AI Chat Paper
Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Luminescent metal halides doped with ns2-metal ions such as 6s2-metal Bi3+ have aroused reviving interest owing to their outstanding optical properties; however, the origin of the photoluminescence (PL) remains controversial and unclear. Herein, we report a strategy for the controlled synthesis of Bi3+-doped vacancy-ordered double perovskite Cs2SnCl6 nanocrystals (NCs) and unravel the triplet excited-state dynamics of Bi3+ through temperature-dependent PL and ultrafast femtosecond transient absorption spectroscopies. Owing to the aliovalent Bi3+ doping in the spatially confined zero-dimensional (0D) structure of Cs2SnCl6, Bi3+ ions experience an enhancive Jahn-Teller distortion in the excited state, which results in intense broadband blue PL originating from the inter-configurational 3P0,1 → 1S0 transitions of Bi3+ at 450 nm, with a large Stokes shift and a quantum yield of 35.2%. Specifically, an unusual thermal-enhanced Jahn-Teller splitting of the excitation band and a remarkable transition of the PL lifetime from ms at 10 K to μs at 300 K were observed, as solid evidence for the isolated Bi3+ emission. These findings clarify the controversy about the PL origin in ns2-metal ion-doped lead-free luminescent metal halides, thereby paving the way for exploring their optoelectronic applications.
Maughan, A. E.; Ganose, A. M.; Bordelon, M. M.; Miller, E. M.; Scanlon, D. O.; Neilson, J. R. Defect tolerance to intolerance in the vacancy-ordered double perovskite semiconductors Cs2SnI6 and Cs2TeI6. J. Am. Chem. Soc. 2016, 138, 8453–8464.
Zhou, L.; Liao, J. F.; Huang, Z. G.; Wang, X. D.; Xu, Y. F.; Chen, H. Y.; Kuang, D. B.; Su, C. Y. All-inorganic lead-free Cs2PdX6 (X = Br, I) perovskite nanocrystals with single unit cell thickness and high stability. ACS Energy Lett. 2018, 3, 2613–2619.
Chen, M.; Ju, M. G.; Carl, A. D.; Zong, Y. X.; Grimm, R. L.; Gu, J. J.; Zeng, X. C.; Zhou, Y. Y.; Padture, N. P. Cesium titanium(IV) bromide thin films based stable lead-free perovskite solar cells. Joule 2018, 2, 558–570.
Wang, X. D.; Huang, Y. H.; Liao, J. F.; Jiang, Y.; Zhou, L.; Zhang, X. Y.; Chen, H. Y.; Kuang, D. B. In situ construction of a Cs2SnI6 perovskite nanocrystal/SnS2 nanosheet heterojunction with boosted interfacial charge transfer. J. Am. Chem. Soc. 2019, 141, 13434–13441.
Folgueras, M. C.; Louisia, S.; Jin, J. B.; Gao, M. Y.; Du, A.; Fakra, S. C.; Zhang, R.; Seeler, F.; Schierle-Arndt, K.; Yang, P. D. Ligand-free processable perovskite semiconductor ink. Nano Lett. 2021, 21, 8856–8862.
Vishnoi, P.; Zuo, J. L.; Cooley, J. A.; Kautzsch, L.; Gómez-Torres, A.; Murillo, J.; Fortier, S.; Wilson, S. D.; Seshadri, R.; Cheetham, A. K. Chemical control of spin-orbit coupling and charge transfer in vacancy-ordered ruthenium(IV) halide perovskites. Angew. Chem., Int. Ed. 2021, 60, 5184–5188.
Lee, B.; Stoumpos, C. C.; Zhou, N. J.; Hao, F.; Malliakas, C.; Yeh, C. Y.; Marks, T. J.; Kanatzidis, M. G.; Chang, R. P. H. Air-stable molecular semiconducting iodosalts for solar cell applications: Cs2SnI6 as a hole conductor. J. Am. Chem. Soc. 2014, 136, 15379–15385.
Shin, H.; Kim, B. M.; Jang, T.; Kim, K. M.; Roh, D. H.; Nam, J. S.; Kim, J. S.; Kim, U. Y.; Lee, B.; Pang, Y. et al. Surface state-mediated charge transfer of Cs2SnI6 and its application in dye-sensitized solar cells. Adv. Energy Mater. 2019, 9, 1803243.
