Ferroelectric phase transitions in small particles and local regions.

Phase transitions in spherical particles of a cubic ferroelectric are considered within Landau-Ginzburg-Devonshire theory. Concentrating on effects of the depolarizing field, we study competition between states with homogeneous polarization and vortex structures. For large radii of the sphere (R>Rc), the phase transition is into a vortex state while for R

Addendum to 'Multiferroic fluorides'.

An additional eight or ten fluorides with multiferroic phases are listed as an addendum to our recent review 'Multiferroic Fluorides' (Scott J F and Blinc R 2011 J. Phys.: Condens. Matter 23 113202).

Multiferroic magnetoelectric fluorides: why are there so many magnetic ferroelectrics?

We review work on multiferroic magnetic fluorides with an aim to correct the popular opinion that magnetic ferroelectrics are rare in nature. After a qualitative summary describing the main families of magnetic fluorides that are piezoelectric and probably ferroelectric, we discuss in detail the most popular recent groups, namely the K(3)Fe(5)F(15) and Pb(5)Cr(3)F(19) families.

Magnetic control of large room-temperature polarization.

Numerous authors have referred to room-temperature magnetic switching of large electric polarizations as 'the Holy Grail' of magnetoelectricity. We report this long-sought effect, obtained using a new physical process of coupling between magnetic and ferroelectric nanoregions. Solid state solutions of PFW [Pb(Fe(2/3)W(1/3))O(3)] and PZT [Pb(Zr(0.53)Ti(0.47))O(3)] exhibit some bi-relaxor qualities, with both ferroelectric relaxor characteristics and magnetic relaxor phenomena. Near 20% PFW the ferroelectric relaxor state is nearly unstable at room temperature against long-range ferroelectricity. Here we report magnetic switching between the normal ferroelectric state and a magnetically quenched ferroelectric state that resembles relaxors. This gives both a new room-temperature, single-phase, multiferroic magnetoelectric, (PbFe(0.67)W(0.33)O(3))(0.2)(PbZr(0.53)Ti(0.47)O(3))(0.8) ('0.2PFW/0.8PZT'), with polarization, loss (<1%), and resistivity (typically 10(8)-10(9) Ω cm) equal to or superior to those of BiFeO(3), and also a new and very large magnetoelectric effect: switching not from +P(r) to -P(r) with applied H, but from P(r) to zero with applied H of less than a tesla. This switching of the polarization occurs not because of a conventional magnetically induced phase transition, but because of dynamic effects: increasing H lengthens the relaxation time by 500 × from<200 ns to>100 µs, and it strongly couples the polarization relaxation and spin relaxations. The diverging polarization relaxation time accurately fits a modified Vogel-Fulcher equation in which the freezing temperature T(f) is replaced by a critical freezing field H(f) that is 0.92 ± 0.07 T. This field dependence and the critical field H(c) are derived analytically from the spherical random bond random field model with no adjustable parameters and an E(2)H(2) coupling. This device permits three-state logic (+P(r),0,-P(r)) and a condenser with >5000% magnetic field change in its capacitance; for H = 0 the coercive voltage is 1.4 V across 300 nm for +P(r) to -P(r) switching, and the coercive magnetic field is 0.5 T for +P(r) to zero switching.

(39)K NMR and EPR study of multiferroic K(3)Fe(5)F(15).

(39)K NMR spectra and relaxation times of polycrystalline K(3)Fe(5)F(15) have been used as a microscopic detector of the local magnetic fields at the magnetic transition at T(N) = 123 K. The NMR lineshape widens abruptly upon crossing T(N) due to the onset of internal magnetic fields, while we find no significant lineshift. The paraelectric to ferroelectric transition at T(c) = 490 K and the magnetic transition at T(N) have also been studied using X-band EPR (electron paramagnetic resonance). An increase and subsequent decrease in the EPR susceptibilities is observed on approaching T(N) from above. There is also a significant increase in the linewidth. At the same time the g-factor first decreases and then increases with decreasing temperature. The local magnetic field is different at different K sites and is much smaller than the magnetic field around the Fe sites. This seems to be consistent with the behaviour of a weak ferrimagnet. The ferrimagnetism does not seem to be due to spin canting as the lattice is disordered, but may arise from thermal blocking of superparamagnetic percolation clusters. The ferroelectric transition at T(c) shows no electronic anomaly, demonstrating that we are dealing with a classical phonon anomaly as found in conventional oxides rather than an electronic transition.

Terahertz emission from tubular pB(Zr,Ti)O3 nanostructures.

