The two-dimensional electronic systems (2DESs) have kept surprising physicists for the last few decades. Examples include the integer and fractional quantum Hall effects, cuprate superconductivity, and graphene. This thesis is intended to develop suitable theoretical tools which can be generalized to study new types of 2DESs with strong correlation feature. The first part of this thesis describes the investigation of heterostructures made by Mott insulators. This work is mostly motivated by the significant improvement of techniques for layer-by-layer growth of transition metal oxides in the last few years. We construct a toy model based on generalized Hubbard model complemented with long-ranged Coulomb interaction, and we study it by Hartree-Fock theory, dynamical mean-field theory, and Thomas-Fermi theory. We argue that interesting 2D strongly correlated electronic systems can be created in such heterostructures under several conditions. Since these 2D systems are formed entirely due to the gap generated by electron-electron interaction, they are not addiabatically connected to a noninteracting electron states. This feature makes these 2D systems distinguish from the ones created in semiconductor heterostructures, and they may be potential systems having non-Fermi liquid behaviors. The second part of this thesis is devoted to the study of collective excitations in high-temperature superconductors. One important achievement in this work is to develop a time-dependent mean-field theory for t-U-J-V model, an effective low energy model for cuprates. The time-dependent mean-field theory is proven to be identical to the generalized random-phase approximation (GRPA) which includes both the bubble and ladder diagrams. We propose that the famous 41 meV magnetic resonance mode observed in the inelastic neutron scattering measurements is a collective mode arising from a conjugation relation, which has been overlooked in previous work, between the antiferromagnetic fluctuation and the phase fluctuation of the d-wave superconducting order parameter near momentum ([pi, pi]). Furthermore, we find that this collective mode signals the strength of the antiferromagnetic fluctuations which are responsible for the suppression of the superfluid density in the underdoped cuprates even at zero temperature. Finally, we perform a complete analysis on an effective model with parameters fitted by experimental data of Bi2212 within the GRPA scheme and conclude that the short-range antiferromagnetic interactions which are a remnant of the parent Mott-insulator are more likely the pairing mechanism of the High-T[subscript c] cuprates. / text

This thesis is comprised of three parts. The first part concerns the investigation of the topochemical reduction of LaSrNiRuO₆ in order to prepare LaSrNiRuO₄ via anion deintercalation. The second part discusses the oxide-for-hydride anion exchanges performed in SrV_1-xTi_xO₃, and the resulting SrV_1-xTi_xO_2-yH_1+y reduction products. Finally, the results from redox-neutral topochemical cation exchange reactions conducted in the three-dimensional perovskite structure of NaTaO₃ are presented along with the characterisation of a novel product of composition Ni_0.5TaO₃. The topochemical reduction of LaSrNiRuO₆ using CaH2 was carried out to produce a novel extended oxide phase with composition LaSrNiRuO₄. This phase is composed of sheets of apex-linked Ni¹⁺O₄ and Ru²⁺O₄ squares in a checkerboard ordered arrangement. To the best of our knowledge, this material is the first example of a B-cation ordered infinite-layer oxide phase. The low oxidation states of the transition-metal cations are confirmed by DFT calculations from which a spin moment S = ½ is determined for the nickel while the ruthenium centres adopt an intermediate-spin S = 1 configuration. LaSrNiRuO4 behaves paramagnetically at room temperature. However, upon cooling (T < 250 K) a phase transition is observed in which the nickel spins interact ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. A possible explanation is given for this observation based on an ordered arrangement of local Jahn-Teller distortions. While investigating the preparation of LaSrNiRuO₄, it was observed that different samples of the LaSrNiRuO₆ starting materials exhibited markedly different reactivity. The observed differing reactivity is inconsistent with the crystal structure and composition of the LaSrNiRuO₆ samples, from which all the materials are identical. Careful investigation of the X-ray diffraction data collected from the LaSrNiRuO6 materials revealed that the reactivity of the samples is a consequence of the microstructure. By quenching or slow-cooling the materials during their synthesis, the size of the crystalline domains formed is affected and this in turn is observed to define the extent to which the topochemical