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Issue 22, 2015
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Critical roles of Mn-ions in enhancing the insulation, piezoelectricity and multiferroicity of BiFeO3-based lead-free high temperature ceramics

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Abstract

A lead-free multiferroic ceramic of BiFe0.96Sc0.04O3–BaTiO3 is a type of ABO3 perovskite structure, belonging to the R3c space group, but exhibiting poor insulation and weak multiferroicity. In this work, the critical roles of Mn-ions in tailoring the electrical and magnetic properties of BiFeO3-based materials are revealed: the introduction of MnO2 into BiFe0.96Sc0.04O3–BaTiO3 induces a dramatic improvement in insulation, piezoelectricity and multiferroicity. New compositions of BiFe0.96Sc0.04O3–BaTiO3 + x mol% MnO2 were synthesized by a conventional solid-state reaction method. All the ceramics possess a perovskite structure, and a morphotropic phase boundary (MPB) of rhombohedral and monoclinic phases is formed at x = 0.5–1.0. The formation of Image ID:c5tc00507h-t1.gif and Image ID:c5tc00507h-t2.gif is noticeably suppressed and the resistivity of the ceramics is increased by ∼100 times after the addition of 0.5–1.0 mol% MnO2, which make the ceramic polarizable and thus give strong ferroelectricity and considerable piezoelectricity. The ceramics with the MPB composition exhibit high electrical insulation (R = 1.2–1.7 × 1010 Ω cm), good piezoelectricity (d33 = 123–143 pC N−1, kp = 0.34–0.35), strong ferroelectricity (Pr = 13.1–17.6 μC cm−2), high Curie temperature (590–596 °C) and excellent temperature stability of piezoelectric and ferroelectric properties. These improvements are greatly associated with the contribution of Mn ions in the ceramics. Surprisingly, sharply enhanced ferromagnetism with Mr = 0.4946 emu g−1 and Ms = 1.0298 emu g−1 is obtained in the ceramic with x = 7.0, almost one thousand times larger than that of an un-doped ceramic. The origin of unusual ferromagnetism is associated with significant changes in magnetic ordering caused by Mn doping. The high magnetoelectric effect (α33 = 429.6 mV cm−1 Oe−1) is obtained after the addition of 2.0 mol% Mn ions. Our study suggests that the present ceramics may have potential applications in advanced memory devices as promising lead-free high temperature piezoelectric and multiferroic materials.

Graphical abstract: Critical roles of Mn-ions in enhancing the insulation, piezoelectricity and multiferroicity of BiFeO3-based lead-free high temperature ceramics

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Publication details

The article was received on 21 Feb 2015, accepted on 07 May 2015 and first published on 08 May 2015


Article type: Paper
DOI: 10.1039/C5TC00507H
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Citation: J. Mater. Chem. C, 2015,3, 5811-5824

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    Critical roles of Mn-ions in enhancing the insulation, piezoelectricity and multiferroicity of BiFeO3-based lead-free high temperature ceramics

    Y. Guo, P. Xiao, R. Wen, Y. Wan, Q. Zheng, D. Shi, K. H. Lam, M. Liu and D. Lin, J. Mater. Chem. C, 2015, 3, 5811
    DOI: 10.1039/C5TC00507H

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