JP2012241078A - Method for producing blue light emitting phosphor - Google Patents
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本発明は、ＳｒとＭｇとＳｉとＥｕとを含み、メルウィナイトと同じ結晶構造を有するケイ酸塩をＥｕで付活した青色発光蛍光体の製造方法に関する。 The present invention relates to a method for producing a blue-emitting phosphor in which a silicate containing Sr, Mg, Si, and Eu and having the same crystal structure as merwinite is activated with Eu.
真空紫外光や紫外光などの光によって励起されると青色光を発光する青色発光蛍光体は、プラズマディスプレイパネル（ＰＤＰ）、冷陰極蛍光ランプ（ＣＣＦＬ）及び白色発光ダイオード（白色ＬＥＤ）などの青色発光源として利用されている。ＰＤＰでは、Ｘｅガスの放電により発生する波長１４６ｎｍと波長１７２ｎｍの真空紫外光が青色発光蛍光体の励起光に用いられる。ＣＣＦＬでは、Ｈｇガスの放電により発生する波長２５４ｎｍの紫外光が青色発光蛍光体の励起光に用いられる。白色ＬＥＤでは、半導体発光素子にて発生する波長３５０〜４３０ｎｍの光が青色発光蛍光体の励起光に用いられる。 Blue light-emitting phosphors that emit blue light when excited by light such as vacuum ultraviolet light and ultraviolet light are blue such as plasma display panels (PDP), cold cathode fluorescent lamps (CCFL), and white light-emitting diodes (white LEDs). It is used as a light source. In the PDP, vacuum ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm generated by discharge of Xe gas is used as excitation light of the blue light emitting phosphor. In the CCFL, ultraviolet light having a wavelength of 254 nm generated by discharge of Hg gas is used as excitation light of the blue light emitting phosphor. In the white LED, light having a wavelength of 350 to 430 nm generated in the semiconductor light emitting element is used as excitation light of the blue light emitting phosphor.
青色発光蛍光体としては、ＳｒとＭｇとＳｉとＥｕとを含み、メルウィナイト（Ｃａ3ＭｇＳｉ2Ｏ8）と同じ結晶構造を有するケイ酸塩をＥｕで付活した青色発光蛍光体（以下、ＳＭＳ青色発光蛍光体ともいう）が知られている。例えば、Ｓｒ3ＭｇＳｉ2Ｏ8の組成式で示されるケイ酸塩をＥｕで付活したＳＭＳ青色発光蛍光体が知られている。ＳＭＳ青色発光蛍光体は、Ｓｒ源粉末とＭｇ源粉末とＳｉ源粉末とＥｕ源粉末とを混合し、得られた粉末混合物を焼成することによって製造するのが一般的である。 As a blue light emitting phosphor, a blue light emitting phosphor (hereinafter referred to as an SMS) in which a silicate having the same crystal structure as that of merwinite (Ca 3 MgSi 2 O 8 ) is activated with Eu, including Sr, Mg, Si and Eu. Also known as a blue-emitting phosphor). For example, an SMS blue light emitting phosphor in which a silicate represented by a composition formula of Sr 3 MgSi 2 O 8 is activated with Eu is known. The SMS blue light-emitting phosphor is generally manufactured by mixing an Sr source powder, an Mg source powder, an Si source powder, and an Eu source powder, and firing the obtained powder mixture.
特許文献１には、蛍光体の製造方法として、酸化ケイ素とストロンチウムを含む無機化合物と付活剤とを含む粉体を、粉砕媒体とともに揺動回転機能を有する混合装置内で、前記混合装置を揺動回転させることにより混合する混合工程と、前記混合工程において混合された粉体混合物を焼成する焼成工程とを含む方法が記載されている。この特許文献１には、ストロンチウムを含む無機化合物の例として、フッ化ストロンチウム、塩化ストロンチウム、臭化ストロンチウム、ヨウ化ストロンチウムなどのストロンチウムのハロゲン化物、炭酸ストロンチウム、水酸化ストロンチウム、酸化ストロンチウム、硝酸ストロンチウム、シュウ酸ストロンチウム、硫酸ストロンチウムが挙げられている。また、特許文献１には、焼成の際、粉体混合物に反応促進剤（フラックス）を混合してもよいとの記載があり、反応促進剤の例として、酸化ホウ素、フッ化アルミニウム、ＬｉＦ、ＮａＦ、ＫＦ、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ、Ｌｉ2ＣＯ3、Ｎａ2ＣＯ3、Ｋ2ＣＯ3、ＮａＨＣＯ3、ＮＨ4Ｃｌ、ＮＨ4Ｉ、ＭｇＦ2、ＣａＦ2、ＳｒＦ2、ＢａＦ2、ＭｇＣｌ2、ＣａＣｌ2、ＳｒＣｌ2、ＢａＣｌ2、ＭｇＩ2、ＣａＩ2、ＳｒＩ2、ＢａＩ2が挙げられている。 In Patent Document 1, as a method for producing a phosphor, a powder containing an inorganic compound containing silicon oxide and strontium and an activator is mixed in a mixing device having a rocking and rotating function together with a grinding medium. A method is described that includes a mixing step of mixing by rocking and rotating, and a baking step of baking the powder mixture mixed in the mixing step. In this Patent Document 1, as examples of inorganic compounds containing strontium, strontium halides such as strontium fluoride, strontium chloride, strontium bromide, strontium iodide, strontium carbonate, strontium hydroxide, strontium oxide, strontium nitrate, Strontium oxalate and strontium sulfate are mentioned. Patent Document 1 also describes that a reaction accelerator (flux) may be mixed with the powder mixture during firing. Examples of the reaction accelerator include boron oxide, aluminum fluoride, LiF, NaF, KF, LiCl, NaCl, KCl, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , NH 4 Cl, NH 4 I, MgF 2 , CaF 2 , SrF 2 , BaF 2 , MgCl 2 , CaCl 2, SrCl 2, BaCl 2, MgI 2, CaI 2, SrI 2, BaI 2 are mentioned.
