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 = 0.25 as for a tricritical point. At about...

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Bibliographic Details
Authors: Massa, Nestor Emilio; del Campo, Leire; de Sousa Meneses, Domingos; Echegut, Patrick; Fabbris, Gilberto F. L.; Azevedo, Gustavo; Martínez Lope, María Jesus; Alonso, José Antonio
Format: Article
Status:Published version
Publication date:2010
Country:Argentina
Institution:Consejo Nacional de Investigaciones Científicas y Técnicas
Repository:CONICET Digital (CONICET)
Language:English
OAI Identifier:oai:ri.conicet.gov.ar:11336/129699
Online Access:http://hdl.handle.net/11336/129699
Access Level:Open access
Keyword:BiFeO3
MULTIFERROIC
FAR INFRARED EMISSIVITY
FAR INFRARED REFLECTIVITY
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
Description
Summary: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 = 0.25 as for a tricritical point. At about 200 K below TN 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 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 TC 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 wüstite XANES profile, the Bi LIII-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.