CN112646580B - A LaPO4:Ce-coated calcium strontium aluminum europium composite luminescent material and its preparation method and application - Google Patents
A LaPO4:Ce-coated calcium strontium aluminum europium composite luminescent material and its preparation method and application Download PDFInfo
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Abstract
本发明提供了一种LaPO4:Ce包覆钙锶铝铕复合发光材料及其制备方法和应用，属于发光材料技术领域。本发明所述LaPO4:Ce包覆钙锶铝铕复合发光材料包括Ca0.49Sr0.49Al2O4:Eu0.02和包覆于所述Ca0.49Sr0.49Al2O4:Eu0.02表面的磷酸镧铈复合物。本发明采用磷酸镧铈复合物包覆Ca0.49Sr0.49Al2O4:Eu0.02，LaPO4:Ce掺杂后的复合材料可吸收紫外光，并且可以在Ca0.49Sr0.49Al2O4:Eu0.02的吸收光谱范围内发射出相应的光谱，从而实现光谱调节的效果。
The invention provides a LaPO 4 :Ce-coated calcium strontium aluminum europium composite luminescent material and a preparation method and application thereof, belonging to the technical field of luminescent materials. The LaPO 4 :Ce-coated calcium strontium aluminum europium composite luminescent material of the present invention includes Ca 0.49 Sr 0.49 Al 2 O 4 :Eu 0.02 and lanthanum phosphate coated on the surface of the Ca 0.49 Sr 0.49 Al 2 O 4 :Eu 0.02 Cerium complex. In the present invention, lanthanum cerium phosphate composite is used to coat Ca 0.49 Sr 0.49 Al 2 O 4 :Eu 0.02 , the composite material doped with LaPO 4 :Ce can absorb ultraviolet light, and can be in Ca 0.49 Sr 0.49 Al 2 O 4 :Eu The corresponding spectrum is emitted in the absorption spectrum range of 0.02 , so as to realize the effect of spectrum adjustment.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material and the preparation method and the application thereof.
Background
The rare earth luminescence is caused by the 4f electron transition of rare earth with different energy levels. Depending on the excitation, luminescence can be classified into photoluminescence, cathodoluminescence, electroluminescence, radioactivity, X-ray luminescence, triboluminescence, chemiluminescence, and bioluminescence. The rare earth luminescence has the advantages of strong absorption capacity, high conversion efficiency, strong transmission capacity and the like, and can be emitted from an ultraviolet spectrum to an infrared spectrum, particularly in a visible light region. Rare earth luminescent materials have been widely used in displays, new light sources, X-ray intensifying screens, etc., and are gradually expanding into new fields.
However, the existing rare earth luminescent materials are single, and the requirements of multiple anti-counterfeiting technologies put forward further requirements on the luminescent anti-counterfeiting technologies. Therefore, the search for novel luminescent materials becomes an important research direction for expanding the application of the novel luminescent materials in the multiple anti-counterfeiting fields.
Disclosure of Invention
The invention aims to provide a LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material has excellent luminescent performance and can widen the application of the luminescent material in multiple anti-counterfeiting fields.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises Ca0.49Sr0.49Al2O4:Eu0.02And coating said Ca0.49Sr0.49Al2O4:Eu0.02Surface lanthanum cerium phosphate compound.
Preferably, the lanthanum cerium phosphate compound is in LaPO by mol percent4The doping amount of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material is 2-10%.
Preferably, the molar ratio of lanthanum ions to cerium ions in the lanthanum-cerium phosphate composite is 9: 1.
The invention provides the LaPO of the technical scheme4The preparation method of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises the following steps:
mixing strontium nitrate, calcium nitrate, europium nitrate, aluminum nitrate, urea and water to obtain a mixed solution; the molar ratio of the strontium nitrate to the calcium nitrate to the europium nitrate to the aluminum nitrate is 0.49:0.49:0.02: 2;
burning the mixed solution to obtain a calcium-strontium-aluminum-europium compound;
mixing the calcium-strontium-aluminum-europium compound, sodium phosphate, lanthanum nitrate, cerium nitrate and water, and performing aqueous solution synthesis to obtain LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material.
