Manufacturing process of a fluorescent adhesive cake

Abstract

The present invention discloses a manufacturing process of a fluorescent glue cake, belonging to the technical field of fluorescent composite materials. The chemical structure of the fluorescent glue cake is shown in Formula (I): A l (B m , C n ): D o (I); in Formula (I), A is one of Na, Mg, and K, B is Si, Ce, C is F, and D is Mn 4+ , 1

Description

Technical Field

[0001] The present invention belongs to the technical field of fluorescent composite materials, and specifically relates to a manufacturing process of a fluorescent glue cake. Background Art

[0002] With the continuous development of lighting and display technologies, white light-emitting diodes (WLEDs) have become the most promising new generation of lighting sources. In WLEDs, phosphor materials play a crucial role, and their performance directly affects the optical performance and service life of WLEDs. Among them, Mn 4+ -doped fluoride red phosphors (general formula: A2MF6:Mn 4+ ) have become an indispensable red light-emitting component in WLEDs due to their unique luminescence characteristics.

[0003] Mn 4+ -doped fluoride red phosphors are narrow-band emission phosphors that can emit strong red light in the wavelength range of 610 - 650 nm, which is the most sensitive wavelength range of the human eye. Compared with other red phosphors, Mn 4+ -doped fluoride red phosphors have the following advantages:

[0004] High luminous efficiency: Mn 4+ -doped fluoride red phosphors have a high luminous efficiency in the red light band, which can effectively improve the luminous efficiency of WLEDs.

[0005] Wide color gamut: Due to their narrow-band emission characteristics, Mn 4+ -doped fluoride red phosphors can broaden the color gamut of WLEDs, making their color rendering index higher and their color rendering performance more excellent.

[0006] Excellent thermal stability: Compared with other red phosphors, Mn 4+ -doped fluoride red phosphors have better thermal stability and less attenuation of luminous intensity at high temperatures.

[0007] Mn 4+ -doped fluoride red phosphors can be compounded with other phosphors and applied in different fields. In the lighting field, they can be compounded with yellow-green GaYAG or yellow YAG phosphors to prepare white LED lamps with a high color rendering index. In the display field, they can be compounded with cerium phosphors and applied to LED backlights to improve the color gamut of liquid crystal displays.

[0008] In lighting applications, Mn 4+ -doped fluoride red phosphors are mainly used on filaments and patches. To improve their stability and brightness, it is usually necessary to increase the particle size of the phosphors. However, in backlight applications, due to the limitation of chip size, it is necessary to use Mn 4+ -doped fluoride red phosphors with a smaller particle size.

[0009] Although Mn 4+ Doped fluoride red phosphor has the above advantages, but there are still some problems to be solved in practical applications, mainly including:

[0010] Low moisture resistance: Mn 4+ Surface Mn of fluoride-doped red phosphor 4+ The ions are very easy to combine with water molecules and be oxidized, resulting in a significant decrease in the luminous intensity of the phosphor. This low moisture resistance seriously restricts its application in high humidity environments.

[0011] The contradiction between particle size and application field: In lighting applications, Mn with larger particle size is required. 4+ Fluoride red phosphors are doped to improve their stability and brightness; however, in backlight applications, due to chip size limitations, phosphors with smaller particle sizes need to be used. This contradiction between particle size and application areas poses a challenge to the preparation and application of materials.

[0012] Agglomeration of phosphors: During the preparation process, Mn 4+ Fluoride-doped red phosphors tend to agglomerate and form large particles, which not only affects the dispersibility of the phosphors but also leads to uneven luminescence.

[0013] The color purity of phosphor is not ideal: At present, Mn 4+ The color purity of fluoride-doped red phosphors needs to be further improved. Improving color purity can make WLEDs have a higher color rendering index and better color rendering performance.

[0014] In summary, Mn 4+ Although doped fluoride red phosphors have excellent luminescence properties, they still have problems such as poor moisture resistance, inconsistency between particle size and application field, serious agglomeration, and unsatisfactory color purity in practical applications. These problems seriously restrict the development of Mn 4+ The promotion and application of fluoride-doped red phosphors urgently requires researchers to propose new solutions.

[0015] In recent years, researchers have proposed some improvement measures to address the above problems. For example, improving the moisture resistance of phosphors by surface coating modification; optimizing the production process and regulating the particle size of phosphors; using core-shell structures to improve the luminescence properties of phosphors. Although these measures have improved the Mn 4+ The performance of fluoride-doped red phosphors is good, but it is still far from practical application. Therefore, the development of new Mn 4+ The preparation technology of fluoride-doped red phosphor and further improving its comprehensive performance are still urgent issues to be solved. Summary of the invention

[0016] 1. Problems to be Solved

[0017] In view of the above deficiencies in the prior art, the object of the present invention is to provide a manufacturing process for fluorescent glue cakes. By using a wet chemical method to synthesize a precursor and then performing coating and heat treatment, fluorescent glue cakes with excellent luminescent properties and stable colors can be obtained. The manufacturing process of this method is relatively simple, the raw materials are easily available, and the cost is relatively low. By optimizing the reaction conditions of each step, large-scale preparation of fluorescent glue cakes can be achieved. Coating a dense Al2O3 film on the surface of the phosphor can significantly improve its moisture resistance. This coating layer can effectively block water molecules and prevent the hydrolysis of Mn 4+ ions, thereby maintaining the stable luminescent properties of the phosphor. Vitrification treatment of the coated phosphor can further improve the moisture resistance while also regulating the particle size distribution of the phosphor to obtain spherical particles with uniform particle size and good dispersibility, which is beneficial for applications in devices such as LEDs. The fluorescent glue cakes prepared by the present invention have high luminous efficiency, good color purity, and an emission peak located at 600 - 630 nm, and are ideal red phosphors. Compared with other red phosphors, the quantum efficiency of this material can reach more than 85% under blue light excitation, which can significantly improve the color rendering index and luminous efficacy of white LEDs. The fluorescent glue cakes of the present invention can be widely applied in fields such as LED lighting and backlight display, and have good application prospects. The white LED light source prepared with this phosphor has obvious advantages in high color rendering, high luminous efficacy, long life, etc., and can replace traditional fluorescent lamps and incandescent lamps, with broad market space. In summary, the fluorescent glue cakes provided by the present invention have obvious technical advantages and application values in solving the problem of unstable performance of existing Mn 4+ -doped fluoride fluorescent glue cakes. This invention enriches the varieties of red phosphors for LEDs and has a positive significance for promoting the development of semiconductor lighting and display technologies.

