Littérature scientifique sur le sujet « Electronic Properties - Exotic Transition Metal Oxides »

Functional oxides with strongly correlated electron systems, such as vanadium dioxide, manganite, and so on, show a metal-insulator transition and an insulator-metal transition (MIT and IMT) with a change in conductivity of several orders of magnitude. Since the discovery of phase separation during transition processes, many researchers have been trying to capture a nanoscale electronic domain and investigate its exotic properties. To understand the exotic properties of the nanoscale electronic domain, we studied the MIT and IMT properties for the VO2 electronic domains confined into a 20 nm length scale. The confined domains in VO2 exhibited an intrinsic first-order MIT and IMT with an unusually steep single-step change in the temperature dependent resistivity (R-T) curve. The investigation of the temperature-sweep-rate dependent MIT and IMT properties revealed the statistical transition behavior among the domains. These results are the first demonstration approaching the transition dynamics: the competition between the phase-transition kinetics and experimental temperature-sweep-rate in a nano scale. We proposed a statistical transition model to describe the correlation between the domain behavior and the observable R-T curve, which connect the progression of the MIT and IMT from the macroscopic to microscopic viewpoints.

Many transition-metal oxides in elevated valence states [e.g. Mn(V), Co(IV), Ni(III), Cu(III) ] present a metastable character and, given the difficulty of their synthesis, have been relatively little studied. However, they are very interesting materials presenting strong electronic correlations that are bound to exotic properties such as superconductivity, metal behavior, metal–insulator transitions or colossal magnetoresistance. The metastability of these compounds requires special synthesis conditions such as the application of high pressure. In the last years, we have prepared and investigated a good number of materials belonging to several families such as RNiO3 (R = rare earths), Ba3Mn2O8 , (Ba,Sr)CoO3 , La2(Ni,Co)O4+δ , etc. In the study and correct characterization of these oxides it has been decisive the use of elastic neutron diffraction, most of the times in powder samples. This technique has allowed us to access the structural details typically related to the octahedral tilting in perovskite structures, the oxygen stoichiometry and order–disorder of the oxygen sublattice, the distinction between close elements in the Periodic Table, the resolution of magnetic structures and, in general, the establishment of a correlation between the structure and the properties of interest. This letter is organized around the binomial "high-pressure synthesis" and "characterization by neutron diffraction" and illustrated with some selected examples among the metastable materials above mentioned.

With the slowing down of Moore’s law, related to conventional scaling of integrated circuits, alternative technologies will require research effort for pushing the limits of new generations of electronic or photonic devices. Perovskite oxides with the ABO3 chemical formula have a very wide range of interesting intrinsic properties such as metal-insulator transition, ferroelectricity, pyroelectricity, piezoelectricity, ferromagnetic and superconductivity. For the integration of such oxides, it is of great interest to combine their properties with traditional electronic, memory and optical devices on the same silicon-based platform. In the context of high-speed chip-to-chip optical interconnects, compact high-resolution beam steering and video-rate RGB hologram generation require the integration of fast and efficient optical modulators on top of silicon CMOS devices. For these applications the integration of high quality electro-optical materials A defect-free material-stack deposition on silicon wafers is hence required. Among the possible materials options, barium titanate (BaTiO3) is one promising candidate due to its large intrinsic Pockels coefficients that can be obtained. In a first part of the talk, we will review the different options to integrate BaTiO3 on Silicon substrate though different templates to control the polarization direction and discuss the influence on the physical, electrical and optical properties. Then in the second section we will discuss the use of perovskites oxide in the field of topological based qubits which is one of the promising methods for realizing fault-tolerant computations. It is recognized that superconductor/topological insulator heterostructure interfaces may be a perfect host for the exotic “Majorana” particles. These have relevant topological protection nature as required for processing information. Therefore, the physics at the superconductor/topological insulator heterostructure interface need to be studied further, starting at the material level. In this work, a candidate material Barium Bismuthate (BBO) is studied utilizing the Oxide Molecular Beam Epitaxy (MBE) process. The perovskite structure provides opportunity for easily tailored functionality through substitutional doping. Incorporation of potassium into the lattice of BBO results in a superconducting phase with Curie temperature as high as ~ 30K. In addition, BBO is according to DFT based studies, predicted to form topological surface states when doped with Fluorine. In our work, we integrate BBO perovskite on Si(001) substrate, using an epitaxially grown strontium titanate (STO) single-crystalline buffer layer and discuss the structural and chemical properties of the heterostructure will be established by utilizing physical characterization techniques such as AFM, and TEM in later stages. This will go hand in hand with the understanding of the ARPES studies and related surface reconstruction of BBO observed by RHEED as a criterion for the high-quality films. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreements No 864483 and 742299)”.

