WO2023120034A1 - 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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WO2023120034A1
WO2023120034A1 PCT/JP2022/043596 JP2022043596W WO2023120034A1 WO 2023120034 A1 WO2023120034 A1 WO 2023120034A1 JP 2022043596 W JP2022043596 W JP 2022043596W WO 2023120034 A1 WO2023120034 A1 WO 2023120034A1
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phosphor
chromium
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content
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French (fr)
Japanese (ja)
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良々歌 中嶋
広樹 坂野
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Denka Co Ltd
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Denka Co Ltd
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Priority to KR1020247023804A priority Critical patent/KR20240121857A/ko
Priority to CN202280083923.0A priority patent/CN118401631A/zh
Priority to JP2023569202A priority patent/JPWO2023120034A1/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
    • C09K11/67—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • 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
    • C09K11/66—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only

Definitions

  • the present disclosure relates to phosphors and phosphor manufacturing methods.
  • Light-emitting devices having light-emitting elements such as light-emitting diodes are used for general lighting, backlights for liquid crystal displays, LED displays, and light-emitting devices for quality inspection.
  • An LED display uses, for example, 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.
  • Various phosphors such as a red phosphor and a green phosphor are used as the wavelength converter.
  • near-infrared light can also be used as a heat source
  • studies are underway on phosphors that emit light in the near-infrared region.
  • a phosphor that emits light in the near-infrared region a phosphor having chromium as a luminescence center is proposed as a candidate.
  • Patent Document 1 in a chemical composition of 1 mol, the molar ratio of the total of Gd and Cr is 1, and the molar ratio of Cr is 0.0085 or more and 0.05 or less, Gd, Cr, and Al and is excited by light having an emission peak wavelength in the range of 380 nm or more and 480 nm or less, and having an emission peak wavelength in the range of 690 nm or more and 790 nm or less.
  • Patent Document 2 discloses a light-emitting device comprising a light-emitting source and a phosphor, wherein the phosphor contains at least a near-infrared light-emitting phosphor that emits near-infrared light when excited. It is
  • a phosphor that emits near-infrared light and has excellent emission intensity is useful.
  • An object of the present disclosure is to provide a phosphor with excellent emission intensity and a method for producing the same.
  • the present disclosure provides the following [1] to [9].
  • the main crystal phase has the same structure as the Li2MgGeO4 crystal phase, Containing tetravalent chromium as an activating element,
  • the integral value of the spectrum with a wavelength of 700 to 900 nm is X
  • the integral value of the spectrum with a wavelength of 1100 to 1300 nm is Y / X value. is 50 or more.
  • the main crystal phase is represented by the general formula: A 2 B(C 1-x Cr x )O 4 (wherein A, B and C represent mutually different metal elements);
  • a in the general formula contains Li
  • the content of Li in A is 90 mol % or more.
  • a composition containing a compound having lithium as a constituent element, a compound having magnesium as a constituent element, a compound having germanium as a constituent element, and a compound having chromium as a constituent element is fired in air to obtain a fired product. process and a step of reducing at least part of chromium in the fired product by heat-treating the fired product at a temperature of 850° C. or less; A method for producing a phosphor, wherein the chromium content is 8 mol % or less with respect to the total amount of germanium and chromium in the composition. [9] The production method according to [8], wherein the heat treatment of the fired product is performed in a reducing atmosphere containing ammonia.
  • the main crystalline phase has the same structure as the Li 2 MgGeO 4 crystalline phase, contains tetravalent chromium as an activating element, and the fluorescence spectrum has a wavelength of 700 to 900 nm.
  • a phosphor in which the value of Y/X is 50 or more, where X is the integrated value of the spectrum with a wavelength of 1100 to 1300 nm and Y is the integrated value.
  • the above-described phosphor can exhibit excellent emission intensity by having the ratio of the integrated intensity of the specific wavelength region in the fluorescence spectrum within a predetermined range.
