Abstract
Auger recombination has been a long-standing obstacle to many prospective applications of colloidal quantum dots (QDs) ranging from lasing, light-emitting diodes to bio-labeling. As such, understanding the physical underpinnings and scaling laws for Auger recombination is essential to these applications. Previous studies of biexciton Auger recombination in various QDs established a universal scaling of biexciton lifetime (τXX) with QD volume (V ): τXX = γV. However, recent measurements on perovskite nanocrystals (NCs), an emerging class of enablers for light harvesting and emitting applications, showed significant deviations from this universal scaling law, likely because the measured NCs are weakly-confined and also have relatively broad size-distributions. Here we study biexciton Auger recombination in mono-dispersed (size distributions within 1.7%–9.0%), quantum-confined CsPbBr3 NCs (with confinement energy up to 410 meV) synthesized using a latest approach based on thermodynamic equilibrium control. Our measurements clearly reproduce the volume-scaling of τXX in confined CsPbBr3 QDs. However, the scaling factor γ (0.085 ± 0.001 ps/nm3) is one order of magnitude lower than that reported for CdSe and PbSe QDs (1.00 ± 0.05 ps/nm3), suggesting unique mechanisms enhancing Auger recombination rate in perovskite NCs.
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References
Landsberg, P. T. Recombination in Semiconductors; Cambridge University Press: Cambridge, UK, 2003.
Klimov, V. I.; Mikhailovsky, A. A.; McBranch, D. W.; Leatherdale, C. A.; Bawendi, M. G. Quantization of multiparticle Auger rates in semiconductor quantum dots. Science 2000, 287, 1011–1013.
Robel, I.; Gresback, R.; Kortshagen, U.; Schaller, R. D.; Klimov, V. I. Universal size-dependent trend in Auger recombination in direct-gap and indirect-gap semiconductor nanocrystals. Phys. Rev. Lett. 2009, 102, 177404.
Pandey, A.; Guyot-Sionnest, P. Multicarrier recombination in colloidal quantum dots. J. Chem. Phys. 2007, 127, 111104.
Pietryga, J. M.; Park, Y. S.; Lim, J.; Fidler, A. F.; Bae, W. K.; Brovelli, S.; Klimov, V. I. Spectroscopic and device aspects of nanocrystal quantum dots. Chem. Rev. 2016, 116, 10513–10622.
Fan, F. J.; Voznyy, O.; Sabatini, R. P.; Bicanic, K. T.; Adachi, M. M.; McBride, J. R.; Reid, K. R.; Park, Y. S.; Li, X. Y.; Jain, A. et al. Continuous-wave lasing in colloidal quantum dot solids enabled by facet-selective epitaxy. Nature 2017, 544, 75–79.
Klimov, V. I.; Mikhailovsky, A. A.; Xu, S.; Malko, A.; Hollingsworth, J. A.; Leatherdale, C. A.; Eisler, H. J.; Bawendi, M. G. Optical gain and stimulated emission in nanocrystal quantum dots. Science 2000, 290, 314–317.
Schaller, R. D.; Klimov, V. I. High efficiency carrier multiplication in PbSe nanocrystals: Implications for solar energy conversion. Phys. Rev. Lett. 2004, 92, 186601.
Ellingson, R. J.; Beard, M. C.; Johnson, J. C.; Yu, P. R.; Micic, O. I.; Nozik, A. J.; Shabaev, A.; Efros, A. L. Highly efficient multiple exciton generation in colloidal PbSe and PbS quantum dots. Nano Lett. 2005, 5, 865–871.
Gao, J. B.; Fidler, A. F.; Klimov, V. I. Carrier multiplication detected through transient photocurrent in device-grade films of lead selenide quantum dots. Nat. Commun. 2015, 6, 8185.
Bae, W. K.; Park, Y. S.; Lim, J.; Lee, D.; Padilha, L. A.; McDaniel, H.; Robel, I.; Lee, C.; Pietryga, J. M.; Klimov, V. I. Controlling the influence of Auger recombination on the performance of quantum-dot light-emitting diodes. Nat. Commun. 2013, 4, 2661.
Bae, W. K.; Brovelli, S.; Klimov, V. I. Spectroscopic insights into the performance of quantum dot light-emitting diodes. MRS Bull. 2013, 38, 721–730.
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.
