Eu(ii)-based halide nanocrystal-diffused glass, method of making and use thereof

Abstract

The application discloses a Eu(II) based halide nanocrystal dispersion glass, and a chemical composition thereof includes, in terms of molar percentage of oxide or halide: SiO2 40-65%, Al2O3+1 / 2AlF3 5-25%, MO+MX2 10-23%, A2O+1 / 2AX 3-15%, Eu2O3+1 / 2EuX3 0.05-7%; wherein, M is an alkaline earth metal element, A is an alkali metal element, and X is a halogen. The application can prepare alkali metal halide and CsEuX3 nanocrystals, realizes controllable precipitation of different crystal phase halide nanocrystals, promotes realization of high-efficiency adjustable light emission in a deep blue light to cyan light range, simultaneously obtains high color purity and high-efficiency light emission, and can have good thermal stability, water resistance and light stability, and has potential application prospects in the fields of solid-state lighting, display backlight sources and X-ray detection and imaging.

Description

Technical Field

[0001] This invention belongs to the field of optical functional glass materials technology, specifically relating to an Eu(II)-based halide nanocrystalline dispersion glass, its preparation method, and its application. Background Technology

[0002] Metal halide perovskite semiconductor materials possess excellent optoelectronic properties. Compared to CsPbX3 perovskite materials, Eu(II)-activated metal halide fluorescent materials exhibit better thermal and photostability. The luminescence of Eu(II)-based fluorescent materials primarily originates from spin-allowed transitions in their 5d-4f orbitals, which can be finely regulated over a wide range through the matrix crystal field. They can be excited by violet or near-ultraviolet light, exhibiting high absorption efficiency, short fluorescence lifetime, and are green and non-toxic, making them highly promising for applications in solid-state lighting, backlight displays, and X-ray fluorescence detection.

[0003] However, both Eu(II) and halides are highly sensitive to oxygen, heat, and moisture. Under the influence of heat and air, Eu(II) is easily oxidized to Eu(III). CsEuX3 nanocrystals prepared by traditional chemical solvent synthesis methods still show an 8% decrease in fluorescence intensity after 5 months, even under a nitrogen atmosphere, which greatly limits their practical application; usually, Eu(II)-based halide fluorescent materials require strict encapsulation.

[0004] Currently, there are relevant literature and patent reports on Eu(II)-doped CsMX3 (M is an alkaline earth metal ion) and CsBr nanocrystalline dispersion glasses, which have significantly improved stability. However, the existing nanocrystals have limited tolerance to Eu(II), and the effective doping content of Eu(II) is low, resulting in poor fluorescence efficiency and spectral modulation ability. On the other hand, the reported Eu(II)-doped CsMX3 nanocrystalline glasses usually use a reducing agent (carbon powder, Al element, SiC, etc.) to reduce Eu(III) in the glass matrix to Eu(II) before doping into the nanocrystals. This not only complicates the glass preparation process, but also results in low spectral purity due to the coexistence of Eu(III) and Eu(II) (J. Mater. Chem. C, 2023,11, 10389-10397). Summary of the Invention

[0005] The main objective of this invention is to address the problem that existing Eu(II)-doped alkali metal halide and CsEuX3 nanocrystal materials are susceptible to degradation of structure and fluorescence performance due to factors such as oxygen, heat, and humidity. The invention provides a series of Eu(II)-based halide nanocrystal dispersion glasses that exhibit highly efficient tunable luminescence in the deep blue to cyan light range, while also possessing good thermal stability, water resistance, and light stability. These glasses have potential applications in fields such as solid-state lighting, display backlights, and X-ray detection and imaging.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: An Eu(II)-based halide nanocrystalline dispersion glass, wherein the chemical composition of the nanocrystalline dispersion glass, based on the molar percentage content of oxides or halides, comprises: SiO2 40-65%, Al2O3+1 / 2AlF3 5-25%, MO+MX2 10-23%, A2O+1 / 2AX 3-15%, Eu2O3+1 / 2EuX3 0.05-7%; wherein M is one or more of Mg, Ca, Sr, and Ba, A is Na, K, or Cs, and X is one or more combinations of Cl, Br, or I.

[0007] Furthermore, the Eu(II)-based halide nanocrystalline dispersed glass is an Eu(II)-doped alkali metal halide or a CsEuX3 nanocrystalline dispersed glass.

