Acid-base properties and zeta potentials of self-assembled monolayers obtained via in situ transformations

Siloxane-anchored, self-assembled monolayers (SAMs) on single crystal Si were prepared with a variety of surface functional groups using a single commercially available surfactant (1-bromo-11-(trichlorosilyl)undecane) followed by in situ transformations. Polar (thioacetate and thiol), nonpolar (methyl), acidic (sulfonic and carboxylic), basic (various amines), and ionic (alkylammonium) surface functionalities were prepared. For primary amine and sulfonate surfaces, the degree of surface charge as a function of pH was determined ex situ using X-ray photoelectron spectroscopy (XPS). Sulfonate SAMs exhibited much higher effective pK(a) (similar to2) than dilute sulfonic acid (-5 to -6), and amine SAMs exhibited much lower pK(a) (similar to3) than dilute organic amines (similar to10). This is attributed to the stabilization of nonionized groups by adjacent ionized groups in the SAM. Zeta potentials of these SAMs as a function of pH were consistent with the XPS results and indicated that ionizable SAM surfaces can generate surface potentials much higher than those of nonionic SAMs (thioacetate, methyl) and typical oxide surfaces.