Block fluoride fluorescent powder, preparation method thereof, mixture and luminescent device

Abstract

The invention discloses block fluoride fluorescent powder and a preparation method thereof, a mixture and a luminescent device, the space group of the block fluoride fluorescent powder is P3m1, the crystal grains of the block fluoride fluorescent powder are tetrakaidecahedron particles with the surface being # imgabs0 # and {0001} crystal plane families, the chemical structural formula of the block fluoride fluorescent powder is AxMaFz: yMn < 4 + >, A is at least one of K, Rb, Na, Li, Cs and NH4 < + >, and M is Ti or Ge or a combination of Ti or Ge and other limited elements; 1.8 < = x < = 2.2, 0.8 < = a < = 1.05, 0.0001 < = y < = 0.2, and 5.8 < = z < = 6.2. The block fluoride fluorescent powder provided by the invention solves the problems that the existing fluorescent powder has an obvious flaky preferential habit, is low in luminous intensity and limited in Mn < 4 + > doping amount, and is difficult to meet the market requirements of LED (Light Emitting Diode) devices.

Description

Technical Field

[0001] The invention relates to the technical field of luminescent materials, and in particular to a bulk fluoride phosphor and a preparation method thereof, a mixture and a luminescent device. Background Art

[0002] White light LED (light emitting diode) is widely used in high-end liquid crystal display due to its high light efficiency, long life, energy saving and green environmental protection, and has become an ideal backlight source for light-emitting devices such as TVs and mobile phones. At the same time, in order to meet the demand for high color gamut coverage of LED backlight sources, the half-peak width of the corresponding red fluorescent material in the device needs to be less than 10nm. Mn 4+ Activated fluoride red powder is the most ideal red fluorescent material with its wide excitation, narrow emission (<10nm), high color coordinates, and high light efficiency. It can make its color gamut reach 100% NTSC (the color gamut space standard established by the United States) color gamut standard, and can meet the color gamut coverage requirements of high-end LED liquid crystal display applications. 4+ (KTF) phosphor) has a peak emission wavelength (631.5nm) that is greater than the current commercial fluoride red powder - K2SiF6:Mn 4+ (KSF) main peak wavelength (629nm), theoretically, can further improve its color gamut coverage.

[0003] Patent document CN 112063384 A provides a manganese-doped K2TiF6 red phosphor and a preparation method thereof, which involves a two-step reaction: the first step is to dissolve potassium permanganate in deionized water, then add potassium hydrogen fluoride, and after it is dissolved, slowly dropwise add a hydrazine hydrochloride aqueous solution, and reduce potassium permanganate by hydrazine hydrochloride to obtain a tetravalent manganese complex; the second step is to dissolve potassium hydrogen fluoride in an aqueous solution, then add potassium fluorotitanate, and then add the tetravalent manganese complex, and react on a rotary mixer to obtain K2TiF6:Mn 4+ Red phosphor.

[0004] The outer surface of the red phosphor grains prepared by this synthesis method is composed of {0001} and The crystal face of the crystal face family is composed of this type of phosphor. It has obvious flake preference habits, low luminous intensity, and Mn 4+ The doping amount is limited and it is difficult to meet the market requirements of LED devices. Summary of the invention

[0005] (I) Purpose of the invention

[0006] The purpose of the present invention is to provide a bulk fluoride phosphor and a preparation method, a mixture and a light-emitting device thereof. The phosphor particles in the present invention are composed of a specific crystal face family, which is conducive to the doping replacement of adsorbed manganese ions, so that the doping efficiency of the activator is improved, so as to solve the problems of the existing phosphors having obvious flake preferential habits, low luminous intensity, and Mn 4+ The doping amount is limited, which makes it difficult to meet the market requirements of LED devices and improve light output efficiency.

[0007] (II) Technical solution

[0008] In order to solve the above problems, the present invention provides a bulk fluoride phosphor in the first aspect, wherein the space group is P3m1, and the crystal grains are composed of a surface The tetradecahedral particles composed of {0001} crystal face family have the chemical structure: x M a F z :yMn 4+ ,in:

[0009] A is K, Rb, Na, Li, Cs and NH4 + At least one of

[0010] M is Ti or Ge, or a combination of Ti and at least one element selected from Si, Ge, Zr, Sn and Hf, or a combination of Ge and at least one element selected from Si, Ti, Zr, Sn and Hf; and 1.8≤x≤2.2, 0.8≤a≤1.05, 0.0001≤y≤0.2, 5.8≤z≤6.2.

[0011] Furthermore, the XRD spectrum of the phosphor includes three characteristic diffraction peaks, namely, (101) ,I (001) and I (002) .

[0012] Furthermore, the I (101) , said I (001) and the I (002) The peak intensity ratio between them satisfies: I (101) / I (002) ≥0.8, I (101) / I (001) ≥0.8.

[0013] Furthermore, when M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, the molar ratio of Ti to M is 50% or more.

[0014] Furthermore, if M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, when the molar ratio of Ti to M is greater than 80%, 1.9≤x≤2.1, 0.95≤a≤1, 0.02≤y≤0.1, and 5.9≤z≤6.1.

[0015] Furthermore, if M is Ti, then x=2, z=6.

