JP5718580B2 - Red phosphor, method for producing the same, and light emitting device - Google Patents
Red phosphor, method for producing the same, and light emitting device Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 348
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000843 powder Substances 0.000 claims description 367
- 238000010304 firing Methods 0.000 claims description 227
- 239000000203 mixture Substances 0.000 claims description 191
- 239000002994 raw material Substances 0.000 claims description 30
- 239000004065 semiconductor Substances 0.000 claims description 24
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229910052693 Europium Inorganic materials 0.000 claims description 8
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 7
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 229910001940 europium oxide Inorganic materials 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 22
- 229910052582 BN Inorganic materials 0.000 description 20
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000005284 excitation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000000918 Europium Chemical class 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 229910004122 SrSi Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、赤色蛍光体およびその製造方法ならびに発光装置に関し、詳しくは、ユーロピウム付活サイアロンからなる赤色蛍光体およびその製造方法ならびに前記赤色蛍光体を用いた発光装置に関する。 The present invention relates to a red phosphor, a method for producing the same, and a light emitting device, and more particularly to a red phosphor comprising europium activated sialon, a method for producing the same, and a light emitting device using the red phosphor.
蛍光体粉末は、たとえば、発光ダイオード（ＬＥＤ：Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）等の発光装置に用いられる。発光装置は、たとえば、基板上に配置され所定の色の光を出射する半導体発光素子と、この半導体発光素子から出射される紫外光、青色光等の光により励起されて可視光を発する蛍光体粉末を封止樹脂である透明樹脂硬化物中に含む発光部とを備える。 The phosphor powder is used for a light emitting device such as a light emitting diode (LED). The light emitting device includes, for example, a semiconductor light emitting element that is arranged on a substrate and emits light of a predetermined color, and a phosphor that emits visible light when excited by light such as ultraviolet light and blue light emitted from the semiconductor light emitting element. A light emitting part including powder in a transparent resin cured product which is a sealing resin.
発光装置の半導体発光素子としては、たとえば、ＧａＮ、ＩｎＧａＮ、ＡｌＧａＮ、ＩｎＧａＡｌＰ等が用いられる。また、蛍光体粉末の蛍光体としては、たとえば、半導体発光素子からの出射光により励起されてそれぞれ青色光、緑色光、黄色光、赤色光の光を出射する青色蛍光体、緑色蛍光体、黄色蛍光体、赤色蛍光体等が用いられる。 For example, GaN, InGaN, AlGaN, InGaAlP or the like is used as the semiconductor light emitting element of the light emitting device. Examples of the phosphor of the phosphor powder include a blue phosphor, a green phosphor, and a yellow phosphor that are excited by light emitted from the semiconductor light emitting element and emit blue light, green light, yellow light, and red light, respectively. A phosphor, a red phosphor or the like is used.
発光装置は、封止樹脂中に赤色蛍光体等の各種の蛍光体粉末を含有させることにより、放射光の色を調整することができる。すなわち、発光チップと、発光チップから放射された光を吸収して所定波長域の光を発光する蛍光体粉末とを組み合わせて用いることにより、発光チップから放射された光と蛍光体粉末から放射された光との作用で、可視光領域の光や白色光を発光させることが可能になる。 The light emitting device can adjust the color of the emitted light by including various phosphor powders such as a red phosphor in the sealing resin. That is, by using a combination of a light-emitting chip and a phosphor powder that absorbs light emitted from the light-emitting chip and emits light in a predetermined wavelength region, light emitted from the light-emitting chip and phosphor powder are emitted. It is possible to emit light in the visible light region or white light by the action of the light.
従来、蛍光体としては、たとえば、特許文献１（国際公開第２００７／１０５６３１号）に、波長２５０ｎｍ乃至５００ｎｍの紫外光〜青色光で励起した際に、波長４９０ｎｍ乃至５８０ｎｍの間に発光ピークを示すサイアロン（Ｓｉ−Ａｌ−Ｏ−Ｎ）構造の緑色蛍光体が開示されている。 Conventionally, as a phosphor, for example, Patent Document 1 (International Publication No. 2007/1055631) shows an emission peak between wavelengths 490 nm and 580 nm when excited with ultraviolet light to blue light having a wavelength of 250 nm to 500 nm. A green phosphor having a sialon (Si—Al—O—N) structure is disclosed.
また、特許文献１の実施例１には、ＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３を原料として用いカーボンるつぼで焼成することにより、黄緑色蛍光体である黄緑色粉体と、橙色蛍光体である橙色粉体と、の２種類の焼結粉体の混合物を得る蛍光体の製造方法が記載されている。また、参考例１には、実施例１と同様の原料を用い、条件を変えて焼成することにより、青色蛍光体である白色粉体、黄緑色蛍光体である黄緑色蛍光体、更には赤色蛍光体である赤色粉体の、２〜３種類の焼結粉体の混合物を得る蛍光体の製造方法が記載されている。 Further, Example 1 of Patent Document 1 includes yellow-green powder that is a yellow-green phosphor by firing with a carbon crucible using SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 as raw materials, A method of manufacturing a phosphor that obtains a mixture of two types of sintered powders, an orange powder that is an orange phosphor, is described. In Reference Example 1, the same raw materials as in Example 1 were used, and the firing was performed under different conditions, so that white powder as a blue phosphor, yellow-green phosphor as a yellow-green phosphor, and red A method of manufacturing a phosphor that obtains a mixture of two to three types of sintered powder of red powder, which is a phosphor, is described.
特許文献１によれば、温度特性の良好な蛍光体が得られる。 According to Patent Document 1, a phosphor having good temperature characteristics can be obtained.
また、発明者の実験によれば、特許文献１の参考例１で得られるサイアロン構造の赤色蛍光体は、従来の赤色蛍光体に比べて、青色光等の短波長の励起光を用いた場合でも赤色光の輝度が高くなることが分かった。このため、赤色蛍光体として、サイアロン構造の赤色蛍光体を用いることが望まれている。 According to the inventors' experiment, the sialon-structured red phosphor obtained in Reference Example 1 of Patent Document 1 uses excitation light having a short wavelength, such as blue light, as compared with the conventional red phosphor. However, it turned out that the brightness of red light increases. For this reason, it is desired to use a red phosphor with a sialon structure as the red phosphor.
しかし、特許文献１に記載された蛍光体の製造方法では、赤色蛍光体を生成しようとする場合でも、焼成後に得られる焼結粉体は、赤色蛍光体や黄緑色蛍光体、更には青色蛍光体等の２〜３種類の焼結粉体の混合物になる。このため、特許文献１に記載された蛍光体の製造方法では、サイアロン構造の赤色蛍光体の製造歩留まりが低いという問題があった。 However, in the phosphor manufacturing method described in Patent Document 1, even when a red phosphor is to be produced, the sintered powder obtained after firing is a red phosphor, a yellow-green phosphor, or a blue phosphor. It becomes a mixture of 2-3 types of sintered powders such as body. For this reason, the phosphor manufacturing method described in Patent Document 1 has a problem in that the manufacturing yield of the sialon-structured red phosphor is low.
本発明は、上記事情に鑑みてなされたものであり、紫外光〜青色光の短波長の励起光を用いた場合でも輝度が高いサイアロン構造の赤色蛍光体を高い歩留まりで製造することができる赤色蛍光体の製造方法、およびこの製造方法で得られる赤色蛍光体、ならびにこの赤色蛍光体を用いた発光装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is capable of producing a high-yield sialon-structured red phosphor with high yield even when using excitation light having a short wavelength of ultraviolet light to blue light. It is an object of the present invention to provide a method for producing a phosphor, a red phosphor obtained by the production method, and a light emitting device using the red phosphor.
本発明は、赤色蛍光体の製造原料であるＳｒＣＯ３、Ｅｕ２Ｏ３等を、Ｎ２含有ガス雰囲気下、特定温度で焼成し、焼成体を解砕して焼成粉末を得る焼成工程を行うことにより、サイアロン構造の赤色蛍光体を高い歩留まりで製造することができることを見出して完成されたものである。 In the present invention, SrCO 3 , Eu 2 O 3 or the like, which is a raw material for producing a red phosphor, is fired at a specific temperature in an N 2 -containing gas atmosphere, and the fired body is crushed to obtain a fired powder. Thus, the present inventors have found that a red phosphor having a sialon structure can be produced with a high yield.
本発明に係る赤色蛍光体の製造方法は、上記問題点を解決するものであり、アルカリ土類金属炭酸塩と窒化珪素と窒化アルミニウムと酸化ユーロピウムとを含む蛍光体原料混合物を耐火るつぼに充填し、Ｎ２含有ガス雰囲気下、１４００℃〜２０００℃で焼成し、焼成体を解砕して赤色蛍光体粉末を得る焼成工程を有する赤色蛍光体の製造方法において、前記焼成工程は、Ｎ２含有ガス気流下、０．１ＭＰａ〜１．０ＭＰａの雰囲気圧力下で焼成して、発光ピーク波長が６４０ｎｍ以上６５０ｎｍ以下である赤色蛍光体である下記一般式（１）
（Ｓｒ１−ｘＥｕｘ）αＳｉβＡｌγＯδＮω （１）
（式（１）中、ｘは０＜ｘ＜１、αは０＜α≦３、βは５≦β≦７、γは３≦γ≦５、δは０．５≦δ≦０．８、ωは５≦ω≦１５を満足する数である。）
で表される組成のユーロピウム付活サイアロン蛍光体を得る工程であり、前記焼成工程を合計２回〜５回繰り返し行うことを特徴とする。
The method for producing a red phosphor according to the present invention solves the above-mentioned problem, and fills a refractory crucible with a phosphor raw material mixture containing alkaline earth metal carbonate, silicon nitride, aluminum nitride, and europium oxide. In the method for producing a red phosphor having a firing step of firing at 1400 ° C. to 2000 ° C. in an N 2 containing gas atmosphere to crush the fired body to obtain a red phosphor powder, the firing step includes N 2 The following general formula (1), which is a red phosphor having a light emission peak wavelength of 640 nm or more and 650 nm or less, which is fired under a gas stream under an atmospheric pressure of 0.1 MPa to 1.0 MPa.
