We report the finding of unusual scale-dependent symmetry below the ferroelectric Curie temperature in the perovskite Pb(Zr1-xTix)O3 single crystals of morphotropic phase boundary compositions. The crystals of tetragonal symmetry (from x-ray diffraction experiments) on sub-micrometer scale exhibit a macroscopic (optically determined) cubic symmetry. This peculiar optical isotropy is explained by the anomalously small size of tetragonal ferroelectric domains. Upon further cooling the crystals transform to the phase consisting of micrometer-sized domains of monoclinic Cm symmetry.
A summary of the work recently carried out on the morphotropic phase boundary (MPB) of PZT is presented. By means of x-ray powder diffraction on ceramic samples of excellent quality, the MPB has been successfully characterized by changing temperature in a series of closely spaced compositions. As a result, an unexpected monoclinic phase has been found to exist in between the well-known tetragonal and rhombohedral PZT phases. A detailed structural analysis, together with the investigation of the field effect in this region of compositions, have led to an important advance in understanding the m…
Results presented in this article demonstrate importance of taking into account such a phenomenon as the solid solution decomposition at the boundaries separating coexisting phases in lead-zirconate-titanate-based solid solutions with compositions belonging to the morphotropic boundary region of the "temperature-composition" phase diagram. It is shown that in the local decomposition of solid solutions in the vicinity of the boundaries separating the tetragonal and rhombohedral phases in lead-zirconate-titanate-based solid solutions lead to the changes of the chemical composition of the solid s…
A first-principles-derived approach is used to study structural, piezoelectric and dielectric properties of Pb(Zr_{1-x}Ti_{x})O_{3} (PZT) solid solutions near the morphotropic phase boundary at low temperature. Three ferroelectric phases are found to exist: a tetragonal phase for larger x compositions, a rhombohedral phase for smaller x compositions, and the recently discovered monoclinic phase in between. In this monoclinic phase, the polarization associated with the Zr atoms behaves differently from the polarization associated with the Ti atoms. As the composition x decreases, the former rot…
We present anelastic and dielectric spectroscopy measurements of PbZr(1-x)Ti(x)O(3) with 0.455 < x < 0.53, which provide new information on the low temperature phase transitions. The tetragonal-to-monoclinic transformation is first-order for x < 0.48 and causes a softening of the polycrystal Young's modulus whose amplitude may exceed the one at the cubic-to-tetragonal transformation; this is explainable in terms of linear coupling between shear strain components and tilting angle of polarization in the monoclinic phase. The transition involving rotations of the octahedra below 200 K is visible…
Temperature dependent structural changes in a nearly pure monoclinic phase composition (x=0.525) of Pb(Zr_xTi_1-x)O_3 (PZT) have been investigated using Rietveld analysis of high-resolution synchrotron powder x-ray diffraction data and correlated with changes in the dielectric constant and planar electromechanical coupling coefficient. Our results show that the intrinsic piezoelectric response of the tetragonal phase of PZT is higher than that of the monoclinic phase. It is also shown that the high piezoelectric response of PZT may be linked with an anomalous softening of the elastic modulus (…
In piezoelectric ceramics the changes in the phase stabilities versus stress and temperature in the vicinity of the phase boundary play a central role. The present study was dedicated to the classical piezoelectric, lead-zirconate-titanate (PZT) ceramic with composition Pb(Zr$_{0.54}$Ti$_{0.46}$)O$_3$ at the Zr-rich side of the morphotropic phase boundary at which both intrinsic and extrinsic contributions to piezoelectricity are significant. The pressure-induced changes in this two-phase (rhombohedral $R3c$+monoclinic $Cm$ at room temperature and $R3c+P4mm$ above 1 GPa pressures) system were …
