Time-reversal symmetry breaking superconductivity with electronic glass in nickelate (La, Pr, Sm)3Ni2O7 films

The discovery of Ruddlesden-Popper (R-P) nickelate superconductors under high pressure heralds a new chapter of high-transition temperature (high-Tc) superconductivity. Recently, ambient-pressure superconductivity is achieved in R-P bilayer nickelate thin films through epitaxial compressive strain, unlocking the potential for understanding the nature of the unconventional superconductivity. Here, through electrical transport study, we report the discovery of time-reversal symmetry (TRS) breaking superconductivity with electronic glass in bilayer nickelate (La, Pr, Sm)3Ni2O7 films. It emerges in the lower-temperature regime of superconducting transition to the zero-resistance state, and is captured by three remarkable characteristics: 1. Unconventional magnetoresistance hysteresis, the direct evidence of TRS breaking, which is robust under different magnetic field orientations and differs fundamentally from trapped vortices or long-range-ordered magnetism. Successive oxygen reductions simultaneously weaken both the superconductivity and hysteresis, revealing their mutual connections to selective electronic orbitals. 2. Magnetic field history-dependence and zero-field non-reciprocity in the current-voltage responses, further substantiating the intrinsic and spontaneous TRS breaking. 3. Logarithmically slow resistance relaxations upon the removal of magnetic field, the hallmarks of glassy dynamics. Distinguished by the striking magnetic field history- and time-dependent properties, our findings uncover an unprecedented superconducting state in the nickelate superconductors, providing phenomenological and conceptual advances for future research on high-Tc superconductivity.