CN102604635B - Zirconium-phosphate-based luminescent material, preparation method thereof, and application thereof - Google Patents
Zirconium-phosphate-based luminescent material, preparation method thereof, and application thereof Download PDFInfo
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- CN102604635B CN102604635B CN201210017384.9A CN201210017384A CN102604635B CN 102604635 B CN102604635 B CN 102604635B CN 201210017384 A CN201210017384 A CN 201210017384A CN 102604635 B CN102604635 B CN 102604635B
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Abstract
The invention discloses a zirconium-phosphate-based luminescent material, a preparation method thereof, and an application thereof. The chemical formula of the luminescent material is M7-7xEu7xZr(PO4)6, wherein M is Sr<2+> or Ba<2+>, x is the dopant amount of Eu<3+>, and x is no smaller than 0 and no greater than 0.5. The luminescent material is prepared by using a high-temperature solid-phase method or a chemical solvent method. The luminescent material provided by the invention can be adopted as a fluorescent material with vacuum ultraviolet VUV and ultraviolet as excitation sources, and can also be used in light emitting diodes, displaying materials, three-primary-color fluorescent lamps, and field emission displays. The luminous intensity of the luminescent material is adjustable, the preparation technology of the luminescent material is simple, the operation is safe and convenient, and the raw materials are cheap and easy to obtain. The method is suitable for scaled productions. Generally, no three-waste is produced during a reaction process. Therefore, the invention assists in establishing a green, environment-friendly, low-energy-consumption, and high-benefit industry.
Description
Technical field
The present invention relates to a kind of zirconium phosphate base luminescent material, preparation method and application thereof, particularly a kind of zirconium phosphate base luminescent material of alkali doped ion, belongs to fluorescent material technical field.
Background technology
The fast development of science and technology has promoted the application of fluorescent material in every field greatly: fluorescent material with three basic colour and white light LEDs for the conventional fluorescent of lighting field; Show and video picture field cathode tube, plasma flat-screen televisions and LED large screen display; The field of nuclear medicine computer CT, SPECT, PET imaging, luminescent material constantly shows its unique advantage.Issue < < medium-term and long-term scientific and technical development program outline (2020) the > > of country of State Council, wherein using large size flat-panel monitor as the problem of first developing, and phosphor becomes the key that realizes this technology.At present commercial various phosphors in various degree exist luminous efficiency low, purity of color is poor, the capable shortcoming such as poor of chemically stable.Therefore, exploitation has the luminescent material of application prospect and improves constantly its performance significant.
Follow the exploitation of novel material system, investigator has been noted that PO
4, ZrO
2and Zr (PO
4)
6group's compound ion luminescence center, can effectively absorb UV-light and vacuum-ultraviolet light, and Energy Efficient is passed to rare earth ion.As: YPO
4: Eu
3+in the efficient red emission of vacuum ultraviolet-excited lower generation, can be used for plasma flat and show red fluorescence material; CaZr (PO
4)
2: Tb
3+at 172nm, excite lower transmitting peak position in 543nm, can be used for PDP green fluorescent material.The excellent vacuum ultraviolet (VUV) luminosity having for zirconium phosphoric acid salt starts extensive concern.The investigator of various countries has mainly launched the research for zirconium phosphoric acid salt luminosity beyond paying close attention to the phosphatic fast-ionic conductor character of zirconium.Exploitation multifunction obtains the inexorable trend that material is following Materials, and a lot of materials are all not only applied in a field, as NaZr (PO
4)
3be a kind of good fast ion conducting material, pass through rare earth ion dopedly simultaneously, this material is also a kind of vacuum ultraviolet-excited luminescent material with application potential.Therefore, exploitation raw materials cost is low, and preparation method is simple, integrates several functions, and luminescent spectrum is regulatable novel excellent luminescent material system within the specific limits, and to improving China's independent intellectual property right level, creating great economic benefit has Great significance.
Summary of the invention
The object of the present invention is to provide a kind of luminous intensity adjustable, zirconium phosphate base luminescent material of the simple and environmental protection of preparation technology and its preparation method and application, for this area increases class new variety, promotes the widespread use of phosphor.
For achieving the above object, the technical solution used in the present invention provides a kind of zirconium phosphate base luminescent material, and its chemical formula is
m 7-7xeu
7xzr (PO
4)
6, wherein,
mfor divalent alkaline-earth metal ion strontium ion Sr
2+or barium ion Ba
2+in a kind of;
xtrivalent europium ion Eu
3+doping, 0≤x≤0.5.