We report on the discovery of a lead-free morphotropic phase boundary in Sm doped BiFeO3 with a simple perovskite structure using the combinatorial thin film strategy. The boundary is a rhombohedral to pseudo-orthorhombic structural transition which exhibits a ferroelectric (FE) to antiferroelectric (AFE) transition at approximately Bi0.86Sm0.14FeO3 with dielectric constant and out-of-plane piezoelectric coefficient comparable to those of epitaxial (001) oriented Pb(Zr,Ti)O3 (PZT) thin films at the MPB. The discovered composition may be a strong candidate of a Pb-free piezoelectric replacement…
The antiferrodistortive (AFD) phase transition for a pseudotetragonal composition of Pb(Zr0.530Ti0.470)O3 (PZT) doped with 6% Sr has been investigated using sound velocity (4 to 320K), high resolution synchrotron X-ray powder diffraction (100 to 800K) and high resolution as well as high flux neutron powder diffraction measurements (4K) to settle the existing controversies about the true ground state of PZT in the morphotropic phase boundary (MPB) region. The multiplet character of the neutron diffraction profiles of (3/2 1/2 1/2)pc (pseudocubic or pc indices) and (3/2 3/2 1/2)pc superlattice p…
We present here the results of structural studies on multiferroic (1-x)Bi(Ni1/2Ti1/2)O3-xPbTiO3 solid solution using Rietveld analysis on powder x-ray diffraction data in the composition range 0.35 to 0.55. We have determined precisely the stability region of various crystallographic phases at room temperature for (1-x)Bi(Ni1/2Ti1/2)O3-xPbTiO3 . Structural transformation from pseudo-cubic to tetragonal phase is observed via phase coexistence region demarcating the morphotropic phase boundary region. The morphotropic phase boundary region consists of coexisting tetragonal and monoclinic structu…
Evidences of a monoclinic phase in unpoled (PbMg1/3Nb2/3O3)1-x-(PbTiO3)x with x=0.35 (PMN-PT 35%) and unpoled (PbZn1/3Nb2/3O3)1-x-(PbTiO3)x with x=0.09 (PZN-PT 9%) are presented from a neutron Rietveld analysis. This monoclinic phase is different from the phase recently evidenced by Noheda and coworkers in PbZr1-xTixO3 with x=0.481 but is identical to the phase observed in poled PZN-PT with x=0.102 by the same authors. The structural resolutions allowed us to compare both structures and to deduce the direction and magnitude of polarization. In PMN-PT 35% and PZN-PT 9% this phase is characteris…
TEM has shown that the strongly piezoelectric material Pb(Zr0.52Ti0.48)O3 separates into two phases at low temperatures. The majority phase is the monoclinic phase previously found by x-ray diffraction. The minority phase, with a nanoscale coherence length, is a slightly distorted variant of the first resulting from the anti-phase rotation of the oxygen octahedra about [111]. This work clears up a recent controversy about the origin of superlattice peaks in these materials, and supports recent theoretical results predicting the coexistence of ferroelectric and rotational instabilities.
The low temperature antiferrodistortive phase transition in a pseudo-tetragonal composition of PZT with x=0.525 is investigated through a combined synchrotron x-ray and neutron powder diffraction study. It is shown that the superlattice peaks cannot be correctly accounted for in the Rietveld refinement using R3c or R3c+Cm structural models, whereas the Cc space group gives excellent fits to the superlattice peaks as well as to the perovskite peaks. This settles at rest the existing controversies about the structure of the ground state phase of PZT in the MPB region.
A phenomenological theory has been proposed for the diffusionless structural phase transitions in crystalline solids here. It has been found that for BaTiO3 single crystal, both the phase transitions and the crystal structures can be predicted with the crystalline anisotropy constants and order parameter dependent strain constants that depend on the temperature. The results have also shown that the morphotropic phase boundaries in PZT crystals arise from the crystalline anisotropy.
Raman spectra of PbZr1-xTixO3 ceramics with titanium concentration varying between 0.40 and 0.60 were measured at 7 K. By observing the concentration-frequency dependence of vibrational modes, we identified the boundaries among rhombohedral, monoclinic, and tetragonal ferroelectric phases. The analysis of the spectra was made in the view of theory group analysis making possible the assignment of some modes for the monoclinic phase.
