Dip-Pen Nanolithography Using the Amide-Coupling Reaction with Interchain Carboxylic Anhydride- Terminated Self-Assembled Monolayers

Herein we report on a new type of dip‐pen nanolithography (DPN), which utilizes an interfacial organic reaction—the amide‐coupling reaction—between chemically activated surfaces and amine ink molecules transferred from an atomic force microscopy tip. As a representative of the chemically activated surfaces that could react with amine compounds, we formed a self‐assembled monolayer terminating in interchain carboxylic anhydride (ICA) groups on gold, and generated chemically derived nanopatterns using alkylamines as ink molecules. Amine inks showed diffusive behavior similar to thiol inks on gold in conventional DPN, and the pattern sizes were controlled by changing the tip dwell times. In addition, nanopatterns of hydrolyzed ICAs were generated by taking advantage of the participation of the water meniscus in the DPN process and the chemical nature of the ICAs. A new type of dip‐pen nanolithography that uses amide‐coupling reactions between chemically activated surfaces and amine compounds transferred from an AFM tip (see figure) is demonstrated. Chemically derived nanopatterns, using alkylamines as ink molecules, are generated by using a self‐assembled monolayer terminating in interchain carboxylic anhydrides on gold.