WO2019220816A1 - 赤色蛍光体及び発光装置 - Google Patents
赤色蛍光体及び発光装置 Download PDFInfo
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- WO2019220816A1 WO2019220816A1 PCT/JP2019/015362 JP2019015362W WO2019220816A1 WO 2019220816 A1 WO2019220816 A1 WO 2019220816A1 JP 2019015362 W JP2019015362 W JP 2019015362W WO 2019220816 A1 WO2019220816 A1 WO 2019220816A1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 238000004438 BET method Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000000790 scattering method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 description 20
- 239000011575 calcium Substances 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 238000010304 firing Methods 0.000 description 11
- 239000002344 surface layer Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009877 rendering Methods 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- -1 calcium nitride Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
-
- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Definitions
- the present invention relates to a red phosphor for LED (Light Emitting Diode) or LD (Laser Diode), and a light emitting device using the red phosphor. More specifically, the present invention relates to a high-luminance red phosphor and a light-emitting device that is excellent in luminance by using the red phosphor.
- a white LED is a device that emits pseudo white light by a combination of a semiconductor light-emitting element and a phosphor.
- a combination of a blue LED and a YAG yellow phosphor is known.
- this type of white LED falls within the white region as its chromaticity coordinate value, it lacks a red light-emitting component, and therefore has a low color rendering property for lighting applications, and is an image display device such as a liquid crystal backlight. Then, there is a problem that color reproducibility is bad. Therefore, in order to compensate for the insufficient red light emitting component, it has been proposed to use a nitride or oxynitride phosphor that emits red light together with the YAG phosphor (Patent Document 1).
- Patent Document 2 describes that a phosphor obtained by activating Eu 2+ on a CASN base crystal (that is, Eu-activated CASN phosphor) emits light with high luminance.
- the light emission color of the CASN phosphor includes many spectral components on the longer wavelength side even in the red region, so that high color rendering with high depth can be realized, but on the other hand, the spectral components with low visibility are also increased. Therefore, there is a demand for further improvement in luminance.
- Patent Document 2 Eu 2+ is added to a parent crystal (generally also described as SCASN) in which a part of Ca in the CaAlSiN 3 is further substituted with Sr (Sr, Ca) AlSiN 3 . It is described that an activated phosphor (ie, Eu-activated SCASN phosphor) can be obtained.
- Patent Document 3 the specific surface area is defined in the SCASN phosphor and CASN phosphor to improve the moisture resistance and suppress the light emission failure in the high temperature and high humidity state, but in order to obtain a high luminance red phosphor Was insufficient.
- Patent Document 4 describes that a high-luminance CASN phosphor can be obtained by controlling the particle diameter within a specific range by setting the raw material in a specific configuration.
- JP 2004-071726 A International Publication No. 2005/052087 Japanese Patent Laying-Open No. 2015-203096 JP 2017-043761 A
- a white LED that emits white light by a combination of a semiconductor light emitting element and a phosphor is required to have high color rendering properties and high luminance.
- the red phosphor CASN phosphor is also required to have a higher brightness than conventional phosphors, but the phosphors described in Patent Documents 1 to 4 described above are actually insufficient.
- the inventors of the present invention can control the median diameter d50 measured by the laser diffraction scattering method of the CASN phosphor and the specific surface area measured by the BET method within a specific range.
- the present inventors have found that higher luminance than that of the phosphor can be obtained and have reached the present invention.
- the present invention can provide the following.
- the emission peak wavelength when excited with light having a wavelength of 455 nm is 645 nm or more and 680 nm or less
- the x value of the CIE chromaticity coordinates of the emission color is 0.662 or more and 0.710 or less
- the y value is 0.290 or more.
- a light emitting device comprising the phosphor according to (1) to (3) and a light emitting element.
- luminance can be provided, and also the light-emitting device which has a high-intensity light-emitting device and the instrument which accommodates a light-emitting device can be provided.
- light-emitting devices to which the present invention can be applied include lighting devices, backlight devices, image display devices, and signal devices.
- Example 1 It is a microscope picture of the fluorescent substance obtained in Example 1 which concerns on embodiment of this invention. 2 is a photomicrograph of the phosphor obtained in Comparative Example 1.
