According to recent experiments and predictions, the orientation of the polarization at the surface of a ferroelectric material can affect its surface chemistry. Here we demonstrate the converse effect: the chemical environment can control the polarization orientation in a ferroelectric film. In situ synchrotron x-ray scattering measurements show that high or low oxygen partial pressure induces outward or inward polarization, respectively, in an ultrathin PbTiO3 film. Ab initio calculations provide insight into surface structure changes observed during chemical switching.

Control and imaging of ferroelectric domains over large areas with nanometer resolution in atomically smooth epitaxial Pb(Zr 0.2 Ti 0.8 )O 3 thin films