WO2019021756A1 - Luminophore et son procédé de production, feuille de luminophore et dispositif d'éclairage - Google Patents

Luminophore et son procédé de production, feuille de luminophore et dispositif d'éclairage Download PDF

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WO2019021756A1
WO2019021756A1 PCT/JP2018/025116 JP2018025116W WO2019021756A1 WO 2019021756 A1 WO2019021756 A1 WO 2019021756A1 JP 2018025116 W JP2018025116 W JP 2018025116W WO 2019021756 A1 WO2019021756 A1 WO 2019021756A1
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phosphor
diffraction
peak
sulfite
intensity
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Japanese (ja)
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和弘 八木橋
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デクセリアルズ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements

Definitions

  • the present invention relates to a phosphor, a method of manufacturing the same, a phosphor sheet, and a lighting device.
  • pseudo white LEDs using a yellow phosphor YAG: Ce have been used in low-priced TVs and displays.
  • the color purity of green and red is reduced because it does not match the characteristics of the red and green color filters.
  • SrGa 2 S 4 Eu phosphor
  • SrGa 2 S 4 Eu phosphor
  • SrGa 2 S 4 in connection with Eu phosphor, for example, SrGa the purpose of improving internal quantum efficiency 2 S 4: Eu phosphor
  • An object of the present invention is to solve the above-mentioned problems in the prior art and to achieve the following objects. That is, the present invention provides a green light emitting phosphor having high color purity while having high luminance, a method for producing the same, a phosphor sheet having the phosphor, and a lighting device having the phosphor sheet. With the goal.
  • the means for solving the problems are as follows. That is, ⁇ 1> A phosphor comprising at least a phosphor represented by the following general formula (1) and satisfying the following conditions (1) to (3).
  • Condition (1): The diffraction intensity maximum peak of the XRD pattern is a diffraction peak belonging to the (422) plane of SrGa 2 S 4 appearing at the diffraction angle 2 ⁇ 23.7 to 24.1 °.
  • Condition (3) A diffraction peak having a relative intensity of 5 to 20% relative to the diffraction intensity maximum peak is present at a diffraction angle 2 ⁇ of 30.0 to 30.4 °.
  • ⁇ 2> The phosphor according to ⁇ 1>, wherein y value of the fluorescent substance based on CIE 1931 color system is 0.687 or more.
  • ⁇ 3> The phosphor according to any one of ⁇ 1> to ⁇ 2>, wherein the internal quantum efficiency of the phosphor is 0.64 or more.
  • a phosphor sheet comprising a phosphor layer containing the phosphor according to any one of ⁇ 1> to ⁇ 3> and a red phosphor.
  • a lighting device comprising the phosphor sheet according to ⁇ 4>.
  • ⁇ 6> A method for producing a phosphor, wherein the phosphor according to any one of ⁇ 1> to ⁇ 3> is produced, A barium sulfide, a strontium compound, and a europium compound are dissolved, and a first liquid containing a powdered gallium compound is mixed with a second liquid containing sulfite to form barium sulfite, strontium sulfite, and europium sulfite.
  • a precipitation and precipitation step of obtaining a precipitate which is a mixture of the contained precipitate and the powdered gallium compound.
  • the above problems in the prior art can be solved, the above object can be achieved, and a phosphor emitting green light with high color purity while having high luminance, a method for producing the same, and the phosphor And a lighting device having the phosphor sheet.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a phosphor sheet end.
  • FIG. 2 is a schematic cross-sectional view showing an edge light type illumination device.
  • FIG. 3 is a schematic cross-sectional view showing a direct type illumination device.
  • FIG. 4 is a graph showing the relationship between the emission peak wavelengths of the phosphors of Examples 1 to 7 and Comparative Examples 1 to 4 and the emission peak intensity.
  • FIG. 5 is a graph showing CIEx, y of the phosphors of Examples 1 to 7 and Comparative Examples 1 to 4.
  • FIG. 6 is an X-ray diffraction pattern of the phosphors of Examples 1, 4, 5, 7 and Comparative Examples 1 to 4.
