CN103952153A - Lu-Sb-doped aluminate green fluorescent powder and preparation method thereof - Google Patents
Lu-Sb-doped aluminate green fluorescent powder and preparation method thereof Download PDFInfo
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- CN103952153A CN103952153A CN201410215759.1A CN201410215759A CN103952153A CN 103952153 A CN103952153 A CN 103952153A CN 201410215759 A CN201410215759 A CN 201410215759A CN 103952153 A CN103952153 A CN 103952153A
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Abstract
The invention relates to Lu-Sb-doped aluminate green fluorescent powder and a preparation method thereof. The Lu-Sb-doped aluminate green fluorescent powder is activated by adopting Ce<3+> and has a general formula of Y[3-x-y-m]Lu[y]Sb[m]Al5O12 : C3<3+>x, wherein x is 0.01-0.2, preferably 0.06-0.08; y is 0.5-4.5, preferably 1.0-4.5; m is 0-0.006, preferably 0.002-0.006. According to the method, YAG (yttrium aluminum garnet) fluorescent powder is doped with element Lu to obtain fluorescent powder with main emission peak at a green waveband, the integral light effect of the fluorescent powder is not reduced, and a high-brightness white LED can be obtained by matching the green fluorescent powder with yellow fluorescent powder and a blue LED chip; if the green fluorescent powder is matched with the blue LED chip, green light can be directly obtained; if the green fluorescent powder is matched with the yellow fluorescent powder and the blue LED chip, cold-tone white light can be obtained; the green fluorescent powder also can be matched with red fluorescent powder and the blue LED chip to obtain white light; and since trace Sb is added, the light-emitting intensity of the prepared fluorescent powder is greatly improved.
Description
Technical field
The present invention relates to aluminate green fluorescent powder of a kind of doped with rare-earth elements lutetium and antimony and preparation method thereof, be particularly useful for blue chip and excite the LED green emitting phosphor of lower use, belong to rare earth luminescent material technical field.
Background technology
Photodiode (LED) is the New Solid illuminating device that development in recent years is got up, and has the advantages such as efficiency is high, the life-span long, pollution-free, energy-conservation.Be widely used in the every field such as liquid crystal screen backlight, pilot lamp, lamps for vehicle, electronics and indoor and outdoor lighting.Its use has far-reaching influence to the Sustainable development of energy-conserving and environment-protective and environment.
For general illumination, people more need white light source.The LED of white light in 1998 succeeds in developing, and this LED is packaged together GaN chip and yttrium aluminum garnet (YAG).GaN chip blue light-emitting (λ p=465nm, Wd=30nm), what high temperature sintering was made contains Ce
3+yAG fluorescent material send sodium yellow after being subject to this blue-light excited and penetrate, peak value 550nm.Blue-ray LED substrate is arranged in bowl type reflection cavity, covers to be mixed with the thin resin layer of YAG, about 200-500nm.The blue light part that LED substrate sends is absorbed by fluorescent material, and the yellow light mix that another part blue light and fluorescent material send, obtains white light.The advantage of this combination is that luminous efficiency is high, and deficiency is to lack transmitting in ruddiness region, so the white light LEDs device colour rendering index of making is lower, colour temperature is higher.Current existing solution is to change YAG:Ce by ion substitution
3+emission peak positions, red shift emission peak, but the deficiency of this mode is to have reduced the overall light efficiency of fluorescent material, is therefore badly in need of the relative YAG:Ce of preparation a kind of transmitting main peak
3+the broad peak fluorescent material of red shift, if transmitting main peak is at the fluorescent material of green position.
With green emitting phosphor cooperation yellow fluorescent powder and blue led chip, can obtain the white light LEDs of high brightness; If use green emitting phosphor to coordinate blue-light LED chip, can directly obtain green glow; If use green emitting phosphor to coordinate yellow fluorescent powder and blue led chip, can obtain cool tone white light; Green emitting phosphor also can coordinate red fluorescence powder and blue led chip and obtain white light.The colour rendering index (CRI) of white light LEDs is relevant with blue chip, YAG fluorescent material, correlated(color)temperature etc., wherein the most important thing is YAG fluorescent material, the LED in different-colour district, and the fluorescent material and the blue chip that use are different.The fluorescent material emission peak that the pipe that target colour temperature is lower is used is longer, the peak value of chip also will be grown, lower than 4000K colour temperature, also to add in addition the fluorescent material glowing, to make up the deficiency of red composition, reach and improve the object of colour rendering index, under the chip keeping and the constant condition of fluorescent material, colour temperature more high color rendering index (CRI) is higher.
