Preparation method of luminescent glass heavily doped with rare earth ions and application of light source

Abstract

The invention provides a preparation method of rare earth ion heavily-doped luminescent glass and application of a light source. The rare earth ion heavily-doped luminescent glass comprises the following components in percentage by mass: 50-68% of black talcum powder, 10-25% of LiF, 10-25% of NaF, 10-25% of CaF2, an externally-doped rare earth compound accounting for 15-25% of the total mass of other raw materials (black talcum powder + LiF + NaF + CaF2), and an externally-doped clarifying agent accounting for 0.5-2% of the total mass of other raw materials (black talcum powder + LiF + NaF + CaF2). The preparation raw materials of the luminescent glass are easy to obtain and low in price, the process is simple, and industrial production is easy; the emission peak of the obtained rare earth doped luminescent glass under the excitation of purple light / ultraviolet light is 450-750 nm, the internal quantum efficiency is greater than or equal to 85%, and the luminous intensity at 150 DEG C is more than 85% of the luminous intensity at room temperature. A light source packaged by the prepared luminescent glass has the characteristics of warm white light output, low color temperature (CCTlt, 4500K), high color rendering index (CRIGt, 90) and high lumen efficiency (LEgt, 851m / W).

Description

Technical Field

[0001] The present invention belongs to the technical field of glass materials, and in particular relates to a method for preparing luminescent glass heavily doped with rare earth ions and the application of a light source. Background Art

[0002] In recent years, global attention to efficient energy utilization, energy conservation, environmental protection, and sustainable development has continued to rise, driving a shift in research in optoelectronic functional materials toward novel materials that combine cost-effectiveness with superior optical properties. Rare earth luminescent materials, with their high conversion efficiency, strong light absorption, narrow spectral bandwidth, high color purity, and long fluorescence lifetime, have achieved breakthrough applications in display technology, lighting systems, laser media, and other fields. Their applications are also gradually expanding into emerging areas such as plant growth regulation, UV disinfection, and medical imaging. In particular, in white-light LED (W-LED) technology, rare earth luminescent materials, through diverse excitation methods such as photoluminescence, provide key support for the environmentally friendly, energy-saving, and long-life characteristics of light sources.

[0003] However, current mainstream W-LED technology relies on a composite packaging system that uses a blue or near-UV chip to excite monochromatic or multicolor phosphors. This phosphor-converted LED (pc-LED) faces significant challenges in its application. For example, the insufficient thermal stability of silicone encapsulation materials can easily lead to uneven spectral dispersion, while reabsorption between multicolor phosphors causes a loss in luminous efficiency. Furthermore, interfacial compatibility issues between traditional phosphors and epoxy resins also limit the long-term reliability of devices. In contrast, luminescent glass, as an emerging matrix material, offers unique advantages. Its high transparency, excellent thermochemical stability, simple manufacturing process, and good rare earth ion solubility not only mitigate phosphor sedimentation issues but also enable innovative applications such as fiber optic integration. Embedding rare earth ions into the glass network through a melt-quenching method creates evenly dispersed luminescent centers, thereby improving device luminous efficiency and color uniformity.

[0004] rare earth Eu 3+ / Tb 3+ / Dy 3+ Eu ions have become an ideal luminescent activator due to their multi-level structure, narrow-band emission, high color purity, and bright colors. 3+ / Tb 3+ / Dy 3+ Doped luminescent glass has been extensively studied by many scholars. For example, publication number CN103803797B proposed a luminescent glass for LED and its preparation method, publication number CN106587601A proposed a borate red luminescent glass and its preparation method, and publication number CN112125514B proposed a rare earth ion Eu doped luminescent glass. 3+Several prior art publications, such as the preparation method of tellurium borate luminescent glass in CN108395097B, a rare-earth-doped luminescent glass and its preparation method, and a borotungstate luminescent glass for near-ultraviolet LED excitation and its preparation method in CN103896489B, all disclose several rare-earth ion-doped luminescent glasses. However, based on their disclosures, these prior art applications all utilize oxide-based glasses primarily composed of silicates, borates, phosphates, phosphosilicates, and borosilicates, resulting in high phonon energies. Furthermore, the rare-earth ion doping concentrations in these disclosed luminescent glasses are low (generally less than 5%, or even less than 1%), preventing them from achieving strong absorption of excitation light. These issues result in low luminous efficiency in these luminescent glasses. Therefore, modifying the glass composition and increasing the rare-earth ion doping concentration are crucial for improving the luminous efficiency of luminescent glasses.

