A fluorescent glass for mid-infrared emission and its preparation method

Abstract

This application discloses a fluorescent glass for mid-infrared emission and its preparation method, belonging to the field of optical materials technology. The method includes the following steps: S1, obtaining phosphor and sulfide glass powder respectively; S2, grinding the mixture containing phosphor and sulfide glass powder, pressing it into shape, and calcining it to obtain the fluorescent glass for mid-infrared emission. Combining the high brightness, wide color gamut, and high stability of phosphor with the low phonon energy and excellent mid-infrared transmittance of sulfide glass, this fluorescent glass can produce strong 2.65μm room temperature fluorescence output under 980nm laser pumping. The preparation method of this application can prepare fluorescent glass materials with a wide emission band in a short time and at a low cost. It is a simple and efficient method for synthesizing mid-infrared fluorescent glass and can expand the selection range of phosphors, resulting in significant economic benefits.

Description

Technical Field

[0001] This application relates to a fluorescent glass for mid-infrared emission and its preparation method, belonging to the field of optical materials technology. Background Technology

[0002] The mid-infrared (MIR) band, primarily encompassing light sources in the 2-5 μm range, has demonstrated significant application potential in spectroscopy, biosensors, medical diagnostics, environmental monitoring, and gas sensing, attracting widespread attention from researchers globally. In particular, many atmospheric pollutants exhibit vibrational absorption characteristics in the infrared region (e.g., CH4: ~3.3 μm, H2S: 2.7 μm, NH3: 2.3 μm), making the development of 2-5 μm mid-infrared light sources of significant scientific and practical value. Chalcogenide glasses, mainly composed of sulfides and selenides of group VI elements such as sulfur (S), selenium (Se), and tellurium (Te), as well as heavy metals such as germanium (Ge), gallium (Ga), and arsenic (As), are valuable due to their high third-order nonlinear coefficient and low phonon energy (<350 cm⁻¹). -10 Chalcogenide glasses are favored for their high refractive index (>2.1) and wide infrared transmission range. Their broad spectral range covers the near-infrared, mid-infrared, and far-infrared bands, making them ideal transmission media in the mid- and far-infrared bands. However, despite their good chemical and thermal stability, chalcogenide glasses suffer from poor mechanical properties, limiting their potential applications. To address this, researchers have introduced high-bond-energy halogens as glass network modifiers to increase the glass's packing density and improve the stability of the glass network structure. Optimizing glass processing can reduce lattice or bond defects in chalcogenide glasses, thereby improving their mechanical properties. However, the preparation process of chalcogenide glasses is relatively complex, requiring long timeframes and demanding experimental conditions. Summary of the Invention

[0003] To address the challenges of balancing high performance, simple processing, and low cost in existing mid-infrared luminescent fluorescent glass technologies, this application provides a method for preparing mid-infrared luminescent fluorescent glass. The method involves mixing and grinding phosphor with sulfide glass powder, followed by co-sintering at a lower temperature. This allows for the rapid and cost-effective preparation of fluorescent glass with mid-infrared luminescent properties, fully utilizing the high brightness, wide color gamut, and high stability of the phosphor, as well as the low phonon energy and excellent mid-infrared light transmittance of the sulfide glass.

[0004] The technical solution adopted in this application is as follows:

[0005] A method for preparing fluorescent glass for mid-infrared emission includes the following steps:

[0006] S1. Obtain phosphor and sulfur halide glass powder respectively;

[0007] S2. Grind the mixture containing phosphor and sulfur halide glass powder, press it into shape, and calcine it to obtain the fluorescent glass for mid-infrared emission.

[0008] Optionally, the preparation method of the phosphor is as follows:

[0009] The fluorescent powder is obtained by calcining and grinding a fluorescent powder raw material containing A2O3, B2O3, and X2O3.

[0010] A is Y and / or Gd;

[0011] B is Ga and / or Al;

[0012] X is Er and / or Tm.

[0013] Optionally, the molar ratio of A2O3, B2O3, and X2O3 is 0.56–0.6:1:0.032–0.16.

[0014] Optionally, the molar ratio of A2O3, B2O3, and X2O3 is 35-37.5:62.5:2-10.

[0015] Optionally, the conditions for calcination I include:

[0016] The calcination temperature for step I is 1000℃-1600℃;

[0017] The roasting time for I is 1-6 hours.

