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Compact high-quality CdSe–CdS core–shell nanocrystals with narrow emission linewidths and suppressed blinking

Nature Materials volume 12, pages 445–451 (2013)Cite this article

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Abstract

High particle uniformity, high photoluminescence quantum yields, narrow and symmetric emission spectral lineshapes and minimal single-dot emission intermittency (known as blinking) have been recognized as universal requirements for the successful use of colloidal quantum dots in nearly all optical applications. However, synthesizing samples that simultaneously meet all these four criteria has proven challenging. Here, we report the synthesis of such high-quality CdSe–CdS core–shell quantum dots in an optimized process that maintains a slow growth rate of the shell through the use of octanethiol and cadmium oleate as precursors. In contrast with previous observations, single-dot blinking is significantly suppressed with only a relatively thin shell. Furthermore, we demonstrate the elimination of the ensemble luminescence photodarkening that is an intrinsic consequence of quantum dot blinking statistical ageing. Furthermore, the small size and high photoluminescence quantum yields of these novel quantum dots render them superior in vivo imaging agents compared with conventional quantum dots. We anticipate these quantum dots will also result in significant improvement in the performance of quantum dots in other applications such as solid-state lighting and illumination.

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Figure 1: Optical properties of new generation CdSe–CdS core–shell QDs.
Figure 2: Morphology, composition and crystal structure characterization of new generation QDs.
Figure 3: Photoluminescence spectral correlation of single-QDs and ensemble QDs obtained through S-PCFS.
Figure 4: Blinking behaviour of new generation CdSe–CdS core–shell QDs and ensemble photoluminescence stability test.
Figure 5: Water-soluble CdSe–CdS core–shell QDs for in vivo imaging.

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References

  1. Dahan, M. et al. Diffusion dynamics of glycine receptors revealed by single-quantum dot tracking. Science 302, 442–445 (2003).

    Article  CAS  Google Scholar 

  2. Stroh, M. et al. Quantum dots spectrally distinguish multiple species within the tumour milieu in vivo. Nature Med. 11, 678–682 (2005).

    Article  CAS  Google Scholar 

  3. Chan, W. C. W. et al. Luminescent quantum dots for multiplexed biological detection and imaging. Curr. Opin. Biotechnol. 13, 40–46 (2002).

    Article  CAS  Google Scholar 

  4. Jaiswal, J. K. & Simon, S. M. Potentials and pitfalls of fluorescent quantum dots for biological imaging. Trends Cell Biol. 14, 497–504 (2004).

    Article  CAS  Google Scholar 

  5. Colvin, V. L., Schlamp, M. C. & Alivisatos, A. P. Light-emitting-diodes made from cadmium selenide nanocrystals and a semiconducting polymer. Nature 370, 354–357 (1994).

    Article  CAS  Google Scholar 

  6. Jang, H. S. et al. White light-emitting diodes with excellent colour rendering based on organically capped CdSe quantum dots and Sr3SiO5: Ce3+, Li+ phosphors. Adv. Mater. 20, 2696–2702 (2008).

    Article  CAS  Google Scholar 

  7. Lim, J. et al. Preparation of highly luminescent nanocrystals and their application to light-emitting diodes. Adv. Mater. 19, 1927–1932 (2007).

    Article  CAS  Google Scholar 

  8. Resch-Genger, U., Grabolle, M., Cavaliere-Jaricot, S., Nitschke, R. & Nann, T. Quantum dots versus organic dyes as fluorescent labels. Nature Methods 5, 763–775 (2008).

    Article  CAS  Google Scholar 

  9. Brokmann, X., Giacobino, E., Dahan, M. & Hermier, J. P. Highly efficient triggered emission of single photons by colloidal CdSe/ZnS nanocrystals. Appl. Phys. Lett. 85, 712–714 (2004).

