Journal
CHEMISTRY OF MATERIALS
Volume 17, Issue 9, Pages 2404-2412Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm047841f
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High-temperature neutron diffraction (ND) experiments have been carried out in two representative members of the Li3xLa2/3-xTiO3 series (x = 0.067 and 0.167), to analyze the influence of temperature on the perovskite structure. In the orthorhombic Li-poor ordered member Li0.2La0.6TiO3 (Cmmm space group), prepared by slowly cooling from 1673 K, the heating of the sample produced the elimination of the octahedral tilting, along, the b-axis (a(0)b-c(0) scheme) at 873 K, requiring higher temperatures to induce the vacancies disordering. In the rhombohedral Li-rich disordered member Li0.5La0.5TiO3 (R (3) over barc space group), prepared by quenching from 1673 K, the sample heating produced the elimination of the octahedral tilting along the [111] direction (a(-)a(-)a(-) scheme) at 1073 K. The elimination of octahedral tilting drived the orthorhombic-tetragonal transformation in the first perovskite and the rhombohedral-cubic transformation in the second perovskite. A detailed analysis of four identified phases showed that distortions of LaO12 cubooctahedra depends on the octahedral tilting and on the vacancy distribution adopted by the perovskite. Finally, the influence of these two parameters, octahedral tilting and vacancy ordering, on the Li mobility of the perovskite series has been discussed.
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