Infrared and Raman spectroscopy of [Pb(Zn1/3Nb2/3)O3]0.92–[PbTiO3]0.08 and [Pb(Mg1/3Nb2/3)O3]0.71–[PbTiO3]0.29 single crystals

Abstract

Far-infrared reflectivity spectra of [Pb(Zn1/3Nb2/3)O3]0.92–[PbTiO3]0.08 and [Pb(Mg1/3Nb2/3)O3]0.71–[PbTiO3]0.29 single crystals were investigated between 10 and 530 K, micro-Raman spectra were recorded between 300 and 800 K. No phonon softening was observed near either of the ferroelectric phase transitions. The low-frequency dielectric anomaly in the paraelectric phase is caused by contribution of dynamic polar nanoclusters with the main dispersion in the microwave range. Infrared and Raman spectra confirm the locally doubled unit cell (Zprim=2) in the paraelectric and ferroelectric phases due to the ordering in the perovskite B sites and occurrence of polar nanoclusters in the paraelectric phase. The lowest-frequency transverse optical (TO1) phonon mode active in the infrared spectra is underdamped in contrast to the recent result of inelastic neutron scattering, where no TO1 mode could be observed for the wave vectors q⩽0.2 Å−1. This discrepancy was explained by different q vectors probed in infrared and neutron experiments. The infrared probe couples with very long-wavelength phonons (q≈10−5 Å−1) which see the homogeneous medium averaged over the nanoclusters, whereas the neutron probe couples with phonons whose wavelength is comparable to the nanocluster size (q⩾10−2 Å−1).