Fabrication of 3D Oriented MOF Micropatterns with Anisotropic Fluorescent Properties

Micropatterning crystalline materials with oriented pores is necessary for the fabrication of devices with anisotropic properties. Crystalline and porous metal–organic frameworks (MOFs) are ideal materials as their chemical and structural mutability enables precise tuning of functional properties for applications ranging from microelectronics to photonics. Herein, a patternable oriented MOF film is designed: by using a photomask under X‐ray exposure, the MOF film decomposes in the irradiated areas, remaining intact in the unexposed regions. The MOF film acts simultaneously as a resist and as functional porous material. While the heteroepitaxial growth from aligned Cu(OH)2 nanobelts is used to deposit oriented MOF films, the sensitivity to radiation is achieved by integrating a brominated dicarboxylate ligand (Br2BDC) into a copper‐based MOF Cu2L2DABCO (DABCO = 1,4‐diazabicyclo[2.2.2]octane; L = BDC/Br2BDC). The lithographed samples act as diffraction gratings upon irradiation with a laser, thus confirming the quality of the extended MOF micropattern. Furthermore, the oriented MOF patterns are functionalized with fluorescent dyes. As a result, by rotating the polarization angle of the laser excitation, the alignment of the dye in the MOF is demonstrated. By controlling the functional response to light, this MOF patterning protocol can be used for the microfabrication of optical components for photonic devices. Deep X‐ray lithography is used for the fabrication of 3D‐oriented metal–organic framework (MOF) micropatterns. MOF films with X‐ray sensitivity are obtained by using a mixed‐linker strategy; the orientation of MOF crystals is achieved via heteroepitaxial growth. Fluorescent guest molecules are immobilized and aligned within spatially controlled and oriented MOF crystals. Such MOF micropatterns show anisotropic optical responses suitable for photonic applications.