CN105441078A - Rare earth ion Eu<2+>-doped Y5Si3O12N fluorescent powder and preparation method therefor - Google Patents

Rare earth ion Eu<2+>-doped Y5Si3O12N fluorescent powder and preparation method therefor Download PDF

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CN105441078A
CN105441078A CN201410520180.6A CN201410520180A CN105441078A CN 105441078 A CN105441078 A CN 105441078A CN 201410520180 A CN201410520180 A CN 201410520180A CN 105441078 A CN105441078 A CN 105441078A
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刘茜
万洁琼
魏钦华
杨华
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to rare earth ion Eu<2+>-doped Y5Si3O12N fluorescent powder and a preparation method therefor. The chemical formula of the Y5Si3O12N fluorescent powder is Y5(1-x)Si3O12N: 5xEu<2+>, wherein Eu<2+> partially replaces Y<3+> and x is 0.3-0.4 mol%.

Description

Rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material and preparation method thereof
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material and preparation method thereof.
Background technology
White light LEDs is the emerging product in illumination market, and compared to traditional lighting system, white light LEDs has the advantages such as the low and fast response time of energy-saving and environmental protection, long service life, operating voltage.White-light LED illumination is generally utilize fluorescent powder coated light to change method to realize, namely excitated fluorescent powder is carried out with the light that LED chip is launched, the fluorescence of final generation is mixed to form white light mutually, specific implementation white light emission mode has three kinds, first yellow fluorescent powder coordinates blue-light LED chip, blue-light excited yellow fluorescent powder, the yellow light mix of unabsorbed blue light and phosphor emission forms white light.Its two be red, green, blue three-color phosphor coordinate UV LED chip, utilize UV-light effectively to excite three primary colors fluorescent powder and mix generation white light, because it has red-green-blue luminescence, the light source of any colour temperature can be deployed in theory, and its color developing is better.Its three be red, green dichromatism fluorescent material coordinate blue-light LED chip, utilize blue-light excited red, green dichromatism fluorescent material, the red-green glow that unabsorbed blue light and fluorescent material send is mixed to form white light.The white-light illuminating device commercialization utilizing first kind of way to produce, but owing to lacking ruddiness in spectrum, cause its colour rendering index lower.Comparatively speaking, the second and the third scheme are the most promising developing direction realizing White-light LED illumination at present, but these two kinds of modes all need red, green fluorescence powder, and high quality available is at present red, green fluorescence powder kind is few, new phosphors research is still immature, synthesis condition is harsh, and patent is almost abroad monopolized, thus in the urgent need to development high luminescence can redness and green emitting phosphor new system.
Y-Si-O-N system material, as Y 2si 3o 3n 4, Y 4si 2o 7n 2, YSiO 2n,Y 6si 3o 9n 4y 2si 3o 3n 4deng, it is as matrix, and when doping with rare-earth ions, the luminescent properties that display is unique, had caused in recent years and shown great attention to, and be considered to potential fluorescent material.In such system, due to Y 3+for+3 valencys, therefore when rare earth doped light emitting ionic, be generally+3 valency rare earth ions and replace Y 3+, as with Ce 3+, Eu 3+and Tb 3+as doping agent.In this system, at present to doped Ce 3+fluorescent material research is more, and trivalent light emitting ionic Eu 3+and Tb 3+emission spectrum be line spectrum, its color developing and luminous efficiency poor, therefore study less.But, compare trivalent Eu 3+ionoluminescence, divalence Eu 2+emmission spectrum be band spectrum, color developing and luminous efficiency good.But due to the limitation of current preparation method, divalence Eu 2+be difficult to stable existence in Y-Si-O-N matrix.
Summary of the invention
The present invention is intended to the deficiency overcoming existing white fluorescence powder, preparation method thereof, the invention provides a kind of rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material and preparation method thereof.
The invention provides a kind of rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material, described Y 5si 3o 12the chemical formula of N fluorescent material is Y 5 (1-x)si 3o 12n:5xEu 2+, Eu 2+part replaces Y 3+, x=0.3 ~ 4.0mol%.