[0016] The second aspect of the present invention provides a method for preparing any one of the above-mentioned bulk fluoride phosphors, the method comprising the following steps:

[0017] S1, weighing the basic raw material and the remaining raw material respectively, uniformly mixing the basic raw material and the remaining raw material according to the chemical structure formula and the stoichiometric ratio, and dissolving the mixed raw materials in an HF aqueous solution to prepare a first solution; wherein, if the fluoride, oxide or fluoromanganate of Ti is used as the basic raw material, the fluoride, oxide or fluoromanganate of at least one of Ge, Si, Zr, Sn and Hf is used as the remaining raw material; if the fluoride, oxide or fluoromanganate of Ge is used as the basic raw material, the fluoride, oxide or fluoromanganate of at least one of Ti, Si, Zr, Sn and Hf is used as the remaining raw material;

[0018] S2, containing K, Rb, Na, Li, Cs and NH4 + Dissolving at least one fluoride in a hydrohalic acid aqueous solution to prepare a second solution, injecting the second solution into the first solution at a rate of 5 to 2 ml / min, mixing, heating and stirring, and filtering to obtain a mixed system;

[0019] S3, adding HF aqueous solution with a mass concentration of 2% to 5%wt to the mixed system, stirring and washing for 3 times, and then washing twice with acetone solution;

[0020] S4, taking the washed mixed system and performing air drying at a temperature of 60-100° C. to obtain a bulk fluoride phosphor.

[0021] Further, in S2, the hydrohalic acid includes HCl, HBr and HI.

[0022] The third aspect of the present invention provides a phosphor mixture, comprising a bulk fluoride phosphor as described in any one of the above descriptions and any one of β-sialon green powder, silicate green powder and quantum dot green powder, or comprising a bulk fluoride phosphor as described in any one of the above descriptions and at least one of aluminate phosphor, nitride red powder, nitride blue-green powder and phosphate blue powder.

[0023] A fourth aspect of the present invention provides a light-emitting device, comprising a phosphor coated on an ultraviolet, purple or blue light LED chip, wherein the phosphor is a bulk fluoride phosphor as described in any one of the above descriptions.

[0024] (III) Beneficial effects

[0025] The present invention provides a bulk fluoride phosphor and a preparation method thereof, a mixture and a light-emitting device, which have the following beneficial effects: since the luminescence characteristics of the fluoride phosphor are closely related to its microscopic morphology, the microscopic morphology includes factors such as grain size, shape, distribution and crystal orientation, which will significantly affect the luminescence efficiency and color purity of the phosphor, the grains of the bulk fluoride phosphor provided by the present invention have a chemical structural formula of: A x M a F z :yMn 4+ , this type of phosphor particles consists of specific and blocky tetradecahedral particles composed of {0001} facets, using The high surface energy of the crystal face can better absorb manganese ions for doping replacement, thereby improving the activator doping efficiency and higher light extraction efficiency. The upper and lower hexagonal bottom surfaces of the fluoride phosphor belong to the {0001} crystal face family, and the twelve trapezoidal side surfaces belong to as well as Crystal plane family. Non-close-packed planes of fluoride phosphors with space group P-3m1 The surface energy is higher, making it easier to adsorb Mn in the liquid phase synthesis process 4+ , effectively increasing Mn 4+ In the chemical structure of the fluoride phosphor, M is Ti or Ge, or a combination of Ti and at least one element selected from Si, Ge, Zr, Sn and Hf, or a combination of Ge and at least one element selected from Si, Ti, Zr, Sn and Hf. In the present invention, the content ratio of each element is controlled by means of component regulation: 1.8≤x≤2.2, 0.8≤a≤1.05, 0.0001≤y≤0.2, 5.8≤z≤6.2, so as to increase the structural stability of the phosphor and make the phosphor have better luminescence performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention is and P3m1 fluoride grains composed of the {0001} crystal plane family;

[0027] Figure 2 This is a SEM image of the fluoride phosphor sample prepared in Example 1 (magnified 800 times);

[0028] Figure 3This is a SEM image of the fluoride phosphor sample prepared in Example 2 (magnified 500 times);

[0029] Figure 4 This is a SEM image of the fluoride phosphor sample prepared in Example 3 (magnified 1000 times);

[0030] Figure 5 This is a SEM image of the fluoride phosphor sample prepared in Example 4 (magnified 500 times);

[0031] Figure 6 This is a SEM image of the fluoride phosphor sample prepared in the comparative example (magnified 500 times);

[0032] Figure 7 This is the standard morphology of the fluoride phosphor prepared in the comparative example;

[0033] Figure 8 The XRD patterns of the fluoride phosphor samples prepared in Examples 1 to 4 and the comparative example. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0035] 1. Technical solution

[0036] To solve the problem of K2TiF6:Mn 4+ There is a problem of flake preference. The first aspect of the present invention provides a bulk fluoride phosphor, such as Figure 1 As shown, its space group is P3m1, and its grains are composed of The tetradecahedral particles composed of {0001} crystal face family have the chemical structure: x M a F z :yMn 4+ ,in:

