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Defect tolerance in chalcogenide perovskite photovoltaic material BaZrS3

硫族钙钛矿光伏材料BaZrS3的缺陷容忍性

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Abstract

Chalcogenide perovskites (CPs) exhibiting lower band gaps than oxide perovskites and higher stability than halide perovskites are promising materials for photovoltaic and optoelectronic applications. For such applications, the absence of deep defect levels serving as recombination centers (dubbed defect tolerance) is a highly desirable property. Here, using density functional theory (DFT) calculations, we study the intrinsic defects in BaZrS3, a representative CP material. We compare Hubbard-U and hybrid functional methods, both of which have been widely used in addressing the band gap problem of semi-local functionals in DFT. We find that tuning the U value to obtain experimental bulk band gap and then using the obtained U value for defect calculations may result in over-localization of defect states. In the hybrid functional calculation, the band gap of BaZrS3 can be accurately obtained. We observe the formation of small S-atom clusters in both methods, which tend to self-passivate the defects from forming mid-gap levels. Even though in the hybrid functional calculations several relatively deep defects are observed, all of them exhibit too high formation energy to play a significant role if the materials are prepared under thermal equilibrium. BaZrS3 is thus expected to exhibit sufficient defect tolerance promising for photovoltaic and optoelectronic applications.

摘要

硫族钙钛矿具有比氧化物钙钛矿更低的带隙以及比卤化物 钙钛矿更高的稳定性, 有望应用于光伏和光电领域. 在这类应用中, 理想的材料往往需要避免存在复合中心的深能级缺陷, 即缺陷容 忍性. 本文采用密度泛函理论(DFT)研究了一种典型硫族钙钛矿材 料BaZrS3的本征缺陷. 我们比较了Hubbard-U和杂化泛函这两种广 泛用于解决DFT中半局域泛函带隙问题的方法. 研究发现, 通过调 整U值获得与实验一致的带隙, 并将该U值用于缺陷计算, 可能会导 致缺陷态过度局域化. 而杂化泛函计算则可以准确得到BaZrS3的带 隙. 采用这两种计算方法均会形成小的S原子团簇, 这些团簇倾向于 通过自钝化来避免产生带隙中的深能级. 尽管在杂化泛函计算中 观察到一些能级相对较深的缺陷, 但是在热平衡条件下制备的材 料中, 由于过高的形成能, 这些缺陷的作用可以被忽略. 因此, BaZrS3具有足够的缺陷容忍性, 有望应用于光伏和光电领域.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (11774365), the Natural Science Foundation of Shanghai (19ZR1421800), Shanghai International Cooperation Project (20520760900), the Opening Project and Science Foundation for Youth Scholar of State Key Laboratory of High Performance Ceramics and Superfine Microstructures (SKL201804 and SKL201803SIC). Zeng H thanks the support by US National Science Foundation (NSF) (CBET-1510121) and US Department of Energy (DOE) (DEEE0007364). Zhang S thanks the support by US NSF (CBET-1510948). Zhang P thanks the support by US NSF (DMR-1506669). Gao W thanks the support by the Fundamental Research Funds for the Central Universities (DUT21RC(3) 033) and the computational resources provided by NERSC of the US DOE (DEAC02-05CH11231), the Texas Advanced Computing Center (TACC) and Shanghai Supercomputer Center.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 201899, China

    Xiaowei Wu  (吴晓维), Jun Chai  (柴骏), Chen Ming  (明辰) & Yi-Yang Sun  (孙宜阳)

  2. School of Physics, Dalian University Technology, Dalian, 116024, China

    Weiwei Gao  (高威帷)

  3. Center for Computational Materials, Oden Institute for Computational Engineering and Sciences, The University of Texas at Austin, Austin, TX, 78712, USA

    Weiwei Gao  (高威帷)

  4. College of Science, China Jiliang University, Hangzhou, 310018, China

    Miaogen Chen  (陈苗根)

  5. Department of Physics, University at Buffalo, The State University of New York, Buffalo, NY, 14260, USA

    Hao Zeng  (曾浩) & Peihong Zhang  (张培鸿)

  6. Department of Physics, Applied Physics & Astronomy, Rensselaer Polytechnic Institute, Troy, NY, 12180, USA

    Shengbai Zhang  (张绳百)

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  1. Xiaowei Wu  (吴晓维)
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  9. Yi-Yang Sun  (孙宜阳)
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Contributions

Sun YY initiated and coordinated the research. Wu X, Chai J and Ming C conducted the defect calculations. Gao W and Zhang P conducted the RPA calculations. Chen M, Zeng H and Zhang S participated in the analysis of the results. Sun YY, Wu X, Gao W, Ming C, Zeng H, Zhang P and Zhang S wrote the paper.

Corresponding authors

Correspondence to Chen Ming  (明辰) or Yi-Yang Sun  (孙宜阳).

Additional information

Xiaowei Wu received her BSc degree from the School of Physics and Electronic Information Engineering, Neijiang Normal University in 2016, and her Master degree from the School of Resources, Environment and Materials, Guangxi University in 2020. She joined the State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences in 2020 as a research assistant. Her current research focuses on the defect properties in energy materials using first-principles calculations.

Weiwei Gao is currently an associate professor at the School of Physics, Dalian University of Technology. He received his PhD degree from the Department of Physics, The State University of New York at Buffalo and did postdoctoral research at Oden Institute for Computational Engineering and Sciences, University of Texas at Austin. His research interests focus on developing new methods for efficient excited-states calculations and applying computational approach on studying novel materials.

Chen Ming received his PhD degree from Fudan University in 2012. He joined the State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences in 2014 as a postdoc and then as a research associate. His research interests are theoretical explorations of novel materials for optoelectronics and energy applications.

Yi-Yang Sun received his PhD degree from the National University of Singapore (NUS) in 2004. He worked as postdoc at the NUS, National Renewable Energy Laboratory, and Rensselaer Polytechnic Institute (RPI). In 2010, he was appointed research assistant professor and later research scientist at the RPI. In 2017, he assumed a professor position at Shanghai Institute of Ceramics, Chinese Academy of Sciences. His research focuses on the study of energy-related materials using the first-principles computations.

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The authors declare that they have no conflict of interest.

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Wu, X., Gao, W., Chai, J. et al. Defect tolerance in chalcogenide perovskite photovoltaic material BaZrS3. Sci. China Mater. 64, 2976–2986 (2021). https://doi.org/10.1007/s40843-021-1683-0

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