Deprotonation of organic cations in hybrid perovskites generates nitrogen-site hydrogen vacancies that activate lone-pair electrons and induce configuration-dependent nonradiative losses. Here, we introduce a novel cyclic A-site organic cation, aziridinium, into the APbI3 perovskite lattice and establish a direct structure–function correlation between the molecular configuration of the organic cation and the lone-pair electron activity associated with nitrogen-site hydrogen vacancies defects. Compared with conventional formamidinium and methylammonium cations, the geometrically constrained, distorted coordination environment of aziridinium promotes facile deprotonation, resulting in a higher tendency for nitrogen-site hydrogen vacancies formation. The deprotonated aziridinium species exhibit markedly enhanced lone-pair electron activity, acting as strong Lewis bases that perturb the local PbI6 octahedra by detaching Pb2+ ions and forming stable Pb–AZ dimers. These defect complexes serve as highly efficient nonradiative recombination centers, yielding an ultrahigh carrier capture coefficient of 10−5 cm3 s−1. This work reveals the decisive influence of A-site cation chemistry on defect energetics and recombination kinetics, emphasizing the necessity of simultaneously optimizing iodide stoichiometry and aziridinium incorporation to suppress nonradiative losses in aziridinium-based halide perovskites.
| [1] |
W. Shockley, W. T. Read, Phys. Rev. 1952, 87, 835.
|
| [2] |
R. N. Hall, Phys. Rev. 1952, 87, 387.
|
| [3] |
J. Park, J. Kim, H.-S. Yun, M. J. Paik, E. Noh, H. J. Mun, M. G. Kim, T. J. Shin, S. I. Seok, Nature 2023, 616, 724.
|
| [4] |
Y. Zhao, F. Ma, Z. Qu, S. Yu, T. Shen, H.-X. Deng, X. Chu, X. Peng, Y. Yuan, X. Zhang, J. You, Science 2022, 377, 531.
|
| [5] |
H. Lu, Y. Liu, P. Ahlawat, A. Mishra, W. R. Tress, F. T. Eickemeyer, Y. Yang, F. Fu, Z. Wang, C. E. Avalos, B. I. Carlsen, A. Agarwalla, X. Zhang, X. Li, Y. Zhan, S. M. Zakeeruddin, L. Emsley, U. Rothlisberger, L. Zheng, A. Hagfeldt, M. Grätzel, Science 2020, 370, eabb8985.
|
| [6] |
Z. Xiong, L. Lan, Y. Wang, C. Lu, S. Qin, S. Chen, L. Zhou, C. Zhu, S. Li, L. Meng, K. Sun, Y. Li, ACS Energy Lett. 2021, 6, 3824.
|
| [7] |
D. Zhang, H. Zhang, H. Guo, F. Ye, S. Liu, Y. Wu, Adv. Funct. Mater. 2022, 32, 2200174.
|
| [8] |
X. Zhang, M. E. Turiansky, J.-X. Shen, C. G. Van De Walle, J. Appl. Phys. 2022, 131, 090901.
|
| [9] |
T. Chen, J. Xie, B. Wen, Q. Yin, R. Lin, S. Zhu, P. Gao, Nat. Commun. 2023, 14, 6125.
|
| [10] |
J. Zhang, Y. Zhong, G. Li, J. Phys. Chem. C 2021, 125, 27016.
|
| [11] |
L. Qiao, W. Fang, R. Long, O. V. Prezhdo, Angew. Chem. Int. Ed. 2020, 59, 4684.
|
| [12] |
L. D. Whalley, P. Van Gerwen, J. M. Frost, S. Kim, S. N. Hood, A. Walsh, J. Am. Chem. Soc. 2021, 143, 9123.
|
| [13] |
X. Zhang, S.-H. Wei, Phys. Rev. Lett. 2022, 128, 136401.
|
| [14] |
W. S. Yang, B.-W. Park, E. H. Jung, N. J. Jeon, Y. C. Kim, D. U. Lee, S. S. Shin, J. Seo, E. K. Kim, J. H. Noh, S. I. Seok, Science 2017, 356, 1376.
