TWI494413B - 螢光體與發光裝置 - Google Patents
螢光體與發光裝置 Download PDFInfo
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- TWI494413B TWI494413B TW101149356A TW101149356A TWI494413B TW I494413 B TWI494413 B TW I494413B TW 101149356 A TW101149356 A TW 101149356A TW 101149356 A TW101149356 A TW 101149356A TW I494413 B TWI494413 B TW I494413B
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- phosphor
- light
- molybdenum
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 129
- 239000004065 semiconductor Substances 0.000 claims description 41
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 18
- 235000019557 luminance Nutrition 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 238000010304 firing Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 150000004767 nitrides Chemical class 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QCLQZCOGUCNIOC-UHFFFAOYSA-N azanylidynelanthanum Chemical compound [La]#N QCLQZCOGUCNIOC-UHFFFAOYSA-N 0.000 description 2
- AJXBBNUQVRZRCZ-UHFFFAOYSA-N azanylidyneyttrium Chemical compound [Y]#N AJXBBNUQVRZRCZ-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- XCNGEWCFFFJZJT-UHFFFAOYSA-N calcium;azanidylidenecalcium Chemical compound [Ca+2].[Ca]=[N-].[Ca]=[N-] XCNGEWCFFFJZJT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241000181331 Saron Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 description 1
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010938 white gold Substances 0.000 description 1
- 229910000832 white gold Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
-
- 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
-
- 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
- H01L2224/481—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
-
