JP6723960B2 - Nitride phosphor and light emitting device - Google Patents
Nitride phosphor and light emitting device Download PDFInfo
- Publication number
- JP6723960B2 JP6723960B2 JP2017160352A JP2017160352A JP6723960B2 JP 6723960 B2 JP6723960 B2 JP 6723960B2 JP 2017160352 A JP2017160352 A JP 2017160352A JP 2017160352 A JP2017160352 A JP 2017160352A JP 6723960 B2 JP6723960 B2 JP 6723960B2
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- phosphor
- nitride
- silicon
- less
- light emitting
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—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
- C09K11/7734—Aluminates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Description
本開示は、窒化物蛍光体及び発光装置に関する。 The present disclosure relates to a nitride phosphor and a light emitting device.
青色光を発する発光素子であるＬＥＤ（Light Emitting Diode）と、この青色光に励起されて緑色発光する蛍光体と、赤色発光する蛍光体とを組み合わせることにより、白色光を放出可能な発光装置が開発されている。例えば、特許文献１には、β型Ｓｉ３Ｎ４結晶構造を有し、緑色に発光するβサイアロン蛍光体と、ＣａＡｌＳｉＮ３：Ｅｕの組成を有する赤色発光の窒化物蛍光体（以下、ＣＡＳＮ蛍光体ともいう）とを、青色ＬＥＤと組合せた白色光を発する発光装置が開示されている。 By combining an LED (Light Emitting Diode) that is a light emitting element that emits blue light, a phosphor that is excited by this blue light to emit green light, and a phosphor that emits red light, a light emitting device that can emit white light is provided. Being developed. For example, in Patent Document 1, a β-sialon phosphor having a β-type Si 3 N 4 crystal structure and emitting green light, and a red-emitting nitride phosphor having a composition of CaAlSiN 3 :Eu (hereinafter referred to as CASN fluorescence) are disclosed. (Also referred to as the body) and a blue LED in combination with a blue LED to emit white light.
またＣＡＳＮ蛍光体のＣａの一部をＳｒに置換した（Ｃａ，Ｓｒ）ＡｌＳｉＮ３：Ｅｕの組成を有する赤色発光の蛍光体（以下、ＳＣＡＳＮ蛍光体ともいう）が知られており、ＣＡＳＮ蛍光体よりも発光ピーク波長を短くすることができるとされている。ＣＡＳＮ蛍光体は、例えば、窒化ケイ素、窒化アルミニウム、窒化カルシウム及び窒化ユウロピウムからなる混合物を焼成することで得られ、ＳＣＡＳＮ蛍光体も同様にして得ることができる（例えば、特許文献２参照）。 Further, a red light emitting phosphor (hereinafter also referred to as SCASN phosphor) having a composition of (Ca,Sr)AlSiN 3 :Eu in which a part of Ca of the CASN phosphor is replaced by Sr is known, and the CASN phosphor is also known. It is said that the emission peak wavelength can be made shorter than that. The CASN phosphor can be obtained, for example, by firing a mixture of silicon nitride, aluminum nitride, calcium nitride and europium nitride, and the SCASN phosphor can be obtained in the same manner (see, for example, Patent Document 2).
発光装置の輝度向上の要求から、発光輝度がより高いＣＡＳＮ蛍光体等の窒化物蛍光体が求められている。本開示に係る一実施形態は、発光輝度の高い窒化物蛍光体を提供することを目的とする。 In order to improve the brightness of the light emitting device, a nitride phosphor such as a CASN phosphor having higher emission brightness is required. An embodiment of the present disclosure aims to provide a nitride phosphor with high emission brightness.
本発明者等は、上記課題に鑑みて更に鋭意研究を重ねた結果、原料を特定の構成にして窒化物蛍光体を製造することで、得られる窒化物蛍光体の発光輝度が向上することを見出し、本発明を完成させた。本発明は以下の態様を包含する。
第一の態様は、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含み、ＢＥＴ法による比表面積が０．１ｃｍ２／ｇ以上０．１６ｃｍ２／ｇ以下であり、平均粒径が２０μｍ以上３０μｍ以下である窒化物蛍光体である。
As a result of further intensive studies in view of the above problems, the inventors of the present invention have manufactured a nitride phosphor with a raw material having a specific structure, thereby improving the emission brightness of the obtained nitride phosphor. Heading, completed the present invention. The present invention includes the following aspects.
The first embodiment includes the alkaline earth metal, aluminum, silicon and europium, the specific surface area by the BET method is not less less 0.1 cm 2 / g or more 0.16 cm 2 / g, an average particle diameter of 20μm or more 30μm or less Which is a nitride phosphor.
本発明に係る一実施形態によれば、発光輝度の高い窒化物蛍光体を提供することができる。 According to one embodiment of the present invention, it is possible to provide a nitride phosphor with high emission brightness.
以下、本発明に係る窒化物蛍光体の製造方法を、実施の形態に基づいて説明する。ただし、以下に示す実施の形態は、本発明の技術思想を例示するものであって、本発明は、以下の窒化物蛍光体の製造方法に限定されない。なお、色名と色度座標との関係、光の波長範囲と単色光の色名との関係等は、ＪＩＳ Ｚ８１１０に従う。また「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。さらに組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 Hereinafter, a method for manufacturing a nitride phosphor according to the present invention will be described based on the embodiments. However, the embodiments described below exemplify the technical idea of the present invention, and the present invention is not limited to the following method for manufacturing a nitride phosphor. Note that the relationship between the color name and the chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, and the like comply with JIS Z8110. The term “process” is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
［窒化物蛍光体の製造方法］
窒化物蛍光体の製造方法は、窒化ケイ素、ケイ素、アルミニウム化合物、カルシウム化合物及びユウロピウム化合物を含む原料混合物を熱処理することを含む。窒化物蛍光体は、例えば下記式（Ｉ）で表される組成を有する。
ＳｒｓＣａｔＡｌｕＳｉｖＮｗ：Ｅｕ （Ｉ）
ここでｓ、ｔ、ｕ、ｖ及びｗはそれぞれ、０．０≦ｓ＜１、０＜ｔ≦１、ｓ＋ｔ≦１、０．９≦ｕ≦１．１、０．９≦ｖ≦１．１、及び２．５≦ｗ≦３．５を満たす。
[Method for producing nitride phosphor]
The method for manufacturing a nitride phosphor includes heat treating a raw material mixture containing silicon nitride, silicon, an aluminum compound, a calcium compound and a europium compound. The nitride phosphor has, for example, a composition represented by the following formula (I).
Sr s Ca t Al u Si v N w: Eu (I)
Here, s, t, u, v, and w are 0.0≦s<1, 0<t≦1, s+t≦1, 0.9≦u≦1.1, and 0.9≦v≦1, respectively. 1 and 2.5≦w≦3.5 are satisfied.
原料混合物は、ケイ素源として窒化ケイ素に加えてケイ素単体も含む。詳細は不明だが、熱処理時においてケイ素単体は窒化されながら反応すると考えられ、これに起因して高温の熱処理による焼結が生じにくくなるものと考えられる。したがって、粒径が大きい窒化物蛍光体を得ることができる。得られる窒化物蛍光体は、発光効率が高く、発光輝度が向上する。 The raw material mixture also contains elemental silicon in addition to silicon nitride as a silicon source. Although the details are unknown, it is considered that the silicon simple substance reacts while being nitrided during the heat treatment, and it is considered that this makes it difficult to cause sintering due to the high temperature heat treatment. Therefore, a nitride phosphor having a large particle size can be obtained. The obtained nitride phosphor has high luminous efficiency and improved luminous brightness.
原料混合物は、窒化ケイ素と、ケイ素と、アルミニウム化合物の少なくとも１種と、ユウロピウム化合物の少なくとも１種とを含む。 The raw material mixture contains silicon nitride, silicon, at least one aluminum compound, and at least one europium compound.
窒化ケイ素は、窒素原子及びケイ素原子を含むケイ素化合物であり、酸素原子を含む窒化ケイ素であってもよい。窒化ケイ素が酸素原子を含む場合、酸素原子は酸化ケイ素として含まれていてもよく、ケイ素の酸窒化物として含まれていてもよい。
窒化ケイ素に含まれる酸素原子の含有率は、例えば２重量％未満であり、１．５重量％以下が好ましい。また酸素原子の含有率は、例えば０．３重量％以上であり、０．４重量％以上が好ましい。酸素量を所定値以上とすることにより反応性を高め、粒子成長を促進することができる。また、酸素量を所定値以下とすることにより、蛍光体粒子の過剰な焼結を抑制し、蛍光体粒子の形状を良化することができる。
窒化ケイ素の純度は、例えば９５重量％以上であり、９９重量％以上が好ましい。窒化ケイ素の純度を所定値以上とすることにより、不純物の影響を少なくして、窒化物蛍光体の発光輝度をより向上させることができる。
Silicon nitride is a silicon compound containing nitrogen atoms and silicon atoms, and may be silicon nitride containing oxygen atoms. When silicon nitride contains an oxygen atom, the oxygen atom may be included as silicon oxide or may be included as an oxynitride of silicon.
The content of oxygen atoms contained in silicon nitride is, for example, less than 2% by weight, preferably 1.5% by weight or less. The oxygen atom content is, for example, 0.3% by weight or more, preferably 0.4% by weight or more. By setting the oxygen amount to a predetermined value or more, the reactivity can be enhanced and the particle growth can be promoted. Further, by setting the amount of oxygen to a predetermined value or less, it is possible to suppress excessive sintering of the phosphor particles and improve the shape of the phosphor particles.
The purity of silicon nitride is, for example, 95% by weight or more, preferably 99% by weight or more. By setting the purity of silicon nitride to a predetermined value or more, the influence of impurities can be reduced and the emission brightness of the nitride phosphor can be further improved.
窒化ケイ素の平均粒径は、例えば０．１μｍ以上１５μｍ以下であり、０．１μｍ以上５μｍ以下が好ましい。窒化ケイ素の平均粒径を所定値以下とすることにより窒化物蛍光体の製造時の反応性を向上させることができる。窒化ケイ素の平均粒径を所定値以上とすることにより、窒化物蛍光体の製造時における過剰な反応を抑制して蛍光体粒子の焼結を防ぐことができる。 The average particle size of silicon nitride is, for example, 0.1 μm or more and 15 μm or less, and preferably 0.1 μm or more and 5 μm or less. By setting the average particle size of silicon nitride to be a predetermined value or less, it is possible to improve the reactivity during the production of the nitride phosphor. By setting the average particle diameter of silicon nitride to be a predetermined value or more, it is possible to suppress excessive reaction during the production of the nitride phosphor and prevent sintering of the phosphor particles.
窒化ケイ素は、市販品から適宜選択して用いてもよく、ケイ素を窒化して製造して用いてもよい。窒化ケイ素は、例えば、原料となるケイ素を希ガス、窒素ガス等の不活性ガス雰囲気中で粉砕し、得られる粉体を窒素雰囲気中で熱処理して窒化することで得ることができる。原料に用いるケイ素単体は高純度であることが好ましく、その純度は例えば３Ｎ（９９．９重量％）以上である。粉砕したケイ素の平均粒径は、例えば０．１μｍ以上１５μｍ以下である。また熱処理温度は、例えば８００℃以上２０００℃以下であり、熱処理時間は、例えば１時間以上２０時間以下である。
得られた窒化ケイ素には、例えば、窒素雰囲気中で粉砕処理を行うことができる。
Silicon nitride may be appropriately selected and used from commercial products, or may be produced by nitriding silicon and used. Silicon nitride can be obtained, for example, by pulverizing raw material silicon in an atmosphere of an inert gas such as a rare gas or nitrogen gas, and heat-treating the obtained powder in a nitrogen atmosphere to nitride. The simple substance of silicon used as the raw material is preferably highly pure, and its purity is, for example, 3N (99.9% by weight) or more. The average particle size of the crushed silicon is, for example, 0.1 μm or more and 15 μm or less. The heat treatment temperature is, for example, 800° C. or more and 2000° C. or less, and the heat treatment time is, for example, 1 hour or more and 20 hours or less.
