WO2012033013A1 - Procédé de production de sialon de type β - Google Patents

Procédé de production de sialon de type β Download PDF

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Publication number
WO2012033013A1
WO2012033013A1 PCT/JP2011/070008 JP2011070008W WO2012033013A1 WO 2012033013 A1 WO2012033013 A1 WO 2012033013A1 JP 2011070008 W JP2011070008 W JP 2011070008W WO 2012033013 A1 WO2012033013 A1 WO 2012033013A1
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WO
WIPO (PCT)
Prior art keywords
acid
mixed
sialon
heating step
producing
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PCT/JP2011/070008
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English (en)
Japanese (ja)
Inventor
真太郎 渡邉
光明 斉藤
秀幸 江本
山田　鈴弥
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電気化学工業株式会社
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Priority to JP2012532954A priority Critical patent/JP5883390B2/ja
Publication of WO2012033013A1 publication Critical patent/WO2012033013A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides

Definitions

  • the present invention relates to a method for producing ⁇ -sialon in which europium (Eu) is dissolved.
  • Patent Document 1 as a method for producing ⁇ -sialon in which Eu is dissolved, acid emission using a mixed acid solution of hydrofluoric acid and sulfuric acid is used to improve the emission intensity of ⁇ -sialon in which Eu is dissolved. It is described. However, Patent Document 1 also describes that the phosphor dissolves when the concentration of the mixed acid solution is high, and that the phosphor dissolves when the temperature reaches 60 ° C. or higher.
  • Patent Document 2 in order to improve the emission intensity of ⁇ -sialon in which Eu is dissolved, the pulverized fired product is reheated at 1300 ° C. to 1600 ° C. in an inert gas other than nitrogen gas, and then 50% fluorine is added.
  • a technique for acid treatment using a mixed acid solution of hydrofluoric acid and 70% nitric acid is disclosed.
  • An object of the present invention is to provide a method for producing ⁇ -sialon in which Eu is dissolved, which can realize higher luminous efficiency with good reproducibility.
  • the present invention is a method for producing ⁇ -sialon in which Eu is dissolved in ⁇ -sialon represented by the general formula: Si 6-z Al z O z N 8-z (0 ⁇ z ⁇ 4.2), A first heating step of firing a raw material mixed powder containing Si, Al, Eu in a nitrogen atmosphere, a second heating step of heat-treating the obtained fired product in an inert gas atmosphere or in vacuum, and a second heating In the mixed acid solution of hydrofluoric acid and nitric acid after the step, there is a step of performing an acid treatment in a temperature range exceeding 60 ° C. and not more than 100 ° C.
  • the present invention includes a first heating step of firing a raw material mixed powder containing Si, Al, and Eu in a nitrogen atmosphere, and a second heating step of heat treating the obtained fired product in an inert gas atmosphere or in vacuum. And a method for producing ⁇ -sialon in which Eu is solid-solved, comprising a step of acid treatment in a mixed acid solution of hydrofluoric acid and nitric acid after the second heating step in a temperature range exceeding 60 ° C. and not exceeding 100 ° C.
  • the raw material mixed powder containing Si, Al, Eu is selected from silicon oxide and / or aluminum oxide, silicon nitride, aluminum nitride, europium metal, oxide, carbonate, nitride or oxynitride It is a powder mixed with a europium compound.
  • the raw materials containing Si and Al are blended so as to satisfy the general formula: Si 6-z Al z O z N 8-z (0 ⁇ z ⁇ 4.2).
  • the Eu content is preferably in the range of 0.1% by mass to 3% by mass. If the Eu content is within the above range, the light emission luminance can be sufficiently obtained.
  • the mixing apparatus When mixing raw materials containing Si, Al, and Eu, there are a dry mixing method, a wet mixing method in an inert solvent that does not substantially react with each component of the raw material, and then a method of removing the solvent. This method can also be applied.
  • the mixing apparatus include a V-type mixer, a rocking mixer, a ball mill, and a vibration mill.
  • the raw material mixed powder After drying the raw material mixed powder as necessary, it is filled in a container such as a crucible in which at least the surface in contact with the raw material is boron nitride and heated in a nitrogen atmosphere.
  • a container such as a crucible in which at least the surface in contact with the raw material is boron nitride and heated in a nitrogen atmosphere.
  • the mixed raw material mixed powder is heated and fired in a temperature range of 1820 ° C. or higher and 2200 ° C. or lower, preferably 1850 ° C. or higher and 2050 ° C. or lower in a nitrogen atmosphere (hereinafter referred to as a first heating step). If the heating temperature is low, Eu cannot enter the ⁇ -type sialon crystal. If the heating temperature is increased more than necessary, it is necessary to apply a high nitrogen pressure to suppress the decomposition of the Eu solid-solution ⁇ -type sialon.
  • the pressure condition in firing is preferably 0.5 MPa or more and 10 MPa or less.
  • the heating time is generally 10 to 20 hours.