  • the peak observed in the wavelength range of 700 to 900 nm corresponds to the emission of trivalent chromium
  • the peak observed in the wavelength range of 1100 to 1300 nm. corresponds to the emission of tetravalent chromium
  • the main crystal phase is represented by the general formula: A 2 B(C 1-x Cr x ) O 4 (wherein A, B, and C represent different metal elements), and the Cr content is C and Cr, it may be 8 mol % or less (corresponding to x being 0.08 or less in the above general formula), or 6 mol % or less.
  • a in the above general formula may contain Li, and the content of Li in A may be 90 mol% or more.
  • B in the above general formula may contain Mg, and the content of Mg in B may be 90 mol % or more.
  • C in the above general formula may contain Ge, and the content of Ge in C may be 90 mol % or more.
  • the maximum value of the peak intensity in the region where the diffraction angle (2 ⁇ ) is 17.0 to 19.5 ° is ⁇ , and the diffraction angle is 20.5 to 23.5 °.
  • the value of ⁇ / ⁇ may be 0.047 or less, where ⁇ is the maximum value of the peak intensity in the region.
  • One aspect of the present disclosure is to bake a composition containing a compound having lithium as a constituent element, a compound having magnesium as a constituent element, a compound having germanium as a constituent element, and a compound having chromium as a constituent element in the atmosphere. obtaining a fired product; and heat-treating the fired product at a temperature of 850° C. or less to reduce at least part of chromium in the fired product, wherein germanium and chromium in the composition
  • a method for producing a phosphor wherein the content of chromium is 8 mol % or less with respect to the total amount of
  • a composition having an adjusted chromium content is fired to form a crystal structure, and then reduced under predetermined conditions to remove tetravalent chromium, which serves as a luminescence center. It is possible to increase the proportion. Due to such action, the above-described phosphor can be manufactured by the method for manufacturing the above-described phosphor.
  • the heat treatment of the fired product may be performed in a reducing atmosphere containing ammonia.
  • FIG. 1 is a diagram showing fluorescence spectra obtained when the phosphors prepared in Examples were irradiated with light having a wavelength of 450 nm.
  • FIG. 2 is a diagram showing powder X-ray diffraction spectra of phosphors prepared in Examples.
  • FIG. 3 is a diagram showing the measurement results of the emission intensity of the phosphors prepared in Examples.
  • each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition.
  • the “steps” used herein may be independent steps or steps performed simultaneously.
  • One embodiment of the phosphor has the same structure as the Li2MgGeO4 crystal phase in the main crystal phase and contains tetravalent chromium as an activating element.
  • the main crystal phase may be represented by the general formula: A 2 B(C 1-x Cr x )O 4 .
  • A, B, and C represent metal elements different from each other.
  • A, B, and C are mainly intended to represent one type of element, respectively, but may be partially substituted to represent two or more types of elements.
  • A is preferably lithium (Li)
  • B magnesium
  • C germanium
  • some of the respective elements are shown below. and may be substituted by elements that are candidates for and.
  • A may be, for example, lithium (Li), sodium (Na), potassium (K), etc., preferably contains Li, more preferably contains 90 mol% or more of Li, and Li is particularly preferred.
  • B may be, for example, magnesium (Mg), zinc (Zn), and calcium (Ca), preferably containing Mg, more preferably containing 90 mol% or more of Mg, is particularly preferred.
  • C may be, for example, germanium (Ge), silicon (Si), tin (Sn), etc., preferably contains Ge, more preferably contains 90 mol% or more of Ge, and Ge is particularly preferred.
  • the notation (C 1-x Cr x ) in the above general formula means that both C and Cr are included, and that Cr is included in a form substituting part of the C site.
  • chromium (Cr) may be introduced into germanium (Ge) sites.
  • the phosphor may be represented by, for example, the general formula: Li 2 Mg(Ge 1-x Cr x )O 4 , where x is, for example, greater than 0 and 0.1 or less, 0.005 may be ⁇ 0.1, 0.005-0.08, 0.005-0.06, 0.005-0.03, or 0.005-0.02.
  • the main crystal phase has the same crystal structure as the Li2MgGeO4 crystal phase, but its space group may be, for example, Pmn21 .
  • the main crystalline phase means the phase with the largest proportion of the produced phase calculated by the powder X-ray diffraction method.
