CN113444521A - Red fluorescent powder and light-emitting device with same - Google Patents
Red fluorescent powder and light-emitting device with same Download PDFInfo
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- 239000000843 powder Substances 0.000 title abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 230000005284 excitation Effects 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 239000005084 Strontium aluminate Substances 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 18
- 229910003564 SiAlON Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
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- 238000000295 emission spectrum Methods 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000011656 manganese carbonate Substances 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical group Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 241000282414 Homo sapiens Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
- C09K11/572—Chalcogenides
- C09K11/576—Chalcogenides with alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7716—Chalcogenides
- C09K11/7718—Chalcogenides with alkaline earth metals
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
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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
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Abstract
The invention provides red fluorescent powder and a light-emitting device with the same. The phosphor at least comprises an M element, an A element, a D element and an R element, wherein the M element comprises one or two of Ca, Sr, Ba and Mg, and also comprises one or two of Na and K; the element A comprises Al or Al and Ga, and also comprises one or two of Sc, Y, Lu and La; the D element is one or two selected from O, N and F, and must contain O; the R element is one or two of Mn, Ce and Eu, and must contain Mn; the phosphor has a structure similar to Sr4Al14O25The same crystal structure. Due to Sc3+Has a larger ionic radius than Al3+Large ionic radius and doping with Sc3+The ions can relieve Mn4+Lattice distortion caused by ion doping and improvement of Mn4+Local area environment ofThereby enhancing Mn4+The light emission intensity of (1). The red fluorescent powder has strong absorption in an ultraviolet-blue light region, and can emit strong narrow-band red light under the excitation of ultraviolet-blue light.
Description
Technical Field
The invention relates to the field of fluorescent materials, in particular to red fluorescent powder and a light-emitting device with the same.
Background
The white light LED is used as a fourth generation light source, and has the characteristics of high luminous efficiency, long service life, good stability, small volume, environmental friendliness and the like, so that the white light LED is widely applied to the fields of illumination and display. White LEDs have a market share of about 80% in the field of liquid crystal display backlights, and have become the main choice for display backlights.
At present, the mainstream realization mode of the white light LED for display is that a blue light chip is matched with red and green fluorescent powder with narrower half wave width. The color purity and half-wave width of the phosphor become key factors affecting the color gamut coverage of the display. At present, commercial fluorescent powder systems in the field of backlight sources are nitric oxide green fluorescent powder and fluoride red fluorescent powder. Wherein the red phosphor plays a key role in the display gamut of the device.
With the advancement of semiconductor lighting technology and the pursuit of higher lighting quality by human beings, it is becoming apparentIn the field of displays, liquid crystal displays are being developed toward higher color reproduction and wide color gamut display. In order to improve the color gamut coverage of the liquid crystal display, the emission wavelength of the red phosphor is required to be longer, and the color coordinate is required to be closer to the deep red region. In the field of illumination, white light LED light sources have been developed from the initial pure pursuit of "high color rendering and high brightness" to the achievement of "high quality" considering performance parameters of light sources such as safety, health, color reduction, saturation, spectrum continuity and the like, and even the pursuit of full-spectrum healthy illumination similar to sunlight, and the development of efficient far-red fluorescent powder matched with the white light LED light sources is urgently needed. Fluoride red has been successfully used for wide color gamut display and high-efficiency full-spectrum illumination, but the poor weather resistance of the fluorescent powder of the system becomes a big bottleneck preventing the wide application of the fluorescent powder, and the Mn at the luminescent center in the fluoride red fluorescent powder4+In a stable crystal field environment and its special 3d3The electronic structure makes it difficult to directly regulate and control the emission wavelength of the fluoride system fluorescent powder to move towards the long wave direction. The south China university invents a novel aluminate red fluorescent powder, the emission wavelength of which is 652nm, the color coordinate is x which is 0.722, and y which is 0.278. Compared with the current commercial fluoride system, the emission wavelength of the aluminate red fluorescent powder is longer, and the color coordinate is closer to the deep red area. Reference may be made in particular to patent document CN 102732250A. Chen Lei et al report that the current light-emitting efficiency of the phosphor is very low, refer to non-patent Materials Research Bulletin 60(2014) 604-. The excitation intensity of the system in a blue light region can be improved by the Cao Yongpi et al through a Na/Mn codoping mode, and the luminescence can be enhanced, and the specific reference can be made to the publication No. CN 105602556A.
