Influences of oxygen pressure on optical properties and interband electronic transitions in multiferroic bismuth ferrite nanocrystalline films grown by pulsed laser deposition

Bismuth ferrite (BiFeO(3)) nanocrystalline films with the crystalline size of 27-40 nm have been grown on c-sapphire substrates under various oxygen pressures of 1 × 10(-4) to 1 Pa by pulsed laser deposition. The X-ray diffraction spectra show that the films are polycrystalline and present the pure rhombohedral phase. It was found that the Raman-active phonon mode E(TO1) shifts towards a higher energy side from 74 to 76 cm(-1) with increasing oxygen pressure, indicating a larger tensile stress in the films deposited at higher oxygen pressure. The X-ray photoelectron spectroscopy analysis suggests that the concentrations of both Fe(2+) ions and oxygen vacancies in the BiFeO(3) films increase with decreasing oxygen pressure. Moreover, the dielectric functions in the photon energy range of 0.47-6.5 eV have been extracted by fitting the transmittance spectra with the Tauc-Lorentz dispersion model. From the transmittance spectra, the fundamental absorption edge is observed to present a redshift trend with increasing the temperature from 8 to 300 K. Note that the optical band gap (E(g)) decreases with increasing the temperature due to the electron-phonon interactions associated with the interatomic distance in the BiFeO(3) films. However, the E(g) decreases from 2.88 to 2.78 eV with decreasing oxygen pressure at 8 K, which can be attributed to the increment of oxygen vacancies leading to the formation of some impurity states between the valence and conduction band. It can be concluded that the oxygen pressure during the film fabrication has the significant effects on microstructure, optical properties, and electronic band structure modification of the BiFeO(3) films.