Engineering Tunable Dual-Dependent Emission in Co-Doped Cs₇Cd₃Br₁₃ Perovskites

Abstract

Cd-based Cs₇Cd₃Br₁₃ perovskites, featuring both tetrahedral and octahedral polyhedral structures, have garnered significant acclaim for their efficient luminescent performance achieved through multi-exciton state regulation by doping. However, it remains controversial whether the doping sites are in the octahedra or tetrahedra of Cs₇Cd₃Br₁₃. To address this, we introduced Pb²⁺ and Sb³⁺ ions and, supported by experimental and theoretical evidence, demonstrated that these ions preferentially occupy the octahedra. Among them, Pb²⁺ ions single doping achieves a near-unity photoluminescence quantum yield of 93.7%, which results in excellent X-ray scintillation performance, high light yield of 41,772 photon MeV⁻¹, and a low detection limit of 29.78 nGy_air s^–1. Moreover, this incorporation of Pb²⁺ and Sb³⁺ enabled an exciton state regulation strategy, resulting in standard white light emission with CIE chromaticity coordinates of (0.33, 0.33). Additionally, a multifaceted optical anticounterfeiting and information encryption scheme was designed based on the differences in optical properties caused by the different sensitivities of [PbBr₆]⁴⁻ octahedron and [SbBr₆]³⁻ octahedron to temperature and excitation wavelengths. These diverse photoluminescence characteristics provide new insights and practical demonstrations for advanced X-ray imaging, lighting, optical encryption, and anticounterfeiting technologies.

Keywords

Cd-based perovskite / dual-dependent emission / multifunctional application / X-ray scintillator

References

[1] C. Ronda, “Challenges in Application of Luminescent Materials, a Tutorial Overview (Invited Review),” Progress in Electromagnetics Research 147 (2014): 81-93.

[2] G. Zissis, P. Bertoldi, and T. Serrenho, Update on the Status of LED-Lighting World Market Since 2018 (2021).

[3] X.-K. Liu, W. Xu, S. Bai, et al., “Metal Halide Perovskites for Light-Emitting Diodes,” Nature Materials 20, no. 1 (2021): 10-21.

[4] Y. Lou, S. Zhang, Z. Gu, et al., “Perovskite Single Crystals: Dimensional Control, Optoelectronic Properties, and Applications,” Materials Today 62 (2023): 225-250.

[5] M. Xu, J. Gu, Z. Fang, et al., “Colorless to Black Switching With High Contrast Ratio via the Electrochemical Process of a Hybrid Organic-Inorganic Perovskite,” Carbon Energy 5, no. 11 (2023): e358.

[6] O. Balitskii, M. Sytnyk, and W. Heiss, “Recent Developments in Halide Perovskite Nanocrystals for Indirect X-Ray Detection,” Advanced Materials Technologies 9 (2024): 2400150.

[7] J. I. Kim, Q. Zeng, S. Park, et al., “Strategies to Extend the Lifetime of Perovskite Downconversion Films for Display Applications,” Advanced Materials 35, no. 43 (2023): 2209784.

[8] H. Mai, X. Wen, X. Li, et al., “Data Driven High Quantum Yield Halide Perovskite Phosphors Design and Fabrication,” Materials Today 74 (2024): 12-21.

[9] G. Vats, B. Hodges, A. J. Ferguson, L. M. Wheeler, and J. L. Blackburn, “Optical Memory, Switching, and Neuromorphic Functionality in Metal Halide Perovskite Materials and Devices,” Advanced Materials 35, no. 37 (2023): 2205459.

[10] J. Fan, W. Li, Q. Zhou, et al., “Metal Halide Perovskites for Direct X-Ray Detection in Medical Imaging: To Higher Performance,” Advanced Functional Materials 34 (2024): 2401017.

[11] S. Lan, B. Pan, Y. Liu, et al., “Preparation and Promising Optoelectronic Applications of Lead Halide Perovskite Patterned Structures: A Review,” Carbon Energy 5, no. 10 (2023): e318.

[12] T. Chang, Q. Wei, R. Zeng, S. Cao, J. Zhao, and B. Zou, “Efficient Energy Transfer in Te⁴⁺-Doped Cs₂ZrCl₆ Vacancy-Ordered Perovskites and Ultrahigh Moisture Stability via A-Site Rb-Alloying Strategy,” Journal of Physical Chemistry Letters 12, no. 7 (2021): 1829-1837.

[13] J. Y. Chun, B. G. Kim, J. Y. Kim, W. Jang, and D. H. Wang, “Passivation Engineering via Silica-Encapsulated Quantum Dots for Highly Sensitive Photodetection,” Carbon Energy 5, no. 9 (2023): e350.

