CN1880404A - A phosphor that can be excited by ultraviolet light and blue light LED to emit red light - Google Patents
A phosphor that can be excited by ultraviolet light and blue light LED to emit red light Download PDFInfo
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- CN1880404A CN1880404A CN 200510078430 CN200510078430A CN1880404A CN 1880404 A CN1880404 A CN 1880404A CN 200510078430 CN200510078430 CN 200510078430 CN 200510078430 A CN200510078430 A CN 200510078430A CN 1880404 A CN1880404 A CN 1880404A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 241001025261 Neoraja caerulea Species 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 12
- 230000005284 excitation Effects 0.000 abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 abstract 1
- 229910052775 Thulium Inorganic materials 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000002609 medium Substances 0.000 description 19
- 238000001228 spectrum Methods 0.000 description 18
- 239000011777 magnesium Substances 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 10
- 239000010431 corundum Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 5
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 206010023126 Jaundice Diseases 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- SKQWEERDYRHPFP-UHFFFAOYSA-N [Y].S=O Chemical class [Y].S=O SKQWEERDYRHPFP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical class [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
一种可被紫外光、蓝光LED激发而发红光的荧光粉，其通式为AMaOb:Mnx，Ry。其中A为Mg，Ca，Sr，Ba，Zn中的1～3种元素的组合；M为Al，Ga，Y，Gd中的1～3种元素的组合；R为Ce，Pr，Nd，Sm，Tb，Dy，Ho，Er，Tm和Cu中1～3种元素的组合；0.9＜a＜25，3＜b＜40，0.0001＜x＜1，0≤y＜0.5。此种荧光粉的制造方法为：按照通式将各原料A、M、Mn、R的单质、化合物或相应的盐类及助熔剂，混合均匀后，通过高温合成，经后处理制成，荧光粉中心粒径D50为2～6μm。本发明的荧光粉具有化学稳定性好、发光强度高、激发波长宽等特点。该荧光粉适合制备紫外光、蓝光激发LED。A fluorescent powder that can be excited by ultraviolet light and blue light LED to emit red light has a general formula of AM a O b :Mn x ,R y . A is a combination of 1 to 3 elements of Mg, Ca, Sr, Ba, and Zn; M is a combination of 1 to 3 elements of Al, Ga, Y, and Gd; R is a combination of 1 to 3 elements of Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Cu; 0.9<a<25, 3<b<40, 0.0001<x<1, 0≤y<0.5. The manufacturing method of the fluorescent powder is as follows: according to the general formula, the single substance, compound or corresponding salt of each raw material A, M, Mn, R and flux are mixed uniformly, synthesized by high temperature, and post-treated to obtain the fluorescent powder. The central particle diameter D 50 is 2 to 6 μm. The fluorescent powder of the present invention has the characteristics of good chemical stability, high luminous intensity, wide excitation wavelength, etc. The fluorescent powder is suitable for preparing ultraviolet light and blue light excited LED.
Description
Technical field
The fluorescent material and the manufacture method thereof that the present invention relates to a kind of can being excited and glow by UV-light, blue-ray LED.(C09K11/77?H05B33/02)
Technical background
The LED that come out the sixties in 20th century obtains develop rapidly in short more than 30 year, particularly succeeding in developing of white light LEDs in 1998 makes LED use and stepped a substantial step from simple sign Presentation Function to illumination functions.
White light LEDs generally uses yttrium aluminum garnet (YAG) fluorescent material of blue light-emitting LED stack by blue-light excited jaundice light at present, synthesizes white light.Owing to only contain indigo plant, yellow these two main ripples in its luminescent spectrum, lack the ruddiness composition, so there is the problem that colour temperature is higher, colour rendering index is on the low side, do not meet the general lighting requirement.Because human eye is much higher than the susceptibility a little less than the light intensity the susceptibility of aberration, for illumination, the color developing of light source is often more important than luminous efficiency.
