Evolution from relaxor-like dielectric to ferroelectric in Ba[(Fe0.5Nb0.5)1−xTix]O3 solid solutions

Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ (x=0.2,0.4,0.6,0.8,0.85,0.9 and 0.95) solid solutions were synthesized by a standard solid-state reaction technique. X-ray diffraction at room temperature and dielectric characteristics over a broad temperature and frequency range were evaluated systematically. The structure of Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ solid solutions changed from cubic to tetragonal with increasing x. A Debye-like dielectric relaxation following the Arrhenius law similar to that in Ba(Fe_0.5Nb_0.5)O₃ was observed at lower temperature in the composition range 0.2≤x≤0.8, while the relaxor ferroelectric, diffused ferroelectric and normal ferroelectric behavior were observed for x=0.85,0.9 and 0.95, respectively. The process of the evolution of relaxor-like dielectric to ferroelectric suggested the changing from dilute polar micro-domains to polar micro-domains, polar micro/macro-domains and then polar macro-domains in the present ceramics.     

Piezoelectric, dielectric and magnetic properties of (1-x)Pb[Zr, Ti, (Mg1/2W1/2), (Ni1/3Nb2/3)]O3+x(Ni, Co, Cu)FeO4 composites

The phase structure, microstructure, piezoelectric properties, dielectric characteristic and the ME effect of magnetoelectric Pb[Zr_0.23Ti_0.36+0.02(Mg_1/2W_1/2)+0.39(Ni_1/3Nb_2/3)]O₃ (PZT)+xNi_0.8Co_0.1Cu_0.1Fe₂O₄ (NCCF) composite ceramics were prepared by the conventional solid state reaction method. The structural analysis of both the constituent phases and their composites was carried out by X-ray diffraction, energy dispersive spectrometry and scanning electron microscopy. The results showed cubic spinel structure for ferrite phase and tetragonal perovskite structure for ferroelectric phase. The piezoelectric constant, dielectric constant, Curie temperature, remanent polarization and coercive electric field decreased with increase of ferrite content. The coercive field strength, saturation magnetization and remanent magnetization increased with increasing ferrite content.     

Temperature-dependent ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films

To investigate temperature-dependent ferroelectric and dielectric properties of ferroelectric films, Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were prepared on Pt-coated silicon substrates by pulsed laser deposition. The ferroelectric and dielectric behaviors have been studied in a wide temperature range from 80 K to room temperature. The saturated polarization (P_sat) decreases with decreasing temperature and decreasing electric field, whereas remnant polarization (P_r) shows a more complex temperature dependence. These results, which can be well explained based on a temperature-dependent charged defects-domain wall interaction model, might be helpful for further understanding the domain switching behavior. Based on these results, an alternative way to investigate temperature-dependent ferroelectric fatigue is proposed and experimentally carried out. The measured fatigue rate is found to be linearly dependent on temperature, consistent with the report on Pb(Zr,Ti)O₃ films. Temperature-dependent dielectric measurements of the films further confirm the above explanation.     

Electric field induced ferroelectricity in PbBO3 perovskites with complex substitution in the B position

Processes of the polarization switching in ceramic relaxors Pb(Mg_1/3Ti_1/3W_1/3)O₃, Pb(Mg_1/4Sc_1/4Nb_1/4W_1/4)O₃, Pb(Mg_1/5Sc_1/5Ti_1/5Nb_1/5W_1/5)O₃, and Pb(Mg_1/6Sc_1/6Ti_1/6Sn_1/6Ta_1/6W_1/6)O₃ have been investigated at frequencies from 50 Hz to 2 kHz in the temperature range 90–300 K for measuring field amplitudes up to 20 kV/cm. It has been demonstrated that, under specific conditions, these materials are characterized by saturated dielectric hysteresis loops, which indicate the appearance of the ferroelectric state induced by the electric field. The dependences of the spontaneous polarization and the coercive field of the relaxors under investigation on their chemical composition, temperature, and frequency of the measuring voltage have been determined.     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