Preferably, described Y 5si 3o 12n fluorescent material is under the excitation wave of wavelength 270-370nm, and emission peak is in the scope of 508-578nm.
Preferably, described Y 5si 3o 12n fluorescent material, along with Eu 2+the increase gradually of concentration, can realize green emission to yellow transformation of launching.
Again, present invention also offers a kind of above-mentioned Y 5si 3o 12the preparation method of N fluorescent material, described method comprises:
1) first Y (NO will be comprised 3) 3, TEOS, Eu (NO 3) 3, SiC stock dispersion in the mixed solvent of water, ethanol composition, then heat and be uniformly mixed solvent and obtain colloidal sol, wherein Y (NO 3) 3molar weight, TEOS theoretical molar amount, Eu (NO 3) 3the ratio of molar weight meets the proportionlity of Y, Si, Eu in the constitutional chemistry formula of described fluorescent material, (2-4) that the actual use molar weight of TEOS is theoretical molar amount doubly, Y (NO 3) 3be 1:(0.2 ~ 0.5 with the mol ratio of SiC);
2) first by step 1) colloidal sol prepared grind into powder after gelation at 120-150 DEG C, then by powder 500-700 DEG C of pre-burnings;
3) by step 2) in the powder of pre-burning in nitrogen atmosphere, calcining at 1500-1700 DEG C, obtain described rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material.
Preferably, step 1) in, the quality of raw material: quality: ethanol quality=(2-4): (4-6): 2.
Preferably, step 1) in, described gelling temperature is 120 DEG C, and the time is 4-8 hour.
Preferably, step 2) in, the temperature rise rate of pre-sinter process is 2-5 DEG C/min, and soaking time is 4-6 hour.
Preferably, step 3) in, the temperature rise rate of calcining process is 10-20 DEG C/min, and soaking time is 6-15 hour, and the flow velocity of nitrogen is 0.7-1.2L/ hour, preferred 0.8L/ hour.
Beneficial effect of the present invention:
1. the invention provides a kind of novel green and yellow fluorescent powder and preparation method thereof, namely with bivalent rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material, selects high stable SiC to be effective reductive agent, overcomes Eu in the past 2+be difficult to stable existence in a difficult problem for Y-Si-O-N lattice.The mechanism of action of reductive agent SiC is as follows:
SiC(s)+2SiO 2(s)→3SiO(g)+CO(g)
3SiO(g)+2N 2(g)→Si 3N 4(s)+1.5O 2(g)
5Y 2O 3(s)+6SiO 2(s)+3CO(g)+N 2(g)→2Y 5Si 3O 12N(s)+3CO 2(g)
Gas phase SiO and the N generated 2there is chemical reaction, generate Si 3n 4, this reaction is gas-phase reaction, in an experiment BN sidewall of crucible is attached with Si 3n 4whisker, confirms above chemical reaction;
2.Y 5si 3o 12n:Eu 2+fluorescent material all has absorption at 270 ~ 370 wave band nm, and emmission spectrum peak position is along with the change (0.3 ~ 4.0mol%) of doping content, and can regulate and control between 508 ~ 578nm wave band, achieve the transformation of green glow yellow emission, spectrum variable range is large;
3. the presoma that the present invention selects is nitrate, and compare metal oxide or nitride, it has better mixing uniformity and reactive behavior, and the precursor powder activity of synthesis is high, effectively can reduce calcining temperature and shorten soaking time;
4. the silicon source that the present invention selects is tetraethoxy, its can in precursor solution with complexing of metal ion, then carry out polycondensation, and then form colloidal sol, make like this precursor material can more effectively dispersed with mix;
5. preparation method of the present invention is compared to traditional Y 5si 3o 12the advantages such as preparation method's (as nitride metal method) of N, has raw material cheap, and preparation condition is gentle.
