WO2011058919A1 - β型サイアロン、その製造方法及びそれを用いた発光装置 - Google Patents
β型サイアロン、その製造方法及びそれを用いた発光装置 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims abstract description 82
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 9
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 239000013078 crystal Substances 0.000 claims description 38
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- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
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- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000002189 fluorescence spectrum Methods 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
-
- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- 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
- 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
-
- 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
Definitions
- the present invention relates to a phosphor used in combination with a light emitting diode chip that emits blue or ultraviolet light, and in particular, ⁇ -sialon in which Eu 2+ that can be used in white LEDs and various light emitting devices is used, its use, and its manufacturing method About.
- the light emitting diode is referred to as an LED (Light Emitting Diode).
- ⁇ -sialon in which divalent europium (Eu) ions are dissolved, is excited by a wide range of wavelengths from ultraviolet to blue light, and has a peak in the wavelength range of 520 to 545 nm. Since it emits the green light it has, it is being put into practical use as a phosphor useful for white LEDs (Patent Document 1).
- the ⁇ -sialon host crystal in which Eu 2+ is dissolved is a solid solution in which ⁇ -type silicon nitride crystal is substituted with aluminum (Al) at the silicon (Si) position and oxygen (O) at the nitrogen (N) position.
- Al aluminum
- O oxygen
- N nitrogen
- unit cell there are two formula quantities of atoms, and therefore, it is represented by the general formula Si 6-z Al z O z N 8-z (z is 0 to 4.2).
- Eu ions serving as the emission center do not replace the Si or Al position, but enter and dissolve in a channel-like space extending in the c-axis direction of the ⁇ -type silicon nitride crystal (Non-patent Document 1).
- the light emission of the divalent Eu ions is due to the 4f-5d transition, and the light emission characteristics greatly depend on the coordination environment of the Eu ions. Therefore, the light emission characteristics can be tuned by the z value and Eu ion concentration which are the composition parameters of ⁇ -sialon.
- the emission intensity becomes maximum at a fluorescence peak wavelength of 540 to 545 nm, and the emission occurs when the fluorescence peak wavelength is out of this range. There existed a problem that intensity fell rapidly (nonpatent literature 2).
- the present inventors have found that the general formula of ⁇ -type sialon host, increasing the z value at Si 6-z Al z O z N 8-z, i.e. by increasing the proportion of Al 2 O 3 in the raw material, Eu 2+ It was confirmed that the fluorescence peak of ⁇ -sialon in which was dissolved in a longer wavelength. On the other hand, when the ratio of Al 2 O 3 is increased, the amount of crystal phase other than ⁇ -type sialon increases, and remarkable sintering progresses between the particles. Therefore, excessive pulverization is necessary for pulverization, and The inventors have obtained the knowledge that the fluorescence characteristics are remarkably lowered due to the difference in composition ratio.
- the present inventors increased the ratio of Al 2 O 3 in the raw material by adding ⁇ -sialon to the raw material in advance and calcining it in producing ⁇ -type sialon in which Eu 2+ is dissolved.
- the present inventors have found that a ⁇ -sialon capable of emitting light with a higher emission efficiency and a longer wavelength than before can be obtained, and the present invention has been achieved.
- ⁇ -sialon added to the raw material is referred to as “additional ⁇ -sialon”.
- the present invention relates to a ⁇ -type sialon in which Eu 2+ is dissolved as a luminescent center in a ⁇ -type sialon host crystal represented by Si 6-z Al z O z N 8-z (z is 0.3 ⁇ z ⁇ 1.5).
- ⁇ -sialon having a fluorescence spectrum peak wavelength of 545 to 560 nm, a half width of 55 nm or more, and an external quantum efficiency of 45% or more when excited with light having a wavelength of 450 nm.
- ⁇ -sialon in which Eu 2+ is dissolved is simply referred to as “ ⁇ -sialon”.
- the ⁇ -sialon of the present invention preferably has a crystal lattice constant a in the range of 0.7614 to 0.7645 nm and a lattice constant c in the range of 0.2914 to 0.2940 nm.
- the element component preferably has an Al content of 2.5 to 12% by mass, an Eu content of 0.15 to 1% by mass, and an oxygen content of 1.4 to 5.5% by mass.
- ⁇ -sialon of the present invention is a diffraction line of a crystal phase other than ⁇ -sialon with respect to the diffraction line intensity of (101) plane of ⁇ -sialon as evaluated by powder X-ray diffraction method.
- the strength is preferably 8% or less.
- the ⁇ -sialon of the present invention preferably has a 50% diameter (D50) in the integrated volume fraction of 7 ⁇ m or more and 30 ⁇ m or less, and a 10% diameter (D10) of 4 ⁇ m in the particle size distribution measured by a laser diffraction scattering method.
- the average minor axis is 7 to 30 ⁇ m.
- the average minor axis is an average value of the lengths of the short sides when the particles are enclosed as a circumscribed rectangle, and is measured by a particle / shape distribution measuring instrument (for example, PITA-1 manufactured by Seishin Enterprise Co., Ltd.). be able to.