[0018] 2. Technical Solutions

[0019] To solve the above problems, the technical solution provided by the present invention is as follows:

[0020] A fluorescent glue cake, the chemical structure of the fluorescent glue cake is shown in formula (I):

[0021] A l (B m , C n ):D o (I);

[0022] In formula (I), A is one of Na, Mg, K, B is Si, Ce, C is F, D is Mn 4+ , 1 < l < 3, 1 < m < 3, 4 < n < 8, 0.01 < o < 0.1.

[0023] Preferably, for the fluorescent glue cake, the chemical structure of the fluorescent glue cake is shown in Formula (II):

[0024] K2(Si,F6):Mn 4+ 0.06 (II).

[0025] The manufacturing process of the fluorescent glue cake includes the following steps:

[0026] (a) Pre-cool 35wt%-45wt% concentration of hydrofluoric acid at low temperature, then add potassium permanganate and stir for the first time. Then add potassium fluoride and stir for the second time. Then add hydrogen peroxide and drip hydrogen peroxide until the whole solution shows a brown color after titration is completed. Stop titration. Then, after the precipitate completely settles to the bottom, remove the upper layer solution and add anhydrous ethanol for washing until neutral. After washing, dry it to obtain the first product;

[0027] (b) Dissolve metasilicic acid in 35wt%-45wt% concentration of hydrofluoric acid and 10wt%-20wt% oxalic acid, and stir for the third time to obtain the second product;

[0028] (c) Dissolve potassium hydrogen fluoride in 35wt%-45wt% concentration of hydrofluoric acid and stir for the fourth time to obtain the third product;

[0029] (d) Mix hydrofluoric acid with the first product and stir for the fifth time. Then, at 5-8 s after the start of the fifth stirring, add the second product and the third product and stir for the sixth time. After stirring stops, let it stand for 2 min-10 min. After the precipitate sinks to the bottom, pour off the upper clear liquid. Wash the precipitate with anhydrous ethanol until neutral, and dry the washed product;

[0030] (e) Perform atomic layer deposition treatment on the product dried in step (d) to obtain a coated product. Then mix the coated product with glass powder, perform high-temperature treatment, and let it cool naturally.

[0031] Preferably, in step (a) of the manufacturing process of the fluorescent glue cake, the low-temperature pre-cooling temperature is 0°C-4°C;

[0032] In step (a), the low-temperature pre-cooling method is ice bath;

[0033] In step (a), the added mass of potassium permanganate is 10-15 times that of hydrofluoric acid;

[0034] In step (a), the first stirring time is 5 min-20 min, and the first stirring speed is 300 rpm-500 rpm;

[0035] In step (a), the added mass of potassium fluoride is 150-250 times that of hydrofluoric acid;

[0036] In step (a), the time of the second stirring is 20 min - 40 min, and the rotation speed of the second stirring is 200 rpm - 400 rpm;

[0037] In step (a), the mass concentration of hydrogen peroxide is 30%, the added mass of hydrogen peroxide is 10 - 20 times that of hydrofluoric acid, the dropping rate of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropping with a separating funnel;

[0038] In step (a), the drying temperature is 60°C - 80°C.

[0039] Preferably, in step (b) of the manufacturing process of the fluorescent glue cake, the mass ratio among metasilicic acid, hydrofluoric acid and oxalic acid is (15 - 25):(100 - 120):(80 - 90);

[0040] In step (b), the time of the third stirring is 30 min - 40 min, and the rotation speed of the second stirring is 250 rpm - 400 rpm;

[0041] In step (c), the mass ratio between potassium hydrogen fluoride and hydrofluoric acid is (45 - 65):(160 - 200);

[0042] In step (d), the time of the fourth stirring is 25 min - 50 min, and the rotation speed of the second stirring is 250 rpm - 300 rpm.

[0043] Preferably, in step (d) of the manufacturing process of the fluorescent glue cake, the mass ratio between hydrofluoric acid and the first product is (400 - 600):(5 - 15);

[0044] In step (d), the time of the fifth stirring is 30 min - 50 min, and the rotation speed of the second stirring is 400 rpm - 600 rpm;

[0045] In step (d), the mass ratio among hydrofluoric acid, the second product and the third product is (1 - 3):(2 - 5):(3 - 5);

[0046] In step (d), the time of the sixth stirring is 10 min - 30 min, and the rotation speed of the second stirring is 400 rpm - 600 rpm;

[0047] In step (d), the drying temperature is 70°C - 90°C.

