With the growing demand for miniaturized, self-powered devices, energy harvesting technologies that can exploit ambient and physiological energy sources have gained increasing attention. Beyond conventional batteries, strategies to convert energy from the human bodyâ such as heat or mechanical deformationâ into electricity are especially attractive for wearable electronics and distributed sensing platforms. These processes often rely on polar materials such as polyvinylidene fluoride (PVDF). However, PVDF, as a fluorinated polymer and so-called â forever chemical,â requires complex synthesis under high-temperature and high-pressure conditions. Achieving functional polarization also involves another high-temperature, high-voltage poling step. The semi-crystalline morphology of PVDF can be tailored through chemical modificationsâ most notably by copolymerizationâ to endow it with intrinsically adjustable electromechanical properties without the need for electrical poling. For example, one may evolve from simple P(VDF-co-trifluoroethylene) [P(VDF-TrFE)]â based copolymers to more complex terpolymers and even tetrapolymers. However, in practice this route has proven infeasible for large-scale manufacture owing to its synthetic complexity and the attendant high production costs. Moreover, fabricating PVDF into ultra-thin films is challenging: thick films are incompatible with microelectrode architectures, while thin films are prone to dielectric breakdown during poling.

To address these limitations, this thesis explores polymer brush architectures as an alternative platform for energy conversion. Through surface-initiated polymerization, polymer chains are grafted at one end and extend in an oriented "brush" conformation. This backbone alignment, in turn, compels the pendant polar moieties to adopt, more or less, the same orientation, thereby generating an intrinsic polarization in the as-grafted thin film without the need for any post-treatments such as electrical poling. This architecture provides intrinsic chain ordering, controllable thickness, and excellent conformality, making it highly compatible with micro- and nanoscale device integration.

This thesis demonstrates standard â textbook-qualityâ pyroelectric responses in polar-functionalized polymer brushes, and confirms that the observed behavior originates from fixed dipole moments in the chain architecture. The results further reveal that the pyroelectric performance primarily arises from the dense, brush-like regions of the film where the chains are highly stretched and aligned. In contrast, in thicker brushes, the upper segments tend to adopt disordered coil conformations that contribute negligibly to the overall polarization, effectively diluting the polarision density.

These findings establish polymer brushes as a tunable platform for pyroelectric energy conversion. Beyond simplifying processing requirements, they also offer a model system for probing structureâ polarization relationships and pave the way for flexible, conformal, and energy-autonomous interfaces in next-generation microelectronic systems.