Silver ion doped tin fluorophosphate glass fluorescent film and preparation method thereof

Abstract

The application discloses a silver ion doped tin fluoro-phosphate glass fluorescent film and a preparation method thereof, and belongs to the technical field of optical functional fluorescent film materials. 3+ The film material comprises glass powder and yellow fluorescent powder YAG:Ce + The glass powder is prepared by doping Ag outside a tin fluoro-phosphate matrix glass. The silver ion doped tin fluoro-phosphate glass fluorescent film provided by the application has a low sintering temperature, excellent film uniformity, low phonon energy, a wide laser excitation threshold and good thermal stability. By adjusting the film preparation process, the optical performance of the film can be controlled and adjusted, the film shows stable absorption and white light emission characteristics in the ultraviolet to visible wave band, and is suitable for the fields of laser illumination, optical coating and novel light emitting devices.

Description

Technical Field

[0001] This invention belongs to the field of optically functional fluorescent thin film materials technology, and particularly relates to a silver ion-doped tin fluorophosphate glass fluorescent thin film and its preparation method. Background Technology

[0002] Against the backdrop of global energy shortages and rapid iteration of green lighting technologies, semiconductor solid-state light sources, with their core advantages such as high luminous efficiency, low power consumption, small size, long lifespan, and environmental friendliness, are gradually replacing traditional incandescent and fluorescent lamps, becoming the mainstream development direction of next-generation lighting technology. As solid-state light sources upgrade towards higher power, higher brightness, and higher integration, multi-chip integrated white LEDs and white laser diodes have become cutting-edge research hotspots. Among these, the luminous efficiency and thermal stability of light conversion materials under high-power excitation conditions have become key technological bottlenecks restricting breakthroughs in the performance and large-scale application of solid-state light sources.

[0003] Currently, mainstream light conversion materials mainly include three categories: phosphors, fluorescent ceramics, and fluorescent glass thin films. Traditional phosphors have high luminous efficiency, but they are prone to thermal quenching under high-power laser or high-current-density excitation, leading to a significant decrease in luminous efficiency. While fluorescent ceramics possess good mechanical strength and thermal stability, they suffer from drawbacks such as high preparation temperatures, complex processes, and high costs, making them unsuitable for the low-cost, large-scale device fabrication requirements. Fluorescent glass thin films, due to their simple processing, controllable thickness, excellent thermal stability, and ease of chip integration, have become an important research direction for high-power light conversion materials.

[0004] However, conventional oxide glass matrices have relatively high phonon energies, which easily induce nonradiative transitions of phosphor ions under high-power excitation, significantly reducing light conversion efficiency. Therefore, low-phonon-energy fluoride and its derivative glass systems have attracted widespread attention. Among them, fluorophosphate glasses combine the excellent film-forming properties of phosphate glasses with the low phonon energy of fluoride glasses, while also possessing a wide optical transmission window and low melting temperature, making them ideal thin-film matrix materials. However, existing fluorophosphate systems generally suffer from problems such as easy aggregation of luminescent ions, poor valence state stability, and poor film uniformity, severely limiting their application in high-performance optoelectronic devices.

[0005] Silver ions, as classic sensitizing ions, can modulate the Sn content in fluorescent films through localized surface plasmon resonance when they exist in the form of nanoclusters or nanoparticles. 2+ With Ce 3+The local electromagnetic field increases the absorption and emission cross-section, significantly improving luminescence efficiency. However, in conventional glass systems, silver ions are prone to aggregation and abnormal valence state transitions, which not only reduce luminescence efficiency but also make it difficult to control the dispersion uniformity during thin film preparation. Therefore, developing a structurally stable, low-phonon-energy fluorophosphate glass system that enables uniform silver ion dispersion and achieving efficient thin film preparation to fundamentally improve the material's luminous efficacy and thermal stability has become a core technical challenge that urgently needs to be addressed in this field. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention proposes a silver ion-doped tin fluorophosphate glass fluorescent thin film and its preparation method. By adjusting the composition ratio of the matrix glass, the doping concentration of Ag ions, and the ratio between glass powder and phosphor, high-brightness white light is emitted with low heat generation under high-power pumping of a 450nm commercial laser.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A silver ion-doped tin fluorophosphate glass fluorescent film comprises glass powder and yellow phosphor YAG:Ce; the glass powder is prepared by external doping AgNO3 onto a tin fluorophosphate matrix glass.