A preparation method for zirconium phosphate base luminescent material, adopts high temperature solid-state method, comprises the steps:
(1) press chemical formula M
7-7xeu
7xzr (PO
4)
6the stoichiometric ratio of middle corresponding element takes raw material, and described raw material is alkali metal containing ion
mcompound,
mfor divalent alkaline-earth metal ion strontium ion Sr
2+or barium ion Ba
2+in a kind of, containing europium ion Eu
3+compound, zirconium dioxide and contain phosphonium ion P
5+compound, 0≤x≤0.5, grinds and mixes, and obtains mixture;
(2) mixture is placed in to alumina crucible, in retort furnace, synthesizes, sintering temperature is at 900～1500 ℃, and soaking time is greater than 5 hours, obtains a kind of zirconium phosphate base luminescent material after cooling.
A preparation method for zirconium phosphate base luminescent material, adopts chemical solution method, comprises the steps:
(1) will be by formula M
7-7xeu
7xzr (PO
4)
6the stoichiometric ratio of middle corresponding element takes containing europium ion Eu
3+compound dissolution in dilute nitric acid solution or distilled water, then add the complexing agent complexing europium ion Eu of appropriate stoichiometric ratio
3+; Europium ion Eu
3+with the mol ratio of complexing agent be 1:1; Described complexing agent is citric acid or ethylenediamine tetraacetic acid (EDTA);
(2) by formula M
7-7xeu
7xzr (PO
4)
6middle corresponding element stoichiometric ratio takes eight hydration zirconium oxychlorides, and water-soluble solution obtains clear solution, then adds the complexing agent complexing zirconium ion of appropriate stoichiometric ratio; The mol ratio of zirconium ion and complexing agent is 1:2; Described complexing agent is citric acid or ethylenediamine tetraacetic acid (EDTA);
(3) will be by formula M
7-7xeu
7xzr (PO
4)
6the compound dissolution that the stoichiometric ratio of middle corresponding element takes alkali metal containing ion M obtains clear solution in water or rare nitric acid;
mfor divalent alkaline-earth metal ion strontium ion Sr
2+or barium ion Ba
2+in a kind of;
(4) solution that mixing step (1), (2) and (3) obtain, is uniformly mixed;
(5) add formula M
7-7xeu
7xzr (PO
4)
6the stoichiometric ratio of middle corresponding element containing phosphonium ion P
5+in the mixing solutions that 4. compound obtains in step, stir and form solution;
(6) the resulting solution of step (5) is dried and formed gel, reheat and obtain aerogel, the aerogel obtaining is ground, obtain precursor powder;
(7) precursor powder step (6) being obtained is placed in alumina crucible, in retort furnace, synthesizes, and first temperature is risen to 200～500 ℃, and insulation is greater than 2 hours; Continue to be warming up to 800～1100 ℃, insulation is greater than 2 hours; Finally be warming up to 1200～1400 ℃, insulation is greater than 3 hours; After cooling, obtain a kind of zirconium phosphate base luminescent material.
Described alkali metal containing ion
mcompound be
moxide compound,
mcarbonate,
mone or more combination of nitrate.
Described containing europium ion Eu
3+compound be a kind of in europium sesquioxide, europium nitrate, or their combination.
Described phosphorous compound is a kind of in primary ammonium phosphate or Secondary ammonium phosphate, or their combination.
Described luminescent material is as take the fluorescent material that vacuum-ultraviolet light VUV and UV-light be excitaton source.
Described luminescent material is as in photodiode, display material, three-color fluorescent lamp or Field Emission Display.
Measuring result demonstration, the feature of zirconium phosphate base luminescent material provided by the invention is: work as formula M
7-7xeu
7xzr (PO
4)
6in,
x=0 o'clock, Sr
7zr (PO
4)
6be good self-activate luminescence material, luminous is broadband emission, and luminous peak position, in 470 nm left and right, has good absorption in vacuum ultraviolet (VUV) region and ultraviolet region, can be luminous for vacuum ultraviolet (VUV) or burst of ultraviolel; Ba
7zr (PO
4)
6glow peak is positioned at 500 nm left and right, in vacuum ultraviolet (VUV) or ultraviolet region, has good absorption, can be luminous for vacuum ultraviolet (VUV) or burst of ultraviolel;
Work as formula M
7-7xeu
7xzr (PO
4)
6 middle 0<x≤0.5 o'clock, along with Eu
3+concentration increases, and luminous highest peak position is all positioned at 613nm, and luminous intensity is high, can be applied as good orange luminescent material.Therefore zirconium phosphate base luminescent material of the present invention can be applicable in photodiode, display material, three-color fluorescent lamp and Field Emission Display.
