A strontium-based mixed halide nanocrystal-diffused glass and a method of making the same

Abstract

A kind of strontium-based mixed halide nanocrystal dispersion glass, the glass is in mole percentage, B2O3: 28~56, Al2O3+1 / 2AlX3: 0~17.5, 24≤MO+MX2≤68, Ln2O3+1 / 2LnX3: 0~4;Wherein, X is one or more than two combinations of Cl or F, M is one or more than two combinations of Ca, Sr or Ba, Ln is rare earth ion.The SrClF and Sr2(B5O9)Cl nanocrystal dispersion glass can be prepared by the application, the controlled precipitation of different crystal phase halide nanocrystals is realized, the strontium-based mixed halide nanocrystal of the application has low phonon energy, rich doping lattice, and promotes the realization of blue light to near-infrared high-efficiency adjustable luminescence.

Description

Technical Field

[0001] This invention belongs to the field of optical functional glass, specifically relating to a strontium-based mixed halide nanocrystalline dispersion glass and its preparation method. Background Technology

[0002] Alkaline earth metal halide matrix materials possess good stability and low phonon energy, making them valuable for applications in lasers, lighting, and displays. However, the single doping site and low solid solubility of rare earth elements in alkaline earth metal halides can easily lead to concentration quenching and low excitation efficiency. In contrast, alkaline earth metal mixed halides (SrClF, Sr2(B5O9)Cl) exhibit multiple luminescent sites and higher solid solubility of rare earth elements, resulting in higher light output efficiency and excitation efficiency during upconversion or downconversion fluorescence. However, the high hygroscopicity, easy dissociation, and difficulty in growing large-size crystals of alkaline earth metal mixed halides limit their practical applications.

[0003] Therefore, how to maintain the excellent optical properties of alkaline earth metal mixed halides while overcoming their defects such as poor chemical stability, hygroscopicity, and difficulty in processing has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0004] This invention provides an alkaline earth metal mixed halide nanocrystalline dispersed glass and its preparation method to solve the above-mentioned technical problems. This invention disperses strontium-based mixed halide nanocrystals in an inorganic glass matrix, utilizing the dense network structure of the glass to provide chemical and thermal protection for the nanocrystals. Through glass composition design and heat treatment process control, the controllable precipitation of different crystal phases (SrClF, Sr2(B5O9)Cl, and their mixed phases) is achieved, thereby obtaining a strontium-based mixed halide nanocrystalline dispersed glass with both high stability and highly efficient tunable luminescence.

[0005] The technical solution of the present invention is as follows: A strontium-based mixed halide nanocrystalline dispersion glass, wherein the chemical composition of the nanocrystalline dispersion glass, in molar percentage of oxides or halides, comprises: B2O3: 28~56, Al2O3+1 / 2AlX3: 0~17.5, 24≤MO+MX2≤68, Ln2O3+1 / 2LnX3: 0~4, wherein X is one or a combination of two of Cl or F, Ln is a rare earth ion, and M is one or a combination of more than two of Ca, Sr or Ba.

[0006] Wherein, AlX3 represents the sum of the molar percentages of AlF3 and AlCl3; MO represents the sum of the molar percentages of the oxides of M (CaO, SrO, BaO). The halides of M (CaF2, CaCl2, SrF2, SrCl) 2、The molar percentages of BaF2 and BaCl2 are summed; Ln2O3 represents the sum of the molar percentages of all rare earth oxides (such as Eu2O3, Ce2O3, Tb2O3, Er2O3, Yb2O3, etc.), and LnX3 represents the sum of the molar percentages of all rare earth halides (such as EuF3, EuCl3, CeCl3, TbF3, YbF3, ErF3, etc.). All components in each expression are expressed as molar percentages, and the value of unadded components is 0.

[0007] Furthermore, the nanocrystals in the strontium-based mixed halide nanocrystal dispersion glass are one or a combination of two of SrClF or Sr2(B5O9)Cl.

[0008] Furthermore, in the nanocrystalline dispersed glass, 28 ≤ B2O3 + Al2O3 ≤ 64.

[0009] Furthermore, in the nanocrystalline dispersed glass, when M includes Sr, 15 ≤ SrO + SrF2 + SrCl2 ≤ 58, and Sr / M ≥ 0.5. Sr / M ≥ 0.5 means that the molar proportion of strontium in all alkaline earth metals (Ca, Sr, Ba) is not less than 50%, thereby ensuring that strontium is the dominant alkaline earth metal.

