In-situ Electrochemical X-ray Diffraction: A Rigorous Method to Navigate within Phase Diagrams Reveals β-Fe1+xSe as Superconductor for All x

We report the precise postsynthetic control of the composition of beta-Fe1+xSe by electrochemistry with simultaneous tracking of the associated structural changes via in situ synchrotron X-ray diffraction. We access the full phase width of 0.01<0.04 and identify the superconducting state below 8 K, which in contrast to earlier reports is independent of the composition. However, in a second set of in situ X-ray diffraction experiments, we demonstrate that beta-Fe1+xSe forms a new phase in the presence of oxygen above a 100 degrees C which has the same anti-PbO type structure but is not superconducting down to 1.8 K. The latter process can be reversed electrochemically to reinstate the superconducting state. These observations exploit the exquisite control afforded by electrochemistry in contrast with classical approaches of chemical synthesis.