特許文献２には、結晶格子歪みの小さいＳＭＳ青色発光蛍光体は発光強度と熱に対する安定性が高いことが記載されていて、この結晶格子歪みの小さいＳＭＳ青色発光蛍光体を製造する方法として、Ｓｒ源粉末とＭｇ源粉末とＳｉ源粉末とＥｕ源粉末との混合物を塩素化合物の存在下で焼成する方法が記載されている。この特許文献２の実施例では、ＳｒＣＯ3粉末とＳｒＣｌ2・６Ｈ2Ｏ粉末と４ＭｇＣＯ3・Ｍｇ（ＯＨ）2・４Ｈ2Ｏ粉末（塩基性炭酸マグネシウム粉末）とＳｉＯ2粉末とＥｕ2Ｏ3粉末を混合した混合物を焼成してＳＭＳ青色発光蛍光体を製造している。なお、この特許文献２の実施例ではＳＭＳ青色発光蛍光体の発光強度は波長２５４ｎｍの紫外光を励起光に用いて測定している。 Patent Document 2 describes that an SMS blue light-emitting phosphor with a small crystal lattice distortion has high light emission intensity and heat stability. As a method for producing the SMS blue light-emitting phosphor with a small crystal lattice distortion, A method is described in which a mixture of Sr source powder, Mg source powder, Si source powder and Eu source powder is fired in the presence of a chlorine compound. In the example of this Patent Document 2, SrCO 3 powder, SrCl 2 .6H 2 O powder, 4MgCO 3 .Mg (OH) 2 .4H 2 O powder (basic magnesium carbonate powder), SiO 2 powder and Eu 2 O 3 are used. An SMS blue light emitting phosphor is manufactured by firing a mixture of powders. In the example of Patent Document 2, the emission intensity of the SMS blue light emitting phosphor is measured using ultraviolet light having a wavelength of 254 nm as excitation light.
上記特許文献１には、蛍光体の製造原料として用いることができるＳｒ源や反応促進剤（フラックス）について種々の化合物が例示されている。しかしながら、特許文献１には、これらの化合物の特定の組み合わせに関する記載はない。 Patent Document 1 exemplifies various compounds for Sr sources and reaction accelerators (flux) that can be used as a raw material for producing phosphors. However, Patent Document 1 does not describe a specific combination of these compounds.
一方、特許文献２にはＳｒＣＯ3粉末とＳｒＣｌ2・６Ｈ2Ｏ粉末とを併用して製造したＳＭＳ青色発光蛍光体は波長２５４ｎｍの紫外光での励起において高い発光強度と熱に対する安定性を示すことが記載されている。しかしながら、特許文献２には、ＰＤＰにおいて蛍光体の励起光として用いられる波長１４６ｎｍや波長１７２ｎｍの真空紫外光での励起に対するＳＭＳ青色発光蛍光体の発光強度については記載がない。
従って、本発明の目的は、ＰＤＰ用の青色発光蛍光体として有利に用いることができる、すなわち波長１４６ｎｍや波長１７２ｎｍの真空紫外光での励起に特に適したＳＭＳ青色発光蛍光体の製造方法を提供することにある。
On the other hand, Patent Document 2 discloses that an SMS blue light emitting phosphor produced by using both SrCO 3 powder and SrCl 2 .6H 2 O powder exhibits high emission intensity and heat stability when excited with ultraviolet light having a wavelength of 254 nm. It is described. However, Patent Document 2 does not describe the emission intensity of the SMS blue light-emitting phosphor with respect to excitation with vacuum ultraviolet light having a wavelength of 146 nm or a wavelength of 172 nm used as excitation light of the phosphor in PDP.
