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

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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 charge carriers in p-type MnO seem to have small-polaron character. For charge carriers bound to centres, dielectric loss, high-frequency conduction and optical absorption are considered. The dielectric loss data relate to Li or Na centres in NiO, CoO and MnO and to Ti, Zr, Sn, Ta, Nb and presumably oxygen vacancy centres in α-Fe2O3. It is concluded from the dependence of dielectric loss on frequency and temperature that bound charge carriers are small polarons. It is shown for the cases of NiO and α-Fe2O3 that apart from small-polaron effects, disorder due to locally varying electric fields determines the nature of dielectric loss. The small-polaron character of bound charge carriers in NiO is corroborated by the behaviour of high-frequency conduction and optical absorption due to centres and also by the magnitude of impurity conduction.