- 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
- H01L2224/80—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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Description
本發明是有關於一種螢光體與使用其之發光裝置,且特別是有關於一種組成式為Aa
Si5
Ot
Nn
:EuZ
的螢光體與使用其之發光裝置。
近年,使用半導體發光的發光裝置被廣泛地使用,特別是發光二極體已被成功開發,此發光裝置較習知的冷陰極燈管、白熾燈等發光設備,具有發光效率高、體積小、低耗電力與低成本等優點,因此可做為各種光源來使用。而半導體發光裝置包含半導體發光元件與螢光體,螢光體可吸收並轉換半導體發光元件所發出的光,藉由半導體發光元件所發出的光與螢光體轉換發出的光兩者混合使用。此種發光裝置可作為螢光燈、車輛照明、顯示器、液晶背光顯示等各種領域使用,其中,以白色發光裝置使用最為廣泛。現行白色發光裝置係採用鈰為活性中心之YAG螢光體(Y3
Al5
O12
:Ce)並搭配發出藍光之半導體發光元件所組成。然而,使用Y3
Al5
O12
:Ce螢光體並搭配發出藍光之半導體發光元件所發出之混合光,其色度座標位於發出藍光之半導體發光元件之色座標與Y3
Al5
O12
:Ce螢光體之色座標連接線上,因而,所發出之混合光為缺乏紅色光之白光,演色性與色彩飽和度明顯不足。此外,Y3
Al5
O12
:Ce的較佳激發光譜區域和半導體發光元件之發光區域並不一致,因此,激發光之轉換效率不佳,高輝度之白光光源
不易獲得。為解決此種色調不良和發光輝度低下的現象,近年積極開發將YAG:Cc螢光體中混入可發出紅光之螢光體,並改良可發出紅光之螢光體的品質,以提高發光輝度。
然而,吸收藍色光進而發出紅色光之螢光體較為稀少,目前業界的開發研究以氮化物、氮氧化物螢光體為主。已知有使用銪(Eu)為活性中心的Sr2
Si5
N8
:Eu螢光體、CaAlSiN3
:Eu螢光體及一般式為Mz
Si12-(m+n)
Alm+n
On
N16-n
:Eu的賽隆螢光體。然而,Sr2
Si5
N8
:Eu螢光體由於發光輝度不佳,應用性受到侷限,近年使用上並不普及;賽隆螢光體本身無耐久性問題,但是螢光體發光輝度明顯不足,商業使用上並不普及。CaAlSiN3
:Eu螢光體雖然有較佳的耐久性,以及較賽隆螢光體為佳的輝度,但業界仍期待能更進一步提高螢光體的發光輝度,以使發光裝置能具有較高的發光效率。
鑒於上述問題,因此本發明之目的在於提供高輝度的螢光體材料,以及提供使用所述的螢光體材料搭配半導體發光元件而構成一高輝度的發光裝置。
根據實施例,提供一種螢光體。螢光體包括組成式為Aa
Si5
Ot
Nn
:EuZ
的組成物。A元素係選自由鈹(Be)、鎂(Mg)、鈣(Ca)、鍶(Sr)及鋇(Ba)元素所構成之群組。1.7<a<2.5。0≦t<1。7<n<9。0.001<z<0.3。螢光體具有10ppm~500ppm的鉬(Mo)。
根據實施例,提供一種發光裝置。發光裝置包括半導
體發光元件與上述螢光體。螢光體受半導體發光元件所發出之光激發,並轉換發出波長相異於半導體發光元件所發出的光。
於實施例中,螢光體包括組成式為Aa
Si5
Ot
Nn
:EuZ
的組成物,並且螢光體具有鉬(Mo)元素。添加鉬後之螢光體,相較於色度相同下之未添加鉬之螢光體具有較高之輝度值。所謂色度相同意味著色度座標x、y差異分別在±0.002之內。
於實施例中,A元素係選自由鈹(Be)、鎂(Mg)、鈣(Ca)、鍶(Sr)及鋇(Ba)元素所構成之群組。A元素較佳係選自由鈣(Ca)、鍶(Sr)及鋇(Ba)元素所構成之群組。1.7<a<2.5,較佳為1.8<a<2.3。0≦t<1,較佳為0≦t<0.5。7<n<9,較佳為7<n<8。
此外,螢光體中含有的鉬含量,對於螢光體的發光輝度有所影響,因此需藉由控制鉬的含量在特定範圍,達到高發光輝度的效果。本發明之螢光體具有鉬(Mo)元素10ppm~500ppm,過多或過少的鉬都會使得輝度下降。於實施例中,螢光體具有鉬元素較佳20ppm~350ppm,更佳為25ppm~200ppm。