Summary of the invention
The object of this invention is to provide one be suitable for LED with green emitting phosphor with and preparation method thereof, for realizing this object, technical scheme provided by the invention is:
The aluminate green fluorescent powder of this doping Lu, Sb, adopts Ce
3+activate, its general formula (1) is: Y
3-x-y-mlu
ysb
mal
5o
12: Ce
3+ x(1) wherein the span of x is 0.01 ~ 0.2, preferably 0.06 ~ 0.08; The span of y is 0.5 ~ 4.5, preferably 1.0 ~ 4.5; The span of m is 0 ~ 0.006, preferably 0.002 ~ 0.006.
The present invention, to the Lu element that adulterates in YAG fluorescent material, obtains launching the fluorescent material of main peak at green wave band, does not reduce the overall light efficiency of fluorescent material, coordinates yellow fluorescent powder and blue led chip with this green emitting phosphor, can obtain the white light LEDs of high brightness; If use this green emitting phosphor to coordinate blue-light LED chip, can directly obtain green glow; If use this green emitting phosphor to coordinate yellow fluorescent powder and blue led chip, can obtain cool tone white light; Also can coordinate red fluorescence powder and blue led chip and obtain white light; Also, by adding wherein micro-antimony element, improve greatly the luminous intensity of the fluorescent material of preparing.
Particularly, it is 530nm ~ 510nm that the light of this green emitting phosphor is penetrated peak value, and this wave band is green light band.
The method of preparing the aluminate green fluorescent powder of this doping Lu, Sb, comprises the following steps:
A) take respectively aluminum oxide, yttrium oxide, cerium oxide, lutecium oxide, weisspiessglanz according to the stoichiometric ratio of general formula (1);
B) difference that obtains fluorescent material particle diameter size and wavelength according to plan is chosen different fusing assistants, and described fusing assistant is one or both in boric acid, aluminum fluoride, and the fusing assistant that accounts for 2-3% mole of general formula (1) is carried out crossing 200 eye mesh screens after dry bulb mill 1.5-2h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 25-30h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
Burn because the present invention only carries out a high temperature to raw material, thereby the sintered material hardness of powder obviously reduces, the powder agglomates of sintering is loose, has not only reduced technological process, and save energy and quality product go up not down; Fusing assistant is carried out to ball-milling processing in advance, the Ball-milling Time of head product is greatly reduced, thereby increased the crystal brightness of the finished product.
Embodiment
Embodiment 1:
An adulterate aluminate green fluorescent powder of Lu, its chemical formula is Y
1.93lu
1al
5o
12: Ce
3+ 0.07
A) Y of 327.1g
2o
3, 382.6g Al
2o
3, 272.1g Lu
2o
3, 18.1g CeO
2;
B) accurately take 20g aluminum fluoride and carry out crossing 200 eye mesh screens after dry bulb mill 2h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 25h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
Embodiment 2:
An adulterate aluminate green fluorescent powder of Lu, Sb, chemical formula is Y
1.926lu
1sb
0.004al
5o
12: Ce
3+ 0.07;
A) accurately take the Y of 326.3g
2o
3, 382.6g Al
2o
3, 272.0g Lu
2o
3, 18.0g CeO
2, 0.87g Sb
2o
3;
B) accurately take 20g boric acid and carry out crossing 200 eye mesh screens after dry bulb mill 1.5h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 30h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
Embodiment 3:
An adulterate aluminate green fluorescent powder of Lu, chemical formula is Y
1.13lu
1.8al
5o
12: Ce
3+ 0.07
A) accurately take the Y of 177.1g
2o
3, 353.6g Al
2o
3, 542.6g Lu
2o
3, 16.7g CeO
2;
B) accurately take 10g aluminum fluoride and 10g boric acid and carry out crossing 200 eye mesh screens after dry bulb mill 1.8h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 27h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
Embodiment 4:
An adulterate aluminate green fluorescent powder of Lu and Sb, chemical formula is Y
1.126lu
1.8sb
0.004al
5o
12: Ce
3+ 0.07
A) accurately take the Y of 176.3g
2o
3, 353.6g Al
2o
3, 542.5g Lu
2o
3, 16.7g CeO
2, 0.80g Sb
2o
3;
B) accurately take 20g aluminum fluoride and carry out crossing 200 eye mesh screens after dry bulb mill 1.6h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 26h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
Comparative example:
A undope aluminate green fluorescent powder of Lu and Sb, chemical formula is Y
2.925al
1.2o
12: Ce
3+ 0.071.
