CN103773370A - Rare earth-aluminate luminous material and preparation method thereof - Google Patents
Rare earth-aluminate luminous material and preparation method thereof Download PDFInfo
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- CN103773370A CN103773370A CN201210413264.0A CN201210413264A CN103773370A CN 103773370 A CN103773370 A CN 103773370A CN 201210413264 A CN201210413264 A CN 201210413264A CN 103773370 A CN103773370 A CN 103773370A
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000004964 aerogel Substances 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000012279 sodium borohydride Substances 0.000 claims description 23
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 12
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 12
- 229940038773 trisodium citrate Drugs 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene arsenic pyrrolidone Polymers 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- IBSDADOZMZEYKD-UHFFFAOYSA-H oxalate;yttrium(3+) Chemical compound [Y+3].[Y+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O IBSDADOZMZEYKD-UHFFFAOYSA-H 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 36
- 239000007864 aqueous solution Substances 0.000 description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- 239000010931 gold Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 238000013019 agitation Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000003836 solid-state method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000010944 silver (metal) Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005136 cathodoluminescence Methods 0.000 description 2
- 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 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 201000000490 flat ductal epithelial atypia Diseases 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a rare earth-aluminate luminous material which has a chemical general formula of Y3-xAl5O12:Lnx,My, wherein Ln is at least one of Ce and Tb; M is doped in Y3-xAl5O12:Lnx and is at least one of Ag, Au, Pt, Pd and Cu metal nanoparticles; x is more than 0 and is less than or equal to 0.5; y is a molar ratio of M to Al; y is more than 0 and is less than or equal to 1*10<-2>. The invention also provides a method for preparing the rare earth-aluminate luminous material. According to the rare earth-aluminate luminous material and the preparation method thereof, the metal nanoparticles are introduced, so that the luminous efficiency of the rare earth-aluminate luminous material under the same excitation condition is greatly improved, and the wavelength of emitted light is not changed.
Description
Technical field
The present invention relates to luminescent material technical field, particularly relate to rare earth-aluminate luminescent material and preparation method thereof.
Background technology
The sixties in 20th century, Ken Shoulder has proposed the imagination based on field emission cathode array (Field EmissiveArrays, FEAs) electron beam micro device, utilizes FEAs Design and manufacture flat pannel display and light source device.The principle of work of this novel feds with and traditional cathode tube (Cathode-Ray Tube, CRT) similar, by luminous picture or the lighting use of being embodied as of beam bombardment red, green, blue three-color phosphor, this kind of device all has potential advantage at aspects such as brightness, visual angle, time of response, operating temperature range, energy consumptions.
One of key factor of the feds of excellent is preparation high-performance fluorescent material.The fluorescent material that feds adopts is at present mainly used for sulfide series, oxide compound series and the oxysulfide series phosphor powder of conventional cathode ray tube and projection TV teletron.It is higher that sulfide series and oxysulfide series phosphor powder have luminosity, and there is the characteristic of certain electroconductibility, but easily decompose under the bombardment of large beam deflection, emit elemental sulfur and " poison " negative electrode needle point, and generate other throw outs and cover phosphor surface, reduce the luminous efficiency of fluorescent material.Oxide compound, aluminate fluorescent powder stability are good, but also have the not high enough shortcoming of luminous efficiency.
Summary of the invention
Based on this, have rare earth-aluminate luminescent material that a kind of luminous efficiency is higher and preparation method thereof is provided.
A kind of rare earth-aluminate luminescent material, has following chemical general formula: Y
3-xal
5o
12: Ln
x, M
y, described Ln is at least one in Ce and Tb, described M is entrained in Y
3-xal
5o
12: Ln
xin, described M is at least one in silver (Ag), gold (Au), platinum (Pt), palladium (Pd) and copper (Cu) metal nanoparticle, 0<x≤0.5, y be M with Al mole ratio, 0<y≤1 × 10
-2.
Therein in an embodiment, 0.01≤x≤0.3.
Therein in an embodiment, 1 × 10
-5≤ y≤5 × 10
-3.
