WO2011077637A1 - 蛍光体および発光装置 - Google Patents
蛍光体および発光装置 Download PDFInfo
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- WO2011077637A1 WO2011077637A1 PCT/JP2010/006793 JP2010006793W WO2011077637A1 WO 2011077637 A1 WO2011077637 A1 WO 2011077637A1 JP 2010006793 W JP2010006793 W JP 2010006793W WO 2011077637 A1 WO2011077637 A1 WO 2011077637A1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 8
- 229910052745 lead Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000004065 semiconductor Substances 0.000 claims description 22
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
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- 239000004332 silver Substances 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
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- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
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- 239000002241 glass-ceramic Substances 0.000 description 1
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
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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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- C09K11/77342—Silicates
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C09K11/7737—Phosphates
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- C09K11/7739—Phosphates with alkaline earth metals with halogens
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- H01L33/50—Wavelength conversion elements
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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- 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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Definitions
- the present invention relates to a phosphor that is efficiently excited and emits light by ultraviolet rays or short-wavelength visible light, and a light-emitting device using the same.
- Various light-emitting elements configured to obtain light of a desired color by combining a light-emitting element and a phosphor that is excited by light generated by the light-emitting element and generates light having a wavelength region different from that of the light-emitting element.
- the device is known.
- LED light emitting diodes
- LD laser diodes
- a white light emitting device As a specific example of such a white light emitting device, a method of combining a plurality of LEDs that emit ultraviolet light or short wavelength visible light and phosphors that emit light of colors such as blue and yellow when excited by ultraviolet light or short wavelength visible light. Etc. are known (see Patent Document 1).
- the above-described light emitting device tends to be higher than the color temperature realized by the conventional light bulb and fluorescent lamp. Therefore, when trying to use the above-mentioned white light emitting device as an indoor lighting device such as a residence or a store, further improvement is required.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a phosphor that can be applied to a light emitting device that emits warm light.
- a white LED that emits light with a light bulb color of 3200K or less can be configured by a combination with a blue phosphor or a blue light emitting element.
- the light emitting device includes a light emitting element that emits ultraviolet light or short wavelength visible light, a first phosphor that emits visible light by being excited by ultraviolet light or short wavelength visible light, and is excited by ultraviolet light or short wavelength visible light.
- a second phosphor that emits visible light of a color different from that of the visible light emitted by the phosphor, and a light emitting device configured to obtain a mixed color by mixing light from each phosphor is there.
- the first phosphor has a general formula (M 2 x , M 3 y , M 4 z ) m M 1 O 3 X (2 / n) (where M 1 is Si, Ge, Ti, Zr and Sn)
- M 1 is Si, Ge, Ti, Zr and Sn
- M 2 is one or more elements including at least Ca selected from the group consisting of Ca, Mg, Cd, Co and Zn
- M 3 is Sr, Ra.
- m is in the range of 1 ⁇ m ⁇ 4/3
- n is in the range of 5 ⁇ n ⁇ 7
- a light emitting device that emits light with a light bulb color of 3200K or less can be realized relatively easily.
- the light emitting device includes a semiconductor light emitting element that emits ultraviolet light or short wavelength visible light, a first phosphor that emits visible light by being excited by ultraviolet light or short wavelength visible light, and is excited by ultraviolet light or short wavelength visible light.
- a second phosphor that emits visible light of a color different from the visible light emitted by the first phosphor, and emits light having a color temperature of 2800K to 3200K using the light from each phosphor. It is configured.
- the light-emitting device described above may be configured to emit light having an illuminance of 50 lx or more at a location 70 cm away when 1 W of power is applied. Thereby, illumination with high efficiency can be realized, and application to a wide range of applications becomes possible.
- a phosphor applicable to a light emitting device that emits warm light can be provided.
- FIG. 6 is a diagram showing the results of X-ray diffraction measurement using phosphor K 1 characteristic X-rays according to the present example using Cu K ⁇ characteristic X-rays.
- FIG. 7 is a diagram showing measurement results of X-ray diffraction using phosphor K 7 characteristic X-rays using Cu K ⁇ characteristic X-rays according to Examples. It is a figure which shows the result of the Rietveld analysis of the fluorescent substance 1 which concerns on a present Example. It is the figure which showed the emission spectrum of the fluorescent substance 1 and the fluorescent substance 6. It is the figure which showed the excitation spectrum of the fluorescent substance 1.
- FIG. 1 is a schematic cross-sectional view of the light emitting device according to the present embodiment.
- a pair of electrodes 14 (anode) and an electrode 16 (cathode) are formed on a substrate 12.
- a semiconductor light emitting element 18 is fixed on the electrode 14 by a mount member 20.
- the semiconductor light emitting element 18 and the electrode 14 are electrically connected by a mount member 20, and the semiconductor light emitting element 18 and the electrode 16 are electrically connected by a wire 22.
- a dome-shaped fluorescent layer 24 is formed on the semiconductor light emitting element 18.
- the substrate 12 is preferably formed of a material having no electrical conductivity but high thermal conductivity.
- a ceramic substrate aluminum nitride substrate, alumina substrate, mullite substrate, glass ceramic substrate
- a glass epoxy substrate aluminum
- a metal substrate such as copper can be used.
- the electrode 14 and the electrode 16 are conductive layers formed of a metal material such as gold or copper.
- the semiconductor light-emitting element 18 is an example of a light-emitting element used in the light-emitting device of the present invention.
- an LED or LD that emits ultraviolet light or short-wavelength visible light can be used.
- Specific examples include InGaN-based compound semiconductors.
- the emission wavelength range of the InGaN-based compound semiconductor varies depending on the In content. When the In content is large, the emission wavelength becomes long, and when it is small, the wavelength tends to be short. However, the InGaN-based compound semiconductor containing In at such an extent that the peak wavelength is around 400 nm is a quantum efficiency in light emission. Has been confirmed to be the highest.
