Comprehensive Investigation of Self-Assembled Monolayer Formation on Ferromagnetic Thin Film Surfaces

We report a simple, universal method for forming high surface coverage SAMs on ferromagnetic thin (≤100 nm) films of Ni, Co, and Fe. Unlike previous reports, our technique is broadly applicable to different types of SAMs and surface types. Our data constitutes the first comprehensive examination of SAM formation on three different ferromagnetic surface types using two different surface-binding chemistries (thiol and isocyanide) under three different preparation conditions: (1) SAM formation on electroreduced films using a newly developed electroreduction approach, (2) SAM formation on freshly evaporated surfaces in the glovebox, and (3) SAM formation on films exposed to atmospheric conditions beforehand. The extent of SAM formation for all three conditions was probed by cyclic voltammetry for surfaces functionalized with either (11-thiolundecyl)ferrocene (Fc-(CH2)11-SH) or (11-isocyanoundecyl)ferrocene (Fc-(CH2)11-NC). SAM formation was also probed for straight-chain molecules, hexadecanethiol and hexadecaneisocyanide, with contact angle measurements, X-ray photoelectron spectroscopy, and reflection−absorption infrared spectroscopy (RAIRS). The results show that high surface coverage SAMs with low surface-oxide content can be achieved for thin, evaporated Ni and Co films using our electroreduction process with thiols. The extent of SAM formation on electroreduced films is comparable to what has been observed for SAMs/Au and to what we observe for SAMs/Ni, Co, and Fe samples prepared in the glovebox.