Thermally Driven Lanthanide Dual-Site Doping Enables High Performance Perovksite Solar Cells via Halide Migration Suppression

Abstract

Wide-bandgap (WBG) perovskite solar cells (PSCs) are critical for tandem architectures but suffer from light-induced halide segregation and non-radiative recombination. Although conventional rare-earth doping passivates defects, it concurrently introduces vacancies and lattice strain that exacerbate halogen migration. Herein, we report a thermally induced doping strategy where Pr³⁺/Sm³⁺ ions pre-embedded in MeO-4PACz diffuse into the perovskite during annealing. Through combined tolerance factor analysis, structural characterization, and DFT calculations, we identify a dual doping mechanism: predominant interstitial incorporation with minor B-site substitution. This approach reduces defect density, increases iodine migration energy barriers (from 0.85 to 0.94 and 1.12 eV), and minimizes lattice distortion. Consequently, the experimental results show that the open-circuit voltage increases from 1.198 V to 1.230 V (Pr³⁺) and 1.233 V (Sm³⁺), and the fill factor increases from 83% to 86%. Finally, the PCE reached 23.04% (Pr³⁺) and 23.39% (Sm³⁺) (20.12% for control) with > 90% stability retention after 1500 h. In addition, the optimized semitransparent WBG device PCE was 19.48% (Pr³⁺) and 19.85% (Sm³⁺), and the PCE of 4-T perovskite was 27.05% (Pr³⁺) and 27.56% (Sm³⁺). This method will be beneficial for the development and application of WBG PSCs and TSCs.

Keywords

all-perovskite tandem solar cells / halide migration inhibition / interstitial doping / rare-earth ions / wide-band gap

References

[1] M. A. Green, E. D. Dunlop, M. Yoshita, et al., “Solar Cell Efficiency Tables (Version 66,” Progress in Photovoltaics: Research and Applications 33 (2025): 795–810.

[2] J. Wen, H. Hu, C. Chen, et al., “Present Status of and Future Opportunities for All-Perovskite Tandem Photovoltaics,” Nature Energy 10 (2025): 681–696.

[3] Z. Ying, S. Su, X. Li, et al., “Antisolvent Seeding of Self-Assembled Monolayers for Flexible Monolithic perovskite/Cu(In,Ga)Se2 Tandem Solar Cells,” Nature Energy 10 (2025): 737–749.

[4] M. Lai, A. Obliger, D. Lu, et al., “Intrinsic Anion Diffusivity in Lead Halide Perovskites Is Facilitated by a Soft Lattice,” Proceedings of the National Academy of Sciences 115 (2018): 11929–11934.

[5] Y. Yuan and J. Huang, “Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability,” Accounts of Chemical Research 49 (2016): 286–293.

[6] T. A. Berhe, W.-N. Su, C.-H. Chen, et al., “Organometal Halide Perovskite Solar Cells: Degradation and Stability,” Energy & Environmental Science 9 (2016): 323–356.

[7] E. T. Hoke, D. J. Slotcavage, E. R. Dohner, A. R. Bowring, H. I. Karunadasa, and M. D. McGehee, “Reversible Photo-Induced Trap Formation in Mixed-Halide Hybrid Perovskites for Photovoltaics,” Chemical Science 6 (2015): 613–617.

[8] M. Keshavarz, M. Ottesen, S. Wiedmann, et al., “Tracking Structural Phase Transitions in Lead-Halide Perovskites by Means of Thermal Expansion,” Advanced Materials 31 (2019): 1900521.

[9] H. Zai, Y. Ma, Q. Chen, and H. Zhou, “Ion Migration in Halide Perovskite Solar Cells: Mechanism, Characterization, Impact and Suppression,” Journal of Energy Chemistry 63 (2021): 528–549.

[10] M. Saliba, T. Matsui, J. Y. Seo, et al., “Cesium-Containing Triple Cation Perovskite Solar Cells: Improved Stability, Reproducibility and High Efficiency,” Energy & Environmental Science 9 (2016): 1989–1997.

[11] Q. Jiang, Y. Zhao, X. Zhang, et al., “Surface Passivation of Perovskite Film for Efficient Solar Cells,” Nature Photonics 13 (2019): 460–466.

