Journal Home > Volume 15 , Issue 1
Nano Research 2022, 15(1): 644-652 https://doi.org/10.1007/s12274-021-3538-1
Research Article | Issue | Published: 14 June 2021

Precursor chemistry towards highly efficient and phase-stable red emitting CsPbI3 perovskite nanocrystals

Show Author's Information Dejian Chen1,2,  Decai Huang1,2,  Mingwei Yang1,2,  Kunyuan Xu1,2,  Jie Hu1,2,  Sisi Liang1,2,  Haomiao Zhu1,2( )
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Key Laboratory of Nanomaterials Fujian Institute of Research on the Structure of MatterChinese Academy of Sciences Fuzhou 350002 China
Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Institute of Rare Earth Materials Haixi Institute Chinese Academy of Sciences, Xiamen 361021 China
Keywords:
stability, perovskite nanocrystals, precursor, CsPbX3, vacancy defect
Topics:
Perovskite
Cite this article:
Chen D, Huang D, Yang M, et al. Precursor chemistry towards highly efficient and phase-stable red emitting CsPbI3 perovskite nanocrystals. Nano Research, 2022, 15(1): 644-652. https://doi.org/10.1007/s12274-021-3538-1
Download citation
EndNote(RIS)
BibTeX

673

Views

39

Downloads

Citations

18

Crossref

17

WoS

15

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

All-inorganic cesium lead halide perovskite nanocrystals (CsPbX3, X = Cl, Br, I) have attracted considerable scientific and technological interest due to their precise bandgap tunability, high color purity and efficient luminescence. Nevertheless, their poor stability in harsh conditions such as moisture, ultraviolet (UV) light irradiation and high temperature, is a major obstacle for their further commercial applications. Herein, by simply using a new type of precursor, namely "HPbX3" (X = Cl, Br, I), we can achieve the coordination equilibrium for Pb precursors during reaction and obtain high-quality perovskite nanocrystals with tremendously enhanced luminous efficiency and chemical stability based on hot-injection method. The prepared α-CsPbI3 nanocrystals exhibit an extremely high photoluminescence quantum yield of 96% and keep stable in air for more than two months without any post-synthesis treatment. Moreover, stability evaluations under UV light irradiation, water or thermal impact are also performed and the results show substantially improved stability of these nanocrystals as compared with the samples prepared using traditional PbI2 as precursor. Through temperature-dependent (10–300 K) steady and transient spectral analysis combined with compositional measurements, it is revealed that the lower structural defect density, which is guaranteed by abundant halogen when using HPbX3 as precursor, is the most important reason for such performance enhancement.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Precursor chemistry towards highly efficient and phase-stable red emitting CsPbI3 perovskite nanocrystals

Show Author's information Dejian Chen1,2, Decai Huang1,2, Mingwei Yang1,2, Kunyuan Xu1,2, Jie Hu1,2, Sisi Liang1,2, Haomiao Zhu1,2( )
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Key Laboratory of Nanomaterials Fujian Institute of Research on the Structure of MatterChinese Academy of Sciences Fuzhou 350002 China
Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Institute of Rare Earth Materials Haixi Institute Chinese Academy of Sciences, Xiamen 361021 China

Abstract

All-inorganic cesium lead halide perovskite nanocrystals (CsPbX3, X = Cl, Br, I) have attracted considerable scientific and technological interest due to their precise bandgap tunability, high color purity and efficient luminescence. Nevertheless, their poor stability in harsh conditions such as moisture, ultraviolet (UV) light irradiation and high temperature, is a major obstacle for their further commercial applications. Herein, by simply using a new type of precursor, namely "HPbX3" (X = Cl, Br, I), we can achieve the coordination equilibrium for Pb precursors during reaction and obtain high-quality perovskite nanocrystals with tremendously enhanced luminous efficiency and chemical stability based on hot-injection method. The prepared α-CsPbI3 nanocrystals exhibit an extremely high photoluminescence quantum yield of 96% and keep stable in air for more than two months without any post-synthesis treatment. Moreover, stability evaluations under UV light irradiation, water or thermal impact are also performed and the results show substantially improved stability of these nanocrystals as compared with the samples prepared using traditional PbI2 as precursor. Through temperature-dependent (10–300 K) steady and transient spectral analysis combined with compositional measurements, it is revealed that the lower structural defect density, which is guaranteed by abundant halogen when using HPbX3 as precursor, is the most important reason for such performance enhancement.

