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Several superconducting transition temperatures in the range of 30-40 K werereported in the recently discovered intercalated FeSe sytem (A1-xFe2-ySe2, A =K, Rb, Cs, Tl). Although the superconducting phases were not yet conclusivelydecided, more than one magnetic phase with particular orders of iron vacancyand/or potassium vacancy were identified, and some were argued to be the parentphase. Here we show the discovery of the presence and ordering of iron vacancyin nonintercalated FeSe (PbO-type tetragonal {\beta}-Fe1-xSe). Three types ofiron-vacancy order were found through analytical electron microscopy, and onewas identified to be nonsuperconducting and magnetic at low temperature. Thisdiscovery suggests that the rich-phases found in A1-xFe2-ySe2 are not exclusivein Fe-Se related superconductors. In addition, the magnetic {\beta}-Fe1-xSephases with particular iron-vacancy orders are more likely to be the parentphase of FeSe superconducting system, instead of the previously assigned{\beta}-Fe1+{\delta}Te.

Fe-vacancy order and superconductivity in PbO-type tetragonal {\beta}-Fe1-xSe