  • the phosphor may contain, in addition to the main crystal phase, a heterophase within the scope of the present disclosure.
  • Heterogeneous phases include, for example, phases having the same crystal composition but different space groups (for example, a crystal structure whose space group is Pnma), or phases having different crystal compositions (for example, MgCr 2 O 4 and the like).
  • the crystal structure of the phosphor can be confirmed by the powder X-ray diffraction method.
  • the content of lithium (Li), magnesium (Mg), germanium (Ge), and chromium (Cr) in the composition of the phosphor was determined by subjecting the object to be measured to acid decomposition under pressure to prepare a sample solution. can be determined by quantitative analysis using an ICP emission spectrometer.
  • the oxygen (O) content can be estimated based on the charge balance from the elemental content of the ICP. Since the elemental composition in the phosphor corresponds to the ratio of each element charged when the phosphor is produced, the elemental composition of the phosphor can also be estimated from the raw material composition.
  • the content of chromium in the main crystal phase can be adjusted according to the emission characteristics required for the phosphor.
  • the main crystal phase is represented by the general formula: A 2 B(C 1-x Cr x ) O 4 (wherein A, B, and C represent mutually different metal elements)
  • the Cr content is , based on the total amount of C and Cr, for example, 10 mol% or less, 8 mol% or less (corresponding to x being 0.08 or less in the above general formula), 7 mol% or less, 6 mol% or less, 5 mol% or less, It may be 2 mol % or less, or 1.5 mol % or less.
  • a heterophase may occur during the manufacturing process.
  • the Cr content is Based on the total amount, it may be, for example, 0.3 mol % or more, 0.5 mol % or more, or 0.7 mol % or more.
  • tetravalent Cr Cr 4+
  • the lower limit of the chromium content is within the above range.
  • the amount can be improved, and the emission intensity of the obtained phosphor can be improved more fully.
  • the content of chromium in the main crystal phase may be adjusted within the range described above, and the main crystal phase has the general formula: A 2 B(C 1-x Cr x )O 4 (in the general formula, A, B, C represents a metal element different from each other), the content of Cr is, for example, 0.3 to 10 mol%, or 0.5 to 1.5 mol%, based on the total amount of C and Cr. It's okay.
  • X is the integrated value of the spectrum with a wavelength of 700 to 900 nm
  • Y is the integrated value of the spectrum with a wavelength of 1100 to 1300 nm.
  • Y/X value is 50 or more.
  • the lower limit of the value of Y/X may be, for example, 60 or more, 100 or more, 200 or more, 400 or more, or 600 or more.
  • the upper limit of the value of Y/X may be, for example, 1500 or less, 1000 or less, 800 or less, or 700 or less.
  • a large Y/X value means that the ratio of tetravalent chromium is high. The incidence rate of Therefore, by setting the upper limit of the value of Y/X within the above range, it is possible to suppress an increase in the proportion of heterogeneous phases during the manufacturing process, and to obtain a phosphor with better optical properties.
  • the integrated values X and Y of the fluorescence spectrum peaks in this specification mean the values determined from the fluorescence spectrum measured using the fluorescence spectrometer for the above phosphor. Specifically, the fluorescence spectrum is obtained by measuring according to the operation described in the examples of this specification.
  • the fluorescence spectrometer for example, "Fluorolog-3-iHR-NIR" (product name) manufactured by HORIBA, Ltd. can be used.
  • MgCr 2 O 4 is generally black and can absorb the excitation light applied to the phosphor and emitted fluorescence, so it is particularly desirable to reduce it.
  • MgCr 2 O 4 shows a peak in the region where the diffraction angle (2 ⁇ ) is 17.0 to 19.5° in the powder X-ray diffraction pattern, and Li 2 MgGeO 4 shows a diffraction angle has a peak in the region of 20.5 to 23.5°.
  • the maximum value of the peak intensity in the region where the diffraction angle (2 ⁇ ) is 17.0 to 19.5° is ⁇
  • the diffraction angle is 20.5 to 23.5°.
  • the value of ⁇ / ⁇ , where ⁇ is the maximum value of the peak intensity in the 5° region can be adjusted to be low.
