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Parallel photon avalanche nanoparticles for tunable emission and multicolour sub-diffraction microscopy

Nature Photonics volume 19, pages 692–700 (2025)Cite this article

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Abstract

Photon avalanche (PA) can generate upconversion luminescent emission that grows steeply as a function of excitation power, effectively exhibiting a high order of nonlinearity (N) that is attractive for applications ranging from photophysics studies to biophotonics. Besides the limitations in available material systems, PA is typically sustained by a single reservoir level, limiting the ability to modulate the chromaticity of the emission as well as leading to small values of N and large excitation thresholds. Here we report a parallel PA mechanism in holmium (Ho3+)-doped nanoparticles for tunable emission at room temperature. The intermediate 5I7 and 5I6 levels of Ho3+ serve as dual reservoir levels that create two parallel energy loops. This activates multiple emissive levels and enables red, green and blue PA emission under 965 nm continuous-wave excitation. By rationally engineering transition kinetics through controlling doping concentration and core/shell configuration, we demonstrate multicolour PA with large N values of 17–22 and mild excitation threshold of ~22 kW cm−2. Moreover, emission can be tailored from almost pure red to intense red, green and blue by modifying the host lattice and introducing additional cross-relaxation pathways by doping with Ce3+/Tm3+. When using the nanoparticles to label biological cells, we demonstrate multicolour imaging on a single-continuous-wave-beam microscope with lateral spatial resolution of 78 nm and 102 nm in the green–blue and red channel, respectively. These findings open the way for manufacturing nonlinear multicolour fluorophores for versatile optical and biological applications.

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Fig. 1: Principles of the PPA.
Fig. 2: PA emissions of Ho3+-doped nanoparticles.
Fig. 3: PPA mechanism and kinetics modulation of Ho3+-doped nanoparticles.
Fig. 4: Single-CW-beam sub-diffraction imaging enabled by PPA.
Fig. 5: PPA-enabled tunable chromaticity and multicolour sub-diffraction imaging.

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Data availability

The data that support the findings of this work are available within the article. Source data are provided with this paper.

Code availability

The codes for numerical simulations of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

L.-D.S., C.-H.Y. and H.D. acknowledge the support from the National Natural Science Foundation of China (numbers 22031002, 21931001, 21927901 and 22205009) and the Ministry of Science and Technology of the People’s Republic of China (numbers 2022YFF0710001, 2023YFB3507101 and 2022YFB3503700). Q.Z. appreciates the support from the National Natural Science Foundation of China (numbers 62335008 and 62122028) and the Guangdong Basic and Applied Basic Research Foundation (number 2023B1515040018).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Hao Dong, Lin-Quan Guan, Yusen Liang, Jin-Wen Zhang, Xiao-Yong Wang, Ze-Yu Lyu, Xiang-Fei Yang, Ling-Dong Sun & Chun-Hua Yan

  2. Centre for Optical and Electromagnetic Research, National Centre for International Research on Green Optoelectronics, Guangdong Provincial Key Laboratory of Optical Information Materials and Technology, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou, China

    Shuqian Qiao, Yusen Liang, Zhimin Zhu, Yue Ni, Xin Guo & Qiuqiang Zhan

  3. MOE Key Laboratory and Guangdong Provincial Key Laboratory of Laser Life Science, Guangdong Engineering Research Centre of Optoelectronic Intelligent Information Perception, South China Normal University, Guangzhou, China

    Qiuqiang Zhan

  4. College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, China

    Chun-Hua Yan

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  1. Hao Dong
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Contributions

H.D., L.-D.S. and C.-H.Y. conceived of this project, designed the experiments and wrote the paper. H.D., S.Q., Y.L., Z.Z., X.-Y.W., Y.N., X.G., Z.-Y.L., X.-F.Y., L.-D.S., Q.Z. and C.-H.Y. performed the experiments. L.-Q.G. and J.-W.Z. carried out the rate equation modelling. L.-D.S., Q.Z. and C.-H.Y. supervised this project. All authors contributed to data analysis, discussions and paper preparation.

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Correspondence to Ling-Dong Sun, Qiuqiang Zhan or Chun-Hua Yan.

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Extended data

Extended Data Table 1 Comparison of the mechanism and characteristics between PPA of Ho3+ and previous multicolour PA
Full size table

Extended Data Fig. 1 PPA mechanism of Ho3+.

The 5I7 level is populated multiplicatively by CR, and serve as the reservoir level in the generation of red PA emission. The 5I6 level is populated via the cooperation of multiple CRs along with proper NRs, and serve as the reservoir level in the generation of green PA emission. The blue PA emission can be generated through additional ESAs and CRs, some of which are participated by the two reservoir levels.

Extended Data Fig. 2 Bright field and PA luminescence imaging of two BS-C-1 cells labelled with Ho3+-doped nanoparticles.

(a–d) Bright field (a), red (R) emission channel (b), green/blue (GB) emission channel (c), and overlay (d) images. Phalloidin-modified LLF:Ho,Ce@LYF nanoparticles were used for targeting the intercellular actin filaments (tunneling nanotubes), while PAA-modified NGF:Ho,Tm nanoparticles were used for entering the cytoplasm. The two cells were connected via the intercellular actin filaments, enabling direct observation of nanoparticle transport through these intercellular structures.

Extended Data Fig. 3 Parallel multicolour sub-cellular imaging with Ho3+-doped PPA nanoparticles.

(a, b) Multicolour sub-cellular imaging in large (a) and small (b) FOVs with red and green/blue PA emissions from phalloidin-modified LLF:Ho,Ce@LYF and PAA-modified NGF:Ho,Tm nanoparticles, respectively. Images in (b) were the enlarged view of the regions of interest in (a). (c) Red PA emission spectra of the intracellular NGF:Ho,Tm and LLF:Ho,Ce@LYF on the actin filaments. (d) PSF profiles and corresponding Gaussian fits along the dashed lines in (b). The pixel dwell time is 200 μs for all images.

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Source Data Extended Data Fig./Table 3

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Dong, H., Guan, LQ., Qiao, S. et al. Parallel photon avalanche nanoparticles for tunable emission and multicolour sub-diffraction microscopy. Nat. Photon. 19, 692–700 (2025). https://doi.org/10.1038/s41566-025-01671-8

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