Direct Observation of Photoexcited Electron Dynamics in Organic Solids Exhibiting Thermally Activated Delayed Fluorescence via Time‐Resolved Photoelectron Emission Microscopy

Abstract Solid‐state films exhibiting thermally activated delayed fluorescence (TADF) can offer high internal electroluminescence (EL) quantum efficiency, even in a simplified device structure. However, the exciton dynamics in solid‐state TADF films, particularly for the unexpected exciton loss processes such as concentration quenching, have not yet been clarified. The dynamics of photoexcited electrons in the TADF process of a 2,4,5,6‐Tetra (9H‐carbazol‐9‐yl) isophthalonitrile (4CzIPN) solid film are observed via time‐resolved photoelectron emission microscopy (TR‐PEEM) and the results are compared with the conventional time‐resolved photoluminescence (TR‐PL) technique. The initial decay process of the photoexcited electrons probed via TR‐PEEM is thoroughly traced in the TR‐PL signal, while unusual long‐lived electrons are detected only through the use of TR‐PEEM. These results indicate that the excitons of 4CzIPN spontaneously dissociate into free carriers within the exciton lifetime, which seems to be a common process that contributes to the exciton loss in polar organic solids.