Regulation of local structure and composition of binary disulfide and thiol self-assembled monolayers using nanografting

Nanografting is used to create spatial confinement, which enables regulation of self-assembly reaction pathways and outcome. The degree and outcome of this regulation is revealed using binary self-assembled monolayers (SAMs) of organothiols and disulfides. In naturally grown systems, these SAMs have more complex morphology when compared with corresponding binary alkanethiol SAMs. Taller molecules form nanodomains of ellipsoidal cap in shape. These domains arrange in various irregular geometries, including 1D worm-like and 2D branches. This observation differs from binary alkanethiol SAMs, where nanodomains are separated and randomly dispersed. During nanografting, more homogeneous morphology was observed compared with naturally grown layers. By varying nanoshaving speed, the nanodomain structure can be regulated from randomly dispersed to more heterogeneous and, finally, to near natural growth. This trend is very similar to mixed alkanethiol systems, where the domain size and separation increase with increasing speed. Different from the alkanethiol systems, the observed structural variations are due to the changes in surface composition, in addition to domain size, shape, and arrangement.