- the present invention is a method for producing a ⁇ -type sialon in which Eu 2+ is dissolved in the ⁇ -type sialon represented by Si 6-z Al z O z N 8-z as a luminescent center. Then, one or more oxides selected from aluminum oxide and silicon oxide, silicon nitride, and aluminum nitride are blended so that the z value is 0.3 or more and 1.5 or less, and further europium oxide or heating In a nitrogen atmosphere, a europium salt that becomes europium oxide and an added ⁇ -sialon having an average particle size of 5 ⁇ m or more and an average circularity of 0.7 or more are added in a range of 5 mass% to 30 mass%.
- a heating step of heating in step a step of obtaining a pulverized sintered body by pulverizing the obtained sintered body, a heating step of heating the pulverized sintered body in a rare gas atmosphere or vacuum, and an acid treatment of the heat-treated product Acid processing Process.
- the ratio of one or more oxides selected from aluminum oxide and silicon oxide is preferably 2.2% by mass or more and 20% by mass or less.
- the present invention is a light emitting device using the ⁇ -sialon as a phosphor, and preferably uses an LED as a light source for exciting the phosphor.
- the ⁇ -sialon of the present invention is excited in a wide wavelength range from ultraviolet to visible light, and efficiently emits green to yellow visible light.
- the ⁇ -sialon of the present invention can adjust the fluorescence wavelength while maintaining high luminous efficiency, and various light emitting elements, particularly ultraviolet LED chips or blue LED chips, can be used as a light source alone or in combination with other phosphors. It can be used for white LEDs.
- the ⁇ -sialon production method of the present invention can produce ⁇ -sialon having excellent light emission characteristics as described above.
- the ⁇ -type sialon of the present invention is a ⁇ -type sialon in which Eu 2+ is dissolved in a ⁇ -type sialon host crystal represented by Si 6-z Al z O z N 8-z as a luminescent center (z is 0.3 ⁇ z ⁇ 1.5), when excited with light having a wavelength of 450 nm, the peak wavelength of the fluorescence spectrum is 545 to 560 nm, the half width is 55 nm or more, and the external quantum efficiency is 45% or more.
- the host crystal of ⁇ -type sialon is a solid solution in which Al is substituted at the Si position of ⁇ -type silicon nitride and O is substituted at the N position. Since there are two formula atoms in the unit cell, the general formula is Si It is represented by 6-z Al z O z N 8-z . Here, the composition z is 0 to 4.2, the solid solution range is very wide, and the molar ratio of (Si, Al) / (N, O) must be maintained at 3/4. . Thus, generally, as a raw material, in addition to Si 3 N 4 , SiO 2 and AlN or Al 2 O 3 and AlN are added and heated to produce a ⁇ -type sialon host crystal.
- the ⁇ -sialon of this embodiment has a peak wavelength of a fluorescence spectrum of 545 nm or more and 560 nm or less when excited with light having a wavelength of 450 nm, a half width of 55 nm or more, and an external quantum efficiency of 45% or more.
- the external quantum efficiency is a ratio of the number of photons emitted with fluorescence to the number of photons of excitation light irradiated on the ⁇ -type sialon.
- a low external quantum efficiency is not preferable because sufficient luminance cannot be obtained in a light emitting device such as a white LED using ⁇ -sialon.
- the composition parameter z value is in the range of 0.3 to 1.5.
- the z value is smaller than 0.3, the fluorescence peak wavelength becomes lower than 545 nm, and when the z value exceeds 1.5, the generation of heterogeneous phase and inter-particle sintering are suppressed even if the production method of the present invention is used. It is difficult to do so, and the light emission intensity is reduced.
- ⁇ -type sialon is produced by firing a mixture of silicon, aluminum nitride and oxide raw material powder at a high temperature. A part of the raw material is volatilized during the firing process, and a Si—Al—O—N glass phase is inevitably produced as a by-product, and in some cases, a different phase such as AlN polytypoid or ⁇ -sialon is generated. Therefore, it is difficult to grasp an accurate z value by a raw material blend composition or a raw material powder composition analysis. There is a lattice constant as an index indicating an accurate z value of ⁇ -sialon.
- the ⁇ -type sialon crystal in order to obtain the above-mentioned fluorescence characteristics, has a lattice constant a of 0.7614 to 0.7645 nm and a lattice constant c of 0.2914 to 0.2940 nm. Is preferred.
- the Al content in ⁇ -sialon is 2.5 to 12% by mass
- the Eu content is 0.15 to 1% by mass
- the oxygen content is 1.4 to 5.5% by mass. It is preferable that
- ⁇ -sialon contains the ⁇ -sialon host crystal phase with a high purity and as much as possible. If possible, it is preferably composed of only the ⁇ -sialon host crystal phase. Even a mixture containing a typical amorphous phase and other crystalline phases may be included as long as the characteristics do not deteriorate.
- the crystal phase different from the ⁇ -type sialon host crystal phase is preferably 8% or less with respect to the diffraction line intensity of the (101) plane of ⁇ -type sialon when evaluated by the powder X-ray diffraction method. Since the crystal phase is preferably a single phase, the lower limit of the diffraction line intensity is zero.