(Sr 1-x Eu x ) α Si β Al γ O δ N ω (1)
(In the formula (1), x is 0 <x <1, α is 0 <α ≦ 3, β is 5 ≦ β ≦ 7, γ is 3 ≦ γ ≦ 5, and δ is 0.5 ≦ δ ≦ 0.8. , Ω is a number satisfying 5 ≦ ω ≦ 15.)
Is a step of obtaining a europium-activated sialon phosphor having a composition represented by formula (1), wherein the firing step is repeated 2 to 5 times in total.
また、本発明に係る赤色蛍光体は、上記問題点を解決するものであり、前記製造方法により得られる赤色蛍光体であって、
下記一般式（１）
（Ｓｒ１−ｘＥｕｘ）αＳｉβＡｌγＯδＮω （１）
（式（１）中、ｘは０＜ｘ＜１、αは０＜α≦３、βは５≦β≦７、γは３≦γ≦５、δは０．５≦δ≦０．８、ωは５≦ω≦１５を満足する数である。）で表される組成のユーロピウム付活サイアロン蛍光体であり、発光ピーク波長が６４０ｎｍ以上６５０ｎｍ以下であり、平均粒径が１μｍ〜５０μｍであることを特徴とする。
The red phosphor according to the present invention solves the above problems, and is a red phosphor obtained by the production method,
The following general formula (1)
(Sr 1-x Eu x ) α Si β Al γ O δ N ω (1)
(In the formula (1), x is 0 <x <1, α is 0 <α ≦ 3, β is 5 ≦ β ≦ 7, γ is 3 ≦ γ ≦ 5, and δ is 0.5 ≦ δ ≦ 0.8. , omega is a number satisfying 5 ≦ ω ≦ 15.) is a europium-activated sialon phosphor composition represented by, emission peak wavelength is at 650nm inclusive 640 nm, average particle size in 1μm~50μm It is characterized by being.
さらに、本発明に係る発光装置は、上記問題点を解決するものであり、基板と、この基板上に配置され紫外光〜青色光を出射する半導体発光素子と、この半導体発光素子からの出射光により励起されて可視光を出射する蛍光体を透明樹脂硬化物中に含み、前記半導体発光素子の発光面を被覆する発光部と、を備え、前記蛍光体は、前記赤色蛍光体を含むことを特徴とする。 Furthermore, the light-emitting device according to the present invention solves the above-described problems. A substrate, a semiconductor light-emitting element that is arranged on the substrate and emits ultraviolet light to blue light, and light emitted from the semiconductor light-emitting element. Including a phosphor that emits visible light when excited by the transparent resin cured product, and covers a light emitting surface of the semiconductor light emitting element, and the phosphor includes the red phosphor. Features.
本発明に係る赤色蛍光体の製造方法によれば、サイアロン構造の赤色蛍光体を高い歩留まりで製造することができる。 According to the method for producing a red phosphor according to the present invention, a red phosphor having a sialon structure can be produced with a high yield.
また、本発明に係る赤色蛍光体によれば、紫外光〜青色光の短波長の励起光を用いた場合でも輝度が高いサイアロン構造の赤色蛍光体が得られる。 In addition, according to the red phosphor according to the present invention, a red phosphor having a sialon structure with high luminance can be obtained even when excitation light having a short wavelength of ultraviolet light to blue light is used.
さらに、本発明に係る発光装置によれば、紫外光〜青色光の短波長の励起光を用いた場合でも輝度が高い発光装置が得られる。 Furthermore, according to the light emitting device of the present invention, a light emitting device having high luminance can be obtained even when excitation light having a short wavelength of ultraviolet light to blue light is used.
本発明に係る赤色蛍光体の製造方法、赤色蛍光体、および発光装置について説明する。 A method for producing a red phosphor, a red phosphor, and a light emitting device according to the present invention will be described.
［赤色蛍光体の製造方法］
本発明に係る赤色蛍光体の製造方法は、蛍光体原料混合物を焼成し、焼成体を解砕して焼成粉末を得る焼成工程を有する。
[Production method of red phosphor]
The method for producing a red phosphor according to the present invention includes a firing step of firing the phosphor raw material mixture and crushing the fired body to obtain a fired powder.
（焼成工程）
焼成工程は、蛍光体原料混合物を焼成し、焼成体を解砕して焼成粉末を得る工程である。
(Baking process)
The firing step is a step of firing the phosphor raw material mixture and crushing the fired body to obtain a fired powder.
＜蛍光体原料混合物＞
蛍光体原料混合物は、アルカリ土類金属炭酸塩と窒化珪素と窒化アルミニウムと酸化ユーロピウムとを含む混合物である。
<Phosphor material mixture>
The phosphor raw material mixture is a mixture containing an alkaline earth metal carbonate, silicon nitride, aluminum nitride, and europium oxide.
前記原料混合物のうちアルカリ土類金属炭酸塩としては、たとえば、Ｍｇ、Ｃａ、Ｓｒ、Ｂａの炭酸塩、具体的にはＳｒＣＯ３等が用いられる。 As the alkaline earth metal carbonate in the raw material mixture, for example, Mg, Ca, Sr, Ba carbonate, specifically, SrCO 3 or the like is used.
蛍光体原料混合物は、アルカリ土類金属炭酸塩と窒化珪素と窒化アルミニウムと酸化ユーロピウムとを含む。蛍光体原料混合物は、さらにフラックス剤として、反応促進剤である塩化ストロンチウムＳｒＣｌ２等を含んでいてもよい。 The phosphor raw material mixture includes alkaline earth metal carbonate, silicon nitride, aluminum nitride, and europium oxide. The phosphor raw material mixture may further contain strontium chloride SrCl 2 as a reaction accelerator as a fluxing agent.
蛍光体原料混合物は、耐火るつぼに充填される。耐火るつぼとしては、たとえば、窒化ホウ素るつぼ、カーボンるつぼ等が用いられる。 The phosphor raw material mixture is filled in a refractory crucible. As the refractory crucible, for example, a boron nitride crucible, a carbon crucible or the like is used.
＜焼成条件＞
耐火るつぼに充填された蛍光体原料混合物は焼成される。焼成装置は、耐火るつぼが配置される内部の焼成雰囲気の組成および圧力、ならびに焼成温度および焼成時間が所定条件に保たれる装置が用いられる。このような焼成装置としては、たとえば、電気炉が用いられる。
<Baking conditions>
The phosphor raw material mixture filled in the refractory crucible is fired. As the baking apparatus, an apparatus is used in which the composition and pressure of the internal baking atmosphere in which the refractory crucible is arranged, the baking temperature and the baking time are maintained under predetermined conditions. For example, an electric furnace is used as such a baking apparatus.
焼成雰囲気としては、Ｎ２含有ガスが用いられる。Ｎ２含有ガスとしては、たとえば、Ｎ２ガスや、Ｎ２とＨ２との混合ガス等が用いられる。 As the firing atmosphere, N 2 -containing gas is used. As the N 2 -containing gas, for example, N 2 gas or a mixed gas of N 2 and H 2 is used.
Ｎ２含有ガス中のＨ２は、蛍光体原料混合物から蛍光体粉末を焼成する際に、還元剤として作用するものである。 H 2 in the N 2 -containing gas acts as a reducing agent when the phosphor powder is fired from the phosphor raw material mixture.
一般的に、蛍光体原料混合物から蛍光体粉末を焼成するときは、蛍光体粉末に対して酸素Ｏを過剰に含む蛍光体原料混合物から適量の酸素Ｏが消失することにより、所定の組成の蛍光体粉末を得る。このとき、Ｎ２含有ガス中にＨ２が含まれると、焼成雰囲気が還元性雰囲気となり、焼成時の酸素Ｏの消失の度合いが大きくなる。 In general, when a phosphor powder is fired from a phosphor raw material mixture, an appropriate amount of oxygen O disappears from the phosphor raw material mixture containing excessive oxygen O with respect to the phosphor powder. Obtain body powder. At this time, if H 2 is contained in the N 2 -containing gas, the firing atmosphere becomes a reducing atmosphere, and the degree of disappearance of oxygen O during firing increases.
このため、Ｎ２含有ガス中にＨ２が含まれる場合は、Ｎ２含有ガス中にＨ２が含まれない場合に比べて、焼成時間を短くすることができる。ただし、Ｎ２含有ガス中のＨ２の含有量が多すぎると、得られる蛍光体粉末の組成が一般式（１）のＳｒサイアロン赤色蛍光体と異なりやすく、このために蛍光体粉末の発光強度が弱くなるおそれがある。 Therefore, when the H 2 contained in the N 2 containing gas, as compared to the case where the N 2 containing gas does not contain H 2, to shorten the baking time. However, if the content of H 2 in the N 2 -containing gas is too large, the composition of the obtained phosphor powder tends to be different from that of the Sr sialon red phosphor of the general formula (1). For this reason, the emission intensity of the phosphor powder May be weakened.
Ｎ２含有ガスが、Ｎ２ガス、またはＮ２とＨ２との混合ガスである場合、Ｎ２含有ガス中のＮ２とＨ２とのモル比率は、Ｎ２：Ｈ２が、通常１０：０〜１：９、好ましくは８：２〜２：８、さらに好ましくは６：４〜４：６である。 N 2 containing gas, if a mixed gas of N 2 gas or N 2 and H 2,, the molar ratio of N 2 and H 2 in N 2 containing gas is, N 2: H 2 is usually 10 : 0 to 1: 9, preferably 8: 2 to 2: 8, more preferably 6: 4 to 4: 6.
Ｎ２含有ガス中のＮ２とＨ２とのモル比率が、上記範囲内、すなわち通常１０：０〜１：９であると、短時間の焼成で、結晶構造の欠陥の少ない高品質な単結晶の蛍光体粉末を得ることができる。 When the molar ratio of N 2 and H 2 in the N 2 -containing gas is within the above range, that is, usually 10: 0 to 1: 9, a high-quality unit with few defects in the crystal structure can be obtained by firing in a short time. Crystalline phosphor powder can be obtained.