|
| [15] |
X. Liu, D. Luo, Z.-H. Lu, J. S. Yun, M. Saliba, S. I. Seok, W. Zhang, Nat. Rev. Chem. 2023, 7, 462.
|
| [16] |
Y. Wang, Y. Wang, T. A. S. Doherty, S. D. Stranks, F. Gao, D. Yang, Nat. Rev. Chem. 2025, 9, 261.
|
| [17] |
X. Zhang, J.-X. Shen, M. E. Turiansky, C. G. Van De Walle, Nat. Mater. 2021, 20, 971.
|
| [18] |
J. Han, Y. Li, P. Zhang, B. Xu, X. Xu, Z. Quan, J. Am. Chem. Soc. 2025, 147, 1291.
|
| [19] |
K. Bu, X. Feng, D. Wang, T. Fu, Y. Ma, S. Guo, H. Luo, Y. Ding, T. Zhai, X. Lü, J. Am. Chem. Soc. 2024, 146, 22469.
|
| [20] |
Y. Liang, X. Cui, F. Li, C. Stampfl, S. P. Ringer, J. Huang, R. Zheng, J. Am. Chem. Soc. 2022, 144, 6770.
|
| [21] |
D. R. Ceratti, A. Zohar, R. Kozlov, H. Dong, G. Uraltsev, O. Girshevitz, I. Pinkas, L. Avram, G. Hodes, D. Cahen, Adv. Mater. 2020, 32, 2002467.
|
| [22] |
W. Zhou, X. Yang, R. Zhou, H. Huang, Y. He, X. Chen, C. Qian, Z. Zheng, H. Yan, Angew. Chem. Int. Ed. 2025, 64, e202503394.
|
| [23] |
H. R. Petrosova, O. I. Kucheriv, S. Shova, I. A. Gural'skiy, Chem. Commun. 2022, 58, 5745.
|
| [24] |
M. I. Bodnarchuk, L. G. Feld, C. Zhu, S. C. Boehme, F. Bertolotti, J. Avaro, M. Aebli, S. H. Mir, N. Masciocchi, R. Erni, S. Chakraborty, A. Guagliardi, G. Rainò, M. V. Kovalenko, ACS Nano 2024, 18, 5684.
|
| [25] |
S. Li, J. Han, Y. Li, W. Liao, J. Rare Earths 2025, 43, 1720.
|
| [26] |
J. Xu, A. Maxwell, Z. Song, A. S. R. Bati, H. Chen, C. Li, S. M. Park, Y. Yan, B. Chen, E. H. Sargent, Nat. Commun. 2024, 15, 2035.
|
| [27] |
W. Zhou, R. Zhou, X. Chen, Z. Zhou, Y. He, C. Qian, H. Yan, Z. Zheng, Y. Zhang, H. Yan, Small 2024, 20, 2405201.
|
| [28] |
C. Zheng, O. Rubel, J. Phys. Chem. C 2017, 121, 11977.
|
| [29] |
C. Zheng, O. Rubel, J. Phys. Chem. Lett. 2018, 9, 874.
|
| [30] |
O. A. Semenikhin, O. I. Kucheriv, L. Sacarescu, S. Shova, I. A. Gural'skiy, Chem. Commun. 2023, 59, 3566.
|
| [31] |
D. Stefańska, M. Ptak, M. Mączka, Molecules 2022, 27, 7949.
|
| [32] |
Q. Teng, T. Shi, Y. Zhao, ChemPhysChem 2019, 20, 602.
|
| [33] |
O. I. Kucheriv, V. Y. Sirenko, H. R. Petrosova, V. A. Pavlenko, S. Shova, I. A. Gural'skiy, Inorg. Chem. Front. 2023, 10, 6953.