A) accurately take the Y of 434.0g
2o
3, 80.4g Al
2o
3, 15.8g CeO
2;
B) accurately take 20g aluminum fluoride and carry out crossing 200 eye mesh screens after dry bulb mill 2h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 30h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
Embodiment 1-4 and comparative example are carried out to performance test, obtain data as follows:
Sample | Emission peak (nm) | CIE coordinate X | CIE coordinate Y | Luminous intensity |
Comparative example | 558 | 0.435 | 0.545 | 100 |
Embodiment 1 | 535 | 0.385 | 0.556 | 88 |
Embodiment 2 | 535 | 0.385 | 0.556 | 96 |
Embodiment 3 | 520 | 0.351 | 0.567 | 84 |
Embodiment 4 | 520 | 0.351 | 0.567 | 92 |
As can be seen from the above table, it is more that the emission peak of the YAG of the Lu that undopes exceeds green wave band 530nm ~ 510nm, but luminous intensity is good; Doping Lu YAG emission peak near or be positioned between green wave band 530nm ~ 510nm, luminous intensity declines to some extent, but doping Sb after luminous intensity have a distinct increment.
Claims (3)
1. the aluminate green fluorescent powder of doping Lu, Sb, adopts Ce3+ to activate, and its general formula (1) is: Y
3-x-y-mlu
ysb
mal
5o
12: Ce
3+ x(1) wherein the span of x is 0.01 ~ 0.2, preferably 0.06 ~ 0.08; The span of y is 0.5 ~ 4.5, preferably 1.0 ~ 4.5; The span of m is 0 ~ 0.006, preferably 0.002 ~ 0.006.
2. the aluminate green fluorescent powder of doping Lu, Sb according to claim 1, is characterized in that it is 530nm ~ 510nm that its light is penetrated peak value.
3. the method for the aluminate green fluorescent powder of preparation doping claimed in claim 1 Lu, Sb, comprises the following steps:
A) take respectively aluminum oxide, yttrium oxide, cerium oxide, lutecium oxide, weisspiessglanz according to the stoichiometric ratio of general formula (1);
B) difference that obtains fluorescent material particle diameter size and wavelength according to plan is chosen different fusing assistants, and described fusing assistant is one or both in boric acid, aluminum fluoride, and the fusing assistant that accounts for 2-3% mole of general formula (1) is carried out crossing 200 eye mesh screens after dry bulb mill 1.5-2h;
C) starting material that a) and b) step obtains are put into biconical mixer and fully mix, mixing time is 25-30h;
D) mixture that c) step obtains is packed into crucible and puts into hyperthermia tunnel Kiln;
E) in hyperthermia tunnel Kiln, pass into the reducing atmosphere of hydrogen: nitrogen=3:1, at 1580 DEG C, constant temperature burns 4.5h;
F) head product that e) step obtains is taken out from crucible, be down to after room temperature, first carry out coarse breaking with excellent pestle, then roller pair breaking;
G) head product that f) step obtains is washed after 5 times with the deionized water of 90 DEG C, put into baking oven and dry;
H) head product that g) step obtains is crossed to 200 eye mesh screens, packaging, obtains finished product.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112745846A (en) * | 2020-12-30 | 2021-05-04 | 河北利福光电技术有限公司 | Green fluorescent powder suitable for high-power device 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 |
CN114574205A (en) * | 2022-03-28 | 2022-06-03 | 中国科学院赣江创新研究院 | Antimony aluminate fluorescent powder and preparation method and application thereof |
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2014
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Patent Citations (2)
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DE102007010719A1 (en) * | 2007-03-06 | 2008-09-11 | Merck Patent Gmbh | Phosphors consisting of doped garnets for pcLEDs |
CN102186944A (en) * | 2008-10-13 | 2011-09-14 | 默克专利有限公司 | Doped garnet fluorescent substance having red shift for PC leds |
Non-Patent Citations (1)
Title |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN112745846A (en) * | 2020-12-30 | 2021-05-04 | 河北利福光电技术有限公司 | Green fluorescent powder suitable for high-power device and preparation method thereof |
CN112745846B (en) * | 2020-12-30 | 2022-11-11 | 河北利福光电技术有限公司 | Green fluorescent powder suitable for high-power device and preparation method thereof |
CN114574205A (en) * | 2022-03-28 | 2022-06-03 | 中国科学院赣江创新研究院 | Antimony aluminate fluorescent powder and preparation method and application thereof |
CN114574205B (en) * | 2022-03-28 | 2023-11-24 | 中国科学院赣江创新研究院 | Antimony aluminate fluorescent powder and preparation method and application thereof |
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Application publication date: 20140730 |