[0005] In addition, China has a wide variety of minerals and rich black talc resources, but traditional applications are mostly limited to ceramic raw materials and industrial additives. Existing technologies such as publication numbers CN105753448B, CN109678461B, CN116589908A, and CN112961578A disclose several methods for preparing glazed tile bodies, ceramic bodies, and coatings, but black talc is only added as an additive, its utilization is insufficient, and no high-value-added products are produced. In addition, fluoride oxide glass is considered to be an excellent luminescent matrix material because it has both the excellent stability and mechanical properties of oxide glass and the low phonon energy of fluoride glass. In view of this, the rare earth ion heavily doped luminescent glass prepared by combining black talc powder, fluoride raw materials, and rare earth ions through a high-temperature melting process and annealing treatment can not only fully utilize the characteristics of black talc, but also achieve high-efficiency luminescence through heavy doping and strong absorption of rare earth ions. The development of this luminescent material not only expands the high-value application of black talc in the optoelectronic field, but also provides an innovative path for achieving high-efficiency luminescence of luminescent glass.

[0006] To this end, the present application proposes a method for preparing rare earth ion heavily doped luminescent glass and the application of the light source. Summary of the Invention

[0007] Therefore, the technical problem addressed by the present invention is to provide a method for preparing luminescent glass heavily doped with rare earth ions and its application as a light source. The raw materials used to prepare the luminescent glass are readily available and inexpensive, the process is simple, and it is amenable to industrial production. The resulting rare earth-doped luminescent glass exhibits an emission peak between 450 and 750 nm under violet / ultraviolet light excitation, an internal quantum efficiency of 85%, and a luminous intensity at 150°C that is at least 85% of the luminous intensity at room temperature. Light sources encapsulated with this luminescent glass exhibit warm white light output, low color temperature (CCT < 4500K), a high color rendering index (CRI > 90), and high lumen efficiency (LE > 85 lm / W).

[0008] In order to solve the above problems, the present invention provides a luminescent glass heavily doped with rare earth ions, comprising the following compositions by mass percentage: black talc: 50-68wt.%, LiF: 10-25wt.%, NaF: 10-25wt.%, CaF2: 10-25wt.%, the content of the doped rare earth compound is 15-25wt.% of the total mass of the other raw materials (black talc + LiF + NaF + CaF2), and the content of the doped clarifier is 0.5-2wt.% of the total mass of the other raw materials (black talc + LiF + NaF + CaF2).

[0009] Preferably, the particle size of black talc powder is 50-100 μm; the rare earth ion in the doped rare earth compound is Tb 3+ or Eu 3+ or Dy 3+ .

[0010] Preferably, the clarifier is one or more combinations of Sb2O3, NH4Cl or NaSbO3.

[0011] A method for preparing rare earth ion heavily doped luminescent glass is also provided, comprising the following steps: S1. Accurately weigh various raw materials according to a predetermined mass ratio, put them into an agate mortar and grind them for 0.5 to 5 hours to obtain a uniform mixture.

[0012] S2. The obtained mixture is put into a molybdenum crucible or a quartz crucible and placed in a glass melting furnace. The temperature is raised to 1500-1700° C. and kept at this temperature for 1-8 hours. During the melting process, the “external field assisted induced homogenization” process is used to obtain clarified glass liquid.

[0013] S3. After the melting is completed, the glass liquid is taken out and poured into water for quenching to obtain glass fragments, which are collected, washed, dried, and ground to obtain glass powder.

[0014] S4. The obtained glass powder is again loaded into a molybdenum crucible or a quartz crucible and placed in a glass melting furnace. The temperature is raised to 800-1300°C and kept warm for 0.5-5h. During the melting process, the "external field assisted induced homogenization" process is also used to obtain a uniformly melted glass liquid.

[0015] S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 500-700° C. and press-form it. Then move it into an annealing furnace at the same temperature and keep it warm for 2-18 hours for annealing. After annealing, cool it to room temperature to obtain luminescent glass.

