Polarons, free charge localisation and effective dielectric permittivity in oxides

This review will deal with several types of free charge localisation in oxides and their consequences on the effective dielectric spectra of such materials. The first one is the polaronic localisation at the unit cell scale on residual impurities in ferroelectric networks. The second one is the collective localisation of free charge at macroscopic interfaces like surfaces, electrodes and grain boundaries in ceramics. Polarons have been observed in many oxide perovskites mostly when cations having several stable electronic configurations are present. In manganites, the density of such polarons is so high as to drive a net lattice of interacting polarons. On the other hand, in ferroelectric materials like BaTiO3 and LiNbO3, the density of polarons is usually very small but they can influence strongly the macroscopic conductivity. The contribution of such polarons to the dielectric spectra of ferroelectric materials is described. Even residual impurities as for example Iron can induce well defined anomalies at very low temperatures. This is mostly resulting from the interaction between localised polarons and the highly polarisable ferroelectric network in which they are embedded. The case of such residual polarons in SrTiO3 will be described in more details, emphasizing the quantum polaron state at liquid helium temperatures. Recently, several non-ferroelectric oxides have been shown to display giant effective dielectric permittivity. It is first shown that the frequency/temperature behaviour of such parameters is very similar in very different compounds (donor doped BaTiO3, CaCu3Ti4O12, LuFe2O4,Li doped NiO,...). This similarity calls for a common origin of the giant dielectric permittivity in these compounds. A space charge localisation at macroscopic interfaces can be the key for such extremely high dielectric permittivity.Comment: 17 pages, 11 figure

Magnetic field tuning of polaron losses in Fe doped BaTiO3 single crystals

Artificial tuning of dielectric parameters can result from interface conductivity in polycrystalline materials. In ferroelectric single crystals, it was already shown that ferroelectric domain walls can be the source of such artificial coupling. We show here that low temperature dielectric losses can be tuned by a dc magnetic field. Since such losses were previously ascribed to polaron relaxation we suggest this results from the interaction of hopping polarons with the magnetic field. The fact that this losses alteration has no counterpart on the real part of the dielectric permittivity confirms that no interface is to be involved in this purely dynamical effect. The contribution of mobile charges hopping among Fe related centers was confirmed by ESR spectroscopy showing maximum intensity at ca T\sim40 K.Comment: Submitte

Interface-driven magnetocapacitance in a broad range of materials

Triggered by the revival of multiferroic materials, a lot of effort is presently undergoing as to find a coupling between a capacitance and a magnetic field. We show in this report that interfaces are the right way of increasing such a coupling provided free charges are localized on these two-dimensional defects. Starting from commercial diodes at room temperature and going to grain boundaries in giant permittivity materials and to ferroelectric domain walls, a clear magnetocapacitance is reported which is all the time more than a few percent for a magnetic field of 90kOe. The only tuning parameter for such strong coupling to arise is the dielectric relaxation time which is reached on tuning the operating frequency and the temperature in many different materials

Linking hopping conductivity to giant dielectric permittivity in oxides

With the promise of electronics breakthrough, giant dielectric permittivity materials are under deep investigations. In most of the oxides where such behavior was observed, charged defects at interfaces are quoted for such giant behavior to occur but the underlying conduction and localization mechanisms are not well known. Comparing macroscopic dielectric relaxation to microscopic dynamics of charged defects resulting from electron paramagnetic resonance investigations we identify the actual charged defects in the case of BaTiO3 ceramics and composites. This link between the thermal activation at these two complementary scales may be extended to the numerous oxides were giant dielectric behavior was found

Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)

The temperature-composition phase diagram of barium calcium titanate zirconate (x(Ba0.7Ca0.3TiO3)(1-x)(BaZr0.2Ti0.8O3); BCTZ) has been reinvestigated using high-resolution synchrotron x-ray powder diffraction. Contrary to previous reports of an unusual rhombohedral-tetragonal phase transition in this system, we have observed an intermediate orthorhombic phase, isostructural to that present in the parent phase, BaTiO3, and we identify the previously assigned T-R transition as a T-O transition. We also observe the O-R transition coalescing with the previously observed triple point, forming a phase convergence region. The implication of the orthorhombic phase in reconciling the exceptional piezoelectric properties with the surrounding phase diagram is discussed

