WO2008062797A1 - Substance fluorescente pour une excitation ultraviolette sous vide - Google Patents

Substance fluorescente pour une excitation ultraviolette sous vide Download PDF

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Publication number
WO2008062797A1
WO2008062797A1 PCT/JP2007/072472 JP2007072472W WO2008062797A1 WO 2008062797 A1 WO2008062797 A1 WO 2008062797A1 JP 2007072472 W JP2007072472 W JP 2007072472W WO 2008062797 A1 WO2008062797 A1 WO 2008062797A1
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weight
phosphor
less
vacuum ultraviolet
ultraviolet light
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PCT/JP2007/072472
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English (en)
Japanese (ja)
Inventor
Tomoko Akai
Kohei Kadono
Wei Liu
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National Institute Of Advanced Industrial Science And Technology
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Priority to JP2008545414A priority Critical patent/JP4982812B2/ja
Publication of WO2008062797A1 publication Critical patent/WO2008062797A1/fr

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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
    • C09K11/7701—Chalogenides
    • C09K11/7703—Chalogenides with alkaline earth metals
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
    • 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
    • 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
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—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
    • C09K11/7744—Chalcogenides
    • C09K11/7746—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
    • C09K11/776—Chalcogenides
    • C09K11/7761—Chalcogenides with alkaline earth metals
    • 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
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • 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
    • C03C2201/50—Doped silica-based glasses containing metals containing alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/42—Fluorescent layers

