Brightly Luminescent Cu-Zn-In-S/ZnS Core/Shell Quantum Dots in Salt Matrices
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Abstract
In the past decades cadmium-free quantum dots (QDs), among which are quaternary colloidal Cu-Zn-In-S/ZnS (CZIS/ZnS) core/shell nanocrystals (NCs), have attracted great scientific interest. Particularly, their low toxicity and the possibility to tune their photoluminescence (PL) properties by varying the composition in the multicomponent system make them highly attractive for applications in light-emitting diodes (LEDs). Thus, the demands for high quality CZIS/ZnS QDs and methods to process them into bulk materials stimulate investigations of these nanomaterials. Herein, we demonstrate the synthesis of CZIS/ZnS core/shell NCs via a surfactant induced nucleation process, which emit in various colors covering the range from 520 nm to 620 nm possessing high photoluminescence quantum yields (PLQYs) up to 47%. Furthermore, the as synthesized NCs were successfully integrated into two different salt matrices [Na2B4O7 (Borax) and LiCl] using two different approaches. The commonly used incorporation of the NCs into Borax salt led to salt crystals emitting from 540 nm to 600 nm with PLQYs up to 24%. By encapsulating the QDs into LiCl, brightly emitting NCs-in-LiCl powders with the PL covering a range from 520 nm to 650 nm with PLQYs of up to 14% were obtained. As a proof of concept, the fabrication of a color conversion LED using NCs encapsulated into LiCl demonstrated the applicability of the encapsulated NCs.
Acknowledgments
We are grateful to S. Goldberg and Dr. J. Simmchen (TU Dresden) for TEM imaging. This work was supported by the German Research Foundation (DFG) under Projects LE 3877/1-1 and EY 16/14-3.
Associated content
Supporting information: TEM images of CZIS/ZnS NCs obtained with and without TOP:S; Table comparing PLQYs and PL maxima of CZIS/ZnS NCs synthesized by varying initial ratio of Zn:Cu from 1.8 to 11 with and without TOP:S in the shell growth step; Table with comparison of PLQYs and PL maxima of CZIS/ZnS NCs (obtained with Zn:Cu=3.6, 7.3, 11) in dispersion and in Borax matrix; Table comparing PLQYs and PL maxima of CZIS/ZnS NCs (obtained with Zn:Cu=1.8–11 and TOP:S addition) in dispersion and in LiCl matrix.
References
1. B. G. D. Scholes, Adv. Funct. Mater. 18 (2008) 1157.10.1002/adfm.200800151Search in Google Scholar
2. D. V. Talapin, J. S. Lee, M. V. Kovalenko, E. V. Shevchenko, Chem. Rev. 110 (2010) 389.10.1021/cr900137kSearch in Google Scholar PubMed
3. M. V. Kovalenko, L. Manna, A. Cabot, Z. Hens, D. V. Talapin, C. R. Kagan, V. I. Klimov, A. L. Rogach, P. Reiss, D. J. Milliron, P. Guyot-Sionnnest, G. Konstantatos, W. J. Parak, T. Hyeon, B. A. Korgel, C. B. Murray, W. Heiss, ACS Nano 9 (2015) 1012.10.1021/nn506223hSearch in Google Scholar PubMed
4. I. J. Kramer, E. H. Sargent, Chem. Rev. 114 (2014) 863.10.1021/cr400299tSearch in Google Scholar PubMed
5. G. H. Carey, A. L. Abdelhady, Z. Ning, S. M. Thon, O. M. Bakr, E. H. Sargent, Chem. Rev. 115 (2015) 12732.10.1021/acs.chemrev.5b00063Search in Google Scholar PubMed
6. L. Li, T. J. Daou, I. Texier, T. T. K. Chi, N. Q. Liem, P. Reiss, Chem. Mater. 21 (2009) 2422.10.1021/cm900103bSearch in Google Scholar
7. T. Pons, E. Pic, N. Lequeux, E. Cassette, L. Bezdetnaya, F. Guillemin, F. Marchal, B. Dubertret, ACS Nano 4 (2010) 2531.10.1021/nn901421vSearch in Google Scholar PubMed
