Modulation of n-Type Units in Bipolar Host Materials toward High-Performance Phosphorescent OLEDs

9′-Pyridinyl-9′ H -9,3′:6′,9″-tercarbazole (PyCz) is a bipolar host material in phosphorescent organic light-emitting diodes (PhOLEDs). A second n-type unit, either pyridine or diphenylphosphine dioxide (DPPO), is introduced onto the pyridine ring of PyCz at para- or metasite to design and prepare four novel “dual n-type unit bipolar host” materials m -BPyCz, p -BPyCz, m -POPyCz, and p -POPyCz. The incorporation of the second n-type unit pulls down the lowest unoccupied molecular orbitals and facilitates electron injection and transportation, resulting in better charge-balancing ability. As a result, these dual n-type unit bipolar hosts exhibit higher efficiencies and slower efficiency roll-off in their blue and green PhOLEDs. In particular, m -POPyCz containing a bulky DPPO as the second n-type unit with a metalinking possesses the best charge-balancing state and generates a maximum external quantum efficiency (η ext ) of 27.0% (corresponding to a current efficiency of 51.9 cd A –1 and a power efficiency of 46.5 lm W –1 ) in its sky-blue device and still remained at a high η ext of 23.6% even at the practical brightness of 1000 cd m –2 . These results clearly demonstrate that the “dual n-type unit bipolar hosts” with an optimized substitution position and steric effect is a new and effective type of host materials for high-performance OLEDs.