The appearance of purple light or ultraviolet LED, it provide fluorescent material with purple light or ultraviolet excitation three primary colors fluorescent powder or multiple illuminant colour obtain white light by way of.Because the energy of UV-light is than blue light height, the white light LEDs light efficiency of preparing can further improve, and its spectral range is wideer simultaneously, and colour rendering index can further increase, and can prepare the LED product of different-colour or different colours as required.But at present the emissive porwer less than the ultraviolet LED of 370nm is extremely low, does not have practical value, and existing led chip development and production field are all in the efficient of making great efforts raising 370～420nm purple light and ultraviolet leds.The three primary colors fluorescent powder that is widely used in compact energy-saving fluorescent lamp at present is not suitable for the demand of this white light LEDs, must develop the three primary colours or the multicolor phosphor of new white light LEDs special use, and the fluorescent material that existing development comes out to be suitable for using is: red fluorescence powder: Y
2O
3: Eu
3+, Y
2O
2S:Eu
3+Deng; Green emitting phosphor BaMgAl
10O
17: Mn
2+, Ca
8Mg (SiO
4)
4Cl
2: Eu
2+, Mn
2+Deng; Blue colour fluorescent powder BaMgAl
10O
17: En
2+, Sr
5(PO
4)
3Cl:Eu
2+Deng.
With in the three primary colors fluorescent powder, red fluorescence powder exists luminous intensity low at the ultraviolet white light LEDs, and problem that luminous efficiency is low and ultraviolet green, blue colour fluorescent powder matching are poor, can't realize having the white than the color reducing power of rich shade.
US6252254 discloses the sulphide fluorescent material SrS:Eu that several ultraviolets glow
2+, (Sr, Ca) S:SrS:Eu
2+, SrY
2S
4: Eu
2+, CaLa
2S
4: Ce
3+Though, the luminous intensity height, the chemical stability of sulfide own is bad; It is the europkium-activated yttrium oxysulfide of trivalent that Chinese patent CN1478855A discloses a kind of purple light excited rouge and powder, though luminous intensity and chemical stability are good, discharges SO in the production process
2, the environmental pollution degree is big.
US6501100 provides orange emitted fluorescence powder: Sr
0.8Eu
0.1Mn
0.1)
2P
2O
7It is the europkium-activated yttrium aluminum garnet of trivalent that Chinese patent CN1397625A discloses the fluorescent material that a kind of ultraviolet glows; It is the compound of the europkium-activated molybdate of trivalent that Chinese patent CN1539914A discloses the fluorescent material that a kind of ultraviolet glows.Contrast finds that the emissive porwer of these three kinds of red fluorescence powders only the invention provides 1/4,1/5 and 1/3 of fluorescent material by experiment.
In the LED encapsulation process, MODEL OF THE PHOSPHOR PARTICLE SIZE also is the important factor that influences the LED luminous intensity.Particle diameter is big, maldistribution, causes fluorescent material non-uniform light in the LED potting resin, and luminous intensity is low.
Summary of the invention
The invention provides a kind of can be by UV-light, blue-ray LED excites and the fluorescent material that glows, main chemical constitution expression is: AM
aO
b: Mn
x, R
y
A is Mg, Ca, Sr, Ba, the combination of 1～3 kind of element among the Zn;
M is Al, Ga, Y, the combination of 1～3 kind of element among the Gd;
R is Eu, Dy, Ce, Pr, Nd, Sn, Sm, Tb, Ho, Er, the combination of 1～3 kind of element among the Tm;
0.9＜a＜25，3＜b＜40，0.0001＜x＜1，0≤y＜0.5。
Wherein excite, launching effect is reasonable is:
8＜a＜20,15＜b＜30,0.0008＜x＜0.1,0≤y＜0.1; This fluorescent material is exciting down at 300nm-500nm light, particularly 400nm and 470nm, presents the emmission spectrum of 630nm-660nm.The scope of excitation spectrum and emmission spectrum is all than broad.
Provided by the invention can be by UV-light, blue-ray LED excites and the manufacture method of red phosphor is as follows: according to general formula with A, M, Mn, the oxide compound of R or corresponding salt and fusing assistant, take by weighing according to molar ratio, after mixing, prior to 600 ~ 1400 ℃ of pre-burnings 1 ~ 15 hour, cooling, pulverize, sieve, after grinding evenly, burnt till 1 ~ 20 hour in 800～1500 ℃ of high temperature again, fluorescent material is pulverized, sieve, after the grinding, be scattered in dispersion medium ethanol or the acetone, by adopting the fluid sedimentation-separation technology to carry out classification, to guarantee that MODEL OF THE PHOSPHOR PARTICLE SIZE DISTRIBUTION is even, final drying obtains fluorescent material.
The material purity A that fluorescent material of the present invention uses is 3N (99.9%), M and R 4N (99.99%).
