0000000000009823
AUTHOR
Mario Maglione
Isothermal relaxation of discommensurations in K2ZnCl4
At the incommensurate-ferroelectric transition temperature T c of K 2 ZnCl 4 , the dielectric susceptibility contains an anomalous contribution both above and below T c . Previous quasi-static dielectric measurements and hysteresis loops demonstrated that this anomalous part arises from the peculiar dynamics of discommensurations. We have used isothermal dielectric measurements to get some insight into the long time dynamics of these discommensurations. We have found that the characteristic relaxation times τ are of the order of 10 4 s in the incommensurate and in the ferroelectric phase. Even more unusual is a non-monotonous relaxation which is observed in a restricted temperature range ab…
Evidence for a glassy dynamics in (Rb-NH 4 ) 2 SO 4 mixed compounds
An orientational glass behavior is evidenced in a [Rb0.7(NH4)0.3]2SO4 mixed crystal. Dielectric experiments (1 kHz–250 MHz) performed along the c-axis evidenced a polydispersive relaxation process. Its temperature dependence follows a Vogel-Fulcher law with a freezing temperature of 12 K.
Fine grain barium titanate: ferroelectric domains and X-ray diffraction diagram
Through three different studies using various kinds of BaTiO/sub 3/ samples: as a powder while heating over the Curie temperature; as a green ceramic as a function of the forming pressure; as a ceramic while applying a D.C. field. It is shown how X-ray diffraction is able to give information about the evolution of the 90/spl deg/ ferroelectric domain microstructure.
Anisotropic and non-heterogeneous continuum percolation in titanium oxynitride thin columnar films
International audience; We report the percolation behaviour of the conductivity of titanium oxynitride films grown by low-pressure metal-organic chemical vapour deposition, composed of TiNxOy mixed with TiO2. The usual DC parameters (t, s and Φc), obtained from the effective media theory equations, are compared to the universal values (s = sun while t < tun because of the film anisotropy). This is the first example of an electrical continuum percolation applied to columnar films with chemically similar conducting and insulating units (non-heterogeneous percolation) whose mixing is based upon the growth temperature during the film growth.
Dielectric properties of barium strontium titanate / non ferroelectric oxide ceramic composites
International audience; Barium strontium titanate ceramics present high dielectric permittivity and tunability. In order to reduce their permettivity and loss tangent while keeping tunability, various composites of barium strontium titanate oxide...
Influence on the phase transitions of barium titanate of the manganese valency, introduced as a substituant in the titanium site
Abstract A small amount of manganese introduced in BaTiO3 modifies strongly the vibrational and electronic properties of the pure compound. Dielectric response and EPR measurements are reported in order to study the influence of the manganese valency on the ferroelectric-paraelectric phase transition.
DC electrical resistivity of Nb-Doped BaTiO3 and EPR measurements
DC electrical resistivity measurements along the c-axis of Nb-doped BaTiO3 single crystals are presented in a wide range of temperature, covering the four phases, with special attention to the rhomboedral one. The temperature dependence of the conductivity leads to convincing arguments in favour of a polaronic mechanism. Below the orthorhombic-rhomboedral transition point, a strong increase of the resistivity is observed. The correlation of this behavior with EPR analysis in the same temperature range, is consistent with a sharp trapping of the ''free'' electrons, when the temperature decreases.
High frequency dielectric relaxation in BaTio3derived materials
Abstract A systematic study of the dielectric relaxation phenomenon has been carried out for ceramics with compositions derived from barium titanate in the frequency and temperature ranges 1 MHz–1 GHz and 250–500 K, respectively. Whatever the composition may be, a minimum of the relaxation frequency and a maximum of the dielectric dispersion appears at each phase transition temperature. The dipole-type relaxation is correlated to coherent displacements of the ions in the octahedron sites ordered either along chains or in 3D-lattice.
Dielectric and E.P.R. studies of Mn-doped barium titanate
Manganese introduced in BaTiO3 as a substituant of titanium is able to trap the electrons produced during a sintering under a very low oxygen pressure. However it strongly modifies the vibrational ...
