WO2022102503A1 - 蛍光体粉末、発光装置、画像表示装置および照明装置 - Google Patents
蛍光体粉末、発光装置、画像表示装置および照明装置 Download PDFInfo
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- 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
- C09K11/646—Silicates
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/77217—Silicon Nitrides or Silicon Oxynitrides
-
- 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
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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
- C09K11/55—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
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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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/77216—Aluminium Nitrides or Aluminium Oxynitrides
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- 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
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- 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
Definitions
- the present invention relates to a phosphor powder, a light emitting device, an image display device and a lighting device.
- Fluorescent materials are usually used to produce white LEDs (Light Emitting Diodes). That is, a phosphor is used as a wavelength conversion material for obtaining white light from blue light emitted from a blue LED. With the widespread use of white LEDs in lighting applications and the study of application of white LEDs to image display devices, the development of phosphors capable of converting blue light into light having a longer wavelength is continuing.
- white LEDs Light Emitting Diodes
- One of the viewpoints for improving the fluorescent substance is to modify the chemical composition of the fluorescent substance.
- the general formula M x (Si, Al) 2 (N, O) 3 ⁇ y (where M is Li and one or more alkaline earth metal elements, 0.52 ⁇ x ⁇ 0.9, 0.06 ⁇ y ⁇ 0.23), a phosphor in which a part of M is substituted with a Ce element, and the Si / Al atomic ratio is 1.5 or more and 6 or less.
- a phosphor having an O / N atomic ratio of 0 or more and 0.1 or less, 5 to 50 mol% of M being Li, and 0.5 to 10 mol% of M being Ce is described.
- the fluorescent substance described in Patent Document 1 has room for improvement in terms of conversion efficiency of blue light, specifically, in terms of increasing internal quantum efficiency.
- the present inventor has made a study this time as one of the purposes of providing a fluorescent substance powder having high internal quantum efficiency and improved conversion efficiency of blue light.
- M x (Si, Al) 2 (N, O) 3 ⁇ y (where M is Li and one or more alkaline earth metal elements, 0.52 ⁇ x ⁇ 0.9, 0.06 ⁇ It is a phosphor represented by y ⁇ 0.36), in which a part of M is substituted with a Ce element, the Si / Al atomic ratio is 1.5 or more and 6 or less, and the O / N atomic ratio is A phosphor powder containing phosphor particles having 0 or more and 0.1 or less, 5 to 50 mol% of M being Li, and 0.5 to 10 mol% of M being Ce.
- a light emitting device including the above-mentioned phosphor powder and a light emitting light source is provided.
- An image display device including the above light emitting device is provided.
- a lighting device including the above light emitting device is provided.
- the fluorophore powder of the present invention has high internal quantum efficiency and good conversion efficiency of blue light.
- XY in the description of the numerical range indicates X or more and Y or less unless otherwise specified.
- “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
- the fluorescent powder of the present embodiment contains fluorescent particles represented by the general formula M x (Si, Al) 2 (N, O) 3 ⁇ y .
- M is Li and one or more alkaline earth metal elements, 0.52 ⁇ x ⁇ 0.9, 0.06 ⁇ y ⁇ 0.36. Further, a part of M is substituted with a Ce element, the Si / Al atomic ratio is 1.5 or more and 6 or less, the O / N atomic ratio is 0 or more and 0.1 or less, and 5 to 50 mol of M. % Is Li, and 0.5 to 10 mol% of M is Ce. Further, the diffuse reflectance X1 of the phosphor powder of the present embodiment with respect to light having a wavelength of 700 nm is 88% or more and 99.9% or less.
- the fluorescent substance powder of the present embodiment is different from the fluorescent substance described in Patent Document 1 in that X1 is at least 88% or more and 99.9% or less.
- the fluorophore powder of the present embodiment efficiently converts blue light into long-wavelength light, for example, in terms of internal quantum efficiency, as compared with the fluorophore described in Patent Document 1.
- Absorption of the fluorescent substance includes light absorption accompanied by an electronic transition of the emission center ion and light absorption unrelated to fluorescence emission derived from impurities and crystal defects of the base material.
- the light absorption when irradiating a phosphor that emits visible light with light in the near infrared region, for example, a wavelength of 700 nm is irrelevant to the fluorescence emission, and is an index for lowering the fluorescence characteristics.
- the present inventors newly prototyped various phosphors represented by the general formula M x (Si, Al) 2 (N, O) 3 ⁇ y . Then, the diffuse reflectance was measured.
- the present inventors include a phosphor represented by the general formula M x (Si, Al) 2 (N, O) 3 ⁇ y , and X1 is 88% or more and 99.9% or less.
- a new fluorescent substance powder was prepared. The present inventor has succeeded in increasing the internal quantum efficiency of the fluorescent substance powder.
- the fluorescent powder of the present embodiment can be produced by using an appropriate material and by selecting an appropriate production method and conditions.
- the "appropriate manufacturing method / manufacturing conditions” include, for example, (i) acid treatment of the fluorescent powder under specific conditions, (ii) appropriate classification treatment (for example, precipitation classification) of the fluorescent powder. (Iii) One or two or more of devising a method for pulverizing the fluorescent substance powder. Details of the manufacturing method and manufacturing conditions will be described later.
- the skeleton structure of the phosphor crystal is composed of the bonds of (Si, Al)-(N, O) tetrahedrons , and the M element is located in the gap.
- the composition of the above general formula is established in a wide range in which the electrical neutrality is maintained by all the parameters of the valence and amount of the M element, the Si / Al ratio, and the N / O ratio.
- the crystal structure of the fluorophore particles contained in the fluorophore powder of the present embodiment is usually based on CaAlSiN3 crystals.
- One of the characteristics of these phosphor particles is that the constituent elements and composition have been significantly changed so that extremely high luminous efficiency can be obtained even with Ce activation.
- the M element is a combination of the Li element and the alkaline earth metal element, and a part thereof is replaced with the Ce element which is the center of light emission.
- the Li element the average valence of the M element can be widely controlled by the combination with the divalent alkaline earth element and the trivalent Ce element.
- the coefficient x of the M element in the above general formula is 0.52 or more and 0.9 or less, preferably 0.6 or more and 0.9 or less, and more preferably 0.7 or more and 0.9 or less.
- the coefficient x exceeds 0.9, that is, when it approaches a CaAlSiN3 crystal, the fluorescence intensity tends to decrease, and when the coefficient x is smaller than 0.52, a large amount of different phases other than the target crystal phase are generated. The fluorescence intensity tends to decrease significantly.
- y is preferably 0.06 or more and 0.36 or less, more preferably 0.1 or more and 0.35 or less, and further preferably 0.06 or more and 0.23 or less.
