WO2012033013A1 - Method for producing β type sialon - Google Patents

Method for producing β type sialon Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
acid
mixed
sialon
heating step
producing
Prior art date
Application number
PCT/JP2011/070008
Other languages
French (fr)
Japanese (ja)
Inventor
真太郎 渡邉
光明 斉藤
秀幸 江本
山田　鈴弥
Original Assignee
電気化学工業株式会社
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 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2012532954A priority Critical patent/JP5883390B2/en
Publication of WO2012033013A1 publication Critical patent/WO2012033013A1/en

Links

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
    • C09K11/0883—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.

Landscapes

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

Abstract

A method for producing a β type sialon which is represented by general formula, Si6-zAlzOzN8-z (0<z≤4.2), into which Eu is dissolved and which comprises; a first heating step of firing a material mixture powder containing Si, Al and Eu in a nitrogen atmosphere; a second heating step of heat treating the obtained fired product in an inert gas atmosphere or in a vacuum; and a step of acid treating the result after the second heating step in a mixed acid solution of a hydrofluoric acid and nitric acid in a temperature range of over 60°C and 100°C or less.

Description

β型サイアロンの製造方法Method for producing β-sialon
　本発明は、ユーロピウム（Ｅｕ）を固溶したβ型サイアロンの製造方法に関する。 The present invention relates to a method for producing β-sialon in which europium (Eu) is dissolved.
　特許文献１には、Ｅｕを固溶したβ型サイアロンの製造方法として、フッ化水素酸と硫酸との混酸溶液を用いた酸処理により、Ｅｕを固溶したβ型サイアロンの発光強度を向上させることが記載されている。しかし、特許文献１には、混酸溶液の濃度が高いと蛍光体が溶解すること、温度が６０℃以上になると蛍光体が溶解することも記載されている。 In Patent Document 1, as a method for producing β-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 β-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.
　特許文献２には、Ｅｕを固溶したβ型サイアロンの発光強度を向上させるため、粉砕した焼成物を窒素ガス以外の不活性ガス中で１３００℃～１６００℃で再加熱した後に、５０％フッ化水素酸と７０％硝酸との混酸溶液を用いて酸処理する技術が開示されている。 In Patent Document 2, in order to improve the emission intensity of β-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.
特開２００５－２５５８８５号公報Japanese Patent Laid-Open No. 2005-255585 国際公開第２００８／０６２７８１号パンフレットInternational Publication No. 2008/062781 Pamphlet
　本発明の目的は、さらに高い発光効率を再現性よく実現できるＥｕを固溶したβ型サイアロンの製造方法を提供することにある。 An object of the present invention is to provide a method for producing β-sialon in which Eu is dissolved, which can realize higher luminous efficiency with good reproducibility.
　本発明は、酸処理工程において、フッ化水素酸と硝酸との混酸溶液を使用した場合、混酸溶液濃度を低くすると、得られた蛍光体の発光強度が低くなるが、高い温度では発光強度が高くなるという新たな知見に基づくものである。この知見は、特許文献１に記載された「混酸溶液の濃度が濃いとＥｕを固溶したβ型サイアロンが溶解するので好ましくない」及び「混酸処理温度は低いほうが良い」という開示と相反する結果である。 In the present invention, when a mixed acid solution of hydrofluoric acid and nitric acid is used in the acid treatment step, the emission intensity of the obtained phosphor is lowered when the concentration of the mixed acid solution is lowered. It is based on the new knowledge that it becomes higher. This finding is contrary to the disclosures of Patent Document 1 that “a high concentration of mixed acid solution is undesirable because β-sialon dissolved in Eu dissolves” and “a lower mixed acid treatment temperature is better”. It is.
