CN101724400A - Method for preparing fluorescent powder for white light LED - Google Patents
Method for preparing fluorescent powder for white light LED Download PDFInfo
- Publication number
- CN101724400A CN101724400A CN200910230558A CN200910230558A CN101724400A CN 101724400 A CN101724400 A CN 101724400A CN 200910230558 A CN200910230558 A CN 200910230558A CN 200910230558 A CN200910230558 A CN 200910230558A CN 101724400 A CN101724400 A CN 101724400A
- Authority
- CN
- China
- Prior art keywords
- solution
- preparation
- precursor powder
- mixed
- white light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 43
- 239000002243 precursor Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000012716 precipitator Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical class [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention relates to a method for preparing fluorescent powder for white light LEDs, which comprises the following process steps: preparing a mixed solution of metal salts containing Y, Al, Ce and Ln(Ln may be Tb, Gd and Pr) a molar ratio determined by a chemical general formula of Y3-x-yAl15O12:Cex, Lny (Ln may be Tb, Gd and Pr) (x is equal to 0.01 to 0.25 and y is equal to 0.01 to 0.25); mixing solution of NH4HCO3 and solution of ammonia or solution of urea to form a composite precipitator; under a condition of intense stirring, slowly dripping the mixed solution of metal salts into solution of the composite precipitator to obtain a white precipitate; and subjecting the precipitate to dehydrating, washing with deionized water, drying at constant temperature, grinding and calcining in an inert atmosphere to obtain target powder. Compared with a high-temperature solid-phase sintering method in the prior art, the method has the advantages that: an H2 reducing atmosphere is saved; the sintering temperature is below 300 to 600 DEG C; the yield is high; the products have excellent optical performance and can be prepared in batch easily.
Description
Technical field
The present invention relates to the adulterated yttrium aluminum garnet class of a kind of double rare-earth elements fluorescent material, be YAG:Ce, Ln (Ln=Tb, Gd, preparation method Pr), it is simple to relate in particular to a kind of preparation technology, sintering temperature is low, the YAG:Ce that luminescent properties is good, Ln (Ln=Tb, Gd, Pr) preparation method of fluorescent material.
Background technology
White light LEDs is a kind of novel " green illumination " solid light source, obvious energy conservation and have the life-span long, volume is little, the brightness advantages of higher, is widely used in aspects such as industry, military affairs, medical science and scientific research, has huge marketable value and social benefit.At present, white light LEDs mainly is to realize with yttrium aluminum garnet (YAG:Ce) phosphor combination of mixing cerium by employing InGaN/GaN base blue chip, but red light intensity deficiency in the emmission spectrum of this fluorescent material causes the white light LEDs colour rendering index on the low side.If mix suitable rare earth ion again, make the emmission spectrum generation red shift of fluorescent material or increase the red emission peak, can improve the colour rendering index of white light LEDs.
At present, YAG:Ce, (Pr) fluorescent material adopts the high temperature solid-phase sintering method to prepare to Ln for Ln=Tb, Gd.General oxide compound (Y with respective element
2O
3, Al
2O
3, CeO
2, Tb
4O
7, Gd
2O
3, Pr
6O
11) make raw material, add fusing assistant BaF
2(or NaF), H
3BO
3, in reducing atmosphere (hydrogen), obtain by high temperature sintering.In high-temperature sintering process, adopting the purpose of reducing atmosphere is in order to make the quadrivalent cerium, part tetravalence terbium, the part tetravalence praseodymium that are entrained in wherein be reduced to trivalent cerium, trivalent terbium, trivalent praseodymium respectively.
Yet, at the YAG:Ce of finding report, Ln (Ln=Tb, Gd, Pr) in the preparation of fluorescent material, exist the pressed powder raw material mix inhomogeneous, sintering temperature is higher (1500 ℃), need reducing gas (hydrogen) to cause great number of issues such as unsafe factor.
Goal of the invention and content
At present YAG:Ce, Ln (Ln=Tb, Gd, Pr) complex process that exists in the preparation of fluorescent material, sintering temperature height, need problems such as hydrogen reducing atmosphere, the object of the present invention is to provide a kind of phosphor for white light LED YAG:Ce, Ln (Ln=Tb, Gd, Pr) liquid phase preparation process promptly adopts compound precipitants to prepare the method for this fluorescent material.The raw material that this method is used does not need mechanically mixing, and sintering temperature is low, does not need hydrogen reducing atmosphere, does not have danger, and the output height is easy to realize producing in batches.