The obtained silicon nitride can be pulverized in a nitrogen atmosphere, for example.
原料混合物に含まれるケイ素は単体のケイ素である。ケイ素の純度は、例えば９５重量％以上であり、９９．９重量％以上が好ましい。ケイ素の純度を所定値以上とすることにより、不純物の影響を少なくして蛍光体の輝度をより向上することができる。
ケイ素の平均粒径は、例えば０．１μｍ以上１００μｍ以下であり、０．１μｍ以上８０μｍ以下が好ましい。ケイ素の平均粒径を所定値以下とすることにより、粒子の内部まで十分に窒化することができる。ケイ素の平均粒径を所定値以上とすることにより、窒化物蛍光体の製造時における過剰な反応を抑制して蛍光体粒子の焼結を抑制することができる。
The silicon contained in the raw material mixture is elemental silicon. The purity of silicon is, for example, 95% by weight or more, preferably 99.9% by weight or more. By setting the purity of silicon to a predetermined value or higher, the influence of impurities can be reduced and the brightness of the phosphor can be further improved.
The average particle size of silicon is, for example, 0.1 μm or more and 100 μm or less, and preferably 0.1 μm or more and 80 μm or less. By setting the average particle diameter of silicon to be equal to or less than the predetermined value, it is possible to sufficiently nitride the inside of the particles. By setting the average particle diameter of silicon to a predetermined value or more, it is possible to suppress excessive reaction during the production of the nitride phosphor and suppress sintering of the phosphor particles.
原料混合物は、窒化ケイ素及びケイ素単体の一部を酸化ケイ素等の他のケイ素化合物に置換した混合物であってもよい。すなわち原料混合物は、窒化ケイ素及びケイ素単体に加えて酸化ケイ素等のケイ素化合物を含むものであってもよい。ケイ素化合物には、酸化ケイ素、酸窒化ケイ素、ケイ酸塩等が含まれる。 The raw material mixture may be a mixture obtained by substituting silicon nitride and a part of silicon simple substance with another silicon compound such as silicon oxide. That is, the raw material mixture may contain a silicon compound such as silicon oxide in addition to silicon nitride and silicon simple substance. The silicon compound includes silicon oxide, silicon oxynitride, silicate and the like.
また原料混合物は窒化ケイ素及びケイ素単体の一部を、ゲルマニウム、スズ、チタン、ジルコニウム、ハフニウム等の第IV族元素の金属化合物、金属単体、合金等に置換した混合物であってもよい。金属化合物としては、酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。 Further, the raw material mixture may be a mixture obtained by substituting a part of silicon nitride and a simple substance of silicon with a metal compound of a Group IV element such as germanium, tin, titanium, zirconium, hafnium, a simple substance of metal or an alloy. Examples of the metal compound include oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides.
原料混合物における窒化ケイ素及びケイ素の総量に対するケイ素の重量比率は、例えば１０重量％以上８５重量％以下であり、２０重量％以上８０重量％以下が好ましく、３０重量％以上８０重量％以下がより好ましい。ケイ素の重量比率を所定値以上とすることにより、窒化物蛍光体の粒子成長時における焼結を抑えることができる。また、窒化ケイ素にはケイ素の窒化反応を促進する作用もあるため、ケイ素の重量比率を所定値以下とする（窒化ケイ素の重量比率を大きくする）ことにより、ケイ素を十分に窒化することができる。 The weight ratio of silicon to the total amount of silicon nitride and silicon in the raw material mixture is, for example, 10% by weight or more and 85% by weight or less, preferably 20% by weight or more and 80% by weight or less, and more preferably 30% by weight or more and 80% by weight or less. .. By setting the weight ratio of silicon to a predetermined value or more, it is possible to suppress the sintering of the nitride phosphor during grain growth. Further, since silicon nitride also has an action of promoting the nitriding reaction of silicon, by setting the weight ratio of silicon to a predetermined value or less (increasing the weight ratio of silicon nitride), silicon can be sufficiently nitrided. ..
アルミニウム化合物としては、アルミニウムを含む酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。またアルミニウム化合物の少なくとも一部に代えてアルミニウム金属単体又はアルミニウム合金等を用いてもよい。アルミニウム化合物として具体的には、窒化アルミニウム（ＡｌＮ）、酸化アルミニウム（Ａｌ２Ｏ３）、水酸化アルミニウム（Ａｌ（ＯＨ）３）等を挙げることができ、これらからなる群から選択される少なくとも１種を用いることが好ましく、窒化アルミニウムがより好ましい。窒化アルミニウムは目的とする蛍光体組成に含まれる元素のみで構成されているため、不純物の混入をより効果的に抑制できる。窒化アルミニウムは、例えば、酸素や水素を含むアルミニウム化合物と比較して、それらの元素の影響を少なくすることができ、金属単体と比較して窒化反応が不要である。アルミニウム化合物は１種単独でも、２種以上を組合せて用いてもよい。 Examples of the aluminum compound include oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides containing aluminum. Further, instead of at least a part of the aluminum compound, a simple substance of aluminum metal or an aluminum alloy may be used. Specific examples of the aluminum compound include aluminum nitride (AlN), aluminum oxide (Al 2 O 3 ), aluminum hydroxide (Al(OH) 3 ), and the like, and at least one selected from the group consisting of these. It is preferred to use seeds, more preferably aluminum nitride. Since aluminum nitride is composed only of the elements contained in the intended phosphor composition, the incorporation of impurities can be suppressed more effectively. Aluminum nitride can reduce the influence of these elements as compared with, for example, an aluminum compound containing oxygen and hydrogen, and does not require a nitriding reaction as compared with a simple metal. The aluminum compounds may be used alone or in combination of two or more.
原料として用いるアルミニウム化合物の平均粒径は、例えば０．１μｍ以上１５μｍ以下であり、０．１μｍ以上１０μｍ以下が好ましい。平均粒径を所定値以下とすることにより窒化物蛍光体の製造時における反応性を向上させることができる。平均粒径を所定値以上とすることにより、窒化物蛍光体の製造時における蛍光体粒子の焼結を防ぐことができる。
またアルミニウム化合物の純度は、例えば９５重量％以上であり、９９重量％以上が好ましい。純度を所定値以上とすることにより、不純物の影響を少なくして蛍光体の発光輝度をより向上することができる。
The average particle size of the aluminum compound used as a raw material is, for example, 0.1 μm or more and 15 μm or less, and preferably 0.1 μm or more and 10 μm or less. By setting the average particle diameter to a predetermined value or less, it is possible to improve the reactivity during the production of the nitride phosphor. By setting the average particle size to a predetermined value or more, it is possible to prevent the phosphor particles from being sintered during the production of the nitride phosphor.
The purity of the aluminum compound is, for example, 95% by weight or more, preferably 99% by weight or more. By setting the purity to a predetermined value or more, the influence of impurities can be reduced and the emission brightness of the phosphor can be further improved.
アルミニウム化合物は、市販品から適宜選択して用いてもよく、所望のアルミニウム化合物を製造して用いてもよい。例えば窒化アルミニウムはアルミニウムの直接窒化法等により製造することができる。 The aluminum compound may be appropriately selected from commercially available products and used, or a desired aluminum compound may be produced and used. For example, aluminum nitride can be manufactured by a direct nitriding method of aluminum or the like.
原料混合物はアルミニウム化合物の少なくとも一部を、ガリウム、インジウム、バナジウム、クロム、コバルト等の第III族元素の金属化合物、金属単体、合金等に置換した混合物であってもよい。金属化合物としては、酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。 The raw material mixture may be a mixture obtained by substituting at least a part of the aluminum compound with a metal compound of a Group III element such as gallium, indium, vanadium, chromium, or cobalt, a simple metal, or an alloy. Examples of the metal compound include oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides.
カルシウム化合物としては、カルシウムを含む水素化物、酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。またカルシウム化合物の少なくとも一部に代えてカルシウム金属単体又はカルシウム合金等を用いてもよい。カルシウム化合物として具体的には、水素化カルシウム（ＣａＨ２）、窒化カルシウム（Ｃａ３Ｎ２）、酸化カルシウム（ＣａＯ）、水酸化カルシウム（Ｃａ（ＯＨ）２）等の無機化合物、及びイミド化合物、アミド化合物等の有機化合物塩を挙げることができ、これらからなる群から選択される少なくとも１種を用いることが好ましく、窒化カルシウムがより好ましい。窒化カルシウムは目的とする蛍光体組成に含まれる元素のみで構成されているため、不純物の混入をより効果的に抑制できる。窒化カルシウムは、例えば、酸素や水素を含むカルシウム化合物と比較して、それらの元素の影響を少なくすることができ、金属単体と比較して窒化反応が不要である。カルシウム化合物は１種単独でも、２種以上を組合せて用いてもよい。 Examples of calcium compounds include hydrides, oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides containing calcium. Moreover, you may use a calcium metal simple substance or a calcium alloy etc. instead of at least one part of a calcium compound. Specific examples of the calcium compound include calcium hydride (CaH 2 ), calcium nitride (Ca 3 N 2 ), calcium oxide (CaO), calcium hydroxide (Ca(OH) 2 ), and other inorganic compounds, and imide compounds. Examples thereof include organic compound salts such as amide compounds, and it is preferable to use at least one selected from the group consisting of these, and calcium nitride is more preferable. Since calcium nitride is composed only of the elements contained in the intended phosphor composition, it is possible to more effectively suppress the inclusion of impurities. Calcium nitride can reduce the influence of those elements as compared with, for example, a calcium compound containing oxygen and hydrogen, and does not require a nitriding reaction as compared with a simple metal. The calcium compounds may be used alone or in combination of two or more.
原料として用いるカルシウム化合物の平均粒径は、例えば０．１μｍ以上１００μｍ以下であり、０．１μｍ以上８０μｍ以下が好ましい。平均粒径を所定値以下とすることにより窒化物蛍光体の製造時における反応性を向上させることができる。平均粒径を所定値以上とすることにより、窒化物蛍光体の製造時における蛍光体粒子の焼結を防ぐことができる。
またカルシウム化合物の純度は、例えば９５重量％以上であり、９９重量％以上が好ましい。純度を所定値以上とすることにより、不純物の影響を少なくして蛍光体の発光輝度をより向上することができる。
The average particle size of the calcium compound used as the raw material is, for example, 0.1 μm or more and 100 μm or less, and preferably 0.1 μm or more and 80 μm or less. By setting the average particle diameter to a predetermined value or less, it is possible to improve the reactivity during the production of the nitride phosphor. By setting the average particle size to a predetermined value or more, it is possible to prevent the phosphor particles from being sintered during the production of the nitride phosphor.
The purity of the calcium compound is, for example, 95% by weight or more, preferably 99% by weight or more. By setting the purity to a predetermined value or more, the influence of impurities can be reduced and the emission brightness of the phosphor can be further improved.
