CN102559185B - Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device - Google Patents
Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device Download PDFInfo
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Abstract
The invention provides a yellow luminescent material with a voelckerite structure and a preparation method thereof as well as a white light-emitting diode device. The yellow luminescent material has a chemical general expression of (Al-xEux)8-yB2+y(PO4)6-y(SiO4)y(O1-zSz)2, wherein A and Eu are divalent metal ions, B is a trivalent metal ion, x is greater than 0 and less than or equal to 0.6, y is greater than or equal to 0 and less than or equal to 6, z is greater than or equal to 0 and less than or equal to 1, A can be alkaline earth metal, Mn or Zn, and B can be a metal in the group IIIA, rare earth metal or Bi.
Description
Technical field
The invention relates to a kind of gold-tinted fluorescent material, and relate to a kind of gold-tinted fluorescent material of oxidapatite kenel especially.
Background technology
Since after early in the twentieth century inventing the photic chip of giving out light based on InGaN, white light-emitting diodes (the white light-emitting diodes in commercial applications; WLEDs) considerable progress has been had.Against the blue light sent in conjunction with InGaN chip and with Y
3al
5o
12: Ce
3+(YAG:Ce
3+) be the gold-tinted that main material sends, the white light obtained has surmounted white heat bulb, compared with even can coming with conventional fluorescent.Compare with conventional light source, white light-emitting diodes is the light source of a kind of durable energy saving environmental protection again.But the photochromic quality of white light-emitting diodes is in white light hue adjustment (white hue tunability), colour temperature and to drill look (color rendering) still to be modified in nature, and the illumination of these character all with daily is relevant.
Most of fluorescent material that current white light-emitting diodes is using, all cannot reach the suitableeest requirement of white light, and quite not enough in the color rendering matter of red light region.Therefore, need for white light-emitting diodes finds novel material to meet the requirement of dialogue light quality.
Summary of the invention
Therefore, an aspect of of the present present invention is providing a kind of yellow fluorescent material with oxidapatite structure, it has (A
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
y(O
1-zs
z)
2chemical general formula, wherein A and Eu is divalent-metal ion, and B is trivalent metal ion, and 0 < x≤0.6,0≤y≤6 and 0≤z≤1.Aforesaid A can be alkaline-earth metal, Mn or Zn, B can be IIIA race metal, rare earth metal or Bi.
According to one embodiment of the invention, as y=z=0, this yellow fluorescent material has (A
1-xeu
x)
8b
2(PO
4)
6o
2chemical general formula.
According to another embodiment of the present invention, as y=6 and z=0 time, this yellow fluorescent material has (A
1-xeu
x)
2b
8(SiO
4)
6o
2chemical general formula.
According to further embodiment of this invention, as y=0 and z=1 time, this yellow fluorescent material has (A
1-xeu
x)
8b
2(PO
4)
6s
2chemical general formula.
According to yet another embodiment of the invention, as y=6 and z=1 time, this yellow fluorescent material has (A
1-xeu
x)
2b
8(SiO
4)
6s
2chemical general formula.
Another aspect of the invention is and provide a kind of white light-emitting diodes, it comprises a kind of blue-light fluorescent material, and any one gold-tinted fluorescent material aforesaid.
Another aspect of the present invention is for providing the preparation method of aforementioned gold-tinted fluorescent material, and it comprises each step below.First take the raw material of the required element conforming with stoichiometric chemistry ratio, wherein the raw metal of this gold-tinted fluorescent material is metal oxide or metal carbonate, phosphate radical raw material is Secondary ammonium phosphate or primary ammonium phosphate, silicate raw material packet silicon oxide-containing, and sulphur raw material packet sulfur-bearing powder.Then these raw materials taken are mixed equably, then these raw materials that calcination mixes, until obtain the product with pure oxygen phosphatic rock crystalline phase, calcination environment is containing aerobic, and calcination temperature is 1200-1400 DEG C.At the temperature of ammonia and 900-1200 DEG C, by Eu
3+be reduced into Eu
2+, to obtain aforesaid gold-tinted fluorescent material.
According to one embodiment of the invention, before reduction step, the product after the calcination that can also homogenize.
The wavelength in the region of mainly giving out light of aforesaid gold-tinted fluorescent material is longer, is comparatively partial to red light region.Therefore, when using above-mentioned yellow fluorescent material to manufacture white light-emitting diodes, can improve white light-emitting diodes release the color rendering matter of white light in red light region, and obtain the white light of better quality.