[0037] A is K, Rb, Na, Li, Cs and NH4 + At least one of

[0038] M is Ti or Ge, or a combination of Ti and at least one element selected from Si, Ge, Zr, Sn and Hf, or a combination of Ge and at least one element selected from Si, Ti, Zr, Sn and Hf; and 1.8≤x≤2.2, 0.8≤a≤1.05, 0.0001≤y≤0.2, 5.8≤z≤6.2; the phosphor particles provided by the present invention are composed of specific And the {0001} crystal plane family composition, according to thermodynamic calculations, the space group is P3m1, which must contain Ti. 4+ The surface energy of each crystal face of the activated fluoride phosphor, Crystal planes have the characteristics of high surface energy. The surface energy of the crystal face is 5.53 kJ / mol. The surface energy of the crystal plane is 3.68 kJ / mol); for Ge-containing fluoride phosphors with space group P3m1, a similar situation exists. The surface energy of the crystal face is higher. As the crystal face energy is higher, it is more conducive to doping and replacing the manganese ions as the luminescence center, so that the doping efficiency of the luminescence center is improved, thereby increasing the light extraction efficiency. The present invention introduces a halogen solvent to change the direction of grain growth, thereby obtaining a specific And the blocky morphology composed of the {0001} crystal plane family, its grain morphology is mainly composed of crystal plane families with high crystal plane energy, so it is more conducive to the efficient utilization of the luminescence center and obtains higher luminescence efficiency.

[0039] The upper and lower hexagonal bottom surfaces of the fluoride phosphor belong to the {0001} crystal plane family, and the twelve trapezoidal side surfaces belong to Crystal face family (such as Figure 1 As shown, there are six crystal planes pointing outward perpendicular to the paper plane. belong Crystal plane family; six crystal planes perpendicular to the paper surface belong Crystal plane group; (0001), Belongs to the {0001} crystal plane family). Figure 7 is the standard morphology of the fluoride phosphor prepared in the comparative example, and Figure 1 Non-close-packed planes of fluoride phosphors with space group P-3m1 The surface energy of the crystal face group is higher, making it easier to adsorb Mn in the liquid phase synthesis process. 4+ , effectively increasing Mn 4+ Therefore, the fluoride particles with this morphology can ensure a higher doping concentration.

[0040] Furthermore, if Figure 8 As shown in the comparison diagram of the subsequent embodiments, the XRD spectrum of the phosphor includes three characteristic diffraction peaks, namely, (101),I (001) and I (002) , indicating that the outer surface of the phosphor particles is composed of non-close-packed surfaces ( The crystal face group composition is used to increase the surface refractive index of the phosphor and the surface Mn 4+ Doping concentration improves its luminous efficiency.

[0041] Furthermore, the I (101) , said I (001) and the I (002) The peak intensity ratio between them satisfies: I (101) / I (002) ≥0.8, I (101) / I (001) ≥0.8, the XRD peak ratio is within this range, indicating that the surface of the phosphor particles is composed of {0001}, Crystal face composition.

[0042] Furthermore, if M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, the molar ratio of Ti to M is more than 50%. Ti-based fluoride is a typical P-3m1 type fluoride. The content of Ti element more than 50% is the basis for ensuring that the space group of the phosphor is P-3m1.

[0043] Furthermore, if M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, when the molar ratio of Ti to M is more than 80%, 1.9≤x≤2.1, 0.95≤a≤1, 0.02≤y≤0.1, and 5.9≤z≤6.1. Under this condition, the Ti element content can be increased to improve the structural stability of the P-3m1 type phosphor, thereby increasing the structural stability of the phosphor and making the phosphor have better luminescence performance.

[0044] Furthermore, if M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, and the proportion of the Ti element is further increased (corresponding to Examples 1-5, 12, etc.) so that the proportion of the Ti element reaches 90%, the surface properties of the crystal surface of the P-3m1 type phosphor can be stabilized, which is conducive to the adjustable and controllable proportion of the crystal surface during the preparation process.

[0045] Furthermore, if M is Ti, then 1.8≤x≤2.05, 6≤z≤6.2. Preferably, if M is Ti, then x=2, z=6, the fluorescent spatial structure is stable, and the internal defects of the fluorescent powder can be effectively reduced to obtain better thermal stability and reliability.

[0046] The second aspect of the present invention provides a method for preparing the bulk fluoride phosphor described in any one of the above descriptions, the method comprising the following steps:

[0047] S1, weighing the basic raw material and the remaining raw material respectively, uniformly mixing the basic raw material and the remaining raw material according to the chemical structure formula and the stoichiometric ratio, and dissolving the mixed raw materials in an HF aqueous solution to prepare a first solution; wherein, if the fluoride, oxide and manganate of Ti are used as the basic raw material, the fluoride, oxide or fluoromanganate of at least one of Ge, Si, Zr, Sn and Hf is used as the remaining raw material; if the fluoride, oxide and fluoromanganate of Ge are used as the basic raw material, the fluoride, oxide or fluoromanganate of at least one of Ti, Si, Zr, Sn and Hf is used as the remaining raw material;

[0048] S2, containing K, Rb, Na, Li, Cs and NH4 + Dissolving at least one fluoride in a hydrohalic acid aqueous solution to prepare a second solution, injecting the second solution into the first solution at a rate of 5 to 2 ml / min, mixing, heating and vigorously stirring, and filtering to obtain a mixed system;

[0049] S3, adding HF aqueous solution with a mass concentration of 2% to 5%wt to the mixed system, stirring and washing for 3 times, and then washing twice with acetone solution;

[0050] S4, taking the washed mixed system and performing air drying at a temperature of 60-100° C. to obtain a bulk fluoride phosphor.

