Sol-gel derived Pb(Sc0.5Nb0.5)O-3 thin films: Processing and dielctric properties

Relaxor Pb(Sc1/2Nb1/2)O-3 (PSN) thin films without pyrochlore phase were processed from the modified alkoxide solution precursors. The preparation of single phase PSN thin films has a narrow processing window due to the appearance of an undesirable pyrochlore phase and volatility of PbO. Thin film processing has been improved through selection of precursor solutions, heat treatment and optimized deposition-condition are optimized. Especially, the effects of Pt substrates seeded with additional layers upper of TiO2 and La0.5Sr0.5CoO3 are investigated through the scanning electron microscopy (SEM) scanning of film/electrode interfaces. Dielectric behaviors of sol-gel derived PSN thin films on two different substrates are observed. They show the evidence of relaxor-like behaviors, i.e. the temperature dependence of the dielectric constant at different applied frequencies. Films on the TiO2/Pt/TiO2/SiO2/Si substrates exhibit better dielectric properties, such as frequency saturation over transition temperature and much lower dielectric loss than those on the La0.5Sr0.5CoO3/Pt/TiO2/SiO2/Si substrates. The differences of transition behaviors between PSN thin films and bulk ceramics are also discussed in relation to the processing temperature, interface phenomena between film and electrode, relatively small thickness and strain effect of films.

Conductivity, dielectric and piezoelectric properties of SrBi4Ti4O15

Strontium Bismuth Titanate is a very promising material for high temperature piezoelectric applications, its elevated ferroelectric phase transition (530°C), linear piezoelectric properties under low field and relatively low room temperature conductivity (compared to others Bismuth Titanates) make it very attractive for precision sensors. However, under severe conditions (low frequency, high field, high temperature or low oxygen partial pressure) some of those advantages disappear. Piezoelectric response is dominated by charge drift in general becomes unstable. Above all, at high temperature and low oxygen partial pressure, a large conductivity increase reduces the piezoelectric efficiency of the material, in this work, electrical conductivity, piezoelectric properties and dielectric permittivity of SrBIT ceramic have been investigated in conditions of high temperature, low oxygen partial pressure, low to moderate driving field and frequency. As a result of this research, a better understanding of SrBIT properties was achieved. Thanks to a careful study of SrBIT processing as a bulk ceramic, a reproducible route was established. Many basic mechanisms leading to both SrBIT crystallization and sintering have been identified. It was demonstrated that a detailed knowledge of the exact processing conditions is required in order to achieve high quality material. DC conductivity measurements were carried out as a function of temperature, oxygen partial pressure and dopant concentration. It was found that the apparent activation energy for conduction for undoped SrBIT was 1 eV between 140 and 220°C and 1.5 eV between 450 and 700°C. Decrease of the activation energy in the lower temperature range has been discussed considering grain boundary conductivity, as a transition from electronic to ionic conduction or as consequence of small polarons conduction. It was shown that lower activation energy resulted from Manganese doping (0.5 eV), this was interpreted as either growing influence of grain boundary conductivity as dopant concentration increases or as shallow hole trap formation. DC conductivity measurements and acceptor/donor doping experiments demonstrated p-type conductivity in the low temperature range (up to 220°C) as donor doping decreases conductivity, while oxygen partial pressure controlled measurements indicated n-type conductivity at higher temperature (above 700°C). An electrical impedance analysis was performed with several equivalent circuits. The aim of these models was to simulate the impedance of SrBIT. The best approximation was found with a distributed element of Havriliak-Negami type. However, as the physical justification for this circuit was not clear, the investigation of the grain, grain boundary and electrode impedances was performed with multiple discrete parallel RC elements. With temperature, grain size and oxygen activity variations, the identification of three separate contributions as grain, grain boundary and electrode was realized. The anisotropy of conductivity and permittivity was demonstrated with textured material and both DC and AC analysis. With the master curves built for the electrical modulus, it was found that the impedance probably related to Bismuth oxide layers produces an additional high frequency are. From this finding and by comparing characteristic relaxation frequencies of undoped, 2 mol.