CN103059849A - Silicophosphate green fluorescent powder activated by Eu<2+> and preparation method as well as application thereof - Google Patents
Silicophosphate green fluorescent powder activated by Eu<2+> and preparation method as well as application thereof Download PDFInfo
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Abstract
The invention discloses a silicophosphate green fluorescent powder activated by Eu<2+> and a preparation method as well as an application of the fluorescent powder. The chemical general formula of the fluorescent powder is Ca15-15xEu15x (PO4)2(SiO4)6, wherein x is mole fraction of Eu<2+> ion replacing Ca<2+> ion, x is more than 0.0001 and not more than 0.20.The fluorescent powder is suitable for excitation of near ultraviolet of 330-420nm and is very coincided with the emission wavelength of a near ultraviolet semiconductor chip. The fluorescent powder emits bright green light in the excitation of the near ultraviolet, and the light intensity is high and the stability is good. The manufacturing method adopted by silicophosphate activated by rare earth europium ion Eu<2+> is simple, good in reproducibility, stable in obtained product quality and easy to operate and industrially produce.
Description
Technical field
The present invention relates to a kind of green fluorescence luminescent material, particularly a kind of under near ultraviolet excitation the fluorescent material of transmitting green fluorescence, it can be applicable to belong to the phosphor technical field in ultraviolet-near ultraviolet type white light LEDs.
Background technology
As natural colour display unit of future generation, light emitting diode has caused people's concern.It can be used to various electron devices, comprising instrument panel, TV (TV) and flat-panel monitor.Wherein white light LEDs (light emitting diode) is compared with traditional mains lighting supply, have energy-conservation, efficient, volume is little, the life-span is long, the advantage such as fast response time, driving voltage are low, anti-vibration has been subject to the extensive concern in the world.
Since first white light LEDs in 1996 comes out, development rapidly, luminous efficiency improves constantly, and is expected to replace traditional lighting sources such as incandescent light, luminescent lamp and high voltage mercury lamp, is called the green illumination light source of tool development prospect of 21st century.At present, the technology of preparing of white light LEDs mainly contains 2 kinds: (1) with three kinds of monochromatic LED combination results of red, green, blue white light, this method can arbitrarily be adjusted color, but power supply is complicated, and cost is higher; (2) mix the formation white light with other luminescent materials of LED de-excitation, namely cooperate the fluorescent material of Yellow light-emitting low temperature with blue-ray LED, perhaps use three kinds of fluorescent material of near ultraviolet LED de-excitation red, green, blue.This method is no matter be all to be better than first method aspect feasibility, practicality or the commercialization, so it has obtained very fast development.Carry out in the scheme of light conversion YAG (Y at two kinds of use fluorescent material
3Al
5O
12): Ce
3+The yellow fluorescent powder combination, this method relative cost is lower, and efficient is higher, but owing to lack red composition, colour rendering index is relatively poor.In addition, because the absorption peak of the light-converting material of blue-light LED chip requires to be positioned at 420-470nm, the fluorescent material that can satisfy this requirement is considerably less, absorption intensity neither be very large, seek this class fluorescent material suitable difficulty is arranged, so the wavelength of led chip along with the development of manufacturing process, more and more moves toward the shortwave direction, " near ultraviolet (360-410nm) type white light LEDs (NUV-LED) " become the most active system of present research.Photochromic stable aspect has more advantage in its color quality, photochromic consistence and the working process.The combination of ultraviolet or near ultraviolet LED and three primary colors fluorescent powder, the method color developing is best, but the fluorescent material luminous efficiency is lower at present, so development of new redness, green and blue colour fluorescent powder efficient, Heat stability is good are the keys that improves the white light LEDs luminous mass.
