Many ferroelectric solid solutions exhibit enhanced electro-mechanical properties at the morphotropic boundary separating two phases with different orientations of polarization. The mechanism of properties enhancement is associated with easy paths for polarization rotation in anisotropically flattened free energy profile. Another mechanism of properties enhancement related to free energy flattening is polarization extension. It is best known at temperature-driven ferroelectric-paraelectric phase transitions and may lead to exceedingly large properties. Its disadvantage is temperature instability of the enhancement. In this paper a temperature-composition phase diagram is proposed that exhibits compositionally driven-phase transitions with easy paths for both polarization rotation and polarization extension.
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…
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.
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…
A simple model to reproduce strong enhancement of dielectric response near the morphotropic phase boundary (MPB) is proposed. This model consists of long-range dipole-dipole interaction and compositional chemical disorder incorporated by the variation in lengths of dipole moments. By applying Monte Carlo simulation, we show that there appears a ferroelectric boundary phase between two types of antiferroelectric phases at an optimal strength of randomness. In the boundary phase, ferroelectric domain becomes remarkably large and flexible to external electric fields, leading to huge dielectric re…
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…
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…
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…
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…
The symmetric studies on the structure-property relationship of the unpoled and poled states of 0.67BiFeO3-0.33BaTiO3 (0.67BF-0.33BT) were conducted to understand the origin of the morphotropic phase boundary (MPB) in BF-BT. A typical relaxor-type dielectric anomaly was observed (Tf, ~627 K). The remnant polarization (Pr) and maximum value of electro-strain (Sm) increase clearly during heating (Pr, ~40 uC/cm2; Sm, 0.191 % under 40 kV/cm at 453 K). The first-cycle electro-strain loops indicate the difference in the polar state between 0.67BF-0.33BT and 0.94BiNaTiO3-0.06BaTiO3. Both the unpoled …
Structure of the morphotropic phase and the phase coexistence region has been investigated in (1-x)Bi(Mg1/2Zr1/2)O3-xPbTiO3 ceramics. The structure is cubic with space group Pm3m for the compositions with x<0.57 and tetragonal with space group P4mm for the compositions with x>0.59. For the compositions with 0.56<x<0.60, both the tetragonal and cubic phases coexist, which suggest very narrow morphotropic phase boundary region of compositional width Δx~0.03. Rietveld refinement of the structure using x-ray diffraction data confirms coexistence of the tetragonal and cubic phases in the MPB region…
Two-dimensional polarity is intriguing but remains in the early stage. Here a structural evolution diagram is established for GeS monolayer, which leads a noncollinear ferrielectric $δ$-phase energetically as stable as the ferroelectric $α$-phase. Its ferrielectricity is induced by the phonon frustration, i.e., the competition between ferroelectric and antiferroelectric modes, providing more routes to tune its polarity. Besides its prominent properties like large band gap, large polarization, and high Curie temperature, more interestingly, the morphotropic phase boundary between $α$- and $δ$-p…
Morphotropic phase boundaries (MPBs) show substantial piezoelectric and dielectric responses, which have practical applications. The predicted existence of MPB in HfO2-ZrO2 solid solution thin film has provided a new way to increase the dielectric properties of a silicon-compatible device. Here, we present a new fabrication design by which the density of MPB and consequently the dielectric constant of HfO2-ZrO2 thin film was considerably increased. The density of MPB was controlled by fabrication of a 10-nm [1 nm-Hf0.5Zr0.5O2 (Ferroelectric)/1 nm-ZrO2 (Antiferroelectric)] nanolaminate followed…
Recently, based on the phase-field modeling, it was predicted that Hf1-xZrxO2 (HZO) exhibits the morphotropic phase boundary (MPB) in its compositional phase diagram. Here, we investigate the effect of structural changes between tetragonal (t) and orthorhombic (o) phases on the ferroelectric and dielectric properties of HZO films to probe the existence of MPB region. The structural analysis show that by adjusting the ozone dosage during the atomic layer deposition process and annealing conditions, different ratios of t- to o-phases (f_(t/o) ) were achieved which consequently affect the ferroel…
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…
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…
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…
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…
Spatially modulated morphotropic phase boundaries in a compressively strained multiferroic thin film
University of Southern California（南加州大学）；University of Michigan, Dearborn（密歇根大学迪尔伯恩分校）；University of California, Berkeley（加州大学伯克利分校）；Cornell University（康奈尔大学）
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…
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…
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…
