面向辐射探测应用的零维金属卤化物闪烁体研究进展

doi:10.15541/jim20250148

摘要/Abstract

摘要： 闪烁体是辐射探测领域的关键材料,在高能物理、医疗诊断、天文学、放射性勘测及国土安全领域有重要应用,但迄今为止鲜有兼具高光产额与能量分辨率、优异环境稳定性与低成本的闪烁体材料,迫切需要发现一种综合性能优异、成本合适的闪烁体。零维(0D)金属卤化物具有高光产额、弱自吸收效应、强环境适应性、良好的辐照稳定性等优势,是下一代闪烁体的优选。本文概述了0D金属卤化物闪烁体及其在辐射探测领域的研究进展,从分子结构出发概述了0D金属卤化物的特点与闪烁发光原理,特别是其独特的自陷激子发光特性;系统总结了具有优异辐射探测性能的Pb基、Cu基、Mn基、Sn基等典型0D金属卤化物材料并对它们进行细致比较;以及该类材料在辐射成像、能谱探测、中子探测等领域的应用。最后,结合研究现状,展望了0D金属卤化物材料在辐射探测领域面临的挑战与机遇。未来,研究者们应致力解决大尺寸低缺陷高透明闪烁单晶生长、更深入的闪烁机理研究以及针对多种形态的闪烁体性能测量标准构建等关键问题。

关键词: 辐射探测, 闪烁体, 零维金属卤化物, 闪烁发光机理, 综述

Abstract: Scintillators are key materials for radiation detection field. They have wide applications in many fields such as high-energy physics, medical diagnostics, astronomy, radioactivity exploration and homeland security. However, most of the reported scintillators (e.g. NaI:Tl and LaBr₃:Ce) can hardly provide a perfect combination of high light yield and energy resolution, excellent ambient stability and low cost. It is urgent to discover novel scintillators with outstanding comprehensive performance and ideal cost. Zero-dimensional (0D) metal halides, possessing abundant advantages such as high light yield, weak self-adsorption, strong ambient adaptability, considerable stability under irradiation, are good candidates of the next-generation scintillators. This review consolidates the recent research progress of 0D metal halide scintillators towards radiation detection applications. First, the basic properties as well as the scintillation mechanism of 0D metal halides are analyzed at molecular scale, especially their unique self-trapped exciton emission characteristic. Then, some typical 0D metal halides which show excellent radiation detection properties are systematically introduced, containing Pb, Cu, Mn and Sn-based structures, and their key scintillation parameters are comprehensively compared. Furthermore, their applications in X-ray imaging, gamma-ray spectrum measurement, and neutron detection are well discussed. Last, the challenges and opportunities in development of 0D metal halide scintillators towards radiation detection are prospected. In the future, researchers should be committed to providing solutions to the issues such as the growth of large-scale, defect-less and highly transparent single crystals, deep and reasonable explanation of scintillation mechanism, and the creation of standard for the methods of performance measurement towards various kinds of scintillators.

Key words: radiation detection, scintillator, 0D metal halides, scintillation mechanism, review

中图分类号:

O799

孙炼, 张磊磊, 薛泽旭, 吴坤, 陈晔, 李志远, 王鲁凯, 王尊刚. 面向辐射探测应用的零维金属卤化物闪烁体研究进展[J]. 无机材料学报, DOI: 10.15541/jim20250148.

SUN Lian, ZHANG Leilei, XUE Zexu, WU Kun, CHEN Ye, LI Zhiyuan, WANG Lukai, WANG Zungang. Research Progress of Zero-dimensional Metal Halide Scintillators towards Radiation Detection Applications[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250148.

参考文献

[1] ZHENG Z, WEI Q, TONG Y,et al. Effect of Zr⁴+ co-doping on neutron/gamma discrimination of Cs₂LaLiBr₆:Ce crystals. Journal of Inorganic Materials, 2024, 39(5): 539.
[2] JANA A, CHO S, PATIL S A, et al. Perovskite: scintillators, direct detectors, and X-ray imagers.Materials Today, 2022, 55: 110.
[3] NIKL M, YOSHIKAWA A.Recent R&D trends in inorganic single-crystal scintillator materials for radiation detection. Advanced Optical Materials, 2015, 3(4): 463.