Therefore, an object of the present invention is to provide a method for producing an SMS blue light-emitting phosphor that can be advantageously used as a blue light-emitting phosphor for PDP, that is, particularly suitable for excitation with vacuum ultraviolet light having a wavelength of 146 nm or a wavelength of 172 nm. There is to do.
本発明者は、Ｓｒ源粉末とＭｇ源粉末とＳｉ源粉末とＥｕ源粉末とを含む混合物を焼成してＳＭＳ青色発光蛍光体を製造するに際して、Ｓｒ源粉末にＳｒＣＯ3とＳｒＢｒ2とを９９．９：０．１〜９５：５の範囲のモル比にて含む粉末を用いて製造したＳＭＳ青色発光蛍光体は、Ｓｒ源粉末にＳｒＣＯ3粉末を単独で使用して製造したＳＭＳ青色発光蛍光体やＳｒＣＯ3粉末とＳｒＣｌ2粉末を併用して製造したＳＭＳ青色発光蛍光体と比べて、波長１４６ｎｍや波長１７２ｎｍの真空紫外光での励起に対する発光強度が高くなることを見出し、本発明に到達した。 The present inventor sinters SrCO 3 and SrBr 2 into 99 Sr source powder when a mixture containing Sr source powder, Mg source powder, Si source powder and Eu source powder is fired to produce an SMS blue light emitting phosphor. The SMS blue light-emitting phosphor manufactured using a powder containing a molar ratio in the range of .9: 0.1 to 95: 5 is the SMS blue light-emitting fluorescence manufactured using SrCO 3 powder alone as the Sr source powder. Found that the emission intensity against excitation with vacuum ultraviolet light having a wavelength of 146 nm or a wavelength of 172 nm is higher than that of an SMS blue light emitting phosphor produced by using a combination of SrCO 3 powder and SrCl 2 powder. did.
従って、本発明は、Ｓｒ源粉末とＭｇ源粉末とＳｉ源粉末とＥｕ源粉末とを含む混合物を焼成して、メルウィナイトと同じ結晶構造を有するケイ酸塩をＥｕで付活した青色発光蛍光体を製造する方法において、Ｓｒ源粉末が、ＳｒＣＯ3とＳｒＢｒ2とを９９．９：０．１〜９５：５の範囲のモル比にて含む粉末であることを特徴とする青色発光蛍光体の製造方法にある。 Accordingly, the present invention provides a blue light-emitting phosphor obtained by firing a mixture containing Sr source powder, Mg source powder, Si source powder and Eu source powder and activating Eu with a silicate having the same crystal structure as merwinite. Wherein the Sr source powder is a powder containing SrCO 3 and SrBr 2 in a molar ratio in the range of 99.9: 0.1 to 95: 5. In the manufacturing method.
本発明の青色発光蛍光体の製造方法の好ましい態様は、次の通りである。
（１）ＳｒＣＯ3とＳｒＢｒ2とのモル比が９９．８：０．２〜９７：３の範囲にある。
（２）Ｓｒ源粉末が、ＳｒＣＯ3粉末とＳｒＢｒ2粉末との混合物である。
The preferable aspect of the manufacturing method of the blue light emission fluorescent substance of this invention is as follows.
(1) The molar ratio of SrCO 3 and SrBr 2 is in the range of 99.8: 0.2 to 97: 3.
(2) The Sr source powder is a mixture of SrCO 3 powder and SrBr 2 powder.
本発明の製造方法を利用して製造したＳＭＳ青色発光蛍光体は、Ｘｅガスの放電によって発生する波長１４６ｎｍや波長１７２ｎｍの真空紫外光での励起に対する発光強度が高いことから、ＰＤＰの青色発光源の蛍光体として有利に用いることができる。 The SMS blue light-emitting phosphor manufactured by using the manufacturing method of the present invention has a high emission intensity against excitation with vacuum ultraviolet light having a wavelength of 146 nm or a wavelength of 172 nm generated by discharge of Xe gas. It can be advantageously used as a phosphor.
