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Nano Research 2019, 12(6): 1437-1444 https://doi.org/10.1007/s12274-019-2386-8
Research Article | Issue | Published: 29 May 2019

CdS magic-size clusters exhibiting one sharp ultraviolet absorption singlet peaking at 361 nm

Show Author's Information Junbin Tang1,  Juan Hui1,  Meng Zhang1,  Hongsong Fan2,  Nelson Rowell3,  Wen Huang4,  Yingnan Jiang5,  Xiaoqin Chen2( ),  Kui Yu1,2,6( )
Institute of Atomic and Molecular Physics,Sichuan University,Chengdu,610065,China;
Engineering Research Center in Biomaterials,Sichuan University,Chengdu,610065,China;
Metrology Research Centre,National Research Council of Canada,Ottawa, Ontario K1A 0R6,Canada;
Laboratory of Ethnopharmacology,West China School of Medicine, Sichuan University,Chengdu,610065,China;
Jilin Ginseng Academy,Changchun University of Chinese Medicine,Changchun,130117,China;
State Key Laboratory of Polymer Materials Engineering,Sichuan University,Chengdu,610065,China;
Keywords:
colloidal semiconductor CdS, magic-size clusters (MSCs), MSC-361, quantum dots (QDs), electronic structures
Topics:
Cadmium sulfideElectronic structureEnergy gapIINanocrystalsSemiconductor quantum dotsVI semiconductors
Cite this article:
Tang J, Hui J, Zhang M, et al. CdS magic-size clusters exhibiting one sharp ultraviolet absorption singlet peaking at 361 nm. Nano Research, 2019, 12(6): 1437-1444. https://doi.org/10.1007/s12274-019-2386-8
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Abstract Full text Electronic supplementary material About this article

We report, for the first time, the synthesis of CdS magic-size clusters (MSCs) which exhibit a single sharp absorption peaking at ~ 361 nm, along with sharp band edge photoemission at ~ 377 nm and broad trap emission peaking at ~ 490 nm. These MSCs are produced in a single-ensemble form without the contamination of conventional quantum dots (QDs) and/or other-bandgap clusters. They are denoted as MSC-361. We present the details of several controlled syntheses done in oleylamine (OLA), using Cd(NO3)2 or Cd(OAc)2 as a Cd source and thioacetamide (TAA) or elementary sulfur (S) as a S source. A high synthetic reproducibility of the reaction of Cd(NO3)2 and TAA to single-ensemble MSC-361 is achieved, the product of which is not contaminated by other bandgap clusters and/or QDs. In some cases, the reaction product exhibits an additional absorption peak at ~ 322 nm. We demonstrate that the two peaks, at 361 and 322 nm, do not evolve synchronously. Therefore, the 322 nm peak is not a higher order electronic transition of MSC-361, but due to the presence of another ensemble, namely MSC-322. The present study suggests that there is an outstanding need for the development of a physical model to narrow the knowledge gap regarding the electronic structure in these colloidal semiconductor CdS MSCs.


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Electronic supplementary material
About this article

CdS magic-size clusters exhibiting one sharp ultraviolet absorption singlet peaking at 361 nm

Show Author's information Junbin Tang1, Juan Hui1, Meng Zhang1, Hongsong Fan2, Nelson Rowell3, Wen Huang4, Yingnan Jiang5, Xiaoqin Chen2( ), Kui Yu1,2,6( )
Institute of Atomic and Molecular Physics,Sichuan University,Chengdu,610065,China;
Engineering Research Center in Biomaterials,Sichuan University,Chengdu,610065,China;
Metrology Research Centre,National Research Council of Canada,Ottawa, Ontario K1A 0R6,Canada;
Laboratory of Ethnopharmacology,West China School of Medicine, Sichuan University,Chengdu,610065,China;
Jilin Ginseng Academy,Changchun University of Chinese Medicine,Changchun,130117,China;
State Key Laboratory of Polymer Materials Engineering,Sichuan University,Chengdu,610065,China;