- the main crystal phase has the same structure as the CaAlSiN 3 crystal phase. Whether or not the main crystal phase of the phosphor has the same structure as the CaAlSiN 3 crystal can be confirmed by powder X-ray diffraction. When the crystal structure is different from CaAlSiN 3 , the emission color is not red and the fluorescence intensity is greatly reduced, which is not preferable.
- the crystal phase is preferably a single phase of the crystal, but may contain a different phase as long as the phosphor characteristics are not greatly affected.
- the skeletal structure of the CaAlSiN 3 crystal is formed by bonding (Si, Al) —N 4 tetrahedrons, and Ca atoms are located in the gaps. A part of Ca 2+ is replaced with Eu 2+ which acts as a luminescent center, so that a red phosphor is obtained.
- the Eu content which is the activator of the phosphor of the present invention is too small, the contribution to light emission tends to be small, and if too large, concentration quenching of the phosphor due to energy transfer between Eu 2+ tends to occur. Therefore, it is preferably 0.01 at% or more and 1.0 at% or less, particularly preferably 0.03 at% or more and 0.5 at% or less.
- the phosphor of the present invention contains a trace amount of oxygen (O) as an inevitable component.
- the M element occupancy, Si / Al ratio, N / O, and the like are adjusted so that the electrical neutrality is maintained as a whole while maintaining the crystal structure.
- an average particle diameter in the phosphor of the present invention refers to the median diameter d50 measured by the laser diffraction scattering method according to JIS R1622: 1995 and R1629: 1997.
- the main crystal phase is preferably a CaAlSiN 3 crystal phase
- the phosphor surface has a layer (hereinafter referred to as a surface layer) containing a chemical composition different from that of the host crystal of the phosphor.
- a surface layer containing a chemical composition different from that of the host crystal of the phosphor.
- an oxide film naturally oxide film is formed on the surface of nitride when exposed to the atmosphere.
- the phosphor of the present invention reduces surface defects by forming layers and surface layers having properties different from those of natural oxide films, or increases light extraction efficiency due to the difference in refractive index between the CaAlSiN 3 crystal phase and the surface layer. A phosphor with high luminous efficiency can be obtained.
- the specific surface area increases with respect to the average particle diameter, but the specific surface area needs to be 1.50 m 2 / g or more and 10.00 m 2 / g or less, and is 2.00 m 2. / G or more, or 7.50 m 2 / g or more is preferable. In the present specification, the specific surface area is measured by the BET method.
- the specific surface area of the phosphor is determined based on the measurement of the specific surface area of the powder (solid) by gas adsorption using JIS Z8830: 2013. taking measurement.
- the surface layer is preferably an oxide film or a hydroxide film having a composition containing oxygen
- the phosphor containing the surface layer preferably has an oxygen content of 1.00% by mass to 3.50% by mass, particularly preferably 1.30% by mass or more and 3.00% or less.
- the phosphor of the present invention is a red phosphor having high color rendering properties and high brightness.
- the emission peak wavelength ( ⁇ p) when excited with light having a peak in the wavelength range of 250 nm to 550 nm (especially when excited with light of 455 nm) is too short, the color rendering properties are low, and when too long, the color rendering property is low. Since it is reddish, 645 nm or more and 680 nm or less are preferable.
- the emission color of the phosphor can be expressed by one of the CIE chromaticity coordinates, the x value and y value of the XYZ color system.
- the x value of the CIE chromaticity coordinates of the phosphor of the present invention is preferably from 0.662 to 0.710, and the y value is preferably from 0.290 to 0.328.
- the x and y values of the CIE chromaticity coordinates of the phosphor can be calculated from the emission spectrum in the range of 465 nm to 780 nm by calculation according to JIS Z8724: 1997.
- the same production method as that for the conventional CaAlSiN 3 phosphor can be used.
- a method of firing the raw material mixed powder that can constitute the composition represented by the above general formula in a predetermined temperature range in a nitrogen atmosphere is exemplified.
- nitrides of constituent elements that is, calcium nitride, silicon nitride, aluminum nitride, and europium nitride are preferably used as raw materials, but oxides can also be used.
- europium oxide which is easily available, may be used as a europium source with a very small addition amount because it acts as a luminescent center.
- the method of mixing the above-mentioned raw materials is not particularly limited, it is appropriate to handle calcium nitride and europium nitride that react violently with moisture and oxygen in the air in a glove box replaced with an inert atmosphere.
