WO2014006987A1 - 蛍光材料、蛍光塗料、蛍光体基板、電子機器およびledパッケージ - Google Patents
蛍光材料、蛍光塗料、蛍光体基板、電子機器およびledパッケージ Download PDFInfo
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- WO2014006987A1 WO2014006987A1 PCT/JP2013/063793 JP2013063793W WO2014006987A1 WO 2014006987 A1 WO2014006987 A1 WO 2014006987A1 JP 2013063793 W JP2013063793 W JP 2013063793W WO 2014006987 A1 WO2014006987 A1 WO 2014006987A1
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- 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
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- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/15—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components having potential barriers, specially adapted for light emission
- H01L27/153—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components having potential barriers, specially adapted for light emission in a repetitive configuration, e.g. LED bars
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- H—ELECTRICITY
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- 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
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- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
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- H—ELECTRICITY
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- 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
- H01L33/58—Optical field-shaping elements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
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- H10K59/877—Arrangements for extracting light from the devices comprising scattering means
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
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- 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
Definitions
- the present invention relates to a fluorescent material, a fluorescent paint, a phosphor substrate, an electronic device, and an LED package that can improve light extraction efficiency.
- a phosphor and a scatterer are arranged in front of the liquid crystal display device, a part of the blue light of the polarization collimated light source is used for blue display, and a part thereof is used.
- a method of performing display by converting colors into red and green with a phosphor is disclosed (for example, see Patent Documents 1 and 2).
- the liquid crystal display that converts the color of the light from the excitation light source using a phosphor not only improves the viewing angle characteristics but also reduces the light loss compared to the liquid crystal display that expresses full color using the color filter method that is currently widely used. High brightness can be realized with low power consumption.
- the organic EL display is a display device having excellent display characteristics such as high contrast, high viewing angle, and high response speed.
- patterning of the RGB light emitting layer using mask vapor deposition is required. Therefore, high definition and large size are difficult.
- a method of emitting RGB phosphors using a monochromatic organic EL element as an excitation light source is disclosed (for example, see Patent Document 3). In the case of this method, since the organic EL layer may be a single color, it is possible to realize high definition and large size at low cost.
- the light extraction efficiency can be calculated according to Snell's law.
- the incident angle is larger than the critical angle, the light is totally reflected at the interface between the media. Therefore, in a phosphor that emits light isotropically, light incident on the interface at an angle larger than the critical angle is totally reflected at the boundary surface, and light cannot enter the adjacent layer. Light that cannot enter an adjacent layer repeats total reflection in the layer and becomes confined.
- the critical angle ⁇ 1 is 41.8 °, and light is incident on the interface between n1 and n2 at ⁇ 1 ⁇ 41.8 °. It can only be taken out through the glass. Accordingly, the light extraction efficiency to the outside is at a very low level of about 10% or more.
- the refractive index of the light emitting part is lowered, a low refractive index layer is disposed between the light emitting part and the transparent substrate for extracting light, or the transparent substrate
- a method of arranging a low refractive index layer on the light extraction surface side is effective.
- Examples of disposing a low refractive index layer include a method of inserting an air layer between an organic EL element functional unit and a transparent substrate (see, for example, Patent Document 4), and blue light emitted from an organic EL element as a phosphor.
- Patent Document 5 There is known a method (for example, see Patent Document 5) in which color conversion is performed by a layer and a low refractive index layer is provided on the light extraction surface side of a transparent substrate to increase light utilization efficiency. It has also been proposed to introduce a hollow silica layer having a low refractive index between the phosphor layer and the substrate (see, for example, Patent Document 6). Furthermore, a method of improving the light extraction efficiency by using a color conversion filter having a refractive index of 1.30 or more and 1.48 or less has been proposed (see, for example, Patent Document 7).
- JP 2000-131683 A Japanese Patent Laid-Open No. 62-194227 Japanese Patent Laid-Open No. 03-152897 JP 2003-045642 A JP 2007-207655 A JP 2003-216601 A JP 2006-190633 A
- Some aspects of the present invention have been made in view of the above circumstances, and fluorescent materials, fluorescent paints, phosphor substrates, and electronic devices that can improve light extraction efficiency without complicating the structure And an LED package.
- the fluorescent material in one embodiment of the present invention includes at least a phosphor and fine particles.
- the fine particles may have a refractive index smaller than that of the phosphor.
- the refractive index of the fine particles may be larger than 1.0 and smaller than 1.3.
- the phosphor may be a perylene dye or a coumarin dye.
- the particle size of the fine particles may be 5 nm or more and 300 nm or less.
- the fine particles may be porous particles or hollow particles.
- the hollow particles may have an outer shell thickness of 5% to 80% with respect to the particle size.
- the ratio of the volume of the fine particles to the solid content of the whole fluorescent material may be 10% or more and 80% or less.
- Fluorescent paint according to another aspect of the present invention includes the fluorescent material described in the above items.
- a phosphor substrate according to still another aspect of the present invention includes the fluorescent material described in the above items.
- the phosphor substrate in yet another aspect of the present invention may include at least a light-transmitting substrate, the phosphor, and the fine particles having a refractive index smaller than that of the substrate and the phosphor.
- a color filter may be further disposed between the phosphor on the fluorescence emission side and the phosphor.
- An electronic device uses the phosphor substrate described in each item.
- An electronic device may include the phosphor substrate described in each of the above items and an excitation light source that excites the phosphor to generate fluorescence.
- the excitation light source may be an organic electroluminescence element that emits ultraviolet light or blue light.
- the excitation light source may be an ultraviolet LED or a blue LED.
- the electronic device may further include a liquid crystal layer that controls excitation light incident on the phosphor substrate from the excitation light source between the excitation light source and the phosphor substrate.
- the electronic device further includes a band-pass filter that transmits only light of a specific wavelength and reflects light other than the specific wavelength between the excitation light source and the phosphor substrate. Also good.
- the phosphor substrate may be divided into a plurality of pixels and may have at least red pixels that emit red light and green pixels that emit green light.
- At least a part of one side or both sides of the red pixel and the green pixel may be surrounded by a light scattering partition.
- LEDAn LED package according to still another aspect of the present invention includes the fluorescent material described in each of the above items.
- a fluorescent material a fluorescent paint, a phosphor substrate, an electronic device, and an LED package that can improve the light extraction efficiency without complicating the structure.
- the fluorescent material is composed of at least a phosphor and fine particles, and may further contain a binder resin.
- 1A to 2D are schematic views showing the fluorescent material of this embodiment.
- the fluorescent material 10 includes a phosphor-containing material 11 in which a phosphor is dissolved or dispersed in a phosphor or a binder resin, and fine particles 12 dispersed in the phosphor-containing material 11.
- the fine particles 12 may have various external shapes such as a spherical shape, a rectangular parallelepiped shape, a conical shape, a triangular pyramid shape, a scale shape, and an indefinite shape. Further, the fine particles 12 may be dispersedly arranged in the phosphor-containing material 11 by mixing the fine particles 12 having a plurality of shapes.
- the soot particles 12 are preferably made of a material having a refractive index smaller than that of the phosphor-containing material 11.
- the fine particles 12 may have a refractive index greater than 1.0 and smaller than 1.3.
- the particle diameter (average particle diameter) of such fine particles is preferably formed in a range of, for example, 5 nm or more and 300 nm or less.
- the soot particles 12 have various outer shapes as described above, and may be porous particles or hollow particles, for example.
- the thickness of the outer shell may be formed in a range of 5% to 80% with respect to the particle size.
- the phosphor-containing material 11 and the fine particles 12 are distributed so that the volume ratio of the fine particles 12 to the total solid content of the fluorescent material 10 is in the range of 10% to 80%. Just do it.
- the fluorescent material 10A of the embodiment shown in FIG. 1A is an example in which spherical and hollow fine particles 12A are regularly dispersed and arranged with respect to the phosphor-containing material 11.
- the fluorescent material 10 ⁇ / b> B of the embodiment shown in FIG. 1B is an example in which spherical and hollow fine particles 12 ⁇ / b> A are irregularly dispersed with respect to the phosphor-containing material 11.
- the fluorescent material 10C of the embodiment shown in FIG. 1C is an example in which fine particles 12AL, 12AS having a plurality of spherical shapes and hollow are irregularly dispersed in the phosphor-containing material 11.
- the fluorescent material 10E of the embodiment shown in FIG. 1E is an example in which porous fine particles 12B and spherical fine particles 12AL and 12AS having a plurality of diameters are irregularly dispersed in the phosphor-containing material 11. It is.
- the fluorescent material 10F of the embodiment shown in FIG. 1F contains a phosphor so that the spherical fine particles 12A are more dispersed toward the light emission surface side (fluorescence emission surface side) F1 of the fluorescent material 10F. This is an example in which the object 11 is deflected and dispersed.
- the fluorescent material 10H of the embodiment shown in FIG. 2B is deflected with respect to the phosphor-containing material 11 so that more spherical fine particles 12A are dispersed toward the light incident surface side F2 of the fluorescent material 10F. This is an example of dispersion.
- the 2C has more spherical and hollow fine particles 12A toward both sides of the light emission surface side (fluorescence emission surface side) F1 and the light incident surface side F2 of the fluorescent material 10F.
- the phosphor-containing material 11 is deflected and dispersed so as to be dispersed.
- the fluorescent material 10J of the embodiment shown in FIG. 2D moves the spherical fine particles 12A toward the middle between the light emission surface side (fluorescence emission surface side) F1 and the light incident surface side F2 of the fluorescent material 10F.
- the phosphor-containing material 11 is deflected and dispersed so as to disperse more.
- the phosphor of this embodiment a known phosphor can be used. Such phosphors are classified into organic phosphor materials and inorganic phosphor materials. Specific examples of these phosphors are given below, but the phosphors are not limited to these materials. Moreover, you may use combining these several fluorescent material, and may use the hybrid type fluorescent substance of an organic fluorescent substance and an inorganic fluorescent substance. In addition, a material having a high absorption rate of excitation wavelength light and a high internal quantum yield is particularly preferable from the viewpoint of high efficiency.
- organic fluorescent materials include blue fluorescent dyes such as stilbenzene dyes: 1,4-bis (2-methylstyryl) benzene, trans-4,4′-diphenylstilbenzene, coumarin dyes: 7- Hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-11-oxo-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-10-carboxylate (coumarin 314 ) 10-acetyl-2,3,6,7-tetrahydro-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one (coumarin 334), anthracene dye: 9 , 10 bis (phenylethynyl) anthracene, perylene and the like.
- blue fluorescent dyes such as stilbenzene dyes: 1,4-bis (2-methylstyryl) benzene, trans-4,4′-dipheny
- green fluorescent dyes examples include coumarin dyes: 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidine (9,9a, 1-gh) coumarin (coumarin 153), 3 -(2'-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2'-benzoimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7), 10- (benzothiazol-2-yl)- 2,3,6,7-tetrahydro-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one (coumarin 545), coumarin 545T, coumarin 545P, naphthalimide dyes: Basic Yellow 51, Solvent Yellow 11, Solvent Yellow 98, Solvent Yellow 116, Solvent Yellow 43, Solvent Yellow 44, Perylene Dye: Lumogen Yellow, Lumogen Green, Solvent Green 5, Fluorescein
- red fluorescent dyes examples include cyanine dyes: 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), DCM-2, DCJTB, and pyridine dyes. : 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate (pyridine 1) and xanthene dyes: rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101 , Rhodamine 110, basic violet 11, sulforhodamine 101, basic violet 11, basic red 2, perylene dyes: lumogen orange, rumogen pink, rumogen red, solvent orange 55, oxazine dye, chrysene dye, thioflavine dye, pyreth Dyes, anthracene dyes, acridone dyes, a
- FIG. 3 shows a thin film in which coumarin 6 is added to polystyrene resin (indicated by triangles in FIG. 3) and a thin film in which rumogen yellow, which is a perylene dye, is added in polystyrene resin (indicated by white circles in FIG. 3).
