Molecular Precursor Route to Bournonite (CuPbSbS₃) Thin Films and Powders

Abstract

Quaternary metal chalcogenides have attracted attention as candidates for absorber materials for inexpensive and sustainable solar energy generation. One of these materials, bournonite (orthorhombic CuPbSbS 3 ), has attracted much interest of late for its properties commensurate with photovoltaic energy conversion. This paper outlines the synthesis of bournonite for the first time by a discrete molecular precursor strategy. The metal dithiocarbamate complexes bis(diethyldithiocarbamato)copper (II) (Cu(S 2 CNEt 2 ) 2 , ( 1 )), bis(diethyldithiocarbamato)lead (II) (Pb(S 2 CNEt 2 ) 2 , ( 2 )), and bis(diethyldithiocarbamato)antimony (III) (Sb(S 2 CNEt 2 ) 3 , ( 3 )) were prepared, characterized, and employed as molecular precursors for the synthesis of bournonite powders and the thin film by solvent-less pyrolysis and spray-coat-pyrolysis techniques, respectively. The polycrystalline powders and thin films were characterized by powder X-ray diffraction (p-XRD), which could be indexed to orthorhombic CuPbSbS 3 . The morphology of the powder at the microscale was studied using scanning electron microscopy (SEM). Energy-dispersive X-ray spectroscopy (EDX) was used to elucidate an approximately 1:1:1:3 Cu/Pb/Sb/S elemental ratio. An optical band gap energy of 1.55 eV was estimated from a Tauc plot, which is close to the theoretical value of 1.41 eV.

A facile synthetic route toward phase-pure colloidal Cu2GeS3 nanostructures mediated through metal xanthate precursors

“…Lewis's research group has extensively explored the versatility of metal xanthates and thiocarbamates for the phase-pure preparation of various exotic multinary metal sulfides. [14][15][16][17] Similarly, Revaprasadu et al have also investigated the suitability of xanthates and thiocarbamates for the preparation of several important nanosized metal sulfides. [18][19][20] However, a thorough literature study has revealed that xanthates have not been explored for the preparation of technologically important Cu 2 GeS 3 nanocrystals.…”

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

“…It is well reported in the literature that the volatile nature and possibility of sublimation at an elevated temperature in some antimony complexes with a sulfur-containing ligand restrict the exact determination of the nature of residue on the basis of weight loss percentage. 42,43 In order to investigate the nature of residue, the complex 1 was furnace heated at a rate of 10 °C min −1 under flowing Ar up to 330 °C. The temperature was maintained for 1 h, after which the heating was stopped and the furnace was cooled to room temperature under flowing Ar.…”

Film Fabrication of Perovskites and their Derivatives for Photovoltaic Applications via Chemical Vapor Deposition

“…In fact, solutions could also be utilized in CVD, such as with aerosol-assisted CVD (AACVD). As an emerging method with a large potential in industrial applications, AACVD has been widely used in the thin-film deposition of traditional functional materials, such as transparent conducting oxides and superhydrophobic materials. , Recently, semiconductor films of perovskites, bournonites, and their derivatives deposited via AACVD have also been investigated as the absorber layer in solar cells. ,− AACVD combines the benefits of solution- and vapor-based deposition. There are basically two kinds of AACVD setups, including hot-wall and cold-wall reactor (Figure ).…”