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The single-crystal growth, stoichiometry, and structure of Rb1-xFe2-ySe2-zSzcrystals with substitution of Se by S are reported. The variation of themagnetic and thermodynamic parameters of samples was studied bydifferential-scanning calorimetry, magnetic susceptibility, conductivity, andspecific heat. The experimental results are discussed within a T-z phasediagram, which includes vacancy-ordered and vacancy-disorderedantiferromagnetic (AFM), superconducting (SC), and non-superconducting phases.The structural study revealed change in the local environment of the Fetetrahedrons depending on substitution: a reduction of the Fe-Fe andFe-Ch(chalcogen) bond lengths and a tendency for the six out of eight bondangles to approach values for a regular tetrahedron suggesting a reduction ofstructural distortions with substitution. With increasing substitution, alowering of the superconducting transition temperature Tc was observed; thepercolation threshold for the SC state is located at the substitution z = 1.2.The SC state was found to coexist with the AFM state that persists in allsamples independent of substitution. The temperature of the transition into theAFM state TN shows a monotonous decrease indicating a weakening of the AFMinteractions with increasing substitution. The AFM phase exhibits aniron-vacancy-ordered structure below the structural transition at Ts. Thetemperature Ts shows a non-monotonous variation: a decrease with increasing zup to 1.3, followed by an increase for further increasing z. The suppression ofthe superconductivity with substitution is accompanied by a significantreduction of the density of states at the Fermi energy and a weakening of theelectronic correlations in the studied system.

Structure, superconductivity, and magnetism in Rb1-xFe1.6Se2-zSz