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WO2023176564A1 - Poudre de phosphore, procédé de production de poudre de phosphore et dispositif électroluminescent - Google Patents

Poudre de phosphore, procédé de production de poudre de phosphore et dispositif électroluminescent Download PDF

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Publication number
WO2023176564A1
WO2023176564A1 PCT/JP2023/008420 JP2023008420W WO2023176564A1 WO 2023176564 A1 WO2023176564 A1 WO 2023176564A1 JP 2023008420 W JP2023008420 W JP 2023008420W WO 2023176564 A1 WO2023176564 A1 WO 2023176564A1
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phosphor powder
phosphor
europium
wavelength
light
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PCT/JP2023/008420
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English (en)
Japanese (ja)
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萌子 田中
智宏 野見山
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デンカ株式会社
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Priority to KR1020247032645A priority Critical patent/KR20240154072A/ko
Priority to JP2024507772A priority patent/JPWO2023176564A1/ja
Publication of WO2023176564A1 publication Critical patent/WO2023176564A1/fr

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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
    • C09K11/7728—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
    • 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
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

Definitions

  • the present disclosure relates to a phosphor powder, a method for manufacturing the phosphor powder, and a light emitting device.
  • Light-emitting devices having light-emitting elements are used in general lighting, backlights for liquid crystal displays, LED displays, and the like.
  • a light emitting element is used that has a light emitting element that emits blue light and a wavelength converter that absorbs primary light from the light emitting element and emits light of a different wavelength.
  • the wavelength converter for example, various phosphors such as red phosphor and green phosphor are used.
  • CASN-based phosphors such as CASN phosphor and SCASN phosphor are known (for example, Patent Document 1). These CASN-based phosphors are generally synthesized by heating raw material powder containing europium oxide or europium nitride, calcium nitride, silicon nitride, and aluminum nitride.
  • phosphors that have emission peak wavelengths in their respective wavelength ranges and exhibit sufficient emission intensity as the green phosphor and red phosphor.
  • the above method is used. It is required to increase the color gamut of the cured resin layer.
  • red phosphors As the emission spectrum of the phosphor shifts to a longer wavelength region and the reddish color deepens, the overlap with the human visibility curve decreases, so the brightness tends to be insufficient. In other words, red phosphors have characteristics that make it difficult to achieve both redness and brightness in order to improve the color rendering of a light-emitting device using the red phosphor.
  • the main crystal phase has the same crystal structure as CaAlSiN 3 and has the general formula: (Sr 1-xy , Ca x , Eu y )AlSi(N,O) 3 [in the general formula , x and y satisfy 0.0100 ⁇ x ⁇ 0.0300 and 0.0500 ⁇ y ⁇ 0.0900].
  • the phosphor powder can function as a red phosphor because the main crystal includes phosphor particles having the same crystal structure as CaAlSiN 3 .
  • the phosphor powder has an elemental ratio of strontium (Sr), calcium (Ca), and europium (Eu) within the predetermined range, so that it emits fluorescence with a sufficient reddish tinge and has excellent brightness. It is now possible to exhibit The reason why such an effect is obtained is not clear, but the present inventors estimate as follows. First, in SCASN phosphors, as the content of calcium in the composition formula decreases (that is, as the proportion of calcium sites in the crystal lattice is replaced by other elements increases), the half-width of the emission spectrum narrows and the luminance increases.
  • the emission peak wavelength shifts to the shorter wavelength side, and the reddish tinge of the fluorescence tends to decrease.
  • concentration quenching occurs as the amount of europium increases, and although the luminous efficiency decreases, the emission peak wavelength tends to shift to the longer wavelength side.
  • Strontium, calcium, and europium are elements that share the same site in the crystal lattice, so in the above phosphor powder, the proportions of strontium, calcium, and europium in the composition formula satisfy the above-mentioned x and y ranges.
  • the emission brightness is improved and the wavelength position is adjusted to increase the overlap with the human visual sensitivity curve, while keeping the emission peak position in a sufficiently reddish wavelength range. It is estimated that the luminescence intensity can be improved.
  • the phosphor powder may have an emission peak wavelength of 635 nm or more when irradiated with light having a wavelength of 455 nm. Since the emission peak wavelength is 635 nm or more, the phosphor powder can be more suitably used as a red phosphor that emits fluorescence with an excellent reddish tint.