Recent structural studies of ferroelectric PbZr(1-x)TixO3 (PZT) with x= 0.48, have revealed a new monoclinic phase in the vicinity of the morphotropic phase boundary (MPB), previously regarded as the the boundary separating the rhombohedral and tetragonal regions of the PZT phase diagram. In the present paper, the stability region of all three phases has been established from high resolution synchrotron x-ray powder diffraction measurements on a series of highly homogeneous samples with 0.42 <=x<= 0.52. At 20K the monoclinic phase is stable in the range 0.46 <=x<= 0.51, and this range narrows …
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…
Complementary diffuse and inelastic synchrotron X-ray scattering measurements of lead zirconate-titanate single crystals with composition near the morphotropic phase boundary (x=0.475) are reported. In the temperature range 293 K < T < 400 K a highly anisotropic quasielastic diffuse scattering is observed. Above 400 K this scattering disappears. Its main features can be reproduced by model of inhomogeneous lattice deformations caused by inclusions of a tetragonal phase into a rhombohedral or monoclinic phase. This observation supports the idea that PZT at its morphotropic phase boundary is ess…
A first-principles-derived approach is developed to study finite-temperature properties of PbZr{1-x}Ti{x}O3 (PZT) solid solutions near the morphotropic phase boundary (MPB). Structural and piezoelectric predictions are in excellent agreement with experimental data and direct first-principles results. A low-temperature monoclinic phase is confirmed to exist, and is demonstrated to act as a bridge between the well-known tetragonal and rhombohedral phases delimiting the MPB. A successful explanation for the large piezoelectricity found in PZT ceramics is also provided.
Properties of Pb(Zr_{1-x}Ti_x)O_3 (PZT) for compositions x near the morphotropic phase boundary and under an electric field are simulated using an ab-initio based approach. Applying an electric field of [111] orientation to tetragonal PZT (e.g., x=0.50) leads to the expected sequence of tetragonal, A-type monoclinic, and rhombohedral structures. However, the application of a field of orientation [001] to rhombohedral PZT (e.g., x=0.47) does not simply reverse this sequence. Instead, the system follows a complicated path involving also triclinic and C-type monoclinic structures. These latter ph…
Anelastic and dielectric spectroscopy measurements on PZT close to the morphotropic (MPB) and antiferroelectric boundaries provide new insight in some controversial aspects of its phase diagram. No evidence is found of a border separating monoclinic (M) from rhombohedral (R) phases, in agreement with recent structural studies supporting a coexistence of the two phases over a broad composition range x < 0.5, with the fraction of M increasing toward the MPB. It is also discussed why the observed maximum of elastic compliance appears to be due to a rotational instability of the polarisation and t…
Recently a new monoclinic phase in the PbZr(1-x)TixO3 ceramic system has been reported by Noheda et al. for the composition x= 0.48. In the present work, samples with Ti contents of x= 0.47 and 0.50, which are both tetragonal below their Curie points, have been investigated. In the sample with x= 0.50, the tetragonal phase was found to transform to a monoclinic phase at about 200 K as the temperature was lowered. The sample with x= 0.47 showed a complicated region of phase coexistence between 440-320 K, becoming rhombohedral at around 300 K. No further symmetry change was found down to 20 K. D…
The competitions between ferroelectric and rotational instabilities in rhombohedral PZT near x = 0.5 are investigated using first principles density functional supercell calculations. As expected, we find a strong ferroelectric instability. However, we also find a substantial R-point rotational instability, close to but not as deep as the ferroelectric one. This is similar to the situation in pure PbZrO_3. These two instabilities are both strongly pressure dependent, but in opposite directions so that lattice compression of less than 1% is sufficient to change their ordering. Because of this, …