  • the upper limit of the ⁇ / ⁇ value may be, for example, 0.047 or less, 0.045 or less, 0.040 or less, or 0.035 or less.
  • the lower limit of the value of ⁇ / ⁇ is not particularly limited, and may be 0 (meaning that MgCr 2 O 4 is not included), for example, 0.020 or more, or 0.020 or more. 030 or more.
  • the value of ⁇ / ⁇ may be adjusted within the above range, and may be, for example, 0.020-0.047, 0.030-0.040, or 0.030-0.035.
  • the maximum values ⁇ and ⁇ of peak intensity in this specification mean values determined by powder X-ray diffraction analysis for the phosphor.
  • the powder X-ray diffraction pattern is specifically measured and determined by the procedure described in the Examples of this specification.
  • the above phosphors may be used alone or in combination with other phosphors. Since the phosphor according to the present disclosure has excellent emission intensity, it can be suitably used for light emitting devices such as LEDs, display devices, and the like.
  • the phosphor may be dispersed in a cured resin and used.
  • the cured resin in this case is not particularly limited, and for example, a resin used as a sealing resin for light emitting devices or the like can be used.
  • An example of a light-emitting device is a light-emitting device that includes a light-emitting element that emits primary light, and a wavelength converter that absorbs part of the primary light and emits secondary light having a longer wavelength than the primary light.
  • the wavelength converting body includes the above phosphor according to the present disclosure.
  • a light-emitting element that emits primary light may be, for example, an InGaN blue LED or the like.
  • the light emitting element and the wavelength converter may be dispersed in a sealing resin or the like.
  • the phosphor described above can be produced, for example, by the following method.
  • One embodiment of the method for producing a phosphor is to prepare a composition containing a compound having lithium as a constituent element, a compound having magnesium as a constituent element, a compound having germanium as a constituent element, and a compound having chromium as a constituent element in the atmosphere.
  • a step of obtaining a fired product by firing at (hereinafter also referred to as a firing step), and a step of reducing at least part of chromium in the fired product by heat-treating the fired product at a temperature of 850 ° C. or less ( hereinafter also referred to as a reduction step).
  • the composition contains a compound that serves as a source of constituent elements of the phosphor, and includes a compound having lithium as a constituent element, a compound having magnesium as a constituent element, a compound having germanium as a constituent element, and chromium as a constituent element. Contains compounds.
  • Compounds containing lithium (Li) as a constituent element may be, for example, carbonates, oxides, fluorides, oxyfluorides, chlorides, nitrides, metals, and the like. Among the above compounds, it is preferable to contain a carbonate from the viewpoint of the stability of the raw material and promotion of the reaction.
  • the compound containing lithium (Li) as a constituent element may be lithium carbonate.
  • Compounds having magnesium (Mg) as a constituent element may be, for example, oxides, fluorides, oxyfluorides, chlorides, nitrides, and metals. Among the above compounds, oxides are preferably contained from the viewpoint of stability of raw materials and reaction promotion.
  • a compound containing magnesium (Mg) as a constituent element may be magnesium oxide.
  • Compounds containing germanium (Ge) as a constituent element may be, for example, oxides, fluorides, oxyfluorides, chlorides, nitrides, and metals. Among the above compounds, oxides are preferably contained from the viewpoint of stability of raw materials and reaction promotion.
  • a compound containing germanium (Ge) as a constituent element may be germanium oxide.
  • Compounds containing chromium (Cr) as a constituent element may be, for example, oxides, fluorides, oxyfluorides, chlorides, nitrides, and metals. Among the above compounds, oxides are preferably contained from the viewpoint of stability of raw materials and reaction promotion.
  • the compound containing chromium (Cr) as a constituent element may be chromium oxide.
  • the content of chromium is 8 mol% or less with respect to the total amount of germanium and chromium in the composition.
  • the upper limit of the chromium content is, for example, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 2 mol% or less, or 1.5 mol with respect to the total amount of germanium and chromium in the composition. % or less.
  • the upper limit of the content of chromium is within the above range, it is possible to suppress the generation of heterogeneous phases and improve the optical properties of the resulting phosphor.