[0051] Furthermore, in step S1, the mass concentration of the HF aqueous solution is 30-50%wt, and the mass concentration of the first solution (fluoride solution) is 10-15%wt.

[0052] Furthermore, in S2, the temperature of the mixing, heating and stirring is 10-70°C. Too low a temperature is not conducive to the growth of fluoride crystals, and too high a temperature will cause the valence state of Mn in the reaction system to change, thereby reducing the luminescence efficiency.

[0053] Furthermore, in S2, the mixing heating temperature stirring time is 50min to 150min. Insufficient stirring time will result in the first solution and the second solution being unable to be mixed evenly. Too long stirring time will easily lead to excessively large particle size, which cannot meet application requirements. The dropping acceleration of the second solution should be controlled between 5 and 12 ml / min. Too fast a dropping acceleration rate is not conducive to the growth of fluoride phosphor crystals, resulting in too low luminous efficiency. Too slow a dropping acceleration rate has no obvious adverse effect on the growth of the crystals, but will consume a lot of time and cost.

[0054] Furthermore, in S2, the hydrohalic acid includes HCl, HBr and HI. In this step, "the hydrohalic acid containing K, Rb, Na, Li, Cs and NH4 +The purpose of "dissolving at least one fluoride in a hydrohalic acid aqueous solution" is that according to the crystal growth theory, the crystal face with a slow crystal face growth rate will become the outer surface of the crystal. During the crystal face growth process, adsorbing impurities on the crystal face can effectively reduce the crystal face growth rate. The crystal surface has high surface energy, which makes it easier to adsorb impurities and regulate its growth rate. Therefore, halogen anions similar to F (such as Cl - Br - ,I - etc.) as impurity elements can effectively reduce Crystal growth rate.

[0055] Furthermore, the mass concentration of the hydrohalic acid aqueous solution used in S2 should be between 10% and 15%. If the mass concentration of the hydrohalic acid is too low, the purpose of controlling the growth of the fluoride phosphor crystals cannot be achieved. If the concentration of the hydrohalic acid solution is too high, it will affect the nucleation and growth of the fluoride phosphor crystals.

[0056] The above control is achieved by creating a specific solution environment with different halogen ion concentrations during the preparation process. The growth rate of the crystal face, that is, the control of the particle surface As well as the proportion of the {0001} crystal plane, it increases the optimal doping concentration of the activator, thereby ensuring that the bulk fluoride can have higher luminescence efficiency and better packaging performance.

[0057] The third aspect of the present invention provides a phosphor mixture, comprising a bulk fluoride phosphor as described in any one of the above descriptions and any one of β-sialon green powder, silicate green powder and quantum dot green powder, or comprising a bulk fluoride phosphor as described in any one of the above descriptions and at least one of aluminate phosphor, nitride red powder, nitride blue-green powder and phosphate blue powder.

[0058] A fourth aspect of the present invention provides a light-emitting device, comprising a phosphor coated on an ultraviolet, purple or blue light LED chip, wherein the phosphor is a bulk fluoride phosphor as described in any one of the above descriptions.

[0059] Second, the above steps are described in detail below in conjunction with specific embodiments:

[0060] Example 1

[0061] The bulk fluoride phosphor provided in this embodiment is prepared by the following method: 23.51 g K2MnF6 and 39.95 g TiO2 are weighed and dissolved in 300 g HF aqueous solution with a mass concentration of 30% to prepare a first solution; in addition, 58.1 g KF is dissolved in 200 g HI solution with a mass concentration of 10% to prepare a second solution; the second solution is then injected into the first solution at a speed of 5 ml / min and mechanically stirred at a stirring temperature of 50°C; after the reaction solution is stirred for 2 hours, the supernatant is removed, 3% HF aqueous solution is added to wash 3 times, then washed with acetone three times, and dried at 60°C to prepare a bulk fluoride phosphor K2TiF6:0.10Mn 4+ .

[0062] Example 2

[0063] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 23.51g of K2MnF6 and 35.96g of TiO2, dissolving them in 300g of a 30% HF aqueous solution to prepare a first solution; further dissolving 59.46g of KF in 200g of a 15% HBr solution as a second solution; then injecting the second solution into the first solution at a speed of 12ml / min, and mechanically stirring at a stirring temperature of 60°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60°C to prepare a bulk fluoride phosphor K 2.05 Ti 0.9 F 6.05 :0.10Mn 4+ .

[0064] Example 3

[0065] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 16.45g of K2MnF6 and 39.95g of TiO2, dissolving them in 300g of a 30% HF aqueous solution to prepare a first solution; further dissolving 55.95g of KF in 200g of a 10% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5ml / min, and mechanically stirring the solution at a stirring temperature of 57°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution with acetone three times, and drying the solution at 60°C to prepare a bulk fluoride phosphor K 1.90 TiF 6.18 :0.07Mn 4+ .

