WO2011106938A1 - 用于白光led光源的发光纳米微晶玻璃及其制备方法 - Google Patents

用于白光led光源的发光纳米微晶玻璃及其制备方法 Download PDF

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WO2011106938A1
WO2011106938A1 PCT/CN2010/070880 CN2010070880W WO2011106938A1 WO 2011106938 A1 WO2011106938 A1 WO 2011106938A1 CN 2010070880 W CN2010070880 W CN 2010070880W WO 2011106938 A1 WO2011106938 A1 WO 2011106938A1
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glass
sio
luminescent
nano
light source
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PCT/CN2010/070880
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English (en)
French (fr)
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周明杰
乔延波
马文波
陈丹平
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海洋王照明科技股份有限公司
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Priority to JP2012555276A priority Critical patent/JP5529296B2/ja
Priority to CN2010800612351A priority patent/CN102712525A/zh
Priority to US13/582,501 priority patent/US9260340B2/en
Priority to EP10846857.0A priority patent/EP2543646A4/en
Priority to PCT/CN2010/070880 priority patent/WO2011106938A1/zh
Publication of WO2011106938A1 publication Critical patent/WO2011106938A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/08—Doped silica-based glasses containing boron or halide
    • C03C2201/10—Doped silica-based glasses containing boron or halide containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/32—Doped silica-based glasses containing metals containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/16—Microcrystallites, e.g. of optically or electrically active material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/20—Glass-ceramics matrix
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/32—Nature of the non-vitreous component comprising a sol-gel process
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/764—Garnet structure A3B2(CO4)3

Definitions

  • the invention belongs to the field of illumination display and optoelectronic technology, and relates to a luminescent glass and a preparation method thereof, in particular to an illuminating nanometer crystal glass for a white light LED light source and a preparation method thereof. Background technique
  • LEDs have been widely used in signal lights, automotive lights, large-screen displays, and lighting because of their long life, low power consumption, and fast startup.
  • the most commonly used white LED is a combination of a blue LED chip and a phosphor to obtain white light.
  • the principle is as follows: The blue chip excites the phosphor to produce yellow light, and the blue light and the yellow light complement each other to produce white light perceived by the human eye.
  • phosphors for white LEDs mainly include yttrium-doped aluminum garnet (YAG:Ce) phosphors, silicate phosphors and nitride phosphors, among which YAG:Ce phosphors are the most widely used.
  • the above-mentioned high-quality phosphor for white LEDs is expensive to manufacture, and in the packaging process, phosphors and glues are required to be mixed, and the phosphors are mixed with the glue.
  • the compatibility of the two is poor, the phosphor is prone to precipitation, resulting in uneven coating, resulting in poor uniformity of light output of the LED device, and the color tone consistency is difficult to ensure, thereby causing high spectral separation color cost of the white LED. Due to the high manufacturing cost and the unreliable quality, the white LED luminescent materials of many domestic packaging factories still rely on imports. Summary of the invention
  • the technical problem to be solved by the present invention is to provide an illuminating nano-ceramic glass for a white LED light source with good stability, low cost and uniform light emission for the above-mentioned defects of the prior art.
  • the technical problem to be further solved by the present invention is to provide a method for preparing a luminescent nano-crystal glass for a white light LED light source with simple preparation process, convenient and reliable operation, and stable product quality.
  • an illuminating nano-ceramic glass for a white light LED light source which is a kind of non-dispersed Y x Gd 3 _ x Al 5 O 12: Ce nano luminescent crystallite A densely packed Si0 2 glass, where 0 ⁇ x ⁇ 3.
  • the luminescent nanometer crystallized glass is based on SiO 2 nanometer microporous glass, and has a chemical formula Y x distributed in the micropores of the SiO 2 nanometer microporous glass.
  • Gd 3 _ x Al 5 0 12 Ce nano luminescent microcrystals
  • the micropore shrinkage is formed to wrap Y x
  • Gd 3 _ x Al 5 O 12 Ce nano-luminous microcrystalline non-porous dense SiO 2 glass.
  • the volume of the micropores in the 810 2 nm microporous glass accounts for 25-40% of the total volume of the SiO 2 nanoporous glass.
  • the SiO ⁇ microporous glass is mainly composed of the following parts by weight:
  • the preparation method of the luminescent nanometer crystal glass for the white light LED light source comprises the following steps: (1), in the oxides, nitrates, chlorides, sulfates, acetates of Y 3+ and Gd 3+ At least one of Al 3+ oxide, nitrate, chloride, sulfate, acetate, and Ce 3+ oxide, nitrate, chloride, sulfate, acetate At least one of the raw materials, the raw material is dissolved in a solvent to prepare a mixed solution of luminescent compound ions, and the mixed solution is Al 3+
  • the concentration is 0.5 ⁇ 2mol/L
  • the concentration of Y 3+ and Gd 3+ is 0.3 ⁇ 1.2mol/L
  • the concentration of Ce 3+ is 0.001 ⁇ 0.2mol/L
  • the solvent is selected by using nitric acid, hydrochloric acid, sulfuric acid or acetic acid; when the raw material selects the nitrate, chloride, and In the case of sulfate or acetate, the solvent is selected from water.
