Base Layer Influence on Protonated Aminosilane Gradient Wettability

Protonated amine gradients have been prepared on silicon wafers via programmed controlled rate infusion (CRI) with varying degrees of hydrophobicity and characterized by X-ray photoelectron spectroscopy (XPS) and static and Wilhelmy plate dynamic contact angle measurements. Initially, base layers were spin coated from sols containing tetramethoxysilane (TMOS) and either phenyltrimethoxysilane (PTMOS), dimethyldimethoxysilane (DMDMOS), or octyltrimethoxysilane (OTMOS, C8). Amine gradients were then prepared from 3-aminopropyltriethoxysilane (APTEOS) via CRI. Gradients were exposed to concentrated HCl vapor for amine protonation. XPS showed that NH2 functional groups were distributed in a gradient fashion as a result of CRI controlling the time of exposure to APTEOS. Interestingly, the overall extent of N modification depended on the type of base layer used for gradient formation. The C8-derived base layer had about half the amount of nitrogen on the surface as compared to those prepared from TMOS, which was attributed to a reduction in the number and accessibility of surface silanol groups. The wettability and contact angle (CA) hysteresis were also dependent on the base layer and varied along the length of the gradient. The greatest CA change across the length of the gradient was observed on the gradient formed on the C8-derived base layer. Likewise, the CA hysteresis was approximately 2 times larger on the C8-modified surfaces, indicative of greater chemical inhomogeneity. In contrast to uniformly modified substrates, Wilhelmy plate CA analysis that involves the immersion of samples gave a unique S-shaped CA distance curve for the gradients. The three curve segments correspond to hydrophilic, hydrophobic, and a middle connecting region. Importantly, these curves give precise CAs along the gradient that reflect the surface chemistry and coverage defined by programmed CRI processing.