  • One aspect of the present disclosure is a light emitting device including a light emitting element that emits primary light, and a wavelength converter that absorbs a portion of the primary light and emits secondary light having a wavelength longer than the wavelength of the primary light.
  • the present invention provides a light emitting device in which the wavelength converter includes the phosphor powder described above.
  • the light-emitting device contains the above-mentioned phosphor powder, it can exhibit excellent color rendering properties. Since the light-emitting device also contains the above-mentioned phosphor powder, it can be expected to exhibit sufficient brightness.
  • One aspect of the present disclosure is to heat-treat a mixed powder containing a raw material powder containing a strontium source, a calcium source, an aluminum source, a silicon source, a nitrogen source, and a europium source and a nucleating agent composed of a CASN-based compound.
  • a firing step for obtaining a fired product and an annealing step for obtaining an annealed product by heat-treating the fired product at a temperature lower than the heat treatment temperature in the firing step, and in the raw material powder, aluminum
  • the ratio of the total amount of strontium, calcium, and europium to the amount of substance exceeds 1.0000, and the amount of calcium is 0.0050 or more with respect to the amount of aluminum, and the amount of europium is Provided is a method for producing a phosphor powder in which the amount is 0.0880 or less.
  • the above method for producing phosphor powder is such that in the raw material powder, the ratio of the total amount of strontium, calcium, and europium to the amount of aluminum exceeds 1, and the amount of calcium and europium is within a predetermined range. Furthermore, by firing in the presence of a nucleating agent to form the desired particles, it is possible to prepare a phosphor powder represented by the above general formula. ing. Conventionally, in the production of CASN-based phosphors, it is common to mix raw materials according to the desired composition, and at that time, the ratio of the total amount of strontium, calcium, and europium to the amount of aluminum is The composition is adjusted so that it becomes 1.
  • a phosphor powder that can exhibit excellent brightness while emitting fluorescence with sufficient redness, and a method for producing the same.
  • a light emitting device that uses the above-described phosphor powder and can exhibit excellent color rendering properties.
  • FIG. 1 is a schematic diagram showing the relationship between the visibility curve and the emission spectrum of the SCASN phosphor.
  • the materials exemplified in this specification can be used alone or in combination of two or more. If there are multiple substances corresponding to each component in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. .
  • One embodiment of the phosphor powder has the main crystalline phase having the same crystal structure as CaAlSiN 3 and has the general formula: (Sr 1-xy , Ca x , Eu y )AlSi(N,O) 3 [General In the formula, x and y satisfy 0.0100 ⁇ x ⁇ 0.0300 and 0.0500 ⁇ y ⁇ 0.0900].
  • the value of x is, for example, 0.0105 or more, 0.0108 or more, 0.0110 or more, or 0 .117 or more, and may be 0.0280 or less, 0.0250 or less, or 0.0240 or less.
  • the value of y may be, for example, 0.0600 or more, 0.0700 or more, or 0.0750 or more, and 0.0880 or less, or 0.0850 or less.
  • the phosphor powder is an aggregation of phosphor particles.
  • the phosphor particles may be CASN phosphors or SCASN phosphors.
  • the crystal structure of the phosphor particles can be confirmed by powder X-ray diffraction.
  • the contents of strontium (Sr), calcium (Ca), europium (Eu), aluminum (Al), and silicon (Si) in the composition of the phosphor particles can be determined by preparing a sample solution by decomposing the measurement target with pressure acid. However, it can be determined by quantitative analysis using an ICP emission spectrometer.
  • the lower limit of the emission peak wavelength of the phosphor powder may be, for example, 635 nm or more, 636 nm or more, 637 nm or more, more than 637 nm, or 638 nm or more.
  • the phosphor powder can be more suitably used as a red phosphor that exhibits a tendency to have better redness.
  • the upper limit of the emission peak wavelength of the phosphor powder may be, for example, 645 nm or less, 642 nm or less, 640 nm or less, less than 640 nm, or 639 nm or less.
  • the emission peak wavelength of the phosphor powder may be adjusted within the above-mentioned range, and may be, for example, 635 to 645 nm.
  • the half-width at the emission peak wavelength of the phosphor powder is relatively small.