[0018] Optionally, the conditions for calcination I include:

[0019] The calcination temperature for calcination I is 1550℃-1580℃;

[0020] The roasting time for I is 3-5 hours.

[0021] Optionally, the preparation method of the sulfur halide glass powder is as follows:

[0022] The sulfur halide glass powder raw material containing Ga2S3, Sb2S3, and CsCl was placed in a vacuum-sealed container, calcined, quenched, annealed, and then ground to obtain the sulfur halide glass powder.

[0023] Optionally, the molar amounts of the components in the sulfur halide glass powder raw material are as follows:

[0024] 30-40 moles of Ga2S3;

[0025] Sb2S3 20-70 moles;

[0026] CsCl 20-70 moles.

[0027] Optionally, the conditions for calcination II include:

[0028] The calcination temperature for II is 900℃-1000℃;

[0029] The roasting time for II is 8-15 hours.

[0030] Optionally, the conditions for calcination II include:

[0031] The firing temperature for calcination II is 920℃-950℃;

[0032] The roasting time for II is 10-14 hours.

[0033] Optionally, the quenching conditions include: cooling to 800℃~900℃ after calcination II, and placing the vacuum-sealed container in a room temperature environment until it cools to room temperature.

[0034] Preferably, the annealing conditions include:

[0035] The annealing temperature is 200℃-350℃;

[0036] The annealing time is 4 to 8 hours.

[0037] Optionally, the vacuum level of the vacuum-sealed container is 10. -1 Pa-10 -3 Pa. Preferably 10. -3 Pa.

[0038] Optionally, the calcination conditions include:

[0039] The calcination temperature is 450℃-600℃;

[0040] The calcination time is 3-6 hours.

[0041] Optionally, the calcination conditions include:

[0042] The calcination temperature is 500℃-530℃;

[0043] The calcination time is 3-4 hours.

[0044] In existing technologies, the synthesis process of sulfide glasses requires vacuum, calcination, and annealing. However, the synthesis of fluorescent glass in this application only requires mixing and grinding glass powder and phosphor powder, pressing into sheets, and sintering, without the need for vacuum and annealing.

[0045] The beneficial effects that this application can produce include:

[0046] The fluorescent glass for mid-infrared emission provided in this application combines the high brightness, wide color gamut, and high stability of phosphors with the low phonon energy and excellent mid-infrared transmittance of sulfide glasses. Under 980nm laser pumping, this fluorescent glass can produce strong 2.65μm room-temperature fluorescence output. The preparation method of this application can prepare fluorescent glass materials with a wide emission band in a short time and at a low cost. It is a simple and efficient method for synthesizing mid-infrared fluorescent glasses and can expand the selection range of phosphors, resulting in significant economic benefits. Attached Figure Description

[0047] Figure 1 Y3Ga5O 12 X-ray diffraction patterns of phosphor and fluorescent glass.

[0048] Figure 2 The fluorescence spectrum of the fluorescent glass in the mid-infrared region is shown in Specific Example 1. Detailed Implementation

[0049] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0050] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0051] Unless otherwise specified, all test methods are conventional and all instrument settings are those recommended by the manufacturer.

[0052] 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.

[0053] Example 1

[0054] Y, Ga, and Er, with a purity of 99.9999%, were precisely weighed and mixed in a molar ratio of Y₂O₃:Ga₂O₃:Er₂O₃ of 36.25:62.5:5 to form the phosphor powder raw material. The raw material was then ground uniformly and placed in a crucible, heated to 1580℃ in a high-temperature furnace, and held at that temperature for 5 hours. After cooling to room temperature, the agglomerated phosphor powder was removed and ground in a mortar to obtain the desired phosphor powder.

[0055] Ga, Sb, and Cs with a purity of 99.9999% were precisely weighed and mixed in a glove box at a molar ratio of Ga₂S₃:Sb₂S₃:CsCl of 30:30:40 to form a sulfur halide glass powder raw material. This raw material was then placed in a clean quartz ampoule, sealed using a matching mechanical valve, and transferred to an automatic sealing machine for further processing, where a vacuum of 10... -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The cooled, sealed quartz ampoules were then placed in a swing furnace and heated to 920°C for 10 hours for homogenization. Subsequently, the temperature was lowered to 850°C, and the quartz ampoules were removed and quickly quenched in room temperature water. To relieve stress, the quartz ampoules were placed in an annealing furnace and annealed for 6 hours at a temperature 30°C below the glass transition temperature. Finally, the ampoules were ground to obtain the final sulfide glass powder.