However, the luminous intensity of the aluminate red phosphor reported in the above patent or literature is still low, and cannot meet the practical application requirements, thereby limiting further applications in the liquid crystal display field and high-quality illumination field.
Disclosure of Invention
The invention mainly aims to provide red fluorescent powder and a light-emitting device with the same, and solves the problems of low luminous efficiency of the red fluorescent powder and low luminous color gamut of the light-emitting device through technical breakthrough.
In order to achieve the above object, in one aspect of the present invention, a red phosphor is provided, which has a composition including at least an M element, an a element, a D element, and an R element, wherein the M element includes one or two of Ca, Sr, Ba, and Mg; the element A comprises Al or Al and Ga, and also comprises one or two of Sc, Y, Lu and La; the D element is one or two selected from O, N and F, and must contain O; the R element comprises one or two of Mn, Ce and Eu, and must contain Mn; the phosphor has a structure similar to Sr4Al14O25The same crystal structure. When the element A is Al and Ga, compared with the element A which is Al, the raw material of the Ga source has certain fluxing property in the sintering process, so that the material has better crystal morphology, and higher luminous intensity is brought.
Further, the M element also contains one or two of Na and K. Na (Na)+Or K+Or Na+And K+The incorporation of (A) is advantageous for maintaining the charge balance of the system, Na+-Mn4+Bond substituted Sr2+-Al3+Bond, change Mn4+The crystal field strength of the crystal solves the problem of Mn4+Occupying Al3+The position is such that the charge imbalance of the system causes the problem of low luminous intensity, and the luminous intensity is remarkably enhanced.
Further, the composition formula of the fluorescent powder is M4Ax-aDyaR, wherein the parameters a, x and y satisfy the following conditions: a is more than 0.001 and less than or equal to 1, x is more than or equal to 12 and less than or equal to 16, and y is more than or equal to 24 and less than or equal to 26, and the proportion is satisfied to obtain a purer crystal structure.
Further, the element M is Sr, the element A comprises Al, and also comprises Sc and/or Lu, the element D is O, and the element R is Mn.
Furthermore, the mole percentage of Sc element in the element A is n, and n is more than or equal to 0.01 percent and less than or equal to 35 percent.
The red luminescent material of the invention has the structure of4Al14O25The same crystal structure. Sr4Al14O25:Mn4+The system has an octahedral structure with a spatial point group of pma (51). Sr4Al14O25The three-dimensional network structure is formed by a layer of octahedron (AlO)6) And two layers of tetrahedrons (AlO)4) Composition of in Sr4Al14O25In the middle, there are two Sr lattice sites, six Al lattice sites and eight O lattice sites, Mn4+Occupies octahedron (AlO)6) And medium Al lattice site. Mn preferred for the red phosphor of the present invention4+The activated red fluorescent powder has strong absorption at 400nm-480nm, is particularly suitable for being excited by a blue chip, emits red light with a main peak position at 650nm +/-1 nm, has a narrow half-peak width of about 20nm, and meets the requirements of being excited by blue light and emitting red light in a narrow band.
In the red phosphor, since Mn is present4+The ionic radius is less than Al3+When Mn is present4+As substituted Al3+Lattice site causes cell shrinkage, and the lattice distortion caused by the cell shrinkage affects Mn4+Stability and luminescence properties of the composition. When Sc, Y, Lu and La elements are doped, Sc3+、Y3+、Lu3+、La3+All of the ionic radii of (A) to (B) are larger than that of Al3+Small, so that when one or two of them are substituted for Al3+In lattice position, the unit cell is expanded to some extent4+Lattice distortion caused by substitution can effectively improve Mn4+Localized environment in the matrix, thereby enhancing Mn4+The red fluorescent powder with higher luminous intensity is obtained. Due to the sequence of the ionic radius of Al3+<Sc3+<Lu3+<Y3+<La3+Thus, relatively speaking, Sc3+Radius closest to Al3+Second is Lu3+Therefore, the two elements are easier to be dissolved into the crystal lattice in a solid solution way, so that the crystal cell is expanded, and the Mn is reduced4+Substituted Al3+The lattice sites bring about the contraction of the unit cell without causing the inverse expansion of the lattice due to the larger difference in ionic radius and the distortion of the lattice. And the introduction of Sc element is beneficial to the material to obtain a better crystal morphology, and the material has crystal grains with high dispersity and larger size.
