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Symmetry-driven engineering of long-range-ordered π–π stacking molecules for high-efficiency perovskite photovoltaics

Nature Synthesis volume 5, pages 64–73 (2026)Cite this article

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Abstract

The development of molecular engineering has substantially increased the power conversion efficiency of inverted p-i-n perovskite solar cells (PSCs) over the past five years, surpassing that of regular n-i-p PSCs. The strategic design of symmetric molecules to alleviate steric hindrance, thereby facilitating long-range-ordered π–π stacking on substrates, offers an effective approach for enhancing the structural organization in molecular self-assembly. Here we synthesize an axially symmetric molecule with homogeneous electron delocalization, (2-(pyren-2-yl)ethyl)phosphonic acid (pPy), which can form a long-range-ordered π–π stacking assembly on indium tin oxide substrates. Additionally, the pPy thin film demonstrates an intense and integrated Debye–Scherrer ring at q = 0.27 Å−1 with a highly ordered face-on orientation and displays more spatial uniform distribution, which effectively facilitates charge transport. The as-fabricated pPy-based PSCs achieve a power conversion efficiency of 26.6% and maintain 94% of the initial efficiency after 3,000 h of continuous simulated solar illumination following the ISOS-L-1I protocol.

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Fig. 1: Symmetric molecular design for π–π stacking.
Fig. 2: Long-range face-on π–π stacking orientation.
Fig. 3: Charge-transport mechanism.
Fig. 4: Photovoltaic performance of the PSCs.

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The authors declare that data supporting the findings of this study are available within the paper and its Supplementary Information files. Source data are provided with this paper.

References

  1. Chen, J. et al. Determining the bonding–degradation trade-off at heterointerfaces for increased efficiency and stability of perovskite solar cells. Nat. Energy 10, 181–190 (2025).

    CAS  Google Scholar 

  2. Wang, D. et al. Binary microcrystal additives enabled antisolvent-free perovskite solar cells with high efficiency and stability. Adv. Energy Mater. 13, 2203649 (2023).

    Article  CAS  Google Scholar 

  3. Wang, D. et al. All-in-one additive enabled efficient and stable narrow-bandgap perovskites for monolithic all-perovskite tandem solar cells. Adv. Mater. 36, 2411677 (2024).

    Article  CAS  Google Scholar 

  4. Liang, Z. et al. Homogenizing out-of-plane cation composition in perovskite solar cells. Nature 624, 557–563 (2023).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  5. Zhu, P. et al. Aqueous synthesis of perovskite precursors for highly efficient perovskite solar cells. Science 383, 524–531 (2024).

    Article  PubMed  CAS  Google Scholar 

  6. Best research-cell efficiency chart. National Renewable Energy Laboratory www.nrel.gov/pv/cell-efficiency.html (2025).

  7. Peng, W. et al. A versatile energy-level-tunable hole-transport layer for multi-composition inverted perovskite solar cells. Energy Environ. Sci. 18, 874–883 (2025).

    Article  CAS  Google Scholar 

  8. Zhang, S. et al. Minimizing buried interfacial defects for efficient inverted perovskite solar cells. Science 380, 404–409 (2023).

    Article  PubMed  CAS  Google Scholar 

  9. Magomedov, A. et al. Self-assembled hole transporting monolayer for highly efficient perovskite solar cells. Adv. Energy Mater. 8, 1801892 (2018).

    Article  Google Scholar 

  10. Al-Ashouri, A. et al. Conformal monolayer contacts with lossless interfaces for perovskite single junction and monolithic tandem solar cells. Energy Environ. Sci. 12, 3356–3369 (2019).

    Article  CAS  Google Scholar 

  11. Al-Ashouri, A. et al. Monolithic perovskite/silicon tandem solar cell with >29% efficiency by enhanced hole extraction. Science 370, 1300–1309 (2020).

    Article  PubMed  CAS  Google Scholar 

  12. Lennard-Jones, J. E. The electronic structure of some diatomic molecules. Trans. Faraday Soc. 25, 668–686 (1929).

    Article  CAS  Google Scholar 

  13. Pauling, L. The nature of the chemical bond. Application of result obtained from the quantum mechanics and from a theory of paramagnetic susceptibility to the structure of molecules. J. Am. Chem. Soc. 53, 1367–1400 (1931).

    Article  CAS  Google Scholar 

  14. Zhao, K. et al. Peri-fused polyaromatic molecular contacts for perovskite solar cells. Nature 632, 301–306 (2024).

    Article  PubMed  CAS  Google Scholar 

  15. Szűcs, R., Bouit, P.-A., Nyulászi, L. & Hissler, M. Phosphorus-containing polycyclic aromatic hydrocarbons. ChemPhysChem 18, 2618–2630 (2017).

