Anti-degradation red phosphor, its manufacturing method and use

Abstract

The present application relates to a degradation-resistant red phosphor, its manufacturing method, and its use, which belong to the technical field of phosphor materials. The degradation-resistant red phosphor of the present application has a core-shell structure, the core-shell structure including a core and a shell, the core and the shell being independently selected from materials represented by Chemical Formula I: A2M (1-x) F6:xMn 4+ The present application is 4+ The atomic percentage of Mn is controlled to be lowest in the innermost layer of the core and highest in the outermost layer of the core. 4+ The content of the phosphor is extremely low, and thus the phosphor core is covered with a shell, which improves the moisture resistance and deterioration prevention ability of the phosphor, and at the same time, in combination with the core, is advantageous in maintaining a relatively high luminous efficiency.

Description

[Technical Field]

[0001] The present application relates to a degradation-resistant red phosphor, its manufacturing method and use, and is in the field of phosphor materials. [Background technology]

[0002] In LED lighting, phosphors are usually mixed and dispersed with silica gel, then spotted into the LED packaging bracket cup with a spin bond. During use, excitation light is emitted from the blue chip and absorbed by the phosphor inside the LED package, after which the phosphor's emitted light propagates through reflection, refraction, and other mechanisms. When the excitation light is irradiated onto the phosphor surface, scattering occurs in the phosphor, resulting in a loss of some of the phosphor's light efficiency.

[0003] A red phosphor with high luminous efficiency should satisfy the following conditions: 1) strong absorption around 450 nm, 2) narrow emission around 630 nm, and 3) little emission above 650 nm. 4+ The fluorescent material has an emission spectrum that matches these characteristics, a color rendering index (CRI) greater than 90, and a luminous efficiency that is significantly superior to conventional red nitride phosphors. However, MnF6 2- Due to the surface hydrolysis of the groups, the fluoride phosphor has poor moisture resistance, and the performance of the corresponding LED package device is prone to degradation during long-term use.

[0004] In the prior art, a reducing agent was used on the surface of phosphor particles to remove Mn 4+ After the activation center nullification treatment, the closer the phosphor particle is to the shell from the inside to the outside, the more Mn 4+ The present invention provides a tetravalent Mn-doped fluoride phosphor that has a core-shell structure and a low content of Mn. This method improves the moisture resistance of the phosphor to some extent, but has a negative effect on the luminous efficiency of the phosphor. Summary of the Invention [Problem to be solved by the invention]

[0005] To address the shortcomings of the prior art, the present application provides a degradation-resistant red phosphor, its manufacturing method, and use, which adopts a core-shell structure, in which the activator concentration is controlled so that it is lowest in the innermost layer of the core and highest in the outermost layer of the core, with an extremely low activator content. In addition, a shell is provided to cover the phosphor core, which is advantageous in improving the moisture resistance and degradation resistance of the phosphor, while at the same time maintaining a relatively high luminous efficiency in combination with the core. [Means for solving the problem]

[0006] The first objective of the present application is to provide a degradation-resistant red phosphor, and the technical solutions adopted are as follows: 1. A degradation-resistant red phosphor, the phosphor having a core-shell structure, the core-shell structure comprising a core and a shell, the core and the shell being independently selected from materials represented by Formula I: A2M (1-x) F6:xMn 4+ In formula I, A includes at least one of Li, Na, K, Rb, and Cs, and M includes at least one of Si, Ge, and Ti, and the innermost layer of the core is Mn 4+ The atomic percentage of Mn in the outermost layer of the core is a. 4+ The atomic percentage of Mn at each location inside the core particle is b, b>a. 4+ The atomic percentage of Mn in the shell is x1, and the range of values ​​of x is a≦x1≦b. 4+ The atomic percentage of Mn is x2, and the value range of x2 is 0≦x2≦0.1%. In the present application, the phosphor is in a particulate form, and the innermost layer of the core refers to the central layer inside the phosphor particle. 4+ The outermost layer of the core is also the layer with the smallest atomic percentage of Mn in the phosphor. 4+ The shell refers to the layer with the highest atomic percentage of Mn, and the shell refers to the portion of the phosphor other than the outermost layer of the core, i.e., the portion from the outermost layer of the core to the outer surface of the phosphor, excluding the outermost layer of the core. 4+By controlling the atomic percentage of Mn to be lowest in the innermost layer of the core and highest in the outermost layer, the activator concentration in the core center of the phosphor can be reduced, which is advantageous to suppress the thermal quenching effect and improve the thermal stability, and the concentration of activator ions on the surface of the core can be increased, which is advantageous to improve the absorption rate of the phosphor for excitation light, further suppress the scattering effect, and improve the luminous efficiency of the corresponding LED device. 4+ By providing a shell with an extremely low content of , the core of the phosphor is covered, which prevents the luminescent center from coming into contact with the external environment, improves the moisture resistance and degradation prevention ability of the phosphor, and, in combination with the core, does not affect the luminous efficiency of the phosphor, which is advantageous in that the phosphor can stably maintain a high luminous intensity during long-term use.

[0007] Furthermore, the value of x2 in the shell is in the range of 0≦x2≦0.05%, which can further improve the moisture resistance and degradation prevention ability of the phosphor particles.

