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

Yasser T Alharbi,David J Lewis,Firoz Alam,Mohamed Missous,Khaled Parvez

doi:10.1021/acs.inorgchem.1c02001

Yasser T Alharbi, David J Lewis + Show 3 more

Open Access

https://doi.org/10.1021/acs.inorgchem.1c02001

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Journal: Inorganic chemistry	Publication Date: Aug 12, 2021
Citations: 10	License type: CC BY 4.0

Affiliation: University of Manchester

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 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.

Highlights

Energy from fossil fuel is problematic as the source is inherently unsustainable and the products of combustion are associated with irreversible and dire climate outcomes.[1]
The Scanning electron microscopy (SEM) images of the powders show that the mixture was drop-casted onto a glass substrate
The crystallites have sheet-like morphology and there were no significant changes in morphology noticed when the growth temperature was increased

Summary

■ INTRODUCTION

Energy from fossil fuel is problematic as the source is inherently unsustainable and the products of combustion are associated with irreversible and dire climate outcomes.[1]. For example, reported the synthesis of ternary copper iron sulfide thin films by simple thermolysis of a mixture of Cu and Fe xanthates.[25] We have demonstrated that mixing of metal dithiocarbamate precursors allows the spray-coating of metal sulfide thin films including examples of binary (1 precursor), ternary (2 precursors), and quaternary (3 precursors) metal sulfide materials (n = 18).[26] For the synthesis of bournonite, this mixed precursor approach could be used to explore off-stoichiometric materials and doped and alloyed derivatives, which are known or predicted to exist.[24,27] Second, molecular precursors tend to form kinetic products due to the rapid decomposition and ultimate crystallization steps involved, which could sidestep the potential formation of PbS and Sb2S3 side products.[18,24] We have recently observed the formation of kinetic products, for example, in the formation of molybdenum−tungsten trioxide alloys.[28] In this paper, we explore for the first time the use of metal dithiocarbamate complexes as precursors toward bournonite.

■ RESULTS AND DISCUSSION

■ CONCLUSIONS

■ REFERENCES