PVDF is prepared firstly in the form of a thin plastic/polymeric like film. Piezoelectric PVDF is an electroded polymer film which has been electrically poled to make it piezoelectric. Poling a PVDF film is a done very specifically.
Thin films of few microns can be synthesised in the lab by dissolving the monomer in the solvent followed by casting. These can be poled in appropriate conditions as suggested by Prof. Shreenivas. The poling conditions can be obtained from the literature.
PVDF is not ferroelectric until it is converted to beta phase (usually by stretching 300% to 500%), PVDF-TrFE is beta phase as cast but needs to be crystallized. Once crystallized it becomes piezoelectric after poling.