[0010] Furthermore, in the nanocrystalline dispersed glass, 36≤2MCl2+3AlCl3+3LnCl3≤76, 0≤3AlF3+2MF2+3LnF3≤80, and F / Cl≤2.

[0011] In the above scheme, when 0.2≤Sr / Cl<0.5 and F / Cl≤0.5, the nanocrystals formed in the glass are Sr2(B5O9)Cl.

[0012] In the above scheme, when Sr / Cl=0.5 and 0.5<F / Cl≤1.25, the nanocrystals formed in the glass are SrClF.

[0013] In the above scheme, when Sr / Cl > 0.5 and 0.5 < F / Cl ≤ 2, the nanocrystals formed in the glass are SrClF and Sr2(B5O9)Cl.

[0014] In the Sr / Cl ratio, Sr is the sum of the molar percentages of Sr in SrO, SrF2, and SrCl2, and Cl is the sum of the molar percentages of Cl in all chlorides (including MCl2, AlCl3, and LnCl3); in the F / Cl ratio, F is the sum of the molar percentages of F in all fluorides (including AlF3, MF2, and LnF3).

[0015] The preparation method of the above-mentioned strontium-based mixed halide nanocrystalline dispersion glass includes the following steps: weighing the raw materials according to the glass composition and mixing them thoroughly, then heating at 1000~1400℃. o Melt within a temperature range of C (10~60min), quench and shape to obtain transparent glass, then process at 500~640℃. o The strontium-based mixed halide nanocrystalline dispersed glass was obtained by heat treatment at temperature C for 1~50h.

[0016] In the aforementioned nanocrystalline dispersed glass, when the rare earth ion in the glass is Eu, the luminescent ion-doped strontium-based mixed halide nanocrystalline dispersed glass emits blue light; when the rare earth ion in the glass is Tb, the luminescent ion-doped strontium-based mixed halide nanocrystalline dispersed glass emits green light; and when the rare earth ions in the glass are Yb and Er, the luminescent ion-doped strontium-based mixed halide nanocrystalline dispersed glass emits near-infrared light.

[0017] The beneficial effects of this invention are as follows: The glass composition involved in this invention can prepare strontium-based mixed halide nanocrystalline dispersion glass in glass, including SrClF and Sr2(B5O9)Cl, which solves the preparation problem of these two nanocrystalline dispersion glasses and combines the stability of glass with the excellent optical properties of strontium-based mixed halide nanocrystals.

[0018] The strontium-based mixed halide nanocrystalline dispersion glass prepared in this invention precipitates different crystal phases according to compositional changes. Both SrClF and Sr2(B5O9)Cl crystal structures contain two different Sr lattice sites, providing multiple doping sites and different crystal field environments for rare earth ions. It has important application prospects in the development of efficient and stable upconversion and downconversion fluorescent materials and devices based on strontium-based mixed halide nanocrystalline dispersion glass. Attached Figure Description

[0019] In the following figures, AP represents the original glass sample, i.e., the glass sample obtained by melting and forming without heat treatment; in the following figures, in the GXX-XXX expression, the first three digits GXX represent the sample number, and the number after "-" represents the heat treatment temperature. o C).

[0020] Figure 1 Eu obtained in Example 1 2+ X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) of Sr2(B5O9)Cl nanocrystalline dispersion glass; Figure 2 Eu obtained in Example 2 2+X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) of Sr2(B5O9)Cl nanocrystalline dispersion glass; Figure 3 Ce obtained in Example 3 3+ X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) of Sr2(B5O9)Cl nanocrystalline dispersion glass; Figure 4 Eu obtained in Example 4 2+ X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) of SrClF nanocrystalline dispersed glass. Figure 5 Er obtained in Example 5 3+ X-ray diffraction pattern of SrClF nanocrystalline dispersed glass; Figure 6 Er obtained in Example 5 3+ Fluorescence spectra of SrClF nanocrystalline dispersed glass under 980 nm near-infrared light excitation: downconversion (a) and upconversion (b) Figure 7 Yb obtained in Example 6 3+ With Er 3+ X-ray diffraction pattern (a) and upconversion fluorescence spectrum under 980 nm near-infrared light excitation (b) of co-doped SrClF nanocrystalline dispersed glass. Figure 8 Tb obtained in Example 7 3+ X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) of SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass. Figure 9 Eu obtained in Example 8 2+ X-ray diffraction pattern (a) and fluorescence spectrum under 365 nm ultraviolet light excitation (b) of SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass. Figure 10 The X-ray diffraction pattern of the SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass obtained in Example 9; Figure 11 The X-ray diffraction pattern of the product obtained in Comparative Example 1; Figure 12 The X-ray diffraction pattern of the product obtained in Comparative Example 2; Figure 13 The X-ray diffraction pattern of the product obtained in Comparative Example 3; Figure 14 The X-ray diffraction pattern of the product obtained in Comparative Example 5; Figure 15 The X-ray diffraction pattern of the product obtained in Comparative Example 6; Figure 16 The X-ray diffraction pattern of the product obtained in Comparative Example 7; Figure 17 The X-ray diffraction pattern of the product obtained in Comparative Example 8; Figure 18 The X-ray diffraction pattern of the product obtained in Comparative Example 9; Figure 19 The X-ray diffraction pattern of the product obtained in Comparative Example 10 is shown.