  • the phosphor of the present invention contains at least a fluorescent substance, and further contains other components such as a coating layer, if necessary.
  • the fluorescent material is represented by the following general formula (1). (Ba y Sr 1-y ) 1-x Ga 2 S 4 : Eu x ... general formula (1) However, in the general formula (1), 0.025 ⁇ x ⁇ 0.20 and 0.15 ⁇ y ⁇ 0.49.
  • the fluorescent material satisfies the following conditions (1) to (3).
  • Condition (3) A diffraction peak having a relative intensity of 5 to 20% relative to the diffraction intensity maximum peak is present at a diffraction angle 2 ⁇ of 30.0 to 30.4 °.
  • the Ga / (Eu + Ba + Sr) ratio (element ratio) is preferably 1.80 to 2.50, and more preferably 1.90 to 2.30.
  • Examples of the emission peak wavelength of the fluorescent substance include 529 nm to 535 nm.
  • Examples of the emission peak intensity (ratio to YAG) of the fluorescent substance include, for example, 2.46 to 3.64.
  • the sample absorption rate of the fluorescent substance may be, for example, 64% to 82%.
  • x based on the CIE 1931 color system of the fluorescent substance 0.271 or less is preferable.
  • Examples of the x value based on the CIE 1931 color system of the fluorescent substance include 0.210 to 0.271, and 0.235 to 0.271.
  • the y value of the fluorescent substance based on the CIE 1931 color system is preferably 0.687 or more.
  • Examples of the y value based on the CIE 1931 color system of the fluorescent substance include, for example, 0.687 to 0.710, and also, 0.687 to 0.695.
  • the internal quantum efficiency of the fluorescent substance is preferably 0.64 (64%) or more.
  • the internal quantum efficiency of the fluorescent substance may be, for example, 0.64 (64%) to 0.80 (80%).
  • the external quantum efficiency of the fluorescent substance is preferably 0.40 (40%) or more.
  • Examples of the external quantum efficiency of the fluorescent substance include 0.40 (40%) to 0.65 (65%).
  • Examples of the luminance (ratio to YAG) of the fluorescent substance include 124% to 187%.
  • the full width at half maximum of the fluorescent material may be, for example, 48 nm to 50 nm.
  • the emission peak wavelength, emission peak intensity, and emission half width in the PL spectrum are measured using an integrating sphere option of a spectrofluorimeter FP-6500 (manufactured by JASCO Corporation).
  • the emission peak intensity is shown as a relative value based on PL spectrum data of a general YAG phosphor P46-Y3 material manufactured by Kasei Optronics.
  • the conversion efficiency of the phosphor As the conversion efficiency of the phosphor, the efficiency of absorbing excitation light (absorptivity), the efficiency of converting absorbed excitation light into fluorescence (internal quantum efficiency), and the efficiency of converting excitation light as a product thereof into fluorescence (external Calculate quantum efficiency).
  • the luminescence characteristics are measured using an integrating sphere option of a spectrofluorimeter FP-6500 (manufactured by JASCO Corporation).
  • the phosphor powder is filled in a dedicated cell, and blue excitation light with a wavelength of 450 nm is irradiated to measure the fluorescence spectrum.
  • the quantum efficiency is calculated using the result from the quantum efficiency calculation software attached to the spectrofluorimeter.
  • the crystallinity is evaluated by X-ray diffraction measurement.
  • the position (2 ⁇ ) and half width of the diffraction peak in the X-ray diffraction (XRD) pattern of the CuK ⁇ ray are measured using a powder X-ray diffractometer (X'Pert PRO manufactured by PANalytical). Perform fitting with the peak search function of the attached analysis software, and analyze the characteristics of the XRD pattern of the phosphor.
  • covered with the fluorine resin as a coating layer is mentioned.
  • covered with the fluorine resin as a coating layer is mentioned.
  • the method for producing a phosphor of the present invention at least includes a precipitation and precipitation step, and further, if necessary, other steps such as a firing step and a coating step.
  • the method of producing the phosphor is a method of producing the phosphor of the present invention.