% Mn and 4 mol.% Nb SrBIT, it was determined that conductivity is higher in the ab plane direction than in the c direction within both perovskite units and Bismuth oxide layers. With conductivity measurements under controlled oxygen partial pressure, it was found that an acceptor-based (intrinsic or extrinsic) model could be used to describe the electrical conductivity under controlled oxygen partial pressure of both undoped and 2 mol.% Mn doped SrBIT. However, as neither a pO2-1/6 region (intrinsic oxygen vacancies compensated by electrons) for undoped SrBIT nor a pO2-1/4 region (oxygen vacancies compensated by singly ionized acceptors) for Mn doped SrBIT were seen, it was concluded that the acceptorcontrolled model is not sufficient for a complete description of SrBIT. For this reason and in order to include the low oxygen partial pressure behavior of undoped SrBIT, a donor-based (intrinsic) model was also considered. The source of intrinsic donors would be in that case Bi3+ cations sitting on Sr2+ sites in the perovskite sublattice. Considering Bismuth vacancies as the negative compensating species, both pO2-1/4 and pO2-independent regions could be predicted with the model. However, even if the donor-controlled model seems to better match conductivity measurements in the full PO2) range, rejecting the acceptor-based model would be an error. It is actually not demonstrated that in SrBIT the concentration of exchanged Bismuth cations is always (all temperature, pressure) larger than the natural acceptor impurity concentration. It is very likely that the cation exchange is dependent of the oxygen partial pressure. It is also not proved as suggested in the literature that direct compensation between exchanged Strontium and Bismuth exists, reducing the net donor-excess. With the acceptor-controlled model, the mass-action constants for reduction and for ionization of intrinsic carriers across the band gap were determined. The band gap of SrBIT was estimated to be 3.5 eV. The ionic conductivity of SrBIT was determined at high temperature with measurements under controlled oxygen partial pressure. It was found that the electrical conductivity of SrBIT is probably mixed (electronic and ionic) as the estimation of the transference number provided quite large values (t=0.8 at 800°C). From electronic and ionic conductivity data, mixed conduction can actually be predicted in a large temperature range (above room temperature). The piezoelectric measurements using direct effect demonstrated that it is actually possible to unlock piezoelectrically active ferroelectric domain walls and create non-linear piezoelectric properties in undoped SrBIT. This occurs above a threshold elastic field, which is thermally activated. With a piezoelectric composite, it was demonstrated that the electromechanical coupling between two different phases creates a piezoelectric relaxation. This one could be positive or negative depending on the respective properties of each composite's component. It was shown experimentally that a small temperature change is sufficient to transform a positive relaxation into a negative one. While these experiments did not provide a detailed microstructural explanation for the piezoelectric relaxation observed in 2 mol.% Mn doped SrBIT, they gave a first insight into an original phenomenological approach. Microstructure and piezoelectric properties were related with the calculation of a piezoelectric relaxation composite made of two textured samples. This demonstrated that a piezoelectric relaxation may occur just because of anisotropy. Microstructural reproduction of this coupling is actually an important feature of Aurivillius phases.