At present, the green emitting phosphor that efficiency of conversion is higher mostly is the sulfide system, this class light-emitting phosphor less stable, and light decay is large or cost is higher, and they very easily absorb deliquescence, and its poor stability can not satisfy the requirement that LED uses.Such as Chinese patent CN1585141A " green fluorescent material of halide silicate green fluorescent material and pyrosilicate and orthosilicate ", this material excitation spectrum a wider range, but glow color is single and luminous intensity a little less than, can not mate with existing fluorescent material, significant limitation is arranged in actual applications.Chinese invention patent CN101597493A " a kind of alkaline-earth metal silicophosphate fluorescent material and manufacture method and application ", chemical constitution is M
3-x-y(PO
4)
2SiO
4: Eu
xR
y, 0.001≤x≤0.1,0.001≤y≤0.2 wherein; By in raw material, adding solubility promoter or after co-precipitation is processed, add again solubility promoter, under the high temperature reaction synthesized emission wavelength can be according to the fluorescent material of adjusting, excitation wave length and width, good chemical stability; Chinese invention patent CN101284990A " a kind of alkaline-earth metal silicophosphate white light emitting phosphor and manufacture method thereof ", the consisting of of this fluorescent material: Ba
aSr
bCa
c(PO
4)
x(SiO
4)
y: Eu
d, Mn
e, 3.9≤a＜9,0≤b≤3,0.1＜c≤1,0.01＜d≤0.1,0.01＜e≤0.1,1＜x≤4,0.1≤y≤2 wherein; Change along with forming, the excitation wavelength range of this fluorescent material is ultraviolet and purple light, excites lower transmitting white at 365nm.But by the europkium-activated Ca of the divalence of near ultraviolet excitation
15(PO
4)
2(SiO
4)
6The silicic acid calcium phosphate green emitting phosphor of structure has no open and report.
Summary of the invention
The luminescent phosphor luminous efficiency is low in order to overcome in the prior art, preparation difficulty, product are impure, can not the actual production utilization etc. many deficiencies, the object of the present invention is to provide a kind of chemical purity high, luminous mass is good, and simple, the eco-friendly Eu of preparation technology
2+The silicic acid calcium phosphate green emitting phosphor light powder, preparation method and the application thereof that activate.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of Eu is provided
2+The silicophosphate green emitting phosphor that activates, its chemical general formula is: Ca
15-15xEu
15x(PO
4)
2(SiO
4)
6, wherein x is Eu
2+Ionic replacement Ca
2+The molar fraction of ion, 0.0001＜x≤0.2.
A kind of aforesaid Eu
2+The preparation method of the silicophosphate green emitting phosphor that activates adopts high temperature solid-state method, may further comprise the steps:
(1) presses chemical formula Ca
15-15xEu
15x(PO
4)
2(SiO
4)
6, wherein 0.0001＜x≤0.2 takes by weighing respectively to contain calcium ion Ca
2+Compound, contain phosphonium ion P
5+Compound, contain silicon ion Si
4+Compound, contain europium ion Eu
3+Compound, mix after the various raw materials that take by weighing are ground respectively, obtain mixture;
(2) with mixture for the first time calcining under air atmosphere, calcining temperature is 500～1000 ℃, and calcination time is 1～20 hour;
(3) behind the naturally cooling, grind and mix, for the second time calcining under reducing atmosphere, described reducing atmosphere is a kind of in following three kinds of atmosphere, or their combination:
The gas atmosphere that carbon granules or gac are produced at combustion synthesis in air;
Calcining temperature is 800～1350 ℃, and calcination time is 3～10 hours, obtains a kind of Eu
2+The silicic acid phosphate green emitting phosphor that activates.
A preferred version provided by the invention is: calcining temperature is 650～1000 ℃ for the first time, and calcination time is 5～9 hours; Calcining temperature is 950～1350 ℃ for the second time, and calcination time is 3～9 hours.