deintercalation of oxide anions takes place. A mechanism to explain this effect is presented in which the greater 'plasticity' of small crystalline domains helps to limit the influence of lattice strain during the reaction. Similar with the observations for the LaSrNiRuO₆ phases, it was found that the reactivity of SrV_0.95Ti_0.05O₃ samples towards topochemical oxide-for-hydride exchange is also determined by the characteristics of the starting materials. The cooling rate can lead to phase segregation in SrV_0.95Ti_0.05O₃ samples which in turn affects the reduction behaviour. A modification of the energy profile for the oxide-for-hydride exchange in SrV_1-xTi_xO₃ phases is proposed on the basis of the electronic configuration that the transition-metal cations adopt upon reduction (d²,V³⁺ and d¹,Ti³⁺). Finally, topochemical exchange reactions can also be carried out between cations in complex transition metal oxides when the mobility of the species to be exchanged is sufficiently greater with respect to the host lattice. The preparation of Ni_0.5TaO₃ from exchange of Na⁺ by Ni²⁺ in NaTaO3 represents a synthetic approach not yet widely explored in the long-standing challenge that the preparation of magnetoelectric multiferroic materials represents. The topochemical reactions studied in this work highlight the possibility of directing and modifying the product phases, by tuning features of the reagents. This is in contrast with the limited control available in thermodynamic processes.

La détection infrarouge, autrefois réservée aux applications militaires et spatiales, connait depuis une dizaine d’années une mutation importante et s’ouvre de plus en plus vers des marchés "grand public". Cette démocratisation est principalement liée aux développements rapides que connaissent les technologies utilisant des bolomètres "non refroidis", qui profitent de leurs compatibilités avec les filières de la microélectronique.La technologie utilisée au CEA/LETI repose sur l’utilisation d’un matériau thermomètre à base de silicium amorphe (également noté "a-Si"). Ce dernier comporte de nombreux avantages dont, principalement, son excellente compatibilité avec les outils "classiques" de la microélectronique. Cependant, l’intégration d’un matériau thermomètre plus performant que le a-Si est nécessaire pour répondre aux défis à venir.Conscient de l’importance de cette problématique "matériau" le laboratoire CEA/LETI développe depuis plusieurs années des matériaux à base d’oxydes de métaux de transition déposés en couches minces.Cette étude s’appuie sur l’ensemble des variantes d’oxydes de métaux de transition étudié dans ce cadre. Cette palette de matériaux, qui se sont révélés très différents dans leur structure et, corrélativement, les mesures de transport dans chacun de ces types, nous ont permis de relier structure et mécanismes de conduction spécifiques à chacun. Une attention particulière a été portée aux mesures de TCR, ou « Temperature Coefficient of Resistance », (facteur à maximiser) et de bruit en 1/f (source de bruit à minimiser), les deux paramètres de choix pour le matériau thermistor.Des grandes tendances qui pilotent la performance d’un matériau thermistor pour la bolométrie ont pu être déduites de ces investigations. Les travaux présentés dans cette thèse permettent d’évaluer le potentiel de tel ou tel compétiteur avant d’en entreprendre le développement. / InfraRed detection, formerly reserved to defense and spatial applications, is currently undergoing deep changes which open new opportunities. Uncooled microbolometer technologies, compatible with classical semiconductors processes, are now able to produce low cost thermal imagers and this will open the door to customer markets in a close future.The technology developed in the CEA/LETI laboratory use the amorphous silicon (noted "a-Si") as the thermistor material. This material has many advantages, in particular, its excellent compatibility with the classical tools used in microelectronic industry. However, better performance in the thermistor material is still needed to address future applications.To handle this challenge, CEA/LETI laboratory is currently developing thermistors made of transition metal oxides thin films. The study presented hereby is based on various transition metal oxides samples deposited in the CEA/LETI Laboratory.Characterization of the structure and the electronic transport for each of these samples allowed us to put in evidence correlations between microscopic structure and conduction mechanisms. Two main figures of merit impacting the overall material performance were investigated : the TCR, Temperature Coefficient of Resistance (which must be maximized) and the 1/f noise (which must be minimized).Finally we conclude this work by highlighting majors outlines governing the performance of a thermistor.

