Dielectric Characteristics of Bi- and Ti-Substituted Pb(Mg1/3Nb2/3)O3

Pb[Mg_1/3Nb_2/3]O₃ was gradually substituted by Bi[Mg_2/3Nb_1/3]O₃ (BiMN) up to 30 mol%, with an overall modification by a constant fraction of PbTiO₃ (10 mol%). Monophasic perovskite powders could be prepared via the B-site precursor route. Ceramic samples of the system showed a typical relaxor behavior of frequency-dependent dielectric dispersion. Values of the maximum dielectric constant decreased substantially with increasing BiMN concentration, whereas corresponding temperatures changed only moderately.     

Influence of Cation Order on the Electric Field-Induced Phase Transition in Pb(Mg1/3Nb2/3)O3-Based Relaxor Ferroelectrics

The effect of cation ordering on an electric field-induced relaxor to normal ferroelectric phase transition in Pb(Mg_1/3Nb_2/3)O₃ (PMN)-based ceramics was investigated. Both A-site La doping and B-site Sc doping were found to enhance the chemical ordering in these relaxor ceramics. However, the enhanced chemical orderings showed different impacts on the dielectric and ferroelectric properties in these perovskite materials. The 5% La doping was observed to shift the dielectric maximum temperature ( T _max) to a significantly lower temperature and suppress the electric field-induced transition to a ferroelectric phase. In contrast, the 5% and 10% Sc doping showed little effect on T _max but strengthened the ferroelectric coupling. The difference is discussed on the basis of cation size and charge imbalance. An electric field-temperature phase diagram is also proposed for the 0.90PMN–0.10Pb(Sc_1/2Nb_1/2)O₃ based on its history dependence of the electric field-induced phase transition.     

Dielectric-State Analysis in Solid-Solution Pb(Yb1/2Ta1/2)O3–Pb(Lu1/2Nb1/2)O3

The structure and temperature dependence of complex lead perovskite dielectrics were investigated for the system (1 − x )Pb(Yb_1/2Ta_1/2)O₃– x Pb(Lu_1/2Nb_1/2)O₃. Superlattice reflections for the compositions 0.8 < x < 1.0 were observed by X-ray diffractometry, and the temperature-composition dielectric-state diagram was determined. In the present study, the disordered middle composition, with 0.2 < x < 0.8, showed a diffuse paraelectric–ferroelectric phase transition, whereas the ordered end compositions, with 0 ≤ x < 0.2 and 0.8 < x ≤ 1.0, revealed successive sharp paraelectric–antiferroelectric and weak antiferroelectric–ferroelectric phase transitions. The dielectric state was confirmed by examining the variation of polarization ( P ) with electric field ( E ).     

Structure and Dielectric Properties of the Ba(Mg1/3Nb2/3)O3-La(Mg2/3Nb1/3)O3 System

A complete range of perovskite solid solutions can be formed in the (1 − x )Ba(Mg_1/3Nb_2/3)O₃- x La(Mg_2/3Nb_1/3)O₃ (BMN-LMN) pseudobinary system. While pure BMN adopts a 1:2 cation ordered structure, 1:1 ordered phases are stabilized for 0.05 ≤ x ≤ 1.0. Dark-field TEM images indicate that the La-doped solid solutions are comprised of large 1:1 ordered domains and no evidence was found for a phase-separated structure. This observation coupled with the systematic variations in the intensities of the supercell reflections supports a charge-balanced "random-site" model for the 1:1 ordering. The substitution of La also induces a transformation from a negative to positive temperature coefficient of capacitance in the region 0.25 ≤ x ≤ 0.5.     