Foregoing invention content aims to provide the simplification summary of this disclosure, possesses basic understanding to make reader to this disclosure.This summary of the invention is not the complete overview of this disclosure, and its purpose is not being pointed out the key/critical assembly of the embodiment of the present invention or defining scope of the present invention.After consulting following description, persond having ordinary knowledge in the technical field of the present invention is when can understand essence spirit of the present invention and other goal of the invention easily, and the technology used in the present invention means and embodiment.
Accompanying drawing explanation
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, being described as follows of institute's accompanying drawings:
Fig. 1 is the preparation flow figure that display has the yellow fluorescent material of oxidapatite structure; Wherein 110,120,130,140,150 represent step.
Fig. 2,3,4 and 5 is respectively Ca
8la
2(PO
4)
6o
2: xEu
2+powder X-ray diffraction spectrogram, photoexcitation spectrogram, photic give out light spectrogram and UV-Vis solid-state reflected light spectrogram.
Fig. 6 is Ca
8la
2(PO
4)
6o
2: 0.03Eu
2+with gold-tinted commodity YAG:Ce
3+the comparing of photoexcitation and photic spectrum of giving out light.
Fig. 7 A-7E shows the photoexcitation of experimental example 1-5 and photic spectrum of giving out light respectively.
Fig. 8 A-8H shows the photoexcitation of experimental example 6-13 and photic spectrum of giving out light respectively.
Fig. 9 shows the photoexcitation of experimental example 14 and photic spectrum of giving out light.
Figure 10 shows the photoexcitation of experimental example 15 and photic spectrum of giving out light.
Figure 11 shows the spectrogram of giving out light of the white light-emitting diodes of experimental example 16-24.
Embodiment
Europium (Europium; Eu) be lanthanon, usually can form the compound of trivalent, because it has 4f
7metastable electronic configuration, but its to excite with giving out light be all linear, the application therefore on fluorescent material is limited.And divalent europium excite with giving out light to be all broadband, to be therefore widely used on photodiode.Giving out light in application, divalent europium because the difference of residing crystalline network, and can have giving out light of different colours, is normally partial to blue light.
Giving out light in application, phosphatic rock (apatite) is a kind of main body (host) material efficiently, and has synthesized oxidapatite (oxyapatite) material containing various rare earth metal at present, and it has Ca
8m
2(PO
4)
6o
2chemical general formula, wherein M is the rare earth ion of trivalent.This series of Ca
8m
2(PO
4)
6o
2compound in, different rare earth cations can be utilized to be used as the light source of various different wave length, such as, to can be the light source of visible ray or near infrared light.
In addition, the part of the phosphate radical in aforementioned oxidapatite structure, also can be replaced by silicate part and replace to complete.Be called silicate oxyapatite (silicate oxyapatite) structure by the oxidapatite structure that silicate replaces entirely, there is Ca
2m
8(SiO
4)
6o
2chemical general formula, wherein M is the rare earth ion of trivalent, is usually also to be responsible for giving out light by rare earth cation.At Ca
2m
8(SiO
4)
6o
2structure in, have 6 Ca
2+by 6 M
3+replace, to balance 6 negative charges that 6 silicates increase.
There is the yellow fluorescent material of oxidapatite structure
A kind of yellow fluorescent material with oxidapatite structure is provided, it has (A at this
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
y(O
1-zs
z)
2chemical general formula.Wherein Eu is divalent ion, and A is also divalent-metal ion, the calcium ion of both replacements above in oxidapatite structure.Therefore, A can be alkaline-earth metal, Zn or Mn.B is trivalent metal ion, replaces the rare earth ion in oxidapatite structure above.Therefore, B can be IIIA race metal, rare earth metal or Bi, wherein IIIA race metal such as can be Al, Ga, In, and rare earth metal such as can be Sc, Y and lanthanon, as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.In superincumbent chemical formula, the numerical range of x, y and z is respectively 0 < x≤0.6,0≤y≤6 and 0≤z≤1.And phosphate radical and silicic acid are with the same position occupied in lattice, O and S also occupies the same position in lattice.
At some in particular cases, (A can be simplified
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
y(O
1-zs
z)
2chemical formula, ask for an interview table one below.
