CN114479839A - Multi-element rare earth sulfide luminescent material and preparation method thereof - Google Patents
Multi-element rare earth sulfide luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multielement rare earth sulfide luminescent material, which has a chemical expression as shown in formula I: a. theaSr1‑1/2aS is bLn, cM formula I; wherein A is selected from one or more of Li, Na and K, Ln is selected from one or more of Ce, Eu and Dy, M is selected from one or more of Ca, Mg, Cl and Br, a, b and c are A, Ln, and M is taken as the mole percentage coefficient of the corresponding doping ions of the doping ions relative to S atoms. The luminescent material can be excited by ultraviolet light and visible light to emit adjustable spectrum, and can be used in the fields of LED illumination and display. The invention also provides a preparation method of the multi-element rare earth sulfide luminescent material, which is a high-temperature solid-phase synthesis method, has simple process and low raw material cost, and is easy to realize industrialization.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a multi-element rare earth sulfide luminescent material and a preparation method thereof.
Background
Compared with the traditional illuminating light, the white light LED has the advantages of energy conservation, environmental protection, long service life, good color rendering property, good response speed and the like. Regarding energy consumption, the energy consumption of a white light LED is only one tenth of that of an incandescent lamp, and is about one fourth of that of an energy-saving lamp. Therefore, the white light LED is more suitable for illumination in daily life of people and has very great application prospect. At present, the preparation method of the rare earth sulfide luminescent material is limited, the preparation process is complex and difficult, the yield is not high, and the generation and danger of polluted gas are accompanied.
Therefore, improvement needs to be made on the basis of the existing rare earth sulfide luminescent material, and the rare earth sulfide luminescent material which has high luminous efficiency, high color purity, high color rendering index, good luminous stability and easy spectrum regulation is provided.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a multi-element rare earth sulfide luminescent material, which has high luminous efficiency and color purity, and can perform spectrum regulation by regulating rare earth doping.
The second purpose of the invention is to provide a preparation method of the multi-element rare earth sulfide luminescent material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a multi-element rare earth sulfide luminescent material, the chemical expression of which is shown as formula I:
AaSr1-1/2as is bLn, cM formula I;
wherein A is selected from one or more of Li, Na and K, Ln is selected from one or more of Ce, Eu and Dy, and M is selected from one or more of Ca, Mg, Cl and Br;
a is 0 to 0.1, b is 0.001 to 0.2, c is 0 to 0.2, preferably a is 0 to 0.035, b is 0.0005 to 0.04, and c is 0 to 0.035.
In the formula I, A, Ln and M are both doping ions, and a, b and c are mole percentage coefficients of the corresponding doping ions relative to S atoms.
The matrix material of the rare earth visible luminescent material provided by the invention is strontium sulfide, and after the matrix material absorbs energy, the energy is transferred to the visible light luminescent center ion, namely the rare earth ion, and visible light is emitted, so that the visible light luminescent intensity is high, and the luminescent efficiency is high. The experimental results show that: when the rare earth visible luminescent material provided by the invention is excited by 276nm ultraviolet light and 430nm blue-green light, the wavelengths of the maximum emission intensities of the materials are different by doping different rare earth ions. When cerium ions are doped, the wavelength of the maximum emission intensity of the material is respectively positioned around 495 nm; when europium ions are doped, the wavelength of the maximum emission intensity of the material is near 620nm, and the half-peak width reaches 78 nm.
The invention also relates to a preparation method of the multi-element rare earth sulfide luminescent material, which comprises the following steps:
(1) mixing a Sr-containing compound, an A-containing compound, an M-containing compound, a sulfur source and an Ln-containing compound to obtain a first mixture;
(2) wrapping the first mixture with a second mixture, sintering, and removing a wrapping layer to obtain the multi-element rare earth sulfide luminescent material;
the second mixture includes one or more of an a-containing compound, silica, silicate, alumina, zirconia, a sulfur source, carbon powder, and an Ln-containing compound.
