JP6256541B2 - Light emitting device - Google Patents

Light emitting device Download PDF

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JP6256541B2
JP6256541B2 JP2016137685A JP2016137685A JP6256541B2 JP 6256541 B2 JP6256541 B2 JP 6256541B2 JP 2016137685 A JP2016137685 A JP 2016137685A JP 2016137685 A JP2016137685 A JP 2016137685A JP 6256541 B2 JP6256541 B2 JP 6256541B2
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phosphor
light emitting
emitting device
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JP2017041629A (en
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昌治 細川
昌治 細川
貞一 涌井
貞一 涌井
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Nichia Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Description

本開示は、発光装置に関する。   The present disclosure relates to a light emitting device.

光源と、この光源からの光で励起されて光源の色相とは異なる色相の光を放出可能な波長変換部材とを組み合わせることで、光の混色の原理により多様な色相の光を放出可能な発光装置が開発されている。特に、発光ダイオード（Light Emitting Diode：以下「ＬＥＤ」と呼ぶ。）と蛍光体とを組み合わせて形成した発光装置は、照明装置、液晶表示装置のバックライト等へと盛んに応用されており、普及が進んでいる。例えば、白色系の混色光を発光する発光装置においては、青緑色、緑色、黄緑色等の短波長に発光する蛍光体と、橙色、赤色等の長波長に発光する蛍光体とを組み合わせることで、液晶表示装置の色再現範囲や照明装置の演色性の改善が可能である。   Combining a light source and a wavelength conversion member that can be excited by the light from this light source and emit light of a hue different from the hue of the light source, it is possible to emit light of various hues based on the principle of light color mixing Equipment has been developed. In particular, a light-emitting device formed by combining a light emitting diode (hereinafter referred to as “LED”) and a phosphor is actively applied to lighting devices, backlights of liquid crystal display devices, and the like. Is progressing. For example, in a light emitting device that emits white mixed color light, a phosphor that emits light at a short wavelength such as blue-green, green, and yellow-green and a phosphor that emits light at a long wavelength such as orange and red are combined. It is possible to improve the color reproduction range of the liquid crystal display device and the color rendering properties of the lighting device.

高エネルギー励起においても輝度低下の少ない蛍光体として、サイアロン蛍光体、酸窒化物蛍光体、窒化物蛍光体等の、結晶構造に窒素を含有する無機結晶を母体とする蛍光体が提案されている。これらのうち窒化物蛍光体の一例として、ＣａＡｌＳｉＮ３を母体結晶としてＥｕ２＋で賦活された赤色蛍光体（以下、「ＣＡＳＮ蛍光体」と呼ぶ。）及びＣＡＳＮ蛍光体のＣａの一部をＳｒに置換した（Ｓｒ，Ｃａ）ＡｌＳｉＮ３：Ｅｕ（以下、「ＳＣＡＳＮ蛍光体」と呼ぶ。）が知られている。ＣＡＳＮ蛍光体及びＳＣＡＳＮ蛍光体は、６１０〜６８０ｎｍと幅広い範囲に発光ピーク波長を有している。これらの発光スペクトルの半値幅は７５〜９５ｎｍである。 Phosphors having a base of an inorganic crystal containing nitrogen in the crystal structure, such as sialon phosphors, oxynitride phosphors, and nitride phosphors, have been proposed as phosphors that have little decrease in luminance even at high energy excitation. . Among these, as an example of a nitride phosphor, a red phosphor (hereinafter referred to as “CASN phosphor”) activated with Eu 2+ using CaAlSiN 3 as a base crystal and a part of Ca of the CASN phosphor in Sr. Substituted (Sr, Ca) AlSiN 3 : Eu (hereinafter referred to as “SCASN phosphor”) is known. The CASN phosphor and SCASN phosphor have emission peak wavelengths in a wide range of 610 to 680 nm. The full width at half maximum of these emission spectra is 75 to 95 nm.

近年、半値幅が７０ｎｍ以下と狭い窒化物蛍光体としてＳｒＬｉＡｌ３Ｎ４：Ｅｕ（以下、「ＳＬＡＮ蛍光体」と呼ぶ。）が提案されている。この化合物の発光ピーク波長は６５０ｎｍ付近である（例えば、特許文献１、非特許文献１参照）。 In recent years, SrLiAl 3 N 4 : Eu (hereinafter referred to as “SLAN phosphor”) has been proposed as a nitride phosphor having a narrow half width of 70 nm or less. The emission peak wavelength of this compound is around 650 nm (see, for example, Patent Document 1 and Non-Patent Document 1).

国際公開第２０１３／１７５３３６号International Publication No. 2013/175336

Nature Materials, NMAT4012, 2014Nature Materials, NMAT4012, 2014

赤色発光の窒化物蛍光体を用いる発光装置において、さらなる演色性と発光効率の改善が求められている。
本開示に係る一実施態様の目的は、優れた演色性と高い発光効率とを有する発光装置を提供することにある。 In a light emitting device using a red light emitting nitride phosphor, further improvement in color rendering properties and light emission efficiency are required.
An object of an embodiment according to the present disclosure is to provide a light emitting device having excellent color rendering properties and high light emission efficiency.

前記課題を解決するための具体的手段は以下の通りであり、本開示は以下の態様を包含する。
４００ｎｍ以上４８０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子と、アルカリ土類金属、アルカリ金属、アルミニウム及びユーロピウムを含む窒化物である第一蛍光体と、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含む窒化物である第二蛍光体と、５００ｎｍ以上５６０ｎｍ以下の波長範囲に発光ピーク波長を有する第三蛍光体とを含む蛍光部材と、を備え、前記第一蛍光体及び第二蛍光体の総含有量に対する第一蛍光体の含有率が５質量％以上９５質量％以下の発光装置である。 Specific means for solving the above problems are as follows, and the present disclosure includes the following aspects.
A light emitting device having an emission peak wavelength in a wavelength range of 400 nm or more and 480 nm or less, a first phosphor which is a nitride containing alkaline earth metal, alkali metal, aluminum and europium, alkaline earth metal, aluminum, silicon and europium A second phosphor that is a nitride containing a phosphor and a third phosphor having an emission peak wavelength in a wavelength range of 500 nm or more and 560 nm or less, and the first phosphor and the second phosphor In the light emitting device, the content of the first phosphor with respect to the total content is 5% by mass or more and 95% by mass or less.

本開示によれば、優れた演色性と高い発光効率とを有する発光装置を提供することができる。   According to the present disclosure, a light emitting device having excellent color rendering properties and high light emission efficiency can be provided.

本実施形態に係る発光装置の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the light-emitting device which concerns on this embodiment. 本実施形態に係る発光装置の他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the light-emitting device which concerns on this embodiment. 本実施形態に係る蛍光体１、蛍光体２ａから２ｄの波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the fluorescent substance 1 which concerns on this embodiment, and fluorescent substance 2a-2d. 本実施形態に係る蛍光体３ａから３ｃ及び４ａから４ｃの波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of fluorescent substance 3a-3c and 4a-4c which concern on this embodiment. 実施例１から４、比較例１及び２に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Examples 1-4 and Comparative Examples 1 and 2. FIG. 比較例２から４に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Comparative Examples 2-4. 実施例５から１０、比較例５及び６に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Examples 5-10 and the comparative examples 5 and 6. FIG. 実施例１１及び比較例１に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Example 11 and Comparative Example 1. FIG. 実施例３、１２及び１３に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Example 3, 12, and 13. FIG. 実施例３、１４及び１５に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Example 3, 14, and 15. FIG. 実施例３、１６及び１７に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Example 3, 16, and 17. FIG. 実施例１８、１９及び比較例７に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Example 18, 19 and the comparative example 7. FIG. 実施例２０、２１及び比較例８に係る発光装置の波長に対する相対発光強度を示す発光スペクトルを例示する図である。It is a figure which illustrates the emission spectrum which shows the relative light emission intensity with respect to the wavelength of the light-emitting device which concerns on Examples 20, 21 and Comparative Example 8. FIG.

以下、本開示に係る発光装置を、実施の形態に基づいて説明する。ただし、以下に示す実施の形態は、本発明の技術思想を例示するものであって、本発明は以下のものに限定されない。なお、色名と色度座標との関係、光の波長範囲と単色光の色名との関係等は、ＪＩＳ Ｚ８１１０に従う。また組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
また蛍光体の平均粒径は、フィッシャー・サブ・シーブ・サイザーズ・ナンバー（Fisher Sub Sieve Sizer's No.）と呼ばれる数値であり、空気透過法を用いて測定される。
蛍光体の半値幅は、蛍光体の発光スペクトルにおいて、最大発光強度の５０％の発光強度を示す発光スペクトルの波長幅を意味する。 Hereinafter, a light-emitting device according to the present disclosure will be described based on embodiments. However, the embodiment described below exemplifies the technical idea of the present invention, and the present invention is not limited to the following. The relationship between the color name and the chromaticity coordinates, the relationship between the wavelength range of light and the color name of monochromatic light, and the like comply with JIS Z8110. Moreover, content of each component in a composition means the total amount of the said some substance which exists in a composition, unless there is particular notice, when the substance applicable to each component exists in a composition in multiple numbers.
The average particle size of the phosphor is a numerical value called a Fisher Sub Sieve Sizer's No., and is measured using an air permeation method.
The full width at half maximum of the phosphor means the wavelength width of the emission spectrum showing the emission intensity of 50% of the maximum emission intensity in the emission spectrum of the phosphor.

［発光装置］
本実施形態の発光装置は、４００ｎｍ以上４８０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子と、アルカリ土類金属、アルカリ金属、アルミニウム及びユーロピウムを含む窒化物である第一蛍光体と、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含む窒化物である第二蛍光体と、５００ｎｍ以上５６０ｎｍ以下の波長範囲に発光ピーク波長を有する第三蛍光体とを含む蛍光部材と、を備え、前記第一蛍光体及び第二蛍光体の総含有量に対する第一蛍光体の含有率が５質量％以上９５質量％以下である。 [Light emitting device]
The light emitting device of the present embodiment includes a light emitting element having an emission peak wavelength in a wavelength range of 400 nm or more and 480 nm or less, a first phosphor that is a nitride containing an alkaline earth metal, an alkali metal, aluminum, and europium, and an alkaline earth. A second phosphor that is a nitride containing a similar metal, aluminum, silicon, and europium, and a third phosphor that has an emission peak wavelength in a wavelength range of 500 nm or more and 560 nm or less. The content rate of the 1st fluorescent substance with respect to the total content of a fluorescent substance and a 2nd fluorescent substance is 5 to 95 mass%.

本実施形態の発光装置は、特定の発光ピーク波長を有する発光素子と、少なくとも２種類の互いに異なる組成を有する赤色発光の窒化物蛍光体と、緑色発光の蛍光体とを組み合わせることにより、発光スペクトルにおける赤色領域の発光成分を制御することができる。詳しくは、第二蛍光体と比べて発光ピーク波長が長く半値幅が狭い第一蛍光体により、発光装置の発光スペクトルにおいて視感度の低い長波成分を低減させる一方、第一蛍光体と比べて発光ピーク波長が短く半値幅が広い第二蛍光体により、発光装置の発光スペクトルにおける赤色領域の発光成分を広く補うことできる。このような第一蛍光体および第二蛍光体を有することにより、本実施形態の発光装置は、優れた演色性と高い発光効率とを達成することが可能となる。   The light emitting device according to the present embodiment combines an emission spectrum by combining a light emitting element having a specific emission peak wavelength, at least two types of red emitting nitride phosphors having different compositions and a green emitting phosphor. It is possible to control the light emission component in the red region. Specifically, the first phosphor having a long emission peak wavelength and a narrow half-value width compared to the second phosphor reduces long wave components having low visibility in the emission spectrum of the light emitting device, while emitting light compared to the first phosphor. The second phosphor having a short peak wavelength and a wide half-value width can widely supplement the light emission component in the red region in the emission spectrum of the light emitting device. By having such a first phosphor and a second phosphor, the light emitting device of this embodiment can achieve excellent color rendering properties and high luminous efficiency.

