English

Synthesis of Pyrazine-based Hole Transport Layer and Its Application in p-i-n Planar Perovskite Solar Cells

• Xu Guiying ^1, ,
• Xue Rongming ^1, ,
• Zhang Moyao ^1, ,
• Li Yaowen ^{1, ,} ,
• Li Yongfang ^1,2,

• 1.

  Laboratory of Advanced Optoelectronic Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu Province, China

• 2.

  Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Yaowen Li, Email: ywli@suda.edu.cn

• Received Date: 19 August 2020
  Accepted Date: 23 September 2020
  Revised Date: 20 September 2020
  Available Online: 15 April 2021
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (51922074, 51673138, 51820105003), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCPTTPA8_2496)

Abstract: Planar p-i-n perovskite solar cells (pero-SCs) with solution-processed fabrication, low cost, flexible device fabrication, and negligible hysteresis have attracted significant interest. Hole transport material (HTM) plays a crucial role in improving the performance of p-i-n planar pero-SCs by facilitating hole extraction and then reducing surface recombination. Two types of HTMs have been used in p-i-n pero-SCs. p-Type inorganic semiconductors, such as NiO, CuI, Cu₂O, CuSCN, and graphene oxide, have shown good efficiency and stability; however, organic semiconductor-based HTMs (e.g., poly[bis(4-phenyl) (2, 4, 6-trimethylphenyl)amine] (PTAA), polyarylamine (poly-TPD), poly(N-9-heptadecanyl-2, 7-carbazole-alt-5, 5-(4, 7-di(thien-2-yl)-2, 1, 3-benzothiadiazole)) (PCDTBT), and triphenylamine or thiophene derivative) have outstanding processability for simple one-step solution process at low temperatures; therefore, they should be investigated further. However, their electrical properties are usually inferior than those of inorganic semiconductors, and additives are required to improve their mobility and conductivity, which complicates device processing and results in hysteresis and poor device stability. Therefore, for the organic semiconductor-based HTMs, new hole transport layer (HTL) materials should be developed with easy synthesis process, highly reproducible photovoltaic performance, and better understanding of the structure–property relationship between the HTL materials and the device performance. Herein, an X-type HTM 4, 4, 4'', 4'''-(pyrazine-2, 3, 5, 6-tetrayl)tetrakis(N, N-bis(4-methoxyphenyl)aniline) (PT-TPA) containing pyrazine as the molecular core and triphenylamine (TPA) derivative as branches was designed and synthesized. We introduce an electron-deficient para-diazine as the core and electron-donating methoxytriphenylamine as the peripheral unit to enhance the dipole moment of PT-TPA, which could induce an intermolecular charge transfer. Compared with 4, 4'', 4'', 4'''-silanetetrayltetrakis(N, N-bis(4-methoxyphenyl)aniline) (Si-OMeTPA), the pyrazine core not only endows PT-TPA with good crystallinity but also improves the charge transfer property and plane conjugation of the molecular center, which significantly enhances the hole mobility of PT-TPA. The p-i-n planar pero-SCs based on dopant-free PT-TPA HTL showed a power conversion efficiency of 17.52%, which is approximately 15% higher than that of the device with a Si-OMeTPA HTL.

Key words:
• Pyrazine
•  /  Hole-transporting layer
•  /  Organic small molecule
•  /  p-i-n planar perovskite solar cell
•  /  Structure and property relationship

• 1. [1]

     Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050. doi: 10.1021/ja809598r

  2. [2]

     Olaleru, S. A.; Kirui, J. K.; Wamwangi, D.; Roro, K. T.; Mwakikunga, B. Sol. Energy 2020, 196, 295. doi: 10.1016/j.solener.2019.12.025

  3. [3]

     Park, N. G. ACS Energy Lett. 2019, 4, 2983. doi: 10.1021/acsenergylett.9b02442

  4. [4]

     Zheng, X.; Hou, Y.; Bao, C.; Yin, J.; Yuan, F.; Huang, Z.; Song, K.; Liu, J.; Troughton, J.; Gasparini, N.; et al. Nat. Energy 2020, 5, 131. doi: 10.1038/s41560-019-0538-4

  5. [5]

     Yang, D.; Sano, T.; Yaguchi, Y.; Sun, H.; Sasabe, H.; Kido, J. Adv. Funct. Mater. 2019, 29, 1970074. doi: 10.1002/adfm.201970074

  6. [6]

     Xue, R.; Zhang, M.; Luo, D.; Chen, W.; Zhu, R.; Yang, Y. M.; Li, Y.; Li, Y. Sci. China Chem. 2020, doi: 10.1007/s11426-020-9741-1

  7. [7]

     Jia, X.; Zuo, C.; Tao, S.; Sun, K.; Zhao, Y.; Yang, S.; Cheng, M.; Wang, M.; Yuan, Y.; Yang J.; et al. Science Bulletin 2019, 64, 1532. doi: 10.1016/j.scib.2019.08.017

