Structural and optical evolution in CeO2 films induced by aluminum doping: A comprehensive study

Abstract

This study investigates the impact of aluminum (Al) doping and oxygen vacancies on the structural, electronic, and optical properties of Cerium Oxide (CeO2) films. The films were fabricated on glass substrates using the solgel spin coating method for both undoped and Al doped CeO2. Theoretical insights from the DFT + U + V method further explore how Al doping and oxygen vacancies influence the electronic structure and optical behavior of ceria. Experimentally, Al doping was found to increase the lattice parameters and reduce the crystallite size without forming secondary phases. Raman spectroscopy revealed a shift to lower wavenumbers in Al-doped samples, while XPS analysis confirmed the presence of both Ce3+ and Ce4+ oxidation states, along with Al3+ and O2- ions. Optical measurements showed a decrease in the optical band gap from 3.14 eV to 2.93 eV as the Al concentration increased to 5 %. Additionally, the optical dielectric constant slightly decreased, whereas optical conductivity improved with the incorporation of aluminum. Theoretical calculations show that oxygen vacancies were shown to reduce the band gap by introducing localized Ce3+ mid-gap states, while Al doping led to a gradual narrowing of the band gap without creating new states within it. The combination of Al doping and oxygen vacancies resulted in both further band gap narrowing and the appearance of mid-gap states. Optical property calculations revealed that both oxygen vacancies and Al doping reduced the intensity of the dielectric functions at 310 nm. Moreover, these two factors had opposing effects on the electron energy loss spectrum (EELS) at low energies: Al doping induced high-intensity peaks, while oxygen vacancies diminished these peaks.