Synthesis of Cu2(Zn1-xCox)SnS4 nanocrystals and formation of polycrystalline thin films from their aqueous dispersions

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Quintenary Cu (Zn Co )SnS is an analog of the promising solar absorber material Cu ZnSnS (CZTS). The initial rapid progress in CZTS has stalled because the similar sizes of Cu and Zn cations lead to facile formation of antisite defects, which are thought to limit the solar cell performance. Cobalt substitution for Zn may reduce cation disorder. Herein, we report the synthesis of wurtzite Cu (Zn Co )SnS across the entire composition range and a systematic study of the substitution of Co into the wurtzite CZTS lattice. The synthesis is based on microwave heating to only 160 °C and uses metal salts and thiourea as precursors and ethylene glycol as the solvent. The Cu (Zn Co )SnS nanocrystals were phase pure wurtzite within the detection limits of X-ray diffraction and Raman scattering. The wurtzite lattice parameters, nanocrystal sizes, and A1 Raman mode peak positions depend on the Co concentration, x. The lattice parameters follow Vegard's law within the accuracy of our measurements, and the A1 Raman mode shifts nearly linearly with x. The nanocrystal size decreases from 8 nm to 4 nm as x increases from 0 to 1. The absorption band edge blue shifted from 1.1 eV for x = 0 to 1.35 eV for x = 1. These values are lower than those predicted by density functional theory calculations and previous attempts at determining the optical band gap for wurtzite Cu ZnSnS (x = 0) and Cu CoSnS (x = 1). Either the band gaps of wurtzite Cu ZnSnS (x = 0) and Cu CoSnS (x = 1) are lower or these materials have significant band tails due to defects. We also prepared polycrystalline Cu (Zn Co )SnS thin films by thermal annealing, in sulfur, of coatings comprised of Cu (Zn Co )SnS nanocrystals. Upon annealing in sulfur, the wurtzite Cu (Zn Co )SnS nanocrystals transformed into larger grains (100 s of nm to microns) that have a kesterite structure. The films with x ≤ 0.4 were phase pure kesterite within the detection limits of XRD and Raman scattering, but, for x ≥ 0.6, secondary phases such as Cu S and Co Zn S were also detected. 2 1-x x 4 2 4 2 1-x x 4 2 1-x x 4 2 4 2 4 2 4 2 4 2 1-x x 4 2 1-x x 4 2 1-x x 4 1.96 0.24 0.76

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Journal of Materials Chemistry A

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