Keywords: stability, perovskite nanocrystals, precursor, CsPbX3, vacancy defect

References(46)

1

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.
DOI Google Scholar
2

Jung, M.; Ji, S. G.; Kim, G.; Seok, S. I. Perovskite precursor solution chemistry: From fundamentals to photovoltaic applications. Chem. Soc. Rev. 2019, 48, 2011–2038.
DOI Google Scholar
3

Akkerman, Q. A.; D'Innocenzo, V.; Accornero, S.; Scarpellini, A.; Petrozza, A.; Prato, M.; Manna, L. Tuning the optical properties of cesium lead halide perovskite nanocrystals by anion exchange reactions. J. Am. Chem. Soc. 2015, 137, 10276–10281.
DOI Google Scholar
4

Li, X. M.; Wu, Y.; Zhang, S. L.; Cai, B.; Gu, Y.; Song, J. Z.; Zeng, H. B. CsPbX3 quantum dots for lighting and displays: Room-temperature synthesis, photoluminescence superiorities, underlying origins and white light-emitting diodes. Adv. Funct. Mater. 2016, 26, 2435–2445.
DOI Google Scholar
5

Swarnkar, A.; Marshall, A. R.; Sanehira, E. M.; Chernomordik, B. D.; Moore, D. T.; Christians, J. A.; Chakrabarti, T.; Luther, J. M. Quantum dot-induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics. Science 2016, 354, 92–95.
DOI Google Scholar
6

Pan, J.; Shang, Y. Q.; Yin, J.; De Bastiani, M.; Peng, W.; Dursun, I.; Sinatra, L.; El-Zohry, A. M.; Hedhili, M. N.; Emwas, A. H. et al. Bidentate ligand-passivated CsPbI3 perovskite nanocrystals for stable near-unity photoluminescence quantum yield and efficient red light-emitting diodes. J. Am. Chem. Soc. 2017, 140, 562–565.
DOI Google Scholar
7

Wang, K.; Jin, Z. W.; Liang, L.; Bian, H.; Bai, D. L.; Wang, H. R.; Zhang, J. R.; Wang, Q.; Liu, S. Z. All-inorganic cesium lead iodide perovskite solar cells with stabilized efficiency beyond 15. Nat. Commun. 2018, 9, 4544.
DOI Google Scholar
8

Wang, Y.; Dar, M. I.; Ono, L. K.; Zhang, T. Y.; Kan, M.; Li, Y. W.; Zhang, L. J.; Wang, X. T.; Yang, Y. G.; Gao, X. Y. et al. Thermodynamically stabilized β-CsPbI3-based perovskite solar cells with efficiencies > 18%. Science 2019, 365, 591–595.
DOI Google Scholar
9

Yi, C. Y.; Luo, J. S.; Meloni, S.; Boziki, A.; Ashari-Astani, N.; Grätzel, C.; Zakeeruddin, S. M.; Röthlisberger, U.; Grätzel, M. Entropic stabilization of mixed A-cation ABX3 metal halide perovskites for high performance perovskite solar cells. Energy Environ. Sci. 2016, 9, 656–662.
DOI Google Scholar
10

Liu, F.; Ding, C.; Zhang, Y. H.; Ripolles, T. S.; Kamisaka, T.; Toyoda, T.; Hayase, S.; Minemoto, T.; Yoshino, K.; Dai, S. Y. et al. Colloidal synthesis of air-stable alloyed CsSn1–xPbxI3 perovskite nanocrystals for use in solar cells. J. Am. Chem. Soc. 2017, 139, 16708–16719.
DOI Google Scholar
11

Yao, J. S.; Ge, J.; Wang, K. H.; Zhang, G. Z.; Zhu, B. S.; Chen, C.; Zhang, Q.; Luo, Y.; Yu, S. H.; Yao, H. B. Few-nanometer-sized α-CsPbI3 quantum dots enabled by strontium substitution and iodide passivation for efficient red-light emitting diodes. J. Am. Chem. Soc. 2019, 141, 2069–2079.
DOI Google Scholar
12

