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High-efficiency colorful perovskite solar cells using TiO2 nanobowl arrays as a structured electron transport layer

TiO2纳米碗阵列作为电子传输层构筑高效率彩色 钙钛矿太阳能电池

Abstract

The rapid development of perovskite solar cells (PSCs) has stimulated great interest in the fabrication of colorful PSCs to meet the needs of aesthetic purposes in varied applications including building integrated photovoltaics and wearable electronics. However, it remains challenging to prepare high-efficiency PSCs with attractive colors using perovskites with broad optical absorption and large absorption coefficients. Here we show that high-efficiency PSCs exhibiting distinct structural colors can be readily fabricated by employing TiO2 nanobowl (NB) arrays as a nanostructured electron transport layer to integrate with a thin overlayer of perovskite on the NB arrays. A new crystalline precursor film based on lead acetate was prepared through a Lewis acid-base adduct approach, which allowed for the formation of a uniform overlayer of high-quality CH3NH3PbI3 crystals on the inner walls of the NBs. The PSCs fabricated using the TiO2 NB arrays showed angle-dependent vivid colors under light illumination. The resultant colorful PSCs exhibited a remarkable photovoltaic performance with a champion efficiency up to 16.94% and an average efficiency of 15.47%, which are record-breaking among the reported colorful PSCs.

摘要

钙钛矿太阳能电池的飞速发展及其在构筑一体化和可穿戴 器件中的应用前景激发了人们对于彩色钙钛矿太阳能电池的浓厚 兴趣, 但如何将可见光宽波段吸收且具有高吸光系数的钙钛矿材 料构筑成高性能的彩色太阳能电池仍是一个挑战. 本文利用TiO2 纳米碗阵列作为结构化的电子传输层, 并在纳米碗内均匀填充一层CH3NH3PbI3钙钛矿薄膜, 成功制备了具有鲜艳结构色的钙钛 矿@TiO2纳米碗阵列薄膜, 其结构色具有显著的角度依赖特征. 通 过路易斯酸碱加合物法制备得到基于醋酸铅的新型晶态中间体薄 膜, 使得高质量的CH3NH3PbI3钙钛矿薄膜能够在纳米碗内均匀填 充. 利用该钙钛矿@TiO2纳米碗薄膜可以制备出具有鲜艳结构色的 平面异质结钙钛矿太阳能电池, 其最高光电转化效率可以达到 16.94%, 平均效率达到15.47%, 均高于现已报道的彩色钙钛矿太阳 能电池的转化效率.

References

  1. 1

    Brenner TM, Egger DA, Kronik L, et al. Hybrid organic-inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties. Nat Rev Mater, 2016, 1: 15007

    CAS  Google Scholar 

  2. 2

    Chen H, Ye F, Tang W, et al. A solvent- and vacuum-free route to large-area perovskite films for efficient solar modules. Nature, 2017, 550: 92–95

    CAS  Google Scholar 

  3. 3

    Tan H, Jain A, Voznyy O, et al. Efficient and stable solution-processed planar perovskite solar cells via contact passivation. Science, 2017, 355: 722–726

    CAS  Google Scholar 

  4. 4

    Rong Y, Hu Y, Mei A, et al. Challenges for commercializing perovskite solar cells. Science, 2018, 361: eaat8235

    Google Scholar 

  5. 5

    Jeon NJ, Na H, Jung EH, et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat Energy, 2018, 3: 682–689

    CAS  Google Scholar 

  6. 6

    Noh JH, Im SH, Heo JH, et al. Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. Nano Lett, 2013, 13: 1764–1769

    CAS  Google Scholar 

  7. 7

    Eperon GE, Burlakov VM, Goriely A, et al. Neutral color semitransparent microstructured perovskite solar cells. ACS Nano, 2014, 8: 591–598

    CAS  Google Scholar 

  8. 8

    Jiang Y, Luo B, Jiang F, et al. Efficient colorful perovskite solar cells using a top polymer electrode simultaneously as spectrally selective antireflection coating. Nano Lett, 2016, 16: 7829–7835

    CAS  Google Scholar 

  9. 9

    Calvo ME. Materials chemistry approaches to the control of the optical features of perovskite solar cells. J Mater Chem A, 2017, 5: 20561–20578

    CAS  Google Scholar 

  10. 10

    Stranks SD, Snaith HJ. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat Nanotech, 2015, 10: 391–402

    CAS  Google Scholar 

  11. 11

    Ergen O, Gilbert SM, Pham T, et al. Graded bandgap perovskite solar cells. Nat Mater, 2017, 16: 522–525

