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Efficiency enhancement of Cu2ZnSnS4 monograin layer solar cells via absorber post-growth treatments

<p>Currently, the efficiency of Cu2ZnSnS4 (CZTS) monograin layer solar cells is mainly limited by the recombination losses in the bulk and at the surface of absorber/buffer that need to be reduced. One approach to significantly improve the performance of CZTS monograin layer solar cells is to post-treat the surfaces of monograin powder crystals before the buffer layer deposition. This study includes the optimization of two sequential post-treatment steps: 1) chemical etching of as-grown powder crystals with Br2 in methanol followed by KCN; and 2) annealing at different temperatures (550&ndash;850&nbsp;&deg;C) under different sulfur vapor pressures (100&ndash;2050&nbsp;Torr) in a two-temperature zone furnace in closed ampoules. Energy-dispersive X-ray spectroscopy, high-resolution scanning electron microscopy and Raman studies using multiwavelength excitation revealed that SnS2 and ZnS secondary phases were formed on the crystals&rsquo; surfaces in the thermal annealing process. At the same time, by increasing the annealing temperature, the ratio of Cu/(Zn&nbsp;+&nbsp;Sn) increased and Zn/Sn decreased in the bulk of annealed CZTS crystals compared to as-grown monograin powder crystals. Optimal conditions for combinational post-treatment to adjust the absorber material composition and to improve monograin layer solar cells&#39; performance were found as follows: the chemical etching of as-grown powders with 1% Br2&ndash;MeOH for 5&nbsp;min&nbsp;+&nbsp;10% KCN for 5&nbsp;min followed by annealing in sealed ampoules at 850&nbsp;&deg;C in a sulfur atmosphere of 2050&nbsp;Torr for 1&nbsp;h. The highest power conversion efficiency of 9.44% was obtained under these conditions.</p>

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