Unexplored Exciplex Formation by Dual Excitation of Donor and Acceptor Layers Optically and Electrically

Abstract Electron donor and acceptor interactions are the fundamentals for the emergence of optoelectronic functions in most organic devices. In particular, exciplexes, which hold the possibility to utilize dark triplets, are widely investigated in organic light‐emitting diodes. However, the relatively low radiative decay rate with a low photoluminescence quantum yield poses further advanced challenges. Traditionally, it is well recognized that exciplexes are formed through a charge transfer process, i.e., direct electron transfer, by photoexciting either a donor or an acceptor component. In this study, the focus is on a long‐range exciplex system where tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA) and 2,4,6‐tris[3‐(diphenylphosphinyl)phenyl]−1,3,5‐triazine (PO‐T2T) serve as the donor and acceptor, respectively. Moreover, 1,2‐bis(triphenylsilyl) benzene (UGH2) and bis[2‐(diphenylphosphino)phenyl]ether oxide (DPEPO), having a wide energy gap and a high triplet energy level, are employed as the double insulating layer to suppressing direct electron transfer between the donor and acceptor. The indirect through‐space exciplex formation is demonstrated by the simultaneous excitation of both donor and acceptor layers optically and electrically, providing a new route for exciplex formation.