Mechanistic Insights into Growth of Surface-Mounted Metal-Organic Framework Films Resolved by Infrared (Nano-) Spectroscopy.

Control over assembly, orientation, and defect-free growth of metal-organic framework (MOF) films is crucial for their future applications. A layer-by-layer approach is considered a suitable method to synthesize highly oriented films of numerous MOF topologies, but the initial stages of the film growth remain poorly understood. Here we use a combination of infrared (IR) reflection absorption spectroscopy and atomic force microscopy (AFM)-IR imaging to investigate the assembly and growth of a surface mounted MOF (SURMOF) film, specifically HKUST-1. IR spectra of the films were measured with monolayer sensitivity and <10 nm spatial resolution. In contrast to the common knowledge of LbL SURMOF synthesis, we find evidence for the surface-hindered growth and large presence of copper acetate precursor species in the produced MOF thin-films. The growth proceeds via a solution-mediated mechanism where the presence of weakly adsorbed copper acetate species leads to the formation of crystalline agglomerates with a size that largely exceeds theoretical growth limits. We report the spectroscopic characterization of physisorbed copper acetate surface species and find evidence for the large presence of unexchanged and mixed copper-paddle-wheels. Based on these insights, we were able to optimize and automatize synthesis methods and produce (100) oriented HKUST-1 thin-films with significantly shorter synthesis times, and additionally use copper nitrate as an effective synthesis precursor.