Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.
Advertisement
Nature Materials volume 24, pages 1450–1456 (2025)
7023
10
8
Metrics details
Although being highly demanded in organic electronics, functional conjugated polymers face challenges on scalable synthesis with batch uniformities. Here a reactivity-regulated sequent cross-coupling carbon–nitrogen polycondensation method is developed to enable the precise synthesis of functional polyarylamines with excellent batch-to-batch uniformity. It is revealed that the stepwise regulation of intermediate reactivities is key to accomplish controllable polycondensation via two sequent palladium-promoted carbon–nitrogen coupling cycles, which is distinct to the unicyclic carbon–carbon coupling. A variety of polyarylamines are prepared to improve the material functionalities, where a ternary polymer consisting of polar substituents is shown to optimize the interfacial and bulk properties of perovskite layers fabricated on top. The corresponding inverted perovskite solar cells achieved remarkable power conversion efficiencies of 25.2% (active area, 5.97 mm2) and 23.2% (active area, 128 mm2), along with decent operational stabilities. Overall, this work provides an effective polymerization method for advanced conjugated polymers to enable high-performance optoelectronics.
This is a preview of subscription content, access via your institution
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$32.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
USD 39.95
Prices may be subject to local taxes which are calculated during checkout
The main data supporting the findings of this study are available within the Article and its Supplementary Information.
Swager, T. M. 50th anniversary perspective: conducting/semiconducting conjugated polymers. A personal perspective on the past and the future. Macromolecules 50, 4867–4886 (2017).
Article CAS Google Scholar
Ding, L. et al. Polymer semiconductors: synthesis, processing, and applications. Chem. Rev. 123, 7421–7497 (2023).
Article CAS PubMed Google Scholar
Yu, Z.-P., Yan, K., Ullah, W., Chen, H. & Li, C.-Z. Conjugated polymers for photon-to-electron and photon-to-fuel conversions. ACS Appl. Polym. Mater. 3, 60–92 (2020).
Article Google Scholar
Sun, F. et al. Soft fiber electronics based on semiconducting polymer. Chem. Rev. 123, 4693–4763 (2023).
Article CAS PubMed Google Scholar
An, C. & Hou, J. Benzo[1,2-b:4,5-b′]dithiophene-based conjugated polymers for highly efficient organic photovoltaics. Acc. Mater. Res. 3, 540–551 (2022).
Article CAS Google Scholar
Freudenberg, J., Jansch, D., Hinkel, F. & Bunz, U. H. F. Immobilization strategies for organic semiconducting conjugated polymers. Chem. Rev. 118, 5598–5689 (2018).
Article CAS PubMed Google Scholar
Fei, C. et al. Strong-bonding hole-transport layers reduce ultraviolet degradation of perovskite solar cells. Science 384, 1126–1134 (2024).
Article CAS PubMed Google Scholar
Li, B. et al. Highly efficient and scalable p-i-n perovskite solar cells enabled by poly-metallocene interfaces. J. Am. Chem. Soc. 146, 13391–13398 (2024).
Article CAS PubMed PubMed Central Google Scholar
Li, H. et al. 2D/3D heterojunction engineering at the buried interface towards high-performance inverted methylammonium-free perovskite solar cells. Nat. Energy 8, 946–955 (2023).
Article CAS Google Scholar
Liang, Z. et al. Homogenizing out-of-plane cation composition in perovskite solar cells. Nature 624, 557–563 (2023).
Article CAS PubMed PubMed Central Google Scholar
Fei, C. et al. Lead-chelating hole-transport layers for efficient and stable perovskite minimodules. Science 380, 823–829 (2023).
Article CAS PubMed Google Scholar
Luo, D. et al. Enhanced photovoltage for inverted planar heterojunction perovskite solar cells. Science 360, 1442–1446 (2018).
Article CAS PubMed Google Scholar
Huang, Y. et al. Finite perovskite hierarchical structures via ligand confinement leading to efficient inverted perovskite solar cells. Energy Environ. Sci. 16, 557–564 (2023).
