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Transient spectral and dynamic properties of magic-size Cd3P2 nanoclusters in the limit of strong confinement

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Abstract

Both semiconductor nanocrystals and organic molecules are important photofunctional materials for an array of applications. It is interesting to examine the intermediate regime between these two families, which can be interpreted as the strong-confinement limit of the nanocrystals or alternatively as the large-size limit of molecules. Here, we choose Cd3P2 magic-size clusters (MSCs) as a unique platform and apply time-resolved spectroscopy to investigate their spectral and dynamic properties. We find that these small clusters display molecular-like vibronic progression on their absorption and emission spectra and a large Stokes shift, which leads to well-separated transient absorption bleach and stimulated emission signals distinct from typical nanocrystals. On the other hand, such small size MSCs can still accommodate biexciton states, and the strongly enhanced Coulombic interactions lead to very fast dephasing of the biexciton resonance as well as rapid biexciton Auger annihilation (1.5 ps). Further, temperature-dependent measurements provide evidence for the transformation of band-edge excitons to localized excitons, with the localization likely driven by the softened lattice in these small-size clusters. These collective results demonstrate that strongly-confined nanoclusters indeed bridge the gap between nanocrystals and molecules, and can be a unique library to search for exotic excited state properties.

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Acknowledgements

K.W. acknowledges financial support from the Chinese Academy of Sciences (YSBR-007), the National Natural Science Foundation of China (22173098, 21975253), the Fundamental Research Funds for the Central Universities (20720220009) and the New Cornerstone Science Foundation through the XPLORER PRIZE.

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Authors and Affiliations

  1. Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, China

    Yuan Liu & Kaifeng Wu

  2. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Yuan Liu, Yuxuan Li, Yupeng Yang, Jingyi Zhu & Kaifeng Wu

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Yuxuan Li, Yupeng Yang & Kaifeng Wu

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  1. Yuan Liu
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  2. Yuxuan Li
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  4. Jingyi Zhu
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  5. Kaifeng Wu
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Correspondence to Jingyi Zhu or Kaifeng Wu.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Liu, Y., Li, Y., Yang, Y. et al. Transient spectral and dynamic properties of magic-size Cd3P2 nanoclusters in the limit of strong confinement. Sci. China Chem. 66, 3628–3635 (2023). https://doi.org/10.1007/s11426-023-1870-1

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  • DOI: https://doi.org/10.1007/s11426-023-1870-1

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