Table one: the kind with the yellow fluorescent material of oxidapatite structure
Because some document can by the chemical general formula Ca of above-mentioned oxidapatite structure
8m
2(PO
4)
6o
2in the number of often kind of element divided by 2, and be simplified to Ca
4m (PO
4)
3the chemical general formula of O, so the above-mentioned chemical general formula with the yellow fluorescent material of oxidapatite structure also can simplify it in the same way.General formula after simplification can (A
1-xeu
x)
4-db
1+d(PO
4)
3-d(SiO
4)
d(O
1-zs
z) representing it, the numerical range of x and z, with identical above, be also 0 < x≤0.6 and 0≤z≤1, and the numerical range of d is 0≤d≤3.
There is the preparation method of the yellow fluorescent material of oxidapatite structure
Also above-mentioned (A is provided at this
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
y(O
1-zs
z)
2the preparation method of yellow fluorescent material, please refer to Fig. 1, and it is the preparation flow figure that display has the yellow fluorescent material of oxidapatite structure.
In the step 110 of Fig. 1, according to the chemical formula wanting the above-mentioned yellow fluorescent material of synthesizing, take the raw material conforming with stoichiometric chemistry ratio respectively.The metal ion aspect of Eu, A and B, can select corresponding metal oxide to originate as it.If the metal ion of Eu, A and B has carbonate, corresponding metal carbonate also can be selected for its source.For example, calcium ion can selective oxidation calcium or calcium carbonate be just its source, and europium ion can select Eu
2o
3for its source.Phosphate radical aspect, can select Secondary ammonium phosphate or primary ammonium phosphate to be its source.Silicate aspect can selective oxidation silicon be its source.Sulphur then can directly select sulphur powder for its source.
Then in the step 120, mixed by desired raw material, blending means such as can be grinding.In step 130, under oxygenated environment (such as air), under the raw material mixed being placed in 1200-1400 DEG C of temperature, carry out calcination (calcine), till the product obtaining having pure oxygen phosphatic rock crystalline phase.Because the calcination of step 130 is carried out under oxygenated environment, so europium ions all in product is all Eu
3+, therefore need the Eu of the calcium ion position occupied in oxidapatite structure
3+be reduced into Eu
2+.
In step 140, can more completely and faster, therefore need the product of step 130 gained to homogenize again once, such as, for grinding once again to allow sequential reduction react.Then, in step 150, allow the product after homogenizing reduce at the temperature of ammonia and 900-1200 DEG C, about need 10 hours.
Embodiment one: at Ca
8la
2(PO
4)
6o
2mix the Eu of different ratios
2+
First, at Ca
8la
2(PO
4)
6o
2mix the Eu of different ratios
2+replace Ca
2+, form a series of (Ca
1-xeu
x)
8la
2(PO
4)
6o
2fluorescent material (in this embodiment, is denoted as Ca
8la
2(PO
4)
6o
2: xEu
2+), observe it photicly how give out light character.In this experimental example, (A
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
y(O
1-zs
z)
2in A
2+for Ca
2+, B
3+for La
3+, and y=z=0, and x is respectively 0,0.001,0.003,0.005,0.007,0.010,0.020,0.030,0.050,0.070 and 0.100.
The solid-state reflected light spectrogram of Fig. 2,3,4 and 5 the powder X-ray diffraction spectrogram of series compound, photoexcitation spectrogram, photic give out light spectrogram and UV-Vis for this reason respectively.As shown in Figure 2, Eu
2+doping, until 10mol%, neither can change Ca
8la
2(PO
4)
6o
2crystalline network.
The photoexcitation spectrogram of Fig. 3 ties up to 630nm monitoring and obtains.As shown in Figure 3, at the blue light place of 450nm, as x value (that is the Eu that is 0.030
2+when doping ratio is 3mol%) time have absorption maximum value.The photic spectrogram of giving out light of Fig. 4 excites at 450nm place and obtains.As shown in Figure 4, when x is 0.030, near 625nm, there is maximum intensity of giving out light.And as shown in Figure 5, in the region being less than below 500nm, doping Eu
2+ca
8la
2(PO
4)
6o
2all there is great absorption intensity.Otherwise do not adulterate Eu
2+ca
8la
2(PO
4)
6o
2, be less than the region of below 500nm then almost without any light absorbing phenomenon.