- the firing container is preferably made of a material that is stable in a high-temperature nitrogen atmosphere and hardly reacts with the raw material mixed powder and its reaction product, and examples thereof include boron nitride, a refractory metal container, and carbon.
- the firing container filled with the raw material mixed powder is taken out from the glove box, quickly set in a firing furnace, and fired at 1600 ° C. to 2000 ° C. in a nitrogen atmosphere. If the calcination temperature is too low, the unreacted residual amount increases, and if it is too high, the main phase having the same crystal structure as CaAlSiN 3 is decomposed, which is not preferable.
- the firing time a time range in which a large amount of unreacted substances are present, grain growth is insufficient, or a disadvantage that productivity is lowered does not occur is selected, and it is preferably 2 hours or more and 24 hours or less.
- the pressure of the firing atmosphere is selected according to the firing temperature.
- the phosphor of the present invention can exist stably at atmospheric pressure at a temperature up to about 1800 ° C., but at a temperature higher than this, it is necessary to use a pressurized atmosphere in order to suppress decomposition of the phosphor.
- the state of the fired product varies depending on the raw material composition and firing conditions, such as powder, lump, and sintered body.
- the baked product is made into a powder of a predetermined size by combining crushing, grinding and / or classification operations.
- the aqueous solution used in the acid treatment step is preferably an aqueous solution of one or more acids such as hydrochloric acid, formic acid, acetic acid, sulfuric acid and nitric acid, and more preferably an aqueous solution containing only hydrochloric acid.
- the phosphor after the pulverization step is dispersed in the acid aqueous solution described above, reacted by stirring for several minutes to several hours, and then heated until boiling as a boiling treatment, and the boiling state is changed from several minutes to several hours. It is the process of maintaining with stirring and then washing with water.
- Impurity elements derived from the firing container, foreign phases generated in the firing process, impurity elements contained in the raw materials, impurity elements mixed in the grinding process can be dissolved and removed by acid treatment, and a surface layer is formed on the phosphor by further boiling. Can be made. Moreover, in order to simplify a process, you may perform the said acid treatment process and a boiling process process simultaneously.
- the control of the surface layer formation can be dealt with by changing the concentration and temperature of the acid solution during the acid boiling treatment step in the phosphor manufacturing method.
- the surface layer can be formed thick by increasing the concentration of the acid solution during the acid boiling treatment step or by raising the temperature of the acid solution.
- the concentration of the acid solution during the acid boiling treatment step is preferably 0.5 mol / l or more and 2.5 mol / l or less, and the temperature is preferably 45 ° C. or more and 100 ° C. or less.
- the phosphor of the present invention can be used in a light emitting device composed of a light emitting light source and a phosphor.
- a light emitting device composed of a light emitting light source and a phosphor.
- ultraviolet light or visible light having a wavelength of 350 nm or more and 500 nm or less as an excitation source, and having a light emission characteristic having a fluorescence peak in the vicinity of a wavelength of 650 nm
- a light source such as an ultraviolet LED or a blue LED.
- white light can be easily obtained by further combining with a green to yellow phosphor and / or a blue phosphor.
- Table 1 shows the average particle diameter, specific surface area, oxygen content, and light emission characteristics of the phosphors of Examples and Comparative Examples.
- Si 3 N 4 , AlN, and Eu 2 O 3 were dry mixed for 10 minutes with a V-type mixer.
- the mixed raw materials were classified with a nylon sieve having an opening of 250 ⁇ m to obtain a raw material mixture.
- the raw material mixture that passed through the sieve was moved into a glove box capable of maintaining a nitrogen atmosphere having a moisture content of 1 mass ppm or less and an oxygen content of 1 mass ppm or less, where Ca 3 N 2 was blended into the raw material mixture and dry-mixed. .
- classification was again performed with a nylon sieve having an opening of 250 ⁇ m. 250 g of the classified raw material was filled into a cylindrical boron nitride container with a lid (N-1 grade manufactured by Denka Co., Ltd.).