Xuan, T. T.; Xie, R. J. Recent processes on light-emitting lead-free metal halide perovskites. Chem. Eng. J. 2020, 393, 124757.
Yin, H.; Chen, J. S.; Guan, P.; Zheng, D. Y.; Kong, Q. K.; Yang, S. Q.; Zhou, P. W.; Yang, B.; Pullerits, T.; Han, K. L. Controlling photoluminescence and photocatalysis activities in lead-free Cs2PtxSn1-xCl6 perovskites via ion substitution. Angew. Chem., Int. Ed. 2021, 60, 22693–22699.
Tang, H. D.; Xu, Y. Q.; Hu, X. B.; Hu, Q.; Chen, T.; Jiang, W. H.; Wang, L. J.; Jiang, W. Lead-free halide double perovskite nanocrystals for light-emitting applications: Strategies for boosting efficiency and stability. Adv. Sci. 2021, 8, 2004118.
Vázquez-Fernández, I.; Mariotti, S.; Hutter, O. S.; Birkett, M.; Veal, T. D.; Hobson, T. D. C.; Phillips, L. J.; Danos, L.; Nayak, P. K.; Snaith, H. J. et al. Vacancy-ordered double perovskite Cs2TeI6 thin films for optoelectronics. Chem. Mater. 2020, 32, 6676–6684.
Peng, H. P.; Xu, L. Y.; Sheng, Y. L.; Sun, W. M.; Yang, Y.; Deng, H. H.; Chen, W.; Liu, J. W. Highly conductive ligand-free Cs2PtBr6 perovskite nanocrystals with a narrow bandgap and efficient photoelectrochemical performance. Small 2021, 17, 2102149.
Zhao, P.; Su, J.; Guo, Y. J.; Wang, L.; Lin, Z. H.; Hao, Y.; Ouyang, X. P.; Chang, J. J. Cs2TiI6: A potential lead-free all-inorganic perovskite material for ultrahigh-performance photovoltaic cells and alpha-particle detection. Nano Res. 2022, 15, 2694–2705.
Saparov, B.; Sun, J. P.; Meng, W. W.; Xiao, Z. W.; Duan, H. S.; Gunawan, O.; Shin, D.; Hill, I. G.; Yan, Y. F.; Mitzi, D. B. Thin-film deposition and characterization of a sn-deficient perovskite derivative Cs2SnI6. Chem. Mater. 2016, 28, 2315–2322.
Maughan, A. E.; Ganose, A. M.; Scanlon, D. O.; Neilson, J. R. Perspectives and design principles of vacancy-ordered double perovskite halide semiconductors. Chem. Mater. 2019, 31, 1184–1195.
Han, X.; Liang, J.; Yang, J. H.; Soni, K.; Fang, Q. Y.; Wang, W. P.; Zhang, J.; Jia, S.; Martí, A. A.; Zhao, Y. et al. Lead-free double perovskite Cs2SnX6: Facile solution synthesis and excellent stability. Small 2019, 15, 1901650.
Li, M. Z.; Xia, Z. G. Recent progress of zero-dimensional luminescent metal halides. Chem. Soc. Rev. 2021, 50, 2626–2662.
Liu, S. P.; Yang, B.; Chen, J. S.; Zheng, D. Y.; Tang, Z.; Deng, W. Q.; Han, K. L. Colloidal synthesis and tunable multicolor emission of vacancy-ordered Cs2HfCl6 perovskite nanocrystals. Laser Photonics Rev. 2022, 16, 2100439.
Sun, S. Q.; Lu, M.; Gao, X. P.; Shi, Z. F.; Bai, X.; Yu, W. W.; Zhang, Y. 0D perovskites: Unique properties, synthesis, and their applications. Adv. Sci. 2021, 8, 2102689.
Tan, Z. F.; Chu, Y. M.; Chen, J. X.; Li, J. H.; Ji, G. Q.; Niu, G. D.; Gao, L.; Xiao, Z. W.; Tang, J. Lead-free perovskite variant solid solutions Cs2Sn1−xTexCl6: Bright luminescence and high anti-water stability. Adv. Mater. 2020, 32, 2002443.