- the ⁇ -sialon according to the present embodiment has a particle size distribution measured by a laser diffraction scattering method, the 50% diameter (D50) in the integrated volume fraction is 7 ⁇ m or more, and the 10% diameter (D10) is 4 ⁇ m or more. Is preferred. Especially preferably, they are 4 micrometers or more and 30 micrometers or less. Particles having a small particle diameter not only have low emission intensity of ⁇ -sialon itself due to the influence of crystal defects and the like, but also have a fluorescence wavelength close to the wavelength of visible light and scatter light.
- the D-type sialon of the present embodiment has a D50 of 30 ⁇ m or less. By removing particles having a large D50 value, uniform mixing into the resin for sealing the LED is facilitated, and the causes of LED chromaticity variation and uneven color on the irradiated surface can be reduced.
- the specific surface area is less than 0.05 m 2 / g or more 0.4 m 2 / g. If the particle size is the same, particles composed of single crystal particles, or particles formed from a small number of relatively large primary particles, rather than particles formed by sintering a large number of small primary particles, This is because the luminous efficiency is high.
- the ⁇ -sialon particle surface is smoother, light scattering on the particle surface is suppressed, and the efficiency of taking excitation light into the particles increases.
- the adhesion between the ⁇ -type sialon particles and the sealing resin is increased.
- the primary particle size and the smoothness of the particle surface have a large correlation with the specific surface area. From such a viewpoint, the specific surface area is preferably in the above range.
- ⁇ -type sialon tends to be columnar due to its crystal structure.
- the degree of columnarity varies depending on the raw material composition, particularly the oxide composition contained therein and / or the firing conditions.
- ⁇ type sialon is adjusted so as to be in the above-mentioned particle size range by combining grinding treatment and classification treatment. Since the columnar particles are easily broken in the direction perpendicular to the major axis, if the columnar particles are pulverized, the minor axis remains unchanged and the major axis becomes shorter.
- the major axis / minor axis ratio of the particles is generally increased. Extremely columnar particles are not preferable because they cause a decrease in dispersibility in the resin that seals the LED and variations in luminance and chromaticity of white LEDs using the LED.
- the problem in the white LED can be solved by setting the average minor axis to 7 to 30 ⁇ m in the ⁇ -sialon having the particle size distribution measured by the laser diffraction scattering method in the above range. I understood.
- the ⁇ -type sialon of the present embodiment is added to a raw material composed of silicon oxide and / or aluminum oxide, silicon nitride, aluminum nitride, and Eu compound (hereinafter referred to as “ ⁇ -type sialon raw material”).
- ⁇ -type sialon raw material a raw material composed of silicon oxide and / or aluminum oxide, silicon nitride, aluminum nitride, and Eu compound.
- the z value is 0.3.
- the pulverized sintered body is heated in a rare gas atmosphere or vacuum to obtain a heat-treated product.
- the obtained heat-processed material is acid-treated.
- the ⁇ sialon thus obtained has a fluorescence peak wavelength shifted to the longer wavelength side, a wide half-value width of the fluorescence spectrum, and high emission intensity.
- the oxide in the raw material forms a liquid phase, and the reaction proceeds in such a manner that Si 3 N 4 and AlN dissolve in the liquid phase and precipitate as ⁇ -sialon.
- ⁇ -sialon raw materials have been converted to ⁇ -sialon
- a small amount of liquid phase remains and small particles of ⁇ -sialon, which have a high dissolution rate in the liquid phase, preferentially dissolve in the liquid phase and become large particles of sialon.
- Grain growth proceeds by reprecipitation upward. That is, the particle size difference of ⁇ -sialon becomes a factor of grain growth. Since ⁇ -sialon for addition added to the raw material mixture is significantly larger than particles of ⁇ -sialon formed at the initial stage of firing from other raw materials, it grows as a nucleus.
- Adding the ⁇ -sialon powder for addition to the ⁇ -sialon raw material has an effect of suppressing sintering between particles, which is a problem particularly in the ⁇ -sialon raw material having a high oxide content and a high z value. .
- By suppressing the sintering between the particles excessive pulverization is not required in order to obtain ⁇ -sialon having a predetermined particle size, and there is an effect of suppressing generation of crystal defects that cause a decrease in fluorescence characteristics.
- Addition of ⁇ -sialon for addition to ⁇ -sialon raw material has an effect of suppressing the generation of a residual phase that cannot be completely dissolved in ⁇ -sialon crystal.
- the size and form of the ⁇ -sialon for addition are important factors.
- the ⁇ -sialon for addition has a size and a form with an average particle diameter of 5 ⁇ m or more and 30 ⁇ m or less and an average circularity of 0.7 or more and 1 or less. If the average particle size is small, the particle size of ⁇ -sialon obtained after firing becomes small, and sufficient fluorescence characteristics cannot be obtained, which is not preferable.
- Average circularity is the average value of circularity defined by (peripheral length of a circle equal to the particle area) ⁇ (peripheral length of particle). can do.
- ⁇ peripheral length of particle
- the average circularity is less than 0.7. If ⁇ -sialon powder having an average circularity smaller than 0.7 is added to the ⁇ -sialon raw material in advance, the particle shape, size and composition of ⁇ -sialon are not uniform, which is not preferable.
