TW201502243A - 色彩穩定之紅光磷光體 - Google Patents
色彩穩定之紅光磷光體 Download PDFInfo
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- TW201502243A TW201502243A TW103109499A TW103109499A TW201502243A TW 201502243 A TW201502243 A TW 201502243A TW 103109499 A TW103109499 A TW 103109499A TW 103109499 A TW103109499 A TW 103109499A TW 201502243 A TW201502243 A TW 201502243A
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- temperature
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011737 fluorine Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 12
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 7
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 6
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 230000005855 radiation Effects 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910018287 SbF 5 Inorganic materials 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910020313 ClF Inorganic materials 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 238000002835 absorbance Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 5
- 229910052743 krypton Inorganic materials 0.000 claims 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 claims 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 54
- 235000012431 wafers Nutrition 0.000 description 29
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- 229910052712 strontium Inorganic materials 0.000 description 16
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- 150000002500 ions Chemical class 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910052788 barium Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- -1 fluoride ions Chemical class 0.000 description 7
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- 239000010936 titanium Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 102100032047 Alsin Human genes 0.000 description 1
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- 229910015999 BaAl Inorganic materials 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910017639 MgSi Inorganic materials 0.000 description 1
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- 150000001252 acrylic acid derivatives Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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- C—CHEMISTRY; METALLURGY
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- 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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- C—CHEMISTRY; METALLURGY
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- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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- 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
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/626—Halogenides
- C09K11/628—Halogenides with alkali or alkaline earth metals
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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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/644—Halogenides
- C09K11/645—Halogenides with alkali or alkaline earth metals
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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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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- 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/674—Halogenides
- C09K11/675—Halogenides with alkali or alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7428—Halogenides
- C09K11/7435—Halogenides with alkali or alkaline earth metals
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- 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
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
-
- 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
- H01L33/52—Encapsulations
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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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/181—Metal complexes of the alkali metals and alkaline earth metals
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- 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
- 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
-
