Quantification of the EELS near-edge structures to study Mn doping in oxides

The L(3) to L(2) white-line intensity ratios of Mn in solid solution in yttria-stabilized zirconia and in Mn oxide standards are measured using different approaches, We show that the L(3)/L(2) ratio alone cannot be used as a means of deducing the oxidation state and that a combined analysis of this ratio and the normalized white-line intensity is required to retrieve the ionicity and magnetic state of the Mn dopant with respect to reference standards. Changes as a function of composition are measured and these are discussed in terms of variations in crystal field parameters associated with possible vacancy interaction. From the oxygen near-edge structure we analyse the localization of the extra electron charge introduced by the dopant and discuss the possible effects of the association of this extra charge with oxygen vacancies in relation to the macroscopic ion conductivity.