  • the upper limit of the half-width at the emission peak wavelength of the phosphor powder is, for example, 75.0 nm or less, 74.8 nm or less, 74.6 nm or less, 74.5 nm or less, 74.4 nm or less, less than 74.4 nm, or 74 nm or less. It may be .3 nm or less.
  • the upper limit of the half width is within the above range, the luminance of the phosphor powder can be further improved.
  • the lower limit of the half-value width at the emission peak wavelength of the phosphor powder may be, for example, 70.0 nm or more, 71.0 nm or more, 72.0 nm or more, 73.0 nm or more, or 73.5 nm or more.
  • the half-width at the emission peak wavelength of the phosphor powder may be within the above-mentioned range, for example, from 70.0 to 75.0 nm, or from 73.5 to 74.3 nm.
  • the emission peak wavelength of a phosphor means a value determined by fluorescence spectrum measurement when irradiated with light with a wavelength of 455 nm.
  • the half-width means Full Width at Half Maximum (FWHM), and can be determined from the fluorescence spectrum obtained by fluorescence spectrum measurement when irradiated with light with a wavelength of 455 nm.
  • the upper limit of the average particle size of the phosphor powder may be, for example, 40.0 ⁇ m or less, 30.0 ⁇ m or less, or 25.0 ⁇ m or less. By setting the upper limit of the average particle size within the above range, it is possible to suppress variations in the chromaticity of the emitted light color when the phosphor powder is used on the LED light emitting surface.
  • the lower limit of the average particle size of the phosphor powder may be, for example, 0.1 ⁇ m or more, 0.5 ⁇ m or more, or 1.0 ⁇ m or more. By setting the lower limit of the average particle size within the above range, reduction in brightness can be further suppressed.
  • the average particle size of the phosphor powder may be adjusted within the above-mentioned range, for example, from 0.1 to 40.0 ⁇ m, from 0.5 to 30.0 ⁇ m, or from 1.0 to 25.0 ⁇ m.
  • the average particle size in this specification refers to the particle size (D50, median diameter).
  • the distribution curve regarding the particle size of the phosphor powder is based on the particle size distribution measurement method using laser diffraction/scattering method described in JIS R 1629:1997 "Method for measuring particle size distribution of fine ceramic raw materials using laser diffraction/scattering method". I will do it.
  • a particle size distribution measuring device can be used for the measurement. Specifically, first, 0.1 g of the phosphor powder to be measured was added to 100 mL of ion-exchanged water, a small amount of sodium hexametaphosphate was added, and the mixture was dispersed for 3 minutes using an ultrasonic homogenizer.
  • the particle size is measured using a particle size distribution measuring device, and D50 is determined from the obtained particle size distribution. D50 is also called the median diameter.
  • D50 is also called the median diameter.
  • the particle size distribution measuring device for example, "Microtrac MT3300EX II” (product name) manufactured by Microtrac Bell Co., Ltd. can be used.
  • the ultrasonic homogenizer for example, “Ultrasonic Homogenizer US-150E” manufactured by Nippon Seiki Seisakusho Co., Ltd. (product name, chip size: ⁇ 20, amplitude: 100%, oscillation frequency: 19.5 KHz, amplitude: approximately 31 ⁇ m) is used. can.
  • the above-mentioned phosphor powder is capable of exhibiting excellent brightness while emitting fluorescence with a sufficient reddish tint, so it is suitable as a phosphor for use in light-emitting devices such as LEDs, display devices, etc. Can be used.
  • the light emitting device etc. obtained in this way can exhibit excellent color rendering properties and sufficient brightness.
  • the above-mentioned phosphor powder can be manufactured, for example, by the following method.
  • One embodiment of the method for producing phosphor powder is a mixed powder containing a raw material powder containing a strontium source, a calcium source, an aluminum source, a silicon source, a nitrogen source, and a europium source, and a nucleating agent composed of a CASN-based compound. and an annealing step to obtain an annealed product by heat-treating the fired product at a temperature lower than the temperature of the heat treatment in the firing step.
  • strontium source calcium source, aluminum source, silicon source, nitrogen source, and europium source are strontium (Sr), calcium (Ca), aluminum (Al), silicon (Si), nitrogen (N), and europium ( means a compound or simple substance that is a source of Eu).
  • strontium nitride is used as the strontium source, the strontium nitride is both a strontium source and a nitrogen source.
  • strontium compound examples include strontium nitride (Sr 3 N 2 ), strontium oxide (SrO), and strontium hydroxide (Sr(OH) 2 ).
