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The reaction of hydrogen-terminated Si(111) and oxide-terminated silicon surfaces with neat anhydrous liquid methanol (CH3OH) has been studied with Fourier transform infrared spectroscopy (FTIR) as a function of solution temperature and immersion time. At 65 °C, reaction of atomically smooth H−Si(111) surfaces with CH3OH (l) results in partially methoxylated silicon surfaces that are free of any detectable subsurface oxidation (Si−O−Si bonds); this is in contrast to observable oxidation found after similar reactions on H−Si(100) surfaces. At long reaction times (t > 3 h), the Si(111) surface saturates with Si-OCH3 sites at a coverage of approximately 30% of a monolayer, with the residual ∼70% comprised of unreacted Si−H sites. The lack of any detectable silicon oxide makes it possible to conclude the following: (i) Reaction mechanisms involving insertion of oxygen atoms from the CH3OH molecule into the subsurface Si−Si back bonds cannot be dominant for (111)-oriented silicon under these conditions. (ii) T...

Investigation of the Chemical Purity of Silicon Surfaces Reacted with Liquid Methanol