A kind of aforesaid Eu
2+The preparation method of the silicophosphate green emitting phosphor that activates, the present invention also provides a kind of employing chemical solution method, may further comprise the steps:
(1) to contain calcium ion Ca
2+Compound, contain phosphonium ion P
5+Compound, contain silicon ion Si
4+Compound, contain europium ion Eu
3+Compound be raw material, press general formula Ca
15-15xEu
15x(PO
4)
2(SiO
4)
6The stoichiometric ratio of middle corresponding element takes by weighing each raw material, wherein 0.0001＜x≤0.2; The raw material that takes by weighing is dissolved in respectively in the nitric acid and with the deionized water dilution, 0.5～2.0wt% by reactant quality in each raw material adds respectively complexing agent again, obtains the mixed solution of each raw material; Described complexing agent is a kind of in citric acid, the oxalic acid, or their combination;
(2) mixed solution with each raw material slowly mixes, and in temperature is to stir 1～2 hour under 50～100 ℃ the condition, obtains fluffy presoma after leaving standstill, drying;
(3) with presoma for the first time calcining in air atmosphere, calcining temperature is 300～500 ℃, and calcination time is 1～8 hour;
(4) behind the naturally cooling, grind and mix, for the second time calcining in air atmosphere, calcining temperature is 500～900 ℃, calcination time is 1～9 hour;
(5) behind the naturally cooling, grind and mix, calcine under reducing atmosphere, described reducing atmosphere is a kind of in following three kinds of atmosphere, or their combination:
Calcining temperature is 700～1300 ℃, and calcination time is 2～8 hours, obtains a kind of silicic acid phosphate green emitting phosphor.
The compound that contains calcium ion of the present invention is: a kind of or their combination in calcium oxide, nitrocalcite, the calcium carbonate; The described compound that contains positively charged ion silicon is a kind of in silicic acid, the tetraethoxy or their combination; Contain compounds of phosphorus and be a kind of in Vanadium Pentoxide in FLAKES, primary ammonium phosphate, ammonium hydrogen phosphate, the ammonium phosphate or their combination; The compound that contains europium ion is a kind of in europium sesquioxide, the europium nitrate or their combination.
A preferred version provided by the invention is: described first time, calcining temperature was 400～500 ℃, and calcination time is 5～8 hours; Calcining temperature is 700～900 ℃ for the second time, and calcination time is 6～9 hours; The third firing temperature is 1000～1300 ℃, and calcination time is 5～8 hours
A kind of aforesaid Eu
2+The silicic acid calcium phosphate green emitting phosphor that activates is applied to illumination or the display device of the white light emitting diode of near ultraviolet excitation.
Compared with prior art, the advantage of technical solution of the present invention is:
1, silicic acid calcium phosphate matrix provided by the invention is easy to realize the filling of bivalent rare earth europium ion in this matrix, and can make rare-earth cation stable existence in matrix.
2, this green emitting phosphor can be excited by near ultraviolet light well, can well be applied near ultraviolet type white light LEDs (NUV-LED) device.
3, the fluorescent material that makes has good luminous intensity, stability, color developing and granularity, is conducive to realize the high-power LED of preparation.
4, the preparation process of substrate material of the present invention is simple, the product easily collecting, and without the waste water and gas discharging, environmental friendliness especially is fit to serialization production.
Description of drawings
Fig. 1 is by the X-ray powder diffraction collection of illustrative plates of the sample of the technology preparation of the embodiment of the invention 1 and the contrast of standard card PDF#50-0905;
Fig. 2 is the luminescent spectrum of sample under near-ultraviolet ray 400 nanometers excite by the preparation of the technology of the present invention solid reaction process;
Fig. 3 is the ultraviolet that obtains of material sample monitoring utilizing emitted light 500 nanometers by the technology of the present invention preparation and the exciting light spectrogram of near ultraviolet region;
Fig. 4 prepares the luminescent spectrum of sample under near-ultraviolet ray 390 nanometers excite by the technology of the present invention chemical synthesis;
Fig. 5 is that excitation wavelength is 355 nanometers among the embodiment, and detecting wavelength is the decay of luminescence curve of 500 nanometers.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1:
Preparation Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6
According to chemical formula Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6In the stoichiometric ratio of each element take by weighing respectively calcium carbonate CaCO
3: 2.853 grams, europium sesquioxide Eu
2O
3: 0.264 gram, primary ammonium phosphate NH
4H
2PO
4: 0.461 gram, silicon-dioxide SiO
2: 0.721 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 900 ℃, then calcination time 7 hours is cooled to room temperature, takes out sample.Fully mixed grinding is even again with the raw material of for the first time calcining, among the reducing atmospheres such as nitrogen (interpolation gac), CO (carbon monoxide converter) gas, hydrogen or nitrogen and hydrogen mixture, carry out again sintering, 1320 ℃ of temperature, calcination time 8 hours, then be chilled to room temperature, take out sample.Namely obtain the rare earth doped divalent europium Eu of powder shaped
2+Phosphorus Calucium Silicate powder green luminescent material.