  • a metal powder containing Si may be used instead of using silicon nitride as the raw material mixed powder. In this case, it is necessary to nitride the metal powder containing Si before the first heating step. Since the nitriding reaction of the Si-containing metal powder proceeds at a temperature of 1400 ° C. or higher and 1600 ° C., the Si-containing metal powder is heated in the above-mentioned temperature range in a nitrogen atmosphere before the first heating step. Convert to Si 3 N 4 .
  • This second heating step is a treatment for further destabilizing the low crystalline portion remaining in the fired product.
  • the low crystalline phase that has become unstable due to the second heating step treatment is removed by a mixed acid solution treatment described later.
  • the heating furnace is filled with an inert gas after the exhaust process (hereinafter referred to as an introduction process).
  • the inert gas is a gas selected from helium, neon, argon, krypton, xenon, radon, and hydrogen, preferably argon and hydrogen.
  • the fired product is heated in a temperature range of 1200 ° C. or higher and 1550 ° C. or lower in a vacuum or in a temperature range of 1300 ° C. or higher and 1550 ° C. or lower in an inert gas atmosphere.
  • the heating temperature is within this temperature range, the decomposition of Eu solid solution ⁇ -sialon can be suppressed.
  • the process proceeds to the acid treatment step.
  • the fired product obtained in the second heating step is pulverized, and the pulverized fired product is dispersed in a mixed acid solution of hydrofluoric acid and nitric acid and stirred in a temperature range exceeding 60 ° C.
  • the acid treatment step is a step of removing the destabilized low crystalline portion by dipping in an acidic liquid.
  • the temperature of the acid treatment is in the temperature range of more than 60 ° C and not more than 100 ° C. If the temperature is too low, the emission intensity of Eu solid-solution ⁇ -sialon decreases.
  • a mixed solution of hydrofluoric acid and nitric acid is a mixture of hydrofluoric acid having a concentration of about 50% and nitric acid having a concentration of about 70% (hereinafter referred to as a mixed stock solution) or a diluted one (hereinafter referred to as a mixed stock solution).
  • the diluted stock solution may be referred to as a mixed acid solution).
  • the concentration of the solution obtained by diluting the mixed stock solution is preferably 25% or more and less than 100%, more preferably 25% or more and 50%.
  • diluted low concentration hydrofluoric acid and nitric acid may be mixed.
  • the mixing ratio of hydrofluoric acid and nitric acid is preferably 1 to 9: 9 to 1, particularly preferably 3 to 1, when about 50% hydrofluoric acid and about 70% nitric acid are mixed. 7: 7-3.
  • the mixed solution is preferably a mixture of concentrated hydrofluoric acid and concentrated nitric acid.
  • Concentrated hydrofluoric acid means a concentration of 40% or more and 60% or less
  • concentrated nitric acid means a concentration of 55% or more and 75% or less.
  • Table 1 shows the processing conditions and light emission characteristics of Examples 1 to 7 and Comparative Examples 1 and 2 described later.
  • ⁇ -type silicon nitride powder U-Kosan SN-E10 grade, oxygen content 1.1 mass%, ⁇ phase content 4.5 mass%) 95.4 mass%, aluminum nitride powder (Tokuyama F grade, Oxygen content 0.8% by mass) 3.0% by mass, aluminum oxide powder (TM-DAR grade manufactured by Daimei Chemical Co., Ltd.) 0.74% by mass, europium oxide powder (RU grade manufactured by Shin-Etsu Chemical Co., Ltd.) 0.71% by mass % Was blended to obtain 600 g of a raw material mixture.
  • the obtained raw material mixture was mixed with a rocking mixer (RM-10, Aichi Electric Co., Ltd.) for 60 minutes in a dry manner, and further passed through a stainless steel sieve having an opening of 150 ⁇ m to obtain a raw material powder.
  • a rocking mixer (RM-10, Aichi Electric Co., Ltd.) for 60 minutes in a dry manner, and further passed through a stainless steel sieve having an opening of 150 ⁇ m to obtain a raw material powder.
  • 170 g of the obtained raw material powder was filled into a cylindrical boron nitride container (N-1 grade manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid having an internal size of 10 cm in diameter, 9 cm in height, and 0.5 cm in thickness.
  • a first heating step in an electric furnace firing was performed at 1950 ° C. for 15 hours in a pressurized nitrogen atmosphere of 0.9 MPa.
  • the obtained fired product was pulverized, and a powder was obtained through a sieve having an opening of 45 ⁇ m.
  • a mixed stock solution was prepared by mixing 25 ml of 50% strength hydrofluoric acid (HF) and 25 ml of 70% strength nitric acid (HNO 3 ). 150 ml of distilled water was added to the mixed stock solution to dilute the concentration of the mixed stock solution to 25% to prepare 200 ml of an HF + HNO 3 aqueous solution. 5 g of the powder after the second heating step was added, and acid treatment was performed for 1 hour while maintaining the HF + HNO 3 aqueous solution at 70 ° C.
  • HF hydrofluoric acid
  • HNO 3 70% strength nitric acid
  • the acid-treated powder was sufficiently washed with distilled water, filtered, dried, and then the phosphor powder of Example 1 was obtained through a sieve having an opening of 45 ⁇ m.