[0008] Furthermore, in the nanocrystalline dispersed glass, Al2O3-1 / 2AlF3≤12%, and 1 / 2AlF3≥3%.

[0009] Furthermore, in the nanocrystalline dispersed glass, 50%≤SiO2+Al2O3+1 / 2AlF3≤75%.

[0010] Furthermore, in the nanocrystalline dispersed glass, 30% ≤ 2MX2 + AX ​​+ 3EuX3 ≤ 55%.

[0011] Furthermore, the MO and A2O are introduced in the form of carbonates or hydroxides.

[0012] In the above scheme, when A is Na, Eu(II)-doped NaX nanocrystals are formed in the glass.

[0013] In the above scheme, when A is K, Eu(II)-doped KX nanocrystals are formed in the glass.

[0014] In the above scheme, when A is Cs and Eu2O3+1 / 2EuX3<1.5%, Eu(II)-doped CsX nanocrystals are formed in the glass; when A is Cs and Eu2O3+1 / 2EuX3≥1.5%, CsEuX3 nanocrystals are formed in the glass.

[0015] The preparation method of the above-mentioned Eu(II)-based halide nanocrystalline dispersion glass includes the following steps: weighing the raw materials according to the glass composition and mixing them thoroughly, then heating at 1150~1400℃. o Melt within a temperature range of C (10~40 min), quench and shape to obtain transparent glass, then process at 480~620°C. oThe Eu(II)-doped alkali metal halide and Eu(II)-based halide nanocrystalline dispersed glass was obtained by heat treatment at temperature C for 1~50h.

[0016] The Eu(II)-doped alkali metal halide or CsEuX3 nanocrystalline dispersion glass prepared by the above scheme modifies and provides various crystal field environments for Eu(II), thereby obtaining tunable emission in the deep blue to cyan range (400-470 nm), with a full width at half maximum (FWHM) of 25-70 nm and a fluorescence efficiency of up to 65%; at 200 o The fluorescence intensity at C is ~62% of the room temperature fluorescence intensity; it has the advantages of high fluorescence efficiency, high color purity, good thermal stability and chemical stability, and has great potential application value in fields such as solid-state lighting, display backlight, and X-ray detection and imaging.

[0017] The Eu(II)-based halide nanocrystals of this invention use Eu(II) as the crystal lattice host, which has the advantages of high efficiency and high absorption. By introducing F element to adjust the glass redox ability and combining crystallization to promote the Eu(III)→Eu(II) reaction to consume the residual Eu(III) in the glass matrix, high color purity and high crystallinity are achieved. Furthermore, controllable crystallization of nanocrystals with different crystal phases can be achieved, providing a variety of Eu(II) crystal field environments, and achieving tunable luminescence (400-470 nm) in the range of deep blue to cyan light.

[0018] Compared with the prior art, the beneficial effects of the present invention include: 1. This invention can prepare alkali metal halides and CsEuX3 nanocrystals, and can achieve the controllable precipitation of halide nanocrystals with different crystal phases, including NaCl, KCl, CsCl, NaBr, KBr, CsBr, NaI, KI, CsI, CsEuCl3, CsEuBr3, CsEuI3 or mixed halogen (such as Cs(Cl / Br) etc.) nanocrystals; these nanocrystals provide diverse crystal field environments for Eu(II), promoting the acquisition of tunable luminescence in the range of deep blue to cyan; it has the characteristics of being green and non-toxic, having good stability, high luminescence efficiency, and wide applicability.

[0019] 2. This invention does not require the introduction of an additional reducing agent. It directly improves the reducing power of the glass system by changing the F content, causing Eu(III) to be reduced to Eu(II) and enter the nanocrystals, thereby obtaining high color purity and high-efficiency luminescence. In addition, the introduction of F changes the density of the glass network structure and promotes the formation of lattice-forming elements (such as Cs). + Eu 2+ X - (etc.) migration, which is conducive to the precipitation of alkali metal halides and CsEuX3 nanocrystals.

[0020] 3. The melt quenching-heat treatment crystallization method used in this invention is simple and can be prepared on a large scale. It avoids the disadvantages of alkali metal halides and CsEuX3 nanocrystals absorbing moisture and Eu(II) being oxidized to Eu(III) under the action of heat and oxygen.

