Brillouin Scattering Study of Ferroelectric Instability of Calcium-Strontium-Barium Niobate Single Crystals.

Uniaxial ferroelectrics with tetragonal tungsten bronze structure are important functional materials with photorefractive, electrooptic, piezoelectric, and pyroelectric properties. SrxBa1-xNb2O6 (SBN100x) with x > 50 is known as a typical uniaxial relaxor ferroelectric, while CaxBa1-xNb2O6 (CBN100x) undergoes nearly normal ferroelectric phase transitions. Single crystals of CSBN100x = [x(CBN28) + (1 - x) (SBN61)] = xCa0.28Ba0.72Nb2O6 + (1 - x) Sr0.61Ba0.39Nb2O6 with nominal x = 0.00, 0.25, 0.50, 0.75, and 1.00 were studied to clarify the dynamical properties at the crossover from relaxor (x = 0) to normal (x = 1) ferroelectric behavior. The longitudinal acoustic (LA) and transverse acoustic (TA) modes and a central peak (CP) related to the relaxation process of polarization fluctuations along the polar c-axis were studied in uniaxial ferroelectric CSBN single crystals as a function of temperature via Brillouin scattering spectroscopy. A CBN28 (x = 1.00) crystal shows the sharp elastic anomaly of the LA mode in the gigahertz range toward Curie temperature, Tc. However, those of CSBN25 (x = 0.25) and SBN61 (x = 0.00) crystals show diffusive anomalies due to stronger random fields. The relaxation time determined from the width of a CP shows a critical slowing down in the vicinity of Tc. The elastic anomaly and slowing down of relaxation time of CSBN100x crystals become diffusive in the vicinity of Tc as the CBN28 content decreases. The origin of the crossover from relaxor to normal ferroelectric phase transitions is discussed in terms of the difference in the A1 and A2 sites' occupancies.

Large Electrocaloric Effect in Relaxor Ferroelectric and Antiferroelectric Lanthanum Doped Lead Zirconate Titanate Ceramics.

Both relaxor ferroelectric and antiferroelectric materials can individually demonstrate large electrocaloric effects (ECE). However, in order to further enhance the ECE it is crucial to find a material system, which can exhibit simultaneously both relaxor ferroelectric and antiferroelectric properties, or easily convert from one into another in terms of the compositional tailoring. Here we report on a system, in which the structure can readily change from antiferroelectric into relaxor ferroelectric and vice versa. To this end relaxor ferroelectric Pb0.89La0.11(Zr0.7Ti0.3)0.9725O3 and antiferroelectric Pb0.93La0.07(Zr0.82Ti0.18)0.9825O3 ceramics were designed near the antiferroelectric-ferroelectric phase boundary line in the La2O3-PbZrO3-PbTiO3 phase diagram. Conventional solid state reaction processing was used to prepare the two compositions. The ECE properties were deduced from Maxwell relations and Landau-Ginzburg-Devonshire (LGD) phenomenological theory, respectively, and also directly controlled by a computer and measured by thermometry. Large electrocaloric efficiencies were obtained and comparable with the results calculated via the phenomenological theory. Results show great potential in achieving large cooling power as refrigerants.

Electric in-plane polarization in multiferroic CoFe2O4/BaTiO3 nanocomposite tuned by magnetic fields.

Ferrimagnetic CoFe2O4 nanopillars embedded in a ferroelectric BaTiO3 matrix are an example for a two-phase magnetoelectrically coupled system. They operate at room temperature and are free of any resource-critical rare-earth element, which makes them interesting for potential applications. Prior studies succeeded in showing strain-mediated coupling between the two subsystems. In particular, the electric properties can be tuned by magnetic fields and the magnetic properties by electric fields. Here we take the analysis of the coupling to a new level utilizing soft X-ray absorption spectroscopy and its associated linear dichroism. We demonstrate that an in-plane magnetic field breaks the tetragonal symmetry of the (1,3)-type CoFe2O4/BaTiO3 structures and discuss it in terms of off-diagonal magnetostrictive-piezoelectric coupling. This coupling creates staggered in-plane components of the electric polarization, which are stable even at magnetic remanence due to hysteretic behaviour of structural changes in the BaTiO3 matrix. The competing mechanisms of clamping and relaxation effects are discussed in detail.

Multiferroic and magnetoelectric materials--novel developments and perspectives.

Magnetoelectric (ME) materials are of utmost interest in view of both fundamental understanding and novel desirable applications. Despite its smallness, the linear ME effect has been shown to control spintronic devices very efficiently, e.g., by using the classic ME antiferromagnet Cr2O3. Similar nano-engineering concepts exist also for type-I multiferroic single phase materials like BiFeO3 and BiMnO3. Record high ME response has been realized in stress-strain coupled multiphase magnetoelectrics like PZT/FeBSiC composites, enabling applications in sensors. In type-II multiferroics, whose ferroelectricity is due to modulated magnetic ordering, the ME coupling is of fundamental interest. Higher-order ME response characterizes disordered systems, which extend the conventional multiferroic scenario toward ME multiglass (e.g., Sr(1-x)MnxTiO3).

Evolution of nanodomains in the uniaxial relaxor Sr0.61Ba0.39Nb2O6:Ce.

The evolution of the nanodomain pattern of the uniaxial relaxor ferroelectric strontium barium niobate doped with cerium was studied by piezoresponse force microscopy (PFM). The fractal-like nanodomains observed at room temperature decay on heating. At temperatures up to about 15 K above the Curie temperature, Tc = 320 K, areas of correlated polarization are still visible. On cooling from the paraelectric state to below Tc, a slow isothermal growth of nanodomain was found. The mean domain size increases according to a logarithmic law as predicted for the three-dimensional random field Ising model.

Two-dimensional Ising model criticality in a three-dimensional uniaxial relaxor ferroelectric with frozen polar nanoregions.

The charge-disordered three-dimensional uniaxial relaxor ferroelectric Sr0.61Ba0.39Nb2O6 splits up into metastable polar nanoregions and paraelectric interfaces upon cooling from above Tc. The frozen polar nanoregions are verified by piezoresponse force microscopy, respond domainlike to dynamic light scattering and dielectric excitation, reveal nonergodicity at T>Tc via global aging, and coalesce into polar nanodomains below Tc. Contrastingly, the percolating system of unperturbed interfaces becomes ferroelectric with two-dimensional Ising-model-like critical exponents alpha=0, beta=1/8, and gamma=7/4, as corroborated by ac calorimetry, second harmonic generation, and susceptometry, respectively.

Magnetoelectric switching of exchange bias.

The perpendicular exchange bias field, H(EB), of the magnetoelectric heterostructure Cr2O3(111)/(Co/Pt)(3) changes sign after field cooling to below the Néel temperature of Cr2O3 in either parallel or antiparallel axial magnetic and electric freezing fields. The switching of H(EB) is explained by magnetoelectrically induced antiferromagnetic single domains which extend to the interface, where the direction of their end spins controls the sign of H(EB). Novel applications in magnetoelectronic devices seem possible.