CN1585141A - White light emitting diode and phosphor for light conversion thereof - Google Patents
White light emitting diode and phosphor for light conversion thereof Download PDFInfo
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- CN1585141A CN1585141A CNA031536514A CN03153651A CN1585141A CN 1585141 A CN1585141 A CN 1585141A CN A031536514 A CNA031536514 A CN A031536514A CN 03153651 A CN03153651 A CN 03153651A CN 1585141 A CN1585141 A CN 1585141A
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- Prior art keywords
- fluorophor
- light
- blue
- phosphor
- white light
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Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 39
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- -1 chlorosilicate magnesium zinc calcium Chemical compound 0.000 claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 19
- 239000000391 magnesium silicate Substances 0.000 claims description 14
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 14
- 235000019792 magnesium silicate Nutrition 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- QGZNMXOKPQPNMY-UHFFFAOYSA-N [Mg].[Cl] Chemical class [Mg].[Cl] QGZNMXOKPQPNMY-UHFFFAOYSA-N 0.000 claims description 13
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004020 luminiscence type Methods 0.000 claims description 5
- 241001025261 Neoraja caerulea Species 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005022 packaging material Substances 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 238000009877 rendering Methods 0.000 description 13
- 238000000295 emission spectrum Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 229910052712 strontium Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 5
- HAYCESPFUISQPN-UHFFFAOYSA-N [Sr].[Cl] Chemical class [Sr].[Cl] HAYCESPFUISQPN-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229910052917 strontium silicate Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 4
- 239000004110 Zinc silicate Substances 0.000 description 4
- ICGLOTCMOYCOTB-UHFFFAOYSA-N [Cl].[Zn] Chemical compound [Cl].[Zn] ICGLOTCMOYCOTB-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- VYZCLCPZAJLOBI-UHFFFAOYSA-N calcium magnesium chloro(trioxido)silane Chemical class [Mg+2].[Ca+2].[O-][Si]([O-])([O-])Cl VYZCLCPZAJLOBI-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 235000019352 zinc silicate Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910017639 MgSi Inorganic materials 0.000 description 3
- BQEHTHYCGRTKNO-UHFFFAOYSA-N [O-]B([O-])O.P.[Sr+2] Chemical compound [O-]B([O-])O.P.[Sr+2] BQEHTHYCGRTKNO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000013464 silicone adhesive Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCMLJYVKYRRZQH-UHFFFAOYSA-N [Mn].[Ca].[Zn] Chemical compound [Mn].[Ca].[Zn] QCMLJYVKYRRZQH-UHFFFAOYSA-N 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- KPVUHKHVGKSEPB-UHFFFAOYSA-N calcium europium Chemical compound [Ca][Eu] KPVUHKHVGKSEPB-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- MQMHJMFHCMWGNS-UHFFFAOYSA-N phosphanylidynemanganese Chemical compound [Mn]#P MQMHJMFHCMWGNS-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a white light LED and its phosphor for light conversion, the LED comprises a light emitting chip, an electrode, a phosphor and a packaging material, wherein the phosphor comprises a chlorosilicate magnesium zinc calcium (CMZSC) co-activated by rare earth ions and manganese ions, and an alkaline earth silicate and a pyrosilicate phosphor co-activated by red light phosphor bivalent europium and bivalent manganese. Such phosphors may be combined with one or more phosphors that convert long wavelength UV radiation emitted by the semiconductor into blue and other visible light to form UV white LEDs and LDs. The CMZSC green phosphor may also be combined with one or more phosphors that convert blue light emitted by the semiconductor compound into yellow and red light, and with a blue semiconductor such as an InGaN chip into a white LED. Its advantages are wide spectrum coverage, high color-developing index and high light conversion efficiency.
Description
One, technical field:
The present invention relates to the conversion of a kind of white light emitting diode and light thereof and use fluorophor, belong to photoelectron and lighting technical field.
Two, background technology:
In later stage nineteen nineties, the appearance of white light emitting diode becomes a hot topic in photoelectron and the illumination section field.White light emitting diode (Light-Emitting Diode is called for short LED) is a kind of new solid light source, and wherein with semiconductor light emitting basket chip, long wave ultraviolet light chip and fluorophor organically combine the main flow that the white light LEDs of forming becomes current domestic and international development.A few years comes, and its development is very fast, and its light efficiency has now substantially exceeded incandescent lamp.White light LEDs has energy-efficient, the solidification antidetonation, start fast, flicker free, plurality of advantages such as nuisanceless is extended to many applications now.People expect that white light LEDs becomes new lighting source of the 4th generation, reaches energy-conservation green illumination purpose.Realize this new solid White-light LED illumination light source, press for the high-efficiency fluorescence body, long wave ultraviolet light and basket light that semiconductor LED and LD (Laser Diode, laser diode) chip is sent are converted to visible light effectively, thereby realize white light LEDs and white light LD.
