X射线诱导光致变色材料机理与应用

doi:10.15541/jim20250025

摘要/Abstract

摘要： X射线诱导光致变色材料(X-ray induced photochromic materials, XP材料)因具有辐射剂量依赖的变色性质,在国防安全、核能开发利用、工业探伤和医学成像等领域具有广泛的应用前景。近年来,国内外科学家已发展了多种XP材料,深入探讨了其辐射变色机制,并作了特异性应用研究,亟需综合论述其变色机理和应用领域。本文综述了X射线辐射变色性质的材料体系,并根据其化学组成和变色特点进行了归纳,对比各种类型XP材料的优缺点,讨论了X射线诱导光致变色的机理,如色心形成和氧化还原反应等过程。最后,介绍了其在X射线探测器以及医学和工业中的潜在应用,并展望了其未来的发展方向。本文对发展性质更优异、场景适用性更灵活的XP材料后续研究具有重要意义,可促进X射线诱导光致变色材料的商业化应用进程。

关键词: 光致变色材料, X射线, 辐射变色, 变色机理, 辐射剂量检测

Abstract: X-ray induced photochromic materials (XP materials), characterized by their radiation dose-dependent coloration properties, exhibit broad application prospects in fields such as national defense and security, nuclear energy development and utilization, industrial nondestructive testing, and medical imaging. In recent years, scientists worldwide have developed diverse XP material systems, conducted in-depth investigations into their radiation-induced coloration mechanisms, and explored their specialized applications, highlighting the urgent need for a comprehensive review of their working principles and application domains. This article systematically summarizes the material systems exhibiting X-ray-induced photochromic behavior, categorizing them based on chemical composition and coloration characteristics. The advantages and limitations of various XP materials are comparatively analyzed, while the underlying mechanisms of X-ray-induced photochromism—such as color center formation and redox processes—are discussed. Furthermore, their potential applications in X-ray detection, medical diagnostics, and industrial monitoring are introduced. Finally, future research directions are proposed to advance the development of XP materials with enhanced performance and broader scenario adaptability. This review holds significant implications for guiding subsequent research on optimizing XP materials and accelerating their commercialization process, thereby facilitating the practical implementation of X-ray-induced photochromic technologies.

Key words: photochromic materials, X-ray, radiochromic, chromic mechanism, radiation dosage measurement

中图分类号:

TQ174

袁龙, 贾如, 袁梦, 张健, 段羽, 孟祥东. X射线诱导光致变色材料机理与应用[J]. 无机材料学报, DOI: 10.15541/jim20250025.

YUAN Long, JIA Ru, YUAN Meng, ZHANG Jian, DUAN Yu, MENG Xiang-dong. X-ray Induced Photochromic Materials, Mechanism and Application[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250025.

