CN113773832A - Fluosilicate red fluorescent powder and preparation method thereof - Google Patents
Fluosilicate red fluorescent powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 36
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 32
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 24
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 24
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 24
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000007873 sieving Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 16
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229940104869 fluorosilicate Drugs 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/617—Silicates
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- H01—ELECTRIC ELEMENTS
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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Abstract
The invention discloses a fluosilicate red fluorescent powder with a chemical formula of Ca1‑xSiO2F2:xMn2+(ii) a Wherein, the value range of x is 0.17-0.56. The invention also discloses a preparation method of the fluorescent powder, which comprises the following steps: (1) weighing raw materials according to the stoichiometric ratio of the chemical formula; (2) mixing the raw materials, adding a fluxing agent for grinding, uniformly mixing and sieving to obtain a mixture; (3) putting the mixture obtained in the step (2) into a crucible, sintering for 4-6 hours in a high-temperature furnace at a sintering temperature of 800-1000 ℃ in a reducing atmosphere, and cooling to obtain the fluosilicate red fluorescent powder; wherein, the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; the addition amount of the fluxing agent is 0.2-0.4% of the total weight of the raw materials, the fluxing agent is a mixture of ammonium fluoride and ammonium chloride, and the weight ratio of the ammonium fluoride to the ammonium chloride is 3.5-8.4: 1. The invention can prepare the product with good dispersibility and uniform particle size distributionThe fluosilicate red fluorescent powder with high luminous performance can meet the application requirement of the fluorescent powder in LED packaging.
Description
Technical Field
The invention relates to the field of LED luminescent materials, in particular to fluosilicate red fluorescent powder and a preparation method thereof.
Background
A Light-Emitting Diode (LED) is a semiconductor electronic component that converts electrical energy into Light energy. Such electronic devices appeared as early as 1962, and only low-intensity red light was emitted in the early stage, and other versions of monochromatic light were developed later, so that light emitted so far has been spread over visible light, infrared light and ultraviolet light, and the width has been increased to a higher level, and the electronic devices are called "fourth generation light sources". Because of its advantages of energy saving, environmental protection, safety, long service life, etc., it has been widely used in various aspects of industry and life, including the fields of indication, display, decoration, backlight source, general illumination, etc.
For a white LED lamp with a wide application, there are three main methods for implementing a white LED: (1) coating yellow fluorescent powder, mainly YAG, Ce on the blue light chip, and mixing the blue light and the yellow light into white light; (2) the chips with three colors of red, green and blue are packaged in a combined way, and the light emitted by the chips is directly mixed into white light; (3) the near ultraviolet chip is used to excite the red, green and blue fluorescent powders to mix into white light. Of the three methods, the method 1 is the most mature and mainstream method at present, but the product color rendering index of the method is low, generally about 70, the color temperature is high, generally above 5500K, and has a certain deviation from the optimal visual requirement of human eyes, so that a certain amount of red fluorescent powder needs to be doped. While the other two methods also require the use of red phosphors to emit the desired red light. In addition, red phosphors are used in many other types of LED light sources or devices. Therefore, there is a great market demand for red phosphors in the LED industry.
The red fluorescent powder with better performance and mature application in the current market is mainly rare earth doped nitride or nitrogen oxide fluorescent powder. However, the fluorescent powder needs rare earth doping, the raw material requirement is special, high-temperature and high-pressure preparation is usually required, and the preparation condition is harsh. Not only has high energy consumption, but also has low yield, so the production cost is high and the price is very expensive. At present, other methods for preparing the fluorescent powder, such as a hydrothermal method, a microwave method, a high-temperature solid phase method and the like, have complex production processes and still have high requirements on equipment. In addition, the absorption peak of the light conversion material of the blue LED is required to be positioned at 420-470 nm, so that the fluorescent material meeting the requirement is very few and has low absorption intensity. The research of such phosphor materials is difficult, and the varieties of phosphors that can be excited by blue light to emit visible light are not many.