- the mount member 20 is, for example, a conductive adhesive such as silver paste or gold-tin eutectic solder, and the lower surface of the semiconductor light emitting element 18 is fixed to the electrode 14.
- the electrode 14 is electrically connected.
- the wire 22 is a conductive member such as a gold wire, and is joined to the upper surface side electrode and the electrode 16 of the semiconductor light emitting element 18 by, for example, ultrasonic thermocompression bonding, and electrically connects both.
- each phosphor described later is sealed in a hemispherical shape (dome shape) covering the upper surface of the substrate 12 including the semiconductor light emitting element 18 by a binder member.
- the phosphor layer 24 is prepared, for example, by preparing a phosphor paste in which a phosphor is mixed in a liquid or gel binder member, and then applying the phosphor paste to the upper surface of the semiconductor light emitting element 18 in a hemispherical form, and then phosphor. It is formed by curing the binder member of the paste.
- the binder member for example, a silicone resin or a fluorine resin can be used.
- the light-emitting device according to this embodiment uses ultraviolet light or short-wavelength visible light as an excitation light source, a binder member having excellent ultraviolet resistance is preferable.
- the fluorescent layer 24 may be mixed with substances having various physical properties other than the phosphor.
- the refractive index can be increased without reducing the transparency of the fluorescent layer 24 by making the particle size of the substance to be mixed nanosize.
- white powder having an average particle size of about 0.3 to 3 ⁇ m such as alumina, zirconia, and titanium oxide, can be mixed in the fluorescent layer 24 as a light scattering agent. Thereby, uneven brightness and chromaticity in the light emitting surface can be prevented.
- the first phosphor is a phosphor that emits visible light when excited by ultraviolet or short wavelength visible light.
- the general formula is (M 2 x , M 3 y , M 4 z ) m M 1 O 3 X (2 / N) (where M 1 is at least one element containing Si selected from the group consisting of Si, Ge, Ti, Zr and Sn, and M 2 is a group consisting of Ca, Mg, Cd, Co and Zn) one or more elements including at least Ca are more selected, M 3 is Sr, Ra, one or more elements including at least Sr selected from the group consisting of Ba and Pb, X is at least one halogen element, M 4 Represents one or more elements including at least Eu 2+ selected from the group consisting of rare earth elements and Mn, m is in the range of 1 ⁇ m ⁇ 4/3, and n is in the range of 5 ⁇ n ⁇ 7.
- the first phosphor can be obtained, for example, as follows.
- compounds represented by the following composition formulas (1) to (4) can be used as raw materials.
- M ′ 1 O 2 (M ′ 1 represents a tetravalent element such as Si, Ge, Ti, Zr, Sn, etc.)
- M ′ 2 O (M ′ 2 represents a divalent element such as Mg, Ca, Sr, Ba, Cd, Co, Zn, etc.)
- M ′ 3 X 2 (M ′ 3 is a divalent element such as Mg, Ca, Pb, Sr, Ba, and Ra, and X is a halogen element.)
- M ′ 4 (M ′ 4 represents a rare earth element such as Eu 2+ and / or Mn.)
- composition formula (1) for example, SiO 2 , GeO 2 , TiO 2 , ZrO 2 , SnO 2 and the like can be used.
- a raw material of the composition formula (2) for example, a carbonate, oxide, hydroxide, or the like of a divalent metal ion can be used.
- the composition formula (3) for example, SrCl 2 , SrCl 2 .6H 2 O, MgCl 2 , MgCl 2 .6H 2 O, CaCl 2 , CaCl 2 .2H 2 O, BaCl 2 , BaCl 2 .2H 2 O the ZnCl 2, MgF 2, CaF 2 , SrF 2, BaF 2, ZnF 2, MgBr 2, CaBr 2, SrBr 2, BaBr 2, ZnBr 2, MgI 2, CaI 2, SrI 2, BaI 2, ZnI 2 or the like Can be used.
- Eu 2 O 3 , Eu 2 (CO 3 ) 3 , Eu (OH) 3 , EuCl 3 , MnO, Mn (OH) 2 , MnCO 3 , MnCl 2 .4H 2 O , Mn (NO 3 ) 2 .6H 2 O, or the like can be used.
- M ′ 1 preferably contains at least Si. Further, Si may be partially replaced with at least one element selected from the group consisting of Ge, Ti, Zr, and Sn. In this case, a compound in which the proportion of Si in M ′ 1 is 80 mol% or more is preferable.
- M ′ 2 contains at least Ca. Further, Ca may be partially replaced with at least one element selected from the group consisting of Mg, Sr, Ba, Zn, Cd, Co, and the like. In this case, a compound in which the proportion of Ca in M ′ 2 is 60 mol% or more is preferable.
- M ′ 3 contains at least Sr. Further, Sr may be partially replaced with at least one element selected from the group consisting of Mg, Ca, Ba, Ra, Pb, and the like. In this case, the compound whose Sr is 30 mol% or more is preferable.
- X preferably contains at least Cl. Further, Cl may be partially replaced with another halogen element. In this case, a compound having a Cl ratio of 50 mol% or more is preferable.
- M ′ 4 is preferably a rare earth element in which divalent Eu is essential, and may contain a rare earth element other than Mn or Eu.
- the first phosphor can be obtained by carefully washing the fired product with warm pure water and washing away excess chloride.
- the first phosphor is excited by ultraviolet light or short wavelength visible light and emits visible light.
