P(VDF-TrFE) copolymers are materials with high relevance in printed organic electronics. These copolymers easily crystallize into the ferroelectric phase without resorting to post-deposition treatments (thermal annealing, poling, or mechanical stretching). The detection of a morphotropic phase boundary further increased the interest in this copolymer system by demonstrating relaxor behavior for higher TrFE content. This prompted an in-depth analysis of the P(VDF-TrFE) chiral chain structure responsible for the relaxor properties. Nevertheless, the efficient application of these materials also depends heavily on the quality and morphology of the crystalline domains. In this work, we combine SAXS and AFM imaging to analyze the structure of the crystalline domains as a function of the TrFE content. The detection of different structural distributions revealed the presence of hierarchical arrangements within the crystalline domains. Furthermore, these hierarchical arrangements were observed to change with the TrFE monomer content, presenting distinct morphologies for low and high TrFE contents, in line with previous works on the morphotropic phase boundary in these systems.
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