本実施形態の発光装置を例えば照明用器具に適用することで、演色性の高い照明用器具を提供することができる。演色性は照射物の色の見え方の指標として、平均演色評価数（Ｒａ）で表される。１９８６年にＣＩＥ（国際照明委員会）が、蛍光ランプ等が具備すべき演色性の指針を公表しており、その指針によれば、使用される場所に応じた好ましいＲａは、一般作業を行う工場では６０以上８０未満、住宅、ホテル、レストラン、店舗、オフィス、学校、病院、精密作業を行う工場などでは８０以上９０未満、臨床検査を行う場所、美術館などでは９０以上とされている。
また特殊演色評価数はＲ９〜Ｒ１５の評価数として表わされ、中でもＲ９は彩度の高い赤色の見え方の指針とされる。食肉などを扱う環境では、Ｒ９の評価数に着目されることが多く、評価数が高いほど好ましい。 By applying the light emitting device of this embodiment to, for example, a lighting fixture, a lighting fixture with high color rendering properties can be provided. The color rendering property is represented by an average color rendering index (Ra) as an index of how the irradiated object appears. In 1986, the CIE (International Commission on Illumination) published guidelines for color rendering properties that fluorescent lamps, etc. should have, and according to these guidelines, the preferred Ra for the place where it is used performs general work. The factories are 60 or more and less than 80, houses, hotels, restaurants, stores, offices, schools, hospitals, factories performing precision work, etc. are 80 or more and less than 90, and places where clinical examinations are performed, museums and the like are 90 or more.
The special color rendering index is expressed as R9 to R15, and R9 is used as a guideline for the appearance of red with high saturation. In an environment where meat or the like is handled, attention is often paid to the evaluation number of R9, and the higher the evaluation number, the better.

本実施形態の発光装置の平均演色評価数Ｒａは、例えば８０以上であり、８５以上が好ましく、９０以上がより好ましく、９５以上がさらに好ましい。なおＲａの上限は１００である。本実施形態の発光装置のＲ９は例えば、３０以上であり、３５以上が好ましく、５０以上がより好ましく、７５以上が特に好ましい。Ｒ９の上限は１００である。   The average color rendering index Ra of the light emitting device of this embodiment is, for example, 80 or more, preferably 85 or more, more preferably 90 or more, and further preferably 95 or more. The upper limit of Ra is 100. R9 of the light emitting device of the present embodiment is, for example, 30 or more, preferably 35 or more, more preferably 50 or more, and particularly preferably 75 or more. The upper limit of R9 is 100.

発光装置が発する光は、発光素子の光と、第一蛍光体、第二蛍光体及び第三蛍光体が発する蛍光との混合色であり、例えば、ＣＩＥ１９３１に規定される色度座標がｘ＝０．３３０から０．５００且つｙ＝０．３３０から０．４５０の範囲に含まれる光とすることができる。
発光装置が発する光の相関色温度は、例えば２７００Ｋ以上６５００Ｋ以下とすることができる。 The light emitted from the light emitting device is a mixed color of the light from the light emitting element and the fluorescence emitted from the first phosphor, the second phosphor, and the third phosphor. For example, the chromaticity coordinates defined in CIE 1931 are x = The light can be included in the range of 0.330 to 0.500 and y = 0.330 to 0.450.
The correlated color temperature of light emitted from the light emitting device can be set to, for example, 2700K or more and 6500K or less.

発光装置の形式は特に制限されず、通常用いられる形式から適宜選択することができる。発光装置の形式としては、ピン貫通型、表面実装型等を挙げることができる。一般にピン貫通型とは、実装基板に設けられたスルーホールに発光装置のリード（ピン）を貫通させて発光装置を固定するものを指す。また表面実装型とは、実装基板の表面において発光装置のリードを固定するものを指す。   The form of the light emitting device is not particularly limited, and can be appropriately selected from commonly used forms. Examples of the light emitting device include a pin penetration type and a surface mounting type. In general, the pin through type refers to a type in which a light emitting device is fixed by penetrating leads (pins) of the light emitting device through through holes provided in a mounting substrate. The surface mount type refers to a type in which the lead of the light emitting device is fixed on the surface of the mounting substrate.

本発明の一実施形態に係る発光装置１００を図面に基づいて説明する。図１は、発光装置１００を示す概略断面図である。発光装置１００は、表面実装型発光装置の一例である。
発光装置１００は、可視光の短波長側（例えば、３８０ｎｍ以上４８５ｎｍ以下の範囲）の光を発し、発光ピーク波長が４３０ｎｍ以上４７０ｎｍ以下の範囲内にある窒化ガリウム系化合物半導体の発光素子１０と、発光素子１０を載置する成形体４０と、を有する。成形体４０は、第１のリード２０及び第２のリード３０と、樹脂部４２とが一体的に成形されてなるものである。あるいは樹脂部４２に代えてセラミックスを材料として既に知られた方法を利用して成形体４０を形成することもできる。成形体４０は底面と側面を持つ凹部を形成しており、凹部の底面に発光素子１０が載置されている。発光素子１０は一対の正負の電極を有しており、その一対の正負の電極はそれぞれ第１のリード２０及び第２のリード３０とワイヤ６０を介して電気的に接続されている。発光素子１０は蛍光部材５０により被覆されている。蛍光部材５０は例えば、発光素子１０からの光を波長変換する蛍光体７０として第一蛍光体７１、第二蛍光体７２及び第三蛍光体７３と樹脂とを含有してなる。 A light emitting device 100 according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing the light emitting device 100. The light emitting device 100 is an example of a surface mount type light emitting device.
The light emitting device 100 emits light on the short wavelength side of visible light (for example, a range of 380 nm to 485 nm), and the light emitting device 10 of a gallium nitride compound semiconductor having an emission peak wavelength in a range of 430 nm to 470 nm, And a molded body 40 on which the light emitting element 10 is placed. The molded body 40 is formed by integrally molding the first lead 20 and the second lead 30 and the resin portion 42. Or it replaces with the resin part 42 and the molded object 40 can also be formed using the method already known by using ceramics as a material. The molded body 40 has a recess having a bottom surface and side surfaces, and the light emitting element 10 is placed on the bottom surface of the recess. The light emitting element 10 has a pair of positive and negative electrodes, and the pair of positive and negative electrodes are electrically connected to the first lead 20 and the second lead 30 through wires 60, respectively. The light emitting element 10 is covered with a fluorescent member 50. The fluorescent member 50 includes, for example, a first fluorescent body 71, a second fluorescent body 72, a third fluorescent body 73, and a resin as a fluorescent body 70 that converts the wavelength of light from the light emitting element 10.

蛍光部材５０は、蛍光体７０を含む波長変換部材としてだけではなく、発光素子１０及び蛍光体７０を外部環境から保護するための部材としても機能する。図１では、蛍光体７０は蛍光部材５０中で偏在している。このように発光素子１０に接近して蛍光体７０を配置することにより、発光素子１０からの光を効率よく波長変換することができ、発光効率の優れた発光装置が構成できる。なお、蛍光体７０を含む蛍光部材５０と、発光素子１０との配置は、それらを接近して配置させる形態に限定されることなく、蛍光体７０への熱の影響を考慮して、蛍光部材５０中で発光素子１０と、蛍光体７０との間隔を空けて配置することもできる。また、蛍光体７０を蛍光部材５０の全体にほぼ均一の割合で混合することによって、色ムラがより抑制された光を得るようにすることもできる。   The fluorescent member 50 functions not only as a wavelength conversion member including the phosphor 70 but also as a member for protecting the light emitting element 10 and the phosphor 70 from the external environment. In FIG. 1, the phosphor 70 is unevenly distributed in the fluorescent member 50. Thus, by arranging the phosphor 70 close to the light emitting element 10, the wavelength of light from the light emitting element 10 can be efficiently converted, and a light emitting device having excellent light emission efficiency can be configured. The arrangement of the fluorescent member 50 including the phosphor 70 and the light emitting element 10 is not limited to the form in which they are arranged close to each other, and the fluorescent member is considered in consideration of the influence of heat on the phosphor 70. 50, the light emitting element 10 and the phosphor 70 may be spaced apart. In addition, by mixing the phosphor 70 with the entire fluorescent member 50 at a substantially uniform ratio, it is possible to obtain light in which color unevenness is further suppressed.

図１では、蛍光体７０である第一蛍光体７１、第二蛍光体７２及び第三蛍光体７３が混合された状態で図示されているが、図２に示すようにそれぞれの蛍光体を配置してもよい。
図２は、本実施形態に係る発光装置の別の一例を示す概略断面図である。図２では、発光素子１０に近い方から順に、第一蛍光体７１、第二蛍光体７２及び第三蛍光体７３が配置されている。これにより、第三蛍光体７３の発光が第一蛍光体７１及び第二蛍光体７２を励起させてしまうことを抑制することができる。また、第三蛍光体７３を最も上に配置することにより、第三蛍光体７３の発光を発光装置の外へ取り出し易くすることができる。
図２では第一蛍光体７１、第二蛍光体７２及び第三蛍光体７３がそれぞれ配置されているが、第一蛍光体７１及び第二蛍光体７２が混合されて配置され、その上に第三蛍光体が配置されていてもよい。 In FIG. 1, the first phosphor 71, the second phosphor 72, and the third phosphor 73, which are the phosphors 70, are illustrated in a mixed state, but the respective phosphors are arranged as shown in FIG. 2. May be.
FIG. 2 is a schematic cross-sectional view showing another example of the light emitting device according to the present embodiment. In FIG. 2, a first phosphor 71, a second phosphor 72, and a third phosphor 73 are arranged in order from the side closer to the light emitting element 10. Thereby, it can suppress that light emission of the 3rd fluorescent substance 73 excites the 1st fluorescent substance 71 and the 2nd fluorescent substance 72. FIG. Further, by placing the third phosphor 73 on the top, it is possible to easily extract the light emitted from the third phosphor 73 out of the light emitting device.
In FIG. 2, the first phosphor 71, the second phosphor 72, and the third phosphor 73 are disposed, respectively, but the first phosphor 71 and the second phosphor 72 are mixed and disposed on the first phosphor 71, the second phosphor 72, and the third phosphor 73. Three phosphors may be arranged.

（発光素子）
発光素子の発光ピーク波長は、４３０ｎｍ以上４７０ｎｍ以下の範囲にあり、発光効率の観点から、４４５ｎｍ以上４５５ｎｍ以下の範囲にあることが好ましい。この範囲に発光ピーク波長を有する発光素子を励起光源として用いることにより、発光素子からの光と蛍光体からの蛍光との混色光を発する発光装置を構成することが可能となる。さらに、発光素子から外部に放射される光を有効に利用することができるため、発光装置から出射される光の損失を少なくすることができ、高効率な発光装置を得ることができる。 (Light emitting element)
The light emission peak wavelength of the light emitting element is in the range of 430 nm to 470 nm, and from the viewpoint of light emission efficiency, it is preferably in the range of 445 nm to 455 nm. By using a light emitting element having an emission peak wavelength in this range as an excitation light source, it is possible to configure a light emitting device that emits mixed light of light from the light emitting element and fluorescence from the phosphor. Furthermore, since light emitted from the light emitting element to the outside can be used effectively, loss of light emitted from the light emitting device can be reduced, and a highly efficient light emitting device can be obtained.