- the raw material (divalent metal halide) of the composition formula (3) it is preferable to weigh an excess amount equal to or higher than the stoichiometric ratio. This is because a part of the halogen element is vaporized and evaporated during firing, and is to prevent the occurrence of crystal defects in the phosphor due to the lack of the halogen element. Moreover, the raw material of the composition formula (3) added in excess is liquefied at the firing temperature and acts as a flux for the solid phase reaction, thereby promoting the solid phase reaction and improving the crystallinity.
- the above-described excessively added raw material of the composition formula (3) exists as an impurity in the manufactured phosphor. Therefore, in order to obtain a phosphor having high purity and high emission intensity, these impurities may be washed away with warm pure water.
- the composition ratio shown in the general formula of the first phosphor of the present embodiment is the composition ratio after the impurities are washed away, and the raw material of the composition formula (3) that is added excessively and becomes impurities as described above. Is not taken into account in this composition ratio.
- the configuration of the second phosphor is not particularly limited, but a blue phosphor having a dominant wavelength of light emission in the range of 455 to 470 nm is preferable.
- the first phosphor that emits light with a dominant wavelength of 577.5 nm or more is suitable for mixing with blue and forming a white light bulb color having a color temperature of 3200 K or less, more preferably 3150 K or less.
- Examples of the second phosphor include compounds represented by the following composition formula.
- the second phosphor can be obtained, for example, as follows.
- the second phosphor uses CaCO 3 , MgCO 3 , CaCl 2 , CaHPO 4 , and Eu 2 O 3 as raw materials, and the molar ratio of these raw materials is CaCO 3 : MgCO 3 : CaCl 2 : CaHPO 4 : Eu 2.
- O 3 0.05 to 0.35: 0.01 to 0.50: 0.17 to 0.50: 1.00: 0.005 to 0.050, and weighed
- Each raw material is put in an alumina mortar and pulverized and mixed for about 30 minutes to obtain a raw material mixture.
- This raw material mixture is put in an alumina crucible and fired at a temperature of 800 ° C.
- the second phosphor can be obtained by carefully washing the fired product with warm pure water and washing away excess chloride.
- the second phosphor emits visible light having a complementary color relationship with the visible light emitted from the first phosphor.
- the mixture was pulverized and mixed for about 30 minutes to obtain a raw material mixture.
- This raw material mixture was packed in a tablet mold and uniaxially compression molded at 100 MPa to obtain a molded body.
- the molded body was put in an alumina crucible and covered, and then fired in air at 1030 ° C. for 36 hours to obtain a fired product.
- the obtained fired product was washed with warm pure water and ultrasonic waves to obtain a base crystal.
- a single crystal having a diameter of 0.2 mm was obtained in the base crystal thus produced.
- the obtained base crystal was subjected to elemental quantitative analysis by the following method to determine the composition ratio (values of a and b in the general formula).
- the crystal system, Brave lattice, space group, and lattice constant of the parent crystal were determined from the X-ray diffraction pattern obtained by Measurement 1 using data processing software (Rigaku: Rapid Auto) as follows.
- Lattice constant: a 13.3030 (12)
- ⁇ b 8.3067
- ⁇ c 9.1567 (12)
- Table 1 shows the atomic coordinates and occupancy of the initial structure model obtained from the single crystal.
- composition ratio of the initial structure model obtained from the single crystal was calculated as in the following formula (2).
- the above-mentioned parent crystal is a crystal having a new structure that is not registered in ICDD (International Center for Diffraction Date), which is an X-ray diffraction database widely used for X-ray diffraction.
- ICDD International Center for Diffraction Date
- Such an analysis method was also applied to each phosphor described later.
- the phosphors and light-emitting devices described above will be described more specifically with reference to the following examples. However, the description of the following materials and manufacturing methods of phosphors and light-emitting devices, the chemical composition of the phosphors, etc.
- the embodiment of the body and the light emitting device is not limited at all.
- the phosphor 1 is a phosphor represented by (Ca 0.6 , Sr 0.25 , Eu 0.15 ) 7/6 SiO 3 Cl 2/6 .
- cristobalite is generated in the phosphor by adding excessive SiO 2 at the mixing ratio of the raw materials.
- the phosphor 1 is manufactured by first using SiO 2 , Ca (OH) 2 , SrCl 2 .6H 2 O, and Eu 2 O 3 with a molar ratio of SiO 2 : Ca (OH) 2 : SrCl 2.
- ⁇ 6H 2 O: Eu 2 O 3 1.0: 0.37: 0.40: 0.07
- the obtained fired product was carefully washed with warm pure water to obtain phosphor 1.
- the phosphor 2 is a phosphor represented by (Ca 0.61 , Sr 0.23 , Eu 0.16 ) 7/6 SiO 3 Cl 2/6 .
- M 1 Si
- M 2 Ca
- M 3 Sr
- X Cl
- M 4 Eu 2+
- m 7/6
- n 6
- the contents x, y, and z of M 2 , M 3 , and M 4 are 0.61, 0.23, and 0.16, respectively.
- cristobalite is generated in the phosphor by adding SiO 2 more excessively than the other phosphors of the examples in the mixing ratio of the raw materials.
- the phosphor 3 is a phosphor represented by (Ca 0.62 , Sr 0.22 , Eu 0.16 ) 7/6 SiO 3 Cl 2/6 .
- the phosphor 4 is a phosphor represented by (Ca 0.61 , Sr 0.21 , Eu 0.18 ) 7/6 SiO 3 Cl 2/6 .
- the phosphor 5 is a phosphor represented by (Ca 0.58 , Sr 0.22 , Ba 0.05 Eu 0.15 ) 7/6 SiO 3 Cl 2/6 .
- cristobalite is generated in the phosphor by adding excessive SiO 2 at the mixing ratio of the raw materials.
- the phosphor 6 is a phosphor represented by (Ca 0.47 , Sr 0.48 , Eu 0.05 ) 7/6 SiO 3 Cl 2/6 .