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.
Efros, A. L.; Nesbitt, D. J. Origin and control of blinking in quantum dots. Nat. Nanotechnol. 2016, 11, 661–671.
Becker, M. A.; Vaxenburg, R.; Nedelcu, G.; Sercel, P. C.; Shabaev, A.; Mehl, M. J.; Michopoulos, J. G.; Lambrakos, S. G.; Bernstein, N.; Lyons, J. L. et al. Bright triplet excitons in caesium lead halide perovskites. Nature 2018, 553, 189–193.
Kovalenko, M. V.; Protesescu, L.; Bodnarchuk, M. I. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals. Science 2017, 358, 745–750.
Protesescu, L.; Yakunin, S.; Bodnarchuk, M. I.; Krieg, F.; Caputo, R.; Hendon, C. H.; Yang, R. X.; Walsh, A.; Kovalenko, M. V. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): Novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett. 2015, 15, 3692–3696.
Makarov, N. S.; Guo, S. J.; Isaienko, O.; Liu, W. Y.; Robel, I.; Klimov, V. I. Spectral and dynamical properties of single excitons, Biexcitons, and Trions in cesium–lead-halide perovskite quantum dots. Nano Lett. 2016, 16, 2349–2362.
Htoon, H.; Hollingsworth, J. A.; Dickerson, R.; Klimov, V. I. Effect of zeroto one-dimensional transformation on multiparticle Auger recombination in semiconductor quantum rods. Phys. Rev. Lett. 2003, 91, 227401.
Padilha, L. A.; Stewart, J. T.; Sandberg, R. L.; Bae, W. K.; Koh, W. K.; Pietryga, J. M.; Klimov, V. I. Aspect ratio dependence of Auger recombination and carrier multiplication in PbSe Nanorods. Nano Lett. 2013, 13, 1092–1099.
Li, Q. Y.; Lian, T. Q. Area- and thickness-dependent biexciton Auger recombination in colloidal CdSe nanoplatelets: Breaking the “universal volume scaling law”. Nano Lett. 2017, 17, 3152–3158.
Dutta, A.; Dutta, S. K.; Das Adhikari, S.; Pradhan, N. Tuning the size of CsPbBr3 nanocrystals: All at one constant temperature. ACS Energy Lett. 2018, 3, 329–334.
Almeida, G.; Goldoni, L.; Akkerman, Q.; Dang, Z. Y.; Khan, A. H.; Marras, S.; Moreels, I.; Manna, L. Role of acid–base equilibria in the size, shape, and phase control of cesium lead bromide nanocrystals. ACS Nano 2018, 12, 1704–1711.
Chen, J. S.; Žídek, K.; Chábera, P.; Liu, D. Z.; Cheng, P. F.; Nuuttila, L.; Al-Marri, M. J.; Lehtivuori, H.; Messing, M. E.; Han, K. L. et al. Size- and wavelength-dependent two-photon absorption cross-section of CsPbBr3 perovskite quantum dots. J. Phys. Chem. Lett. 2017, 8, 2316–2321.
Castañeda, J. A.; Nagamine, G.; Yassitepe, E.; Bonato, L. G.; Voznyy, O.; Hoogland, S.; Nogueira, A. F.; Sargent, E. H.; Cruz, C. H. B.; Padilha, L. A. Efficient biexciton interaction in perovskite quantum dots under weak and strong confinement. ACS Nano 2016, 10, 8603–8609.
Maes, J.; Balcaen, L.; Drijvers, E.; Zhao, Q.; De Roo, J.; Vantomme, A.; Vanhaecke, F.; Geiregat, P.; Hens, Z. Light absorption coefficient of CsPbBr3 perovskite nanocrystals. J. Phys. Chem. Lett. 2018, 9, 3093–3097.
Brennan, M. C.; Zinna, J.; Kuno, M. Existence of a size-dependent stokes shift in CsPbBr3 perovskite nanocrystals. ACS Energy Lett. 2017, 2, 1487–1488.
Brennan, M. C.; Herr, J. E.; Nguyen-Beck, T. S.; Zinna, J.; Draguta, S.; Rouvimov, S.; Parkhill, J.; Kuno, M. Origin of the size-dependent stokes shift in CsPbBr3 perovskite nanocrystals. J. Am. Chem. Soc. 2017, 139, 12201–12208.
