WO2016140029A1 - 蛍光体 - Google Patents
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- WO2016140029A1 WO2016140029A1 PCT/JP2016/053962 JP2016053962W WO2016140029A1 WO 2016140029 A1 WO2016140029 A1 WO 2016140029A1 JP 2016053962 W JP2016053962 W JP 2016053962W WO 2016140029 A1 WO2016140029 A1 WO 2016140029A1
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- phosphor
- mcusi
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- 239000013078 crystal Substances 0.000 claims abstract description 41
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 33
- 238000005259 measurement Methods 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- 229910052788 barium Inorganic materials 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 78
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000005284 excitation Effects 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 238000000695 excitation spectrum Methods 0.000 description 17
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- 239000002994 raw material Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
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- 238000006243 chemical reaction Methods 0.000 description 9
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- 229910016066 BaSi Inorganic materials 0.000 description 7
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- 238000005245 sintering Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 2
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- 229910017976 MgO 4 Inorganic materials 0.000 description 1
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- 239000003929 acidic solution Substances 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 229910052906 cristobalite Inorganic materials 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 150000002823 nitrates Chemical class 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
-
- 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
- C09D7/40—Additives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/0059—Measuring for diagnostic purposes; Identification of persons using light, e.g. diagnosis by transillumination, diascopy, fluorescence
- A61B5/0062—Arrangements for scanning
- A61B5/0066—Optical coherence imaging
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/0059—Measuring for diagnostic purposes; Identification of persons using light, e.g. diagnosis by transillumination, diascopy, fluorescence
- A61B5/0071—Measuring for diagnostic purposes; Identification of persons using light, e.g. diagnosis by transillumination, diascopy, fluorescence by measuring fluorescence emission
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
- C09K11/592—Chalcogenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
Definitions
- the present invention relates to a phosphor that is excited by visible light and can emit near-infrared light.
- a near infrared spectroscopic measurement device using a near infrared light emitting element is rich in moisture such as living organisms and fruits and vegetables. Particularly suitable for evaluation of inclusions.
- OCT optical coherence tomography
- silicon has the highest photoresponsiveness in the near infrared region, so if visible light can be converted into near infrared light, the power generation efficiency will be further improved. Can be increased.
- a phosphor capable of emitting near-infrared light it is possible to develop new fluorescent paints and printed fluorescent paints.
- ultraviolet fluorescent pigments have been mainly used for anti-counterfeit printing used for banknotes and the like. If this can be replaced with a near-infrared fluorescent pigment, it cannot be detected with the naked eye, but a new anti-counterfeit printing that can be detected with solid-state image sensors using photodiodes such as silicon and InGaAs, and equipment using photomultiplier tubes Is possible.
- the infrared glass phosphor used in the OCT apparatus includes Yb 2 O 3 and Nd 2 O 3 , and further includes Bi 2 O 3 and B 2 O 3.
- Patent Document 2 Japanese Patent Publication No. 2004-526330 discloses a near-infrared emitter that is excited by near-infrared light using a glass-ceramic material doped with transition metal ions, and is also proposed for use in an OCT apparatus. Has been.
- the infrared glass phosphor used in the OCT apparatus includes Yb 2 O 3 and Nd 2 O 3 , and further includes Bi 2 O 3 and B 2 O 3.
- An infrared glass phosphor containing glass was disclosed.
- the present invention is intended to provide a new phosphor that is excited by visible light in a wide band and can emit near-infrared light with high intensity.
- the present invention relates to a crystal phase represented by the formula (1): MCuSi 2 O 6 (wherein M is one or more of Ba, Sr and Ca), and the formula (2): MCuSi. 4 O 10 (wherein M is a crystal phase represented by one or more of Ba, Sr and Ca), and powder X-ray diffraction measurement (XRD) using CuK ⁇ rays
- a phosphor is characterized in that the ratio ⁇ of the diffraction peak intensity of MCuSi 4 O 10 to the diffraction peak intensity of MCuSi 2 O 6 is 0 ⁇ ⁇ 0.50.
- the phosphor proposed by the present invention is excited by visible light in a wide band and can emit near-infrared light with high intensity. Therefore, as described above, as a phosphor constituting a light-emitting element mounted on a near-infrared spectroscopic measurement apparatus or an optical coherence tomographic image apparatus (OCT), light reception mounted on a solar cell, a solar power generation apparatus, or the like. It can also be suitably used as a wavelength conversion material constituting the element. Moreover, the phosphor proposed by the present invention can be suitably used as a phosphor to be included in a fluorescent paint printed material or a printed material having a near infrared light emitting image recognition unit.
