Negative U centers, percolation, and the insulator-metal transition in high-Tc superconductors

The mechanism of formation of −U centers in high-Tc superconductors (HTSCs) is considered. It is shown that the transition from the insulator to the metallic state on doping passes through a certain range of dopant concentrations in which it becomes possible for local transitions of singlet electron pairs to occur from oxygen ions to two neighboring cations (a −U center), while single-electron transitions are still forbidden. Conduction arises in such systems at a concentration of −U centers exceeding the percolation threshold for the orbitals of singlet hole pairs. A phase diagram constructed on the basis of the proposed model for the HTSC compounds of the Ln-214 class is in complete agreement with experiment. The mechanisms of formation and relaxation of free hole carriers are considered. It is shown that a distinctive feature of the normal state of HTSCs is the dominant contribution of electron-electron scattering to the charge carrier relaxation processes. It is concluded from the analysis presented that HTSCs comprise a special class of solids in which a nonstandard mechanism of superconductivity, different from the BCS mechanism, is realized.