本発明のＳＭＳ青色発光蛍光体の製造方法は、Ｓｒ源粉末とＭｇ源粉末とＳｉ源粉末とＥｕ源粉末とを含む混合物を焼成してＳＭＳ青色発光蛍光体を製造する方法の改良であって、その主な特徴点は、Ｓｒ源粉末にＳｒＣＯ3とＳｒＢｒ2とを含む粉末を用いる点にある。ＳｒＣＯ3とＳｒＢｒ2の割合は、モル比で９９．９：０．１〜９５：５の範囲、好ましくは９９．８：０．２〜９７：３の範囲にある。Ｓｒ源粉末の例としては、ＳｒＣＯ3とＳｒＢｒ2とを含む組成物の粉末及びＳｒＣＯ3粉末とＳｒＢｒ2粉末の混合物を挙げることができる。Ｓｒ源粉末はＳｒＣＯ3粉末とＳｒＢｒ2粉末の混合物であることが好ましい。 The method for producing the SMS blue light emitting phosphor of the present invention is an improvement of the method for producing the SMS blue light emitting phosphor by firing a mixture containing Sr source powder, Mg source powder, Si source powder and Eu source powder. The main feature is that a powder containing SrCO 3 and SrBr 2 is used as the Sr source powder. The ratio of SrCO 3 and SrBr 2 is in the range of 99.9: 0.1 to 95: 5, preferably 99.8: 0.2 to 97: 3 in terms of molar ratio. Examples of the Sr source powder include a powder of a composition containing SrCO 3 and SrBr 2 and a mixture of SrCO 3 powder and SrBr 2 powder. The Sr source powder is preferably a mixture of SrCO 3 powder and SrBr 2 powder.
本発明において、Ｓｒ源粉末以外の原料粉末、すなわちＭｇ源粉末、Ｓｉ源粉末及びＥｕ源粉末はそれぞれ、酸化物粉末であってもよいし、水酸化物、ハロゲン化物、炭酸塩（塩基性炭酸塩を含む）、硝酸塩、シュウ酸塩などの加熱により酸化物を生成する化合物の粉末であってもよい。上記の原料粉末はそれぞれ一種を単独で使用してもよいし、二種以上を併用してもよい。 In the present invention, the raw material powder other than the Sr source powder, that is, the Mg source powder, the Si source powder, and the Eu source powder may be oxide powders, hydroxides, halides, carbonates (basic carbonates), respectively. Salt), nitrates, oxalates, etc., and powders of compounds that generate oxides upon heating. Each of the above raw material powders may be used alone or in combination of two or more.
本発明において、Ｓｒ源粉末を含む各原料粉末は、純度が９９質量％以上であることが好ましい。また、各原料粉末の平均粒子径は、５μｍ以下であることが好ましく、０．０１〜５μｍの範囲にあることが好ましい。 In this invention, it is preferable that each raw material powder containing Sr source powder is 99 mass% or more in purity. Moreover, it is preferable that the average particle diameter of each raw material powder is 5 micrometers or less, and it exists in the range of 0.01-5 micrometers.
Ｓｒ源粉末、Ｍｇ源粉末、Ｓｉ源粉末、Ｅｕ源粉末の配合比は、原料粉末混合物中のＳｒ、Ｍｇ、Ｓｉ及びＥｕの含有量がＭｇの量を１モルとしたときに、ＳｒとＥｕとの合計が２．９〜３．１モルの範囲の量で、Ｓｉが１．９〜２．１モルの範囲の量となり、さらにＥｕが０．００１〜０．２モルの範囲の量となる割合であることが好ましい。 The compounding ratio of the Sr source powder, Mg source powder, Si source powder, and Eu source powder is such that when the content of Sr, Mg, Si, and Eu in the raw material powder mixture is 1 mol of Mg, Sr and Eu The amount of Si in the range of 1.9 to 2.1 mol, and the amount of Eu in the range of 0.001 to 0.2 mol. The ratio is preferably
原料粉末の混合方法には、乾式混合法及び湿式混合法のいずれかの方法を採用することができる。湿式混合法で原料粉末を混合する場合は、回転ボールミル、振動ボールミル、遊星ミル、ペイントシェーカー、ロッキングミル、ロッキングミキサー、ビーズミル、撹拌機などを用いることができる。溶媒には、水や、エタノール、イソプロピルアルコールなどの低級アルコールを用いることができる。 Either a dry mixing method or a wet mixing method can be adopted as a method for mixing the raw material powders. When the raw material powder is mixed by a wet mixing method, a rotating ball mill, a vibrating ball mill, a planetary mill, a paint shaker, a rocking mill, a rocking mixer, a bead mill, a stirrer, or the like can be used. As the solvent, water, lower alcohols such as ethanol and isopropyl alcohol can be used.
原料粉末混合物の焼成は、大気雰囲気下にて仮焼した後、還元性ガス雰囲気下にて焼成する方法によって実施することが好ましい。大気雰囲気下での仮焼温度は一般に６００〜８５０℃の範囲の温度である。仮焼時間は一般に０．５〜１００時間の範囲にある。還元性ガスとしては、０．５〜５．０体積％の水素と９９．５〜９５．０体積％の不活性気体とを含む混合ガスを挙げることができる。不活性気体の例としては、アルゴン及び窒素を挙げることができる。還元性ガス雰囲気下での焼成温度は一般に９００〜１３００℃の範囲の温度である。焼成時間は、一般に０．５〜１００時間の範囲にある。 The firing of the raw material powder mixture is preferably carried out by a method of calcining in a reducing gas atmosphere after calcining in an air atmosphere. The calcination temperature in the atmosphere is generally in the range of 600 to 850 ° C. The calcining time is generally in the range of 0.5 to 100 hours. Examples of the reducing gas include a mixed gas containing 0.5 to 5.0% by volume of hydrogen and 99.5 to 95.0% by volume of an inert gas. Examples of inert gases include argon and nitrogen. The firing temperature in a reducing gas atmosphere is generally in the range of 900 to 1300 ° C. The firing time is generally in the range of 0.5 to 100 hours.
