Experimental demonstration of hybrid improper ferroelectricity and presence of abundant charged walls in (Ca,Sr)₃Ti₂O₇ crystals

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Standing on successful first principles predictions for new functional ferroelectric materials, a number of new ferroelectrics have been experimentally discovered. Utilizing trilinear coupling of two types of octahedron rotations, hybrid improper ferroelectricity has been theoretically predicted in ordered perovskites and the Ruddlesden-Popper compounds (Ca₃Ti₂O₇, Ca₃Mn₂O₇, and (Ca/Sr/Ba)₃(Sn/Zr/Ge)₂O₇). However, the ferroelectricity of these compounds has never been experimentally confirmed and even their polar nature has been under debate. Here we provide the first experimental demonstration of room-temperature switchable polarization in the bulk crystals of Ca₃Ti₂O₇ as well as Sr-doped Ca₃Ti₂O₇. In addition, (Ca,Sr)₃Ti₂O₇ is found to exhibit an intriguing ferroelectric domain structure resulting from orthorhombic twins and (switchable) planar polarization. The planar domain structure accompanies abundant charged domain walls with conducting head-to-head and insulating tail-to-tail configurations, which exhibit two-order-of-magnitude conduction difference. These discoveries provide new research opportunities not only on new stable ferroelectrics of Ruddlesden-Popper compounds, but also on meandering conducting domain walls formed by planar polarization.