Derivatization of optically transparent materials with diazonium reagents for spectroscopy of buried interfaces

This paper presents a method to derivatize a wide variety of substrate materials that are frequently used in spectroscopic characterizations with molecular layers through the reduction of aromatic diazonium reagents. The method relies on an ultrathin (5 nm) layer of a reactive metal (e.g., Ti or Al) deposited as a primer that subsequently mediates the reduction of aromatic diazonium reagents from acetonitrile solution. Following surface modification, the Ti can be oxidized to provide a passivated support surface. Raman, Infrared, UV-vis and X-ray photoelectron spectroscopic techniques are used to characterize the molecular layers on the metal primer surface. When a Ti primer layer is derivatized via diazonium reduction, the molecule is shown to be present on the ultrathin Ti layer on Au, Al, quartz, Si/SiO(x), glass, and polyethylene surfaces. For molecules bound to a Ti primer, the molecular layer was found to be stable to sonication in acetone or acetonitrile, a 1 h exposure to boiling water, and a 30 min exposure to 0.1 M acid or base. The approach also permits spectroscopic characterization of buried thin-film molecular layers on optically transparent substrates after deposition of thick top metal contacts.