- ⁇ -sialon grain growth occurs preferentially in the major axis direction of primary particles (particles close to a single crystal)
- ⁇ -sialon for addition uses secondary particles as a result of sintering several small primary particles. It is preferable to be composed of larger single crystal particles than those formed, and the particle aspect ratio (a value obtained by dividing the major axis diameter by the minor axis diameter) is preferably smaller.
- the addition amount of ⁇ -sialon for addition is preferably 5 to 30% by mass. If the addition amount is small, it is not preferable because formation and sintering of new ⁇ -sialon particles and grain growth proceed separately from the ⁇ -sialon particles for addition. When the amount added is large, the factors of grain growth increase, so that the growth of individual particles becomes small and the effect of adding ⁇ -sialon for addition cannot be obtained, which is not preferable.
- the constituent elements and composition of the ⁇ -sialon for addition are not particularly limited. This is because in the excitation of ultraviolet to blue light, the fluorescence characteristics of ⁇ -sialon are mainly expressed in a region close to the powder surface. However, it is preferable to use an additional ⁇ -sialon containing an impurity element such as iron that contains a different luminescent center element or inhibits light emission because it significantly affects the characteristics of the ⁇ -sialon layer formed on the surface. Absent.
- the mixed raw material containing ⁇ -sialon for addition can be obtained by a dry mixing method, a wet mixing method in an inert solvent that does not substantially react with each component of the raw material, and then removing the solvent.
- a mixing apparatus a V-type mixer, a rocking mixer, a ball mill, a vibration mill, etc. are used suitably.
- the mixed raw material containing the additive ⁇ -sialon is filled in a material that does not react with the mixed raw material in the firing process, for example, a container made of boron nitride, and heated in a nitrogen atmosphere, so that the solid solution reaction proceeds. can get.
- the heating temperature range is preferably 1800 to 1950 ° C.
- the heat treatment temperature is low, the grain growth of ⁇ -sialon hardly proceeds and it is difficult to obtain sufficient fluorescence characteristics.
- the heat treatment temperature is increased, the amount of crystal defects generated in the grain growth process is increased, and this absorbs visible light, so that the fluorescence characteristics are deteriorated.
- the granular or massive sintered body obtained by heat treatment is combined with pulverization, pulverization and / or classification operations to form a ⁇ -sialon having a predetermined size.
- ⁇ -sialon As a phosphor for LED, it is desirable to set D10 and D50 within a predetermined range as described above.
- the sintered body is subjected to a sieve classification process with an opening of 20 to 45 ⁇ m to obtain a powder that has passed through the sieve, or the sintered body is generally pulverized by a ball mill, a vibration mill, a jet mill or the like.
- pulverizing to a predetermined particle size using a machine is mentioned.
- excessive pulverization not only generates fine particles that easily scatter light, but also generates crystal defects on the particle surface, causing a decrease in the luminous efficiency of ⁇ -sialon.
- ⁇ -sialon obtained by the treatment only by sieving classification and the pulverization treatment by the jet mill pulverizer without pulverization treatment finally showed high luminous efficiency.
- the luminous efficiency of ⁇ -sialon obtained by the above-described method is further improved by performing the following treatment.
- the ⁇ -sialon is heat-treated in a rare gas atmosphere or in a vacuum to change the luminescence inhibitory factor present in the ⁇ -sialon into an acid-soluble state, and then acid-treated.
- the light emission inhibiting factor there are crystal defects and heterogeneous phases that inhibit visible light emission.
- ⁇ -sialon When heat-treated ⁇ -sialon is acid-treated, the light emission inhibiting factor changed by heating is dissolved and removed, and the fluorescence characteristics are improved.
- the acid used in the acid treatment one or more acids selected from hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid are used, and an aqueous solution containing these acids is used.
- the ⁇ -sialon that has been subjected to the heat treatment is dispersed in an aqueous solution containing the above-described acid, and is reacted by stirring for about several minutes to several hours. After the acid treatment, the ⁇ -sialon particles and the acid are separated with a filter or the like and then washed thoroughly with water.
- the method for producing ⁇ -sialon of the present invention can be applied to a wide range of z values, and in particular, the z value is set to a range of 0.3 to 1.5 higher than the conventionally known z value range. It is desirable from the viewpoints of preventing sintering during sintering and suppressing the formation of different phases. Specifically, the production method is effective when the ratio of the oxide in the starting material excluding ⁇ -sialon for addition is 2.2 to 20% by mass.
- a ⁇ -type sialon raw material is filled into a cylindrical boron nitride vessel with a lid (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.), and is heated at 2000 ° C. in a pressurized nitrogen atmosphere of 0.8 MPa in an electric furnace of a carbon heater. Heat treatment was performed for 15 hours. The obtained sintered body was a lightly agglomerated lump, and could be loosened manually. After mild crushing, three types of ⁇ -sialon for addition having different particle sizes and particle shapes were produced by the following operation.
- the sintered body that had been mildly crushed was pulverized with a supersonic jet pulverizer (PJM-80SP, manufactured by Nippon Pneumatic Industry Co., Ltd.).
- the crushing conditions were a sample supply rate of 50 g / min and a pulverization air pressure of 0.3 MPa.
