CN103074062B - 荧光体及其发光装置 - Google Patents
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000004020 luminiscence type Methods 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical group [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 16
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 13
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052733 gallium Inorganic materials 0.000 abstract description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052738 indium Inorganic materials 0.000 abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 12
- 230000009466 transformation Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
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- 238000002156 mixing Methods 0.000 description 7
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- 239000004411 aluminium Substances 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910016569 AlF 3 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- -1 YF 3 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
- H01L2224/85909—Post-treatment of the connector or wire bonding area
- H01L2224/8592—Applying permanent coating, e.g. protective coating
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Abstract
一种荧光体及其发光装置。所述荧光体的通式为((LumA1-m)zCe1-z)3Q5O12,0<m<1,0<z<1,A包含钇(Y)元素、镧(La)元素、钆(Gd)元素中一种或几种,Q包含铝(Al)元素、镓(Ga)元素、铟(In)元素中的一种或几种,1.74≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤1.35。
Description
技术领域
本发明涉及荧光体,特别是使用荧光体的发光装置。
背景技术
近年,使用半导体发光的发光装置被广泛地使用,特别是发光二极管已被成功开发,此发光装置较已知的冷阴极灯管、白炽灯等发光设备,具有高发光效率、体积小、低耗电力与低成本等优点,因此可作为各种光源来使用。而半导体发光装置包含半导体发光组件与荧光体,荧光体可吸收并转换半导体发光组件所发出的光,藉由半导体发光组件所发出的光与荧光体转换发出的光两者混合使用。此种发光装置可作为荧光灯、车辆照明、显示器、液晶背光显示等各种领域使用。
现行的白光二极管发光装置,主要藉由补色原理进行开发。由半导体发光组件发出蓝光,往荧光体入射后,荧光体吸收并转换为黄光发出,蓝光与黄光混合同时进入人眼时,人则感受为白光。例如若使用InGaN为发蓝光的半导体,黄色荧光体为(Y,Gd)3(Al,Ga)5O12:Ce,则可达到上述效果。
又,亦可利用发出紫外线的发光组件与可发出RGB(红色、绿色、蓝色)光的荧光体组合,放出白色光。再者,亦有使用放出紫外线的发光组件,使发出蓝色光的荧光体发光,藉由该蓝色光使发出黄色光的荧光体激发,发出荧光,而混合发出白色等光。