[0016] Preferably, the "external field assisted induced homogenization" process described in steps S2 and S4 means that during the glass melting process, repeated oscillations of the external field (electric field, magnetic field, etc.) cause fluctuations in concentration and changes in microscopic pressure near the internal interface of the glass liquid, thereby promoting the diffusion of various ions in the glass liquid and achieving uniform melting of the glass.

[0017] Preferably, the heating rate of the glass melting furnace in S2 and S4 is 1-10°C / min; after the glass annealing in S5 is completed, the annealing furnace is cooled to room temperature at a rate of 5-20°C / min.

[0018] Preferably, during the glass melting process, when the external field is an electric field, the applied alternating electric field frequency is 50 Hz; if the external field is a magnetic field, the applied alternating frequency is 100 Hz.

[0019] It is also used to provide a method for preparing a white light source, using a screen printing process to 10 O 17 :Eu 2+ Blue powder, Ba2SiO4:Eu 2+ Green powder, (Sr,Ca)AlSiN3:Eu 2+ Red powder, Y2O3:Eu 3+ Several fluorescent powders in the red powder and low-melting-point glass powder are solidified on the above-mentioned luminescent glass and combined with the LED chip to obtain a white light emitting light source.

[0020] In summary, compared with the prior art, this application has the following technical effects: 1. The invention has low investment, cheap raw materials, simple production process, and no strict production conditions, and is suitable for industrial production; 2. The luminescent glass prepared by the present invention achieves heavy doping of rare earth ions (>15wt.%), and the rare earth ions do not exhibit "segregation" and are evenly distributed; 3. The rare earth ion heavily doped luminescent glass obtained by this invention has an emission peak between 450 and 750 nm under violet / ultraviolet light excitation, an internal quantum efficiency of 85% or higher, and a luminous intensity at 150°C that is at least 85% of that at room temperature. The encapsulated white light source exhibits warm white light output, a low color temperature (CCT < 4500K), a high color rendering index (CRI > 90), and a high lumen efficiency (LE > 85 lm / W), making it particularly suitable for white light illumination, screen displays, and other fields. 4. The present invention uses black talc powder as the main raw material and prepares rare earth ion heavily doped luminescent glass after high-temperature melting and annealing processes. This not only expands the high-value application of black talc in the optoelectronic field, but also provides an innovative path to achieve high-efficiency luminescence of luminescent glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a flow chart of a method for preparing a rare earth ion heavily doped luminescent glass according to the present invention; Figure 2 The rare earth Eu of the present invention 3+ Excitation spectrum of ion-doped luminescent glass; Figure 3 The rare earth Eu of the present invention 3+ Emission spectra of ion-doped luminescent glasses; Figure 4 The rare earth Tb of the present invention 3+ Emission spectra of ion-doped luminescent glasses; Figure 5 The rare earth Dy of the present invention 3+ Emission spectra of ion-doped luminescent glasses; Figure 6 The rare earth Eu of the present invention 3+ Quantum efficiency test chart of ion-doped luminescent glass. DETAILED DESCRIPTION

[0022] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0023] Example 1: The present invention provides a luminescent glass heavily doped with rare earth ions, comprising the following compositions by mass percentage: black talc: 50-68wt.%, LiF: 10-25wt.%, NaF: 10-25wt.%, CaF2: 10-25wt.%, the content of the doped rare earth compound is 15-25wt.% of the total mass of the other raw materials (black talc + LiF + NaF + CaF2), and the content of the doped clarifier is 0.5-2wt.% of the total mass of the other raw materials (black talc + LiF + NaF + CaF2).

[0024] The particle size of black talc powder is 50-100 μm; the rare earth ion in the doped rare earth compound is Tb 3+ or Eu 3+ or Dy 3+ The raw materials are the corresponding rare earth oxides or rare earth carbonates.

[0025] The clarifier is one or more combinations of Sb2O3, NH4Cl or NaSbO3.

[0026] In this embodiment, the prepared rare earth-doped luminescent glass emits strong red light, green light, or yellow-green light under violet light / ultraviolet light excitation, with an emission peak between 450 and 750 nm, an internal quantum efficiency ≥85%, and a luminescence intensity at 150°C of more than 85% of the luminescence intensity at room temperature.