　本発明は、一般式：Ｓｉ6-zＡｌzＯzＮ8-z（０＜ｚ≦４．２）で示されるβ型サイアロンにＥｕを固溶したβ型サイアロンの製造方法であって、Ｓｉ、Ａｌ、Ｅｕを含有する原料混合粉末を窒素雰囲気中で焼成する第一加熱工程と、得られた焼成物を不活性ガス雰囲気中又は真空中で熱処理する第二加熱工程と、第二加熱工程後にフッ化水素酸と硝酸の混酸溶液中、６０℃を超え１００℃以下の温度範囲で酸処理する工程を有する。 The present invention is a method for producing β-sialon in which Eu is dissolved in β-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.
　本発明の方法により、高い発光効率を有するＥｕを固溶したβ型サイアロンを再現性よく製造することができる。 By the method of the present invention, β-sialon in which Eu having high luminous efficiency is dissolved can be produced with good reproducibility.
　本発明は、Ｓｉ、Ａｌ、Ｅｕを含有する原料混合粉末を窒素雰囲気中で焼成する第一加熱工程と、得られた焼成物を不活性ガス雰囲気中又は真空中で熱処理する第二加熱工程と、第二加熱工程後にフッ化水素酸と硝酸の混酸溶液中、６０℃を超え１００℃以下の温度範囲で酸処理する工程とからなる、Ｅｕを固溶したβ型サイアロンの製造方法である。
　Ｓｉ、Ａｌ、Ｅｕを含有する原料混合粉末とは、酸化ケイ素及び／又は酸化アルミニウムと、窒化ケイ素と、窒化アルミニウムと、ユーロピウムの金属、酸化物、炭酸塩、窒化物又は酸窒化物から選ばれるユーロピウム化合物とを混合した粉末である。 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 β-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.
　Ｓｉ、Ａｌを含有する原料は、一般式：Ｓｉ6-zＡｌzＯzＮ8-z（０＜ｚ≦４．２）を満たすように配合する。 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).
　Ｅｕ含有量は、０．１質量％以上３質量％以下の範囲であることが好ましい。Ｅｕ含有量が上記の範囲内であれば発光輝度を十分に得ることができる。 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.
　Ｓｉ、Ａｌ、Ｅｕを含有する原料を混合する場合、乾式混合する方法、原料各成分と実質的に反応しない不活性溶媒中で湿式混合した後に溶媒を除去する方法などがあり、本発明では何れの方法も適用できる。混合装置としては、Ｖ型混合機、ロッキングミキサー、ボールミル、振動ミルがある。 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. Examples of the mixing apparatus include a V-type mixer, a rocking mixer, a ball mill, and a vibration mill.
　原料混合粉末を必要に応じて乾燥後、少なくとも当該原料が接する面を窒化ホウ素とした坩堝等の容器内に充填し、窒素雰囲気中で加熱する。 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.
　混合した原料混合粉末を窒素雰囲気下、１８２０℃以上２２００℃以下、好ましくは１８５０℃以上２０５０℃以下の温度範囲で加熱して焼成する（以降、第一加熱工程という）。加熱温度が低いと、Ｅｕがβ型サイアロン結晶中に入り込むことができず、加熱温度を必要以上に高くすると、高い窒素圧力をかけてＥｕ固溶β型サイアロンの分解を抑制する必要がある。焼成における圧力条件は、０．５ＭＰａ以上１０ＭＰａ以下が好ましい。加熱時間は一般的に１０時間～２０時間である。 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 β-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 β-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.
　原料混合粉末として窒化ケイ素を用いる代わりに、Ｓｉを含有する金属粉末であっても良い。この場合、Ｓｉを含有する金属粉末を第一加熱工程の前に窒化処理しておくことが必要である。Ｓｉを含有する金属粉末の窒化反応は、１４００℃以上１６００℃の温度で進行するため、第一加熱工程の前にＳｉを含有する金属粉末を窒素雰囲気下、上記温度範囲で加熱してＳｉをＳｉ3Ｎ4に変換する。 Instead of using silicon nitride as the raw material mixed powder, a metal powder containing Si may be used. 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 .
　次に、第一加熱工程の後、さらに、得られた焼成物を真空中又は窒素ガス以外のガス雰囲気中で加熱する（以降、第二加熱工程という。）。この第二加熱工程は、焼成物中に残存する低結晶性部分を更に不安定にするための処理である。第二加熱工程処理により不安定になった低結晶相は、後述する混酸溶液処理によって除去される。 Next, after the first heating step, the obtained fired product is further heated in a vacuum or a gas atmosphere other than nitrogen gas (hereinafter referred to as a second heating step). 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.
　低結晶性部分を不安定化するためには、低結晶性部分を構成する元素である窒素と酸素を極力含まない雰囲気中で焼成物を加熱処理することが望ましい。第二加熱工程を窒素ガス以外のガス雰囲気中で行う場合、排気工程後、加熱炉内に不活性ガスを充填する（以降、導入工程という。）。不活性ガスはヘリウム、ネオン、アルゴン、クリプトン、キセノン、ラドン、水素から選ばれるガスであり、好ましくはアルゴン、水素である。 In order to destabilize the low crystalline part, it is desirable to heat-treat the fired product in an atmosphere containing as little nitrogen and oxygen as the elements constituting the low crystalline part as much as possible. When the second heating process is performed in a gas atmosphere other than nitrogen gas, 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.