[14] T. Kou, Q. Wei, T. Chang, et al., “A Mild Synthesis of 0D Mn²⁺-Doped Cs₃CdBr₅ Metal Halide for White Light-Emitting Diodes and X-Ray Imaging,” Laser & Photonics Reviews 19, no. 2 (2025): 2400953.

[15] C. Wang, Y. Ding, Y. Wang, et al., “Metal Halide Perovskites for Solar-to-Chemical Energy Conversion in Aqueous Media,” Carbon Energy 6, no. 11 (2024): e500.

[16] Y. Zhao, L. Gao, Q. Wang, et al., “Reinforced Sno₂ Tensile-Strength and ‘Buffer-Spring’ Interfaces for Efficient Inorganic Perovskite Solar Cells,” Carbon Energy 6, no. 6 (2024): e468.

[17] T. Kou, T. Chang, Q. Wei, et al., “Heterovalent Ion Doped 0D Cs₃CdBr₅ With Near-Unity Photoluminescence Yield and Multifunctional Applications,” Journal of Materials Science & Technology 225 (2025): 87-94.

[18] S. Ge, H. Peng, Q. Wei, et al., “Realizing Color-Tunable and Time-Dependent Ultralong Afterglow Emission in Antimony-Doped CsCdCl₃ Metal Halide for Advanced Anti-Counterfeiting and Information Encryption,” Advanced Optical Materials 11, no. 14 (2023): 2300323.

[19] J. Guo, Q. Hu, M. Lu, et al., “Pb²⁺ Doped CsCdBr₃ Perovskite Nanorods for Pure-Blue Light-Emitting Diodes,” Chemical Engineering Journal 427 (2022): 131010.

[20] H. Xu, W. Liang, Z. Zhang, et al., “2D Perovskite Mn²⁺-Doped Cs₂CdBr₂Cl₂ Scintillator for Low-Dose High-Resolution X-Ray Imaging,” Advanced Materials 35, no. 26 (2023): 2300136.

[21] Y. Gao, X. Han, Q. Wei, et al., “Efficient Orange Emission in Mn²⁺-Doped Cs₃Cd₂Cl₇ Perovskites With Excellent Stability,” Journal of Physical Chemistry Letters 13, no. 31 (2022): 7177-7184.

[22] Y. Dai, Q. Wei, T. Chang, et al., “Efficient Self-Trapped Exciton Emission in Ruddlesden-Popper Sb-Doped Cs₃Cd₂Cl₇ Perovskites,” Journal of Physical Chemistry C 126, no. 27 (2022): 11238-11245.

[23] K. D. Sieber, P. S. Bryan, H. R. Luss, et al., “Preparation and Characterization of Cs₇Cd₃Br₁₃,” Journal of Solid State Chemistry 100, no. 1 (1992): 1-8.

[24] R. E. Marsh, “On the Space Group of Cs₇Cd₃Br₁₃,” Journal of Solid State Chemistry 105, no. 2 (1993): 607-608.

[25] Y. Qiu, Z. Ma, G. Dai, X. Fu, and Z. Ma, “All-Inorganic Luminescent Ternary Cadmium Halide Cs₇Cd₃Br₁₃ With Two Types of Cd-Centered Polyhedrons,” Inorganic Chemistry 61, no. 7 (2022): 3288-3295.

[26] C. Yang, B. Ke, Q. Wei, et al., “Luminescence and Mechanism of Mn²⁺ Substitution in Cs₇Cd₃Br₁₃ With Two Types of Coordination Number,” Inorganic Chemistry 62, no. 7 (2023): 3075-3083.

[27] M. Gao, Y. Pan, C. Peng, et al., “White Light Emission From Single-Component Cs₇Cd₃Br₁₃:Pb²⁺, Mn²⁺ Crystals With High Quantum Efficiency and Enhanced Thermodynamic Stability,” Chemistry of Materials 35, no. 2 (2023): 773-782.

[28] Y. Ye, K. Li, L. Niu, J. Ren, and C. Liu, “0D Cs₃Cd_1-xMn_xBr₅ Nanocrystals Embedded in Glass for Optical Thermometry,” Advanced Optical Materials 12, no. 6 (2024): 2301886.

[29] H. Tang, Z. Jia, Y. Xu, Y. Liu, and Q. Lin, “Enhanced Photoluminescence Quantum Yield of Metal Halide Perovskite Microcrystals for Multiple Optoelectronic Applications,” Small 20, no. 4 (2024): 2304336.

[30] D. Schwarzenbach, H. Birkedal, M. Hostettler, and P. Fischer, “Neutron Diffraction Investigation of the Temperature Dependence of Crystal Structure and Thermal Motions of Red HgI₂,” Acta Crystallographica. Section B: Structural Science 63, no. 6 (2007): 828-835.

