Influence of Humidity on Layer-by-Layer Growth and Structure in Coordination Networks

Metal-organic frameworks (MOFs) are promising materials because of their high designability of pores and functionalities. Especially, MOF thin films and their properties have been investigated toward applications in nanodevices. Typically, MOF thin films are fabricated by using a bottom-up method such as layer-by-layer (LbL) growth in air. Because the water molecules can coordinate and be replaced with organic linkers during synthesis, humidity conditions will be expected to influence the LbL growth processes. In this study, we fabricated MOF thin films composed of Zn²⁺, tetrakis-(4-carboxyphenyl)-porphyrin (TCPP), and 4,4'-bipyridyl (bpy) at 10 and 40% relative humidity (RH) conditions. Then, we investigated the humidity effects on chemical compositions of TCPP and bpy, periodic structure, orientation, and surface morphology. At high RH, coordination replacement of water with the organic linkers becomes more competitive than that at low RH, resulting in a different TCPP/bpy composition ratio between the two RH conditions. Also, more frequent coordination replacements of water with the organic linkers at high RH led to the formation of phases other than that observed at low RH, loss of growth orientation, and rough surface. The findings clarified the importance of controlling the RH condition during LbL growth to obtain the desired coordination networks.