参考文献

[1] GLASS B.The genetic hazards of nuclear radiations.Science, 1957, 126(3267): 241.
[2] DU M H, WANG J, XU S J,et al. Super-elastic scintillating fibers and fabrics for efficient and visual radiation detection. Adv. Fiber Mater., 2023, 5(4): 1493.
[3] LUO Z C, WU Y Y, WANG Y A,et al. Clinical radiation dose verification by topographic persistent luminescence dosimetry. Nano Today, 2023, 50: 101854.
[4] CAO C T, TONEY M F, SHAM S K,et al. Emerging X-ray imaging technologies for energy materials. Materials Today, 2020, 34: 132.
[5] HAN J S, LEE S H, GO H, et al. High-performance cold cathode X-ray tubes using a carbon nanotube field electron emitter. Acs Nano, 2022, 16(7): 10231.
[6] NAKAJIMA T, MURAYAMA Y, MATSUZAWA T, et al. Development of a new highly sensitive LiF thermoluminescence dosimeter and its applications. Nucl. Instrum. Methods, 1978, 157(1): 155.
[7] ZHANG H, YANG Z, ZHOU M,et al. Reproducible X-ray imaging with a perovskite nanocrystal scintillator embedded in a transparent amorphous network structure. Adv. Mater., 2021, 33(40): 2102529.
[8] COLETTE D, MAZON D, BARNSLEY R, et al. Conceptual study of energy resolved x-ray measurement and electron temperature reconstruction on ITER with low voltage ionization chambers. Rev. Sci. Instrum., 2021, 92(8): 083511.
[9] PAN L, LIU Z F, WELTON C, et al. Ultrahigh-flux X-ray detection by a Solution-grown Perovskite CsPbBr₃ Single-crystal semiconductor detector. Adv Mater, 2023, 35(25): 2211840.
[10] THIRIMANNE H M, JAYAWARDENA K, PARNELL A J, et al. High sensitivity organic inorganic hybrid X-ray detectors with direct transduction and broadband response. Nat Commun, 2018, 9: 2926.
[11] LEISTNER A L, PIANOWSKI Z L.Smart photochromic materials triggered with visible light.European Journal of Organic Chemistry, 2022, 2022(19): e202101271.
[12] BEAUMONT J, HART M.Multiple Bragg reflection monochromators for synchrotron X radiation.Journal of Physics E: Scientific Instruments, 1974, 7(10): 823.
[13] KAYANI A B, KURIAKOSE S, MONSHIPOURI M,et al. UV photochromism in transition metal oxides and hybrid materials. Small, 2021, 17(32): 2100621.
[14] WANG X, SHI H F, MA H L,et al. Organic phosphors with bright triplet excitons for efficient X-ray-excited luminescence. Nat. Photonics, 2021, 15(3): 187.
[15] KAWAMURA I, KAWAMOTO H, FUJIMOTO Y,et al. Isomerization behavior of diarylethene-type photochromic compounds under X-ray irradiation: application to dosimetry. Jpn. J. Appl. Phys., 2020, 59(4): 046004.
[16] YANG D D, ZHENG H W, XUE J H,et al. Effect of lattice water on the photochromic property/photochromism of a Zn(II)-viologen coordination polymers. Journal of Molecular Structure, 2024, 1311: 138340.
[17] WU J, TAO C, LI Y,et al. Methylviologen-templated layered bimetal phosphate: a multifunctional X-ray-induced photochromic material. Chem. Sci., 2014, 5(11): 4237.
[18] HAN Y-F, XU X-M, WANG S-H, et al. Reusable radiochromic semiconductive MOF for dual-mode X-ray detection using color change and electric signal. Chem. Eng. J., 2022, 437: 135468.
[19] LU L, PENG S C, ZHAO L,et al. Visualized X-ray dosimetry for multienvironment applications. Nano Lett., 2023, 23(18): 8753.
[20] YUAN M, JIA R, JIANG X, et al. Room-temperature X-ray induced photochromic properties of tungsten oxide. Mater. Lett., 2023, 349: 134688.
[21] YANG Z, HU J, VAN DER HEGGEN D, et al. A versatile photochromic dosimeter enabling detection of X‐ray, ultraviolet, and visible photons. Laser & Photonics Reviews, 2023, 17(5): 2200809.
[22] LIU J, LU Y, LI J,et al. UV and X-ray dual photochromic properties of three CPs based on a new viologen ligand. Dyes Pigm., 2020, 177: 108276.