The luminescence mechanism of zirconium phosphate luminescent material of the present invention is mainly divided into following two kinds:
1. work as formula M
7-7xeu
7xzr (PO
4)
6during middle x=0, Sr
7zr (PO
4)
6luminous be a kind of self-trapping exciton luminescent material, be with PO
4and ZrPO
4as luminescence center, at 150nm, there is wide band absorption, under room temperature condition, launch peak position at the blue light of 470nm left and right.
2. work as formula M
7-7xeu
7xzr (PO
4)
6 middle 0<x≤0.5 o'clock, M
7-7xeu
7xzr (PO
4)
6eu
3+the luminescent material that doping obtains, luminescence center is by PO
4and Zr (PO
4)
6to Eu
3+ion energy transmits, simultaneously Eu
3+the electronic level of ion intrinsic also absorbs the light of specific wavelength.So the wide band absorption that the excitation spectrum of such material comprises substrate material luminophore and Eu
3+f-f characteristic absorbance.Luminous highest peak position is all positioned at 613nm, and luminous intensity is high, can be applied as good orange luminescent material.
Compared with prior art, zirconium phosphate base luminescent material of the present invention has the following advantages:
1, substrate material Sr
7zr (PO
4)
6be good self-activate luminescence material, for the luminous peak position of broadband emission is at 470-500nm, in vacuum ultraviolet (VUV) region and ultraviolet region, have good absorption, can be luminous for vacuum ultraviolet (VUV) or burst of ultraviolel.
2, Eu
3+the M of doping
7-7xeu
7xzr (PO
4)
6luminous highest peak position is all positioned at 613nm, and luminous intensity is high, can be applied as good orange luminescent material.
3, zirconium phosphate base luminescent material luminous intensity of the present invention is adjustable, preparation technology is simple, operational safety is reliable, raw material is cheap and easy to get, is suitable for large-scale production, and reaction process produces without the technique three wastes, belongs to environmental protection, less energy-consumption, high benefit industry.
Accompanying drawing explanation
Fig. 1 is the Sr that the embodiment of the present invention 1 makes
7zr (PO
4)
6the X-ray powder diffraction collection of illustrative plates of sample and the comparison of standard card PDF#29-0407;
Fig. 2 is the Sr that the embodiment of the present invention 1 makes
7zr (PO
4)
6sample is monitored the exciting light spectrogram that 470nm obtains at ambient temperature;
Fig. 3 is the made Sr of the embodiment of the present invention 1
7zr (PO
4)
6sample excites the emmission spectrum obtaining at 146nm;
Fig. 4 is the Sr that the embodiment of the present invention 2 makes
6.65eu
0.35zr (PO
4) the sample excitation spectrum and the utilizing emitted light spectrogram that monitor at ambient temperature;
Fig. 5 is the Sr that the embodiment of the present invention 3 makes
5.6eu
1.4zr (PO
4)
6the excitation spectrum that sample monitors at ambient temperature and utilizing emitted light spectrogram;
Fig. 6 is the Ba that the embodiment of the present invention 4 makes
7zr (PO
4)
6the X-ray powder diffraction collection of illustrative plates of sample and the comparison of standard card PDF#29-0407;
Fig. 7 is the Ba that the embodiment of the present invention 4 makes
7zr (PO
4)
6the excitation spectrum that sample monitors at ambient temperature and utilizing emitted light spectrogram;
Fig. 8 is the Ba that the embodiment of the present invention 5 makes
6.51eu
0.49zr (PO
4)
6the excitation spectrum that sample monitors at ambient temperature and utilizing emitted light spectrogram.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
According to chemical formula Sr
7zr (PO
4)
6in the stoichiometric ratio of each element, take respectively SrCO
3: 5.1671 grams, ZrO
2: 0.6161 gram, NH
4h
2pO
4: 3.451 grams.In agate mortar, grind, and fully mix.The powder mixing is calcined for the first time under air atmosphere, and temperature is 350 ℃, and insulation 2h, takes out sample after being naturally cooled to room temperature.The powder of calcining for the first time is again fully ground in agate mortar, carry out sintering for the second time under air atmosphere, temperature is 1000 ℃,, insulation 5h, naturally cools to room temperature.Process before repeating, carries out final sintering again, and temperature is 1300 ℃, and insulation 8h naturally cools to room temperature and obtains ultimate aim product.