Abstract

We report, for the first time, the synthesis of CdS magic-size clusters (MSCs) which exhibit a single sharp absorption peaking at ~ 361 nm, along with sharp band edge photoemission at ~ 377 nm and broad trap emission peaking at ~ 490 nm. These MSCs are produced in a single-ensemble form without the contamination of conventional quantum dots (QDs) and/or other-bandgap clusters. They are denoted as MSC-361. We present the details of several controlled syntheses done in oleylamine (OLA), using Cd(NO3)2 or Cd(OAc)2 as a Cd source and thioacetamide (TAA) or elementary sulfur (S) as a S source. A high synthetic reproducibility of the reaction of Cd(NO3)2 and TAA to single-ensemble MSC-361 is achieved, the product of which is not contaminated by other bandgap clusters and/or QDs. In some cases, the reaction product exhibits an additional absorption peak at ~ 322 nm. We demonstrate that the two peaks, at 361 and 322 nm, do not evolve synchronously. Therefore, the 322 nm peak is not a higher order electronic transition of MSC-361, but due to the presence of another ensemble, namely MSC-322. The present study suggests that there is an outstanding need for the development of a physical model to narrow the knowledge gap regarding the electronic structure in these colloidal semiconductor CdS MSCs.

Keywords: colloidal semiconductor CdS, magic-size clusters (MSCs), MSC-361, quantum dots (QDs), electronic structures

References(53)

1

Zhang, H. T.; Hyun, B. R.; Wise, F. W.; Robinson, R. D. A generic method for rational scalable synthesis of monodisperse metal sulfide nanocrystals. Nano Lett. 2012, 12, 5856-5860.
DOI Google Scholar
2

Wang, Y.; Zhou, Y.; Zhang, Y; Buhro, W. E. Magic-size Ⅱ−Ⅵ nanoclusters as synthons for flat colloidal nanocrystals. Inorg. Chem. 2015, 54, 1165-1177.
DOI Google Scholar
3

Nevers, D. R.; Williamson, C. B.; Hanrath, T.; Robinson, R. D. Surface chemistry of cadmium sulfide magic-sized clusters: A window into ligand-nanoparticle interactions. Chem. Commun. 2017, 53, 2866-2869.
DOI Google Scholar
4

Son, J. S.; Park, K.; Kwon, S. G.; Yang, J.; Choi, M. K.; Kim, J.; Yu, J. H.; Joo, J.; Hyeon, T. Dimension-controlled synthesis of CdS nanocrystals: From 0D quantum dots to 2D nanoplates. Small 2012, 8, 2394-2402.
DOI Google Scholar
5

Li, Z.; Qin, H. Y.; Guzun, D.; Benamara, M.; Salamo, G.; Peng, X. G. Uniform thickness and colloidal-stable CdS quantum disks with tunable thickness: Synthesis and properties. Nano Res. 2012, 5, 337-351.
DOI Google Scholar
6

Li, M. J.; Ouyang, J. Y.; Ratcliffe, C. I.; Pietri, L.; Wu, X. H.; Leek, D. M.; Moudrakovski, I.; Lin, Q.; Yang, B.; Yu, K. CdS magic-sized nanocrystals exhibiting bright band gap photoemission via thermodynamically driven formation. ACS Nano 2009, 3, 3832-3838.
DOI Google Scholar
7

Zhu, T. T.; Zhang, B. W.; Zhang, J.; Lu, J.; Fan, H. S.; Rowell, N.; Ripmeester, J. A.; Han, S.; Yu, K. Two-step nucleation of CdS magic-size nanocluster MSC-311. Chem. Mater. 2017, 29, 5727-5735.
DOI Google Scholar
8

Zhang, B. W.; Zhu, T. T.; Ou, M. Y.; Rowell, N.; Fan, H. S.; Han, J. T.; Tan, L.; Dove, M. T.; Ren, Y.; Zuo, X. B. et al. Thermally-induced reversible structural isomerization in colloidal semiconductor CdS magic-size clusters. Nat. Commun. 2018, 9, 2499.
DOI Google Scholar
9