Two novel lithium host materials were investigated using structural and electrochemical analysis; the cathode material Li₂CoSiO₄ and the LiMO₂ class of anodes (where M is a transition metal ion). Li₂CoSiO₄ materials were produced utilising a combination of solid state and hydrothermal synthesis conditions. Three Li₂CoSiO₄ polymorphs were synthesised; β[subscript(I)], β[subscript(II)] and γ₀. The Li₂CoSiO₄ polymorphs formed structures based around a distorted Li₃PO₄ structure. The β[subscript(II)] material was indexed to a Pmn2₁ space group, the β[subscript(I)] polymorph to Pbn2₁ and the γ₀ material was indexed to the P2₁/n space group. A varying degree of cation mixing between lithium and cobalt sites was observed across the polymorphs. The β[subscript(II)] polymorph produced 210mAh/g of capacity on first charge, with a first discharge capacity of 67mAh/g. It was found that the β[subscript(I)] material converted to the β[subscript(II)] polymorph during first charge. The γ₀ polymorph showed almost negligible electrochemical performance. Capacity retention of all polymorphs was poor, diminishing significantly by the tenth cycle. The effect of mechanical milling and carbon coating upon β[subscript(II)], β[subscript(I)] and γ₀ materials was also investigated. Various Li[subscript(1+x)]V[subscript(1-x)]O₂ materials (where 0≤X≤0.2) were produced through solid state synthesis. LiVO₂ was found to convert to Li₂VO₂ on discharge, this process was found to be strongly dependent on the amount of excess lithium in the system. The Li₁.₀₈V₀.₉₂O₂ material had the highest first discharge capacity at 310mAh/g. It was found that the initial discharge consisted of several distinct electrochemical processes, connected by a complicated relationship, with significant irreversible capacity on first discharge. Several other LiMO₂ systems were investigated for their ability to convert to layered Li₂MO₂ structures on low voltage discharge. While LiCoO₂ failed to convert to a Li₂CoO₂ structure, LiMn₀.₅Ni₀.₅O₂ underwent an addition type reaction to form Li₂Mn₀.₅Ni₀.₅O₂. A previously unknown Li₂Ni[subscript(X)]Co[subscript(1-X)]O₂ structure was observed, identified during the discharge of LiNi₀.₃₃Co₀.₆₆O₂.

A reação de redução de oxigênio (RRO) foi estudada em eletrocatalisadores formados por nanopartículas de óxidos puros e mistos de metais de transição de Mn, Co e Ni, além de estrutura tipo espinel, e por nanopartículas de Ag, Au e Ag3M (M= Au, Pt, Pd e Cu) suportadas em carbono Vulcan, em eletrólito alcalino. Os óxidos de metais de transição foram sintetizados por decomposição térmica de seus respectivos nitratos e as nanopartículas a base de prata e ouro foram sintetizadas por redução química com borohidreto. Os eletrocatalisadores foram caracterizados por Difratometria e Espectroscopia de Absorção de Raios X (somente para os óxidos de transição). Os materiais a base de óxidos de manganês, mostraram-se com alta atividade para a RRO, para os quais os resultados espectroscópicos in situ evidenciaram a ocorrência da redução do Mn(IV) para Mn(III), na região de início da RRO. Assim, as atividades eletrocatalíticas foram associadas à ocorrência da transferência de elétrons do Mn(III) para o O2. Entretanto, apresentaram forte desativação após ciclagem potenciodinâmica, o que foi associado à formação da fase Mn3O4, conforme indicado por difratometria de Raios X, após os experimentos eletroquímicos, que é eletroquimicamente inativa. Já o material formado pela estrutura do tipo espinel de MnCo2O4 apresentou alta atividade e estabilidade frente à ciclagem e à RRO. A alta atividade eletrocatalítica foi relacionada a ocorrência do par redox CoII/CoIII em maiores valores de potencial