  • Examples of the calcium compound include calcium nitride (Ca 3 N 2 ), calcium oxide (CaO), and calcium hydroxide (Ca(OH) 2 ).
  • Examples of the aluminum compound include aluminum nitride (AlN), aluminum oxide (Al 2 O 3 ), and aluminum hydroxide (Al(OH) 3 ).
  • silicon compounds include silicon nitride (Si 3 N 4 ) and silicon oxide (SiO 2 ).
  • silicon nitride it is preferable to use one with a high ⁇ fraction.
  • the ⁇ fraction of silicon nitride may be, for example, 80% by mass or more, 90% by mass or more, or 95% by mass or more. When the ⁇ fraction of silicon nitride is within the above range, growth of primary particles of the inorganic compound can be promoted.
  • Europium source means a compound or simple substance that serves as a source of europium.
  • the compound having europium as a constituent element may be, for example, any one of a nitride, an oxide, an oxynitride, and a hydroxide, but preferably an oxide.
  • europium compounds include europium oxides (europium oxide), europium nitrides (europium nitride), and europium halides.
  • europium halides include europium fluoride, europium chloride, europium bromide, and europium iodide.
  • the compound of europium preferably comprises europium oxide.
  • the valence of europium in the europium compound may be divalent or trivalent, and preferably divalent.
  • the ratio of the total amount of strontium, calcium, and europium to the amount of aluminum exceeds 1.0000, and the amount of calcium is 0.0050 or more based on the amount of aluminum. , and the amount of europium is 0.0880 or less.
  • the lower limit of the ratio of the total amount of strontium, calcium, and europium to the amount of aluminum is, for example, 1.0200 or more, 1.0300 or more, 1.0400 or more, 1.0450 or more. , or 1.0500 or more.
  • the upper limit of the ratio of the total amount of strontium, calcium, and europium to the amount of aluminum is, for example, 1.5000 or less, 1.4000 or less, 1.3000 or less, 1.2000 or less , or 1.1000 or less.
  • the ratio of the total amount of strontium, calcium, and europium to the amount of aluminum may be adjusted within the above range, for example, more than 1.0000 and less than or equal to 1.5000, and more than 1.0000. It may be 1.3000 or less, or 1.0200 to 1.2000.
  • the lower limit of the amount of calcium in the raw material powder is, for example, 0.0050 or more, 0.0100 or more, 0.0105 or more, 0.0108 or more, 0.0110 or more, 0. It may be 0.0130 or more, or 0.0150 or more.
  • the upper limit of the calcium content in the raw material powder may be, for example, 0.0280 or less, 0.0250 or less, 0.0240 or less, or 0.0220 or less, based on the aluminum content.
  • the amount of calcium in the raw material powder may be adjusted within the above-mentioned range, and may be, for example, 0.0050 to 0.0280 based on the amount of aluminum.
  • the lower limit of the amount of europium in the raw material powder may be, for example, 0.0550 or more, 0.0600 or more, 0.0650 or more, or 0.0700 or more, based on the amount of aluminum.
  • the upper limit of the amount of europium in the raw material powder may be, for example, 0.0880 or less, 0.0860 or less, 0.0850 or less, or 0.0830 or less, based on the amount of aluminum.
  • the amount of europium in the raw material powder may be adjusted within the above-mentioned range, and may be, for example, 0.0550 to 0.0880 based on the amount of aluminum.
  • the nucleating agent composed of a CASN-based compound blended into the mixed powder may have the same crystal structure as CaAlSiN 3 and may contain a luminescent center element.
  • the firing in the firing step may be performed, for example, by filling a heat-resistant lidded container with the mixed powder to be fired and heating the container together.
  • a heat-resistant lidded container examples include boron nitride, tungsten, molybdenum, and tantalum.
  • An electric furnace or the like can be used for heating.
  • the firing temperature in the firing process may be constant throughout the process.
  • the firing temperature in the firing step may be, for example, 1500°C or higher, or 1550°C or higher.
  • the firing temperature in the firing step may be, for example, 2000°C or lower, 1980°C or lower, or 1950°C or lower.
  • the firing temperature in the firing step can be adjusted within the above-mentioned range, and may be, for example, 1500 to 2000°C or 1550 to 1950°C.