然而,由于目前使用的发光装置领域越来越广泛,且市售的黄色荧光体(Y,Gd)3(Al,Ga)5O12:Ce系列,其发光辉度明显不足,无法满足业界需求,且在提升发光辉度的同时,易造成发光色度发生偏移现象。因此如何能满足应用于各种发光装置并同时达到辉度提升的荧光体,已成现行荧光体技术开发重点之一。
发明内容
本发明涉及荧光体与发光装置,具有优异的发光特性。
一种荧光体,所述荧光体的通式为((LumA1-m)zCe1-z)3Q5O12,其中0<m<1,0<z<1,A包含钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种,Q包含铝(Al)元素、镓(Ga)元素、铟(In)元素中的一种或几种,Lu为镏元素,O为氧元素,Ce为铈元素,1.74≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤1.35。
进一步地,0.1≤(1-m)*z*3≤1.27。
所述荧光体的通式中A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种。
在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.349<x<0.444,0.538<y<0.584。
所述荧光体的通式中A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种,2.5≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤0.21。
在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.370<x<0.400,0.570<y<0.580。
所述荧光体的通式中A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种,2.3≤(m*z+1-z)*3≤2.49,0.22≤(1-m)*z*3≤0.70。
在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.400<x<0.418,0.560<y<0.570。
所述荧光体的通式中A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种,1.70≤(m*z+1-z)*3≤2.29,0.8≤(1-m)*z*3≤1.35。
在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.418<x<0.426,0.545<y<0.560。
所述荧光体的通式中,
A的通式为LanGdgY1-n-g,0≤n<1,0≤g<1,
Q的通式为AlrGajIn1-r-j,0<r≤1,0≤j<1,
n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1,(1-z)*3=0.095~0.135,j*5=0~0.3。
一种荧光体,通式为((LumA1-m)zCe1-z)3Q5O12,其中0<m<1,0<z<1,A包含钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种,Q包含铝(Al)元素、镓(Ga)元素、铟(In)元素中的一种或几种,Lu为镏元素,O为氧元素,Ce为铈元素,0.7≤(m*z+1-z)*3≤0.8,2.2≤(1-m)*(z)*3≤2.35。
其中,A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种。
在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.450<x<0.486,0.504<y<0.545。
其中,0.504<y<0.532。
所述荧光体,A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种,0.7≤(m*z+1-z)*3≤0.77,2.20≤(1-m)*z*3≤2.30。
在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.451<x<0.480,0.525<y<0.545。
所述荧光体的通式中,
A的通式为LanGdgY1-n-g,0≤n<1,0≤g<1,
Q的通式为AlrGajIn1-r-j,0<r≤1,0≤j<1,
n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1,(1-z)*3=0.095~0.135,j*5=0~0.3。