Definitions

  • the present invention relates to a phosphor for vacuum ultraviolet light excitation.
  • vacuum ultraviolet light having a wavelength of 172 nm is light having a higher energy than the absorption edge of the host crystal
  • the luminescent ions are directly excited by ultraviolet light as in the case of excitation with mercury rays, and fluorescence of visible light is emitted.
  • the direct excitation mechanism that occurs there are not many crystals in which the force indirect excitation that requires visible fluorescence to occur due to the indirect excitation mechanism in which the energy absorbed by the matrix moves to the emission center efficiently occurs.
  • Patent Document 1 a method of improving the coating of the phosphor surface
  • Patent Documents 2 and 3 a method of improving the coating of the phosphor surface
  • Patent Documents 4 and 5 a method of improving the coating of the phosphor surface
  • a plasma display device can be cited in addition to the mercury-free fluorescent lamp.
  • the plasma display uses Xe's 147nm emission line, and phosphors include Zn SiO: Mn (green), (Y Gd) BO: Eu (red), BaMgAl 2 O: Eu (blue) or the like is used.
  • chromaticity CI
  • X and Y values in E coordinates are important.
  • a phosphor derived from a rare earth f-transition that exhibits a sharp emission peak is desirable, but a phosphor exhibiting adequate color purity provides a sufficient strength and intensity.
  • BaMgAl 2 O 3: Eu using fd transition or Zn SiO 2: Mn using dd transition is used.
  • Non-Patent Document 1 it has also been reported that many rare earth metals exhibit a light emission phenomenon in a powder obtained by sintering porous silica powder (Non-Patent Documents 2 and 3). However, these phosphors are not practical enough because the fluorescence intensity by vacuum ultraviolet light excitation is as low as 10% to 20% compared to commercially available phosphors.
  • Patent Document 1 JP 2002-38148
  • Patent Document 2 JP-A 2005--60670
  • Patent Document 3 JP 2003-213254 A
  • Patent Document 4 JP 2004-197044
  • Patent Document 5 JP-A 2005--60679
  • Patent Document 6 JP 2003-155478 A
  • Patent document 7 JP-A-2005-142037
  • Patent Document 8 JP 2005-060679
  • Non-Patent Document 1 Chemistry Letters 86 (23): 231908 (2005)
  • Non-Patent Document 2 Proceedings of the 67th Annual Conference of the Japan Society of Applied Physics, P.1323
  • Non-Patent Document 3 Proceedings of the 19th Autumn Symposium, p.79
  • the main object of the present invention is a phosphor excited by ultraviolet light in the vacuum ultraviolet region, which can be used stably over a long period of time, has high emission intensity, and can exhibit appropriate chromaticity. It is to provide a novel phosphor for vacuum ultraviolet light excitation.
  • porous silica is used as a base material, and a sensitizer comprising a light emitting element comprising a rare earth element and at least one alkali metal element selected from the group consisting of Li, Na, K, Rb and Cs is used. It has been found that a phosphor for vacuum ultraviolet light excitation that can achieve the above-described object can be obtained by the method of firing after doping, and the present invention has been completed here.
  • the present invention provides the following phosphor for vacuum ultraviolet light excitation.
  • Porous silica is doped with a rare earth element that exhibits fluorescence by f_transfer and at least one alkali metal element selected from the group consisting of Li, Na, K, Rb, and Cs, and then fired. Obtained phosphor for vacuum ultraviolet light excitation.
  • Porous silica contains 95% by weight or more of SiO, pore diameter of lnm to 10nm, specific surface
  • the phosphor for vacuum ultraviolet light excitation according to item 1 which is a porous body having a product force of 00 m 2 / g to 800 m 2 / g.
  • the content of the rare earth element is 0.01 to 12% by weight, and the content of at least one alkali metal element selected from the group consisting of Li, Na, K, Rb and Cs is 0.01 to 9% by weight. 4.
  • the porous silica further includes at least one selected from the group consisting of Ba, Er, In and Gd.
  • Item 6 The phosphor for vacuum ultraviolet light excitation according to any one of Items 1 to 5, obtained by doping a seed element and firing the seed element.
  • the phosphor for vacuum ultraviolet light excitation according to any one of the above items 1 to 5, which is a phosphor emitting green light containing Na at 1% by weight or less and K at 3% by weight or less.
  • Tb 0.01 to 12% by weight of Tb, 0.01 to 9% by weight of at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs, and 0.4% by weight or less of Li
  • alkali metal selected from the group consisting of Li, Na, K, Rb and Cs
  • 0.4% by weight or less of Li The phosphor for vacuum ultraviolet light excitation according to Item 6, wherein the phosphor emits green light and contains Na 1 wt% or less, K 3 wt% or less, and Gd 0.01 to 9 wt%.
  • phosphor 1 1. 1% to 12% by weight of at least one element selected from the group consisting of Eu and Sm and at least one alkali metal selected from the group force consisting of Li, Na, K, Rb and Cs 0.0 1-9% by weight of the above phosphor, which is a phosphor emitting red light containing 0.4% by weight or less of Li, 1% by weight or less of Na, 3% by weight of K or less, and 0.01-9% by weight of Gd 6.
