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In this work, Bi3.25La0.75Ti3O12 (BLT) thin films were prepared by sol-gel coatings followed by rapid thermal annealing in Ar, O2 and atmosphere ambient, respectively.The XPS depth profile and the correlation among annealing ambient, ferroelectric characteristics and surface chemistry of the BLT thin films were investigated.The BLT thin film annealed in Ar showed weaker crystallization, less dense surface and smaller polarization value than that annealed in O2.X-ray photoelectron spectroscopy results indicated the inferior fatigue characteristics of the sample annealed in Ar was the comprehensive result of oxygen vacancies vicinity to Bi and Ti ion in the thin film.