CN105189696B - 颜色稳定的发射红色的磷光体 - Google Patents
颜色稳定的发射红色的磷光体 Download PDFInfo
- Publication number
- CN105189696B CN105189696B CN201480028317.4A CN201480028317A CN105189696B CN 105189696 B CN105189696 B CN 105189696B CN 201480028317 A CN201480028317 A CN 201480028317A CN 105189696 B CN105189696 B CN 105189696B
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- Prior art keywords
- phosphor
- combinations
- doping
- oxidiser
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 38
- 239000011737 fluorine Substances 0.000 claims abstract description 38
- 239000007800 oxidant agent Substances 0.000 claims abstract description 30
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 16
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 11
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910020440 K2SiF6 Inorganic materials 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 14
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910003202 NH4 Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 2
- 229910014263 BrF3 Inorganic materials 0.000 claims description 2
- 229910014271 BrF5 Inorganic materials 0.000 claims description 2
- 229910020323 ClF3 Inorganic materials 0.000 claims description 2
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 2
- 229910004014 SiF4 Inorganic materials 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- XHVUVQAANZKEKF-UHFFFAOYSA-N bromine pentafluoride Chemical compound FBr(F)(F)(F)F XHVUVQAANZKEKF-UHFFFAOYSA-N 0.000 claims description 2
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 2
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 2
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 0.000 claims description 2
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- IGELFKKMDLGCJO-UHFFFAOYSA-N xenon difluoride Chemical compound F[Xe]F IGELFKKMDLGCJO-UHFFFAOYSA-N 0.000 claims description 2
- RPSSQXXJRBEGEE-UHFFFAOYSA-N xenon tetrafluoride Chemical compound F[Xe](F)(F)F RPSSQXXJRBEGEE-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 41
- 239000011572 manganese Substances 0.000 description 36
- 229920001296 polysiloxane Polymers 0.000 description 18
- 239000000523 sample Substances 0.000 description 15
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- 238000000137 annealing Methods 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
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- 150000002500 ions Chemical class 0.000 description 9
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- 229910004074 SiF6 Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
- -1 KrF Chemical compound 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910020826 NaAlF6 Inorganic materials 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910003564 SiAlON Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
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- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
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- 238000010129 solution processing Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical class C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000120527 Kemerovo virus Species 0.000 description 1
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
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- 229920002098 polyfluorene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 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
-
- 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
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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
- C09K11/61—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
-
- 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
- C09K11/62—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
-
- 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
- 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
- C09K11/67—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
-
- 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
- C09K11/74—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
用于合成颜色稳定的掺杂Mn4+的磷光体的方法,所述方法包括在升高的温度下使式I的前体与含氟氧化剂以气态形式接触,以形成颜色稳定的掺杂Mn4+的磷光体Ax[MFy]:Mn4+(I),其中A为Li、Na、K、Rb、Cs、NR4或它们的组合;M为Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;R为H、低级烷基或它们的组合;x为[MFy]离子电荷的绝对值;且y为5、6或7。
