Research Progress on Zero-dimensional Metal Halide Scintillators towards Radiation Detection Applications

doi:10.15541/jim20250148

Abstract

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-absorption, strong ambient adaptability, and considerable stability under irradiation, are good candidates for the next-generation scintillators. This review consolidates the recent research progress on 0D metal halide scintillators towards applications in radiation detection. Firstly, 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 growth of large-scale, defect-less and highly transparent single crystals, deep and reasonable explanation of scintillation mechanism, and creation of standard for the methods of performance measurement towards various kinds of scintillators.

Key words: radiation detection, scintillator, zero-dimensional metal halide, scintillation mechanism, review

CLC Number:

O799

SUN Lian, ZHANG Leilei, XUE Zexu, WU Kun, CHEN Ye, LI Zhiyuan, WANG Lukai, WANG Zungang. Research Progress on Zero-dimensional Metal Halide Scintillators towards Radiation Detection Applications[J]. Journal of Inorganic Materials, 2026, 41(2): 159-176.

Figures/Tables 11

Fig. 1 Schematic illustration of different derivations of metal halide scintillators[11]

Fig. 2 Crystal structures of several typical 0D metal halides[13-18] CsSnCl3[13]; Cs2ZrCl6[14]; Cs3Cu2I5[15]; A2SbCl5[16]; Rb7Sb3Cl16[17]; A3Bi2I9[18]

Fig. 3 Calculated band structures (a-c) and partial wave density of states (d-f) of Cs2ZrX6 (X=Cl, Br, I)[21]

Fig. 4 Formation and luminescence mechanism of STEs[20,25 -26] (a) Self-trapping represented by a ball interacting with a rubber sheet[25]; (b) Schematic of typical STEs process (GS represents ground state, FE represents free exciton state, FC represents free carrier state, STE represents self-trapped exciton state, Eg represents bandgap energy, Eb represents exciton binding energy, Est represents self-trapping energy, Ed represents lattice deformation energy, and EPL represents emission energy)[26]; (c) Schematic of the luminescence processes in 0D perovskites (LD represents lattice distortion, EPL,S represents singlet state emission energy, and EPL,T represents triplet state emission energy)[20]

Fig. 5 Proposed decay mechanism of Cs3Cu2I5:Mn single crystal under low-energy UV and high-energy ray excitation[29]

Fig. 6 Pb-based 0D metal halides[44,46,49] (a, b) Crystal structures of (a) CsPbBr3 and (b) Cs4PbBr6; (c) Photo of large-scale CsPbBr3@Cs4PbBr6[44]; (d) PL spectra of Cs4PbBr6-xClx single crystal and application for X-ray imaging[49]; (e) CIE chromaticity coordinates (0.14, 0.19) of the blue emission from (C9NH20)7(PbCl4)Pb3Cl11·CH3CN single crystals[46]

Fig. 7 Cu-based 0D metal halides[56,59,66 -67] (a) Crystal structure of Cs3Cu2I5[56]; (b) As-grown 7 mm diameter Cs3Cu2I5 crystal ingot, a polished sample, and 137Cs gamma-ray spectra of ϕ7 mm×1 mm Cs3Cu2I5 single crystal[59]; (c) Photograph of colloidal solution of Cs3Cu2X5 (X=Cl, Br, I) nanocrystals (NCs) in hexane and their thin films under UV light (λ=254 nm)[66]; (d) An ideal model method used for quantitative analysis of structural deformation for Cs3Cu2X5[67]

Fig. 8 Mn-based 0D metal halides[76,78 -81] (a) Crystal structure of Cs3MnBr5[76]; (b) Photography of flexible Cs3MnBr5@PDMS film under ambient light, UV light and bending, with X-ray images of chip using Cs3MnBr5@PDMS film[78]; (c) Illustration of the closest Mn-Mn distance and luminescent efficiency for the selected 0D Mn2+-based metal halides[79]; (d) Images of a (C38H34P2)MnBr4 single crystal under daylight and UV light[80]; (e) Illustration of bulky molecules at A site in A2MnBr4, and images of a (Gua)2MnBr4 bulk single crystal under ambient light and UV irradiation (365 nm)[81]

Fig. 9 Other 0D metal halides[86,99,105] (a) Crystal structure of Cs3.2K0.8SnBr6 determined by Rietveld refinement, change in a and c lattice parameters upon Cs+ substitution by Rb+ and K+, and image of Cs4-xAxSn(Br,I)6 powders under 365 nm UV light[86]; (b) Radioluminescence (RL)/PL spectra of Gua3SbCl6 powders as a function of temperature[99]; (c) Picture of 12-mm diameter as-grown Cs4EuBr6 single crystal and 137Cs pulse height spectra measured with Cs4EuBr6[105]

Fig. 10 Applications of 0D metal halides in radiation detection fields[60,112,118,122,127,129] (a) Crystal structure and X-ray radioluminescence of (PPN)2SbCl5[112]; (b) Optical images of Cs3Cu2Cl5 films, and schematic diagram of the sample upright and attached on the Cs3Cu2Cl5 film[118]; (c) Comparison of Cs3Cu2I5 and other scintillators for γ-ray dosimetry[122];(d) Crystal structure, picture of as-grown crystal and pulse height spectra of Cs3Cu2I5:Tl[60]; (e) Neutron detection properties of Cs3Cu2I5:6Li[127]; (f) Crystal structure and photos of (C19H34N)2MnBr4 under β-ray irradiation[129]

