A novel approach is reported for obtaining ambipolar electroactive polymers via in situ electropolymerization for vertical organic electrochemical transistor (vOECT) applications. It is shown that electropolymerization is a practical and efficient method to obtain copolymers without contamination from chemical polymerization processes. To this end, two monomers, G-DTP-Bu-NDI and G-DTP-G-NDI, are proposed, comprising naphthalene diimide (NDI) as the acceptor core and dithienopyrrole (DTP) as the donor unit, capable of forming carbon-carbon bonds under the influence of an electric current. The incorporation of oligo(oxyethylene) (OEG) side groups ensures their amphiphilicity. Both compounds underwent successful electrochemical polymerization, resulting in thin, porous, uniform polymer layers on the electrode surface. The synthesized polymers are further examined using electrochemical and spectroelectrochemical techniques in both organic and aqueous electrolytes. Regardless of the electrolyte medium (aqueous or non-aqueous), poly(G-DTP-Bu-NDI), and poly(G-DTP-G-NDI) exhibit stable electroactivity, as demonstrated by numerous scans showing ambipolar redox behavior. Both polymers are tested as components of vertical OECTs, following in situ electrochemical deposition within a 350 nm channel. The recorded transfer characteristics suggest that the fabricated donor-acceptor (D-A) compounds hold promise for developing a new generation of ambipolar ECT devices.

Bioelectronics Materials and Devices Laboratory Central European Institute of Technology Brno University of Technology Purkyňova 123 Brno 61200 Czech Republic

Cardinal Stefan Wyszynski University Faculty of Mathematics and Natural Sciences School of Exact Sciences Woycickiego 1 3 Warsaw 01 938 Poland

Linköping University Laboratory of Organic Electronics ITN Bredgatan 33 Norrköping 60174 Sweden

Warsaw University of Technology Faculty of Chemistry Noakowskiego 3 Warsaw 00 664 Poland

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