Purpose of the present invention can be realized by following technical scheme.
The preparation method of phosphor for white light LED of the present invention adopts following processing step:
(1) preparation of mixed salt solution (M liquid):
According to chemical general formula Y
3-x-yAl
5O
12: Ce
x, Ln
y(Pr) mol ratio of (x=0.01～0.25, y=0.01～0.25) is mixed with and contains Y, Al, Ce, Ln (Ln=Tb, Gd, mixed salt solution Pr) for Ln=Tb, Gd.
(2) preparation of composite precipitation agent solution (P liquid):
With NH
4HCO
3Solution and NH
3H
2O solution according to the mixed of mol ratio 1: 0.1～10 as compound precipitants; Perhaps with NH
4HCO
3Solution and urea soln according to the mixed of mol ratio 1: 0.1～10 as compound precipitants.
(3) preparation of precursor powder:
The powerful stirring down slowly joins M liquid in the P liquid, obtains white precipitate; To obtain precursor powder after this throw out dehydration, deionized water wash, freeze-day with constant temperature, the grinding.
(4) sintering of precursor powder:
This precursor powder is put into atmosphere furnace, after the employing inert atmosphere protection carries out sintering, naturally cool to room temperature and can obtain fluorescent material of the present invention.
Wherein, described mixed salt solution is the mixing solutions of yttrium nitrate solution, aluminum nitrate solution, cerous nitrate solution, terbium chloride solution, Gadolinium trinitrate solution, praseodymium nitrate solution.In the preparation of described precursor powder, throw out is used the deionized water thorough washing after adopting centrifugal dewatering, till detecting the existence of no nitrate ion and chlorion; The gained throw out needs 30～100 ℃ of freeze-day with constant temperature 1～10 hour.In the sintering of described precursor powder, the control sintering temperature is 900～1200 ℃, and soaking time is 1～10 hour; Inert atmosphere adopts nitrogen or argon gas.
Specifically:
With a certain amount of Y (NO
3)
36H
2O, Al (NO
3)
39H
2O, Ce (NO
3)
36H
2O is mixed with certain density solution with deionized water dissolving respectively.Tb
4O
7With dissolving with hydrochloric acid and be mixed with certain density TbCl
3Solution, Gd
2O
3And Pr
2O
3Powder is with dilute nitric acid dissolution and be mixed with certain density Gd (NO
3)
3And Pr (NO
3)
3Solution.According to chemical general formula Y
3-x-yAl
5O
12: Ce
x, Ln
y(Pr) mol ratio of (x=0.01～0.25, y=0.01～0.25) is mixed with and contains Y, Al, Ce, Ln (Ln=Tb, Gd, mixed salt solution Pr) for Ln=Tb, Gd.
With NH
4HCO
3Solution and NH
3H
2O solution or NH
4HCO
3Solution mixes as compound precipitants according to different mol ratio ratio (changing to 1: 10 from 1: 0.1 respectively) with urea soln.
Under powerful agitation condition, the mixed salt solution for preparing slowly is added drop-wise in the composite precipitation agent solution.After dropwising, obtain white precipitate, leave standstill 30 minutes natural subsidence, outwell supernatant liquid then, throw out is carried out centrifugation and uses deionized water washing sediment 3 times.With the gained throw out put into thermostatic drying chamber 30～100 ℃ dry 1～10 hour down, dry back is taken out presoma and is ground with mortar and obtains precursor powder.
Precursor powder is placed porcelain boat, put into the atmosphere furnace burner hearth, adopt inert atmosphere (nitrogen or argon gas) protection, temperature is warmed up to 900～1200 ℃ gradually, is incubated after 1～10 hour, naturally cools to room temperature and obtains target powder.
The present invention compared with prior art has following technological merit:
(1) YAG:Ce of the present invention preparation, Ln (Ln=Tb, Gd, Pr) fluorescent material 460nm blue-light excited down, the light that sends is fit to white light LEDs and uses.