Many ferroelectric devices are based on doped lead zirconate titanate (PZT) ceramics with compositions near the morphotropic phase boundary (MPB), at which the relevant material's properties approach their maximum. Based on a synchrotron x-ray diffraction study of MPB PZT, bulk fatigue is unambiguously found to arise from a less effective field induced tetragonal-to-monoclinic transformation, at which the degradation of the polarization flipping is detected by a less intense and more diffuse anomaly in the atomic displacement parameter of lead. The time dependence of the ferroelectric response…
The PZT material near the morphotropic phase boundary where a monoclinic phase was observed is studied. A theory of the tetragonal to monoclinic phase transition was developed within the Landau free energy approach. The phase transition from the tetragonal to the monoclinic phase is of the first order near the second order. Dielectric response near the phase transition from the tetragonal to the monoclinic phase was studied for the crystal and for the ceramic and polycrystalline material taking into account the diagonal 33 and the off diagonal 31 components of susceptibility. The later diverge…
Neutron diffraction data obtained on single crystals of PbZr1-xTixO3 with x = 0.325 and x = 0.460, which lie on the pseudorhombohedral side of the morphotropic phase boundary, suggest a coexistence of rhombohedral (R3m/R3c) and monoclinic (Cm) domains and that monoclinic order is enhanced by Ti substitution. A monoclinic phase with a doubled unit cell (Cc) is ruled out as the ground state.
A monoclinic phase was recently discovered near the morphotropic phase boundary in several high-performance piezoelectric perovskite solid solutions, but its properties have not been reported. In this paper the dielectric, piezo- and ferroelectric properties of the monoclinic Pm phase in the (1-x)Pb(Mg1/3Nb2/3)O3 -xPbTiO3 perovskite system are studied. In a (001)-oriented crystal of composition x=0.33, ferroelectric hysteresis loops with remanent polarization of 23 uC/cm^2 are displayed. In poled monoclinic crystals, under unipolar drive up to 10 kV/cm, the domain walls remain unchanged, the p…
We observed that electric field induces phase transition from tetragonal to rhombohedral in polycrystalline morphotropic lead zirconate titanate (PZT) films, as reported in 2011 for bulk PZT. Moreover, we evidenced that this field-induced phase transition is strongly correlated with PZT film piezoelectric properties, that is to say the larger the phase transition, the larger the longitudinal piezoelectric coefficient d 33,eff . Although d 33,eff is already comprised between as 150 to 170 pm/V, our observation suggests that one could obtain larger d 33,eff values, namely 250 pm/V, by optimizing…
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=…
Piezoelectric PZT solid solutions were studied as a function of pressure and temperature. Moderate pressure is found to induce phase transitions to monoclinic phases (Cm,Cc) for Ti-rich PZT, which are the same ferroelectric phases responsible for the high piezoelectric properties of the MPB. The following transformation sequence P4mm -> Cm -> Cc -> F1 -> F-1 was identified upon increasing pressure. Compression behaviour is dominated by: (1) a rotation and a reduction of the spontaneouspolarization and (2) octahedral tilting leading to unit cell doubling. Future studies as a function of pressur…
Ceramic solid solutions of PbZr(1-x)TixO3 (PZT) with compositions of about x= 0.50 are well-known for their extraordinarily large piezoelectric responses. The latter are highly anisotropic, and it was recently shown that, for the rhombohedral compositions (x< 0.5), the piezoelectric coefficients were largest away from the polar direction, contrary to common belief. Shortly afterwards a low-symmetry monoclinic phase was observed by synchrotron x-ray diffraction at around x=0.50. Similar behavior and features are also present in a number of related lead-based strongly-piezoelectric single crysta…
A morphotropic phase boundary driven by epitaxial strain has been observed in a lead-free multiferroic BiFeO3 thin films and the strain-driven phase transitions were widely reported to be iso-symmetric Cc-Cc ones by recent works. In this paper, we suggest that the tetragonal-like BiFeO3 phase identified in epitaxial films on (001) LaAlO3 single crystal substrates is monoclinic MC. This MC phase is different from MA type monoclinic phase reported in BiFeO3 films grown on low mismatch substrates, such as SrTiO3. This is confirmed not only by synchrotron x-ray studies but also by piezoresponse fo…