[0027] Example 2: Reference Figure 1 、 Figure 2 and Figure 3 As shown, the present invention provides a rare earth Eu 3+ A method for preparing ion-heavily doped luminescent glass comprises the following steps: S1. Weigh the raw materials: black talc powder: 15.7500 g; LiF: 6.0606 g; NaF: 4.8485 g; CaF2: 3.4673 g; Sb2O3: 0.3015 g; Eu2O3: 4.5005 g. Mix the raw materials in an agate mortar and grind for 1 hour to obtain a uniform mixture.

[0028] S2. The obtained mixture is loaded into a molybdenum crucible and placed in a glass melting furnace. The temperature is raised from room temperature to 1550°C at a heating rate of 5°C / min and kept warm for 2.5 hours. At the same time, the "electric field assisted induced homogenization" process is adopted during the melting of the raw materials. An alternating electric field with a frequency of 50 Hz is applied throughout the whole process to obtain a clear glass liquid.

[0029] S3. After the melting is completed, the glass liquid is quickly taken out and poured into water for water quenching to obtain glass debris, which is collected and washed, dried, and ground to obtain glass powder.

[0030] S4. The obtained glass powder is loaded into a molybdenum crucible again and placed in a glass melting furnace. The temperature is raised from room temperature to 900°C at a heating rate of 5°C / min and kept at this temperature for 1 hour. The "electric field assisted induced homogenization" process is also adopted during the melting process. An alternating electric field with a frequency of 50 Hz is applied throughout the whole process to obtain a uniformly melted glass liquid.

[0031] S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 580°C and press into shape. Then move it into an annealing furnace at the same temperature and keep it warm for 8 hours for annealing. After the annealing is completed, cool the annealing furnace to room temperature at a rate of 10°C / min to obtain homogeneous, bubble-free luminescent glass.

[0032] The rare earth Eu obtained in this example 3+ The emission peak of the ion-doped luminescent glass under 395nm violet light excitation is between 550 and 750nm, the internal quantum efficiency is 92.22%, and the luminous intensity at 150℃ is 90.3% of the luminous intensity at room temperature. 10 O 17 :Eu 2+ Blue powder, Ba2SiO4:Eu 2+ Green powder, low melting point glass powder, 395nm LED and Eu 3+ The doped luminescent glass is encapsulated, and the color coordinates of the white light source after encapsulation are (0.3679, 0.3850), with warm white light emission, color temperature CCT of 4403K, color rendering index CRI of 92.8, and lumen efficiency LE of 90.5lm / W.

[0033] Example 3: Reference Figure 1 、 Figure 2 、 Figure 3 as well as Figure 6 As shown, the present invention provides a rare earth Eu 3+ A method for preparing ion-heavily doped luminescent glass comprises the following steps: S1. Weigh the raw materials: black talc powder: 18.9000g; LiF: 3.6364g; NaF: 4.5455g; CaF2: 3.0151g; Sb2O3: 0.0905g; NH4Cl: 0.1508g; Eu2(CO3)3: 6.3006g. Mix the above raw materials in an agate mortar and grind for 2 hours to obtain a uniform mixture.

[0034] S2. The obtained mixture is loaded into a molybdenum crucible and placed in a glass melting furnace. The temperature is raised from room temperature to 1650°C at a heating rate of 4°C / min and kept warm for 3.5 hours. At the same time, a "magnetic field assisted induced homogenization" process is adopted during the melting of the raw materials. An alternating magnetic field with a frequency of 100 Hz is applied throughout the entire process to obtain a clear glass liquid.

[0035] S3. After the melting is completed, the glass liquid is quickly taken out and poured into water for water quenching to obtain glass debris, which is collected and washed, dried, and ground to obtain glass powder.

[0036] S4. The obtained glass powder is loaded into a quartz crucible again and placed in a glass melting furnace. The temperature is raised from room temperature to 1200°C at a heating rate of 4°C / min and kept at this temperature for 2 hours. The "magnetic field assisted induced homogenization" process is also adopted during the melting process. An alternating magnetic field with a frequency of 100 Hz is applied throughout the entire process to obtain a uniformly melted glass liquid.

