TWI390009B - Microparticles and the use of its red fluorescence conversion medium - Google Patents
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- TWI390009B TWI390009B TW95117499A TW95117499A TWI390009B TW I390009 B TWI390009 B TW I390009B TW 95117499 A TW95117499 A TW 95117499A TW 95117499 A TW95117499 A TW 95117499A TW I390009 B TWI390009 B TW I390009B
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- 238000006243 chemical reaction Methods 0.000 title claims description 18
- 239000011859 microparticle Substances 0.000 title claims description 7
- 239000010419 fine particle Substances 0.000 claims description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- -1 lithium acetate Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7751—Vanadates; Chromates; Molybdates; Tungstates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
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- 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
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- H—ELECTRICITY
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- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
- H10H20/8512—Wavelength conversion materials
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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- Inorganic Compounds Of Heavy Metals (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本發明係關於一種新穎之微粒子及使用其之紅色螢光變換媒介。
能吸收特定之電磁波，並發出更低能量之可見光之螢光物質，已廣為人所知悉。其中，尤以無機螢光體，其可作為電漿顯示器、陰極射線管、螢光燈、白色發光二極體等之發光裝置之關鍵性物質，並因其高耐久性而在廣大範圍之用途上被利用。
然而，傳統上所使用之無機螢光體，必須以近1000℃高溫煅燒，其設備上之負擔甚大。而且，可發出紅色光且為透明之無機螢光體還未為人所知悉。
舉例而言，可發出非專利文獻1記載之紅色發光無色螢光體，就必須以高溫處理使其結晶化。同時，所獲得之無機螢光體，其係白色粉末，會使可見光反射而為非透明者。
非專利文獻：色材，74[10]，495(2001)
本發明之目的，係提供一種新穎之微粒子及使用其之紅色螢光變換媒介、發光裝置及資訊傳遞媒介。
根據本發明，可提供以下之微粒子、及紅色螢光變換媒介等。
1.一種微粒子，其特徵為至少含有以下述化學式表示，且數平均粒徑為100nm以下之金屬氧化物，Ax
Ly
Mz
Ou
(式中，A為選自Li、Na、K、Cs、Rb之鹼金屬或銀，L為選自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu之三價之稀土類，M為W、Mo、Cr、Mn、Ru、Os、Ir或Re，x為0~2，y為0.5~2，z為0.5~4，u為5~10。)
2.如1之微粒子，其中有平均50%以上之波長400~700nm之光透過者。
3.如1或2之微粒子，其中該金屬氧化物係在500℃以下之溫度所合成者。
4.一種包含於如1~3中任一項之微粒子之金屬氧化物之製造方法，其特徵係自含有A之鹽、含有L之鹽、及含有M之鹽或含有M之氧化物，於500℃以下之溫度下合成者。
5.一種紅色螢光變換媒介，其特徵係包含如1~3中任一項之微粒子。
6.一種發光裝置或資訊傳遞媒介，其特徵係以包含如5之紅色螢光變換媒介所構成者。
7.一種分散體，其特徵係將如1~3中任一項之微粒子，分散於溶劑或樹脂中者。
8.一種螢光油墨，其特徵係將如1~3中任一項之微粒子，分散於溶劑或樹脂中者。
9.一種如5之紅色螢光變換媒介之製造方法，其特徵係使用如7之螢光油墨所製造者。