- the O / N atomic ratio (molar ratio) is 0 or more and 0.1 or less, preferably 0.01 or more and 0.08 or less, and more preferably 0.02 or more and 0.07 or less. If the O / N atomic ratio is too large, the amount of heterogeneous phase produced increases, the luminous efficiency decreases, the covalent bond of the crystal decreases, and the temperature characteristics tend to deteriorate (luminance decreases at high temperatures).
- the Si / Al atomic ratio is 1.5 or more and 6 or less, preferably 2 or more and 4 or less, and more preferably 2.5 or more and 4 or less.
- the Li content in the phosphor particles is 5 to 50 mol%, preferably 15 to 45 mol%, and more preferably 25 to 45 mol% of the M element.
- the effect of Li is likely to be exhibited at 5 mol% or more, but if it exceeds 50 mol%, the crystal structure of the target phosphor cannot be maintained and a heterogeneous phase is generated, and the luminous efficiency tends to decrease.
- the "Li content” is the Li content in the finally obtained fluorophore powder, not the amount based on the raw material formulation.
- the Li compound used as a raw material has a high vapor pressure and easily volatilizes, and when an attempt is made to synthesize a nitride / oxynitride at a high temperature, a considerable amount of Li compound volatilizes. That is, since the Li content of the raw material compounding base greatly deviates from the content in the final product, it does not mean the Li content in the phosphor.
- the content of Ce which is the emission center of the phosphor particles, tends to be too small, the contribution to emission tends to be small, and if it is too large, the concentration of the phosphor tends to be quenched by energy transfer between Ce 3+ . Therefore, the content of Ce is 0.5 to 10 mol%, preferably 0.5 to 5 mol% of the M element.
- the alkaline earth metal element used as the M element in the above general formula may be any element, but when Ca is used, high fluorescence intensity is obtained and the crystal structure is stabilized in a wide composition range. Therefore, it is preferable that the M element contains Ca.
- the M element may be a combination of a plurality of alkaline earth metal elements, and for example, a part of the Ca element may be replaced with the Sr element.
- the crystal structure of the phosphor particles is an orthorhombic system, and may have the same structure as the CaAlSiN3 crystal described above.
- the range of this lattice constant reflects the constituent elements and composition described above.
- the crystal phase present in the phosphor particles is preferably the above-mentioned crystal single phase.
- the phosphor particles may contain a different phase as long as the fluorescence characteristics are not significantly affected.
- Examples of the heterogeneous phase having a low effect on the fluorescence characteristics in the case of blue light excitation include ⁇ -sialon, AlN, LiSi 2 N 3 , LiAlSi 2 N 4 , and the like.
- the amount of the heterogeneous phase is preferably such that the diffraction line intensity of the other crystal phase is 40% or less with respect to the strongest diffraction line intensity of the crystal phase when evaluated by the powder X-ray diffraction method.
- the fluorophore powder of this embodiment is excited by light in a wide wavelength range from ultraviolet to visible light. For example, when irradiated with blue light having a wavelength of 455 nm, it may exhibit broad fluorescence emission having a peak wavelength of 570 to 610 nm and a half width of the fluorescence spectrum of 125 nm or more.
- a fluorescent substance powder is suitable as a fluorescent substance for a wide range of light emitting devices.
- the fluorescent substance powder of the present embodiment has excellent heat resistance and chemical stability, and the brightness decreases due to a temperature rise, like the conventional nitride / oxynitride-based fluorescent material represented by CaAlSiN 3 . Has small properties. Such properties are particularly suitable for applications where durability is required.
- the diffuse reflectance X1 of the fluorescent powder of the present embodiment with respect to light having a wavelength of 700 nm is 88% or more and 99.9% or less.
- X1 is preferably 90% or more and 99.9% or less, more preferably 92% or more and 99.9% or less, and particularly preferably 95% or more and 99.9% or less.
- the diffuse reflectance X2 of the phosphor powder of the present embodiment with respect to light having a fluorescence peak wavelength is preferably 85% or more and 95% or less, and more preferably 85.5% or more and 92% or less.
- X2 is within such a numerical range, the emission intensity tends to be higher.
- the phosphor is irradiated with light having a fluorescence peak wavelength, not only non-emission absorption due to impurities and crystal defects but also absorption accompanying electron transition of the emission center ion occurs. Therefore, X2 is smaller than X1.
- light absorption near the peak wavelength can be an index of re-excited light emission that causes a decrease in efficiency. That is, it is considered that the moderately large X2 means that the contribution of the excitation light emission is small, and the moderately large X2 further improves the fluorescence characteristics.
- the difference between X2 and X1 is preferably 4% or more and 8% or less, more preferably 4% or more and 7% or less, and particularly preferably 4% or more and 6% or less.
- X2-X1 is 4% or more and 8% or less means that the fluorescence characteristics are improved by increasing the absorption rate when excited by blue light and the fluorescence characteristics are decreased by re-excited emission. It is considered to mean that the balance is good, and thus the characteristics of the phosphor are further improved.
- the volume-based cumulative 50% diameter D50 (so-called median diameter) of the fluorescent powder of the present embodiment measured by the laser diffraction / scattering method is preferably 8 ⁇ m or more and 25 ⁇ m or less, more preferably 10 ⁇ m or more and 20 ⁇ m or less. It is more preferably 12 ⁇ m or more and 20 ⁇ m or less.
- the volume-based cumulative 10 % diameter D10 of the fluorescent powder of the present embodiment measured by the laser diffraction / scattering method is preferably 2 ⁇ m or more and 15 ⁇ m or less, and more preferably 5 ⁇ m or more and 12 ⁇ m or less.
- the relatively large value of D 10 corresponds to a relatively small amount of fine powder (too fine fluorescent particle, which tends to reduce the conversion efficiency of blue light) in the fluorescent powder. Therefore, when D 10 is a large value to some extent, the conversion efficiency of blue light tends to be higher.
- the volume-based cumulative 90% diameter D 90 of the fluorescent powder of the present embodiment measured by the laser diffraction / scattering method is preferably 15 ⁇ m or more and 50 ⁇ m or less, and more preferably 18 ⁇ m or more and 40 ⁇ m or less.
- D 90 is not too large corresponds to the small amount of coarse particles in the fluorophore powder.
- a phosphor powder in which D 90 is not too large is effective in reducing the chromaticity variation of the light emitting device.
- the preferable particle size ( D50 , etc.) of the fluorescent powder of the present embodiment is relatively large, the diffuse reflectance of the fluorescent powder of the present embodiment tends to be relatively large.
- the fluorescent substance powder of the present embodiment is, for example, a series of steps including the following (1) to (4), a series of steps including (1) to (3) and (5), or (1) to (5).
- the step of producing the phosphor powder includes (4) an acid treatment step and / or (5) a classification step (preferably precipitation classification).
- a classification step preferably precipitation classification.
- an appropriate raw material powder is usually mixed to obtain a raw material mixed powder.