Fig. 6 is Ca
8la
2(PO
4)
6o
2: 0.03Eu
2+with gold-tinted commodity Y
3al
5o
12: Ce
3+(be denoted as YAG:Ce at this
3+) the comparing of photoexcitation and photic spectrum of giving out light, wherein solid line is Ca
8la
2(PO
4)
6o
2: 0.03Eu
2+spectrum, dotted line is YAG:Ce
3+spectrum.As shown in Figure 6, Ca
8la
2(PO
4)
6o
2: 0.03Eu
2+there is wider photoexcitation spectrum and photic spectrum of giving out light, and wavelength of giving out light comparatively is partial to red light region, therefore can solve YAG:Ce well known in the art
3+in the problem drilling look deficiency of red light region.
Embodiment two: use different A
2+synthesize (A
1-xeu
x)
8b
2(PO
4)
6o
2
As y=z=0, (A can be obtained
1-xeu
x)
8b
2(PO
4)
6o
2chemical general formula.The experimental example be synthesized at this has A
2+there is the Ca of 0.89mol%
2+, and the Mg of 10mol%
2+, Sr
2+, Ba
2+, Mn
2+, Zn
2+, and Eu
2+doping ratio be 1mol%.B
3+then be all La
2+.
In table two, list above-mentioned Mg
2+, Sr
2+, Ba
2+, Mn
2+, Zn
2+eight-coordinate ionic radius and the relevant photic data of giving out light of above-mentioned experimental example.Known from the data of table two, although the A replaced
2+ionic radius from 89pm to 142pm not etc., but it is given out light, the wavelength at scope and the place that gives out light is all roughly the same.Different A is replaced in the display of this result
2+ion, to (Ca
0.89a
0.1eu
0.01)
8la
2(PO
4)
6o
2photoexcitation and photic characteristics influence of giving out light little.
In Fig. 7 A-7E, show the photoexcitation of experimental example 1-5 and photic spectrum of giving out light respectively.From Fig. 7 A-7E, except (the Ca of experimental example 3
0.89mn
0.1eu
0.01)
8la
2(PO
4)
6o
2photoexcitation and photic spectrum of giving out light comparatively special outside, photoexcitation and the photic spectral shape of giving out light of experimental example 1,2,4,5 are all similar.This result shows again replaces different A
2+ion, to (Ca
0.89a
0.1eu
0.01)
8la
2(PO
4)
6o
2photoexcitation and photic characteristics influence of giving out light little.
Table two: (Ca
0.89a
0.1eu
0.01)
8la
2(PO
4)
6o
2relevant photic data of giving out light
Embodiment three: use different B
3+synthesize (A
1-xeu
x)
8b
2(PO
4)
6o
2
As y=z=0, (A can be obtained
1-xeu
x)
8b
2(PO
4)
6o
2chemical general formula.In the experimental example that this is synthesized, A
2+be all Ca
2+, Eu
2+doping ratio be 1mol%.B
3+part, has 90mol% to be La
3+, have 10mol% to be respectively Al
3+, Ga
3+, Sc
3+, In
3+, Lu
3+, Y
3+or Gd
3+.
In table three, list above-mentioned Al
3+, Ga
3+, Sc
3+, In
3+, Lu
3+, Y
3+and Gd
3+hexa-coordinate ionic radius and the relevant photic data of giving out light of above-mentioned experimental example.Known from the data of table two, although the B replaced
3+ionic radius from 53.5pm to 103pm not etc., but it is given out light, the wavelength at scope and the place that gives out light is all roughly the same.Different B is replaced in the display of this result
3+ion, to (Ca
0.99eu
0.01)
8(La
0.9b
0.1)
2(PO
4)
6o
2photoexcitation and photic characteristics influence of giving out light little.
Table three: (Ca
0.99eu
0.01)
8(La
0.9b
0.1)
2(PO
4)
6o
2relevant photic data of giving out light
In Fig. 8 A-8H, show the photoexcitation of experimental example 6-13 and photic spectrum of giving out light respectively.From Fig. 8 A-8H, except (the Ca of experimental example 13
0.99eu
0.01)
8(La
0.9bi
0.1)
2(PO
4)
6o
2photoexcitation and photic spectrum of giving out light comparatively special outside, the photoexcitation of experimental example 6-12 is all similar with photic spectral shape of giving out light, and also routine 2-5 is similar with previous experiments.This result shows again replaces different B
3+ion, to (Ca
0.99eu
0.01)
8(La
0.9b
0.1)
2(PO
4)
6o
2photoexcitation and photic characteristics influence of giving out light little.