A preparation method for rare earth-aluminate luminescent material, comprising:
At least one metal salt solution in Ag, Au, Pt, Pd and Cu is mixed and reacted with auxiliary agent and reductive agent, thereby make the colloidal sol that contains M; Described M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle;
According to M and Al mole ratio y, by aluminum oxide (Al
2o
3) aerogel contain M described in being dissolved to colloidal sol in, at 50 ℃ ~ 75 ℃ temperature, stir 0.5h ~ 3h, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5h ~ 4h, the alumina aerogels of the M that obtains adulterating, 0<y≤1 × 10
-2; And
According to Y
3-xal
5o
12: Ln
x, M
yeach element mole ratio, take compound, the compound of Ln and the alumina aerogels of described doping M of yttrium (Y), grind and be placed in reducing atmosphere, and be warming up to 1300 ℃ ~ 1700 ℃ processing 2h ~ 8h, furnace cooling is cooled to room temperature, and obtaining chemical general formula is Y
3-xal
5o
12: Ln
x, M
yrare earth-aluminate luminescent material, described Ln is at least one in Ce and Tb, described M is entrained in Y
3-xal
5o
12: Ln
xin, 0<x≤0.5.
In an embodiment, in described metal salt solution, the concentration of metal ion is 5.5 × 10 therein
-5mol/L ~ 6 × 10
-3mol/L.
Therein in an embodiment, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate, and the concentration of the addition of described auxiliary agent in the colloidal sol of the described M of containing is 1 × 10
-4g/mL ~ 5 × 10
-3g/mL.
In an embodiment, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride therein, and the mol ratio of the addition of described reductive agent and the metal ion of described metal salt solution is 0.4:1 ~ 12:1.
Therein in an embodiment, described in make the colloidal sol that contains M reaction times be 10 minutes ~ 45 minutes.
In an embodiment, described reducing atmosphere is nitrogen (N therein
2) and hydrogen (H
2) mixed atmosphere, carbon dust (C) atmosphere, carbon monoxide (CO) atmosphere and hydrogen atmosphere at least one.
In an embodiment, described Y compound is yttrium oxide, Yttrium trinitrate, yttrium carbonate or yttrium oxalate therein; The compound of described Ln is oxide compound, nitrate, carbonate or the oxalate of Ln.
Above-mentioned rare earth-aluminate luminescent material and preparation method, by having introduced metal nanoparticle, the luminous efficiency of rare earth-aluminate luminescent material under same shooting conditions is greatly improved, and radiative wavelength do not change.Rare earth-aluminate luminescent material of the present invention has good luminescent properties, after being stimulated radiative purity of color and brightness all higher, can be applied in feds.
Accompanying drawing explanation
Fig. 1 is the schema of the rare earth-process for preparing aluminate luminescent materials of an embodiment;
Fig. 2 is rare earth-aluminate luminescent material of preparing of embodiment 2 and traditional luminescent material cathodoluminescence spectrum comparison diagram under 1.5kv voltage.
Embodiment
Below in conjunction with embodiment and accompanying drawing, rare earth-aluminate luminescent material and preparation method thereof is described in further detail.
A kind of rare earth-aluminate luminescent material that present embodiment provides is a kind of fluorescent material, and it is rare earth-aluminate luminescent material of having introduced metal nanoparticle M, and this rare earth-aluminate luminescent material has following chemical general formula: Y
3-xal
5o
12: Ln
x, M
y, Ln is at least one in Ce and Tb, M is entrained in Y
3-xal
5o
12: Ln
xin, M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, 0<x≤0.5, y be M with Al mole ratio, 0<y≤1 × 10
-2.
In other embodiments, the scope of x can be 0.01≤x≤0.3.The scope of y can be 1 × 10
-5≤ y≤5 × 10
-3.
Above-mentioned rare earth-aluminate luminescent material, matrix take rare earth-aluminate as luminescent material, introduce metal nanoparticle, the adulterated rare earth-aluminate luminescent material of metal nanoparticle of acquisition, by surface plasma effect, make this rare earth-aluminate luminescent material under same shooting conditions, its luminous efficiency is greatly improved, and radiative wavelength does not change.Above-mentioned rare earth-aluminate luminescent material has good stability, the better advantage of luminescent properties.