[0066] Example 4

[0067] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 16.92g of K2MnF6 and 31.96g of TiO2, dissolving them in 300g of HF aqueous solution with a mass concentration of 30%, to prepare a first solution; further dissolving 42.75g of KF in 200g of HBr solution with a mass concentration of 13%, as a second solution; then injecting the second solution into the first solution at a speed of 5ml / min, and mechanically stirring at a stirring temperature of 65°C; after stirring the reaction solution for 2h, removing the supernatant, adding 4% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60°C to prepare a bulk fluoride phosphor K 1.84 TiF 6.2 :0.09Mn 4+ .

[0068] Example 5

[0069] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 5.64g of K2MnF6 and 30.36g of TiO2, dissolving them in 300g of 40% HF aqueous solution to prepare a first solution; further dissolving 18.68g of LiF in 200g of 10% HCl solution as a second solution; then injecting the second solution into the first solution at a speed of 5ml / min, and mechanically stirring at a stirring temperature of 10°C; after stirring the reaction solution for 2.5h, removing the supernatant, adding 5% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60°C to prepare a bulk fluoride phosphor Li 1.8 Ti 0.95 F 6.2 :0.06Mn 4+ .

[0070] Example 6

[0071] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 1.18g of K2MnF6, 23.97g of TiO2, and 12.02g of SiO2 and dissolving them in 300g of a 50% HF aqueous solution to prepare a first solution; further dissolving 40.31g of NaF in 200g of a 15% HCl solution as a second solution; then injecting the second solution into the first solution at a rate of 5ml / min, and mechanically stirring at a stirring temperature of 70°C; after stirring the reaction solution for 1h, removing the supernatant, adding a 3% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 1000°C to prepare a bulk fluoride phosphor Na 1.92 Ti 0.6 Si 0.4F6:0.01Mn 4+ .

[0072] Example 7

[0073] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 8.23 ​​g of K2MnF6 and 37.16 g of TiO2, dissolving them in 300 g of a 40% HF aqueous solution to prepare a first solution; further dissolving 56.63 g of KF in 200 g of a 10% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 63° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60° C. to prepare a bulk fluoride phosphor K 1.95 Ti 0.93 F 5.95 :0.07Mn 4+ .

[0074] Example 8

[0075] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 20.00g of K2MnF6, 9.8g of SnO2, and 27.97g of TiO2 and dissolving them in 300g of a 40% HF aqueous solution to prepare a first solution; further dissolving 113.19g of RbF in 200g of a 10% HCl solution as a second solution; then injecting the second solution into the first solution at a speed of 12ml / min, and mechanically stirring at a stirring temperature of 53°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60°C to prepare a bulk fluoride phosphor Rb 2.2 Ti 0.7 Sn 0.13 F 6.2 :0.17Mn 4+ .

[0076] Example 9

[0077] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 18.80g of K2MnF6, 23.97g of TiO2, and 12.24g of HfO2, dissolving them in 300g of a 40% HF aqueous solution to prepare a first solution; further dissolving 140.05g of RbF in 200g of a 15% HBr solution as a second solution; then injecting the second solution into the first solution at a speed of 9ml / min, and mechanically stirring the solution at a stirring temperature of 73°C; after stirring the reaction solution for 65min, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 86°C to prepare a bulk fluoride phosphor Cs 2.1 Ti 0.6 Hf 0.24 F 6.1 :0.16Mn 4+ .

[0078] Example 10

[0079] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 65.88g of K2MnF, 31.96g of TiO2, and 55.19g of GeO2, dissolving them in 300g of a 40% HF aqueous solution to prepare a first solution; further dissolving 55.19g of KF in 200g of a 10% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5ml / min, and mechanically stirring the solution at a stirring temperature of 61°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60°C to prepare a bulk fluoride phosphor K 1.90 Ti 0.8 Ge 0.05 F 5.9 :0.05Mn 4+ .

[0080] Embodiment 11

[0081] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 64.70 grams of Na2MnF and 39.95 grams of TiO2, dissolving them in 300 grams of HF aqueous solution with a mass concentration of 35%, to prepare a first solution; further dissolving 41.99 grams of NaF in 200 grams of HI solution with a mass concentration of 14%, as a second solution; then injecting the second solution into the first solution at a speed of 8 ml / min, and mechanically stirring at a stirring temperature of 68° C.; after stirring the reaction solution for 2 hours, removing the supernatant, adding 3% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60° C. to prepare a bulk fluoride phosphor Na2TiF 6.16 :0.04Mn 4+ .

[0082] Example 12

[0083] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 14.10 g of K2MnF6, 35.96 g of TiO2, and 2.55 g of HfO2 and dissolving them in 320 g of a 45% HF aqueous solution to prepare a first solution; further dissolving 37.04 g of NH4F in 200 g of a 10% HCl solution as a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 63°C; after stirring the reaction solution for 2 hours, removing the supernatant, adding a 5% HF aqueous solution to wash three times, then washing with acetone three times, and drying at 70°C to prepare a bulk fluoride phosphor (NH4)2Ti 0.9 Hf 0.05 F 6.18 :0.12Mn 4+ .

[0084] Embodiment 13

[0085] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 1.76 g of K2MnF6, 37.92 g of TiO2, and 1.23 g of ZrO2 and dissolving them in 300 g of a 40% HF aqueous solution to prepare a first solution; further dissolving 56.69 g of KF in 200 g of a 12% HCl solution as a second solution; then injecting the second solution into the first solution at a speed of 8 ml / min, and mechanically stirring the solution at a stirring temperature of 63° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 5% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 77° C. to prepare a bulk fluoride phosphor K 1.95 Ti 0.95 Zr 0.02 F6.05 :0.03Mn 4+ .