　第二加熱工程において、焼成物は、真空中１２００℃以上１５５０℃以下の温度範囲又は不活性ガス雰囲気中１３００℃以上１５５０℃以下の温度範囲で加熱される。加熱温度がこの温度範囲内であれば、Ｅｕ固溶β型サイアロンの分解を抑制することができる。 In the second heating step, 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. When the heating temperature is within this temperature range, the decomposition of Eu solid solution β-sialon can be suppressed.
　第二加熱工程後、酸処理工程に進む。この酸処理工程では、第二加熱工程により得られた焼成物を粉砕し、粉砕焼成物をフッ化水素酸と硝酸の混酸溶液に分散させ、６０℃を超えた温度範囲で攪拌する。酸処理工程は、酸性の液体中に浸すことにより、不安定化させた低結晶性部分を除去する工程である。 After the second heating step, the process proceeds to the acid treatment step. In this 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.
　酸処理の温度は、６０℃を超え１００℃以下の温度範囲である。過度に低温度であるとＥｕ固溶のβ型サイアロンの発光強度が低下する。 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 β-sialon decreases.
　フッ化水素酸と硝酸の混合溶液は、約５０％濃度のフッ化水素酸と約７０％濃度の硝酸とを混合したもの（以降、混合原液という。）又はその混合原液を希釈したもの（以下、混合原液を希釈したものを混酸溶液という。）であってもよい。混合原液を希釈した溶液の濃度は、２５％以上１００％未満が好ましく、さらに好ましくは２５％以上５０％である。高濃度のフッ化水素酸及び硝酸の混合溶液を希釈するのではなく、希釈された低濃度のフッ化水素酸及び硝酸を混合してもよい。 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%. Instead of diluting a mixed solution of high concentration hydrofluoric acid and nitric acid, diluted low concentration hydrofluoric acid and nitric acid may be mixed.
　フッ化水素酸と硝酸の混合比は、約５０％濃度のフッ化水素酸と約７０％濃度の硝酸を混合する場合は、１～９：９～１の比率が好ましく、特に好ましくは３～７：７～３である。 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.
　前記混合溶液は、濃フッ化水素酸及び濃硝酸を混合したものが好ましい。濃フッ化水素酸とはその濃度が４０％以上６０％以下、濃硝酸とは、その濃度が５５％以上７５％以下のものをいう。 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, and concentrated nitric acid means a concentration of 55% or more and 75% or less.
　以下、本発明の実施例について、表１を参照しつつ詳細に説明する。表１は、後述する実施例１～７及び比較例１、２の処理条件と発光特性を示したものである。 Hereinafter, embodiments of the present invention will be described in detail with reference to Table 1. Table 1 shows the processing conditions and light emission characteristics of Examples 1 to 7 and Comparative Examples 1 and 2 described later.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　α型窒化ケイ素粉末（宇部興産社製ＳＮ－Ｅ１０グレード、酸素含有量１．１質量％、β相含有量４．５質量％）９５．４質量％、窒化アルミニウム粉末（トクヤマ社製Ｆグレード、酸素含有量０．８質量％）３．０質量％、酸化アルミニウム粉末（大明化学社製ＴＭ－ＤＡＲグレード）０．７４質量％、酸化ユーロピウム粉末（信越化学工業社製ＲＵグレード）０．７１質量％を配合し、原料混合物６００ｇを得た。 α-type silicon nitride powder (U-Kosan SN-E10 grade, oxygen content 1.1 mass%, β 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.
　得られた原料混合物をロッキングミキサー（愛知電機社製ＲＭ－１０）により６０分間乾式で混合し、更に目開き１５０μｍのステンレス製篩を全通させて原料粉末を得た。 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 μm to obtain a raw material powder.
　得られた原料粉末を内寸で直径１０ｃｍ×高さ９ｃｍ×厚さ０．５ｃｍの蓋付きの円筒型窒化ホウ素製容器（電気化学工業社製Ｎ－１グレード）に１７０ｇ充填し、カーボンヒーターの電気炉で第一の加熱工程として、０．９ＭＰａの加圧窒素雰囲気中、１９５０℃で１５時間の焼成を行った。得られた焼成物を解砕し、目開き４５μｍの篩を通して粉末を得た。 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. As 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 μm.
　得られた粉末を内寸で直径６ｃｍ×高さ３．５ｃｍ×厚さ０．５ｃｍの蓋付きの円筒型窒化ホウ素製容器（電気化学工業社製Ｎ－１グレード）に２０ｇ充填し、カーボンヒーターの電気炉で、第二の加熱工程として、真空中、１４００℃で８時間の加熱処理を行った。 20 g of the obtained powder is packed into a cylindrical boron nitride container (N-1 grade manufactured by Denki Kagaku Kogyo Co., Ltd.) with a lid having an internal size of 6 cm in diameter, 3.5 cm in height and 0.5 cm in thickness, and a carbon heater In the electric furnace, as a second heating step, heat treatment was performed in vacuum at 1400 ° C. for 8 hours.
