Cocrystal Engineering: Toward Solution-Processed Near-Infrared 2D Organic Cocrystals for Broadband Photodetection

Large-area 2D cocrystals with strong near-infrared (NIR) absorption have been designed and prepared. Driven by the intermolecular charge-transfer (CT) interactions, zinc tetraphenylporphyrin (donor) and C₆₀ (acceptor) self-assemble into a NIR cocrystal with absorption wavelength up to 1080 nm. By tailoring the growth solvents and processes, the cocrystal morphologies can be tuned from 1D nanowires, 2D nanosheets to large-area 2D cocrystal films with length reaching several millimeters. Owing to the highly ordered donor-acceptor arrangement, the CT absorption in the 2D cocrystals is enhanced and is comparable to singlet absorption. The uniform 2D cocrystals, with enhanced CT absorption in the NIR region, displays a high responsivity of 2424 mA W^-1 to NIR light and a fast response time of 0.6 s. The excellent device performance is attributed to the generation of long-lived free charge carriers as revealed by transient absorption spectroscopy and optimization of device configuration.