Utilize the led chip of blue light-emitting and the rare-earth garnet that can be activated by the trivalent cerium of blue-light excited emission gold-tinted, as Y
3Al
5O
12: Ce, (Y, Gd)
3(Al, Ga)
5O
12: Ce fluorophor (abbreviating YAG:Ce usually as) can be formed the LED that emits white light (United States Patent (USP) 5998925), this yellow fluorophor people since the sixties in last century have carried out sufficient research (Blasse G and Bril A.J Chem Phys.1967,47 (12): 5139, Weber MJ etc.; Appl phys lett.1978,33:410, Liu Xingren etc.; Phys Rev B:Condens Matt.1989,39 (16): 10633), this class fluorophor can be converted to gold-tinted effectively with the blue light of semiconductor chip emission.But the performance of this white light LEDs reaches as illumination and is restricted the shortcoming that exists some urgent needs to overcome to a great extent.Because in the emission spectrum of employed YAG:Ce system fluorophor, lack some look composition, as blue green light and ruddiness composition.This not only causes the color reductibility of white light LEDs of manufacturing poor, and color rendering index is low, the more important thing is utilize this method be difficult to so far to produce low look show (≤4000K), the white light LEDs of high color rendering index (CRI) (Ra＞80).At present, this fluorophor improves very difficulty again with the efficient that blue light is converted to gold-tinted.Another shortcoming of this yellow YAG:Ce fluorophor is effectively to be excited to royal purple light by 360-420nm long wave ultraviolet, and luminous efficiency is low.
In recent years, the ultraviolet LED that has emission wavelength and be about 370nm, 382nm, 395nm and 405nm is developed successively, and royal purple light-emitting diode LED and the laser diode LD of emission 395 and 405nm have been realized commercialization.Utilize this UVLED and LED to realize white light, can reach the higher white light of light efficiency, but need the very high red, green, blue three-color phosphor of luminous efficiency.The Y that people are familiar with
2O
3: Bi, Eu fluorophor are used as the red material (United States Patent (USP) 6255670B1,2001) of long wave UV white light LEDs recently.It is to utilize Bi
3+Ion has absorption in long wave UV district, will absorb energy delivery then and give Eu
3+, make it to launch the sharp peak of 611nm spectral line ruddiness (J.Electrochen.Sol, 1967,114:1137, luminous journal 1981,2:31).But under the optical excitation, luminous efficiency is low outside the royal purple of 420-370nm scope for this red material, only at shorter ultraviolet light, excites down efficient very high as 254nm.The Y that colour TV is used
2O
2Also there is similar problem in the S:Eu red-emitting phosphors.
Liu's row Renhe is opened and has been invented the europkium-activated calcium magnesium chloro-silicate Ca of divalence dawn
8Mg (SiO
4)
4Cl
2: Eu (be called for short CMSC:Eu) green-emitting phosphor and reported it luminosity (J.Electrochem Soc, 1992,139:622).Subsequently, people such as Liu Hangren is again to Eu
2+The chlorine zinc silicate calcium Ca that activates
8Zn (SiO
4)
4Cl
2: Eu (being called for short CZSC:Eu) and Ce in these two kinds of new fluorophor
3+, Mn
2+Luminosity, Ce
3+-Eu
2+, Eu
2+-Mn
2+Interionic energy delivery has carried out studying (J.Rare Earth, 1993,11:102; Jilin University's natural science journal, 1996, No.4:91; Spectroscopy and spectrum analysis, 1998,18:645 etc.).Applied for Chinese invention patent (CN1186103A) in 1996.This class fluorophor is launched very strong green glow, the light energy use efficiency height at ultraviolet light and blue-light excited following.Recently, GE company utilizes the Eu of people's inventions such as Liu's row benevolence
2+And Mn
2+Coactivated calcium magnesium chloro-silicate is as the green-emitting phosphor (United States Patent (USP) 6255670B1,2001) of ultraviolet white light LEDs; And the green-emitting phosphor (United States Patent (USP) 6504179B1,2003) of the white light LEDs that German Osram company excites as blue chip.
