Au‐Polaritons Regulated Molecular Dipoles on Empowering the Giant Pyroelectric Response of Highly Oriented Dipoles of PVDF Thin Films

Abstract Ferroelectric polymers reinforced with noble metals enable advanced sensors, photodetectors, flexible electronics, and energy harvesters. This study investigates the effects of integrating hexagonal nanogold (n‐Au) into poly(vinylidene fluoride) (PVDF), a prominent ferroelectric polymer, to advance the structure‐property relationship in hybrid materials for next‐generation sensor and energy conversion technologies. The fabricated Au‐PVDF thin films (≤100 nm) are exhibiting a nearly pure β ‐PVDF phase with edge‐on orientation of (300) lattice planes. This is a unique 2D architecture that is achieved by balancing Au‐PVDF interfacial charges and plasmonic effects, resulting in enhanced piezo‐ and pyro‐electric responses. Plasmon polaritons confined within the polymer matrix regulate collective dipole dynamics and electron transport in network channels, leading to surface‐enhanced light absorption across the UV to IR spectrum. A pyroelectric device constructed using n‐Au‐PVDF thin films demonstrates superior performance with an in‐plane pyroelectric coefficient of 20.6 µC·m − 2 ·K −1 , generating 5.9 nA and 4.5 V under thermal fluctuations from 294 to 301 K. The improved response time is reduced to 20 ms, representing an 80 % improvement over the performance in PVDF composite pyroelectrics. It highlights the potential of n‐Au‐PVDF hybrids for applications in smart sensors, flexible electronics, waste‐energy harvesting, and advanced photodetectors.