[23] LIU J, LU Y, LU W.Sun, UV and X-ray triple photochromic properties of three coordination polymers based on 1, 1′-bis (3-carboxylatobenzyl)-4, 4′-bipyridinium ligand.CrystEngComm, 2020, 22(12): 2121.
[24] ASAI K, KOSHIMIZU M, FUJIMOTO Y.Isomerization behavior of spiropyran-based compounds upon X-ray irradiation.Radiat Meas, 2017, 106: 166.
[25] DU J, YANG Z, LIN H,et al. Inorganic photochromic materials: Recent advances, mechanism, and emerging applications. Responsive Materials, 2024, 2(2): e20240004.
[26] LIU L, HU H, PAN W,et al. Robust organogel scintillator for self‐healing and ultra‐flexible X‐ray imaging. Adv. Mater., 2024, 36(13): 2311206.
[27] GUO P-Y, SUN C, ZHANG N-N,et al. An inorganic-organic hybrid photochromic material with fast response to hard and soft X-rays at room temperature. Chem Commun, 2018, 54(36): 4525.
[28] ZHANG F, ZHOU Y C, CHEN Z P,et al. Large-area X-Ray scintillator screen based on cesium hafnium chloride microcrystals films with high sensitivity and stability. Laser Photonics Rev., 2023, 17(5): 2200848.
[29] SUN F, XU H, HONG W,et al. 2D CuInP₂Se₆ in high‐sensitivity UV‐vis and X‐ray detection. Adv. Funct. Mater., 2024, 34(22): 2313776.
[30] BYRON H C, SWAIN C, PATURI P,et al. Highly tuneable photochromic sodalites for dosimetry, security marking and imaging. Adv. Funct. Mater., 2023, 33(42): 2303398.
[31] SAMOILENKO Y, KAGANOVSKII Y, LIPOVSKII A,et al. CW laser discoloration of X-ray irradiated silver doped silicate glasses. Opt. Mater., 2008, 30(11): 1715.
[32] YUAN W, NIU G, XIAN Y,et al. In situ regulating the order-disorder phase transition in Cs₂AgBiBr₆ single crystal toward the application in an X‐ray detector. Adv. Funct. Mater., 2019, 29(20): 1900234.
[33] TANG H T, LIU S B, FANG Z H,et al. High-resolution X-ray time-lapse imaging from fluoride nanocrystals embedded in glass matrix. Advanced Optical Materials, 2022, 10(12): 2102836.
[34] SONG Y, ZHAO H, ZI Y,et al. X-ray-irradiation-induced discoloration and persistent radioluminescence for reversible dual-mode imaging and detection applications. ACS Energy Lett., 2023, 8(5): 2232.
[35] ZHANG H, YANG Z, ZHOU M,et al. Reproducible X‐ray imaging with a perovskite nanocrystal scintillator embedded in a transparent amorphous network structure. Adv. Mater., 2021, 33(40): 2102529.
[36] HU Y, SUN Y, HOU S,et al. UV and X-ray induced photochromic material based on defect state exchanges. Chem. Eng. J., 2024, 495: 153600.
[37] OU X, QIN X, HUANG B,et al. High-resolution X-ray luminescence extension imaging. Nature, 2021, 590(7846): 410.
[38] ZUO J, KEIL P, GRUNDMEIER G.Synthesis and characterization of photochromic Ag-embedded TiO₂ nanocomposite thin films by non-reactive RF-magnetron sputter deposition.Appl. Surf. Sci., 2012, 258(18): 7231.
[39] HOLTON W C.Paramagnetic resonance of F centers in alkali halides.Phys. Rev., 1962, 125(1): 89.
[40] SEITZ F.Color centers in alkali halide crystals.Rev. Mod. Phys., 1946, 18(3): 384.
[41] BYRON H C, SWAIN C, LASTUSAARI P P C R H L B. Highly tuneable photochromic sodalites for dosimetry, security marking and imaging.Adv. Funct. Mater., 2023, 33(42): 2303389.
[42] SONG Y Y, ZHAO H P, ZI Y Z,et al. X-ray-irradiation-induced discoloration and persistent radioluminescence for reversible dual-mode imaging and detection applications. ACS Energy Lett., 2023, 8(5): 2232.
[43] HOYA J, LABORDE J I, RICHARD D, et al. Destabilisation of nanoporous membranes through GB grooving and grain growth. Comput. Mater. Sci., 2017, 139: 1.
[44] ZHU Y, SUN H Q, JIA Q N, et al. Site-selective occupancy of Eu²+ toward high luminescence switching contrast in BaMgSiO₄-based photochromic materials. Adv. Opt. Mater., 2021, 9(6): 2001626.