[0048] Preferably, in step (e) of the manufacturing process of the fluorescent glue cake, the method of atomic layer deposition treatment is as follows:

[0049] Place the dried product in the reaction chamber of atomic layer deposition. Evacuate to 10 Pa under a nitrogen atmosphere, heat the reaction chamber to a reaction temperature of 50°C - 90°C, introduce trimethylaluminum vapor as the aluminum source precursor, with the introduction time being 0.1 s - 10 s. Stop the introduction, purge the reaction chamber with nitrogen, with the purging time being 1 s - 60 s. Then introduce ozone gas into the reaction chamber, with the introduction time being 0.1 s - 10 s. Purge the reaction chamber with nitrogen again until a 1-nm film layer is deposited. Cool down to room temperature under a nitrogen atmosphere to obtain the film-coated product;

[0050] The manufacturing process of the glass powder in step (e) is as follows:

[0051] Mix B2O3, SiO2, ZnO, and Na2O in a mass ratio of 10:60:20:10, calcine at 1000°C - 1200°C for 2 h - 4 h, cool down to room temperature, ball mill and pass through a 200-mesh sieve to obtain it;

[0052] The mass ratio between the film-coated product and the glass powder in step (e) is 1:(6 - 10);

[0053] The temperature of the high-temperature treatment in step (e) is 700°C - 800°C, and the time of the high-temperature treatment is 10 min - 30 min.

[0054] 3. Beneficial effects

[0055] In the application of phosphors, particle size is a key parameter, which directly affects the optical properties and application effects of phosphors. In the fields of lighting and display, different application scenarios have different requirements for the particle size of phosphors. For example, in the lighting field, a larger particle size helps to improve the stability and brightness of phosphors, while in backlight applications, due to the limitation of chip size, phosphors with a smaller particle size are required. The technology of this application can precisely control the particle size of fluoride phosphors by optimizing the manufacturing process to meet the needs of different markets. Specifically, by adjusting the amount of HF in the KHF2 solution and the stirring speed, products with different particle sizes can be prepared. For example, increasing the amount of HF can obtain products with a large particle size, while increasing the stirring speed can obtain products with a small particle size. This flexible particle size control ability enables our products to be widely applied to various lighting and display scenarios. Mn 4+ The doped fluoride red phosphor has low moisture resistance because the Mn 4+ ions on its surface are easily oxidized after combining with water, resulting in a decrease in luminescence intensity. Therefore, its low moisture resistance has always been an important factor restricting its application. By coating a dense high-temperature resistant inorganic film on the surface of the phosphor, water molecules can be effectively prevented from combining with Mn 4+The contact of ions can thus significantly improve the moisture resistance of the powder. The thickness of this inorganic film is controllable, and the coating thickness can be adjusted by setting the number of cycles, thereby indirectly controlling the particle size of the powder. In addition, this surface coating treatment not only improves the moisture resistance but also significantly enhances the thermal stability and chemical stability of the powder. In traditional inorganic coating treatments, vitrification is a commonly used method, but it needs to be carried out under high-temperature conditions, which may have an adverse impact on the powder. The technology of this application can reduce the impact of high temperature on the powder by performing vitrification after coating a layer of high-temperature-resistant inorganic film on the surface. This optimized vitrification process makes the coating layer more uniform and dense, providing better protection for the surface. Specifically, the vitrification treatment uses a mixture of B2O3 - SiO2 - ZnO - Na2O and is calcined at high temperature to form a uniform glass layer. This treatment not only improves the moisture resistance and thermal stability of the powder but also enhances its mechanical strength, making the phosphor more durable in practical applications. The production process of this application is simple and efficient, suitable for large-scale industrial production. By optimizing each production step, we can improve production efficiency and reduce production costs while ensuring product quality. This efficient production process makes our products more competitive in the market. In summary, the technology of this application has significant advantages over the commonly used technologies in the current market in terms of particle size control, moisture resistance improvement, vitrification treatment, and production efficiency. These advantages enable our products to better meet market demands and stand out in the fierce market competition. Description of the Drawings

[0056] Figure 1 is the scanning electron microscope image of the fluorescent glue cake in Example 5 of the present invention;

[0057] Figure 2 is the particle size diagram of the fluorescent glue cake in Example 5 of the present invention. Detailed Embodiments

[0058] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0059] It should be noted that in the present invention, the parts by weight involved are all in the international standard unit of kilograms (Kg).

[0060] Example 1

[0061] A fluorescent glue cake, the chemical structure of the fluorescent glue cake is shown in Formula (III): A2(B2, C5):D 0.02(III);

[0062] In formula (III), A is Na, B is Ce, C is F, and D is Mn 4+ .

[0063] The manufacturing process of the fluorescent glue cake includes the following steps: (a) Pre-cool 35 wt% hydrofluoric acid at low temperature, then add potassium permanganate and stir for the first time. Then add potassium fluoride and stir for the second time. Then add hydrogen peroxide and dropwise add hydrogen peroxide until the whole solution shows a brown color after titration is completed. Stop titration. Then, after the precipitate completely settles to the bottom, remove the upper layer solution and add anhydrous ethanol for washing until it is neutral. After washing, dry it to obtain the first product;

[0064] It should be noted that the low-temperature pre-cooling temperature in step (a) is 0 °C;

[0065] The low-temperature pre-cooling method in step (a) is ice bath;

[0066] The added mass of potassium permanganate in step (a) is 10 times that of hydrofluoric acid;

[0067] The stirring time for the first time in step (a) is 5 min, and the stirring speed for the first time is 500 rpm;

[0068] The added mass of potassium fluoride in step (a) is 150 times that of hydrofluoric acid;

[0069] The stirring time for the second time in step (a) is 20 min, and the stirring speed for the second time is 400 rpm;

[0070] The mass concentration of hydrogen peroxide in step (a) is 30%, the added mass of hydrogen peroxide is 10 times that of hydrofluoric acid, the dropping speed of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropwise addition with a separating funnel;

[0071] The drying temperature in step (a) is 60 °C.

[0072] (b) Dissolve metasilicic acid in 35 wt% hydrofluoric acid and 20 wt% oxalic acid, and stir for the third time to obtain the second product;

[0073] It should be noted that the mass ratio of metasilicic acid, hydrofluoric acid, and oxalic acid in step (b) is 15:120:80;

[0074] The stirring time for the third time in step (b) is 30 min, and the stirring speed for the second time is 400 rpm.

