Direct Observation of Radical States and the Correlation with Performance Degradation in Organic Light-Emitting Diodes During Device Operation

Microscopic characterization of radical states in organic light‐emitting diodes (OLEDs) during device operation is useful for elucidating the degradation mechanism because the radical formation has been considered as non‐radiative recombination centers. Electron spin resonance (ESR) spectroscopy is suitable for such characterization because it can directly observe radicals in OLEDs. In this work, the detailed ESR investigation into the radical states in OLEDs during device operation is firstly reported using a typical light‐emitting Alq3‐based OLEDs. The simultaneous measurements of the ESR signal and the luminance of the same OLED are performed to study the direct correlation between the radical states and the performance degradation. These characteristics show that the luminance monotonically decreases and an ESR signal concomitantly increases as the duration of the device operation increases after operating the OLED. Using the analysis of density functional theory (DFT) calculation, the origin of the newly emerged ESR signal is ascribed to the cationic species due to decomposed Alq3 molecules. The elucidation of the radical species formed in OLEDs during device operation has been demonstrated at a molecular level for the first time. This ESR analysis would provide useful knowledge for understanding the degradation mechanism in the OLEDs at the molecular level