The europkium-activated chlorine strontium silicate of divalence Sr
4Si
3O
3Cl
4Eu (British patent 1087655,1967; J.Lumin1971,3:467) and Sr
8(SiO
4O
12) Cl
8: Eu
2+(Z Anorg.Allg Chem.1994,620:451; Mat ResBull 2001, luminosity 36:2051) is in the news.And another kind of Eu
2+The phosphorus strontium borate 2SrO that activates, 0.84P
2O
5.0.16B
2O
3: Eu
2+Fluorophor is also by report (Mitsubishi Electric's skill newspaper, 1978,52,701).They launch strong blue green light under ultraviolet excitation, attempt to be used for the improvement of fluorescent lamp chromaticity matter, but be not used in the white light LEDs.
Eu
2+, Ce
3+The M of Ji Huoing respectively
3MgSi
2O
3The luminosity of (M=Ba, Sr, Ca) alkaline-earth silicate be in the news respectively (J.Electrochem Soc, 1970,117:381; J.Chem Phys.1968,115:1181; Journal of Inorganic Materials 1999,14 (2): 317; J Alloys Compd, 2000,23:189).Report in early days, at M
3MgSi
2O
8: Eu, Mn and BaMg
2Si
2O
7: effective Eu, can take place in two kinds of silicate of Mn in Eu
2+→ Mn
2+Energy delivery, and obtain Mn
2+Red emission (J.Electrochem Soc.1968,115:733; 1970,117:381), but do not obtain so far to use.
Three, summary of the invention:
It is wide to the purpose of this invention is to provide a kind of emission spectrum coverage, color rendering index height, light conversion efficiency height, the high quality white light LED that weatherability is good; Another object of the present invention provides the light conversion fluorophor of making this white light LEDs.
The objective of the invention is to realize by following mode:
White light LEDs of the present invention comprises luminescence chip, electrode, fluorophor, encapsulating material, it is characterized in that including in the fluorophor green-emitting phosphor that adopts rare earth ion europium, cerium and the coactivated chlorine magnesium silicate of manganese ion zinc calcium system, its compound consist of (Ca
1-x-yEu
xCe
y)
8(Mg
1-a-zZN
aMn
z) (SiO
4)
4Cl
2, the fluorophor of one at least in 0≤a in the formula≤1,0＜x≤0.2,0≤y≤0.1,0≤z≤0.1 and the two kind of silicate red-emitting phosphors, the composition of its compound is respectively:
(1) (Ba
1-x-bEu
xM
b) (Mg
1-aZn
aMn
z)
2Si
2O
7Mesosilicate, M=Sr and/or Ca in the formula, 0＜x≤0.15,0≤b≤1,0≤a≤1,0＜z≤0.3;
(2) (Ba
1-b-x-yMbEu
xCe
y)
3(Mg
1-a-zZn
aMn
z) Si
2O
8, M=Sr and/or Ca in the formula, 0≤b≤0.6,0≤a≤1,0＜x≤0.15,0≤y≤0.02,0≤z≤0.2.
White light LEDs light conversion of the present invention includes blue green light and the green-emitting phosphor that blue-ray LED, long wave UV LED and LD use with fluorophor, is that its compound consists of by the coactivated chlorine magnesium silicate of rare earth ion europium, cerium and manganese ion zinc calcium system fluorophor:
(Ca
1-x-yEu
xCe
y)
8(Mg
1-a-zZn
aMn
z) (SiO
4)
4Cl
2, 0≤a in the formula≤1,0＜x≤0.2,0≤y≤0.1,0≤z≤0.1 when containing trivalent cerium ion in forming, also should add the monoacidic base metal ion, as Li
+As the charge compensation agent.This class fluorophor can effectively be excited by the wavelength of the very wide ultraviolet light of spectral region to blue light, emission blue green light---green glow.For example, the 455nm's of usefulness InGaN LED emission is blue-light excited following, launches strong band blue green light or green glow.Therefore, they are to make white light LEDs or needed good blue green light of LD and green-emitting phosphor.
White light LEDs light of the present invention conversion also includes at least a in two kinds of silicate red-emitting phosphors of long wave UV and blue purple LED or LD light conversion usefulness with fluorophor, its compound is formed and is respectively:
(1) (Ba
1-x-bEu
xM
b) (Mg
1-aZn
aMn
z)
2Si
2O
7Mesosilicate, M=Sr and/or Ca in the formula, 0＜x≤0.15,0≤b≤1,0≤a≤1,0＜z≤0.3;
(2) (Ba
1-b-x-yMbEu
xCe
y)
3(Mg
1-a-zZn
aMn
z) Si
2O
3, M=Sr and/or Ca in the formula, 0≤b≤0.6,0≤a≤1,0＜x≤0.15,0≤y≤0.02,0≤z≤0.2.In forming, contain Ce
3+During ion, can add alkali metal ion, as Li
+Do the charge compensation agent.
