Correlation between the unit cell parameters and electronic transitions in Bi1-xEuxFeO3 thin films

Among AFeO3 (A being divalent or trivalent cation) perovskites, BiFeO3 (BFO) exhibits unique as well as complex electronic structure. In the present study local structure of BFO have been manipulated systematically and correlation with the electronic structure has been presented in detail. An electronic energy-level diagram of polycrystalline Bi1-xEuxFeO3 (0 ≤ x ≤ 0.225) has been presented. Using detailed quantitative structural analysis, diffuse reflectance spectrum and the Kubelka-Munk model, the effect of local structural modification on the electronic structure has been investigated. Systematic structural modification has been achieved by Eu3+ substitution which affects bond length, bond angle, and octahedral rotation, consequently, drives the system towards a higher symmetry configuration. Changes in the multiple electronic transitions in pure BFO thin films as a function of Eu3+ substitution have been investigated in detail. An additional change is the emergence of the 4f levels of the rare earth substituent in the valence and conduction bands, Charge-transfer, and doubly degenerated d-d transitions (6A1g→4T2g and 6A1g→4T1g) have been traced as a function of local changes at the unit cell level. In centrosymmetric configuration, 6A1g→4T1g electronic transition is found to be forbidden by the Laporte Rule.