- the normalized luminance is the light absorption rate at a wavelength of 450 nm when a thin film containing a phosphor at each irradiation time is irradiated with blue light having a peak wavelength of 450 nm at an illuminance of 120 W / m 2 and excited with 450 nm light.
- the product of the internal quantum yield of Is defined as the ratio of the internal quantum yield to the product. According to FIG. 3, it can be seen that the light resistance is improved by 1 to 2 digits in the thin film to which the lumogenic dye is added as compared with coumarin 6.
- Examples of the inorganic phosphor material include blue phosphors such as Sr 2 P 2 O 7 : Sn 4+ , Sr 4 Al 14 O 25 : Eu 2+ , BaMgAl 10 O 17 : Eu 2+ , SrGa 2.
- blue phosphors such as Sr 2 P 2 O 7 : Sn 4+ , Sr 4 Al 14 O 25 : Eu 2+ , BaMgAl 10 O 17 : Eu 2+ , SrGa 2.
- green phosphors examples include (BaMg) Al 16 O 27 : Eu 2+ , Mn 2+ , Sr 4 Al 14 O 25 : Eu 2+ , (SrBa) Al 12 Si 2 O 8 : Eu 2+ , (BaMg) 2 SiO 4 : Eu 2+ , Y 2 SiO 5 : Ce 3+ , Tb 3+ , Sr 2 P 2 O 7 —Sr 2 B 2 O 5 : Eu 2+, (BaCaMg) 5 (PO 4 ) 3 Cl : Eu 2+ , Sr 2 Si 3 O 8 -2SrCl 2 : Eu 2+ , Zr 2 SiO 4 , MgAl 11 O 19 : Ce 3+ , Tb 3+ , Ba 2 SiO 4 : Eu 2+ , Sr 2 SiO 4 : Eu 2+ , (BaSr) SiO 4 : Eu 2+ and the like.
- red phosphor examples include Y 2 O 2 S: Eu 3+ , YAlO 3 : Eu 3+ , Ca 2 Y 2 (SiO 4 ) 6 : Eu 3+ , LiY 9 (SiO 4 ) 6 O 2.
- these inorganic phosphors may be subjected to surface modification treatment as necessary.
- the method include a chemical treatment such as a silane coupling agent, a physical treatment by adding fine particles of submicron order, and a combination thereof.
- an inorganic material it is preferable to use an inorganic material.
- the average particle size (d 50 ) is preferably 0.5 ⁇ m to 50 ⁇ m. If the average particle size is 1 ⁇ m or less, the luminous efficiency of the phosphor may be rapidly reduced. Further, if it is 50 ⁇ m or more, it may be difficult to pattern at a high resolution.
- FIG. 21 is a diagram showing the relationship between the low refractive index fine particles added to the phosphor layer and the result of the apparent brightness evaluation.
- a phosphor layer was formed by spin-coating a phosphor solution obtained by adding fine particles having various refractive indexes to a green phosphor having a refractive index of 1.5 on a glass on which a green color filter was formed.
- Table 1 shows the type of fine particles, the refractive index, and the volume ratio of the fine particles to the phosphor layer.
- the fine particles added to the phosphor layer preferably have a refractive index of 1.0 or more and 1.3 or less. Moreover, since the refractive index of vacuum is 1.0, there is no substance having a refractive index of less than 1.0. As described above, it can be said that the addition of the low refractive index fine particles to the phosphor layer is effective in improving the light extraction efficiency.
- the fine particles having a refractive index of 1.3 or less for example, a fluorine-based polymer having a low refractive index, porous fine particles such as porous silica, hollow fine particles such as hollow silica, or a combination thereof can be used.
- the porous fine particles are fine particles having an infinite number of pores.
- the hollow fine particles are fine particles having a hollow structure (balloon structure) inside.
- the porous or hollow fine particles include inorganic particles made of silica, titania, zinc sulfide, cadmium sulfide, and organic particles made of resin.
- an organic-inorganic hybrid material in which a hydrocarbon polymer is bonded to silica on the surface of hollow silica for example, may be used.
- the refractive index of the porous particles and the hollow particles means an apparent refractive index of the entire hollow particles.
- the value represented by the following formula 1 is adopted as the refractive index of the porous particles and the hollow particles.
- n p is the refractive index of the hollow particles
- n s is the refractive index of the material of the portion other than the voids of the porous or hollow particles
- the void portion of the n c is porous or hollow particles
- X represents the volume fraction of the portion other than the voids of the porous or hollow particles.
- Hollow particles are particles in which voids are formed inside one particle.
- the inner voids are covered with silicon oxide. Therefore, the refractive index of hollow fine particles is lower than that of ordinary non-hollow particles because of the air filling the inside of the voids.
- the refractive index of ordinary silica particles is 1.46.
- the hollow silica particles can have a refractive index of 1.3 or less.
- the hollow particles for example, a production method disclosed in JP-A-2001-233611 can be preferably used.
- the gas contained therein may be an inert gas other than air or nitrogen.
- the thickness of the outer shell is desirably 10% or more of the particle diameter, and therefore the porosity is 73% or less.
- the porosity becomes 8% or less, and the effect of lowering the refractive index may hardly appear.
- the average particle size of the fine particles is preferably in the range of 5 nm to 300 nm.
- the average particle size is larger than 300 nm, light is scattered by Mie scattering and geometric optical scattering, and it looks whitish and transparency is lowered.
- the average particle size is smaller than 5 nm, the fine particles are aggregated and may not be uniformly dispersed in the phosphor layer.
- the average particle diameter is more preferably in the range of 10 nm to 50 nm.
- the volume of fine particles should be less than 90% of the phosphor layer. If it is 90% or more, it becomes difficult to form the phosphor layer as a uniform thin film. In addition, when the volume of the fine particles is 10% or less of the phosphor layer, the volume of the hollow portion in the phosphor layer is not sufficiently large, so that the effect of reducing the refractive index is difficult to obtain. In order to form the phosphor layer as a uniform thin film and to sufficiently obtain the effect of lowering the refractive index, the volume of the fine particles is particularly preferably 50% or more and 80% or less of the phosphor layer.
- the binder resin material is preferably a translucent resin.
- the resin material include acrylic resin, melamine resin, polyester resin, polyurethane resin, alkyd resin, epoxy resin, butyral resin, polysilicone resin, polyamide resin, polyimide resin, melanin resin, phenol resin, polyvinyl alcohol, polyvinyl Hydrine, hydroxyethyl cellulose, carboxyl methyl cellulose, aromatic sulfonamide resin, urea resin, benzoguanamine resin, triacetyl cellulose (TAC), polyether sulfone, polyether ketone, nylon, polystyrene, melamine beads, polycarbonate, polyvinyl chloride, Polyvinylidene chloride, polyvinyl acetate, polyethylene, polymethyl methacrylate, poly MBS, medium density polyethylene, high density polyethylene, tetrafluoroethylene Oroechiren, poly trifluorochloroethylene, polytetrafluoroethylene and the like.
- fluorescent paint When the fluorescent material described above is formed on a substrate by a wet process to obtain a phosphor substrate, it is preferable to use a fluorescent paint in which the fluorescent material is applied.
- the fluorescent paint of the present embodiment is obtained by using the above-described fluorescent material and adding an appropriate solvent and an appropriate binder resin that dissolve or disperse the fluorescent material. Further, other compositions may be added for adjusting the viscosity and the like.
- the phosphor substrate of the present embodiment is a fluorescent paint containing the above-described fluorescent material, for example, a spin coating method, a dipping method, a doctor blade method, a discharge coating method, a coating method such as a spray coating method, an inkjet method, a relief printing method, It can be obtained by coating on a substrate by a known wet process such as an intaglio printing method, a screen printing method, or a printing method such as a micro gravure coating method.
- a fluorescent material such as a resistance heating vapor deposition method, an electron beam (EB) vapor deposition method, a molecular beam epitaxy (MBE) method, a sputtering method, and an organic vapor deposition (OVPD) method can be used without forming a coating liquid such as a fluorescent paint.
- the phosphor substrate can also be obtained by patterning the substrate by a dry process or a laser transfer method.
- FIG. 4 is a schematic cross-sectional view showing the display device of the first embodiment.
- the cross section of FIG. 4 is a cross section when the display device 100 ⁇ / b> A is cut along a plane orthogonal to the upper surface of the substrate 30.
- a schematic diagram of a cross section when the display device is cut along a plane orthogonal to the upper surface of the substrate 30 may be referred to as a cross sectional view of the display device.
- the display device 100A includes a phosphor substrate 20 and a light source substrate 21 bonded to the phosphor substrate 20 with an adhesive layer 24 interposed therebetween.
- the phosphor substrate 20 is formed by forming the phosphor material of the above-described embodiment (see FIGS. 1A to 2D, etc.) on the substrate, and an image is formed by three sub-pixels that respectively display red, green, and blue. One pixel which is the minimum unit is configured.
- a sub pixel that performs red display is referred to as a red sub pixel PR
- a sub pixel that performs green display is referred to as a green sub pixel PG
- a sub pixel that performs blue display is referred to as a blue sub pixel PB.
- the light source substrate 21 includes a substrate 29 and a light source 22 disposed on the phosphor substrate 20 side of the substrate 29. From the light source 22, ultraviolet light or blue light is emitted as the excitation light L1.
- the phosphor substrate 20 receives the excitation light L1 emitted from the light source 22, and red fluorescence L2 is generated in the red sub-pixel PR.
- Green fluorescence L2 is generated in the green sub-pixel PG.
- Blue fluorescence L2 is generated in the blue sub-pixel PB, or blue light from the excitation light source is scattered by a scatterer disposed in the blue sub-pixel PB. Then, full color display is performed by these three color lights of red, green and blue.
- the phosphor substrate 20 includes a substrate 30, phosphor layers 31R, 31G, and 31B, partition walls 35, and color filters 34R, 34G, and 34B.
- the phosphor layers 31 ⁇ / b> R, 31 ⁇ / b> G, and 31 ⁇ / b> B are provided on the substrate 30, and generate fluorescence L ⁇ b> 2 by excitation light L ⁇ b> 1 incident from above the substrate 30.
- the barrier ribs 35 surround the side surfaces of the phosphor layers 3R, 3G, 3B.
- the excitation light incident surface 31 a on which the excitation light L 1 of the phosphor layers 31 R, 31 G, 31 B is incident is exposed from the opening of the partition wall 35. That is, the excitation light incident surface 31a is a surface on which the excitation light L1 emitted from the light source 22 can enter.
- the excitation light L1 is converted into fluorescence L2 in the phosphor layers 31R, 31G, and 31B, and the fluorescence L2 is emitted from the emission surface 31b of the phosphor layers 31R, 31G, and 31B.
- the phosphor layers 31R, 31G, and 31B are composed of a plurality of phosphor layers divided for each sub-pixel, and the plurality of phosphor layers 31R, 31G, and 31B are made of different phosphor materials in order to emit different color light depending on the sub-pixel. It is configured.
- a wavelength selective transmission / reflection member that transmits the excitation light L1 and reflects the fluorescence L2 emitted from the phosphor layers 31R, 31G, and 31B on the outer surface side of the excitation light incident surface 31a of the phosphor layers 31R, 31G, and 31B.
- a pass filter may be formed. Note that “transmitting excitation light” means transmitting at least light corresponding to the peak wavelength of excitation light. Further, “reflect the fluorescence generated in the phosphor layers 31R, 31G, 31B” means that at least the light corresponding to the respective emission peak wavelengths from the phosphor layers 31R, 31G, 31B is reflected.
