Ultrafast Synthesis of Large-Area Conductive Metal-Organic Frameworks on Substrates for Flexible Chemiresistive Sensing.

The widespread use of electrically conductive metal-organic frameworks (EC-MOFs) in high-performance devices is limited by the lack of facile methods for synthesizing large-area thin films on the desired substrates. Herein, we propose a spin-coating interfacial self-assembly approach to synthesize high-quality centimeter-sized copper benzenehexathiol (Cu-BHT) MOFs on diverse substrates in only 5 s. The film thickness (ranging from 5 to 35 nm) and surface morphology can be precisely tuned by controlling the reaction time. The gas sensor based on the 10 nm thick Cu-BHT film exhibits a low limit of detection (0.23 ppm) and high selectivity value (>30) in sensing NH at ultralow driving voltages (0.01 V). Moreover, the Cu-BHT films retain their initial sensor performance after 1000 repetitive bending cycles at a bending radius of 3 mm. Density functional theory calculations suggest that Cu sites induced by crystal particles on the film surface can improve the sensing performance. This facile and ultrafast approach for synthesis of large-area EC-MOF films on diverse substrates with tunable thickness on a nanometer scale should facilitate application of EC-MOFs in flexible electronic device arrays.