　５０％濃度のフッ化水素酸（ＨＦ）２５ｍｌ及び７０％濃度の硝酸（ＨＮＯ3）２５ｍｌを混合して混合原液とした。混合原液に蒸留水１５０ｍｌを加え、混合原液の濃度を２５％に希釈し、ＨＦ＋ＨＮＯ3水溶液２００ｍｌを調整した。第二の加熱工程後の粉末５ｇを投入し、ＨＦ＋ＨＮＯ3水溶液を７０℃に保ちながら１時間の酸処理を行った。 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.
　酸処理後の粉末は、蒸留水にて十分に酸を洗い流して濾過し、乾燥させた後、目開き４５μｍの篩を通して実施例１の蛍光体粉末を得た。 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 μm.
　次に、実施例１の蛍光体粉末に対して積分球を用いて全光束発光スペクトル測定を行った（参考文献：照明学会誌、第８３巻　第２号　平成１１年　ｐ８７－９３、ＮＢＳ標準蛍光体の量子効率の測定、大久保和明他、著）。励起光には、分光したキセノンランプ光源を使用した。 Next, total luminous emission spectrum measurement was performed on the phosphor powder of Example 1 using an integrating sphere (Reference: Journal of the Illuminating Science Society, Vol. 83, No. 2, 1999, p87-93, NBS standard fluorescence) Measurement of quantum efficiency of the body, Kazuaki Okubo et al. A spectral xenon lamp light source was used as the excitation light.
　製造されたβ型サイアロンの評価は、表１にあるように、光吸収率、内部量子効率、外部量子効率の発光特性で行った。 As shown in Table 1, the manufactured β-sialon was evaluated by the light emission characteristics of light absorption rate, internal quantum efficiency, and external quantum efficiency.
　この評価にあっては、試料部に反射率が９９％の標準反射板（Ｌａｂｓｐｈｅｒｅ社、スペクトラロン（登録商標））をセットして励起光のスペクトルを測定し、励起波長が４５５ｎｍの場合は４５０～４６５ｎｍの波長範囲のスペクトルから励起光フォトン数（Ｑｅｘ）を算出し、次いで、試料部に蛍光体をセットして、得られたスペクトルデータから励起反射光フォトン数（Ｑｒｅｆ）及び蛍光フォトン数（Ｑｅｍ）を算出し、得られた三種類のフォトン数から、光吸収率（＝（Ｑｅｘ－Ｑｒｅｆ）×１００）、内部量子効率（＝Ｑｅｍ／（Ｑｅｘ－Ｑｒｅｆ）×１００）及び外部量子効率（＝Ｑｅｍ／Ｑｅｘ×１００）を求めた。励起反射光フォトン数は、励起光フォトン数と同じ波長範囲で、蛍光フォトン数は、励起光が４５５ｎｍの場合、４６５～８００ｎｍの範囲で算出した。 In this evaluation, 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. When the excitation wavelength is 455 nm, 450 is used. The number of excitation light photons (Qex) is calculated from the spectrum in the wavelength range of ˜465 nm, then a phosphor is set on the sample portion, and the number of excitation reflected light photons (Qref) and the number of fluorescence photons (Q Qem) is calculated, and the light absorption rate (= (Qex−Qref) × 100), internal quantum efficiency (= Qem / (Qex−Qref) × 100) and external quantum efficiency (from the three types of photons obtained) = Qem / Qex × 100). 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.
　実施例１における発光特性は、光吸収率７２．５％、内部量子効率６９．９％、外部量子効率５０．７％であった。 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%.
　実施例２のβ型サイアロンの製造方法は、酸処理の温度を８０℃とした以外は、実施例１と同じ条件であり、光吸収率７１．８％、内部量子効率７１．４％、外部量子５１．２％であった。 The production method of β-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%.
　実施例３のβ型サイアロンの製造方法は、酸処理の温度を９０℃とした以外は、実施例１と同じ条件であり、光吸収率７１．２％、内部量子効率７２．０％、外部量子５１．３％であった。 The production method of β-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%.
　実施例４は、酸処理工程を、５０％濃度のフッ化水素酸（ＨＦ）１５ｍｌ及び７０％濃度の硝酸（ＨＮＯ3）３５ｍｌを混合して混合原液とし、混合原液に蒸留水１５０ｍｌを加え、混合原液を希釈し濃度が２５％となるようにＨＦ＋ＨＮＯ3水溶液２００ｍｌを調整した。第二の加熱工程後の粉末５ｇを投入し、ＨＦ＋ＨＮＯ3水溶液を８０℃に保ちながら１時間の酸処理を行った以外、実施例１と同様に行った。実施例４の場合、光吸収率７１．６％、内部量子効率７０．９％、外部量子効率５０．８％であった。 In Example 4, 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. In the case of Example 4, the light absorption rate was 71.6%, the internal quantum efficiency was 70.9%, and the external quantum efficiency was 50.8%.
