Shell-thickness dependent optical properties of CdSe/CdS core/shell nanocrystals coated with thiol ligands
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Using CdSe/CdS core/shell nanocrystals with 1–10 monolayers of CdS shell as the model system, we studied effects of thiol ligands on optical properties of the nanocrystals. The core/shell nanocrystals with original ligands possessed near unity photoluminescence (PL) quantum yield and single-exponential PL decay dynamics. The effects of thiol ligands on optical properties were found to depend on the shell thickness, environment (with/without oxygen), and excitation power (single- or multi-exciton). Systematic and quantitative results reported in this work should provide necessary information for fundamental understanding and technical applications of quantum dots (QDs) coated with thiol ligands.
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Shell-thickness dependent optical properties of CdSe/CdS core/shell nanocrystals coated with thiol ligands
Abstract
Using CdSe/CdS core/shell nanocrystals with 1–10 monolayers of CdS shell as the model system, we studied effects of thiol ligands on optical properties of the nanocrystals. The core/shell nanocrystals with original ligands possessed near unity photoluminescence (PL) quantum yield and single-exponential PL decay dynamics. The effects of thiol ligands on optical properties were found to depend on the shell thickness, environment (with/without oxygen), and excitation power (single- or multi-exciton). Systematic and quantitative results reported in this work should provide necessary information for fundamental understanding and technical applications of quantum dots (QDs) coated with thiol ligands.
References(45)
Brus, L. E. Electron–electron and electron–hole interactions in small semiconductor crystallites: The size dependence of the lowest excited electronic state. J. Chem. Phys. 1984, 80, 4403–4409.
Bruchez, M., Jr.; Moronne, M.; Gin, P.; Weiss, S.; Alivisatos, A. P. Semiconductor nanocrystals as fluorescent biological labels. Science 1998, 281, 2013–2016.
Chan, W. C. W.; Nie, S. M. Quantum dot bioconjugates for ultrasensitive nonisotopic detection. Science 1998, 281, 2016–2018.
Greenham, N. C.; Peng, X. G.; Alivisatos, A. P. Charge separation and transport in conjugated-polymer/ semiconductor-nanocrystal composites studied by photoluminescence quenching and photoconductivity. Phys. Rev. B 1996, 54, 17628–17637.
Colvin, V. L.; Schlamp, M. C.; Allvisatos, A. P. Light- emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer. Nature 1994, 370, 354–357.
Coe, S.; Woo, W. K.; Bawendi, M. G.; Bulović, V. Electroluminescence from single monolayers of nanocrystals in molecular organic devices. Nature 2002, 420, 800–803.
Dai, X. L.; Zhang, Z. X.; Jin, Y. Z.; Niu, Y.; Cao, H. J.; Liang, X. Y.; Chen, L. W.; Wang, J. P.; Peng, X. G. Solution-processed, high-performance light-emitting diodes based on quantum dots. Nature 2014, 515, 96–99.
Yin, Y. D.; Alivisatos, A. P. Colloidal nanocrystal synthesis and the organic–inorganic interface. Nature 2005, 437, 664–670.
Peng, X. G. An essay on synthetic chemistry of colloidal nanocrystals. Nano Res. 2009, 2, 425–447.
Pradhan, N.; Reifsnyder, D.; Xie, R. G.; Aldana, J.; Peng, X. G. Surface ligand dynamics in growth of nanocrystals. J. Am. Chem. Soc. 2007, 129, 9500–9509.
Aldana, J.; Lavelle, N.; Wang, Y. J.; Peng, X. G. Size- dependent dissociation pH of thiolate ligands from cadmium chalcogenide nanocrystals. J. Am. Chem. Soc. 2005, 127, 2496–2504.
Aldana, J.; Wang, Y. A.; Peng, X. G. Photochemical instability of CdSe nanocrystals coated by hydrophilic thiols. J. Am. Chem. Soc. 2001, 123, 8844–8850.
Wuister, S. F.; De Donega, C.; Meijerink, A. Influence of thiol capping on the exciton luminescence and decay kinetics of CdTe and CdSe quantum dots. J. Phys. Chem. B 2004, 108, 17393–17397.