Lu, M.; Zhang, X. Y.; Zhang, Y.; Guo, J.; Shen, X. Y.; Yu, W. W.; Rogach, A. L. Simultaneous strontium doping and chlorine surface passivation improve luminescence intensity and stability of CsPbI3 nanocrystals enabling efficient light-emitting devices. Adv. Mater. 2018, 30, 1804691.
DOI Google Scholar
13

Bai, D. L.; Bian, H.; Jin, Z. W.; Wang, H. R.; Meng, L. N.; Wang, Q.; Liu, S. Z. Temperature-assisted crystallization for inorganic CsPbI2Br perovskite solar cells to attain high stabilized efficiency 14.81%. Nano Energy 2018, 52, 408–415.
DOI Google Scholar
14

Wang, Y.; Zhang, T. Y.; Kan, M.; Zhao, Y. X. Bifunctional stabilization of all-inorganic α-CsPbI3 perovskite for 17% efficiency photovoltaics. J. Am. Chem. Soc. 2018, 140, 12345–12348.
DOI Google Scholar
15

Dutta, A.; Dutta, S. K.; Das Adhikari, S.; Pradhan, N. Phase-stable CsPbI3 nanocrystals: The reaction temperature matters. Angew. Chem. , Int. Ed. 2018, 57, 9083–9087.
DOI Google Scholar
16

Imran, M.; Caligiuri, V.; Wang, M. J.; Goldoni, L.; Prato, M.; Krahne, R.; De Trizio, L.; Manna, L. Benzoyl halides as alternative precursors for the colloidal synthesis of lead-based halide perovskite nanocrystals. J. Am. Chem. Soc. 2018, 140, 2656–2664.
DOI Google Scholar
17

Brennan, M. C.; Draguta, S.; Kamat, P. V.; Kuno, M. Light-induced anion phase segregation in mixed halide perovskites. ACS Energy Lett. 2018, 3, 204–213.
DOI Google Scholar
18

Seth, S.; Ahmed, T.; De, A.; Samanta, A. Tackling the defects, stability, and photoluminescence of CsPbX3 perovskite nanocrystals. ACS Energy Lett. 2019, 4, 1610–1618.
DOI Google Scholar
19

Pradhan, N. Tips and twists in making high photoluminescence quantum yield perovskite nanocrystals. ACS Energy Lett. 2019, 4, 1634–1638.
DOI Google Scholar
20

Dai, J. F.; Xi, J.; Zu, Y. Q.; Li, L.; Xu, J.; Shi, Y. F.; Liu, X. Y.; Fan, Q. H.; Zhang, J. J.; Wang, S. P. et al. Surface mediated ligands addressing bottleneck of room-temperature synthesized inorganic perovskite nanocrystals toward efficient light-emitting diodes. Nano Energy 2020, 70, 104467.
DOI Google Scholar
21

Wang, F.; Yu, H.; Xu, H. H.; Zhao, N. HPbI3: A new precursor compound for highly efficient solution-processed perovskite solar cells. Adv. Funct. Mater. 2015, 25, 1120–1126.
DOI Google Scholar
22

Pang, S. P.; Zhou, Y. Y.; Wang, Z. W.; Yang, M. J.; Krause, A. R.; Zhou, Z. M.; Zhu, K.; Padture, N. P.; Cui, G. L. Transformative evolution of organolead triiodide perovskite thin films from strong room-temperature solid-gas interaction between HPbI3-CH3NH2 precursor pair. J. Am. Chem. Soc. 2016, 138, 750–753.
DOI Google Scholar
23

Xiang, S. S.; Fu, Z. H.; Li, W. P.; Wei, Y.; Liu, J. M.; Liu, H. C.; Zhu, L. Q.; Zhang, R. F.; Chen, H. N. Highly air-stable carbon-based α-CsPbI3 perovskite solar cells with a broadened optical spectrum. ACS Energy Lett. 2018, 3, 1824–1831.
DOI Google Scholar
24

Jiang, Y. Z.; Yuan, J.; Ni, Y. X.; Yang, J. E.; Wang, Y.; Jiu, T. G.; Yuan, M. J.; Chen, J. Reduced-dimensional α-CsPbX3 perovskites for efficient and stable photovoltaics. Joule 2018, 2, 1356–1368.
DOI Google Scholar
25