- cristobalite is generated in the phosphor by adding excessive SiO 2 at the mixing ratio of the raw materials.
- phosphors 7 to 12 are listed as other examples in which a single-phase phosphor having no cristobalite was made as a prototype.
- the phosphor 7 is a phosphor represented by (Ca 0.63 , Sr 0.33 , Eu 0.04 ) 7/6 SiO 3 Cl 2/6 .
- the phosphor 8 is a phosphor represented by (Ca 0.58 , Sr 0.12 , Eu 0.30 ) 7/6 SiO 3 Cl 2/6 .
- the phosphor 9 is a phosphor represented by (Ca 0.48 , Sr 0.40 , Eu 0.12 ) 7/6 SiO 3 Cl 2/6 .
- the phosphor 10 is a phosphor represented by (Ca 0.60 , Sr 0.30 , Eu 0.10 ) 7/6 SiO 3 Cl 2/6 .
- the phosphor 11 is a phosphor represented by (Ca 0.65 , Sr 0.27 , Eu 0.08 ) 7/6 SiO 3 Cl 2/6 .
- M 1 Si
- M 2 Ca
- M 3 Sr
- X Cl
- M 4 Eu 2+
- m 7/6
- n 6
- M 2 , M 3 , M 4 contents x, y, z are 0.65, 0.27, 0.08, respectively.
- the phosphor 12 is a phosphor represented by (Ca 0.71 , Sr 0.22 , Eu 0.07 ) 7/6 SiO 3 Cl 2/6 .
- FIG. 2 is a diagram showing measurement results of X-ray diffraction using phosphors 1 to 6 according to the present embodiment using Cu K ⁇ characteristic X-rays.
- FIG. 3 is a diagram showing measurement results of X-ray diffraction using phosphors 7 to 12 according to this example using Cu K ⁇ characteristic X-rays.
- the phosphors 1 to 12 have very similar X-ray diffraction patterns, indicating that the phosphors have the same crystal structure.
- SiO 2 was further added and baked more excessively than in the other phosphors of the example, a strong cristobalite diffraction peak was observed at the arrowed portion in FIG.
- the total of 6 samples from phosphor 7 to phosphor 12 have a single phase without cristobalite with no peak observed around 22 degrees indicated by the arrow.
- a powdery phosphor sample was used as a powder base crystal, and the BL02B2 large Debye-Scherrer camera of the Super Photon-8 GeV (SPring-8), a high-intensity photoscience research center.
- SPring-8 Super Photon-8 GeV
- precise X-ray diffraction measurement was performed using X-rays having a wavelength of 0.8022 mm (hereinafter referred to as measurement 3).
- measurement 3 Rietveld analysis was performed on the diffraction pattern observed in Measurement 3, and the phosphor composition and the lattice constant were specified.
- FIG. 4 is a diagram illustrating a result of Rietveld analysis of the phosphor 1 according to this example.
- Table 2 shows the composition ratios of phosphors 1 to 6 calculated from Rietveld analysis.
- Table 3 shows the composition ratios of the phosphors 7 to 12. The composition analysis of the phosphors 7 to 12 was performed using a fluorescent X-ray apparatus.
- Table 4 shows the lattice constants and R WP (d> 0.66 ⁇ ) values of phosphors 1 to 6 calculated by Rietveld analysis.
- the value of R WP (d> 0.66 ⁇ ) is good for all phosphors, and the reliability of the analysis result is high.
- the phosphors 1 to 5 as examples are smaller in the calculated lattice constant than the phosphor 6 as a comparative example. This can also be seen from the fact that the diffraction patterns of the phosphors 1 to 5 shown in FIGS. 2 and 3 are shifted to a higher angle side than the diffraction pattern of the phosphor 6.
- the emission dominant wavelength and the emission intensity ratio are shown in Table 5.
- the emission intensity ratio is shown as a ratio when the emission intensity measured when the phosphor 6 is irradiated with excitation light of 400 nm is taken as 100.
- the phosphors 1 to 5 and 7 to 11 of the examples are yellow phosphors that emit light at a long wavelength of 577.6 nm or more.
- the emission intensity of the phosphors 1 to 5 and 7 to 11 is 34 to 103% of the phosphor 6 having a dominant wavelength of 575.5 nm although it emits light having a long wavelength, and exhibits high emission intensity.
- the emission intensity of the phosphor 12 is as low as 13% of the phosphor 6.
- the phosphors 1 to 5 and 7 to 11 of the examples have the value of x in the general formula (M 2 x , M 3 y , M 4 z ) m M 1 O 3 X 2 / n (the total of the metal elements is The ratio of the Ca element in the case of 1 is in the range of 0.45 to 0.8, and the higher the value of x, the longer the dominant wavelength tends to become longer. More preferably, the value of x is in the range of 0.48 to 065.
- the phosphors 1 to 5 and 7 to 11 of the examples have the values of z in the general formula (M 2 x , M 3 y , M 4 z ) m M 1 O 3 X 2 / n (the total of the metal elements is The ratio of the Eu element in the case of 1 is 0.03 or more and 0.35 or less, and in particular, the phosphor 4 having a high z value is the most in spite of the dominant wavelength being a long wave. High emission intensity was shown. More preferably, the value of z is 0.04 or more and 0.30 or less.
- the phosphors 1 to 5 and 7 to 11 of the examples have y values in the general formula (M 2 x , M 3 y , M 4 z ) m M 1 O 3 X 2 / n (the total of the metal elements is 1) (the ratio of Sr element + Ba element) in the range of 0.05 to 0.45. More preferably, the value of z is 0.12 or more and 0.40 or less.
- FIG. 5 is a diagram showing emission spectra of phosphor 1 and phosphor 6.
