Ferroelectricity in the magnetic E-phase of orthorhombic perovskites

We show that the symmetry of the spin zigzag chain E phase of the orthorhombic perovskite manganites and nickelates allows for the existence of a finite ferroelectric polarization. The proposed microscopic mechanism is independent of spin-orbit coupling. We predict that the polarization induced by the E-type magnetic order can potentially be enhanced by up to 2 orders of magnitude with respect to that in the spiral magnetic phases of TbMnO3 and similar multiferroic compounds.     

Ferroelectric smectic phase formed by achiral straight core mesogens

We report electro-optic experiments in liquid crystalline freestanding films of achiral hockey stick shaped mesogens with a straight aromatic core. The material forms two smectic mesophases. In the higher temperature phase, a spontaneous polarization exists in the smectic layer plane and the films show polar switching in electric fields. It is the first example of a ferroelectric phase formed by nearly rodlike achiral mesogens. Mirror symmetry of the phase is spontaneously broken. We propose a molecular configuration similar to a synclinic ferroelectric (C(S)P(F)) high temperature phase and an anticlinic, probably antiferroelectric (C(A)P(A)) low temperature phase.     

Multiferroicity induced by dislocated spin-density waves

We uncover a new pathway towards multiferroicity, showing how magnetism can drive ferroelectricity without relying on inversion symmetry breaking of the magnetic ordering. Our free-energy analysis demonstrates that any commensurate spin-density-wave ordering with a phase dislocation, even if it is collinear, gives rise to an electric polarization. Because of the dislocation, the electronic and magnetic inversion centers do not coincide, which turns out to be a sufficient condition for multiferroic coupling. The novel mechanism explains the formation of multiferroic phases at the magnetic commensurability transitions, such as the ones observed in YMn(2)O(5) and related compounds. We predict that in these multiferroics an oscillating electrical polarization is concomitant with the uniform polarization. On the basis of our theory, we put forward new types of magnetic materials that are potentially ferroelectric.     

Magnetic inversion symmetry breaking and ferroelectricity in TbMnO3

TbMnO3 is an orthorhombic insulator where incommensurate spin order for temperature T(N)<41 K is accompanied by ferroelectric order for T<28 K. To understand this, we establish the magnetic structure above and below the ferroelectric transition using neutron diffraction. In the paraelectric phase, the spin structure is incommensurate and longitudinally modulated. In the ferroelectric phase, however, there is a transverse incommensurate spiral. We show that the spiral breaks spatial inversion symmetry and can account for magnetoelectricity in TbMnO3.     

Symmetry and magnetic field driven transitions in the 2D triangular lattice compound RbFe(MoO4)2

The temperature versus magnetic field phase diagram of the 2D triangular lattice and multiferroic compound RbFe(MoO(4))(2) is analysed from the point of view of symmetry. The paramagnetic space group and its irreducible representations are used in order to obtain the magnetic symmetry of the possible modulated phases and characterize the restrictions imposed by this symmetry on the corresponding magnetic structures. Superspace symmetry is considered in the case of incommensurate phases. It is shown that the experimentally observed phases correspond to different isotropy subgroups originating in the same irreducible representation of the paramagnetic symmetry group. The relevant couplings between the primary transverse spin modulation and the electric polarization, the in-plane magnetization and the secondary longitudinal magnetic modulation are discussed. The mechanisms for the destabilization of the improper ferroelectric chiral phase and the origin of the different orientation of the spins with respect to the external field in the two collinear phases are analysed from a symmetry based perspective.     

Electronic structure and improper electric polarization of samarium orthoferrite

The band structure and distributions of the electron and spin densities of samarium orthoferrite have been calculated within the framework of the first-principles density functional theory in the LSDA + U approximation taking into account the collinear antiferromagnetic ordering of the magnetic moments of iron and samarium cations. The possibility of inducing a ferroelectric state at temperatures below the antiferromagnetic ordering temperature of the magnetic sublattice formed by samarium cations has been considered using the results of the group-theoretical analysis. In the high-temperature range, the formation of regions with a spontaneous electric polarization is possible in the presence of additional factors that reduce the symmetry of the crystal.     

EFFECTS OF LONG-RANGE INTERACTIONS ON THE FERROELECTRIC FILM

The effect of long-range interactions on the spontaneous polarization and the Curie temperature of the ferroelectric film is investigated by use of the Landau theory. On the assumption that the nearest-neighbour interaction remains constant, we find that the spontaneous polarization and the phase transition temperature increase with the enhancement of the long-range interactions. In the case of positive extrapolation length, the critical thickness of the ferroelectric film, in which a size-driven phase transition occurs, decreases with the enhancement of the long-range interactions.     