- OCT optical coherence tomographic image apparatus
- FIG. 2 is a diagram showing an XRD pattern of a phosphor (sample) obtained in Example 1.
- FIG. 6 is a diagram showing an XRD pattern of a phosphor (sample) obtained in Example 2.
- FIG. It is the figure which showed the XRD pattern of the fluorescent substance (sample) obtained by the comparative example 1. It is the figure which showed the XRD pattern of the fluorescent substance (sample) obtained by the comparative example 2. It is the figure which showed the XRD pattern of the fluorescent substance (sample) obtained by the comparative example 3. It is the figure which showed the XRD pattern of the fluorescent substance (sample) obtained in the comparative example 4.
- Example 1 and the comparative example 1 show the excitation spectrum and fluorescence spectrum of Example 1 and the comparative example 1 as a relative value when the maximum value of the excitation intensity and fluorescence intensity of a vertical axis
- FIG. It is the figure which showed the excitation spectrum and fluorescence spectrum of Example 1, Example 2, and the comparative example 4 as a relative value when the maximum value of the excitation intensity of a vertical axis
- the phosphor according to an example of the present embodiment has the formula (1): MCuSi 2 O 6 (wherein M is one or more of Ba, Sr and Ca). And a crystal phase (referred to as “MCuSi 2 O 6 crystal phase”) and a formula (2): MCuSi 4 O 10 (wherein M is one or two of Ba, Sr and Ca) And a phosphor containing at least a crystal phase (referred to as “MCuSi 4 O 10 crystal phase”).
- MCuSi 2 O 6 crystal phase a crystal phase
- MCuSi 4 O 10 crystal phase a phosphor containing at least a crystal phase
- the present phosphor may be a polycrystal composed of a plurality of crystal phases or a mixture containing a plurality of crystal phases.
- crystal phase when expressed as an MCuSi 2 O 6 crystal phase, if the “crystal phase” contains MCuSi 2 O 6 as a main component, it cannot be detected that other components such as XRD exist in the crystal phase. It may contain components. The same applies to other crystal phases.
- the MCuSi 2 O 6 crystal phase is preferably the main crystal phase.
- the diffraction peak intensity derived from the crystal phase of MCuSi 2 O 6 is the diffraction peak intensity derived from any other crystal phase. Is preferably larger.
- the ratio ⁇ of peak intensity is 0 ⁇ ⁇ 0.50. If MCuSi 2 O 6 and MCuSi 4 O 10 are included in such a range, the excitation spectrum band can be expanded while maintaining the fluorescence spectrum intensity.
- the ratio ⁇ of the diffraction peak intensity of MCuSi 4 O 10 to the diffraction peak intensity of MCuSi 2 O 6 is preferably 0 ⁇ ⁇ 0.50, and more preferably 0 ⁇ ⁇ 0.31. Particularly preferred, and more preferably 0 ⁇ ⁇ 0.10.
- the content of each crystal phase is expressed not by chemical analysis but by the diffraction peak intensity of each crystal phase in the XRD pattern.
- the content of each crystal phase is indicated by chemical analysis, for example, flux While it is difficult to accurately express the characteristics of this phosphor because it is greatly affected by the amount of additive added, the effect of the amount of additive added can be expressed by the diffraction peak intensity of each crystal phase in the XRD pattern. This is because the characteristics of the phosphor can be expressed more accurately.
- the phosphor preferably further contains a SiO 2 crystal phase. However, the phosphor does not have to contain a SiO 2 crystal phase.
- the present phosphor contains a SiO 2 crystal phase, SiO 2 with respect to the diffraction peak intensity of MCuSi 2 O 6 in the XRD pattern obtained by measuring the present phosphor by powder X-ray diffraction measurement (XRD) using CuK ⁇ rays.
- the ratio ⁇ of the diffraction peak intensity is preferably 0 ⁇ ⁇ 0.45. If the SiO 2 crystal phase is included in such a range, scattering of excitation light can be prevented and higher fluorescence spectrum intensity can be obtained.
- the ratio ⁇ of the diffraction peak intensity of SiO 2 is preferably 0 ⁇ ⁇ 0.45, particularly preferably 0.16 ⁇ , more preferably ⁇ ⁇ 0.35, and more preferably ⁇ ⁇ 0.3. It is particularly preferable that 0.20 ⁇ or ⁇ ⁇ 0.25 is more preferable.
- the phosphor may or may not contain a BaSi 2 O 5 phase. This is because at present, neither the advantage nor the defect due to the inclusion of the BaSi 2 O 5 phase has been confirmed.
- a part of Cu in the formula (1): MCuSi 2 O 6 or the formula (2): MCuSi 4 O 10 or both is substituted with Mg or Zn or both.
