CN108410453B - Europium-doped single-matrix white-light fluorescent material and preparation method and application thereof - Google Patents
Europium-doped single-matrix white-light fluorescent material and preparation method and application thereof Download PDFInfo
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- 239000011159 matrix material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000001110 calcium chloride Substances 0.000 claims abstract description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 15
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- 239000012190 activator Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a europium-doped single-matrix white-light fluorescent material and a preparation method and application thereof, and relates to the technical field of rare earth luminescent materials. A europium-doped single-matrix white-light fluorescent material with a chemical formula of Ca12A114O33xEu, wherein x is more than or equal to 0.005 and less than or equal to 0.02. The europium-doped single-matrix white fluorescent material can realize white light emission under the excitation of near ultraviolet light. A method for preparing a europium-doped single-matrix white light fluorescent material comprises the following steps: mixing Al (NO)3)3·9H2O、CaCl2Citric acid and Eu (NO)3)3Mixing to prepare gel, and carrying out heat treatment and calcination on the gel to obtain the europium-doped single-matrix white-light fluorescent material. The preparation method has the advantages of low synthesis temperature, convenient operation and high safety.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a europium-doped single-matrix white-light fluorescent material and a preparation method and application thereof.
Background
The white light LED has been primarily applied in the field of solid-state lighting due to the advantages of energy conservation, environmental protection and the like, is a revolution in the history of human lighting, and related industries of the white light LED are important breakthrough openings for dealing with international financial crisis and maintaining stable and rapid development of economy and are also important ways for promoting technical revolution, cultivating emerging industries, promoting energy conservation and emission reduction and dealing with global climate change. At present, the scheme of generating white light based on phosphor light conversion is still the mainstream of the current application and research due to the characteristics of simple process, high efficiency and the like. Although the near ultraviolet LED chip matched with red, green and blue three-primary-color fluorescent powder can provide excellent color uniformity and color rendering index, the luminous efficiency of the device is limited by reabsorption of light among different fluorescent powder and proportion regulation of the light; meanwhile, the luminous intensity of the red powder is far weaker than that of the green powder and the blue powder which are excited at the same time, and the chemical stability and the color purity under the working environment are also to be further improved. Therefore, the development of the novel single-matrix white-light fluorescent powder suitable for the near ultraviolet LED chip is urgent, full-color luminescence is realized in a single matrix, the proportion regulation and control of a fluorescent powder mixture, light reabsorption and asynchronous light decay under long-time work are avoided, and the luminous efficiency and the color reducibility of a device are improved.
At present, the single-matrix white light fluorescent powder is mainly realized by the following ways: one is a single-matrix white light fluorescent powder co-activated by two ions, including Eu2+/Mn2+、Eu2+/Ce3+、Ce3+/Mn2+、Tm3+/Dy3+、Eu3+/Dy3+The isoco-activated single-matrix white fluorescent powder based on energy transfer is very limited in adjusting the luminous color, and most of energy is wasted in the energy transfer process; the other is a single-matrix white light fluorescent powder co-activated by three ions, which comprises Ce3+/Tb3+/Mn2+、Eu2+/Tb3+/Mn2+、Eu2+/Tb3+/Tm3+、Dy3+/Tm3+/Eu3 +And the like, because of the existence of a plurality of different activators, the spectral distribution is difficult to regulate and the difference of the peak intensity ratio is large, and the thermal stability of the material is also reduced. Therefore, the fluorescent powder which adopts single matrix and single active ion to realize white light emission can effectively solve the problem of single matrixThe problem that the spectrum distribution and the peak intensity are difficult to regulate and control is caused by unreasonable proportion of the coactivator white light fluorescent powder.
Disclosure of Invention
The invention aims to provide a europium-doped single-matrix white fluorescent material which can realize white light emission under the excitation of near ultraviolet light.
The invention also aims to provide a preparation method of the europium-doped single-matrix white-light fluorescent material, which has the advantages of low synthesis temperature, convenient operation and high safety.
The invention also aims to provide an application of the europium-doped single-matrix white light fluorescent material in white light LEDs.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a europium-doped single-matrix white-light fluorescent material with a chemical formula of Ca12A114O33xEu, wherein x is more than or equal to 0.005 and less than or equal to 0.02.
A method for preparing a europium-doped single-matrix white light fluorescent material comprises the following steps: mixing Al (NO)3)3·9H2O、CaCl2Citric acid and Eu (NO)3)3Mixing to prepare gel, and carrying out heat treatment and calcination on the gel to obtain the europium-doped single-matrix white-light fluorescent material.