　実施例５は、５０％濃度のフッ化水素酸３５ｍｌ及び７０％濃度の硝酸１５ｍｌを混合して混合原液とした以外は実施例４と同じ条件の製造方法である。実施例５の場合、光吸収率７１．７％、内部量子効率７１．３％、外部量子効率５１．１％であった。 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. In Example 5, the light absorption rate was 71.7%, the internal quantum efficiency was 71.3%, and the external quantum efficiency was 51.1%.
　実施例６は、５０％濃度のフッ化水素酸を５０ｍｌ及び７０％濃度の硝酸５０ｍｌを混合して混合原液とした。混合原液に蒸留水１００ｍｌを加え、混合原液を希釈し濃度が５０％となるＨＦ＋ＨＮＯ3水溶液２００ｍｌを調整した。第二の加熱工程後の粉末５ｇを投入し、ＨＦ＋ＨＮＯ3水溶液を８０℃に保ちながら１時間の酸処理を行った以外同様なものである。実施例６の場合、光吸収率７４．７％、内部量子効率７０．０％、外部量子効率５２．３％であった。 In 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%.
　実施例７は、実施例６の酸処理における酸に蒸留水を用いず、原液濃度１００％のものを１００ｍｌ用いた以外は実施例６と同様に行った。実施例７では、光吸収率７２．９％、内部量子効率７２．６％、外部量子効率５２．９％であった。 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. In Example 7, the light absorption rate was 72.9%, the internal quantum efficiency was 72.6%, and the external quantum efficiency was 52.9%.
（比較例１）
　比較例１は、酸処理温度を６０℃にした以外は実施例１と同じ条件とした。光吸収率は７２．０％、内部量子効率は６９．２％、外部量子効率は４９．８％であった。 (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%.
（比較例２）
　比較例２は、酸処理温度を３５℃にした以外は実施例６と同じ条件で行った。比較例２の場合、光吸収率は７３．６％、内部量子効率は６８．８％、外部量子効率は５０．６％であった。 (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%.
　実施例１、２、３と比較例１から、酸処理の温度を上げることにより、光吸収率、内部量子効率並びに外部量子効率がともに向上することがわかる。処理温度は、６０℃を超え１００℃以下であればよく、７０℃以上９０℃以下が好ましい。 From Examples 1, 2, 3 and Comparative Example 1, it can be seen that the light absorption rate, the internal quantum efficiency and the external quantum efficiency are all improved by increasing the acid treatment temperature. Processing temperature should just exceed 60 degreeC and 100 degrees C or less, and 70 to 90 degreeC is preferable.
　実施例１～５と比較例２から、酸処理工程における混酸溶液の濃度が薄くとも、特に混合原液を希釈して濃度が２５％以上５０％の範囲では、従来例である比較例２より光吸収率、内部量子効率、外部量子効率の何れもが向上していることがわかる。比較例１及び２から、混酸溶液濃度を薄くすると発光特性が低下することがわかる。 From Examples 1 to 5 and Comparative Example 2, even if the concentration of the mixed acid solution in the acid treatment step is low, the mixed stock solution is diluted and the concentration is in the range of 25% to 50%. It can be seen that all of the absorption rate, internal quantum efficiency, and external quantum efficiency are improved. From Comparative Examples 1 and 2, it can be seen that when the mixed acid solution concentration is decreased, the light emission characteristics are lowered.
　表には示さなかったが、実施例及び比較例で用いたβ型サイアロンを配合したシリコーン封止樹脂をＬＥＤの発光面に積層した発光装置を作製した。実施例１～７のβ型サイアロンを用いた場合、発光させてから、８０℃×湿度４０％の高温に２時間おいた後でも、発光特性の低下が見られなかった。これに対して、比較例1及び２のβ型サイアロンを用いた発光装置にあっては、発光特性の低下が見られた。 Although not shown in the table, a light emitting device was fabricated in which a silicone sealing resin containing β-sialon used in Examples and Comparative Examples was laminated on the light emitting surface of the LED. When the β-sialons of Examples 1 to 7 were used, no deterioration in the light emission characteristics was observed even after 2 hours at 80 ° C. × 40% humidity after light emission. On the other hand, in the light emitting devices using the β-sialons of Comparative Examples 1 and 2, the emission characteristics were deteriorated.
　本発明のβ型サイアロンは、蛍光体として用いた場合、紫外から青色光の幅広い波長で励起され、高輝度の緑色発光を示すことから、青色又は紫外光を光源とする白色ＬＥＤの蛍光体として好適に使用でき、照明器具、画像表示装置などに好適に使用できる。 The β-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.