発光素子の発光スペクトルの半値幅は、例えば３０ｎｍ以下とすることができる。
発光素子にはＬＥＤなどの半導体発光素子を用いることが好ましい。光源として半導体発光素子を用いることによって、高効率で入力に対する出力のリニアリティが高く、機械的衝撃にも強い安定した発光装置を得ることができる。
半導体発光素子としては、例えば、窒化物系半導体（ＩｎＸＡｌＹＧａ１−Ｘ−ＹＮ、ここでＸ及びＹは、０≦Ｘ、０≦Ｙ、Ｘ＋Ｙ≦１を満たす）を用いた青色、緑色等に発光する半導体発光素子を用いることができる。 The half width of the emission spectrum of the light emitting element can be set to 30 nm or less, for example.
It is preferable to use a semiconductor light emitting element such as an LED as the light emitting element. By using a semiconductor light emitting element as a light source, it is possible to obtain a stable light emitting device with high efficiency, high output linearity with respect to input, and strong against mechanical shock.
As a semiconductor light emitting element, for example, a blue color using a nitride semiconductor (In X Al Y Ga 1- XYN, where X and Y satisfy 0 ≦ X, 0 ≦ Y, and X + Y ≦ 1). A semiconductor light emitting element that emits green light or the like can be used.

（蛍光部材）
蛍光部材は、発光素子から発せられる光を吸収し、赤色に発光する第一蛍光体の少なくとも１種と、赤色に発光する第二蛍光体の少なくとも１種と、緑色に発光する第三蛍光体の少なくとも１種とを含み、第一蛍光体及び第二蛍光体の総含有量に対する第一蛍光体の含有率が５質量％以上９５質量％以下である。第一蛍光体及び第二蛍光体は互いに異なる組成を有している。第一蛍光体、第二蛍光体及び第三蛍光体（以下、併せて単に「蛍光体」ともいう。）の構成比率を適宜選択することで発光装置の発光効率、演色性等の特性を所望の範囲とすることができる。蛍光部材は、例えば、蛍光体と樹脂とを含むことができる。 (Fluorescent material)
The fluorescent member absorbs light emitted from the light emitting element, and at least one first phosphor that emits red light, at least one second phosphor that emits red light, and a third phosphor that emits green light And the content of the first phosphor with respect to the total content of the first phosphor and the second phosphor is 5 mass% or more and 95 mass% or less. The first phosphor and the second phosphor have different compositions. Desirable characteristics such as luminous efficiency and color rendering properties of the light emitting device by appropriately selecting the composition ratio of the first phosphor, the second phosphor and the third phosphor (hereinafter, also simply referred to as “phosphor”). Range. The fluorescent member can include, for example, a phosphor and a resin.

第一蛍光体
蛍光部材は、アルカリ土類金属、アルカリ金属、アルミニウム及びユーロピウムを含む窒化物を含む第一蛍光体の少なくとも１種を含む。第一蛍光体は、例えば、下記式（Ｉ）で表される組成を有する。
Ｍａ ｘＭｂ ｙＡｌ３Ｎｚ：Ｅｕ （Ｉ）
式中、Ｍａは、Ｃａ、Ｓｒ及びＢａからなる群から選択される少なくとも１種の元素であり、Ｓｒ及びＣａの少なくとも一方を含むことが好ましく、少なくともＳｒを含むことがより好ましい。ＭａがＣａ及びＳｒの少なくとも一方を含む場合、Ｍａに含まれるＣａ及びＳｒの総モル比率は、例えば８５モル％以上であり、９０モル％以上が好ましい。 1st fluorescent substance The fluorescent member contains at least 1 sort (s) of 1st fluorescent substance containing the nitride containing an alkaline-earth metal, an alkali metal, aluminum, and europium. The first phosphor has, for example, a composition represented by the following formula (I).
M a x M b y Al 3 N z : Eu (I)
In the formula, M a is at least one element selected from the group consisting of Ca, Sr and Ba, preferably including at least one of Sr and Ca, and more preferably including at least Sr. If M a contains at least one of Ca and Sr, the total molar ratio of Ca and Sr contained in the M a is, for example, 85 mol% or more, preferably at least 90 mol%.

Ｍｂは、Ｌｉ、Ｎａ及びＫからなる群から選択される少なくとも１種の元素であり、少なくともＬｉを含むことが好ましい。ＭｂがＬｉを含む場合、Ｍｂに含まれるＬｉのモル比率は、例えば８０モル％以上であり、９０モル％以上が好ましい。 Mb is at least one element selected from the group consisting of Li, Na, and K, and preferably contains at least Li. If M b contains Li, the molar ratio of Li contained in the M b is, for example, 80 mol% or more, preferably at least 90 mol%.

ｘは、０．５≦ｘ≦１．５を満たし、好ましくは０．６≦ｘ≦１．２を満たし、より好ましくは０．８≦ｘ≦１．１を満たす。ｙは、０．５≦ｙ≦１．２を満たし、好ましくは０．６≦ｙ≦１．１を満たし、より好ましくは０．６≦ｙ≦１．０５を満たす。ｚは、３．５≦ｚ≦４．５を満たし、好ましくは３．６≦ｚ≦４．４を満たす。
Ｅｕの組成比は、アルミニウムの組成比３を基準にすると、発光効率の点で、例えば０．００２以上０．０２０以下であり、０．００５以上０．０１５以下が好ましい。
なお、第一蛍光体中に含まれる不純物として、原料や大気中からと考えられる酸素の含有量が２．５重量％以下であることが好ましく、後述するフラックスとしてフッ素を含む化合物をフラックスとして加えた場合、フッ素の含有量が１．０重量％以下であることが好ましい。 x satisfies 0.5 ≦ x ≦ 1.5, preferably satisfies 0.6 ≦ x ≦ 1.2, and more preferably satisfies 0.8 ≦ x ≦ 1.1. y satisfies 0.5 ≦ y ≦ 1.2, preferably satisfies 0.6 ≦ y ≦ 1.1, and more preferably satisfies 0.6 ≦ y ≦ 1.05. z satisfies 3.5 ≦ z ≦ 4.5, and preferably satisfies 3.6 ≦ z ≦ 4.4.
The composition ratio of Eu is, for example, 0.002 or more and 0.020 or less, and preferably 0.005 or more and 0.015 or less in terms of luminous efficiency, based on aluminum composition ratio 3.
As impurities contained in the first phosphor, the content of oxygen considered to be from the raw material or the atmosphere is preferably 2.5% by weight or less, and a fluorine-containing compound is added as a flux to be described later. In this case, the fluorine content is preferably 1.0% by weight or less.

第一蛍光体の発光スペクトルにおける半値幅は例えば、７０ｎｍ以下であり、６５ｎｍ以下が好ましく、６０ｎｍ以下がより好ましく、５５ｎｍ以下が更に好ましい。また半値幅は例えば４０ｎｍ以上であり、４５ｎｍ以上が好ましく、５０ｎｍ以上がより好ましい。
第一蛍光体は、極大励起波長を例えば４００ｎｍ以上５７０ｎｍ以下の波長範囲に有し、４２０ｎｍ以上４６０ｎｍ以下の波長範囲に有することが好ましい。第一蛍光体は、発光ピーク波長を例えば６３０ｎｍ以上６７０ｎｍ以下の波長範囲に有し、６４０ｎｍ以上６６０ｎｍ以下の波長範囲に有することが好ましい。 The half width in the emission spectrum of the first phosphor is, for example, 70 nm or less, preferably 65 nm or less, more preferably 60 nm or less, and further preferably 55 nm or less. The half width is, for example, 40 nm or more, preferably 45 nm or more, and more preferably 50 nm or more.
The first phosphor preferably has a maximum excitation wavelength in a wavelength range of 400 nm to 570 nm, for example, and a wavelength range of 420 nm to 460 nm. The first phosphor has an emission peak wavelength in a wavelength range of, for example, 630 nm to 670 nm, and preferably in a wavelength range of 640 nm to 660 nm.

第一蛍光体では、希土類であるユウロピウム（Ｅｕ）が発光中心となる。ただし第一蛍光体における発光中心は、ユーロピウムのみに限定されず、その一部を他の希土類金属やアルカリ土類金属に置き換えて、Ｅｕと共賦活させたものも使用できる。２価希土類イオンであるＥｕ２＋は適当な母体を選べば安定に存在し、発光する効果を奏する。 In the first phosphor, the rare earth europium (Eu) is the emission center. However, the emission center in the first phosphor is not limited to europium, and a part of which is partially activated by other rare earth metals or alkaline earth metals and co-activated with Eu can be used. Eu 2+, which is a divalent rare earth ion, exists stably if an appropriate matrix is selected, and has the effect of emitting light.

第一蛍光体の平均粒径は、発光効率の観点から、例えば２μｍ以上３０μｍ以下であり、３μｍ以上２５μｍ以下が好ましい。
平均粒径は大きいほうが、励起光の吸収率及び発光効率がより高くなる傾向がある。このように、光学特性に優れた第一蛍光体を後述する発光装置に含有させることにより、発光装置の発光効率がより向上する。
また第一蛍光体は、上記の平均粒径値を有する蛍光体粒子が、頻度高く含有されていることが好ましい。すなわち、粒度分布は狭い範囲に分布していることが好ましい。粒度分布のバラツキが小さい蛍光体を用いることにより、より色ムラが抑制され、より良好な色調を有する発光装置が得られる。 The average particle diameter of the first phosphor is, for example, 2 μm or more and 30 μm or less, and preferably 3 μm or more and 25 μm or less from the viewpoint of light emission efficiency.
The larger the average particle size, the higher the absorption rate and emission efficiency of excitation light tend to be higher. Thus, the luminous efficiency of a light-emitting device improves more by making the light-emitting device mentioned later contain the 1st fluorescent substance excellent in the optical characteristic.
Moreover, it is preferable that the first phosphor contains the phosphor particles having the above average particle diameter value with high frequency. That is, the particle size distribution is preferably distributed in a narrow range. By using a phosphor having a small variation in particle size distribution, color unevenness is further suppressed, and a light emitting device having a better color tone can be obtained.

蛍光部材中の第一蛍光体の含有量は、例えば樹脂１００質量部に対して０．１質量部以上３０質量部以下であり、０．５質量部以上２５質量部以下が好ましい。   Content of the 1st fluorescent substance in a fluorescent member is 0.1 to 30 mass parts with respect to 100 mass parts of resin, for example, and 0.5 to 25 mass parts is preferable.

