Direct Photopatterning of Zeolitic Imidazolate Frameworks via Photoinduced Fluorination

Abstract

Precise and effective patterning strategies are essential for integrating metal–organic frameworks (MOFs) into microelectronics, photonics, sensors, and other solid-state devices. Direct lithography of MOFs with light and other irradiation sources has emerged as a promising patterning strategy. However, existing direct lithography methods often rely on the irradiation-induced amorphization of the MOFs structures and the breaking of strong covalent bonds in their organic linkers. High-energy sources (such as X-rays or electron beams) and large irradiation doses – conditions unfavorable for scalable patterning – are thus required. Here, we report a photoinduced fluorination chemistry for patterning various zeolitic imidazolate frameworks (ZIFs) under mild UV irradiation. Using UV doses as low as 10 mJ cm⁻², light-sensitive fluorine-containing molecules covalently bond to ZIFs and enhance their stability in water. This creates a water-stability contrast between ZIFs in exposed and unexposed regions, enabling scalable direct photolithography of ZIFs with high resolution (2 μm) on 4-inch wafers and flexible substrates. The patterned ZIFs preserve their original crystallinity and porous properties while gaining increased hydrophobicity. This allows for the demonstration of a water-responsive fluorescent MOFs array with implications in sensing and multicolor information encryption.