Ceramic-Processing Perspectives on Colloidal CIGS and CZTSSe Thin-Film Solar Absorbers: Green-Body Formation, Reactive Chalcogenization, and Defect Engineering

Colloidal processing provides a scalable non-vacuum route for fabricating CIGS and CZTSSe thin-film absorbers, but nanoparticle-derived films should be treated as constrained particulate green bodies rather than as simple chemically deposited semiconductor layers. This review reorganizes colloidal chalcogenide photovoltaics using ceramic-processing concepts: ink dispersion, green-body packing, capillary drying stress, ligand burnout, constrained shrinkage, reactive chalcogenization, transient liquid-assisted coarsening, secondary-phase control, defect chemistry, and interface reactions. The central argument is that film densification and grain growth are necessary but insufficient for high-performance CZTSSe devices. Residual carbon, Sn loss, Cu/Zn disorder, ZnSe or Cu_2−xSe secondary phases, excessive MoSe₂, and nonideal absorber/buffer band alignment can dominate open-circuit-voltage loss, fill factor, and carrier collection even when the absorber appears dense in cross-sectional microscopy. By linking ceramic-processing variables to photovoltaic loss mechanisms, this review identifies practical routes for improving colloidal chalcogenide solar cells: controlled ligand exchange and binder burnout, high-green-density precursor design, moderated chalcogen chemical potential, transient liquid management, depth-resolved phase analysis, and integrated front/back-interface engineering.