  • the lower limit of the firing time in the firing step may be, for example, 0.5 hours or more, 1.0 hours or more, 1.5 hours or more, 3.0 hours or more, or 4.0 hours or more.
  • the upper limit of the firing time in the firing step may be, for example, 30.0 hours or less, 20.0 hours or less, 10.0 hours or less, or 8.0 hours or less.
  • the firing time in the firing step can be adjusted within the above-mentioned range, and may be, for example, 0.5 to 30.0 hours, 1.5 to 10.0 hours, or 4.0 to 8.0 hours.
  • the firing time refers to the time (holding time) during which the temperature of the surrounding environment of the object to be heated reaches a predetermined temperature and is maintained at that temperature.
  • the firing step may be performed under atmospheric pressure or under pressure.
  • the lower limit of the firing pressure in the firing process may be, for example, 0.1 MPaG or more, or 0.2 MPaG or more.
  • the upper limit of the firing pressure in the firing step may be, for example, 1.0 MPaG or less, or 0.9 MPaG or less.
  • the pressure of the firing process can be adjusted within the above-mentioned range, and may be, for example, 0.1 to 1.0 MPaG, or 0.1 to 0.9 MPaG.
  • Pressure in this specification means gauge pressure.
  • the firing step is preferably performed in an atmosphere containing at least one selected from the group consisting of a rare gas and an inert gas.
  • the rare gas may contain, for example, argon, helium, etc., may contain argon, or may consist of argon.
  • the inert gas may contain, for example, nitrogen, or may consist of nitrogen.
  • the annealed product is obtained by heat-treating the fired product at a temperature lower than the temperature of the heat treatment in the firing step.
  • the temperature of the heat treatment in the annealing step may be, for example, 1200°C or higher, 1250°C or higher, or 1300°C or higher.
  • the temperature of the heat treatment in the annealing step may be, for example, 1450°C or lower, 1400°C or lower, or 1350°C or lower.
  • the upper limit of the temperature of the heat treatment is within the above range, crystal defects can be sufficiently reduced while further suppressing decomposition of the main phase.
  • the temperature of the heat treatment in the annealing step can be adjusted within the above-mentioned range, and may be, for example, 1200 to 1450°C or 1250 to 1350°C.
  • the lower limit of the heat treatment time in the annealing step may be, for example, 0.5 hours or more, 1.0 hours or more, 1.5 hours or more, 3.0 hours or more, or 4.0 hours or more.
  • the upper limit of the heat treatment time in the annealing step may be, for example, 30.0 hours or less, 20.0 hours or less, 10.0 hours or less, 8.0 hours or less, or 5.0 hours or less.
  • the heat treatment time in the annealing step can be adjusted within the above-mentioned range, and may be, for example, 0.5 to 30.0 hours, 1.5 to 10.0 hours, or 4.0 to 8.0 hours.
  • the annealing step may be performed under atmospheric pressure or under increased pressure.
  • the lower limit of the pressure in the annealing step may be, for example, 0.1 MPaG or more, or 0.2 MPaG or more.
  • the upper limit of the pressure in the annealing step may be, for example, 1.0 MPaG or less, or 0.9 MPaG or less.
  • the pressure of the annealing process can be adjusted within the above-mentioned range, and may be, for example, 0.1 to 1.0 MPaG, or 0.1 to 0.9 MPaG.
  • the annealing step is preferably performed in an atmosphere containing at least one selected from the group consisting of a rare gas and an inert gas.
  • the rare gas may contain, for example, argon, helium, etc., may contain argon, or may consist of argon.
  • the inert gas may contain, for example, nitrogen, or may consist of nitrogen.
  • the method for manufacturing the phosphor powder described above may include other steps in addition to the firing step and the annealing step.
  • Other processes include, for example, a crushing process, a classification process, and an acid treatment process.
  • the crushing process is a process of crushing the fired product obtained in the firing process or the annealed product obtained in the annealing process to adjust the particle size, since it may be obtained in the form of a lump.
  • a mortar or the like may be used, or a general crusher or crusher may also be used.
  • the crusher and crusher include a ball mill, a jet mill, and a Henschel mixer.
  • Agglomerates of fired products may be crushed using a method with relatively high strength, but when disintegrating agglomerates of annealed products, scratches, cracks, etc. may occur on the surface of the phosphor particles. From the viewpoint of suppressing this, it is desirable to perform crushing under gentle conditions. From the viewpoint of crushing under mild conditions, for example, the crushing step is preferably performed by wet ball milling in which a medium such as ion-exchanged water coexists. Additionally, zirconia balls can be used in the ball mill.
