Journal Home > Volume 15 , Issue 10
Nano Research 2022, 15(10): 9368-9376 https://doi.org/10.1007/s12274-022-4607-9
Research Article | Issue | Published: 06 July 2022

Ultra-stable and color-tunable manganese ions doped lead-free cesium zinc halides nanocrystals in glasses for light-emitting applications

Show Author's Information Kai Li1,  Ying Ye1,  Wenchao Zhang1,  Yao Zhou1,  Yudong Zhang1,  Shisheng Lin2,3,  Hang Lin2,3,  Jian Ruan1,  Chao Liu1( )
State Key Laboratory of Silicate Materials for Architectures (SMART), Wuhan University of Technology, 122 Luoshi Road, Hongshan, Wuhan 430070, China
CAS Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China
Keywords:
lead-free, light-emitting diode (LED), cesium zinc halides nanocrystals, long-term-stability
Topics:
Light emitting diodes
Cite this article:
Li K, Ye Y, Zhang W, et al. Ultra-stable and color-tunable manganese ions doped lead-free cesium zinc halides nanocrystals in glasses for light-emitting applications. Nano Research, 2022, 15(10): 9368-9376. https://doi.org/10.1007/s12274-022-4607-9
Download citation
EndNote(RIS)
BibTeX

886

Views

75

Downloads

Citations

19

Crossref

18

WoS

20

Scopus

2

CSCD

Abstract Full text Electronic supplementary material About this article

All inorganic CsPbX3 (X = Cl, Br, and I) perovskite nanocrystals have made unprecedented radical progresses for opto-electronic applications, but their instability and toxicity of lead impede their wide applications. Herein, we report the first precipitation of lead-free Mn:Cs2ZnX4 nanocrystals in glasses. Efficient green and red photoluminescence are realized from these Mn:Cs2ZnX4 nanocrystals in glasses. By adjusting the size and halide component in these nanocrystals, coordination environment of Mn2+ ions can be tuned, leading to tunable photoluminescence with improved quantum efficiency. It is illustrated that in-situ precipitation of these Mn:Cs2ZnX4 nanocrystals in glasses significantly improves their thermal-, chemical-, and photo-stabilities, making them promising for light-emitting diodes with stable chromaticity coordinates.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Ultra-stable and color-tunable manganese ions doped lead-free cesium zinc halides nanocrystals in glasses for light-emitting applications

Show Author's information Kai Li1, Ying Ye1, Wenchao Zhang1, Yao Zhou1, Yudong Zhang1, Shisheng Lin2,3, Hang Lin2,3, Jian Ruan1, Chao Liu1( )
State Key Laboratory of Silicate Materials for Architectures (SMART), Wuhan University of Technology, 122 Luoshi Road, Hongshan, Wuhan 430070, China
CAS Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China

Abstract

All inorganic CsPbX3 (X = Cl, Br, and I) perovskite nanocrystals have made unprecedented radical progresses for opto-electronic applications, but their instability and toxicity of lead impede their wide applications. Herein, we report the first precipitation of lead-free Mn:Cs2ZnX4 nanocrystals in glasses. Efficient green and red photoluminescence are realized from these Mn:Cs2ZnX4 nanocrystals in glasses. By adjusting the size and halide component in these nanocrystals, coordination environment of Mn2+ ions can be tuned, leading to tunable photoluminescence with improved quantum efficiency. It is illustrated that in-situ precipitation of these Mn:Cs2ZnX4 nanocrystals in glasses significantly improves their thermal-, chemical-, and photo-stabilities, making them promising for light-emitting diodes with stable chromaticity coordinates.

Keywords: lead-free, light-emitting diode (LED), cesium zinc halides nanocrystals, long-term-stability

References(51)

1

Yin, W. J.; Shi, T. T.; Yan, Y. F. Unique properties of halide perovskites as possible origins of the superior solar cell performance. Adv. Mater. 2014, 26, 4653–4658.
DOI Google Scholar
2

Green, M. A.; Ho-Baillie, A.; Snaith, H. J. The emergence of perovskite solar cells. Nat. Photonics 2014, 8, 506–514.
DOI Google Scholar
3

Shi, D.; Adinolfi, V.; Comin, R.; Yuan, M. J.; Alarousu, E.; Buin, A.; Chen, Y.; Hoogland, S.; Rothenberger, A.; Katsiev, K. et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 2015, 347, 519–522.
DOI Google Scholar
4