[0086] Embodiment 14

[0087] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 23.51 g K2MnF6, 6.16 g ZrO2, and 31.96 g TiO2 and dissolving them in 300 g HF aqueous solution with a mass concentration of 40% to prepare a first solution; further dissolving 52.59 g KF in 200 g HCl solution with a mass concentration of 10% to prepare a second solution; then injecting the second solution into the first solution at a speed of 5 ml / min, and mechanically stirring at a stirring temperature of 55° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding 4% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 100° C. to prepare a bulk fluoride phosphor K 1.8 Ti 0.8 Zr 0.1 F 6.2 :0.20Mn 4+ .

[0088] Embodiment 15

[0089] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 18.80 g of K2MnF6, 31.96 g of TiO2, and 3.77 g of SnO2, dissolving them in 300 g of a 30% HF aqueous solution to prepare a first solution; further dissolving 57.52 g of KF in 200 g of a 15% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 60° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60° C. to prepare a bulk fluoride phosphor K 1.98 Ti 0.8 Sn 0.05 F 6.02. :0.16Mn 4+ .

[0090] Example 16

[0091] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 4.70 g of K2MnF6, 19.98 g of TiO2, and 15.02 g of SiO2 and dissolving them in 300 g of a 40% HF aqueous solution to prepare a first solution; further dissolving 56.56 g of KF in 200 g of a 15% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 60° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60° C. to prepare a bulk fluoride phosphor K 1.94 Ti 0.50 Si 0.5 F 6.10 :0.04Mn 4+ .

[0092] Embodiment 17

[0093] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 2.13 g of K2MnF6, 3.17 g of TiO22, and 0.04 g of GeO22, dissolving them in 300 g of a 45% HF aqueous solution to prepare a first solution; further dissolving 55.78 g of KF in 200 g of a 15% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 60° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60° C. to prepare a bulk fluoride phosphor K 1.92 Ti 0.58 Ge 0.40 F 6.08 :0.02Mn 4+ .

[0094] Embodiment 18

[0095] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 13.98 g of K2MnF6 and 37.14 g of TiO2, dissolving them in 300 g of a 50% HF aqueous solution to prepare a first solution; further dissolving 56.69 g of KF in 200 g of a 10% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 63° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution with acetone three times, and drying the solution at 60° C. to prepare a bulk fluoride phosphor K1.95 Ti 0.93 F 6.15 :0.13Mn 4+ .

[0096] Embodiment 19

[0097] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 21.59g of K2MnF6 and 29.96g of TiO2, dissolving them in 300g of HF aqueous solution with a mass concentration of 30%, to prepare a first solution; further dissolving 132.91g of CsF in 200g of 10% HCl solution with a mass concentration as a second solution; then injecting the second solution into the first solution at a speed of 5ml / min, and mechanically stirring at a stirring temperature of 63°C; after stirring the reaction solution for 2h, removing the supernatant, adding 3% HF aqueous solution to wash 3 times, then washing with acetone three times, and drying at 60°C to prepare a bulk fluoride phosphor Cs 2.00 Ti 0.75 F 6.20. :0.20Mn 4+ .

[0098] Embodiment 20

[0099] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 67.56g of K2MnF, 31.96g of TiO2, and 11.30g of SnO2, dissolving them in 350g of a 45% HF aqueous solution to prepare a first solution; further dissolving 55.78g of KF in 200g of a 10% HCl solution as a second solution; then injecting the second solution into the first solution at a rate of 5ml / min, and mechanically stirring at a stirring temperature of 63°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60°C to prepare a bulk fluoride phosphor K 1.92 Ti 0.80 Sn 0.15 F6:0.07Mn 4+ .

[0100] Embodiment 21

[0101] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 65.325g of K2MnF, 33.96g of TiO2, and 6.16g of ZrO2, dissolving them in 300g of a 40% HF aqueous solution to prepare a first solution; further dissolving 58.1g of KF in 200g of a 10% HCl solution to prepare a second solution; then injecting the second solution into the first solution at a rate of 5ml / min, and mechanically stirring the solution at a stirring temperature of 63°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution with acetone three times, and drying the solution at 60°C to prepare a bulk fluoride phosphor K 2.00 Ti 0.85 Zr 0.10 F 6.00 :0.05Mn 4+ .

[0102] Embodiment 22

[0103] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 21.30g of K2MnF6 and 35.96g of TiO2, dissolving them in 300g of HF aqueous solution with a mass concentration of 35%, to prepare a first solution; further dissolving 23.35g of Li2O in 200g of 10% HCl solution with a mass concentration as a second solution; then injecting the second solution into the first solution at a speed of 5ml / min, and mechanically stirring at a stirring temperature of 63°C; after stirring the reaction solution for 2h, removing the supernatant, adding 3% HF aqueous solution to wash 3 times, then washing with acetone three times, and drying at 60°C to prepare a bulk fluoride phosphor Li 1.8 Ti 0.9 F 6.2 :0.20Mn 4+ .

