WO2020255881A1 - 蛍光体及び蛍光体の製造方法 - Google Patents

蛍光体及び蛍光体の製造方法 Download PDF

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WO2020255881A1
WO2020255881A1 PCT/JP2020/023237 JP2020023237W WO2020255881A1 WO 2020255881 A1 WO2020255881 A1 WO 2020255881A1 JP 2020023237 W JP2020023237 W JP 2020023237W WO 2020255881 A1 WO2020255881 A1 WO 2020255881A1
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phosphor
potassium
silicon
solution
compound
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French (fr)
Japanese (ja)
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真義 市川
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Denka Co Ltd
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Denka Co Ltd
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Priority to KR1020227001239A priority Critical patent/KR20220024538A/ko
Priority to CN202080043958.2A priority patent/CN113966377B/zh
Priority to JP2021528183A priority patent/JPWO2020255881A1/ja
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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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/61—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/617—Silicates
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/61—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/61—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/615—Halogenides
    • C09K11/616—Halogenides with alkali or alkaline earth metals

Definitions

  • the present disclosure relates to a fluorescent substance and a method for producing the fluorescent substance.
  • LEDs Light emitting diodes
  • an LED having a blue light emitting diode and a yellow phosphor is generally used.
  • green phosphors and red phosphors have come to be used in combination instead of yellow phosphors. From the viewpoint of improving color rendering properties, various red phosphors have been studied.
  • an image display device or the like using an LED is required to have excellent moisture resistance. Therefore, the phosphor used for the LED is also required to have excellent moisture resistance.
  • the fluoride phosphors activated with Mn 4+ known as a red phosphor (e.g., K 2 SiF 6: Mn 4+ and the like) are not be said moisture resistance necessarily sufficient moisture resistance of the fluoride phosphor Improvements are being considered.
  • M is at least one selected from Ti, Zr, Hf, Si, Ge and Sn
  • a is a method for producing a fluoride phosphor represented by 0 ⁇ a ⁇ 0.2).
  • a solution containing at least Mn and F, a solution containing at least K and F, and a solution containing at least Si and F are mixed to form a phosphor core having a composition represented by the above general formula.
  • the step is a step of mixing the phosphor core and a solution containing a reducing agent to form a surface region in the phosphor core in which the concentration of tetravalent Mn is lower than the internal region of the phosphor particles.
  • a method for producing a fluoride phosphor characterized by containing it has been proposed.
  • An object of the present disclosure is to provide a method for producing a fluorescent substance having excellent moisture resistance and reliability. It is also an object of the present disclosure to provide a fluorescent material having excellent moisture resistance and reliability.
  • K 2 SiF 6 A method for producing a phosphor containing Mn 4+, comprising the step of fluoride phosphor, a compound containing potassium, is contacted with a solution containing a reducing agent and silicon compounds , Provide a method for producing a phosphor.
  • the above-mentioned method for producing a phosphor can produce a phosphor having excellent moisture resistance and reliability by having a step of contacting a fluoride phosphor with a solution containing the above-mentioned specific component.
  • the potassium-containing compound may contain at least one selected from the group consisting of potassium acetate, potassium nitrate, and potassium hydroxide.
  • the reducing agent may contain hydrogen peroxide.
  • the solution may contain at least one selected from the group consisting of water and alcohol.
  • the silicon compound may contain a compound represented by the general formula: Si (OR 1 ) (OR 2 ) (OR 3 ) (OR 4 ).
  • R 1 , R 2 , R 3 and R 4 each independently represent a monovalent hydrocarbon group.
  • K 2 SiF 6 a body portion including a Mn 4+, attached to the body portion, a phosphor having a coating portion containing silicon and oxygen, X with respect to the surface of the phosphor
  • a phosphor in which the ratio of silicon to potassium measured by photoelectron spectroscopy is 0.52 or more, and the ratio of silicon to potassium in the main body portion is lower than the ratio of silicon to potassium in the coating portion.
  • the above-mentioned fluorescent material has a predetermined coating portion on the surface of the main body portion, and therefore has excellent moisture resistance and reliability.
  • the ratio of oxygen to potassium in the phosphor as measured by X-ray photoelectron spectroscopy may be 0.20 or more.
  • FIG. 1 is a schematic cross-sectional view showing an example of a phosphor.