[4] SHEN Y Q, SHI Y, PAN Y B, et al. Fabrication and 2D-mapping of Pr: Lu₃Al₅O₁₂ scintillator ceramics with high light yield and fast decay time.Journal of Inorganic Materials, 2014, 29(5): 534.
[5] GLODO J, WANG Y, SHAWGO R,et al. New developments in scintillators for security applications. Physics Procedia, 2017, 90: 285.
[6] DI FULVIO A, SHIN T H, HAMEL M C,et al. Digital pulse processing for NaI(Tl) detectors. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2016, 806: 69.
[7] HAWRAMI R, ARIESANTI E, FARSONI A,et al. Growth and evaluation of improved CsI:Tl and NaI:Tl scintillators, Crystals, 2022, 12(11): 1517.
[8] BIZARRI G, DORENBOS P.Charge carrier and exciton dynamics in LaBr₃:Ce³+ scintillators: experiment and model.Physical Review B, 2007, 75(18): 184302.
[9] MOSZYŃSKI M, NASSALSKI A, SYNTFELD-KAŻUCH A,et al. Temperature dependences of LaBr₃(Ce), LaCl₃, 2006, 568(2): 739.
[10] GUO S, LIU K, LIN Z,et al. Temperature dependence of Ce luminescence characteristics in LaBr₃: Ce crystal. Journal of Luminescence, 2025, 277: 120956.
[11] ZHOU L, LIAO J F, KUANG D B.An overview for zero-dimensional broadband emissive metal-halide single crystals.Advanced Optical Materials, 2021, 9(17): 2100544.
[12] WELLS H L. Über die cäsium- und kalium-bleihalogenide. Zeitschrift fur Anorganische Chemie, 1893, 3(1): 195.
[13] PAUL D K, HOSSAIN A K M A. A comprehensive DFT + U investigation of electrical, optical, and structural properties of doped CsSnCl₃ perovskite: unveiling optoelectronic potential.Computational Materials Science, 2024, 231: 112585.
[14] CHEN B, GUO Y, WANG Y,et al. Multiexcitonic emission in zero-dimensional Cs₂ZrCl₆:Sb³+ perovskite crystals. Journal of the American Chemical Society, 2021, 143(42): 17599.
[15] TSUJI M, SASASE M, IIMURA S,et al. Room-temperature solid-state synthesis of Cs₃Cu₂I₅ thin films and formation mechanism for its unique local structure. Journal of the American Chemical Society, 2023, 145(21): 11650.
[16] SUN C, DENG Z, LI Z,et al. Achieving near-unity photoluminescence quantum yields in organic-inorganic hybrid antimony (III) chlorides with the [SbCl₅] geometry. Angewandte Chemie International Edition, 2023, 62(10): e202216720.
[17] ZHANG B, PINCHETTI V, ZITO J, et al. Isolated [SbCl₆]³- octahedra are the only active emitters in Rb₇Sb₃Cl₁₆ Nanocrystals. ACS Energy Letters, 2021, 6(11): 3952.
[18] ECKHARDT K, BON V, GETZSCHMANN J,et al. Crystallographic insights into (CH₃NH₃)₃(Bi₂I₉): a new lead-free hybrid organic-inorganic material as a potential absorber for photovoltaics. Chemical Communications, 2016, 52(14): 3058.
[19] DING M, WU Q, SHEN Y,et al.(C₈H₇N₂O₂)₂[Bi₂Br₈]·2H₂O and (C₈H₇N₂O₂)₆[Bi₂Cl₁₀]Cl₂·2H₂O: exploring birefringent crystals in hybrid halide systems. Inorganic Chemistry, 2024, 63(21): 9701.
[20] LI M, XIA Z.Recent progress of zero-dimensional luminescent metal halides.Chemical Society Reviews, 2021, 50(4): 2626.
[21] LIU J, LI M, HAN Q,et al. Theoretical investigation of the structural stability, electronic and optical properties of the double perovskite Cs₂ZrX₆(X=Cl, Br, I). Materials Science in Semiconductor Processing, 2024, 171: 107984.
