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Graphene oxide doping of the hole injection layer enables 23.6% efficiency in perovskite solar cells with carbon electrodes

Nature Energy (2025)Cite this article

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Abstract

Carbon-based perovskite solar cells (C-PSCs) processed at low temperature are gaining attention due to their enhanced stability and cost-effectiveness. However, these benefits are offset by reduced device performance, primarily stemming from inefficient charge transfer between the hole transport layer (HTL) and the carbon electrode. Here we report the use of graphene oxide functionalized with carboxy groups (GO-COOH) as a dopant for the HTL material 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (Spiro-OMeTAD) to facilitate interfacial charge transfer and immobilize lithium ions to improve both device performance and stability. We demonstrate electron transfer between GO-COOH and Spiro-OMeTAD, where the delocalized electrons in GO-COOH enable p-doping without exposure to oxygen, leading to a strong π–π-conjugated HTL–carbon interface. The formation of Li–C bonds immobilizes the mobile lithium ions, further improving device stability. As a result, the C-PSCs achieve a power conversion efficiency of 23.6%, maintaining 98.7% of their initial performance after 1,000 h of continuous illumination. These results bring the performance of C-PSCs closer to that of devices employing metal electrodes.

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Fig. 1: p-Doping of Spiro-OMeTAD by GO-COOH.
Fig. 2: Mechanism of GO-COOH doping and Li+ ion fixation.
Fig. 3: Impact of GO-COOH on the charge transport kinetics of the HTL.
Fig. 4: Photovoltaic performance and durability of low-temperature processed C-PSCs.

Data availability

The data that support the findings of this study are available within the Article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank S. M. Zakeeruddin and M. Grätzel for their help with the initial phase of preparation of this paper, X. Gao at the Instrumental Analysis Center of Dalian University of Technology for electron microscopy testing and W. Sun (Dalian University of Technology) for surface potential measurements. Y.W. acknowledges support from the National Natural Science Foundation of China (22109019), the Liaoning Provincial Central Guidance Fund for Local S & T Development (Category B of the Youth Science Fund Program: 2025JH6/101000004) and the Fundamental Research Funds for the Central Universities (DUT23RC(3)002). Yantao Shi acknowledges support from the National Natural Science Foundation of China (52272193) and the Fundamental Research Funds for the Central Universities (DUT22LAB602). Z.Z. acknowledges support from the Science Technology and Innovation Committee of Shenzhen Municipality (JCYJ20220818101018038) and a Research Grants Council of Hong Kong Grant (N_CityU102/23, C4005-22Y, C1055-23G and 11306521). G.M. acknowledges support from the Spring City Plan: the High-level Talent Promotion and Training Project of Kunming (2022SCP005) and Yunnan Fundamental Research Projects (202301AT070081). X.W. acknowledges support from the Research Grants Council of the Hong Kong Special Administrative Region, China, through a fellowship award (CityU PDFS2425-1S11).

Author information

Author notes

  1. These authors contributed equally: Yudi Wang, Wenrui Li, Xin Wu, Guanghao Meng.

Authors and Affiliations

  1. State Key laboratory of Fine Chemicals, School of Chemistry, Frontier Science Center for Smart Materials, Dalian University of Technology, Dalian, China

    Yudi Wang, Wenrui Li, Qiuyu Liu, Wenpei Zhao, Yanying Shi, Shuhong Wang, Ziyang Tian, Linghui Zhang, Jie Zhang & Yantao Shi

  2. Department of Chemistry, City University of Hong Kong, Hong Kong, China

    Yudi Wang, Xin Wu, Bo Li, Francesco Vanin & Zonglong Zhu

  3. Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Key Laboratory of Education Ministry for Advance Technique and Preparation of Renewable Energy Materials, Yunnan Normal University, Kunming, China

    Guanghao Meng

  4. School of Environmental and Chemical Engineering, Dalian University, Dalian, China

    Hongjiang Li

  5. Shenzhen Research Institute, City University of Hong Kong, Shenzhen, China

    Zonglong Zhu

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Contributions

Y.W., Yantao Shi and Z.Z. conceived the idea together. Y.W. and X.W. developed the concept and analysed the data. Y.W. and W.L. designed the experiments and characterization measurements. G.M. and H.L. performed and analysed the theoretical DFT calculations. Y.W., W.L., Yanying Shi, Z.T. and L.Z. contributed to the fabrication of high-performance devices. S.W. performed the C-AFM and AFM measurements. Q.L., X.W., B.L. and F.V. helped to draw the illustrations. J.Z. and W.Z. performed the device stability tests. Y.W., W.L. and X.W. wrote the paper with comments from all of the other authors.

Corresponding authors

Correspondence to Yudi Wang, Zonglong Zhu or Yantao Shi.

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Nature Energy thanks Yue Hu, Luigi Vesce and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–4, Figs. 1–42 and Tables 1–6.

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Supplementary Data 1

J–V source data for Supplementary Fig. 12.

Supplementary Data 2

J–V source data for Supplementary Fig. 27.

Supplementary Data 3

J–V source data for Supplementary Fig. 29.

Supplementary Data 4

J–V source data for Supplementary Fig. 32.

Supplementary Data 5

J–V source data for Supplementary Fig. 34.

Supplementary Data 6

J–V source data for Supplementary Fig. 36.

Supplementary Data 7

J–V source data for Supplementary Table 4.

Source data

Source Data Fig. 4

J–V source data for Fig. 4b,c,f–h.

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Wang, Y., Li, W., Wu, X. et al. Graphene oxide doping of the hole injection layer enables 23.6% efficiency in perovskite solar cells with carbon electrodes. Nat Energy (2025). https://doi.org/10.1038/s41560-025-01893-8

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