Thermodynamic evidence of the ferroelectric Berry phase in europium-based ferrobismuthite Eu2Bi2Fe4O12

GIL REBAZA, A.V.; DELUQUE TORO, C.E.; MEDINA CHANDUVÍ, H.H.; LANDÍNEZ TÉLLEZ, D.A.; ROA-ROJAS, J.

JOURNAL OF ALLOYS AND COMPOUNDS

ELSEVIER SCIENCE SA

Año: 2021 vol. 884

0925-8388

The possible low temperature biferroic feature of Eu 2 Bi 2 Fe 4 O 12 complex perovskites was recently reported. The aim of this work is to present a theoretical study of the structural, magnetic, electronic and ferroelectric properties of this material. Several energy minimization processes were performed for three types of ca­tionic distributions, different angles of rotation, octahedral inclination, and some kinds of magnetic or­ dering. The results reveal that the most stable crystallographic arrangement corresponds to an intercalateddistribution of the Eu 3+ and Bi 3+ cations between the FeO 6 octahedra. Similarly, energy is minimized for rotations and octahedral inclinations corresponding to angles θ e = 12.86° and φ e = 13.32°, respectively. With respect to the distribution of magnetic moments, the results reveal that a G-type antiferromagnetic con­ figuration is the most energetically favorable. The electronic structure is studied from ab initio calculations following the formalism of density functional theory and the pseudopotential plane wave method. In this formalism, the exchange and correlation mechanisms are described by means of the generalized gradient approach (GGA + U), considering spin polarization. The ferroelectric characteristic is analysed by de­termining ferroelectric polarization based on the calculation of the Berry phase. The theoretical results obtained are consistent with the experimental reports, which is why the Eu2Bi2Fe4O12 material is expected to exhibit biferroic behavior at low temperatures, because the Berry phase introduces hybridizations be­tween the 3d-Fe and 2p-O states that favor the occurrence of Dzyaloshinskii-Moriya interactions, which facilitate the occurrence of ferroelectricity coexisting with weak ferromagnetism. An extensive study of the thermodynamic properties in the presence and absence of the Berry phase is undertaken by means of the Debye quasi harmonic model. The specific heat difference with and without the Berry phase reveals theoccurrence of a ferroelectric transition at T = 113 K without the application of external pressure. When the applied pressure is incremented, a systematic increase in the transition temperature is observed due to the reduction of overlap between the 3d-Fe orbitals and the 2p-O orbitals in the compressed octahedra of perovskite.