Abstract
In semiconductor manufacturing of 3-D nano-structures, modified kinetics have been encountered for the aqueous chemical etching of thin films in nano-confined spaces. A popular explanation relies on changes in reactant concentration from the overlap of electrostatic double layers (EDL) on opposite walls of the nano-structures. In this study, the cycloaddition of dibenzylcyclooctyne-PEG3-alcohol (DBCO) to a linear azide-terminated SAM was performed in nanochannels of width varying from 62 to 32 nm. ATR-FTIR was used to monitor the reaction kinetics, characterize water structuring and determine the pH in nanochannels. Reaction kinetics were slower in nanochannels as compared to a planar surface, while pH shifts were observed in absence of EDL overlap, with a significant influence of channel width. Actually only the overall decrease in reaction rate could be explained by EDL overlap. The discussion shows that the water structuring measured in nanochannels may play a significant role in the observed phenomena.
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