Skip to main content
SpringerLink
Log in

Reconstructing the amorphous and defective surface for efficient and stable perovskite solar cells

高效稳定钙钛矿太阳能电池中非晶和缺陷表面的重构

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

The surfaces of perovskite solar cells (PSCs) are significant in determining the devices’ efficiencies and stabilities. Here, we first uncover that the 4-tert-butylpyridine (tBP), as an essential additive in hole transport layers (HTLs), could recrystallize the amorphous and defective perovskite surface layers and passivate the defective sites on grain surfaces. The reconstruction induces a larger surface work function and mitigates the interface energy level misalignment between perovskite and HTLs, enlarging the photovoltage of the device. Then, we engineer the chemical bonding strength and develop a more effective HTL additive 4-tert-butylpiperidine (tBPp), which possesses a stronger interaction with perovskite surface defective sites than tBP. With the enhanced adsorption, the tBPp-reconstructed perovskite surface exhibits lower densities of defects and better stability under the stimuli of heat, light and humidity. As a result, the optimized tBPp PSC reaches a champion efficiency of 24.2% with much better operation stability. Tracked at the maximum power point under a continuous bias, the unsealed devices in a N2 atmosphere can nearly maintain their initial efficiency after continuous light exposure for over 1200 h. Our findings provide an underlying understanding of the HTL additives, which markedly affect the efficiency and stability of n-i-p PSCs.

摘要

钙钛矿太阳能电池的表界面性质是影响器件效率和稳定性的关键因素. 本文中, 我们首次发现空穴传输层中的添加剂4-叔丁基吡啶(tBP)可将钙钛矿非晶态和缺陷表面层进行重结晶, 并且钝化晶粒表面的缺陷位. 该重构可使钙钛矿的表面功函数增大, 降低了钙钛矿与空穴传输层之间界面能级失配, 提高了器件的光电压. 进一步地, 我们通过化学键合强度计, 开发了更有效的空穴传输层添加剂4-叔丁基哌啶(tBPp), 它比tBP具有钙钛矿表面缺陷位点更强的相互作用. 得益于吸附能的增强, 经tBPp重构钙钛矿表面缺陷态密度降低, 且在热、光、湿度的作用下稳定性更好. 基tBPp作为添加剂的钙钛矿电池最高效率达到了24.2%. 在氮气气氛中进最大功率点跟踪测试, 未封装的设备在连续光照超过1200小时后几乎可以保持其初始效率. 本工作全面揭示了空穴传输层中添加剂对于钙钛矿池的效率和稳定性的重要性, 并提供了系统和基础性理解.

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.

Institutional subscriptions

Similar content being viewed by others

References

  1. Lee MM, Teuscher J, Miyasaka T, et al. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science, 2012, 338: 643–647

    Article  CAS  Google Scholar 

  2. Kim HS, Lee CR, Im JH, et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci Rep, 2012, 2: 591

    Article  Google Scholar 

  3. Jeong M, Choi IW, Go EM, et al. Stable perovskite solar cells with efficiency exceeding 24.8% and 0.3-V voltage loss. Science, 2020, 369: 1615–1620

    Article  CAS  Google Scholar 

  4. Yoo JJ, Seo G, Chua MR, et al. Efficient perovskite solar cells via improved carrier management. Nature, 2021, 590: 587–593

    Article  CAS  Google Scholar 

  5. Min H, Lee DY, Kim J, et al. Perovskite solar cells with atomically coherent interlayers on SnO2 electrodes. Nature, 2021, 598: 444–450

    Article  CAS  Google Scholar 

  6. Hui W, Chao L, Lu H, et al. Stabilizing black-phase formamidinium perovskite formation at room temperature and high humidity. Science, 2021, 371: 1359–1364

    Article  CAS  Google Scholar 

  7. Li N, Niu X, Li L, et al. Liquid medium annealing for fabricating durable perovskite solar cells with improved reproducibility. Science, 2021, 373: 561–567