Transition metal oxides with ABO3 or BO2 structures have become one of the major research fields in solid state science, as they exhibit an impressive variety of unusual and exotic phenomena with potential for their exploitation in real-world applications [...]

As silicon-based transistors have approached their physical limits, it is urgent to explore alternative materials with a suitable bandgap and high mobility for next generation electronic logic devices. Two‐dimensional (2D) materials have attracted significant attention in the last few years due to their potential exotic transport physics and technological applications in various fields, such as a significant device downscaling for high intensity integration. Recently, a variety of 2D materials have been explored, including graphene [1] and transition metal dichalcogenides (TMDs), e.g., MoS2 [2,3], WS2 [4], and PtSe2 [5-7]. Although most research has focused on TMDs, recently 2D layered metal monochalcogenides, e.g., GaSe, have attracted increasing interest as a result of their unique electronic properties, making this class of materials different from TMDs. GaSe crystal structure comprises vertically stacked Ga-Se-Se-Ga layers with relatively weak van der Waals interactions. There are two main GaSe polytypes which differ in the stacking sequence of the basis layer units. Side- and top-view schematics of β‐GaSe and ε‐GaSe are shown in Fig. 1a. In this study, the electronic structure of both GaSe layered material polytypes is investigated using density functional theory (DFT) as implemented in QuantumATK [8]. Brillouin-zone integrations were performed according to the Monkhorst-Pack scheme [9] with a density of approximately 10 k-points per angstrom. Geometry optimizations were performed with the convergence criterion of 0.02 eV/Å [10]. Van der Waals (vdW) interactions improve the structural and electronic properties description obtained by DFT calculations and is included in our calculations through D3 version of Grimme’s dispersion corrections [11]. To provide an improved determination of the bandgap energies, the GW (G: Green's function and W: screened Coulomb interaction) method in conjunction with a many body perturbation theory (MBPT) correction could be used. However, GW technique is computationally very expensive and could be implemented for systems with very limited number of atoms [12,13]. Hence, for this study, methods such as Heyd-Scuseria-Ernzerhof (HSE) hybrid functional [14,15] and GGA-1/2 [16] methods were included in our model to achieve more accurate bandgap compared to the experimental values. The β‐GaSe exhibits a DFT-obtained direct bandgap of ~1 eV while the corrected value is 2 eV. ε‐GaSe, however, shows slight indirect bandgap of 0.8 eV (DFT) and 1.7 eV (corrected), with just 25 meV difference between the indirect gap and indirect gap. A double-gate Schottky barrier field-effect transistor (FET) consisting of Ti source and drain contacts and ultrathin GaSe channel is also investigated. Schematic of the FET is shown in Fig. 1b. The device performance analysis such as current-voltage characteristics, subthreshold slope, and on/off ratio are carried out by means of non-equilibrium Green’s function together with DFT Hamiltonian [17]. The output characteristic of the proposed device exhibits an ON/OFF current ratio of more than 7 orders of magnitude. The presence of point defects in ultrathin 2D films is largely inevitable [18], even under optimized synthesis conditions, which can be either engineered and considered as a useful feature, or undesirable. In either case, understanding the impacts of point defects on the electronic structure of 2D materials are required to allow application-based optimization. In this talk, to provide insight into the defect-induced modifications to the GaSe electronic properties, in particular the properties of the states associated with the defects, we will compare the band-structure of the pristine GaSe with the band-structure of the GaSe with Ge and Se vacancies, for both GaSe polytypes. We have also fabricated back-gated devices by mechanically exfoliating ultrathin GaSe flakes from bulk crystal onto oxide-on-Si substrate. Fig. 1c shows an SEM image of the device. Our experimental results demonstrate the basic transport characteristics of thin-film transistor, which may offer more opportunities for potential applications such as photodetectors, gas sensors, and optoelectronic devices, in addition to nanoelectronics FETs, due to GaSe large bandgap. References: [1] Nature Materials, 6, 183, 2007. [2] 2D Materials, 8, 025008, 2020. [3] 2D Materials, 7, 025040, 2020. [4] ACS Materials Letters, 2, 511, 2020. [5] ACS Omega, 4, pp. 17487-17493, 2019. [6] Advanced Functional Materials, 2103936, 2021. [7] Advanced Functional Materials, 2105722, 2021. [8] J. Phys.: Condens. Matter, 32 015901, 2020 [9] Phys. Rev. B, 13, 5188, 1976. [10] J. Applied Physics, 129, 015701, 2021. [11] J. Chem. Phys., 132, 154104, 2010. [12] J. Phys.: Condens. Matter, 29 065301, 2017. [13] Appl. Phys. Lett., 110, 093111, 2017. [14] J. Chem. Phys. 118, 8207, 2003. [15] Applied Materials Today, 25, 101163, 2021. [16] AIP Advances, 1, 032119, 2011. [17] J. Phys.: Condens. Matter., 30, 414003, 2018. [18] Npj 2D Materials and Applications, 5, 14, 2021. . Figure 1