Referring to accompanying drawing 1, it is that the XRD test result shows that prepared material is phosphorus Calucium Silicate powder Ca by the X-ray powder diffraction collection of illustrative plates of the material sample of present embodiment technical scheme preparation and the comparison of standard card PDF#50-0905
15(PO
4)
2(SiO
4)
6Monophase materials.
Referring to accompanying drawing 2, it is 5% concentration Eu
2+Ion is at Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6Excite the luminescent spectrum that obtains with near-ultraviolet light 400nm in the fluorescent material, the main center emission wavelength of this material is the green emitting wave band of about 500nm, calculate by CIE simultaneously, the coordinate of learning it is x=0.135, y=0.562, also just in time drop on green area, it can finely be applicable to the white light LEDs that near-ultraviolet light is excitation light source.
Referring to accompanying drawing 3, from the exciting light spectrogram of near ultraviolet region, can finding out that the material sample monitoring utilizing emitted light 500nm by the technology of the present invention preparation is obtained, the green emitting of this material excite the mainly near ultraviolet between 330 ~ 420 nm (NUV) zone, source, can mate well the near ultraviolet LED chip.
Referring to accompanying drawing 5, it is that the material sample for preparing by the present embodiment technical scheme is 355 nanometers in excitation wavelength, and detecting wavelength is the decay of luminescence curve of 500 nanometers, and be 1600 nanoseconds the fall time that can calculate this green emitting phosphor from figure.
Embodiment 2:
Preparation Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6
According to chemical formula Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6In the stoichiometric ratio of each element take by weighing respectively calcium oxide CaO:3.996 gram, europium nitrate Eu (NO
3)
3: 1.268 grams, Vanadium Pentoxide in FLAKES P
2O
5: 0.710 gram, silicon-dioxide SiO
2: 1.803 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 950 ℃, then calcination time 6 hours is cooled to room temperature, takes out sample.Fully mixed grinding is even again with the raw material of for the first time calcining, among the reducing atmospheres such as nitrogen (interpolation gac), CO (carbon monoxide converter) gas, hydrogen or nitrogen and hydrogen mixture, carry out again sintering, 1300 ℃ of temperature, calcination time 8 hours, then be chilled to room temperature, take out sample.Namely obtain the rare earth doped divalent europium Eu of powder shaped
2+Phosphorus Calucium Silicate powder green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Embodiment 3:
Preparation Ca
13.5Eu
1.5(PO
4)
2(SiO
4)
6
According to chemical formula Ca
13.5Eu
1.5(PO
4)
2(SiO
4)
6In the stoichiometric ratio of each element take by weighing respectively calcium carbonate CaCO
3: 2.703 grams, europium nitrate Eu (NO
3)
3: 1.014 grams, primary ammonium phosphate NH
4H
2PO
4: 0.461 gram, silicon-dioxide SiO
2: 0.721 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 850 ℃, then calcination time 8 hours is cooled to room temperature, takes out sample.Fully mixed grinding is even again with the raw material of for the first time calcining, among the reducing atmospheres such as nitrogen (interpolation gac), CO (carbon monoxide converter) gas, hydrogen or nitrogen and hydrogen mixture, carry out again sintering, 1350 ℃ of temperature, calcination time 7 hours, then be chilled to room temperature, take out sample.Namely obtain the rare earth doped divalent europium Eu of powder shaped
2+Phosphorus Calucium Silicate powder green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Embodiment 4:
Preparation Ca
13.5E
1.5(PO
4)
2(SiO
4)
6
According to chemical formula Ca
13.5Eu
1.5(PO
4)
2(SiO
4)
6In the stoichiometric ratio of each element take by weighing respectively nitrocalcite Ca (NO
3)
2: 4.431 grams, europium sesquioxide Eu
2O
