Gas‐Phase Fluorination of Hexagonal Boron Nitride

Abstract Hexagonal boron nitride ( h BN) has received much attention in recent years as a 2D dielectric material with potential applications ranging from catalysts to electronics. h BN is a stable covalent compound with a planar hexagonal lattice and is relatively unreactive to most chemical environments, making the chemical functionalization of h BN challenging. Here, a simple, scalable strategy to fluorinate h BN using a direct gas‐phase fluorination technique is reported. The nature of fluorine bonding to the h BN lattice and their chemical coordination are described based on various characterization studies and theoretical models. The fluorine functionalized h BN shows a bandgap reduction and displays a semiconducting behavior due to the fluorination process. Additionally, the fluorinated h BN shows significant improvement in its thermal and friction properties, which could be substantial in applications such as lubricants and thermal fluids. Theory and simulations reveal that the enhanced friction properties of fluorinated h BN result from reduced inter‐planar interaction energy by electrostatic repulsion of intercalated fluorine atoms between h BN layers without significant disruption of the in‐plane lattice. This technique paves the way for the fluorination of several other 2D structures for various applications such as magnetism and functional nanoscale electronic devices.