title: Iron vacancy in tetragonal Fe1-xS crystals and its effect on the structure and superconductivity.
abstract: Understanding the effects of non-stoichiometry on the structure and physical properties of tetragonal Fe chalcogenides is of great importance, especially for developing fascinating superconductivity in this system, which might be very sensitive to the non-stoichiometry. In this study, a series of Fe1-xS single crystals were synthesized by a hydrothermal method, which show varying concentrations of Fe vacancies (0 ≤ x ≤ 0.1) in the structure. Based on the crystal samples, the effects of vacancies on the crystal structure and physical properties were studied. The vacancy-free sample (x = 0) showed a metallic state in resistance and superconductivity below 4.5 K, whereas for the samples with Fe vacancies (x ≥ 0.05), the SC was degraded and the sample exhibited semiconducting behavior. Structural analysis showed that the Fe vacancy decreases the lattice parameter a, but elongates c, leading to enhanced tetragonality in Fe1-xS. Selected-area electron diffraction showed that the vacancy in Fe1-xS was disordered, which is different from the scenario in FeSe-based materials. On combining the abovementioned results with the first-principles calculations, it was speculated that the disappearance of SC in non-stoichiometric Fe1-xS resulted from the localization of the 3d electrons of Fe. Moreover, the accompanied metal-insulator transition induced by Fe vacancy mainly belonged to the Mott mechanism because the vacancy did not significantly alter the band structure. These results not only provide deep insight into the effect of Fe vacancy in Fe chalcogenides, but also provide a basis to effectively induce SC in Fe sulfides by decreasing the number of Fe vacancies.
authors.affiliation: Department of Chemistry, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China. wxyuanwz@163.com.
authors.forename: Zhongnan
authors.initials: Z
authors.lastname: Guo
authors.affiliation: Department of Chemistry, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China. wxyuanwz@163.com.
authors.forename: Fun
authors.initials: F
authors.lastname: Sun
authors.affiliation: Department of Chemistry, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China. wxyuanwz@163.com.
authors.forename: Bingling
authors.initials: B
authors.lastname: Han
authors.affiliation: Department of Physical Chemistry, State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China.
authors.forename: Kun
authors.initials: K
authors.lastname: Lin
authors.affiliation: Department of Chemistry, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China. wxyuanwz@163.com.
authors.forename: Liang
authors.initials: L
authors.lastname: Zhou
authors.affiliation: Department of Chemistry, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, China. wxyuanwz@163.com.
authors.forename: Wenxia
authors.identifier: http://orcid.org/0000-0002-3521-3538
authors.initials: W
authors.lastname: Yuan