[0021] The present invention will be further described in detail below through specific embodiments. These embodiments are based on the technology of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the embodiments given below.

[0022] Table 1 Glass composition of Examples 1-9

[0023]

[0024] Example 1

[0025] A Eu 2+ The preparation method of doped Sr2(B5O9)Cl nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 39%, Al2O3: 12%, SrCl2: 20%, SrO: 15%, CaCl2: 10%, EuCl3: 4%.

[0026] 2) After mixing thoroughly, place the mixture in a crucible and melt it at 1350°C. o After quenching at 350°C for 20 min, the temperature was increased to 350°C. o Annealing at C for 3 hours yields colorless and transparent glass, denoted as G1. The original glass (G1-AP) is placed in a heat treatment furnace at 580°C. o Eu was obtained by heat treatment at C for 10 hours. 2+ The doped Sr2(B5O9)Cl nanocrystalline dispersed glass is designated G1-580.

[0027] Figure 1 a is the XRD pattern of the product obtained in this embodiment. Figure 1 As can be seen from this, the crystal diffraction peaks of sample G1-580 match those of Sr2(B5O9)Cl crystal (PDF#97-24-6037), proving that Sr2(B5O9)Cl nanocrystals have precipitated in the glass, and Eu... 2+The dopant was incorporated into the Sr2(B5O9)Cl nanocrystals. Figure 1 b shows the fluorescence spectra of AP and heat-treated samples under 365 nm UV excitation. Figure 1 (b) It can be seen that, compared with the untreated sample, after heat treatment, due to Eu 2+ When doped into the Sr2(B5O9)Cl crystal with lower phonon energy, its fluorescence peak half width at half maximum (FWHM) narrowed from 62 nm to 35 nm; the fluorescence peak also blue-shifted from 436 nm to 426 nm, and the fluorescence quantum efficiency increased from 11% to 42%.

[0028] Example 2

[0029] A Eu 2+ The preparation method of doped Sr2(B5O9)Cl nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 48%, AlF3: 10%, AlCl3: 12%, SrCl2: 10%, SrO: 5%, CaCl2: 10%, BaO: 3%, Eu2O3: 2%.

[0030] 2) After mixing thoroughly, place the mixture in a crucible and melt it at 1300°C. o After quenching at 40°C for 40 minutes, the temperature was increased to 400°C. o Annealing at C for 3 hours yielded colorless and transparent glass, denoted as G2. The original glass (G2-AP) was placed in a heat treatment furnace at 640°C. o Eu was obtained by heat treatment at C for 5 hours. 2+ The Sr2(B5O9)Cl nanocrystalline dispersed glass is designated as G2-640.

[0031] Figure 2 a is the XRD pattern of the product obtained in this embodiment. Figure 2 As can be seen from this, the crystal diffraction peaks of sample G2-640 match those of Sr2(B5O9)Cl crystal (PDF#97-24-6037), proving that Sr2(B5O9)Cl nanocrystals have precipitated in the glass, and Eu... 2+ The dopant was incorporated into the Sr2(B5O9)Cl nanocrystals. Figure 2 b shows the fluorescence spectra of AP and heat-treated samples under 365 nm UV excitation. Figure 2 (b) It can be seen that, compared with the untreated sample, after heat treatment, due to Eu 2+ The doping was incorporated into the Sr2(B5O9)Cl crystal, resulting in narrowband blue light emission.