Cation Ordering Transformations in the Ba(Zn1/3Nb2/3)O3-La(Zn2/3Nb1/3)O3 System

Single-phase perovskites were formed in the (1−_x)Ba(Zn_1/3Nb_2/3)O₃-( _x )La(Zn_2/3Nb_1/3)O₃ system for compositions with 0.0≤ x ≤0.6. Although the stability of the trigonal "1:2" ordered structure of the Ba(Zn_1/3Nb_2/3)O₃ end member is very limited (0.0≤ x ≤0.05), low levels of lanthanum induce a transformation to a cubic, "1:1" ordered structure that has a broad range of homogeneity (0.05≤ x ≤0.6). Samples with x > 0.6 were comprised of La₃NbO₇, ZnO, and a perovskite with x = 0.6. The cubic 1:1 phases were fully ordered and no evidence was found for a compositionally segregated microstructure. These observations could not be reconciled in terms of a "space-charge" model; rather, they supported a charge-balanced, "random-site" structure for the 1:1 cation-ordered Ba(β_1/2'β_1/2")O₃ phases.     

Electromechanical Testing and Modeling of a Pb(Mg1/3Nb2/3)O3-PbTiO3-BaTiO3 Relaxor Ferroelectric

Compressive prestress effects on the electrical and mechanical properties of relaxor ferroelectric materials were studied as a function of temperature for several formulations of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-BaTiO₃ (PMN-PT-BT) ceramics. Experimentally measured polarization and strain, induced by an ac electric field, decreased as compressive stress increased. Effective Young's moduli also were measured under constant dc electric fields. A significant decrease in modulus was observed with increasing field. The prestress and modulus experiments were modeled analytically using a proposed relaxor ferroelectric constitutive law. In general, excellent agreement between the model and experiments was obtained, indicating that the model accurately predicted the coupled behavior of this relaxor ferroelectric material.     

Dielectric Behavior of the Relaxor Pb(Mg1/3Nb2/3)O3—PbTiO3 Solid-Solution System in the Microwave Region

Dielectric behavior of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃—PbTiO₃ solid-solution system was studied from—50° to 200°C in the 100 to 12 × 10⁹ Hz frequency region, and a broad dielectric relaxation was measured for compositions throughout the system. The relative microwave permittivity of the composition 0.9Pb(Mg_1/3Nb_2/3)O₃·0.1 PbTiO₃ decreased by 1 order of magnitude from the 1-MHz value of 11800, and similar decreases were observed for other compositions in the system. Dielectric loss (tan δ) values ranged from 0.5 to 1.0 at microwave frequency. The temperature of the broad dielectric constant maximum shifts toward higher values with increased frequency.     

Structure and Dielectric Properties of Pb(Sc2/3W1/3)O3–Pb(Zr/Ti)O3 Relaxors

The structure and dielectric properties of (1− x )Pb(Sc_2/3W_1/3)O₃–( x )Pb(Zr/Ti)O₃ ceramics have been investigated over a full substitution range. All compositions with x < 0.5 adopt a cubic perovskite structure; however, for x ≤ 0.25 a doubled cell results from a 1:1 ordered distribution of the B-site cations. The structural order in Pb(Sc_2/3W_1/3)O₃ (PSW) can be described by a random-site model with one cation site occupied by Sc³⁺ and the other by a random distribution of (Sc_1/3³⁺W_2/3⁶⁺). The ordering is destabilized in solid solutions of PSW with PbZrO₃ (PSW–PZ), but stabilized by PbTiO₃ in the (1− x )PSW–( x )PT system. The changes in order are accompanied by alterations in the dielectric response of the two systems. For PSW–PZ the temperature of the permittivity maximum ( T _ɛ,max) increases linearly with x ; however, for PSW–PT T _ɛ,max decreases in the ordered region (up to x = 0.25) and then increases rapidly as the order is lost. Similar effects were produced by modifying the degree of order of (0.75)PSW–(0.25)PT; when the order parameter was reduced from ∼1.0 to ∼0.65, T _ɛ,max increased by more than 60°C.     

Dielectric Properties and Relaxation in (1−x)BiScO3–xBa(Mg1/3Nb2/3)O3 Solid Solutions

The dielectric properties and frequency dispersion associated with a dielectric relaxation were evaluated within the perovskite (1− x )BiScO₃– x Ba(Mg_1/3Nb_2/3)O₃ solid solution systems (0.7 ≤ x ≤ 1). With increasing BiScO₃, the room-temperature dielectric permittivity at low frequency (100 Hz) increased up to 115 at x = 0.7, and a dielectric relaxation phenomenon was evident. Relaxation parameters were analyzed using several Arrhenius-type equations, and the microwave dielectric property measurement using rectangular wave-guide method enabled confirmation of the extrapolated value of the Arrhenius plot. The result of the microwave dielectric property measurement was also checked with J -function fitting based on the frequency-dependent Gaussian distribution of the associated dielectric loss data at low frequency.     