Zhang, J.; Hao, X. Y.; Rowell, N.; Kreouzis, T.; Han, S.; Fan, H. S.; Zhang, C. C.; Hu, C. W.; Zhang, M.; Yu, K. Individual pathways in the formation of magic-size clusters and conventional quantum dots. J. Phys. Chem. Lett. 2018, 9, 3660-3666.
DOI Google Scholar
10

Nevers, D. R.; Williamson, C. B.; Savitzky, B. H.; Hadar, I.; Banin, U.; Kourkoutis, L. F.; Hanrath, T.; Robinson, R. D. Mesophase formation stabilizes high-purity magic-sized clusters. J. Am. Chem. Soc. 2018, 140, 3652-3662.
DOI Google Scholar
11

Yu, W. W.; Peng X. G. Formation of high-quality CdS and other Ⅱ-Ⅵ semiconductor nanocrystals in noncoordinating solvents: Tunable reactivity of monomers. Angew. Chem., Int. Ed. 2002, 41, 2368-2371.
DOI
12

Pan, D. C.; Ji, X. L.; An, L. J.; Lu, Y. F. Observation of nucleation and growth of CdS nanocrystals in a two-phase system. Chem. Mater. 2008, 20, 3560-3566.
DOI Google Scholar
13

Ouyang, J. Y.; Kuijper, J.; Brot, S.; Kingston, D.; Wu, X. H.; Leek, D. M.; Hu, M. Z.; Ripmeester, J. A.; Yu, K. Photoluminescent colloidal CdS nanocrystals with high quality via noninjection one-pot synthesis in 1-octadecene. J. Phys. Chem. C 2009, 113, 7579-7593.
DOI Google Scholar
14

Yu, Q. Y.; Liu, C. Y. Study of magic-size-cluster mediated formation of CdS nanocrystals: Properties of the magic-size clusters and mechanism implication. J. Phys. Chem. C 2009, 113, 12766-12771.
DOI Google Scholar
15

Zanella, M.; Abbasi, A. Z.; Schaper, A. K.; Parak, W. J. Discontinuous growth of Ⅱ-Ⅵ semiconductor nanocrystals from different materials. J. Phys. Chem. C 2010, 114, 6205-6215.
DOI Google Scholar
16

Fojtik, A.; Weller, H.; Koch, U.; Henglein, A. Photo-chemistry of colloidal metal sulfides 8. photo-physics of extremely small CdS particles: Q-state CdS and magic agglomeration numbers. Ber. Bunsenges. Phys. Chem. 1984, 88, 969-977.
DOI Google Scholar
17

Vossmeyer, T.; Katsikas, L.; Giersig, M.; Popovic, I. G.; Diesner, K.; Chemseddine, A.; Eychmueller, A.; Weller, H. CdS nanoclusters: Synthesis, characterization, size dependent oscillator strength, temperature shift of the excitonic transition energy, and reversible absorbance shift. J. Phys. Chem. 1994, 98, 7665-7673.
DOI Google Scholar
18

Samanta, A; Deng, Z. T.; Liu, Y.; Yan, H. A perspective on functionalizing colloidal quantum dots with DNA. Nano Res. 2013, 6, 853-870.
DOI Google Scholar
19

Zhang, L. B.; Jean, S. R.; Ahmed, S.; Aldridge, P. M.; Li, X. Y.; Fan, F. J.; Sargent, E. H.; Kelley, S. O. Multifunctional quantum dot DNA hydrogels. Nat. Commun. 2017, 8, 381.
DOI Google Scholar
20

Luo, W. N.; Jiu, T. G.; Kuang, C. Y.; Li, B. R.; Lu, F. S.; Fang, J. F. Dithiol treatments enhancing the efficiency of hybrid solar cells based on PTB7 and CdSe nanorods. Nano Res. 2015, 8, 3045-3053.
DOI Google Scholar
21