Fan, Q. Q.; Biesold-McGee, G. V.; Ma, J. Z.; Xu, Q. N.; Pan, S.; Peng, J.; Lin, Z. Q. Lead-free halide perovskite nanocrystals: Crystal structures, synthesis, stabilities, and optical properties. Angew. Chem., Int. Ed. 2020, 59, 1030–1046.
DOI Google Scholar
5

Sun, S. Q.; Lu, M.; Gao, X. P.; Shi, Z. F.; Bai, X.; Yu, W. W.; Zhang, Y. 0D perovskites: Unique properties, synthesis, and their applications. Adv. Sci. (Weinh. ) 2021, 8, 2102689.
Google Scholar
6

Li, H. M.; Lin, H.; Ouyang, D.; Yao, C. L.; Li, C.; Sun, J. Y.; Song, Y. L.; Wang, Y. F.; Yan, Y. F.; Wang, Y. et al. Efficient and stable red perovskite light-emitting diodes with operational stability > 300 h. Adv. Mater. 2021, 33, 2008820.
DOI Google Scholar
7

Liu, Z.; Qiu, W. D.; Peng, X. M.; Sun, G. W.; Liu, X. Y.; Liu, D. H.; Li, Z. C.; He, F. R.; Shen, C. Y.; Gu, Q. et al. Perovskite light-emitting diodes with EQE exceeding 28% through a synergetic dual-additive strategy for defect passivation and nanostructure regulation. Adv. Mater. 2021, 33, 2103268.
DOI Google Scholar
8

Shen, Y.; Wu, H. Y.; Li, Y. Q.; Shen, K. C.; Gao, X. Y.; Song, F.; Tang, J. X. Interfacial nucleation seeding for electroluminescent manipulation in blue perovskite light-emitting diodes. Adv. Funct. Mater. 2021, 31, 2170331.
DOI Google Scholar
9

Lou, S. Q.; Xuan, T. T.; Wang, J. (INVITED) stability:A desiderated problem for the lead halide perovskites. Opt. Mater. X 2019, 1, 100023.
Google Scholar
10

Luo, B. B.; Li, F.; Xu, K.; Guo, Y.; Liu, Y.; Xia, Z. G.; Zhang, J. Z. B-site doped lead halide perovskites:Synthesis, band engineering, photophysics, and light emission applications. J. Mater. Chem. C 2019, 7, 2781–2808.
Google Scholar
11

Wang, Z.; Zhang, Y. Q.; Liu, X. D.; Yu, Y. X.; Xu, F. C.; Ding, J.; Liang, X. J.; Yang, K. Q.; Xiang, W. D. High stability and strong luminescence CsPbBr3/Cs4PbBr6 perovskite nanocomposite: Large-scale synthesis, reversible luminescence, and anti-counterfeiting application. Adv. Mater. Technol. 2021, 6, 2100654.
DOI Google Scholar
12

Akkerman, Q. A.; Rainò, G.; Kovalenko, M. V.; Manna, L. Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals. Nat. Mater. 2018, 17, 394–405.
DOI Google Scholar
13

Chen, W. W.; Hao, J. Y.; Hu, W.; Zang, Z. G.; Tang, X. S.; Fang, L.; Niu, T. C.; Zhou, M. Enhanced stability and tunable photoluminescence in perovskite CsPbX3/ZnS quantum dot heterostructure. Small 2017, 13, 1604085.
DOI Google Scholar
14

Shao, G. Z.; Zhao, Y.; Yu, Y. X.; Yang, H. S.; Liu, X. D.; Zhang, Y. J.; Xiang, W. D.; Liang, X. J. Bright emission and high photoluminescence CsPb2Br5 NCs encapsulated in mesoporous silica with ultrahigh stability and excellent optical properties for white light-emitting diodes. J. Mater. Chem. C 2019, 7, 13585–13593.
Google Scholar
15

Ercan, E.; Tsai, P. C.; Chen, J. Y.; Lam, J. Y.; Hsu, L. C.; Chueh, C. C.; Chen, W. C. Stretchable and ambient stable perovskite/polymer luminous hybrid nanofibers of multicolor fiber mats and their white LED applications. ACS Appl. Mater. Interfaces 2019, 11, 23605–23615.
DOI Google Scholar
16

