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Analysis on the defect states of FAxMA1−xPbI3 perovskite single crystals grown by inverse-temperature crystallization

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Abstract

The FA0.6MA0.4PbI3, FA0.8MA0.2PbI3 and FAPbI3 perovskite single crystals were prepared by the inverse temperature crystallization method. From the deep level transient spectroscopy (DLTS) measurement and optical conduction DLTS, the FA0.6MA0.4PbI3 and FA0.8MA0.2PbI3 samples had the majority carrier defects of E2 and E3 with Ea of 0.52 and 0.59 eV, which were positioned below the conduction band minimum, and the FAPbI3 sample had the minority carrier defect of H2 with Ea of 0.60 eV above the valence band maximum. The origin of the defect states of E2, E3 and H2 are related to FA-I antisite defects, Pb interstitial defects and iodine vacancy, respectively. Among the samples, the defect density (Nt) of H2 on FAPbI3 was lower than that of any other sample, although the normalized integrated photoluminescence intensity of the FA0.8MA0.2PbI3 sample was higher than that of any other sample. This is due to the fact that H2 was a minority carrier defect and E2 and E3 were majority carrier defects.

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References

  1. F.O. Saouma, D.Y. Park, S.H. Kim, M.S. Jeong, J.I. Jang, Multiphoton absorption coefficients of organic-inorganic lead halide perovskites CH3NH3PbX3 (X = Cl, Br, I) single crystals. Chem. Mater. 29, 6876–6882 (2017)

    Article  Google Scholar 

  2. H. Nagaoka, F. Ma, D.W. de Quilettes, S.M. Vorpahl, M.S. Glaz, A.E. Colbert, M.E. Ziffer, D.S. Ginge, Zr incorporation into TiO2 electrodes reduces hysteresis and improves performance in hybrid perovskite solar cells while increasing carrier lifetimes. J. Phys. Chem. Lett. 6, 669–675 (2015)

    Article  Google Scholar 

  3. Y. Jiang, E.J. Juarez-Perez, Q. Ge, S. Wang, M.R. Leyden, L.K. Ono, S.R. Raga, J. Hu, Y. Qi, Post-annealing of MAPbI3 perovskite films with methylamine for efficient perovskite solar cells. Mater. Horiz. 3, 548–555 (2016)

    Article  Google Scholar 

  4. C. Qin, T. Matsushima, D. Klotz, T. Fujihara, C. Adachi, The relation of phase-transition effects and thermal stability of planar perovskite solar cells. Adv. Sci. 6, 1801079 (2019)

    Article  Google Scholar 

  5. M.N.F. Hoque, N. Islam, Z. Li, G. Ren, K. Zhu, Z. Fan, Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal-Cubic Structural Phase Transition. Chem. Sus. Chem. 9, 2692–2698 (2016)

    Article  Google Scholar 

  6. S. Jiang, Y. Luan, J.I. Jang, T. Baikie, X. Huang, R. Li, F.O. Saouma, Z. Wang, T.J. White, J. Fang, Phase Transitions of Formamidinium Lead Iodide Perovskite under Pressure. J. Am. Chem. Soc. 140, 13952–13957 (2018)

    Article  Google Scholar 

  7. O.J. Weber, B. Charles, M.T. Weller, Phase behaviour and composition in the formamidinium–methylammonium hybrid lead iodide perovskite solid solution. J. Mater. Chem. A 4, 15375–15382 (2016)

    Article  Google Scholar 

  8. A.F. López, B. Charles, M.I. Alonso, M. Garriga, M.C. Quiles, M.T. Weller, A.R. Goñi, Phase Diagram of Methylammonium/Formamidinium Lead Iodide Perovskite Solid Solutions from Temperature-Dependent Photoluminescence and Raman Spectroscopies. J. Phys. Chem. C 124, 3448–3458 (2020)

    Article  Google Scholar 

  9. E. Aydin, M.D. Bastiani, S.D. Wolf, Defect and Contact Passivation for Perovskite Solar Cells. Adv. Mater. 31, 1900428 (2019)

    Article  Google Scholar 

  10. J. Wang, W.J. Yin, Revisiting the iodine vacancy surface defects to rationalize passivation strategies in perovskite solar cells. J. Phys. Chem. Lett. 13, 6694–6700 (2022)

    Article  Google Scholar 

  11. A. Mohanty, D. Swain, S. Govinda, T.N.G. Row, D.D. Sarma, Phase diagram and dielectric properties of MA1−xFAxPbI3. ACS Energy Lett. 4, 2045–2051 (2019)