In above-mentioned two kinds of silicate, Eu
2+Part replaces alkaline-earth metal M
2+And Mn
2+Part replaces Mg
2+Ion occupies octahedra case, in the long wave ultraviolet of semiconducting compound led chip emission---under the exciting of royal purple light, Eu
2+Absorb energy effectively, pass to Mn
2+Thereby, produce ruddiness, therefore, can be used as the red composition of UV white light LEDs.
In changing with fluorophor, white light LEDs light of the present invention can also include three kinds of efficient emission blue green light fluorophor that relate to long wave UV and blue purple LED and LD light conversion usefulness: (Sr
1-xEu
x)
4Si
3O
8Cl
4(being called for short SSC4:Eu), (Sr
1-xEu
x)
8(Si
4O
12) Cl
3(being called for short SSC8:Eu) and 2 (Sr
1-xEu
x) 0.84P
2O
50.16B
2O
3(being called for short SPB:Eu).They can effectively be excited by the InGaN LED of UV light and royal purple light, the emission blue green light, and the emission peak of preceding two kinds of chlorine strontium silicates is positioned at the 490nm place, and the emission peak of SPB:Eu is 480nm.The luminous Eu that all belongs to of these fluorophor
2+The transition emission of 5d → 4f configuration.Eu
2+Can absorb the UV-royal purple light that led chip sends under the direct current forward current drives effectively, the electron transition that is energized into the 5d attitude is launched visible blue green light to 4f ground state, realizes the conversion of UV → visible light.They are used as the blue green light composition of UV white light LEDs, improve the color rendering of white light LEDs and improve color rendering index.
Divalent europium of the present invention, bivalent manganese, trivalent europium-doped chlorine magnesium silicate zinc calcium is bluish-green-and the preparation method of green-emitting phosphor is as described below.Press constitutional chemistry metering ratio, accurately take by weighing corresponding high-purity oxidation cooperation and the calcium chloride of containing of calcium, magnesium, zinc, manganese, rare earth element and silicon and alkali metal as raw material, as CaCO
3, MgO, ZnO, MnCO
3, Eu
2O
3, CeO
2And Li
2CO
3And CaCl
2Excessive CaCl
2Be necessary.Above-mentioned raw materials fully grind be mixed even after, be placed in the corundum crucible, in the weakly reducing atmosphere under 1000-1200 ℃, calcination 1-4 hour, can make needed fluorophor.Its body colour is green, deepens with europium concentration.The gas that reducing atmosphere can use carbon granules to burn in air and produce also can adopt N
2Gas and small amount of H
2, as 95%N
2+ 5%H
2Mist.
Divalent europium of the present invention, the preparation method of the coactivated alkaline-earth silicate fluorophor of trivalent cerium and bivalent manganese is described below.According to forming (Ba
1-b-x-yMbEu
xCe
y) (Mg
1-a-zZn
aMn
z) SiO
2O
8Stoichiometric accurately takes by weighing relevant oxysalt raw material, alkaline earth metal carbonate, SiO
2, MgO or Mg (OH)
24MgCO
35H
2O, Eu
2O
3, CeO
2And the salt of manganese, as MnO
2, MnCO
3, MnF
2If use CeO
2, need add the small amount of alkali metal, as Li
+Salt is done the charge compensation agent.Be mixed their mills even, put into corundum crucible, in 1000-1300 ℃ of weakly reducing atmosphere calcination 1-5 hour.M is Sr, and Ca can partly replace Ba, and the emission spectrum that their effect can be regulated fluorophor moves.
The coactivated alkaline earth mesosilicate of divalent europium of the present invention and bivalent manganese phosphor preparation method is described as follows, by (Ba
1-x-bEu
xM
b) (Mg
1-a-zZn
aMn
z)
2Si
2O
7Constitutional chemistry metering ratio takes by weighing BaCO
3, SrCO
3, CaCO
3, MgO, ZnO, SiO
2, Eu
2O
3, MnCO
3, or other manganese salt.Add a small amount of flux, as MgCl
2, BaF
2Deng after, fully mill be mixed even after, put into high-purity Al
2O
3In the crucible, in 1000-1300 ℃ weakly reducing atmosphere calcination 1-5 hour.Take out and use the hot deionized water washed product, in 130 ℃ of baking ovens, dry.Producing the week reduction gas methods can be that carbon grain combustion produces also available N
2Gas and small amount of H
2The gas that gas mixes.