    CAS  Google Scholar 

  12. 12

    Cui D, Yang Z, Yang D, et al. Color-tuned perovskite films prepared for efficient solar cell applications. J Phys Chem C, 2016, 120: 42–47

    CAS  Google Scholar 

  13. 13

    Esfandyarpour M, Garnett EC, Cui Y, et al. Metamaterial mirrors in optoelectronic devices. Nat Nanotech, 2014, 9: 542–547

    CAS  Google Scholar 

  14. 14

    Brongersma ML, Cui Y, Fan S. Light management for photovoltaics using high-index nanostructures. Nat Mater, 2014, 13: 451–460

    CAS  Google Scholar 

  15. 15

    Yang X, Wu J, Liu T, et al. Patterned perovskites for optoelectronic applications. Small Methods, 2018, 2: 1800110

    Google Scholar 

  16. 16

    Deng Y, Wang Q, Yuan Y, et al. Vividly colorful hybrid perovskite solar cells by doctor-blade coating with perovskite photonic nanostructures. Mater Horiz, 2015, 2: 578–583

    CAS  Google Scholar 

  17. 17

    Meng K, Gao S, Wu L, et al. Two-dimensional organic-inorganic hybrid perovskite photonic films. Nano Lett, 2016, 16: 4166–4173

    CAS  Google Scholar 

  18. 18

    Quiroz COR, Bronnbauer C, Levchuk I, et al. Coloring semitransparent perovskite solar cells via dielectric mirrors. ACS Nano, 2016, 10: 5104–5112

    Google Scholar 

  19. 19

    Lee KT, Jang JY, Park SJ, et al. Incident-angle-controlled semitransparent colored perovskite solar cells with improved efficiency exploiting a multilayer dielectric mirror. Nanoscale, 2017, 9: 13983–13989

    CAS  Google Scholar 

  20. 20

    Lu JH, Yu YL, Chuang SR, et al. High-performance, semitransparent, easily tunable vivid colorful perovskite photovoltaics featuring Ag/ITO/Ag microcavity structures. J Phys Chem C, 2016, 120: 4233–4239

    CAS  Google Scholar 

  21. 21

    Lee KT, Fukuda M, Joglekar S, et al. Colored, see-through perovskite solar cells employing an optical cavity. J Mater Chem C, 2015, 3: 5377–5382

    CAS  Google Scholar 

  22. 22

    Zhang W, Anaya M, Lozano G, et al. Highly efficient perovskite solar cells with tunable structural color. Nano Lett, 2015, 15: 1698–1702

    CAS  Google Scholar 

  23. 23

    Lee KT, Jang JY, Zhang J, et al. Highly efficient colored perovskite solar cells integrated with ultrathin subwavelength plasmonic nanoresonators. Sci Rep, 2017, 7: 10640

    Google Scholar 

  24. 24

    Liu D, Wang L, Cui Q, et al. Planar metasurfaces enable high-efficiency colored perovskite solar cells. Adv Sci, 2018, 5: 1800836

    Google Scholar 

  25. 25

    Lee KT, Jang JY, Ha NY, et al. High-performance colorful semitransparent perovskite solar cells with phase-compensated microcavities. Nano Res, 2018, 11: 2553–2561

    CAS  Google Scholar 

  26. 26

    Ye X, Qi L. Two-dimensionally patterned nanostructures based on monolayer colloidal crystals: Controllable fabrication, assembly, and applications. Nano Today, 2011, 6: 608–631

    CAS  Google Scholar 

  27. 27

    Wang WH, Qi LM. Light Management with Patterned Micro- and nanostructure arrays for photocatalysis, photovoltaics, and optoelectronic and optical devices. Adv Funct Mater, 2019, 355: 1807275

    Google Scholar 

  28. 28

    Vogel N, Retsch M, Fustin CA, et al. Advances in colloidal assembly: The design of structure and hierarchy in two and three dimensions. Chem Rev, 2015, 115: 6265–6311

    CAS  Google Scholar 

  29. 29

    Wang W, Jin C, Qi L. Hierarchical CdS nanorod@SnO2 nanobowl arrays for efficient and stable photoelectrochemical hydrogen generation. Small, 2018, 14: 1801352

    Google Scholar 

  30. 30

    Arain Z, Liu C, Yang Y, et al. Elucidating the dynamics of solvent engineering for perovskite solar cells. Sci China Mater, 2019, 62: 161–172

