Electrical and optical properties of narrow-band materials

The electrical and optical properties of materials which are characterized by narrow bands in the vicinity of the Fermi energy are discussed. For such materials, electronic correlations and the electron-phonon coupling must be considered explicitly. Correlations in f bands and in extremely narrow d bands can be handled in the ionic limit of the Hubbard Hamiltonian. It is shown that free carriers in such bands form small polarons which contribute to conduction only by means of thermally activated hopping. Wider bands may also exist near the Fermi energy. Carriers in these bands may form large polarons and give a bandlike contribution to conductivity. A model is proposed for determining the density of states of pure stoichiometric crystals, beginning with the free-ion energy levels, and taking into account the Madelung potential, screening and covalency effects, crystalline-field stabilizations, and overlap effects. Exciton states are considered explicitly. The Franck-Condon principle necessitates the construction of different densities of states for electrical conductivity and optical absorption. Because of the bulk of experimental data presently available, the model is applied primarily to NiO. The many-particle density of states of pure stoichiometric NiO is calculated and is shown to be in agreement with the available experimental data. When impurities are present or nonstoichiometry exists, additional transitions must be discussed from first principles. The case of Li-doped NiO is discussed in detail. The calculations are consistent with the large mass of experimental information on this material. It is concluded that the predominant mechanism for conduction between 200 and 1000 degrees K is the transport of hole-like large polarons in the oxygen 2p band. A method for representing the many-particle density of states on an effective one-electron diagram is discussed. It is shown that if correlations are important, donor or acceptor levels cannot be drawn as localized levels in the energy gap when multiple conduction or valence bands are present. This result comes about because extrinsic ionization energies of two correlated bands differ by an energy which bears no simple relation to the difference in energies of the intrinsic excitations, which are conventionally used to determine the relative positions of the bands.