An angle-resolved photoemission spectroscopy study allowed us to identify cation interdiffusion and stoichiometry gradients at the interface between a nanosized TiO2 blocking layer and a transparent conductive Cd-Sn oxide substrate. A stoichiometry gradient for the Sn cations is already found in the bare Cd-Sn oxide layer. When TiO2 ultrathin layers are deposited by RF sputtering on the Cd-Sn oxide layer, Ti is found to partially replace Sn, resulting in a Cd-Sn-Ti mixed oxide layer with a thickness ranging from 0.85 to 3.3 nm. The band gap profile across the junction has been reconstructed for three TiO2 layers, resulting in a valence band offset decrease (and a conduction band offset increase) with the blocking layer thickness. The results are related to the cell efficiencies in terms of charge injection and recombination processes.
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