- nitrides of constituent elements that is, silicon nitride, aluminum nitride, lithium nitride, cerium nitride, nitrides of alkaline earth elements (for example, calcium nitride) and the like are preferably used.
- the nitride powder is unstable in the air, the particle surface is covered with an oxide layer, and even when a nitride raw material is used, as a result, a certain amount of oxide is contained in the raw material. ing.
- a part of the nitride may be used as an oxide (including a compound which becomes an oxide by heat treatment).
- oxides include cerium oxide and the like.
- lithium compounds are remarkably volatilized by heating, and most of them may volatilize depending on the firing conditions. Therefore, it is preferable to determine the blending amount of the lithium compound in consideration of the volatile amount in the firing process according to the firing conditions.
- nitride raw material powders lithium nitride, cerium nitride, and nitrides of alkaline earth elements react violently with moisture in the air. Therefore, it is preferable to handle these in a glove box substituted with an inert atmosphere.
- a predetermined amount of silicon nitride, aluminum nitride and various oxide raw material powders that can be handled in air are weighed and sufficiently mixed in air in advance to prepare a premixed powder. Then, (ii), it is preferable to prepare a raw material mixed powder by mixing the premixed powder and a substance that easily reacts with water such as lithium nitride in the glove box.
- the raw material mixed powder prepared in the step of preparing the raw material mixed powder (1) is filled in an appropriate container and heated using a baking furnace or the like.
- the firing temperature is preferably 1600 to 2000 ° C., more preferably 1700 to 1900 ° C. from the viewpoint of sufficiently advancing the reaction and suppressing the volatilization of lithium.
- the calcination time is preferably 2 to 24 hours, more preferably 4 to 16 hours, from the viewpoint of sufficiently advancing the reaction and suppressing the volatilization of lithium.
- the firing step is preferably performed in a nitrogen atmosphere. Further, it is preferable to appropriately adjust the pressure of the firing atmosphere. Specifically, the pressure in the firing atmosphere is preferably 0.5 MPa ⁇ G or more. When the firing temperature is particularly 1800 ° C. or higher, the phosphor tends to be easily decomposed, but the high pressure in the firing atmosphere can suppress the decomposition of the phosphor. Incidentally, in consideration of industrial productivity, the pressure in the firing atmosphere is preferably less than 1 MPa ⁇ G.
- the container for filling the raw material mixed powder is preferably made of a material that is stable in a high temperature nitrogen atmosphere and does not react with the raw material mixed powder and its reaction products.
- the material of the container is preferably boron nitride.
- the pulverized product obtained in (3) above is immersed in an acidic aqueous solution.
- acid treatment removes or reduces the "heterogeneous phase" of the fluorophore that does not contribute to light emission or reduces luminous efficiency.
- the fact that the diffuse reflectance X1 of the phosphor powder is 88% or more and 99.9% or less may correspond to the removal or reduction of the heterogeneous phase.
- the acidic aqueous solution examples include an acidic aqueous solution containing one kind of acid selected from acids such as hydrofluoric acid, nitric acid, and hydrochloric acid, and a mixed acid aqueous solution obtained by mixing two or more kinds of the above acids.
- acids such as hydrofluoric acid, nitric acid, and hydrochloric acid
- a mixed acid aqueous solution obtained by mixing two or more kinds of the above acids As the acid, nitric acid or hydrochloric acid is preferable, and hydrochloric acid is more preferable.
- the concentration of the acidic aqueous solution is appropriately set depending on the strength of the acid used, and is, for example, 0.5 to 50% by mass, preferably 1 to 30% by mass, and more preferably 1 to 10% by mass.
- the temperature at which the acid treatment is carried out is preferably 25 ° C. or higher and 90 ° C.
- the acid treatment time is preferably 15 minutes or more and 80 minutes or less, and preferably 15 minutes or more and 60 minutes or less. After the acid treatment, it is preferable to thoroughly wash the fluorescent powder with water and dry it.
- Classification (precipitation classification) step In order to reduce the amount of fine powder (too fine phosphor particles that tend to reduce the conversion efficiency of blue light) in the powder, it is preferable to perform an appropriate classification treatment. In order to effectively remove fine powder, the classification method is preferably settling classification as described below.
- the powder obtained in the crushing step of the fired product or (4) the powder subjected to the acid treatment step is dispersed in a suitable liquid, for example, an aqueous sodium hexametaphosphate solution in a container.
- a suitable liquid for example, an aqueous sodium hexametaphosphate solution in a container.
- the dispersion is allowed to stand for a certain period of time to precipitate powders in the dispersion having a relatively large particle size. After that, the supernatant liquid is discharged.
- a new aqueous solution of sodium hexametaphosphate is placed in the container in which the precipitate remains, the phosphor is dispersed, the mixture is allowed to stand, and the supernatant liquid is discharged.
- the operation is repeated a plurality of times.
- “Multiple times" is preferably 5 times or more. There is no particular upper limit on the number of times, but from the viewpoint of cost and the like, it is, for example, 15 times or less,
- the fact that the diffuse reflectance X1 of the phosphor powder is 88% or more and 99.9% or less may correspond to the fact that the amount of fine powder in the phosphor powder is small.
- the specific conditions for classification are not particularly limited as long as a phosphor powder having a diffuse reflectance X1 of 88% or more and 99.9% or less can be finally obtained. Although it is only a guide, it is preferable to set the classification conditions so that fine powder having a particle size of 10 ⁇ m or less is removed, and it is more preferable to set the classification conditions so that fine powder having a particle size of 7.5 ⁇ m or less is removed. ..
- Stokes' equation regarding the sedimentation velocity of particles can be referred to.
- a light emitting device can be obtained by combining the phosphor powder of the present embodiment with a light emitting light source.
- the luminescent light source typically emits ultraviolet light or visible light.
- the light emitting source is a blue LED
- the blue light emitted from the light emitting light source hits the phosphor powder, and the blue light is converted into light having a longer wavelength.
- the fluorescent substance powder of the present embodiment can be used as a wavelength conversion material for converting blue light into light having a longer wavelength.
- FIG. 1 is a schematic cross-sectional view showing an example of the structure of a light emitting device.
- the light emitting device 100 includes a light emitting element 120, a heat sink 130, a case 140, a first lead frame 150, a second lead frame 160, a bonding wire 170, a bonding wire 172, and a complex 40.
- the light emitting element 120 is mounted in a predetermined area on the upper surface of the heat sink 130. By mounting the light emitting element 120 on the heat sink 130, the heat dissipation of the light emitting element 120 can be improved.
- a package substrate may be used instead of the heat sink 130.
- the light emitting element 120 is a semiconductor element that emits excitation light.
- the light emitting element 120 for example, an LED chip that generates light having a wavelength of 300 nm or more and 500 nm or less, which corresponds to blue light from near-ultraviolet light, can be used.
