A mid-infrared luminescent sulpho-halide glass ceramic containing BaCl2 nanocrystals and its preparation method and application

Abstract

The application discloses a kind of mid-infrared luminescent sulphohalide glass ceramic containing BaCl2 nanocrystal and its preparation method and application, belong to solid-state luminescent material field.The application contains BaCl2 nanocrystal mid-infrared luminescent sulphohalide glass ceramic, including:GeS2, Sb2S3, BaCl2;The molar ratio of GeS2, Sb2S3, BaCl2 is (58-82) :(12.5-16.5) :(10-25) or (45-73) :(17.5-24.5) :(2-30);The mid-infrared luminescent sulphohalide glass ceramic further includes rare earth sulfide.The mid-infrared luminescent sulphohalide glass ceramic structure is stable, can realize high thermal stability and anti-crystallization performance, and can effectively improve the solubility of rare earth ions in glass matrix, ensure high transmittance and low fluorescence loss in 2-5 μm wavelength range, under 980 nanometer laser pumping, the material can produce strong 2.78 μm room temperature fluorescence output.

Description

Technical Field

[0001] This application relates to a mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals, its preparation method and application, belonging to the field of solid luminescent materials. Background Technology

[0002] Since the industrial era, greenhouse gas emissions from human society have increased significantly, with carbon dioxide (CO2) having a particularly prominent impact on climate change. In the mid-infrared band, CO2 molecules exhibit significantly stronger absorption characteristics than in the near-infrared band. Sulfohalite glasses, due to their high transmittance in the mid-infrared emission region and mature fabrication processes, are considered ideal materials for monitoring CO2 concentration. Sulfohalite glasses combine the advantages of chalcogenide and halide glasses, exhibiting a wide transmittance spectrum, strong nonlinear effects, and excellent physicochemical properties in the infrared band. In particular, their high glass transition temperature makes them a strong candidate for optical glass materials capable of transmitting light from the visible to the mid- and far-infrared. To further improve the performance of sulfohalite glasses, researchers have performed controlled microcrystallization treatment, resulting in sulfohalite microcrystalline glasses with excellent optical properties, low thermal expansion coefficient, and high microhardness. Furthermore, by dissolving rare-earth ions in the glass matrix, their lower phonon energy can be utilized to enhance the quantum efficiency of radiation emission, making it possible to achieve mid-infrared emission in rare-earth ion-doped chalcogenide glasses. Therefore, rare-earth ion-doped chalcogenide glasses have attracted widespread research attention as a promising material for developing novel lasers in the mid-infrared region. However, how to efficiently improve the solubility of rare-earth ions, thereby enhancing the luminescence performance of chalcogenide glasses in the mid-infrared region, remains an unsolved challenge. Summary of the Invention

[0003] According to one aspect of this application, a mid-infrared luminescent sulfide glass-ceramic containing BaCl2 nanocrystals is provided. This mid-infrared luminescent sulfide glass-ceramic has a stable structure, achieving high thermal stability and anti-crystallization performance. It can also effectively improve the solubility of rare earth ions in the glass matrix, ensuring high transmittance and low fluorescence loss in the 2-5 μm wavelength range. Under 980 nm laser pumping, this material can generate strong 2.78 μm room temperature fluorescence output. It can be used as a glass-ceramic material for mid-infrared fluorescence and laser output in gas sensing, biomedicine, and infrared countermeasures.

[0004] This application relates to mid-infrared luminescent sulfur halide glass ceramics containing BaCl2 nanocrystals, including:

[0005] GeS2, Sb2S3, BaCl2;

[0006] The molar ratio of GeS2, Sb2S3 and BaCl2 is (58-82):(12.5-16.5):(10-25) or (45-73):(17.5-24.5):(2-30);

[0007] The mid-infrared luminescent sulfur halide glass ceramic also includes rare earth sulfides;

[0008] When the rare earth sulfide is X2S3, the molar ratio of GeS2, Sb2S3, BaCl2 and X2S3 is (60-82):(12.5-16.5):(10-25):(0.5-2.5) or (49.5-73):(17.5-24.5):(2-30):(0.5-2.5).