(2) target powder that adopts the compound precipitants sintering of different mixing proportion to obtain does not need to grind.
(3) compare with prior art high temperature solid-phase sintering method, the present invention does not need hydrogen reducing atmosphere, and sintering temperature is low 300～600 ℃, the output height, and product has the good optical performance, is easy to realize batch preparations.
Description of drawings
Fig. 1 is by the YAG:Ce of the inventive method preparation, the XRD figure of Tb fluorescent material
Fig. 2 is by the YAG:Ce of the inventive method preparation, the excitation spectrum of Tb fluorescent material
Fig. 3 is by the YAG:Ce of the inventive method preparation, the emmission spectrum of Tb fluorescent material
Fig. 4 is by the YAG:Ce of the inventive method preparation, the XRD figure of Gd fluorescent material
Fig. 5 is by the YAG:Ce of the inventive method preparation, the excitation spectrum of Gd fluorescent material
Fig. 6 is by the YAG:Ce of the inventive method preparation, the emmission spectrum of Gd fluorescent material
Fig. 7 is by the YAG:Ce of the inventive method preparation, the XRD figure of Pr fluorescent material
Fig. 8 is by the YAG:Ce of the inventive method preparation, the excitation spectrum of Pr fluorescent material
Fig. 9 is by the YAG:Ce of the inventive method preparation, the emmission spectrum of Pr fluorescent material
Embodiment
Embodiment 1:
(1) preparation of mixed salt solution
According to chemical general formula Y
3-x-yAl
5O
12: Ce
x, Tb
y(x=0.06, mol ratio y=0.03) is mixed with and contains Y
3+, Al
3+, Ce
3+, Tb
3+Mixed salt solution.
Specifically:
In stink cupboard, with 0.5608gTb
4O
7Powder is put into beaker, adds the hydrochloric acid soln of 21mL0.5mol/L then in beaker, constantly stirs, and until complete reaction, is mixed with the TbCl that 100mL concentration is 0.03mol/L then
3Solution.
With 2.229g Y (NO
3)
36H
2O powder, 3.752g Al (NO
3)
39H
2O powder, 0.052g Ce (NO
3)
36H
2The O powder is put into beaker, adds the TbCl of 2.0mL 0.03mol/L again
3Solution adds the 200mL deionized water then, constantly stirs to make the pressed powder dissolving, obtains mixed salt solution.
(2) preparation of composite precipitation agent solution
With 31.600g NH
4HCO
3Powder with deionized water dissolving after, be mixed with the NH of 200mL 2mol/L
4HCO
3Solution.Get the NH that the 14ml strong aqua is mixed with 100mL 2mol/L
3H
2O solution.Get the above-mentioned NH of 181.8mL
4HCO
3The above-mentioned NH of solution and 18.2mL
3H
2O solution (the mol ratio ratio is 1: 0.1) mixes as compound precipitants.
(3) preparation of precursor powder
The resulting mixed salt solution of (1) step is added drop-wise in the resulting beaker that fills compound precipitants of (2) step, and constantly stirs.After dropwising, obtain white precipitate, leave standstill 30 minutes natural subsidence, outwell supernatant liquid then, throw out is carried out centrifugation and uses deionized water washing sediment 3 times.With the gained throw out put into thermostatic drying chamber 60 ℃ dry 3 hours down, dry back is taken out presoma and is ground with mortar and obtains precursor powder.
(4) sintering of precursor powder
The resulting precursor powder of (3) step is placed porcelain boat, put into the atmosphere furnace burner hearth, adopt the nitrogen atmosphere protection, temperature is warmed up to 900 ℃ gradually, is incubated after 2 hours, naturally cools to room temperature and obtains Y
2.91Ce
0.06Tb
0.03Al
5O
12Powder.
The XRD figure of products therefrom is seen accompanying drawing 1.Each diffraction peak and standard card JCPDS No33-0040 match as can be seen from accompanying drawing 1, are indicated as the body-centered cubic phase, do not have other dephasign.
