Cyano-Substituted Head-to-Head Polythiophenes: Enabling High-Performance n-Type Organic Thin-Film Transistors

Polythiophenes, built on the electron-rich thiophene unit, typically possess high-lying energy levels of the lowest unoccupied molecular orbitals (LUMOs) and show hole-transporting properties. In this study, we develop a series of n-type polythiophenes, P1-P3, based on head-to-head-linked 3,3'-dialkoxy-4,4'-dicyano-2,2'-bithiophene (BTCNOR) with distinct side chains. The BTCNOR unit shows not only highly planar backbone conformation enabled by the intramolecular noncovalent sulfur-oxygen interaction but also significantly suppressed LUMO level attributed to the cyano-substitution. Hence, all BTCNOR-based polymer semiconductors exhibit low-lying LUMO levels, which are ∼1.0 eV lower than that of regioregular poly(3-hexylthiophene) (rr-P3HT), a benchmark p-type polymer semiconductor. Consequently, all of the three polymers can enable unipolar n-type transport characteristics in organic thin-film transistors (OTFTs) with low off-currents ( I_offs) of 10^-10-10^-11 A and large current on/off ratios ( I_on/ I_offs) at the level of 10⁶. Among them, polymer P2 with a 2-ethylhexyl side chain offers the highest film ordering, leading to the best device performance with an excellent electron mobility (μ_e) of 0.31 cm² V^-1 s^-1 in off-center spin-cast OTFTs. To the best of our knowledge, this is the first report of n-type polythiophenes with electron mobility comparable to the hole mobility of the benchmark p-type rr-P3HT and approaching the electron mobility of the most-studied n-type polymer, poly(naphthalene diimide- alt-bithiophene) (i.e., N2200). The change of charge carrier polarity from p-type (rr-P3HT) to n-type (P2) with comparable mobility demonstrates the obvious effectiveness of our structural modification. Adoption of n-hexadecyl (P1) and 2-butyloctyl (P3) side chains leads to reduced film ordering and results in 1-2 orders of magnitude lower μ_es, showing the critical role of side chains in optimizing device performance. This study demonstrates the unique structural features of head-to-head linkage containing BTCNOR for constructing high-performance n-type polymers, i.e., the alkoxy chain for backbone conformation locking and providing polymer solubility as well as the strong electron-withdrawing cyano group for lowering LUMO levels and enabling n-type performance. The design strategy of BTCNOR-based polymers provides useful guidelines for developing n-type polythiophenes.