Neutral and metallic vs. charged and semiconducting surface layer in acceptor doped CeO2

The monomolecular surface layer of acceptor doped CeO2may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures. Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9–x(SDC) containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O2–x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions. The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO. It leads to the following predictions: the highly reduced surface of SDC is metallic and neutral, the metallic surface electron density of state is gs= 0.9 × 1038J-1·m-2(1.4 × 1015eV-1·cm-2), the electron effective mass is meff,s=3.3me, and the phase diagram of the reduced surface has the α(fcc) structure as in the bulk. In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting. The surface of PCO maintains high Pr3+defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk. The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO2are reviewed, as well as the key theoretical considerations applied in coping with this problem. For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.