The fusing assistant that fluorescent material of the present invention uses comprises NH
4Cl, NH
4F, (NH
4)
2HPO
4, NaCl, CaCl
2, Li
2CO
3, Na
2CO
3CaF
2, MgF
2, K
3PO
4, H
3BO
3In 1～3 kind, the ratio of adding is 0.05 ~ 10wt%.
Fluorescent material of the present invention burns till and adopts the twice firing technology, and it is more even to guarantee that each raw material mixes, and reacts more abundant.Effect high temperature firing condition preferably is: 800 ~ 1300 ℃ of pre-burnings 6～12 hours, and 1000～1400 ℃ were burnt till 6～15 hours, and firing atmosphere is an oxidizing atmosphere.
The pulverizing of fluorescent material of the present invention, general comminution by gas stream and the quick ball-grinding machine of using of grinding, preliminary assurance obtains the thinner fluorescent material of particle diameter, helps improving in the classification process productive rate of fluorescent material.
The fluorescent material particle diameter also is the important factor that influences luminous intensity, and the too little and resin of particle diameter is not easy to mix, and luminous intensity is low; Though the fluorescent material that particle diameter is big helps improving luminous intensity, for the fluorescent material that is applied to LED, cause non-uniform light easily.The invention provides the medium particle diameter D of fluorescent material
50In 2～6 mu m ranges.
The chemical constitution of fluorescent material of the present invention itself has determined its stability of structure, so chemical stability is good.
The object of the invention provide a kind of can be at 300nm-500nm light, particularly 400nm and 470nm excite down, the red fluorescence powder and the manufacture method thereof that present the 630nm-680nm emmission spectrum, this fluorescent material has that luminous intensity height, chemical stability are good, excitation wave length and width, granularity are little, characteristics such as narrowly distributing, manufacture method is simple, pollution-free.This fluorescent material is applicable to the red fluorescence powder that ultraviolet excitation LED is required on the one hand, is applicable on the other hand in yttrium aluminum garnet (YAG) fluorescent material that is doped to blue-light excited jaundice light, improves the colour rendering index of GaN base white light LEDs.
Description of drawings
Fig. 1 is (Sr
0.6Ba
0.1Mg
0.3) (Y
0.3Al
0.4Ga
0.3)
16O
24: Mn
0.005Tm
0.01Eu
0.01Excite, emmission spectrum (654nm excites).
Fig. 2 is (Sr
0.6Ba
0.1Mg
0.3) (Y
0.3Al
0.4Ga
0.3)
16O
24: Mn
0.005Tm
0.01Eu
0.01Emmission spectrum (470nm excites).
Fig. 3 is (Sr
0.6Ba
0.1Mg
0.3) (Y
0.3Al
0.4Ga
0.3)
16O
24: Mn
0.005Tm
0.01Eu
0.01The fluorescent material particle diameter.
Embodiment
Embodiment one: (Sr
0.6Ba
0.1Mg
0.3) (Y
0.3Al
0.4Ga
0.3)
16O
24: Mn
0.005Tm
0.01Eu
0.01
SrCO
38.856g Ga
2O
344.98g alkali formula magnesium 3.022g
BaCO
3 1.973g MnCO
3 0.115g
Y
2O
3 54.19g Tm
2O
3 0.193g
Al
2O
3?32.64g Eu
2O
3 0.176g
Fusing assistant 2.6g (CaF
2, (NH
4)
2HPO
4, Li
2CO
3)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 1000 ℃ of pre-burnings are 8 hours under oxygen atmosphere, and cooling is ground back 1350 ℃ of high temperature and burnt till, and the time is 10 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 5.6 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 654nm.It excites (400nm excites), emmission spectrum (654nm excites) to see Fig. 1, and emmission spectrum (470nm excites) is seen Fig. 2, and the fluorescent material particle diameter is seen Fig. 3.
Embodiment two: (Sr
0.1Ca
0.9) (Gd
0.3Al
0.7)
18O
28: Mn
0.03Dy
0.02Sm
0.01
SrCO
3 1.471g MnSO
4.H
2O 0.507g
CaCO
3 9.000g Dy
2O
3 0.373g
Gd
2O
3 97.90g Sm
2O
3 0.174g
Al
2O
3 64.26g
Fusing assistant 2.4g (NH
4F 1.0g MgF
20.5g H
3BO
30.9g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 1200 ℃ of pre-burnings are 6 hours under oxygen atmosphere, and cooling is ground back 1400 ℃ of high temperature and burnt till, and the time is 6 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 4.8 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 650nm.
