Ferroelectric polymer nanowires grown using a template-wetting method are shown to achieve an orientated 'self-poled' structure resulting from the confined growth process. Self-poling is highly desirable as it negates the need for high electric fields, mechanical stretching and/or high temperatures typically associated with poling treatments in ferroelectric polymers, as required for piezoelectric and/or pyroelectric applications. Here, we present differential scanning calorimetry, infrared spectroscopy and dielectric permittivity measurements on as-fabricated template-grown polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)) nanowires, and quantitatively compare the results with spin-cast films of the same composition that have been electrically poled, both before and after subsequent de-poling temperature treatment. The measurements reveal remarkably similar trends between the physical properties of the as-grown nanowires and the electrically poled film samples, providing insight into the material structure of the 'self-poled' nanowires. In addition, piezo-response force microscopy (PFM) data is presented that allow s for unambiguous identification of self-poling in ferroelectric polymer nanostructures, and indicates the suitability of the template-wetting approach in fabricating nanowires that can be used directly for piezoelectric/pyroelectric applications, without the need for post-deposition poling/processing.The authors are grateful for financial support from the European Research Council through an ERC Starting Grant (Grant no. ERC-2014-STG-639526, NANOGEN). R.A.W. thanks the EPSRC Cambridge NanoDTC, EP/G037221/1, for studentship funding.This is the author accepted manuscript. It is currently under an indefinite embargo pending publication by Wiley
