WO2012074105A1 - Yellow phosphor and method for manufacturing same - Google Patents

Yellow phosphor and method for manufacturing same Download PDF

Info

Publication number
WO2012074105A1
WO2012074105A1 PCT/JP2011/077952 JP2011077952W WO2012074105A1 WO 2012074105 A1 WO2012074105 A1 WO 2012074105A1 JP 2011077952 W JP2011077952 W JP 2011077952W WO 2012074105 A1 WO2012074105 A1 WO 2012074105A1
Authority
WO
WIPO (PCT)
Prior art keywords
phosphor
sio
raw material
yellow phosphor
production method
Prior art date
Application number
PCT/JP2011/077952
Other languages
French (fr)
Japanese (ja)
Inventor
戸田　健司
和義 上松
峰夫 佐藤
雅 石垣
義貴 川上
鉄 梅田
Original Assignee
国立大学法人新潟大学
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人新潟大学, 住友化学株式会社 filed Critical 国立大学法人新潟大学
Publication of WO2012074105A1 publication Critical patent/WO2012074105A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7741—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides
    • C09K11/7789—Oxysulfides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

Definitions

  • the present invention relates to a yellow phosphor and a method for producing the same.
  • the white LED is composed of a combination of an LED chip that emits light in the ultraviolet to blue region (wavelength of about 380 to 500 nm) and a phosphor that emits light when excited by the light emitted from the LED chip.
  • White colors having various color temperatures can be realized based on the combination of the LED chip and the phosphor.
  • Patent Document 1 discloses a phosphor represented by Y 3 Al 5 O 12 : Ce (YAG: Ce).
  • Y 3 Al 5 O 12 is a host crystal of the phosphor
  • Ce is a luminescent ion activated by the host crystal.
  • Patent Documents 2 and 3 disclose phosphors represented by Li 2 SrSiO 4 : Eu.
  • the phosphor represented by Li 2 SrSiO 4 : Eu is excellent in emission color.
  • the phosphor represented by Li 2 SrSiO 4 : Eu efficiently absorbs blue light emitted from a blue LED and exhibits a broad yellow light emission having a peak near 570 nm.
  • the phosphor represented by Li 2 SrSiO 4 : Eu can sufficiently maintain the emission intensity even when exposed to high temperatures.
  • a phosphor such as Li 2 SrSiO 4 : Eu is required to further improve the emission intensity.
  • An object of the present invention is to obtain a yellow phosphor having higher emission intensity (high luminance).
  • a raw material mixture containing M 1 , M 2 , and L and SiO are mixed and fired, and yellow fluorescence represented by M 1 2a (M 2 b L c ) M 3 d O 4
  • a method for producing a yellow phosphor comprising a step of generating a body.
  • another aspect of the present invention is a method for producing a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 , wherein the yellow phosphor comprises at least M 1 , It is manufactured by firing a mixture of a raw material mixture containing M 2 and L and SiO.
  • the raw material mixture further contains an M 3 -containing raw material different from SiO, and the ratio of the Si element derived from the SiO to the total amount of the element M 3 in the yellow phosphor is 0.00. It may be from 001 to 50 atomic%. That is, the raw material mixture containing a substance different from SiO as an M 3 -containing raw material may be mixed with SiO and fired. In this case, 0.001 atomic% or more and 50 atomic% of the element M 3 in the phosphor The following may be derived from SiO.
  • the L may be at least one element including Eu selected from rare earth elements, Bi and Mn, and the Eu may include divalent Eu.
  • M 1 may be Li and M 3 may be Si.
  • M 2 may be only Sr, Sr and Ba, or Sr and Ca.
  • the a may be 0.9 to 1.1 (0.9 or more and 1.1 or less).
  • Another aspect of the present invention provides a yellow phosphor that can be produced by the above production method, and a light emitting device or a white LED having the yellow phosphor.
  • the emission intensity (luminance) of the obtained yellow phosphor can be further increased.
  • the present embodiment relates to a phosphor that emits yellow light (yellow phosphor).
  • Yellow light emission refers to light emission having a peak in the vicinity of a wavelength of 560 nm to 590 nm.
  • the yellow phosphor that is the target of the present embodiment is represented by the formula M 1 2a (M 2 b L c ) M 3 d O 4 (wherein M 1 represents at least one element selected from alkali metals, and M 2 Represents at least one element selected from alkaline earth metals (Ca, Sr, Ba), M 3 represents at least one element selected from Si and Ge, and L comprises a rare earth element, Bi and Mn. Represents at least one element selected from the group, a is from 0.1 to 1.5, b is from 0.8 to 1.2, and c is from 0.005 to 0.2. , D is 0.8 to 1.2).
  • the M 1 is preferably one or more (particularly one) element selected from Li, Na, and K, and more preferably Li.
  • M 2 is preferably one or more (especially one) element selected from Ca, Sr and Ba, and more preferably Sr.
  • M 2 preferably further contains Ba and / or Ca, and more preferably contains Ca.
  • L is an element that is activated in the host crystal as a luminescent ion, and preferably contains at least Eu.
  • L is Eu alone or a combination with one or more elements of L elements (rare earth elements, Bi, Mn) other than Eu and Eu.
  • Particularly preferred L is Eu.
  • Eu as L preferably contains at least divalent Eu (Eu 2+ ).
  • M 3 is preferably Si.
  • M 1 is Li.
  • the lower limit of a is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and particularly preferably 0.95 or more.
  • the upper limit of a is preferably 1.2 or less, more preferably 1.1 or less, and particularly preferably 1.05 or less.
  • the lower limit of b is preferably 0.8 or more, and more preferably 0.9 or more.
  • the upper limit of b is preferably 1.1 or less, and more preferably 1.05 or less. In other words, the b is preferably 0.8 to 1.1, more preferably 0.9 to 1.05.
  • the lower limit of c is preferably 0.01 or more, and more preferably 0.015 or more.
  • the upper limit of c is preferably 0.1 or less, more preferably 0.05 or less. In other words, the c is preferably 0.01 to 0.1, and more preferably 0.015 to 0.05.
  • the value of b + c and the lower limit of d may be the same or different, and are preferably 0.9 or more, more preferably 0.95 or more.
  • the value of b + c and the upper limit of d may be the same or different, and are preferably 1.1 or less, more preferably 1.05 or less. In other words, the value of b + c and d may be the same or different, preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably. 1.
  • the ratio of a to b + c (a / (b + c)), the ratio of a to d (a / d), and the ratio of b + c to d ((b + c) / d) may be the same or different. For example, it is 0.9 to 1.1, preferably 0.95 to 1.05.
  • the phosphor is preferably hexagonal or trigonal.
  • the phosphor can be manufactured by firing a mixture of a raw material mixture containing at least M 1 , M 2 , and L and SiO. That is, the phosphor is a yellow fluorescent material represented by M 1 2a (M 2 b L c ) M 3 d O 4 by mixing and baking a raw material mixture containing M 1 , M 2 , and L and SiO. It can be manufactured by a method including a step of generating a body.
  • SiO 2 is generally used as a raw material for the Si component of the silicate phosphor.
  • the manufacturing method according to the present embodiment is different from a normal method in that SiO is used as a raw material for the Si component.
  • SiO acts as a source of M 3 components.
  • SiO has an action of efficiently reducing the L component (especially europium). Therefore, the L component can be sufficiently reduced, and the luminance of the yellow phosphor can be increased.
  • the SiO is preferably powdered SiO.
  • the metal element-containing substance may be an oxide of each metal M 1 , M 2 , L, or M 3 , or a substance that decomposes or oxidizes at a high temperature (particularly the firing temperature) to form an oxide. May be.
  • Substances that form this oxide include hydroxides, nitrides, oxynitrides, acid derivatives, salts (such as carbonates, nitrates, and oxalates).
  • the first raw material is preferably selected from hydroxides, oxides and carbonates of metal M 1 (particularly lithium).
  • a particularly preferable first raw material contains lithium hydroxide (LiOH), lithium oxide (Li 2 O), or lithium carbonate (Li 2 CO 3 ). These 1st raw materials may be used individually by 1 type, and may combine multiple.
  • the second raw material include a hydroxide, oxide or carbonate of metal M 2 (especially strontium, barium, calcium, etc.). More specifically, the second raw material is selected from, for example, strontium hydroxide (Sr (OH) 2 ), strontium oxide (SrO), and strontium carbonate (SrCO 3 ). These 2nd raw materials may be used individually by 1 type, and may combine multiple.
  • the third raw material is preferably a hydroxide, oxide, carbonate or chloride of metal L (especially europium).
  • the third raw material includes, for example, europium hydroxide (Eu (OH) 2 , Eu (OH) 3 ), europium oxide (EuO, Eu 2 O 3 ), europium carbonate (EuCO 3 , Eu 2 (CO 3 ) 3 ), It is selected from europium chloride (EuCl 2 , EuCl 3 ) and europium nitrate (Eu (NO 3 ) 2 , Eu (NO 3 ) 3 ). These third raw materials may be used alone or in combination.
  • Preferred examples of the fourth raw material include oxides, acid derivatives, and salts of metal M 3 (particularly silicon).
  • a preferable fourth raw material includes, for example, silicon dioxide, silicic acid, or silicate.
  • the atomic ratio of the elements M 1 , M 2 , L, and M 3 supplied from each raw material is expressed by the formula M 1 2a (M 2 b L c ) M 3 d O 4.
  • M 1 2a (M 2 b L c ) M 3 d O 4. Are mixed within a range satisfying the relationship of a, b, c and d.
  • the amount is preferably such that That is, of the element M 3 in the phosphor, 0.001 atomic% or more and 50 atomic% or less, preferably 0.005 atomic% or more and 20 atomic% or less of SiO is used in such an amount. It is recommended.
  • Li 1.96 Sr 0.98 Eu 0.02 SiO 4 which is one of the preferred compositions of the phosphor obtained by the manufacturing method according to the present embodiment, the following may be performed.
  • SiO is used so that the usage ratio is 1.0 atomic% with respect to the total Si-containing material.
  • the mixing ratio of SrCO 3 , Li 2 CO 3 , SiO 2 and Eu 2 O 3 contained in the raw material mixture (metal compound mixture) is such that the molar ratio of Li: Sr: Eu: Si is 1.96: 0.98: 0. .02: 1.0 may be set.
  • the first to third raw materials (preferably the first to fourth raw materials) and SiO may be mixed by a wet method or a dry method.
