Vapor-Phase Plotting of Organosilane Chemical Gradients

Vapor-phase plotting of organosilane-based self-assembled monolayer (SAM) gradients is demonstrated for the first time. Patterned SAMs are formed by delivering gas-phase organotrichlorosilane precursors to a reactive silica surface using a heated glass capillary. The capillary is attached via a short flexible tube to a reservoir containing the precursor dissolved in toluene. The proximal end of the capillary is positioned at an experimentally optimized distance of 30 μm above the substrate during film deposition. The capillary is mounted to a stepper-motor-driven X, Y plotter for raster scanning above the surface. Two different organotrichlorosilane precursors are employed in this initial demonstration: n-octyltrichlorosilane and 3-cyanopropyltrichlorosilane. The dependence of SAM deposition on ambient relative humidity, capillary-substrate separation, raster-scanning speed, and solvent viscosity and volatility is explored and optimum deposition conditions are identified. The optimized procedures are used to plot uniformly modified square "pads" and gradients of the silanes. Film formation is verified and the gradient profiles are obtained by sessile drop water contact angle measurements, spectroscopic ellipsometry measurements of film thickness, and X-ray photoelectron spectroscopy mapping. The resolution of the plotting process is currently in the millimeter range and depends on capillary diameter and distance from the substrate surface. Vapor-phase plotting affords a unique direct-write method for producing patterned and chemically graded SAMS that may find applications in microfluidic devices, planar chromatography, and optical and electronic devices.