[31] J. Wu, F. Lin, S. Zhang, et al., “One-Dimensional Organic-Inorganic Hybrid Double Perovskites With Near-Unity Photoluminescence Quantum Yield and Advanced Multifunctional Applications,” Chemistry of Materials 36, no. 8 (2024): 3851-3860.

[32] J. Wu, X. Li, X. Lian, et al., “Ultrafast Study of Exciton Transfer in Sb(III)-Doped Two-Dimensional [NH₃(CH₂)₄NH₃]CdBr₄ Perovskite,” ACS Nano 15, no. 9 (2021): 15354-15361.

[33] S. Kaviani, D. A. Tayurskii, O. V. Nedopekin, and I. Piyanzina, “DFT Insight Into Cd²⁺, Hg²⁺, Pb²⁺, Sn²⁺, As³⁺, Sb³⁺, and Cr³⁺ Heavy Metal Ions Adsorption Onto Surface of Bowl-Like B30 Nanosheet,” Journal of Molecular Liquids 365 (2022): 120131.

[34] R. Lin, Q. Guo, Q. Zhu, Y. Zhu, W. Zheng, and F. Huang, “All-Inorganic CsCu₂I₃ Single Crystal With High-PLQY (≈15.7%) Intrinsic White-Light Emission via Strongly Localized 1D Excitonic Recombination,” Advanced Materials 31, no. 46 (2019): 1905079.

[35] D. Liang, M. Wang, S. Zhao, et al, “Luminescence Improvement of Hybrid Zinc-Based Halides via Sb³⁺-Doping for Flexible X-Ray Imaging,” Laser & Photonics Reviews 18, no. 11 (2024): 2400244.

[36] Y. Cao, G. Qi, L. Sui, et al., “Pressure-Induced Emission Enhancements of Mn²⁺-Doped Cesium Lead Chloride Perovskite Nanocrystals,” ACS Materials Letters 2, no. 4 (2020): 381-388.

[37] Y. Zhang, L. Zhu, Z. Yang, et al., “Transient Photoinduced Pb²⁺ Disproportionation for Exciton Self-Trapping and Broadband Emission in Low-Dimensional Lead Halide Perovskites,” Journal of the American Chemical Society 146, no. 11 (2024): 7831-7838.

[38] J. Liao, C. Chen, Y. Bai, J. Yao, B. Zou, and R. Zeng, “Tunable Emission of Pb(II) and Sb(III) Codoped 2D Hybrid BDACdBr₄ Metal Halides for Cryptographic Anticounterfeiting Applications,” ACS Applied Electronic Materials 5, no. 9 (2023): 5224-5233.

[39] T. Chang, H. Wang, Y. Gao, et al., “Component Engineering to Tailor the Structure and Optical Properties of Sb-Doped Indium-Based Halides,” Inorganic Chemistry 61, no. 3 (2022): 1486-1494.

[40] Y. Li, C. Zhang, X. Zhang, et al., “Intrinsic Point Defects in Inorganic Perovskite CsPbI₃ From First-Principles Prediction,” Applied Physics Letters 111, no. 16 (2017): 162106.

[41] Q. Wei, T. Chang, R. Zeng, et al., “Self-Trapped Exciton Emission in a Zero-Dimensional (TMA)₂SbCl₅·DMF Single Crystal and Molecular Dynamics Simulation of Structural Stability,” Journal of Physical Chemistry Letters 12, no. 30 (2021): 7091-7099.

[42] Y. Jing, Y. Liu, J. Zhao, and Z. Xia, “Sb³⁺ Doping-Induced Triplet Self-Trapped Excitons Emission in Lead-Free Cs₂SnCl₆ Nanocrystals,” Journal of Physical Chemistry Letters 10, no. 23 (2019): 7439-7444.

[43] J. Luo, X. Wang, S. Li, et al., “Efficient and Stable Emission of Warm-White Light from Lead-Free Halide Double Perovskites,” Nature 563, no. 7732 (2018): 541-545.

[44] W. Zhu, R. Li, X. Liu, et al., “Photophysical Properties of Copper Halides With Strongly Confined Excitons and Their High-Performance X-Ray Imaging,” Advanced Functional Materials 34, no. 26 (2024): 2316449.

[45] I. Holl, E. Lorenz, and G. Mageras, “A Measurement of the Light Yield of Common Inorganic Scintillators,” IEEE Transactions on Nuclear Science 35, no. 1 (1988): 105-109.

[46] L. Qiu, G. Si, X. Bao, et al., “Interfacial Engineering of Halide Perovskites and Two-Dimensional Materials,” Chemical Society Reviews 52, no. 1 (2023): 212-247.

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