Improved optical quality of heteroepitaxially grown metal-organic framework thin films by modulating the crystal...

Fabricating high-quality thin films of metal-organic frameworks (MOFs) is important for integrating MOFs in various applications. Specifically, optical/electrical devices require MOF thin films that are crystallographically oriented, with closely packed crystals and smooth surfaces. Although the heteroepitaxial growth approach of MOFs on metal hydroxides has been demonstrated to control the orientation of the three crystallographic axes, the fabrication of MOF thin films with both three-dimensional crystallographic orientation and smooth surfaces remains a challenge. In this study, we report the fabrication of high-quality thin films of MOFs with closely packed MOF crystals, smooth surfaces, optical transparency, and crystal alignment by modulating the crystal growth of MOFs using the heteroepitaxial growth approach. High-quality thin films of Cu-paddlewheel-based pillar-layered MOFs are fabricated on oriented Cu(OH)₂ thin films via epitaxial growth using acetate ions as modulators to control the crystal morphology. Increasing the modulator concentration results in a uniform crystal shape with a relatively long one-dimensional pore direction and uniform heterogeneous nucleation over the entire film. The MOF thin films fabricated using the modulator exhibit high optical transparency. High-quality MOF thin films with dense and flat surfaces will pave the way for integrating MOFs into sophisticated optical and electrical devices.