Magnetic suppression for a possible Fe-poor organic–inorganic hybrid superconductor Fe14Se16(tepa)0.8 (tepa = tetraethylenepentamine) with a superconducting transition at ∼42 K

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Composition/structure-dependent superconductivity for FeSe-based superconductors attracted great attention not only due to their high superconducting transition temperatures (TC), but also for understanding the origin of iron-based superconductivity. Here, we report a new Fe-poor organic-inorganic hybrid material Fe14Se16(tepa)0.8 with a paramagnetic-diamagnetic transition at ∼42 K grown by a high-temperature organic-solution-phase method with soluble iron/selenium sources in a tepa solution, alternative to previous intercalation strategies. The Fe14Se16(tepa)0.8 phase is in a tetragonal layered hybrid structure with a nanoplate shape. Composition analyses reveal a Fe-poor characteristic of the hybrid in contrast to previous FeSe-intercalated superconductor, and selected area electron diffraction pattern is featured by Fe3Se4 superstructures with a √2 × √2 of Fe vacancy order. Ab initio density functional calculations show that minus Fe3Se4 ions are stable in the hybrid and ∼0.25e−/Fe0.75Se is obviously larger than the reported values of approximately 0.2e−/FeSe in other FeSe-intercalated superconductors. Typical hysteresis loops and temperature dependence of dc/ac susceptibilities of the Fe14Se16(tepa)0.8 measured below ∼42 K suggest a presence of the Meissner effect in this material. Effects of synthesis conditions on structures and magnetic properties of the hybrids show a magnetic evolution from a long-range ferrimagnetic (FIM) order of Fe14Se16(tepa) to a coexistence of FIM and superconducting (SC) orders of Fe14Se16(tepa)0.9 and an SC order of Fe14Se16(tepa)0.8. X-ray absorption spectrum (XAS) confirms the presence of ferric/ferrous irons. Mössbauer studies reveal that the high-TC superconductivity originates from a suppression of the FIM order through tuning the spin states of irons from high-spin Fe3+ (S = 5/2) and Fe2+ (S = 2) in the Fe14Se16(tepa) to low-spin Fe3+ (S = 1/2) and Fe2+ (S = 0) in the Fe14Se16(tepa)0.8. Although no zero resistance is detected even at a temperature of 2 K, the resistivity at 2 K decreases by more than 1600 times compared to that in a normal state calculated by a variable range hopping (VRH) model, suggesting that the high-TC superconductivity of Fe14Se16(tepa)0.8 is possible.