Description
背景
基于通过Mn4+活化的络合氟化物材料的发射红色的磷光体,例如描述于US7358542、US7497973和US7648649中的那些,可与发射黄色/绿色的磷光体例如YAG:Ce或其它石榴石组合物组合使用,以从蓝色LED获得热白光(黑体轨迹上的CCTs<5000K,显色指数(CRI)>80),等于通过电流荧光、白炽灯和卤素灯产生的光。这些材料强烈地吸收蓝光并有效地在约610-635nm之间发射,带有少量的深红色/NIR发射。因此,相较于在低视觉灵敏度的深红色中具有显著发射的红色磷光体,所述材料的发光效能被最大化。在蓝色(440-460nm)激发下,量子效率可超过85%。
虽然使用掺杂Mn4+的氟化物主体的照明系统的效能和CRI可相当高,但一个潜在性限制在于它们在高温高湿(HTHH)条件下对降解的敏感度。使用合成后加工步骤可减少这种降解,如US8252613中所描述。然而,期望进一步改进材料的稳定性。
简述
简而言之,一方面,本发明涉及用于合成颜色稳定的掺杂Mn4+的磷光体的方法。式I的前体与含氟氧化剂以气态形式在升高的温度下接触,以形成颜色稳定的掺杂Mn4+的磷光体。
Ax[MFy]:Mn4+
I
其中
A为Li、Na、K、Rb、Cs、NR4或它们的组合;
M为Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;
R为H、低级烷基或它们的组合;
x为[MFy]离子电荷的绝对值;和
y为5、6或7。
在另一方面,本发明涉及可通过所述方法生产的颜色稳定的掺杂Mn4+的磷光体。
附图
当参考附图阅读以下详述时,将更好地理解本发明的这些和其它特点、方面和优点,附图中相似的字符表示的相似的部件,其中:
图1为依照本发明的一个实施方案的照明设备的截面示意图。
图2为依照本发明的另一个实施方案的照明设备的截面示意图。
图3为依照本发明的再一个实施方案的照明设备的截面示意图。
图4为依照本发明的一个实施方案的照明设备的剖面侧透视图。
图5为表面安装式装置(SMD)背光LED的透视示意图。
详述
在根据本发明的方法中,使颜色稳定磷光体的非颜色稳定前体退火,或经受升高的温度,同时与含有含氟氧化剂的气氛接触。所述前体为式I的由Mn4+活化的络合氟化物材料。在本发明上下文中,术语“络合氟化物材料或磷光体”,表示含有至少一个配位中心的配位化合物,所述配位中心由作为配体的氟化物离子环绕,并按需由反离子电荷补偿。在一个实例中,K2SiF6:Mn4+的配位中心为Si,且反离子为K。偶尔将络合氟化物写为简单的二元氟化物的组合,但这种表述不表明围绕配位中心的配体的配位数。方括号(为了简单而偶尔忽略)表明它们包括的络合离子是不同于简单氟化物离子的新化学物类。活化剂离子(Mn4+)还作为取代主体晶格中心(例如,硅)的一部分的配位中心。所述主体晶格(包括反离子)可进一步改良活化剂离子的激发和发射性质。
非颜色稳定的前体具有与颜色稳定的磷光体类似的名义组成,但缺乏成品的颜色稳定性。在掺杂Mn4+的式I的前体和颜色稳定的磷光体中锰的量的范围为约0.3重量%-约1.5重量%,基于所述前体或颜色稳定的磷光体的总重量。含有约0.5重量%Mn的K2SiF6:Mn4+在退火前后在高光通量条件下一般比含有约0.68重量%Mn的K2SiF6:Mn4+在退火前后更具颜色稳定性。对于K2SiF6:Mn4+,Mn的量的范围为约0.50重量%-约0.85重量%,更具体地为0.65重量%-约0.75重量%。
在特定的实施方案中,所述前体的配位中心,即式I中的M,为Si、Ge、Sn、Ti、Zr或它们的组合。更特别地,所述配位中心为Si、Ge、Ti或它们的组合,并且所述反离子,或式I中的A,为Na、K、Rb、Cs或它们的组合,且y为6。式I的前体的实例包括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+。在特定的实施方案中,式I的前体为K2SiF6:Mn4+。
虽然发明人不希望限于任何特定的理论来解释由于使所述前体经受根据本发明的过程可引起的颜色稳定性的改进,但假定所述前体可含有缺陷,例如位错、F-空穴、阳离子空穴、Mn3+离子、Mn2+离子、OH-替换F-、或提供非辐射再组合途径的表面或空隙的H+/OH-基团,并通过在升高的温度下将它们暴露于氧化剂来使它们复原或除去。
前体与含氟氧化剂接触时所处的温度范围可为约200℃-约700℃,特别是在接触期间为约350℃-约600℃,并且在一些实施方案中为约200℃-约700℃。在本发明的多个实施方案中,温度为至少100℃,特别地为至少225℃,且更特别地为至少350℃。使磷光体前体与氧化剂接触经足以将它转化为颜色稳定的磷光体的一段时间。时间与温度相互关联,并且可被同时调节,例如,增加时间的同时降低温度,或提高温度的同时减少时间。在特别的实施方案中,时间为至少1小时,特别是至少4小时,更特别为至少6小时,且最特别为至少8小时。在具体的实施方案中,使前体与氧化剂接触经至少8小时的时段,且温度为至少250℃,例如,在约250℃下经约4小时并随后在约350℃的温度下经约4小时。
所述含氟氧化剂可以为F2、HF、SF6、BrF5、NH4HF2、NH4F、KF、AlF3、SbF5、ClF3、BrF3、KrF、XeF2、XeF4、NF3、SiF4、PbF2、ZnF2、SnF2、CdF2或它们的组合。在特别的实施方案中,所述含氟氧化剂为F2。可改变气氛中氧化剂的量,特别是结合时间和温度的改变,以获得颜色稳定的磷光体。在含氟氧化剂为F2的情况中,气氛可包括至少0.5%的F2,尽管在一些实施方案中,较低浓度可有效。特别地,气氛可包括至少5%的F2且更特别地为至少20%的F2。气氛可另外地包括氮、氦、氖、氩、氪、氙与含氟氧化剂的任何组合。在特别的实施方案中,气氛由约20%的F2和约80%的氮组成。
使前体与含氟氧化剂接触的方式并非关键的,并且可按足以将前体转换为具有期望性质的颜色稳定的磷光体的任何方式来完成。在一些实施方案中,可向含有前体的室加料并随后密封,使得当加热室时增进过压,在其它实施方案中,氟和氮的混合物始终在退火过程中流动,以保证更加均匀的压力。在一些实施方案中,可在一段时间后引入另外剂量的含氟氧化剂。
在另一方面,本发明涉及用于合成颜色稳定的掺杂Mn4+的磷光体的方法,所述方法包括在升高的温度下使前体与含氟氧化剂以气态形式接触,以形成颜色稳定的掺杂Mn4+的磷光体,其中所述前体选自以下:
(A) A2[MF5]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;且其中M选自Al、Ga、In和它们的组合;
(B) A3[MF6]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;且其中M选自Al、Ga、In和它们的组合;
(C) Zn2[MF7]:Mn4+,其中M选自Al、Ga、In和它们的组合;
(D) A[ln2F7]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;
(E) A2[MF6]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;且其中M选自Ge、Si、Sn、Ti、Zr和它们的组合;
(F) E[MF6]:Mn4+,其中E选自Mg、Ca、Sr、Ba、Zn和它们的组合;且其中M选自Ge、Si、Sn、Ti、Zr和它们的组合;
(G) Ba0.65Zr0.35F2.70:Mn4+;和
(H) A3[ZrF7]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4;和
(I) 它们的组合。
以上描述所述方法中使用的时间、温度和含氟氧化剂。
可通过在含水氢氟酸中使用式II
Ax[MFy]
II
的组合物的饱和溶液处理颗粒形式的磷光体来提高在根据本发明的方法中退火的磷光体的颜色稳定性和量子效率,如描述于US8252613。磷光体与溶液接触时所处的温度范围为约20℃-约50℃。产生颜色稳定的磷光体所需的时间段的范围为约1分钟-约5小时,特别是约5分钟-约1小时。含水HF溶液中氢氟酸的浓度范围为约20%w/w-约70%w/w,特别是约40%w/w-约70%w/w。更低浓度的溶液可导致更低的磷光体产率。
根据本发明的一个实施方案的照明设备或发光组件或灯10示于图1。照明设备10包括显示为发光二极管(LED)芯片12的半导体辐射源和电连接到LED芯片的导线14。所述导线14可以是通过较厚的导线框16支撑的薄线或所述导线可以为自支撑电极,并且可省略导线框。导线14向LED芯片12提供电流并由此致使它发射辐射。
灯可包括任何半导体蓝光源或紫外线光源,当将这些光源发射的辐射导向磷光体时可产生白光。在一个实施方案中,半导体光源是与多种杂质掺杂的发射蓝光的LED。因此,所述LED可包含基于任何合适的III-V、II-VI或IV-IV半导体层的半导体二极管,并具有约250-550nm的发射波长。特别地,所述LED可含有至少一种包含GaN、ZnSe或SiC的半导体层。例如,所述LED可包含通过式IniGajAlkN(其中0≤i;0≤j;0≤k和I+j+k=1)表示的氮化物化合物半导体,并具有大于约250nm和小于约550nm的发射波长。在特别的实施方案中,所述芯片为发射近UV或蓝色的LED,并具有约400-约500nm峰值发射波长。这些LED半导体为本领域所已知。为了方便,本文中将辐射源描述为LED。然而,该术语在本文中用于表示包括所有半导体辐射源,包括例如半导体激光二极管。另外,虽然本文论述的本发明的示例性结构的概要讨论涉及基于无机LED的光源,但应理解,除非另作说明,否则可通过另一种辐射源替代LED芯片,并且对半导体、半导体LED或LED芯片的任何引用仅表示任何适当的辐射源,其包括但不受限于有机发光二极管。