- 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
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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)
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Abstract
本發明係關於一種用於合成色彩穩定之Mn4+摻雜磷光體之方法,其包括使呈氣態形式之式I之前體在升溫下與含氟氧化劑接觸以形成該色彩穩定之Mn4+摻雜磷光體Ax[MFy]:Mn4+ I其中A係Li、Na、K、Rb、Cs、NR4或其組合;M係Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或其組合;R係H、低碳烷基或其組合;x係[MFy]離子之電荷之絕對值;且y係5、6或7。
Description
基於錯合氟化物材料之藉由Mn4+活化之紅光磷光體(例如US 7,358,542、US 7,497,973及US 7,648,649中所述之彼等)可與黃/綠光磷光體(例如YAG:Ce或其他石榴石組合物)組合用於自藍色LED獲得暖白光(在黑體部位上CCTs<5000K,演色性指數(CRI)>80),該暖白光等效於藉由電流螢光燈、白熾燈及鹵素燈產生者。該等材料顯著吸收藍光且在約610-635nm之間有效發射且深紅/NIR發射極少。因此,發光效率與在眼睛敏感性不良之較深紅色區具有顯著發射之紅色磷光體相比最大化。在藍色(440-460nm)激發下,量子效率可超過85%。
儘管使用Mn4+摻雜氟化物主體之照明系統之效率及CRI可極高,但一個潛在限制係其在高溫高濕度(HTHH)條件下易於降解。可能使用合成後處理步驟來減少此降解,如US 8,252,613中所述。然而,期望進一步改良材料之穩定性。
簡言之,在一態樣中,本發明係關於合成色彩穩定之Mn4+摻雜磷光體之製程。使式I之前體與呈氣態形式之含氟氧化劑在升溫下接觸以形成色彩穩定之Mn4+摻雜磷光體Ax[MFy]:Mn4+ I
其中A係Li、Na、K、Rb、Cs、NR4或其組合;
M係Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或其組合;R係H、低碳烷基或其組合;x係[MFy]離子之電荷之絕對值;且y係5、6或7。
10‧‧‧照明裝置
12‧‧‧發光二極體晶片
14‧‧‧引線
16‧‧‧引線框
18‧‧‧外殼
20‧‧‧包封劑
22‧‧‧磷光體組合物
24‧‧‧白光
112‧‧‧發光二極體晶片
120‧‧‧包封劑材料
122‧‧‧磷光體組合物
124‧‧‧白光
212‧‧‧發光二極體晶片
218‧‧‧包封
222‧‧‧磷光體組合物
224‧‧‧白光
226‧‧‧輻射
412‧‧‧發光二極體晶片
416‧‧‧引線
420‧‧‧包封劑材料
430‧‧‧反射杯
432‧‧‧導線
550‧‧‧表面安裝器件型發光二極體
552‧‧‧發光窗
554‧‧‧光引導構件
在參考附圖閱讀下文詳細說明時將更好地理解本發明之該等及其他特徵、態樣及優點,其中在所有附圖中相同字符代表相同部分。
圖1係根據本發明一實施例之照明裝置之示意性剖視圖;圖2係根據本發明另一實施例之照明裝置之示意性剖視圖;圖3係根據本發明另一實施例之照明裝置之示意性剖視圖;圖4係根據本發明一實施例之照明裝置之剖面側面透視圖;圖5係表面安裝器件(SMD)背光LED之示意性透視圖。
在本發明製程中,非色彩穩定之前體退火至色彩穩定之磷光體,或經受升溫,同時與含有含氟氧化劑之氣氛接觸。前體係藉由式I之Mn4+活化之錯合氟化物材料。在本發明情況下,術語「錯合氟化物材料或磷光體」意指配位化合物,其含有至少一個由起配位體作用之氟化物離子包圍且視需要由相對離子補償電荷之配位中心。
在一個實例K2SiF6:Mn4+中,配位中心係Si且相對離子係K。錯合氟化物偶爾記錄為簡單二元氟化物之組合,但此一表述不指示配位中心周圍之配位體之配位數。方括號(為簡潔起見偶爾省略)指示,其包括之錯離子係不同於簡單氟化物離子之新化學物質。活化劑離子(Mn4+)亦起配位中心作用,取代主體晶格中心(例如Si)之一部分。主體晶格(包括相對離子)可進一步改變活化劑離子之激發及發射性質。
非色彩穩定之前體具有與非色彩穩定之磷光體類似但終產物缺
少色彩穩定性之標稱組成。式I之Mn4+摻雜前體中及色彩穩定之磷光體中之錳量基於前體或色彩穩定之磷光體之總重量介於約0.5重量%至約0.8重量%範圍內。在高光通量條件下,含有約0.5wt% Mn之K2SiF6:Mn4+在退火之前及之後之色彩穩定性通常高於含有約0.68wt% Mn之K2SiF6:Mn4+在退火之前及之後之色彩穩定性。對於K2SiF6:Mn4+,Mn量介於約0.53wt%至約0.76wt%範圍內,更具體而言約0.65wt%至約0.7wt%範圍內。