第二蛍光体
蛍光部材は、アルカリ土類金属、アルミニウム、ケイ素及びユーロピウムを含む窒化物である第二蛍光体の少なくとも１種を含む。第二蛍光体は、例えば、下記式（II）で表される組成を有する。
ＳｒｓＣａｔＡｌｕＳｉｖＮｗ：Ｅｕ （II）
ｓ、ｔ、ｕ、ｖ及びｗはそれぞれ、０．０≦ｓ＜１．０、０．０＜ｔ≦１．０、ｓ＋ｔ≦１．０、０．９≦ｕ≦１．１、０．９≦ｖ≦１．１、２．５≦ｗ≦３．５を満たす。
Ｅｕの組成比は、ＳｒとＣａの組成比の和（ｓ＋ｔ＝１．０）を基準にすると、発光効率の点で、例えば０．００２以上０．０４以下であり、０．００４以上０．０３以下が好ましい。
なお、第二蛍光体中に含まれる不純物として、原料や大気中からと考えられる酸素の含有量が１．５重量％以下であることが好ましく、後述するフラックスとしてフッ素を含む化合物をフラックスとして加えた場合、フッ素の含有量が０．５重量％以下であることが好ましい。 Second phosphor The phosphor member includes at least one second phosphor that is a nitride containing an alkaline earth metal, aluminum, silicon, and europium. The second phosphor has, for example, a composition represented by the following formula (II).
Sr s Ca t Al u Si v N w: Eu (II)
s, t, u, v and w are 0.0 ≦ s <1.0, 0.0 <t ≦ 1.0, s + t ≦ 1.0, 0.9 ≦ u ≦ 1.1, 0, respectively. It satisfies 9 ≦ v ≦ 1.1 and 2.5 ≦ w ≦ 3.5.
The composition ratio of Eu is, for example, 0.002 or more and 0.04 or less, and 0.004 or more and 0.004 or less in terms of luminous efficiency, based on the sum of the composition ratios of Sr and Ca (s + t = 1.0). 03 or less is preferable.
As impurities contained in the second phosphor, the content of oxygen considered to be from the raw material or the atmosphere is preferably 1.5% by weight or less, and a fluorine-containing compound is added as a flux to be described later. In this case, the fluorine content is preferably 0.5% by weight or less.

第二蛍光体の発光スペクトルにおける半値幅は例えば、７０ｎｍ以上であり、７５ｎｍ以上が好ましい。また半値幅は例えば１００ｎｍ以下であり、９５ｎｍ以下が好ましく、８５ｎｍ以下がより好ましい。
第二蛍光体は、４００ｎｍ以上４８０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子からの光による励起され易さを考慮して、その励起スペクトルが、少なくとも４００ｎｍ以上４８０ｎｍ以下の波長範囲にある程度の強度を有することが好ましい。第二蛍光体は、発光ピーク波長を例えば６００ｎｍ以上６５５ｎｍ以下の波長範囲に有し、６０５ｎｍ以上６５０ｎｍ以下の波長範囲に有することが好ましい。 The half width in the emission spectrum of the second phosphor is, for example, 70 nm or more, and preferably 75 nm or more. The half width is, for example, 100 nm or less, preferably 95 nm or less, and more preferably 85 nm or less.
In consideration of the ease with which the second phosphor is excited by light from a light emitting element having an emission peak wavelength in the wavelength range of 400 nm to 480 nm, the excitation spectrum has a certain degree of excitation spectrum in the wavelength range of at least 400 nm to 480 nm. It is preferable to have strength. The second phosphor has an emission peak wavelength in the wavelength range of 600 nm to 655 nm, for example, and preferably in the wavelength range of 605 nm to 650 nm.

第一蛍光体の半値幅は、第二蛍光体の半値幅よりも狭いことが好ましい。これにより赤色領域における発光スペクトルを所望の態様に容易に調整することができる。第二蛍光体に対する第一蛍光体の半値幅の比（第一蛍光体／第二蛍光体）は、例えば０．５以上０．９以下であり、０．６以上０．８以下が好ましい。また第二蛍光体と第一蛍光体の半値幅の差は、例えば１５ｎｍ以上５０ｎｍ以下であり、２０ｎｍ以上４５ｎｍ以下が好ましい。   The half width of the first phosphor is preferably narrower than the half width of the second phosphor. Thereby, the emission spectrum in the red region can be easily adjusted to a desired mode. The ratio of the half width of the first phosphor to the second phosphor (first phosphor / second phosphor) is, for example, 0.5 or more and 0.9 or less, and preferably 0.6 or more and 0.8 or less. Moreover, the difference of the half value width of a 2nd fluorescent substance and a 1st fluorescent substance is 15 nm or more and 50 nm or less, for example, and 20 nm or more and 45 nm or less are preferable.

第一蛍光体の発光ピーク波長は、第二蛍光体の発光ピーク波長以上であることが好ましく、第二蛍光体の発光ピーク波長よりも長い方がより好ましい。第一蛍光体の発光ピーク波長が第二蛍光体の発光ピーク波長以上であり、半値幅が第一蛍光体の方が第二蛍光体よりも短いことで、赤色領域における発光スペクトルを所望の態様に、より容易に調整することができる。第一蛍光体と第二蛍光体の発光ピーク波長に差がある場合、その差は０ｎｍよりも大きければよく、例えば５５ｎｍ以下であり、４５ｎｍ以下が好ましい。   The emission peak wavelength of the first phosphor is preferably not less than the emission peak wavelength of the second phosphor, and more preferably longer than the emission peak wavelength of the second phosphor. The emission peak wavelength of the first phosphor is equal to or greater than the emission peak wavelength of the second phosphor, and the half-value width of the first phosphor is shorter than that of the second phosphor. In addition, it can be adjusted more easily. When there is a difference between the emission peak wavelengths of the first phosphor and the second phosphor, the difference should be larger than 0 nm, for example, 55 nm or less, preferably 45 nm or less.

第二蛍光体の平均粒径は、発光効率の観点から、例えば２μｍ以上３０μｍ以下であり、３μｍ以上２５μｍ以下が好ましい。   The average particle diameter of the second phosphor is, for example, 2 μm or more and 30 μm or less, and preferably 3 μm or more and 25 μm or less from the viewpoint of light emission efficiency.

蛍光部材中の第二蛍光体の含有量は、例えば樹脂１００質量部に対して０．１質量部以上２５質量部以下であり、０．５質量部以上２０質量部以下が好ましい。   Content of the 2nd fluorescent substance in a fluorescent member is 0.1 to 25 mass parts with respect to 100 mass parts of resin, for example, and 0.5 to 20 mass parts is preferable.

蛍光部材中の第一蛍光体及び第二蛍光体の総含有量に対する第一蛍光体の含有率は、５質量％以上９５質量％以下である。第一蛍光体の含有率を所定値以上とすることで演色性がより向上する傾向がある。一方、第一蛍光体の含有率を所定値以下とすることで発光効率がより向上する傾向がある。そのため、優れた演色性と高い発光効率とを達成する点で、蛍光部材中の第一蛍光体及び第二蛍光体の総含有量に対する第一蛍光体の含有率は、３０質量％以上９０質量％以下が好ましく、４０質量％以上７０質量％以下がより好ましい。   The content rate of the 1st fluorescent substance with respect to the total content of the 1st fluorescent substance and the 2nd fluorescent substance in a fluorescent member is 5 to 95 mass%. There exists a tendency for color rendering property to improve more by making content rate of a 1st fluorescent substance more than predetermined value. On the other hand, the light emission efficiency tends to be further improved by setting the content of the first phosphor to a predetermined value or less. Therefore, the content ratio of the first phosphor with respect to the total content of the first phosphor and the second phosphor in the phosphor member is 30% by mass to 90% by mass in terms of achieving excellent color rendering properties and high luminous efficiency. % Or less is preferable, and 40 mass% or more and 70 mass% or less are more preferable.

第三蛍光体
蛍光部材は、５００ｎｍ以上５６０ｎｍ以下の波長範囲に発光ピーク波長を有する第三蛍光体の少なくとも１種を含む。第一蛍光体及び第二蛍光体に加えて第三蛍光体を含むことで所望の発色光を得ることができる。 Third phosphor The fluorescent member includes at least one third phosphor having an emission peak wavelength in a wavelength range of 500 nm or more and 560 nm or less. By including the third phosphor in addition to the first phosphor and the second phosphor, a desired colored light can be obtained.

第三蛍光体の発光スペクトルにおける半値幅は例えば、９０ｎｍ以上であり、９５ｎｍ以上が好ましい。また半値幅は例えば１２５ｎｍ以下であり、１２０ｎｍ以下が好ましい。第三蛍光体の半値幅が所定の範囲であることで、より優れた演色性を達成することができる。
第三蛍光体は、発光ピーク波長を５００ｎｍ以上５６０ｎｍ以下の波長範囲に有するが、５０５ｎｍ以上５５５ｎｍ以下の波長範囲に有することが好ましい。第三蛍光体は、極大励起波長を例えば４２０ｎｍ以上４８０ｎｍ以下の波長範囲に有し、４３０ｎｍ以上４７０ｎｍ以下の波長範囲に有することが好ましい。 The half width in the emission spectrum of the third phosphor is, for example, 90 nm or more, and preferably 95 nm or more. Moreover, a half value width is 125 nm or less, for example, and 120 nm or less is preferable. When the half width of the third phosphor is within a predetermined range, more excellent color rendering can be achieved.
The third phosphor has an emission peak wavelength in a wavelength range of 500 nm to 560 nm, preferably in a wavelength range of 505 nm to 555 nm. The third phosphor preferably has a maximum excitation wavelength in a wavelength range of 420 nm to 480 nm, for example, in a wavelength range of 430 nm to 470 nm.

第三蛍光体として具体的には、下記式（IIIａ）又は（IIIｂ）で表される組成を有する蛍光体を１種以上含むことが好ましい。
Ｌｎ３Ａｌ５−ｐＧａｐＯ１２：Ｃｅ （IIIａ）
式中、ＬｎはＹ、Ｌｕ、Ｇｄ及びＴｂからなる群から選択される少なくとも１種の元素であり、０．０≦ｐ≦３．０を満たす。
Ｌａ３−ｑＹｑＳｉ６Ｎ１１：Ｃｅ （IIIｂ）
０．０≦ｑ≦１．５を満たす。 Specifically, the third phosphor preferably contains at least one phosphor having a composition represented by the following formula (IIIa) or (IIIb).
Ln 3 Al 5-p Ga p O 12: Ce (IIIa)
In the formula, Ln is at least one element selected from the group consisting of Y, Lu, Gd, and Tb, and satisfies 0.0 ≦ p ≦ 3.0.
La 3-q Y q Si 6 N 11: Ce (IIIb)
Satisfies 0.0 ≦ q ≦ 1.5.

式（IIIａ）又は（IIIｂ）で表される組成を有する蛍光体におけるＣｅ賦活量は特に制限されず、目的に応じて選択できる。Ｃｅ賦活量は、例えば式（IIIａ）ではＬｎの３に対して０．００１以上０．３以下であり、式（IIIｂ）ではＳｉの６に対して０．０１以上１．０以下である。   The Ce activation amount in the phosphor having the composition represented by the formula (IIIa) or (IIIb) is not particularly limited and can be selected according to the purpose. The Ce activation amount is, for example, 0.001 or more and 0.3 or less with respect to 3 of Ln in the formula (IIIa), and 0.01 or more and 1.0 or less with respect to 6 of Si in the formula (IIIb).

蛍光部材に含まれる第三蛍光体の平均粒径が所定値以上であると蛍光体の光吸収がより多くなり、発光効率がより向上する傾向がある。一方、平均粒径が所定値以下であると、発光装置を製造したとき、発光装置間の色度のばらつきをより抑制できる傾向がある。そのため、第三蛍光体の平均粒径は、例えば、２μｍ以上３５μｍ以下であり、３μｍ以上３０μｍ以下が好ましい。   If the average particle size of the third phosphor contained in the fluorescent member is greater than or equal to a predetermined value, the phosphor absorbs more light and the luminous efficiency tends to be further improved. On the other hand, when the average particle size is less than or equal to a predetermined value, when the light emitting device is manufactured, there is a tendency that variation in chromaticity between the light emitting devices can be further suppressed. Therefore, the average particle diameter of the third phosphor is, for example, 2 μm or more and 35 μm or less, and preferably 3 μm or more and 30 μm or less.

