Chemically induced renormalization phenomena in Pb-based relaxor ferroelectrics under high pressure

The pressure-induced phase transition sequence in PbSc(0.5)Ta(0.5)O(3) (PST) and PbSc(0.5)Nb(0.5)O(3) (PSN) heavily doped with homo- and heterovalent cations on the A- or B-site of the perovskite-type structure (ABO(3)) was analysed by in situ synchrotron x-ray diffraction and Raman spectroscopy up to pressures of 25 GPa. We focused on the structural phenomena occurring above the first pressure-induced phase transition at p(c1) from a relaxor state to a non-polar rhombohedral phase with antiphase tilting of the BO(6) octahedra. The samples studied were PST doped with Nb(5+) and Sn(4+) on the B-site, PST doped with Ba(2+) and La(3+) on the A-site and PSN doped with Sr(2+) and La(3+) on the A-site. All of them exhibit a second pressure-induced phase transition at p(c2), similar to pure PST and PSN. The second transition involves the development of either order of antiparallel Pb(2+) displacements and complementary a(+)b(-)b(-) octahedral tilts, or a(-)b(-)b(-) (0 ≤ a < b) tilting alone. As in pure PST and PSN, the second phase transition is preceded by the occurrence of unequal octahedral tilts on the local scale. The substitution of Nb(5+) for Ta(5+) as well as the coupled substitution of Sn(4+) for Sc(3+) + Ta(5+) on the octahedral B sites increases the second critical pressure. The doping by Nb(5+) also reduces the length of coherence of antipolar Pb(2+) order developed at p(c2). The isovalent substitution of the larger Ba(2+) for Pb(2+) on the A-site suppresses the antipolar Pb(2+) order due to the induced local elastic stresses and thus significantly increases p(c2). The substitution of smaller cations for Pb(2+) on the A-site generally favours the development of long-range order of antiparallel Pb(2+) displacements because of the chemically enhanced a(-)a(-)a(-) octahedral tilts. However, this ordering is less when the dopant is aliovalent, due to the charge imbalance on the A-site. For all of the relaxors studied here, the dynamic compressibility estimated from the pressure derivative of the wavenumber of the soft mode associated with the first phase transition is larger in the pressure interval between p(c1) and p(c2) than above p(c2). The dynamic compressibility of the phase above p(c2) decreases if the antipolar Pb(2+) order is disturbed.