  • Precipitation precipitation process There is no particular limitation on the precipitation precipitation step, as long as it is a step of mixing a first liquid and a second liquid to obtain a precipitate, and can be appropriately selected according to the purpose.
  • the first liquid dissolves a barium compound, a strontium compound, and a europium compound, and contains a powdered gallium compound.
  • Examples of a method of obtaining the first liquid include a method of dissolving a barium compound, a strontium compound, and a europium compound in water and mixing powder of a gallium compound therein.
  • barium compound examples include barium nitrate [Ba (NO 3 ) 2 ], barium oxide [BaO], barium bromide [BaBr 2 .xH 2 O], barium chloride [BaCl 2 .xH 2 O], and barium acetate.
  • barium nitrate [Ba (NO 3 ) 2 barium oxide [BaO], barium bromide [BaBr 2 .xH 2 O], barium chloride [BaCl 2 .xH 2 O], and barium acetate.
  • barium iodide [BaI 2 .xH 2 O] barium hydroxide [Ba (OH) 2 ]
  • barium sulfide [BaS] or the like can be used.
  • strontium compound examples include strontium nitrate [Sr (NO 3 ) 2 ], strontium oxide [SrO], strontium bromide [SrBr 2 .xH 2 O], strontium chloride [SrCl 2 .xH 2 O], strontium carbonate [SrCO 3 ], Strontium borate [SrC 2 O 4 ⁇ H 2 O], Strontium fluoride [SrF 2 ], Strontium iodide [SrI 2 ⁇ xH 2 O], Strontium sulfate [SrSO 4 ], Strontium hydroxide [Sr (OH) 2 ⁇ x H 2 O], strontium sulfide [SrS] or the like can be used.
  • europium compound for example, europium nitrate [Eu (NO 3) 3 ⁇ xH 2 O], oxalate europium [Eu 2 (C 2 O 4 ) 3 ⁇ xH 2 O], europium carbonate [Eu 2 (CO 3) 3 ⁇ x H 2 O], europium sulfate [Eu 2 (SO 4 ) 3 ], europium chloride [EuCl 3 ⁇ x H 2 O], europium fluoride [EuF 3 ], europium hydride [EuH x ], europium sulfide [EuS ], tri -i- propoxy europium [Eu (O-i-C 3 H 7) 3], europium acetate [Eu (O-CO-CH 3) 3] , or the like can be used.
  • Examples of the powdery gallium compound include gallium oxide [Ga 2 O 3 ], gallium sulfate [Ga 2 (SO 4 ) 3 .xH 2 O], gallium nitrate [Ga (NO 3 ) 3 .xH 2 O], and odor Gallium fluoride [GaBr 3 ], gallium chloride [GaCl 3 ], gallium iodide [GaI 3 ], gallium sulfide (II) [GaS], gallium sulfide (III) [Ga 2 S 3 ], gallium oxyhydroxide [GaOOH] Etc. can be used.
  • the second liquid contains sulfite.
  • the method of dissolving a sulfite in water is mentioned, for example.
  • ammonium sulfite sodium sulfite, potassium sulfite etc. are mentioned, for example.
  • the precipitate is a mixture of the precipitate and the powdered gallium compound.
  • the precipitate contains barium sulfite, strontium sulfite and europium sulfite.
  • the barium compound, the strontium compound, and the europium compound are dissolved and uniform, so that barium sulfite, strontium sulfite, and europium sulfite are uniformly mixed even in the precipitate. .
  • the powdered gallium compound, barium sulfite, strontium sulfite and europium sulfite are uniformly mixed.
  • cleaning cleaning with water is mentioned until it becomes 0.1 mS / cm or less in conductivity.
  • ⁇ Firing process> If it is a process which bakes the said precipitate under the atmosphere containing hydrogen sulfide as said baking process, there is no restriction
  • a firing temperature in the firing step for example, 900 ° C. to 950 ° C. may be mentioned.
  • the firing time in the firing step may be, for example, 1 hour to 5 hours.
  • the objective it can select suitably, For example, the amount of 0.1 L / min-0.5 L / min of hydrogen sulfide is baked It is possible to supply in the atmosphere.