[0008] This invention specifies that the thin film is made of AgNO3-doped tin fluorophosphate glass powder and YAG:Ce 3+ Composed of yellow phosphors, it achieves a basic light-emitting architecture with low phonon energy, high thermal stability, and wide excitation threshold. It combines the film-forming properties of phosphate glass with the low phonon advantages of fluoride glass, making it suitable for high-power laser lighting scenarios.

[0009] Furthermore, the glass powder and the yellow phosphor YAG:Ce 3+ The mass ratio is 1:(1-9), preferably 1:4.

[0010] This invention limits the use of glass powder and YAG:Ce 3+ With a mass ratio of 1:(1-9), the density of luminescent centers and light conversion efficiency can be adjusted, avoiding weak luminescence due to excessively low phosphor concentration and quenching due to excessively high concentration, thus ensuring the luminescence intensity and uniformity of the thin film.

[0011] Furthermore, the external doping amount of the AgNO3 is 0-1.0% in molar percentage, and is not 0.

[0012] An appropriate amount of Ag exists as nanoclusters / particles, enhancing Sn through localized surface plasmon resonance. 2+ Ce 3+While emitting light, Ag's high thermal conductivity also forms a thermally conductive network, improving the thermal quenching threshold and luminescence efficiency. The role of Ag doping is that when Ag exists in the form of nanoclusters or nanoparticles, its surface plasmon resonance effect can alter the Sn content in the glass. 2+ Ce in thin films 3+ The surrounding local electromagnetic field increases the absorption and emission cross-sections, further improving luminescence efficiency. Furthermore, Ag, a metal with ultra-high thermal conductivity, can be incorporated into the tin fluorophosphate glass system to construct an efficient heat-conducting network, broadening the thermal quenching threshold under high-power excitation. In tests on the matrix glass, as the Ag ion doping concentration increased, both the excitation and emission intensities of the tin fluorophosphate glass showed a trend of first increasing and then decreasing, with the optimal doping concentration being 0.2%.

[0013] Furthermore, in molar percentage, the raw material composition of the tin fluorophosphate matrix glass includes: SnO: 10%, SnF2: 5%, ZnF2: 45%, P2O5: 40%.

[0014] This invention limits the glass composition ratio of tin fluorophosphate matrix, which can ensure low melting temperature, excellent film-forming properties, and low phonon energy of the glass, providing a foundation for uniform dispersion of silver ions and stable film preparation.

[0015] This invention also provides a method for preparing a silver ion-doped tin fluorophosphate glass fluorescent thin film, comprising the following steps: (1) Weigh SnO, SnF2, ZnF2, P2O5 and AgNO3 raw materials according to molar percentage, mix them evenly and place them in a crucible, preheat, melt, homogenize and clarify to obtain glass liquid; cast the glass liquid into a shape, anneal it to obtain glass block, grind and sieve the glass block to obtain glass powder; (2) The glass powder is mixed with yellow phosphor YAG:Ce 3+ Mix, add organic adhesive, and grind and disperse to obtain a composite slurry; (3) The composite slurry is coated on the surface of the substrate, and then dried and sintered to obtain the silver ion-doped tin fluorophosphate glass fluorescent film.

[0016] This invention provides a three-step preparation method (glass powder preparation → composite slurry preparation → coating and sintering to form a film), which is simple, has good repeatability, and low cost. It can achieve controllable adjustment of film thickness and optical properties and is suitable for large-scale production.

[0017] Furthermore, the preheating temperature is 400°C, and the preheating time is 20 minutes; The melting temperature is 1000℃ and the melting time is 40 minutes; The specific preparation steps of the glass block are as follows: pour the molten glass into a mold that has been preheated to 350°C, then place it in a muffle furnace that has been heated to 300°C, keep it at that temperature for 2-3 hours, then turn off the muffle furnace and cool it to room temperature to obtain the glass block. The sieving process involves passing the material through a 200-mesh sieve.

[0018] This invention defines precise temperature and time parameters for preheating, melting, and annealing, which can ensure that the glass melt is homogenized, clear, and bubble-free, and that the glass block is stress-free and structurally stable, thereby improving the purity of glass powder and the quality of film formation.