Cao, F.; Yu, D. J.; Xu, X. B.; Cai, B.; Gu, Y.; Dong, Y. H.; Shen, Y. L.; Zeng, H. B. Water-assisted synthesis of blue chip excitable 2D halide perovskite with green-red dual emissions for white LEDs. Small Methods 2019, 3, 1900365.
DOI Google Scholar
26

Xi, J.; Piao, C. C.; Byeon, J.; Yoon, J.; Wu, Z. X.; Choi, M. Rational core-shell design of open air low temperature in situ processable CsPbI3 quasi-nanocrystals for stabilized p-i-n solar cells. Adv. Energy Mater. 2019, 9, 1901787.
DOI Google Scholar
27

Duan, C. Y.; Cui, J.; Zhang, M. M.; Han, Y.; Yang, S. M.; Zhao, H.; Bian, H. T.; Yao, J. X.; Zhao, K.; Liu, Z. K. et al. Precursor engineering for ambient-compatible antisolvent-free fabrication of high-efficiency CsPbI2Br perovskite solar cells. Adv. Energy Mater. 2020, 10, 2000691.
DOI Google Scholar
28

Ke, W. J.; Spanopoulos, I.; Stoumpos, C. C.; Kanatzidis, M. G. Myths and reality of HPbI3 in halide perovskite solar cells. Nat. Commun. 2018, 9, 4785.
DOI Google Scholar
29

Pei, Y. H.; Liu, Y.; Li, F. M.; Bai, S.; Jian, X.; Liu, M. Z. Unveiling property of hydrolysis-derived DMAPbI3 for perovskite devices: Composition engineering, defect mitigation, and stability optimization. iScience 2019, 15, 165–172.
DOI Google Scholar
30

Bian, H.; Wang, H. R.; Li, Z. Z.; Zhou, F. G.; Xu, Y. K.; Zhang, H.; Wang, Q.; Ding, L. M.; Liu, S. Z.; Jin, Z. W. Unveiling the effects of hydrolysis-derived DMAI/DMAPbIx intermediate compound on the performance of CsPbI3 solar cells. Adv. Sci. 2020, 7, 1902868.
DOI Google Scholar
31

Cai, Y. T.; Wang, H. R.; Li, Y.; Wang, L.; Lv, Y.; Yang, X. Y.; Xie, R. J. Trimethylsilyl iodine-mediated synthesis of highly bright red-emitting CsPbI3 perovskite quantum dots with significantly improved stability. Chem. Mater. 2019, 31, 881–889.
DOI Google Scholar
32

Liu, F.; Zhang, Y. H.; Ding, C.; Kobayashi, S.; Izuishi, T.; Nakazawa, N.; Toyoda, T.; Ohta, T.; Hayase, S.; Minemoto, T. et al. Highly luminescent phase-stable CsPbI3 perovskite quantum dots achieving near 100% absolute photoluminescence quantum yield. ACS Nano 2017, 11, 10373–10383.
DOI Google Scholar
33

Huang, H. L.; Zhao, F. C.; Liu, L. G.; Zhang, F.; Wu, X. G.; Shi, L. J.; Zou, B. S.; Pei, Q. B.; Zhong, H. Z. Emulsion synthesis of size-tunable CH3NH3PbBr3 quantum dots: An alternative route toward efficient light-emitting diodes. ACS Appl. Mater. Interfaces 2015, 7, 28128–28133.
DOI Google Scholar
34

Berhe, T. A.; Su, W. N.; Chen, C. H.; Pan, C. J.; Cheng, J. H.; Chen, H. M.; Tsai, M. C.; Chen, L. Y.; Dubale, A. A.; Hwang, B. J. Organometal halide perovskite solar cells: Degradation and stability. Energy Environ. Sci. 2016, 9, 323–356.
DOI Google Scholar
35

Wei, Y.; Cheng, Z. Y.; Lin, J. An overview on enhancing the stability of lead halide perovskite quantum dots and their applications in phosphor-converted LEDs. Chem. Soc. Rev. 2019, 48, 310–350.
DOI Google Scholar
36