Table 1 Scintillation properties of typical 0D metal halides

Type	Luminescence emission peak/nm	Light yield/(ph·MeV^-1)	Decay time/ns	Ref.
Cs₃Cu₂I₅:Mn	445^a	95772^a	3^a	[29]
(C₃N₃H₁₁O)₂PbBr₆·4H₂O	568^b	-	15.4^c	[45]
Cs₄PbBr₆	523^b	19000^b	179.6^c	[47]
CsPbBr₃@Cs₄PbBr₆	523^b	64000^b	2.1^c	[48]
CsPbBr₅Cl	518^b	~4426^b	0.62^c	[49]
bMOF⊃MAPbBr₃	517^c	-	37.7^c	[50]
Cs₃Cu₂I₅:Tl	440^b	87000^a	807.5^a	[60]
[AEPipz]CuBr₃·Br·H₂O	500^c	62400^b	1.2×10^5a	[68]
Cs₃Cu₂I₅single crystal	436^b	32695^a	39^a	[69]
(TBA)CuBr₂	498^c	24134^b	2.3×10^5a	[70]
(Bmpip)₂Cu₂Br₄	~650^b	16000^b	56.2^a (²⁴¹Am)	[71]
[BzTPP]₂Cu₂I₄	529^c	27706^b	1.9×10^3c	[72]
(C₈H₂₀N)₂Cu₂Br₄	468^b	91300^b	1.4×10^6c	[73]
Cs₃MnI₅	540^c	33600^b	4.0×10^5c	[77]
(C₁₀H₁₆N)₂MnBr₄	518^c	-	3.3×10^5c	[79]
(C₃₈H₃₄P₂)MnBr₄	517^b	~80000^b	3.2×10^5c	[80]
(Gua)₂MnBr₄	520^b	21061^b	2.0×10^8b	[81]
(ETP)₂MnBr₄	520^b	~35000±2000^b	3.0×10^5c	[82]
Mn(ttpo)Br₂	-	12840^b	6×10^5c	[83]

References 130

[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. DOI URL
[2]	JANA A, CHO S, PATIL S A, et al. Perovskite: scintillators, direct detectors, and X-ray imagers. Materials Today, 2022, 55: 110. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[8]	BIZARRI G, DORENBOS P. Charge carrier and exciton dynamics in LaBr₃:Ce³⁺ scintillators: experiment and model. Physical Review B, 2007, 75(18): 184302. DOI URL
[9]	MOSZYŃSKI M, NASSALSKI A, SYNTFELD-KAŻUCH A, et al. Temperature dependences of LaBr₃(Ce), LaCl₃(Ce) and NaI(Tl) scintillators. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2006, 568(2): 739. DOI URL
[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. DOI URL
[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. DOI URL
[12]	WELLS H L. Über die cäsium- und kalium-bleihalogenide. Zeitschrift fur Anorganische Chemie, 1893, 3(1): 195. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI PMID
[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. DOI URL
[20]	LI M, XIA Z. Recent progress of zero-dimensional luminescent metal halides. Chemical Society Reviews, 2021, 50(4): 2626. DOI PMID
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[25]	SMITH M D, KARUNADASA H I. White-light emission from layered halide perovskites. Accounts of Chemical Research, 2018, 51(3): 619. DOI PMID
[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. DOI URL
[27]	MURRAY R B, MEYER A. Scintillation response of activated inorganic crystals to various charged particles. Physical Review, 1961, 122(3): 815. DOI URL
[28]	BIZARRI G. Scintillation mechanisms of inorganic materials: from crystal characteristics to scintillation properties. Journal of Crystal Growth, 2010, 312(8): 1213. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[33]	LECOQ P, KORZNIK M. Scintillator developments for high energy physics and medical imaging. 1999 IEEE Nuclear Science Symposium and Medical Imaging Conference, Seattle, 1999, 1: 1-5.
[34]	RONDA C. Scintillators for medical imaging. Optical Materials: X, 2024, 22: 100293. DOI URL
[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. DOI URL
[36]	WANG J X, SHEKHAH O, BAKR O M, et al. Energy transfer- based X-ray imaging scintillators. Chem, 2025, 11(1): 102273. DOI URL
[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. DOI URL
[38]	NIKL M, MIHOKOVA E, NITSCH K, et al. Photoluminescence of Cs₄PbBr₆ crystals and thin films. Chemical Physics Letters, 1999, 306(5): 280. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI PMID
[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: 5190. DOI
[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. DOI PMID
[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. DOI URL
[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. DOI PMID
[49]	WU X, ZHOU Q, WU H, et al. Cs₄PbBr_6-_xCl_x single crystals with tunable emission for X-ray detection and imaging. The Journal of Physical Chemistry C, 2021, 125(48): 26619. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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)₂Zn_1-_xMn_xBr₄ solid solutions. The Journal of Physical Chemistry Letters, 2020, 11(15): 5956. DOI URL
[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: 4329. DOI
[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 International Edition, 2025, 137(5): e202417018.
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI PMID
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI
[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. DOI URL
[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. DOI URL
[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. DOI PMID
[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. DOI URL
[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. DOI URL
[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. DOI URL
[116]	YANG B, YIN L, NIU G, et al. Lead-free halide Rb₂CuBr₃ as sensitive X-ray scintillator. Advanced Materials, 2019, 31(44): 1904711. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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, 9(8): 2500273. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI URL
[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. DOI
[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.