Spontaneous ferroelectricity in strained low-temperature monoclinic Fe₃O₄: A first-principles study

Abstract

As a single-phase multiferroic material, Fe₃O₄ exhibits spontaneous ferroelectric polarization below 38 K. However, the nature of the ferroelectricity in Fe₃O₄ and effect of external disturbances such as strain on it remains ambiguous. Here, the spontaneous ferroelectric polarization of low-temperature monoclinic Fe₃O₄ was investigated by first-principles calculations. The pseudo-centrosymmetric FeB42−FeB43 pair has a different valence state. The noncentrosymmetric charge distribution results in ferroelectric polarization. The initial ferroelectric polarization direction is in the −x and −z directions. The ferroelectricity along the y axis is limited owing to the symmetry of the Cc space group. Both the ionic displacement and charge separation at the FeB42−FeB43 pair are affected by strain, which further influences the spontaneous ferroelectric polarization of monoclinic Fe₃O₄. The ferroelectric polarization along the z axis exhibits an increase of 45.3% as the strain changes from 6% to −6%.

Keywords

spontaneous ferroelectric polarization / charge ordering / biaxial strain / Berry phase / modern theory of polarization

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