[0032] Example 3

[0033] A Ce 3+ The preparation method of doped Sr2(B5O9)Cl nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 46%, AlCl3: 20%, SrF2: 18%, SrO: 12%, CeCl3: 4%.

[0034] 2) After mixing thoroughly, place the mixture in a crucible and melt it at 1400°C. o C / 10 min, after quenching, at 450 o Annealing at C for 3 hours yielded colorless and transparent glass, designated G3. The original glass (G3-AP) was placed in a heat treatment furnace at 620°C. o Ce was obtained by heat treatment at C for 10 hours. 3+ The doped Sr2(B5O9)Cl nanocrystalline dispersed glass is designated as G2-620.

[0035] Figure 3 a is the XRD pattern of the product obtained in this embodiment. Figure 3 As can be seen from this, the crystal diffraction peaks of sample G3-620 match those of Sr2(B5O9)Cl crystal (PDF#97-24-6037), proving that Sr2(B5O9)Cl nanocrystals have precipitated in the glass, and Ce... 3+ The dopant was incorporated into the Sr2(B5O9)Cl nanocrystals. Figure 3 b shows the fluorescence spectra of AP and heat-treated samples under 365 nm UV excitation. Figure 3 (b) It can be seen that, compared with the untreated sample, after heat treatment, due to Ce 3+ When doped into the Sr2(B5O9)Cl crystal with low phonon energy, its fluorescence peak half-width at half-maximum broadened, changing from 40 nm to 51 nm; the fluorescence peak also redshifted from 378 nm to 383 nm, and the fluorescence quantum efficiency increased from 17% to 53%.

[0036] Example 4

[0037] A Eu 2+ The preparation method of SrClF nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 56%, AlCl3: 16%, SrF2: 24%, EuF3: 4%.

[0038] 2) After mixing thoroughly, place the mixture in a crucible and melt at 1250°C. o After quenching at 350°C for 30 minutes, the temperature was reduced to 350°C. oAnnealing at C for 3 hours yielded colorless and transparent glass, designated G4. The original glass (G4-AP) was placed in a heat treatment furnace at 580°C. o Eu was obtained by heat treatment at C for 10 hours. 2+ The SrClF nanocrystalline dispersion glass is designated G4-580.

[0039] Figure 4 a is the XRD pattern of the product obtained in this embodiment. Figure 4 As can be seen from this, the crystal diffraction peaks of sample G4-580 match those of SrClF crystal (PDF#05-08-8672), proving that SrClF nanocrystals have precipitated in the glass, and Eu... 2+ The dopant has been incorporated into the SrClF nanocrystals. Figure 4 b shows the fluorescence spectra of AP and heat-treated samples under 365 nm UV excitation. Figure 4 b indicates that after heat treatment, SrClF nanocrystals are Eu 2+ The low phonon energy environment provided significantly enhanced its blue light intensity, with the full width at half maximum (FWHM) of its fluorescence peak changing from 71 nm to 31 nm; the fluorescence peak also red-shifted from 459 nm to 405 nm. This is due to the presence of two different Sr groups within the SrClF nanocrystals. 2+ Lattice sites, which in turn enable Eu 2+ It exhibits two emission peaks at 395 nm and 405 nm. Furthermore, the optical alkalinity of the glass itself provides strong reducing power; during the heat-induced crystallization and growth of SrClF nanocrystals, some Eu in the glass matrix... 3+ Reduced to Eu 2+ And doped into the nanocrystals, which in turn leads to the Eu content in the glass matrix of the G4-580 sample. 3+ The intensity of the red fluorescence was lower than that of the G4-AP sample.

[0040] Example 5

[0041] A type of Er 3+ The preparation method of SrClF nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 35%, Al2O3: 3%, AlF3: 19%, SrCl2: 30%, BaO: 12%, Er2O3: 1%.

[0042] 2) After mixing thoroughly, place the mixture in a crucible and melt it under conditions of 1000°C. o After quenching at 60°C for 60 minutes, the temperature was increased to 300°C. o Annealing at C for 3 hours yielded colorless and transparent glass, designated G5. The original glass (G5-AP) was placed in a heat treatment furnace at 500°C.o Er was obtained by heat treatment at C for 10 hours. 3+ The SrClF nanocrystalline dispersed glass is designated G5-500.