- the obtained crushed powder was subjected to a classification treatment with an airflow classifier (manufactured by Seishin Enterprise Co., Ltd., Crusheal N2.5).
- the classification conditions were a sample supply speed of 50 g / min, a classification air volume of 4.0 m / m 3 , and a rotation speed of 2000 rpm.
- the recovered coarse powder side was designated as ⁇ -sialon A for addition
- the fine powder side was designated as ⁇ -sialon B for addition.
- the ⁇ -sialon C for addition was obtained by passing the sintered body through a sieve having an opening of 45 ⁇ m using a vibration sieve without pulverizing the sintered body with a supersonic jet pulverizer.
- a sieve having an opening of 45 ⁇ m using a vibration sieve without pulverizing the sintered body with a supersonic jet pulverizer for the three types of ⁇ -type sialons A, B, and C obtained as described above, powder X using Cu K ⁇ rays using an X-ray diffractometer (manufactured by Rigaku Corporation, ULTIMA IV) When the line diffraction measurement (XRD) was performed, only the ⁇ -type sialon host was present as a crystal phase.
- particle size distribution measurement was performed by a laser diffraction / scattering method using a particle size distribution measuring apparatus (LS-230 type, manufactured by Beckman Coulter, Inc.). The adjustment of the sample for particle size distribution measurement was performed according to the silicon nitride measurement conditions in Table 1 attached to JIS R 1629-1997.
- the average circularity of ⁇ -sialon for addition was measured with a particle size / shape distribution measuring instrument (PITA-1) manufactured by Seishin Enterprise Co., Ltd.
- the measurement sample was ultrasonically dispersed in a 0.5 mass% hexametaphosphoric acid aqueous solution to prepare a sample solution. Distilled water was used as a measurement solvent, and the objective lens of a CCD camera for capturing an image was 10 times.
- an average value of about 5000 pieces of data having an equivalent circle diameter of 2.5 ⁇ m or more was taken. Table 1 shows the average particle diameter and average circularity of the ⁇ -sialon for addition.
- ⁇ Manufacture of ⁇ -type sialon> ⁇ -type silicon nitride powder (SN-E10 grade, Ube Industries, Ltd., oxygen content 1.0 mass%) 75.37 mass%, aluminum nitride powder (F grade, Tokuyama Corporation, oxygen content 0.8 mass%) ) 4.32% by mass, aluminum oxide powder (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 4.60% by mass, europium oxide powder (RU grade manufactured by Shin-Etsu Chemical Co., Ltd.) 0.71% by mass, ⁇ -type for addition 15% by mass of Sialon A was mixed by using a V-type mixer (“S-3” manufactured by Tsutsui Rika Kagaku Co., Ltd.), and further passed through a sieve having an opening of 250 ⁇ m to remove agglomeration, thereby obtaining a mixed raw material. .
- the obtained mixed raw material was filled in a cylindrical boron nitride container with a lid, and was subjected to heat treatment at 1900 ° C. for 15 hours in a pressurized nitrogen atmosphere of 0.8 MPa in an electric furnace of a carbon heater.
- the obtained sintered body was a lightly aggregated lump.
- crushing is performed with a supersonic jet crusher under the conditions of a sample supply rate of 50 g / min and a crushing air pressure of 0.5 MPa, and further classification is performed with an airflow classifier.
- the particle size distribution was adjusted to remove fine powder (recovery was on the coarse powder side).
- the classification conditions were a sample supply speed of 50 g / min, a classification air volume of 2.0 m / m 3 , and a rotation speed of 2000 rpm.
- the diffuse reflectance of the powder was measured with an ultraviolet-visible spectrophotometer (JASCO Corp., V-550) equipped with an integrating sphere unit, the average diffuse reflectance in the wavelength range of 650 to 800 nm was calculated. It was 90.8%.
- the sintered compact powder was filled in a cylindrical boron nitride container with a lid, and was subjected to a heat treatment at 1500 ° C. for 8 hours in an atmospheric pressure argon atmosphere in an electric furnace of a carbon heater.
- the color of the obtained powder changed from green before processing to dark green.
- the powder was subjected to a 1: 1 mixed acid treatment of 50% hydrofluoric acid and 70% nitric acid. During the treatment, the suspension changed from dark green to bright green. Thereafter, filtration, washing with water and drying were performed to obtain a ⁇ -sialon powder.
- the average diffuse reflectance of the obtained powder in the wavelength range of 650 to 800 nm was 95.9%, which was higher than before heating.
- the crystal phase was a single phase of ⁇ -sialon.
- the obtained powder X-ray diffraction pattern was subjected to Rietveld analysis using an analysis program JADE manufactured by Rigaku Corporation.
- the Al and Eu contents were measured with an ICP emission spectroscopic analyzer (CIROS-120, manufactured by Rigaku Corporation) after the powder was dissolved by an alkali melting method.
- the oxygen content was measured with an oxygen / nitrogen analyzer (EMGA-920, manufactured by Horiba, Ltd.).
- the Al, Eu, and oxygen contents of this powder were 4.7% by mass, 0.4% by mass, and 2.7% by mass, respectively.
