TWI491706B - Green luminescent phosphor and light emitting device - Google Patents
Green luminescent phosphor and light emitting device Download PDFInfo
- Publication number
- TWI491706B TWI491706B TW100135604A TW100135604A TWI491706B TW I491706 B TWI491706 B TW I491706B TW 100135604 A TW100135604 A TW 100135604A TW 100135604 A TW100135604 A TW 100135604A TW I491706 B TWI491706 B TW I491706B
- Authority
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- Taiwan
- Prior art keywords
- phosphor
- light
- sample
- luminance
- emitting device
- Prior art date
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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 53
- 239000002223 garnet Substances 0.000 claims description 28
- 235000019557 luminance Nutrition 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 40
- 239000000203 mixture Substances 0.000 description 20
- 238000004020 luminiscence type Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 238000009877 rendering Methods 0.000 description 12
- 229910052733 gallium Inorganic materials 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 230000000638 stimulation Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000001748 luminescence spectrum Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 4
- 229910001632 barium fluoride Inorganic materials 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000004936 stimulating effect Effects 0.000 description 4
- 229910016036 BaF 2 Inorganic materials 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- 241000511976 Hoya Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- -1 yttrium activated calcium sulfide Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- 229910018119 Li 3 PO 4 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 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
- 229910052788 barium Inorganic materials 0.000 description 1
- LYSTYSFIGYAXTG-UHFFFAOYSA-L barium(2+);hydrogen phosphate Chemical compound [Ba+2].OP([O-])([O-])=O LYSTYSFIGYAXTG-UHFFFAOYSA-L 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- HKSVWJWYDJQNEV-UHFFFAOYSA-L strontium;hydron;phosphate Chemical compound [Sr+2].OP([O-])([O-])=O HKSVWJWYDJQNEV-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- 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
