Investigation of Cu2ZnSnS4 nanoparticles for thin-film solar cell applications

We study the effect of the annealing atmosphere on grain growth of ligand-free and ligand-coated Cu2ZnSnS4 (CZTS) nanoparticle-based thin films by thermal analysis. We use thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) to simultaneously monitor mass changes and evolved gases of both nanoparticle powders and inks. The investigation focuses on annealing in air, nitrogen and forming gas (5% H2 in Ar), i.e., oxidizing, inert, and reducing atmospheres. We find that the oleylamine capping ligands thermally decompose into smaller organic fragments starting below its boiling point, with a slightly higher decomposition rate in reducing atmosphere. With nanoparticle inks, very modest grain growth is observed, with no differences between the atmospheres. Conversely, with nanoparticle powders, micron-sized grains appear all over for the ligand-free sample and some micron-sized grains are seen with inert atmosphere for the ligand-coated powder. The starting material is thus very important for grain growth.