Grain Boundary and Size Effect on the Dielectric, Infrared and Raman Response of SrTiO3 Nanograin Ceramics

ISSN： 0015-0193

Source： Ferroelectrics, Vol.363, Iss.1, 2008-01, pp. : 227-244

Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.

Previous Menu Next

Abstract

The recently revealed giant grain size effect on dielectric properties in undoped SrTiO3 ceramics (J. Petzelt et al., J. Phys.: Condens. Matter 19, 196222 (2007) and references therein), was extended to smaller grains of 80 nm mean grain size. Like for previously studied ceramics with larger grain size, in addition to dielectric permittivity also the infrared and Raman responses were studied and discussed. It was shown that the reduced effective permittivity is fully accounted for by the infrared soft mode behaviour and, similar to single crystals and other ceramics studied, no dielectric dispersion appears below the THz frequency range. The rather universal (independent of the grain size and sintering process) double dead layer structure was proposed to be responsible for the observed changes in the infrared and Raman spectra, allowing the grain core to keep the single crystal dielectric function. The outer dead layer shell (obviously charged due to an oxygen deficit) is very thin (∼ 1 nm) having frequency and temperature independent low permittivity (∼ 10) and is responsible for the static permittivity suppression. The inner layer of only slightly distorted perovskite structure is polar with local polarization normal to grain boundaries gradually decreasing towards the grain centre. This polarization and/or the thickness of the polar layers, which compensate the charged grain boundaries, appear to increase on decreasing temperature, particularly below the structural phase transition. Its nature is still not fully understood. In agreement with our previous suggestions, from the Raman data it can be also concluded that in the low-temperature tetragonal phase of all SrTiO3 ceramics, the local tetragonal axes tend perpendicular to the grain boundaries and the tetragonality is strongly reduced compared to single crystals.