Elastic, dielectric, and piezoelectric anomalies and Raman spectroscopy of 0.5Ba(Ti0.8Zr0.2)O3-0.5(Ba0.7Ca0.3)TiO3

The solid solution 0.5Ba(Ti0.8Zr0.2)O-3-0.5(Ba0.7Ca0.3)TiO3 (BCZT) is a promising lead-free piezoelectric material with exceptionally high piezoelectric coefficients. The strong response is related to structural instabilities close to ambient temperature. We report here on temperature-induced anomalies in the dielectric, piezoelectric, and elastic coefficients and Raman spectroscopy of ceramic BCZT. The data indicate ferroelectric-ferroelectric structural phase transitions in this material in addition to those previously reported. An anomaly is also observed above the Curie temperature T-C and is associated with the loss of polar structure that persists thirty degrees above T-C. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4714703]

Ferroelectric Polymer Gates for Persistent Field Effect Control of Ferromagnetism in (Ga,Mn)As Layers

Sebastian Riester

The growing demand for higher computing power and element density continuously drives the development of novel device concepts. One group of materials currently attracting a lot of interest are the magnetoelectric multiferroics, due to their potential for creating devices with novel functionalities. These materials exhibit coupled ferroelectric and ferromagnetic behavior. Although the focus is on homogeneous multiferroics like bismuth ferrite, the stronger multiferroic coupling that is possible in composite multiferroics makes them attractive for many potential applications (e.g. spintronic logic and memory elements). In particular, electric field-mediated multiferroic composites promise worthwhile compatibility with CMOS circuitry. The present work explores a multiphase multiferroic system where the ferroelectric gate controls a dilute magnetic semiconductor (DMS) channel via the nonvolatile field effect associated with the spontaneous polarization. The system consists of a copolymer of vinylidene fluoride and trifluoroethylene [P(VDF-TrFE)] as the ferroelectric gate and an ultra-thin magnetic layer of (Ga,Mn)As which is one of the most well-established DMS and is considered a chief candidate for spintronic applications. The main outcomes of this research can be summarized as follows: A widely recognized incompatibility between ferroelectrics and group III-V semiconductors has been solved by the integration of a polymer ferroelectric onto a DMS in a multiferroic transistor configuration. Nonvolatile electric field control of ferromagnetism in a (Ga,Mn)As channel has been successfully demonstrated. Several pieces of evidence including the change of hysteretic properties, ferromagnetic Curie temperature shift and magnetoresistance behavior attest to the field effect-mediated multiferroic coupling in this system. Low ferroelectric gate operation voltages below 10 V were achieved through aggressive P(VDF-TrFE) thickness reduction without diminishing the gate effect strength. Polarization screening at the semiconductor/ferroelectric interface was identified as the main issue limiting the ferroelectric gate effect. A significant enhancement of the multiferroic coupling has been reached by thinning the (Ga,Mn)As channel down to 3 nm without compromising the ferromagnetic properties. From the Curie temperature response to ferroelectric gating, that follows the same trend for samples with thicknesses ranging from 3 to 7 nm, we conclude that the 2D limit has not been reached for the thinnest channels and the 3D models describing the ferromagnetic coupling are valid for this case. The ferroelectric control of ferromagnetism has been quantitatively interpreted in terms of existing models for hole-mediated exchange in (Ga,Mn)As.

EPFL2010

Solid Solutions of Lead Metaniobate-Stabilization of the Ferroelectric Polymorph and the Effect on the Lattice Parameters, Dielectric, Ferroelectric, and Piezoelectric Properties

Alberto Biancoli, Dragan Damjanovic, Barbara Maraston Fraygola, Mtabazi Geofrey Sahini, Nava Setter

Ferroelectric orthorhombic lead metaniobate (PbNb2O6) is known to be metastable with respect to the thermodynamically stable nonferroelectric rhombohedral polymorph. The high-temperature tetragonal to low temperature rhombohedral phase transition is reconstructive and thereby sluggish; ferroelectric PbNb2O6 is obtained by quenching from the stable phase field of the tetragonal polymorph. We report on the stabilization of the ferroelectric tungsten bronze polymorphs of PbNb2O6 by minor chemical substitution in the series [(1 - x) PbNb2O6-xBiTiNbO(6)], [(1 - x)PbNb2O6-xNa(0.5)Bi(0.5)Nb(2)O(6)], [(1 - x)PbNb2O6-xK(0.5)Bi(0.5)Nb(2)O(6)], and [(1 - x)PbNb2O6-xCaTiO(3)]. The high- temperature tungsten bronze polymorph is entropy stabilized with respect to the stable rhombohedral polymorph, and we propose that the tungsten bronze is further entropy stabilized by chemical substitution, reducing the transition temperature of the rhombohedral polymorph and further disfavoring the kinetics of the undesired phase transition. Optimized solid-state synthesis and processing to obtain dense ceramics were developed for the solid solutions, and the dielectric, ferroelectric, and piezoelectric properties of the PbNb2O6 solid solutions are reported. Curie temperature is suppressed with chemical substitution in all the systems. Lattice cell parameters display systematic variation with composition, reducing the molar volume, and the lattice parameter ratio 2b/a with increasing degree of substitution, reflecting a suppression of the polarization along the (010) direction due to chemical substitution. The piezoelectric properties improved with increasing substitution level probably due to the ease of poling of the materials with lower T-c. However, some improvements seen with 2% CaTiO3 were not accompanied by T-c decrease.

Wiley-Blackwell2014

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