Ferroelectric-based nanocomposites : towards multifunctional materials
Nanoparticle technologies open the routes for nanostructured materials which combine individual physical properties or generate new functions. In the field of ferroelectric materials the development of dense nanocomposites requires breakthroughs in the elaboration step. Here, we propose a flexible process to obtain ferroelectric−magnetic nanostructured materials using the assembly of superparamagnetic nanoparticles around ferroelectric cores. The appropriate shaping and sintering of these nanocomposites called nanoraspberries enables a tuning of the physical properties of the resulting dense composite: coexistence between ferroelectricity, piezoelectricity, and superparamagnetism is clearl…
Space-charge relaxation in perovskites.
We report a dielectric anomaly in several perovskites at intermediate frequencies 10\ensuremath{\le}f\ensuremath{\le}${10}^{7}$ Hz in the temperature range 400 \ifmmode^\circ\else\textdegree\fi{}C \ensuremath{\le}T\ensuremath{\le}800 \ifmmode^\circ\else\textdegree\fi{}C. We have found this dielectric maximum in more than 100 samples of various shapes and textures. This anomaly is shown to arise from a Debye dielectric dispersion that slows down following an Arrhenius law. We have established a link between this dielectric relaxation and the conductivity. We propose that it can be achieved through a space-charge model that quantitatively agrees with the experimental results in the lower temp…
Structural and in depth characterization of newly designed conducting/insulating TiN O /TiO2 multilayers obtained by one step LP-MOCVD growth
Abstract TiNxOy/TiO2 multilayers have been grown by LP-MOCVD using titanium isopropoxide (TIP) precursor during the whole growth, but with an ammonia flow interrupted for the TiO2 layers. The one step growth process used to grow these structures allowed to stack the conducting and insulating layers without any growth breakdown. SIMS and TEM analyses showed the presence of an alternated insulating/conducting layers structure. Moreover, electrical measurements allowed to measure the dielectric part of insulating TiO2 stacked in these structures, whose permittivity was found to be about 80 for a MOS structure. Thus, such multilayers may lead to very promising applications in the microelectroni…
The Ba2LnFeNb4O15 “tetragonal tungsten bronze”: Towards RT composite multiferroics
Several Niobium oxides of formula Ba2LnFeNb4O15 (Ln = La, Pr, Nd, Sm, Eu, Gd) with the Tetragonal Tungsten Bronze (TTB) structure have been synthesised by conventional solid-state methods. The Neodymium, Samarium and Europium compounds are ferroelectric with Curie temperature ranging from 320 to 440K. The Praseodymium and Gadolinium compounds behave as relaxors below 170 and 300 K respectively. The Praseodymium, Neodymium, Samarium, Europium and Gadolinium compounds exhibit magnetic hysteresis loops at room temperature originating from traces of a barium ferrite secondary phase. The presence of both ferroelectric and magnetic hysteresis loops at room temperature allows considering these mat…
Experimental evidence for a local disorder in pure and doped perovskites
Abstract In the soft mode picture, the ferroelectric phase transitions in most of ABO3 perovskites are triggered by the long wavelength oscillations of the B ions against their oxygen cage. There is now a lot of experimental evidence that this picture is incomplete. An extra contribution has to be included in the dynamical response. This contribution is usually thought to arise from local lattice distorsions; this is what will be called local disorder. A complete understanding of this local disorder requires the experimental determination of the microscopic origin, of the dynamics and spatial extension of the lattice distorsions. A useful way to summarize these requirements is to use the co…
Non-Linearity Extremum in Niobium Doped Potassium Tantalate
We report non-linear dielectric measurements in the KTaO 3 :Nb system (x Nb ≤ 0.05). The non-linear susceptibility diverges at low temperatures and reaches maximum values in the intermediate range (0.0075 ≤ x Nb ≤ 0.02). To account for this extremum non linearity, we propose a model of temperature dependent clusters which fits with a number of experimental reports. We also suggest that this model may be applied to the related compounds SrTiO 3 :Ca and KTaO 3 :Na.
