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Title: Critical roles of Mn-ions in enhancing the insulation, piezoelectricity and multiferroicity of BiFeO3-based lead-free high temperature ceramics
Authors: Guo, Y
Xiao, P
Wen, R
Wan, Y
Zheng, Q
Shi, D
Lam, KH 
Liu, M
Lin, D
Issue Date: 2015
Publisher: Royal Society of Chemistry
Source: Journal of materials chemistry C, 2015, v. 3, no. 22, p. 5811-5824 How to cite?
Journal: Journal of materials chemistry C 
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 and 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.
ISSN: 2050-7526
EISSN: 2050-7534
DOI: 10.1039/c5tc00507h
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