title: Structural characterization of 4-bromostyrene self-assembled monolayers on si(111).
abstract: Organic functionalization of silicon holds promise for a variety of applications ranging from molecular electronics to biosensing. Because the performance and reliability of organosilicon devices will be intimately tied to the detailed structure of the organic adlayers, it is imperative to develop systematic strategies for forming and characterizing self-assembled monolayers (SAMs) on silicon with submolecular spatial resolution. In this study, we use 4-bromostyrene for the photochemical growth of Br-terminated SAMs on Si(111). A variety of experimental and theoretical techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), X-ray standing waves (XSW), X-ray fluorescence (XRF), and density functional theory (DFT) have been employed to determine the coverage and conformation of the 4-bromostryene molecules within the SAM. In particular, AFM verifies a continuous and atomically flat SAM, and the XRR data indicate a SAM thickness of 8.50 A and a molecular coverage of 46% of the surface silicon atoms. Because the DFT calculations indicate a molecular length of 8.89 A, the measured XRR thickness implies a molecular tilt angle of approximately 17 degrees. The XRR analysis also suggests that the Br atoms are preserved on top of the SAM in agreement with XPS measurements that show bromine bound solely to carbon and not to silicon. XRF reveals a Br atomic coverage of 50%, again in close agreement to that found by XRR. Single-crystal Bragg diffraction XSW is used to generate a three-dimensional map of the Br distribution within the SAM, which in conjunction with the XRR result suggests that the 4-bromostyrene molecules are tilted such that the Br atoms are located over the T4 sites at a height of 8.50 A above the top bulklike Si(111) layer. The direction of molecular tilt toward the T4 sites is consistent with that predicted by the DFT calculation. Overall, through this unique suite of complementary structural characterization techniques, it is concluded that the Br functional handle is preserved at the top of the SAM and is available for further substitutional chemistry.
authors.affiliation: Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208-3108, USA.
authors.forename: Rajiv
authors.initials: R
authors.lastname: Basu
authors.forename: Jui-Ching
authors.initials: JC
authors.lastname: Lin
authors.forename: Chang-Yong
authors.initials: CY
authors.lastname: Kim
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Schmitz
authors.forename: Nathan L
authors.initials: NL
authors.lastname: Yoder
authors.forename: Joshua A
authors.initials: JA
authors.lastname: Kellar
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bedzyk
authors.forename: Mark C
authors.initials: MC
authors.lastname: Hersam
mesh_terms: D018625:Microscopy, Atomic Force; D008958:Models, Molecular; D008968:Molecular Conformation; D012825:Silicon / Q000737:chemistry*; D013057:Spectrum Analysis; D013343:Styrenes / Q000737:chemistry*
chemical_list: D013343:Styrenes; C519197:4-bromostyrene; D012825:Silicon