4.8 Article

Observation of Stabilized Monoclinic Phase as a Bridge at the Morphotropic Phase Boundary between Tetragonal Perovskite PbVO3 and Rhombohedral BiFeO3

Journal

CHEMISTRY OF MATERIALS
Volume 32, Issue 8, Pages 3615-3620

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.0c00944

Keywords

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Funding

  1. Japan Society for the Promotion of Science (JSPS) [16H02393, 18H05208, 19H05625]
  2. National Natural Science Foundation of China [21805215]
  3. Kanagawa Institute of Industrial Science and Technology
  4. World Research Hub Initiative (WRHI) of Tokyo Institute of Technology

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A morphotropic phase boundary (MPB) with coexisting tetragonal and monoclinic phases was observed in perovskite-type (ABO(3)) (1 - x)PbVO3-xBiFeO(3) solid solutions that were synthesized with a high-pressure and high temperature method. At x = 0.95, the single monoclinic phase as an intermediate between tetragonal (PbVO3) and rhombohedral (BiFeO3) phases was identified by Rietveld refinement of synchrotron X-ray powder diffraction data at room temperature, and the monoclinic phase persisted in a wide temperature range. This phase also showed a polarization rotation as a function of temperature. In the tetragonal phase with 0 <= x <= 0.8, a large tetragonal distortion existed in a wide temperature range from room temperature to similar to 900 K, and it showed little dependence on temperature, indicating that the thermal stability of the perovskite structure was enhanced compared with pristine PbVO3, which decomposes at 570 K. Correspondingly, the spontaneous polarization (P-s), which originates from the hybridization between A/B site cations and oxygen, maintained a high value (>100 mu C/cm(2)) in the tetragonal phase. The present study not only provides direct evidence of a monoclinic phase acting as a bridge between morphotropic phases but also suggests the potential of polar perovskites with strong polarity, i.e., PbVO3, as highperformance piezoelectric materials.

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