In this review article, we summarise the key electronic features of transition metal oxides that govern their OER catalytic properties, and how such electronic descriptors are applied for OER electrocatalysts design.

Nanostructures of transition metal di-chalcogenides (TMDCs) exhibit exotic thermal, chemical and electronic properties, enabling diverse applications from thermoelectrics and catalysis to nanoelectronics.

Transition metal oxides constitute a large class of materials with variety of very interesting properties and important technological utility. A subset with perovskite structure has been the subject matter of the current theoretical investigation with an emphasis on their electronic and structural behavior. An analytical and a computational method are used to calculate physical entities like lattice parameters, bulk moduli, band structures, density of electronic states and charge density distributions for various topologies. Results are discussed and compared with the available experimental findings.

Low-dimensional spin systems with S = 1/2 and a singlet ground state attract intensive research efforts because of the quantum nature of their ground state. Since the discovery of the singlet plaquette CaV4O9 compound more attention has been paid to chemical analogues with S = 1/2, V4+ (d1) ions. For example, the V2O5 network exhibits the characteristics of layered and crystallographic shear structures and there is a large vanadium oxide bronze family, MxV2O5 (M = alkali, alkaline earth metals), which shows several original [V2O5] networks. For this reason, the atomic architectures of V2O5 and its derivatives provide a stage where various lower-dimensional quantum critical phenomena can be realised. Compounds in the series LixV2O5 were synthesised via soft chemistry methods and characterised structurally and magnetically via high-resolution x-ray and neutron diffraction and magnetization measurements using a SQUID magnetometer. Additional weaker peaks observed in certain of the diffraction patterns suggested the occurrence of charge ordering of vanadium ions in an incommensurately modulated superstructure for some of the E-LixV2O5 and E'-LixV2O5 phases. Having discovered a possible magnetic transition (Tf ~ 25 K) in one of these dilute-spin phases, Li0.50V2O5, believed to be associated with the low-dimensional, chain-like arrangement of the V4+ (S = 1/2, d1) cations over the non-magnetic V5+(S = 0, d0) network, a local probe, SR, was applied to investigate its ground state and the ground states of other members of the series LixV2O5 with x = 0.55, 0.64 and 0.72 which also exhibit interesting magnetic behaviour. Lack of oscillation in the SR data revealed the absence of any long-range magnetic order for Li0.50V2O5, Li0.55V2O5, Li0.64V2O5, and Li0.72V2O5, supportive of a true one-dimensional ground state, suggesting the formation of domains of one-dimensional antiferromagnetic chains, consistent with the Bonner-Fisher model for low-dimensional magnetic behaviour which provided a good fit to the SQUID data collected.