焼成により得られたＳＭＳ青色発光蛍光体は、必要に応じて分級処理、塩酸や硝酸などの鉱酸による酸洗浄処理、ベーキング処理を行なってもよい。 The SMS blue light-emitting phosphor obtained by firing may be subjected to classification treatment, acid cleaning treatment with a mineral acid such as hydrochloric acid or nitric acid, and baking treatment as necessary.
本発明の製造方法により得られるＳＭＳ青色発光蛍光体は、メルウィナイト（Ｃａ3ＭｇＳｉ2Ｏ8）と同じ結晶構造を有するケイ酸塩をＥｕで付活した青色発光蛍光体である。メルウィナイトと同じ結晶構造を有することは、Ｘ線回折パターンより確認することができる。 The SMS blue light-emitting phosphor obtained by the production method of the present invention is a blue light-emitting phosphor obtained by activating Eu with a silicate having the same crystal structure as that of merwinite (Ca 3 MgSi 2 O 8 ). It can be confirmed from the X-ray diffraction pattern that it has the same crystal structure as merwinite.
本発明の製造方法により得られるＳＭＳ青色発光蛍光体は、Ｓｒ3ＭｇＳｉ2Ｏ8の組成式で示されるケイ酸塩をＥｕで付活した青色発光蛍光体であってもよいし、Ｓｒ3ＭｇＳｉ2Ｏ8の組成式で示されるケイ酸塩の一部をＢｒで置換したケイ酸塩をＥｕで付活した青色発光蛍光体であってもよい。但し、Ｂｒの含有量は、Ｍｇの含有量を１モルとしたときに一般に０．０３モル以下である。さらに、本発明の製造方法により得られるＳＭＳ青色発光蛍光体はＢａやＣａを含有していてもよい。但し、Ｂａの含有量は、Ｍｇの含有量を１モルとしたときに一般に０．４モル以下、好ましくは０．２モル以下、より好ましくは０．０８モル以下、特に好ましくは０．０１モル以下である。Ｃａの含有量は、Ｍｇの含有量を１モルとしたときに一般に０．０８モル以下、好ましくは０．０１モル以下である。 The SMS blue light-emitting phosphor obtained by the production method of the present invention may be a blue light-emitting phosphor in which a silicate represented by the composition formula of Sr 3 MgSi 2 O 8 is activated with Eu, or Sr 3 MgSi A blue light emitting phosphor in which a silicate obtained by substituting a part of the silicate represented by the composition formula of 2 O 8 with Br is activated with Eu may be used. However, the Br content is generally 0.03 mol or less when the Mg content is 1 mol. Furthermore, the SMS blue light-emitting phosphor obtained by the production method of the present invention may contain Ba or Ca. However, the content of Ba is generally 0.4 mol or less, preferably 0.2 mol or less, more preferably 0.08 mol or less, particularly preferably 0.01 mol when the Mg content is 1 mol. It is as follows. The Ca content is generally 0.08 mol or less, preferably 0.01 mol or less, when the Mg content is 1 mol.
本発明の製造方法により得られるＳＭＳ青色発光蛍光体は原料粉末の粒子径にもよるが、Ｓｒ源粉末にＳｒＣＯ3粉末を単独で使用して製造したＳＭＳ青色発光蛍光体やＳｒＣＯ3粉末とＳｒＣｌ2粉末を併用して製造したＳＭＳ青色発光蛍光体と比べて、通常は、粒子径が微細で、かつ粒子径の均一性が高い。 The SMS blue light-emitting phosphor obtained by the production method of the present invention depends on the particle diameter of the raw material powder, but the SMS blue light-emitting phosphor or SrCO 3 powder and SrCl produced by using SrCO 3 powder alone as the Sr source powder. Compared with the SMS blue light-emitting phosphor produced by using two powders together, the particle diameter is usually fine and the uniformity of the particle diameter is high.
