Use of Raman spectroscopy to determine the site occupancy of dopants in BaTiO3

Chemical doping is one of the major methods by which the properties of BaTiO3 are modified to induce various device characteristics. Doping strategies are generally separated into iso- and alio-valent (donors and acceptors) and into A- and B-site species within the perovskite structure. The A1g octahedral breathing mode at ∼800 cm−1 in BaTiO3 is Raman inactive for compositions with single B-site species. However, this mode becomes Raman active if more than one B-site species is present, including titanium vacancies, VT′′′′. Moreover, the relative intensity of the A1g breathing mode is qualitatively related to the concentration of the species replacing Ti in the B-site. This article illustrates some clear cases where the A1g octahedral breathing mode can be utilized to verify the site occupancy of dopants in BaTiO3 when used in conjunction with more conventional indirect methods such as x-ray diffraction (Vegard’s Law) and dielectric measurements as a function of temperature.