Refer to Fig. 1, the preparation method of the rare earth-aluminate luminescent material of an embodiment comprises the following steps:
S101, mixes at least one the metal salt solution in Ag, Au, Pt, Pd and Cu react with auxiliary agent and reductive agent, thereby making the colloidal sol that contains M; M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle.
In the present embodiment, concentration of salt solution is flexible configuration according to actual needs, and in metal salt solution, the concentration of metal ion can be 5.5 × 10
-5mol/L ~ 6 × 10
-3mol/L.Auxiliary agent can be at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate or sodium laurylsulfonate.The addition of auxiliary agent is 1 × 10 in the concentration of the colloidal sol that contains M
-4g/mL ~ 5 × 10
-3g/mL, adds auxiliary agent and can prevent metal nanoparticle reunion.Reductive agent can be at least one in hydrazine hydrate, xitix, Trisodium Citrate or sodium borohydride.The mol ratio of the addition of reductive agent and the metal ion of metal salt solution can be 0.4:1 ~ 12:1.Reaction times can be 10 minutes ~ 45 minutes.
S102, according to M and Al mole ratio y, alumina aerogels is dissolved in the colloidal sol that contains M, at 50 ℃ ~ 75 ℃ temperature, stir 0.5h ~ 3h, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5h ~ 4h, obtain the adulterating alumina aerogels of M, 0<y≤1 × 10
-2.
In the present embodiment, ultrasonic can be under the power of 500W ultrasonic about 10 minutes.Dry can be to be to carry out under 60 ℃ ~ 150 ℃ conditions in temperature.In this process, alumina aerogels has the network structure of porous, and density is low, and specific surface area is large, can be high temperature resistant, therefore can understand combination with metal nano, and can obtain the alumina aerogels doped with metal nanoparticle.
S103, according to Y
3-xal
5o
12: Ln
x, M
yeach element mole ratio, take respectively compound, the compound of Ln and the alumina aerogels of described doping M of Y, grind and be placed in reducing atmosphere, and be warming up to 1300 ℃ ~ 1700 ℃ and process 2h ~ 8h, furnace cooling is cooled to room temperature, obtaining chemical general formula is Y
3-xal
5o
12: Ln
x, M
yrare earth-aluminate luminescent material, M is entrained in Y
3-xal
5o
12: Ln
xin, 0<x≤0.5.
In the present embodiment, if reducing atmosphere can be at least one in mixed atmosphere, carbon dust atmosphere, carbon monoxide atmosphere and the medium reducing atmosphere of hydrogen atmosphere of nitrogen and hydrogen.In weakly reducing atmosphere, the metal ion of high valence state can be reduced into the metal ion of lower valency, or protection metal ion is not oxidized.Y compound can be yttrium oxide, Yttrium trinitrate, yttrium carbonate or yttrium oxalate.The compound of Ln can be oxide compound, nitrate, carbonate or the oxalate of Ln.
In the preparation method of above-mentioned rare earth-aluminate luminescent material, the colloidal sol that first preparation contains metal nanoparticle, then adopt alumina aerogels adsorbing metal nanoparticle, obtain the alumina aerogels doped with metal nanoparticle, prepare again metal nano particle-doped rare earth-aluminate luminescent material take the alumina aerogels doped with metal nanoparticle as raw material, make this rare earth-aluminate luminescent material under same shooting conditions, its luminous efficiency is greatly improved, and radiative wavelength does not change.And above-mentioned preparation method's technique is simple, equipment requirements is low, pollution-free, be easy to control, be suitable for suitability for industrialized production.
Describe below in conjunction with specific embodiment.
