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.