Molecular precursor-mediated facile synthesis of photo-responsive stibnite Sb2S3 nanorods and tetrahedrite Cu12Sb4S13 nanocrystals

Abstract

Stibnite Sb₂S₃ and tetrahedrite Cu₁₂Sb₄S₁₃ nanostructures being economical, environmentally benign and having a high absorption coefficient are highly promising materials for energy conversion applications. However, producing these materials especially tetrahedrite in the phase pure form is a challenging task. In this report we present a structurally characterized single source molecular precursor [Sb(4,6-Me₂pymS)₃] for the facile synthesis of binary Sb₂S₃ as well as ternary Cu₁₂Sb₄S₁₃ in oleylamine (OAm) at a relatively lower temperature. The as-prepared Sb₂S₃ and Cu₁₂Sb₄S₁₃ nanostructures were thoroughly checked for their phase purity, elemental composition and morphology by powder X-ray diffraction (pXRD), electron dispersive spectroscopy (EDS) and electron microscopy techniques. pXRD and EDS studies confirm the formation of phase pure, crystalline orthorhombic Sb₂S₃ and cubic Cu₁₂Sb₄S₁₃. The SEM, TEM and HRTEM images depict the formation of well-defined nanorods and nearly spherical nanocrystals for Sb₂S₃ and Cu₁₂Sb₄S₁₃, respectively. The Sb₂S₃ nanorods and Cu₁₂Sb₄S₁₃ nanocrystals exhibit an optical bandgap of ∼1.88 and 2.07 eV, respectively, which are slightly blue-shifted relative to their bulk bandgap, indicating the quantum confinement effect. Finally, efficient photoresponsivity and good photo-stability were achieved in the as-prepared Sb₂S₃ and Cu₁₂Sb₄S₁₃ nanostructure-based prototype photo-electrochemical cell, which make them promising candidates for alternative low-cost photon absorber materials.