蛍光部材における第三蛍光体の含有量は、例えば、樹脂１００質量部に対して１０質量部以上２００質量部以下であり、２０質量部以上１８０質量部以下が好ましい。   Content of the 3rd fluorescent substance in a fluorescent member is 10 mass parts or more and 200 mass parts or less with respect to 100 mass parts of resin, for example, and 20 mass parts or more and 180 mass parts or less are preferable.

蛍光部材における第一蛍光体及び第二蛍光体の総含有量に対する第三蛍光体の含有量の質量比率は、目的の色温度への調整のし易さを考慮して、例えば５０％以上２０００％以下であり、１００％以上１７００％以下が好ましい。また蛍光部材に含まれる蛍光体が一蛍光体、第二蛍光体及び第三蛍光体からなる場合、第一蛍光体及び第二蛍光体の総含有量に対する第三蛍光体の含有量の質量比率は、目的の色温度への調整のし易さを考慮して、例えば３００％以上１８００％以下であり、４００％以上１７００％以下が好ましい。更に発光装置の色温度、蛍光体の比重等に応じて第三蛍光体の質量比率は様々に変化し得る。例えば、色温度が高い領域では第三蛍光体の比率が高くすることができ、逆に色温度が低い領域では第三蛍光体の比率は低くすることができる。   The mass ratio of the content of the third phosphor to the total content of the first phosphor and the second phosphor in the fluorescent member is, for example, 50% or more and 2000 in consideration of ease of adjustment to the target color temperature. % Or less, preferably 100% or more and 1700% or less. Further, when the phosphor contained in the fluorescent member is composed of one phosphor, the second phosphor and the third phosphor, the mass ratio of the content of the third phosphor to the total content of the first phosphor and the second phosphor Considering easiness of adjustment to the target color temperature, for example, it is 300% or more and 1800% or less, and preferably 400% or more and 1700% or less. Furthermore, the mass ratio of the third phosphor can be variously changed according to the color temperature of the light emitting device, the specific gravity of the phosphor, and the like. For example, the ratio of the third phosphor can be increased in a region where the color temperature is high, and conversely, the ratio of the third phosphor can be decreased in a region where the color temperature is low.

また例えば蛍光体の比重が大きい場合は、蛍光体の体積比率が減るために重量比が多くなる傾向になる。例えば色温度を４０００Ｋ、蛍光体の比重を５．５ｇ／ｃｍ３を境目とした場合、色温度が４０００Ｋより大きく、比重が５．５ｇ／ｃｍ３以上の場合、第三蛍光体比率は、例えば１０００％以上１８００％以下であり、１１００％以上１７００％以下が好ましい。また色温度が４０００Ｋより大きく、比重が５．５ｇ／ｃｍ３未満の場合、第三蛍光体比率は、例えば１０００％以上１７００％以下であり、１１００％以上１６００％以下が好ましい。また色温度が４０００Ｋ以下で比重が５．５ｇ／ｃｍ３以上の場合、第三蛍光体比率は、例えば５００％以上１３００％以下であり、６００％以上１２００％以下が好ましい。また色温度が４０００Ｋ以下で比重が５．５ｇ／ｃｍ３未満の場合、第三蛍光体比率は、例えば３００％以上１２００％以下であり、４００％以上１１００％以下が好ましい。 Further, for example, when the specific gravity of the phosphor is large, the weight ratio tends to increase because the volume ratio of the phosphor decreases. For example, when the color temperature is 4000 K and the specific gravity of the phosphor is 5.5 g / cm 3 , when the color temperature is greater than 4000 K and the specific gravity is 5.5 g / cm 3 or more, the third phosphor ratio is, for example, It is 1000% or more and 1800% or less, and preferably 1100% or more and 1700% or less. When the color temperature is greater than 4000 K and the specific gravity is less than 5.5 g / cm 3 , the third phosphor ratio is, for example, 1000% to 1700%, and preferably 1100% to 1600%. When the color temperature is 4000 K or less and the specific gravity is 5.5 g / cm 3 or more, the third phosphor ratio is, for example, 500% or more and 1300% or less, and preferably 600% or more and 1200% or less. When the color temperature is 4000 K or less and the specific gravity is less than 5.5 g / cm 3 , the third phosphor ratio is, for example, 300% or more and 1200% or less, and preferably 400% or more and 1100% or less.

第四蛍光体
蛍光部材は、４８５ｎｍ以上５４０ｎｍ以下の波長範囲に発光ピーク波長を有する第四蛍光体の少なくとも１種を含んでいてもよい。このような第四蛍光体を更に含むことで、発光装置の発光スペクトルにおいて第三蛍光体だけでは不足し得る特定の発光成分を第四蛍光体による発光成分で補うことができ、より優れた演色性を有する発光装置とすることができる。 Fourth phosphor The fluorescent member may include at least one fourth phosphor having an emission peak wavelength in a wavelength range of 485 nm or more and 540 nm or less. By further including such a fourth phosphor, it is possible to supplement a specific light emitting component that can be insufficient with only the third phosphor in the emission spectrum of the light emitting device with the light emitting component by the fourth phosphor, and to achieve a better color rendering The light emitting device can be made to have the property.

第四蛍光体は、発光ピーク波長を４８０ｎｍ以上５４０ｎｍ以下の波長範囲に有するが、４８５ｎｍ以上５３０ｎｍ以下の波長範囲に有することが好ましい。
第四蛍光体の発光スペクトルにおける半値幅は、例えば、８０ｎｍ以下であり、７５ｎｍ以下が好ましい。また半値幅は例えば４０ｎｍ以上であり、５０ｎｍ以上が好ましい。第四蛍光体の半値幅が所定値以上であると、発光装置の発光スペクトルが、ある特定の発光成分に偏ることを抑制できる傾向がある。一方、第四蛍光体の半値幅が所定値以下であると、比較的半値幅が広い第三蛍光体の発光スペクトルとの重なりを抑制できる傾向がある。このように第三蛍光体の発光スペクトルを考慮して第四蛍光体の発光特性を調節することで、発光装置の演色性と発光効率とをより向上することができる。
第四蛍光体は、４００ｎｍ以上４８０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子からの光による励起され易さを考慮して、その励起スペクトルが、少なくとも４００ｎｍ以上４８０ｎｍ以下の波長範囲にある程度の強度を有することが好ましい。 The fourth phosphor has an emission peak wavelength in the wavelength range of 480 nm to 540 nm, preferably in the wavelength range of 485 nm to 530 nm.
The half width in the emission spectrum of the fourth phosphor is, for example, 80 nm or less, and preferably 75 nm or less. Moreover, a half value width is 40 nm or more, for example, and 50 nm or more is preferable. When the half width of the fourth phosphor is equal to or larger than a predetermined value, the emission spectrum of the light emitting device tends to be suppressed from being biased to a specific light emitting component. On the other hand, when the half width of the fourth phosphor is not more than a predetermined value, there is a tendency that the overlap with the emission spectrum of the third phosphor having a relatively wide half width can be suppressed. In this way, by adjusting the light emission characteristics of the fourth phosphor in consideration of the emission spectrum of the third phosphor, the color rendering properties and the light emission efficiency of the light emitting device can be further improved.
In consideration of the ease with which the fourth phosphor is excited by light from a light emitting element having an emission peak wavelength in the wavelength range of 400 nm to 480 nm, the excitation spectrum has a certain degree of excitation spectrum in the wavelength range of at least 400 nm to 480 nm. It is preferable to have strength.

第四蛍光体として具体的には、より優れた演色性を達成することができる点で、下記式（IVａ）、（IVｂ）又は（IVｃ）で表される組成を有する蛍光体を１種以上含むことが好ましい。
Ｍｃ ８ＭｇＳｉ４Ｏ１６Ｘ２：Ｅｕ （IVａ）
式中、Ｍｃは、Ｃａ、Ｓｒ及びＢａからなる群から選択される少なくとも１種の元素であり、Ｘは、Ｃｌ、Ｆ及びＢｒからなる群から選択される少なくとも１種の元素である。
Ｍｄ ４Ａｌ１４Ｏ２５：Ｅｕ （IVｂ）
式中、Ｍｄは、Ｃａ、Ｓｒ及びＢａからなる群から選択される少なくとも１種の元素である。
Ｍｅ ２ＳｉＯ４：Ｅｕ （IVｃ）
式中、ＭｅはＣａ、Ｓｒ、Ｂａ及びＭｇからなる群から選択される少なくとも１種の元素である。 Specifically, as the fourth phosphor, one or more phosphors having a composition represented by the following formula (IVa), (IVb) or (IVc) can be achieved in that more excellent color rendering can be achieved. It is preferable to include.
M c 8 MgSi 4 O 16 X 2: Eu (IVa)
Wherein, M c is, Ca, at least one element selected from the group consisting of Sr and Ba, X is at least one element selected from the group consisting of Cl, F and Br.
M d 4 Al 14 O 25 : Eu (IVb)
In the formula, M d is at least one element selected from the group consisting of Ca, Sr and Ba.
M e 2 SiO 4: Eu ( IVc)
Wherein, M e is at least one element selected from the group consisting of Ca, Sr, Ba and Mg.

式（IVａ）、（IVｂ）又は（IVｃ）で表される組成を有する蛍光体におけるＥｕ賦活量は、例えば式（IVａ）ではＭｃの８に対して０．０５以上１．０以下であり、式（IVｂ）ではＭｄの４に対して０．１以上１．０以下であり、式（IVｃ）ではＭｅの２に対して０．０１以上０．４以下である。 Formula (IVa), Eu-activated amount of phosphor having a composition represented by (IVb) or (IVc) is, for example, with respect to 8 of the M c the formula (IVa) be 0.05 to 1.0 , it is 4 0.1 to 1.0 with respect to formula (IVb) in M d, is 0.01 to 0.4 relative to 2 of the M e formula (IVc).

蛍光部材に含まれる第四蛍光体の平均粒径が所定値以上であると蛍光体への光吸収がより多くなり、発光効率がより向上する傾向がある。一方、平均粒径が所定値以下であると、発光装置を製造したとき、発光装置間の色度のばらつきをより抑制できる傾向がある。そのため、第四蛍光体の平均粒径は、例えば、２μｍ以上３５μｍ以下であり、３μｍ以上３０μｍ以下が好ましい。   If the average particle size of the fourth phosphor contained in the fluorescent member is greater than or equal to a predetermined value, the light absorption into the phosphor is increased, and the light emission efficiency tends to be further improved. On the other hand, when the average particle size is less than or equal to a predetermined value, when the light emitting device is manufactured, there is a tendency that variation in chromaticity between the light emitting devices can be further suppressed. Therefore, the average particle diameter of the fourth phosphor is, for example, 2 μm or more and 35 μm or less, and preferably 3 μm or more and 30 μm or less.

蛍光部材における第四蛍光体の含有量は、例えば、樹脂１００質量部に対して０．１質量部以上１００質量部以下であり、０．２質量部以上８０質量部以下が好ましい。含有量が前記範囲であるとより優れた演色性を達成することができる。   Content of the 4th fluorescent substance in a fluorescent member is 0.1 to 100 mass parts with respect to 100 mass parts of resin, for example, and 0.2 to 80 mass parts is preferable. When the content is within the above range, more excellent color rendering can be achieved.