- FIG. 6 shows phosphor 1 It is the figure which showed the excitation spectrum.
- the phosphor according to the present embodiment is more excited by near-ultraviolet light and short-wavelength visible light, and emits yellow light on the longer wave side than the excitation light. I understand that.
- the phosphor 6 in the phosphor having a large content of elements (Ca, Mg, Zn, Cd, Co) having a small ionic radius, the peak wavelength of the emission spectrum of the phosphor has a longer wavelength side. Shift to. Therefore, the phosphor according to the example can be applied to a warm light emitting device having a relatively low color temperature.
- the light-emitting device according to the example uses the following specific configuration in the light-emitting device shown in FIG.
- the configuration of the light emitting device described below is common in the examples and comparative examples except for the type of phosphor used.
- an aluminum nitride substrate was used as the substrate 12, and an electrode 14 (anode) and an electrode 16 (cathode) were formed on the surface using gold.
- the semiconductor light emitting element 18 a 1 mm square LED (SemiLEDs: MvpLED TM SL-V-U40AC) having an emission peak at 405 nm is used. Then, the lower surface of the LED is adhered onto the silver paste (Able Stick: 84-1LMISS4) dropped on the electrode 14 (anode) using a dispenser, and the silver paste is cured at 175 ° C. for 1 hour. I let you.
- a ⁇ 45 ⁇ m gold wire was used as the wire 22, and this gold wire was bonded to the upper surface side electrode of the LED and the electrode 16 (cathode) by ultrasonic thermocompression bonding. Further, various phosphors or a mixture of a plurality of phosphors were mixed in a silicone resin (manufactured by Toray Dow Corning Silicone Co., Ltd .: JCR6126) as a binder member so as to be 1.4 vol% to prepare a phosphor paste.
- a silicone resin manufactured by Toray Dow Corning Silicone Co., Ltd .: JCR6126
- the dome-shaped phosphor layer 24 is fixed by curing for 1.5 hours in a 150 ° C. environment. Formed.
- the phosphor 13 is a phosphor represented by (Ca 4.67 Mg 0.5 ) (PO 4 ) 3 Cl: Eu 0.08 .
- the phosphor 13 is an example of the second phosphor described above.
- This raw material mixture was put in an alumina crucible and fired at a temperature of 800 ° C. or more and less than 1200 ° C. for 3 hours in an N 2 atmosphere containing 2 to 5% of H 2 to obtain a fired product.
- the obtained fired product was carefully washed with warm pure water to obtain the phosphor 13.
- the phosphor 1 was used as the first phosphor and the phosphor 13 was used as the second phosphor, and a light emitting device was fabricated using a phosphor paste in which these were mixed.
- a mixed phosphor obtained by mixing phosphors 1 and 9 at a weight ratio of 2: 1 is used.
- ⁇ Comparative example> the phosphor 6 was used as the first phosphor and the phosphor 13 was used as the second phosphor, and a light emitting device was fabricated using a phosphor paste in which these were mixed.
- a mixed phosphor in which the phosphors 6 and 9 are mixed at a weight ratio of 2: 1 is used.
- the light emitting devices according to the examples and comparative examples were caused to emit light by supplying a current of 350 mA in an integrating sphere, and the luminous flux ratio and the spectral spectrum were measured with a spectroscope (manufactured by Instrument System: CAS140B-152). The measurement results will be described in detail below.
- Table 6 shows the luminous flux ratio and chromaticity coordinates (Cx, Cy) when a driving current of 350 mA is applied to each light emitting device.
- the luminous flux ratio is shown as a relative value with the luminous flux being 100 when a driving current of 350 mA is applied to the light emitting device of the comparative example.
- FIG. 7 is a diagram illustrating an emission spectrum of the light emitting device according to the example and the comparative example.
- the light-emitting device according to the example is a comparative example in which light is emitted in white with high visibility even though it emits light with a light bulb color (color temperature of about 2800K to 3200K) with low visibility.
- a luminous flux equivalent to that of the light emitting device can be obtained.
- FIG. 8 is a diagram illustrating chromaticity coordinates of light emitted from the light emitting devices according to the example and the comparative example on the chromaticity diagram.
- FIG. 9 is an enlarged view of a part of FIG. Note that regions A1 to A5 in the figure indicate the range of chromaticity standards corresponding to the classification of fluorescent lamps.
- the chromaticity coordinates of the example are indicated by black circles, and the chromaticity coordinates of the comparative example are indicated by black triangles.
- the chromaticity coordinates of the emitted light are chromaticity of the light bulb color. It is in the standard (area A5).
- the light emitting device includes a semiconductor light emitting element 18 that emits ultraviolet light or short wavelength visible light, a first phosphor that emits yellow light when excited by ultraviolet light or short wavelength visible light, and ultraviolet light or short light. And a second phosphor that emits blue light, and is configured to emit light having a color temperature of 2800 K or more and 3200 K or less using light from each phosphor.
- the light-emitting device uses a semiconductor light-emitting element as a light source, includes two phosphors that emit light when excited by light from the light source, and emits light having a color temperature of 2800K to 3200K. Therefore, it is possible to emit light of a light bulb color having a relatively low color temperature with lower power consumption than conventional light bulbs and fluorescent lamps.
- this light-emitting device has sufficient light emission intensity even though the first phosphor having the peak wavelength of the emission spectrum on the longer wavelength side than the peak wavelength of the visibility curve is used. .
- the light-emitting device can emit light with an illuminance of 100 lux (lx) or more.
- illuminance preferably, light of 300 lux or more may be emitted. More preferably, the light of 500 lux or more may be emitted.
- the light-emitting device may be configured to emit light having an illuminance of 50 lux or more at a location 70 cm away when 1 W of power is applied.