Dielectric relaxation in crystals and ceramics derived from BaTiO3
Abstract A dielectric relaxation is reported in a crystal of BaTiO3 and in ceramics with composition (Ba1-yCay)TiO3 (0≤y≤0.2) in the frequency and temperature ranges 106 to 109 Hz and 350 to 450 K, respectively. A minimum of the relaxation frequency occurs close to the ferroelectric Curie temperature. The relaxation is of dipolar-type.
Conductimetry and impedance spectroscopy study of low pressure metal organic chemical vapor deposition TiN O films as a function of the growth temperature: a percolation approach
Abstract Titanium oxinitride thin films have been grown by low pressure metal organic chemical vapor deposition (LP-MOCVD) using titanium isopropoxide, Ti(OCH(CH 3 ) 2 ) 4 (TIP) and NH 3 precursors in a growth temperature range from 450 to 750°C on sapphire substrates. The electrical behaviour of these films was studied between 400 and 173 K, revealing three different behaviours, ranking from a hopping conductivity (450–500°C) to a conducting one (700–750°C), with a dual behaviour for the intermediate growth temperatures. Moreover, at room temperature, both conductimetry and impedance spectroscopy highlighted a percolation behaviour, interpreted in terms of continuum percolation. The effect…
Selective growth and optical properties of sputtered BaTiO3films
we report the growth of BaTiO 3 thin films by standard Radio Frequency sputtering. Without any in situ or post annealing, these polycristalline films are oriented relative to the substrate even when it is amorphous. We show that this preferential orientation may be monitored using a DC Bias during the film growth. At room temperature, cubic films of (100) and (110) orientations have been achieved, on fused silica substrate. Some optical waveguiding properties of these films have been studied. The resulting film index is 2.26 and the optical step index at the substrate interface is sharp. This allows the use of standard RF sputtering techniques to monitor oriented BaTiO 3 films for linear op…
Relaxor ferroelectric ceramics of LiTaO3-type
Abstract A ferroelectric relaxation has been identified in Li1-xCax (Ta1-xZrx)O3(x = 0.15 and 0.20) ceramics with LiTaO3-type structure. The relaxation frequency fr is minimum and the dispersion step (ϵ′S - ϵ′∞) is maximum at TC. When x increases, a higher conductivity associated with a lower activation energy and a decrease of the magnitude of fr at Tc are observed, while the unit cell volume becomes larger, TC lower and the transition more diffuse.
Growth and characterization of AP-MOCVD iron doped titanium dioxide thin films
Abstract Atmospheric pressure metal organic chemical vapor deposition (AP-MOCVD) was used to prepare iron doped titanium dioxide thin films. Thin films, between 40 and 150 nm thick, were deposited on Si, SiO 2 and Al 2 O 3 substrates using titanium tetra isopropoxide and ferrocene as metal organic precursors. TiO 2 iron doping was achieved in the range of 1–4 at.%. The film morphology and thickness, polycrystalline texture and doping content were studied using respectively scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The influence of growth temperature, deposition time, substrate type and dopant partial pressure were studied. Electr…
X-ray thermal-diffuse-scattering study of soft modes in paraelectricBaTiO3
Anomalous x-ray thermal diffuse scattering (TDS) from the paraelectric ${\mathrm{BaTiO}}_{3}$ has been measured as a function of temperature using synchrotron radiation. Sheets of intensities that were previously reported have been confirmed. The origin of the observed TDS intensities is attributed to the soft on-(100) TA modes and overdamped [010${]}_{\mathrm{TO}}$ mode for reduced wave vector qg0.25 and 0.25, respectively. In agreement with the previous neutron inelastic scattering experiment, our results support the notion of the one-dimensionally correlated optic motion of atoms.
Ferroelectricity and orientational glass behavior in the [Rbx(NH4)1−x]2SO4system
Abstract The ordering in the electric dipole subsystem of the [Rbx(NH4)1−x]22SO4 family is investigated. The microscopic origin of ferroelectricity for x=0 is discussed, and evidences for the existence of orientational glass behavior in highly substituted crystals are presented.