  • Tm from 0.01 to 12% by weight, at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs from 0.01 to 9% by weight, and Li by 0.4% % Or less, Na is 1% by weight or less, K is 3% by weight or less, and a phosphor emitting blue light containing 0.01 to 9% by weight of at least one element selected from the group consisting of Er and In 6 Vacuum ultraviolet light excitation described in Appointed phosphor.
  • alkali metal selected from the group consisting of Li, Na, K, Rb and Cs from 0.01 to 9% by weight, and Li by 0.4% % Or less
  • Na is 1% by weight or less
  • K is 3% by weight or less
  • a phosphor emitting blue light containing 0.01 to 9% by weight of at least one element selected from the group consisting of Er and In 6 Vacuum ultraviolet light excitation described in Appointed phosphor.
  • Tm from 0.02 to 12% by weight, 0.01 to 9% by weight of at least one alkali metal selected from the group consisting of Li, Na, K, Rb and Cs, and 0.4% by weight of Li
  • the phosphor for vacuum ultraviolet light excitation of the present invention comprises amorphous silica as a main component and a specific light emitting element and a sensitizer component immobilized thereto, and is irradiated with ultraviolet light in the vacuum ultraviolet region or lower. By doing so, it emits strong fluorescence stably over a long period of time.
  • FIG. 1 is a drawing showing a fluorescence spectrum of a blue phosphor obtained in Example 4.
  • FIG. 2 is a drawing showing the fluorescence spectrum of the green phosphor obtained in Example 10.
  • FIG. 3 is a drawing showing the fluorescence spectrum of the red phosphor obtained in Example 13.
  • FIG. 4 is a chromaticity coordinate showing the chromaticity values of the phosphors of Examples 10, 13, 17, and 4 and commercially available phosphors.
  • the phosphor for vacuum ultraviolet light excitation according to the present invention is obtained by using porous silica as a base material, doping a rare earth element and a specific sensitizer, and then firing.
  • the porous silica used in the present invention may be a porous body mainly composed of SiO.
  • SiO porous silica
  • the pore shape of the porous silica is preferably a continuous pore so that ions can be introduced from the outside into the inside.
  • the pore diameter is preferably about 1 nm to 10 nm, more preferably about 2 nm to 4 nm.
  • the pore diameter is a value obtained by the BET method using the nitrogen adsorption method.
  • the particle diameter of the porous silica is not particularly limited, but it is usually preferable that the average particle diameter is in the range of about 1, 1 m to 30, 1 m. 3, 1 m to 20, m It is more preferable to be a degree.
  • the average particle size of the porous silica is a value measured by a particle size distribution measuring method using a laser diffraction and scattering method of JIS R 16 29-1997 using an optical particle size measuring device.
  • the specific surface area of porous silica is more preferably be 100m 2 / g ⁇ 800m 2 / g approximately is preferred instrument 3 00m 2 / g ⁇ 600m 2 / g approximately.
  • the specific surface area is a value obtained by the BET method using the nitrogen adsorption method.
  • the Fe content should be less than lOOppm! /.
  • the method for producing the porous silica is not particularly limited as long as the method can produce the porous silica satisfying the above-described conditions.
  • a commercially available silica gel production method in which silica colloid is agglomerated can be used.
  • borosilicate glass is spinodal phase-separated into boric acid phase and silicic force phase, and the boric acid phase is leached with acid to form porous silica. It can be obtained in the same way.
  • the latter method is particularly advantageous in that the pore diameter and the surface area can be freely changed.
  • a rare earth element that exhibits fluorescence by f_shift is used as the light emitting element.
  • rare earth elements include Tb, Eu, Sm, Tm, and Dy. From these rare earth elements, the element to be used may be determined according to the target emission color. For example, Tb can be used to obtain a phosphor emitting green light, Eu or Sm can be used to obtain a phosphor emitting red light, and a phosphor emitting blue light can be obtained. Tm can be used to do this.
  • the content of the rare earth element in the phosphor for vacuum ultraviolet light excitation according to the present invention can be appropriately determined according to the target emission intensity. In general, the content of rare earth elements is preferably about 0.01 to 12% by weight, more preferably about 0.5 to 5% by weight, based on the entire phosphor.
  • the rare earth element is considered to be fixed in an ionic state using amorphous silica as a base material.
  • the phosphor for vacuum ultraviolet light excitation of the present invention it is necessary to use at least one alkali metal element selected from the group consisting of Li, Na, K, Rb and Cs as a sensitizer.
  • the sensitizers together with the rare earth elements described above the luminous intensity can be greatly increased, and a high-luminance luminescent material can be obtained.
  • Rb and Cs are particularly effective in increasing the emission intensity.
  • the content of at least one alkali metal element selected from the group power consisting of Li, Na, K, Rb and Cs is preferably about 0.01 to 9% by weight. 0.1 to 2% by weight It is more preferable to set the degree. However, for each element of Li, Na, and K, even if the amount is within the above range, if the amount added is too large, the emission intensity may decrease. Therefore, the Li content is preferably about 0.4% by weight or less, the Na content is about 1% by weight or less, and the K content is preferably about 3% by weight or less.
