A high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals and its preparation method and application

Abstract

The present invention discloses a high-heat-dissipation tellurite fluorescent glass doped with micronized silica crystals, as well as its preparation method and application, relating to the field of laser lighting technology. The raw materials of the micronized silica crystal-doped tellurite fluorescent glass include: yttrium aluminum garnet yellow phosphor, micronized silica crystals, and precursor glass powder. The precursor glass powder comprises, by mole percentage, 59-70% TeO2, 10-20% ZnO, 10-20% Na2O, and 1-10% Al2O3. The mass of the yttrium aluminum garnet yellow phosphor accounts for 1-15% of the mass of the precursor glass powder, and the mass of the micronized silica crystals accounts for 10-25% of the mass of the precursor glass powder. The fluorescent glass of the present invention has high luminescence performance, excellent thermal stability, and a high laser irradiation threshold, meeting the high-performance requirements of white-light laser lighting. It also has the significant advantages of a simple preparation process, environmental friendliness, and low production cost.

Description

Technical Field

[0001] The present invention relates to the field of laser lighting technology, and in particular to a high-heat-dissipating tellurite fluorescent glass doped with micron silicon dioxide crystals, and a preparation method and application thereof. Background Art

[0002] Semiconductor solid-state light sources have gradually replaced traditional light sources due to their significant advantages, including high luminous efficacy, low power consumption, long life, and environmental friendliness. The method of using blue light chips to excite yellow phosphors is a common method used in white light illumination. Improving the photothermal performance of yellow phosphors and the phosphor conversion materials they comprise is of great significance to the development of white light illumination technology.

[0003] Fluorescence conversion materials primarily include fluorescent glass, fluorescent ceramics, and single crystals. However, when excited by high-power blue laser chips, traditional fluorescent glass, fluorescent ceramics, and other fluorescent conversion materials are prone to cracking due to high temperatures, as well as reduced luminous efficiency and thermal quenching of the phosphor. Furthermore, the difficulty and high cost of preparing single crystals limit their large-scale application. Heat dissipation methods such as external heat sinks or highly thermally conductive substrates increase the cost and structural complexity of lighting devices, seriously affecting the photothermal performance of white light laser lighting.

[0004] Prior art has combined borosilicate glass with phosphors to create fluorescent glass. However, borosilicate glass's high melting temperature requires temperatures exceeding 1,000 degrees Celsius to produce. This high melting temperature places extremely high demands on the manufacturing process, and high temperatures can also damage the phosphors. Furthermore, borosilicate's low refractive index creates a mismatch with that of the phosphors, affecting light reflection and scattering. This results in suboptimal improvements in white light performance and makes it difficult to meet practical requirements.

[0005] Compared to borosilicate glass, tellurite glass has a lower melting temperature and higher refractive index, making it compatible with commercial phosphors and an ideal phosphor conversion material. However, tellurite glass has a low thermal conductivity and rapidly heats up under high-power laser irradiation, leading to thermal quenching of the phosphor, thus limiting its application in laser lighting.

[0006] Therefore, on the basis of improving the heat dissipation capacity of tellurite fluorescent glass, preparing fluorescent glass materials with high refractive index, low melting point and high thermal conductivity, and then enriching the types of fluorescent glass and ensuring its performance are technical problems that need to be solved urgently in the field of laser lighting. Summary of the Invention

[0007] The purpose of the present invention is to provide a high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals and a preparation method and application thereof, so as to solve the problems existing in the above-mentioned prior art.

[0008] To achieve the above object, the present invention provides the following solutions:

[0009] The present invention provides a tellurite fluorescent glass doped with micron silicon dioxide crystals, the raw materials of which include the following components:

[0010] Yttrium aluminum garnet yellow phosphor, micronized silica crystals, and precursor glass powder;

[0011] The precursor glass powder is composed of the following components in terms of mole percentage: TeO2 59-70%, ZnO 10-20%, Na2O 10-20% and Al2O3 1-10%;

[0012] The mass of the yttrium aluminum garnet yellow phosphor is 1 to 15% of the mass of the precursor glass powder; the mass of the micron silicon dioxide crystal is 10 to 25% of the mass of the precursor glass powder.

[0013] Furthermore, the precursor glass powder is composed of the following components in terms of mole percentage: TeO2 65%, ZnO 15%, Na2O 15% and Al2O3 5%;

[0014] The mass of the yttrium aluminum garnet yellow phosphor is 15% of the mass of the precursor glass powder; the mass of the micron silicon dioxide crystal is 20% of the mass of the precursor glass powder.

