Raman spectra of sodium niobate (NaNbO 3 ) were obtained in all phases and revealed a significant disorder in the high-temperature U, T2 and T1 phases and a complicated folding of the Brillouin zone at the transitions into modulated S, R, P and N phases associated with the competitive zone-boundary soft modes (in-phase and out-of phase octahedral tilts) along the M-T-R line. An extensive Raman study combined with x-ray diffraction (XRD) and dielectric measurements confirmed the presence of the incommensurate (INC) phase in sodium niobate. XRD experiments revealed the invar effect in the temperature interval 410-460 K corresponding to the INC phase associated with rotations of the NbO 6 octahedra modulated along the b-direction. Our experiments suggest that the phase P consists of three phases: monoclinic (P m ) between 250 and 410 K, INC between 410 and 460 K, and orthorhombic (P o ) between 460 and 633 K. At the low-temperature transition to the ferroelectric rhombohedral N phase all folded modes originating from the M-and T-points of the Brillouin zone abruptly disappear, Raman spectra in the N phase become much simpler and all peaks were assigned.
Precursor dynamics of a cubic to tetragonal ferroelectric phase transition in BaTiO3 is studied by the accurate measurement of the second harmonic generation (SHG) integral intensities. A finite signal holds for the SHG integrated intensity above the ferroelectric Curie temperature T(c)=403 K. Above the Burn's temperature T(d)≈580 K, the power law with the exponent γ=1 shows normal SHG nature originating from the hyper-Raman scattering by dynamical polar excitations, while, below T(d), a SHG signal from polar nanoregions becomes dominant with the larger exponent γ=2. Such a crossover of the power law exponent near T(d) is discussed on the basis of the effective Hamiltonian method and Monte Carlo simulation.
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