在具體實施例中,前體之配位中心(亦即式I中之M)係Si、Ge、Sn、Ti、Zr或其組合。更具體而言,配位中心係Si、Ge、Ti或其組合,且相對離子或式I中之A係Na、K、Rb、Cs或其組合,且y為6。式I之前體之實例包括K2[SiF6]:Mn4+、K2[TiF6]:Mn4+、K2[SnF6]:Mn4+、Cs2[TiF6]、Rb2[TiF6]、Cs2[SiF6]、Rb2[SiF6]、Na2[TiF6]:Mn4+、Na2[ZrF6]:Mn4、K3[ZrF7]:Mn4+、K3[BiF6]:Mn4+、K3[YF6]:Mn4+、K3[LaF6]:Mn4+、K3[GdF6]:Mn4+、K3[NbF7]:Mn4+、K3[TaF7]:Mn4+。在具體實施例中,式I之前體係K2SiF6:Mn4+。
儘管發明者不希望受限於用任何具體理論來解釋可自使前體經受本發明製程而獲得之色彩穩定性之改良,但假定前體可含有諸如以下等缺陷:差排、F-空位、陽離子空位、Mn3+離子或提供非輻射重組路徑之表面或間隙H+/OH-基團,且該等缺陷可藉由在升溫下暴露於氧化劑中來彌補或移除。
使前體與含氟氧化劑接觸之溫度在接觸期間可介於約200℃至約500℃範圍內,具體而言在約350℃至約450℃範圍內。在本發明之各個實施例中,該溫度為至少100℃,具體而言約225℃,且更具體而言約350℃。使磷光體前體與氧化劑接觸足夠長時間段以將該前體轉化為色彩穩定之磷光體。時間與溫度相互關聯且可一起調節,例如,在延長時間的同時降低溫度,或在升高溫度的同時縮短時間。在具體實
施例中,時間為至少2小時,具體而言至少4小時,更具體而言至少6小時,且最具體而言至少8小時。在特定實施例中,使前體與氧化劑在至少250℃下接觸至少8小時時間,例如在約250℃下接觸約4小時,隨後在約350℃溫度下接觸約4小時。
含氟氧化劑可為F2、HF、BrF5、NH4HF2、NH4F、KF、AlF3、SbF5、ClF3、BrF3 SbF5、KrF、XeF2、XeF4、NF3或其組合。在具體實施例中,含氟氧化劑係F2。可具體而言結合時間及溫度之改變來改變氣氛中氧化劑之量以獲得色彩穩定之磷光體。倘若含氟氧化劑係F2,則氣氛可包括至少0.5% F2,但在一些實施例中較低濃度可有效。具體而言,氣氛可包括至少5% F2,更具體而言至少20% F2,且甚至更具體而言至少35% F2。氣氛可另外包括與氟氣呈任一組合之氮、氦、氖、氬、氮、氙。在具體實施例中,氣氛由約20% F2及約80%氮組成。
使前體與含氟氧化劑接觸之方式無關緊要且可以任何足以將前體轉化為具有期望性質之色彩穩定之磷光體之方式來完成。在一些實施例中,可向含有前體之室投藥然後將其密封以使得在加熱室時產生超壓,且在其他實施例中,在整個退火製程中使氟氮混合物流動以確保更均勻的壓力。在一些實施例中,可在一段時間後引入另一劑量之含氟氧化劑。
在本發明製程中退火之磷光體之色彩穩定性及量子效率可藉由用式II組合物於水性氫氟酸中之飽和溶液處理呈微粒形式之磷光體來增強,如US 8,252,613中所述。
Ax[MFy]II
使磷光體與該溶液接觸之溫度介於約20℃至約50℃範圍內。產生色彩穩定之磷光體所需之時間段介於約1分鐘至約5小時範圍內,具
體而言在約5分鐘至約1小時範圍內。氫氟酸於HF水溶液中之濃度介於約20% w/w至約70% w/w範圍內,具體而言在約40% w/w至約70% w/w範圍內。較低濃度之溶液可降低磷光體之產率。
根據本發明一實施例之照明裝置或發光總成或燈10顯示於圖1中。照明裝置10包括顯示為發光二極體(LED)晶片12之半導體輻射源及電連接至LED晶片之引線14。引線14可為由較粗引線框16支撐之細線,或引線可為自支撐電極且可省略引線框。引線14向LED晶片12提供電流且由此使其發射輻射。
燈可包括任何半導體藍色或UV光源,該光源在其所發射輻射被引導至磷光體上時能產生白光。在一實施例中,半導體光源係摻雜有各種雜質之藍光LED。因此,LED可包含基於任何適宜III-V、II-VI或IV-IV半導體層且發射波長為約250至550nm之半導體二極體。具體而言,LED可含有至少一個包含GaN、ZnSe或SiC之半導體層。舉例而言,LED可包含由式IniGajAlkN(其中0i;0j;0k且I+j+k=1)表示之發射波長大於約250nm且小於約550nm之氮化物化合物半導體。在具體實施例中,晶片係峰值發射波長為約400至約500nm之近uv或藍光LED。該等LED半導體為業內已知。為方便起見,輻射源在本文中闡述為LED。然而,如本文所用之該術語意欲涵蓋所有半導體輻射源,包括(例如)半導體雷射二極體。此外,儘管本文所論述發明之實例性結構之一般論述係關於基於無機LED之光源,但應理解,除非另外說明,否則可用另一輻射源替代LED晶片,且對半導體、半導體LED或LED晶片之任何提及僅代表任何適當輻射源,包括(但不限於)有機發光二極體。