  • the classification step may be a step of removing fine particles that reduce the luminance of the phosphor powder.
  • the method for producing the phosphor powder described above includes a classification step.
  • a decantation method may be used.
  • the object to be treated for example, phosphor powder that has undergone a crushing process
  • a dispersion liquid is prepared and stirred, and then the phosphor powder in the dispersion liquid is precipitated, and the supernatant liquid is This is done by removing.
  • the precipitate is collected by filtration and dried to obtain a phosphor powder from which fine particles have been removed.
  • the above-described preparation of the dispersion liquid and removal of the supernatant may be repeated.
  • the dispersion medium include an aqueous solution of sodium hexametaphosphate.
  • the acid treatment step may be a step of reducing the content of impurities that do not contribute to light emission by treating the phosphor powder with an acid.
  • acids include hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid.
  • the acid may include at least one selected from the group consisting of hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid, and may be a mixed acid, but is preferably hydrochloric acid.
  • the acid treatment step is performed by bringing the phosphor powder into contact with the above-mentioned acid. Specifically, the above-mentioned phosphor powder is put into an aqueous solution containing the above-mentioned acid, a dispersion liquid is prepared, and the process is performed for a predetermined period of time while stirring.
  • the lower limit of the stirring time in the acid treatment step may be, for example, 0.1 hour or more, 0.5 hour or more, or 1.0 hour or more.
  • the upper limit of the stirring time may be, for example, 6.0 hours or less, 3.0 hours or less, or 1.5 hours or less.
  • the aqueous solution may be subjected to the acid treatment while being cooled, heated, or boiled. It may be. After the acid treatment, the phosphor powder may be washed with water to remove the acid and dried. The temperature during drying may be, for example, 100 to 120°C. The drying time may be, for example, about 12 hours.
  • the above-described phosphor powder is suitable as a phosphor for use in light-emitting devices such as display devices.
  • One embodiment of the light emitting device includes a light emitting element that emits primary light, and a wavelength converter that absorbs a portion of the primary light and emits secondary light having a wavelength longer than the wavelength of the primary light. It is a device.
  • the light emitting element that emits primary light may be, for example, an InGaN blue LED.
  • the wavelength converter includes the phosphor powder described above.
  • the wavelength converter may contain other phosphors in addition to the phosphor powder described above.
  • Other phosphors may include, for example, red phosphor, yellow phosphor, yellow-green phosphor, green phosphor, etc. other than the above-mentioned phosphor powder.
  • Other phosphors can be selected depending on the use of the phosphor composition, and can be selected and combined depending on, for example, the brightness, color, color rendering properties, etc. required of the light emitting device. Examples of the red phosphor include conventional CASN-based phosphors.
  • Examples of the green to yellow phosphor include YAG phosphor, LuAG phosphor, and the like.
  • Examples of the yellow phosphor include Ca- ⁇ -SiAlON phosphor, and examples of the green phosphor include ⁇ -SiAlON phosphor.
  • the light emitting element and wavelength converter may be dispersed in a sealing resin or the like.
  • a sealing resin it is desirable that it is colorless in itself, and it is possible to use a resin that has excellent transparency to visible light wavelengths.
  • the sealing resin one that is generally recognized to be transparent can be used.
  • the above-mentioned resin may be, for example, a silicone resin or an acrylic resin.
  • the relative luminous efficiency is generally determined based on the standard relative luminous efficiency curve by the Commission Internationale de l'Eclairage (CIE). The more the light has an emission spectrum that overlaps with the standard luminous efficiency curve, the brighter the light will feel to humans.
  • CIE Commission Internationale de l'Eclairage
  • the standard luminous efficiency curve draws a curve close to a normal distribution that peaks around 550 nm and spreads from 400 to 700 nm. For example, in bright places, humans are said to feel most strongly the light around 555 nm.
  • the emission spectrum of SCASN phosphors generally has a region that overlaps with the standard luminous efficiency curve, so SCASN phosphors are considered useful as red phosphors.
  • SCASN phosphors generally have an emission spectrum ranging from 600 to 800 nm.
