Fabrication of high band gap kesterite solar cell absorber materials for tandem applications

Using the thermal annealing of evaporated metallic precursors in successive H₂Se and H₂S atmospheres, it was possible to reproducibly manufacture kesterite absorber material for solar cell applications with a sulfur content varying from 30% to 100%. Respective band gaps for these sulfur inclusions were measured at approximately 1.45 eV and 2.0 eV. A recipe was devised for which results could be reproduced within an error margin of ±5% and the influence of the H₂S pressure during the post sulfurization was negligible on all measurable and observable parameters. The evolution of the S/Se ratio in the sample was observed to be linearly dependent on the annealing time. It was also observed that at very early stages of the post-sulfurization, both the original Cu₂(Zn,Ge)Se₄ (CZGSe) and a primary Cu₂(Zn,Ge)(S,Se)₄ (CZGSSe) phase with a sulfur inclusion of ~30% coexist in the sample. The (112) x-ray diffraction (XRD) reflection of the CZGSe phase progressively disappears in favor for the first mixed CZGSSe phase. Using grazing incidence-XRD, the S/Se ratio was shown to be inhomogeneous. Indeed, the XRD measurement of the top layers led to the calculation of higher sulfur inclusions than was the case when measuring the bulk material. Top-scanning electron microscopy (SEM) as well as cross-SEM measurements were taken in order to determine the impact of the sulfur inclusion on the crystal growth and the overall quality of the produced absorber layers. The obtained images revealed a reduction in crystal size and the appearance of numerous holes in the layer as the S/Se ratio is increased.