Stacking Variants and Superconductivity in the Bi–O–S System

High-temperature superconductivity has a range of applications from sensors to energy distribution. Recent reports of this phenomenon in compounds containing electronically active BiS2 layers have the potential to open a new chapter in the field of superconductivity. Here we report the identification and basic properties of two new ternary Bi–O–S compounds, Bi2OS2 and Bi3O2S3. The former is non-superconducting; the latter likely explains the superconductivity at Tc = 4.5 K previously reported in “Bi4O4S3”. The superconductivity of Bi3O2S3 is found to be sensitive to the number of Bi2OS2-like stacking faults; fewer faults correlate with increases in the Meissner shielding fractions and Tc. Elucidation of the electronic consequences of these stacking faults may be key to the understanding of electronic conductivity and superconductivity which occurs in a nominally valence-precise compound.