  • the SiO 2 nanometer microporous glass is placed in the mixed solution prepared by the step (1) and soaked for 30 minutes to 5 hour.
  • the immersed SiO 2 nanometer microporous glass is first dried to room temperature at room temperature, and then placed in a high temperature furnace. The temperature is gradually increased to 1150 ⁇ 1250 °C, and the SiO 2 nanoporous glass after soaking is sintered at this temperature for 2 ⁇ 4 hours, and then cooled to room temperature after sintering, and taken out to obtain luminescent nanometer for white LED light source. Glass-ceramic; wherein the temperature rise rate is not higher than 15 ° C / min in the temperature range below 400 ° C and above 900 ° C.
  • the SiO 2 nanometer microporous glass is mainly composed of the following parts by weight: SiO 2 94.0 ⁇ 98.0, B 2 O 3 1.0 ⁇ 3.0, A1 2 0 3 1 ⁇ 0 ⁇ 3 ⁇ 0.
  • Y x Gd 3 _ x Al 5 0 12 Ce luminescent nanocrystallites are dispersed, and the luminescent nanocrystalline glass can generate yellow luminescence under blue light excitation, and can be used for a white LED light source.
  • Y x Gd 3 _ x Al 5 O 12 Ce luminescent nanocrystallite can be well dispersed in the glass, effectively reducing the non-radiative transition of luminescent ions in the glass, and avoiding the concentration quenching effect caused by the cluster.
  • the volume of the micropores accounts for 25-40% of the total volume of the SiO 2 nanoporous glass, ensuring a sufficient amount of luminescent particles in the micropores, so that the glass of the invention has good luminescent properties.
  • the nanoporous glass substrate has good permeability to ultraviolet light, which is very favorable for the absorption of the excitation wavelength by the luminescent ions, thereby improving the luminous efficiency.
  • the invention adopts SiO ⁇ ft rice microporous glass as the substrate, and the porous SiO 2 nanoporous glass material is very suitable for preparing nano materials, especially the 810 2 nanometer microporous glass is transparent in the visible light region, and can be used as the light function nanometer.
  • the matrix material of the particles Due to the special pore structure of 810 2 nanometer microporous glass, nanometer-sized luminescent particles can be made through micropores. After SiO 2 nanoporous glass is sintered, micropore shrinkage closes the luminescent particles to form dense, non-porous and transparent.
  • the glass-ceramic with high mechanical strength, and the luminescent particles are enclosed in the glass, the product can maintain its chemical stability for a long time.
  • the luminescent nanocrystalline glass in the invention has a high content of 810 2 and a composition similar to quartz glass, and has excellent physical and chemical properties similar to quartz glass, such as good chemical stability, high mechanical strength, low thermal expansion coefficient, and thermal shock resistance. Wait. These excellent properties enable the glass of the present invention to be used in many special fields, especially in harsh environments such as high temperature, high pressure, high vibration and humidity, and high power, high repetition rate solid state.
  • Luminescent nano-ceramic glass provides a system A new approach to nanomaterials, especially a new method for preparing luminescent nanocrystalline transparent glass materials.
  • Ce luminescent nano crystallite glass of the invention has the advantages of simple process, reliable product performance and low cost.
  • the use of this new type of luminescent material for white LED packaging can solve many problems of current phosphor and glue hybrid packaging, and has great investment development value and broad application market.
  • Example 2 is an emission spectrum of Y 3 Al 5 0 12 :Ce nanocrystalline glassware prepared in Example 1 under excitation of 460 nm blue light. detailed description
  • Example 1 Y 3 Al 5 0 12 : Ce Nanocrystalline glass is a non-porous dense SiO 2 glass in which nano luminescent crystallites of the formula Y 3 Al 5 0 12 :Ce are dispersed.
  • Y 3 Al 5 0 12 :Ce nanocrystalline glass was prepared according to the preparation flow chart shown in FIG. Ho step is prepared: 1.149g weighed using an analytical balance analytically pure ⁇ ( ⁇ 3) 3 ⁇ 63 ⁇ 4 ⁇ ( yttrium nitrate hexahydrate), 1.875g analytically pure ⁇ 1 ( ⁇ 0 3) 3 ⁇ 6 ⁇ 2 0 ( hexahydrate of aluminum nitrate And 0.0043 g of analytically pure Ce(N0 3 ) 3 '6H 2 0 (cerium nitrate hexahydrate) dissolved in 10 ml of distilled water to prepare 0.3 mol/L 3+ , 0.5 mol/L Al 3+ and 0.001 mol /L Ce 3+ mixed solution.
  • Y 3 Al 5 O 12 :Ce nanocrystalline glass is a non-porous dense SiO 2 glass in which nano luminescent crystallites of the formula Y 3 Al 5 O 12 :Ce are dispersed.
  • the SiO 2 nanoporous glass was immersed in the mixed solution for 1 hour, and then taken out, dried at room temperature until the surface was dried, and then placed in a high temperature furnace.
  • the high temperature furnace was first raised to 400 ° C at a rate of 10 ° C / min, and then 15
  • the speed of °C/min was raised to 900 °C, then it was raised to 1200 °C at 5 °C/min, and sintered at 1200 °C for 2 h.