  • each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component in the composition are present, unless otherwise specified. ..
  • An embodiment of a method for manufacturing a phosphor, K 2 SiF 6 A method of manufacturing a phosphor containing Mn 4+, contacting the fluoride phosphor, a compound containing potassium, a solution containing a reducing agent and silicon compounds It has a step of making it.
  • K 2 SiF 6 a body portion including a Mn 4+, adhered to the surface of the body portion, it is possible to produce a phosphor having a coating portion containing silicon and oxygen .
  • the produced fluorescent substance has a coating portion on at least a part of the surface of the fluoride phosphor, and therefore has excellent moisture resistance and reliability.
  • Moisture resistance reliability as used herein means performance evaluated using the maintenance rate of internal quantum efficiency measured by the method described in the examples of the present specification as an index.
  • the step of bringing the fluoride phosphor into contact with the solution may be, for example, a method of dispersing the fluoride phosphor in the solution, or a method of spraying the solution on the fluoride phosphor. Good.
  • the order of blending the fluoride phosphor, the compound containing potassium, the reducing agent, and the silicon compound may be appropriately adjusted. That is, the order may be such that the fluoride phosphor and the silicon compound are added to the solution containing the potassium-containing compound and the reducing agent, and the fluoride fluorescence is added to the solution containing the potassium-containing compound and the reducing agent.
  • the order may be that the silicon compound is added after the body is added.
  • the step of contacting the fluoride phosphor with the solution is a method of adding the fluoride phosphor and the silicon compound to the solution containing the potassium-containing compound and the reducing agent
  • the step is for a certain period of time while stirring the solution. It is preferable to carry out over.
  • a fluoride phosphor and a silicon compound are added to a solution containing a compound containing potassium and a reducing agent, and the mixture is stirred for about 1 minute to 72 hours and then allowed to stand for about 1 to 30 minutes for fluorescence. It is preferably a step of obtaining a body.
  • the stirring time may be adjusted according to the pH of the solution, the type and amount of the silicon compound, and the like.
  • the stirring time is preferably 3 to 24 hours from the viewpoint of reactivity and productivity.
  • the phosphor obtained in the step of bringing the fluoride phosphor into contact with the solution can be recovered by solid-liquid separation by, for example, filtration, centrifugation, decantation, or the like.
  • Fluoride phosphor is a fluoride represented by K 2 SiF 6, may be those part of the tetravalent element in the site is substituted with manganese.
  • some of its constituent elements potassium (K), silicon (Si), fluorine (F), and manganese (Mn) may be replaced with other elements, and the valences are different.
  • Part of the element in the crystal may be missing by being replaced by the element.
  • the other element may be at least one selected from the group consisting of, for example, sodium (Na), germanium (Ge), titanium (Ti), and oxygen (O).
  • the method for producing a phosphor may further include a step of preparing a fluoride phosphor.
  • the method for producing a fluorescent substance may further include a step of washing the prepared fluoride phosphor, a step of drying, a step of classifying, and the like, in addition to the step of preparing the fluoride phosphor.
  • a compound serving as a potassium source, a compound serving as a silicon source, a compound serving as a fluorine source, a compound serving as a manganese source, or the like is dissolved in a hydrofluoric acid or a hydrofluoric acid aqueous solution. It may be a step of preparing a prepared solution, heating the solution and evaporating to dryness to prepare a fluoride phosphor, and cooling the above solution to precipitate a fluoride phosphor to prepare a fluoride phosphor.
  • the fluoride phosphor is prepared by adding a poor solvent for the fluoride phosphor to the solution to reduce the solubility of the fluoride phosphor and precipitating the fluoride phosphor. It may be a process or the like.
  • Examples of the compound serving as a potassium source include a fluorinated product of potassium (for example, KHF 2 and the like) and a fluoride of potassium (for example, KF and the like).
  • Examples of the compound serving as a silicon source include silicon dioxide (SiO 2 ), hydrogen silicate (H 2 SiF 6 ), potassium silicate (K 2 SiF 6 ) and the like.
  • Hydrofluoric acid and aqueous hydrofluoric acid solution can be a source of fluorine as well as a compound that is a source of potassium. When an aqueous hydrofluoric acid solution is used, the concentration of hydrofluoric acid may be, for example, 40 to 70% by mass.