[22] HAN D, SHI H, MING W,et al. Unraveling luminescence mechanisms in zero-dimensional halide perovskites. Journal of Materials Chemistry C, 2018, 6(24): 6398.
[23] HOANG T B, MOSES A F, ZHOU H L,et al. Observation of free exciton photoluminescence emission from single wurtzite GaAs nanowires. Applied Physics Letters, 2009, 94(13): 133105.
[24] ZHANG Y, TU D, WANG L,et al. Transition metal ion-doped cesium lead halide perovskite nanocrystals: doping strategies and luminescence design. Materials Chemistry Frontiers, 2024, 8(1): 192.
[25] SMITH M D, KARUNADASA H I.White-light emission from layered halide perovskites.Accounts of Chemical Research, 2018, 51(3): 619.
[26] LI S, LUO J, LIU J,et al. Self-trapped excitons in all-inorganic halide perovskites: fundamentals, status, and potential applications. The Journal of Physical Chemistry Letters, 2019, 10(8): 1999.
[27] MURRAY R B, MEYER A.Scintillation response of activated inorganic crystals to various charged particles.Physical Review, 1961, 122(3): 815.
[28] BIZARRI G.Scintillation mechanisms of inorganic materials: from crystal characteristics to scintillation properties.Journal of Crystal Growth, 2010, 312(8): 1213.
[29] YAO Q, LI J, LI X,et al. Achieving a record scintillation performance by micro-doping a heterovalent magnetic ion in Cs₃Cu₂I₅ single-crystal. Advanced Materials, 2023, 35(44): 2304938.
[30] TONGUC B T, ARSLAN H AL-BURIAHI M S. Studies on mass attenuation coefficients, effective atomic numbers and electron densities for some biomolecules.Radiation Physics and Chemistry, 2018, 153: 86.
[31] DORENBOS P, HAAS J, EIJK C.Non-proportionality in the scintillation response and the energy resolution obtainable with scintillation crystals.IEEE Transactions on Nuclear Science, 1995, 42(6): 2190.
[32] MOSZYŃSKI M, SYNTFELD-KAŻUCH A, SWIDERSKI L,et al. Energy resolution of scintillation detectors. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2016, 805: 25.
[33] LECOQ P, KORZNIK M.Scintillator Developments for High Energy Physics and Medical Imaging, 1999 IEEE Nuclear Science Symposium. Conference Record. 1999 Nuclear Science Symposium and Medical Imaging Conference (Cat. No.99CH37019), 1999, 1: 1-5.
[34] RONDA C.Scintillators for medical imaging.Optical Materials: X, 2024, 22: 100293.
[35] TANG Y, DENG M, LIU Q,et al. Reducing luminescence intensity and suppressing irradiation-induced darkening of Bi₄Ge₃O₁₂ by Ce-doping for radiation detection. Advanced Optical Materials, 2024, 12(2): 2301332.
[36] WANG J X, SHEKHAH O, BAKR O M,et al. Energy transfer-based X-ray imaging scintillators. Chem, 2025, 11(1): 102273.
[37] YIN J, ZHANG Y, BRUNO A,et al. Intrinsic lead ion emissions in zero-dimensional Cs₄PbBr₆ nanocrystals. ACS Energy Letters, 2017, 2(12): 2805.
[38] NIKL M, MIHOKOVA E, NITSCH K,et al. Photoluminescence of Cs₄PbBr₆ crystals and thin films. Chemical Physics Letters, 1999, 306(5): 280.
[39] AKKERMAN Q A, PARK S, RADICCHI E,et al. Nearly monodisperse insulator Cs₄PbX₆(X=Cl, Br, I) nanocrystals, their mixed halide compositions, and their transformation into CsPbX₃ Nanocrystals. Nano Letters, 2017, 17(3): 1924.
[40] BAO Z, TSENG Y J, YOU W,et al. Efficient luminescence from CsPbBr₃ nanoparticles embedded in Cs₄PbBr₆. The Journal of Physical Chemistry Letters, 2020, 11(18): 7637.
[41] SAIDAMINOV M I, ALMUTLAQ J, SARMAH S, et al. Pure Cs₄PbBr₆: highly luminescent zero-dimensional perovskite solids. ACS Energy Letters, 2016, 1(4): 840.