  • the sintered glass was taken out to room temperature with the furnace.
  • Y 3 Al 5 O 12 :Ce nanocrystalline glass was prepared, which produced yellow light emission under blue light excitation.
  • Example 3: Y 3 Al 5 O 12 :Ce nanocrystalline glass is a non-porous dense SiO 2 glass in which nano luminescent crystallites of the formula Y 3 Al 5 O 12 :Ce are dispersed.
  • Preparation step 2.746 g of analytically pure Y 2 (SO 4 ) 3 _83 ⁇ 4O (barium sulfate octahydrate), 4.998 g of analytically pure A1 2 (S0 4 ) 3 8H 2 0 (aluminum sulfate octahydrate) was weighed using an analytical balance. ) and 0.202g analytically pure Ce (SO 4) 2 -4H 2 O ( tetrahydrate ceric sulfate) was dissolved in 10ml of distilled water, formulated containing 0.9mol / LY 3+, 1.5 mol / LAl 3+ and 0.05mol / A mixed solution of L Ce 3+ .
  • the SiO 2 nanoporous glass was immersed in the mixed solution for 8 hours, and then taken out, dried at room temperature until the surface was dried, and then placed in a high temperature furnace.
  • the high temperature furnace was first raised to 400 ° C at a rate of 10 ° C / min, and then 15 The speed of °C/min is increased to 900 °C, then it is raised to 1100 °C at 5 °C/min, and sintered at 1100 °C for 4 h.
  • the sintered glass is cooled to room temperature with the furnace. Out.
  • Y 3 Al 5 O 12: Ce nanocrystalline glass was produced, which produced yellow light emission under blue light excitation.
  • Example 4: Y 3 Al 5 O 12 :Ce nanocrystalline glass is a non-porous dense SiO 2 glass in which nano luminescent crystallites of the formula Y 3 Al 5 0 12 :Ce are dispersed.
  • Preparation steps 0.135 g of analytically pure cerium oxide (Y 2 O 3 :», 0.102 g of analytically pure ⁇ 1 2 ⁇ 3 (; alumina) and 0.172 g of analytically pure CeO 2 (yttrium oxide:) were weighed using an analytical balance. Dissolved in 10 ml of nitric acid to prepare a mixed solution containing 0.12 mol/L 3+ , 0.2 mol/L Al 3+ and 0.1 mol/L Ce 3+ . Soak the SiO 2 nanoporous glass in the mixed solution for 10 h. After taking out, it is dried at room temperature until the surface is dried and placed in a high-temperature furnace.
  • the high-temperature furnace is first raised to 400 ° C at a rate of 10 ° C / min, and then raised to 900 ° C at a rate of 15 ° C / min, after The temperature was raised to 1150 ° C at 5 ° C / min, and sintered at 1150 ° C for 2.5 h. The sintered glass was taken out to room temperature with the furnace. After cutting and polishing, Y 3 Al 5 O 12 :Ce was prepared. Nanocrystalline glass, which produces yellow luminescence under blue light excitation.
  • Example 5 Y 1 5 Gd 1 5 Al 5 O 12 :Ce Nanocrystalline glass is a nano luminescent microcrystal dispersed with the chemical formula Y Gdi sAlsOisiCe Non-porous dense Si0 2 glass.
  • Preparation step 0.910 g of analytically pure ⁇ 3 ⁇ 6 ⁇ 2 ⁇ (cerium chloride hexahydrate), 1.115 g of analytically pure GdCl 3 '6H 2 0 (chlorinated hexahydrate), 2.414 g analysis were weighed using an analytical balance.
  • A1C1 3 '6H 2 0 (aluminum chloride hexahydrate) and 0.075 g of analytically pure CeCl 3 H 2 0 (cerium chloride heptahydrate) are dissolved in 10 ml of distilled water to prepare 0.3 mol/L 3+ A mixed solution of 0.3 mol/L Gd 3+ , 1 mol/L Al 3+ and 0.02 mol/L Ce 3+ .
  • the SiO 2 nanoporous glass was immersed in the mixed solution for 10 hours, and then taken out, dried at room temperature until the surface was dried, and then placed in a high temperature furnace.
  • YGd 2 Al 5 O 12 :Ce Nanocrystalline glass is a non-porous dense SiO 2 glass in which nano luminescent crystallites of the formula YGd 2 Al 5 O 12 :Ce are dispersed.
  • the high temperature furnace was first raised to 400 ° C at a rate of 10 ° C / min, and then 15 The speed of °C/min was raised to 900 °C, then it was raised to 1300 °C at a speed of 5 °C/min, and sintered at 1300 °C for 5 h. After sintering, it was taken out to cool at room temperature. After cutting and polishing, YGd 2 Al 5 0 12 :Ce nanocrystalline glass was produced, which produced yellow luminescence under blue light excitation.
  • Example 7: Gd 3 Al 5 0 12 :Ce Nanocrystalline glass is a non-porous dense SiO 2 glass in which nano luminescent crystallites of the formula Gd 3 Al 5 O 12 :Ce are dispersed.
