Crystallization-Driven Helical Conjugated Polymer Nanowires for Circularly Polarized Light-Addressable Ferroelectric Physical Unclonable Functions

Abstract

Supramolecular helices of conjugated polymers (CPs) offer versatile chiroptical selectivity, yet their responses are often limited to passive optical readouts and lack stability as nonvolatile electrical states. Here, we report crystallization-driven helical CP nanowires (NWs) that enable circularly polarized light (CPL)-addressable ferroelectric physically unclonable functions (PUFs). The crystallization-driven self-assembly of P3HT-b-PMMA, directed by enantiomeric limonene as a chirality trigger, generates P- and M-helical pi-pi stacked NWs. These nanotemplates are integrated into a ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) matrix, forming chiral-ferroelectric hybrid films that preserve both molecular stacking of CP and beta-phase crystallinity of ferroelectric polymer. We demonstrate that the PMMA corona of the NWs mediates the interfacial interaction with the ferroelectric matrix, transcribing supramolecular helicity into helicity-dependent remanent polarization, establishing handedness-selective polarization landscapes under CPL excitation. These stochastic spatial polarization states serve as robust multiscale entropy sources, yielding 256-bit identifiers with near-ideal bit uniformity (similar to 0.5) and inter-device Hamming distance distributions (similar to 0.4). By stabilizing supramolecular chirality as remanent polarization within an interpenetrated hybrid network, this work establishes a hybrid optoelectric PUF platform that significantly expands the dimension of secure encoding in soft polymer electronics.