(5) luminescent properties test
Accompanying drawing 2 is prepared Y
2.91Ce
0.06Tb
0.03Al
5O
12The excitation spectrum of fluorescent material (the monitoring wavelength is 530nm), as can be seen, excitation spectrum is rendered as wide absorption band near 460nm from accompanying drawing 2, and the blue chip that is fit to 460nm excites.Accompanying drawing 3 is prepared YAG:Ce, the emmission spectrum of Tb fluorescent material (usefulness 460nm's is blue-light excited), and from accompanying drawing 3 as can be seen, emmission spectrum is rendered as wide emission band, and glow peak is positioned at about 530nm, and the luminous intensity height.
Embodiment 2:
(1) preparation of mixed salt solution
According to chemical general formula Y
3-x-yAl
5O
12: Ce
x, Gd
y(x=0.06, mol ratio y=0.03) is mixed with and contains Y
3+, Al
3+, Ce
3+, Gd
3+Mixed salt solution.
That is, in stink cupboard, with 0.5438g Gd
2O
3Powder is put into beaker, adds the salpeter solution of 18mL 0.5mol/L then in beaker, constantly stirs, and until complete reaction, is mixed with the Gd (NO of 100mL 0.03mol/L then
3)
3Solution.With 2.229g Y (NO
3)
36H
2O powder, 3.752g Al (NO
3)
39H
2O powder, 0.052g Ce (NO
3)
36H
2The O powder is put into beaker, adds the Gd (NO of 2mL 0.03mol/L again
3)
3Solution adds the 200mL deionized water then, constantly stirs to make the pressed powder dissolving, obtains containing Y
3+, Al
3+, Ce
3+, Gd
3+Mixed salt solution.
(2) preparation of composite precipitation agent solution
With 31.600gNH
4HCO
3Powder with deionized water dissolving after, be mixed with the NH of 200mL 2mol/L
4HCO
3Solution.Get the NH that the 14ml strong aqua is mixed with 100mL 2mol/L
3H
2O solution.Get the above-mentioned NH of 181.8mL
4HCO
3The above-mentioned NH of solution and 18.2mL
3H
2O solution (the mol ratio ratio is 1: 0.1) mixes as compound precipitants.
(3) preparation of precursor powder
The resulting mixed salt solution of (1) step is added drop-wise in the resulting beaker that fills compound precipitants of (2) step, and constantly stirs.After dropwising, obtain white precipitate, leave standstill 30 minutes natural subsidence, outwell supernatant liquid then, throw out is carried out centrifugation and uses deionized water washing sediment 3 times.With the gained throw out put into thermostatic drying chamber 60 ℃ dry 3 hours down, dry back is taken out presoma and is ground with mortar and obtains precursor powder.
(4) sintering of precursor powder
The resulting precursor powder of (3) step is placed porcelain boat, put into the atmosphere furnace burner hearth, adopt the nitrogen atmosphere protection, temperature is warmed up to 900 ℃ gradually, is incubated after 2 hours, naturally cools to room temperature and obtains Y
2.91Ce
0.06Gd
0.03Al
5O
12Powder.
The XRD figure of products therefrom is seen accompanying drawing 4.Each diffraction peak and standard card JCPDS No.33-0040 match as can be seen from accompanying drawing 4, are indicated as the body-centered cubic phase, do not have other dephasign.
(5) luminescent properties test
Accompanying drawing 5 is prepared Y
2.91Ce
0.06Gd
0.03Al
5O
12The excitation spectrum of fluorescent material (the monitoring wavelength is 530nm), as can be seen, excitation spectrum is rendered as wide absorption band near 460nm from accompanying drawing 5, and the blue chip that is fit to 460nm excites.Accompanying drawing 6 is prepared Y
2.91Ce
0.06Gd
0.03Al
5O
12The emmission spectrum of fluorescent material (usefulness 460nm's is blue-light excited), from accompanying drawing 6 as can be seen, emmission spectrum is rendered as wide emission band, and glow peak is positioned at about 530nm, and the luminous intensity height.
Embodiment 3:
(1) preparation of mixed salt solution
According to chemical general formula Y
3-x-yAl
5O
12: Ce
x, Pr
y(x=0.06, mol ratio y=0.03) is mixed with and contains Y
3+, Al
3+, Ce
3+, Pr
3+Mixed salt solution.
