Self-assembled monolayer films from liquid and supercritical carbon dioxide

We report the formation of self-assembled monolayers (SAMs) on gold substra tes by exposure to n-alkanethiols [CH3(CH2)(n-1)SH; n = 8, 10, 12, 16, and 18] in liquid and supercritical carbon dioxide. The results of this novel s tudy show that an environmentally friendly solvent can be used to form high ly crystalline SAMs with few gauche defects and that pressure as well as ex posure time can be used to affect the structural and barrier properties of the monolayer film. Reflectance infrared spectroscopy, electrochemical impe dance spectroscopy, and wetting measurements were used to characterize the SAMs. The effects of pressure (76-300 bar) and adsorption time (3-90min) on the formation of the SAMs were explored. The overall chain density of thes e SAMs was greater than that for SAMs formed in common organic solvents suc h as ethanol. The properties of the SAMs were slightly affected by the pres sure during formation. At 35 degreesC, as the carbon dioxide pressure incre ased (from 76 to about 140 bar), the packing density and resistance of the SAM increased. SAMs prepared at higher pressures ranging from about 140 to 300 bar exhibited similar resistances, capacitances, and canted structures. There was also no significant difference in using liquid (25 degreesC and 103 bar) or supercritical (35 degreesC and 103 bar) carbon dioxide for SAM formation. Supercritical carbon dioxide also enabled the formation of SAMs using polar adsorbates (-OH- and -CO2H-terminated thiols) to prepare high-e nergy surfaces that are wet by water.