- the partition wall 35 has a laminated structure of a light absorption layer 36 having a light absorption property and a light scattering layer 37 having a light scattering property from the substrate 30 side.
- the shape of the partition wall 35 is a taper shape such that the opening on the side away from the substrate 30 is wider than the opening on the side in contact with the substrate 30.
- the partition wall 35 may be formed of a material that reflects the fluorescence generated in the phosphor layer 31. Thereby, the fluorescent component which escapes from the phosphor layer 31 to the side can be reflected. Further, only the surface of the partition wall 35 may be covered with a reflective material. Examples of such a reflective material include reflective metals such as aluminum, silver, gold, aluminum-lithium alloys, aluminum-neodymium alloys, and aluminum-silicon alloys.
- the shape of the partition wall 35 various shapes surrounding the phosphor layers 31R, 31G, and 31B, such as a lattice shape and a stripe shape, can be adopted.
- a red color filter 34R is provided between the substrate 30 and the red phosphor layer 31R.
- a green color filter 34G is provided between the substrate 30 and the green phosphor layer 31G.
- a blue color filter 34B is provided between the substrate 30 and the blue phosphor layer 31B.
- the film thickness of the color filter 34 is desirably thicker than the film thickness of the light absorption layer 36.
- the color filter 34 is thinner than the light absorption layer 36, the side surface of the phosphor layer 31 and the light absorption layer 36 are in contact with each other. Thereby, the light emission from the phosphor layer 31 is absorbed by the light absorption layer 36, and the light extraction efficiency is lowered.
- the structural member and the formation method of the phosphor substrate 20 according to the present embodiment will be specifically described, the structural member and the formation method of the phosphor substrate 20 are not limited thereto.
- the substrate 30 for the phosphor substrate 20 used in the present embodiment needs to take out the fluorescence L2 from the phosphor layers 31R, 31G, 31B to the outside, it is in the light emitting region of the phosphor layers 31R, 31G, 31B. It is necessary to transmit the fluorescence L2. Therefore, as the substrate 30 for the phosphor substrate 20, for example, an inorganic material substrate made of glass, quartz or the like, a plastic substrate made of polyethylene terephthalate, polycarbazole, polyimide, or the like can be used. However, the substrate 30 for the phosphor substrate 20 is not limited to these substrates.
- the phosphor layers 31R, 31G, and 31B according to the present embodiment are made of the above-described phosphor material, that is, a phosphor in which fine particles are dispersed and mixed, and an ultraviolet light emitting organic EL element, a blue light emitting organic EL element, an ultraviolet light emitting LED, It is composed of a red phosphor layer 31R, a green phosphor layer 31G, and a blue phosphor layer 31B that absorb the excitation light L1 from the light source 2 such as a blue LED and emit red, green, and blue light.
- the blue phosphor layer 31B is not provided, and the blue excitation light L1 may be emitted from the blue subpixel PB. Further, in the case of applying directional blue light emission as the light source 22, the blue phosphor layer 31 ⁇ / b> B is not provided, and the directional excitation light L ⁇ b> 1 can be scattered to be extracted as isotropic light. A simple light scattering layer may be applied.
- a phosphor layer that emits cyan light and yellow light to the pixels as necessary.
- the color reproduction range can be further expanded as compared with a display device using pixels that emit three primary colors of red, green, and blue.
- the thickness of the phosphor layer 31 is usually about 100 nm to 100 ⁇ m, preferably 1 ⁇ m to 100 ⁇ m. If the film thickness is less than 100 nm, it is impossible to sufficiently absorb the excitation light from the light source, so that the light emission efficiency decreases, and the color purity deteriorates due to the mixture of the transmitted light of the excitation light with the required color. Such a phenomenon occurs. Further, in order to increase absorption of excitation light from the light source and reduce transmitted light of excitation light to such an extent that the color purity is not adversely affected, the film thickness is preferably 1 ⁇ m or more. Further, when the film thickness exceeds 100 ⁇ m, the excitation light from the light source is already sufficiently absorbed, so that the efficiency is not increased, the material is consumed only, and the material cost is increased.
- the light scattering particles may be composed of an organic material, an inorganic material, or an organic material and an inorganic material. Although it may be comprised by the combination of these, it is preferable that it is comprised by the inorganic material. This makes it possible to diffuse or scatter light having directivity from the light source 22 more isotropically and effectively.
- the light scattering particles have high transparency.
- the light scattering particles are preferably particles in which fine particles having a higher refractive index than the base material are dispersed in a low refractive index base material.
- the particle size of the light scattering particle is in the Mie scattering region, so the particle size of the light scattering particle is 100 nm to 500 nm. The degree is preferred.
- the main component is an oxide of at least one metal selected from the group consisting of silicon, titanium, zirconium, aluminum, indium, zinc, tin, and antimony.
- the main component includes particles (fine particles).
- examples thereof include silica beads, alumina beads, titanium oxide beads, zirconia oxide beads, zinc oxide beads, and barium titanate (BaTiO 3 ).
- particles composed of an organic material
- the light scattering particles for example, polymethyl methacrylate beads, acrylic beads, acrylic-styrene copolymer beads, melamine beads, high refractive index melamine beads, polycarbonate
- examples thereof include beads, styrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde beads, and silicone beads.
- the resin material used by mixing with the light scattering particles described above is preferably a translucent resin.
- the resin material include acrylic resin, melamine resin, nylon, polystyrene, melamine beads, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, polymethyl methacrylate, poly MBS, medium density polyethylene, High density polyethylene, tetrafluoroethylene, polytrifluoroethylene chloride, polytetrafluoroethylene and the like can be mentioned.
- fine particles having a refractive index of 1.3 or less similar to that added to the phosphor layer are added to the scatterer layer, and the scatterer The refractive index of the layer may be lowered.
- the low refractive index fine particles may be uniformly dispersed or may exist with a concentration gradient.
- Partition wall As a material of the partition wall 35, a black matrix or metal used as a partition wall of a conventional display can be used. However, in order to improve the light extraction efficiency to the emission side, a resin with a low refractive index is used. It is desirable to use a light-scattering partition wall made of a light-scattering material in which light-scattering particles having a refractive index higher than that of the resin are dispersed. More preferably, in order to achieve both high contrast and high light extraction efficiency, after forming a light absorption layer of about 0.01 ⁇ m to 3 ⁇ m on the substrate, the light absorption layer has a ground contact area smaller than the ground contact area to the substrate.
- a light scattering layer having a thickness of about 1 ⁇ m to 100 ⁇ m is formed so as to be in contact with the absorption layer.
- the thickness of the light scattering layer needs to be sufficiently thicker than the thickness of the light absorption layer.
- the resin examples include acrylic resin, melamine resin, nylon, polystyrene, melamine beads, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyethylene, polymethyl methacrylate, poly MBS, medium density polyethylene, and high density polyethylene. , Tetrafluoroethylene, polytrifluoroethylene chloride, polytetrafluoroethylene and the like.
- the light scattering particles when an inorganic material is used, for example, an oxide of at least one metal selected from the group consisting of silicon, titanium, zirconium, aluminum, indium, zinc, tin, and antimony is used. Examples thereof include particles (fine particles) having a main component. Examples thereof include silica beads, alumina beads, titanium oxide beads, zirconia oxide beads, zinc oxide beads, and barium titanate (BaTiO 3 ).
- organic materials for example, polymethyl methacrylate beads, acrylic beads, acrylic-styrene copolymer beads, melamine beads, high refractive index melamine beads, polycarbonate beads, styrene beads, Examples include crosslinked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde beads, and silicone beads.
- Examples of the method for forming the partition wall 35 include a photolithography method, a screen printing method, a vapor deposition method, a sand blast method, and a transfer method.
- the formation by a photolithography method is desirable because a partition wall having high definition and a high aspect ratio can be formed at low cost.
- the partition wall material can be made into a negative photoresist, or instead of a photopolymerizable monomer or a photopolymerization initiator. It is possible to make a positive photoresist by adding a photosensitizer such as diazonaphthoquinone, and patterning can be performed by photolithography.
- the vertical and horizontal size of the opening of the partition wall 35 is preferably about 20 ⁇ m ⁇ 20 ⁇ m to about 500 ⁇ m ⁇ 500 ⁇ m.
- the color filter is provided between the light extraction side substrate 30 and the phosphor layers 31R, 31G, and 31B.
- a conventional color filter can be used as the color filter.
- the color purity of the red subpixel PR, the green subpixel PG, and the blue subpixel PB can be increased, and the color reproduction range of the display device 100A can be expanded.
- the red color filter 34R facing the red phosphor layer 31R absorbs excitation light that excites the red phosphor layer 31R of external light. For this reason, it is possible to reduce or prevent light emission of the red phosphor layer 31R due to external light, and it is possible to reduce or prevent a decrease in contrast. Further, the red color filter 34R can prevent the excitation light L1 that is not absorbed and transmitted by the red phosphor layer 31R from leaking outside. For this reason, it is possible to prevent a decrease in the color purity of the light emission due to the color mixture by the light emission from the red phosphor layer 31R and the excitation light L1.
- the green color filter 34G facing the green phosphor layer 31G absorbs excitation light that excites the green phosphor layer 31G of external light. For this reason, it becomes possible to reduce or prevent light emission of the green phosphor layer 31G due to external light, and it is possible to reduce or prevent a decrease in contrast. Further, the green color filter 34G can prevent the excitation light L1 that is not absorbed and transmitted by the green phosphor layer 31G from leaking outside. For this reason, it is possible to prevent a decrease in color purity of the light emission due to the color mixture by the light emission from the green phosphor layer 31G and the excitation light L1.
- the blue color filter 34B facing the blue phosphor layer 31B absorbs excitation light that excites the blue phosphor layer 31B of external light. For this reason, it becomes possible to reduce or prevent light emission of the blue phosphor layer 31B due to external light, and it is possible to reduce or prevent a decrease in contrast. Further, the blue color filter 34B can prevent the excitation light L1 that is not absorbed and transmitted by the blue phosphor layer 31B from leaking outside. For this reason, it is possible to prevent a decrease in the color purity of the light emission due to the color mixture by the light emission from the blue phosphor layer 3B and the excitation light L1.
- FIG. 5 is a cross-sectional view showing the phosphor substrate 20A of the first embodiment.
- the basic structure of the phosphor substrate 20A of the present embodiment is the same as that of the phosphor substrate shown in the first embodiment of the display device, and the phosphor layers 31RA, 31GA, and the like provided in the region surrounded by the partition walls 35.
- the shape of 31BA is different from the phosphor substrate in the first embodiment of the display device.
- the same components as those in FIG. 4 are denoted by the same reference numerals, and detailed description thereof is omitted.
- the side cross-sectional shapes of the phosphor layers 31RA, 31GA, and 31BA in the region surrounded by the partition walls 35 are concave shapes.
- the peripheral portions of the phosphor layers 31RA, 31GA, and 31BA are disposed along the side surfaces of the partition walls 35.
- the phosphor layers 31RA, 31GA, 31BA have a flat upper surface at the center of the phosphor layers 31RA, 31GA, 31BA.
- the height of the upper surface of the central part of the phosphor layers 31RA, 31GA, 31BA is substantially half the height of the partition wall 35.
- the height of the peripheral portions of the phosphor layers 31RA, 31GA, and 31BA is substantially the same as the height of the partition walls 35.
- the excitation light traveling from the light source toward the pixel is prevented from being absorbed by the partition wall 35 or transmitted through the partition wall 35. Therefore, the light extraction efficiency can be improved.
- FIG. 6 is a cross-sectional view of the display device 100B of the second embodiment.
- the basic configuration of the display device 100B of the present embodiment is the same as that of the display device of the first embodiment, and the configuration of the partition walls 35B is different from the display device of the first embodiment. Therefore, in the present embodiment, the description of the basic configuration of the display device 100B is omitted, and the partition wall 35B will be described.