[0015] Furthermore, the micron silicon dioxide crystals are tetragonal micron silicon dioxide crystals.

[0016] Furthermore, the particle size of the micron silicon dioxide crystals is 1 to 20 μm.

[0017] Furthermore, the method for preparing the micronized silicon dioxide crystals comprises the following steps:

[0018] Amorphous silicon dioxide powder with a purity of ≥99.9% is heated at 1600° C. for 1 hour, cooled to room temperature, then kept at 1300-1500° C. for 6-10 hours, cooled to room temperature again, and then ground to obtain the micron silicon dioxide crystals.

[0019] The present invention also provides a method for preparing the above-mentioned micron-silicon dioxide crystal-doped tellurite fluorescent glass, comprising the following steps:

[0020] After the TeO2, ZnO, Na2O and Al2O3 are mixed and ground, the precursor glass powder is first melted, cast and ground;

[0021] Mixing the precursor glass powder with the yttrium aluminum garnet yellow phosphor and micron silicon dioxide crystals, and performing a second melting to obtain a mixed glass liquid;

[0022] The mixed glass liquid is solidified and formed, and then annealed to obtain the micron silicon dioxide crystal-doped tellurite fluorescent glass.

[0023] Furthermore, the temperature of the first melting is 850-950° C., and the time is 30-50 min; the temperature of the second melting is 550-650° C., and the time is 10-30 min.

[0024] Furthermore, the solidification molding temperature is 350-450° C.; the annealing temperature is 250-350° C., and the annealing time is 3 hours.

[0025] More preferably, after the first melting and casting, a heat treatment step is further included, specifically, the heat treatment temperature is 250-350° C. and the time is 1-5 hours.

[0026] The present invention further provides the use of the above-mentioned micron silicon dioxide crystal-doped tellurite fluorescent glass in white light laser lighting.

[0027] The present invention has strict restrictions on the amount of micron silicon dioxide crystals added, and the amount added cannot exceed the limited range. Otherwise, the transparency of the fluorescent glass will be reduced and the luminescence will be poor because the glass network formation body is not dense enough.

[0028] The purpose of the second melting in the present invention is to lower the melting temperature of the fluorescent glass, shorten the time the fluorescent powder is exposed to high temperature during the preparation process, and thus reduce the damage to the crystal structure of the fluorescent powder caused by high temperature.

[0029] The micron-silicon dioxide crystals in the raw material components of the tellurite fluorescent glass of the present invention have a high thermal conductivity coefficient, which can enhance the heat dissipation capacity of the fluorescent glass. In addition, they have a low light absorption coefficient and a good reflection effect. While enhancing the heat dissipation performance of the tellurite fluorescent glass, they can also act as scattering centers, thereby significantly enhancing the luminous intensity and laser damage threshold of the high-heat dissipation tellurite fluorescent glass doped with the micron-silicon dioxide crystals.

[0030] By adjusting the composition of the tellurite glass, the present invention ensures excellent fluidity and suitable density in the molten state, allowing the micronized silica crystals to have good wettability in the glass. This ensures that the silica crystals are fully in contact with the molten glass during the doping process, eliminating the formation of pores and improving the density of the fluorescent glass. Furthermore, the silica crystals can disperse themselves in the fluorescent glass during the melting process, without the clustering and agglomeration that occurs with other high-thermal-conductivity powders, thus improving the uniformity of the fluorescent glass.

[0031] The present invention discloses the following technical effects:

[0032] The high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals of the present invention has efficient luminescence performance, excellent thermal stability, and a high laser irradiation threshold, which can meet the high-performance requirements of white-light laser lighting; at the same time, it has the significant advantages of simple preparation process, green environmental protection, and low production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0034] Figure 1 High-definition transmission electron microscope and diffraction images of the tetragonal micron silicon dioxide crystal prepared in Example 1 of the present invention;

[0035] Figure 2 XRD images of the micronized silicon dioxide crystals obtained in Example 1 and the tellurite fluorescent glass materials obtained in Examples 2, 3, and 6 of the present invention;

[0036] Figure 3 Transmittance spectra of the high-heat-dissipation tellurite fluorescent glass doped with micronized silica crystals prepared in Examples 4 to 7 of the present invention and the tellurite glass matrix material prepared in Comparative Example 1 in the 300-800 nm wavelength range (the insets, from left to right, are actual images of the materials of Comparative Example 1 and Examples 4 to 7 under white light irradiation, respectively);