  • general-purpose devices such as a ball mill, a V-type mixer and a stirrer can be used.
  • the firing chamber atmosphere that is, the firing atmosphere
  • the firing atmosphere may be any of an inert gas atmosphere, an oxidizing gas atmosphere, and a reducing gas atmosphere.
  • an appropriate amount of carbon may be added to the raw material mixture (metal compound mixture) and fired.
  • FIG. 1 is a schematic view showing an embodiment of a firing processing apparatus for firing a raw material mixture. The firing is performed by, for example, putting the mixture 5 of the raw material mixture and SiO in the firing chamber 30 and heating.
  • Examples of the inert gas include nitrogen and argon.
  • Examples of the oxidizing gas include oxygen, oxygen-containing inert gas (nitrogen, argon, etc.), and air.
  • Examples of the reducing gas include a mixed gas of 0.1 to 10% by volume of hydrogen and an inert gas (nitrogen, argon, etc.), or 10 to 100% by volume (preferably 50 to 100% by volume) of NH. 3 and an inert gas (nitrogen, argon, etc.). These gases may be pressurized as necessary.
  • a preferable firing atmosphere is a mixed gas of 0.1 to 10% by volume (more preferably 2 to 8% by volume, particularly preferably 4 to 6% by volume) hydrogen and an inert gas (particularly nitrogen).
  • Calcination may be repeated a plurality of times.
  • the firing atmosphere may be changed between the first firing and the second firing, and the firing atmosphere may be changed in the third and subsequent firings.
  • calcination when calcination is performed in an inert gas atmosphere or an oxidizing gas atmosphere, it is preferable to perform calcination in a reducing gas atmosphere thereafter.
  • Calcination temperature is usually 700 to 1000 ° C., preferably 750 to 950 ° C., more preferably 800 to 900 ° C.
  • the firing time is usually 1 to 100 hours, preferably 10 to 90 hours, and more preferably 20 to 80 hours.
  • the method according to the present embodiment includes a raw material mixture, if necessary, at a temperature lower than the calcination (eg, 500 to 800 ° C.) for a predetermined time (eg, 1 to 100 hours, preferably 10 to 90 hours). And a step of calcining the raw material mixture may be further included.
  • a temperature lower than the calcination eg, 500 to 800 ° C.
  • a predetermined time eg, 1 to 100 hours, preferably 10 to 90 hours.
  • reaction accelerator is selected from, for example, alkali metal halides, alkali metal carbonates, alkali metal hydrogen carbonates, ammonium halides, boron oxides (B 2 O 3 ), and boron oxo acids (H 3 BO 3 ).
  • the alkali metal halide is preferably an alkali metal fluoride or an alkali metal chloride, such as LiF, NaF, KF, LiCl, NaCl, or KCl.
  • the alkali metal carbonate is, for example, Li 2 CO 3 , Na 2 CO 3 or K 2 CO 3 .
  • the alkali metal bicarbonate is, for example, NaHCO 3 .
  • the ammonium halide is, for example, NH 4 Cl or NH 4 I.
  • the phosphor obtained by the manufacturing method according to the present embodiment may contain a halogen element derived from the raw material mixture, that is, one or more elements of F, Cl, Br, or I.
  • the total content of halogen elements may be equal to or less than the total content of halogen elements contained in the raw material, preferably 50% or less, and more preferably 25% or less.
  • the calcined product or the fired product may be subjected to any one or more of pulverization, mixing, washing, and classification.
  • pulverization and mixing for example, a ball mill, a V-type mixer, a stirrer, a jet mill or the like can be used.
  • a high-luminance phosphor can be obtained.
  • a phosphor is a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 . Since the yellow phosphor obtained by the above production method has high emission intensity, it can be suitably used in a light emitting device (for example, white LED).
  • a white LED is composed of a light emitting element (LED chip) that emits ultraviolet to blue light (having a wavelength of about 200 to 550 nm, preferably about 380 to 500 nm), and a fluorescent layer containing a phosphor.
  • This white LED can be manufactured by a method disclosed in, for example, Japanese Patent Application Laid-Open Nos. 11-31845 and 2002-226846. That is, for example, a white LED can be manufactured by a method in which the light emitting element is sealed with a translucent resin such as an epoxy resin or a silicone resin, and the surface thereof is covered with a phosphor. If the amount of the phosphor is appropriately set, the white LED emits a desired white color.
  • a translucent resin such as an epoxy resin or a silicone resin
  • FIG. 2 is a cross-sectional view showing an embodiment of a light emitting device.
  • the light emitting device 1 illustrated in FIG. 2 includes a light emitting element 10 and a fluorescent layer 20 provided on the light emitting element 10.
  • the phosphor forming the fluorescent layer 20 receives the light from the light emitting element 10 and is excited to emit fluorescence.
  • White light emission can be obtained by appropriately setting the type, amount, and the like of the phosphor constituting the phosphor layer 20. That is, a white LED can be configured.
  • the light emitting device or the white LED according to this embodiment is not limited to the form shown in FIG. 2 and can be appropriately modified without departing from the gist of the present invention.
  • the yellow fluorescent substance obtained by the manufacturing method which concerns on this embodiment may be included independently, and the other fluorescent substance may be further included.
  • Other phosphors include, for example, BaMgAl 10 O 17 : Eu, (Ba, Sr, Ca) (Al, Ga) 2 S 4 : Eu, BaMgAl 10 O 17 : (Eu, Mn), BaAl 12 O 19 :( Eu, Mn), (Ba, Sr, Ca) S: (Eu, Mn), YBO 3 : (Ce, Tb), Y 2 O 3 : Eu, Y 2 O 2 S: Eu, YVO 4 : Eu, ( Ca, Sr) S: Eu, SrY 2 O 4 : Eu, Ca—Al—Si—O—N: Eu, (Ba, Sr, Ca) Si 2 O 2 N 2 : Eu, ⁇ -sialon, CaSc 2 O 4 : Selected from Ce and Li— (Ca, Mg) —Ln—A
  • Examples of the light emitting element that emits light having a wavelength of 200 nm to 550 nm include an ultraviolet LED chip and a blue LED chip.
  • GaN, In i Ga 1-i N (0 ⁇ i ⁇ 1), In i Al j Ga 1- jN (0 ⁇ i ⁇ 1, 0 ⁇ j ⁇ 1, i + j) are used as light emitting layers.
  • a semiconductor having a layer such as ⁇ 1) is used.
  • the emission wavelength can be changed by changing the composition of the light emitting layer.
  • the phosphor obtained by the manufacturing method according to the present embodiment is a light emitting device other than a white LED, for example, a light emitting device whose phosphor excitation source is vacuum ultraviolet light (for example, PDP); a light emitting device whose phosphor excitation source is ultraviolet light (For example, a backlight for a liquid crystal display, a three-wavelength fluorescent lamp); It can also be used for a light emitting device (for example, CRT or FED) in which the phosphor excitation source is an electron beam.
  • a light emitting device whose phosphor excitation source is vacuum ultraviolet light (for example, PDP); a light emitting device whose phosphor excitation source is ultraviolet light (For example, a backlight for a liquid crystal display, a three-wavelength fluorescent lamp); It can also be used for a light emitting device (for example, CRT or FED) in which the phosphor excitation source is an electron beam.
  • a light emitting device for example, a light emitting device
  • the emission intensity of the phosphors obtained in the following examples was determined using a fluorescence spectrometer (FP-6500 manufactured by JASCO Corporation).
  • An X-ray diffractometer (RINT2000 manufactured by Rigaku) was used for X-ray diffraction (XRD) measurement of the phosphor.
  • XRD X-ray diffraction
  • the valence ratio of Eu in the phosphor was evaluated by X-ray absorption fine structure (XAFS) measurement.
  • XAFS measurement was performed by the transmission method using the beam line BL14B2 at SPring-8.
  • BaMgAl 10 O 17 : Eu 2+ (BAM) was used as a standard sample of Eu 2+ (6792 eV).
  • Eu 3+ (6980 eV) europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%) was used.
  • the X-ray absorption near edge structure (XANES) spectrum was obtained by processing the XAFS data of each sample based on the background using an analysis program (Rigaku REX2000). Thereafter, pattern fitting of the XANES spectrum of each sample was performed using the XANES spectra of the Eu 2+ standard sample and Eu 3+ standard sample, and the ratio of Eu 2+ in the sample was calculated from the ratio of Eu 2+ peaks.
  • the content of oxygen in the crystalline substance was measured using EMGA-920 manufactured by Horiba.
  • the non-dispersive infrared absorption method was used for the oxygen content.
  • Comparative Example 1 Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) were weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0. Were mixed by a dry ball mill for 6 hours to obtain a metal compound mixture.
  • the metal compound mixture was heated (baked) for 24 hours at a temperature of 800 ° C. in an N 2 atmosphere containing 5% by volume of H 2 . This was gradually cooled to room temperature to obtain a phosphor containing a compound represented by the formula Li 1.96 (Sr 0.98 Eu 0.02 ) SiO 4 .
  • the ratio of divalent Eu (Eu 2+ ) in the total Eu of the phosphor was 14%.
  • Comparative Example 2 Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) were weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0. Were mixed by a dry ball mill for 6 hours to obtain a metal compound mixture.
  • the metal compound mixture was heated (baked) at a temperature of 800 ° C. for 24 hours and gradually cooled to room temperature.
  • the obtained fired product is pulverized, and further heated (fired) at a temperature of 800 ° C. for 24 hours in an N 2 atmosphere containing 5% by volume of H 2 to obtain the formula Li 1.96 (Sr 0.98 Eu 0 0.02 )
  • a phosphor containing a compound represented by SiO 4 was obtained.
  • the ratio of divalent Eu (Eu 2+ ) in the total Eu of the phosphor was 17%.
  • SYMBOLS 1 Light-emitting device, 5 ... Mixture of raw material mixture and SiO, 10 ... Light emitting element, 20 ... Fluorescent layer, 30 ... Baking chamber.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)

Abstract

The present invention pertains to a method for manufacturing a yellow phosphor, including a step for generating a yellow phosphor represented by M1 2a(M2 bLc)M3 dO4 by mixing and firing SiO and a raw mixture containing M1, M2 and L.

