Hydrophobic monolayer preparation by Langmuir–Blodgett and chemical adsorption techniques
Alkylsiloxane and perfluoroalkylsiloxane monolayers are prepared on siliceous surfaces using the techniques of Langmuir–Blodgett deposition and solid–liquid chemical adsorption. Acid-catalyzed hydrolysis and polycondensation reactions provide two-dimensional siloxane networks at the liquid–vapor interface, which can be compressed to mean molecular areas of 
22 and 32 Å2 for pendent hydrocarbon and fluorocarbon chains, respectively. Subsequent Langmuir–Blodgett transfer onto glass substrates at moderate surface pressures leads to compact monolayers for single-component precursors, while mixed alkyl- and perfluoroalkylsilanes produce nonhomogeneous films characterized by transfer ratios greater than unity. As an alternate monolayer preparation technique, silane polymerization was performed directly on siliceous surfaces via a chemical adsorption mechanism. XPS analysis of a chemically adsorbed 1H,1H,2H,2H-perfluorodecylsiloxane film confirms a single adsorbed monolayer thickness in which the pendent fluoroalkyl chains align nonperpendicularly with respect to the surface. The surface free energy was determined to be 11.4 dyn cm−1 based on static contact angle measurements. AFM imaging shows the presence of surface defects due to oligomer deposition during the drying process. The use of solubilized trichloro-based silane coupling agents under anhydrous conditions is shown to produce surfaces with a minimal number of surface defects. The presence of undissolved silane material in the bulk solution significantly increases the number of surface defects.