Chen, Z.; Gu, Z. G.; Fu, W. Q.; Wang, F.; Zhang, J. A confined fabrication of perovskite quantum dots in oriented MOF thin film. ACS Appl. Mater. Interfaces 2016, 8, 28737–28742.
DOI Google Scholar
17

Huang, S. Q.; Li, Z. C.; Kong, L.; Zhu, N. W.; Shan, A. D.; Li, L. Enhancing the stability of CH3NH3PbBr3 quantum dots by embedding in silica spheres derived from tetramethyl orthosilicate in “Waterless” toluene. J. Am. Chem. Soc. 2016, 138, 5749–5752.
DOI Google Scholar
18

Ai, B.; Liu, C.; Wang, J.; Xie, J.; Han, J. J.; Zhao, X. J. Precipitation and optical properties of CsPbBr3 quantum dots in phosphate glasses. J. Am. Ceram. Soc. 2016, 99, 2875–2877.
DOI Google Scholar
19

Ye, Y.; Zhang, W. C.; Zhao, Z. Y.; Wang, J.; Liu, C.; Deng, Z.; Zhao, X. J.; Han, J. J. Highly luminescent cesium lead halide perovskite nanocrystals stabilized in glasses for light-emitting applications. Adv. Opt. Mater. 2019, 7, 1801663.
DOI Google Scholar
20

Zhang, B. W.; Zhang, K.; Li, L. F.; Xu, C. C.; Wang, R. F.; Wang, C.; Yang, J.; Yang, Y.; Wang, J.; Qiu, F. et al. Enhancing stability and luminescence quantum yield of CsPbBr3 quantum dots by embedded in borosilicate glass. J. Alloys Compd. 2021, 874, 159962.
DOI Google Scholar
21

Kong, Q. K.; Yang, B.; Chen, J. S.; Zhang, R. L.; Liu, S. P.; Zheng, D. Y.; Zhang, H. L.; Liu, Q. T.; Wang, Y. Y.; Han, K. L. Phase engineering of cesium manganese bromides nanocrystals with color-tunable emission. Angew. Chem., Int. Ed. 2021, 60, 19653–19659.
DOI Google Scholar
22

Shankar, H.; Ghosh, S.; Kar, P. Highly stable blue fluorescent lead free all-inorganic Cs2ZnX4 2D perovskite nanocrystals. J. Alloys Compd. 2020, 844, 156148.
DOI Google Scholar
23

Zhang, Z. X.; Zhao, R. T.; Teng, S. Y.; Huang, K. K.; Zhang, L. J.; Wang, D. Y.; Yang, W. S.; Xie, R. G.; Pradhan, N. Color tunable self-trapped emissions from lead-free all inorganic IA-IB bimetallic halides Cs-Ag-X (X = Cl, Br, I). Small 2020, 16, 2004272.
DOI Google Scholar
24

Zhao, X. H.; Wu, M.; Liu, H.; Wang, Y. X.; Wang, K.; Yang, X. Y.; Zou, B. Pressure-treated engineering to harvest enhanced green emission in Mn-based organic-inorganic metal halides at ambient conditions. Adv. Funct. Mater. 2021, 32, 2109277.
Google Scholar
25

Jellicoe, T. C.; Richter, J. M.; Glass, H. F. J.; Tabachnyk, M.; Brady, R.; Dutton, S. E.; Rao, A.; Friend, R. H.; Credgington, D.; Greenham, N. C. et al. Synthesis and optical properties of lead-free cesium tin halide perovskite nanocrystals. J. Am. Chem. Soc. 2016, 138, 2941–2944.
DOI Google Scholar
26

Fu, P. F.; Huang, M. L.; Shang, Y. Q.; Yu, N.; Zhou, H. L.; Zhang, Y. B.; Chen, S. Y.; Gong, J. K.; Ning, Z. J. Organic-inorganic layered and hollow tin bromide perovskite with tunable broadband emission. ACS Appl. Mater. Interfaces 2018, 10, 34363–34369.
DOI Google Scholar
27

Roccanova, R.; Yangui, A.; Nhalil, H.; Shi, H. L.; Du, M. H.; Saparov, B. Near-unity photoluminescence quantum yield in blue-emitting Cs3Cu2Br5–xIx (0 ≤ x ≤ 5). ACS Appl. Electron. Mater. 2019, 1, 269–274.
DOI Google Scholar
28