[42] ZHANG H, LIAO Q, WU Y,et al. Pure zero-dimensional Cs₄PbBr₆ single crystal rhombohedral microdisks with high luminescence and stability. Physical Chemistry Chemical Physics, 2017, 19(43): 29092.
[43] YIN J, YANG H, SONG K,et al. Point defects and green emission in zero-dimensional perovskites. The Journal of Physical Chemistry Letters, 2018, 9(18): 5490.
[44] CAO F, YU D, MA W,et al. Shining emitter in a stable host: design of halide perovskite scintillators for X-ray imaging from commercial concept. ACS Nano, 2020, 14(5): 5183.
[45] CUI B B, HAN Y, HUANG B,et al. Locally collective hydrogen bonding isolates lead octahedra for white emission improvement. Nature Communications, 2019, 10(1): 5190.
[46] ZHOU C, LIN H, WORKU M,et al. Blue emitting single crystalline assembly of metal halide clusters. Journal of the American Chemical Society, 2018, 140(41): 13181.
[47] PENG G, AN B, CHEN H,et al. Self-organizing pixelated Cs₄PbBr₆ scintillator plate for large-area, ultra-flexible, high spatial resolution and stable X-Ray imaging. Advanced Optical Materials, 2023, 11(1): 2201751.
[48] XU Q, WANG J, SHAO W,et al. A solution-processed zero-dimensional all-inorganic perovskite scintillator for high resolution gamma-ray spectroscopy detection. Nanoscale, 2020, 12(17): 9727.
[49] WU X, ZHOU Q, WU H,et al. Cs₄PbBr₆-_xCl_x single crystals with tunable emission for X-ray detection and imaging. The Journal of Physical Chemistry C, 2021, 125(48): 26619.
[50] WU H, RAN P, YAO L, et al. Confinement of methylammonium lead bromide nanocrystals in metal-organic frameworks as a stable scintillator for high-performance X-ray imaging. Chemical Engineering Journal, 2024, 491: 152098.
[51] SHI W, ZHANG X, MATRAS-POSTOLEK K,et al. Mn-derived Cs₄PbX₆ nanocrystals with stable and tunable wide luminescence for white light-emitting diodes. Journal of Materials Chemistry C, 2022, 10(10): 3886.
[52] QIU Y, MA Z, DAI G,et al. Doped 0D Cs₄PbCl₆ single crystals featuring full-visible-region colorful luminescence. Journal of Materials Chemistry C, 2022, 10(16): 6227.
[53] LI Y, CHEN L, GAO R,et al. Nanosecond and highly sensitive scintillator based on all-inorganic perovskite single Crystals. ACS Applied Materials & Interfaces, 2022, 14(1): 1489.
[54] HAN J, LI Y, SHEN P,et al. Pressure-induced free exciton emission in a quasi-zero-dimensional hybrid lead halide. Angewandte Chemie International Edition, 2024, 63(1): e202316348.
[55] CHEN S, GAO J, CHANG J,et al. Family of highly luminescent pure ionic copper (I) bromide based hybrid materials. ACS Applied Materials & Interfaces, 2019, 11(19): 17513.
[56] JUN T, SIM K, IIMURA S, et al. Lead-free highly efficient blue-emitting Cs₃Cu₂I₅ with 0D electronic structure.Advanced Materials, 2018, 30(43): 1804547.
[57] YUAN D.Air-stable bulk halide single-crystal scintillator Cs₃Cu₂I₅ by melt growth: Intrinsic and Tl doped with high light yield.ACS Applied Materials & Interfaces, 2020, 12(34): 38333.
[58] STAND L, RUTSTROM D, KOSCHAN M,et al. Crystal growth and scintillation properties of pure and Tl-doped Cs₃Cu₂I₅. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2021, 991: 164963.
[59] CHENG S, BEITLEROVA A, KUCERKOVA R,et al. Zero-dimensional Cs₃Cu₂I₅ perovskite single crystal as sensitive X-ray and γ-ray scintillator. Physica Status Solidi (RRL) - Rapid Research Letters, 2020, 14(11): 2000374.
