Wurtzite CZTS nanocrystals and phase evolution to kesterite thin film for solar energy harvestingElectronic supplementary information (ESI) available: Experimental details, characterizations, FE-SEM, EDS, photo images of an RTA system, a graphite box and fabricated solar cell device and schematic diagram of sulfurization process, average photovoltaic performances, band gap energy plots. See DOI: 10.1039/c5cp02007g

A quaternary indium- and gallium-free kesterite (KS)-based compound, copper zinc tin sulfide (Cu 2 ZnSnS 4 , CZTS), has received significant attention for its potential applications in low cost and sustainable solar cells. It is well known that the reaction time, reactivity of the precursors, and types of capping ligands used during the synthesis of colloidal nanocrystals (NCs) strongly influence the crystallographic phase of the NCs. In this research, a non-toxic and green synthetic strategy for both the synthesis of CZTS NCs and the fabrication of a highly efficient CZTS absorber layers using an ink formulation without a toxic solvent, which meets the comprehensive framework for green chemistry that covers major aspects of the environmental strain, is demonstrated. In particular, pure metastable wurtzite (WZ) CZTS NCs are synthesized using the environmentally harmless, polyol mediated hot-injection (HI) technique at a low reaction temperature. The influence of the reaction time on the properties of the CZTS NCs is investigated in detail. Based on detailed reaction time dependent phase evolution, a possible growth and formation mechanism is proposed. Furthermore, a scalable, low cost, binder free ink formulation process without ligand exchange is developed using ethanol as the dispersal solvent. The as-prepared WZ-derived CZTS NC thin films are observed to undergo a phase transformation to KS during annealing in a sulfur vapor atmosphere via rapid thermal annealing above 500 °C, and surprisingly, this process results in fully sintered, compact and uniform CZTS thin films with large sized grains. The best solar cell device fabricated using a CZTS absorber that was sulfurized at an optimized temperature exhibits a power conversion efficiency of 2.44%, which is the highest efficiency obtained using the polyol-based HI route. A quaternary indium- and gallium-free kesterite (KS)-based compound, copper zinc tin sulfide (Cu 2 ZnSnS 4 , CZTS), has received significant attention for its potential applications in low cost and sustainable solar cells.