[0075] (c) Dissolve potassium hydrogen fluoride in 35 wt% hydrofluoric acid and stir for the fourth time to obtain the third product;

[0076] It should be noted that the mass ratio between potassium bifluoride and hydrofluoric acid in step (c) is 45:200.

[0077] (d) Mix hydrofluoric acid with the first product, stir for the fifth time, then add the second product and the third product 5 s after the start of the fifth stirring, stir for the sixth time, let it stand for 10 min after the stirring stops, pour off the supernatant after the precipitate sinks to the bottom, wash the precipitate with absolute ethanol until neutral, and dry the washed product;

[0078] It should be noted that the time for the fourth stirring in step (d) is 25 min, and the rotation speed for the second stirring is 300 rpm.

[0079] It should be noted that the mass ratio between hydrofluoric acid and the first product in step (d) is 400:15;

[0080] In step (d), the time for the fifth stirring is 30 min, and the rotation speed for the second stirring is 600 rpm;

[0081] In step (d), the mass ratio between hydrofluoric acid and the second product and the third product is 1:5:3;

[0082] In step (d), the time for the sixth stirring is 10 min, and the rotation speed for the second stirring is 600 rpm;

[0083] In step (d), the drying temperature is 70 °C.

[0084] (e) Subject the product dried in step (d) to atomic layer deposition treatment to obtain a film-coated product, then mix the film-coated product with glass powder, perform high-temperature treatment, and let it cool naturally;

[0085] The method for atomic layer deposition treatment in step (e) is as follows: Place the dried product in the reaction chamber of atomic layer deposition, evacuate to 10 Pa under a nitrogen atmosphere, heat the reaction chamber to a reaction temperature of 50 °C, introduce trimethylaluminum vapor as the aluminum source precursor, with an introduction time of 10 s, stop the introduction, purge the reaction chamber with nitrogen, with a purge time of 1 s, then introduce ozone gas into the reaction chamber, with an introduction time of 10 s, and purge the reaction chamber with nitrogen again until a 1-nm film layer is deposited, and cool to room temperature under a nitrogen atmosphere to obtain the film-coated product;

[0086] The manufacturing process of the glass powder in step (e) is as follows: Mix B2O3, SiO2, ZnO, and Na2O in a mass ratio of 10:60:20:10, calcine at 1000 °C for 4 h, cool to room temperature, ball mill and pass through a 200-mesh sieve to obtain it;

[0087] In step (e), the mass ratio between the film-coated product and the glass powder is 1:6;

[0088] In step (e), the temperature of the high-temperature treatment is 700 °C, and the time of the high-temperature treatment is 30 min.

[0089] Example 2

[0090] A fluorescent glue cake, and the chemical structure of the fluorescent glue cake is shown in formula (V): A2(B2, C5):D 0.09 (V);

[0091] In formula (V), A is Mg, B is Si, C is F, and D is Mn 4+ .

[0092] The manufacturing process of the fluorescent glue cake includes the following steps: (a) Pre-cool 45 wt% hydrofluoric acid at low temperature, then add potassium permanganate and stir for the first time, then add potassium fluoride and stir for the second time, then add hydrogen peroxide and dropwise add hydrogen peroxide until the whole solution shows a brown color after titration is completed, stop titration, then wait for the precipitate to completely settle to the bottom, remove the upper layer solution, and add anhydrous ethanol for washing until neutral, and dry after washing to obtain the first product;

[0093] It should be noted that the temperature of the low-temperature pre-cooling in step (a) is 4 °C;

[0094] The method of low-temperature pre-cooling in step (a) is ice bath;

[0095] The added mass of potassium permanganate in step (a) is 15 times that of hydrofluoric acid;

[0096] The time of the first stirring in step (a) is 20 min, and the rotation speed of the first stirring is 300 rpm;

[0097] The added mass of potassium fluoride in step (a) is 250 times that of hydrofluoric acid;

[0098] The time of the second stirring in step (a) is 40 min, and the rotation speed of the second stirring is 200 rpm;

[0099] The mass concentration of hydrogen peroxide in step (a) is 30%, the added mass of hydrogen peroxide is 20 times that of hydrofluoric acid, the dropping speed of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropwise addition with a separating funnel;

[0100] The drying temperature in step (a) is 80 °C.

[0101] (b) Dissolve metasilicic acid in 45 wt% hydrofluoric acid and 10 wt% oxalic acid, and stir for the third time to obtain the second product;

[0102] It should be noted that the mass ratio of metasilicic acid, hydrofluoric acid and oxalic acid in step (b) is 25:100:90;

[0103] In step (b), the time of the third stirring is 40 min, and the rotation speed of the second stirring is 250 rpm.

[0104] (c) Dissolve potassium bifluoride in hydrofluoric acid with a concentration of 45 wt%, and perform the fourth stirring to obtain the third product;

[0105] It should be noted that the mass ratio between potassium bifluoride and hydrofluoric acid in step (c) is 65:160.

[0106] (d) Mix hydrofluoric acid with the first product, perform the fifth stirring, then add the second product and the third product 8 s after the start of the fifth stirring, perform the sixth stirring, let it stand for 2 min after the stirring stops, pour off the supernatant after the precipitate sinks to the bottom, wash the precipitate with absolute ethanol until neutral, and dry the washed product;

[0107] It should be noted that the time of the fourth stirring in step (d) is 50 min, and the rotation speed of the second stirring is 250 rpm.