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- 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
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector 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
- H01L2224/32221—Disposition the layer connector 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
- H01L2224/32225—Disposition the layer connector 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 non-metallic, e.g. insulating substrate with or without metallisation
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- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
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- H01L2224/32245—Disposition the layer connector 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
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- H01L2224/32245—Disposition the layer connector 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
- H01L2224/32257—Disposition the layer connector 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 the layer connector connecting to a bonding area disposed in a recess of the surface of the item
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- 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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- H—ELECTRICITY
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- 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
- H01L2224/48225—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 non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—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 non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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- 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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- H01L2224/01—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
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- 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
- H01L2224/48257—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 die pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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
- H01L2224/484—Connecting portions
- H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
- H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
- H01L2224/491—Disposition
- H01L2224/49105—Connecting at different heights
- H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
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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)
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Description
本發明係關於由發光元件吸收藍色系的光,而能夠發出綠色系的光之螢光體。特別是關於適合使用於能夠利用於被要求有演色性之照明用光源、或液晶之背光等的白色系發光二極體之螢光體。及關於使用此螢光體之半導體發光裝置。
以往已知有使用吸收藍色系光或紫外線,將波長轉換為紅色、黃色或綠色等長波長可見光之螢光體,並藉由組合此螢光體得到白色等可見光。
特別是,作為短波長區域之可見光或紫外線的光源者,係使用半導體發光元件、例如氮化鎵(GaN)系藍色發光二極體等。而組合波長轉換材料之螢光體來構成,且發出白色等可見光之半導體發光裝置,具有消費電力小、壽命長的特徵,近年來作為影像顯示裝置或照明裝置之發光源而受到注目。
此外,此半導體發光裝置,係藉由波長轉換材料之螢光體吸收GaN系藍色發光二極體所發出之藍色區域的可見光而發出黃色光,且與未被此螢光體吸收之發光二極體的藍色光混色,而發出白色光(例如參照專利文獻1)。
但是,此白色光係以藍色光與其互補色之黃色光來形成,因此會有演色性缺乏之問題。
作為改善了以藍色光與黃色光形成之白色光的演色性者,例如有組合藍色光發光二極體、綠色系發光螢光體與紅色發光螢光體以形成白色光者(例如參照專利文獻2)。
作為上述綠色系發光螢光體者,例如可列舉具有岩鹽型結晶構造之鹼土類金屬硫化物螢光體(例如鈰活化之硫化鈣(CaS:Ce)螢光體)、或以2價銪活化之鹼土類金屬原矽酸鹽螢光體(例如(Sr,Ba)2
SiO4
:Eu2+
螢光體)等。
但是,該等之硫化物系螢光體或原矽酸鹽螢光體,就化學安定性或發光輝度等方面,仍然有不充分的問題。
該等之外,作為綠色系發光螢光體者,已知有於已知作為黃色發光螢光體之鈰活化之釔鋁石榴石(YAG:Ce)螢光體當中,將鋁的一部分以鎵(Ga)取代藉以使發光色朝短波長側偏移,而發出綠色區域之光的螢光體,例如Y3
(Al,Ga)5
O12
:Ce螢光體(例如參照專利文獻1)。
但是,因為係以鎵取代,故會有發光輝度降低之問題、或於高溫時發光輝度降低之問題。特別是近年來,要求使用高輸出型之發光元件,因此高輸出時之發光元件所散發之熱的影響而造成之輝度降低係成為重大的問題。
又,亦提出有於母體之釔位置的一部分使用鎦(Lu)的石榴石系螢光體(例如參照專利文獻3)。亦已知藉由於母體之一部分使用鎦,發光色會朝短波長側偏移,且相較於上述專利文獻1之以鎵取代的石榴石系螢光體,具有高溫時之發光輝度不易降低之特徵(例如參照專利文獻4)。但是,發光輝度本身不充分,故要求有更加高輝度之綠色系發光螢光體。
由別的觀點而言,為了更提高半導體發光裝置之演色性,作為綠色系發光螢光體係被要求更加短波長側之發光色。以日本工業規格JIS-Z-8701之附屬書所定義之「主波長」來表示發光色時,亦即由CIE1931XYZ色彩系統中無彩顏色之色度座標的x=0.3333、y=0.3333的點、與在連結發光色之色度座標x,y的延長線上之光譜軌跡的交點之波長係為主波長。
此處使用分光器等,得到以450nm之藍色光激發螢光體後之發光光譜。其中係使用由470nm至780nm之波長範圍來計算以求得色度座標x、y、且將由此色度座標x、y來求得之主波長,定義為本申請案之主波長。以此主波長來顯現各種螢光體之發光色時,例如YAG:Ce系螢光體主波長具有約573nm附近之發光色;以鎵取代一部分之Y3
(Al,Ga)5
O12
:Ce螢光體,雖然依組成而定,但主波長能夠具有約556nm至568nm附近的發光色。
但是,如上所述,Y3
(Al,Ga)5
O12
:Ce螢光體其輝度不充分,具有在高溫時輝度降低之問題。因此,由更提高半導體發光裝置之演色性的市場需求而言,係被要求於主波長在更加短波長側,例如約554nm以上、約562nm以下之範圍具有發光色、且具有高發光輝度,於高溫時之發光輝度的降低更少之優良綠色系發光螢光體。
再者,例如用於液晶背光之光源的情況時,當為越接近液晶背光之彩色濾光片的穿透特性(分光特性)的發光色,光的穿透效率越佳,能夠達到鮮豔的色彩再現。當為綠色的情況時,由穿透率之峰值在約520~530nm前後看來,即使為用於液晶背光之光源時,如上所述,係被要求在更短波長側發光、且具有高發光輝度、高溫時之發光輝度的降低更少之優良的綠色系發光螢光體。以下,本說明書中之「演色性」,亦包含於如此之液晶背光用途中的色彩再現性的意思。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開平10-242513號公報(第1-2頁)(第5頁)
專利文獻2:日本專利第4101468號公報(第1-2頁)
專利文獻3:日本特開2005-8844號公報(第1-2頁)