  • the SiO 2 nanoporous glass was immersed in the mixed solution for 10 hours, and then taken out, dried at room temperature until the surface was dried, and placed in a high temperature furnace.
  • the high temperature furnace was first raised to 400 ° C at a rate of 10 ° C / min. Then increase to 900 ° C at 15 ° C / min, then rise to 1300 ° C at 5 ° C / min, After sintering at 1300 ° C for 2 h, the sintered glass was taken out to room temperature with the furnace.
  • Gd 3 Al 5 O 12: Ce nanocrystalline glass was prepared, which produced yellow light emission under blue light excitation.
  • Preparation steps 1.014 g of analytically pure Y(CH 3 COO) 3 4H 2 O (cerium acetate tetrahydrate), 1.020 g of analytically pure Al(CH 3 COO) 3 (aluminum acetate) and 0.0407 g were weighed using an analytical balance. Pure Ce(CH 3 COO) 3 -5H 2 O (ruthenium acetate pentahydrate) is dissolved in 10ml of distilled water and formulated into 0.3mol/LY 3+ , 0.5mol/L Al 3+ and O.Olmol/L Ce 3+ Mixed solution.
  • the SiO 2 nanoporous glass was immersed in the mixed solution for 24 hours, and then taken out, dried at room temperature until the surface was dried, and placed in a high temperature furnace.
  • the high temperature furnace was first raised to 400 ° C at a rate of 10 ° C / min, and then 15
  • the speed of °C/min was raised to 900 °C, then it was raised to 1200 °C at 5 °C/min, and sintered at 1200 °C for 4 h. After sintering, it was cooled to room temperature with the furnace. After cutting and polishing, Y 3 Al 5 0 12 :Ce nanocrystalline glass was prepared, which produced yellow luminescence under blue light excitation.

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Description

用于白光 LED光源的发光纳米微晶玻璃及其制备方法 技术领域
本发明属于照明显示及光电子技术领域， 涉及一种发光玻璃及其制备方 法， 尤其涉及一种用于白光 LED光源的发光纳米微晶玻璃及其制备方法。 背景技术
由于发光二极管（LED)具有寿命长、 能耗低、启动快等优点， 使得 LED 器件已被广泛应用于信号灯、汽车灯、大屏幕显示及照明等领域。 目前最常用 的白光 LED是采用蓝光 LED芯片与荧光粉组合来获取白光。其原理是： 蓝光 芯片激发荧光粉产生黄色发光，蓝光与黄光互补产生人眼感受到的白光。 目前 用于白光 LED的荧光粉主要有掺铈的^铝石榴石（YAG:Ce)荧光粉， 硅酸盐 荧光粉和氮化物荧光粉等， 其中 YAG:Ce荧光粉的应用最多。然而， 由于荧光 粉颗粒的形状和粒度大小不好控制， 造成上述用于白光 LED的高质量荧光粉 的制作成本高， 并且在封装过程中， 需要荧光粉与胶混合， 在荧光粉与胶混合 的混合物中， 二者的相容性差， 荧光粉易发生沉淀， 导致布胶不均匀， 造成 LED器件的出光均匀性差， 色调一致性难以保证， 从而造成了白光 LED高昂 的分光分色成本。 由于制造成本高、 品质不易保证， 目前国内很多封装厂的白 光 LED发光材料仍然依赖进口。 发明内容
本发明要解决的技术问题在于，针对现有技术的上述缺陷，提供一种稳定 性好、 成本低、 出光均匀的用于白光 LED光源的发光纳米微晶玻璃。 本发明进一步要解决的技术问题在于，提供一种制备工艺简单、操作方便 可靠、 产品质量稳定的用于白光 LED光源的发光纳米微晶玻璃的制备方法。
本发明解决其技术问题所采用的技术方案是： 一种用于白光 LED光源的 发光纳米微晶玻璃， 是一种分散有 YxGd3_xAl5O12:Ce纳米发光微晶的无孔密实 的 Si02玻璃， 其中 0≤x≤3。
用于白光 LED光源的发光纳米微晶玻璃中， 所述的发光纳米微晶玻璃是 以 Si02纳米微孔玻璃为基材， 在 Si02纳米微孔玻璃的微孔内分布有化学式为 YxGd3_xAl5012:Ce纳米发光微晶， 将含有该纳米发光微晶的 Si02纳米微孔玻璃 经烧结后， 微孔收缩形成包裹有 YxGd3_xAl5O12:Ce纳米发光微晶的无孔密实的 SiO2玻璃.