- One electrode (not shown) arranged on the upper surface side of the light emitting element 120 is connected to the surface of the first lead frame 150 via a bonding wire 170 such as a gold wire.
- the other electrode (not shown) formed on the upper surface of the light emitting element 120 is connected to the surface of the second lead frame 160 via a bonding wire 172 such as a gold wire.
- the case 140 is formed with a substantially funnel-shaped recess whose hole diameter gradually increases upward from the bottom surface.
- the light emitting element 120 is provided on the bottom surface of the recess.
- the wall surface of the recess surrounding the light emitting element 120 serves as a reflector.
- the complex 40 is filled in the recess where the wall surface is formed by the case 140.
- the complex 40 is a wavelength conversion member that converts the excitation light emitted from the light emitting element 120 into light having a longer wavelength.
- the complex 40 is obtained by dispersing at least the fluorescent powder of the present embodiment in a sealing material 30 such as a resin. In order to obtain higher quality white light, the encapsulant 30 may contain not only the fluorescent powder of the present embodiment but also other fluorescent powder.
- the light emitting device 100 emits a mixed color of the light of the light emitting element 120 and the light emitted from the phosphor particles 1 excited by absorbing the light emitted from the light emitting element 120.
- the light emitting device 100 preferably emits white light by mixing the light of the light emitting element 120 and the light generated from the phosphor particles 1.
- a surface mount type light emitting device is illustrated, but the light emitting device is not limited to the surface mount type, and is a cannonball type, a COB (chip on board) type, or a CSP (chip scale package) type. You may.
- the usage of the light emitting device examples include an image display device such as a display and a lighting device.
- a liquid crystal display can be manufactured by using the light emitting device 100 as a backlight.
- a lighting device by using one or a plurality of light emitting devices 100 and providing appropriate wiring.
- Example 1 ⁇ Manufacturing of fluorescent powder> (Example 1)
- premixing was performed. Specifically, among the raw materials shown in Table 1, Si 3N 4 , AlN and CeO 2 are mixed (dry blended) for 30 minutes using a small V-type mixer, and then made of nylon having an opening of 150 ⁇ m. It was sieved with the sieve of. This gave a premixed powder.
- the rest of the raw materials (Ca 3 N 2 and Li 3 N) shown in Table 1 are added to the premixed powder, and the mixture is sufficiently dry-blended, and then a sieve having an opening of 500 ⁇ m is added. It was sieved with. As a result, a raw material mixed powder was obtained.
- the pulverized calcined product was put into hydrochloric acid and treated with acid. Specifically, first, 35 to 37% by mass hydrochloric acid and distilled water were mixed at a volume ratio of 50 mL: 300 mL to prepare an aqueous hydrochloric acid solution heated to 80 ° C. The calcined product pulverized in (3) was added to this aqueous hydrochloric acid solution, and the mixture was stirred for 0.5 hours for acid treatment. The acid-treated calcined product was thoroughly washed with distilled water and then dried at 110 ° C. for 3 hours. Then, coarse / aggregated particles were removed by passing through a sieve having an opening of 45 ⁇ m.
- a 0.05 mass% sodium hexametaphosphate aqueous solution was prepared. Then, this aqueous solution was put into a container having an inner diameter of 70 mm and a height of 120 mm up to a height of 110 mm. Next, the acid-treated calcined product was put into a container containing the above aqueous solution, sufficiently stirred and dispersed, and then allowed to stand for 22 minutes. After standing, the supernatant liquid was discharged 90 mm from the top. Then, an aqueous sodium hexametaphosphate solution was added to a height of 110 mm, and the powder was dispersed again by stirring to perform the same treatment.
- Example 2 A fluorescent powder was obtained in the same manner as in Example 1 except that precipitation classification was not performed.
- Example 3 (A) The raw materials shown in Table 1 were used. (B) No acid treatment was performed (the calcined product crushed by a jet mill was subjected to sedimentation classification without undergoing acid treatment). A phosphor powder was obtained in the same manner as in Example 1 except that (c) the pulverized air pressure in jet mill pulverization was set to 0.6 MPa.
- Example 4 A fluorescent powder was obtained in the same manner as in Example 1 except that (a) the raw materials shown in Table 1 were used and (b) precipitation classification was not performed.
- Example 5 For the acid treatment, a fluorescent substance powder was obtained in the same manner as in Example 4 except that nitric acid having a concentration of 60% by mass was used instead of hydrochloric acid.
- Example 6 (A) The raw materials shown in Table 1 were used, and (b) the acid treatment was not performed (the fired product crushed by the jet mill was subjected to precipitation classification without undergoing acid treatment. A fluorescent powder was obtained in the same manner as in Example 1 except for the above.
- Example 7 (A) The raw materials shown in Table 1 were used, and (b) the acid treatment was not performed (the calcined product crushed by a jet mill was subjected to sedimentation classification without undergoing acid treatment. ) And (c) The calcined product crushed by a jet mill was passed through a sieve having an opening of 45 ⁇ m to remove coarse / aggregated particles, and then subjected to sedimentation classification. Similarly, a phosphor powder was obtained.
- Example 8 (A) The raw materials shown in Table 1 were used, and (b) the acid treatment was not performed (the calcined product crushed by a jet mill was subjected to sedimentation classification without undergoing acid treatment. ), (C) The pulverized air pressure in jet mill pulverization was set to 0.4 MPa, and (d) the calcined product pulverized by the jet mill was passed through a sieve having an opening of 45 ⁇ m to obtain coarse / aggregated particles. A phosphor powder was obtained in the same manner as in Example 1 except that the particles were removed and subjected to sedimentation classification.
- composition of some fluorescent powders was analyzed as follows. Amounts of Ca, Li, Ce, Si and Al: The phosphor powder was dissolved by an alkaline melting method, and then measured by an ICP emission spectrophotometer (CIROS-120 manufactured by Rigaku Co., Ltd.). Amount of O and N: Measured by an oxygen-nitrogen analyzer (EMGA-920, manufactured by HORIBA). Based on the measurement results, x, y, Si / Al atomic ratio, O / N atomic ratio, Li ratio of M, and Ce of M in the general formula M x (Si, Al) 2 (N, O) 3 ⁇ y . The ratio was calculated.
- the phosphor powder was dissolved by a pressurized acid decomposition method with a mixed acid of hydrofluoric acid and nitric acid, and then measured by an ICP emission spectroscopic analyzer.
- the chemical composition of the fluorescent powders of Examples 4 and 5 has not been measured.
- the manufacturing process up to crushing the fired product is the same in Examples 3 and 4 and 5, and the composition of the raw material mixed powders in Examples 4 and 5 is the same as in Example 3.
