TY - JOUR
T1 - Systematic Band Gap Tuning of BaSnO3 via Chemical Substitutions: The Role of Clustering in Mixed-Valence Perovskites
AU - Usanmaz, Demet
AU - Lee, Seunghun
AU - Wang, Haihang
AU - Gopal, Priya
AU - Shin, Jongmoon
AU - Iftekhar Jaim, H. M.
AU - Zhang, Xiaohang
AU - Jeong, Se-Young
AU - Curtarolo, Stefano
AU - Fornari, Marco
AU - Buongiorno Nardelli, Marco
AU - Takeuchi, Ichiro
PY - 2017
Y1 - 2017
N2 - By combining high-throughput experiments and first-principles calculations based on the DFT-ACBN0 approach, we have investigated the energy band gap of Sr-, Pb-, and Bi-substituted BaSnO 3 over wide concentration ranges. We show that the band gap energy can be tuned from 3 to 4 eV by chemical substitution. Our work indicates the importance of considering the mixed-valence nature and clustering effects upon substitution of BaSnO 3 with Pb and Bi. Starting from the band gap of ∼3.4 eV for pure BaSnO 3 , we find that Pb substitution changes the gap in a nonmonotonic fashion, reducing it by as much as 0.3 eV. Bi substitution provides a monotonic reduction but introduces electronic states into the energy gap due to Bi clustering. Our findings provide new insight into the ubiquitous phenomena of chemical substitutions in perovskite semiconductors with mixed-valence cations that underpin their physical properties.
AB - By combining high-throughput experiments and first-principles calculations based on the DFT-ACBN0 approach, we have investigated the energy band gap of Sr-, Pb-, and Bi-substituted BaSnO 3 over wide concentration ranges. We show that the band gap energy can be tuned from 3 to 4 eV by chemical substitution. Our work indicates the importance of considering the mixed-valence nature and clustering effects upon substitution of BaSnO 3 with Pb and Bi. Starting from the band gap of ∼3.4 eV for pure BaSnO 3 , we find that Pb substitution changes the gap in a nonmonotonic fashion, reducing it by as much as 0.3 eV. Bi substitution provides a monotonic reduction but introduces electronic states into the energy gap due to Bi clustering. Our findings provide new insight into the ubiquitous phenomena of chemical substitutions in perovskite semiconductors with mixed-valence cations that underpin their physical properties.
KW - band gap
KW - chemical substitution
KW - Clustering
KW - mixed-valence perovskites
UR - https://pubs.acs.org/doi/10.1021/acs.chemmater.7b03381
U2 - 10.1021/acs.chemmater.7b03381
DO - 10.1021/acs.chemmater.7b03381
M3 - Article
VL - 29
JO - Chemistry of Materials
JF - Chemistry of Materials
ER -