Scattering scanning near-field optical microscopy (s-SNOM) has been established as an excellent tool to probe domains in ferroelectric crystals at room temperature. Here, we apply the s-SNOM possibilities to quantify low-temperature phase transitions in barium titanate single crystals by both temperature-dependent resonance spectroscopy and domain distribution imaging. The ortho- rhombic-to-tetragonal structural phase transition at 263K manifests in a change of the spatial arrangement of ferroelectric domains as probed with a tunable free-electron laser. More intrigu- ingly, the domain distribution unravels non-favored domain configurations upon sample recovery to room temperature as explainable by increased sample disorder. Ferroelectric domains and topo- graphic influences are clearly deconvolved even at low temperatures, since complementing our s- SNOM nano-spectroscopy with piezoresponse force microscopy and topographic imaging using one and the same atomic force microscope and tip.
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