[0021] 4. The nanocrystalline dispersed glass obtained by this invention has broad application prospects in the field of high-performance X-ray imaging. In X-ray fluorescence detection, using the large-area transparent nanocrystalline dispersed glass obtained by this invention as a scintillator, its light yield reaches 42558 ph / MeV, and its spatial resolution is 30 lp / mm. Attached Figure Description

[0022] Figure 1 Transmission electron microscopy image of the Eu(II)-doped CsBr nanocrystalline dispersed glass obtained in Example 1; Figure 2 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the Eu(II)-doped CsBr nanocrystalline dispersed glass obtained in Example 1 under 365 nm ultraviolet light excitation are shown. Figure 3 The illustration shows the actual blue LED assembled from the Eu(II)-doped CsBr nanocrystalline dispersed glass obtained in Example 1 and a 365 nm ultraviolet LED, along with its electroluminescence spectrum. Figure 4 The X-ray diffraction pattern (a) and fluorescence spectrum (b) under 365 nm ultraviolet light excitation of the Eu(II)-doped KBr nanocrystalline dispersion glass obtained in Example 2 are shown. Figure 5 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the Eu(II)-doped NaBr nanocrystalline dispersed glass obtained in Example 3 under 365 nm ultraviolet light excitation are shown. Figure 6 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the Eu(II)-doped CsI nanocrystalline dispersion glass obtained in Example 4 are shown. Figure 7 The X-ray diffraction pattern (a) and fluorescence spectrum (b) under 365 nm ultraviolet light excitation of the Eu(II)-doped KI nanocrystalline dispersion glass obtained in Example 5 are shown. Figure 8 The X-ray diffraction pattern (a) and fluorescence spectrum (b) under 365 nm ultraviolet light excitation of the Eu(II)-doped NaI nanocrystalline dispersion glass obtained in Example 6 are shown. Figure 9 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the Eu(II)-doped CsCl nanocrystalline dispersion glass obtained in Example 7 are shown. Figure 10 The X-ray diffraction pattern (a) and fluorescence spectrum (b) under 365 nm ultraviolet light excitation of the Eu(II)-doped Cs(Cl / Br) nanocrystalline dispersion glass obtained in Example 8 are shown. Figure 11 The X-ray diffraction pattern (a) and fluorescence spectrum (b) under 365 nm ultraviolet light excitation of the Eu(II)-doped Cs(Br / I) nanocrystalline dispersion glass obtained in Example 9 are shown. Figure 12 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the CsEuCl3 nanocrystalline dispersion glass obtained in Example 10 under 365 nm ultraviolet light excitation are shown. Figure 13 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the CsEuBr3 nanocrystalline dispersion glass obtained in Example 11 under 365 nm ultraviolet light excitation are shown. Figure 14 The fluorescence spectrum (a), spatial resolution photograph (b), and circuit structure (c) of the CsEuBr3 nanocrystalline dispersion glass obtained in Example 11 under X-ray irradiation are shown. Figure 15 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the CsEuI3 nanocrystalline dispersion glass obtained in Example 12 under 365 nm ultraviolet light excitation are shown. Figure 16 The X-ray diffraction pattern (a) and fluorescence spectrum (b) of the product obtained in Comparative Example 1 under 365 nm ultraviolet light excitation are shown. Figure 17 The X-ray diffraction pattern of the product obtained in Comparative Example 2 is shown.

[0023] Figure 18 The X-ray diffraction pattern of the product obtained in Comparative Example 3 is shown.

[0024] Figure 19 The X-ray diffraction pattern of the product obtained in Comparative Example 4 is shown.

[0025] Figure 20 The X-ray diffraction pattern of the product obtained in Comparative Example 6 is shown. Detailed Implementation

[0026] The present invention will be further described in detail below through specific implementation examples. These implementation examples are based on the technology of the present invention, and detailed implementation methods and specific operating procedures are given. However, the scope of protection of the present invention is not limited to the implementation examples given below.

[0027] Example 1

[0028] An Eu(II)-doped CsBr nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 40%, Al2O3 5%, AlF3 10%, CaO 8%, CaBr2 15%, Cs2O 10%, CsBr 10%, EuBr3 2%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature of 1150°C. o C / 40min; after quenching and forming, then at 520 o Incubate at C for 10 h to obtain Eu 2+ CsBr-doped nanocrystalline dispersed glass.