[0008] Preferably, x1 shows an increasing tendency from the inside to the outside in the radial direction of the core. In the present application, x1 shows an increasing tendency from the inside to the outside in the radial direction means that the Mn 4+ The content of Mn tends to increase overall from the inside to the outside in the radial direction. In other words, the horizontal axis represents the distance from the innermost layer in the radial direction, and the 4+ However, in the two adjacent layers from the inside to the outside in the radial direction of the phosphor particle, the Mn content in the phosphor particles increases. 4+ The atomic percentage of Mn may increase, decrease, or remain constant. 4+ By controlling the atomic percentage of Mn to increase from the inside to the outside in the radial direction of the core, the Mn in the innermost and outermost layers of the phosphor core can be 4+ The content relationship is ensured, and at the same time, the Mn content in each case inside the core is 4+ The content of the phosphor particles is smoothly shifted from the inside to the outside in the radial direction, ensuring the absorption efficiency of the core with respect to the excitation light, which is advantageous in promoting an improvement in the luminous efficiency of the phosphor particles.

[0009] Preferably, the increasing tendency is such that x1 increases linearly and uniformly from the inside to the outside in the radial direction of the core. In the present application, "increasing linearly and uniformly" means that Mn increases linearly and uniformly from the inside to the outside in the radial direction of the core. 4+ The atomic percentage of Mn in the core maintains the same linear increasing trend. 4+ The atomic percentage of Mn increases linearly and uniformly as the phosphor particle approaches the outermost layer of the core. 4+ The concentration of Mn is high. 4+ By controlling the content of so that it tends to increase uniformly in the core, the phosphor can sufficiently absorb the excitation light, and the conversion efficiency of the phosphor can be improved, which is advantageous in further improving the luminous efficiency of the phosphor.

[0010] Preferably, in the core, the value of a is in the range of 0≦a≦0.1%, and the value of b is in the range of 0.3%≦b≦5%. 4+ By controlling the atomic percentage range of Mn in the core from the innermost layer to the outermost layer, 4+ It is advantageous to adjust the content distribution of the activator to ensure the concentration of the activator on the surface and inside of the core, and to improve the absorption efficiency of the phosphor.

[0011] Preferably, in the core, 0.2%≦(ba)≦5%, and more preferably 0.5%≦(ba)≦2%.

[0012] Illustratively, the value range of a is 0≦a≦0.01%, and the value range of b is 0.5%≦b≦1.5%.

[0013] Preferably, in the core, the value of a is 0 and the value of b is in the range of 0.7%≦b≦1%. For example, in the core, the value of a is 0 and the value of b is in the range of 0.7%≦b≦0.85%.

[0014] Preferably, in the phosphor, b>x2.

[0015] Preferably, in the phosphor, 0≦x2 / b≦1 / 10.

[0016] Preferably, the degradation resistant red phosphor has an average particle size of 5 to 40 μm, for example, 25 to 40 μm.

[0017] Preferably, the shell has an average thickness of 0.1 to 2 μm. Using a shell with this average thickness is advantageous in improving the moisture resistance and degradation prevention ability of the phosphor, as well as in preventing scattering of excitation light and promoting sufficient luminous efficiency of the core.

[0018] The second objective of the present application is to provide a method for manufacturing a degradation-resistant red phosphor, and the technical solutions adopted are as follows: A method for producing any of the degradation-resistant red phosphors described above, comprising: Step 1) dissolving A salt in a hydrofluoric acid solution to form a base solution A; Step 2) dissolving a K2MnF6 series in an equal mass of H2MF6 solution to prepare a BX solution series with different K2MnF6 concentrations; and Step 3) sequentially adding the BX solution series to the base solution A, controlling the K2MnF6 concentration so that the first BX solution added has the lowest concentration and the last BX solution added has the highest concentration. and step 3) adding H2MF6 solution to the core mixture to obtain a core mixture, which is then used to prepare a shell, i.e., to obtain the degradation-resistant red phosphor, wherein the A salt is at least one selected from the group consisting of fluoride, hydrogen fluoride, sulfate, nitrate, hydrogen sulfate, carbonate, and hydrogen carbonate of A, where A is any one selected from Li, Na, K, Rb, and Cs, and M in the H2MF6 is any one selected from Si, Ge, and Ti. The present application employs K2MnF6 and H2MF6 solutions to prepare a series of BX solutions with increasing concentrations of K2MnF6, which react instantly when mixed with the base solution A to form A2MF6:Mn 4+ By producing a precipitate and controlling the concentration of K2MnF6 in the BX solution added at the beginning and end, Mn 4+The atomic percentage of is lowest in the innermost layer of the core and highest in the outermost layer, which is beneficial to improving the thermal stability and luminous efficiency of the entire phosphor. H2MF6 is then reacted with base solution A to produce a shell, which improves the moisture resistance and anti-degradation ability of the phosphor without affecting the luminous efficiency of the phosphor.

[0019] Preferably, in step 3), the BX solution series is added to the base solution A in a sequential order of increasing K2MnF6 concentration. 4+ This results in a core in which the atomic percentage of the phosphor tends to increase from the inside to the outside in the radial direction, and further improves the absorption rate of the phosphor for excitation light.

[0020] Preferably, in step 2), the extraction of the K2MnF6 series is to sequentially extract K2MnF6 whose mass increases in an arithmetic progression. 4+ The atomic percentage of the phosphor increases linearly and uniformly from the inside to the outside in the radial direction, which is advantageous for improving the absorption effect and conversion efficiency of the phosphor for the excitation light. Optionally, the tolerance for the mass increase in the arithmetic progression is 0.1 to 0.3 g.

[0021] Preferably, the mass concentration of the H2MF6 solution is 10-15%, and the mass of K2MnF6 used for every 5-7.5 g of H2MF6 in the BX solution series is 0-3 g.

[0022] Preferably, the mass concentration of the hydrofluoric acid solution is 35 to 55%, and the volume of the hydrofluoric acid solution used for every 15 to 25 g of A salt in the base liquid A solution is 200 to 300 mL.

[0023] Preferably, the mass of the BX solution series added in step 3) is 100 to 1300 g, and the mass of the H2MF6 solution added to the core mixture system is 5 to 200 g.