    Article  PubMed  Google Scholar 

  16. Zeng, J. et al. Small-molecule hole transport materials for >26% efficient inverted perovskite solar cells. J. Am. Chem. Soc. 147, 725–733 (2025).

    Article  PubMed  CAS  Google Scholar 

  17. Deng, J.-H. et al. π–π stacking interactions: non-negligible forces for stabilizing porous supramolecular frameworks. Sci. Adv. 6, eaax9976 (2020).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  18. Zou, W. et al. Side-chain symmetry-breaking strategy on porphyrin donors enables high-efficiency binary all-small-molecule organic solar cells. SusMat. 4, e203 (2024).

    Article  CAS  Google Scholar 

  19. Chen, S. et al. Symmetry-induced orderly assembly achieving high-performance perylene diimide-based nonfullerene organic solar cells. CCS Chem. 3, 78–84 (2021).

    Article  CAS  Google Scholar 

  20. Jiang, W. et al. Spin-coated and vacuum-processed hole-extracting self-assembled multilayers with H-aggregation for high-performance inverted perovskite solar cells. Angew. Chem. Int. Ed. 63, e202411730 (2024).

    Article  CAS  Google Scholar 

  21. Liao, X. et al. Manipulating molecular stacking to achieve high electron mobility in 2D conjugated ultra-narrow bandgap non-fullerene acceptors with absorption beyond 1000 nm. Adv. Funct. Mater. 34, 2405728 (2024).

    Article  CAS  Google Scholar 

  22. Ren, J. et al. Optimizing molecular packing via steric hindrance for reducing non-radiative recombination in organic solar cells. Angew. Chem. Int. Ed. 63, e202406153 (2024).

    Article  CAS  Google Scholar 

  23. He, R. et al. Improving interface quality for 1-cm2 all-perovskite tandem solar cells. Nature 618, 80–86 (2023).

    Article  PubMed  CAS  Google Scholar 

  24. Zhao, S. et al. Cross-plane transport in a single-molecule two-dimensional van der Waals heterojunction. Sci. Adv. 6, eaba6714 (2020).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  25. Wan, Y. et al. Facilely achieving near-infrared-II J-aggregates through molecular bending on a donor–acceptor fluorophore for high-performance tumor phototheranostics. ACS Nano 18, 27949–27961 (2024).

    Article  PubMed  CAS  Google Scholar 

  26. Wang, D. et al. Rigid molecules anchoring on NiOx enable >26% efficiency perovskite solar cells. Joule 9, 101815 (2025).

    Article  CAS  Google Scholar 

  27. Gao, Z.-W. et al. Eutectic molecule ligand stabilizes photoactive black phase perovskite. Nat. Photon. 19, 258–263 (2025).

    Article  CAS  Google Scholar 

  28. Ni, Z. et al. Resolving spatial and energetic distributions of trap states in metal halide perovskite solar cells. Science 367, 1352–1358 (2020).

    Article  PubMed  CAS  Google Scholar 

  29. Zhang, J. et al. Tuning perovskite surface polarity via dipole moment engineering for efficient hole-transport-layer-free Sn–Pb mixed-perovskite solar cells. ACS Appl. Mater. Interfaces 15, 15321–15331 (2023).

    Article  PubMed  CAS  Google Scholar 

  30. Khenkin, M. V. et al. Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures. Nat. Energy 5, 35–49 (2020).

    Article  Google Scholar 

  31. Li, M., Liu, M., Qi, F., Lin, F. R. & Jen, A. K. Y. Self-assembled monolayers for interfacial engineering in solution-processed thin-film electronic devices: design, fabrication, and applications. Chem. Rev. 124, 2138–2204 (2024).

    Article  PubMed  CAS  Google Scholar 

  32. Ameen, S. et al. 3,6-Bis(methylthio)-9H-carbazole based self-assembled monolayer for highly efficient and stable inverted perovskite solar cells. Angew. Chem. Int. Ed. 64, e202423206 (2025).

    Article  CAS  Google Scholar 

  33. Torres Merino, L. V. et al. Impact of the valence band energy alignment at the hole-collecting interface on the photostability of wide band-gap perovskite solar cells. Joule 8, 2585–2606 (2024).