［実施例１］
炭酸ストロンチウム（ＳｒＣＯ3）粉末（純度：９９．７質量％、レーザー回折散乱法により測定された平均粒子径：０．９μｍ）と臭化ストロンチウム六水和物（ＳｒＢｒ2・６Ｈ2Ｏ）粉末（純度：９９質量％）とを、モル比で９９．２：０．８となる割合にて混合して、Ｓｒ源粉末を得た。得られたＳｒ源粉末と、酸化ユウロピウム（Ｅｕ2Ｏ3）粉末（純度：９９．９質量％、レーザー回折散乱法により測定された平均粒子径：２．７μｍ）と、酸化マグネシウム（ＭｇＯ）粉末（気相法により製造したもの、純度：９９．９８質量％、ＢＥＴ比表面積より換算された平均粒子径：０．２μｍ）と、酸化ケイ素（ＳｉＯ2）粉末（純度：９９．９質量％、ＢＥＴ比表面積より換算された平均粒子径：０．０１μｍ）とを、Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比で２．９９５：０．００５：１：２．０００となるようにそれぞれ秤量し、水中にてボールミルを用いて１５時間湿式混合して粉末混合物のスラリーを得た。得られたスラリーをスプレードライヤーにより噴霧乾燥して、平均粒子径が４０μｍの粉末混合物を得た。得られた粉末混合物をアルミナ坩堝に入れて、大気雰囲気下にて８００℃の温度で３時間焼成し、次いで室温まで放冷した後、２体積％水素−９８体積％アルゴンの混合ガス雰囲気下にて１２００℃の温度で３時間焼成した。そして、得られた焼成物を室温まで放冷した後、水洗して乾燥した。乾燥後の焼成物のＸ線回折パターンを測定したところ、得られた焼成物は、メルウィナイトと同じ結晶構造を有するＳＭＳ青色発光蛍光体であることが確認された。得られたＳＭＳ青色発光蛍光体について、波長１４６ｎｍ及び波長１７２ｎｍの真空紫外光励起による発光強度と粒度分布を下記の方法により測定した。その結果を表１に示す。
[Example 1]
Strontium carbonate (SrCO 3 ) powder (purity: 99.7% by mass, average particle diameter measured by laser diffraction scattering method: 0.9 μm) and strontium bromide hexahydrate (SrBr 2 .6H 2 O) powder ( (Purity: 99% by mass) was mixed at a molar ratio of 99.2: 0.8 to obtain an Sr source powder. The obtained Sr source powder, europium oxide (Eu 2 O 3 ) powder (purity: 99.9% by mass, average particle diameter measured by laser diffraction scattering method: 2.7 μm), and magnesium oxide (MgO) powder (Producted by vapor phase method, purity: 99.98% by mass, average particle size converted from BET specific surface area: 0.2 μm) and silicon oxide (SiO 2 ) powder (purity: 99.9% by mass, Average particle diameter converted from the BET specific surface area: 0.01 μm) and a molar ratio of Sr: Eu: Mg: Si to be 2.995: 0.005: 1: 2.000, A powder mixture slurry was obtained by wet mixing in water using a ball mill for 15 hours. The obtained slurry was spray-dried with a spray dryer to obtain a powder mixture having an average particle size of 40 μm. The obtained powder mixture was put in an alumina crucible, calcined at a temperature of 800 ° C. for 3 hours in an air atmosphere, then allowed to cool to room temperature, and then in a mixed gas atmosphere of 2 vol% hydrogen-98 vol% argon. And calcined at 1200 ° C. for 3 hours. The obtained fired product was allowed to cool to room temperature, washed with water and dried. When the X-ray diffraction pattern of the fired product after drying was measured, it was confirmed that the obtained fired product was an SMS blue light-emitting phosphor having the same crystal structure as merwinite. About the obtained SMS blue light emission fluorescent substance, the light emission intensity and particle size distribution by the vacuum ultraviolet light excitation of wavelength 146nm and wavelength 172nm were measured with the following method. The results are shown in Table 1.
［発光強度の測定方法］
試料のＳＭＳ青色発光蛍光体に波長１４６ｎｍ又は波長１７２ｎｍの真空紫外光を照射して、発光スペクトルを測定し、得られた発光スペクトルの４００〜５００ｎｍの波長範囲の中で最大ピーク強度を求め、これを発光強度とする。発光強度は、後述の比較例１で製造したＳＭＳ青色発光蛍光体の発光強度を１００とした相対値で示す。
[Measurement method of luminescence intensity]
The sample blue light emitting phosphor is irradiated with vacuum ultraviolet light having a wavelength of 146 nm or a wavelength of 172 nm, the emission spectrum is measured, and the maximum peak intensity in the wavelength range of 400 to 500 nm of the obtained emission spectrum is obtained. Is the emission intensity. The light emission intensity is shown as a relative value with the light emission intensity of the SMS blue light emitting phosphor manufactured in Comparative Example 1 described later as 100.
