Evolution of the optical properties and the electrical resistivity of CaMnO3 during the substitution of Mo for Mn ions

The reflectance, the optical density, and the optical conductivity spectra of CaMn_{1 ? x} Mo _x O₃ (x ≤ 0.07) polycrystals are studied over a wide spectral region. The substitution of Mo⁶⁺ ions for Mn⁴⁺ ions leads to a strong decrease in the first high-energy phonon band, which is related to vibrations in the MnO₆ octahedron. The appearance of band-type charge carriers is detected in CaMn_{1 ? x} Mo _x O₃ with x ≤ 0.04, and carrier localization is observed in CaMn_0.93Mo_0.07O₃. This localization increases at T < 160 K, i.e., during the transition from the paramagnetic to the antiferromagnetic state with orbital ordering and a monoclinic structure. The optical conductivity spectrum of CaMn_0.93Mo_0.07O₃ exhibits a strong shift of fundamental absorption bands, which is associated with a change in the band structure because of a decrease in the splitting of the 3d levels of Mn in the crystal field.