Piezoelectric and ferroelectric ceramics with a high Curie temperature (Tc) have attracted a growing attention owning to their applications under severe environments. In this work, phase structure, dielectric, ferroelectric and piezoelectric properties of (0.975-x)BiScO3-xPbTiO3-0.025Pb(Cd1/3Nb2/3)O3 ceramics (x = 0.58-0.64) were studied. A composition-induced structural transformation occurs from rhombohedral phase to tetragonal phase through an intermediate monoclinic phase with the increasing PT concentration. The relationship between structure and electrical properties of the system were discussed. The BS-xPT-PCN system near the morphotropic phase boundary (x = 0.62) exhibits excellent piezoelectric and ferroelectric performances with d33 = 508 pC/N, kp = 56%, and Pr = 40 uC/cm2. The high-temperature piezoelectricity of the sample with MPB (x = 0.62) was characterized by an in situ XRD. The excellent thermal stability of the crystal structure and the piezoelectric property indicate that the BS-xPT-PCN system is a promising candidate for high temperature piezoelectric applications.
The contributory mechanisms associated with high piezoelectric response in piezoelectric ceramics have been examined by in-situ electric field dependent high energy synchro x-ray diffraction study. A comparative study of electric field induced lattice strain and the propensity for non-180o domain switching on two closeby compositions of a high performance piezoelectric alloy (1-x)PbTiO3-(x)BiScO3, one within the morphotropic phase boundary (MPB) region exhibiting d33 of 425 pC/N and another just outside the MPB region exhibiting d33 of 260 pC/N, unravelled that, inspite of the MPB specimen exh…
The lattice strain and domain switching behaviour was investigated as a function of cyclic field and grain orientation for a pseudorhombohedral composition of the high Curie point piezoelectric system xBiScO3 - (1-x)PbTiO3 (x = 0.40) by in-situ electric field diffraction technique with high energy synchrotron x-rays. Along the field direction, the system exhibts five time large strain along 100 as compared to the 111 direction. A one-to-one correspondence between the 200 lattice strain and the 111 domain switching suggests a strong correlation between the two phenomena.
We report a first-principles study of a class of (BiScO3)_{1-x}-(PbTiO3)_x (BS-PT) alloys recently proposed by Eitel et al. as promising materials for piezoelectric actuator applications. We show that (i) BS-PT displays very large structural distortions and polarizations at the morphotropic phase boundary (MPB) (we obtain a c/a of ~1.05-1.08 and P_tet of ~1.1 C/m^2); (ii) the ferroelectric and piezoelectric properties of BS-PT are dominated by the onset of hybridization between Bi/Pb-6p and O-2p orbitals, a mechanism that is enhanced upon substitution of Pb by Bi; and (iii) the piezoelectric r…
There is a general perception that large piezoelectric response in ferroelectric alloys requires tuning the system towards a morphotropic phase boundary (MPB), i.e., a composition driven inter-ferroelectric instability. Here we show that high piezoelectric response can be realized even in non-MPB alloy systems. This is demonstrated on (1-x)PbTiO3-(x)Bi(Zr0.5Ni0.5)O3 (PT-BNZ) by a comprehensive study involving electric-field and temperature dependent XRD, Raman spectroscopy, dielectric, piezoelectric and high field electrostrain measurements. We found that poling-field irreversibly suppresses t…
Using data obtained from first-principles calculations, we show that the position of the morphotropic phase boundary (MPB) and transition temperature at MPB in ferroelectric perovskite solutions can be predicted with quantitative accuracy from the properties of the constituent cations. We find that the mole fraction of PbTiO$_3$ at MPB in Pb(B$'$B$''$)O$_3$-PbTiO$_3$, BiBO$_3$-PbTiO$_3$ and Bi(B$'$B$''$)O$_3$-PbTiO$_3$ exhibits a linear dependence on the ionic size (tolerance factor) and the ionic displacements of the B-cations as found by density functional theory calculations. This dependenc…
The domain structure of (1-x)Pb(Mg1/3Nb2/3)O3- xPbTiO3 single crystals with composition x ~ 0.33 in the range of the morphotropic phase boundary (MPB) was studied. Based on the analysis of spontaneous strain compatibility and charge of domain walls, we have established the permissible domain arrangements for the ferroelectric phases of different symmetry, which are expected to occur in the range of the MPB. Examination of (001)-oriented unpoled and electrically poled (along the [001] direction) crystal plates in polarizing microscope reveals a monophase state with the domain structure compatib…