Polar relaxation mode in pure and iron-doped barium titanate
A dielectric relaxation peak is reported in ${\mathrm{BaTiO}}_{3}$ and in ${\mathrm{BaTi}}_{1\mathrm{\ensuremath{-}}\mathrm{x}}$${\mathrm{Fe}}_{\mathrm{x}}$${\mathrm{O}}_{3}$. It is nearly monodispersive, centered in the ${10}^{8}$-Hz range, and slowest at the transition temperature ${T}_{c}$\ensuremath{\simeq}413 K from the cubic to the tetragonal phase. Iron doping lowers ${T}_{c}$ and slows down this relaxation mode.
Relaxations Below Glass Transition Temperature in Bread and Its Components
ABSTRACT Dry glassy bread, cooked gluten, and gelatinized wheat starch-sucrose mixtures were prepared. Dielectric properties were studied as a function of temperature at different frequencies ranging from 100 to 1,000 kHz. Both bread and starch samples exhibited a tan δ peak at -53°C at 10 kHz, which is associated with a secondary relaxation characterized by an activation energy of 50 kJ/mol. The gluten sample did not show any relaxation in the temperature range studied. The magnitude of the relaxation peak was sensitive to the sucrose concentration of the starch sample. The higher the sucrose content, the greater the amplitude of the peak. Such an effect is attributed to a greater β-relaxa…
X-Ray diffraction diagram evolution of a BaTiO3ceramic under an electric field
Abstract The X-ray diffraction diagrams of a coarse grained pure BaTiO3 ceramic have been recorded as a function of the applied electric D.C. field. This field was perpendicular to the X-ray incoming surface. The experimental device used allows to record diffraction diagrams while the electric field step by step increases. The intensity ratio of the 002 line over the 200 line increases with the applied electric field. The evolution of the X-ray diffraction line intensities is in correlation with the first polarization curve of the ferroelectric ceramic. These results evidence a contribution of the 90° ferroelectric domains pattern to the X-ray diffraction diagram of BaTiO3.
Optical studies of laser-induced gray-tracking in KTP
We have studied gray-tracking induced by a pulsed and polarized 532-nm laser beam in flux grown KTiOPO/sub 4/ (KTP) crystals. Transmission spectra measured under polarized light give different results: gray-tracking leads to an increase in the initial anisotropy of the linear optical properties of KTP, and the polar axis is the most sensitive to this process. The dynamics of relaxation of gray-tracking is anisotropic and depends on the wavelength under analysis. We show a possible induced modification of the crystal surface and also the existence of an intensity above which gray-tracking reaches the saturation point. We then measure the temperature above which gray-tracking no longer exists.
Electrostatic model and NMR results for EFG tensors in tetragonal BaTiO3
Abstract We present 47,49Ti and 135,137Ba NMR second-order quadrupolar rotation patterns in a tetragonal single domain crystal of BaTiO3. These data will be analysed in terms of a ionic polarizable point multipole model.
Molecular Mobility in Glassy Bread: A Multispectroscopy Approach
ABSTRACT The molecular mobility in low-moisture (<9%, web) white bread was studied as a function of temperature using pulsed-proton nuclear magnetic resonance (NMR), and dielectric and dynamic mechanical spectroscopies. The water was mobile, even in glassy samples. Different processes below glass transition temperature (sub-Tg) were observed, and a relaxation map of the studied system was drawn. These results have been interpreted and extrapolated to suggest that the Tg is not a universal predictive parameter for the physical stability of glassy food.
Dielectric relaxation and conductivity in ferroelectric perovskites
Abstract Ferroelectric ABO3 perovskites are usually well known for their high dielectric susceptibility. Under selected impurity substitutions their conductivity may be strongly increased. The interaction between electronic conductivity and lattice polarizability may take place over different length scales. At high temperatures (T > 300 K), this interaction length is macroscopic leading to space charges. At low temperatures (T < 50 K), the polaronic interaction is restricted to a few unit cells. In the special case of SrTiO3, these polaronic excitons are sensitive to the quantum fluctuations which lead to the new concept of quantum polarons.
