Crystal structure and properties of a new member of oxy-bismuth-sulfide family SmO 0.5 F 0.

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We have synthesized two new Eu-based compounds, EuSr2Bi2S4F4 and Eu2SrBi2S4F4 which are derivatives of Eu3Bi2S4F4, an intrinsic superconductor with Tc = 1.5 K. They belong to a tetragonal structure (SG: I4/mmm, Z = 2), similar to the parent compound Eu3Bi2S4F4. Our structural and 151 Eu Mössbauer spectroscopy studies show that in EuSr2Bi2S4F4, Eu-atoms exclusively occupy the crystallographic 2a-sites. In Eu2SrBi2S4F4, 2a-sites are fully occupied by Eu-atoms and the other half of Eu-atoms and Sr-atoms together fully occupy 4e-sites in a statistical distribution. In both compounds Eu atoms occupying the crystallographic 2a-sites are in a homogeneous mixed valent state ~ 2.6 -2.7. From our magnetization studies in an applied H  9 Tesla, we infer that the valence of Eu-atoms in Eu2SrBi2S4F4 at the 2a-sites exhibits a shift towards 2+. Our XPS studies corroborate the occurrence of valence fluctuations of Eu and after Ar-ion sputtering show evidence of enhanced population of Eu 2+ -2 states. Resistivity measurements, down to 2 K suggest a semi-metallic nature for both compounds.

We investigate the external hydrostatic pressure effect on the superconducting transition temperature (Tc) of new layered superconductors Bi4O4S3 and NdO0.5F0.5BiS2. Though the Tc is found to have a moderate decrease from 4.8 K to 4.3 K (dTconset/dP = –0.28 K/GPa) for Bi4O4S3 superconductor, the same increases from 4.6 K to 5 K (dTconset/dP = 0.44 K/GPa) up to 1.31 GPa followed by a sudden decrease from 5 K to 4.7 K up to 1.75 GPa for NdO0.5F0.5BiS2 superconductor. The variation of Tc in these systems may be correlated to an increase or decrease of the charge carriers in the density of states under externally applied pressure. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)