カルシウム化合物は、市販品から適宜選択して用いてもよく、所望のカルシウム化合物を製造して用いてもよい。例えば、窒化カルシウムは、原料となるカルシウムを不活性ガス雰囲気中で粉砕し、得られた粉体を窒素雰囲気中で熱処理して窒化することで得ることができる。原料に用いるカルシウムは高純度であることが好ましく、その純度は例えば２Ｎ（９９重量％）以上である。粉砕したカルシウムの平均粒径は、例えば０．１μｍ以上１５μｍ以下である。また熱処理温度は、例えば６００℃以上９００℃以下であり、熱処理時間は、例えば１時間以上２０時間以下である。
得られた窒化カルシウムには、例えば、不活性ガス雰囲気中で粉砕処理を行うことができる。
The calcium compound may be appropriately selected and used from commercially available products, or a desired calcium compound may be produced and used. For example, calcium nitride can be obtained by pulverizing raw material calcium in an inert gas atmosphere and subjecting the obtained powder to heat treatment in a nitrogen atmosphere to nitride. The calcium used as a raw material is preferably highly pure, and its purity is, for example, 2N (99% by weight) or more. The average particle size of the crushed calcium is, for example, 0.1 μm or more and 15 μm or less. The heat treatment temperature is, for example, 600° C. or higher and 900° C. or lower, and the heat treatment time is, for example, 1 hour or longer and 20 hours or shorter.
The obtained calcium nitride can be pulverized in an inert gas atmosphere, for example.
原料混合物はカルシウム化合物の少なくとも一部を、マグネシウム、バリウム等のアルカリ土類金属；リチウム、ナトリウム、カリウム等のアルカリ金属；ホウ素、アルミニウム等の第III族元素；の金属化合物、金属単体、合金等に置換した混合物であってもよい。金属化合物としては、水素化物、酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。 The raw material mixture contains at least a part of a calcium compound, an alkaline earth metal such as magnesium and barium; an alkali metal such as lithium, sodium and potassium; a group III element such as boron and aluminum; a metal compound, a simple metal, an alloy, etc. It may be a mixture substituted with. Examples of metal compounds include hydrides, oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides.
ユウロピウム化合物としては、ユウロピウムを含む酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。またユウロピウム化合物の少なくとも一部に代えてユウロピウム金属単体又はユウロピウム合金等を用いてもよい。ユウロピウム化合物として具体的には、酸化ユウロピウム（Ｅｕ２Ｏ３）、窒化ユウロピウム（ＥｕＮ）、フッ化ユウロピウム（ＥｕＦ３）等を挙げることができ、これらからなる群から選択される少なくとも１種が好ましく、酸化ユウロピウムがより好ましい。窒化ユウロピウム（ＥｕＮ）は、目的とする蛍光体組成に含まれる元素のみで構成されているため、不純物の混入をより効果的に抑制できる。また、酸化ユウロピウム（Ｅｕ２Ｏ３）、フッ化ユウロピウム（ＥｕＦ３）はフラックスとしても作用があり、好ましく用いられる。ユウロピウム化合物は１種単独でも、２種以上を組合せて用いてもよい。 Examples of the europium compound include oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides containing europium. Further, a europium metal simple substance, a europium alloy or the like may be used instead of at least a part of the europium compound. Specific examples of the europium compound include europium oxide (Eu 2 O 3 ), europium nitride (EuN), europium fluoride (EuF 3 ), and the like, and at least one selected from the group consisting of these is preferable. , Europium oxide is more preferable. Since europium nitride (EuN) is composed only of the elements contained in the intended phosphor composition, it is possible to more effectively suppress the inclusion of impurities. Further, europium oxide (Eu 2 O 3 ) and europium fluoride (EuF 3 ) have a function as a flux and are preferably used. The europium compounds may be used alone or in combination of two or more.
原料として用いるユウロピウム化合物の平均粒径は、例えば０．０１μｍ以上２０μｍ以下であり、０．０５μｍ以上１０μｍ以下が好ましい。ユウロピウム化合物の平均粒径を所定値以上とすることにより、製造時における蛍光体粒子の凝集を抑制できる。ユウロピウム化合物の平均粒径を所定値以下とすることにより、より均一に賦活された蛍光体粒子を得ることができる。
またユウロピウム化合物の純度は、例えば９５重量％以上であり、９９．５重量％以上が好ましい。純度を所定値以上とすることにより、不純物の影響を少なくして蛍光体の発光輝度をより向上することができる。
The average particle size of the europium compound used as the raw material is, for example, 0.01 μm or more and 20 μm or less, preferably 0.05 μm or more and 10 μm or less. By setting the average particle size of the europium compound to be a predetermined value or more, it is possible to suppress the aggregation of the phosphor particles during production. By setting the average particle size of the europium compound to be a predetermined value or less, more uniformly activated phosphor particles can be obtained.
The purity of the europium compound is, for example, 95% by weight or more, preferably 99.5% by weight or more. By setting the purity to a predetermined value or more, the influence of impurities can be reduced and the emission brightness of the phosphor can be further improved.
ユウロピウム化合物は、市販品から適宜選択して用いてもよく、所望のユウロピウム化合物を製造して用いてもよい。例えば、窒化ユウロピウムは、原料となるユウロピウムを不活性ガス雰囲気中で粉砕し、得られた粉体を窒素雰囲気中で熱処理して窒化することで得ることができる。粉砕したユウロピウムの平均粒径は、例えば０．１μｍ以上１０μｍ以下である。また熱処理温度は、例えば６００℃以上１２００℃以下であり、熱処理時間は、例えば１時間以上２０時間以下である。
得られた窒化ユウロピウムは、例えば、不活性ガス雰囲気中で粉砕処理を行うことができる。
The europium compound may be appropriately selected and used from commercial products, or a desired europium compound may be produced and used. For example, europium nitride can be obtained by pulverizing europium as a raw material in an inert gas atmosphere, and heat-treating the obtained powder in a nitrogen atmosphere to nitride. The average particle size of the pulverized europium is, for example, 0.1 μm or more and 10 μm or less. The heat treatment temperature is, for example, 600° C. or more and 1200° C. or less, and the heat treatment time is, for example, 1 hour or more and 20 hours or less.
The obtained europium nitride can be pulverized in an inert gas atmosphere, for example.
原料混合物はユウロピウム化合物の少なくとも一部を、スカンジウム（Ｓｃ）、イットリウム（Ｙ）、ランタン（Ｌａ）、セリウム（Ｃｅ），プラセオジム（Ｐｒ）、ネオジム（Ｎｄ）、サマリウム（Ｓｍ）、ガドリニウム（Ｇｄ）、テルビウム（Ｔｂ）、ジスプロシウム（Ｄｙ）、ホルミウム（Ｈｏ）、エルビウム（Ｅｒ）、ツリウム（Ｔｍ），イッテルビウム（Ｙｂ），ルテチウム（Ｌｕ）等の希土類元素の金属化合物、金属単体、合金等に置換した混合物であってもよい。金属化合物としては、酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。 The raw material mixture contains at least a part of the europium compound, scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd). Substituted with rare earth metal compounds such as terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu), simple metals, alloys It may be a mixture. Examples of the metal compound include oxides, hydroxides, nitrides, oxynitrides, fluorides and chlorides.
原料混合物は、必要に応じてカルシウム化合物の一部を、ストロンチウム化合物、金属ストロンチウム、ストロンチウム合金等に置換した混合物であってもよい。ストロンチウム化合物としては、ストロンチウムを含む水素化物、酸化物、水酸化物、窒化物、酸窒化物、フッ化物、塩化物等を挙げることができる。 The raw material mixture may be a mixture in which a part of the calcium compound is replaced with a strontium compound, a metal strontium, a strontium alloy, or the like, if necessary. Examples of the strontium compound include hydride, oxide, hydroxide, nitride, oxynitride, fluoride and chloride containing strontium.
ストロンチウム化合物は、市販品から適宜選択してもよく、所望のストロンチウム化合物を製造して用いてもよい。例えば、窒化ストロンチウムは、窒化カルシウムと同様にして製造することができる。ストロンチウムの窒化物は、カルシウムの窒化物と異なり、窒素量が任意の値を取りやすく、ＳｒＮｘとして表される。ここでｘは、例えば０．５以上１以下である。 The strontium compound may be appropriately selected from commercial products, or a desired strontium compound may be produced and used. For example, strontium nitride can be manufactured similarly to calcium nitride. Unlike the nitride of strontium, the nitride of strontium easily has an arbitrary amount of nitrogen and is represented as SrN x . Here, x is, for example, 0.5 or more and 1 or less.
原料混合物がストロンチウム原子を含む場合、原料混合物中のカルシウム原子とストロンチウム原子の総量中のストロンチウム原子数の比率は、例えば０．１モル％以上９９．９モル％以下であり、０．１モル％以上９８モル％以下が好ましい。このようなストロンチウム原子の含有量とすることにより、窒化物蛍光体の発光ピーク波長を所望の値に調整することができる。 When the raw material mixture contains strontium atoms, the ratio of the number of strontium atoms in the total amount of calcium atoms and strontium atoms in the raw material mixture is, for example, 0.1 mol% or more and 99.9 mol% or less, and 0.1 mol% It is preferably not less than 98 mol% and not more than 98 mol %. By setting the content of such strontium atom, the emission peak wavelength of the nitride phosphor can be adjusted to a desired value.
原料混合物における窒化ケイ素、ケイ素、アルミニウム化合物、カルシウム化合物及びユウロピウム化合物の混合比は、上記式（Ｉ）で表される組成を有する窒化物蛍光体が得られる限り特に制限されず、所望の組成に応じて適宜選択すればよい。例えば、原料混合物に含まれるケイ素原子とアルミニウム原子とのモル比はｕ：ｖであり、好ましくは０．９:１．１以上１．１：０．９以下である。また、カルシウム原子（場合によりストロンチウム原子を含む）とアルミニウム原子とのモル比は、（ｓ＋ｔ）：ｕであり、好ましくは０．９:１以上１．１１：１以下である。また、カルシウム原子（場合によりストロンチウム原子を含む）及びユウロピウム原子の総モル量中のユウロピウム原子のモル比は、例えば１：０．０５以上１：０．００１以下であり、好ましくは１：０．０３以上１：０．００３以下である。 The mixing ratio of silicon nitride, silicon, an aluminum compound, a calcium compound and a europium compound in the raw material mixture is not particularly limited as long as the nitride phosphor having the composition represented by the above formula (I) is obtained, and the desired composition is obtained. It may be selected as appropriate. For example, the molar ratio of silicon atoms and aluminum atoms contained in the raw material mixture is u:v, preferably 0.9:1.1 or more and 1.1:0.9 or less. The molar ratio of calcium atoms (including strontium atoms in some cases) and aluminum atoms is (s+t):u, and preferably 0.9:1 or more and 1.11:1 or less. The molar ratio of europium atoms in the total molar amount of calcium atoms (including strontium atoms in some cases) and europium atoms is, for example, 1:0.05 or more and 1:0.001 or less, preferably 1:0. It is 03 or more and 1:0.003 or less.
例えば、Ｃａ：Ｅｕ：Ａｌ：Ｓｉ＝０．９９３：０．００７：１：１の組成比となるように、窒化カルシウム、酸化ユウロピウム、窒化アルミニウム、窒化ケイ素及びケイ素を混合して原料混合物を調製し、後述する方法で熱処理することにより、
Ｃａ０．９９３Ｅｕ０．００７ＡｌＳｉＮ３
で表される窒化物蛍光体を得ることができる。
ただし、この窒化物蛍光体の組成は、原料混合物の配合比率より推定される代表組成である。酸化ユウロピウムを用いていること、更に各原料には１重量％程度の酸素を含むために、得られる蛍光体中にも実際には一定量の酸素を含む場合があるが、代表組成を示すために酸素を除いた化学式で示している。また、熱処理の際に原料の一部が分解し、飛散等が生じたりするため仕込みの組成とは多少異なることもあり得る。しかしながら、各原料の配合比率を変更することにより、目的とする窒化物蛍光体の組成を変更することができる。ここではストロンチウムを含まない組成で説明したが、ストロンチウムを含む組成でも同様であることは言うまでもない。
For example, a raw material mixture is prepared by mixing calcium nitride, europium oxide, aluminum nitride, silicon nitride and silicon so that the composition ratio of Ca:Eu:Al:Si is 0.993:0.007:1:1. Then, by heat treatment by the method described below,
Ca 0.993 Eu 0.007 AlSiN 3
A nitride phosphor represented by can be obtained.