專利文獻4:中國專利第200710132014.9號說明書(圖2、圖6)
如此,就習知的綠色系發光螢光體而言,無法滿足具有高發光輝度、在高溫時亦能維持發光輝度、同時半導體發光裝置之演色性亦更加提高的市場需求。
本發明為了達到滿足此市場需求的目的,係提供主波長在約554nm以上、約562nm附近之範圍具有發光色、且具有高發光輝度、在高溫時之發光輝度的降低更少之適於半導體發光裝置的優良綠色系發光螢光體。
發明者等人,為了解決上述課題,進行各種探討的結果,發現了以下所揭示的特定組成之綠色系發光螢光體,係為主波長在約554nm以上、約562nm附近之範圍具有發光色、且具有高發光輝度、具有在高溫時之發光輝度的降低更少之、演色性高的半導體發光裝置所必須的優良特性之螢光體。
第1發明之石榴石系的綠色系發光螢光體,其特徵為係以(Lu1-x
Cex
)3+d
Al5-d
O12
之式表示,x為0.005≦x≦0.14、d為0.03≦d≦0.5。
而藉由上述組成的鈰活化之鎦‧鋁‧石榴石(LuAG:Ce)系之綠色系發光螢光體,主波長在約554nm以上、約562nm附近之範圍具有發光色、且具有高發光輝度、具有在高溫時之發光輝度的降低更少之、演色性高之半導體發光裝置所必須之優良特性的綠色系發光螢光體。
第2發明之石榴石系綠色系發光螢光體,係如第1發明之石榴石系綠色系發光螢光體,其中d為0.045≦d≦0.2。
而藉由使d在上述值之範圍,綠色系發光螢光體會具有更佳之發光色與發光輝度。
第3發明之半導體發光裝置,其特徵為至少具備第1或第2發明之石榴石系綠色系發光螢光體與半導體發光元件。而藉由使用第1或第2之石榴石系綠色系發光螢光體,演色性優良、且高溫時的輝度降低少,因此會成為高輸出時之輝度降低少之效率良好的半導體發光裝置。
依照本發明之石榴石系綠色系發光螢光體,可得到一種綠色系發光螢光體,其係主波長在約554nm以上、約562nm附近之範圍具有發光色、且具有高發光輝度、具有高溫時之發光輝度的降低更少的特性,且具有可適合使用於演色性高之半導體發光裝置之優良特性。
又,依照本發明之至少具備石榴石系綠色系發光螢光體與半導體發光元件的半導體發光裝置,其演色性優良、且高溫時之輝度的降低少,因此可得到即使於高輸出時,輝度降低亦少,且效率佳之半導體發光裝置。
以下,說明製造本發明之一實施形態中之石榴石系綠色系發光螢光體之步驟。
首先,準備鎦(Lu)之原料例如氧化鎦(Lu2
O3
)、鋁之原料例如氧化鋁(Al2
O3
)、作為賦活劑之鈰(Ce)的原料例如氧化鈰(CeO2
),來作為螢光體原料。
將該等螢光體原料、與作為助焊劑之例如氟化鋇(BaF2
)或氟化鍶(SrF2
)等秤量指定之量,使用球磨機混合等充分混合而得到原料之混合粉末。此時之助焊劑的量,係使用原料總質量之0.1%~10%左右。
將此混合粉末填充至耐熱性容器、例如氧化鋁坩堝等,置入電爐中,於還原環境中例如氮-氧混合氣體氣流中,以例如約1000℃至1800℃之燒成溫度,更佳為1400℃至1600℃之燒成溫度,進行約2小時至12小時之燒成。燒成後冷卻,藉由球磨機等分散/粉碎。接著進行用以去除殘留助焊劑之水及酸洗淨,接著經過乾燥步驟、篩選步驟,而得到指定粒度之螢光體。
再者,作為螢光體原料,主要例示了氧化物,此外,只要係會於高溫分解而成為氧化物之化合物,例如碳酸鹽、草酸鹽、氫氧化物等,則能夠用作螢光體材料。
又,作為助焊劑,雖例示有如氟化鋇(BaF2
)或氟化鍶(SrF2
)之氟化物,但此外亦可使用氯化物等之鹵化物、或構成螢光體之元素的鹵化物、硼酸。又,該等之氟化物中亦可進一步加入磷酸氫鋇(BaHPO4
)、磷酸氫鍶(SrHPO4
)、磷酸鋰(Li3
PO4
)等鹼土類金屬之磷酸氫鹽或鹼金屬磷酸鹽。
接著,作為本發明之一實施形態,說明關於具備上述矽酸鹽系螢光體之半導體發光裝置的構成。
圖6為顯示本發明之一實施形態中之半導體發光裝置的剖面圖。
此半導體發光裝置,於引線框架101之前端具有杯狀凹陷之安裝座部10。作為放出由近紫外至藍色區域之光的半導體發光元件,例如具有絕緣基板之半導體發光元件11係以例如環氧樹脂等所構成之黏著劑12固定於此杯狀之安裝座部10。設於上述半導體發光元件11之上側面的P型電極13a,係藉由例如Au、Al、Cu等所構成的金屬導線15a而連接於引線框架101之電極部13b。又,設於上述半導體發光元件11之上側面的N型電極14a,係藉由金屬導線15b而連接於右側之引線框架102的電極部14b。
此外,螢光體21係充分地混合,而填充於杯狀的安裝座部10內。進一步地,上述半導體發光元件11及引線框架101,102之上部,係藉由例如透明的環氧樹脂等之壓模樹脂30而密封,而形成砲彈形狀之半導體發光裝置。
此圖6所示之砲彈形狀的半導體發光裝置,為了效率良好地將由半導體發光元件11發出的光聚光,引線框架101之安裝座部10係形成為杯狀,所放射的光係具有朝向圖6之上方的指向性。
進一步,將半導體發光元件11配置於杯狀之安裝座部10之底部,並且將螢光體21填充於此安裝座部10,藉由該等螢光體21,由半導體發光元件11所發出之近紫外至藍色區域、例如390nm至470nm波長之光會進行波長轉換,而由螢光體21發出綠色區域或紅色區域等之光。
然後,藉由自半導體發光元件11發出之光、與自螢光體21發出之光的混色,由圖6之半導體發光裝置會放射出白色區域的光。