Ｎ２含有ガス中のＮ２とＨ２とのモル比率は、焼成装置のチャンバー内に連続的に供給されるＮ２とＨ２とを、Ｎ２とＨ２との流量の比率が上記比率になるように供給するとともに、チャンバー内の混合ガスを連続的に排出することにより、上記比率、すなわち通常１０：０〜１：９にすることができる。 The molar ratio of N 2 and H 2 in N 2 containing gas is a N 2 and H 2 which is continuously fed into the chamber of the calciner, N 2 and the ratio of the flow rate the ratio of H 2 And the mixture gas in the chamber is continuously discharged to achieve the above ratio, that is, usually 10: 0 to 1: 9.
焼成雰囲気であるＮ２含有ガスは、焼成装置のチャンバー内で気流を形成させるように流通させると、焼成が均一に行われるため好ましい。 It is preferable that the N 2 -containing gas as the firing atmosphere be circulated in a chamber of the firing apparatus so as to form an air flow because firing is performed uniformly.
焼成雰囲気であるＮ２含有ガスの圧力は、通常０．１ＭＰａ（略１ａｔｍ）〜１．０ＭＰａ、好ましくは０．５ＭＰａ〜０．８ＭＰａである。 The pressure of the N 2 -containing gas that is the firing atmosphere is usually 0.1 MPa (approximately 1 atm) to 1.0 MPa, preferably 0.5 MPa to 0.8 MPa.
焼成雰囲気の圧力が０．１ＭＰａ未満であると、焼成前にるつぼに仕込んだ蛍光体原料混合物に比較して、焼成後に得られる蛍光体粉末の組成が一般式（１）のＳｒサイアロン赤色蛍光体と異なりやすく、このために蛍光体粉末の発光強度が弱くなるおそれがある。 When the pressure of the firing atmosphere is less than 0.1 MPa, the composition of the phosphor powder obtained after firing is Sr sialon red phosphor of the general formula (1) as compared with the phosphor raw material mixture charged in the crucible before firing. Therefore, the emission intensity of the phosphor powder may be weakened.
焼成雰囲気の圧力が１．０ＭＰａを超えると、圧力が１．０ＭＰａ以下の場合と比較しても焼成条件に特に変化がなく、エネルギーの無駄遣いになるため好ましくない。 When the pressure of the firing atmosphere exceeds 1.0 MPa, the firing conditions are not particularly changed even when the pressure is 1.0 MPa or less, which is not preferable because energy is wasted.
焼成温度は、１４００℃〜２０００℃、好ましくは１６００℃〜１８００℃、さらに好ましくは１６５０℃〜１７５０℃である。 The firing temperature is 1400 ° C to 2000 ° C, preferably 1600 ° C to 1800 ° C, more preferably 1650 ° C to 1750 ° C.
焼成温度が１４００℃〜２０００℃の範囲内にあると、短時間の焼成で、結晶構造の欠陥の少ない高品質な単結晶の蛍光体粉末を得ることができる。 When the firing temperature is in the range of 1400 ° C. to 2000 ° C., high-quality single crystal phosphor powder with few crystal structure defects can be obtained by firing in a short time.
焼成温度が１４００℃未満であると、得られる蛍光体粉末が紫外〜青色光により励起されて出射する光の色が、赤色以外の色、たとえば緑色等の色になるおそれがある。 If the firing temperature is less than 1400 ° C., the phosphor powder obtained is excited by ultraviolet to blue light, and the color of the emitted light may be a color other than red, such as green.
焼成温度が２０００℃を超えると、焼成の際のＮとＯの消失度合いが大きくなることにより得られる蛍光体粉末の組成が一般式（１）のＳｒサイアロン赤色蛍光体と異なりやすく、このために蛍光体粉末の発光強度が弱くなるおそれがある。 When the firing temperature exceeds 2000 ° C., the composition of the phosphor powder obtained by increasing the degree of disappearance of N and O during firing tends to be different from that of the Sr sialon red phosphor of the general formula (1). There is a possibility that the emission intensity of the phosphor powder is weakened.
焼成時間は、通常０．５時間〜２０時間、好ましくは４時間〜１０時間、さらに好ましくは４時間〜５時間である。 The firing time is usually 0.5 hours to 20 hours, preferably 4 hours to 10 hours, and more preferably 4 hours to 5 hours.
焼成時間が０．５時間未満である場合または２０時間を超える場合は、得られる蛍光体粉末の組成が一般式（１）のＳｒサイアロン赤色蛍光体と異なりやすく、このために蛍光体粉末の発光強度が弱くなるおそれがある。 When the firing time is less than 0.5 hours or exceeds 20 hours, the composition of the obtained phosphor powder is likely to be different from that of the Sr sialon red phosphor of the general formula (1), and for this reason, the phosphor powder emits light. There is a risk that strength may be weakened.
焼成時間は、焼成温度が高い場合は、０．５時間〜２０時間の範囲内で短い時間とすることが好ましく、焼成温度が低い場合は、０．５時間〜２０時間の範囲内で長い時間とすることが好ましい。 The firing time is preferably a short time within a range of 0.5 hours to 20 hours when the firing temperature is high, and a long time within a range of 0.5 hours to 20 hours when the firing temperature is low. It is preferable that
焼成後の耐火るつぼ中には、赤色蛍光体粉末等の蛍光体粉末からなる焼成体が生成される。焼成体は、通常、弱く固まった塊状になっている。焼成体を乳棒等を用いて軽く解砕すると、赤色蛍光体粉末が得られる。ここで赤色蛍光体粉末とは、紫外〜青色光により励起されて出射する光の色が赤色である蛍光体粉末を意味する。 In the fire-resistant crucible after firing, a fired body made of phosphor powder such as red phosphor powder is generated. The fired body is usually in the form of a weak and solid lump. When the fired body is lightly crushed using a pestle or the like, a red phosphor powder is obtained. Here, the red phosphor powder means a phosphor powder in which the color of light emitted by being excited by ultraviolet to blue light is red.
焼成体の解砕により、焼成工程は終了する。解砕で得られた赤色蛍光体粉末は、一般式（１）の組成を有するＳｒサイアロン赤色蛍光体の粉末になる。
なお、焼成条件によっては、耐火るつぼ中の焼成体の全てが赤色蛍光体粉末にならず、一部が赤色以外の色の蛍光体粉末になる場合がある。たとえば、焼成装置のチャンバー内の熱分布の不均一や耐火るつぼの熱分布の不均一等のために、耐火るつぼ内の焼成体の上側の部分、すなわちるつぼの蓋を取ったときの焼成体の表面側の部分が赤色蛍光体粉末からなるとともに、焼成体の下側の部分、すなわちるつぼの底部側の焼成体の部分が緑色蛍光体粉末からなる場合がある。
The firing step is completed by crushing the fired body. The red phosphor powder obtained by crushing becomes a powder of Sr sialon red phosphor having the composition of the general formula (1).
Depending on the firing conditions, all of the fired body in the refractory crucible may not be a red phosphor powder, and a part thereof may be a phosphor powder of a color other than red. For example, due to non-uniform heat distribution in the chamber of the baking apparatus, non-uniform heat distribution in the refractory crucible, etc. In some cases, the surface side portion is made of red phosphor powder, and the lower portion of the fired body, that is, the fired body portion on the bottom side of the crucible is made of green phosphor powder.
このような場合は、上記焼成工程をさらに１回〜４回連続して繰り返し、合計２回〜５回行うと、焼成体を解砕した蛍光体粉末が赤色蛍光体粉末の単一相に近づく、すなわち、赤色蛍光体粉末の収率が高くなるため好ましい。 In such a case, when the firing process is repeated 1 to 4 times in succession for a total of 2 to 5 times, the phosphor powder obtained by crushing the fired body approaches the single phase of the red phosphor powder. That is, it is preferable because the yield of the red phosphor powder is increased.
具体的には、はじめに、１回目の焼成工程の途中で得られた焼成体を解砕して、赤色蛍光体粉末と、赤色以外の色の蛍光体粉末とからなる蛍光体粉末混合物を得る。次に、この蛍光体粉末混合物を、１回目の焼成工程における蛍光体原料混合物と同様にして、耐火るつぼに充填し、１回目の焼成工程と同じ焼成条件で２回目の焼成工程を行い、焼成体を解砕して蛍光体粉末を得る。得られた蛍光体粉末は、通常、１回目の焼成工程で得られた蛍光体粉末に比較して、赤色蛍光体粉末の割合が高くなる。 Specifically, first, a fired body obtained in the middle of the first firing step is crushed to obtain a phosphor powder mixture composed of a red phosphor powder and a phosphor powder of a color other than red. Next, this phosphor powder mixture is filled in a refractory crucible in the same manner as the phosphor raw material mixture in the first firing step, and the second firing step is performed under the same firing conditions as the first firing step. The body is crushed to obtain phosphor powder. The obtained phosphor powder usually has a higher proportion of red phosphor powder than the phosphor powder obtained in the first firing step.
２回目の焼成工程終了後に得られる蛍光体粉末が、依然、赤色蛍光体粉末と赤色以外の色の蛍光体粉末とからなる蛍光体粉末混合物である場合において、赤色蛍光体粉末の収率をより高くしたいときは、２回目の焼成工程と同様にして、３回目の焼成工程をさらに行う。 In the case where the phosphor powder obtained after the completion of the second baking process is still a phosphor powder mixture composed of a red phosphor powder and a phosphor powder of a color other than red, the yield of the red phosphor powder is further increased. When it is desired to make it higher, the third baking step is further performed in the same manner as the second baking step.
このようにして、焼成工程終了後に得られる蛍光体粉末が、依然、赤色蛍光体粉末と赤色以外の色の蛍光体粉末とからなる蛍光体粉末混合物である場合において、赤色蛍光体粉末の収率をより高くしたいときは、必要により、焼成工程を繰り返し、最大で合計５回まで焼成工程を行う。 In this way, when the phosphor powder obtained after the firing step is still a phosphor powder mixture consisting of a red phosphor powder and a phosphor powder of a color other than red, the yield of the red phosphor powder When it is desired to make the temperature higher, the firing process is repeated as necessary, and the firing process is performed up to a total of 5 times.