用于白光 LED光源的发光纳米微晶玻璃中， 8102纳米微孔玻璃中的微孔 的体积占 SiO2纳米微孔玻璃总体积的 25~40%。
用于白光 LED光源的发光纳米微晶玻璃中， 所述的 SiO^米微孔玻璃主 要由以下重量份数的成分组成：
SiO2 94.0-98.0
B2O3 1.0-3.0
A1203 1.0〜3.0。
用于白光 LED光源的发光纳米微晶玻璃的制备方法， 包括以下歩骤： ( 1 )、 以 Y3+、 Gd3+的氧化物、硝酸盐、 氯化物、 硫酸盐、 乙酸盐中的至 少一种、 Al3+的氧化物、 硝酸盐、 氯化物、 硫酸盐、 乙酸盐中的至少一种 和 Ce3+的氧化物、 硝酸盐、 氯化物、 硫酸盐、 乙酸盐中的至少一种为原料， 将上 述原料溶解于溶剂中制成发光化合物离子的混合溶液， 所述混合溶液中 Al3+ 浓度为 0.5~2mol/L、 Y3+与 Gd3+的浓度和为 0.3~1.2mol/L、 Ce3+浓度为浓度为 0.001~0.2mol/L;
(2 )、 选取具有联通微孔的 SiO^fi米微孔玻璃为基材， 其中 SiO2纳米微 孔玻璃的微孔体积占 SiO2纳米微孔玻璃总体积的 25~40%; 将 SiO2纳米微孔 玻璃放入步骤 （1 ) 制成的混合溶液中浸泡 10分钟以上；
(3 )、 将浸泡后的 SiO2纳米微孔玻璃逐步升温至 1100~1300°C下烧结 1~5 小时， 制得用于白光 LED光源的发光纳米微晶玻璃。
用于白光 LED光源的发光纳米微晶玻璃的制备方法中， 当原料选择各离 子的氧化物时， 溶剂选用硝酸、 盐酸、硫酸或乙酸来溶解； 当原料选择各离子 的硝酸盐、 氯化物、 硫酸盐或乙酸盐时， 则溶剂选用水来溶解。
用于白光 LED光源的发光纳米微晶玻璃的制备方法中，所述歩骤（2 )中， 将 Si02纳米微孔玻璃放入歩骤 （1 ) 制成的混合溶液中浸泡 30分钟〜 5小时。
用于白光 LED光源的发光纳米微晶玻璃的制备方法中，所述歩骤（3 )中， 先将浸泡后的 Si02纳米微孔玻璃室温下晾至表面干燥， 然后再置于高温炉中 逐歩升温至 1150~1250°C，在此温度下对浸泡后的 SiO2纳米微孔玻璃烧结 2~4 小时， 烧结后随炉冷却至室温， 取出， 制得用于白光 LED光源的发光纳米微 晶玻璃； 其中在 400°C以下和 900°C以上的温度区间， 升温速度不高于 15°C/min。
用于白光 LED光源的发光纳米微晶玻璃的制备方法中， 所述的 Si02纳米 微孔玻璃主要由以下重量份数的成分组成： SiO2 94.0~98.0、B2O3 1.0~3.0、 A1203 1·0~3·0。
本发明的发光纳米微晶玻璃中， 分散有 YxGd3_xAl5012:Ce发光纳米微晶， 该发光纳米微晶玻璃能在蓝光激发下产生黄色发光， 可用于白光 LED光源。 并且 YxGd3_xAl5O12:Ce发光纳米微晶能在玻璃中能够良好地分散， 有效降低了 发光离子在玻璃中的非辐射跃迁，避免了团簇引起的浓度猝灭效应。此外微孔 的体积占 SiO2纳米微孔玻璃总体积的 25~40%，保证了微孔内有足够数量的发 光粒子， 使本发明的玻璃具有良好的发光性能。再者， 这种纳米微孔玻璃基材 对紫外光有良好的透过性能，非常有利于发光离子对激发波长的吸收，从而提 高发光效率。
本发明选用 SiO^ft米微孔玻璃为基材， 多孔的 SiO2纳米微孔玻璃材料很 适合来制备纳米材料， 尤其是 8102纳米微孔玻璃在可见光区是透明的， 可以 作为光功能纳米粒子的基质材料。 由于 8102纳米微孔玻璃特殊的孔结构， 能 够通过微孔制成纳米尺寸的发光粒子， SiO2纳米微孔玻璃经烧结后，微孔收縮 将发光粒子封闭起来，形成密实、无孔、透明、具有较高机械强度的微晶玻璃， 并且发光粒子被封闭在玻璃中， 产品能长久保持其化学稳定性。
本发明中的发光纳米微晶玻璃中 8102含量高， 成分类似于石英玻璃， 具 有类似于石英玻璃的优异物理和化学性能， 例如化学稳定性好、 机械强度高、 低热膨胀系数、耐热冲击等。这些优良性能使得本发明的玻璃能够被应用在许 多特殊的领域中， 尤其是应用在一些恶劣环境中， 例如高温、 高压、 高振动和 潮湿环境下的照明与显示，高功率高重复频率的固态激光领域，长期露天工作 的太阳能材料领域等等。
