Utility and constraint on the use of pump-probe photoelectron spectroscopy for detecting time-resolved surface photovoltage

► The pump-probe PES method for detecting time-resolved surface photovoltage (SPV) is analyzed. ► The simulation for the trip of the electron from the sample to the analyzer revealed its utility and constraint. ► The basic time-resolution is determined by the pump-spot radius and the electron energy. ► The lifetime of the SPV that is shorter than the time-resolution can be correctly monitored.