Preferably, when the M is selected from one or more of Ca and Mg,
the Sr-containing compound is selected from one or more of Sr-containing carbonate, Sr-containing sulfate, Sr-containing oxalate, Sr-containing acetate and Sr-containing hydroxide;
the A-containing compound is selected from one or more of A-containing carbonate, A-containing sulfide, A-containing oxide and A-containing hydroxide;
the M-containing compound is selected from one or more of M-containing oxide, M-containing carbonate, M-containing oxalate, M-containing nitrate, M-containing sulfate and M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, Ln-containing oxide and Ln-containing sulfate.
Preferably, when M is selected from one or more of Cl and Br,
the Sr-containing compound is selected from one or more of Sr-containing carbonate, Sr-containing sulfate, Sr-containing oxalate, Sr-containing acetate and Sr-containing hydroxide;
the A-containing compound is selected from one or more of A-containing carbonate, A-containing sulfide, A-containing oxide, A-containing hydroxide and A-containing halide;
the M-containing compound is selected from one or more of M-containing oxide, M-containing carbonate, M-containing oxalate, M-containing halide, M-containing nitrate, M-containing sulfate and M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, Ln-containing oxide, Ln-containing sulfate and Ln-containing halide;
at least one of the compound containing A, the compound containing M and the Ln compound is halide.
Preferably, the amount ratio of the Sr-containing compound, the A-containing compound, the M-containing compound, the sulfur source and the Ln-containing compound in the first mixture is (0.95-1): 0-0.1): 0-0.2): 2-3): 0.001-0.2.
Preferably, the amount ratio of the substances containing the A compound, the M compound, the sulfur source and the Ln compound in the second mixture is (0-0.1): 0-0.2): 2-3): 0.001-0.2.
Preferably, the mass ratio of the second mixture to the first mixture is preferably 0.2-5: 1, and more preferably 0.5-4: 1.
The present invention preferably places the first mixture and the second mixture in a crucible for sintering. A portion of the second mixture may be placed in a flat position at the bottom of the crucible, the first mixture may be placed on top of the second mixture, and the remaining second mixture may be placed on top of the first mixture and sintered. According to the invention, the second mixture is used as a wrapping raw material, a wrapping layer is formed during sintering, and the wrapping layer can improve the saturated vapor pressure of the first mixture, accelerate the ion diffusion speed and prevent the first mixture from melting or subliming during the sintering process.
Preferably, the sintering temperature is 600-1500 ℃, more preferably 900-1300 ℃; the sintering time is 1-20h, more preferably 2-4 h; the sintering atmosphere is air atmosphere.
After the sintering is finished, the coating layer of the obtained sintered product is removed. Because the cooled wrapping layers are loose in texture and easy to peel off, the upper wrapping layer and the lower wrapping layer can be removed by pinching with bare hands. And grinding the sintered product without the coating layer to obtain the multi-element rare earth sulfide luminescent material.
The luminescent material can be excited by ultraviolet light and visible light to emit adjustable spectrum, and can be used in the fields of LED illumination and display.
The invention has the beneficial effects that:
the invention provides a multielement rare earth sulfide luminescent material, which has a chemical expression as shown in formula I: a. theaSr1-1/ 2aS is bLn, cM formula I; wherein A is selected from one or more of Li, Na and K, Ln is selected from one or more of Ce, Eu and Dy, M is selected from one or more of Ca, Mg, Cl and Br, a, b and c are A, Ln, and M is taken as the mole percentage coefficient of the corresponding doping ions of the doping ions relative to S atoms. The luminescent material can be excited by ultraviolet light and visible light to emit adjustable spectrum, and can be used in the fields of LED illumination and display.
The invention also provides a preparation method of the multi-element rare earth sulfide luminescent material, which is a high-temperature solid-phase synthesis method, has simple process and low raw material cost, and is easy to realize industrialization.