  • the lower limit of the chromium content may be, for example, 0.3 mol % or more, 0.5 mol % or more, or 0.7 mol % or more with respect to the total amount of germanium and chromium in the composition.
  • the content of chromium in the composition may be adjusted within the above range, for example, 0.3 to 8 mol%, or 0.5 to 1.5 mol, relative to the total amount of germanium and chromium in the composition. %.
  • the above composition may contain other components in addition to the compound having lithium as a constituent element, the compound having magnesium as a constituent element, the compound having germanium as a constituent element, and the compound having chromium as a constituent element.
  • Other components include, for example, a compound having sodium (Na) as a constituent element, a compound having zinc (Zn) as a constituent element, a compound having calcium (Ca) as a constituent element, and a compound having strontium (Sr) as a constituent element.
  • the above composition can be prepared by weighing and mixing each compound. Dry mixing or wet mixing may be used for mixing.
  • the dry mixing method may be, for example, a method of mixing each component using a V-type mixer or the like.
  • the wet mixing method may be, for example, a method of adding a solvent such as water or a dispersion medium to prepare a solution or slurry, mixing the components, and then removing the solvent or dispersion medium.
  • the lower limit of the heating temperature (firing temperature) in the firing step may be, for example, 800°C or higher, 900°C or higher, 1000°C or higher, or 1100°C or higher. Reaction can be accelerated because the lower limit of the heating temperature is within the above range.
  • the upper limit of the heating temperature in the firing step may be, for example, 1600° C. or less, 1500° C. or less, 1400° C. or less, or 1300° C. or less. When the upper limit of the heating temperature is within the above range, volatilization of the raw material components can be suppressed.
  • the heating temperature in the firing step may be adjusted within the range described above, and may be, for example, 800-1600°C or 1100-1300°C.
  • the lower limit of the heating time (firing time) in the firing step may be, for example, 3 hours or longer, 4 hours or longer, 5 hours or longer, or 6 hours or longer. When the lower limit of the heating time is within the above range, the reaction can be promoted.
  • the upper limit of the heating time in the firing step may be, for example, 11 hours or less, 10 hours or less, 9 hours or less, or 8 hours or less. When the upper limit of the heating time is within the above range, volatilization of raw material components can be suppressed.
  • the heating time in the firing step may be adjusted within the range described above, and may be, for example, 3 to 11 hours, or 6 to 8 hours.
  • the firing time, heating time, and the like in this specification mean the time (holding time) for maintaining the temperature after the temperature of the surrounding environment of the object reaches a predetermined temperature.
  • the rate of temperature increase when the temperature is increased to a predetermined temperature and the rate of temperature decrease when the temperature is decreased to room temperature can be adjusted as appropriate.
  • the rate of temperature increase in the firing step may be, for example, 2 to 15°C/min, 5 to 12°C/min, or 8 to 10°C/min.
  • the temperature drop rate in the firing step may be, for example, 2 to 15°C/min, 5 to 12°C/min, or 8 to 10°C/min.
  • the firing process is carried out in the atmosphere.
  • the number of times of heat treatment in the firing step may be one time, but may be, for example, two times or more, and may be two to five times, or two to four times.
  • the heating temperature, heating time, atmosphere during heating, and pressure during heating in the first firing step are the same as the heating temperature, heating time, and heating time in the above-described heating step. atmosphere and pressure during heating can be applied.
  • the heating temperature, heating time, atmosphere during heating, and pressure during heating in and after the second firing step may be the same as or different from those in the first firing step. However, even if the heating temperature, heating time, atmosphere during heating, and pressure during heating in the second and subsequent firing steps are different from those in the first firing step, within the conditions shown for the above heating step.
  • the fired material prepared in the firing process described above is heat-treated at a temperature of 850°C or less.
  • the reduction treatment at least part of the chromium whose valence increased during the process of obtaining the fired product can be reduced, and the ratio of tetravalent chromium that contributes to light emission can be increased.
