Paper: 2019 Light-assisted diazonium functionalization of graphene and spatial heterogeneities in reactivity

Light-assisted diazonium functionalization of graphene and spatial heterogeneities in reactivity

Reviews and Highlights Quantum Science Molecular and Soft-matter Ultrafast Nano-optics and Nanophotonics Mineralogy and Geochemistry

Yunqi Li, Wan Li, Michael Wojcik, Bowen Wang, Liang-Chun Lin, Markus B. Raschke, Ke Xu
The Journal of Physical Chemistry Letters 10 (17), 4788-4793 (2019)
DOI PDF

The reaction of monolayer graphene with aryl diazonium salts is a popular approach for functionalizing graphene under ambient conditions. We here apply interference reflection microscopy (IRM), a label-free optical technique, to study the in situ reaction dynamics of the representative diazonium reaction of graphene with 4-nitrobenzenediazonium tetrafluoroborate (4-NBD) at high spatiotemporal resolution and further correlate results with atomic force microscopy, Raman spectroscopy, and infrared scattering scanning near-field optical microscopy. Interestingly, we find the reaction to be significantly promoted by a low (0.5 W/cm2) level of blue visible light, whereas at the same intensity level, red light has negligible effects on reaction rate. We further report rich spatial heterogeneities for the reaction, including enhanced reactivity at graphene edges and an unexpected flake-to-flake variation in reaction rate. Moreover, we demonstrate direct photopatterning for the 4-NBD functionalization, achieving 400 nm patterning resolution.