JP2012017455A - Method for producing oxide fluorescent particle and light-emitting device - Google Patents
Method for producing oxide fluorescent particle and light-emitting device Download PDFInfo
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本発明は、酸化物蛍光粒子の製造方法、及びこの方法により得られた酸化物蛍光粒子を用いた発光デバイスに関する。 The present invention relates to a method for producing oxide fluorescent particles, and a light-emitting device using the oxide fluorescent particles obtained by this method.
照明及びディスプレイ分野において、蛍光体は波長変換材料としていろいろな製品に使われている。蛍光体の製造方法としては、各構成元素の酸化物等の化合物を混合し、高温にて反応させることで得る方法が一般的である。また、各構成元素の反応や結晶成長を促すために、フラックスと呼ばれる低融点の化合物を添加することもある。 In the field of illumination and display, phosphors are used in various products as wavelength conversion materials. As a method for producing a phosphor, a method obtained by mixing compounds such as oxides of respective constituent elements and reacting them at a high temperature is common. Moreover, in order to promote reaction of each constituent element and crystal growth, a low melting point compound called flux may be added.
このような従来の製造方法によって得られる蛍光粒子は、一般に不定形、柱状、平板状、多面体などの形状になるが、高温で合成するため、また、複数の元素を化合させるため、粒子同士がネッキングや融着によって様々な形状となり、得られた蛍光粒子は、一定の形状をもつことがない。そのため、蛍光粒子を製造する際には、一般に分級による粗大粒子の除去や、解粒によるネッキングの切り離しがなされるが、このことによって蛍光粒子の製造歩留まりが減少し、また、蛍光体の発光特性が低下する。更に、蛍光体形状によっては、蛍光の取り出し効率が低下するおそれがある。 The fluorescent particles obtained by such a conventional manufacturing method generally have an irregular shape, a columnar shape, a flat plate shape, a polyhedron shape, etc., but in order to synthesize at a high temperature and to combine a plurality of elements, the particles are separated from each other. Various shapes are formed by necking or fusion, and the obtained fluorescent particles do not have a certain shape. For this reason, when producing fluorescent particles, coarse particles are generally removed by classification and necking is separated by pulverization. This reduces the production yield of fluorescent particles, and the phosphor emission characteristics. Decreases. Furthermore, depending on the shape of the phosphor, the fluorescence extraction efficiency may decrease.
本発明は、上記問題を解決するためになされたものであり、粒子同士のネッキングや粒子の粗大化が起きにくく、簡単な解粒、分級の工程により、又はこれらの工程を経なくとも、球形状乃至略球形状の形状が安定した酸化物蛍光粒子を製造することができる方法、及びこの方法により得られた酸化物蛍光粒子を用いた発光デバイスを提供することを目的とする。 The present invention has been made in order to solve the above problems, and it is difficult for necking of particles or coarsening of particles to occur, and the spheres can be obtained by simple pulverization and classification processes or without these processes. It is an object of the present invention to provide a method capable of producing oxide fluorescent particles having a stable shape or a substantially spherical shape, and a light-emitting device using the oxide fluorescent particles obtained by this method.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、Ｓｃ及びＹを含む希土類から選ばれる１種類以上の希土類金属と、Ａｌ，Ｇａ，Ｉｎ，Ｓｉ及びＧｅから選ばれる１種類以上の金属とを含む金属材料を溶融して合金とし、該合金を平均粒径が５０μｍ以下の球形状乃至略球形状の微粒子とし、該合金微粒子を酸化することにより酸化物蛍光粒子を製造すれば、粒子同士のネッキングや粒子の粗大化が起きにくく、簡単な解粒、分級の工程により、又はこれらの工程を経なくとも、球形状乃至略球形状の、形状が安定した酸化物蛍光粒子を製造することができることを見出し、本発明をなすに至った。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have selected one or more rare earth metals selected from rare earths including Sc and Y, and Al, Ga, In, Si and Ge. A metal material containing at least one kind of metal is melted to form an alloy, the alloy is made into spherical or substantially spherical fine particles having an average particle size of 50 μm or less, and oxide fine particles are produced by oxidizing the alloy fine particles. In this way, necking of particles and coarsening of particles are unlikely to occur, and a spherical or substantially spherical oxide-stable oxide fluorescence can be obtained by simple pulverization and classification processes or without these processes. The inventors have found that particles can be produced, and have made the present invention.