[0108] It should be noted that the mass ratio between hydrofluoric acid and the first product in step (d) is 600:5;

[0109] In step (d), the time of the fifth stirring is 50 min, and the rotation speed of the second stirring is 400 rpm;

[0110] In step (d), the mass ratio between hydrofluoric acid and the second product and the third product is 3:2:5;

[0111] In step (d), the time of the sixth stirring is 30 min, and the rotation speed of the second stirring is 400 rpm;

[0112] In step (d), the drying temperature is 90 °C.

[0113] (e) Perform atomic layer deposition on the product dried in step (d) to obtain a film-coated product, then mix the film-coated product with glass powder, perform high-temperature treatment, and then cool it naturally;

[0114] The method of atomic layer deposition in step (e) is as follows: Place the dried product in the reaction chamber of atomic layer deposition, evacuate to 10 Pa under a nitrogen atmosphere, heat the reaction chamber to a reaction temperature of 90 °C, introduce trimethylaluminum vapor as the aluminum source precursor, the introduction time is 0.1 s, stop the introduction, purge the reaction chamber with nitrogen, the purge time is 60 s, then introduce ozone gas into the reaction chamber, the introduction time is 0.1 s, and purge the reaction chamber with nitrogen again until a 1-nm film layer is deposited, and cool it to room temperature under a nitrogen atmosphere to obtain the film-coated product;

[0115] The manufacturing process of the glass powder in step (e) is as follows: Mix B2O3, SiO2, ZnO and Na2O according to the mass ratio of 10:60:20:10, calcine at 1200 °C for 2 h, cool down to room temperature, ball mill and pass through a 200-mesh sieve to obtain it.

[0116] The mass ratio between the coated product and the glass powder in step (e) is 1:10.

[0117] In step (e), the temperature of the high-temperature treatment is 800 °C and the time of the high-temperature treatment is 10 min.

[0118] Example 3

[0119] A fluorescent glue cake, the chemical structure of the fluorescent glue cake is shown in formula (VI): A2(B2, C7):D 0.03 (VI);

[0120] In formula (VI), A is K, B is Ce, C is F, and D is Mn 4+ .

[0121] The manufacturing process of the fluorescent glue cake includes the following steps: (a) Pre-cool 35 wt% hydrofluoric acid at low temperature, then add potassium permanganate and stir for the first time, then add potassium fluoride and stir for the second time, then add hydrogen peroxide, and dropwise add hydrogen peroxide until the whole solution shows a brown color after titration is completed, stop titration, then wait for the precipitate to completely settle to the bottom, remove the upper layer solution, and add anhydrous ethanol for washing until it is neutral, and dry after washing to obtain the first product.

[0122] It should be noted that the low-temperature pre-cooling temperature in step (a) is 0 °C;

[0123] The low-temperature pre-cooling method in step (a) is ice bath;

[0124] The added mass of potassium permanganate in step (a) is 10 times that of hydrofluoric acid;

[0125] The stirring time for the first time in step (a) is 5 min and the stirring speed for the first time is 300 rpm;

[0126] The added mass of potassium fluoride in step (a) is 150 times that of hydrofluoric acid;

[0127] The stirring time for the second time in step (a) is 20 min and the stirring speed for the second time is 200 rpm;

[0128] In step (a), the mass concentration of hydrogen peroxide is 30%, the added mass of hydrogen peroxide is 10 times that of hydrofluoric acid, the dropping speed of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropping with a separating funnel;

[0129] The drying temperature in step (a) is 60 °C.

[0130] (b) Dissolve metasilicic acid in hydrofluoric acid with a concentration of 35 wt% and oxalic acid with a concentration of 10 wt%, and stir for the third time to obtain a second product;

[0131] It should be noted that the mass ratio of metasilicic acid, hydrofluoric acid and oxalic acid in step (b) is 15:100:80;

[0132] The time for the third stirring in step (b) is 30 min, and the rotation speed of the second stirring is 250 rpm.

[0133] (c) Dissolve potassium hydrogen fluoride in hydrofluoric acid with a concentration of 35 wt% - 45 wt%, and stir for the fourth time to obtain a third product;

[0134] It should be noted that the mass ratio of potassium hydrogen fluoride to hydrofluoric acid in step (c) is 45:160.

[0135] (d) Mix hydrofluoric acid with the first product, stir for the fifth time, then add the second product and the third product 5 s after the start of the fifth stirring, stir for the sixth time, let it stand for 2 min after the stirring stops, pour off the supernatant after the precipitate sinks to the bottom, wash the precipitate with absolute ethanol until neutral, and dry the washed product;

[0136] It should be noted that the time for the fourth stirring in step (d) is 25 min, and the rotation speed of the second stirring is 250 rpm.

[0137] It should be noted that the mass ratio of hydrofluoric acid to the first product in step (d) is 400:5;

[0138] The time for the fifth stirring in step (d) is 30 min, and the rotation speed of the second stirring is 400 rpm;

[0139] The mass ratio of hydrofluoric acid to the second product and the third product in step (d) is 1:2:3;

[0140] The time for the sixth stirring in step (d) is 10 min, and the rotation speed of the second stirring is 400 rpm;

[0141] The drying temperature in step (d) is 70 °C.

[0142] (e) Subject the product dried in step (d) to atomic layer deposition treatment to obtain a film-coated product, then mix the film-coated product with glass powder, perform high-temperature treatment, and then cool it naturally;

[0143] The method of atomic layer deposition treatment in step (e) is as follows: Place the dried product in the reaction chamber of atomic layer deposition, evacuate to 10 Pa under a nitrogen atmosphere, heat the reaction chamber to a reaction temperature of 50 °C, introduce trimethylaluminum vapor as the aluminum source precursor, with an introduction time of 0.1 s, stop the introduction, purge the reaction chamber with nitrogen, with a purge time of 1 s, then introduce ozone gas into the reaction chamber, with an introduction time of 0.1 s, and purge the reaction chamber with nitrogen again until a 1 nm film layer is deposited. Cool down to room temperature under a nitrogen atmosphere to obtain the film-coated product;

[0144] The manufacturing process of the glass powder in step (e) is as follows: Mix B2O3, SiO2, ZnO, and Na2O according to a mass ratio of 10:60:20:10, calcine at 1000 °C for 2 h, cool down to room temperature, ball mill and pass through a 200-mesh sieve to obtain it;

[0145] The mass ratio between the film-coated product and the glass powder in step (e) is 1:6;

[0146] The temperature of the high-temperature treatment in step (e) is 700 °C, and the time of the high-temperature treatment is 10 min.