However, the composition of this nitride phosphor is a typical composition estimated from the blending ratio of the raw material mixture. Since europium oxide is used, and since each raw material contains about 1% by weight of oxygen, the phosphor obtained may actually contain a certain amount of oxygen. The chemical formula is shown without oxygen. Further, during the heat treatment, a part of the raw material is decomposed and scattering or the like may occur, so that the composition may be slightly different from the charged composition. However, the composition of the intended nitride phosphor can be changed by changing the blending ratio of each raw material. Although the composition not containing strontium has been described here, it goes without saying that the same applies to a composition containing strontium.
原料混合物は、必要に応じて別途準備した式（Ｉ）で表される組成物（窒化物蛍光体）を更に含んでいてもよい。原料混合物が窒化物蛍光体を含む場合、その含有量は原料混合物の総量中に、例えば１重量％以上５０重量％以下とすることができる。 The raw material mixture may further include a separately prepared composition (nitride phosphor) represented by the formula (I), if necessary. When the raw material mixture contains a nitride phosphor, the content thereof can be, for example, 1% by weight or more and 50% by weight or less in the total amount of the raw material mixture.
原料混合物は、必要に応じてハロゲン化物等のフラックスを含んでいてもよい。原料混合物がフラックスを含むことで、原料間の反応がより促進され、更には固相反応がより均一に進行するために粒径が大きく、発光特性により優れた蛍光体を得ることができる。これは例えば、準備工程における熱処理の温度が、フラックスであるハロゲン化物等の液相の生成温度とほぼ同じか、それ以上であるためと考えられる。ハロゲン化物としては、希土類金属、アルカリ土類金属、アルカリ金属の塩化物、フッ化物等を利用できる。フラックスとしては、陽イオンの元素比率を目的物組成になるような化合物として加えることもできるし、更に目的物組成に各原料を加えた後に、添加する形で加えることもできる。
原料混合物がフラックスを含む場合、その含有量は原料混合物中に例えば２０重量％以下であり、１０重量％以下が好ましい。またその含有量は例えば０．１重量％以上である。このようなフラックス含有量とすることにより、蛍光体の発光輝度を低下させることなく、反応を促進させることができるからである。
The raw material mixture may contain a flux such as a halide as needed. When the raw material mixture contains the flux, the reaction between the raw materials is further promoted, and further, the solid-phase reaction proceeds more uniformly, so that the particle size is large and a phosphor excellent in light emission characteristics can be obtained. It is considered that this is because, for example, the temperature of the heat treatment in the preparation step is almost the same as or higher than the temperature at which the liquid phase of the halide or the like that is the flux is generated. As the halide, a rare earth metal, an alkaline earth metal, a chloride of an alkali metal, a fluoride or the like can be used. The flux may be added as a compound such that the element ratio of cations becomes the target composition, or may be added after adding each raw material to the target composition.
When the raw material mixture contains a flux, the content thereof is, for example, 20% by weight or less, preferably 10% by weight or less, in the raw material mixture. The content is, for example, 0.1% by weight or more. This is because by setting such a flux content, the reaction can be promoted without lowering the emission brightness of the phosphor.
原料混合物は、所望の原料化合物を所望の配合比に秤量した後に、ボールミルなどを用いた混合方法、ヘンシェルミキサー、Ｖ型ブレンダ―などの混合機、乳鉢と乳棒を用いた混合方法等を用いて原料化合物を混合することで得ることができる。混合は、乾式混合で行うこともできるし、溶媒等を加えて湿式混合で行うこともできる。 The raw material mixture is prepared by measuring a desired raw material compound at a desired mixing ratio and then using a mixing method using a ball mill or the like, a Henschel mixer, a mixer such as a V-type blender, or a mixing method using a mortar and a pestle. It can be obtained by mixing the raw material compounds. The mixing can be performed by dry mixing, or can be performed by wet mixing by adding a solvent and the like.
原料混合物の熱処理温度は、例えば１２００℃以上であり、１５００℃以上が好ましく、１９００℃以上がより好ましい。また熱処理温度は、例えば２２００℃以下であり、２１００℃以下が好ましく、２０５０℃以下がより好ましい。１２００℃以上の温度で熱処理することで、Ｅｕが結晶中に入り込み易く、所望の窒化物蛍光体が効率よく形成される。また熱処理温度が２２００℃以下であると形成される窒化物蛍光体の分解が抑制される傾向がある。 The heat treatment temperature of the raw material mixture is, for example, 1200° C. or higher, preferably 1500° C. or higher, and more preferably 1900° C. or higher. The heat treatment temperature is, for example, 2200°C or lower, preferably 2100°C or lower, and more preferably 2050°C or lower. By performing the heat treatment at a temperature of 1200° C. or higher, Eu easily enters the crystal and the desired nitride phosphor is efficiently formed. Further, when the heat treatment temperature is 2200° C. or lower, decomposition of the nitride phosphor formed tends to be suppressed.
原料混合物の熱処理における雰囲気は、例えば窒素ガスを含む雰囲気であり、実質的に窒素ガス雰囲気であることが好ましい。窒素ガスを含む雰囲気とすることにより、原料に含まれるケイ素を窒化させることもできる。また、窒化物である原料や蛍光体の分解を抑制することができる。原料混合物の熱処理の雰囲気が窒素ガスを含む場合、窒素ガスに加えて、水素、アルゴン等の希ガス、二酸化炭素、一酸化炭素、酸素、アンモニアなどの他のガスを含んでいてもよい。また原料混合物の熱処理の雰囲気における窒素ガスの含有率は、例えば９０体積％以上であり、９５体積％以上が好ましい。窒素以外の元素を含むガスの含有率を所定値以下とすることにより、それらのガス成分が不純物を形成し蛍光体の発光輝度を低下させる可能性をより小さくすることができる。 The atmosphere in the heat treatment of the raw material mixture is, for example, an atmosphere containing nitrogen gas, and preferably a substantially nitrogen gas atmosphere. By setting the atmosphere containing nitrogen gas, silicon contained in the raw material can be nitrided. Further, it is possible to suppress decomposition of the raw material which is a nitride and the phosphor. When the heat treatment atmosphere of the raw material mixture contains nitrogen gas, it may contain, in addition to nitrogen gas, a rare gas such as hydrogen or argon, or another gas such as carbon dioxide, carbon monoxide, oxygen, or ammonia. The nitrogen gas content in the heat treatment atmosphere of the raw material mixture is, for example, 90% by volume or more, preferably 95% by volume or more. By setting the content rate of the gas containing an element other than nitrogen to a predetermined value or less, it is possible to further reduce the possibility that these gas components form impurities and reduce the emission brightness of the phosphor.
原料混合物の熱処理における圧力は、例えば、常圧から２００ＭＰａとすることができる。生成する窒化物蛍光体の分解を抑制する観点から、圧力は高い方が好ましく、０．１ＭＰａ以上２００ＭＰａ以下が好ましく、０．６ＭＰａ以上１．２ＭＰａ以下が工業的な設備の制約も少なく、より好ましい。 The pressure in the heat treatment of the raw material mixture can be, for example, normal pressure to 200 MPa. From the viewpoint of suppressing decomposition of the generated nitride phosphor, higher pressure is preferable, 0.1 MPa or more and 200 MPa or less is preferable, and 0.6 MPa or more and 1.2 MPa or less is more preferable because there are few restrictions on industrial equipment. ..
原料混合物の熱処理は、単一の温度で行ってもよく、２以上の熱処理温度を含む多段階で行ってもよい。多段階で熱処理を行う場合、例えば８００℃以上１４００℃以下で一段階目の熱処理を行い、その後、徐々に昇温して１５００℃以上２１００℃以下で二段階目の熱処理を行ってもよい。 The heat treatment of the raw material mixture may be performed at a single temperature or may be performed in multiple stages including two or more heat treatment temperatures. When performing the heat treatment in multiple stages, for example, the first-stage heat treatment may be performed at 800° C. or higher and 1400° C. or lower, and then the second stage heat treatment may be performed by gradually increasing the temperature at 1500° C. or higher and 2100° C.
原料混合物の熱処理では、例えば室温から所定の温度に昇温して熱処理する。昇温に要する時間は、例えば１時間以上４８時間以下であり、２時間以上２４時間以下が好ましく、３時間以上２０時間以下であることがより好ましい。昇温に要する時間が１時間以上であると、蛍光体粒子の粒子成長が充分に進行する傾向があり、またＥｕが蛍光体粒子の結晶中に入り込み易くなる傾向がある。 In the heat treatment of the raw material mixture, for example, the temperature is raised from room temperature to a predetermined temperature and the heat treatment is performed. The time required to raise the temperature is, for example, 1 hour or more and 48 hours or less, preferably 2 hours or more and 24 hours or less, and more preferably 3 hours or more and 20 hours or less. If the time required for temperature increase is 1 hour or more, the particle growth of the phosphor particles tends to proceed sufficiently, and Eu tends to easily enter the crystals of the phosphor particles.
原料混合物の熱処理においては所定温度での保持時間を設けてもよい。保持時間は、例えば０．５時間以上４８時間以下であり、１時間以上３０時間以下が好ましく、２時間以上２０時間以下であることがより好ましい。保持時間を所定値以上とすることにより均一な粒子成長をより促進することができる。また、保持時間を所定値以下とすることにより蛍光体の分解をより抑制することができる。 In the heat treatment of the raw material mixture, a holding time at a predetermined temperature may be provided. The holding time is, for example, 0.5 hours or more and 48 hours or less, preferably 1 hour or more and 30 hours or less, and more preferably 2 hours or more and 20 hours or less. By setting the holding time to a predetermined value or more, uniform grain growth can be further promoted. Further, by setting the holding time to a predetermined value or less, the decomposition of the phosphor can be further suppressed.
原料混合物の熱処理における所定温度から室温までの降温時間は、例えば０．１時間以上２０時間以下であり、１時間以上１５時間以下が好ましく、３時間以上１２時間以下であることがより好ましい。なお、所定温度から室温まで降温する間に適宜選択される温度での保持時間を設けてもよい。この保持時間は、例えば、窒化物蛍光体の発光輝度がより向上するように調節される。降温中の所定の温度における保持時間は例えば、０．１時間以上２０時間以下であり、１時間以上１０時間以下が好ましい。また保持時間における温度は、例えば１０００℃以上１８００℃未満であり、１２００℃以上１７００℃以下が好ましい。 The temperature lowering time from the predetermined temperature to the room temperature in the heat treatment of the raw material mixture is, for example, 0.1 hour or more and 20 hours or less, preferably 1 hour or more and 15 hours or less, and more preferably 3 hours or more and 12 hours or less. It should be noted that a holding time at a temperature appropriately selected may be provided while the temperature is lowered from the predetermined temperature to room temperature. This holding time is adjusted, for example, so that the emission brightness of the nitride phosphor is further improved. The holding time at a predetermined temperature during cooling is, for example, 0.1 hour or more and 20 hours or less, and preferably 1 hour or more and 10 hours or less. The temperature during the holding time is, for example, 1000°C or higher and lower than 1800°C, preferably 1200°C or higher and 1700°C or lower.
原料混合物の熱処理は、例えばガス加圧電気炉を用いて行うことができる。
また、原料混合物の熱処理は、例えば原料混合物を、黒鉛等の炭素材質又は窒ホウ素（ＢＮ）材質のルツボ、ボート等に充填して用いて行うことができる。炭素材質、窒化ホウ素材質以外に、アルミナ（Ａｌ２Ｏ３）、Ｍｏ材質等を使用することもできる。中でも窒化ホウ素材質のルツボ、ボートを用いることが好ましい。
The heat treatment of the raw material mixture can be performed using, for example, a gas pressure electric furnace.
