A combined X-ray diffraction and Raman scattering study of the phase transitions in Sr1−xCaxTiO3 (x=0.04, 0.06, and 0.12)

Results of powder X-ray diffraction and Raman scattering studies on the phase transitions in Sr1−xCaxTiO3 (SCT) are presented for x=0.04x=0.04, 0.06 and 0.12 in the temperature range 8–473 K. It is proposed that the space group of SCT in the composition range 0.06⩽x⩽0.350.06⩽x⩽0.35 is ImmaImma with a0b-b-a0b-b- tilt system and not I4/mcmI4/mcm with a0a0c-a0a0c- tilt system, as assumed by earlier workers. The lowering of the crystal symmetry from I4/mcmI4/mcm to ImmaImma is supported by the observation of additional Raman lines, in agreement with the factor group analysis for the ImmaImma space group. The structural Eg mode, characteristics of the non-cubic phase, is shown to be present even in the cubic phases of x=0.06x=0.06 and x=0.12x=0.12 but not of x=0.04x=0.04 indicating the change in the local structure of the cubic phase of SCT for x⩾0.06x⩾0.06. The presence of symmetry forbidden TO2 mode in the Raman spectra of the cubic phase of SCT for x<0.06x<0.06 and its absence for x⩾0.06x⩾0.06 provides yet another characteristic feature distinguishing the I4/mcmI4/mcm and ImmaImma space groups. The implications of the change in the tilt system from a0a0c-a0a0c- to a0b-b-a0b-b- on the development of the polar order is also discussed.

Graphical abstractThis work reports the combine powder X-ray diffraction and Raman scattering studies in Sr1−xCaxTiO3 (SCT) for the compositions x=0.04x=0.04, 0.06 and 0.12. It is proposed that the space group of SCT in the composition range 0.06⩽x⩽0.350.06⩽x⩽0.35 is ImmaImma with a0b-b-a0b-b- tilt system and not I4/mcmI4/mcm with a0a0c-a0a0c- tilt system, as assumed by earlier workers. The lowering of the crystal symmetry from I4/mcmI4/mcm to ImmaImma is supported by the observation of additional Raman lines, in agreement with the factor group analysis for the ImmaImma space group.Figure optionsDownload full-size imageDownload as PowerPoint slide