Space-charge effects in high-energy photoemission

Pump-and-probe photoelectron spectroscopy (PES) with femtosecond pulsed sources opens new perspectives in the investigation of the ultrafast dynamics of physical and chemical processes at the surfaces and interfaces of solids. Nevertheless, for very intense photon pulses a large number of photoelectrons are simultaneously emitted and their mutual Coulomb repulsion is sufficiently strong to significantly modify their trajectory and kinetic energy. This phenomenon, referred as space-charge effect, determines a broadening and shift in energy for the typical PES structures and a dramatic loss of energy resolution. In this article we examine the effects of space charge in PES with a particular focus on time-resolved hard X-ray (similar to 10 keV) experiments. The trajectory of the electrons photoemitted from pure Cu in a hard X-ray PES experiment has been reproduced through N-body simulations and the broadening of the photoemission core-level peaks has been monitored as a function of various parameters (photons per pulse, linear dimension of the photon spot, photon energy). The energy broadening results directly proportional to the number N of electrons emitted per pulse (mainly represented by secondary electrons) and inversely proportional to the linear dimension a of the photon spot on the sample surface, in agreement with the literature data about ultraviolet and soft X-ray experiments. The evolution in time of the energy broadening during the flight of the photoelectrons is also studied. Despite its detrimental consequences on the energy spectra, we found that space charge has negligible effects on the momentum distribution of photoelectrons and a momentum broadening is not expected to affect angle-resolved experiments. Strategy to reduce the energy broadening and the feasibility of hard X-ray PES experiments at the new free-electron laser facilities are discussed. (C) 2016 Elsevier B.V. All rights reserved.