Programmable Photothermal and Pyroelectric Responses in a Flexible PVDF-Based Hybrid Film for Stimuli-Responsive Biointerfaces

External thermal and electrical stimulations are widely explored to promote tissue regeneration; yet, integrating both modalities into a single, programmable soft film remains challenging. Here, we present a flexible photoresponsive hybrid film composed of a poly(vinylidene fluoride) matrix incorporating polydopamine-coated BaTiO₃ nanoparticles, fabricated via spin-coating. This composite (denoted as PVDF/PDA@BTO) exhibits a dual-mode functionality that enables both steady and pulsed stimulations within a single biocompatible platform. Under continuous near-infrared irradiation, the film delivers stable photothermal outputs, maintaining target temperatures of 37 or 42 °C. Under pulsed irradiation, transient thermal variations trigger the pyroelectric response of BaTiO₃, producing synchronized voltage outputs tunable by pulse duration, with ∼250 mV generated during a 0.25 s pulse. As a proof of concept, the film significantly accelerated rewarming and tissue repair in a mouse frostbite model. This work demonstrates a facile strategy for constructing programmable, multifunctional polymer-inorganic hybrid films with potential in on-demand bioelectronic interfaces and soft therapeutic devices.