Cette thèse porte sur les propriétés de transport anormal des oxydes de métaux de transition, en particulier de la surface de SrTiO₃ ou de l’interface entre SrTiO₃ et LaAlO₃. Dans ces systèmes on observe l’apparition de gaz d’électrons bidimensionnels. Des mesures d’Effet Hall non linéaire indiquent que ces gaz sont constitués de plusieurs sortes de porteurs de charge, et que leurs populations varient de manière non monotone sous l’effet du dopage électrostatique. L’effet des propriétés électrostatiques et des corrélations électroniques sur ces variations sont discutées. Celles-ci sont à l’origine de réponses remarquables en ce qui concerne la conversion du spin en charge dans ces systèmes à l’aide d’un modèle de liaisons fortes et de la théorie de la réponse linéaire. Les effets conjoints du spin-orbite atomique et de la brisure de symétrie d’inversion à l’interface verrouille les nombres quantiques de spin, de caractère orbital et d’impulsion des électrons, et induit des textures de spin complexe dans l’espace réciproque. Ces textures sont responsables de l’apparition des effets Edelstein et Hall de spin dans ces hétérostructures et sont caractéristiques de la nature multi-orbitale de ces systèmes électroniques. Enfin nous conduirons une étude ab initio des hétérostructures STO/LAO/STO pour expliquer les observations expérimentales de nouvelles manières de former un gaz d’électrons à ces interfaces d’oxydes. Nous discuterons des rôles respectifs de la chimie, de l’électrostatique et des défauts dans l’apparition de ce gaz
The anomalous transport properties of transition metal oxides, in particular the surface of SrTiO₃ or at the interface between SrTiO₃ and LaAlO₃ is investigated in this thesis. These systems host two-dimensional electron gases. Nonlinear Hall Effect measurements suggest that several species of carriers are present in these systems, and that their population is varying on a nontrivial manner upon electrostatic doping. The role of the electrostatics properties of the electron gas and of the electronic correlations are discussed in this light. Next we discuss the spin to charge conversion of these systems thanks to tight-binding modeling and linear response theory. The complex interplay between atomic spin-orbit coupling and the inversion symmetry breaking at the interface leads to a complex spin-orbital-momentum locking of the electrons, inducing spin textures. These spin textures are responsible for the appearance of the Edelstein and Spin Hall Effect in these heterostructures and are characteristic of the multi-orbital character of these electronic systems. Finally an ab initio study of STO/LAO/STO heterostructures is performed to explain experimental evidence of new ways to produce an electron gas at this interface. The respective roles of the chemistry, electrostatics and defects are discussed

