Porphyrin-Based MOF Thin Film on Transparent Conducting Oxide: Investigation of Growth, Porosity and Photoelectrochemical Properties

Synthesizing metal-organic frameworks (MOFs) composites with a controlled morphology is an important requirement to access materials of desired patterning and composition. Since the last decade, MOF growth from sacrificial metal oxide layer is increasingly developed as it represents an efficient pathway to functionalize a large number of substrates. In this study, porphyrin-based Al-PMOF thin films were grown on conductive transparent oxide substrates from sacrificial layers of ALD-deposited alumina oxide. The control of the solvent composition and the number of atomic layer deposition (ALD) cycles allow us to tune the crystallinity, morphology and thickness of the produced thin films. Photophysical studies evidence that Al-PMOF thin films present light absorption and emission properties governed by the porphyrinic linker, without any quenching upon increasing the film thickness. Al-PMOF thin films obtained through this methodology present a remarkably high optical quality both in terms of transparency and coverage. The porosity of the samples is demonstrated by ellipsometry and used for Zn(II) insertion inside the MOF thin film. The multifunctional transparent, porous and luminescent thin film grown on fluorine-doped tin oxide (FTO) is used as an electrode capable of photoinduced charge separation upon simulated sunlight irradiation.