The preparation method of the europkium-activated chlorine strontium silicate of divalence of the present invention blue-green fluorophor as described below.By (Sr1-xEu
x)
4Si
3O
8Cl
4(Sr
1-xEu
x)
3(Si
4O
12) Cl
8Constitutional chemistry metering ratio takes by weighing SrCO
3, SiO
2, SrCl
2And Eu
2O
3, and manganese salt, as MnCO
3, MnO
2Or MnF
2Deng raw material, fully mill is mixed evenly, puts into corundum crucible, gives heat 3 hours at about 850 ℃, and taking-up is regrinded, calcination several hours in 900-950 ℃ of weakly reducing atmosphere then, and weakly reducing atmosphere can be 5%H
2+ 95%N
2About the also available carbon granules of mist at high temperature burn and produce weak reducing gas.Product grinds slightly, uses the superfluous thing of hot deionized water flush away, dries to get final product in 130 ℃ of baking ovens.
The europkium-activated phosphorus strontium borate of divalence of the present invention blue-green phosphor preparation method is described below, by the salt that contains strontium, as SrHPO
4, SrCO
3, H
3BO
3, (NH
4)
2HPO
4, Eu2O
3And MnCO
3Or other manganese salt is as raw material.By consisting of 2SrO0.84P
2O
50.16B
2O
3: the xEu stoichiometric, accurately take by weighing corresponding raw material, fully mill is mixed evenly, puts into beautiful crucible, calcination a few hours in 1050-1250 ℃ of weakly reducing atmosphere.The concentration of europium is generally 1-3mol/%.Use hot wash, 130 ℃ of oven dry down produce weak reducing gas method as mentioned above.
Advantage of the present invention is concerning chlorine magnesium silicate zinc calcium fluorophor, owing to according to radiationless energy delivery principle, make Eu
2+And Mn
2+Luminous enhancing, the topped scope of emission spectrum is wideer, favourable chromaticity is given birth to the x that sits and the raising of improvement of y value and color rendering index Ra.Eu of the present invention
2+, Ce
3++ Eu
2+, Ce
3++ Eu
2++ Mn
2+, Eu
2++ Mn
2+Chlorine magnesium silicate zinc calcium (CMZSC) that multiple activator mixes and chlorine zinc silicate calcium (CZSC) green-emitting phosphor are not only to long wave ultraviolet light, royal purple light and blue light conversion efficiency height, launch strong green glow, and in the emission spectrum greater than increasing in shared ratio calcium magnesium chloro-silicate (CMSC) system of the orange red composition of 580nm.Therefore, these advantages of green-emitting phosphor of the present invention not only make the light conversion efficiency of the ultraviolet of launching among the LED and blue light improve, and the color rendering index of favourable white light LEDs improves.They and the semiconducting compound of launching long wave ultraviolet light or blue light, (Ca, Sr) combination of S:Eu fluorophor can be made into the white light LEDs of logical high, the different-colour that color rendering index is satisfied of light as the InGaN chip of ultraviolet and blue light and other fluorophor such as YAG:Ce system yellow fluorescence and alkaline earth sulfide.
Another advantage of the present invention is to utilize Eu
2+-Mn
2+The radiationless energy delivery alkaline-earth silicate M that obtains to glow (Mg, Zn)
2Si
2O
7: Eu
2+, Mn
2+And M
3(Mg, Zn) Si
5O
8: Eu
2+-Mn
2+(Ca), they are used as the in demand red composition of UV white light LEDs for M=Ba, Sr, and this class silicate phosphor can effectively be excited by the long wave UV-royal purple light that LED launches, and the emission spectrum scope is at the ruddiness of 560-760nm scope.Utilize part Sr
2+And Ca
2+Replace Ba
2+, Zn
2+Replace magnesium and can regulate Mn
2+Red emission wavelength and spectrum.This class silicate preparation is simple, stable performance, and weatherability is good, and the temperature quenching characteristic is good.Therefore, red-emitting phosphors of the present invention is suitable for use as the red composition of ultraviolet white light LEDs, select for use the green and blue emitting phophor of red-emitting phosphors of the present invention and other to mix by a certain percentage, again with launch long wave ultraviolet light such as 380nm or 395nmInGaN led chip organic assembling and can make high-quality white light LEDs.