Liu, Y.; Rong, X. M.; Li, M. Z.; Molokeev, M. S.; Zhao, J.; Xia, Z. G. Incorporating rare-earth terbium(III) ions into Cs2AgInCl6: Bi nanocrystals toward tunable photoluminescence. Angew. Chem., Int. Ed. 2020, 59, 11634–11640.
Arfin, H.; Kshirsagar, A. S.; Kaur, J.; Mondal, B.; Xia, Z. G.; Chakraborty, S.; Nag, A. ns2 electron (Bi3+ and Sb3+) doping in lead-free metal halide perovskite derivatives. Chem. Mater. 2020, 32, 10255–10267.
Dave, K.; Fang, M. H.; Bao, Z.; Fu, H. T.; Liu, R. S. Recent developments in lead-free double perovskites: Structure, doping, and applications. Chem. Asian J. 2020, 15, 242–252.
Zhou, B.; Liu, Z. X.; Fang, S. F.; Zhong, H. Z.; Tian, B. B.; Wang, Y.; Li, H. N.; Hu, H. L.; Shi, Y. M. Efficient white photoluminescence from self-trapped excitons in Sb3+/Bi3+-codoped Cs2NaInCl6 double perovskites with tunable dual-emission. ACS Energy Lett. 2021, 6, 3343–3351.
Su, B. B.; Li, M. Z.; Song, E. H.; Xia, Z. G. Sb3+-doping in cesium zinc halides single crystals enabling high-efficiency near-infrared emission. Adv. Funct. Mater. 2021, 31, 2105316.
Cheng, X. W.; Li, R. F.; Zheng, W.; Tu, D. T.; Shang, X. Y.; Gong, Z. L.; Xu, J.; Han, S. Y.; Chen, X. Y. Tailoring the broadband emission in all-inorganic lead-free 0D in-based halides through Sb3+ doping. Adv. Opt. Mater. 2021, 9, 2101975.
Chen, B.; Guo, Y.; Wang, Y.; Liu, Z.; Wei, Q.; Wang, S. X.; Rogach, A. L.; Xing, G. C.; Shi, P.; Wang, F. Multiexcitonic emission in zero-dimensional Cs2ZrCl6: Sb3+ perovskite crystals. J. Am. Chem. Soc. 2021, 143, 17599–17606.
Zhang, G. D.; Dang, P. P.; Xiao, H.; Lian, H. Z.; Liang, S.; Yang, L.; Cheng, Z. Y.; Li, G. G.; Lin, J. Antimony-doped lead-free zero-dimensional tin(IV)-based organic-inorganic metal halide hybrids with high photoluminescence quantum yield and remarkable stability. Adv. Opt. Mater. 2021, 9, 2101637.
Zeng, R. S.; Bai, K.; Wei, Q. L.; Chang, T.; Yan, J.; Ke, B.; Huang, J. L.; Wang, L. S.; Zhou, W. C.; Cao, S. et al. Boosting triplet self-trapped exciton emission in Te(IV)-doped Cs2SnCl6 perovskite variants. Nano Res. 2021, 14, 1551–1558.
Jing, Y. Y.; Liu, Y.; Zhao, J.; Xia, Z. G. Sb3+ doping-induced triplet self-trapped excitons emission in lead-free Cs2SnCl6 nanocrystals. J. Phys. Chem. Lett. 2019, 10, 7439–7444.
Sun, H. T.; Zhou, J. J.; Qiu, J. R. Recent advances in bismuth activated photonic materials. Prog. Mater. Sci. 2014, 64, 1–72.
Locardi, F.; Sartori, E.; Buha, J.; Zito, J.; Prato, M.; Pinchetti, V.; Zaffalon, M. L.; Ferretti, M.; Brovelli, S.; Infante, I. et al. Emissive Bi-doped double perovskite Cs2Ag1−xNaxInCl6 nanocrystals. ACS Energy Lett. 2019, 4, 1976–1982.
Xiong, P. X.; Li, Y. Y.; Peng, M. Y. Recent advances in super broad infrared luminescence bismuth-doped crystals. iScience 2020, 23, 101578.