    Article  Google Scholar 

  12. H. Kim, H.R. Byun, M.S. Jeong, Synthesis and Characterization of Multiple-Cation Rb(MAFA)PbI3 Perovskite Single Crystals. Sci. Rep. 9, 2022 (2019)

    Article  ADS  Google Scholar 

  13. S. Du, L. Jing, X. Cheng, Y. Yuan, J. Ding, T. Zhou, X. Zhan, H. Cui, Incorporation of cesium ions into MA1−xCsxPbI3 single crystals: crystal growth, enhancement of stability, and optoelectronic properties. J. Phys. Chem. Lett. 9, 5833–5839 (2018)

    Article  Google Scholar 

  14. K. Wang, Q. Yao, J. Zhang, L. Jing, X. Cheng, C. Shang, C. Li, F. Chen, T. Zhou, H. Zhu, T. Li, H. Li, Z. Wang, J. Ding, How ternary cations and binary halogens stabilize trigonal FA1−x−yMAxCsyPbI3−zBrz perovskites: from a single crystal perspective. Chem. Mater. 34, 1179–1190 (2022)

    Article  Google Scholar 

  15. L. Li, M. Su, X. Qiu, X. Zhao, X. Zhu, W. Wei, L. Huang, G. Li, Y. Wang, W.H. Sun, Lattice relaxation effect in CsxMA(1–x)PbBr 3 single crystal to enhance optoelectronic performance of perovskite photodetectors. Ceram. Int. 48, 436–445 (2022)

    Article  Google Scholar 

  16. N. Liu, C. Yam, First-principles study of intrinsic defects in formamidinium lead triiodide perovskite solar cell absorbers. Phys. Chem. Chem. Phys. 20, 6800–6804 (2018)

    Article  Google Scholar 

  17. W.J. Yin, T. Shi, Y. Yan, Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl. Phys. Lett. 104, 063903 (2014)

    Article  ADS  Google Scholar 

  18. D. Meggiolaro, S.G. Motti, E. Mosconi, A.J. Barker, J. Ball, C.A.R. Perini, F. Deschler, A. Petrozza, F.D. Angelis, Iodine chemistry determines the defect tolerance of lead-halide perovskites. Energy Environ. Sci. 11, 702–713 (2018)

    Article  Google Scholar 

  19. A.F. López, B. Charles, M.I. Alonso, M. Garriga, M.T. Weller, A.R. Goñi, Photoluminescence of Bound-Exciton Complexes and Assignment to Shallow Defects in Methylammonium/Formamidinium Lead Iodide Mixed Crystals. Adv. Optical Mater. 9, 2001969 (2021)

    Article  Google Scholar 

  20. Z. Ni, H. Jiao, C. Fei, H. Gu, S. Xu, Z. Yu, G. Yang, Y. Deng, Q. Jiang, Y. Liu, Y. Yan, J. Huang, Evolution of defects during the degradation of metal halide perovskite solar cells under reverse bias and illumination. Nat. Energy 7, 65–73 (2022)

    Article  ADS  Google Scholar 

  21. L. Duan, A. Uddin, Defects and stability of perovskite solar cells: a critical analysis. Mater. Chem. Front. 6, 400–417 (2022)

    Article  Google Scholar 

  22. Y. Chen, H. Zhou, Defects chemistry in high-efficiency and stable perovskite solar cells. J. Appl. Phys. 128, 060903 (2020)

    Article  ADS  Google Scholar 

  23. T. Wu, J. Li, Y. Zou, H. Xu, K. Wen, S. Wan, S. Bai, T. Song, J.A. McLeod, S. Duhm, F. Gao, B. Sun, High-Performance Perovskite Light-Emitting Diode with Enhanced Operational Stability Using Lithium Halide Passivation. Angew. Chem. Int. Ed. 59, 4099–4105 (2020)

    Article  Google Scholar 

  24. G. Maculan, A.D. Sheikh, A.L. Abdelhady, M.I. Saidaminov, M.A. Haque, B. Murali, E. Alarousu, O.F. Mohammed, T. Wu, O.M. Bakr, CH3NH3PbCl3 single crystals: inverse temperature crystallization and visible-blind UV-photodetector. J. Phys. Chem. Lett. 6, 3781–3786 (2015)

    Article  Google Scholar 

  25. S. Rong, Y. Xiao, J. Jiang, Q. Zeng, Y. Li, Strongly enhanced PL and photoconductivity in erbium-doped MAPbBr 3 single crystals. J. Phys. Chem. C 124, 8992–8998 (2020)

    Article  Google Scholar 

  26. L. Chen, H. Wang, W. Zhang, F. Li, Z. Wang, X. Wang, Y. Shao, J. Shao, Surface passivation of MAPbBr 3 perovskite single crystals to suppress ion migration and enhance photoelectronic performance. ACS Appl. Mater. Interfaces 14, 10917–10926 (2022)