em relação ao CoOx e MnOx, devido a interações entre os átomos de Co e Mn no reticulo espinélico. Contrariamente ao observado nos óxidos com maior quantidade de manganês, o espinel mostrou-se altamente estável, o que foi associada à não alteração de sua estrutura no intervalo de potenciais que a RRO ocorre. Para os materiais bimetálicos a base de prata e ouro, os experimentos eletroquímicos indicaram maior atividade eletrocatalítica para o material de Ag3Au/C. Neste caso, a alta atividade foi associada a dois efeitos principais: (i) a um efeito sinergético, no qual os átomos de ouro atuam na região de ativação, favorecendo a adição de hidrogênio e os átomos vizinhos de prata proporcionam a quebra da ligação O-O, conduzindo a RRO pelo caminho de quatro elétrons por molécula de O2; (ii) ao aumento força da ligação Ag-O, devido à interação da Ag com o Au, resultando em maior atividade para a quebra da ligação O-O, aumentando a atividade da Ag para a RRO, em relação à atividade da Ag pura. Assim, a RRO apresentou menor sobrepotencial e maior número de elétrons em Ag3Au/C, quando comparado com as demais nanopartículas bimetálicas. / The oxygen reduction reaction (ORR) was studied on electrocatalysts composed by pure and mixed transition metal oxides of Mn, Co, and Ni, including spinel-like structures, and by Ag, Au, and Ag3M/C (M= Au, Pt, Pd e Cu) bimetallic nanoparticles, in alkaline electrolyte. The transition metal oxides were synthesized by thermal decomposition of their nitrates, and the silver and gold-based nanoparticles by chemical reduction using borohydride. The electrocatalysts were characterized by X-Ray Diffraction and X-Ray Absorption Spectroscopy (in the case of the metal oxides). The manganese-based oxide materials showed high activity for the ORR, in which the in situ spectroscopic results evidenced the Mn(IV) to Mn(III) reduction, in the range of the ORR onset. In this case, the electrocatalytic activities were correlated to the transfer of electron from Mn(III) to O2. However, they presented strong deactivation after several potentiodynamic cycles, which was ascribed to the formation of the electrochemically inactive phase of Mn3O4, as indicated by the XRD results, after the electrochemical experiments. On the other hand, the MnCo2O4 spinel-like material showed high activity and stability for the ORR. Its high electocatalytic activity was attributed to the CoII/CoIII redox pair, taking place at higher potentials, in relation to that of the CoOx e MnOx pure phases, due to the Co and Mn interactions in the spinel lattice. Contrarily to the behavior observed for the manganese-based materials, the spinel oxide presented high stability, which was ascribed to the non alteration of its crystallographic structure in the range of potentials tha the ORR takes place. For the Au and Ag-based materials, the electrochemical experiments indicated higher electrocatalytic activities for Ag3Au/C. In this case, its higher activity as associated to two main aspects: (i) to a synergetic effect, in which the gold atoms act in the activation region, facilitating the hydrogen addition, and the neighboring Ag atoms promoting the O-O bond breaking, leading the ORR to the 4-electrons pathway; (ii) to the increased Ag-O bond strength, due to the electronic interaction between Ag and the Au atoms, resulting in a faster O-O bond breaking, enhancing the electrocatalytic activity of the Ag atoms in the Ag3Au/C nanoparticle, in relation to that on the pure Ag. Therefore, the ORR presented lower overpotential and higher number of electrons in the Ag3Au/C electrocatalyst, when compared to the other investigated bimetallic nanoparticles.

No description available.