The heat treatment of the raw material mixture can be performed, for example, by filling the raw material mixture into a crucible, a boat, or the like made of a carbon material such as graphite or a boron nitride (BN) material. In addition to the carbon material and the boron nitride material, alumina (Al 2 O 3 ) and Mo material may be used. Above all, it is preferable to use a crucible or boat made of boron nitride.
原料混合物の熱処理後には、熱処理で得られる窒化物蛍光体に解砕、粉砕、分級操作等の処理を組合せて行う整粒工程を含んでいてもよい。整粒工程により所望の粒径の粉末を得ることができる。具体的には、窒化物蛍光体を粗粉砕した後に、ボールミル、ジェットミル、振動ミルなどの一般的な粉砕機を用いて所定の粒径に粉砕することができる。ただし、過剰な粉砕を行うと蛍光体粒子表面に欠陥が生じて、輝度低下を引き起こすこともある。粉砕で生じた粒径の異なるものが存在する場合には、分級を行い、粒径を整えることもできる。 After the heat treatment of the raw material mixture, a sizing step may be included in which the nitride phosphor obtained by the heat treatment is combined with treatments such as crushing, crushing, and classification operations. A powder having a desired particle size can be obtained by the sizing process. Specifically, after the nitride phosphor is roughly pulverized, it can be pulverized to a predetermined particle size by using a general pulverizer such as a ball mill, a jet mill and a vibration mill. However, excessive pulverization may cause defects on the surface of the phosphor particles, resulting in a decrease in brightness. When there are particles having different particle sizes generated by pulverization, classification can be performed to adjust the particle size.
［窒化物蛍光体］
本開示は、上記製造方法で製造される窒化物蛍光体を包含する。窒化物蛍光体は、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含むことが好ましく、上記式（Ｉ）で表される組成を有することがより好ましい。窒化物蛍光体は、その製造に用いられる原料混合物がケイ素と窒化ケイ素を組み合わせて含むことで、製造時の熱処理における焼結が抑制され、粒径が大きくなり高輝度を達成できる。
[Nitride phosphor]
The present disclosure includes a nitride phosphor manufactured by the above manufacturing method. The nitride phosphor preferably contains an alkaline earth metal, aluminum, silicon and europium, and more preferably has a composition represented by the above formula (I). Since the raw material mixture used for the production of the nitride phosphor contains silicon and silicon nitride in combination, the sintering during the heat treatment during the production is suppressed, the particle size becomes large, and high brightness can be achieved.
窒化物蛍光体は、例えば２００ｎｍ以上６００ｎｍ以下の範囲の光を吸収して、６０５ｎｍ以上６７０ｎｍ以下の範囲に発光ピーク波長を有する光を発する赤色発光の蛍光体である。窒化物蛍光体の励起波長は４２０ｎｍ以上４７０ｎｍ以下の範囲にあることが好ましい。窒化物蛍光体の発光スペクトルにおける半値幅は、例えば７０ｎｍ以上９５ｎｍ以下である。 The nitride phosphor is, for example, a red-emitting phosphor that absorbs light in the range of 200 nm to 600 nm and emits light having an emission peak wavelength in the range of 605 nm to 670 nm. The excitation wavelength of the nitride phosphor is preferably in the range of 420 nm or more and 470 nm or less. The full width at half maximum in the emission spectrum of the nitride phosphor is, for example, 70 nm or more and 95 nm or less.
窒化物蛍光体の比表面積は、例えば０．３ｍ２／ｇ未満であり、０．２７ｍ２／ｇ以下が好ましく、０．２ｍ２／ｇ以下がより好ましく、０．１６ｍ２／ｇ以下が更に好ましく、０．１５ｍ２／ｇ以下がより更に好ましく、０．１３ｍ２／ｇ以下が特に好ましい。また比表面積は、例えば０．０５ｍ２／ｇ以上であり、０．１ｍ２／ｇ以上が好ましい。比表面積が０．３ｍ２／ｇ未満であると光吸収及び変換効率がより向上し、より高輝度を達成できる傾向がある。 The specific surface area of the nitride phosphor is, for example 0.3m less than 2 / g, preferably from 0.27 m 2 / g or less, more preferably 0.2 m 2 / g, still is 0.16 m 2 / g or less preferably, even more preferably from 0.15 m 2 / g or less, particularly preferably 0.13 m 2 / g. The specific surface area is, for example, 0.05 m 2 / g or more, more preferably 0.1 m 2 / g. When the specific surface area is less than 0.3 m 2 /g, light absorption and conversion efficiency are further improved, and higher brightness tends to be achieved.
窒化物蛍光体の比表面積はＢＥＴ法で測定される。具体的には、島津製作所製ジェミニ２３７０を用いて、動的定圧法により算出する。 The specific surface area of the nitride phosphor is measured by the BET method. Specifically, it is calculated by the dynamic constant pressure method using Gemini 2370 manufactured by Shimadzu Corporation.
窒化物蛍光体の平均粒径は、例えば１５μｍ以上であり、１８μｍ以上が好ましく、２０μｍ以上がより好ましい。また平均粒径は、例えば３０μｍ以下であり、２５μｍ以下が好ましい。平均粒径が１５μｍ以上であると光吸収及び変換効率がより向上し、よりより高輝度を達成できる傾向がある。また３０μｍ以下であると取扱い性がより向上し、窒化物蛍光体を用いる発光装置の生産性がより向上する傾向がある。
窒化物蛍光体の平均粒径は、例えば１５μｍ以上３０μｍ以下の範囲である。また、この粒径値を有する蛍光体が、頻度高く含有されていることが好ましい。また、粒度分布も狭い範囲に分布しているものが好ましい。このように粒径、及び粒度分布のバラツキが小さい蛍光体を用いることにより、より色ムラが抑制され、良好な色調を有する発光装置が得られる。
The average particle size of the nitride phosphor is, for example, 15 μm or more, preferably 18 μm or more, and more preferably 20 μm or more. The average particle size is, for example, 30 μm or less, preferably 25 μm or less. When the average particle size is 15 μm or more, light absorption and conversion efficiency are further improved, and higher brightness tends to be achieved. Further, when it is 30 μm or less, the handleability is further improved, and the productivity of the light emitting device using the nitride phosphor tends to be further improved.
The average particle size of the nitride phosphor is, for example, in the range of 15 μm or more and 30 μm or less. Further, it is preferable that the phosphor having this particle size value is contained frequently. Further, it is preferable that the particle size distribution is distributed in a narrow range. By using a phosphor having a small variation in particle size and particle size distribution in this way, it is possible to obtain a light emitting device in which color unevenness is further suppressed and a good color tone is obtained.
窒化物蛍光体の平均粒径は、フィッシャーサブシーブサイザー（Fisher Sub Sieve Sizer）を用いる空気透過法で得られるＦ．Ｓ．Ｓ．Ｓ．Ｎ．（Fisher Sub Sieve Sizer's No.）である。具体的には、気温２５℃、湿度７０％ＲＨの環境下において、１ｃｍ３分の試料を計り取り、専用の管状容器にパッキングした後、一定圧力の乾燥空気を流し、差圧から比表面積を読み取り、平均粒径に換算した値である。 The average particle size of the nitride phosphor is determined by the F.F. method obtained by an air permeation method using a Fisher Sub Sieve Sizer. S. S. S. N. (Fisher Sub Sieve Sizer's No.). Specifically, in an environment of a temperature of 25° C. and a humidity of 70% RH, a sample of 1 cm 3 is weighed and packed in a dedicated tubular container, and then dry air having a constant pressure is flowed to determine the specific surface area from the differential pressure. It is the value read and converted into the average particle size.
窒化物蛍光体は、発光輝度を向上させる観点から、ＢＥＴ法による比表面積が０．３ｍ２／ｇ未満、且つ平均粒径が１８μｍ以上であることが好ましく、比表面積が０．２ｍ２／ｇ以下、且つ平均粒径が２０μｍ以上であることがより好ましく、比表面積が０．１６ｍ２／ｇ以下、且つ平均粒径が２０μｍ以上であることが更に好ましい。また比表面積は０．１ｍ２／ｇ以上であり、平均粒径は、３０μｍ以下であることが好ましく、２５μｍ以下であることがより好ましい。 From the viewpoint of improving the emission brightness, the nitride phosphor preferably has a specific surface area by BET method of less than 0.3 m 2 /g and an average particle diameter of 18 μm or more, and a specific surface area of 0.2 m 2 /g. It is more preferable that the average particle diameter is 20 μm or more, the specific surface area is 0.16 m 2 /g or less, and the average particle diameter is 20 μm or more. Further, the specific surface area is 0.1 m 2 /g or more, and the average particle diameter is preferably 30 μm or less, more preferably 25 μm or less.
窒化物蛍光体は、発光輝度を向上させる観点から、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含む窒化物であって、ＢＥＴ法による比表面積が０．１ｍ２／ｇ以上０．１６ｍ２／ｇ以下であり、平均粒径が２０μｍ以上３０μｍ以下であることが好ましく、上記式（Ｉ）で表される組成を有し、ＢＥＴ法による比表面積が０．１ｍ２／ｇ以上０．１６ｍ２／ｇ以下であり、平均粒径が２０μｍ以上３０μｍ以下であることがより好ましい。また窒化物蛍光体は、発光輝度を向上させる観点から、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含む窒化物であって、ＢＥＴ法による比表面積が０．１ｍ２／ｇ以上０．１５ｍ２／ｇ以下であり、平均粒径が２０μｍ以上３０μｍ以下であることも好ましく、上記式（Ｉ）においてｓ＝０である組成を有し、ＢＥＴ法による比表面積が０．１ｍ２／ｇ以上０．１５ｍ２／ｇ以下であり、平均粒径が２０μｍ以上３０μｍ以下であることがより好ましい。 Nitride phosphor, from the viewpoint of improving the light emission luminance, an alkaline earth metal, aluminum, a nitride containing silicon and europium, specific surface area by BET method of 0.1 m 2 / g or more 0.16 m 2 / g or less, the average particle diameter is preferably 20 μm or more and 30 μm or less, the composition has the composition represented by the above formula (I), and the specific surface area by the BET method is 0.1 m 2 /g or more and 0.16 m 2 or more. /G or less and the average particle size is more preferably 20 μm or more and 30 μm or less. The nitride phosphor is, from the viewpoint of improving the light emission luminance, an alkaline earth metal, aluminum, a nitride containing silicon and europium, specific surface area by BET method of 0.1 m 2 / g or more 0.15 m 2 /G or less, the average particle size is preferably 20 μm or more and 30 μm or less, the composition has a composition of s=0 in the above formula (I), and the specific surface area by the BET method is 0.1 m 2 /g or more 0 It is more preferable that it is 0.15 m 2 /g or less and the average particle diameter is 20 μm or more and 30 μm or less.
窒化物蛍光体は、少なくとも一部に結晶性が高い構造を有していることが好ましい。例えばガラス体（非晶質）は構造が不規則であり結晶性が低いため、その生産工程における反応条件が厳密に一様になるよう管理できなければ、蛍光体中の成分比率が一定せず、色度ムラ等を生じる傾向がある。これに対し、本実施形態に係る窒化物蛍光体は、少なくとも一部に結晶性が高い構造を有している粉体ないし粒体であることで製造及び加工し易くなる傾向がある。また、窒化物蛍光体は、有機媒体に均一に分散することが容易にできるため、発光性プラスチック、ポリマー薄膜材料等を調製することが容易にできる。具体的に、窒化物蛍光体は、例えば５０重量％以上、より好ましくは８０重量％以上が結晶性を有する構造である。これは、発光性を有する結晶相の割合を示し、５０重量％以上、結晶相を有していれば、実用に耐え得る発光が得られるため好ましい。ゆえに結晶相が多いほど発光輝度がより向上し、加工し易くなる。 It is preferable that the nitride phosphor has a structure having high crystallinity in at least a part thereof. For example, a glass body (amorphous) has an irregular structure and low crystallinity, so if the reaction conditions in the production process cannot be controlled so as to be strictly uniform, the component ratio in the phosphor will not be constant. , Chromaticity unevenness and the like tend to occur. On the other hand, the nitride phosphor according to the present embodiment tends to be easily manufactured and processed because it is a powder or granule having a structure with high crystallinity at least in part. In addition, since the nitride phosphor can be easily dispersed uniformly in the organic medium, a luminescent plastic, a polymer thin film material, etc. can be easily prepared. Specifically, the nitride phosphor has a structure in which, for example, 50% by weight or more, and more preferably 80% by weight or more has crystallinity. This indicates the proportion of the crystal phase having a light emitting property, and if the crystal phase is 50% by weight or more, it is preferable because light emission that can withstand practical use can be obtained. Therefore, the more the crystal phase is, the more the emission brightness is improved, and the processing becomes easier.
