Liu Jinxin, Fu Shuai, Fu Yubin, Chen Yunxu, Tadayon Kian, Hambsch Mike, Pohl Darius, Yang Ye, Müller Alina, Zhao Fengxiang, Mannsfeld Stefan C B, Gao Lei, Bonn Mischa, Feng Xinliang, Dong Renhao
Max Planck Institute for Microstructure Physics, Halle (Saale) 06120, Germany.
Center for Advancing Electronics Dresden and Faculty of Chemistry and Food Chemistry, TUD Dresden University of Technology, Dresden 01067, Germany.
J Am Chem Soc. 2025 May 28;147(21):18190-18196. doi: 10.1021/jacs.5c04515. Epub 2025 May 15.
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.
作为新兴的电活性材料，可控合成确保长程π电子离域的高度有序二维（2D）共轭配位聚合物（c-CP）薄膜对于推动高性能（光）电子学至关重要。在此，我们首次通过在氨（NH₃）辅助下的化学气相沉积，利用其对配体的去质子化作用和作为额外配位物种的竞争作用，在惰性衬底上实现了高度结晶的2D c-CP薄膜的生长。所得的Fe-HHB（HHB = 六羟基苯）薄膜展现出大面积均匀性，晶粒尺寸增大了2个数量级，这转化为电导率（从0.002提升至3 S/cm）、电荷迁移率、弹性模量和硬度的显著提高。为验证这种NH₃辅助合成的通用性，还制备了对比性的Cu-HHB和Cu-BHT（BHT = 六硫醇苯）2D c-CP薄膜，其电导率分别从51显著提高至113以及从595提高至905 S/cm。大大提高的结晶度，再加上所开发的合成策略与当前器件集成技术的高度兼容性，为开发基于c-CP的电子产品铺平了道路。