Therefore, the element a is preferably Al or Sc. But Sc3+The substitution is more than 35%, the crystal structure is changed, and less than 0.01% does not play a role in enhancing luminescence.
The excitation spectrum peak wavelength of the fluorescent powder is 250-500 nm, and the emission wavelength is in a range of 625-670 nm.
The preparation method of the material comprises the steps of accurately weighing oxides, carbonates, nitrates and the like of the M element, the A element, the D element and the R element as raw materials, weighing the raw materials according to respective molecular formulas, and fully mixing and grinding the raw materials in a mortar for 20-100min to obtain a mixture. Heating to 1200-1400 ℃ under the atmosphere conditions of air atmosphere or air/nitrogen and the like, and preserving the heat for 2-10 h. And cooling the furnace to obtain a sintered product, taking out the sintered product, crushing, washing, sieving and drying to obtain the fluorescent powder.
According to another aspect of the present application, there is provided a light emitting device including a phosphor including the above-described red phosphor and an excitation light source.
Further, the phosphor also comprises other phosphors, and the other phosphors comprise (Y, Gd, Lu, Tb)3(Al,Ga)5O12:Ce3+、β-SiAlON:Eu2+、La3Si6N11:Ce3+、(Ba,Sr)Si2O2N2:Eu2+One or more of (a).
The narrow-band red fluorescent powder is combined and packaged with one or more colors of fluorescent powder such as yellow fluorescent powder, green fluorescent powder, yellow-green fluorescent powder, cyan fluorescent powder and the like, and white light emission can be obtained under the excitation of a blue light chip. (Y, Gd, Lu, Tb)3(Al,Ga)5O12:Ce3+Is yellow or yellow-green phosphor, beta-SiAlON: Eu2+Is yellow-green phosphor, La3Si6N11:Ce3+Is yellow phosphor, (Ba, Sr) Si2O2N2:Eu2+Cyan phosphor or cyan-green phosphor.
Compared with the prior art that fluoride red powder and beta-SiAlON are Eu2+Green powder combined packaged light-emitting device, fluorescent powder and light-emitting deviceOther phosphors, e.g. (Y, Gd, Lu, Tb)3(Al,Ga)5O12:Ce3+、β-SiAlON:Eu2+、La3Si6N11:Ce3+、(Ba,Sr)Si2O2N2:Eu2+The combined use can ensure that the light-emitting device emits white light with high luminous efficiency, high color rendering and low color temperature, and meets the practical application requirements in the fields of wide color gamut display and high-quality illumination.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is an XRD diffraction pattern of phosphors prepared in comparative example, example 1, example 2 and example 3 of the present invention;
FIG. 2 shows excitation spectra of phosphors prepared in comparative example, example 1, example 2 and example 3 of the present invention;
FIG. 3 shows emission spectra of phosphors prepared in comparative example, example 1, example 2 and example 3 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Comparative example
According to Sr4Al13.99O250.01Mn in a stoichiometric ratio, accurately weighing SrCO3(99.9%),Al2O3(99.9%),MnCO3(99.9%) and put in a mortar to be fully mixed and ground for 30min to obtain a mixture. And raising the temperature of the mixture to 1200 ℃ at a heating rate of 10 ℃/min under an air atmosphere, and then preserving the heat at 1200 ℃ for 6 h. And naturally cooling the furnace temperature to room temperature to obtain a sintered product, taking out the sintered product, crushing, washing, sieving and drying to obtain the comparative example fluorescent powder, wherein the relative emission intensity of the comparative example fluorescent powder is 100. The phosphor was subjected to X-ray scanning to obtain FIG. 1, in which a target material was usedThe target is a Co target, the scanning Bragg angle is 20-80 degrees, and the scanning speed is 5 degrees/min; the fluorescent powder is subjected to fluorescence spectrum test, and an excitation spectrum is obtained with the excitation monitoring wavelength of 650nm and is shown in figure 2. The excitation wavelength was 450nm and the resulting emission spectrum is shown in FIG. 3.