传统的高温熔融制备发光玻璃的过程中，玻璃形成体化合物的化学活性很 高，很容易导致玻璃形成体的化合物与纳米粒子反应，难以制备单分散的纳米 粒子发光纳米粒子。本发明通过将 SiO2纳米微孔玻璃浸入活性离子溶液引入发 光离子， 再经过 1100~1300°C的高温固相烧结， 克服了石英玻璃中制备单分散 发光纳米粒子的难题，得到了均匀单分散的发光纳米微晶玻璃，提供了一种制 备纳米材料的新途径， 尤其是一种制备发光纳米微晶透明玻璃材料的新方法。 本发明 YxGd3_xAl5O12:Ce发光纳米微晶玻璃制备方法工艺简单、 产品性能 可靠且成本较低。 采用这种新型发光材料进行白光 LED封装能够解决目前荧 光粉与胶混合封装的诸多问题， 具有巨大的投资开发价值和广阔的应用市场。 附图说明
图 1为 YxGd3_xAl5O12:Ce发光纳米微晶玻璃的制备流程图；
图 2为实施例 1制备出的 Y3Al5012:Ce纳米微晶玻璃在 460nm蓝光激发下 的发射光谱。 具体实施方式
实施例 1 : Y3Al5012:Ce纳米微晶玻璃是一种分散有化学式为 Y3Al5012:Ce 的纳米发光微晶的无孔密实 Si02玻璃。
按照图 1所示的制备流程图制备 Y3Al5012:Ce纳米微晶玻璃。 制备歩骤为： 使用分析天平称取 1.149g分析纯的 Υ(ΝΟ3)3·6¾Ο (六水合硝酸钇)、 1.875g分 析纯的 Α1(Ν03)3·6Η20 (六水合硝酸铝)和 0.0043g分析纯的 Ce(N03)3'6H20 (六 水合硝酸铈)溶于 10ml的蒸馏水中， 配制成含有 0.3mol/L Y3+、 0.5 mol/L Al3+ 和 0.001mol/L Ce3+的混合溶液。将 Si02纳米微孔玻璃浸泡到混合溶液中 lh后 取出， 在室温下晾至表面干燥后置入高温炉中， 高温炉先以 10°C/min的速度 升到 400°C，再以 15°C/min的速度升到 900°C，之后以 5°C/min速度升到 1200 °C， 在 1200°C下保温烧结 2h， 烧结后的玻璃随炉冷却至室温取出。 经过切割和抛 光后， 制备出的 Y3Al5O12:Ce 纳米微晶玻璃。 如图 2 所示， 是制备出的 Y3Al5012:Ce纳米微晶玻璃在 460nm蓝光激发下的发射光谱， 图中显示该玻璃 在蓝光激发下产生黄色发光。 实施例 2: Y3Al5O12:Ce纳米微晶玻璃是一种分散有化学式为 Y3Al5O12:Ce 的纳米发光微晶的无孔密实 Si02玻璃。
制备步骤： 使用分析天平称取 4.596g分析纯的 Υ(ΝΟ3)3·6Η2Ο (六水合硝酸 钇）、 7.500g 分析纯的 Α1(ΝΟ3)3·6Η20 (六水合硝酸铝）和 0.868g 分析纯的 Ce(NO3)3-6H2O (；六水合硝酸铈:)溶于 10ml的蒸馏水中， 配制成含有 1.2mol/L Y3+、 2 mol/LAl3+和 0.2mol/L Ce3+的混合溶液。 将 SiO2纳米微孔玻璃浸泡到混 合溶液中 lh后取出， 在室温下晾至表面干燥后置入高温炉中， 高温炉先以 10°C/min的速度升到 400 °C，再以 15°C/min的速度升到 900 °C，之后以 5 °C/min 速度升到 1200°C， 在 1200°C下保温烧结 2h， 烧结后的玻璃随炉冷却至室温取 出。 经过切割和抛光后， 制备出的 Y3Al5O12:Ce纳米微晶玻璃， 该玻璃在蓝光 激发下产生黄色发光。 实施例 3 : Y3Al5O12:Ce纳米微晶玻璃是一种分散有化学式为 Y3Al5O12:Ce 的纳米发光微晶的无孔密实 Si02玻璃。
制备歩骤：使用分析天平称取 2.746g分析纯的 Y2(SO4)3_8¾O (八水合硫酸 钇)、 4.998g分析纯的 A12(S04)3 8H20 (十八水合硫酸铝)和 0.202g分析纯的 Ce(SO4)2-4H2O (四水合硫酸铈)溶于 10ml 的蒸馏水中， 配制成含有 0.9mol/L Y3+、 1.5 mol/LAl3+和 0.05mol/L Ce3+的混合溶液。将 SiO2纳米微孔玻璃浸泡到 混合溶液中 8h后取出， 在室温下晾至表面干燥后置入高温炉中， 高温炉先以 10°C/min的速度升到 400°C，再以 15°C/min的速度升到 900 °C，之后以 5 °C/min 速度升到 1100°C， 在 1100°C下保温烧结 4h， 烧结后的玻璃随炉冷却至室温取 出。 经过切割和抛光后， 制备出 Y3Al5O12:Ce纳米微晶玻璃， 该玻璃在蓝光激 发下产生黄色发光。 实施例 4: Y3Al5O12:Ce纳米微晶玻璃是一种分散有化学式为 Y3Al5012:Ce 的纳米发光微晶的无孔密实 SiO2玻璃。