Yang, Z. Y.; Fan, J. Z.; Proppe, A. H.; de Arquer, F. P. G.; Rossouw, D.; Voznyy, O.; Lan, X. Z.; Liu, M.; Walters, G.; Quintero-Bermudez, R. et al. Mixed-quantum-dot solar cells. Nat. Commun. 2017, 8, 1325.
DOI Google Scholar
22

Empedocles, S A.; Neuhauser, R.; Shimizu, K. T.; Bawendi, M. G. Photoluminescence from single semiconductor nanostructures. Adv. Mater. 1999, 11, 1243-1256.
DOI
23

Cui, J.; Beyler, A. P.; Marshall, L. F.; Chen, O.; Harris, D. K.; Wanger, D. D.; Brokmann, X.; Bawendi, M. G. Direct probe of spectral inhomogeneity reveals synthetic tunability of single-nanocrystal spectral linewidths. Nat. Chem. 2013, 5, 602-606.
DOI Google Scholar
24

Kasuya, A.; Sivamohan, R.; Barnakov, Y. A.; Dmitruk, I. M.; Nirasawa, T.; Romanyuk, V. R.; Kumar, V.; Mamykin, S. V.; Tohji, K.; Jeyadevan, B. et al. Ultra-stable nanoparticles of CdSe revealed from mass spectrometry. Nat. Mater. 2004, 3, 99-102.
DOI Google Scholar
25

Beecher, A. N.; Yang, X. H.; Palmer, J. H.; LaGrassa, A. L.; Juhas, P.; Billinge, S. J. L.; Owen, J. S. Atomic structures and gram scale synthesis of three tetrahedral quantum dots. J. Am. Chem. Soc. 2014, 136, 10645-10653.
DOI Google Scholar
26

Ekimov, A. I.; Hache, F.; Schanne-Klein, M. C.; Ricard, D.; Flytzanis, C.; Kudryavtsev, I. A.; Yazeva, T. V.; Rodina, A. V.; Efros, A. L. Absorption and intensity-dependent photoluminescence measurements on CdSe quantum dots: Assignment of the first electronic transitions. J. Opt. Soc. Am. B 1993, 10, 100-107.
DOI Google Scholar
27

Norris, D. J.; Bawendi, M. G. Measurement and assignment of the size-dependent optical spectrum in CdSe quantum dots. Phys. Rev. B 1996, 53, 16338-16346.
DOI Google Scholar
28

Liu, M. Y.; Wang, K.; Wang, L. X.; Han, S.; Fan, H. S.; Rowell, N.; Ripmeester, J. A.; Renoud, R.; Bian, F. G.; Zeng, J. R. et al. Probing intermediates of the induction period prior to nucleation and growth of semiconductor quantum dots. Nat. Commun. 2017, 8, 15467.
DOI Google Scholar
29

Wang, L. X.; Hui, J.; Tang, J. B.; Rowell, N.; Zhang, B. W.; Zhu, T. T.; Zhang, M.; Hao, X. Y.; Fan, H. S.; Zeng, J. R. et al. Precursor self-assembly identified as a general pathway for colloidal semiconductor magic-size clusters. Adv. Sci. 2018, 5, 1800632.
DOI Google Scholar
30

LaMer, V. K.; Dinegar, R. H. Theory, production and mechanism of formation of monodispersed hydrosols. J. Am. Chem. Soc. 1950, 72, 4847-4854.
DOI Google Scholar
31

van Embden, J.; Mulvaney, P. Nucleation and growth of CdSe nanocrystals in a binary ligand system. Langmuir 2005, 21, 10226-10233.
DOI Google Scholar
32

Steckel, J. S.; Yen, B. K. H.; Oertel, D. C.; Bawendi, M. G. On the mechanism of lead chalcogenide nanocrystal formation. J. Am. Chem. Soc. 2006, 128, 13032-13033.
DOI Google Scholar
33