このように焼成工程を連続して繰り返すことにより赤色蛍光体粉末の収率が高くなる理由は、以下のとおりであると考えられる。 The reason why the yield of the red phosphor powder is increased by repeating the firing step in this manner is considered as follows.
すなわち、焼成体の一部が赤色蛍光体粉末以外の蛍光体粉末、たとえば緑色蛍光体粉末等になるのは、緑色蛍光体粉末等の酸素Ｏ等の組成が一般式（１）の組成を満たしていないからであると解される。 That is, a part of the fired body becomes a phosphor powder other than the red phosphor powder, such as a green phosphor powder, because the composition of oxygen O or the like of the green phosphor powder satisfies the composition of the general formula (1). It is understood that it is not.
一方、本発明で上記焼成工程を行うと、被焼成物である蛍光体原料混合物や蛍光体粉末混合物から酸素Ｏが除去される。酸素Ｏの除去の度合いは、焼成工程を繰り返して行うことにより高くなる。 On the other hand, when the firing step is performed in the present invention, oxygen O is removed from the phosphor raw material mixture and phosphor powder mixture, which are the objects to be fired. The degree of removal of oxygen O is increased by repeating the firing process.
このため、焼成工程終了後に得られる蛍光体粉末が、赤色蛍光体粉末と赤色蛍光体以外の色の蛍光体粉末とからなる蛍光体粉末混合物である場合は、焼成工程をさらに繰り返すことにより、蛍光体粉末混合物から酸素Ｏが徐々に除去されて、得られる蛍光体粉末の酸素Ｏ等の組成が一般式（１）の組成を満たすようになるものと考えられる。 For this reason, when the phosphor powder obtained after the firing process is a phosphor powder mixture comprising a red phosphor powder and a phosphor powder of a color other than the red phosphor, the firing process is further repeated, It is considered that oxygen O is gradually removed from the body powder mixture, and the composition of oxygen O and the like in the obtained phosphor powder satisfies the composition of the general formula (1).
なお、焼成工程の合計繰り返し回数が６回以上になると、過反応になり、すなわち酸素Ｏが除去されすぎることにより、赤色蛍光体粉末の収率が低くなるおそれがある。 Note that if the total number of repetitions of the firing step is 6 times or more, overreaction occurs, that is, oxygen O is removed excessively, which may reduce the yield of the red phosphor powder.
以上の本発明に係る赤色蛍光体の製造方法で得られる赤色蛍光体は、以下に示す本発明に係る赤色蛍光体となる。 The red phosphor obtained by the above-described method for producing a red phosphor according to the present invention is the red phosphor according to the present invention described below.
［赤色蛍光体］
本発明に係る赤色蛍光体は、本発明に係る赤色蛍光体の製造方法で得られる赤色蛍光体であり、下記一般式（１）
（Ｓｒ１−ｘＥｕｘ）αＳｉβＡｌγＯδＮω （１）
（式（１）中、ｘは０＜ｘ＜１、αは０＜α≦３、βは５≦β≦９、γは１≦γ≦５、δは０．５≦δ≦２、ωは５≦ω≦１５を満足する数である。）
で表される組成のユーロピウム付活サイアロン蛍光体である。このユーロピウム付活サイアロン蛍光体を、以下、「Ｓｒサイアロン赤色蛍光体」ともいう。
[Red phosphor]
The red phosphor according to the present invention is a red phosphor obtained by the method for producing a red phosphor according to the present invention, and the following general formula (1)
(Sr 1-x Eu x ) α Si β Al γ O δ N ω (1)
(In the formula (1), x is 0 <x <1, α is 0 <α ≦ 3, β is 5 ≦ β ≦ 9, γ is 1 ≦ γ ≦ 5, δ is 0.5 ≦ δ ≦ 2, ω Is a number satisfying 5 ≦ ω ≦ 15.)
Is a europium activated sialon phosphor having the composition This europium-activated sialon phosphor is hereinafter also referred to as “Sr sialon red phosphor”.
一般式（１）において、ｘは、０＜ｘ＜１、好ましくは０．０２５≦ｘ≦０．５、さらに好ましくは０．２５≦ｘ≦０．５を満足する数である。 In the general formula (1), x is a number that satisfies 0 <x <1, preferably 0.025 ≦ x ≦ 0.5, and more preferably 0.25 ≦ x ≦ 0.5.
ｘが０であると焼成工程で得られる焼成体が蛍光体にならず、ｘが１であると赤色蛍光体粉末の発光効率が低くなる。 When x is 0, the fired body obtained in the firing step is not a phosphor, and when x is 1, the luminous efficiency of the red phosphor powder is low.
また、ｘは０＜ｘ＜１の範囲内で小さい数になるほど赤色蛍光体の発光効率が低下しやすくなる。さらに、ｘは０＜ｘ＜１の範囲内で大きい数になるほどＥｕ濃度の過剰のために濃度消光を起こしやすくなる。 Also, the smaller the x is in the range of 0 <x <1, the easier it is for the luminous efficiency of the red phosphor to decrease. Furthermore, as x becomes larger in the range of 0 <x <1, the concentration quenching is more likely to occur due to the excessive Eu concentration.
このため、ｘは０＜ｘ＜１のうちでも、０．０２５≦ｘ≦０．５を満足する数が好ましく、０．２５≦ｘ≦０．５を満足する数がさらに好ましい。 For this reason, x is preferably a number satisfying 0.025 ≦ x ≦ 0.5, and more preferably a number satisfying 0.25 ≦ x ≦ 0.5, even if 0 <x <1.
一般式（１）において、Ｓｒの総合的な添え字（１−ｘ）αは０＜（１−ｘ）α＜３を満足する数である。また、Ｅｕの総合的な添え字ｘαは０＜ｘα＜３を満足する数である。すなわち、一般式（１）において、ＳｒおよびＥｕの総合的な添え字は、それぞれ０を超え３未満を満足する数である。
一般式（１）においてＳｉの添え字であるβは５≦β≦９を満足する数である。
一般式（１）においてＡｌの添え字であるγは１≦γ≦５を満足する数である。
一般式（１）においてＯの添え字であるδは０．５≦δ≦２を満足する数である。
一般式（１）においてＮの添え字であるωは５≦ω≦１５を満足する数である。
一般式（１）において添え字β、γ、δおよびωが、それぞれ上記範囲外の数になると、焼成で得られる蛍光体の組成が、一般式（１）で表されるＳｒサイアロン赤色蛍光体と異なるものになるおそれがある。
一般式（１）で表されるＳｒサイアロン赤色蛍光体は、通常、単結晶の粉末の形態をとる。
In the general formula (1), the total subscript (1-x) α of Sr is a number satisfying 0 <(1-x) α <3. Further, the overall subscript xα of Eu is a number satisfying 0 <xα <3. That is, in the general formula (1), the total subscripts of Sr and Eu are numbers exceeding 0 and less than 3, respectively.
In the general formula (1), β as a subscript of Si is a number satisfying 5 ≦ β ≦ 9.
In the general formula (1), γ which is a subscript of Al is a number satisfying 1 ≦ γ ≦ 5.
In the general formula (1), δ as a subscript of O is a number satisfying 0.5 ≦ δ ≦ 2.
In the general formula (1), ω, which is a subscript of N, is a number satisfying 5 ≦ ω ≦ 15.
When the subscripts β, γ, δ, and ω in the general formula (1) are numbers outside the above ranges, the phosphor composition obtained by firing has the Sr sialon red phosphor represented by the general formula (1). May be different.
The Sr sialon red phosphor represented by the general formula (1) usually takes the form of a single crystal powder.
Ｓｒサイアロン赤色蛍光体の粉末は、平均粒径が、好ましくは１μｍ〜５０μｍである。ここで、平均粒径とは、コールターカウンター法による測定値であり、体積累積分布の中央値Ｄ５０を意味する。 The Sr sialon red phosphor powder has an average particle size of preferably 1 μm to 50 μm. Here, the average particle diameter is a value measured by the Coulter counter method, it means the median D 50 of the cumulative volume distribution.
Ｓｒサイアロン赤色蛍光体の粉末の平均粒径が１μｍ未満であったり５０μｍを超えたりすると、透明樹脂硬化物中にＳｒサイアロン赤色蛍光体の粉末や他の色の蛍光体粉末を分散させ、半導体発光素子からの出射光を照射して赤色光や他の色の光を出射させる構造の発光装置を作製した場合に、発光装置からの光の取り出し効率が低下するおそれがある。 When the average particle size of the Sr sialon red phosphor powder is less than 1 μm or more than 50 μm, the Sr sialon red phosphor powder or other color phosphor powders are dispersed in the cured transparent resin, and the semiconductor light emission When a light-emitting device having a structure in which light emitted from the element is irradiated to emit red light or other color light, the light extraction efficiency from the light-emitting device may be reduced.
一般式（１）で表されるＳｒサイアロン赤色蛍光体は、紫外光〜青色光を受光すると励起され、赤色光を出射する。 The Sr sialon red phosphor represented by the general formula (1) is excited when it receives ultraviolet light to blue light and emits red light.
ここで、紫外光〜青色光とは、紫外光〜青色光の波長域内にピーク波長を有する光を意味する。紫外光〜青色光は、３７０ｎｍ〜４７０ｎｍの範囲内にピーク波長を有する光であることが好ましい。 Here, the ultraviolet light to blue light means light having a peak wavelength in the wavelength range of ultraviolet light to blue light. The ultraviolet light to blue light is preferably light having a peak wavelength in the range of 370 nm to 470 nm.
紫外光〜青色光の受光により、一般式（１）で表されるＳｒサイアロン赤色蛍光体から出射される赤色光は、５８０ｎｍ〜６５０ｎｍの範囲内にピーク波長を有する光になる。 By receiving ultraviolet light to blue light, red light emitted from the Sr sialon red phosphor represented by the general formula (1) becomes light having a peak wavelength in the range of 580 nm to 650 nm.