在照明裝置10中,磷光體組合物22輻射性耦合至LED晶片12。輻射性耦合意指元件彼此結合,因此輻射從一個元件傳送至另一元件。藉由任何適當方法將磷光體組合物22沈積在LED 12上。舉例而言,
可形成磷光體之基於水之懸浮液,且作為磷光體層施加至LED表面。在一種所述方法中,將磷光體顆粒隨機懸浮於其中之聚矽氧漿液置於LED周圍。此方法僅例示磷光體組合物22及LED 12之可能位置。因此,可藉由在LED晶片12上方塗佈並乾燥磷光體懸浮液將磷光體組合物22塗佈於LED晶片12之發光表面上方或直接塗佈於該表面上。在基於聚矽氧之懸浮液之情形中,在適當溫度下使懸浮液硬化。外殼18及包封劑20應透明以容許白光24傳送穿過彼等元件。儘管不欲加以限制,但在一些實施例中,磷光體組合物之中值粒徑介於約1至約50微米範圍內,具體而言介於約15至約35微米範圍內。
在其他實施例中,將磷光體組合物22散佈在包封劑材料20內,而非直接在LED晶片12上形成。可將磷光體(呈粉末形式)散佈在包封劑材料20之單一區域內或遍及包封劑材料之整個體積。LED晶片12發射之藍光與磷光體組合物22發射之光混合,且混合光表現為白光。若欲將磷光體散佈在包封劑20之材料內,則可將磷光體粉末添加至聚合物或聚矽氧前體中,加載在LED晶片12周圍,然後可使聚合物前體硬化以固化聚合物或聚矽氧材料。亦可使用其他已知磷光體散佈方法,例如轉移加載。
在一些實施例中,包封劑材料20係具有折射率R之聚矽氧基質,且除了磷光體組合物22以外含有吸光度低於約5%且折射率為R±0.1之稀釋劑材料。稀釋劑材料之折射率為1.7,具體而言1.6,且更具體而言1.5。在具體實施例中,稀釋劑材料具有式II,且折射率為約1.4。將無光學活性之材料添加至磷光體/聚矽氧混合物可產生跨越帶之更平穩之通量分佈且可減少對磷光體之損傷。適用於稀釋劑之材料包括立方晶系(cubic)氟化物化合物,例如LiF、MgF2、CaF2、SrF2、AlF3、K2NaAlF6、KMgF3、CaLiAlF6、KLiAlF6及K2SiF6,其折射率介於約1.38(AlF3及K2NaAlF6)至約1.43(CaF2)範圍內;以及聚合物,其
折射率介於約1.254至約1.7範圍內。適合用作稀釋劑之聚合物之非限制性實例包括聚碳酸酯、聚酯、耐侖(nylon)、聚醚醯亞胺、聚醚酮以及衍生自苯乙烯、丙烯酸酯、甲基丙烯酸酯、乙烯基、乙酸乙烯酯、乙烯、環氧丙烷及環氧乙烷單體之聚合物,及其共聚物(包括鹵化及未鹵化衍生物)。可在聚矽氧硬化之前將該等聚合物粉末直接納入聚矽氧包封劑中。
在另一實施例中,將磷光體組合物22塗佈至外殼18之表面上,而非在LED晶片12上方形成。較佳將磷光體組合物塗佈在外殼18之內表面上,但若期望,可將磷光體塗佈在外殼之外表面上。可將磷光體組合物22塗佈在外殼之整個表面上或僅塗佈在外殼表面之頂部部分上。LED晶片12發射之UV/藍光與磷光體組合物22發射之光混合,且所混合光表現為白光。當然,磷光體可位於任何兩個或所有三個位置或位於任一其他適宜位置,例如與外殼分離或整合至LED中。
圖2圖解說明本發明系統之第二種結構。除非另外指明,否則圖1-4中之相應編號(例如圖1中之12及圖2中之112)係指每一圖式中之相應結構。圖2中實施例之結構類似於圖1,但磷光體組合物122散佈在包封劑材料120內,而非直接在LED晶片112上形成。可將磷光體(呈粉末形式)散佈在包封劑材料之單一區域內或遍及包封劑材料之整個體積。LED晶片112發射之輻射(由箭頭126指示)與磷光體122發射之光混合,且所混合光表現為白光124。若欲將磷光體散佈在包封劑材料120內,則可將磷光體粉末添加至聚合物前體中,且加載於LED晶片112周圍。然後可使聚合物或聚矽氧前體硬化以固化聚合物或聚矽氧。亦可使用其他已知磷光體散佈方法,例如轉移模製。
圖3圖解說明本發明系統之第三種可能的結構。圖3中所示實施例之結構類似於圖1,但將磷光體組合物222塗佈至包封218之表面上,而非在LED晶片212上方形成。較佳將磷光體組合物222塗佈在包
封218之內表面上,但若期望可將磷光體塗佈在包封之外表面上。可將磷光體組合物222塗佈在包封之整個表面上,或僅塗佈在包封表面之頂部部分上。LED晶片212發射之輻射226與磷光體組合物222發射之光混合,且所混合光表現為白光224。當然,可組合圖1-3之結構,且磷光體可位於任何兩個或所有三個位置或位於任一其他適宜位置,例如與包封分離或整合至LED中。
在上述結構中之任一者中,燈亦可包括複數個嵌入包封劑材料中之散射顆粒(未顯示)。散射顆粒可包含(例如)氧化鋁或氧化鈦。散射顆粒有效散射自LED晶片發射之定向光,吸收之量較佳可忽略不計。