  • the above-mentioned phosphor powder has a specific proportion of strontium, calcium, and europium in the composition formula that satisfies the above-mentioned x and y ranges, so that the peak position of the emission spectrum is at short wavelengths. It has a larger overlap with the standard luminous efficiency curve and exhibits sufficient brightness. Furthermore, since it exhibits a sufficient reddish tint, the above-mentioned phosphor powder can be a useful red phosphor for manufacturing display elements with excellent brightness.
  • Example 1 [Preparation of nucleating agent] First, in a container, 60.61 g of ⁇ -type silicon nitride (Si 3 N 4 , manufactured by Ube Industries, Ltd., SN-E10 grade), 53.13 g of aluminum nitride (AlN, manufactured by Tokuyama Corporation, E grade), and 13.68 g of europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.) was added and premixed.
  • ⁇ -type silicon nitride Si 3 N 4 , manufactured by Ube Industries, Ltd., SN-E10 grade
  • AlN aluminum nitride
  • Eu 2 O 3 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a glove box 240 g of the above mixture was filled into a lidded container made of tungsten. After closing the lid of this lidded container, it was taken out from the glove box and placed in an electric furnace equipped with a carbon heater. Thereafter, the electric furnace was sufficiently evacuated until the pressure in the electric furnace became 0.1 PaG or less.
  • the temperature inside the electric furnace was raised to 600°C. After reaching 600° C., nitrogen gas was introduced into the electric furnace and the pressure inside the electric furnace was adjusted to 0.9 MPaG. Thereafter, the temperature in the electric furnace was raised to 1950° C. under a nitrogen gas atmosphere, and after reaching 1950° C., heat treatment was performed for 8 hours. Thereafter, heating was terminated and the mixture was cooled to room temperature. After cooling to room temperature, a red mass was collected from the container. The collected lumps were crushed in a mortar and passed through a sieve to prepare core particles (nucleating agent) with an average particle size of 16 ⁇ m.
  • a glove box 240 g of the above mixed powder was filled into a tungsten container with a lid. After closing the lid of this lidded container, it was taken out from the glove box and placed in an electric furnace equipped with a carbon heater. Thereafter, the electric furnace was sufficiently evacuated until the pressure in the electric furnace became 0.1 PaG or less.
  • the temperature inside the electric furnace was raised to 600°C. After reaching 600° C., nitrogen gas was introduced into the electric furnace and the pressure inside the electric furnace was adjusted to 0.9 MPaG. Thereafter, the temperature in the electric furnace was raised to 1950° C. under a nitrogen gas atmosphere, and after reaching 1950° C., heat treatment was performed for 8 hours. Thereafter, heating was terminated and the mixture was allowed to cool to room temperature. After cooling to room temperature, a red mass was collected from the container. The collected lumps were crushed, passed through a sieve, and the particle size was adjusted to obtain a fired powder.
  • the obtained fired powder was filled into a tungsten container, quickly transferred into an electric furnace equipped with a carbon heater, and sufficiently evacuated until the pressure in the furnace became 0.1 PaG or less. Heating was started while evacuation continued, and when the temperature reached 600° C., argon gas was introduced into the furnace and the pressure of the atmosphere inside the furnace was adjusted to atmospheric pressure. Even after starting the introduction of argon gas, the temperature continued to rise to 1350°C. After the temperature reached 1350°C, heat treatment was carried out for 8 hours. Thereafter, heating was terminated and the mixture was cooled to room temperature. After cooling to room temperature, the annealed powder was collected from the container. The collected powder was passed through a sieve to adjust the particle size. In this way, an annealed powder was obtained.
  • the annealed powder was added to 2.0 M hydrochloric acid at room temperature so that the slurry concentration was 25% by mass, and immersed for 1 hour. In this way, acid treatment was performed. After the acid treatment, the hydrochloric acid slurry was boiled for 1 hour while stirring. The slurry after the boiling treatment was cooled to room temperature and filtered, and the acid treatment liquid was separated from the solid component to obtain an acid treatment product. The acid-treated product was dried by placing it in a dryer set at a temperature in the range of 100 to 120° C. for 12 hours to obtain acid-treated powder.
  • the acid-treated powder was filled into an alumina crucible, heated in the air at a temperature increase rate of 10°C/min, and heat-treated at 400°C for 3 hours. After the heat treatment, the mixture was left to stand until the temperature reached room temperature to obtain a heat-treated powder.
