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Research Article

Boosting self-trapped exciton emission from Cs3Cu2I5 nanocrystals by doping-enhanced exciton-phonon coupling

Xiaohan Li1,2, Aijun Liu1,2, Zhaoyu Wang2,4( ), Youchao Wei2,3, Qun Lin2, Yameng Chen2, Yongsheng Liu1,2,3( ), Maochun Hong1,2,3,4( )
College of Chemistry, Fuzhou University, Fuzhou 350116, China
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
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Graphical Abstract

A doping-enhanced exciton-phonon coupling effect is observed in Cs3Cu2I5 nanocrystals (NCs), remarkably enhancing their self-trapped exciton emission. Consequently, an X-ray detector based on these alkaline-earth metal ions doped Cs3Cu2I5 NCs delivers an X-ray imaging resolution of up to 10 lp·mm−1 and a low detection limit of 0.37 μGyair·s−1.

Abstract

Self-trapped excitons (STEs) emission from halide perovskites with strong exciton-phonon coupling has attracted considerable attention due to the widespread application in optoelectronic devices. Nevertheless, the in-depth understanding of the relationship between exciton-phonon coupling and luminescence intensity remains incomplete. Herein, a doping-enhanced exciton-phonon coupling effect is observed in Cs3Cu2I5 nanocrystals (NCs), which leads to a remarkable increasement of their STEs emission efficiency. Mechanism study shows that the hetero-valent substitution of Cu+ with alkaline-earth metal ions (AE2+) causes a greater degree of Jahn–Teller distortion between the ground state and excited state structures of [Cu2I5]3− clusters as evidenced by our spectral analysis and first-principles calculations. As a consequence, an X-ray detector based on these Cs3Cu2I5:AE NCs delivers an X-ray imaging resolution of up to 10 lp·mm−1 and a low detection limit of 0.37 μGyair·s−1, disclosing the potential of doping-enhanced exciton-phonon coupling effect in improving STEs-emission and practical application for X-ray imaging.

Keywords

Cs3Cu2I5nanocrystalsself-trapped excitonexciton-phonon couplingX-ray image

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References

[1]

Guo, Q. X.; Zhao, X.; Song, B. X.; Luo, J. J.; Tang, J. Light emission of self-trapped excitons in inorganic metal halides for optoelectronic applications. Adv. Mater. 2022, 34, 2201008.
Crossref Google Scholar
[2]

Zhang, F.; Zhou, Y. C.; Chen, Z. P.; Wang, M.; Ma, Z. Z.; Chen, X.; Jia, M. C.; Wu, D.; Xiao, J. W.; Li, X. J. et al. Thermally activated delayed fluorescence zirconium-based perovskites for large-area and ultraflexible X-ray scintillator screens. Adv. Mater. 2022, 34, 2204801.
Crossref Google Scholar
[3]

Wang, Q.; Zhou, Q.; Nikl, M.; Xiao, J. W.; Kucerkova, R.; Beitlerova, A.; Babin, V.; Prusa, P.; Linhart, V.; Wang, J. K. et al. Highly resolved X-ray imaging enabled by In(I) doped perovskite-like Cs3Cu2I5 single crystal scintillator. Adv. Opt. Mater. 2022, 10, 2200304.
Crossref Google Scholar
[4]

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.
Crossref Google Scholar
[5]

Tian, T. F.; Xiong, X. H.; Zhao, Y. X.; Li, H.; Wang, W.; Wang, L. Ultra-wideband warm white light emission from self-trapped excitons in CsAgCl2. J. Alloys Compd. 2022, 895, 162632.
Crossref Google Scholar
[6]

Luo, J. J.; Wang, X. M.; Li, S. R.; Liu, J.; Guo, Y. M.; Niu, G. D.; Yao, L.; Fu, Y. H.; Gao, L.; Dong, Q. S. et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature 2018, 563, 541–545.
Crossref Google Scholar
[7]

Wolf, N. R.; Connor, B. A.; Slavney, A. H.; Karunadasa, H. I. Doubling the stakes: The promise of halide double perovskites. Angew. Chem., Int. Ed. 2021, 60, 16264–16278.
Crossref Google Scholar
[8]

Locardi, F.; Samoli, M.; Martinelli, A.; Erdem, O.; Magalhaes, D. V.; Bals, S.; Hens, Z. Cyan emission in two-dimensional colloidal Cs2CdCl4: Sb3+ ruddlesden-popper phase nanoplatelets. ACS Nano 2021, 15, 17729–17737.
Crossref Google Scholar
[9]

