Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Spin splitting in a polarized quasi-two-dimensional exciton gas

We have observed a large spin splitting between "spin" +1 and -1 heavy-hole excitons, having unbalanced populations, in undoped GaAs/AlAs quantum wells in the absence of any external magnetic field. Time-resolved photoluminescence spectroscopy, under excitation with circularly polarized light, reveals that, for high excitonic density and short times after the pulsed excitation, the emission from majority excitons lies above that of minority ones. The amount of the splitting, which can be as large as 50% of the binding energy, increases with excitonic density and presents a time evolution closely connected with the degree of polarization of the luminescence. Our results are interpreted on the light of a recently developed model, which shows that, while intraexcitonic exchange interaction is responsible for the spin relaxation processes, exciton-exciton interaction produces a breaking of the spin degeneracy in two-dimensional semiconductors.