García-Rodríguez, R.; Hendricks, M. P.; Cossairt, B. M.; Liu, H. T.; Owen, J. S. Conversion reactions of cadmium chalcogenide nanocrystal precursors. Chem. Mater. 2013, 25, 1233-1249.
DOI Google Scholar
34

Yu, K.; Liu, X. Y.; Chen, Q. Y.; Yang, H. Q.; Yang, M. L.; Wang, X. Q.; Wang, X.; Cao, H.; Whitfield, D. M.; Hu, C. W. et al. Mechanistic study of the role of primary amines in precursor conversions to semiconductor nanocrystals at low temperature. Angew. Chem. , Int. Ed. 2014, 53, 6898-6904.
DOI Google Scholar
35

Yu, K.; Liu, X. Y.; Qi, T.; Yang, H. Q.; Whitfield, D. M.; Chen, Q. Y.; Huisman, E. J. C.; Hu, C. W. General low-temperature reaction pathway from precursors to monomers before nucleation of compound semiconductor nanocrystals. Nat. Commun. 2016, 7, 12223.
DOI Google Scholar
36

Xie, L. S.; Shen, Y.; Franke, D.; Sebastián, V.; Bawendi, M. G.; Jensen, K. F. Characterization of indium phosphide quantum dot growth intermediates using MALDI-TOF mass spectrometry. J. Am. Chem. Soc. 2016, 138, 13469-13472.
DOI Google Scholar
37

Bowers, M. J.; McBride, J. R.; Rosenthal, S. J. White-light emission from magic-sized cadmium selenide nanocrystals. J. Am. Chem. Soc. 2005, 127, 15378-15379.
DOI Google Scholar
38

Cossairt, B. M.; Owen, J. S. CdSe clusters: At the interface of small molecules and quantum dots. Chem. Mater. 2011, 23, 3114-3119.
DOI Google Scholar
39

Rosson, T. E.; Claiborne, S. M.; McBride, J. R.; Stratton, B. S.; Rosenthal, S. J. Bright white light emission from ultrasmall cadmium selenide nanocrystals. J. Am. Chem. Soc. 2012, 134, 8006-8009.
DOI Google Scholar
40

Dolai, S.; Nimmala, P. R.; Mandal, M.; Muhoberac, B. B.; Dria, K.; Dass, A.; Sardar, R. Isolation of bright blue light-emitting CdSe nanocrystals with 6.5 kDa core in gram scale: High photoluminescence efficiency controlled by surface ligand chemistry. Chem. Mater. 2014, 26, 1278-1285.
DOI Google Scholar
41

Yu, W. W.; Qu, L. H.; Guo, W. Z.; Peng, X. G. Experimental determination of the extinction coefficient of CdTe, CdSe, and CdS nanocrystals. Chem. Mater. 2003, 15, 2854-2860.
DOI Google Scholar
42

Jasieniak, J.; Smith, L.; van Embden, J.; Mulvaney, P. Re-examination of the size-dependent absorption properties of CdSe quantum dots. J. Phys. Chem. C 2009, 113, 19468-19474.
DOI Google Scholar
43

Ouyang, J. Y.; Zaman, M. B.; Yan, F. J.; Johnston, D.; Li, G.; Wu, X. H.; Leek, D.; Ratcliffe, C. I.; Ripmeester, J. A.; Yu, K. Multiple families of magic-sized CdSe nanocrystals with strong bandgap photoluminescence via noninjection one-pot syntheses. J. Phys. Chem. C 2008, 112, 13805-13811.
DOI Google Scholar
44

Yu, K.; Ouyang, J. Y.; Zaman, M. B.; Johnston, D.; Yan, F. J.; Li, G.; Ratcliffe, C. I.; Leek, D. M.; Wu, X. H.; Stupak, J. et al. Single-sized CdSe nanocrystals with bandgap photoemission via a noninjection one-pot approach. J. Phys. Chem. C 2009, 113, 3390-3401.
DOI Google Scholar
45