[0029] Figure 1 The image shown is a transmission electron microscope (TEM) image of the product obtained in this embodiment. Analysis of the high-resolution TEM image and the corresponding Fourier transform diagram shows that the nanocrystals in the glass match the cubic CsBr crystal (PDF#78-0615). The interplanar spacings marked in the image are 4.178 Å and 3.557 Å, respectively, slightly smaller than the (111) and (200) planes of the CsBr crystal (PDF#78-0615). This is because the smaller ionic radius Eu(II) has replaced the larger ionic radius Cs. + This result demonstrates that CsBr crystals were precipitated in the glass, and that Eu(II) doping was incorporated into the CsBr crystals. Figure 2 (a) is the XRD pattern of the product obtained in this embodiment. Figure 2 (a) It can be seen that in addition to the glass “bun peak”, there is also a sharp crystal diffraction peak; the diffraction angle of the crystal diffraction peak is slightly larger than that of the diffraction peak of CsBr crystal (PDF#78-0615), which further proves that Eu(II) doped CsBr nanocrystals have been precipitated in the glass.

[0030] Figure 2 (b) For the untreated sample and 520 o Fluorescence spectrum of Eu(II)-doped CsBr nanocrystalline dispersed glass obtained after C / 10 h heat treatment under 365 nm UV excitation. Figure 2 (b) It can be seen that, compared with the untreated sample, after heat treatment, due to the Eu(II) doping into the CsBr crystal with lower phonon energy, its fluorescence peak half width at half maximum (FWHM) is narrower, changing from 71 nm to 26 nm; the fluorescence peak also redshifts from 436 nm to 446 nm, and the fluorescence quantum efficiency increases from 15% to 52%. Figure 3 (a) is 520 oThe fluorescence intensity of the Eu(II)-doped CsBr nanocrystalline dispersed glass obtained after heat treatment at C / 10 h is shown in the graph as a function of temperature under 365 nm ultraviolet light excitation. The graph shows that when the temperature increases to 150... o At C, its fluorescence intensity can still retain about 62% of the initial room temperature fluorescence intensity. Figure 3 (b) is the actual blue LED assembled with a 365 nm ultraviolet LED (illustration) and its electroluminescence spectrum. As can be seen from the actual image, the assembled LED emits blue light with high color purity and high brightness under different current driving conditions.

[0031] Example 2

[0032] An Eu(II)-doped KBr nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 40%, Al2O3 15%, AlF3 20%, CaBr2 11%, SrBr2 10.9%, K2O 3%, EuBr3 0.1%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1250°C. o C / 20 min; after quenching and forming, then at 540 o After heating at C for 10 h, Eu(II)-doped KBr nanocrystalline dispersed glass was obtained.

[0033] Figure 4 (a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of KBr crystal (PDF#36-1471); the fluorescence spectrum under 365 nm ultraviolet excitation is as follows. Figure 4 As shown in (b), it exhibits a deep blue emission of 431 nm and a fluorescence peak with a full width at half maximum (FWHM) of 25 nm.

[0034] Example 3

[0035] An Eu(II)-doped NaBr nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 51%, Al2O3 15%, AlF3 6%, BaBr2 20%, Na2O 6%, EuBr3 2%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1400°C. o C / 10 min; after quenching and forming, then at 600 o After heating at C for 1 h, Eu(II)-doped NaBr nanocrystalline dispersed glass was obtained.

[0036] Figure 5 (a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of NaBr crystal (PDF#36-1456); the fluorescence spectrum under 365 nm ultraviolet light excitation is as follows. Figure 5 As shown in (b), it exhibits blue-violet emission at 429 nm and a fluorescence peak with a full width at half maximum (FWHM) of 25 nm.

[0037] Example 4

[0038] An Eu(II)-doped CsI nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 65%, Al2O3 2%, AlF3 6%, CaI2 15%, Cs2O 6%, CsI 5%, Eu2O3 1%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1350°C. o After quenching and shaping at 20 min (C), it is then heated to 580 °C. o After heating at C for 5 h, Eu(II)-doped CsI nanocrystalline dispersed glass was obtained.

[0039] Figure 6 (a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of CsI crystal (PDF#78-0616); the fluorescence spectrum under 365 nm ultraviolet excitation is as follows. Figure 6 As shown in (b), it exhibits cyan emission at 460 nm and a fluorescence peak with a full width at half maximum (FWHM) of 64 nm.