- the light-emitting device of the present invention can be used for various lamps, for example, lighting lamps, displays, vehicle lamps, traffic lights, and the like.
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Abstract
Description
第1の蛍光体は、紫外又は短波長可視光により励起され可視光を発光する蛍光体であり、一般式が(M2 x,M3 y,M4 z)mM1O3X(2/n)(ここで、M1はSi、Ge、Ti、Zr及びSnからなる群より選ばれる少なくともSiを含む1種以上の元素、M2はCa、Mg、Cd、Co及びZnからなる群より選ばれる少なくともCaを含む1種以上の元素、M3はSr、Ra、Ba及びPbからなる群より選ばれる少なくともSrを含む1種以上の元素、Xは少なくとも1種のハロゲン元素、M4は希土類元素及びMnからなる群より選ばれる少なくともEu2+を含む1種以上の元素を示す。また、mは1≦m≦4/3、nは5≦n≦7の範囲である。また、x、y、zは、x+y+z=1、0.45≦x≦0.8、0.05≦y≦0.45、0.03≦z≦0.35を満たす範囲である。)で表される蛍光体である。
(1)M’1O2(M’1はSi、Ge、Ti、Zr、Sn等の4価の元素を示す。)
(2)M’2O(M’2はMg、Ca、Sr、Ba、Cd、Co、Zn等の2価の元素を示す。)
(3)M’3X2(M’3はMg、Ca、Pb、Sr、Ba、Ra等の2価の元素、Xはハロゲン元素を示す。)
(4)M’4(M’4はEu2+等の希土類元素及び/又はMnを示す。)
第2の蛍光体は、その構成が特に限定されるものではないが、発光のドミナント波長が455~470nmの範囲にある青色蛍光体が好ましい。この青色と加色混合して、色温度3200K以下、より好ましくは3150K以下の電球色の白色を構成するためには、ドミナント波長577.5nm以上で発光する第1の蛍光体が適当である。第2の蛍光体としては、以下の組成式で示される化合物が挙げられる。
(Ca,M)5(PO4)3X:Eu(Mは2価のアルカリ土類金属、Xはハロゲン元素)
Sr5(PO4)3X:Eu(Xはハロゲン元素)
BaMgAl10O17:Eu
次に、本実施の形態に係る蛍光体の結晶構造等の決定について説明する。以下では、ある物質を一例として説明するが、後述の各蛍光体も同様の方法によって結晶構造等を決定することができる。
母体結晶の単結晶の結晶成長は、以下の手順で実施した。まず、SiO2、CaO、SrCl2の各原料を、これらのモル比がSiO2:CaO:SrCl2=1:0.71:1.07となるように秤量し、秤量した各原料をアルミナ乳鉢に入れ約30分粉砕混合し、原料混合物を得た。この原料混合物をタブレット型に詰め100MPaで一軸圧縮成型をし、成形体を得た。この成形体をアルミナ坩堝に入れ蓋をした後に、大気中で1030℃で36時間焼成し、焼成物を得た。得られた焼成物を温純水と超音波で洗浄し、母体結晶を得た。このようにして生成した母体結晶の中にΦ0.2mmの単結晶を得た。
母体結晶を炭酸ナトリウムにより白金坩堝中で融解した後に、希硝酸で溶解処理して定容とした。この溶液についてICP発光分光分析装置(SIIナノテクノロジー株式会社製:SPS-4000)を用いSi量を測定した。
(2)金属元素の定量分析
母体結晶を不活性ガス下で過塩素酸、硝酸及びフッ化水素酸で加熱分解し、希硝酸で溶解処理して定容とした。この溶液について前述のICP発光分光分析装置を用い金属元素量を測定した。
(3)Clの定量分析
母体結晶を管状電気炉で燃焼し、発生ガスを吸着液に吸着させた。この溶液についてDionex社製DX-500を用いイオンクロマトグラフ法でCl量を決定した。
(4)Oの定量分析
母体結晶をLECO社製の窒素酸素分析装置TC-436を用い、試料をアルゴン中で熱分解し、発生酸素を赤外線吸収法で定量した。
SiO2・1.05(Ca0.6,Sr0.4)O・0.15SrCl2・・・式(1)
結晶系:単斜晶
ブラベ格子:底心単斜格子
空間群:C2/m
格子定数:
a=13.3036(12)Å
b=8.3067(8)Å
c=9.1567(12)Å
α=γ=90°
β=110.226(5)°
V=949.50(18)Å3
SiO2・1.0(Ca0.6,Sr0.4)O・0.17SrCl2・・・式(2)
(Ca0.51,Sr0.49)7/6SiO3Cl2/6・・・式(3)
蛍光体1は、(Ca0.6,Sr0.25,Eu0.15)7/6SiO3Cl2/6で表される蛍光体である。蛍光体1は、前述の一般式(M2 x,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.60,0.25,0.15となるように合成されている。また、蛍光体1は、原料の混合比においてSiO2を過剰に添加することで、蛍光体内にクリストバライトが生成されている。蛍光体1の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1.0:0.37:0.40:0.07となるように秤量し、秤量した各原料をアルミナ乳鉢に入れ約30分粉砕混合し、原料混合物を得た。この原料混合物をアルミナ坩堝に入れ、還元雰囲気の電気炉で所定の雰囲気(H2:N2=5:95)、温度1030℃で5~40時間焼成し、焼成物を得た。得られた焼成物を温純水で丹念に洗浄し、蛍光体1を得た。
蛍光体2は、(Ca0.61,Sr0.23,Eu0.16)7/6SiO3Cl2/6で表される蛍光体である。蛍光体2は、一般式(M2 x,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.61,0.23,0.16となるように合成されている。また、蛍光体2は、原料の混合比において、SiO2を実施例の他の蛍光体よりも更に過剰に添加することで、蛍光体内にクリストバライトが生成されている。蛍光体2の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1.0:0.16:0.18:0.03となるように秤量し、その後は蛍光体1と同様の方法で蛍光体2を得た。
蛍光体3は、(Ca0.62,Sr0.22,Eu0.16)7/6SiO3Cl2/6で表される蛍光体である。蛍光体3は、一般式(M2 x,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.62,0.22,0.16となるように合成されている。なお、蛍光体3の製造では、原料中モル比でCaをSrより多く添加した。また、蛍光体3は、原料の混合比においてSiO2を過剰に添加することで、蛍光体内にクリストバライトが生成されている。蛍光体3の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1.0:0.54:0.42:0.08となるように秤量し、その後は蛍光体1と同様の方法で蛍光体3を得た。