Preferably, the molar ratio of the aluminum nitrate to the urea is 1 (10-20).
Preferably, the combustion temperature is 600 ℃ and the combustion time is 2.5-3.5 min.
Preferably, the molar ratio of the calcium-strontium-aluminum-europium complex to the sodium phosphate is 10: 1.
Preferably, the molar ratio of the calcium-strontium-aluminum-europium complex to the lanthanum nitrate to the cerium nitrate is 10:0.9: 0.1.
Preferably, the temperature of the aqueous solution synthesis is 50 ℃, and the time is 1-3 h.
The invention provides the LaPO of the technical scheme4Ce-coated calcium-strontium-aluminum-europium composite luminescent material or LaPO prepared by the preparation method of the technical scheme4The application of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material in the multiple anti-counterfeiting field.
The invention provides a LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises Ca0.49Sr0.49Al2O4:Eu0.02And coating said Ca0.49Sr0.49Al2O4:Eu0.02Surface lanthanum cerium phosphate compound. In the composite luminescent material provided by the invention, CaO-SrO-Al is formed2O3Co-doped with Eu luminescent material, Eu2+As the ion activation center of the luminescent material, excellent luminescent performance is generated; simultaneously adopts lanthanum-cerium phosphate compound to coat Ca0.49Sr0.49Al2O4:Eu0.02，LaPO4The Ce doped composite material can absorb ultraviolet light and can absorb the ultraviolet light in Ca0.49Sr0.49Al2O4:Eu0.02The corresponding spectrum is emitted in the absorption spectrum range, thereby realizing the effect of spectrum adjustment.
The invention adopts an aqueous solution synthesis method to prepare the LaPO4 Ce-coated calcium-strontium-aluminum-europium composite luminescent material, the method is simple to operate and easy to synthesize, can realize the controllable preparation of the luminescent material, and has important significance for adjusting the physical and chemical properties and expanding the application of the luminescent material in the biological field.
The luminescent material prepared by the invention is an inorganic material, and has advantages in luminescence and preservation compared with the existing organic material (easy to oxidize and difficult to maintain for a long time) for anti-counterfeiting.
Drawings
FIG. 1 shows Ca of comparative example 10.49Sr0.49Al2O4:Eu0.02XRD spectrum of (1);
FIG. 2 shows Ca of samples prepared in examples 1 to 3 and comparative example 10.49Sr0.49Al2O4:Eu0.02XRD pattern of (a);
FIG. 3 shows Ca of samples prepared in examples 1 to 3 and comparative example 10.49Sr0.49Al2O4:Eu0.02The most intense peak XRD pattern of (1);
FIG. 4 shows Ca prepared in comparative example 10.49Sr0.49Al2O4:Eu0.02Emission spectra under different excitation states;
FIG. 5 shows Ca of samples prepared in examples 1 to 3 and comparative example 10.49Sr0.49Al2O4:Eu0.02The emission spectrum of (a);
FIG. 6 is a diagram showing samples of examples 1 to 3 and comparative example 1 under fluorescent lamp irradiation;
FIG. 7 is a graph showing the luminescence state of the samples of examples 1 to 3 and comparative example 1 under the excitation of an ultraviolet lamp at 254 nm;
FIG. 8 is a graph showing the luminescence state of the samples of examples 1 to 3 and comparative example 1 under excitation of an ultraviolet lamp at 365 nm.
Detailed Description
The invention provides a LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises Ca0.49Sr0.49Al2O4:Eu0.02And coating said Ca0.49Sr0.49Al2O4:Eu0.02Of surfacesA lanthanum cerium phosphate composite.
The LaPO provided by the invention4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises Ca0.49Sr0.49Al2O4:Eu0.02. The material is CaO-SrO-Al2O3Co-doped with Eu luminescent material, Eu2+As the ion activation center of the luminescent material, excellent luminescent performance is generated.
