Small-polaron versus band conduction in some transition-metal oxides

Abstract In this paper an attempt is made to establish the nature of free charge carriers and of charge carriers bound to centres in p-type NiO, CoO and MnO and in n-type MnO and α-Fe2O3. For free charge carriers, d.c. conductivity, Seebeck coefficient and Hall effect are considered. Effects arising from inhomogeneous conduction and impurity conduction are discussed. Impurity conduction appears to have a strong influence on transport properties in the case of α-Fe2O3, less so in NiO, whereas no influence of this effect has been found in CoO and MnO. It is shown that NiO and CoO do not exhibit the features characteristic of small-polaron conductors but rather can be consistently conceived of as large-polaron band semiconductors. It is suggested that magnetic resistance due to exchange coupling between charge-carrier spin and cation spins plays an important role. The anomalous behaviour of the Hall effect in NiO and α-Fe2O3 is extensively discussed. In contradistinction to NiO, CoO and n-type MnO, free char...

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