Therefore, the development of new compositions of red phosphors and the improvement of the current synthesis methods of red phosphors have received much attention.
Disclosure of Invention
One of the objectives of the present invention is to provide a fluosilicate red phosphor with a chemical formula of Ca1-xSiO2F2:xMn2+(ii) a Wherein, the value range of x is 0.17-0.56.
The second purpose of the invention is to provide a preparation method of the fluosilicate red fluorescent powder, which comprises the following steps:
(1) according to the chemical formula Ca1-xSiO2F2:xMn2+Weighing raw materials according to the stoichiometric ratio;
(2) mixing the raw materials, adding a fluxing agent for grinding, uniformly mixing and sieving to obtain a mixture;
(3) putting the mixture obtained in the step (2) into a crucible, sintering for 4-6 hours in a high-temperature furnace at a sintering temperature of 800-1000 ℃ in a reducing atmosphere, and cooling to obtain the fluosilicate red fluorescent powder;
wherein, the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; the addition amount of the fluxing agent is 0.2-0.4% of the total weight of the raw materials, the fluxing agent is a mixture of ammonium fluoride and ammonium chloride, and the weight ratio of the ammonium fluoride to the ammonium chloride is 3.5-8.4: 1.
According to another specific embodiment of the invention, the embodiment of the invention discloses a preparation method of fluorosilicate red phosphor, and the step (1) further comprises the following steps: stirring the raw materials in ethanol, filtering, drying at 100 ℃, and sieving.
According to another specific embodiment, the embodiment of the invention discloses a preparation method of fluorosilicate red fluorescent powder, wherein the value of x is 0.4; in the step (1), the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; in the step (2), the addition amount of the fluxing agent is 0.3% of the total weight of the raw materials, and the weight ratio of the ammonium fluoride to the ammonium chloride is 4: 1; in the step (3), the sintering temperature is 850 ℃ and the sintering time is 5 hours.
According to another specific embodiment, the embodiment of the invention discloses a preparation method of fluorosilicate red fluorescent powder, wherein the value of x is 0.17; in the step (1), the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; in the step (2), the addition amount of the fluxing agent is 0.4% of the total weight of the raw materials, and the weight ratio of the ammonium fluoride to the ammonium chloride is 6: 1; in the step (3), the sintering temperature is 950 ℃ and the sintering time is 4 hours.
According to another specific embodiment, the embodiment of the invention discloses a preparation method of fluorosilicate red fluorescent powder, wherein the value of x is 0.56; in the step (1), the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; in the step (2), the addition amount of the fluxing agent is 0.2% of the total weight of the raw materials, and the weight ratio of the ammonium fluoride to the ammonium chloride is 8.4: 1; in the step (3), the sintering temperature is 1000 ℃, and the sintering time is 6 hours.
According to another specific embodiment, the invention discloses a preparation method of fluorosilicate red phosphor, wherein the reducing atmosphere is H2And N2The mixed atmosphere of (A), the H2The volume ratio of the water-soluble organic acid is 25 percent.
Compared with the prior art, the invention has the following advantages:
with Mn4+The excitation replaces the excitation of rare earth ions, the raw materials are cheap and easy to obtain, and compared with the conventional nitride fluorescent powder, the production cost is greatly reduced, and the economic benefit is higher. The prepared red fluorescent powder has good dispersibility, uniform particle size distribution (the particle size can be 4-30 mu m), sharp emission peak shape and stable luminous performance, and can meet the application requirements of the fluorescent powder in LED packaging, such as the field of LED illumination or backlight. In addition, the product has stable physicochemical properties and is easy to store for a long time.