[0009] X is selected from any one of Er, Dy, Ho, Tb, and Pr;

[0010] When the rare earth sulfides are Er2S3 and A2S3, the molar ratio of GeS2, Sb2S3, BaCl2, Er2S3 and A2S3 is (58-82):(12.5-16.5):(10-25):(0.5-2.5):(0.01-2) or (47.5-73):(17.5-24.5):(2-30):(0.5-2.5):(0.01-2);

[0011] A represents Tm and / or Yb;

[0012] When the rare earth sulfides are Pr2S3 and Dy2S3, the molar ratio of GeS2, Sb2S3, BaCl2, Pr2S3 and Dy2S3 is (58-82):(12.5-16.5):(10-25):(0.5-2.5):(0.01-2) or (47.5-73):(17.5-24.5):(2-30):(0.5-2.5):(0.01-2).

[0013] Optionally, the molar ratio of GeS2 to Sb2S3 is (2-6):1.

[0014] Optionally, the microstructure of the mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals is characterized by: spherical BaCl2 nanocrystals distributed in the glass matrix, with an average size of 5-10 nanometers for the BaCl2 grains.

[0015] Optionally, the average size of the BaCl2 grains is 7 nanometers.

[0016] This application also provides a method for preparing a mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals, comprising: vacuuming, calcining, and annealing a mixture of Ge, Sb, S, BaCl2, and X (Ⅰ), or a mixture of Ge, Sb, S, BaCl2, Er, and A (Ⅱ), or a mixture of Ge, Sb, S, BaCl2, Pr, and Dy (Ⅲ) to obtain the mid-infrared luminescent sulfur halide glass ceramic.

[0017] Optionally, the vacuum is evacuated to a vacuum level of 10. -1 -10 -3 Pa.

[0018] Specifically, the vacuum is evacuated to a vacuum level of 10. -3 Pa.

[0019] Optionally, the calcination temperature is 900-1000℃, and the calcination time is 8-15h.

[0020] Preferably, the roasting temperature is 920-950℃ and the roasting time is 10-12h.

[0021] Optionally, the annealing temperature is 200-350°C.

[0022] This application also provides the application of the mid-infrared luminescent sulfide glass ceramic containing BaCl2 nanocrystals in CO2 gas sensing materials.

[0023] The beneficial effects that this application can produce include:

[0024] 1) The mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals provided in this application has a stable structure, can achieve high thermal stability and anti-crystallization performance, and can effectively improve the solubility of rare earth ions in the glass matrix, ensuring high transmittance and low fluorescence loss in the 2-5μm wavelength range. Under 980nm laser pumping, the material can produce strong 2.78μm room temperature fluorescence output.

[0025] 2) The mid-infrared luminescent sulfur halide glass-ceramic containing BaCl2 nanocrystals provided in this application can be used as a glass-ceramic material for gas sensing, biomedicine, and mid-infrared fluorescence and laser output in infrared countermeasures.

[0026] 3) The mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals provided in this application has good mid-infrared luminescence performance and can introduce a variety of rare earth elements at low cost. Attached Figure Description

[0027] Figure 1 The X-ray diffraction pattern of the precursor glass in Example 4;

[0028] Figure 2 X-ray diffraction pattern of the glass-ceramic in Example 4;

[0029] Figure 3 Example 4: BaCl2:Er 3+ / Tm 3+ Transmission electron microscopy image of nanocrystalline sulfur halide glass ceramic, with a size of 50 nm;

[0030] Figure 4 BaCl2:Er in Examples 2-5 3+ Steady-state emission spectra of nanocrystalline sulfide glass ceramics and BaCl2:Er 3+ / Tm 3+ Steady-state emission spectrum of nanocrystalline sulfohalide glass ceramics;

