High-Mobility Semiconducting Two-Dimensional Conjugated Covalent Organic Frameworks with p-Type Doping

Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are emerging as a unique class of semiconducting 2D conjugated polymers for (opto)electronics and energy storage. Doping is one of the common, reliable strategies to control the charge carrier transport properties, but the precise mechanism underlying COF doping has remained largely unexplored. Here we demonstrate molecular iodine doping of a metal-phthalocyanine-based pyrazine-linked 2D c-COF. The resultant 2D c-COF ZnPc-pz-I₂ maintains its structural integrity and displays enhanced conductivity by 3 orders of magnitude, which is the result of elevated carrier concentrations. Remarkably, Hall effect measurements reveal enhanced carrier mobility reaching ∼22 cm² V^-1 s^-1 for ZnPc-pz-I₂, which represents a record value for 2D c-COFs in both the direct-current and alternating-current limits. This unique transport phenomenon with largely increased mobility upon doping can be traced to increased scattering time for free charge carriers, indicating that scattering mechanisms limiting the mobility are mitigated by doping. Our work provides a guideline on how to assess doping effects in COFs and highlights the potential of 2D c-COFs to display high conductivities and mobilities toward novel (opto)electronic devices.