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Migrating photon avalanche in different emitters at the nanoscale enables 46th-order optical nonlinearity

Nature Nanotechnology volume 17, pages 524–530 (2022)Cite this article

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Abstract

A photon avalanche (PA) effect that occurs in lanthanide-doped solids gives rise to a giant nonlinear response in the luminescence intensity to the excitation light intensity. As a result, much weaker lasers are needed to evoke such PAs than for other nonlinear optical processes. Photon avalanches are mostly restricted to bulk materials and conventionally rely on sophisticated excitation schemes, specific for each individual system. Here we show a universal strategy, based on a migrating photon avalanche (MPA) mechanism, to generate huge optical nonlinearities from various lanthanide emitters located in multilayer core/shell nanostructrues. The core of the MPA nanoparticle, composed of Yb3+ and Pr3+ ions, activates avalanche looping cycles, where PAs are synchronously achieved for both Yb3+ and Pr3+ ions under 852 nm laser excitation. These nanocrystals exhibit a 26th-order nonlinearity and a clear pumping threshold of 60 kW cm−2. In addition, we demonstrate that the avalanching Yb3+ ions can migrate their optical nonlinear response to other emitters (for example, Ho3+ and Tm3+) located in the outer shell layer, resulting in an even higher-order nonlinearity (up to the 46th for Tm3+) due to further cascading multiplicative effects. Our strategy therefore provides a facile route to achieve giant optical nonlinearity in different emitters. Finally, we also demonstrate applicability of MPA emitters to bioimaging, achieving a lateral resolution of ~62 nm using one low-power 852 nm continuous-wave laser beam.

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Fig. 1: Theoretical and experimental PA studies in Yb3+/Pr3+ co-doped nanoparticles.
Fig. 2: The characterizations of PA effect in Yb3+/Pr3+ co-doped nanoparticles.
Fig. 3: Demonstration of migrating photon avalanche (MPA).
Fig. 4: Set-up, single-nanoparticle imaging and subcellular filament imaging of ultralow-power, single-CW-beam, MPA nanoscopy.

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Data availability

Source data are provided with this paper. The data that support the findings of this study are available within the paper and the Supplementary Information. Other relevant data are available from the corresponding author upon reasonable request.

Code availability

The MATLAB-based codes for theoretical modelling and numerical simulations are available from the corresponding author upon reasonable request.

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Acknowledgements

Q.Z acknowledges support from the National Natural Science Foundation of China (62122028, 11974123), the Guangdong Provincial Science Fund for Distinguished Young Scholars (2018B030306015), the Guangdong Provincial Natural Science Fund Projects (2019A050510037), the Guangdong Innovative Research Team Program (201001D0104799318) and the Guangdong College Student Scientific and Technological Innovation ‘Climbing Program’ Special Fund (pdjh2021a0127). J.W. and H.L. acknowledge support from the Swedish Research Council (VR 2016-03804), the Carl Tryggers Foundation (CTS 18:229), the ÅForsk Foundation (19-424), the Olle Engkvists Foundation (200-0514) and the Swedish Foundation for Strategic Research (SSF ITM17-0491). We acknowledge D. Yang and G. Dong at South China University of Technology for help in measuring the ytterbium emission decay time.

Author information

Author notes

  1. These authors contributed equally: Yusen Liang, Zhimin Zhu, Shuqian Qiao.

Authors and Affiliations

  1. Centre for Optical and Electromagnetic Research, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou, P. R. China

    Yusen Liang, Zhimin Zhu, Shuqian Qiao, Xin Guo, Rui Pu, Huan Tang, Tingting Peng & Qiuqiang Zhan

  2. Experimental Biomolecular Physics, Department of Applied Physics, KTH Royal Institute of Technology, Stockholm, Sweden

    Haichun Liu & Jerker Widengren

  3. 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, P. R. China

    Hao Dong & Ling-Dong Sun

  4. MOE Key Laboratory of Laser Life Science, Institute of Laser Life Science, Guangdong Engineering Research Centre of Optoelectronic Intelligent Information Perception, South China Normal University, Guangzhou, P. R. China

    Qiuqiang Zhan

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Contributions

Q.Z. conceived and designed the project. Y.L., and Z.Z. built the optical system. Y.L., Q.Z. and Z.Z. were responsible for the theoretical analysis and simulation. S.Q., T.P. and Y.L. were responsible for fabrication and characterization of nanoparticles. Y.L., Z.Z., S.Q., R.P. and H.T. acquired and processed data. S.Q. and X.G. prepared the samples for imaging. Z.Z. and Y.L. were responsible for super-resolution imaging. Y.L., Z.Z., Q.Z., S.Q., H.L. and H.D. analysed the data with input from L.-D.S. and J.W. The paper was written by Q.Z., Z.Z., Y.L., H.L and R.P. All authors commented on the data and on the final version of the manuscript. Q.Z. supervised the project.

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Correspondence to Qiuqiang Zhan.