[0031] Figure 5 BaCl2:Er in Examples 2, 6 and 7 3+ / Tm 3+ Steady-state emission spectrum of nanocrystalline sulfide glass ceramics in the mid-infrared region. Detailed Implementation

[0032] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0033] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0034] In this embodiment, the X-ray diffraction instrument used was a Rigaku-miniflex 600 X-ray polycrystalline diffractometer (XRD) with a Cu target, a test range of 10-80°, and a test rate of 5° / min. Fluorescence performance was measured using an FLS920 (Edinburgh) fluorescence spectrometer with an excitation wavelength of 980 nm.

[0035] Example 1:

[0036] Ge, Sb, and S with a purity of 99.9999% and BaCl2, Er, and Tm with analytical purity were precisely weighed in a ratio of 60GeS2:20Sb2S3:20BaCl2:0.50Er2S3:0.10Tm2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0037] Example 2

[0038] Ge, Sb, and S with a purity of 99.9999% and BaCl2, Er, and Tm with analytical purity were precisely weighed in a ratio of 60GeS2:20Sb2S3:3.4BaCl2:0.50Er2S3:0.20Tm2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0039] Example 3

[0040] Ge, Sb, and S with a purity of 99.9999% and BaCl2 and Er with analytical purity were precisely weighed in a ratio of 60GeS2:20Sb2S3:3.4BaCl2:0.5Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0041] Example 4

[0042] Ge, Sb, and S with a purity of 99.9999%, and BaCl2 and Er with analytical purity, were precisely weighed in a ratio of 60GeS2:20Sb2S3:5.11BaCl2:0.5Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then annealed in an annealing furnace at 350℃, and after cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0043] Example 5

[0044] Ge, Sb, and S with a purity of 99.9999%, and BaCl2 and Er with analytical purity, were precisely weighed in a ratio of 60GeS2:20Sb2S3:8.88BaCl2:0.5Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0045] Figure 4 BaCl2:Er in Examples 2-5 3+ Steady-state emission spectra of nanocrystalline sulfide glass ceramics and BaCl2:Er 3+ / Tm 3+ The steady-state emission spectrum of nanocrystalline sulfide glass ceramics, from Figure 4 It can be seen that, using an FLS920 fluorescence spectrometer, under 980 nm laser irradiation, BaCl2:Er 3+ The emission peaks of the glass-ceramic samples are located at 524 nm, 540 nm, 666 nm, 720 nm, and 808 nm, respectively belonging to Er. 3+ exist 2 H 11 / 2 → 4 I 15 / 2 , 4 S 3 / 2 → 4 I 15 / 2 , 4 F 7 / 2 → 4 I 13 / 2 , 4 I 9 / 2 → 4 I 15 / 2 The emission peaks of the glass ceramic at 540 nm and 666 nm showed a gradual change with the BaCl2 content, and a significant splitting of the emission peak at 666 nm was observed. As the BaCl2 content gradually increased from 4% to 10%, the emission color of the glass ceramic changed from green to yellow to red. Furthermore, Er was also detected. 3+ Its own excited state transition ( 4 F 7 / 2 → 4 I 13 / 2 Emission at 720nm. With the addition of Tm 3+ After sensitization, under 980nm excitation, Er3+ Emissions decreased at 540nm, 666nm, and 1530nm, and those not excited had Tm. 3+ : 3 F 2,3 → 3 H6 transition (700nm) emission, enhancing Er 3+ The 2.78μm emission mainly occurs through the following process: Er 3+ : 4 I 13 / 2 →Tm 3+ : 3 F4, some electrons in the excited state fall back to Tm through radiative relaxation. 3+ : 3 The H6 level emits at 1.8 μm. Part of it undergoes cross-relaxation, causing Er... 3+ : 4 I 13 / 2 Electrons at the energy level are excited to 4 I 9 / 2 The energy level promotes emission at 2.78 μm. Furthermore, Er... 3+ : 4 I 13 / 2 Electrons at energy levels undergo cross-relaxation, causing Tm to... 3+ : 3 The electron transition at the F4 energy level to... 3 On H4, energy is then transferred to Er. 3+ : 4 I 9 / 2 The energy level enhancement at 2.78 μm also resulted in enhanced emission at 800 nm. This was achieved through monitoring... 4 I 11 / 2 and 4 I 13 / 2 From the energy level lifetime and fluorescence emission, it can be seen that due to the enhancement of the above two processes, Er 3+ Emission enhancement at 2.78 μm, and Er 3+ : 4 I 13 / 2 Energy level lifetime at Tm 3+ There was no significant reduction after incorporation.

