Study of 0.9PMN–0.1PT Dielectric Behaviour in Relation to the Nanostructure

Abstract

(1 - x)PbMg1/3Nb2/3O3-xPbTiO3 ceramics with x = 0, 0.1 were prepared with a 12 mol% MgO excess to obtain dense and perovskite phase materials after sintering. The dielectric characterization has revealed that a local polarization appears at a Td temperature largely above the temperature of the maximum of permittivity (Tm, respectively -13 ○C and +36 ○C for x = 0 and 0.1). This phenomena is consistent with the nucleation of polar clusters. Moreover, a dielectric relaxation is observed for 0.9PMN-0.1PT-0.12MgO, in a large frequency range (100 Hz – 1 GHz), which corresponds to a multi-Debye process with broadening of the relaxation time distribution as the temperature decreases. This suggests a nucleation and growth mechanism of polar clusters with decreasing temperature, which can result from the successive transitions of different compositions. This hypothesis was confirmed by the identification of large chemical heterogeneities on a nanometric scale by TEM using two spectroscopy techniques (EDXS and EELS), because of the association of low and high atomic number elements in the materials, different types of equipment and also the simulation of the patterns with standards. In fact, these quantitative analyses have revealed large fluctuations of the local composition around the nominal one: lead and magnesium deficient areas enriched in niobium coexist with nanodomains largely enriched in lead and slightly in magnesium, which the size depends on the titanium content. The origin of these heterogeneities in correlation with the reactions sequences during calcination and sintering is discussed: in particular the addition of titanium contributes, by stabilizing the perovskite phase, to limit the diffusion of lead oxide, which consequently increases the homogeneity of the ceramics. Due to such heterogeneities, the material remains mainly paraelectric up to very low temperatures. This effect can be balanced by the application of a high electric field which induces the growth of the polar clusters by displacement of their interface with the paraelectric matrix and orientation of their polarization in the direction of the electric field which can lead to a macroscopic ferroelectric transition in specific conditions of temperature and electric field intensity. These different mechanisms relax in a frequency range which depends on the temperature and on the amplitude of the electric field.