[0024] Preferably, the BX solution series and H2MF6 solution are stirred at 10 to 50°C during the addition process, and after stirring is completed, the supernatant is removed, washed, and dried.

[0025] Preferably, the addition rates of the BX solution series and the H2MF6 solution are both 10 to 50 mL / s, and the stirring time is 2 to 5 hours.

[0026] Preferably, in the A salt, A is element K, i.e., the A salt is a potassium salt. Optionally, the A salt is potassium hydrogen fluoride.

[0027] Furthermore, the mass concentration of the hydrofluoric acid solution is 40% to 55%.

[0028] Preferably, in the H2MF6, M is Si, and the H2MF6 solution is a H2SiF6 solution, i.e., a fluorosilicic acid solution.

[0029] A third object of the present invention is to provide use of any of the above-mentioned degradation-resistant red phosphors or degradation-resistant red phosphors produced by any of the above-mentioned production methods in the field of LCD backlights or LED lighting.

[0030] A fourth object of the present invention is to provide a liquid crystal backlight comprising an excitation chip and a phosphor coated on the excitation chip, wherein the phosphor is any one of the above-mentioned anti-deterioration red phosphors, or the phosphor is an anti-deterioration red phosphor manufactured by any one of the above-mentioned manufacturing methods.

[0031] A fifth object of the present invention is to provide an illumination device comprising a light-emitting device, the light-emitting device comprising an excitation chip and a phosphor coated on the excitation chip, the phosphor being any one of the degradation-resistant red phosphors described above, or the phosphor being a degradation-resistant red phosphor manufactured by any one of the manufacturing methods described above. [Brief explanation of the drawings]

[0032] [Figure 1] 1 is a schematic diagram showing the radial distribution of the relative content of Mn4+ in degradation-resistant red phosphor particles of Examples 1 to 5. FIG. [Figure 2] 1A and 1B are SEM photographs of phosphor particles in a specific embodiment before cutting, where the left is a planar SEM photograph of the phosphor particle and the right is a 45° side SEM photograph after the phosphor particle has been cut to expose a new cross section. [Figure 3] 1 is a diagram showing the position of EDS spot scanning analysis for degradation-resistant red phosphor particles of Example 1. FIG. [Figure 4] FIG. 10 is a diagram showing the positions of EDX line scan analysis on the degradation-prevented red phosphor particles of Example 5. [Figure 5] 10 shows the results of EDX line scanning analysis of degradation-preventing red phosphor particles of Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0033] In order to clarify the objectives, technical solutions and advantages of the present application, the present application will be described in more detail below with reference to specific examples. The following embodiments are exemplary embodiments used to explain the principles of the present application, namely, red phosphor A2M (1-x) F6:xMn 4+ where A and M are preferably K and Si, respectively, and the synthetic raw materials are preferably potassium hydrogen fluoride, fluorosilicic acid, etc., but it should be understood that the present invention is not limited thereto. Those skilled in the art can make various modifications and improvements without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.

[0034] For the sake of brevity, this application explicitly discloses only a few numerical ranges. However, any lower limit may be combined with any upper limit to form an open range, and any lower limit may be combined with any other lower limit to form an open range, and similarly, any upper limit may be combined with any other upper limit to form an open range. Furthermore, although not expressly stated, unless otherwise stated, each point or single value between the endpoints of a range is intended to be included in the range. Thus, each point or single value may serve as its own lower or upper limit, or may be combined with any other point or single value, or with other lower or upper limits, to form an open range.

[0035] K2SiF6:Mn 4+ Compared to conventional red phosphors, red phosphors have the advantage of higher luminous efficiency, but their low moisture resistance makes them prone to performance degradation, which affects their effectiveness in LED lighting. While improving the moisture resistance of conventional red phosphors inevitably has a negative impact on luminous efficiency, there is a strong demand for red phosphors that combine high moisture resistance with high luminous efficiency.

[0036] In order to solve the above problems, the present application provides a degradation-resistant red phosphor, the degradation-resistant red phosphor having a core-shell structure, the core-shell structure including a core and a shell, the core and the shell being independently selected from materials represented by chemical formula I: A2M (1-x) F6:xMn 4+ In formula I, A includes at least one of Li, Na, K, Rb, and Cs, and M includes at least one of Si, Ge, and Ti, and the innermost layer of the core is Mn 4+ The atomic percentage of Mn in the outermost layer of the core is a. 4+ The atomic percentage of Mn at each location inside the core particle is b, b>a. 4+ The atomic percentage of Mn in the shell is x1, and the range of x is a≦x1≦b. 4+The atomic percentage of is x2, and the range of values ​​for x2 is 0≦x2≦0.1%.

[0037] Illustratively, in Formula I, 0 <x≦0.05である。

[0038] In some embodiments, x1 tends to increase from the inside to the outside in the radial direction of the core. In this application, the direction from the inside to the outside in the radial direction of the core refers to the direction starting from the innermost layer of the core to the point on the outermost layer of the core that is closest to the innermost layer of the core, and the innermost layer of the core refers to the first core layer formed first during the production of the degradation-resistant red phosphor, i.e., the first core layer formed by reacting the base solution A solution with the BX solution that was added first. In the phosphor particles of this application, the region where the innermost core layer is located is the region with the lowest concentration of activator.

[0039] In some specific embodiments, the core is divided into n layers from the inside to the outside in the radial direction, n is an integer and the value of n is in the range of 5≦n≦20, and Mn 4+ The atomic percentages of Mn are the same, and the atomic percentages between different layers are Mn from the inside to the outside along the radial direction of the core. 4+ The atomic percentage of shows an increasing trend.

