Novel integrated reference-counter electrode for electrochemical measurements of HOMO and LUMO levels in small-molecule thin-film semiconductors for OLEDs

Organic light-emitting diodes (OLEDs) are a prominent display technology, yet the accurate characterization of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels in their constituent materials remains challenging. This study introduces a novel integrated reference-counter electrode (IRCE) assembly, leveraging a gel polymer electrolyte with an embedded silver quasi-reference electrode, facilitating the electrochemical measurement of HOMO and LUMO levels in small molecular thin-film semiconductors. Calibration of the IRCE against ferrocene enables the establishment of an absolute energy scale. Comparative stability tests against a standard Ag/AgNO 3 reference electrode confirm the IRCE's reliability. Electrochemical characterization using cyclic voltammetry was performed on prototypical OLED materials, including NPB, TCTA, PO-T2T neat films, and an NPB:PO-T2T exciplex film. While NPB and PO-T2T exhibited stable voltammograms, TCTA showed signs of electropolymerization. Additionally, the HOMO level of the NPB:PO-T2T exciplex was slightly shifted compared to that of NPB, suggesting interactions within the exciplex. The results demonstrated the IRCE's capability to accurately determine frontier energy levels in thin films, paving the way for better device modeling and a better understanding of underlying electronic processes in organic semiconductors. 1. Introduced a novel electrolyte/reference electrode assembly, referred to as IRCE. 2. Calibrated IRCE against ferrocene for an absolute energy scale. 3. IRCE shows stability similar to Ag/AgNO 3 reference electrode. 4. IRCE enables electrochemical characterization of small-molecule thin film organic semiconductors. 5. Demonstrated electrochemical characterization of HOMO/LUMO levels in OLED materials.