Bottom‐Up Fabrication of Semiconductive Metal–Organic Framework Ultrathin Films

Abstract Though generally considered insulating, recent progress on the discovery of conductive porous metal–organic frameworks (MOFs) offers new opportunities for their integration as electroactive components in electronic devices. Compared to classical semiconductors, these metal–organic hybrids combine the crystallinity of inorganic materials with easier chemical functionalization and processability. Still, future development depends on the ability to produce high‐quality films with fine control over their orientation, crystallinity, homogeneity, and thickness. Here self‐assembled monolayer substrate modification and bottom‐up techniques are used to produce preferentially oriented, ultrathin, conductive films of Cu‐CAT‐1. The approach permits to fabricate and study the electrical response of MOF‐based devices incorporating the thinnest MOF film reported thus far (10 nm thick).