[0046] Example 6

[0047] Ge, Sb, and S with a purity of 99.9999% and BaCl2, Er, and Tm with analytical purity were precisely weighed in a ratio of 60GeS2:20Sb2S3:5.1BaCl2:0.50Er2S3:0.20Tm2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0048] Example 7

[0049] Ge, Sb, and S with a purity of 99.9999% and BaCl2, Er, and Tm with analytical purity were precisely weighed in a ratio of 60GeS2:20Sb2S3:8.8BaCl2:0.50Er2S3:0.20Tm2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0050] Figure 5 BaCl2:Er in Examples 2, 6 and 7 3+ / Tm 3+ The steady-state emission spectrum of nanocrystalline sulfide glass ceramics in the mid-infrared region shows that, using an FLS920 fluorescence spectrometer, the glass ceramic sample exhibits excellent mid-infrared fluorescence performance under 980 nm laser irradiation at room temperature.

[0051] Example 8:

[0052] Ge, Sb, and S with a purity of 99.9999%, and BaCl2 and Er with analytical purity, were precisely weighed in a ratio of 60GeS2:20Sb2S3:20BaCl2:0.43Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0053] Example 9:

[0054] Ge, Sb, and S with a purity of 99.9999%, and analytical grade BaCl2 and Er, were precisely weighed in a ratio of 60GeS2:10Sb2S3:30BaCl2:0.43Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0055] Example 10:

[0056] Ge, Sb, and S with a purity of 99.9999%, and BaCl2 and Er with analytical purity, were precisely weighed in a ratio of 60GeS2:5Sb2S3:35BaCl2:0.43Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10.-3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0057] Example 11:

[0058] Ge, Sb, and S with a purity of 99.9999%, and BaCl2 and Er with analytical purity, were precisely weighed in a ratio of 50GeS2:10Sb2S3:40BaCl2:0.43Er2S3 (mol). The mixture was then placed into quartz ampoules in a glove box. The open end of the quartz ampoule was connected to a vacuum system to remove air and moisture, and the vacuum was evacuated to a degree of 10. -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The quartz ampoules were then placed in a swing furnace and heated to 950℃ and held at that temperature for 10 hours. Subsequently, the quartz ampoules were removed and rapidly quenched in water vertically. The cooled quartz ampoules were then placed in an annealing furnace and annealed at 200℃ or 350℃. After cutting, the sulfide microcrystalline glass was obtained. The visible and mid-infrared emission spectra of the samples at room temperature were measured using an FLS920 fluorescence spectrometer. The central wavelength of the mid-infrared emission was observed to be 2.78 μm, corresponding to Er... 3+ exist 4 I 11 / 2 → 4 I 13 / 2 Leap forward.

[0059] Figure 1 The image shows the X-ray diffraction pattern of the precursor glass in Example 4. The X-ray diffraction data indicates that the heat-treated precursor glass exhibits GeS2 peaks in the matrix glass, but no crystalline phase has precipitated.

[0060] Figure 2 The X-ray diffraction pattern of the glass-ceramic in Example 4 shows that the sample was amorphous after quenching, and BaCl2 crystalline phase precipitated in the glass matrix after heat treatment. The XRD peak positions can be matched one by one with the standard card.

