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Alkanethiols HS(CH2)nCH3 (n = 7, 11, 15, 17) and the hydroxy functional thiol HS(CH2)12OH are shown to adsorb from solution onto zinc selenide crystals and form well-organized monolayers. The chemisorption of these organosulfur compounds has been studied using transmission Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and surface wetting properties. FTIR indicates that the longer chain alkanethiols (n = 15, 17) form well-defined SAMs with crystalline-like conformations of the chains within the monolayers. As the chain length decreases, there is less conformational order present in the monolayers. The orientation of the largely trans-zigzag alkyl chains on the surface is at a slight tilt off the surface normal direction, as indicated by the dichroism of the infrared spectra and the chain-length-dependent scaling of the mass coverage of the SAM. The structural data obtained by XPS and FTIR are compatible with the inferences derived from measurements of surface wetting properties. The thickness of the SAM layers calculated using XPS is found to be comparable to the thickness of alkanethiol SAMs formed on gold and other metal surfaces. Changes in the surface of the ZnSe crystal because of chemisorption of the thiols are illustrated by data from AFM imaging. The feasibility of forming cohesive patterned monolayers by microcontact printing is also demonstrated.


Originally published as:

Noble-Luginbuhl, Alison R., and Ralph G. Nuzzo. “Assembly and Characterization of SAMs Formed by the Adsorption of Alkanethiols on Zinc Selenide Substrates.” Langmuir 17, no. 13 (June 2001): 3937–44.

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