  • the instruments and the like for handling the hydrofluoric acid are made of chemically stable fluororesin.
  • a fluororesin-made instrument or the like it is possible to suppress the mixing of impurities.
  • the compound serving as a manganese source may include, for example, a compound capable of supplying manganese of +7 valence or less, preferably a compound capable of supplying manganese of +4 valence or less, and more preferably a compound capable of supplying +4 valent manganese. May be contained, and more preferably, it is a compound capable of supplying +4 valent manganese.
  • the compound serving as a manganese source preferably contains a compound that is easily dissolved in a solvent such as hydrofluoric acid and is capable of forming MnF 6 2- complex ions in an aqueous solution, and more preferably the general formula: K 2 SiF.
  • the fluoride crystal represented by 6 contains K 2 MnF 6 capable of dissolving +4 valent manganese as a solid solution, and more preferably K 2 MnF 6 .
  • the particle size of the fluoride phosphor may be adjusted according to the intended use of the phosphor to be produced.
  • the volume median diameter (D50) of the fluoride phosphor may be, for example, 5 to 30 ⁇ m, 10 to 30 ⁇ m, 20 to 30 ⁇ m, or 25 to 30 ⁇ m.
  • the volume median diameter (D50) of the fluoride phosphor is 30 ⁇ m or less, it is possible to suppress inconveniences such as a mixture of the phosphor and the resin causing clogging at the potting nozzle when manufacturing an LED element or the like. it can.
  • the volume median diameter (D50) of the fluoride phosphor may be, for example, 0.1 to 5 ⁇ m or 1 to 5 ⁇ m in addition to the relatively large volume median diameter (D50) described above.
  • the volume median diameter (D50) means a value obtained from a volume-based cumulative distribution curve measured according to the laser diffraction / scattering method described in JIS Z 8825: 2013.
  • the solution to be contacted with the fluoride phosphor contains a compound containing potassium, a reducing agent and a silicon compound.
  • the potassium-containing compound, the reducing agent, and the silicon compound may be, for example, partially or completely dispersed in the solution, or may be completely dissolved and ionized.
  • the potassium-containing compound may be a compound that increases the potassium (K) concentration in the solution that comes into contact with the fluoride phosphor.
  • K potassium
  • the potassium-containing compound preferably contains at least one selected from the group consisting of potassium acetate, potassium nitrate, and potassium hydroxide, and more preferably contains potassium acetate.
  • the reducing agent may be a compound capable of reducing manganese contained in the fluoride phosphor in the step of bringing the fluoride phosphor into contact with the above solution.
  • the fluoride phosphor is partially hydrolyzed when it comes into contact with water, moisture in the atmosphere, or the like, and a colored compound containing manganese (for example, a black compound) is formed on the surface of the fluoride phosphor. Can form. When such a colored compound is formed, the optical properties of the fluoride phosphor or the phosphor may be deteriorated. Therefore, it is desirable not to use water as a treatment for fluoride phosphors.
  • the formation of a colored compound can be suppressed by containing a reducing agent in the above solution, and even when water is used as a solvent, optics can be suppressed.
  • a phosphor having excellent properties can be produced.
  • the reducing agent is a compound different from the silicon compound, preferably a compound containing no silicon.
  • the reducing agent may contain at least one selected from the group consisting of compounds that generate hydroxyl radicals. Examples of the compound that generates hydroxyl radicals include hydrogen peroxide and the like.
  • the reducing agent preferably contains hydrogen peroxide, and more preferably hydrogen peroxide. Hydrogen peroxide can reduce manganese having a valence of 4 or less while suppressing the influence on the fluoride phosphor itself.
  • the silicon compound is a compound containing oxygen and silicon, and is a compound capable of forming a coating portion on at least a part of the surface of the fluoride phosphor.
  • the silicon compound may contain, for example, a compound represented by the general formula: Si (OR 1 ) (OR 2 ) (OR 3 ) (OR 4 ).
  • R 1 , R 2 , R 3 and R 4 each independently represent a monovalent hydrocarbon group.
  • R 1 , R 2 , R 3 , and R 4 may be the same or different.