Drawings
FIG. 1 shows Na0.24Sr0.88XRD data for 0.005Ce,0.01 Mn.
FIG. 2 shows Na0.28Sr0.86S is the excitation spectrum and the emission spectrum of 0.01 Ce.
FIG. 3 is Li0.6Sr0.7S is the excitation spectrum and the emission spectrum of 0.01Eu and 0.001 Ca.
FIG. 4 shows sample Na0.28Sr0.86S0.01 Ce and Li0.6Sr0.7S is 0.01Eu and 0.001Ca, and the fluorescence spectrum of the LED is encapsulated.
FIG. 5 shows the excitation spectrum and emission spectrum of SrS 0.01Eu,0.01Ce, and 0.01 Ca.
FIG. 6 is K0.16Sr0.92S is a shape image of 0.02Cu and 0.01 Al.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
According to the chemical formula Na0.24Sr0.880.005Ce and 0.01Mn, accurately weighing sodium carbonate, strontium oxide, cerium oxide and manganese oxide, mixing well, and adding Al2O3Sulfur powder and carbon particles as a coating layer. Al mentioned above2O3The mass ratio of the sulfur powder to the carbon particles is 0.01:1:0.5, and the mass ratio of the mixture of the sodium carbonate, the strontium oxide, the cerium oxide and the manganese oxide to the coating layer is 1:1. Sintering in air at 1300 ℃ for 2 hours, cooling to room temperature, taking out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material. The phase structure of the rare earth sulfide luminescent material obtained by the invention is tested by using an Empyrean X-ray powder diffractometer, and the test result is shown in figure 1. Fig. 1 is an X-ray diffraction spectrum of the visible light emitting material prepared in example 1 of the present invention. As can be seen from fig. 1, the main phase of the luminescent material prepared in example 1 of the present invention is SrS.
Example 2
According to the chemical formula Na0.28Sr0.86S is 0.01Ce, sodium carbonate, strontium carbonate and cerium carbonate are accurately weighed and mixed uniformly, and ZrO is added2Sulfur powder and carbon particles as a coating layer, the above-mentioned ZrO2The mass ratio of the sulfur powder to the carbon particles is 0.01:1:0.4, and the mass ratio of the mixture of the sodium carbonate, the strontium carbonate and the cerium carbonate to the coating layer is 1: 0.5. Sintering the mixture for 2 hours at 900 ℃ in the air, cooling the mixture to room temperature, taking the mixture out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared in the embodiment 2 of the invention is SrS.
The obtained rare earth sulfide luminescent material is subjected to fluorescence spectrum test by using Edinburgh FLS980, as shown in FIG. 2. When the rare earth sulfide luminescent material is excited by 276nm ultraviolet light, the wavelength of the maximum emission intensity of the rare earth sulfide luminescent material is positioned near 495 nm; with green emission of 536nm, the intensities of the maximum excitation intensities of the rare earth sulfide luminescent materials were located near 275nm and 430nm, respectively.
Example 3
According to the formula Li0.6Sr0.7S is the ratio of the substance amount of each element in 0.01Eu and 0.001Ca, lithium hydroxide, strontium sulfate, europium oxide and calcium oxide are accurately weighed and mixed evenly, and SiO is used2Sulfur powder and carbon particles as a coating layer, the above SiO2The mass ratio of the sulfur powder to the carbon particles is 0.02:1:0.5, and the mass ratio of the mixture of the lithium hydroxide, the strontium sulfate, the europium oxide and the calcium oxide to the coating layer is 1: 2. Sintering in air at 1050 ℃ for 2 hours, cooling to room temperature, taking out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared in the embodiment 3 of the invention is SrS.
The obtained rare earth sulfide luminescent material is subjected to fluorescence spectrum test by using Edinburgh FLS980, as shown in FIG. 3. When the rare earth sulfide luminescent material is excited by adopting blue light with the wavelength of 430nm, the wavelength of the maximum emission intensity of the rare earth sulfide luminescent material is positioned near 620nm, and the half-peak width reaches 78 nm; when 617nm red light emission is adopted, the intensity of the maximum excitation intensity of the rare earth sulfide luminescent material is respectively positioned near 275nm and 430 nm.