Article CAS Google Scholar
Sun, Y. et al. Bright and stable perovskite light-emitting diodes in the near-infrared range. Nature 615, 830–835 (2023).
Article CAS PubMed Google Scholar
Zhao, X. & Tan, Z.-K. Large-area near-infrared perovskite light-emitting diodes. Nat. Photon. 14, 215–218 (2019).
Article Google Scholar
Jiang, Q. & Zhu, K. Rapid advances enabling high-performance inverted perovskite solar cells. Nat. Rev. Mater. 9, 399–419 (2024).
Article CAS Google Scholar
Veres, J., Ogier, S. D., Leeming, S. W., Cupertino, D. C. & Khaffaf, S. M. Low‐k insulators as the choice of dielectrics in organic field‐effect transistors. Adv. Funct. Mater. 13, 199–204 (2003).
Article CAS Google Scholar
Mathijssen, S. G. J. et al. Dynamics of threshold voltage shifts in organic and amorphous silicon field-effect transistors. Adv. Mater. 19, 2785–2789 (2007).
Article CAS Google Scholar
Zhang, W. et al. Systematic improvement in charge carrier mobility of air stable triarylamine copolymers. J. Am. Chem. Soc. 131, 10814–10815 (2009).
Article CAS PubMed Google Scholar
Wang, Y. et al. PTAA as efficient hole transport materials in perovskite solar cells: a review. Sol. RRL 6, 2200234 (2022).
Article CAS Google Scholar
Xu, X. et al. Improving contact and passivation of buried interface for high‐efficiency and large‐area inverted perovskite solar cells. Adv. Funct. Mater. 32, 2109968 (2021).
Article Google Scholar
Chen, R. et al. Robust hole transport material with interface anchors enhances the efficiency and stability of inverted formamidinium–cesium perovskite solar cells with a certified efficiency of 22.3%. Energy Environ. Sci. 15, 2567–2580 (2022).
Article CAS Google Scholar
Wu, X. et al. Backbone engineering enables highly efficient polymer hole‐transporting materials for inverted perovskite solar cells. Adv. Mater. 35, 2208431 (2023).
Article CAS Google Scholar
Miyaura, N. & Suzuki, A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 95, 2457–2483 (1995).
Article CAS Google Scholar
Burke, D. J. & Lipomi, D. J. Green chemistry for organic solar cells. Energy Environ. Sci. 6, 2053–2066 (2013).
Article CAS Google Scholar
Xiong, H. et al. General room-temperature Suzuki–Miyaura polymerization for organic electronics. Nat. Mater. 23, 695–702 (2024).
Article CAS PubMed Google Scholar
Yamamoto, T., Hayashi, Y. & Yamamoto, A. A novel type of polycondensation utilizing transition metal-catalyzed C–C coupling. I. Preparation of thermostable polyphenylene type polymers. Bull. Chem. Soc. Jpn 51, 2091–2097 (1978).
Article CAS Google Scholar
Kim, Y. et al. Sequentially fluorinated PTAA polymers for enhancing Voc of high-performance perovskite solar cells. Adv. Energy Mater. 8, 1801668 (2018).
Article Google Scholar
Kim, Y. et al. Methoxy-functionalized triarylamine-based hole-transporting polymers for highly efficient and stable perovskite solar cells. ACS Energy Lett. 5, 3304–3313 (2020).
Article CAS Google Scholar
Lim, C. et al. Oligo(ethylene glycol)-incorporated hole transporting polymers for efficient and stable inverted perovskite solar cells. J. Mater. Chem. A 11, 6615–6624 (2023).
Article CAS Google Scholar
Wang, K.-L. et al. High-performance organic photorefractive materials containing 2-ethylhexyl plasticized poly(triarylamine). J. Mater. Chem. C 8, 13357–13367 (2020).