- the container filled with the raw material was taken out from the glove box, and immediately set in an electric furnace of a carbon heater, and the inside of the furnace was sufficiently evacuated to 0.1 Pa or less. While evacuating, heating was started, nitrogen gas was introduced at 650 ° C., and the atmospheric pressure in the furnace was set to 0.1 MPa. Even after the introduction of the gas, the temperature was raised to 1850 ° C. as it was, and firing was performed at 1850 ° C. for 8 hours.
- the sample collected from the furnace was a red lump, crushed in a mortar, and finally passed through a sieve having an opening of 75 ⁇ m.
- the obtained phosphor sample was subjected to powder X-ray diffraction using CuK ⁇ rays using an X-ray diffractometer (Ultrama IV manufactured by Rigaku Corporation).
- the obtained X-ray diffraction pattern was found to have the same diffraction pattern as the CaAlSiN 3 crystal.
- the average particle size was measured by a laser diffraction / scattering method using a particle size distribution measuring device (Microtrack MT3000II manufactured by Microtrack Bell Co., Ltd.).
- the specific surface area was measured in accordance with JIS Z 8830: 2013 gas specific surface area measurement by gas adsorption using a specific surface area measuring device (Macsorb HM-1201 type manufactured by Mountec Co., Ltd.). The measurement sample was sampled in advance at 4.0 g after a degassing treatment at 300 ° C. for 20 minutes in a nitrogen gas flow at 0.30 MPa.
- the oxygen content was measured using an oxygen nitrogen analyzer (EMGA-920, manufactured by Horiba, Ltd.). For measurement, put the sample in a graphite crucible, remove the surface adsorbate at 280 ° C. (melting voltage 0.5 KW), then raise the temperature to 2400 ° C. (melting voltage 5.5 KW), and use the same conditions with an empty graphite crucible in advance. The amount of oxygen was obtained by subtracting the measured value of the background treated with.
- EMGA-920 oxygen nitrogen analyzer
- Fluorescence measurement was performed using a spectrofluorometer (F-7000, manufactured by Hitachi High-Technologies Corporation) corrected with rhodamine B and a sub-standard light source.
- F-7000 spectrofluorometer
- rhodamine B corrected with rhodamine B and a sub-standard light source.
- a solid sample holder attached to the photometer was used, and an emission spectrum at an excitation wavelength of 455 nm was obtained.
- the emission peak wavelength obtained from the obtained emission spectrum was 652 nm.
- the CIE chromaticity coordinate x value and y value in the XYZ color system defined by JIS Z8701: 1999 were calculated from the emission spectrum in the range of 465 nm to 780 nm in accordance with JIS Z8724: 1997.
- the x value was 0.671 and the y value was 0.326. Since the emission peak intensity varies depending on the measurement apparatus and conditions, the unit is arbitrary, and the comparison was made relative to the Examples and Comparative Examples measured under the same conditions. In Table 1, the emission peak intensity is shown as a relative value with the emission peak intensity of Example 1 as 100% as a reference. It is determined that 99% or more is excellent luminance.
- Table 1 shows the evaluation results of the phosphor obtained in Example 1. Moreover, the microscope picture of the fluorescent substance obtained in Example 1 is shown in FIG.
- Comparative Example 1 A phosphor powder was produced under the same conditions as in Example 1 except that boiling treatment with a hydrochloric acid solution was not performed. The emission characteristics of the phosphor obtained in Comparative Example 1 are shown in Table 1 together with the results of Example 1. A micrograph of the phosphor obtained in Comparative Example 1 is shown in FIG. It is understood that the structure is clearly different from the phosphor of Example 1 described above.
- Examples 2 to 5, Comparative Examples 2 to 5 The same raw material powder as in Example 1 was used, pulverized and classified so as to have the average particle diameter shown in Table 1, and the boiling concentration was changed by changing the acid concentration and temperature shown in Table 1, and the same as in Example 1 Under the conditions, phosphor powders of Examples 2 to 5 and Comparative Examples 2 to 5 were produced. The emission characteristics of the phosphors obtained in Examples 2 to 5 and Comparative Examples 2 to 5 are shown in Table 1 together with the results of Example 1.
- the brightness was improved by controlling the average particle diameter, specific surface area, and oxygen content in the phosphor within specific ranges.
- the CaAlSiN 3 phosphor of the present invention is excited by blue light and exhibits high-luminance red light emission. Therefore, the CaAlSiN 3 phosphor can be suitably used as a phosphor for white LED using blue light as a light source. It can use suitably for light-emitting devices, such as.