従って、本発明は、下記の酸化物蛍光粒子の製造方法及び発光デバイスを提供する。
請求項１：
Ｓｃ及びＹを含む希土類から選ばれる１種類以上の希土類金属と、Ａｌ，Ｇａ，Ｉｎ，Ｓｉ及びＧｅから選ばれる１種類以上の金属とを含む金属材料を溶融して合金とし、該合金を平均粒径が５０μｍ以下の球形状乃至略球形状の微粒子に形成し、該合金微粒子を酸化することを特徴とする酸化物蛍光粒子の製造方法。
請求項２：
Ｙ，Ｇｄ及びＬｕから選ばれる１種類以上の希土類金属と、Ｃｅ，Ｎｄ及びＴｂから選ばれる１種類以上の希土類金属と、Ａｌ及びＧａから選ばれる１種類以上の金属とを含む金属材料を溶融して合金とし、該合金を平均粒径が５０μｍ以下の球形状乃至略球形状の微粒子に形成し、該合金微粒子を酸化することを特徴とする酸化物蛍光粒子の製造方法。
請求項３：
上記金属材料が、更に、Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｆｒ，Ｂｅ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ及びＲａから選ばれる１種類以上の金属を含むことを特徴とする請求項１又は２記載の酸化物蛍光粒子の製造方法。
請求項４：
回転ディスクアトマイザーを用いて、上記球形状乃至略球形状の微粒子を形成することを特徴とする請求項１乃至３のいずれか１項記載の酸化物蛍光粒子の製造方法。
請求項５：
平均真円度が０．３以下の酸化物蛍光粒子を製造することを特徴とする請求項１乃至４のいずれか１項記載の酸化物蛍光粒子の製造方法。
請求項６：
請求項１乃至５のいずれか１項記載の方法により得られた酸化物蛍光粒子を用いたことを特徴とする発光デバイス。
Accordingly, the present invention provides the following method for producing oxide fluorescent particles and a light emitting device.
Claim 1:
A metal material containing at least one rare earth metal selected from rare earths including Sc and Y and at least one metal selected from Al, Ga, In, Si and Ge is melted to form an alloy, and the alloy is averaged. A method for producing oxide fluorescent particles, comprising forming spherical or substantially spherical fine particles having a particle size of 50 μm or less and oxidizing the alloy fine particles.
Claim 2:
Melting a metal material containing one or more rare earth metals selected from Y, Gd and Lu, one or more rare earth metals selected from Ce, Nd and Tb, and one or more metals selected from Al and Ga. A method for producing oxide fluorescent particles, comprising forming an alloy into spherical or substantially spherical fine particles having an average particle diameter of 50 μm or less and oxidizing the alloy fine particles.
Claim 3:
The metal material further contains one or more kinds of metals selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra. The manufacturing method of the oxide fluorescent particle of description.
Claim 4:
The method for producing oxide fluorescent particles according to any one of claims 1 to 3, wherein the spherical or substantially spherical fine particles are formed using a rotating disk atomizer.
Claim 5:
The method for producing oxide fluorescent particles according to any one of claims 1 to 4, wherein the oxide fluorescent particles having an average roundness of 0.3 or less are produced.
Claim 6:
A light-emitting device using the oxide fluorescent particles obtained by the method according to claim 1.
