journal article·2025-01-28Open access

Band Gap Narrowing in Lead-Halide Perovskites by Dynamic Defect Self-Doping for Enhanced Light Absorption and Energy Upconversion

Yongliang Shi, Weibin Chu, Lili Zhang, Bipeng Wang, Wissam A. Saidi, Jin Zhao, Oleg V. Prezhdo

Chemistry of Materials· Volume 37· Issue 2

Abstract

High Resolution Image Download MS PowerPoint Slide Metal halide perovskites (MHP) have attracted great attention in the photovoltaic industry due to their high and rapidly rising power conversion efficiencies, currently over 25%. However, hybrid organic–inorganic MHPs are inherently chemically unstable, limiting their application. All-inorganic MHPs perovskites, such as CsPbI 3, have many merits, but their stable conversion efficiency is lower, around 18%, due to a larger band gap causing a mismatch with the solar spectrum. Choosing α-CsPbI 3 as a prototypical system, we demonstrate a new general concept of dynamic defects that fluctuate between deep and shallow states, and increase the range of absorbed solar photons, without accelerating the nonradiative electron–hole recombination. In their deeper energy state, the defects narrow the band gap and allow the harvesting of light with longer wavelengths. Fluctuating to shallower energies, the defects allow the escape of photogenerated charges into bands, enabling charge transport and resulting in the defect-mediated upconversion of thermal energy into electricity. Defect covalency and participation of low-frequency anharmonic vibrations decouple trapped charges from free charge carriers, minimizing nonradiative charge carrier losses. Our findings demonstrate that defect covalency and defect dynamics are unique and important properties of MHPs, and can be used to optimize MHPs for efficient solar energy harvesting and optoelectronic applications.
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Research context

OpenAlex topics: Perovskite Materials and Applications · Chalcogenide Semiconductor Thin Films · Quantum Dots Synthesis And Properties

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433, China

Center for Spintronics and Quantum Systems, State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China

Key Laboratory of Computational Physical Sciences (Ministry of Education), Institute of Computational Physical Sciences, Fudan University, Shanghai 200433, China

Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States

Key Laboratory of Material Physics, Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450001, China

Department of Chemical Engineering, University of Southern California, Los Angeles, California 90089, United States

National Energy Technology Laboratory, 626 Cochran Mill Road, Pittsburgh, Pennsylvania 15236, United States

Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States

Department of Physics and ICQD/Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China

Department of Physics and Astronomy, University of Southern California, Los Angeles, California 90089, United States

Funding

Division of Chemistry · Center for Strategic Scientific Initiatives, National Cancer Institute · National Natural Science Foundation of China · Chinese Academy of Sciences · Innovation Program for Quantum Science and Technology

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