[0104] Embodiment 23

[0105] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 7.455 g of K2MnF6, 30.14 g of SnO2, and 23.97 g of TiO2 and dissolving them in 300 g of a 30% HF aqueous solution to prepare a first solution; further dissolving 119.7 g of CsF in 200 g of a 10% HCl solution as a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 63° C. After stirring the reaction solution for 2 h, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60° C. to prepare a bulk fluoride phosphor Cs 1.80Ti 0.6 Sn 0.4 F 6.08 :0.07Mn 4+ .

[0106] Embodiment 24

[0107] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 626.4g of K2MnF6, 41.2g of GeO2, and 10.7g of HfO2 and dissolving them in 300g of a 45% HF aqueous solution to prepare a first solution; further dissolving 60.2g of KF in 200g of a 12% HCl solution as a second solution; then injecting the second solution into the first solution at a rate of 5ml / min, and mechanically stirring at a stirring temperature of 73°C; after stirring the reaction solution for 2h, removing the supernatant, adding a 3% HF aqueous solution to wash 3 times, then washing with acetone 3 times, and drying at 60°C to prepare a bulk fluoride phosphor K 1.9 Ge 0.8 Hf 0.1 F 6.2 :0.18Mn 4+ .

[0108] Embodiment 25

[0109] The present embodiment provides a bulk fluoride phosphor, which is prepared by the following method: weighing 13.2 g of K2MnF6, 42.2 g of GeO2, and 9.8 g of SnO2 and dissolving them in 300 g of a 35% HF aqueous solution to prepare a first solution; further dissolving 47.6 g of KF in 200 g of a 10% HCl solution as a second solution; then injecting the second solution into the first solution at a rate of 5 ml / min, and mechanically stirring the solution at a stirring temperature of 73° C. After stirring the reaction solution for 2 hours, removing the supernatant, adding a 3% HF aqueous solution to wash the solution three times, then washing the solution three times with acetone, and drying the solution at 60° C. to prepare a bulk fluoride phosphor K 1.9 Ge 0.82 Sn 0.13 F 6.2 :0.13Mn 4+ .

[0110] Comparative Example

[0111] The comparative example provides a fluoride phosphor. Without introducing halogen ions, the following method is used: 19.17 g of K2MnF6 and 33.96 g of TiO2 are weighed and dissolved in 300 g of HF aqueous solution with a mass concentration of 30% to prepare a comparative example first solution; in addition, 56.63 g of KF is dissolved in 200 g of HF solution with a mass concentration of 10% to prepare a comparative example second solution; the comparative example second solution is then injected into the comparative example first solution at a speed of 5 ml / min and mechanically stirred at a stirring temperature of 63°C; after the reaction solution is stirred for 2 hours, the supernatant is removed, 3% HF aqueous solution is added to wash 3 times, then washed with acetone 3 times, and dried at 60°C to prepare a fluoride phosphor K 1.95 Ti 0.85 F 6.07 :0.18Mn 4+ .

[0112] The fluoride phosphors prepared in the above examples 1-25 and the KTF phosphors prepared in the comparative example were tested for luminescence intensity and XRD respectively. The test conditions are as follows:

[0113] (1) The brightness and color coordinates of the samples in this paper were tested under 460nm blue light excitation using the HAAS-2000 high-precision fast spectroradiometer from Hangzhou Yuanfang, with a light intensity sensitivity of 0.01mcd and a color coordinate accuracy of (x, y)±0.0015;

[0114] (2) A JOBIN YVON-SPEX FluoroMAX-4 fluorescence spectrometer was used, with an excitation source of 150W Xe lamp, a scanning step of 1nm, an integration time of 0.1s, and excitation and emission slits of 0.5nm. The test results are shown in Table 1.

[0115] Table 1: Test results of Examples 1-23 of the present invention and comparative examples

[0116]

[0117]

[0118] From the above, it can be seen that the bulk phosphor I prepared in Examples 1-25 (101) / I (001) The value is between 0.80 and 1.33, I (101) / I (002) The fluoride phosphors prepared in Examples 1 to 23 of the present invention are 0.8 to 2.44, and the size is similar to that of the comparative example. and blocky polyhedral grains composed of {0001} crystal planes. Figure 6 The SEM image of the fluoride phosphor sample prepared in the comparative example is shown in FIG. Figure 2-5 The scanning electron microscope image shown in FIG. 1 shows that the fluoride phosphor prepared in the embodiment of the present invention is a regular tetrahedron crystal. From the data in Table 1, it can be seen that when the activator concentration is lower than that in the comparative example, a higher luminescence intensity is obtained, which proves that the Mn in the embodiment of the present invention is 4+ The effective doping concentration is higher.

[0119] Moreover, the luminescence intensity of the bulk phosphors prepared in Examples 1-25 of the present invention is greater than that of the comparative example; and the activator concentrations thereof are less than that of the comparative example.

[0120] In addition, the XRD peak ratios of the fluoride phosphors prepared in Examples 1-4 and the KTF phosphors prepared in the comparative example were respectively measured. The test conditions and results are as follows:

[0121] The XRD peak ratio test was conducted using the X'Pert PRO MPDX powder diffractometer from PANalytical. The X-ray source was Cu Kα and the X-ray wavelength was The tube voltage is 40 kV, the tube current is 250 mA, the scanning range 2θ is 10-90° (or 20-70°), the scanning step is 0.02°, and the scanning speed is 8° per minute;

[0122] The results are as follows Figure 8 As shown, the horizontal axis is 2θ (2theta), and the vertical axis is intensity (Intensiy, unit AU). Compared with the comparative example, the XRD diffraction diagram of the embodiment of the present invention is (101) The diffraction peak is stronger, indicating that the outer surface of the fluoride phosphor corresponding to the embodiment The proportion of crystal faces is higher.