［発光装置］
本開示は前記窒化物蛍光体を含む発光装置を包含する。発光装置は、例えば３８０ｎｍ以上４７０ｎｍ以下の範囲に発光ピーク波長を有する発光素子と、前記窒化物蛍光体を含む第一蛍光体を少なくとも含む蛍光部材とを備える。蛍光部材は、緑色から黄色に発光する第二蛍光体を更に含んでいてもよい。発光装置が発する光は、発光素子の光と蛍光部材が発する蛍光との混合色であり、例えば、ＣＩＥ１９３１に規定される色度座標が、ｘ＝０．２２０以上０．３４０以下且つｙ＝０．１６０以上０．３４０以下の範囲に含まれる光であることが好ましく、ｘ＝０．２２０以上０．３３０以下且つｙ＝０．１７０以上０．３３０以下の範囲に含まれる光であることがより好ましい。
[Light emitting device]
The present disclosure includes a light emitting device including the nitride phosphor. The light emitting device includes, for example, a light emitting element having an emission peak wavelength in the range of 380 nm to 470 nm and a fluorescent member including at least a first phosphor containing the nitride phosphor. The fluorescent member may further include a second phosphor that emits green to yellow light. The light emitted by the light emitting device is a mixed color of the light of the light emitting element and the fluorescence emitted by the fluorescent member. For example, the chromaticity coordinates defined by CIE1931 are x=0.220 or more and 0.340 or less and y=0. The light is preferably in the range of 160 to 0.340, and is preferably in the range of x=0.220 to 0.330 and y=0.170 to 0.330. More preferable.
本実施形態に係る発光装置１００の一例を図面に基づいて説明する。図１は、本発明に係る発光装置の一例を示す概略断面図１００である。発光装置１００は、表面実装型発光装置の一例である。
発光装置１００は、可視光の短波長側（例えば、３８０ｎｍ以上４８５ｎｍ以下の範囲）の光を発し、発光ピーク波長が、例えば４４０ｎｍ以上４６０ｎｍ以下である窒化ガリウム系化合物半導体の発光素子１０と、発光素子１０を載置する成形体４０と、を有する。成形体４０は第１のリード２０及び第２のリード３０と、樹脂部４２とが一体的に成形されてなるものである。あるいは樹脂部４２に代えてセラミックスを材料として既に知られた方法を利用して成形体４０を形成することもできる。成形体４０は底面と側面を持つ凹部を形成しており、凹部の底面に発光素子１０が載置されている。発光素子１０は一対の正負の電極を有しており、その一対の正負の電極はそれぞれ第１のリード２０及び第２のリード３０とワイヤ６０を介して電気的に接続されている。発光素子１０は蛍光部材５０により被覆されている。蛍光部材５０は発光素子１０からの光を波長変換する蛍光体７０として例えば赤色蛍光体（第一蛍光体７１）及び緑色蛍光体（第二蛍光体７２）と、樹脂とを含有してなる。
An example of the light emitting device 100 according to the present embodiment will be described based on the drawings. FIG. 1 is a schematic sectional view 100 showing an example of a light emitting device according to the present invention. The light emitting device 100 is an example of a surface mount light emitting device.
The light emitting device 100 emits light on the short wavelength side of visible light (for example, in the range of 380 nm to 485 nm), and a light emitting element 10 of a gallium nitride-based compound semiconductor having an emission peak wavelength of, for example, 440 nm to 460 nm, and light emission. And a molded body 40 on which the element 10 is mounted. The molded body 40 is formed by integrally molding the first lead 20 and the second lead 30, and the resin portion 42. Alternatively, the molded body 40 can be formed by using a known method using ceramics as a material instead of the resin portion 42. The molded body 40 has a recess having a bottom surface and side surfaces, and the light emitting element 10 is mounted on the bottom surface of the recess. The light emitting element 10 has a pair of positive and negative electrodes, and the pair of positive and negative electrodes are electrically connected to the first lead 20 and the second lead 30 via wires 60, respectively. The light emitting element 10 is covered with a fluorescent member 50. The fluorescent member 50 contains, for example, a red fluorescent material (first fluorescent material 71) and a green fluorescent material (second fluorescent material 72) as a fluorescent material 70 that converts the wavelength of light from the light emitting element 10, and a resin.
蛍光部材５０は、蛍光体７０を含む波長変換部材としてだけではなく、発光素子１０や蛍光体７０を外部環境から保護するための部材としても機能する。図１では、蛍光体７０は蛍光部材５０中で偏在している。このように発光素子１０に接近して蛍光体７０を配置することにより、発光素子１０からの光を効率よく波長変換することができ、発光輝度の優れた発光装置とできる。なお、蛍光体７０を含む蛍光部材５０と、発光素子１０との配置は、それらを接近して配置させる形態に限定されることなく、蛍光体７０への熱の影響を考慮して、蛍光部材５０中で発光素子１０と、蛍光体７０との間隔を空けて配置することもできる。また、蛍光体７０を蛍光部材５０の全体にほぼ均一の割合で混合することによって、色ムラがより抑制された光を得るようにすることもできる。 The fluorescent member 50 functions not only as a wavelength conversion member including the phosphor 70, but also as a member for protecting the light emitting element 10 and the phosphor 70 from the external environment. In FIG. 1, the phosphor 70 is unevenly distributed in the fluorescent member 50. By arranging the phosphor 70 close to the light emitting element 10 in this manner, the wavelength of the light from the light emitting element 10 can be efficiently converted, and a light emitting device having excellent emission brightness can be obtained. The arrangement of the fluorescent member 50 including the phosphor 70 and the light emitting element 10 is not limited to the form in which they are arranged close to each other, and the effect of heat on the phosphor 70 is taken into consideration. It is also possible to arrange the light emitting element 10 and the phosphor 70 in 50 with a space therebetween. Further, by mixing the phosphor 70 in the entire fluorescent member 50 at a substantially uniform ratio, it is possible to obtain light in which color unevenness is further suppressed.
（発光素子）
発光素子の発光ピーク波長は、例えば３８０ｎｍ以上４７０ｎｍ、好ましくは４４０ｎｍ以上４６０ｎｍ以下の範囲にある。この範囲に発光ピーク波長を有する発光素子を励起光源として用いることにより、発光素子からの光と蛍光体からの蛍光との混色光を発する発光装置を構成することが可能となる。さらに、発光素子から外部に放射される光を有効に利用することができるため、発光装置から出射される光の損失を少なくすることができ、高効率な発光装置を得ることができる。
(Light emitting element)
The emission peak wavelength of the light emitting element is, for example, in the range of 380 nm to 470 nm, preferably 440 nm to 460 nm. By using a light emitting element having an emission peak wavelength in this range as an excitation light source, it becomes possible to configure a light emitting device that emits mixed color light of light from the light emitting element and fluorescence from the phosphor. Further, since the light emitted from the light emitting element to the outside can be effectively used, the loss of the light emitted from the light emitting device can be reduced, and a highly efficient light emitting device can be obtained.
発光素子の発光スペクトルの半値幅は、例えば、３０ｎｍ以下とすることができる。
発光素子には半導体発光素子を用いることが好ましい。光源として半導体発光素子を用いることによって、高効率で入力に対する出力のリニアリティが高く、機械的衝撃にも強い安定した発光装置を得ることができる。
半導体発光素子としては、例えば、窒化物系半導体（ＩｎＸＡｌＹＧａ１−Ｘ−ＹＮ、ここでＸ及びＹは、０≦Ｘ、０≦Ｙ、Ｘ＋Ｙ≦１を満たす）を用いた青色、緑色等に発光する半導体発光素子を用いることができる。
The full width at half maximum of the emission spectrum of the light emitting element can be set to, for example, 30 nm or less.
A semiconductor light emitting element is preferably used as the light emitting element. By using the semiconductor light emitting element as the light source, it is possible to obtain a stable light emitting device having high efficiency, high linearity of output with respect to input, and strong against mechanical shock.
As the semiconductor light emitting device, for example, a nitride-based semiconductor (In X Al Y Ga 1-X-Y N, where X and Y satisfy 0≦X, 0≦Y, and X+Y≦1) is used. A semiconductor light emitting element that emits green light or the like can be used.
（蛍光部材）
発光装置は、発光素子から発せられる光の一部を吸収して波長変換する蛍光部材を備える。蛍光部材は、赤色に発光する第一蛍光体の少なくとも１種を含み、緑色から黄色に発光する第二蛍光体の少なくとも１種を含んでいてもよい。第一蛍光体には前記窒化物蛍光体が含まれる。第二蛍光体には５００ｎｍ以上５８０ｎｍ以下の範囲に発光ピーク波長を有する蛍光を発する緑色蛍光体から適宜選択される蛍光体を用いることができる。第二蛍光体の発光ピーク波長、発光スペクトル等を適宜選択することで発光装置の相関色温度、演色性等の特性を所望の範囲とすることができる。蛍光部材は、蛍光体に加えて樹脂を含んでいてもよい。発光装置は、蛍光体及び樹脂を含み、発光素子を被覆する蛍光部材を備えることができる。
(Fluorescent member)
The light emitting device includes a fluorescent member that absorbs a part of the light emitted from the light emitting element and converts the wavelength. The fluorescent member may include at least one kind of first fluorescent material that emits red light, and may include at least one kind of second fluorescent material that emits green to yellow light. The first phosphor includes the nitride phosphor. As the second phosphor, a phosphor appropriately selected from a green phosphor that emits fluorescence having an emission peak wavelength in the range of 500 nm to 580 nm can be used. By appropriately selecting the emission peak wavelength, the emission spectrum, etc. of the second phosphor, the characteristics such as the correlated color temperature and the color rendering of the light emitting device can be set within a desired range. The fluorescent member may include a resin in addition to the fluorescent substance. The light emitting device may include a fluorescent member that includes a phosphor and a resin and covers the light emitting element.
第一蛍光体に含まれる窒化物蛍光体の詳細は既述の通りである。発光装置における第一蛍光体の含有量は、例えば蛍光部材に含まれる樹脂１００重量部に対して０．１重量部以上５０重量部以下とすることができ、１重量部３０重量部以下であることが好ましい。 The details of the nitride phosphor contained in the first phosphor are as described above. The content of the first phosphor in the light emitting device can be, for example, 0.1 parts by weight or more and 50 parts by weight or less, and 1 part by weight 30 parts by weight or less with respect to 100 parts by weight of the resin contained in the fluorescent member. It is preferable.
