Light-Assisted Diazonium Functionalization of Graphene and Spatial Heterogeneities in Reactivity

Author
Abstract
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/cm<sup>2</sup>) 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.
Year of Publication
2019
Journal
The Journal of Physical Chemistry Letters
Number of Pages
4788-4793
Date Published
2019-08
ISSN Number
1948-7185
URL
https://pubs.acs.org/doi/full/10.1021/acs.jpclett.9b02225
DOI
10.1021/acs.jpclett.9b02225
JILA PI
Associated Institutes
Journal Article