In situ temperature-dependent Raman-scattering experiments under an external dc electric field E have been performed on PbSc 0:5 Ta [110]. This indicates that the actual polar B-cation shifts are along the cubic body diagonals, implying a rhombohedral structure of the polar nanoregions. The T ? ðEÞ-dependence reveals that the local structural distortions associated with locally coupled polar displacements of B-site cations reach saturation near 0.5 kV/cm. When Pb 2þ is partially replaced by Ba 2þ , the strong increase of T ? with E occurs if the electric field is applied along the [110] direction. This indicates that the substitution disorder on the A-site lowers the symmetry of the polar nanoregions to orthorhombic or monoclinic. The T ? ðEÞ dependence determined from the B-cation localized mode shows saturation near 2.0 kV/cm, indicating that the zero-field structural state of PST-Ba exhibits less coupled polar shifts of B-site cations as compared to that of PST. According to the E-dependence of the Raman scattering near 55 cm À1 , for both compounds the overall response of the Pb system to the external electric field in the vicinity of T ? ðEÞ resembles antiferroelectric behavior, which along with the fact that the coupling between the B-site cations is ferroelectric, suggests that the polar nanoregions in Pb-based relaxors are ferrielectric in nature.

Raman spectroscopy at different temperatures and under an external electric field E was applied to PbSc0.5Nb0.5O3 single crystals in order to gain further insights into the mesoscopic-scale coupling processes in perovskite-type (ABO3) relaxor ferroelectrics. Parallel and cross-polarized Raman spectra were collected between 800-80 K with E applied along the cubic [1 0 0], [1 1 0] or [1 1 1] crystallographic directions. The analysis was focused on the field-induced changes in the temperature evolution of three low-energy phonon modes: the Pb-localized mode near 50 cm(-1), the Pb-BO3 translation mode near 150 cm(-1), and the B-cation-localized mode near 250 cm(-1). The results show that competitive ferroelectric (FE) and antiferroelectric (AFE) coupling exists within the system of off-centred Pb(2+) cations, within the system of off-centred B-site cations as well as between off-centred Pb(2+) and B-site cations. The strong AFE-type coupling between Pb(2+) cations along the cubic body diagonal significantly influences the coupling between the B-site cations via the Pb-BO3 mode and results in AFE-type behaviour of the 'microscopic' T* determined from the B-cation-localized mode near 250 cm(-1), which explains the previously reported non-trivial field dependence of the 'macroscopic' characteristic temperatures: the temperature of the dielectric-permittivity maximum Tm, T*, and the Burns temperature TB. The comparative analysis between PbSc0.5Nb0.5O3 and PbSc0.5Ta0.5O3 indicates that two major displacive order parameters couple to form a relaxor state in B-site complex perovskites: the FE order associated with polar shifts of B-site cations and the AFE order associated with polar shifts of A-site cations. The latter penetrates through both polar and non-polar regions, but it is highly frustrated due to the high density of translation-symmetry faults in the chemical NaCl-type B-site order. The frustrated AFE order of off-centred A-site cations might be the key factor for the existence of a relaxor state.

Lead-based ABO3-type relaxors and related systems have numerous applications in modern technical devices because of their remarkably high dielectric permittivity and piezoelectric/electroelastic and electro-optic coefficients. However, lead is not desired from an environmental point of view, and to switch to alternative alkali-, Ba-, or Bi-based relaxor systems, one must understand in great detail the structural mesoscopic order and coupling processes responsible for the outstanding performance and multifunctionality of the exemplar Pb-based compounds. To elucidate the type of ferroic coupling, three relaxor compounds PbSc0.5Ta0.5O3 (PST), Pb0.78Ba0.22Sc0.5Ta0.5O3 (PST-Ba), and PbSc0.5Nb0.5O3 (PSN), were studied by polarized Raman scattering and acoustic emission at different temperatures and under an external electric field. The results reveal the coexistence of mesoscopic-scale ferroelectric and antiferroelectric coupling, which are predominantly related to B-site cations and A-site Pb cations, respectively. This suggests that the polar structural state of relaxors is frustrated ferrielectric. The presence of A-site cations with affinity to off-center is significant for the development of mesoscopic-scale antiferroelectric order coexisting with the mesoscopic-scale ferroelectric order.