Microfluidic Surface Titrations of Electroactive Thin Films.

We report the use of microfluidic surface titrations (MSTs) for studying electroactive self-assembled monolayers (eSAMs) and other thin films. The technique of MST utilizes a microfluidic generation-collection dual channel electrode (DCE) configuration to quantify the charge associated with electroactive thin films that might or might not be in direct contact with an electrode surface. This technique allows for quantitative measurement of surface coverages, Γ, as low as 30 pmol cm ^-2 for electrodeposited Cu thin films. Additionally, we show that it is possible to quantify Γ for ferrocene (Fc)-terminated alkylthiols in mixed-monolayer eSAMs. Interestingly, MSTs sometimes reveal a two-fold higher eSAM concentration compared to direct electrochemical measurements. This finding suggests that in these instances not all the constituent Fc-moieties of the eSAM are in sufficiently close proximity to the surface to be addressable via direct electrochemistry.