螢光體中,0.001<z<0.3。若螢光體之發光中心的Eu數量過少,會使得螢光體的發光輝度降低。若螢光體之發光中心的Eu數量過高,由於Eu原子間的相互干擾而造成濃度消光的現象,以致輝度減低。較佳地,當0.01<z<0.05時,發光輝度更佳。
當使用455nm光源照射本發明之螢光體時,螢光體受激發而發出之發光主波長為580nm~680nm,其發光色調之CIE 1931色度座標(x,y)為0.45≦x≦0.72,0.2≦y≦0.5。發光主波長係指發光光譜中發光強度最大的波長。
本發明的螢光體製造時,矽元素的原料可使用含氮化合物、含氧化合物、任何形式的化合物或矽的元素態。例如,可混合使用矽元素的氮化物(Si3
N4
)/氧化物(SiOx
)。所謂「含氧化合物」可包含氧化物、碳酸鹽、草酸鹽等化合物。含氮化合物的情況,亦是指具有矽元素與氮的化合物。
欲達到本發明之鉬的含量範圍,較佳可藉由外添加方式燒成實施。添加的鉬的前驅物並無特別限制,可為鉬金屬、碳酸鉬、氮化鉬、氧化鉬、氫氧化鉬、氫化鉬等各種實施樣態。其中以氧化鉬的實施效果較佳。例如三氧化鉬、二氧化鉬等的氧化鉬,其中尤以三氧化鉬效果最佳。
本發明螢光體原料可為各種不同形式之前驅物,為方便起見以下以氮化物與氧化物原料作為實施方式說明。A元素與Si元素的氧化物或氮化物原料雖可為市售原料,但是因為純度越高越好,因此最好準備3N(99.9%)以上的原料為佳。各原料粒子的粒徑從促進反應的觀點而言,最好為微粒子,但是隨原料的粒徑、形狀之不同,所獲得螢光體的粒徑、形狀亦將有所變化。因此只要配合最終所獲得螢光體要求的粒徑,準備具有近似粒徑之氮化物、氧化物原料即可。Eu元素之原料以市售氧化物、氮化物原料或金屬為佳,純度越高越好,最好準備2N(99%)以上,尤以3N(99.9%)以上的原料為佳。
原料的混合方式,可為乾式法、濕式法。例如乾式球磨法或加入液體的濕式球磨法等多種實施方式,並不侷限於單一方式。秤取、混合Ca3
N2
、Sr3
N2
、Si3
N4
、Ba3
N2
時,因為此等化合物較易被氧化,因而在非活性環境下的手套箱內進行操作較為適當。此外,因為各原料元素的氮化物較容易受水分的影響,因此,用於充填手套箱之非活性氣體最好使用經充分去除水分的氣體。此外,若為濕式混合法,當所使用的液體為純水時,原料將遭分解,因此,必須選擇適當的有機溶劑。混合裝置可使用球磨機或研缽等通常所使用的裝置。
製備螢光體時可依一定比例秤量、混合各原料,置入坩堝中,再置入高溫爐中燒成。燒成時使用之高溫爐,因燒成溫度為高溫,故較佳為使用金屬電阻加熱方式或石墨電阻加熱方式之高溫爐。作為燒成之方法,較佳的是常壓燒成法或氣壓(以氣體加壓)燒成法等外部未施加機械性加壓之燒成方法。坩鍋較佳為不純物含量極低之高純度材質,如Al2
O3
坩鍋、Si3
N4
坩鍋、AlN坩鍋、賽隆坩鍋、BN(氮化硼)坩鍋等可在非活性環境中使用的坩鍋,其中以使用BN坩鍋為最佳,因其對於避免源自坩鍋的不純物混入的效果最佳。燒成氣氛為非氧化性氣體,例如,可為氮、氫、氨、氬等或前述氣體之任意組合。螢光體之燒成溫度為1200℃以上、2200℃以下,更佳為1400℃以上、2000℃以下,升溫速度為3~15℃/min。較低溫下燒成可得較細微螢光體,較高溫下燒成可得粒徑較大螢光體。燒成時間根據原料種類不同而有所差異,一般反應時間為1~12小時
較佳。燒成時在非活性環境下之壓力,例如是在0.5 MPa以下(尤以0.1 MPa以下為佳)進行燒成。燒成完成後,冷卻至室溫,可使用球磨、或工業用粉碎機械等方式粉碎,再經過水洗、過濾、乾燥、分級等步驟,即可得到本發明之螢光體。
為了獲得高輝度之螢光體,螢光體於燒成時,因助熔劑之添加、原料中的雜質、處理過程汙染等因素的影響,包含在所述之螢光體組成中的雜質含量應盡可能的小。特別是氟元素、硼元素、氯元素、碳元素等元素大量存在時,將抑制發光。因此可選擇較高純度的原料,和控制合成步驟避免汙染,使得前述氟、硼、氯、碳等元素的含量分別小於1000 ppm。
