Ultrafast In Situ 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 in situ 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 NH3 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 Cu2c sites induced by crystal particles on the film surface can improve the sensing performance. This facile and ultrafast approach for in situ 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.