本發明之微粒子，其特徵為至少含有以下述化學式表示之金屬氧化物。
Ax
Ly
Mz
Ou
式中，A為選自Li、Na、K、Cs、Rb之鹼金屬或銀，較佳者為Li、K。L為選自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu之三價之稀土類，較佳者為Eu、Tb。M為W、Mo、Cr、Mn、Ru、Os、Ir或Re，較佳者為W、Mo。x為0~2，較佳為0.5~2：y為0.5~2；z為0.5~4，較佳為1~4；u為5~10，較佳為6~10。)
較佳之金屬氧化物，例如有KEuMo2
O8
、KEuW2
O8
、LiEuMo2
O8
、LiEuW2
O8
等。
本發明之金屬氧化物，其數平均粒徑，一般係100nm以下，較佳為80nm以下。數平均粒徑，可依據離心分離、薄膜過濾等加以調整。
本發明之微粒子，較佳係透明者，具體而言，則為有平均50%以上之波長400~700nm之光透過者。透過性，係將微粒子分散於1,4－丁二醇等溶劑或樹脂中，再使波長400~700nm之光透過來加以測定。此時，光路徑係以10mm換算，一般其平均為50%以上，較佳則為平均為75%以上者。
透明之微粒子，可以散亂少且有效率地發出螢光。再者，因為係透明之故，很少使產品著色，必要時可使必須之部分發光。
構成本發明之微粒子之金屬氧化物，可使用含有A之鹽、含有L之鹽、及含有M之鹽或含有M之氧化物，於100℃至500℃以下之溫度下進行合成。惟，x＝0時則無需使用含有A之鹽。舉例而言，如為LiEuW2
O8
時，可自醋酸鋰等酸鋰鹽、醋酸銪(III)等酸銪鹽、及磷鎢酸等之酸鎢鹽或含鎢氧化物，在1,4－丁二醇、1,3－丁二醇等之乙二醇溶劑等溶劑中，於200℃以下之溫度加以合成。此時，溶劑係以預先在150~200℃預熱者為較佳。反應時間，一般為30~180分鐘，惟並不限於此，可適當地加以設定。反應壓力，一般為1.0~5.0氣壓，惟並不限於此，可適當地加以設定。
本發明之微粒子，其可為金屬氧化物單獨，亦可為金屬氧化物與有機殘基(例如烷基、烷基氧基、烷基羰基、烷基羰基氧基)所鍵結者。有機殘基所鍵結之金屬氧化物，例如有(CH3
COO)2
LiEuW2
O7
等。可藉由將具有有機殘基之羧酸(鹽)、羧酸酐(鹽)、醇、酯等，在溶劑中定量地或過剩地(亦可作為溶劑而使用)使其溶解，並在微粒子生成時使其與金屬氧化物發生反應、鍵結，從而能形成具有有機殘基之金屬氧化物。藉由鍵結該有機殘基，其對於各種溶劑之分散性可提高，透明性亦可提高。
因為上述之金屬氧化物可發出紅色光，本發明之微粒子可作為紅色螢光變換媒介而使用。
所謂紅色，一般係指波長580~700nm之光。舉例而言，LiEuW2
O8
會吸收波長200~425nm之光，而發出紅色光。
紅色螢光變換媒介，一般係本發明之微粒子分散於溶劑或樹脂等之媒介中者。
微粒子中所包含之金屬氧化物，為防止結晶構造之破壞、螢光性之消滅，亦可以二氧化矽等金屬氧化物或有機物等進行表面修飾。
進而，在金屬氧化物之表面，為提高對於媒介之分散性，舉例而言，亦可以長鏈烷基、磷酸、樹脂等，將表面修飾或塗佈。
媒介，係將微粒子加以分散、保持之媒介，其係以透明者為較佳，並可選擇玻璃或透明樹脂等透明材料。
具體而言，有聚甲基甲基丙烯酸酯、聚丙烯酸酯、聚碳酸酯、聚乙烯醇、聚乙烯吡咯烷酮、羥乙基纖維素、羧甲基纖維素等之透明樹脂(高分子)。
再者，亦可選擇適用於光微影法之感光性樹脂。
舉例而言，有具有丙烯酸系、甲基丙烯酸系、聚肉桂酸乙烯系、環橡膠矽等之反應性乙烯基之光硬化性型光阻材料。
再者，使用印刷法時，可選擇使用透明樹脂之印刷油墨(清漆)。舉例而言，有聚氯乙烯樹脂、三聚氰胺樹脂、苯酚樹脂、醇酸樹脂、環氧樹脂、聚胺基甲酸乙酯樹脂、聚酯樹脂、馬來酸樹脂、聚醯胺樹脂之單體、低聚物、聚合物。
這些樹脂，亦可為熱硬化型者。再者，這些樹脂，可單獨使用一種樹脂，亦可混合多數種類而加以使用。
紅色螢光變換媒介，可將微粒子及媒介，使用米爾法或超音波分散法等習知之方法，再使用混合、分散之分散液而製作。
此時，可使用前述透明媒介之優良溶劑。可使用該分散液，藉由光微影法或各種印刷法，而製作紅色螢光變換媒介之圖型。
如將紅色螢光變換媒介，使用在溶劑或樹脂中分散有微粒子之螢光油墨，並以旋轉塗佈法、噴墨法等濕式法進行製造時，因為其係可形成均一之膜之故而為較佳者。
在此，微粒子及透明媒介之混合比(微粒子/透明媒介：重量比)，會因為微粒子之比重、粒徑而有所不同，惟較佳係1/20~4/6，最佳則為1/9~3/7者。
再者，在不危害及本發明目的之範圍內，亦可在紅色螢光變換媒介中，添加紫外線吸收劑、分散劑、整平劑等。
含有本發明之紅色螢光變換媒介，並可構成發光裝置或資訊傳遞媒介。資訊傳遞媒介，例如有照明、操縱盤、電視等。
將醋酸鋰2.5mmol(0.255g)、醋酸銪(III)2.5mmol(1.003g)、及磷鎢酸0.4167mmol(1.200g)，投入於以180℃預熱之1，4-丁二醇50mL中，於室溫下攪拌，並使其進行80分鐘之熟成，而製得透明分散液。該透明分散液，如以465nm光激化時會發出紅色光。
如此地，目的之微粒子(金屬氧化物)可於低溫下簡單地加以製造。
關於將透明分散液以水加以稀釋之溶液，藉由動態光散亂法進行粒子徑分布測定。其結果如圖1所示。由圖1中，可知分散有直徑約40nm之奈米粒子。
透明分散液之螢光、激態光譜係示於圖2中。圖2中，可觀測到藉由Eu3+