Chen, X. Z.; Li, Y.; Huang, K.; Huang, L.; Tian, X. M.; Dong, H. F.; Kang, R.; Hu, Y. H.; Nie, J. M.; Qiu, J. R. et al. Trap energy upconversion-like near-infrared to near-infrared light rejuvenateable persistent luminescence. Adv. Mater. 2021, 33, 2008722.
Zhang, W.; Zheng, W.; Li, L. Y.; Huang, P.; Gong, Z. L.; Zhou, Z. W.; Sun, J. Y.; Yu, Y.; Chen, X. Y. Dual-band-tunable white-light Emission from Bi3+/Te4+ emitters in perovskite-derivative Cs2SnCl6 microcrystals. Angew. Chem., Int. Ed. 2022, 61, e202116085.
Tan, Z. F.; Li, J. H.; Zhang, C.; Li, Z.; Hu, Q. S.; Xiao, Z. W.; Kamiya, T.; Hosono, H.; Niu, G. D.; Lifshitz, E. et al. Highly efficient bule-emitting Bi-doped Cs2SnCl6 perovskite variant: Photoluminescence induced by impurity doping. Adv. Funct. Mater. 2020, 30, 2004738.
Liu, S. P.; Yang, B.; Chen, J. S.; Wei, D. H.; Zheng, D. Y.; Kong, Q. K.; Deng, W. Q.; Han, K. L. Efficient thermally activated delayed fluorescence from all-inorganic cesium zirconium halide perovskite nanocrystals. Angew. Chem., Int. Ed. 2020, 59, 21925–21929.
Xiong, G. T.; Yuan, L. F.; Jin, Y. H.; Wu, H. Y.; Li, Z. Z.; Qu, B. Y.; Ju, G. F.; Chen, L.; Yang, S. H.; Hu, Y. H. Aliovalent doping and surface grafting enable efficient and stable lead-free blue-emitting perovskite derivative. Adv. Opt. Mater. 2020, 8, 2000779.
Arfin, H.; Nag, A. Origin of luminescence in Sb3+- and Bi3+-doped Cs2SnCl6 perovskites: Excited state relaxation and spin-orbit coupling. J. Phys. Chem. Lett. 2021, 12, 10002–10008.
Liu, R. X.; Zhang, W. J.; Liu, W. J.; Li, G. J. Synthesis of a Bi3+-doped Cs2HfCl6 double perovskite with highly efficient blue light emission at room temperature. Inorg. Chem. 2021, 60, 10451–10458.
Liu, M. Z.; Duan, C. K.; Tanner, P. A.; Ma, C. G.; Yin, M. Rationalizing the photoluminescence of Bi3+ and Sb3+ in double perovskite halide crystals. J. Phys. Chem. C 2021, 125, 26670–26678.
Swart, H. C.; Kroon, R. E. Ultraviolet and visible luminescence from bismuth doped materials. Opt. Mater. :X 2019, 2, 100025.
Krasnikov, A.; Mihokova, E.; Nikl, M.; Zazubovich, S.; Zhydachevskyy, Y. Luminescence spectroscopy and origin of luminescence centers in Bi-doped materials. Crystals 2020, 10, 208.
Dang, P. P.; Liu, D. J.; Li, G. G.; Al Kheraif, A. A.; Lin, J. Recent advances in bismuth ion-doped phosphor materials: Structure design, tunable photoluminescence properties, and application in white LEDs. Adv. Opt. Mater. 2020, 8, 1901993.
Lou, B. B.; Wen, J.; Ning, L. X.; Yin, M.; Ma, C. G.; Duan, C. K. Understanding the defect levels and photoluminescence in a series of bismuth-doped perovskite oxides: First-principles study. Phys. Rev. B 2021, 104, 115101.
Pelle, F.; Jacquier, B.; Denis, J. P.; Blanzat, B. Optical properties of Cs2NaBiCl6. J. Lumin. 1978, 17, 61–72.
Wolfert, A.; Blasse, G. Luminescence of Bi3+-doped crystals of Cs2NaYBr6 and Cs2NaLaCl6. J. Solid State Chem. 1985, 59, 133–142.
Wei, J.; Zheng, W.; Huang, P.; Gong, Z. L.; Liu, Y.; Lu, S.; Li, Z.; Chen, X. Y. Direct photoinduced synthesis of lead halide perovskite nanocrystals and nanocomposites. Nano Today 2021, 39, 101179.