[0040] In some specific embodiments, the lower limit of n is any value selected from 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19, and the upper limit of n is any value selected from 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, and the range of values ​​of n is any value selected from the lower limit and upper limit.

[0041] In some specific embodiments, the increasing trend is such that x1 increases linearly or nonlinearly from the inside to the outside in the radial direction of the core.

[0042] In some specific embodiments, the increasing tendency is a tendency that x1 increases linearly and uniformly from the inside to the outside in the radial direction of the core. In this application, the term "increasing linearly and uniformly" means that Mn increases linearly and uniformly from the inside to the outside in the radial direction of the core. 4+ The atomic percentage of Mn in Example 1 of FIG. 4+ The relative content of Mn between any two adjacent layers of the core increases. 4+ The increasing trend of atomic percentage of

[0043] The present application further provides a method for producing any of the degradation-resistant red phosphors described above, comprising: Step 1) dissolving A salt in a hydrofluoric acid solution to prepare a base solution A; Step 2) dissolving a series of K2MnF6 salts in equal masses of H2MF6 solutions to prepare a series of BX solutions with different K2MnF6 concentrations; and Step 3) sequentially adding the series of BX solutions to the base solution A, with the first BX solution having the lowest K2MnF6 concentration and the last BX solution having the lowest K2MnF6 concentration. and 3) controlling the temperature of the reaction mixture to be the highest, thereby obtaining a core mixture, which is then used to prepare a core, and adding an H2MF6 solution to the core mixture, which is then used to prepare a shell, i.e., obtaining the degradation-resistant red phosphor, wherein the A salt is at least one selected from the group consisting of fluoride, hydrogen fluoride, sulfate, nitrate, hydrogen sulfate, carbonate, and hydrogen carbonate of A, where A is any one selected from the group consisting of Li, Na, K, Rb, and Cs, and in the H2MF6, M is any one selected from the group consisting of Si, Ge, and Ti.

[0044] In some exemplary embodiments, the fluoride of A may be any one selected from lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride; the hydrogen fluoride salt of A may be any one selected from LiHF, NaHF, KHF, RbHF, and CsHF; the sulfate salt of A may be any one selected from LiSO, NaSO, KSO, RbSO, and CsSO; and the nitrate salt of A may be any one selected from LiNO, NaNO, or , KNO3, RbNO3, and CsNO3, the hydrogen sulfate salt of A may be any one selected from LiHSO4, NaHSO4, KHSO4, RbHSO4, and CsHSO4, the carbonate salt of A may be any one selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, and Cs2CO3, and the hydrogen carbonate salt of A may be any one selected from LiHCO3, NaHCO3, KHCO3, RbHCO3, and CsHCO3.

[0045] In some example embodiments, H2MF6 may be any one selected from H2SiF6, H2GeF6, and H2TiF6.

[0046] In some embodiments, sequentially adding the series of BX solutions to the base solution A in step 3) means sequentially adding the series of BX solutions to the base solution A in order of increasing K2MnF6 concentration.

[0047] In some specific embodiments, collecting the K2MnF6 series in step 2) is performed by adding the following: n The K2MnF6 raw material is collected as a1, a2, a3, ..., a n indicates a sequentially increasing trend, n is an integer, and the value range of n is 5≦n≦20.

[0048] In some specific embodiments, the value of n is in the range of 10≦n≦20.

[0049] In some specific embodiments, the masses are a1, a2, a3, ..., a n Each of the K2MnF6 raw materials was dissolved in H2MF6 solution, and the resulting BX solutions with increasing K2MnF6 concentration were named BX1, BX2, BX3, ..., BX n and write BX1, BX2, BX3, ..., BX n The concentration of K2MnF6 in the solution shows a tendency to increase gradually.

[0050] In some specific examples, the value range of a1 is 0≦a1≦0.01 g, and when a1 is 0, the mass of K2MnF6 increases from 0, and the concentration of K2MnF6 in the BX1 solution in the prepared BX solution series is 0.

[0051] In some specific embodiments, the BX solution series is added to the base A solution in increasing order of concentration, and the series of BX solutions is represented by BX1 to BX n The solutions are added to the base A solution in sequence and reacted in sequence to produce a core, which is divided into n layers in the radial direction from the inside to the outside, and each added BX solution reacts with the base A solution to form one layer of the core.

[0052] In some specific embodiments, the mass of H2MF6 in the BX solution and the H2MF6 solution added each time in step 3) is the same, and the number of times the H2MF6 solution is added to the core mixture system is 1 to 5.

[0053] In some specific embodiments, a n The value range is 2.5g≦a n ≦3g.

[0054] In some specific embodiments, the mass concentration of the H2MF6 solution is 10 to 15%, and the mass of the H2MF6 solution is 40 to 60 g, for example, the mass of the H2MF6 solution is 50 g.

[0055] In some specific embodiments, the mass of the A salt is 15 to 25 g.

[0056] In some specific embodiments, the mass concentration of the hydrofluoric acid solution is 35 to 55%, and the volume of the hydrofluoric acid solution is 200 to 300 mL, for example, the volume of the hydrofluoric acid solution is 250 mL.

[0057] In some specific embodiments, the washing is carried out by sequentially adding an aqueous HF solution and anhydrous ethanol, and stirring the solution, and the mass concentration of the aqueous HF solution is 3 to 10%.

[0058] In some specific embodiments, the drying is carried out at a temperature of 50 to 70°C.

[0059] Example The technical solutions of the present application will be described below with reference to specific examples. All raw materials used in the following examples are from common commercial products, and all devices or equipment used are purchased from conventional commercial sales channels.