Claims (3)

  1. 　一般式：Ｓｉ6-zＡｌzＯzＮ8-z（０＜ｚ≦４．２）で示されるβ型サイアロンにＥｕを固溶したβ型サイアロンの製造方法であって、Ｓｉ、Ａｌ、Ｅｕを含有する原料混合粉末を窒素雰囲気中で焼成する第一加熱工程と、得られた焼成物を不活性ガス雰囲気中又は真空中で熱処理する第二加熱工程と、第二加熱工程後にフッ化水素酸と硝酸の混酸溶液中、６０℃を超え１００℃以下の温度範囲で酸処理を行う工程とからなるβ型サイアロンの製造方法。 A method for producing β-sialon in which Eu is dissolved in β-sialon represented by the general formula: Si 6-z Al z O z N 8-z (0 <z ≦ 4.2), wherein Si, Al, A first heating step of firing the raw material mixed powder containing Eu in a nitrogen atmosphere, a second heating step of heat-treating the obtained fired product in an inert gas atmosphere or in a vacuum, and fluorination after the second heating step A method for producing β-sialon, comprising a step of performing acid treatment in a mixed acid solution of hydrogen acid and nitric acid in a temperature range exceeding 60 ° C and not more than 100 ° C.
  2. 　前記混酸溶液が、濃フッ化水素酸及び濃硝酸を混合したものである請求項１記載のβ型サイアロンの製造方法。 The method for producing β-sialon according to claim 1, wherein the mixed acid solution is a mixture of concentrated hydrofluoric acid and concentrated nitric acid.
  3. 　前記混酸溶液が、濃フッ化水素酸及び濃硝酸を混合して希釈したものであって、希釈率が２５％以上である請求項１記載のβ型サイアロンの製造方法。 The method for producing β-sialon according to claim 1, wherein the mixed acid solution is diluted by mixing concentrated hydrofluoric acid and concentrated nitric acid, and the dilution rate is 25% or more.
PCT/JP2011/070008 2010-09-09 2011-09-02 Method for producing β type sialon WO2012033013A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012532954A JP5883390B2 (en) 2010-09-09 2011-09-02 Method for producing β-sialon