|
| [34] |
B. M. Weckhuysen, S. Kitagawa, M. Tsapatsis, ChemPhysChem 2018, 19, 339.
|
| [35] |
Q. Ji, Y. Wu, X. Gao, T. Zhang, Y. Zhou, Y. Zhang, M. Ju, J. Wang, X. C. Zeng, Angew. Chem. Int. Ed. 2023, 62, e202213386.
|
| [36] |
S. Nosé, J. Chem. Phys. 1984, 81, 511.
|
| [37] |
W. G. Hoover, Phys. Rev. A 1985, 31, 1695.
|
| [38] |
J. Shamsi, A. S. Urban, M. Imran, L. De Trizio, L. Manna, Chem. Rev. 2019, 119, 3296.
|
| [39] |
Q. Wei, Y. Ke, Z. Ning, Energy Environ. Mater. 2020, 3, 541.
|
| [40] |
C. Freysoldt, B. Grabowski, T. Hickel, J. Neugebauer, G. Kresse, A. Janotti, C. G. Van De Walle, Rev. Mod. Phys. 2014, 86, 253.
|
| [41] |
Q. Shi, T. Pullerits, Energy Environ. Mater. 2025, 8, e70062.
|
| [42] |
D. Luo, R. Su, W. Zhang, Q. Gong, R. Zhu, Nat. Rev. Mater. 2019, 5, 44.
|
| [43] |
R. Pässler, Czech. J. Phys. B 1974, 24, 322.
|
| [44] |
X. Zhang, M. E. Turiansky, J.-X. Shen, C. G. Van De Walle, Phys. Rev. B 2020, 101, 140101.
|
| [45] |
K. Huang, Contemp. Phys. 1981, 22, 599.
|
| [46] |
J. Zhou, S. Wang, M. Huang, X.-G. Gong, S. Chen, Phys. Rev. B 2025, 111, 115202.
|
| [47] |
Q. Ji, Q. Fang, X. Wei, Y. Zhang, Y. Wu, X. Gao, X. Li, C. Ning, M.-G. Ju, Nano Lett. 2025, 25, 5875.
|
| [48] |
W. Chu, Q. Zheng, O. V. Prezhdo, J. Zhao, W. A. Saidi, Sci. Adv. 2020, 6, eaaw7453.
|
| [49] |
G. Kresse, D. Joubert, Phys. Rev. B 1999, 59, 1758.
|
| [50] |
G. Kresse, J. Furthmüller, Phys. Rev. B 1996, 54, 11169.
|
| [51] |
J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.
|
| [52] |
S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 2010, 132, 154104.
|
| [53] |
W. Reckien, F. Janetzko, M. F. Peintinger, T. Bredow, J. Comput. Chem. 2012, 33, 2023.
|
| [54] |
J. Heyd, G. E. Scuseria, M. Ernzerhof, J. Chem. Phys. 2003, 118, 8207.
|
| [55] |
W.-T. Geng, Y.-C. Liu, N. Xu, G. Tang, Y. Kawazoe, V. Wang, Nat. Protoc. 2025, 20, 3143.
|
| [56] |
A. M. Ganose, A. J. Jackson, D. O. Scanlon, J. Open Source Softw. 2018, 3, 717.
|
| [57] |
Y. Kumagai, F. Oba, Phys. Rev. B 2014, 89, 195205.
|
| [58] |
A. Stoliaroff, S. Jobic, C. Latouche, J. Comput. Chem. 2018, 39, 2251.
|
| [59] |
A. Alkauskas, Q. Yan, C. G. Van De Walle, Phys. Rev. B 2014, 90, 075202.
|
| [60] |
M. E. Turiansky, A. Alkauskas, M. Engel, G. Kresse, D. Wickramaratne, J.-X. Shen, C. E. Dreyer, C. G. Van De Walle, Comput. Phys. Commun. 2021, 267, 108056.
|
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