    CAS  Google Scholar 

  31. 31

    Zheng H, Dai S, Zhou K, et al. New-type highly stable 2D/3D perovskite materials: the effect of introducing ammonium cation on performance of perovskite solar cells. Sci China Mater, 2019, 62: 508–518

    CAS  Google Scholar 

  32. 32

    Shao J, Guo X, Shi N, et al. Acenaphthylene-imide based small molecules/TiO2 bilayer as electron-transporting layer for solution-processing efficient perovskite solar cells. Sci China Mater, 2019, 62: 497–507

    CAS  Google Scholar 

  33. 33

    Liu J, Li N, Dong Q, et al. Tailoring electrical property of the low-temperature processed SnO2 for high-performance perovskite solar cells. Sci China Mater, 2019, 62: 173–180

    CAS  Google Scholar 

  34. 34

    Wang W, Ma Y, Qi L. High-performance photodetectors based on organometal halide perovskite nanonets. Adv Funct Mater, 2017, 27: 1603653

    Google Scholar 

  35. 35

    Huang F, Pascoe AR, Wu WQ, et al. Effect of the microstructure of the functional layers on the efficiency of perovskite solar cells. Adv Mater, 2017, 29: 1601715

    Google Scholar 

  36. 36

    Zhao Y, Zhu K. Organic-inorganic hybrid lead halide perovskites for optoelectronic and electronic applications. Chem Soc Rev, 2016, 45: 655–689

    CAS  Google Scholar 

  37. 37

    Hörantner MT, Zhang W, Saliba M, et al. Templated micro-structural growth of perovskite thin films via colloidal monolayer lithography. Energy Environ Sci, 2015, 8: 2041–2047

    Google Scholar 

  38. 38

    Zheng X, Wei Z, Chen H, et al. Designing nanobowl arrays of mesoporous TiO2 as an alternative electron transporting layer for carbon cathode-based perovskite solar cells. Nanoscale, 2016, 8: 6393–6402

    CAS  Google Scholar 

  39. 39

    Hu X, Huang Z, Zhou X, et al. Wearable large-scale perovskite solar-power source via nanocellular scaffold. Adv Mater, 2017, 29: 1703236

    Google Scholar 

  40. 40

    Wang W, Dong J, Ye X, et al. Heterostructured TiO2 nanorod@nanobowl arrays for efficient photoelectrochemical water splitting. Small, 2016, 12: 1469–1478

    CAS  Google Scholar 

  41. 41

    Yoon KY, Ahn HJ, Kwak MJ, et al. A selectively decorated Ti-FeOOH co-catalyst for a highly efficient porous hematite-based water splitting system. J Mater Chem A, 2016, 4: 18730–18736

    CAS  Google Scholar 

  42. 42

    Lee JW, Kim HS, Park NG. Lewis acid-base adduct approach for high efficiency perovskite solar cells. Acc Chem Res, 2016, 49: 311–319

    Google Scholar 

  43. 43

    Zhang W, Saliba M, Moore DT, et al. Ultrasmooth organic-inorganic perovskite thin-film formation and crystallization for efficient planar heterojunction solar cells. Nat Commun, 2015, 6: 6142

    CAS  Google Scholar 

  44. 44

    Jeon NJ, Noh JH, Kim YC, et al. Solvent engineering for high-performance inorganic-organic hybrid perovskite solar cells. Nat Mater, 2014, 13: 897–903

    CAS  Google Scholar 

  45. 45

    Pham ND, Tiong VT, Chen P, et al. Enhanced perovskite electronic properties via a modified lead(II) chloride Lewis acid-base adduct and their effect in high-efficiency perovskite solar cells. J Mater Chem A, 2017, 5: 5195–5203

    CAS  Google Scholar 

  46. 46

    Zhang T, Guo N, Li G, et al. A controllable fabrication of grain boundary PbI2 nanoplates passivated lead halide perovskites for high performance solar cells. Nano Energy, 2016, 26: 50–56

    Google Scholar 

  47. 47

    Liu FZ, Dong Q, Wong MK, et al. Is excess PbI2 beneficial for perovskite solar cell performance? Adv Energy Mater, 2016, 6: 1502206

    Google Scholar 

  48. 48

    Jiang Q, Chu Z, Wang P, et al. Planar-structure perovskite solar cells with efficiency beyond 21%. Adv Mater, 2017, 29: 1703852