[0037] Figure 4 Emission spectra of the high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals prepared in Examples 4 to 7 of the present invention and the tellurite fluorescent glass material prepared in Comparative Example 2 in the 480-700 nm wavelength range;

[0038] Figure 5A line graph showing the relationship between luminous flux and laser irradiation density of the high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals prepared in Examples 4 to 7 of the present invention and the tellurite fluorescent glass material prepared in Comparative Example 2 under 450nm blue laser excitation;

[0039] Figure 6 The line graphs are the relationship between the temperature of the high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals prepared in Example 6 of the present invention and the tellurite fluorescent glass prepared in Comparative Example 2 under 450nm blue laser excitation and the laser irradiation density (the illustrations are the two materials at 6W / mm 2 Infrared thermal imaging image under blue laser irradiation of laser irradiation density). DETAILED DESCRIPTION

[0040] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0041] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0042] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0043] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0044] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0045] Unless otherwise specified, the raw materials used in the examples of the present invention were purchased from commercial sources.

[0046] Unless otherwise specified, the "room temperature" described in the embodiments of the present invention is within the range of 20 to 30°C.

[0047] The technical solution of the present invention is further illustrated by the following examples.

[0048] Example 1

[0049] Preparation of tetragonal micronized silica crystals:

[0050] Amorphous silicon dioxide powder with a purity of ≥99.9% was heated at 1600°C for 1 hour, cooled to room temperature, then kept at 1400°C for 10 hours, cooled to room temperature again and ground to obtain micron silicon dioxide crystals with a particle size of 1 to 20 μm.

[0051] The micronized silicon dioxide crystals prepared in Example 1 were observed using a high-resolution transmission electron microscope. Figure 1 The left image shows an image of a 2μm diameter micronized silica crystal. The inset in the left image is a high-resolution electron diffraction pattern, showing neatly arranged square diffraction spots with high symmetry. This demonstrates that after high-temperature heat treatment, the amorphous silica powder has developed a distinct crystalline structure. The right image shows the morphology of the silica crystal at a 10nm scale, with clearly visible lattice fringes and a 0.316nm spacing, consistent with the lattice spacing of tetragonal silica.

[0052] Example 2

[0053] Preparation of high-thermal tellurite fluorescent glass doped with micronized silica crystals:

[0054] (1) According to the amounts of the raw materials shown in Table 1, yttrium aluminum garnet yellow phosphor, micronized silica crystals (prepared in Example 1), TeO2, ZnO, Na2O, and Al2O3 were weighed;

[0055] (2) TeO2, ZnO, Na2O and Al2O3 are mixed and ground evenly, placed in an alumina crucible, and placed in a silicon carbon rod electric furnace at 900°C for melting (first melting) for 40 minutes to obtain glass liquid, which is then poured into a 400°C mold for casting and molding, and then quickly transferred to a muffle furnace heated to 300°C, kept warm for 3 hours, and then cooled to room temperature to obtain a precursor glass and grind it to obtain a precursor glass powder with fine particles and uniform size;

[0056] (3) The obtained precursor glass powder, micron silica crystals and yttrium aluminum garnet yellow phosphor are mixed evenly and poured into a crucible together, and placed in a silicon carbon rod electric furnace at 600°C for melting (second melting) for 20 minutes to obtain a mixed glass liquid (clear, uniform and bubble-free). The mixed glass liquid is poured into a mold preheated to 400°C for solidification and quickly transferred to a muffle furnace heated to 300°C for annealing. After keeping warm for 3 hours, it is cooled to room temperature to obtain a high-heat tellurite fluorescent glass material doped with micron silica crystals.

[0057] Example 3

[0058] Preparation of high-thermal tellurite fluorescent glass doped with micronized silica crystals:

[0059] (1) According to the amounts of the raw materials shown in Table 1, yttrium aluminum garnet yellow phosphor, micronized silica crystals (prepared in Example 1), TeO2, ZnO, Na2O, and Al2O3 were weighed;

[0060] The preparation process of steps (2)-(3) is the same as that of Example 2.

[0061] Example 4

[0062] Preparation of high-thermal tellurite fluorescent glass doped with micronized silica crystals:

[0063] (1) According to the amounts of the raw materials shown in Table 1, yttrium aluminum garnet yellow phosphor, micronized silica crystals (prepared in Example 1), TeO2, ZnO, Na2O, and Al2O3 were weighed;

[0064] The preparation process of steps (2)-(3) is the same as that of Example 2.

