LAUSR

Abstract Germanium-based wide band gap kesterite semiconductor Cu2ZnGe(S,Se)4 (CZGeSSe) is considered a very promising absorber compound as top cell in tandem devices. Autonomy to tailor the band gap from ~1.47 eV (Cu2ZnGeSe4-CZGeSe) to ~2.2 eV (Cu2ZnGeS4-CZGeS), as well as non-toxic constituents makes this compound a strong candidate for further scientific exploration. However, the record efficiency of Cu2ZnGeSe4 solar cells is still significantly lower than those of its predecessors Cu2ZnSn(SxSe1-x)4 (CZTSSe), Cu(In,Ga)Se2 (CIGS) and CdTe thin-film solar cells. The comprehensive understanding of the factors limiting the performance of Cu2ZnGeSe4 based solar cells is the purpose of this work, by combining a complete characterization of the morphological, structural, compositional and optoelectronic properties of Cu2ZnGeSe4 absorbers and devices. Besides, an in-depth investigation of the main limitations is carried out, specifically focusing on studying the origin of the large VOC deficit, the main recombination mechanisms, electric transport properties, band tails and possible Cu2ZnGeSe4/CdS band offset effects. The champion CZGeSe solar cell device reported in this work shows an efficiency of 6.5%, Voc of 606 mV, JSC of 17.8 mA/cm2 and FF of 60%. The results presented here demonstrate that the large voltage deficit of CZGeSe solar cells could be mainly ascribed to a Fermi level pinning at the interface, while modifications of the buffer layer to induce a “spike” at the p-n junction could be beneficial. Additionally, low carrier diffusion lengths and lifetimes, along with possible back contact recombination, are identified as the main culprits for the limited carrier collection for low-energy photons. Finally, some strategies are proposed to face and overcome most of these issues and to help improving the CZGeSe performance.