Skip to main content
SpringerLink
Log in

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

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  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.

    Article  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  Google Scholar 

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

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  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.

    Article  CAS  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.

    Article  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.

    Article  CAS  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.

    Article  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  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.

    Article  CAS  Google Scholar 

Download references

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).

Author information

Authors and Affiliations

  1. CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Dejian Chen, Decai Huang, Mingwei Yang, Kunyuan Xu, Jie Hu, Sisi Liang & Haomiao Zhu

  2. Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare Earth Materials, Haixi Institute, Chinese Academy of Sciences, Xiamen, 361021, China

    Dejian Chen, Decai Huang, Mingwei Yang, Kunyuan Xu, Jie Hu, Sisi Liang & Haomiao Zhu

Authors
  1. Dejian Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Decai Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mingwei Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kunyuan Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jie Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sisi Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Haomiao Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Haomiao Zhu.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

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 Res. 15, 644–652 (2022). https://doi.org/10.1007/s12274-021-3538-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-021-3538-1

Keywords

Search

Navigation