[0019] Furthermore, the organic adhesive is a terpineol-ethyl cellulose organic adhesive. The organic adhesive, glass powder, and yellow fluorescent powder YAG:Ce are then combined. 3+ The mass ratio of the mixed powders is 0.08:0.2.

[0020] This invention uses terpineol-ethyl cellulose organic adhesive, which has moderate viscosity and good dispersibility, allowing glass powder and phosphor to be mixed evenly. During sintering, the adhesive can be fully discharged, ensuring the density and optical uniformity of the film.

[0021] Furthermore, the substrate is a sapphire substrate, which has excellent thermal conductivity and chemical stability, making it suitable for high-power laser excitation scenarios. It also has an auxiliary thin-film heat dissipation function, thereby improving the device's lifespan.

[0022] Furthermore, the drying temperature is 120°C, and the drying time is 12 hours; The sintering process is carried out at a temperature of 420℃ for 20 minutes. Low-temperature sintering does not damage the luminescent properties of the phosphor, while simultaneously achieving complete removal of the organic adhesive and densification of the glass powder, thus ensuring the optical properties and structural stability of the thin film.

[0023] The present invention also provides the application of silver ion-doped tin fluorophosphate glass fluorescent thin film in the preparation of laser lighting devices, optical coatings or light-emitting devices.

[0024] This invention limits the application of thin films to laser lighting devices, optical coatings, and light-emitting devices. Leveraging the advantages of white light emission, high brightness, and high thermal stability, it adapts to the needs of high-power optoelectronic devices and broadens the application scenarios of optical functional thin films.

[0025] Compared with the prior art, the present invention has the following advantages and technical effects: (1) The silver ion-doped tin fluorophosphate glass fluorescent film of the present invention has excellent luminescence performance and maintains the low melting temperature characteristic of fluorophosphate glass. The preparation process of the obtained fluorescent film sample is simple, reproducible, and has low production cost, making it easy to obtain glass fluorescent film materials with high optical quality.

[0026] (2) This invention introduces an appropriate amount of silver ions into a tin fluorophosphate glass substrate, utilizing its surface plasmon resonance effect to alter the local electronic field of the luminescent ions, thereby increasing their absorption and emission cross-sections and further improving luminous efficiency. This thin film emits high-quality white light under 7W laser excitation from a 450nm commercial laser. The luminous flux reaches 1240 lm, and the luminous efficacy remains at 180 lm / W, with all performance characteristics superior to the undoped sample.

[0027] (3) The silver ion-doped tin fluorophosphate glass fluorescent film prepared by the present invention has good thermal conductivity and optical uniformity. It emits white light with a color rendering index of 75 under 450nm blue light excitation. Compared with the undoped sample, it has a wider thermal quenching threshold and a temperature 5℃ lower than the undoped sample under 7W power excitation. Attached Figure Description

[0028] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a comparison of the excitation-emission spectra of Ag-doped glass powders with different concentrations in Examples 1-5. Figure 2 The luminous flux of the tin fluorophosphate glass fluorescent thin film prepared for comparative examples 6-10 as a function of excitation power is shown in the curve. Figure 3 The light flux of the thin films prepared in Comparative Example 9 and Example 1 varies with excitation power. Figure 4 The curves showing the color index Ra of the films prepared in Comparative Example 9 and Example 1 as a function of excitation power are shown. Detailed Implementation