That is, in stink cupboard, with 0.4948g Pr
2O
3Powder is put into beaker, adds the salpeter solution of 18mL 0.5mol/L then in beaker, constantly stirs, and until complete reaction, is mixed with the Pr (NO of 100mL 0.03mol/L then
3)
3Solution.With 2.229g Y (NO
3)
36H
2O powder, 3.752g Al (NO
3)
39H
2O powder, 0.052g Ce (NO
3)
36H
2The O powder is put into beaker, adds the Pr (NO of 2mL 0.03mol/L again
3)
3Solution adds the 200mL deionized water then, constantly stirs to make the pressed powder dissolving, obtains containing Y
3+, Al
3+, Ce
3+, Pr
3+Mixed salt solution.
(2) preparation of composite precipitation agent solution
With 31.600g NH
4HCO
3Powder with deionized water dissolving after, be mixed with the NH of 200mL 2mol/L
4HCO
3Solution.Get the NH that the 14ml strong aqua is mixed with 100mL 2mol/L
3H
2O solution.Get the above-mentioned NH of 181.8mL
4HCO
3The above-mentioned NH of solution and 18.2mL
3H
2O solution (the mol ratio ratio is 1: 0.1) mixes as compound precipitants.
(3) preparation of precursor powder
The resulting mixed salt solution of (1) step is added drop-wise in the resulting beaker that fills compound precipitants of (2) step, and constantly stirs.After dropwising, obtain white precipitate, leave standstill 30 minutes natural subsidence, outwell supernatant liquid then, throw out is carried out centrifugation and uses deionized water washing sediment 3 times.With the gained throw out put into thermostatic drying chamber 60 ℃ dry 3 hours down, dry back is taken out presoma and is ground with mortar and obtains precursor powder.
(4) sintering of precursor powder
The resulting precursor powder of (3) step is placed porcelain boat, put into the atmosphere furnace burner hearth, adopt the nitrogen atmosphere protection, temperature is warmed up to 900 ℃ gradually, is incubated after 2 hours, naturally cools to room temperature and obtains Y
2.91Ce
0.06Pr
0.03Al
5O
12Powder.
The XRD figure of products therefrom is seen accompanying drawing 7.Each diffraction peak and standard card JCPDS No.33-0040 match as can be seen from accompanying drawing 7, are indicated as the body-centered cubic phase, do not have other dephasign.
(5) luminescent properties
Accompanying drawing 8 is prepared Y
2.91Ce
0.06Pr
0.03Al
5O
12The excitation spectrum of fluorescent material (the monitoring wavelength is 530nm), as can be seen, excitation spectrum is rendered as wide absorption band near 460nm from accompanying drawing 8, and the blue chip that is fit to 460nm excites.Accompanying drawing 9 is prepared Y
2.91Ce
0.06Pr
0.03Al
5O
12The emmission spectrum of fluorescent material (usefulness 460nm's is blue-light excited), from accompanying drawing 9 as can be seen, emmission spectrum is rendered as wide emission band, and glow peak is positioned at about 530nm, and the luminous intensity height.Other embodiment is as follows:
Preparation technology is with embodiment 1,2,3, and its technical data is as shown in the table.
Claims (4)
1. the preparation method of a phosphor for white light LED is characterized in that, this preparation method adopts following steps:
(1) preparation of mixed salt solution (M liquid):
According to chemical general formula Y
3-x-yAl
5O
12: Ce
x, Ln
y(Pr) mol ratio of (x=0.01～0.25, y=0.01～0.25) is mixed with and contains Y, Al, Ce, Ln (Ln=Tb, Gd, mixed salt solution Pr) for Ln=Tb, Gd.
(2) preparation of composite precipitation agent solution (P liquid):
With NH
4HCO
3Solution and NH
3H
2O solution according to the mixed of mol ratio 1: 0.1～10 as compound precipitants; Perhaps with NH
4HCO
3Solution and urea soln according to the mixed of mol ratio 1: 0.1～10 as compound precipitants.
(3) preparation of precursor powder:
The powerful stirring down slowly joins M liquid in the P liquid, obtains white precipitate; To obtain precursor powder after this throw out dehydration, deionized water wash, freeze-day with constant temperature, the grinding.
(4) sintering of precursor powder:
This precursor powder is put into atmosphere furnace, after the employing inert atmosphere protection carries out sintering, naturally cool to room temperature and can obtain fluorescent material of the present invention.
