Nanoscale Resolution of Electric-field Induced Motion in Ionic Diblock Copolymer Thin Films

JW Dugger and W Li and MT Chen and TE Long and RJL Welbourn and MWA Skoda and JF Browning and R Kumar and BS Lokitz, ACS APPLIED MATERIALS & INTERFACES, 10, 32678-32687 (2018).

DOI: 10.1021/acsami.8b11220

Understanding the responses of ionic block copolymers to applied electric fields is crucial when targeting applications in areas such as energy storage, microelectronics, and transducers. This work shows that the identity of counterions in ionic diblock copolymers substantially affects their responses to electric fields, demonstrating the importance of ionic species for materials design. In situ neutron reflectometry measurements revealed that thin films containing imidazolium based cationic diblock copolymers, tetrafluoroborate counteranions led to film contraction under applied electric fields, while bromide counteranions drove expansion under similar field strengths. Coarse-grained molecular dynamics simulations were used to develop a fundamental understanding of these responses, uncovering a nonmonotonic trend in thickness change as a function of field strength. This behavior was attributed to elastic responses of microphase separated diblock copolymer chains resulting from variations in interfacial tension of polymer-polymer interfaces due to the redistribution of counteranions in the presence of electric fields.

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