CN102173774A - Cerium terbium yttrium garnet doped transparent ceramic fluorescent material and preparation method thereof - Google Patents
Cerium terbium yttrium garnet doped transparent ceramic fluorescent material and preparation method thereof Download PDFInfo
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- CN102173774A CN102173774A CN2011100320773A CN201110032077A CN102173774A CN 102173774 A CN102173774 A CN 102173774A CN 2011100320773 A CN2011100320773 A CN 2011100320773A CN 201110032077 A CN201110032077 A CN 201110032077A CN 102173774 A CN102173774 A CN 102173774A
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000919 ceramic Substances 0.000 title claims abstract description 8
- XVHSGURABNBIFT-UHFFFAOYSA-N [Ce].[Y].[Tb] Chemical compound [Ce].[Y].[Tb] XVHSGURABNBIFT-UHFFFAOYSA-N 0.000 title abstract 2
- 239000002223 garnet Substances 0.000 title abstract 2
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 229910002106 crystalline ceramic Inorganic materials 0.000 claims description 67
- 239000011222 crystalline ceramic Substances 0.000 claims description 67
- 239000002585 base Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 23
- 229910052771 Terbium Inorganic materials 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 15
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 238000005056 compaction Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 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 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 terbium peroxide Chemical class 0.000 claims description 3
- 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 claims description 3
- GWYXTVGANSBRNB-UHFFFAOYSA-N terbium(iii) oxide Chemical compound O=[Tb]O[Tb]=O GWYXTVGANSBRNB-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 5
- 238000009694 cold isostatic pressing Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000007731 hot pressing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 241001025261 Neoraja caerulea Species 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
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Abstract
The cerium terbium yttrium garnet doped transparent ceramic fluorescent material comprises Tb3-xCexAl5O12(wherein x is more than or equal to 0.001 and less than or equal to 0.03). The preparation method specifically comprises the following steps: according to Tb3-xCexAl5O12Preparing raw materials, adding 0.3-0.7 wt% of tetraethoxysilane as an additive, performing ball milling, drying and tabletting on powder, performing cold isostatic pressing on the powder at the pressure of more than 200MPa to prepare a blank, and presintering at the temperature of 200-800 ℃ for 0.5-5 hours to remove organic components; finally putting the mixture into a vacuum or hot-pressing sintering furnace for sintering to obtain Tb3-xCexAl5O12A transparent ceramic fluorescent material. The transparent ceramic fluorescent material can be excited by a commercial GaInN blue light LED, has color temperature close to ideal white light, and has ageing resistance and light decay resistance.
Description
Technical field
The present invention relates to a kind of crystalline ceramics fluorescent material, particularly a kind of doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material and preparation method thereof.
Background technology
Photodiode (LED) white-light illuminating has advantages such as less energy-consumption, high reliability, long lifetime, no mercury.The realization technological line of white light LEDs mainly contains following several at present: RGB three-primary color LED mixed type, fluorescent material transformant, single-chip multi layer quantum well type.From industrialization factors such as technical matters maturity, production costs, fluorescent material transformant white light LEDs is present mainstream technology, and its main implementation is for to excite gold-tinted fluorescent material synthesize white light then by blue-ray LED; Perhaps produce white light emission by the ultraviolet LED excited white light fluorescent powder.Wherein, adopt blue-ray LED to excite the technological line of gold-tinted fluorescent material to become present mainstream technology, the white light emission of its specific implementation for exciting Ce:YAG fluorescent material to realize by the GaInN blue-ray LED owing to it has higher quantum yield.But the white light LEDs of this kind structure still has problems: on the one hand, this kind white light LEDs is normally sneaked into Ce:YAG fluorescent material in Resins, epoxy or the silica gel when encapsulation, and the heat dispersion of these two kinds of organic packaged materials is all relatively poor and easily aging, and light decay is serious in time to make the device luminous efficiency.On the other hand,, cause the colour temperature of this structure white light LED too high, be not suitable for interior lighting owing to lack the ruddiness composition in the fluorescence spectrum of Ce:YAG fluorescent material.In recent years, Ce:TAG fluorescent material is widely studied owing to it has the desired color temperature (6500K) and the high-luminous-efficiency that approach the nature white light.Yet, because the restriction of packaged materials such as Resins, epoxy, silica gel, the temperature cancellation performance of Ce:TAG is good not as Ce:YAG in addition, makes GaInN blue-ray LED+Ce:TAG gold-tinted fluorescent material transformant white light LEDs (especially high-power product) still face the problem of light decay.In addition, because the density of Ce:TAG fluorescent material is more a lot of than big, it is settled down to the bottom of organic packaged material easily in encapsulation process, owing to can not effectively being excited the luminous efficiency that reduces LED.And fluorescent material is prepared into the transparent ceramic material with certain transparency, and can avoid using organic packaged material, weaken the light decay effect to a great extent, can simplify the packaging process of LED simultaneously.The present invention makes transparent ceramic material with Ce:TAG fluorescent material exactly, makes it satisfy the problem of ideal white light colour temperature and solution light decay simultaneously.