Embodiment 1
High temperature solid-state method preparation
Take 51.8mg Platinic chloride (H
2ptCl
66H
2o) be dissolved in the deionized water of 17mL; After Platinic chloride dissolves completely, take 40.0mg Trisodium Citrate and 60.0mg sodium laurylsulfonate, and be dissolved in chloroplatinic acid aqueous solution under the environment of magnetic agitation; Take 1.9mg sodium borohydride and be dissolved in 10mL deionized water, obtaining 10mL concentration is 5 × 10
-3the sodium borohydride aqueous solution of mol/L, prepare 10mL concentration is 5 × 10 simultaneously
-2the hydrazine hydrate solution of mol/L; Under the environment of magnetic agitation, first in chloroplatinic acid aqueous solution, drip 0.4mL sodium borohydride aqueous solution, stirring reaction 5 minutes, and then drip 2.6mL5 × 10 in chloroplatinic acid aqueous solution
-2the hydrazine hydrate solution of mol/L, continues reaction 40 minutes afterwards, and obtaining 20mLPt content is 5 × 10
-3the Pt nanoparticle sol of mol/L.The wherein mol ratio 1.32:1 of the addition of reductive agent and the metal ion of described metal salt solution.
Take alumina aerogels 0.6117g, being dissolved into 12mLPt content is 5 × 10
-3in mol/LPt nanoparticle sol, at 50 ℃, stir 3h, then ultrasonic 10 minutes, then be dried at 60 ℃, dried sample is ground evenly, precalcining 4h at 600 ℃, obtains the alumina aerogels that contains Pt nanoparticle.
Take respectively the yttrium carbonate (Y of 1.0698g
2(CO
3)
3), 0.0046g cerous carbonate (Ce
2(CO
3)
3) and the alumina aerogels that contains Pt nanoparticle of 0.5098g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1700 ℃ of thermal reduction 2h of weakly reducing atmosphere, be cooled to room temperature, the luminescent material of the Pt nanoparticle that can obtain adulterating
High temperature solid-state method preparation
The preparation of Ag nanoparticle sol: take 0.68mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.4mL; After Silver Nitrate dissolves completely, take 8.4mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 22.8mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 3 × 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 1.6mL3 × 10 that add in silver nitrate aqueous solution
-2the sodium borohydride aqueous solution of mol/L, continues reaction 10 minutes afterwards, and obtaining 20mLAg content is 2 × 10
-4the Ag nanoparticle sol of mol/L.The wherein mol ratio 12:1 of the addition of reductive agent and the metal ion of described metal salt solution.
Take alumina aerogels 0.6117g, being dissolved into 15mLAg content is 2 × 10
-4in the Ag nanoparticle sol of mol/L, at 60 ℃, stir 2h, then ultrasonic 10 minutes, then be dried at 80 ℃, dried sample is ground evenly, precalcining 2h at 800 ℃, obtains the alumina aerogels that contains Ag nanoparticle.
Take respectively the yttrium oxide (Y of 0.6503g
2o
3), 0.0448g terbium peroxide (Tb
4o
7) and the alumina aerogels 0.5098g that contains Ag nanoparticle, being placed in agate mortar is fully ground to and mixes, then by powder transfer in corundum crucible, in retort furnace under carbon dust atmosphere 1500 ℃ of thermal reduction 4h, be cooled to room temperature, the luminescent material of the Ag nanoparticle that can obtain adulterating
As shown in Figure 2, rare earth-aluminate luminescent material of preparing for embodiment 2 and the cathodoluminescence spectrum comparison diagram of traditional luminescent material under 1.5kv voltage.Wherein curve 1 is the luminescent material Y of doping Ag nanoparticle
2.88al
5o
12: Tb
0.12, Ag
2.5 × 10-4luminescent spectrum, curve 2 is not metal nano particle-doped luminescent material Y
2.88al
5o
12: Tb
0.12luminescent spectrum.
As shown in Figure 2, at the emission peak at 544nm place, the luminescent material Y of doping Ag nanoparticle
2.88al
5o
12: Tb
0.12, Ag
2.5 × 10-4the more not metal nano particle-doped luminescent material Y of luminous intensity
2.88al
5o
12: Tb
0.12luminous intensity strengthened 40%.