Description

黄色蛍光体及びその製造方法Yellow phosphor and method for producing the same
　本発明は黄色蛍光体及びその製造方法に関するものである。 The present invention relates to a yellow phosphor and a method for producing the same.
　白色ＬＥＤは、紫外から青色の領域の光（波長が３８０～５００ｎｍ程度）を放出するＬＥＤチップと、該ＬＥＤチップから放出される光で励起されて発光する蛍光体との組み合わせから構成される。ＬＥＤチップと蛍光体との組み合わせ基づいて様々な色温度の白色を実現することができる。 The white LED is composed of a combination of an LED chip that emits light in the ultraviolet to blue region (wavelength of about 380 to 500 nm) and a phosphor that emits light when excited by the light emitted from the LED chip. White colors having various color temperatures can be realized based on the combination of the LED chip and the phosphor.
　紫外から青色の領域の光によって励起され発光する蛍光体は、白色ＬＥＤに好適に用いることができる。白色ＬＥＤ用の蛍光体として、例えば、特許文献１にはＹ３Ａｌ５Ｏ１２：Ｃｅ（ＹＡＧ：Ｃｅ）で示される蛍光体が開示されている。この蛍光体は、Ｙ３Ａｌ５Ｏ１２が蛍光体の母体結晶であり、Ｃｅが母体結晶に賦活される発光イオンである。 A phosphor that emits light when excited by light in the ultraviolet to blue region can be suitably used for a white LED. As a phosphor for white LED, for example, Patent Document 1 discloses a phosphor represented by Y 3 Al 5 O 12 : Ce (YAG: Ce). In this phosphor, Y 3 Al 5 O 12 is a host crystal of the phosphor, and Ce is a luminescent ion activated by the host crystal.
　特許文献２、３には、Ｌｉ２ＳｒＳｉＯ４：Ｅｕで示される蛍光体が開示されている。Ｌｉ２ＳｒＳｉＯ４：Ｅｕで示される蛍光体は、発光色に優れる。Ｌｉ２ＳｒＳｉＯ４：Ｅｕで示される蛍光体は、青色ＬＥＤから放出される青色光を効率よく吸収し、５７０ｎｍ付近にピークを有するブロードな黄色発光を示す。さらに、Ｌｉ２ＳｒＳｉＯ４：Ｅｕで示される蛍光体は、高温に曝された状態でも発光強度を十分に維持できる。 Patent Documents 2 and 3 disclose phosphors represented by Li 2 SrSiO 4 : Eu. The phosphor represented by Li 2 SrSiO 4 : Eu is excellent in emission color. The phosphor represented by Li 2 SrSiO 4 : Eu efficiently absorbs blue light emitted from a blue LED and exhibits a broad yellow light emission having a peak near 570 nm. Furthermore, the phosphor represented by Li 2 SrSiO 4 : Eu can sufficiently maintain the emission intensity even when exposed to high temperatures.
特開平１０－２４２５１３号公報Japanese Patent Laid-Open No. 10-242513 国際公開第０３／８０７６３号International Publication No. 03/80763 特開２００６－２３７１１３号公報JP 2006-237113 A
　しかし、例えば、Ｌｉ２ＳｒＳｉＯ４：Ｅｕのような蛍光体に関して、さらなる発光強度の向上が求められている。 However, for example, a phosphor such as Li 2 SrSiO 4 : Eu is required to further improve the emission intensity.
　本発明の目的は、発光強度がより高い（高輝度）黄色蛍光体を得ることにある。 An object of the present invention is to obtain a yellow phosphor having higher emission intensity (high luminance).
　本発明の一側面は、Ｍ１、Ｍ２、及びＬを含む原料混合物とＳｉＯとを混合し焼成して、Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４で表される黄色蛍光体を生成させる工程を含む、黄色蛍光体の製造方法を提供する。言い換えると、本発明の別の側面は、Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４で表される黄色蛍光体を製造する方法あって、上記黄色蛍光体は、少なくともＭ１、Ｍ２、及びＬを含む原料混合物とＳｉＯとを混合したものを焼成することによって製造される。但し、Ｍ１はアルカリ金属から選択される少なくとも一種の元素であり、Ｍ２はアルカリ土類金属から選択される少なくとも一種の元素であり、Ｍ３はＳｉである、又は、Ｓｉ及びＧｅ（Ｓｉ及びＧｅから選択される少なくとも一種の元素）であり、Ｌは希土類元素、Ｂｉ及びＭｎから選択される少なくとも一種の元素である。ａは、０．１～１．５（０．１以上、１．５以下）であり、ｂは、０．８～１．２（０．８以上、１．２以下）であり、ｃは、０．００５～０．２（０．００５以上、０．２以下）であり、ｄは、０．８～１．２（０．８以上、１．２以下）である。前記製造方法は、前記原料混合物が、ＳｉＯとは異なるＭ３含有原料を更に含有し、前記黄色蛍光体中の元素Ｍ３の全量に対して、前記ＳｉＯに由来するＳｉ元素の割合が０．００１～５０原子％であってもよい。すなわちＳｉＯとは異なる物質をＭ３含有原料として含む前記原料混合物をＳｉＯと混合して焼成してもよく、この場合、蛍光体中の元素Ｍ３のうち０．００１原子％以上、５０原子％以下が、ＳｉＯに由来してもよい。前記Ｌが、希土類元素、Ｂｉ及びＭｎから選択される、Ｅｕを含む少なくとも一種の元素であってもよく、このＥｕは２価のＥｕを含むことができる。また、Ｍ１がＬｉであり、Ｍ３がＳｉであってもよい。Ｍ２は、Ｓｒのみである、Ｓｒ及びＢａである、又は、Ｓｒ及びＣａであってもよい。前記ａは０．９～１．１（０．９以上、１．１以下）であってもよい。ｂ、ｃ及びｄは、ｂ＋ｃ＝１、ｄ＝１を満たしてもよい。 According to one aspect of the present invention, a raw material mixture containing M 1 , M 2 , and L and SiO are mixed and fired, and yellow fluorescence represented by M 1 2a (M 2 b L c ) M 3 d O 4 Provided is a method for producing a yellow phosphor, comprising a step of generating a body. In other words, another aspect of the present invention is a method for producing a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 , wherein the yellow phosphor comprises at least M 1 , It is manufactured by firing a mixture of a raw material mixture containing M 2 and L and SiO. Where M 1 is at least one element selected from alkali metals, M 2 is at least one element selected from alkaline earth metals, and M 3 is Si, or Si and Ge (Si And at least one element selected from Ge) and L is at least one element selected from rare earth elements, Bi and Mn. a is 0.1 to 1.5 (0.1 or more and 1.5 or less), b is 0.8 to 1.2 (0.8 or more and 1.2 or less), and c is 0.005 to 0.2 (0.005 or more and 0.2 or less), and d is 0.8 to 1.2 (0.8 or more and 1.2 or less). In the manufacturing method, the raw material mixture further contains an M 3 -containing raw material different from SiO, and the ratio of the Si element derived from the SiO to the total amount of the element M 3 in the yellow phosphor is 0.00. It may be from 001 to 50 atomic%. That is, the raw material mixture containing a substance different from SiO as an M 3 -containing raw material may be mixed with SiO and fired. In this case, 0.001 atomic% or more and 50 atomic% of the element M 3 in the phosphor The following may be derived from SiO. The L may be at least one element including Eu selected from rare earth elements, Bi and Mn, and the Eu may include divalent Eu. Further, M 1 may be Li and M 3 may be Si. M 2 may be only Sr, Sr and Ba, or Sr and Ca. The a may be 0.9 to 1.1 (0.9 or more and 1.1 or less). b, c and d may satisfy b + c = 1 and d = 1.
　本発明の別の側面は上記製造方法によって製造することのできる黄色蛍光体及び上記黄色蛍光体を有する発光装置又は白色ＬＥＤを提供する。 Another aspect of the present invention provides a yellow phosphor that can be produced by the above production method, and a light emitting device or a white LED having the yellow phosphor.
　本発明によれば、得られる黄色蛍光体の発光強度（輝度）をより高めることができる。 According to the present invention, the emission intensity (luminance) of the obtained yellow phosphor can be further increased.
原料混合物を焼成する焼成処理装置の一実施形態を示す模式図である。It is a schematic diagram which shows one Embodiment of the baking processing apparatus which bakes a raw material mixture. 発光装置の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of a light-emitting device.
　以下、本発明の好適な実施形態について詳細に説明する。本明細書において、用語「金属元素」は、Ｓｉ、Ｇｅなどの半金属元素も含む意味で使用される。 Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, the term “metal element” is used to include a semi-metal element such as Si or Ge.
　本実施形態は黄色発光を示す蛍光体（黄色蛍光体）に関する。黄色発光とは波長５６０ｎｍ～５９０ｎｍ付近にピークがある発光を指す。本実施形態の対象となる黄色蛍光体は、式Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４（式中、Ｍ１はアルカリ金属から選択される少なくとも一種の元素を示し、Ｍ２はアルカリ土類金属（Ｃａ、Ｓｒ、Ｂａ）から選択される少なくとも一種の元素を示し、Ｍ３はＳｉ及びＧｅから選択される少なくとも一種の元素を示し、Ｌは希土類元素、Ｂｉ及びＭｎからなる群から選択される少なくとも一種の元素を示す。ａは、０．１～１．５であり、ｂは、０．８～１．２であり、ｃは、０．００５～０．２であり、ｄは、０．８～１．２である）で表される。 The present embodiment relates to a phosphor that emits yellow light (yellow phosphor). Yellow light emission refers to light emission having a peak in the vicinity of a wavelength of 560 nm to 590 nm. The yellow phosphor that is the target of the present embodiment is represented by the formula M 1 2a (M 2 b L c ) M 3 d O 4 (wherein M 1 represents at least one element selected from alkali metals, and M 2 Represents at least one element selected from alkaline earth metals (Ca, Sr, Ba), M 3 represents at least one element selected from Si and Ge, and L comprises a rare earth element, Bi and Mn. Represents at least one element selected from the group, a is from 0.1 to 1.5, b is from 0.8 to 1.2, and c is from 0.005 to 0.2. , D is 0.8 to 1.2).
　前記Ｍ１は、好ましくはＬｉ、Ｎａ、及びＫから選択される一種又は二種以上（特に一種）の元素であり、より好ましくはＬｉである。 The M 1 is preferably one or more (particularly one) element selected from Li, Na, and K, and more preferably Li.
　Ｍ２は、好ましくはＣａ、Ｓｒ及びＢａから選択される一種又は二種以上（特に一種）の元素であり、より好ましくはＳｒである。Ｍ２がＳｒを含む場合、Ｍ２はさらにＢａ及び／又はＣａを含むことが好ましく、Ｃａを含むことがより好ましい。 M 2 is preferably one or more (especially one) element selected from Ca, Sr and Ba, and more preferably Sr. When M 2 contains Sr, M 2 preferably further contains Ba and / or Ca, and more preferably contains Ca.
　Ｌは発光イオンとして母体結晶に賦活される元素であり、少なくともＥｕを含むことが好ましい。例えば、Ｌは、Ｅｕ単独、又はＥｕ及びＥｕ以外のＬ元素（希土類元素、Ｂｉ、Ｍｎ）の一種以上の元素との組合せである。特に好ましいＬは、Ｅｕである。さらに、ＬとしてのＥｕが少なくとも２価のＥｕ（Ｅｕ２＋）を含むことが好ましい。 L is an element that is activated in the host crystal as a luminescent ion, and preferably contains at least Eu. For example, L is Eu alone or a combination with one or more elements of L elements (rare earth elements, Bi, Mn) other than Eu and Eu. Particularly preferred L is Eu. Further, Eu as L preferably contains at least divalent Eu (Eu 2+ ).
　Ｍ３は、好ましくはＳｉである。Ｍ３がＳｉであるとき、Ｍ１がＬｉであることが好ましい。 M 3 is preferably Si. When M 3 is Si, it is preferable that M 1 is Li.