本発明の方法で製造した蛍光粒子は、合金粒子を酸化する前の時点で、独立した球形状乃至略球形状となっており、これを酸化して酸化物とした後も、粒子の形状を保ったままの球形状乃至略球形状の酸化物蛍光粒子となる。また、ネッキングや粒子の粗大化が起き難く、通常の蛍光粒子製造に必要な解粒、分級工程が不要又は非常に容易になるという利点がある。また、形状が球形状乃至略球形状で一定していることから、蛍光体の混合や塗布での粒子の並びや配置のコントロールがしやすく、これにより蛍光体からの蛍光の取り出し効率が向上する。 The fluorescent particles produced by the method of the present invention have an independent spherical shape or a substantially spherical shape before the alloy particles are oxidized. The spherical or substantially spherical oxide fluorescent particles are kept as they are. Further, there is an advantage that necking and particle coarsening hardly occur, and the pulverization and classification steps necessary for normal fluorescent particle production are unnecessary or very easy. In addition, since the shape is constant in a spherical shape or a substantially spherical shape, it is easy to control the arrangement and arrangement of the particles in the mixing and application of the phosphor, thereby improving the efficiency of extracting the fluorescence from the phosphor. .
本発明の製造方法により得られた蛍光粒子は、ネッキングや融着が非常に少なく、蛍光粒子製造工程において、ネッキングや融着を解消するための解粒や分級工程が軽減できる。また、従来の蛍光粒子と比較して、粒度分布をシャープにすることができ、実際に蛍光粒子を使用する場合に、粒子の塗布や混合工程において、流動性がよく、取り扱いが容易である。また、形状が一定であることにより、蛍光体の発光の取り出し効率が向上する。 The fluorescent particles obtained by the production method of the present invention have very little necking and fusion, and in the fluorescent particle production process, the pulverization and classification steps for eliminating necking and fusion can be reduced. In addition, the particle size distribution can be sharpened as compared with conventional fluorescent particles, and when fluorescent particles are actually used, they are good in fluidity and easy to handle in the particle coating and mixing process. Further, since the shape is constant, the light emission efficiency of the phosphor is improved.
以下、本発明について詳細に説明する。
本発明において、酸化物蛍光粒子（酸化物蛍光体の粒子）は、酸化物蛍光粒子を構成する２種類以上の金属材料を溶融して合金とし、平均粒径が５０μｍ以下の球形状乃至略球形状の微粒子に形成し、更に、球形状乃至略球形状の合金微粒子を酸化することにより製造される。
Hereinafter, the present invention will be described in detail.
In the present invention, the oxide fluorescent particles (oxide phosphor particles) are formed by melting two or more kinds of metal materials constituting the oxide fluorescent particles into an alloy and having an average particle diameter of 50 μm or less in a spherical or substantially spherical shape. It is manufactured by forming spherical fine particles and further oxidizing spherical or substantially spherical alloy fine particles.
溶融して合金化する処理においては、金属単体又は金属２成分以上からなる合金を酸化物蛍光粒子中の金属の比率に合わせて混合し、融点以上の温度で溶融させる。溶融させる際の雰囲気は、真空又はアルゴンなどの不活性ガス雰囲気とする。溶解された合金の溶湯は、これを直接、球形状乃至略球形状の微粒子を形成する処理に用いてもよく、また、一旦、棒状、塊状に鋳造してもよい。 In the process of melting and alloying, a single metal or an alloy composed of two or more metal components is mixed in accordance with the ratio of the metal in the oxide fluorescent particles and melted at a temperature equal to or higher than the melting point. The atmosphere for melting is an inert gas atmosphere such as vacuum or argon. The molten alloy melt may be used directly in a process of forming spherical or substantially spherical fine particles, or may be once cast into a rod shape or a lump shape.
