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Adsorption of Trimethyl Phosphite at the Ge(100)-2 × 1 Surface by Nucleophilic Reaction

Although phosphorus adsorption on semiconductors has potential applications in sensors, adhesion promoters, wear-resistant coatings, and monolayer doping for ultrashallow junction transistors, it has been the subject of few studies. Adsorption of trimethyl phosphite at the Ge(100)-2 × 1 surface is studied in this work by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. Trimethyl phosphite adsorbs by dissociation of a methoxy C–O bond, forming dimethyl germylphosphonate and methyl species at the surface. These results demonstrate a method for formation of covalent Ge–P bonds at the Ge(100)-2 × 1 surface by reaction of a P–O–R group, which is common to many phosphorus-containing functional groups. Moreover, this reaction is directly analogous to several known reactions of trialkyl phosphites in solution showing that the Ge(100)-2 × 1 surface can mimic nucleophilic/electrophilic molecular reactants in organophosphorus chemistry. By showing...