Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing

Abstract

Fabrication of metal-organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal-organic frameworks (SURMOFs) has several requirements: Mild conditions, low temperatures, day-long reaction times, and non-aggressive solvents. We herein present a fast method for the preparation of the first MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50-2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in-situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. SEM data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a PMMA layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as Fabry-Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the UV-Vis regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds, led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

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“…For example, high-quality, optically transparent HKUST-1 (Hong Kong University of Science and Technology 1) thin films can currently be grown only in an inert, humidity-controlled atmosphere. [14] Some of us demonstrated recently that MIL-68(In) (Matériaux de l'Institut Lavoisier) thin films can indeed be made within minutes, [15] but MIL-68(In) currently remains a unique example in those terms.…”