制备步骤： 使用分析天平称取 0.135g分析纯的氧化钇 (Y2O3:»、 0.102g分析 纯的 Α12Ο3 (；氧化铝)和 0.172g分析纯的 CeO2 (氧化铈:)溶于 10ml的硝酸中， 配 制成含有 0.12mol/L Y3+、 0.2 mol/L Al3+和 O. lmol/L Ce3+的混合溶液。 将 Si02 纳米微孔玻璃浸泡到混合溶液中 10h后取出，在室温下晾至表面干燥后置入高 温炉中， 高温炉先以 10°C/min的速度升到 400°C， 再以 15°C/min的速度升到 900°C， 之后以 5°C/min速度升到 1150°C， 在 1150°C下保温烧结 2.5h， 烧结后 的玻璃随炉冷却至室温取出。 经过切割和抛光后， 制备出 Y3Al5O12:Ce纳米微 晶玻璃， 该玻璃在蓝光激发下产生黄色发光。 实施例 5： Y1 5Gd1 5Al5O12:Ce 纳米微晶玻璃是一种分散有化学式为 Y Gdi sAlsOisiCe的纳米发光微晶的无孔密实 Si02玻璃。
制备歩骤：使用分析天平称取 0.910g分析纯的 Υα3·6Η2Ο (六水合氯化钇)、 1.115g分析纯的 GdCl3'6H20 (六水合氯化礼)、 2.414g分析纯的 A1C13'6H20(六 水合氯化铝)和 0.075g分析纯的 CeCl3 H20 (七水合氯化铈)溶于 10ml的蒸馏 水中， 配制成含有 0.3mol/L Y3+、 0.3mol/L Gd3+、 lmol/L Al3+和 0.02mol/L Ce3+ 的混合溶液。 将 SiO2纳米微孔玻璃浸泡到混合溶液中 10h后取出， 在室温下 晾至表面干燥后置入高温炉中，高温炉先以 10°C/min的速度升到 400°C，再以 15°C/min的速度升到 900 °C , 之后以 5°C/min速度升到 1200 °C， 在 1200°C下 保温烧结 2h， 烧结后的玻璃随炉冷却至室温取出。 经过切割和抛光后， 制备 出 Y^Gd^A O^Ce纳米微晶玻璃， 该玻璃在蓝光激发下产生黄色发光。 实施例 6 : YGd2Al5O12:Ce 纳米微晶玻璃是一种分散有化学式为 YGd2Al5O12:Ce的纳米发光微晶的无孔密实 SiO2玻璃。
使用分析天平称取 0.676g分析纯的 Y(CH3COO)34H20 (四水合乙酸钇)、 1.804g 分析纯的 Gd(NO3)3'6H2O (六水合硝酸礼）、 3.75g 分析纯的 Α1(Ν03)3·6Η20 (六水合硝酸铝)和 0.087g分析纯的 Ce(NO3)3_6H2O (六水合硝酸 铈)溶于 10ml的蒸馏水， 配制成 0.2mol/L Y3+、 0.4mol/L Gd3+、 lmol/L Al3+和 0.02mol/L Ce3+的混合溶液。 将 Si02纳米微孔玻璃浸泡到混合溶液中 24h后取 出， 在室温下晾至表面干燥后置入高温炉中， 高温炉先以 10°C/min的速度升 到 400°C，再以 15°C/min的速度升到 900°C，之后以 5°C/min速度升到 1300°C， 在 1300°C下保温烧结 5h， 烧结后随炉冷却至室温取出。 经过切割和抛光后， 制备出 YGd2Al5012:Ce纳米微晶玻璃， 该玻璃在蓝光激发下产生黄色发光。 实施例 7 : Gd3Al5012:Ce 纳米微晶玻璃是一种分散有化学式为 Gd3Al5O12:Ce的纳米发光微晶的无孔密实 SiO2玻璃。
使用分析天平称取 2.706g分析纯的 Gd(N03 6H20 (六水合硝酸礼)、 3.75g 分析纯的 Α1(ΝΟ3)3·6Η2Ο (六水合硝酸铝)和 0.434g分析纯的 Ce(NO3)3'6H2O (六 水合硝酸铈)溶于 10ml的蒸馏水中， 配制成含有 0.6mol/L Gd3+、 lmol/L Al3+和 0.1mol/L Ce3+的混合溶液。将 SiO2纳米微孔玻璃浸泡到混合溶液中 10h后取出， 在室温下晾至表面干燥后置入高温炉中， 高温炉先以 10°C/min 的速度升到 400°C， 再以 15°C/min的速度升到 900°C， 之后以 5°C/min速度升到 1300°C， 在 1300°C下保温烧结 2h， 烧结后的玻璃随炉冷却至室温取出。 经过切割和抛 光后， 制备出的 Gd3Al5O12:Ce纳米微晶玻璃， 该玻璃在蓝光激发下产生黄色 发光。 实施例 8: Y3Al5O12:Ce纳米微晶玻璃是一种分散有化学式为 Y3Al5O12:Ce 的纳米发光微晶的无孔密实 Si02玻璃。
