Metastable alloying structures in MAPbI3−xClx crystals
Source abstract
Abstract
Abstract Chlorine incorporation engineering has been widely used in optoelectronic devices based on methylammonium lead iodide (MAPbI3) perovskites. However, the characteristics of I/Cl alloying structures in MAPbI3−xClx mixed-halide perovskites and their influences on the optoelectronic properties have been issues of a long-standing controversy. Here, we present a detailed study of the I/Cl alloying structures in MAPbI3−xClx (x = 0.0 to 0.3) single crystals. We found that a small amount of Cl can substitute for the iodide of the PbI3 inorganic lattice, leading to a phase transition from the tetragonal to cubic phase and anomalous cation dynamics evolution. Analyses based on time-dependent X-ray diffraction, 207Pb NMR, and 2H NMR indicate that the alloying structures of the MAPbI3−xClx crystals are metastable and decompose over time. In addition, the photocurrent response measurement of MAPbI3−xClx proved a close correlation between the alloying structures and photoelectric properties of the material. This work sheds light on the essential understanding of the I/Cl alloying structure and provides a plausible explanation for the controversy regarding the role of chloride ions in optoelectronic devices.
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Research context
OpenAlex topics: Perovskite Materials and Applications · Solid-state spectroscopy and crystallography · Quantum Dots Synthesis And Properties
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References (44)
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1. Green, M. A., Ho-Baillie, A. & Snaith, H. J. The emergence of perovskite solar cells. Nat. Photonics 8, 506 (2014).10.1038/nphoton.2014.134 ↗
2. Park, N.-G. Perovskite solar cells: an emerging photovoltaic technology. Mater. Today 18, 65–72 (2015).10.1016/j.mattod.2014.07.007 ↗
3. Jiang, Q. et al. Surface passivation of perovskite film for efficient solar cells. Nat. Photonics 13, 460–466 (2019).10.1038/s41566-019-0398-2 ↗
4. Dou, L. et al. Solution-processed hybrid perovskite photodetectors with high detectivity. Nat. Commun. 5, 1–6 (2014).
5. Lin, K. et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature 562, 245–248 (2018).10.1038/s41586-018-0575-3 ↗
6. Chin, X. Y., Cortecchia, D., Yin, J., Bruno, A. & Soci, C. Lead iodide perovskite light-emitting field-effect transistor. Nat. Commun. 6, 7383 (2015).
7. Zhu, H. et al. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors. Nat. Mater. 14, 636–642 (2015).10.1038/nmat4271 ↗
8. Saidaminov, M. I. et al. High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization. Nat. Commun. 6, 7586 (2015).
9. Dong, Q. et al. Electron-hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals. Science 347, 967–970 (2015).10.1126/science.aaa5760 ↗
10. Shi, D. et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347, 519–522 (2015).10.1126/science.aaa2725 ↗
11. Tsai, H. et al. Light-induced lattice expansion leads to high-efficiency perovskite solar cells. Science 360, 67–70 (2018).10.1126/science.aap8671 ↗
12. Akkerman, Q. A. et al. Fully inorganic ruddlesden–popper double Cl–I and triple Cl–Br–I lead halide perovskite nanocrystals. Chem. Mater. 31, 2182–2190 (2019).10.1021/acs.chemmater.9b00489 ↗
13. Colella, S. et al. MAPbI3-xCl x mixed halide perovskite for hybrid solar cells: the role of chloride as dopant on the transport and structural properties. Chem. Mater. 25, 4613–4618 (2013).10.1021/cm402919x ↗
14. Zhang, M. et al. Composition-dependent photoluminescence intensity and prolonged recombination lifetime of perovskite CH3NH3PbBr3−x Clx films. Chem. Commun. 50, 11727–11730 (2014).10.1039/C4CC04973J ↗
15. Wang, Y. et al. Fully-ambient-processed mesoscopic semitransparent perovskite solar cells by islands-structure-MAPbI3-xClx-NiO composite and Al2O3/NiO interface engineering. Nano Energy 49, 59–66 (2018).10.1016/j.nanoen.2018.04.036 ↗
16. Huang, J., Wang, M., Ding, L., Deng, J. & Yao, X. Efficiency enhancement of the MAPbI3− xClx-based perovskite solar cell by a two-step annealing procedure. Semiconductor Sci. Technol. 31, 025009 (2015).10.1088/0268-1242/31/2/025009 ↗
17. Long, M. et al. Large‐grain formamidinium PbI3–xBrx for high‐performance perovskite solar cells via intermediate halide exchange. Adv. Energy Mater. 7, 1601882 (2017).10.1002/aenm.201601882 ↗
18. Heo, J. H., Lee, S.-C., Jung, S.-K., Kwon, O.-P. & Im, S. H. Efficient and thermally stable inverted perovskite solar cells by introduction of non-fullerene electron transporting materials. J. Mater. Chem. A 5, 20615–20622 (2017).10.1039/C7TA06900F ↗
19. Chen, Q. et al. The optoelectronic role of chlorine in CH3NH3PbI3(Cl)-based perovskite solar cells. Nat. Commun. 6, 7269 (2015).
