Electronic properties of phases in the quasi-binary Bi2Se3–Bi2S3 system
We explored the properties of the quasi-binary Bi2Se3–Bi2S3 system over a wide compositional range. X-ray diffraction analysis demonstrates that rhombohedral crystals can be synthesized within the solid solution interval 0–22 mol% Bi2S3, while at 33 mol% Bi2S3 only orthorhombic crystals are obtained. Core level photoemission spectroscopy reveals the presence of Bi3+, Se2− and S2− species and the absence of metallic species, thus indicating that S incorporation into Bi2Se3 proceeds prevalently through the substitution of Se with S. Spin- and angle-resolved photoemission spectroscopy shows that topological surface states develop on the surfaces of the Bi2Se3−ySy (y ≤0.66) rhombohedral crystals, in close analogy with the prototypical case of Bi2Se3, while the orthorhombic crystals with higher S content turn out to be trivial semiconductors. Our results connect unambiguously the phase diagram and electronic properties of the Bi2Se3–Bi2S3 system.