此處,藉由將螢光體21填充於杯狀之安裝座部10,來自半導體發光元件11的光會效率良好地轉換,而提高半導體發光裝置之輝度,但螢光體21並不一定必須填充於安裝座部10內整體,而亦可依照需要填充為凹狀、或填充為凸狀。
進一步地,亦可不將螢光體21填充於杯狀之安裝座部10內,而係分散於密封樹脂30內。
圖7為顯示本發明之另一實施形態中之半導體發光裝置的剖面圖。
此半導體發光裝置,係於例如具有耐熱性之環氧玻璃所構成之直方體形狀的印刷配線基板16上,藉由以環氧樹脂所構成之黏著劑12,來黏著具有絕緣性基板之半導體發光元件11。設於此半導體發光元件11之上側面的P型電極13a與N型電極14a,係藉由金屬導線15a,15b,各自連接於印刷配線基板16上側面之電極部16a,16b。該等電極部16a,16b,係透過連接印刷配線基板16之上側面與下側面之未圖示的剖面圓弧狀之通孔,繞至作為安裝面之印刷配線基板16的下側面,而延伸至此安裝面的兩端部。再者,上述印刷配線基板16,亦可使用絕緣性薄膜。
然後,於上述印刷配線基板16上,係以包覆上述半導體發光元件11整體的方式,將作為經分散螢光體21之密封樹脂的例如透光性環氧樹脂等之壓模樹脂32,形成為如圖7所示之梯形剖面,以形成晶片零件形狀之半導體發光裝置。
螢光體21係至少含有本發明之一實施形態之石榴石系綠色系發光螢光體,進一步地,於本發明之綠色系發光螢光體之外,亦可為含有發出紅色區域之光的其他螢光體、例如氮氧化物系螢光體、或CaAlSiN3
系螢光體、硫化物系螢光體等的混合物。此紅色發光螢光體之選擇,可配合本發明之石榴石系綠色系發光螢光體的發光特性等來作適當的選擇。
本發明之半導體發光裝置,不限定於上述構造,只要係由半導體發光元件11發出之由近紫外至藍色區域的光,藉由至少含有本發明之一實施形態的石榴石系綠色系發光螢光體的螢光體21來進行波長轉換,然後藉由將自半導體發光裝置11發出的光、與自螢光體21發出的光混色,而放射白色區域之光的半導體發光裝置即可。
接著,作為上述一實施形態之實施例,針對本發明之綠色系發光螢光體與其特性,與習知之綠色系發光螢光體比較來進行說明。
秤量作為原料之193.0g氧化鎦(Lu2
O3
)(Lu 0.97莫耳)、5.164g之氧化鈰(CeO2
)(Ce 0.03莫耳)、80.72g之氧化鋁(Al2
O3
)(Al 1.5833莫耳),進一步秤量作為助焊劑之8.4g氟化鋇(BaF2
)(原料質量之約3%),將該等原料與助焊劑使用球磨機充分地混合。
將此混合物填充於氧化鋁坩堝中,於1420℃、氮氣97%+氫氣3%之混合氣體的還原環境中燒成8小時。
之後,花約3小時慢慢冷卻至室溫,將所得到之燒成物,經過球磨機之分散及研磨步驟、水及酸之洗淨步驟、乾燥步驟與篩選步驟(通過350網目),得到目標之綠色系發光螢光體。將此作為試樣1-(1)。此試樣1-(1)之組成比雖可以(Lu0.97
Ce0.03
)3
Al4.75
O11.625
表示,但以本來之石榴石系結晶式之(Lu1-x
Cex
)3+d
Al5-d
O12
式表示時,x=0.03、d=0.0968。
對所得到之試樣1-(1),首先以雷射繞射式粒度分布測定裝置(型式:SALD-2100島津製作所製)來測定粒度分布。此結果示於圖1。此時之平均粒徑D50為25.0μm。
接著,使用分光螢光光度計(型式:F-4500日立製作所製),以激發光為450nm來測定發光光譜。此結果示於圖2。
然後,由所得之發光光譜,算出依據日本工業規格JIS-Z-8724之CIE1931XYZ色彩系統中的色度座標x,y。此時,為了避開用作激發光之450nm附近的藍色光之影響,計算對象之波長範圍係設為470nm至780nm。算出的結果,試樣1-(1)之色度座標為x=0.373、y=0.571。
進一步地,由所得之色度座標x,y,依據日本工業規格JIS-Z-8701附屬書,求出主波長及刺激純度。結果,主波長為561.0nm、刺激純度為83.5%。
接著,為了比較,作為習知螢光體,係由Y3
(Al,Ga)5
O12
:Ce螢光體、與化學計量組成之Lu3
Al5
O12
:Ce螢光體中,製成發光色之主波長與試樣1-(1)之561.0nm大致相同之以下組成之螢光體,分別稱為比較例2-(1)、比較例3-(1)。
比較例2-(1):(Y0.975
Ce0.025
)3
(Al0.6
Ga0.4
)5
O12
比較例3-(1):(Lu0.98
Ce0.02
)3
Al5
O12
再者為了參考,亦製成YAG:Ce螢光體作為習知之黃色發光螢光體,而稱為比較例1。
比較例1:(Y0.975
Ce0.025
)3
Al5
O12
關於該等比較例等的製造,除了進一步使用氧化釔(Y2
O3
)作為釔原料、使用氧化鎵(Ga2
O3
)作為鎵原料,使用各自配合組成比之原料以外,係與試樣1-(1)同樣的方式製成螢光體。
對如此而得之比較例1、比較例2-(1)、比較例3-(1),亦與試樣1-(1)同樣地測定發光光譜、算出色度座標x,y、求出主波長與刺激純度。
進一步地,測定實際以藍色LED激發後的發光輝度、與高溫時之輝度維持率。
首先,為了測定實際上以藍色LED激發後之發光輝度,係使用複數個的於室溫(約25℃)下在460nm具有發光峰值波長的發光二極體作為激發光源,朝向對象螢光體試樣照射。使用輝度計(型式:LS-110 Konica Minolta製)來測定由發光後之螢光體來的光。此時,於輝度計的前段部分設置會濾除500nm以下之波長的銳波濾光器(型式:Y-50 HOYA CANDEO OPTRONICS公司製),以去除激發光之藍色光的影響。