[0043] Figure 5 This is the XRD pattern of the product obtained in this embodiment. Figure 5 It can be seen that the crystal diffraction peaks of the G5-500 sample match the diffraction peaks of the SrClF crystal (PDF#05-08-8672), which proves that SrClF nanocrystals have precipitated in the glass, and Er 3+ The dopant has been incorporated into the SrClF nanocrystals. Figure 6 a and 6b are the downconversion and upconversion fluorescence spectra of AP and heat-treated samples under 980 nm near-infrared excitation. Figure 6 As can be seen from this, the conversion fluorescence intensity of the G5-500 sample at 1540 nm is higher than that of the G5-AP sample. Figure 6 In sample b, the upconversion fluorescence intensity of the G5-500 sample at 525 nm and 545 nm was significantly higher than that of the G5-AP sample. This phenomenon indicates that Er in SrClF nanocrystals... 3+ In a low phonon environment, efficient upconversion and downconversion fluorescence processes can be achieved through efficient multiphoton absorption or phonon relaxation.

[0044] Example 6

[0045] A Yb 3+ With Er 3+ The preparation method of co-doped SrClF nanocrystalline dispersed glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 44%, Al2O3: 9%, AlF3: 10%, SrCl2: 20%, SrO: 8%, BaCl2: 8%, YbF3: 0.5%, ErF3: 0.5%.

[0046] 2) After mixing thoroughly, place the mixture in a crucible and melt at 1200°C. o After quenching at 350°C for 30 minutes, the temperature was reduced to 350°C. o Annealing at C for 3 hours yielded colorless and transparent glass, designated G6. The original glass (G6-AP) was placed in a heat treatment furnace at 560°C. o Yb was obtained by heat treatment at C for 10 hours. 3+ With Er 3+ The SrClF nanocrystalline dispersion glass is designated as G6-560.

[0047] Figure 7 a is the XRD pattern of the product obtained in this embodiment. Figure 7As can be seen from this, the crystal diffraction peaks of sample G6-560 match those of SrClF crystal (PDF#05-08-8672), proving that SrClF nanocrystals have precipitated in the glass, and Er 3+ With Yb 3+ Co-doping was incorporated into the SrClF nanocrystals. Figure 7 b shows the upconversion fluorescence spectra of AP and heat-treated samples under 980 nm near-infrared light excitation. Yb 3+ Ions exhibit strong absorption of 980 nm photons and can react with Er. 3+ The efficient energy transfer of ions not only resulted in higher upconversion fluorescence intensities at 525 nm and 545 nm for the G6-560 sample compared to the G6-AP sample, but also the appearance of upconversion luminescence at 650 nm. Compared to the G5-500 sample, the introduction of Yb... 3+ Ions increased Er 3+ The efficiency of two-photon and three-photon upconversion of ions greatly enhances the fluorescence intensity of the G6-560 sample at 525 nm and 650 nm.

[0048] Example 7

[0049] A type of Tb 3+ The preparation method of SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 45%, AlF3: 16%, SrCl2: 20%, SrO: 5%, CaF2: 10%, TbF3: 4%.

[0050] 2) After mixing thoroughly, place the mixture in a crucible and melt at 1250°C. o After quenching at 350°C for 30 minutes, the temperature was reduced to 350°C. o Annealing at C for 3 hours yielded colorless and transparent glass, designated G7. The original glass (G7-AP) was placed in a heat treatment furnace at 600°C. o Tb was obtained by heat treatment at C for 10 hours. 3+ The SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass is designated as G7-600.

[0051] Figure 8a shows the XRD pattern of the product obtained in this embodiment. The crystal diffraction peaks of sample G7 match the diffraction peaks of the Sr2(B5O9)Cl and SrClF crystal phases, respectively, proving that SrClF and Sr2(B5O9)Cl nanocrystals are simultaneously precipitated in the glass. Compared with Example 4, increasing the Sr content, after meeting the Sr amount required for SrClF nanocrystals, the remaining Sr further promotes the precipitation of Sr2(B5O9)Cl nanocrystals, thereby achieving the coexistence of two Sr-based mixed halide nanocrystals. Figure 8 b shows the fluorescence spectra of AP and heat-treated samples, with 490 nm, 540 nm, 587 nm, and 623 nm wavelengths derived from Tb. 3+ The luminescence from ion transitions at different energy levels resulted in a strong green fluorescence in the glass as a whole. The heat-treated sample contained both Sr₂(B₅O₉)Cl and SrClF nanocrystals, and was a Tb₂ sample. 3+ Ions provide a variety of doping environments and luminescence centers, so the fluorescence intensity of the G7-600 sample is higher than that of the original glass.