[0147] Example 4

[0148] A fluorescent adhesive cake, and the chemical structure of the fluorescent adhesive cake is shown in formula (VII): A2(B2, C6):D 0.07 (VII);

[0149] In formula (VII), A is K, B is Si, C is F, and D is Mn 4+ .

[0150] The manufacturing process of the fluorescent adhesive cake includes the following steps: (a) Pre-cool 45 wt% hydrofluoric acid at low temperature, then add potassium permanganate, stir for the first time, then add potassium fluoride, stir for the second time, then add hydrogen peroxide, dropwise add hydrogen peroxide until the whole solution shows a brown color after titration is completed, stop titration, then wait for the precipitate to completely settle to the bottom, remove the upper layer solution, and add anhydrous ethanol for washing until neutral, and dry after washing to obtain the first product;

[0151] It should be noted that the low-temperature pre-cooling temperature in step (a) is 4 °C;

[0152] The low-temperature pre-cooling method in step (a) is ice bath;

[0153] The added mass of potassium permanganate in step (a) is 15 times that of hydrofluoric acid;

[0154] The stirring time for the first time in step (a) is 20 min, and the stirring speed for the first time is 500 rpm;

[0155] The added mass of potassium fluoride in step (a) is 250 times that of hydrofluoric acid;

[0156] In step (a), the time of the second stirring is 40 min, and the rotation speed of the second stirring is 400 rpm;

[0157] In step (a), the mass concentration of hydrogen peroxide is 30%, the added mass of hydrogen peroxide is 20 times that of hydrofluoric acid, the dropping rate of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropping with a separating funnel;

[0158] In step (a), the drying temperature is 80 °C.

[0159] (b) Dissolve metasilicic acid in 45 wt% hydrofluoric acid and 20 wt% oxalic acid, and perform the third stirring to obtain the second product;

[0160] It should be noted that in step (b), the mass ratio of metasilicic acid, hydrofluoric acid and oxalic acid is 25:120:90;

[0161] In step (b), the time of the third stirring is 40 min, and the rotation speed of the second stirring is 400 rpm.

[0162] (c) Dissolve potassium hydrogen fluoride in 45 wt% hydrofluoric acid, and perform the fourth stirring to obtain the third product;

[0163] It should be noted that in step (c), the mass ratio of potassium hydrogen fluoride to hydrofluoric acid is 65:200.

[0164] (d) Mix hydrofluoric acid with the first product, perform the fifth stirring, then add the second product and the third product 8 s after the start of the fifth stirring, perform the sixth stirring, let it stand for 10 min after the stirring stops, pour off the supernatant after the precipitate sinks to the bottom, wash the precipitate with absolute ethanol until neutral, and dry the washed product;

[0165] It should be noted that in step (d), the time of the fourth stirring is 50 min, and the rotation speed of the second stirring is 300 rpm.

[0166] It should be noted that in step (d), the mass ratio of hydrofluoric acid to the first product is 600:15;

[0167] In step (d), the time of the fifth stirring is 50 min, and the rotation speed of the second stirring is 600 rpm;

[0168] In step (d), the mass ratio of hydrofluoric acid to the second product and the third product is 3:5:5;

[0169] In step (d), the time of the sixth stirring is 30 min, and the rotation speed of the second stirring is 600 rpm;

[0170] The drying temperature in step (d) is 90 °C.

[0171] (e) The product dried in step (d) is subjected to atomic layer deposition treatment to obtain a film-coated product, and then the film-coated product is mixed with glass powder, heat-treated at a high temperature, and naturally cooled;

[0172] The method of atomic layer deposition treatment in step (e) is as follows: Place the dried product in the reaction chamber of atomic layer deposition, evacuate to 10 Pa under a nitrogen atmosphere, heat the reaction chamber to a reaction temperature of 90 °C, introduce trimethylaluminum vapor as the aluminum source precursor, the introduction time is 10 s, stop the introduction, purge the reaction chamber with nitrogen, the purge time is 60 s, then introduce ozone gas into the reaction chamber, the introduction time is 10 s, and purge the reaction chamber with nitrogen again until a 1 nm film layer is deposited, and cool to room temperature under a nitrogen atmosphere to obtain the film-coated product;

[0173] The manufacturing process of the glass powder in step (e) is as follows: Mix B2O3, SiO2, ZnO and Na2O according to a mass ratio of 10:60:20:10, calcine at 1200 °C for 4 h, cool to room temperature, ball mill and pass through a 200-mesh sieve to obtain it;

[0174] The mass ratio between the film-coated product and the glass powder in step (e) is 1:10;

[0175] The temperature of the high-temperature treatment in step (e) is 800 °C, and the time of the high-temperature treatment is 30 min.

[0176] Example 5

[0177] A fluorescent rubber cake, and the chemical structure of the fluorescent rubber cake is shown in formula (II): K2(Si,F6):Mn 4+ 0.06 (II).

