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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References
Mochalin, V. N., Shenderova, O., Ho, D. & Gogotsi, Y. The properties and applications of nanodiamonds. Nature Nanotech. 7, 11–23 (2012).
Hui, Y. Y., Cheng, C-L. & Chang, H-C. Nanodiamonds for optical bioimaging. J. Phys. 43, 374021 (2010).
Barnard, A. S. & Sternberg, M. Substitutional nitrogen in nanodiamond and Bucky-diamond particles. J. Phys. Chem. B 109, 17107–17112 (2005).
Wang, C., Kurtsiefer, C., Weinfurter, H. & Burchard, B. Single photon emission from SiV centres in diamond produced by ion implantation. J. Phys. B 39, 37–41 (2006).
Neu, E., Agio, M. & Becher, C. Photophysics of single silicon vacancy centers in diamond: implications for single photon emission. Opt. Express 20, 19956–19971 (2012).
Evanko, D. The new fluorescent probes on the block. Nature Methods 5, 218–219 (2008).
Biju, V., Itoh, T., Anas, A., Sujith, A. & Ishikawa, M. Semiconductor quantum dots and metal nanoparticles: syntheses, optical properties, and biological applications. Anal. Bioanal. Chem. 391, 2469–2495 (2008).
Taylor, A., Wilson, K. M., Murray, P., Fernig, D. G. & Lévy, R. Long-term tracking of cells using inorganic nanoparticles as contrast agents: are we there yet? Chem. Soc. Rev. 41, 2707–2717 (2012).
Barnard, A. S., Vlasov, I. I. & Ralchenko, V. G. Predicting the distribution and stability of photoactive defect centers in nanodiamond biomarkers. J. Mater. Chem. 19, 360–365 (2009).
Raty, J-Y., Galli, G., Bostedt, C., van Buuren, T. W. & Terminello, L. J. Quantum confinement and fullerenelike surface reconstructions in nanodiamonds. Phys. Rev. Lett. 90, 037401 (2003).
Bolker, A., Saguy, C., Tordjman, M. & Kalish, R. Quantum confinement and Coulomb blockade in isolated nanodiamond crystallites. Phys. Rev. B 88, 035442 (2013).
Bradac, C. et al. Observation and control of blinking nitrogen-vacancy centres in discrete nanodiamonds. Nature Nanotech. 5, 345–349 (2010).
Vlasov, I. I. et al. Nanodiamond photoemitters based on strong narrow-band luminescence from silicon-vacancy defects. Adv. Mater. 21, 808–812 (2009).
Lewis, R. S., Anders, E. & Draine, B. T. Properties, detectability and origin of interstellar diamonds in meteorites. Nature 339, 117–121 (1989).
Daulton, T. L., Eisenhour, D. D., Bernatowicz, T. J., Lewis, R. S. & Buseck, P. R. Genesis of presolar diamonds: comparative high-resolution transmission electron microscopy study of meteoritic and terrestrial nano-diamonds. Geochim. Cosmochim. Acta 60, 4853–4872 (1996).
Shiryaev, A. A. et al. Spectroscopic study of impurities and associated defects in nanodiamonds from Efremovka (CV3) and Orgueil (CI) meteorites. Geochim. Cosmochim. Acta 75, 3155–3165 (2011).
Goss, J. P., Jones, R., Breuer, S. J., Briddon, P. R. & Öberg, S. The twelve-line 1.682 eV luminescence center in diamond and the vacancy-silicon complex. Phys. Rev. Lett. 77, 3041–3044 (1996).
Erwin, S. C. et al. Doping semiconductor nanocrystals. Nature 436, 91–94 (2005).
Chang, Y. K. et al. Quantum confinement effect in diamond nanocrystals studied by X-ray-absorption spectroscopy. Phys. Rev. Lett. 82, 5377–5380 (1999).
Berg, T. et al. Quantum confinement observed in the X-ray absorption spectrum of size distributed meteoritic nanodiamonds. J. Appl. Phys. 104, 064303 (2008).
Amari, S., Lewis, R. S. & Anders, E. Interstellar grains in meteorites: I. Isolation of SiC, graphite and diamond; size distributions of SiC and graphite. Geochim. Cosmochim. Acta 58, 459–470 (1994).
Clark, C. D., Kanda, H., Kiflawi, I. & Sittas, G. Silicon defects in diamond. Phys. Rev. B 51, 16681–16688 (1995).
Neu, E. et al. Single photon emission from silicon-vacancy colour centres in chemical vapour deposition nano-diamonds on iridium. New J. Phys. 13, 025012 (2011).
Sternschulte, H., Thonke, K., Sauer, R., Münzinger, P. & Michler, P. 1.681-eV luminescence center in chemical-vapor-deposited homoepitaxial diamond films. Phys. Rev. B 50, 14554–14560 (1994).
Krichevsky, O. & Bonnet, G. Fluorescence correlation spectroscopy: the technique and its applications. Rep. Prog. Phys. 65, 251–297 (2002).
Neugart, F. et al. Dynamics of diamond nanoparticles in solution and cells. Nano Lett. 7, 3588–3591 (2007).
Kitson, S. C., Jonsson, P., Rarity, J. G. & Tapster, P. R. Intensity fluctuation spectroscopy of small numbers of dye molecules in a microcavity. Phys. Rev. 58, 620–627 (1998).
Neu, E. et al. Narrowband fluorescent nanodiamonds produced from chemical vapor deposition films. Appl. Phys. Lett. 98, 243107 (2011).
Gali, A. & Maze, J. R. An ab initio study on split silicon-vacancy defect in diamond: electronic structure and related properties. Preprint at http://arXiv.org/pdf/1310.2137 (2013).
Gali, A. Time-dependent density functional study on the excitation spectrum of point defects in semiconductors. Phys. Status Solidi B 248, 1337–1346 (2011).
Iakoubovskii, K., Adriaenssens, G. J., Dogadkin, N. N. & Shiryaev, A. A. Optical characterization of some irradiation-induced centers in diamond. Diam. Relat. Mater. 10, 18–26 (2001).
Gendron, P-O., Avaltroni, F. & Wilkinson, K. J. Diffusion coefficients of several rhodamine derivatives as determined by pulsed field gradient–nuclear magnetic resonance and fluorescence correlation spectroscopy. J. Fluoresc. 18, 1093–1101 (2008).
Müller, C. B. et al. Precise measurement of diffusion by multi-color dual-focus fluorescence correlation spectroscopy. EPL Eur. Lett. 83, 46001 (2008).
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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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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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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DOI: https://doi.org/10.1038/nnano.2013.255