Fig. 1 is the Sr that the present embodiment makes
7zr (PO
4)
6the X-ray powder diffraction collection of illustrative plates of sample and the comparison of standard card PDF#29-0407.As seen from Figure 1, the prepared Sr of the present embodiment
7zr (PO
4)
6it is pure phase.
Fig. 2 and Fig. 3 are respectively the Sr that the present embodiment makes
7zr (PO
4)
6the excitation spectrum that sample monitors at ambient temperature and utilizing emitted light spectrogram.From Fig. 2 and Fig. 3: the prepared Sr of the present embodiment
7zr (PO
4)
6material is a kind of self-excitation blue light emitting material, and transmitting peak position, in 470nm left and right, is a kind of good blue VUV fluorescent material.
Embodiment 2
According to chemical formula Sr
6.65eu
0.35zr (PO
4)
6in the stoichiometric ratio of each element, take respectively Eu
2o
3: 0.308 gram, SrCO
3: 4.909 grams, ZrO
2: 0.6161 gram, NH
4h
2pO
4: 3.451 grams.In agate mortar, grind, and fully mix.The powder mixing is calcined for the first time under air atmosphere, and temperature is 350 ℃, and insulation 2 ~ 10h, takes out sample after being naturally cooled to room temperature.The powder of calcining for the first time is again fully ground in agate mortar, carry out sintering for the second time under air atmosphere, temperature is 1000 ℃, and insulation 2 ~ 10h, naturally cools to room temperature.Process before repeating, carries out final sintering again, and temperature is 1300 ℃, and insulation 3 ~ 10h naturally cools to room temperature and obtains ultimate aim product.
Fig. 4 is the Sr that the present embodiment makes
6.65eu
0.35zr (PO
4)
6the excitation spectrum that material sample monitors at ambient temperature and utilizing emitted light spectrogram.As seen from Figure 4: the prepared Sr of the present embodiment
6.65eu
0.35zr (PO
4)
6material is a kind of red emitting material, and transmitting peak position, in 613nm left and right, is a kind of good red light material.
Embodiment 3
According to chemical formula Sr
6.65eu
0.35zr (PO
4)
6in the stoichiometric ratio of each element, take respectively Eu
2o
3: 1.232 grams, SrCO
3: 4.134 grams, ZrO
2: 0.6161 gram, NH
4h
2pO
4: 3.451 grams.In agate mortar, grind, and fully mix.The powder mixing is calcined for the first time under air atmosphere, and temperature is 350 ℃, and insulation 2 ~ 10h, takes out sample after being naturally cooled to room temperature.The powder of calcining for the first time is again fully ground in agate mortar, carry out sintering for the second time under air atmosphere, temperature is 1000 ℃,, insulation 2 ~ 10h, naturally cools to room temperature.Process before repeating, carries out final sintering again, and temperature is 1300 ℃, and insulation 3 ~ 10h naturally cools to room temperature and obtains ultimate aim product.
Fig. 5 is the Sr that the present embodiment makes
5.6eu
1.4zr (PO
4)
6the excitation spectrum that material sample monitors at ambient temperature and utilizing emitted light spectrogram.As seen from Figure 5: the prepared Sr of the present embodiment
6.65eu
0.35zr (PO
4)
6be a kind of orange light luminescent material, transmitting peak position, in 613nm left and right, is a kind of good fluorescent orange material.
Embodiment 4
Take ZrOCl
28H
21.426 grams of O (analytical pure), are dissolved in 40ml deionized water, add 1.854 grams of citric acids as complexing agent, stir pH value to 7～8 of using ammoniacal liquor regulator solution after 30 minutes under room temperature;
Take BaCO
3: 6.91 grams, be dissolved in the 2mol/L dilute nitric acid solution of 35ml and obtain clear solution;
Two kinds of solution that above-mentioned steps is obtained mix, and stir and make evenly;
Add Secondary ammonium phosphate (NH
4h
2pO
4, analytical pure) and 3.451 grams, stir and make to form vitreosol;
Vitreosol is dried at the temperature of 80～100 ℃ and form gel.Be warming up to again 180～300 ℃ and form aerogel, the aerogel obtaining is put into mortar and grind acquisition precursor powder.