Orthorhombic and monoclinic ferroelectric phases investigated by Raman spectroscopy in PZN-4.5%PT and PZN-9%PT crystals

Polarized Raman spectra measurements have been performed on orientated single crystals of Pb[(Zn_1/3Nb_2/3)_0.955Ti_0.045]O₃ (PZN-4.5%PT) and Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZN-9%PT) poled by an electric field along the pseudo-cubic direction in order to determine the nature of the induced ferroelectric phases. Under field-cooled (FC) conditions the ferrolectric phase transition sequence, tetragonal-orthorhombic-rhombohedral, was observed in PZN-4.5%PT. Comparison between the phase transitions induced in PZN-9%PT and PZN-4.5%PT crystals in FC shows that the low- temperature ferroelectric phase in PZN-9%PT cannot be orthorhombic and it can be attributed to the monoclinic phase. The characteristic temperatures found by Raman spectroscopy correspond to those obtained by dielectric measurements and by X-ray diffraction reported previously.     

Si基Bi3.25La0.75Ti3O12铁电薄膜的制备与特性研究

采用Sol-Gel工艺低温制备了Si基Bi_3.25La_0.75Ti₃O₁₂铁电薄膜.研究了退火温度对薄膜微观结构、介电特性与铁电性能的影响.500℃退火处理的Bi_3.25La_0.75Ti₃O₁₂薄膜未能充分晶化，晶粒细小且有非晶团聚，介电与铁电性能均较差.高于550℃退火处理的Bi_3.25La_{0.75 关键词： 铁电薄膜 3.25}La_0.75Ti₃O₁₂')" href="#">Bi_3.25La_0.75Ti₃O₁₂ Sol-Gel工艺     

Bias field effects on the dielectric properties of 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 single crystals with different orientations

The domain states and phase transitions in 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ single crystals were investigated by studying their relative permittivity under various dc bias at constant heating and cooling rates. The orientation dependence of the bias field effect was revealed by examining the temperature dependence of relative permittivity as a function of crystal orientation (the 〈111〉, 〈011〉 and 〈001〉 directions) and dc bias field. The crystals basically have a macrodomain rhombohedral ferroelectric state in the ferroelectric phase under zero dc bias. External bias field could modulate the domain state and induce a stable macrodomain state in the crystals. Also, it is proposed that the dc bias applied along the 〈001〉 or 〈011〉 direction could induce a tetragonal ferroelectric phase or an orthorhombic ferroelectric phase, respectively, in an intermediate temperature range.     

Spontaneous phase transition from relaxor to macrodomain ferroelectric state in single-crystal PbSc0.5Nb0.5O3-BaSc0.5Nb0.5O3 solid solutions

The cooling of Pb_1?x Ba_xSc_0.5Nb_0.5O₃ solid solutions with x≤0.04 leads to a spontaneous transition from a relaxor to a macrodomain ferroelectric state, accompanied by anomalous variation of the dielectric and optical properties of the material. As the barium content in the system increases, the relaxor state becomes more stable and eventually “freezes” at x≈0.05. The crystals with x=0.06 exhibited the appearance of a macrodomain ferroelectric phase induced both by an external electric field with a strength of 1.5 kV/cm and by an internal electric field formed in the course of dielectric aging.     

High pyroelectric power generation of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 single crystal

We report the pyroelectric power generation of a relaxor ferroelectric 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN–PT) single crystal. For a temperature variation rate of 0.5 K/s, the PMN–PT generated a closed-circuit current of 10 nA and an open-circuit voltage of 1.1 V at room temperature. The pyroelectric current and voltage of the PMN–PT single crystal were proportional to the temperature variation rate and were sharply enhanced near the structural phase-transition temperature. Additionally, the PMN–PT pyroelectric generator produced stable power for excessive thermal cycling and was highly sensitive to random thermal fluctuations. Our results indicate the potential importance of PMN–PT for high-power pyroelectric generator applications.     