一种发光装置,包括:一发光组件;以及一如上述任一所述的荧光体,所述荧光体在受到所述发光组件所发出的激发光的激发后,发出异于该激发光波长的光。
附图说明
图1是为一实施例中发光装置的剖面图;
图2是荧光体光特性的测量装置。
符号说明
11箱体;12样品槽;13光源;14光导引管;
15反射镜;16辉度计;21发光单元;22荧光层;
23封装层;211基座;212凹形承载面;213发光组件;
214连接线;215导线;221荧光体。
具体实施方式
下文特举较佳实施例,并配合附图,作详细说明如下:
本发明的实施例关于一种荧光体,其通式表示为((LumA1-m)zCe1-z)3Q5O12,其中符号「Lu」表示镏元素,符号「Ce」表示铈元素,符号「O」表示氧元素。A包含钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种。Q包含铝(Al)元素、镓(Ga)元素、铟(In)元素中的一种或几种。
在通式中,Lu摩尔数:A摩尔数:Ce摩尔数:Q摩尔数:O摩尔数可表示为m*z*3:(1-m)*z*3:(1-z)*3:5:12,其中符号「*」表示数学上的乘号,「-」表示数学上的减号。换句话说,在荧光体中,当O为12摩尔份时,Lu为m*z*3摩尔份,A为(1-m)*z*3摩尔份,Ce为(1-z)*3摩尔份,Q为5摩尔份。
0<m<1,0<z<1。
于一实施例中,在荧光体中,当O为12摩尔份时,Ce为0.095~0.135摩尔份,亦即,(1-z)*3=0.095~0.135。
于一实施例中,A是钇(Y)元素、镧(La)元素、钆(Gd)元素中的一种或几种。举例来说,A的通式可表示为LanGdgY1-n-g,0≤n<1,0≤g<1。换句话说,在荧光体中,当O为12摩尔份时,La为n*(1-m)*z*3摩尔份,Gd为g*(1-m)*z*3摩尔份,Y为(1-n-g)*(1-m)*z*3摩尔份。于一实施例中,n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1。
于一实施例中,Q是铝(Al)元素、镓(Ga)元素、铟(In)元素中的一种或几种。举例来说,Q的通式可表示为AlrGajIn1-r-j,0<r≤1,0≤j<1。换句话说,在荧光体中,当O为12摩尔份时,Al为r*5摩尔份,Ga为j*5摩尔份,In为(1-r-j)*5摩尔份。于一实施例中,j*5=0~0.3。
于一实施例中,1.74≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤1.35(亦即,在荧光体中,当O为12摩尔份时,Lu摩尔份与Ce摩尔份的总和为1.74至3.0,A的摩尔份为0.1~1.35)。或者,0.1≤(1-m)*z*3≤1.27。在此例中,以波长为455nm的光照射激发下,荧光体发出光的CIE1931色坐标为0.349<x<0.444,0.538<y<0.584。
例如,当荧光体符合2.5≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤0.21时,在以波长为455nm的光照射激发下,荧光体发出光的CIE1931色坐标为0.370<x<0.400,0.570<y<0.580。
例如,当荧光体符合2.3≤(m*z+1-z)*3≤2.49,0.22≤(1-m)*z*3≤0.70时,在以波长为455nm的光照射激发下,荧光体发出光的CIE1931色坐标为0.400<x<0.418,0.560<y<0.570。
例如,当荧光体符合1.70≤(m*z+1-z)*3≤2.29,0.8≤(1-m)*z*3≤1.35时,在以波长为455nm的光照射激发下,荧光体发出光的CIE1931色坐标为0.418<x<0.426,0.545<y<0.560。
于另一实施例中,荧光体符合0.7≤(m*z+1-z)*3≤0.8,2.2≤(1-m)*(z)*3≤2.35。在此例中,在以波长为455nm的光照射激发下,荧光体发出光的CIE1931色坐标为0.450<x<0.486,0.504<y<0.545。或者,0.504<y<0.532。
例如,当荧光体符合0.7≤(m*z+1-z)*3≤0.77,2.20≤(1-m)*z*3≤2.30时,在以波长为455nm的光照射激发下,荧光体发出光的CIE1931色坐标为0.451<x<0.480,0.525<y<0.545。
实施例中,荧光体系为粉体。
实施例的荧光体可藉由多种方式实施完成,例如较佳可组合下述数种方式实施:藉由坩埚内壁上形成保护层、荧光体烧结条件、烧结次数、多次水洗等多种方式实施。