  • the fluorescent substance in the phosphor of the present invention can be obtained by the firing step.
  • the covering step is not particularly limited as long as it is a step of covering the surface of the fluorescent material obtained by the firing step with a covering layer, and can be appropriately selected according to the purpose.
  • the coating step can be performed, for example, by coating a fluorine-based resin in a non-water-based atmosphere.
  • the fluorescent material obtained above is mixed with the fluorine-based resin solution, Mix with a mix rotor etc.
  • the powder is collected by suction filtration, and the powder is dried at a temperature of about 80 ° C. to 100 ° C. for 0.5 hour to 1.5 hours. Thereby, the fluorescent substance which has the coating layer by a fluorine resin on the surface can be obtained.
  • the phosphor sheet of the present invention has at least a phosphor layer, and optionally, other members such as a water vapor barrier film.
  • the phosphor layer contains at least the phosphor of the present invention and a red phosphor, and further contains other components such as a resin as required.
  • the phosphor layer is formed, for example, by dispersing the phosphor of the present invention and the red phosphor in the layered resin.
  • Red Phosphor There is no restriction
  • red phosphor examples include (ME: Eu) S, (M: Sm) x (Si, Al) 12 (O, N) 16 , ME 2 Si 5 N 8 : Eu, (ME: Eu) SiN 2 , (ME: Eu) AlSiN 3 , (ME: Eu) 3 SiO 5 , (Ca: Eu) SiN 2 , (Ca: Eu) AlSiN 3 , Y 2 O 3 : Eu, YVO 4 : Eu, Y ( P, V) O 4 : Eu, 3.5 MgO ⁇ 0.5 MgF 2 ⁇ Ge 2 : Mn, CaSiO 3 : Pb, Mn, Mg 6 As O 11 : Mn, (Sr, Mg) 3 (PO 4 ) 3 : Sn And La 2 O 2 S: Eu, Y 2 O 2 S: Eu, and the like.
  • CaS: Eu or (Ba, Sr) 3 SiO 5 : Eu capable of realizing a wide color gamut is preferably used.
  • “ME” means at least one type of atom selected from the group consisting of Ca, Sr and Ba
  • “M” is at least one type selected from the group consisting of Li, Mg and Ca It means an atom.
  • the front of ":” shows a mother body, and after “:” shows an activator.
  • Resin As said resin, the polyolefin copolymer, the hardened
  • a styrene-type copolymer or its hydrogenated substance can be mentioned.
  • a styrene-based copolymer or a hydrogenated product thereof a styrene-ethylene-butylene-styrene block copolymer or a hydrogenated product thereof, a styrene-ethylene-propylene block copolymer or a hydrogenated product thereof is preferably mentioned.
  • hydrogenated products of styrene-ethylene-butylene-styrene block copolymer can be particularly preferably used from the viewpoint of transparency and gas barrier properties.
  • Examples of the photocurable (meth) acrylic resin include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like, and among these, the heat resistance after photocuring From these, urethane (meth) acrylate can be preferably used. By containing such a photocurable (meth) acrylic resin, excellent light resistance and low water absorption can be obtained.
  • water vapor barrier film examples include a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate such as PET (polyethylene terephthalate) or a film. Moreover, you may use the thing of multilayer structures, such as PET / SiOx / PET.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a phosphor sheet end.
  • the phosphor layer 11 is sandwiched between the first water vapor barrier film 12 and the second water vapor barrier film 13.
  • the phosphor layer 11 contains the above-mentioned phosphor of the present invention which emits green fluorescence and a red phosphor which emits red fluorescence of a wavelength of 620 to 660 nm by irradiation of blue excitation light, and the irradiated blue light is converted to white light. Convert.
  • Zn 2 SiO 4 Mn
  • Y 3 Al 5 O 12 Ce 3+
  • (Y, Gd) Al 3 (BO 3 ) 4 Tb 3 +
  • Ca 3 Sc 2 Si 3 O 12 Ce
  • CaSc 2 O 4 Ce
  • Ba 3 Si 6 O 12 N 2 Eu
  • ⁇ -Sialon Eu 2+ etc. from 1 type or 2 or more types in combination It is also good.
