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The etch bath contained KCN at a concentration of 0.1 M in a NaOH/KCl buffer at pH 12. 1-Octauol (Fluka) was added to this bath for experiments on the healing of defects as follows: First, 2.0 mL (excess) of octanol was added to 250 mL of the cyanide bath. The mixture was sonicated for 30 min and stored at room temperature for ∼ 12 h to ensure equilibration. The aqueous solution was then separated in a phase-separation funnel and diluted by 2 with a cyanide solution. Half-saturation of the etch bath with octanol was preferred over full saturation to prevent phase separation. All etch solutions were used at 25 °C with moderate stirring.
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Elucidating on the molecular level how octanol contributes to the protection of Au covered with ECT is difficult. The insertion of one or a few octanol molecules in defects in the monolayer is plausible and may occur concurrently with the formation of a film of octanol over the alkanethiol monolayer. Octanol does not seem to form a film on Au alone because even adding a large excess of octanol to the etch bath does not significantly slow the etching of the Au.
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