當本發明的螢光體以粉體的形式使用時,螢光體粉體的平均粒徑最好在30μm以下。理由是因為螢光體粉體的發光主要係發生於粒子表面上,若平均粒徑(本發明中所謂的「平均粒徑」係指體積中數粒徑(D50))在30μm以下,將可確保粉體每單位重量的表面積,避免輝度降低。此外,將粉體塗佈於發光元件之上的情況,可提高粉體的密度,就此觀點而言,亦可避免輝度降低。另外,從螢光體粉末的發光效率觀點而言,平均粒徑以大於1μm為較佳。依上述,本發明螢光體粉體的平均粒徑最好在1μm以上且30μm以下,尤以3.0μm以上且20μm以下的粒徑為佳。此處所謂的「平均粒徑(D50)」,係利用Beckman Coulter公司製MultiSizer-3,以庫爾特法(體積中數粒徑D50)進行測定所得的值。
本發明之螢光體適用於螢光顯示管(VFD)、場發射顯示器(FED)、電漿顯示器(PDP)、陰極射線管(CRT)、發光二極體(LED)等。尤其是,本發明的螢光體當使用455nm光源照射時,發光主波長為580nm~680nm,發光色調之CIE 1931色度座標(x,y)為,0.45≦x≦0.72,0.2≦y≦0.5,且發光輝度高,因此特別適用於發光二極體。
本發明之發光裝置包含半導體發光元件及本發明之螢光體。半導體發光元件以發出波長為300~550nm之光者為較佳,尤其以發出330~420nm之紫外(或紫)光半導體發光元件或420~500nm之藍色半導體發光元件較佳。作為此等發光元件,半導體發光元件可為硫化鋅或氮化鎵等各種半導體,而以發光效率而言,使用氮化鎵半導體較佳。氮化鎵發光元件可藉由有機金屬化學氣相沉積法(MOCVD)或氫化物氣相磊晶法(HVPE)等方法於基板上形成氮化物半導體,以Inα
Alβ
Ga1-α-β
N(0≦α、0≦β、α+β<1)所形成的半導體發光元件最佳。半導體構造可為MIS接合、PIN接合、PN接合等均質構造、異質接面構造或雙異質接面構造。此外,可藉由調整半導體層之材料或其混晶度來控制其發光波長。
本發明之發光裝置中,除了將本發明之螢光體單獨使用外,亦可與具有其他發光特性之螢光體一起使用,以構成可發出所想要之顏色的發光裝置。例如,使用330~420nm之紫外光半導體發光元件搭配在此波長被激發而發出420nm以上且500nm以下波長之藍色螢光體、發出
500nm以上且570nm以下之波長之綠色螢光體、以及本發明之螢光體之組合。前述藍色螢光體舉例可為BaMgAl10
O17
:Eu,綠色螢光體可為β-賽隆螢光體。依此構成,當半導體發光元件所發出之紫外線照射於螢光體時,會發出紅、綠、藍之三色光,經由其混合而成為白色之發光裝置。
此外,尚可使用420~500nm之藍色半導體發光元件搭配在此波長被激發而發出550nm以上且600nm以下之波長的黃色螢光體、以及本發明之螢光體之組合。前述黃色螢光體,例如可為Y3
Al5
O12
:Ce。依此構成,當半導體發光元件所發出之藍色光照射於螢光體時,會發出紅、黃之二色光,將此等與半導體發光元件本身之藍色光混合而成為白色或帶燈泡色之照明器具。
此外,尚可使用420~500nm之藍色半導體發光元件搭配在此波長被激發而發出500nm以上且570nm以下之波長的綠色螢光體、以及本發明螢光體之組合。此種綠色螢光體舉例可為β-賽隆螢光體。依此構成,當半導體發光元件所發出之藍色光照射於螢光體時,會發出紅、綠之二色光,將此等與半導體發光元件本身之藍色光混合而成為白色之照明器具。
以下,就本發明實施例加以說明,但是本發明並不僅限定於此。
測量方法:
(1)螢光體輝度及色度座標:螢光體以TOPCON輝度計SR-3A使用455nm照射測量。輝度值量測差異為±0.3%以內。
(2)螢光體發光主波長:以Jobin YVON的Fluoro Max-3進行量測。發光主波長係指使用455nm光激發螢光體時,螢光體最大發光強度的波長。
(3)螢光體組成元素之分析:
(3-1a)儀器:以Jobin YVON的ULTIMA-2型感應耦合電漿原子放射光譜儀(ICP)進行元素含量之量測。
(3-1b)樣品前處理:準確秤取0.1g的樣品,於白金坩鍋內,加入Na2
CO3