［発光装置］
本発明に係る発光装置は、上記の本発明に係る赤色蛍光体、すなわちＳｒサイアロン赤色蛍光体を用いる発光装置である。
[Light emitting device]
The light emitting device according to the present invention is a light emitting device using the red phosphor according to the present invention, that is, the Sr sialon red phosphor.
具体的には、本発明に係る発光装置は、基板と、この基板上に配置される半導体発光素子と、この半導体発光素子からの出射光により励起されて可視光を出射する蛍光体を透明樹脂硬化物中に含み、半導体発光素子の発光面を被覆する発光部とを備え、発光部に用いられる蛍光体はＳｒサイアロン赤色蛍光体を含む発光装置である。 Specifically, a light-emitting device according to the present invention includes a substrate, a semiconductor light-emitting element disposed on the substrate, and a phosphor that emits visible light when excited by light emitted from the semiconductor light-emitting element. The phosphor used in the light emitting unit is a light emitting device including a Sr sialon red phosphor.
発光装置は、発光部中に含まれる蛍光体がＳｒサイアロン赤色蛍光体のみであれば、発光装置の出射面から赤色光を出射する。 The light emitting device emits red light from the emission surface of the light emitting device if the phosphor contained in the light emitting unit is only Sr sialon red phosphor.
また、本発明に係る発光装置は、発光部中に、Ｓｒサイアロン赤色蛍光体に加え、青色蛍光体および緑色蛍光体を含むようにすると、各色の蛍光体から出射される赤色光、青色光および緑色光の混色により、発光装置の出射面から白色光を出射する白色光発光装置とすることもできる。 Further, in the light emitting device according to the present invention, when the light emitting unit includes the blue phosphor and the green phosphor in addition to the Sr sialon red phosphor, the red light, the blue light emitted from each color phosphor, A white light emitting device that emits white light from the emission surface of the light emitting device by mixing green light can also be obtained.
さらに、本発明に係る発光装置は、Ｓｒサイアロン赤色蛍光体に加え、他の赤色蛍光体を含んでいてもよい。 Furthermore, the light emitting device according to the present invention may include other red phosphors in addition to the Sr sialon red phosphor.
（基板）
基板としては、たとえば、アルミナ、窒化アルミニウム（ＡｌＮ）等のセラミックス、ガラスエポキシ樹脂等が用いられる。基板がアルミナ板や窒化アルミニウム板であると、熱伝導性が高く、ＬＥＤ光源の温度上昇を抑制することができるため好ましい。
(substrate)
As the substrate, for example, ceramics such as alumina and aluminum nitride (AlN), glass epoxy resin, and the like are used. It is preferable that the substrate is an alumina plate or an aluminum nitride plate because the thermal conductivity is high and the temperature rise of the LED light source can be suppressed.
（半導体発光素子）
半導体発光素子は、基板上に配置される。
(Semiconductor light emitting device)
The semiconductor light emitting element is disposed on the substrate.
半導体発光素子としては、紫外光〜青色光を出射する半導体発光素子が用いられる。ここで、紫外光〜青色光とは、紫外光〜青色光の波長域内にピーク波長を有する光を意味する。紫外光〜青色光は、３７０ｎｍ〜４７０ｎｍの範囲内にピーク波長を有する光であることが好ましい。 As the semiconductor light emitting element, a semiconductor light emitting element that emits ultraviolet light to blue light is used. Here, the ultraviolet light to blue light means light having a peak wavelength in the wavelength range of ultraviolet light to blue light. The ultraviolet light to blue light is preferably light having a peak wavelength in the range of 370 nm to 470 nm.
紫外光〜青色光を出射する半導体発光素子としては、たとえば、紫外発光ダイオード、紫色発光ダイオード、青色発光ダイオード、紫外レーザダイオード、紫色レーザダイオードおよび青色レーザダイオード等が用いられる。なお、半導体発光素子がレーザダイオードの場合、上記ピーク波長とは、ピーク発振波長を意味する。 As the semiconductor light emitting element that emits ultraviolet light to blue light, for example, an ultraviolet light emitting diode, a purple light emitting diode, a blue light emitting diode, an ultraviolet laser diode, a purple laser diode, a blue laser diode, or the like is used. When the semiconductor light emitting element is a laser diode, the peak wavelength means a peak oscillation wavelength.
（発光部）
発光部は、半導体発光素子からの出射光である紫外光〜青色光により励起されて可視光を出射する蛍光体を透明樹脂硬化物中に含むものであり、半導体発光素子の発光面を被覆するように形成される。
(Light emitting part)
The light emitting part includes a phosphor that is excited by ultraviolet light to blue light that is emitted light from the semiconductor light emitting element and emits visible light in the transparent resin cured product, and covers the light emitting surface of the semiconductor light emitting element. Formed as follows.
発光部に用いられる蛍光体は、少なくとも上記の本発明に係る赤色蛍光体、すなわちＳｒサイアロン赤色蛍光体を含む。 The phosphor used in the light emitting unit includes at least the red phosphor according to the present invention, that is, the Sr sialon red phosphor.
また、発光部に用いられる蛍光体は、Ｓｒサイアロン赤色蛍光体と、Ｓｒサイアロン赤色蛍光体以外の蛍光体とを含むものであってもよい。Ｓｒサイアロン赤色蛍光体以外の蛍光体としては、たとえば、青色蛍光体、緑色蛍光体、黄色蛍光体、紫色蛍光体、橙色蛍光体、Ｓｒサイアロン赤色蛍光体以外の赤色蛍光体等を用いることができる。蛍光体としては、通常、粉末状のものが用いられる。 Moreover, the phosphor used in the light emitting unit may include a Sr sialon red phosphor and a phosphor other than the Sr sialon red phosphor. Examples of the phosphor other than the Sr sialon red phosphor include a blue phosphor, a green phosphor, a yellow phosphor, a purple phosphor, an orange phosphor, and a red phosphor other than the Sr sialon red phosphor. . As the phosphor, a powdery one is usually used.
発光部において、蛍光体は透明樹脂硬化物中に含まれる。通常、蛍光体は透明樹脂硬化物中に分散される。 In the light emitting part, the phosphor is contained in the cured transparent resin. Usually, the phosphor is dispersed in a cured transparent resin.
発光部に用いられる透明樹脂硬化物は、透明樹脂、すなわち透明性の高い樹脂を硬化させたものである。透明樹脂としては、たとえば、シリコーン樹脂、エポキシ樹脂等が用いられる。シリコーン樹脂のうちでは、ジメチルシリコーン樹脂が、ＵＶ耐性が高いため好ましい。 The transparent resin cured product used for the light emitting part is obtained by curing a transparent resin, that is, a highly transparent resin. As the transparent resin, for example, a silicone resin or an epoxy resin is used. Among silicone resins, dimethyl silicone resin is preferable because of its high UV resistance.
発光部は、たとえば、はじめに透明樹脂と蛍光体とを混合して、蛍光体が透明樹脂中に分散した蛍光体スラリーを調製し、次に、蛍光体スラリーを半導体発光素子に塗布し硬化させることにより得られる。 For example, the light emitting unit first mixes a transparent resin and a phosphor to prepare a phosphor slurry in which the phosphor is dispersed in the transparent resin, and then applies the phosphor slurry to the semiconductor light emitting element and cures it. Is obtained.
蛍光体スラリーは、たとえば、１００℃〜１６０℃に加熱することにより硬化させることができる。 The phosphor slurry can be cured, for example, by heating to 100 ° C to 160 ° C.
図１は、本発明に係る発光装置の発光スペクトルの一例である。
具体的には、半導体発光素子としてピーク波長が４００ｎｍの紫色光を出射する紫色ＬＥＤを用いるとともに、蛍光体として一般式（１）で表されるＳｒサイアロン赤色蛍光体のみを用いた、赤色発光装置の発光スペクトルである。
FIG. 1 is an example of an emission spectrum of a light emitting device according to the present invention.
Specifically, a red light emitting device using a violet LED emitting violet light having a peak wavelength of 400 nm as a semiconductor light emitting element and using only a Sr sialon red phosphor represented by the general formula (1) as a phosphor. Is an emission spectrum.
なお、紫色ＬＥＤは、順方向降下電圧Ｖｆが３．１９５Ｖ、順方向電流Ｉｆが２０ｍＡである。 The purple LED has a forward voltage drop Vf of 3.195 V and a forward current If of 20 mA.
図１に示すように、蛍光体として一般式（１）で表されるＳｒサイアロン赤色蛍光体を用いた赤色発光装置は、紫色光等の短波長の励起光を用いた場合でも発光強度が高い。 As shown in FIG. 1, the red light emitting device using the Sr sialon red phosphor represented by the general formula (1) as the phosphor has a high emission intensity even when excitation light having a short wavelength such as violet light is used. .
以下に実施例を示すが、本発明はこれらに限定されて解釈されるものではない。 Examples are shown below, but the present invention is not construed as being limited thereto.
［参考例１］
はじめに、原料として、ＳｒＣＯ３を３１．２ｇと、ＡｌＮを４３．３ｇと、Ｓｉ３Ｎ４を１６．２ｇと、Ｅｕ２Ｏ３を９．３０ｇと、反応促進剤としてのフラックス剤を適量と、を乾式混合した後、得られた原料混合物を窒化ホウ素るつぼに充填した。
[ Reference Example 1 ]
First, as raw materials, 31.2 g of SrCO 3 , 43.3 g of AlN, 16.2 g of Si 3 N 4 , 9.30 g of Eu 2 O 3 , and an appropriate amount of fluxing agent as a reaction accelerator After dry mixing, the obtained raw material mixture was filled in a boron nitride crucible.
次に、原料混合物を充填した窒化ホウ素るつぼを電気炉内に載置した後、電気炉内に窒素Ｎ２と水素Ｈ２とをそれぞれ１Ｌ／ｍｉｎで連続的に供給するとともに、電気炉から適宜排気した。これにより、電気炉内に、窒素Ｎ２と水素Ｈ２とをモル比８：２で含む０．１ＭＰａの窒素含有ガスが流通するようにした。 Next, after placing the boron nitride crucible filled with the raw material mixture in the electric furnace, nitrogen N 2 and hydrogen H 2 are continuously supplied into the electric furnace at a rate of 1 L / min, respectively. Exhausted. As a result, a 0.1 MPa nitrogen-containing gas containing nitrogen N 2 and hydrogen H 2 at a molar ratio of 8: 2 circulated in the electric furnace.