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-202514 2010-09-09
JP2010202514 2010-09-09

Publications (1)

Publication Number Publication Date
WO2012033013A1 true WO2012033013A1 (en) 2012-03-15

Family

ID=45810614

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/070008 WO2012033013A1 (en) 2010-09-09 2011-09-02 Method for producing β type sialon

Country Status (3)

Country Link
JP (1) JP5883390B2 (en)
TW (1) TWI450947B (en)
WO (1) WO2012033013A1 (en)

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 (en) * 2004-03-12 2005-09-22 National Institute For Materials Science Phosphor and its manufacturing method
WO2008062781A1 (en) * 2006-11-20 2008-05-29 Denki Kagaku Kogyo Kabushiki Kaisha Fluorescent substance and production method thereof, and light emitting device
JP2010241995A (en) * 2009-04-08 2010-10-28 Denki Kagaku Kogyo Kk beta-TYPE SIALON PHOSPHOR, METHOD FOR PRODUCING THE SAME AND APPLICATION OF THE SAME
WO2010143590A1 (en) * 2009-06-09 2010-12-16 電気化学工業株式会社 Β-sialon phosphor, use thereof and method for producing same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712868A (en) * 2005-02-28 2010-05-26 电气化学工业株式会社 Fluorescent substance and process for producing the same, and luminescent element using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255885A (en) * 2004-03-12 2005-09-22 National Institute For Materials Science Phosphor and its manufacturing method
WO2008062781A1 (en) * 2006-11-20 2008-05-29 Denki Kagaku Kogyo Kabushiki Kaisha Fluorescent substance and production method thereof, and light emitting device
JP2010241995A (en) * 2009-04-08 2010-10-28 Denki Kagaku Kogyo Kk beta-TYPE SIALON PHOSPHOR, METHOD FOR PRODUCING THE SAME AND APPLICATION OF THE SAME
WO2010143590A1 (en) * 2009-06-09 2010-12-16 電気化学工業株式会社 Β-sialon phosphor, use thereof and method for producing same

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

Also Published As

Publication number Publication date
JP5883390B2 (en) 2016-03-15
TWI450947B (en) 2014-09-01
JPWO2012033013A1 (en) 2014-01-20
TW201217495A (en) 2012-05-01

Similar Documents

Publication Publication Date Title
JP4740379B1 (en) β-type sialon phosphor, its use and method for producing β-type sialon phosphor
JP6572373B1 (en) Method for producing β-sialon phosphor
WO2010143590A1 (en) Β-sialon phosphor, use thereof and method for producing same
WO2014030637A1 (en) METHOD FOR PRODUCING β-SIALON, β-SIALON, AND LIGHT-EMITTING DEVICE
EP2093272A1 (en) Fluorescent substance and production method thereof, and light emitting device
WO2019188377A1 (en) Phosphor, production method for same, and light-emitting device
KR20150084867A (en) Phosphor, light-emitting element and lighting device
WO2011055665A1 (en) PROCESS FOR PRODUCING β-SIALON FLUORESCENT MATERIAL
WO2012046288A1 (en) β-SIALON PHOSPHOR, METHOD FOR PRODUCING SAME, AND USE OF SAME
WO2012042957A1 (en) PROCESS FOR PRODUCTION OF β-SIALON
WO2014057695A1 (en) Method for producing phosphor
JP2019199531A (en) MANUFACTURING METHOD OF β TYPE SIALON PHOSPHOR
CN113785030B (en) Surface-coated phosphor particle, method for producing surface-coated phosphor particle, and light-emitting device
WO2011158608A1 (en) PRODUCTION METHOD FOR β-SIALON
WO2020209148A1 (en) Surface-coated fluorescent particles, production method for surface-coated fluorescent particles, and light-emitting device
JP5883390B2 (en) Method for producing β-sialon
JP2010275437A (en) Alpha type sialon phosphor, and light-emitting element using the same
JP5185829B2 (en) Rare earth activated aluminum nitride powder and method for producing the same
TWI485230B (en) Method for manufacturing β-sialon fluorescent body
WO2012032818A1 (en) Method for producing eu-doped β-sialon
TWI651292B (en) Phosphor, illuminating device and manufacturing method thereof
JP6903455B2 (en) Fluorescent material manufacturing method, phosphor and light emitting element and light emitting device
JP2013237713A (en) β TYPE SIALON, LIGHT-EMITTING DEVICE, AND METHOD OF MANUFACTURING β TYPE SIALON
JP2012057071A (en) METHOD FOR PRODUCING β TYPE SIALON
JP2022116885A (en) Method for producing phosphor powder

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: 11823488

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012532954

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11823488

Country of ref document: EP

Kind code of ref document: A1