[0060] Example 1 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.77%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The method for producing the degradation-resistant red phosphor of this example is as follows: Step 1) dissolving 21 g of KHF2 in 250 mL of 40% by mass hydrofluoric acid solution to prepare base solution A; Step 2) A series of K2MnF6 samples are collected and dissolved in 50 g of 10 mass% fluorosilicic acid solution in increasing order of mass to prepare a series of BX solutions with increasing concentrations of K2MnF6. The BX solution series is added to the base solution A in increasing order of concentration, and the number of additions is A1, A2, A3, ..., A 16 A core mixture system is obtained and used to manufacture a core. 50 g of a 10% by mass fluorosilicic acid solution is added to the core mixture system three times, and the number of times of addition is A. 17 , A 18 , A 19 and used to produce the shell (number of times added: A1 to A 19 The mass of the K2MnF6 raw material contained in step (1) is shown in Table 1 below), and in the process of adding the BX solution series and the fluorosilicic acid solution, the stirring is controlled at 40°C, and after stirring for 2 hours, the supernatant is discarded, and a 5 mass% HF aqueous solution is added, and the mixture is stirred and washed twice, and then washed twice with absolute ethanol, and then dried under a blow-drying condition at 60°C to obtain the degradation-resistant red phosphor of the present invention.

[0061] Example 2 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows an increasing trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.80%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The manufacturing method of the degradation-resistant red phosphor of this example differs from Example 1 only in that in step 2), the K2MnF6 raw material whose mass increases is collected separately to prepare a BX solution series, and the masses of the K2MnF6 raw material contained in the BX solution series added in step 3) are shown in Table 1 below.

[0062] Example 3 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows an increasing trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.82%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.02%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The manufacturing method of the degradation-resistant red phosphor of this example differs from Example 1 only in that in step 2), the K2MnF6 raw material whose mass increases is collected separately to prepare a BX solution series, and the masses of the K2MnF6 raw material contained in the BX solution series added in step 3) are shown in Table 1 below.

[0063] Example 4 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows an increasing trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.79%. 4+The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The manufacturing method of the degradation-resistant red phosphor of this example differs from Example 1 only in that in step 2), the K2MnF6 raw material whose mass increases is collected separately to prepare a BX solution series, and the masses of the K2MnF6 raw material contained in the BX solution series added in step 3) are shown in Table 1 below.

[0064] Example 5 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows an increasing trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.81%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.02%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The manufacturing method of the degradation-resistant red phosphor of this example differs from Example 1 only in that in step 2), the K2MnF6 raw material whose mass increases is collected separately to prepare a BX solution series, and the masses of the K2MnF6 raw material contained in the BX solution series added in step 3) are shown in Table 1 below.

[0065] Example 6 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn in the innermost layer of the phosphor core 4+The atomic percentage of Mn in the outermost layer of the core is 0. 4+ The atomic percentage of Mn at each location inside the phosphor core particle is 0.77%. 4+ is x1, and x1 is randomly distributed from the inside to the outside in the radial direction of the core except for the innermost layer and the outermost layer of the core, and the value range of x1 is 0≦x1≦0.77%, and Mn in the shell 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The manufacturing method of the degradation-resistant red phosphor of this example differs from Example 1 only in that in step 2), the K2MnF6 raw material whose mass increases is collected separately to prepare a BX solution series, and the masses of the K2MnF6 raw material contained in the BX solution series added in step 3) are shown in Table 1 below.

[0066] Example 7 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn in the innermost layer of the phosphor core 4+ The atomic percentage of Mn in the outermost layer of the core is 0. 4+ The atomic percentage of Mn at each location inside the phosphor core particle is 5%. 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction, and the value range of x1 is 0≦x1≦5%. 4+ The atomic percentage of is x2, and the range of values ​​for x2 is 0≦x2≦0.1%.

[0067] Example 8 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn in the innermost layer of the phosphor core 4+ The atomic percentage of Mn in the outermost layer of the core is 0.1%. 4+ The atomic percentage of Mn at each location inside the phosphor core particle is 0.3%. 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction, and the value range of x1 is 0.1%≦x1≦0.3%. 4+ The atomic percentage of is x2, and the range of values ​​of x2 is 0≦x2≦0.01%.

[0068] Example 9 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn 4+ where Mn in the innermost layer of the phosphor core 4+ The atomic percentage of Mn in the outermost layer of the core is 0. 4+ The atomic percentage of Mn is 2% at each location inside the phosphor core particle. 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction, and the value range of x1 is 0≦x1≦2%. 4+ The atomic percentage of is x2, and the range of values ​​of x2 is 0≦x2≦0.05%.

[0069] Example 10 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KSi (1-x) F6:xMn4+ where Mn in the innermost layer of the phosphor core 4+ The atomic percentage of Mn in the outermost layer of the core is 0. 4+ The atomic percentage of Mn at each location inside the phosphor core particle is 0.5%. 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction, and the value range of x1 is 0≦x1≦0.5%. 4+ The atomic percentage of is x2, and the range of values ​​of x2 is 0≦x2≦0.01%.

[0070] Example 11 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: LiSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction of the core, the value range of x1 is 0≦x1≦0.81%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The method for producing the degradation-resistant red phosphor of this embodiment differs from that of Example 1 only in that Li2CO3 is used instead of KHF2 in step 1) and dissolved in a hydrofluoric acid solution.

[0071] Example 12 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: CsSi (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.80%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The method for producing the degradation-resistant red phosphor of this example differs from Example 1 only in that CsF is used instead of KHF2 in step 1) and dissolved in a hydrofluoric acid solution.

[0072] Example 13 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KGe (1-x) F6:xMn 4+ where Mn at each location inside the core particle 4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction of the core, and the value range of x1 is 0≦x1≦0.82%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The method for producing a degradation-resistant red phosphor in this example differs from Example 1 only in that a H2GeF6 solution is used instead of a fluorosilicic acid solution in steps 2) and 3).