Zhang, C. G.; Zhang, M. R.; Zheng, W.; Wei, J. J.; Wang, S. T.; Huang, P.; Cheng, X. W.; Dai, T.; Chen, Z.; Chen, X. Y. A new class of luminescent nanoprobes based on main-group Sb3+ emitters. Nano Res. 2022, 15, 179–185.
Zhang, W.; Wei, J. J.; Gong, Z. L.; Huang, P.; Xu, J.; Li, R. F.; Yu, S. H.; Cheng, X. W.; Zheng, W.; Chen, X. Y. Unveiling the excited-state dynamics of Mn2+ in 0D Cs4PbCl6 perovskite nanocrystals. Adv. Sci. 2020, 7, 2002210.
Galkowski, K.; Mitioglu, A.; Miyata, A.; Plochocka, P.; Portugall, O.; Eperon, G. E.; Wang, J. T. W.; Stergiopoulos, T.; Stranks, S. D.; Snaith, H. J. et al. Determination of the exciton binding energy and effective masses for methylammonium and formamidinium lead tri-halide perovskite semiconductors. Energy Environ. Sci. 2016, 9, 962–970.
Chen, J. W.; Wang, J.; Xu, X. B.; Li, J. H.; Song, J. Z.; Lan, S.; Liu, S. N.; Cai, B.; Han, B. N.; Precht, J. T. et al. Efficient and bright white light-emitting diodes based on single-layer heterophase halide perovskites. Nat. Photonics 2021, 15, 238–244.
Stadler, W.; Hofmann, D. M.; Alt, H. C.; Muschik, T.; Meyer, B. K.; Weigel, E.; Müller-Vogt, G.; Salk, M.; Rupp, E.; Benz, K. W. Optical investigations of defects in Cd1−xZnxTe. Phys. Rev. B 1995, 51, 10619–10630.
De Jong, M.; Seijo, L.; Meijerink, A.; Rabouw, F. T. Resolving the ambiguity in the relation between stokes shift and huang-rhys parameter. Phys. Chem. Chem. Phys. 2015, 17, 16959–16969.
Jacobs, P. W. M.; Oyama, K. Optical absorption of s2 configuration ions in alkali halide crystals: I. Lineshape of the A band in In+-doped crystals. J. Phys. C:Solid State Phys. 1975, 8, 851–864.
Oomen, E. W. J. L.; Smit, W. M. A.; Blasse, G. On the luminescence of Sb3+ in Cs2NaMCl6 (with M = Sc, Y, La): A model system for the study of trivalent s2 ions. J. Phys. C:Solid State Phys. 1986, 19, 3263–3272.
Donker, H.; Smit, W. M. A.; Blasse, G. On the luminescence of CaO: Sn2+. Phys. Status Solidi B 1988, 145, 333–342.
Donker, H.; Smit, W. M. A.; Blasse, G. On the luminescence of Te4+ in A2ZrCl6 (A = Cs, Rb) and A2ZrCl6 (A = Cs, Rb, K). J. Phys. Chem. Solids 1989, 50, 603–609.
Donker, H.; Van Schaik, W.; Smit, W. M. A.; Blasse, G. On the luminescence of selenium(IV) in A2ZrCl6 (A = Cs, Rb). Chem. Phys. Lett. 1989, 158, 509–514.
Vandersteen, A. C.; Vanhesteren, J. J. A.; Slok, A. P. Luminescence of the Bi3+ ion in compounds LiLnO2 and NaLnO2 (Ln = Sc, Y, La, Gd, Lu). J. Electrochem. Soc. 1981, 128, 1327–1333.
Jacobs, P. W. M. Alkali halide crystals containing impurity ions with the ns2 ground-state electronic configuration. J. Phys. Chem. Solids 1991, 52, 35–67.
Blasse, G.; Van der Steen, A. C. Luminescence characteristics of Bi3+-activated oxides. Solid State Commun. 1979, 31, 993–994.
Van Der Steen, A. C.; Dijcks, L. T. F. The luminescence properties of alkaline-earth oxides activated with 6s2 ions. Phys. Status Solidi B 1981, 104, 283–292.