EPFL2000

Pulsed laser deposition of (SrBa)Nb2O6 thin films and their properties

Anna Infortuna

Strontium barium niobate (SrxBa1-xNb2O6, shortly SBN) is a solid solution system with tetragonal tungsten bronze crystal structure. It exhibits a ferroelectric phase with only one polar axis and a transition temperature depending on the Sr/Ba ratio. This thesis studies the growth of SBN thin films, in order to obtain a ferroelectric thin film model system for the study of 180° domain switching close to the ferroelectric phase transition. SBN has been chosen not only because uniaxial, but because it is possible to tune the temperature of phase transition varying the Sr/Ba ratio. It is thus possible to study electric properties of the phase transition close to room temperature, where conduction phenomena related to defects are normally lower. Thin films of SBN were grown by Pulsed Laser Deposition in a vacuum system constructed during this thesis work. For the formulation of a model it is desirable to have a system as close as possible to a single crystal. Therefore deposition parameters have been optimized to grow SBN thin films with the polar axis oriented perpendicular to the film plane. The films are integrated in parallel plate capacitor structures, in order to measure dielectric properties. The stability of the ferroelectric phase is found to be sensitive to impurities; contaminants with concentration below 1% induce a lowering of the transition temperature of about 100°C. Strain as well has influence on the phase transition; in the case of substrate with thermal expansion coefficients different from the SBN ones, the SBN film is under stress. A 0.6% tensile strain induces a lowering of the transition temperature of about 100°C, this is the case of silicon single crystal substrate. Grown on strontium titanate single crystals (STO), whose thermo-mechanical properties are close to the one of SBN, the films exhibit a phase transition temperature compatible with the one measured on single crystals. The obtained films suffer from leakage that is reduced by thermal treatment in oxygen rich atmosphere. The oxygen vacancies, created during the deposition process, are considered to be responsible of leakage. Vacancies recovery upon annealing does not eliminate the problem, and measurement of polarization at room temperature is difficult. However, piezoelectric measurements performed on individual grains, with atomic force microscope, prove that these have ferroelectric properties; by these experiment has been proved that it is possible to switch the polarization. Films with a disordered structure of grains are much less leaky than the ones with columnar grains spanning the whole cross section. These observations lead to the conclusion that conduction goes trough the grain boundaries. On STO single crystals, SBN grows epitaxial in Volmer-Weber mode. With a suitable preparation of the substrate surface, it is possible to induce the growth of films with different orientations of the polar axis: in the film plane, perpendicular to it or inclined of 45°. A model is proposed, explaining the epitaxial relation with the substrate on the basis of the perovskite kernel contained in the unit cell of the tetragonal tungsten bronze structure. The film grows from the nucleation of the perovskite structure that rules the orientation of the film; the high temperature at which the substrate is kept during the deposition, assure the necessary mobility for the arriving atoms to organize in the SBN structure around these nuclei. The study of literature data allows to state that such a model is valid not only for substrates with perovskite structure, but can be extended to substrates with a cubic crystal structure, like magnesium oxide.

EPFL2005

Surface-stimulated phenomena in the polarization response of ferroelectrics

Guido Gerra

The integration of ferroelectrics in electronic devices requires that they be used in the form of thin films, which implies that for such systems finite-size effects related to the presence of a ferroelectric-electrode interface become important. In this thesis, a number of theoretical studies are presented on the properties of metal-ferroelectric-metal structures, focusing on the impact of the metal-ferroelectric interface on the polarization response of the system. First, a model for reverse domain nucleation in ferroelectrics is introduced, which takes into account the ferroelectric-electrode coupling in both the homogeneous and random cases. The model provides a solution to the coercivity paradox—i.e., the large discrepancy between the observed and predicted coercive fields. The possibility of non-thermally activated nucleation of reverse domains is demonstrated. It is found that small inhomogeneities in the ferroelectric-electrode interface may lead to an exponentially wide spectrum of waiting times for switching. The model predicts that switching is facilitated near morphotropic phase boundaries in perovskite-type ferroelectrics. In order to quantitatively analyze the size-effect problem in metal-ferroelectric-metal systems, an approach is developed which combines first-principles calculations and phenomenological theory. The parameters of the model can be extracted from calculations on ultrathin films, while experimentally verifiable predictions can be made on thick films. Using the developed approach, it is demonstrated how the size effect can be separated into two distinct contributions: a long-range electrostatic and a short-range "chemical" one. By considering symmetric SrRuO3/BaTiO3/SrRuO3 heterostructures with different types of termination (TiO2–TiO2 or RuO2–RuO2), it is shown that the balance between the long-range and the short-range contribution to the size effect can be essentially affected by the type of termination of the ferroelectric and by the polarization hardness of the electrode. The leading role of the long-range contribution to the size effect in SrRuO3/BaTiO3/SrRuO3 heterostructures is demonstrated. Application of the approach to the case of SrRuO3/BaTiO3/SrRuO3 heterostructures with asymmetric interfaces enables to provide a quantitative description of a number of manifestations of such asymmetry in films of technologically meaningful thickness. In particular, it is found that the asymmetry exerts a poling effect on the films, leading to a smearing of the phase transition, to an induced piezoelectric response above the transition temperature, and to the reversal of the polarization asymmetry by application of biaxial strain. Another important result of such calculations is the observation that the ionic relaxations in the metal-oxide electrode play a crucial role in stabilizing the ferroelectric phase of the films. Comparison with frozen-phonon calculations shows that the degree of softness of the SrRuO3 lattice has an essential impact on the screening of ferroelectric polarization, reducing the critical thickness for ferroelectricity of the system. These results provide a possible explanation for the observed beneficial impact of oxide electrodes on the switching and dielectric properties of ferroelectric capacitors.

EPFL2008