    Article  CAS  Google Scholar 

  10. Fisher, B., Caruge, J. M., Zehnder, D. & Bawendi, M. Room-temperature ordered photon emission from multiexciton states in single CdSe core–shell nanocrystals. Phys. Rev. Lett. 94, 087403 (2005).

    Article  Google Scholar 

  11. Popovic, Z. et al. A nanoparticle size series for in vivo fluorescence imaging. Angew. Chem. Int. Ed. 49, 8649–8652 (2010).

    Article  CAS  Google Scholar 

  12. Reiss, P., Protiere, M. & Li, L. Core/shell semiconductor nanocrystals. Small 5, 154–168 (2009).

    Article  CAS  Google Scholar 

  13. Jun, S., Jang, E. J. & Chung, Y. S. Alkyl thiols as a sulphur precursor for the preparation of monodisperse metal sulphide nanostructures. Nanotechnology 17, 4806–4810 (2006).

    Article  CAS  Google Scholar 

  14. Nirmal, M. et al. Fluorescence intermittency in single cadmium selenide nanocrystals. Nature 383, 802–804 (1996).

    Article  CAS  Google Scholar 

  15. Kuno, M. et al. Fluorescence intermittency in single InP quantum dots. Nano Lett. 1, 557–564 (2001).

    Article  CAS  Google Scholar 

  16. Frantsuzov, P., Kuno, M., Janko, B. & Marcus, R. A. Universal emission intermittency in quantum dots, nanorods and nanowires. Nature Phys. 4, 519–522 (2008).

    Article  Google Scholar 

  17. Hohng, S. & Ha, T. Near-complete suppression of quantum dot blinking in ambient conditions. J. Am. Chem. Soc. 126, 1324–1325 (2004).

    Article  CAS  Google Scholar 

  18. Fomenko, V. & Nesbitt, D. J. Solution control of radiative and nonradiative lifetimes: A novel contribution to quantum dot blinking suppression. Nano Lett. 8, 287–293 (2008).

    Article  CAS  Google Scholar 

  19. Hammer, N. I. et al. Coverage-mediated suppression of blinking in solid state quantum dot conjugated organic composite nanostructures. J. Phys. Chem. B 110, 14167–14171 (2006).

    Article  CAS  Google Scholar 

  20. Mahler, B. et al. Towards non-blinking colloidal quantum dots. Nature Mater. 7, 659–664 (2008).

    Article  CAS  Google Scholar 

  21. Chen, Y. et al. ‘Giant’ multishell CdSe nanocrystal quantum dots with suppressed blinking. J. Am. Chem. Soc. 130, 5026–5027 (2008).

    Article  CAS  Google Scholar 

  22. Wang, X. et al. Non-blinking semiconductor nanocrystals. Nature 459, 686–689 (2009).

    Article  CAS  Google Scholar 

  23. Li, J. J. et al. Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction. J. Am. Chem. Soc. 125, 12567–12575 (2003).

    Article  CAS  Google Scholar 

  24. Munro, A. M., Jen-La Plante, I., Ng, M. S. & Ginger, D. S. Quantitative study of the effects of surface ligand concentration on CdSe nanocrystal photoluminescence. J. Phys. Chem. C 111, 6220–6227 (2007).

    Article  CAS  Google Scholar 

  25. Wuister, S. F., Donega, C. D. & Meijerink, A. Influence of thiol capping on the exciton luminescence and decay kinetics of CdTe and CdSe quantum. J. Phys. Chem. B 108, 17393–17397 (2004).

    Article  CAS  Google Scholar 

  26. Gomez, D. E., van Embden, J. & Mulvaney, P. Spectral diffusion of single semiconductor nanocrystals: The influence of the dielectric environment. Appl. Phys. Lett. 88, 154106 (2006).

    Article  Google Scholar 

  27. Van Embden, J., Jasieniak, J. & Mulvaney, P. Mapping the optical properties of CdSe/CdS heterostructure nanocrystals: The effects of core size and shell thickness. J. Am. Chem. Soc. 131, 14299–14309 (2009).

