JP2018087323A - Fluorescent material, method of producing the same, and light emitting device - Google Patents
Fluorescent material, method of producing the same, and light emitting device Download PDFInfo
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 50
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 229910052800 carbon group element Inorganic materials 0.000 claims abstract description 13
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
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- 239000006185 dispersion Substances 0.000 claims description 52
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
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- 239000003637 basic solution Substances 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
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Abstract
Description
本発明は、蛍光体、その製造方法及び発光装置に関する。 The present invention relates to a phosphor, a manufacturing method thereof, and a light emitting device.
励起光源として青色を発光する発光素子と、励起光源からの光によって励起されて、赤色を発光する蛍光体及び緑色を発光する蛍光体とを組み合わせて白色光を放出する発光装置が知られている。このような発光装置は、一般照明、車載照明、ディスプレイ、液晶用バックライト等の幅広い分野での使用が進められている。 A light-emitting device that emits white light by combining a light-emitting element that emits blue light as an excitation light source and a phosphor that emits red light and a phosphor that emits green light when excited by light from the excitation light source is known. . Such light emitting devices are being used in a wide range of fields such as general lighting, in-vehicle lighting, displays, and backlights for liquid crystals.
青色域に励起帯を有し、発光ピークの半値幅の狭い赤色に発光する蛍光体として、例えば特許文献１に開示されるＫ２ＳｉＦ６：Ｍｎ４＋の組成を有するフッ化物蛍光体が知られている。 As a phosphor that has an excitation band in a blue region and emits red light with a narrow half-value width of an emission peak, for example, a fluoride phosphor having a composition of K 2 SiF 6 : Mn 4+ disclosed in Patent Document 1 is known. ing.
しかしながら、従来技術で開示されている赤色に発光する蛍光体を用いて発光装置を構成した場合、蛍光体の耐久性に改善の余地がある。照明用途で発光装置を使用する場合は、より高い耐久性が求められる。
そこで、本発明の一態様は、耐久性に優れる赤色に発光する蛍光体、その製造方法及び発光装置を提供することを目的とする。
However, when a light emitting device is configured using a phosphor that emits red light as disclosed in the prior art, there is room for improvement in the durability of the phosphor. When the light emitting device is used for illumination, higher durability is required.
In view of the above, an object of one embodiment of the present invention is to provide a phosphor that emits red light with excellent durability, a manufacturing method thereof, and a light-emitting device.
前記課題を解決するための手段は、以下の通りであり、本発明は、以下の態様を包含する。
本発明の第一の態様は、Ｍｎと、アルカリ金属元素及びＮＨ４ ＋からなる群より選ばれる少なくとも一種の元素と、第４族元素及び第１４族元素からなる群より選ばれる少なくとも一種の元素とを組成に有するフッ化物を含む蛍光体コアと、前記蛍光体コアの表面に配置されたアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方とを含む、蛍光体である。
Means for solving the above-mentioned problems are as follows, and the present invention includes the following aspects.
In a first aspect of the present invention, Mn, at least one element selected from the group consisting of alkali metal elements and NH 4 +, and at least one element selected from the group consisting of Group 4 elements and Group 14 elements And a phosphor core containing a fluoride having the composition and at least one of aluminum hydroxide particles and calcium hydroxide particles disposed on the surface of the phosphor core.
本発明の第二の態様は、前記蛍光体を含む第一蛍光体と、３８０ｎｍ以上４７０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子を含む発光装置である。 A second aspect of the present invention is a light emitting device including a first phosphor containing the phosphor and a light emitting element having an emission peak wavelength in a wavelength range of 380 nm to 470 nm.
本発明の第三の態様は、Ｍｎと、アルカリ金属元素及びＮＨ４ ＋からなる群より選ばれる少なくとも一種の元素と、第４族元素及び第１４族元素からなる群より選ばれる少なくとも一種の元素とを組成に有するフッ化物を含む蛍光体コアを準備することと、前記蛍光体コアを液媒体に分散させた分散液中で、前記蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させることと、前記蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させた蛍光体と液媒体とを分離することを含む、蛍光体の製造方法である。 In a third aspect of the present invention, at least one element selected from the group consisting of Mn, at least one element selected from the group consisting of alkali metal elements and NH 4 +, and Group 4 elements and Group 14 elements is used. And preparing a phosphor core containing a fluoride having a composition in a dispersion liquid in which the phosphor core is dispersed in a liquid medium, the aluminum hydroxide particles and the calcium hydroxide particles on the phosphor core A method of producing a phosphor, comprising: attaching at least one of the phosphor; and separating a phosphor having at least one of aluminum hydroxide particles and calcium hydroxide particles attached to the phosphor core and a liquid medium. It is.
本発明の一実施形態によれば、耐久性に優れる赤色に発光する蛍光体、その製造方法及び発光装置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 phosphor that emits red light with excellent durability, a method for manufacturing the same, and a light emitting device.
以下、本開示に係る蛍光体、その製造方法及び発光装置を説明する。ただし、以下に示す実施の形態は、本発明の技術思想を具体化するための例示であって、本発明を以下のものに限定するものではない。なお、本明細書において、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作用が達成されれば、本用語に含まれる。また、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, the phosphor, the manufacturing method thereof, and the light emitting device according to the present disclosure will be described. However, the embodiment described below is an example for embodying the technical idea of the present invention, and the present invention is not limited to the following. In this specification, the relationship between color names and chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, and the like comply with JIS Z8110. In addition, the term “process” is not limited to an independent process, and is included in this term if the intended action of the process is achieved even 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 there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .
蛍光体
本発明の第一の実施形態よれば、蛍光体は、Ｍｎと、アルカリ金属元素及びＮＨ４ ＋からなる群より選ばれる少なくとも一種の元素と、第４族元素及び第１４族元素からなる群より選ばれる少なくとも一種の元素とを組成に有するフッ化物を含む蛍光体コアと、前記蛍光体コアの表面に配置されたアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方とを含む。蛍光体コアに含まれるフッ化物の組成に含まれるＭｎは、好ましくはＭｎ４＋であり、例えばＭｎ４＋又はＭｎ４＋としてＭｎを含む複合フッ化物の形態である。「蛍光」とは光が照射されると発光することを意味する。
Phosphor According to the first embodiment of the present invention, the phosphor comprises Mn, at least one element selected from the group consisting of an alkali metal element and NH 4 + , a Group 4 element, and a Group 14 element. A phosphor core containing a fluoride having at least one element selected from the group in composition, and at least one of aluminum hydroxide particles and calcium hydroxide particles disposed on the surface of the phosphor core. Mn contained in the composition of the fluoride contained in the phosphor core is preferably Mn 4+ , for example, in the form of a composite fluoride containing Mn as Mn 4+ or Mn 4+ . “Fluorescence” means light emission when irradiated with light.
蛍光体コアの表面へのアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子の付着は、ファンデルワールス力、静電相互作用等の物理的な相互作用、部分的な化学反応による化学的な相互作用等のいずれによるものであってもよい。例えば化学的な相互作用による場合は、蛍光体コアを構成する元素と、水酸化物中に含まれるアルミニウム及びカルシウムの少なくとも一方が、酸素を介して結合する部分的な化学反応によってアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子が蛍光体コアに付着されると考えられる。また、アルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子は、粒子状態で蛍光体コアの表面に付着されているが、後述する二酸化ケイ素を含む膜状物中に含まれている状態で蛍光体コアの表面に付着されていてもよい。アルミニウム水酸化物粒子は、例えば水酸化アルミニウム（Ａｌ（ＯＨ）３）粒子、水酸化酸化アルミニウム（ＡｌＯ（ＯＨ））粒子が挙げられる。カルシウム水酸化物粒子は、例えば水酸化カルシウム（Ｃａ（ＯＨ）２）粒子が挙げられる。 Adhesion of aluminum hydroxide particles and / or calcium hydroxide particles to the surface of the phosphor core is caused by chemical interactions such as van der Waals forces, physical interactions such as electrostatic interactions, and partial chemical reactions. Any of interaction and the like may be used. For example, in the case of chemical interaction, aluminum hydroxide is formed by a partial chemical reaction in which at least one of the elements constituting the phosphor core and aluminum and calcium contained in the hydroxide is bonded via oxygen. It is believed that the particles and / or calcium hydroxide particles are attached to the phosphor core. In addition, aluminum hydroxide particles and / or calcium hydroxide particles are adhered to the surface of the phosphor core in a particle state, but are fluorescent in a state where they are contained in a film containing silicon dioxide described later. It may be attached to the surface of the body core. Examples of the aluminum hydroxide particles include aluminum hydroxide (Al (OH) 3 ) particles and aluminum hydroxide oxide (AlO (OH)) particles. Examples of the calcium hydroxide particles include calcium hydroxide (Ca (OH) 2 ) particles.
従来の発光装置は、フッ化物を含む蛍光体粒子と樹脂とを含む蛍光部材を備えており、この蛍光体粒子の表面にフッ化物中に含まれているフッ素が多く存在する。そして、蛍光体粒子の表面に存在するフッ素の影響により、蛍光体粒子と樹脂の密着性が低下するものと考えられる。
このように蛍光体粒子と樹脂の密着性が低い蛍光部材を備えた発光装置において、発光素子に高電流を流して発光させた場合に、樹脂が膨張すると、蛍光体粒子と樹脂が界面で剥離することがある。蛍光体粒子と樹脂の界面で剥離が発生すると、蛍光体粒子と樹脂の間の僅かな空隙が形成される。蛍光体粒子と樹脂の間の僅かな空隙で光が散乱され、蛍光体粒子への励起光の入射量の低下と、蛍光体粒子から発光装置の外に取り出される光量が低下すると考えられる。
A conventional light emitting device includes a fluorescent member including a phosphor particle containing a fluoride and a resin, and a large amount of fluorine contained in the fluoride exists on the surface of the phosphor particle. And it is thought that the adhesiveness of fluorescent substance particle and resin falls by the influence of the fluorine which exists on the surface of fluorescent substance particle.
In such a light emitting device having a fluorescent member with low adhesion between the phosphor particles and the resin, if the resin expands when a high current is passed through the light emitting element, the phosphor particles and the resin peel at the interface. There are things to do. When peeling occurs at the interface between the phosphor particles and the resin, a slight gap is formed between the phosphor particles and the resin. It is considered that light is scattered in a slight gap between the phosphor particles and the resin, the amount of excitation light incident on the phosphor particles is decreased, and the amount of light extracted from the phosphor particles to the outside of the light emitting device is decreased.
本発明の第一の実施形態によれば、蛍光体は、特定の組成を有するフッ化物を含む蛍光体コアの表面にアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方が付着している。そのため、このアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子が、フッ化物からわずかに発生するフッ素ガス（Ｆ２）、フッ化水素ガス（ＨＦ）、又はフッ化ケイ素ガス（ＳｉＦ４）等のフッ素（Ｆ）を含むガスを化学的又は物理的に捕捉する。蛍光体コアからわずかに発生するフッ素を含むガスが蛍光体コアの表面に付着されたアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子によって捕捉されるため、フッ素を含むガスによって生じる樹脂の劣化を抑制することができる。樹脂の劣化が抑制されるため、蛍光体と樹脂の密着性の低下が抑制される。本発明の一実施形態によれば、蛍光体は、蛍光体と樹脂との密着性の低下が抑制されるため、色度座標におけるｘ値及びｙ値の変化が少なく、色度変化が抑制され、優れた耐久性を有する発光装置を構成することができる。 According to the first embodiment of the present invention, the phosphor has at least one of aluminum hydroxide particles and calcium hydroxide particles attached to the surface of the phosphor core containing a fluoride having a specific composition. . Therefore, the aluminum hydroxide particles and / or calcium hydroxide particles are slightly generated from fluoride, such as fluorine gas (F 2 ), hydrogen fluoride gas (HF), or silicon fluoride gas (SiF 4 ). The gas containing fluorine (F) is chemically or physically trapped. Deterioration of the resin caused by the fluorine-containing gas because the fluorine-containing gas generated slightly from the phosphor core is captured by the aluminum hydroxide particles and / or calcium hydroxide particles attached to the surface of the phosphor core. Can be suppressed. Since deterioration of the resin is suppressed, a decrease in adhesion between the phosphor and the resin is suppressed. According to one embodiment of the present invention, since the phosphor is suppressed from lowering the adhesion between the phosphor and the resin, the change in the x value and the y value in the chromaticity coordinates is small, and the chromaticity change is suppressed. Thus, a light emitting device having excellent durability can be configured.
蛍光体コアに含まれるフッ化物が、以下の式（１）で表される組成を有することが好ましい。また、蛍光体コアに含まれるフッ化物が、少なくとも組成にカリウム（Ｋ）とケイ素（Ｓｉ）を含むことが好ましい。
Ａ２［Ｍ１−ｐＭｎ４＋ ｐＦ６］ （１）
式（１）中、Ａはアルカリ金属元素及びＮＨ４ ＋からなる群から選ばれる少なくとも一種の元素であり、Ｍは第４族元素及び第１４族元素からなる群から選ばれる少なくとも一種の元素であり、ｐは０＜ｐ＜０．１を満たす数である。
蛍光体コアに含まれるフッ化物の詳細は、既述のとおりである。
It is preferable that the fluoride contained in the phosphor core has a composition represented by the following formula (1). Moreover, it is preferable that the fluoride contained in the phosphor core contains at least potassium (K) and silicon (Si) in the composition.
A 2 [M 1-p Mn 4+ p F 6] (1)
In formula (1), A is at least one element selected from the group consisting of alkali metal elements and NH 4 + , and M is at least one element selected from the group consisting of Group 4 elements and Group 14 elements. And p is a number satisfying 0 <p <0.1.
The details of the fluoride contained in the phosphor core are as described above.
本発明の第一の実施形態によれば、蛍光体は、蛍光体コアの表面に配置された二酸化ケイ素を更に含むことが好ましい。二酸化ケイ素は、蛍光体コアの表面に付着されていることが好ましい。蛍光体コアの表面への二酸化ケイ素の付着は、蛍光体コア中の元素とケイ素（Ｓｉ）が酸素（Ｏ）を介した化学的な相互作用によるものであることが好ましい。蛍光体コアの表面への二酸化ケイ素の付着は、ファンデルワールス力、静電相互作用等の物理的な相互作用によるものであってもよい。また、二酸化ケイ素は、アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を含む膜状物となって、蛍光体コアの表面に付着されることが好ましい。二酸化ケイ素を含む膜状物により、アルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子を、蛍光体コアの表面により強固に配置することができるので、それらの粒子が蛍光体コアから脱離することを防ぐことができる。 According to the first embodiment of the present invention, the phosphor preferably further includes silicon dioxide disposed on the surface of the phosphor core. Silicon dioxide is preferably attached to the surface of the phosphor core. The adhesion of silicon dioxide to the surface of the phosphor core is preferably due to chemical interaction between the element in the phosphor core and silicon (Si) via oxygen (O). The attachment of silicon dioxide to the surface of the phosphor core may be due to physical interactions such as van der Waals forces and electrostatic interactions. Moreover, it is preferable that silicon dioxide becomes a film-like material containing at least one of aluminum hydroxide particles and calcium hydroxide particles and is attached to the surface of the phosphor core. With the film-like material containing silicon dioxide, aluminum hydroxide particles and / or calcium hydroxide particles can be arranged more firmly on the surface of the phosphor core, so that these particles are detached from the phosphor core. Can be prevented.
蛍光体コアの表面に配置されたアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子中のアルミニウム及びカルシウムの合計の含有量は、蛍光体１００質量％に対して、好ましくは０．１質量％以上５．０質量％以下の範囲であり、より好ましくは０．２質量％以上４．０質量％以下の範囲であり、さらに好ましくは０．２質量％以上３．０質量％以下の範囲である。蛍光体コアの表面に配置されたアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子中のアルミニウム及びカルシウムの合計の含有量が、０．１質量％以上５．０質量％以下の範囲内であれば、前記蛍光体は、発光特性の低下を抑制し、優れた耐久性を有する。アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方とは、アルミニウム水酸化物粒子単独でもよく、カルシウム水酸化物粒子単独でもよく、アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の混合物でもよい。 The total content of aluminum and calcium in the aluminum hydroxide particles and / or calcium hydroxide particles arranged on the surface of the phosphor core is preferably 0.1% by mass with respect to 100% by mass of the phosphor. In the range of 5.0% by mass or less, more preferably in the range of 0.2% by mass or more and 4.0% by mass or less, and further preferably in the range of 0.2% by mass or more and 3.0% by mass or less. is there. The total content of aluminum and calcium in the aluminum hydroxide particles and / or calcium hydroxide particles arranged on the surface of the phosphor core is within a range of 0.1% by mass or more and 5.0% by mass or less. If present, the phosphor suppresses a decrease in light emission characteristics and has excellent durability. At least one of the aluminum hydroxide particles and calcium hydroxide particles may be aluminum hydroxide particles alone, calcium hydroxide particles alone, or a mixture of aluminum hydroxide particles and calcium hydroxide particles. .
蛍光体コアの表面に配置された二酸化ケイ素に含まれるケイ素の含有量は、蛍光体１００質量％に対して、好ましくは０．１質量％以上１０．０質量％以下の範囲であり、より好ましくは１．０質量％以上８．０質量％以下の範囲であり、さらに好ましくは１．５質量％以上５．０質量％以下の範囲である。蛍光体コアの表面に配置された二酸化ケイ素に含まれるケイ素の含有量が、０．１質量％以上１０．０質量％以下の範囲内であれば、蛍光体の発光特性の低下を抑制し、アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を蛍光体コアの表面に配置させることができる。 The content of silicon contained in silicon dioxide disposed on the surface of the phosphor core is preferably in the range of 0.1% by mass or more and 10.0% by mass or less, more preferably 100% by mass of the phosphor. Is 1.0 mass% or more and 8.0 mass% or less, More preferably, it is 1.5 mass% or more and 5.0 mass% or less. If the content of silicon contained in the silicon dioxide disposed on the surface of the phosphor core is in the range of 0.1% by mass or more and 10.0% by mass or less, it is possible to suppress a decrease in the emission characteristics of the phosphor, At least one of the aluminum hydroxide particles and the calcium hydroxide particles can be arranged on the surface of the phosphor core.
蛍光体コアの表面に配置されたアルミニウム水酸化物粒子中のアルミニウム、カルシウム水酸化物粒子中のカルシウム、膜状物である二酸化ケイ素中のケイ素の蛍光体中の含有率は、ＩＣＰ−ＡＥＳ（高周波誘導結合プラズマ発光分光分析法）を用いて測定することができる。 The content of aluminum in the aluminum hydroxide particles, calcium in the calcium hydroxide particles, and silicon in the silicon dioxide film, which is disposed on the surface of the phosphor core, in the phosphor is ICP-AES ( It can be measured using high frequency inductively coupled plasma emission spectroscopy.
Ｍｎ４＋で賦活されたフッ化物を含む蛍光体コアは、可視光の短波長領域の光を吸収して赤色に発光可能である。可視光の短波長領域の励起光は、主に青色領域の光であることが好ましい。励起光は、具体的には、３８０ｎｍ以上４８５ｎｍ以下の波長範囲に発光ピーク波長が存在することが好ましく、発光ピーク波長が３８０ｎｍ以上４７０ｎｍ以下の波長範囲に発光ピーク波長が存在することがより好ましい。励起光が、前記波長範囲に発光ピーク波長を有するものであれば、蛍光体の発光効率を向上させることができる。 A phosphor core containing a fluoride activated with Mn 4+ can absorb red light in the short wavelength region of visible light and emit red light. The excitation light in the short wavelength region of visible light is preferably mainly blue light. Specifically, the excitation light preferably has an emission peak wavelength in a wavelength range of 380 nm to 485 nm, and more preferably an emission peak wavelength in a wavelength range of 380 nm to 470 nm. If the excitation light has an emission peak wavelength in the wavelength range, the luminous efficiency of the phosphor can be improved.
また、蛍光体は、発光スペクトルの発光ピーク波長が６１０ｎｍ以上６５０ｎｍ以下の範囲に存在することが好ましい。また蛍光体の発光スペクトルの半値幅は、小さいことが好ましく、具体的には１０ｎｍ以下であることが好ましい。 In addition, the phosphor preferably has an emission peak wavelength of an emission spectrum in a range of 610 nm to 650 nm. In addition, the half width of the emission spectrum of the phosphor is preferably small, specifically 10 nm or less.
蛍光体は、体積平均粒径が１μｍ以上１００μｍ以下の範囲であることが好ましく、２μｍ以上８０μｍ以下の範囲であることがより好ましく、５μｍ以上７０μｍ以下の範囲であることが更に好ましい。蛍光体は、その体積平均粒径が１μｍ以上１００μｍ以下の範囲内であれば、高い発光強度を維持し、耐久性を向上させることができる。蛍光体は、その体積平均粒径が１μｍ以上１００μｍ以下の範囲内であれば、発光装置を製造する際の作業性を向上させることができる。また、蛍光体の粒子の粒度分布が、１μｍ以上１００μｍの範囲内にピークを有する単一ピークの粒度分布であることが好ましく、分布幅の狭い粒度分布であることがより好ましい。本明細書において、蛍光体の体積平均粒径は、レーザー回折式粒度分布測定装置（ＭＡＬＶＥＲＮ社製ＭＡＳＴＥＲ ＳＩＺＥＲ ２０００）により測定される粒径（メジアン径）である。 The phosphor preferably has a volume average particle size in the range of 1 μm to 100 μm, more preferably in the range of 2 μm to 80 μm, and still more preferably in the range of 5 μm to 70 μm. If the volume average particle diameter is in the range of 1 μm or more and 100 μm or less, the phosphor can maintain high emission intensity and improve durability. When the phosphor has a volume average particle diameter in the range of 1 μm or more and 100 μm or less, the workability in manufacturing the light emitting device can be improved. In addition, the particle size distribution of the phosphor particles is preferably a single peak particle size distribution having a peak in the range of 1 μm to 100 μm, and more preferably a narrow particle size distribution. In the present specification, the volume average particle diameter of the phosphor is a particle diameter (median diameter) measured by a laser diffraction particle size distribution measuring apparatus (MASTER SIZER 2000 manufactured by MALVERN).
蛍光体の製造方法
本発明の第二の実施形態によれば、蛍光体の製造方法は、Ｍｎと、アルカリ金属元素及びＮＨ４ ＋からなる群より選ばれる少なくとも一種の元素と、第４族元素及び第１４族元素からなる群より選ばれる少なくとも一種の元素とを組成に有するフッ化物を含む蛍光体コアを準備することと（以下、「準備工程」ともいう。）、前記蛍光体コアを液媒体に分散させた分散液中で、前記蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させることと（以下、「付着工程」ともいう。）、前記蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させた蛍光体と液媒体とを分離すること（以下、「分離工程」ともいう。）を含む。
Method for Producing Phosphor According to the second embodiment of the present invention, the method for producing a phosphor includes Mn, at least one element selected from the group consisting of an alkali metal element and NH 4 +, and a Group 4 element. And a phosphor core containing a fluoride having at least one element selected from the group consisting of Group 14 elements in the composition (hereinafter also referred to as “preparation step”), and the phosphor core as a liquid Attaching at least one of aluminum hydroxide particles and calcium hydroxide particles to the phosphor core in a dispersion liquid dispersed in a medium (hereinafter, also referred to as “attachment step”), and the phosphor core. Separating the phosphor having at least one of aluminum hydroxide particles and calcium hydroxide particles attached thereto and the liquid medium (hereinafter also referred to as “separation step”).
準備工程
準備工程では、Ｍｎと、アルカリ金属元素及びＮＨ４ ＋からなる群から選ばれる少なくとも一種の元素と、第４族元素及び第１４族元素からなる群から選ばれる少なくとも一種の元素とを組成に有するフッ化物を含む蛍光体コアを準備する。蛍光体コアは、そのままでも励起光を吸収して発光する蛍光体としての機能を有する。蛍光体コアは市販品から適宜選択して準備してもよく、例えば特開２０１２−２２４５３６号公報に記載されている既に公知の方法に従って蛍光体を製造して準備してもよい。
Preparation Step In the preparation step, Mn, at least one element selected from the group consisting of alkali metal elements and NH 4 +, and at least one element selected from the group consisting of Group 4 elements and Group 14 elements are composed. A phosphor core containing a fluoride is prepared. The phosphor core has a function as a phosphor that absorbs excitation light and emits light as it is. The phosphor core may be prepared by appropriately selecting from commercially available products. For example, the phosphor core may be prepared by preparing a phosphor according to an already known method described in JP 2012-224536 A.
蛍光体コアに含まれるフッ化物は、少なくとも組成にカリウム（Ｋ）とケイ素（Ｓｉ）を含むことが好ましい。フッ化物は以下の式（１）で表される組成を有することが好ましい。
Ａ２［Ｍ１−ｐＭｎ４＋ ｐＦ６］ （１）
式（１）中、Ａはアルカリ金属元素及びＮＨ４ ＋からなる群から選ばれる少なくとも一種の元素であり、Ｍは第４族元素及び第１４族元素からなる群から選ばれる少なくとも一種の元素であり、ｐは０＜ｐ＜０．１を満たす数である。
The fluoride contained in the phosphor core preferably contains at least potassium (K) and silicon (Si) in the composition. The fluoride preferably has a composition represented by the following formula (1).
A 2 [M 1-p Mn 4+ p F 6] (1)
In formula (1), A is at least one element selected from the group consisting of alkali metal elements and NH 4 + , and M is at least one element selected from the group consisting of Group 4 elements and Group 14 elements. And p is a number satisfying 0 <p <0.1.
式（１）におけるＡは、アルカリ金属元素及びＮＨ４ ＋からなる群から選ばれる少なくとも一種の元素であり、少なくともＫを含み、Ｌｉ、Ｎａ、Ｒｂ、Ｃｓ及びＮＨ４ ＋からなる群から選択される少なくとも一種の元素をさらに含んでいてもよく、Ｋを主成分とするアルカリ金属元素を含むことがさらに好ましい。ここで「Ｋを主成分とする」とは、式（１）のＡにおけるＫの含有率が８０モル％以上であることを意味し、９０モル％以上であることが好ましく、９５モル％以上であることがより好ましい。 A in Formula (1) is at least one element selected from the group consisting of alkali metal elements and NH 4 + , and includes at least K, and is selected from the group consisting of Li, Na, Rb, Cs, and NH 4 +. At least one kind of element may be further contained, and it is more preferred that an alkali metal element mainly composed of K is contained. Here, “having K as a main component” means that the content of K in A in the formula (1) is 80 mol% or more, preferably 90 mol% or more, and preferably 95 mol% or more. It is more preferable that
式（１）におけるＭは、第４族元素及び第１４族元素からなる群から選択される少なくとも一種の元素であり、Ｍは、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、ハフニウム（Ｈｆ）、ケイ素（Ｓｉ）、ゲルマニウム（Ｇｅ）及びスズ（Ｓｎ）からなる群から選択される少なくとも一種の元素であることが好ましく、式（１）におけるＭは、ケイ素（Ｓｉ）、又はケイ素（Ｓｉ）及びゲルマニウム（Ｇｅ）を含むことがより好ましく、ケイ素（Ｓｉ）、又はケイ素（Ｓｉ）及びゲルマニウム（Ｇｅ）であることが更に好ましい。 M in Formula (1) is at least one element selected from the group consisting of Group 4 elements and Group 14 elements, and M is titanium (Ti), zirconium (Zr), hafnium (Hf), silicon. Preferably, it is at least one element selected from the group consisting of (Si), germanium (Ge), and tin (Sn), and M in formula (1) is silicon (Si), silicon (Si), and germanium. More preferably, (Ge) is included, and silicon (Si), or silicon (Si) and germanium (Ge) are more preferable.
式（１）におけるＭがケイ素（Ｓｉ）、又はケイ素（Ｓｉ）及びゲルマニウム（Ｇｅ）を含む場合、Ｓｉ及びＧｅの少なくとも一方の一部が、Ｔｉ、Ｚｒ及びＨｆを含む第４族元素、並びにＣ及びＳｎを含む第１４族元素からなる群から選択される少なくとも一種の元素で置換されていてもよい。式（１）におけるＭ中のＳｉ及びＧｅの総含有率は、例えば、９０モル％以上であることが好ましく、９５モル％以上であることがより好ましい。 When M in Formula (1) includes silicon (Si) or silicon (Si) and germanium (Ge), at least one of Si and Ge includes a Group 4 element including Ti, Zr, and Hf, and It may be substituted with at least one element selected from the group consisting of Group 14 elements including C and Sn. The total content of Si and Ge in M in Formula (1) is, for example, preferably 90 mol% or more, and more preferably 95 mol% or more.
式（１）における変数ｐは、発光効率と発光強度の観点から、０＜ｐ＜０．１を満たす数であることが好ましく、０．０１≦ｐ＜０．０９を満たす数であることがより好ましく、０．０２≦ｐ≦０．０８を満たす数であることがさらに好ましい。 The variable p in the formula (1) is preferably a number satisfying 0 <p <0.1, and a number satisfying 0.01 ≦ p <0.09, from the viewpoint of light emission efficiency and light emission intensity. More preferably, the number is more preferably 0.02 ≦ p ≦ 0.08.
付着工程
付着工程では、準備した蛍光体コアを液媒体に分散させた分散液中で、アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を前記蛍光体コアに付着させる。
Adhesion step In the adhesion step, at least one of aluminum hydroxide particles and calcium hydroxide particles is adhered to the phosphor core in a dispersion obtained by dispersing the prepared phosphor core in a liquid medium.
付着工程は、蛍光体コアを分散させた分散液に、ケイ素化合物と、塩基性溶液とを加え、アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方と、二酸化ケイ素とを含む膜状物を前記蛍光体コアに付着させる工程を含むことが好ましい。二酸化ケイ素を含む膜状物により、アルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子を、蛍光体コアの表面により強固に配置することができるので、それらの粒子が蛍光体コアから脱離することを防ぐことができる。 The attaching step includes adding a silicon compound and a basic solution to a dispersion in which the phosphor core is dispersed, and forming a film-like material containing at least one of aluminum hydroxide particles and calcium hydroxide particles and silicon dioxide. It is preferable that the method includes a step of attaching to the phosphor core. With the film-like material containing silicon dioxide, aluminum hydroxide particles and / or calcium hydroxide particles can be arranged more firmly on the surface of the phosphor core, so that these particles are detached from the phosphor core. Can be prevented.
蛍光体コアを分散させた分散液に、アルミニウム塩と、塩基性溶液とを加え、アルミニウム水酸化物粒子を蛍光体コアに付着させることを含むことが好ましい。これにより、アルミニウム塩と塩基性溶液とを加えることで形成されたアルミニウム水酸化物粒子が含まれる溶液に、さらに蛍光体コアを加える他の方法と比較して、アルミニウム水酸化物粒子を蛍光体コアに均一に付着させることができると考えられる。 It is preferable to include adding an aluminum salt and a basic solution to the dispersion liquid in which the phosphor core is dispersed, and attaching the aluminum hydroxide particles to the phosphor core. As a result, the aluminum hydroxide particles are added to a solution containing aluminum hydroxide particles formed by adding an aluminum salt and a basic solution, compared to other methods in which a phosphor core is further added. It is thought that it can adhere uniformly to the core.
蛍光体コアを分散させた分散液に、ケイ素化合物と、アルミニウム塩と、塩基性溶液とを加えることによって、蛍光体コアにアルミニウム水酸化物粒子と二酸化ケイ素を含む膜状物を付着させることを含むことが好ましい。これにより、蛍光体コアにアルミニウム水酸化物粒子を付着させた後、それを分散液から取り出し、更に別工程で二酸化ケイ素を含む膜状物を付着させる他の方法と比較して、付着工程以降の工程数が減るため、作業性を向上させることができる。また、上記他の方法と比較して、付着したアルミニウム水酸化物粒子が作業の途中で蛍光体コアから脱離することを防ぐことができる。 By adding a silicon compound, an aluminum salt, and a basic solution to a dispersion liquid in which the phosphor core is dispersed, a film-like material containing aluminum hydroxide particles and silicon dioxide is attached to the phosphor core. It is preferable to include. As a result, after the aluminum hydroxide particles are attached to the phosphor core, it is removed from the dispersion, and compared with other methods of attaching a film-like material containing silicon dioxide in a separate step, Therefore, the workability can be improved. Moreover, compared with the said other method, it can prevent that the adhered aluminum hydroxide particle detach | desorbs from a fluorescent substance core in the middle of work.
蛍光体コアを分散させた分散液に、ケイ素化合物と、カルシウム塩と、塩基性溶液とを加え、蛍光体コアにカルシウム水酸化物粒子と二酸化ケイ素を含む膜状物を付着させることを含むことが好ましい。カルシウム塩は、例えば水酸化カルシウム（Ｃａ（ＯＨ）２）が挙げられる。これにより、蛍光体コアにカルシウム水酸化物粒子を付着させた後、それを分散液から取り出し、更に別工程で二酸化ケイ素を含む膜状物を付着させる他の方法と比較して、付着工程以降の工程数が減るため、作業性を向上させることができる。また、上記他の方法と比較して、付着したカルシウム水酸化物粒子が作業の途中で蛍光体コアから脱離することを防ぐことができる。 Adding a silicon compound, a calcium salt, and a basic solution to a dispersion in which the phosphor core is dispersed, and attaching a film-like material containing calcium hydroxide particles and silicon dioxide to the phosphor core. Is preferred. An example of the calcium salt is calcium hydroxide (Ca (OH) 2 ). Thereby, after attaching calcium hydroxide particles to the phosphor core, it is removed from the dispersion, and compared with other methods of attaching a film-like material containing silicon dioxide in another step, the adhesion step and thereafter Therefore, the workability can be improved. Further, compared with the other methods described above, it is possible to prevent the adhered calcium hydroxide particles from being detached from the phosphor core during the work.
液媒体は、通常用いられる液体から適宜選択することができる。液媒体として具体的には、メタノール、エタノール、イソプロピルアルコール等のアルコール系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、ジエチルエーテル、ジイソプロピルエーテル等のエーテル系溶剤などの有機溶剤や水を用いることができる。液媒体は、アルミニウム塩が溶解しやすく、後述するケイ素化合物を使用する場合にも共通溶媒として使用しやすいアルコール系溶剤を用いることが好ましい。また、分散液にケイ素化合物を加える場合には、ケイ素化合物の加水分解反応及び縮合反応を促進するために、水を含むことが好ましい。 The liquid medium can be appropriately selected from commonly used liquids. Specifically, organic solvents such as alcohol solvents such as methanol, ethanol and isopropyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as diethyl ether and diisopropyl ether, and water can be used as the liquid medium. . As the liquid medium, it is preferable to use an alcohol-based solvent that easily dissolves the aluminum salt and is easy to use as a common solvent even when a silicon compound described later is used. Moreover, when adding a silicon compound to a dispersion liquid, in order to accelerate | stimulate the hydrolysis reaction and condensation reaction of a silicon compound, it is preferable to contain water.
蛍光体コアに対する液媒体の質量比率は、蛍光体コア１００質量部に対して、好ましくは液媒体を１００質量部以上１０００質量部以下の範囲であり、より好ましくは１００質量部以上８００質量部以下の範囲であり、さらに好ましくは１５０質量部以上５００質量部以下の範囲である。蛍光体コアに対する液媒体の質量比率が１００質量部以上１０００質量部以下の範囲内であると、蛍光体コアを液媒体に略均一に分散させることができ、蛍光体コアの表面にほぼ均一にアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子を付着させることが可能となる。 The mass ratio of the liquid medium to the phosphor core is preferably in the range of 100 parts by mass to 1000 parts by mass, more preferably 100 parts by mass to 800 parts by mass with respect to 100 parts by mass of the phosphor core. More preferably, it is the range of 150 to 500 parts by mass. When the mass ratio of the liquid medium to the phosphor core is in the range of 100 parts by mass or more and 1000 parts by mass or less, the phosphor core can be dispersed substantially uniformly in the liquid medium, and substantially uniformly on the surface of the phosphor core. Aluminum hydroxide particles and / or calcium hydroxide particles can be attached.
分散液に加えられるアルミニウム塩は、塩化アルミニウム、硫酸アルミニウム、及び硝酸アルミニウムからなる群から選ばれる少なくとも一種であることが好ましい。アルミニウム塩は、好ましくは純水に溶解し、アルミニウム塩水溶液として、分散液に加えることが好ましい。
アルミニウム塩と塩基性溶液は分散液中で速やかに反応して、アルミニウム水酸化物粒子が生成され、アルミニウム水酸化物粒子が分散液中で蛍光体コアの表面に略均一に付着される。
The aluminum salt added to the dispersion is preferably at least one selected from the group consisting of aluminum chloride, aluminum sulfate, and aluminum nitrate. The aluminum salt is preferably dissolved in pure water and added to the dispersion as an aluminum salt aqueous solution.
The aluminum salt and the basic solution react quickly in the dispersion to produce aluminum hydroxide particles, and the aluminum hydroxide particles adhere substantially uniformly to the surface of the phosphor core in the dispersion.
分散液に加えられるアルミニウム塩は、アルミニウム塩中のアルミニウムの量が、液媒体に分散される蛍光体コア１００質量部に対して、好ましくは０．１質量部以上１０．０質量部以下の範囲であり、より好ましくは０．２質量部以上８．０質量部以下の範囲であり、さらに好ましくは０．３質量部以上７．０質量部以下の範囲である。分散液に加えられるアルミニウム塩の量が０．１質量部以上１０．０質量部以下の範囲内であると、蛍光体の発光特性を妨げることなく、アルミニウム水酸化物粒子を蛍光体コアに付着させることができる。 The aluminum salt added to the dispersion is preferably in the range of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the phosphor core dispersed in the liquid medium. More preferably, it is the range of 0.2 mass part or more and 8.0 mass part or less, More preferably, it is the range of 0.3 mass part or more and 7.0 mass part or less. When the amount of the aluminum salt added to the dispersion is in the range of 0.1 parts by mass or more and 10.0 parts by mass or less, the aluminum hydroxide particles adhere to the phosphor core without disturbing the light emission characteristics of the phosphor. Can be made.
分散液に加えられる塩基性溶液は、アンモニア水溶液、水酸化ナトリウム水溶液、水酸化カリウム水溶液、炭酸ナトリウム水溶液、及び炭酸カリウム水溶液からなる群から選ばれる少なくとも一種であることが好ましい。塩基性溶液は、準備しやすい一般的な塩基性水溶液を用いることにより、アルミニウム水酸化物粒子を蛍光体コアに付着させることが容易にできる。 The basic solution added to the dispersion is preferably at least one selected from the group consisting of an aqueous ammonia solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous potassium carbonate solution. The basic solution can easily attach the aluminum hydroxide particles to the phosphor core by using a general basic aqueous solution that is easy to prepare.
塩基性溶液中の塩基性化合物の量は、分散液に加えられたアルミニウム塩との化学反応により、アルミニウム水酸化物粒子が生成される量であればよい。塩基性溶液中の塩基性化合物の量は、分散液に分散される蛍光体コア１００質量部に対して、好ましくは０．１質量部以上、より好ましくは０．５質量部以上、さらに好ましくは１．０質量部以上であり、好ましくは１０．０質量部以下、より好ましくは９．０質量部以下、さらに好ましくは８．０質量部以下である。 The amount of the basic compound in the basic solution may be an amount such that aluminum hydroxide particles are generated by a chemical reaction with the aluminum salt added to the dispersion. The amount of the basic compound in the basic solution is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 100 parts by mass of the phosphor core dispersed in the dispersion. 1.0 mass part or more, preferably 10.0 mass parts or less, more preferably 9.0 mass parts or less, and even more preferably 8.0 mass parts or less.
分散液に加えられるケイ素化合物は、加水分解反応及び縮合反応により、二酸化ケイ素を含む化合物又はそのゲル状の化合物の膜状物を形成し得るケイ素化合物であることが好ましい。ケイ素化合物は、ゾルゲル法で利用されるアルコキシケイ素化合物、これらのアルコキシケイ素化合物の部分加水分解物等が挙げられる。ケイ素化合物は、具体的には、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシランからなる群から選ばれる少なくとも一種であることが好ましい。 The silicon compound added to the dispersion is preferably a silicon compound capable of forming a film containing a compound containing silicon dioxide or a gel-like compound thereof by hydrolysis and condensation reactions. Examples of the silicon compound include alkoxy silicon compounds used in the sol-gel method, and partial hydrolysates of these alkoxy silicon compounds. Specifically, the silicon compound is preferably at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.
蛍光体コアが分散された分散液中に、ケイ素化合物と、カルシウム塩及び／又はアルミニウム塩と、塩基性溶液とを加えることによって、具体的にはゾルゲル法により、カルシウム水酸化物粒子及びアルミニウム水酸化物粒子の少なくとも一方と二酸化ケイ素とを含む膜状物を蛍光体コアに付着させることができる。 By adding a silicon compound, a calcium salt and / or an aluminum salt, and a basic solution to the dispersion liquid in which the phosphor core is dispersed, specifically, calcium hydroxide particles and aluminum water are obtained by a sol-gel method. A film-like material containing at least one of oxide particles and silicon dioxide can be attached to the phosphor core.
アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方と、二酸化ケイ素とを含む膜状物は、蛍光体コアの表面の少なくとも一部に配置され、蛍光体コアに付着されていればよい。アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方と、二酸化ケイ素とを含む膜状物は、蛍光体コアの表面の５０％以上に配置されていることが好ましく、７０％以上に配置されていることがより好ましい。例えば、蛍光体コアのＳＥＭ写真において、蛍光体コアの表面を１００％として、膜状物が好ましくは蛍光体コアの表面の約半分以上（５０％以上）に配置され、膜状物がより好ましくは蛍光体コアの表面の約７０％以上に配置されている。アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方と、二酸化ケイ素とを含む膜状物は、蛍光体コアの表面に点在して配置されてもよい。 The film-like material containing at least one of aluminum hydroxide particles and calcium hydroxide particles and silicon dioxide may be disposed on at least a part of the surface of the phosphor core and attached to the phosphor core. The film-like material containing at least one of aluminum hydroxide particles and calcium hydroxide particles and silicon dioxide is preferably disposed at 50% or more of the surface of the phosphor core, and is disposed at 70% or more. More preferably. For example, in the SEM photograph of the phosphor core, the surface of the phosphor core is 100%, and the film-like material is preferably arranged at about half or more (50% or more) of the surface of the phosphor core, and the film-like material is more preferred. Is disposed on about 70% or more of the surface of the phosphor core. The film-like material containing at least one of aluminum hydroxide particles and calcium hydroxide particles and silicon dioxide may be disposed in a scattered manner on the surface of the phosphor core.
分散液に加えられるケイ素化合物の質量は、分散液中で加水分解反応及び縮合反応により、蛍光体コアの表面に膜状物が形成される質量であればよい。分散液に加えられるケイ素化合物の質量は、液媒体に分散される蛍光体コア１００質量部に対して、好ましくは５質量部以上、より好ましくは１０質量部以上、さらに好ましくは１５質量部以上となり、好ましくは３０質量部以下、より好ましくは２５質量部以下、さらに好ましくは２０質量部以下である。分散液中には、ケイ素化合物の加水分解反応を促進するために、ケイ素化合物の質量の半分以下からケイ素化合物の質量以上の量の水が存在していることが好ましい。分散液に加えられるケイ素化合物の量が前記範囲内であると、蛍光体の発光特性を妨げることなく、アルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方と二酸化ケイ素とを含む膜状物を蛍光体コアに付着させることができる。 The mass of the silicon compound added to the dispersion liquid may be any mass so long as a film-like material is formed on the surface of the phosphor core by the hydrolysis reaction and the condensation reaction in the dispersion liquid. The mass of the silicon compound added to the dispersion is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more with respect to 100 parts by mass of the phosphor core dispersed in the liquid medium. The amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less. In order to promote the hydrolysis reaction of the silicon compound, it is preferable that water in an amount of less than half of the mass of the silicon compound to more than the mass of the silicon compound is present in the dispersion. When the amount of the silicon compound added to the dispersion is within the above range, a film-like material containing at least one of aluminum hydroxide particles and calcium hydroxide particles and silicon dioxide without disturbing the light emission characteristics of the phosphor. Can be attached to the phosphor core.
分散液に加えられるカルシウム塩の量は、分散液に分散される蛍光体コア１００質量部に対して、好ましくは１．０質量部以上１５．０質量部以下の範囲であり、より好ましくは２．０質量部以上１２．０質量部以下の範囲であり、さらに好ましくは３．０質量部以上１０．０質量部以下の範囲である。分散液に加えられるカルシウム塩の量が１．０質量部以上１５．０質量部以下の範囲内であると、蛍光体の発光特性を妨げることなく、カルシウム水酸化物粒子を蛍光体コアに付着させることができる。 The amount of calcium salt added to the dispersion is preferably in the range of 1.0 to 15.0 parts by weight, more preferably 2 to 100 parts by weight of the phosphor core dispersed in the dispersion. The range is 0.0 parts by mass or more and 12.0 parts by mass or less, more preferably 3.0 parts by mass or more and 10.0 parts by mass or less. When the amount of calcium salt added to the dispersion is in the range of 1.0 part by mass or more and 15.0 parts by mass or less, calcium hydroxide particles adhere to the phosphor core without disturbing the light emission characteristics of the phosphor. Can be made.
分離工程
分離工程では、蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させた蛍光体と液媒体とを分離する。分離は、例えば、濾過、遠心分離の固液分離手段により行うことができる。固液分離して得られる蛍光体には、洗浄処理、乾燥処理等を必要に応じて行ってもよい。洗浄処理は、例えば、エタノール、イソプロピルアルコール等のアルコール、アセトン等のケトン溶剤、水を用いて行うことができる。また乾燥処理は、室温で行ってもよく、加熱して行ってもよい。乾燥処理で加熱する場合、例えば９５℃から１１５℃とすることができる。乾燥時間は、例えば８時間から２０時間とすることができる。
Separation step In the separation step, the phosphor having at least one of aluminum hydroxide particles and calcium hydroxide particles attached to the phosphor core is separated from the liquid medium. Separation can be performed, for example, by solid-liquid separation means such as filtration and centrifugation. The phosphor obtained by solid-liquid separation may be subjected to washing treatment, drying treatment and the like as necessary. The cleaning treatment can be performed using, for example, an alcohol such as ethanol or isopropyl alcohol, a ketone solvent such as acetone, or water. The drying treatment may be performed at room temperature or may be performed by heating. When heating by a drying process, it can be 95 degreeC to 115 degreeC, for example. The drying time can be, for example, 8 hours to 20 hours.
発光装置
本発明の一実施形態によれば、発光装置は、本発明の一実施形態による蛍光体を含む第一蛍光体と、３８０ｎｍ以上４７０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子とを含む。前記発光装置は、前記第一蛍光体及び樹脂を含む蛍光部材と前記発光素子を含む。
Light Emitting Device According to one embodiment of the present invention, a light emitting device includes a first phosphor including the phosphor according to one embodiment of the present invention, and a light emitting element having a light emission peak wavelength in a wavelength range of 380 nm to 470 nm. Including. The light emitting device includes a fluorescent member including the first phosphor and a resin and the light emitting element.
発光装置は、５００ｎｍ以上５８０ｎｍ以下の波長範囲に発光ピーク波長を有する第二蛍光体を更に含むことが好ましい。第二蛍光体が、前記第一蛍光体及び樹脂とともに、蛍光部材に含まれていることが好ましい。 It is preferable that the light emitting device further includes a second phosphor having an emission peak wavelength in a wavelength range of 500 nm or more and 580 nm or less. It is preferable that the second phosphor is contained in the phosphor member together with the first phosphor and the resin.
発光装置の一例を図面に基づいて詳細に説明する。図１は、発光装置１００の一例を示す概略断面図である。 An example of the light emitting device will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the light emitting device 100.
発光装置１００は、凹部を有するパッケージ４０と、発光素子１０と、発光素子１０を被覆する蛍光部材５０とを備える。パッケージ４０は、正負一対のリード電極２０、３０と、熱可塑性樹脂又は熱硬化性樹脂を含む樹脂部４２とが一体的に成形されてなるものである。発光素子１０は、パッケージ４０に形成された凹部内に配置されており、パッケージ４０に配置された正負一対のリード電極２０、３０に導電性ワイヤ６０によって電気的に接続されている。蛍光部材５０は、蛍光体７０を含む封止樹脂が凹部内に充填されることで形成されており、発光素子１０を被覆している。蛍光部材５０は、例えば、封止樹脂と発光素子１０からの光を波長変換する蛍光体７０を含む。更に蛍光体７０は、本形態の蛍光体を含む第一蛍光体７１と、本形態の蛍光体以外の蛍光体を含む第二蛍光体７２とを含む。正負一対のリード電極２０、３０は、その一部がパッケージ４０の外側に露出されている。これらのリード電極２０、３０を介して、外部から電力の供給を受けて発光装置１００が発光する。 The light emitting device 100 includes a package 40 having a recess, the light emitting element 10, and a fluorescent member 50 that covers the light emitting element 10. The package 40 is formed by integrally molding a pair of positive and negative lead electrodes 20 and 30 and a resin portion 42 containing a thermoplastic resin or a thermosetting resin. The light emitting element 10 is disposed in a recess formed in the package 40, and is electrically connected to a pair of positive and negative lead electrodes 20, 30 disposed in the package 40 by a conductive wire 60. The fluorescent member 50 is formed by filling the recess with a sealing resin including the phosphor 70 and covers the light emitting element 10. The fluorescent member 50 includes, for example, a phosphor 70 that converts the wavelength of light from the sealing resin and the light emitting element 10. Furthermore, the phosphor 70 includes a first phosphor 71 including the phosphor of the present embodiment and a second phosphor 72 including a phosphor other than the phosphor of the present embodiment. A part of the pair of positive and negative lead electrodes 20, 30 is exposed to the outside of the package 40. The light emitting device 100 emits light upon receiving power supply from the outside via the lead electrodes 20 and 30.
蛍光部材
蛍光体７０は、封止樹脂とともに発光素子１０を被覆する蛍光部材５０を構成する。封止樹脂としては、シリコーン樹脂、エポキシ樹脂等が挙げられる。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。
Fluorescent member The phosphor 70 constitutes the fluorescent member 50 that covers the light emitting element 10 together with the sealing resin. Examples of the sealing resin include a silicone resin and an epoxy resin. 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.
蛍光部材５０は、封止樹脂及び蛍光体７０に加えて、フィラー、光拡散材等を更に含んでいてもよい。例えば、光拡散材を含むことで、発光素子１０からの指向性を緩和させ、視野角を増大させることができる。フィラーは光拡散材として作用するものであってもよい。フィラーとしては、例えばシリカ、酸化チタン、酸化亜鉛、酸化ジルコニウム、アルミナ等を挙げることができる。蛍光部材５０がフィラーを含む場合、フィラーの含有量は、例えば、樹脂１００質量部に対して１質量部以上２０質量部以下の範囲とすることができる。 The fluorescent member 50 may further include a filler, a light diffusing material, and the like in addition to the sealing resin and the phosphor 70. For example, by including a light diffusing material, the directivity from the light emitting element 10 can be relaxed and the viewing angle can be increased. The filler may act as a light diffusing material. Examples of the filler include silica, titanium oxide, zinc oxide, zirconium oxide, and alumina. When the fluorescent member 50 includes a filler, the content of the filler can be, for example, in a range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin.
発光素子
発光素子１０は、可視光の短波長側（例えば３８０ｎｍ以上４８５ｎｍ以下の範囲）に発光スペクトルを有する光を発し、３８０ｎｍ以上４７０ｎｍ以下の波長範囲に発光ピーク波長を有する。発光素子１０の発光ピーク波長は、４４０ｎｍ以上４６０ｎｍ以下の波長範囲内にあることがより好ましい。この波長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第一蛍光体及び第二蛍光体からの蛍光の混色光を発する発光装置を得ることができる。
発光素子は、窒化ガリウム系半導体（ＩｎＸＡｌＹＧａ１−Ｘ−ＹＮ、０≦Ｘ、０≦Ｙ、Ｘ＋Ｙ≦１）を用いた半導体発光素子を用いることが好ましい。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。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。
Light-Emitting Element The light-emitting element 10 emits light having an emission spectrum on the short wavelength side of visible light (for example, in a range of 380 nm to 485 nm), and has an emission peak wavelength in a wavelength range of 380 nm to 470 nm. The emission peak wavelength of the light emitting element 10 is more preferably in the wavelength range of 440 nm or more and 460 nm or less. By using a light emitting element having an emission peak wavelength in this wavelength range as an excitation light source, a light emitting device that emits mixed color light of light from the light emitting element and fluorescence from the first phosphor and the second phosphor can be obtained.
As the light-emitting element, a semiconductor light-emitting element using a gallium nitride semiconductor (In X Al Y Ga 1-XY N, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) is preferably used. By using a semiconductor light emitting element, a stable light emitting device with high efficiency, high output linearity with respect to input, and strong mechanical shock can be obtained. The half width of the emission spectrum of the light emitting element can be set to 30 nm or less, for example.
第一蛍光体及び第二蛍光体
蛍光体７０は、発光素子１０から発せられる光の少なくとも一部を吸収し、発光素子１０から発せられる光の波長とは異なる波長に変換する。蛍光体７０は、本発明の一実施形態の蛍光体を含む第一蛍光体７１と、第一蛍光体７１と異なる波長範囲に発光ピーク波長を有する第二蛍光体７２を用いることが好ましい。
第二蛍光体７２として、例えば、（Ｙ，Ｇｄ，Ｔｂ，Ｌｕ）３（Ａｌ，Ｇａ）５Ｏ１２：Ｃｅ、Ｃａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ、ＣａＳｃ２Ｏ４：Ｃｅ、（Ｃａ，Ｓｒ，Ｂａ）２ＳｉＯ４：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）８ＭｇＳｉ４Ｏ１６（Ｆ，Ｃｌ，Ｂｒ）２：Ｅｕ、Ｓｉ６−ｚＡｌｚＯｚＮ８−ｚ：Ｅｕ（０＜ｚ≦４．２）、（Ｂａ，Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｍｎ、（Ｓｒ、Ｂａ，Ｃａ）Ｇａ２Ｓ４：Ｅｕ、（Ｌａ，Ｙ）３Ｓｉ６Ｎ１１：Ｃｅ、（Ｃａ，Ｓｒ，Ｂａ）３Ｓｉ６Ｏ９Ｎ４：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ、（Ｂａ，Ｓｒ，Ｃａ)Ｓｉ２Ｏ２Ｎ２：Ｅｕ、（Ｓｒ，Ｃａ）ＬｉＡｌ３Ｎ４：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）２Ｓｉ５Ｎ８：Ｅｕ、（Ｃａ，Ｓｒ）ＡｌＳｉＮ３：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）Ｓ：Ｅｕ、３．５ＭｇＯ・０．５ＭｇＦ２・ＧｅＯ２：Ｍｎ等を挙げることができる。これらのうち、５００ｎｍ以上５８０ｎｍ以下の波長範囲に発光ピーク波長を有する第二蛍光体として、例えば、（Ｙ，Ｇｄ，Ｔｂ，Ｌｕ）３（Ａｌ，Ｇａ）５Ｏ１２：Ｃｅ、（Ｃａ，Ｓｒ，Ｂａ）８ＭｇＳｉ４Ｏ１６（Ｆ，Ｃｌ，Ｂｒ）２：Ｅｕ、Ｓｉ６−ｚＡｌｚＯｚＮ８−ｚ：Ｅｕ（０＜ｚ≦４．２）、（Ｂａ，Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｍｎを挙げることができる。
First phosphor and second phosphor The phosphor 70 absorbs at least part of the light emitted from the light emitting element 10 and converts it to a wavelength different from the wavelength of the light emitted from the light emitting element 10. As the phosphor 70, it is preferable to use a first phosphor 71 including the phosphor of one embodiment of the present invention and a second phosphor 72 having an emission peak wavelength in a wavelength range different from that of the first phosphor 71.
As the second phosphor 72, for example, (Y, Gd, Tb, Lu) 3 (Al, Ga) 5 O 12 : Ce, Ca 3 Sc 2 Si 3 O 12 : Ce, CaSc 2 O 4 : Ce, (Ca , Sr, Ba) 2 SiO 4 : Eu, (Ca, Sr, Ba) 8 MgSi 4 O 16 (F, Cl, Br) 2: Eu, Si 6-z Al z O z N 8-z: Eu (0 <Z ≦ 4.2), (Ba, Sr) MgAl 10 O 17 : Mn, (Sr, Ba, Ca) Ga 2 S 4 : Eu, (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, (Sr, Ca) LiAl 3 N 4 : Eu, (Ca, Sr, Ba) 2 Si 5 N 8 : Eu, (Ca, Sr) AlSiN 3 : Eu, (Ca, Sr, Ba) S: Eu, 3.5MgO · 0.5MgF 2 · GeO 2 : Mn, and the like can be given. Among these, for example, (Y, Gd, Tb, Lu) 3 (Al, Ga) 5 O 12 : Ce, (Ca, Sr) can be used as the second phosphor having an emission peak wavelength in the wavelength range of 500 nm to 580 nm. , Ba) 8 MgSi 4 O 16 (F, Cl, Br) 2 : Eu, Si 6-z Al z O z N 8 -z : Eu (0 <z ≦ 4.2), (Ba, Sr) MgAl 10 O 17 : Mn can be mentioned.
第二蛍光体７２は、発光効率の観点から、その体積平均粒径が、好ましくは２．０μｍ以上５０．０μｍ以下の範囲であり、より好ましくは５．０μｍ以上４５．０μｍ以下の範囲であり、さらに好ましくは１０．０μｍ以上４０．０μｍ以下の範囲である。 From the viewpoint of luminous efficiency, the second phosphor 72 preferably has a volume average particle size in the range of 2.0 μm to 50.0 μm, more preferably in the range of 5.0 μm to 45.0 μm. More preferably, it is in the range of 10.0 μm or more and 40.0 μm or less.
以下、本発明の実施例を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。 Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.
蛍光体コアの製造
Ｋ２ＭｎＦ６を１６．２５ｇ秤量し、それを５５質量％ＨＦ水溶液１０００ｇに溶解して、溶液Ａを調製した。またＫＨＦ２を１９５．１０ｇ秤量し、それを５５質量％ＨＦ水溶液２００ｇに溶解させて溶液Ｂを調製した。４０質量％Ｈ２ＳｉＦ６水溶液４５０ｇを秤量したものを溶液Ｃとした。
次に溶液Ａを、室温で撹拌しながら、約２０分かけて溶液Ａに溶液Ｂと溶液Ｃとをそれぞれ滴下した。得られた沈殿物を固液分離後、ＩＰＡ（イソプロピルアルコール）洗浄を行い、７０℃で１０時間乾燥することで、Ｋ２[Ｓｉ０．９６２Ｍｎ４＋ ０．０３８Ｆ６]で表される組成を有するフッ化物を含む粒子状の蛍光体コアを作製した。
Production of phosphor core 16.25 g of K 2 MnF 6 was weighed and dissolved in 1000 g of a 55% by mass HF aqueous solution to prepare a solution A. Further, 195.10 g of KHF 2 was weighed and dissolved in 200 g of a 55% by mass HF aqueous solution to prepare a solution B. A solution C was prepared by weighing 450 g of 40% by mass H 2 SiF 6 aqueous solution.
Next, solution B and solution C were added dropwise to solution A over about 20 minutes while stirring solution A at room temperature. The resulting precipitate is subjected to solid-liquid separation, followed by washing with IPA (isopropyl alcohol) and drying at 70 ° C. for 10 hours, whereby the composition represented by K 2 [Si 0.962 Mn 4+ 0.038 F 6 ] A particulate phosphor core containing a fluoride having the above was produced.
実施例１
蛍光体コア５０ｇを、液媒体であるエタノール(純度９９．５％以上)９０ｇに加えて分散させて、分散液を得た。分散液は、粒子状の蛍光体コアを含むスラリーとなった。分散液に、純水に塩化アルミニウムを加えた塩化アルミニウム水溶液（アルミニウム濃度１２．７質量％）を３．９ｇと、塩基性溶液としてアンモニア水（アンモニウム濃度１８．０質量％）１０．７ｇとを加えた。塩化アルミニウム水溶液及びアンモニア水を加えた分散液を十分に撹拌した。分散液をろ過して、スラリーから蛍光体を分離し、次いで乾燥して粒子状の蛍光体を得た。実施例１の蛍光体は、粒子状の蛍光体コアの表面に、アルミニウム水酸化物粒子が付着していた。
Example 1
50 g of the phosphor core was added to 90 g of ethanol (purity 99.5% or more) as a liquid medium and dispersed to obtain a dispersion. The dispersion became a slurry containing a particulate phosphor core. To the dispersion, 3.9 g of an aluminum chloride aqueous solution (aluminum concentration 12.7% by mass) obtained by adding aluminum chloride to pure water, and 10.7 g of aqueous ammonia (ammonium concentration 18.0% by mass) as a basic solution. added. The dispersion added with an aqueous aluminum chloride solution and aqueous ammonia was sufficiently stirred. The dispersion was filtered to separate the phosphor from the slurry, and then dried to obtain a particulate phosphor. In the phosphor of Example 1, aluminum hydroxide particles adhered to the surface of the particulate phosphor core.
実施例２
分散液に、塩化アルミニウム水溶液（アルミニウム濃度１２．７質量％）を１１．８ｇ加えたこと以外は、実施例１と同様にして、粒子状の蛍光体を得た。実施例２の蛍光体は、粒子状の蛍光体コアの表面にアルミニウム水酸化物粒子が付着していた。
Example 2
A particulate phosphor was obtained in the same manner as in Example 1 except that 11.8 g of an aluminum chloride aqueous solution (aluminum concentration 12.7% by mass) was added to the dispersion. In the phosphor of Example 2, aluminum hydroxide particles adhered to the surface of the particulate phosphor core.
実施例３
分散液に、塩化アルミニウム水溶液（アルミニウム濃度１２．７質量％）を１９．７ｇ加えたこと以外は、実施例１と同様にして、粒子状の蛍光体を得た。実施例３の蛍光体は、粒子状の蛍光体コアの表面にアルミニウム水酸化物粒子が付着していた。
Example 3
A particulate phosphor was obtained in the same manner as in Example 1 except that 19.7 g of an aluminum chloride aqueous solution (aluminum concentration 12.7% by mass) was added to the dispersion. In the phosphor of Example 3, aluminum hydroxide particles adhered to the surface of the particulate phosphor core.
実施例４
蛍光体コア５０ｇを、液媒体であるエタノール(純度９９．５％以上)９０ｇに加えて分散させて、分散液を得た。分散液は、粒子状の蛍光体コアを含むスラリーとなった。分散液に、テトラエトキシシラン（Ｓｉ（ＯＣ２Ｈ５）４）を８．９ｇと、純水を８．９ｇと、塩化アルミニウム水溶液（アルミニウム濃度１２．７質量％）を３．９ｇと、塩基性溶液としてアンモニア水（アンモニウム濃度１８．０質量％）１０．７ｇとを加えた。分散液を十分に撹拌し、テトラエトキシシランを加水分解反応及び縮合反応させた。分散液をろ過して、スラリーから蛍光体を分離し、次いで乾燥して粒子状の蛍光体を得た。実施例４の蛍光体は、粒子状の蛍光体コアの表面に、アルミニウム水酸化物粒子と二酸化ケイ素を含む膜状物が付着していた。
Example 4
50 g of the phosphor core was added to 90 g of ethanol (purity 99.5% or more) as a liquid medium and dispersed to obtain a dispersion. The dispersion became a slurry containing a particulate phosphor core. In the dispersion, 8.9 g of tetraethoxysilane (Si (OC 2 H 5 ) 4 ), 8.9 g of pure water, 3.9 g of an aqueous aluminum chloride solution (aluminum concentration 12.7% by mass), and a base 10.7 g of aqueous ammonia (ammonium concentration: 18.0% by mass) was added as a neutral solution. The dispersion was sufficiently stirred to hydrolyze and condense tetraethoxysilane. The dispersion was filtered to separate the phosphor from the slurry, and then dried to obtain a particulate phosphor. In the phosphor of Example 4, a film-like material containing aluminum hydroxide particles and silicon dioxide was adhered to the surface of the particulate phosphor core.
実施例５
分散液に、塩化アルミニウム水溶液（アルミニウム濃度１２．７質量％）を１１．８ｇ加えたこと以外は、実施例４と同様にして、粒子状の蛍光体を得た。実施例５の蛍光体は、粒子状の蛍光体コアの表面に、アルミニウム水酸化物粒子と二酸化ケイ素を含む膜状物が付着していた。
Example 5
A particulate phosphor was obtained in the same manner as in Example 4 except that 11.8 g of an aqueous aluminum chloride solution (aluminum concentration 12.7% by mass) was added to the dispersion. In the phosphor of Example 5, a film-like material containing aluminum hydroxide particles and silicon dioxide was adhered to the surface of the particulate phosphor core.
実施例６
分散液に、塩化アルミニウム水溶液（アルミニウム濃度１２．７質量％）を１９．７ｇ加えたこと以外は、実施例４と同様にして、粒子状の蛍光体を得た。実施例６の蛍光体は、粒子状の蛍光体コアの表面に、アルミニウム水酸化物粒子と二酸化ケイ素を含む膜状物が付着していた。
Example 6
A particulate phosphor was obtained in the same manner as in Example 4 except that 19.7 g of an aqueous aluminum chloride solution (aluminum concentration 12.7% by mass) was added to the dispersion. In the phosphor of Example 6, a film-like material containing aluminum hydroxide particles and silicon dioxide was adhered to the surface of the particulate phosphor core.
実施例７
蛍光体コア５０ｇを、水酸化カルシウム粉末２．８ｇと共に、液媒体であるエタノール(純度９９．５％以上)９０ｇに加えて分散させて、分散液を得た。分散液は、蛍光体コアを含むスラリーとなった。分散液に、テトラエトキシシラン（Ｓｉ（ＯＣ２Ｈ５）４）を８．９ｇと、純水を８．９ｇと、塩基性溶液としてアンモニア水（アンモニウム濃度１８．０質量％）１０．７ｇとを加えた。分散液を十分に撹拌し、テトラエトキシシランを加水分解反応及び縮合反応させた。分散液をろ過して、スラリーから蛍光体を分離し、次いで乾燥して粒子状の蛍光体を得た。実施例７の蛍光体は、粒子状の蛍光体コアの表面に、水酸化カルシウム粒子と二酸化ケイ素を含む膜状物が付着していた。
Example 7
A phosphor core (50 g) was added to and dispersed in 90 g of ethanol (purity 99.5% or more) as a liquid medium together with 2.8 g of calcium hydroxide powder to obtain a dispersion. The dispersion became a slurry containing a phosphor core. In the dispersion, 8.9 g of tetraethoxysilane (Si (OC 2 H 5 ) 4 ), 8.9 g of pure water, 10.7 g of ammonia water (ammonium concentration 18.0% by mass) as a basic solution, Was added. The dispersion was sufficiently stirred to hydrolyze and condense tetraethoxysilane. The dispersion was filtered to separate the phosphor from the slurry, and then dried to obtain a particulate phosphor. In the phosphor of Example 7, a film containing calcium hydroxide particles and silicon dioxide adhered to the surface of the particulate phosphor core.
比較例１
蛍光体コアを、粒子状の比較例１の蛍光体とした。
Comparative Example 1
The phosphor core was the particulate phosphor of Comparative Example 1.
発光装置の作製
上記で得られた各蛍光体を第一蛍光体とした。Ｙ３Ａｌ５Ｏ１２：Ｃｅで表される組成を有する蛍光体を第二蛍光体とした。
発光装置が発する光の色度座標がｘ＝０．３８０、ｙ＝０．３８０付近となるように、質量比を調節した第一蛍光体及び第二蛍光体をシリコーン樹脂に添加し、混合分散した後、更に脱泡することにより蛍光体含有樹脂組成物を得た。次にこの蛍光体含有樹脂組成物をＬＥＤパッケージ（発光素子の発光ピーク波長４５５ｎｍ）の発光素子上に注入、充填し、さらに１５０℃で４時間加熱することで樹脂組成物を硬化させて蛍光体部材とした。このような工程により各第一蛍光体を含む発光装置をそれぞれ作製した。
Production of Light-Emitting Device Each phosphor obtained above was used as a first phosphor. A phosphor having a composition represented by Y 3 Al 5 O 12 : Ce was used as the second phosphor.
The first phosphor and the second phosphor adjusted in mass ratio are added to the silicone resin so that the chromaticity coordinates of the light emitted from the light emitting device are in the vicinity of x = 0.380 and y = 0.380, and mixed and dispersed. Then, the phosphor-containing resin composition was obtained by further defoaming. Next, this phosphor-containing resin composition is injected and filled on a light emitting device of an LED package (light emission peak wavelength of 455 nm), and further heated at 150 ° C. for 4 hours to cure the resin composition and phosphor. It was set as a member. A light emitting device including each first phosphor was produced by such a process.
各蛍光体について、以下の測定を行った。 The following measurements were performed for each phosphor.
組成分析
誘導結合プラズマ発光分析装置（Perkin Elmer（パーキンエルマー）社製）を用いて、ＩＣＰ−ＡＥＳ（高周波誘導結合プラズマ発光分光分析法）により、蛍光体コア、実施例１から７の蛍光体及び比較例１の蛍光体について、各元素の定量分析を行った。Ａｌ及びＣａについては、蛍光体について測定したＡｌ及び／又はＣａの測定量を蛍光体コアの表面に配置されたアルミニウム水酸化物粒子及び／又はカルシウム水酸化物粒子中のＡｌ及び／又はＣａの含有量（質量％）として求めた。また、蛍光体コアのＫの含有量（質量％）とＳｉの含有量（質量％）と、蛍光体のＫの含有量（質量％）とＳｉの含有量（質量％）を同様に測定した。蛍光体のＳｉの含有量（質量％）から蛍光体コアに含まれるＳｉの含有量を差し引き、その差に相当するＳｉの含有量（質量％）を、蛍光体コアの表面に配置された二酸化ケイ素中のケイ素の含有量（質量％）とした。その結果を示す表１において、アルミニウム水酸化物粒子中のＡｌ、カルシウム水酸化物粒子中のＣａ、二酸化ケイ素中のＳｉの含有量を、蛍光体における各元素の含有量（質量％）として表す。
Composition analysis Using an inductively coupled plasma emission analyzer (manufactured by Perkin Elmer), ICP-AES (High Frequency Inductively Coupled Plasma Atomic Emission Spectroscopy), the phosphor core, the phosphors of Examples 1 to 7 and About the fluorescent substance of the comparative example 1, each element was quantitatively analyzed. For Al and Ca, the measured amount of Al and / or Ca measured for the phosphor is the amount of Al and / or Ca in the aluminum hydroxide particles and / or calcium hydroxide particles arranged on the surface of the phosphor core. It calculated | required as content (mass%). In addition, the K content (% by mass) and the Si content (% by mass) of the phosphor core, the K content (% by mass) and the Si content (% by mass) of the phosphor were measured in the same manner. . The Si content (mass%) in the phosphor core is subtracted from the Si content (mass%) of the phosphor, and the Si content (mass%) corresponding to the difference is subtracted from the dioxide dioxide disposed on the surface of the phosphor core. The silicon content (% by mass) in silicon was used. In Table 1 showing the results, the contents of Al in the aluminum hydroxide particles, Ca in the calcium hydroxide particles, and Si in the silicon dioxide are expressed as the contents (mass%) of each element in the phosphor. .
フーリエ変換赤外分光装置によって測定される赤外吸収スペクトル
水酸化アルミニウム、実施例３の蛍光体、比較例１の蛍光体について、フーリエ変換赤外分光装置（製品名：Ｎｉｃｏｌｅｔ ｉＳ５０、サーモフィッシャー サイエンティフィック社製、以下「ＦＴ−ＩＲ」ともいう。）を用いて、全反射法（ＡＴＲ法：Attenuated total reflection）により、赤外吸収スペクトルを測定した。結果を図２に示す。
Infrared absorption spectrum measured by a Fourier transform infrared spectroscope For aluminum hydroxide, the phosphor of Example 3, and the phosphor of Comparative Example 1, a Fourier transform infrared spectroscope (product name: Nicolet iS50, Thermo Fisher Scientific) Infrared absorption spectrum was measured by the total reflection method (ATR method: Attenuated total reflection) using Fick Co., Ltd. (hereinafter also referred to as “FT-IR”). The results are shown in FIG.
ＳＥＭ画像
走査型電子顕微鏡（ＳＥＭ）を用いて、実施例１、実施例４、及び比較例１の蛍光体のＳＥＭ写真を得た。図３Ａは、実施例１に係る蛍光体のＳＥＭ写真を示し、図３Ｂは、実施例１に係る蛍光体を部分拡大したＳＥＭ写真である。図４Ａは、実施例４に係る蛍光体のＳＥＭ画像を示す写真であり、図４Ｂは、実施例４に係る蛍光体のＳＥＭ画像の部分拡大図の一例を示す写真である。図５Ａは、比較例１に係る蛍光体のＳＥＭ画像を示す写真であり、図５Ｂは、比較例１に係る蛍光体のＳＥＭ画像の部分拡大図の一例を示す写真である。
SEM images SEM photographs of the phosphors of Example 1, Example 4, and Comparative Example 1 were obtained using a scanning electron microscope (SEM). FIG. 3A shows an SEM photograph of the phosphor according to Example 1, and FIG. 3B is an SEM photograph in which the phosphor according to Example 1 is partially enlarged. 4A is a photograph showing a SEM image of the phosphor according to Example 4, and FIG. 4B is a photograph showing an example of a partially enlarged view of the SEM image of the phosphor according to Example 4. FIG. FIG. 5A is a photograph showing an SEM image of the phosphor according to Comparative Example 1, and FIG. 5B is a photograph showing an example of a partially enlarged view of the SEM image of the phosphor according to Comparative Example 1.
各発光装置について、以下の測定を行った。 The following measurements were performed for each light emitting device.
耐久性評価
得られた発光装置は、８５℃の高温の環境試験機内にて電流２５０ｍＡで連続点灯させ、７００時間経過させて、耐久性試験を行った。耐久性試験前の発光装置の色度座標におけるｘ値、ｙ値を初期値とし、この初期値から耐久性試験後の発光装置のｘ値、ｙ値の差分の絶対値をΔｘ、Δｙとした。また、比較例１の蛍光体を第一蛍光体として用いた発光装置の光束の初期値を１００とし、各発光装置の初期値の相対光束（Ｐｉ）を測定した。また、耐久性試験前の各発光装置の光束を１００とし、耐久性試験後の各発光装置の相対光束（Ｐｏ）を測定した。結果を表１に示す。
Durability Evaluation The obtained light-emitting device was continuously lit at a current of 250 mA in a high-temperature environmental test machine at 85 ° C., and a durability test was performed after 700 hours had elapsed. The x and y values in the chromaticity coordinates of the light emitting device before the durability test are set as initial values, and the absolute values of the difference between the x value and y value of the light emitting device after the durability test from the initial values are Δx and Δy. . Further, the initial value of the luminous flux of the light emitting device using the phosphor of Comparative Example 1 as the first phosphor was set to 100, and the relative luminous flux (Pi) of the initial value of each light emitting device was measured. Further, the luminous flux of each light emitting device before the durability test was set to 100, and the relative luminous flux (Po) of each light emitting device after the durability test was measured. The results are shown in Table 1.
外観写真
耐久性試験の前と後において、実施例４に係る蛍光体を用いた発光装置の蛍光部材の上面の一部の外観写真と、比較例１に係る蛍光体を用いた発光装置の蛍光部材の上面の一部の外観写真を得た。図６Ａは、耐久性試験前の実施例４に係る蛍光体を用いた発光装置の蛍光部材の上面の一部を示す外観写真であり、図６Ｂは、耐久性試験後の実施例４に係る蛍光体を用いた発光装置の蛍光部材の上面の一部を示す外観写真である。図７Ａは、耐久性試験前の比較例１に係る蛍光体を用いた発光装置の蛍光部材の上面の一部を示す外観写真であり、図７Ｂは、耐久性試験後の比較例１に係る蛍光体を用いた発光装置の蛍光部材の上面の一部を示す外観写真である。
Appearance Photograph Before and after the durability test, an appearance photograph of a part of the upper surface of the fluorescent member of the light emitting device using the phosphor according to Example 4, and the fluorescence of the light emitting device using the phosphor according to Comparative Example 1 An appearance photograph of a part of the upper surface of the member was obtained. 6A is an external view photograph showing a part of the upper surface of the fluorescent member of the light emitting device using the phosphor according to Example 4 before the durability test, and FIG. 6B relates to Example 4 after the durability test. It is an external appearance photograph which shows a part of upper surface of the fluorescent member of the light-emitting device using fluorescent substance. 7A is an appearance photograph showing a part of the upper surface of the fluorescent member of the light emitting device using the phosphor according to Comparative Example 1 before the durability test, and FIG. 7B is according to Comparative Example 1 after the durability test. It is an external appearance photograph which shows a part of upper surface of the fluorescent member of the light-emitting device using fluorescent substance.
表１に示すように、実施例１から７は、初期値の相対光束Ｐｉが比較例１と同じか、比較例１よりも若干低いものの、７００時間経過後の相対光束Ｐｏはいずれも比較例１よりも高い数値となっており、初期光束の低下を抑制でき、優れた耐久性を有していた。また、実施例１から７は、いずれもΔｘが０．０１以下、Δｙが０．０２以下であり、色度座標における初期値からｘ値及びｙ値の変化が小さく、色度変化が抑制され、優れた耐久性を有していた。
比較例１は、７００時間経過後の相対光束Ｐｏが５０％以下に低下した。また、比較例１は、色度座標における初期値からｘ値及びｙ値の変化が大きくなった。
As shown in Table 1, in Examples 1 to 7, although the relative light flux Pi of the initial value is the same as or slightly lower than that of Comparative Example 1, the relative light flux Po after 700 hours is a comparative example. It was a numerical value higher than 1, and it was possible to suppress a decrease in the initial luminous flux and to have excellent durability. In each of Examples 1 to 7, Δx is 0.01 or less and Δy is 0.02 or less, and the change in x value and y value is small from the initial value in the chromaticity coordinates, and the change in chromaticity is suppressed. Had excellent durability.
In Comparative Example 1, the relative luminous flux Po after 700 hours had decreased to 50% or less. Further, in Comparative Example 1, the change in the x value and the y value from the initial value in the chromaticity coordinates was large.
表１に示すように、実施例１から６の相対光束Ｐｏと、実施例７の相対光束Ｐｏを比較すると、実施例１から６の方が、実施例７よりも相対光束Ｐｏの低下が抑制されている。これは、フッ素と反応する活性化エネルギーは、フッ素と結合するカチオンの分極率に支配され、アルミニウムの方がカルシウムよりも分極率が小さいため、アルミニウムの方がフッ素と反応する活性エネルギーが小さく、フッ素と反応しやすいためと考えられる。すなわち、アルミニウム水酸化物粒子の方が水酸化カルシウム粒子よりもフッ素と反応しやすく、フッ素を捕捉しやすいと考えられる。また、アルミニウム水酸化物粒子の結晶構造は、水酸化カルシウム粒子の結晶構造よりも脆弱であり、アルミニウム水酸化物粒子の方が、水酸化カルシウム粒子よりもフッ素と反応しやすく、フッ素を捕捉しやすいと考えられる。これらの理由から、アルミニウム水酸化物粒子は、水酸化カルシウム粒子よりも、蛍光体コアの表面に存在しているフッ素や、蛍光体コアからわずかに発生するフッ素を含むガスを捕捉しやすいため、樹脂との密着性が向上し、初期光束が高くすることができ、また、樹脂の劣化を抑制して、初期光束の低下が抑制されていると考えられる。 As shown in Table 1, when the relative light beam Po of Examples 1 to 6 and the relative light beam Po of Example 7 are compared, the decrease of the relative light beam Po is suppressed in Example 1 to 6 than in Example 7. Has been. This is because the activation energy that reacts with fluorine is governed by the polarizability of the cation that binds to fluorine, and since aluminum has a smaller polarizability than calcium, aluminum has a smaller activation energy that reacts with fluorine, This is thought to be because it easily reacts with fluorine. That is, it is considered that aluminum hydroxide particles are more likely to react with fluorine than calcium hydroxide particles and trap fluorine. The crystal structure of the aluminum hydroxide particles is more fragile than the crystal structure of the calcium hydroxide particles, and the aluminum hydroxide particles react more easily with fluorine than the calcium hydroxide particles, and capture fluorine. It is considered easy. For these reasons, the aluminum hydroxide particles are easier to capture the fluorine-containing gas that is present on the surface of the phosphor core and the fluorine-containing gas slightly generated from the phosphor core than the calcium hydroxide particles. It is considered that the adhesiveness with the resin is improved, the initial luminous flux can be increased, and the deterioration of the resin is suppressed to suppress the decrease of the initial luminous flux.
図２に示すように、実施例３は、ＦＴ−ＩＲによって測定された赤外吸収スペクトルにおいて、３０００ｃｍ−１以上３６００ｃｍ−１以下の波数領域において、水酸化アルミニウム（Ａｌ（ＯＨ）３）及び／又は水酸化酸化アルミニウム（ＡｌＯ（ＯＨ））に由来するピークが確認された。この結果から、実施例３の蛍光体は、水酸化アルミニウム（Ａｌ（ＯＨ）３）粒子及び／又は水酸化酸化アルミニウム（ＡｌＯ（ＯＨ））粒子が蛍光体コアに配置されていると考えられる。
一方、図２に示すように、比較例１は、ＦＴ−ＩＲによって測定された赤外吸収スペクトルにおいて、３０００ｃｍ−１以上３６００ｃｍ−１以下の波数領域において、水酸化アルミニウム（Ａｌ（ＯＨ）３）及び／又は水酸化酸化アルミニウム（ＡｌＯ（ＯＨ））に由来するピークが確認されなかった。
As shown in FIG. 2, Example 3, in it is the infrared absorption spectrum measured by FT-IR, the 3000 cm -1 or 3600 cm -1 The following wavenumber regions, aluminum hydroxide (Al (OH) 3) and / Alternatively, a peak derived from aluminum hydroxide oxide (AlO (OH)) was confirmed. From this result, it is considered that the phosphor of Example 3 has aluminum hydroxide (Al (OH) 3 ) particles and / or aluminum hydroxide oxide (AlO (OH)) particles arranged in the phosphor core.
On the other hand, as shown in FIG. 2, Comparative Example 1, in the infrared absorption spectrum measured by FT-IR, in the following wavenumber regions 3000 cm -1 or 3600 cm -1, aluminum hydroxide (Al (OH) 3) And / or a peak derived from aluminum hydroxide oxide (AlO (OH)) was not confirmed.
図３Ａ及び図３ＢのＳＥＭ写真に示すように、実施例１は、蛍光体コアの表面に蛍光体コアよりも粒径の小さいアルミニウム水酸化物粒子が配置されていることが確認できる。 As shown in the SEM photographs of FIGS. 3A and 3B, it can be confirmed that in Example 1, aluminum hydroxide particles having a particle diameter smaller than that of the phosphor core are arranged on the surface of the phosphor core.
図４Ａ及び図４ＢのＳＥＭ写真に示されるように、実施例４は、蛍光体コアの表面に付着されているアルミニウム水酸化物粒子の量が、実施例１の蛍光体コアの表面に付着されているアルミニウム水酸化物粒子の量よりも少なく見える。
実施例１と実施例４は、第一蛍光体中のアルミニウムの含有量（質量％）が同じであるため、実施例１と実施例４では、蛍光体コアの表面に同程度の量のアルミニウム水酸化物粒子が付着されると考えられる。実施例４の蛍光体コアの表面に付着されているアルミニウム水酸化物粒子の量が、実施例１の蛍光体コアの表面に付着されているアルミニウム水酸化物粒子の量よりも少なく見えるのは、実施例４の蛍光体コアの表面には、二酸化ケイ素とアルミニウム水酸化物粒子を含む膜状物が形成されており、この膜状物中にアルミニウム水酸化物粒子が埋め込まれた状態となって、蛍光体コアの表面に付着されているためと考えられる。
As shown in the SEM photographs of FIGS. 4A and 4B, Example 4 shows that the amount of aluminum hydroxide particles attached to the surface of the phosphor core is attached to the surface of the phosphor core of Example 1. Looks less than the amount of aluminum hydroxide particles that are.
Since Example 1 and Example 4 have the same aluminum content (mass%) in the first phosphor, in Example 1 and Example 4, aluminum of the same amount is formed on the surface of the phosphor core. It is thought that hydroxide particles adhere. The amount of aluminum hydroxide particles attached to the surface of the phosphor core of Example 4 appears to be less than the amount of aluminum hydroxide particles attached to the surface of the phosphor core of Example 1. A film-like material containing silicon dioxide and aluminum hydroxide particles is formed on the surface of the phosphor core of Example 4, and the aluminum hydroxide particles are embedded in this film-like material. This is considered to be because it is attached to the surface of the phosphor core.
一方、図５Ａ及び図５ＢのＳＥＭ写真に示されるように、比較例１は、蛍光体コアの表面に小さな粒子が配置されていることは確認できなかった。 On the other hand, as shown in the SEM photographs of FIGS. 5A and 5B, Comparative Example 1 could not confirm that small particles were arranged on the surface of the phosphor core.
図６Ａ及び図６Ｂの外観写真に示すように、実施例４に係る蛍光体を用いた発光装置の蛍光部材の上面の一部は、耐久性試験前と７００時間の耐久性試験後とでは、蛍光部材の上面の一部に大きな変化は見られず、耐久性試験後でもクラックなどは見当たらなかった。図６Ｂに示す耐久性試験後の外観写真から、実施例４に係る蛍光体を用いた発光装置は、耐久性に優れていることが確認できた。なお、図６Ｂにおいて、一部黒色に見える部分は、耐久性試験中又は写真撮影時に発光装置の蛍光部材の上面に付着した塵埃等であると推測される。 6A and 6B, a part of the upper surface of the fluorescent member of the light emitting device using the phosphor according to Example 4 is before the durability test and after the 700 hour durability test. There was no significant change in part of the upper surface of the fluorescent member, and no cracks were found even after the durability test. From the appearance photograph after the durability test shown in FIG. 6B, it was confirmed that the light emitting device using the phosphor according to Example 4 was excellent in durability. Note that in FIG. 6B, the part that appears to be partly black is assumed to be dust or the like attached to the upper surface of the fluorescent member of the light-emitting device during the durability test or during photography.
図７Ａ及び図７Ｂの外観写真に示すように、比較例１に係る蛍光体を用いた発光装置の蛍光部材の上面の一部は、図７Ａの耐久性試験前にはクラックが存在していないが、図７Ｂの７００時間の耐久性試験後には、クラックが発生していた。図７Ｂに示す発光装置の蛍光部材の上面の一部に確認されたクラックは、比較例１に係る蛍光体と樹脂との界面に形成された複数の解離を起因として発生していると推測される。 7A and 7B, a part of the upper surface of the fluorescent member of the light emitting device using the phosphor according to Comparative Example 1 does not have a crack before the durability test of FIG. 7A. However, cracks occurred after the 700-hour durability test of FIG. 7B. It is estimated that the crack confirmed on a part of the upper surface of the fluorescent member of the light emitting device shown in FIG. 7B is caused by a plurality of dissociations formed at the interface between the phosphor and the resin according to Comparative Example 1. The
本開示の製造方法によって耐久性の優れた蛍光体を得ることができる。本開示の蛍光体は、発光装置に用いることができ、本開示の発光装置は、優れた耐久性を有し、発光ダイオードを励起光源とし、ディスプレイ、バックライト用の光源、一般照明、車載照明等の幅広い分野での使用することができる。 A phosphor having excellent durability can be obtained by the manufacturing method of the present disclosure. The phosphor of the present disclosure can be used for a light-emitting device, and the light-emitting device of the present disclosure has excellent durability, uses a light-emitting diode as an excitation light source, a display, a light source for backlight, general illumination, and in-vehicle illumination. It can be used in a wide range of fields.
１０：発光素子、４０：パッケージ、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, 40: package, 50: fluorescent member, 71: first phosphor, 72: second phosphor, 100: light emitting device.
Claims (14)
Ａ２［Ｍ１−ｐＭｎ４＋ ｐＦ６］ （１）
（式中、Ａは、アルカリ金属元素又はＮＨ４ ＋からなる群より選択される少なくとも一種の元素であり、Ｍは、第４族元素及び第１４族元素からなる群より選択される少なくとも一種の元素であり、ｐは０．０＜ｐ＜０．１を満たす数である。） The phosphor according to claim 1, wherein the phosphor core includes a fluoride having a composition represented by the following formula (1).
A 2 [M 1-p Mn 4+ p F 6] (1)
(In the formula, A is at least one element selected from the group consisting of alkali metal elements or NH 4 + , and M is at least one element selected from the group consisting of Group 4 elements and Group 14 elements) And p is a number satisfying 0.0 <p <0.1.)
前記蛍光体コアを液媒体に分散させた分散液中で、前記蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させることと、
前記蛍光体コアにアルミニウム水酸化物粒子及びカルシウム水酸化物粒子の少なくとも一方を付着させた蛍光体と液媒体とを分離することを含む、蛍光体の製造方法。 Fluoride having a composition comprising Mn, at least one element selected from the group consisting of alkali metal elements and NH 4 +, and at least one element selected from the group consisting of Group 4 elements and Group 14 elements Preparing a phosphor core;
In a dispersion liquid in which the phosphor core is dispersed in a liquid medium, attaching at least one of aluminum hydroxide particles and calcium hydroxide particles to the phosphor core;
A method for producing a phosphor, comprising: separating a phosphor in which at least one of aluminum hydroxide particles and calcium hydroxide particles is attached to the phosphor core and a liquid medium.
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