JP5330684B2 - Blue-emitting phosphor particles - Google Patents
Blue-emitting phosphor particles Download PDFInfo
- Publication number
- JP5330684B2 JP5330684B2 JP2007337403A JP2007337403A JP5330684B2 JP 5330684 B2 JP5330684 B2 JP 5330684B2 JP 2007337403 A JP2007337403 A JP 2007337403A JP 2007337403 A JP2007337403 A JP 2007337403A JP 5330684 B2 JP5330684 B2 JP 5330684B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor particles
- emitting phosphor
- blue light
- blue
- silicon dioxide
- 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.)
- Expired - Fee Related
Links
- 239000002245 particle Substances 0.000 title claims description 135
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 126
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 34
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 24
- 229910052637 diopside Inorganic materials 0.000 claims description 24
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017639 MgSi Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/77922—Silicates
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Description
本発明は、基本組成式がＭｅＭｇＳｉ2Ｏ6：Ｅｕ2+で表される、ディオプサイド結晶構造を有する青色発光蛍光体粒子に関し、特にＸｅ2分子線に相当する波長１７２ｎｍの真空紫外線の励起による発光輝度が向上した青色発光蛍光体粒子に関する。 The present invention relates to blue-emitting phosphor particles having a diopside crystal structure, whose basic composition formula is represented by MeMgSi 2 O 6 : Eu 2+ , and in particular, excitation of vacuum ultraviolet rays having a wavelength of 172 nm corresponding to a Xe 2 molecular beam. The present invention relates to a blue light emitting phosphor particle having improved light emission luminance.
カラー表示のプラズマディスプレイパネル（以下、単にＰＤＰという）は、希ガスの放電により発生した真空紫外線を蛍光体に照射して、蛍光体を励起させることにより、青色、緑色、赤色の可視光を得て、その組み合わせにより画像を表示する。希ガスとしては、一般にＸｅ（キセノン）とＮｅ（ネオン）との混合ガスが用いられている。この混合ガスでは、Ｘｅが放電ガスであり、Ｎｅはバッファガスである。Ｘｅの放電により発生する主な真空紫外線は、波長１４７ｎｍのＸｅの共鳴線と、波長１７２ｎｍ（１７３ｎｍと記載されている文献もある）のＸｅ2の分子線である。通常、蛍光体の発光に利用されるのは、波長１４７ｎｍのＸｅ共鳴線である。 Plasma display panels for color display (hereinafter simply referred to as PDP) emit blue, green and red visible light by irradiating the phosphor with vacuum ultraviolet rays generated by rare gas discharge to excite the phosphor. Then, an image is displayed by the combination. As the rare gas, a mixed gas of Xe (xenon) and Ne (neon) is generally used. In this mixed gas, Xe is a discharge gas and Ne is a buffer gas. The main vacuum ultraviolet rays generated by the discharge of Xe are the Xe resonance line having a wavelength of 147 nm and the Xe 2 molecular beam having a wavelength of 172 nm (some literatures are described as 173 nm). Usually, the Xe resonance line having a wavelength of 147 nm is used for light emission of the phosphor.
このようなＰＤＰに用いられる青色発光用の蛍光体粒子としては、基本組成式がＢａＭｇＡｌ10Ｏ17：Ｅｕ2+で表されるＢＡＭ：Ｅｕ2+青色発光蛍光体粒子や、基本組成式がＭｅＭｇＳｉ2Ｏ6：Ｅｕ2+で表される、ディオプサイド結晶構造を有する青色発光蛍光体粒子（但し、Ｍｅは、Ｃａ、Ｓｒ及びＢａからなる群より選ばれる一種以上のアルカリ土類金属元素）が知られている。 As the phosphor particles for blue light emission used for such PDP, BAM: Eu 2+ blue light-emitting phosphor particles whose basic composition formula is represented by BaMgAl 10 O 17 : Eu 2+ , and the basic composition formula is MeMgSi Blue light-emitting phosphor particles having a diopside crystal structure represented by 2 O 6 : Eu 2+ (where Me is one or more alkaline earth metal elements selected from the group consisting of Ca, Sr and Ba) It has been known.
ディオプサイド結晶構造の青色発光蛍光体粒子は、ＢＡＭ：Ｅｕ2+青色発光蛍光体粒子と比べて、結晶構造が安定で経時的な安定性が高いという利点がある。しかし、ディオプサイド結晶構造の青色発光蛍光体粒子は、ＢＡＭ：Ｅｕ2+青色発光蛍光体粒子と比べて、発光輝度が低いという問題がある。 Compared with BAM: Eu 2+ blue light-emitting phosphor particles, the blue light-emitting phosphor particles having a diopside crystal structure have an advantage that the crystal structure is stable and the stability over time is high. However, the blue light-emitting phosphor particles having a diopside crystal structure have a problem that the emission luminance is lower than that of the BAM: Eu 2+ blue light-emitting phosphor particles.
特に最近では、ＰＤＰの発光効率を向上させることを目的として、希ガス中のＸｅガスの割合を多くする傾向にある。この希ガス中のＸｅガスの割合が多くなると、Ｘｅの放電により発生する真空紫外線は、波長１７２ｎｍの分子線の割合が多くなる。このため、波長１７２ｎｍの真空紫外線での励起による発光輝度を向上させることが重要である。 In particular, recently, for the purpose of improving the luminous efficiency of PDP, the ratio of Xe gas in rare gas tends to be increased. As the ratio of Xe gas in the rare gas increases, the ratio of molecular beams having a wavelength of 172 nm increases in the vacuum ultraviolet rays generated by the discharge of Xe. For this reason, it is important to improve the light emission luminance by excitation with vacuum ultraviolet light having a wavelength of 172 nm.