    Article  CAS  Google Scholar 

  8. Kim M, Jeong J, Lu H, et al. Conformal quantum dot-SnO2 layers as electron transporters for efficient perovskite solar cells. Science, 2022, 375: 302–306

    Article  CAS  Google Scholar 

  9. Habisreutinger SN, Noel NK, Snaith HJ, et al. Investigating the role of 4-tert butylpyridine in perovskite solar cells. Adv Energy Mater, 2017, 7: 1601079

    Article  Google Scholar 

  10. Wang S, Huang Z, Wang X, et al. Unveiling the role of tBP-LiTFSI complexes in perovskite solar cells. J Am Chem Soc, 2018, 140: 16720–16730

    Article  CAS  Google Scholar 

  11. Juarez-Perez EJ, Leyden MR, Wang S, et al. Role of the dopants on the morphological and transport properties of spiro-MeOTAD hole transport layer. Chem Mater, 2016, 28: 5702–5709

    Article  CAS  Google Scholar 

  12. Wang S, Sina M, Parikh P, et al. Role of 4-tert-butylpyridine as a hole transport layer morphological controller in perovskite solar cells. Nano Lett, 2016, 16: 5594–5600

    Article  CAS  Google Scholar 

  13. Namatame M, Yabusaki M, Watanabe T, et al. Direct observation of dramatically enhanced hole formation in a perovskite-solar-cell material spiro-OMeTAD by Li-TFSI doping. Appl Phys Lett, 2017, 110: 123904

    Article  Google Scholar 

  14. Lamberti F, Gatti T, Cescon E, et al. Evidence of spiro-OMeTAD de-doping by tert-butylpyridine additive in hole-transporting layers for perovskite solar cells. Chem, 2019, 5: 1806–1817

    Article  CAS  Google Scholar 

  15. Yue Y, Salim NT, Wu Y, et al. Enhanced stability of perovskite solar cells through corrosion-free pyridine derivatives in hole-transporting materials. Adv Mater, 2016, 28: 10738–10743

    Article  CAS  Google Scholar 

  16. Zhang J, Zhang T, Jiang L, et al. 4-tert-Butylpyridine free hole transport materials for efficient perovskite solar cells: A new strategy to enhance the environmental and thermal stability. ACS Energy Lett, 2018, 3: 1677–1682

    Article  CAS  Google Scholar 

  17. Ezike SC, Alabi AB, Ossai AN, et al. Stability-improved perovskite solar cells through 4-tertbutylpyridine surface-passivated perovskite layer fabricated in ambient air. Optical Mater, 2021, 112: 110753

    Article  CAS  Google Scholar 

  18. Liu C, Ding W, Zhou X, et al. Efficient and stable perovskite solar cells prepared in ambient air based on surface-modified perovskite layer. J Phys Chem C, 2017, 121: 6546–6553

    Article  CAS  Google Scholar 

  19. Wu YH, Shi XQ, Ding XH, et al. Incorporating 4-tert-butylpyridine in an antisolvent: A facile approach to obtain highly efficient and stable perovskite solar cells. ACS Appl Mater Interfaces, 2018, 10: 3602–3608

    Article  CAS  Google Scholar 

  20. Shi Y, Wang X, Zhang H, et al. Effects of 4-tert-butylpyridine on perovskite formation and performance of solution-processed perovskite solar cells. J Mater Chem A, 2015, 3: 22191–22198

    Article  CAS  Google Scholar 

  21. Zheng X, Chen B, Dai J, et al. Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations. Nat Energy, 2017, 2: 17102

    Article  CAS  Google Scholar 

  22. Chen S, Liu Y, Xiao X, et al. Identifying the soft nature of defective perovskite surface layer and its removal using a facile mechanical approach. Joule, 2020, 4: 2661–2674