The LaPO provided by the invention4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises Ca coated on the Ca0.49Sr0.49Al2O4:Eu0.02Surface lanthanum cerium phosphate compound. In the invention, the lanthanum-cerium-phosphoric acid compound is in LaPO by mol percent4The doping amount of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material is preferably 2-10%, and more preferably 3-8%. In the present invention, the molar ratio of lanthanum ions and cerium ions in the lanthanum-cerium phosphate composite is preferably 9: 1.
The invention provides the LaPO of the technical scheme4The preparation method of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises the following steps:
mixing strontium nitrate, calcium nitrate, europium nitrate, aluminum nitrate, urea and water to obtain a mixed solution; the molar ratio of the strontium nitrate to the calcium nitrate to the europium nitrate to the aluminum nitrate is 0.49:0.49:0.02: 2;
burning the mixed solution to obtain a calcium-strontium-aluminum-europium compound;
mixing the calcium-strontium-aluminum-europium compound, sodium phosphate, lanthanum nitrate, cerium nitrate and water, and performing aqueous solution synthesis to obtain LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material.
The method comprises the steps of mixing strontium nitrate, calcium nitrate, europium nitrate, aluminum nitrate, urea and water to obtain a mixed solution.
In the invention, in order to avoid inaccurate weighing in air environment caused by water absorption of strontium nitrate, the strontium nitrate is used for preparation at present, and the preparation process of the strontium nitrate is preferably strontium carbonate (SrCO)3) Diluting with deionized water, stirring, adding concentrated nitric acid (97 wt.%) to obtain solutionObserving the reaction, stopping adding concentrated nitric acid when NO bubbles appear, heating and stirring at 50 deg.C to obtain strontium nitrate (Sr (NO)3)2) Solid for subsequent preparation. In the present invention, the concentrated nitric acid is mixed with SrCO3The molar ratio of (a) to (b) is preferably 1: 2. The stirring process is not particularly limited in the present invention, and the raw materials can be uniformly mixed according to a process well known in the art.
In the invention, the molar ratio of the strontium nitrate to the calcium nitrate to the europium nitrate to the aluminum nitrate is 0.49:0.49:0.02: 2; the molar ratio of the aluminum nitrate to the urea is preferably 1 (10-20), and more preferably 1: 17.5. The invention has no special limit on the dosage of the water and can ensure that the reaction is carried out smoothly. The urea is used as a combustion agent to promote the combustion reaction; on the other hand, urea is used as a reducing agent, and Eu is used as a reducing agent3+Reduction to Eu2+And the combined action of urea and Sr ensures Eu3+Conversion to Eu2+And will not be oxidized.
After the mixed solution is obtained, the mixed solution is combusted to obtain the calcium-strontium-aluminum-europium compound. In the present invention, the combustion is preferably carried out in a muffle furnace; the combustion temperature is preferably 600 ℃, the combustion time is preferably 2.5-3.5 min, and more preferably 2 minutes and 52 seconds.
After the calcium-strontium-aluminum-europium compound is obtained, the calcium-strontium-aluminum-europium compound, sodium phosphate, lanthanum nitrate, cerium nitrate and water are mixed for aqueous solution synthesis to obtain LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material. In the invention, the molar ratio of the calcium-strontium-aluminum-europium complex to the sodium phosphate is preferably 10: 1; the molar ratio of the calcium-strontium-aluminum-europium compound to the lanthanum nitrate to the cerium nitrate is preferably 10:0.9: 0.1; the water is preferably deionized water; the dosage ratio of the water to the calcium-strontium-aluminum-europium complex is preferably 15mL:0.1 mmol.