  • the manufactured ⁇ -sialon was evaluated by the light emission characteristics of light absorption rate, internal quantum efficiency, and external quantum efficiency.
  • a standard reflector (Labsphere, Spectralon (registered trademark)) having a reflectivity of 99% is set on the sample portion, and the spectrum of the excitation light is measured.
  • the excitation wavelength is 455 nm, 450 is used.
  • the number of excitation reflected light photons was calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescent photons was calculated in the range of 465 to 800 nm when the excitation light was 455 nm.
  • Example 1 The light emission characteristics in Example 1 were a light absorption rate of 72.5%, an internal quantum efficiency of 69.9%, and an external quantum efficiency of 50.7%.
  • the production method of ⁇ -sialon of Example 2 is the same as that of Example 1 except that the acid treatment temperature is set to 80 ° C., light absorption rate 71.8%, internal quantum efficiency 71.4%, external The quantum was 51.2%.
  • the production method of ⁇ -sialon of Example 3 is the same as that of Example 1 except that the acid treatment temperature was set to 90 ° C., light absorption rate 71.2%, internal quantum efficiency 72.0%, external The quantum was 51.3%.
  • the acid treatment step is performed by mixing 15 ml of 50% strength hydrofluoric acid (HF) and 35 ml of 70% strength nitric acid (HNO 3 ) to obtain a mixed stock solution, and adding 150 ml of distilled water to the mixed stock solution, The mixed stock solution was diluted to adjust 200 ml of an HF + HNO 3 aqueous solution so that the concentration became 25%.
  • the same procedure as in Example 1 was performed except that 5 g of the powder after the second heating step was added and the acid treatment was performed for 1 hour while maintaining the HF + HNO 3 aqueous solution at 80 ° C.
  • the light absorption rate was 71.6%
  • the internal quantum efficiency was 70.9%
  • the external quantum efficiency was 50.8%.
  • Example 5 is a production method under the same conditions as in Example 4 except that 35 ml of 50% hydrofluoric acid and 15 ml of 70% nitric acid were mixed to obtain a mixed stock solution.
  • the light absorption rate was 71.7%
  • the internal quantum efficiency was 71.3%
  • the external quantum efficiency was 51.1%.
  • Example 6 50 ml of 50% strength hydrofluoric acid and 50 ml of 70% strength nitric acid were mixed to obtain a mixed stock solution. 100 ml of distilled water was added to the mixed stock solution, and the mixed stock solution was diluted to prepare 200 ml of an HF + HNO 3 aqueous solution having a concentration of 50%. It is the same except that 5 g of the powder after the second heating step is added and the acid treatment is performed for 1 hour while keeping the HF + HNO 3 aqueous solution at 80 ° C. In the case of Example 6, the light absorption rate was 74.7%, the internal quantum efficiency was 70.0%, and the external quantum efficiency was 52.3%.
  • Example 7 was performed in the same manner as in Example 6 except that distilled water was not used as the acid in the acid treatment of Example 6 and 100 ml of the stock solution having a concentration of 100% was used.
  • the light absorption rate was 72.9%
  • the internal quantum efficiency was 72.6%
  • the external quantum efficiency was 52.9%.
  • Comparative Example 1 In Comparative Example 1, the same conditions as in Example 1 were used except that the acid treatment temperature was 60 ° C. The light absorption rate was 72.0%, the internal quantum efficiency was 69.2%, and the external quantum efficiency was 49.8%.
  • Comparative Example 2 Comparative Example 2 was performed under the same conditions as in Example 6 except that the acid treatment temperature was set to 35 ° C. In the case of Comparative Example 2, the light absorption rate was 73.6%, the internal quantum efficiency was 68.8%, and the external quantum efficiency was 50.6%.
  • a light emitting device was fabricated in which a silicone sealing resin containing ⁇ -sialon used in Examples and Comparative Examples was laminated on the light emitting surface of the LED.
  • a silicone sealing resin containing ⁇ -sialon used in Examples and Comparative Examples was laminated on the light emitting surface of the LED.
  • the ⁇ -sialon of the present invention when used as a phosphor, is excited with a wide range of wavelengths from ultraviolet to blue light and exhibits high-luminance green light emission. It can be used suitably and can be used suitably for a lighting fixture, an image display apparatus, etc.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne un procédé de production d'un SiAlON de type β qui est représenté par la formule générale Si6-zAlzOzN8-z (0 < z ≤ 4,2), dans lequel Eu est dissous et qui comprend ; une première étape de chauffage consistant en une cuisson d'une poudre d'un mélange de matières contenant Si, Al et Eu dans une atmosphère d'azote ; une seconde étape de chauffage consistant en un traitement thermique du produit cuit obtenu dans une atmosphère de gaz inerte ou dans un vide ; et une étape de traitement par un acide du produit résultant après la seconde étape de chauffage dans une solution d'acide mixte d'un acide fluorhydrique et d'acide nitrique dans une plage de température d'au-dessus de 60°C et 100°C ou moins.
PCT/JP2011/070008 2010-09-09 2011-09-02 Procédé de production de sialon de type β WO2012033013A1 (fr)

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JP2012532954A JP5883390B2 (ja) 2010-09-09 2011-09-02 β型サイアロンの製造方法

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JP2010-202514 2010-09-09
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10190044B2 (en) 2015-08-07 2019-01-29 Nichia Corporation Method for producing β-sialon fluorescent material
US10563124B2 (en) 2016-06-30 2020-02-18 Nichia Corporation Method of producing nitride fluorescent material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255885A (ja) * 2004-03-12 2005-09-22 National Institute For Materials Science 蛍光体とその製造方法
WO2008062781A1 (fr) * 2006-11-20 2008-05-29 Denki Kagaku Kogyo Kabushiki Kaisha Substance fluorescente et son procédé de fabrication, et dispositif électroluminescent
JP2010241995A (ja) * 2009-04-08 2010-10-28 Denki Kagaku Kogyo Kk β型サイアロン蛍光体とその製造方法、およびその用途
WO2010143590A1 (fr) * 2009-06-09 2010-12-16 電気化学工業株式会社 Phosphore de β-sialon, utilisation de celui-ci et procédé de production de celui-ci

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101982891A (zh) * 2005-02-28 2011-03-02 电气化学工业株式会社 荧光体及其制造方法及使用了该荧光体的发光元件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255885A (ja) * 2004-03-12 2005-09-22 National Institute For Materials Science 蛍光体とその製造方法
WO2008062781A1 (fr) * 2006-11-20 2008-05-29 Denki Kagaku Kogyo Kabushiki Kaisha Substance fluorescente et son procédé de fabrication, et dispositif électroluminescent
JP2010241995A (ja) * 2009-04-08 2010-10-28 Denki Kagaku Kogyo Kk β型サイアロン蛍光体とその製造方法、およびその用途
WO2010143590A1 (fr) * 2009-06-09 2010-12-16 電気化学工業株式会社 Phosphore de β-sialon, utilisation de celui-ci et procédé de production de celui-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10190044B2 (en) 2015-08-07 2019-01-29 Nichia Corporation Method for producing β-sialon fluorescent material
US10563124B2 (en) 2016-06-30 2020-02-18 Nichia Corporation Method of producing nitride fluorescent material

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JP5883390B2 (ja) 2016-03-15
TWI450947B (zh) 2014-09-01
TW201217495A (en) 2012-05-01
JPWO2012033013A1 (ja) 2014-01-20

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