[0040] Example 5

[0041] An Eu(II)-doped KI nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 60%, Al2O3 12%, AlF3 6%, CaI2 13%, KI 8%, Eu2O3 1%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at 1300°C. o After quenching and shaping at 30 min (C), it is then heated to 600 °C. o After heating at C for 10 h, Eu(II)-doped KI nanocrystalline dispersed glass was obtained.

[0042] Figure 7(a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of the KI crystal (PDF#04-0471); the fluorescence spectrum under 365 nm UV excitation is as follows. Figure 7 As shown in (b), it exhibits blue emission at 440 nm and a fluorescence peak with a full width at half maximum (FWHM) of 39 nm.

[0043] Example 6

[0044] The preparation method of an Eu(II)-doped NaI nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 40%, Al2O3 12%, AlF3 8%, BaI2 19%, Na2O 10%, NaI 10%, Eu2O3 1%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1350°C. o After quenching and shaping at 20 min (C), it is then heated to 600 °C. o After heating at C for 10 h, Eu(II)-doped NaI nanocrystalline dispersed glass was obtained.

[0045] Figure 8 (a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of NaI crystal (PDF#89-3617); the fluorescence spectrum under 365 nm ultraviolet light excitation is as follows. Figure 8 As shown in (b), it exhibits blue emission at 437 nm and a fluorescence peak with a full width at half maximum (FWHM) of 31 nm.

[0046] Example 7

[0047] An Eu(II)-doped CsCl nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 52%, Al2O3 13%, AlF3 10%, MgCl2 10%, Cs2O 5%, CsCl 8%, EuCl3 2%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1300°C. o After quenching and shaping at 20 min (C), it is then heated to 540 °C. o After heating at C for 10 h, Eu(II)-doped CsCl nanocrystalline dispersion glass was obtained.

[0048] Figure 9(a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of CsCl crystal (PDF#73-0390); the fluorescence spectrum under 365 nm ultraviolet excitation is as follows. Figure 9 As shown in (b), it exhibits blue emission at 437 nm and a fluorescence peak with a full width at half maximum (FWHM) of 26 nm.

[0049] Example 8

[0050] An Eu(II)-doped Cs(Cl / Br) nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 45%, Al2O3 14%, AlF3 7%, CaCl2 8%, CaBr2 15%, Cs2O 2%, CsCl 7%, EuCl3 1%, EuBr3 1%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1250°C. o After quenching and shaping at 30 min (C), it is then heated to 540 °C. o After heating at C for 10 h, Eu(II)-doped Cs(Cl / Br) nanocrystalline dispersed glass was obtained.

[0051] Figure 10 (a) is its X-ray diffraction pattern, with sharp crystal diffraction peaks between those of CsCl crystal (PDF#78-0614) and CsBr crystal (PDF#78-0615); its fluorescence spectrum under 365 nm ultraviolet light excitation is shown below. Figure 10 As shown in (b), it exhibits blue emission at 439 nm and a fluorescence peak with a full width at half maximum (FWHM) of 27 nm.

[0052] Example 9

[0053] An Eu(II)-doped Cs(Br / I) nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 40%, Al2O3 5%, AlF3 10%, MgO 5%, MgBr2 17.1%, Cs2O 10%, CsI 10%, EuBr3 2.9%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1250°C. o After quenching and shaping at 20 min (C / 20°C), it is then heated to 620°C. o After heating at C for 10 h, Eu(II)-doped Cs(Br / I) nanocrystalline dispersed glass was obtained.

[0054] Figure 11 (a) is its X-ray diffraction pattern, with sharp crystal diffraction peaks between those of CsBr crystal (PDF#73-0391) and CsI crystal (PDF#77-2185); its fluorescence spectrum under 365 nm ultraviolet light excitation is shown below. Figure 10 As shown in (b), it exhibits blue emission at 451 nm and a fluorescence peak with a full width at half maximum (FWHM) of 31 nm.

[0055] Example 10

[0056] A CsEuCl3 nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 42%, Al2O3 8%, AlF3 10%, CaCl2 20%, Cs2O 3%, CsCl 10%, Eu2O3 7%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1300°C. o After quenching and shaping at 30 min (C), it is then heated to 540 °C. o CsEuCl3 nanocrystalline dispersed glass was obtained by holding the glass at C for 10 h.