2. the preparation method of phosphor for white light LED as claimed in claim 1, it is characterized in that, in the preparation of described precursor powder, after throw out adopts centrifugal dewatering, use the deionized water thorough washing, till detecting the existence of no nitrate ion and chlorion.
3. the preparation method of phosphor for white light LED as claimed in claim 1 is characterized in that, in the preparation of described precursor powder, the gained throw out needs 30～100 ℃ of freeze-day with constant temperature 1～10 hour.
4. the preparation method of phosphor for white light LED as claimed in claim 1 is characterized in that, in the sintering of described precursor powder, the control sintering temperature is 900～1200 ℃, and soaking time is 1～10 hour; Inert atmosphere adopts nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102305588A CN101724400B (en) | 2009-11-30 | 2009-11-30 | Method for preparing fluorescent powder for white light LED |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102305588A CN101724400B (en) | 2009-11-30 | 2009-11-30 | Method for preparing fluorescent powder for white light LED |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101724400A true CN101724400A (en) | 2010-06-09 |
| CN101724400B CN101724400B (en) | 2013-09-11 |
Family
ID=42445969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102305588A Expired - Fee Related CN101724400B (en) | 2009-11-30 | 2009-11-30 | Method for preparing fluorescent powder for white light LED |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101724400B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703078A (en) * | 2012-06-25 | 2012-10-03 | 重庆文理学院 | Secondary excitation type yellowish green fluorescent powder and preparation method thereof |
| CN102936497A (en) * | 2012-11-08 | 2013-02-20 | 广州有色金属研究院 | Main emission peak changeable and adjustable fluorescent material and preparation method thereof |
| CN103289697A (en) * | 2012-03-02 | 2013-09-11 | 河南森源电气股份有限公司 | Preparation method of high-performance YAG (yttrium aluminium garnet) yellow fluorescent powder |
| CN103590111A (en) * | 2013-09-29 | 2014-02-19 | 温州大学 | Annealing method of cerium-doped yttrium aluminium garnet wafer for white-light LED (Light Emitting Diode) |
| CN103992796A (en) * | 2014-05-30 | 2014-08-20 | 盐城工学院 | Method for preparing yellow phosphor with photo-enhanced function |
| CN112266239A (en) * | 2020-10-19 | 2021-01-26 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-color-rendering-index fluorescent ceramic for white light LED/LD and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718669A (en) * | 2005-07-14 | 2006-01-11 | 上海交通大学 | Method of preparing cerium activated yttrium aluminium garnet ultrafine fluorescent powder using coprecipitation |
| CN101134896A (en) * | 2007-10-16 | 2008-03-05 | 厦门大学 | Method for preparing rare earth doping yttrium aluminium garnet fluorescent powder by oxalic acid non-homogeneous phase deposition |
-
2009
- 2009-11-30 CN CN2009102305588A patent/CN101724400B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718669A (en) * | 2005-07-14 | 2006-01-11 | 上海交通大学 | Method of preparing cerium activated yttrium aluminium garnet ultrafine fluorescent powder using coprecipitation |
| CN101134896A (en) * | 2007-10-16 | 2008-03-05 | 厦门大学 | Method for preparing rare earth doping yttrium aluminium garnet fluorescent powder by oxalic acid non-homogeneous phase deposition |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289697A (en) * | 2012-03-02 | 2013-09-11 | 河南森源电气股份有限公司 | Preparation method of high-performance YAG (yttrium aluminium garnet) yellow fluorescent powder |
| CN102703078A (en) * | 2012-06-25 | 2012-10-03 | 重庆文理学院 | Secondary excitation type yellowish green fluorescent powder and preparation method thereof |
| CN102703078B (en) * | 2012-06-25 | 2015-11-25 | 重庆文理学院 | A kind of Secondary excitation type yellowish green fluorescent powder and preparation method thereof |
| CN102936497A (en) * | 2012-11-08 | 2013-02-20 | 广州有色金属研究院 | Main emission peak changeable and adjustable fluorescent material and preparation method thereof |