Summary of the invention
In order to overcome the defective of above-mentioned prior art, the invention provides a kind of doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material and preparation method thereof, this material can effectively solve traditional organic packaged material weak heat-dissipating, easy aging caused light decay problem, it is simple, low-cost that its preparation method has technology, advantage such as toxicological harmless generation in the preparation process.
Technical solution of the present invention is as follows:
A kind of doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material, its characteristics are that the concrete component of this material is Tb
3-xCe
xAl
5O
12, wherein the span of x is: 0.001≤x≤0.03.
Doped with cerium and terbium yttrogarnet crystalline ceramics Preparation of Fluorescent Material method has two kinds of schemes:
First kind of scheme step is as follows:
1. adopt commercial cerium oxide, terbium peroxide or terbium sesquioxide or aluminic acid terbium and the alumina powder jointed raw material of doing, after the concrete value of selected x, press Tb
3-xCe
xAl
5O
12Form and configure powder raw material;
2. the tetraethoxy that adds 0.3wt%～0.7wt% is as additive, and with powder mixing, refinement, the powder oven dry is after granulation, compressing tablet through ball milling; The back imposes the above cold isostatic pressure of 200MPa to it and is pressed into base substrate, removes organic composition in 0.5～5 hour 200～800 ℃ of pre-burnings again;
3. put into vacuum sintering furnace or hot-pressed sintering furnace sintering some hrs at a certain temperature at last, obtain Tb
3-xCe
xAl
5O
12Doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material.
The purity of described powder raw material is not less than 99.9%;
Second kind of scheme step is as follows:
1. be initial feed with Terbium trinitrate or terbium chloride, aluminum nitrate or aluminum chloride, cerous nitrate or Cerium II Chloride, after the concrete value of selected x, press Tb
3-xCe
xAl
5O
12Form and configure raw material; Employing is the chemical coprecipitation of precipitation agent with urea or bicarbonate of ammonia or is that stablizer adopts the sol-gel method wet chemical method to prepare Tb with the citric acid
3-xCe
xAl
5O
12Precursor is after 800～1200 ℃ of calcinings got Tb in 0.5～10 hour
3-xCe
xAl
5O
12Powder;
2. the tetraethoxy that adds 0.3～0.7wt% carries out ball milling with described powder, after injection forming or cold isostatic compaction are made base substrate, removes organic composition in 0.5～5 hour 200～800 ℃ of pre-burnings again;
3. put into vacuum sintering furnace or hot-pressed sintering furnace sintering some hrs at a certain temperature at last, obtain Tb
3-xCe
xAl
5O
12Doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material.
The temperature of described vacuum sintering is 1400～1650 ℃, and soaking time is 0.5～50 hour; Vacuum tightness in the vacuum sintering furnace is better than 3 * 10
-2Pa;
The temperature of described hot pressed sintering is 900～1500 ℃, is 0.2～10MPa to the ceramic body applied pressure, and soaking time is 0.5～30 hour.
Compared with prior art, beneficial effect of the present invention:
(1) Tb
3-xCe
xAl
5O
12The crystalline ceramics fluorescent material has better colour temperature.
(2), effectively avoided because organic packaged material weak heat-dissipating, the light decay phenomenon that easily wears out and cause owing in the LED encapsulation process, can need not or reduce and use Resins, epoxy or silica gel.
(3) preparation technology is simple, the yield rate height, and cost is low, easily batch preparations.