Domain Walls Motions in Barium Titanate Ceramics
The shear modulus and mechanical loss at low frequencies (0.01, 0.3, 1 Hz) are measured by an inverted pendulum for BaTiO 3 ceramic with large grain sizes. The permittivity and dielectric losses are also investigated for the same material at higher frequencies between 1 and 100 kHz as function of temperature. Those results show several relaxation peaks in the ferroelectric phases. The activation energy of each peak is obtained to be 0.29, 0.45, 0.68, 0.92 eV. The influences of strain amplitude and thermal treatments are studied specially for the mechanical relaxation peak located in the tetragonal phase. All the relaxation peaks could be associated to the interaction of oxygen vacancies in …
Non-linear dielectric behaviour and glass phase in Sr1-xCaxTiO3(x= 0.002 andx= 0.003)
This work reports a study of the temperature and electric field dependence of the dielectric constant of strontium calcium titanate. The first part of the paper is focused on the analysis of a mean-field model for the polar clusters generated by the random impurities of calcium. It is shown that the dipolar moments within each cluster can be represented by an equivalent quantum two-level system. General expressions for the temperature and field dependence of the Edward-Anderson order parameter and of the electrical polarization are given. Analytical solutions are also obtained in the limit of high temperatures and in the limit of high tunnelling frequencies. The second part of the work repo…
Comment on “Indications of aT=0Quantum Phase Transition inSrTiO3”
A Comment on the Letter by Daniel E. Grupp and Allen M. Goldman, Phys. Rev. Lett. 78, 3511 (1997). The authors of the Letter offer a Reply.
Les céramiques pour l’électronique et l’électrotechnique
International audience; Ce chapitre est consacré au très vaste domaine des céramiques pour l’électronique et l’électrotechnique : céramiques résistives, conductrices, supraconductrices, diélectriques, magnétiques, linéaires ou non linéaires, piézoélectriques, multifonctionnelles. En perpétuelle évolution: de plus en plus petites, de moins en moins chères, de plus en plus intégrées…
BST ceramics: Effect of attrition milling on dielectric properties
Abstract The effect of grain size on the dielectric properties of Ba0.6Sr0.4TiO3 (BST) ceramics is investigated. Attrition milling is chosen to obtain nanometre particle size from micrometre particle size powders. Fine grained ceramics are obtained by hot uniaxial pressing (HUP). Additionally, the present study is focused on the effect of the nature of milling balls on loss tangent and permittivity. For that, three kinds of balls are tested: calcia, yttria or ceria stabilised zirconia balls. The properties of these samples are evaluated in the range of MHz. The balls induce an involuntary doping of powders which modifies the dielectric properties, especially the Curie temperature and loss t…
Electron-relaxation-mode interaction in BaTiO3:Nb.
Dielectric relaxation was previously reported in ${\mathrm{BaTiO}}_{3}$ and ${\mathrm{BaTiO}}_{3}$:Fe single crystals at radio frequencies [M. Maglione et al., Phys. Rev. B 40, 11 441 (1989)]. We have measured the dielectric dispersion in four ${\mathrm{BaTiO}}_{3}$:Nb samples (${\mathit{x}}_{\mathrm{Nb}}$0.3 at. %) as a function of frequency (10f${10}^{9}$ Hz) and temperature (20T450 K). The electronic conductivity of ${\mathrm{BaTiO}}_{3}$:Nb enhances drastically the relaxation step at all temperatures. In the rhombohedral phase of ${\mathrm{BaTiO}}_{3}$:Nb (T180 K), an unusual slowing down of the relaxation motion is measured. The relaxation time increases to more than ${10}^{\mathrm{\en…
Dielectric relaxation of space charges and polarons in ferroelectric perovskites
Abstract In all ferroelectric perovskites, intentionally introduced or “unwanted” point defects do play a role in the dielectric spectra and in the conductivity. Above room temperature, space charge relaxation at the electrodes interfaces are observed. This can be of interest in the context of the nowadays applications of ferroelectric thin films. At liquid helium temperatures much more localised dielectric relaxation occurs. Special emphasis will be brought on SrTiO3 which has received renewed interest at the beginning of the nineties and for which a wealth of reliable experimental data are available. Considering that a gradual freezing of polarized objects is occurring at low temperatures…