| CN102936497B (en) * | 2012-11-08 | 2014-12-31 | 广州有色金属研究院 | Main emission peak changeable and adjustable fluorescent material and preparation method thereof |
| CN103590111A (en) * | 2013-09-29 | 2014-02-19 | 温州大学 | Annealing method of cerium-doped yttrium aluminium garnet wafer for white-light LED (Light Emitting Diode) |
| CN103590111B (en) * | 2013-09-29 | 2016-04-06 | 温州大学 | A kind of method for annealing of white light LEDs cerium dropped yttrium aluminum garnet wafer |
| CN103992796A (en) * | 2014-05-30 | 2014-08-20 | 盐城工学院 | Method for preparing yellow phosphor with photo-enhanced function |
| CN112266239A (en) * | 2020-10-19 | 2021-01-26 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-color-rendering-index fluorescent ceramic for white light LED/LD and preparation method thereof |
| CN112266239B (en) * | 2020-10-19 | 2022-11-25 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-color-rendering-index fluorescent ceramic for white light LED/LD and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101724400B (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pavitra et al. | A novel strategy for controllable emissions from Eu 3+ or Sm 3+ ions co-doped SrY 2 O 4: Tb 3+ phosphors | |
| CN100378192C (en) | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method | |
| Zhang et al. | Citrate sol-gel combustion preparation and photoluminescence properties of YAG: Ce phosphors | |
| CN101724400B (en) | Method for preparing fluorescent powder for white light LED | |
| Yongqing et al. | Properties of red-emitting phosphors Sr2MgSi2O7: Eu3+ prepared by gel-combustion method assisted by microwave | |
| Guo et al. | A potential red‐emitting phosphor BaGd2 (MoO4) 4: Eu3+ for near‐UV white LED | |
| Xianju et al. | LiY1–xEux (MoO4) 2 as a promising red-emitting phosphor of WLEDs synthesized by sol-gel process | |
| Ma et al. | Synthesis, crystal structure and photoluminescence properties of novel Ba3Lu4O9: Ce3+ orange-red phosphors for white light emitting diodes | |
| Sun et al. | Photoluminescence Characteristics of Dy3+ Doped Y3 Ga5 O12 Phosphors for White Light Emitting Diodes | |
| Bhagyalekshmi et al. | Luminescence dynamics of Eu3+ activated and co-activated defect spinel zinc titanate nanophosphor for applications in WLEDs | |
| Wei et al. | Luminescence properties of garnet Y2Mg2Al2Si2O12: Ce3+ phosphors | |
| Du et al. | Luminescence properties of Ba2Mg (BO3) 2: Eu2+ red phosphors synthesized by a microwave-assisted sol-gel route | |
| Baklanova et al. | Synthesis and luminescence properties of Tb3+ and Dy3+ doped Li7La3Hf2O12 with tetragonal garnet structure | |
| Cao et al. | Spectral photoluminescence properties of YAG: Ce, R (R: Gd3+, Pr3+, Gd3+ and Pr3+) transparent fluorescent thin film prepared by pulse laser deposition | |
| Wang et al. | Synthesis and luminescence properties of SrGd2O4: Eu3+ red phosphors | |
| CN102994084B (en) | Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof | |
| Guangsheng et al. | Effect of Eu3+ contents on structure and luminescence properties of Na3Bi2-x (PO4) 3: xEu3+ and Na3Bi1-x (PO4) 2: xEu3+ phosphors | |
| Popovici et al. | Synthesis and characterization of cerium doped yttrium-gadolinium aluminate phosphors by wet-chemical synthesis route | |
| CN102199427A (en) | Fluorescent material with molybdate and tungstate as matrixes as well as preparation method and application thereof | |
| CN101775286B (en) | Preparation method of orange red fluorescent powder for white LED | |
| Muresan et al. | Rare earth activated yttrium aluminate phosphors with modulated luminescence | |
| CN101735810B (en) | Method for preparing rare-earth doped dodecacalcium heptaluminate light-accumulating luminescent powder emitting indigo light | |
| CN114196398A (en) | Mn for plant lighting4+Doped high-luminous-efficiency aluminate fluorescent material and preparation method thereof | |
| CN103849386B (en) | A kind of colloidal sol auto-combustion method prepares the method for aluminate blue fluorescent powder | |
| Yao et al. | Luminescent properties of Sr 2 ZnSi 2 O 7: Eu 2+ phosphors prepared by combustion-assisted synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130911 Termination date: 20181130 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |