Mapping the structural transitions controlled by the trilinear coupling in Ca3-xSrxTi2O7

We present the results of the high-temperature neutron and x-ray diffraction experiments on the Ca3-xSrxTi2O7 (x=0.5, 0.8, 0.85, 0.9) compounds. The ferro- to paraelectric transition in these hybrid improper ferroelectric materials arises from the so-called trilinear coupling. Depending on the strontium content, various structures and phase transitions, different from theoretical predictions, emerge. The in situ x-ray powder diffraction indicates a direct ferro- to paraelectric transition between the orthorhombic A2(1)am and the tetragonal undistorted I4/mmm phase for x <= 0.6. We identified a reduction in the trilinear coupling robustness by increasing the Sr-doping level to lead to the emergence of the intermediate tetragonal P4(2)/mnm phase and the gradual suppression of the orthorhombic phase. The observed character of the structure transitions and the Ca3-xSrxTi2O7 phase diagram are discussed in the framework of theoretical models of other related hybrid improper ferroelectric systems.