  • the monovalent hydrocarbon group may be, for example, an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group may be, for example, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
  • R 1, R 2, R 3 , and R 4 the reactivity of the adjustment of the silicon compound, and the concentration of the fluoride phosphor contained in the solution, the solution temperature, and depending on the pH or the like, adjusted You may.
  • the silicon compound may be, for example, tetraalkyl orthosilicate or the like.
  • tetraalkyl orthosilicate examples include tetramethyl orthosilicate (TMS), tetraethyl orthosilicate (TEOS), and tetrapropyl orthosilicate (TPOS).
  • TMS tetramethyl orthosilicate
  • TEOS tetraethyl orthosilicate
  • TPOS tetrapropyl orthosilicate
  • the silicon compound preferably contains tetraethyl orthosilicate, and more preferably tetraethyl orthosilicate. Tetraethyl orthosilicate is easily available and reaction control is also easy.
  • the above solution may contain other components in addition to the potassium-containing compound, the reducing agent and the silicon compound.
  • Other components may include, for example, a solvent such as water, a pH adjuster, a surfactant and the like.
  • the solvent may contain, for example, at least one selected from the group consisting of water and alcohol. Although it is desirable not to use water in the treatment of the fluoride phosphor, it is also possible to use water in the method for producing the fluorescent substance of the present disclosure as described above because the solution contains a reducing agent. Further, when the above solution contains water, the reaction of the silicon compound can be further promoted.
  • the solvent is preferably a mixed solvent containing water and alcohol, and more preferably a mixed solvent of water and alcohol. When the solution contains water and alcohol, a phosphor having higher moisture resistance and reliability can be produced.
  • the alcohol may be, for example, a linear alcohol having 1 to 5 carbon atoms.
  • the alcohol may contain at least one selected from the group consisting of methanol, ethanol, and propanol.
  • the content of methanol may be, for example, 10% by mass or more, 15% by mass or more, or 30% by mass or more, and 60% by mass or less or 50% by mass or less, based on the total amount of the mixed solvent. It may be there.
  • the content of methanol may be adjusted within the above range, and may be, for example, 10 to 60% by mass, 10 to 50% by mass, or 15 to 50% by mass based on the total amount of the mixed solvent. Good.
  • the pH adjuster examples include acetic acid, hydrochloric acid, ammonia, ammonium acetate and the like.
  • the pH regulator preferably comprises acetic acid.
  • the surfactant is, for example, a cationic surfactant or the like.
  • the cationic surfactant may be, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, polyvinylpyrrolidone or the like.
  • the content of the potassium-containing compound in the above solution may be, for example, 1 part by mass or more, 4 parts by mass or more, 10 parts by mass or more, or 13 parts by mass or more based on 100 parts by mass of the fluoride phosphor.
  • the content of the potassium-containing compound in the above solution may be, for example, 30 parts by mass or less, or 25 parts by mass or less, based on 100 parts by mass of the fluoride phosphor.
  • the content of the compound containing potassium in the above solution may be adjusted within the above range. For example, 1 to 30 parts by mass, 1 to 25 parts by mass, and 4 to 25 parts by mass based on 100 parts by mass of the fluoride phosphor. It may be 10 to 25 parts by mass or 13 to 25 parts by mass.
  • the content of the reducing agent in the above solution may be adjusted according to the total amount of manganese contained in the fluoride phosphor.
  • the content of the reducing agent in the above solution is preferably 100 parts by mass or more based on the total amount of manganese contained in the fluoride phosphor.
  • the upper limit of the content of the reducing agent in the above solution is not particularly limited, but may be, for example, 3000 parts by mass or less, or 1500 parts by mass or less.
  • the content of the reducing agent in the above solution may be adjusted within the above range, and may be, for example, 100 to 3000 parts by mass or 100 to 1500 parts by mass.
  • the content of the silicon compound in the above solution may be adjusted according to the volume median diameter (D50) of the fluoride phosphor, the temperature and pH of the above solution, and the like.
  • the content of the silicon compound in the above solution may be, for example, 0.02 to 3.0 mol with respect to 100.0 parts by mass of the fluoride phosphor (D50: 5 ⁇ m), and the fluoride phosphor (D50: 30 ⁇ m). )
  • 100.0 parts by mass for example, it may be 0.004 to 0.3 mol.
  • the above-mentioned method for producing a fluorescent substance may include, for example, a step of heat-treating the fluorescent substance and a step of crushing the fluorescent substance after the above-mentioned step.