波長１７２ｎｍの真空紫外線での励起による発光輝度が向上したディオプサイド結晶構造の青色発光蛍光体粒子として、特許文献１には、カルシウム源粉末、ユウロピウム源粉末、マグネシウム源粉末及び珪素源粉末を、所定量のフッ素源と共に還元性雰囲気下にて加熱焼成して製造した、一般式がＣａＭｇＳｉ2Ｏ6：Ｅｕ2+で表される青色発光蛍光体粒子が開示されている。この特許文献１によれば、フッ素源の量を最適化することによって、波長１７２ｎｍの真空紫外線での励起による発光輝度が１０〜３０％程度向上する。しかしながら、実施例に記載されている青色発光蛍光体粒子の発光輝度は、ＢＡＭ：Ｅｕ2+青色発光蛍光体粒子の発光輝度１００とした相対値で４９〜５５であり、従ってディオプサイド結晶構造を有する青色発光蛍光体粒子については、さらなる発光輝度の向上が望まれる。
本発明の目的は、特にＸｅ2分子線の励起による発光輝度が向上した基本組成式がＭｅＭｇＳｉ2Ｏ6：Ｅｕ2+で表される、ディオプサイド結晶構造を有する青色発光蛍光体を提供することにある。 An object of the present invention is to provide a blue light-emitting phosphor having a diopside crystal structure, in which a basic composition formula in which emission luminance is improved particularly by excitation of Xe 2 molecular beam is represented by MeMgSi 2 O 6 : Eu 2+. There is.
本発明は、ＭｅＭｇＳｉ2Ｏ6：Ｅｕ2+で表される、ディオプサイド結晶構造を有する青色発光蛍光体粒子（但し、Ｍｅは、Ｃａである）であって、厚さが２〜５ｎｍの範囲にあるアモルファス二酸化珪素層で表面が被覆されていることを特徴とする青色発光蛍光体粒子、及びＭｅＭｇＳｉ 2 Ｏ 6 ：Ｅｕ 2+ で表される、ディオプサイド結晶構造を有する青色発光蛍光体粒子（但し、Ｍｅは、ＣａとＳｒの組み合わせである）であって、厚さが５〜８ｎｍの範囲にあるアモルファス二酸化珪素層で表面が被覆されていることを特徴とする青色発光蛍光体粒子にある。 The present invention, M eMgSi 2 O 6: represented by Eu 2+, blue-emitting phosphor particles having a diopside crystalline structure (where, Me is a is Ca) a, thickness 2-5 Blue light-emitting phosphor particles whose surface is coated with an amorphous silicon dioxide layer in the range of nm , and blue light emission having a diopside crystal structure represented by MeMgSi 2 O 6 : Eu 2+ Fluorescent particles (where Me is a combination of Ca and Sr), the surface of which is coated with an amorphous silicon dioxide layer having a thickness in the range of 5 to 8 nm. Body particles .
本発明の青色発光蛍光体粒子は、Ｘｅ2分子線に相当する波長１７２ｎｍの真空紫外線の励起による輝度が、従来のディオプサイド結晶構造を有する青色発光蛍光体と比較して、高い値を示す。従って、本発明の青色発光蛍光体粒子は、希ガス中のＸｅガスの割合が多いＰＤＰ用の青色発光蛍光体として有利に使用することができる。 The blue light-emitting phosphor particles of the present invention show a higher luminance than that of a conventional blue light-emitting phosphor having a diopside crystal structure when excited by vacuum ultraviolet light having a wavelength of 172 nm corresponding to the Xe 2 molecular beam. . Therefore, the blue light-emitting phosphor particles of the present invention can be advantageously used as a blue light-emitting phosphor for PDP having a large proportion of Xe gas in a rare gas.
本発明の青色発光蛍光体粒子は、基本組成式がＭｅＭｇＳｉ2Ｏ6：Ｅｕ2+で表される、ディオプサイド（ＣａＭｇＳｉ2Ｏ6）結晶構造を有する青色発光蛍光体粒子からなる。Ｍｅは、Ｃａ単体、またはＣａとＳｒの組み合わせであることが好ましい。ＣａとＳｒの組み合わせの場合、ＣａとＳｒとの比率は、原子比で９：１〜１：９の範囲にあることが好ましい。 The blue light-emitting phosphor particles of the present invention are blue light-emitting phosphor particles having a diopside (CaMgSi 2 O 6 ) crystal structure whose basic composition formula is represented by MeMgSi 2 O 6 : Eu 2+ . M e is preferably a combination of Ca alone or Ca and Sr,. In the case of a combination of Ca and Sr, the ratio of Ca and Sr is preferably in the range of 9: 1 to 1: 9 in atomic ratio.
本発明の青色発光蛍光体粒子は、その表面がアモルファス二酸化珪素層で被覆されている点に特徴がある。アモルファス二酸化珪素層がアモルファスであること及びその厚みは、透過型電子顕微鏡を用いて二酸化珪素層の断面の構造を観察することによって確認することができる。 Blue-emitting phosphor particles of the present invention is characterized in that is coated on its surface there Amorphous silicon dioxide layer. Whether the amorphous silicon dioxide layer is amorphous and its thickness can be confirmed by observing the cross-sectional structure of the silicon dioxide layer using a transmission electron microscope.
本発明の青色発光蛍光体粒子を構成するＭｅ、Ｍｇ、Ｓｉ及びＥｕの各原子の比率は、ディオプサイド結晶構造を形成する比率である限り特に制限はない。通常、Ｍｅ、Ｍｇ、Ｓｉ及びＥｕの各原子の比率は、Ｍｇを１として、Ｍｅが０．８〜１．２の範囲、Ｓｉが１．８〜２．４の範囲、Ｅｕが０．００５〜０．１の範囲にあり、Ｅｕ／（Ｍｅ＋Ｅｕ）は、０．００４〜０．１１の範囲にある。 The ratio of each atom of Me, Mg, Si, and Eu constituting the blue-emitting phosphor particle of the present invention is not particularly limited as long as it is a ratio that forms a diopside crystal structure. Usually, the ratio of each atom of Me, Mg, Si and Eu is such that Mg is 1, Me is in the range of 0.8 to 1.2, Si is in the range of 1.8 to 2.4, and Eu is 0.005. In the range of ~ 0.1, Eu / (Me + Eu) is in the range of 0.004 to 0.11.
ディオプサイド結晶構造を有する青色発光蛍光体粒子は、Ｍｅ源粉末、Ｍｇ源粉末、Ｓｉ源粉末及びＥｕ源粉末を、ディオプサイド結晶構造を有する青色発光蛍光体粒子を生成する割合にて混合して、得られた粉末混合物を還元性雰囲気下にて、焼成することによって製造することができる。 Blue light-emitting phosphor particles having a diopside crystal structure are prepared by mixing Me source powder, Mg source powder, Si source powder, and Eu source powder at a ratio to generate blue light-emitting phosphor particles having a diopside crystal structure. And it can manufacture by baking the obtained powder mixture in reducing atmosphere.