  • the phosphor layer 11 is formed by depositing a resin composition containing the powder-like phosphor of the present invention and a red phosphor.
  • the cover member 14 has an end portion of the first water vapor barrier film 12 and an end portion of the second water vapor barrier film 13 having a water vapor transmission rate of 1 g / m 2 / day or less. Is preferably sealed.
  • the cover member 14 it is possible to use a pressure-sensitive adhesive tape in which a pressure-sensitive adhesive 142 is applied to a substrate 141 having a water vapor transmission rate of 1 g / m 2 / day or less.
  • the base material 141 metal foil such as aluminum foil or the like and the water vapor barrier films 12, 13 can be used.
  • aluminum foil may use either glossy white aluminum or non-lustrous black aluminum, it is preferable to use white aluminum when a good color tone at the end of the phosphor sheet is required.
  • the width W of the cover member 14 to be attached onto the water vapor barrier film is preferably 1 mm to 10 mm, and more preferably 1 mm to 5 mm from the viewpoint of water vapor barrier properties and strength. According to the cover member 14 having such a configuration, it is possible to prevent water vapor from entering the phosphor layer from the end of the water vapor barrier film, and to prevent deterioration of the phosphor in the phosphor layer. .
  • the lighting device of the present invention comprises the phosphor sheet of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an edge light type illumination device. As shown in FIG. 2, the illumination device diffuses blue light of the blue LED 31 and the blue LED 31 incident from the side, and a light guide plate 32 that emits uniform light on the surface, and phosphor that obtains white light from blue light A so-called "edge light type backlight" including the sheet 33 and the optical film 34 is configured.
  • the blue LED 31 constitutes a so-called "LED package” having an InGaN-based LED chip as a blue light emitting element.
  • the light guide plate 32 uniformly emits light from the end face of a transparent substrate such as an acrylic plate.
  • the phosphor sheet 33 is, for example, a phosphor sheet shown in FIG.
  • the powder of the phosphor contained in the phosphor sheet 33 has an average particle diameter of several ⁇ m to several tens of ⁇ m. Thereby, the light scattering effect of the phosphor sheet 33 can be improved.
  • the optical film 34 is made of, for example, a reflective polarizing film, a diffusion film, or the like for improving the visibility of the liquid crystal display device.
  • FIG. 3 is a schematic cross-sectional view showing a direct type illumination device.
  • the lighting device includes a substrate 42 on which blue LEDs 41 are two-dimensionally arranged, a diffusion plate 43 for diffusing the blue light of the blue LEDs 41, and a distance from the substrate 42.
  • a so-called "direct-type backlight” is provided, which includes a phosphor sheet 33 for obtaining the light intensity and an optical film 34.
  • the blue LED 41 constitutes a so-called "LED package” having, for example, an InGaN-based LED chip as a blue light emitting element.
  • the substrate 42 is made of a glass cloth base material using a resin such as phenol, epoxy, polyimide, etc.
  • blue LEDs 41 are equally spaced at a predetermined pitch, and two corresponding to the entire surface of the phosphor sheet 33. Placed in a dimension.
  • the mounting surface of the blue LED 41 on the substrate 42 may be subjected to a reflection process as necessary.
  • the substrate 42 and the phosphor sheet 33 are spaced apart by about 10 to 50 mm, and the illumination device constitutes a so-called "remote phosphor structure".
  • the gap between the substrate 42 and the phosphor sheet 33 is held by a plurality of support columns and reflectors, and the support columns and reflectors are provided so as to surround the space formed by the substrate 42 and the phosphor sheet 33 in four directions. .
  • the diffusion plate 43 diffuses the emitted light from the blue LED 41 in such a wide range that the shape of the light source can not be seen, and has a total light transmittance of, for example, 20% or more and 80% or less.
  • the present invention is not limited to the above-described embodiment, and it goes without saying that various updates can be added without departing from the scope of the present invention.
  • the example which applied the illuminating device to the back light source for display apparatuses was shown in above-mentioned embodiment, you may apply to the light source for illumination.
  • the optical film 34 is often unnecessary.
  • the phosphor-containing resin may have not only a flat sheet shape but also a three-dimensional shape such as a cup shape.
  • the conversion efficiency of the phosphor As the conversion efficiency of the phosphor, the efficiency of absorbing excitation light (absorptivity), the efficiency of converting absorbed excitation light into fluorescence (internal quantum efficiency), and the efficiency of converting excitation light as a product thereof into fluorescence (external Quantum efficiency was calculated.
  • the luminescence characteristics were measured using an integrating sphere option of a spectrofluorimeter FP-6500 (manufactured by JASCO Corporation).
  • the phosphor powder was filled in a dedicated cell, and blue excitation light with a wavelength of 450 nm was irradiated to measure the fluorescence spectrum.
  • the quantum efficiency was calculated using the result from the quantum efficiency calculation software attached to the spectrofluorimeter.
  • europium compounds (Eu (NO 3) 3 ⁇ nH 2 O) 1.115g, barium compound (Ba (NO 3) 2) 3.822g, and strontium compounds (Sr (NO 3) 2) 17 It is .539g.
  • a europium compound, a barium compound and a strontium compound were added to 300 ml of pure water, and the mixture was sufficiently stirred until the unsolved portion disappeared, to obtain a mixed solution containing Eu, Ba and Sr.
  • 18.744 g of a powdery gallium compound (powdery Ga 2 O 3 ) was added so that the molar amount of Ga was 2.0 times the sum of the molar amounts of Eu, Ba, and Sr.
  • the mixture was sufficiently stirred to prepare a mixed solution of nitrate and gallium oxide powder.
  • 15.4 g of ammonium sulfite having a number of moles of 1.15 times the total number of moles of Eu, Ba, and Sr was dissolved in 100 ml of pure water to prepare a sulfite solution.
  • the sulfite solution was added dropwise to the above mixed solution of nitrate and gallium oxide powder to obtain a precipitate / precipitate.
  • the precipitate / precipitate is a mixture of europium sulfite, barium and strontium powder and gallium oxide powder. Then, the precipitates were washed with pure water, filtered, and dried at 120 ° C.
  • a powder mixture containing Eu, Ba, Ga, and Sr was obtained by passing a wire mesh with a nominal opening of 100 ⁇ m.
  • This powder mixture is a mixture containing europium sulfite-barium-strontium powder [powder composed of (Ba, Sr, Eu) SO 3 ] and gallium oxide.
  • the powder mixture was then fired in an electric furnace. The firing conditions were as follows. The temperature was raised to 925 ° C. in 1.5 hours, then held at 925 ° C. for 1.5 hours, and then allowed to cool to room temperature in 2 hours.
  • the above sample preparation method is described as a wet method in Table 1.
  • Examples 2 to 7 and Comparative Examples 1 to 3 As shown in Table 1, the composition formula (Ba y Sr 1-y) 1-x Ga 2 S 4: in the phosphor represented by Eu x, x values of the examples and comparative examples, shown in y value The weight values of the respective raw materials were calculated so as to be 0.1 molar amount by the composition ratio. Other than this, a wet method in the same manner as in Example 1, the Examples, and Comparative Examples (Ba y Sr 1-y) 1-x Ga 2 S 4: to obtain phosphor particles consisting of Eu x.
  • the powder mixture was put in an alumina baking boat and baked in an electric furnace.
  • the above-mentioned trial production method is described in Table 1 as a dry method.
  • the evaluation results of the light emission characteristics of Examples 2 to 7 are also shown in Table 2.
  • the emission peak wavelength was 529 to 535 nm
  • the emission peak intensity was 2.46 to 3.64 (YAG ratio)
  • the luminance was 124.7 to 187.0% (YAG ratio)
  • the emission half width was 48 to 50 nm.
  • the CIEx, y chromaticity point showed coordinates in the range of (0.235, 0.695) to (0.271, 0.687).
  • the absorptivity is 66.4 to 81.8%
  • the internal quantum efficiency is 64.6 to 79.0%
  • the external quantum efficiency is 43.4 to 64.6%. .