Embodiment three: Ca (Gd
0.1Al
0.9)
14O
22: Mn
0.005Eu
0.01Ho
0.02
CaCO
3 10.00g MnCO
3 0.057g
Gd
2O
3?25.38g Eu
2O
3 0.176g
Al
2O
3?64.26g Ho
2O
3 0.378g
Fusing assistant 1.9g (NH
4Cl 0.8g NaCl 0.4g K
3PO
40.7g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 900 ℃ of pre-burnings are 9 hours under oxygen atmosphere, and cooling is ground back 1380 ℃ of high temperature and burnt till, and the time is 6 hours.After pulverizing, sieving fluorescent material is scattered in the medium-acetone, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 4.0 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 647.
Embodiment four: (Mg
0.5Zn
0.5) (Al
0.8Ga
0.2)
12O
19: Mn
0.06Pr
0.01
Alkali formula magnesium 5.037g Ga
2O
322.17g
ZnO 4.068g MnO
2 0.521g
Al
2O
3 48.96g Pr
6O
11?0.170g
Fusing assistant 1.6g ((NH
4)
2HPO
41.0g Li
2CO
30.6g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 800 ℃ of pre-burnings are 10 hours under oxygen atmosphere, and cooling is ground back 1200 ℃ of high temperature and burnt till, and the time is 12 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 3.2 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 642nm.
Embodiment five: (Sr
0.4Ca
0.5Ba
0.1) (Ga
0.1Al
0.6Y
0.03)
10O
16: Mn
0.06Sn
0.05Er
0.04
SrCO
3 5.880g Y
2O
3 33.87g
CaCO
3 5.000g MnCO
3 0.688
BaCO
3 1.973g SnO
2 0.754
Ga
2O
3?9.372g Er
2O
3 0.765g
Al
2O
3?30.60g
Fusing assistant 2.3g (CaF
21.3g MgF
21g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 1250 ℃ of pre-burnings are 6 hours under oxygen atmosphere, and cooling is ground back 1450 ℃ of high temperature and burnt till, and the time is 6 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 4.3 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 646nm.
Embodiment six: (Mg
0.7Sr
0.3) (Ga
0.1Al
0.6Gd
0.3)
12O
19: Mn
0.005Tm
0.01Ho
0.02
SrCO
3 4.428g Gd
2O
3 65.27g
MgCO
3 5.901g MnSO
4.H
2O 0.085g
Ga
2O
3 11.25g Tm
2O
3 0.193g
Al
2O
3 36.72g Ho
2O
3 0.378g
Fusing assistant 1.2g (NH
4Cl 0.6g H
3BO
30.6g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 1050 ℃ of pre-burnings are 8 hours under oxygen atmosphere, and cooling is ground back 1250 ℃ of high temperature and burnt till, and the time is 12 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 2.5 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 643nm.
Embodiment seven: (Mg
0.6Ca
0.4) Y
14O
22: Mn
0.005Eu
0.01Ho
0.02
MgCO
3 5.058g MnCO
3 6.874g
CaCO
3 4.000g Eu
2O
3 0.176g
Y
2O
3 158.06g Ho
2O
3 0.378g
Fusing assistant 5.6g (NH
4F 2.9g MgF
22.7g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 1000 ℃ of pre-burnings are 7 hours under oxygen atmosphere, and cooling is ground back 1350 ℃ of high temperature and burnt till, and the time is 9 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the continuous fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 5.5 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 640nm.
Embodiment eight: (Ca
0.9Zn
0.1) (Ga
0.1Al
0.9)
12O
19: Mn
0.005Tm
0.01Ho
0.02
CaO 5.4g Al
2O
3 55.08g
ZnO 0.814g MnO
2 0.044g
Ga
2O
3 11.25g Tm
2O
3 0.193g Ho
2O
3 0.378g
Fusing assistant 0.6g (MgF
20.6g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 800 ℃ of pre-burnings are 8 hours under oxygen atmosphere, and cooling is ground back 1250 ℃ of high temperature and burnt till, and the time is 6 hours.After pulverizing, sieving fluorescent material is scattered in the medium-acetone, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 3.5 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 639nm.