坩埚可为氧化铝、氮化硼或石墨等材质,种类并无限制。坩埚内壁上的保护层,可使用各种原料于高温下烧结形成。例如,可使用欲烧结的荧光体原料成份之一或其混合物做为保护层原料烧结而得。保护层的烧结条件可为850~1800℃、0.5~10h,温度太低或时间太短时不易形成有效保护层,时间太长或温度太高则不符合经济效益。此一保护层可避免坩埚中硅、钙等杂质于高温下析出进入荧光体,因而影响荧光体性质。
另外于烧结气氛中,多次烧结能使荧光体原料进入晶格中,将不纯物析出,因而达到有效控制荧光体中杂质含量,提高荧光体的发光性质与安定性。藉由多次水洗,则易于将表面附着的不纯物洗去,因而避免影响荧光体的发光性质。
荧光体原料来源可为金属氧化物、金属化合物或可利用加热形成氧化物者,并不局限单一来源。例如以钇元素为例,可为氧化钇、氢化钇、碳酸钇、氢氧化钇、氧化铝钇、钇化铝等。原料的混合方式,可为干式法、湿式法。例如干式球磨法或加入溶剂的湿式球磨法等多种实施方式,并不局限于单一方式。
在此,亦可因应需要在原料中添加助熔剂,助熔剂可为卤化物,例如:NaF、KF、BaF3、SrF2、MgF2、AlF3、YF3、NaCl、BaCl2等。于实施例中,以荧光体为100重量份为基准,助熔剂为0.01~5重量份。
制备荧光体时可依一定比例秤量、混合各原料,置入具保护层的坩埚中,一起置入高温炉中烧结。烧结气氛为非氧化性气体,例如,可为氮、氢、氨、氩等或前述气体的任意组合。荧光体的烧结温度为1000℃以上1800℃以下,更佳为1200℃以上1600℃以下,升温速度为5~15℃/min。于此温度范围内烧结,较低温下烧结可得较细微荧光体,较高温下烧结可得粒径较大荧光体。烧结时间根据原料种类不同而有所差异,一般反应时间为0.5~5小时较佳。
烧结完成后,冷却至室温,可使用球磨或工业用粉碎机械等方式粉碎,之后经过水洗、过滤、干燥、分级等步骤,即可得到本发明的荧光体。荧光体D50粒径较佳为0.5μm~30μm,更佳为2μm至20μm。D50粒径在此范围内的荧光体易于涂布和填充使用,因而能提升发光效率。若荧光体粒径过小将影响发光辉度,粒径过大则有容易沉降、不易使用等问题。且本发明的荧光体可吸收光波长范围较佳介于200nm至550nm之间。而且该荧光体转换后所发出之光的主波长较佳介于500nm至600nm之间。
实施例的荧光体可应用在各种发光装置中,包含荧光显示管(VFD)、场发射显示器(FED)、电浆显示器(PDP)、阴极射线管(CRT)、发光二极管(LED)等。
于一实施例中,发光装置包括发光组件与一如上所述荧光体,其中荧光体在受到发光组件所发出的激发光的激发后,发出异于激发光波长的光。
发光组件可为半导体发光组件,例如包括硫化锌或氮化镓等各种半导体,而以发光效率而言,使用氮化镓半导体较佳。发光组件藉由有机金属化学气相沉积法(MOCVD)或氢化物气相磊晶法(HVPE)等方法于基板上形成氮化物半导体,InαAlβGa1-α-βN(0≤α、0≤β、α+β<1)所形成的发光组件最佳,半导体构造可为MIS接合、PIN接合、PN接合等均质构造、异质接面构造或双异质接面构造。可藉由半导体层的材料或其混晶度来选择各种的发光波长。较佳地,该发光装置中发光组件可发出300nm~550nm波长的光。更佳地,发出330nm~500nm波长的光。实施例的荧光体可与透光性材质混合形成波长转换材料。透光性材质可为环氧树脂、硅利康树脂(siliconeresin)、玻璃、热塑性塑料等各种可透光材质。波长转换材料可为至少含有一种荧光体所形成的单层波长转换材料或以积层方式配置的复数层波长转换材料。波长转换材料设置于发光半导体组件的发光路径上,例如:将波长转换材料直接涂布于发光组件表面上、将波长转换材料模制成型覆盖发光组件做为封止材料、将波长转换材料形成于封止材料表面、将波长转换材料形成于光学板或光学膜上并配置于LED灯的投光侧前方。
图1是一实施例中发光装置的剖面图。发光装置包含一发光单元21、一荧光层22及一封装层23。
其中,该发光单元21包括一可导电且具有一凹型承载面212的基座211、一设置于该凹型承载面212且与该基座211电连接的发光组件213、一与该发光组件213电连接的连接线214、一与连接线214电连接的导线215;其中,该基座211与该导线215可配合自外界提供电能至该发光组件213,该发光组件213可将电能转换成光能向外发出。本实施例是将一市售发光波长455nm,InGaN的发光组件213(制造商:奇力光电)以导电银胶(型号:BQ6886,制造商:UNINWELL)黏合在该基座211的凹型承载面212上,接着自该发光组件213顶面延伸出与该发光组件213电连接的该连接线214及该导线215。