  • the alkali metal element when used within the above-described content range, about 0.6 to 1.6 mol, more preferably within the range of 0.7 to 1.3, with respect to 1 mol of the rare earth element, the emission intensity is particularly high. It can be greatly improved.
  • the emission intensity can be further improved by further containing Ba, Er, In, Gd or the like, if necessary.
  • the content of Ba, Er, In, Gd, etc. is a force that can be appropriately determined according to the target emission intensity.
  • the emission intensity is within the range of about 0.01 to 9% by weight.
  • porous silica is doped with a luminescent element and a sensitizer.
  • the method of doping the luminescent element and the sensitizer is not particularly limited, for example, a method of doping the target element by a vapor phase method such as a CVD method, a solution containing the luminescent element and the sensitizer component.
  • a method of immersing porous silica in the inside can be applied.
  • the method of immersing in a solution is advantageous in that the element is homogeneously doped.
  • the concentration of rare earth elements in the solution to be used is usually preferably about 0.01 mol / L to 6 mol / L. More preferably, it is about ⁇ 3 mol / L.
  • the concentration of at least one alkali metal element selected from the group consisting of Li, Na, K, Rb and Cs is usually preferably about 0.01 mol / L to 6 mol / L. It is more preferable to set it to about 03 mol / L to 3 mol / L.
  • the concentration of these components is preferably about 0.05 to 6 mol / L! /.
  • water is used as a solvent of the solution! /.
  • the above-described light emitting element and sensitizer may be a compound that is soluble in the solvent used.
  • nitrates, chlorides and the like can be used.
  • the porous silica may be added to the solution, stirred and sufficiently dispersed and allowed to stand.
  • the temperature of the solution should normally be about 0 ° C to room temperature, and the immersion time should be about 10 minutes to 2 hours.
  • the firing temperature is preferably about 850 ° C to 1250 ° C, more preferably about 1000 to 1100 ° C. If the baking temperature is too low or too high, sufficient fluorescence intensity cannot be obtained, which is not preferable.
  • the firing time is usually about 2 to 6 hours.
  • the firing atmosphere is not particularly limited, but for Eu3 + , firing in an oxygen atmosphere that can reduce the amount of Eu2 + that does not contribute to red light emission is particularly desirable.
  • the phosphor for vacuum ultraviolet light excitation obtained by the above-described method is obtained by immobilizing a light emitting element and a sensitizer in amorphous silica.
  • the obtained phosphor is excited by irradiation with ultraviolet rays in the vacuum ultraviolet region and emits strong! / Fluorescence.
  • Silica as a base material is a short wavelength light with high ultraviolet transmittance. It can be used stably for a long period of time as a light emitter that can be easily excited by UV light and is less susceptible to defects caused by UV irradiation. Furthermore, with regard to color purity, purer red (R) and green (G) compared to commercially available ones.
  • the phosphor for vacuum ultraviolet light excitation according to the present invention can be obtained by selecting the kind of rare earth element.
  • the phosphor of the desired emission color can be obtained.
  • Specific examples of such a phosphor having a specific emission color are as follows.
  • the phosphor for vacuum ultraviolet light excitation that emits green light is selected from the group consisting of Li, Na, K, Rb, and Cs with 0.01 to 12 wt% of Tb based on the whole phosphor.
  • Examples include phosphors containing 0.01 to 9% by weight of at least one alkali metal element, 0.4% by weight or less of Li, 1% by weight or less of Na, and 3% by weight or less of K.
  • a phosphor for vacuum ultraviolet light excitation that emits red light
  • 0.01% to 12% by weight of at least one element selected from the group force consisting of Eu and Sm based on the whole phosphor, Li, At least one alkali metal element selected from the group consisting of Na, K, Rb and Cs is 0.01 to 9 wt%, Li is 0.4 wt% or less, Na is 1 wt% or less, and K is 3 wt%
  • An example is a phosphor containing at most%.
  • Tm is 0.01 to 12% by weight, based on the whole phosphor, and a group force consisting of Li, Na, K, Rb and Cs is selected.
  • Examples include phosphors containing 0.01 to 9% by weight of at least one alkali metal element, 0.4% by weight or less of Li, 1% by weight or less of Na, and 3% by weight or less of K.
  • a phosphor for vacuum ultraviolet light excitation that emits green light with enhanced emission intensity 0.01 to 12% by weight of Tb, Li, Na, K, Rb, and Cs, based on the whole phosphor At least one alkali metal element selected from the group consisting of 0.01 to 9% by weight, Li 0.4% or less, Na 1% or less, K 3% or less, Gd 0.01 Examples thereof include phosphors containing ⁇ 9% by weight.
  • a phosphor for vacuum ultraviolet light excitation that emits red light with enhanced emission intensity 0.01% or more of at least one element selected from the group consisting of Eu and Sm is used based on the whole phosphor.
  • Tm is 0.01% to 12% by weight based on the whole phosphor, and Li, Na, K, Rb and Cs.
