Infrared Characterization of Interfacial Si-O Bond Formation on Silanized Flat SiO2/Si Surfaces

Chemical functionalization of silicon oxide (SiO2) surfaces with silane molecules is an important technique for a variety of device and sensor applications. Quality control of self-assembled monolayers (SAMs) is difficult to achieve because of the lack of a direct measure for newly formed interfacial Si-O bonds. Herein we report a sensitive measure of the bonding interface between the SAM and SiO2, whereby the longitudinal optical (LO) phonon mode of SiO2 provides a high level of selectivity for the characterization of newly formed interfacial bonds. The intensity and spectral position of the LO peak, observed upon silanization of a variety of silane molecules, are shown to be reliable fingerprints of formation of interfacial bonds that effectively extend the Si-O network after SAM formation. While the IR absorption intensities of functional groups (e.g., >C=O, CH2/CH3) depend on the nature of the films, the blue-shift and intensity increase of the LO phonon mode are common to all silane molecules investigated and their magnitude is associated with the creation of interfacial bonds only. Moreover, results from this study demonstrate the ability of the LO phonon mode to analyze the silanization kinetics of SiO2 surfaces, which provides mechanistic insights on the self-assembly process to help achieve a stable and high quality SAM.