  • the evaluation results of the light emission characteristics of Comparative Examples 1 to 4 are also shown in Table 2.
  • the emission peak wavelength was 528 to 538 nm, the emission peak intensity was 1.25 to 3.43 (YAG ratio), the luminance was 68.1 to 192.7% (YAG ratio), and the emission half width was 48 to 54 nm.
  • the CIEx, y chromaticity points became discrete coordinate positions in the range of CIEx value of 0.231 to 0.288 and CIEy value of 0.672 to 0.686.
  • the absorptivity was 62.6 to 80.1%
  • the internal quantum efficiency was 37.6 to 75.3%
  • the external quantum efficiency was 24.9 to 60.3%. .
  • Examples 1 to 7 and Comparative Examples 1 to 4 are indicated by “ ⁇ ”.
  • the Green chromaticity points (0.210, 0.710) of NTSC are indicated by " ⁇ ”.
  • the chromaticity points of Examples 1 to 7 moved in the range of (0.271, 0.687) to (0.235, 0.695) almost on a single curve as the wavelength became shorter.
  • the CIE y values of Examples 1 to 7 are larger than Comparative Examples 1 to 4 and close to the Green chromaticity point of NTSC, it is understood that Examples 1 to 7 have higher green color purity.
  • Table 3 shows the evaluation results of the crystallinity of the phosphors of Examples 1 to 7 and Comparative Examples 1 to 4.
  • the X-ray diffraction patterns of Examples 1, 4, 5, 7 and Comparative Examples 1 to 4 are shown in FIG.
  • the crystals of Examples 1 to 7 had unique crystal structures. Specifically, a diffraction peak appears at a diffraction angle 2 ⁇ of 30.0 to 30.4 °, and the relative intensity with respect to the maximum peak shows a certain range.
  • a peak having a relative intensity of 8.8% with respect to the diffraction intensity maximum peak appeared at the position of 30.2 °.
  • Comparative Example 1 the X-ray diffraction pattern is shown in FIG. 6, but the peak of the diffraction intensity maximum appears a diffraction peak belonging to the (422) plane of SrGa 2 S 4 at the diffraction angle 2 ⁇ of 24.06 °.
  • the second peak of the diffraction intensity shows a diffraction peak belonging to the (444) plane at a diffraction angle 2 ⁇ of 38.42 °, but no peak appears at a diffraction angle 2 ⁇ of 30.0 to 30.4 ° .
  • the relative intensity to the diffraction intensity maximum peak is 5 to 3 at a diffraction angle 2 ⁇ of 30.0 to 30.4 °. It is characterized by having a 20% diffraction peak.
  • the diffraction intensity maximum peak is a diffraction peak belonging to the (422) plane of SrGa 2 S 4 appearing at a diffraction angle 2 ⁇ of 23.7 ° to 24.1 °.

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Abstract

La présente invention concerne un luminophore qui est représenté par la formule générale (1) et qui contient au moins une substance fluorescente qui satisfait aux conditions (1) à (3). Formule générale (1) : (BaySr1-y)1-xGa2S4:Eux (dans la formule générale (1), 0,025 ≤ x ≤ 0,20 et 0,15 ≤ y ≤ 0,49 sont satisfaites). Condition (1) : le pic maximal de l'intensité de diffraction dans un motif XRD est un pic de diffraction qui apparaît à un angle de diffraction 2θ = 23,7° à 24,1° et est attribué au plan (422) de SrGa2S4. Condition (2) : le deuxième pic le plus haut de l'intensité de diffraction apparaît à un angle de diffraction 2θ = 38,1° à 38,5° et est attribué au plan (444) de SrGa2S4. Condition (3) : les pics de diffraction ayant une intensité relative de 5 à 20 % du pic maximal de l'intensité de diffraction apparaissent à un angle de diffraction 2θ = 30,0° à 30,4°.
PCT/JP2018/025116 2017-07-26 2018-07-02 Luminophore et son procédé de production, feuille de luminophore et dispositif d'éclairage WO2019021756A1 (fr)

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