[0037] S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 680°C and press it into shape. Then move it into an annealing furnace at the same temperature and keep it warm for 10 hours for annealing. After the annealing is completed, cool the annealing furnace to room temperature at a rate of 15°C / min to obtain homogeneous, bubble-free luminescent glass.

[0038] The rare earth Eu obtained in this example 3+ The emission peak of the ion-doped luminescent glass under 395nm violet light excitation is between 550 and 750nm, the internal quantum efficiency is 89.31%, and the luminous intensity at 150℃ is 89.6% of the luminous intensity at room temperature. 10 O 17 :Eu 2+ Blue powder, Ba2SiO4:Eu 2+ Green powder, low melting point glass powder, 395nm LED and Eu 3+ The doped luminescent glass is encapsulated, and the color coordinates of the white light source after encapsulation are (0.3539, 0.3165), with warm white light emission, color temperature CCT of 4474K, color rendering index CRI of 91.2, and lumen efficiency LE of 94.8lm / W.

[0039] Example 4: Reference Figure 1 and Figure 4 As shown, the present invention provides a rare earth Tb 3+ A method for preparing ion-heavily doped luminescent glass comprises the following steps: S1. Weigh the raw materials: black talc powder: 17.7000g; LiF: 4.0909g; NaF: 4.6970g; CaF2: 3.6181g; Sb2O3: 0.3015g; NaSbO3: 0.1837g; Tb2O3: 6.0606g. Mix the above raw materials in an agate mortar and grind for 2 hours to obtain a uniform mixture.

[0040] S2. The obtained mixture is loaded into a molybdenum crucible and placed in a glass melting furnace. The temperature is raised from room temperature to 1580°C at a heating rate of 8°C / min and kept warm for 2 hours. At the same time, a "magnetic field assisted induced homogenization" process is adopted during the melting of the raw materials. An alternating magnetic field with a frequency of 100 Hz is applied throughout the entire process to obtain a clear glass liquid.

[0041] S3. After the melting is completed, the glass liquid is quickly taken out and poured into water for water quenching to obtain glass debris, which is collected and washed, dried, and ground to obtain glass powder.

[0042] S4. The obtained glass powder is loaded into a quartz crucible again and placed in a glass melting furnace. The temperature is raised from room temperature to 950°C at a heating rate of 8°C / min and kept at this temperature for 1.5 hours. The "magnetic field assisted induced homogenization" process is also adopted during the melting process. An alternating magnetic field with a frequency of 100 Hz is applied throughout the entire process to obtain a uniformly melted glass liquid.

[0043] S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 600°C and press it into shape. Then move it into an annealing furnace at the same temperature and keep it warm for 8 hours for annealing. After the annealing is completed, cool the annealing furnace to room temperature at a rate of 10°C / min to obtain homogeneous, bubble-free luminescent glass.

[0044] The rare earth Tb obtained in this embodiment 3+ The emission peak of the ion-doped luminescent glass under 375nm ultraviolet light excitation is between 400 and 650nm, the internal quantum efficiency is 86.55%, and the luminous intensity at 150℃ is 90.2% of the luminous intensity at room temperature. (Sr,Ca)AlSiN3:Eu 2+ Red powder, BaMgAl 10 O 17 :Eu 2+ Blue powder, low melting point glass powder, 375nm LED and Tb 3+ The doped luminescent glass is encapsulated, and the color coordinates of the white light source after encapsulation are (0.3598, 0.3351), with warm white light emission, color temperature CCT of 4369K, color rendering index CRI of 92.5, and lumen efficiency LE of 88.9lm / W.

[0045] Example 5: Reference Figure 1 and Figure 5 As shown, the present invention provides a rare earth Dy 3+ A method for preparing ion-heavily doped luminescent glass comprises the following steps: S1. Weigh the raw materials: black talc powder: 18.6000 g; LiF: 3.7879 g; NaF: 4.0909 g; CaF2: 3.6181 g; NaSbO3: 0.3673 g; Dy2O3: 5.4005 g. Mix the raw materials in an agate mortar and grind for 1.5 hours to obtain a uniform mixture.