[0057] Figure 12 (a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of CsEuCl3 crystal (PDF#42-1008); the fluorescence spectrum under 365 nm ultraviolet light excitation is as follows. Figure 12 As shown in (b), it exhibits blue emission at 440 nm and a fluorescence peak with a full width at half maximum (FWHM) of 30 nm.

[0058] Example 11

[0059] A CsEuBr3 nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 45%, Al2O3 7%, AlF3 10%, CaBr2 15%, Cs2O 10%, CsBr 10%, EuBr3 3%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1200°C. o After quenching and shaping at 40 min (C), it is then heated to 560 °C. o C, 580 o CsEuBr3 nanocrystalline dispersed glass was obtained by holding the glass at C for 10 h.

[0060] Figure 13 (a) is 560 oThe X-ray diffraction pattern of the C / 10 h heat-treated sample shows sharp crystal diffraction peaks that match those of CsEuBr3 crystal (PDF#1-76-3243); the fluorescence spectrum under 365 nm UV excitation is shown below. Figure 13 As shown in (b), it exhibits blue emission at 447 nm and a fluorescence peak with a full width at half maximum (FWHM) of 26 nm.

[0061] Figure 14 (a) Under the same test conditions, commercial BGO and 580 o The fluorescence spectrum of the C / 10 h heat-treated sample under X-ray irradiation was calculated to be 580. o The irradiated fluorescence intensity of the C / 10 h heat-treated sample was 5.35 times that of BGO, corresponding to a light yield of 42558 ph / MeV; Figure 14 As shown in (b), its spatial resolution can reach 30 lp / mm; Figure 14 (c) shows the USB flash drive under sunlight (above) and at 580. o The C / 10 h heat-treated sample is a scintillator, and the X-ray fluorescence imaging of it (below) clearly shows the complex circuit structure inside the USB flash drive.

[0062] Example 12

[0063] A CsEuI3 nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 45%, Al2O3 6%, AlF3 6%, CaI2 19%, Cs2O 10%, CsI 10%, Eu2O3 4%; 2) After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1250°C. o After quenching and shaping at 30 min (C), it is then heated to 580 °C. o CsEuI3 nanocrystalline dispersed glass was obtained by holding the glass at C for 10 h.

[0064] Figure 15 (a) is its X-ray diffraction pattern, whose sharp crystal diffraction peaks match those of CsEuI3 crystal (PDF#44-0213); the fluorescence spectrum under 365 nm ultraviolet excitation is as follows. Figure 15 As shown in (b), it emits a sky-blue light at 460 nm and has a fluorescence peak with a full width at half maximum (FWHM) of 65 nm.

[0065] Comparative Example 1 A Eu 2+ The preparation method of doped alkali metal halide-based glass includes the following steps: Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 47%, Al2O3 5%, AlF3 5%, CaBr2 10%, SrBr2 10%, Cs2O 10%, CsBr 10%, EuBr3 3%; after mixing the raw materials evenly, place them in an alumina crucible and melt them at 1250°C. o After quenching and shaping at 30 min (C), it is then heated to 620 °C. o After holding at C for 10 hours, CsBr crystals precipitated in the glass, but due to the low content of AlF3, a large amount of Eu was present in the glass. 3+ It was not restored to Eu 2+ Even after heat treatment, a large amount of Eu remains. 3+ The red glow caused Eu in the glass to... 2+ If the content is too low, Eu cannot be formed. 2+ Doped CsBr nanocrystals. Figure 16 The X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) are shown.

[0066] Comparative Example 2 Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 42%, Al2O3 16%, AlF3 6%, CaBr2 20%, Cs2O 8%, CsBr 5%, EuBr3 3%. After mixing the raw materials evenly, place them in an alumina crucible and melt them at 1250°C. o After quenching and shaping at 30 min (C), it is then heated to 620 °C. o Keep warm at C for 10 hours.

[0067] In this comparative example, due to the excessively high content of Al2O3 relative to AlF3 (Al2O3-1 / 2AlF3=13%), no nanocrystals precipitated in the glass (see...). Figure 17 ).

[0068] Comparative Example 3 Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 52%, Al2O3 13%, AlF3 10%, MgCl2 10%, Cs2O 5%, CsCl 8%, Eu2O3 1%. After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1300°C. o After quenching and shaping at 20 min (C), it is then heated to 540 °C. o After being kept at C for 10 hours, no crystals precipitated in the glass.