Dong, Y. T.; Qiao, T.; Kim, D.; Parobek, D.; Rossi, D.; Son, D. H. Precise control of quantum confinement in cesium lead halide perovskite quantum dots via thermodynamic equilibrium. Nano Lett. 2018, 18, 3716–3722.
Cottingham, P.; Brutchey, R. L. On the crystal structure of colloidally prepared CsPbBr3 quantum dots. Chem. Commun. 2016, 52, 5246–5249.
Wu, K. F.; Liang, G. J.; Shang, Q. Y.; Ren, Y. P.; Kong, D. G.; Lian, T. Q. Ultrafast interfacial electron and hole transfer from CsPbBr3 perovskite quantum dots. J. Am. Chem. Soc. 2015, 137, 12792–12795.
Koscher, B. A.; Swabeck, J. K.; Bronstein, N. D.; Alivisatos, A. P. Essentially trap-free CsPbBr3 colloidal nanocrystals by postsynthetic thiocyanate surface treatment. J. Am. Chem. Soc. 2017, 139, 6566–6569.
Wang, J. H.; Ding, T.; Leng, J.; Jin, S. Y.; Wu, K. F. “Intact” carrier doping by pump–pump–probe spectroscopy in combination with interfacial charge transfer: A case study of CsPbBr3 nanocrystals. J. Phys. Chem. Lett. 2018, 9, 3372–3377.
Klimov, V. I. Multicarrier interactions in semiconductor nanocrystals in relation to the phenomena of Auger recombination and carrier multiplication. Annu. Rev. Condens. Matter Phys. 2014, 5, 285–316.
Mondal, N.; Samanta, A. Complete ultrafast charge carrier dynamics in photo-excited all-inorganic perovskite nanocrystals (CsPbX3). Nanoscale 2017, 9, 1878–1885.
de Jong, E. M. L. D.; Yamashita, G.; Gomez, L.; Ashida, M.; Fujiwara, Y.; Gregorkiewicz, T. Multiexciton lifetime in all-inorganic CsPbBr3 perovskite nanocrystals. J. Phys. Chem. C 2017, 121, 1941–1947.
Aneesh, J.; Swarnkar, A.; Kumar Ravi, V.; Sharma, R.; Nag, A.; Adarsh, K. V. Ultrafast exciton dynamics in colloidal CsPbBr3 perovskite nanocrystals: Biexciton effect and Auger recombination. J. Phys. Chem. C 2017, 121, 4734–4739.
Yarita, N.; Tahara, H.; Ihara, T.; Kawawaki, T.; Sato, R.; Saruyama, M.; Teranishi, T.; Kanemitsu, Y. Dynamics of charged excitons and Biexcitons in CsPbBr3 perovskite nanocrystals revealed by femtosecond transientabsorption and single-dot luminescence spectroscopy. J. Phys. Chem. Lett. 2017, 8, 1413–1418.
Eperon, G. E.; Jedlicka, E.; Ginger, D. S. Biexciton Auger recombination differs in hybrid and inorganic halide perovskite quantum dots. J. Phys. Chem. Lett. 2018, 9, 104–109.
Efros, A. L.; Rosen, M.; Kuno, M.; Nirmal, M.; Norris, D. J.; Bawendi, M. Band-edge exciton in quantum dots of semiconductors with a degenerate valence band: Dark and bright exciton states. Phys. Rev. B 1996, 54, 4843–4856.
Park, Y. S.; Guo, S. J.; Makarov, N. S.; Klimov, V. I. Room temperature single-photon emission from individual perovskite quantum dots. ACS Nano 2015, 9, 10386–10393.
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We gratefully acknowledge financial supports from the Ministry of Science and Technology of China (No. 2018YFA028703) and the National Natural Science Foundation of China (No. 21773239).
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Biexciton Auger recombination in mono-dispersed, quantum-confined CsPbBr3 perovskite nanocrystals obeys universal volume-scaling
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Li, Y., Ding, T., Luo, X. et al. Biexciton Auger recombination in mono-dispersed, quantum-confined CsPbBr3 perovskite nanocrystals obeys universal volume-scaling. Nano Res. 12, 619–623 (2019). https://doi.org/10.1007/s12274-018-2266-7
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DOI: https://doi.org/10.1007/s12274-018-2266-7