- MgO 4 and ZnO 4 are formed in the crystal structure, self-absorption of light emission by adjacent CuO 4 is prevented, and improvement in quantum efficiency can be expected.
- the phosphor preferably further contains one or more elements selected from the group consisting of Li, Na, K, B, P, F, Cl, Br and I. At this time, the content of these elements is preferably 0.005 to 3% by mass, more preferably 0.008% by mass or more and 2% by mass or less, and particularly preferably 0.01% by mass or more or 1% by mass or less. It is particularly preferred. When this phosphor contains these elements, the emission peak intensity can be increased as a result. These elements can be added as part of the sintering aid.
- the present phosphor may contain an element component other than the above as long as it is less than 20% by mass. This is because it is considered that the content of this level does not affect the characteristics of the present phosphor.
- the present phosphor is not limited to its form such as a thin film, plate or particle. However, it is preferably in the form of particles from the viewpoint of processability to a light emitting element mounting apparatus or a printed material to be used.
- This phosphor can be manufactured by the following manufacturing method.
- the manufacturing method of this fluorescent substance is not limited to the manufacturing method demonstrated below.
- This phosphor mixes M element raw material in Formula (1): MCuSi 2 O 6 , Cu raw material, and silicon raw material, adds a flux (sintering aid) as necessary, and fires the mixture. You can get it.
- examples of the M element raw material include oxides, carbonates, nitrates, acetates, and the like of the M element (one or more elements selected from Ba, Sr, and Ca).
- examples of the Cu raw material include Cu oxides, carbonates, sulfates and metals.
- examples of the silicon raw material include silicon oxide, carbide, nitride, and silicon. In addition, it is preferable not to add a reducing agent from a viewpoint of keeping the oxidation number of Cu bivalent.
- the mixing ratio (molar ratio) of the M element raw material and the Cu raw material is preferably 1.5: 1.0 to 0.8: 1.0, and more preferably 1.3: 1.0 to 0.9: 1.0, particularly 1.2: 1.0 to 1.0: 1.0 is particularly preferable.
- the mixing ratio (mass ratio) of the Cu raw material and the silicon raw material is preferably 1.0: 2.0 to 1.0: 5.0, and more preferably 1.0: 3.0 to 1.0. : 4.5, and particularly preferably 1.0: 3.5 to 1.0: 4.2.
- the chemical reaction can be promoted and the amount of unreacted material can be reduced.
- a flux (sintering aid) containing one or more elements selected from the group consisting of Li, Na, K, B, P, F, Cl, Br and I can be mentioned. Of these, Li, Na, K, B, F, Cl and the like are particularly preferable.
- the blending amount (mass ratio) of the flux (sintering aid) is preferably 0.1 to 15% with respect to the total weight of the mixed M element raw material, Cu raw material and silicon raw material, in particular 1% or more or It is even more preferable that it is 10% or less, particularly 2% or more or 7% or less.
- the firing atmosphere is not a reducing atmosphere
- an appropriate atmosphere can be adopted.
- an inert gas atmosphere, an air atmosphere, an oxidizing atmosphere, or the like can be employed.
- the firing temperature may be 700 to 1100 ° C. This is because the reaction is difficult to proceed at a temperature lower than 700 ° C., but may melt at a temperature higher than 1100 ° C.
- the first baking can be performed in a temperature range of 700 to 900 ° C.
- the second baking can be performed in a temperature range of 800 to 1100 ° C. after pulverizing the obtained baking powder.
- the baking powder can be washed with an acidic solution such as water or hydrochloric acid, and then the second baking can be performed.
- an acidic solution such as water or hydrochloric acid
- This phosphor is excited by visible light and can emit near infrared light. That is, this phosphor has a feature that it has an excitation spectrum in the visible light region (380 nm to 750 nm) and an emission peak in the near infrared region (750 nm to 2500 nm).
- the excitation band width of 80% or more of the maximum excitation intensity can be 90 nm or more, more preferably 100 nm or more, and still more preferably 150 nm or more.
- the phosphor can further increase the emission intensity in the near infrared region by containing a crystal phase represented by MCuSi 4 O 10 or a crystal phase such as cristobalite, tridymite, or quartz represented by SiO 2. It has the characteristics.
- the phosphor is mixed with, for example, an organic resin or an inorganic filler, such as glass particles or a metal oxide, if necessary, together with a solvent or a dispersant, applied as a liquid composition, and then dried or / And it solidifies through hardening etc. and can be used as forms, such as a fluorescent substance composition layer or a fluorescent substance composition filling.