この状態で電気炉内を加熱し、るつぼ内の混合物を、１４００℃で５時間焼成した。 In this state, the inside of the electric furnace was heated, and the mixture in the crucible was fired at 1400 ° C. for 5 hours.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 When the fired body in the crucible was observed after firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
焼成体を解砕し、赤色粉末を採取した後、赤色粉末に対し容量比で１０倍量の水で洗浄し、乾燥後、２００メッシュ、目開き７５μｍのふるいで分級して、赤色粉末を得た。また、焼成体を解砕して採取した緑色粉末についても同様に洗浄、乾燥、分級して、緑色粉末を得た。 After crushing the fired body and collecting the red powder, it is washed with 10 times the volume of water with respect to the red powder, dried, and then classified with a sieve of 200 mesh and an opening of 75 μm to obtain a red powder. It was. Further, the green powder collected by crushing the fired body was similarly washed, dried and classified to obtain a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
Ｓｒサイアロン赤色蛍光体の理論収量に対する焼成体中のＳｒサイアロン赤色蛍光体の歩留まりは、５０％であった。 The yield of the Sr sialon red phosphor in the fired body relative to the theoretical yield of the Sr sialon red phosphor was 50%.
得られたＳｒサイアロン赤色蛍光体について組成、発光ピーク波長および平均粒径を調べた。平均粒径は、コールターカウンター法による測定値であり、体積累積分布の中央値Ｄ５０の値である。 The composition, emission peak wavelength, and average particle size of the obtained Sr sialon red phosphor were examined. The average particle diameter is a value measured by the Coulter counter method, the value of the median D 50 of the cumulative volume distribution.
また、洗浄、乾燥、分級後の赤色粉末と緑色粉末とを混合した粉末混合物、すなわちＳｒサイアロン赤色蛍光体と緑色蛍光体との粉末混合物について輝度を調べた。なお、輝度は、後述の参考例６の試料の輝度を１００％としたときの相対値（％）として示す。 Further, the luminance of the powder mixture obtained by mixing the red powder and the green powder after washing, drying and classification, that is, the powder mixture of the Sr sialon red phosphor and the green phosphor was examined. The luminance is shown as a relative value (%) when the luminance of a sample of Reference Example 6 described later is 100%.
表１に、焼成条件を示す。表２に、焼成体の組成、焼成体の発光ピーク波長、粉末混合物の輝度、Ｓｒサイアロン赤色蛍光体の歩留まり、および平均粒径を示す。 Table 1 shows the firing conditions. Table 2 shows the composition of the fired body, the emission peak wavelength of the fired body, the brightness of the powder mixture, the yield of the Sr sialon red phosphor, and the average particle diameter.
以下に示す参考例２〜１３、実施例１についても、表１に焼成条件を示し、表２に焼成体の組成、焼成体の発光ピーク波長、粉末混合物の輝度、Ｓｒサイアロン赤色蛍光体の歩留まり、および平均粒径を示す。 Regarding Reference Examples 2 to 13 and Example 1 shown below, Table 1 shows the firing conditions, Table 2 shows the composition of the fired body, the emission peak wavelength of the fired body, the brightness of the powder mixture, and the yield of the Sr sialon red phosphor. And mean particle size.
なお、以下に示す実施例および比較例において、焼成体の組成、焼成体の発光ピーク波長とは、焼成体を解砕した焼成粉末が赤色蛍光体を含むときは赤色蛍光体について測定した組成および発光ピーク波長を示し、焼成体を解砕した焼成粉末が赤色蛍光体を含まないときは適宜定めた測定対象について測定した組成および発光ピーク波長を示す。 In the following examples and comparative examples, the composition of the fired body and the emission peak wavelength of the fired body are the composition measured for the red phosphor when the fired powder obtained by pulverizing the fired body contains a red phosphor, and When the fired powder obtained by pulverizing the fired body does not contain a red phosphor, the composition and the light emission peak wavelength measured with respect to an appropriately determined measurement object are shown.
さらに、以下に示す実施例および比較例において、粉末混合物とは単一相の粉末を含む意味で用いる。たとえば、洗浄、乾燥、分級後の粉末が赤色蛍光体粉末のみからなるときは、この場合の粉末混合物とは赤色蛍光体粉末を意味する。
［参考例２および３］
焼成条件を表１に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[ Reference Examples 2 and 3]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 1.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 When the fired body in the crucible was observed after firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 Analysis of the red powder composition is Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13, was Sr sialon red phosphor satisfying general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［参考例４］
（１回目の焼成工程）
焼成条件を表１に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[ Reference Example 4 ]
(First firing step)
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 1.
この１回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the first firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder mixture obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 After the second firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［参考例５］
（１回目の焼成工程）
焼成条件を表１に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[ Reference Example 5 ]
(First firing step)
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 1.
この１回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the first firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder mixture obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the second firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（３回目の焼成工程）
２回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Third firing process)
The powder mixture obtained in the second firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この３回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 When the fired body in the crucible was observed after the third firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［参考例６］
（１回目の焼成工程）
焼成条件を表１に示すように変えた以外は、参考例１と同様にして、１回目の焼成を行った。
[ Reference Example 6 ]
(First firing step)
The first firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 1.
この１回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the first firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。
(Second firing step)
The powder mixture obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step. After the second firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder.
焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（３回目の焼成工程）
２回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Third firing process)
The powder mixture obtained in the second firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この３回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 When the fired body in the crucible was observed after the third firing, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（４回目の焼成工程）
３回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Fourth firing step)
The powder mixture obtained in the third firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この４回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the fourth firing, the fired body was one lump made of only red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
得られたＳｒサイアロン赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、赤色蛍光体の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor, the emission peak wavelength of the fired product, the luminance of the red phosphor, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
［参考例７］
（１回目の焼成工程）
焼成条件を表１に示すように変えた以外は、参考例１と同様にして、１回目の焼成を行った。
[ Reference Example 7 ]
(First firing step)
The first firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 1.
この１回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the first firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。
(Second firing step)
The powder mixture obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step. After the second firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder.
焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（３回目および４回目の焼成工程）
２回目の焼成工程後、２回目の焼成工程と同じ焼成工程をさらに２回繰り返して行うことにより、３回目の焼成工程と４回目の焼成工程とを行った。
(3rd and 4th firing steps)
After the second baking step, the third baking step and the fourth baking step were performed by repeating the same baking step as the second baking step twice.
この３回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。 When the fired body in the crucible was observed after the third firing, the fired body was one lump composed of a red powder and a green powder.
３回目の焼成後、焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the third firing, the fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
４回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the fourth firing, the fired body was one lump made of only red powder.
４回目の焼成後、焼成体を解砕し、赤色粉末を得た。 After the fourth firing, the fired body was crushed to obtain a red powder.
（５回目の焼成工程）
４回目の焼成工程で得られた赤色粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。この５回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。
(5th firing step)
The red powder obtained in the fourth firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step. When the fired body in the crucible was observed after the fifth firing, the fired body was one lump made of only red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
得られたＳｒサイアロン赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、赤色蛍光体の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 The resulting Sr sialon red phosphor, in the same manner as in Reference Example 1, the emission peak wavelength of the sintered body were measured and the yield of the red phosphor brightness, and Sr sialon red phosphor.
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
［参考例８および９］
焼成条件を表１に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[ Reference Examples 8 and 9]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 1.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。また、焼成体のうち、大部分は赤色粉末であった。 When the fired body in the crucible was observed after firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion. Moreover, most of the fired bodies were red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［参考例１０〜１３、実施例１］
表２に示す各組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例２と同様にして、焼成を行った。
[ Reference Examples 10 to 13, Example 1 ]
Firing was carried out in the same manner as in Reference Example 2 except that the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture were changed so that a fired body having each composition shown in Table 2 was obtained. went.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 When the fired body in the crucible was observed after firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、および粉末混合物の輝度を測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired product and the luminance of the powder mixture were measured in the same manner as in Reference Example 1 .
表２中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 2, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［比較例１］
焼成条件を表３に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[Comparative Example 1]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 3.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は緑色粉末からなる一つの塊になっていた。 When the fired body in the crucible was observed after firing, the fired body was a lump made of green powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a green powder.
緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体（組成：ＳｒＳｉ２Ｏ２Ｎ２：Ｅｕ）であった。なお、母体組成の全く異なる蛍光体が得られたため、Ｅｕ濃度は測定しなかった。 When the green powder was analyzed, it was a green phosphor (composition: SrSi 2 O 2 N 2 : Eu) not satisfying the general formula (1). Since phosphors having completely different matrix compositions were obtained, the Eu concentration was not measured.
得られた緑色蛍光体について、参考例１と同様にして、緑色蛍光体の発光ピーク波長、緑色蛍光体の輝度、Ｓｒサイアロン赤色蛍光体の歩留まり、および平均粒径を測定した。 For the obtained green phosphor, the emission peak wavelength of the green phosphor, the luminance of the green phosphor, the yield of the Sr sialon red phosphor, and the average particle size were measured in the same manner as in Reference Example 1 .
表４に、焼成体の組成、焼成体の発光ピーク波長、粉末混合物の輝度、Ｓｒサイアロン赤色蛍光体の歩留まり、および平均粒径を示す。 Table 4 shows the composition of the fired body, the emission peak wavelength of the fired body, the brightness of the powder mixture, the yield of the Sr sialon red phosphor, and the average particle diameter.
表４中、焼成粉末の組成は緑色蛍光体の組成、発光ピーク波長は緑色蛍光体の発光ピーク波長を示す。 In Table 4, the composition of the fired powder indicates the composition of the green phosphor, and the emission peak wavelength indicates the emission peak wavelength of the green phosphor.
