High-pressure structural studies of Li x La1/3NbO3 (x = 1/6, 1/3, 1/2, 2/3)

The high-pressure behavior of Li x La1/3NbO3 (x = 1/6, 1/3, 1/2, 2/3) perovskites where Li cations were substituted for the existing vacancies was studied using synchrotron X-ray diffraction. It was shown that all these materials undergo irreversible pressure-induced amorphization around 14.5 GPa regardless of the Li concentration. The Li-inserted materials were found to exhibit a standard pressure response (bulk modulus pressure derivative B 0′ ~4) when in the crystalline phase, whereas La1/3NbO3 shows a linear volume contraction versus pressure, i.e., B 0′ ~(−1). These results suggest that the structural collapse is not a consequence of cation disorder resulting from the Nb atoms (B-site) migrating to the A-site vacancies. The observed pressure response can be understood by increased occupancy of the A-sites opposing the tilting of the NbO6 octahedra. The pressure evolution of the Nb oxidation state is discussed.