    Article  CAS  Google Scholar 

  23. Xie J, Yan K, Zhu H, et al. Identifying the functional groups effect on passivating perovskite solar cells. Sci Bull, 2020, 65: 1726–1734

    Article  CAS  Google Scholar 

  24. Wang R, Xue J, Wang KL, et al. Constructive molecular configurations for surface-defect passivation of perovskite photovoltaics. Science, 2019, 366: 1509–1513

    Article  CAS  Google Scholar 

  25. Liu Z, Liu F, Duan C, et al. Polymerization stabilized black-phase FAPbI3 perovskite solar cells retain 100% of initial efficiency over 100 days. Chem Eng J, 2021, 419: 129482

    Article  CAS  Google Scholar 

  26. Ma Z, Yu R, Xu Z, et al. Crosslinkable and chelatable organic ligand enables interfaces and grains collaborative passivation for efficient and stable perovskite solar cells. Small, 2022, 18: 2201820

    Article  CAS  Google Scholar 

  27. Jung EH, Jeon NJ, Park EY, et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature, 2019, 567: 511–515

    Article  CAS  Google Scholar 

  28. Yoo JJ, Wieghold S, Sponseller MC, et al. An interface stabilized perovskite solar cell with high stabilized efficiency and low voltage loss. Energy Environ Sci, 2019, 12: 2192–2199

    Article  CAS  Google Scholar 

  29. Jang YW, Lee S, Yeom KM, et al. Intact 2D/3D halide junction perovskite solar cells via solid-phase in-plane growth. Nat Energy, 2021, 6: 63–71

    Article  CAS  Google Scholar 

  30. Zhao S, Qin M, Wang H, et al. Cascade type-II 2D/3D perovskite heterojunctions for enhanced stability and photovoltaic efficiency. Sol RRL, 2020, 4: 2000282

    Article  CAS  Google Scholar 

  31. Zhang J, Bai D, Jin Z, et al. 3D-2D-0D interface profiling for record efficiency all-inorganic CsPbBrI2 perovskite solar cells with superior stability. Adv Energy Mater, 2018, 8: 1703246

    Article  Google Scholar 

  32. Azmi R, Ugur E, Seitkhan A, et al. Damp heat-stable perovskite solar cells with tailored-dimensionality 2D/3D heterojunctions. Science, 2022, 376: 73–77

    Article  CAS  Google Scholar 

  33. Abdi-Jalebi M, Andaji-Garmaroudi Z, Cacovich S, et al. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation. Nature, 2018, 555: 497–501

    Article  CAS  Google Scholar 

  34. Wu WQ, Rudd PN, Ni Z, et al. Reducing surface halide deficiency for efficient and stable iodide-based perovskite solar cells. J Am Chem Soc, 2020, 142: 3989–3996

    Article  CAS  Google Scholar 

  35. Tan S, Huang T, Yavuz I, et al. Stability-limiting heterointerfaces of perovskite photovoltaics. Nature, 2022, 605: 268–273

    Article  CAS  Google Scholar 

  36. Li C, Li H, Zhu Z, et al. Perovskite passivation strategies for efficient and stable solar cells. Sol RRL, 2021, 5: 2000579

    Article  CAS  Google Scholar 

  37. Back H, Kim G, Kim H, et al. Highly stable inverted methylammonium lead tri-iodide perovskite solar cells achieved by surface re-crystallization. Energy Environ Sci, 2020, 13: 840–847

    Article  CAS  Google Scholar 

  38. Kong W, Zhao C, Xing J, et al. Enhancing perovskite solar cell performance through femtosecond laser polishing. Sol RRL, 2020, 4: 2000189

    Article  CAS  Google Scholar 

  39. Yadavalli SK, Chen M, Hu M, et al. Electron-beam-induced cracking in organic-inorganic halide perovskite thin films. Scripta Mater, 2020, 187: 88–92