Ferroelectric polarization flop in a frustrated magnet MnWO4 induced by a magnetic field

The relationship between magnetic order and ferroelectric properties has been investigated for MnWO4 with a long-wavelength magnetic structure. Spontaneous electric polarization is observed in an elliptical spiral spin phase. The magnetic-field dependence of electric polarization indicates that the noncollinear spin configuration plays a key role for the appearance of the ferroelectric phase. An electric polarization flop from the b direction to the a direction has been observed when a magnetic field above 10 T is applied along the b axis. This result demonstrates that an electric polarization flop can be induced by a magnetic field in a simple system without rare-earth 4f moments.     

应变作用下EuTiO_3材料磁性的格林函数理论研究

基于自旋波和格林函数理论,研究了低温下二维应变诱导的EuTiO_3在铁电四方相下的磁性性质,主要讨论了在铁电四方相下Eu离子在铁磁性和反铁磁性有序时系统沿不同高对称性方向的自旋波散射和磁化.我们发现施加外加应变不仅可改变晶格结构的对称性,还可以通过改变电子自旋之间的交换耦合作用,进而改变该材料的磁性散射和磁化等.     

应变作用下EuTiO3材料磁性的格林函数理论研究

基于自旋波和格林函数理论,研究了低温下二维应变诱导的EuTiO3在铁电四方相下的磁性性质,主要讨论了在铁电四方相下Eu离子在铁磁性和反铁磁性有序时系统沿不同高对称性方向的自旋波散射和磁化。我们发现施加外加应变不仅可改变晶格结构的对称性,还可以通过改变电子自旋之间的交换耦合作用,进而改变该材料的磁性散射和磁化等。     

Polarization-based adjustable memory behavior in relaxor ferroelectrics

The irreversible decay of the spontaneous polarization above the phase-transition temperature is a limiting factor in any application of ferroelectric crystals. Here we show that electric fields applied at high temperatures induce a preferred direction in the crystal which is stable even after repeated heating and cooling through the phase transition. This preference in direction leads to a reorientation of domains in the ferroelectric phase. We use pyroelectric measurements to show that the directional preference originates from internal charge carriers interacting with domain walls.     

Ferroelectricity in spiral magnets

It was recently observed that the ferroelectrics showing the strongest sensitivity to an applied magnetic field are spiral magnets. We present a phenomenological theory of inhomogeneous ferroelectric magnets, which describes their thermodynamics and magnetic field behavior, e.g., dielectric susceptibility anomalies at magnetic transitions and sudden flops of electric polarization in an applied magnetic field. We show that electric polarization can also be induced at domain walls and that magnetic vortices carry electric charge.     

4-(cyanomethyl)anilinium perchlorate: a new displacive-type molecular ferroelectric

A new organic ferroelectric compound, 4-(cyanomethyl)anilinium perchlorate, proceeds a second-order phase transition from a paraelectric phase (P2(1)/m) to a ferroelectric phase (P2(1)) at 184 K. A perfect ferroelectric hysteresis loop was observed even at 10 KHz. It is the first example of a molecule-based organic ferroelectric whose polarization can be switched at such a high frequency. The temperature dependent second harmonic generation effect shows that the second-order nonlinear coefficient is nearly zero above T(c) and proportional to the spontaneous polarization below T(c), suggesting the occurrence of symmetry breaking, in good agreement with crystal structural determination. The origin of ferroelectricity was ascribed to the displacements of -NH(3)(+) cations and ClO(4)(-) anions from the symmetric positions including a small part of the order-disorder behaviors of the ClO(4)(-) anions.     

High-T(c) ferroelectricity emerging from magnetic degeneracy in cupric oxide

Cupric oxide is multiferroic at unusually high temperatures. From density functional calculations we find that the low-T magnetic phase is paraelectric, and the higher-T one is ferroelectric with a size and direction of polarization in good agreement with experiments. By mapping the ab?initio results on to an effective spin model, we show that the system has a manifold of almost degenerate ground states. In the high-T magnetic state noncollinearity and inversion symmetry breaking stabilize each other via the Dzyaloshinskii-Moriya interaction. This leads to an unconventional mechanism for multiferroicity, with the particular property that nonmagnetic impurities enhance the effect.     