- the 50% diameter (D50) in the volume-based integrated fraction is 16.2 ⁇ m
- the 10% diameter (D10) is 9.4 ⁇ m. Met.
- the short diameter of ⁇ -sialon was measured under the same conditions as the circularity measurement of ⁇ -sialon for addition. About 5,000 particles having an equivalent circle diameter of 2.5 ⁇ m or more were measured, and the average value of the short diameter at which the cumulative particle area was 50% of the total particle area was determined. The average minor axis thus determined was 14.1 ⁇ m.
- the specific surface area of ⁇ -sialon was measured by a constant volume gas adsorption method using a specific surface area measuring device (BELSORP-mini) manufactured by Nippon Bell Co., Ltd., and calculated by BET multipoint analysis.
- the measurement sample was previously degassed for 2 hours or more at 305 ° C. in a flow of atmospheric pressure N 2 .
- Nitrogen was used as the adsorbate, and the molecular cross section was 16.2 ⁇ 10 ⁇ 20 m 2 .
- the specific surface area of the ⁇ -sialon of Example 1 obtained in this way was 0.14 m 2 / g.
- ⁇ -sialon The light emission characteristics of ⁇ -sialon were evaluated by the following method. ⁇ -sialon was filled so that the surface of the concave cell was smooth, and an integrating sphere was attached. Blue light dispersed at a wavelength of 455 nm from a light emission source (Xe lamp) was introduced into the integrating sphere using an optical fiber. A ⁇ -sialon sample was irradiated with blue light as an excitation source, and the spectrum of the fluorescence and reflected light of the sample was measured using a spectrophotometer (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.). The peak wavelength and the half width were obtained from the obtained fluorescence spectrum. The peak wavelength was 550 nm and the half width was 60 nm.
- MCPD-7000 spectrophotometer
- External quantum efficiency was determined as follows. A standard reflector (Spectralon manufactured by Labsphere, Inc.) having a reflectance of 99% is set on the sample part, and the spectrum of the excitation light dispersed at a wavelength of 455 nm is measured, and the excitation light photon is measured from the spectrum in the wavelength range of 450 to 465 nm. The number (Qex) was calculated. Next, ⁇ -sialon was set on the sample portion, irradiated with blue light dispersed at a wavelength of 455 nm, and the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) were calculated from the obtained spectrum data.
- Qref the number of excited reflected light photons
- Qem fluorescent photons
- the number of excitation reflected light photons was calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm.
- the absorption rate, internal quantum efficiency, and external quantum efficiency of ⁇ -sialon of Example 1 were 69%, 81%, and 56%, respectively.
- Example 2 the same ⁇ -sialon raw material as in Example 1 was used, except for europium oxide and ⁇ -sialon for addition, so that the z value was 0.35, and produced by the same treatment as in Example 1. Is.
- the compounding ratio of europium oxide in the ⁇ -sialon raw material of Example 2 is the same as that of Example 1 in an external ratio with respect to 1 mol of ⁇ -sialon represented by Si 6-z Al z O z N 8-z .
- the ⁇ -sialon for addition was 15% by mass.
- Example 3 was produced by the same treatment as in Example 1 using the same ⁇ -sialon raw material as in Example 1, except for europium oxide and ⁇ -sialon for addition, so that the z value was 0.55. Is.
- the compounding ratio of europium oxide in the ⁇ -sialon raw material of Example 3 is the same as that of Example 1 in an external ratio with respect to 1 mol of ⁇ -sialon represented by Si 6-z Al z O z N 8-z .
- the ⁇ -sialon for addition was 15% by mass.
- Example 4 was produced by the same treatment as in Example 1 using the same ⁇ -sialon raw material as in Example 1, except for europium oxide and ⁇ -sialon for addition, so that the z value was 0.8. Is.
- the compounding ratio of europium oxide in the ⁇ -sialon raw material of Example 4 is the same as that of Example 1 in an external ratio with respect to 1 mol of ⁇ -sialon represented by Si 6-z Al z O z N 8-z .
- the ⁇ -sialon for addition was 15% by mass.
- Example 5 was produced by the same treatment as in Example 1 using the same ⁇ -sialon raw material as in Example 1, except for europium oxide and ⁇ -sialon for addition, so that the z value was 1.0. Is.
- the compounding ratio of europium oxide in the ⁇ -sialon raw material of Example 5 is the same as that of Example 1 in an external ratio with respect to 1 mol of ⁇ -sialon represented by Si 6-z Al z O z N 8-z .
- the ⁇ -sialon for addition was 15% by mass.
- Example 6 was produced by the same treatment as in Example 1 using the same ⁇ -sialon raw material as in Example 1, except for europium oxide and ⁇ -sialon for addition, so that the z value was 1.5. Is.
- the compounding ratio of europium oxide in the ⁇ -type sialon raw material of Example 6 is the same as that of Example 1 with respect to 1 mol of ⁇ -type sialon represented by Si 6-z Al z O z N 8-z .
- the ⁇ -sialon for addition was 15% by mass.
- z values of 0.25 (Comparative Example 1) and 2.0 (Comparative Example 2) were produced by the same process as in Example 1.
