Acoustic emission measurements are combined with strain, dielectric, and polarization measurements to detect phase transitions in 0.94Na0.5Bi0.5TiO3–0.06BaTiO3 single crystals during thermal cycling as well as electric field cycling at both room temperature and 140°C. All phase transitions known from the literature (cubic↔tetragonal↔trigonalI↔trigonalII) are determined to be of first order, and the existence of the ferroelectric trigonal II phase at room temperature and its transformation into an antiferroelectric phase during heating above 130°C is established.
High-frequency dielectric studies of Bi 0.85 Nd 0.15 FeO 3 ceramics performed betweeen 100 and 900 K reveal hardening of most polar phonons on cooling below antiferroelectric phase transition, which occurs near 600 K. Moreover, a strong THz dielectric relaxation is seen in paraelectric phase. Its relaxation frequency softens on cooling towards T C ≈ 600 K, its dielectric strength simultaneously decreases and finaly the relaxation disappears from the spectra below 450 K. Both phonon and dielectric relaxation behavior is responsible for a decrease in the dielectric permittivity at the antiferroelectric phase transition. Origin of unusual strong THz dielectric relaxation in paraelectric phase is discussed. Bi 0.85 Nd 0.15 FeO 3 structrure lies on the phase boundary between polar rhombohedral and non-polar orthorhombic phase and owing to this the polarization rotation and polarization extension can enhance the piezoelectric response of this system. Similarities and discrepancies with leadbased piezoelectric perovskites, exhibiting morphotrophic phase boundary between two ferroelectric phases, are discussed.
Complex dielectric properties of Pb(Fe1/2Nb1/2)O3 ceramics were investigated in a broad frequency range from 100 Hz up to 90 THz. A broad dielectric anomaly was observed near the temperature of the ferroelectric phase transition (TC1 = 376 K). Below 1 MHz, the anomaly is strongly influenced by conductivity of the sample, but higher frequency data taken up to 81 MHz reveal a broad and frequency independent peak at TC1 typical for a diffuse ferroelectric phase transition. Surprisingly, dielectric permittivity measured at 37 GHz exhibits a peak shifted by 25 K above TC1, which indicates polar nanoregions with dynamics in microwave frequency region. A dielectric relaxation, which appears in THz region below 700 K, slows down towards TC1 and again hardens below TC2 = 356 K. This central mode drives both phase transitions, so they belong to order–disorder type, although the polar phonons exhibit anomalies near both phase transitions. In the paraelectric phase, infrared reflectivity spectra correspond to local Fm3¯m structure due to short-range chemical ordering of Fe and Nb cations on the B perovskite sites. Moreover, each polar phonon is split due to two different cations on the B sites. Recently, Manley et al. [Nat. Commun. 5, 3683 (2014)] proposed a new mechanism of creation of polar nanoregions in relaxor ferroelectrics. They argued, based on their inelastic neutron scattering studies of PMN–PT, that the TO1 phonon is split and interaction of both components gives rise to so called Anderson phonon localization, which can produce regions of trapped standing waves and these waves induce polar nanoregions in relaxors. We cannot exclude or confirm this mechanism, but we show that the splitting of polar phonons is a common feature for all complex perovskites with relaxor ferroelectric behavior and it can be also observed in canonical ferroelectric BaTiO3, where the soft mode is split in paraelectric phase due to a strong lattice anharmonicity.
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