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.
Crossref Google Scholar
[10]

Li, S.; Xu, J.; Li, Z. G.; Zeng, Z. C.; Li, W.; Cui, M. H.; Qin, C. C.; Du, Y. P. One-dimensional lead-free halide with near-unity greenish-yellow light emission. Chem. Mater. 2020, 32, 6525–6531.
Crossref Google Scholar
[11]

Wang, L. T.; Shi, Z. F.; Ma, Z. Z.; Yang, D. W.; Zhang, F.; Ji, X. Z.; Wang, M.; Chen, X.; Na, G. R.; Chen, S. et al. Colloidal synthesis of ternary copper halide nanocrystals for high-efficiency deep-blue light-emitting diodes with a half-lifetime above 100 h. Nano Lett. 2020, 20, 3568–3576.
Crossref Google Scholar
[12]

Sun, J. Y.; Zheng, W.; Huang, P.; Zhang, M. R.; Zhang, W.; Deng, Z. H.; Yu, S. H.; Jin, M. Y.; Chen, X. Y. Efficient near-infrared luminescence in lanthanide-doped vacancy-ordered double perovskite Cs2ZrCl6 phosphors via Te4+ sensitization. Angew. Chem., Int. Ed. 2022, 61, e202201993.
Crossref Google Scholar
[13]

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, 2100434.
Crossref Google Scholar
[14]

Gao, F.; Zhu, X. N.; Feng, Q. S.; Zhong, W. H.; Liu, W. Z.; Xu, H. Y.; Liu, Y. C. Deep-blue emissive Cs3Cu2I5 perovskites nanocrystals with 96.6% quantum yield via InI3-assisted synthesis for light-emitting device and fluorescent ink applications. Nano Energy 2022, 98, 107270.
Crossref Google Scholar
[15]

Lian, L. Y.; Zheng, M. Y.; Zhang, W. Z.; Yin, L. X.; Du, X. Y.; Zhang, P.; Zhang, X. W.; Gao, J. B.; Zhang, D. L.; Gao, L. et al. Efficient and reabsorption-free radioluminescence in Cs3Cu2I5 nanocrystals with self-trapped excitons. Adv. Sci. 2020, 7, 2000195.
Crossref Google Scholar
[16]

Yang, B.; Yin, L. X.; Niu, G. D.; Yuan, J. H.; Xue, K. H.; Tan, Z. F.; Miao, X. S.; Niu, M.; Du, X. Y.; Song, H. S. et al. Lead-free halide Rb2CuBr3 as sensitive X-ray scintillator. Adv. Mater. 2019, 31, 1904711.
Crossref Google Scholar
[17]

Li, J. W.; Inoshita, T.; Ying, T. P.; Ooishi, A.; Kim, J.; Hosono, H. A highly efficient and stable blue-emitting Cs5Cu3Cl6I2 with a 1D chain structure. Adv. Mater. 2020, 32, 2002945.
Crossref Google Scholar
[18]

Jun, T.; Sim, K.; Iimura, S.; Sasase, M.; Kamioka, H.; Kim, J.; Hosono, H. Lead-free highly efficient blue-emitting Cs3Cu2I5 with 0D electronic structure. Adv. Mater. 2018, 30, 1804547.
Crossref Google Scholar
[19]

Hu, X. D.; Yan, P.; Ran, P.; Lu, L. P.; Leng, J.; Yang, Y. M.; Li, X. M. In situ fabrication of Cs3Cu2I5: Tl nanocrystal films for high-resolution and ultrastable X-ray imaging. J. Phys. Chem. Lett. 2022, 13, 2862–2870.
Crossref Google Scholar
[20]

Wang, C. Y.; Liang, P.; Xie, R. J.; Yao, Y.; Liu, P.; Yang, Y. T.; Hu, J.; Shao, L. Y.; Sun, X. W.; Kang, F. Y. et al. Highly efficient lead-free (Bi, Ce)-codoped Cs2Ag0.4Na0.6InCl6 double perovskites for white light-emitting diodes. Chem. Mater. 2020, 32, 7814–7821.
Crossref Google Scholar
[21]

Cheng, P. F.; Zheng, D. Y.; Feng, L.; Liu, Y. F.; Liu, J. X.; Li, J. T.; Yang, Y.; Wang, G. X.; Han, K. L. Doped all-inorganic cesium zirconium halide perovskites with high-efficiency and tunable emission. J. Energy Chem. 2022, 65, 600–604.
Crossref Google Scholar
[22]