  • the reduction step may be performed in a reducing atmosphere, and the reducing atmosphere may contain, for example, ammonia, hydrocarbons, carbon monoxide, hydrogen, and the like. Reduction of chromium can be promoted more by setting the reducing atmosphere as described above. From the viewpoint of suppressing the presence of hexavalent chromium due to insufficient reduction of chromium in the reduction step, the reducing atmosphere may be an atmosphere containing ammonia, preferably an ammonia atmosphere.
  • the flow rate of the atmosphere in the reduction process is, for example, 0.001 to 2.5 mL/min, 0.1 to 2.0 mL/min, 0.5 to 1.5 mL/min when using a furnace core tube with an inner diameter of 70 mm, Or it may be 0.8-1.2 mL/min.
  • the lower limit of the heating temperature in the reduction step may be, for example, 300°C or higher, 400°C or higher, 500°C or higher, 600°C or higher, 650°C or higher, or 700°C or higher.
  • the upper limit of the heating temperature in the reduction step may be, for example, 850° C. or lower, less than 850° C., 820° C. or lower, 800° C. or lower, or 750° C. or lower.
  • the heating temperature in the reduction step may be adjusted within the range described above, and may be, for example, 300-820°C, 600-820°C, 650-800°C, or 650-750°C.
  • the lower limit of the heating time in the reduction step may be 2 hours or longer, 3 hours or longer, 4 hours or longer, or 5 hours or longer.
  • the upper limit of the heating time in the reduction step may be 11 hours or less, 10 hours or less, 9 hours or less, or 8 hours or less.
  • the heating time in the reduction step may be adjusted within the above range, and may be, for example, 2 to 11 hours, or 7 to 8 hours.
  • the rate of temperature increase in the reduction step may be, for example, 2-15°C/min, 5-12°C/min, or 8-10°C/min.
  • the temperature drop rate in the reduction step may be, for example, 2 to 15°C/min, 5 to 12°C/min, or 8 to 10°C/min.
  • the manufacturing method described above may have other steps in addition to the firing step and the reduction step.
  • Other steps include, for example, a pulverization step, a classification step, an acid treatment step, and the like.
  • the pulverization step may be, for example, a step of pulverizing the fired product obtained in the firing step or the heat-treated product obtained in the reduction step.
  • a step of pulverizing the fired product obtained in the firing step or the heat-treated product obtained in the reduction step For example, by pulverizing the fired product obtained in the firing step before sending it to the reduction step to adjust the particle size, the surface area of the fired product can be increased and the efficiency of reduction in the subsequent reduction step can be improved. . Further, by pulverizing the heat-treated material obtained in the reduction step, the particle size of the phosphor can be adjusted according to the application.
  • a general crusher or crusher can be used in the crushing process.
  • a mortar, ball mill, vibration mill, jet mill, and the like can be used.
  • "pulverization” in this specification includes “crushing”.
  • Example 1 ⁇ Manufacturing method of phosphor> Lithium carbonate (Li 2 CO 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.), magnesium oxide (MgO, manufactured by Kanto Chemical Co., Ltd.), germanium oxide (GeO 2 , manufactured by Kojundo Chemical Laboratory Co., Ltd.), and Chromium oxide (Cr 2 O 3 , manufactured by Kojundo Chemical Laboratory Co., Ltd.) was measured so that the molar ratio of Li: Mg: Ge: Cr was 2: 1: 0.995: 0.005, A composition (raw material powder) was obtained by dry mixing.
  • the heat-treated product was used as the phosphor of Example 1.
  • the obtained phosphor is represented by the general formula: Li 2 Mg(Ge 1-x Cr x )O 4 (x is 0.005), and the main crystal phase has the same structure as the Li 2 MgGeO 4 crystal phase. It was confirmed.
  • Example 2 A phosphor was obtained in the same manner as in Example 1, except that the treatment temperature in the reduction step was changed to 700°C.
  • Example 3 A phosphor was obtained in the same manner as in Example 1, except that the treatment temperature in the reduction step was changed to 800°C.