蛍光体4は、(Ca0.61,Sr0.21,Eu0.18)7/6SiO3Cl2/6で表される蛍光体である。蛍光体4は、一般式(M2 x,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.61,0.21,0.18となるように合成されている。なお、蛍光体4の製造では、原料中のモル比でCaをSrより多く添加し、また原料中のEuを通常の1.5倍に増やした。また、蛍光体4は、原料の混合比においてSiO2を過剰に添加することで、蛍光体内にクリストバライトが生成されている。蛍光体4の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1.0:0.50:0.45:0.14となるように秤量し、その後は蛍光体1と同様の方法で蛍光体4を得た。
蛍光体5は、(Ca0.58,Sr0.22,Ba0.05Eu0.15)7/6SiO3Cl2/6で表される蛍光体である。蛍光体5は、一般式(M2 x,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr及びBa、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.58,0.27,0.15となるように合成されている。また、蛍光体5は、原料の混合比においてSiO2を過剰に添加することで、蛍光体内にクリストバライトが生成されている。蛍光体5の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、BaCO3、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:BaCO3:Eu2O3=1.0:0.50:0.45:0.05:0.09となるように秤量し、その後は蛍光体1と同様の方法で蛍光体5を得た。
<蛍光体6>
蛍光体6は、(Ca0.47,Sr0.48,Eu0.05)7/6SiO3Cl2/6で表される蛍光体である。蛍光体6は、一般式(M2 x,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.47,0.48,0.05となるように合成されている。また、蛍光体6は、原料の混合比においてSiO2を過剰に添加することで、蛍光体内にクリストバライトが生成されている。蛍光体6の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1.1:0.45:1.0:0.13となるように秤量し、その後は蛍光体1と同様の方法で蛍光体6を得た。
以下に、クリストバライトを無くした単相の蛍光体を試作した他の実施例として、蛍光体7~蛍光体12を挙げる。
蛍光体7は、(Ca0.63,Sr0.33,Eu0.04)7/6SiO3Cl2/6で表される蛍光体である。蛍光体7は、一般式(M2 z,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.63,0.33,0.04となるように合成されている。蛍光体7の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1:0.61:0.57:0.02となるように秤量し、その後は蛍光体1と同様の方法で蛍光体6を得た。
蛍光体8は、(Ca0.58,Sr0.12,Eu0.30)7/6SiO3Cl2/6で表される蛍光体である。蛍光体8は、一般式(M2 z,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.58,0.12,0.30となるように合成されている。蛍光体8の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1:0.41:0.36:0.23となるように秤量し、その後は蛍光体1と同様の方法で蛍光体8を得た。
蛍光体9は、(Ca0.48,Sr0.40,Eu0.12)7/6SiO3Cl2/6で表される蛍光体である。蛍光体9は、一般式(M2 z,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.48,0.40,0.12となるように合成されている。蛍光体9の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1:0.18:0.18:0.03となるように秤量し、その後は蛍光体1と同様の方法で蛍光体9を得た。
蛍光体10は、(Ca0.60,Sr0.30,Eu0.10)7/6SiO3Cl2/6で表される蛍光体である。蛍光体10は、一般式(M2 z,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.60,0.30,0.10となるように合成されている。蛍光体10の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1:0.22:0.14:0.03となるように秤量し、その後は蛍光体1と同様の方法で蛍光体10を得た。
蛍光体11は、(Ca0.65,Sr0.27,Eu0.08)7/6SiO3Cl2/6で表される蛍光体である。蛍光体11は、一般式(M2 z,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.65,0.27,0.08となるように合成されている。蛍光体11の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1:0.22:0.13:0.03となるように秤量し、その後は蛍光体1と同様の方法で蛍光体11を得た。
蛍光体12は、(Ca0.71,Sr0.22,Eu0.07)7/6SiO3Cl2/6で表される蛍光体である。蛍光体12は、一般式(M2 z,M3 y,M4 z)mM1O3X2/nにおいて、M1=Si、M2=Ca、M3=Sr、X=Cl、M4=Eu2+、m=7/6、n=6、M2,M3,M4の各含有量x,y、zは、それぞれ0.71,0.22,0.07となるように合成されている。蛍光体12の製造は、まず、SiO2、Ca(OH)2、SrCl2・6H2O、及びEu2O3の各原料をこれらのモル比がSiO2:Ca(OH)2:SrCl2・6H2O:Eu2O3=1:0.24:0.12:0.03となるように秤量し、その後は蛍光体1と同様の方法で蛍光体12を得た。