[0029] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0030] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0031] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0032] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0033] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0034] This invention provides a method for preparing a silver ion-doped tin fluorophosphate glass fluorescent thin film, comprising the following steps: (1) Preparation of glass powder: According to the molar percentage, SnO, SnF2, ZnF2, P2O5 and AgNO3 raw materials were weighed and ground evenly in an agate mortar to form a mixture. The mixture was then placed in a platinum crucible, covered with a crucible lid and placed in a muffle furnace at 400℃ for 20 min. The preheated platinum crucible was transferred to a silicon carbide rod electric furnace at 1000℃ for 40 min to melt, homogenize and clarify to obtain a uniform glass melt without bubbles. The glass melt was poured into a mold that had been preheated to 350℃ and then placed in a muffle furnace that had been heated to 300℃. After holding at this temperature for 2-3 h, the muffle furnace was closed and the temperature was lowered to room temperature to obtain a glass block. The block was then ground into powder and passed through a 200-mesh sieve to obtain a uniform glass powder. (2) Preparation of composite slurry: glass powder and yellow phosphor YAG:Ce 3+ Mix, add terpineol-ethyl cellulose organic gum, and grind and disperse thoroughly to form a composite slurry with moderate viscosity and uniform dispersion; (3) Preparation of silver ion-doped tin fluorophosphate glass fluorescent film: After uniformly coating the composite paste on the surface of the sapphire substrate, it is placed in an oven and dried at 120°C for 12 hours to remove organic solvents and form a green film. Then it is transferred to an annealing furnace and sintered at 420°C for 20 minutes to achieve full removal of organic adhesive and densification of glass powder while maintaining the luminescence performance of phosphor. Finally, it is naturally cooled to room temperature with the furnace, thus obtaining silver ion-doped tin fluorophosphate glass fluorescent film on the sapphire substrate.

[0035] In step (1) of the following preferred embodiment of the present invention, the molar percentages are SnO: 10%, SnF2: 5%, ZnF2: 45%, and P2O5: 40%.

[0036] In step (1) of the following preferred embodiment of the present invention, the glass powder is prepared by external doping of AgNO3 on a tin fluorophosphate matrix glass. The external doping amount of AgNO3 is 0-1.0% (e.g., 0.1%, 0.2%, 0.5% or 1.0%, preferably 0.2%), and is not 0.

[0037] In step (2) of the following preferred embodiment of the present invention, the glass powder and the yellow phosphor YAG:Ce 3+ The mass ratio is 1:(1-9), such as 1:1, 1:1.5, 1:2.3, 1:4 or 1:9, preferably 1:4.

[0038] A silver ion-doped tin fluorophosphate glass fluorescent film can be prepared using the above preparation method.

[0039] The silver ion-doped tin fluorophosphate glass fluorescent film described above can be used in the fabrication of laser lighting devices, optical coatings, or light-emitting devices.

[0040] The silver ion-doped tin fluorophosphate glass fluorescent thin film provided by this invention has a low sintering temperature, excellent film uniformity, low phonon energy, wide laser excitation threshold, and good thermal stability. By controlling the thin film preparation process, its optical properties can be controllably adjusted, exhibiting stable absorption and white light emission characteristics in the ultraviolet to visible wavelength range, making it suitable for laser lighting, optical coatings, and novel light-emitting devices.

[0041] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃.

[0042] The "glass melt" mentioned in the embodiments of the present invention is preferably a clear, uniform glass melt without bubbles.

[0043] All raw materials used in the embodiments of this invention were purchased commercially, including SnO, SnF2, ZnF2, P2O5, and AgNO3, which were purchased from Aladdin, and the yellow fluorescent powder YAG:Ce. 3+ Purchased from GRINM Advanced Materials Co., Ltd.

[0044] All raw materials used in this invention were purchased from the market.

[0045] The technical solution of the present invention will be further illustrated by the following embodiments.

[0046] Comparative Example 1 Weigh out SnO:10%, SnF2:5%, ZnF2:45%, and P2O5:40% as raw materials for tin fluorophosphate matrix glass. Grind them evenly in an agate mortar to form a mixture, then place it in a crucible, cover the crucible, and preheat it in a muffle furnace at 400℃ for 20 minutes. Transfer the preheated platinum crucible to a silicon carbide rod electric furnace at 1000℃ and melt it for 40 minutes. After homogenization and clarification, a uniform, bubble-free glass melt is obtained. Pour the glass melt into a mold preheated to 350℃, then place it in a muffle furnace preheated to 300℃ and hold it for 2.5 hours. After that, turn off the muffle furnace and cool it to room temperature to obtain a glass block. Grind it into powder, pass it through a 200-mesh sieve, and obtain a uniform glass powder (denoted as 0% Ag doped glass powder). Perform optical property tests on the glass powder, and the results are as follows. Figure 1 As shown.

[0047] Comparative Example 2 Similar to Comparative Example 1, the difference is that in step (1), 0.1% AgNO3 (denoted as 0.1% Ag-doped glass powder) is added to the tin fluorophosphate matrix glass.

