Structural transformations in Pb1 − xBi4 + xTi4 − xMnxO15(x = 0.2 and 0.4): a Raman scattering study

Prasetyo, Anton, Mihailova, Boriana, Suendo, Veinardi, Nugroho, A. A., Zulhadjri, Zulhadjri and Ismunandar, Ismunandar (2016) Structural transformations in Pb1 − xBi4 + xTi4 − xMnxO15(x = 0.2 and 0.4): a Raman scattering study. Journal of Raman Spectroscopy, 48 (2). pp. 292-297. ISSN 0377-0486

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Abstract

The temperature evolution of the Raman scattering of Pb1 − xBi4 + xTi4 − xMnxO15 (x = 0.2 and 0.4) on cooling from 850 to 140–130 K was studied in order to elucidate the effect of B-site Mn3+ doping accompanied by the increase in the A-site Bi3+ content on the structural transformations in four-layer Aurivillius-type compound (An − 1Bi2BnO3n + 3, n = 4). The ferroelectric–paraelectric transition (Tc ~800 K for x = 0.2 and ~765 K for x = 0.4) is well mirrored by the Raman scattering near 60 cm−1 arising from the so-called rigid layer mode. The temperature dependence of the phonon mode near 42 cm−1 arising from A-site Pb/Bi displacements indicates a second structural transformation near 570 K and 400 K for x = 0.2 and 0.4, respectively, similar to that observed for Mn-free PbBi4Ti4O15. This structural alteration resembles a thermodynamically second-order phase transition for all three compounds and the critical temperature (Ta) decreases with the increase in the A-site Bi3+ amount, related to the heterovalent substitution (Mn3+ for Ti4+) on the B site; Ta = 600, 570, 400 K for x = 0, 0.2, 0.4, respectively. The BO6 tilting and bending mode near 220 cm−1 also shows an anomaly at Ta, and, thus, this second structural transformation was attributed to subtle rearrangements of A-site cations accompanied by octahedral BO6 tilting in the perovskite-like blocks. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Item Type:	Journal Article
Keywords:	Aurivillius structure-type; ferroelectric phase transition; phonon modes; temperature dependence
Divisions:	Faculty of Mathematics and Sciences > Department of Chemistry
Depositing User:	Faizuddin Harliansyah
Date Deposited:	24 May 2018 17:32

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