Pang, P. Y.; Jin, G. R.; Liang, C.; Wang, B. Z.; Xiang, W.; Zhang, D. L.; Xu, J. W.; Hong, W.; Xiao, Z. W.; Wang, L. et al. Rearranging low-dimensional phase distribution of quasi-2D perovskites for efficient sky-blue perovskite light-emitting diodes. ACS Nano 2020, 14, 11420–11430.
Crossref Google Scholar
[23]

Qing, J.; Ramesh, S.; Xu, Q.; Liu, X. K.; Wang, H. Y.; Yuan, Z. C.; Chen, Z.; Hou, L. T.; Sum, T. C.; Gao, F. Spacer cation alloying in ruddlesden-popper perovskites for efficient red light-emitting diodes with precisely tunable wavelengths. Adv. Mater. 2021, 33, 2104381.
Crossref Google Scholar
[24]

Yuan, S.; Wang, Z. K.; Xiao, L. X.; Zhang, C. F.; Yang, S. Y.; Chen, B. B.; Ge, H. T.; Tian, Q. S.; Jin, Y.; Liao, L. S. Optimization of low-dimensional components of quasi-2D perovskite films for deep-blue light-emitting diodes. Adv. Mater. 2019, 31, 1904319.
Crossref Google Scholar
[25]

Pei, Y. F.; Tu, D. T.; Li, C. L.; Han, S. Y.; Xie, Z.; Wen, F.; Wang, L. P.; Chen, X. Y. Boosting near-infrared luminescence of lanthanide in Cs2AgBiCl6 double perovskites via breakdown of the local site symmetry. Angew. Chem., Int. Ed. 2022, 61, e202205276.
Crossref Google Scholar
[26]

Gao, M. Y.; Zhang, Y.; Lin, Z. N.; Jin, J. B.; Folgueras, M. C.; Yang, P. D. The making of a reconfigurable semiconductor with a soft ionic lattice. Matter 2021, 4, 3874–3896.
Crossref Google Scholar
[27]

Ahmed, G. H.; Liu, Y.; Bravić, I.; Ng, X.; Heckelmann, I.; Narayanan, P.; Fernández, M. S.; Monserrat, B.; Congreve, D. N.; Feldmann, S. Luminescence enhancement due to symmetry breaking in doped halide perovskite nanocrystals. J. Am. Chem. Soc. 2022, 144, 15862–15870.
Crossref Google Scholar
[28]

Wang, X. J.; Zhang, X. Z.; Yan, S.; Liu, H.; Zhang, Y. H. Nearly-unity quantum yield and 12-hour afterglow from a transparent perovskite of Cs2NaScCl6:Tb. Angew. Chem., Int. Ed. 2022, 61, e202210853.
Crossref Google Scholar
[29]

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.
Crossref Google Scholar
[30]

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.
Crossref Google Scholar
[31]

Fattal, H.; Creason, T. D.; Delzer, C. J.; Yangui, A.; Hayward, J. P.; Ross, B. J.; Du, M. H.; Glatzhofer, D. T.; Saparov, B. Zero-dimensional hybrid organic-inorganic indium bromide with blue emission. Inorg. Chem. 2021, 60, 1045–1054.
Crossref Google Scholar
[32]

Liang, D. H.; Liu, X. H.; Luo, B. B.; Qian, Q. K.; Cai, W. S.; Zhao, S. Y.; Chen, J. Z.; Zang, Z. G. High quantum yield of In-based halide perovskites for white light emission and flexible X-ray scintillators. EcoMat 2023, 5, e12296.
Crossref Google Scholar
[33]

Yang, B.; Chen, J. S.; Hong, F.; Mao, X.; Zheng, K. B.; Yang, S. Q.; Li, Y. J.; Pullerits, T.; Deng, W. Q.; Han, K. L. Lead-free, air-stable all-inorganic cesium bismuth halide perovskite nanocrystals. Angew. Chem., Int. Ed. 2017, 56, 12471–12475.
Crossref Google Scholar
[34]

Cheng, S. L.; Nikl, M.; Beitlerova, A.; Kucerkova, R.; Du, X. Y.; Niu, G. D.; Jia, Y. C.; Tang, J.; Ren, G. H.; Wu, Y. T. Ultrabright and highly efficient all-inorganic zero-dimensional perovskite scintillators. Adv. Opt. Mater. 2021, 9, 2100460.
Crossref Google Scholar
[35]

