Langmuir, Vol.24, No.15, 7889-7896, 2008
AFM forces measured between gold surfaces coated with self-assembled monolayers of 1-hexadecanethiol
An atomic force microscope (AFM) was used to measure the forces between gold surfaces with and without hydrophobizing them by the self-assembly of 1-hexadecanethiol. The forces measured between bare gold surfaces were fitted to the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory with a Hamaker constant of 1.2 x 10(-20) J, which was close to the value determined using the methylene iodide contact angle method but was lower than that calculated using the Lifshitz theory. When the surfaces were hydrophobized in a 0.01 mM thiol-in-ethanol solution for 10 min, the measured forces exhibited a long-range force with a decay length of 35 nm. Despite its high water contact angle (105 degrees), the force curve was smooth and exhibited no steps. When the surfaces were hydrophobized in a 1 mM thiol solution for longer than 6 h, however, the force curves exhibited steps, indicating that the long-range attractions were caused by bridging bubbles. When the measurements were conducted after washing the substrates with organic solvents, the steps disappeared and long-range attractive forces appeared. In the presence of ethanol, the water contact angle decreased to below 90 degrees, the attraction became weaker, and the force curves became smooth. On the basis of the results obtained in the present work, possible mechanisms for the long-range attractions are discussed.