Accompanying drawing explanation
Fig. 1 shows Y obtained under different calcination time in two embodiments of the present invention 4.985si 3o 12n:0.015Eu 2+(x=0.3mol%) X-ray diffractogram (XRD) of fluorescent material, in figure, bottom inserts Y 5si 3o 12the standard X-ray diffraction spectrum of N phase;
Fig. 2 shows Y obtained in two embodiments of the present invention 4.975si 3o 12n:0.025Eu 2+(x=0.5mol%) fluorescent powder excitation spectrum (emission wavelength lambda at normal temperatures emin=490nm, 514nm, figure, mark is respectively 1,2) and emmission spectrum (excitation wavelength lambda exin=282nm, 365nm, figure, mark is respectively 3,4);
Fig. 3 shows the different Eu of doping obtained in six embodiments of the present invention 2+the Y of concentration 5 (1-x)si 3o 12n fluorescent powder emmission spectrum (excitation wavelength lambda at normal temperatures ex=365nm), in figure 1,2,3,4,5,6 represent Eu respectively 2+doping content is the fluorescent material of x=0.3mol%, 0.5mol%, 1.0mol%, 2.0mol%, 3.0mol%, 4.0mol%, and along with the increase of doping content, emmission spectrum Dependent Red Shift, can realize the modulation from 508 ~ 578nm wave band;
Fig. 4 shows the coordinate of fluorescent material on chromaticity coordinates figure prepared in six embodiments, and in figure 1,2,3,4,5,6 represent Eu respectively 2+doping content is that the fluorescent material of x=0.3mol%, 0.5mol%, 1.0mol%, 2.0mol%, 3.0mol%, 4.0mol% is at l exduring=365nm shooting conditions, the chromaticity coordinates change in location of emmission spectrum, shows green glow the transformation of yellow emission, spectrum variable range is large.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The present invention relates to fluorescent material field, specifically, relate to the preparation method of a kind of white light LEDs and other illumination and technique of display green and yellow fluorescent powder, belong to technical field of function materials.Meanwhile, preparation condition of the present invention is gentle, operates fairly simple, is easy to realize scale production.
The invention provides a kind of rare earth ion Eu 2+the Y of doping 5si 3o 12n white-light LED fluorescence powder material and preparation method thereof.The preparation process of this phosphor material powder is as follows: first will form Y 5si 3o 12precursor material and the doped raw material of N press Y 5 (1- x)si 3o 12n:5xEu proportioning is dissolved in alcohol water mixed solvent, after stirring, adds appropriate SiC, reheats and be stirred to solation; Leave standstill 4 ~ 8h under 120 DEG C of conditions in an oven afterwards, complete gelation; Take out grinding, in retort furnace under air atmosphere 500 ~ 700 DEG C carry out pre-burning, take out grinding after cooling, then adopt high pure nitrogen atmosphere, carry out 1500 ~ 1700 DEG C of calcinings; Finally cool to room temperature with the furnace.
Luminescence center Eu in the present invention 2+mix Y 5si 3o 12time in N lattice, Eu 2+replace Y 3+case is aliovalent replacement.And Eu ion is+3 valencys in presoma, therefore select SiC as reductive agent, by Eu 3+be reduced to Eu 2+, realize Eu 2+the banded emmission spectrum of feature.
The fluorescent material invented all has absorption, with Eu at 270 ~ 370nm wave band 2+the change (0.3 ~ 4.0mol%) of doping content, can realize launching peak position in the regulation and control of 508 ~ 578nm scope, namely realize green glow the transmitting that gold-tinted changes, spectrum variable range is large, is applicable to the fluorescent material building UV LED chip, has luminous intensity high, the advantages such as excitation wave length and width, has potential using value in White-light LED illumination and other illumination and technique of display field.
Described rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material, its chemical formula is Y 5 (1-x)si 3o 12n:5xEu, namely uses Eu 2+part replaces Y 3+, described Eu 2+at Y 5si 3o 12in N matrix, doping content is x=0.3 ~ 4.0mol%.
