In the present work we analyze these spectra by means of partial density of states (pDOS) as calculated from a single ion pair of the respective ionic liquid using density functional theory (DFT). Subsequently we reconstruct the XPS and UPS spectra by considering photoemission cross sections and analyze the MIES spectra by pDOS, which provides us decisive hints to the ionic liquid surface structure.

We have measured the bulk and surface electronic structure of several ionic liquids of alkyl-imidazolium cations with different alkyl chains (EMIm, BMIm, HMIm, OMIm) and bis(trifluoromethylsulfonyl)imide anions (Tf2N) by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS He I and He II) as well as metastable induced electron spectroscopy (MIES). The results are compared with the densities of states (DOS) calculated by density functional theory (DFT). By XPS we found the stoichiometry of the respective ILs reproduced, and different carbon atom positions reflected by the splitting of the C(1s)-from the trifluor-methyl groups (CF3) of the anion with highest binding energy to the alkyl chains of the cation with the lowest one. Furthermore with increasing alkyl chain length the peak related to the alkyl group appears at slightly lower binding energy. The more bulk-sensitive XPS spectra reveal only minor differences in the valence band structure for the studied ionic liquids, whereas the more surface-sensitive methods UPS and especially MIES display distinct changes in the peakintensities for varying the alkyl chain length. This is a strong indication for either a non-stoichiometric composition of the upmost molecular layer of the IL-surface and/or a reorientation of the cations, probably turning the alkyl chains to the surface.

"This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively." Keppler, Angela; Himmerlich, Marcel; Ikari, Tomonori; Marschewski, Marcel; Pachomow, Evgenij; Höfft, Oliver; Maus-Friedrichs, Wolfgang; Endres, Frank; Krischok, Stefan Radiation induced degradation effects are studied for a model ionic liquid (IL) - [EMIm]Tf 2 N -in order to distinguish in which way the results of X-ray based material analysis methods can be falsified by the radiation supplied by typical X-ray sources itself. Photoelectron spectroscopy is commonly used for determining the electronic structure of ionic liquids. Degradation effects, which often occur e.g. in organic materials during X-ray or electron irradiation, are potentially critical for the interpretation of data obtained from ionic liquids. The changes of the chemical composition as well as the radiation-induced desorption of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]Tf 2 N) fragments are analysed by X-ray photoelectron spectroscopy (XPS) as well as quadrupole mass spectroscopy (QMS) upon exposure to monochromated or non-monochromated AlKa X-rays from typical laboratory sources. During the irradiation of [EMIm]Tf 2 N, an increasing carbon concentration is observed in both cases and especially the [Tf 2 N] À ion is strongly altered. This observation is supported by the results from the QMS analysis which revealed a variety of different IL fragments that are desorbed during X-ray irradiation. It is shown that the decomposition rate is directly linked to the photon flux on the sample and hence has to be considered when planning an XPS experiment. However, for typical experiments on this particular IL the measurements suggest that the changes are on a larger time scale as typically required for spectra acquisition, in particular if monochromated X-ray sources are used.

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We investigated the effect of ion-beam irradiation of the 3C-SiC(111) surface on the growth of graphene by the SiC surface-decomposition method. When a 3C-SiC(111) surface was irradiated by 1 keV Ar+ions at a dose of 4.5 × 1015cm2in an ultra-high-vacuum chamber and then annealed at 1200 °C for 1 min, the formation of graphene layers was promoted in comparison with that in the absence of ion-beam irradiation. X-ray photoelectron spectroscopy studies showed that Ar ion bombardment of the 3C-SiC(111) caused breakage of surface bonds and helped Si atoms to desorb from the surface.