[0061] Figure 3 Example 4: BaCl2:Er 3+ / Tm 3+Transmission electron microscopy (TEM) image of nanocrystalline sulfohalide glass ceramic. Observation of the sample using TEM revealed the precipitation of BaCl2 grains with a particle size of approximately 7 nm.

[0062] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A mid-infrared luminescent chalcohalide glass-ceramic containing BaCl2 nanocrystals, characterized in that, include: GeS2, Sb2S3, BaCl2; The molar ratio of GeS2, Sb2S3 and BaCl2 is (58-82):(12.5-16.5):(10-25) or (45-73):(17.5-24.5):(2-30). The mid-infrared luminescent sulfur halide glass ceramic also includes rare earth sulfides; When the rare earth sulfide is X2S3, the molar ratio of GeS2, Sb2S3, BaCl2 and X2S3 is (60-82):(12.5-16.5):(10-25):(0.5-2.5) or (49.5-73):(17.5-24.5):(2-30):(0.5-2.5). X is selected from any one of Er, Dy, Ho, Tb, and Pr; When the rare earth sulfides are Er2S3 and A2S3, the molar ratio of GeS2, Sb2S3, BaCl2, Er2S3 and A2S3 is (58-82):(12.5-16.5):(10-25):(0.5-2.5):(0.01-2) or (47.5-73):(17.5-24.5):(2-30):(0.5-2.5):(0.01-2). A represents Tm and / or Yb; When the rare earth sulfides are Pr2S3 and Dy2S3, the molar ratio of GeS2, Sb2S3, BaCl2, Pr2S3 and Dy2S3 is (58-82):(12.5-16.5):(10-25):(0.5-2.5):(0.01-2) or (47.5-73):(17.5-24.5):(2-30):(0.5-2.5):(0.01-2). The microstructure of the mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals is characterized by: spherical BaCl2 nanocrystals distributed in the glass matrix, with an average size of 5-10 nanometers for the BaCl2 grains.

2. The mid-infrared luminescent glass-ceramics containing BaCl2 nanocrystals according to claim 1, characterized in that, The microstructure of the mid-infrared luminescent sulfur halide glass ceramic containing BaCl2 nanocrystals is characterized by: spherical BaCl2 nanocrystals distributed in the glass matrix, with an average size of 7 nanometers for the BaCl2 grains.

3. A method for the preparation of mid-infrared luminescent nanocrystal- containing BaCl2 sulpho-halide glass-ceramics according to any one of claims 1-2, characterized in that, include: The mid-infrared luminescent sulfur halide glass ceramic is obtained by vacuuming, calcining, and annealing a mixture of Ge, Sb, S, BaCl2, X (Ⅰ), Ge, Sb, S, BaCl2, Er, A (Ⅱ), or Ge, Sb, S, BaCl2, Pr, Dy (Ⅲ).

4. The method for preparing mid-infrared luminescent sulfur halide glass-ceramics containing BaCl2 nanocrystals according to claim 3, characterized in that, The roasting temperature is 900-1000℃, and the roasting time is 8-15h.

5. The method of claim 4, wherein the BaCl2 nanocrystal-containing mid-infrared luminescent chalcohalide glass ceramic is prepared by the steps of: The roasting temperature is 920-950℃, and the roasting time is 10-12h.

6. The method for preparing mid-infrared luminescent sulfur halide glass-ceramics containing BaCl2 nanocrystals according to claim 3, characterized in that, vacuumed to a vacuum degree of 10 -1 -10 -3 Pa.

7. The method for preparing mid-infrared luminescent sulfur halide glass-ceramics containing BaCl2 nanocrystals according to claim 3, characterized in that, The annealing temperature is 200-350℃.

8. The application of the mid-infrared luminescent sulfide glass ceramic containing BaCl2 nanocrystals as described in any one of claims 1-2 in a CO2 gas sensing material.

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