The europium-doped single-matrix white light fluorescent material is applied to white light LEDs.
The europium-doped single-matrix white-light fluorescent material of the embodiment of the invention, and the preparation method and the application thereof have the beneficial effects that:
the invention prepares Eu2+And Eu3+Mixed valence ion co-activated single-matrix white light fluorescent material, Eu2+And Eu3+The single-matrix white-light fluorescent material co-activated by the mixed valence ions avoids a large amount of energy loss caused by an energy transfer system. Using Eu2+4f of65d1→4f7Broadband blue-green emission and Eu generated by transition between energy levels3+Is/are as follows5D0→7FJ(J ═ 0,1,2,3,4) transitions between levels produce linear orange-red light emission, resulting in white light emission. Furthermore, since Eu2+And Eu3+The fluorescent powder system combining the two luminescent characteristics has more flexible and adjustable luminescent properties, thereby meeting some specific requirements in specific practical application.
The preparation method of the europium-doped single-matrix white-light fluorescent material provided by the invention has the advantages of low synthesis temperature, convenience and safety in operation, and no use of CO and H2Reducing gas with equal danger, and preparing Eu directly in air2+And Eu3+White light fluorescent material co-activated by mixed valence ions utilizes reducing atmosphere formed in the combustion process of citric acid to perform Eu excitation3+Non-equivalent substitution of Ca2+Based on that, Eu is further promoted3+Is reduced to Eu2+(ii) a And through reasonably designing process parameters, the Eu is restrained3+Adjusting the degree of self-reduction of Eu2+/Eu3+The proportion of (A) is higher, and more excellent white light emission is obtained. The europium-doped single-matrix white-light fluorescent material prepared by the method has uniform particle size and does not need further ball milling.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below. It is appreciated that the following drawings depict only certain embodiments of the invention and are therefore not to be considered limiting of its scope. For a person skilled in the art, it is possible to derive other relevant figures from these figures without inventive effort.
FIG. 1 is an XRD diffraction pattern of a europium-doped single-matrix white-light fluorescent material provided in example 1 of the present invention;
FIG. 2 is a SEM test result of the europium-doped single-matrix white-light fluorescent material provided in example 1 of the present invention;
FIG. 3 is a fluorescence spectrum of a europium-doped single-matrix white-light fluorescent material provided in example 1 of the present invention;
fig. 4 is a chromaticity diagram of the europium-doped single-host white fluorescent material provided in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The europium-doped single-matrix white-light fluorescent material of the embodiment of the invention, and the preparation method and the application thereof are specifically described below.
The europium-doped single-matrix white-light fluorescent material provided by the embodiment of the invention has a chemical formula of Ca12A114O33xEu, wherein x is more than or equal to 0.005 and less than or equal to 0.02. Further, in a preferred embodiment of the present invention, the europium element represents Eu2+And Eu3+Two valence states.
Eu2+And Eu3+The single-matrix white-light fluorescent material co-activated by the mixed valence ions avoids a large amount of energy loss caused by an energy transfer system. Using Eu2+4f of65d1→4f7Broadband blue-green emission and Eu generated by transition between energy levels3+Is/are as follows5D0→7FJ(J ═ 0,1,2,3,4) transitions between levels produce linear orange-red light emission, resulting in white light emission. Furthermore, since Eu2+And Eu3+The fluorescent powder system combining the two luminescent characteristics has more flexible and adjustable luminescent properties, thereby meeting some specific requirements in specific practical application.
Ca12A114O33Is a wide band gap oxide material with a plurality of lattice sites and can be replaced by ions with proper ionic radius, because of Ca12A114O33The crystal field around the cations of the material is modulated by the anionic groups in the cage and the symmetry of the material is significantly reduced. As can be seen from the comparison of the ionic radii,ca with low symmetry2+Ions with Eu3+Are very similar in ionic radius, so that Eu is3+Ions are readily taken into Ca12A114O33Lattice substitution of Ca2+Two Eu ions, because of different charges, in order to maintain the electrovalence balance of the whole system3+Will substitute for three Ca2+Accompanied by the generation of a hole [ V ]Ca]"and two defects having a positive charge [ EuCa]*Under continuous thermal activation, [ V ]Ca]"two electrons carried by the Eu ions are released and simultaneously emitted to two defects3+Trapped thereby causing Eu to3+Is reduced to Eu2+. At high temperature, Eu will be absorbed although the host material will absorb oxygen from the surrounding environment2+Re-oxidation to Eu3+But Ca12A114O33The crystal structure of (A) is a three-dimensional network structure composed of a close packing of sub-nanometer-sized cages, and such a structure can surround Eu reduced by defects2+Thereby protecting Eu2+So as not to be completely oxidized by the outside air, and the final result of mixed valence Eu ion doping is formed. Meanwhile, Ca is considered12A114O33The skeleton of the rare earth is of a nano structure and is positively charged, which is beneficial to the uniform doping of rare earth ions and the forbidden release of 4f electron transition of the rare earth ions, so that the luminescence of the rare earth ions can be obviously enhanced, and the Eu can be realized3+And Eu2+Good fluorescence emission.
