We fabricated well-ordered, crystalline mono- and multilayers of disk-shaped thermally activated delayed fluorescence (TADF) molecules such as 4CzIPN, 2CzPN, and 5CzBN. The slow deposition of these molecules on flat substrates such as Ag(111) at room temperature resulted in the formation of well-ordered and homogeneous monolayers. Moreover, the multilayer of the 4CzIPN was also found to be well-ordered and flat when deposited on highly oriented pyrolytic graphite (HOPG). The electronic states of the crystalline monolayer and multilayer of 4CzIPN were found to be nearly the same, suggesting that the electronic states of both layers are not altered significantly by adsorption on substrates. Indeed, we also confirmed the delayed fluorescence from the crystalline multilayer of 4CzIPN on the HOPG substrate even in an ambient condition. These results show promising applications of crystalline films of disk-shaped TADF-molecules such as 4CzIPN for organic light-emitting diodes devices with high outcoupling efficiency.
The photophysical properties of six types of carbazole benzonitrile (CzBN) derivatives are investigated in different solvents to examine the thermally activated delayed fluorescence (TADF) activation via reducing the energy gap between the singlet charge-transfer and triplet locally excited states, ΔEST(LE). Relative to the ΔEST(LE) values for the CzBN derivatives in the low polarity solvent toluene (ϵ∼2), a reduction of ΔEST(LE) for the CzBN derivatives in the polar solvent acetonitrile (ϵ∼37) was confirmed while maintaining fairly constant ΔEST values. Notably, TADF activation was observed in acetonitrile for some CzBN derivatives that are TADF inactive in toluene. A numerical analysis of various rate constants revealed the cause of TADF activation as an increase in the reverse intersystem crossing rate and a suppression of the non-radiative decay rate of the triplet states. The positive effect of ΔEST(LE) was limited, however, as an excessive decrease in ΔEST(LE) facilitates the nonradiative deactivation of the triplet states, leading to a loss of the TADF efficiency. This paper shows that ΔEST(LE) provides a measure of TADF activation and that appropriate regulation of ΔEST(LE) is required to achieve high TADF efficiency.
We hereby report the results of our direct investigation into the excited-state dynamics of thermally activated delayed fluorescence (TADF) molecules in solution using pump-probe transient absorption spectroscopy (TAS). We found that the charge-transfer (CT) state commonly stated for TADF molecules encompasses two forms: localized and delocalized CT states. A highly efficient TADF molecule, 4CzIPN [Uoyama et al., Nature, 492, 234-238 (2012)], showed both the localized and delocalized CT states, while an inefficient TADF molecule, 2CzPN, exhibited only a localized CT state. By analyzing the time profile of triplet species observed in TAS, we propose that the reverse intersystem crossing (RISC) of 4CzIPN occurs via a mutual interaction in multiple energy levels of localized neutral and CT states, and delocalized CT states.