の励起スペクトルを示した図である。図5、図6に示されているように、本実施の形態に係る蛍光体は、近紫外光及び短波長可視光でより励起されるものであり、励起光より長波側の黄色発光をすることがわかる。
実施例に係る発光装置は、図1に示した発光装置において下記の具体的な構成を用いたものである。下記の発光装置の構成は、用いた蛍光体の種類を除き、実施例及び比較例において共通の構成である。
蛍光体13は、(Ca4.67Mg0.5)(PO4)3Cl:Eu0.08で表される蛍光体である。蛍光体13は、前述の第2の蛍光体の一例である。蛍光体13の製造は、まず、CaCO3、MgCO3、CaCl2、CaHPO4、及びEu2O3の各原料を、これらのモル比がCaCO3:MgCO3:CaCl2:CaHPO4:Eu2O3=0.42:0.5:3.0:1.25:0.04となるよう秤量し、秤量した各原料をアルミナ乳鉢に入れ約30分粉砕混合し、原料混合物を得た。この原料混合物をアルミナ坩堝に入れ、2~5%のH2を含むN2雰囲気中で、温度800℃以上1200℃未満で3時間焼成し、焼成物を得た。得られた焼成物を温純水で丹念に洗浄し、本蛍光体13を得た。
本実施例は、第1の蛍光体として蛍光体1を用い、第2の蛍光体として蛍光体13を用いたものであり、これらが混合された蛍光体ペーストを用いて発光装置を作製した。本実施例では、蛍光体1及び9を重量比2:1で混ぜ合わせた混合蛍光体が用いられている。
本比較例は、第1の蛍光体として蛍光体6を用い、第2の蛍光体として蛍光体13を用いたものであり、これらが混合された蛍光体ペーストを用いて発光装置を作製した。本比較例では、蛍光体6及び9を重量比2:1で混ぜ合わせた混合蛍光体が用いられている。
実施例及び比較例に係る発光装置を積分球内で350mAの電流を投入し発光させ、分光器(Instrument System社製:CAS140B-152)で発光光束比及び分光スペクトルを測定した。その測定結果を以下詳述する。
Claims (4)
- 一般式が(M2 x,M3 y,M4 z)mM1O3X(2/n)
(ここで、M1はSi、Ge、Ti、Zr及びSnからなる群より選ばれる少なくともSiを含む1種以上の元素、M2はCa、Mg、Cd、Co及びZnからなる群より選ばれる少なくともCaを含む1種以上の元素、M3はSr、Ra、Ba及びPbからなる群より選ばれる少なくともSrを含む1種以上の元素、Xは少なくとも1種のハロゲン元素、M4は希土類元素及びMnからなる群より選ばれる少なくともEu2+を含む1種以上の元素を示す。また、mは1≦m≦4/3、nは5≦n≦7の範囲である。また、x、y、zは、x+y+z=1、0.45≦x≦0.8、0.05≦y≦0.45、0.03≦z≦0.35を満たす範囲である。)で表される蛍光体。 - 紫外線又は短波長可視光を発する発光素子と、
前記紫外線又は短波長可視光により励起され可視光を発光する第1の蛍光体と、
前記紫外線又は短波長可視光により励起され、前記第1の蛍光体が発光する可視光とは異なる色の可視光を発光する第2の蛍光体と、
を備え、各蛍光体からの光を混合して混合色を得るように構成された発光装置であって、
前記第1の蛍光体は、一般式が(M2 x,M3 y,M4 z)mM1O3X(2/n)
(ここで、M1はSi、Ge、Ti、Zr及びSnからなる群より選ばれる少なくともSiを含む1種以上の元素、M2はCa、Mg、Cd、Co及びZnからなる群より選ばれる少なくともCaを含む1種以上の元素、M3はSr、Ra、Ba及びPbからなる群より選ばれる少なくともSrを含む1種以上の元素、Xは少なくとも1種のハロゲン元素、M4は希土類元素及びMnからなる群より選ばれる少なくともEu2+を含む1種以上の元素を示す。また、mは1≦m≦4/3、nは5≦n≦7の範囲である。また、x、y、zは、x+y+z=1、0.45≦x≦0.8、0.05≦y≦0.45、0.03≦z≦0.35を満たす範囲である。)で表される発光装置。 - 紫外線又は短波長可視光を発する半導体発光素子と、
前記紫外線又は短波長可視光により励起され可視光を発光する第1の蛍光体と、
前記紫外線又は短波長可視光により励起され、前記第1の蛍光体が発光する可視光とは異なる色の可視光を発光する第2の蛍光体と、
を備え、各蛍光体からの光を用いて色温度が2800K以上3200K以下の光を発するように構成された発光装置。 - 1Wの電力が投入された場合に、70cm離れた場所の照度が50lx以上となる光を発するように構成された請求項3に記載の発光装置。
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WO2013065271A1 (ja) * | 2011-11-02 | 2013-05-10 | 株式会社小糸製作所 | 蛍光体 |
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JP2015129254A (ja) * | 2013-12-03 | 2015-07-16 | パナソニックIpマネジメント株式会社 | 酸塩化物蛍光体、発光装置、照明装置、及び車両 |
WO2020246395A1 (ja) * | 2019-06-04 | 2020-12-10 | 株式会社小糸製作所 | 蛍光体、波長変換部材および照明装置 |
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WO2020246395A1 (ja) * | 2019-06-04 | 2020-12-10 | 株式会社小糸製作所 | 蛍光体、波長変換部材および照明装置 |
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Also Published As
Publication number | Publication date |
---|---|
EP2518128B1 (en) | 2018-08-01 |
JP5840499B2 (ja) | 2016-01-06 |
EP2518128A1 (en) | 2012-10-31 |
CN102666782A (zh) | 2012-09-12 |
US20150048406A1 (en) | 2015-02-19 |
US9337399B2 (en) | 2016-05-10 |
KR101422970B1 (ko) | 2014-07-23 |
US20120256222A1 (en) | 2012-10-11 |
EP2518128A4 (en) | 2015-04-15 |
JPWO2011077637A1 (ja) | 2013-05-02 |
KR20120094133A (ko) | 2012-08-23 |
CN102666782B (zh) | 2016-02-10 |
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