First-principles study of (BiScO3){1-x}-(PbTiO3){x} piezoelectric alloys

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 responses of BS-PT and Pb(Zr_{1-x}Ti_x)O3 (PZT) at the MPB are comparable, at least as far as the computed values of the piezoelectric coefficient d_15 are concerned. While our results are generally consistent with experiment, they also suggest that certain intrinsic properties of BS-PT may be even better than has been indicated by experiments to date. We also discuss results for PZT that demonstrate the prominent role played by Pb displacements in its piezoelectric properties.Comment: 6 pages, with 3 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/ji_bi/index.htm

Ab-initio design of perovskite alloys with predetermined properties: The case of Pb(Sc_{0.5} Nb_{0.5})O_{3}

A first-principles derived approach is combined with the inverse Monte Carlo technique to determine the atomic orderings leading to prefixed properties in Pb(Sc_{0.5}Nb_{0.5})O_{3} perovskite alloy. We find that some arrangements between Sc and Nb atoms result in drastic changes with respect to the disordered material, including ground states of new symmetries, large enhancement of electromechanical responses, and considerable shift of the Curie temperature. We discuss the microscopic mechanisms responsible for these unusual effects.Comment: 5 pages with 2 postscript figures embedde

Properties of Pb(Zr,Ti)O3_3 ultrathin films under stress-free and open-circuit electrical boundary conditions

A first-principles-based scheme is developed to simulate properties of (001) PbO-terminated Pb(Zr$_{1-x}$Ti$_{x}$)O$_3$ thin films that are under stress-free and open-circuit boundary conditions. Their low-temperature spontaneous polarization never vanishes down to the minimal thickness, and continuously rotates between the in-plane and directions when varying the Ti composition around x=0.50. Such rotation dramatically enhances piezoelectricity and dielectricity. Furthermore, the order of some phase transitions changes when going from bulk to thin films.Comment: 11 pages, 3 figure

Towards multicaloric effect with ferroelectrics

This work was supported in part by the National Science Foundation (Grant No. CMMI-#1361713) and by DOE Ames Laboratory on “The Caloric Materials Consortium”. L.B. acknowledges the support of ARO Grant No. W911NF-16-1-0227. B.D. acknowledges a public grant overseen by the French National Research Agency (ANR) as part of the “Investissements d’Avenir” program (Grant No. ANR-10-LABX-0035, Labex NanoSaclay) and Fonds National de la Recherche du Luxembourg (FNR) through InterMobility Project No. 16/1159210 “MULTICALOR”.Utilizing thermal changes in solid state materials strategically offers caloric-based alternatives to replace current vapor-compression technology. To make full use of multiple forms of the entropy and achieve higher efficiency for designs of cooling devices, the multicaloric effect appears as a cutting-edge concept encouraging researchers to search for multicaloric materials with outstanding caloric properties. Here we report the multicaloric effect in BaTiO3 single crystals driven simultaneously by mechanical and electric fields and described via a thermodynamic phenomenological model. It is found that the multicaloric behavior is mainly dominated by the mechanical field rather than the electric field, since the paraelectric-to-ferroelectric transition is more sensitive to mechanical field than to electric field. The use of uniaxial stress competes favorably with pressure due to its much higher caloric strength and negligible elastic thermal change. It is revealed that multicaloric response can be significantly larger than just the sum of mechanocaloric and electrocaloric effects in temperature regions far above the Curie temperature but cannot exceed this limit near the Curie temperature. Our results also show the advantage of the multicaloric effect over the mechanically-mediated electrocaloric effect or electrically-mediated mechanocaloric effect. Our findings therefore highlight the importance of ferroelectric materials to develop multicaloric cooling.PostprintPeer reviewe

Soft Phonon Anomalies in the Relaxor Ferroelectric Pb(Zn_1/3Nb_2/3)_0.92Ti_0.08O_3

Neutron inelastic scattering measurements of the polar TO phonon mode dispersion in the cubic relaxor Pb(Zn_1/3Nb_2/3)_0.92Ti_0.08O_3 at 500K reveal anomalous behavior in which the optic branch appears to drop precipitously into the acoustic branch at a finite value of the momentum transfer q=0.2 inverse Angstroms, measured from the zone center. We speculate this behavior is the result of nanometer-sized polar regions in the crystal.Comment: 4 pages, 4 figure

Spin Switching and Magnetization Reversal in Single-Crystal NdFeO\u3csub\u3e3\u3c/sub\u3e

We report an experimental and computational study of single-crystal NdFeO3, which features two inequivalent magnetic sublattices, namely, Fe and Nd sublattices that are coupled in an antiparallel fashion. This paper reveals that a strong interaction between 3d and 4f electrons of the two sublattices along with a spin-lattice coupling drives an extremely interesting magnetic state that is highly sensitive to the orientation and history of weak magnetic field. The following phenomena are particularly remarkable: (1) sharply contrasting magnetization M(T) along the a and c axes; (2) a first-order spin switching along the a axis below 29 K when the system is zero-field-cooled; and (3) a progressive magnetization reversal when the system is field-cooled. The intriguing magnetic behavior is captured in our first-principles density functional theory calculations

Nonlinear phonon Hall effects in ferroelectrics: its existence and non-volatile electrical control

Nonlinear Hall effects have been previously investigated in non-centrosymmetric systems for electronic systems. However, they only exist in metallic systems and are not compatible with ferroelectrics since these latter are insulators, hence limiting their applications. On the other hand, ferroelectrics naturally break inversion symmetry and can induce a non-zero Berry curvature. Here, we show that a non-volatile electric-field control of heat current can be realized in ferroelectrics through the nonlinear phonon Hall effects. More precisely, based on Boltzmann equation under the relaxation-time approximation, we derive the equation for nonlinear phonon Hall effects, and further show that the behaviors of nonlinear phonon (Boson) Hall effects are very different from nonlinear Hall effects for electrons (Fermion). Our work provides a route for electric-field control of thermal Hall current in ferroelectrics.Comment: 16 pages, 2 figure

Virtual-crystal approximation that works: Locating a composition phase boundary in Pb(Zr_{1-x}Ti_3)O_3

We present a new method for modeling disordered solid solutions, based on the virtual crystal approximation (VCA). The VCA is a tractable way of studying configurationally disordered systems; traditionally, the potentials which represent atoms of two or more elements are averaged into a composite atomic potential. We have overcome significant shortcomings of the standard VCA by developing a potential which yields averaged atomic properties. We perform the VCA on a ferroelectric oxide, determining the energy differences between the high-temperature rhombohedral, low-temperature rhombohedral and tetragonal phases of Pb(Zr_{1-x}Ti_x)O_3 at x=0.5 and comparing these results to superlattice calculations and experiment. We then use our new method to determine the preferred structural phase at x=0.4. We find that the low-temperature rhombohedral phase becomes the ground state at x=0.4, in agreement with experimental findings.Comment: 5 pages, no figure

Phenomenological theory of phase transitions in highly piezoelectric perovskites

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 phenomenological parameter space. The theory describes both PZT and PZN-PT types of phase diagrams, including the newly found monoclinic and orthorhombic phases. Anomalously large piezoelectric coefficients are predicted in the vicinity of the phase transition lines.Comment: RevTex4, 8 pages, 2 figures. Dramatically changed after referees' Comments, to appear in Phys. Rev. B, 1 April 200