Direct Compositional Analysis of Ordered Domains in Pure and La-Doped Pb(Mg1/3Nb2/3)O3 by Analytical Electron Microscopy Techniques

The ordered domain structures in Pb(Mg_1/3Nb_2/3)O₃(PMN) and Pb_{1– x} La _x (Mg_1/3Nb_2/3)O₃ are identified using high-resolution transmission electron microscopy (HRTEM) and nanobeam diffractometry (NBD). The chemical compositions in the ordered domains and in the disordered matrices are also acquired using energy-dispersive spectroscopy (EDS). The best matching computer-simulated HRTEM image has a Mg²⁺/Nb²⁺ ratio of return ½. There is no obvious chemical composition difference between the ordered domains and the disordered matrices. The number of the normalized total positive valence electrons remains almost constant in the ordered domains and in the disordered matrices for all the samples. The reason for the growth of the ordered domains in La-doped PMN also is discussed.     

Ferroelectric and Structural Properties of the Pb(Sc1/2Nb1/2)1-x,Tix,O3 System

Extensive solid solution was observed in the system Pb(Sc_1/2/,Nb_1/2,)_1-x,Ti_x,O₃. In the range 0 ≤ x ≤ 0.425 a rhombohedral ferroelectric phase was stable at 25° C. In the range 0.45 ≤ x ≤ 1.00 a tetragonal ferroelectric phase was stable at this temperature. The phase diagram of the system below 500° C strongly resembles that of PbZrO₃−PbTiO₃. The compound Pb(Sc_1/2Nb_1/2)O₃ exhibited rhombohedral perovskite cell symmetry below the ferroelectric ↔ paraelectric transition temperature, and the angle a was acute. The radial coupling coefficient was 0.46 for the composition Sc_1/2Nb_1/2)_0.575Ti_0.4250O₃. At 25°C this composition consisted primarily of the rhombohedral phase with a small amount of the tetragonal phase present. The ferroelectric ↔ paraelectric transition occurred over a temperature range in the rhombohedral phase field. The spontaneous polarization was finite at temperatures considerably above the temperature of the permittivity maximum for a given rhombohedral solid solution.     

Perovskite Phase Formation in the Relaxor System [Pb(Fe1/2Nb1/2)O3]1-x–[Pb(Zn1/3Nb2/3)O3]x

Phase formation and dielectric properties of the compositions in the system [Pb(Fe_1/2Nb_1/2)O₃]₁_ _x –[Pb(Zn_1/3Nb_2/3)O₃] _x were investigated as possible materials for multilayer ceramic capacitors. The formation of the phase with perovskite structure and dielectric properties of ceramics at room temperature in the entire composition range are presented. The undesirable pyrochlore phase can be suppressed up to x = 0.6 by adopting calcination of B-site oxides, followed by reaction with PbO. Compositions in the single-phase range can be sintered at less than 1000°C.     

Large Pyroelectric Effect in Relaxor-Based Ferroelectric Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals

The pyroelectric properties of (1− x )Pb(Mg_1/3Nb_2/3)O_{3− x} PbTiO₃ (PMN− x PT) single crystals with various compositions and orientations have been investigated using a dynamic method. Excellent pyroelectric performances can be achieved in 〈111〉-oriented rhombohedral PMN− x PT (0.24≤ x ≤0.30) crystals, where the measurement direction corresponds to the polar axis of the crystal. At room temperature, the pyroelectric coefficient and the detectivity figure of merit ( F _d ) for the 〈111〉-oriented PMN–0.28PT single crystal are 8.55 × 10⁻⁴ C·(m²·K)⁻¹ and 9.89 × 10⁻⁵ Pa^−1/2 (100 Hz), respectively, superior to those of the widely used pyroelectric materials. They are also weak temperature dependent and nearly independent of frequency. These outstanding pyroelectric performances make the single crystals a promising candidate for uncooled infrared detectors and thermal imagers.     

Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

B-Site Order–Disorder Transition in Pb(Mg1/3Nb2/3)O3–Pb(Mg1/2W1/2)O3 Triggered by Mechanical Activation

B-site cation order–disorder transition induced by mechanical activation was observed in Pb(Mg_1/3Nb_2/3)O₃–Pb(Mg_1/2W_1/2)O₃ (PMN–PMW) solid solution, which was examined using both XRD diffraction and Raman spectroscopic study. The order–disorder transition is composition dependent. Mechanical activation triggers the B-site disordering, which can be steadily recovered by thermal annealing at elevated temperature, i.e., at temperatures around 600°C. Raman spectroscopy demonstrated that there existed tiny ordered microdomains in 0.4PMN·0.6PMW subjected to up to 20 h of mechanical activation, although they cannot be shown by X-ray diffraction. This is a result of the equilibrium between the mechanical destruction and temperature-facilitated recovering at the collision points during mechanical activation. It is therefore unlikely that a complete disordering can be realized in PMN–PMW by mechanical activation. The disordering in PMN–PMW triggered by mechanical activation occurs simultaneously with the refinement in crystallite size at the initial stage of mechanical activation, suggesting that the fragmentation of crystallites is responsible for the order–disorder transition at least during the initial stage of mechanical activation.     

Preparation of Dense Lead Magnesium Niobate–Lead Titanate (Pb(Mg1/3Nb2/3)O3–PbTiO3) Ceramics by Spark Plasma Sintering

The effect of spark plasma sintering (SPS) on the densification behavior of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ ceramics has been investigated. Specimens with a density of >99% of the theoretical density (TD) were obtained using SPS treatment at 900°C. Through normal sintering at 1200°C, however, the density of the specimen was only ∼92% of TD.     

Structural Studies of Ordering in the (Pb1-xBax)(Mg1/3Nb2/3)O3 Crystalline Solution Series

The ordered structures of the (Pb_{1- x} Ba _x )(Mg_1/3Nb_2/3)O₃crystalline solution series were investigated by selected area electron diffraction (SAED) and high-resolution electron microscopy (HREM). At low Ba contents (e.g., x < 0.40), the ordered structure was found to be isostructural with Pb(Mg_1/3Nb_2/3)O₃, with a doubled unit cell characterized by 1/3{111} superlattice reflections. At higher Ba contents (e.g., x > 0.60), the ordered structure was characterized by 1/3{111} superlattice reflections. For intermediate Ba contents (e.g., x - 0.60), diffuse scattering along the {111} between diffuse 1/2{111} and 1/3{111} reflections was observed. The ordering is attributed to the distribution of the B-site cations between multiple sublattices. Strong fluctuations in the B-site cation ratio between ordered and disordered regions are believed not to exist; however, the possibility of weak fluctuations is consistent with the observed lattice images.     

Direct Imaging of Atomic Ordering in Undoped and La-Doped Pb(Mg1/3Nb2/3)O3

In this paper, we report the first direct observations of local ordering in undoped and La-doped Pb(Mg_1/3Nb_2/3)O₃ (PMN) on an atomic scale by high-resolution (∼1.26 Å) Z -contrast imaging. The 1:1 ordering occurs by a variation in the occupancy of Mg and Nb cations between B^I and B^II sublattices. In ordered regions, the B^II sublattice is dominantly occupied by Nb cations, but a small Mg occupancy cannot be excluded. The Mg cations were found to dominantly occupy the B^I sublattice. Within the B^I sublattice, the local Mg/Nb ratio was found to vary among the various B^I sublattices. The results show that the random-site model, rather than the space-charge model, is a better structural model for the 1:1 ordering observed in PMN. A random distribution of Mg and Nb cations on the B^I sublattice within 1:1 ordered regions is believed to be responsible for the relaxor behavior of mixed B-site cation relaxors, such as PMN.