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Abstract
Description
実施例1の蛍光体の原料として、α型窒化ケイ素粉末(Si3N4、宇部興産株式会社製SN-E10グレード)、窒化カルシウム粉末(Ca3N2、Materion社製)、窒化アルミニウム粉末(AlN、トクヤマ株式会社製Eグレード)、酸化ユーロピウム(Eu2O3、信越化学工業株式会社製RUグレード)を、Ca:Eu:Al:Si=0.994:0.006:1.00:1.00となる比率で用いた。
平均粒子径は、粒度分布測定装置(マイクロトラック・ベル株式会社製マイクロトラックMT3000II)を用い、レーザー回折・散乱法により測定を行った。
比表面積は、比表面積測定装置(マウンテック社製Macsorb HM-1201型)を用いて、JIS Z 8830:2013 ガス吸着による粉体(固体)の比表面積測定に準拠して行った。測定試料は、あらかじめ0.30MPaでの窒素ガスフロー中、300℃、20分の脱気処理後、4.0gサンプリングしたものとした。
酸素含有量は、酸素窒素分析装置(堀場製作所製、EMGA-920)を用いて測定した。測定は、サンプルを黒鉛ルツボに入れ、280℃(融解電圧0.5KW)で表面吸着物を除去し、その後2400℃(融解電圧5.5KW)まで昇温し、予め空の黒鉛ルツボで同条件で処理したバックグラウンドの測定値を差し引き酸素量を得た。
ローダミンBと副標準光源により補正を行った分光蛍光光度計(日立ハイテクノロジーズ社製、F-7000)を用いて蛍光測定を行った。測定には、光度計に付属の固体試料ホルダーを使用し、励起波長455nmでの発光スペクトルを求めた。得られた発光スペクトルより求めた発光ピーク波長は652nmであった。更に発光スペクトルにおいて、465nmから780nmの範囲の発光スペクトルからJIS Z8724:1997に準じ、JIS Z8701:1999で規定されるXYZ表色系におけるCIE色度座標x値、y値を算出した。x値は0.671、y値は0.326であった。発光ピーク強度は、測定装置や条件によって変化するため単位は任意であり、同一条件で測定した実施例及び比較例での相対で比較した。表1では発光ピーク強度を、基準として実施例1の発光ピーク強度を100%とした相対値で示した。99%以上を優れた輝度と判定する。
塩酸溶液による煮沸処理を行わないこと以外、実施例1と同じ条件で蛍光体粉末を作製した。比較例1で得られた蛍光体の発光特性を実施例1の結果と合わせて表1に示す。また比較例1で得られた蛍光体の顕微鏡写真を図2に示す。上述した実施例1の蛍光体とは構造が明らかに異なっていることが理解される。
実施例1と同じ原料粉末を使用し、表1に示す平均粒子径になるよう粉砕、分級を行い、更に表1に示す酸濃度、温度を変えて煮沸処理を行った以外実施例1と同じ条件で実施例2~5、比較例2~5の蛍光体粉末を作製した。実施例2~5、比較例2~5で得られた蛍光体の発光特性を実施例1の結果と合わせて表1に示す。
配合比がCa:Eu:Al:Si=0.988:0.012:1.00:1.00となるよう原料の比率を調整したこと以外実施例1と同じ条件で実施例6の蛍光体粉末を作製した。得られた蛍光体の発光特性を実施例1の結果と合わせて表1に示す。
Claims (4)
- 主結晶相がCaAlSiN3と同一の結晶構造を有し、Ca元素の一部がEu元素で置換されている蛍光体であって、レーザー回折散乱法で測定したメディアン径d50が12.0μm以上22.0μm以下、BET法で測定した比表面積が1.50m2/g以上10.00m2/g以下である蛍光体。
- 酸素含有量が1.00質量%以上3.50質量%以下である請求項1に記載の蛍光体。
- 455nmの波長の光で励起した際の発光ピーク波長が645nm以上680nm以下で、発光色のCIE色度座標のx値が0.662以上0.710以下、y値が0.290以上0.328以下である請求項1乃至2に記載の蛍光体。
- 請求項1乃至3に記載の蛍光体と、発光素子とを有する発光装置。
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