Local structure of Fe-doped In 2 O 3 $\mathrm{In}_{2}\mathrm{O}_{3}$ films investigated by X-ray absorption fine structure spectroscopy

Abstract

\((\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}\)\((x=0.07, 0.09, 0.16, 0.22, 0.31)\) films were deposited on Si (100) substrates by RF-magnetron sputtering technique. The influence of Fe doping on the local structure of films was investigated by X-ray absorption spectroscopy (XAS) at Fe K-edge and L-edge. For the \((\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}\) films with \(x=0.07, 0.09 \mbox{ and } 0.16\), Fe ions dissolve into \(\mathrm{In}_{2}\mathrm{O}_{3}\) and substitute for \(\mathrm{In}^{3+}\) sites with a mixed-valence state (\(\mathrm{Fe}^{2+}/\mathrm{Fe}^{3+}\)) of Fe ions. However, a secondary phase of Fe metal clusters is formed in the \((\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}\) films with \(x=0.22 \mbox{ and } 0.31\). The qualitative analyses of Fe-K edge extended X-ray absorption fine structure (EXAFS) reveal that the Fe–O bond length shortens and the corresponding Debye–Waller factor (\(\sigma^{2}\)) increases with the increase of Fe concentration, indicating the relaxation of oxygen environment of Fe ions upon substitution. The anomalously large structural disorder and very short Fe–O distance are also observed in the films with high Fe concentration. Linear combination fittings at Fe L-edge further confirm the coexistence of \(\mathrm{Fe}^{2+}\) and \(\mathrm{Fe}^{3+}\) with a ratio of \({\sim}3:2\) (\(\mathrm{Fe}^{2+}: \mathrm{Fe}^{3+}\)) for the \((\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}\) film with \(x=0.16\). However, a significant fraction (\({\sim}40~\mbox{at\%}\)) of the Fe metal clusters is found in the \((\mathrm{In}_{1-x}\mathrm{Fe}_{x})_{2}\mathrm{O}_{3}\) film with \(x=0.31\).