How small amounts of Ge modify the formation pathways and crystallization of kesterites

The inclusion of Ge into the synthesis of Cu2ZnSn(S,Se)4 absorbers for kesterite solar cells has been proven to
be a very efficient way to boost the device efficiency in a couple of recent publications. This highlights the
importance to elucidate the mechanisms by which Ge improves the kesterite solar cells properties to such a
large extent. In this contribution, we first show how controlling the position and thickness of a very thin
(10–15 nm) layer of Ge greatly influences the crystallization of kesterite thin films prepared in a sequential
process. Typically, Cu2ZnSnSe4 (CZTSe) films form in a bi-layer structure with large grains in the upper region
and small grains at the back. By introducing Ge nanolayers below our precursors, we observe that large
CZTSe grains extending over the whole absorber thickness are formed. Additionally, we observe that Ge
induces fundamental changes in the formation mechanism of the kesterite absorber. In a detailed analysis of
the phase evolution with and without Ge, we combine the results of X-ray fluorescence, X-ray diffraction
and Raman spectroscopy to demonstrate how the Ge influences the preferred reaction scheme during the
selenization. We reveal that the presence of Ge causes a large change in the in-depth elemental distribution,
induces a stabilizing Cu–Sn intermixing, and thus prevents drastic compositional fluctuations during the
annealing process. This finally leads to a change from a tri-molecular towards, mainly, a bi-molecular CZTSe
formation mechanism. Kesterite thin films with surprisingly large crystals of several microns in diameter can
be fabricated using this approach. The results are related to the increase in device performance, where power
conversion efficiencies of up to 11.8% were obtained. Finally, the consequences of the disclosed crystallization
pathways and the extension to other chalcogenide technologies are discussed.