8. E. Arici, N. S. Sariciftci, D. Meissner, Adv. Funct. Mater. 13 (2003) 165.10.1002/adfm.200390024Search in Google Scholar
9. H. Nakamura, W. Kato, M. Uehara, K. Nose, T. Omata, S. Otsuka-Yao-Matsuo, M. Miyazaki, H. Maeda, Chem. Mater. 18 (2006) 3330.10.1021/cm0518022Search in Google Scholar
10. R. Xie, M. Rutherford, X. Peng, J. Am. Chem. Soc. 131 (2009) 5691.10.1021/ja9005767Search in Google Scholar PubMed
11. S.L. Castro, S. G. Bailey, R. P. Raffaelle, K. K. Banger, A. F. Hepp, J. Phys. Chem. B 108 (2004) 12429.10.1021/jp049107pSearch in Google Scholar
12. W. Zhang, X. Zhong, Inorg. Chem. 50 (2011) 4065.10.1021/ic102559eSearch in Google Scholar PubMed
13. H.-J. Pan, C.-W. Lai, S.-W. Chou, P.-T. Chou, Mater. Express 2 (2012) 224.10.1166/mex.2012.1072Search in Google Scholar
14. R. Lesyuk, B. Cai, U. Reuter, N. Gaponik, D. Popovych, V. Lesnyak, Small Methods 1 (2017) 1700189.10.1002/smtd.201700189Search in Google Scholar
15. F. Meinardi, H. McDaniel, F. Carulli, A. Colombo, K. A. Velizhanin, N. S. Makarov, R. Simonutti, V. I. Klimov, S. Brovelli, Nat. Nanotechnol. 10 (2015) 878.10.1038/nnano.2015.178Search in Google Scholar PubMed
16. R. Sumner, S. Eiselt, T. B. Kilburn, C. Erickson, B. Carlson, D. R. Gamelin, S. McDowall, D. L. Patrick, J. Phys. Chem. C 121 (2017) 3252.10.1021/acs.jpcc.6b12379Search in Google Scholar
17. R. Lesyuk, V. Lesnyak, A. Herguth, D. Popovych, Y. Bobitski, C. Klinke, N. Gaponik, J. Mater. Chem. C 5 (2017) 11790.10.1039/C7TC02945DSearch in Google Scholar
18. T. Otto, M. Müller, P. Mundra, V. Lesnyak, H. V. Demir, N. Gaponik, A. Eychmüller, Nano Lett. 12 (2012) 5348.10.1021/nl3027444Search in Google Scholar PubMed
19. M. Müller, M. Kaiser, G. M. Stachowski, U. Resch-Genger, N Gaponik, A. Eychmüller, Chem. Mater. 26 (2014) 3231.10.1021/cm5009043Search in Google Scholar
20. M. Adam, Z. Wang, A. Dubavik, G. M. Stachowski, C. Meerbach, Z. Soran-Erdem, C. Rengers, H. V. Demir, N. Gaponik, A. Eychmüller, Adv. Funct. Mater. 25 (2015) 2638.10.1002/adfm.201500552Search in Google Scholar
21. M. Adam, R. Tietze, N. Gaponik, A. Eychmüller, Z. Phys. Chem. 229 (2015) 109.10.1515/zpch-2014-0598Search in Google Scholar
22. M. Adam, T. Erdem, G. M. Stachowski, Z. Soran-Erdem, J. F. L. Lox, C. Bauer, J. Poppe, H. V. Demir, N. Gaponik, A. Eychmüller, ACS Appl. Mater. Interfaces 7 (2015) 23364.10.1021/acsami.5b08377Search in Google Scholar PubMed
23. S. Kalytchuk, M. Adam, O. Tomanec, R. Zbořil, N. Gaponik, A. L. Rogach, ACS Photonics 4 (2017) 1459.10.1021/acsphotonics.7b00222Search in Google Scholar
24. M. Adam, N. Gaponik, A. Eychmüller, T. Erdem, Z. Soran-Erdem, H. V. Demir, J. Phys. Chem. Lett. 7 (2016) 4117.10.1021/acs.jpclett.6b01699Search in Google Scholar PubMed
25. C. Guhrenz, A. Benad, C. Ziegler, D. Haubold, N. Gaponik, A. Eychmüller, Chem. Mater. 28 (2016) 9033.10.1021/acs.chemmater.6b03980Search in Google Scholar
26. A. Benad, C. Guhrenz, C. Bauer, F. Eichler, M. Adam, C. Ziegler, N. Gaponik, A. Eychmüller, ACS Appl. Mater. Interfaces 8 (2016) 21570.10.1021/acsami.6b06452Search in Google Scholar PubMed
27. T. Erdem, Z. Soran-Erdem, V. K. Sharma, Y. Kelestemur, M. Adam, N. Gaponik, H. V. Demir, Nanoscale 7 (2015) 17611.10.1039/C5NR02696BSearch in Google Scholar PubMed
28. T. Erdem, Z. Soran-Erdem, P. L. Hernandez-Martinez, V. K. Sharma, H. Akcali, I. Akcali, N. Gaponik, A. Eychmüller, H. V. Demir, Nano Res. 8 (2014) 860.10.1007/s12274-014-0568-ySearch in Google Scholar
29. W. K. Bae, K. Char, H. Hur, S. Lee, Chem. Mater. 20 (2008) 531.10.1021/cm070754dSearch in Google Scholar