Embodiment
The invention will be further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this.
Embodiment 1
1. adopting purity is 99.% commercial cerium oxide (CeO
2), terbium peroxide (Tb
4O
7) and aluminum oxide (Al
2O
3) powder, x value 0.001 is pressed Tb
2.999Ce
0.001Al
5O
12Composition configures powder raw material 30g altogether,
2. the tetraethoxy (TEOS) that adds 0.3wt% is as additive, and with powder mixing, refinement, the powder oven dry is after granulation, compressing tablet through means such as ball millings; The back imposes the above cold isostatic pressure of 200MPa to it and is pressed into base substrate, removes organic composition in 0.5 hour 200 ℃ of pre-burnings again;
3. put into vacuum sintering furnace at last in 1400 ℃ of sintering 0.5 hour, the vacuum tightness in sintered heat insulating stage is better than 2.5 * 10
-3Pa obtains Tb
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 2
The sintered heat insulating temperature is 1650 ℃, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 3
The sintered heat insulating temperature is 1500 ℃, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 4
The sintered heat insulating time is 50 hours, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 5
The sintered heat insulating time is 10 hours, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 6
Material purity is 99.99%, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 7
Material purity is 99.999%, and other conditions can obtain Tb with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 8
The add-on of positive tetraethyl orthosilicate is 0.7wt%, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 9
Calcined temperature is 800 ℃, and the pre-burning time is 5 hours, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 10
Calcined temperature is 400 ℃, and the pre-burning time is 3 hours, and other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 11
X value 0.03 is pressed Tb
2.97Ce
0.03Al
5O
12Chemical constitution configuration raw material, other conditions can obtain Tb with embodiment 1
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 12
Press Tb
2.97Ce
0.03Al
5O
12Chemical constitution configuration raw material, the sintered heat insulating temperature is 1500 ℃, other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 13
Press Tb
2.97Ce
0.03Al
5O
12Chemical constitution configuration raw material, the sintered heat insulating temperature is 1650 ℃, other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 14
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 900 ℃, and base substrate is applied the pressure of 0.2MPa, and soaking time is 0.5 hour, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 15
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 1500 ℃, and base substrate is applied the pressure of 0.2MPa, and soaking time is 0.5 hour, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 16
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 1100 ℃, and base substrate is applied the pressure of 0.2MPa, and soaking time is 50 hours, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 17
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 900 ℃, and base substrate is applied the pressure of 10MPa, and soaking time is 0.5 hour, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 18
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 900 ℃, and base substrate is applied the pressure of 10MPa, and soaking time is 20 hours, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 19
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 1050 ℃, and base substrate is applied the pressure of 10MPa, and soaking time is 20 hours, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 20
With Tb
2.97Ce
0.03Al
5O
12Base substrate is put into the hot pressed sintering sintering, and holding temperature is 1200 ℃, and base substrate is applied the pressure of 5MPa, and soaking time is 20 hours, and other conditions can obtain Tb with embodiment 11
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 21
1. with Terbium trinitrate (Tb (NO
3)
3), aluminum nitrate (Al (NO
3)
3), cerous nitrate (Ce (NO
3)
3) be initial feed, the value 0.001 of selected x is pressed Tb
2.999Ce
0.001Al
5O
12Form the configuration initial feed altogether behind the 50g, with its molten 1000 ml water solution of making, after dropwise splash into urea (CO (NH
2)
2) in the precipitant solution, obtain containing Ce (OH)
3, Ce
2(CO
3)
3, Tb (OH)
3, Tb
2(CO
3)
3, Al (OH)
3, Tb
2(CO
3)
3Tb
2.999Ce
0.001Al
5O
12The precursor throw out is after 800 ℃ of calcinings got Tb in 0.5 hour
2.999Ce
0.001Al
5O
12Powder,
2. the TEOS that adds 0.5wt% carries out ball milling with this powder, after injection forming or cold isostatic compaction are made base substrate, removes organic composition in 3 hours 400 ℃ of pre-burnings again;
3. put into vacuum sintering furnace at last 1400 ℃ of sintering temperatures 0.5 hour, obtain Tb
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 22
The sintered heat insulating temperature is 1650 ℃ of temperature, and other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 23
The sintered heat insulating temperature is 1500 ℃ of temperature, and other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 24