在照明设备10中,磷光体组合物22辐射耦合至LED芯片12。辐射耦合表示元件彼此关联,使得辐射从一个传输至另一个。通过任何适当的方法将磷光体组合物22沉积在LED12上。例如,可形成磷光体的水基悬浮液,并将其涂敷为LED表面的磷光体层。在这样的一种方法中,将其中磷光体颗粒随机悬浮的硅酮浆料置于LED周围。该方法仅为磷光体组合物22和LED12的示例性可能位置。因此,可通过在LED芯片12上涂布和干燥磷光体悬浮液来将磷光体组合物22涂布在LED芯片12的发光面上方或直接涂布在LED芯片12的发光面上。在硅酮基悬浮液的情况中,使悬浮液在适当的温度下固化。壳体18和封装材料20两者应均为透明的,以使得白光24透射通过那些元件。虽然不旨在限制,但在一些实施方案中,磷光体组合物的中值粒径范围为约1-约50微米,特别为约15-约35微米。
在其它实施方案中,将磷光体组合物22散置在封装材料20中,而非直接形成于LED芯片12上。可将磷光体(以粉末形式)散置在密封剂材料20的单一区域内或遍布封装材料的整个体积。通过LED芯片12发射的蓝光与通过磷光体组合物22发射的光混合,且所述混合光呈现为白光。如果将磷光体散置于封装材料20内,则可将磷光体粉末加入至聚合物或硅酮前体中,并装料于LED芯片12周围,随后可使所述聚合物前体固化来使聚合物或硅酮材料固化。还可使用其它已知的磷光体散置方法,例如转移装料。
在一些实施方案中,封装材料20为具有折射度R的硅酮基体,并且除磷光体组合物22之外,还含有具有小于约5%吸光率和R±0.1折射度的稀释剂材料。所述稀释剂材料具有的折射指数为≤1.7,特别为≤1.6,且更特别为≤1.5。在特别的实施方案中,稀释剂材料为式II,并且具有约1.4的折射指数。将无光学活性的材料加入至磷光体/硅酮混合物可产生通过磷光体/封装材料混合物的更为渐变的光通量分布,并且可导致对磷光体更少的损坏。用于稀释剂的合适的材料包括氟化物化合物和聚合物,所述氟化物为例如LiF、MgF2、CaF2、SrF2、AlF3、K2NaAlF6、KMgF3、CaLiAlF6、K2LiAlF6和K2SiF6,它们所具有的折射指数范围为约1.38(AlF3和K2NaAlF6)-约1.43(CaF2),且所述聚合物具有的折射指数的范围为约1.254-约1.7。适合用作稀释剂的聚合物的非限制性实例包括聚碳酸酯、聚酯、尼龙、聚醚酰亚胺、聚醚酮和衍生于苯乙烯、丙烯酸酯、甲基丙烯酸酯、乙烯基、乙酸乙烯酯、乙烯、环氧丙烷和环氧乙烷单体的聚合物以及它们的共聚物,包括卤化和非卤化的衍生物。可将这些聚合物粉末在硅酮固化之前直接结合至硅酮封装材料中。
在再一个实施方案中,将磷光体组合物22涂布在壳体18表面上,而非在LED芯片12上形成。虽然,若期望,可将磷光体涂布在壳体的外表面上,但优选将磷光体组合物涂布在壳体18的内表面上。可将磷光体组合物22涂布在壳体的整个表面或仅仅是壳体表面的顶部。通过LED芯片12发射的UV/蓝光与通过磷光体组合物22发射的光混合,且所述混合光呈现为白光。当然,可将磷光体设置于任何两个或全部三个位置或在任何其它合适的位置,例如与壳体分开或结合至LED。
图2说明根据本发明系统的第二种结构。除非另作说明,否则来自图1-4(例如图1中的12和图2中的112)中相应的数字与各图中相应的结构相关。图2的实施方案的结构与图1的类似,除了将磷光体组合物122散置在封装材料120的内部而非直接形成于LED芯片112上。可将磷光体(以粉末形式)散置在封装材料的单一区域内或遍及封装材料的整个体积。通过LED芯片112发射的辐射(用箭头126标明)与通过磷光体122发射的光混合,且所述混合光呈现为白光124。如果将磷光体散置在密封剂材料120内部,则可将磷光体粉末加入至聚合物前体,并装料在LED芯片112周围。随后可使聚合物或硅酮前体固化以使聚合物或硅酮固化。还可使用其它已知的磷光体散置方法,例如转移模塑。
图3说明根据本发明系统的第三种可能的结构。图3所示实施方案的结构与图1的类似,除了将磷光体组合物222涂布在外壳218表面上而非形成于LED芯片212上方。虽然,若期望,可将磷光体涂布在外壳的外表面上,但优选将磷光体组合物222涂布在外壳218的内表面上。可将磷光体组合物222涂布在外壳的整个表面上,或仅仅是外壳表面的顶部。通过LED芯片212发射的辐射226与通过磷光体组合物222发射的光混合,且所述混合光呈现为白光224。当然,可组合图1-3的结构,可将磷光体设置在任何两个或全部三个位置或在任何其它合适的位置,例如与壳体分开或结合至LED。
在以上任何结构中,灯还可包括嵌入封装材料的多个散射颗粒(未显示)。所述散射颗粒可包含例如氧化铝或二氧化钛。所述散射颗粒有效地散射由LED芯片发射的定向光,优选地具有可忽略的吸收量。
如图4中第四种结构所示,可将LED芯片412安装在反射杯430中。所述杯430可由例如氧化铝、二氧化钛或本领域已知的其它介电粉末的介电材料制成或用所述介电材料涂布,或通过反射金属(例如铝或银)涂布。图4的实施方案的其余结构与任何前述图的那些相同,并可包括两个导线416,导电线432和封装材料420。反射杯430由第一导线416和导电线432支撑,并用于电连接LED芯片412和第二导线416。
另一个结构(特别是用于背光应用)为表面安装式装置(“SMD”)型的发光二极管550,例如图5中所说明。这种SMD为“侧面发射型”并在光导构件554的突起部分上具有发光窗552。SMD组合件可包括如以上限定的LED芯片和通过由LED芯片发射的光激发的磷光体材料。其它背光装置包括但不受限于电视、电脑、智能手机、平板电脑和其它具有包括半导体光源的显示器的便携式装置;和根据本发明的颜色稳定的掺杂Mn4+的磷光体。
当使用发射350-550nm的LED和一种或多种其它适当的磷光体时,产生的照明系统将产生具有白色的光。灯10还可包括嵌入封装材料的散射颗粒(未显示)。所述散射颗粒可包含例如氧化铝或二氧化钛。所述散射粒子有效地散射由LED芯片发射的定向光,优选具有可忽略的吸收量。
除颜色稳定的掺杂Mn4+的磷光体之外,磷光体组合物22可包括一种或多种其它的磷光体。当结合发射范围在约250-550nm辐射的蓝色或近紫外LED用于照明设备时,通过组件发射产生的光将为白光。可将其它磷光体,例如绿色、蓝色、黄色、红色、橙色或其它颜色的磷光体用于共混物中,以定制产生的光的白色并产生特定的光谱功率分布。其它适合用于磷光体组合物22的材料包括电致发光聚合物,例如聚芴,优选为聚(9,9-二辛基芴)和其共聚物,例如共聚(9,9'-二辛基芴-双-N,N'-(4-丁基苯基)二苯胺)(F8-TFB);聚(乙烯基咔唑)和聚亚苯基亚乙烯基和它们的衍生物。此外,发光层可包括蓝色、黄色、橙色、绿色或红色的磷光染料或金属络合物,或它们的组合。适用作磷光染料的材料包括但不受限于三-(1-苯基异喹啉)铱(III)(红色染料)、三-(2-苯基吡啶)铱(绿色染料)和铱(III)双(2-(4,6-二芴苯基)吡啶-N,C2)(蓝色染料)。还可使用市售可得的来自ADS(American DyesSource, Inc.)的荧光和磷光金属络合物。ADS绿色染料包括ADS060GE、ADS061 GEADS063GE和ADS066GE、ADS078GE和ADS090GE。ADS蓝色染料包括ADS064BE、ADS065BE和ADS070BE。ADS红色染料包括ADS067RE、ADS068RE、ADS069RE、ADS075RE、ADS076RE,ADS067RE和ADS077RE。
适用于磷光体组合物22的磷光体包括但不受限于:((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<x≤0.10,0≤y≤0.5,0≤z≤0.5,0≤w≤x;
(Ca,Ce)3Sc2Si3O12(CaSiG);
(Sr,Ca,Ba)3Al1-xSix04+xF1-x:Ce3+(SASOF));
(Ba,Sr,Ca)5(PO4)3(CI,F,Br,OH):Eu2+,Mn2+;(Ba,Sr,Ca)BPO5:Eu2+,Mn2+;(Sr,Ca)10(PO4)6*νB2O3:Eu2+(其中0<v≤1);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0<ξ<0.2);(Ba,Sr,Ca)2(Mg,Zn)Si2O7:Eu2+ (Sr,Ca,Ba)(Al,Ga,ln)2S4:Eu2+;(Y,Gd,Tb,La,Sm,Pr,Lu)3(Al,Ga)5-αO12-3/2α:Ce3+(其中0<α<0.5);(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-vCevCal+uLiwMg2-wPw(Si,Ge)3-wO12-u/2(其中-0.5≤u<1,0<v≤0.1,和0≤w≤0.2);(Y,Lu,Gd)2-φCaφSi4N6+φC1-φ:Ce3+,(其中0≤φ≤0.5);(Lu,Ca,Li,Mg,Y),掺杂Eu2+和/或Ce3 +的α-SiAlON;(Ca,Sr,Ba)SiO2N2:Eu2+, Ce3+;β-SiAlON:Eu2+,3.5MgO*0.5MgF2*GeO2:Mn4+;Ca1-c-fCecEUfAl1+cSi1-cN3,(其中0≤c≤0.2,0≤f≤0.2);Ca1-h-rCehEurAl1-h(Mg,Zn)hSiN3,(其中0≤h≤0.2,0≤r≤0.2);Ca1-2s-tCes(Li,Na)sEutAlSiN3,(其中0≤s≤0.2,0≤f≤0.2,s+t>0);和Ca1-σ-χ-ɸCeσ(Li,Na)χEuɸAl1+σ-χSi1-σ+χN3,(其中0≤σ≤0.2,0≤χ≤0.4,0≤ɸ≤0.2)。
磷光体共混物中各个单独磷光体的比例可取决于所期望的光输出的特征而变化。可调节多个实施方案的磷光体共混物中单独磷光体的相对比率,使得当共混它们的发射并用于LED照明装置时,产生CIE色度图上预定x和y值的可见光。如所述,优选产生白光。这种白光可例如具有范围为约0.20-约0.55的x值和范围为约0.20-约0.55的y值。然而,如所述,磷光体组合物中各种磷光体确切的特性和数量可根据终端用户的需求而变化。例如,所述材料可用于旨在用于液晶显示器(LCD)背光的LED。在该应用中,将基于在穿过LCD/滤色器组合后期望的白色、红色、绿色和蓝色适当地调整LED色点。
结合颜色稳定的磷光体并用于背光或通用发光照明的LED装置在超过2000小时的装置操作下可具有<1.5麦克亚当椭圆(Macadam ellipses)的色移,并且,在特别的实施方案中,在超过2000小时可具有<1的麦克亚当椭圆,其中磷光体/聚合物复合物与LED芯片表面直接接触,LED电光转换效率大于40%,且LED电流密度大于2A/cm2。在加速试验中,其中磷光体/聚合物复合物与LED芯片表面直接接触,LED电光转换效率大于18%,且LED电流密度大于70A/cm2,LED装置在超过30分钟可具有<1.5麦克亚当椭圆的色移。
本发明颜色稳定的掺杂Mn4+的磷光体可用于除上述那些应用之外的应用中。例如,可将所述材料用作荧光灯、阴极射线管、等离子体显示装置或液晶显示器(LCD)中的磷光体。还可将所述材料用作电磁热量计、γ射线照相机、计算机断层扫描仪或激光器中的闪烁剂。这些用途仅为示例性而非限制性。
实施例
通用程序
硅酮带样品的制备
通过混合待测试的500mg材料和1.50g硅酮(Sylgard 184)制备样品。将混合物在真空室脱气约15分钟。将混合物(0.70g)注入圆盘形模板(28.7mm直径和0.79mm厚度)并在90℃下烘烤30分钟。将样品切割为近似5mm x 5mm尺寸的正方形,用于测试。
稳定性测试
高光通量条件
在446nm发射的激光二极管与光纤耦合,并在它的另一个末端具有准直仪。功率输出为310mW,且样品的光束直径为700微米。这等同于样品表面上80W/cm2的通量。使用1米(直径)的积分球收集光谱功率分布(SPD)谱,其为来自激光的散射辐射和来自受激磷光体的发射的组合,并使用光谱仪软件(Specwin)处理数据。在约21小时的期间内通过分别将400nm-500nm和550nm-700nm的SPD积分,每隔两分钟记录激光和磷光体发射的积分功率。排除前90分钟的测量,以避免由于激光热稳定化的影响。如下计算由于激光损坏造成的强度损失的百分比:
虽然仅绘制了来自磷光体的发射器功率,但监测了激光器发射的积分功率和它的峰位,以保证在实验期间激光保持稳定(变化少于1%)。
高温高湿(HHTH)处理
用于高温高湿(HTHH)处理的样品通过以下制成:将磷光体粉末与两部分甲基硅酮粘合剂(RTV-615,Momentive Performance Materials)以0.9g磷光体:0.825g硅酮(A+B部分)的比例混合。随后将磷光体/硅酮混合物注入铝样品支座并在90℃下固化20分钟。对照样品在氮气下贮藏,并将用于暴露于HTHH条件的样品置于85℃/85%RH受控气氛室中。定期除去这些HTHH样品,并将它们在450nm激发下的发光强度与对照样品比较。
实例1-12在氟气氛下退火
程序
将掺杂Mn,含有基于前体材料的总重量的0.68重量%Mn的氟硅酸钾(PFS:Mn)前体K2SiF6:Mn置于炉室中。所述炉室被抽空并用含有氟气和氮气的气氛填充。随后将室加热至期望的退火温度。在保持期望的时间量后,将室冷却至室温。将氟氮混合物排出,多次使用氮将室填充并吹扫,以确保在打开室之前氟气完全除去。
对于实施例1-5,室中的气氛由20%氟气和80%氮气组成。对于实施例6,气氛由5%氟气和95%氮气组成。表1中表明用于初次退火时段的炉设定点温度和时间(T1和t1)和用于二次退火时段(若有)的炉设定点温度和时间(T2和t2)。由于炉设置和将样品相对于对照热电偶在炉中放置的方式,炉中的实际样品温度比炉设定点高25-75℃。
在高光通量条件下测试具有重量%Mn的范围为0.68-0.73重量%的前体PFS:Mn和产物磷光体(比较实施例1)的稳定性,且结果示于表1。退火材料比不经热处理的材料经受显著更小的损坏。
表1
实施例2 退火的磷光体的后处理
通过将粉末(~10g)放入含有100mL K2SiF6饱和溶液(最初通过在室温下向40% HF加入~17g的K2SiF6,搅拌并过滤溶液来制备)的特氟龙烧杯来使用K2SiF6的饱和溶液处理来自实施例2的退火PFS磷光体粉末。缓慢地搅拌悬浮液,并过滤剩余物和在真空下干燥。通过在丙酮中洗涤3-5次并将滤液加热至100℃经10分钟来进行从干燥的滤液中进一步除去HF。在HHTH条件下,在85℃/85%RH经620小时评估经后处理的磷光体连同未退火但经后处理的PFS样品的稳定性。经后处理的样品在高温/高湿条件下经受更少的劣化,保持约94%的发射强度,而未退火的样品保持约86%的发射强度。
比较实施例2-7
如以下表2所示,在高光通量条件下测试未退火的样品和具有Mn含量范围为0.5-0.85重量%的未经处理的PFS前体。
实施例7-12
如表2所示,在425-550℃的炉设定点温度使PFS前体的样品退火经4-8小时的时间范围。退火之后,在48%HF中的饱和K2SiF6溶液中如实施例2处理所有样品。在高光通量条件下测试退火的磷光体,且结果示于表2。
实施例13 稀释的PFS硅酮带
未退火的K2SiF6:Mn(0.68重量%Mn)与硅酮前体混合,并形成由87.8体积%硅酮和12.2体积%PFS组成的固体带。含有1:1的K2SiF6:Mn(0.68重量%Mn)(掺杂的PFS)和K2SiF6(0重量%Mn)(无掺杂的PFS)的混合物的对照物具有75.6体积%硅酮、12.2%无掺杂的PFS和12.2体积%掺杂的PFS的最终组成。
在高光通量条件下使所述带经受稳定性测试。24小时后稀释的PFS样品的功率强度损失为约2.5%,且显著低于对照物。
实施例14 降低的Mn水平
在高光通量条件下测试含有基于前体材料总重量的0.53重量%Mn的掺杂Mn的氟硅酸钾(PFS:Mn)前体K2SiF6:Mn,结果示于表3。含有较低Mn水平的材料比没有经过热处理的对照物(比较实施例8)经受显著更少的损坏。
表3
实施例 | 激光损坏 | %Mn | 注释 |
比较实施例8 | 6%-9% | 0.68-0.73 | 没有退火 |
14 | 3.4% | 0.53 | Mn4+减少25% |
实施例15 备选炉中更高的退火温度
在示于表4的条件下使含有基于前体材料总重量的0.84重量%Mn的掺杂Mn的氟硅酸钾(PFS:Mn)前体K2SiF6:Mn,在不同的炉中退火,所述炉的设定点温度接近炉的最高温度。在退火步骤之后,使用实施例2中的后处理过程加工材料。在高光通量的条件下测试磷光体和退火的未经处理的样品(比较实施例9)。结果示于表4。退火和经后处理的材料比未经热处理的对照物经受显著更少的损坏。此外,蓝色LED激发下的磷光体量子效率比初始对照样品高~7.5%。
表4
实施例 | 激光损坏 | 相对量子效率 | %Mn | 条件 |
比较实施例9 | 10.9% | 100 | 0.84% | 没有退火 |
15 | 1.5% | 107.5 | 0.82% | 540℃,10psia 20%F2/80%N2,经8小时 |
实施例16和17 LED组装和试验程序
使用利用实施例2(实施例16)和5(实施例17)中的条件退火的K2SiF6:Mn4+磷光体和未退火的K2SiF6:Mn4+磷光体(比较实施例10和11)制成LED组合件。这些磷光体与掺杂Ce3+的石榴石和硅酮粘合剂共混,并沉积在与典型的3030 LED组合件类似的组合件中,所述3030 LED组合件具有~4000K色温的两个发射蓝光的LED芯片。所述组合件随后连接于印刷电路板。这些组合件中的LED尺寸为约0.65mm x 0.65mm;采用该LED面积,LED电流密度定义为:LED电流密度=驱动电流/[(LED面积)*(组合件中的LED数目)]。
在30mA下,在47℃的环境温度(T环境)下操作比较实施例10和实施例16的装置经4000小时。在700mA的驱动电流下,在60℃的板温度(T板)下操作比较实施例11和实施例17的装置经30分钟。通过使用上式,30mA的驱动电流产生约为3.6A/cm2的LED电流密度,且700mA的驱动电流产生约为83A/cm2的LED电流密度。不含磷光体的类似的LED组合件在100mA驱动电流和60℃的板温度下产生54%的电光转换效率(定义为发射的光功率除以输入电功率),并且在700mA的驱动电流和60℃的板温度下产生22%的光电转换效率。在不同驱动电流和环境/板温度条件下操作LED后,通过使用经校准的积分球光谱仪在不同的时间测量LED装置的光谱功率分布来获得装置色点。结果示于表5和6。
虽然本文仅说明和描述了本发明的某些特点,但本领域技术人员将想到许多的修改和变化。因此,应理解,所附权利要求旨在覆盖所有落入本发明真实精神内的这些修改和变化。
Claims (24)
1.用于合成颜色稳定的掺杂Mn4+的磷光体的方法,所述方法包括在温度范围为200℃-700℃下使式I
Ax[MFy]:Mn4+
I
的非颜色稳定前体与含氟氧化剂以气态形式接触,以形成颜色稳定的掺杂Mn4+的磷光体;
其中
A为Li、Na、K、Rb、Cs或它们的组合;
M为Si、Ge、Sn、Ti、Zr、Al、Ga、In、Sc、Hf、Y、La、Nb、Ta、Bi、Gd或它们的组合;
x为所述[MFy]离子电荷的绝对值;和
y为5、6或7。
2.根据权利要求1的方法,其中所述含氟氧化剂为F2、无水HF、BrF5、NH4HF2、NH4F、AlF3、SF6、SbF5、ClF3、BrF3、KrF、XeF2、XeF4、NF3、PbF2、ZnF2、SiF4、SnF2、CdF2或它们的组合。
3.根据权利要求1的方法,其中所述含氟氧化剂为F2。
4.根据权利要求1的方法,其中所述温度范围为350℃-600℃。
5.根据权利要求1的方法,其中所述磷光体前体与含氟氧化剂接触经至少1小时的时段。
6.根据权利要求1的方法,其中所述磷光体前体与含氟氧化剂接触经至少4小时的时段。
7.根据权利要求1的方法,其中所述磷光体前体与含氟氧化剂接触经至少6小时的时段。
8.根据权利要求1的方法,其中所述磷光体前体与含氟氧化剂接触经至少8小时的时段。
9.根据权利要求1的方法,其中所述磷光体前体与含氟氧化剂在至少250℃的温度下接触经至少8小时的时段。
10.根据权利要求1的方法,其中所述温度初始为250℃经4小时,并随后为350℃经4小时。
11.根据权利要求1的方法,其中含有所述含氟氧化剂的气氛包含至少0.5%的氟。
12.根据权利要求1的方法,其中含有所述含氟氧化剂的气氛包含至少5%的氟。
13.根据权利要求1的方法,其中含有所述含氟氧化剂的气氛包含至少20%的氟。
14.根据权利要求1的方法,其中含有所述含氟氧化剂的气氛另外包含氮、氦、氖、氩、氪、氙或它们的组合。
15.根据权利要求1的方法,其中含有所述含氟氧化剂的气氛包含20%的氟和80%的氮。
16.根据权利要求1的方法,其中M为Si、Ge、Sn、Ti、Zr或它们的组合。
17.根据权利要求1的方法,其中
A为Na、K、Rb、Cs或它们的组合;
M为Si、Ge、Ti或它们的组合;和
y为6。
18.根据权利要求1的方法,其中所述磷光体前体为K2SiF6:Mn4+。
19.根据权利要求1的方法,所述方法另外包括使颗粒形式的所述颜色稳定的掺杂Mn4+的磷光体与式II的组合物的饱和溶液在含水氢氟酸中接触
Ax[MFy];
II。
20.通过根据权利要求1的方法制备的颜色稳定的掺杂Mn4+的磷光体。
21.一种照明设备,所述照明设备包括
半导体光源;和通过根据权利要求1的方法制备的颜色稳定的掺杂Mn4+的磷光体。
22.用于合成颜色稳定的掺杂Mn4+的磷光体的方法,所述方法包括在温度范围为200℃-700℃下使非颜色稳定前体与含氟氧化剂以气态形式接触,以形成颜色稳定的掺杂Mn4+的磷光体,其中所述非颜色稳定前体选自
(A) A2[MF5]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;且其中M选自Al、Ga、In和它们的组合;
(B) A3[MF6]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;且其中M选自Al、Ga、In和它们的组合;
(C) Zn2[MF7]:Mn4+,其中M选自Al、Ga、In和它们的组合;
(D) A[In2F7]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;
(E) A2[MF6]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4和它们的组合;且其中M选自Ge、Si、Sn、Ti、Zr和它们的组合;
(F) E[MF6]:Mn4+,其中E选自Mg、Ca、Sr、Ba、Zn和它们的组合;且其中M选自Ge、Si、Sn、Ti、Zr和它们的组合;
(G) Ba0.65Zr0.35F2.70:Mn4+;和
(H) A3[ZrF7]:Mn4+,其中A选自Li、Na、K、Rb、Cs、NH4;和它们的组合。
23.根据权利要求22的方法,其中所述温度范围为500℃-600℃。
24.一种照明设备,所述照明设备包括半导体光源;和根据权利要求22的方法制备的颜色稳定的掺杂Mn4+的磷光体。
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Families Citing this family (77)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014165225A (ja) * | 2013-02-21 | 2014-09-08 | Toshiba Lighting & Technology Corp | 発光モジュールおよび照明装置 |
US9698314B2 (en) * | 2013-03-15 | 2017-07-04 | General Electric Company | Color stable red-emitting phosphors |
US9580648B2 (en) * | 2013-03-15 | 2017-02-28 | General Electric Company | Color stable red-emitting phosphors |
US9868898B2 (en) * | 2013-03-15 | 2018-01-16 | General Electric Company | Processes for preparing color stable red-emitting phosphors |
US9399732B2 (en) * | 2013-08-22 | 2016-07-26 | General Electric Company | Processes for preparing color stable manganese-doped phosphors |
US10230022B2 (en) | 2014-03-13 | 2019-03-12 | General Electric Company | Lighting apparatus including color stable red emitting phosphors and quantum dots |
JP6094522B2 (ja) | 2014-04-10 | 2017-03-15 | 日亜化学工業株式会社 | フッ化物蛍光体の製造方法 |
US9512356B2 (en) * | 2014-05-01 | 2016-12-06 | General Electric Company | Process for preparing red-emitting phosphors |
US9546318B2 (en) * | 2014-05-01 | 2017-01-17 | General Electric Company | Process for preparing red-emitting phosphors |
US10563121B2 (en) * | 2014-06-12 | 2020-02-18 | Current Lighting Solutions, Llc | Red-emitting phosphors and associated devices |
US9567516B2 (en) * | 2014-06-12 | 2017-02-14 | General Electric Company | Red-emitting phosphors and associated devices |
US9376615B2 (en) * | 2014-06-12 | 2016-06-28 | General Electric Company | Color stable red-emitting phosphors |
US9371481B2 (en) * | 2014-06-12 | 2016-06-21 | General Electric Company | Color stable red-emitting phosphors |
US9385282B2 (en) * | 2014-06-12 | 2016-07-05 | General Electric Company | Color stable red-emitting phosphors |
US9512357B2 (en) * | 2014-07-22 | 2016-12-06 | General Electric Company | Red-emitting phosphors, associated processes and devices |
EP2988340B1 (en) * | 2014-08-18 | 2017-10-11 | Seoul Semiconductor Co., Ltd. | Light emitting diode package and manufacturing method thereof |
TWI509844B (zh) * | 2014-09-19 | 2015-11-21 | Unity Opto Technology Co Ltd | Applied to the backlight of the LED light-emitting structure |
KR101809793B1 (ko) | 2014-09-30 | 2017-12-15 | 니치아 카가쿠 고교 가부시키가이샤 | 불화물 형광체 및 그 제조 방법 및 발광 장치 |
US10047286B2 (en) * | 2014-10-27 | 2018-08-14 | General Electric Company | Color stable red-emitting phosphors |
JP2016088950A (ja) * | 2014-10-30 | 2016-05-23 | 信越化学工業株式会社 | 赤色蛍光体 |
JP6303980B2 (ja) * | 2014-10-30 | 2018-04-04 | 信越化学工業株式会社 | Mn賦活複フッ化物蛍光体の処理方法 |
BR112017008966A2 (pt) * | 2014-11-21 | 2017-12-26 | Gen Electric | ?processo para a síntese de um fósforo, fósforo, aparelhos de iluminação e dispositivo de luz de fundo? |
US9890328B2 (en) | 2014-12-12 | 2018-02-13 | General Electric Company | Phosphor compositions and lighting apparatus thereof |
US9982190B2 (en) * | 2015-02-20 | 2018-05-29 | General Electric Company | Color stable red-emitting phosphors |
TWI696726B (zh) | 2015-03-05 | 2020-06-21 | 美商通用電機股份有限公司 | 發紅光磷光體、彼之製法及含彼之裝置 |
JP2016204432A (ja) * | 2015-04-16 | 2016-12-08 | 三菱化学株式会社 | 蛍光体、発光装置、照明装置及び画像表示装置 |
JP5952938B1 (ja) * | 2015-04-21 | 2016-07-13 | シャープ株式会社 | 発光装置および画像表示装置 |
US10174248B2 (en) | 2015-05-18 | 2019-01-08 | General Electric Company | Process for improved halide materials |
JP6704001B2 (ja) * | 2015-05-18 | 2020-06-03 | ゼネラル・エレクトリック・カンパニイ | Mnドープされたフッ化物燐光体を製造するための方法 |
CN107771207B (zh) * | 2015-06-01 | 2022-01-18 | 卡任特照明解决方案有限责任公司 | 颜色稳定红色发射磷光体 |
US9871173B2 (en) | 2015-06-18 | 2018-01-16 | Cree, Inc. | Light emitting devices having closely-spaced broad-spectrum and narrow-spectrum luminescent materials and related methods |
MY182260A (en) * | 2015-06-23 | 2021-01-18 | Gen Electric | Phosphor compositions and lighting apparatus thereof |
TWI598538B (zh) * | 2015-07-31 | 2017-09-11 | 宏齊科技股份有限公司 | 無需使用預儲電源的可攜式發光裝置及其發光二極體封裝結構 |
JP6222288B2 (ja) * | 2015-08-07 | 2017-11-01 | 日亜化学工業株式会社 | βサイアロン蛍光体の製造方法 |
CN108352432B (zh) * | 2015-09-10 | 2021-09-14 | 英特曼帝克司公司 | 用于一般照明及显示器背光的磷光体转换白光发光装置和光致发光化合物 |
US11901492B2 (en) | 2015-09-10 | 2024-02-13 | Intematix Corporation | High color rendering white light emitting devices and high color rendering photoluminescence compositions |
FR3043687B1 (fr) * | 2015-11-13 | 2020-07-03 | Universite Blaise Pascal Clermont Ii | Procede sol-gel de synthese d'un materiau luminescent de formulation generale axbyfz:mn |
JP7067857B2 (ja) | 2015-11-17 | 2022-05-16 | 株式会社東芝 | 蛍光体、およびその製造方法、ならびにその蛍光体を用いた発光装置 |
EP3380581B1 (en) * | 2015-11-26 | 2020-07-15 | General Electric Company | Processes for synthesizing red-emitting phosphors and related red-emitting phosphors |
WO2017104406A1 (ja) | 2015-12-18 | 2017-06-22 | 三菱化学株式会社 | 蛍光体、発光装置、照明装置および画像表示装置 |
KR102530756B1 (ko) * | 2016-01-13 | 2023-05-10 | 삼성전자주식회사 | 불화물계 형광체, 불화물계 형광체 제조방법 및 발광장치 |
JP6443417B2 (ja) * | 2016-02-29 | 2018-12-26 | 日亜化学工業株式会社 | 窒化物蛍光体の製造方法、窒化物蛍光体及び発光装置 |
US10754081B2 (en) | 2016-03-07 | 2020-08-25 | Current Lighting Solutions, Llc | Devices containing a remote phosphor package with red line emitting phosphors and green emitting quantum dots |
US10851293B2 (en) * | 2016-04-14 | 2020-12-01 | Current Lighting Solutions, Llc | Phosphor materials for light sources and method for manufacturing the same |
US10883045B2 (en) * | 2016-05-02 | 2021-01-05 | Current Lighting Solutions, Llc | Phosphor materials including fluidization materials for light sources |
EP3455327A1 (en) * | 2016-05-09 | 2019-03-20 | General Electric Company | Manganese-doped phosphor materials for high power density applications |
WO2017210080A1 (en) * | 2016-06-02 | 2017-12-07 | General Electric Company | Red-emitting phosphors and associated devices |
MY190456A (en) | 2016-06-27 | 2022-04-21 | Gen Electric | Coated manganese doped phosphors |
US10072206B2 (en) * | 2016-06-30 | 2018-09-11 | General Electric Company | Processes for preparing color stable red-emitting phosphors |
US9929321B2 (en) * | 2016-08-04 | 2018-03-27 | Kabushiki Kaisha Toshiba | Phosphor, producing method thereof and light-emitting device employing the phosphor |
US10193030B2 (en) * | 2016-08-08 | 2019-01-29 | General Electric Company | Composite materials having red emitting phosphors |
US11114591B2 (en) * | 2016-08-17 | 2021-09-07 | Current Lighting Solutions, Llc | Core-shell materials with red-emitting phosphors |
US11702348B2 (en) | 2016-08-19 | 2023-07-18 | Current Lighting Solutions, Llc | Purified potassium hexafluoromanganate and methods for purifying potassium hexafluoromanganate |
KR20190068580A (ko) * | 2016-10-12 | 2019-06-18 | 메르크 파텐트 게엠베하 | LED 솔리드 스테이트 광원용 변환 발광성 재료로서 Mn4+ 활성화 발광 재료 |
EP3541891B1 (en) * | 2016-11-17 | 2023-04-26 | Current Lighting Solutions, LLC | Coated red line emitting phosphors |
US11193059B2 (en) | 2016-12-13 | 2021-12-07 | Current Lighting Solutions, Llc | Processes for preparing color stable red-emitting phosphor particles having small particle size |
US10793773B2 (en) | 2017-03-16 | 2020-10-06 | Current Lighting Solutions, Llc | Color stable red-emitting phosphors |
CA3063060A1 (en) * | 2017-04-12 | 2018-10-18 | Current Lighting Solutions, Llc | Devices containing a remote phosphor package with red line emitting phosphors and green emitting quantum dots |
CN107033891B (zh) * | 2017-06-13 | 2019-07-16 | 温州大学 | 一种基于氟锆酸盐的白光led用红光材料及其制备方法 |
US20190048258A1 (en) | 2017-08-10 | 2019-02-14 | General Electric Company | Coated manganese doped phosphors |
JP2019044017A (ja) * | 2017-08-30 | 2019-03-22 | デンカ株式会社 | フッ化物蛍光体及び発光装置 |
JP2019044018A (ja) * | 2017-08-30 | 2019-03-22 | デンカ株式会社 | フッ化物蛍光体及び発光装置 |
CN109423276B (zh) * | 2017-09-05 | 2022-03-15 | 厦门稀土材料研究所 | 一种高效稳定的Mn4+掺杂氟化物发光材料及其制备方法 |
WO2019054979A1 (en) | 2017-09-12 | 2019-03-21 | General Electric Company | METHODS FOR PREPARING COLOR-STABLE RED EMITTING LUMINOPHORES |
WO2019054986A1 (en) * | 2017-09-12 | 2019-03-21 | General Electric Company | METHODS FOR PREPARING PHOSPHORES EMITTING IN STABLE COLOR RED |
US10541353B2 (en) | 2017-11-10 | 2020-01-21 | Cree, Inc. | Light emitting devices including narrowband converters for outdoor lighting applications |
EP3768800B1 (de) | 2018-03-20 | 2022-04-20 | LITEC-Vermögensverwaltungsgesellschaft mbH | Mn-aktivierte oxidohalogenide als konversionsleuchtstoffe für led-basierte festkörperlichtquellen |
CN111057535A (zh) * | 2018-10-16 | 2020-04-24 | 云南民族大学 | 一种Mn4+掺杂的氟化物同质包裹的红色发光晶体制备方法 |
DE102018218159B4 (de) * | 2018-10-24 | 2024-01-25 | OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung | Roter leuchtstoff, verfahren zur herstellung eines leuchtstoffs und konversions-led |
US11862758B2 (en) | 2018-11-28 | 2024-01-02 | Lawrence Livermore National Security, Llc | Systems and methods for fluoride ceramic phosphors for LED lighting |
JP6821133B2 (ja) | 2018-12-20 | 2021-01-27 | 日亜化学工業株式会社 | フッ化物蛍光体の製造方法 |
US11261375B2 (en) | 2019-05-22 | 2022-03-01 | General Electric Company | Method to enhance phosphor robustness and dispersability and resulting phosphors |
CN110429167B (zh) * | 2019-07-17 | 2020-12-08 | 武汉大学 | 实现高空间颜色均匀性的led封装方法 |
EP4136177A4 (en) | 2020-04-14 | 2024-07-24 | Gen Electric | INK COMPOSITIONS AND FILMS CONTAINING NARROW-BAND EMITTING LUMINOPHORIC MATERIALS |
JP7057530B2 (ja) * | 2020-12-21 | 2022-04-20 | 日亜化学工業株式会社 | フッ化物蛍光体の製造方法 |
US12018194B2 (en) * | 2021-08-20 | 2024-06-25 | Seoul Semiconductor Co., Ltd. | Color stable Mn-activated oxidofluorides as conversion luminescent materials for LED-based solid state light sources |
US20230279292A1 (en) * | 2022-03-04 | 2023-09-07 | Seoul Semiconductor Co., Ltd. | NOVEL Mn(VI) - ACTIVATED OXIDOFLUORIDES AS LUMINESCENT MATERIALS FOR SOLID STATE LIGHT SOURCES |
Family Cites Families (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2522074A (en) | 1946-05-03 | 1950-09-12 | Univ Rochester | Method of rendering infrared radiation visible employing doubly activated alkaline earth sulfide phosphors |
US3576756A (en) | 1968-06-12 | 1971-04-27 | Mallinckrodt Chemical Works | Fluocomplexes of titanium, silicon, tin and germanium, activated by tetravalent manganese |
GB1360690A (en) | 1973-02-16 | 1974-07-17 | Gen Electric Co Ltd | Luminescent materials |
US4479886A (en) | 1983-08-08 | 1984-10-30 | Gte Products Corporation | Method of making cerium activated yttrium aluminate phosphor |
US6103296A (en) | 1998-04-22 | 2000-08-15 | Osram Sylvania Inc. | Method for improving the screen brightness of gadolinium oxysulfide x-ray phosphors |
CN1157462C (zh) | 2002-04-15 | 2004-07-14 | 清华大学 | 一种制备纳米级氟化物基质上转换荧光材料的方法 |
US6800373B2 (en) * | 2002-10-07 | 2004-10-05 | General Electric Company | Epoxy resin compositions, solid state devices encapsulated therewith and method |
WO2006028271A2 (en) | 2004-09-10 | 2006-03-16 | Showa Denko K.K. | Process for producing manganese fluoride |
US7270773B2 (en) | 2005-01-10 | 2007-09-18 | General Electric Company | Quantum-splitting fluoride-based phosphors, method of producing, and radiation sources incorporating same |
US7497973B2 (en) | 2005-02-02 | 2009-03-03 | Lumination Llc | Red line emitting phosphor materials for use in LED applications |
US7358542B2 (en) | 2005-02-02 | 2008-04-15 | Lumination Llc | Red emitting phosphor materials for use in LED and LCD applications |
US7648649B2 (en) | 2005-02-02 | 2010-01-19 | Lumination Llc | Red line emitting phosphors for use in led applications |
