In this letter a method to simultaneously measure the physical and the polarization thickness of a 90° domain wall in a ferroelectric perovskite is presented. This method combines accurate atomic force microscopy and piezoresponse force microscopy scans of the same area with little drift and an analysis of the entire scanned area. It is found that the physical thickness is significantly narrower (about seven and a half times) than the polarization thickness in a 90° domain wall in BaTiO3. Evidence of the trapping of defects at such domain walls is also found.

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