Micropatterned Charge Heterogeneities via Vapor Deposition of Aminosilanes

Aminosilanes are routinely employed for charge reversal or to create coupling layers on oxide surfaces. We present a chemical vapor deposition method to pattern mica surfaces with regions of high-quality aminosilane (3-amino-propyltriethoxysilane, APTES) monolayers. The approach relies on the vapor deposition of an aminosilane through a patterned array of through-holes in a PDMS (poly(dimethylsiloxane)) membrane that acts as a mask. In aqueous solutions the surfaces have regular patterns of charge heterogeneities with minimal topographical variations over large areas. This versatile dry lift-off deposition method alleviates issues with multilayer formation and can be used to create charge patterns on curved surfaces. We identify the necessary steps to achieve high quality monolayers and charge reversal of the underlying mica surface: (1) hexane extraction to remove unreacted PDMS oligomers from the membrane that would otherwise deposit on and contaminate the substrate, (2) oxygen plasma treatment of the top of the membrane surfaces to generate a barrier layer that blocks APTES transport through the PDMS, and (3) low of the vapor pressure of APTES during deposition to minimize APTES condensation at the mica membrane vapor contact lines and to prevent multilayer formation. Under these conditions, AFM imaging shows that the monolayers have a height of 0.9 +/- 0.2 nm with an increase in height up to 3 nm at the mica-membrane-vapor contact lines. Fluorescence imaging demonstrates pattern fidelity on both flat and curved surfaces, for feature sizes that vary between 6.5 and 40 mu m. We verify charge reversal by measuring the double layer forces between a homogeneous (unpattemed) APTES monolayers and a mica surface in aqueous solution, and we characterize the surface potential of APTES monolayers by measuring the double-layer forces between identical APTES surfaces. We obtain a surface potential of +110 +/- 6 mV at pH 4.0.