The raw materials used composition of described fluorescent material can be converted as oxide compound, by yttrium oxide (Y 2o 3), europium sesquioxide (Eu 2o 3), silicon-dioxide (SiO 2) composition, and extra reductive agent silicon carbide (SiC) composition added.The mass percent of its raw materials used each component by conversion oxide compound is as follows:
The mass percent sum of above-mentioned each component is 100%;
Y 5si 3o 12nitrogenous source in N matrix is that after presoma pre-treatment, the powder of gained is calcined, at N in carbon tube furnace 2under the effect of atmosphere, N 2be reduced to N 3-, N 3-participate in reaction, enter in lattice, generate Y 5si 3o 12n product.
Form Y 5si 3o 12the precursor material of N is Yttrium trinitrate (Y (NO 3) 3), tetraethoxy (TEOS), described dopant material is europium nitrate (Eu (NO 3) 3), reductive agent is silicon carbide (SiC).
Actual amount mol ratio Y (NO 3) 3: TEOS=2:3=10:15, and theoretical amount mol ratio Y (NO 3) 3: TEOS=5:3=10:6, i.e. TEOS actual excessive 150%, calculation formula is (15-6)/6*100%=150%, and this is because TEOS is volatile, and actual amount need higher than Theoretical Calculation consumption.
At Y 5si 3o 12in N substrate fluorescent powder, described doping with rare-earth ions is Eu 2+, and the valence state of raw materials used middle Eu is Eu 3+, therefore select effective reductive agent to be SiC, actual amount mol ratio (Y (NO 3) 3: TEOS:SiC)=2:3:1.
Described alcohol water mixed solvent is by deionized water and dehydrated alcohol, is (4 ~ 6) in mass ratio: 2 compositions.
Described pre-burning, by the temperature rise rate of 2 ~ 5 DEG C/min, in air atmosphere, rises to pretreatment temperature 500 ~ 700 DEG C from room temperature in retort furnace.
Described calcining rises to calcining temperature 1500 ~ 1700 DEG C from room temperature, N by the temperature rise rate of 10-20 DEG C/min in hot-pressed sintering furnace 2flow velocity is 0.8L/h, and calcination time is 6 ~ 15h.
The present invention provides Eu 2+the Y of doping 5si 3o 12n new phosphors and preparation method thereof.Eu prepared by the present invention 2+the Y of doping 5si 3o 12n, under low doping concentration, emmission spectrum is positioned at green light band, is green emitting phosphor, can meet the demand now to green emitting phosphor; And when doping content increases further, yellow emission can be realized, emission spectrum variable range is large, has a good application prospect.
Beneficial effect of the present invention:
1. the invention provides a kind of novel green and yellow fluorescent powder and preparation method thereof, namely with bivalent rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material, selects high stable SiC to be effective reductive agent, overcomes Eu in the past 2+be difficult to stable existence in a difficult problem for Y-Si-O-N lattice.The mechanism of action of reductive agent SiC is as follows:
SiC(s)+2SiO 2(s)→3SiO(g)+CO(g)
3SiO(g)+2N 2(g)→Si 3N 4(s)+1.5O 2(g)
5Y 2O 3(s)+6SiO 2(s)+3CO(g)+N 2(g)→2Y 5Si 3O 12N(s)+3CO 2(g)
Gas phase SiO and the N generated 2there is chemical reaction, generate Si 3n 4, this reaction is gas-phase reaction, in an experiment BN sidewall of crucible is attached with Si 3n 4whisker, confirms above chemical reaction;
2.Y 5si 3o 12n:Eu 2+fluorescent material all has absorption at 270 ~ 370 wave band nm, and emmission spectrum peak position is along with the change (0.3 ~ 4.0mol%) of doping content, and can regulate and control between 508 ~ 578nm wave band, achieve the transformation of green glow yellow emission, spectrum variable range is large;