Sutton, R. J.; Filip, M. R.; Haghighirad, A. A.; Sakai, N.; Wenger, B.; Giustino, F.; Snaith, H. J. Cubic or orthorhombic? revealing the crystal structure of metastable black-phase CsPbI3 by theory and experiment. ACS Energy Lett. 2018, 3, 1787–1794.
DOI Google Scholar
37

Marronnier, A.; Roma, G.; Boyer-Richard, S.; Pedesseau, L.; Jancu, J. M.; Bonnassieux, Y.; Katan, C.; Stoumpos, C. C.; Kanatzidis, M. G.; Even, J. Anharmonicity and disorder in the black phases of cesium lead iodide used for stable inorganic perovskite solar cells. ACS Nano 2018, 12, 3477–3486.
DOI Google Scholar
38

Diroll, B. T.; Nedelcu, G.; Kovalenko, M. V.; Schaller, R. D. High-temperature photoluminescence of CsPbX3 (X= Cl, Br, I) nanocrystals. Adv. Funct. Mater. 2017, 27, 1606750.
DOI Google Scholar
39

Balena, A.; Perulli, A.; Fernandez, M.; De Giorgi, M. L.; Nedelcu, G.; Kovalenko, M. V.; Anni, M. Temperature dependence of the amplified spontaneous emission from CsPbBr3 nanocrystal thin films. J. Phys. Chem. C 2018, 122, 5813–5819.
DOI Google Scholar
40

Lee, S. M.; Moon, C. J.; Lim, H.; Lee, Y.; Choi, M. Y.; Bang, J. Temperature-dependent photoluminescence of cesium lead halide perovskite quantum dots: Splitting of the photoluminescence peaks of CsPbBr3 and CsPb(Br/I)3 quantum dots at low temperature. J. Phys. Chem. C 2017, 121, 26054–26062.
DOI Google Scholar
41

Lanzetta, L.; Aristidou, N.; Haque, S. A. Stability of lead and tin halide perovskites: The link between defects and degradation. J. Phys. Chem. Lett. 2020, 11, 574–585.
DOI Google Scholar
42

Aristidou, N.; Eames, C.; Sanchez-Molina, I.; Bu, X. N.; Kosco, J.; Islam, M. S.; Haque, S. A. Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells. Nat. Commun. 2017, 8, 15218.
DOI Google Scholar
43

Zhao, T.; Chueh, C. C.; Chen, Q.; Rajagopal, A.; Jen, A. K. Y. Defect passivation of organic-inorganic hybrid perovskites by diammonium iodide toward high-performance photovoltaic devices. ACS Energy Lett. 2016, 1, 757–763.
DOI Google Scholar
44

Wang, Q.; Chen, B.; Liu, Y.; Deng, Y. H.; Bai, Y.; Dong, Q. F.; Huang, J. S. Scaling behavior of moisture-induced grain degradation in polycrystalline hybrid perovskite thin films. Energy Environ. Sci. 2017, 10, 516–522.
DOI Google Scholar
45

Lu, M.; Zhang, X. Y.; Bai, X.; Wu, H.; Shen, X. Y.; Zhang, Y.; Zhang, W.; Zheng, W. T.; Song, H. W.; Yu, W. W. et al. Spontaneous silver doping and surface passivation of CsPbI3 perovskite active layer enable light-emitting devices with an external quantum efficiency of 11.2%. ACS Energy Lett. 2018, 3, 1571–1577.
DOI Google Scholar
46

Li, F.; Liu, Y.; Wang, H. L.; Zhan, Q.; Liu, Q. L.; Xia, Z. G. Postsynthetic surface trap removal of CsPbX3 (X = Cl, Br, or I) quantum dots via a ZnX2/hexane solution toward an enhanced luminescence quantum yield. Chem. Mater. 2018, 30, 8546–8554.
DOI Google Scholar
File
12274_2021_3538_MOESM1_ESM.pdf (4.5 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 23 February 2021
Revised: 14 April 2021
Accepted: 25 April 2021
Published: 14 June 2021
Issue date: January 2022

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This research was financially supported by the Priority Research Project of Xiamen (No. 3502Z20191015). J. H. acknowledges the Chinese Academy of Sciences Pioneer "Hundred Talents Program" Young Talents (Class C).

Return