Yu, K.; Hu, M. Z.; Wang, R. B.; Le Piolet, M.; Frotey, M.; Zaman, M. B.; Wu, X. H.; Leek, D. M.; Tao, Y.; Wilkinson, D. et al. Thermodynamic equilibrium-driven formation of single-sized nanocrystals: Reaction media tuning CdSe magic-sized versus regular quantum dots. J. Phys. Chem. C 2010, 114, 3329-3339.
DOI Google Scholar
46

Liu, Y. H.; Wang, F. D.; Wang, Y. Y.; Gibbons, P. C.; Buhro, W. E. Lamellar assembly of cadmium selenide nanoclusters into quantum belts. J. Am. Chem. Soc. 2011, 133, 17005-17013.
DOI Google Scholar
47

Yu, K. CdSe magic-sized nuclei, magic-sized nanoclusters and regular nanocrystals: Monomer effects on nucleation and growth. Adv. Mater. 2012, 24, 1123-1132.
DOI Google Scholar
48

Wang, Y. Y.; Liu, Y. H.; Zhang, Y.; Wang, F. D.; Kowalski, P. J.; Rohrs, H. W.; Loomis, R. A.; Gross, M. L.; Buhro, W. E. Isolation of the magic-size CdSe nanoclusters[(CdSe)13(n-octylamine)13] and [(CdSe)13(oleylamine)13]. Angew. Chem. , Int. Ed. 2012, 51, 6154-6157.
DOI Google Scholar
49

Dolai, S.; Dutta, P.; Muhoberac, B. B.; Irving, C. D.; Sardar, R. Mechanistic study of the formation of bright white light-emitting ultrasmall CdSe nanocrystals: Role of phosphine free selenium precursors. Chem. Mater. 2015, 27, 1057-1070.
DOI Google Scholar
50

Zhu, D. K.; Hui, J.; Rowell, N.; Liu, Y. Y.; Chen, Q. Y.; Steegemans, T.; Fan, H. S.; Zhang, M.; Yu, K. Interpreting the ultraviolet absorption in the spectrum of 415 nm-bandgap CdSe magic-size clusters. J. Phys. Chem. Lett. 2018, 9, 2818-2824.
DOI Google Scholar
51

Hsieh, T. E.; Yang, T. W.; Hsieh, C. Y.; Huang, S. J.; Yeh, Y. Q.; Chen, C. H.; Li, E. Y.; Liu, Y. H. Unraveling the structure of magic-size (CdSe)13 cluster pairs. Chem. Mater. 2018, 30, 5468-5477.
DOI Google Scholar
52

Liu, Y. Y.; Willis, M.; Rowell, N.; Luo, W. Z.; Fan, H. S.; Han, S.; Yu, K. Effect of small molecule additives in the prenucleation stage of semiconductor CdSe quantum dots. J. Phys. Chem. Lett. 2018, 9, 6356-6363.
DOI Google Scholar
53

Wang, R. B.; Ouyang, J. Y.; Nikolaus, S.; Brestaz, L.; Zaman, M. B.; Wu, X. H.; Leek, D.; Ratcliffe, C. I.; Yu, K. Single-sized colloidal CdTe nanocrystals with strong bandgap photoluminescence. Chem. Commun. 2009, 962-964.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 06 February 2019
Revised: 17 March 2019
Accepted: 18 March 2019
Published: 29 May 2019
Issue date: June 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

K. Y. acknowledges financial support from the National Natural Science Foundation of China(Nos. 21773162 and 21573155), the Fundamental Research Funds for the Central Universities (No. SCU2015A002), the State Key Laboratory of Polymer Materials Engineering of Sichuan University (No. sklpme2018-2-08), and the Open Project of Key State Laboratory for Supramolecular Structures and Materials of Jilin University for SKLSSM 201830. H. F. and W. H. thank the National Major Scientific and Technological Special Project for "Significant New Drugs Development" (Nos. 2018ZX09201009-005-004 and 2018ZX09201009-005-001). We thank Sichuan Univ of Analytical & Testing Center. We are in debt to Dr. Shanling Wang (Analytical & Testing Center, Sichuan University) for TEM.

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