Embodiment nine: Ca (Ga
0.2Al
0.8)
12O
19: Mn
0.001
CaCO
3 10g MnO
2 0.009g
Ga
2O
322.50g fusing assistant 0.8g (NH
4F 0.8g)
Al
2O
3 48.96g
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 900 ℃ of pre-burnings are 6 hours under oxygen atmosphere, and cooling is ground back 1300 ℃ of high temperature and burnt till, and the time is 12 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 4.1 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 641nm.
Embodiment ten: Sr (Gd
0.3Al
0.7)
16O
28: Mn
0.08
SrCO
3 14.71g MnCO
3 1.84g
Gd
2O
3 87.03g Al
2O
3 57.12g
Fusing assistant 1.2g (Li
2CO
30.6 MgF
20.6g)
Above-mentioned raw materials is put into the corundum ball grinder after grinding evenly on the shredder, and in 95 porcelain crucibles of packing into, 1200 ℃ of pre-burnings are 6 hours under oxygen atmosphere, and cooling is ground back 1330 ℃ of high temperature and burnt till, and the time is 8 hours.After pulverizing, sieving fluorescent material is scattered in the ethanol medium, adopts the fluid sedimentation-separation technology to carry out classification, obtain the material that medium particle diameter is 5.6 μ m after the drying.Excite down at 300nm-500nm light (particularly 400nm and 470nm), present the emmission spectrum of 630nm-680nm.Peak wavelength is 649nm.
Claims (5)
1 one kinds of fluorescent material that can be excited by UV-light, blue-ray LED and glow is characterized in that main chemical constitution expression is: AM
aO
b: Mn
x, R
y, the medium particle diameter D of fluorescent material
50Be 2～6 μ m;
Wherein, A is Mg, Ca, Sr, Ba, the combination of 1～3 kind of element among the Zn;
M is Al, Ga, Y, the combination of 1～3 kind of element among the Gd;
R is Eu, Dy, Ce, Pr, Nd, Sn, Sm, Tb, Ho, Er, the combination of 1～3 kind of element among Tm and the Cu;
0.9＜a＜25，3＜b＜40，0.0001＜x＜1，0≤y＜0.5。
2, a kind of can the being excited according to claim 1 and fluorescent material that glows is characterized in that 8＜a＜20,15＜b＜30,0.0008＜x＜0.1,0≤y＜0.1 by UV-light, blue-ray LED.
3, a kind of can being excited and the manufacture method of the fluorescent material that glows by UV-light, blue-ray LED, it is characterized in that according to oxide compound or corresponding salt and the fusing assistant of general formula A, M, Mn, R, take by weighing according to molar ratio, after mixing, prior to 600～1400 ℃ of pre-burnings in the oxygen atmosphere 1～15 hour, cooling, grind evenly after, burnt till 1～20 hour in 800～1500 ℃ of high temperature again, through pulverizing, sieve, making after the classification, drying;
Described fusing assistant comprises NH
4Cl, NH
4F, (NH
4)
2HPO
4, NaCl, CaCl
2, Li
2CO
3, Na
2CO
3CaF
2, MgF
2, K
3PO
4, H
3BO
3In 1～3 kind, the ratio of adding is 0.05～10wt%.
4, according to claim 3 a kind of can be by UV-light, blue-ray LED excites and the manufacture method of red phosphor, it is characterized in that in oxygen atmosphere 800～1300 ℃ of pre-burnings 6～12 hours, after cooling, the grinding evenly, burnt till 6～15 hours in 1000～1400 ℃ again, through pulverizing, sieve, making after the classification, drying.
5, according to claim 3 a kind of can be by UV-light, blue-ray LED excites and the manufacture method of red phosphor, it is characterized in that described classification process is: fluorescent material is scattered in ethanol or acetone, carries out classification by adopting the fluid sedimentation-separation technology.
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| CN101570688A (en) * | 2008-04-28 | 2009-11-04 | 大连路明发光科技股份有限公司 | Red luminescent material and luminescent device using same |
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| CN105219378A (en) * | 2015-09-28 | 2016-01-06 | 杭州电子科技大学 | A kind of silicate blue fluorescent powder for white-light LED and preparation method thereof |
| CN106967424A (en) * | 2015-11-11 | 2017-07-21 | 日亚化学工业株式会社 | Manufacture method, nitride phosphor and the light-emitting device of nitride phosphor |
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