Lead-Free Aurivillius Phase Bi2LaNb1.5Mn0.5O9: Structure, Ferroelectric, Magnetic, and Magnetodielectric Effects

Tio Putra Wendari; Syukri Arief; Nandang Mufti; Graeme R Blake; Jacob Baas; Veinardi Suendo; Anton Prasetyo; Andon Insani; Zulhadjri Zulhadjri

doi:10.1021/acs.inorgchem.1c03624

Lead-Free Aurivillius Phase Bi₂LaNb_1.5Mn_0.5O₉: Structure, Ferroelectric, Magnetic, and Magnetodielectric Effects

Inorg Chem. 2022 Jun 13;61(23):8644-8652. doi: 10.1021/acs.inorgchem.1c03624. Epub 2022 May 27.

Authors

Tio Putra Wendari¹, Syukri Arief¹, Nandang Mufti², Graeme R Blake³, Jacob Baas³, Veinardi Suendo⁴, Anton Prasetyo⁵, Andon Insani⁶, Zulhadjri Zulhadjri¹

Affiliations

¹ Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas, Kampus Limau Manis, Padang 25163, Indonesia.
² Center of Advanced Materials for Renewable Energy, Universitas Negeri Malang, Jl. Semarang 5, Malang 65145, Indonesia.
³ Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
⁴ Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia.
⁵ Department of Chemistry, Faculty of Science and Technology, Universitas Islam Negeri Maulana Malik Ibrahim Malang, Jl. Gajayana 50, Malang 65144, Indonesia.
⁶ Center for Science and Technology of Advanced Materials, National Nuclear Energy Agency of Indonesia, Puspiptek Serpong, Tangerang Selatan 15314, Indonesia.

PMID: 35622976
DOI: 10.1021/acs.inorgchem.1c03624

Abstract

Aurivillius phase Bi₂LaNb_1.5Mn_0.5O₉, derived from ferroelectric PbBi₂Nb₂O₉ by simultaneous substitution of the A-site and B-site cations, was synthesized using a molten-salt method. Here, we discuss the structure-property relationships in detail. X-ray and neutron diffraction show that Bi₂LaNb_1.5Mn_0.5O₉ adopts an A2₁am orthorhombic crystal structure. Rietveld refinement analysis, supported by Raman spectroscopy, indicates that the Bi³⁺ ions occupy the bismuth oxide blocks, La³⁺ ions occupy the perovskite A-site, and Nb⁵⁺/Mn³⁺ ions occupy the perovskite B-site. Ferroelectric ordering takes place at 535 K, which coexists with local ferromagnetic order below 65 K. The cation disorder on the B-site results in relaxor-ferroelectric behavior, and the short-range ferromagnetic order can be attributed to Mn³⁺/Mn⁴⁺ double-exchange. Magnetodielectric coupling measured at 5 K and 100 kHz in a field of 5 T suggests the existence of intrinsic spin-lattice coupling with a magnetodielectric coefficient of 0.20%. These findings will provide significant impetus for further research into potential devices based on the magnetodielectric effect in Aurivillius materials.