所得之發光輝度,係以比較例1為100的相對發光輝度。
接著,為了測定高溫時之輝度維持率,係藉由以下構成之裝置來測定使螢光體之溫度變化後之情況時的發光輝度變化。
於厚度約5mm左右、長寬之長度為約45mm左右之鋁板的上側面,設置直徑約30mm、深度約2mm之圓柱狀凹部且作為試樣保持器,進一步,設置由側面到達底部之中央部分的橫洞,將溫度感測器插入此橫洞,使其能夠測定試樣保持器之溫度。
於試樣保持器裝填作為對象之螢光體粉末,將此試樣保持器置於加熱板上使其能夠加熱。進一步地,使用複數個之於460nm具有發光峰值波長的發光二極體作為激發光源,朝向此螢光體照射,使用輝度計(型式:LS-100 Konica Minolta製)來測定由發光後之螢光體來的光。此時,於輝度計的前段部分設置會濾除500nm以下之波長的銳波濾光器(型式:Y-50 HOYA CANDEO OPTRONICS公司製),以去除激發光之藍色光的影響。
藉由加熱板使試樣保持器中之螢光體粉末溫度由室溫(約25℃)變化至約200℃,同時記錄試樣保持器之溫度與輝度。
溫度感測器:鉑電阻溫度計Pt100(型式:TR-8110 T&D公司製)
資料記錄器:MEMORY HiLOGGER(型式:8420-50日置電機公司製)
將所得之結果,以橫軸為溫度、縱軸為以溫度25℃時之發光輝度為100%時之相對輝度維持率,以比較例1、比較例2-(1)及試樣1-(1)為代表來作圖。作圖後之圖係示於圖3。又,由如此所得之輝度維持率,亦求得以室溫(25℃)之比較例1的發光輝度為100時在200℃之相對發光輝度。
以上,對比較例1、比較例2-(1)、比較例3-(1)及試樣1-(1),整理主波長、刺激純度、相對發光輝度及溫度200℃之相對發光輝度,示於表1。
由表1所示結果,比較主波長在561nm附近之螢光體的比較例2-(1)、比較例3-(1)及試樣1-(1)時,相較於習知螢光體之比較例2-(1)及比較例3-(1),明顯可知本發明的螢光體即試樣1-(1)其相對輝度較兩者更高、且刺激純度亦更高,進一步地,可知200℃之相對發光輝度亦壓倒性地優於該等。
如此,作為用以得到同等之主波長的螢光體,相較於習知螢光體,可知本發明之石榴石系綠色系發光螢光體具有優越的特徵。
接著,顯示發光色之主波長較上述561nm左右更為短波長側的例子。
除了使用196.98g之氧化鎦(Lu2
O3
)(Lu0.99莫耳)與1.721g之氧化鈰(CeO2
)(Ce0.01莫耳)以外,係與前述試樣1-(1)完全同樣的方式製成螢光體、將其稱為試樣1-(2)。此試樣1-(2)之組成比雖可用(Lu0.99
Ce0.01
)3
Al4.75
O11.625
表示,但以本來之石榴石系結晶之式(Lu1-x
Cex
)3+d
Al5-d
O12
式來表示時,x=0.01、d=0.0968。
對所得之試樣1-(2),與試樣1-(1)相同地測定發光光譜、算出色度座標x,y、求出主波長與刺激純度。結果,色度座標為x=0.344、y=0.577、主波長為556.2nm、刺激純度為76.7%。
為了與試樣1-(2)比較,作為習知螢光體,係由Y3
(Al,Ga)5
O12
:Ce螢光體、與化學計量組成之Lu3
Al5
O12
:Ce螢光體當中,以與上述比較例2-(1)及比較例3-(1)相同的方式,製成發光色之主波長與試樣1-(2)之556.2nm大致相同之以下組成的螢光體,分別稱為比較例2-(2)、比較例3-(2)。
比較例2-(2):(Y0.99
Ce0.01
)3
(Al0.63
Ga0.37
)5
O12
比較例3-(2):(Lu0.995
Ce0.005
)3
Al5
O12
對如此方式得到之比較例2-(2)、比較例3-(2),亦與試樣1-(2)相同地測定發光光譜、算出色度座標x,y、求出主波長與刺激純度。
進一步,對該等試樣1-(2)、比較例2-(2)及比較例3-(2),以與試樣1-(1)相同之方式,測定實際以藍色LED激發後之發光輝度、與高溫時之輝度維持率。
以上,對比較例1、比較例2-(2)、比較例3-(2)及試樣1-(2),整理主波長、刺激純度、相對發光輝度及200℃之相對發光輝度,並示於表2。
由表2所示之結果,比較主波長在556nm附近之螢光體的比較例2-(2)、比較例3-(2)及試樣1-(2)時,相較於習知之螢光體的比較例2-(2)及比較例3-(2),明顯可知本發明之螢光體即試樣1-(2),其相對發光輝度較兩者更高、且刺激純度亦更高,進一步地,200℃之相對發光輝度亦壓倒性地優於該等。
如此,可知主波長在556nm附近之螢光體,本發明之石榴石系綠色系發光螢光體相較於習知螢光體,亦具有優越的特徵。
接著,作為本發明之另一形態之實施例,針對本發明之綠色系發光螢光體(Lu1-x
Cex
)3+d
Al5-d
O12
中,將Ce濃度之x固定為0.03時之d值與螢光體的特性來說明。
如表3所示,除了變更各元素之組成比外,係以與前述實施例1中之試樣1-(1)相同的方式製成螢光體,分別稱為試樣2-(1)至試樣2-(12)。
對該等試樣2-(1)至試樣2-(12),亦與實施例1相同地測定主波長、刺激純度、以比較例1為100時之相對發光輝度,且同樣地將其結果與試樣1-(1)之結果一起示於表3。