Les isolants de Mott sont un exemple parfait de l’impact des corrélations électroniques locales sur les propriétés macroscopiques des matériaux. En variant légèrement le dopage ou la pression, un métal peut se transformer en un isolant. Ces propriétés peuvent être modifiées de manière très rapide en plaçant ces matériaux loin de l'équilibre. Nous avons étudié un prototype de Mott-Hubbard, V2O3 dopé en Cr, en utilisant l'état de l’art des techniques pompe-sonde, à savoir la photoémission résolue en angle, la réflectivité optique, la spectroscopie THz, et la diffraction des rayons X. La réponse électronique du système, après une excitation laser femtoseconde, qui a été maintenue pour chaque expérience à une longueur d'onde de 800 nm, a pu être déconvoluée de la réponse du réseau. Une étude comparative de ces réponses transitoires démontre un fort couplage électron-phonon dans ce prototype de matériau fortement corrélé. Avant thermalisation, le poids spectral est transféré de la bande de Hubbard inférieure vers le gap de Mott. Sur une échelle de temps plus long un état métastable est stabilisé par un changement structural. Pour mieux comprendre la réponse transitoire des isolants de Mott, nous avons également étudié un autre composé de Mott, BaCo1-xNixS2. Les tendances générales des isolants de Mott après photoexcitation ont été analysées en utilisant un modèle à deux orbitales. Nous interprétons que le remplissage du gap comme un changement spécifique des occupations orbitales. / Mott insulators are a perfect example of how local electronic correlations can change macroscopic properties of materials. Varying slightly the doping or the pressure can transform a metal to an insulator. These properties can be modified extremely rapidly by driving these materials far from equilibrium. We have investigated the model Mott-Hubbard material Cr-doped V2O3 using state of the art pump-probe techniques, namely angle resolved photoelectron spectroscopy, optical reflectivity, THz time-domain spectroscopy, and X-ray diffraction. We were able to unequivocally disentangle the electronic and the lattice response of the system to a femtosecond laser excitation, which was kept in all cases at a wavelength of 800 nm. We present a comparative study of these transient responses, which demonstrates the strong electron-phonon coupling of this strongly correlated model material. We show that before thermalization, spectral weight is transferred from the lower Hubbard band towards the Mott gap. On a longer time scale a metastable state is stabilized by the lattice structure. To further understand the transient response of Mott insulators, we have also studied another Mott compound, BaCo1-xNixS2. The general trends of photoexcitation in Mott insulators are analyzed using a two orbital model. We argue that the filling of the gap can be due to a change of the specific orbital fillings.

Transition-metal oxides (TMOs) display numerous fascinating and complex properties, such as mixed-valency, low dimensionality, lattice distortion, and phase transition, etc. These properties arise from the partially filled d- or f-electron shells of TM cations and are often accompanied by the intriguing interplay between degrees of freedom. To understand the complexity of d-electron TMOs, this thesis is primarily focused on studying their underlying electronic structure using X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES), X-ray photoemission spectroscopy (XPS), and resonant inelastic X-ray scattering (RIXS). The measurements at the O K- and TM L-edges are achieved by taking advantage of high-flux and high-resolution synchrotron radiation light with tunable monochromatic photon energy. Four electronically and structurally distinctive oxides are selected as representative TMOs for investigation in this thesis. To begin with, through a comparative study of WO3 and Na0.67WO3 crystals, the narrowing of the conduction band is observed with Na doping and the core-hole energy shift in the O K-edge XAS process is experimentally determined. Indirect and direct band gaps of photoanode WO3 are measured from the resonant XES with polarization-dependent experimental geometry. The other sodium bronze studied is quasi-one-dimensional β-Na0.33V2O5 polycrystalline film. The film stoichiometry, preferential orientation, and orbital anisotropy are well characterized by a variety of photon and electron techniques and compared to density-functional theory (DFT) calculation. The V 3d orbital splitting of β-Na0.33V2O5 is surveyed by the V L-edge RIXS and compared with isoelectronic β-Sr0.17V2O5 regarding distortions to VO6 octahedra. Furthermore, the complex electronic structure of Mott insulators La1-xLuxVO3 is investigated to understand their spin-orbital phase diagram. The effects of rare-earth size on the O 2p hybridization states and the local crystal field of VO6 octahedron are found to agree with the prediction of DFT calculation and the evolution of crystal structure. The changes of experimental spectra with temperature are associated with Jahn-Teller distortion and orbital ordering due to structural phase transition. Lastly, the band structure and low-energy excitations of spinel MnV2O4 are explored using soft x-ray spectroscopies and theoretical calculations. The presence of Hubbard bands and the mixing between V and Mn 3d states are suggested both experimentally and theoretically.

