Title: Octahedral and polar phase transitions in freestanding films of SrTiO3

Abstract: From extreme strain to bending, the possibilities in the manipulation of freestanding films of oxide perovskites bring a novel landscape to their properties and brings them one step closer to their application. It is therefore of great importance to fully understand the inherent properties of such films, in which dimensionality and surface effects can play a major role in defining the properties of the materials ground state. This paper reports the properties of freestanding (FS) films of the canonical oxide, SrTiO3 (STO) with thicknesses 20, 30, 40 and 80 nm. We show that the relaxed ultrathin STO FS films become polar at temperatures as high as 85 K, in contrast to the quantum paraelectric behavior of bulk. Our findings are based on the softening of the ferroelectric mode towards the ferroelectric transition temperature Tc and its consecutive hardening below Tc with further decreasing temperature, probed with THz time domain spectroscopy in transmission mode. We find almost no thickness dependence in Tc. Moreover, we characterize the antiferrodistortive (AFD) phase transition in STO FS by X-ray diffraction (XRD) probing superlattice reflections characteristic for the rotation of the TiO6 octahedra. Our results point to a higher phase transition temperature in comparison to bulk STO, as well as an unbalanced domain population favoring the rotation axis to be in plane. X-ray linear dichroism results further show a preferential Ti xz/yz orbital occupancy at the surface, but with a complete degeneracy in the t2g states in the inner part of the film indicating that the AFD distortion does not strongly affect the t2g splitting. These findings demonstrate that STO FS films have clearly different properties than bulk.