[0073] Example 14 The degradation-resistant red phosphor of this embodiment has a core-shell structure, which includes a core and a shell, and the core and the shell are independently selected from materials represented by Formula I: KTi (1-x) F6:xMn 4+ where Mn at each location inside the core particle4+ The atomic percentage of Mn in the shell is x1, and x1 shows a linear and uniform increase trend from the inside to the outside in the radial direction of the core, the value range of x1 is 0≦x1≦0.81%. 4+ The atomic percentage of is x2, and the value range of x2 is 0≦x2≦0.01%. The degradation-resistant red phosphor of this example has an average particle size of 30 μm, where the average shell thickness is 1.8 μm. The method for producing a degradation-resistant red phosphor in this example differs from Example 1 only in that a H2TiF6 solution is used instead of a fluorosilicic acid solution in steps 2) and 3).

[0074] Comparative Example 1 The phosphor of this comparative example differs from Example 1 only in that it contains only a core of the degradation-resistant red phosphor of Example 1, but does not contain a shell. In the manufacturing method of the phosphor of this comparative example, in step 3), the BX solution series is added to the base solution A in order of increasing concentration, and the number of additions is A1, A2, A3, ..., A 16 and the number of additions is A1 to A 16 The masses of the K2MnF6 raw materials contained in the above are shown in Table 1 below, and are shown in A1 to A2 in step 3) of Example 1. 16 The mass of the K2MnF6 raw material was the same as that of the corresponding raw material, and the only difference from Example 6 was that the fluorosilicic acid solution was not added after the BX solution was added.

[0075] Comparative Example 2 The phosphor of this comparative example has Mn at each location inside the core particle of the phosphor. 4+ The atomic percentage of is x1, and x1 is uniformly distributed from the inside to the outside in the radial direction, which is different from Example 1. In the manufacturing method of the phosphor of this comparative example, in step 2), 16 equivalent parts of K2MnF6 raw material are taken, and 1.35 g of each part is dissolved in 50 g of 10 mass% fluorosilicic acid solution to prepare a series of BX solutions with equal K2MnF6 concentrations. In step 3), the series of BX solutions are added to the base solution A, respectively, and the number of additions is designated as A1, A2, A3, ..., A 16and Mn 4+ The only difference from Example 1 is that a core having a uniformly distributed atomic percentage of SiO 2 was prepared, and the preparation of the shell was the same as in Example 1.

[0076] Comparative Example 3 The phosphor of this comparative example differs from Comparative Example 2 only in that it contains only the core of the phosphor of Comparative Example 2, and does not contain a shell. The method for producing the phosphor of this comparative example differs from comparative example 2 only in that in step 3), after the BX solution series is added to the base solution A, no fluorosilicic acid solution is added.

[0077] The mass of K2MnF6 in the BX solution series and the fluorosilicic acid solution added in step 3) in Examples 1 to 6 and Comparative Example 1

[0078] [Table 1]

[0079] As can be seen from Table 1, in Examples 1 to 5, a series of BX solutions were prepared using K2MnF6 raw materials with gradually increasing masses, which were then used to produce cores. The mass of the K2MnF6 raw material used to produce the core in Example 1 increased in an arithmetic progression with a tolerance of 0.18 g. The increasing trend in Examples 2 to 5 was nonlinear. In Example 6, the masses of the K2MnF6 raw material contained in the first and last BX solutions added during core production were a minimum of 0 g and a maximum of 2.70 g, respectively, with the mass of the K2MnF6 raw material in the remaining additions being controlled to be random. In Comparative Example 1, the mass of the K2MnF6 raw material used to produce the core was the same as in Example 1, but no shell was produced.

[0080] Test Example 1 The degradation-resistant red phosphors of Examples 1 to 5 were cut using a dual ion beam FIB-SEM (Focused Ion Beam Scanning Electron Microscope) and EDS spectrum analysis was performed from the body center to the surface of the new surface. Taking Example 1 as an example, Figure 2 shows an SEM image of the degradation-resistant red phosphor before cutting, where the left image is a planar SEM image of the phosphor particle and the right image is a 45° lateral SEM image of the phosphor particle cut to expose the new cross section. Figure 3 shows the scanning positions for EDS spot scanning analysis of the degradation-resistant red phosphor particle of Example 1. The radial distribution of Mn atomic percentage from the innermost layer of the core to the outermost layer of the shell of the degradation-resistant red phosphor particles of Examples 1 to 5 obtained by EDS spectrum analysis is shown in Table 2 below.

[0081] Radial distribution table of Mn atomic percentage for Examples 1 to 5

[0082] [Table 2]

[0083] As can be seen from Table 2, the degradation-resistant red phosphors of Examples 1 to 5 are divided into 16 layers from the inside to the outside in the radial direction of the core, and the shell is divided into 3 layers from the inside to the outside in the radial direction. The Mn atomic percentage shows an increasing trend from the inside to the outside in the radial direction of the core, and although each individual value is equal to or slightly decreases from the previous value, it does not affect the overall increasing trend of the Mn atomic percentage in the radial direction of the core. Here, the innermost layer of the core does not contain Mn atoms and the Mn atomic percentage is 0%, the Mn atomic percentage of the outermost layer of the core is between 0.77 and 0.82%, and the Mn atomic percentage in the shell is between 0 and 0.02%. Here, the Mn atomic percentage of Example 1 increases linearly and uniformly overall in the radial direction of the core.