如圖4中之第四種結構所示,可將LED晶片412安裝在反射杯430中。杯430可由介電材料製成或經該材料塗佈(例如氧化鋁、氧化鈦或業內已知之其他介電粉末)或可經反射金屬(例如鋁或銀)塗佈。圖4中實施例之結構之其餘部分與先前圖式中之任一者相同,且可包括兩根引線416、導線432及包封劑材料420。反射杯430係由第一引線416支撐且使用導線432來電連接LED晶片412與第二引線416。
另一結構(尤其對於背光應用)係表面安裝器件(「SMD」)型發光二極體550,例如如圖5中所圖解說明。此SMD係「側面發射型」且在光引導構件554之突出部分上具有發光窗552。SMD包裝可包含如上文所定義之LED晶片及藉由自LED晶片發射之光激發之磷光體材料。
在與350至550nm之LED發射及一或多種其他適當磷光體一起使用時,所得照明系統將產生具有白色之光。燈10亦可包括嵌入包封劑材料中之散射顆粒(未顯示)。散射顆粒可包含(例如)氧化鋁或氧化鈦。散射顆粒有效散射自LED晶片發射之定向光,吸收之量較佳可忽略不計。
除了色彩穩定之Mn4+摻雜磷光體以外,磷光體組合物22可包括
一或多種其他磷光體。在與約250至550nm範圍內之藍光或近UV LED發射輻射組合用於照明裝置中時,總成發射之所得光將為白光。可在摻合物中使用其他磷光體(例如綠色、藍色、橙色或其他色彩之磷光體)以定製所得光之白色並產生較高CRI來源。
適用於磷光體組合物22中之磷光體包括(但不限於):((Sr1-z(Ca,Ba,Mg,Zn)z)1-(x+w)(Li,Na,K,Rb)wCex)3(Al1-ySiy)O4+y+3(x-w)F1-y-3(x-w),0<x0.10,0y0.5,0z0.5,0wx;(Ca,Ce)3Sc2Si3O12(CaSiG);(Sr,Ca,Ba)3Al1-xSixO4+xF1-x:Ce3+((Ca,Sr,Ce)3(Al,Si)(O,F)5(SASOF));(Ba,Sr,Ca)5(PO4)3(Cl,F,Br,OH):Eu2+,Mn2+;(Ba,Sr,Ca)BPO5:Eu2+,Mn2+;(Sr,Ca)10(PO4)6*νB2O3:Eu2+(其中0<ν1);Sr2Si3O8*2SrCl2:Eu2+;(Ca,Sr,Ba)3MgSi2O8:Eu2+,Mn2+;BaAl8O13:Eu2+;2SrO*0.84P2O5*0.16B2O3:Eu2+;(Ba,Sr,Ca)MgAl10O17:Eu2+,Mn2+;(Ba,Sr,Ca)Al2O4:Eu2+;(Y,Gd,Lu,Sc,La)BO3:Ce3+,Tb3+;ZnS:Cu+,Cl-;ZnS:Cu+,Al3+;ZnS:Ag+,Cl-;ZnS:Ag+,Al3+;(Ba,Sr,Ca)2Si1-ξO4-2ξ:Eu2+(其中0ξ0.2);(Ba,Sr,Ca)2(Mg,Zn)Si2O7:Eu2+;(Sr,Ca,Ba)(Al,Ga,In)2S4:Eu2+;(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+(其中0α0.5);(Ca,Sr)8(Mg,Zn)(SiO4)4Cl2:Eu2+,Mn2+;Na2Gd2B2O7:Ce3+,Tb3+;(Sr,Ca,Ba,Mg,Zn)2P2O7:Eu2+,Mn2+;(Gd,Y,Lu,La)2O3:Eu3+,Bi3+;(Gd,Y,Lu,La)2O2S:Eu3+,Bi3+;(Gd,Y,Lu,La)VO4:Eu3+,Bi3+;(Ca,Sr)S:Eu2+,Ce3+;SrY2S4:Eu2+;CaLa2S4:Ce3+;(Ba,Sr,Ca)MgP2O7:Eu2+,Mn2+;
(Y,Lu)2WO6:Eu3+,Mo6+;(Ba,Sr,Ca)βSiγNμ:Eu2+(其中2β+4γ=3μ);Ca3(SiO4)Cl2:Eu2+;(Lu,Sc,Y,Tb)2-u-vCevCa1+uLiwMg2-wPw(Si,Ge)3-wO12-u/2(其中-0.5u1,0<v0.1,且0w0.2);(Y,Lu,Gd)2-φCaφSi4N6+φC1-φ:Ce3+,(其中0φ0.5);經Eu2+及/或Ce3+摻雜之(Lu,Ca,Li,Mg,Y),α-SiAlON;(Ca,Sr,Ba)SiO2N2:Eu2+,Ce3+;3.5MgO*0.5MgF2*GeO2:Mn4+;Ca1-c-fCecEufAl1+cSi1-cN3,(其中0c0.2,0f0.2);Ca1-h-rCehEurAl1-h(Mg,Zn)hSiN3,(其中0h0.2,0r0.2);Ca1-2s-tCes(Li,Na)sEutAlSiN3,(其中0s0.2,0f0.2,s+t>0);及Ca1-σ-χ-ΦCeσ(Li,Na)χEuΦAl1+σ-χSi1-σ+χN3,(其中0σ0.2,0χ0.4,0Φ0.2)。