Stoichiometry and Grain Boundaries Control by Spark Plasma Sintering in Ba0.6Sr0.4TiO3:Mn/MgO Composites

LaNbO4/La3NbO7 and LaNbO4/LaNb3O9 cer-cer composites were prepared by impregnating Ca-doped LaNbO4 powder, synthesized by spray pyrolysis, with La- or Nb-precursor solutions. The sintering of the calcined powders was investigated by dilatometry, and dense composites were prepared by conventional sintering, hot pressing, and spark plasma sintering. The particle size of the starting powders was about 50 nm, and the average grain size of the dense materials ranged from 100 nm and upwards, depending on the sintering temperature, sintering procedure, and the phase composition. The unit cell parameters of LaNbO4 showed a finite size effect and approached the cell parameters of tetragonal LaNbO4 with decreasing crystallite size, both for the single-phase material and the composites. The minority phase (La3NbO7 or LaNb3O9) were observed as isolated grains and accumulated at triple points and not along the grain boundaries, pointing to a large dihedral angle between the phases. The calcium-solubility in the minority phases was larger than in LaNbO4, which corresponds well with previous reports. The electrical conductivity of the heterodoped materials was similar to, or lower than, that for Ca-doped LaNbO4

Effect of electric and magnetic stresses on ferroelectric single crystals and ceramics

La présence de charges libres a des conséquences considérables sur les propriétés diélectriques des matériaux. Pour mettre en évidence ces contributions, nous avons étudié l influence de contraintes électriques et magnétiques sur des monocristaux de BaTiO3 dopé Fer et de KTiOPO4 (KTP). Dans BaTiO3, l application d un champ magnétique perturbe le mécanisme de pertes diélectriques résultant de mécanismes polaroniques. Dans le KTP c est la localisation des ions K+ qui est perturbée par un champ électrique comme nous l avons démontré en étudiant la séparation des raies de résonances piézoélectriques. Dans une deuxième partie, nous avons synthétisé et étudié la polarisation de phosphates de composition BaFeTi(PO4)3 and BiFe2(PO4)3. Cependant, l ion Bi3+ n est jamais positionné sur son site d inversion, ce qui est prometteur. Enfin, nous avons étudié la spinelle Co3O4 par spectroscopie diélectrique et RPE et nous avons montré l induction d un état polaire sous l effet d un champ magnétique.The mobility of free charges and its localization mechanism has considerable effect on the dielectric properties of the materials. Therefore single crystal of Fe doped BaTiO3 and KTiOPO4 (KTP) which have predominantly electronic and ionic conductivity respectively were studied under external stresses like electric and magnetic field. The application of external magnetic field affects the hopping of electrons which lead to tuning of polaron losses in BaTiO3 whereas in case of KTP localization of K+ ions give rise to splitting of piezoelectric resonance and it can be tuned by external electric field. In the second part new phosphates of formula BaFeTi(PO4)3 and BiFe2(PO4)3 were synthesized to look for polarization property. However Bi3+ ions are not localized on their inversion symmetry site which is promising. Finally spinel Co3O4 was investigated under dielectric and Electron Paramagnetic Resonance spectroscopy which reveal an induction of polar state under external magnetic field.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF

Evolution des propriétés diélectriques, ferroélectriques et électromécaniques dans le système pseudo-binaire (1-x)BaTi0.8Zr0.2O3- xBa0.7Ca0.3TiO3 / Corrélations structures et propriétés