- the production procedure differs between Example 3 and Examples 4 and 5, it is unlikely that the difference has a great influence on the chemical composition. Therefore, the measurement of the chemical composition of the fluorescent powders of Examples 4 and 5 was omitted.
- the chemical composition of the fluorescent powder of Example 8 is similar to that of Example 7. Further, although the production procedure differs between Examples 7 and 8, it is unlikely that the difference has a great influence on the chemical composition. Therefore, the measurement of the chemical composition of the fluorescent substance powder of Example 8 was omitted.
- the diffuse reflectance was measured using a device in which an integrating sphere device (ISV-469) was attached to an ultraviolet visible spectrophotometer (V-550) manufactured by JASCO Corporation. At the time of measurement, baseline correction was performed with a standard reflector (Spectralon). A solid sample holder filled with a fluorescent substance powder is attached to a predetermined position in the apparatus, and the diffuse reflection spectrum is measured in the wavelength range of 500 to 850 nm, and the light having a wavelength of 700 nm and the light having the fluorescence peak wavelength of the fluorescent substance powder are measured. The diffuse reflectance for (described later) was determined.
- the particle size distribution was measured by a laser diffraction / scattering method based on JIS R 1629: 1997 using LS13 320 (manufactured by Beckman Coulter, Inc.). Water was used as the measurement solvent.
- a small amount of the fluorescent substance powder was added to an aqueous solution containing 0.05% by mass of sodium hexametaphosphate as a dispersant.
- a dispersion treatment was performed with a horn-type ultrasonic homogenizer (output 300 W, horn diameter 26 mm) to prepare a dispersion liquid. An appropriate amount of this dispersion was added to the measuring solvent, and the particle size distribution was measured. From the obtained cumulative volume frequency distribution curve, 10% volume diameter (D 10 ), 50% volume diameter (D 50 ), and 90% volume diameter (D 90 ) were determined.
- the fluorescence spectrum of the phosphor powder was measured using a spectral fluorometer (F-7000, manufactured by Hitachi High-Tech Science Co., Ltd.) corrected with Rhodamine B and a substandard light source. Specifically, the spectrum of fluorescence emitted by exciting the phosphor powder with monochromatic light having a wavelength of 455 nm was measured, and the fluorescence peak intensity and the fluorescence peak wavelength were obtained.
- the fluorescence peak intensity varies depending on the measuring device and conditions.
- the fluorescence peak intensity shown in the table below is a value when the fluorescence peak intensity of the standard sample (YAG, more specifically, P46Y3 manufactured by Mitsubishi Chemical Corporation) is set to 100.
- This monochromatic light (excitation light) was applied to the phosphor powder filled in the recessed portion of the concave cell, and the fluorescence spectrum was measured. From the obtained spectral data, the peak wavelength was obtained, and the number of excited reflected photons (Qref) and the number of fluorescent photons (Qem) were calculated. The number of excited reflected photons was calculated in the wavelength range of 450 nm or more and 465 nm or less, and the number of fluorescent photons was calculated in the range of 465 nm or more and 800 nm or less.
- Table 1 summarizes various types of information.