- an organic resin or an inorganic filler such as glass particles or a metal oxide
- this phosphor Since this phosphor is excited by visible light and can emit near-infrared light, it can be used for a near-infrared light-emitting element, using the near-infrared light-emitting element, As a phosphor constituting a light emitting element mounted on a light emitting element mounting device such as an optical coherence tomography apparatus (OCT), as a wavelength conversion material constituting a light receiving element mounted on a light receiving element mounting device such as a solar power generation device Moreover, it can use suitably as a fluorescent substance included in the fluorescent paint used for the fluorescent paint printed matter or the printed matter provided with the image recognition part of near infrared light emission.
- OCT optical coherence tomography apparatus
- this near-infrared light emitting element a near-infrared light emitting element including this phosphor
- the phosphor is mounted as a wavelength conversion material for a near infrared light source.
- the light receiving element containing this fluorescent substance is used for a solar power generation device, since the visible light component of sunlight can be converted into near-infrared light, power generation efficiency can be further improved.
- the phosphor can be mounted as a wavelength conversion material on the light receiving side.
- light-receiving elements using silicon photodiodes are known to have high spectral sensitivity in the near-infrared light wavelength band of 800 to 1000 nm, and in the peak wavelength band of near-infrared light emission of this phosphor. It is excellent in matching with certain 900 to 950 nm and is suitable as a wavelength conversion material.
- this phosphor emits near-infrared light even when an electron beam or X-ray is used as an excitation source, for example, if X-rays are used as an excitation source, an X-ray diagnostic apparatus for medical or security use as a scintillation material Application to is also possible.
- a fluorescent paint printed material used for anti-counterfeit printing used for banknotes can be produced and cannot be detected with the naked eye, but made of silicon or InGaAs.
- New anti-counterfeit printing that can be sensed by a solid-state imaging device using a photodiode such as a photo diode or a device using a photomultiplier tube can be performed.
- these fluorescent paints are blended with a transparent resin component as a matrix and mixed with an inorganic component or organic component flow regulator, an organic solvent, or the like, and are prepared as an ink or a paste.
- the resin component include an epoxy resin, a phenol resin, a silicone resin, an acrylic resin, and polymethyl methacrylate.
- glass particles that are light scattering components may be mixed as necessary.
- XRD measurement> The phosphors (samples) obtained in the examples and comparative examples were used as samples for powder X-ray diffraction measurement (XRD), this sample was mounted on a holder, and MXP18 (Bruker AXS Co., Ltd.) was used.
- the XRD pattern was obtained by measuring the angle and intensity of the diffraction line under the following conditions.
- Excitation band width of 80% or more of maximum excitation intensity is 120 nm or more
- B Excitation band width of 80% or more of maximum excitation intensity is 90 nm or more
- C Excitation band width of 80% or more of maximum excitation intensity is less than 90 nm
- the fluorescence spectrum at the excitation wavelength (620 nm, 570 nm, 520 nm) was evaluated according to the following criteria.
- Example 1 BaCO 3 , CuO, and SiO 2 were mixed at a molar ratio of 1: 1: 3.5, and BaCl 2 was added as a flux in an amount of 3% by mass with respect to the mixture and mixed. This mixture was put in an alumina crucible and baked in the air at 1000 ° C. for 24 hours to obtain a phosphor (sample).
- the XRD pattern of the obtained phosphor (sample) is shown in FIG.
- the obtained phosphor (sample) was a compound containing a BaCuSi 2 O 6 phase as a main crystal phase and containing a SiO 2 phase, a small amount of BaCuSi 4 O 10 phase and a BaSi 2 O 5 phase.
- the amount of Cl contained in this compound was 0.02% by mass with fluorescent X-rays.
- Example 2 BaCO 3 , CuO and SiO 2 were mixed at a molar ratio of 1: 1: 4, and BaCl 2 was added as a flux in an amount of 3% by mass with respect to the mixture and mixed. This mixture was put in an alumina crucible and baked in the air at 1000 ° C. for 24 hours to obtain a phosphor (sample).
- the XRD pattern of the obtained phosphor (sample) is shown in FIG.
- the obtained phosphor (sample) was a compound having a BaCuSi 2 O 6 phase as a main crystal phase and containing a SiO 2 phase, a BaCuSi 4 O 10 phase, and a BaSi 2 O 5 phase.
- the amount of Cl contained in this compound was 0.01% by mass with fluorescent X-rays.
- the XRD pattern of the obtained phosphor (sample) is shown in FIG.
- the obtained phosphor (sample) was a single phase of BaCuSi 4 O 10 .
- the content of halogen elements such as Cl, alkali metals such as Na, and P in this phosphor (sample) was all less than 0.005% by mass with fluorescent X-rays.
- the XRD pattern of the obtained phosphor (sample) is shown in FIG.