The invention uses distant HAAS-2000 to test the chromaticity and luminosity index of the LED device on the obtained rare earth sulfide luminescent material, as shown in figure 4. The invention adopts organic silica gel:Na0.28Sr0.86S:0.01Ce:Li0.6Sr0.7s:0.01Eu,0.001 Ca: 10:1:2 by mass ratio, and coated on a 430nm blue chip, and tested after curing at 100 ℃ for 1 hour. In FIG. 4, the peak position around 430nm is attributed to the blue chip; the peak position near 490-550 nm is classified as Na0.28Sr0.86S is 0.01 Ce; the peak position around 640nm is attributed to Li0.6Sr0.7S:0.01Eu,0.001Ca。
Example 4
Accurately weighing strontium carbonate, europium oxide, cerium carbonate and calcium hydroxide according to the proportion of the substances of each element in the chemical formula SrS of 0.01Eu,0.01Ce and 0.01Ca, fully and uniformly mixing, and then using CaSiO3Sulfur powder and carbon particles as a coating layer, the CaSiO3The mass ratio of the sulfur powder to the carbon particles is 0.015:1:0.6, and the mass ratio of the mixture of strontium carbonate, europium oxide, cerium carbonate and calcium hydroxide to the coating layer is 1: 3. Sintering in air at 1000 ℃ for 2 hours, cooling to room temperature, taking out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared in the embodiment 4 of the invention is SrS.
The obtained rare earth sulfide luminescent material is subjected to fluorescence spectrum test by using Edinburgh FLS980, as shown in FIG. 5. When the invention is excited by blue light with the wavelength of 430nm, the wavelength of the maximum emission intensity of the rare earth sulfide luminescent material is near 480nm and 620 nm; when 617nm red light emission is adopted, the intensity of the maximum excitation intensity of the rare earth sulfide luminescent material is respectively positioned near 275nm and 430 nm.
Comparative example 1
According to the chemical formula Na0.44Sr0.78S is 0.01Cr and 0.002Ca, sodium hydroxide, strontium carbonate, chromium sulfate and calcium sulfate are accurately weighed and mixed uniformly, and ZrO is added2Sulfur powder and carbon powder as coating layer, and the above-mentioned ZrO2The mass ratio of the sulfur powder to the carbon particles is 0.02:1:0.45, and the mass ratio of the mixture of sodium hydroxide, strontium carbonate, chromium sulfate and calcium sulfate to the coating layer is 1: 1.5. Sintering in air at 1300 ℃ for 2 hours, cooling to room temperature, taking out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared in comparative example 1 is SrS.
Comparative example 2
Accurately weighing strontium sulfate, copper oxide and calcium hydroxide according to the mass ratio of each element in the chemical formula SrS:0.015Cu and 0.05Ca, fully and uniformly mixing, and adding Al2O3Sulfur powder and carbon particles as a coating layer, and the Al2O3The mass ratio of the sulfur powder to the carbon particles is 0.005:1:0.4, and the mass ratio of the mixture of the strontium sulfate, the copper oxide and the calcium hydroxide to the coating layer is 1: 2. Sintering the mixture for 2 hours at 1200 ℃ in the air, cooling the mixture to room temperature, taking the mixture out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared in comparative example 2 is SrS.
Comparative example 3
According to the chemical formula K0.16Sr0.92S is 0.02Cu,0.01Al, potassium carbonate, strontium oxide, copper sulfate and aluminum oxide are accurately weighed and mixed uniformly, and sulfur powder and carbon particles are used as a coating layer, wherein the mass ratio of the sulfur powder to the carbon particles is 1:0.45, and the mass ratio of the mixture of the potassium carbonate, the strontium oxide, the copper sulfate and the aluminum oxide to the coating layer is 1: 3. Sintering in air at 1000 deg.C for 2 hr, cooling to room temperature, taking out, removing coating layer, and grinding to obtain rare earth sulfide luminescent materialAnd (4) feeding.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared by comparative example 3 is SrS.