以下に示す比較例２〜８、参考例１４および実施例２についても、表３に焼成条件を示し、表４に焼成体の組成、焼成体の発光ピーク波長、粉末混合物の輝度およびＳｒサイアロン赤色蛍光体の歩留まりを示す。
［比較例２］
焼成条件を表３に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[Comparative Example 2]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 3.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 When the fired body in the crucible was observed after firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表４中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 4, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［比較例３〜７］
焼成条件を表３に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[Comparative Examples 3 to 7]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 3.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末からなる一つの塊になっていた。 When the fired body in the crucible was observed after firing, the fired body was one lump made of red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、Ｓｒサイアロン構造でなく一般式（１）を満たさない赤色蛍光体であった。 When the red powder was analyzed, it was not a Sr sialon structure but a red phosphor not satisfying the general formula (1).
具体的には、比較例３〜７の赤色蛍光体の組成はＳｒ２Ｓｉ５Ｎ８：Ｅｕであった。なお、母体組成の全く異なる蛍光体が得られたため、Ｅｕ濃度は測定しなかった。 Specifically, the composition of the red phosphors of Comparative Examples 3 to 7 was Sr 2 Si 5 N 8 : Eu. Since phosphors having completely different matrix compositions were obtained, the Eu concentration was not measured.
得られた赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、赤色蛍光体の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 The resulting red phosphor, in the same manner as in Reference Example 1, the emission peak wavelength of the sintered body were measured and the yield of the red phosphor brightness, and Sr sialon red phosphor.
表４中、焼成粉末の組成は赤色蛍光体の組成、発光ピーク波長は赤色蛍光体の発光ピーク波長を示す。 In Table 4, the composition of the calcined powder indicates the composition of the red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the red phosphor.
［参考例１４］
（１回目の焼成工程）
焼成条件を表３に示すように変えた以外は、参考例１と同様にして、１回目の焼成を行った。
[ Reference Example 14 ]
(First firing step)
The first firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 3.
この１回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the first firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder. The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末混合物を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。
(Second firing step)
The powder mixture obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step. After the second firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a green powder.
焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 The fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
（３回目〜５回目の焼成工程）
２回目の焼成工程後、２回目の焼成工程と同じ焼成工程をさらに３回繰り返して行うことにより、３回目、４回目、および５回目の焼成工程を行った。
(The third to fifth firing steps)
After the second baking step, the same baking step as the second baking step was repeated three more times to perform the third, fourth, and fifth baking steps.
３回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。 When the fired body in the crucible was observed after the third firing, the fired body was one lump composed of a red powder and a green powder.
３回目の焼成後、焼成体を解砕し、赤色粉末と緑色粉末とからなる粉末混合物を得た。 After the third firing, the fired body was crushed to obtain a powder mixture composed of a red powder and a green powder.
４回目の焼成後の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 After firing after the fourth firing, the fired body in the crucible was observed. As a result, the fired body was a single lump made of only red powder.
４回目の焼成後、焼成体を解砕し、赤色粉末を得た。 After the fourth firing, the fired body was crushed to obtain a red powder.
５回目の焼成後の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 After firing after the fifth firing, the fired body in the crucible was observed. As a result, the fired body was a single lump made of only red powder.
５回目の焼成後、焼成体を解砕し、赤色粉末を得た。 After the fifth firing, the fired body was crushed to obtain a red powder.
（６回目の焼成工程）
５回目の焼成工程で得られた赤色粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Sixth firing step)
The red powder obtained in the fifth firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この６回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と黒色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には黒色粉末が生成されており、底部側の部分には赤色粉末が生成されていた。 After the sixth firing, the fired body in the crucible was observed. As a result, the fired body was one lump composed of a red powder and a black powder. Specifically, black powder was generated in the top side (surface side) portion of the fired body in the crucible, and red powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および黒色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a black powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、黒色粉末を分析したところ、一般式（１）を満たさず、蛍光体でもなかった。 On the other hand, when the black powder was analyzed, it did not satisfy the general formula (1) and was not a phosphor.
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表４中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 4, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と黒色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and black powder obtained after washing | cleaning, drying, and classification was used.
［実施例２］
焼成条件を表３に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[ Example 2 ]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 3.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末と緑色粉末とからなる一つの塊になっていた。具体的には、るつぼ内の焼成体の頂部側（表面側）の部分には赤色粉末が生成されており、底部側の部分には緑色粉末が生成されていた。 When the fired body in the crucible was observed after firing, the fired body was one lump composed of a red powder and a green powder. Specifically, red powder was generated in the top side (surface side) portion of the fired body in the crucible, and green powder was generated in the bottom side portion.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末および緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder and a green powder.
赤色粉末を分析したところ、組成がＳｒ１．５Ｅｕ０．５Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たすＳｒサイアロン赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1.5 Eu 0.5 Si 7 Al 3 O 1 N 13 and the Sr sialon red phosphor satisfying the general formula (1).
一方、緑色粉末を分析したところ、一般式（１）を満たさない緑色蛍光体であった。 On the other hand, when the green powder was analyzed, it was a green phosphor that did not satisfy the general formula (1).
得られたＳｒサイアロン赤色蛍光体および粉末混合物について、参考例１と同様にして、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained Sr sialon red phosphor and powder mixture, the emission peak wavelength of the fired body, the luminance of the powder mixture, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表４中、焼成粉末の組成はＳｒサイアロン赤色蛍光体の組成、発光ピーク波長はＳｒサイアロン赤色蛍光体の発光ピーク波長を示す。 In Table 4, the composition of the fired powder indicates the composition of the Sr sialon red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the Sr sialon red phosphor.
なお、輝度を測定した粉末混合物としては、洗浄、乾燥、分級後に得られた赤色粉末と緑色粉末とを混合したものを用いた。 In addition, as a powder mixture which measured the brightness | luminance, what mixed the red powder and green powder obtained after washing | cleaning, drying, and classification was used.
［比較例８］
焼成条件を表３に示すように変えた以外は、参考例１と同様にして、焼成を行った。
[Comparative Example 8]
Firing was performed in the same manner as in Reference Example 1 except that the firing conditions were changed as shown in Table 3.
焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末からなる一つの塊になっていた。 When the fired body in the crucible was observed after firing, the fired body was one lump made of red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、Ｓｒサイアロン構造でなく一般式（１）を満たさない赤色蛍光体（組成：Ｓｒ２Ｓｉ５Ｎ８：Ｅｕ）であった。なお、母体組成の全く異なる蛍光体が得られたため、Ｅｕ濃度は測定しなかった。 When the red powder was analyzed, it was not a Sr sialon structure but a red phosphor (composition: Sr 2 Si 5 N 8 : Eu) not satisfying the general formula (1). Since phosphors having completely different matrix compositions were obtained, the Eu concentration was not measured.
得られた赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、赤色蛍光体の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを測定した。 For the obtained red phosphor, the emission peak wavelength of the fired product, the luminance of the red phosphor, and the yield of the Sr sialon red phosphor were measured in the same manner as in Reference Example 1 .
表４中、焼成粉末の組成は赤色蛍光体の組成、発光ピーク波長は赤色蛍光体の発光ピーク波長を示す。 In Table 4, the composition of the calcined powder indicates the composition of the red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the red phosphor.
［比較例９］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Example 9]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was one lump made of only red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、組成がＥｕ３Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たさない赤色蛍光体であった。 When the red powder was analyzed, the composition was Eu 3 Si 7 Al 3 O 1 N 13 and the red phosphor did not satisfy the general formula (1).
得られた赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、および赤色蛍光体の輝度を測定した。 For the obtained red phosphor, the emission peak wavelength of the fired product and the luminance of the red phosphor were measured in the same manner as in Reference Example 1 .
表６に、焼成体の組成、焼成体の発光ピーク波長、粉末混合物の輝度、およびＳｒサイアロン赤色蛍光体の歩留まりを示す。 Table 6 shows the composition of the fired body, the emission peak wavelength of the fired body, the brightness of the powder mixture, and the yield of the Sr sialon red phosphor.
表６中、焼成粉末の組成は赤色蛍光体の組成、発光ピーク波長は赤色蛍光体の発光ピーク波長を示す。 In Table 6, the composition of the fired powder indicates the composition of the red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the red phosphor.
以下に示す比較例１０〜１６についても、表５に焼成条件を示し、表６に焼成体の組成、焼成体の発光ピーク波長、粉末混合物の輝度およびＳｒサイアロン赤色蛍光体の歩留まりを示す。
［比較例１０および１１］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Examples 10 and 11]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は黄色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was one lump made of only yellow powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、黄色粉末を得た。 In the same manner as in Reference Example 1 , the fired product was crushed, washed, dried, and classified to obtain a yellow powder.
黄色粉末を分析したところ、比較例１０は組成がＳｒ１Ｅｕ１Ｓｉ１１Ａｌ３Ｏ１Ｎ１３、比較例１１は組成がＳｒ１Ｅｕ１Ｓｉ７Ａｌ７Ｏ１Ｎ１３であり、共に一般式（１）を満たさない黄色蛍光体であった。 When the yellow powder was analyzed, Comparative Example 10 had a composition of Sr 1 Eu 1 Si 11 Al 3 O 1 N 13 , and Comparative Example 11 had a composition of Sr 1 Eu 1 Si 7 Al 7 O 1 N 13. It was a yellow phosphor not satisfying (1).
得られた黄色蛍光体について、参考例１と同様にして、黄色蛍光体の発光ピーク波長、および黄色蛍光体の輝度を測定した。 For the obtained yellow phosphor, the emission peak wavelength of the yellow phosphor and the luminance of the yellow phosphor were measured in the same manner as in Reference Example 1 .
表６中、焼成粉末の組成は黄色蛍光体の組成、発光ピーク波長は黄色蛍光体の発光ピーク波長を示す。 In Table 6, the composition of the calcined powder indicates the composition of the yellow phosphor, and the emission peak wavelength indicates the emission peak wavelength of the yellow phosphor.
