The depth profiles of the polarization in films of polyvinylidene fluoride (PVDF) as well as in vinylidene‐fluoride–trifluoroethylene (VDF‐TrFE) copolymer films polarized by a focused electron beam were investigated using the piezoelectrically generated pressure step method. The dominant polarization exhibits a broad maximum inside the film. The position of this maximum depends not only on the energy of the incident electrons but also on the material parameters of the sample. Close to the surface exposed to the electron beam we have in addition observed a small secondary maximum of opposite polarization (amounting to about 1 mC/m2). A qualitative model is presented for the poling of films of PVDF and its copolymers with TrFE by focused electron beam accounting for most of the observed features. The application of electron beams for the poling of ferroelectric films allows the production of piezoelectric bimorphs. By using a well‐focused electron beam also ferroelectric domains of very small lateral dimensions can be created which could become important for ferroelectric data storage.