[0065] Example 5

[0066] Preparation of high-thermal tellurite fluorescent glass doped with micronized silica crystals:

[0067] (1) According to the amounts of the raw materials shown in Table 1, yttrium aluminum garnet yellow phosphor, micronized silica crystals (prepared in Example 1), TeO2, ZnO, Na2O, and Al2O3 were weighed;

[0068] The preparation process of steps (2)-(3) is the same as that of Example 2.

[0069] Example 6

[0070] Preparation of high-thermal tellurite fluorescent glass doped with micronized silica crystals:

[0071] (1) According to the amounts of the raw materials shown in Table 1, yttrium aluminum garnet yellow phosphor, micronized silica crystals (prepared in Example 1), TeO2, ZnO, Na2O, and Al2O3 were weighed;

[0072] The preparation process of steps (2)-(3) is the same as that of Example 2.

[0073] Example 7

[0074] Preparation of high-thermal tellurite fluorescent glass doped with micronized silica crystals:

[0075] (1) According to the amounts of the raw materials shown in Table 1, yttrium aluminum garnet yellow phosphor, micronized silica crystals (prepared in Example 1), TeO2, ZnO, Na2O, and Al2O3 were weighed;

[0076] The preparation process of steps (2)-(3) is the same as that of Example 2.

[0077] Comparative Example 1

[0078] Preparation of tellurite glass matrix materials:

[0079] (1) According to the amounts of each raw material shown in Table 1, weigh TeO2, ZnO, Na2O and Al2O3;

[0080] (2) TeO2, ZnO, Na2O and Al2O3 were mixed and ground evenly, placed in an alumina crucible, and placed in a silicon carbon rod electric furnace at 900°C for melting (first melting) for 40 minutes to obtain glass liquid. The above glass liquid was poured into a 400°C mold for casting and then quickly transferred to a muffle furnace heated to 300°C. After keeping warm for 3 hours, it was cooled to room temperature to obtain a precursor glass and polished to obtain a smooth and transparent tellurite glass matrix material.

[0081] Comparative Example 2

[0082] (1) According to the amounts of each raw material shown in Table 1, weigh yttrium aluminum garnet yellow phosphor, TeO2, ZnO, Na2O and Al2O3;

[0083] (2) TeO2, ZnO, Na2O and Al2O3 are mixed and ground evenly, placed in an alumina crucible, and placed in a silicon carbon rod electric furnace at 900°C for melting (first melting) for 40 minutes to obtain glass liquid, which is then poured into a 400°C mold for casting and molding, and then quickly transferred to a muffle furnace heated to 300°C, kept warm for 3 hours, and then cooled to room temperature to obtain a precursor glass and grind it to obtain a precursor glass powder with fine particles and uniform size;

[0084] (3) The obtained precursor glass powder and yttrium aluminum garnet yellow phosphor are evenly mixed and poured into a crucible, and placed in a silicon carbon rod electric furnace at 600°C for melting (second melting) for 20 minutes, and then poured into a mold that has been preheated to 400°C for solidification and forming, and quickly transferred to a muffle furnace that has been heated to 300°C for annealing treatment. After keeping the temperature for 3 hours, it is cooled to room temperature to obtain a tellurite fluorescent glass material.

[0085] Table 1

[0086]

[0087]

[0088] Comparative Example 3

[0089] The only difference from Example 6 is that the micron silicon dioxide crystals are replaced with amorphous silicon dioxide powder of equal mass.

[0090] Comparative Example 4

[0091] The only difference from Example 6 is that the micron silicon dioxide crystals are replaced with micron boron nitride powder of equal mass.

[0092] The performance tests were performed on the materials prepared in Examples 2-7 and Comparative Examples 1-4:

[0093] 1. Transmission electron microscope images

[0094] The micronized silica crystals obtained in Example 1 were observed using a transmission electron microscope, producing high-definition transmission electron microscope images and electron diffraction patterns. The left image shows that the silica crystals have a diameter of approximately 2 μm. This micron-sized size is highly suitable for use as light scattering centers and thermal conductivity. The inset in the left image is an electron diffraction pattern of the silica crystals. When the incident electron beam meets a certain angle with the crystal face within the crystal, the electron beam is reflected and intensified by the crystal face, resulting in the diffraction spots shown in the image. Figure 1 The diffraction spots in the image are neatly arranged, showing a high degree of symmetry and regularity, indicating that the crystal structure of the silicon dioxide crystal prepared by the present invention has symmetrical crystal planes and a periodic repeatability. This ordered crystal structure provides a stable channel for heat conduction, reducing the scattering and obstruction of thermal phonons during conduction, thereby improving thermal conductivity. The lattice spacing in the right figure belongs to the (111) crystal plane of tetragonal silicon dioxide, which also proves that the preparation of tetragonal silicon dioxide crystals was successful.

[0095] 2.XRD pattern

[0096] Using Cu~K αThe XRD patterns of the micronized silicon dioxide crystals obtained in Example 1 and the tellurite fluorescent glass materials obtained in Examples 2, 3 and 6 were measured by X-ray diffraction in radiation mode. Figure 2 As shown. It can be seen that Example 1 completely corresponds to the characteristic peaks shown in the micron silica crystal standard card, proving that the micron silica crystal was successfully synthesized. In other examples, yttrium aluminum garnet yellow phosphor (Y3Al5O 12 ) and micron-silica crystal phases, which confirms that the micron-silica crystals will not introduce impurities into the tellurite fluorescent glass and the yttrium aluminum garnet yellow phosphor crystals are not destroyed.

[0097] 3. Transmission spectrum

[0098] The tellurite glass matrix material prepared in Comparative Example 1 and the high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals prepared in Examples 4 to 7 were measured in the 300-800 nm band using a spectrophotometer and an ultraviolet-visible-near-infrared spectrometer to obtain transmission spectra, as shown in FIG. Figure 3 The illustrations from left to right are the actual pictures of the samples of Comparative Example 1 and Examples 4 to 7 under white light irradiation.

[0099] from Figure 3 It can be seen that the high-heat tellurite fluorescent glass doped with micronized silica crystals prepared by the present invention has good transmittance, and as the content of micronized silica increases, the transmittance of the fluorescent glass in visible light gradually decreases, which proves that the silica crystals play a certain light scattering role in the fluorescent glass. Excessive transparency causes the excitation light source to directly penetrate the glass, and it is impossible to achieve effective scattering and uniform distribution of light. Therefore, when designing and preparing fluorescent glass, it is necessary to comprehensively consider the balance between scattering and transparency. Micronized silica particles can act as scatterers to disperse the incident light, causing the light to be reflected and refracted multiple times inside the fluorescent glass, thereby enhancing the absorption and conversion of the excitation light source by the phosphor, thereby obtaining higher luminous efficiency.

[0100] 4. Fluorescence spectrum

[0101] The fluorescence spectra of the high-heat-dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals prepared in Examples 4 to 7 and the tellurite fluorescent glass material obtained in Comparative Example 2 were tested under 450 nm laser diode pumping. Figure 4 As shown in Figure 2, broadband luminescence with a central wavelength of 540 nm is obtained under the pumping of a 450 nm laser diode. It can be seen that since the micron-sized silicon dioxide crystals act as scattering centers, their introduction significantly improves the emission intensity of the tellurite fluorescent glass material.

[0102] 5. Laser irradiation threshold test

[0103] The high heat dissipation tellurite fluorescent glass doped with micronized silicon dioxide crystals prepared in Examples 4 to 7 and the tellurite fluorescent glass materials prepared in Comparative Examples 2 to 3 were tested for luminous flux and laser irradiation density. The results are shown in FIG. Figure 5 .Depend on Figure 5 It can be seen that under 450nm blue laser irradiation, the introduction of micronized silica crystals enhances the heat dissipation capacity of the glass, making the material more difficult to break under high-power laser irradiation. The sample of Example 6 has the best luminous efficiency and laser irradiation threshold. Compared with Comparative Example 2, the maximum laser power density that this micronized silica crystal-doped high-heat-dissipation tellurite fluorescent glass can withstand is increased by about 40%. At 7W / mm 2 Under the laser power density of 100 nm, the luminous flux remains at 550 lm, while Comparative Example 2 at this time is thermally quenched due to the excessive temperature of the phosphor and no longer emits light. The laser irradiation threshold of the tellurite fluorescent glass material prepared in Comparative Example 3 does not show a significant improvement compared to Comparative Example 2. This is because the heat dissipation capacity of amorphous silica powder is much lower than that of tetragonal silica crystals, and it cannot bring additional heat dissipation effect to the fluorescent glass. The sample obtained in Comparative Example 4 has no obvious glass luster and the luminescence effect is extremely poor. This is because the composite effect of boron nitride and tellurite fluorescent glass is poor, and it cannot be spontaneously and evenly dispersed inside the fluorescent glass during the melting process like micron silica crystals, resulting in the agglomeration of boron nitride clusters, which hinders luminescence.