We present here the results of the room temperature dielectric constant measurements and Rietveld analysis of the powder x-ray diffraction data on $(1-x)[Pb(Mg_{1/3}Nb_{2/3})O_3]-xPbTiO_3$(PMN-$x$PT) in the composition range $0.20 \leq x \leq 0.45$ to show that the morphotropic phase boundary (MPB) region contains two monoclinic phases with space groups Cm (or $M_B$ type) and Pm (or $M_C$ type) stable in the composition ranges $0.27 \leq x \leq 0.30$ and $0.31 \leq x \leq 0.34$, respectively. The structure of PMN-$x$PT in the composition ranges $0 \leq x \leq$ 0.26, and $0.35 \leq x \leq1$ is …
High resolution x-ray powder diffraction measurements on poled PbZr(1-x)TixO3 (PZT) ceramic samples close to the rhombohedral-tetragonal phase boundary (the so-called morphotropic phase boundary, MPB) have shown that for both rhombohedral and tetragonal compositions, the piezoelectric elongation of the unit cell does not occur along the polar directions but along those directions associated with the monoclinic distortion. This work provides the first direct evidence for the origin of the very high piezoelectricity in PZT.
For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family namely BaTiO3, KNbO3, PbTiO3 Na1/2Bi1/2TiO3 the dielectric and piezoelectric properties of BaTiO3 is considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibits anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from…
Results of Rietveld analysis of the synchrotron XRD data on Pb(Zr_xTi_1-x)O_3 (PZT) for 0.525\leqx\leq0.60 are presented to show the absence of rhombohedral phase on the Zr-rich side of the morphotropic phase boundary (MPB). Our results reveal that the structure of PZT is monoclinic in the Cm space group for 0.525\leq x\leq 0.60. The nature of the monoclinic distortion changes from pseudo-tetragonal for 0.525\leqx\leq0.54 to pseudo-rhombohedral for x>0.54.
The origin of the very large piezoelectric response observed in the vicinity of the morphotropic phase boundary (MPB) in perovskite lead zirconate titanate and related systems has been under intensive studies. Polarization rotation ideas are frequently invoked to explain the piezoelectric properties. It was recently reported that lead titanate undergoes a phase transformation sequence $P4mm\to Pm\to Cm\to R\bar{3}c$ at 10 K as a function of hydrostatic pressure [M. Ahart et al. Nature Letters. \textbf{451}, 545 (2008)]. We demonstrate that this interpretation is not correct by (i) simulating t…
We report neutron inelastic scattering experiments on single crystal PbMg$_{1/3}$Nb$_{2/3}$O$_{3}$ doped with 32\% PbTiO$_{3}$, a relaxor ferroelectric that lies close to the morphotropic phase boundary. When cooled under an electric field $\mathbf{E} \parallel$ [001] into tetragonal and monoclinic phases, the scattering cross section from transverse acoustic (TA) phonons polarized parallel to $\mathbf{E}$ weakens and shifts to higher energy relative to that under zero-field-cooled conditions. Likewise, the scattering cross section from transverse optic (TO) phonons polarized parallel to $\mat…
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…
In this work, we address the issue of peaking of piezoelectric response at a particular composition in the morphotropic phase boundary (MPB) region of (Pb0.940Sr0.06)(ZrxTi1-x)O3 (PSZT) piezoelectric ceramics. We present results of synchrotron x-ray powder diffraction, dielectric, piezoelectric and sound velocity studies to critically examine the applicability of various models for the peaking of physical properties. It is shown that the models based on the concepts of phase coexistence, polarization rotation due to monoclinic structure, tricritical point and temperature dependent softening of…
In this review we address some of the experimental challenges found in the x-ray diffraction characterization of the low-symmetry phases recently discovered in the PZT, PZN-PT and PMN-PT piezoelectric systems around their morphotropic phase boundaries. In particular, we discuss the need for special care in the preparation of powder samples made from single crystals in order to avoid degradation and peak-broadening effects.
