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Molecular-sized fluorescent nanodiamonds

Abstract

Doping of carbon nanoparticles with impurity atoms is central to their application1,2. However, doping has proven elusive for very small carbon nanoparticles because of their limited availability and a lack of fundamental understanding of impurity stability in such nanostructures3. Here, we show that isolated diamond nanoparticles as small as 1.6 nm, comprising only 400 carbon atoms, are capable of housing stable photoluminescent colour centres, namely the silicon vacancy (SiV)4,5. Surprisingly, fluorescence from SiVs is stable over time, and few or only single colour centres are found per nanocrystal. We also observe size-dependent SiV emission supported by quantum-chemical simulation of SiV energy levels in small nanodiamonds. Our work opens the way to investigating the physics and chemistry of molecular-sized cubic carbon clusters and promises the application of ultrasmall non-perturbative fluorescent nanoparticles as markers in microscopy and sensing.

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Figure 1: Structure of SiV centre in diamond.
Figure 2: Photoluminescence analysis of the meteoric nanodiamonds.
Figure 3: HRTEM analysis of meteoritic nanodiamonds.
Figure 4: FCS measurement of luminescent meteoritic nanodiamonds and a dye molecule (Rhodamine 6G (Rh 6G)).
Figure 5: Detailed analysis of a fluorescent spot presumably containing only few emitters.

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Acknowledgements

This work was supported in part by Russian Foundation for Basic Research (RFBR) grants nos 11-02-01432, 12-05-00208 and 12-03-00787, a grant from Russian Academy of Science (RAS) programme no. 24, a grant of the President of the Russian Federation for leading scientific schools (no. 3076.2012.2), an National Institutes of Health (NIH) grant (no. C09-00053), the European Commission, EU FP7 grants Diamond based atomic nanotechnologies (DIAMANT) and Development of diamond intracellular nanoprobes for oncogen transformation dynamics monitoring in living cells (DINAMO), as well as the European Research Council (ERC) (via project Spin Quantum Technologies (SQUTEC) Biology and Quantum (BioQ)), the Deutsche Forschungsgemeinschaft (DFG) (via Sonderforschungsbereiches (SFB) 716) and the Volkswagenstiftung.

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Contributions

I.V., J.W., P.H. and F.J. designed and coordinated the experiment. I.V., A.A.S., L.F.S., A.V.F., O.I.L., V.I.K. and I.S. prepared and characterized the sample. U.K. and J.B. carried out the high-resolution electron microscopy. T.R., S.S. and S.Y.L. designed, set up and carried out fluorescence measurements. A.G., D.A. and M.V. carried out the calculations and analysed the simulation data. I.V., T.R., S.Y.L., A.G., P.H. and J.W. wrote the manuscript.

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Correspondence to Jörg Wrachtrup.

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Vlasov, I., Shiryaev, A., Rendler, T. et al. Molecular-sized fluorescent nanodiamonds. Nature Nanotech 9, 54–58 (2014). https://doi.org/10.1038/nnano.2013.255

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