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.     

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.     

Anisotropic polarization response of polar nanostructures in relaxor-type lead lanthanum zirconate titanate ferroelectric ceramics

Polar nanoregions (PNRs) in relaxor-type PLZT ferroelectric ceramics and their response to the out-of-plane, in-plane electric fields were investigated by the high-resolution piezoresponse force microscopy. Anisotropic polarization switching kinetic behaviors of PNRs were found in relaxor PLZT ceramics. Normal, stable ferroelectric domain states were formed through the coalescence of PNRs in the out-of-plane field, while in the high in-plane electric field, the polarization dynamic behaviors of PNRs show spatial inhomogeneity due to the anisotropy random fields in the ferroelectric PLZT ceramics.     

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.     

Broad-band dielectric spectroscopy of tetragonal PLZT x /40/60

The dielectric behaviour of tetragonal PLZT x/40/60 ceramics doped with lanthanum (x?=?5,?12 and 15%) has been investigated at 100–10¹⁴?Hz. Dielectric, THz and infrared spectra were measured from 500 to 20?K. For x?≥?12 relaxor ferroelectric behaviour was observed. All three samples showed an additional relaxational mode below phonons. Analysis of the phonon modes for ferroelectric PLZT 5/40/60 is presented together with the complete dielectric behaviour.     

High-resolution calorimetric study of pb(mg_{1/3}nb_{2/3})o_{3} single crystal

Motivated by the long-standing unresolved enigma of the relaxor ferroelectric ground state, we performed a high-resolution heat capacity and polarization study of the field-induced phase transition in the relaxor ferroelectric single crystal Pb(Mg_{1/3}Nb_{2/3})O_{3} (PMN) oriented along the [110] direction. We show that the discontinuous evolution of polarization as a function of the electric field or temperature is a consequence of a true first order transition from a glassy to ferroelectric state, which is accompanied by an excess heat capacity anomaly and released latent heat. We also find that in a zero field there is no ferroelectric phase transition in bulk PMN at any temperature, indicating that the nonergodic dipolar glass phase persists down to the lowest temperatures.     

Field cooled and zero field cooled 207Pb NMR and the local structure of relaxor PbMg1/3Nb2/3O3

An isotropic 207Pb NMR spectrum corresponding to the glassy matrix with spherical shell type Pb shifts from the cubic sites, as well as an anisotropic spectral component corresponding to polar nanoclusters with a Pb shift parallel to the [111] direction, have been observed in a PbMg(1/3)Nb(2/3)O3 (PMN) single crystal. This represents a microscopic confirmation of the model of relaxors first proposed by Burns and Dacol. A sudden increase in the intensity of the anisotropic cluster line is seen for electric fields larger than the critical field around 210 K. This demonstrates the occurrence of an orientational percolation type transition to the field-induced ferroelectric phase with about 50% of the Pb nuclei still remaining in the spherical glass matrix. A similar though smaller increase of the intensity of this line is also seen in the zero field cooled data, demonstrating that relaxor PMN is an incipient ferroelectric.     

Solid-state single and triple-quantum 93Nb MAS NMR studies of ferroelectric Pb(Mg1/3Nb2/3)O3 and a related pyrochlore

Pb(Mg1/3Nb2/3)O3 (PMN), a well-known relaxor ferroelectric material, and a related pyrochlore phase have been studied by single- and triple-quantum 93Nb MAS NMR spectroscopy. The assignment of the NMR resonances has been attempted.     

