Abstract This review emphasizes the recent advancements and prospects of thin-film kesterite-based photovoltaic (PV) applications using magnesium, iron and nickel. The quest for novel materials employed in solar cells has resulted in incorporating these elements into the composition of kesterite as substitutes or modifiers (dopants) for zinc. This integration has induced notable repercussions on the structural, optoelectronics and morphological properties, which are reviewed. The first section of this paper offers a comprehensive review of the general characteristics of kesterite minerals. These crucial materials exhibit a high absorption coefficient (104 cm–1) and an optical band gap of 1.0–1.8 eV. Moreover, they are free of critical raw materials, non-toxic and sustainable. The second section depicts the substitution or modification of zinc by magnesium in kesterite. Additionally, this paper provides a comprehensive review of the quaternary and pentanary systems Cu2MgSn(S,Se)4 and Cu2Zn1–xMgxSnS4, highlighting their advantages and drawbacks. In the last section, a review of the quaternary or pentanary systems is conducted, namely Cu2ZnxFe1–xSnS4 and Cu2ZnxNi1–xSnS4, along with their effects on optoelectronic properties. In conclusion, various methods for obtaining modified or substituted kesterite materials using magnesium, iron and nickel have demonstrated sustainability, scalability for industrial production and potential candidacy as substitutes for conventional PV materials. The prospects for pentanary materials (Cu2Zn1‑xMgxSnS4, Cu2Zn1‑xFexSnS4 and Cu2Zn1‑xNixSnS4) are to overcome the efficiency record of kesterite reported in 2014, which was 12.6 % for Cu2ZnSn(S,Se)4, and to enhance its optoelectronic properties through synthesis conditions that comply with the principles of green chemistry.
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