Electrochemically partitioned assembly of organosulfur monolayers and nanoparticles

Partitionally assembled organosulfur monolayers were prepared by using an electrochemically assisted assembly method on gold films that were preseparated into two regions insulated from each other. Cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the n-dodecanethiol (DDT) and the 11-mercaptoundecanoic acid (MUA) monolayers, which were separately assembled on different substrate regions. CV results indicated that both the DDT- and MUA-coated gold electrodes showed a blocking property toward the negatively charged redox probe Fe(CN)6(3-). However, when positively charged Ru(NH3)6(3+) was used as the redox probe, the MUA- and DDT-modified electrodes showed quasireversible and blocking CV features, respectively. These phenomena were attributed to different interactions between the negatively charged MUA surface and the negatively or positively charged redox probes. XPS spectra obtained on the MUA modified region exhibited an O(1s) peak and a small discrete C(1s) peak, which arose from the oxygen and the carbon atoms in the carboxylic acid groups, respectively. For the DDT-modified region, these two peaks were absent. CV and XPS experimental results provided strong evidence that different SAMs were selectively deposited onto different regions of the preexisting patterns of the substrate by electrochemically partitioned assembly. The partitionally assembled sulfur-based monolayers with different terminal groups were used to form location-selective nanoparticle assemblies. This electrochemically partitioned assembly technique has great potential in controllable constructions of molecular layers and nanostructures on different surface microarchitectures that are closely integrated on one substrate but insulated from each other.