The sintered heat insulating time is 50 hours, and other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 25
The sintered heat insulating time is 10 hours, and other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 26
The TEOS add-on is 0.3wt%, and other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 27
The TEOS add-on is 0.7wt%, and other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 28
The interior vacuum tightness of stove is better than 2 * 10 during insulation
-4Pa, other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 29
Calcining temperature is that calcination time is that other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 30
Calcined temperature is that the pre-burning time is that other conditions obtain Tb with embodiment 21
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 31
1. the value of X is 0.3, presses Tb
2.97Ce
0.03Al
5O
12Form, take by weighing Cerium II Chloride (CeCl
3), terbium chloride (TbCl
3), aluminum chloride (AlCl
3) etc. initial feed 50g altogether, with its molten 1000 ml water solution of making, adding the 1wt% citric acid is stablizer, uses magnetic stirring apparatus to stir and be heated to 60 ℃, obtains Tb
2.97Ce
0.03Al
5O
12Precursor colloidal sol is with this colloidal sol ageing 24 hours, after 1000 ℃ of calcinings got Tb in 5 hours
2.97Ce
0.03Al
5O
12Powder,
2. the TEOS that adds 0.7wt% carries out ball milling with this powder, after injection forming or cold isostatic compaction are made base substrate, removes organic composition in 4 hours 600 ℃ of pre-burnings again;
3. put into vacuum sintering furnace at last 1400 ℃ of following sintering 0.5 hour, obtain Tb
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 32
Holding temperature is 1650 ℃, and other conditions obtain Tb with embodiment 31
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 33
Holding temperature is 1500 ℃, and other conditions obtain Tb with embodiment 31
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 34
The sintered heat insulating time is 50 hours, and other conditions can obtain Tb equally with embodiment 31
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 35
The sintered heat insulating time is 20 hours, and other conditions can obtain Tb equally with embodiment 31
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 36
The interior vacuum tightness of stove is better than 1 * 10 during insulation
-4Pa, other conditions can obtain Tb equally with 31
2.97Ce
0.03Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 37
1. the value of selected X is 0.015, presses Tb
2.985Ce
0.015Al
5O
12Form, take by weighing terbium chloride (TbCl
3), aluminum chloride (AlCl
3), Cerium II Chloride (CeCl
3) etc. initial feed 50g altogether, with its molten 1000 ml water solution of making, adding the 1wt% citric acid is stablizer, uses magnetic stirring apparatus to stir and be heated to 60 ℃, obtains Tb
2.985Ce
0.015Al
5O
12Precursor colloidal sol, with this colloidal sol ageing 24 as a child, after 1200 ℃ of calcinings got Tb in 10 hours
2.985Ce
0.015Al
5O
12Powder,
2. the TEOS that adds 0.3wt～0.7wt% carries out ball milling with this powder, after injection forming or cold isostatic compaction are made base substrate, removes organic composition in 2 hours 500 ℃ of pre-burnings again;
3. put into hot-pressed sintering furnace at last base substrate is applied the pressure of 0.2MPa,, obtain Tb 1500 ℃ of sintering temperatures 0.5 hour
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 38
The sintered heat insulating time is 50 hours, and other conditions can obtain Tb equally with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 39
The sintered heat insulating time is 10 hours, and other conditions can obtain Tb equally with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 40
With Tb
2.985Ce
0.015Al
5O
12Ceramic body is put into hot-pressed sintering furnace and is applied 10MPa pressure, and the sintered heat insulating temperature is 900 ℃, and other conditions obtain Tb with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 41
With Tb
2.985Ce
0.015Al
5O
12Ceramic body is put into hot-pressed sintering furnace and is applied 5MPa pressure, and other conditions obtain Tb with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 42
Holding temperature is 1400 ℃, and other conditions obtain Tb with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 43
Holding temperature is 1050 ℃, and other conditions obtain Tb with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 44
Calcining temperature is 900 ℃, and calcination time is 3 hours, and other conditions obtain Tb with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 45
Calcined temperature is 800 ℃, and the pre-burning time is 5 hours, and other conditions obtain Tb with embodiment 37
2.985Ce
0.015Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 46
Employing purity is 99.9% commercial cerium oxide (CeO
2), terbium sesquioxide (Tb
2O
3) and aluminum oxide (Al
2O
3) powder is initial feed, other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Embodiment 47
Employing purity is 99.9% commercial cerium oxide (CeO
2), aluminic acid terbium (TbAlO
3) and aluminum oxide (Al
2O
3) powder is initial feed, other conditions can obtain Tb equally with embodiment 1
2.999Ce
0.001Al
5O
12The crystalline ceramics fluorescent material.