Cheng, P. F.; Feng, L.; Liu, Y. F.; Zheng, D. Y.; Sang, Y. B.; Zhao, W. Y.; Yang, Y.; Yang, S. Q.; Wei, D. H.; Wang, G. X. et al. Doped zero-dimensional cesium zinc halides for high-efficiency blue light emission. Angew. Chem., Int. Ed. 2020, 59, 21414–21418.
DOI Google Scholar
29

Xu, K. M.; Wei, Q.; Wang, H.; Yao, B.; Zhou, W. J.; Gao, R.; Chen, H.; Li, H. S.; Wang, J. T.; Ning, Z. J. The 3D-structure-mediated growth of zero-dimensional Cs4SnX6 nanocrystals. Nanoscale 2022, 14, 2248–2255.
DOI Google Scholar
30

Su, B. B.; Li, M. Z.; Song, E. H.; Xia, Z. G. Sb3+-doping in cesium zinc halides single crystals enabling high-efficiency near-infrared emission. Adv. Funct. Mater. 2021, 31, 2105316.
DOI Google Scholar
31

Morad, V.; Cherniukh, I.; Pöttschacher, L.; Shynkarenko, Y.; Yakunin, S.; Kovalenko, M. V. Manganese(II) in tetrahedral halide environment: Factors governing bright green luminescence. Chem. Mater. 2019, 31, 10161–10169.
DOI Google Scholar
32

Li, S. R.; Luo, J. J.; Liu, J.; Tang, J. Self-trapped excitons in all-inorganic halide perovskites: Fundamentals, status, and potential applications. J. Phys. Chem. Lett. 2019, 10, 1999–2007.
DOI Google Scholar
33

Williams, R. T.; Song, K. S.; Faust, W. L.; Leung, C. H. Off-center self-trapped excitons and creation of lattice defects in alkali halide crystals. Phys. Rev. B 1986, 33, 7232–7240.
DOI Google Scholar
34

Fowler, W. B.; Marrone, M. J.; Kabler, M. N. Theory of self-trapped exciton luminescence in halide crystals. Phys. Rev. B 1973, 8, 5909–5919.
DOI Google Scholar
35

Zhu, D. X.; Zaffalon, M. L.; Pinchetti, V.; Brescia, R.; Moro, F.; Fasoli, M.; Fanciulli, M.; Tang, A. W.; Infante, I.; De Trizio, L. et al. Bright blue emitting Cu-doped Cs2ZnCl4 colloidal nanocrystals. Chem. Mater. 2020, 32, 5897–5903.
DOI Google Scholar
36

Su, B. B.; Zhou, G. J.; Huang, J. L.; Song, E. H.; Nag, A.; Xia, Z. G. Mn2+-doped metal halide perovskites: Structure, photoluminescence, and application. Laser Photonics Rev. 2021, 15, 2000334.
DOI Google Scholar
37

Zhou, Q.; Dolgov, L.; Srivastava, A. M.; Zhou, L.; Wang, Z. L.; Shi, J. X.; Dramicanin, M. D.; Brik, M. G.; Wu, M. M. Mn2+ and Mn4+ red phosphors: Synthesis, luminescence and applications in WLEDs. A review. J. Mater. Chem. C 2018, 6, 2652–2671.
DOI Google Scholar
38

Lin, S. S.; Lin, H.; Ma, C. G.; Cheng, Y.; Ye, S. Z.; Lin, F. L.; Li, R. F.; Xu, J.; Wang, Y. S. High-security-level multi-dimensional optical storage medium: Nanostructured glass embedded with LiGa5O8: Mn2+ with photostimulated luminescence. Light Sci. Appl. 2020, 9, 22.
DOI Google Scholar
39

Su, B. B.; Molokeev, M. S.; Xia, Z. G. Mn2+-based narrow-band green-emitting Cs3MnBr5 phosphor and the performance optimization by Zn2+ alloying. J. Mater. Chem. C 2019, 7, 11220–11226.
DOI Google Scholar
40

Rao, J. L.; Purandar, K. Electronic absorption spectrum of Mn2+ ions doped in diglycine barium chloride monohydrate. Solid State Commun. 1981, 37, 983–986.
DOI Google Scholar
41

Peng, H.; Huang, T.; Zou, B. S.; Tian, Y.; Wang, X. X.; Guo, Y. C.; Dong, T. T.; Yu, Z. M.; Ding, C. J.; Yang, F. et al. Organic-inorganic hybrid manganese bromine single crystal with dual-band photoluminescence from polaronic and bipolaronic excitons. Nano Energy 2021, 87, 106166.
DOI Google Scholar
42

