Synchrotron radiation photoemission spectroscopy of the oxygen modified CrCl3 surface

We investigate the experimentally challenging CrCl3 surface by photon energy dependent photoemission (PE). The core and valence electrons after cleavage of a single crystal, either in a ultra-high vacuum (UHV) or in air, are studied by keeping the samples at 150 °C, aiming at confirming the atomic composition with respect to the expected bulk atomic structure. A common spectroscopic denominator revealed by data is the presence of a stable, but only partially ordered Cl-O-Cr surface. The electronic core levels (Cl 2p, Cr 2p and 3p), the latter ones of cumbersome component determination, allowed us to quantify the electron charge transfer to the Cr atom as a net result of this modification and the increased exchange interaction between metal and ligand atoms. In particular, the analysis of multiplet components by the CMT4XPS code evidenced the charge transfer to be favored, and similarly the reduced crystal field due to the established polarization field. Though it is often claimed that a significant amount of Cl and Cr atomic vacancies has to be included, such a possibility can be excluded on the basis of the sign and the importance of the shift in the binding energy of core level electrons. The present methodological approach can be of great impact to quantify the structure of ordered sub-oxide phases occurring in mono or bi-layer Cr trihalides.