The microscopic mechanism of the occurrence of ferroelectric properties in M-type barium hexaferrites is investigated by experimental and first-principle computation methods. The analysis of magnetic, X-ray, and Mössbauer measurements of BaFe12O19 samples ascertains the correlation between the thermal factor in the process of annealing samples and their functional properties. The occurrence of the remnant polarization in barium hexaferrites at room temperature contradicts the description of their crystal structure in the framework of centrosymmetric space group P63∕mmc (No. 194), in which one of the symmetry operations is inversion center. Therefore, the crystal structure of BaFe12O19 was analyzed in the frameworks of SG P63∕mmc (No. 194) and non-centrosymmetric SG P63mc (No. 186). The computed value of polarization for a non-centrosymmetric unit cell is ∼ 3.5 μC∕cm2. The analysis of polarization was carried out on a path connecting the polar P63mc and non-polar P63∕mmc structures and considered in terms of the total energy barrier. Our result allows ascertaining a direct relationship between the remnant polarization of the unit cell and the broken spatial-inversion symmetry in the crystal structure of M-type barium hexaferrite.

This project has received funding from the EU - H2020 research and innovation programme under grant agreement No 654360 having benefitted from the access provided by CSIC/ICMAB in Barcelona (ES) within the framework of the Nanoscience Foundries and Fine Analysis (NFFA: ID 1026) Europe Transnational Access Activity. (European grants to support the infrastructure of European centres of collective usage and mobile activity of researchers). Alex V. Trukhanov thanks NUST MISIS for support within the framework of the “Priority 2030″ (K6-2022-043). The authors thank to Dr. D.B. Migas for help with calculations of initial crystal structures.

With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

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