Ｍｅ源粉末、Ｍｇ源粉末、Ｓｉ源粉末及びＥｕ源粉末の各原料粉末は、酸化物、もしくは炭酸塩、硝酸塩、水酸化物、フッ化物及び塩化物などの加熱より酸化物を生成する化合物であることが好ましい。Ｍｅ源粉末、Ｍｇ源粉末、Ｓｉ源粉末又はＥｕ源粉末の一部もしくは全部に、融剤（フラックス）として作用するフッ化物もしくは塩化物を用いることが好ましい。 Each raw material powder of Me source powder, Mg source powder, Si source powder and Eu source powder is an oxide or a compound that generates an oxide by heating such as carbonate, nitrate, hydroxide, fluoride and chloride. Preferably there is. It is preferable to use a fluoride or chloride acting as a flux (flux) for a part or all of the Me source powder, Mg source powder, Si source powder or Eu source powder.
粉末混合物は、還元性雰囲気下での焼成の前に、大気雰囲気下にて、６００〜９００℃の温度で仮焼してもよい。 The powder mixture may be calcined at a temperature of 600 to 900 ° C. in an air atmosphere before firing in a reducing atmosphere.
粉末混合物を還元性雰囲気下にて焼成する際の温度は、１０００〜１５００℃の範囲にあることが好ましい。粉末混合物の焼成を行なう際の還元性雰囲気は、水素ガスを１〜１０体積％の範囲にて含むアルゴンガスあるいは窒素ガス雰囲気であることが好ましい。焼成時間は、一般に１〜１００時間の範囲である。 The temperature at which the powder mixture is fired in a reducing atmosphere is preferably in the range of 1000 to 1500 ° C. The reducing atmosphere when firing the powder mixture is preferably an argon gas or nitrogen gas atmosphere containing hydrogen gas in a range of 1 to 10% by volume. The firing time is generally in the range of 1 to 100 hours.
上記のようにして得られる青色発光蛍光体粒子の発光輝度を向上させるために、青色発光蛍光体粒子を大気雰囲気中にて再焼成するアニール処理や、酸水溶液に接触させる酸処理を行なってもよい。 In order to improve the emission luminance of the blue light-emitting phosphor particles obtained as described above, annealing treatment for refiring the blue light-emitting phosphor particles in the air atmosphere or acid treatment for contacting with an acid aqueous solution may be performed. Good.
アニール処理の処理温度は、３００〜１５００℃の範囲、好ましくは４００〜１０００℃の範囲、より好ましくは５５０〜１０００℃の範囲である。処理時間は、一般に１０分〜１０時間の範囲である。 The treatment temperature of the annealing treatment is in the range of 300 to 1500 ° C, preferably in the range of 400 to 1000 ° C, more preferably in the range of 550 to 1000 ° C. The treatment time is generally in the range of 10 minutes to 10 hours.
酸処理に用いる酸溶液の例としては塩酸水溶液、硝酸水溶液及び硫酸水溶液が挙げられる。特に塩酸水溶液が好ましい。酸溶液の濃度は０．０５〜１０モル／Ｌの範囲にあることが好ましい。処理時間は、一般に１０分〜１０時間の範囲である。 Examples of the acid solution used for the acid treatment include a hydrochloric acid aqueous solution, a nitric acid aqueous solution, and a sulfuric acid aqueous solution. A hydrochloric acid aqueous solution is particularly preferable. The concentration of the acid solution is preferably in the range of 0.05 to 10 mol / L. The treatment time is generally in the range of 10 minutes to 10 hours.
青色発光蛍光体粒子の表面をアモルファス二酸化珪素層で被覆する方法としては、アルコール溶媒中にて、蛍光体粒子、加水分解性珪素化合物及び水を混合して、加水分解性珪素化合物を加水分解縮合させ、生成した珪素含有化合物を蛍光体粒子の表面に付着させることによって珪素含有化合物層付き蛍光体粒子を得て、次いで該珪素含有化合物層付き蛍光体粒子を焼成する方法が挙げられる。 As a method of coating the surface of the blue light emitting phosphor particles with an amorphous silicon dioxide layer, the phosphor particles, the hydrolyzable silicon compound and water are mixed in an alcohol solvent to hydrolyze and condense the hydrolyzable silicon compound. There is a method in which phosphor particles with a silicon-containing compound layer are obtained by attaching the produced silicon-containing compound to the surface of the phosphor particles, and then firing the phosphor particles with a silicon-containing compound layer.
アルコール溶媒の例としては、メタノール、エタノールなどの炭素原子数１〜６の低級アルコールを挙げることができる。 Examples of alcohol solvents include lower alcohols having 1 to 6 carbon atoms such as methanol and ethanol.
加水分解性珪素化合物の例としては、一般式ＳｉＲ1 aＲ2 4-aで表される化合物を挙げることができる。この一般式において、Ｒ1は有機官能基、Ｒ2は加水分解性官能基、ａは、０〜２の整数を表す。 Examples of the hydrolyzable silicon compound include compounds represented by the general formula SiR 1 a R 2 4-a . In this general formula, R 1 represents an organic functional group, R 2 represents a hydrolyzable functional group, and a represents an integer of 0 to 2.
有機官能基Ｒ1の例としては、アルキル基（例、メチル基、エチル基）及びアルケニル基（例、ビニル基、アリル基）などの炭化水素基が挙げられる。炭化水素基は、炭素原子数が６以下であることが好ましい。加水分解性官能基Ｒ2は、加水分解反応によりシラノール基を生成する官能基であり、その例としては、アルコシキ基（例、メトキシ基、エトキシ基）及びハロゲン元素（例、塩素、臭素）を挙げることができる。
加水分解性珪素化合物は、反応速度の観点から、テトラメチルオルソシリケート及びテトラエチルオルソシリケート（ＴＥＯＳ）又は四塩化珪素であることが好ましい。
Examples of the organic functional group R 1 include hydrocarbon groups such as alkyl groups (eg, methyl group, ethyl group) and alkenyl groups (eg, vinyl group, allyl group). The hydrocarbon group preferably has 6 or less carbon atoms. The hydrolyzable functional group R 2 is a functional group that generates a silanol group by hydrolysis reaction. Examples thereof include an alkoxy group (eg, methoxy group, ethoxy group) and a halogen element (eg, chlorine, bromine). Can be mentioned.
