Highly Crystalline Rubrene Light‐Emitting Diodes with Epitaxial Growth

Conventional organic optoelectronic devices suffer from low carrier mobility limited by the static and dynamic disorder. Organic crystals with long‐range order can circumvent the effects of disorder and significantly improve the charge transport. While highly ordered organic crystals offer the desirable electronic coupling strength and charge transport, their integration into large‐area optoelectronic devices remains a challenge. Here, monolithic integrated triclinic crystal rubrene light‐emitting diodes (LEDs) are presented using epitaxial growth with functional additives being engineered into the films. Superior charge transport, excellent operational and long‐term stability in these light‐emitting devices are demonstrated. By comparing two rubrene‐based LEDs, one made from amorphous and one from crystalline rubrene layers, their exciton dynamics are estimated using comprehensive transient electroluminescence simulation. The crystalline LEDs show high triplet‐triplet annihilation (TTA) rate constant similar to TTA rate constant of triclinic single crystals determined by optical spectroscopy. At the same time, the crystalline phase enhances drastically the singlet‐fission and bimolecular annihilation rates, which reduces the overall performance of the LED compared to its amorphous counterpart. Finally, an outlook on the potential applications of rubrene and/or its derivatives crystalline films are provided for enhancing the performance of organic and hybrid optoelectronic devices. In this study, monolithically integrated highly crystalline triclinic rubrene light‐emitting diodes are presented using epitaxial growth with functional additives being engineered into the films. The devices show excellent charge transport, operational, and long‐term stability. This study paves the way for advancing the performance of organic and hybrid optoelectonic devices with rubrene and/or its derivatives crystalline films.