Ces dernières années, les oxydes de métaux de transition ont suscité de grands intérêts du point de vue fondamental et technologique. A cet égard, nous nous concentrons sur deux types d'oxydes : le première, le Perovskite double Pb2FeMoO6, avec un potentiel d'application sur des appareils magnétorésistances et spintroniques ; le deuxième, la zircone ZrO2 avec de excellentes propriétés mécaniques et diélectriques pour être utilisée dans les domaines de matériaux structuraux et fonctionnels. Dans la présente étude, nous utilisons la méthode ab-initio (first-principles calculation) pour étudier les détails des orbites décomposés des structures électroniques et des propriétés magnétiques du Pb2FeMoO6 massif de structure parfaite, massif avec des défauts et en structure de plaque. En même temps, les détails des orbites décomposés des structures électroniques, les propriétés mécaniques, dynamiques et diélectriques de six phases de la ZrO2 (cubique, tétragonale, monoclinique, orthorhombique I (Pbca), orthorhombique II (Pnma) et (Pca21)) ont également été étudiés. D'abord nous allons faire les calculs ab-initio sur les propriétés structurales, électroniques et magnétiques de double pérovskite Pb2FeMoO6 massif avec structure parfaite, massif avec défauts et en structure de plaque. La densité des états orbitaux décomposés montre le champ cristallin octaédrique des six atomes d'oxygène autour de métal de transition (des Fe ou des Mo) et divise les cinq états dégénérés des atomes libres de Fe ou Mo dans un états triplement dégénéré t2g (dxy, dyz et dzx) avec une énergie plus faible et dans un états doublement dégénéré eg (dz2 et dx2-y2) avec une énergie plus élevée. La nature semi-métalliques et les propriétés de transport complètes (100%) de spin de polarisation de Pb2FeMoO6 massif et en structures de plaque reflètent un grand potentiel d’application dans les dispositifs magnéto-résistifs et spintroniques. Le caractère semi-métallique est maintenu pour le composé Pb2FeMoO6 désordonné contenant d’antisites Fe(Mo), de lacunes de VFe, VO ou VPb, alors qu'il disparaît quand les antisites Mo(Fe), les échanges entre Fe-Mo ou les lacunes de VMo sont présents même la concentration de défauts est réduite jusqu'à C = 6,25%. Ainsi, les antisites Mo(Fe), les échanges entre Fe-Mo ou les lacunes de VMo doivent être évités afin de préserver le caractère semi-métallique du composé Pb2FeMoO6 et donc être utilisables dans des dispositifs magnéto-résistifs et spintroniques.Ensuite, basé sur la rigidité élastique constantes individuelle calculée Cij de six phases de ZrO2, les propriétés élastiques et mécaniques des agrégats polycristallins ont été prédits. Nous avons donc examiné le caractère isolant de la phase cubique/tétragonale de ZrO2 sous forme film avec différentes combinaisons et différentes épaisseurs possibles dans des plans avec des faibles indices de Miller [(001), (110) et (111)] (pour la phase cubique) et [(001), (100), (110), (101) et (111)] pour la phase tétragonale. Il se trouve que pour les différentes combinaisons et épaisseurs possibles dans ces trois / cinq plans avec faibles indices de Miller, seulement ZrO2-terminé sous forme d’un film orienté dans le plan (110)/(100) et O-terminé sous forme d’un film orienté (111)/(101) des phases cubique/tétragonale de ZrO2 maintiennent le caractère isolant même les épaisseurs d’empilement est réduit jusqu'à deux et trois couches atomiques. Puisque cubique et tétragonale ZrO2 ont grande anisotropie élastique, comme un exemple, le stress et l'énergie de déformation densité ont été calculées pour tous {hkl} -oriented grains d'un film ZrO2 cubique polycristallin
Transition-metal oxides have attracted exceptional research interest in recent years from both fundamental and technological perspectives. In this respect, we focus on two types of oxides, first, the double perovskite, Pb2FeMoO6 for a potential magnetoresistive and spintronics device application, second, zirconia ZrO2 with great mechanical and dielectric properties can be widely used in both structural and functional material fields. In this thesis we use first-principles calculations (ab-initio) to study systematically the detailed orbital-decomposed electronic structures and magnetic properties of Pb2FeMoO6 in the perfected bulk, defected bulk and slab structures. The detailed orbital-decomposed electronic structures, the mechanical, dynamical and dielectric properties of the ZrO2 in six phases (cubic, tetragonal, monoclinic, orthoI (Pbca), orthoII (Pnma) and (Pca21)) have also been studied.Firstly, considering the comparable ionic radius of Pb2+ (1.49Å) with that of Sr2+ (1.44Å), we propose for the first time to substitute Sr2+ ion with Pb2+ ion in Sr2FeMoO6 and a detailed study has been performed on the Pb2FeMoO6 in the perfected bulk, defected bulk and slab structures. The half-metallic nature and a complete (100%) spin-polarized transport properties reflect the bulk and especially slab Pb2FeMoO6 a potential application in magnetoresistive and spintronics devices; The detailed orbital-decomposed density of states show the octahedral crystal-field of the six oxygen atoms around transition-metal Fe or Mo atoms splits the five-fold degenerate states of the free Fe or Mo atoms into triply degenerate t2g (dxy, dyz and dzx) states with lower energy and doubly degenerate eg (dz2 and dx2-y2) states with higher energy, which cannot be observed in previous partial density of states ( ); The Fe3+ and Mo5+ ions are in the (3d5, s=5/2) and (4d1, s=1/2) states with positive and negative magnetic moments respectively and thus antiferromagnetic coupling via oxygen between them; The half-metallic character is maintained for the disordered Pb2FeMoO6 compounds containing FeMo antisite, VFe, VO, or VPb vacancy, while it vanishes when MoFe antisite, Fe-Mo interchange or VMo vacancy are presented even the defect concentration reduce down to C=6.25%. So the MoFe antisite, Fe-Mo interchange or VMo vacancy defects have to be avoided in order to preserve the half-metallic character of the Pb2FeMoO6 compounds and thus usable in magnetoresistive and spintronics devices.Secondly, based on the calculated individual elastic stiffness constants Cij of six ZrO2 phases, the elastic and mechanical properties of the polycrystalline aggregates have been predicted. We further exam the insulating characters of the cubic/tetragonal ZrO2 slabs with various possible terminations and thicknesses within three [(001), (110) and (111)]/five [(001), (100), (110), (101) and (111)] lower index Miller planes. It is found for the first time that among various possible terminations and thicknesses within these three/five lower index Miller planes, only ZrO2-terminated slabs of the (110)/(100) Miller plane and O-terminated slabs of the (111)/(101) Miller plane of cubic/tetragonal ZrO2 maintain the insulating character and thus usable as a gate dielectric oxide in IC industry even the slab thicknesses reduce down to 2 and 3 atomic layers, respectively; Since cubic and tetragonal ZrO2 have larger elastic anisotropy, both stress and strain energy density have been calculated for all {hkl}-oriented grains of a cubic ZrO2 polycrystalline film as one example

