Electron Transfer Enhanced by a Minimal Energetic Driving Force at the Organic‐Semiconductor Interface

Abstract The energetic driving force for electron transfer must be minimized to realize efficient optoelectronic devices including organic light‐emitting diodes (OLEDs) and organic photovoltaics (OPVs). Exploring the dynamics of a charge‐transfer (CT) state at an interface leads to a comprehension of the relationship between energetics, electron‐transfer efficiency, and device performance. Here, we investigate the electron transfer from the CT state to the triplet excited state (T 1 ) in upconversion OLEDs with 45 material combinations. By analyzing the CT emission and the singlet excited‐state emission from triplet–triplet annihilation via the dark T 1 , their energetics and electron‐transfer efficiencies are extracted. We demonstrate that the CT→T 1 electron transfer is enhanced by the stronger CT interaction and a minimal energetic driving force (<0.1 eV), which is explained using the Marcus theory with a small reorganization energy of <0.1 eV. Through our analysis, a novel donor–acceptor combination for the OLED is developed and shows an efficient blue emission with an extremely low turn‐on voltage of 1.57 V. This work provides a solution to control interfacial CT states for efficient optoelectronic devices without energy loss.