- the black layer 38 is provided on the upper surface of the light scattering layer 37. Thereby, since a part of the excitation light emitted from the light source 22 is absorbed by the black layer 38, light leakage to adjacent pixels can be suppressed and color mixing can be avoided.
- the thickness of the black layer 38 is thinner than the thickness of the light scattering layer 37.
- the thickness of the black layer 38 is about 0.01 ⁇ m to 3 ⁇ m.
- the width of the black layer 38 is equal to the width of the upper surface of the light scattering layer 37.
- the black layer 38 is provided on the upper surface of the light scattering layer 37 and the light absorption layer 36 is provided on the lower surface of the light scattering layer 37.
- the present invention is not limited to this.
- the black layer 38 may be provided only on the upper surface of the light scattering layer 37, and the light absorption layer 36 may not be provided on the lower surface of the light scattering layer 37.
- FIG. 7 is a cross-sectional view of a display device 100C according to the third embodiment.
- the basic configuration of the display device 100C of the present embodiment is the same as that of the display device of the second embodiment, in that the planarization layer 33 is provided on the upper surfaces of the phosphor layers 31R, 31G, and 31B, and the upper surface of the planarization layer 33.
- the fourth embodiment is different from the fourth embodiment in that a band pass filter 32 is provided. Therefore, in this embodiment, the description of the basic configuration of the display device 100C is omitted.
- the planarizing layer 33 is formed on the upper surfaces of the phosphor layers 31R, 31G, 31B of the phosphor substrate 20C.
- a band pass filter 32 is provided on the upper surfaces of the planarizing layer 33 and the partition walls 35C.
- the bandpass filter 32 transmits light in the blue region (light in the wavelength range of 435 nm to 480 nm) and transmits light from green to the near infrared region ( A function of reflecting light outside the wavelength range of the blue region.
- the band-pass filter 32 is made of, for example, a thin film such as gold or silver, or a dielectric multilayer film.
- the blue light emitted from the light source 2 can be transmitted through the band pass filter 32 and converted in wavelength by the phosphor layer 31 to emit green light or red light. Further, since the band pass filter 32 reflects the green light and red light toward the band pass filter 32 again to the phosphor layer side, the green light and red light can be efficiently used, and more light is emitted. The improvement of the extraction efficiency can be expected.
- the band pass filter 32 is provided on the upper surface of the planarization layer 33, but the present invention is not limited to this.
- the band pass filter 32 may be provided on the upper surface of each phosphor layer 31R, 31G, 31B formed in the opening of the partition 3 without providing the planarizing layer 33. That is, the band pass filter 32 only needs to be provided between the light source substrate 21 and the phosphor substrate 20C.
- the bandpass filter 32 transmits light in the ultraviolet region (light in the wavelength range of 360 nm to 435 nm) and emits light from green to the near infrared region. It may have a function of reflecting (light outside the wavelength range of the ultraviolet region). Thereby, the ultraviolet light emitted from the light source 22 is transmitted through the band-pass filter 32 and can be converted in wavelength by the phosphor layer 31 to emit green light or red light. Furthermore, since the band pass filter 32 reflects the green light and red light toward the band pass filter 32 again to the phosphor layer side, the green light and red light can be used efficiently.
- the light source 22 As the light source 22 for exciting the phosphor layers 31R, 31G, and 31B, ultraviolet light and blue light are preferable.
- the light source 22 include an ultraviolet LED, a blue LED, an ultraviolet light emitting inorganic EL, a blue light emitting inorganic EL, an ultraviolet light emitting organic EL, a blue light emitting organic EL, and the like, but this embodiment is limited to these light sources. is not. Further, by directly switching these light sources 22, it is possible to control ON / OFF of light emission for displaying an image.
- a layer having a shutter function such as a liquid crystal is arranged between the phosphor layers 31R, 31G, and 31B and the light source 22, and it is possible to control ON / OFF of light emission by controlling the layer. is there. It is also possible to control ON / OFF of both the light source 22 and the layer having a shutter function such as liquid crystal.
- the light source 22 a known ultraviolet LED, blue LED, ultraviolet light emitting inorganic EL, blue light emitting inorganic EL, ultraviolet light emitting organic EL, blue light emitting organic EL, or the like can be used.
- the light source 22 is not particularly limited, and can be manufactured using a known material or a known manufacturing method.
- the ultraviolet light preferably emits light having a main emission peak of 360 nm to less than 435 nm
- the blue light preferably emits light having a main emission peak of 435 nm to 480 nm.
- the light source 22 desirably has directivity. Directivity refers to the property that the intensity of light varies depending on the direction. The directivity may be provided at the time when light enters the phosphor layer. It is desirable that the light source 22 allows parallel light to enter the phosphor layer.
- the degree of directivity of the light source 22 is preferably a half width of ⁇ 30 degrees or less, more preferably ⁇ 10 degrees or less. This is because when the half-value width is larger than 30 degrees, light emitted from the backlight is incident on a pixel other than a desired pixel and excites an undesired phosphor to reduce color purity and contrast.
- the light source 22 ⁇ / b> A will be described as an example that can be suitably used for the light source 22.
- an LED light emitting diode
- a known LED can be used.
- an ultraviolet light emitting inorganic LED and a blue light emitting inorganic LED are suitable. These LEDs include, for example, a first buffer layer 43, an n-type contact layer 44, a second n-type cladding layer 45, a first n-type cladding layer 46, an active layer 47, a first layer on one surface of a substrate 39.
- a p-type cladding layer 48, a second p-type cladding layer 49, and a second buffer layer 40 are sequentially stacked, a cathode 42 is formed on the n-type contact layer 44, and an anode 41 is formed on the second buffer layer 40.
- the specific structure of LED is not restricted to the above-mentioned thing.
- an organic EL element can be used as the light source 22B.
- a known organic EL can be used.
- the organic EL element 22B includes, for example, an anode 51, a hole injection layer 53, a hole transport layer 54, a light emitting layer 55, a hole prevention layer 56, an electron transport layer 57, an electron injection layer 58, and a cathode 59 on one surface of the substrate 39.
- An edge cover 52 is formed so as to cover the end face of the anode 51.
- the organic EL element 23B only needs to include an organic EL layer including at least a light emitting layer (organic light emitting layer) 55 made of an organic light emitting material between the anode 51 and the cathode 59.
- a light emitting layer organic light emitting layer
- the specific configuration is as described above. It is not limited to.
- layers from the hole injection layer 53 to the electron injection layer 58 may be referred to as an organic EL layer.
- the organic EL element 22B is provided in a matrix corresponding to each of the red sub-pixel PR, the green sub-pixel PG, and the blue sub-pixel PB shown in FIG. 4, and is individually controlled to be turned on / off. Yes.
- the driving method of the plurality of organic EL elements 2B may be active matrix driving or passive matrix driving.
- an inorganic EL element can be used as the light source 22C.
- a known inorganic EL element can be used.
- an ultraviolet light emitting inorganic EL element and a blue light emitting inorganic EL element are suitable.
- These inorganic EL elements are, for example, light sources having a configuration in which a first electrode 61, a first dielectric layer 62, a light emitting layer 63, a second dielectric layer 64, and a second electrode 65 are sequentially stacked on one surface of a substrate 39. 22C.
- the specific configuration of the inorganic EL element is not limited to the above.
- FIG. 11 is a schematic cross-sectional view of a display device 200 according to the fourth embodiment.
- the display device 200 is a configuration example in which a liquid crystal element 70 that is an optical member is inserted between a phosphor substrate 20D and a light source substrate 21D composed of an LED light source.
- components common to the display device 100 of the first embodiment shown in FIG. 4 are denoted by the same reference numerals, and detailed description thereof is omitted.
- the liquid crystal element 70 is configured to be able to control the voltage applied to the liquid crystal layer 78 for each pixel using a pair of electrodes 73 and 74, and to control the transmittance of light emitted from the entire surface of the light source for each pixel. . That is, the liquid crystal element 70 has a function as an optical shutter that selectively transmits light from the LED light source substrate 21D for each pixel.
- the liquid crystal element 70 includes a pair of polarizing plates 71 and 72, electrodes 73 and 74, alignment films 75 and 76, and a substrate 77.
- the liquid crystal layer 78 is sandwiched between the alignment films 75 and 76.
- one optically anisotropic layer is disposed between the liquid crystal cell and one polarizing plate 71 or 72, or the optically anisotropic layer is disposed between the liquid crystal cell and both polarizing plates 71 and 72. 2 may be arranged.
- the type of liquid crystal cell is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include TN mode, VA mode, OCB mode, IPS mode, and ECB mode. Further, the liquid crystal element 70 may be passively driven or may be actively driven using a switching element such as a TFT.
- the phosphor substrate 20D, the liquid crystal element 70, and the LED light source element substrate 21D are joined and integrated through the adhesive layer 24. That is, the surface of the phosphor substrate 20D on which the phosphor layers 31R, 31G, and 31B are formed and the polarizing plate 71 of the liquid crystal element 70 are bonded together via the adhesive layer 24, and the LED of the LED light source element substrate 21D is formed. And the polarizing plate 72 of the liquid crystal element 70 are bonded to each other with the adhesive layer 24 interposed therebetween.
- At least one of the polarizing plates 71 and 72 preferably has an extinction ratio of 10,000 or more at a wavelength of 435 nm or more and 480 nm or less.
- the extinction ratio can be measured, for example, by a rotating analyzer method using a Glan-Thompson prism.
- the polarization transmittance refers to the transmittance when ideal polarized light is incident using a Glan-Thompson prism.
- the contrast and transmittance mainly in the region of 550 nm, and the quenching in the short wavelength region of 490 nm or less of the iodine polarizing plate used in the conventional liquid crystal is about 2000 to 3000 (the extinction ratio in the green region and the red region is about 10,000).
- the polarizing plate for a blue excitation type display using the blue light backlight according to the present embodiment, an optimum design can be made for the blue region, so that the extinction ratio in the blue region is 10,000 or more.
- a polarizing plate is used.
- the contrast of the panel can be increased by using a polarizing plate having a high extinction ratio.
- a polarizing plate with a high extinction ratio has high transmittance, the light use efficiency of the backlight can be increased, and power consumption can be reduced.
- FIG. 12 is a schematic cross-sectional view of a display device 300 according to the fifth embodiment.
- the display device 300 is a configuration example in which a phosphor substrate 20E and an organic EL element light source substrate 21E including an organic EL element light source are stacked.
- the same reference numerals are given to components common to the display device 100A of the first embodiment, and detailed description thereof is omitted.
- the organic EL element light source substrate 21E is provided on one surface of the substrate 39, and an organic electroluminescence unit (hereinafter referred to as “organic EL”) in which an organic layer 83 is sandwiched between a first electrode 81 and a second electrode 82. And a sealing film 85 that seals the organic EL portion 84.
- organic EL organic electroluminescence unit
- the first electrode 82 is provided on one surface of the substrate 39, and includes a reflective electrode 91 and a transparent electrode 92 provided on the reflective electrode 91.
- the organic layer 83 is sequentially stacked from the first electrode 82 side toward the second electrode 86 side, and the hole injection layer 93, the hole transport layer 94, the organic light emitting layer 95, the electron transport layer 96, and the electron injection layer 97 are stacked. It is composed of
- the phosphor substrate 20E and the organic EL element light source substrate 21E are joined and integrated through the adhesive layer 24. That is, the surface of the phosphor substrate 20E on which the phosphor layers 31R, 31G, and 31B are formed and the light emitting surface of the organic EL element light source substrate 21E are bonded together via the adhesive layer 24.
- Examples of the electronic device provided with the display device of the embodiment include a mobile phone shown in FIG. 13A and a television receiver shown in FIG. 13B.