Ce travail de thèse a pour objectif la caractérisation des propriétés physico-chimiques descéramiques de composition (1-x) BaTi0.8Zr0.2O3-x Ba0.7Ca0.3TiO3 préparées par frittage conventionnelet frittage flash (SPS). Les études structurales réalisées au voisinage du point triple (x 0.32) à l aidede la diffraction des RX de haute résolution (synchrotron) sur poudre ont introduit des modificationsmajeures sur le diagramme de phase température-composition déjà proposé. La réponseélectromécanique géante mesurée est alors corrélée à la dégénérescence du profil de l énergie libreinduite par les instabilités structurales. De plus, la flexibilité de la polarisation sous contraintesthermique et électrique est couplée à un assouplissement de la maille cristalline. Ces deuxcaractéristiques contribuent ensemble à une réponse électromécanique colossale via une forteactivité des murs de domaine. La dégradation des propriétés diélectriques, ferroélectriques etpiézoélectriques pour les céramiques BCTZ (x=0.32 et 0.5) élaborées par frittage flash estessentiellement attribuée aux fluctuations importantes de composition et à la stabilisation de laconfiguration des murs de domaines avec la diminution de la taille des grains.The aim of this work is to make a full characterization of the structural, microstructural, dielectric,ferroelectric and piezoelectric properties of the perovskite-structured oxides (1-x) BaTi0.8Zr0.2O3-xBa0.7Ca0.3TiO3 prepared by a conventional solid-state reaction method (conventional sintering) andSPS fabrication technique. Using high-resolution synchrotron x-ray powder diffraction, the structuralinvestigations carried out close to the triple point (x 0.32) have introduced significant corrections tothe previously published composition-temperature phase diagram. The colossal electromechanicalresponse was then correlated to a strongly degenerate free energy landscape caused by structuralinstabilities. Furthermore, the coupling between the high polarization flexibility under electric andthermal stresses and the lattice softening gives rise to a giant electromechanical response due tohigh domain wall activities. The decrease of the dielectric, ferroelectric and piezoelectric propertiesof BCTZ ceramics (x=0.32 and 0.5) processed by SPS was essentially attributed to the largecompositional fluctuations and stable domain wall configurations as the grain size decreased.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF

Enhancing the ferroelectric performance of P(VDF-co-TrFE) through modulation of crystallinity and polymorphism

The functional properties of P(VDF-co-TrFE) are strongly dependent on its structure, which, in turn, depends on processing conditions applied. In this work we investigate the P(VDF-co-TrFE) processing structure-function relationships, in order to find the thermal conditions that result in optimum ferroelectric performance in thin film configuration. Our results show that annealing temperature affects mostly the remnant polarization value, P, while annealing time has a severe effect on the coercive field, E-c, An optimized ferroelectric functionality, in terms of high P-r of about 90 mC/m(2) and low E-c of 50 MV/m, is achieved and rationalized through structural analysis by means of GIWAXS. The best performing structure exhibits a high degree of crystallinity, a preferential orientation of the crystallites with the polymer chains parallel to the substrate and the occurrence of three ferroelectric phases. A deconvolution study demonstrates the presence of a moderately unstable ferroelectric phase that is designated to facilitate ferroelectric switching. Our findings show that a single step of 15 min annealing at 135 degrees C leads to high performance P(VDF-co-TrFE) structure, proving that the 2 h-long annealing step that is traditionally applied is not necessary. (C) 2018 Elsevier Ltd. All rights reserved.</p

Low-losses, highly tunable Ba0. 6Sr0. 4TiO3/MgO composite

Spark plasma sintering SPS is an efficient tool to obtain highly densified ferroelectric-dielectric ceramic composites with clean interfaces and tunable properties. Dielectric MgO and ferroelectric Ba0.6Sr0.4TiO3 BST were combined in two-dimensional multilayer and three-dimensional random powders design. Their unmodified BST Curie temperature proves the suppression of interdiffusion while dielectric losses are below 0.5% and the tunability is 40% at room temperature. The composites and pure BST with similar densities 95% were obtained, owing reliable comparison of their dielectric properties. Such SPS ceramics can be used as experimental input for simulation and are potential candidates for high frequency applications