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Evidence for time-reversal symmetry breaking of the superconducting state near twin-boundary interfaces in FeSe

Junctions and interfaces consisting of unconventional superconductors provide an excellent experimental playground to study exotic phenomena related to the phase of the order parameter. Not only the complex structure of unconventional order parameters have an impact on the Josephson effects, but also may profoundly alter the quasi-particle excitation spectrum near a junction. Here, by using spectroscopic-imaging scanning tunneling microscopy, we visualize the spatial evolution of the local density of states (LDOS) near twin boundaries (TBs) of the nodal superconductor FeSe. The $π/2$ rotation of the crystallographic orientation across the TB twists the structure of the unconventional order parameter, which may, in principle, bring about a zero-energy LDOS peak at the TB. The LDOS at the TB observed in our study, in contrast, does not exhibit any signature of a zero-energy peak and an apparent gap amplitude remains finite all the way across the TB. The low-energy quasiparticle excitations associated with the gap nodes are affected by the TB over a distance more than an order of magnitude larger than the coherence length $ξ_{ab}$. The modification of the low-energy states is even more prominent in the region between two neighboring TBs separated by a distance $\approx7ξ_{ab}$. In this region the spectral weight near the Fermi level ($\approx\pm$0.2~meV) due to the nodal quasiparticle spectrum is almost completely removed. These behaviors suggest that the TB induces a fully-gapped state, invoking a possible twist of the order parameter structure which breaks time-reversal symmetry.