The existing controversies about the space group symmetries of Pb(ZrxTi1-x)O3 (PZT) above and below antiferrodistortive (AFD) phase transition temperature (TAFD) in the Zr4+- rich (0.620<x<0.940) compositions are addressed using the results of dielectric, synchrotron x-ray powder diffraction (SXRPD) and neutron powder diffraction (NPD) studies. These compositions undergo an AFD phase transition above room temperature due to tilting of oxygen octahedral leading to a superlattice phase of PZT. We have substituted 6% Sr2+ at Pb2+-site to enhance the tilt angle and thereby the intensity of the sup…
A ferroelectric monoclinic phase of space group $Cm$ ($M_A$ type) has been discovered in 0.65Pb(Mg$_{1/3}$Nb$_{2/3})O_3$-0.35PbTiO$_3$ by means of high resolution synchrotron X-ray diffraction. It appears at room temperature in a single crystal previously poled under an electric field of 43 kV/cm applied along the pseudocubic [001] direction, in the region of the phase diagram around the morphotropic phase boundary between the rhombohedral (R3m) and the tetragonal (P4mm) phases. The monoclinic phase has lattice parameters a = 5.692 A, b = 5.679 A, c = 4.050 A and $β$ = $90.15^{\circ}$, with th…
We find an unexpected tetragonal-to-monoclinic-to-rhombohedral-to-cubic phase transition sequence induced by pressure, and a morphotropic phase boundary in a pure compound using first-principles calculations. Huge dielectric and piezoelectric coupling constants occur in the transition regions, comparable to those observed in the new complex single-crystal solid-solution piezoelectrics such as Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$-PbTiO$_{3}$, which are expected to revolutionize electromechanical applications. Our results show that morphotropic phase boundaries and giant piezoelectric effects do not …
Recently discovered fine structure of the morphotropic phase boundaries in highly piezoelectric mixture compounds PZT, PMN-PT, and PZN-PT demonstrates the importance of highly non-linear interactions in these systems. We show that an adequate Landau-type description of the ferroelectric phase transitions in these compounds is achieved by the use of a twelfth-order expansion of the Landau potential in terms of the phenomenological order parameter. Group-theoretical and catastrophe-theory methods are used in constructing the appropriate Landau potential. A complete phase diagram is calculated in…
Here, we report the unusual behaviour shown by the (BiFeO3)1-x-(PbTiO3)x (BF-xPT) films prepared using a multilayer deposition approach by chemical solution deposition method. Thin film samples of various compositions were prepared by depositing several bilayers of BF and PT precursors by varying the BF or PT layer thicknesses. X-ray diffraction showed that final samples of all compositions show mixing of the two compounds resulting in a single phase mixture, also confirmed by transmission electron microscopy. In contrast to bulk equilibrium compositions, our samples show a monoclinic (MA type…
Lead titanate (PbTiO3) is a classical example of a ferroelectric perovskite oxide illustrating a displacive phase transition accompanied by a softening of a symmetry-breaking mode. The underlying assumption justifying the soft-mode theory is that the crystal is macroscopically sufficiently uniform so that a meaningful free energy function can be formed. In contrast to PbTiO3, experimental studies show that the phase transition behaviour of lead-zirconate-titanate solid solution (PZT) is far more subtle. Most of the studies on the PZT system have been dedicated to ceramic or powder samples, in …
The results are presented of anelastic and dielectric spectroscopy measurements on large grain ceramic PZT with compositions near the two morphotropic phase boundaries (MPBs) that the ferroelectric (FE) rhombohedral phase has with the Zr-rich antiferroelectric and Ti-rich FE tetragonal phases. These results are discussed together with similar data from previous series of samples, and reveal new features of the phase diagram of PZT, mainly connected with octahedral tilting and its coupling with the polar modes. Additional evidence is provided of what we interpret as the onset of the tilt instab…