- the compounding ratio of europium oxide in the ⁇ -sialon raw materials of Comparative Examples 1 and 2 is the same as that of Example 1 in an external ratio with respect to 1 mol of ⁇ -sialon represented by Si 6-z Al z O z N 8-z.
- the ⁇ -sialon for addition was 15% by mass.
- Table 2 shows the blending ratios of the ⁇ -sialon raw materials of Examples 1 to 6 and Comparative Examples 1 and 2. As described above, europium oxide was constant in molar ratio, and ⁇ -sialon for addition was 15% by mass.
- Tables 3 and 4 show the design z values of Examples 1 to 6 and Comparative Examples 1 and 2 and the measurement results thereof.
- the amount of different phase in Table 3 is the ratio of the maximum diffraction line intensity of the crystal phase other than ⁇ -sialon to the diffraction line intensity of the (101) plane of ⁇ -type sialon crystal. did.
- the fluorescence peak wavelength shifted to the longer wavelength side, and the half-width of the spectrum increased.
- the full width at half maximum of Examples 1 to 6 was 56 nm to 71 nm.
- the absorption rate changes corresponding to the change in the content of the raw material Eu in the ⁇ -sialon. That is, when the raw material z value exceeds 1.5, the Eu content is drastically lowered and the absorption rate is lowered.
- Example 7 the same ⁇ -sialon raw material as in Example 1 was used, and excluding europium oxide and ⁇ -sialon A for addition, blending was performed so that the z value was 0.45. Mixing and firing were performed under the same conditions as in Example 1, and the sample after firing was observed with a scanning electron microscope (hereinafter referred to as SEM). The SEM image of Example 7 is shown in FIG.
- Example 8 the additive ⁇ -sialon B was used and mixed and fired under the same conditions as in Example 7. SEM observation was performed about the sample after baking. The SEM image of Example 8 is shown in FIG.
- Comparative Example 3 was obtained without addition of ⁇ -sialon for addition, and Comparative Example 4 was conducted with addition sialon C, and was fired at the same blending ratio and conditions as in Example 7.
- FIG. 3 shows an SEM image of Comparative Example 3
- FIG. 4 shows an SEM image of Comparative Example 4.
- Table 5 shows the ⁇ -sialon raw materials and additive ⁇ -sialons used in Examples 7 to 8 and Comparative Examples 3 to 4.
- the microstructure of ⁇ -sialon varies greatly depending on the type of ⁇ -sialon for addition.
- Comparative Example 3 which does not contain ⁇ -sialon for addition clearly has a small particle size
- Comparative Example 4 which uses ⁇ -sialon C for addition having a small circularity shows a microstructure in which large particles and small particles are mixed. .
- Examples 7 and 8 in which the shape and size of the ⁇ -sialon for addition were controlled, a microstructure having columnar particles having a long minor axis and a uniform particle size was obtained. It can be seen that by forming ⁇ -sialon particles having a relatively long particle minor axis diameter and a uniform size at the firing stage, ⁇ -sialon of columnar particles having a uniform particle size can be obtained.
- Example 7 and 8 and Comparative Example 4 were crushed by a jet mill under the same conditions as in Example 1. However, particle size adjustment by airflow classification was not performed.
- the obtained sample was annealed and acid-treated in an Ar atmosphere in the same manner as in Example 1 to evaluate the fluorescence characteristics.
- Comparative Example 3 as described above, the same pulverization / classification treatment as in the other Examples and Comparative Examples could not be performed.
- a high-speed stamp mill manufactured by Nippon Ceramic Science Co., Ltd., ANS-143PL, thin and hammer
- Alumina a high-speed stamp mill
- a sieve with a 1 mm opening is passed through a 150 ⁇ m sieve using a vibrating sieve, and a sample is annealed in an Ar atmosphere as in Example 1.
- the acid treatment was performed, and the fluorescence characteristics were evaluated.
- the ⁇ -sialon of the present invention is excited at a wide range of wavelengths from ultraviolet to blue light and emits high-brightness green to yellow light, and therefore can be suitably used as a white LED phosphor using blue or ultraviolet light as a light source. Furthermore, since the ⁇ -sialon of the present invention has little decrease in luminance at high temperatures and is excellent in heat resistance and moisture resistance, the lighting device using the ⁇ -sialon described above has luminance and light emission with respect to changes in the operating environment temperature. Small color change and excellent long-term stability.
