Octadecyl phosphoric acid ester has been found to produce oriented, well-ordered monolayers on a flat tantalum(V) oxide surface, via self-assembly from a heptane/propan-2-ol solution. By means of contact angle, optical waveguide lightmode spectroscopy (OWLS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and X-ray photoelectron spectroscopy (XPS) measurements, it has been shown that these layers closely resemble those formed by the corresponding thiol−gold system, with respect to packing density, inclination, and order. The system shows promise as an approach to functionalizing oxide surfaces with well-ordered organic monolayers, with potential applications in the fields of biochemical analysis and sensors.

We use ambient-pressure X-ray photoelectron spectroscopy (APXPS) to study chemical changes, including hydroxylation and water adsorption, at copper oxide surfaces from ultrahigh vacuum to ambient relative humidities of ∼5%. Polycrystalline CuO and CuO surfaces were prepared by selective oxidation of metallic copper foils. For both oxides, hydroxylation occurs readily, even at high-vacuum conditions. Hydroxylation on both oxides plateaus near ∼0.01% relative humidity (RH) at a coverage of ∼1 monolayer. In contrast to previous studies, neither oxide shows significant accumulation of molecular water; rather, both surfaces show a high affinity for adventitious carbon contaminants. Results of isobaric and isothermic experiments are compared, and the strengths and potential drawbacks of each method are discussed. We also provide critical evaluations of the effects of the hot filament of the ion pressure gauge on the reactivity of gas-phase species, the peak fitting procedure on the quantitative analysis of spectra, and rigorous accounting of carbon contamination on data analysis and interpretation. This work underscores the importance of considering experimental design and data analysis protocols during APXPS experiments with water vapor in order to minimize misinterpretations arising from these factors.

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