Relaxor ferroelectrics are applied in electronic devices such as actuators and sonars. Morphotrophic phase boundaries (MPBs) with monoclinic structures are known for their high piezoelectricity and electromechanical coupling factors in solid solutions of PbTiO$_{3}$ and relaxor ferroelectrics (Pb(Mg$_{1/3}$, Nb$_{2/3}$)O$_{3}$ or Pb(Zn$_{1/3}$, Nb$_{1/3}$)O$_{3}$). However, the monoclinic structures related to polar nanosize domains (polar nanoregions) exhibiting the relaxor properties of dielectric dispersion have not been reported. Using transmission electron microscopy and synchrotron x-ray…
Enhanced domain mobility is considered as one of the important characteristics of morphotropic phase boundary (MPB) ferroelectrics exhibiting a very large piezoelectric response. For nearly two decades, Rayleigh analysis of dielectric and piezoelectric response at sub-coercive fields has been used as a phenomenological tool to determine the relative contribution of domain walls in influencing polar properties in these systems. The high value of the extrinsic Rayleigh coefficient at the MPB is generally attributed to enhanced domain mobility. Using coercive field as a measure of hindrance to do…
Structural phase transformations in (001)-oriented (1-x)Pb(Mg1/3Nb2/3O3)-32%PbTiO3 (PMN-x%PT) crystals have been investigated by x-ray diffraction. A C->T->MC sequence was observed in both the field-cooled (FC) and zero-field-cooled (ZFC) conditions. Most interestingly, an anomalous increase in the C->T phase boundary with increasing field has been observed, which is seemingly a common characteristic of crystals whose compositions are in the vicinity of the MPB, irrespective of the width of the T and MC phase regions.
The symmetry was examined using neutron diffraction method on Pb(Zn1/3Nb2/3)O3 -9%PbTiO3 (PZN/9PT) which has a composition at the morphotropic phase boundary (MPB) between Pb(Zn1/3Nb2/3)O3 and PbTiO3. The results were compared with those of other specimens with same composition but with different prehistory. The equilibrium state of all examined specimens is not the mixture of rhombohedral and tetragonal phases of the end members but exists in a new polarization rotation line Mc# (orthorhombic-monoclinic line). Among examined specimens, one exhibited tetragonal symmetry at room temperature but…
Here, we report the existence of large remnant polarization and dielectric constant in PbTiO3 buffered polycrystalline (BiFeO_3)_{1-x} (PbTiO_3)_x thin films of composition x = 0.25, 0.30 and 0.35 around the morphotropic phase boundary. The films were deposited by chemical solution deposition on platinized silicon substrates. Films reveal a perovskite structure with a tendency to retain rhombohedral structure even at higher PbTiO_3 content than that reported in bulk. We observe very large remnant polarization, ~75 microC/cm^2, and high dielectric constant, ~2400 at 1 kHz for x = 0.3, which lie…
Ferroelectric perovskite oxides possess a large electrocaloric (EC) effect, but usually at high temperatures near the ferroelectric/paraelectric phase transition temperature, which limits their potential application as next-generation solid-state cooling devices. We use classical molecular dynamics to study the electric field induced phase transitions and EC effect in PMN-PT (PbMg1/3Nb2/3O3-PbTiO3). We find that the maximum EC strength of PMN-PT occurs within the morphotropic phase boundary (MPB) region at 300 K. The large adiabatic temperature change is caused by easy rotation of polarization…
The structural characteristics of the perovskite- based ferroelectric Pb(Zn1/3Nb2/3)O3-9%PbTiO3 at the morphotropic phase boundary (MPB) region (x≃0.09) have been analyzed. The analysis is based on the symmetry adapted free energy functions under the assumption that the total polarization and the unit cell volume are conserved during the transformations between various morphotropic phases. Overall features of the relationships between the observed lattice constants at various conditions have been consistently explained. The origin of the anomalous physical properties at MPB is discussed.
