Abstract
Virtually all known fluorophores exhibit mysterious episodes of emission intermittency. A remarkable feature of the phenomenon is a power-law distribution of on- and off-times observed in colloidal semiconductor quantum dots, nanorods, nanowires and some organic dyes. For nanoparticles, the resulting power law extends over an extraordinarily wide dynamic range: nine orders of magnitude in probability density and five to six orders of magnitude in time. Exponents hover about the ubiquitous value of −3/2. Dark states routinely last for tens of seconds—practically forever on quantum mechanical timescales. Despite such infinite states of darkness, the dots miraculously recover and start emitting again. Although the underlying mechanism responsible for this phenomenon remains a mystery and many questions persist, we argue that substantial theoretical progress has been made.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$209.00 per year
only $17.42 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Cook, R. J. & Kimble, H. J. Possibility of direct observation of quantum jumps. Phys. Rev. Lett. 54, 1023–1026 (1985).
Moerner, W. E. & Orrit, M. Illuminating single molecules in condensed matter. Science 283, 1670–1676 (1999).
Wustholz, K. L. et al. Dispersive kinetics from single molecules oriented in single crystals of potassium acid phthalate. J. Phys. Chem. C 111, 9146–9156 (2007).
Yeow, E. K. L., Melnikov, S. M., Bell, T. D. M., De Schryver, F. C. & Hofkens, J. Characterizing the fluorescence intermittency of photobleaching kinetics of dye molecules immobilized on a glass surface. J. Phys. Chem. A 110, 1726–1734 (2006).
Hoogenboom, J. P., van Dijk, E. M. H. P., Hernando, J., van Hulst, N. F. & Garcia-Parajo, M. F. Power-law-distributed dark states are the main pathway for photobleaching of single organic molecules. Phys. Rev. Lett. 95, 097401 (2005).
Hoogenboom, J. P., Hernando, J., van Dijk, E. M. H. P., van Hulst, N. F. & Garcia-Parajo, M. F. Power-law blinking in the fluorescence of single organic molecules. ChemPhysChem 8, 823–833 (2007).
Schuster, J., Cichos, F. & von Borczyskowski, C. Blinking of single molecules in various environments. Opt. Spectrosc. 98, 778–783 (2005).
Haase, M. et al. Exponential and power-law kinetics in single-molecule fluorescence intermittency. J. Phys. Chem. B 108, 10445–10450 (2004).
Dickson, R. M., Cubitt, A. B., Tsien, R. Y. & Moerner, W. E. On/off blinking and switching behavior of single green fluorescent protein molecules. Nature 388, 355–358 (1997).
Vanden Bout, D. A. et al. Discrete intensity jumps and intramolecular electronic energy transfer in the spectroscopy of single conjugated polymer molecules. Science 277, 1074–1077 (1997).
Nirmal, M. et al. Fluorescence intermittency in single cadmium selenide nanocrystals. Nature 383, 802–804 (1996).
Kuno, M., Fromm, D. P., Hamann, H. F., Gallagher, A. & Nesbitt, D. J. Nonexponential ‘blinking’ kinetics of single CdSe quantum dots: A universal power law behavior. J. Chem. Phys. 112, 3117–3120 (2000).
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).
Shimizu, K. T. et al. Blinking statistics in single semiconductor nanocrystal quantum dots. Phys. Rev. B 63, 205316 (2001).
Pelton, M., Grier, D. G. & Guyot-Sionnest, P. Characterizing quantum-dot blinking using noise power spectra. Appl. Phys. Lett. 85, 819–821 (2004).
Pelton, M., Smith, G., Scherer, N. F. & Marcus, R. A. Evidence for a diffusion-controlled mechanism for fluorescence blinking of colloidal quantum dots. Proc. Natl Acad. Sci. 104, 14249–14254 (2007).
Zhang, K., Chang, H., Fu, A., Alivisatos, A. P. & Yang, H. Continuous distribution of emission states from single CdSe/ZnS quantum dots. Nano Lett. 6, 843–847 (2006).
Schlegel, G., Bohnenberger, J., Potapova, I. & Mews, A. Fluorescence decay time of single semiconductor nanocrystals. Phys. Rev. Lett. 88, 137401 (2002).
Fisher, B. R., Eisler, H. J., Stott, N. E. & Bawendi, M.G. Emission intensity dependence and single exponential behavior in single colloidal quantum dot fluorescence lifetimes. J. Phys. Chem. B 108, 143–148 (2004).
Chung, I. & Bawendi, M.G. Relationship between single quantum-dot intermittency and fluorescence intensity decays from collections of dots. Phys. Rev. B 70, 165304 (2004).
Neuhauser, R. G., Shimizu, K. T., Woo, W. K., Empedocles, S. A. & Bawendi, M. G. Correlation between fluorescence intermittency and spectral diffusion in single semiconductor quantum dots. Phys. Rev. Lett. 85, 3301–3304 (2000).
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).
Stefani, F. D., Zhong, X., Knoll, W., Han, M. & Kreiter, M. Memory in quantum-dot photoluminescence blinking. New J. Phys. 7, 197 (2005).