Drawings
FIG. 1 shows a fluorescence spectrum of a fluorosilicate red phosphor of example 1 of the present invention;
FIG. 2 shows an SEM image of a fluorosilicate red phosphor of example 1 of the present invention;
FIG. 3 shows an X-ray diffraction pattern of a fluorosilicate red phosphor of example 1 of the present invention along with a standard card.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention is described in connection with the embodiments for the purpose of covering alternatives or modifications that may be extended based on the claims of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
The chemical formula of the fluosilicate red fluorescent powder is Ca0.6SiO2F2:0.4Mn2+The preparation method comprises the following steps:
(1) according to the chemical formula Ca0.6SiO2F2:0.4Mn2+Weighing and mixing the raw materials of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide according to the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving;
(2) adding ammonium fluoride and ammonium chloride which are 0.3 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 4: 1;
(3) putting the mixture obtained in the step (2) into a crucible, and putting the crucible into a high-temperature furnace in H2And N2Sintering for 5 hours under the conditions of reducing atmosphere and 850 ℃, and cooling to obtain manganese-doped fluosilicate red fluorescent powder Ca0.6SiO2F2:0.4Mn2+。
Example 2
The chemical formula of the fluosilicate red fluorescent powder is Ca0.83SiO2F2:0.17Mn2+The preparation method comprises the following steps:
(1) according to the chemical formula Ca0.83SiO2F2:0.17Mn2+Weighing and mixing the raw materials of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide according to the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving;
(2) adding ammonium fluoride and ammonium chloride which are 0.4 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 6: 1;
(3) putting the mixture obtained in the step (2) into a crucible, and putting the crucible into a high-temperature furnace in H2And N2Sintering for 4 hours under the conditions of reducing atmosphere and 950 ℃, and cooling to obtain manganese-doped fluosilicate red fluorescent powder Ca0.83SiO2F2:0.17Mn2+。
Example 3
The chemical formula of the fluosilicate red fluorescent powder is Ca0.44SiO2F2:0.56Mn2+The preparation method comprises the following steps:
(1) according to the chemical formula Ca0.44SiO2F2:0.56Mn2+Weighing and mixing the raw materials of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide according to the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving;
(2) adding ammonium fluoride and ammonium chloride which are 0.2 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 8.4: 1;
(3) putting the mixture obtained in the step (2) into a crucible, and putting the crucible into a high-temperature furnace in H2And N2Sintering for 6 hours under the conditions of reducing atmosphere and 1000 ℃, and cooling to obtain manganese-doped fluosilicate red fluorescent powder Ca0.44SiO2F2:0.56Mn2+。
Example 4
The chemical formula of the fluosilicate red fluorescent powder is Ca0.6SiO2F2:0.4Mn2+The preparation method comprises the following steps:
(1) according to the chemical formula Ca0.6SiO2F2:0.4Mn2+Weighing and mixing the raw materials of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide according to the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving;
(2) adding ammonium fluoride and ammonium chloride which are 0.3 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 6: 1;
(3) putting the mixture obtained in the step (2) into a crucible, and putting the crucible into a high-temperature furnace in H2And N2Sintering for 5 hours under the conditions of reducing atmosphere and 850 ℃, and cooling to obtain manganese-doped fluosilicate red fluorescent powder Ca0.6SiO2F2:0.4Mn2+。
Example 5
The chemical formula of the fluosilicate red fluorescent powder is Ca0.6SiO2F2:0.4Mn2+The preparation method comprises the following steps:
(1) according to the chemical formula Ca0.6SiO2F2:0.4Mn2+Weighing and mixing the raw materials of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide according to the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving;
(2) adding ammonium fluoride and ammonium chloride which are 0.4 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 8.4: 1;
(3) putting the mixture obtained in the step (2) into a crucible, and putting the crucible into a high-temperature furnace in H2And N2Sintering for 5 hours under the conditions of reducing atmosphere and 850 ℃, and cooling to obtain manganese-doped fluosilicate red fluorescent powder Ca0.6SiO2F2:0.4Mn2+。
Comparative example 1
Chemical composition of Ca1-xSiO2F2:xMn2+(ii) a Wherein, x value range is 0.15, and the preparation method is characterized by comprising the following steps:
(1) is composed of Ca according to the chemical formula1-xSiO2F2:xMn2+Weighing raw materials which are a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide in the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving, wherein the value range of x is 0.15;
(2) adding ammonium fluoride and ammonium chloride which are 0.15 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 3.5: 1;
(3) putting the mixture obtained in the step 2 into a crucible, and putting the crucible in a high-temperature furnace in H2/N2Sintering for 3.5 hours under the conditions of reducing atmosphere and 750 ℃, and cooling to obtain the manganese-doped fluosilicate red fluorescent powder.