[0084] In order to more intuitively reflect the increasing tendency of the Mn element content in Examples 1 to 5, the Mn content in the degradation-resistant red phosphor particles in Examples 1 to 5 is 4+FIG. 1 shows a schematic diagram of the radial distribution of the relative content of Mn. In FIG. 1, the content in the outermost layer of each example core is taken as the reference (denoted as 1.0), and the black circles on the image indicate the Mn content at different positions in the inner radial direction of the phosphor particle. 4+ 1 shows the relative content of Mn at the center of the body inside the degradation-resistant red phosphor particles of Examples 1 to 5, and the points where the content could not be obtained are indicated by white circles. 4+ As it moves away from the body center and approaches the outermost layer of the core, Mn 4+ The relative content of Mn in Example 1 shows an increasing trend. 4+ The relative content of Mn in the phosphor particles of Examples 1 to 5 shows a linear and uniform increasing trend. 4+ The relative content of Mn is highest in the outermost layer of the core, followed by Mn on the shell. 4+ The relative content of approaches or reaches zero.

[0085] An FIB-SEM focused ion beam scanning electron microscope was used to perform an EDX test on the surface of the degradation-resistant red phosphor particles of Example 5 after cutting them, from the body center to the surface. The EDX line scan positions are shown in Figure 4, and the obtained EDX line scan analysis results are shown in Figure 5. The line scan results show that the degradation-resistant red phosphor particles show a tendency for the Mn content to increase gradually from the innermost layer to the outermost layer of the core, and that the content of Mn, the activator in the shell, shows a tendency for it to decrease rapidly.

[0086] Test Example 2 Aging tests were conducted on the phosphors of Examples 1 to 6 and Comparative Examples 1 to 3, and the luminous flux of each Example and Comparative Example was measured at 0, 250, 500, 750, and 1000 hours. Table 3 shows the test method and equipment used in the 1000-hour aging test, and Table 4 shows the aging test data for the KSF phosphors produced in the Examples and Comparative Examples. (Explanation: KSF-0 is the sample of Comparative Example 1, KSF-1 is the sample of Example 1, KSF-2 is the sample of Example 2, KSF-3 is the sample of Example 3, KSF-4 is the sample of Example 4, KSF-5 is the sample of Example 5, KSF-6 is the sample of Example 6, KSF-7 is the sample of Comparative Example 2, and KSF-8 is the sample of Comparative Example 3.)

[0087] Test method and equipment for aging tests in Examples 1 to 6 and Comparative Examples 1 to 3

[0088] [Table 3]

[0089] Luminous flux and brightness ratio results of Examples 1 to 6 and Comparative Examples 1 to 3 in aging tests

[0090] [Table 4]

[0091] As can be seen from Table 4, the LED devices manufactured using the phosphors of Examples 1 to 6 and Comparative Example 1 had initial luminous fluxes of 126.34 lm to 128.35 lm under an environment of 85°C and 85% RH, whereas the LED device using the phosphor of Comparative Example 2 only had an initial luminous flux of 117.48 lm, and the initial luminous flux of Comparative Example 3 was 120.83 lm. This indicates that the initial luminous flux of the core of Comparative Example 2 decreased by 2.8% after the addition of the shell. By controlling the Mn content of the innermost and outermost layers of the core, the present application has demonstrated that the luminous efficiency of the phosphor is not affected even when a shell with a relatively low atomic percentage of Mn is used. It was found that this was advantageous in ensuring high luminous intensity. As the test time increased, the luminous flux of the LED device using the phosphor of Comparative Example 1 gradually decreased, with the brightness ratio decreasing by about 1% every 250 hours. After 1000 hours, the luminous flux was only 123.47 lm, and the brightness was only 96.2% of the initial brightness, a decrease of 3.8% compared to the previous year. However, the luminous flux of the LED devices using the degradation-resistant red phosphors of Examples 1 to 6 decreased less, and even after 1000 hours of high-temperature, high-humidity environment test, the luminous flux still remained at 125.10 lm to 127.05 lm, the brightness still reached 98.9% to 99.2% of the initial brightness, and the brightness ratio level was maintained at approximately 99%. 4+By providing a shell with an extremely low content of , the phosphor core is covered, and on the premise that the luminous efficiency of the phosphor is not affected, the moisture resistance and degradation prevention ability of the phosphor are significantly improved, and it is clear that the phosphor can maintain high luminous intensity even when used for a long period of time in a harsh environment of high temperature and humidity.

[0092] Furthermore, comparing Examples 1 to 5 horizontally, Example 1 employs a method in which the Mn atomic percentage increases linearly and uniformly throughout the radial direction of the core, and the measured initial luminous flux was the highest at 128.21 lm. In addition, the luminous flux decline during the aging test was the lowest, with the brightness ratio remaining at 99.2% after 1000 hours, a decline of only 1.8%. By controlling the Mn atomic percentage to increase linearly and uniformly in the radial direction of the core, the present application ensures the conversion efficiency of the phosphor, and reduces the impact of harsh environments on the luminous flux during long-term use after combination with the shell, which is advantageous for ensuring higher luminous efficiency.

[0093] Test Example 3 The phosphor samples of Examples 1 and 7 to 10 were each enclosed in a light bulb by the method shown in Table 3 of Test Example 2, and the luminous flux of each example sample was tested. The results are shown in Table 5 below.

[0094] Luminous flux results for samples of Example 1 and Examples 7 to 10

[0095] [Table 5]

[0096] As can be seen from Table 5, the luminous flux of the phosphor samples of Examples 1 and 7 to 10 can reach between 119.35 and 128.21 lm, showing strong luminous performance. Here, the luminous flux of the phosphors of Examples 1, 9, and 10, in which the difference in atomic percentage of the activator between the outermost layer and the innermost layer of the core is 0.5% to 2%, is 124.20 to 128.21 lm, which is further improved compared to Examples 7 and 8. 4+It can be seen that controlling the atomic percent content distribution of is advantageous to improving the absorption efficiency of the phosphor, and thus better light-emitting performance can be obtained.