　前記ａの下限は、好ましくは０．５以上であり、より好ましくは０．８以上であり、さらに好ましくは０．９以上であり、特に好ましくは０．９５以上である。またａの上限は、好ましくは１．２以下であり、さらに好ましくは１．１以下であり、特に好ましくは１．０５以下である。 The lower limit of a is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and particularly preferably 0.95 or more. The upper limit of a is preferably 1.2 or less, more preferably 1.1 or less, and particularly preferably 1.05 or less.
　前記ｂの下限は、好ましくは０．８以上であり、より好ましくは０．９以上である。前記ｂの上限は、好ましくは１．１以下であり、より好ましくは１．０５以下である。言い換えると、前記ｂは、好ましくは０．８～１．１であり、より好ましくは０．９～１．０５である。 The lower limit of b is preferably 0.8 or more, and more preferably 0.9 or more. The upper limit of b is preferably 1.1 or less, and more preferably 1.05 or less. In other words, the b is preferably 0.8 to 1.1, more preferably 0.9 to 1.05.
　前記ｃの下限は、好ましくは０．０１以上であり、より好ましくは０．０１５以上である。前記ｃの上限は、好ましくは０．１以下であり、より好ましくは０．０５以下である。言い換えると、前記ｃは、好ましくは０．０１～０．１であり、より好ましくは０．０１５～０．０５である。 The lower limit of c is preferably 0.01 or more, and more preferably 0.015 or more. The upper limit of c is preferably 0.1 or less, more preferably 0.05 or less. In other words, the c is preferably 0.01 to 0.1, and more preferably 0.015 to 0.05.
　ｂ＋ｃの値及びｄの下限は、同一であっても、異なってもよく、好ましくは０．９以上であり、より好ましくは０．９５以上である。ｂ＋ｃの値及びｄの上限は、同一であっても、異なってもよく、好ましくは１．１以下であり、より好ましくは１．０５以下である。言い換えると、ｂ＋ｃの値及びｄは、同一であっても、異なってもよく、好ましくは０．９～１．１であり、より好ましくは０．９５～１．０５であり、更により好ましくは１である。 The value of b + c and the lower limit of d may be the same or different, and are preferably 0.9 or more, more preferably 0.95 or more. The value of b + c and the upper limit of d may be the same or different, and are preferably 1.1 or less, more preferably 1.05 or less. In other words, the value of b + c and d may be the same or different, preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably. 1.
　ａとｂ＋ｃとの比（ａ／（ｂ＋ｃ））、ａとｄとの比（ａ／ｄ）、ｂ＋ｃとｄとの比（（ｂ＋ｃ）／ｄ）は、同一であっても、異なってもよく、例えば、０．９～１．１であり、好ましくは０．９５～１．０５である。 The ratio of a to b + c (a / (b + c)), the ratio of a to d (a / d), and the ratio of b + c to d ((b + c) / d) may be the same or different. For example, it is 0.9 to 1.1, preferably 0.95 to 1.05.
　本実施形態に係る製造方法によって得られる蛍光体の組成は、ａ、ｂ＋ｃ、ｄの値がいずれも１±０．０３の範囲内にあることが好ましく、１であることが特に好ましい。Ｍ１がＬｉであり、Ｍ３がＳｉであり、かつＭ２がＳｒ単独である、又はＳｒ及びＣａであることが好ましい。 In the composition of the phosphor obtained by the manufacturing method according to this embodiment, the values of a, b + c, and d are all preferably in the range of 1 ± 0.03, and particularly preferably 1. It is preferable that M 1 is Li, M 3 is Si, and M 2 is Sr alone, or Sr and Ca.
　前記蛍光体は、六方晶又は三方晶であることが好ましい。 The phosphor is preferably hexagonal or trigonal.
　前記蛍光体は、少なくともＭ１、Ｍ２、及びＬを含む原料混合物とＳｉＯとを混合したものを焼成することによって製造できる。すなわち、前記蛍光体は、Ｍ１、Ｍ２、及びＬを含む原料混合物とＳｉＯとを混合し焼成して、Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４で表される黄色蛍光体を生成させる工程を含む方法によって製造できる。通常シリケート系蛍光体のＳｉ成分の原料としては、ＳｉＯ２が一般的である。本実施形態に係る製造方法は、Ｓｉ成分の原料としてＳｉＯを用いる点で通常の方法とは異なる。ＳｉＯは、Ｍ３成分の供給源として作用する。更にＳｉＯは、Ｌ成分（特にユウロピウム）を効率的に還元する作用も有している。そのためＬ成分を十分に還元することができ、黄色蛍光体の輝度を高めることができる。前記ＳｉＯは、粉末状のＳｉＯであることが好ましい。 The phosphor can be manufactured by firing a mixture of a raw material mixture containing at least M 1 , M 2 , and L and SiO. That is, the phosphor is a yellow fluorescent material represented by M 1 2a (M 2 b L c ) M 3 d O 4 by mixing and baking a raw material mixture containing M 1 , M 2 , and L and SiO. It can be manufactured by a method including a step of generating a body. Usually, SiO 2 is generally used as a raw material for the Si component of the silicate phosphor. The manufacturing method according to the present embodiment is different from a normal method in that SiO is used as a raw material for the Si component. SiO acts as a source of M 3 components. Furthermore, SiO has an action of efficiently reducing the L component (especially europium). Therefore, the L component can be sufficiently reduced, and the luminance of the yellow phosphor can be increased. The SiO is preferably powdered SiO.
　前記原料混合物は、より詳細には、元素Ｍ１を含む物質（第１原料）、元素Ｍ２を含む物質（第２原料）、元素Ｌを含む物質（第３原料）の混合物である。Ｍ３成分はＳｉＯから供給されるため、原料混合物は必ずしもＭ３を含む物質（Ｍ３含有原料；第４原料）を含む必要はない。好ましくは原料混合物は、第４原料（ただしＳｉＯは除く）を含む。前記元素Ｍ１、Ｍ２、Ｌ、及びＭ３はいずれも金属元素（半金属元素を含む）である。そのため、本明細書では前記第１～第４原料を金属元素含有物質と称する場合があり、それらの混合物を金属化合物混合物と称する場合がある。前記金属元素含有物質は、各金属Ｍ１、Ｍ２、Ｌ、又はＭ３の酸化物であってもよいし、高温（特に焼成温度）で分解又は酸化して酸化物を形成する物質であってもよい。この酸化物を形成する物質には、水酸化物、窒化物、酸窒化物、酸誘導体、塩（炭酸塩、硝酸塩、シュウ酸塩など）などが含まれる。 The raw material mixture, more particularly, material (first material) containing an element M 1, material (second material) containing the element M 2, which is a mixture of substances (third material) containing an element L. Since M 3 components supplied from the SiO, the raw material mixture is not necessarily material containing M 3; need not include (M 3 containing feedstock fourth raw material). Preferably, the raw material mixture includes a fourth raw material (excluding SiO). All of the elements M 1 , M 2 , L, and M 3 are metal elements (including metalloid elements). Therefore, in the present specification, the first to fourth raw materials may be referred to as metal element-containing substances, and a mixture thereof may be referred to as a metal compound mixture. The metal element-containing substance may be an oxide of each metal M 1 , M 2 , L, or M 3 , or a substance that decomposes or oxidizes at a high temperature (particularly the firing temperature) to form an oxide. May be. Substances that form this oxide include hydroxides, nitrides, oxynitrides, acid derivatives, salts (such as carbonates, nitrates, and oxalates).
　第１原料は、好ましくは金属Ｍ１（特にリチウム）の水酸化物、酸化物、及び炭酸塩から選ばれる。特に好ましい第１原料は、水酸化リチウム（ＬｉＯＨ）、酸化リチウム（Ｌｉ２Ｏ）又は炭酸リチウム（Ｌｉ２ＣＯ３）を含む。これら第１原料は、１種を単独で使用してもよく、複数を組み合わせてもよい。 The first raw material is preferably selected from hydroxides, oxides and carbonates of metal M 1 (particularly lithium). A particularly preferable first raw material contains lithium hydroxide (LiOH), lithium oxide (Li 2 O), or lithium carbonate (Li 2 CO 3 ). These 1st raw materials may be used individually by 1 type, and may combine multiple.
　第２原料の好ましい例には、金属Ｍ２（特にストロンチウム、バリウム、カルシウムなど）の水酸化物、酸化物又は炭酸塩が含まれる。より具体的には、第２原料は、例えば、水酸化ストロンチウム（Ｓｒ（ＯＨ）２）、酸化ストロンチウム（ＳｒＯ）及び炭酸ストロンチウム（ＳｒＣＯ３）から選ばれる。これら第２原料は、１種を単独で使用してもよく、複数を組み合わせてもよい。 Preferable examples of the second raw material include a hydroxide, oxide or carbonate of metal M 2 (especially strontium, barium, calcium, etc.). More specifically, the second raw material is selected from, for example, strontium hydroxide (Sr (OH) 2 ), strontium oxide (SrO), and strontium carbonate (SrCO 3 ). These 2nd raw materials may be used individually by 1 type, and may combine multiple.
　第３原料は、金属Ｌ（特にユウロピウム）の水酸化物、酸化物、炭酸塩又は塩化物であることが好ましい。第３原料は、例えば、水酸化ユウロピウム（Ｅｕ（ＯＨ）２、Ｅｕ（ＯＨ）３）、酸化ユウロピウム（ＥｕＯ、Ｅｕ２Ｏ３）、炭酸ユウロピウム（ＥｕＣＯ３、Ｅｕ２（ＣＯ３）３）、塩化ユウロピウム（ＥｕＣｌ２、ＥｕＣｌ３）及び硝酸ユウロピウム（Ｅｕ（ＮＯ３）２、Ｅｕ（ＮＯ３）３）から選ばれる。これら第３原料は、１種を単独で使用してもよく、複数を組み合わせてもよい。 The third raw material is preferably a hydroxide, oxide, carbonate or chloride of metal L (especially europium). The third raw material includes, for example, europium hydroxide (Eu (OH) 2 , Eu (OH) 3 ), europium oxide (EuO, Eu 2 O 3 ), europium carbonate (EuCO 3 , Eu 2 (CO 3 ) 3 ), It is selected from europium chloride (EuCl 2 , EuCl 3 ) and europium nitrate (Eu (NO 3 ) 2 , Eu (NO 3 ) 3 ). These third raw materials may be used alone or in combination.
　第４原料（Ｍ３含有原料）としては、好ましくは金属Ｍ３（特に珪素）の酸化物、酸誘導体及び塩などが挙げられる。好ましい第４原料には、例えば、二酸化珪素、珪酸又は珪酸塩が含まれる。 Preferred examples of the fourth raw material (M 3 -containing raw material) include oxides, acid derivatives, and salts of metal M 3 (particularly silicon). A preferable fourth raw material includes, for example, silicon dioxide, silicic acid, or silicate.
　第１原料～第４原料、及びＳｉＯは、各原料から供給される元素Ｍ１、Ｍ２、Ｌ、Ｍ３の原子比が、式Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４におけるａ、ｂ、ｃ、ｄの関係を満足する範囲内で混合する。 In the first to fourth raw materials and SiO, the atomic ratio of the elements M 1 , M 2 , L, and M 3 supplied from each raw material is expressed by the formula M 1 2a (M 2 b L c ) M 3 d O 4. Are mixed within a range satisfying the relationship of a, b, c and d.
　またＳｉＯの使用量は、還元剤として使用する場合には、原料混合物の質量を１とした場合、０．００１～１（０．００１以上、１以下）であり、好ましくは０．００５～０．５（０．００５以上、０．５以下）であり、さらに好ましくは０．１～０．３（０．１以上、０．３以下）である。ＳｉＯを原料として使用する場合、ＳｉＯとは異なる物質もＭ３含有原料として原料混合物に配合することができる。この場合、ＳｉＯの使用量は、黄色蛍光体中の元素Ｍ３の全量に対して、前記ＳｉＯに由来するＳｉ元素の割合が０．００１～５０原子％、好ましくは０．００５～２０原子％となるような量とすることが好ましい。すなわち、蛍光体中の元素Ｍ３のうち、０．００１原子％以上、５０原子％以下、好ましくは０．００５原子％以上、２０原子％以下がＳｉＯに由来する程度の量のＳｉＯを使用することが推奨される。 When used as a reducing agent, the amount of SiO used is 0.001 to 1 (0.001 or more and 1 or less), preferably 0.005 to 0 when the mass of the raw material mixture is 1. 0.5 (0.005 or more and 0.5 or less), more preferably 0.1 to 0.3 (0.1 or more and 0.3 or less). When SiO is used as a raw material, a substance different from SiO can be blended in the raw material mixture as an M 3 -containing raw material. In this case, the amount of SiO used is such that the proportion of Si element derived from SiO is 0.001 to 50 atomic%, preferably 0.005 to 20 atomic%, with respect to the total amount of element M 3 in the yellow phosphor. The amount is preferably such that That is, of the element M 3 in the phosphor, 0.001 atomic% or more and 50 atomic% or less, preferably 0.005 atomic% or more and 20 atomic% or less of SiO is used in such an amount. It is recommended.