[0052] Example 8

[0053] A Eu 2+ The preparation method of SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass includes the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 28%, SrCl2: 20%, SrF2: 15%, SrO: 23%, BaF2: 10%, Eu2O3: 4%.

[0054] 2) After mixing thoroughly, place the mixture in a crucible and melt it at 1100°C. o After quenching at 350°C for 20 min, the temperature was increased to 350°C. o Annealing at C for 3 hours yielded colorless and transparent glass, denoted as G8. The original glass (G8-AP) was placed in a heat treatment furnace at 540°C. o Eu was obtained by heat treatment at C for 10 hours. 2+ The SrClF and Sr2(B5O9)Cl nanocrystalline dispersed glass is designated as G8-540.

[0055] Figure 9 a is G8 heat treatment 580 o The X-ray diffraction pattern after C shows that the diffraction peaks of sample G8-580 match those of the Sr2(B5O9)Cl crystalline phase and SrClF, confirming that SrClF and Sr2(B5O9)Cl nanocrystals were simultaneously precipitated in the glass. Compared to Example 7, increasing the relative Sr content and decreasing the relative F content significantly weakened the diffraction peak intensity of SrClF nanocrystals, indicating a reduction in the amount of SrClF nanocrystals precipitated. Figure 9 b shows the fluorescence spectra of AP and heat-treated samples. SrClF and Sr2(B5O9)Cl nanocrystals are Eu. 2+ Ions provide a variety of Sr 2+ The substitution sites, even with the introduction of high Eu₂O₃ content, maintain efficient narrowband blue light emission, with a blue fluorescence peak at 426 nm, a full width at half maximum (FWHM) of 37 nm, and a fluorescence efficiency of 66%. Compared to the single nanocrystals in Examples 1 and 4, the coexistence of two nanocrystals in this example significantly improves Eu₂O₃ emission. 2+ The ions have greater solid solubility, allowing for Eu doping. 2+ The higher effective content of ions results in higher blue light efficiency than the other two crystal types, while the Eu content in the glass matrix... 3+ The ion content decreased significantly.

[0056] Example 9

[0057] A SrClF and Sr2(B5O9)Cl nanocrystalline dispersion glass is prepared by the following steps: 1) Weigh the raw materials according to the following molar percentages of oxides or halides: B2O3: 40%, Al2O3: 14%, AlF3: 7%, SrO: 21%, CaCl2: 8%, BaCl2: 10%.

[0058] 2) After mixing thoroughly, place the mixture in a crucible and melt it at 1300°C. o After quenching at 350°C for 40 minutes, the temperature was reduced to 350°C. o Annealing at C for 3 hours yields colorless and transparent glass, denoted as G9. The original glass (G9-AP) is placed in a heat treatment furnace at 620°C. o SrClF and Sr2(B5O9)Cl nanocrystalline dispersed glass was obtained by heat treatment at C for 10 hours, denoted as G9-620. Figure 10 G9 heat treatment 620 o The X-ray diffraction pattern after C shows that the diffraction peaks of sample G9-620 match the diffraction peaks of Sr2(B5O9)Cl and SrClF crystalline phases, proving that SrClF and Sr2(B5O9)Cl nanocrystals were simultaneously precipitated in the glass.

[0059] Table 2 Glass composition in Comparative Examples 1 and 2

[0060] Comparative Example 1 Weigh the raw materials according to the following molar percentages: B₂O₃: 58%, AlCl₃: 16%, SrF₂: 24%, EuF₃: 2%. Mix thoroughly and place in a crucible. Melt at 1250°C. oAfter quenching and shaping at 20 min (C), it is then heated to 580 °C. o After being kept at C for 10 hours, no crystals precipitated in the glass.

[0061] Compared to Example 4, the B2O3 content in this comparative example exceeds the scope of the claims of this invention, resulting in no nanocrystals precipitating in the glass (see Example 4). Figure 11 ).

[0062] Comparative Example 2 Weigh the raw materials according to the following molar percentages: B₂O₃: 54%, AlCl₃: 16%, SrF₂: 24%, BaF₂: 2%, EuF₃: 4%. Mix thoroughly and place in a crucible. Melt at 1250°C. o After quenching and shaping at 20 min (C), it is then heated to 580 °C. o Keep warm at C for 10 hours.