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 novel strain-driven morphotropic phase boundary (MPB) in highly-strained BiFeO3 thin film is featured by ordered mixed phase nanodomains (MPNs). Through scanning probe microscopy and synchrotron X-ray diffraction, eight structural variants of the MPNs are identified. Detailed polarization configurations within the MPNs are resolved using angular-dependent piezoelectric force microscopy. Guided by the obtained results, deterministic manipulation of the MPNs has been demonstrated by controlling the motion of the local probe. These findings are important for in-depth understanding of the ultr…
We have proposed the polarization rotation theory to understand the underlying physics of the large piezoelectric effect in ferroelectric crystals by referring to the coherent rotation model in ferromagnetism. When both the electric field energy and crystalline anisotropy energy are taken into account, the polarization in BaTiO3 crystal can be rotated toward the field direction. The numerical results have indicated the highly anisotropic polarization rotations and the field-induced-phases with different symmetries in the crystal. This theory is helpful for understanding the polarization revers…
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…
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…
The polarization and strain response of ferroelectric materials at fields below the macroscopic coercive field is of a paramount importance for the operation of many electronic devices. The response of real ferroelectric and related materials is in general complex and difficult to interpret. The reason for this is that many processes in a ferroelectric material contribute to its properties, often concurrently. Examples include motion of ferroelectric and ferroelastic domains, presence of domains within domains, dynamics of different types of polar nano-entities, interaction of polar nano-entit…
The effect of polarization rotation on the performance of metal oxide semiconductor field-effect transistors was investigated with a Landau-Ginzburg-Devonshire theory based model. In this analytical model, depolarization field, polarization rotations and the electrostatic properties of the doped silicon substrate are considered to illustrate the size effect of ferroelectric oxides and the stability of polarization in each direction. Based on this model, we demonstrate that MOSFET operation could be achieved by polarization reorientation with a low operating voltage, if the thickness of ferroel…
We use molecular dynamics simulations to understand the mechanisms of polarization switching in ferroelectric BaTiO$_3$ achieved with external electric field. For tetragonal and orthorhombic ferroelectric phases, we determine the switching paths, and show that polarization rotation through intermediate monoclinic phases (a) facilitates switching at low fields (b) is responsible for a sharp anisotropy in polarization switching. We develop understanding of this through determination of detailed electric field-temperature phase diagrams, that are fundamental to technological applications based on…
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…
We study the electrocaloric effect in the classic ferroelectric BaTiO3 through a series of phase transitions driven by applied electric field and temperature. We find both negative and positive electrocaloric effects, with the negative electrocaloric effect, where temperature decreases with applied field, in monoclinic phases. Macroscopic polarization rotation is evident through the monoclinic and orthorhombic phases under applied field, and is responsible for the negative electrocaloric effect.
Ferroelectrics are characterized by domain structures as are other ferroics. At the nanoscale though, ferroelectrics may exhibit non-trivial or exotic polarization configurations under proper electrostatic and elastic conditions. These polar states may possess emerging properties not present in the bulk compounds and are promising for technological applications. Here, the observation of rotational polarization topologies at the nanoscale by means of aberration-corrected scanning transmission electron microscopy is reported in BaTiO3/SrTiO3 superlattices grown on cubic SrTiO3(001). The transiti…
A key property that drives research in ferroelectric perovskite oxides is their strong piezoelectric response in which an electric field is induced by an applied strain, and vice-versa for the converse piezoelectric effect. We have achieved an experimental enhancement of the piezoelectric response and dielectric tunability in artificially layered epitaxial PbTiO$_{3}$/CaTiO$_{3}$ superlattices through an engineered rotation of the polarization direction. As the relative layer thicknesses within the superlattice were changed from sample to sample we found evidence for polarization rotation in m…
This work presents the results for the Faraday rotation in pure and Cr-doped lead germanate crystals studied in the course of proper ferroelectric phase transition. We show that the increment of the Faraday rotation appearing at the phase transition is caused by a combined magneto-electrooptic effect induced by spontaneous polarization. It is proportional to the square of spontaneous polarization. The phenomenon revealed by us corresponds to combined effects of crystal optics, which appear due to common action of different fields.
