Nanoscale Piezoelectric Properties and Phase Separation in Pure and La-Doped BiFeO₃ Films Prepared by Sol-Gel Method

Pure BiFeO₃ (BFO) and doped Bi_0.9La_0.1FeO₃ (BLFO) thin films were prepared on Pt/TiO₂/SiO₂/Si substrates by a modified sol-gel technique using a separate hydrolysis procedure. The effects of final crystallization temperature and La doping on the phase structure, film morphology, and nanoscale piezoelectric properties were investigated. La doping and higher crystallization temperature lead to an increase in the grain size and preferred (102) texture of the films. Simultaneously, a decrease in the average effective piezoelectric coefficient (about 2 times in La-doped films) and an increase in the area of surface non-polar phase (up to 60%) are observed. Phase separation on the films' surface is attributed to either a second phase or to a non-polar perovskite phase at the surface. As compared with undoped BFO, La-doping leads to an increase in the average grain size and self-polarization that is important for future piezoelectric applications. It is shown that piezoelectric activity is directly related to the films' microstructructure, thus emphasizing the role of annealing conditions and La-doping that is frequently used to decrease the leakage current in BFO-based materials.