[0063] Compared to Example 4, this comparative example showed a slight increase in F content, resulting in an F / Cl ratio higher than 1.25. This prevented the precipitation of SrClF nanocrystals, instead causing the precipitation of SrF2 nanocrystals (see Example 4). Figure 12 ).

[0064] Table 3 Glass composition in Comparative Examples 3 and 4

[0065] Comparative Example 3 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 26%, AlCl₃: 2%, SrCl₂: 20%, SrF₂: 15%, SrO: 23%, BaF₂: 10%, Eu₂O₃: 4%. Mix thoroughly and place in a crucible. Melt at 1100°C. o After quenching and forming at 20 min (C), it is then heated to 540 °C. o After being kept at a temperature of C for 10 hours, the resulting glass completely lost its transparency.

[0066] Compared to Example 8, this comparative example slightly reduced the B2O3 content, resulting in an excessively low level of glass network-forming elements. Although SrClF and Sr2(B5O9)Cl nanocrystals could precipitate in the glass, the glass completely lost its transparency (see Example 8). Figure 13 ).

[0067] Comparative Example 4 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 28%, SrCl₂: 20%, SrF₂: 18%, SrO: 25%, BaF₂: 10%, Eu₂O₃: 2%. Mix thoroughly and place in a crucible. Melt at 1100°C. o After quenching and shaping at 20 min (C), it is then heated to 540 °C.o Keep warm at C for 10 hours.

[0068] Compared to Example 8, this comparative example only slightly increased the SrO content, resulting in an excessively high glass body that could not form glass.

[0069] Table 4 Glass composition in Comparative Examples 5 and 6

[0070] Comparative Example 5 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 48%, AlF₃: 10%, AlCl₃: 12%, SrCl₂: 10%, SrO: 3%, CaCl₂: 10%, BaO: 5%, Eu₂O₃: 12%. Mix thoroughly and place in a crucible. Melt at 1300 °C. o After quenching and shaping at 40 min (C), it is then heated to 640 °C. o After being kept at C for 10 hours, no crystals precipitated in the glass.

[0071] Compared to Example 2, this comparative example only slightly reduces the SrO content without changing the total amount of alkaline earth metals in the composition, resulting in an insufficient Sr content (Sr / M < 0.5), preventing the glass from precipitating SrClF or Sr2(B5O9)Cl nanocrystals. Figure 14 ).

[0072] Comparative Example 6 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 48%, AlF₃: 10%, AlCl₃: 12%, SrCl₂: 12%, SrO: 3%, CaCl₂: 10%, BaO: 3%, Eu₂O₃: 12%. Mix thoroughly and place in a crucible. Melt at 1300 °C. o After quenching and shaping at 40 min (C), it is then heated to 640 °C. o Keep warm at C for 10 hours.

[0073] Compared to Example 2, this comparative example only slightly increased the Cl content without changing the total amount of alkaline earth metals in the composition, resulting in an excessively high halogen content in the glass. Although Sr2(B5O9)Cl nanocrystals could precipitate in the glass, the glass completely lost its transparency (see Example 2). Figure 15 ).

[0074] Table 5 Glass composition in Comparative Example 7

[0075] Comparative Example 7 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 46%, AlF₃: 20%, SrCl₂: 22%, SrO: 8%, CeCl₃: 4%. Mix thoroughly and place in a crucible. Melt at 1400°C. o After quenching and shaping at 10 min (C / 10), it is then heated to 620 °C. o After being kept at C for 10 hours, no crystals precipitated in the glass.

[0076] Compared to Example 3, this comparative example kept all other components unchanged, only slightly increasing the F content, resulting in an excessively high F content in the glass, with F / Cl > 0.5. This made the glass unable to meet the precipitation conditions for Sr-based mixed halide nanocrystals, and Sr2(B5O9)Cl nanocrystals failed to precipitate (see Example 3). Figure 16 ).

[0077] Table 6 Glass composition in Comparative Example 8

[0078] Comparative Example 8 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 42%, AlF₃: 14%, AlCl₃: 5%, SrO: 21%, CaCl₂: 8%, BaCl₂: 10%. Mix thoroughly and place in a crucible. Melt at 1300°C. o After quenching and shaping at 40 min (C), it is then heated to 620 °C. o After being kept at C for 10 hours, no crystals precipitated in the glass.