Another advantage of the present invention is europkium-activated chlorine strontium silicate of divalence and phosphorus strontium borate fluorophor, excites down at long wave ultraviolet-blue-ray LED, can launch strong blue green light (480-500nm).Therefore, can be used for the bluish-green composition of white light LEDs high-color rendering and other fluorophor in conjunction with making the good white light LEDs of color rendering.
Advantage of the present invention also shows by transmitted wave ultraviolet light-blue-light semiconductor luminescence chip and three-color phosphor and is combined into the white light LEDs that colour temperature can be random.Utilize several fluorophor of the present invention and BaMg
2Al
16O
27: Eu, BaMgAl
10O
17: Eu or (Ba, Sr, Ca, Mg)
5(PO
4)
3: Eu blue emitting phophor combination, also can with 3.5MgO0.5MgF
2GeO
2: Mn
4+Red combination of materials is made the UV white light LEDs of different-colour.
Another advantage of the present invention is that high quality white light LED is by blue light-emitting InGaN semiconductor chip and chlorine magnesium silicate zinc calcium system fluorophor of the present invention and Ce
3+The rare-earth garnet such as the YAG:Ce that activate, YAG:Ce, Pr yellow fluorophor and/or other red-emitting phosphors are as (Ca, Sr) S:Eu organically forms.The InGaN led chip drives down as If=20mA at forward current, and the blue light about emission 450nm excites chlorine magnesium silicate zinc calcium fluorophor of the present invention and other yellow or/and red-emitting phosphors.Bluish-green-the green glow of chlorine magnesium silicate zinc calcium fluorophor emission is filled up the spectrum that lacks the 480-510nm wave band in the emission spectrum of white light LEDs, and the color rendering index Ra of white light LEDs is improved.
Four, description of drawings:
Fig. 1 is the structural representation of a kind of plane white light LEDs;
Fig. 2 is the structural representation of the luminescence unit of semiconductor light emitting chip and the combination of fluorescent material glue-line,
Fig. 3 is the europkium-activated chlorine magnesium silicate of divalence of the present invention zinc calcium Ca
sZn (SiO
4)
4Cl:Eu
2+Excitation spectrum of green-emitting phosphor (a) and emission spectrum (b), curve 1: λ
Ex=395nm, curve 2: λ
Ex=460nm;
Fig. 4 is (Ba
0.96Eu
0.04) (Mg
1.8Mn
0.2) Si
2O
7(a) excitation spectrum of mesosilicate red-emitting phosphors, curve 1: λ
Ex=655nm, 2:400nm reaches (b) emission spectrum λ
Ex=380nm.
Fig. 5 is (Sr
0.92Eu
0.02)
4Si
3O
8(a) excitation spectrum λ of Cl chlorine strontium silicate blue green light fluorophor
Ex=490nm and (b) emission spectrum λ
Ex=380nm.
Five, embodiment:
With reference to accompanying drawing 1, white light LEDs of the present invention comprises semiconductor light emitting chip 1, electrode 2, fluorophor 4, encapsulating material 5, lead-in wire 6, electrode pin 7,8, opaque support 9, fluorophor 4 includes the green-emitting phosphor that adopts rare earth ion europium, cerium and the coactivated chlorine magnesium silicate of manganese ion zinc calcium system, its compound consist of (Ca
1-x-yEu
xCe
y)
8(Mg
1-a-zZn
aMn
z) (SiO
4)
4Cl
2, the fluorophor of one at least in 0≤a in the formula≤1,0＜x≤0.2,0≤y≤0.1,0≤z≤0.1 and the two kind of silicate red-emitting phosphors, the composition of its compound is respectively:
(1) (Ba
1-x-bEu
xM
b) (Mg
1-aZn
aMn
x)
2Si
2O
7Mesosilicate, M=Sr and/or Ca in the formula, 0＜x≤0.15,0≤b≤1,0≤a≤1,0＜z≤0.3;
(2) (Ba
1-b-x-yMbEu
xCe
y)
3(Mg
1-a-xZn
aMn
x) Si
2O
3, M=Sr and/or Ca in the formula, 0≤b≤0.6,0≤a≤1,0＜x≤0.15,0≤y≤0.02,0≤z≤0.2.
Encapsulating material 5 can be the resin of anti-UV and weatherability, as transparent epoxy resin, and transparent silicone adhesive etc., also available SiO
2Or TiO
2As the scattering of light agent, make the white light of LED photochromic more even.Fluorophor among the present invention and mixed with resin are coated in around the semiconductor light emitting chip; Or fluorophor is evenly dispersed in the encapsulating material, and major part is suspended in the encapsulating material, do not contact with the semiconductor light emitting chip, also can apply the skim diaphragm earlier around semiconductor chip, and then be coated with phosphor gel.Potting resin not only plays protection chip anchor leg, support makes it to become a mass action, plays the optically focused prismatic action again.White light LEDs can be packaged into different structures such as hemisphere, bullet shaped and planar shaped.
