Understanding of Fluorination Dependence on Electron Mobility and Stability of Naphthalenediimide-Based Polymer Transistors in Environment with 100% Relative Humidity

A family of copolymers (P(NDIOD-T2Fx)) based on naphthalenediimide (NDI) and 2,2′-bithiophene (T2) units with different amounts of 3,3′-difluoro-2,2′-bithiophene (T2F) decoration were synthesized, characterized, and used in n-type organic field-effect transistors (OFETs). With increasing T2F content in the backbone, we observe increased melting and crystallization transitions, blue-shifted absorptions, and deeper-lying highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels, together with improved hydrophobicity. The highest electron mobility of 4.48 × 10^-1 cm² V^-1 s^-1 was obtained for P(NDIOD-T2F0) without a T2F unit, which is attributed to the larger domain grains and crystallites, as well as a more tightly packed and oriented crystalline structure, as evidenced from the morphological study. In contrast, P(NDIOD-T2F100) with the highest T2F content has superior air stability, showing greater than 25% electron mobility retention after 30 days in wet conditions of 100% relative humidity without encapsulation. Even P(NDIOD-T2F100) is able to operate normally after 30 min of immersion in water, which is due to the synergistic contributions from the deep HOMO/LUMO levels and improved hydrophobicity. This study advances our fundamental understanding of how the morphology/crystallinity, device performance, and device stability of n-type copolymers are tuned by incorporating different concentrations of T2F in the backbone, shedding light on an important modification for air- and water-stable n-type materials for future OFET applications.