蛍光部材における第三蛍光体の総含有量に対する第四蛍光体の含有量の質量比率は、例えば１質量％以上２００質量％以下であり、５質量％以上１８０質量％以下が好ましい。含有量が前記範囲であるとより優れた演色性を達成することができる。また例えば、第三蛍光体が式（IIIａ）で表される組成を有し、第四蛍光体が式（IVａ）で表される組成を有する場合、第三蛍光体の総含有量に対する第四蛍光体の含有量の質量比率は、例えば１質量％以上２００質量％であり、５質量％以上１８０質量％以下が好ましい。また例えば、第三蛍光体が式（IIIａ）で表される組成を有し、第四蛍光体が式（IVｂ）で表される組成を有する場合、第三蛍光体の総含有量に対する第四蛍光体の含有量の質量比率は、例えば５質量％以上１６０質量％であり、１０質量％以上１４０質量％以下が好ましい。   The mass ratio of the content of the fourth phosphor to the total content of the third phosphor in the fluorescent member is, for example, 1% by mass to 200% by mass, and preferably 5% by mass to 180% by mass. When the content is within the above range, more excellent color rendering can be achieved. For example, when the third phosphor has a composition represented by the formula (IIIa) and the fourth phosphor has a composition represented by the formula (IVa), the fourth phosphor with respect to the total content of the third phosphor. The mass ratio of the phosphor content is, for example, 1% by mass to 200% by mass, and preferably 5% by mass to 180% by mass. For example, when the third phosphor has a composition represented by the formula (IIIa) and the fourth phosphor has a composition represented by the formula (IVb), the fourth phosphor with respect to the total content of the third phosphor. The mass ratio of the phosphor content is, for example, 5% by mass to 160% by mass, and preferably 10% by mass to 140% by mass.

その他の蛍光体
発光装置は、第一蛍光体、第二蛍光体、第三蛍光体及び第四蛍光体以外のその他の蛍光体を必要に応じて含んでいてもよい。その他の蛍光体としては、Ｃａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ、ＣａＳｃ２Ｏ４：Ｃｅ、（Ｂａ，Ｓｒ，Ｃａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ、Ｓｉ６−ｚＡｌｚＯｚＮ８−ｚ：Ｅｕ（０＜ｚ≦４．２）、（Ｃａ，Ｓｒ，Ｂａ）Ｇａ２Ｓ４：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）２Ｓｉ５Ｎ８：Ｅｕ、（Ｃａ，Ｓｒ，Ｂａ）Ｓ：Ｅｕ、Ｋ２（Ｓｉ，Ｔｉ，Ｇｅ）Ｆ６：Ｍｎ等を挙げることができる。発光装置がその他の蛍光体を含む場合、その含有量は、例えば蛍光体の総量中に１０質量％以下であり、１質量％以下が好ましい。 Other phosphors The light-emitting device may include other phosphors other than the first phosphor, the second phosphor, the third phosphor, and the fourth phosphor as necessary. Other phosphors include Ca 3 Sc 2 Si 3 O 12 : Ce, CaSc 2 O 4 : Ce, (Ba, Sr, Ca) Si 2 O 2 N 2 : Eu, (Ca, Sr, Ba) 3 Si 6 O 12 N 2: Eu, Si 6-z Al z O z N 8-z: Eu (0 <z ≦ 4.2), (Ca, Sr, Ba) Ga 2 S 4: Eu, (Ca, Sr , Ba) 2 Si 5 N 8 : Eu, (Ca, Sr, Ba) S: Eu, K 2 (Si, Ti, Ge) F 6 : Mn, and the like. When the light emitting device contains other phosphors, the content thereof is, for example, 10% by mass or less, and preferably 1% by mass or less in the total amount of the phosphors.

上記蛍光体の製造方法は、例えば、以下のようにして製造することができる。蛍光体の組成に含有される元素の単体や酸化物、炭酸塩、窒化物、塩化物、フッ化物、硫化物などを原料とし、これらの各原料を所定の組成比となるように秤量する。また、原料にさらにフラックスなどの添加材料を適宜加え、混合機を用いて湿式又は乾式で混合する。なお、フラックスを加える場合、フラックスは例えばフッ化バリウムのようなアルカリ土類金属のフッ化物が挙げられる。その含有量は、上述の第一蛍光体の場合、フッ素の量に換算して０．０１重量％以上１．５重量％以下とすることが好ましい。上述の第二蛍光体の場合、フッ素の量に換算して１．５重量％以下とすることが好ましい。これにより、固相反応を促進させて均一な大きさの粒子を形成することが可能となる。   The manufacturing method of the said fluorescent substance can be manufactured as follows, for example. A single element or oxide, carbonate, nitride, chloride, fluoride, sulfide or the like contained in the phosphor composition is used as a raw material, and each of these raw materials is weighed so as to have a predetermined composition ratio. Further, an additive material such as a flux is appropriately added to the raw material, and mixed by a wet or dry method using a mixer. In addition, when adding a flux, the flux is an alkaline earth metal fluoride such as barium fluoride. In the case of the first phosphor described above, the content is preferably 0.01% by weight or more and 1.5% by weight or less in terms of the amount of fluorine. In the case of the above-mentioned second phosphor, it is preferably 1.5% by weight or less in terms of the amount of fluorine. Thereby, it becomes possible to promote solid-phase reaction and form particles of uniform size.

混合機は工業的に通常用いられているボールミルの他、振動ミル、ロールミル、ジェットミルなどの粉砕機を用いてもよい。粉砕機を用いて粉砕することで比表面積を大きくすることもできる。また、粉末の比表面積を一定範囲とするために、工業的に通常用いられている沈降槽、ハイドロサイクロン、遠心分離器などの湿式分離機、サイクロン、エアセパレータなどの乾式分級機を用いて分級することもできる。上記の混合した原料をＳｉＣ、石英、アルミナ、ＢＮ等の坩堝に詰め、アルゴン、窒素などの不活性雰囲気、水素を含む還元雰囲気、または大気中での酸化雰囲気にて焼成を行う。焼成は所定の温度及び時間で行う。焼成されたものを粉砕、分散、濾過等して目的の蛍光体粉末を得る。固液分離は濾過、吸引濾過、加圧濾過、遠心分離、デカンテーションなどの工業的に通常用いられる方法により行うことができる。乾燥は、真空乾燥機、熱風加熱乾燥機、コニカルドライヤー、ロータリーエバポレーターなどの工業的に通常用いられる装置により行うことができる。   The mixer may be a ball mill that is usually used in industry, or a crusher such as a vibration mill, a roll mill, or a jet mill. The specific surface area can be increased by pulverization using a pulverizer. In addition, in order to keep the specific surface area of the powder within a certain range, it is classified using a wet classifier such as a sedimentation tank, hydrocyclone, and centrifugal separator, and a dry classifier such as a cyclone and an air separator, which are usually used in industry. You can also The mixed raw materials are packed in a crucible made of SiC, quartz, alumina, BN, or the like, and fired in an inert atmosphere such as argon or nitrogen, a reducing atmosphere containing hydrogen, or an oxidizing atmosphere in the air. Firing is performed at a predetermined temperature and time. The fired product is pulverized, dispersed, filtered, etc. to obtain the desired phosphor powder. Solid-liquid separation can be performed by industrially used methods such as filtration, suction filtration, pressure filtration, centrifugation, and decantation. Drying can be performed by industrially used apparatuses such as a vacuum dryer, a hot-air heating dryer, a conical dryer, and a rotary evaporator.

その他の成分
蛍光部材は、蛍光体及び樹脂に加えてその他の成分を必要に応じて含んでいてもよい。その他の成分としては、シリカ、チタン酸バリウム、酸化チタン、酸化アルミニウム等のフィラー、光安定化剤、着色剤等を挙げることができる。蛍光部材がその他の成分、例えばフィラーを含む場合、その含有量は樹脂１００質量部に対して、０．０１質量部以上２０質量部以下とすることができる。 Other components The fluorescent member may contain other components as needed in addition to the phosphor and the resin. Examples of other components include fillers such as silica, barium titanate, titanium oxide, and aluminum oxide, light stabilizers, and colorants. When a fluorescent member contains another component, for example, a filler, the content can be 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of resin.

以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

発光装置の製造に先立ち、以下のように蛍光体を準備した。
第一蛍光体として、ＳｒＬｉＡｌ３Ｎ４：Ｅｕで表される組成を有する蛍光体１を準備した。第二蛍光体として、（Ｓｒ，Ｃａ）ＡｌＳｉＮ３：Ｅｕで表される組成を有する蛍光体２を準備した。第三蛍光体として、Ｙ３（Ａｌ,Ｇａ）５Ｏ１２：Ｃｅで表される組成を有する蛍光体３ａ及びＬｕ３Ａｌ５Ｏ１２：Ｃｅで表される組成を有する蛍光体３ｂを準備した。第四蛍光体として、Ｃａ８ＭｇＳｉ４Ｏ１６Ｃｌ２：Ｅｕで表される組成を有する蛍光体４ａ、Ｓｒ４Ａｌ１４Ｏ２５：Ｅｕで表される組成を有する蛍光体４ｂ及び（Ｓｒ,Ｂａ）２ＳｉＯ４：Ｅｕで表される組成を有する蛍光体４ｃを準備した。 Prior to manufacturing the light emitting device, a phosphor was prepared as follows.
A phosphor 1 having a composition represented by SrLiAl 3 N 4 : Eu was prepared as the first phosphor. As the second phosphor, phosphor 2 having a composition represented by (Sr, Ca) AlSiN 3 : Eu was prepared. As the third phosphor, a phosphor 3a having a composition represented by Y 3 (Al, Ga) 5 O 12 : Ce and a phosphor 3b having a composition represented by Lu 3 Al 5 O 12 : Ce were prepared. . A fourth phosphor, Ca 8 MgSi 4 O 16 C l2: phosphor 4a having a composition represented by Eu, Sr 4 Al 14 O 25 : phosphor having a composition represented by Eu 4b and (Sr, Ba ) 2 SiO 4: it was prepared phosphor 4c having a composition represented by Eu.

準備した各蛍光体の発光ピーク波長、半値幅（最大発光強度の５０％に相当する発光強度における波長幅を表す）を表１に示す。併せて、図３Ａ及び３Ｂに４６０ｎｍで励起した時の各蛍光体の最大発光強度を１００％とした場合の波長に対する相対発光強度である発光スペクトルを示す。なお、蛍光体４ｂの半値幅については、４６０ｎｍで励起した場合に短波側が励起光の影響を受けるために、４００ｎｍで励起した場合の半値幅を示す。
また第二蛍光体の半値幅に対する第一蛍光体（蛍光体１）の半値幅の比を、蛍光体２ａから２ｄの第二蛍光体について、それぞれ示す。 Table 1 shows the emission peak wavelength and the half width (representing the wavelength width at the emission intensity corresponding to 50% of the maximum emission intensity) of each of the prepared phosphors. In addition, FIGS. 3A and 3B show emission spectra as relative emission intensities with respect to wavelengths when the maximum emission intensity of each phosphor when excited at 460 nm is 100%. In addition, about the half value width of the fluorescent substance 4b, since the short wave side is influenced by excitation light when excited at 460 nm, the half value width when excited at 400 nm is shown.
The ratio of the half width of the first phosphor (phosphor 1) to the half width of the second phosphor is shown for the second phosphors 2a to 2d, respectively.