Jeong, S.; Achermann, M.; Nanda, J.; Ivanov, S.; Klimov, V. I.; Hollingsworth, J. A. Effect of the thiol–thiolate equilibrium on the photophysical properties of aqueous CdSe/ZnS nanocrystal quantum dots. J. Am. Chem. Soc. 2005, 127, 10126–10127.
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 2007, 111, 6220–6227.
Munro, A. M.; Ginger, D. S. Photoluminescence quenching of single CdSe nanocrystals by ligand adsorption. Nano Lett. 2008, 8, 2585–2590.
Chen, O.; Zhao, J.; Chauhan, V. P.; Cui, J.; Wong, C.; Harris, D. K.; Wei, H.; Han, H. -S.; Fukumura, D.; Jain, R. K. et al. Compact high-quality CdSe–CdS core–shell nanocrystals with narrow emission linewidths and suppressed blinking. Nat. Mater. 2013, 12, 445–451.
Tarafder, K.; Surendranath, Y.; Olshansky, J. H.; Alivisatos, A. P.; Wang, L. -W. Hole transfer dynamics from a CdSe/ CdS quantum rod to a tethered ferrocene derivative. J. Am. Chem. Soc. 2014, 136, 5121–5131.
Ding, T. X.; Olshansky, J. H.; Leone, S. R.; Alivisatos, A. P. Efficiency of hole transfer from photoexcited quantum dots to covalently linked molecular species. J. Am. Chem. Soc. 2015, 137, 2021–2029.
Hohng, S.; Ha, T. Near-complete suppression of quantum dot blinking in ambient conditions. J. Am. Chem. Soc. 2004, 126, 1324–1325.
Zhang, A. D.; Dong, C. Q.; Liu, H.; Ren, J. C. Blinking behavior of CdSe/CdS quantum dots controlled by alkylthiols as surface trap modifiers. J. Phys. Chem. C 2013, 117, 24592–24600.
Gómez, D. E.; van Embden, J.; Jasieniak, J.; Smith, T. A.; Mulvaney, P. Blinking and surface chemistry of single CdSe nanocrystals. Small 2006, 2, 204–208.
Qin, H. Y.; Niu, Y.; Meng, R. Y.; Lin, X.; Lai, R. C.; Fang, W.; Peng, X. G. Single-dot spectroscopy of zinc-blende CdSe/CdS core/shell nanocrystals: Nonblinking and correlation with ensemble measurements. J. Am. Chem. Soc. 2014, 136, 179–187.
Mahler, B.; Spinicelli, P.; Buil, S.; Quelin, X.; Hermier, J. -P.; Dubertret, B. Towards non-blinking colloidal quantum dots. Nat. Mater. 2008, 7, 659–664.
Malko, A. V.; Park, Y. S.; Sampat, S.; Galland, C.; Vela, J.; Chen, Y. F.; Hollingsworth, J. A.; Klimov, V. I.; Htoon, H. Pump-intensity- and shell-thickness-dependent evolution of photoluminescence blinking in individual core/shell CdSe/CdS nanocrystals. Nano Lett. 2011, 11, 5213–5218.
Ghosh, Y.; Mangum, B. D.; Casson, J. L.; Williams, D. J.; Htoon, H.; Hollingsworth, J. A. 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. 2012, 134, 9634–9643.
Nan, W. N.; Niu, Y.; Qin, H. Y.; Cui, F.; Yang, Y.; Lai, R. C.; Lin, W. Z.; Peng, X. G. Crystal structure control of zinc-blende CdSe/CdS core/shell nanocrystals: Synthesis and structure-dependent optical properties. J. Am. Chem. Soc. 2012, 134, 19685–19693.
Pu, C. D.; Zhou, J. H.; Lai, R. C.; Niu, Y.; Nan, W. N.; Peng, X. G. Highly reactive, flexible yet green Se precursor for metal selenide nanocrystals: Se-octadecene suspension (Se-SUS). Nano Res. 2013, 6, 652–670.