［粒度分布の測定方法］
粒度分布は、レーザー回折散乱法により測定する。測定装置には、マイクロトラックＨＲＡ９３２０−Ｘ１００（日機装（株）製）を用い、分散溶媒には水を使用する。試料のＳＭＳ青色発光蛍光体（約２０ｍｇ）と水（約４０ｍＬ）とを混合し、超音波ホモジナイザー（ＵＳ−１５０Ｔ、（株）日本精機製作所製）を用いて超音波を３分間照射して、ＳＭＳ青色発光蛍光体を水中に分散させる。超音波照射後、得られた分散液の粒度分布をただちに測定する。表１中、Ｄ10は粒子径の積算篩下分布が１０％となる粒子径を、Ｄ50は粒子径の積算篩下分布が５０％となる粒子径（メジアン径）を、Ｄ90は粒子径の積算篩下分布が９０％となる粒子径を意味する。
[Measuring method of particle size distribution]
The particle size distribution is measured by a laser diffraction scattering method. Microtrac HRA9320-X100 (manufactured by Nikkiso Co., Ltd.) is used as the measuring device, and water is used as the dispersion solvent. The sample SMS blue light-emitting phosphor (about 20 mg) and water (about 40 mL) were mixed, and ultrasonic waves were irradiated for 3 minutes using an ultrasonic homogenizer (US-150T, manufactured by Nippon Seiki Seisakusho). An SMS blue-emitting phosphor is dispersed in water. After ultrasonic irradiation, the particle size distribution of the obtained dispersion is measured immediately. In Table 1, D 10 is the particle size cumulative undersize particle size distribution is 10%, D 50 is the particle size cumulative undersize particle size distribution is 50% (median diameter), D 90 is the particle It means the particle diameter at which the cumulative sieve distribution of the diameter is 90%.
［比較例１］
Ｓｒ源粉末に臭化ストロンチウム六水和物粉末を加えずに、炭酸ストロンチウム粉末のみを使用したこと以外は実施例１と同様にして、ＳＭＳ青色発光蛍光体を製造し、波長１４６ｎｍ及び波長１７２ｎｍの真空紫外光励起による発光強度と粒度分布を測定した。その結果を表１に示す。
[Comparative Example 1]
An SMS blue light emitting phosphor was produced in the same manner as in Example 1 except that only the strontium carbonate powder was used without adding the strontium bromide hexahydrate powder to the Sr source powder, and the wavelengths of 146 nm and 172 nm were produced. The emission intensity and particle size distribution by vacuum ultraviolet light excitation were measured. The results are shown in Table 1.
［比較例２］
Ｓｒ源粉末に、炭酸ストロンチウム粉末と塩化ストロンチウム六水和物（ＳｒＣｌ2・６Ｈ2Ｏ）粉末（純度：９９．９質量％）とをモル比で９９．２：０．８となる割合にて混合して得た粉末混合物を使用したこと以外は実施例１と同様にして、ＳＭＳ青色発光蛍光体を製造し、波長１４６ｎｍ及び波長１７２ｎｍの真空紫外光励起による発光強度と粒度分布を測定した。その結果を表１に示す。
[Comparative Example 2]
Sr source powder, strontium carbonate powder and strontium chloride hexahydrate (SrCl 2 .6H 2 O) powder (purity: 99.9% by mass) in a molar ratio of 99.2: 0.8 An SMS blue light-emitting phosphor was produced in the same manner as in Example 1 except that the powder mixture obtained by mixing was used, and the emission intensity and particle size distribution by excitation with vacuum ultraviolet light at a wavelength of 146 nm and a wavelength of 172 nm were measured. The results are shown in Table 1.