Elastic and anelastic relaxations in the relaxor ferroelectric Pb(Mg1/3Nb2/3)O3: II. Strain-order parameter coupling and dynamic softening mechanisms

Elastic and anelastic behaviour of single crystal and ceramic samples of Pb(Mg(1/3)Nb(2/3))O(3) has been investigated at frequencies of ~0.1-1.2 MHz through the temperature interval 10-800 K by resonant ultrasound spectroscopy (RUS). Comparison with data from the literature shows that softening of the shear modulus between the Burns temperature and the freezing interval is independent of frequency. The softening is attributed to coupling between acoustic modes and the relaxation mode(s) responsible for central peaks in Raman and neutron scattering spectra below the Burns temperature, and can be described with Vogel-Fulcher parameters. Shear elastic compliance and dielectric permittivity show similar patterns of temperature dependence through the freezing interval, demonstrating strong coupling between ferroelectric polarization and strain such that the response to applied stress is more or less the same as the response to an applied electric field, with a frequency dependence consistent with Vogel-Fulcher-like freezing in both cases. Differences in detail show, however, that shearing induces flipping between different twin orientations, in comparison with the influence of an electric field, which induces 180° flipping: the activation energy barrier for the former appears to be higher than for the latter. Below the freezing interval, the anelastic loss also has a similar pattern of evolution to the dielectric loss, signifying again that essentially the same mechanism is involved in the freezing process. Overall softening at low temperatures is attributed to the contributions of strain relaxations due to coupling with the local ferroelectric order parameter and of coupling between acoustic modes and continuing relaxational modes of the polar nanostructure. Dissipation is attributed to movement of boundaries between PNRs or between correlated clusters of PNRs. Overall, strain coupling is fundamental to the development of the characteristic strain, dielectric and elastic properties of relaxors.     

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.     

Transparent ferroelectric ceramics PbMg1/3Nb2/3O3-xPbZr0.53Ti0.47O3: Dielectric and electro-optical properties

Lanthanum-free high-transparency ferroelectric ceramics PbMg_1/3Nb_2/3O₃?xPbZr_0.53Ti_0.47O₃ (PMN-xPZT) have been prepared for the first time by a two-stage sintering method. The dielectric and electro-optical properties of the PMN-xPZT ceramics of different compositions, with the values of x both far from the morphotropic phase boundary (x = 10, 16, 23%) and close to it (x = 33%), have been studied. It has been shown that, in compositions lying closer to the morphotropic phase boundary (x = 23 and 33%), one observes, with no electric field applied, a first-order phase transition to a macrodomain ferroelectric phase, whereas the compositions far from the boundary (x = 10, 16%) persist in the relaxor cubic phase down to the low-temperature domain. It has been found that, in the ceramic with x = 33%, the quadratic electro-optical coefficients have at high temperatures (T > 340 K) the largest value among the relaxor systems, which expands the temperature interval of applicability of these solid solutions in industry.     

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.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

Nd含量对Bi_(6-x)Nd_xFe_(1.4)Ni_(0.6)Ti_3O_(18)多晶材料多铁性的影响

采用柠檬酸-硝酸盐法制备了Bi_(6-x)Nd_xFe_(1.4)Ni_(0.6)Ti_3O_(18)(BNFNT-x,x=0.00,0.10,0.20,0.25和0.30)前驱液,再经过干燥、烧结过程制备了单相多晶材料.研究发现,少量Nd掺杂有助于提高样品的铁电性能,BNFNT-0.25样品的铁电性能(2Pr)最大,约达到19.7μC/cm~2.室温下BNFNT-0.20样品磁性能(2Ms)最大约达到4.132 emu/g(1 emu/g=10–3 A·m~2/g).变温介电损耗结果表明Nd掺杂降低了Fe~(3+)和Fe~(2+)间的电子转移或跃迁的激活能.X射线光电子能谱结果表明小量Nd掺杂有助于增强Bi离子稳定性,对改善样品的铁电性能有积极意义.     

Anisotropic dielectric properties of PbYb1/2Ta1/2O3 single crystals

PbYb_1/2Ta_1/2O₃ single crystals were obtained for the first time. They were grown by the flux method. The PbOPbF₂B₂O₃ system was used as a solvent. Dielectric investigations were carried out in 1 0 0_c, 1 1 0_c and 1 1 1_c pseudocubic directions. These studies pointed to anisotropy of dielectric properties. Frequency-independent ε′(T) and ε″(T) maxima related to the antiferroelectric–paraelectric (AFE—PE) phase transition are observed for all directions at 562 K. The frequency-dependent ε′(T) and ε″(T) maxima near 400 K related to the ferroelectric (FE)–AFE phase transition are observed only in 1 1 1_c direction. The hysteresis loops were observed in this direction only. These results point that ferroelectric relaxor properties appear only in 1 1 1_c direction. We propose to consider the ferroelectric phase as ferrielectric one.     

Polarized Micro-Raman Study of the Temperature-Induced Phase Transition In 0.67 Pb（Mg1/3Nb2/3）O3-0.33PbTiO3

Polarized Raman spectra of ferroelectric relaxor 0.67Pb（Mg1/3Nb2/3）O3-0.33PbTiO3 （0.67PMN-0.33PT） single crystal are systematically investigated in a wide temperature range from -196 to 600℃ by micro-Raman scattering technique. The results clearly reveal that there are two structural phase transitions in such composite ferroelectric relaxor： the rhombohedral-tetragonal （R- T） phase transition and the tetragonal-cubic （T- C） phase transition. The former occurs at about TR-T =34℃, corresponding to the vanishing of the soft A1 mode at 106cm^-1 recorded in the parallel polarization. The latter appears at about TT-C = 144℃, which can be verified with the vanishing of mode at 780cm^-1 measured in the crossed polarization.     

Heat capacity of PMN near an electric-field-induced phase transition

The heat capacity of a single crystal of Pb(Mg_1/3Nb_2/3)O₃ (PMN) in an electric filed with E = 3 kV/cm applied along the [111] direction has been measured using adiabatic calorimetry over the temperature range 170–250 K. Anomalies in C _p have been found, which correspond to a field-induced phase transition from a relaxor to a ferroelectric state at 225 K under field cooling conditions or at 235–240 K on the subsequent field heating. The field-induced ferroelectric phase persists in a metastable state at low temperatures and is destroyed on zero-field heating at 210 K. The small entropy change ΔS = 0.028R in the field-induced phase transition suggests an insignificant change in the volume fraction of existing polar nanoregions.     

Soft phonon anomalies in the relaxor ferroelectric Pb(Zn(1/3)Nb(2/3))0.92Ti0.08O3

Neutron inelastic scattering measurements of the polar transverse optic phonon mode dispersion in the cubic relaxor Pb(Zn(1/3)Nb(2/3))0.92Ti0.08O3 at 500 K reveal anomalous behavior in which the optic branch appears to drop precipitously into the acoustic branch at a finite value of the momentum transfer q = 0.2 A(-1) measured from the zone center. We speculate that this behavior is the result of nanometer-sized polar regions in the crystal.     

Inelastic neutron scattering study of the relaxor ferroelectric PbMg1/3Nb2/3O3 at high temperatures

Results of inelastic neutron scattering experiments between 300 K and 900 K on the relaxor ferroelectric PbMg _1/3 Nb _2/3 O₃ are presented. Within a mode-coupling analysis the data are consistent with the observation of a strongly damped quasi-optic excitation. It is demonstrated that below K a dynamical crossover takes place manifesting itself by a narrow central peak. This crossover is accompanied by the appearance of strong damping of the transverse acoustic phonons, with the damping constant proportional to q⁴. Different physical models of the crossover are discussed. Received 8 February 1999     

Coexistence of ergodicity and nonergodicity in LaFeO(3)-modified Bi(1/2)(Na(0.78)K(0.22))(1/2)TiO(3) relaxors

The effect of LaFeO(3) addition to Bi(1/2)(Na(0.78)K(0.22))(1/2)TiO(3) ceramics on the phase stability and macroscopic functional properties was investigated. Similarly to other chemical modifiers known in the literature, LaFeO(3) addition suppresses an electric-field-induced long-range ferroelectric order, giving rise to a giant unipolar strain of ～0.3% at 2?mol% LaFeO(3) addition. Time-dependent changes in polarization and strain hysteresis loops both during successive electrical cycling and after removal of the electric field suggest that a specimen with 2?mol% LaFeO(3) consists of both ergodic and nonergodic phases, which is unique among the known relaxor materials.