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

作者：Jinxin Liu, Shuai Fu, Yubin Fu, Yunxu Chen, Kian Tadayon, Mike Hambsch, Darius Pohl, Ye Yang, Alina Müller, Fengxiang Zhao, Stefan C. B. Mannsfeld, Lei Gao, Mischa Bonn, Xinliang Feng, Renhao Dong⧫ · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c04515 · 被引用次数：7 · 研究领域：Organic Electronics and Photovoltaics、Metal-Organic Frameworks: Synthesis and Applications、ZnO doping and properties

High Resolution Image Download MS PowerPoint Slide 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 3 ) 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 3 -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.