  • the step of heat-treating the phosphor is a step of heating the phosphor obtained by bringing the fluoride phosphor into contact with the solution to reduce the content of the solvent and the like.
  • the step of heat-treating the phosphor may be, for example, a drying step.
  • the temperature of the heat treatment in the drying step may be referred to as the drying temperature
  • the time of the heat treatment in the drying step may be referred to as the drying time.
  • the temperature of the heat treatment may be, for example, 250 ° C. or lower, 200 ° C. or lower, 150 ° C. or lower or 100 ° C. or lower, and may be 60 ° C. or higher or 80 ° C. or higher.
  • the temperature of the heat treatment may be adjusted within the above range, and may be, for example, 60 to 250 ° C, 60 to 200 ° C, 60 to 150 ° C, 60 to 100 ° C, or 80 to 100 ° C.
  • the time of the heat treatment may be, for example, 1 minute to 24 hours, and is preferably 2 to 10 hours from the viewpoint of the water content reduction rate and productivity of the phosphor.
  • One embodiment of the phosphor is a phosphor having a main body portion containing K 2 SiF 6 : Mn 4+ and a coating portion adhering to the main body portion and containing silicon and oxygen, and the surface of the phosphor is relative to the surface of the phosphor.
  • the ratio of silicon to potassium measured by X-ray photoelectron spectroscopy is 0.52 or more, and the ratio of silicon to potassium in the main body portion is lower than the ratio of silicon to potassium in the coating portion.
  • FIG. 1 is a schematic cross-sectional view showing an example of a phosphor.
  • the phosphor 10 has a main body portion 2 and a covering portion 4 provided on the surface 2a of the main body portion 2.
  • the covering portion 4 is shown as an example of an aggregate of deposits 4a adhering to the surface 2a of the main body portion 2, but the covering portion 4 is uniformly provided on the surface 2a of the main body portion 2. It may be a layer (for example, a layer formed by integrating a plurality of deposits 4a). Further, although the covering portion 4 is shown in FIG. 1 as an example of covering the entire surface of the main body portion 2, it may cover at least a part of the surface of the main body portion 2.
  • the ratio of silicon to potassium (Si / K) measured by X-ray photoelectron spectroscopy on the surface of the phosphor 10 is 0.52 or more, but 0.55 or more, 0.60 or more, 0.70 or more, or It may be 0.80 or more.
  • the fluorescent substance 10 is excellent in moisture resistance reliability.
  • the ratio of silicon to potassium (Si / K) measured by X-ray photoelectron spectroscopy on the surface of the phosphor 10 may be, for example, 2.5 or less, or 1.25 or less. When the ratio of silicon to potassium in the phosphor 10 is 2.5 or less, the fluorescent substance 10 can maintain good optical characteristics.
  • the ratio of silicon to potassium (Si / K) measured by X-ray photoelectron spectroscopy on the surface of the phosphor 10 may be adjusted within the above range, for example, 0.52 to 2.5, 0.55 to 0.55. It may be 2.5, 0.60 to 2.5, 0.70 to 2.5, 0.80 to 2.5, or 0.8 to 1.25.
  • the ratio of silicon to potassium described above means a value calculated using the ratio of potassium and silicon obtained from the result of composition analysis measured by X-ray photoelectron spectroscopy to the phosphor 10. In this specification, the measurement by X-ray photoelectron spectroscopy is performed according to the conditions described in Examples described later.
  • the ratio of oxygen to potassium (O / K) measured by X-ray photoelectron spectroscopy on the surface of the phosphor 10 is, for example, 0.20 or more, 0.30 or more, 0.50 or more, 0.70 or more, or It may be 0.80.
  • the ratio of oxygen to potassium (O / K) measured by X-ray photoelectron spectroscopy on the surface of the phosphor 10 may be, for example, 4.0 or less, or 1.5 or less. When the ratio of oxygen to potassium of the fluorescent substance 10 is 4.0 or less, the fluorescent substance 10 can maintain good optical characteristics.
  • the ratio of oxygen to potassium (O / K) measured by X-ray photoelectron spectroscopy on the surface of the phosphor 10 may be adjusted within the above range, for example, 0.20 to 4.0, 0.30 to 0.30. It may be 4.0, 0.50 to 4.0, 0.70 to 4.0, 0.80 to 4.0, 0.70 to 1.5, or 0.80 to 4.0.