- a cellular phone 400 illustrated in FIG. 13A includes a main body 410, a display unit 420, an audio input unit 430, an audio output unit 440, an antenna 450, an operation switch 460, and the like.
- the display device of the above embodiment is used as the display unit 420. It has been.
- a television receiver 500 illustrated in FIG. 13B includes a main body cabinet 510, a display unit 520, a speaker 530, a stand 540, and the like, and the display device of the above embodiment is used for the display unit 520. In such an electronic device, since the display device of the above-described embodiment is used, an electronic device having excellent display quality can be realized.
- the display device can be applied to, for example, a portable game machine shown in FIG. 14A.
- a portable game machine 600 illustrated in FIG. 14A includes an operation button 610, an LED lamp 620, a housing 630, a display unit 640, an infrared port 650, and the like.
- the display apparatus which concerns on one Embodiment of this invention can be applied suitably as the display part 640.
- FIG. By applying the display device according to an embodiment of the present invention to the display unit 640 of the portable game machine 600, a high contrast image can be displayed with low power consumption.
- the display device according to an embodiment of the present invention can be applied to, for example, a notebook computer shown in FIG. 14B.
- a notebook computer 700 illustrated in FIG. 14B includes a keyboard 710, a pointing device 720, a housing 730, a display unit 740, a camera 750, an external connection port 760, a power switch 770, and the like.
- a display device according to an embodiment of the present invention can be suitably applied as the display unit 740 of the notebook personal computer 700.
- the notebook computer 700 capable of displaying a high contrast image can be realized.
- the display device according to an embodiment of the present invention can be applied to, for example, the ceiling light shown in FIG. 15A.
- a ceiling light 800 shown in FIG. 15A includes an illumination unit 810, a hanging tool 820, a power cord 830, and the like.
- the display apparatus which concerns on one Embodiment of this invention can be applied suitably as the illumination part 810.
- FIG. 8 By applying the display device according to an embodiment of the present invention to the illumination unit 810 of the ceiling light 800, illumination light with a free color tone can be obtained, and a lighting fixture with high light performance can be realized. In addition, it is possible to realize a lighting fixture capable of emitting surface light with high color purity with uniform illuminance.
- the display device according to an embodiment of the present invention can be applied to, for example, a lighting stand shown in FIG. 15B.
- An illumination stand 900 shown in FIG. 15B includes an illumination unit 910, a stand 920, a power switch 930, a power cord 940, and the like.
- the display apparatus which concerns on one Embodiment of this invention can be applied suitably as the illumination part 910.
- FIG. 15B By applying the display device according to an embodiment of the present invention to the illumination unit 910 of the illumination stand 900, illumination light with a free color tone can be obtained, and an illumination fixture with high light performance can be realized. In addition, it is possible to realize a lighting fixture capable of emitting surface light with high color purity with uniform illuminance.
- the display device according to the embodiment of the present invention can be applied to, for example, the tablet terminal shown in FIG.
- a tablet terminal 1000 illustrated in FIG. 16 includes a display unit (touch panel) 1010, a camera 1020, a housing 1030, and the like.
- the display apparatus which concerns on one Embodiment of this invention can be applied suitably as the display part 1010.
- FIG. 10 By applying the display device according to an embodiment of the present invention to the display unit 1010 of the tablet terminal 1000, it is possible to display a good image with low power consumption and a wide viewing angle.
- the phosphor substrate according to one embodiment of the present invention can be applied to, for example, the LED package shown in FIG.
- electrode patterns 1120a and 1120b are formed on a substrate 1110, an LED chip 1130 is mounted thereon, and is electrically connected to the electrode patterns 1120a and 1120b by wires 1140 and the like.
- a reflective frame 1150 is mounted on the substrate 1110 so as to incorporate the LED chip 1130, and a reflective layer 1160 is formed inside the reflective frame 1150.
- the reflective layer 1160 is formed by reflecting or painting aluminum (Al) and / or silver (Ag) having a high reflectance to form a reflective surface. Further, a phosphor layer 1170 is formed in a space in which the LED chip 1130 inside the reflection frame 1150 is mounted. This includes a phosphor 1180a, a low refractive index fine particle 1180b, a diffusing agent 1180c and the like on a transparent resin. The LED chip 1130 is sealed. By applying the phosphor according to an embodiment of the present invention to the LED package 1100, an LED package with low power consumption and high luminance can be realized.
- a green phosphor layer 100 g of a toluene solution in which 10 wt% of PMMA was dissolved was added to 0.1 g of coumarin 545T, and the mixture was heated and stirred to prepare a coating solution for forming a green phosphor.
- the prepared green phosphor forming coating solution was applied onto the substrate using a spinner. Subsequently, it was dried by heating in a vacuum oven (100 ° C., 10 mmHg) for 4 hours to form a green phosphor layer having a refractive index of 1.50, thereby obtaining a phosphor substrate.
- Example 1-1 As the substrate, 0.7 mm glass was used. This was washed with water, then subjected to pure water ultrasonic cleaning for 10 minutes, acetone ultrasonic cleaning for 10 minutes, and isopropyl alcohol vapor cleaning for 5 minutes, and dried at 100 ° C. for 1 hour.
- the prepared green phosphor forming coating solution was applied onto the substrate using a spinner. Subsequently, it was dried by heating in a vacuum oven (100 ° C., 10 mmHg) for 4 hours to form a green phosphor layer having a refractive index of 1.26 to obtain a phosphor substrate.
- Example 1-2 As the substrate, 0.7 mm glass was used. This was washed with water, then subjected to pure water ultrasonic cleaning for 10 minutes, acetone ultrasonic cleaning for 10 minutes, and isopropyl alcohol vapor cleaning for 5 minutes, and dried at 100 ° C. for 1 hour.
- the prepared green phosphor forming coating solution was applied onto the substrate using a spinner. Subsequently, it was heated and dried in a vacuum oven (100 ° C., 10 mmHg) for 4 hours to form a green phosphor layer to obtain a phosphor substrate.
- Comparative Example 2 A phosphor substrate was prepared in the same manner as described in Comparative Example 1. A band-pass filter having a transmittance of 85% light at a wavelength of 460 nm and a transmittance of visible light at a wavelength of 480 nm or more is 5% or less is bonded to the phosphor substrate using a thermosetting transparent elastomer. It was.
- Example 2-1 A phosphor substrate was prepared in the same manner as described in Example 1-1.
- a band-pass filter having a transmittance of 85% light at a wavelength of 460 nm and a transmittance of visible light at a wavelength of 480 nm or more is 5% or less is bonded to the phosphor substrate using a thermosetting transparent elastomer. It was.
- Example 2-2 A phosphor substrate was prepared in the same manner as described in Example 1-2.
- a band-pass filter having a transmittance of 85% light at a wavelength of 460 nm and a transmittance of visible light at a wavelength of 480 nm or more is 5% or less is bonded to the phosphor substrate using a thermosetting transparent elastomer. It was.
- a black partition material As a black partition material, a BK resist manufactured by Tokyo Ohka Co., Ltd. was applied using a spin coater. Then, it prebaked at 70 degreeC for 15 minutes, and formed the coating film with a film thickness of 1 micrometer. This coating film was covered with a mask (pixel pitch 500 ⁇ m, line width 50 ⁇ m) capable of forming a desired image pattern, irradiated with i-line (100 mJ / cm 2 ) and exposed. Next, development was performed using an aqueous sodium carbonate solution as a developer, and rinse treatment was performed with pure water, whereby a pixel pattern-like structure 1208 was obtained.
- a mask pixel pitch 500 ⁇ m, line width 50 ⁇ m
- a white photosensitive composition composed of an epoxy resin, an acrylic resin, a rutile titanium oxide, a photopolymerization initiator, and an aromatic solvent was stirred and mixed to obtain a negative resist.
- a negative resist was applied onto the substrate 1201 using a spin coater. Then, it prebaked at 80 degreeC for 10 minute (s), and formed the coating film with a film thickness of 50 micrometers.
- the coated film was covered with a mask (pixel pitch 500 ⁇ m, line width 50 ⁇ m) capable of forming a desired image pattern, and i-line (300 mJ / cm 2 ) was irradiated for exposure. Subsequently, it developed using the alkaline developing solution, and obtained the pixel pattern-like structure. Subsequently, using a hot-air circulation type drying furnace, post-baking was performed at 140 ° C. for 60 minutes to produce partition walls 1204 for partitioning dots.
- a red color filter 1209R, a green color filter 1209G, and a blue color filter 1209B were formed in a pattern on the area partitioned by the partition 1204.
- the red phosphor layer 1221, the green phosphor layer 1222, and the blue light scattering layer 1223 were patterned in the region partitioned by the partition wall 1203. .
- red phosphor layer 1221 In the step of forming the red phosphor layer 1221, first, 100 g of a dichlorobenzene solution in which 10 wt% polystyrene is dissolved is added to 0.01 g of the red phosphor rhodamine 6G, and the mixture is heated and stirred to prepare a red phosphor forming coating solution. Produced. Next, the prepared red phosphor forming coating solution was applied in a pattern to the area partitioned by the partition 1204 by a dispenser method. Subsequently, it was heated and dried in a vacuum oven (200 ° C., 10 mmHg) for 4 hours, and a red phosphor layer 1221 having a refractive index of 1.50 was formed (FIG. 18C).
- the step of forming the green phosphor layer 1222 first, 100 g of a dichlorobenzene solution in which 10 wt% of polystyrene was dissolved was added to 0.01 g of coumarin 6, and the mixture was heated and stirred to prepare a green phosphor forming coating solution. Next, the produced green phosphor-forming coating solution was applied in a pattern to a region partitioned by the partition 1204 by a dispenser technique. Subsequently, it was dried by heating in a vacuum oven (conditions of 200 ° C. and 10 mmHg) for 4 hours to form a green phosphor layer 1222 having a refractive index of 1.50 (FIG. 18D).
- the blue light scattering layer 1223 In the formation process of the blue light scattering layer 1223, first, 5 g of titanium oxide having an average particle diameter of 200 nm as light scattering particles is added to 30 g of a resin “LuxPrint 8155” manufactured by Teijin DuPont Co., Ltd. as a binder resin. After thorough mixing for 30 minutes, the mixture was stirred for 15 minutes using a “Primix 40-40” dispersion stirrer manufactured by Primix to obtain a coating solution for forming a blue light scattering layer.
- a resin “LuxPrint 8155” manufactured by Teijin DuPont Co., Ltd. as a binder resin. After thorough mixing for 30 minutes, the mixture was stirred for 15 minutes using a “Primix 40-40” dispersion stirrer manufactured by Primix to obtain a coating solution for forming a blue light scattering layer.
- the prepared blue light scattering layer forming coating solution was applied in a pattern to a region partitioned by the partition 1204 by a dispenser method. Subsequently, it was dried by heating in a vacuum oven (200 ° C., 10 mmHg) for 4 hours, and a blue firefly scatterer layer having a refractive index of 1.60 was patterned. (FIG. 18E). Thus, the phosphor substrate 1240 was completed.
- FIG. 19 is a cross-sectional view showing a display device 1300 of Comparative Example 3.
- the display device 1300 includes a backlight 1312, a liquid crystal substrate 1390, and a phosphor substrate 1240.
- the backlight 1312 includes a light source 1313 and a light guide plate 1314.
- As the light source 1313 a blue LED (peak wavelength: 450 nm) having a directivity with a half width of 10 degrees was used.
- the liquid crystal substrate 1390 includes a first polarizing plate 1391, a first substrate 1393, a liquid crystal layer 1398, a second substrate 1394, and a second polarizing plate 1392.
- the first polarizing plate 1391 and the second polarizing plate 1392 have an extinction ratio of 12000 at a wavelength of 435 nm to 480 nm.
