Ultrafast relaxation dynamics of the antiferrodistortive phase in Ca doped SrTiO3

The ultrafast dynamics of the octahedral rotation in $\mathrm{Ca}:\mathrm{SrTi}{\mathrm{O}}_{3}$ is studied by time-resolved x-ray diffraction after photoexcitation over the band gap. By monitoring the diffraction intensity of a superlattice reflection that is directly related to the structural order parameter of the soft-mode driven antiferrodistortive phase in $\mathrm{Ca}:\mathrm{SrTi}{\mathrm{O}}_{3}$, we observe an ultrafast relaxation on a 0.2 ps timescale of the rotation of the oxygen octahedron, which is found to be independent of the initial temperature despite large changes in the corresponding soft-mode frequency. A further, much smaller reduction on a slower picosecond timescale is attributed to thermal effects. Time-dependent density-functional-theory calculations show that the fast response can be ascribed to an ultrafast displacive modification of the soft-mode potential towards the normal state induced by holes created in the oxygen $2p$ states.