Phase separation of a mixed self-assembled monolayer prepared via a stepwise method.

Self-assembled monolayers (SAMs), a molecular-level assembly that forms spontaneously, provide a vehicle for investigating specific interactions at interfaces. This is particularly true for mixed SAMs that are composed of organosilanes with different chain lengths and/or chemical functionalities because they offer an adjustable surface for constructing 3D structures containing a variety of moieties. We recently observed that coadsorbed monolayers with different organosilanes on a Si wafer were separated into several tens or hundreds of nanometer domains that were rich in individual components. Several organosilanes, such as octadecyltrichlorosilane (OTS), octadecyltrimethoxysilane (OTMS), (3-mercaptopropyl)trimethoxysilane (MPTMS), and (3-aminopropryl)trimethoxysilane (APTMS), were used for regional separation. In this study, we propose a stepwise deposition method, namely, the deposition of a second siliane on a SAM substrate that creates intentional defects in the first silane. The surface morphologies were adjusted by the deposition sequence and immersion time of the silanes. As a result, a mixed SAM prepared by the proposed method showed effectively functionalized films compared to that prepared by the one-step method.