3. the presoma that the present invention selects is nitrate, and compare metal oxide or nitride, it has better mixing uniformity and reactive behavior, and the precursor powder activity of synthesis is high, effectively can reduce calcining temperature and shorten soaking time;
4. the silicon source that the present invention selects is tetraethoxy, its can in precursor solution with complexing of metal ion, then carry out polycondensation, and then form colloidal sol, make like this precursor material can more effectively dispersed with mix;
5. preparation method of the present invention is compared to traditional Y 5si 3o 12the advantages such as preparation method's (as nitride metal method) of N, has raw material cheap, and preparation condition is gentle.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following processing parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
Raw material is Y by the mass ratio of folding synthesis oxide 2o 3: Eu 2o 3: SiO 2: (SiC)=5.61:0.03:4.49:(1) (being equivalent to Eu doping x=0.3mol%) measure Yttrium trinitrate (Y (NO 3) 3), tetraethoxy (TEOS), europium nitrate (Eu (NO 3) 3), silicon carbide (SiC) each raw material, above-mentioned all raw materials are dissolved in the mixed solvent that deionized water and dehydrated alcohol form, the wherein total mass of constitutive material: deionized water quality: dehydrated alcohol quality=1.9:3:1, heated and stirred is to colloidal sol, put into baking oven afterwards and leave standstill 6h under 120 DEG C of conditions, take out grinding, put into retort furnace and rise to 600 DEG C by the temperature rise rate of 5 DEG C/min from room temperature, pre-treatment 6h in air atmosphere, again gained powder is put into hot pressing furnace afterwards and rise to 1560 DEG C by the temperature rise rate of 10 DEG C/min from room temperature, at the N of 0.8L/h flow 2calcine 6h under atmosphere, cool to room temperature with the furnace, obtain Y 4.985si 3o 12n:0.015Eu 2+(x=0.3mol%) fluorescent powder.Synthetic powder degree of crystallinity is high, XRD diffraction facies analysis result as shown in Figure 1.Detect and learn that phosphor material powder obtained by the present embodiment transmitting peak position is at room temperature at 508nm (l ex=365nm), chromaticity coordinates position is (0.277,0.406), belongs to green emission fluorescent material.
Embodiment 2
On the basis of embodiment 1, increase Eu 2+doping.By folding synthesis oxide mass ratio be Y 2o 3: Eu 2o 3: SiO 2: (SiC)=5.60:0.04:4.49:(1) (being equivalent to Eu doping x=0.5mol%) measure Yttrium trinitrate (Y (NO 3) 3), tetraethoxy (TEOS), europium nitrate (Eu (NO 3) 3), silicon carbide (SiC) each raw material, above-mentioned all raw materials are dissolved in the mixed solvent that deionized water and dehydrated alcohol form, the wherein total mass of constitutive material: deionized water quality: dehydrated alcohol quality=1.9:3:1, heated and stirred is to colloidal sol, put into baking oven afterwards and leave standstill 6h under 120 DEG C of conditions, take out grinding, put into retort furnace and rise to 600 DEG C by the temperature rise rate of 5 DEG C/min from room temperature, pre-treatment 6h in air atmosphere, again gained powder is put into hot pressing furnace afterwards and rise to 1560 DEG C by the temperature rise rate of 10 DEG C/min from room temperature, at the N of 0.8L/h flow 2calcine 6h under atmosphere, cool to room temperature with the furnace, obtain Y 4.975si 3o 12n:0.025Eu 2+(x=0.5mol%) fluorescent powder.Detect and learn that phosphor material powder obtained by the present embodiment transmitting peak position is at room temperature at 510nm (l ex=365nm), chromaticity coordinates position is (0.277,0.406).The excitation spectrum of this fluorescent material and emission spectrum as shown in Figure 2, are green emission.