The precursor powder obtaining is placed in to alumina crucible, in retort furnace, synthesizes.Heat-up rate with 5 ℃ of per minutes rises to 350 ℃, and insulation is greater than 5h, continues to rise to 1000 ℃ with the heat-up rate of 3 ℃ of per minutes, insulation is greater than 5h, finally with 3 ℃ of per minutes, is warming up to 1300 ℃ again, and insulation is greater than 6h, naturally cool to room temperature, the product obtaining after grinding is Ba
7zr (PO
4)
6material.
Fig. 6 is the Ba that the present embodiment makes
7zr (PO
4)
6the X-ray powder diffraction collection of illustrative plates of material sample and the comparison of standard card PDF#29-0407.As seen from Figure 6: the prepared Ba of the present embodiment
7zr (PO
4)
6material is pure phase.
Fig. 7 is the Ba that the present embodiment makes
7zr (PO
4)
6the excitation spectrum that material sample monitors at ambient temperature and utilizing emitted light spectrogram.As seen from Figure 7: the prepared Ba of the present embodiment
7zr (PO
4)
6material is a kind of self-excitation green light luminescent material, and transmitting peak position, in 500nm left and right, is a kind of good green fluorescent material.
Embodiment 5
Take ZrOCl
28H
21.426 grams of O (analytical pure), are dissolved in 40ml deionized water, add 1.854 grams of citric acids as complexing agent, stir pH value to 7～8 of using ammoniacal liquor regulator solution after 30 minutes under room temperature;
Take BaCO
3: 6.424 grams, be dissolved in the 2mol/L dilute nitric acid solution of 32.55ml and obtain clear solution;
Take Eu
2o
3: 0.4312 gram, be dissolved in the 2mol/L dilute nitric acid solution of 7.35ml, then add appropriate citric acid, stir and make evenly;
Three kinds of solution that above-mentioned steps is obtained mix, and stir and make evenly;
Add Secondary ammonium phosphate (NH
4h
2pO
4, analytical pure) and 3.451 grams, stir and form vitreosol;
The vitreosol obtaining is dried at the temperature of 80～100 ℃ and form gel.Be warmed up to again 180～300 ℃ and form aerogel, the aerogel obtaining is put into mortar and grind acquisition precursor powder;
Precursor powder is placed in to alumina crucible, in retort furnace, synthesizes.Heat-up rate with 5 ℃ of per minutes rises to 350 ℃, and insulation is greater than 5h, continues to rise to 1000 ℃ with the heat-up rate of 3 ℃ of per minutes, insulation is greater than 5h, finally with 3 ℃ of per minutes, is warming up to 1300 ℃ again, and insulation is greater than 6h, naturally cool to room temperature, the product obtaining after grinding is: Ba
6.51eu
0.49zr (PO
4)
6material.
Fig. 8 is the Ba that the present embodiment makes
6.51eu
0.49zr (PO
4)
6the excitation spectrum that material sample monitors at ambient temperature and utilizing emitted light spectrogram.The prepared Ba of the present embodiment
6.51eu
0.49zr (PO
4)
6material is a kind of orange light luminescent material, and transmitting peak position, in 613nm left and right, is a kind of good UV fluorescent orange material.
Claims (8)
1. a zirconium phosphate base luminescent material, is characterized in that: its chemical formula is
m 7-7xeu
7xzr (PO
4)
6, wherein,
mfor divalent alkaline-earth metal ion strontium ion Sr
2+or barium ion Ba
2+in a kind of;
xtrivalent europium ion Eu
3+doping, 0 < x≤0.5.
2. a preparation method for zirconium phosphate base luminescent material as claimed in claim 1, is characterized in that adopting high temperature solid-state method, comprises the steps:
(1) press chemical formula M
7-7xeu
7xzr (PO
4)
6the stoichiometric ratio of middle corresponding element takes raw material, and described raw material is alkali metal containing ion
mcompound,
mfor divalent alkaline-earth metal ion strontium ion Sr
2+or barium ion Ba
2+in a kind of, containing europium ion Eu
3+compound, zirconium dioxide and contain phosphonium ion P
5+compound, 0 < x≤0.5, grinds and mixes, and obtains mixture;
(2) mixture is placed in to alumina crucible, in retort furnace, synthesizes, sintering temperature is at 900～1500 ℃, and soaking time is greater than 5 hours, obtains a kind of zirconium phosphate base luminescent material after cooling.