表１
────────────────────────────────────────
発光強度 粒度分布
Ｓｒ源粉末の組成 ────────────────────────
（モル比） １４６ｎｍ １７２ｎｍ Ｄ10 Ｄ50 Ｄ90
────────────────────────────────────────
実施例１ ＳｒＣＯ3：ＳｒＢｒ2 １０８ １２９ １．５ ３．５ ６．３
＝９９．２：０．８
────────────────────────────────────────
比較例１ ＳｒＣＯ3単独 １００ １００ １．１ ４．９ ３８．７
比較例２ ＳｒＣＯ3：ＳｒＣｌ2 １０６ １２５ ４．３ ７．９ １４．２
＝９９．２：０．８
────────────────────────────────────────
Table 1
────────────────────────────────────────
Luminescence intensity Particle size distribution
Composition of Sr source powder ────────────────────────
(Molar ratio) 146 nm 172 nm D 10 D 50 D 90
────────────────────────────────────────
Example 1 SrCO 3 : SrBr 2 108 129 1.5 3.5 6.3
= 99.2: 0.8
────────────────────────────────────────
Comparative Example 1 SrCO 3 alone 100 100 1.1 4.9 38.7
Comparative Example 2 SrCO 3 : SrCl 2 106 125 4.3 7.9 14.2
= 99.2: 0.8
────────────────────────────────────────
表１の結果から明らかなように、Ｓｒ源粉末にＳｒＣＯ3粉末とＳｒＢｒ2粉末とを併用して製造したＳＭＳ青色発光蛍光体（実施例１）は、Ｓｒ源粉末にＳｒＣＯ3粉末を単独で使用して製造したＳＭＳ青色発光蛍光体（比較例１）、Ｓｒ源粉末にＳｒＣＯ3粉末とＳｒＣｌ2粉末とを併用して製造したＳＭＳ青色発光蛍光体（比較例２）と比較して、真空紫外光励起に対して高い発光強度を示す。また、実施例１のＳＭＳ青色発光蛍光体は、比較例１、２のＳＭＳ青色発光蛍光体と比較してＤ50が小さく、Ｄ10からＤ90まで粒子径範囲が狭いことから、微細でかつ粒子径の均一性が高いことが分かる。 As is clear from the results in Table 1, the SMS blue light-emitting phosphor (Example 1) produced by using the Sr source powder in combination with the SrCO 3 powder and the SrBr 2 powder has the SrCO 3 powder alone in the Sr source powder. Compared with the SMS blue light emitting phosphor (Comparative Example 1) manufactured using the Sr source powder, the SrCO 3 powder and the SrCl 2 powder are used in combination with the Sm source light emitting phosphor (Comparative Example 2). High emission intensity with respect to ultraviolet light excitation. In addition, the SMS blue light-emitting phosphor of Example 1 has a small D 50 compared to the SMS blue light-emitting phosphors of Comparative Examples 1 and 2, and the particle diameter range from D 10 to D 90 is narrow. It can be seen that the uniformity of the particle size is high.
［実施例２〜５］
Ｓｒ源粉末の炭酸ストロンチウム粉末と臭化ストロンチウム六水和物粉末との配合比（モル比）を、下記の表２に記載の配合比としたこと以外は、実施例１と同様にして、ＳＭＳ青色発光蛍光体を製造し、波長１４６ｎｍ及び波長１７２ｎｍの真空紫外光励起による発光強度を測定した。その結果を表２に示す。
[Examples 2 to 5]
SMS was conducted in the same manner as in Example 1 except that the blending ratio (molar ratio) of the strontium carbonate powder and strontium bromide hexahydrate powder as the Sr source powder was the blending ratio shown in Table 2 below. A blue-emitting phosphor was manufactured, and the emission intensity by excitation with vacuum ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm was measured. The results are shown in Table 2.
表２
────────────────────────────────────────
発光強度
Ｓｒ源粉末の配合比（モル比） ────────────────
ＳｒＣＯ3：ＳｒＢｒ2 １４６ｎｍ １７２ｎｍ
────────────────────────────────────────
実施例２ ９９．５：０．５ １１２ １３４
実施例３ ９８．３：１．７ １０９ １３０
実施例４ ９７．５：２．５ １０７ １２５
実施例５ ９６．７：３．３ １０５ １２５
────────────────────────────────────────
Table 2
────────────────────────────────────────
Luminous intensity
Compounding ratio (molar ratio) of Sr source powder ────────────────
SrCO 3 : SrBr 2 146 nm 172 nm
────────────────────────────────────────
Example 2 99.5: 0.5 112 134
Example 3 98.3: 1.7 109 130
Example 4 97.5: 2.5 107 125
Example 5 96.7: 3.3 105 125
────────────────────────────────────────
表２の結果から明らかなように、Ｓｒ源粉末にＳｒＣＯ3粉末とＳｒＢｒ2粉末とを本発明の割合で併用することによって、真空紫外光励起での発光強度が高いＳＭＳ青色発光蛍光体を製造することが可能となる。 As is apparent from the results in Table 2, by using SrCO 3 powder and SrBr 2 powder in the ratio of the present invention in combination with the Sr source powder, an SMS blue light emitting phosphor having high emission intensity by vacuum ultraviolet light excitation is manufactured. It becomes possible.
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| JP2015086340A (en) * | 2013-11-01 | 2015-05-07 | 宇部マテリアルズ株式会社 | White light-emitting phosphor and white light-emitting device |
| CN106634972A (en) * | 2016-11-08 | 2017-05-10 | 中山职业技术学院 | Single-phase phosphor for white LED and preparation method of single-phase phosphor |
| CN116410745A (en) * | 2021-12-31 | 2023-07-11 | 江苏博睿光电股份有限公司 | Fluorescent powder material |
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| CN106634972A (en) * | 2016-11-08 | 2017-05-10 | 中山职业技术学院 | Single-phase phosphor for white LED and preparation method of single-phase phosphor |
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| CN116410745B (en) * | 2021-12-31 | 2023-10-24 | 江苏博睿光电股份有限公司 | Fluorescent powder material |
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