Article CAS Google Scholar
Uehling, M. R., King, R. P., Krska, S. W., Cernak, T. & Buchwald, S. L. Pharmaceutical diversification via palladium oxidative addition complexes. Science 363, 405–408 (2019).
Article CAS PubMed Google Scholar
Arora, R. & Lautens, M. Photoexcited nickel-catalyzed carbohalogenation. ACS Catal. 14, 1970–1975 (2024).
Article CAS Google Scholar
Yokoyama, A. et al. Chain-growth polymerization for the synthesis of polyfluorene via Suzuki-Miyaura coupling reaction from an externally added initiator unit. J. Am. Chem. Soc. 129, 7236–7237 (2007).
Article CAS PubMed Google Scholar
Xu, C., Dong, J., He, C., Yun, J. & Pan, X. Precise control of conjugated polymer synthesis from step-growth polymerization to iterative synthesis. Giant 14, 100154 (2023).
Article CAS Google Scholar
Lee, S. M., Park, K. H., Jung, S., Park, H. & Yang, C. Stepwise heating in Stille polycondensation toward no batch-to-batch variations in polymer solar cell performance. Nat. Commun. 9, 1867 (2018).
Article PubMed PubMed Central Google Scholar
McCann, S. D., Reichert, E. C., Arrechea, P. L. & Buchwald, S. L. Development of an aryl amination catalyst with broad scope guided by consideration of catalyst stability. J. Am. Chem. Soc. 142, 15027–15037 (2020).
Article CAS PubMed PubMed Central Google Scholar
Download references
This research was funded by the National Natural Science Foundation of China (no. 22125901), the National Key Research and Development Program of China (no. 2019YFA0705900), the Fundamental Research Funds for the Central Universities (no. 226-2024-00005) and the Scientific Research Project of China Three Gorges Corporation (no. 202303014). We thank P. Qian and B. Shi from the Department of Chemistry, Zhejiang University, for technical support on scale synthesis.
These authors contributed equally: Ziqiu Shen, Yanchun Huang.
State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, People’s Republic of China
Ziqiu Shen, Yanchun Huang, Yuan Dong, Kangrong Yan, Hongzhen Chen & Chang-Zhi Li
PubMed Google Scholar
PubMed Google Scholar
PubMed Google Scholar
PubMed Google Scholar
PubMed Google Scholar
PubMed Google Scholar
C.-Z.L. and Z.S. developed the concept. C.-Z.L., Z.S., Y.H. and K.Y. designed the experiments. C.-Z.L. and H.C. supervised the project. Z.S. conducted the synthesis experiments. Y.H. and Z.S. performed the PSC fabrication and characterization. Y.H., Z.S., Y.D. and K.Y. carried out the film measurements and analysis. Z.S., Y.H. and C.-Z.L. prepared the manuscript. All authors provided feedback and commented on the manuscript.
Correspondence to Chang-Zhi Li.
The authors declare no competing interests.
Nature Materials thanks Mohammad Khaja Nazeeruddin, Yanlin Song and Atsushi Wakamiya for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Figs. 1–25 and Tables 1–7.
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
Reprints and permissions
Shen, Z., Huang, Y., Dong, Y. et al. Precise synthesis of advanced polyarylamines for efficient perovskite solar cells. Nat. Mater. 24, 1450–1456 (2025). https://doi.org/10.1038/s41563-025-02199-6
Download citation
Received:
Accepted:
Published:
Version of record:
Issue date:
DOI: https://doi.org/10.1038/s41563-025-02199-6
Anyone you share the following link with will be able to read this content:
Sorry, a shareable link is not currently available for this article.
Provided by the Springer Nature SharedIt content-sharing initiative
Nature Materials (2025)
Nature Communications (2025)
Nature Synthesis (2025)
Advertisement
Nature Materials (Nat. Mater.)
ISSN 1476-4660 (online)
ISSN 1476-1122 (print)
© 2026 Springer Nature Limited
Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.
