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Microscopic morphology independence in linear absorption cross-section of CsPbBr3 nanocrystals

CsPbBr3纳米晶微观形貌非依赖的线性吸收截面

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Abstract

Multiple morphologies of colloidal perovskite nanocrystals (NCs) diversify their optical and electronic properties. Among them, the linear absorption cross-section (σ) is a primary parameter to determine their intrinsic photophysical features, and consequently, application potential. Herein, three morphologies of all-inorganic hybrid colloidal perovskite CsPbBr3 NCs, nanocubes (NBs), nanoplatelets (NLs), and nanowires (NWs), were targeted, and their linear σ values were obtained through femtosecond transient absorption (TA) spectroscopy analysis. At high excitation energy well above the bandgap, the σ per particle of all CsPbBr3 NCs linearly increased with the particle volume (VNC) regardless of the morphology with the value of σ400 = 9.45 × 104 cm−1 × VNC (cm2). Density functional theory (DFT) calculation confirmed the negligible influence of shapes on the optical selection rules. The Einstein spontaneous emission coefficients calculated from the σ values define the intrinsic radiative recombination rate. However, reduced size dependence is observed when the excitation energy is close to the bandgap (i.e., at 460 nm) with the value of σ460 = 2.82 × 108 cm0.65 × (VNC)0.45 (cm2). This should be ascribed to the discrete energy levels as well as lower density of states close to the band edge for perovskite NCs. These results provide in-depth insight into the optical characteristics for perovskite NCs.

摘要

胶体钙钛矿纳米晶的形貌变化赋予其不同的光学和电子特 性, 其中, 线性吸收截面是决定材料本征光物理特性及其应用潜力 的主要参数. 本文研究了三种不同形貌的全无机钙钛矿CsPbBr3纳 米晶(纳米立方体、纳米片和纳米线), 通过飞秒瞬态吸收光谱分析 了它们的线性吸收截面值σ. 在高于带隙的能量激发下, 单个 CsPbBr3纳米晶的吸收截面值与形貌无关, 且随着粒子的体积(VNC) 呈σ400 = 9.45 × 104 cm−1 × VNC (cm2)趋势变化. 密度泛函理论证实 了形貌对光学选择规则基本没有影响, 同时, 根据吸收截面值也计 算得到了定义本征辐射复合率的爱因斯坦自发辐射系数. 然而, 当 激发能接**带隙(460 nm)时, 吸收截面值对纳米晶尺寸的依赖关系 变弱, 取值满足σ460 = 2.82 × 108 cm0.65 × (VNC)0.45 (cm2), 这主要归因 于钙钛矿纳米晶的离散能级及靠**带边的较低的态密度. 本文的 研究结果为洞悉钙钛矿纳米晶的光学特性提供了深入的见解.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC, U1862111), China Scholarship Council (201706990062), Independent Research Fund Denmark-Nature Sciences (DFF-7014-00302), Independent Research Fund Denmark-Sapere Aude starting grant (7026-00037A), Swedish Research Council VR starting grant (2017-05337), grants VR2018-06011, and VR2018-05090, the Research Fund for international Young Scientists from NSFC, China (21950410515) and Swedish Energy Agency.

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Authors and Affiliations

  1. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation and School of New Energy and Materials, Southwest Petroleum University, Chengdu, 610500, China

    Fengying Zhang  (张凤英), Shiqian Wei  (卫诗倩) & Ying Zhou  (周莹)

  2. Department of Chemical Physics and NanoLund Chemical Center, Lund University, P.O. Box 124, 22100, Lund, Sweden

    Fengying Zhang  (张凤英), Yuchen Liu  (刘禹辰), Junsheng Chen  (陈俊生), Tõnu Pullerits & Kaibo Zheng  (郑凯波)

  3. College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China

    Fengying Zhang  (张凤英) & Rongxing He  (何荣幸)

  4. Department of Chemistry, Technical University of Denmark, DK-2800, Kongens Lyngby, Denmark

    Kaibo Zheng  (郑凯波)

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  1. Fengying Zhang  (张凤英)
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  8. Kaibo Zheng  (郑凯波)
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Contributions

Zhang F designed and engineered the samples; Liu Y, Wei S and Chen J assisted to perform the experiments; Zhou Y, He R and Pullerits T helped to modify the manuscript; Zheng K led the project.

Corresponding authors

Correspondence to Rongxing He  (何荣幸), Tõnu Pullerits or Kaibo Zheng  (郑凯波).

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Conflict of interest

The authors declare that they have no conflict of interest.

Fengying Zhang received her PhD degree from Southwest University in 2019. During her PhD period, she studied at Lund University as a visiting PhD, dedicated to the study of material spectroscopy. Then, she joined the School of New Energy and Materials, Southwest Petroleum University as a lecturer, and has engaged in material-related scientific research.

Rongxing He is a professor at Southwest University, China. He received his PhD from Sichuan University in 2006. Then, he joined the School of Chemistry and Chemical Engineering, Southwest University. His main research interests include molecular spectroscopy and photochemistry, electrochemical catalysis and reaction mechanism, and photoelectric functional materials.

Tõnu Pullerits obtained his PhD degree in 1991 from the Institute of Physics at Tartu University, Estonia. He is currently full professor and head of the Chemical Physics Division at Lund University. He has been a member of the Royal Swedish Academy of Sciences since 2016. His research interests include energy transport in molecular systems, ultrafast charge carrier dynamics and photophysics in photovoltaic materials, and coherence multidimensional spectroscopy.

Kaibo Zheng obtained his PhD degree in 2010 from the Department of Materials Science at Fudan University. Then, he joined the Chemical Physics Division at Lund University, Sweden, as a postdoctoral fellow. He is currently a senior researcher in chemical physics, Lund University, and dual affiliated as a senior researcher at the Department of Chemistry, Technical University of Denmark. His research interests include the structure and photophysics of semiconductor and perovskite quantum dots as light harvesting materials.

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Zhang, F., Liu, Y., Wei, S. et al. Microscopic morphology independence in linear absorption cross-section of CsPbBr3 nanocrystals. Sci. China Mater. 64, 1418–1426 (2021). https://doi.org/10.1007/s40843-020-1555-1

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