[0123] The present invention provides a bulk fluoride phosphor and a preparation method thereof, a mixture and a light-emitting device, which have the following advantages:

[0124] 1. The outer surface of the bulk fluoride phosphor provided by the present invention is as well as

[0125] The tetradecahedral particles are composed of {0001} crystal faces. The crystal surface energy is high, which can effectively increase the Mn 4+ The effective doping concentration increases the luminescence intensity;

[0126] 2. Introducing halogen ions during the preparation process can effectively change as well as

[0127] {0001} crystal face growth rate, so that it is exposed to the outer surface of the fluoride phosphor;

[0128] 3. The preparation process of the present invention is simple and suitable for large-scale batch production;

[0129] 4. This type of bulk fluorinated phosphor particles is applied to LEDs. When encapsulated, it can effectively reduce the device's correlated color temperature, making its light output efficiency higher and obtaining a higher display color gamut.

[0130] The descriptions in the specific embodiments of the present invention are related to the well-known technologies in the art, and can be implemented with reference to the well-known technologies. The present invention has been verified through repeated experiments and has achieved satisfactory trial results.

[0131] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any familiar technicians can make equivalent replacements or changes according to the technical solutions and improved concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A bulk fluoride phosphor, characterized in that: Its space group is P3m1, and its grains are composed of The tetradecahedral particles composed of {0001} crystal face family have the chemical structure: x M a F z :yMn 4+ ,in: A is K, Rb, Na, Li, Cs and NH4 + At least one of M is Ti or Ge, or a combination of Ti and at least one element selected from Si, Ge, Zr, Sn and Hf, or a combination of Ge and at least one element selected from Si, Ti, Zr, Sn and Hf; and 1.8≤x≤2.2, 0.8≤a≤1.05, 0.0001≤y≤0.2, 5.8≤z≤6.

2.

2. The bulk fluoride phosphor according to claim 1, characterized in that: The XRD spectrum of the phosphor includes three characteristic diffraction peaks, namely, (101) ,I (001) and I (002) .

3. The bulk fluoride phosphor according to claim 2, characterized in that: I (101) , said I (001) and the I (002) The peak intensity ratio between them satisfies: I (101) / I (002) ≥0.8, I (101) / I (001) ≥0.

8.

4. The bulk fluoride phosphor according to claim 1, characterized in that: When M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, the molar ratio of Ti to M is 50% or more.

5. The bulk fluoride phosphor according to claim 1, characterized in that: If M is a combination of Ti and at least one element selected from Si, Ge, Zr, Sn, and Hf, when the molar ratio of Ti to M is greater than 80%, 1.9≤x≤2.1, 0.95≤a≤1, 0.02≤y≤0.1, and 5.9≤z≤6.

1.

6. The bulk fluoride phosphor according to claim 5, characterized in that: If M is Ti, then 1.8≤x≤2.05, 6≤z≤6.

2.

7. The method for preparing a bulk fluoride phosphor according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, weighing the basic raw material and the remaining raw material respectively, uniformly mixing the basic raw material and the remaining raw material according to the chemical structure and the stoichiometric ratio, and dissolving the mixed raw materials in an HF aqueous solution to prepare a first solution; wherein, if the fluoride, oxide or fluoromanganate of Ti is used as the basic raw material, the fluoride, oxide or fluoromanganate of at least one of Si, Zr, Sn and Hf is used as the remaining raw material; if the fluoride, oxide or fluoromanganate of Ge is used as the basic raw material, the fluoride, oxide or fluoromanganate of at least one of Ti, Si, Zr, Sn and Hf is used as the remaining raw material; S2, containing K, Rb, Na, Li, Cs and NH4 + Dissolving at least one fluoride in a hydrohalic acid aqueous solution to prepare a second solution, injecting the second solution into the first solution at a rate of 5 to 2 ml / min, mixing, heating and stirring, and filtering to obtain a mixed system; S3, adding HF aqueous solution with a mass concentration of 2% to 5%wt to the mixed system, stirring and washing for 3 times, and then washing twice with acetone solution; S4, taking the washed mixed system and performing air drying at a temperature of 60-100° C. to obtain a bulk fluoride phosphor.

8. The method for preparing bulk fluoride phosphor according to claim 7, characterized in that: In S2, the hydrohalic acid includes HCl, HBr and HI.

9. A phosphor mixture, characterized in that: It comprises the bulk fluoride phosphor as described in any one of claims 1 to 6 and any one of β-sialon green powder, silicate green powder and quantum dot green powder, or it comprises the bulk fluoride phosphor as described in any one of claims 1 to 6 and at least one of aluminate phosphor, nitride red powder, nitride blue-green powder and phosphate blue powder.

10. A light emitting device, characterized in that: A phosphor coated on an LED chip comprising ultraviolet light, violet light or blue light, wherein the phosphor is the bulk fluoride phosphor as claimed in any one of claims 1 to 6.

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