该荧光层22包覆该发光组件213。该荧光层22中所含的荧光体221在受到该发光组件213所发出光的激发后,会转换发出异于激发光波长的光,于本实施例中,该荧光层22是将含有荧光体221的聚硅烷氧树脂涂布在该发光组件213外表面,并经干燥硬化后而形成。
该封装层23包覆该发光单元21部分的基座211、连接线214、部分的导线215及该荧光层22。
本发明的发光装置中,除了可将本发明的荧光体单独使用外,亦可与具有其他发光特性的荧光体搭配一起使用,以构成可发出所需颜色的发光装置。
例如,将420nm~500nm的蓝色发光组件、发出600nm~650nm的红色的荧光体(如CaAlSiN3:Eu)以及本发明的荧光体组合制备一发光装置。当发光组件所发出蓝光照射于该荧光体时,会分别发出红光及黄光,将该等光与发光组件的蓝光混合而成为白色的发光装置(如照明器具、发光二极管等)。
以下,就本发明实施例加以具体说明,但是本发明并不仅限定于此。
测量方法及原料来源说明:
(1)荧光体发光光谱:
荧光体光特性的测量装置如图2所示。测量方式是取样品1.8克置入直径2公分的样品槽12中,并经压平使样品均匀分布于样品槽12,样品槽12置于黑色箱体11的内部,使用光源波长为455nm的发光源13,距离样品5公分高度,垂直照射样品,并经过一反射镜15使荧光水平式导引进入辉度计16(TOPCON制,机型为SR-3A)。反射镜15置于直径2公分的光导引管14中并导引荧光体所发出的荧光。光导引管与光源成45°角,反射镜15距样品槽12为8公分,而辉度计16距离反射镜15为40公分。辉度计16使用field1°侦测模式。
(2)荧光体D50粒径分析:以BeckmanCoulterMultisizer-3进行测量。D50表示该次试验中,粒径小于该值(D50)的颗粒总体积占全部颗粒总体积的50%。
(3)原料来源分别为:
Y2O3(Sigma-Aldrich)
Al2O3(SasolNorthAmericaPuralBT)
CeO2(上海跃龙新材料股份有限公司)
AlF3(Metalleareearthlimted)
Gd2O3(宏帆铝业材料有限公司)
Ga2O3(Sigma-Aldrich)
Lu2O3(广州建丰五矿稀土有限公司)
La2O3(常熟盛昌稀土冶炼厂)
(4)发光组件的准备:
发光组件中,使用发光中心为455nm的市售蓝色发光二极管组件。于此实施例中所使用者为以碳化硅作为基板的InGaN发光二极管组件。
<制造荧光体>
荧光体的制造方法是使原料Y2O3、Al2O3(SasolPuralBT)、Ga2O3、CeO2、AlF3、Lu2O3、La2O3、Gd2O3均匀混合,其中各原料采用的比例是使混合原料符合表1所示的条件。取10克的混合原料与20~30克纯水均匀混合,取前述含水的混合原料于500ml氧化铝坩埚内壁均匀涂布,此坩埚置入高温炉中加热,炉内气氛为氮气,由室温缓缓升温,于1500℃下恒温约4小时,进行烧结,之后缓缓降至室温冷却,利用前述处理方式于坩埚内壁形成保护层。将混合原料置入具保护层的坩埚中,该坩埚置入高温炉中,炉内气氛为纯氮气的环境,由室温缓缓升温,于1450℃下恒温约4小时,进行烧结,之后缓缓降至室温冷却。经由粉碎、球磨、水洗二次、过滤、干燥等步骤,再次置入高温炉中,炉内气氛为体积比氮气:氢气=95%:5%的环境,由室温缓缓升温,于1200℃下恒温约2小时,进行烧结,之后缓缓降至室温冷却。经由粉碎、球磨、水洗二次、过滤、干燥、分级等步骤。
再次置入高温炉中,炉内气氛为体积比氮气:氢气=95%:5%的环境,由室温缓缓升温,于1500℃下恒温约4小时,进行烧结,之后缓缓降至室温冷却。经由粉碎、球磨、水洗二次、过滤、干燥、分级等步骤,可获得荧光体。荧光体的平均粒径D50为13μm。
注:
实施例1至实施例6的荧光体符合条件:1.74≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤1.35(亦即,在荧光体中,当O为12摩尔份时,Lu摩尔份与Ce摩尔份的总和为1.74至3.0;Y摩尔份、La摩尔份与Gd摩尔份的总和为0.1~1.35。以实施例1为例,其(m*z+1-z)*3等于Lu+Ce=2.78+0.12=2.90,且(1-m)*z*3等于Y+La+Gd=0.10+0+0=0.1。
实施例7至实施例9的荧光体符合条件:0.7≤(m*z+1-z)*3≤0.8,2.2≤(1-m)*(z)*3≤2.35(亦即,在荧光体中,当O为12摩尔时,Lu摩尔数与Ce摩尔数的总和为0.7至0.8;Y摩尔数、Gd摩尔数与La摩尔数的总和为2.2~2.35)。