次に、得られた合金を用いて、球形状乃至略球形状の微粒子を形成する。このような形状の微粒子は、合金の溶湯から球形状乃至略球形状の微粒子を形成する手法、例えば、回転ディスクアトマイザーなどを用い、固体状の合金を用いる場合は合金を溶融させた上で、溶湯を微小液滴に形成して固化させることにより形成することができる。形成する合金微粒子の大きさは、通常、酸化後に得られる酸化物蛍光粒子の大きさと同程度である。合金微粒子の形成時の雰囲気は、真空又はアルゴンなどの不活性ガス雰囲気とすることができ、また、後に合金微粒子を酸化するので、酸素を含む雰囲気、例えば、大気雰囲気であってもよい。 Next, spherical or substantially spherical fine particles are formed using the obtained alloy. The fine particles having such a shape are formed by using spherical or substantially spherical fine particles from a molten alloy, for example, a rotating disk atomizer, and when a solid alloy is used, after melting the alloy, It can be formed by forming molten metal into fine droplets and solidifying them. The size of the alloy fine particles to be formed is usually about the same as the size of the oxide fluorescent particles obtained after oxidation. The atmosphere at the time of forming the alloy fine particles can be an atmosphere of an inert gas such as vacuum or argon. Further, since the alloy fine particles are oxidized later, an atmosphere containing oxygen, for example, an air atmosphere may be used.
次に、得られた合金微粒子を大気雰囲気等の酸素を含む雰囲気で加熱して酸化する。酸化温度は、蛍光体の組成によって異なるが、１０００〜１８００℃が好ましい。この加熱の時間は、通常３０分〜１０時間である。また、この酸化の上記加熱温度までの昇温速度は、速すぎると合金の燃焼熱などで、微粒子同士が融着することがあるため、通常、５０℃／時間以下、特に１０〜３０℃／時間のゆっくりとした速度で昇温することが好ましい。この酸化処理後、冷却すれば、酸化物蛍光粒子が得られる。 Next, the obtained alloy fine particles are heated and oxidized in an atmosphere containing oxygen such as an air atmosphere. The oxidation temperature varies depending on the phosphor composition, but is preferably 1000 to 1800 ° C. The heating time is usually 30 minutes to 10 hours. Further, if the temperature rise rate to the above heating temperature of this oxidation is too fast, fine particles may be fused with each other due to the heat of combustion of the alloy. It is preferable to raise the temperature at a slow rate of time. If this oxidation treatment is followed by cooling, oxide fluorescent particles can be obtained.
合金微粒子の製造においては、一部形状が悪いもの、例えば箔状のものや、ひょうたん型など、球形状からかけ離れた形状のものが含まれる場合があるが、その場合は、酸化処理の前又は酸化処理の後に、分級や傾斜法などによって、形状不良の粒子をより分けることができる。また、必要に応じて、粒径を揃えるための分級を実施することも可能である。 In the production of alloy fine particles, there are cases in which a part of the shape is bad, for example, a foil shape, a gourd shape, or a shape far from a spherical shape. After the oxidation treatment, poorly shaped particles can be further separated by classification or a gradient method. Moreover, it is also possible to carry out classification for uniforming the particle diameter as necessary.
酸化処理により得られた酸化物蛍光粒子は、その賦活剤の種類によっては、更に、高温アニール処理を施してもよい。この高温アニール処理は、大気雰囲気等の酸化雰囲気、又はＨ2＋Ｎ2ガス、Ｈ2＋Ａｒガス等の、水素ガスなどを含む還元雰囲気で実施することが好ましく、また、１３００〜１８００℃の温度で、２〜６時間実施することが好ましい。この高温アニール処理により、酸化物蛍光粒子の吸収率や発光効率を向上させることができる。 The oxide fluorescent particles obtained by the oxidation treatment may be further subjected to a high-temperature annealing treatment depending on the type of the activator. This high-temperature annealing treatment is preferably performed in an oxidizing atmosphere such as an air atmosphere or a reducing atmosphere containing hydrogen gas such as H 2 + N 2 gas or H 2 + Ar gas, and at a temperature of 1300 to 1800 ° C. , Preferably 2 to 6 hours. By this high-temperature annealing treatment, the absorption rate and luminous efficiency of the oxide fluorescent particles can be improved.
本発明の製造方法は、
（Ａ）Ｓｃ及びＹを含む希土類、即ち、Ｓｃ，Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ及びＬｕから選ばれる１種類以上、好ましくは２種類以上の希土類金属、特に、Ｙ，Ｇｄ及びＬｕから選ばれる１種類以上の希土類金属及びＣｅ，Ｎｄ及びＴｂから選ばれる１種類以上の希土類金属と、
（Ｂ）Ａｌ，Ｇａ，Ｉｎ，Ｓｉ及びＧｅから選ばれる１種類以上の金属、特に、Ａｌ及びＧａから選ばれる１種類以上の金属
とを含む酸化物蛍光粒子の製造に好適である。酸化物蛍光粒子は、更に、
（Ｃ）Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｆｒ，Ｂｅ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ及びＲａから選ばれる１種類以上の金属
を含んでいてもよい。
The production method of the present invention comprises:
(A) Rare earth containing Sc and Y, that is, one kind selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu Or more, preferably two or more rare earth metals, in particular one or more rare earth metals selected from Y, Gd and Lu, and one or more rare earth metals selected from Ce, Nd and Tb,
(B) It is suitable for the production of oxide fluorescent particles containing one or more metals selected from Al, Ga, In, Si and Ge, particularly one or more metals selected from Al and Ga. The oxide fluorescent particles are further
(C) One or more metals selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra may be included.
蛍光体として具体的には、下記組成式（１）
（Ａ1-xＢx）3Ｃ5Ｏ12 （１）
（式中、ＡはＹ，Ｇｄ及びＬｕから選ばれる１種類以上の希土類元素、ＢはＣｅ，Ｎｄ及びＴｂから選ばれる１種類以上の希土類元素、ＣはＡｌ及びＧａから選ばれる１種類以上の元素であり、ｘは０．００２≦ｘ≦０．２である。）
で示されるガーネット相（ＹＡＧ相）を含有する蛍光体が挙げられる。このガーネット相は、蛍光粒子における主相であり、粒子中、通常、９９体積％以上がガーネット相であることが好ましい。また、蛍光体としては、（Ｂａ，Ｓｒ，Ｃａ）2ＳｉＯ4：Ｅｕ、（Ｂａ，Ｓｒ，Ｃａ）3ＳｉＯ5：Ｅｕ等のシリケート系蛍光体も好適である。
Specifically, as the phosphor, the following composition formula (1)
(A 1-x B x ) 3 C 5 O 12 (1)
Wherein A is one or more rare earth elements selected from Y, Gd and Lu, B is one or more rare earth elements selected from Ce, Nd and Tb, and C is one or more kinds selected from Al and Ga. And x is 0.002 ≦ x ≦ 0.2.)
And a phosphor containing a garnet phase (YAG phase) shown in FIG. This garnet phase is the main phase in the fluorescent particles, and it is preferable that 99% by volume or more of the particles is usually the garnet phase. As the phosphor, silicate phosphors such as (Ba, Sr, Ca) 2 SiO 4 : Eu and (Ba, Sr, Ca) 3 SiO 5 : Eu are also suitable.
このような酸化物蛍光粒子は、製造する蛍光体の種類に応じて、（Ａ）成分の金属と、（Ｂ）成分の金属と、必要に応じて（Ｃ）成分の金属とを適宜選定し、それらを含む金属単体、金属２成分以上からなる合金、又はそれらの混合物を金属材料として用いて、溶融、微粒子化及び酸化の各処理を実施すればよい。 For such oxide fluorescent particles, the metal of component (A), the metal of component (B), and the metal of component (C) are appropriately selected according to the type of phosphor to be produced. In addition, each of the melting, atomization, and oxidation treatments may be performed using a single metal containing them, an alloy composed of two or more metal components, or a mixture thereof as a metal material.
本発明の製造方法により、平均粒径が５０μｍ以下、特に５〜５０μｍの酸化物蛍光粒子を製造することができる。平均粒径はＤ５０（メジアン径：累積５０ｖｏｌ％における粒径）として求めることができる。 By the production method of the present invention, oxide fluorescent particles having an average particle size of 50 μm or less, particularly 5 to 50 μm can be produced. An average particle diameter can be calculated | required as D50 (median diameter: particle diameter in accumulation 50 vol%).