The preparation method of the europium-doped single-matrix white light fluorescent material provided by the embodiment of the invention comprises the following steps:
obtaining Al (NO) in stoichiometric ratio3)3·9H2O、CaCl2Citric acid and Eu (NO)3)3In the examples of the present invention, CaCl2With Eu (NO)3)3The ratio of the number of moles of (a) to (b) is 1:0.005 to 0.02, the number of moles of citric acid to Al (NO)3)3·9H2O、CaCl2And Eu (NO)3)3The ratio of the total moles of (A) is 0.5-2: 1.
Mixing Al (NO)3)3·9H2O、CaCl2Placing the mixture and citric acid in a beaker, adding distilled water and stirring uniformly. Measuring pre-configured Eu (NO)3)3The solution is placed in a beaker and stirred evenly to form transparent sol.
Sealing the beaker, stirring and refluxing for 0.5-2 h while heating on a constant-temperature magnetic stirrer, unsealing, continuously heating on the constant-temperature magnetic stirrer while stirring, and continuously evaporating water until a transparent gel is formed.
And (3) placing the beaker filled with the transparent gel into an electrothermal blowing drying oven, and carrying out heat treatment for 2-4 h at the temperature of 150-200 ℃ to form fluffy precursor powder. And (3) calcining the precursor powder in a rapid-heating box-type resistance furnace at 900-1100 ℃ for 2-4 h in an air atmosphere to obtain the europium-doped single-matrix white-light fluorescent material.
In the preparation method of the europium-doped single-matrix white-light fluorescent material, the synthesis temperature is low, the operation is convenient and safe, and CO and H are not used2Reducing gas with equal danger, and preparing Eu directly in air2+And Eu3+White light fluorescent material co-activated by mixed valence ions utilizes reducing atmosphere formed in the combustion process of citric acid to perform Eu excitation3+Non-equivalent substitution of Ca2+Based on that, Eu is further promoted3+Is reduced to Eu2+(ii) a And through reasonably designing process parameters, the Eu is restrained3+Adjusting the degree of self-reduction of Eu2+/Eu3+The proportion of (A) is higher, and more excellent white light emission is obtained. The europium-doped single-matrix white-light fluorescent material prepared by the method has uniform particle size and does not need further ball milling.
The europium-doped single-matrix white light fluorescent material provided by the invention can realize white light emission under the excitation of near ultraviolet light, and can be used in the field of white light LEDs.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a europium-doped single-matrix white-light fluorescent material with a chemical formula of Ca12A114O330.005Eu, which is mainly prepared by the following steps:
weighing 37.87gAl (NO) as raw material3)3·9H2O、9.6gCaCl2Mixing with 78.98g citric acid, placing in a beaker, adding distilled water, stirring, and measuring 2.16ml pre-prepared 0.2mol/l Eu (NO)3)3Putting the solution into a beaker, uniformly stirring to form transparent sol, sealing the beaker, heating on a constant-temperature magnetic stirrer while stirring and refluxing for 0.5h, unsealing, continuously heating on the constant-temperature magnetic stirrer while stirring, and continuously evaporating water until transparent gel is formed. And then placing the beaker filled with the transparent gel in an electrothermal blowing dry box at 150 ℃ for heat treatment for 4 hours to form fluffy precursor powder. And (3) calcining the precursor powder in a rapid heating box type resistance furnace at 900 ℃ for 2h in an air atmosphere to obtain 10g of europium-doped single-matrix white-light fluorescent material.