We report intense terahertz emission from lead zirconate titanate (PZT) tubular nanostructures, which have a wall thickness around 40 nm and protrude on n-type Si substrates. Such emission is totally absent in flat PZT films or bulk; hence the effect is attributed to the nanoscale geometry of the tubes. The terahertz radiation is emitted within 0.2 ps, and the spectrum exhibits a broad peak from 2 to 8 THz. This is a gap in the frequency spectrum of conventional semiconductor terahertz devices, such as ZnTe, and an order of magnitude higher frequency peak than that in the well-studied p-InAs, due to the abnormally large carrier concentration gradient in the nanostructured PZT. The inferred mechanism is optical rectification within a surface accumulation layer, rather than the Dember effect. The terahertz emission is optically pumped, but since the tubes exhibit ferroelectric switching, electrically driven emission may also be possible. EPR reveals 02 molecules adsorbed onto the nanotubes, which may play some role in the emission.

Measurement of the 3D Born-Oppenheimer potential of a proton in a hydrogen-bonded system via Deep Inelastic Neutron Scattering: the superprotonic conductor Rb(3)H(SO(4))(2).

We report the first direct measurement of the proton 3-D Born-Oppenheimer potential in any material. The proton potential surfaces in the hydrogen-bonded superprotonic conductor Rb(3)H(SO(4))(2) are extracted from the momentum distribution measured using Deep Inelastic Neutron Scattering (DINS). The potential has a single minimum along the bond direction, which accounts for the absence of the antiferroelectric transition seen in the deuterated material. The measured potential is in qualitative agreement with phenomenological double Morse potentials that have been used to describe hydrogen bonds in other systems.

The giant electromechanical response in ferroelectric relaxors as a critical phenomenon.

The direct conversion of electrical energy to mechanical work by a material is relevant to a number of applications. This is illustrated by ferroelectric 'relaxors' such as Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT; refs 5, 6): these materials exhibit a giant electromechanical (piezoelectric) response that is finding use in ultrasonic and medical applications, as well as in telecommunications. The origins of this effect are, however, still unclear. Here we show that the giant electromechanical response in PMN-PT (and potentially other ferroelectric relaxors) is the manifestation of critical points that define a line in the phase diagram of this system. Specifically, in the electric-field-temperature-composition phase diagram of PMN-PT (the composition being varied by changing the PT concentration), a first-order paraelectric-ferroelectric phase transition terminates in a line of critical points where the piezoelectric coefficient is maximum. Above this line, supercritical evolution is observed. On approaching the critical point, both the energy cost and the electric field necessary to induce ferroelectric polarization rotations decrease significantly, thus explaining the giant electromechanical response of these relaxors.

Field cooled and zero field cooled 207Pb NMR of the relaxor ferroelectric PMN.

A 2.8 kV/cm electric field has been applied parallel to the external magnetic field along the [111] direction of a PMN single crystal and the 207Pb NMR spectra were measured at 9.1 T. Whereas the zero field cooled (ZFC) spectrum exhibits a Gaussian-like line shape, the FC spectrum clearly shows a two peak structure. One of the two peaks coincides with the ZFC spectrum. The other peak is shifted by about 100 kHz towards lower frequencies with respect to the ZFC peak and seems to be characteristic for the ferroelectric state. The ferroelectric shift agrees with the predictions of the spherical random bond-random field model.

Dynamics of the pinned modulation wave in incommensurate bis (4-chlorophenyl) sulfone (BCPS).

We show that both the anomalously huge resonance-frequency dependence of the (35)Cl nuclear quadrupole resonance (NQR) spin-lattice relaxation time in BCPS, reported here for the first time, and its anomalous temperature dependence can be explained by large-scale fluctuations of the pinned modulation wave instead of small-scale fluctuations (phasons and amplitudons). The results were obtained by measuring the laboratory (T(1Q)) and rotating frame (T(1Q,rho)) (35)Cl relaxation times. This is the first time that an effective resonance frequency dependence of the spin-lattice relaxation rate was measured in pure NQR.

Lifshitz point in the phase diagram of a ferroelectric liquid crystal in an external magnetic field

The Lifshitz point in the (H,T) phase diagram of a ferroelectric liquid crystal in a transverse magnetic field has been determined using photon correlation spectroscopy and linear electrooptic response measurements. The extrapolated Lifshitz magnetic field is 25(1+/-0.1) T for a smectic-C* material with an unperturbed helical period of approximately 6 &mgr;m, and the Lifshitz point is located approximately 100 mK above the zero-field transition temperature. We have observed the reentrant helical modulated smectic-C* phase just below the lambda line. The width of this phase is 100 mK at the low temperature critical field H(c) and decreases continuously to zero as we approach the Lifshitz point. The phase boundary between the reentrant phase and the smectic-A phase is of second order, whereas the phase boundary with the unwound smectic-&Cmacr;(*) phase is of first order far away from the Lifshitz point and becomes of second order close to the Lifshitz point. The order parameter dynamics is discussed within the Landau theory.