[12] D. Koo, Y. Choi, U. Kim, et al., “Mesoporous Structured MoS2 as an Electron Transport Layer for Efficient and Stable Perovskite Solar Cells,” Nature Nanotechnology 20 (2025): 75–82.

[13] D. Kim, H. J. Jung, I. J. Park, et al., “Efficient, Stable Silicon Tandem Cells Enabled by Anion-Engineered Wide-Bandgap Perovskites,” Science 368 (2020): 155–160.

[14] S. G. Schmidt, M. G. Malle, A. K. Nielsen, et al., “The Dopamine Transporter Antiports Potassium to Increase the Uptake of Dopamine,” Nature Communications 13 (2022): 2446.

[15] M. De Bastiani, A. J. Mirabelli, Y. Hou, et al., “Efficient Bifacial Monolithic Perovskite/Silicon Tandem Solar Cells via Bandgap Engineering,” Nature Energy 6 (2021): 167–175.

[16] K. Wang, L. Zheng, T. Zhu, et al., “Efficient Perovskite Solar Cells by Hybrid Perovskites Incorporated With Heterovalent Neodymium Cations,” Nano Energy 61 (2019): 352–360.

[17] A. Pramanick, X. P. Wang, C. Hoffmann, S. O. Diallo, M. R. V. Jørgensen, and X. L. Wang, “Microdomain Dynamics in Single-Crystal BaTiO₃ During Paraelectric-Ferroelectric Phase Transition Measured With Time-of-Flight Neutron Scattering,” Physical Review B 92 (2015): 174103.

[18] I. Robinson and R. Harder, “Coherent X-Ray Diffraction Imaging of Strain at the Nanoscale,” Nature Materials 8 (2009): 291–298.

[19] J.-W. Lee, S. Tan, S. I. Seok, Y. Yang, and N.-G. Park, “Rethinking the a Cation in Halide Perovskites,” Science 375 (2022): eabj1186.

[20] W. Xiang, Z. Wang, D. J. Kubicki, et al., “Europium-Doped CsPbI2Br for Stable and Highly Efficient Inorganic Perovskite Solar Cells,” Joule 3 (2019): 205–214.

[21] R. D. Shannon, “Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chalcogenides,” Acta Crystallographica Section A 32 (1976): 751–767.

[22] J. Y. Kim, J.-W. Lee, H. S. Jung, H. Shin, and N.-G. Park, “High-Efficiency Perovskite Solar Cells,” Chemical Reviews 120 (2020): 7867–7918.

[23] V. M. Goldschmidt, “Crystal Structure and Chemical Constitution,” Transactions of the Faraday Society 25 (1929): 253–283.

[24] Y. Zhao, I. Yavuz, M. Wang, et al., “Suppressing Ion Migration in Metal Halide Perovskite via Interstitial Doping With a Trace Amount of Multivalent Cations,” Nature Materials 21 (2022): 1396–1402.

[25] L. Pauling, “The Nature of the Chemical Bond. IV. the Energy of Single Bonds and the Relative Electronegativity of Atoms,” Journal of the American Chemical Society 54 (1932): 3570–3582.

[26] A. L. Allred and E. G. Rochow, “A Scale of Electronegativity Based on Electrostatic Force,” Journal of Inorganic and Nuclear Chemistry 5 (1958): 264–268.

[27] Infrared and Raman Characteristic Group Frequencies: Tables and Charts, “3rd Ed by George Socrates (The University of West London, Middlesex, U.K.). J. Wiley and Sons: Chichester. 2001. xviii + 348 pp. $185.00. ISBN: 0-471-85298-8,” Journal of the American Chemical Society 124 (2002): 1830.

[28] G. Herzberg and S. Mrozowski, “Molecular Spectra and Molecular Structure. I. Spectra of Diatomic Molecules,” American Journal of Physics 19 (1951): 390–391.

[29] J. C. Slater, “Atomic Shielding Constants,” Physical Review 36 (1930): 57–64.

[30] K. Miyata, D. Meggiolaro, M. T. Trinh, et al., “Large Polarons in Lead Halide Perovskites,” Science Advances 3 (2017): e1701217.

[31] G. G. C. Quarti, E. Mosconi, P. Bruno, et al., “The Raman Spectrum of the CH₃NH₃PbI₃ Hybrid Perovskite: Interplay of Theory and Experiment,” Journal of Physical Chemistry Letters 5 (2014): 279–284.

