To reach reasonable conversion efficiencies of approximately 10% and above with CdTe thin film solar cells an activation step involving chlorine at elevated temperatures seems to be necessary before back contact formation. This activation process has been simulated in an ultrahigh-vacuum (UHV) system. Solar cells with a maximum efficiency of 9.1% have been prepared using this process. In addition the effect of the CdCl2 activation process on the electronic properties of each solar cell layer, SnO2, CdS and CdTe has been investigated in situ using photoelectron spectroscopy. The effects of the activation on the Fermi level position of all investigated layers is presented and discussed. (C) 2003 Elsevier Science B.V. All rights reserved.