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Abstract
Description
本発明のβ型サイアロンは、Si6-zAlzOzN8-zで示されるβ型サイアロンホスト結晶に発光中心としてEu2+を固溶したβ型サイアロン(zは0.3≦z≦1.5である)であって、波長450nmの光で励起した場合の蛍光スペクトルのピーク波長が545~560nm、半値幅が55nm以上、外部量子効率が45%以上である。
(1)焼成過程で生成する異相にEuが取り込まれるために、β型サイアロン結晶内に固溶するEu2+量が低下すること、及び
(2)焼結体の粉体化工程で過度の粉砕が必要となり、その際にβサイアロン結晶に欠陥が生成すること、
により、発光強度が大幅に低下することにつながると考えられた。
本実施形態のβ型サイアロンは、酸化ケイ素及び/又は酸化アルミニウムと、窒化ケイ素と、窒化アルミニウムと、Eu化合物とからなる原料(以下、「β型サイアロン原料」という。)に添加用β型サイアロンを加えた混合原料(以下、単に「混合原料」という。)を窒素雰囲気下、1800℃~2200℃で焼成することによって得られる。
α型窒化ケイ素粉末(宇部興産株式会社製SN-E10グレード、酸素含有量1.0質量%)95.43質量%、窒化アルミニウム粉末(トクヤマ株式会社製Fグレード、酸素含有量0.8質量%)3.04質量%、酸化アルミニウム粉末(大明化学株式会社製TM-DARグレード)0.74質量%、酸化ユーロピウム粉末(信越化学工業株式会社製RUグレード)0.79質量%を、V型混合機(筒井理化学器械株式会社製「S-3」)を用いて混合し、更に目開き250μmの篩を全通させ凝集を取り除き、β型サイアロン原料を得た。配合比は、β型サイアロンの一般式:Si6-zAlzOzN8-zにおいて、酸化ユーロピウムを除いて、z=0.25となるように設計したものである。
上記のようにして得られた3種類の添加用β型サイアロンA,B,Cに対して、X線回折装置(株式会社リガク製、ULTIMA IV)を用い、CuのKα線を用いた粉末X線回折測定(XRD)を行ったところ、β型サイアロンホストのみが結晶相として存在していた。
α型窒化ケイ素粉末(宇部興産株式会社製SN-E10グレード、酸素含有量1.0質量%)75.37質量%、窒化アルミニウム粉末(トクヤマ株式会社製Fグレード、酸素含有量0.8質量%)4.32質量%、酸化アルミニウム粉末(大明化学株式会社製TM-DARグレード)4.60質量%、酸化ユーロピウム粉末(信越化学工業株式会社製RUグレード)0.71質量%、添加用β型サイアロンA 15質量%を、V型混合機(筒井理化学器械株式会社製「S-3」)を用いて混合し、更に目開き250μmの篩を全通させて凝集を取り除き、混合原料を得た。配合比は、β型サイアロンの一般式:Si6-zAlzOzN8-zにおいて、酸化ユーロピウムと添加用β型サイアロンを除いて、z=0.65となるように設計したものである。
焼成段階で、ある程度粒子短軸径が長く、サイズが揃ったβ型サイアロン粒子を形成することにより、粒子サイズの揃った柱状粒子のβ型サイアロンが得られることがわかる。
Claims (10)
- Si6-zAlzOzN8-zで示されるβ型サイアロンホスト結晶に発光中心としてEu2+を固溶したβ型サイアロン(zは0.3≦z≦1.5である)であって、波長450nmの光で励起した場合の蛍光スペクトルのピーク波長が545~560nm、半値幅が55nm以上、外部量子効率が45%以上である、β型サイアロン。
- β型サイアロンの格子定数aが0.7614nm以上0.7645nm以下、格子定数cが0.2914nm以上0.2940nm以下の範囲であって、波長450nmの光で励起した場合の蛍光スペクトルのピーク波長が545nm以上560nm以下、半値幅が55nm以上、外部量子効率が45%以上である、β型サイアロン。
- Al含有量が2.5以上12質量%以下、Eu含有量が0.15以上1質量%、酸素含有量が1.4質量%以上5.5質量%以下である、請求項1又は2に記載のβ型サイアロン。
- 粉末X線回折法によるβ型サイアロンの(101)面の回折線強度に対し、β型サイアロン以外の結晶相の回折線強度が8%以下である、請求項1~3のいずれか一項に記載のβ型サイアロン。
- レーザー回折散乱法によって測定した粒子径分布で積算体積分率におけるD50が7μm以上30μm以下であり、D10が4μm以上、かつ比表面積が0.4m2/g以下である、請求項1~4のいずれか一項に記載のβ型サイアロン。
- 平均短径が7μm以上30μm以下である、請求項1~5のいずれか一項に記載のβ型サイアロン。
- Si6-zAlzOzN8-zで示されるβ型サイアロンに発光中心としてEu2+を固溶したβ型サイアロンを製造する方法であって、上記z値が0.3以上1.5以下となるように酸化アルミニウム及び酸化ケイ素から選ばれる1種以上の酸化物と、窒化ケイ素と、窒化アルミニウムとを配合し、さらに酸化ユーロピウム又は加熱により酸化ユーロピウムになるユーロピウム塩、及び平均粒子径が5μm以上、かつ、平均円形度が0.7以上のβ型サイアロンを5質量%以上30質量%以下加えて、窒素雰囲気下で加熱して焼結体を得る工程と、得られた焼結体を粉砕する工程と、粉砕焼結体を希ガス雰囲気又は真空中で加熱する工程と、加熱処理物を酸処理する工程とを含む、β型サイアロンの製造方法。
- 前記酸化物の割合が2.2質量%以上20質量%以下である、請求項7記載のβ型サイアロンの製造方法。
- 請求項1~6のいずれか一項に記載のβ型サイアロンを用いた発光装置。
- 請求項1~6のいずれか一項に記載のβサイアロンを励起する光源としてLEDを用いた請求項9記載の発光装置。
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