- ND is an abbreviation for Not Directed.
- each raw material described in the column of "raw materials used" in Table 1 is as follows.
- Ca 3 N 2-1 Ca 3 N 2 manufactured by Taiheiyo Cement Co., Ltd.
- Ca 3 N 2 -2 Ca 3 N 2 manufactured by CERAC (currently Matterion)
- Li 3 N-1 Li 3 N manufactured by Materion Japan Ltd.
- Li 3 N-2 Li 3 N manufactured by CERAC (currently Matterion)
- Li 3 N-3 Li 3 N manufactured by High Purity Chemistry Laboratory
- CeO 2-1 CeO 2 manufactured by Shin-Etsu Chemical Co., Ltd., C grade
- Si 3 N 4-1 Si 3 N 4 , E10 grade manufactured by Ube Corporation
- AlN-1 Tokuyama AlN, E grade
- the fluorophore particles represented by the general formula M x (Si, Al) 2 (N, O) 3 ⁇ y are contained, and the diffuse reflectance X1 is 88% or more and 99.9% or less.
- the fluorescent powders (Examples 1 to 8) showed good fluorescence peak intensity, internal quantum efficiency and external quantum efficiency.
- the phosphor powder having a diffuse reflectance X1 of less than 88% (Comparative Example 1) was inferior to Examples 1 to 8 in at least the internal quantum efficiency.
- Fluorescent particle 30 Encapsulant 40 Complex 100 Light emitting device 120 Light emitting element 130 Heat sink 140 Case 150 First lead frame 160 Second lead frame 170 Bonding wire 172 Bonding wire
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Abstract
Description
照明用途での白色LEDの普及や、画像表示装置への白色LEDの適用検討などに伴い、青色光をより長波長の光に変換可能な蛍光体の開発が継続されている。
例えば、特許文献1には、一般式Mx(Si,Al)2(N,O)3±y(ただし、MはLi及び一種以上のアルカリ土類金属元素であり、0.52≦x≦0.9、0.06≦y≦0.23)で示され、Mの一部がCe元素で置換されている蛍光体であって、Si/Al原子比が1.5以上6以下であり、かつO/N原子比が0以上0.1以下であり、Mの5~50mol%がLiであり、Mの0.5~10mol%がCeである蛍光体が記載されている。
一般式Mx(Si,Al)2(N,O)3±y(ただし、MはLi及び一種以上のアルカリ土類金属元素であり、0.52≦x≦0.9、0.06≦y≦0.36)で示され、Mの一部がCe元素で置換されている蛍光体であって、Si/Al原子比が1.5以上6以下であり、かつO/N原子比が0以上0.1以下であり、Mの5~50mol%がLiであり、Mの0.5~10mol%がCeである蛍光体粒子を含む蛍光体粉末であって、
波長700nmの光に対する拡散反射率X1が、88%以上99.9%以下である蛍光体粉末
が提供される。
上記の蛍光体粉末と、発光光源とを備える発光装置
が提供される。
上記の発光装置を備える画像表示装置
が提供される。
上記の発光装置を備える照明装置
が提供される。
図面において、同様な構成要素には同様の符号を付し、適宜説明を省略する。
図面はあくまで説明用のものである。図面中の各部材の形状や寸法比などは、必ずしも現実の物品と対応しない。
本実施形態の蛍光体粉末は、一般式Mx(Si,Al)2(N,O)3±yで表される蛍光体粒子を含む。この一般式において、MはLi及び一種以上のアルカリ土類金属元素、0.52≦x≦0.9、0.06≦y≦0.36である。また、Mの一部はCe元素で置換されており、Si/Al原子比は1.5以上6以下であり、O/N原子比は0以上0.1以下であり、Mの5~50mol%はLiであり、Mの0.5~10mol%はCeである。
また、本実施形態の蛍光体粉末の、波長700nmの光に対する拡散反射率X1は、88%以上99.9%以下である。
本発明者らは、上記の光吸収の影響を定量的に評価するため、一般式Mx(Si,Al)2(N,O)3±yで表される様々な蛍光体を新たに試作し、拡散反射率を測定した。その結果、波長700nmの拡散反射率X1が大きいときに、内部量子効率が高くなる傾向があることを知見した。この知見に基づき、本発明者らは、一般式Mx(Si,Al)2(N,O)3±yで表される蛍光体を含み、かつ、X1が88%以上99.9%以下である蛍光体粉末を新たに作製した。そして本発明者は、蛍光体粉末の、内部量子効率を高めることに成功した。
蛍光体結晶の骨格構造は、(Si,Al)-(N,O)4正四面体が結合することにより構成されており、その間隙にM元素が位置するものである。上記一般式の組成は、M元素の価数と量、Si/Al比、N/O比のパラメータの全体により電気的中性が保たれる幅広い範囲で成立する。上記一般式で示される代表的な蛍光体として、M元素がCaでx=1、更にSi/Al=1、O/N=0となるCaAlSiN3がある。CaAlSiN3のCaの一部がEuで置換された場合には赤色蛍光体に、Ceで置換された場合には黄~橙色蛍光体になる。
上記一般式において、M元素はLi元素とアルカリ土類金属元素の組み合わせであり、その一部が発光中心となるCe元素で置換されている。Li元素を用いることにより、二価のアルカリ土類元素及び三価のCe元素との組み合わせにより、M元素の平均価数を幅広く制御できる。また、Li+のイオン半径は非常に小さく、その量により結晶サイズを大きく変化させることができ、多様な蛍光発光が得られる。
上記一般式におけるM元素の係数xは、0.52以上0.9以下、好ましくは0.6以上0.9以下、より好ましくは0.7以上0.9以下である。係数xが0.9を越える、つまりCaAlSiN3結晶に近づくと蛍光強度が低下する傾向にあり、係数xが0.52よりも小さいと、目的とする結晶相以外の異相が多量に生成するために蛍光強度が著しく低下する傾向がある。
念のため述べておくと、「Li含有量」とは、最終的に得られる蛍光体粉末中のLi含有量であり、原料配合ベースの量ではない。原料に使用するLi化合物は蒸気圧が高く揮発しやすく、高温で窒化物・酸窒化物を合成しようとした場合、相当な量が揮発する。つまり、原料配合ベースのLi量は最終生成物中の含有量とは大きく乖離しているので、蛍光体中のLi含有量を意味しない。
既に述べたように、本実施形態の蛍光体粉末の、波長700nmの光に対する拡散反射率X1は、88%以上99.9%以下である。X1は、好ましくは90%以上99.9%以下、さらに好ましくは92%以上99.9%以下、特に好ましくは95%以上99.9%以下である。
本実施形態の蛍光体粉末の粒径分布を適切に設計することで、量子効率をより高めたり、諸性能のバランスを高めたりすることができる場合がある。