第二蛍光体は、例えば５００ｎｍ以上５８０ｎｍ以下、好ましくは５２０ｎｍ以上５５０ｎｍ以下の範囲に発光ピーク波長を有する蛍光を発する。第二蛍光体は、下記式（ＩＩａ）で表される組成を有するβサイアロン蛍光体、下記式（ＩＩｂ）で表される組成を有するシリケート蛍光体、下記式（ＩＩｃ）で表される組成を有するハロシリケート蛍光体、下記式（ＩＩｄ）で表される組成を有するチオガレート蛍光体、下記式（ＩＩｅ）で表される組成を有する希土類アルミン酸塩蛍光体、下記式（ＩＩｆ）で表されるアルカリ土類アルミン酸塩蛍光体及び下記式（ＩＩｇ）で表されるアルカリ土類リン酸塩蛍光体からなる群から選択される少なくとも１種であることが好ましい。特に、第二蛍光体として、下記式（ＩＩｃ）、（ＩＩe）、（ＩＩｆ）または（ＩＩｇ）で表される組成を有する蛍光体の少なくとも１種を選択して、第一蛍光体とともに蛍光部材に含むことにより、発光装置の演色性を向上させることができる点で好ましい。
Ｓｉ６−ｗＡｌｗＯｗＮ８−ｗ：Ｅｕ （ＩＩａ）
（式中、ｗは、０＜ｗ≦４．２を満たす。）
（Ｂａ，Ｓｒ，Ｃａ，Ｍｇ）２ＳｉＯ４：Ｅｕ （ＩＩｂ）
（Ｃａ，Ｓｒ，Ｂａ）８ＭｇＳｉ４Ｏ１６（Ｆ，Ｃｌ，Ｂｒ）２：Ｅｕ （ＩＩｃ）
（Ｂａ，Ｓｒ，Ｃａ）Ｇａ２Ｓ４：Ｅｕ （ＩＩｄ）
（Ｙ，Ｌｕ，Ｇｄ）３（Ａｌ，Ｇａ）５Ｏ１２：Ｃｅ （ＩＩe）
（Ｓｒ，Ｃａ，Ｂａ）４Ａｌ１４Ｏ２５：Ｅｕ （ＩＩｆ）
（Ｃａ，Ｓｒ，Ｂａ）５（ＰＯ４）３（Ｃｌ，Ｂｒ）：Ｅｕ （ＩＩｇ）
組成式（ＩＩａ）中、ｗは、０．０１＜ｗ＜２を満たすことが好ましい。
The second phosphor emits fluorescence having an emission peak wavelength in the range of, for example, 500 nm to 580 nm, preferably 520 nm to 550 nm. The second phosphor includes a β-sialon phosphor having a composition represented by the following formula (IIa), a silicate phosphor having a composition represented by the following formula (IIb), and a composition represented by the following formula (IIc). Having a halosilicate phosphor, a thiogallate phosphor having a composition represented by the following formula (IId), a rare earth aluminate phosphor having a composition represented by the following formula (IIe), represented by the following formula (IIf) At least one selected from the group consisting of an alkaline earth aluminate phosphor and an alkaline earth phosphate phosphor represented by the following formula (IIg) is preferable. In particular, as the second phosphor, at least one kind of phosphor having a composition represented by the following formula (IIc), (IIe), (IIf) or (IIg) is selected, and the phosphor member together with the first phosphor is selected. It is preferable that the light emitting device can be improved in the color rendering properties by including it in (1).
Si 6-w Al w O w N 8-w :Eu (IIa)
(In the formula, w satisfies 0<w≦4.2.)
(Ba, Sr, Ca, Mg) 2 SiO 4 :Eu (IIb)
(Ca, Sr, Ba) 8 MgSi 4 O 16 (F, Cl, Br) 2: Eu (IIc)
(Ba,Sr,Ca)Ga 2 S 4 :Eu (IId)
(Y, Lu, Gd) 3 (Al, Ga) 5 O 12: Ce (IIe)
(Sr,Ca,Ba) 4 Al 14 O 25 :Eu (IIf)
(Ca,Sr,Ba) 5 (PO 4 ) 3 (Cl,Br):Eu (IIg)
In the composition formula (IIa), w preferably satisfies 0.01<w<2.
発光装置に含まれる第二蛍光体の平均粒径は、発光輝度の観点から、２μｍ以上３５μｍ以下であることが好ましく、５μｍ以上３０μｍ以下であることがより好ましい。
第二蛍光体の平均粒径は、第一蛍光体の平均粒径と同様にして測定される。
The average particle size of the second phosphor included in the light emitting device is preferably 2 μm or more and 35 μm or less, and more preferably 5 μm or more and 30 μm or less, from the viewpoint of emission brightness.
The average particle size of the second phosphor is measured in the same manner as the average particle size of the first phosphor.
発光装置における第二蛍光体の含有量は、例えば蛍光部材に含まれる樹脂１００重量部に対して１重量部以上７０重量部以下とすることができ、２重量部以上５０重量部以下であることが好ましい。 The content of the second phosphor in the light emitting device may be, for example, 1 part by weight or more and 70 parts by weight or less, and 2 parts by weight or more and 50 parts by weight or less, relative to 100 parts by weight of the resin contained in the fluorescent member. Is preferred.
発光装置における第一蛍光体の第二蛍光体に対する含有比（第一蛍光体／第二蛍光体）は、例えば重量基準で０．０１以上１０以下とすることができ、０．１以上１以下が好ましい。 The content ratio of the first phosphor to the second phosphor in the light emitting device (first phosphor/second phosphor) can be, for example, 0.01 or more and 10 or less on a weight basis, and 0.1 or more and 1 or less. Is preferred.
その他の蛍光体
発光装置は、第一の蛍光体及び第二の蛍光体以外のその他の蛍光体を必要に応じて含んでいてもよい。その他の蛍光体としては、Ｃａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ、ＣａＳｃ２Ｏ４：Ｃｅ、（Ｌａ，Ｙ）３Ｓｉ６Ｎ１１：Ｃｅ、（Ｃａ，Ｓｒ，Ｂａ）３Ｓｉ６Ｏ９Ｎ４：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ、（Ｂａ，Ｓｒ，Ｃａ)Ｓｉ２Ｏ２Ｎ２：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）２Ｓｉ５Ｎ８：Ｅｕ、Ｋ２（Ｓｉ，Ｔｉ，Ｇｅ）Ｆ６：Ｍｎ等を挙げることができる。発光装置がその他の蛍光体を含む場合、その含有量は、例えば第一蛍光体及び第二蛍光体の総量に対して１０重量％以下であり、１重量％以下である。
Other Phosphors The light emitting device may include other phosphors other than the first phosphor and the second phosphor as necessary. Other phosphor, Ca 3 Sc 2 Si 3 O 12: Ce, CaSc 2 O 4: Ce, (La, Y) 3 Si 6 N 11: Ce, (Ca, Sr, Ba) 3 Si 6 O 9 N 4: Eu, (Ca, Sr, Ba) 3 Si 6 O 12 N 2: Eu, (Ba, Sr, Ca) Si 2 O 2 N 2: Eu, (Ca, Sr, Ba) 2 Si 5 N 8 : Eu, K 2 (Si, Ti, Ge) F 6: Mn , and the like. When the light emitting device includes another phosphor, the content thereof is, for example, 10% by weight or less and 1% by weight or less with respect to the total amount of the first phosphor and the second phosphor.
蛍光部材を構成する樹脂としては、熱可塑性樹脂及び熱硬化性樹脂が挙げられる。熱硬化性樹脂として、具体的には、エポキシ樹脂、シリコーン樹脂などを挙げることができる。蛍光部材は、蛍光体及び樹脂以外のその他の成分を必要に応じて含んでいてもよい。その他の成分としては、シリカ、チタン酸バリウム、酸化チタン、酸化アルミニウム等のフィラー、光安定化剤、着色剤等を挙げることができる。蛍光部材が、その他の成分として、例えばフィラーを含む場合、その含有量は樹脂１００重量部に対して、０．０１重量部以上２０重量部以下とすることができる。 Examples of the resin that constitutes the fluorescent member include a thermoplastic resin and a thermosetting resin. Specific examples of the thermosetting resin include epoxy resin and silicone resin. The fluorescent member may include other components other than the fluorescent substance and the resin, if necessary. Examples of other components include fillers such as silica, barium titanate, titanium oxide and aluminum oxide, light stabilizers and colorants. When the fluorescent member contains, for example, a filler as another component, the content thereof can be 0.01 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the resin.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
（実施例１）
原料化合物となる窒化カルシウム（Ｃａ３Ｎ２）と、窒化ケイ素（Ｓｉ３Ｎ４）及びケイ素単体（Ｓｉ）と、窒化アルミニウム（ＡｌＮ）と、酸化ユウロピウム（Ｅｕ２Ｏ３）とをＣａ：Ｓｉ：Ａｌ：Ｅｕ＝０．９９３：１．１：０．９：０．００７のモル比となるように秤量し、混合した。ここで窒化ケイ素とケイ素単体の配合割合は、窒化ケイ素が４１．６重量％、ケイ素単体が５８．４重量％となるようにした。得られた混合原料を窒化ホウ素製ルツボに充填し、窒素雰囲気で０．９２ＭＰａ（ゲージ圧）の圧力、２０００℃、２時間、熱処理することにより、窒化物蛍光体を得た。
(Example 1)
Calcium nitride (Ca 3 N 2 ) serving as a raw material compound, silicon nitride (Si 3 N 4 ) and silicon simple substance (Si), aluminum nitride (AlN), and europium oxide (Eu 2 O 3 ) are mixed with Ca:Si. :Al:Eu=0.993:1.1:0.9:0.007 were weighed and mixed so that the molar ratio would be. Here, the compounding ratios of silicon nitride and silicon simple substance were such that silicon nitride was 41.6% by weight and silicon simple substance was 58.4% by weight. The obtained mixed raw material was filled in a boron nitride crucible and heat-treated in a nitrogen atmosphere at a pressure of 0.92 MPa (gauge pressure) at 2000° C. for 2 hours to obtain a nitride phosphor.
（実施例２）
窒化ケイ素とケイ素単体の配合割合を、窒化ケイ素が３７．５重量％、ケイ素単体が６２．５重量％となるようにしたこと以外は、実施例１と同様にして窒化物蛍光体を得た。
(Example 2)
A nitride phosphor was obtained in the same manner as in Example 1 except that the compounding ratio of silicon nitride and silicon simple substance was 37.5% by weight of silicon nitride and 62.5% by weight of silicon simple substance. ..
（実施例３）
窒化ケイ素とケイ素単体の配合割合を、窒化ケイ素が２０．５重量％、ケイ素単体が７９．５重量％となるようにしたこと以外は、実施例１と同様にして窒化物蛍光体を得た。
(Example 3)
A nitride phosphor was obtained in the same manner as in Example 1 except that the compounding ratios of silicon nitride and silicon simple substance were such that silicon nitride was 20.5% by weight and silicon simple substance was 79.5% by weight. ..
（実施例４）
窒化ケイ素とケイ素単体の配合割合を、窒化ケイ素が７０．６重量％、ケイ素単体が２９．４重量％となるようにしたこと以外は、実施例１と同様にして窒化物蛍光体を得た。
(Example 4)
A nitride phosphor was obtained in the same manner as in Example 1 except that the composition ratio of silicon nitride and silicon simple substance was 70.6% by weight of silicon nitride and 29.4% by weight of silicon simple substance. ..
（実施例５）
窒化ケイ素とケイ素単体の配合割合を、窒化ケイ素が８４．４重量％、ケイ素単体が１５．６重量％となるようにしたこと以外は、実施例１と同様にして窒化物蛍光体を得た。
(Example 5)
A nitride phosphor was obtained in the same manner as in Example 1 except that the compounding ratios of silicon nitride and silicon simple substance were such that silicon nitride was 84.4% by weight and silicon simple substance was 15.6% by weight. ..
（比較例１）
ケイ素単体を用いずに、窒化ケイ素のみを用いたこと以外は、実施例１と同様にして窒化物蛍光体を得た。
(Comparative Example 1)
A nitride phosphor was obtained in the same manner as in Example 1 except that only silicon nitride was used without using silicon simple substance.
（比較例２）
窒化ケイ素を用いずに、ケイ素単体のみを用いたこと以外は、実施例１と同様にして窒化物蛍光体を得た。
(Comparative example 2)
A nitride phosphor was obtained in the same manner as in Example 1 except that silicon alone was used without using silicon nitride.
得られた窒化物蛍光体について以下の評価を行った。
平均粒径
Ｆ．Ｓ．Ｓ．Ｓ．（Fisher Sub Sieve Sizer）を用い、気温２５℃、湿度７０％ＲＨの環境下において、１ｃｍ３分の試料を計り取り、専用の管状容器にパッキングした後、一定圧力の乾燥空気を流し、差圧から比表面積を読み取り、平均粒径を算出した。
The following evaluation was performed on the obtained nitride phosphor.
Average particle size F.I. S. S. S. (Fisher Sub Sieve Sizer), at a temperature of 25° C. and a humidity of 70% RH, weigh out a sample of 1 cm 3 minutes, pack it in a dedicated tubular container, and then let dry air at a constant pressure flow to give a differential pressure. The specific surface area was read from and the average particle size was calculated.
比表面積
島津製作所製ジェミニ２３７０を用いて、取扱い説明書に準じて動的定圧法により算出した。
Specific surface area Using a Gemini 2370 manufactured by Shimadzu Corporation, it was calculated by the dynamic constant pressure method according to the instruction manual.
発光特性
日立ハイテク製のＦ−４５００を用い、４６０ｎｍで励起させた時の発光スペクトルを測定した。この得られた発光スペクトルのエネルギー値：ＥＮＧ（％）、発光ピーク波長：λｐ（ｎｍ）を求めた。
Luminescence characteristics F-4500 manufactured by Hitachi High-Tech was used to measure the luminescence spectrum when excited at 460 nm. The energy value of the obtained emission spectrum: ENG (%) and the emission peak wavelength: λp (nm) were determined.
表１に平均粒径、比表面積、λｐ、ＥＮＧ（％）を示す。ＥＮＧ（％）は、比較例１の窒化物蛍光体のエネルギー値を１００％とした相対値である。また図２に得られた発光スペクトルを示す。 Table 1 shows the average particle diameter, specific surface area, λp, and ENG (%). ENG (%) is a relative value when the energy value of the nitride phosphor of Comparative Example 1 is 100%. The emission spectrum obtained is shown in FIG.
比較例１はケイ素単体を用いずに、２０００℃で焼成した蛍光体であり、これを基準としてＥＮＧを表している。窒化ケイ素とケイ素単体を併用した実施例１から５は、比表面積が０．３ｍ２／ｇ未満、且つ平均粒径が１８μｍ以上となっており、ＥＮＧも高くなり発光特性が良好であった。 Comparative Example 1 is a phosphor fired at 2000° C. without using silicon alone, and ENG is expressed on the basis of this. In Examples 1 to 5 in which silicon nitride and silicon alone were used in combination, the specific surface area was less than 0.3 m 2 /g, the average particle size was 18 μm or more, and the ENG was also high and the light emission characteristics were good.
また、図３と図４に比較例１及び実施例１の窒化物蛍光体の走査型電子顕微鏡（ＳＥＭ）写真を示す。図３に示す比較例１では大きな粒子に微小粒子が混在している。これは、高温で焼成することで、粒子同士が焼結してしまい、分散する粉砕工程において、粒子も粉砕されて微粒子化が生じているためと思われる。図４に示す実施例１では微小粒子が存在しておらず、焼成品を粉砕しても、焼結が少ないために粒子の粉砕が生じていないことが分かる。実施例１の窒化物蛍光体では、粉砕工程で粒子を痛めることが少なく、図４に示すように粒子の表面が滑らかであり、発光輝度が低い微小粒子が混在しないためにＥＮＧが高くなっていると思われる。本実施例の窒化物蛍光体を含む発光装置においては、レイリー散乱を引き起こすような微小粒子も少ないと考えられることにより、発光素子から射出された光の発光装置内部（発光素子）へ向かっての散乱が抑制され、発光装置外部、すなわち光取り出し面へ向かっての散乱（例えば、ミー散乱）が促進されるので、発光効率が高い発光装置とすることができる。
これは例えば原料に窒化ケイ素とケイ素単体を併用することで、窒化ケイ素よりも酸素量を低減させて焼結を抑え、更にケイ素が窒化ケイ素化するときの体積変化も利用できたことにより、粒子成長と焼結性を制御できたためと考えられる。
3 and 4 show scanning electron microscope (SEM) photographs of the nitride phosphors of Comparative Example 1 and Example 1. In Comparative Example 1 shown in FIG. 3, fine particles are mixed with large particles. It is considered that this is because the particles are sintered by firing at a high temperature, and the particles are also pulverized in the pulverization step in which they are dispersed, resulting in atomization. In Example 1 shown in FIG. 4, fine particles do not exist, and it can be seen that even if the fired product is crushed, the particles are not crushed because the amount of sintering is small. In the nitride phosphor of Example 1, the particles are less likely to be damaged in the pulverizing step, the surface of the particles is smooth as shown in FIG. 4, and the ENG is high because fine particles having low emission brightness are not mixed. It seems that In the light emitting device including the nitride phosphor of the present embodiment, it is considered that there are few fine particles that cause Rayleigh scattering, so that the light emitted from the light emitting element travels toward the inside of the light emitting device (light emitting element). Since scattering is suppressed and scattering (for example, Mie scattering) toward the outside of the light emitting device, that is, toward the light extraction surface is promoted, a light emitting device with high emission efficiency can be obtained.
This is because, for example, by using silicon nitride and silicon simple substance together as a raw material, the amount of oxygen is reduced compared to silicon nitride to suppress sintering, and the volume change when silicon is converted into silicon nitride can be utilized. This is probably because the growth and sinterability could be controlled.
一方、窒化ケイ素を用いない比較例２では、粒径と比表面積が大きくなり、ＥＮＧが低下している。これは蛍光体形成とケイ素の窒化工程とを同時に行っているため、ケイ素の窒化が不十分なために特性低下していると考えられる。窒化ケイ素とケイ素単体を併用することにより窒化ケイ素がケイ素の窒化作用を促進していることが関連していると考えられる。 On the other hand, in Comparative Example 2 in which silicon nitride is not used, the particle size and the specific surface area are large and the ENG is low. It is considered that this is because the phosphor formation and the silicon nitriding step are performed at the same time, and the characteristics are deteriorated due to insufficient nitridation of silicon. It is considered that it is related that silicon nitride promotes the nitriding action of silicon by using silicon nitride and silicon alone.
（実施例６）
ストロンチウム化合物として窒化ストロンチウムを用い、原料混合物の組成をＳｒ：Ｃａ：Ｓｉ：Ａｌ：Ｅｕ＝０．０９９：０．８９１：１．１：０．９：０．０１のモル比となるように変更し、窒化ケイ素とケイ素単体の配合割合を窒化ケイ素が３７．５重量％、ケイ素単体が６２．５重量％となるように変更したこと以外は実施例１と同様にして窒化物蛍光体を得た。
(Example 6)
Strontium nitride was used as the strontium compound, and the composition of the raw material mixture was changed to a molar ratio of Sr:Ca:Si:Al:Eu=0.099:0.891:1.1:0.9:0.01. Then, a nitride phosphor was obtained in the same manner as in Example 1 except that the mixing ratio of silicon nitride and silicon simple substance was changed so that silicon nitride was 37.5 wt% and silicon simple substance was 62.5 wt %. It was
（比較例３）
ケイ素単体を用いずに、窒化ケイ素のみを用いたこと以外は、実施例６と同様にして窒化物蛍光体を得た。
(Comparative example 3)
A nitride phosphor was obtained in the same manner as in Example 6 except that only silicon nitride was used without using silicon simple substance.
得られた窒化物蛍光体を上記と同様に評価した。表２に平均粒径、比表面積、λｐ、ＥＮＧ（％）を示す。ＥＮＧ（％）は、比較例１の窒化物蛍光体のエネルギー値を１００％とした相対値である。また図５に得られた発光スペクトルを示す。 The obtained nitride phosphor was evaluated in the same manner as above. Table 2 shows the average particle size, specific surface area, λp, and ENG (%). ENG (%) is a relative value when the energy value of the nitride phosphor of Comparative Example 1 is 100%. The emission spectrum obtained is shown in FIG.
表２及び図５に示される通り、発光ピーク波長は実施例６が６５７ｎｍ、比較例３が６６３ｎｍと実施例１よりも長くなっている。これはＥｕ量を変更した影響が大きいと考えられる。実施例６も実施例１から５と同じように原料にケイ素単体を加えることで、比表面積が０．２ｍ２／ｇ以下と小さく、比較例３よりも発光特性が高くなっており、良好な結果であった。 As shown in Table 2 and FIG. 5, the emission peak wavelength is 657 nm in Example 6 and 663 nm in Comparative Example 3, which is longer than that in Example 1. It is considered that this is largely influenced by changing the Eu amount. In Example 6, as in Examples 1 to 5, by adding a simple substance of silicon to the raw material, the specific surface area was as small as 0.2 m 2 /g or less, and the light emitting property was higher than that in Comparative Example 3, which was excellent. It was a result.
本発明に係る一実施形態の製造方法で得られる窒化物蛍光体を用いた発光装置は、照明用の光源等として好適に利用できる。特に照明用光源、ＬＥＤディスプレイ、バックライト光源、信号機、照明式スイッチ及び各種インジケータ等に好適に利用できる。特に発光輝度の高い窒化物蛍光体等が得られるので、産業上の利用価値は極めて高い。 The light emitting device using the nitride phosphor obtained by the manufacturing method of the embodiment according to the present invention can be suitably used as a light source for illumination or the like. In particular, it can be suitably used for an illumination light source, an LED display, a backlight light source, a traffic light, an illumination switch, various indicators and the like. In particular, since a nitride phosphor having a high emission brightness can be obtained, its industrial utility value is extremely high.
１０：発光素子、５０：蛍光部材、７１：第一蛍光体、７２：第二蛍光体、１００：発光装置 10: light emitting element, 50: fluorescent member, 71: first fluorescent material, 72: second fluorescent material, 100: light emitting device
Claims (6)
ＳｒｓＣａｔＡｌｕＳｉｖＮｗ：Ｅｕ （Ｉ）
（ｓ、ｔ、ｕ、ｖ及びｗはそれぞれ、０≦ｓ＜１、０＜ｔ≦１、ｓ＋ｔ≦１、０．９≦ｕ≦１．１、０．９≦ｖ≦１．１、及び２．５≦ｗ≦３．５を満たす） The nitride phosphor according to claim 1, wherein the nitride phosphor has a composition represented by the following formula (I).
Sr s Ca t Al u Si v N w: Eu (I)
(S, t, u, v, and w are 0≦s<1, 0<t≦1, s+t≦1, 0.9≦u≦1.1, 0.9≦v≦1.1, and 2.5≦w≦3.5 is satisfied)
前記第一蛍光体が請求項１から４のいずれか１項に記載の窒化物蛍光体を含む発光装置。 A fluorescent member including the first phosphor, and a light emitting element having an emission peak wavelength in a range of 380 nm to 470 nm,
A light emitting device in which the first phosphor includes the nitride phosphor according to any one of claims 1 to 4 .
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| TW201713749A (en) | 2017-04-16 |
| JP6202154B2 (en) | 2017-09-27 |
| JP2017210626A (en) | 2017-11-30 |
| TWI599637B (en) | 2017-09-21 |
| KR20170026123A (en) | 2017-03-08 |
| CN106479491B (en) | 2019-08-23 |
| JP2017043761A (en) | 2017-03-02 |
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| KR101848556B1 (en) | 2018-04-12 |
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