（実施例１〜４、比較例１、２）
発光装置の作製
発光波長４５４ｎｍの青色発光ＬＥＤ（発光素子）に、表２に示す第一蛍光体、第二蛍光体及び第三蛍光体を組み合わせて、以下のようにして発光装置を作製した。
発光装置が発する混色光の色度座標がｘ＝０．４５０、ｙ＝０．４００付近となるように配合した蛍光体をシリコーン樹脂に添加し、混合分散した後、更に脱泡することにより蛍光体含有樹脂組成物を得た。次にこの蛍光体含有樹脂組成物を発光素子の上に注入、充填し、さらに加熱することで樹脂組成物を硬化させた。このような工程により発光装置をそれぞれ作製した。 (Examples 1-4, Comparative Examples 1 and 2)
Production of Light Emitting Device A blue light emitting LED (light emitting element) having an emission wavelength of 454 nm was combined with the first phosphor, the second phosphor, and the third phosphor shown in Table 2 to produce a light emitting device as follows.
A phosphor blended so that the chromaticity coordinates of the mixed-color light emitted from the light-emitting device are in the vicinity of x = 0.450 and y = 0.400 is added to the silicone resin, mixed and dispersed, and then defoamed to obtain fluorescence. A body-containing resin composition was obtained. Next, the phosphor-containing resin composition was poured and filled on the light emitting element, and further heated to cure the resin composition. Each of the light emitting devices was manufactured through such a process.

図４に実施例１から４と比較例１、２の発光装置の発光スペクトルを示す。表２の「第一質量比率（％）」は第一蛍光体と第二蛍光体の総量に対する第一蛍光体の質量比率（％）を表す。色度座標ｘ、ｙが発光装置の色度を表す。Ｒａは平均演色評価数、Ｒ９は赤味の指標となる特殊演色評価数を表す。光束比は比較例１の光束を基準（１００．０）とした場合の相対光束を示す。   FIG. 4 shows emission spectra of the light emitting devices of Examples 1 to 4 and Comparative Examples 1 and 2. “First mass ratio (%)” in Table 2 represents the mass ratio (%) of the first phosphor to the total amount of the first phosphor and the second phosphor. The chromaticity coordinates x and y represent the chromaticity of the light emitting device. Ra represents an average color rendering index, and R9 represents a special color rendering index serving as a reddish index. The luminous flux ratio indicates the relative luminous flux when the luminous flux of Comparative Example 1 is used as a reference (100.0).


比較例１は第二蛍光体を加えずに第一蛍光体と第三蛍光体のみを組合せた場合であり、一方、比較例２は第一蛍光体を加えずに第二蛍光体と第三蛍光体のみを組合せた場合である。実施例１〜４は第一蛍光体の質量比率が、それぞれ９０％、７０％、５０％、３０％となるように配合した。
光束比は、第二蛍光体の比率が高まるほど、すなわち、第一蛍光体の比率が低くなるほど明るくなっている。これは第二蛍光体の発光ピーク波長のほうが第一蛍光体の発光ピーク波長よりも短波に位置するために、光束に影響を与える視感度が高くなるためと考えられる。Ｒａ及びＲ９については、波長の異なる蛍光体１と蛍光体２の組合せの場合、蛍光体１を用いた場合と蛍光体２を用いた場合の中間の値になるのが一般的である。しかしながら、実施例に示されるように一定の発光特性差を有する蛍光体を組み合わせることで、図４に示すように、各実施例で発光装置のスペクトルが変化していき、５５０ｎｍから７００ｎｍの赤色成分の形状が、例えば、６００ｎｍ付近の発光強度が、比較例２よりも実施例１、２及び３のほうが小さくなるため、Ｒａ及びＲ９を高めることができたと考えられる。 Comparative Example 1 is the case where only the first phosphor and the third phosphor are combined without adding the second phosphor, while Comparative Example 2 is the second phosphor and the third phosphor without adding the first phosphor. This is a case where only phosphors are combined. Examples 1 to 4 were blended so that the mass ratios of the first phosphor were 90%, 70%, 50%, and 30%, respectively.
The luminous flux ratio increases as the ratio of the second phosphor increases, that is, as the ratio of the first phosphor decreases. This is presumably because the luminous peak wavelength of the second phosphor is positioned at a shorter wavelength than the emission peak wavelength of the first phosphor, so that the visibility that affects the luminous flux is increased. As for Ra and R9, in the case of the combination of the phosphor 1 and the phosphor 2 having different wavelengths, the values are generally intermediate between the case where the phosphor 1 is used and the case where the phosphor 2 is used. However, by combining phosphors having a certain light emission characteristic difference as shown in the examples, the spectrum of the light emitting device changes in each example as shown in FIG. 4, and the red component from 550 nm to 700 nm. For example, since the emission intensity in the vicinity of 600 nm is smaller in Examples 1, 2, and 3 than in Comparative Example 2, Ra and R9 can be increased.

（比較例３、４）
発光装置の作製
第一蛍光体の代わりに発光ピーク波長が蛍光体１と同じ蛍光体２ｂを用いて、表３に示す蛍光体の組合せに変更した以外は実施例１と同様の方法で、発光装置を作製した。表３には比較例２のデータも併せて示す。また、表中の質量比率（％）は蛍光体２ａと蛍光体２ｂの総質量中の蛍光体２ｂの質量比（％）を示す。 (Comparative Examples 3 and 4)
Production of light-emitting device A phosphor 2b having the same emission peak wavelength as that of phosphor 1 was used in place of the first phosphor, and the light emission was performed in the same manner as in Example 1 except that the phosphor combinations shown in Table 3 were changed. A device was made. Table 3 also shows the data of Comparative Example 2. The mass ratio (%) in the table indicates the mass ratio (%) of the phosphor 2b in the total mass of the phosphor 2a and the phosphor 2b.

比較例２から４の発光装置の発光スペクトルを図５に示す。比較例３及び４は発光波長が異なる蛍光体２ａと蛍光体２ｂの組合せである。蛍光体２ｂに対する蛍光体２ａの半値幅の比は０．８５であり、半値幅比が０．８よりも大きい。これらの組合せのＲａ、Ｒ９は単に蛍光体比率により変化しているだけと考えられ、組合せによる演色性の向上は見られていない。これは図５の発光スペクトルに示すように蛍光体の配合比の変更により、発光スペクトルにおける５００ｎｍから６００ｎｍ付近の成分変化がほとんどないことからも分かる。また、単に６００ｎｍよりも長い長波側の成分が更に長波長側へ移動しているだけである。   The emission spectra of the light emitting devices of Comparative Examples 2 to 4 are shown in FIG. Comparative Examples 3 and 4 are combinations of phosphor 2a and phosphor 2b having different emission wavelengths. The ratio of the half width of the phosphor 2a to the phosphor 2b is 0.85, and the half width ratio is larger than 0.8. It is considered that Ra and R9 of these combinations merely change depending on the phosphor ratio, and no improvement in color rendering properties is observed by the combination. As can be seen from the emission spectrum of FIG. 5, there is almost no change in the component from 500 nm to 600 nm in the emission spectrum due to the change in the blending ratio of the phosphors. Further, the long wave side component longer than 600 nm is merely shifted to the long wavelength side.

（実施例５から１０、比較例５、６）
発光装置の作製
表４に示す第一蛍光体、第二蛍光体及び第三蛍光体の組合せに変更した以外は実施例１と同様の方法で、発光装置を作製した。表４の「第一質量比率（％）」は第一蛍光体と第二蛍光体の総量に対する第一蛍光体の質量比率（％）を表す。 (Examples 5 to 10, Comparative Examples 5 and 6)
Production of Light-Emitting Device A light-emitting device was produced in the same manner as in Example 1, except that the combination of the first phosphor, the second phosphor, and the third phosphor shown in Table 4 was changed. “First mass ratio (%)” in Table 4 represents the mass ratio (%) of the first phosphor to the total amount of the first phosphor and the second phosphor.

比較例５は第一蛍光体を加えずに第二蛍光体と第三蛍光体のみを組合せた場合であり、一方、比較例６は第二蛍光体を加えずに第一蛍光体と第三蛍光体のみを組合せた場合である。実施例５から１０では、第一蛍光体の質量比率がそれぞれ１０％２０％、３０％、４０％、５０％、７０％となるように配合した。
比較例５及び６は比較例１及び２よりもＲａ、Ｒ９が低い。一方、実施例９及び１０は、比較例１及び２よりもＲａ及びＲ９が高い。光束比は、第二蛍光体の比率が高まるほど、すなわち第一蛍光体の比率が低くなるほど高くなっている。図６に示すように、各実施例５から１０で発光装置の発光スペクトルが変化していき、５５０ｎｍから７００ｎｍの赤色成分の発光スペクトル形状が特徴的である。すなわち、例えば、６００ｎｍ付近の発光強度が、比較例５よりも実施例８のほうで小さくなるため、基準光に近づいてＲａ及びＲ９を高めることができたと考えられる。 Comparative Example 5 is a case where only the second phosphor and the third phosphor are combined without adding the first phosphor, while Comparative Example 6 is the first phosphor and the third phosphor without adding the second phosphor. This is a case where only phosphors are combined. In Examples 5 to 10, the first phosphors were blended so that the mass ratios were 10%, 20%, 30%, 40%, 50%, and 70%, respectively.
Comparative Examples 5 and 6 have lower Ra and R9 than Comparative Examples 1 and 2. On the other hand, Examples 9 and 10 have higher Ra and R9 than Comparative Examples 1 and 2. The luminous flux ratio increases as the ratio of the second phosphor increases, that is, as the ratio of the first phosphor decreases. As shown in FIG. 6, the emission spectrum of the light emitting device changes in each of Examples 5 to 10, and the emission spectrum shape of the red component from 550 nm to 700 nm is characteristic. That is, for example, since the emission intensity in the vicinity of 600 nm is smaller in Example 8 than in Comparative Example 5, it is considered that Ra and R9 can be increased by approaching the reference light.

（実施例１１）
表５に示す第一蛍光体、第二蛍光体及び第三蛍光体の組合せに変更した以外は実施例１と同様の方法で、発光装置を作製した。表５には比較例１のデータを併せて示す。表５の「第一質量比率（％）」は第一蛍光体と第二蛍光体の総量に対する第一蛍光体の質量比率（％）を表す。 (Example 11)
A light emitting device was produced in the same manner as in Example 1 except that the combination of the first phosphor, the second phosphor, and the third phosphor shown in Table 5 was changed. Table 5 also shows the data of Comparative Example 1. “First mass ratio (%)” in Table 5 represents the mass ratio (%) of the first phosphor to the total amount of the first phosphor and the second phosphor.

実施例１１及び比較例１の発光装置の発光スペクトルを図７に示す。第一蛍光体及び第二蛍光体を加えた実施例１１は、第二蛍光体を加えていない比較例１よりもＲａとＲ９が高い。第二蛍光体は、先に述べた実施例における蛍光体２ａよりも発光ピーク波長が長い蛍光体２ｂであり、同様に演色性を高める効果がある。このように第二蛍光体の発光ピーク波長を変更しても、第一蛍光体と第二蛍光体を組み合わせることで５００ｎｍ以上６３０ｎｍ以下の発光成分を調整することができ、これにより得られる発光スペクトルが基準光に近づくため演色性を高めることができたと考えられる。   The emission spectra of the light emitting devices of Example 11 and Comparative Example 1 are shown in FIG. In Example 11 in which the first phosphor and the second phosphor were added, Ra and R9 were higher than those in Comparative Example 1 in which the second phosphor was not added. The second phosphor is a phosphor 2b having an emission peak wavelength longer than that of the phosphor 2a in the above-described embodiment, and has the same effect of improving color rendering. Thus, even if the emission peak wavelength of the second phosphor is changed, the emission component of 500 nm to 630 nm can be adjusted by combining the first phosphor and the second phosphor, and the emission spectrum obtained thereby It is thought that the color rendering was able to be improved because of approaching the reference light.