The hydrolyzable silicon compound is preferably tetramethyl orthosilicate and tetraethyl orthosilicate (TEOS) or silicon tetrachloride from the viewpoint of reaction rate.
加水分解性珪素化合物の加水分解縮合は、必要に応じてアルカリ触媒の存在下にて行なう。アルカリ触媒の例としては、アンモニア、及び水酸化ナトリウムや水酸化カリウムなどのアルカリ金属の水酸化物を挙げることができる。 Hydrolytic condensation of the hydrolyzable silicon compound is performed in the presence of an alkali catalyst as necessary. Examples of the alkali catalyst include ammonia and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide.
珪素含有化合物層付き蛍光体粒子の焼成温度は、一般に７５０℃以下、好ましくは３５０〜７００℃の範囲である。焼成時間は、一般に１０分〜１０時間の範囲である。 The firing temperature of the phosphor particles with a silicon-containing compound layer is generally 750 ° C. or lower, preferably 350 to 700 ° C. The firing time is generally in the range of 10 minutes to 10 hours.
［比較例１］
Ｃａ：Ｍｇ：Ｓｉ：Ｅｕのモル比が、０．９７５：１：２．０００：０．０２５となるように炭酸カルシウム粉末（純度：９９．９９質量％、平均粒子径：３．８７μｍ）１５．０１ｇ、塩基性炭酸マグネシウム粉末（純度：９９．９９質量％、平均粒子径：１１．０８μｍ）１５．５８ｇ、二酸化珪素粉末（純度：９９．９質量％、平均粒子径：３．８７μｍ）２０．００ｇ、酸化ユウロピウム（純度：９９．９質量％、平均粒子径：２．７１μｍ）０．７３３ｇ、塩化カルシウム粉末（純度：９９．９質量％）３．６７５ｇをそれぞれ秤量した。なお、各原料粉末の平均粒子径はいずれもレーザ回折散乱法により測定した値である。秤量した各原料粉末を、純水７５０ｍＬと共にボールミルに投入して、２４時間湿式混合した後、乾燥して、粉末混合物を得た。
[Comparative Example 1]
Calcium carbonate powder (purity: 99.99 mass%, average particle size: 3.87 μm) so that the molar ratio of Ca: Mg: Si: Eu is 0.975: 1: 2.000: 0.025 15 0.01 g, basic magnesium carbonate powder (purity: 99.99% by mass, average particle size: 11.08 μm) 15.58 g, silicon dioxide powder (purity: 99.9% by mass, average particle size: 3.87 μm) 20 0.000 g, europium oxide (purity: 99.9% by mass, average particle size: 2.71 μm) 0.733 g, and calcium chloride powder (purity: 99.9% by mass) 3.675 g were weighed. The average particle diameter of each raw material powder is a value measured by a laser diffraction scattering method. Each raw material powder weighed was put into a ball mill together with 750 mL of pure water, wet-mixed for 24 hours, and then dried to obtain a powder mixture.
得られた粉末混合物を、アルミナ坩堝に入れて、大気雰囲気中にて、８５０℃の温度で３時間焼成し、次いで室温まで放冷した後、２体積％水素−９８体積％アルゴンの混合ガス雰囲気中にて、１０５０℃の温度で３時間焼成して、粉末焼成物を得た。 The obtained powder mixture was put in an alumina crucible, calcined at 850 ° C. for 3 hours in an air atmosphere, and then allowed to cool to room temperature, and then mixed gas atmosphere of 2 volume% hydrogen-98 volume% argon. Inside, it baked at the temperature of 1050 degreeC for 3 hours, and the powder baked material was obtained.
得られた粉末焼成物を、濃度０．１モル／Ｌの塩酸水溶液に３０分間接触させた後、水で洗浄し、乾燥した後、アルミナ坩堝に入れて、大気雰囲気中にて６００℃の温度で１時間アニールした。 The obtained powder fired product was brought into contact with a 0.1 mol / L hydrochloric acid aqueous solution for 30 minutes, washed with water, dried, then placed in an alumina crucible and a temperature of 600 ° C. in an air atmosphere. For 1 hour.
アニール後の粉末焼成物のＸ線回折パターンを測定した結果、粉末焼成物はディオプサイド結晶構造を有することが確認された。また、粉末焼成物に波長１７２ｎｍの真空紫外線を照射した結果、青色の発光が確認された。これらの結果から、粉末焼成物はディオプサイド結晶構造を有する青色発光蛍光体粒子であることが確認された。青色発光蛍光体粒子の平均粒子径は２．８μｍであった。 As a result of measuring the X-ray diffraction pattern of the fired powder after annealing, it was confirmed that the fired powder had a diopside crystal structure. Moreover, as a result of irradiating the powder fired product with vacuum ultraviolet rays having a wavelength of 172 nm, blue light emission was confirmed. From these results, it was confirmed that the fired powder was blue-emitting phosphor particles having a diopside crystal structure. The average particle diameter of the blue light emitting phosphor particles was 2.8 μm.