    Article  CAS  Google Scholar 

  28. Clark, M. D., Kumar, S. K., Owen, J. S. & Chan, E. M. Focusing nanocrystal size distributions via production control. Nano Lett. 11, 1976–1980 (2011).

    Article  CAS  Google Scholar 

  29. Chen, O. et al. Synthesis of metal-selenide nanocrystals using selenium dioxide as the selenium precursor. Angew. Chem. Int. Ed. 47, 8638–8641 (2008).

    Article  CAS  Google Scholar 

  30. Mahler, B., Lequeux, N. & Dubertret, B. Ligand-controlled polytypism of thick-shell CdSe/CdS nanocrystals. J. Am. Chem. Soc. 132, 953–959 (2010).

    Article  CAS  Google Scholar 

  31. Chen, O. et al. Surface-functionalization-dependent optical properties of II–VI semiconductor nanocrystals. J. Am. Chem. Soc. 133, 17504–17512 (2011).

    Article  CAS  Google Scholar 

  32. Marshall, L. F., Cui, J., Brokmann, X. & Bawendi, M. G. Extracting spectral dynamics from single chromophores in solution. Phys. Rev. Lett. 105, 053005 (2010).

    Article  Google Scholar 

  33. Brokmann, X., Bawendi, M., Coolen, L. & Hermier, J. P. Photon-correlation Fourier spectroscopy. Opt. Express 14, 6333–6341 (2006).

    Article  Google Scholar 

  34. Kuno, M., Fromm, D. P., Hamann, H. F., Gallagher, A. & Nesbitt, D. J. ‘On’/‘off’ fluorescence intermittency of single semiconductor quantum dots. J. Chem. Phys. 115, 1028–1040 (2001).

    Article  CAS  Google Scholar 

  35. Empedocles, S. A., Neuhauser, R., Shimizu, K. & Bawendi, M. G. Photoluminescence from single semiconductor nanostructures. Adv. Mater. 11, 1243–1256 (1999).

    Article  CAS  Google Scholar 

  36. Brokmann, X. et al. Statistical ageing and nonergodicity in the fluorescence of single nanocrystals. Phys. Rev. Lett. 90, 120601 (2003).

    Article  CAS  Google Scholar 

  37. Chung, I. H. & Bawendi, M. G. Relationship between single quantum-dot intermittency and fluorescence intensity decays from collections of dots. Phys. Rev. B 70, 165304 (2004).

    Article  Google Scholar 

  38. Nair, G., Zhao, J. & Bawendi, M. G. Biexciton quantum yield of single semiconductor nanocrystals from photon statistics. Nano Lett. 11, 1136–1140 (2011).

    Article  CAS  Google Scholar 

  39. Park, Y. S. et al. Near-unity quantum yields of biexciton emission from CdSe/CdS nanocrystals measured using single-particle spectroscopy. Phys. Rev. Lett. 106, 187401 (2011).

    Article  Google Scholar 

  40. Zhao, J., Chen, O., Strasfeld, D. B. & Bawendi, M. G. Biexciton quantum yield heterogeneities in single CdSe (CdS) core (shell) nanocrystals and its correlation to exciton blinking. Nano Lett. 12, 4477–4483 (2012).

    Article  CAS  Google Scholar 

  41. Spinicelli, P. et al. Bright and grey states in CdSe-CdS nanocrystals exhibiting strongly reduced blinking. Phys. Rev. Lett. 102, 136801 (2009).

    Article  CAS  Google Scholar 

  42. Cichos, F., von Borczyskowski, C. & Orrit, M. Power-law intermittency of single emitters. Curr. Opin. Colloid Interface Sci. 12, 272–284 (2007).

    Article  CAS  Google Scholar 

  43. Gomez, D. E., Califano, M. & Mulvaney, P. Optical properties of single semiconductor nanocrystals. Phys. Chem. Chem. Phys. 8, 4989–5011 (2006).

