Growth of Fe‐BDC Metal‐Organic Frameworks onto Functionalized Si (111) Surfaces

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Abstract
The realization of metal‐organic framework (MOF) layers onto solid surfaces is a prerequisite for their integration into devices. This work reports the direct growth of Fe3+/benzene di‐carboxylate MOFs onto functionalized silicon surfaces, compatible with a wide range of MOF synthesis conditions. The co‐nucleation and growth of different crystalline phases are evidenced, whose coverage depends on the surface chemistry and/or the solution composition. Three structural phases – the cubic MIL‐101(Fe), a hexagonal phase with a structure close to MOF‐235 and a MIL‐53(Fe) with a monoclinic symmetry ‐ are identified through characteristic crystal shapes and their structural parameters inferred from X‐Ray Diffraction. In addition to the oriented growth of 3D crystallites, the formation of two‐dimensional MIL‐101 nano‐crystallites or thin layers/islands exhibiting extended monocrystalline domains with (111) texture is also demonstrated through high‐resolution atomic force microscopy. Post‐synthesis treatments reveal a weak adhesion of the hexagonal phase, indicating a different surface anchoring.

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