Correlation between enhanced lattice polarizability and high piezoelectric response in BiScO3-PbTiO3

Piezoelectric and ex situ electric-field induced structural studies were carried out on closely spaced compositions in the morphotropic phase boundary region of (1 - x) PbTiO3-(x)BiScO3. While the common approach of zero field structural analysis failed to provide a unique relationship between the anomalous piezoresponse of x = 0.3725 and structural factor(s), ex situ study of electric-field induced structural changes revealed that the composition exhibiting the highest piezoelectric response is the one which also exhibits significantly enhanced polarizability of the lattices of both coexisting (monoclinic and tetragonal) phases. The enhanced lattice polarizability manifests as a significant fraction of the monoclinic phase transforming irreversibly to the tetragonal phase after electric poling. DOI: 10.1103/PhysRevB.87.064106

Competing structural phase transition scenarios in the giant tetragonality ferroelectric BiFeO3-PbTiO3: Isostructural vs multiphase transition

A systematic x-ray and neutron powder diffraction study of the giant tetragonality multiferroic (1-x) BiFeO3-(x) PbTiO3 have revealed that the compositions close to the morphotropic phase boundary present two different structural phase transition scenarios on cooling from the cubic phase: (i) cubic -> tetragonal (T-2) + tetragonal (T-1) -> tetragonal (T-1) and (ii) cubic -> tetragonal (T-2) + tetragonal (T-1) + rhombohedral (R3c) -> tetragonal (T-1) + rhombohedral (R3c). The comparatively larger tetragonality (c/a - 1) of the T-1 phase as compared to the coexisting isostructural T-2 phase is shown to be a result of significantly greater degree of overlap of the Pb/Bi-6s and Ti/Fe-3d with the O-2p orbitals as compared to that in the T-2 phase. The formation/suppression of the minor metastable rhombohedral phase seems to be governed by subtle play of local kinetic factors. In the scenario when the minor rhombohedral (R) phase is formed along with the tetragonal phases it is able to accommodate the large transformation stress in the system due to formation of the tetragonal phases, and prevent the solid from disintegration into powder after sintering. When the metastable rhombohedral phase is not formed, the large transformation strain ruptures the grain boundaries leading to fragmentation of the dense solid to powder. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4792215]

Metastable morphotropic phase boundary state in the multiferroic BiFeO3-PbTiO3

Temperature-time study of the magnetoelectric multiferroic (1-x)BiFeO3-(x)PbTiO3 by x-ray and electron diffraction on the reported morphotropic phase boundary (MPB) compositions revealed that this MPB does not correspond to the equilibrium state. The MPB like state is rather of metastable nature and arise due to kinetic arrest of metastable rhombohedral (R3c) phase, along with the equilibrium tetragonal (P4mm) phase. The life time of the metastable R3c nuclei is very sensitive to composition and temperature, and nearly diverges at x -> 0.27. The MPB like state appears only if the system is cooled before the metastable R3c nuclei could vanish. These findings resolve the long standing controversy with regard to seemingly erratic phase formation behaviour reported by different groups and provides a rational basis for developing genuine equilibrium MPB compositions in this system for better piezoelectric properties. (C) 2013 AIP Publishing LLC.

Stabilization of metastable tetragonal phase in a rhombohedral magnetoelectric multiferroic BiFeO3-PbTiO3

The phase formation behaviour of the magnetoelectric multiferroic 0.8BiFeO(3)-0.2PbTiO(3) was studied as a function of heat treatment at different temperatures of a sol-gel derived powder. While under ordinary synthesis conditions this composition exhibits antiferromagnetic ordering and a rhombohedral structure; the sol-gel-enabled low-temperature synthesis could stabilize a tetragonal metastable phase along with the stable rhombohedral phase, mimicking a morphotropic phase boundary state. The phase coexistence state exhibits relatively enhanced ferromagnetic correlation. The same system with a relatively higher PbTiO3 concentration, 0.65BiFeO(3)-0.35PbTiO(3), on the other hand, exhibits a rhombohedral metastable phase. These results suggest that the occurrence of metastable phases is a very common feature in the BiFeO3-PbTiO3 magnetoelectric ferroelectric system and that it affects the ferroelectric and magnetic properties of system quite remarkably.