Embodiment 3
High temperature solid-state method preparation
Take 41.2mg hydrochloro-auric acid (AuCl
3hCl4H
2o) be dissolved in the deionized water of 16.6mL; After hydrochloro-auric acid dissolves completely, take 28mg Trisodium Citrate and 12mg cetyl trimethylammonium bromide, and be dissolved in aqueous solution of chloraurate under the environment of magnetic agitation; Take 3.8mg sodium borohydride and 35.2mg xitix is dissolved into respectively in 10mL deionized water, obtaining 10mL concentration is 1 × 10
-2the sodium borohydride aqueous solution of mol/L and 10mL concentration are 2 × 10
-2the aqueous ascorbic acid of mol/L; Under the environment of magnetic agitation, first in aqueous solution of chloraurate, add 0.08mL sodium borohydride aqueous solution, stirring reaction adds 3.32mL2 × 10 after 5 minutes again in aqueous solution of chloraurate
-2the aqueous ascorbic acid of mol/L, continues reaction 30 minutes afterwards, and obtaining 20mLAu content is 5 × 10
-3the Au nanoparticle sol of mol/L.The wherein mol ratio 0.672:1 of the addition of reductive agent and the metal ion of described metal salt solution.
Take alumina aerogels 0.6117g, being dissolved into 12mLAu content is 1 × 10
-2in the Au nanoparticle sol of mol/L, at 75 ℃, stir 0.5h, then ultrasonic 10 minutes, then be dried at 150 ℃, dried sample is ground evenly, precalcining 0.5h at 1200 ℃, obtains the alumina aerogels that contains metal ion.
Then take the yttrium oxide (Y of 0.5645g
2o
3)
3, 0.1868g terbium peroxide (Tb
4o
7) and contain Au nanoparticle alumina aerogels 0.5098g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, the N that is 95% in volume fraction in tube furnace
2the lower 1450 ℃ of thermal reduction 6h of H2 weakly reducing atmosphere with volume fraction is 5%, are cooled to room temperature, the luminescent material of the Au nanoparticle that can obtain adulterating
Embodiment 4
High temperature solid-state method preparation
The preparation of Pd nanoparticle sol: take 0.44mg Palladous chloride (PdCl
22H
2o) be dissolved in the deionized water of 19mL; After Palladous chloride dissolves completely, take 11.0mg Trisodium Citrate and 4.0mg sodium lauryl sulphate, and be dissolved in palladium chloride aqueous solution under the environment of magnetic agitation; Take 3.8mg sodium borohydride molten in 10mL deionized water, obtaining concentration is 1 × 10
-2the sodium borohydride reduction liquid of mol/L; Under the environment of magnetic agitation, in palladium chloride aqueous solution, add fast 1mL1 × 10
-2the sodium borohydride aqueous solution of mol/L, continues reaction 20 minutes afterwards, and obtaining 20mLPd content is 1 × 10
-4the Pd nanoparticle sol of mol/L.The wherein mol ratio 5:1 of the addition of reductive agent and the metal ion of described metal salt solution.
Take alumina aerogels 0.3058g, being dissolved into 15mLPd content is 1 × 10
-4in the Pd nanoparticle sol of mol/L, at 65 ℃, stir 1.5h, then ultrasonic 10 minutes, then be dried at 120 ℃, dried sample is ground evenly, precalcining 2h at 1100 ℃, obtains the alumina aerogels that contains Pd nanoparticle.
Take respectively 1.4844g Yttrium trinitrate (Y (NO
3)
3), 0.0652g cerous nitrate (Ce (NO
3)
3), 0.1379g Terbium trinitrate (Tb (NO
3)
3) and the alumina aerogels 0.5098g that contains Pd nanoparticle, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2the lower 1400 ℃ of thermal reduction 4h of weakly reducing atmosphere, be cooled to room temperature, can obtain doping Pd nanoparticle
luminescent material.
Embodiment 5
High temperature solid-state method preparation
Take 0.17mg Silver Nitrate (AgNO
3) be dissolved in the deionized water of 18.2mL; After Silver Nitrate dissolves completely, take 2mg Trisodium Citrate and be dissolved in silver nitrate aqueous solution under the environment of magnetic agitation; Take 0.285mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 7.5 × 10
-4the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 1.8mL7.5 × 10 that add in silver nitrate aqueous solution
-4the sodium borohydride aqueous solution of mol/L, continues reaction 10 minutes afterwards, and obtaining 20mLAg content is 5 × 10
-5the Ag nanoparticle sol of mol/L.The wherein mol ratio 1.35:1 of the addition of reductive agent and the metal ion of described metal salt solution.