［実施例１］
上記比較例１にて製造したディオプサイド結晶構造を有する青色発光蛍光体粒子２．５ｇと、エタノール５０ｍＬとを、１００ｍＬビーカーに投入し、青色発光蛍光体粒子をエタノール中に分散させた。分散液を撹拌しながら、該分散液にテトラエチルオルソシリケート（純度：９９．９９９質量％）５ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として５０質量％）を添加した。次いで、分散液に濃度２．８質量％のアンモニア水２ｍＬを１０分かけて滴下し、さらに、１時間撹拌を続けた。撹拌終了後、分散液を遠心分離して、青色発光蛍光体粒子を回収した。回収した青色発光蛍光体粒子を、真空乾燥した後、アルミナ坩堝に入れて、大気雰囲気中にて、４００℃の温度で１時間焼成した。焼成後の青色発光蛍光体粒子の表面を透過型電子顕微鏡（日本電子（株）製、ＪＥＭ−２０１０Ｆ型）を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ９ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 1]
2.5 g of blue light emitting phosphor particles having a diopside crystal structure produced in Comparative Example 1 above and 50 mL of ethanol were put into a 100 mL beaker, and the blue light emitting phosphor particles were dispersed in ethanol. While stirring the dispersion, 5 mL of tetraethyl orthosilicate (purity: 99.999% by mass) (50% by mass in terms of silicon dioxide with respect to the blue light emitting phosphor particles) was added to the dispersion. Next, 2 mL of aqueous ammonia having a concentration of 2.8% by mass was added dropwise to the dispersion over 10 minutes, and stirring was further continued for 1 hour. After the stirring was completed, the dispersion was centrifuged to collect blue light emitting phosphor particles. The collected blue light-emitting phosphor particles were vacuum-dried, placed in an alumina crucible, and fired at 400 ° C. for 1 hour in an air atmosphere. As a result of observing the surface of the blue light-emitting phosphor particles after firing with a transmission electron microscope (JEM-2010F type, manufactured by JEOL Ltd.), the surface of the blue light-emitting phosphor particles has a uniform thickness of 9 nm. It was confirmed that an amorphous silicon dioxide layer was formed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光スペクトルを励起波長１７２ｎｍとして分光蛍光光度計により測定し、その発光スペクトルの最大ピーク値を発光輝度として計測した。この発光輝度を、同じ条件で測定した比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表１に示す。 The emission spectrum of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured with a spectrofluorometer at an excitation wavelength of 172 nm, and the maximum peak value of the emission spectrum was measured as the emission luminance. This emission luminance is shown in Table 1 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 1 measured under the same conditions as 100.
［実施例２］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を３ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として３０質量％）とした以外は、実施例１と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ５ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 2]
In the same manner as in Example 1, except that the amount of tetraethyl orthosilicate added was 3 mL (30% by mass as the amount of silicon dioxide converted to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the luminescent phosphor particles. As a result of observing the surface of the blue light emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 5 nm is formed on the surface of the blue light emitting phosphor particles. Was confirmed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表１に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 1 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 1 as 100.
［実施例３］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を２ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として２０質量％）とした以外は、実施例１と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ３ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 3]
In the same manner as in Example 1, except that the amount of tetraethyl orthosilicate added was 2 mL (20% by mass as the amount of silicon dioxide converted to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the luminescent phosphor particles. As a result of observing the surface of the blue light-emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 3 nm is formed on the surface of the blue light-emitting phosphor particles. Was confirmed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表１に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 1 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 1 as 100.
［実施例４］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を１ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として１０質量％）とした以外は、実施例１と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ２ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 4]
In the same manner as in Example 1, except that the amount of tetraethyl orthosilicate added was 1 mL (10% by mass as silicon dioxide equivalent to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the luminescent phosphor particles. As a result of observing the surface of the blue light emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 2 nm is formed on the surface of the blue light emitting phosphor particles. Was confirmed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表１に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 1 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 1 as 100.
［比較例２］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を０．５ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として５質量％）とした以外は、実施例１と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。得られた青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ１ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Comparative Example 2]
The same procedure as in Example 1 was conducted except that the amount of tetraethyl orthosilicate added was 0.5 mL (5% by mass as the amount of silicon dioxide converted to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the blue light emitting phosphor particles. As a result of observing the surface of the obtained blue light-emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 1 nm was formed on the surface of the blue light-emitting phosphor particles. It was confirmed that
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表１に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 1 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 1 as 100.
［比較例３］
市販のＢＡＭ：Ｅｕ2+青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表１に示す。
[Comparative Example 3]
The emission luminance of commercially available BAM: Eu 2+ blue-emitting phosphor particles was measured in the same manner as in Example 1. This emission luminance is shown in Table 1 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 1 as 100.
表１
────────────────────────────────────────
アモルファス二酸化素層 相対発光輝度*
の厚み（ｎｍ） （対ＢＡＭ：Ｅｕ2+青色発光蛍光体粒子）
────────────────────────────────────────
実施例１** ９ １０３（５６．６）
実施例２ ５ １０４（５７．１）
実施例３ ３ １０７（５８．８）
実施例４ ２ １０７（５８．８）
────────────────────────────────────────
比較例１ ０ １００（５４．９）
比較例２ １ １０１（５５．５）
比較例３ ０ １８２（１００）
────────────────────────────────────────
＊）相対発光輝度は、比較例１の青色発光蛍光体粒子の発光輝度を１００とした相対値。括弧内は、比較例３（市販のＢＡＭ：Ｅｕ2+青色発光蛍光体粒子）の発光輝度を１００とした相対値。
＊＊）実施例１は、本発明の実施例ではない。
Table 1
────────────────────────────────────────
Amorphous dioxide layer Relative luminance *
Thickness (nm) (vs BAM: Eu 2+ blue-emitting phosphor particles)
────────────────────────────────────────
Example 1 ** 9 103 (56.6)
Example 2 5 104 (57.1)
Example 3 3 107 (58.8)
Example 4 2 107 (58.8)
────────────────────────────────────────
Comparative Example 1 0 100 (54.9)
Comparative Example 2 1 101 (55.5)
Comparative Example 3 0 182 (100)
────────────────────────────────────────
*) The relative light emission luminance is a relative value with the light emission luminance of the blue light emitting phosphor particles of Comparative Example 1 as 100. The values in parentheses are relative values with the emission luminance of Comparative Example 3 (commercially available BAM: Eu 2+ blue-emitting phosphor particles) as 100.
**) Example 1 is not an example of the present invention.
表１の結果から明らかなように、ディオプサイド結晶構造を有する青色発光蛍光体粒子（ＣａＭｇＳｉ2Ｏ6：Ｅｕ2+）の表面にアモルファス二酸化珪素層を２ｎｍ以上の厚さとなるように形成することにより、Ｘｅ2分子線に相当する波長１７２ｎｍの真空紫外線の励起による発光輝度が向上する。 As is apparent from the results in Table 1, an amorphous silicon dioxide layer is formed to a thickness of 2 nm or more on the surface of blue light emitting phosphor particles (CaMgSi 2 O 6 : Eu 2+ ) having a diopside crystal structure. As a result, the luminance of light emitted by excitation of vacuum ultraviolet rays having a wavelength of 172 nm corresponding to the Xe 2 molecular beam is improved.