DIELECTRIC RELAXATION BEHAVIOR OF CERAMICS IN THE Pb(Zn1/3Nb2/3)O3-BaTiO3-PbTiO3 SYSTEM

The dielectric properties of ceramics in Pb(Zn_1/3Nb_2/3)O₃-BaTiO₃-PbTiO₃ system were characterized using dielectric-temperature spectra. A spontaneous (zero field) relaxor-normal ferroelectric tran sition was observed for tetragonal rich compositions. A significant hysteresis effect accompanied by this transition, similar to first-order phase transition of normal ferroelectrics. This behavior was different from that of other relaxors, in which such transitions occurred only under a biased dc field. This observation was explained in terms of a thermally driven transformation from an ensemble of polar microregions to normal long-range ferroelectric state (micro-macro domain transition), which was attributed to the internal field resulting from the tetragonal strain.     

High electric-field-induced strain of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals in multilayer actuators

An optimum composition range (29%≤x≤31%) of 〈001〉 oriented (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃(PMNT) crystals was ascertained for multilayer actuator applications, which exhibited high-strain and low-hysteresis behavior. A −1.5 kV/cm negative E-field can be applied to PMNT ferroelectric samples with low hysteresis. Forty layer actuators with individual element sizes of 7×7×0.7 mm³ were fabricated under identical processing conditions using two different materials: (1) single crystal PMNT and (2) commercial PZT-SF ceramics. Under free-load conditions, 48 μm displacements can been achieved in PMNT actuators at electric fields ranging from −1.5 to 10 kV/cm, which is more than twice the displacement of the PZT-SF actuators driven from −10 to 10 kV/cm. Under 4 kg loading, the displacements in PMNT stain actuators are decreased to 42.5 μm.     

Low- and infralow-frequency dielectric properties of the Pb(Mg1/3Nb2/3)O3 + 2 wt % Li2O ceramics

A dielectric response of the Pb(Mg_1/3Nb_2/3)O₃ ferroelectric ceramics with impurity of 2 wt % Li has been studied. The phase transition has been found to exhibit a relaxor character, as is the case in PMN without Li. However, unlike pure PMN, the dielectric response dispersion in PMN + 2 wt % Li₂O has been described by the Cole-Cole equation at temperatures below the temperature of the low-frequency maximum of the permittivity. An analysis of the dispersion parameters in a wide temperature range has demonstrated that it can be due to the relaxation of domain walls in PMN + 2 wt % Li₂O that appear most likely because of the existence of anomalously coarse grains in PMN + 2 wt % Li₂O.     

Magnetoelectric properties of particulate and bi-layer PMN-PT/CoFe2O4 composites

Our studies comprise electrical dielectric and magnetoelectric properties of CoFe₂O₄ (CFO) and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ [PMN-PT] magnetoelectric composites. The individual phases were prepared by conventional ceramic method. The particulate composites of ferrite and ferroelectric phases were prepared in ferroelectric rich region. Presence of both the phases in the composites was confirmed using X-ray diffraction techniques. The scanning electron microscopic images recorded in backscattered mode were used to study the microstructure of composites. Lattice constant, dielectric constant, electrical resistivity, ferroelectric, and magnetic properties of individual as well as particulate composites were studied. Further the bi-layer composites were made using the discs obtained from the powders of individual phases where hot press technique was employed to obtain disc of individual phases. CFO phase used in bi-layer composites was obtained using chemical co-precipitation technique. Magnetoelectric (ME) measurements were carried out on both, particulate and layered magnetoelectric composites. Comparison of ME signal obtained from particulate and layered composites revealed that the layered composites gives superior magnetoelectric signal. ME data obtained for layered composites show good agreement with the theoretical model.     

