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Full pattern Le-Bail refinement using x-ray powder diffraction profiles ofSr1-xCaxTiO3 for x=0.02, 0.04 in the temperature range 12 to 300 K revealsanomalies in the unit cell parameters at 170, 225 K due to anantiferrodistortive (cubic to tetragonal I4/mcm) phase transition and at ~32,~34 K due to a transition to a polar phase (tetragonal I4/mcm to orthorhombicIc2m), respectively. The lower transition temperatures obtained by us are inexcellent agreement with those reported on the basis of the dielectric studiesby Bednorz and Muller, [10] who attributed these to ferroelectric transition.Rietveld analysis of the diffraction profiles of the polar phase revealsoff-centre displacements of both Sr2+/Ca2+ and Ti4+ ions in the X-Y plane along<110> pseudocubic directions, in agreement with the experimentally reporteddirection of easy polarization by Bednorz and Muller, but the resulting dipolemoments are shown to be ferrielectrically coupled in the neighbouring (001)planes along the [001] direction leading to anomalously low values of thespontaneous polarization at 12K.

applied physics letters

Structural Basis for the Anomalously Low Spontaneous Polarisation Values  of the Polar Phase of Sr1-xCaxTiO3 (x=0.02, 0.04): Evidence for a  Ferrielectric Ordering