Morphological Effects on the Performance of Broadband Organic Photomultiplication Photodetectors Containing Selenium Substituted Non‐Fullerene Acceptors

Abstract Organic photodetectors (OPDs) with spectral response extending from ultraviolet to near‐infrared domains are of great interest for many applications. Morphological impact on the performance of photomultiplication (PM)‐type OPDs, however, is still rarely investigated so far. Herein, a non‐fullerene acceptor, Y6‐Se‐HD, is synthesized, in which heavier selenium atoms substitute the sulfur atoms in the core of Y6, and used for fabricating PM‐OPDs. The resulting devices exhibit remarkable PM effects in a very broadband spectral range covering from 320 to 1090 nm. A maximum EQE value of ≈6500% at 860 nm is achieved at a low bias of −1.0 V. As compared with the device prepared with Y6 molecules, the Y6‐Se‐HD OPDs exhibited much enhanced performance. From the morphological analysis, we infer that Y6‐Se‐HD almost covers the entire active layer and avoids the direct contact of the hole‐trapping donor polymers with the Ag electrode, thereby resulting in stronger charge trapping and preventing possible charge recombination and/or quenching. Furthermore, finer phase separation between the donor and acceptor molecules also facilitates hole trapping and strengthens the PM effects. This research highlights the importance of morphological effects on the PM‐OPDs and demonstrates one approach for controlling the device morphology.