Layer‐by‐Layer Growth of Preferred‐Oriented MOF Thin Film on Nanowire Array for High‐Performance Chemiresistive Sensing

High‐quality MOF thin films with high orientation and controlled thickness are extremely desired for applications. However, they have been only successfully fabricated on flat substrates. Those MOF 2D thin films are limited by low exposed area and slow mass transport. To overcome these issues, MOF 3D thin films with good crystallinity, preferred orientation, and precisely controllable thickness in nanoscale were successfully prepared in a controllable layer‐by‐layer manner on nanowire array substrate for the first time. The as‐prepared Cu‐HHTP 3D thin film is superior to corresponding 2D thin films and showed one of the highest sensitivity, lowest LOD, and fastest response among all reported chemiresistive NH3 sensing materials at RT. This work provides a feasible approach to grow preferred‐oriented 3D MOF thin film, offering new perspectives for constructing MOF‐based heterostructures for advanced applications. Semiconducting MOF 3D thin films with good crystallinity, preferred orientation, as well as precisely controllable thickness in nanoscale were successfully prepared in a layer‐by‐layer manner on a nanowire array substrate. Compared to 2D thin films, the Cu‐HHTP 3D thin film shows one of the highest sensitivity, lowest LOD and fastest response speed among all reported chemiresistive NH3 sensing materials at RT.