Photo-assisted Ultrafast Scanning Electron Microscopy (USEM) maps the dynamics of surface photovoltages and local electric fields in semiconducting samples. Photovoltages and their gradients close to surface affect the emission yield and the detection efficiency of secondary electrons (SE), leading to photoexcited SE 2D patterns. In this work, we present a method to characterize the evolution of the patterns up to ultrafast regime. These results reveal the role of surface states in affecting the external field dynamics at picoseconds. Moreover, we show that tiny changes in surface preparation express deeply different photoexcited voltage signals. We investigate the relation between the surface chemistry of Si and photo-induced SE contrast