[60] CHENG S, NIKL M, BEITLEROVA A,et al. Ultrabright and highly efficient all-inorganic zero-dimensional perovskite scintillators. Advanced Optical Materials, 2021, 9(13): 2100460.
[61] WANG Q, ZHOU Q, NIKL M,et al. Highly resolved X-Ray imaging enabled by In(I) doped perovskite-like Cs₃Cu₂I₅ single crystal scintillator. Advanced Optical Materials, 2022, 10(11): 2200304.
[62] HU Y, YAN X, ZHOU L,et al. Improved energy transfer in Mn-doped Cs₃Cu₂I₅ microcrystals induced by localized lattice distortion. The Journal of Physical Chemistry Letters, 2022, 13(46): 10786.
[63] HAPOSAN T, ARRAMEL A, MAULIDA P Y D,et al. All-inorganic copper-halide perovskites for large-Stokes shift and ten-nanosecond-emission scintillators. Journal of Materials Chemistry C, 2024, 12(7): 2398.
[64] HUNYADI M, SAMU G F, CSIGE L,et al. Scintillator of polycrystalline perovskites for high-sensitivity detection of charged-particle radiations. Advanced Functional Materials, 2022, 32(48): 2206645.
[65] YANG Q, WEI H, LI G,et al. Spectral adjustable Re-Cs₃Cu₂I₅ nanocrystal-in-glass composite with long-term stability. Chemical Engineering Journal, 2024, 483: 149288.
[66] LIAN L, ZHENG M, ZHANG W,et al. Efficient and reabsorption-free radioluminescence in Cs₃Cu₂I₅ nanocrystals with self-trapped excitons. Advanced Science, 2020, 7(11): 2000195.
[67] ZHU W, LI R, LIU X,et al. Photophysical properties of copper halides with strongly confined excitons and their high-performance X-Ray imaging. Advanced Functional Materials, 2024, 34(26): 2316449.
[68] LIN N, WANG X, ZHANG H Y,et al. Zero-dimensional copper(I) halide microcrystals as highly efficient scintillators for flexible X-ray imaging. ACS Applied Materials & Interfaces, 2024, 16(31): 41165.
[69] YAO Q, LI J, LI X,et al. High-quality Cs₃Cu₂I₅ single-crystal is a fast-decaying scintillator. Advanced Optical Materials, 2022, 10(23): 2201161.
[70] LIAN L, WANG X, ZHANG P,et al. Highly luminescent zero-dimensional organic copper halides for X-ray scintillation. The Journal of Physical Chemistry Letters, 2021, 12(29): 6919.
[71] XU T, LI Y, NIKL M,et al. Lead-free zero-dimensional organic-copper (I) halides as stable and sensitive X-ray scintillators. ACS Applied Materials & Interfaces, 2022, 14(12): 14157.
[72] LIN N, WANG R C, ZHANG S Y,et al. 0D hybrid cuprous halide as an efficient light emitter and X-ray scintillator. Laser & Photonics Reviews, 2023, 17(12): 2300427.
[73] SU B, JIN J, HAN K,et al. Ceramic wafer scintillation screen by utilizing near-unity blue-emitting lead-free metal halide (C₈H₂₀N)₂Cu₂Br₄. Advanced Functional Materials, 2023, 33(5): 2210735.
[74] KOIDL P.Jahn-Teller effect in the ⁴T₁(1) and ⁴T₂(1) states of tetrahedrally coordinated Mn²+.Physica Status Solidi (b), 1976, 74(2): 477.
[75] KRETOV M K, ISKANDAROVA I M, POTAPKIN B V,et al. Simulation of structured ⁴T₁→⁶A₁ emission bands of Mn²+ impurity in Zn₂SiO₄: A first-principle methodology. Journal of Luminescence, 2012, 132(8): 2143.
[76] SU B, MOLOKEEV M, XIA Z.Mn²+-based narrow-band green-emitting Cs₃MnBr₅ phosphor and the performance optimization by Zn²+ alloying.Journal of Materials Chemistry C, 2019, 7(36): 11220.
[77] KONG Q, MENG X, JI S,et al. Highly reversible cesium manganese iodine for sensitive water detection and X-ray imaging. ACS Materials Letters, 2022, 4(9): 1734.
