Citation: Ge Yang, Mu Xulin, Lu Yue, Sui Manling. Photoinduced Degradation of Lead Halide Perovskite Thin Films in Air[J]. Acta Physico-Chimica Sinica, ;2020, 36(8): 190503. doi: 10.3866/PKU.WHXB201905039 shu

Photoinduced Degradation of Lead Halide Perovskite Thin Films in Air

Ge Yang ^1,2 ,
Mu Xulin ^1,2 ,
Lu Yue ^1,2,, ,
Sui Manling ^1,2,,

1.
Institute of Microstructure and Property of Advanced Materials, Beijing University of Technology, Beijing 100124, P. R. China
2.
Beijing Key Laboratory of Microstructure and Properties of Solids, Beijing University of Technology, Beijing 100124, P. R. China

Corresponding author: Lu Yue, luyuerr@163.com Sui Manling, mlsui@bjut.edu.cn
Received Date: 8 May 2019
Revised Date: 5 June 2019
Accepted Date: 6 June 2019
Available Online: 14 June 2019
Fund Project: The project was supported by the National Key Research and Development Program of China (2016YFB0700700), the National Natural Science Fund for Innovative Research Groups, China (51621003), the National Natural Science Foundation of China (11704015), the Scientific Research Key Program of Beijing Municipal Commission of Education, China (KZ201310005002), and Beijing Municipal Found for Scientific Innovation, China (PXM2019_014204_500031)Beijing Municipal Found for Scientific Innovation, China PXM2019_014204_500031the National Natural Science Fund for Innovative Research Groups, China 51621003the National Key Research and Development Program of China 2016YFB0700700the National Natural Science Foundation of China 11704015the Scientific Research Key Program of Beijing Municipal Commission of Education, China KZ201310005002

