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A reactivity-controlled epitaxial growth strategy for synthesizing large nanocrystals

Nature Synthesis volume 2, pages 296–304 (2023)Cite this article

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Abstract

Large ZnSe nanocrystals are expected to be promising blue-light emitters with an emission peak of 455–475 nm, which is important for the construction of display apparatus. The final size of ZnSe nanocrystals via one-step injection can be varied by the reactivity of the Zn and Se precursors; however, it has a limit of <5 nm. To describe the key factors in determining the final size of ZnSe nanocrystals, we proposed a nuclei number-considered LaMer model based on the Maxwell–Boltzmann distribution of crystal embryos. As a result, a general strategy of reactivity-controlled epitaxial growth was developed to synthesize large ZnSe nanocrystals through sequential injection of high-reactivity and low-reactivity Zn and Se precursors. The resultant ZnSe nanocrystals achieved pure blue emission between 455 and 470 nm. We further fabricated stable, large ZnSe/ZnS core–shell nanocrystals with photoluminescence quantum yields up to approximately 60%. Moreover, the reactivity-controlled epitaxial growth strategy is versatile and could be used to synthesize large ZnSe, CdSe and PbSe nanocrystals with average sizes up to 35 nm, 76 nm and 87 nm, respectively. The control of quantum-confined and classical effects in these large semiconductor nanocrystals will open up new directions for fundamental research and application exploration.

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Fig. 1: The synthesis of ZnSe nanocrystals through a hot-injection method.
Fig. 2: Nucleation and growth model of nanocrystals.
Fig. 3: Epitaxial growth of large ZnSe nanocrystals.
Fig. 4: Optical, morphology and structural characterization of large ZnSe/ZnS core–shell nanocrystals.
Fig. 5: TEM images of large CdSe and PbSe nanocrystals.

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Data availability

The authors declare that the data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

This work was supported by Beijing Natural Science Foundation (Z210018, H.Z.), National Natural Science Foundation of China (61735004, H.Z.) and BOE Technology Group Co., Ltd. We would like to thank the Experimental Center of Advanced Materials of Beijing Institute of Technology for the support in materials synthesis and characterization. Z.L. and R.L. acknowledge the support from the S&T Program of Hebei under grant (216Z0601G, R.L.). The authors would like to acknowledge H. Bao (Beijing Institute of Technology) for checking the calculation of the diffusion-controlled model.

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Authors and Affiliations

  1. National Engineering Research Center for Rare Earth, General Research Institute for Nonferrous Metals, Beijing, China

    Zhiwei Long & Ronghui Liu

  2. MIIT Key Laboratory for Low-dimensional Quantum Structure and Devices, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing, China

    Zhiwei Long, Mingrui Liu, Xian-gang Wu, Kai Gu & Haizheng Zhong

  3. MIIT Key Laboratory for Low-dimensional Quantum Structure and Devices, School of Optics and Photonics, Beijing Institute of Technology, Beijing, China

    Gaoling Yang

  4. BOE Technology Group Co., Ltd, Beijing, China

    Zhuo Chen & Yang Liu

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  1. Zhiwei Long
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Contributions

H.Z., Y.L. and Z.C. conceptualized the project. H.Z., R.L. and G.Y. supervised the project. Z.L., M.L. and K.G. performed the materials synthesis and conducted the characterization measurements. H.Z., Z.L. and X.W. proposed the nucleation model. Z.L., G.Y. and H.Z. analysed the results and wrote the draft of the manuscript with subsequent input of the other authors.

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Correspondence to Gaoling Yang, Ronghui Liu or Haizheng Zhong.

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Peer review information

Nature Synthesis thanks Zuliang Du, Guohua Jia and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. The primary handling editor was Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Figs. 1–25, Tables 1–2 and Sections 1–4.

Supplementary Data Fig. 1

Statistical Source Data for Supplementary Figs. 1–9, 11–15, 17–21, 24 and 25.

Supplementary Data Fig. 2

Unprocessed TEM and STEM images for Supplementary Figs. 1, 10, 11, 22 and 23.

Source data

Source Data Fig. 1

Raw data of absorption and PL spectra, and plots of PL peak, UV peak, FWHM and diameter.

Source Data Fig. 2

Raw data of the plots of absorbance and nanocrystal concentration at different reaction conditions. Raw data of plots of standard deviation and the simulation data. Calculation data of diffusion radius.

Source Data Fig. 3

Raw data of absorption and PL spectra of different growth processes of ZnSe nanocrystals.

Source Data Fig. 3

Unprocessed TEM images of ZnSe nanocrystals with different sizes.

Source Data Fig. 4

Raw data of absorption and PL spectra of ZnSe core and ZnSe/ZnS core–shell nanocrystals. Raw data of plots of PLQY, PL peak and FWHM. Raw data of XRD patterns for ZnSe core and ZnSe/ZnS core–shell nanocrystals.

Source Data Fig. 4

Unprocessed TEM images of ZnSe and ZnSe/ZnS nanocrystals as well as their corresponding HRTEM images.

Source Data Fig. 5

Unprocessed TEM images of CdSe and PbSe nanocrystals with different sizes.

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Long, Z., Liu, M., Wu, Xg. et al. A reactivity-controlled epitaxial growth strategy for synthesizing large nanocrystals. Nat. Synth 2, 296–304 (2023). https://doi.org/10.1038/s44160-022-00210-5

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