[0097] The above description is merely a specific embodiment of the present disclosure, but the scope of protection of the present disclosure is not limited thereto, and those skilled in the art can easily imagine modifications or replacements within the technical scope disclosed in the present disclosure, which are included in the scope of protection of the present disclosure. Therefore, equivalent changes according to the claims of the present disclosure are within the scope embraced by the present disclosure.

[0098] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority from a Chinese patent application filed on June 25, 2023, bearing application number 202310724565.3 and entitled "Anti-degradation red phosphor, its manufacturing method and use," the entire contents of which are incorporated herein by reference.

Claims

1. 1. A degradation-resistant red phosphor having a core-shell structure, the core-shell structure comprising a core and a shell, the core and the shell being independently selected from materials represented by Chemical Formula I: A ２ M （１－ｘ） F ６ : xMn ４＋ Chemical formula I In Formula I, A includes at least one of Li, Na, K, Rb, and Cs; M includes at least one of Si, Ge, and Ti; Here, the Mn in the innermost layer of the core ４＋ The atomic percentage of Mn in the outermost layer of the core is a. ４＋ The atomic percentage of Mn at each location inside the core particle is b, b>a. ４＋ The atomic percentage of x １ and the range of the value of x is a≦x １ ≦b, Mn in the shell ４＋ The atomic percentage of x ２ and x ２ The value range of x is 0≦x ２ ≦0.1%.

2. x １ shows an increasing tendency from the inside to the outside in the radial direction of the core, 2. The degradation-resistant red phosphor of claim 1.

3. The increasing tendency is x １ tends to increase linearly and uniformly from the inside to the outside in the radial direction of the core, The degradation-resistant red phosphor of claim 2 .

4. In the core, the range of the value of a is 0≦a≦0.1%, and the range of the value of b is 0.3%≦b≦5%.

2. The degradation-resistant red phosphor of claim 1.

5. In the core, the range of the value of a is 0≦a≦0.01%, and the range of the value of b is 0.5%≦b≦1.5%.

5. The degradation-resistant red phosphor of claim 4.

6. In the phosphor, b>x ２ characterized in that 2. The degradation-resistant red phosphor of claim 1.

7. In the phosphor, 0≦x ２ / b≦1 / 10, 2. The degradation-resistant red phosphor of claim 1.

8. The average particle size of the degradation-resistant red phosphor is 5 to 40 μm, and the average thickness of the shell is 0.1 to 2 μm.

2. The degradation-resistant red phosphor of claim 1.

9. Step 1) dissolving A salt in hydrofluoric acid solution, referred to as base solution A; K ２ MnF ６ Each series is H ２ Midfielder ６ Dissolved in the solution, K ２ MnF ６ Step 2) preparing a series of BX solutions with different concentrations of The BX solution series was added to the base solution A solution in order, and the K of the first BX solution added was ２ MnF ６ The concentration of the BX solution added last is the lowest. ２ MnF ６ The concentration of the core mixture is controlled to be the highest, and the core mixture is used to manufacture the core. ２ Midfielder ６ and step 3) adding the solution and using it to prepare a shell, i.e., to obtain the degradation-resistant red phosphor; The A salt is at least one selected from the group consisting of fluorides, hydrogen fluorides, sulfates, nitrates, hydrogen sulfates, carbonates, and hydrogen carbonates of A, and A is any one selected from the group consisting of Li, Na, K, Rb, and Cs. ２ Midfielder ６ wherein M is any one selected from Si, Ge, and Ti. A method for producing the degradation-resistant red phosphor according to any one of claims 1 to 8.

10. In step 3), the BX solution series is added to the base solution A solution in order to add the BX solution series to the base solution A solution. ２ MnF ６ to the base solution A in an order of increasing concentration. A method for producing the degradation-resistant red phosphor according to claim 9.

11. In step 2), the K ２ MnF ６ Taking a series is a series of K where the mass increases in an arithmetic progression. ２ MnF ６ The method is characterized in that: A method for producing the degradation-resistant red phosphor according to claim 10.

12. The H ２ Midfielder ６ The mass concentration of the solution is 10 to 15%, and 5 to 7.5 g of H ２ Midfielder ６ K used every time ２ MnF ６ has a mass of 0 to 3 g, The mass concentration of the hydrofluoric acid solution is 35 to 55%, and the volume of the hydrofluoric acid solution used for every 15 to 25 g of A salt in the base liquid A solution is 200 to 300 mL. A method for producing the degradation-resistant red phosphor according to claim 9.

13. The mass of the BX solution series added in step 3) is 100 to 1300 g, and the amount of H added to the core mixture is ２ Midfielder ６ 10. The method for producing a degradation-resistant red phosphor according to claim 9, wherein the mass of the solution is 5 to 200 g.

14. Use of the degradation-resistant red phosphor according to any one of claims 1 to 8 or the degradation-resistant red phosphor produced by the production method according to any one of claims 9 to 13 in the field of LCD backlights or LED lighting.

15. An excitation chip and a phosphor coated on the excitation chip, The phosphor is a degradation-resistant red phosphor according to any one of claims 1 to 8, or 14. A liquid crystal display backlight, wherein the phosphor is a degradation-resistant red phosphor manufactured by the manufacturing method according to claim 9.

16. a light emitting device; the light-emitting device includes an excitation chip and a phosphor coated on the excitation chip; The phosphor is a degradation-resistant red phosphor according to any one of claims 1 to 8, or 14. A lighting device, wherein the phosphor is a degradation-resistant red phosphor manufactured by the manufacturing method according to claim 9.

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