[0056] Phosphor and thiohalite glass powder were mixed and ground with anhydrous ethanol. The mixture was then pressed into sheets using a Φ12 mold (10 MPa, 2 min), placed in a crucible, and held at 500℃ for 3 h to obtain fluorescent glass. The visible and mid-infrared emission spectra of the phosphor sample and fluorescent glass at room temperature were measured using an FLS920 fluorescence spectrometer, revealing a central wavelength of 2.65 μm for the mid-infrared emission.

[0057] Example 2

[0058] Gd2O3, Ga2O3, and Er2O3 with a purity of 99.99% were precisely weighed and mixed in a molar ratio of 35.25:62.5:1.25 to form a fluorescent powder raw material. The powder raw material was ground evenly and placed in a crucible. It was then heated to 1580℃ in a high-temperature furnace and kept at that temperature for 5 hours. After cooling to room temperature, the agglomerated fluorescent powder was removed and ground in a mortar to obtain the desired fluorescent powder.

[0059] Ga, Sb, and Cs with a purity of 99.9999% were precisely weighed and mixed in a glove box at a molar ratio of Ga₂S₃:Sb₂S₃:CsCl of 35:35:30 to form a sulfur halide glass powder raw material. This raw material was then placed in a clean quartz ampoule, sealed using a matching mechanical valve, and transferred to an automatic sealing machine for further processing, where a vacuum of 10... -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The cooled, sealed quartz ampoules were then placed in a swing furnace and heated to 920°C for 10 hours for homogenization. Subsequently, the temperature was lowered to 850°C, and the quartz ampoules were removed and quickly quenched in room temperature water. To relieve stress, the quartz ampoules were placed in an annealing furnace and annealed for 6 hours at a temperature 30°C below the glass transition temperature. Finally, the ampoules were ground to obtain the final sulfide glass powder.

[0060] Phosphor powder and thiohalite glass powder were mixed and ground with anhydrous ethanol. The mixture was then pressed into sheets using a Φ12 mold (10 MPa, 2 min), placed in a crucible, and held at 500℃ for 3 h to obtain fluorescent glass. The visible and mid-infrared emission spectra of the fluorescent glass samples at room temperature were measured using an FLS920 fluorescence spectrometer, revealing a central wavelength of 2.65 μm for mid-infrared emission.

[0061] Example 3

[0062] Y₂O₃, Ga₂O₃, and Er₂O₃ with a purity of 99.99% were precisely weighed and mixed in a molar ratio of Y₂O₃:Ga₂O₃:Er₂O₃ of 36.25:62.5:1.25 to prepare the phosphor powder raw material. The raw material was then ground uniformly and placed in a crucible, heated to 1580℃ in a high-temperature furnace, and held at that temperature for 5 hours. After cooling to room temperature, the agglomerated phosphor powder was ground in a mortar to obtain the desired phosphor powder.

[0063] Ga, Sb, and Cs with a purity of 99.9999% were precisely weighed and mixed in a glove box at a molar ratio of Ga₂S₃:Sb₂S₃:CsCl of 30:30:40 to form a sulfur halide glass powder raw material. This raw material was then placed in a clean quartz ampoule, sealed using a matching mechanical valve, and transferred to an automatic sealing machine for further processing, where a vacuum of 10... -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The cooled, sealed quartz ampoules were then placed in a swing furnace and heated to 920°C for 10 hours for homogenization. Subsequently, the temperature was lowered to 850°C, and the quartz ampoules were removed and quickly quenched in room temperature water. To relieve stress, the quartz ampoules were placed in an annealing furnace and annealed for 6 hours at a temperature 30°C below the glass transition temperature. Finally, the ampoules were ground to obtain the final sulfide glass powder.

[0064] Phosphor powder and sulfide glass powder were mixed and ground with anhydrous ethanol. The mixture was then pressed into sheets using a Φ12 mold (10 MPa, 2 min), placed in a crucible, and held at 500℃ for 3 h to obtain the fluorescent glass. The Y3Ga5O content was measured using X-ray polycrystalline diffraction. 12 X-ray diffraction patterns of phosphor and fluorescent glass are shown below. Figure 1 As shown, the visible and mid-infrared emission spectra of the phosphor sample and fluorescent glass at room temperature were measured using an FLS920 fluorescence spectrometer. The results are as follows. Figure 2 As shown, the center wavelength of the mid-infrared emission can be observed to be 2.65 nm.