磷光體摻合物之每一個別磷光體之比率可端視期望光輸出之特徵而變化。在各個實施例磷光體摻合物中,可調節個別磷光體之相對比例以使得在摻和其發射並用於LED照明器件時,產生在CIE色度圖上具有預定x及y值之可見光。如所陳述,較佳產生白光。此白光可(例如)具有在約0.30至約0.55範圍內之x值及在約0.30至約0.55範圍內之y值。然而,如所陳述,磷光體組合物中每一磷光體之確切身份及數量可根據最終使用者之需要而變化。舉例而言,材料可用於意欲用於液晶顯示器(LCD)背光之LED。在此應用中,在通過LCD/濾色器組合後將基於期望的白色、紅色、綠色及藍色適當地調諧LED色點。
本發明之色彩穩定之Mn4+摻雜磷光體可用於除了上文所述應用以外之應用中。舉例而言,材料可用作螢光燈、陰極射線管、電漿顯示器件或液晶顯示器(LCD)中之磷光體。材料亦可用作電磁熱量計、γ射線照相機、電腦斷層攝影掃描儀或雷射中之閃爍體。該等用途僅為實例性且無限制性。
樣品係藉由將500mg欲測試材料與1.50g聚矽氧(Sylgard 184)混合來製備。將混合物在真空室中脫氣約15分鐘。將混合物(0.70g)傾倒至碟狀模板(直徑為28.7mm且厚0.79mm)中並在90℃下烘焙30分鐘。將樣品切成5×5mm2方塊用於測試。
將在446nm發射之雷射二極體耦合至光學纖維,在該光學纖維之另一端具有準直儀。功率輸出為310mW且在樣品處之光束直徑為700微米。此等效於樣品表面上80W/cm2之通量。用1米(直徑)積分球收集作為來自雷射之散射輻射與來自激發磷光體之發射之組合之光譜功率分佈(SPD)光譜,並用光譜儀軟體(Specwin)處理數據。以2分鐘間隔記錄(藉由分別積分來自400nm至500nm及550nm至700nm之SPD)來自雷射及磷光體發射之積分功率。棄去最初90分鐘之量測以避免因雷射之熱穩定所致之效應。由於雷射損傷所致之強度損失之百
分比計算如下:
儘管僅繪製來自磷光體之射極功率,但監測來自雷射發射之積分功率以及其峰位置以確保雷射在實驗期間保持穩定(變化小於1%)。
用於高溫高濕度(HTHH)處理之樣品係藉由將磷光體粉末以0.9g磷光體對0.825g聚矽氧(部分A+B)之比率混合至兩部分式甲基聚矽氧黏合劑(RTV-615,Momentive Performance Materials)中來製造。然後將磷光體/聚矽氧混合物傾倒至鋁樣品保持器中並在90℃下硬化20分
鐘。將對照樣品儲存在氮下,且將用於暴露至HTHH條件之樣品置入85℃/85% RH受控氣氛室中。定期移除該等HTHH樣品並將其在450nm激發下之發光強度與對照樣品相比較。
將基於前體材料之總重量含有0.68wt% Mn之Mn摻雜之氟矽酸鉀(PFS:Mn)前體(K2SiF6:Mn,Shin-Etsu Chemical)置於爐室中。使用機械幫浦排空爐室並用氮及氮、氟混合物多次掃氣。在多個抽吸及掃氣循環後,用含有氟氣及氮氣之氣氛將爐室填充至約1個大氣壓之壓力。然後將該室加熱至期望退火溫度。在保持期望時間長度後,將該室冷卻至室溫。排空氟氮混合物,將該室用氮填充並掃氣若干次以確保在開啟該室之前完全移除氟氣。
對於實例1-5,該室中之氣氛係由20%氟氣及80%氮氣組成。對於實例6,氣氛係由5%氟氣及95%氮氣組成。第一退火階段之溫度及時間(T1及t1)以及第二退火階段(若存在)之溫度及時間(T2及t2)指示於表1中。
在高光通量條件下測試Mn wt%介於0.68-0.73wt%範圍內之前體PFS:Mn及產物磷光體之穩定性,且結果顯示於表1中。退火材料經歷之損傷顯著小於未經熱處理之材料。
藉由將粉末(約10g)置於含有100mL K2SiF6之飽和溶液(首先藉由在室溫下在40% HF中添加約17g K2SiF6,攪拌並過濾溶液來製造)之Teflon燒杯中來用K2SiF6之飽和溶液處理實例2之退火PFS磷光體粉末。緩慢攪拌懸浮液,且過濾殘留物並在真空下乾燥。藉由在丙酮中洗滌3-5次並將濾液加熱至100℃且保持10min自經乾燥濾液進一步移除HF。在HHTH條件下在85℃/85%RH下經620小時測試後處理磷光體以及未經退火但經後處理之PFS樣品之穩定性。後處理樣品在高溫/高濕度條件下經歷較少降解,從而維持約94%發射強度,而未退火樣品維持約86%發射強度。
將K2SiF6:Mn(Shin-Etsu Chemical)(0.68wt% Mn)與聚矽氧前體混合並形成為由87.8體積%聚矽氧及12.2體積% PFS組成之固體帶。對照含有K2SiF6:Mn(0.68wt% Mn)(經摻雜PFS)與K2SiF6(0wt% Mn)(未摻雜PFS)之1:1混合物,最終組成為75.6 vol%聚矽氧、12.2%未摻雜PFS及12.2 vol%經摻雜PFS。
使該等帶在高光通量條件下經受穩定性測試。在24小時後,稀釋PFS樣品之功率強度損失為約2.5%,且顯著低於對照之損失。
在高光通量條件下測試基於前體材料之總重量含有0.53wt% Mn之Mn摻雜之氟矽酸鉀(PFS:Mn)前體(K2SiF6:Mn,Shin-Etsu Chemical),且結果顯示於表2中。退火材料經歷之損傷顯著小於未經熱處理之對照。
