Ultralow‐Dose Direct Photopatterning of Metal–Organic Frameworks for Scalable Device Integration

Abstract

The integration of metal–organic frameworks (MOFs) into microelectronic and optoelectronic devices requires patterning strategies that combine high sensitivity, structural preservation, and compatibility with scalable fabrication. Direct optical patterning offers a photoresist‐free route to achieve this, yet existing approaches are limited by inefficient photochemical processes that require high irradiation doses, thereby constraining throughput and risking material degradation. Here, we report an ultralow‐dose direct patterning for MOFs that enables high‐fidelity feature definition at exposure doses down to 0.6 mJ cm−2. The approach relies on a molecularly engineered thiol–ene click‐induced crosslinking mechanism that generates strong solubility contrast under light irradiation, allowing negative‐tone pattern formation while preserving the intrinsic crystallinity and porosity of MOFs. By establishing a structure‐excitation‐reactivity relationship, we identify key molecular parameters governing photopatterning sensitivity, enabling rational tuning of the process. The resulting platform supports large‐area, multipixel patterning on rigid and flexible substrates and enables direct integration of patterned MOF films into diffraction grating‐based photonic devices. This study introduces a molecularly guided photochemical design principle for low‐dose photopatterning, providing a platform for the scalable integration of MOFs into next‐generation electronic and photonic devices.