Time dependent changes in 13.5 nm extreme ultraviolet (EUV) reflectivity of Ru mirrors due to variations in surface composition were investigated. The surface properties of Ru films were analyzed in situ by means of X-ray photoelectron spectroscopy (XPS), and further verified by Auger electron spectroscopy (AES). Moreover, the impact on EUV reflectivity (EUVR) with time was examined in situ via continuous and/or discrete EUV exposures. The rapid decrease in EUVR was observed in the presence of photoelectrons (PEs) from Ru mirror of the EUV setup, whereas no significant variation was recorded by screening out additional PEs. Detailed XPS and AES analyses suggest that carbon deposition via dissociation of residual hydrocarbons plays a dominant role in the presence of additional PEs, and thus reduces the reflectivity rapidly. Using EUV photoelectron spectroscopy, systematic reduction of the secondary electron yield from the Ru mirror surface was observed in consecutive scans, and therefore supports the formation of carbonaceous Ru surface in the presence of additional PEs. © 2012 American Institute of Physics.