- the liquid crystal is driven by an active matrix driving method using TFTs. Pixels of the liquid crystal substrate 1390 are partitioned by a black matrix 1395.
- a band pass filter 1315 that transmits light in the blue region and reflects light from the green region to the near infrared region was bonded to the first knitted light plate 1391 through the first adhesive layer 1321.
- the phosphor substrate 1240 prepared by the above method was bonded to a liquid crystal substrate 1390 provided with a band-pass filter 1315 with the second adhesive layer 1322 interposed therebetween.
- a thermosetting transparent elastomer was used as the first adhesive layer 1321 and the second adhesive layer 1322.
- Example 3-1 As the substrate 101, 0.7 mm glass was used. This was washed with water, then subjected to pure water ultrasonic cleaning for 10 minutes, acetone ultrasonic cleaning for 10 minutes, and isopropyl alcohol vapor cleaning for 5 minutes, and dried at 100 ° C. for 1 hour.
- a black partition material As a black partition material, a BK resist manufactured by Tokyo Ohka Co., Ltd. was applied using a spin coater. Then, it prebaked at 70 degreeC for 15 minutes, and formed the coating film with a film thickness of 1 micrometer. This coating film was covered with a mask (pixel pitch 500 ⁇ m, line width 50 ⁇ m) capable of forming a desired image pattern, irradiated with i-line (100 mJ / cm 2 ) and exposed. Subsequently, it developed using the sodium carbonate aqueous solution as a developing solution, and the rinse process was performed with the pure water, and the pixel-pattern-like structure 102 was obtained.
- a mask pixel pitch 500 ⁇ m, line width 50 ⁇ m
- a white photosensitive composition composed of an epoxy resin, an acrylic resin, a rutile titanium oxide, a photopolymerization initiator, and an aromatic solvent was stirred and mixed to obtain a negative resist.
- a negative resist was applied onto the substrate 1201 using a spin coater. Then, it prebaked at 80 degreeC for 10 minute (s), and formed the coating film with a film thickness of 50 micrometers.
- the coated film was covered with a mask (pixel pitch 500 ⁇ m, line width 50 ⁇ m) capable of forming a desired image pattern, and i-line (300 mJ / cm 2 ) was irradiated for exposure. Subsequently, it developed using the alkaline developing solution, and obtained the pixel pattern-like structure. Subsequently, using a hot-air circulation type drying furnace, post-baking was performed at 140 ° C. for 60 minutes to produce partition walls 1204 for partitioning dots.
- a red phosphor layer 1209R, a green phosphor layer 1209G, and a blue light scattering layer 1209B were formed in a pattern on the area partitioned by the partition 1204.
- red phosphor layer 1209R In the formation process of the red phosphor layer 1209R, first, 100 g of a dichlorobenzene solution in which 10 wt% polystyrene is dissolved is added to 0.01 g of the red phosphor rhodamine 6G, and a hollow with a refractive index of 1.21 and a particle diameter of 20 nm is added. 40 g of silica was added, and the mixture was heated and stirred to prepare a red phosphor-forming coating solution. Next, the prepared red phosphor forming coating solution was applied in a pattern to the area partitioned by the partition 1204 by a dispenser method. Subsequently, it was heated and dried in a vacuum oven (200 ° C., 10 mmHg) for 4 hours to form a red phosphor layer 1209R having a refractive index of 1.50.
- a dichlorobenzene solution in which 10 wt% polystyrene is dissolved is added to
- the step of forming the green phosphor layer 1209G first, 100 g of a dichlorobenzene solution in which 10 wt% polystyrene is dissolved is added to 0.01 g of coumarin, and then 40 g of hollow silica having a refractive index of 1.21 and a particle diameter of 20 nm is added. Then, the mixture was heated and stirred to prepare a green phosphor forming coating solution. Next, the produced green phosphor-forming coating solution was applied in a pattern to a region partitioned by the partition 1204 by a dispenser technique. Subsequently, it was dried by heating in a vacuum oven (200 ° C., 10 mmHg) for 4 hours to form a green phosphor layer 1209G having a refractive index of 1.50.
- the blue light scattering layer 1209B In the formation process of the blue light scattering layer 1209B, first, 5 g of titanium oxide having an average particle diameter of 200 nm as light scattering particles is added to 30 g of a resin “LuxPrint 8155” manufactured by Teijin DuPont Co., Ltd. as a binder resin, and further a refractive index of 1 .10 g of hollow silica with a particle size of 20 nm and 21 g were added, and after thorough mixing for 30 minutes in an automatic mortar, the mixture was stirred for 15 minutes using a Primix dispersion stirrer “Filmix 40-40” to produce a blue light scattering layer A forming coating solution was obtained.
- a resin “LuxPrint 8155” manufactured by Teijin DuPont Co., Ltd. as a binder resin
- a refractive index of 1 .10 g of hollow silica with a particle size of 20 nm and 21 g were added, and after thorough mixing for 30 minutes in an automatic
- the prepared blue light scattering layer forming coating solution was applied in a pattern to a region partitioned by the partition 1204 by a dispenser method. Subsequently, it was dried by heating in a vacuum oven (200 ° C., 10 mmHg) for 4 hours, and a blue firefly scatterer layer 1209B having a refractive index of 1.60 was patterned. Thus, the phosphor substrate was completed.
- Example 3-2 As the substrate 1201, 0.7 mm glass was used. This was washed with water, then subjected to pure water ultrasonic cleaning for 10 minutes, acetone ultrasonic cleaning for 10 minutes, and isopropyl alcohol vapor cleaning for 5 minutes, and dried at 100 ° C. for 1 hour.
- a black partition material As a black partition material, a BK resist manufactured by Tokyo Ohka Co., Ltd. was applied using a spin coater. Then, it prebaked at 70 degreeC for 15 minutes, and formed the coating film with a film thickness of 1 micrometer. This coating film was covered with a mask (pixel pitch 500 ⁇ m, line width 50 ⁇ m) capable of forming a desired image pattern, irradiated with i-line (100 mJ / cm 2 ) and exposed. Subsequently, it developed using the sodium carbonate aqueous solution as a developing solution, and the rinse process was performed with the pure water, and the pixel-pattern-like structure 102 was obtained.
- a mask pixel pitch 500 ⁇ m, line width 50 ⁇ m
- a white photosensitive composition composed of an epoxy resin, an acrylic resin, a rutile titanium oxide, a photopolymerization initiator, and an aromatic solvent was stirred and mixed to obtain a negative resist.
- a negative resist was applied onto the substrate 1201 using a spin coater. Then, it prebaked at 80 degreeC for 10 minute (s), and formed the coating film with a film thickness of 50 micrometers.
- the coated film was covered with a mask (pixel pitch 500 ⁇ m, line width 50 ⁇ m) capable of forming a desired image pattern, and i-line (300 mJ / cm 2 ) was irradiated for exposure. Subsequently, it developed using the alkaline developing solution, and obtained the pixel pattern-like structure. Subsequently, using a hot-air circulation type drying furnace, post-baking was performed at 140 ° C. for 60 minutes to produce partition walls 1204 for partitioning dots.
- a red phosphor layer 1209R, a green phosphor layer 1209G, and a blue light scattering layer 1209B were formed in a pattern on the area partitioned by the partition 1204.
- red phosphor layer 1209R In the formation process of the red phosphor layer 1209R, first, 100 g of a toluene solution in which 10 wt% polystyrene is dissolved is added to 0.05 g of Lummogen Red F305, and then 40 g of hollow silica having a refractive index of 1.21 and a particle diameter of 20 nm is added. Then, the mixture was heated and stirred to prepare a red phosphor forming coating solution.
- the prepared red phosphor forming coating solution was applied in a pattern to the region partitioned by the partition 1204 by a dispenser method. Subsequently, it was dried by heating in a vacuum oven (200 ° C., 10 mmHg) for 4 hours to form a red phosphor layer 1209R.
- the green phosphor layer 1209G In the formation process of the green phosphor layer 1209G, first, 100 g of a toluene solution in which 10 wt% polystyrene is dissolved is added to 0.05 g of Lummogen Yellow F083, and hollow silica having a refractive index of 1.21 and a particle diameter of 20 nm is further added. 40 g was added and heated and stirred to prepare a green phosphor-forming coating solution.
- the prepared green phosphor forming coating solution was applied in a pattern to the region partitioned by the partition 1204 by a dispenser method. Subsequently, it was dried by heating in a vacuum oven (200 ° C., 10 mmHg) for 4 hours to form a green phosphor layer 1209G.
- the blue light scattering layer 1209B In the formation process of the blue light scattering layer 1209B, first, 5 g of titanium oxide having an average particle diameter of 200 nm as light scattering particles is added to 30 g of a resin “LuxPrint 8155” manufactured by Teijin DuPont Co., Ltd. as a binder resin, and further a refractive index of 1 .10 g of hollow silica with a particle size of 20 nm and 21 g were added, and after thorough mixing for 30 minutes in an automatic mortar, the mixture was stirred for 15 minutes using a Primix dispersion stirrer “Filmix 40-40” to produce a blue light scattering layer A forming coating solution was obtained.
- a resin “LuxPrint 8155” manufactured by Teijin DuPont Co., Ltd. as a binder resin
- a refractive index of 1 .10 g of hollow silica with a particle size of 20 nm and 21 g were added, and after thorough mixing for 30 minutes in an automatic
- the prepared blue light scattering layer forming coating solution was applied in a pattern to a region partitioned by the partition 1204 by a dispenser method. Subsequently, it was dried by heating in a vacuum oven (200 ° C., 10 mmHg) for 4 hours, and a blue firefly scatterer layer 1209B having a refractive index of 1.60 was patterned. Thus, the phosphor substrate was completed.