  • the ratio of silicon to potassium (Si / K) in the main body 2 is lower than the ratio of silicon to potassium in the coating 4.
  • the ratio of silicon to potassium in the main body 2 is derived from the ratio of silicon to potassium in the above-mentioned fluoride phosphor. In the case of K 2 SiF 6 , the value is theoretically 0.5, and generally 0.4 to 0.5, although it varies depending on the preparation conditions.
  • the internal quantum efficiency of the phosphor 10 can be, for example, 80% or more.
  • the phosphor 10 also maintains an internal quantum efficiency of 70% or higher even after a test of exposure to a high temperature and high humidity environment (exposure test under conditions of temperature: 60 ° C. and humidity: 90% RH for 25 hours). Can be.
  • the internal quantum efficiency of the phosphor 10 can sufficiently maintain the initial internal quantum efficiency even after the test of exposure to the high temperature and high humidity environment.
  • the maintenance rate of the internal quantum efficiency after the test with respect to the internal quantum efficiency before the test exposed to the high temperature and high humidity environment can be, for example, 90% or more, 93% or more, or 95% or more, and is excellent in moisture resistance reliability. ..
  • Example 1 [Preparation of KMF (K 2 MnF 6 )]
  • KMF K 2 MnF 6
  • hydrofluoric acid concentration: 40% by mass
  • 260.00 g of potassium hydrogen fluoride powder manufactured by Kanto Chemical Co., Ltd.
  • 12.00 g were added.
  • An aqueous hydrofluoric acid solution was prepared by dissolving potassium permanganate powder (manufactured by Kanto Chemical Co., Ltd.).
  • KSF Fluoride Fluorescent Substance: KSF (K 2 SiF 6 )
  • KSF was prepared by the method shown below.
  • 200 mL of hydrofluoric acid concentration: 55% by mass, manufactured by Stella Chemifa
  • 25.6 g of potassium bifluoride powder was measured here.
  • An aqueous solution of hydrofluoric acid was prepared by dissolving (manufactured by Yakuhin Co., Ltd.).
  • the solution was stirred for a while to complete the precipitation of the yellow powder.
  • the yellow powder was precipitated by terminating the stirring and allowing the solution to stand. Then, the supernatant was removed, and the yellow powder was washed with hydrofluoric acid (manufactured by Stella Chemifa) and methanol (manufactured by Kanto Chemical Co., Inc.). After washing, the yellow powder was collected by filtration. After the recovered yellow powder was dried, it was classified using a nylon sieve having a mesh size of 75 ⁇ m, and 20.3 g of KSF (fluoride phosphor) in the form of a yellow powder was obtained as the powder that passed through the sieve. The volume median diameter (D50) of the KSF was 28 ⁇ m.
  • a phosphor was prepared by treating the KSF (fluoride phosphor) prepared as described above with a solution containing a compound containing potassium, a manganese reducing agent and a silicon compound. Specifically, it is as follows. First, in a container, 0.14 g of potassium acetate (AcK), 1 g of hydrogen peroxide solution (H 2 O 2 , concentration: 30% by mass, manufactured by Kanto Chemical Co., Inc.), 6.8 g (23.1 mmol) of tetra.
  • AcK potassium acetate
  • H 2 O 2 concentration: 30% by mass, manufactured by Kanto Chemical Co., Inc.
  • An aqueous solution was prepared by measuring ethoxysilane (TEOS, manufactured by Kanto Chemical Co., Inc.), 0.839 g of acetic acid (AcOH), and 470 g of ion-exchanged water. Next, 10.0 g of the KSF was added, and the aqueous solution was stirred at a rotation speed of 250 rpm for 10 hours. The amount of manganese in the above KSF was 0.97% by mass based on the total amount of fluoride phosphor.
  • TEOS ethoxysilane
  • AcOH acetic acid
  • the solid content was precipitated by completing the stirring and allowing the aqueous solution to stand. Then, the supernatant was removed, methanol was added, and the mixture was stirred to wash the solid content. After washing, the solid content was recovered by filtration, and the recovered solid content was dried under the condition of 100 ° C. for 3 hours. After drying, the mixture was classified using a nylon sieve having a mesh size of 75 ⁇ m, and 8.70 g of a yellow powdery phosphor was obtained as a powder that passed through the sieve.