Zhao, X.; Jin, T.; Gao, W. R.; Niu, G. D.; Zhu, J. S.; Song, B. X.; Luo, J. J.; Pan, W. C.; Wu, H. D.; Zhang, M. Y. et al. Embedding Cs3Cu2I5 scintillators into anodic aluminum oxide matrix for high-resolution X-ray imaging. Adv. Opt. Mater. 2021, 9, 2101194.
Crossref Google Scholar
[36]

Lian, L. Y.; Zheng, M. Y.; Zhang, P.; Zheng, Z.; Du, K.; Lei, W.; Gao, J. B.; Niu, G. D.; Zhang, D. L.; Zhai, T. Y. et al. Photophysics in Cs3Cu2X5 (X = Cl, Br, or I): Highly luminescent self-trapped excitons from local structure symmetrization. Chem. Mater. 2020, 32, 3462–3468.
Crossref Google Scholar
[37]

Chen, H. J.; Pina, J. M.; Yuan, F. L.; Johnston, A.; Ma, D. X.; Chen, B.; Li, Z. L.; Dumont, A.; Li, X. Y.; Liu, Y. A. et al. Multiple self-trapped emissions in the lead-free halide Cs3Cu2I5. J. Phys. Chem. Lett. 2020, 11, 4326–4330.
Crossref Google Scholar
[38]

Luo, Z. S.; Li, Q.; Zhang, L. M.; Wu, X. T.; Tan, L.; Zou, C.; Liu, Y. J.; Quan, Z. W. 0D Cs3Cu2X5 (X = I, Br, and Cl) nanocrystals: Colloidal syntheses and optical properties. Small 2020, 16, 1905226.
Crossref Google Scholar
[39]

Du, P.; Luo, L. H.; Cheng, W. Neoteric Mn2+-activated Cs3Cu2I5 dazzling yellow-emitting phosphors for white-LED. J. Am. Ceram. Soc. 2020, 103, 1149–1155.
Crossref Google Scholar
[40]

Xu, Q.; Wang, J.; Zhang, Q. D.; Ouyang, X.; Ye, M. H.; Xie, W. T.; Yan, X. W.; Li, D. Y.; Ouyang, X. P.; Tang, X. B. et al. Solution-processed lead-free bulk 0D Cs3Cu2I5 single crystal for indirect gamma-ray spectroscopy application. Photonics Res. 2021, 9, 351–356.
Crossref Google Scholar
[41]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Crossref Google Scholar
[42]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[43]

Momma, K.; Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Cryst. 2011, 44, 1272–1276.
Crossref Google Scholar
[44]

Hu, X. D.; Li, Y. L.; Wu, Y.; Chen, W. W.; Zeng, H. B.; Li, X. M. One-pot synthesis of Cs3Cu2I5 nanocrystals based on thermodynamic equilibrium. Mater. Chem. Front. 2021, 5, 6152–6159.
Crossref Google Scholar
[45]

Cheng, P. F.; Sun, L.; Feng, L.; Yang, S. Q.; Yang, Y.; Zheng, D. Y.; Zhao, Y.; Sang, Y. B.; Zhang, R. L.; Wei, D. H. et al. Colloidal synthesis and optical properties of all-inorganic low-dimensional cesium copper halide nanocrystals. Angew. Chem., Int. Ed. 2019, 58, 16087–16091.
Crossref Google Scholar
[46]

Guo, Z. H.; Li, J. Z.; Gao, Y.; Cheng, J. J.; Zhang, W. J.; Pan, R. K.; Chen, R.; He, T. C. Multiphoton absorption in low-dimensional cesium copper iodide single crystals. J. Mater. Chem. C 2020, 8, 16923–16929.
Crossref Google Scholar
Nano Research
Volume 16 Issue 7,
July 2023
Pages 10476-10482
DOI: 10.1007/s12274-023-5708-9
Cite this article:
Li X, Liu A, Wang Z, et al. Boosting self-trapped exciton emission from Cs3Cu2I5 nanocrystals by doping-enhanced exciton-phonon coupling. Nano Research, 2023, 16(7): 10476-10482. https://doi.org/10.1007/s12274-023-5708-9
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Nanocrystals

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Received: 18 February 2023
Revised: 23 March 2023
Accepted: 02 April 2023
Published: 06 May 2023
© Tsinghua University Press 2023
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