Example 1
According to (Sr)3.9Na0.1)(Al13.93Sc0.06)O250.01Mn in a stoichiometric ratio, accurately weighing SrCO3(99.9%),Al2O3(99.9%),Sc2O3(99.9%),MnCO3(99.9%),Na2CO3(99.9%) and put in a mortar to be fully mixed and ground for 30min to obtain a mixture. And (3) heating the mixture to 900 ℃ at the heating rate of 10 ℃/min under the air atmosphere, preserving the heat for 1h, then heating to 1250 ℃, and preserving the heat for 5 h. And (3) naturally cooling the furnace temperature to room temperature to obtain a sintered product, taking out the sintered product, crushing, washing, sieving and drying to obtain the fluorescent powder of the embodiment 1, wherein the relative emission intensity of the fluorescent powder is 197. Carrying out X-ray scanning on the fluorescent powder to obtain a graph 1, wherein a target material is a Co target, the scanning Bragg angle is 20-80 degrees, and the scanning speed is 5 degrees/min; the fluorescent powder is subjected to fluorescence spectrum test, and an excitation spectrum is obtained with the excitation monitoring wavelength of 650nm and is shown in figure 2. The excitation wavelength was 450nm and the resulting emission spectrum is shown in FIG. 3.
Example 2
According to (Sr)3.9Na0.4)(Al13.93Sc0.06)O250.01Mn in a stoichiometric ratio, accurately weighing SrCO3(99.9%),Al2O3(99.9%),Sc2O3(99.9%),MnCO3(99.9%),Na2CO3(99.9%) and put in a mortar to be fully mixed and ground for 30min to obtain a mixture. And (3) heating the mixture to 900 ℃ at the heating rate of 10 ℃/min under the air atmosphere, preserving the heat for 1h, then heating to 1200 ℃, and preserving the heat for 4 h. And (3) naturally cooling the furnace temperature to room temperature to obtain a sintered product, taking out the sintered product, crushing, washing, sieving and drying to obtain the fluorescent powder of the embodiment 2, wherein the relative emission intensity of the fluorescent powder is 200. X-ray scanning the phosphor to obtain a graph1, wherein the target material is a Co target, the scanning Bragg angle is 20-80 degrees, and the scanning speed is 5 degrees/min; the fluorescent powder was subjected to fluorescence spectrum test, and the excitation spectrum was obtained at a monitoring wavelength of 650nm and shown in FIG. 2. The excitation wavelength was 450nm and the resulting emission spectrum is shown in FIG. 3.
Example 3
According to (Sr)3.4Na0.6)(Al13.93Sc0.06)O250.01Mn in a stoichiometric ratio, accurately weighing SrCO3(99.9%),Al2O3(99.9%),Sc2O3(99.9%),MnCO3(99.9%),Na2CO3(99.9%) and put in a mortar to be fully mixed and ground for 30min to obtain a mixture. Heating the mixture to 900 ℃ at a heating rate of 10 ℃/min under an air atmosphere, preserving heat for 1h, then heating to 1350 ℃, and preserving heat for 5 h. And (3) naturally cooling the furnace temperature to room temperature to obtain a sintered product, taking out the sintered product, crushing, washing, sieving and drying to obtain the fluorescent powder of the embodiment 3, wherein the relative emission intensity of the fluorescent powder is 244. Carrying out X-ray scanning on the fluorescent powder to obtain a graph 1, wherein a target material is a Co target, the scanning Bragg angle is 20-80 degrees, and the scanning speed is 5 degrees/min; the fluorescent powder was subjected to fluorescence spectrum test, and the excitation spectrum was obtained at a monitoring wavelength of 650nm and shown in FIG. 2. The excitation wavelength was 450nm and the resulting emission spectrum is shown in FIG. 3.