Need to prove,, can obtain the crystalline ceramics fluorescent material of respective components equally, do not enumerate one by one, but do not influence the protection domain of claim of the present invention at this by other conditions of being stated in claims of the present invention.
The Tb of the present invention's preparation
3-xCe
xAl
5O
12The crystalline ceramics fluorescent material, through experiment and analysis revealed, crystalline ceramics fluorescent material of the present invention can be excited by commercial GaInN blue-ray LED, has near the ideal white light colour temperature, and has anti-aging, anti-light decay performance.This material can need not or reduce in the LED encapsulation process and use Resins, epoxy or silica gel, thereby has effectively avoided because organic packaged material weak heat-dissipating, the light decay phenomenon that easily wears out and cause; Material preparation process of the present invention is simple, the yield rate height, and cost is low, easily batch preparations.
Claims (6)
1. doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material, the concrete component that it is characterized in that this material is Tb
3-xCe
xAl
5O
12, wherein the span of x is: 0.001≤x≤0.03.
2. the described doped with cerium and terbium yttrogarnet of claim 1 crystalline ceramics Preparation of Fluorescent Material method is characterised in that the concrete steps of this method are:
1. adopt commercial cerium oxide, terbium peroxide or terbium sesquioxide or aluminic acid terbium and the alumina powder jointed raw material of doing, after the concrete value of selected x, press Tb
3-xCe
xAl
5O
12Form and configure powder raw material;
2. the tetraethoxy that adds 0.3wt%～0.7wt% is as additive, and with powder mixing, refinement, the powder oven dry is after granulation, compressing tablet through ball milling; The back imposes the above cold isostatic pressure of 200MPa to it and is pressed into base substrate, removes organic composition in 0.5～5 hour 200～800 ℃ of pre-burnings again;
3. put into vacuum sintering furnace or hot-pressed sintering furnace sintering some hrs at a certain temperature at last, obtain Tb
3-xCe
xAl
5O
12Doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material.
3. crystalline ceramics Preparation of Fluorescent Material method according to claim 2 is characterized in that the purity of described powder raw material is not less than 99.9%;
4. the described Tb of claim 1
3-xCe
xAl
5O
12The preparation method of crystalline ceramics is characterized in that the step of this method is as follows:
1. be initial feed with Terbium trinitrate or terbium chloride, aluminum nitrate or aluminum chloride, cerous nitrate or Cerium II Chloride, after the concrete value of selected x, press Tb
3-xCe
xAl
5O
12Form and configure raw material; Employing is the chemical coprecipitation of precipitation agent with urea or bicarbonate of ammonia or is that stablizer adopts the sol-gel method wet chemical method to prepare Tb with the citric acid
3-xCe
xAl
5O
12Precursor is after 800～1200 ℃ of calcinings got Tb in 0.5～10 hour
3-xCe
xAl
5O
12Powder;
2. the tetraethoxy that adds 0.3～0.7wt% carries out ball milling with described powder, after injection forming or cold isostatic compaction are made base substrate, removes organic composition in 0.5～5 hour 200～800 ℃ of pre-burnings again;
3. put into vacuum sintering furnace or hot-pressed sintering furnace sintering some hrs at a certain temperature at last, obtain Tb
3-xCe
xAl
5O
12Doped with cerium and terbium yttrogarnet crystalline ceramics fluorescent material.
5. according to claim 2 or 4 described crystalline ceramics Preparation of Fluorescent Material methods, the temperature that it is characterized in that described vacuum sintering is 1400～1650 ℃, and soaking time is 0.5～50 hour; Vacuum tightness in the vacuum sintering furnace is better than 3 * 10
-2Pa;
6. according to claim 2 or 4 described crystalline ceramics Preparation of Fluorescent Material methods, the temperature that it is characterized in that described hot pressed sintering is 900～1500 ℃, is 0.2～10MPa to the ceramic body applied pressure, and soaking time is 0.5～30 hour.