由表3所示之結果,可知試樣2-(3)至試樣2-(10)及試樣1-(1)、亦即d值為0.03以上、0.5以下之試樣,相較於化學計量組成之試樣2-(1),主波長偏移於短波長側2nm以上、且相對發光輝度亦幾乎不降低,具有較佳特徵。進一步,可知d值為0.045以上之試樣,主波長大致偏移於短波長側3nm以上,而為更佳。
再者,d值超過0.2時,主波長之偏移效果並不如此大、且刺激純度有降低的傾向,故d值較佳為0.045以上、0.2以下。
再者,d值未達0.03而過小時,主波長偏移之效果亦小、又d值超過0.5而過大時,發光輝度會降低。
由以上所述,d值較佳為0.03以上、0.5以下;更佳為0.045以上、0.2以下。
於此,進行粉末X射線繞射分析,確定本發明之綠色系發光螢光體與化學計量組成之Lu3
Al5
O12
:Ce螢光體有如何不同。
對d值為0亦即化學計量組成之試樣2-(1)與d值為0.0968之試樣1-(1),藉由X射線繞射裝置(型式:XRD-6100島津製作所製),使用Cu管球進行粉末X射線繞射分析。其結果之粉末X射線繞射圖形係示於圖4。由圖4可明顯得知,化學計量組成之Lu3
Al5
O12
:Ce螢光體之試樣2-(1)、與本發明之實施例的一例之試樣1-(1),其粉末X射線繞射圖形幾乎相同,可知試樣1-(1)維持著鎦‧鋁‧石榴石(LuAG)之構造。
進一步地,為了修正測定時誤差之指標,分別對試樣2-(1)與試樣1-(1),使用添加10質量%氧化釔(Y2
O3
)且充分混合者,來精密地測定於2θ 55°~60°之範圍。並且與以同樣方式僅測定Y2
O3
之數據疊合,特別地,將藉由使用57.5°附近之峰值位置來調整,修正測定時之機械誤差後之X射線繞射圖形示於圖5。由此圖5可明顯得知,相較於化學計量組成之LuAG:Ce螢光體的試樣2-(1),可知本發明之實施例的一例亦即試樣1-(1)雖僅少許,但峰值整體之2θ朝低角度側偏移。
以波長λ之X射線進行粉末X射線繞射時,結晶之晶格面間隔D與繞射角度θ之間具有布拉格方程式D=λ/(2sinθ)之關係式。
峰值位置向低角度側偏移,意指上述式中θ變小,因此結晶之晶格常數變大。
而石榴石構造為金屬離子A,B,C之複合氧化物的一個結晶構造。其一般式係以A3
B2
C3
O12
表示。A在被8個氧圍繞之8配位的位置。B在被6個氧圍繞之6配位的位置。且C在被4個氧圍繞之4配位的位置。鎦‧鋁‧石榴石(LuAG)的情況時,若為化學計量組成,則8配位的位置有Lu3+
、6配位的位置有Al3+
、4配位的位置有Al3+
、當於(Lu+Ce)與Al之平衡中使Al不足量時,在維持石榴石之結晶構造之下,Lu3+
會進入本來Al3+
所在的6配位位置之一部分。如此的現象稱為反位置(anti-position)。因為Lu3+
之離子半徑比Al3+
大,故6配位位置之晶格會擴大,使晶格常數變大。此一事實係與粉末X射線繞射之峰值位置向低角度側偏移、亦即晶格常數變大的事實一致。
再者,此現象亦可由螢光體之發光色的變化來推測。
亦即如本說明書之先前技術中所述,習知之Y3
Al5
O12
:Ce螢光體中,將Al之一部分以離子半徑大的Ga取代後的Y3
(Al,Ga)5
O12
:Ce,其發光色亦比Y3
Al5
O12
:Ce螢光體之發光色更向短波長偏移。此時,Ga3+
係取代上述說明之6配位的Al3+
。Ga3+
之離子半徑亦比Al3+
大,因此6配位之位置的晶格擴大。
推測本發明之螢光體亦如上所述,d值較化學計量組成之0更大,成為Al不足量,Lu3+
會進入本來Al3+
所在的6配位位置之一部分,因此6配位之位置的晶格擴大,即使不使用Ga,結果亦可得到與上述Ga取代同樣之螢光體發光色向短波長偏移的效果。
亦即本發明之特徵為,係可在維持LuAG之石榴石構造,且維持其優良特徵之下,成功地藉由使6配位之位置的晶格擴大,使螢光體之發光波長向短波長側偏移者。
接著,說明本發明之綠色系發光螢光體(Lu1-x
Cex
)3+d
Al5-d
O12
中,將d值固定為0.0968時,Ce之濃度x與螢光體之特性。
如表4所示,除了使Ce濃度、亦即將Lu取代為Ce之量變更以外,係以與前述實施例1中之試樣1-(1)相同的方式製成螢光體,分別稱為試樣3-(1)至試樣3-(9)。
對該等試樣3-(1)至試樣3-(9),亦與實施例1相同地測定主波長、刺激純度、以比較例1為100時的相對發光輝度,同樣地將其結果與試樣1-(1)及試樣1-(2)的結果一起示於表4。
由表4所示之結果,可知藉由使Ce濃度x變化,主波長及相對發光輝度會變化,試樣3-(2)至試樣3-(7)、試樣1-(1)及試樣1-(2)、亦即Ce濃度x為0.005以上、0.14以下之範圍內的試樣,主波長在約554nm至約562nm之範圍、且相對發光輝度亦成為大致70以上。用途或與其他螢光體之組合中,即使相對發光輝度多少較差,然對欲選擇主波長之情況時亦己足夠,因此可適合使用上述Ce濃度x之範圍的試樣。
進一步地,可知Ce濃度x為0.01以上、0.05以下範圍之試樣,相對發光輝度為90以上,而為更佳。
再者,Ce濃度x未達0.005而過小時,發光輝度會進一步降低,又Ce濃度x超過0.14而過大時,發光輝度會顯著降低,而且主波長亦會向長波長側移動。
由以上所述,Ce濃度x較佳為0.005以上、0.14以下;更佳為0.01以上、0.05以下。
已確認此傾向在d=0.0968以外的情況時,亦即d為0.03以上、0.5以下時,亦有同樣的傾向。