[0046] S2. The obtained mixture is loaded into a molybdenum crucible and placed in a glass melting furnace. The temperature is raised from room temperature to 1620°C at a heating rate of 7°C / min and kept warm for 3 hours. At the same time, the "electric field assisted induced homogenization" process is adopted during the melting of the raw materials. An alternating electric field with a frequency of 50 Hz is applied throughout the whole process to obtain a clear glass liquid.

[0047] S3. After the melting is completed, the glass liquid is quickly taken out and poured into water for water quenching to obtain glass debris, which is collected and washed, dried, and ground to obtain glass powder.

[0048] S4. The obtained glass powder is loaded into a quartz crucible again and placed in a glass melting furnace. The temperature is raised from room temperature to 1150°C at a heating rate of 7°C / min and kept at this temperature for 2 hours. The "electric field assisted induced homogenization" process is also adopted during the melting process. An alternating magnetic field with a frequency of 50 Hz is applied throughout the whole process to obtain a uniformly melted glass liquid.

[0049] S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 650°C and press it into shape. Then move it into an annealing furnace at the same temperature and keep it warm for 10 hours for annealing. After the annealing is completed, cool the annealing furnace to room temperature at a rate of 15°C / min to obtain homogeneous, bubble-free luminescent glass.

[0050] The rare earth Dy obtained in this embodiment 3+ The emission peak of the ion-doped luminescent glass under 350nm ultraviolet light excitation is between 400 and 750nm, the internal quantum efficiency is 88.90%, and the luminous intensity at 150℃ is 89.5% of the luminous intensity at room temperature. 3+ Red powder, low melting point glass powder, 350nm LED and Dy 3+ The doped luminescent glass is encapsulated, and the color coordinates of the white light source after encapsulation are (0.3632, 0.3201), with warm white light emission, color temperature CCT of 4120K, color rendering index CRI of 90.8, and lumen efficiency LE of 91.2lm / W.

[0051] Example 6: Reference Figure 1 and Figure 4 As shown, the present invention provides a rare earth Tb 3+ A method for preparing ion-heavily doped luminescent glass comprises the following steps: S1. Weigh the raw materials: black talc powder: 16.5000g; LiF: 4.5455g; NaF: 5.3030g; CaF2: 3.7688g; NH4Cl: 0.2261g; NaSbO3: 0.2296g; Tb2O3: 5.1005g. Mix the above raw materials in an agate mortar and grind for 1.5 hours to obtain a uniform mixture.

[0052] S2. The obtained mixture is loaded into a molybdenum crucible and placed in a glass melting furnace. The temperature is raised from room temperature to 1550°C at a heating rate of 6°C / min and kept warm for 3 hours. At the same time, the "electric field assisted induced homogenization" process is adopted during the melting of the raw materials. An alternating electric field with a frequency of 50 Hz is applied throughout the whole process to obtain a clear glass liquid.

[0053] S3. After the melting is completed, the glass liquid is quickly taken out and poured into water for water quenching to obtain glass debris, which is collected and washed, dried, and ground to obtain glass powder.

[0054] S4. The obtained glass powder is loaded into a quartz crucible again and placed in a glass melting furnace. The temperature is raised from room temperature to 920°C at a heating rate of 6°C / min and kept warm for 1.5 hours. The "electric field assisted induced homogenization" process is also adopted during the melting process. An alternating magnetic field with a frequency of 50 Hz is applied throughout the whole process to obtain a uniformly melted glass liquid.

[0055] S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 650°C and press it into shape. Then move it into an annealing furnace at the same temperature and keep it warm for 6 hours for annealing. After the annealing is completed, cool the annealing furnace to room temperature at a rate of 10°C / min to obtain homogeneous, bubble-free luminescent glass.

[0056] The rare earth Tb obtained in this embodiment 3+ The emission peak of the ion-doped luminescent glass under 375nm ultraviolet light excitation is between 400 and 650nm, the internal quantum efficiency is 88.33%, and the luminous intensity at 150℃ is 87.6% of the luminous intensity at room temperature. (Sr,Ca)AlSiN3:Eu 2+ Red powder, BaMgAl 10 O 17 :Eu 2+ Blue powder, low melting point glass powder, 375nm LED and Tb 3+ The doped luminescent glass is encapsulated, and the color coordinates of the white light source after encapsulation are (0.3555, 0.3225), with warm white light emission, color temperature CCT of 4449K, color rendering index CRI of 91.8, and lumen efficiency LE of 85.9lm / W.

