Unusual Strong Incommensurate Modulation in a Tungsten-Bronze-Type Relaxor PbBiNb₅O₁₅

Pb- or Bi-based perovskite oxides have been widely studied and used because of their large ferroelectric polarization features induced by stereochemically active 6s² lone pair electrons. It is intriguing whether this effect could exist in other related systems. Herein, we designed and synthesized a mixed Pb and Bi A site polar compound, PbBiNb₅O₁₅, with the TTB framework. The as-synthesized material turns out to be a relaxor with weak macroscopic ferroelectricity but adopts strong local polarizations. Whats more, unusual five orders of incommensurate satellite reflections with strong intensities were observed under the electron diffraction, suggesting that the modulation is highly developed with large amplitudes. The structural modulation was solved with a (3 + 1)D superspace group using high-resolution synchrotron radiation combined with anomalous dispersion X-ray diffraction technique to distinguish Pb from Bi. We show that the strong modulation mainly originates from lone-pair driven Pb²⁺-Bi³⁺ ordering in the large pentagonal caves, which can suppress the local polarization in x-y plane in long ranges. Moreover, the as-synthesized ceramics display strong relaxor ferroelectric feature with transition temperature near room temperature and moderate dielectric properties, which could be functionalized to be electromechanical device materials.