Probing Surface-Adlayer Conjugation on Organic-Modified Si(111) Surfaces with Microscopy, Scattering, Spectroscopy, and Density Functional Theory

Abstract

Highly conjugated molecules bound to silicon are promising candidates for organosilicon electronic devices and sensors. In this study, 1-bromo-4-ethynylbenzene was synthesized and reacted with a hydrogen-passivated Si(111) surface via ultraviolet irradiation. Through an array of characterization and modeling tools, the binding configuration and morphology of the reacted molecule were thoroughly analyzed. Atomic force microscopy confirmed an atomically flat surface morphology following reaction, while X-ray photoelectron spectroscopy verified reaction to the surface via the terminal alkyne moiety. In addition, synchrotron X-ray characterization, including X-ray reflectivity, X-ray fluorescence, and X-ray standing wave measurements, enabled sub-angstrom determination of the position of the bromine atom with respect to the silicon lattice. This structural characterization was quantitatively compared with density functional theory (DFT) calculations, thus enabling the π-conjugation of the terminal carbon atom...