具体的には、本実施形態の蛍光体粉末の、レーザ回折散乱法で測定される体積基準累積50%径D50(いわゆるメジアン径)は、好ましくは8μm以上25μm以下、より好ましくは10μm以上20μm以下、さらに好ましくは12μm以上20μm以下である。
本実施形態の蛍光体粉末は、例えば、以下の(1)~(4)を含む一連の工程、(1)~(3)および(5)を含む一連の工程、または(1)~(5)を含む一連の工程により製造可能である。蛍光体粉末の拡散反射率を適切に調整する観点で、蛍光体粉末の製造工程は、(4)酸処理工程および/または(5)分級工程(好ましくは沈降分級)を含むことが好ましい。
(1)原料混合粉の調製工程
(2)焼成工程
(3)焼成物の粉砕工程
(4)酸処理工程
(5)分級工程(好ましくは沈降分級)
原料混合粉の調製工程においては、通常、適当な原料粉末を混合して、原料混合粉を得る。
原料粉末としては、構成元素の窒化物、即ち窒化ケイ素、窒化アルミニウム、窒化リチウム、窒化セリウム、アルカリ土類元素の窒化物(例えば窒化カルシウム)などが好適に使用される。一般的に、窒化物粉末は空気中では不安定であり、粒子表面が酸化物層で覆われており、窒化物原料を使用した場合でも、結果的に、ある程度の酸化物が原料に含まれている。蛍光体のO/N比を制御する場合、これらを考慮するとともに、酸素が不足する場合は、窒化物の一部を酸化物(加熱処理により酸化物になる化合物を含む)としてもよい。酸化物の例としては、酸化セリウムなどを上げることができる。
作業の効率性の観点から、(i)まず、空気中で取り扱い可能な窒化ケイ素、窒化アルミニウム及び各種酸化物原料粉末を所定量秤量し、予め空気中で十分に混合して予備混合粉を調製し、(ii)その後、グローブボックス内で、予備混合粉と、窒化リチウム等の水分と反応しやすい物質とを混合して、原料混合粉を調製することが好ましい。
焼成工程では、(1)原料混合粉の調製工程で調製した原料混合粉を、適当な容器に充填して、焼成炉などを用いて加熱する。
焼成時間は、反応を十分に進める観点と、リチウムの揮発を抑える観点から、2~24時間が好ましく、4~16時間がより好ましい。
ちなみに、工業的生産性を考慮すると、焼成雰囲気の圧力は1MPa・G未満が好ましい。
(2)で得られる焼成物は、通常、塊状であるため、機械的に力を加えることである程度小さいサイズに粉砕することが好ましい。
粉砕には、クラッシャー、乳鉢、ボールミル、振動ミル、ジェットミル、スタンプミル等の各種装置を用いることができる。これら装置のうち2つ以上を組み合わせて粉砕してもよい。後掲の実施例においては、まずスタンプミルを用いて焼成物の粗粉砕物を得、その後、その粗粉砕物を、ジェットミルを用いてより細かく粉砕している。詳細は不明であるが、このような粉砕を行うことにより、拡散反射率X1が88%以上99.9%以下である蛍光体粉末を得やすい。
酸処理工程では、例えば、酸性水溶液中に、上記(3)で得られた粉砕物を浸漬する。詳細は不明であるが、酸処理により、蛍光体の、発光に寄与しないまたは発光効率を下げる「異相」が除去または低減されると考えらえる。ちなみに、前述のとおり、蛍光体粉末の拡散反射率X1が88%以上99.9%以下であるということは、異相が除去または低減されたことに対応する可能性がある。
酸性水溶液の濃度は、用いる酸の強さによって適宜設定されるが、例えば0.5~50質量%、好ましくは1~30質量%、より好ましくは1~10質量%である。
酸処理を実施する際の温度は、25℃以上90℃以下が好ましく、60℃以上90℃以下がより好ましい。比較的高温で処理することにより、拡散反射率X1が88%以上99.9%以下である蛍光体粉末を得やすい。
酸処理の時間(浸漬時間)は、15分以上80分以下が好ましく、15分以上60分以下が好ましい。
酸処理の後には、蛍光体粉末を十分に水洗し、乾燥させることが好ましい。
粉末中の微粉(青色光の変換効率を下げる傾向がある、微細すぎる蛍光体粒子)の量を低減するため、適切な分級処理を行うことが好ましい。効果的に微粉を除去するため、分級の方法は、以下に説明するような沈降分級であることが好ましい。
次に、その分散液を一定時間静置して、分散液中の粉末のうち、粒径が比較的大きいものを沈殿させる。
その後、上澄み液を排出する。
さらにその後、沈殿物が残った容器内に、新たにヘキサメタリン酸ナトリウム水溶液を入れ、蛍光体を分散し、静置し、上澄み液を排出する操作を複数回繰り返す。「複数回」とは、好ましくは5回以上である。回数の上限は特にないが、コスト等の観点から、例えば15回以下、具体的には10回以下である。
本実施形態の蛍光体粉末と、発光光源とを組み合わせることで、発光装置を得ることができる。
発光光源は、典型的には紫外線又は可視光を発光する。例えば、発光光源が青色LEDである場合、発光光源から発せられる青色光が蛍光体粉末に当たり、そして青色光はより長波長の光に変換される。すなわち、本実施形態の蛍光体粉末は、青色光をより長波長の光に変換する波長変換材料として使用可能である。
図1は、発光装置の構造の一例を示す概略断面図である。図1に示されるように、発光装置100は、発光素子120、ヒートシンク130、ケース140、第1リードフレーム150、第2リードフレーム160、ボンディングワイヤ170、ボンディングワイヤ172および複合体40を備える。
複合体40は、樹脂などの封止材30中に、少なくとも本実施形態の蛍光体粉末が分散したものである。より品質の高い白色光を得るため、封止材30は、本実施形態の蛍光体粉末だけでなく、その他の蛍光体粉末を含んでもよい。
発光装置100は、発光素子120の光と、発光素子120から発せられる光を吸収して励起される蛍光体粒子1から発せられる光との混合色を発する。発光装置100は、発光素子120の光と蛍光体粒子1から発生する光との混色により白色を発光することが好ましい。
(実施例1)
(1)原料混合粉の調製
まず、予備混合を行った。具体的には、表1に記載の原料のうち、Si3N4,AlNおよびCeO2を、小型V型混合機を用いて30分間混合(ドライブレンド)し、その後、目開き150μmのナイロン製の篩で通篩した。これにより予備混合粉を得た。
次に、窒素雰囲気のグローブボックス内で、予備混合粉に、表1に記載の原料の残り(Ca3N2およびLi3N)を加え、十分にドライブレンドし、その後、目開き500μmの篩で通篩した。これにより原料混合粉を得た。
原料混合粉を窒化ホウ素製の容器に充填した。この容器を炉に入れ、原料混合粉を、0.72MPa・GのN2雰囲気下、1800℃で8時間焼成した。
(2)で得られた焼成物を、スタンプミルを用いて粉砕した。スタンプミルによる粉砕は、目開き250μmの振動篩の通過率が90%を超えるまで繰り返した。
スタンプミルによる粉砕を経た焼成物を、さらに、ジェットミル(日本ニューマチック工業製、PJM-80SP)を用いて粉砕した。粉砕条件は、試料供給速度:50g/min、粉砕エア圧:0.3MPaとした。
粉砕された焼成物を、塩酸中に投入して酸処理した。
具体的には、まず、35~37質量%塩酸と、蒸留水とを、体積比で50mL:300mLで混合し、80℃に熱した塩酸水溶液を準備した。この塩酸水溶液に、(3)で粉砕された焼成物を投入し、0.5時間攪拌して酸処理した。
酸処理された焼成物を、蒸留水で十分に洗浄し、その後、110℃で3h乾燥させた。そして、目開き45μmの篩を通過させて、粗大/凝集粒子を除いた。
まず、0.05質量%ヘキサメタリン酸ナトリウム水溶液を調製した。そして、この水溶液を内径70mm、高さ120mmの容器に高さ110mmまで入れた。
次に、上記の水溶液を入れた容器内に、酸処理された焼成物を投入し、十分に攪拌し分散させ、その後22分間静置した。静置後、上澄み液を上から90mm分排出した。その後、ヘキサメタリン酸ナトリウム水溶液を高さ110mmまで入れ、再び粉末を攪拌により分散させて同様の処理を行った。この操作を7回繰り返し、酸処理粉末に含まれる微粉を除いた(ちなみに、ストークスの式に基づけば、分級点は7.5μmである。)
その後、容器底部のスラリーを水洗しながら濾過を行い、固形分を回収し、それを110℃、3時間の条件で乾燥し、目開き45μmの篩を通過させて、凝集粒子を解砕した。
以上により、蛍光体粉末を得た。