Equilibrium phases in the multiferroic BiFeO3-PbTiO3 system - a revisit

The(1-x) BiFeO3-(x) PbTiO3 solid solution exhibiting a Morphotropic Phase Boundary (MPB) has attracted considerable attention recently because of its unique features such as multiferroic, high Curie point (T-C similar to 700 degrees C) and giant tetragonality (c/a -1 similar to 0.19). Different research groups have reported different composition range of MPB for this system. In this work we have conclusively proved that the wide composition range of MPB reported in the literature is due to kinetic arrest of the metastable rhombohedral phase and that if sufficient temperature and time is allowed the metastable phase disappears. The genuine MPB was found to be x=0.27 for which the tetragonal and the rhombohedral phases are in thermodynamic equilibrium. In-situ high temperature structural study of x=0.27 revealed the sluggish kinetics associated with the temperature induced structural transformation. Neutron powder diffraction study revealed that themagnetic ordering at room temperature occurs in the rhombohedral phase. The magnetic structure was found to be commensurate G-type antiferromagnetic with magnetic moments parallel to the c-direction (of the hexagonal cell). The present study suggests that the equilibrium properties in this solid solution series should be sought for x=0.27.

Ferroelectric phase coexistence by crystallite size reduction in BiFeO3-PbTiO3

Size effect in ferroelectrics has been extensively investigated in the past with the general consensus that the long-range ferroelectric ordering gradually disappears with decreasing crystallite size, eventually leading to the paraelectric state. In this paper, we show that the compositions exhibiting giant tetragonality (c/a similar to 1.18) of the ferroelectric alloy system BiFeO3-PbTiO3 transform from a pure tetragonal phase to a state comprising tetragonal and rhombohedral phases as the average crystallite size is reduced from similar to 10 to similar to 1 mu m. It is argued that the increased surface energy in the smaller sized crystallites creates an equivalent compressive stress that drives the system towards tetragonal-rhombohedral criticality.

Analogous stress and electric field driven structural transformation and decrease in polarization coherence on poling around the morphotropic phase boundary in BiScO3-PbTiO3

The nature of the stress and electric field driven structural and microstructural transformations in the morphotropic phase boundary (MPB) compositions of the high Curie point piezoelectric system BiScO3-PbTiO3 has been examined by ex situ based techniques. Using a powder poling technique, which is based on the concept of exploiting the irreversible structural change that occurs after the application of a strong electric field and stress independently, it was possible to ascertain that both moderate stress and electric field induce identical structural transformation-a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. Moreover, analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, we demonstrate that the criticality associated with the interferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques.

Field induced domain switching as the origin of anomalous lattice strain along non-polar direction in rhombohedral BiScO3-PbTiO3 close to the morphotropic phase boundary

The lattice strain and domain switching behavior of xBiScO(3)-(1-x) PbTiO3 (x = 0.40) was investigated as a function of cyclic field and grain orientation by in situ X-ray diffraction during application of electric fields. The electric field induced 200 lattice strain was measured to be five times larger than the 111 lattice strain in pseudorhombohedral xBiScO(3)-(1-x) PbTiO3 (x = 0.40). It is shown that the anomalous 200 lattice strain is not an intrinsic phenomenon, but arises primarily due to stress associated with the reorientation of the 111 domains in dense polycrystalline ceramic. (C) 2015 AIP Publishing LLC.

Anomalous reduction in domain wall displacement at the morphotropic phase boundary of the piezoelectric alloy system PbTiO3-BiScO3

A comparative study of field-induced domain switching and lattice strain was carried out by in situ electric-field-dependent high-energy synchrotron x-ray diffraction on a morphotropic phase boundary (MPB) and a near-MPB rhombohedral/pseudomonoclinic composition of a high-performance piezoelectric alloy (1-x) PbTiO3-(x)BiScO3. It is demonstrated that the MPB composition showing large d(33) similar to 425 pC/N exhibits significantly reduced propensity of field-induced domain switching as compared to the non-MPB rhombohedral composition (d(33) similar to 260 pC/N). These experimental observations contradict the basic premise of the martensitic-theory-based explanation which emphasizes on enhanced domain wall motion as the primary factor for the anomalous piezoelectric response in MPB piezoelectrics. Our results favor field-induced structural transformation to be the primary mechanism contributing to the large piezoresponse of the critical MPB composition of this system.

Stability of Fe3+ -VO defect pairs in polycrystalline Pb(Ti,Zr)O3

The intensity of the EPR signal with g = 5.985 arising from a ferric ion â oxygen vacancy defect pair (Fe3+ â VO) in PbTiO3, varies with the extent of PbO nonstoichiometry at constant Fe3+ content due to an increased oxygen vacancy concentration. In PZT solid solutions, the signal intensity decreases with an increase in Zr. A lower intensity is also noticed for Fe3+ â VO signals in PbZrO3. This behaviour is explained on the basis of PbO nonstoichiometry arising from independent Pb- and O-vacancies as well as the randomly distributed crystallographic shear (CS) plane defects. The contribution to PbO nonstoichiometry from CS planes is larger in high zirconium compositions of PZT.

