Enhancing the Backbone Coplanarity of n‑Type Copolymers for Higher Electron Mobility and Stability in Organic Electrochemical Transistors

• Published in: Chemistry of materials Vol. 34; no. 19; pp. 8593 - 8602
• Main Authors: Maria, Iuliana P., Griggs, Sophie, Rashid, Reem B., Paulsen, Bryan D., Surgailis, Jokubas, Thorley, Karl, Le, Vianna N., Harrison, George T., Combe, Craig, Hallani, Rawad, Giovannitti, Alexander, Paterson, Alexandra F., Inal, Sahika, Rivnay, Jonathan, McCulloch, Iain
• Format: Journal Article
• Language: English
• Published: American Chemical Society 11.10.2022
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.2c01552

Electron-transporting (n-type) conjugated polymers have recently been applied in numerous electrochemical applications, where both ion and electron transport are required. Despite continuous efforts to improve their performance and stability, n-type conjugated polymers with mixed conduction still lag behind their hole-transporting (p-type) counterparts, limiting the functions of electrochemical devices. In this work, we investigate the effect of enhanced backbone coplanarity on the electrochemical activity and mixed ionic-electronic conduction properties of n-type polymers during operation in aqueous media. Through substitution of the widely employed electron-deficient naphthalene diimide (NDI) unit for the core-extended naphthodithiophene diimide (NDTI) units, the resulting polymer shows a more planar backbone with closer packing, leading to an increase in the electron mobility in organic electrochemical transistors (OECTs) by more than two orders of magnitude. The NDTI-based polymer shows a deep-lying lowest unoccupied molecular orbital level, enabling operation of the OECT closer to 0 V vs Ag/AgCl, where fewer parasitic reactions with molecular oxygen occur. Enhancing the backbone coplanarity also leads to a lower affinity toward water uptake during cycling, resulting in improved stability during continuous electrochemical charging and ON–OFF switching relative to the NDI derivative. Furthermore, the NDTI-based polymer also demonstrates near-perfect shelf-life stability over a month-long test, exhibiting a negligible decrease in both the maximum on-current and transconductance. Our results highlight the importance of polymer backbone design for developing stable, high-performing n-type materials with mixed ionic-electronic conduction in aqueous media.