沈降分級を行わなかった以外は、実施例1と同様にして、蛍光体粉末を得た。
(a)原料として表1に記載のものを用いたこと(b)酸処理を行わなかったこと(ジェットミルで粉砕された焼成物を、酸処理を経ずに、沈降分級に供したこと)、および、(c)ジェットミル粉砕における粉砕エア圧を0.6MPaとしたこと以外は、実施例1と同様にして、蛍光体粉末を得た。
(a)原料として表1に記載のものを用いたこと、および、(b)沈降分級を行わなかったこと以外は、実施例1と同様にして、蛍光体粉末を得た。
酸処理について、塩酸に代えて、濃度60質量%の硝酸を用いた以外は、実施例4と同様にして、蛍光体粉末を得た。
(a)原料として表1に記載のものを用いたこと、および、(b)酸処理を行わなかったこと(ジェットミルで粉砕された焼成物を、酸処理を経ずに、沈降分級に供したこと)以外は、実施例1と同様にして、蛍光体粉末を得た。
(a)原料として表1に記載のものを用いたこと、および、(b)酸処理を行わなかった以外は、実施例4と同様にして、蛍光体粉末を得た。
(a)原料として表1に記載のものを用いたこと、(b)酸処理を行わなかったこと(ジェットミルで粉砕された焼成物を、酸処理を経ずに、沈降分級に供したこと)、および、(c)ジェットミルで粉砕された焼成物を、目開き45μmの篩を通過させて、粗大/凝集粒子を除去したうえで、沈降分級に供したこと以外は、実施例1と同様にして、蛍光体粉末を得た。
(a)原料として表1に記載のものを用いたこと、(b)酸処理を行わなかったこと(ジェットミルで粉砕された焼成物を、酸処理を経ずに、沈降分級に供したこと)、(c)ジェットミル粉砕における粉砕エア圧を0.4MPaとしたこと、および、(d)ジェットミルで粉砕された焼成物を、目開き45μmの篩を通過させて、粗大/凝集粒子を除去したうえで、沈降分級に供したこと以外は、実施例1と同様にして、蛍光体粉末を得た。
一部の蛍光体粉末ついて、以下のように組成を分析した。
Ca、Li、Ce、SiおよびAlの量:アルカリ融解法により蛍光体粉末を溶解させ、その後、ICP発光分光分析装置(株式会社リガク製CIROS-120)により測定した。
OおよびNの量:酸素窒素分析装置(HORIBA社製、EMGA-920)により測定した。
測定結果に基づき、一般式Mx(Si,Al)2(N,O)3±yにおけるx、y、Si/Al原子比、O/N原子比、MのLi比率、および、MのCe比率を求めた。
また、不純物であるCr元素とFe元素については、フッ化水素酸と硝酸の混酸で加圧酸分解法により蛍光体粉末を溶解させ、その後、ICP発光分光分析装置により測定した。
同様に、実施例8の蛍光体粉末の化学組成は、実施例7と類似する。また、実施例7と8との間で、製造手順は相違するものの、その相違は化学組成に大きな影響を及ぼすとは考え難い。よって、実施例8の蛍光体粉末の化学組成の測定は省略した。
拡散反射率は、日本分光社製紫外可視分光光度計(V-550)に積分球装置(ISV-469)を取り付けた装置を用いて測定した。測定に際しては、標準反射板(スペクトラロン)でベースライン補正を行った。
蛍光体粉末を充填した固体試料ホルダーを装置内の所定の位置に取り付けて、500~850nmの波長範囲で拡散反射スペクトルを測定し、波長700nmの光、および、蛍光体粉末の蛍光ピーク波長の光(後述)に対する拡散反射率を求めた。
粒径分布は、LS13 320(ベックマン・コールター株式会社製)を用い、JIS R 1629:1997に準拠したレーザ回折散乱法により測定した。測定溶媒には水を使用した。
具体的な手順として、まず、分散剤としてヘキサメタリン酸ナトリウムを0.05質量%加えた水溶液に少量の蛍光体粉末を投入した。次に、ホーン式の超音波ホモジナイザー(出力300W、ホーン径26mm)で分散処理を行って分散液を作製した。この分散液を測定溶媒に適量添加して粒径分布を測定した。得られた累積体積頻度分布曲線から、10%体積径(D10)、50%体積径(D50)および90%体積径(D90)を求めた。
(蛍光ピーク強度)
ローダミンBと副標準光源で補正を行った分光蛍光光度計(日立ハイテクサイエンス社製、F-7000)を用いて、蛍光体粉末の蛍光スペクトルを測定した。具体的には、波長455nmの単色光で蛍光体粉末を励起させることにより発せられる蛍光のスペクトルを測定し、蛍光ピーク強度および蛍光ピーク波長を求めた。
蛍光ピーク強度は測定装置や条件によって変化する。後掲の表に記載の蛍光ピーク強度は、標準試料(YAG、より具体的には三菱ケミカル社製P46Y3)の蛍光ピーク強度を100としたときの値である。
分光光度計(大塚電子株式会社製MCPD-7000)を用い、各蛍光体粉末の内部量子効率および外部量子効率を、以下の手順で求めた。
(1)蛍光体粉末を、凹型セルの窪み部分に、表面が平滑になるように充填した。この凹型セルを、積分球内の所定の位置(試料部)に取り付けた。この積分球に、発光光源(Xeランプ)から455nmの波長に分光した単色光を、光ファイバーを用いて導入した。この単色光(励起光)を、凹型セルの窪み部分に充填された蛍光体粉末に照射し、蛍光スペクトルを測定した。得られたスペクトルデータから、ピーク波長を求め、また、励起反射光フォトン数(Qref)及び蛍光フォトン数(Qem)を算出した。励起反射光フォトン数は450nm以上465nm以下の波長範囲で蛍光フォトン数は、465nm以上800nm以下の範囲で算出した。
(2)また、試料部に、凹型セルの代わりに、反射率が99%の標準反射板(Labsphere社製スペクトラロン)を取り付けて、波長455nmの励起光のスペクトルを測定した。そして、450nm以上465nm以下の波長範囲のスペクトルから励起光フォトン数(Qex)を算出した。
(3)上記(1)および(2)で求めたQref、QemおよびQexから、以下式に基づき内部量子効率および外部量子効率を算出した。
内部量子効率=(Qem/(Qex-Qref))×100
外部量子効率=(Qem/Qex)×100
表1中、「N.D.」はNot Detectedの略である。
Ca3N2-2:CERAC社(現:Materion社)製のCa3N2
Li3N-2:CERAC社(現:Materion社)製のLi3N
Li3N-3:高純度化学研究所製のLi3N
一方、拡散反射率X1が88%未満である蛍光体粉末(比較例1)は、少なくとも内部量子効率において、実施例1~8に劣っていた。
30 封止材
40 複合体
100 発光装置
120 発光素子
130 ヒートシンク
140 ケース
150 第1リードフレーム
160 第2リードフレーム
170 ボンディングワイヤ
172 ボンディングワイヤ
Claims (8)
- 一般式Mx(Si,Al)2(N,O)3±y(ただし、MはLi及び一種以上のアルカリ土類金属元素であり、0.52≦x≦0.9、0.06≦y≦0.36)で示され、Mの一部がCe元素で置換されている蛍光体であって、Si/Al原子比が1.5以上6以下であり、かつO/N原子比が0以上0.1以下であり、Mの5~50mol%がLiであり、Mの0.5~10mol%がCeである蛍光体粒子を含む蛍光体粉末であって、
波長700nmの光に対する拡散反射率X1が、88%以上99.9%以下である蛍光体粉末。 - 請求項1に記載の蛍光体粉末であって、
当該蛍光体粉末の蛍光ピーク波長の光に対する拡散反射率X2が、85%以上95%以下である蛍光体粉末。 - 請求項1または2に記載の蛍光体粉末であって、
波長700nmの光に対する拡散反射率X1と、蛍光ピーク波長の光に対する拡散反射率X2との差X1-X2が、4%以上8%以下である蛍光体粉末。 - 請求項1~3のいずれか1項に記載の蛍光体粉末であって、
レーザ回折散乱法で測定される体積基準累積50%径D50が、8μm以上25μm以下である蛍光体粉末。 - 請求項1~4のいずれか1項に記載の蛍光体粉末と、発光光源とを備える発光装置。
- 請求項5に記載の発光装置であって、
発光光源が紫外線又は可視光を発光する発光装置。 - 請求項5または6に記載の発光装置を備える画像表示装置。
- 請求項5または6に記載の発光装置を備える照明装置。
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