TWI389337B (zh) | 2005-05-12 | 2013-03-11 | Panasonic Corp | 發光裝置與使用其之顯示裝置及照明裝置,以及發光裝置之製造方法 |
EP1892268B1 (en) | 2005-06-14 | 2015-10-28 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition and sheet containing phosphor, and light emitting element using such composition and sheet |
US7834541B2 (en) * | 2006-10-05 | 2010-11-16 | Global Oled Technology Llc | OLED device having improved light output |
JP2008274254A (ja) | 2007-03-30 | 2008-11-13 | Mitsubishi Chemicals Corp | 蛍光体及びその製造方法、蛍光体含有組成物、発光装置、並びに画像表示装置及び照明装置 |
WO2009005035A1 (ja) | 2007-06-29 | 2009-01-08 | Mitsubishi Chemical Corporation | 蛍光体、蛍光体の製造方法、蛍光体含有組成物、並びに発光装置 |
US7847309B2 (en) | 2007-07-16 | 2010-12-07 | GE Lighting Solutions, LLC | Red line emitting complex fluoride phosphors activated with Mn4+ |
US8137586B2 (en) * | 2007-09-14 | 2012-03-20 | Osram Sylvania Inc. | Phosphor blend for a compact fluorescent lamp and lamp containing same |
KR101592836B1 (ko) | 2008-02-07 | 2016-02-05 | 미쓰비시 가가꾸 가부시키가이샤 | 반도체 발광 장치, 백라이트, 컬러 화상 표시 장치, 및 그들에 사용하는 형광체 |
CN102790164B (zh) | 2008-03-03 | 2016-08-10 | Ge磷光体技术有限责任公司 | 发光装置 |
JP5545665B2 (ja) | 2008-03-25 | 2014-07-09 | 国立大学法人群馬大学 | 蛍光体の製造方法 |
JP5239043B2 (ja) * | 2008-07-18 | 2013-07-17 | シャープ株式会社 | 発光装置および発光装置の製造方法 |
JP5682104B2 (ja) | 2008-09-05 | 2015-03-11 | 三菱化学株式会社 | 蛍光体及びその製造方法と、その蛍光体を用いた蛍光体含有組成物及び発光装置、並びに、その発光装置を用いた画像表示装置及び照明装置 |
JP2010093132A (ja) | 2008-10-09 | 2010-04-22 | Sharp Corp | 半導体発光装置およびそれを用いた画像表示装置、液晶表示装置 |
US8703016B2 (en) | 2008-10-22 | 2014-04-22 | General Electric Company | Phosphor materials and related devices |
US9175214B2 (en) | 2009-12-17 | 2015-11-03 | Koninklijke Philips N.V. | Lighting device with light source and wavelength converting element |
US9133390B2 (en) | 2009-12-17 | 2015-09-15 | Koninklijke Philips N.V. | Light emitting diode device with luminescent material |
US8593062B2 (en) | 2010-04-29 | 2013-11-26 | General Electric Company | Color stable phosphors for LED lamps and methods for preparing them |
US8057706B1 (en) * | 2010-07-27 | 2011-11-15 | General Electric Company | Moisture-resistant phosphor and associated method |
US8210698B2 (en) | 2010-07-28 | 2012-07-03 | Bridgelux, Inc. | Phosphor layer having enhanced thermal conduction and light sources utilizing the phosphor layer |
JP4974310B2 (ja) | 2010-10-15 | 2012-07-11 | 三菱化学株式会社 | 白色発光装置及び照明器具 |
US8252613B1 (en) * | 2011-03-23 | 2012-08-28 | General Electric Company | Color stable manganese-doped phosphors |
MY167700A (en) | 2011-04-08 | 2018-09-21 | Shinetsu Chemical Co | Preparation of complex fluoride and complex fluoride phosphor |
JP5418548B2 (ja) | 2011-07-06 | 2014-02-19 | 日亜化学工業株式会社 | フッ化物蛍光体及びそのフッ化物蛍光体を用いた発光装置 |
JP5375906B2 (ja) | 2011-09-13 | 2013-12-25 | 日亜化学工業株式会社 | フッ化物蛍光体及びそれを用いた発光装置 |
JP5512905B1 (ja) | 2011-12-16 | 2014-06-04 | コーニンクレッカ フィリップス エヌ ヴェ | Ledアプリケーションのためのマンガン活性化ヘキサフルオロケイ酸 |
JP6297505B2 (ja) | 2012-02-16 | 2018-03-20 | コーニンクレッカ フィリップス エヌ ヴェKoninklijke Philips N.V. | 半導体led用のコーティングされた狭帯域赤色発光フルオロケイ酸塩 |
WO2013138347A1 (en) | 2012-03-12 | 2013-09-19 | Nitto Denko Corporation | Emissive compacts and method of making the same |
JP5840540B2 (ja) | 2012-03-15 | 2016-01-06 | 株式会社東芝 | 白色照明装置 |
US9343613B2 (en) | 2012-03-29 | 2016-05-17 | Koninklijke Philips N.V. | Phosphor in inorganic binder for LED applications |
US20150132585A1 (en) | 2012-04-18 | 2015-05-14 | Nitto Denko Corporation | Phosphor Ceramics and Methods of Making the Same |
CN102719242B (zh) * | 2012-05-29 | 2014-12-03 | 温州大学 | 一种含氟化物Mn4+掺杂的红光材料及其制备方法 |
CN102827601B (zh) | 2012-09-17 | 2014-08-20 | 中国科学院福建物质结构研究所 | 氟化物荧光粉体材料及其半导体发光器件 |
CN102851026B (zh) | 2012-10-15 | 2014-07-02 | 温州大学 | 一种二基色白光led用红光材料及其制备方法 |
EP2915197B1 (en) | 2012-11-01 | 2020-02-05 | Lumileds Holding B.V. | Led-based device with wide color gamut |
US9698314B2 (en) * | 2013-03-15 | 2017-07-04 | General Electric Company | Color stable red-emitting phosphors |
US20150069299A1 (en) | 2013-09-11 | 2015-03-12 | Nitto Denko Corporation | Phosphor Ceramics and Methods of Making the Same |
JP6094532B2 (ja) * | 2013-12-27 | 2017-03-15 | 日亜化学工業株式会社 | フッ化物蛍光体の製造方法 |
JP5804149B2 (ja) * | 2014-01-30 | 2015-11-04 | 信越化学工業株式会社 | 複フッ化物蛍光体の製造方法及び処理方法 |
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