Devonshire theory provides a successful phenomenological description of many cubic perovskite ferroelectrics such as BaTiO3 via a sixth-order expansion of the free energy in the polar order parameter. However, the recent discovery of a novel monoclinic ferroelectric phase in the PZT system by Noheda et al. (Appl. Phys. Lett. 74, 2059 (1999)) poses a challenge to this theory. Here, we confirm that the sixth-order Devonshire theory cannot support a monoclinic phase, and consider extensions of the theory to higher orders. We show that an eighth-order theory allows for three kinds of equilibrium p…
We combine high-pressure x-ray diffraction, high-pressure Raman scattering, and optical microscope to investigate a series of PMN-xPT solid solutions (x=0.2, 0.3, 0.33, 0.35, 0.37, 0.4) in diamond anvil cells up to 20 GPa at 300 K. The Raman spectra show a peak centered at 380 cm-1 above 6 GPa for all samples, in agreement with previous observations. X-ray diffraction measurements are consistent with this spectral change indicating structural phase transition; we find that the triplet at the pseudo cubic (220) Bragg peak merges into a doublet above 6 GPa. Our results indicate that the morphotr…
Ferroelectric and dielectric properties of polydomain (twinned) single-crystal Pb(Zr1-xTix)O3 thin films are described with the aid of a nonlinear thermodynamic theory, which has been developed recently for epitaxial ferroelectric films with dense laminar domain structures. For Pb(Zr1-xTix)O3 (PZT) films with compositions x = 0.9, 0.8, 0.7, 0.6, 0.5, and 0.4, the "misfit strain-temperature" phase diagrams are calculated and compared with each other. It is found that the equilibrium diagrams of PZT films with x > 0.7 are similar to the diagram of PbTiO3 films. They consist of only four differen…
High-strain piezoelectric materials are often ceramics with a complicated constitution. In particular, PZT is used with compositions near to a so-called morphotropic phase boundary, where not only different variants of the same phase (domains), but different phases may coexist. Micro-mechanical models for ferroelectric ceramics would be much more realistic, if these effects could be incorporated. In this paper, we consider the conditions of mechanical and electrical compatibility of ferroelectric domain structures. We are able to address the question of coexistence of different crystallographi…
We review some of the current research on two of the ultra-high piezoelectric relaxors Pb(Mg1/3Nb2/3)O3 (PMN) and Pb(Zn1/3Nb2/3)O3 (PZN). The discovery of a monoclinic phase in Pb(Zr1-xTix)O3 (PZT) in 1999 by Noheda et al. forced a reassessment of the structural symmetries found near the morphotropic phase boundary in PZT, as well as in the PbTiO3 (PT) doped systems PZN-PT, and PMN-PT. All three systems are now known to have nearly identical phase diagrams that exhibit a rhombohedral-monoclinic-tetragonal structural sequence with increasing PbTiO3 concentration. The dynamical properties of the…
The complex elastic compliance and dielectric susceptibility of (Na_{0.5}Bi_{0.5})_{1-x}Ba_{x}TiO_{3} (NBT-BT) have been measured in the composition range between pure NBT and the morphotropic phase boundary included, 0 <= x <= 0.08. The compliance of NBT presents sharp peaks at the rhombohedral/tetragonal and tetragonal/cubic transitions, allowing the determination of the tetragonal region of the phase diagram, up to now impossible due to the strong lattice disorder and small distortions and polarizations involved. In spite of ample evidence of disorder and structural heterogeneity, the R-T t…
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…
A first-principles-derived scheme, that incorporates ferroelectric and antiferrodistortive degrees of freedom, is developed to study finite-temperature properties of PbZr1-xTixO3 solid solutions near its morphotropic phase boundary. The use of this numerical technique (i) resolves controversies about the monoclinic ground-state for some Ti compositions, (ii) leads to the discovery of an overlooked phase, and (iii) yields three multiphase points, that are each associated with four phases. Additional neutron diffraction measurements strongly support some of these predictions.