之f-f遷移之激態及紅色發光峰部。此外，該圖中，PLE表示激態光譜，PL則表示發光光譜。
進而，如將該透明分散液分散於1，4-丁二醇中，並使波長400~700nm之光透過時，光路徑以10mm換算，平均有65%透過者。
將醋酸鋰2.5mmol(0.255g)、醋酸銪(III)2.5mmol(1.003g)、及磷鎢酸0.4167mmol(1.200g)，投入於以180℃預熱之1，4－丁二醇10mL中，於室溫下以攪拌子攪拌，並使其進行80分鐘之熟成，而製得半透明凝膠。本實施例中，係以實施例1之5倍濃度製作分散體。
測定X射線繞射之結果，半透明凝膠為非晶體物質。
將半透明凝膠以10℃/分鐘升溫，並以600℃煅燒1小時而製得粉末樣品。將該粉末樣品及NaYW2
O8
之X射線繞射圖示於圖3中。圖3中，上方者為粉末樣品，下方者則為NaYW2
O8
。藉由將粉末樣品之圖與具有鐵鋁酸四鈣(Celite)型結構之NaYW2
O8
之圖加以比較，即可確認有鐵鋁酸四鈣型結晶結構之LiEuW2
O8
產生。
透明分散凝膠之螢光、激態光譜係示於圖4中。如圖4所示者，在螢光、激態光譜中，可觀測到藉由Eu3 ＋
之f－f遷移之激態及紅色發光峰部。
除使用密閉有1，4－丁二醇之耐壓容器，預熱至600℃以外，其餘皆與實施例2相同地進行，而製得其樣品。該樣品係失去透明性而為白色者。
本發明之紅色螢光變換媒介，其可使用於民生用及工業用之顯示器(廣告等)、資訊傳遞媒介等。具體而言，可使用於看板、行動電話、PDA、汽車導航系統、顯示器、電視、照明等。
圖1：係就實施例1所得到之透明分散液，藉由動態光散亂法所測定之粒子徑分布之標示圖。
圖2：係實施例1所得到之透明分散液之螢光、激態光譜圖。
圖3：係NaYW2
O8
與實施例2所得到之粉末樣品之X射線繞射圖。
圖4：實施例2所得到之透明分散凝膠之螢光、激態光譜圖。
Claims (6)
- 一種透明微粒子，其特徵為至少含有以下述化學式表示，且數平均粒徑為100nm以下之金屬氧化物的平均50%以上之波長400~700nm之光透過者，而前述金屬氧化物係自含有A之鹽、含有L之鹽、及含有M之鹽或含有M之氧化物，於200℃以下之溫度下合成者，Ax Ly Mz Ou (式中，A為選自Li、K之鹼金屬，L為選自Eu、Tb之三價之稀土類，M為W或Mo，x為0~2，y為0.5~2，z為0.5~4，u為5~10)。
- 一種包含於如申請專利範圍第1項之透明微粒子之金屬氧化物之製造方法，其特徵係自含有A之鹽、含有L之鹽、及含有M之鹽或含有M之氧化物，於200℃以下之溫度下合成者。
- 一種紅色螢光變換媒介，其特徵係包含如申請專利範圍第1項之透明微粒子。
- 一種發光裝置或資訊傳遞媒介，其特徵係以包含如申請專利範圍第3項之紅色螢光變換媒介所構成者。
- 一種分散體，其特徵係將如申請專利範圍第1項之透明微粒子，分散於溶劑或樹脂中者。
- 一種螢光油墨，其特徵係將如申請專利範圍第1 項之透明微粒子，分散於溶劑或樹脂中者。
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| WO2008139397A1 (en) * | 2007-05-15 | 2008-11-20 | Philips Intellectual Property & Standards Gmbh | Novel color filters for color displays and light sources |
| CN102212364A (zh) * | 2011-04-01 | 2011-10-12 | 中国科学院上海光学精密机械研究所 | 铕激活的钼酸盐红色荧光粉及其制备方法 |
| CN103289691B (zh) * | 2012-02-28 | 2015-11-04 | 海洋王照明科技股份有限公司 | 铜铱双掺杂钨酸盐发光材料、制备方法及其应用 |
| KR20140074516A (ko) * | 2012-12-10 | 2014-06-18 | 서울바이오시스 주식회사 | 질화갈륨계 반도체층 성장 방법 및 발광 소자 제조 방법 |
| DE102014107268A1 (de) * | 2014-05-22 | 2015-11-26 | H1 Energy Bv | Energieumwandlungssystem |
| CN106544020B (zh) * | 2016-09-23 | 2019-03-22 | 长安大学 | 纳米银颗粒增强的稀土掺杂钨酸盐发光材料及制备方法 |
| CN110951337A (zh) * | 2019-10-23 | 2020-04-03 | 广东华斓汽车材料研究院 | 一种水性路标漆、制备方法及设备 |
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| US20090127510A1 (en) | 2009-05-21 |
| JP5009792B2 (ja) | 2012-08-22 |
| CN101180380B (zh) | 2013-01-09 |
| KR20080018987A (ko) | 2008-02-29 |
| KR101262409B1 (ko) | 2013-05-08 |
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