　例えば、本実施形態に係る製造方法によって得られる蛍光体の好ましい組成の一つであるＬｉ１．９６Ｓｒ０．９８Ｅｕ０．０２ＳｉＯ４を得るためには以下のようにすればよい。例えば、ＳｉＯは、使用割合が全Ｓｉ含有物質に対して１．０原子％となるように用いる。原料混合物（金属化合物混合物）に含まれるＳｒＣＯ３、Ｌｉ２ＣＯ３、ＳｉＯ２及びＥｕ２Ｏ３の混合比率は、Ｌｉ：Ｓｒ：Ｅｕ：Ｓｉのモル比が１．９６：０．９８：０．０２：１．０となるように定めればよい。このとき、ＳｉＯの使用割合は、全Ｓｉ含有物質に対して１．０原子％であるので、ＳｉＯ２：ＳｉＯ＝０．９９：０．０１となればよい。 For example, in order to obtain Li 1.96 Sr 0.98 Eu 0.02 SiO 4 , which is one of the preferred compositions of the phosphor obtained by the manufacturing method according to the present embodiment, the following may be performed. For example, SiO is used so that the usage ratio is 1.0 atomic% with respect to the total Si-containing material. The mixing ratio of SrCO 3 , Li 2 CO 3 , SiO 2 and Eu 2 O 3 contained in the raw material mixture (metal compound mixture) is such that the molar ratio of Li: Sr: Eu: Si is 1.96: 0.98: 0. .02: 1.0 may be set. At this time, since the use ratio of SiO is 1.0 atomic% with respect to the total Si-containing material, it may be SiO 2 : SiO = 0.99: 0.01.
　前記第１～第３原料（好ましくは第１～第４原料）及びＳｉＯは、湿式の方法で混合してもよく、乾式の方法で混合してもよい。この混合には、例えば、ボールミル、Ｖ型混合機及び攪拌機などの汎用装置が使用できる。 The first to third raw materials (preferably the first to fourth raw materials) and SiO may be mixed by a wet method or a dry method. For this mixing, for example, general-purpose devices such as a ball mill, a V-type mixer and a stirrer can be used.
　原料混合物とＳｉＯとの混合物を焼成する場合、通常のＭ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４で表される蛍光体を焼成する場合に採用されている条件と同等の条件を採用できる。例えば、焼成室の雰囲気、すなわち焼成雰囲気は、不活性ガス雰囲気、酸化性ガス雰囲気、還元性ガス雰囲気のいずれでもよい。なお強い還元性雰囲気下で原料混合物とＳｉＯとの混合物を焼成する場合には、上記原料混合物（金属化合物混合物）に適量の炭素を添加して焼成してもよい。図１は、原料混合物を焼成する焼成処理装置の一実施形態を示す模式図である。上記焼成は、例えば、原料混合物とＳｉＯとの混合物５を焼成室３０に入れて加熱することによって行われる。 When firing a mixture of a raw material mixture and SiO, conditions equivalent to those employed when firing a phosphor represented by ordinary M 1 2a (M 2 b L c ) M 3 d O 4 are used. Can be adopted. For example, the firing chamber atmosphere, that is, the firing atmosphere, may be any of an inert gas atmosphere, an oxidizing gas atmosphere, and a reducing gas atmosphere. When firing the mixture of the raw material mixture and SiO in a strong reducing atmosphere, an appropriate amount of carbon may be added to the raw material mixture (metal compound mixture) and fired. FIG. 1 is a schematic view showing an embodiment of a firing processing apparatus for firing a raw material mixture. The firing is performed by, for example, putting the mixture 5 of the raw material mixture and SiO in the firing chamber 30 and heating.
　前記不活性ガスは、窒素、アルゴンが例示できる。前記酸化性ガスは、例えば、酸素、酸素を含有する不活性ガス（窒素、アルゴンなど）及び空気が挙げられる。前記還元性ガスには、例えば、０．１～１０体積％の水素と不活性ガス（窒素、アルゴンなど）との混合ガス、又は１０～１００体積％（好ましくは５０～１００体積％）のＮＨ３と不活性ガス（窒素、アルゴンなど）との混合ガスが含まれる。これらガスは、必要に応じて、加圧されていてもよい。 Examples of the inert gas include nitrogen and argon. Examples of the oxidizing gas include oxygen, oxygen-containing inert gas (nitrogen, argon, etc.), and air. Examples of the reducing gas include a mixed gas of 0.1 to 10% by volume of hydrogen and an inert gas (nitrogen, argon, etc.), or 10 to 100% by volume (preferably 50 to 100% by volume) of NH. 3 and an inert gas (nitrogen, argon, etc.). These gases may be pressurized as necessary.
　好ましい焼成雰囲気は、０．１～１０体積％（より好ましくは２～８体積％、特に好ましくは４～６体積％）水素と不活性ガス（特に窒素）との混合ガスである。 A preferable firing atmosphere is a mixed gas of 0.1 to 10% by volume (more preferably 2 to 8% by volume, particularly preferably 4 to 6% by volume) hydrogen and an inert gas (particularly nitrogen).
　焼成は、複数回繰り返し行ってもよい。このとき、第一回目の焼成と、第二回目の焼成とで焼成雰囲気を変更してもよく、第三回目以降の焼成でも焼成雰囲気を変更してもよい。例えば、不活性ガス雰囲気下又は酸化性ガス雰囲気下で焼成した場合は、その後さらに還元性ガス雰囲気下で焼成を行うことが好ましい。 Calcination may be repeated a plurality of times. At this time, the firing atmosphere may be changed between the first firing and the second firing, and the firing atmosphere may be changed in the third and subsequent firings. For example, when calcination is performed in an inert gas atmosphere or an oxidizing gas atmosphere, it is preferable to perform calcination in a reducing gas atmosphere thereafter.
　焼成温度は、通常、７００～１０００℃であり、好ましくは７５０～９５０℃であり、より好ましくは８００～９００℃である。焼成時間は、通常、１～１００時間であり、好ましくは１０～９０時間であり、より好ましくは２０～８０時間である。 Calcination temperature is usually 700 to 1000 ° C., preferably 750 to 950 ° C., more preferably 800 to 900 ° C. The firing time is usually 1 to 100 hours, preferably 10 to 90 hours, and more preferably 20 to 80 hours.
　本実施形態に係る方法は、前記焼成に先立って、必要に応じて、焼成よりも低温（例えば５００～８００℃）で所定時間（例えば１～１００時間、好ましくは１０～９０時間）、原料混合物を保持して、原料混合物を仮焼する工程を更に含んでいてもよい。 Prior to the calcination, the method according to the present embodiment includes a raw material mixture, if necessary, at a temperature lower than the calcination (eg, 500 to 800 ° C.) for a predetermined time (eg, 1 to 100 hours, preferably 10 to 90 hours). And a step of calcining the raw material mixture may be further included.
　本実施形態に係る方法では、必要により、反応促進剤の存在下で仮焼又は焼成を行ってもよい。反応促進剤を用いることによって、得られる蛍光体の発光強度をより向上できる。反応促進剤は、例えばアルカリ金属ハロゲン化物、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、ハロゲン化アンモニウム、ホウ素の酸化物（Ｂ２Ｏ３）及びホウ素のオキソ酸（Ｈ３ＢＯ３）から選ばれる。前記アルカリ金属ハロゲン化物は、好ましくはアルカリ金属のフッ化物又はアルカリ金属の塩化物であり、例えば、ＬｉＦ、ＮａＦ、ＫＦ、ＬｉＣｌ、ＮａＣｌ又はＫＣｌである。前記アルカリ金属炭酸塩は、例えば、Ｌｉ２ＣＯ３、Ｎａ２ＣＯ３又はＫ２ＣＯ３である。前記アルカリ金属炭酸水素塩は、例えば、ＮａＨＣＯ３である。前記ハロゲン化アンモニウムは、例えば、ＮＨ４Ｃｌ又はＮＨ４Ｉである。 In the method according to this embodiment, if necessary, calcination or baking may be performed in the presence of a reaction accelerator. By using the reaction accelerator, the emission intensity of the obtained phosphor can be further improved. The reaction accelerator is selected from, for example, alkali metal halides, alkali metal carbonates, alkali metal hydrogen carbonates, ammonium halides, boron oxides (B 2 O 3 ), and boron oxo acids (H 3 BO 3 ). . The alkali metal halide is preferably an alkali metal fluoride or an alkali metal chloride, such as LiF, NaF, KF, LiCl, NaCl, or KCl. The alkali metal carbonate is, for example, Li 2 CO 3 , Na 2 CO 3 or K 2 CO 3 . The alkali metal bicarbonate is, for example, NaHCO 3 . The ammonium halide is, for example, NH 4 Cl or NH 4 I.
　本実施形態に係る製造方法によって得られる蛍光体は、原料混合物に由来するハロゲン元素、すなわちＦ、Ｃｌ、Ｂｒ又はＩの１種以上の元素を含有していてもよい。ハロゲン元素の合計含有量は、原料中に含有されるハロゲン元素の合計量に対して同量以下であれば良く、好ましくは５０％以下、さらに好ましくは２５％以下である。 The phosphor obtained by the manufacturing method according to the present embodiment may contain a halogen element derived from the raw material mixture, that is, one or more elements of F, Cl, Br, or I. The total content of halogen elements may be equal to or less than the total content of halogen elements contained in the raw material, preferably 50% or less, and more preferably 25% or less.
　仮焼物又は焼成物に対して、必要により、粉砕、混合、洗浄及び分級のうちいずれか一つ以上の処理を施してもよい。粉砕、混合には、例えば、ボールミル、Ｖ型混合機、攪拌機、ジェットミルなどが使用できる。 If necessary, the calcined product or the fired product may be subjected to any one or more of pulverization, mixing, washing, and classification. For pulverization and mixing, for example, a ball mill, a V-type mixer, a stirrer, a jet mill or the like can be used.
　本実施形態に係る製造方法によれば、ＳｉＯを用いて焼成しているため、高輝度な蛍光体を得ることができる。このような蛍光体は、Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４で表される黄色蛍光体である。上記製法によって得られる黄色蛍光体は高い発光強度を有するため、発光装置（例えば白色ＬＥＤ）において好適に用いることができる。白色ＬＥＤは、紫外から青色の光（波長が２００～５５０ｎｍ程度、好ましくは３８０～５００ｎｍ程度）を放出する発光素子（ＬＥＤチップ）と、蛍光体を含む蛍光層とから構成される。この白色ＬＥＤは、例えば、特開平１１－３１８４５号公報、特開２００２－２２６８４６号公報等に開示の方法によって製造することができる。すなわち、例えば、前記発光素子を、エポキシ樹脂、シリコーン樹脂などの透光性樹脂で封止し、その表面を蛍光体で覆う方法により白色ＬＥＤを製造できる。蛍光体の量を適宜設定すれば、白色ＬＥＤが所望の白色を発光するようになる。 According to the manufacturing method according to the present embodiment, since it is baked using SiO, a high-luminance phosphor can be obtained. Such a phosphor is a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 . Since the yellow phosphor obtained by the above production method has high emission intensity, it can be suitably used in a light emitting device (for example, white LED). A white LED is composed of a light emitting element (LED chip) that emits ultraviolet to blue light (having a wavelength of about 200 to 550 nm, preferably about 380 to 500 nm), and a fluorescent layer containing a phosphor. This white LED can be manufactured by a method disclosed in, for example, Japanese Patent Application Laid-Open Nos. 11-31845 and 2002-226846. That is, for example, a white LED can be manufactured by a method in which the light emitting element is sealed with a translucent resin such as an epoxy resin or a silicone resin, and the surface thereof is covered with a phosphor. If the amount of the phosphor is appropriately set, the white LED emits a desired white color.
　図２は、発光装置の一実施形態を示す断面図である。図２に示す発光装置１は、発光素子１０と、発光素子１０上に設けられた蛍光層２０とを備える。蛍光層２０を形成する蛍光体は、発光素子１０からの光を受光して励起されて蛍光を発光する。蛍光層２０を構成する蛍光体の種類、量等を適宜設定することにより、白色の発光を得ることができる。すなわち、白色ＬＥＤを構成することができる。本実施形態に係る発光装置又は白色ＬＥＤは、図２に示す形態に何ら限定されるものではなく、本発明の趣旨を逸脱しない範囲で適宜変形が可能である。 FIG. 2 is a cross-sectional view showing an embodiment of a light emitting device. The light emitting device 1 illustrated in FIG. 2 includes a light emitting element 10 and a fluorescent layer 20 provided on the light emitting element 10. The phosphor forming the fluorescent layer 20 receives the light from the light emitting element 10 and is excited to emit fluorescence. White light emission can be obtained by appropriately setting the type, amount, and the like of the phosphor constituting the phosphor layer 20. That is, a white LED can be configured. The light emitting device or the white LED according to this embodiment is not limited to the form shown in FIG. 2 and can be appropriately modified without departing from the gist of the present invention.
　前記蛍光体としては、本実施形態に係る製造方法により得られる黄色蛍光体を単独で含んでいてもよいし、他の蛍光体を更に含んでいてもよい。他の蛍光体は、例えば、ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ、（Ｂａ，Ｓｒ，Ｃａ）（Ａｌ，Ｇａ）２Ｓ４：Ｅｕ、ＢａＭｇＡｌ１０Ｏ１７：（Ｅｕ，Ｍｎ）、ＢａＡｌ１２Ｏ１９：（Ｅｕ，Ｍｎ）、（Ｂａ，Ｓｒ，Ｃａ）Ｓ：（Ｅｕ，Ｍｎ）、ＹＢＯ３：（Ｃｅ，Ｔｂ）、Ｙ２Ｏ３：Ｅｕ、Ｙ２Ｏ２Ｓ：Ｅｕ、ＹＶＯ４：Ｅｕ、（Ｃａ，Ｓｒ）Ｓ：Ｅｕ、ＳｒＹ２Ｏ４：Ｅｕ、Ｃａ－Ａｌ－Ｓｉ－Ｏ－Ｎ：Ｅｕ、（Ｂａ，Ｓｒ，Ｃａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ、β－サイアロン、ＣａＳｃ２Ｏ４：Ｃｅ及びＬｉ－（Ｃａ，Ｍｇ）－Ｌｎ－Ａｌ－Ｏ－Ｎ：Ｅｕ（ただし、ＬｎはＥｕ以外の希土類金属元素を表す）から選ばれる。 As said fluorescent substance, the yellow fluorescent substance obtained by the manufacturing method which concerns on this embodiment may be included independently, and the other fluorescent substance may be further included. Other phosphors include, for example, BaMgAl 10 O 17 : Eu, (Ba, Sr, Ca) (Al, Ga) 2 S 4 : Eu, BaMgAl 10 O 17 : (Eu, Mn), BaAl 12 O 19 :( Eu, Mn), (Ba, Sr, Ca) S: (Eu, Mn), YBO 3 : (Ce, Tb), Y 2 O 3 : Eu, Y 2 O 2 S: Eu, YVO 4 : Eu, ( Ca, Sr) S: Eu, SrY 2 O 4 : Eu, Ca—Al—Si—O—N: Eu, (Ba, Sr, Ca) Si 2 O 2 N 2 : Eu, β-sialon, CaSc 2 O 4 : Selected from Ce and Li— (Ca, Mg) —Ln—Al—O—N: Eu (where Ln represents a rare earth metal element other than Eu).
　波長２００ｎｍ～５５０ｎｍの光を発する発光素子としては、紫外ＬＥＤチップ、青色ＬＥＤチップなどが挙げられる。これらＬＥＤチップには発光層としてＧａＮ、ＩｎｉＧａ１－ｉＮ（０＜ｉ＜１）、ＩｎｉＡｌｊＧａ１－ｉ－ｊＮ（０＜ｉ＜１、０＜ｊ＜１、ｉ＋ｊ＜１）などの層を有する半導体が用いられる。発光層の組成を変化させることにより、発光波長を変化させることができる。 Examples of the light emitting element that emits light having a wavelength of 200 nm to 550 nm include an ultraviolet LED chip and a blue LED chip. In these LED chips, GaN, In i Ga 1-i N (0 <i <1), In i Al j Ga 1- jN (0 <i <1, 0 <j <1, i + j) are used as light emitting layers. A semiconductor having a layer such as <1) is used. The emission wavelength can be changed by changing the composition of the light emitting layer.
　本実施形態に係る製造方法によって得られる蛍光体は、白色ＬＥＤ以外の発光装置、例えば、蛍光体励起源が真空紫外線である発光装置（例えば、ＰＤＰ）；蛍光体励起源が紫外線である発光装置（例えば、液晶ディスプレイ用バックライト、三波長形蛍光ランプ）；蛍光体励起源が電子線である発光装置（例えば、ＣＲＴやＦＥＤ）などにも使用できる。 The phosphor obtained by the manufacturing method according to the present embodiment is a light emitting device other than a white LED, for example, a light emitting device whose phosphor excitation source is vacuum ultraviolet light (for example, PDP); a light emitting device whose phosphor excitation source is ultraviolet light (For example, a backlight for a liquid crystal display, a three-wavelength fluorescent lamp); It can also be used for a light emitting device (for example, CRT or FED) in which the phosphor excitation source is an electron beam.
　以下、実施例を挙げて本発明をより具体的に説明する。本発明はもとより下記実施例によって制限を受けるものではない。前記及び後記の趣旨に適合し得る範囲で適当に変更を加えた態様により本発明を実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples. Of course, it is possible to implement the present invention in a mode appropriately modified within a range that can be adapted to the above-described and the gist of the following, all of which are included in the technical scope of the present invention.
　なお以下の実施例で得られる蛍光体の発光強度は、蛍光分光測定装置（日本分光（株）製ＦＰ－６５００）を用いて決定した。蛍光体のＸ線回折（ＸＲＤ）測定には、Ｘ線回折装置（リガク製ＲＩＮＴ２０００）を用いた。蛍光体中のＥｕの価数割合は、Ｘ線吸収微細構造（ＸＡＦＳ）測定によって評価した。 The emission intensity of the phosphors obtained in the following examples was determined using a fluorescence spectrometer (FP-6500 manufactured by JASCO Corporation). An X-ray diffractometer (RINT2000 manufactured by Rigaku) was used for X-ray diffraction (XRD) measurement of the phosphor. The valence ratio of Eu in the phosphor was evaluated by X-ray absorption fine structure (XAFS) measurement.
　ＸＡＦＳ測定は、ＳＰｒｉｎｇ－８においてビームラインＢＬ１４Ｂ２を用いて透過法で行った。Ｅｕ－Ｌ３吸収端である６６５０～７６００ｅＶを測定領域とした。Ｅｕ２＋（６９７２ｅＶ）の標準試料は、ＢａＭｇＡｌ１０Ｏ１７：Ｅｕ２＋（ＢＡＭ）を用いた。Ｅｕ３＋（６９８０ｅＶ）の標準試料は、酸化ユウロピウム（信越化学工業株式会社製、純度９９．９９％）を用いた。Ｘ線吸収端近傍構造（ＸＡＮＥＳ）スペクトルは、解析プログラム（リガク製ＲＥＸ２０００）を用い、各試料のＸＡＦＳデータをバックグラウンドに基づいて処理することによって得た。その後、Ｅｕ２＋標準試料及びＥｕ３＋標準試料のＸＡＮＥＳスペクトルを用いて、各試料のＸＡＮＥＳスペクトルのパターンフィッティングを行い、Ｅｕ２＋ピークの割合から、試料中のＥｕ２＋の割合を算出した。 XAFS measurement was performed by the transmission method using the beam line BL14B2 at SPring-8. The Eu-L3 absorption edge, 6650-7600 eV, was used as the measurement region. BaMgAl 10 O 17 : Eu 2+ (BAM) was used as a standard sample of Eu 2+ (6792 eV). As a standard sample of Eu 3+ (6980 eV), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%) was used. The X-ray absorption near edge structure (XANES) spectrum was obtained by processing the XAFS data of each sample based on the background using an analysis program (Rigaku REX2000). Thereafter, pattern fitting of the XANES spectrum of each sample was performed using the XANES spectra of the Eu 2+ standard sample and Eu 3+ standard sample, and the ratio of Eu 2+ in the sample was calculated from the ratio of Eu 2+ peaks.
　結晶性物質中の酸素の含有量は、堀場製作所製ＥＭＧＡ－９２０を用いて測定した。酸素の含有量については非分散型赤外吸収法を用いた。 The content of oxygen in the crystalline substance was measured using EMGA-920 manufactured by Horiba. The non-dispersive infrared absorption method was used for the oxygen content.
　比較例１
　炭酸リチウム（関東化学株式会社製、純度９９％）、炭酸ストロンチウム（堺化学工業株式会社製、純度９９％以上）、酸化ユウロピウム（信越化学工業株式会社製、純度９９．９９％）、及び二酸化珪素（日本アエロジル株式会社製：純度９９．９９％）を、Ｌｉ：Ｓｒ：Ｅｕ：Ｓｉの原子比が１．９６：０．９８：０．０２：１．０となるように秤取し、これらを乾式ボールミルにより６時間混合して金属化合物混合物を得た。 Comparative Example 1
Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) were weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0. Were mixed by a dry ball mill for 6 hours to obtain a metal compound mixture.
　５体積％のＨ２を含有するＮ２雰囲気中、前記金属化合物混合物を温度８００℃で２４時間加熱（焼成）した。これを室温まで徐冷して、式Ｌｉ１．９６（Ｓｒ０．９８Ｅｕ０．０２）ＳｉＯ４で表される化合物を含有する蛍光体を得た。蛍光体の全Ｅｕ中の２価のＥｕ（Ｅｕ２＋）の割合は１４％であった。 The metal compound mixture was heated (baked) for 24 hours at a temperature of 800 ° C. in an N 2 atmosphere containing 5% by volume of H 2 . This was gradually cooled to room temperature to obtain a phosphor containing a compound represented by the formula Li 1.96 (Sr 0.98 Eu 0.02 ) SiO 4 . The ratio of divalent Eu (Eu 2+ ) in the total Eu of the phosphor was 14%.
　比較例２
　炭酸リチウム（関東化学株式会社製、純度９９％）、炭酸ストロンチウム（堺化学工業株式会社製、純度９９％以上）、酸化ユウロピウム（信越化学工業株式会社製、純度９９．９９％）、及び二酸化珪素（日本アエロジル株式会社製：純度９９．９９％）を、Ｌｉ：Ｓｒ：Ｅｕ：Ｓｉの原子比が１．９６：０．９８：０．０２：１．０となるように秤取し、これらを乾式ボールミルにより６時間混合して金属化合物混合物を得た。 Comparative Example 2
Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) were weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0. Were mixed by a dry ball mill for 6 hours to obtain a metal compound mixture.
　５体積％のＨ２を含有するＮ２雰囲気中、前記金属化合物混合物を温度８００℃で２４時間加熱（焼成）し、室温まで徐冷した。得られた焼成物を粉砕し、さらに５体積％のＨ２を含有するＮ２雰囲気中で、温度８００℃で２４時間加熱（焼成）することで式Ｌｉ１．９６（Ｓｒ０．９８Ｅｕ０．０２）ＳｉＯ４で表される化合物を含有する蛍光体を得た。蛍光体の全Ｅｕ中の２価のＥｕ（Ｅｕ２＋）の割合は１７％であった。 In a N 2 atmosphere containing 5% by volume of H 2 , the metal compound mixture was heated (baked) at a temperature of 800 ° C. for 24 hours and gradually cooled to room temperature. The obtained fired product is pulverized, and further heated (fired) at a temperature of 800 ° C. for 24 hours in an N 2 atmosphere containing 5% by volume of H 2 to obtain the formula Li 1.96 (Sr 0.98 Eu 0 0.02 ) A phosphor containing a compound represented by SiO 4 was obtained. The ratio of divalent Eu (Eu 2+ ) in the total Eu of the phosphor was 17%.
　１…発光装置、５…原料混合物とＳｉＯとの混合物、１０…発光素子、２０…蛍光層、３０…焼成室。
  DESCRIPTION OF SYMBOLS 1 ... Light-emitting device, 5 ... Mixture of raw material mixture and SiO, 10 ... Light emitting element, 20 ... Fluorescent layer, 30 ... Baking chamber.

Claims (11)

  1. 　Ｍ１、Ｍ２、及びＬを含む原料混合物とＳｉＯとを混合し焼成して、Ｍ１ ２ａ（Ｍ２ ｂＬｃ）Ｍ３ ｄＯ４で表される黄色蛍光体を生成させる工程を含み、
    　Ｍ１はアルカリ金属から選択される少なくとも一種の元素であり、
    　Ｍ２はアルカリ土類金属から選択される少なくとも一種の元素であり、
    　Ｍ３はＳｉである、又は、Ｓｉ及びＧｅであり、
    　Ｌは希土類元素、Ｂｉ及びＭｎから選択される少なくとも一種の元素であり、
    　ａは、０．１～１．５であり、
    　ｂは、０．８～１．２であり、
    　ｃは、０．００５～０．２であり、
    　ｄは、０．８～１．２である、
    黄色蛍光体の製造方法。     Including a step of mixing a raw material mixture containing M 1 , M 2 , and L and SiO and firing to produce a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 ,
    M 1 is at least one element selected from alkali metals,
    M 2 is at least one element selected from alkaline earth metals,
    M 3 is Si or Si and Ge;
    L is at least one element selected from rare earth elements, Bi and Mn,
    a is 0.1 to 1.5;
    b is 0.8 to 1.2;
    c is 0.005 to 0.2,
    d is 0.8 to 1.2,
    A method for producing a yellow phosphor.
  2. 　前記原料混合物が、ＳｉＯとは異なるＭ３含有原料を更に含有し、
    　前記黄色蛍光体中の元素Ｍ３の全量に対して、前記ＳｉＯに由来するＳｉ元素の割合が０．００１～５０原子％である、請求項１に記載の製造方法。     The raw material mixture further contains an M 3 -containing raw material different from SiO,
    The production method according to claim 1, wherein the ratio of Si element derived from SiO is 0.001 to 50 atomic% with respect to the total amount of element M 3 in the yellow phosphor.
  3. 　Ｌが、希土類元素、Ｂｉ及びＭｎから選択される、Ｅｕを含む少なくとも一種の元素である、請求項１又は２に記載の製造方法。 The production method according to claim 1 or 2, wherein L is at least one element including Eu selected from rare earth elements, Bi and Mn.
  4. 　Ｌが、希土類元素、Ｂｉ及びＭｎから選択される、２価のＥｕを含む少なくとも一種の元素である、請求項３に記載の製造方法。 The production method according to claim 3, wherein L is at least one element containing divalent Eu selected from rare earth elements, Bi and Mn.
  5. 　Ｍ１がＬｉであり、Ｍ３がＳｉである、請求項１～４のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 4, wherein M 1 is Li and M 3 is Si.
  6. 　Ｍ２が、Ｓｒのみである、Ｓｒ及びＢａである、又は、Ｓｒ及びＣａである、請求項１～５のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 5, wherein M 2 is only Sr, Sr and Ba, or Sr and Ca.
  7. 　ａが、０．９～１．１である、請求項１～６のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 6, wherein a is from 0.9 to 1.1.
  8. 　ｂ＋ｃが１であり、ｄが１である、請求項１～７のいずれか一項に記載の製造方法。 The production method according to any one of claims 1 to 7, wherein b + c is 1 and d is 1.
  9. 　請求項１～８のいずれか一項に記載の方法によって製造することのできる黄色蛍光体。 A yellow phosphor that can be produced by the method according to any one of claims 1 to 8.
  10. 　請求項９に記載の黄色蛍光体を有する発光装置。 A light emitting device comprising the yellow phosphor according to claim 9.
  11. 　請求項９に記載の黄色蛍光体を有する白色ＬＥＤ。 A white LED having the yellow phosphor according to claim 9.
PCT/JP2011/077952 2010-12-02 2011-12-02 Yellow phosphor and method for manufacturing same WO2012074105A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-269353 2010-12-02
JP2010269353A JP2012116980A (en) 2010-12-02 2010-12-02 Yellow phosphor and manufacturing method therefor

