The Mn(2+)/Mn(3+) state of La0.7Ce0.3MnO3 by oxygen reduction and photodoping

Films of cerium-doped LaMnO3, which has been intensively discussed as an electron-doped counterpart to hole-doped mixed-valence lanthanum manganites during the past decade, were analyzed by x-ray photoemission spectroscopy with respect to their manganese valence under photoexcitation. The comparative analysis of the Mn 3s exchange splitting of La0.7Ce0.3MnO3 (LCeMO) films in the dark and under illumination clearly shows that both oxygen reduction and illumination are able to decrease the Mn valence towards a mixed 2+/3+ state, independently of the film thickness and the degree of CeO2 segregation. Charge-injection from the photoconductive SrTiO3 substrate into the Mn eg band with carrier lifetimes in the range of tens of seconds and intrinsic generation of electron-hole pairs within the films are discussed as two possible sources of the Mn valence shift and the subsequent electron doping.