Influence of surface treatment on the smectic ordering within porous glass

The influence of the surface treatment on the Sm-A-N phase transition of the 8CB (octylcyanobiphenyl) liquid crystal confined to controlled pore glass (CPG) matrices is studied. The characteristic linear size of voids in the chosen CPG matrix is 0.2 &mgr;m. The voids' surface was either nontreated or silane treated enforcing tangential or homeotropic anchoring, respectively. In both cases the x-ray measurements reveal a qualitative change of the temperature dependence of the smectic order-parameter correlation length in comparison to the bulk sample. In addition, the apparent smectic pretransitional ordering is observed for the silane-treated sample. A theoretical description based on the Landau-de Gennes type approach is developed to explain the experimental data. The surface positional anchoring strength of the silane-treated sample is estimated to be of the order of 10(-4) J/m(2) and at least 100 times weaker for the nontreated case.

Interlayer molecular exchange in an anticlinically ordered chiral liquid crystal

The interlayer molecular exchange has been determined in the antiferroelectric smectic-C(*)(A) phase of alphad(2) deuterated 4-(1-methylheptyloxycarbonyl)phenyl4(')-octyloxybiphenyl-4-carboxylat e via quadrupolar deuteron NMR self-diffusion in the spatially varying electric field gradient produced by the anticlinic smectic layer structure. The interlayer self-diffusion coefficient is here by two orders of magnitude smaller than in synclinically ordered smectic phases. The results support the entropic suppression model of the origin of anticlinic smectic ordering. The applied technique could possibly allow for a new insight into the local structure of the intermediate "clock" phases.

Atomic force microscope evidence for the existence of smecticlike surface layers in the isotropic phase of a nematic liquid crystal

Using a temperature controlled atomic force microscope we have observed presmectic layering in the isotropic phase of 4-cyano-4(')-n-octylbiphenyl (8CB) on silanated glass. The first molecular layer shows a smecticlike compressibility modulus of B approximately 10(7) N/m(2) and is stable more than 20 K beyond the bulk clearing point. It is followed by a presmectic modulation that increases when cooling towards the isotropic-nematic transition. In the bulk isotropic phase, the layers cover approximately 70% of the glass surface, indicating a clusterlike organization.

Crossover from glassy to inhomogeneous-ferroelectric nonlinear dielectric response in relaxor ferroelectrics.

The temperature dependence of the dielectric nonlinearities in a PMN single crystal and in 9/65/35 PLZT ceramics has been determined by measuring the first and third harmonic response as well as the dielectric behavior as a function of the dc electric field. In zero field a paraelectric-to-glass, and, in a high enough dc field, a glass-to-ferroelectriclike crossover in the temperature dependence of the nonlinear response have been observed. Both crossovers agree with the predictions of the spherical random-bond-random-field model. Relaxors thus undergo in zero field a transition to a spherical glass, while above the critical field a transition into a ferroelectric state occurs.

1-370 GHz EPR linewidths for K3CrO8: a comprehensive test for the Anderson-Weiss model.

Electron paramagnetic resonance (EPR) measurements have been carried out over the frequency range of 1-370 GHz on single crystals of potassium peroxychromate (K3CrO8) with the view of examining the current models of exchange narrowing of EPR signals in solids. K3CrO8 has a simple (tetragonal) lattice structure, can be grown as single crystals pure or diluted with an isostructural diamagnetic host K3NbO8, and its paramagnetism can be described by a very simple (S = 12, I = 0) spin Hamiltonian. The measurements were made at various orientations of single crystals in the Zeeman field, with emphasis on the principal directions of the g-tensor. For essentially all orientations, the linewidth decreases monotonically for measurements at resonance frequencies, omega0, from 1 to about 100 GHz, and then starts to increase at higher omega0. In order to delineate the spin exchange effects from other sources of line broadening, the measurements were repeated with a diluted spin system, K3NbO8 containing approximately/= 0.5 mole % of K3CrO8, representing the broadening effect of all the magnetic field dependent terms, such as the broadening due to the g-strain and sample holder/waveguide magnetization at the high field utilized, up to 14 T. Using these data, the K3CrO8 linewidths were analyzed in terms of the current models of spin exchange narrowing in three-dimensional systems. A reasonably good agreement was found with the Anderson-Weiss model, when modified for various line broadening effects. The accuracy of the analysis procedure was confirmed by the comparison of the presently determined values of the exchange constant, J, and the dipolar field, Hp, with their values obtained by dc magnetic susceptibility measurements and theoretical analysis, respectively; the agreement was within 5% for J (=1.35 K) and about 25% for Hp (160 G). However, some deviations and unusual splittings were noted in measurements at 370 GHz, whose origin remains unclear.