In the invention, the process of mixing the calcium-strontium-aluminum-europium complex, the sodium phosphate, the lanthanum nitrate, the cerium nitrate and the water is preferably to mix the calcium-strontium-aluminum-europium complex, the sodium phosphate and the water, stir for 30min, and then add the lanthanum nitrate and the cerium nitrate into the obtained mixture. The process of mixing the calcium-strontium-aluminum-europium complex, the sodium phosphate and the water and the process of stirring are not particularly limited in the invention, and the mixing process can be carried out according to the processes well known in the field.
In the invention, the aqueous solution synthesis process is preferably carried out under stirring conditions, the temperature of the aqueous solution synthesis is preferably 50 ℃, and the time is preferably 1-3 h, and more preferably 3 h. During the synthesis of the aqueous solution, a small amount of deionized water is preferably added according to actual needs to keep stirring normally.
In the aqueous solution synthesis process, lanthanum nitrate, cerium nitrate and phosphate radical form a lanthanum-cerium phosphate compound, and the lanthanum-cerium phosphate compound is coated on the surface of the calcium-strontium-aluminum-europium compound.
After the aqueous solution synthesis is completed, the invention preferably carries out centrifugation, drying and grinding on the obtained materials in sequence to obtain LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material. In the invention, the centrifugation is preferably performed four times, and the time of each centrifugation is preferably 10 min; the rotation speed of the centrifugation is not particularly limited in the invention, and the rotation speed is known in the field; the temperature of the drying is preferably 60 ℃. The process of the present invention is not particularly limited, and may be carried out according to a process known in the art. The invention is to the LaPO4The particle size of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material is not particularly limited, and the particle size of the luminescent material known in the art may be sufficient.
The invention provides the LaPO of the technical scheme4Ce-coated calcium-strontium-aluminum-europium composite luminescent material or LaPO prepared by the preparation method of the technical scheme4The application of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material in the multiple anti-counterfeiting field. The method of the present invention is not particularly limited, and the method may be applied by a method known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
0.49mmol of strontium carbonate (SrCO)3) Diluting with deionized water, stirring, adding 0.98mmol of concentrated nitric acid (mass fraction of 97%), observing reaction, stopping adding concentrated nitric acid when NO bubbles appear, heating and stirring at 50 deg.C to obtain strontium nitrate (Sr (NO) (with NO content of nitric acid)3)2) A solid;
to 0.49mmol Sr (NO)3)2、0.49mmol Ca(NO3)2·4H2O、0.02mmol Eu(NO3) 3·6H2Adding 10mL of deionized water into the O to obtain a first mixed solution;
to 2mmol Al (NO)3)3·9H2Adding 10mL of deionized water into O and 2.2g of urea to obtain a second mixed solution;
adding the first mixed solution into the second mixed solution, putting the obtained solution into a crucible of a muffle furnace, preheating to 600 ℃, and heating for 2 min and 52 sec to obtain a Ca-Sr-Al-Eu complex Ca0.49Sr0.49Al2O4: Eu0.02；
Mixing 0.1mmol of the calcium-strontium-aluminum-europium complex, sodium phosphate (0.01mmol) and 15mL of deionized water, stirring for 30min, adding 0.09mmol of lanthanum nitrate and 0.01mmol of cerium nitrate into the obtained mixture, synthesizing an aqueous solution at 50 ℃ for 1h, centrifuging the obtained product for 4 times, centrifuging for 10min each time, drying at 60 ℃, and grinding to obtain LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material is marked as 1h LaPO4:Ce@Ca0.49Sr0.49Al2O4:Eu0.02The lanthanum cerium phosphate compound is in LaPO4The doping amount of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material is 9 percent.
Example 2
This example differs from example 1 only in that: the time for aqueous solution synthesis is 2h, which is recorded as 2h LaPO4:Ce@Ca0.49Sr0.49Al2O4:Eu0.02。
Example 3
This example differs from example 1 only in that: the time for aqueous solution synthesis is 3h, which is recorded as 3h LaPO4:Ce@Ca0.49Sr0.49Al2O4:Eu0.02。
Comparative example 1
Ca prepared in example 10.49Sr0.49Al2O4:Eu0.02Comparative example 1.