[32] R. Zhuang, L. Wang, J. Qiu, et al., “Effect of Molecular Configuration of Additives on Perovskite Crystallization and Hot Carriers Behavior in Perovskite Solar Cells,” Chemical Engineering Journal 463 (2023): 142449.

[33] J. Han, S. Luo, X. Yin, et al., “Hybrid PbS Quantum-Dot-in-Perovskite for High-Efficiency Perovskite Solar Cell,” Small 14 (2018): 1801016.

[34] Q. Zhang, S. Xiong, J. Ali, et al., “Polymer Interface Engineering Enabling High-Performance Perovskite Solar Cells With Improved Fill Factors of Over 82,” Journal of Materials Chemistry C 8 (2020): 5467–5475.

[35] Z. Song, W. Xu, Y. Wu, et al., “Incorporating of Lanthanides Ions Into Perovskite Film for Efficient and Stable Perovskite Solar Cell,” Small 16 (2020): 2001770.

[36] J. Xia, Y. Zhang, C. Xiao, et al., “Tailoring Electric Dipole of Hole-Transporting Material P-Dopants for Perovskite Solar Cells,” Joule 6 (2022): 1689–1709.

[37] X. Wang, J. Wu, Y. Yang, et al., “High Performance and Stable Perovskite Solar Cells Using Vanadic Oxide as a Dopant for Spiro-OMeTAD,” Journal of Materials Chemistry A 7 (2019): 13256–13264.

[38] Z. Song, W. Xu, Y. Wu, et al., “Incorporating of Lanthanides Ions Into Perovskite Film for Efficient and Stable Perovskite Solar Cells,” Small 16 (2020): 2001770.

[39] H. Li, Y. Peng, W. Zhou, et al., “Enhancing Performance and Stability of p-i-n Perovskite Solar Cells With Ag-Cu Codeposited Alloy Electrodes,” ACS Applied Materials & Interfaces 16 (2024): 36471–36478.

[40] J. Cao, S. X. Tao, P. A. Bobbert, C.-P. Wong, and N. Zhao, “Interstitial Occupancy by Extrinsic Alkali Cations in Perovskites and Its Impact on Ion Migration,” Advanced Materials 30 (2018): 1707350.

[41] R. Wu, J. Yao, S. Wang, et al., “Ultracompact, Well-Packed Perovskite Flat Crystals: Preparation and Application in Planar Solar Cells With High Efficiency and Humidity Tolerance,” ACS Applied Materials & Interfaces 11 (2019): 11283–11291.

[42] Y. Ma, N. Wei, Q. Wang, et al., “Ultrathin PEDOT:PSS/rGO Aerogel Providing Tape-Like Self-Healable Electrode for Sensing Space Electric Field With Electrochemical Mechanism,” Advanced Electronic Materials 5 (2019): 1900637.

[43] L. Yang, Z. Fang, Y. Jin, et al., “Suppressing Halide Segregation via Pyridine-Derivative Isomers Enables Efficient 1.68 eV Bandgap Perovskite Solar Cells,” Advanced Materials 36 (2024): 2311923.

[44] J. Zheng, L. Zhu, Z. Shen, et al., “Effects of the Incorporation Amounts of CdS and Cd(SCN2H4)2Cl2 on the Performance of Perovskite Solar Cells,” International Journal of Minerals, Metallurgy, and Materials 29 (2022): 283–291.

[45] Z. H. Zheng, F. M. Li, J. Gong, et al., “Pre-Buried Additive for Cross-Layer Modification in Flexible Perovskite Solar Cells With Efficiency Exceeding 22%,” Advanced Materials 34 (2022): 2109879.

[46] X. Sun, B. He, J. Zhu, et al., “Multifunctional Brominated Graphene Oxide Boosted Charge Extraction for High-Efficiency and Stable All-Inorganic CsPbBr3 Perovskite Solar Cells,” Chemical Engineering Journal 412 (2021): 128727.

[47] X. Yu, H. He, Y. Hui, et al., “Additive Engineering for Efficient Wide-Bandgap Perovskite Solar Cells With Low Open-Circuit Voltage Losses,” Frontiers in Chemistry 12 (2024): 1441057.

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2025 The Author(s). Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.