［比較例４］
Ｃａ：Ｓｒ：Ｍｇ：Ｓｉ：Ｅｕのモル比が、０．４７５：０．５００：１：２．０００：０．０２５となるように、炭酸カルシウム粉末（純度：９９．９９質量％、平均粒子径：３．８７μｍ）５．４１７ｇ、炭酸ストロンチウム粉末（純度：９９．９９質量％、平均粒子径：９．０８μｍ）１２．３０ｇ、塩基性炭酸マグネシウム粉末（純度：９９．９９質量％、平均粒子径：１１．０８μｍ）１５．５８ｇ、二酸化珪素粉末（純度：９９．９質量％、平均粒子径：３．８７μｍ）２０．００ｇ、酸化ユウロピウム（純度：９９．９質量％、平均粒子径：２．７１μｍ）０．７３３ｇ、塩化カルシウム粉末（純度：９９．９質量％）３．６７５ｇをそれぞれ秤量した。なお、各原料粉末の平均粒子径はいずれもレーザ回折散乱法により測定した値である。秤量した各原料粉末を、純水７５０ｍＬと共にボールミルに投入して、２４時間湿式混合した後、乾燥して、粉末混合物を得た。
[Comparative Example 4]
Calcium carbonate powder (purity: 99.99% by mass, average particle size) so that the molar ratio of Ca: Sr: Mg: Si: Eu is 0.475: 0.500: 1: 2.000: 0.025 Diameter: 3.87 μm) 5.417 g, strontium carbonate powder (purity: 99.99% by mass, average particle size: 9.08 μm) 12.30 g, basic magnesium carbonate powder (purity: 99.99% by mass, average particle) Diameter: 11.08 μm) 15.58 g, silicon dioxide powder (purity: 99.9% by mass, average particle size: 3.87 μm) 20.00 g, europium oxide (purity: 99.9% by mass, average particle size: 2) 0.771 g) and calcium chloride powder (purity: 99.9% by mass) 3.675 g were weighed. The average particle diameter of each raw material powder is a value measured by a laser diffraction scattering method. Each raw material powder weighed was put into a ball mill together with 750 mL of pure water, wet-mixed for 24 hours, and then dried to obtain a powder mixture.
得られた粉末混合物を、アルミナ坩堝に入れて、大気雰囲気中にて、８５０℃の温度で３時間焼成し、次いで室温まで放冷した後、２体積％水素−９８体積％アルゴンの混合ガス雰囲気中にて、１０５０℃の温度で３時間焼成して、粉末焼成物を得た。 The obtained powder mixture was put in an alumina crucible, calcined at 850 ° C. for 3 hours in an air atmosphere, and then allowed to cool to room temperature, and then mixed gas atmosphere of 2 volume% hydrogen-98 volume% argon. Inside, it baked at the temperature of 1050 degreeC for 3 hours, and the powder baked material was obtained.
得られた粉末焼成物を、濃度０．１モル／Ｌの塩酸水溶液に３０分間接触させた後、水で洗浄し、乾燥した後、アルミナ坩堝に入れて、大気雰囲気中にて６００℃の温度で１時間アニールした。 The obtained powder fired product was brought into contact with a 0.1 mol / L hydrochloric acid aqueous solution for 30 minutes, washed with water, dried, then placed in an alumina crucible and a temperature of 600 ° C. in an air atmosphere. For 1 hour.
アニール後の粉末焼成物のＸ線回折パターンを測定した結果、粉末焼成物はディオプサイド結晶構造を有することが確認された。また、粉末焼成物に波長１７２ｎｍの真空紫外線を照射した結果、青色の発光が確認された。これらの結果から、粉末焼成物はディオプサイド結晶構造を有する青色発光蛍光体粒子であることが確認された。青色発光蛍光体粒子の平均粒子径は５．０μｍであった。 As a result of measuring the X-ray diffraction pattern of the fired powder after annealing, it was confirmed that the fired powder had a diopside crystal structure. Moreover, as a result of irradiating the powder fired product with vacuum ultraviolet rays having a wavelength of 172 nm, blue light emission was confirmed. From these results, it was confirmed that the fired powder was blue-emitting phosphor particles having a diopside crystal structure. The average particle diameter of the blue light emitting phosphor particles was 5.0 μm.
［実施例５］
上記比較例４にて製造したディオプサイド結晶構造を有する青色発光蛍光体粒子２．５ｇと、エタノール５０ｍＬとを、１００ｍＬビーカーに投入し、青色発光蛍光体粒子をエタノール中に分散させた。分散液を撹拌しながら、該分散液にテトラエチルオルソシリケート（純度：９９．９９９質量％）５ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として５０質量％）を添加した。次いで、分散液に濃度２．８質量％のアンモニア水２ｍＬを１０分かけて滴下し、さらに、１時間撹拌を続けた。撹拌終了後、分散液を遠心分離して、青色発光蛍光体粒子を回収した。回収した青色発光蛍光体粒子を、真空乾燥した後、アルミナ坩堝に入れて、大気雰囲気中にて、４００℃の温度で１時間焼成した。焼成後の青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ１３ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 5]
The blue light emitting phosphor particles having a diopside crystal structure produced in Comparative Example 4 and 2.5 g of ethanol and 50 mL of ethanol were put into a 100 mL beaker, and the blue light emitting phosphor particles were dispersed in ethanol. While stirring the dispersion, 5 mL of tetraethyl orthosilicate (purity: 99.999% by mass) (50% by mass in terms of silicon dioxide with respect to the blue light emitting phosphor particles) was added to the dispersion. Next, 2 mL of aqueous ammonia having a concentration of 2.8% by mass was added dropwise to the dispersion over 10 minutes, and stirring was further continued for 1 hour. After the stirring was completed, the dispersion was centrifuged to collect blue light emitting phosphor particles. The collected blue light-emitting phosphor particles were vacuum-dried, placed in an alumina crucible, and fired at 400 ° C. for 1 hour in an air atmosphere. As a result of observing the surface of the blue light-emitting phosphor particles after firing using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 13 nm was formed on the surface of the blue light-emitting phosphor particles. It was confirmed that
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例４の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表２に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 2 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 4 as 100.