[0057] It is easy for those skilled in the art to understand that, under the premise of no conflict, the above-mentioned advantageous methods can be freely combined and superimposed.

[0058] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention. The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art may make various improvements and variations without departing from the technical principles of the present invention, and such improvements and variations shall also be considered within the scope of protection of the present invention.

Claims

1. A luminescent glass heavily doped with rare earth ions, characterized in that: The composition is as follows by mass percentage: black talc: 50-68wt.%, LiF: 10-25wt.%, NaF: 10-25wt.%, CaF2: 10-25wt.%, the content of the doped rare earth compound is 15-25wt.% of the total mass of other raw materials (black talc + LiF + NaF + CaF2), and the content of the doped clarifier is 0.5-2wt.% of the total mass of other raw materials (black talc + LiF + NaF + CaF2).

2. The rare earth ion heavily doped luminescent glass according to claim 1, characterized in that: The particle size of black talc powder is 50-100 μm; the rare earth ion in the doped rare earth compound is Tb 3+ or Eu 3+ or Dy 3+ .

3. The rare earth ion heavily doped luminescent glass according to claim 1, characterized in that: The clarifier is one or more combinations of Sb2O3, NH4Cl or NaSbO3.

4. A method for preparing a luminescent glass heavily doped with rare earth ions, according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1, according to the predetermined mass ratio accurately weighed various raw materials, put them into the agate mortar and grind for 0.5 to 5h to obtain a uniform mixture; S2, the resulting mixture is placed in a molybdenum crucible or a quartz crucible and placed in a glass melting furnace, heated to 1500 ~ 1700 ℃ and kept warm for 1 ~ 8 hours, and the "external field assisted induced homogenization" process is used during the melting process to obtain a clarified glass liquid; S3, after the melting is completed, the glass liquid is removed and poured into water for quenching to obtain glass debris, which is collected for washing, drying, and grinding to obtain glass powder; S4, the obtained glass powder is again loaded into a molybdenum crucible or a quartz crucible and placed in a glass melting furnace, heated to 800-1300°C and kept warm for 0.5-5h. During the melting process, the "external field assisted induced homogenization" process is also used to obtain a uniformly melted glass liquid; S5. Pour the obtained uniformly melted glass liquid onto a mold preheated to 500-700° C. and press-form it. Then move it into an annealing furnace at the same temperature and keep it warm for 2-18 hours for annealing. After annealing, cool it to room temperature to obtain luminescent glass.

5. The method for preparing a rare earth ion heavily doped luminescent glass according to claim 4, characterized in that: The "external field-assisted induced homogenization" process described in steps S2 and S4 refers to the process in which, during the glass melting process, repeated oscillations of an external field (electric field, magnetic field) cause fluctuations in concentration and changes in microscopic pressure near the internal interface of the glass liquid, thereby promoting the diffusion of various ions in the glass liquid and achieving uniform melting of the glass.

6. The method for preparing a rare earth ion heavily doped luminescent glass according to claim 4, characterized in that: The heating rate of the glass melting furnace in S2 and S4 is 1-10°C / min; after the glass annealing in S5 is completed, the annealing furnace is cooled to room temperature at a rate of 5-20°C / min.

7. The method for preparing a rare earth ion heavily doped luminescent glass according to claim 5, characterized in that: During the glass melting process, when the external field is an electric field, the applied alternating electric field frequency is 50 Hz; if the external field is a magnetic field, the applied alternating frequency is 100 Hz.

8. A method for preparing a white light source, characterized in that: BaMgAl is printed by screen printing. 10 O 17 :Eu 2+ Blue powder, Ba2SiO4:Eu 2+ Green powder, (Sr,Ca)AlSiN3:Eu 2+ Red powder, Y2O3:Eu 3+ The fluorescent powder in the red powder and the low-melting-point glass powder are solidified on the luminescent glass heavily doped with rare earth ions as claimed in any one of claims 1 to 3, and combined with an LED chip to obtain a white light emitting source.

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