[0048] Comparative Example 3 Similar to Comparative Example 1, the difference is that in step (1), 0.2% AgNO3 (denoted as 0.2% Ag-doped glass powder) is added to the tin fluorophosphate matrix glass.

[0049] Comparative Example 4 Similar to Comparative Example 1, the difference is that in step (1), 0.5% AgNO3 (denoted as 0.5% Ag-doped glass powder) is added to the tin fluorophosphate matrix glass.

[0050] Comparative Example 5 Similar to Comparative Example 1, the difference is that in step (1), 1.0% AgNO3 (referred to as 1.0% Ag-doped glass powder) is added to the tin fluorophosphate matrix glass.

[0051] Figure 1 This is a comparison of the excitation-emission spectra of Ag-doped glass powders with different concentrations in Examples 1-5. Figure 1 It can be seen that the luminescence intensity exhibits a significant and regular change with the Ag doping concentration. Specifically, as the Ag doping concentration increases from 0% to 0.2%, the luminescence intensity continuously increases, reaching its maximum value in Comparative Example 3, which is approximately 30% stronger than the undoped Comparative Example 1. Subsequently, when the Ag doping concentration is further increased to 0.5%, the luminescence intensity begins to decrease but remains higher than the undoped sample. When the Ag doping concentration reaches 1.0%, the luminescence intensity decreases significantly and even falls below that of the undoped sample. This trend of initial enhancement followed by weakening can be attributed to the localized surface plasmon resonance effect of Ag. Specifically, with appropriate Ag doping, the surface plasmon resonance generated by Ag nanoparticles can enhance the local electromagnetic field, thereby increasing the Sn...2+ The radiative transition probability of Ag can enhance luminescence; however, when the Ag doping concentration is too high, excessive Ag may cause Ag particles to agglomerate or form non-radiative energy transfer channels, which may lead to concentration quenching effect and decrease luminescence intensity.

[0052] Comparative Example 6 The 0% Ag-doped glass powder prepared in Comparative Example 1 was mixed with yellow phosphor YAG:Ce 3+ According to a mass ratio of 1:1 (i.e., the mass percentage concentration of 0% Ag-doped glass powder is 50wt%, the yellow phosphor YAG:Ce is used...), 3+ Mix the powders (with a mass percentage concentration of 50wt%), weigh 0.2g of the resulting mixed powder, and add 0.08g of terpineol-ethyl cellulose organic gum. Grind and disperse the mixture thoroughly to form a composite slurry with moderate viscosity and uniform dispersion. A composite slurry was uniformly coated onto the surface of a sapphire substrate to a thickness of 110 μm. The substrate was then placed in an oven and dried at 120°C for 12 hours to remove organic solvents and form a green film. Subsequently, it was transferred to an annealing furnace and sintered at 420°C for 20 minutes. Finally, it was allowed to cool naturally to room temperature in the furnace to obtain a tin fluorophosphate glass fluorescent film. The luminous flux was then measured under 450 nm commercial laser pumping, and the results are as follows: Figure 2 As shown.

[0053] Comparative Example 7 Similar to Comparative Example 6, the difference lies in the fact that 0% Ag-doped glass powder and yellow phosphor YAG:Ce 3+ The mass ratio is 1:1.5 (i.e., the mass percentage concentration of 0% Ag-doped glass powder is 40 wt%, and the yellow phosphor YAG:Ce is 1:1.5). 3+ The mass percentage concentration is 60 wt%.

[0054] Comparative Example 8 Similar to Comparative Example 6, the difference lies in the fact that 0% Ag-doped glass powder and yellow phosphor YAG:Ce 3+ The mass ratio is 1:2.3 (i.e., the mass percentage concentration of 0% Ag-doped glass powder is 30 wt%, and the yellow phosphor YAG:Ce is 30 wt%). 3+ The mass percentage concentration is 70 wt%.

[0055] Comparative Example 9 Similar to Comparative Example 6, the difference lies in the fact that 0% Ag-doped glass powder and yellow phosphor YAG:Ce 3+ The mass ratio is 1:4 (i.e., the mass percentage concentration of 0% Ag-doped glass powder is 20 wt%, and the yellow phosphor YAG:Ce is 4 wt%). 3+ The mass percentage concentration is 80 wt%.