[0065] Example 4

[0066] Gd₂O₃, Ga₂O₃, and Tm₂O₃ with a purity of 99.99% were precisely weighed and mixed in a molar ratio of 35.25:62.5:1.25 (Gd₂O₃:Ga₂O₃:Tm₂O₃). The raw materials for the fluorescent powder were then ground uniformly and placed in a crucible. The crucible was heated to 1580℃ in a high-temperature furnace and held for 5 hours. After cooling to room temperature, the agglomerated fluorescent powder was removed and ground in a mortar to obtain the desired fluorescent powder.

[0067] Ga, Sb, and Cs with a purity of 99.9999% were precisely weighed and mixed in a glove box at a molar ratio of Ga₂S₃:Sb₂S₃:CsCl of 35:35:30 to form a sulfur halide glass powder raw material. This raw material was then placed in a clean quartz ampoule, sealed using a matching mechanical valve, and transferred to an automatic sealing machine for further processing, where a vacuum of 10... -3 After Pa, the quartz ampoules were sealed using an oxyhydrogen flame torch. The cooled, sealed quartz ampoules were then placed in a swing furnace and heated to 920°C for 10 hours for homogenization. Subsequently, the temperature was lowered to 850°C, and the quartz ampoules were removed and quickly quenched in room temperature water. To relieve stress, the quartz ampoules were placed in an annealing furnace and annealed for 6 hours at a temperature 30°C below the glass transition temperature. Finally, the ampoules were ground to obtain the final sulfide glass powder.

[0068] Phosphor powder and thiohalite glass powder were mixed and ground with anhydrous ethanol. The mixture was then pressed into sheets using a Φ12 mold (10 MPa, 2 min), placed in a crucible, and held at 500℃ for 3 h to obtain fluorescent glass. The visible and mid-infrared emission spectra of the fluorescent glass samples at room temperature were measured using an FLS920 fluorescence spectrometer, revealing a central wavelength of 2.65 μm for mid-infrared emission.

[0069] 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 method for preparing fluorescent glass for mid-infrared emission, characterized in that, Includes the following steps: S1. Obtain phosphor and sulfur halide glass powder respectively; S2. Grind the mixture containing phosphor and sulfur halide glass powder, press it into shape, and calcine it to obtain the fluorescent glass for mid-infrared emission. The preparation method of the phosphor is as follows: The fluorescent powder is obtained by calcining and grinding a fluorescent powder raw material containing A2O3, B2O3, and X2O3. A is Y and / or Gd; B is Ga and / or Al; X is Er and / or Tm; The molar ratio of A2O3, B2O3, and X2O3 is 0.56~0.6:1:0.032~0.16; The preparation method of the sulfur halide glass powder is as follows: The sulfur halide glass powder raw material containing Ga2S3, Sb2S3, and CsCl was placed in a vacuum-sealed container, calcined, quenched, annealed, and then ground to obtain the sulfur halide glass powder. The molar amounts of the components in the sulfur halide glass powder raw material are as follows: Ga2S3 30-40 moles; Sb2S3 20-70 moles; CsCl2 0-70 moles.

2. The preparation method according to claim 1, characterized in that, The conditions for calcination I include: The calcination temperature for step I is 1000℃-1600℃; The roasting time for I is 1-6 hours.

3. The preparation method according to claim 1, characterized in that, The conditions for roasting II include: The calcination temperature for II is 900℃-1000℃; The roasting time for II is 8-15 hours.

4. The preparation method according to claim 1, characterized in that, The quenching conditions include: after calcination II, the temperature is reduced to 800℃~900℃, and the vacuum-sealed container is placed in a room temperature environment until it cools down to room temperature. The annealing conditions include: The annealing temperature is 200℃-350℃; The annealing time is 4 to 8 hours.

5. The preparation method according to claim 4, characterized in that, The vacuum level of the vacuum-sealed container is 10. -1 Pa-10 -3 Pa.

6. The preparation method according to claim 1, characterized in that, The calcination conditions include: The calcination temperature is 450℃-600℃; The calcination time is 3-6 hours.

Images