[0069] Compared to Example 7, this comparative example only reduced the Cl content, resulting in no nanocrystals precipitating in the glass matrix (see Example 7). Figure 18 ).

[0070] Comparative Example 4 Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 40%, Al2O3 5%, AlF3 10%, MgBr2 22.1%, Cs2O 10%, CsI 10%, EuBr3 2.9%. After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1250°C. o After being quenched and formed at 20°C, the resulting glass completely loses its transparency.

[0071] Compared to Example 9, this comparative example only increased the Br content, resulting in an excessively high halogen content in the glass. Although Cs(Br / I) nanocrystals could precipitate in the glass, the glass completely lost its transparency (see Example 9). Figure 19 ) Comparative Example 5 Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 63%, Al2O3 12%, AlF3 6%, CaI2 10%, KI 8%, Eu2O3 1%. After mixing the raw materials evenly, place them in an alumina crucible and melt them at 1300°C. o C / 30min.

[0072] Compared to Example 5, this comparative example shows a slight increase in SiO2 content, which prevents the composition from forming glass.

[0073] Comparative Example 6 Weigh the raw materials according to the following molar percentages of oxides or halides: SiO2 35%, Al2O3 5%, AlF3 10%, MgO 5%, MgBr2 17.1%, Cs2O 10%, CsI 15%, EuBr3 2.9%. After mixing the raw materials evenly, place them in an alumina crucible and melt them at a high temperature. The specific melting conditions are 1250°C. o C / 20 min.

[0074] Compared to Example 9, the SiO2 content was reduced in this comparative example, resulting in an overly porous glass network. This glass composition was able to precipitate Cs(Br / I) nanocrystals, but the prepared untreated glass completely lost its transparency (see Example 9). Figure 20 ).

[0075] Finally, it should be noted that the above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. However, any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention and based on the structure of the present invention should be included within the protection scope of the present invention.

Claims

1. A Eu(II)-based halide nanocrystalline dispersed glass, characterized in that, The chemical composition of the nanocrystalline dispersed glass, in terms of the molar percentage of oxides or halides, includes: SiO2 40-65%, Al2O3+1 / 2AlF3 5-25%, MO+MX2 10-23%, A2O+1 / 2AX 3-15%, Eu2O3+1 / 2EuX3 0.05-7%; wherein, M is an alkaline earth metal element, A is an alkali metal element, and X is a halogen.

2. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, The Eu(II)-based halide nanocrystalline dispersion glass is an Eu(II)-doped alkali metal halide or a CsEuX3 nanocrystalline dispersion glass.

3. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, In the nanocrystalline dispersed glass, Al2O3-1 / 2AlF3≤12%, and 1 / 2AlF3≥3%.

4. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, In the nanocrystalline dispersed glass, 50%≤SiO2+Al2O3+1 / 2AlF3≤75%.

5. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, In the nanocrystalline dispersed glass, 30%≤2MX2+AX+3EuX3≤55%.

6. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, When A is Na, Eu(II)-doped NaX nanocrystals are formed in the glass; when A is K, Eu(II)-doped KX nanocrystals are formed in the glass.

7. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, When A is Cs and Eu2O3+1 / 2EuX3<1.5%, Eu(II)-doped CsX nanocrystals are formed in the glass. When A is Cs and Eu2O3+1 / 2EuX3≥1.5%, CsEuX3 nanocrystals are formed in the glass.

8. The Eu(II)-based halide nanocrystalline dispersion glass according to claim 1, characterized in that, M is one or more of Mg, Ca, Sr, and Ba; A is Na, K, or Cs; and the halogen is one or more of Cl, Br, or I.

9. A method for preparing the Eu(II)-based halide nanocrystalline dispersed glass according to any one of claims 1 to 8, characterized in that, The process includes the following steps: after thoroughly mixing the raw materials weighed according to the glass composition, the mixture is melted at high temperature, quenched and shaped to obtain transparent glass, and then heat-treated to obtain the Eu(II)-based halide nanocrystalline dispersion glass.

10. The preparation method according to claim 9, characterized in that, The high-temperature melting temperature is 1150~1400℃. o C; Heat treatment temperature is 480~620℃ o C, the heat preservation time is 1~50 h.

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