Octahedral Dominance and Band Gap Tuning via Pb<sup>2+</sup>-Driven Structural Evolution in α-β-γ CsZnI<sub>3</sub>

In the quest for stable, lead-reduced perovskites, this study unravels the structural and electronic evolution of CsZnI<sub>3</sub> across its α, β, and γ phases. DFT calculations spotlight the tetrahedral γ phase—with elongated Zn–I bonds (3.17 Å)—as the most stable, sidestepping the oc...

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Bibliographic Details
Main Authors: Baoyun Liang, Ang Li, Ziming Kuang, Yating Qu, Hao Xu, Tianyi Tang, Tingting Shi, Weiguang Xie
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Solids
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Online Access:https://www.mdpi.com/2673-6497/6/2/30
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Summary:In the quest for stable, lead-reduced perovskites, this study unravels the structural and electronic evolution of CsZnI<sub>3</sub> across its α, β, and γ phases. DFT calculations spotlight the tetrahedral γ phase—with elongated Zn–I bonds (3.17 Å)—as the most stable, sidestepping the octahedral distortions of its metallic α and β counterparts. Pb<sup>2+</sup> doping (>50%) drives a transformation to mixed octahedral–tetrahedral coordination, slashing the wide 3.15 eV bandgap to a solar-optimal 2.20 eV via lattice shrinkage. Above 50% doping, an optimum emerges—balancing structural integrity with efficient light absorption. These findings elevate Zn-doped or Zn-Pb-based compounds as promising and tunable perovskites for next-gen photovoltaics.
ISSN:2673-6497