Comparative example 2
ChemistryComposition of Ca1-xSiO2F2:xMn2+(ii) a Wherein, x value range is 0.6, and the preparation method is characterized by comprising the following steps:
(1) is composed of Ca according to the chemical formula1-xSiO2F2:xMn2+Weighing raw materials which are a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide in the stoichiometric ratio, stirring in ethanol, filtering, drying at 100 ℃, and sieving, wherein the value range of x is 0.6;
(2) adding ammonium fluoride and ammonium chloride accounting for 0.45 percent of the weight of the raw materials, grinding, uniformly mixing and sieving to obtain a mixture, wherein the weight ratio of the ammonium fluoride to the ammonium chloride is 8.9: 1;
(3) putting the mixture obtained in the step 2 into a crucible, and putting the crucible in a high-temperature furnace in H2/N2Sintering for 6.5 hours under the conditions of reducing atmosphere and 1050 ℃, and cooling to obtain the manganese-doped fluosilicate red fluorescent powder.
The luminescent properties of the phosphors prepared in examples 1 to 5 and comparative examples 1 to 2 were respectively tested, and specific performance test data are shown in table 1.
TABLE 1 luminescence properties of phosphors of examples and comparative examples
| Color temperature (K) | CIE-X | CIE-Y | Luminous flux | Light efficiency (lm/w) | Color rendering index | |
| Example 1 | 5383 | 0.3086 | 0.3106 | 33.314 | 111.23 | 81 |
| Example 2 | 5531 | 0.3075 | 0.307 | 29.9228 | 109.28 | 79.9 |
| Example 3 | 5390 | 0.3088 | 0.309 | 30.9325 | 109.49 | 80 |
| Example 4 | 5516 | 0.3095 | 0.3083 | 31.7746 | 109.09 | 80 |
| Example 5 | 5393 | 0.3061 | 0.3049 | 32.9518 | 109.91 | 80.5 |
| Comparative example 1 | 5789 | 0.3094 | 0.306 | 30.4631 | 107.99 | 79.2 |
| Comparative example 2 | 6914 | 0.3066 | 0.3087 | 29.773 | 105.55 | 80.5 |
FIG. 1 shows a fluorescence spectrum of a fluorosilicate red phosphor prepared in example 1 of the present invention, wherein the excitation wavelength is 465 nm; the emission wavelength was 633 nm. As can be seen from Table 1 and FIG. 1, the ammonium fluoride and the ammonium chloride are used as the fluxing agent, the addition amount of the fluxing agent and the weight ratio of the ammonium fluoride to the ammonium chloride are controlled to be 3.5-8.4: 1, and the prepared fluosilicate red fluorescent powder is greatly improved in luminous intensity and good in stability. FIG. 2 shows an SEM image of a fluorosilicate red phosphor of example 1 of the present invention, and it can be seen from FIG. 2 that the fluorosilicate red phosphor prepared in the present application has a particle size of about 5 μm.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more detailed description of the invention, taken in conjunction with the specific embodiments thereof, and that no limitation of the invention is intended thereby. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (7)
1. The fluosilicate red fluorescent powder is characterized in that the chemical formula of the fluosilicate red fluorescent powder is Ca1- xSiO2F2:xMn2+(ii) a Wherein, the value range of x is 0.17-0.56.
