Effects of Planarization of the Triphenylamine Unit on the Electronic and Transport Properties of Triarylamine–Fluorene Copolymers in Both Doped and Undoped Forms

Triarylamine-alt-fluorene (TAF) copolymers are widely used for hole injection and transport in organic electronics. Despite suggestions to planarize the triphenylamine moiety, little research has been conducted. Here, we report a comprehensive investigation of the effects of planarization on the electronic and transport properties of a model TAF polymer semiconductor core. We compared the conventional twisted-propeller N-4-methoxyphenyl-N,N-diphenylamine-4′,4″-diyl (TA) unit and its planarized bridged analogue (bTA) where adjacent o,o′-positions are linked by 1,1-dimethylmethylene. We studied both polyelectrolyte and non-polyelectrolyte forms of this core in both doped and undoped states. We found that planarization leads to an unprecedented trap-free transport of holes, and a pronounced enhancement of their mobility in the undoped state though less so in the doped state. Planarization also induces a slight reduction in the ionization energy of the undoped polymer, consequently lowering the work function of the doped polymer. This is accompanied by small spectral shifts: a red shift in the first absorption band of the undoped polymer and a blue shift in the first absorption band of the polaron. Furthermore, this study unveils new fundamental features of TAF polymers: (i) Doping induces the formation of three polaron bands within the subgap. (ii) Absorption of both neutral and polaron segments exhibit a linear intensity relationship with doping level. (iii) Electrical conductivity reaches a maximum at the half-doped state, varying as σ ∼ (x (1 – x))3 for 0.1 ≲ x ≲ 0.9, where x is the doping level. Finally, we demonstrate the successful integration of these self-compensated hole-doped TAF polymers as efficient hole injection layers in organic semiconductor diodes.