Dielectric and optical properties of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)<Subscript>0.8</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>3</Subscript> (PMNT-0.2) ferroelectric relaxor single crystals

The dielectric and optical (optical transmission, small-angle light scattering, birefringence) properties of PMNT-0.2 single crystals and their variation induced by a dc electric field have been studied. The birefringence was found to increase anomalously at the transition from the rhombohedral ferroelectric to the inhomogeneous relaxor phase (the spontaneous ferroelectric transition temperature T_sp). Below T_sp, the dielectric and optical properties were observed to exhibit anomalies originating from reorientation and growth of domains in size. Unlike ferroelectric relaxors of the type of PbB′_1/3B′_2/3O₃ and PbB′_1/2B′_1/2O₃, in PMNT-0.2 neither induction of the ferroelectric phase by an electric field nor thermally stimulated destruction of the ferroelectric state occurs through the percolation mechanism (i.e., they are not accompanied by anomalously narrow maxima in small-angle light scattering). This is attributed to the inhomogeneous structure of the relaxor phase, as a result of which the phase transition does not take place simultaneously in various regions of the crystal.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Mn3TeO6 – a new multiferroic material with two magnetic substructures

From magnetic susceptibility, dielectric permittivity, electric polarization and specific heat measurements we discover spin‐induced ferroelectricity and magnetoelectric coupling in Mn₃TeO₆ and observe two successive magnetic transitions at low temperatures. A non‐ferroelectric intermediate magnetic state occurs below 23 K and a multiferroic ground state emerges below 21 K. Moreover, Mn₃TeO₆ is a candidate for a multiferroic material where two types of incommensurate spin structures, cycloidal and helical, coexist. Theoretically, both spin substructures may contribute to the macro electric polarization via different mechanisms. This could open new ways of manipulating the ferroelectric polarization in a multiferroic material. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Electro‐optical interferometric microscopy of periodic and aperiodic ferroelectric structures

The ferroelectric domain structures of periodically poled KTiOPO₄ and two‐dimensional short range ordered poled LiNbO₃ crystals are determined non‐invasively by interferometric measurements of the electro‐optically induced phase retardation. Owing to the sign reversal of the electro‐optical coefficients upon domain inversion, a π phase shift is observed for the inverted domains. The microscopic setup provides diffraction‐limited spatial resolution allowing us to reveal the nonlinear and electro‐optical modulation patterns in ferroelectric crystals in a non‐destructive manner and to determine the poling period, duty cycle and short‐range order as well as detect local defects in the domain structure. Conversely, knowing the ferroelectric domain structure, one can use electro‐optical microscopy so as to infer the distribution of the electric field therein.

     

Effect of the annealing temperature of thin Hf0.3Zr0.7O2 films on their energy storage behavior

With increasing annealing temperature (T_anneal), the magnitude of the electric fields for the antiferroelectric‐to‐ferro‐electric (E_AF) and ferroelectric‐to‐antiferroelectric (E_FA) transition of a 9.2 nm thick Hf_0.3Zr_0.7O₂ film decreased. The energy storage densities of the Hf_0.3Zr_0.7O₂ films crystallized at 400 °C, 500 °C, and 600 °C were as large as 42.2 J/cm³, 40.4 J/cm³, and 28.3 J/cm³, respectively, at the electric field of 4.35 MV/cm. The maximum dielectric constant of the Hf_0.3Zr_0.7O₂ film crystallized at 600 °C was the largest (～46) as it had the smallest E_AF and E_FA, whereas the leakage current density of the film crystallized at 400 °C was the smallest. The 400 °C of T_anneal was the optimum condition for energy storage application. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Temperature‐dependent ferroelectric dynamic hysteresis properties of modified PMN–PZT relaxor ceramics

Temperature‐dependent ferroelectric dynamic hysteresis properties of modified Pb(Mg_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PMN–PZT) ceramics have been investigated in a wide range from 298 to 433 K. Interestingly, it was found that back‐switching polarization P_bc increased while the hysteresis area 〈A 〉, coercive field E_c, saturation polarization P_s, and remnant polarization P_r all decreased linearly with temperature below 398 K (close to the macro–micro domain transition temperature T_nr). A set of simple linear temperature scaling relations was established, which is different from the power‐law scaling relations for soft and hard PZT ceramics. At further increased temperature, double‐loop features appeared and the ferroelectric properties varied nonlinearly due to the reversible macro–micro domain transition in the T > T_nr region. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ferroelectric phenomena in CdSnO<Subscript>3</Subscript>: A first-principles studies

The phonon spectrum of cubic cadmium metastannate and parameters of the crystal structure of its distorted phases were calculated from first principles within the density functional theory. It is shown that the phonon spectrum and the energy spectrum of the distorted phases in α-CdSnO₃ resemble surprisingly the corresponding characteristics of CdTiO₃. The ground state of α-CdSnO₃ is the ferroelectric Pbn2₁ phase, the energy gain from the phase transition to this phase from the nonpolar phase Pbnm is ∼30 meV, and the spontaneous polarization is 0.25 C/m². The analysis of the eigenvector of the ferroelectric mode in α-CdSnO₃ and the partial densities of states indicates that the ferroelectric instability in this crystal, which does not contain transition d-element atoms, is associated with the formation of a covalent bonding between Cd and O atoms.     

Effect of the la concentration on the dielectric and optical properties of the transparent ferroelectric ceramics 75PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-25PbTiO<Subscript>3</Subscript>

The dielectric, optical, and electro-optical properties of transparent ferroelectric ceramics 75PbMg_1/3Nb_2/3O₃-25PbTiO₃ (75PMN-25PT) with different La concentrations (2, 3, and 4 at %) have been studied. It has been shown that all the samples under study undergo a diffuse phase transition, and the degree of diffuseness increases with an increase in the La concentration. The temperature dependences of the optical transmission in different regimes of applying an electric field and the quadratic electro-optical effect have been investigated. It has been found that, at room temperature, the maximum electro-optical effect is observed in the ceramics with a La concentration of 3 at %. This is explained by the fact that the measurement temperature is close to the Vogel-Fulcher temperature at which the minimum electric field is required to induce ferroelectric states from the relaxor phase.     

<Emphasis Type="Italic">E-T</Emphasis> phase diagram of lead magnesium niobate relaxor ferroelectric in the Mandelstam-Brillouin scattering spectra

The results of studying the velocity of hypersonic longitudinal acoustic phonons over a wide temperature range under an applied constant electric field in the PbMg_1/3Nb_2/3O₃ (PMN) relaxor ferroelectric are reported. An analysis of the experimental data on the basis of the existing E-T phase diagrams shows the necessity of a substantial change in the current concepts. Two radically different states—with the reversible and irreversible behavior of velocity—have been observed experimentally in the induced ferroelectric phase. A modified _E-T phase diagram of the PMN crystal is suggested.     

Synthesis and Raman investigation of sol–gel‐derived relaxor ferroelectric thin films

Pb(Fe_2/3W_1/3)O₃ (PFW) thin films were deposited on platinized silicon substrate by a chemical solution deposition technique. Room‐temperature X‐ray diffraction (XRD) revealed a pure cubic crystal structure of the investigated material. The microstructure indicated good homogeneity and density of the thin films. A Raman spectroscopic study was carried out on PFW to study the polar nano‐regions in the temperature range 85–300 K. The Raman spectra showed a change in the peak intensity and a shift towards the lower wavenumber side with temperature. The Raman spectra also revealed the transition from the relaxor to the paraelectric state of PFW. There was no evidence of a soft mode in the low‐temperature region, in contrast to the normal ferroelectric behavior. The polar nano‐regions tend to grow and join at low temperatures (∼85 K), which become smaller with increase in temperature. The presence of strong Raman spectra in the cubic phase of the material is due to the presence of distributed Fm3m(Z = 2) symmetry nano‐ordered regions in the Pm3m(Z = 1) cubic phase. Copyright © 2007 John Wiley & Sons, Ltd.     

Ferroelectric-ferromagnetic correlations in BiMnO<Subscript>3</Subscript> perovskite within Landau theory: comparison with experiment

Here we present a simple model formulated in the spirit of Landau theory in order to qualitatively describe magnetoelectric multiferroics. The system consists of two coupled single-component order parameters P and M which represent ferroelectric and ferromagnetic phases, respectively. We show that the magnetoelectric coupling strongly renormalizes the original magnetic transition temperature, T _M ?\rightarrow T _RM (with T _RM ≫ T _M ), as well as generates an additional anomaly in ferroelectric subsystem at T _RM . Under the influence of both magnetic and electric fields the concept of Arrot plot is reproduced by the Arrot planes. We compare obtained results with available experimental data for the BiMnO₃ which undergoes ferroelectric transition below 700 K (T _f ) and ferromagnetic transition at 100 K (T _RM ). The results are in good overall agreement with experimental data for the ferroelectromagnetic BiMnO₃. We also estimate the contribution of Gaussian fluctuations of both order parameters, that lead to corrections to the mean-field specific heat. Those corrections are still insufficient even though other quantities agree quite well with experiment. We calculate the temperature dependence of the coherence length for both types of order as well.     

Raman tensor analysis of (K0.5Na0.5)NbO3–LiSbO3 lead‐free ceramics and its application to study grain/domain orientation

A quantitative polarized Raman analysis of ferroelectric grain/domain orientation in LiSbO₃ (LS‐modified) (K_0.5Na_0.5)NbO₃ (KNN) ceramics is presented, based on the analysis of the complex orientation dependence in space of their Raman‐active modes. Complete sets of Raman tensor elements of A_g, and E_g phonon modes for orthorhombic/tetragonal structures of KNN have been determined. Through this spectroscopic algorithm, quantitative information could be extracted in terms of three Euler angles in space for KNN samples consisting of mixed phases, thus enabling quantitative visualization of the local distribution of grains/domains in the solid angle. As an application of the method, we quantitatively examined the unknown crystallographic grain orientation patterns on the surfaces of pure KNN and of KNN‐0.05LS ceramics. These two samples were useful to clarify a polymorphic phase transition from the orthorhombic to the tetragonal phase taking place in the LS‐modified KNN system. Thus, we demonstrated that polarized Raman spectroscopy is a valuable and efficient tool for nondestructive three‐dimensional assessments of grain/domain orientation in ferroelectric materials with complex polymorphic structures. We believe that the data shown here represent a typical scenario encountered in grain/domain orientation assessments of piezoelectric perovskites. Copyright © 2012 John Wiley & Sons, Ltd.     

Lattice dynamics and ferroelectric instability in ordered and disordered PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

The dynamic Born charges and the frequency spectra of lattice oscillations in the crystals of ordered and disordered PbSc_1/2Ta_1/2O₃ (PST) and PbSc_1/2Nb_1/2O₃ (PSN) solid solutions have been calculated within the framework of the generalized Gordon-Kim model with allowance for the dipole and quadrupole polarizabilities. The phonon spectra of both compounds contain ferroelectric soft modes. The influence of various interactions on the magnitude of dynamic charges and ferroelectric instability in PSN and PST solid solutions has been studied and it is shown that both these charges and the ferroelectric instability are determined by the competition between long-range dipole-dipole interactions and short-range dipole-charge interactions, the determining role played by the interaction of Nb (Ta) cations and oxygen anions in the Nb-O (Ta-O) bond direction.     

Hysteresis phenomena in the course of polarization evolution in a sinusoidal electric field in lead magnesium niobate crystals

The processes of polarization evolution in single crystals of the PbMg_1/3Nb_2/3O₃ model ferroelectric relaxor in a sinusoidal electric field are investigated at temperatures near and above the temperature T _d 0 of destruction of the induced ferroelectric state upon heating in zero electric field. The polarization switching current loops are measured in the ac electric field applied along the 〈111〉 and 〈110〉 pseudocubic directions. The electroluminescence intensity loops are obtained under the combined action of ac and dc electric fields applied along the 〈100〉 direction. In a certain temperature range above T _d 0 and the freezing temperature T _f in lead magnesium niobate, there are electric current anomalies, that correspond to the dynamic formation and subsequent destruction of the ferroelectric macroregions throughout each half-cycle of the ac electric field. The measurements of electroluminescence hysteresis loops demonstrate that the observed depolarization delay (related to the ac electric field amplitude) increases with an increase in the dc electric field and decreases as the ac field amplitude increases. The nature of the observed phenomena is discussed.     

Investigation on optical properties of Bi<Subscript>2.85</Subscript>La<Subscript>0.15</Subscript>TiNbO<Subscript>9</Subscript> thin films by prism coupling technique

Layered-perovskite ferroelectric Bi_2.85La_0.15TiNbO₉ (LBTN) optical waveguiding thin films were grown on fused silica substrates by pulsed laser deposition (PLD). X-ray diffraction (XRD) revealed that the film is highly (00l) textured. We observed sharp and distinct transverse electric (TE) and transverse magnetic (TM) multimodes and measured the refractive indices of LBTN thin films at 632.8 nm. The ordinary and extraordinary refractive indices were calculated to be n _TE=2.358 and n _TM=2.464, respectively. The film homogeneity and the film-substrate interface were analyzed using an improved version of the inverse Wentzel–Kramer–Brillouin (iWKB) method. The refractive index of the film remains constant at n ₀ within the waveguiding layer. The average transmittance of the film is 70% in the wavelength range of 400–1400 nm and the optical waveguiding properties were evaluated by the optical prism coupling method. Our results showed that the LBTN films are very good electro-optical active material.     

