The spectral linewidth of an ensemble of fluorescent emitters is dictated by the combination of single-emitter linewidths and sample inhomogeneity. For semiconductor nanocrystals, efforts to tune ensemble linewidths for optical applications have focused primarily on eliminating sample inhomogeneities, because conventional single-molecule methods cannot reliably build accurate ensemble-level statistics for single-particle linewidths. Photon-correlation Fourier spectroscopy in solution (S-PCFS) offers a unique approach to investigating single-nanocrystal spectra with large sample statistics and high signal-to-noise ratios, without user selection bias and at fast timescales. With S-PCFS, we directly and quantitatively deconstruct the ensemble linewidth into contributions from the average single-particle linewidth and from sample inhomogeneity. We demonstrate that single-particle linewidths vary significantly from batch to batch and can be synthetically controlled. These findings delineate the synthetic challenges facing underdeveloped nanomaterials such as InP and InAs core–shell particles and introduce new avenues for the synthetic optimization of fluorescent nanoparticles.
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Murray, C. B., Norris, D. J. & Bawendi, M. G. Synthesis and characterization of nearly monodisperse CdE (E = S, Se, Te) semiconductor nanocrystallites. J. Am. Chem. Soc. 115, 8706–8715 (1993).
Greytak, A. B. et al. Alternating layer addition approach to CdSe/CdS core/shell quantum dots with near-unity quantum yield and high on-time fractions. Chem. Sci. 3, 2028–2034 (2012).
Hines, M. A. & Guyot-Sionnest, P. Synthesis and characterization of strongly luminescing ZnS-capped CdSe nanocrystals. J. Phys. Chem. 100, 468–471 (1996).
Wang, X. et al. Non-blinking semiconductor nanocrystals. Nature 459, 686–689 (2009).
Medintz, I. L., Uyeda, H. T., Goldman, E. R. & Mattoussi, H. Quantum dot bioconjugates for imaging, labelling and sensing. Nature Mater. 4, 435–446 (2005).
Steckel, J. S. et al. Color-saturated green-emitting QD-LEDs. Angew. Chem. Int. Ed. 45, 5796–5799 (2006).
Tang, J. & Sargent, E. H. Infrared colloidal quantum dots for photovoltaics: fundamentals and recent progress. Adv. Mater. 23, 12–29 (2011).
Konstantatos, G. et al. Ultrasensitive solution-cast quantum dot photodetectors. Nature 442, 180–183 (2006).
Eisler, H-J. et al. Color-selective semiconductor nanocrystal laser. Appl. Phys. Lett. 80, 4614–4616 (2002).
Bawendi, M. G., Steigerwald, M. L. & Brus, L. E. The quantum mechanics of larger semiconductor clusters (‘quantum dots'). Annu. Rev. Phys. Chem. 41, 477–496 (1990).
Moerner, W. E. & Fromm, D. P. Methods of single-molecule fluorescence spectroscopy and microscopy. Rev. Sci. Instrum. 74, 3597–3619 (2003).
Empedocles, S. A., Neuhauser, R., Shimizu, K. T. & Bawendi, M. G. Photoluminescence from single semiconductor nanostructures. Adv. Mater. 11, 1243–1256 (1999).
Gómez, D. E., Califano, M. & Mulvaney, P. Optical properties of single semiconductor nanocrystals. Phys. Chem. Chem. Phys. 8, 4989–5011 (2006).
Gómez, 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).
Brokmann, X., Bawendi, M., Coolen, L. & Hermier, J-P. Photon-correlation Fourier spectroscopy. Opt. Express 14, 6333–6341 (2006).
Brokmann, X., Marshall, L. F. & Bawendi, M. G. Revealing single emitter spectral dynamics from intensity correlations in an ensemble fluorescence spectrum. Opt. Express 17, 4509–4517 (2009).
Marshall, L. F., Cui, J., Brokmann, X. & Bawendi, M. G. Extracting spectral dynamics from single chromophores in solution. Phys. Rev. Lett. 105, 053005 (2010).
