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
1. [1]
  Yixuan Gao , Lingxing Zan , Wenlin Zhang , Qingbo Wei . Comprehensive Innovation Experiment: Preparation and Characterization of Carbon-based Perovskite Solar Cells. University Chemistry, 2024, 39(4): 178-183. doi: 10.3866/PKU.DXHX202311091
2. [2]
  Rui Li , Huan Liu , Yinan Jiao , Shengjian Qin , Jie Meng , Jiayu Song , Rongrong Yan , Hang Su , Hengbin Chen , Zixuan Shang , Jinjin Zhao . 卤化物钙钛矿的单双向离子迁移. Acta Physico-Chimica Sinica, 2024, 40(11): 2311011-. doi: 10.3866/PKU.WHXB202311011
3. [3]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
4. [4]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
5. [5]
  Xin Han , Zhihao Cheng , Jinfeng Zhang , Jie Liu , Cheng Zhong , Wenbin Hu . Design of Amorphous High-Entropy FeCoCrMnBS (Oxy) Hydroxides for Boosting Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2025, 41(4): 100033-. doi: 10.3866/PKU.WHXB202404023
6. [6]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
7. [7]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
8. [8]
  Zeyuan WANG , Songzhi ZHENG , Hao LI , Jingbo WENG , Wei WANG , Yang WANG , Weihai SUN . Effect of I₂ interface modification engineering on the performance of all-inorganic CsPbBr₃ perovskite solar cells. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1290-1300. doi: 10.11862/CJIC.20240021
9. [9]
  Xiaoyao YIN , Wenhao ZHU , Puyao SHI , Zongsheng LI , Yichao WANG , Nengmin ZHU , Yang WANG , Weihai SUN . Fabrication of all-inorganic CsPbBr₃ perovskite solar cells with SnCl₂ interface modification. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 469-479. doi: 10.11862/CJIC.20240309
10. [10]
  Li Jiang , Changzheng Chen , Yang Su , Hao Song , Yanmao Dong , Yan Yuan , Li Li . Electrochemical Synthesis of Polyaniline and Its Anticorrosive Application: Improvement and Innovative Design of the “Chemical Synthesis of Polyaniline” Experiment. University Chemistry, 2024, 39(3): 336-344. doi: 10.3866/PKU.DXHX202309002
11. [11]
  Pengyu Dong , Yue Jiang , Zhengchi Yang , Licheng Liu , Gu Li , Xinyang Wen , Zhen Wang , Xinbo Shi , Guofu Zhou , Jun-Ming Liu , Jinwei Gao . NbSe₂纳米片优化钙钛矿太阳能电池的埋底界面. Acta Physico-Chimica Sinica, 2025, 41(3): 2407025-. doi: 10.3866/PKU.WHXB202407025
12. [12]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-. doi: 10.3866/PKU.WHXB202402006
13. [13]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
14. [14]
  Aoyu Huang , Jun Xu , Yu Huang , Gui Chu , Mao Wang , Lili Wang , Yongqi Sun , Zhen Jiang , Xiaobo Zhu . Tailoring Electrode-Electrolyte Interfaces via a Simple Slurry Additive for Stable High-Voltage Lithium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100037-. doi: 10.3866/PKU.WHXB202408007
15. [15]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
16. [16]
  Yipeng Zhou , Chenxin Ran , Zhongbin Wu . Metacognitive Enhancement in Diversifying Ideological and Political Education within Graduate Course: A Case Study on “Solar Cell Performance Enhancement Technology”. University Chemistry, 2024, 39(6): 151-159. doi: 10.3866/PKU.DXHX202312096
17. [17]
  Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo . 氰基修饰的苝二酰亚胺衍生物作为膜厚不敏感型阴极界面材料用于高效有机太阳能电池. Acta Physico-Chimica Sinica, 2025, 41(3): 2406007-. doi: 10.3866/PKU.WHXB202406007
18. [18]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
19. [19]
  Wei HE , Jing XI , Tianpei HE , Na CHEN , Quan YUAN . Application of solar-driven inorganic semiconductor-microbe hybrids in carbon dioxide fixation and biomanufacturing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 35-44. doi: 10.11862/CJIC.20240364
20. [20]
  Xinxin JING , Weiduo WANG , Hesu MO , Peng TAN , Zhigang CHEN , Zhengying WU , Linbing SUN . Research progress on photothermal materials and their application in solar desalination. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1033-1064. doi: 10.11862/CJIC.20230371

Get Citation

PDF

XML

Metrics

PDF Downloads(16)
Abstract views(806)
HTML views(163)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of Cs-Rich CH(NH2)2)xCs1−xPbI3 Perovskite Films Using Additives with Low Sublimation Temperature

Metrics

通讯作者: 陈斌, bchen63@163.com

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