A widely used assignment scheme for Si 2p core-level photoemission studies of silicon oxidation relies solely on the formal oxidation state of the silicon. The tacit assumption of this assignment methodology is that second-neighbor effects have no measurable effect on observed Si 2p binding energies. In this letter, new experiments are combined with literature precedents to make the case that the second-neighbor effects play an important role in determining binding energy shifts.
We briefly review the controversy concerning the proper methodology for the assignment of soft x‐ray photoemission Si 2p core levels at Si/SiO2 interfaces. Evidence for Second nearest neighbor effects in the photoemission spectra of analogous free molecules in the gas phase are surveyed for the purpose of placing this controversy within a wider context. Physisorption experiments have been performed to inquire whether the second nearest neighbor effects found in free molecules are in any way reduced in their magnitude owing to the proximity to the highly polarizable Si surface. No evidence for such a diminution have been found.
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