Piezo- and pyroelectric materials are of interest, for example, for energy harvesting applications, for the development of tactile sensors, as well as neuromorphic computing. This study reports the observation of pyro- and piezoelectricity in thin surface-attached polymer brushes containing zwitterionic and electrolytic side groups that are prepared via surface-initiated polymerization. The pyro- and piezoelectric properties of the surface-grafted polyelectrolyte brushes are found to sensitively depend on and can be tuned by variation of the counterion. The observed piezo- and pyroelectric properties reflect the structural complexity of polymer brushes, and are attributed to a complex interplay of the non-uniform segment density within these films, together with a non-uniform distribution of counterions and specific ion effects. The fabrication of thin pyroelectric films by surface-initiated polymerization is an important addition to the existing strategies toward such materials. Surface-initiated polymerization, in particular, allows for facile grafting of polar thin polymer films from a wide range of substrates via a straightforward two-step protocol that obviates the need for multistep laborious synthetic procedures or thin film deposition protocols. The ability to produce polymer brushes with piezo- and pyroelectric properties opens up new avenues of application of these materials, for example, in energy harvesting or biosensing.
Keywords: Hofmeister series; counterions; energy conversion; piezoelectricity; polyelectrolyte brushes; pyroelectricity.
© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.