[45] JIN Y H, HU Y H, YUAN L F,et al. Multifunctional near-infrared emitting Cr³+-doped Mg₄Ga₈Ge₂O₂₀ particles with long persistent and photostimulated persistent luminescence, and photochromic properties. J. Mater. Chem. C, 2016, 4(27): 6614.
[46] RABIN H, KLICK C C.Formation of F centers at low and room temperatures.Phys. Rev., 1960, 117(4): 1005.
[47] ROY R.ChemInform abstract: ceramics by the solution‐sol‐gel route.ChemInform, 1988, 19(18): 1664.
[48] BAI X, XU Z, ZI Y Z,et al. Dual-functional X-ray photochromic phosphor: high-performance detection and 3D imaging. Adv. Funct. Mater., 2024, 34(37): 2402452.
[49] PATHAK N, GUPTA S K, GHOSH P S, et al. Probing local site environments and distribution of manganese in SrZrO₃:Mn; PL and EPR spectroscopy complimented by DFT calculations. RSC Adv., 2015, 5(23): 17501.
[50] ZHANG Y Y, LUO L H, LI K X, et al. Reversible up- conversion luminescence modulation based on UV- VIS light- controlled photochromism in Er³+doped Sr₂SnO₄. J. Mater. Chem. C, 2018, 6(48): 13148.
[51] LEE S H, CHEONG H M, LIU P,et al. Raman spectroscopic studies of gasochromic a-WO₃ thin films. Electrochimica Acta, 2001, 46(13/14): 1995.
[52] YUAN M, JIA R, JIANG X,et al. Room-temperature X-ray induced photochromic properties of tungsten oxide. Mater. Lett., 2023, 349: 134688.
[53] HE Y, WU Z, FU L,et al. Photochromism and size effect of WO₃ and WO₃-TiO₂ aqueous sol. Chem. Mater., 2003, 15(21): 4039.
[54] EGRANOV A, SIZOVA T Y, SHENDRIK R Y,et al. Instability of some divalent rare earth ions and photochromic effect. Journal of Physics and Chemistry of Solids, 2016, 90: 7.
[55] SCOULER W, SMAKULA A.Coloration of pure and doped calcium fluoride crystals at 20 ℃ and -190 ℃.Physical Review, 1960, 120(4): 1154.
[56] LU L, PENG S, ZHAO L,et al. Visualized X-ray dosimetry for multienvironment applications. Nano Letters, 2023, 23(18): 8753.
[57] SUN Y H, LI C L, WANG W F,et al. A photochromic and scintillation Eu-MOF with visual X-ray detection in bright and dark environments. Chem. Commun., 2022, 58(25): 4056.
[58] JIN Y, HU Y, YUAN L,et al. Multifunctional near-infrared emitting Cr³+-doped Mg₄Ga₈Ge₂O₂₀ particles with long persistent and photostimulated persistent luminescence, and photochromic properties. J. Mater. Chem. C, 2016, 4(27): 6614.
[59] COLETTE D, MAZON D, BARNSLEY R,et al. Conceptual study of energy resolved X-ray measurement and electron temperature reconstruction on ITER with low voltage ionization chambers. Rev. Sci. Instrum., 2021, 92(8): 083511.
[60] PAN L, LIU Z, WELTON C,et al. Ultrahigh‐flux X‐ray detection by a solution‐grown perovskite CsPbBr₃ single‐crystal semiconductor detector. Adv. Mater., 2023, 35(25): 2211840.
[61] YANG L, ZHANG H, ZHOU M,et al. High-stable X-ray imaging from all-inorganic perovskite nanocrystals under a high dose radiation. J. Phys. Chem. Lett., 2020, 11(21): 9203.
[62] LIU J, SHABBIR B, WANG C,et al. Flexible, printable soft‐X‐ray detectors based on all‐inorganic perovskite quantum dots. Adv. Mater., 2019, 31(30): 1901644.
[63] ZHANG Y, SUN R, OU X,et al. Metal halide perovskite nanosheet for X-ray high-resolution scintillation imaging screens. ACS Nano, 2019, 13(2): 2520.
[64] LI L Q, TAO L T, WANG L X, et al. Monolithic integration of perovskite heterojunction on TFT backplanes through vapor deposition for sensitive and stable X-ray imaging. Sci. Adv., 2024, 10(17): eadj8659.
[65] ZHAO J, ZHAO L, DENG Y,et al. Perovskite-filled membranes for flexible and large-area direct-conversion X-ray detector arrays. Nat. Photonics, 2020, 14(10): 612.
[66] LI W, XU Y, PENG J, et al. Evaporated perovskite thick junctions for X-ray detection. ACS Appl. Mater. Interfaces, 2021, 13(2): 2971-2978.