20. Lian, Z. et al. Perovskite CH3NH3PbI3 (Cl) single crystals: rapid solution growth, unparalleled crystalline quality, and low trap density toward 108 cm–3. J. Am. Chem. Soc. 138, 9409–9412 (2016).10.1021/jacs.6b05683 ↗
21. Fan, L. et al. Elucidating the role of chlorine in perovskite solar cells. J. Mater. Chem. A 5, 7423–7432 (2017).10.1039/C7TA00973A ↗
22. Zhang, H. et al. Controlled substitution of chlorine for iodine in single‐crystal nanofibers of mixed perovskite MAPbI3–xClx. Small 12, 3780–3787 (2016).10.1002/smll.201601201 ↗
23. Zhang, C. et al. MAPbCl3-mediated decomposition process to tune Cl/PbI2 distribution in MAPbI3 films. ACS Energy Lett. 3, 1801–1807 (2018).10.1021/acsenergylett.8b00837 ↗
24. Min, H. et al. Efficient, stable solar cells by using inherent bandgap of α-phase formamidinium lead iodide. Science 366, 749–753 (2019).10.1126/science.aay7044 ↗
25. Liu, J. & Prezhdo, O. V. Chlorine doping reduces electron–hole recombination in lead iodide perovskites: time-domain ab initio analysis. J. Phys. Chem. Lett. 6, 4463–4469 (2015).10.1021/acs.jpclett.5b02355 ↗
26. Quarti, C., Mosconi, E., Umari, P. & De Angelis, F. Chlorine incorporation in the CH3NH3PbI3 perovskite: small concentration, big effect. Inorg. Chem. 56, 74–83 (2017).10.1021/acs.inorgchem.6b01681 ↗
27. Saidaminov, M. I. et al. High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization. Nat. Commun. 6, 1–6 (2015).
28. Liu, Y. et al. Two‐inch‐sized perovskite CH3NH3PbX3 (X=Cl, Br, I) crystals: growth and characterization. Adv. Mater. 27, 5176–5183 (2015).10.1002/adma.201502597 ↗
29. Li, B., Isikgor, F. H., Coskun, H. & Ouyang, J. The effect of methylammonium iodide on the supersaturation and interfacial energy of the crystallization of methylammonium lead triiodide single crystals. Angew. Chem. Int. Ed. 56, 16073–16076 (2017).10.1002/anie.201710234 ↗
30. Baikie, T. et al. Synthesis and crystal chemistry of the hybrid perovskite (CH3 NH3) Pbl3 for solid-state sensitised solar cell applications. J. Mater. Chem. A 1, 5628–5641 (2013).10.1039/c3ta10518k ↗
31. Wang, Q. et al. Transition from the tetragonal to cubic phase of organohalide perovskite: the role of chlorine in crystal formation of CH3NH3PbI3 on TiO2 substrates. J. Phys. Chem. Lett. 6, 4379–4384 (2015).10.1021/acs.jpclett.5b01682 ↗
32. Rosales, B. A. et al. Persistent dopants and phase segregation in organolead mixed-halide perovskites. Chem. Mater. 28, 6848–6859 (2016).10.1021/acs.chemmater.6b01874 ↗
33. Askar, A. M. et al. Composition-tunable formamidinium lead mixed halide perovskites via solvent-free mechanochemical synthesis: decoding the Pb environments using solid-state NMR spectroscopy. J. Phys. Chem. Lett. 9, 2671–2677 (2018).10.1021/acs.jpclett.8b01084 ↗
34. Bernard, G. M. et al. Methylammonium cation dynamics in methylammonium lead halide perovskites: a solid-state NMR perspective. J. Phys. Chem. A 122, 1560–1573 (2018).10.1021/acs.jpca.7b11558 ↗
35. Fabini, D. H. et al. Universal dynamics of molecular reorientation in hybrid lead iodide perovskites. J. Am. Chem. Soc. 139, 16875–16884 (2017).10.1021/jacs.7b09536 ↗
36. Wang, J. et al. A small lattice change induces significant dynamic changes of CH3NH3+ caged in hybrid perovskite crystals: toward understanding the interplay between host lattices and guest molecules. Inorg. Chem. 58, 7426–7432 (2019).10.1021/acs.inorgchem.9b00497 ↗
37. Franssen, W. M., van Es, S. G., Dervişoğlu, R., de Wijs, G. A. & Kentgens, A. P. Symmetry, dynamics, and defects in methylammonium lead halide perovskites. J. Phys. Chem. Lett. 8, 61–66 (2017).10.1021/acs.jpclett.6b02542 ↗
38. Kubicki, D. J. et al. Cation dynamics in mixed-cation (MA) x (FA) 1–x PbI3 hybrid perovskites from solid-state NMR. J. Am. Chem. Soc. 139, 10055–10061 (2017).10.1021/jacs.7b04930 ↗
39. Kim, M. et al. Methylammonium chloride induces intermediate phase stabilization for efficient perovskite solar cells. Joule 3, 2179–2192 (2019).10.1016/j.joule.2019.06.014 ↗
40. Walsh, A., Scanlon, D. O., Chen, S., Gong, X. & Wei, S. H. Self‐regulation mechanism for charged point defects in hybrid halide perovskites. Angew. Chem. Int. Ed. 54, 1791–1794 (2015).10.1002/anie.201409740 ↗
41. Christians, J. A., Habisreutinger, S. N., Berry, J. J. & Luther, J. M. Stability in perovskite photovoltaics: a paradigm for newfangled technologies. ACS Energy Lett. 3, 2136–2143 (2018).10.1021/acsenergylett.8b00914 ↗
42. Brennan, M. C. et al. Superlattices are greener on the other side: how light transforms self-assembled mixed halide perovskite nanocrystals. ACS Energy Lett. 5, 1465–1473 (2020).10.1021/acsenergylett.0c00630 ↗
43. Brennan, M. C., Ruth, A., Kamat, P. V. & Kuno, M. Photoinduced anion segregation in mixed halide perovskites. Trends Chem. 2, https://doi.org/10.1016/j.trechm.2020.01.010 (2020).10.1016/j.trechm.2020.01.010 ↗
44. Draguta, S. et al. Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites. Nat. Commun. 8, 1–8 (2017).10.1038/s41467-017-00284-2 ↗