- the obtained phosphor (sample) was a compound having a BaCuSi 2 O 6 phase as a main crystal phase and a trace amount of BaSi 2 O 5 phase.
- the contents of halogen elements such as Cl, alkali metals such as Na, and P contained in this compound were all less than 0.005% by mass with fluorescent X-rays.
- the XRD pattern of the obtained phosphor (sample) is shown in FIG.
- the obtained phosphor (sample) was a compound having a SiO 2 phase as a main crystal phase and containing a BaCuSi 2 O 6 phase and a small amount of BaSi 2 O 5 phase.
- the contents of halogen elements such as Cl, alkali metals such as Na, and P contained in this compound were all less than 0.005% by mass with fluorescent X-rays.
- the XRD pattern of the obtained phosphor (sample) is shown in FIG.
- the obtained phosphor (sample) was a compound containing a BaCuSi 4 O 10 phase and a BaCuSi 2 O 6 phase as main crystal phases and containing a SiO 2 phase and a BaSi 2 O 5 phase.
- the contents of halogen elements such as Cl, alkali metals such as Na, and P contained in this compound were all less than 0.005% by mass with fluorescent X-rays.
- FIG. 7 is a diagram showing the excitation spectrum and the fluorescence spectrum of Example 1 and Comparative Example 1 as relative values when the maximum value of the excitation intensity and the fluorescence intensity on the vertical axis is normalized as 1.
- FIG. Focusing on the excitation spectrum, Example 1 has small wavelength dependence, and the intensity difference is within 20% in the range of 500 nm to 650 nm. That is, it can be seen that if excitation is performed at a wavelength in this range, the difference in fluorescence intensity can be suppressed to within 20%, and the wavelength dependency is small. This indicates that the conversion efficiency to near infrared light can be further enhanced by using a white light source or a plurality of monochromatic light sources.
- the excitation wavelength is highly dependent, and the excitation wavelength band in which the difference in fluorescence intensity can be suppressed within 20% is limited to a narrow range of 615 to 680 nm. That is, the excitation light source that can be used is limited to the red light source, and the conversion efficiency to near-infrared light is kept low.
- FIG. 8 is a diagram showing the excitation spectrum and the fluorescence spectrum of Example 1, Example 2, and Comparative Example 4 when the maximum values of the excitation intensity and the fluorescence intensity on the vertical axis are normalized as 1.
- FIG. 8 When matching the XRD patterns of the respective embodiments, with an increase in BaCuSi 4 O 10 phase was found that the wavelength dependency of the excitation spectrum is increased. This is consistent even when the results of the BaCuSi 4 O 10 single phase of Comparative Example 1 are taken into account.
- FIG. 9 is a diagram comparing excitation spectrum intensity and fluorescence spectrum intensity of Example 1, Example 2, and Comparative Example 4. It can be seen that the spectrum intensity is higher in the order of Example 2> Example 1> Comparative Example 4. As in Example 2, the excitation efficiency in the range of 580 to 700 nm is increased by intentionally including the BaCuSi 4 O 10 phase while the BaCuSi 2 O 6 phase is the main crystal phase, and the fluorescence intensity is improved accordingly. I found out that However, it has also been confirmed that if there are too many BaCuSi 4 O 10 phases, the wavelength dependence of the excitation band tends to increase.
- Example 1 The excitation spectrum intensity and fluorescence spectrum intensity of Example 1 and Comparative Examples 2 and 3 were compared (see Table 1). The spectrum intensity was higher in the order of Example 1> Comparative Example 2 ⁇ Comparative Example 3. On the other hand, the content of the SiO 2 phase was large in the order of Comparative Example 3> Example 1> Comparative Example 2.
- alkaline earth metals such as Ba, Sr and Ca have similar properties, it is considered that the same effect as in the above embodiment can be obtained even if Sr or Ca is used instead of Ba or together with Ba. Can do.
