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arXiv: 1608.01424
Pristine single-walled carbon nanotubes (SWCNTs) are rather inert to O$_2$ and N$_2$, which for low doses chemisorb only on defect sites or vacancies of the SWCNTs at the ppm level. However, very low doping has a major effect on the electronic properties and conductivity of the SWCNTs. Already at low O$_2$ doses (80 L), the X-ray photoelectron spectroscopy (XPS) O 1s signal becomes saturated, indicating nearly all the SWCNT's vacancies have been oxidized. As a result, probing vacancy oxidation on SWCNTs via XPS yields spectra with rather low signal-to-noise ratios, even for metallicity-sorted SWCNTs. We show that, even under these conditions, the first principles density functional theory calculated Kohn-Sham O 1s binding energies may be used to assign the XPS O 1s spectra for oxidized vacancies on SWCNTs into its individual components. This allows one to determine the specific functional groups or bonding environments measured. We find the XPS O 1s signal is mostly due to three O-containing functional groups on SWCNT vacancies: epoxy (C$_2$$>$O), carbonyl (C$_2$$>$C$=$O), and ketene (C$=$C$=$O), as ordered by abundance. Upon oxidation of nearly all the SWCNT's vacancies, the central peak's intensity for the metallic SWCNT sample is 60\% greater than for the semiconducting SWCNT sample. This suggests a greater abundance of O-containing defect structures on the metallic SWCNT sample. For both metallic and semiconducting SWCNTs, we find O$_2$ does not contribute to the measured XPS O~1s spectra.
Condensed Matter - Materials Science, ADSORPTION, Condensed Matter - Mesoscale and Nanoscale Physics, 103018 Materialphysik, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, DISSOCIATION, OXYGEN, ELECTRONIC-PROPERTIES, SYSTEMS, DENSITY, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), GRAPHENE OXIDE, FUNCTIONALIZATION, SENSITIVITY, 103018 Materials physics
Condensed Matter - Materials Science, ADSORPTION, Condensed Matter - Mesoscale and Nanoscale Physics, 103018 Materialphysik, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, DISSOCIATION, OXYGEN, ELECTRONIC-PROPERTIES, SYSTEMS, DENSITY, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), GRAPHENE OXIDE, FUNCTIONALIZATION, SENSITIVITY, 103018 Materials physics
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