    Article  CAS  Google Scholar 

  40. Kaneko R, Kanda H, Shibayama N, et al. Gradient 1D/3D perovskite bilayer using 4-tert-butylpyridinium cation for efficient and stable perovskite solar cells. Sol RRL, 2021, 5: 2000791

    Article  CAS  Google Scholar 

  41. Sun K, Hu Z, Shen B, et al. Lewis acid-base interaction-induced porous PbI2 film for efficient planar perovskite solar cells. ACS Appl Energy Mater, 2018, 1: 2114–2122

    Article  CAS  Google Scholar 

  42. Dong G, Ha J, Yang Y, et al. 4-tert Butylpyridine induced MAPBI3 film quality enhancement for improving the photovoltaic performance of perovskite solar cells with two-step deposition route. Appl Surf Sci, 2019, 484: 637–645

    Article  CAS  Google Scholar 

  43. Zhang H, Cheng J, Li D, et al. Toward all room-temperature, solution-processed, high-performance planar perovskite solar cells: A new scheme of pyridine-promoted perovskite formation. Adv Mater, 2017, 29: 1604695

    Article  Google Scholar 

  44. Lin Y, Bai Y, Fang Y, et al. Enhanced thermal stability in perovskite solar cells by assembling 2D/3D stacking structures. J Phys Chem Lett, 2018, 9: 654–658

    Article  CAS  Google Scholar 

  45. Zhao S, Xie J, Cheng G, et al. General nondestructive passivation by 4-fluoroaniline for perovskite solar cells with improved performance and stability. Small, 2018, 14: 1803350

    Article  Google Scholar 

  46. Adinolfi V, Yuan M, Comin R, et al. The in-gap electronic state spectrum of methylammonium lead iodide single-crystal perovskites. Adv Mater, 2016, 28: 3406–3410

    Article  CAS  Google Scholar 

  47. Zu F, Amsalem P, Ralaiarisoa M, et al. Surface state density determines the energy level alignment at hybrid perovskite/electron acceptors interfaces. ACS Appl Mater Interfaces, 2017, 9: 41546–41552

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22005354 and 62025403), Guangdong Basic and Applied Basic Research Foundation (2019A1515110905), and Shenzhen Fundamental Research Program (JCYJ20200109142425294). This work was in part supported by funds from Guangdong Science and Technology Program (2019ZT08L075 and 2019QN01L118). Also, it was in part supported by the Innovation and Technology Commission of Hong Kong SAR(ITS/390/18).

Author information

Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials, Shenzhen Campus of Sun Yat-sen University, Shenzhen, 518107, China

    Jiangsheng Xie  (谢江生), Tian Chen  (陈甜), Bin Wen  (温彬), Qixin Yin  (尹奇欣), Shichen Wei  (韦世宸), Shengcai Zhu  (朱升财) & Pingqi Gao  (高平奇)

  2. Institute for Solar Energy Systems, Guangdong Provincial Key Laboratory of Photovoltaic Technology, State Key Laboratory of Optoelectronic Materials and Technologies, Sun Yat-sen University, Guangzhou, 510275, China

    Jiangsheng Xie  (谢江生), Tian Chen  (陈甜), Bin Wen  (温彬), Qixin Yin  (尹奇欣) & Pingqi Gao  (高平奇)

  3. Department of Electronic Engineering, The Chinese University of Hong Kong, Hong Kong, 999077, China

    Jiangsheng Xie  (谢江生), Shenghe Zhao  (赵生合), Keyou Yan  (严克友) & Jianbin Xu  (许建斌)

  4. State Key Laboratory of Silicon Materials and School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China

    Pengjie Hang  (杭鹏杰) & Xuegong Yu  (余学功)

  5. School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, and National Engineering Laboratory for VOCs Pollution Control Technology and Equipment, South China University of Technology, Guangzhou, 510006, China

    Keyou Yan  (严克友)