  • phosphors for vacuum ultraviolet light excitation that emit blue light with enhanced emission intensity include 0.02% to 12% by weight of Tm, Li, Na, K, 0.01 to 9 wt% of at least one alkali metal element selected from the group consisting of Rb and Cs, 0.4 wt% or less of Li, 1 wt% or less of Na, 3 wt% or less of K, and Ba Examples thereof include phosphors containing 0.01 to 1% by weight.
  • the phosphor for vacuum ultraviolet light excitation of the present invention can be effectively used for various applications as a phosphor for vacuum ultraviolet light excitation utilizing the above-described excellent characteristics.
  • it can be used as a phosphor in a lighting device, a display device, a mercury-free fluorescent lamp, a plasma display, etc.
  • the fluorescent lamp using the phosphor of the present invention is a liquid crystal display, a copy device, a scanner device, etc. Is available.
  • a borosilicate glass having the composition (% by weight) shown in Table 1 below was melted at 1400 ° C., rapidly cooled, and then pulverized to an average particle size of about 8 to 9 m. Next, it was treated with 1N nitric acid at 90 ° C. for 2 hours, collected by filtration, and washed with water to obtain porous silica.
  • Table 2 shows the specific surface area, pore diameter and average particle diameter of the obtained porous silica.
  • the specific surface area and the pore diameter are values obtained by the BET method using a nitrogen adsorption method, and the average particle diameter is a value measured using an optical particle size measuring apparatus.
  • a commercially available silica gel Tosoh Silica Co., Ltd. (CX-200: Symbol E) and Nagara Science Co., Ltd. Siri Force Gel (NA-300H: Symbol F) were used for pulverization and classification.
  • Each porous silica obtained by the above-described method was immersed in a solution containing a luminescent element and a sensitizer shown in Tables 3 to 8 below at 20 ° C for about 1 hour, and then collected by filtration.
  • the phosphors for vacuum ultraviolet light excitation were obtained by firing at the temperatures shown in Tables 3 to 8 for 2 hours. Tb was fired in air for 6 hours, Tm was fired in a reducing atmosphere for 2 hours, and Eu was fired in an oxygen atmosphere for 2 hours.
  • Tables 3 to 8 below show the peak intensity of light emission for each phosphor.
  • the Tb-containing green phosphor has a peak intensity of 543 nm
  • the Eu-containing red phosphor has a peak intensity of 610 nm
  • the Tm-containing blue phosphor has a peak intensity of 458 nm.
  • Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 2 Porous silica used F F F C C C F
  • Examples 1 to 6 shown in Table 3 show fluorescence intensities of blue light emitting phosphors containing Tm as a luminescent element and Cs as a sensitizer. As compared with the phosphor of Comparative Example 1 that does not contain Cs, it is obvious that the fluorescence intensity is improved.
  • Examples 7 to 12 shown in Table 4 relate to green light-emitting phosphors containing Tb as a luminescent element and Cs or Rb as a sensitizer element! / Indicates the fluorescence intensity. Contains no sensitizer ingredients Compared with the phosphor of Comparative Example 2, an improvement in fluorescence intensity is observed.
  • Examples 13 to 16 shown in Table 5 show the fluorescence intensities of red light emitting phosphors containing Eu as a light emitting element and Rb or Cs as a sensitizer element. It is clear that the fluorescence intensity is improved as compared with the phosphor of Comparative Example 3 containing no sensitizer component.
  • Examples 17 to 18 shown in Table 6 show the fluorescence intensities of red light emitting phosphors containing Sm as a luminescent element and Rb or Cs as a sensitizer element. It is clear that the fluorescence intensity is improved as compared with the phosphor of Comparative Example 4 which does not contain a sensitizer component.
  • Examples 19 to 25 shown in Table 7 show the fluorescence intensities of green phosphors containing Tb as a luminescent element and Li, Na or K as a sensitizer element.
  • Comparative Examples 6 to 8 are examples in which the amount of Li, Na or K added is large. When the amount of these components added is excessive, a decrease in fluorescence intensity is observed.
  • FIGS. 1 to 3 show the phosphors of the phosphors obtained in Example 4, Example 10, and Example 13.
  • FIG. 4 is chromaticity coordinates showing chromaticity values of the phosphors of Examples 10, 13, 17 and 4 and commercially available phosphors. Compared to the commercially available ones, B and G are especially shifted in the direction that people feel B and G.

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Abstract

L'invention concerne une nouvelle substance fluorescente pour une excitation ultraviolette sous vide. Cette substance est obtenue par le dopage d'une silice poreuse par au moins un élément choisi dans le groupe constitué par les lanthanides qui présentent une fluorescence par transitions f-f, Rb et Cs, puis par cuisson de la silice ainsi dopée. Cette substance fluorescente est excitée par la lumière ultraviolette dans la région ultraviolette sous vide, et peut être utilisée de façon stable pendant une longue période de temps. De plus, cette substance fluorescente a une intensité lumineuse élevée, tout en présentant une chromaticité suffisante.
PCT/JP2007/072472 2006-11-21 2007-11-20 Substance fluorescente pour une excitation ultraviolette sous vide WO2008062797A1 (fr)

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CN116997633A (zh) * 2021-03-15 2023-11-03 松下知识产权经营株式会社 荧光体和使用了它的太阳能电池模块

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