2. A method of preparing the fluorosilicate red phosphor of claim 1, comprising the steps of:
(1) according to the chemical formula Ca1-xSiO2F2:xMn2+Weighing raw materials according to the stoichiometric ratio;
(2) mixing the raw materials, adding a fluxing agent for grinding, uniformly mixing and sieving to obtain a mixture;
(3) putting the mixture obtained in the step (2) into a crucible, sintering for 4-6 hours in a high-temperature furnace at a sintering temperature of 800-1000 ℃ in a reducing atmosphere, and cooling to obtain the fluosilicate red fluorescent powder;
wherein the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; the addition amount of the fluxing agent is 0.2-0.4% of the total weight of the raw materials, the fluxing agent is a mixture of ammonium fluoride and ammonium chloride, and the weight ratio of the ammonium fluoride to the ammonium chloride is 3.5-8.4: 1.
3. The method for preparing a fluorosilicate red phosphor of claim 2, wherein step (1) further comprises the steps of: stirring the raw materials in ethanol, filtering, drying at 100 ℃, and sieving.
4. The method of claim 2, wherein x is 0.4; in the step (1), the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; in the step (2), the addition amount of the fluxing agent is 0.3% of the total weight of the raw materials, and the weight ratio of the ammonium fluoride to the ammonium chloride is 4: 1; in the step (3), the sintering temperature is 850 ℃ and the sintering time is 5 hours.
5. The method of claim 2, wherein x is 0.17; in the step (1), the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; in the step (2), the addition amount of the fluxing agent is 0.4% of the total weight of the raw materials, and the weight ratio of the ammonium fluoride to the ammonium chloride is 6: 1; in the step (3), the sintering temperature is 950 ℃ and the sintering time is 4 hours.
6. The method of claim 2, wherein x is 0.56; in the step (1), the raw material is a mixture of calcium fluoride, potassium fluoride, silicon dioxide, oxalic acid and manganese dioxide; in the step (2), the addition amount of the fluxing agent is 0.2% of the total weight of the raw materials, and the weight ratio of the ammonium fluoride to the ammonium chloride is 8.4: 1; in the step (3), the sintering temperature is 1000 ℃, and the sintering time is 6 hours.
7. The method of preparing a fluorosilicate red phosphor of any one of claims 2 to 6, wherein the reducing atmosphere is H2And N2The mixed atmosphere of (A), the H2The volume ratio of the water-soluble organic acid is 25 percent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449687A (en) * | 2013-09-25 | 2015-03-25 | 海洋王照明科技股份有限公司 | Manganese-titanium co-doped indium fluosilicate luminescent film as well as preparation method and application thereof |
| CN104877675A (en) * | 2015-05-12 | 2015-09-02 | 岭南师范学院 | Mixed-valence-state europium (Eu) ion doped single-matrix color-adjustable fluorescent powder and preparation method thereof |
| CN105950139A (en) * | 2016-06-29 | 2016-09-21 | 东台市天源荧光材料有限公司 | Manganese ion activated fluorosilicate red fluorescent powder and preparation method thereof |
| CN106118637A (en) * | 2016-06-27 | 2016-11-16 | 东台市天源荧光材料有限公司 | A kind of fluosilicate red fluorescence powder and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449687A (en) * | 2013-09-25 | 2015-03-25 | 海洋王照明科技股份有限公司 | Manganese-titanium co-doped indium fluosilicate luminescent film as well as preparation method and application thereof |
| CN104877675A (en) * | 2015-05-12 | 2015-09-02 | 岭南师范学院 | Mixed-valence-state europium (Eu) ion doped single-matrix color-adjustable fluorescent powder and preparation method thereof |
| CN106118637A (en) * | 2016-06-27 | 2016-11-16 | 东台市天源荧光材料有限公司 | A kind of fluosilicate red fluorescence powder and preparation method thereof |
| CN105950139A (en) * | 2016-06-29 | 2016-09-21 | 东台市天源荧光材料有限公司 | Manganese ion activated fluorosilicate red fluorescent powder and preparation method thereof |
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