Citation: Lü Peiliang, Gao Caiyun, Sun Xiuhong, Sun Mingliang, Shao Zhipeng, Pang Shuping. Synthesis of Cs-Rich CH(NH₂)₂)_xCs_1−xPbI₃ Perovskite Films Using Additives with Low Sublimation Temperature[J]. Acta Physico-Chimica Sinica, ;2021, 37(4): 200903. doi: 10.3866/PKU.WHXB202009036 shu

Synthesis of Cs-Rich CH(NH₂)₂)_xCs_1−xPbI₃ Perovskite Films Using Additives with Low Sublimation Temperature

Lü Peiliang ^1,2 ,
Gao Caiyun ^1,2 ,
Sun Xiuhong ² ,
Sun Mingliang ^1,, ,
Shao Zhipeng ^2,, ,
Pang Shuping ^2,,

1.
School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, Shandong Province, China
2.
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong Province, China

Corresponding author: Sun Mingliang, mlsun@ouc.edu.cn Shao Zhipeng, shaozp@qibebt.ac.cn Pang Shuping, pangsp@qibebt.ac.cn
Received Date: 9 September 2020
Revised Date: 24 October 2020
Accepted Date: 26 October 2020
Available Online: 2 November 2020
Fund Project: The project was supported by the Young Taishan Scholars (tsqn201812110) and the National Natural Science Foundation of China (51822209, 51902324)the Young Taishan Scholars tsqn201812110the National Natural Science Foundation of China 51822209the National Natural Science Foundation of China 51902324