  8. [8]

     Cheng, M.; Zuo, C.; Wu, Y.; Li, Z.; Xu, B.; Hua, Y.; Ding, L. Science Bulletin 2020, 65 (15), 1237. doi: 10.1016/j.scib.2020.04.021

  9. [9]

     Sathiyan, G.; Syed. A. A.; Chen, C.; Wu, C.; Tao, L.; Ding, X.; Miao, Y.; Li, G.; Cheng, M.; Ding L. Nano Energy 2020, 72, 104673. doi: 10.1016/j.nanoen.2020.104673

  10. [10]

      Bi, C.; Wang, Q.; Shao, Y.; Yuan, Y.; Xiao, Z.; Huang, J. Nat. Commun. 2015, 6, 7747. doi: 10.1038/ncomms8747

  11. [11]

      Huang, C.; Fu, W.; Li, C. Z.; Zhang, Z.; Qiu, W.; Shi, M.; Heremans, P.; Jen, A. K. Y.; Chen, H. J. Am. Chem. Soc. 2016, 138, 2528. doi: 10.1021/jacs.6b00039

  12. [12]

      张婧, 何有军, 闵杰.物理化学学报, 2018, 34, 1221. doi: 10.3866/PKU.WHXB201803231Zhang, J.; He, Y.; Min, J. Acta Phys. -Chim. Sin. 2018, 34, 1221. doi: 10.3866/PKU.WHXB201803231

  13. [13]

      Xu, L.; Chen, X.; Jin, J.; Liu, W.; Dong, B.; Bai, X.; Song, H.; Reiss, P. Nano Energy 2019, 63, 103860. doi: 10.1016/j.nanoen.2019.103860

  14. [14]

      Son, M. K.; Steier, L.; Schreier, M.; Mayer, M. T.; Luo, J.; Grätzel, M. Energy Environ. Sci. 2017, 10, 912. doi: 10.1039/C6EE03613A

  15. [15]

      Zhao, D.; Sexton, M.; Park, H. Y.; Baure, G.; Nino, J. C.; So, F. Adv. Energy Mater. 2015, 5, 1401855. doi: 10.1002/aenm.201500436

  16. [16]

      Li, X.; Liu, X.; Wang, X.; Zhao, L.; Jiu, T.; Fang, J. J. Mater. Chem. A 2015, 3, 15024. doi: 10.1039/C5TA04712A

  17. [17]

      Meng, L.; You, J.; Guo, T. F.; Yang, Y. Acc. Chem. Res. 2016, 49, 155. doi: 10.1021/acs.accounts.5b00404

  18. [18]

      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

  19. [19]

      Wang, Y. K.; Yuan, Z. C.; Shi, G. Z.; Li, Y. X.; Li, Q.; Hui, F.; Sun, B. Q.; Jiang, Z.; Liao, L. Adv. Funct. Mater. 2016, 26, 1375. doi: 10.1002/adfm.201504245

  20. [20]

      Labban, A. E.; Chen, H.; Kirkus, M.; Barbe, J.; Del Gobbo, S.; Neophytou, M.; McCulloch, I.; Eid, J. Adv. Energy Mater. 2016, 6, 1502101. doi: 10.1002/aenm.201502101

  21. [21]

      Chen, H.; Fu, W.; Huang, C.; Zhang, Z.; Li, S.; Ding, F.; Shi, M.; Li, C. Z.; Jen, A. K. Y.; Chen, H. Adv. Energy Mater. 2017, 7, 1700012. doi: 10.1002/aenm.201700012

  22. [22]

      Xue, R.; Zhang, M.; Xu, G.; Zhang, J.; Chen, W.; Chen, H.; Yang, M.; Cui, C.; Li, Y.; Li, Y. J. Mater. Chem. A 2018, 6, 404. doi: 10.1039/C7TA09716F

  23. [23]

      Lin, H.; Chen, S.; Hu, H.; Zhang, L.; Ma, T.; Lai, J. Y. L.; Li, Z.; Qin, A.; Huang, X.; Tang, B.; Yan, H. Adv. Mater. 2016, 28, 8546. doi: 10.1002/adma.201600997

  24. [24]

      Liu, Y.; Lai, J. Y. L.; Chen, S.; Li, Y.; Jiang, K.; Zhao, J.; Li, Z.; Hu, H.; Ma, T.; Lin, H.; et al. J. Mater. Chem. A 2015, 3, 13632. doi: 10.1039/C5TA03093E

  25. [25]

      Liu, Y.; Mu, C.; Jiang, K.; Zhao, J.; Li, Y.; Zhang, L.; Li, Z.; Lai, J.; Hu, H.; Ma, T.; et al. Adv. Mater. 2015, 27, 1015. doi: 10.1002/adma.201404152

  26. [26]