  • the obtained heat-treated powder was subjected to powder X-ray diffraction using CuK ⁇ rays using an X-ray diffraction apparatus (manufactured by Rigaku Co., Ltd., trade name: Ultima IV).
  • the same diffraction pattern as CaAlSiN 3 crystal was observed, and it was confirmed that the main crystal phase had the same crystal structure as CaAlSiN 3 crystal.
  • the heat-treated powder was designated as the phosphor powder of Example 1.
  • Example 2 Comparative Examples 1 to 4
  • a phosphor powder was prepared in the same manner as in Example 1, except that the mixing ratio was adjusted so that the breakdown (molar ratio) of the amount of each element in the raw material powder was as shown in Table 1.
  • composition ratio The phosphor powder was subjected to pressure acid decomposition to prepare a sample solution, and the sample solution was quantitatively analyzed using an ICP emission spectrometer to determine the composition ratio of the elements constituting the phosphor powder.
  • the fluorescence spectrum of the phosphor powder was measured using a spectrofluorometer (trade name: F-7000, manufactured by Hitachi High-Technologies Corporation) that was corrected with Rhodamine B and a secondary standard light source.
  • a solid sample holder attached to the photometer was used to measure the fluorescence spectrum at an excitation wavelength of 455 nm.
  • the peak wavelength and half-value width of the emission spectrum were determined from the obtained fluorescence spectrum.
  • a kneaded product was obtained by blending phosphor powder and LuAG yellow phosphor (emission peak wavelength is 535 nm when receiving excitation light with a wavelength of 455 nm) into a silicone resin, degassing and kneading.
  • a white LED was prepared by potting the obtained kneaded product into a surface mount type package to which a blue LED element with a peak wavelength of 450 nm was bonded, and thermosetting it.
  • the compounding ratio of the phosphor powder and the YAG phosphor was adjusted so that the chromaticity coordinates (x, y) of the white LED were (0.460, 0.411) during energization and light emission.
  • the special color rendering index R9 and total luminous flux when the obtained white LED was energized and emitted were measured using a total luminous flux measuring device (manufactured by Otsuka Electronics Co., Ltd., an integrating hemisphere with a diameter of 500 mm and a spectrophotometer (MCPD-9800). (combined device).
  • a phosphor powder that can exhibit excellent brightness while emitting sufficient reddish fluorescence, and a method for producing the same.
  • a light emitting device that uses the above-described phosphor powder and can exhibit excellent color rendering properties.

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Abstract

Un aspect de la présente invention concerne une poudre de phosphore qui contient des particules de phosphore qui ont une phase cristalline principale qui a la même structure cristalline que CaAlSiN3, tout en étant représentée par la formule générale (Sr1-x-y, Cax, Euy)AlSi(N, O)3 (dans laquelle x et y satisfont 0,0100 ≤ x ≤ 0,0300 et 0,0500 ≤ y ≤ 0,0900).
PCT/JP2023/008420 2022-03-15 2023-03-06 Poudre de phosphore, procédé de production de poudre de phosphore et dispositif électroluminescent WO2023176564A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120080704A1 (en) * 2010-09-30 2012-04-05 Chi Mei Corporation Method of providing a phosphor with a precisely controlled element composition, a phosphor provided by the same, a phosphor, and a light emitting device comprising the said phosphor
US20150308657A1 (en) * 2012-12-21 2015-10-29 Grirem Advanced Materials Co., Ltd. Oxynitride orange-red fluorescent substance and light-emitting film or sheet and light-emitting device comprising the same
CN110157417A (zh) * 2018-02-12 2019-08-23 有研稀土新材料股份有限公司 一种近红外光发光材料及包含其的发光装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120080704A1 (en) * 2010-09-30 2012-04-05 Chi Mei Corporation Method of providing a phosphor with a precisely controlled element composition, a phosphor provided by the same, a phosphor, and a light emitting device comprising the said phosphor
US20150308657A1 (en) * 2012-12-21 2015-10-29 Grirem Advanced Materials Co., Ltd. Oxynitride orange-red fluorescent substance and light-emitting film or sheet and light-emitting device comprising the same
CN110157417A (zh) * 2018-02-12 2019-08-23 有研稀土新材料股份有限公司 一种近红外光发光材料及包含其的发光装置

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