Infrared absorption of atomic and molecular vibrations in solids can be affected by electronic contributions through non-adiabatic interactions, such as the Fano effect. Typically, the infrared-absorption lineshapes are modified, or infrared-forbidden modes are detectable as a modulation of the electronic absorption. In contrast to such known phenomena, we report here the observation of a giant-infrared-absorption band in reduced graphene oxide, arising from the coupling of electronic states to the asymmetric stretch mode of a yet-unreported structure, consisting of oxygen atoms aggregated at the edges of defects. Free electrons are induced by the displacement of the oxygen atoms, leading to a strong infrared absorption that is in phase with the phonon mode. This new phenomenon is only possible when all other oxygen-containing chemical species, including hydroxyl, carboxyl, epoxide and ketonic functional groups, are removed from the region adjacent to the edges, that is, clean graphene patches are present.
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The authors acknowledge the financial support of the SWAN-NRI program and Texas Instruments (TI), the technical expertise of J-F. Veyan and in-depth discussions with L. Colombo (TI) and with R. M. Wallace, E. Vogel, J. Kim, M. Kim, J-F. Veyan and W. Kirk at UT Dallas.
The authors declare no competing financial interests.
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Acik, M., Lee, G., Mattevi, C. et al. Unusual infrared-absorption mechanism in thermally reduced graphene oxide. Nature Mater 9, 840–845 (2010). https://doi.org/10.1038/nmat2858
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