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Abstract
Description
また、光干渉断層画像装置(OCT)は、近赤外光を用いるために、一般的なX線断層撮影よりも生体損傷性が低いばかりか、断層撮影画像の空間分解能に優れているという特徴を有している。
また、シリコンを用いた太陽電池や太陽光発電装置において、シリコンは近赤外領域の光応答性が最も高いため、仮に可視光を近赤外光に変換することができれば、発電効率をより一層高めることができる。
例えば特許文献1(特開2008-185378号公報)において、OCT装置に用いる赤外ガラス蛍光体として、Yb2O3及びNd2O3を含み、さらにBi2O3及びB2O3からなるガラスを含有し、青色光で励起する近赤外発光蛍光体が開示されている。 また、特許文献2(特表2004-526330号公報)には、遷移金属イオンをドープしたガラス-セラミック材料で近赤外光励起される近赤外発光体が開示され、OCT装置への展開も提案されている。
しかしながら、従来から知られている近赤外発光蛍光体は僅かであった。例えば特許文献1(特開2008-185378号公報)において、OCT装置に用いる赤外ガラス蛍光体として、Yb2O3及びNd2O3を含み、さらにBi2O3及びB2O3からなるガラスを含有する赤外ガラス蛍光体が開示されている程度であった。
MCuSi2O6結晶相とMCuSi4O10結晶相とを含むことにより、蛍光スペクトル強度を維持しつつ励起スペクトルの帯域を広げることができる。
かかる範囲でMCuSi2O6及びMCuSi4O10を含んでいれば、蛍光スペクトル強度を維持しつつ励起スペクトルの帯域を広げることができる。
かかる観点から、MCuSi2O6の回折ピーク強度に対するMCuSi4O10の回折ピーク強度の比率βは0<β≦0.50であるのが好ましく、中でも0<β≦0.31であるのが特に好ましく、その中でも0<β≦0.10であるのがさらに好ましい。
本蛍光体がSiO2結晶相を含む場合、CuKα線を用いた粉末X線回折測定(XRD)で本蛍光体を測定して得られるXRDパターンにおいて、MCuSi2O6の回折ピーク強度に対するSiO2の回折ピーク強度の比率αが0<α<0.45であるのが好ましい。かかる範囲でSiO2結晶相を含めば、励起光の散乱を防ぎ、より高い蛍光スペクトル強度を得ることができる。
かかる観点から、SiO2の回折ピーク強度の比率αは、0<α<0.45、中でも0.16<αであるのが好ましく、その中でもα<0.35、中でもさらにα<0.3であるのが特に好ましく、その中でも0.20<α或いはα<0.25であるのがさらに好ましい。
なお、本蛍光体は、BaSi2O5相を含んでいても、含んでいなくてもよい。現時点では、BaSi2O5相を含有することによる利点も欠点も確認できていないからである。
本蛍光体がこれらの元素を含むと、結果的に発光ピーク強度を高めることができる。これらの元素は、焼結助剤の一部として添加することができる。
本蛍光体は、次の製造方法によって製造することができる。但し、本蛍光体の製造方法が、次に説明する製造方法に限定されるものではない。
Cu原料としては、Cuの酸化物、炭酸塩、硫酸塩、金属などを挙げることができる。
ケイ素原料としては、ケイ素の酸化物、炭化物、窒化物、ケイ素などを挙げることができる。
なお、還元剤は、Cuの酸化数を2価に保つ観点から添加しない方が好ましい。
フラックス(焼結助剤)としては、例えばLi、Na、K、B、P、F、Cl、Br及びIからなる群から選ばれる一種又は二種以上の元素を含むフラックス(焼結助剤)を挙げることができる。中でも、Li、Na、K、B、F、Clなどは特に好ましい。
フラックス(焼結助剤)の配合量(質量割合)は、M元素原料とCu原料とケイ素原料を混合した総重量に対して0.1~15%であるのが好ましく、特に1%以上或いは10%以下、その中でも特に2%以上或いは7%以下であるのがより一層好ましい。
焼成温度は700~1100℃であればよい。700℃未満では、反応が進みにくい一方、1100℃以上では融けてしまう可能性があるからである。
さらに、1回目の焼成後に水や塩酸などの酸性溶液で焼成粉を洗浄した後に、2回目の焼成を行うこともできる。こうすることで、各焼成段階により適した焼結助剤の配合量に調整することができ、最終製品である本蛍光体中に含まれるLi、Na、K、B、P、F、Cl、Br及びIの元素量もより最適な範囲に制御しやすくなる。
本蛍光体は、可視光によって励起され、近赤外光を発光することができる。すなわち、本蛍光体は、可視光領域(380nm~750nm)に励起スペクトルを有し、且つ、近赤外領域(750nm~2500nm)に発光ピークを有するという特徴を有している。