  • Example 2 A fluorescent substance was obtained in the same manner as in Example 1 except that the blending ratio of each component, the treatment conditions, and the drying conditions were changed as shown in Table 1.
  • monochromatic Al-K ⁇ rays are used as the X-ray source, output: 36 W, detection angle: 90 °, path energy: 200.00 eV (wide spectrum) and 50.0 eV (narrow spectrum [O1s, F1s, Under the conditions of Si2p, K2p, Ca2p, Cl2p, Mn2p]), the ratio of elements on the surface of the phosphor and KSF was measured with respect to the measurement region of 400 ⁇ m ⁇ 200 ⁇ m, and the ratio of silicon to potassium (Si / K). And the ratio of oxygen to potassium (O / K) was calculated.
  • the charge neutralization was performed by emitting a current of 100 ⁇ A using an electron gun.
  • a standard reflector manufactured by Labsphere, trade name: Spectralon having a reflectance of 99% was set in the side opening ( ⁇ 10 mm) of the integrating sphere ( ⁇ 60 mm).
  • Monochromatic light dispersed at a wavelength of 455 nm from a light emitting light source (Xe lamp) was introduced into the integrating sphere by an optical fiber, and the spectrum of the reflected light was measured by a spectroscope.
  • the number of excited photons (Qex) was calculated from the spectrum in the wavelength range of 450 to 465 nm.
  • a concave cell filled with a phosphor so as to have a smooth surface is set in the opening of the integrating sphere, irradiated with the monochromatic light having a wavelength of 455 nm, and the spectrum of the reflected light and fluorescence of the excitation is measured. Measured by a spectroscope. From the obtained spectral data, the number of excited reflected light photons (Qref) and the number of fluorescent photons (Qem) were calculated. The number of excited reflected light photons was calculated in the same wavelength range as the number of excited light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm.

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PCT/JP2020/023237 2019-06-21 2020-06-12 蛍光体及び蛍光体の製造方法 Ceased WO2020255881A1 (ja)

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WO2022255219A1 (ja) * 2021-05-31 2022-12-08 日亜化学工業株式会社 フッ化物蛍光体、その製造方法及び発光装置
JP2022184763A (ja) * 2021-05-31 2022-12-13 日亜化学工業株式会社 フッ化物蛍光体、その製造方法及び発光装置
WO2023037831A1 (ja) * 2021-09-09 2023-03-16 信越化学工業株式会社 被覆ｋｓｆ蛍光体、該蛍光体の製造方法、該蛍光体を含有する硬化性シリコーン組成物及び光半導体装置
WO2025150472A1 (ja) * 2024-01-11 2025-07-17 デンカ株式会社 フッ化物蛍光体粒子、複合体、発光装置およびフッ化物蛍光体の製造方法
US12545836B2 (en) 2021-06-21 2026-02-10 Nichia Corporation Fluoride phosphor and method of producing the same, wavelength conversion member, and light emitting device

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KR102907720B1 (ko) * 2024-06-10 2026-01-05 주식회사 유제이엘 내습 및 내열성 적색 형광체, 이의 합성 방법 및 이를 포함하는 발광 장치

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WO2022255219A1 (ja) * 2021-05-31 2022-12-08 日亜化学工業株式会社 フッ化物蛍光体、その製造方法及び発光装置
JP2022184763A (ja) * 2021-05-31 2022-12-13 日亜化学工業株式会社 フッ化物蛍光体、その製造方法及び発光装置
US12545836B2 (en) 2021-06-21 2026-02-10 Nichia Corporation Fluoride phosphor and method of producing the same, wavelength conversion member, and light emitting device
WO2023037831A1 (ja) * 2021-09-09 2023-03-16 信越化学工業株式会社 被覆ｋｓｆ蛍光体、該蛍光体の製造方法、該蛍光体を含有する硬化性シリコーン組成物及び光半導体装置
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WO2025150472A1 (ja) * 2024-01-11 2025-07-17 デンカ株式会社 フッ化物蛍光体粒子、複合体、発光装置およびフッ化物蛍光体の製造方法

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JPWO2020255881A1 (https=) 2020-12-24
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