[0079] Compared to Example 9, this comparative example reduces the F content, resulting in an F / Cl ratio below 0.5, which makes the glass unable to meet the precipitation conditions for Sr-based mixed halide nanocrystals (see Example 9). Figure 17 ).

[0080] Table 7 Glass composition in Comparative Example 9

[0081] Comparative Example 9 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 45%, AlF₃: 16%, SrCl₂: 15%, SrO: 10%, CaF₂: 10%, TbF₃: 4%. Mix thoroughly and place in a crucible. Melt at 1250°C. o After quenching and shaping at 30 min (C), it is then heated to 600 °C. o Keep warm at C for 10 hours.

[0082] Compared to Example 7, this comparative example only reduced the Cl content, resulting in an F / Cl ratio higher than 2. This failed to meet the precipitation conditions for Sr-based mixed halide nanocrystals, instead forming SrF2 nanocrystals (see Example 7). Figure 18 ).

[0083] Table 8 Glass composition in Comparative Example 10

[0084] Comparative Example 10 Weigh the raw materials according to the following molar percentages of oxides or halides: B₂O₃: 44%, Al₂O₃: 12%, AlF₃: 7%, SrCl₂: 20%, SrO: 8%, BaCl₂: 8%, YbF₃: 0.5%, ErF₃: 0.5%. Mix thoroughly and place in a crucible. Melt at 1250°C. o After quenching and shaping at 30 min (C), it is then heated to 600 °C. o After being kept at C for 10 hours, no crystals precipitated in the glass.

[0085] Compared to Example 6, this comparative example only changed the F content, and the F / Cl ratio was less than 0.5, which could not meet the precipitation conditions for Sr-based mixed halide nanocrystals, and no crystals precipitated. (See Example 6) Figure 19 ).

[0086] 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 strontium-based mixed halide nanocrystalline dispersion glass, characterized in that, The strontium-based mixed halide nanocrystalline dispersion glass comprises, by molar percentage of oxides or halides: B2O3: 28~56, Al2O3+1 / 2AlX3: 0~17.5, 24≤MO+MX2≤68, Ln2O3+1 / 2LnX3: 0~4, wherein X is one or a combination of two of Cl or F, Ln is a rare earth ion, and M is one or a combination of more than two of Ca, Sr or Ba.

2. The strontium-based mixed halide nanocrystalline dispersion glass according to claim 1, characterized in that, The nanocrystals in the strontium-based mixed halide nanocrystalline dispersion glass are one or a combination of SrClF or Sr2(B5O9)Cl.

3. The strontium-based mixed halide nanocrystalline dispersion glass according to claim 1, characterized in that, In the nanocrystalline dispersed glass, 28 ≤ B2O3 + Al2O3 ≤ 64.

4. The strontium-based mixed halide nanocrystalline dispersion glass according to claim 1, characterized in that, In the nanocrystalline dispersed glass, when M includes Sr, 15≤SrO+SrF2+SrCl2≤58, and Sr / M≥0.

5.

5. The strontium-based mixed halide nanocrystalline dispersion glass according to claim 1, characterized in that, 36≤2MCl2+3AlCl3+3LnCl3≤76, 0≤3AlF3+2MF2+3LnF3≤80, and F / Cl≤2.

6. The strontium-based mixed halide nanocrystalline dispersion glass according to claim 1, characterized in that, When 0.2≤Sr / Cl<0.5 and F / Cl≤0.5, the nanocrystals formed in the glass are Sr2(B5O9)Cl; When Sr / Cl = 0.5 and 0.5 < F / Cl ≤ 1.25, the nanocrystals formed in the glass are SrClF; When Sr / Cl > 0.5 and 0.5 < F / Cl ≤ 2, the nanocrystals formed in the glass are SrClF and Sr2(B5O9)Cl.

7. The method for preparing strontium-based mixed halide nanocrystalline dispersed glass according to claim 1, characterized in that, The steps include: weighing the raw materials according to the glass composition and mixing them thoroughly, then heating at 1000~1400℃. o Melt within a temperature range of C for 10-60 minutes, quench and shape to obtain transparent glass, and then at 500-640°C. o The strontium-based mixed halide nanocrystalline dispersed glass was obtained by heat treatment at temperature C for 1 to 50 hours.

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