Embodiment 3
On the basis of embodiment 2, increase Eu further 2+doping.By folding synthesis oxide mass ratio be Y 2o 3: Eu 2o 3: SiO 2: (SiC)=5.40:0.35:4.49:(1) (being equivalent to Eu doping x=4.0mol%) measure Yttrium trinitrate (Y (NO 3) 3), tetraethoxy (TEOS), europium nitrate (Eu (NO 3) 3), silicon carbide (SiC) each raw material, above-mentioned all raw materials are dissolved in the mixed solvent that deionized water and dehydrated alcohol form, the wherein total mass of constitutive material: deionized water quality: dehydrated alcohol quality=1.9:3:1, heated and stirred is to colloidal sol, put into baking oven afterwards and leave standstill 6h under 120 DEG C of conditions, take out grinding, put into retort furnace and rise to 600 DEG C by the temperature rise rate of 5 DEG C/min from room temperature, pre-treatment 6h in air atmosphere, again gained powder is put into hot pressing furnace afterwards and rise to 1560 DEG C by the temperature rise rate of 10 DEG C/min from room temperature, at the N of 0.8L/h flow 2calcine 6h under atmosphere, cool to room temperature with the furnace, obtain Y 4. 8si 3o 12n:0.2Eu 2+(x=4.0mol%) fluorescent powder.Detect and learn that phosphor material powder obtained by the present embodiment transmitting peak position is at room temperature at 578nm, chromaticity coordinates position is (0.445,0.482), belongs to yellow emission.Compared to Eu 2+doping content is the fluorescent material of 0.3mol% gained, its emission spectrum red shift 70nm, namely by changing rare earth ion Eu 2+doping content, can realize the regulation and control in a big way of phosphor emission spectrum peak position, emission spectrum red shift effect as shown in Figure 3, different Eu 2+as shown in Figure 4, namely the emmission spectrum of fluorescent material can from green glow modulation to gold-tinted for the chromaticity coordinates of doping content gained fluorescent material.
Embodiment 4
On the basis of embodiment 1, improve calcining temperature.By folding synthesis oxide mass ratio be Y 2o 3: Eu 2o 3: SiO 2: (SiC)=5.61:0.03:4.49:(1) (being equivalent to Eu doping x=0.3mol%) measure Yttrium trinitrate (Y (NO 3) 3), tetraethoxy (TEOS), europium nitrate (Eu (NO 3) 3), silicon carbide (SiC) each raw material, above-mentioned all raw materials are dissolved in the mixed solvent that deionized water and dehydrated alcohol form, the wherein total mass of constitutive material: deionized water quality: dehydrated alcohol quality=1.9:3:1, heated and stirred is to colloidal sol, put into baking oven afterwards and leave standstill 6h under 120 DEG C of conditions, take out grinding, put into retort furnace and rise to 600 DEG C by the temperature rise rate of 5 DEG C/min from room temperature, pre-treatment 6h in air atmosphere, again gained powder is put into hot pressing furnace afterwards and rise to 1600 DEG C by the temperature rise rate of 10 DEG C/min from room temperature, at the N of 0.8L/h flow 2calcine 6h under atmosphere, cool to room temperature with the furnace, obtain Y 4.985si 3o 12n:0.015Eu 2+(x=0.3mol%) fluorescent powder.Synthetic powder degree of crystallinity is high, XRD diffraction facies analysis result as shown in Figure 1.

Claims (8)

1. a rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material, is characterized in that, described Y 5si 3o 12the chemical formula of N fluorescent material is Y 5 (1-x)si 3o 12n:5 xeu 2+, Eu 2+part replaces Y 3+, x=0.3-4.0mol%.
2. Y according to claim 1 5si 3o 12n fluorescent material, is characterized in that, described Y 5si 3o 12n fluorescent material is under the excitation wave of wavelength 270-370nm, and emission peak is in the scope of 508-578nm.
3. Y according to claim 1 and 2 5si 3o 12n fluorescent material, is characterized in that, described Y 5si 3o 12n fluorescent material, along with Eu 2+the increase gradually of concentration, can realize green emission to yellow transformation of launching.
4. arbitrary described Y in a claim 1-3 5si 3o 12the preparation method of N fluorescent material, is characterized in that, described method comprises:
1) first Y (NO will be comprised 3) 3, TEOS, Eu (NO 3) 3, SiC stock dispersion in the mixed solvent of water, ethanol composition, then heat and be uniformly mixed solvent and obtain colloidal sol, wherein Y (NO 3) 3molar weight, TEOS theoretical molar amount, Eu (NO 3) 3the ratio of molar weight meets the proportionlity of Y, Si, Eu in the constitutional chemistry formula of described fluorescent material, (2-4) that the actual use molar weight of TEOS is theoretical molar amount doubly, Y (NO 3) 3be 1:(0.2 ~ 0.5 with the mol ratio of SiC);
2) colloidal sol first prepared by step 1) grind into powder after gelation at 120-150 DEG C, then by powder 500-700 DEG C of pre-burnings;
3) by step 2) in the powder of pre-burning in nitrogen atmosphere, calcining at 1500-1700 DEG C, obtain described rare earth ion Eu 2+the Y of doping 5si 3o 12n fluorescent material.
