A photoelectron spectroscopy and x-ray absorption study of single crystal with adsorbed Cs: on the origin of the states affected by electron doping and evidence for spatially resolved electron doping

Abstract

The influence of electron doping, via deposition of small amounts of Cs, on the electronic structure of has been studied by high-resolution photoelectron spectroscopy (PES) and x-ray absorption spectroscopy (XAS), utilizing synchrotron radiation. The changes in the electronic structure were monitored by PES of the valence band and of the O 1s, Bi 4f, Bi 5d, Ca 2p and Sr 3d core levels, and by XAS at the O 1s, Cu 2p and Ca 2p edges. The experimental data suggest that the loss of the Fermi edge and the loss of spectral intensity down to about 2 eV below the Fermi level, and the substantial loss of spectral intensity of the pre-edge structure in the O 1s XAS spectrum are mainly due to annihilation of states with O 2p character in the Cu - O layer. It is evident from bulk- and surface-sensitive XAS spectra that the electron doping by Cs affects the electronic structure more strongly close to the surface. This implies that the doping occurs locally and that the charge transfer between the different layers in the unit cell is not uniform. Thus it seems possible to alter the electronic properties of locally through spatially resolved electron doping. When larger amounts of Cs are deposited, a chemical reaction occurs which causes a disruption of the Bi - O layer. This deposition regime is characterized by the presence of caesium oxide and reduced (metallic) Bi.