Effect of the burn-out step on the microstructure of the solution-processed Cu(In,Ga)Se₂ solar cells

For the development of the photovoltaic industry cheap methods for the synthesis of Cu(In_,Ga)Se₂ (CIGSe) based solar cells are required. In this work, CIGSe thin films were obtained by a solution-based method using oxygen-bearing derivatives. With the aim of improving the morphology of the printed CIGSe layers, we investigated two different annealing conditions of the precursor layer, consisting of (1) a direct selenization step (reference process), and (2) a pre-treatment thermal step prior to the selenization. We showed that the use of an Air/H₂S burn-out step prior to the selenization step increases the CIGSe grain size and reduces the carbon content. However, it leads to the reduction of the solar cell efficiency from 4.5% in the reference sample down to 0.5% in the annealed sample. Detailed transmission electron microscopy analysis, including high angle annular dark field scanning transmission electron microscopy and energy dispersive X-ray mapping, was applied to characterize the microstructure of the film and to determine the relationship between microstructure and the solar cell performance. We demonstrated that the relatively low efficiency of the reference solar cells is related not only to the nanosize of the CIGSe grains and presence of the pores in the CIGSe layer, but also to the high amount of secondary phases, namely, In/Ga oxide (or hydroxide) amorphous matter, residuals of organic matter (carbon), and copper sulfide that is formed at the CIGSe/MoSe₂ interface. The annealing in H₂S during the burn-out step leads to the formation of the copper sulfide at all grain boundaries and surfaces in the CIGSe layer, which results in the noticeably efficiency drop. - Highlights: • Cu(Ga,In)Se₂ solar cells were synthesized by a solution-based method. • The morphology of the CIGSe layer improves during the annealing. • The efficiency of the reference sample is 4.5% and of the annealed is 0.5%. • Upon the annealing, copper sulfide segregates at the surface of the CIGSe grains. • Presence of the admixture phases leads to the drop of solar cells efficiency