5. preparation method according to claim 4, is characterized in that, in step 1), and the quality of raw material: quality: ethanol quality=(2-4): (4-6): 2.
6. the preparation method according to claim 4 or 5, is characterized in that, in step 1), described gelling temperature is 120 DEG C, and the time is 4-8 hour.
7., according to described preparation method arbitrary in claim 4-6, it is characterized in that, step 2) in, the temperature rise rate of pre-sinter process is 2-5 DEG C/min, and soaking time is 4-6 hour.
8., according to described preparation method arbitrary in claim 4-7, it is characterized in that, in step 3), the temperature rise rate of calcining process is 10-20 DEG C/min, and soaking time is 6-15 hour, and the flow velocity of nitrogen is 0.7-1.2L/ hour, preferred 0.8L/ hour.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106281312A (en) * 2016-07-15 2017-01-04 烟台希尔德新材料有限公司 A kind of rear-earth-doped nitrogen oxides red emitter and illuminating device
CN106947470A (en) * 2017-03-31 2017-07-14 英特美光电（苏州）有限公司 LED and remote fluorescence device small size salt a kind of novel processing step
CN112340712A (en) * 2020-11-09 2021-02-09 厦门大学 Nitrogen oxide elastic stress luminescent material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102952542A (en) * 2012-10-24 2013-03-06 江苏博睿光电有限公司 Nitride or nitrogen oxide fluorescent powder and preparation method thereof
CN103119126A (en) * 2010-09-17 2013-05-22 株式会社东芝 Phosphor and light-emitting device
CN103146386A (en) * 2013-03-15 2013-06-12 河北大学 Europium doped lanthanide silicon oxynitride and preparation method thereof
CN103525419A (en) * 2013-09-27 2014-01-22 中国科学院长春应用化学研究所 Method for preparing nitrogen oxygen silicate luminescent material in normal pressure and at low temperature
CN103881706A (en) * 2012-12-21 2014-06-25 有研稀土新材料股份有限公司 Nitrogen oxide fluorescent powder, preparation method thereof and luminescent device containing the fluorescent powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103119126A (en) * 2010-09-17 2013-05-22 株式会社东芝 Phosphor and light-emitting device
CN102952542A (en) * 2012-10-24 2013-03-06 江苏博睿光电有限公司 Nitride or nitrogen oxide fluorescent powder and preparation method thereof
CN103881706A (en) * 2012-12-21 2014-06-25 有研稀土新材料股份有限公司 Nitrogen oxide fluorescent powder, preparation method thereof and luminescent device containing the fluorescent powder
CN103146386A (en) * 2013-03-15 2013-06-12 河北大学 Europium doped lanthanide silicon oxynitride and preparation method thereof
CN103525419A (en) * 2013-09-27 2014-01-22 中国科学院长春应用化学研究所 Method for preparing nitrogen oxygen silicate luminescent material in normal pressure and at low temperature

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FA-CHUN LU 等: "Photoluminescence properties of Y5Si3O12N:Ce3+ blue-emitting phosphors for white LED", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
FA-CHUN LU等: "Synthesis and Photoluminescence of a Novel Green-Emitting La5Si3O12N: Eu2+", 《J.AM.CERAM.SOC.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106281312A (en) * 2016-07-15 2017-01-04 烟台希尔德新材料有限公司 A kind of rear-earth-doped nitrogen oxides red emitter and illuminating device
CN106947470A (en) * 2017-03-31 2017-07-14 英特美光电（苏州）有限公司 LED and remote fluorescence device small size salt a kind of novel processing step
CN112340712A (en) * 2020-11-09 2021-02-09 厦门大学 Nitrogen oxide elastic stress luminescent material and preparation method thereof

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