Ammonia-Assisted Chemical Vapor Deposition Growth of Two-Dimensional Conjugated Coordination Polymer Thin Films.

As emerging electroactive materials, the controlled synthesis of highly ordered two-dimensional (2D) conjugated coordination polymer (c-CP) films ensuring the long-range π-electron delocalization is essential for advancing high-performance (opto-)electronics. Here, we demonstrate the growth of highly crystalline 2D c-CP thin films on inert substrates by chemical vapor deposition with the assistance of ammonia (NH) for the first time, leveraging its deprotonation effect on ligands and competing effect as additional coordinating species. The resulting Fe-HHB (HHB = hexahydroxybenzene) films exhibit large-area uniformity and a 2 order-of-magnitude increase in crystal grain size, which translates into significant improvements in electrical conductivity (from 0.002 to 3 S/cm), charge mobility, elastic modulus, and hardness. To verify the generality of this NH-assisted synthesis, the contrast Cu-HHB and Cu-BHT (BHT = hexathiolbenzene) 2D c-CP thin films are also prepared and deliver significantly improved electrical conductivities from 51 to 113 and from 595 to 905 S/cm, respectively. The greatly improved crystallinity, combined with the high compatibility of the developed synthetic strategy with current device integration technologies, paves the way for developing c-CP-based electronics.