Polarization hysteresis loops, x-ray diffraction (XRD) and temperature dependent dielectric constant under different electric fields for <110> oriented 0.7 Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 single crystals were measured. The field-induced phase transition and the process of depolarization were discussed. The results show that with the electric field increasing, the crystal form changes along via polar-axis reorientation and polarization rotation. However, the depolarization process is not just the reversal of the polarization process. It is noticed that just from the temperature dependent dielectric …
A Boltzmann statistical approach for the analysis of polarization states in mixed phase ferroelectric materials: application to morphological phase boundary
Here, we report a combined experimental-theoretical study showing that collective application of rare earth doping on A-site and epitaxial strain to ferroelectric bismuth titanate does not lead to a very large c-axis polarization as reported previously. Further first principles calculations based on the examination of polarization tensor suggest that simultaneous Bi and Ti site doping could result in moderate polarization along c-axis of bismuth titanate which is typically a preferential axis of film growth and thus enabling c axis oriented films to have appreciable polarization. This approach…
The importance of a high shear coefficient d15 (or d24) to the piezoelectric properties of domain-engineered and polycrystalline ferroelectrics is discussed. The extent of polarization rotation, as a mechanism of piezoelectric response, is directly correlated to the shear coefficient. The terms "rotator" and "extender" are introduced to distinguish the contrasting behaviors of crystals such as 4mm BaTiO3 and PbTiO3. In "rotator" ferroelectrics, where d15 is high relative to the longitudinal coefficient d33, polarization rotation is the dominant mechanism of piezoelectric response; the maximum …
Using the previously developed model we explore the processes of polarization rotation in antiferroelectric crystals of squaric acid by the electric fields directed arbitrarily within the $ac$ plane. Except for some particular directions of the field, the two-step polarization reorientation at low temperatures is predicted: first, to the noncollinear phase with perpendicular sublattice polarizations and then to the collinear ferroelectric phase. However, when the field is directed along the axis of spontaneous sublattice polarizations, the intermediate noncollinear phase is absent; when the fi…
Our first-principles computations show that the ground state of PbTiO$_3$ under hydrostatic pressure transforms discontinuously from $P4mm$ to $R3c$ at 9 GPa. Spontaneous polarization decreases with increasing pressure so that the $R3c$ phase transforms to the centrosymmetric $R\bar{3}c$ phase at around 30 GPa. The first-order phase transition between tetragonal and rhombohedral phase is exceptional since there is no evidence for a bridging phase. The essential feature of the $R3c$ and $R\bar{3}c$ phases is that they allow the oxygen octahedron to increase its volume $V_B$ at the expense of cu…
A pseudospin model for description of the influence of the electric field, confined to the plane of sublattice polarization, on the two-dimensional squaric acid antiferroelectrics is developed. The system behavior is analyzed in terms of the parameters of ferroelectric and antiferroelectric ordering, as well as the non-collinearity angle $θ$, which is the angle between sublattice polarizations. The temperature-electric field $T-E_1$ phase diagram is constructed. Most of the field-induced transitions are found to be associated with polarization rotation. The observed phases include the collinea…
Using the previously developed model we revisit the problem of the electric field induced polarization rotation in antiferroelectric crystals of squaric acid. We test an alternative set of the model parameters, according to which the dipole moments associated with the H$_2$C$_4$O$_4$ groups are assumed to be parallel to the diagonals of the $ac$ plane. The $T$-$E$ phase diagrams and the polarization curves $P(E)$ for the fields directed along the $a$ axis and along one of the diagonals are considered. Comparison of the theoretical results with the newly published experimental data confirm the …
We report the observation a continuous rotation of the polarization in Mn$_{0.95}$Co$_{0.05}$WO$_{4}$ under magnetic field. At zero field, this compound shows a transition into the spiral magnetic and ferroelectric phase at 12.2K, which is the ground state, with the polarization oriented along the b-axis. Increasing b-axis magnetic fields rotate the ferroelectric polarization continuously toward the a-axis, indicating a rotation of the spin spiral plane. This rotation extends over a large field and temperature range. At a constant magnetic field of 3 Tesla, the polarization also rotates from t…
Materials with optical activity can rotate the polarization plane of transmitted light. The most typical example is the natural optical activity, which has the symmetry property of changing sign after space inversion but being invariant to time inversion. Faraday rotation exhibits the opposite: it is invariant to space inversion but changes sign after time reversal. Here, we demonstrate that in a magnetoelectric material, another type of polarization rotation is possible. This effect is investigated in magnetoelectric YbAl3(BO3)4 under the viewpoint of time and space inversion symmetry argumen…
A new technical method is developed for soft x-ray spectroscopy of near-edge x-ray absorption fine structure (NEXAFS). The measurement is performed with continuously rotating linearly polarized light over 2$π$, generated by a segmented undulator. A demonstration of the rotational NEXAFS experiment was successfully made with a 2D film, showing detailed polarization-dependence in intensity of the molecular orbitals. The present approach provides varieties of technical opportunities that are compatible with the state-of-the-art experiments in nano-space and under the $operando$ condition.
Light-matter coupling is investigated by rotating, by an angle θ, the polarization of linearly polarized microwaves with respect to the long-axis of GaAs/AlGaAs Hall-bar electron devices. At low microwave power, P, experiments show a strong sinusoidal variation in the diagonal resistance R_{xx} vs. θat the oscillatory extrema, indicating a linear polarization sensitivity in the microwave radiation-induced magnetoresistance oscillations. Surprisingly, the phase shift θ_{0} for maximal oscillatory R_{xx} response under photoexcitation appears dependent upon the radiation-frequency f, the extremu…
