The monolayer functionalization of covalent semiconductors such as Si (100) single crystal with boron-containing compounds, including boron trichloride, boric acid, and 4-fluorophenylboronic acid were studied in order to understand the interactions of these molecules with the different terminated surfaces (H-, and Cl-Si(100)) for designing possible silicon doping processes. And the surface modification of oxide semiconductors such as TiO2 and Al2O3 nanoparticles with 4-fluorophenylboronic acid in solution was investigated in order to understand the attachment chemistry and to develop spectroscopic labels for surface characterization. The study of those modified materials was followed by X-ray photoelectron spectroscopy (XPS) primarily for the Si(100) single crystal and also solid-state NMR (ss-NMR), and infrared spectroscopy for the TiO2 and Al2O3 nanoparticles to determine the binding modes of the attached compound. Density functional theory was utilized to supplement the analysis, interpret the results of spectroscopic measurements, and interrogate the surface stability of possible surface species. The results obtained in these studies confirm the attachment of the boron trichloride, boric acid, and 4-fluorophenylboronic acid showing selectivity for the Cl terminated-Si(100) surface, the possible surface species and stability are evaluated with density functional theory. The attachment chemistry of 4-fluorophenylboronic acid on the TiO2 and Al2O3 nanoparticles was confirmed with high coverage and the type of attachments in each metal oxide are described. This work provides a fundamental understanding of reacting functionalized semiconductor surfaces with boron-containing molecules. In the case of flat surfaces, these reactions can be used for monolayer doping or as a deposition resist. For oxide nanomaterials, the same approach can be used for spectroscopic labeling or for further functionalization.

Monolayer functionalization of semiconductors surfaces with boron-containing precursors

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