The adsorption of CO2 molecules on monolayer epitaxial graphene on a SiC(0001) surface at 30 K was investigated by temperature-programmed desorption and X-ray photoelectron spectroscopy. The desorption energy of CO2 on graphene was determined to be (30.1–25.1) ± 1.5 kJ/mol at low coverages and approached the sublimation energy of dry ice (27–25 kJ/mol) with increasing the coverage. The adsorption of CO2 on graphene was thus categorized into physisorption, which was further supported by the binding energies of CO2 in core-level spectra. The adsorption states of CO2 on graphene were theoretically examined by means of the van der Waals density functional (vdW-DF) method that includes nonlocal correlation. The experimental desorption energy was successfully reproduced with high accuracy using vdW-DF calculations; the optB86b-vdW functional was found to be most appropriate to reproduce the desorption energy in the present system.

Graphene is a promising material for next-generation devices owing to its excellent electronic properties. Graphene devices do not, however, exhibit the high performance that is expected considering graphene’s intrinsic electronic properties. Operando, i.e., gate-controlled, photoelectron nanospectroscopy is needed to observe electronic states in device operation conditions. We have achieved, for the first time, pinpoint operando core-level photoelectron nanospectroscopy of a channel of a graphene transistor. The direct relationship between the graphene’s binding energy and the Fermi level is reproduced by a simulation assuming linear band dispersion. This operando nanospectroscopy will bridge the gap between electronic properties and device performance.

The linear band dispersion of graphene's bands near the Fermi level gives rise to its unique electronic properties, such as a giant carrier mobility, and this has triggered extensive research in applications, such as graphene field-effect transistors (GFETs). However, GFETs generally exhibit a device performance much inferior compared to the expected one. This has been attributed to a strong dependence of the electronic properties of graphene on the surrounding interfaces. Here we study the interface between a graphene channel and SiO2, and by means of photoelectron spectromicroscopy achieve a detailed determination of the course of band alignment at the interface. Our results show that the electronic properties of graphene are modulated by a hydrophilic SiO2 surface, but not by a hydrophobic one. By combining photoelectron spectromicroscopy with GFET transport property characterization, we demonstrate that the presence of electrical dipoles in the interface, which reflects the SiO2 surface electrochemistry, determines the GFET device performance. A hysteresis in the resistance vs. gate voltage as a function of polarity is ascribed to a reversal of the dipole layer by the gate voltage. These data pave the way for GFET device optimization.

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The functionalization of graphene is important in practical applications of graphene, such as in catalysts. However, the experimental study of the interactions of adsorbed molecules with functionalized graphene is difficult under ambient conditions at which catalysts are operated. Here, the adsorption of CO2 on an oxygen-functionalized epitaxial graphene surface was studied under near-ambient conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). The oxygen-functionalization of graphene is achieved in situ by the photo-induced dissociation of CO2 with X-rays on graphene in a CO2 gas atmosphere. The oxygen species on the graphene surface is identified as the epoxy group by XPS binding energies and thermal stability. Under near-ambient conditions of 1.6 mbar CO2 gas pressure and 175 K sample temperature, CO2 molecules are not adsorbed on the pristine graphene, but are adsorbed on the oxygen-functionalized graphene surface. The increase in the adsorption energy of CO2 on the oxygen-functionalized graphene surface is supported by first-principles calculations with the van der Waals density functional (vdW-DF) method. The adsorption of CO2 on the oxygen-functionalized graphene surface is enhanced by both the electrostatic interactions between the CO2 and the epoxy group and the vdW interactions between the CO2 and graphene. The detailed understanding of the interaction between CO2 and the oxygen-functionalized graphene surface obtained in this study may assist in developing guidelines for designing novel graphene-based catalysts.