The purpose of the present work is to report studies on structural phase transition for PMN-xPT single crystal, with melt PbTiO3 composition around the MPB (x = 0.35 mol %), using infrared spectroscopy technique. The study was centered on monitoring the behavior of the stretching-(Nb-O), stretching-(Ti-O) and stretching-(Mg-O) stretching modes as a function of temperature. Singularities observed between 198 and 300 K suggested a possible coexistence between the monoclinic and tetragonal phases, not revealed by others techniques, for PMN-PT composition studied near MPB.
Strong piezoelectricity in the perovskite-type PbZr(1-x)TixO3 (PZT) and Pb(Zn1/3Nb2/3)O3-PbTiO3 (PZN-PT) systems is generally associated with the existence of a morphotropic phase boundary (MPB) separating regions with rhombohedral and tetragonal symmetry. An x-ray study of PZN-9%PT has revealed the presence of a new orthorhombic phase at the MPB, and a near-vertical boundary between the rhombohedral and orthorhombic phases, similar to that found for PZT between the rhombohedral and monoclinic phases. We discuss the results in the light of a recent theoretical paper by Vanderbilt and Cohen, wh…
Despite the technological significance of the tetragonal PbTiO3 for the piezoelectric transducer industry, its high pressure behaviour is quite controversial as two entirely different scenarios, involving pressure induced (1) morphotropic phase boundary (MPB) like structural transition with concomitant rotation of the ferroelectric polarization vector and (2) antiferrodistortive (AFD) phase transition followed by emergence of a reentrant ferroelectric phase, have been proposed in recent theoretical and experimental studies. We have attempted to address these controversies through a high resolu…
We identify a first-order, isosymmetric transition between a ferrielectric (FiE) and ferroelectric (FE) state in $A$-site ordered LaScO$_{3}$/BiScO$_{3}$ and LaInO$_{3}$/BiInO$_{3}$ superlattices. Such a previously unreported ferroic transition is driven by the easy switching of cation displacements without changing the overall polarization direction or crystallographic symmetry. Epitaxial strains less than 2% are predicted to be sufficient to transverse the phase boundary, across which we capture a ~5X increase in electric polarization. In a fashion similar to classic Pb-based perovskite cera…
The perovskite-like ferroelectric system PbZr(1-x)Ti(x)O3 (PZT) has a nearly vertical morphotropic phase boundary (MPB) around x=0.45-0.50. Recent synchrotron x-ray powder diffraction measurements by Noheda et al. [Appl. Phys. Lett. 74, 2059 (1999)] have revealed a new monoclinic phase between the previously-established tetragonal and rhombohedral regions. In the present work we describe a Rietveld analysis of the detailed structure of the tetragonal and monoclinic PZT phases on a sample with x= 0.48 for which the lattice parameters are respectively: at= 4.044 A, ct= 4.138 A, at 325 K, and am=…
Bulk single-crystal relaxor-ferroelectrics, like Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT), are widely known for their large piezoelectricity. This is attributed to polarization rotation which is facilitated by the presence of various crystal symmetries for compositions near a morphotropic phase boundary (MPB). Relaxor-ferroelectric thin films, which are necessary for low-voltage applications, suffer a reduction in their piezoelectric response due to clamping by the passive substrate. To understand the microscopic behavior of this adverse phenomenon, we employ AC electric field driven in-operando synch…
