Automated Spin-Assisted Layer-by-Layer Epitaxy Produces Highly Oriented Mixed-Linker MOF Thin Films

Abstract

Control over crystallographic orientation in metal-organic framework (MOF) thin films is crucial for exploiting their anisotropic properties in sensing, catalysis, and separation. Achieving reproducible, highly oriented films remains challenging, especially for mixed-linker, pillared-layered frameworks. Here we present an automated, spin-assisted layer-by-layer liquid-phase epitaxy (LbL-LPE) strategy that enables rapid, ambient-condition fabrication of highly oriented, mixed-linker MOF thin films, demonstrated for Zn2BDC2DABCO (BDC = terephthalate, DABCO = 1,4-diazabicyclo[2.2.2]octane). Correlative process monitoring by grazing-incidence wide-angle X-ray scattering (GIWAXS), grazing-angle infrared (GI-IR) and UV-Vis spectroscopy, contact-angle measurements, scanning electron microscopy (SEM), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) ensure formation of uniform films with exceptional out-of-plane (001) orientation (degree of orientation >85%, Hermans parameter ~0.95) and excellent reproducibility. This strategy enables highly reproducible, high-throughput fabrication of orientation-controlled MOF thin films, providing a generalizable alternative to conventional LbL approaches. By enabling reproducible and entirely automated fabrication of highly anisotropic architectures, this work establishes a platform for integrating oriented MOFs into next-generation optoelectronic, sensing, and membrane devices where directional transport and ordered pore alignment are essential.