In this work we report the optimisation of the solution processable TADF exciplex emitter in OLED devices formed by the small molecules 9-[2,8]-9-carbazole-[dibenzothiophene-S,S-dioxide]-carbazole (DCz-DBTO2) and 4,4′-cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine] (TAPC). This exciplex, previously reported by Jankus et al. , has gave vacuum deposited devices having respectively current efficiency, power efficiency and EQE of 32.3 cd/A, 26.7 lm/W and 10.3 % obtained for with DCz-DBTO2:TAPC wt% ratio of 30:70. In this work we optimised the thickness and ratio of the exciplex layer using two different solvents, chlorobenzene and chloroform. The best results were achieved when the two solvents were mixed, adding 5 vol% of chlorobenzene to chloroform. With this solvent mixture comparable results to evaporated devices were achieved, 27.5 ± 3.5 cd/A, 16.5 ± 2.0 lm/W and EQE of 8.9 ± 0.6 % at the same DCz-DBTO2:TAPC wt% ratio of 30:70, demonstrating the suitability of small molecule TADF exciplexes as solution processable emissive layer for OLEDs.
We present a combined detailed spectroscopic and quantum chemical study on the bipolar host materials BPTRZ and MBPTRZ in solution and in neat film. In the two compounds, the hole transporting carbazole is separated from the electron transporting triazine moiety by a fully aromatic but non-conjugated meta-linked biphenyl unit. The two materials differ by an additional steric twist at the biphenyl in MBPTRZ, which is achieved by methyl-substitution in 2- and 2′-position of the biphenyl. We find that while the twist shifts the triplet state in MBPTRZ to higher energies (3.0 eV in solution) compared to BPTRZ (2.8 eV in solution), this also localizes electron density on the carbazole moiety, leading to excimer formation in neat films.
Two new donor (D)–acceptor (A) type molecules, PXZ-DBTO2 and PXZ-Ph-DBTO2, configured with phenoxazine donor and dibenzothiophene-S,S-dioxide acceptor are reported. PXZ-Ph-DBTO2, with a phenyl group introduced at the ortho position of PXZ, was used to probe the effects of the congested aryl substitution on the molecular conformation and electronic coupling toward the acceptor core, as well as the thermally activated delayed fluorescence behavior. The highly twisted donor–acceptor configurations of these two molecules were confirmed by X-ray analysis. Different D–A conformations stemmed from the steric interactions between the phenyl group and acceptor core, which leads the nitrogen lone pair electrons of the PXZ-Ph-DBTO2 donor to conjugate across the D–A bridge, whereas in PXZ-DBTO2 the lone pairs remain localized on the donor and strongly mix with the donor π electrons. However, both PXZ-Ph-DBTO2 and PXZ-DBTO2 have the same energy splitting between the charge-transfer states and local donor triplet states, ΔEST, close to 70 meV. PXZ-DBTO2 exhibits a far more efficient thermally activated delayed fluorescence due to nearly 2 orders of magnitude faster reverse intersystem crossing rate as compared to that of PXZ-Ph-DBTO2. Detailed photophysical analysis of both molecules indicates that the presence of the phenyl group on the donor disrupts the π–π/n−π orbital mixing across the N–C bridge that plays a fundamental role in the excited state dynamics and vibronic coupling governing the reverse intersystem crossing rate and thus the efficiency of thermally activated delayed fluorescence. Devices employing PXZ-DBTO2 as an emitting dopant gave an external quantum efficiency (EQE) of 16.7% (42 cd m–2) and a limited efficiency roll-off (15.7% at 1000 cd m–2), whereas the device based on PXZ-Ph-DBTO2 produced a maximum EQE up to 20.6%, but with a significant efficiency roll-off (8.8% at 1000 cd m–2) ascribed to the much faster reverse intersystem crossing rate of PXZ-DBTO2.