    Google Scholar 

  49. 49

    He YT, Wang WH, Qi LM. HPbI3 as a bifunctional additive for morphology control and grain boundary passivation toward efficient planar perovskite solar cells. ACS Appl Mater Interfaces, 2018, 10: 38985–38993

    CAS  Google Scholar 

  50. 50

    Rong Y, Tang Z, Zhao Y, et al. Solvent engineering towards controlled grain growth in perovskite planar heterojunction solar cells. Nanoscale, 2015, 7: 10595–10599

    CAS  Google Scholar 

  51. 51

    Green MA, Ho-Baillie A, Snaith HJ. The emergence of perovskite solar cells. Nat Photon, 2014, 8: 506–514

    CAS  Google Scholar 

  52. 52

    Xia Y, Ran C, Chen Y, et al. Management of perovskite intermediates for highly efficient inverted planar heterojunction perovskite solar cells. J Mater Chem A, 2017, 5: 3193–3202

    CAS  Google Scholar 

  53. 53

    Cao XB, Li YH, Fang F, et al. High quality perovskite films fabricated from Lewis acid-base adduct through molecular exchange. RSC Adv, 2016, 6: 70925–70931

    CAS  Google Scholar 

  54. 54

    Zuo L, Gu Z, Ye T, et al. Enhanced photovoltaic performance of CH3NH3PbI3 perovskite solar cells through interfacial engineering using self-assembling monolayer. J Am Chem Soc, 2015, 137: 2674–2679

    CAS  Google Scholar 

  55. 55

    Bi C, Wang Q, Shao Y, et al. Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells. Nat Commun, 2015, 6: 7747

    CAS  Google Scholar 

  56. 56

    Zhang W, Pathak S, Sakai N, et al. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells. Nat Commun, 2015, 6: 10030

    CAS  Google Scholar 

  57. 57

    Kolle M, Salgard-Cunha PM, Scherer MRJ, et al. Mimicking the colourful wing scale structure of the Papilio Blumei butterfly. Nat Nanotech, 2010, 5: 511–515

    CAS  Google Scholar 

  58. 58

    Diao YY, Liu XY, Toh GW, et al. Multiple structural coloring of silk-fibroin photonic crystals and humidity-responsive color sensing. Adv Funct Mater, 2013, 23: 5373–5380

    CAS  Google Scholar 

  59. 59

    Umh HN, Yu S, Kim YH, et al. Tuning the structural color of a 2D photonic crystal using a bowl-like nanostructure. ACS Appl Mater Interfaces, 2016, 8: 15802–15808

    CAS  Google Scholar 

  60. 60

    Si H, Liao Q, Zhang Z, et al. An innovative design of perovskite solar cells with Al2O3 inserting at ZnO/perovskite interface for improving the performance and stability. Nano Energy, 2016, 22: 223–231

    CAS  Google Scholar 

  61. 61

    Li W, Zhang W, Van Reenen S, et al. Enhanced UV-light stability of planar heterojunction perovskite solar cells with caesium bromide interface modification. Energy Environ Sci, 2016, 9: 490–498

    CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21673007). The authors were grateful to Xue Zhou and Prof. Mingzhu Li for their kind help in the measurement of the reflection spectra of the perovskite@TiO2 NB array.

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Affiliations

Authors

Contributions

Qi L conceived the study. Wang W designed and performed the experiments. He Y participated in the materials preparation and data analysis. Wang W and Qi L wrote the manuscript. Qi L supervised the project. All authors contributed to the general discussion.

Corresponding author

Correspondence to Limin Qi.

Additional information

Wenhui Wang received her PhD degree in physical chemistry from Peking University under the supervision of Prof. Limin Qi in 2018. Currently, she is working at National University of Singapore as a research fellow. Her present research interests focus on the in-situ growth and assembly of metal nanoparticles using liquid cell TEM.

Limin Qi received his PhD degree from Peking University in 1998. He then went to the Max Planck Institute of Colloids and Interfaces as a postdoctoral fellow. In 2000, he joined the College of Chemistry at Peking University, where he has been a full professor since 2004. His research interests include colloidal chemistry, nanomaterials, self-assembly, energy-related materials, and biomimetic materials chemistry.

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Wang, W., He, Y. & Qi, L. High-efficiency colorful perovskite solar cells using TiO2 nanobowl arrays as a structured electron transport layer. Sci. China Mater. 63, 35–46 (2020). https://doi.org/10.1007/s40843-019-9452-1

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Keywords

  • perovskite
  • solar cells
  • nanobowl arrays
  • structural color
  • nanostructures