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| CN103160280A (en) * | 2011-12-08 | 2013-06-19 | 陈引幹 | Yttrium aluminum garnet fluorescent material, preparation method thereof and light emitting diode device comprising yttrium aluminum garnet fluorescent material |
| CN104844171A (en) * | 2015-04-27 | 2015-08-19 | 安徽省含山县顺天纺织有限公司 | Glass bead containing light alumina ceramic eyelet |
| CN106282722A (en) * | 2016-08-16 | 2017-01-04 | 安徽瑞泰新材料科技有限公司 | A kind of cement grinding system special aluminium oxide ceramics ball and preparation method thereof |
| CN106316381A (en) * | 2016-08-08 | 2017-01-11 | 屠秀芬 | Preparation method of YAG-nano terbium oxide composite magneto-optical transparent ceramic |
| WO2017157157A1 (en) * | 2016-03-18 | 2017-09-21 | 深圳市绎立锐光科技开发有限公司 | Method for preparing fluorescent ceramic provided with aluminum nitride substrate, and related fluorescent ceramic |
| CN109896853A (en) * | 2017-12-11 | 2019-06-18 | 上海航空电器有限公司 | With more low-expansion ceramic composite, preparation method and light supply apparatus |
| CN111285674A (en) * | 2018-12-07 | 2020-06-16 | 上海航空电器有限公司 | Ultrathin fluorescent ceramic for high-power laser lighting, preparation method and optical system |
| CN112125659A (en) * | 2020-10-15 | 2020-12-25 | 贵州赛义光电科技有限公司 | Fluorescent ceramic for warm white lighting and preparation method thereof |
| WO2022100647A1 (en) * | 2020-11-11 | 2022-05-19 | 中国科学院福建物质结构研究所 | Green fluorescent ceramic material, preparation method therefor and use thereof |
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| CN103160280A (en) * | 2011-12-08 | 2013-06-19 | 陈引幹 | Yttrium aluminum garnet fluorescent material, preparation method thereof and light emitting diode device comprising yttrium aluminum garnet fluorescent material |
| US9085733B2 (en) | 2011-12-08 | 2015-07-21 | National Cheng Kung University | Yttrium aluminum garnet phosphor, method for preparing the same, and light-emitting diode containing the same |
| CN104844171A (en) * | 2015-04-27 | 2015-08-19 | 安徽省含山县顺天纺织有限公司 | Glass bead containing light alumina ceramic eyelet |
| WO2017157157A1 (en) * | 2016-03-18 | 2017-09-21 | 深圳市绎立锐光科技开发有限公司 | Method for preparing fluorescent ceramic provided with aluminum nitride substrate, and related fluorescent ceramic |
| CN106316381A (en) * | 2016-08-08 | 2017-01-11 | 屠秀芬 | Preparation method of YAG-nano terbium oxide composite magneto-optical transparent ceramic |
| CN106282722A (en) * | 2016-08-16 | 2017-01-04 | 安徽瑞泰新材料科技有限公司 | A kind of cement grinding system special aluminium oxide ceramics ball and preparation method thereof |
| CN109896853A (en) * | 2017-12-11 | 2019-06-18 | 上海航空电器有限公司 | With more low-expansion ceramic composite, preparation method and light supply apparatus |
| CN109896853B (en) * | 2017-12-11 | 2022-07-15 | 上海航空电器有限公司 | Ceramic composite with lower expansion coefficient, preparation method and light source device |
| CN111285674A (en) * | 2018-12-07 | 2020-06-16 | 上海航空电器有限公司 | Ultrathin fluorescent ceramic for high-power laser lighting, preparation method and optical system |
| CN112125659A (en) * | 2020-10-15 | 2020-12-25 | 贵州赛义光电科技有限公司 | Fluorescent ceramic for warm white lighting and preparation method thereof |
| WO2022100647A1 (en) * | 2020-11-11 | 2022-05-19 | 中国科学院福建物质结构研究所 | Green fluorescent ceramic material, preparation method therefor and use thereof |
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Application publication date: 20110907 |