3: 0.528 gram, ammonium phosphate (NH
4)
3PO
4: 0.597 gram, silicon-dioxide SiO
2: 0.721 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 1000 ℃, then calcination time 5 hours is cooled to room temperature, takes out sample.Fully mixed grinding is even again with the raw material of for the first time calcining, among the reducing atmospheres such as nitrogen (interpolation gac), CO (carbon monoxide converter) gas, hydrogen or nitrogen and hydrogen mixture, carry out again sintering, 1350 ℃ of temperature, calcination time 7 hours, then be chilled to room temperature, take out sample.Namely obtain the rare earth doped divalent europium Eu of powder shaped
2+Phosphorus Calucium Silicate powder green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Embodiment 5:
Preparation Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6
According to chemical formula Ca
14.25Eu
0.75(PO
4)
2(SiO
4)
6In the stoichiometric ratio of each element, take by weighing respectively nitrocalcite Ca (NO
3)
2 .4H
2The O:3.365 gram, europium sesquioxide Eu
2O
3: 0.132 gram, primary ammonium phosphate NH
4H
2PO
4: 0.230 gram, tetraethoxy Si (OC
2H
5)
4: 1.250 restrain, and take by weighing the citric acid of the 0.5wt% of above medicine total mass again; First with the Si (OC that takes by weighing
2H
5)
4With deionized water, ethanol, nitric acid heated and stirred dissolving (control pH=2), then add an amount of citric acid and stirred 2 hours; Then with the Eu that takes by weighing
2O
3℃ carry out stir process with an amount of deionized water, nitric acid and citric acid post-heating to 50; Above-mentioned two kinds of solution are mixed, add therein again Ca (NO
3)
2 .4H
2O, NH
4H
2PO
4Heated and stirred, and add several times appropriate amount of deionized water and nitric acid, continue to stir 2 hours, to leave standstill, oven dry obtains fluffy presoma; Calcining temperature is 450 ℃ for the first time, calcination time 6 hours; Calcining temperature is 900 ℃ for the second time, calcination time 7 hours; The third firing temperature is 1250 ℃, and calcination time 8 hours namely obtains the rare earth doped divalent europium Eu of powder shaped
2+Phosphorus Calucium Silicate powder green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.Fig. 4 is its utilizing emitted light spectrogram under 390nm excites, and can lead to the same conclusion, and just intensity changes to some extent.This has verified that well this green emitting phosphor can be excited by the good multi-wavelength of near ultraviolet region.
Embodiment 6:
Preparation Ca
13.5Eu
1.5(PO
4)
2(SiO
4)
6
According to chemical formula Ca
13.5Eu
1.5(PO
4)
2(SiO
4)
6In the stoichiometric ratio of each element, take by weighing respectively calcium carbonate CaCO
3: 2.703 grams, europium nitrate Eu (NO
3)
3: 1.014 grams, primary ammonium phosphate NH
4H
2PO
4: 0.460 gram, tetraethoxy Si (OC
2H
5)
4: 2.500 restrain, and take by weighing the citric acid of the 0.5wt% of above medicine total mass again; First with the Si (OC that takes by weighing
2H
5)
4With deionized water, ethanol, nitric acid heated and stirred dissolving (control pH=2), then add an amount of citric acid and stirred 2 hours; Then with the CaCO that takes by weighing
3℃ carry out stir process with an amount of deionized water, nitric acid and citric acid post-heating to 50; Above-mentioned two kinds of solution are mixed, add therein again Eu (NO
3)
3, NH
4H
2PO
4Heated and stirred, and add several times appropriate amount of deionized water and nitric acid, continue to stir 2 hours, to leave standstill, oven dry obtains fluffy presoma; Calcining temperature is 500 ℃ for the first time, calcination time 5 hours; Calcining temperature is 850 ℃ for the second time, calcination time 9 hours; The third firing temperature is 1300 ℃, and calcination time 7 hours namely obtains the rare earth doped divalent europium Eu of powder shaped
2+Phosphorus Calucium Silicate powder green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum and extinction curve are similar to embodiment 1.