［比較例１２］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Example 12]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was one lump made of only red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、組成がＳｒ１Ｅｕ１Ｓｉ７Ａｌ３Ｎ１３であり、一般式（１）を満たさない赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1 Eu 1 Si 7 Al 3 N 13 and the red phosphor did not satisfy the general formula (1).
得られた赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、および赤色蛍光体の輝度を測定した。 For the obtained red phosphor, the emission peak wavelength of the fired product and the luminance of the red phosphor were measured in the same manner as in Reference Example 1 .
表６中、焼成粉末の組成は赤色蛍光体の組成、発光ピーク波長は赤色蛍光体の発光ピーク波長を示す。 In Table 6, the composition of the fired powder indicates the composition of the red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the red phosphor.
［比較例１３］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Example 13]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は黄色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was one lump made of only yellow powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、黄色粉末を得た。 In the same manner as in Reference Example 1 , the fired product was crushed, washed, dried, and classified to obtain a yellow powder.
黄色粉末を分析したところ、組成がＳｒ１Ｅｕ１Ｓｉ７Ａｌ３Ｏ３Ｎ１３であり、一般式（１）を満たさない黄色蛍光体であった。 When the yellow powder was analyzed, the composition was Sr 1 Eu 1 Si 7 Al 3 O 3 N 13 and the yellow phosphor did not satisfy the general formula (1).
得られた黄色蛍光体について、参考例１と同様にして、黄色蛍光体の発光ピーク波長、および黄色蛍光体の輝度を測定した。 For the obtained yellow phosphor, the emission peak wavelength of the yellow phosphor and the luminance of the yellow phosphor were measured in the same manner as in Reference Example 1 .
表６中、焼成粉末の組成は黄色蛍光体の組成、発光ピーク波長は黄色蛍光体の発光ピーク波長を示す。 In Table 6, the composition of the calcined powder indicates the composition of the yellow phosphor, and the emission peak wavelength indicates the emission peak wavelength of the yellow phosphor.
［比較例１４］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Example 14]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は緑色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was one lump made of only green powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、緑色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a green powder.
緑色粉末を分析したところ、組成がＳｒ１Ｅｕ１Ｓｉ７Ａｌ３Ｏ１Ｎ１であり、一般式（１）を満たさない緑色蛍光体であった。 When the green powder was analyzed, the composition was Sr 1 Eu 1 Si 7 Al 3 O 1 N 1 and the green phosphor did not satisfy the general formula (1).
得られた緑色蛍光体について、参考例１と同様にして、緑色蛍光体の発光ピーク波長、および緑色蛍光体の輝度を測定した。 For the obtained green phosphor, the emission peak wavelength of the green phosphor and the luminance of the green phosphor were measured in the same manner as in Reference Example 1 .
表６中、焼成粉末の組成は緑色蛍光体の組成、発光ピーク波長は緑色蛍光体の発光ピーク波長を示す。 In Table 6, the composition of the fired powder indicates the composition of the green phosphor, and the emission peak wavelength indicates the emission peak wavelength of the green phosphor.
［比較例１５］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Example 15]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は赤色粉末のみからなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was one lump made of only red powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、赤色粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a red powder.
赤色粉末を分析したところ、組成がＳｒ１Ｅｕ１Ｓｉ７Ａｌ３Ｏ１Ｎ１９であり、一般式（１）を満たさない赤色蛍光体であった。 When the red powder was analyzed, the composition was Sr 1 Eu 1 Si 7 Al 3 O 1 N 19 and the red phosphor did not satisfy the general formula (1).
得られた赤色蛍光体について、参考例１と同様にして、焼成体の発光ピーク波長、および赤色蛍光体の輝度を測定した。 For the obtained red phosphor, the emission peak wavelength of the fired product and the luminance of the red phosphor were measured in the same manner as in Reference Example 1 .
表６中、焼成粉末の組成は赤色蛍光体の組成、発光ピーク波長は赤色蛍光体の発光ピーク波長を示す。 In Table 6, the composition of the fired powder indicates the composition of the red phosphor, and the emission peak wavelength indicates the emission peak wavelength of the red phosphor.
［比較例１６］
（１回目の焼成工程）
焼成条件を表５に示すように変えるとともに、表６に示す組成の焼成体が得られるように、原料混合物におけるＳｒＣＯ３、ＡｌＮ、Ｓｉ３Ｎ４およびＥｕ２Ｏ３の配合量を変えた以外は参考例４と同様にして、１回目の焼成を行った。
[Comparative Example 16]
(First firing step)
Other than changing the blending amounts of SrCO 3 , AlN, Si 3 N 4 and Eu 2 O 3 in the raw material mixture so that the firing conditions are changed as shown in Table 5 and a fired body having the composition shown in Table 6 is obtained. Were fired for the first time in the same manner as in Reference Example 4 .
１回目の焼成後の焼成体を解砕し、粉末を得た。 The fired body after the first firing was crushed to obtain a powder.
（２回目の焼成工程）
１回目の焼成工程で得られた粉末を窒化ホウ素るつぼに充填し、１回目の焼成工程と同じ焼成条件で焼成した。
(Second firing step)
The powder obtained in the first firing step was filled in a boron nitride crucible and fired under the same firing conditions as in the first firing step.
この２回目の焼成後、るつぼ内の焼成体を観察したところ、焼成体は粉末からなる一つの塊になっていた。 When the fired body in the crucible was observed after the second firing, the fired body was a lump made of powder.
参考例１と同様にして、焼成体を解砕し、洗浄し、乾燥し、分級して、焼成粉末を得た。 In the same manner as in Reference Example 1 , the fired body was crushed, washed, dried, and classified to obtain a fired powder.
焼成粉末を分析したところ、組成がＳｒ３Ｓｉ７Ａｌ３Ｏ１Ｎ１３であり、一般式（１）を満たさず、蛍光体でもなかった。 When the calcined powder was analyzed, the composition was Sr 3 Si 7 Al 3 O 1 N 13 and it did not satisfy the general formula (1) and was not a phosphor.
得られた焼成粉末は、蛍光体でなかったため、焼成粉末の発光ピーク波長、および焼成粉末の輝度の測定は行わなかった。 Since the obtained fired powder was not a phosphor, the emission peak wavelength of the fired powder and the brightness of the fired powder were not measured.
Claims (4)
前記焼成工程は、Ｎ２含有ガス気流下、０．１ＭＰａ〜１．０ＭＰａの雰囲気圧力下で焼成して、発光ピーク波長が６４０ｎｍ以上６５０ｎｍ以下である赤色蛍光体である下記一般式（１）
（Ｓｒ１−ｘＥｕｘ）αＳｉβＡｌγＯδＮω （１）
（式（１）中、ｘは０＜ｘ＜１、αは０＜α≦３、βは５≦β≦７、γは３≦γ≦５、δは０．５≦δ≦０．８、ωは５≦ω≦１５を満足する数である。）
で表される組成のユーロピウム付活サイアロン蛍光体を得る工程であり、
前記焼成工程を合計２回〜５回繰り返し行うことを特徴とする赤色蛍光体の製造方法。 A phosphor raw material mixture containing an alkaline earth metal carbonate, silicon nitride, aluminum nitride, and europium oxide is filled in a refractory crucible and fired at 1400 ° C. to 2000 ° C. in an N 2 -containing gas atmosphere to crush the fired body. In the method for producing a red phosphor having a firing step to obtain a red phosphor powder,
The firing step is a red phosphor having an emission peak wavelength of 640 nm or more and 650 nm or less, which is fired under an N 2 -containing gas stream under an atmospheric pressure of 0.1 MPa to 1.0 MPa.
(Sr 1-x Eu x ) α Si β Al γ O δ N ω (1)
(In the formula (1), x is 0 <x <1, α is 0 <α ≦ 3, β is 5 ≦ β ≦ 7, γ is 3 ≦ γ ≦ 5, and δ is 0.5 ≦ δ ≦ 0.8. , Ω is a number satisfying 5 ≦ ω ≦ 15.)
A europium-activated sialon phosphor having a composition represented by:
The method for producing a red phosphor, wherein the firing step is repeated 2 to 5 times in total.
下記一般式（１）
（Ｓｒ１−ｘＥｕｘ）αＳｉβＡｌγＯδＮω （１）
（式（１）中、ｘは０＜ｘ＜１、αは０＜α≦３、βは５≦β≦７、γは３≦γ≦５、δは０．５≦δ≦０．８、ωは５≦ω≦１５を満足する数である。）
で表される組成のユーロピウム付活サイアロン蛍光体であり、
発光ピーク波長が６４０ｎｍ以上６５０ｎｍ以下であり、平均粒径が１μｍ〜５０μｍであることを特徴とする赤色蛍光体。 A red phosphor obtained by the production method according to claim 1,
The following general formula (1)
(Sr 1-x Eu x ) α Si β Al γ O δ N ω (1)
(In the formula (1), x is 0 <x <1, α is 0 <α ≦ 3, β is 5 ≦ β ≦ 7, γ is 3 ≦ γ ≦ 5, and δ is 0.5 ≦ δ ≦ 0.8. , Ω is a number satisfying 5 ≦ ω ≦ 15.)
A europium-activated sialon phosphor having a composition represented by :
A red phosphor having an emission peak wavelength of 640 nm or more and 650 nm or less and an average particle diameter of 1 μm to 50 μm.
この基板上に配置され紫外光〜青色光を出射する半導体発光素子と、
この半導体発光素子からの出射光により励起されて可視光を出射する蛍光体を透明樹脂硬化物中に含み、前記半導体発光素子の発光面を被覆する発光部と、を備え、
前記蛍光体は、請求項２に記載の赤色蛍光体を含むことを特徴とする発光装置。 A substrate,
A semiconductor light emitting device arranged on the substrate and emitting ultraviolet light to blue light;
A phosphor that is excited by the light emitted from the semiconductor light emitting element and emits visible light is contained in the transparent resin cured product, and includes a light emitting portion that covers the light emitting surface of the semiconductor light emitting element,
The light emitting device according to claim 2, wherein the phosphor includes the red phosphor according to claim 2.
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