Example 2
This example provides a europium-doped single-matrix white-light fluorescent material with a chemical formula of Ca12A114O330.01Eu, which is mainly prepared by the following steps:
weighing 37.87gAl (NO) as raw material3)3·9H2O、9.6gCaCl2Adding 59.37g citric acid into a beaker, adding distilled water, stirring, and measuring 4.33ml pre-prepared 0.2mol/l Eu (NO)3)3Putting the solution in a beaker, uniformly stirring to form transparent sol, sealing the beaker, heating on a constant-temperature magnetic stirrer while stirring and refluxing for 1h, unsealing, continuously heating on the constant-temperature magnetic stirrer while stirring, and continuously evaporating water until transparent gel is formed. And then placing the beaker filled with the transparent gel into an electrothermal blowing dry box at 160 ℃ for heat treatment for 3 hours to form fluffy precursor powder. And (3) calcining the precursor powder in a rapid heating box type resistance furnace at 1000 ℃ for 3h in an air atmosphere to obtain 10g of europium-doped single-matrix white-light fluorescent material.
Example 3
This example provides a europium-doped single radicalA white fluorescent material with a chemical formula of Ca12A114O330.015Eu, which is mainly prepared by the following steps:
weighing 37.87gAl (NO) as raw material3)3·9H2O、9.6gCaCl2Adding 39.67g citric acid into a beaker, adding distilled water, stirring, and measuring 6.49ml pre-prepared 0.2mol/l Eu (NO)3)3Putting the solution into a beaker, uniformly stirring to form transparent sol, sealing the beaker, heating on a constant-temperature magnetic stirrer while stirring and refluxing for 1.5h, unsealing, continuously heating on the constant-temperature magnetic stirrer while stirring, and continuously evaporating water until transparent gel is formed. And then placing the beaker filled with the transparent gel into an electrothermal blowing dry box at 180 ℃ for heat treatment for 2 hours to form fluffy precursor powder. And (3) calcining the precursor powder in a rapid heating box type resistance furnace at 1100 ℃ for 4h in an air atmosphere to obtain 10g of europium-doped single-matrix white-light fluorescent material.
Example 4
This example provides a europium-doped single-matrix white-light fluorescent material with a chemical formula of Ca12A114O330.02Eu, which is mainly prepared by the following steps:
weighing 37.87gAl (NO) as raw material3)3·9H2O、9.6gCaCl2Adding 19.88g citric acid into a beaker, adding distilled water, stirring, and measuring 8.65ml pre-prepared 0.2mol/l Eu (NO)3)3Putting the solution in a beaker, uniformly stirring to form transparent sol, sealing the beaker, heating and stirring for refluxing for 2h on a constant-temperature magnetic stirrer, unsealing, continuously heating and stirring on the constant-temperature magnetic stirrer, and continuously evaporating water until transparent gel is formed. And then placing the beaker filled with the transparent gel in an electrothermal blowing dry box at 200 ℃ for heat treatment for 2 hours to form fluffy precursor powder. And (3) calcining the precursor powder in a rapid heating box type resistance furnace at 1050 ℃ for 3h in air atmosphere to obtain 10g of europium-doped single-matrix white-light fluorescent material.
Test example 1
XRD phase analysis and microstructure test of the europium-doped single-matrix white-light fluorescent material.
Phase composition analysis was performed on the europium-doped single-matrix white-light fluorescent materials provided in examples 1 to 4 with an X-ray diffractometer (XRD, D/Max2500), and microscopic morphology analysis was performed with a scanning electron microscope (SEM, JEOL-6310).
The test results of examples 1-4 were substantially the same, and the test results of example 1 were used as an example for analysis. As can be seen from FIG. 1, the XRD patterns of the prepared powders can be calibrated by using a standard card JCPDS09-0413, and the peak positions of the diffraction peaks respectively correspond to Ca12Al14O33Characteristic diffraction peaks of each crystal face of the phase indicate that the main crystal phases of the prepared samples are Ca12Al14O33Phase, and no peaks of other species phases exist. Shows that Eu enters Ca12Al14O33In the crystal lattice of (1), and Ca is not destroyed12Al14O33The crystal structure of (1). FIG. 2 is a SEM test result of the europium-doped single-matrix white-light fluorescent material provided in example 1, wherein the scanning electron microscope test result shows that the sample has uniform particle size and does not need further ball milling.
Test example 2
And (3) testing the fluorescence spectrum of the europium-doped single-matrix white-light fluorescent material under the excitation of 395nm near ultraviolet light.
The europium-doped single-matrix white-light fluorescent material provided in examples 1 to 4 was subjected to a fluorescence spectrum test under 395nm near ultraviolet excitation by using an F4600 type fluorescence spectrometer, the test wavelength range was 400 to 800nm, the test results of example 1 were taken as an example for analysis, and the test results are shown in FIG. 3.
As can be seen from FIG. 3, the europium-doped single-host white-light phosphor provided in example 1 of the present invention exhibits Eu under 395nm near-UV excitation2+4f of65d1→4f7Broadband blue-green characteristic emission and Eu generated by transition between energy levels3+Is/are as follows5D0→7FJ(J-0, 1,2,3,4) Linear orange-Red light signature generated by transitions between energy levelsAnd (4) shooting.