    Article  CAS  Google Scholar 

  44. Ghosh, Y. et al. New insights into the complexities of shell growth and the strong influence of particle volume in nonblinking ‘giant’ core/shell nanocrystal quantum dots. J. Am. Chem. Soc. 134, 9634–9643 (2012).

    Article  CAS  Google Scholar 

  45. Malko, A. V. et al. Pump-intensity- and shell-thickness-dependent evolution of photoluminescence blinking in individual core/shell CdSe/CdS nanocrystals. Nano Lett. 11, 5213–5218 (2011).

    Article  CAS  Google Scholar 

  46. Gomez, D. E., van Embden, J., Jasieniak, J., Smith, T. A. & Mulvaney, P. Blinking and surface chemistry of single CdSe nanocrystals. Small 2, 204–208 (2006).

    Article  CAS  Google Scholar 

  47. CRC Handbook of Chemistry and Physics 85th edn (CRC, 2005).

  48. Bardou, F., Bouchaud, J. P., Aspect, A. & Cohen-Tannoudji, C. Levy Statistics and Laser Cooling (Cambridge Univ. Press, 2001).

    Book  Google Scholar 

  49. Lee, S. F. & Osborne, M. A. Brightening, blinking, bluing and bleaching in the life of a quantum dot: Friend or foe? ChemPhysChem 10, 2174–2191 (2009).

    Article  CAS  Google Scholar 

  50. Zhang, J., Campbell, R. E., Ting, A. Y. & Tsien, R. Y. Creating new fluorescent probes for cell biology. Nature Rev. Mol. Cell Biol. 3, 906–918 (2002).

    Article  CAS  Google Scholar 

  51. Brown, E. B. et al. In vivo measurement of gene expression, angiogenesis and physiological function in tumours using multiphoton laser scanning microscopy. Nature Med. 7, 864–868 (2001).

    Article  CAS  Google Scholar 

  52. Liu, W. et al. Compact biocompatible quantum dots via RAFT-mediated synthesis of imidazole-based random copolymer ligand. J. Am. Chem. Soc. 132, 472–483 (2010).

    Article  CAS  Google Scholar 

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Acknowledgements

The work received support from the NIH through grants 5-U54-CA119349 (M.G.B.) and 5R01CA126642 (M.G.B., D.F., R.K.J.), the ARO through the Institute for Soldier Nanotechnologies (W911NF-07-D-0004), and the NSF through a Collaborative Research in Chemistry Program (CHE-0714189) (M.G.B.). This work made use of the MRSEC Shared Experimental Facilities at MIT, supported by the National Science Foundation under award number DMR-08-19762 and the MIT DCIF NMR spectrometer funded through National Science Foundation Grants CHE-9808061 and DBI-9729592.

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA

    Ou Chen, Jing Zhao, Jian Cui, Cliff Wong, Daniel K. Harris, He Wei, Hee-Sun Han & Moungi G. Bawendi

  2. Massachusetts General Hospital and Harvard Medical School, 100 Blossom Street, Boston, Massachusetts 02114, USA

    Vikash P. Chauhan, Dai Fukumura & Rakesh K. Jain

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  1. Ou Chen
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Contributions

O.C. and M.G.B. conceived and designed the project. O.C. performed the bulk of the experimental work with help from J.Z., V.P.C., J.C., C.W., D.K.H., H.W. and H-S.H. The data was analysed by O.C., J.Z., V.P.C., J.C., C.W. and M.G.B. All authors discussed the results and took part in producing the manuscript.

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Correspondence to Moungi G. Bawendi.

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Chen, O., Zhao, J., Chauhan, V. et al. Compact high-quality CdSe–CdS core–shell nanocrystals with narrow emission linewidths and suppressed blinking. Nature Mater 12, 445–451 (2013). https://doi.org/10.1038/nmat3539

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