Effects of Zn impurities on the electronic properties of Pr doped CaTiO 3

Abstract

Microcosmic investigations of weak red-emitting materials are crucial for their further development and application. In this work, we have focused on the band structures and electronic properties of Pr mono- and (Zn, Pr) co-doped CaTiO 3 using density functional theory. Zn substitution for Ca or Ti tends to form clusters energetically with Pr substituting for Ca in CaTiO 3. In Pr mono-doped CaTiO 3, the O 2p→Ti 3d transition in CaTiO 3 host corresponds to the centered 330 nm excitation spectra. The gap states above the valence band of ∼1.30 eV and ∼2.06 eV are hybridized by Pr 4f, O 2p and Ti 3d orbitals. They are mainly due to Pr 4f orbitals in CaTiO 3:Pr. The former gap level is related to red emission at 614 nm due to 1D 2→ 3H 4 transition of Pr 3+ activator. The latter is related to the excitation spectra centered at 380 nm due to the low-lying Pr-to-mental intervalence charge transfer transitions (Pr 3+–O 2−–Ti 4+⇌Pr 4+–O 2−–Ti 3+). The band structures of (Zn, Pr) co-doped CaTiO 3 keep the similar gap levels to those in Pr mono-doped CaTiO 3. The incorporation of Zn brings out the two stronger localized gap states, which are hybridized by Pr 4f, O 2p and Ti 3d orbitals, in comparison with those in Pr mono-doped CaTiO 3. Therefore, when Zn impurities are added into Pr doped CaTiO 3, the present calculations visualize the two enhanced levels and the distorted structures around Pr.