Examples 4 to 40
According to the stoichiometric proportion of the fluorescent powder in the table 1-table 5, the corresponding raw materials of hydrochloride and oxide are accurately weighed and put in a mortar for fully mixing and grinding to obtain a mixture. Heating the mixture to 1200-1400 ℃ in air atmosphere, and keeping the temperature for 2-10 h. And obtaining a sintered product after the furnace temperature is naturally reduced to the room temperature, taking out the sintered product, crushing, washing, sieving and drying the sintered product, obtaining the fluorescent powder corresponding to the embodiments 4-40 according to corresponding sintering parameters, and performing a fluorescence spectrum test on the fluorescent powder, wherein the monitoring wavelength is 650nm, the emission monitoring wavelength is 450nm, and the luminous intensity is specifically shown in tables 1-5.
The composition and luminescence of the raw materials in comparative example and examples 1 to 40 are shown in tables 1 to 5 below.
TABLE 1 examples 1-10
Table 2 examples 11 to 22
TABLE 3 examples 23 to 28
TABLE 4 examples 29 to 36
TABLE 5 examples 37-40
Since numerous limitations are included, no undue redundancy is to be inferred, and equivalents, modifications, and equivalents in the patent claims should be included within the scope and boundaries of the present invention.
As shown in FIG. 1, the XRD diffraction pattern of the invention is shown, and Sr is arranged at the lowest part4Al14O25Standard card (PDF # 74-1810). The diffraction patterns of example 1, example 2 and example 3 were as described above. As can be seen from the figure, the main phase of the sample prepared by the invention is Sr4Al14O25. As can be seen from the above description, the above-described embodiments of the present invention achieve the following technical effects:
as can be seen from Table 1, Mn is associated with the luminescence center in a certain range for the red phosphor4+Increasing the luminous intensity graduallyIncrease, exceed the optimum Mn4+Concentration, the concentration quenching luminescence intensity is gradually reduced due to the increase of luminescence center ions; from examples 1 to 10, over Na+Ions and Sc3+The luminous intensity of the light-emitting diode can be increased by 48 to 100 percent by ion codoping; in addition, the lattice distortion degree can be improved by Y, Lu and La except Sc element, so that the luminous intensity is increased, the Sc element has the best addition effect, and the luminous intensity is increased most.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (9)
1. The red phosphor is characterized in that the composition of the phosphor at least comprises an M element, an A element, a D element and an R element, wherein the M element comprises one or two of Ca, Sr, Ba and Mg; the element A comprises Al or Al and Ga, and also comprises one or two of Sc, Y, Lu and La; the D element is one or two selected from O, N and F, and must contain O; the R element comprises one or two of Mn, Ce and Eu, and must contain Mn; the phosphor has a structure similar to Sr4Al14O25The same crystal structure.
2. The red phosphor of claim 1, wherein the M element further contains one or both of Na and K.
3. The red phosphor of claim 2, wherein the M element contains Na, wherein Na is present in an amount of b in a molar ratio of 2.5% to 25%.
4. According to the claimsThe red phosphor according to claim 1 or 2, wherein the composition formula of the phosphor is M4Ax-aDyaR, wherein the parameters a, x and y satisfy the following conditions: a is more than 0.001 and less than or equal to 1, x is more than or equal to 12 and less than or equal to 16, and y is more than or equal to 24 and less than or equal to 26.
5. The red phosphor of claim 4, wherein the M element is Sr, the A element comprises Al, and further comprises Sc and/or Lu, the D element is O, and the R element is Mn.
6. A red phosphor according to claim 5, wherein the element A is Al and Sc.
7. The red phosphor of claim 6, wherein the mole percentage of Sc element in A element is n, and n is 0.01% to 35%.
8. A light-emitting device comprising a phosphor and an excitation light source, wherein the phosphor comprises the red phosphor according to any one of claims 1 to 7.
9. The light-emitting device according to claim 8, wherein the phosphor further comprises another phosphor comprising (Y, Gd, Lu, Tb)3(Al,Ga)5O12:Ce3+、β-SiAlON:Eu2+、La3Si6N11:Ce3+、(Ba,Sr)Si2O2N2:Eu2+One or more of (a).
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CN114854413A (en) * | 2022-04-08 | 2022-08-05 | 渤海大学 | Matrix luminescent near-infrared fluorescent material without doping activator and preparation method thereof |
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