[78] XU M, YANG X, YANG X, et al. Heating revival of Cs₃MnBr₅ for anti-counterfeiting and large-area flexible X-ray imaging. Optical Materials, 2024, 156: 115959.
[79] ZHOU G, LIU Z, HUANG J,et al. Unraveling the near-unity narrow-band green emission in zero-dimensional Mn²+-based metal halides: a case study of (C₁₀H₁₆N)₂Zn₁-_xMn_xBr₄ solid solutions. The Journal of Physical Chemistry Letters, 2020, 11(15): 5956.
[80] XU L J, LIN X, HE Q,et al. Highly efficient eco-friendly X-ray scintillators based on an organic manganese halide. Nature Communications, 2020, 11(1): 4329.
[81] WU Y, ZHU Y, AHMED A A,et al. Excitation-dependent anti-thermal quenching in zero-dimensional manganese bromides for photoluminescence and X-ray scintillation. Angewandte Chemie, 2025, 137(5): 1
[82] LI B, XU Y, ZHANG X,et al. Zero-dimensional luminescent metal halide hybrids enabling bulk transparent medium as large-area X-ray scintillators. Advanced Optical Materials, 2022, 10(10): 2102793.
[83] LU J, GAO J, WANG S, et al. Improving X-ray scintillating merits of zero-dimensional organic-manganese (II) halide hybrids via enhancing the ligand polarizability for high-resolution imaging. Nano Letters, 2023, 23(10): 4351.
[84] LIU L, HU H, PAN W,et al. Robust organogel scintillator for self-healing and ultra-flexible X-ray imaging. Advanced Materials, 2024, 36(13): 2311206.
[85] ANDREWS R H, CLARK S J, DONALDSON J D, et al. Solid-state properties of materials of the type Cs₄MX₆(where M = Sn or Pb and X = Cl or Br).Journal of the Chemical Society, Dalton Transactions, 1983, 4: 767.
[86] BENIN B M, DIRIN D N, MORAD V,et al. Highly emissive self-trapped excitons in fully inorganic zero-dimensional tin halides. Angewandte Chemie International Edition, 2018, 57(35): 11329.
[87] WANG A, LI J, ZHANG Y, et al. Double-shell encapsulation of lead-free tin halide perovskite for self-powered smart windows. Small, 2024, 20(51): 2404149.
[88] LIU Y, YANG B, YU Z,et al. Eu³+@Cs₄SnBr₆ NCs-doped silicate glass with efficient tunable white light emission via energy transfer and multi-emission photoluminescence properties. Materials Today Chemistry, 2024, 42: 102387.
[89] HUANG Y, LU X, WU H,et al., Improving photoluminescence properties of lead-free Cs₄SnBr₆ zero-dimensional perovskite via Mn²+/Sb³+ co-doping. Journal of Luminescence, 2025, 277: 120930.
[90] ZHOU C, LIN H, TIAN Y,et al. Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency. Chemical Science, 2018, 9(3): 586.
[91] ZHOU C, TIAN Y, YUAN Z, et al. Highly efficient broadband yellow phosphor based on zero-dimensional tin mixed-halide perovskite.ACS Applied Materials & Interfaces, 2017, 9(51): 44579.
[92] SONG G, LI M, YANG Y, et al. Lead-free tin(IV)-based organic-inorganic metal halide hybrids with excellent stability and blue-broadband emission. The Journal of Physical Chemistry Letters, 2020, 11(5): 1808.
[93] ZHOU L, ZHOU S, LIU X,et al. Embedding Te⁴+ into Sn⁴+-based metal halide to passivate structure defects for high-performance light-emitting application. Inorganic Chemistry, 2024, 63(22): 10335.
[94] LIU X, LI K, SHAO W,et al. Revealing the structure-luminescence relationship in robust Sn(IV)-based metal halides by Sb³+ doping. Inorganic Chemistry, 2024, 63(11): 5158.
[95] WEI S, TIE S, SHEN K,et al. High-performance X-ray detector based on liquid diffused separation induced Cs₃Bi₂I₉ single crystal. Advanced Optical Materials, 2021, 9(22): 2101351.