Upward renormalization of fluctuations in CsMnBr3 with increasing temperature

The temperature dependence of the spin-wave gap in the triangular antiferromagnet CsMnBr3 was studied above the three-dimensional ordering temperature T(N)=8.3 K along the main symmetry directions using inelastic neutron scattering. We find at T(N) two gapped dispersive modes, whose energy increases with temperature. Moreover, the width of the spin-wave band along the [110] direction increases also. In a second session, polarization analysis was applied in order to extract explicitly the components with in-plane and out-of-plane character. The results show that both gapped modes (with axial and radial symmetry) renormalize upwards with rising temperature. We show that this behavior is not compatible with spin-wave theory. In addition, we find a new magnetic anomaly in the paramagnetic phase.     

Order-parameter coupling in the improper ferroelectric lawsonite

Low-temperature specific heat and thermal expansion measurements are used to study the hydrogen-based ferroelectric lawsonite over the temperature range 1.8 K ≤ T ≤ 300 K. The second-order phase transition near 125 K is detected in the experiments, and the low-temperature phase is determined to be improper ferroelectric and co-elastic. In the ferroelectric phase T ≤ 125 K, the spontaneous polarization P(s) is proportional to (1) the volume strain e(s), and (2) the excess entropy ΔS(e). These proportionalities confirm the improper character of the ferroelectric phase transition. We develop a structural model that allows the off-centering of hydrogen positions to generate the spontaneous polarization. In the low-temperature limit we detect a Schottky anomaly (two-level system) with an energy gap of Δ ～ 0.5 meV.     

Narrow Waveguide Based on Ferroelectric Domain Wall

Ferroelectric materials are spontaneous symmetry breaking systems that are characterized by ordered electric polarizations.Similar to its ferromagnetic counterpart,a ferroelectric domain wall can be regarded as a soft interface separating two different ferroelectric domains.Here we show that two bound state excitations of electric polarization(polar wave),or the vibration and breathing modes,can be hosted and propagate within the ferroelectric domain wall.In particular,the vibration polar wave has zero frequency gap,thus is constricted deeply inside ferroelectric domain wall,and can even propagate in the presence of local pinnings.The ferroelectric domain wall waveguide as demonstrated here offers a new paradigm in developing ferroelectric information processing units.     

Aspects of symmetry in the problem of phase transitions in improper ferroelectrics

The term ‘improper’ ferroelectrics has recently come to be used for ferroelectrics in which the spontaneous polarizationP _s is not a transition parameter. From the standpoint of symmetry therefore, the new (polar) symmetry group is no longer the highest common sub-group of the crystal symmetry and the spontaneous polarization symmetry (polar vector symmetry group ∞mm). The concept of an improper ferroelectric has therefore been revised to include transitions from polar to polar groups. It is shown that in the general cases where other parameters are permissible, the problem has to be solved using the symmetry of directions. The present analysis on the bases of irreducible representation of polar crystals establishes all the possible cases where spontaneous polarization is accompanied by spontaneous magnetisation, optical activity and more complex phenomena. The symmetry changes and the polarization configurations in Gd(MoO₄)₃, boracites, (NH₄)₂BeF₄, alkali trihydrogen selenite family have been discussed in the light of the extended concept of an ‘improper’ ferroelectric.     

Polarization as a Berry Phase

The macroscopic polarization of a crystalline dielectric is best defined as a Berry phase of the electronic Bloch wavefunctions, a feature that is best exemplified by the spontaneous polarization of a ferroelectric crystal for which a microscopic theory was previously unavailable.     

Field-temperature phase diagrams in chiral tilted smectics,evidencing ferroelectric and ferrielectric phases

Usual ferroelectric compounds undergo a paraelectric-to-ferroelectric phase transition when the susceptibility of the electric polarization density changes its sign. The temperature is the only thermodynamic field that governs the phase transition. Chiral tilted smectics may also present an improper ferroelectricity when there is a tilt angle between the average long axis direction and the layer normal. The tilt angle is the order parameter of the phase transition which is governed by the temperature. Although the electric susceptibility remains positive, a polarization proportional to the tilt appears due to their linear coupling allowed by the chiral symmetry. Further complications come in when the chirality increases, as new phases are encountered with the same tilt inside the layers but a distribution of the azimuthal direction which is periodic with a unit cell of two (SmC(A)*, three (SmC(Fi1)*, four (SmC(Fi2)* or more (SmC(alpha)* layers. In most of these phases, the layer normal is a symmetry axis so there is no macroscopic polarization except for the SmC(Fi1)* in which the average long axis is tilted so the phase is ferrielectric. By studying a particular compound with only a SmC(Fi2)* and a SmC(alpha)* phase, we show that we recover the uniformly tilted ferroelectric SmC* when applying an electric field. We are thus led to build field-temperature phase diagrams for this class of compounds by combining different experimental techniques described here.