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

Quaternary metal chalcogenides have attracted attention as candidates for absorber materials for inexpensive and sustainable solar energy generation. One of these materials, bournonite (orthorhombic CuPbSbS3), 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(S2CNEt2)2, (1)), bis(diethyldithiocarbamato)lead (II) (Pb(S2CNEt2)2, (2)), and bis(diethyldithiocarbamato)antimony (III) (Sb(S2CNEt2)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 CuPbSbS3. 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.

Direct synthesis of nanostructured silver antimony sulfide powders from metal xanthate precursors.

Silver(I) ethylxanthate [AgS2COEt] (1) and antimony(III) ethylxanthate [Sb(S2COEt)3] (2) have been synthesised, characterised and used as precursors for the preparation of AgSbS2 powders and thin films using a solvent-free melt method and spin coating technique, respectively. The as-synthesized AgSbS2 powders were characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The crystalline AgSbS2 powder was investigated using XRD, which shows that AgSbS2 has cuboargyrite as the dominant phase, which was also confirmed by Raman spectroscopy. SEM was also used to study the morphology of the resulting material which is potentially nanostructured. EDX spectra gives a clear indication of the presence of silver (Ag), antimony (Sb) and sulfur (S) in material, suggesting that decomposition is clean and produces high quality AgSbS2 crystalline powder, which is consistent with the XRD and Raman data. Electronic properties of AgSbS2 thin films deposited by spin coating show a p-type conductivity with measured carrier mobility of 81 cm2 V-1 s-1 and carrier concentration of 1.9 × 1015 cm-3. The findings of this study reveal a new bottom-up route to these compounds, which have potential application as absorber layers in solar cells.

Scalable and Universal Route for the Deposition of Binary, Ternary, and Quaternary Metal Sulfide Materials from Molecular Precursors.

A range of binary, ternary (CFS), and quaternary (CZTS) metal sulfide materials have been successfully deposited onto the glass substrates by air-spray deposition of metal diethyldithiocarbamate molecular precursors followed by pyrolysis (18 examples). The as-deposited materials were characterized by powder X-ray diffraction (p-XRD), Raman spectroscopy, secondary electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy, which in all cases showed that the materials were polycrystalline with the expected elemental stoichiometry. In the case of the higher sulfides, EDX spectroscopy mapping demonstrated the spatial homogeneity of the elemental distributions at the microscale. By using this simple and inexpensive method, we could potentially fabricate thin films of any given main group or transition metal chalcogenide material over large areas, theoretically on substrates with complex topologies.