Packing density of HS(CH2)(n)COOH self-assembled monolayers.

Self-assembled monolayers (SAMs) of HS(CH(2))(n)COOH, n = 5, 10, 15 deposited from ethanol solution onto gold are prepared by five approaches, and their packing densities are evaluated by X-ray photoelectron spectroscopy (XPS) measurements. The five approaches are: (1) direct deposition; (2) acetic-acid-assisted deposition; (3) butyl-amine-assisted deposition; (4) displacement of a preformed HS(CH(2))(n)CH(3) (n = 5, 10, 15) SAMs; and (5) co-deposition with HS(CH(2))(n)CH(3) (n = 5, 10, 15). Packing density metrics are calculated from measurements of SAM and substrate photoemission intensities and their attenuations by two methods. In one case the attenuated photoemissions are expressed as a ratio relative to comparable measurements on an experimental HS(CH(2))(n)CH(3) model system. In the other case a new method is introduced where a calculated attenuation based on theoretical random coil and extended chain models is used as the reference to determine a packing density fraction. Packing densities are also correlated with the S2p(Au-bonded):Au4f peak area ratios and with shifts in the C1s binding energies. SAMs prepared by the direct deposition are a partial multilayer where a second molecular layer is physisorbed onto the SAM and not removable by solvent washing. The addition of acetic acid to the deposition solution disrupts dimer associations of HS(CH(2))(n)COOH in solution and at the surface of the monolayer and yields the most ordered monolayer with the highest density of -COOH groups. The addition of butyl amine results in a labile ammonium carbonate ion pair formation but results in a lower packing density in the SAM. The displacement of the preformed HS(CH(2))(n)CH(3) SAM and the co-deposition of HS(CH(2))(n)CH(3) with HS(CH(2))(n)COOH result in SAMs with little incorporation of the -COOH component.