In the 4d transition metal oxides, the extension of the 4d orbitals leads to comparable and thus competitive kinetic and coulomb energies. As a result, small perturbations can induce significant changes in their physical properties, giving rise to a class of exotic phenomena that are rarely found in other materials. The ruthenates materials with readily tunable parameters open an avenue to study the strong electronic correlation in the rarely explored territory: the 4d transition metal oxides. The bilayered system, Ca3Ru2O7, belongs to the Ruddlesden-Popper series in which the physical properties are intimately linked to the lattice degrees of freedom. Ca3Ru2O7, with its quasi-2D and severe structure distortion, is believed to be placed in a unique position at which the role of orbital degrees of freedom is highlighted. The system displays strikingly different behaviors when the field is applied along different crystalline axes. A ferromagnetic (FM) state with full spin polarization is achieved for B||a-axis, but colossal magnetoresistance is realized only for B||b-axis by avoiding the ferromagnetic state. In addition, for B rotating within the ac-plane, slow and strong SdH oscillations periodic in 1/B are observed for T.1.5 K in the presence of metamagnetism. For B|| [110], oscillations are also observed but periodic in B (rather than 1/B) and persist up to 15 K. These properties together with highly unusual spin-charge-lattice coupling near the Mott transition (48 K) are driven by the orbital degrees of freedom. Complex thermodynamic properties are also observed in the other ruthenates system such as Sr4Ru3O10 and Pr3RuO7. The Sr4Ru3O10 is a triple-layered system that shows a dedicate balance between fluctuations and order. Besides the anomaly at TC=102K, anomalous behavior at low temperatures are also observed in the thermal study, indicative of an unusual magnetic order in this material. The Pr3RuO7 shows one-dimensional structure with zig-zag chain of corner sharing RuO6 octahedra running in parallel with the rows of edge-shared PrO8 pseudo-cubes. Magnetic and thermal properties studies on its single crystals indicate that the exchange interaction is strongly anisotropic. A Schottky-type anomaly at low temperature suggests that the gorderedh chain Pr ions are still sensitive to a crystal field.