本蛍光体は、例えば、有機系樹脂や無機フィラー、例えばガラス粒子や金属酸化物等と、必要に応じてさらに溶媒や分散剤などと共に混合し、液状組成物として塗布成形した後、乾燥又は/及び硬化などを経て固形化し、蛍光体組成物層又は蛍光体組成物充填物等の形態として用いることが可能である。
分光測定装置においては、本蛍光体は近赤外光源の波長変換材料として搭載される。
太陽光分光測定装置においては、本蛍光体を受光側の波長変換材料として搭載することができる。特に、シリコン製フォトダイオードを用いた受光素子は、近赤外光の800~1000nmの波長帯域で高い分光感度を持つことが知られており、本蛍光体の近赤外発光のピーク波長帯域である900~950nmとのマッチング性に優れ波長変換材料として好適である。
これらの蛍光塗料は、本蛍光体に加え、透明な樹脂成分をマトリックスとして、無機成分や有機成分の流動調整材、有機溶剤などと混合し、インクやペーストとして調合される。樹脂成分としては、エポキシ樹脂、フェノール樹脂、シリコーン樹脂、アクリル樹脂、ポリメタクリル酸メチルなどを挙げることができる。この他、必要に応じて光散乱成分であるガラス粒子などを混合してもよい。
本明細書において「X~Y」(X,Yは任意の数字)と表現する場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」或いは「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)或いは「Y以下」(Yは任意の数字)と表現した場合、「Xより大きいことが好ましい」或いは「Y未満であることが好ましい」旨の意図も包含する。
実施例及び比較例で得られた蛍光体(サンプル)を粉末X線回折測定(XRD)用のサンプルとし、このサンプルをホルダーに装着し、MXP18(ブルカー・エイエックスエス(株)社製)を使用し、下記条件で回折線の角度と強度を測定し、XRDパターンを得た。
(管電圧)40kV
(管電流)150mA
(サンプリング間隔)0.02°
(スキャンスピード)4.0°/min
(開始角度)5.02°
(終了角度)80°
実施例及び比較例で得られた蛍光体(サンプル)を発光特性測定用のサンプルとし、分光蛍光光度計(日本分光(株)社製 FP-8600)を用いて、励起側と蛍光側のバンド幅はともに10nm、走査速度1000nm/minの条件で、励起スペクトル及び蛍光スペクトルを測定した。
A:最大励起強度の80%以上の励起帯幅が120nm以上
B:最大励起強度の80%以上の励起帯幅が90nm以上
C:最大励起強度の80%以上の励起帯幅が90nm未満
A:ピーク強度が4000カウント以上
B:ピーク強度が3000カウント以上4000カウント未満
C:ピーク強度が3000カウント未満
前記した4つの評価項目、つまり評価励起スペクトルの励起帯幅および各励起波長(620nm、570nm、520nm)における蛍光スペクトルのピーク強度、について次の基準で評価した。
AA:4つの評価項目が全てA
A:4つの評価項目がAまたはBで、且つAが2個以上
B:4つの評価項目がAまたはBで、且つAが1個以下
C:4つの評価項目でCが1個以上
BaCO3、CuO及びSiO2を、モル比で1:1:3.5となるように混合し、更にフラックスとしてBaCl2を前記混合物に対し3質量%となる量を加えて混合した。この混合物をアルミナ坩堝に入れて大気中で、1000℃×24時間焼成して蛍光体(サンプル)を得た。
得られた蛍光体(サンプル)は、BaCuSi2O6 相を主結晶相とし、SiO2相、微量のBaCuSi4O10相とBaSi2O5相を含有する化合物であった。
この化合物中に含まれるCl量は、蛍光X線で0.02質量%であった。
BaCO3、CuO及びSiO2を、モル比で1:1:4となるように混合し、更にフラックスとしてBaCl2を前記混合物に対し3質量%となる量を加えて混合した。この混合物をアルミナ坩堝に入れて大気中で、1000℃×24時間焼成して蛍光体(サンプル)を得た。
得られた蛍光体(サンプル)は、BaCuSi2O6 相を主結晶相とし、SiO2相、BaCuSi4O10相、BaSi2O5相を含有する化合物であった。
この化合物中に含まれるCl量は、蛍光X線で0.01質量%であった。
BaCO3、CuO及びSiO2を、モル比で1:1:4となるように秤量し、アセトン中で湿式混合した。
この混合物をアルミナ坩堝に入れて大気中で、960℃×16時間焼成して、蛍光体(サンプル)を得た。
得られた蛍光体(サンプル)は、BaCuSi4O10 の単相であった。
この蛍光体(サンプル)中のCl等のハロゲン元素、Na等のアルカリ金属、Pの含有量は、蛍光X線で何れも0.005質量%未満であった。
BaCO3、CuO及びSiO2を、モル比で1:1:2となるように混合し、この混合物をアルミナ坩堝に入れて大気中で、1000℃×24時間焼成して蛍光体(サンプル)を得た。