Claims (7)
1. Eu
2+The silicophosphate green emitting phosphor that activates, it is characterized in that: its chemical general formula is: Ca
15-15xEu
15x(PO
4)
2(SiO
4)
6, wherein x is Eu
2+Ionic replacement Ca
2+The molar fraction of ion, 0.0001＜x≤0.2.
2. Eu as claimed in claim 1
2+The preparation method of the silicophosphate green emitting phosphor that activates adopts high temperature solid-state method, it is characterized in that may further comprise the steps:
(1) presses chemical formula Ca
15-15xEu
15x(PO
4)
2(SiO
4)
6, wherein 0.0001＜x≤0.2 takes by weighing respectively to contain calcium ion Ca
2+Compound, contain phosphonium ion P
5+Compound, contain silicon ion Si
4+Compound, contain europium ion Eu
3+Compound, mix after the various raw materials that take by weighing are ground respectively, obtain mixture;
(2) with mixture for the first time calcining under air atmosphere, calcining temperature is 500～1000 ℃, and calcination time is 1～20 hour;
(3) behind the naturally cooling, grind and mix, for the second time calcining under reducing atmosphere, described reducing atmosphere is a kind of in following three kinds of atmosphere, or their combination:
Calcining temperature is 800～1350 ℃, and calcination time is 3～10 hours, obtains a kind of Eu
2+The silicic acid phosphate green emitting phosphor that activates.
3. Eu according to claim 2
2+The preparation method of the silicic acid calcium phosphate that activates, it is characterized in that: the described compound that contains calcium ion is: a kind of or their combination in calcium oxide, calcium hydroxide, nitrocalcite, the calcium carbonate; The described compound that contains positively charged ion silicon is a kind of in silicon-dioxide, the silicic acid or their combination; Contain compounds of phosphorus and be a kind of in Vanadium Pentoxide in FLAKES, primary ammonium phosphate, ammonium hydrogen phosphate, the ammonium phosphate or their combination; The compound that contains europium ion is a kind of in europium sesquioxide, the europium nitrate or their combination.
4. Eu according to claim 2
2+The preparation method of the silicic acid calcium phosphate that activates is characterized in that: calcining temperature is 650～1000 ℃ for the first time, and calcination time is 5～9 hours; Calcining temperature is 950～1350 ℃ for the second time, and calcination time is 3～9 hours.
5. Eu as claimed in claim 1
2+The preparation method of the silicophosphate green emitting phosphor that activates adopts chemical solution method, it is characterized in that may further comprise the steps:
(1) to contain calcium ion Ca
2+Compound, contain phosphonium ion P
5+Compound, contain silicon ion Si
4+Compound, contain europium ion Eu
3+Compound be raw material, press general formula Ca
15-15xEu
15x(PO
4)
2(SiO
4)
6The stoichiometric ratio of middle corresponding element takes by weighing each raw material, wherein 0.0001＜x≤0.2; The raw material that takes by weighing is dissolved in respectively in the nitric acid and with the deionized water dilution, 0.5～2.0wt% by reactant quality in each raw material adds respectively complexing agent again, obtains the mixed solution of each raw material; Described complexing agent is a kind of in citric acid, the oxalic acid, or their combination;
(2) mixed solution with each raw material slowly mixes, and in temperature is to stir 1～2 hour under 50～100 ℃ the condition, obtains fluffy presoma after leaving standstill, drying;
(3) with presoma for the first time calcining in air atmosphere, calcining temperature is 300～500 ℃, and calcination time is 1～8 hour;
(4) behind the naturally cooling, grind and mix, for the second time calcining in air atmosphere, calcining temperature is 500～900 ℃, calcination time is 1～9 hour;
(5) behind the naturally cooling, grind and mix, calcine under reducing atmosphere, described reducing atmosphere is a kind of in following three kinds of atmosphere, or their combination:
Calcining temperature is 700～1300 ℃, and calcination time is 2～8 hours, obtains a kind of silicic acid phosphate green emitting phosphor.