  6. Department of Physics, The Chinese University of Hong Kong, Hong Kong, 999077, China

    Minchao Qin  (秦敏超) & Xinhui Lu  (路新慧)

Authors
  1. Jiangsheng Xie  (谢江生)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Shenghe Zhao  (赵生合)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pengjie Hang  (杭鹏杰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tian Chen  (陈甜)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bin Wen  (温彬)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qixin Yin  (尹奇欣)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Shichen Wei  (韦世宸)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Shengcai Zhu  (朱升财)
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Xuegong Yu  (余学功)
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Minchao Qin  (秦敏超)
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Xinhui Lu  (路新慧)
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Keyou Yan  (严克友)
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Jianbin Xu  (许建斌)
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Pingqi Gao  (高平奇)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Xie J conceived the idea and wrote the manuscript. Yan K, Xu J and Gao P supervised the work and revised the manuscript. Zhao S synthesized and characterized the 1D crystals. Xie J and Zhao S prepared the devices and performed the XRD, SEM, UPS, PL and Mott-Schottky analysis. Chen T and Wen B helped measure the PL and XRD. Xie J and Hang P fabricated and characterized most of the perovskite solar cells. Yin Q, Wei S and Zhu S performed the DFT calculation. Hang P estimated the long-term thermal stability of the devices. Qin M and Lu X carried out the GIWAXS measurement. All authors discussed the results.

Corresponding authors

Correspondence to Jiangsheng Xie  (谢江生), Keyou Yan  (严克友), Jianbin Xu  (许建斌) or Pingqi Gao  (高平奇).

Additional information

Supplementary information

Supporting data are available in the online version of the paper.

Jiangsheng Xie is an associate professor at the School of Materials, Sun Yat-sen University, China. He got his PhD degree from Zhejiang University in 2017. He joined the Chinese University of Hong Kong and did postdoctoral research at the Department of Electronic Engineering and Department of Physics. In November 2019, he joined Sun Yat-sen University as an associate professor. His research interests include perovskite materials and photovoltaic devices.

Shenghe Zhao received a PhD degree in 2020 from the Chinese University of Hong Kong. Now, he is a postdoc at the Department of Electronic Engineering, the Chinese University of Hong Kong. His research interests mainly focus on perovskite solar cells and perovskite light-emitting diodes.

Keyou Yan received his PhD degree in 2013 from the Hong Kong University of Science and Technology. After three-year postdoctoral research, he joined the Chinese University of Hong Kong as an assistant professor. Since 2018, he has been a full professor at the South China University of Technology. His research interests are new-generation photoelectric materials for energy and environmental application, including perovskite solar cells/light emitting diodes, quantum structure devices and environmental detection.

Jianbin Xu received his BSc and MSc degrees from Nanjing University in 1983 and 1986, respectively, and PhD degree from The University of Konstanz. Afterwards, he joined the Department of Electronic Engineering, the Chinese University of Hong Kong. He has been a professor at the department since the midst of 2002. His research interests include solar energy technology, especially hybrid perovskite solar cells, two-dimensional semiconductor materials and devices, organic solid state electronic semiconductors and the optoelectronic devices.

Pingqi Gao is a professor at the School of Materials, Sun Yat-sen University, China. He received his PhD degree at the Department of Physics, Lanzhou University in 2010. He worked at Nanyang Technological University and Ningbo Institute of Materials Technology & Engineering, Chinese academy of sciences and joined Sun Yat-sen University in 2018. His research focuses on developing new semiconducting materials and processes for solar energy conversion and design transition metal-based catalysts for electrochemical applications.

Conflict of interest

The authors declare that they have no conflict of interest.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xie, J., Zhao, S., Hang, P. et al. Reconstructing the amorphous and defective surface for efficient and stable perovskite solar cells. Sci. China Mater. 66, 1323–1331 (2023). https://doi.org/10.1007/s40843-022-2266-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-022-2266-9

Keywords

Search

Navigation