[96] WANG J, LI Y, MA L,et al. Air-stabilized lead-free hexagonal Cs₃Bi₂I₉ nanocrystals for ultrahigh-performance optical detection. Advanced Functional Materials, 2022, 32(30): 2203072.
[97] ZHOU C, WORKU M, NEU J,et al. Facile preparation of light emitting organic metal halide crystals with near-unity quantum efficiency. Chemistry of Materials, 2018, 30(7): 2374.
[98] MCCALL K M, MORAD V, BENIN B M,et al., Efficient lone-pair-driven luminescence: structure-property relationships in emissive 5s² metal halides. ACS Materials Letters, 2020, 2(9): 1218.
[99] ZAFFALON M L, WU Y, COVA F,et al. Zero-dimensional Gua₃SbCl₆ crystals as intrinsically reabsorption-free scintillators for radiation detection. Advanced Functional Materials, 2023, 33(48): 2305564.
[100] XIE J L, HUANG Z Q, WANG B,et al. New lead-free perovskite Rb₇Bi₃Cl₁₆ nanocrystals with blue luminescence and excellent moisture-stability. Nanoscale, 2019, 11(14): 6719.
[101] TANG Y, LIANG M, CHANG B,et al. Lead-free double halide perovskite Cs₃BiBr₆ with well-defined crystal structure and high thermal stability for optoelectronics. Journal of Materials Chemistry C, 2019, 7(11): 3369.
[102] LIU X, ZHANG W, XU R,et al. Bright tunable luminescence of Sb³+ doping in zero-dimensional lead-free halide Cs₃ZnCl₅ perovskite crystals. Dalton Transactions, 2022, 51(26): 10029.
[103] MARAYATHUNGAL J H, DAS D K, BAKTHAVATSALAM R,et al. Mn²+-activated zero-dimensional metal (Cd, Zn) halide hybrids with near-unity PLQY and zero thermal quenching. The Journal of Physical Chemistry C, 2023, 127(18): 8618.
[104] HOU C, LIU X, WANG Z,et al. Designing guanidine-based lead-free hybrid indium perovskites with highly efficient intrinsic broadband emissions. Journal of Materials Chemistry C, 2024, 12(20): 7426.
[105] WU Y, HAN D, CHAKOUMAKOS B C,et al. Zero-dimensional Cs₄EuX₆(X = Br, I) all-inorganic perovskite single crystals for gamma-ray spectroscopy. Journal of Materials Chemistry C, 2018, 6(25): 6647.
[106] SAEKI K, FUJIMOTO Y, KOSHIMIZU M,et al. Comparative study of scintillation properties of Cs₂HfCl₆ and Cs₂ZrCl₆. Applied Physics Express, 2016, 9(4): 042602.
[107] ZHANG F, ZHOU Y, CHEN Z,et al. Thermally activated delayed fluorescence zirconium-based perovskites for large-area and ultraflexible X-ray scintillator screens. Advanced Materials, 2022, 34(43): 2204801.
[108] SWIDERSKI L, BRYLEW K, JANIAK L,et al. Cs₂ZrCl₆ scintillation properties studied using γ-ray spectroscopy and Compton coincidence technique. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2023, 1057: 168735.
[109] ZHU W, MA W, SU Y,et al. Low-dose real-time X-ray imaging with nontoxic double perovskite scintillators. Light: Science & Applications, 2020, 9(1): 112.
[110] YAO S Y, LI H, ZHOU M,et al. Visualization of X-rays with an ultralow detection limit via zero-dimensional perovskite scintillators. ACS Applied Materials & Interfaces, 2022, 14(51): 56957.
[111] MORAD V, SHYNKARENKO Y, YAKUNIN S,et al. Disphenoidal zero-dimensional lead, tin, and germanium halides: Highly emissive singlet and triplet self-trapped excitons and X-ray scintillation. Journal of the American Chemical Society, 2019, 141(25): 9764.
[112] HE Q, ZHOU C, XU L,et al. Highly stable organic antimony halide crystals for X-ray scintillation. ACS Materials Letters, 2020, 2(6): 633.
[113] ZHOU W, ZHU X, YU J,et al. High-quality Cs₃Cu₂I₅@PMMA scintillator films assisted by multiprocessing for X-ray imaging. ACS Applied Materials & Interfaces, 2023, 15(32): 38741.