      Xu, L.; Zhang, Q. Sci. China Mater. 2017, 60, 1093. doi: 10.1007/s40843-016-5170-2

  27. [27]

      Zhu, Y.; Champion, R.; Jenekhe, S. Macromolecules 2006, 39, 8712. doi: 10.1021/ma061861g

  28. [28]

      Zhou, E.; Cong, J.; Yamakawa, S.; Wei, Q.; Nakamura, M.; Tajima, K.; Yang, C.; Hashimoto, K. Macromolecules 2010, 43, 2873. doi: 10.1021/ma100039q

  29. [29]

      Chen, M.; Nie, H.; Song, B.; Li, L.; Sun, J. Z.; Qin, A.; Tang, B. Z. J. Mater. Chem. C 2016, 4, 2901. doi: 10.1039/C5TC03299G

  30. [30]

      Liu, F.; Wu, F.; Tu, Z.; Liao, Q.; Gong, Y.; Zhu, L.; Li, Q.; Li, Z. Adv. Funct. Mater. 2019, 29, 1901296. doi: 10.1002/adfm.201901296

  31. [31]

      Zhang, D.; Xu, P.; Wu, T.; Ou, Y.; Yang, X.; Sun, A.; Cui, B.; Sun, H.; Hua, Y. J. Mater. Chem. A 2019, 7, 5221. doi: 10.1039/C8TA12139G

  32. [32]

      Hua, Y.; Chen, S.; Zhang, D.; Xu, P.; Sun, A.; Ou, Y.; Wu, T.; Sun, H.; Cui, B.; Zhu, X. J. Mater. Chem. A 2019, 7, 10200. doi: 10.1039/C9TA01731C

  33. [33]

      Zhao, Y.; Xu, G.; Guo, X.; Xia, Y.; Cui, C.; Zhang, M.; Song, B.; Li, Y.; Li, Y. J. Mater. Chem. A 2015, 3, 17991. doi: 10.1039/C5TA03801D

  34. [34]

      Zhang, P.; Li, C.; Li, Y.; Yang, X.; Chen, L.; Xu, B.; Tian, W.; Tu, Y. Chem. Commun. 2013, 49, 4917. doi: 10.1039/C3CC41321G

  35. [35]

      Deepa, M.; Salado, M.; Calio, L.; Kazim, S.; Shivaprasad, S. M.; Ahmad, S. Phys. Chem. Chem. Phys. 2017, 19, 4069. doi: 10.1039/C6CP08022G

  36. [36]

      Saliba, M.; Matsui, T.; Seo, J. Y.; Domanski, K.; Correa-Baena, J. P.; Nazeeruddin, M. K.; Zakeeruddin, S. M.; Tress, W.; Abate, A.; Hagfeldt, A.; Grätzel, M. Energy Environ. Sci. 2016, 9, 1989. doi: 10.1039/C5EE03874J

  37. [37]

      Ge, Q. Q.; Shao, J. Y.; Ding, J.; Deng, L. Y.; Zhou, W. K.; Chen, Y. X.; Ma, J. Y.; Wan, L. J.; Yao, J.; Hu, J. S.; Zhong, Y. W. Angew. Chem. Int. Ed. 2018, 57, 10959. doi: 10.1002/anie.201806392

  38. [38]

      Luo, D.; Yang, W.; Wang, Z.; Sadhanala, A.; Hu, Q.; Su, R.; Shivanna, R.; Trindade, G. F.; Watts, J. F.; Xu, Z.; et al. Science 2018, 360, 1442. doi: 10.1126/science.aap9282

  39. [39]

      Tu, Y.; Yang, X.; Su, R.; Luo, D.; Cao, Y.; Zhao, L.; Liu, T.; Yang, W.; Zhang, Y.; Xu, Z.; et al. Adv. Mater. 2018, 30, 1805085. doi: 10.1002/adma.201805085

  40. [40]

      Li, Y.; Zhao, Y.; Chen, Q.; Yang, Y.; Liu, Y.; Hong, Z.; Liu, Z.; Hsieh, Y. T.; Meng, L.; Li, Y.; Yang, Y. J. Am. Chem. Soc. 2015, 137, 15540. doi: 10.1021/jacs.5b10614

  41. [41]

      Cowan, S. R.; Roy, A.; Heeger, A. J. Phys. Rev. B 2010, 82, 245207. doi: 10.1103/PhysRevB.82.245207

  42. [42]

      Mandoc, M. M.; Kooistra, F. B.; Hummelen, J. C.; Boer, B. d.; Blom, P. W. M. Appl. Phys. Lett. 2007, 91, 263505.doi: 10.1063/1.2821368

  43. [43]

      Liu, X.; Yu, Z.; Wang, T.; Chiu, K.; Lin, F.; Gong, H.; Ding, L.; Cheng, Y. Adv. Energy Mater. 2020, 2001958. doi: 10.1002/aenm.202001958

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