Coolen, L., Brokmann, X., Spinicelli, P. & Hermier, J-P. Emission characterization of a single CdSe–ZnS nanocrystal with high temporal and spectral resolution by photon-correlation Fourier spectroscopy. Phys. Rev. Lett. 100, 027403 (2008).
Banin, U., Cerullo, G., Guzelian, A. & Bardeen, C. Quantum confinement and ultrafast dephasing dynamics in InP nanocrystals. Phys. Rev. B 55, 7059–7067 (1997).
Kim, S. et al. Highly luminescent InP/GaP/ZnS nanocrystals and their application to white light-emitting diodes. J. Am. Chem. Soc. 134, 3804–3809 (2012).
Allen, P. M. et al. InAs(ZnCdS) quantum dots optimized for biological imaging in the near-infrared. J. Am. Chem. Soc. 132, 470–471 (2010).
Reiss, P., Protière, M. & Li, L. Core/shell semiconductor nanocrystals. Small 5, 154–168 (2009).
Aharoni, A., Mokari, T., Popov, I. & Banin, U. Synthesis of InAs/CdSe/ZnSe core/shell1/shell2 structures with bright and stable near-infrared fluorescence. J. Am. Chem. Soc. 128, 257–264 (2006).
Johnson, I. & Spence, M. T. Z. (eds) Molecular Probes Handbook, A Guide to Fluorescent Probes and Labeling Technologies 11th edn (Life Technologies, 2010).
Nguyen, D. T. et al. Excitonic homogeneous broadening in single-wall carbon nanotubes. Chem. Phys. 413, 102–111 (2013).
Empedocles, S. A. & Bawendi, M. G. Influence of spectral diffusion on the line shapes of single CdSe nanocrystallite quantum dots. J. Phys. Chem. B 103, 1826–1830 (1999).
Kelley, A. M. Electron–phonon coupling in CdSe nanocrystals. J. Phys. Chem. Lett. 1, 1296–1300 (2010).
Sagar, D. et al. Size dependent, state-resolved studies of exciton–phonon couplings in strongly confined semiconductor quantum dots. Phys. Rev. B 77, 235321 (2008).
Salvador, M. R., Hines, M. A. & Scholes, G. D. Exciton–bath coupling and inhomogeneous broadening in the optical spectroscopy of semiconductor quantum dots. J. Chem. Phys. 118, 9380–9388 (2003).
Salvador, M. R., Graham, M. W. & Scholes, G. D. Exciton–phonon coupling and disorder in the excited states of CdSe colloidal quantum dots. J. Chem. Phys. 125, 184709 (2006).
Chernikov, A. et al. Phonon-assisted luminescence of polar semiconductors: Fröhlich coupling versus deformation-potential scattering. Phys. Rev. B 85, 035201 (2012).
Brovelli, S. et al. Nano-engineered electron–hole exchange interaction controls exciton dynamics in core–shell semiconductor nanocrystals. Nature Commun. 2, 280 (2011).
Chen, O. et al. Compact high-quality CdSe–CdS core–shell nanocrystals with narrow emission linewidths and suppressed blinking. Nature Mater. 12, 445–451 (2013).
Haustein, E. & Schwille, P. Fluorescence correlation spectroscopy: novel variations of an established technique. Annu. Rev. Biophys. Biomol. Struct. 36, 151–169 (2007).
This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering (award no. DE-FG02-07ER46454) and by the National Institutes of Health through the MIT Laser Biomedical Resource Center (award no. P41EB015871-26A1). J.C. acknowledges support from the National Science Foundation Graduate Research Fellowship Program. D.D.W. acknowledges support from the Fannie and John Hertz Foundation. The authors thank QD Vision for providing the InP core–shell sample and J. Cordero for help with synthesis.
The authors declare no competing financial interests.
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Cui, J., Beyler, A., Marshall, L. et al. Direct probe of spectral inhomogeneity reveals synthetic tunability of single-nanocrystal spectral linewidths. Nature Chem 5, 602–606 (2013). https://doi.org/10.1038/nchem.1654
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