Holes bound as small polarons to acceptor defects in oxide materials: why are their thermal ionization energies so...

Holes bound to acceptor defects in oxide materials usually need comparatively high energies, of the order of 0.5-1.0 eV, to be ionized thermally to the valence band maximum. It is discussed that this has to be attributed to the stabilization of such holes by mainly short range interactions with the surrounding lattice, leading to the formation of small O(-) polarons. This is tantamount to the localization of the hole at only one of several equivalent oxygen ions next to the defect. The hole stabilizing energies can be determined experimentally from the related intense optical absorption bands. This paper exploits previous phenomenological studies of bound-hole small polarons in order to account for the large hole stabilization energies on this basis. A compilation demonstrates that bound-hole small polarons occur rather often in oxides and also in some related materials. The identification of such systems is based on EPR and optical studies and also on recent advanced electronic structure calculations.