Understanding
the mechanism of interaction between organic polymers
and dopants is of great significance to further enhance the performances
of flexible electronics. Here, the two doping mechanisms of charge
transfer complex (CTC) and integer charge transfer (ICT) are found
to coexist in p−π conjugated PTAA doped with the strong
acceptor F4-TCNQ, and their correlation is affected by the HJ-aggregate
state of the doped polymer. The growth of the J-aggregate caused by
the increase of CTC would lead to a corresponding formation of ICT.
The doping efficiency was dominated by the CTC/ICT ratio. On the basis
of the analysis of the optical, electrical, and morphological properties
of PTAA:F4-TCNQ films, we optimized the CTC/ICT ratio to achieve the
efficient hole transport layers that are used in solution-processed
flexible phosphorescent organic light-emitting diodes with p–i–n
structure. The optimal device presents a very high current efficiency
(CE) of 31.12 cd/A and a low turn-on voltage of 3.6 V.