The relaxor ferroelectric PbMg 1/3 Nb 2/3 O3 was investigated by means of broad-band dielectric and Fourier Transform Infrared (FTIR) transmission spectroscopy in the frequency range from 1 MHz to 15 THz at temperatures between 20 and 900 K using PMN films on infrared transparent sapphire substrates. While thin film relaxors display reduced dielectric permittivity at low frequencies, their high frequency intrinsic or lattice response is shown to be the same as single crystal/ceramic specemins. It was observed that in contrast to the results of inelastic neutron scattering, the optic soft mode was underdamped at all temperatures. On heating, the TO1 soft phonon followed the Cochran law with an extrapolated critical temperature equal to the Burns temperature of 670 K and softened down to 50 cm −1 . Above 450 K the soft mode frequency leveled off and slightly increased above the Burns temperature. A central mode, describing the dynamics of polar nanoclusters appeared below the Burns temperature at frequencies near the optic soft mode and dramatically slowed down below 1 MHz on cooling below room temperature. It broadened on cooling, giving rise to frequency independent losses in microwave and lower frequency range below the freezing temperature of 200 K. In addition, a new heavily damped mode appeared in the FTIR spectra below the soft mode frequency at room temperature and below. The origin of this mode as well as the discrepancy between the soft mode damping in neutron and infrared spectra is discussed.
We report a neutron scattering study of a ferroelectric phase transition in Sr 0.61 Ba 0.39 Nb 2 O 6 (SBN-61). The ferroelectric polarization is along the crystallographic c-axis but the transverse acoustic branch propagating along the <1, 1, 0> direction does not show any anomaly associated with the this transition. We find no evidence for a soft transverse optic phonon. We do, however, observe elastic diffuse scattering. The intensity of this scattering increases as the sample is cooled from a temperature well above the phase transition. The susceptibility associated with this diffuse scattering follows well the anomaly of the dielectric permittivity of SBN-61. Below T c the shape of this scattering is consistent with the scattering expected from ferroelectric domain walls. Our results suggest that despite apparent chemical disorder SBN-61 behaves as a classic order-disorder uniaxial ferroelectric with critical fluctuations in the range < 10 −11 s.
We present a fully atomistic model of polar nanoregions (PNRs) in the relaxor ferroelectric PbMg 1/3 Nb 2/3 O 3. Our molecular dynamics calculations reproduce both the characteristic form of the neutron diffuse scattering distribution and its temperature dependence. A shell model was used with a modified version of a published interatomic potential that was based on ab initio calculations. The parameters of this potential were optimized for the present work to provide a better description of the O atom interactions, as these are particularly important for neutron scattering. At high temperatures the Pb ions are displaced from their mean site positions in a direction that has an isotropic distribution, but at low temperatures the distribution condenses into eight localized sites displaced from the average position along each of the eight possible 1 1 1 directions. At intermediate temperatures (300 K) the distribution is cuboidal with some preference for 1 1 1 displacements but with all possible displacement directions present. Longitudinal correlations between the displacements of Pb-Mg/Nb and Pb-O increase monotonically in magnitude as the temperature changes from 700 K to 10 K with the sign of the Pb-O correlation being negative. At low temperatures this increase in correlation results in polar nanoregions that are clearly visible in plots of the local structure, although the exact form of these domains is more difficult to visualize. We show that the form of these PNRs can be revealed by an examination of conditional displacement distributions at low temperatures. Therein a strongly anisotropic cooperative displacement behavior is found. Remnants of this correlation pattern persist at much higher temperatures, but progressively a relatively smaller proportion of the Pb ions appears to be taking part and there is a substantially larger random component. It seems likely that the onset of the characteristic structured diffuse scattering at around 400 K coincides with the appearance of this cooperative displacement behavior.
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