovery of rock salt structure entropy-stabilized (ES)(MgCoNiCuZn)O in 2015. Herein, we report a set of novel entropy-stabilized fluorite oxides: Zr0.2Hf0.2Ce0.2Sn0.2Mn0.2O2-{\delta}, Zr0.2Hf0.2Ti0.2Mn0.2Ce0.2O2-{\delta}, Zr0.225Hf0.225Ti0.225Mn0.225Ce0.1O2-{\delta}, and Zr0.2Hf0.2Ti0.2Mn0.2Ce0.1Ta0.05Fe0.05O2-{\delta} synthesized using standard solid-state reaction. These compounds have been investigated using X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy techniques to discern their structural, microstructural, and chemical properties. The configurational-entropy dominated phase stability and hence the entropy stabilization of the compounds is confirmed by cyclic heat treatments. The mismatch in the ionic radii and oxidation state of the cations are the key factors in achieving a single-phase fluorite structure. Further, screening of physical properties including thermal conductivity, optical band gap, magnetic properties, and impedance spectroscopy is discussed. Thermal conductivity of 1.4-1.7 Wm-1K-1 is observed at 300 K and remains mostly invariant across a wide temperature range (300K-1073K), favorable for thermal barrier coating applications. These ES samples have an optical band gap of 1.6-1.8 eV, enabling light absorption across the visible spectrum and hence could be promising for photocatalytic applications. The impedance spectroscopy data of the entropy-stabilized samples reveal the presence of electronic contributions with small activation energy (0.3-0.4 eV) across a temperature range of 298K-423K. These observations in ES fluorite systems show potential for their multifunctional applications via further optimization and confirm the great chemical versatility of entropy-stabilized oxides.Comment: 13 Pages, 9 Figures 1 Tabl

Matériaux céramiques thermoélectriques pour la production d'électricité propre

Ce travail de thèse porte sur l élaboration et la caractérisation des propriétés physiques et chimiques d une nouvelle famille de composés thermoélectriques, et plus particulièrement le composé BiCuSeO. Les composés de cette famille, dite 1111, présentent une structure en couche de type ZrCuSiAs. L une des particularités de cette structure est la nature distincte des couches qui la composent, la couche Bi2O2 étant décrite comme isolante tandis que la couche Cu2Se2 est appelée couche conductrice. L étude approfondie du composé BiCuSeO montre qu en dépit d un facteur de puissance (S ) relativement modéré, ce composé est un matériau thermoélectrique prometteur, notamment à haute température. En effet, BiCuSeO présente une conductivité thermique remarquablement faible, qui permet d atteindre des facteurs de mérite relativement élevés. De plus, BiCuSeO présente de nombreuses voies d améliorations possibles. L une d elle concerne l étude d un dopage aliovalent sur le site du bismuth. L analyse des résultats a montré que l insertion d un élément divalent permet d optimiser la concentration des porteurs de charges, entrainant ainsi une forte augmentation du facteur de mérite du composé. Une autre voie possible d exploration est l étude de l influence de l ion chalcogène, au travers notamment de la substitution du sélénium par le tellure, avec l obtention d une solution solide complète BiCuSe(1-x)Te(x)O. L étude des propriétés électriques des composés de cette série a permis de mettre en évidence la présence d une transition métal semi-conducteur métal pour les fractions de tellure inférieures à 0.5. Ainsi, bien que l influence du tellure sur le facteur de puissance soit relativement limitée en raison de cette anomalie, des résultats intéressants ont été obtenus pour les fractions de tellure élevées. Par ailleurs, des problématiques autour d une méthode de synthèse alternative du matériau ainsi que sa stabilité sous air sont également abordées dans ce travail.This thesis addresses the issues of the elaboration and the characterization of the chemical and physical properties of a new family of thermoelectric materials, the oxychalcogenides with the general formula BiCuSeO. This compound, called 1111, cristallises in the ZrCuSiAs structure-type. One feature of this structure lies in the fact that the layers are considered as electronically distinct: the Bi2O2 layers are described as the insulating layers whereas the chalcogenide layers Cu2Se2 are presented as the conductive ones. The study of BiCuSeO exhibits that in spite of a relatively moderate power factor (S ), this compound is very promising as possible thermoelectric material, especially at high temperature. Indeed, BiCuSeO shows a remarkably low thermal conductivity, which can achieve relatively high figures of merit. In addition, BiCuSeO offers many ways for improvement. One of them concerns the study of aliovalent doping on the bismuth site. The results showed that the insertion of a divalent element optimizes the charge carriers concentration, leading to a sharp increase in the figure of merit of the compound. Another possible way of exploration lies the study of the influence of the chalcogen ion, notably through the substitution of selenium and tellurium, with a complete solid-solution BiCuSe(1-x)Te(x)O. The study of the electrical properties of this solid solution has highlighted the presence of a metal - semiconductor - metal transition for tellurium fractions below 0.5. Thus, although the influence of tellurium on the power factor is relatively limited due to this anomaly, interesting results were obtained for the high tellurium fractions. In addition, issues around an alternative method of synthesis of the material and its stability in air are also discussed in this work.PARIS11-SCD-Bib. électronique (914719901) / SudocSudocFranceF