[0104] 6. Temperature and laser irradiation density test

[0105] The tellurite fluorescent glass material prepared in Comparative Example 2 and the tellurite fluorescent glass of Example 6 with the best luminous performance were irradiated with a 450nm blue laser. The laser irradiation density was continuously adjusted, and the temperature of the fluorescent glass was measured using an infrared temperature measuring gun. The relationship between the working temperature and the laser irradiation density was obtained, in which the illustrations are the two samples at 6W / mm 2 Infrared thermal imaging of laser irradiation density under blue laser irradiation, the results are shown in Figure 6 .Depend on Figure 6 It can be seen that under 450nm blue laser irradiation, the introduction of micron silicon dioxide crystals significantly reduces the temperature of the material under laser irradiation. 2 Under the laser irradiation density of 8W / mm, the tellurite fluorescent glass material prepared in Comparative Example 2 has been thermally quenched due to the high temperature. However, the tellurite fluorescent glass obtained in Example 6 is still working, and the working temperature is reduced by 54.3℃ compared with the former until 8W / mm 2 Thermal quenching occurs only when the laser irradiation density is above 0.

[0106] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A tellurite fluorescent glass doped with micronized silicon dioxide crystals, characterized in that: The raw materials include the following components: Yttrium aluminum garnet yellow phosphor, micronized silica crystals, and precursor glass powder; The precursor glass powder is composed of the following components in terms of mole percentage: TeO2 59-70%, ZnO 10-20%, Na2O 10-20% and Al2O3 1-10%; The mass of the yttrium aluminum garnet yellow phosphor is 1 to 15% of the mass of the precursor glass powder; the mass of the micron silicon dioxide crystal is 10 to 25% of the mass of the precursor glass powder.

2. The micronized silicon dioxide crystal-doped tellurite fluorescent glass according to claim 1, characterized in that: The precursor glass powder consists of the following components in terms of mole percentage: TeO2 65%, ZnO 15%, Na2O 15% and Al2O3 5%; The mass of the yttrium aluminum garnet yellow phosphor is 15% of the mass of the precursor glass powder; the mass of the micron silicon dioxide crystal is 20% of the mass of the precursor glass powder.

3. The micron-silicon dioxide crystal-doped tellurite fluorescent glass according to claim 1, characterized in that: The micron silicon dioxide crystals are tetragonal micron silicon dioxide crystals.

4. The micron-silicon dioxide crystal-doped tellurite fluorescent glass according to claim 1, characterized in that: The particle size of the micron silicon dioxide crystals is 1 to 20 μm.

5. The micron-silicon dioxide crystal-doped tellurite fluorescent glass according to claim 1, characterized in that: The preparation method of the micron silicon dioxide crystals comprises the following steps: Amorphous silicon dioxide powder with a purity of ≥99.9% is heated at 1600° C. for 1 hour, cooled to room temperature, then kept at 1300-1500° C. for 6-10 hours, cooled to room temperature again, and then ground to obtain the micron silicon dioxide crystals.

6. The method for preparing the tellurite fluorescent glass doped with micronized silicon dioxide crystals according to any one of claims 1 to 5, characterized in that: The following steps are involved: After the TeO2, ZnO, Na2O and Al2O3 are mixed and ground, the precursor glass powder is first melted, cast and ground; Mixing the precursor glass powder with the yttrium aluminum garnet yellow phosphor and micron silicon dioxide crystals, and performing a second melting to obtain a mixed glass liquid; The mixed glass liquid is solidified and formed, and then annealed to obtain the micron silicon dioxide crystal-doped tellurite fluorescent glass.

7. The preparation method according to claim 6, characterized in that The temperature of the first melting is 850-950° C., and the time is 30-50 min; the temperature of the second melting is 550-650° C., and the time is 10-30 min.

8. The preparation method according to claim 6, characterized in that The solidification molding temperature is 350-450° C.; the annealing temperature is 250-350° C., and the annealing time is 3 hours.

9. Use of the tellurite fluorescent glass doped with micronized silicon dioxide crystals according to any one of claims 1 to 5 in white light laser lighting.

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