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Abstract
Description
本願は、2012年7月4日に、日本に出願された特願2012-150446号に基づき優先権を主張し、その内容をここに援用する。
これらを解決するために、例えば、単色の有機EL素子を励起光源として用い、RGBの蛍光体を発光させる方法が開示されている(例えば、特許文献3参照)。この方式の場合、有機EL層は単色でよいので、低コストで高精細化、大型化を実現することが可能となる。
即ち、本発明の一態様における蛍光材料は、少なくとも蛍光体と微粒子とを含む。
前記微粒子の屈折率は、1.0よりも大きく、1.3よりも小さくてもよい。
前記蛍光体は、ペリレン系色素またはクマリン系色素であってもよい。
前記微粒子の粒径は、5nm以上、300nm以下であってもよい。
前記中空粒子は、外殻の厚さが粒径に対して5%以上、80%以下であってもよい。
前記蛍光材料全体の固形分に占める前記微粒子の体積の割合は、10%以上、80%以下であってもよい。
本発明のさらに他の態様における蛍光体基板は、蛍光の出射側を成す前記基板と、前記蛍光体との間にカラーフィルターを更に配していてもよい。
また、本発明のさらに他の態様における電子機器は、前記各項記載の蛍光体基板と、前記蛍光体を励起して蛍光を生じさせる励起光源とを備えていてもよい。
前記励起光源は、紫外光LEDまたは青色光LEDであってもよい。
本発明のさらに他の態様における電子機器は、前記励起光源と前記蛍光体基板の間に、特定波長の光のみを透過し、前記特定波長以外の光を反射させるバンドパスフィルターを更に含んでいてもよい。
蛍光材料は、少なくとも蛍光体と微粒子とから構成されており、更にバインダー樹脂を含んでいても良い。図1Aから図2Dは、本実施形態の蛍光材料を示す模式図である。蛍光材料10は、蛍光体あるいはバインダー樹脂に蛍光体が溶解または分散された蛍光体含有物11と、この蛍光体含有物11に分散された微粒子12とから構成されている。微粒子12は、その外形形状が、例えば、球形、直方体、円錐形、三角錐形、鱗片形、不定形など、各種形状であればよい。また微粒子12は、これら複数の形状の微粒子12が混在して蛍光体含有物11に分散配置されていても良い。
図1Bに示す実施形態の蛍光材料10Bは、球形で中空を成す微粒子12Aを、蛍光体含有物11に対して不規則に分散させた例である。
図1Cに示す実施形態の蛍光材料10Cは、複数の直径の球形で中空を成す微粒子12AL,12ASを、蛍光体含有物11に対して不規則に分散させた例である。
図1Dに示す実施形態の蛍光材料10Dは、多孔質の微粒子12Bを、蛍光体含有物11に対して不規則に分散させた例である。
図1Eに示す実施形態の蛍光材料10Eは、多孔質の微粒子12Bと、複数の直径の球形で中空を成す微粒子12AL,12ASとを、蛍光体含有物11に対して不規則に分散させた例である。
図1Fに示す実施形態の蛍光材料10Fは、球形で中空を成す微粒子12Aを、この蛍光材料10Fの光出射面側(蛍光出射面側)F1に向かってより多く分散するように、蛍光体含有物11に対して偏向分散させた例である。
図2Aに示す実施形態の蛍光材料10Gは、球形で中空を成す微粒子12A、三角錐形で中空を成す微粒子12C、および直方体で中空を成す微粒子12Dを、蛍光体含有物11に対して不規則に分散させた例である。
図2Bに示す実施形態の蛍光材料10Hは、球形で中空を成す微粒子12Aを、この蛍光材料10Fの光入射面側F2に向かってより多く分散するように、蛍光体含有物11に対して偏向分散させた例である。
図2Cに示す実施形態の蛍光材料10Iは、球形で中空を成す微粒子12Aを、この蛍光材料10Fの光出射面側(蛍光出射面側)F1および光入射面側F2の両側に向かってより多く分散するように、蛍光体含有物11に対して偏向分散させた例である。
図2Dに示す実施形態の蛍光材料10Jは、球形で中空を成す微粒子12Aを、この蛍光材料10Fの光出射面側(蛍光出射面側)F1と光入射面側F2との中間付近に向かってより多く分散するように、蛍光体含有物11に対して偏向分散させた例である。
本実施形態の蛍光体としては、公知の蛍光体を用いることができる。このような蛍光体は、有機系蛍光体材料と無機系蛍光体材料に分類され、これらの具体的な化合物を以下に例示するが、蛍光体はこれらの材料に限定されるものではない。
また、これら複数の蛍光材料を組み合わせて使用してもよいし、有機蛍光体と無機蛍光体のハイブリッド型蛍光体を用いても良い。
また、高効率の点から励起波長光の吸収率が高く、内部量子収率の高い材料が特に好ましい。
蛍光体層の屈折率を制御するために蛍光体に対して微粒子を分散、混合させる。外部への光取出し効率を向上させるためには、蛍光体よりも屈折率の低い微粒子を蛍光体に混合することが効果的である。図21は、蛍光体層に添加した低屈折率微粒子と、見た目明るさ評価の結果との関係を示す図である。緑色カラーフィルターを形成したガラス上に、屈折率1.5の緑色蛍光体に様々な屈折率を有する微粒子を添加した蛍光体溶液をスピン塗布をして蛍光体層を形成した。微粒子の種類、屈折率、および微粒子が蛍光体層に占める体積率を、表1に示す。蛍光体層を乾燥後、蛍光体層側から青色LEDを照射して、ガラス側から明るさを目視評価した。複数の評価者により、明るさを目視で5段階評価(微粒子を添加しなかった場合の明るさを3とし、数字が大きくなるほど明るい。)した。結果を平均化したところ、図21に示すように、添加する微粒子の屈折率が1.3以上になると、見た目評価において、明るさが急激に低下するように感じられることが分かった。従って、蛍光体層に添加する微粒子は、1.0以上、1.3以下の屈折率を有することが好ましい。また、真空の屈折率が1.0であることから、屈折率1.0未満の物質は存在しない。以上のように、蛍光体層に低屈折率微粒子を添加することは、光取出し効率向上に有効であるといえる。
なお、ここでいう多孔質微粒子とは、細孔を無数に有する微粒子のことである。
また、中空微粒子とは、内部に中空構造(バルーン構造)を持つ微粒子のことである。
多孔質または中空微粒子としては、シリカ、チタニア、硫化亜鉛、硫化カドニウムなどから成る無機粒子や、樹脂から成る有機粒子が挙げられる。
また、微粒子の分散性を高めるために、例えば中空シリカの表面のシリカに炭化水素系ポリマーが結合しているような、有機-無機ハイブリッド型の材料でも良い。
なお、ここでいう多孔質粒子、中空粒子の屈折率とは、中空粒子全体としての見かけとしての屈折率を意味する。便宜的に多孔質粒子、中空粒子の屈折率として、下記の式1で表わされる値を採用することとする。式(1)中、npは中空粒子の屈折率であり、nsは多孔質または中空粒子の空隙以外の部分の材料の屈折率であり、ncは多孔質または中空粒子の空隙部部分の屈折率であり、xは多孔質または中空粒子の空隙以外の部分の体積分率を示す。
np=x・ns+(1-x)・nc ・・・(1)
またそれら微粒子が多孔質シリカや中空シリカであった場合、内部に含有する気体は、空気や窒素の他、不活性ガスであっても良い。
上述した蛍光材料をウエットプロセスにて基板上に形成して蛍光体基板を得るような場合には、蛍光材料を塗液化した蛍光塗料とするのが好ましい。本実施形態の蛍光塗料は、上述した蛍光材料を用いて、この蛍光材料を溶解または分散するような適切な溶剤と適切なバインダー樹脂とを添加することによって得られる。また粘度等調節のためにそれ以外の組成物を添加しても良い。
本実施形態の蛍光体基板は、上述した蛍光材料を含む蛍光塗料を、例えばスピンコーティング法、ディッピング法、ドクターブレード法、吐出コート法、スプレーコート法等の塗布法、インクジェット法、凸版印刷法、凹版印刷法、スクリーン印刷法、マイクログラビアコート法等の印刷法等による公知のウエットプロセスによって基板上に塗布することで得ることができる。
図4は、第1実施形態の表示装置を示す断面模式図である。ここで、図4の断面は、表示装置100Aを基板30の上面に直交する平面で切断したときの断面である。以下、表示装置を基板30の上面に直交する平面で切断したときの断面の模式図を、表示装置の断面図ということがある。
蛍光体基板20では、光源22から射出された励起光L1を受けて、赤色サブ画素PRにおいて赤色の蛍光L2が生じる。緑色サブ画素PGにおいて緑色の蛍光L2が生じる。青色サブ画素PBにおいて青色の蛍光L2が生じるか、または励起光源からの青色光が青色サブ画素PB内に配置された散乱体によって散乱する。そして、これら赤色、緑色および青色の3つの色光によってフルカラー表示が行われる。
このように、隔壁35に蛍光体層から発生した蛍光を反射したり散乱したりするような材料を用い、更にはバンドパスフィルターを形成することによって、蛍光体層から透明基板外部への光取出し効率をよりいっそう向上させることが可能である。
また、隔壁35の形状は、基板30と離れた側の開口部が基板30と接する側の開口部よりも広くなるようなテーパー形状となっている。
このような隔壁とすることによって、励起光を画素部に効率良く入射させると共に、外光反射を抑制し、コントラストの高い表示を得ることが可能となる。
本実施形態で用いられる蛍光体基板20用の基板30は、蛍光体層31R,31G,31Bからの蛍光L2を外部に取り出す必要がある事から、蛍光体層31R,31G,31Bの発光領域で、蛍光L2を透過する必要がある。そのため、蛍光体基板20用の基板30としては、例えば、ガラス、石英等からなる無機材料基板、ポリエチレンテレフタレート、ポリカルバゾール、ポリイミド等からなるプラスチック基板等を用いることができる。ただし、蛍光体基板20用の基板30はこれらの基板に限定されるものではない。
本実施形態の蛍光体層31R,31G,31Bは、上述した蛍光材料、即ち蛍光体に微粒子を分散、混合させたものからなり、紫外発光有機EL素子、青色発光有機EL素子、紫外発光LED、青色LED等の光源2からの励起光L1を吸収し、赤色、緑色、青色に発光する赤色蛍光体層31R、緑色蛍光体層31G、青色蛍光体層31Bから構成されている。ただし、光源22として青色発光を適用する場合、青色蛍光体層31Bは設けず、青色励起光L1を青色サブ画素PBからの発光としてもよい。また、光源22として指向性を有する青色発光を適用する場合は、青色蛍光体層31Bは設けず、当該指向性を有する励起光L1を散乱し、等方発光にして外部へ取り出すことができるような光散乱層を適用してもよい。
一方、青色蛍光体層31Bの代わりとして光散乱層を適用する場合、光散乱粒子は、有機材料により構成されていてもよいし、無機材料により構成されていてもよいし、有機材料と無機材料の組み合わせによって構成されていても良いが、無機材料により構成されていることが好ましい。これにより、光源22からの指向性を有する光を、より等方的に効果的に拡散または散乱させることが可能となる。
例えば、シリカビーズ、アルミナビーズ、酸化チタンビーズ、酸化ジルコニアビーズ、酸化亜鉛ビーズ、チタン酸バリウム(BaTiO3)等が挙げられる。
隔壁35の材料としては、従来のディスプレイの隔壁として使用されているブラックマトリックスや金属を使用することができるが、出射側への光取出し効率を向上させるためには、低屈折率の樹脂中に樹脂よりも高屈折率の光散乱性粒子を分散させた光散乱性材料で形成された光散乱性の隔壁とすることが望ましい。より好ましくは、高コントラストと高光取出し効率を両立させるために、基板上に0.01μm~3μm程度の光吸収層を形成した後に、光吸収層の基板への接地面積よりも小さい接地面積で光吸収層に接地するような膜厚1μm~100μm程度の光散乱層を形成する。但し、光散乱効果による光取出し効率の向上のため、光散乱層の膜厚は光吸収層の膜厚に比べて十分に厚くする必要がある。
本実施形態の蛍光体基板20において、カラーフィルターは、光取り出し側の基板30と蛍光体層31R,31G,31Bとの間に設けられる。カラーフィルターとしては、従来のカラーフィルターを用いることが可能である。ここで、カラーフィルターを設けることによって、赤色サブ画素PR、緑色サブ画素PG、青色サブ画素PBの色純度を高める事が可能となり、表示装置100Aの色再現範囲を拡大する事ができる。
以下、本実施形態の蛍光体基板20について、図5を参照して説明する。
図5は、第1実施形態の蛍光体基板20Aを示す断面図である。
本実施形態の蛍光体基板20Aの基本構成は、表示装置の第1実施形態に示された蛍光体基板と同様であり、隔壁35に囲まれた領域に設けられた蛍光体層31RA,31GA,31BAの形状が表示装置の第1実施形態における蛍光体基板と異なっている。