The embodiment four: (A that silicate replaces
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
yo
2
As z=0, (A can be obtained
1-xeu
x)
8-yb
2+y(PO
4)
6-y(SiO
4)
yo
2chemical general formula.In the experimental example that this is synthesized, A
2+for Ca
2+, Eu
2+doping ratio be 1mol%, B
3+for La
3+, and y=1.Therefore, the chemical formula of gained is (Ca
0.99eu
0.01)
7la
3(PO
4)
5(SiO
4) O
2, its relevant photic data rows of giving out light is in table four.Fig. 9 shows the photoexcitation of experimental example 14 and photic spectrum of giving out light.
From table four and Fig. 9, (Ca
0.99eu
0.01)
7la
3(PO
4)
5(SiO
4) O
2little with the photic data difference of giving out light of previous experiments example 1-13, show after replacing phosphate radical by silicate, to the photoexcitation of this series compound and photic characteristics influence of giving out light little.
Table four: (Ca
0.99eu
0.01)
7la
3(PO
4)
5(SiO
4) O
2relevant photic data of giving out light.
Embodiment five: S
2-(the A replaced
1-xeu
x)
8b
2(PO
4)
6(O
1-zs
z)
2
As y=0, (A can be obtained
1-xeu
x)
8b
2(PO
4)
6(O
1-zs
z)
2chemical general formula.In the experimental example that this is synthesized, A
2+for Ca
2+, Eu
2+doping ratio be 1mol%, B
3+for La
3+, and z=0.1.Therefore, the chemical formula of gained is (Ca
0.99eu
0.01)
8la
3(PO
4)
6(O
0.9s
0.1)
2, its relevant photic data rows of giving out light is in table five.Figure 10 shows the photoexcitation of experimental example 15 and photic spectrum of giving out light.
Table five: (Ca
0.99eu
0.01)
7la
3(PO
4)
5(SiO
4) O
2relevant photic data of giving out light.
From table five and Figure 10, (Ca
0.99eu
0.01)
8la
3(PO
4)
6(O
0.9s
0.1)
2little with the photic data difference of giving out light of previous experiments example 1-13, show by S
2-replace O
2-afterwards, to the photoexcitation of this series compound and photic characteristics influence of giving out light little.
The embodiment six: (Ca of different concns
0.97eu
0.03)
8la
2(PO
4)
6o
2
In the application of white light-emitting diodes
In this embodiment, use the InGaN blue chip that can send 460nm blue light, in its sealing, mix (the Ca of different concns
0.97eu
0.03)
8la
2(PO
4)
6o
2, form white light-emitting diodes.(the Ca of white light-emitting diodes
0.97eu
0.03)
8la
2(PO
4)
6o
2doping content is listed in table six.
The table six: (Ca becoming white light-emitting diodes
0.97eu
0.03)
8la
2(PO
4)
6o
2the chromaticity coordinates value of doping content and the white light that sends thereof.
| Experimental example | Doping content (wt%) | Tristimulus coordinates (x, y) |
| 16 | 50 | (0.586，0.405) |
| 17 | 45 | (0.557，0.406) |
| 18 | 40 | (0.512，0.385) |
| 19 | 35 | (0.473，0.325) |
| 20 | 30 | (0.430，0.325) |
| 21 | 25 | (0.376，0.280) |
| 22 | 20 | (0.346，0.256) |
| 23 | 15 | (0.306，0.225) |
| 24 | 10 | (0.277，0.192) |
In fig. 11, the spectrogram of giving out light of the white light-emitting diodes of display experimental example 16-24, list in table six experimental example 16-24 white light-emitting diodes release the chromaticity coordinate value of white light.Known from the data of Figure 11 and table six, as (the Ca in sealing
0.97eu
0.03)
8la
2(PO
4)
6o
2when fluorescent material doping content is successively decreased, the intensity of relatively giving out light of the blue chip near 460nm can increase progressively, and the intensity of relatively giving out light of yellow fluorescent powder near 625nm can be successively decreased.Therefore, make white light-emitting diodes release white light chromaticity coordinate value can from (0.586,0.405) orange light along with fluorescent material doping weight reduce and be adjusted to (0.277,0.192) cold white light.