Stefani, F. D., Zhong, X., Knoll, W., Kreiter, M. & Han, M. Quantification of photoinduced and spontaneous quantum-dot luminescence blinking. Phys. Rev. B 72, 125304 (2005).
Hohng, S. & Ha, T. Near-complete suppression of quantum dot blinking in ambient conditions. J. Am. Chem. Soc. 126, 1324–1325 (2004).
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).
Fu, Y., Zhang, J. & Lakowicz, J. R. Suppressed blinking in single quantum dots (QDs) immobilized near silver island films (SIFs). Chem. Phys. Lett. 447, 96–100 (2007).
Park, S. J., Link, S., Miller, W. L., Gesquiere, A. & Barbara, P. F. Effect of electric field on the photoluminescence intensity of single CdSe nanocrystals. Chem. Phys. 341, 169–174 (2007).
Wang, S., Querner, C., Emmons, T., Drndić, M. & Crouch, C. H. Fluorescence blinking statistics from CdSe core and core–shell nanorods. J. Phys. Chem. B 110, 23221–23227 (2006).
Protasenko, V. V., Gordeyev, S. & Kuno, M. Spatial and intensity modulation of nanowire emission induced by mobile charges. J. Am. Chem. Soc. 129, 13160–13171 (2007).
Protasenko, V. V., Hull, K. L. & Kuno, M. Disorder-induced optical heterogeneity in single CdSe nanowires. Adv. Mater. 17, 2942–2949 (2005).
Glennon, J. J., Tang, R., Buhro, W. E. & Loomis, R. A. Synchronous photoluminescence intermittency (blinking) along whole semiconductor quantum wires. Nano Lett. 7, 3290–3295 (2007).
Kadanoff, L. P. Static phenomena near critical points—theory and experiment. Rev. Mod. Phys. 39, 395–431 (1967).
Cichos, F., von Borczyskowski, C. & Orrit, M. Power-law intermittency of single emitters. Curr. Opin. Colloid Interface Sci. 12, 272–284 (2007).
Gomez, D. E., Califano, M. & Mulvaney, P. Optical properties of single semiconductor nanocrystals. Phys. Chem. Chem. Phys. 8, 4989–5011 (2006).
Margolin, G., Protasenko, V., Kuno, M. & Barkai, E. Power law blinking quantum dots: Stochastic and physical models. Adv. Chem. Phys. 133, 327–356 (2006).
Tang, J. & Marcus, R. A. Single particle versus ensemble average: From power-law intermittency of a single quantum dot to stretched exponential fluorescence decay of an ensemble. J. Chem. Phys. 123, 054704 (2005).
Sher, P. H. et al. Power law carrier dynamics in semiconductor nanocrystals at nanosecond timescales. Appl. Phys. Lett. 92, 101111 (2008).
Margolin, G. & Barkai, E. Nonegrodicity of blinking nanocrystals and other Levy-walk processes. Phys. Rev. Lett. 94, 080601 (2005).
Bianco, S., Grigolini, P. & Paradisi, P. Fluorescence intermittency in blinking quantum dots: Renewal or slow modulation? J. Chem. Phys. 123, 174704 (2005).
Efros, A. L. & Rosen, M. Random telegraph signal in the photoluminescence intensity of a single quantum dot. Phys. Rev. Lett. 78, 1110–1113 (1997).
Verberk, R., van Oijen, A. M. & Orrit, M. Simple model for the power-law blinking of single semiconductor nanocrystals. Phys. Rev. B 66, 233202 (2002).
Tang, J. & Marcus, R. A. Diffusion-controlled electron transfer processes and power-law statistics of fluorescence intermittency of nanoparticles. Phys. Rev. Lett. 95, 107401 (2005).
Frantsuzov, P. A. & Marcus, R. A. Explanation of quantum dot blinking without the long-lived trap hypothesis. Phys. Rev. B. 72, 155321 (2005).
Krauss, T. D. & Brus, L. E. Charge, polarizability, and photoionization of single semiconductor nanocrystals. Phys. Rev. Lett. 83, 4840–4843 (1999).
Janko, B. & Ambegaokar, V. Parity fluctuations between Coulomb blockaded superconducting islands. Phys. Rev. Lett. 75, 1154–1157 (1995).
Acknowledgements
The authors would like to acknowledge the support of NSF, ONR and DOE-BES.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Frantsuzov, P., Kuno, M., Jankó, B. et al. Universal emission intermittency in quantum dots, nanorods and nanowires. Nature Phys 4, 519–522 (2008). https://doi.org/10.1038/nphys1001
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/nphys1001
This article is cited by
-
Electric-field-induced colour switching in colloidal quantum dot molecules at room temperature
Nature Materials (2023)
-
Probing Single-molecule Interfacial Electron Transfer Inside a Single Lipid Vesicle
Journal of Fluorescence (2023)
-
All-optical fluorescence blinking control in quantum dots with ultrafast mid-infrared pulses
Nature Nanotechnology (2021)
-
Intrinsic luminescence blinking from plasmonic nanojunctions
Nature Communications (2021)
-
Verification of Type-A and Type-B-HC Blinking Mechanisms of Organic–Inorganic Formamidinium Lead Halide Perovskite Quantum Dots by FLID Measurements
Scientific Reports (2020)