  • ICP emission spectroscopic analysis method The composition was analyzed using a multi-type ICP emission spectrometer (Agilent's device, model number: 5110VDV type). 10 mg of phosphor was placed in a platinum crucible, 2 g of an alkaline flux was added, and the mixture was melted in an electric furnace. After standing to cool, 20 mL of hydrochloric acid (HCl) was added to the platinum crucible and dissolved by heating in a hot bath to obtain a solution. The resulting solution was then made up to 100 mL. This 100 mL solution was diluted 10-fold with pure water to prepare a test solution, which was set in the above apparatus and analyzed for its composition.
  • HCl hydrochloric acid
  • the fluorescent material to be measured was filled in a quartz cell and attached to the opening of the integrating sphere.
  • a monochromatic light with a wavelength of 450 nm from a xenon lamp as a light emission source was introduced into the integrating sphere as excitation light for the phosphor using an optical fiber.
  • the fluorescent substance to be measured was irradiated with the monochromatic light, which is the excitation light, and the fluorescence spectrum was measured.
  • a spectrophotometer manufactured by HORIBA, trade name: Fluorolog-3-iHR-NIR was used for the measurement.
  • the fluorescent material to be measured was filled in a quartz cell and attached to the opening of the integrating sphere.
  • Monochromatic light with a wavelength of 676 nm from a xenon lamp as a light emission source was introduced into the integrating sphere as excitation light for the phosphor using an optical fiber.
  • the fluorescent substance to be measured was irradiated with the monochromatic light, which is the excitation light, and the fluorescence spectrum was measured.
  • a spectrophotometer (trade name: Fluorolog-3-iHR-NIR, manufactured by HORIBA, Ltd.) was used for the measurement. From the obtained fluorescence spectrum data, the intensity ratio when the emission intensity of Example 1 was set to 1.0 was determined.

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* Cited by examiner, † Cited by third party
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JP2020188044A (ja) * 2019-05-10 2020-11-19 国立研究開発法人物質・材料研究機構 発光装置
WO2020262200A1 (ja) * 2019-06-26 2020-12-30 デンカ株式会社 蛍光体、蛍光体の製造方法、発光素子、発光装置および画像表示装置

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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020188044A (ja) * 2019-05-10 2020-11-19 国立研究開発法人物質・材料研究機構 発光装置
WO2020262200A1 (ja) * 2019-06-26 2020-12-30 デンカ株式会社 蛍光体、蛍光体の製造方法、発光素子、発光装置および画像表示装置

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JOUSSEAUME C., VIVIEN D., KAHN-HARARI A., DEROUET J., RIBOT F., VILLAIN F.: "Spectroscopic characterization of chromium (IV, V, VI) in Cr:Li2MSiO4 (M=Mg,Zn)", JOURNAL OF APPLIED PHYSICS, vol. 93, no. 10, 15 May 2003 (2003-05-15), 2 Huntington Quadrangle, Melville, NY 11747, pages 6006 - 6015, XP012057780, ISSN: 0021-8979, DOI: 10.1063/1.1568152 *
JOUSSEAUME, C. VIVIEN, D. KAHN-HARARI, A. MALKIN, B.Z.: "Long-lifetime fluorescence and crystal field calculation in Cr^4^+-doped Li"2MSiO"4, M=Mg, Zn", OPTICAL MATERIALS, vol. 24, no. 1-2, 1 October 2003 (2003-10-01), NL , pages 143 - 150, XP004463629, ISSN: 0925-3467, DOI: 10.1016/S0925-3467(03)00118-6 *
VIVIEN, D. ANINO, C. THERY, J.: "New Cr^4^+ activated compounds in tetrahedral sites for tunable laser applications", OPTICAL MATERIALS, vol. 8, no. 1-2, 1 July 1997 (1997-07-01), NL , pages 121 - 128, XP004115013, ISSN: 0925-3467, DOI: 10.1016/S0925-3467(97)00039-6 *
ZHUANG YIXI, TANABE SETSUHISA, QIU JIANRONG: "Wavelength Tailorability of Broadband Near-Infrared Luminescence in Cr 4+ -Activated Transparent Glass-Ceramics", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 97, no. 11, 1 November 2014 (2014-11-01), US , pages 3519 - 3523, XP093073769, ISSN: 0002-7820, DOI: 10.1111/jace.13128 *

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