The physics of transition metal oxides is controlled by the combination and competition of several degrees of freedom, in particular the charge, the spin and the orbital state of the electrons. One important parameter responsible for the physical properties is the density of charge carriers which determines the oxidization state of the transition metal ions. The central objective in this work is the study of transition metal oxides in which the charge carrier density is adjusted and controlled via lithium intercalation/deintercalation using electrochemical methods. Lithium exchange can be achieved with a high degree of accuracy by electrochemical methods. The magnetic properties of various intermediate compounds are studied. Among the materials under study the mixed valent vanadium-oxide multiwall nanotubes represent a potentially technologically relevant material for lithium-ion batteries. Upon electron doping of VOx-NTs, the data confirm a higher number of magnetic V4+ sites. Interestingly, room temperature ferromagnetism evolves after electrochemical intercalation of Li, making VOx-NTs a novel type of self-assembled nanoscaled ferromagnets. The high temperature ferromagnetism was attributed to formation of nanosize interacting ferromagnetic spin clusters around the intercalated Li ions. This behavior was established by a complex experimental study with three different local spin probe techniques, namely, electron spin resonance (ESR), nuclear magnetic resonance (NMR) and muon spin relaxation spectroscopies. Sr2CuO2Br2 was another compound studied in this work. The material exhibits CuO4 layers isostructural to the hole-doped high-Tc superconductor La2-xSr2CuO4. Electron doping is realized by Li-intercalation and superconductivity was found below 9K. Electrochemical treatment hence allows the possibility of studying the electronic phase diagram of LixSr2CuO2Br2, a new electron doped superconductor. The effect of electrochemical lithium doping on the magnetic properties was also studied in tunnel-like alpha-MnO2 nanostructures. Upon lithium intercalation, Mn4+ present in alpha-MnO2 will be reduced to Mn3+, resulting in a Mn mixed valency in this compound. The mixed valency and different possible interactions arising between magnetic spins give a complexity to the magnetic properties of doped alpha-MnO2.

Silicon nitride on steel sliding contacts may provide advantageous tribological properties over traditional self-mated pairs, however the friction and wear behavior at high sliding speeds (>1 m/s) is not well understood. Previous studies at low sliding speeds (< 1 m/s) have found that the wear mechanisms change as a function of the operating parameters, e.g. atmosphere, sliding speed, load, and temperature, due to the formation of transition metal oxides such as Fe2O3 and Fe3O4. This study detected transient effects of the dry silicon nitride on steel contact over a range of sliding speeds to understand their relation to tribochemical reactions and the resulting tribological behavior. Two sets of dry silicon nitride on steel experiments were conducted at 1.45 GPa maximum Hertzian pressure. The first set were low sliding speed reciprocating experiments, conducted at an average of 0.06 m/s, conducted at variable operating temperature, ranging from 23 °C to 1000 °C. In the low sliding speed experiments, transitions of the wear mechanism from adhesive wear, to abrasive wear, then to oxidative wear was observed when the operating temperature increased. The second set were high sliding speed experiments, conducted at variable sliding speeds, ranging from 1 m/s to 16 m/s. In the high sliding speed experiments, a transition from adhesive wear to oxidative wear was observed when the sliding speed surpassed 4.5 m/s. The high sliding speed experiments were accompanied by in-situ instrumentation which detected the presence of a tribofilm which correlated to a reduction in friction, and its formation was linked to tribochemical reactions induced by high flash temperatures. Both sets of experiments had a maximum estimated contact temperature of 1000 °C where oxidative wear was prevalent. Although, the low sliding speed experiments underwent severe bulk oxidation and thermal softening effects, while the high sliding speed experiments experienced localized flash heating events with temperatures sufficient to form a semi-coherent tribofilm that was lubricious and significantly improved wear resistance. Therefore, the effects of transition metal oxides in sliding contacts are determined to be significantly influenced on their mechanisms of formation and interrelated to the operating parameters as found for dry sliding silicon nitride on steel contacts.