Performance testing
1) Ca of comparative example 10.49Sr0.49Al2O4:Eu0.02XRD testing was performed on the material, and the results are shown in FIG. 1; as shown in FIG. 1, Ca0.49Sr0.49Al2O4:Eu0.02The material has been completely crystallized and has a single structure.
2) XRD testing was performed on the samples of examples 1-3 with Ca of comparative example 10.49Sr0.49Al2O4:Eu0.02Materials for comparison, see figure 2; as can be seen from FIG. 2, Ca in comparative example 10.49Sr0.49Al2O4:Eu0.02There are many narrow peaks, the crystalline state is better, and the peak positions of the samples prepared in examples 1 to 3 are changed, but the peak intensities after the treatment at different time are different, and the peak intensity effect of the sample of example 3 is better, which shows that the crystallization effect is better.
3) XRD test was performed on the samples of examples 1 to 3, and the position of the strongest characteristic peak of XRD was analyzed using Ca of comparative example 10.49Sr0.49Al2O4:Eu0.02Materials for comparison, see figure 3; as can be seen from FIG. 3, Ca in comparative example 10.49Sr0.49Al2O4:Eu0.02The strongest peak was produced at 29.63 ℃ and Ca was found to be present in the samples of examples 1-30.49Sr0.49Al2O4:Eu0.02The characteristic peak of (2) disappears, and the whole appears as a characteristic peak common to both after coating.
4) Ca prepared in comparative example 10.49Sr0.49Al2O4:Eu0.02In different excitation lightThe fluorescence spectrum analysis was performed, and the results are shown in FIG. 4; as can be seen from FIG. 4, Ca0.49Sr0.49Al2O4:Eu0.02The peak positions of the spectra are substantially at the same position, and strong light emission peaks exist around 630nm and 700nm, respectively. Further, Ca0.49Sr0.49Al2O4:Eu0.02The emission is most intense under the excitation spectrum of 254 nm.
5) The samples prepared in examples 1 to 3 were subjected to fluorescence spectrum analysis (excitation wavelength of 254 nm) using Ca of comparative example 10.49Sr0.49Al2O4:Eu0.02For comparison, the results are shown in FIG. 5; as can be seen from fig. 5, the peak positions of the spectra of the respective samples are substantially at the same position, and strong emission peaks exist in the vicinity of 630nm and 700nm, respectively. Furthermore, 3h LaPO prepared in example 34:Ce@Ca0.49Sr0.49Al2O4:Eu0.02The emission is most intense under the excitation spectrum of 254 nm.
6) The samples of examples 1 to 3 and comparative example 1 were irradiated under fluorescent lamp irradiation and ultraviolet lamp light emission characteristics, the samples were placed under a fluorescent lamp, and then irradiated with an ultraviolet lamp and observed for photography, and the results are shown in fig. 6 to 8:
FIG. 6 is a real image of samples of examples 1 to 3 and comparative example 1 under fluorescent lamp irradiation (sample images of comparative example 1, example 2 and example 3 from left to right in this order); as can be seen from FIG. 6, the sample showed no luminescence under the irradiation of the fluorescent lamp.
FIG. 7 is a graph showing the luminescence state of the samples of examples 1 to 3 and comparative example 1 under the excitation of an ultraviolet lamp at 254nm (sample graphs of comparative example 1, example 2 and example 3 in order from left to right); FIG. 8 is a graph showing the luminescence state of the samples of examples 1 to 3 and comparative example 1 under 365nm excitation by an ultraviolet lamp (the sample graphs of comparative example 1, example 2 and example 3 are shown from left to right). As can be seen from fig. 7 and 8, under the excitation condition of the ultraviolet lamp, the sample of comparative example 1 appears yellow-green light, and the samples of examples 1 to 3 appear red light, that is, the yellow-green light before coating in comparative example 1 converts energy, so that the spectral peak positions of the materials coated in examples 1 to 3 are shifted to the red region.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. LaPO4The Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises Ca0.49Sr0.49Al2O4:Eu0.02And coating said Ca0.49Sr0.49Al2O4:Eu0.02Surface lanthanum cerium phosphate compound.