1g混合均勻後,以1200℃高溫爐熔融(溫度條件:由室溫升溫2小時到達1200℃,於1200℃恆溫5小時),待熔融物冷卻後加入酸溶液,例如25ml HCl(36%),並加熱溶解至澄清,冷卻後置入100ml PFA定量瓶中,以純水定量至標線。
(3-2a)儀器:Horiba的氮氧分析儀。型號EMGA-620W。
(3-2b)測量:將螢光體20mg置入錫膠囊內,放置於坩堝中,進行量測。
準備所需之鈣金屬(3N7,99.97%)、鍶金屬(4N,99.99%)和鋇金屬(2N,99%),粉碎後分別置於純氮氣氛下直接燒
成形成氮化物,反應條件分別為750℃、700℃、700℃下燒成24小時。可分別獲得氮化鈣(Ca3
N2
)、氮化鍶(Sr3
N2
)和氮化鋇(Ba3
N2
)的化合物。
實施例1~實施例5、比較例1~比較例3的螢光體製造方式相同,差異主要在於三氧化鉬(MoO3
)的使用量不同,以下以實施例3為例說明螢光體的製造方法。
在實施例3中,是秤取204.648g合成例1合成之氮化鍶(Sr3
N2
)化合物、250.000g之氮化矽(Si3
N4
,純度3N)及4.892g之氧化銪(Eu2
O3
,純度4N)、0.046g之三氧化鉬(MoO3
,純度2N)在氮氣環境下於手套箱中使用研缽進行混合,形成一螢光體起始原料,其中三氧化鉬原料佔螢光體起始原料(表1的Mo wt.%欄)0.003wt.%。
然後,將螢光體起始原料置入以氮化硼為材質之燒成容器中,接著將含有起始原料之燒成容器置入含有高純度氮氣之高溫爐中,氮氣氣體流量為80升/分,依10℃/min的升溫速度升溫至1800℃,並在1800℃下保持8小時,且高溫爐操作壓力維持在0.1 MPa,以進行燒成。燒成後,依10℃/min的降溫速率降至室溫,再經由粉碎、球磨、水洗二次、過濾、乾燥及分級等步驟,即獲得螢光體。
實施例3之氮氧分析儀及ICP分析結果為螢光體具有組成式Sr1.926
Si5
O0.108
N7.416
:Eu0.021
,亦即,Aa
Si5
Ot
Nn
:EuZ
式中,A元素為Sr,a=1.926,t=0.108,n=7.416,
z=0.021。螢光體之鉬含量87 ppm。
實施例6與實施例3的螢光體製造方式相同,差異主要在於三氧化鉬(MoO3
)改成使用二氧化鉬(MoO2
),其中二氧化鉬原料佔螢光體起始原料(表1的Mo wt.%欄)0.010wt.%。
實施例7與實施例3的螢光體製造方式相同,差異主要在於實施例7的螢光體起始原料是秤取90.846g合成例1合成之氮化鍶(Sr3
N2
)化合物、137.423g合成例1合成之氮化鋇(Ba3
N2
)化合物、224.000g之氮化矽(Si3
N4
,純度3N)及7.418g之氧化銪(Eu2
O3
,純度4N)、0.046g之三氧化鉬(MoO3
,純度2N)在氮氣環境下於手套箱中使用研缽進行混合,以形成螢光體起始原料,其中三氧化鉬原料佔螢光體起始原料(表1的Mo wt.%欄)0.010wt.%。
實施例8與實施例3的螢光體製造方式相同,差異主要在於實施例8的螢光體起始原料是秤取5.326g合成例1合成之氮化鈣(Ca3
N2
)、193.954g合成例1合成之氮化鍶(Sr3
N2
)化合物、252.000g之氮化矽(Si3
N4
,純度3N)及8.345g之氧化銪(Eu2
O3
,純度4N)、0.046g之三氧化鉬
(MoO3
,純度2N)在氮氣環境下於手套箱中使用研缽進行混合,形成螢光體起始原料。
表1列示各實施例與比較例之螢光體起始原料使用的鉬來源化合物及其所占的重量比。此外,表1也列示得到的螢光體性質,包括具有的A元素、鉬元素含量(Mo(ppm))、與色度座標x、y下的發光輝度。螢光體之發光光譜之主波長係指發光強度最大的波長。
根據表1,在色度相同下,實施例1、2、6~8之輝度高於比較例1;在色度相同下,實施例3~5之輝度高於比較例2。
接著,將前述本發明各實施例的螢光體樣品與半導體發光元件進行封裝後製得本發明之發光裝置。
參閱第2圖,本發明發光裝置實施例包含一半導體發光元件21、一螢光層22及一封裝層23。