As an excellent photoelectric material, metal halide perovskites have been rapidly developed in the photovoltaic field. The power conversion efficiency of solar cells based on perovskite materials now exceeds 24%, which is close to the conversion efficiency of silicon-based solar cells. However, organic-inorganic hybrid perovskite materials are sensitive to light, oxygen, and moisture, particularly when combined in the ambient environment, limiting their commercial application in perovskite devices due to their poor environmental stability. Therefore, a comprehensive understanding of the degradation mechanism is the key for development of an effective method to inhibit the degradation of perovskite materials. Herein, the photo-induced degradation process of CH₃NH₃PbI₃ films in air was studied by conventional optical and structural characterization methods, including ultraviolet-visible (UV-Vis) absorption spectroscopy, X-ray diffraction (XRD) and advanced transmission electron microscopy (TEM) equipped with a probe spherical aberration corrector. The CH₃NH₃PbI₃ films were first decomposed into hexagonal PbI₂ and amorphous phase, and subsequently oxidized to the amorphous phase under the combined effects of light and oxygen. The molecular formula of the amorphous phase was further confirmed as PbI_2−2xO_x (0.4 < x < 0.6) via X-ray energy dispersive spectroscopy (EDS) and electron energy loss spectroscopy (EELS). Further analysis showed that the film degradation is mainly related to superoxide (O₂^•−) formed by combination of oxygen molecules and photoelectrons in the perovskite film. The organic part of the CH₃NH₃PbI₃ is oxidized by O₂^•− and CH₃NH₃PbI₃ is decomposed to form volatile products, such as CH₃NH₂ and I₂, then degraded into PbI₂, and oxidized to form the amorphous PbI_2−2xO_x. Therefore, during the initial degradation of film under light soaking in air, the degradation sites are mainly located at the interface between CH₃NH₃PbI₃ and air. Many pores were observed on the film surface due to the large loss of volatile decomposition products during the initial degradation. The films then converted to a honeycomb hollow morphology due to the continuous consumption of material under light soaking, reducing the mass of the film as well. Finally, the entire film was oxidized to form an amorphous structure. Herein, for the first time, we report that the formation of amorphous oxides is accompanied by the degradation of perovskite film. This study presents a new understanding of the photo-induced degradation mechanism of perovskite films in air and provides novel theoretical guidance to promote the long-term stability of perovskite solar cells.
- Perovskite film,
- Photo-oxidation degradation,
- Transmission electron microscopy,
- Microstructure evolution,
- Amorphous phase
1. [1]
  De Wolf, S.; Holovsky, J.; Moon, S. J.; Loper, P.; Niesen, B.; Ledinsky, M.; Haug, F. J.; Yum, J. H.; Ballif, C. J. Phys. Chem. Lett. 2014, 5, 1035. doi: 10.1021/jz500279b doi: 10.1021/jz500279b
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]
  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
4. [4]
  Steirer, K. X.; Schulz, P.; Teeter, G.; Stevanovic, V.; Yang, M.; Zhu, K.; Berry, J. J. ACS Energy Lett. 2016, 1, 360. doi: 10.1021/acsenergylett.6b00196 doi: 10.1021/acsenergylett.6b00196
5. [5]
  Jeon, N. J.; Noh, J. H.; Kim, Y. C.; Yang, W. S.; Ryu, S.; Seok, S. I. Nat. Mater. 2014, 13, 897. doi: 10.1038/nmat4014 doi: 10.1038/nmat4014
6. [6]
  Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050. doi: 10.1021/ja809598r doi: 10.1021/ja809598r
7. [7]
  https://www.nrel.gov/pv/assets/pdfs/best-reserch-cell-efficiencies (accessed May 1, 2019).
8. [8]
  Tang, X. F.; Brandl, M.; May, B.; Levchuk, I.; Hou, Y.; Richter, M.; Chen, H. W.; Chen, S.; Kahmann, S.; Osvet, A.; et al. J. Mater. Chem. A 2016, 4, 15896. doi: 10.1039/c6ta06497c doi: 10.1039/c6ta06497c
9. [9]
  Yang, J. L.; Siempelkamp, B. D.; Liu, D. Y.; Kelly, T. L. ACS Nano 2015, 9, 1955. doi: 10.1021/nn506864k doi: 10.1021/nn506864k
10. [10]
  Aristidou, N.; Sanchez-Molina, I.; Chotchuangchutchaval, T.; Brown, M.; Martinez, L.; Rath, T.; Haque, S. A. Angew. Chem. Int. Ed. 2015, 54, 8208. doi: 10.1002/anie.201503153 doi: 10.1002/anie.201503153
11. [11]
  Nie, W.; Tsai, H.; Asadpour, R.; Blancon, J. C.; Neukirch, A. J.; Gupta, G.; Crochet, J. J.; Chhowalla, M.; Tretiak, S.; Alam, M. A.; et al. Science 2015, 347, 522. doi: 10.1126/science.aaa0472 doi: 10.1126/science.aaa0472
12. [12]
  Zhou, Y.; Yang, M.; Vasiliev, A. L.; Garces, H. F.; Zhao, Y.; Wang, D.; Pang, S.; Zhu, K.; Padture, N. P. J. Mater. Chem. A 2015, 3, 9249. doi: 10.1039/c4ta07036d doi: 10.1039/c4ta07036d
13. [13]
  Chen, H. Adv. Funct. Mater. 2017, 27, 1605654. doi: 10.1002/adfm.201605654 doi: 10.1002/adfm.201605654
14. [14]
  Shai, X. X.; Li, D.; Liu, S. S.; Li, H.; Wang, M. K. Acta Phys. -Chim. Sin. 2016, 32, 2159. doi: 10.3866/PKU.WHXB201606072
15. [15]
  Rong, Y.; Hu, Y.; Mei, A.; Tan, H.; Saidaminov, M. I.; Seok, S. I.; McGehee, M. D.; Sargent, E. H.; Han, H. Science 2018, 361, eaat8235. doi: 10.1126/science.aat8235 doi: 10.1126/science.aat8235