[0056] Comparative Example 10 Similar to Comparative Example 6, the difference lies in the fact that 0% Ag-doped glass powder and yellow phosphor YAG:Ce 3+ The mass ratio is 1:9 (i.e., the mass percentage concentration of 0% Ag-doped glass powder is 10 wt%, and the yellow phosphor YAG:Ce is 9 wt%). 3+ The mass percentage concentration is 90 wt%.

[0057] Figure 2 The luminous flux of the tin fluorophosphate glass fluorescent films prepared for Comparative Examples 6-10 is shown as a function of excitation power. The test results indicate that before thermal quenching, the luminous flux of all samples monotonically increases with increasing excitation power. However, at the same power, the luminous flux of the yellow phosphor YAG:Ce... 3+ Concentration has a significant impact on output luminous flux. With the yellow phosphor YAG:Ce 3+ As the concentration was increased sequentially from 50% to 60%, 70%, and 80%, the luminous flux of the sample increased progressively; however, when the concentration was further increased to 90%, the luminous flux decreased. The reason for this is that when the yellow phosphor YAG:Ce... 3+ When the concentration is below 80%, the light-emitting center density increases with increasing phosphor content, and the light conversion efficiency continues to improve; however, when the concentration exceeds 80%, excessively high levels of the yellow phosphor YAG:Ce... 3+ The excessively small spacing between adjacent phosphor particles due to the load enhances resonant energy transfer, making it easier for excitation energy to dissipate through non-radiative channels, resulting in concentration quenching and a decrease in luminous efficiency. In particular, Comparative Example 9 exhibited the highest luminous flux output at all excitation powers, achieving approximately 1100 lm at an excitation power of 6W, demonstrating the best overall performance.

[0058] Example 1 A method for preparing a silver ion-doped tin fluorophosphate glass fluorescent thin film includes the following steps: (1) Preparation of glass powder: Weigh out SnO:10%, SnF2:5%, ZnF2:45%, P2O5:40% raw materials as tin fluorophosphate matrix glass, and dop 0.2% AgNO3 in the tin fluorophosphate matrix glass. Grind the mixture evenly in an agate mortar to form a mixture, place it in a crucible, cover the crucible and preheat it in a muffle furnace at 400℃ for 20min. Transfer the preheated platinum crucible to a silicon carbide rod electric furnace at 1000℃ and melt it for 40min. After homogenization and clarification, a uniform glass melt without bubbles is obtained. Pour the glass melt into a mold that has been preheated to 350℃, and then put it into a muffle furnace that has been heated to 300℃. After holding it at 2.5h, turn off the muffle furnace and cool it to room temperature to obtain a glass block. Then grind it into powder and pass it through a 200-mesh sieve to obtain a uniform glass powder (denoted as 0.2% Ag doped glass powder). (2) Preparation of composite slurry: 0.2% Ag-doped glass powder and yellow phosphor YAG:Ce were mixed. 3+ Mix according to a mass ratio of 1:4, weigh 0.2g of the resulting mixed powder, add 0.08g of terpineol-ethyl cellulose organic gum, and grind and disperse thoroughly to form a composite slurry with moderate viscosity and uniform dispersion; (3) Preparation of silver ion-doped tin fluorophosphate glass fluorescent film: 0.15g of composite paste was uniformly coated (coating thickness was 110μm) on the surface of sapphire substrate and then placed in an oven at 120℃ for 12h to remove organic solvent and form a green film. Then it was transferred to an annealing furnace and sintered at 420℃ for 20min to achieve full removal of organic adhesive and densification of glass powder while maintaining the luminescence performance of phosphor. Finally, it was naturally cooled to room temperature with the furnace to obtain silver ion-doped tin fluorophosphate glass fluorescent film on sapphire substrate.

