Quantifying the Selective Modification of Au(111) Facets via Electrochemical and Electroless Treatments for...

Manipulating the composition of a mixed alkylthiol self-assembled monolayer (SAM) modified gold surface using both electrochemical and electroless methods is demonstrated. Through the use of fluorophore labeled thiolated DNA and in situ fluorescence microscopy with a gold single crystal bead electrode, a procedure was developed to study and quantify the selective desorption of an alkylthiolate SAM. This method enabled a self-consistent measurement of the removal of the SAM from the 111 surface compared to the 100 surface region at various potentials. A 20-fold increase in the electrochemical removal and replacement of the SAM from the 111 surface over the 100 surface was realized at -0.8 V/AgAgCl. A related procedure was developed for the solution-based electroless removal of the SAM using NaBH₄ achieving a similar selectivity at the same potential. Unfortunately, in the electroless process fine control over the reducing potential was difficult to achieve. In addition, working in the presence of O₂ complicates the solution potential measurement due to depolarization by the reduction of O₂, resulting in a less clear relationship between selectivity and measured solution potential. Interestingly, the electrochemical method was not disturbed by the presence of O₂. In preparation for work with Au nanorods, electrochemical measurements were performed in electrolyte that included 1 mM CTAB and was found to not interfere with this method. Preliminary results are promising for using this methodology for treatment of acid-terminated alkylthiol modified Au nanorods.