6. Eu according to claim 5
2+The preparation method of the silicic acid calcium phosphate that activates, it is characterized in that: the described compound that contains calcium ion is: a kind of or their combination in calcium oxide, nitrocalcite, the calcium carbonate; The described compound that contains positively charged ion silicon is a kind of in silicic acid, the tetraethoxy or their combination; Contain compounds of phosphorus and be a kind of in Vanadium Pentoxide in FLAKES, primary ammonium phosphate, ammonium hydrogen phosphate, the ammonium phosphate or their combination; The compound that contains europium ion is a kind of in europium sesquioxide, the europium nitrate or their combination.
7. Eu according to claim 5
2+The preparation method of the silicic acid calcium phosphate that activates is characterized in that: calcining temperature is 400～500 ℃ for the first time, and calcination time is 5～8 hours; Calcining temperature is 700～900 ℃ for the second time, and calcination time is 6～9 hours; The third firing temperature is 1000～1300 ℃, and calcination time is 5～8 hours
A kind of Eu as claimed in claim 1
2+The silicic acid calcium phosphate green emitting phosphor that activates is applied to illumination or the display device of the white light emitting diode of near ultraviolet excitation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952151A (en) * | 2014-03-13 | 2014-07-30 | 中国计量学院 | Europium ion activated silicon phosphate green fluorescent powder and its preparation method |
| CN104910916A (en) * | 2015-05-06 | 2015-09-16 | 周口师范学院 | Novel apatite structural luminescent material with adjustable luminescent colors and application thereof |
| CN105694870A (en) * | 2016-03-17 | 2016-06-22 | 常州工程职业技术学院 | Eu<3+> activated magnesium and sodium orthosilicate red fluorescent powder as well as preparation method and application thereof |
| CN112210375A (en) * | 2020-09-24 | 2021-01-12 | 东台市天源光电科技有限公司 | Rare earth doped silicate fluorescent powder and preparation method thereof |
| TWI786027B (en) * | 2022-06-24 | 2022-12-01 | 南臺學校財團法人南臺科技大學 | Fluorescent powder containing nano-agglomerates and preparation method thereof |
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| CN103952151A (en) * | 2014-03-13 | 2014-07-30 | 中国计量学院 | Europium ion activated silicon phosphate green fluorescent powder and its preparation method |
| CN104910916A (en) * | 2015-05-06 | 2015-09-16 | 周口师范学院 | Novel apatite structural luminescent material with adjustable luminescent colors and application thereof |
| CN105694870A (en) * | 2016-03-17 | 2016-06-22 | 常州工程职业技术学院 | Eu<3+> activated magnesium and sodium orthosilicate red fluorescent powder as well as preparation method and application thereof |
| CN105694870B (en) * | 2016-03-17 | 2018-08-07 | 常州工程职业技术学院 | A kind of Eu3+The positive sodium magnesium silicate red fluorescence powder and its preparation method and application of activation |
| CN112210375A (en) * | 2020-09-24 | 2021-01-12 | 东台市天源光电科技有限公司 | Rare earth doped silicate fluorescent powder and preparation method thereof |
| TWI786027B (en) * | 2022-06-24 | 2022-12-01 | 南臺學校財團法人南臺科技大學 | Fluorescent powder containing nano-agglomerates and preparation method thereof |
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