儘管本文中僅闡釋並說明本發明之某些特徵,但熟習此項技術者將想出多種修改及變化。因此,應理解,隨附申請專利範圍意欲涵蓋所有落在本發明之真實精神內之該等修改及變化。
10‧‧‧照明裝置
12‧‧‧發光二極體晶片
14‧‧‧引線
16‧‧‧引線框
18‧‧‧外殼
20‧‧‧包封劑
22‧‧‧磷光體組合物
24‧‧‧白光
Claims (33)
- 一種用於合成色彩穩定之Mn4+摻雜磷光體之方法,該方法包含使式I之前體Ax[MFy]:Mn4+ I在升溫下與呈氣態形式之含氟氧化劑接觸以形成該色彩穩定之Mn4+摻雜磷光體;其中A係Li、Na、K、Rb、Cs、NR4或其組合;M係Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或其組合;R係H、低碳烷基或其組合;x係[MFy]離子之電荷之絕對值;且y係5、6或7。
- 如請求項1之方法,其中該含氟氧化劑係F2、無水HF、BrF5、NH4HF2、NH4F、AlF3、SbF5、ClF3、BrF3 SbF5、KrF、XeF2、XeF4、NF3或其組合。
- 如請求項1之方法,其中該含氟氧化劑係F2。
- 如請求項1之方法,其中該溫度為至少100℃。
- 如請求項1之方法,其中該溫度為至少350℃。
- 如請求項1之方法,其中該溫度為至少225℃。
- 如請求項1之方法,其中該溫度介於約200℃至約500℃範圍內。
- 如請求項1之方法,其中該溫度介於約350℃至約450℃範圍內。
- 如請求項1之方法,其中使該磷光體前體與反應物接觸至少2小時時間。
- 如請求項1之方法,其中使該磷光體前體與反應物接觸至少4小 時時間。
- 如請求項1之方法,其中使該磷光體前體與反應物接觸至少約6小時時間。
- 如請求項1之方法,其中使該磷光體前體與反應物接觸約8小時時間。
- 如請求項1之方法,其中使該磷光體前體與反應物在至少250℃溫度下接觸至少8小時時間。
- 如請求項1之方法,其中該溫度最初為約250℃並保持約4小時,然後為約350℃並保持約4小時。
- 如請求項1之方法,其中該氣氛包含至少0.5%氟。
- 如請求項1之方法,其中該氣氛包含至少5%氟。
- 如請求項1之方法,其中該氣氛包含至少20%氟。
- 如請求項1之方法,其中該氣氛包含至少35%氟。
- 如請求項1之方法,其中該氣氛另外包含氮、氦、氖、氬、氪、氙或其組合。
- 如請求項1之方法,其中該氣氛包含約20%氟及約80%氮。
- 如請求項1之方法,其中M係Si、Ge、Sn、Ti、Zr或其組合。
- 如請求項1之方法,其中A係Na、K、Rb、Cs或其組合;M係Si、Ge、Ti或其組合;且Y為6。
- 如請求項1之方法,其中該磷光體前體係K2SiF6:Mn4+。
- 如請求項1之方法,其使該磷光體前體與包含氟氣之氣氛在約250℃溫度下接觸至少4小時時間,然後在約350℃溫度下接觸至少4小時時間。
- 如請求項1之方法,其另外包含使呈微粒形式之該色彩穩定之 Mn4+摻雜磷光體與式II組合物於水性氫氟酸中之飽和溶液接觸Ax[MFy];II。
- 如請求項26之方法,其中該接觸步驟係在介於約20℃至約50℃範圍內之溫度下實施。
- 如請求項26之方法,其中該接觸步驟係實施介於約1分鐘至約5小時範圍內之時間。
- 如請求項26之方法,其中該時間介於約5分鐘至約1小時範圍內。
- 一種色彩穩定之Mn4+摻雜磷光體,其係藉由如請求項1至29中任一項之方法來製備。
- 一種照明裝置,其包含半導體光源;及如請求項1至29中任一項之方法製備之色彩穩定之Mn4+摻雜磷光體。
- 一種照明裝置,其包含半導體光源;及輻射地耦合至該光源且分散於具有折射率R之聚矽氧基質中之磷光體摻合物;其中該磷光體摻合物包含式I之Mn4+摻雜磷光體Ax[MFy]:Mn4+ I及吸光度小於約5%且折射率為R±0.1之稀釋劑材料;其中A係Li、Na、K、Rb、Cs、NR4或其組合;M係Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Y、La、Nb、Ta、Bi、Gd或其組合; R係H、低碳烷基或其組合;x係[MFy]離子之電荷之絕對值;且y係5、6或7。
- 如請求項32之照明裝置,其中該稀釋劑材料之折射率為1.7。
- 如請求項31之照明裝置,其中該稀釋劑材料具有式II Ax[MFy]II。
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TWI616515B (zh) * | 2015-09-10 | 2018-03-01 | 英特曼帝克司公司 | 用於一般照明與顯示器背光源之磷光體轉換白光發光裝置及光致發光化合物 |
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