Publications (1)

Publication Number Publication Date
WO2012074105A1 true WO2012074105A1 (en) 2012-06-07

Family

ID=46172026

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/077952 WO2012074105A1 (en) 2010-12-02 2011-12-02 Yellow phosphor and method for manufacturing same

Country Status (3)

Country Link
JP (1) JP2012116980A (en)
TW (1) TW201241153A (en)
WO (1) WO2012074105A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2014941A (en) 2014-07-16 2016-04-12 Asml Netherlands Bv Lithographic apparatus, device manufacturing method and associated data processing apparatus and computer program product.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006090865A1 (en) * 2005-02-23 2006-08-31 Sumitomo Chemical Company, Limited Phosphor, light emitting device and white light emitting diode

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006090865A1 (en) * 2005-02-23 2006-08-31 Sumitomo Chemical Company, Limited Phosphor, light emitting device and white light emitting diode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KENJI TODA ET AL.: "Kitai kara Tsukuru Jisedai Shomeiyo Hakko Zairyo Retort Pack no Hogo Film kara Keikotai ga Dekita!", SHUKI THE JAPAN SOCIETY OF APPLIED PHYSICS GAKUJUTSU KOENKAI NO PREVIEW HAPPYO, 1 September 2010 (2010-09-01), Retrieved from the Internet <URL:http://www.jsap.or.jp/pressrelease/press-100901.html> *

Also Published As

Publication number Publication date
TW201241153A (en) 2012-10-16
JP2012116980A (en) 2012-06-21

Similar Documents

Publication Publication Date Title
JP5717075B2 (en) Phosphor, method for manufacturing the same, light emitting device, and image display device
TWI408210B (en) Green fluorescent materials, methods of fabricating the same and emission devices using the green fluorescent materials
JP5578739B2 (en) Alkaline earth metal silicate phosphor and method for producing the same
JP5706441B2 (en) Strontium oxyorthosilicate phosphor with improved stability to radiation load and resistance to atmospheric humidity
WO2012074102A1 (en) Method for producing crystalline material
JP2006232906A (en) Fluorescent substance and light-emitting apparatus using the same
JP2012531488A (en) Luminescent material with Eu2 + -doped silicate phosphor
WO2016076380A1 (en) Phosphor, light-emitting device, illumination device, and image display device
JP6421806B2 (en) Aluminate phosphor manufacturing method, aluminate phosphor and light emitting device
JP2019065112A (en) Aluminate phosphor, light-emitting device and method for producing aluminate phosphor
WO2012074103A1 (en) Crystalline material, and light-emitting device and white led using same
WO2012074105A1 (en) Yellow phosphor and method for manufacturing same
WO2012063685A1 (en) Yellow phosphor and manufacturing method therefor
JP2017186459A (en) Nitride phosphor powder and production method thereof
WO2012074104A1 (en) Phosphor manufacturing method
JP5870256B2 (en) Phosphor and light emitting device
WO2012043879A1 (en) Phosphor and method for producing same
JP7152667B2 (en) Phosphor manufacturing method and phosphor
WO2015111626A1 (en) Fluorescent material and light-emitting device
JP2016121300A (en) Phosphor
JP5385961B2 (en) Phosphor and light emitting device using the same
JP2019044159A (en) Aluminate phosphor and light emitting device
KR20160055216A (en) Method for producing silicate phosphor
JP2017066340A (en) Oxide phosphor and light emitting device prepared therewith
WO2016072407A1 (en) Phosphor and light-emitting device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11844954

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11844954

Country of ref document: EP

Kind code of ref document: A1