High temperature emissivity, reflectivity, and x-ray absorption of BiFeO3

We report on the lattice evolution of BiFeO3 as function of temperature using far infrared emissivity, reflectivity, and x-ray absorption local structure. A power law fit to the lowest frequency soft phonon in the magnetic ordered phase yields an exponent beta=0.25 as for a tricritical point. At about 200 K below T-N similar to 640 K it ceases softening as consequence of BiFeO3 metastability. We identified this temperature as corresponding to a crossover transition to an order-disorder regime. Above similar to 700 K strong band overlapping, merging, and smearing of modes are consequence of thermal fluctuations and chemical disorder. Vibrational modes show band splits in the ferroelectric phase as emerging from triple degenerated species as from a paraelectric cubic phase above T-C similar to 1090 K. Temperature dependent x-ray absorption near edge structure (XANES) at the Fe K edge shows that lower temperature Fe3+ turns into Fe2+. While this matches the FeO wustite XANES profile, the Bi L-III-edge downshift suggests a high temperature very complex bond configuration at the distorted A perovskite site. Overall, our local structural measurements reveal high temperature defect-induced irreversible lattice changes, below, and above the ferroelectric transition, in an environment lacking of long-range coherence. We did not find an insulator to metal transition prior to melting. (C) 2010 American Institute of Physics. [doi:10.1063/1.3486515]