[0059] Figure 3 The figures show the luminous flux of the films prepared in Comparative Example 9 and Example 1 as a function of excitation power. The test results show that as the blue laser power increases from 1W to 6W, the luminous flux of both samples exhibits a monotonically increasing trend. However, the luminous flux of Example 1 is consistently higher than that of Comparative Example 9 at all powers, and the difference widens with increasing power: at 1W, the difference is 20 lm; when the power increases to 6W, Comparative Example 9 reaches 1100 lm before thermal quenching, while Example 1 continues its upward trend, achieving 1142 lm at 6W, and its saturation excitation power can be extended to 7W. This significant improvement is attributed to the localized surface plasmon resonance effect of Ag nanoparticles, i.e., the enhanced local electromagnetic field generated by Ag nanoparticles effectively improves the luminous flux of YAG:Ce. 3+ The high radiative transition probability and excellent thermal conductivity properties improve light conversion efficiency and thermal stability, enabling Example 1 to exhibit better luminescence performance under high-power excitation.

[0060] Figure 4 The graphs show the color rendering index (Ra) of the films prepared in Comparative Example 9 and Example 1 as a function of excitation power. The test results show that the Ra value of Example 1 is higher than that of Comparative Example 9 at all excitation powers: at 1W excitation, the Ra of Comparative Example 9 is 71, while that of Example 1 increases to 75; when the excitation power increases to 6W, the Ra of Comparative Example 9 decreases to 67, while that of Example 1 remains at a relatively high level of 72. This advantage is attributed to Ag's ultra-high thermal conductivity, which integrates into the tin fluorophosphate glass structure to construct an efficient thermally conductive network, resulting in a more balanced spectral distribution, suppressing thermal quenching at high power, maintaining the stability of the emission spectrum, and thus effectively delaying the decay of the color rendering index. This indicates that the introduction of Ag not only improves the luminescence efficiency but also significantly improves the color rendering performance and high-power stability of the fluorescent glass film.

[0061] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A silver ion-doped tin fluorophosphate glass fluorescent thin film, characterized in that, It includes glass powder and yellow phosphor YAG:Ce; the glass powder is composed of tin fluorophosphate matrix glass externally doped with Ag. + Prepared from [material name].

2. The silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 1, characterized in that, The glass powder and the yellow fluorescent powder YAG:Ce 3+ The mass ratio is 1:

4.

3. The silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 1, characterized in that, Mole percentage meter, the Ag + The external doping amount is 0.2%.

4. The silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 1, characterized in that, According to molar percentage, the raw material composition of the tin fluorophosphate matrix glass includes: SnO: 10%, SnF2: 5%, ZnF2: 45%, P2O5: 40%.

5. A method for preparing a silver ion-doped tin fluorophosphate glass fluorescent thin film as described in any one of claims 1-4, characterized in that, Includes the following steps: (1) Weigh out SnO, SnF2, ZnF2, P2O5 and Ag according to mole percentage. + The raw materials are mixed evenly and placed in a crucible. After preheating, melting, homogenizing and clarifying, a glass melt is obtained. The glass melt is poured into a mold and annealed to obtain a glass block. The glass block is then ground and sieved to obtain glass powder. (2) The glass powder is mixed with yellow phosphor YAG:Ce 3+ Mix, add organic adhesive, and grind and disperse to obtain a composite slurry; (3) The composite slurry is coated on the surface of the substrate, and then dried and sintered to obtain the silver ion-doped tin fluorophosphate glass fluorescent film.

6. The method for preparing silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 5, characterized in that, The preheating temperature is 400℃ and the preheating time is 20 minutes; The melting temperature is 1000℃ and the melting time is 40 minutes; The specific preparation steps of the glass block are as follows: pour the molten glass into a mold that has been preheated to 350°C, then place it in a muffle furnace that has been heated to 300°C, keep it at that temperature for 2-3 hours, then turn off the muffle furnace and cool it to room temperature to obtain the glass block.

7. The method for preparing silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 5, characterized in that, The organic adhesive is terpineol-ethyl cellulose organic adhesive.

8. The method for preparing silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 5, characterized in that, The substrate is a sapphire substrate.

9. The method for preparing silver ion-doped tin fluorophosphate glass fluorescent thin film according to claim 5, characterized in that, The drying temperature is 120℃, and the drying time is 12 hours; The sintering temperature was 420℃ and the sintering time was 20 minutes.

10. The application of a silver ion-doped tin fluorophosphate glass fluorescent thin film as described in any one of claims 1-4 in the fabrication of laser lighting devices, optical coatings, or light-emitting devices.

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