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Hybrid Ligand Exchange of Cu(In,Ga)S2 Nanoparticles for Carbon Impurity Removal in Solution-Processed Photovoltaics

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    Hybrid Ligand Exchange of Cu(In,Ga)S2 Nanoparticles for Carbon Impurity Removal in Solution-Processed Photovoltaics
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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 12, 5091–5103
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    https://doi.org/10.1021/acs.chemmater.0c00966
    Published May 5, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The solution processing of Cu(In,Ga)(S,Se)2 photovoltaics from colloidal nanoparticles has long suffered from deleterious carbonaceous residues originating from long chain native ligands. This impurity carbon has been observed to hinder grain formation during selenization and leave a discrete residue layer between the absorber layer and the back contact. In this work, organic and inorganic ligand exchanges were investigated to remove tightly bound native oleylamine ligands from Cu(In,Ga)S2 nanoparticles, thereby removing the source of carbon contamination. However, incomplete ligand removal, poor colloidal stability, and/or selective metal etching were observed for these methods. As such, an exhaustive hybrid organic/inorganic ligand exchange was developed to bypass the limitations of individual methods. A combination of microwave-assisted solvothermal pyridine ligand stripping followed by inorganic capping with diammonium sulfide was developed and yielded greater than 98% removal of native ligands via a rapid process. Despite the aggressive ligand removal, the nanoparticle stoichiometry remained largely unaffected when making use of the hybrid ligand exchange. Furthermore, highly stable colloidal ink formulations using nontoxic dimethyl sulfoxide were developed, supporting stable nanoparticle mass concentrations exceeding 200 mg/mL. Scalable blade coating of the ligand-exchanged nanoparticle inks yielded remarkably smooth and microcrack free films with an RMS roughness less than 7 nm. Selenization of ligand-exchanged nanoparticle films afforded substantially improved grain growth as compared to conventional nonligand-exchanged methods, yielding an absolute improvement in device efficiency of 2.8%. Hybrid ligand exchange nanoparticle-based devices reached total area power conversion efficiencies of 12.0%, demonstrating the feasibility and promise of ligand-exchanged colloidal nanoparticles for the solution processing of Cu(In,Ga)(S,Se)2 photovoltaics.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c00966.

    • 1H-NMR comparison of alkene region single- and four times-washed CIGS nanoparticles, HAADF STEM image of as-synthesized CIGS nanoparticles, mixture components, and gas chromatogram from GC–MS of a freeze-pump thawed oleyalmine mixture, 1H-NMR of pyridine region from hybrid ligand-exchanged nanoparticles, XRD and Raman of various ligand exchanges compared as-synthesized nanoparticles, optical micrograph, and profilometry scan of the film surface, Raman of a selenized hybrid ligand-exchanged film’s C–C region, STEM-EDS comparison of a selenized hybrid ligand exchange film and conventionally prepared film, quantitative elemental distribution in fine grain layers, neighboring device parameters and averages for conventional and hybrid ligand-exchanged devices, and Ncv versus width extracted from capacitance–voltage measurements (PDF)

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    Cite this: Chem. Mater. 2020, 32, 12, 5091–5103
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.0c00966
    Published May 5, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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