由以上所述,可知以(Lu1-x
Cex
)3+d
Al5-d
O12
之式表示、x為0.005≦x≦0.14、且d為0.03≦d≦0.5為特徵的石榴石系綠色系發光螢光體,係為具有在主波長約554nm以上、約562nm附近之範圍具有發光色、且有高發光輝度,高溫時之發光輝度的降低更少之演色性高的半導體發光裝置所必要之優良特性的螢光體。再者,作為更佳之x或d的範圍者,x為0.01≦x≦0.05、d為0.045≦d≦0.2。
本發明之石榴石系綠色系發光螢光體,係具有主波長在約554nm以上、約562nm附近之範圍具有發光色、且具有高發光輝度、高溫時之發光輝度的降低更少之適合於半導體發光裝置的優良特徵,因此能夠適合使用於特別要求演色性或高輸出之半導體發光裝置等。又,本發明之半導體發光裝置,演色性優良、高輸出時輝度亦不易降低,因而特別能夠適合使用於照明用光源或液晶背光用光源等。
10...安裝座部
11...半導體發光元件
12...黏著劑
13a...P型電極
13b、14b、16a、16b...電極部
14a...N型電極
15a、15b...金屬導線
16...印刷配線基板
21...螢光體
30、32...壓模樹脂
101、102...引線框架
圖1為顯示本發明之一實施形態的螢光體之粒度分布之圖。
圖2為顯示本發明之一實施形態的螢光體之發光光譜之圖。
圖3為顯示對本發明之一實施形態的螢光體溫度之輝度維持率的圖。
圖4為本發明之一實施形態的螢光體之粉末X射線繞射圖形。
圖5為本發明之一實施形態的螢光體之粉末X射線繞射圖形中,2θ為55~60°之範圍的詳細圖。
圖6為顯示本發明之一實施形態中之半導體發光裝置的剖面圖。
圖7為顯示本發明之另一實施形態中之半導體發光裝置的剖面圖。
Claims (3)
- 一種石榴石系綠色系發光螢光體,其特徵為:係以(Lu1-x Cex )3+d Al5-d O12 之式表示,且x為0.005≦x≦0.14、d為0.03≦d≦0.5。
- 如申請專利範圍第1項之石榴石系綠色系發光螢光體,其中d為0.045≦d≦0.2。
- 一種半導體發光裝置,其特徵為:至少具備如申請專利範圍第1或2項之石榴石系綠色系發光螢光體與半導體發光元件。
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JPWO2014002722A1 (ja) * | 2012-06-26 | 2016-05-30 | デンカ株式会社 | 蛍光体、発光装置及び照明装置 |
JP2015528187A (ja) * | 2012-07-18 | 2015-09-24 | コーニンクレッカ フィリップス エヌ ヴェ | 混合チャンバ及びリモート蛍光体射出窓を備えた調整可能相関色温度のledベース白色光源 |
JPWO2015129586A1 (ja) * | 2014-02-27 | 2017-03-30 | 京セラ株式会社 | 太陽電池モジュール |
KR101516522B1 (ko) * | 2014-03-11 | 2015-05-04 | 희성금속 주식회사 | 루테튬 가넷계 형광체 및 이를 포함하는 발광장치 |
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CN111286330A (zh) | 2018-12-06 | 2020-06-16 | 松下知识产权经营株式会社 | 荧光体及使用了它的半导体发光装置 |
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CN1169587A (zh) * | 1996-06-28 | 1998-01-07 | 电子科技大学 | 高亮度、高分辨率单晶彩色投影显示管 |
US20060158097A1 (en) * | 2003-03-17 | 2006-07-20 | Thomas Juestel | Illumination system comprising a radiation source and a fluorescent material |
US20100084962A1 (en) * | 2007-03-06 | 2010-04-08 | Merck Patent Gesellschaft | Luminophores made of doped garnet for pcleds |
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US20060158097A1 (en) * | 2003-03-17 | 2006-07-20 | Thomas Juestel | Illumination system comprising a radiation source and a fluorescent material |
US20100084962A1 (en) * | 2007-03-06 | 2010-04-08 | Merck Patent Gesellschaft | Luminophores made of doped garnet for pcleds |
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