[0178] The manufacturing process of the fluorescent rubber cake includes the following steps: (a) Low-temperature pre-cool the hydrofluoric acid with a concentration of 40 wt%, then add potassium permanganate, stir for the first time, then add potassium fluoride, stir for the second time, then add hydrogen peroxide, dropwise add hydrogen peroxide until the whole solution shows a brown color after titration is completed, stop titration, then wait for the precipitate to completely settle to the bottom, remove the upper layer solution, and add anhydrous ethanol for washing, wash until neutral, and dry after washing to obtain the first product;

[0179] It should be noted that the low-temperature pre-cooling temperature in step (a) is 4 °C;

[0180] The low-temperature pre-cooling method in step (a) is ice bath;

[0181] The added mass of potassium permanganate in step (a) is 13 times that of hydrofluoric acid;

[0182] The time of the first stirring in step (a) is 10 min, and the rotation speed of the first stirring is 400 rpm;

[0183] The added mass of potassium fluoride in step (a) is 150 - 250 times that of hydrofluoric acid;

[0184] The time of the second stirring in step (a) is 30 min, and the rotation speed of the second stirring is 300 rpm;

[0185] In step (a), the mass concentration of hydrogen peroxide is 30%, the added mass of hydrogen peroxide is 15 times that of hydrofluoric acid, the dropping speed of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropping with a separating funnel;

[0186] The drying temperature in step (a) is 70 °C.

[0187] (b) Dissolve metasilicic acid in hydrofluoric acid with a concentration of 40 wt% and oxalic acid with a concentration of 15 wt%, and perform the third stirring to obtain the second product;

[0188] It should be noted that the mass ratio of metasilicic acid, hydrofluoric acid and oxalic acid in step (b) is 20:110:85;

[0189] The time of the third stirring in step (b) is 35 min, and the rotation speed of the second stirring is 300 rpm.

[0190] (c) Dissolve potassium hydrogen fluoride in hydrofluoric acid with a concentration of 40 wt%, and perform the fourth stirring to obtain the third product;

[0191] It should be noted that the mass ratio of potassium hydrogen fluoride to hydrofluoric acid in step (c) is 55:180.

[0192] (d) Mix hydrofluoric acid with the first product, perform the fifth stirring, then add the second product and the third product 7 s after the start of the fifth stirring, perform the sixth stirring, let it stand for 7 min after the stirring stops, pour off the supernatant after the precipitate sinks to the bottom, wash the precipitate with absolute ethanol until it is neutral, and dry the washed product;

[0193] It should be noted that the time of the fourth stirring in step (d) is 40 min, and the rotation speed of the second stirring is 280 rpm.

[0194] It should be noted that the mass ratio of hydrofluoric acid to the first product in step (d) is 500:10;

[0195] In step (d), the time for the fifth stirring is 30 min - 50 min, and the rotation speed for the second stirring is 400 rpm - 600 rpm;

[0196] In step (d), the mass ratio of hydrofluoric acid to the second product and the third product is 2:4:4;

[0197] In step (d), the time for the sixth stirring is 20 min, and the rotation speed for the second stirring is 500 rpm;

[0198] In step (d), the drying temperature is 80 °C.

[0199] (e) The product dried in step (d) is subjected to atomic layer deposition treatment to obtain a film-coated product, and then the film-coated product is mixed with glass powder, subjected to high-temperature treatment, and naturally cooled;

[0200] The method of atomic layer deposition treatment in step (e) is as follows: Place the dried product in the reaction chamber of atomic layer deposition, evacuate to 10 Pa under a nitrogen atmosphere, heat the reaction chamber to a reaction temperature of 80 °C, introduce trimethylaluminum vapor as the aluminum source precursor, with an introduction time of 5 s, stop the introduction, purge the reaction chamber with nitrogen, with a purge time of 40 s, then introduce ozone gas into the reaction chamber, with an introduction time of 6 s, and purge the reaction chamber with nitrogen again until a 1-nm film layer is deposited, and cool to room temperature under a nitrogen atmosphere to obtain the film-coated product;

[0201] The manufacturing process of the glass powder in step (e) is as follows: Mix B2O3, SiO2, ZnO, and Na2O in a mass ratio of 10:60:20:10, calcine at 1100 °C for 3 h, cool to room temperature, ball mill and pass through a 200-mesh sieve to obtain it;

[0202] In step (e), the mass ratio between the film-coated product and the glass powder is 1:8;

[0203] In step (e), the temperature of the high-temperature treatment is 750 °C, and the time of the high-temperature treatment is 20 min.

[0204] Test plan

[0205] Referring to the test method of the prior art, the patent authorization announcement number: CN104893718B (color-stable manganese-doped phosphor), conduct high-temperature and high-humidity tests, and perform HTHH treatment with reference to the standard (IEC60068-2-78), at a temperature of 85 °C, a relative humidity of 85%, for a duration of 1000 h, use a 615-nm excitation light source, test the luminescence intensity of the sample before and after HTHH treatment, and finally calculate the quantum efficiency (QE) of the sample.

[0206] Table 1 Test results

[0207] QE before treatment, % QE after treatment, % Example 1 100 90.2 Example 2 100 85.6 Example 3 100 93.5 Example 4 100 97.8 Example 5 100 98.4

[0208] As shown in Table 1 test, the results show that under high temperature and high humidity conditions, the quantum efficiency (QE) of different schemes all decreases after treatment, but the decrease amplitude is different. Specifically:

[0209] Example 1: The QE decreases from 100% to 90.2% before and after treatment.

[0210] Example 2: The QE decreases from 100% to 85.6% before and after treatment.

[0211] Example 3: The QE decreases from 100% to 93.5% before and after treatment.

[0212] Example 4: The QE decreases from 100% to 97.8% before and after treatment.

[0213] Example 5: The QE decreases from 100% to 98.4% before and after treatment.

