Vliv velikosti a hranic zrn na dielektrickou, infračervenou a ramanovskou odezvu SrTiO3 nanokeramiky

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

journal article - other

en

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 (ca 1 nm) having frequency and temperature independent low permittivity (ca 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.

Článek rozšiřuje nedávno objevený obrovský vliv velikosti zrn na dielektrické vlastnosti SrTiO3 keramiky až do nanokeramické oblasti. K tomu sloužila nedávno poprvé připravená hutná (98%t.h.) SrTiO3 keramika s velikostí zrn 80um.

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 (ca 1 nm) having frequency and temperature independent low permittivity (ca 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.

SrTiO3 nanokeramika, spark plazma sintering, mrtvá vrstva, efektivní infračervená a dielektrická odezva, ramanovská odezva

Strontium titanate nanoceramics; core-shell composite; dead layer; effective dielectric and infrared response; raman response

2008

01.01.2008

0015-0193

FERROELECTRICS

363

1

227–244

18