Chemical components of perovskite layers play a key role in improving the efficiency and stability of perovskite solar cells. Pure inorganic perovskites exhibit good thermal and light stabilities; however, the smaller radius of Cs⁺ leads to a poor perovskite phase stability. In this case, the Cs-rich (CH(NH₂)₂)_xCs_1−xPbI₃ ((CH(NH₂)₂⁺=FA⁺) perovskite seems more promising because it simultaneously offers the above-mentioned properties, while not forming an unstable perovskite phase. Thus far, the synthesis of Cs-rich FA_xCs_1−xPbI₃ perovskite has been realized by introducing excess formamidinium iodide (FAI) as an additive. However, FAI sublimates at a high temperature and excessive FAI sublimation necessitates even greater temperatures. Therefore, it is difficult to precisely control the ratio of the sublimated FAI from the perovskite film. Herein, the precise synthesis of Cs-rich FA_xCs_1−xPbI₃ perovskites at relatively low sublimation temperatures using amine additives, such as methylammonium iodide (MAI), dimethylamine iodide (DMAI), ethylamine iodide (EAI), ammonium iodide (NH₄I), and formamidine acetate (FAAC), was studied. The reaction temperature was reduced when utilizing these additives. Moreover, the window period for the preparation has been widened, which is particularly important for the preparation of pure phase Cs-rich FA_xCs_1−xPbI₃ perovskite films for large devices. In the experiment, perovskite FA_0.15Cs_0.85PbI₃ was selected because of its good stability. The reaction process of the additive that assisted perovskite preparation was studied. Firstly, 0.85 mmol of MAI, DMAI, EAI, FAAC, and NH₄I each were added to 1 mmol of FA_0.15Cs_0.85PbI₃ solution. Then, the precursor solution was spin-coated and thermally annealed. The FA_0.15Cs_0.85PbI₃ films were formed by sublimation of the additives during thermal annealing. The influence of different additives on the film formation process was traced using X-ray diffraction (XRD) measurements and UV-visible absorbance spectra (UV-Vis abs). The results showed that MAI and DMAI could be used as additives in the preparation of FA_0.15Cs_0.85PbI₃ films. The strong intermolecular interaction between these additives and PbI₂ could benefit the formation of Cs₄PbI₆ and prevent the formation of δ-CsPbI₃. Cs⁺ is easier to migrate in Cs₄PbI₆ than in δ-CsPbI₃, which provides a necessary condition for the ion exchange reaction. Simultaneously, the mild sublimation temperature of the additives ensured that the films maintain their perovskite phase. Finally, pure phase Cs-rich FA_xCs_1−xPbI₃ perovskites were prepared using this method at a relatively lower temperature of 200 ℃. The XRD and UV-Vis absorption results confirmed the precise synthesis of FA_0.15Cs_0.85PbI₃. The FA_0.15Cs_0.85 PbI₃ solar cells synthesized with MAI and DMAI achieved the maximum power conversion efficiencies of 15.6% and 15.1%, respectively.
- Inorganic halide perovskite,
- Formamidine,
- Doping,
- Additive,
- Solar cell
1. [1]
  Lee, M. M.; Teuscher, J.; Miyasaka, T.; Murakami, T. N.; Snaith, H. J. Science 2012, 338, 643. doi: 10.1126/science.1228604 doi: 10.1126/science.1228604
2. [2]
  Stranks, S. D.; Eperon, G. E.; Grancini, G.; Menelaou, C.; Alcocer, M. J.; Leijtens, T.; Herz, L. M.; Petrozza, A.; Snaith, H. J. Science 2013, 342, 341. doi: 10.1126/science.1243982 doi: 10.1126/science.1243982
3. [3]
  Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050. doi: 10.1021/ja809598r doi: 10.1021/ja809598r
4. [4]
  NREL Research Cell Record Efficiency Chart NREL, 2019.
5. [5]
  Wehrenfennig, C.; Eperon, G. E.; Johnston, M. B.; Snaith, H. J.; Herz, L. M. Adv. Mater. 2014, 26, 1584. doi: 10.1002/adma.201305172 doi: 10.1002/adma.201305172
6. [6]
  Huang, Y.; Sun, Q. D.; Xu, W.; He, Y.; Yin, W. J. Acta Phys. -Chim. Sin. 2017, 33, 1730. doi: 10.3866/PKU.WHXB201705042
7. [7]
  Yang, W. S.; Park, B. W.; Jung, E. H.; Jeon, N. J.; Kim, Y. C.; Lee, D. U.; Shin, S. S.; Seo, J.; Kim, E. K.; Noh, J. H.; Seok, S. I. Science 2017, 356, 1376. doi: 10.1126/science.aan2301 doi: 10.1126/science.aan2301
8. [8]