    Article  Google Scholar 

  27. M. I. Alonso, B. Charles, A. F. López, M. Garriga, M. T. Weller, A. R. Goñi1, Spectroscopic ellipsometry study of FAxMA1−xPbI3 hybrid perovskite single crystals. J. Vac. Sci. Technol. B 37, 062901 (2019)

  28. T.K.O. Vu, D.U. Lee, K.S. Lee, D.Y. Park, M.S. Jeong, E.K. Kim, Defect states of organic lead halide single crystals grown by inverse-temperature crystallization. Appl. Phys. Lett. 115, 153302 (2019)

    Article  ADS  Google Scholar 

  29. G. Murugadoss, P. Arunachalam, S.K. Panda, M.R. Kumar, J.R. Rajabathar, H.A. Lohedan, M.D. Wasmiah, Crystal stabilization of α-FAPbI3 perovskite by rapid annealing method in industrial scale. J. Mater. Res. Technol. 12, 1924–1930 (2021)

    Article  Google Scholar 

  30. T.J. Jacobsson, J.P.C. Baena, M. Pazoki, M. Saliba, K. Schenk, M. Grätzel, A. Hagfeldt, Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells. Energy Environ. Sci. 9, 1706–1724 (2016)

    Article  Google Scholar 

  31. X. Xu, X. Yu, J. Yang, T. Ying, X. Cui, Y. Jing, G. Lv, Z. Liu, W. Li, X. Li, To define nonradiative defects in semiconductors: An accurate DLTS simulation based on first-principle. Comput. Mater. Sci. 215, 111760 (2022)

    Article  Google Scholar 

  32. Y. Tokumaru, H. Okushi, DLTS Measurement on Au-Doped Si p+n Junctions and Its Computer Simulation. Jpn. J. Appl. Phys. 19, 2441–2449 (1980)

    Article  ADS  Google Scholar 

  33. E.K. Kim, H.Y. Cho, S.K. Min, S.H. Choh, S. Namba, Effects of leakage current on isothermal capacitance transient spectroscopy signals for midgap levels in GaAs. J. Appl. Phys. 6, 1380–1383 (1990)

    Article  ADS  Google Scholar 

  34. K. Dmowski, B. Lepley, E. Losson, M.E. Bouabdellati, A method to correct for leakage current effects in deep level transient spectroscopy measurements on Schottky diodes. J. Appl. Phys. 74, 3936–3943 (1993)

    Article  ADS  Google Scholar 

  35. M.C. Chen, D.V. Lang, W.C.D. Smith, A.M. Sergent, J.P. Harbison, Effects of leakage current on deep level transient spectroscopy. Appl. Phys. Lett. 44, 790–792 (1984)

    Article  ADS  Google Scholar 

  36. T.K.O. Vu, Y.H. Kim, C.W. Ahn, M.H. Kim, I.K. Han, E.K. Kim, Optimization of optoelectrical properties during synthesizing methylammonium lead iodide perovskites via a two-step dry process. J. Mater. Res. Technol. 14, 1–9 (2021)

    Article  Google Scholar 

  37. X. Ren, B. Zhang, L. Zhang, J. Wen, B. Che, D. Bai, J. You, T. Chen, S. Liu, Deep-Level Transient Spectroscopy for Effective Passivator Selection in Perovskite Solar Cells to Attain High Efficiency over 23%. Chemsuschem 14, 3182–3189 (2021)

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2021R1A2C1093652, 2022M3I8A2085434, 2022R1A2C2091945, 2021R1I1A1A01060493).

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  1. Kyoung Su Lee and Dae Young Park contributed equally to this work.

Authors and Affiliations

  1. Department of Physics and Research Institute of Natural Sciences, Hanyang University, Seoul, 04763, Republic of Korea

    Kyoung Su Lee & Eun Kyu Kim

  2. Department of Physics and Department of Energy Engineering, Hanyang University, Seoul, 04763, Republic of Korea

    Dae Young Park & Mun Seok Jeong

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KSL: writing—original draft preparation, carrying out measurements; DYP: Formal analysis and investigation, methodology; MSJ: supervision, funding acquisition; EKK: supervision, review and editing, funding acquisition.

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Correspondence to Mun Seok Jeong or Eun Kyu Kim.

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Lee, K.S., Park, D.Y., Jeong, M.S. et al. Analysis on the defect states of FAxMA1−xPbI3 perovskite single crystals grown by inverse-temperature crystallization. Appl. Phys. A 130, 393 (2024). https://doi.org/10.1007/s00339-024-07564-x

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