Koole, R.; Luigjes, B.; Tachiya, M.; Pool, R.; Vlugt, T. J. H.; de Donega, C.; Meijerink, A.; Vanmaekelbergh, D. Differences in cross-link chemistry between rigid and flexible dithiol molecules revealed by optical studies of CdTe quantum dots. J. Phys. Chem. C 2007, 111, 11208–11215.
Nadeau, J. L.; Carlini, L.; Suffern, D.; Ivanova, O.; Bradforth, S. E. Effects of β-mercaptoethanol on quantum dot emission evaluated from photoluminescence decays. J. Phys. Chem. C 2012, 116, 2728–2739.
Bullen, C.; Mulvaney, P. The effects of chemisorption on the luminescence of CdSe quantum dots. Langmuir 2006, 22, 3007–3013.
Ji, X. H.; Copenhaver, D.; Sichmeller, C.; Peng, X. G. Ligand bonding and dynamics on colloidal nanocrystals at room temperature: The case of alkylamines on CdSe nanocrystals. J. Am. Chem. Soc. 2008, 130, 5726–5735.
Nirmal, M.; Dabbousi, B. O.; Bawendi, M. G.; Macklin, J. J.; Trautman, J. K.; Harris, T. D.; Brus, L. E. Fluorescence intermittency in single cadmium selenide nanocrystals. Nature 1996, 383, 802–804.
Chen, Y. F.; Vela, J.; Htoon, H.; Casson, J. L.; Werder, D. J.; Bussian, D. A.; Klimov, V. I.; Hollingsworth, J. A. "Giant" multishell CdSe nanocrystal quantum dots with suppressed blinking. J. Am. Chem. Soc. 2008, 130, 5026–5027.
Spinicelli, P.; Buil, S.; Quélin, X.; Mahler, B.; Dubertret, B.; Hermier, J. P. Bright and grey states in CdSe–CdS nanocrystals exhibiting strongly reduced blinking. Phys. Rev. Lett. 2009, 102, 136801.
Galland, C.; Ghosh, Y.; Steinbrück, A.; Sykora, M.; Hollingsworth, J. A.; Klimov, V. I.; Htoon, H. Two types of luminescence blinking revealed by spectroelectrochemistry of single quantum dots. Nature 2011, 479, 203–207.
Javaux, C.; Mahler, B.; Dubertret, B.; Shabaev, A.; Rodina, A. V.; Efros, A. L.; Yakovlev, D. R.; Liu, F.; Bayer, M.; Camps, G. et al. Thermal activation of non-radiative Auger recombination in charged colloidal nanocrystals. Nat. Nanotechnol. 2013, 8, 206–212.
Liu, F.; Biadala, L.; Rodina, A. V.; Yakovlev, D. R.; Dunker, D.; Javaux, C.; Hermier, J. P.; Efros, A. L.; Dubertret, B.; Bayer, M. Spin dynamics of negatively charged excitons in CdSe/CdS colloidal nanocrystals. Phys. Rev. B 2013, 88, 035302.
Galland, C.; Ghosh, Y.; Steinbrück, A.; Hollingsworth, J. A.; Htoon, H.; Klimov, V. I. Lifetime blinking in nonblinking nanocrystal quantum dots. Nat. Commun. 2012, 3, 908.
Jha, P. P.; Guyot-Sionnest, P. Trion decay in colloidal quantum dots. ACS Nano 2009, 3, 1011–1015.
Song, N. H.; Zhu, H. M.; Jin, S. Y.; Lian, T. Q. Hole transfer from single quantum dots. ACS Nano 2011, 5, 8750–8759.
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. 2000, 112, 3117–3120.
Schlegel, G.; Bohnenberger, J.; Potapova, I.; Mews, A. Fluorescence decay time of single semiconductor nanocrystals. Phys. Rev. Lett. 2002, 88, 137401.
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 2004, 108, 143–148.
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Acknowledgements
This work was supported in part by the National Natural Science Foundation of China (NSFC) (Nos. 21233005 and 91433204) and Fundamental Research Funds for the Central Universities (No. 2014FZA3006).
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