    Article  CAS  Google Scholar 

  34. Noether, E. Invariante variation problems. Nachr. Ges. Wiss. Göttingen, Math.-Phys. Kl. 1918, 235–257 (1918).

    Google Scholar 

  35. Huang, J. GIWAXS script. Gitee https://gitee.com/swordshinehjy/giwaxs-script (2025).

Download references

Acknowledgements

B.X. acknowledges the National Key Research and Development Project from the Ministry of Science and Technology of China (2021YFB3800101), the Guangdong Basic and Applied Basic Research Foundation (2023A1515012797, 2023B1515120031), the Shenzhen Science and Technology Innovation Committee (JCYJ20220530113205013, JCYJ20220818100211025, SGDX20230116091649013), SUSTech Energy Institute for Carbon Neutrality (High Level of Special Funds, G03034K001) and the Project for Building a Science and Technology Innovation Center Facing South Asia and Southeast Asia (202403AP140015). Y.Z. acknowledges the National Natural Science Foundation of China (62204108). P.Z. acknowledges the National Natural Science Foundation of China (224B2904). The authors also acknowledge the technical support from SUSTech Core Research Facilities and the Center for Computational Science and Engineering, and the beamline BL14B1 of the Shanghai Synchrotron Radiation Facility (SSRF) for assistance with the GIWAXS measurements.

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Author notes

  1. These authors contributed equally: Peide Zhu, Zhixin Liu, Xia Lei.

Authors and Affiliations

  1. Department of Materials Science and Engineering, and Shenzhen Engineering Research and Development Center for Flexible Solar Cells, Southern University of Science and Technology, Shenzhen, China

    Peide Zhu, Zhixin Liu, Xia Lei, Siru He, Deng Wang, Jie Zeng, Lida Wang, Fei Su, Wenbo Peng, Zhiwei Lei, Zhitong Li, Xingzhu Wang & Baomin Xu

  2. Key University Laboratory of Highly Efficient Utilization of Solar Energy and Sustainable Development of Guangdong, Southern University of Science and Technology, Shenzhen, China

    Peide Zhu, Zhixin Liu, Xia Lei, Siru He, Deng Wang, Jie Zeng, Lida Wang, Fei Su, Wenbo Peng, Zhiwei Lei, Zhitong Li & Baomin Xu

  3. Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China

    Deng Wang & Jie Zeng

  4. Key Laboratory of Photovoltaic and Energy Conservation Material, Institute of Solid-State Physics, Hefei Institutes of Physical Science (HIPS), Chinese Academy of Sciences, Hefei, China

    Zheng Liang & Xu Pan

  5. College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing, China

    Yuxin Sun

  6. School of Energy and Environment, Department of Materials Science and Engineering, Centre for Functional Photonics (CFP), City University of Hong Kong, Hong Kong, China

    Hsien-Yi Hsu

  7. Engineering and Research Center for Integrated New Energy Photovoltaics & Energy Storage Systems of Hunan Province and School of Electrical Engineering, University of South China, Hengyang, China

    Xingzhu Wang

  8. Shenzhen Putai Technology Co. Ltd, Shenzhen, China

    Xingzhu Wang

  9. Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic University, Shenzhen, China

    Jingbai Li

  10. Sustainable Energy and Environment Thrust, Function Hub, The Hong Kong University of Science and Technology (Guangzhou), Guangzhou, China

    Yong Zhang

  11. SUSTech Energy Institute for Carbon Neutrality, Southern University of Science and Technology, Shenzhen, China

    Baomin Xu

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Contributions

P.Z., Z. Liu, Y.Z., X.W. and B.X. supervised the project. P.Z. conceptualized the research idea and designed the experimental framework. P.Z. and Z. Liu analysed the experimental data. P.Z. and Z. Liu wrote the paper. P.Z., Y.Z., Z. Liu, H.-Y.H. and B.X. revised the paper. Z. Liu contributed to synthesizing the mPy and pPy molecules and characterizing the molecule films and perovskite solar cells. X.L. and J.L. contributed to the DFT calculation and molecular dynamics simulations. S.H. and Y.S. contributed to the DFT calculation. L.W. contributed to the TGA of the mPy and pPy molecules. D.W. and J.Z. performed the TAS measurement and analysis. Z. Lei, F.S. and W.P. contributed to fabricating the inverted perovskite solar cells and performing the stability test. Z. Liang, Z. Li and X.P. contributed to space-charge-limited analysis. All authors contributed to discussions about the paper.

Corresponding authors

Correspondence to Xingzhu Wang, Jingbai Li, Yong Zhang or Baomin Xu.

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Nature Synthesis thanks Toshinori Matsushima, Hyunjung Shin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Zhu, P., Liu, Z., Lei, X. et al. Symmetry-driven engineering of long-range-ordered π–π stacking molecules for high-efficiency perovskite photovoltaics. Nat. Synth 5, 64–73 (2026). https://doi.org/10.1038/s44160-025-00896-3

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