其中,半導體發光元件21包括一可導電且具有一概呈凹型的承載面212的基座211、一設置於凹型承載面212且與基座211電連接的發光二極體晶粒213、一連接線214與發光二極體晶粒213電連接、一導線215與連接線214電連接;其中,基座211與導線215可配合自外界提供電能至發光二極體晶粒213,發光二極體晶粒213可將接受之電能轉換成光能向外發出。本實施例是將一市售發光波長455nm,InGaN的藍色發光二極體晶粒213(製造商:奇力光電)以導電銀膠(型號:BQ6886,製造商:UNINWELL)黏合在基座211的承載面212上,接著自發光二極體晶粒213頂面延伸出與發光二極體晶粒213電連接的連接線214及導線215。
前述螢光層22包覆發光二極體晶粒213。螢光層22中所含的螢光體221在受到發光二極體晶粒213所發出之光的激發後,會轉換發出異於激發光波長的光,於本實施
例中,螢光層22是將含有35重量%螢光體221的聚矽烷氧樹脂塗佈在發光二極體晶粒213外表面,並經乾燥硬化後而形成。
封裝層23包覆半導體發光元件21部分的基座211、連接線214、部分的導線215及螢光層22。
綜上所述,實施例的螢光體具有高輝度。且螢光體搭配半導體發光元件,可同時得到高輝度的發光裝置。
21‧‧‧半導體發光元件
22‧‧‧螢光層
23‧‧‧封裝層
211‧‧‧基座
212‧‧‧承載面
213‧‧‧發光二極體晶粒
214‧‧‧連接線
215‧‧‧導線
221‧‧‧螢光體
第1圖是本發明發光裝置實施例的透視圖。
21‧‧‧半導體發光元件
22‧‧‧螢光層
23‧‧‧封裝層
211‧‧‧基座
212‧‧‧承載面
213‧‧‧發光二極體晶粒
214‧‧‧連接線
215‧‧‧導線
221‧‧‧螢光體
Claims (7)
- 一種螢光體,其中該螢光體包括組成式為Aa Si5 Ot Nn :EuZ 的組成物,該A元素係選自由鈹(Be)、鎂(Mg)、鈣(Ca)、鍶(Sr)及鋇(Ba)元素所構成之群組,1.7<a<2.5,0≦t<1,7<n<9,0.001<z<0.3,該螢光體具有10ppm~500ppm的鉬(Mo)。
- 如申請專利範圍第1項所述之螢光體,其中該螢光體具有20ppm~350ppm的鉬(Mo)。
- 如申請專利範圍第1項所述之螢光體,其中該螢光體具有25ppm~200ppm的鉬(Mo)。
- 如申請專利範圍第1項所述之螢光體,其中1.8<a<2.3,0≦t<0.5,7<n<8,0.01<z<0.05。
- 如申請專利範圍第1項所述之螢光體,其中該A元素係選自由鈣(Ca)、鍶(Sr)及鋇(Ba)元素所構成之群組。
- 如申請專利範圍第1項所述之螢光體,其中使用455nm光源照射該螢光體,該螢光體受激發而發出之發光主波長為580nm~680nm,其發光色調之CIE 1931色度座標(x,y)為0.45≦x≦0.72,0.2≦y≦0.5。
- 一種發光裝置,包括:一半導體發光元件;以及一螢光體,包括如申請專利範圍第1項至第6項中任一項所述之螢光體,其中該螢光體受該半導體發光元件所發出之光激發,並轉換發出波長相異於該半導體發光元件所發出的光。
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CN201310130888.6A CN103881710B (zh) | 2012-12-22 | 2013-04-16 | 荧光体与发光装置 |
US14/034,587 US9157024B2 (en) | 2012-12-22 | 2013-09-24 | Phosphor and light emitting device |
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TW201425523A (zh) | 2014-07-01 |
CN103881710A (zh) | 2014-06-25 |
US20140175970A1 (en) | 2014-06-26 |
US9157024B2 (en) | 2015-10-13 |
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