Yan, S. Y.; Tian, W. L.; Chen, H.; Tang, K. X.; Lin, T. T.; Zhong, G. Y.; Qiu, L. Z.; Pan, X. Y.; Wang, W. Z. Synthesis of 0D manganese-based organic-inorganic hybrid perovskite and its application in lead-free red light-emitting diode. Adv. Funct. Mater. 2021, 31, 2100855.
DOI Google Scholar
43

Almutlaq, J.; Mir, W. J.; Gutiérrez-Arzaluz, L.; Yin, J.; Vasylevskyi, S.; Maity, P.; Liu, J. K.; Naphade, R.; Mohammed, O. F.; Bakr, O. M. CsMnBr3: Lead-free nanocrystals with high photoluminescence quantum yield and picosecond radiative lifetime. ACS Mater. Lett. 2021, 3, 290–297.
DOI Google Scholar
44

Ma, Y. Y.; Song, Y. R.; Xu, W. J.; Zhong, Q. Q.; Fu, H. Q.; Liu, X. L.; Yue, C. Y.; Lei, X. W. Solvent-free mechanochemical syntheses of microscale lead-free hybrid manganese halides as efficient green light phosphors. J. Mater. Chem. C 2021, 9, 9952–9961.
Google Scholar
45

Xiao, H.; Dang, P. P.; Yun, X. H.; Li, G. G.; Wei, Y.; Wei, Y.; Xiao, X.; Zhao, Y. J.; Molokeev, M. S.; Cheng, Z. Y. et al. Solvatochromic photoluminescent effects in all-inorganic manganese(II)-based perovskites by highly selective solvent-induced crystal-to-crystal phase transformations. Angew. Chem., Int. Ed. 2021, 60, 3699–3707.
DOI Google Scholar
46

Yan, S. Y.; Tang, K. X.; Lin, Y. J.; Ren, Y. H.; Tian, W. L.; Chen, H.; Lin, T. T.; Qiu, L. Z.; Pan, X. Y.; Wang, W. Z. Light-emitting diodes with manganese halide tetrahedron embedded in anti-perovskites. ACS Energy Lett. 2021, 6, 1901–1911.
DOI Google Scholar
47

Li, C. Y.; Bai, X. W.; Guo, Y. C.; Zou, B. S. Tunable emission properties of manganese chloride small single crystals by pyridine incorporation. ACS Omega 2019, 4, 8039–8045.
DOI Google Scholar
48

Bai, X. W.; Zhong, H. Z.; Chen, B. K.; Chen, C.; Han, J. B.; Zeng, R. S.; Zou, B. S. Pyridine-modulated Mn ion emission properties of C10H12N2MnBr4 and C5H6NMnBr3 single crystals. J. Phys. Chem. C. 2018, 122, 3130–3137.
DOI Google Scholar
49

Peng, H.; Zou, B. S.; Guo, Y. C.; Xiao, Y. H.; Zhi, R. N.; Fan, X. Y.; Zou, M.; Wang, J. P. Evolution of the structure and properties of mechanochemically synthesized pyrrolidine incorporated manganese bromide powders. J. Mater. Chem. C 2020, 8, 6488–6495.
DOI Google Scholar
50

Wei, J. H.; Liao, J. F.; Wang, X. D.; Zhou, L.; Jiang, Y.; Kuang, D. B. All-inorganic lead-free heterometallic Cs4MnBi2Cl12 perovskite single crystal with highly efficient orange emission. Matter 2020, 3, 892–903.
DOI Google Scholar
51
Dang, Z. Y.; Shamsi, J.; Palazon, F.; Imran, M.; Akkerman, Q. A.; Park, S.; Bertoni, G.; Prato, M.; Brescia, R.; Manna, L. In situ transmission electron microscopy study of electron beam-induced transformations in colloidal cesium lead halide perovskite nanocrystals. ACS Nano 2017, 11, 2124–2132.
File
12274_2022_4607_MOESM1_ESM.pdf (2.2 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 01 March 2022
Revised: 19 May 2022
Accepted: 01 June 2022
Published: 06 July 2022
Issue date: October 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was financially supported by the Key Research and Development Program of Hubei Province, China (No. 2021BAA206).

Return