Asymmetric Additive‐Assisted Organic Solar Cells with Much Better Energy Harvesting and Wireless Communication Performance

Abstract Organic solar cells (OSCs), exhibiting better sensitivity to different light intensities and higher power conversion efficiencies (PCEs) under indoor illumination, have great potential to be simultaneously used for solar energy harvesting and optical communication. However, the poor intrinsic molecular stacking and phase separation in active layers significantly hinder the charge transport and extraction in OSCs for achieving this aim. Here, an effective heterohalogen‐substitution asymmetric additive strategy is proposed to fine‐tune the non‐covalent interaction with nonfullerene molecules and optimize the morphology of active layer, which greatly boosts both the OSC photovoltaic performance with the PCEs of up to 18.30% and 29.52% under AM 1.5G and indoor light illumination respectively, and the ‒3 dB communication bandwidths of 4.11, 3.14, and 3.04 MHz at red, green, and blue (RGB) wavelengths respectively. Of particular note, combining the wavelength division multiplexing and adaptive bit‐loading technologies, the visible light communication system comprised of the RGB light sources and additive‐treated OSCs delivers more remarkable data throughput of 302.7 Mb s −1 and higher harvesting power of 7.38 mW simultaneously, presenting an excellent self‐powered capability for enhanced endurance. This work demonstrates that high‐performance OSCs with excellent energy harvesting and wireless communication capacity can be perfectly achieved by a heterohalogen‐substitution asymmetric additive strategy.