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Nature Nanotechnology thanks Artur Bednarkiewicz, Giuseppe Vicidomini and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Simulation results for the Yb/Pr(15/0.5%) system.

The population density for each state was simulated under different excitation intensities, including a, the excited state of Yb3+, 2F7/2; b, the metastable state of Pr3+, 1G4, 3H6; c, the excited state of Pr3+, 1D2, 3P0 and 3P1. The excitation intensity dependent curves show clear thresholds and the slopes are much steeper than one (one-photon absorption) or two (tow-photon absorption). These results indicated that all the excited states shown here are involved in the photon avalanches.

Source data

Extended Data Fig. 2 The in-depth analysis of the effect of doping concentration on photon avalanche.

a, The lifetime curves of the 1008-nm emission (Yb3+) in NaYF4:Yb/Pr(x/0.5%)@NaYF4 (x=2, 15, 50) under 980-nm laser excitation. b, The calculated excitation intensity dependent population density for the Yb/Pr(2/0.5%), Yb/Pr(15/0.5%) and Yb/Pr(50/0.5%) systems. PA can be built in high doping but with different pumping thresholds. c, The calculated excitation intensity dependent population density for the Yb/Pr(15/0.35%), Yb/Pr(15/0.5%) and Yb/Pr(15/0.75%) systems. d, The calculated upconversion luminescence quantum yields (UCQY) of photon avalanche nanoparticles NaYF4:Yb/Pr(15/0.5%)@NaYF4 under 852-nm PA excitation and 980-nm upconversion excitation, respectively, indicate the much higher emission efficiency of PA (at the order of 20%) compared to traditional upconversion luminescence (at the order of 2% even less).

Source data

Extended Data Fig. 3 The effect of temperature on photon avalanche.

a, Schematic drawing of temperature control setup. b, Power dependence curves of NaYF4:Yb/Pr(15/0.5%)@ NaYF4 under different temperature conditions. It can be seen from the results that the nonlinear slope decreases slowly with rising temperature because the increasing temperature leads to the acceleration of phonon relaxation and affects the population of the metastable state, hindering the construction of PA. This also indicates that the heating effect of MPA nanoparticles caused by the laser itself is not obvious for the experiments under room temperature, otherwise the elevated temperature will weaken the PA nonlinearity.

Source data

Extended Data Fig. 4 Schematic energy diagram for illustrating MPA activated with Tm3+ or Ho3+.

The photon avalanche is built up in the Yb3+/Pr3+ co-doped core and both Yb3+ and Pr3+ are avalanched. A fraction of avalanching energy from the Yb3+/Pr3+ co-doped core can be transferred to the Yb3+/Tm3+ or Yb3+/Ho3+ co-doped shell via the Yb3+ sublattice. Consequently, photon avalanche can be extended to Tm3+ or Ho3+ with multiplicative amplification of nonlinearity in MPA.

Extended Data Fig. 5 MPA super-resolution imaging for NaYF4:Yb/Pr(15/0.5%) @NaYF4 nanoparticles (26 nm in diameter) sparsely distributed on the glass slide.

a-j, A sequence of images with different excitation intensity (from 828 to 76 kW cm-2) were captured. The greatly narrowed effective point spread functions (PSFs) of the imaging spots with the decreasing laser power clearly show the advantages of giant nonlinearity in MPA nanoparticles, and low-power, single-beam super-resolution microscopy. k, These MPA nanoparticles did not show any photobleaching after one-hour continuous laser-scanning imaging and exhibited giant photon budget, which overcomes the photobleaching issue in some other super-resolutions imaging and is of outmost importance for biological imaging applications. l, The effective FWHM of MPA imaging is dependent on the excitation intensity because the nonlinearity order varies with the excitation intensity. The green curve is calculated according to the formula \(d = \lambda /2{{{\mathrm{NA}}}}\sqrt N\) (N means the experimentally measured nonlinearity order from the power dependence curve, Fig. 1d) and red squares denote the measured FWHMs of the imaging under different excitation intensities.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–15, Tables 1–4 and references.

Source data

Source Data Fig. 1

Source data for the results shown in Fig. 1.

Source Data Fig. 2

Source data for the results shown in Fig. 2.

Source Data Fig. 3

Source data for the results shown in Fig. 3.

Source Data Fig. 4

Source data for the results shown in Fig. 4.

Source Data Extended Data Fig. 1

Source data for the results shown in Extended Data Fig. 1.

Source Data Extended Data Fig. 2

Source data for the results shown in Extended Data Fig. 2.

Source Data Extended Data Fig. 3

Source data for the results shown in Extended Data Fig. 3.

Source Data Extended Data Fig. 5

Source data for the results shown in Extended Data Fig. 5.

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Liang, Y., Zhu, Z., Qiao, S. et al. Migrating photon avalanche in different emitters at the nanoscale enables 46th-order optical nonlinearity. Nat. Nanotechnol. 17, 524–530 (2022). https://doi.org/10.1038/s41565-022-01101-8

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