16. [16]
  Huang, Y; Sun, Q. D.; Xu, W.; He, Y.; Yin, W. J. Acta Phys. -Chim. Sin. 2017, 33, 1730. doi: 10.3866/PKU.WHXB201705042
17. [17]
  Boyd, C. C.; Cheacharoen, R.; Leijtens, T.; McGehee, M. D. Chem. Rev. 2018, 119, 3418. doi: 10.1021/acs.chemrev.8b00336 doi: 10.1021/acs.chemrev.8b00336
18. [18]
  Sun, Q.; Fassl, P.; Becker-Koch, D.; Bausch, A.; Rivkin, B.; Bai, S.; Hopkinson, P. E.; Snaith, H. J.; Vaynzof, Y. Adv. Energy Mater. 2017, 7, 1700977. doi:10.1002/aenm.201700977 doi: 10.1002/aenm.201700977
19. [19]
  Bryant, D.; Aristidou, N.; Pont, S.; Sanchez-Molina, I.; Chotchunangatchaval, T.; Wheeler, S.; Durrant, J. R.; Haque, S. A. Energy Environ. Sci. 2016, 9, 1655. doi: 10.1039/c6ee00409a doi: 10.1039/c6ee00409a
20. [20]
  Aristidou, N.; Eames, C.; Sanchez-Molina, I.; Bu, X.; Kosco, J.; Islam, M. S.; Haque, S. A. Nat. Commun. 2017, 8, 15218. doi: 10.1038/ncomms15218 doi: 10.1038/ncomms15218
21. [21]
  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
22. [22]
  Wu, Y.; Islam, A.; Yang, X.; Qin, C.; Liu, J.; Zhang, K.; Peng, W.; Han, L. Energy Environ. Sci. 2014, 7, 2934. doi: 10.1039/c4ee01624f doi: 10.1039/c4ee01624f
23. [23]
  Ouyang, Y.; Shi, L.; Li, Q.; Wang, J. Small Methods 2019, 1900154. doi: 10.1002/smtd.201900154 doi: 10.1002/smtd.201900154
24. [24]
  Li, Y.; Zhao, Z.; Lin, F.; Cao, X.; Cui, X.; Wei, J. Small 2017, 13, 1604125. doi:10.1002/smll.201604125 doi: 10.1002/smll.201604125
25. [25]
  Rothmann, M. U.; Li, W.; Zhu, Y.; Liu, A.; Ku, Z. L.; Bach, U.; Etheridge, J.; Cheng, Y. B. Adv. Mater. 2018, 30, 1802769. doi: 10.1002/adma.201802769 doi: 10.1002/adma.201802769
26. [26]
  Pennycook, S. J.; Nellist, P. D. Z-Contrast Scanning Transmission Electron Microscopy. In Impact of Electron and Scanning Probe Microscopy on Materials Research; Rickerby, D. G., Valdrè, G., Valdrè, U., Eds.; Springer Netherlands: Dordrecht, The Netherlangds, 1999; pp. 161–207.
27. [27]
  Jung, H. J.; Kim, D.; Kim, S.; Park, J.; Dravid, V. P.; Shin, B. Adv. Mater. 2018, 30, e1802769. doi: 10.1002/adma.201802769 doi: 10.1002/adma.201802769
1. [1]
  Xinyuan Shi , Chenyangjiang , Changyu Zhai , Xuemei Lu , Jia Li , Zhu Mao . Preparation and Photoelectric Performance Characterization of Perovskite CsPbBr₃ Thin Films. University Chemistry, 2024, 39(6): 383-389. doi: 10.3866/PKU.DXHX202312019
2. [2]
  Yingqi BAI , Hua ZHAO , Huipeng LI , Xinran REN , Jun LI . Perovskite LaCoO₃/g-C₃N₄ heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 480-490. doi: 10.11862/CJIC.20240259
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  Yao Ma , Xin Zhao , Hongxu Chen , Wei Wei , Liang Shen . Progress and Perspective of Perovskite Thin Single Crystal Photodetectors. Acta Physico-Chimica Sinica, 2025, 41(4): 100030-. doi: 10.3866/PKU.WHXB202309045
7. [7]
  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
8. [8]
  Lin Song , Dourong Wang , Biao Zhang . Innovative Experimental Design and Research on Preparing Flexible Perovskite Fluorescent Gels Using 3D Printing. University Chemistry, 2024, 39(7): 337-344. doi: 10.3866/PKU.DXHX202310107
9. [9]
  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
10. [10]
  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
11. [11]
  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
12. [12]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
13. [13]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
14. [14]
  Zizheng LU , Wanyi SU , Qin SHI , Honghui PAN , Chuanqi ZHAO , Chengfeng HUANG , Jinguo PENG . Surface state behavior of W doped BiVO₄ photoanode for ciprofloxacin degradation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 591-600. doi: 10.11862/CJIC.20230225
15. [15]
  Yinyin Qian , Rui Xu . Utilizing VESTA Software in the Context of Material Chemistry: Analyzing Twin Crystal Nanostructures in Indium Antimonide. University Chemistry, 2024, 39(3): 103-107. doi: 10.3866/PKU.DXHX202307051
16. [16]
  Yujia LI , Tianyu WANG , Fuxue WANG , Chongchen WANG . Direct Z-scheme MIL-100(Fe)/BiOBr heterojunctions: Construction and photo-Fenton degradation for sulfamethoxazole. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 481-495. doi: 10.11862/CJIC.20230314
17. [17]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
18. [18]
  Jiaxin Su , Jiaqi Zhang , Shuming Chai , Yankun Wang , Sibo Wang , Yuanxing Fang . Optimizing Poly(heptazine imide) Photoanodes Using Binary Molten Salt Synthesis for Water Oxidation Reaction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408012-. doi: 10.3866/PKU.WHXB202408012
19. [19]
  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
20. [20]
  Yuan GAO , Yiming LIU , Chunhui WANG , Zhe HAN , Chaoyue FAN , Jie QIU . A hexanuclear cerium oxo cluster stabilized by furoate: Synthesis, structure, and remarkable ability to scavenge hydroxyl radicals. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 491-498. doi: 10.11862/CJIC.20240271

Get Citation

PDF

XML

Metrics

PDF Downloads(20)
Abstract views(1767)
HTML views(486)

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