図5において、図4と共通の構成要素には同一の符号を付し、詳細な説明は省略する。
以下、本発明の第2実施形態の表示装置100Bについて、図6を参照して説明する。
図6は、第2実施形態の表示装置100Bの断面図である。
本実施形態の表示装置100Bの基本構成は、第1実施形態の表示装置と同様であり、隔壁35Bの構成が第1実施形態の表示装置と異なる。したがって、本実施形態では、表示装置100Bの基本構成の説明は省略し、隔壁35Bについて説明する。
以下、本発明の第3実施形態の表示装置100Cについて、図7を参照して説明する。
図7は、第3実施形態の表示装置100Cの断面図である。
本実施形態の表示装置100Cの基本構成は第2実施形態の表示装置と同様であり、蛍光体層31R,31G,31Bの上面に平坦化層33が設けられた点、平坦化層33の上面にバンドパスフィルター32が設けられた点が第4実施形態と異なる。したがって、本実施形態では、表示装置100Cの基本構成の説明は省略する。
次に、上記実施形態に係る光源22について説明する。
蛍光体層31R,31G,31Bを励起する光源22としては、紫外光、青色光が好ましい。光源22としては、例えば、紫外LED、青色LED、紫外発光無機EL、青色発光無機EL、紫外発光有機EL、青色発光有機EL等が挙げられるが、本実施形態はこれらの光源に限定されるものではない。また、これらの光源22を直接スイッチングする事で、画像を表示する為の、発光のON/OFFをコントロールする事が可能である。また、蛍光体層31R,31G,31Bと光源22との間に、液晶の様なシャッター機能を有する層を配置し、それを、コントロールする事で発光のON/OFFをコントロールする事も可能である。
また、液晶の様なシャッター機能を有する層と光源22とを両方共ON/OFFをコントロールする事も可能である。
図8に示すように、LED(発光ダイオード)を光源22Aとして用いることができる。LEDとしては、公知のLEDを用いる事が可能で、例えば、紫外発光無機LED、青色発光無機LEDが好適である。これらのLEDは、例えば、基板39の一面に第1のバッファ層43、n型コンタクト層44、第2のn型クラッド層45、第1のn型クラッド層46、活性層47、第1のp型クラッド層48、第2のp型クラッド層49、第2のバッファ層40が順次積層され、n型コンタクト層44上に陰極42が形成され、第2のバッファ層40上に陽極41が形成された構成の光源22Aである。なお、LEDの具体的な構成は前記のものに限ることはない。
図9に示すように、有機EL素子を光源22Bとして用いることができる。本実施形態で用いられる有機EL素子は、公知の有機ELを用いる事が可能である。有機EL素子22Bは、例えば、基板39の一面に陽極51、正孔注入層53、正孔輸送層54、発光層55、正孔防止層56、電子輸送層57、電子注入層58、陰極59が順次積層された構成の光源22Bである。陽極51の端面を覆うようにエッジカバー52が形成されている。
複数の有機EL素子2Bの駆動方法は、アクティブマトリクス駆動でもよいし、パッシブマトリクス駆動でもよい。
図10に示すように、無機EL素子を光源22Cとして用いることができる。無機EL素子としては、公知の無機EL素子を用いる事が可能で、例えば、紫外発光無機EL素子、青色発光無機EL素子が好適である。これらの無機EL素子は、例えば、基板39の一面に第1電極61、第1誘電体層62、発光層63、第2誘電体層64、および第2電極65が順次積層された構成の光源22Cである。なお、無機EL素子の具体的な構成は前記のものに限定されるものではない。
図11は、第4実施形態の表示装置200の断面模式図である。表示装置200は、蛍光体基板20DとLED光源から成る光源基板21Dとの間に、光学部材である液晶素子70を装入した構成例である。図11において、図4に示す第1実施形態の表示装置100と共通する構成要素については、同じ符号を付し、詳細な説明は省略する。
消光比=(偏光板透過軸方向の偏光透過率)/(偏光板吸収軸方向の偏光透過率)
なお、偏光透過率とは、グラントムソンプリズムを用いて、理想的な偏光光を入射したときの透過率を指す。
図12は、第5実施形態の表示装置300の断面模式図である。表示装置300は、蛍光体基板20Eと有機EL素子光源から成る有機EL素子光源基板21Eとを積層した構成例である。図12において、第1実施形態の表示装置100Aと共通する構成要素については、同じ符号を付し、詳細な説明は省略する。
有機EL素子光源基板21Eは、基板39上の一方の面に設けられ、第一電極81と第二電極82の間に、有機層83が挟持されてなる有機エレクトロルミネッセンス部(以下、「有機EL部」と言う。)84と、有機EL部84を封止する封止膜85から成る。
有機層83は、第一電極82側から第二電極86側に向かって順に積層された、正孔注入層93、正孔輸送層94、有機発光層95、電子輸送層96および電子注入層97から構成されている。
前記実施形態の表示装置を備えた電子機器の例として、図13Aに示す携帯電話機、図13Bに示すテレビ受信装置などが挙げられる。
図13Aに示す携帯電話機400は、本体410、表示部420、音声入力部430、音声出力部440、アンテナ450、操作スイッチ460等を備えており、表示部420に前記実施形態の表示装置が用いられている。
図13Bに示すテレビ受信装置500は、本体キャビネット510、表示部520、スピーカー530、スタンド540等を備えており、表示部520に前記実施形態の表示装置が用いられている。
このような電子機器においては、前記実施形態の表示装置が用いられているため、表示品位に優れた電子機器を実現することができる。
そして、表示部640として本発明の一実施形態に係る表示装置が好適に適用できる。本発明の一実施形態に係る表示装置を携帯型ゲーム機600の表示部640に適用することによって、少ない消費電力で高いコントラストの映像を表示することができる。
そして、表示部1010として本発明の一実施形態に係る表示装置を好適に適用できる。本発明の一実施形態に係る表示装置をタブレット端末1000の表示部1010に適用することによって、低消費電力で視野角の広い良好な映像を表示することができる。
本発明の一実施形態に係る蛍光体基板は、例えば、図17に示すLEDパッケージに適用できる。図17に示すLEDパッケージ1100は、基板1110に電極パターン1120a、1120bがそれぞれ形成され、その上にはLEDチップ1130が実装されワイヤ1140等で上記電極パターン1120a、1120bに電気的に連結される。上記基板1110上にLEDチップ1130を内蔵するよう反射フレーム1150が装着され、上記反射フレーム1150の内側には反射層1160が形成される。
基板として、0.7mmのガラスを用いた。これを水洗後、純水超音波洗浄10分、アセトン超音波洗浄10分、イソプロピルアルコール蒸気洗浄5分を行い、100℃にて1時間乾燥させた。
基板として、0.7mmのガラスを用いた。これを水洗後、純水超音波洗浄10分、アセトン超音波洗浄10分、イソプロピルアルコール蒸気洗浄5分を行い、100℃にて1時間乾燥させた。
基板として、0.7mmのガラスを用いた。これを水洗後、純水超音波洗浄10分、アセトン超音波洗浄10分、イソプロピルアルコール蒸気洗浄5分を行い、100℃にて1時間乾燥させた。
比較例1に記載の方法と同様の方法で蛍光体基板を作成した。
蛍光体基板の上に、波長460nmの光の透過率が85%であり、波長480nm以上の可視光の透過率が5%以下であるバンドパスフィルターを、熱硬化性透明エラストマーを用いて貼り合わせた。
実施例1-1に記載の方法と同様の方法で蛍光体基板を作成した。
蛍光体基板の上に、波長460nmの光の透過率が85%であり、波長480nm以上の可視光の透過率が5%以下であるバンドパスフィルターを、熱硬化性透明エラストマーを用いて貼り合わせた。
実施例1-2に記載の方法と同様の方法で蛍光体基板を作成した。
蛍光体基板の上に、波長460nmの光の透過率が85%であり、波長480nm以上の可視光の透過率が5%以下であるバンドパスフィルターを、熱硬化性透明エラストマーを用いて貼り合わせた。
図18Aに示すように、基板1201として、0.7mmのガラスを用いた。これを水洗後、純水超音波洗浄10分、アセトン超音波洗浄10分、イソプロピルアルコール蒸気洗浄5分を行い、100℃にて1時間乾燥させた。
次に、作製した赤色蛍光体形成用塗液を、ディスペンサー手法で、隔壁1204で区画された領域にパターン塗布した。引き続き真空オーブン(200℃、10mmHgの条件)で4時間加熱乾燥し、屈折率1.50の赤色蛍光体層1221をパターン形成した(図18C)。
次に、作製した緑色蛍光体形成用塗液を、ディスペンサー手法で、隔壁1204で区画された領域にパターン塗布した。引き続き真空オーブン(200℃、10mmHgの条件)で4時間加熱乾燥し、屈折率1.50の緑色蛍光体層1222をパターン形成した(図18D)。
以上により蛍光体基板1240を完成させた。
表示装置1300は、バックライト1312と液晶基板1390と蛍光体基板1240とから成っている。
バックライト1312は光源1313と、導光板1314と、を備えている。光源1313としては半値幅10度の指向性を有する青色LED(ピーク波長450nm)を用いた。
基板101として、0.7mmのガラスを用いた。これを水洗後、純水超音波洗浄10分、アセトン超音波洗浄10分、イソプロピルアルコール蒸気洗浄5分を行い、100℃にて1時間乾燥させた。
次に、作製した赤色蛍光体形成用塗液を、ディスペンサー手法で、隔壁1204で区画された領域にパターン塗布した。引き続き真空オーブン(200℃、10mmHgの条件)で4時間加熱乾燥し、屈折率1.50の赤色蛍光体層1209Rをパターン形成した。
次に、作製した緑色蛍光体形成用塗液を、ディスペンサー手法で、隔壁1204で区画された領域にパターン塗布した。引き続き真空オーブン(200℃、10mmHgの条件)で4時間加熱乾燥し、屈折率1.50の緑色蛍光体層1209Gをパターン形成した。
以上により蛍光体基板を完成させた。
基板1201として、0.7mmのガラスを用いた。これを水洗後、純水超音波洗浄10分、アセトン超音波洗浄10分、イソプロピルアルコール蒸気洗浄5分を行い、100℃にて1時間乾燥させた。
以上により蛍光体基板を完成させた。
Claims (18)
- 蛍光体と、微粒子とを含む蛍光材料。
- 前記微粒子は前記蛍光体よりも屈折率が小さい請求項1記載の蛍光材料。
- 前記微粒子の屈折率は、1.0よりも大きく、1.3よりも小さい請求項1または2記載の蛍光材料。
- 前記蛍光体は、ペリレン系色素またはクマリン系色素である請求項1ないし3いずれか1項記載の蛍光材料。
- 前記微粒子は多孔質粒子または中空粒子である請求項1に項記載の蛍光材料。
- 請求項1に記載の蛍光材料を含む蛍光塗料。
- 請求項1に記載の蛍光材料を含む蛍光体基板。
- 光透過性の基板と、前記蛍光体と、前記基板および前記蛍光体よりも小さな屈折率を有する前記微粒子とを少なくとも備える請求項7記載の蛍光体基板。
- 蛍光の出射側を成す前記基板と、前記蛍光体との間にカラーフィルターを更に含む請求項7記載の蛍光体基板。
- 請求項7に記載の蛍光体基板を用いた電子機器。
- 請求項7に記載の蛍光体基板と、前記蛍光体を励起して蛍光を生じさせる励起光源とを備える電子機器。
- 前記励起光源は、紫外光または青色光を発する有機エレクトロルミネッセンス素子である請求項11記載の電子機器。
- 前記励起光源は、紫外光LEDまたは青色光LEDである請求項12記載の電子機器。
- 前記励起光源と前記蛍光体基板の間に、前記励起光源から前記蛍光体基板に入射する励起光を制御する液晶層を更に配した請求項11に記載の電子機器。
- 前記励起光源と前記蛍光体基板の間に、特定波長の光のみを透過し、前記特定波長以外の光を反射させるバンドパスフィルターを更に有する請求項11に記載の電子機器。
- 前記蛍光体基板は複数の画素に区画され、赤色発光する赤色画素と、緑色に発光する緑色画素とを少なくとも有する請求項11に記載の電子機器。
- 前記赤色画素、前記緑色画素の一方、または両方の側面における少なくとも一部が光散乱性の隔壁によって囲まれている請求項16に記載の電子機器。
- 請求項1に記載の蛍光材料を含むLEDパッケージ。
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