The obtained rare earth sulfide luminescent material is subjected to morphology image test by using a JSM-7900F type field emission scanning electron microscope, as shown in FIG. 6. FIG. 6 is a morphology image of a sulfide luminescent material prepared in comparative example 3 of the present invention, and it can be seen from FIG. 6 that the powder prepared in comparative example 3 of the present invention has an irregular shape and a particle size of 5 to 30 μm.
Comparative example 4
According to the chemical formula K0.4Sr0.8S0.80.4Cl and 0.1Mn, namely accurately weighing potassium chloride, strontium carbonate and manganese oxide, fully mixing the components, and then using SiO to prepare a mixture2Sulfur powder and carbon particles as a coating layer, the above SiO2The mass ratio of the sulfur powder to the carbon particles is 0.02:1:0.6, and the mass ratio of the mixture of potassium chloride, strontium carbonate and manganese oxide to the coating layer is 1:1. Sintering the mixture for 2 hours at 1500 ℃ in the air, cooling the mixture to room temperature, taking the mixture out, removing the coating layer, and fully grinding the sintered product without the coating layer to obtain the rare earth sulfide luminescent material.
The phase structure of the obtained rare earth sulfide luminescent material is tested by using an Empyrean X-ray powder diffractometer, the X-ray diffraction pattern of the rare earth sulfide luminescent material is similar to that of figure 1, and the main phase of the luminescent material prepared in the embodiment 8 of the invention is SrS.
The multi-element rare earth sulfide luminescent material provided by the invention has higher luminous intensity and luminous efficiency. When the material is excited by ultraviolet light and visible light with different wavelengths, the wavelength of the maximum emission intensity of the material is different when different rare earth ions are doped. Taking doped europium ion as an example, the wavelength of the maximum emission intensity of the material is near 620nm, and the half-peak width reaches 78 nm. Most red phosphors, such as manganese-based materials, have a half-peak width of no more than 10 nm. The red fluorescent powder plays roles in adjusting color temperature, improving color rendering and color saturation in the white light LED device, and can realize illumination and display of wide color gamut.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A multi-element rare earth sulfide luminescent material is characterized in that the chemical expression is shown as formula I:
AaSr1-1/2as is bLn, cM formula I;
wherein A is selected from one or more of Li, Na and K, Ln is selected from one or more of Ce, Eu and Dy, and M is selected from one or more of Ca, Mg, Cl and Br;
a＝0～0.1，b＝0.001～0.2，c＝0～0.2。
2. the multi-element rare earth sulfide luminescent material as claimed in claim 1, wherein a is 0 to 0.035, b is 0.0005 to 0.04, and c is 0 to 0.035.
3. The method for preparing a multiple rare earth sulfide luminescent material according to claim 1 or 2, wherein the method comprises the steps of:
(1) mixing a Sr-containing compound, an A-containing compound, an M-containing compound, a sulfur source and an Ln-containing compound to obtain a first mixture;
(2) wrapping the first mixture with a second mixture, sintering, and removing a wrapping layer to obtain the multi-element rare earth sulfide luminescent material;
the second mixture includes one or more of an a-containing compound, silica, a silicate, alumina, zirconia, a sulfur source, carbon powder, and an Ln-containing compound.
4. The method according to claim 3, wherein when M is one or more selected from Ca and Mg,
the Sr-containing compound is selected from one or more of Sr-containing carbonate, Sr-containing sulfate, Sr-containing oxalate, Sr-containing acetate and Sr-containing hydroxide;
the A-containing compound is selected from one or more of A-containing carbonate, A-containing sulfide, A-containing oxide and A-containing hydroxide;
the M-containing compound is selected from one or more of M-containing oxide, M-containing carbonate, M-containing oxalate, M-containing nitrate, M-containing sulfate and M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, Ln-containing oxide and Ln-containing sulfate.