30. M. Grabolle, M. Spieles, V. Lesnyak, N. Gaponik, A. Eychmüller, U. Resch-Genger, Anal. Chem. 81 (2009) 6285.10.1021/ac900308vSearch in Google Scholar
31. J. C. De Mello, H. F. Wittmann, R. Friend, Adv. Mater. 9 (1997) 230.10.1002/adma.19970090308Search in Google Scholar
32. H. Zhong, Y. Zhou, M. Ye, Y. He, J. Ye, C. He, C. Yang, Y. Li, Chem. Mater. 20 (2008) 6434.10.1021/cm8006827Search in Google Scholar
33. J. Feng, M. Sun, F. Yang, X. Yang, Chem. Commun. 47 (2011) 6422.10.1039/c1cc11754hSearch in Google Scholar PubMed
34. I. Tsuji, H. Kato, H. Kobayashi, A. Kudo, J. Phys. Chem. 109 (2005) 7323.10.1021/jp044722eSearch in Google Scholar PubMed
35. L. De Trizio, L. Manna, Chem. Rev. 116 (2016) 10852.10.1021/acs.chemrev.5b00739Search in Google Scholar PubMed PubMed Central
36. G. B. Dhanaraj, V. K. Prasad, M. Dudley, Handbook of Crystal Growth, Springer, New York, 2010.10.1007/978-3-540-74761-1Search in Google Scholar
37. A. Holden, P. Morrison, Crystals and crystal growing, MIT Press, Cambridge, MA, 1982.Search in Google Scholar
38. K.-T. Wilke, J. Bohm, Kristallzüchtung (in German), Harri Deutsch Verlag, Frankfurt am Main, 1988.Search in Google Scholar
39. S. Kalytchuk, O. Zhovtiuk, A. L. Rogach, Appl. Phys. Lett. 103 (2013) 103105.10.1063/1.4820406Search in Google Scholar
40. K. H. Ibnaouf, S. Prasad, M. S. A. Salhi, A. Hamdan, M. B. Zaman, L. E. Mir, J. Luminescence 149 (2014) 369.10.1016/j.jlumin.2014.01.054Search in Google Scholar
Supplementary Material
The online version of this article offers supplementary material (https://doi.org/10.1515/zpch-2017-1086).
©2019 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- Editorial
- Nanosized Matter
- Extinction Coefficient of Plasmonic Nickel Sulfide Nanocrystals and Gold-Nickel Sulfide Core-Shell Nanoparticles
- Thermal cis-to-trans Isomerization of Azobenzene Side Groups in Metal-Organic Frameworks investigated by Localized Surface Plasmon Resonance Spectroscopy
- Brightly Luminescent Cu-Zn-In-S/ZnS Core/Shell Quantum Dots in Salt Matrices
- Role of Tryptophan in Protein–Nanocrystals Interaction: Energy or Charge Transfer
- Synthesis of InP/ZnS Nanocrystals and Phase Transfer by Hydrolysis of Ester
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- Yolk Type Asymmetric Ag–Cu2O Hybrid Nanoparticles on Graphene Substrate as Efficient Electrode Material for Hybrid Supercapacitors
- Electrospun CuO Nanofibre Assemblies for H2S Sensing
- Review
- Two-Dimensional Oxides: Recent Progress in Nanosheets
Articles in the same Issue
- Frontmatter
- Editorial
- Nanosized Matter
- Extinction Coefficient of Plasmonic Nickel Sulfide Nanocrystals and Gold-Nickel Sulfide Core-Shell Nanoparticles
- Thermal cis-to-trans Isomerization of Azobenzene Side Groups in Metal-Organic Frameworks investigated by Localized Surface Plasmon Resonance Spectroscopy
- Brightly Luminescent Cu-Zn-In-S/ZnS Core/Shell Quantum Dots in Salt Matrices
- Role of Tryptophan in Protein–Nanocrystals Interaction: Energy or Charge Transfer
- Synthesis of InP/ZnS Nanocrystals and Phase Transfer by Hydrolysis of Ester
- Amine Capped Gold Colloids at Oxidic Supports: Their Electronic Interactions
- Yolk Type Asymmetric Ag–Cu2O Hybrid Nanoparticles on Graphene Substrate as Efficient Electrode Material for Hybrid Supercapacitors
- Electrospun CuO Nanofibre Assemblies for H2S Sensing
- Review
- Two-Dimensional Oxides: Recent Progress in Nanosheets