2. LaPO according to claim 14The Ce-coated calcium-strontium-aluminum-europium composite luminescent material is characterized in that the lanthanum-cerium-phosphoric acid composite is coated on LaPO by mol percent4The doping amount of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material is 2-10%.
3. LaPO according to claim 1 or 24The Ce-coated calcium-strontium-aluminum-europium composite luminescent material is characterized in that the molar ratio of lanthanum ions to cerium ions in the lanthanum-cerium phosphate composite is 9: 1.
4. LaPO according to any one of claims 1 to 34The preparation method of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material comprises the following steps:
mixing strontium nitrate, calcium nitrate, europium nitrate, aluminum nitrate, urea and water to obtain a mixed solution; the molar ratio of the strontium nitrate to the calcium nitrate to the europium nitrate to the aluminum nitrate is 0.49:0.49:0.02: 2;
burning the mixed solution to obtain a calcium-strontium-aluminum-europium compound;
mixing the calcium-strontium-aluminum-europium compound, sodium phosphate, lanthanum nitrate, cerium nitrate and water, and performing aqueous solution synthesis to obtain LaPO4Ce-coated calcium-strontium-aluminum-europium composite luminescent material。
5. The preparation method according to claim 4, wherein the molar ratio of the aluminum nitrate to the urea is 1 (10-20).
6. The method according to claim 4, wherein the combustion temperature is 600 ℃ and the combustion time is 2.5-3.5 min.
7. The method of claim 4, wherein the molar ratio of the calcium-strontium-aluminum-europium complex to the sodium phosphate is 10: 1.
8. The preparation method according to claim 4 or 7, wherein the molar ratio of the calcium-strontium-aluminum-europium complex to the lanthanum nitrate to the cerium nitrate is 10:0.9: 0.1.
9. The preparation method according to claim 4, wherein the temperature of the aqueous solution synthesis is 50 ℃ and the time is 1-3 h.
10. LaPO according to any one of claims 1 to 34Ce-coated calcium-strontium-aluminum-europium composite luminescent material or LaPO prepared by the preparation method of any one of claims 4 to 94The application of the Ce-coated calcium-strontium-aluminum-europium composite luminescent material in the multiple anti-counterfeiting field.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2028376A1 (en) * | 1969-06-11 | 1970-12-17 | Matsushita Electronics Corp, , Kadoma, Osaka (Japan) | Phosphor and process for its manufacture |
| JP2001311076A (en) * | 2000-04-26 | 2001-11-09 | Samsung Sdi Co Ltd | Yttrium silicate phosphor using surface coating and method for producing the same |
| DE10122850A1 (en) * | 2001-05-11 | 2002-11-14 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Luminescent composition used for a low pressure discharge lamp contains europium-doped strontium borophosphate and europium-doped strontium aluminate |
| CN108796247A (en) * | 2018-07-11 | 2018-11-13 | 钢研集团稀土科技有限公司 | The minimizing technology of calcium strontium foreign ion in a kind of rare earth feed liquid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2028376A1 (en) * | 1969-06-11 | 1970-12-17 | Matsushita Electronics Corp, , Kadoma, Osaka (Japan) | Phosphor and process for its manufacture |
| JP2001311076A (en) * | 2000-04-26 | 2001-11-09 | Samsung Sdi Co Ltd | Yttrium silicate phosphor using surface coating and method for producing the same |
| DE10122850A1 (en) * | 2001-05-11 | 2002-11-14 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Luminescent composition used for a low pressure discharge lamp contains europium-doped strontium borophosphate and europium-doped strontium aluminate |
| CN108796247A (en) * | 2018-07-11 | 2018-11-13 | 钢研集团稀土科技有限公司 | The minimizing technology of calcium strontium foreign ion in a kind of rare earth feed liquid |
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