比较例1至比较例6的荧光体不符合实施例1至实施例6的荧光体的条件,也不符合实施例7至实施例9的荧光体的条件。
<荧光体的光学特性>
表2为荧光体以相同测量条件所得的发光光谱结果。从表2的结果可知,实施例的荧光体的发光强度大于比较例的荧光体的发光强度。由实验数据可发现,唯有荧光体组成式同时符合请求项范围1.74≤(m*z+1-z)*3≤3.0,0.1≤(1-m)*z*3≤1.35时,荧光体才能满足业界所需色度坐标,并明显提升荧光体的发光强度达到高辉度效果。
※发光强度以实施例9为基准视为100%。
虽然本发明已以较佳实施例揭露如上,然其并非用以限定本发明,任何熟悉此项技艺者,在不脱离本发明的精神和范围内,当可做些许更动与润饰,因此本发明的保护范围当以权利要求的保护范围所界定者为准。
Claims (9)
1.一种荧光体,其特征在于,所述荧光体的通式为((LumA1-m)zCe1-z)3Q5O12,其中0<m<1,0<z<1,Lu为镥元素,O为氧元素,Ce为铈元素,0.1≤(1-m)*z*3≤0.21,2.79≤(m*z+1-z)*3≤2.9,其中
A的通式为LanGdgY1-n-g,0≤n<1,0≤g<1,
Q的通式为AlrGajIn1-r-j,0<r≤1,0≤j<1,以及
n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1,(1-z)*3=0.095~0.135,j*5=0~0.3。
2.根据权利要求1所述的荧光体,其特征在于,在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.370<x<0.400,0.570<y<0.580。
3.一种荧光体,其特征在于,所述荧光体的通式为((LumA1-m)zCe1-z)3Q5O12,其中0<m<1,0<z<1,Lu为镥元素,O为氧元素,Ce为铈元素,2.3≤(m*z+1-z)*3≤2.4,0.6≤(1-m)*z*3≤0.7,其中,
A的通式为LanGdgY1-n-g,0≤n<1,0≤g<1,
Q的通式为AlrGajIn1-r-j,0<r≤1,0≤j<1,以及
n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1,(1-z)*3=0.095~0.135,j*5=0~0.3。
4.根据权利要求3所述的荧光体,其特征在于,在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.400<x<0.418,0.560<y<0.570。
5.一种荧光体,其特征在于,所述荧光体的通式为((LumA1-m)zCe1-z)3Q5O12,其中0<m<1,0<z<1,Lu为镥元素,O为氧元素,Ce为铈元素,1.70≤(m*z+1-z)*3≤2.29,0.8≤(1-m)*z*3≤1.35,其中
A的通式为LanGdgY1-n-g,0≤n<1,0≤g<1,
Q的通式为AlrGajIn1-r-j,0<r≤1,0≤j<1,
n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1,(1-z)*3=0.095~0.135,j*5=0~0.3。
6.根据权利要求5所述的荧光体,其特征在于,在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.418<x<0.426,0.545<y<0.560。
7.一种荧光体,其特征在于,所述荧光体的通式为((LumA1-m)zCe1-z)3Q5O12,其中0<m<1,0<z<1,Lu为镥元素,O为氧元素,Ce为铈元素,0.7≤(m*z+1-z)*3≤0.8,2.2≤(1-m)*(z)*3≤2.3,其中
A的通式为LanGdgY1-n-g,0≤n<1,0≤g<1,
Q的通式为AlrGajIn1-r-j,0<r≤1,0≤j<1,
n*(1-m)*z*3=0~0.1,g*(1-m)*z*3=0~0.1,(1-z)*3=0.095~0.135,j*5=0~0.3。
8.根据权利要求7所述的荧光体,其特征在于,在以波长为455nm的光照射激发下,所述荧光体发出光的CIE1931色坐标为0.450<x<0.486,0.504<y<0.545。
9.一种发光装置,其特征在于,包括:
一发光组件;以及
一如权利要求1至8任一所述的荧光体,所述荧光体在受到所述发光组件所发出的激发光的激发后,发出异于该激发光波长的光。
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