The present invention is further described by the following embodiment:
Embodiment 1: take by weighing CaCO
310.50g, ZnO 1.2g, SiO
23.61g, CaCl
25.00g it is even that mill is mixed, and puts into corundum crucible, takes out after 3 hours at 1150 ℃ of constant temperature and be cooled to beautiful room temperature, obtains white host material.Take by weighing Eu then
2O
30.079g, Li
2CO
30.52g and above-mentioned host material mixer mill is equal, puts into crucible again, calcination is 3 hours in the weakly reducing atmosphere that 1000 ℃ of carbon grain combustions produce.Take out, with deionized water wash, sieve, dry, obtain the Ca that body colour is a green
8Zn (SiO
4)
4Ce:0.1Eu fluorophor (CZSC:Eu).By this CZSC:Eu green-emitting phosphor, second kind (Y, Gd)
3Al
5O
12: the Ce yellow fluorophor, selecting emission wavelength for use is that the InGaN of 455nm is the chip of LED, makes luminescence unit by technology shown in Figure 2.Behind the semiconductor light emitting chip 1 solid crystalline substance, carefully apply skim transparent protective resin layer 3 in the above and on every side, cover on chip 1 top electrodes 2.After the layer to be protected adhesive curing, will contain the transparent resin adhesive 5 of two kinds of fluorophor 4 of 3: 7 weight ratios, carefully be coated in above the protective layer 3 with on every side; After treating that phosphor gel is solidified, be packaged into the white light LEDs of difformity and specification at last with transparent epoxy resin.In case of necessity, in encapsulating material, add very small amount of scattered agent SiO
2Or TiO
2, so that white light is photochromic more even.Under forward current If=20mA DC power supply (general forward voltage is about 3 volts), measure the photoelectric property of white light LEDs, the emission spectrum of this white light LEDs is the blue spectrum by the emission of InGaN chip, and the spectrum of the rare-earth garnet yellow fluorophor emission that the europkium-activated chlorine zinc silicate of divalence calcium green-emitting phosphor and trivalent cerium activate is formed.The colour temperature 6400K of this white light LEDs, chromaticity coordinate x=0.31, y=0.33, color rendering index Ra=85, if without chlorine zinc silicate calcium europium fluorophor, Ra has only 80, and light intensity is also low slightly.
Embodiment 2: press embodiment 1 selected semiconductor blue chip and fluorophor, make the plane white light LEDs by packaging technology shown in Figure 1.The solid crystalline substance of chip 1 on the negative electricity plate 7, is gone up positive electrode 2 and electrode 8 ultra-sonic welded by lead-in wire 6 with the chip top below, and element is fixing by opaque support 9, fills with fluorescent material 4 and resin glue 5 then in groove, promptly can be made into the plane white light LEDs.
Embodiment 3: take by weighing BaCO
315.00g, Eu
2O
30.557g, Mg (OH)
2, 4MgCO
3, 5H
2O 13.90g, MnO
21.376g, SiO
29.60g, NH
4It is even that Cl 1.00g mill is mixed, and puts into corundum crucible, calcination 3 hours in the weak reducing atmosphere that 1200 ℃ of carbon grain combustions produce, and product washes, sieve, dry and obtain (Ba0.96Eu
0.04) (Mg
1.8Mn
0.2) Si
2O
7Red-emitting phosphors and the divalent europium and the coactivated chlorine magnesium silicate of the bivalent manganese zinc calcium CMZSC:Eu that produce by embodiment 1 method, Mn green-emitting phosphor and BaMgAl
10O
17: the Eu blue emitting phophor mixes than 0.40: 0.55: 0.05 by relative weight.Silicone adhesive with ultraviolet resistance is made into arogel then, and carefully being coated in emission wavelength is on the InGaN royal purple optical chip of 395nm, treat that arogel solidifies after, the transparent epoxy resin with ultraviolet resistance is packaged into common 5 white light LEDs at last.
Embodiment 4: select for use the material mixture ratio of embodiment 3 and chip and fluorophor to mix with the silicone or the epoxy resin of ultraviolet resistance.Become the plane white light LEDs by embodiment 2 methods, reach and implement 3 effect same.