  Jung, E. H.; Jeon, N. J.; Park, E. Y.; Moon, C. S.; Shin. T. J.; Yang, T. Y.; Noh, J. H.; Seo, J. Nature 2019, 567, 511. doi: 10.1038/s41586-019-1036-3 doi: 10.1038/s41586-019-1036-3
9. [9]
  Wang, J.; Zhang, J.; Zhou, Y.; Liu, H.; Xue, Q.; Li, X.; Chueh, C. C.; Yip, H. L.; Zhu, Z.; Jen, A. K. Y. Nat. Commun. 2020, 11, 177. doi: 10.1038/s41467-019-13909-5 doi: 10.1038/s41467-019-13909-5
10. [10]
  Jena, A. K.; Kulkarni, A.; Miyasaka, T. Chem. Rev. 2019, 119, 3036. doi: 10.1021/acs.chemrev.8b00539 doi: 10.1021/acs.chemrev.8b00539
11. [11]
  Zhou, W.; Zhao, Y.; Zhou, X.; Fu, R.; Li, Q.; Zhao, Y.; Liu, K.; Yu, D.; Zhao, Q. J. Phys. Chem. Lett. 2017, 8, 4122. doi: 10.1021/acs.jpclett.7b01851 doi: 10.1021/acs.jpclett.7b01851
12. [12]
  Binek, A.; Hanusch, F. C.; Docampo, P.; Bein, T. J. Phys. Chem. Lett. 2015, 6, 1249. doi: 10.1021/acs.jpclett.5b00380 doi: 10.1021/acs.jpclett.5b00380
13. [13]
  Chen, W.; Zhang, J.; Xu, G.; Xue, R.; Li, Y.; Zhou, Y.; Hou, J.; Li, Y. Adv. Mater. 2018, 30, e1800855. doi: 10.1002/adma.201800855 doi: 10.1002/adma.201800855
14. [14]
  Liang, J.; Zhao, P, ; Wang, C.; Wang, Y.; Hu, Y.; Zhu, G.; Ma, L.; Liu, J.; Jin, Z. J. Am. Chem. Soc. 2017, 139, 14009. doi: 10.1021/jacs.7b07949.5156 doi: 10.1021/jacs.7b07949.5156
15. [15]
  Saparov, B.; Mitzi, D, B. Chem. Rev. 2016, 116, 4558. doi: 10.1021/acs.chemrev.5b00715.516 doi: 10.1021/acs.chemrev.5b00715.516
16. [16]
  Wei, D.; Ma, F.; Wang, R.; Dou, S.; Cui, P.; Huang, H.; Ji, J.; Jia, E.; Jia, X.; Sajid, S.; et al. Adv. Mater. 2018, 30, e1707583. doi: 10.1002/adma.201707583.315 doi: 10.1002/adma.201707583.315
17. [17]
  Stoumpos, C. C.; Malliakas, C. D.; Kanatzidis, M. G. Inorg. Chem. 2013, 52, 9019. doi: 10.1021/ic401215x doi: 10.1021/ic401215x
18. [18]
  Jing, C. Q.; Wu, J. H, ; Cao, Y. Y.; Che, H. X.; Zhao, X. M.; Yue, M.; Liao, Y. Y.; Yue, C. Y.; Lei, X. W. Chem. Commun. 2020, 56, 5925. doi: 10.1039/d0cc01779e doi: 10.1039/d0cc01779e
19. [19]
  De Marco, N.; Zhou, H.; Chen, Q.; Sun, P.; Liu, Z.; Meng, L.; Yao, E. P.; Liu, Y.; Schiffer, A.; Yang, Y. Nano Lett. 2016, 16, 1009. doi: 10.1021/acs.nanolett.5b04060 doi: 10.1021/acs.nanolett.5b04060
20. [20]
  Saliba, M.; Correa-Baena, J. P.; Grätzel, M.; Hagfeldt, A.; Abate, A. Angew. Chem. Int. Ed. 2018, 57, 2554. doi: 10.1002/anie.201703226.151 doi: 10.1002/anie.201703226.151
21. [21]
  Marronnier, A.; Roma, G.; Boyer-Richard, S.; Pedesseau, L.; Jancu, J. M.; Bonnassieux, Y.; Katan, C.; Stoumpos, C. C.; Kanatzidis, M. G.; Even, J. ACS Nano 2018, 12, 3477. doi: 10.1021/acsnano.8b00267.1651 doi: 10.1021/acsnano.8b00267.1651
22. [22]
  Ke, W.; Spanopoulos, I.; Stoumpos, C. C.; Kanatzidis, M. G. Nat. Commun. 2018, 9, 4785.doi: 10.1038/s41467-018-07204-y.5151 doi: 10.1038/s41467-018-07204-y.5151
23. [23]
  Zhang, J.; Yang, L.; Zhong, Y.; Hao, H.; Yang, M.; Liu, R. Phys. Chem. Chem. Phys. 2019, 21, 11175. doi: 10.1039/c9cp01211g doi: 10.1039/c9cp01211g
24. [24]
  Pang, S.; Hu, H.; Zhang, J.; Lv, S.; Yu, Y.; Wei, F.; Qin, T.; Xu, H.; Liu, Z.; Cui, G. Chem. Mater. 2014, 26, 1485. doi: 10.1021/cm404006p doi: 10.1021/cm404006p
25. [25]
  Luo, P.; Zhou, S.; Zhou, Y.; Xia, W.; Sun, L.; Cheng, J.; Xu, C.; Lu, Y. ACS Appl. Mater. Interfaces. 2017, 9, 42708. doi: 10.1021/acsami.7b12939.3 doi: 10.1021/acsami.7b12939.3
26. [26]
  Luo, P.; Xia, W.; Zhou, S.; Sun, L.; Cheng, J.; Xu, C.; Lu, Y. J. Phys. Chem. Lett. 2016, 7, 3603. doi: 10.1021/acs.jpclett.6b01576.2 doi: 10.1021/acs.jpclett.6b01576.2
27. [27]
  Shao, Z.; Meng, H.; Du, X.; Sun, X.; Lv, P.; Gao, C.; Rao, Y.; Chen, C.; Li, Z.; Wang, X.; Cui, G.; Pang, S. Adv. Mater. 2020, e2001054. doi: 10.1002/adma.202001054 doi: 10.1002/adma.202001054
28. [28]
  Li, Z.; Wang, L.; Liu, R.; Fan, Y.; Meng, H.; Shao, Z.; Cui, G.; Pang, S. Adv. Energy Mater. 2019, 9, 1902142. doi: 10.1002/aenm.201902142 doi: 10.1002/aenm.201902142
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Synthesis of Cs-Rich CH(NH2)2)xCs1−xPbI3 Perovskite Films Using Additives with Low Sublimation Temperature

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Synthesis of Cs-Rich CH(NH₂)₂)_xCs_1−xPbI₃ Perovskite Films Using Additives with Low Sublimation Temperature