Test example 3
And (3) analyzing the luminous chromaticity of the europium-doped single-matrix white-light fluorescent material.
Colorimetric analysis was performed on the emission color of the europium-doped single-matrix white-light fluorescent material by using ColorCoordinate software, the color coordinates of the sample were calculated, and the analysis was performed by taking the calculation result of example 1 as an example, and the calculation result is shown in fig. 4.
As can be seen from fig. 4, the color coordinates of the europium-doped single-matrix white fluorescent material provided in example 1 of the present invention are within the white light range.
In summary, in the europium-doped single-matrix white-light fluorescent material provided by the invention, the europium element represents Eu2+And Eu3+Two valence states, using Eu2+Broad band blue-green emission and Eu generation3+The resulting linear orange-red light is emitted, resulting in white light emission. The preparation method of the europium-doped single-matrix white-light fluorescent material provided by the invention has the advantages of low synthesis temperature, convenience and safety in operation, and no use of CO and H2Reducing gas with equal danger, and preparing Eu directly in air2+And Eu3+The white light fluorescent material co-activated by the mixed valence ions has uniform particle size and does not need further ball milling. The europium-doped single-matrix white light fluorescent material provided by the invention can be applied to a white light LED.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments 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.
Claims (5)
1. A preparation method of a europium-doped single-matrix white light fluorescent material is characterized by comprising the following steps: mixing Al (NO)3)3·9H2O、CaCl2Citric acid and Eu (NO)3)3Mixing to prepare gel, and carrying out heat treatment and calcination on the gel to obtain the europium-doped single-matrix white-light fluorescent material;
the gel is subjected to heat treatment at the temperature of 150-200 ℃ for 2-4 h to obtain precursor powder, and then is calcined at the temperature of 900-1100 ℃ for 2-4 h in an air atmosphere;
the chemical formula of the europium-doped single-matrix white light fluorescent material is Ca12A114O33xEu, wherein x is more than or equal to 0.005 and less than or equal to 0.02, and the europium element in the europium-doped single-matrix white-light fluorescent material presents Eu2+And Eu3+Two valence states.
2. The method of claim 1, wherein the gel is prepared by the method comprising:
adding the Al (NO)3)3·9H2O, the CaCl2Mixing the citric acid with a proper amount of water to prepare a mixed solution, and mixing the Eu (NO) prepared in advance3)3Mixing the aqueous solution with the mixed solution, and stirring to form sol; heating the sol to obtain the gel.
3. The method of claim 2, wherein the CaCl is doped with europium to form a single-matrix white light fluorescent material2With said Eu (NO)3)3The molar ratio of (a) to (b) is 1:0.005 to 0.02.
4. The method of claim 2, wherein the molar ratio of the citric acid to the Al (NO) is higher than that of the europium-doped single-matrix white-light emitting phosphor3)3·9H2O, the CaCl2And said Eu (NO)3)3The ratio of the total moles of (A) is 0.5-2: 1.
5. The method of claim 2, wherein the heating the sol comprises: and sealing the sol, stirring and refluxing for 0.5-2 h at constant temperature, unsealing, and continuously stirring at constant temperature to form the gel.
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| JP2004300261A (en) * | 2003-03-31 | 2004-10-28 | Sumitomo Chem Co Ltd | Phosphor |
| CN101812294A (en) * | 2010-03-23 | 2010-08-25 | 东北师范大学 | White light emitting dysprosium-doped dodecacalcium heptaluminate fluorescent powder used for LED and preparation method thereof |
| CN105219382A (en) * | 2015-10-10 | 2016-01-06 | 广西师范学院 | Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application |
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| JP2004300261A (en) * | 2003-03-31 | 2004-10-28 | Sumitomo Chem Co Ltd | Phosphor |
| CN101812294A (en) * | 2010-03-23 | 2010-08-25 | 东北师范大学 | White light emitting dysprosium-doped dodecacalcium heptaluminate fluorescent powder used for LED and preparation method thereof |
| CN105219382A (en) * | 2015-10-10 | 2016-01-06 | 广西师范学院 | Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application |
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| 新型铕锶共掺杂mCaO•nAl2O3荧光粉的制备及其发光机理研究;边虹宇;《中国博士学位论文全文数据库信息科技辑》;20180115(第01期);第26页最后一段，第27页第1段，第29页第3段，图2.5，第38页表2.4 * |
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