Frequency and temperature dependence of the electrical conductivity of KTaO3; Li and PbTiO3; La, Cu: Indication of a low temperature polaron mechanism
Abstract Recently, the concept of polarons has again been at the focus of solid-state research, as it can constitute the basis for understanding the high-temperature superconductivity or the colossal magnetoresistance of materials. More than a decade ago there were some indications that polarons play an important role in explaining low temperature maxima in imaginary part of the dielectric constant e ″ ( T ) in ABO3 perovskites. In the present work we report the ac electrical conductivities of KTaO3; Li and PbTiO3; La, Cu and their frequency and temperature dependence. The real part of the complex ac conductivity was found to follow the universal dielectric response σ ′ ∝ ν s . A detailed t…
Correlation Between the Electrical Properties and the Morphology of Low-Pressure MOCVD Titanium Oxynitride Thin Films Grown at Various Temperatures
Titanium oxynitride (TiN x O y ) thin films were deposited by low-pressure metal-organic CVD (LP-MOCVD) on (100) silicon, sapphire, and polycrystalline alumina substrates. Titanium isopropoxide (TIP) and ammonia were used as precursors. The influence of the growth temperature, ranking from 450°C to 750°C, was investigated by scanning electron microscopy (SEM), and electrical DC measurements. Rutherford back-scattering (RBS) measurements were used to determine the N/O ratio in the films. The surface observations of the deposited films showed two morphological transitions. The resistivity decreased with the growth temperature, while the nitrogen content increased. Moreover, for the highest de…
Local disorder studied inSrTiO3at low temperature by EXAFS spectroscopy
The temperature dependence of the local distortions in ${\mathrm{SrTiO}}_{3}$ has been studied by EXAFS spectroscopy at the titanium K edge (4982 eV). The oxygen-ion Debye-Waller factor ${\mathrm{\ensuremath{\sigma}}}_{0}^{2}$ has been determined from 4.5 to 240 K. The antiferrodistortive transition at 105 K is evidenced by a step in this Debye-Waller factor. At about 31 K, a maximum of ${\mathrm{\ensuremath{\sigma}}}_{0}^{2}$ is detected and the EXAFS oscillations due to the first oxygen shell increase. This is the signature of a maximum disorder in the lattice vibrations in this temperature range. A quasiharmonic model with a sinusoidal modulation of the Ti-O distance cannot account for t…
Crystal structure transformations induced by surface stresses in BaTiO3and BaTiO3@SiO2nanoparticles and ceramics
International audience; Lattice structure transformations in nanopowders of ferroelectric BaTiO3 and BaTiO3@SiO2 core-shell nanostructured ceramics were studied by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) at the temperatures 120–450 K and particle size of 300 and 500 nm. NMR spectra of all studied samples in the paraelectric phase are identical to the spectra in bulk material indicating their perfect perovskite structure without visible influence of particle surface. However, we have found that surface of particles essentially influence the ferroelectric phase transitions detected by both NMR and EPR techniques. The strongest changes as compared to bulk mat…
Polaronic relaxation in perovskites
We report a low-temperature loss anomaly in several oxidic perovskites such as ${\mathrm{KTaO}}_{3}$, ${\mathrm{KTaO}}_{3}$:Nb, ${\mathrm{SrTiO}}_{3}$, ${\mathrm{SrTiO}}_{3}$:Ca, ${\mathrm{PbTiO}}_{3}$:La, Cu, and ${\mathrm{BaTiO}}_{3}$:La. We show that this anomaly arises from a low-frequency dielectric relaxation. The activation energy and the relaxation time of this process are nearly the same for all the investigated perovskites disregarding their composition, texture, and ferroelectric properties. We thus ascribe the loss anomaly to the localization of polarons on residual defects. Although the dielectric losses in ${\mathrm{SrTiO}}_{3}$ and ${\mathrm{SrTiO}}_{3}$:Ca are qualitatively …