Compatibility of RuO2 electrodes with PZT ceramics

Because of its high electrical conductivity and good diffusion barrier properties ruthenium dioxide (RuO2) is a good electrode material for use with ferroelectric lead zirconate-titanate (PZT) solid solutions. Under certain conditions, RuO2 can react with PZT to form lead ruthenate (Pb2Ru2O6.5) during processing at elevated temperatures resulting in lead depletion from PZT. The standard Gibbs energies of formation of RuO2 and Pb2Ru2O6.5 and activities of components of the PZT solid solution have been determined recently. Using this data along with older thermodynamic information on PbZrO3 and PbTiO3, the stability domain of Pb2Ru2O6.5 is computed as a function of PZT composition, temperature and oxygen partial pressure in the gas phase. The results show PbZrO3-rich compositions are more prone to react with RuO2 at all temperatures. Increasing temperature and decreasing oxygen partial pressure suppress the reaction. Graphically displayed are the reaction zones as a function of oxygen partial pressure and PZT composition at temperatures 973, 1173 and 1373 K.

Thermodynamic activities in the Pb(Zr1-XTiX)O-3 solid solution at 1373 K

Although Pb(Zr1-XTiX)O-3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1-XTiX)O-3 solid solution with cubic perovskite structure and (Zr1-YTiY)O-2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs-Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1-YTiY)02 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model: Delta G(E.M) (J mol(-1)) = X-PbTiO3 X-PbZrO3(5280X(PbTiO3) - 1980X(PbZrO3)) where Delta G(E.M) is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution. (C) 2007 Elsevier B.V. All rights reserved.

Investigation of true remnant polarization response in heterostructured artificial biferroics

Epitaxial bilayered thin films composed of ferromagnetic La0.6Sr0.4MnO3 and ferroelectric 0.7Pb (Mg1/3Nb2/3)O3-0.3(PbTiO3) were fabricated on LaAlO3 (100) substrates by pulsed laser ablation. Ferroelectric, ferromagnetic and magneto-dielectric characterizations performed earlier indicated the possible existence of strain-mediated magneto-electric coupling in these biferroic heterostructures. In order to investigate their true remnant polarization characteristics, usable in devices, room-temperature polarization versus electric field, positive-up negative-down (PUND) pulse polarization studies and remnant hysteresis measurements were carried out. The PUND and remnant hysteresis measurements revealed the significant contribution of the non-remnant component in the observed polarization hysteresis response of these heterostructures. (C) 2010 Published by Elsevier Ltd

Low temperature fabrication and impedance spectroscopy of PMN-PT ceramics

Single phase perovskite 0.9Pb(Mg1/3Nb2/3)O-3-0.1(PbTiO3) ceramics were prepared using the columbite precursor method after optimizing the synthesis conditions. X-ray diffraction (XRD) studies were carried out to verify the phase formation at each processing step. Scanning electron microscopy (SEM) was employed to observe the microstructure of the sintered ceramics. Impedance and modulus spectroscopic data were used to gain an insight into the electrical properties of the samples and with a view to observing the relaxations in them. (C) 1999 Elsevier Science Ltd.

Electrical properties of La-graded heterostructure of Pb1?xLaxTiO3 thin films

La-graded heterostructure films were prepared by sol-gel technique on platinum substrates and electrical properties of these films were compared with those of conventional thin films of similar compositions. X-ray diffraction results indicate the pure perovskite polycrystalline structure of these films. Atomic Force Microscopy analysis revealed a finer grain size and relatively lower surface roughness. Relatively higher values of Pm and Pr (69 and 38 ?C cm?2, respectively) and excellent dielectric properties with lower loss (K=1900, tan ?=0.035 at 100 kHz) were observed for La-graded heterostructure films. Also lower leakage current density (not, vert, similar2.5 nA cm?2) and a higher onset field (not, vert, similar50 kV cm?1) of space charge conduction indicated higher breakdown strength and good leakage current characteristics. The ac electric field dependence of the permittivity at sub-switching fields was analyzed in the framework of the Rayleigh dynamics of domain walls. The estimated irreversible domain wall displacement contribution to the total dielectric permittivity was 17 and 9% for conventional 15 at.% La doped PbTiO3 and La-graded heterostructure films, respectively. The improved dielectric and polarization behavior of La-graded heterostructure films may be attributed to homogenous dopant distribution compared to the conventional 15 at.% La doped PbTiO3 films.