Electrical Conductivity Boost: In Situ Polypyrrole Polymerization in Monolithically Integrated Surface‐Supported Metal‐Organic Framework Templates

Abstract Recent progress in synthesizing and integrating surface‐supported metal‐organic frameworks (SURMOFs) has highlighted their potential in developing hybrid electronic devices with exceptional mechanical flexibility, film processability, and cost‐effectiveness. However, the low electrical conductivity of SURMOFs has limited their use in devices. To address this, researchers have utilized the porosity of SURMOFs to enhance electrical conductivity by incorporating conductive materials. This study introduces a method to improve the electrical conductivity of HKUST‐1 templates by in situ polymerization of conductive polypyrrole (PPy) chains within the SURMOF pores (named as PPy@HKUST‐1). Nanomembrane‐origami technology is employed for integration, allowing a rolled‐up metallic nanomembrane to contact the HKUST‐1 films without causing damage. After a 24 h loading period, the electrical conductivity at room temperature reaches approximately 5.10⁻⁶ S m⁻¹. The nanomembrane‐based contact enables reliable electrical characterization even at low temperatures. Key parameters of PPy@HKUST‐1 films, such as trap barrier height, dielectric constant, and tunneling barrier height, are determined using established conduction mechanisms. These findings represent a significant advancement in real‐time control of SURMOF conductivity, opening pathways for innovative electronic‐optoelectronic device development. This study demonstrates the potential of SURMOFs to revolutionize hybrid electronic devices by enhancing electrical conductivity through intelligent integration strategies.