5. The method according to claim 3, wherein when M is one or more selected from Cl and Br,
the Sr-containing compound is selected from one or more of Sr-containing carbonate, Sr-containing sulfate, Sr-containing oxalate, Sr-containing acetate and Sr-containing hydroxide;
the A-containing compound is selected from one or more of A-containing carbonate, A-containing sulfide, A-containing oxide, A-containing hydroxide and A-containing halide;
the M-containing compound is selected from one or more of M-containing oxide, M-containing carbonate, M-containing oxalate, M-containing halide, M-containing nitrate, M-containing sulfate and M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, Ln-containing oxide, Ln-containing sulfate and Ln-containing halide;
at least one of the compound containing A, the compound containing M and the Ln compound is halide.
6. The method according to claim 3, wherein the first mixture contains the Sr-containing compound, the A-containing compound, the M-containing compound, the sulfur source and the Ln-containing compound in an amount of (0.95-1): 0-0.1): 0-0.2): 2-3): 0.001-0.2.
7. The method of claim 3, wherein the amount ratio of the A-containing compound, the M-containing compound, the sulfur source and the Ln-containing compound in the second mixture is (0-0.1): (0-0.2): (2-3): (0.001-0.2).
8. The preparation method according to claim 3, wherein the mass ratio of the second mixture to the first mixture is 0.2-5: 1.
9. The preparation method according to claim 8, wherein the mass ratio of the second mixture to the first mixture is 0.5-4: 1.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2108355C1 (en) * | 1997-01-17 | 1998-04-10 | Институт неорганической химии СО РАН | Inorganic pigment on the base of sulfide of metal and method for its production |
| CN1202513A (en) * | 1997-06-12 | 1998-12-23 | 肖志国 | Long persistence luminous sulfide material and producing method |
| WO2002011173A1 (en) * | 2000-07-28 | 2002-02-07 | Osram Opto Semiconductors Gmbh | Luminescence conversion based light emitting diode and phosphors for wavelength conversion |
| WO2008111878A2 (en) * | 2007-03-09 | 2008-09-18 | Victor Andreevich Vorobiev | Light-converting material and a composition for the production thereof |
| WO2011083885A1 (en) * | 2010-01-06 | 2011-07-14 | 금호전기주식회사 | Oxysulfide-based red phosphor, and white led and led package using same |
| CN109054811A (en) * | 2018-08-01 | 2018-12-21 | 东台市天源光电科技有限公司 | Sulfide red fluorescent powder and preparation method thereof and the light emitting device for using the fluorescent powder |
-
2022
- 2022-02-23 CN CN202210167593.5A patent/CN114479839B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2108355C1 (en) * | 1997-01-17 | 1998-04-10 | Институт неорганической химии СО РАН | Inorganic pigment on the base of sulfide of metal and method for its production |
| CN1202513A (en) * | 1997-06-12 | 1998-12-23 | 肖志国 | Long persistence luminous sulfide material and producing method |
| WO2002011173A1 (en) * | 2000-07-28 | 2002-02-07 | Osram Opto Semiconductors Gmbh | Luminescence conversion based light emitting diode and phosphors for wavelength conversion |
| WO2008111878A2 (en) * | 2007-03-09 | 2008-09-18 | Victor Andreevich Vorobiev | Light-converting material and a composition for the production thereof |
| WO2011083885A1 (en) * | 2010-01-06 | 2011-07-14 | 금호전기주식회사 | Oxysulfide-based red phosphor, and white led and led package using same |
| CN109054811A (en) * | 2018-08-01 | 2018-12-21 | 东台市天源光电科技有限公司 | Sulfide red fluorescent powder and preparation method thereof and the light emitting device for using the fluorescent powder |
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