High-resolution aberration-corrected transmission electron microscopy aided by statistical parameter estimation theory is used to quantify localized displacements at a (110) twin boundary in orthorhombic CaTiO3. The displacements are 3–6 pm for the Ti atoms and confined to a thin layer. This is the first direct observation of the generation of ferroelectricity by interfaces inside this material which opens the door for domain boundary engineering.
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