[0214] These results indicate that Example 5 shows the smallest decrease in quantum efficiency under high temperature and high humidity conditions, demonstrating good stability and durability. In contrast, Example 2 has the largest decrease in quantum efficiency, and its chemical structure may need to be further optimized or the treatment process improved to enhance its performance in harsh environments. Through these tests, important data support can be provided for subsequent material improvement and application. In addition, for the fluorescent glue cake prepared in Example 5, its scanning electron microscope structure diagram is as Figure 1 shown, and its particle size distribution is as Figure 2 shown. The obtained fluorescent glue cake has good particle crystallization quality and a relatively smooth surface. This smooth surface helps to improve its luminescence performance. The average particle size of the fluorescent glue cake particles is 4.82 um, and most of the powder particles have a particle size concentrated between 3.6 and 6.5 um, showing relative uniformity in the particle size distribution.

[0215] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but rather to the broadest scope consistent with the principles and novel features disclosed herein.

Claims

1. A manufacturing process of a fluorescent glue cake, comprising the following steps: (a) Pre-cool hydrofluoric acid with a concentration of 35wt%-45wt% at a low temperature, then add potassium permanganate and stir for the first time. Then add potassium fluoride and stir for the second time. Then add hydrogen peroxide and drip hydrogen peroxide until the whole solution shows a brownish color after titration is completed. Stop titration. Then, after the precipitate completely settles to the bottom, remove the upper solution and add anhydrous ethanol for washing until it is neutral. After washing, dry it to obtain the first product; (b) Dissolve metasilicic acid in hydrofluoric acid with a concentration of 35wt%-45wt% and oxalic acid with a concentration of 10wt%-20wt%, and stir for the third time to obtain the second product; (c) Dissolve potassium hydrogen fluoride in hydrofluoric acid with a concentration of 35wt%-45wt% and stir for the fourth time to obtain the third product; (d) Mix hydrofluoric acid with the first product and stir for the fifth time. Then, at 5 - 8 s after the start of the fifth stirring, add the second product and the third product and stir for the sixth time. After stirring stops, let it stand for 2 min - 10 min. After the precipitate settles to the bottom, pour off the upper clear liquid. Wash the precipitate with anhydrous ethanol until it is neutral, and dry the washed product; (e) Subject the product dried in step (d) to atomic layer deposition treatment to obtain a film-coated product. Then mix the film-coated product with glass powder, perform high-temperature treatment, and then cool it naturally; Among them, the mass ratio of metasilicic acid, hydrofluoric acid, and oxalic acid in step (b) is (15 - 25):(100 - 120):(80 - 90); The stirring time for the third time in step (b) is 30 min - 40 min, and the rotation speed for the second stirring is 250 rpm - 400 rpm; Among them, the method of atomic layer deposition treatment in step (e) is as follows: Place the dried product in the reaction chamber of atomic layer deposition. Under a nitrogen atmosphere, evacuate to 10 Pa, heat the reaction chamber to a reaction temperature of 50°C - 90°C, introduce trimethylaluminum vapor as the aluminum source precursor, and the introduction time is 0.1 s - 10 s. Stop introducing, and purge the reaction chamber with nitrogen for 1 s - 60 s. Then introduce ozone gas into the reaction chamber, and the introduction time is 0.1 s - 10 s. Purge the reaction chamber with nitrogen again until a 1 nm film layer is deposited. Cool it to room temperature under a nitrogen atmosphere to obtain the film-coated product.

2. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: The low-temperature pre-cooling temperature in step (a) is 0°C - 4°C; The low-temperature pre-cooling method in step (a) is ice bath; The added mass of potassium permanganate in step (a) is 10 - 15 times that of hydrofluoric acid.

3. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: The stirring time for the first time in step (a) is 5 min - 20 min, and the rotation speed for the first stirring is 300 rpm - 500 rpm; The added mass of potassium fluoride in step (a) is 150 - 250 times that of hydrofluoric acid.

4. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: In step (a), the time of the second stirring is 20 min - 40 min, and the rotation speed of the second stirring is 200 rpm - 400 rpm; In step (a), the mass concentration of hydrogen peroxide is 30%, the added mass of hydrogen peroxide is 10 times - 20 times that of hydrofluoric acid, the dropping rate of hydrogen peroxide is 1 drop / s, and the dropping method of hydrogen peroxide is dropping with a separating funnel; In step (a), the drying temperature is 60 °C - 80 °C.

5. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: In step (c), the mass ratio between potassium bifluoride and hydrofluoric acid is (45 - 65):(160 - 200); In step (d), the time of the fourth stirring is 25 min - 50 min, and the rotation speed of the second stirring is 250 rpm - 300 rpm.

6. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: In step (d), the mass ratio between hydrofluoric acid and the first product is (400 - 600):(5 - 15); In step (d), the time of the fifth stirring is 30 min - 50 min, and the rotation speed of the second stirring is 400 rpm - 600 rpm.

7. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: In step (d), the mass ratio between hydrofluoric acid and the second product and the third product is (1 - 3):(2 - 5):(3 - 5); In step (d), the time of the sixth stirring is 10 min - 30 min, and the rotation speed of the second stirring is 400 rpm - 600 rpm; In step (d), the drying temperature is 70 °C - 90 °C.

8. The manufacturing process of the fluorescent glue cake according to claim 1, wherein: The manufacturing process of the glass powder in step (e) is as follows: Mix B2O3, SiO2, ZnO and Na2O according to a mass ratio of 10:60:20:10, calcine at 1000 °C - 1200 °C for 2 h - 4 h, cool down to room temperature, ball mill and pass through a 200-mesh sieve to obtain it; In step (e), the mass ratio between the film-coated product and the glass powder is 1:(6 - 10); In step (e), the temperature of the high-temperature treatment is 700 °C - 800 °C, and the time of the high-temperature treatment is 10 min - 30 min.

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