[67] QIAN W, XU X, WANG J,et al. An aerosol-liquid-solid process for the general synthesis of halide perovskite thick films for direct-conversion X-ray detectors. Matter, 2021, 4(3): 942.
[68] LIU L, LI W, FENG X, et al. Energy transfer assisted fast X‐ray detection in direct/indirect hybrid perovskite wafer. Adv. Sci., 2022, 9(15): 2103735.
[69] XIA M L, SONG Z H, WU H D,et al. Compact and large-area perovskite films achieved via soft-pressing and multi-functional polymerizable binder for flat-panel X-ray imager. Adv. Funct. Mater., 2022, 32(16): 2110729.
[70] DEUMEL S, VAN BREEMEN A, GELINCK G,et al. High-sensitivity high-resolution X-ray imaging with soft-sintered metal halide perovskites. Nat. Electron., 2021, 4(9): 681.
[71] DU X Y, LIU Y M, PAN W C,et al. Chemical potential diagram guided rational tuning of electrical properties: a case study of CsPbBr₃ for X-ray detection. Adv. Mater., 2022, 34(17): 2110252.
[72] ZHOU Y, ZHAO L, NI Z Y, et al. Heterojunction structures for reduced noise in large-area Heterojunction structures for reduced noise in large-area and sensitive perovskite X-ray detectors. Sci. Adv., 2021, 7(36): eabg6716.
[73] CHEN C, SUN J K, ZHANG Y J,et al. Flexible viologen‐based porous framework showing X‐ray induced photochromism with single‐crystal‐to‐single‐crystal transformation. Angew Chem., 2017, 129(46): 14650.
[74] LU H, XIE J, WANG X Y,et al. Visible colorimetric dosimetry of UV and ionizing radiations by a dual-module photochromic nanocluster. Nat. Commun., 2021, 12(1): 2798.
[75] YANG Z, HU J, VAN DER HEGGEN D,et al. A versatile photochromic dosimeter enabling detection of X‐Ray, ultraviolet, and visible photons. Laser Photonics Rev., 2023, 17(5): 2200809.
[76] ZHANG F, ZHOU Y, CHEN Z,et al. Large‐area X‐ray scintillator screen based on cesium hafnium chloride microcrystals films with high sensitivity and stability. Laser Photonics Rev., 2023, 17(5): 2200848.
[77] ABDOLLAHI A, ROGHANI-MAMAQANI H, RAZAVI B,et al. Photoluminescent and chromic nanomaterials for anticounterfeiting technologies: recent advances and future challenges. ACS Nano, 2020, 14(11): 14417.
[78] BAR N, CHOWDHURY P.A brief review on advances in rhodamine B based chromic materials and their prospects.ACS Appl. Electron. Mater., 2022, 4(8): 3749.
[79] WUTTIG M, YAMADA N.Phase-change materials for rewriteable data storage.Nat. Mater., 2007, 6(11): 824.
[80] SUN H Q, LI X F, ZHU Y, et al. Achieving multicolor emission readout and tunable photoswitching via multiplexing of dual lanthanides in ferroelectric oxides. J. Mater. Chem. C, 2019, 7(19): 5782.
[81] YANG Z, DU J, MARTIN L I,et al. Designing photochromic materials with large luminescence modulation and strong photochromic efficiency for dual‐mode rewritable optical storage. Adv. Opt. Mater., 2021, 9(20): 2100669.
[82] LI X, GUAN L, LI Y,et al. Optical control of Er³+-doped M_0.5Bi_2.5Nb₂O₉(M = Li, Na, K) materials for thermal stability and temperature sensing using photochromic reactions. J. Mater. Chem. C, 2020, 8(44): 15685.
[83] SONG Y Y, ZHAO H P, ZI Y Z,et al. X-ray-irradiation-induced discoloration and persistent radioluminescence for reversible dual-mode imaging and detection applications. ACS Energy Lett., 2023, 8(5): 2232.
[84] ZHANG H, ZHANG X, SUN W,et al. All‐solid‐state transparent variable infrared emissivity devices for multi‐mode smart windows. Adv. Funct. Mater., 2024, 34(16): 2307356.
[85] CHOI K, CHON J W, GU M,et al. Low‐distortion holographic data storage media using free‐radical ring‐opening polymerization. Adv. Funct. Mater., 2009, 19(22): 3560.
[86] XIAO Y, XIONG P, ZHANG S, et al. Cation-defect-induced self-reduction towards efficient mechanoluminescence in Mn²+-activated perovskites. Mater. Horiz., 2023, 10(9): 3476.