Electronic phase diagram of NdFe1-xRhxAsO

We report on the electrical resistivity, thermoelectric power and electronic phase diagram of rhodium-doped NdFeAsO. Rhodium doping suppresses the structural phase transition and spin density wave observed in the undoped material, and superconductivity emerges at x close to 0.05, despite the distortion of FeAs4 tetrahedra induced by the large size difference between Rh and Fe elements. The Tc(x) curve is dome-like, and the highest Tc is reached at x = 0.1, with Tconset = 18K. An upturn of the electrical resistivity above Tc has been observed, with a Kondo like behaviour above Tc and a Fermi-liquid behaviour close to room temperature.Comment: 17 pages, 10 figure

Electronic phase diagram of NdFe1-xRhxAsO

We report on the electrical resistivity, thermoelectric power and electronic phase diagram of rhodium-doped NdFeAsO. Rhodium doping suppresses the structural phase transition and spin density wave observed in the undoped material, and superconductivity emerges at x close to 0.05, despite the distortion of FeAs4 tetrahedra induced by the large size difference between Rh and Fe elements. The Tc(x) curve is dome-like, and the highest Tc is reached at x = 0.1, with Tconset = 18K. An upturn of the electrical resistivity above Tc has been observed, with a Kondo like behaviour above Tc and a Fermi-liquid behaviour close to room temperature.Comment: 17 pages, 10 figure

The theoretical account of the ligand field bonding regime and magnetic anisotropy in the DySc₂N@C₈₀ single ion magnet endohedral fullerene

Considering the DySc₂N@C₈₀ system as a prototype for Single Ion Magnets (SIMs) based on endohedral fullerenes, we present methodological advances and state-of-the art computations analysing the electronic structure and its relationship with the magnetic properties due to the Dy(III) ion. The results of the quantum chemical calculations are quantitatively decrypted in the framework of ligand field (LF) theory, extracting the full parametric sets and interpreting in heuristic key the outcome. An important result is the characterization of the magnetic anisotropy in the ground and excited states, drawing the polar maps of the state-specific magnetization functions that offer a clear visual image of the easy axes and account for the pattern of response to perturbations by the magnetic field applied from different space directions. The state-specific magnetization functions are derivatives with respect to the magnetic field, taken for a given eigenvalue of the computed spectrum. The methodology is based on the exploitation of the data from the black box of the ab initio spin–orbit (SO) calculations. The ground state is characterized by the Jz = ±15/2 quantum numbers with easy axis along the Dy–N bond. The implemented dependence on the magnetic field allowed the first-principles simulation of the magnetic properties. The computational approach to the properties of endohedral fullerenes is an important goal, helping to complement the scarcity of the experimental data on such systems, determined by the limited amount of sample

Morphological, structural, optical, and electrical study of nanostructured thin films: Charge transport mechanism of p-type Co3O4

Morphological, structural, optical, and electrical study of nanostructured thin films: Charge transport mechanism of p-type Co3O

In- and out-plane transport properties of chemical vapor deposited TiO2 anatase films

Due to their polymorphism, TiO2 films are quintessential components of state-of-the-art functional materials and devices for various applications from dynamic random access memory to solar water splitting. However, contrary to other semiconductors/dielectric materials, the relationship between structural/morphological and electrical properties at the nano and microscales remains unclear. In this context, the morphological characteristics of TiO2 films obtained by metal–organic chemical vapor deposition (MOCVD) and plasma-enhanced chemical vapor deposition (PECVD), the latter including nitrogen doping, are investigated and they are linked to their in- and out-plane electrical properties. A transition from dense to tree-like columnar morphology is observed for the MOCVD films with increasing deposition temperature. It results in the decrease in grain size and the increase in porosity and disorder, and subsequently, it leads to the decrease in lateral carrier mobility. The increase in nitrogen amount in the PECVD films enhances the disorder in their pillar-like columnar morphology along with a slight increase in density. A similar behavior is observed for the out-plane current between the low temperature MOCVD films and the undoped PECVD ones. The pillar-like structure of the latter presents a lower in-plane resistivity than the low temperature MOCVD films, whereas the out-plane resistivity is lower. The tree-like columnar structure exhibits poor in- and out-plane conductivity properties, whereas pillar-like and dense TiO2 exhibits similar in- and out-plane conductivities even if their morphologies are noticeably different