A High-Pressure Raman Study of Mixed Perovskites BaCexZr1−xO3 (0≤x≤1)

• Published in: Journal of solid state chemistry Vol. 149; no. 2; pp. 298 - 307
• Main Authors: Chemarin, C., Rosman, N., Pagnier, T., Lucazeau, G.
• Format: Journal Article
• Language: English
• Published: San Diego, CA Elsevier Inc 01.02.2000; Elsevier
• Subjects: compressibility; Condensed matter: structure, mechanical and thermal properties; Crystalline state (including molecular motions in solids); Crystallographic aspects of phase transformations; pressure effects; Exact sciences and technology; high pressure; perovskite; phase diagram; Physics; Raman spectroscopy; Structure of solids and liquids; crystallography; compressibility; phase diagram; perovskite; Raman spectroscopy; high pressure; Raman spectra; Phase diagrams; Inorganic compounds; Compressibility; Pressure effects; Phase transformations; Transition element compounds; Perovskites; Rare earth compounds; Experimental study; Very high pressure; Solid solutions; Zirconium oxides; Barium oxides; Chemical composition; Cerium oxides; Crystal structure
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1006/jssc.1999.8530

A high-pressure Raman study of polycrystalline samples of BaCexZr1−xO3 is performed at room temperature. The evolution of Raman spectra with pressure is compared to the evolution of the Raman spectra of BaZrO3 and BaCeO3. The effect of composition on the pressure-induced phase transitions is monitored from the Raman spectra. Transitions toward lower symmetry phases as pressure increases are evidenced. A phase diagram in the binary system BaZrO3–BaCeO3 based on the Raman spectra characteristic of the different structures of BaCeO3 (Pnma, Imma, R3c, Pm3m) is proposed. The transition pressures toward low-symmetry structures decrease when Ce is replaced for Zr. This study allows us to interpret the BaCexZr1−xO3 (0≤x≤1) Raman spectra at ambient pressure on the basis of nanodomains and nanophases. These objects tend to disappear upon pressure increase. The octahedra to dodecahedra volumes ratio is used as a critical parameter that is able to reproduce qualitatively some of the phase transitions in the mixed perovskites BaCexZr1−xO3. In order to calculate this parameter vs pressure, a derivation of the samples' compressibility based on a polyhedral approach is performed and is found in the range [0.7×10−11–1.0×10−11 Pa−1].