Take alumina aerogels 0.6117g, being dissolved into 2.4mLAg content is 5 × 10
-5in the Ag nanoparticle sol of mol/L, at 65 ℃, stir 1.5h, then ultrasonic 10 minutes, then be dried at 120 ℃, dried sample is ground evenly, precalcining 3h at 900 ℃, obtains the alumina aerogels that contains Ag nanoparticle.
Then take the yttrium oxalate (Y of 1.2723g
2(C
2o
4)
3), the Sedemesis (Ce of 0.0653g
2(C
2o
4)
3) and the alumina aerogels 0.5098g that contains Ag nanoparticle, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, in tube furnace under CO reducing atmosphere 1300 ℃ of thermal reduction 8h, be cooled to room temperature, the Ag nanoparticle that can obtain adulterating
luminescent material.
Embodiment 6
High temperature solid-state method preparation
Take in the ethanol that 2mg cupric nitrate is dissolved into 16mL, after dissolving completely, stir while add 12mgPVP, then slowly splash into 0.4mg sodium borohydride molten to obtain in 10mL ethanol 1 × 10
-3the sodium borohydride alcoholic solution 4mL of mol/L, continues stirring reaction 10 minutes, and obtaining 20mLCu content is 5 × 10
-4the Cu nanometer particle colloid of mol/L.The mol ratio 0.4:1 of the addition of reductive agent and the metal ion of described metal salt solution
Take alumina aerogels 0.6117g, be dissolved into 12mL5 × 10
-4in the Cu nanometer particle colloid of mol/L, at 70 ℃, stir 1h, then ultrasonic 10 minutes, then be dried at 70 ℃, dried sample is ground evenly, precalcining 2h at 800 ℃, obtains the alumina aerogels that contains Cu nanoparticle.
Then take the yttrium oxide (Y of 0.6097g
2o
3)
3, 0.1121g terbium peroxide (Tb
4o
7) and the Al that contains Cu nanoparticle
2o
3aerogel 0.5098g, is placed in agate mortar and is fully ground to and mixes, then by powder transfer in corundum crucible, 1600 ℃ of thermal treatment 3h in retort furnace, then the N that is 95% in volume fraction in tube furnace
2with the volume fraction H that is 5%
2under weakly reducing atmosphere, in 1400 ℃ of thermal reduction 2h, be cooled to room temperature, can obtain doped with Cu nanoparticle luminescent material
Embodiment 7
High temperature solid-state method preparation
Take 6.2mg hydrochloro-auric acid (AuCl
3hCl4H
2and 2.5mg Silver Nitrate (AgNO O)
3) be dissolved in the deionized water of 28mL; After dissolving completely, take 22mg Trisodium Citrate and 20mgPVP, and under the environment of magnetic agitation, be dissolved in above-mentioned mixing solutions; Take freshly prepd 5.7mg sodium borohydride molten in 10mL deionized water, obtaining 10mL concentration is 1.5 × 10
-2the sodium borohydride aqueous solution of mol/L; Under the environment of magnetic agitation, toward disposable 2mL1.5 × 10 that add in above-mentioned mixing solutions
-2the sodium borohydride aqueous solution of mol/L, continues reaction 20 minutes afterwards, and obtaining the total metal concentration of 30mL is 1 × 10
-3the Ag of mol/L and Au nanoparticle sol.The wherein mol ratio 1:1 of the addition of reductive agent and the metal ion of described metal salt solution.
Take alumina aerogels 0.6117g, be dissolved into the total metal concentration 1 × 10 of 15mL
-3in the Ag/Au nanoparticle sol of mol/L, at 60 ℃, stir 2h, then ultrasonic 10 minutes, then 80 ℃ dry, dried sample is ground evenly, precalcining 4h at 1000 ℃, obtains the alumina aerogels of Ag and Au nanoparticle sol.