［実施例６］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を３ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として３０質量％）とした以外は、実施例５と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ８ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 6]
In the same manner as in Example 5, except that the amount of tetraethyl orthosilicate added was 3 mL (30% by mass as the amount of silicon dioxide converted to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the luminescent phosphor particles. As a result of observing the surface of the blue light-emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 8 nm is formed on the surface of the blue light-emitting phosphor particles. Was confirmed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例４の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表２に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 2 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 4 as 100.
［実施例７］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を２ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として２０質量％）とした以外は、実施例５と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ５ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 7]
In the same manner as in Example 5, except that the amount of tetraethyl orthosilicate added was 2 mL (20% by mass as the amount of silicon dioxide converted to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the luminescent phosphor particles. As a result of observing the surface of the blue light emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 5 nm is formed on the surface of the blue light emitting phosphor particles. Was confirmed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例４の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表２に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 2 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 4 as 100.
［実施例８］
青色発光蛍光体粒子２．５ｇに対して、テトラエチルオルソシリケートの添加量を１ｍＬ（青色発光蛍光体粒子に対する二酸化珪素換算量として１０質量％）とした以外は、実施例５と同様にして、青色発光蛍光体粒子の表面にアモルファス二酸化珪素層を形成した。青色発光蛍光体粒子の表面を実施例１と同様に透過型電子顕微鏡を用いて観察した結果、青色発光蛍光体粒子の表面には厚さ３ｎｍの均一なアモルファス二酸化珪素層が形成されていることが確認された。
[Example 8]
In the same manner as in Example 5, except that the amount of tetraethyl orthosilicate added was 1 mL (10% by mass as silicon dioxide equivalent to the blue light-emitting phosphor particles) with respect to 2.5 g of the blue light-emitting phosphor particles. An amorphous silicon dioxide layer was formed on the surface of the luminescent phosphor particles. As a result of observing the surface of the blue light-emitting phosphor particles using a transmission electron microscope in the same manner as in Example 1, a uniform amorphous silicon dioxide layer having a thickness of 3 nm is formed on the surface of the blue light-emitting phosphor particles. Was confirmed.
得られたアモルファス二酸化珪素層付き青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例４の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表２に示す。 The emission luminance of the resulting blue light-emitting phosphor particles with an amorphous silicon dioxide layer was measured in the same manner as in Example 1. This emission luminance is shown in Table 2 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 4 as 100.
［比較例５］
市販のＢＡＭ：Ｅｕ2+青色発光蛍光体粒子の発光輝度を実施例１と同様に測定した。この発光輝度を、比較例４の青色発光蛍光体粒子の発光輝度を１００とした相対値として下記の表２に示す。
[Comparative Example 5]
The emission luminance of commercially available BAM: Eu 2+ blue-emitting phosphor particles was measured in the same manner as in Example 1. This emission luminance is shown in Table 2 below as a relative value with the emission luminance of the blue-emitting phosphor particles of Comparative Example 4 as 100.
表２
────────────────────────────────────────
アモルファス二酸化素層 相対発光輝度*
の厚み（ｎｍ） （対ＢＡＭ：Ｅｕ2+青色発光蛍光体粒子）
────────────────────────────────────────
実施例５** １３ １０３（６０．６）
実施例６ ８ １０８（６３．５）
実施例７ ５ １０５（６１．８）
実施例８** ３ １０３（６０．６）
────────────────────────────────────────
比較例４ ０ １００（５８．８）
比較例５ ０ １７０（１００）
────────────────────────────────────────
＊）相対発光輝度は、比較例４の青色発光蛍光体粒子の発光輝度を１００とした相対値。括弧内は、比較例５（市販のＢＡＭ：Ｅｕ2+青色発光蛍光体粒子）の発光輝度を１００とした相対値。
＊＊）実施例５及び実施例８は、本発明の実施例ではない。
Table 2
────────────────────────────────────────
Amorphous dioxide layer Relative luminance *
Thickness (nm) (vs BAM: Eu 2+ blue-emitting phosphor particles)
────────────────────────────────────────
Example 5 ** 13 103 (60.6)
Example 6 8 108 (63.5)
Example 7 5 105 (61.8)
Example 8 ** 3 103 (60.6)
────────────────────────────────────────
Comparative Example 4 0 100 (58.8)
Comparative Example 5 0 170 (100)
────────────────────────────────────────
*) The relative light emission luminance is a relative value with the light emission luminance of the blue light-emitting phosphor particles of Comparative Example 4 as 100. The values in parentheses are relative values with the light emission luminance of Comparative Example 5 (commercially available BAM: Eu 2+ blue light emitting phosphor particles) as 100.
**) Examples 5 and 8 are not examples of the present invention.
表２の結果から明らかなように、カルシウムの一部をストロンチウムに置換したディオプサイド結晶構造を有する青色発光蛍光体粒子［（Ｃａ，Ｓｒ）ＭｇＳｉ2Ｏ6：Ｅｕ2+］についても、表面に２ｎｍ以上の厚さのアモルファス二酸化珪素層を形成することにより、Ｘｅ2分子線に相当する波長１７２ｎｍの真空紫外線の励起による発光輝度が向上する。 As is apparent from the results in Table 2, the surface of blue-emitting phosphor particles [(Ca, Sr) MgSi 2 O 6 : Eu 2+ ] having a diopside crystal structure in which a part of calcium is substituted with strontium In addition, by forming an amorphous silicon dioxide layer having a thickness of 2 nm or more, emission luminance is improved by excitation of vacuum ultraviolet rays having a wavelength of 172 nm corresponding to the Xe 2 molecular beam.