得られた蛍光体(サンプル)は、BaCuSi2O6相を主結晶相とし、微量のBaSi2O5相を含有する化合物であった。
この化合物中に含まれるCl等のハロゲン元素、Na等のアルカリ金属、Pの含有量は、蛍光X線で何れも0.005質量%未満であった。
BaCO3、CuO及びSiO2を、モル比で1:1:3となるように混合し、この混合物をアルミナ坩堝に入れて大気中で、1000℃×24時間焼成して蛍光体(サンプル)を得た。
得られた蛍光体(サンプル)は、SiO2相を主結晶相とし、BaCuSi2O6相、微量のBaSi2O5相を含有する化合物であった。
この化合物中に含まれるCl等のハロゲン元素、Na等のアルカリ金属、Pの含有量は、蛍光X線で何れも0.005質量%未満であった。
BaCO3、Cu2CO3・(OH)2・H2O及びSiO2を、モル比で1:0.5:4となるように混合し、エタノール中で湿式混合した。この混合物をアルミナ坩堝に入れて大気中で、1100℃×24時間焼成して蛍光体(サンプル)を得た。
得られた蛍光体(サンプル)は、BaCuSi4O10相とBaCuSi2O6相が主な結晶相であり、SiO2相、BaSi2O5相を含有する化合物であった。
この化合物中に含まれるCl等のハロゲン元素、Na等のアルカリ金属、Pの含有量は、蛍光X線で何れも0.005質量%未満であった。
図7は、縦軸の励起強度と蛍光強度の最大値を1として規格化した時の相対値として、実施例1、比較例1の励起スペクトルと蛍光スペクトルを示した図である。
励起スペクトルに着目すると、実施例1は波長依存性が小さく、500nm~650nmの範囲で強度差が20%以内に収まっている。すなわち、この範囲の波長で励起すれば、蛍光強度差を20%以内に抑えることができ、波長依存性が小さいことが分かる。このことは、白色光源や複数の単色光源を用いれば、近赤外光への変換効率をより一層高められることを示すものである。
図8は、縦軸の励起強度と蛍光強度の最大値を1として規格化した時の実施例1、実施例2、比較例4の励起スペクトルと蛍光スペクトルを示した図である。
各実施例のXRDパターンと照合すると、BaCuSi4O10相の増加に伴い、励起スペクトルの波長依存性が大きくなることが分かった。これは、比較例1のBaCuSi4O10単相の結果を加味しても矛盾しない。
スペクトル強度は、実施例2>実施例1>比較例4 の順に高いことが分かる。実施例2のように、BaCuSi2O6相を主結晶相としつつ、意図的にBaCuSi4O10相を含有させることで、580~700nmの範囲の励起効率が上がり、それに伴い蛍光強度を向上させることができることが分かった。但し、BaCuSi4O10相が多すぎると、励起帯の波長依存性が強くなる傾向があることも確認されている。
実施例1、比較例2及び3の励起スペクトル強度と蛍光スペクトル強度を比較した(表1参照)。
スペクトル強度は、実施例1>比較例2≒比較例3の順に高かった。これに対し、SiO2相の含有量は、比較例3>実施例1>比較例2の順に多かった。
なお、SiO2主ピーク(2θ26.6°付近)は、BaCuSi2O6のピーク(2θ27.1°付近)と重なるため、強度比の算出には不適当と判断した。
Claims (8)
- 式(1):MCuSi2O6(式中のMは、Ba、Sr及びCaのうちの1種又は2種以上からなる)で示される結晶相と、式(2):MCuSi4O10(式中のMは、Ba、Sr及びCaのうちの1種又は2種以上からなる)で示される結晶相とを含み、且つ、
CuKα線を用いた粉末X線回折測定(XRD)で得られるXRDパターンにおいて、MCuSi2O6の回折ピーク強度に対するMCuSi4O10の回折ピーク強度の比率βが0<β≦0.50であることを特徴とする蛍光体。 - さらにSiO2結晶相を含み、且つ、CuKα線を用いた粉末X線回折測定(XRD)で得られるXRDパターンにおいて、MCuSi2O6の回折ピーク強度に対するSiO2の回折ピーク強度の比率αが0<α<0.45であることを特徴とする請求項1記載の蛍光体。
- 式(1):MCuSi2O6又は式(2):MCuSi4O10又はこれら両方の式おけるCuの一部がMg又はZn又は両方で置換された化合物を含むことを特徴とする請求項1又は2に記載の蛍光体。
- さらにLi、Na、K、B、P、F、Cl、Br及びIからなる群から選ばれる一種又は二種以上の元素を0.005~3質量%含むことを特徴とする請求項1~3の何れかに記載の蛍光体。
- 請求項1~4の何れかに記載の蛍光体を備えた近赤外発光素子。
- 請求項5に記載の近赤外発光素子を備えた装置。
- 請求項1~4の何れかに記載の蛍光体を含有する蛍光塗料。
- 請求項7記載の蛍光塗料を用いた蛍光体印刷物。
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