Calorimetric evidence for two phase transitions in Ba1−xKxFe2As2 with fermion pairing and quadrupling states

Materials that break multiple symmetries allow the formation of four-fermion condensates above the superconducting critical temperature (Tc). Such states can be stabilized by phase fluctuations. Recently, a fermionic quadrupling condensate that breaks the Z2 time-reversal symmetry was reported in Ba1−xKxFe2As2. A phase transition to the new state of matter should be accompanied by a specific heat anomaly at the critical temperature where Z2 time-reversal symmetry is broken ( $${T}_{{{{{{{{\rm{c}}}}}}}}}^{{{{{{{{\rm{Z2}}}}}}}}} \, > \, {T}_{{{{{{{{\rm{c}}}}}}}}}$$ T c Z2 > T c ). Here, we report on detecting two anomalies in the specific heat of Ba1−xKxFe2As2 at zero magnetic field. The anomaly at the higher temperature is accompanied by the appearance of a spontaneous Nernst effect, indicating the breakdown of Z2 symmetry. The second anomaly at the lower temperature coincides with the transition to a zero-resistance state, indicating the onset of superconductivity. Our data provide the first example of the appearance of a specific heat anomaly above the superconducting phase transition associated with the broken time-reversal symmetry due to the formation of the novel fermion order.