Then take the Yttrium trinitrate (Y (NO of 1.5944g
3)
3), 0.0652g cerous nitrate (Ce (NO
3)
3) and the Al that contains Ag and Au nanoparticle
2o
3aerogel 0.5098g, be placed in agate mortar and be fully ground to and mix, then by powder transfer in corundum crucible, 1500 ℃ of thermal reduction 3h under the mixing reducing atmosphere of carbon dust and CO gas, be cooled to room temperature, the luminescent material of can obtain adulterating Ag and Au nanoparticle
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. rare earth-aluminate luminescent material, is characterized in that, has following chemical general formula: Y
3-xal
5o
12: Ln
x, M
y, described Ln is at least one in Ce and Tb, described M is entrained in Y
3-xal
5o
12: Ln
xin, described M is at least one in Ag, Au, Pt, Pd and Cu metal nanoparticle, 0<x≤0.5, y be M with Al mole ratio, 0<y≤1 × 10
-2.
2. rare earth-aluminate luminescent material according to claim 1, is characterized in that, 0.01≤x≤0.3.
3. rare earth-aluminate luminescent material according to claim 1, is characterized in that, 1 × 10
-5≤ y≤5 × 10
-3.
4. a preparation method for rare earth-aluminate luminescent material, is characterized in that, comprising:
At least one metal salt solution in Ag, Au, Pt, Pd and Cu is mixed and reacted with auxiliary agent and reductive agent, thereby make the colloidal sol that contains M; Described M is selected from least one in Ag, Au, Pt, Pd and Cu metal nanoparticle;
According to M and Al mole ratio y, in the colloidal sol that contains M described in alumina aerogels is dissolved to, at 50 ℃ ~ 75 ℃ temperature, stir 0.5h ~ 3h, ultrasonic, dry, after grinding, at 600 ℃ ~ 1200 ℃, calcine 0.5h ~ 4h, obtain the adulterating alumina aerogels of M, 0<y≤1 × 10
-2; And
According to Y
3-xal
5o
12: Ln
x, M
yeach element mole ratio, take respectively compound, the compound of Ln and the alumina aerogels of described doping M of Y, grind and be placed in reducing atmosphere, and be warming up to 1300 ℃ ~ 1700 ℃ and process 2h ~ 8h, furnace cooling is cooled to room temperature, obtaining chemical general formula is Y
3-xal
5o
12: Ln
x, M
yrare earth-aluminate luminescent material, described Ln is at least one in Ce and Tb, described M is entrained in Y
3-xal
5o
12: Ln
xin, 0<x≤0.5.
5. the preparation method of rare earth-aluminate luminescent material according to claim 4, is characterized in that, in described metal salt solution, the concentration of metal ion is 5.5 × 10
-5mol/L ~ 6 × 10
-3mol/L.
6. the preparation method of rare earth-aluminate luminescent material according to claim 4, it is characterized in that, described auxiliary agent is at least one in polyethylene arsenic pyrrolidone, Trisodium Citrate, cetyl trimethylammonium bromide, sodium lauryl sulphate and sodium laurylsulfonate, and the concentration of the addition of described auxiliary agent in the colloidal sol of the described M of containing is 1 × 10
-4g/mL ~ 5 × 10
-3g/mL.
7. the preparation method of rare earth-aluminate luminescent material according to claim 4, it is characterized in that, described reductive agent is at least one in hydrazine hydrate, xitix, Trisodium Citrate and sodium borohydride, and the mol ratio of the addition of described reductive agent and the metal ion of described metal salt solution is 0.4:1 ~ 12:1.
8. the preparation method of rare earth-aluminate luminescent material according to claim 4, is characterized in that, described in make the colloidal sol that contains M reaction times be 10 minutes ~ 45 minutes.
9. the preparation method of rare earth-aluminate luminescent material according to claim 4, is characterized in that, described reducing atmosphere is at least one in mixed atmosphere, carbon dust atmosphere, carbon monoxide atmosphere and the hydrogen atmosphere of nitrogen and hydrogen.
10. the preparation method of rare earth-aluminate luminescent material according to claim 4, is characterized in that, described Y compound is yttrium oxide, Yttrium trinitrate, yttrium carbonate or yttrium oxalate; The compound of described Ln is oxide compound, nitrate, carbonate or the oxalate of Ln.
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