Generally, because the wavelength with the region of mainly giving out light of the yellow fluorescent material of oxidapatite structure of above-mentioned each experimental example is longer, comparatively red light region is partial to.Therefore, when using above-mentioned yellow fluorescent material to manufacture white light-emitting diodes, can improve white light-emitting diodes release the color rendering matter of white light in red light region, and obtain the white light of better quality.
Although the present invention discloses as above with embodiment; so itself and be not used to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, therefore protection scope of the present invention is when being as the criterion depending on the appended claim person of defining.
Claims (6)
1. there is a yellow fluorescent material for oxidapatite structure, it has (A
1-xeu
x)
8b
2(PO
4)
6(O
1-zs
z)
2chemical general formula, wherein A and Eu is divalent-metal ion, and B is trivalent metal ion, and 0<x≤0.6 and 0≤z≤1, wherein A is Mg or Zn, and B is IIIA race metal, Bi, Sc, Y, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
2. yellow fluorescent material as claimed in claim 1, wherein as z=0, this yellow fluorescent material has (A
1-xeu
x)
8b
2(PO
4)
6o
2chemical general formula.
3. yellow fluorescent material as claimed in claim 1, wherein as z=1, this yellow fluorescent material has (A
1-xeu
x)
8b
2(PO
4)
6s
2chemical general formula.
4. a white light-emitting diodes, comprises:
One blue-light fluorescent material; And
One gold-tinted fluorescent material, it has (A
1-xeu
x)
8b
2(PO
4)
6(O
1-zs
z)
2chemical general formula, wherein A and Eu is divalent-metal ion, and B is trivalent metal ion, and 0<x≤0.6 and 0≤z≤1, wherein A is Mg or Zn, and B is IIIA race metal, Bi, Sc, Y, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
5. a preparation method for gold-tinted fluorescent material as claimed in claim 1, comprises:
Take the raw material of the required element conforming with stoichiometric chemistry ratio, wherein the raw metal of this gold-tinted fluorescent material is metal oxide or metal carbonate, phosphate radical raw material is Secondary ammonium phosphate or primary ammonium phosphate, silicate raw material packet silicon oxide-containing, and sulphur raw material packet sulfur-bearing powder;
Mix these raw materials taken equably;
These raw materials that calcined mixed is good, until obtain the product with pure oxygen phosphatic rock crystalline phase, calcination environment is containing aerobic, and calcining temperature is 1200 – 1400 DEG C; And
At the temperature of ammonia and 900 – 1200 DEG C, by Eu
3+be reduced into Eu
2+, to obtain gold-tinted fluorescent material as claimed in claim 1.
6. preparation method as claimed in claim 5, wherein before reduction step, more comprises the product after the calcining that homogenizes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010614571.6A CN102559185B (en) | 2010-12-20 | 2010-12-20 | Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010614571.6A CN102559185B (en) | 2010-12-20 | 2010-12-20 | Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device |
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| CN104293352A (en) * | 2014-09-30 | 2015-01-21 | 杭州电子科技大学 | Phosphate blue fluorescent powder for white-light LED (Light-Emitting Diode) and preparation method thereof |
| CN104576632B (en) * | 2014-12-30 | 2019-01-01 | 欧普照明股份有限公司 | A kind of illumination module and the lighting device with the illumination module |
| CN104910916B (en) * | 2015-05-06 | 2016-08-24 | 周口师范学院 | A kind of glow color adjustable New Phosphorus lime stone structure light-emitting material and application thereof |
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| CN109825297A (en) * | 2018-12-05 | 2019-05-31 | 中国计量大学 | A kind of phosphate green emitting phosphor and preparation method thereof |
| CN112779009A (en) * | 2021-02-05 | 2021-05-11 | 淮阴师范学院 | High-sensitivity optical temperature sensing luminescent material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101892052A (en) * | 2009-05-18 | 2010-11-24 | 华映视讯（吴江）有限公司 | Red light luminescent material, manufacturing method thereof and white light emitting device |
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| CN101892052A (en) * | 2009-05-18 | 2010-11-24 | 华映视讯（吴江）有限公司 | Red light luminescent material, manufacturing method thereof and white light emitting device |
Non-Patent Citations (1)
| Title |
|---|
| Structural and Spectroscopic Characterization of Nominal Yb3+Ca8La2(PO4)6O2 Oxyapatite Single Crystal Fibers Grown by the Micro-Pulling-Down Method;Georges Boulon et al;《Advanced Functional Materials》;20010831;第11卷;第263-270页 * |
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