[114] MA W, LIANG D, QIAN Q,et al. Near-unity quantum yield in zero-dimensional lead-free manganese-based halides for flexible X-ray imaging with high spatial resolution. eScience, 2023, 3(2): 100089.
[115] DUAN R, CHEN Z, XIANG D,et al. Large-area flexible scintillator screen based on copper-based halides for sensitive and stable X-ray imaging. Journal of Luminescence, 2023, 253: 119482.
[116] YANG B, YIN L, NIU G,et al. Lead-free halide Rb₂CuBr₃ as sensitive X-Ray scintillator. Advanced Materials, 2019, 31(44): 1904711.
[117] HAN L, SUN B, GUO C,et al. Photophysics in zero-dimensional potassium-doped cesium copper chloride Cs₃Cu₂Cl₅ nanosheets and its application for high-performance flexible X-ray detection. Advanced Optical Materials, 2022, 10(6): 2102453.
[118] QIU F, PENG G, XU Y,et al. Sequential vacuum evaporated copper metal halides for scalable, flexible, and dynamic X-ray detection. Advanced Functional Materials, 2023, 33(36): 2303417.
[119] WANG Z, WEI Y, LIU C,et al., Mn²+-activated Cs₃Cu₂I₅ nano-scintillators for ultra-high resolution flexible X-ray imaging. Laser & Photonics Reviews, 2023, 17(6): 2200851.
[120] CAO S, ZHU Y, HE P, et al. Cost-effective fabrication of copper(I) halide arrays with mitigated optical crosstalk for high-definition X-ray radiography. Chemical Engineering Journal, 2025, 508: 161139.
[121] WANG H, ZHANG S, XIA Z.Composition modulation of Cs₂ZrCl₆-based scintillator film via vapor deposition for large-area X-ray imaging.Small Methods, 2025, DOI: 10.1002/smtd.202500273.
[122] SONG X, LIU L, WAN P,et al. Ultrabroad dynamic all-solid-state radiation dose detector based on a 0D Cs₃Cu₂I₅ perovskite-like single crystal. ACS Applied Electronic Materials, 2023, 5(12): 6805.
[123] WANG Q, WANG C, SHI H, et al. Exciton-harvesting enabled efficient charged particle detection in zero-dimensional halides.Light: Science & Applications, 2024, 13(1): 190.
[124] GAO L, LI Q, SUN J L, et al. Gamma-ray irradiation stability of zero-dimensional Cs₃Cu₂I₅ metal halide scintillator single crystals. The Journal of Physical Chemistry Letters, 2023, 14(5): 1165.
[125] MYKHAYLYK V, NAGORNY S S, NAHORNA V V,et al. Growth, structure, and temperature dependent emission processes in emerging metal hexachloride scintillators Cs₂HfCl₆ and Cs₂ZrCl₆. Dalton Transactions, 2022, 51(17): 6944.
[126] WU J, DING J, HUANG X,et al. Fabrication and microstructure of Gd₂O₂S:Tb scintillation ceramics from water-bath synthesized nano-powders: influence of H₂SO₄/Gd₂O₃ molar ratio. Journal of Inorganic Materials, 2023, 38(4): 452.
[127] WANG Q, WANG C, WANG Z,et al. Achieving efficient neutron and gamma discrimination in a highly stable ⁶Li-loaded Cs₃Cu₂I₅ perovskite scintillator. The Journal of Physical Chemistry Letters, 2022, 13(39): 9066.
[128] YAO L, GUI W, ZHOU X,et al. Bright lead-free Cs₃Cu₂I₅ perovskite scintillators for thermal neutron detection. Materials Advances, 2023, 4(17): 3714.
[129] LIAN L, QI W, DING H,et al. Highly luminescent zero-dimensional lead-free manganese halides for β-ray scintillation. Nano Research, 2022, 15(9): 8486.
[130] WEI C H, DONG S, XU Z,et al. Controllable multi-exciton zero-dimensional antimony-based metal halides for white-light emission and β-ray detection. Angewandte Chemie International Edition, 2024, 63(51): e2024122.