Amorphous transition metal oxides [aTMOs], have emerged as innovative functional materials for wide-ranging electronic, optical and energy-related applications. However, no systematic and broadly applicable method exists to assess their atomic-scale correlations, and since the optical and electronic processes are local structure-dependent, still there are not well-stablished mechanisms that suitably explain the physical properties of aTMOs. This thesis presents experimental and theoretical studies of the atomic short-range order, optical and electronic properties, and state-defects induced by Li+-ion-intercalation and oxygen-vacancies in amorphous titanium aTiO2 and tungsten aWO3 thin-film oxides. Those properties play a key role for application in high energy-density Li+-ion batteries and in switchable dynamical modulation of solar-irradiation transmittance for energy efficient "smart windows", where the disorder-dependent Li+-ion-intercalation and oxygen-vacancy-induced defect-states influence charge-carrier transfer mechanisms. After introducing the scope of this thesis, the fundamental theoretical concepts describing the experimental findings on amorphous solids are reviewed. Thereafter, a comprehensive analysis on the optical absorption phenomena experimentally observed in oxygen-deficient and Li+-ion-intercalated aLixTiO2−y and aLixWO3−y thin-films and a discussion on the electrochromic properties are presented. The optical absorption is described in the framework of the small polaron absorption model. Finally, a state-of-the-art systematic procedure involving theory and experiment in a self-consistent computational framework is implemented to unveil the atomic-scale structure of aTiO2 and aWO3, and its role for the electronic properties. The procedure is based in Reverse Monte Carlo [RMC] and Finite Difference Method [FDM] simulations of X-ray-Absorption spectra to construct a disordered theoretical model having the same bonding and coordination distribution as the experimental system. Ab-initio molecular dynamics simulations and density functional theory are then used to assess defect-states induced by Li+-ion-intercalation and oxygen-vacancies in aTiO2 and aWO3 oxides. The schemes introduced in this study offer a consistent route to experimentally and theoretically assess the role of the atomic-scale structure on the optical and electronic properties of aTiO2 and aWO3 and could be extended to the study of other aTMOs. The final results provide crucial insight towards the understanding of optical and electronic mechanisms where disorder-dependent ion-intercalation and oxygen-vacancy-induced localized defect-states influence charge transfer mechanisms of crucial importance for wide ranging optical and energy-related application of aTiO2 and aWO3 oxides.

Prior to 2010, most research on the physics and chemistry of transition metal oxides was dominated by compounds of the 3d-transition elements such as Cr, Mn, Fe, Co, Ni, and Cu. These materials exhibited novel, important phenomena that include giant magnetoresistance in manganites, as well as high-temperature superconductivity in doped La₂CuO₄ and related cuprates. The discovery in 1994 of an exotic superconducting state in Sr₂RuO₄ shifted some interest toward ruthenates. Moreover, the realization in 2008 that a novel variant of the classic Mott metal-insulator transition was at play in Sr₂IrO₄ provided the impetus for a burgeoning group of studies of the influence of strong spin-orbit interactions in “heavy” (4d- and 5d-) transition-element oxides. This book reviews recent experimental and theoretical evidence that the physical and structural properties of 4d- and 5d-oxides are decisively influenced by strong spin-orbit interactions that compete or collaborate with comparable Coulomb, magnetic exchange, and crystalline electric field interactions. The combined effect leads to unusual ground states and magnetic frustration that are unique to this class of materials. Novel couplings between the orbital/lattice and spin degrees of freedom, which lead to unusual types of magnetic order and other exotic phenomena, challenge current theoretical models. Of particular interest are recent investigations of iridates and ruthenates focusing on strong spin-orbit interactions that couple the lattice and spin degrees of freedom.

Recent works have suggested that the defect induced magnetism in Diluted Magnetic Semiconductors (DMSs), Transition Metal Oxides (TMOs) and related materials is facilitated and enhanced by codoping and the synergistic action between the codopants. In the present work we demonstrate that the proposed defect synergy is the result of the interplay among correlated spin-polarization processes which take place in a successive way in neighborhoods centered at the codopants and include their first nearest neighbors. These processes result in a reduction in the superexchange coupling which in turn causes an enhancement in the ferromagnetic coupling (FMC) among the magnetic dopants. The proposed FMC is demonstrated using ab initio calculations of the electronic properties of codoped ZnO, GaN and TiO2.

Several oxides of vanadium undergo a transition from a semiconductor or insulating state to a metal phase at a critical temperature. VO2 undergoes this transition near 68°C, while V2O5 undergoes a similar phase transition near 257°C, and V2O3 undergoes a similar transition near 150 K. During the transition a change in oxide crystal structure is accompanied by large changes in electrical and optical behavior. Thin films of vanadium oxides are capable of reversibly switching from the semiconductor to the metallic state at high speeds with high spatial resolution. Therefore, these oxides have potential use, particularly in thin film form, for a wide variety of applications involving thermally activated electronic or optical switching devices. Such films are of considerable technical interest because of applications in chemical sensors, energy-conserving coatings, transparent conductors, and switching materials. The numerous potential electronic, optic, and optoelectronic device applications which have been suggested have stimulated work on the preparation of thin films by a variety of techniques, including chemical vapor deposition, solgel, evaporation, and sputter deposition.