TY - JOUR
T1 - On the thermodynamic of Cu-Zn disorder formation and electronic structure changes of alkaline-earth M-doped kesterite Cu2ZnSnS4 (M = Be, Mg, Ca)
AU - Abdillah, Nurfauzi
AU - Ayukaryana, Nur Rahmawati
AU - Agusta, Mohammad Kemal
AU - Rusydi, Febdian
AU - Shukri, Ganes
N1 - Publisher Copyright:
© 2024
PY - 2025/2/15
Y1 - 2025/2/15
N2 - The kesterite Cu2ZnSnS4 (ks-CZTS) is a promising beyond-Si low-cost photovoltaic absorber material. However, the inherent low open-circuit voltage due to cation disorder formation has been hindering its commercial utilization. Herein, by means of first-principles density functional theory (DFT) calculations, we investigate the effect of alkaline-earth dopant on the energetics of CuZn + ZnCu antisite defect pair and Cu–Zn disorder formation and the corresponding ks-Cu2Zn1-xMxSnS4 (ks-CZMTS) (M = Be, Mg, Ca) electronic structure variation. We find that the incorporation of each of the three alkaline-earth dopants into ks-CZTS by Zn substitution increases the overall formation energy of Cu–Zn disorder. This indicates that the M-doped ks-CZTS has better stability against the formation of the Cu–Zn disorder as compared to the pristine ks-CZTS. Further, the incorporation of either Be, Mg, and Ca as a Zn-substituted dopant shows a marginal change on the electronic structure of the M-doped ks-CZTS compared to that of the pristine one. These findings point out that incorporating alkaline-earth elements into ks-CZTS is a promising avenue to suppress the formation of unwanted cation disorder and simultaneously preserve the semiconductor characteristic of ks-CZTS.
AB - The kesterite Cu2ZnSnS4 (ks-CZTS) is a promising beyond-Si low-cost photovoltaic absorber material. However, the inherent low open-circuit voltage due to cation disorder formation has been hindering its commercial utilization. Herein, by means of first-principles density functional theory (DFT) calculations, we investigate the effect of alkaline-earth dopant on the energetics of CuZn + ZnCu antisite defect pair and Cu–Zn disorder formation and the corresponding ks-Cu2Zn1-xMxSnS4 (ks-CZMTS) (M = Be, Mg, Ca) electronic structure variation. We find that the incorporation of each of the three alkaline-earth dopants into ks-CZTS by Zn substitution increases the overall formation energy of Cu–Zn disorder. This indicates that the M-doped ks-CZTS has better stability against the formation of the Cu–Zn disorder as compared to the pristine ks-CZTS. Further, the incorporation of either Be, Mg, and Ca as a Zn-substituted dopant shows a marginal change on the electronic structure of the M-doped ks-CZTS compared to that of the pristine one. These findings point out that incorporating alkaline-earth elements into ks-CZTS is a promising avenue to suppress the formation of unwanted cation disorder and simultaneously preserve the semiconductor characteristic of ks-CZTS.
KW - CuZnSnS
KW - Density functional theory
KW - Dopant
KW - Electronic structure
KW - Kesterite
UR - http://www.scopus.com/inward/record.url?scp=85212064378&partnerID=8YFLogxK
U2 - 10.1016/j.matchemphys.2024.130262
DO - 10.1016/j.matchemphys.2024.130262
M3 - Article
AN - SCOPUS:85212064378
SN - 0254-0584
VL - 332
JO - Materials Chemistry and Physics
JF - Materials Chemistry and Physics
M1 - 130262
ER -