3. a preparation method for zirconium phosphate base luminescent material as claimed in claim 1, is characterized in that adopting chemical solution method, comprises the steps:
(1) will be by formula M
7-7xeu
7xzr (PO
4)
6the stoichiometric ratio of middle corresponding element takes containing europium ion Eu
3+compound dissolution in dilute nitric acid solution or distilled water, then add the complexing agent complexing europium ion Eu of appropriate stoichiometric ratio
3+; Europium ion Eu
3+with the mol ratio of complexing agent be 1:1; Described complexing agent is citric acid or ethylenediamine tetraacetic acid (EDTA);
(2) by formula M
7-7xeu
7xzr (PO
4)
6middle corresponding element stoichiometric ratio takes eight hydration zirconium oxychlorides, and water-soluble solution obtains clear solution, then adds the complexing agent complexing zirconium ion of appropriate stoichiometric ratio; The mol ratio of zirconium ion and complexing agent is 1:2; Described complexing agent is citric acid or ethylenediamine tetraacetic acid (EDTA);
(3) will be by formula M
7-7xeu
7xzr (PO
4)
6the compound dissolution that the stoichiometric ratio of middle corresponding element takes alkali metal containing ion M obtains clear solution in water or rare nitric acid;
mfor divalent alkaline-earth metal ion strontium ion Sr
2+or barium ion Ba
2+in a kind of;
(4) solution that mixing step (1), (2) and (3) obtain, is uniformly mixed;
(5) add formula M
7-7xeu
7xzr (PO
4)
6the stoichiometric ratio of middle corresponding element containing phosphonium ion P
5+in the mixing solutions that compound obtains in step (4), stir and form solution;
(6) the resulting solution of step (5) is dried and formed gel, reheat and obtain aerogel, the aerogel obtaining is ground, obtain precursor powder;
(7) precursor powder step (6) being obtained is placed in alumina crucible, in retort furnace, synthesizes, and first temperature is risen to 200～500 ℃, and insulation is greater than 2 hours; Continue to be warming up to 800～1100 ℃, insulation is greater than 2 hours; Finally be warming up to 1200～1400 ℃, insulation is greater than 3 hours; After cooling, obtain a kind of zirconium phosphate base luminescent material.
4. according to the preparation method of a kind of zirconium phosphate base luminescent material described in claim 2 or 3, it is characterized in that: described alkali metal containing ion
mcompound be
moxide compound,
mcarbonate,
mone or more combination of nitrate.
5. according to the preparation method of the zirconium phosphate base luminescent material described in claim 2 or 3, it is characterized in that: described containing europium ion Eu
3+compound be a kind of in europium sesquioxide, europium nitrate, or their combination.
6. according to the preparation method of a kind of zirconium phosphate base luminescent material described in claim 2 or 3, it is characterized in that: containing phosphonium ion P
5+compound be a kind of in primary ammonium phosphate or Secondary ammonium phosphate, or their combination.
7. an application for zirconium phosphate base luminescent material as claimed in claim 1, is characterized in that: described luminescent material is as take the fluorescent material that vacuum-ultraviolet light VUV and UV-light be excitaton source.
8. an application for zirconium phosphate base luminescent material as claimed in claim 1, is characterized in that: described luminescent material is for photodiode, display material, three-color fluorescent lamp or Field Emission Display.
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| CN102936498B (en) * | 2012-11-11 | 2013-12-04 | 青岛大学 | Zirconium phosphate-based elastic stress luminescent material and preparation method thereof |
| CN104388085B (en) * | 2014-11-26 | 2016-06-29 | 中国计量学院 | A kind of white light LEDs phosphate orange fluorescent powder and preparation method thereof |
| CN105255491B (en) * | 2015-11-05 | 2018-03-09 | 上海师范大学 | A kind of photochromic adjustable fluorescent material and preparation method thereof |
| CN108865135A (en) * | 2018-08-01 | 2018-11-23 | 苏州大学张家港工业技术研究院 | Eu3+Ion-activated phosphate base fluorescent material and its preparation and application |
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| New Compounds with Eulytine Structure: Crystal Chemistry and Luminescence;G. BLASSE;《JOURNAL OF SOLID STATE CHEMISTRY》;19701231;第2卷;第27-30页（"1.Introduction"） * |
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