Implement 5: select calcium magnesium chloro-silicate system CMSC:Eu for use, Ce, Mn, chlorine strontium silicate Sr
4Si
3O
8Cl
4: Eu, and magnesium silicate strontium barium (Ba, Sr)
3MgSi
2O
8: Eu, Mn and BaMg
2Al
16O
27: Eu is respectively green, blue-green, redness and blue emitting phophor, by relative weight than 0.33: 0.06: 0.35: 0.26 silicone adhesive that mixes back and ultraviolet resistance is made into uniform arogel, carefully is coated in emission wavelength and is on the semiconductor chip of ultraviolet light of 382nm.After treating that arogel solidifies, the transparent epoxy resin with ultraviolet light is packaged into common 5 hemisphere white light LEDs at last.Under forward current If=2OmA drove, acquisition correlated colour temperature was 6400K, the white light LEDs of color rendering index Ra=85.
Claims (3)
1, a kind of white light emitting diode comprises luminescence chip, electrode, fluorophor, encapsulating material, it is characterized in that in the fluorophor: include the green-emitting phosphor that adopts rare earth ion europium, cerium and the coactivated chlorine magnesium silicate of manganese ion zinc calcium system, its compound consist of (Ca
1-x-yEu
xCe
y)
8(Mg
1-a-zZn
aMn
z) (SiO
4)
4Cl
2, the fluorophor of one at least in 0≤a in the formula≤1,0＜x≤0.2,0≤y≤0.1,0≤z≤0.1 and the two kind of silicate red-emitting phosphors, the composition of its compound is respectively:
(1) (Ba
1-x-bEu
xM
b) (Mg
1-aZn
aMn
z)
2Si
2O
7Mesosilicate, M=Sr and/or Ca in the formula, 0＜x≤0.15,0≤b≤1,0≤a≤1,0＜z≤0.3;
(2) (Ba
1-b-x-yMbEu
xCe
y)
3(Mg
1-a-zZn
aMn
z) Si
2O
8, M=Sr and/or Ca in the formula, 0≤b≤0.6,0≤a≤1,0＜x≤0.15,0≤y≤0.02,0≤z≤0.2.
2, fluorophor is used in a kind of white light LEDs light conversion, it is characterized in that:
Fluorophor includes blue green light and the green-emitting phosphor that blue-ray LED, long wave UV LED and LD use, and is that its compound consists of by the coactivated chlorine magnesium silicate of rare earth ion europium, cerium and manganese ion zinc calcium system fluorophor:
(Ca
1-x-yEu
xCe
y)
8(Mg
1-a-zZn
aMn
z) (SiO
4)
4Cl
2, 0≤a in the formula≤1,0＜x≤0.2,0≤y≤0.1,0≤z≤0.1 when containing trivalent cerium ion in forming, also should add the monoacidic base metal ion;
White light LEDs light of the present invention conversion also includes at least a in two kinds of silicate red-emitting phosphors of long wave UV and blue purple LED or LD light conversion usefulness with fluorophor, its compound is formed and is respectively:
(1) (Ba
1-x-bEu
xM
b) (Mg
1-aZn
aMn
z)
2Si
2O
7Mesosilicate, M=Sr and/or Ca in the formula, 0＜x≤0.15,0≤b≤1,0≤a≤1,0＜z≤0.3;
(2) (Ba
1-b-x-yMbEu
xCe
y)
3(Mg
1-a-zZn
aMn
z) Si
2O
8, M=Sr and/or Ca in the formula, 0≤b≤0.6,0≤a≤1,0＜x≤0.15,0≤y≤0.02,0≤z≤0.2.In forming, contain Ce
3+During ion, can add alkali metal ion, as Li
+Do the charge compensation agent.
3, white light LEDs light conversion according to claim 2 is with including three kinds of efficient emission blue green light fluorophor that relate to long wave UV and blue purple LED and LD light conversion usefulness in the fluorophor: (Sr
1-xEu
x)
4Si
3O
8Cl
4, (Sr
1-xEu
x)
8(Si
4O
12) Cl
8And 2 (Sr
1-xEu
x) 0.84P
2O
50.16B
2O
3
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| CNB031536514A CN100383988C (en) | 2003-08-20 | 2003-08-20 | White light emitting diode and phosphor for light conversion thereof |
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| CNB031536514A CN100383988C (en) | 2003-08-20 | 2003-08-20 | White light emitting diode and phosphor for light conversion thereof |
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| CN1186103A (en) * | 1996-12-26 | 1998-07-01 | 中国科学院长春物理研究所 | Green fluorescent powder and preparation thereof |
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