Claims (2)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007337403A JP5330684B2 (en) | 2007-12-27 | 2007-12-27 | Blue-emitting phosphor particles |
| TW097150253A TW200940685A (en) | 2007-12-27 | 2008-12-23 | Blue light-emitting fluophor |
| KR1020080133582A KR101538173B1 (en) | 2007-12-27 | 2008-12-24 | Blue light-emitting phosphor |
| CNA2008101895259A CN101469264A (en) | 2007-12-27 | 2008-12-29 | Blue light-emitting fluophor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007337403A JP5330684B2 (en) | 2007-12-27 | 2007-12-27 | Blue-emitting phosphor particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009155546A JP2009155546A (en) | 2009-07-16 |
| JP5330684B2 true JP5330684B2 (en) | 2013-10-30 |
Family
ID=40827075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007337403A Expired - Fee Related JP5330684B2 (en) | 2007-12-27 | 2007-12-27 | Blue-emitting phosphor particles |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5330684B2 (en) |
| KR (1) | KR101538173B1 (en) |
| CN (1) | CN101469264A (en) |
| TW (1) | TW200940685A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009049056A1 (en) * | 2009-10-12 | 2011-04-14 | Osram Gesellschaft mit beschränkter Haftung | Process for coating a silicate phosphor |
| CN106025043B (en) * | 2016-05-30 | 2017-07-28 | 江苏博睿光电有限公司 | New concept-based phosphor with implanted edge angles and penetration diffusion layer and light-emitting device |
| KR102021328B1 (en) * | 2017-12-27 | 2019-09-16 | 주식회사 디엔에스 | Blue phosphor nanoparticles having a core cell structure and blue light emitting diode using the same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3234526B2 (en) * | 1996-08-29 | 2001-12-04 | 松下電器産業株式会社 | Plasma display panel and method of manufacturing phosphor for plasma display |
| JP2002069442A (en) * | 2000-09-01 | 2002-03-08 | Showa Denko Kk | Silica film coated with light emitting grain |
| JP3985478B2 (en) * | 2000-09-29 | 2007-10-03 | 住友化学株式会社 | Phosphor for vacuum ultraviolet light-excited light emitting device |
| JP2003238954A (en) * | 2002-02-18 | 2003-08-27 | Matsushita Electric Ind Co Ltd | Plasma display apparatus |
| DE10307282A1 (en) * | 2003-02-20 | 2004-09-02 | Osram Opto Semiconductors Gmbh | Coated phosphor, light-emitting device with such phosphor and method for its production |
| JP2005120320A (en) * | 2003-10-20 | 2005-05-12 | Sony Corp | Light emitter, method for producing the same, and fed and pdp devices using light emitter |
| JP4524469B2 (en) * | 2004-06-03 | 2010-08-18 | Ｄｏｗａエレクトロニクス株式会社 | Phosphor particles, method for producing the same, plasma display panel, illumination device, and LED |
| JP4861722B2 (en) * | 2005-03-01 | 2012-01-25 | 宇部マテリアルズ株式会社 | Blue light emitting phosphor powder and method for producing the same |
| JP2007224262A (en) * | 2005-08-18 | 2007-09-06 | Sumitomo Chemical Co Ltd | Phosphor particle |
| JP2008111080A (en) * | 2006-10-31 | 2008-05-15 | Mitsubishi Chemicals Corp | Method of surface-treating fluorescent substance, fluorescent substance, fluorescent substance-containing composition, light emitting device, image display device, and illuminating device |
| KR20090016416A (en) * | 2007-08-10 | 2009-02-13 | 우베 마테리알즈 가부시키가이샤 | A blue light-emitting phosphor |
-
2007
- 2007-12-27 JP JP2007337403A patent/JP5330684B2/en not_active Expired - Fee Related
-
2008
- 2008-12-23 TW TW097150253A patent/TW200940685A/en unknown
- 2008-12-24 KR KR1020080133582A patent/KR101538173B1/en not_active IP Right Cessation
- 2008-12-29 CN CNA2008101895259A patent/CN101469264A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TW200940685A (en) | 2009-10-01 |
| CN101469264A (en) | 2009-07-01 |
| KR101538173B1 (en) | 2015-07-20 |
| JP2009155546A (en) | 2009-07-16 |
| KR20090071457A (en) | 2009-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4796774B2 (en) | Phosphor containing boron and rare earth metal, and light source incorporating the phosphor | |
| JP5225539B2 (en) | Phosphors containing phosphates and / or boric acid of group IIIA, IVA, and lanthanide series metals, and light sources incorporating the phosphors | |
| JP4844567B2 (en) | Method for producing blue-emitting phosphor | |
| JP5330684B2 (en) | Blue-emitting phosphor particles | |
| JP2009074090A (en) | Phosphor for vacuum-ultraviolet ray-excited light-emitting element | |
| KR101323508B1 (en) | A method for preparing a fluorine-containing magnesium oxide powder | |
| JP4861722B2 (en) | Blue light emitting phosphor powder and method for producing the same | |
| JP4222099B2 (en) | Phosphor for vacuum ultraviolet light-emitting device | |
| JP4702565B2 (en) | Manganese-activated rare earth aluminate phosphor and fluorescent lamp using the same | |
| JP5230214B2 (en) | Blue light emitting phosphor powder and method for producing the same | |
| JP2005336488A (en) | Blue fluorophor for plasma display panel and method for producing the same, and plasma display panel | |
| JP2007217510A (en) | Blue light-emitting phosphor | |
| JP4639125B2 (en) | Method for producing blue-emitting phosphor | |
| JP5390305B2 (en) | Luminescent laminate | |
| JP2004026922A (en) | Fluorescent substance for vacuum ultraviolet light excitation light emission element | |
| JP4016724B2 (en) | Phosphor for vacuum ultraviolet light-emitting device | |
| JP4147915B2 (en) | Blue phosphor for vacuum ultraviolet light-emitting device | |
| JP2006206619A (en) | Phosphor | |
| JP4232559B2 (en) | Phosphor for vacuum ultraviolet light-emitting device | |
| JP4440068B2 (en) | Blue phosphor | |
| JP5484833B2 (en) | Phosphor powder composition | |
| JP2006104445A (en) | Fluorescent substance for vacuum ultraviolet-excited light-emitting diode | |
| JP2004217865A (en) | Phosphor | |
| JP2005314596A (en) | Phosphor for vacuum ultraviolet ray-excited luminescent element | |
| JP2004217709A (en) | Phosphor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100312 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120727 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120814 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121015 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130702 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130726 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |