Phase transition at a nanometer scale detected by acoustic emission within the cubic phase Pb(Zn1/3Nb2/3)O3-xPbTiO3 relaxor ferroelectrics

Pb(Zn(1/3)Nb(2/3))O3-xPbTiO(3) (x=4.5%-12%) relaxor ferroelectric crystals have been studied by means of acoustic emission (AE) in the 400-540 K temperature range. An anomalous AE activity independent of the ground state relaxor/morphotropic/ferroelectric crossover has been revealed at around 500 K, and it is associated with the "waterfall" feature related to the existence of polar nanoregions (PNRs). The 500 K AE anomaly is attributed to local martensitelike cubic-to-tetragonal ferroelectric transitions within the PNRs imbedded in a nonpolar (cubic) matrix.     

Elastic and anelastic relaxations in the relaxor ferroelectric Pb(Mg1/3Nb2/3)O3: I. Strain analysis and a static order parameter

The structural evolution of Pb(Mg(1/3)Nb(2/3))O(3) (PMN) has been reviewed in terms of characteristic temperatures, length scales and timescales, with a view to considering the overall relaxor behaviour from the perspectives of strain and elasticity. A conventional analysis of lattice parameter data in terms of spontaneous strain and strain/order parameter coupling shows that even though a normal phase transition does not occur the relaxor ordering process is accompanied by a significant volume strain which follows the pattern of a static order parameter evolving according to that expected for a tricritical phase transition with T(c) ≈ 350 K. This matches the evolution of the intensity of the elastic central peak in neutron scattering spectra, and reflects the development of static (or quasistatic) polar nanoregions (PNRs) as if by a mean-field phase transition. Use of a Landau free energy expansion, which includes Γ4(-) order parameter components to describe ferroelectric contributions and an R1(+) order parameter to describe cation ordering together with their formal coupling with strain, then allows the pattern of elastic softening expected for a cubic → rhombohedral phase transition to be anticipated. The extent to which observed softening differs from this static mean-field pattern serves to highlight the additional roles of local heterogeneity and relaxation dynamics in determining the relaxor properties of PMN.     

Low-temperature phase transformations of PbZr(1-x)Ti(x)O(3) in the morphotropic phase-boundary region

We present anelastic and dielectric spectroscopy measurements of PbZr(1-x)Ti(x)O(3) with 0.455 < or = x < or = 0.53, which provide new information on the low-temperature phase transitions. The tetragonal-to-monoclinic transformation is first order for x < 0.48 and causes a softening of the polycrystal Young's modulus whose amplitude may exceed the one at the cubic-to-tetragonal transformation; this is explainable in terms of linear coupling between shear strain components and tilting angle of polarization in the monoclinic phase. The transition involving rotations of the octahedra below 200 K is visible both in the dielectric and anelastic losses, and it extends within the tetragonal phase, as predicted by recent first-principle calculations.     

Temperature-dependent Brillouin scattering studies of surface acoustic modes in Nd0.5Sr0.5MnO3

Brillouin scattering experiments are carried out to study the surface acoustic waves in Nd_0.5Sr_0.5MnO₃ as a function of temperature in the range of 40-300 K covering the metal-insulator and charge-ordering phase transitions. The surface modes include surface Rayleigh wave, pseudo-surface acoustic wave (PSAW) and high velocity PSAW. The observed softening of the sound velocities for the surface modes below paramagnetic to ferromagnetic transition, T_c is related to the softening of the C₄₄ elastic constant. The subsequent hardening of the sound velocity below the charge ordering transition temperature T_co is attributed to the coupling of the acoustic phonon to the charge ordered state via long range ordering of the strong Jahn-Teller (JT) distortion.     

Inelastic light scattering studies of diffuse phase transition in ferroelectric Sr1.9Ca0.1NaNb5O15 thin films

The dynamic behavior of highly oriented ferroelectric Sr_1.9Ca_0.1NaNb₅O₁₅ thin films has been investigated by Brillouin light scattering over a wide temperature range between 25 and 450 °C. The temperature variations of the full‐width at half‐maximum (FWHM) of the central peak (CP) are found to exhibit marked changes around the Curie temperature (T_c = 246 °C). The CP reveals a relaxational mode behavior, which is attributed to thermally activated fast relaxation of polar nanoregions (PNRs). The width of the CP decreases steadily upon cooling from ∼400 °C to T_c and shows little subsequent change within the ferroelectric state, indicating an increase of the number of PNRs and a slowing down of their dynamics. By using a modified superparaelectric model, the activation energy (H₀) of the relaxation processes and the Burns temperature (T_B) are determined to be 2939 and 385 °C, respectively. The evidence for this diffuse phase transition provided by Brillouin scattering is in agreement with results obtained from the temperature‐dependent dielectric permittivity, refractive index, and Raman spectra. Copyright © 2011 John Wiley & Sons, Ltd.     

Field-induced reentrant novel phase and a ferroelectric-magnetic order coupling in HoMnO3

A reentrant novel phase is observed in the hexagonal ferroelectric HoMnO3 in the presence of magnetic fields in the temperature range defined by a plateau of the dielectric constant anomaly. The plateau evolves with fields from a narrow dielectric peak at the Mn-spin rotation transition at 32.8 K in zero field. The anomaly appears both as a function of temperature and as a function of magnetic field without detectable hysteresis. This is attributed to the indirect coupling between the ferroelectric (FE) and antiferromagnetic (AFM) orders, arising from an FE-AFM domain wall effect.     

Direct observation of the formation of polar nanoregions in Pb(Mg1/3Nb2/3)O3 using neutron pair distribution function analysis

Using neutron pair distribution function analysis over the temperature range from 1000 to 15 K, we demonstrate the existence of local polarization and the formation of medium-range, polar nanoregions (PNRs) with local rhombohedral order in a prototypical relaxor ferroelectric Pb(Mg(1/3)Nb(2/3))O3. We estimate the volume fraction of the PNRs as a function of temperature and show that this fraction steadily increases from 0% to a maximum of approximately 30% as the temperature decreases from 650 to 15 K. Below T approximately 200 K the volume fraction of the PNRs becomes significant, and PNRs freeze into the spin-glass-like state.     

Ferroelectric,magnetoelectric and photoelectric properties of BiFeO3 /LaNiO3 heterostructure

BiFeO₃/LaNiO₃ (BFO/LNO) heterostructure was fabricated on quartz substrate via RF sputtering method. The microstructure and surface morphology of the BFO/LNO heterostructure was demonstrated. BFO layer shows good ferroelectric and weak ferromagnetic characters at room temperature. The dielectric constants of the heterostructure under an applied magnetic field 1.2T and zero field are both decreased with increasing frequency at room temperature and the dielectric constant under the applied magnetic field is larger, which is attributed to the coupling between the electric and magnetic dipoles, and further demonstrated in the framework of the Ginzburg-Landau theory for second phase transition. Additionally, the photoconductivity of the heterostructure under blue-laser illumination was observed, and the photoconductivity increase with the enhanced power of the blue-laser.     

Influence of the A and B vacancies on the dielectric and structural properties of the PLZT 8/60/40 ferroelectric ceramic system

The lanthanum modified lead zirconate titanate (PLZT) ferroelectric ceramics, considering La/Zr/Ti ratio of 8/60/40 and vacancies in A or B sites of the perovskite structure, have been analyzed by using X-ray diffraction, dielectric response, polarized light microscopy and ferroelectric hysteresis. No remarkable differences are observed between samples with A or B vacancies from the X-ray diffraction patterns and ferroelectric hysteresis loops. However, the dielectric measurements have revealed a significant decrease in the maximum values for the real part of the dielectric permittivity and an enhancement of the relaxor behavior in the systems where A vacancies have been considered. On the other hand, the anomalies observed in the temperature dependence of the remanent polarization suggest a frozen out in the dynamic of Nanometric Polar Regions (PNRs) around the same region of temperatures for both samples.     

Elastic and anelastic anomalies associated with the antiferromagnetic ordering transition in wüstite, FexO

The elastic and anelastic properties of three different samples of Fe(x)O have been determined in the frequency range 0.1-2 MHz by resonant ultrasound spectroscopy and in the range 0.1-50 Hz by dynamic mechanical analysis in order to characterize ferroelastic aspects of the magnetic ordering transition at T(N) ~ 195 K. No evidence was found of separate structural and magnetic transitions but softening of the shear modulus was consistent with the involvement of bilinear coupling, λe(4)q, between a symmetry-breaking strain, e(4), and a structural order parameter, q. Unlike a purely ferroelastic transition, however, C(44) does not go to zero at the critical temperature, T*(c), due to the intervention of the magnetic ordering at a higher temperature. The overall pattern of behaviour is nevertheless consistent with what would be expected for a system with separate structural and magnetic instabilities, linear-quadratic coupling between the structural (q) and magnetic (m) driving order parameters, λqm(2), and T(N) > T*(c). Comparison with data from the literature appears to confirm the same pattern in MnO and NiO, with a smaller difference between T(N) and T*(c) in the former and a larger difference in the latter. Strong attenuation of acoustic resonances at high frequencies and a familiar pattern of attenuation at low frequencies suggest that twin walls in the rhombohedral phase have typical ferroelastic properties. Acoustic dissipation in the stability field of the cubic phase is tentatively attributed to anelastic relaxations of the defect ordered structure of non-stoichiometric wüstite or of the interface between local regions of wüstite and magnetite, with a rate controlling step determined by the diffusion of iron.     

Acoustic properties of multiferroic PbFe1/2Ta1/2O3

The longitudinal acoustic wave velocity and attenuation in PbFe_1/2Ta_1/2O₃ ceramics have been measured by pulse-echo technique in the temperature range from 4.2 to 530 K. The anomalies observed in the sound velocity and attenuation behavior versus temperature were correlated with Burns temperature, temperature range of the coexistence of relaxor ferroelectric and antiferromagnetic states, and a suggested second antiferromagnetic phase transition at low temperatures.     

Field history dependence of nonlinear dielectric properties of Ba0.6Sr0.4TiO3 ceramics under bias electric field: Polarization behavior of polar nano-regions

Nonlinear dielectric properties of Ba_0.6Sr_0.4TiO₃ ceramics prepared by citrate method were investigated under bias electric field with respect to field history. X-ray diffraction analysis and temperature dependence of the dielectric constant (ε_r) confirmed a macroscopically paraelectric state for the specimen at room temperature. A slim polarization versus electric field (P-E) hysteresis loop of the specimen at room temperature indicated the existence of polar nano-regions (PNRs) superimposed on the paraelectric background. The nonlinear dielectric properties in continuous cycles of bias field sweep displayed a strong sensitivity to the field history. This phenomenon was qualitatively explained in terms of an irreversible polarization evolution of the PNRs under the bias fields. A considerable decline of the tunability with the cycle number suggests an appreciable contribution of the PNRs to the dielectric nonlinearity. The polarization and size of the PNRs were determined by fitting the dielectric constants to a multipolarization mechanism model.     

Acoustic properties of glycine phosphite crystals with an admixture of glycine phosphate

Acoustic and dielectric anomalies in the region of the ferroelectric phase transition in crystals of glycine phosphite (GPI) with a 2 mol % admixture of glycine phosphate (GP) are studied. The acoustic anomalies were found to differ strongly from those observed in nominally pure glycine phosphite crystals. A theoretical analysis of the acoustic and dielectric properties of the crystals was carried out within the model of a pseudoproper ferroelectric phase transition. It is shown that the acoustic anomalies, as well as the temperature dependences of the dielectric constant (for various external electric fields) and pyroelectric current observed in the vicinity of the phase transition in GPI-GP crystals, can be adequately described when the macroscopic polarization present in these crystals above the phase transition temperature is taken into account. The thermodynamic-potential parameters describing electrostriction and the biquadratic relation between the polarization and strain turned out to be close to those characterizing a nominally pure GPI crystal. An irreversible phase transition was observed to occur in GPI-GP crystals at T = 240 K, i.e., above the ferroelectric phase transition temperature.     

Strain and temperature-dependent dielectric permittivity of cubic SrTiO3: Self-consistent phonon theory calculations

We examine the strain effect on the dielectric permittivity of cubic SrTiO₃ (STO) with Self-Consistent Phonon (SCP) theory calculations. Despite the soft mode frequency overestimation with this theory scheme and workflow, our calculations predict the correct tendency of TO1 with respect to temperature and strain. We found that a uniform tensile strain leads to softer TO1 modes. In addition, the TO1 frequency drops suddenly to zero at a specific temperature in the presence of a ferroelectric transition. The square linear relation between TO1 and temperature is used to estimate the Curie Temperature (T_C), and the STO dielectric permittivity calculated with the Lyddane-Sachs-Teller relation follows the Curie-Weiss (CW) law; which can also be used to determine another T_C value. Results from both approaches are in good agreement with each other and show that T_C increases significantly even when the applied tensile strain is only a few percent.     

Acoustic longitudinal mode coupling in w-shaped Al/Ge Co-doped fibre

This paper proposes a novel fibre structure aiming at distributed temperature and strain sensing. Utilizing Al₂O₃ and GeO₂ as dopants to form a w-shaped acoustic waveguide, it realizes modal coupling between longitudinal acoustic modes of its inner and outer core layers, leading to a dual-peak or multi-peak Brillouin gain spectrum. The relationship between the acoustic mode coupling properties and the fibre materials, doping concentrations and structural parameters are investigated, showing that the positions of mode coupling points in acoustic dispersion curves and the coupling intensities can be designed flexibly. A specific fibre design for the discriminative sensing of temperature and strain under a pump wavelength of 1.55 μm is given. The responses of its Brillouin gain properties on temperature and strain are analysed theoretically, demonstrating its potential for distributed fibre Brillouin sensing.     

Interplay of couplings between antiferrodistortive, ferroelectric, and strain degrees of freedom in monodomain PbTiO3/SrTiO3 superlattices

We report first-principles calculations on the coupling between epitaxial strain, polarization, and oxygen octahedra rotations in monodomain (PbTiO(3))(n)/(SrTiO(3))(n) superlattices. We show how the interplay between (i) the epitaxial strain and (ii) the electrostatic conditions can be used to control the orientation of the main axis of the system. The electrostatic constrains at the interface facilitate the polarization rotation and, as a consequence, we predict large piezoelectric responses at epitaxial strains smaller than those required considering only strain effects. In addition, ferroelectric (FE) and antiferrodistortive (AFD) modes are strongly coupled. Usual steric arguments cannot explain this coupling and a covalent model is proposed to account for it. The energy gain due to the FE-AFD coupling decreases with the periodicity of the superlattice, becoming negligible for n ≥ 3.     

Leakage current, ferroelectric and structural properties in Pb1−xBaxTiO3 thin films prepared by chemical route

Single-phase perovskite structure Pb_1−xBa_xTiO₃ thin films (x=0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO₂/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively.     

单相ABO3型多铁材料的磁电耦合及磁电性质研究

实验发现多铁性钙钛矿物质YMnO₃和BiMnO₃在接近磁有序相变温度时,其介电常数和正切损失会出现异常,这些现象说明在物质的磁性和介电性质之间存在耦合.通过对系统磁性和铁电性之间可能磁电耦合方式的分析,考虑在系统哈密顿量中加入与自旋关联和极化相关的耦合项,对铁电子系统应用软模理论,对磁性运用基于海森伯模型的量子平均场近似,研究了外磁场诱导的极化、介电的变化和外电场诱导的磁化的变化等,并将以上结果与实验进行了比较和分析,较为合理地解释了一些多铁钙钛矿物质中的磁电现 关键词： 多铁 磁电耦合 铁电 铁磁     

Elastic and anelastic properties of ferroelectric SrTi(18)O3 in the kHz-MHz regime

Resonant ultrasound spectroscopy has been used to follow elastic softening in SrTi(18)O3 in the frequency range ～0.2-1 MHz. A dramatic softening of C44 occurs as the Curie temperature T(c) = 24 K is approached from above or below, which correlates with the development of a central peak in Raman and Brillouin spectra. This is attributed to strong coupling between the acoustic mode and the central peak mode. A weaker anomaly is seen in a resonance mode which is believed to be controlled by 1/2(C11-C12). Significant attenuation accompanies this softening and an additional dissipation peak has also been observed at ～80-90 K. This extends earlier work by a factor of 150,000× from the 30 GHz regime and helps address the question as to whether the ferroelectricity is stimulated primarily by a soft mode into a homogeneous ground state or by clustering of rhombohedral nanoregions into an inhomogeneous ground state.     

Electric field effects on the dielectric and acoustic anomalies of Pb[(Mg1/3Nb2/3)0.83Ti0.17]O3 single crystals studied by dielectric and Brillouin spectroscopies

The effect of the electric field on the dielectric and acoustic properties of Pb[(Mg_1/3Nb_2/3)_0.83Ti_0.17]O₃ single crystals was investigated as functions of temperature and the electric field strength. The dielectric constant and the acoustic mode behaviors exhibited typical relaxor behaviors when there was no bias field. The longitudinal acoustic mode showed splitting under a moderate electric field of 1 kV/cm applied along the [001] direction, indicating coexistence of macroscopic/mesoscopic ferroelectric states and relaxor states. Further increase in the electric field up to 2 kV/cm induced a clear ferroelectric phase transition, which became smeared out due to the proximity of the electric field to the critical point. The electric field-temperature phase diagram of Pb[(Mg_1/3Nb_2/3)_0.83Ti_0.17]O₃ was suggested based on the observed field-induced changes in the dielectric and the acoustic properties.