制备步骤： 使用分析天平称取 1.014g分析纯的 Y(CH3COO)34H2O (四水 合乙酸钇）、 1.020g 分析纯的 Al(CH3COO)3 (乙酸铝）和 0.0407g 分析纯的 Ce(CH3COO)3-5H2O (五水合乙酸铈)溶于 10ml的蒸馏水，配制成 0.3mol/L Y3+、 0.5mol/L Al3+和 O.Olmol/L Ce3+的混合溶液。 将 SiO2纳米微孔玻璃浸泡到混合 溶液中 24h后取出， 在室温下晾至表面干燥后置入高温炉中， 高温炉先以 10°C/min的速度升到 400 °C，再以 15°C/min的速度升到 900 °C，之后以 5 °C/min 速度升到 1200°C， 在 1200°C下保温烧结 4h， 烧结后随炉冷却至室温取出。 经 过切割和抛光后， 制备出 Y3Al5012:Ce纳米微晶玻璃， 该玻璃在蓝光激发下产 生黄色发光。

Claims

权 利 要 求
1、 一种用于白光 LED光源的发光纳米微晶玻璃， 其特征在于， 是一种 分散有化学式为 YxGd3— xAl5O12:Ce的纳米发光微晶的无孔密实 Si02玻璃， 其 中 0≤x≤3。
2、 根据权利要求 1所述的用于白光 LED光源的发光纳米微晶玻璃， 其 特征在于， 所述的发光纳米微晶玻璃是以 SiO^ft米微孔玻璃为基材， 在 SiO2 纳米微孔玻璃的微孔内分布有化学式为 YxGd3_xAl5O12:Ce纳米发光微晶，将含 有该纳米发光微晶的 Si02纳米微孔玻璃经烧结后， 微孔收縮形成包裹有 YxGd3-xAl5012:Ce纳米发光微晶的无孔密实的 SiO2玻璃。
3、 根据权利要求 2所述的用于白光 LED光源的发光纳米微晶玻璃， 其 特征在于，所述的 SiO^ft米微孔玻璃中的微孔体积占 SiO2纳米微孔玻璃总体 积的 25~40%。
4、 根据权利要求 2或 3所述的用于白光 LED光源的发光纳米微晶玻璃， 其特征在于， 所述的 SiO2纳米微孔玻璃主要由以下重量份数的成分组成：
SiO2 94.0-98.0
B203 1.0-3.0
Α1203 1 ·0~3·0。
5、 用于白光 LED光源的发光纳米微晶玻璃的制备方法， 其特征在于， 包括以下步骤：
( 1 )、 以 Y3+、 Gd3+的氧化物、 硝酸盐、 氯化物、 硫酸盐、 乙酸盐中的 至少一种、 Al3+的氧化物、 硝酸盐、 氯化物、 硫酸盐、 乙酸盐中的至少一种和 Ce3+的氧化物、 硝酸盐、 氯化物、硫酸盐、 乙酸盐中的至少一种为原料， 将上 述原料溶解于溶剂中制成发光化合物离子的混合溶液， 所述混合溶液中 Al3+ 浓度为 0.5~2mol/L、 Y3+与 Gd3+的浓度和为 0.3~1.2mol/L、 Ce3+浓度为浓度为 0.001~0.2mol/L;
(2 )、 选取具有联通微孔的 SiO^ft米微孔玻璃为基材， 其中 SiO2纳米微 孔玻璃的微孔体积占 SiO^ft米微孔玻璃总体积的 25~40%; 将 SiO^米微孔 玻璃放入步骤 （1 ) 制成的混合溶液中浸泡 10分钟以上；
(3 )、 将浸泡后的 SiO2纳米微孔玻璃逐歩升温至 1100~1300°C烧结 1~5 小时， 制得用于白光 LED光源的发光纳米微晶玻璃。
6、 根据权利要求 5所述的用于白光 LED光源的发光纳米微晶玻璃的制 备方法， 其特征在于， 当原料选择各离子的氧化物时， 溶剂选用硝酸、 盐酸、 硫酸或乙酸来溶解； 当原料选择各离子的硝酸盐、 氯化物、 硫酸盐或乙酸盐 时， 则溶剂选用水来溶解。
7、 根据权利要求 5所述的用于白光 LED光源的发光纳米微晶玻璃的制 备方法， 其特征在于， 所述步骤（2 ) 中， 将 SiO^A米微孔玻璃放入歩骤（1 ) 制成的混合溶液中浸泡 30分钟〜 5小时。
8、 根据权利要求 5所述的用于白光 LED光源的发光纳米微晶玻璃的制 备方法， 其特征在于， 所述步骤（3 ) 中， 先将浸泡后的 SiO^ft米微孔玻璃室 温下晾至表面干燥，然后再置于高温炉中逐歩升温至 1150~1250°C，在此温度 下对浸泡后的 Si02纳米微孔玻璃烧结 2~4小时， 烧结后随炉冷却至室温， 取 出，制得用于白光 LED光源的发光纳米微晶玻璃；其中在 400°C以下和 900 °C 以上的温度区间， 升温速度不高于 15°C/min。
9、 根据权利要求 5所述的用于白光 LED光源的发光纳米微晶玻璃的制 备方法， 其特征在于， 所述的 SiO2纳米微孔玻璃主要由以下重量份数的成分 组成： SiO2 94.0〜98.0、 Β2Ο3 1.0~3.0、 Α12Ο3 1·0~3·0。
PCT/CN2010/070880 2010-03-05 2010-03-05 用于白光led光源的发光纳米微晶玻璃及其制备方法 WO2011106938A1 (zh)

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