Structure refinement of large domain relaxors in the Pb(Mg1/3Ta2/3)O3-PbZrO3 system

The relaxor ferroelectric compound Pb(Mg_0.3Ta_0.6Zr_0.1)O₃ (PMT-PZ) was studied by X-ray, neutron and electron diffraction and transmission electron microscopy in the as-sintered and annealed states. The as-sintered sample was comprised of nanometer-sized 1:1 chemically ordered domains dispersed in a disordered matrix. After annealing at 1325°C the domain size increased to ∼30 nm and the degree of order exceeded 95% in terms of the volume fraction of the ordered domains, yet the sample retained its diffuse, frequency dependent relaxor characteristics. Refinements of the chemically ordered structure using the Rietveld analysis revealed that the octahedral (B) site occupancies were in excellent agreement with a “random site” model for the chemical ordering. In this charge-balanced model for the 1:1 ordered Pb(β′_1/2β″_1/2)O₃ structure the Ta cations predominantly occupy the β″ site, while the β′ site is populated by a random distribution of the Mg, Zr and remaining Ta cations. Large temperature factors for Pb and O atoms are observed in both as-sintered and annealed samples, indicating localized displacements of the Pb and O atoms. The mixed occupancy of the β′ position appears to be responsible for the relaxor characteristics in the dielectric response in spite of the growth of the chemical domains.     

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.     

Structural and electrical properties of 0.7Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>–0.3PbTiO<Subscript>3</Subscript> thin films grown on Ir/MgO buffered Si(100) substrates

Thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN-PT) have been grown on Ir/MgO buffered Si(100) substrates at different substrate temperatures by pulsed laser deposition. Crystalline phases as well as preferred orientations in the PMN-PT films were investigated by X-ray diffraction analysis (XRD). The microstructure, dielectric and ferroelectric properties of PMN-PT film prepared at 650 °C were studied. The results show that the film prepared at 650 °C exhibits pure perovskite phase and single c-axis orientation. The dielectric constant and dissipation factor of the single c-axis oriented film are 1000 and 0.04 at a frequency of 1 kHz, while the remnant polarization and coercive field are about 13.0 μC/cm² and 100 kV/cm under an electric field of 480 kV/cm, respectively. PACS 81.15.Fg; 77.80.-e; 77. 22.Ej; 77.55.+f; 85.50.Gk     

Structure and ferroelectric properties of BaBi3.8M0.2(Ti3.8Nb0.2)O15 (M=Mg, Ca, Sr and Ba) ceramics

Bismuth layer structured compounds BaBi_3.8M_0.2(Ti_3.8Nb_0.2)O₁₅, with M=Mg, Ca, Sr and Ba, were synthesized through a modified chemical route. Phase and structure of the compounds were analyzed by X-ray diffraction. The structure of Mg²⁺ based compound was orthorhombic, while it was tetragonal for the other three compositions. Experimental results indicate that Mg²⁺ prefers to substitute in the Bi₂O₂ layer. The room temperature permittivity was maximum for Ba²⁺ based compound (∼432). The piezoelectric coefficient was significantly enhanced in Mg²⁺ based compound. The Curie temperature was found to decrease gradually in the order Mg>Ca>Sr>Ba based compound. There was a marked improvement in the relaxor behavior and remnant polarization for Ba²⁺ based compound. The structural changes and dielectric, ferroelectric and piezoelectric properties of all the compounds was discussed and co-related.     

Phase diagram of the relaxor (1−x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 investigated by dielectric and Raman spectroscopies

Lead zinc niobate-lead titanate[(1−x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃] (PZN-PT) crystals with x=4.5% and x=12% have been investigated using dielectric and Raman measurements over a range of temperatures. Above room temperature, dielectric measurements show that both compositions exhibit structural phase transitions according to the phase diagram proposed by Kuwata et al. [Ferroelectrics 387 (1981) 579]. Below room temperature, an anomaly at around 180 K for the x=12% sample is observed, suggesting another phase transition. Raman measurements are used to study all phase transitions.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.