The Valence Transition Model of Pseudogap, Charge-Order and Superconductivity in Electron- and Hole-Doped Copper Oxides

TL;DR

This paper proposes a valence transition model for cuprates, explaining pseudogap, charge order, and superconductivity through a discrete ionicity change and charge density wave states, unifying various experimental observations.

Contribution

It introduces a comprehensive valence transition framework that links doping, charge order, and superconductivity in cuprates and iridates, with testable predictions.

Findings

Discontinuous Cu ionicity change at optimal doping and pseudogap transition.

Coexistence of charge density wave and broken rotational symmetry in the pseudogap state.

Superconductivity arises from destabilization of a paired Wigner crystal in a quarter-filled band.

Abstract

We present a valence transition model for electron- and hole-doped cuprates, within which there occurs a discrete jump in ionicity Cu$^{2+} \to$ Cu$^{1+}$ upon doping, at or near optimal doping in the electron-doped compounds and at the pseudogap phase transition in the hole-doped materials. Doped cuprates have negative charge-transfer gaps, just as rare earth nickelates and BaBiO$_3$. Because of strong correlations and small $d-p$ electron hoppings the systems behave as effective $\frac{1}{2}$-filled Cu-band in the undoped state, and as correlated two-dimensional geometrically frustrated nearly $\frac{1}{4}$-filled O-band in the doped state. The theory gives the simplest yet most comprehensive understanding of experiments in the normal states. The robust antiferromagnetism in the conventional T$^\prime$ crystals, the strong role of oxygen deficiency in driving superconductivity and charge carrier sign corresponding to holes at optimal doping are all manifestations of the same quantum state. In the hole-doped pseudogapped state, a biaxial commensurate period 4 charge density wave state of O$^{1-}$-Cu$^{1+}$-O$^{1-}$ spin-singlets coexists with broken rotational C$_4$ symmetry. Finite domains of this broken symmetry state will exhibit the polar Kerr effect. Superconductivity within the model results from a destabilization of the $\frac{1}{4}$-filled band paired Wigner crystal [Phys. Rev. B {\bf 93}, 165110 and {\bf 93}, 205111]. We posit that a similar valence transition, Ir$^{4+} \to$ Ir$^{3+}$, occurs in electron-doped SrIr$_2$O$_4$. We make testable theoretical predictions on cuprates and iridates. Finally, we note that there exist an unusually large number of unconventional superconductors that exhibit superconductivity proximate to exotic charge ordered states, whose bandfillings are also $\frac{1}{4}$, exactly where the paired Wigner crystal is most stable.