Trapped charge‐induced pyroelectric‐like transient response in single high‐resistivity Sb2Se3 nanowires

Dynamic scanning photocurrent microscopy was applied to Sb₂Se₃ crystalline single nanowires (NWs) to analyze their transient photocurrent responses. These NWs exhibited switching behavior with rapid rise and decay times upon illumination by laser pulses. The estimated spectral responsivity and external quantum efficiency for a freshly‐prepared NW at a bias voltage of 0.3 V and excitation wavelength of 488 nm were ～16.9 mA/W and ～42.9%, respectively. A pyroelectric‐like current transient was observed with reduced spectral responsivity when nonpolar Sb₂Se₃ single‐crystalline NWs were excited by laser pulses. Because Sb₂Se₃ NWs were nonpyroelectric or ferroelectric, the pyroelectric‐like current could possibly be attributed to temperature dependent nonlinear space‐charge distributions. Defects produced by the external electrical bias generated and re‐distributed space charges in the NWs. As a result, the temperature dependent inhomogeneous electric field led to nonlinear expansions or contractions of the lattice (electrostriction) that can produce pyroelectric current. We obtained a lower bound of equivalent pyroelectric coefficient α ≥ 60.09 μC/m² K from these materials by fitting the electrical transients. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Optical studies of delayed relaxation in Pb<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>Sc<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (PBSN-6) solid solutions

The temperature dependences of the permittivity, birefringence, optical transmittance, and small-angle light scattering and their variations with time are studied for single crystals of the Pb_0.94Ba_0.06Sc_0.5Nb_0.5O₃ relaxor (PBSN-6) in the heterophase region of coexistence of different phases. It is shown that an electric field induces a phase transition to the ferroelectric state, which manifests itself within some time (delay time τ) after application of the electric field to the crystal. The observed dependence of the temperature of this transition on the heating rate of the sample and the changes in the birefringence and small-angle light scattering intensity with time confirm the kinetic character of the induced transition. Temperature dependences of the delay time τ for different electric fields are constructed. It is revealed that, at low temperatures, the delay time τ decreases with increasing temperature. This agrees with the behavior of τ in classical relaxors. At the Vogel-Fulcher temperature, however, one observes that dτ/dT reverses sign and τ increasing as the temperature continues to increase. This anomalous behavior of τ in the heterophase region is accounted for by the coexistence of the cubic relaxor and rhombohedral macrodomain phases.     

Temperature‐dependent Raman scattering in ferroelectric Bi4−xNdxTi3O12(x = 0, 0.5, 0.85) single crystals

The temperature‐dependent Raman spectra of ferroelectric Bi_4−xNd_xTi₃O₁₂(x = 0, 0.5, 0.85) single crystals were recorded from 100 to 800 K. It was found that there is a critical Nd content x₀ between 0.5 and 0.85. The Nd³⁺ ions prefer to replace Bi³⁺ ions in pseudo‐perovskite layers when x < x₀, while they might begin to incorporate into (Bi₂O₂)²⁺ layers when x ≥ x₀. Nd substitution leads to a decrease in the ferroelectric–paraelectric transition temperature (T_c). A monoclinic distortion of orthorhombic structure occurs in Bi₄Ti₃O₁₂ crystals at temperatures below 200 K. Copyright © 2009 John Wiley & Sons, Ltd.     

Room temperature ferroelectricity of tetragonally strained SrTiO3 thin films on single crystal Rh substrates

Epitaxial SrTiO₃ thin films were deposited on single crystalline Rh substrates by pulsed laser deposition. The tetragonally stained structure of the SrTiO₃ thin films with a c/a ratio of 1.04 was confirmed by x-ray diffraction experiments. The SrTiO₃ thin films exhibited good ferroelectric properties with a high remanent polarization (2P_r) of 8 μC/cm² and a canonical ferroelectric piezoresponse hysteresis loop at room temperature. We estimated a high activation electric field of about 6.4 MV/cm for domain wall creeping. This activation electric field is higher than that of typical ferroelectric materials such as PbTiO₃.     

Proton conductivity and ferroelectric phase transition in hydrogen-bonded ferroelectric NH4IO3

We report on the ac dielectric permittivity (ε) and the electric conductivity (σ_ω), as function of the temperature 300?K?T4IO₃. The main feature of our measured parameters is that, the compound undergoes a ferroelectric phase transition of an improper character, at (368?±?1)K from a high temperature paraelectric phase I (Pm2₁ b) to a low temperature ferroelectric phase II (Pc21n). The electric conduction seems to be protonic. The frequency dependent conductivity has a linear response following the universal power law (σ_{( ω )}?=?A(T)ω ^{s (T)}). The temperature dependence of the frequency exponent s suggests the existence of two types of conduction mechanisms.