また、本発明の製造方法により、平均真円度が０．３以下、特に０．２以下、とりわけ０．１以下の酸化物蛍光粒子を製造することができる。平均真円度の下限は理想的には０であるが、通常０．０１以上である。真円度は、電子顕微鏡等による観察などにより得られる粒子の投影像において、その外周に対する外接円の直径と内接円の直径とを計測し、これらから、下記式
真円度＝｛（外接円の直径）−（内接円の直径）｝／［｛（外接円の直径）＋（内接円の直径）｝÷２］
から求めることができる。
In addition, by the production method of the present invention, oxide fluorescent particles having an average roundness of 0.3 or less, particularly 0.2 or less, and particularly 0.1 or less can be produced. The lower limit of the average roundness is ideally 0, but is usually 0.01 or more. The roundness is measured by measuring the diameter of the circumscribed circle and the diameter of the inscribed circle with respect to the outer periphery of the projected image of the particle obtained by observation with an electron microscope or the like. Circle diameter)-(diameter of inscribed circle)} / [{(diameter of circumscribed circle) + (diameter of inscribed circle)} / 2]
Can be obtained from
更に、本発明の製造方法により、安息角が１〜４０°、特に２〜３０°、とりわけ５〜２０°である酸化物蛍光粒子を製造することができる。 Furthermore, oxide fluorescent particles having an angle of repose of 1 to 40 °, particularly 2 to 30 °, and particularly 5 to 20 ° can be produced by the production method of the present invention.
安息角が小さい流動性が高い蛍光粒子は、封止樹脂への充填再現性がよく、ＬＥＤ等の発光デバイスに用いられる封止樹脂を含む蛍光体層を薄くすることができる。封止樹脂は熱劣化・紫外線劣化により着色するので、封止樹脂を減らすことによりＬＥＤ寿命を延ばすことができる。更に、分散指数が低く粒度分布が狭い蛍光粒子は、青色ＬＥＤと黄色発光蛍光体で擬似白色を発する白色ＬＥＤの場合、青色と黄色のＬＥＤ内の色均一性が高い白色ＬＥＤを与える。 The fluorescent particles having a small repose angle and high fluidity have good reproducibility of filling the sealing resin, and can make the phosphor layer containing the sealing resin used in a light emitting device such as an LED thin. Since the sealing resin is colored due to heat deterioration and ultraviolet light deterioration, the life of the LED can be extended by reducing the sealing resin. Further, the fluorescent particles having a low dispersion index and a narrow particle size distribution give a white LED having high color uniformity in the blue and yellow LEDs in the case of a white LED emitting a pseudo white color with a blue LED and a yellow light emitting phosphor.
本発明の蛍光粒子は、ＬＥＤ等の発光デバイス等に好適に用いることができ、例えば、蛍光粒子を波長変換材料として、励起光を発光する発光体上に積層して用いることができ、発光ダイオードの波長変換用の蛍光体として好適である。本発明の蛍光粒子を用いると、これをエポキシ樹脂、シリコーン樹脂等の樹脂、無機ガラス等に分散して、発光体に積層する積層体を製造する際、積層体中で均一分散が可能であり、積層体の基材中の分散性が良好となり、蛍光粒子のばらつきが少ない積層体を得ることができる。 The fluorescent particles of the present invention can be suitably used for light emitting devices such as LEDs. For example, the fluorescent particles can be used by being stacked on a light emitting body that emits excitation light using a fluorescent particle as a wavelength conversion material. It is suitable as a phosphor for wavelength conversion. When the fluorescent particles of the present invention are used, they can be dispersed in an epoxy resin, a resin such as a silicone resin, inorganic glass, etc. to produce a laminate to be laminated on a light emitter, and can be uniformly dispersed in the laminate. In addition, the dispersibility of the laminate in the base material becomes good, and a laminate with little variation in fluorescent particles can be obtained.
本発明の蛍光粒子は、発光ダイオードに用いられる発光素子からの光を波長変換するために用いる蛍光体として好適であり、本発明の蛍光粒子は、発光ダイオード、これを用いた照明装置、液晶パネル用バックライト装置などに好適に使用できる。 The fluorescent particle of the present invention is suitable as a phosphor used for wavelength conversion of light from a light emitting element used in a light emitting diode. The fluorescent particle of the present invention is a light emitting diode, an illumination device using the same, a liquid crystal panel. It can be suitably used for a backlight device for use.
以下に実施例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
［実施例１］
純度９９．９％のイットリウムと、純度９９．９％のアルミニウムと、純度９９．９％のセリウムとを、各々Ｙ：Ａｌ：Ｃｅ＝２．９４：５：０．０６のモル比でタングステン容器に入れて真空溶解炉で溶融して合金とした。この合金を直径２０ｍｍの円柱状金型に鋳込んで合金棒とした。得られた合金棒を、回転ディスクアトマイザーを用いて球形状の合金粒子とした。得られた球形状の合金粒子は、平均粒径が３５μｍであった。
[Example 1]
A tungsten container containing 99.9% pure yttrium, 99.9% pure aluminum, and 99.9% pure cerium in a molar ratio of Y: Al: Ce = 2.94: 5: 0.06, respectively. And melted in a vacuum melting furnace to obtain an alloy. This alloy was cast into a cylindrical mold having a diameter of 20 mm to obtain an alloy bar. The obtained alloy rod was made into spherical alloy particles using a rotating disk atomizer. The obtained spherical alloy particles had an average particle size of 35 μm.
次に、この合金粒子を大気炉に入れ、昇温速度３０℃／時間で１３００℃まで昇温して、同温度で８時間維持した後、冷却して取り出し、酸化物蛍光粒子を得た。得られた酸化物蛍光粒子をＸＲＤで定性分析したところＹＡＧ相（ガーネット相）であった。このＹＡＧ：Ｃｅ粒子を還元雰囲気炉にて、Ａｒ９８ｖｏｌ％、水素２ｖｏｌ％の雰囲気下、１６００℃で８時間アニールした。アニール後のＹＡＧ：Ｃｅ粒子は４５０ｎｍの励起光で黄色発光を示した。 Next, the alloy particles were put into an atmospheric furnace, heated to 1300 ° C. at a temperature rising rate of 30 ° C./hour, maintained at the same temperature for 8 hours, then cooled and taken out to obtain oxide fluorescent particles. When the obtained oxide fluorescent particles were qualitatively analyzed by XRD, they were YAG phase (garnet phase). The YAG: Ce particles were annealed in a reducing atmosphere furnace at 1600 ° C. for 8 hours in an atmosphere of Ar 98 vol% and hydrogen 2 vol%. The annealed YAG: Ce particles showed yellow emission with 450 nm excitation light.
一方、得られた黄色発光蛍光体のアニール前後の吸収率及び内部量子効率を、励起波長４５０ｎｍ、発光範囲４８０〜７８０ｎｍの範囲で積分球を用いて測定した。結果を表１に示す。アニール後の吸収率は０．９８、内部量子効率は、０．９２と高い値を示した。また、この蛍光粒子の安息角を測定したところ、２２°であり、流動性が非常に良好であった。更に、蛍光粒子を電子顕微鏡で観察したところ、図１に示されるように、球形状乃至略球形状の粒子であり、蛍光粒子の電子顕微鏡像からランダムに３０個を抽出して真円度を画像解析により評価したところ、０．１８（平均値）であった。 On the other hand, the absorptance before and after annealing and the internal quantum efficiency of the obtained yellow light-emitting phosphor were measured using an integrating sphere in an excitation wavelength of 450 nm and an emission range of 480 to 780 nm. The results are shown in Table 1. The absorptance after annealing was 0.98, and the internal quantum efficiency was as high as 0.92. Further, the angle of repose of the fluorescent particles was measured and found to be 22 ° and the fluidity was very good. Furthermore, when the fluorescent particles were observed with an electron microscope, as shown in FIG. 1, they were spherical or substantially spherical particles, and 30 particles were randomly extracted from the electron microscopic image of the fluorescent particles to obtain roundness. When evaluated by image analysis, it was 0.18 (average value).
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