Acceptor‐Donor‐Acceptor‐Configured Delayed Fluorescence Emitters for Efficient Orange‐Red and White Devices with Low Roll‐off

Abstract Organic light‐emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) materials are promising for the realization of highly efficient emitters. However, severe efficiency roll‐off at high brightness still remains as a huge challenge for TADF‐based OLEDs. Herein, rod‐like orange‐red TADF emitters of 2BNCz‐PZ and 2BNtCz‐PZ with acceptor‐donor‐acceptor (A‐D‐A) configuration are developed by bearing dihydrophenazine donor and discoidal rigid boron, nitrogen‐contained polycyclic aromatic hydrocarbons acceptors. Both emitters exhibit hybrid long‐range/short‐range charge‐transfer excitation for small singlet‐triplet energy splitting, short delayed lifetime, and high photoluminescence quantum yield, leading to fast singlet radiation rate over 10⁷ s⁻¹ and fast reverse intersystem crossing rate over 10⁶ s⁻¹. Furthermore, a horizontal emitting dipole orientation factor over 90% is realized. The optimized orange‐red OLED based on 2BNtCz‐PZ presents a maximum external quantum efficiency (EQE) of 31.0% and a slight EQE roll‐off to 22.2% at 1 000 cd m⁻² with emission peak over 600 nm. In addition, the single‐emitting layer white OLEDs achieve a maximum EQE of 30.6% due to the use of these orange‐red dopants with intense charge‐transfer absorption band. This work reveals the potential of the rod‐like A‐D‐A configuration for constructing highly efficient orange‐red TADF emitters with low‐efficiency roll‐off.