Electrical transport in light rare-earth molybdates

Abstract

Rare-earth molybdates of the type R₂(MoO₄)₃ with R=La, Ce, Pr, Nd, Sm and Eu were prepared and characterized, and the electrical conductivity, σ and Seebeck coefficient, S in the temperature range 450–1200 K were measured. These molybdates are concluded to be insulating solids with a band gap which increases slowly going down the series from 2.30 eV for La molybdate to 3.20 eV for Eu molybdate. The plots of log σ and S versus T ⁻¹ show, in general, three linear regions with two break temperatures T ₁ and T ₂ occurring due to a change in the conduction mechanism. At higher temperatures the intrinsic conduction in these solids occurs via a band mechanism. The O²⁻ ∶2p and Mo⁶⁺ ∶4d orbitals form the valence and conduction bands, respectively. These bands are the main support of conduction in La, Sm and Eu molybdates; however, for Ce, Pr and Nd molybdates 4fⁿ levels fall within the band gap and become very effective in electrical conduction. The main charge-carrying entities seem to be electrons in Ce, Pr and Nd molybdates and holes in La, Sm and Eu molybdates. On the basis of mobility calculations of charge carriers it is concluded that the charge carriers in these bands become polarons which are, in fact, the charge carrying entities. At lower temperatures electrical conduction is mainly extrinsic. Cerium molybdate shows a semiconductor-semimetal transition around 940 K.