（実施例１２から１７）
発光装置の作製
表６に示す第一蛍光体、第二蛍光体、第三蛍光体及び第四蛍光体の組合せに変更した以外は実施例１と同じ方法で、発光装置を作製した。第三蛍光体に対する第四蛍光体の質量比率（％）を「第四質量比率（％）」として表６に示す。表６の「第一質量比率（％）」は第一蛍光体と第二蛍光体の総量に対する第一蛍光体の質量比率（％）を表す。 (Examples 12 to 17)
Production of Light-Emitting Device A light-emitting device was produced in the same manner as in Example 1 except that the combination of the first phosphor, the second phosphor, the third phosphor, and the fourth phosphor shown in Table 6 was changed. Table 6 shows the mass ratio (%) of the fourth phosphor to the third phosphor as “fourth mass ratio (%)”. “First mass ratio (%)” in Table 6 represents the mass ratio (%) of the first phosphor to the total amount of the first phosphor and the second phosphor.


実施例１２から１７は、実施例３の蛍光体の組合せに第四蛍光体をそれぞれ加えたものである。第四蛍光体として、実施例１４及び１５は蛍光体４ａ、実施例１２及び１３は蛍光体４ｂ、実施例１６及び１７は蛍光体４ｃを用いている。なお、第三蛍光体に対する第四蛍光体の質量比率について、実施例１３が実施例１２の約２倍量であり、実施例１５が実施例１４の約２．５倍量であり、実施例１７が実施例１６の約２倍量となっている。
実施例１２から１７は実施例３よりも光束比がわずかに低下しているが、Ｒａ及びＲ９が高くなっており、高い演色性を有していることが分かる。これは例えば、蛍光体４ａ及び４ｂは蛍光体３ａよりも短波側に発光ピーク波長を有することから、図８Ａから図８Ｃに示す発光装置の発光スペクトルから分かるように、４９０ｎｍから５５０ｎｍ付近の発光成分を増やし、それに伴い、５５０ｎｍから６６０ｎｍの発光成分が減少した影響で、基準光に近づいたためと考えられる。 In Examples 12 to 17, the fourth phosphor is added to the combination of the phosphors of Example 3. As the fourth phosphor, Examples 14 and 15 use phosphor 4a, Examples 12 and 13 use phosphor 4b, and Examples 16 and 17 use phosphor 4c. In addition, about the mass ratio of the 4th fluorescent substance with respect to a 3rd fluorescent substance, Example 13 is about twice the amount of Example 12, Example 15 is about 2.5 times the amount of Example 14, Example 17 is about twice as much as Example 16.
In Examples 12 to 17, the luminous flux ratio is slightly lower than that in Example 3, but Ra and R9 are high, and it can be seen that the color rendering properties are high. This is because, for example, the phosphors 4a and 4b have a light emission peak wavelength on the short-wave side of the phosphor 3a, and therefore, as can be seen from the light emission spectra of the light emitting devices shown in FIGS. This is considered to be due to the fact that the reference light is approached due to the influence of the decrease in the light emission component from 550 nm to 660 nm.

（実施例１８から２１、比較例７、８）
表７に示す第一蛍光体、第二蛍光体及び第三蛍光体の組合せに変更した以外は実施例１と同じ方法で、実施例１８から２１、比較例７、８の発光装置を調製した。表７の「第一質量比（％）」は第一蛍光体と第二蛍光体の総量に対する第一蛍光体の質量比率（％）を表す。 (Examples 18 to 21, Comparative Examples 7 and 8)
Except having changed into the combination of the 1st fluorescent substance shown in Table 7, the 2nd fluorescent substance, and the 3rd fluorescent substance, it was the same method as Example 1, and the light-emitting device of Examples 18-21 and Comparative Examples 7 and 8 was prepared. . “First mass ratio (%)” in Table 7 represents the mass ratio (%) of the first phosphor to the total amount of the first phosphor and the second phosphor.

実施例１８から２１、比較例７、８の発光装置の発光スペクトルを図９Ａ及び９Ｂに示す。実施例１８から２１は第二蛍光体の発光ピーク波長が２０ｎｍ程度異なる蛍光体２ｃ、蛍光体２ｄを用いて、蛍光体１と蛍光体３ｂを組み合わせて発光装置を作製した。光束比の基準は、これらの実施例と同じ蛍光体３ｂを用いた比較例６を１００％としている。実施例１８、１９で用いた蛍光体２ｃは６１０ｎｍに発光ピーク波長を有する蛍光体であり、蛍光体２ａよりも発光ピーク波長が約１０ｎｍ短いものの、蛍光体１と組み合わせることにより、Ｒａ、Ｒ９を高くする効果が見られている。実施例２０、２１で用いた蛍光体２ｄは発光ピーク波長が６２９ｎｍであり、蛍光体２ａよりも波長の長いものの、これらも同じようにＲａ、Ｒ９が高くなっている。図９Ａ及び９Ｂの発光スペクトルを見ると、いずれの実施例も比較例よりも基準光に近いスペクトルを示すために演色性が高くなっていると考えられる。実施例１８、１９と実施例２０、２１を比較すると第二蛍光体に相当する５７０ｎｍから６３０ｎｍ付近の成分比が異なっている。より発光ピーク波長が短い蛍光体２ｃを使用する組合せが５８０〜６００ｎｍ付近の成分が多くなる傾向があり、第二蛍光体の発光ピーク波長が長いほうがＲａ、Ｒ９も光束も高く、より発光特性に優れる。   The emission spectra of the light emitting devices of Examples 18 to 21 and Comparative Examples 7 and 8 are shown in FIGS. 9A and 9B. In Examples 18 to 21, a phosphor 2c and a phosphor 2d having different emission peak wavelengths of the second phosphor by about 20 nm were used to produce a light emitting device by combining the phosphor 1 and the phosphor 3b. The standard of the luminous flux ratio is 100% in Comparative Example 6 using the same phosphor 3b as in these examples. The phosphor 2c used in Examples 18 and 19 is a phosphor having an emission peak wavelength at 610 nm. Although the emission peak wavelength is about 10 nm shorter than that of the phosphor 2a, Ra and R9 are combined by combining with the phosphor 1. The effect of increasing is seen. The phosphor 2d used in Examples 20 and 21 has an emission peak wavelength of 629 nm and a wavelength longer than that of the phosphor 2a, but Ra and R9 are similarly high. When the emission spectra of FIGS. 9A and 9B are viewed, it is considered that the color rendering properties are higher in any of the examples because the spectrum is closer to the reference light than in the comparative example. When Examples 18 and 19 are compared with Examples 20 and 21, the component ratios in the vicinity of 570 nm to 630 nm corresponding to the second phosphor are different. The combination using phosphor 2c having a shorter emission peak wavelength tends to have more components in the vicinity of 580 to 600 nm. The longer the emission peak wavelength of the second phosphor, the higher the light flux of Ra and R9, and the higher the emission characteristics. Excellent.

以上のように、本開示に係る発光装置によれば、半値幅の比が所定の範囲であり、発光ピーク波長が異なる赤色発光の第一蛍光体及び第二蛍光体と、黄色発光の第三蛍光体を組み合わせることによって、基準光に近い発光スペクトルを発現できる。そのため平均演色評価数等で評価される演色性を高めることができるだけでなく、発光効率の向上と両立することが可能となった。また発光装置は、上記蛍光体に緑色発光の第四蛍光体を組み合わせることにより、さらに演色性を高めることができた。   As described above, according to the light-emitting device according to the present disclosure, the first phosphor and the second phosphor that emit red light having a half-width ratio in a predetermined range and different emission peak wavelengths, and the third that emits yellow light. By combining the phosphors, an emission spectrum close to the reference light can be expressed. Therefore, it is possible not only to improve the color rendering properties evaluated by the average color rendering index, but also to improve the luminous efficiency. In addition, the light emitting device was able to further improve the color rendering by combining the above phosphor with a green-emitting fourth phosphor.

本開示の発光装置は、照明用光源、ＬＥＤディスプレイ、バックライト光源、信号機、照明式スイッチ、各種センサ及び各種インジケータ等に好適に利用できるので、産業上の利用価値は極めて高い。   Since the light emitting device of the present disclosure can be suitably used for an illumination light source, an LED display, a backlight light source, a traffic light, an illumination switch, various sensors, various indicators, and the like, the industrial utility value is extremely high.

１０：発光素子、５０：蛍光部材、７１：第一蛍光体、７２：第二蛍光体、７３：第三蛍光体、１００：発光装置   10: Light emitting element, 50: Fluorescent member, 71: First phosphor, 72: Second phosphor, 73: Third phosphor, 100: Light emitting device

Claims (14)

４００ｎｍ以上４８０ｎｍ以下の波長範囲に発光ピーク波長を有する発光素子と、
下記式（Ｉ）で表される組成を有し、６３０ｎｍ以上６７０ｎｍ以下の波長範囲に発光ピーク波長を有する第一蛍光体と、下記式（II）で表される組成を有し、６００ｎｍ以上６５５ｎｍ以下の波長範囲に発光ピーク波長を有する第二蛍光体と、５００ｎｍ以上５６０ｎｍ以下の波長範囲に発光ピーク波長を有する第三蛍光体とを含む蛍光部材と、
を備え、
前記第一蛍光体の含有率は、前記第一蛍光体及び前記第二蛍光体の総含有量に対して５質量％以上９５質量％以下であり、
前記第一蛍光体の発光ピーク波長は、前記第二蛍光体の発光ピーク波長以上であり、
前記第一蛍光体の発光スペクトルの半値幅は、４０ｎｍ以上７０ｎｍ以下であって、前記第二蛍光体の発光スペクトルの半値幅に対する比が０．５以上０．８以下である発光装置。
Ｍａ ｘＭｂ ｙＡｌ３Ｎｚ：Ｅｕ （Ｉ）
（式（Ｉ）中、Ｍａは、Ｃａ、Ｓｒ、Ｂａ及びＭｇからなる群から選択される少なくとも１種の元素であり、Ｍｂは、Ｌｉ、Ｎａ及びＫからなる群から選択される少なくとも１種の元素であり、ｘ、ｙ及びｚはそれぞれ、０．５≦ｘ≦１．５、０．５≦ｙ≦１．２及び３．５≦ｚ≦４．５を満たす。）
ＳｒｓＣａｔＡｌｕＳｉｖＮｗ：Ｅｕ （II）
（式（II）中、ｓ、ｔ、ｕ、ｖ及びｗは、それぞれ、０．０≦ｓ＜１．０、０．０＜ｔ≦１．０、ｓ＋ｔ≦１．０、０．９≦ｕ≦１．１、０．９≦ｖ≦１．１、２．５≦ｗ≦３．５を満たす。） A light emitting element having an emission peak wavelength in a wavelength range of 400 nm or more and 480 nm or less;
A first phosphor having a composition represented by the following formula (I) and having an emission peak wavelength in a wavelength range of 630 nm to 670 nm and a composition represented by the following formula (II), 600 nm to 655 nm A fluorescent member comprising: a second phosphor having an emission peak wavelength in the following wavelength range; and a third phosphor having an emission peak wavelength in a wavelength range of 500 nm to 560 nm;
With
The content of the first phosphor is 5% by mass to 95% by mass with respect to the total content of the first phosphor and the second phosphor,
The emission peak wavelength of the first phosphor is not less than the emission peak wavelength of the second phosphor,
The light emitting device , wherein a half width of an emission spectrum of the first phosphor is 40 nm or more and 70 nm or less, and a ratio to a half width of an emission spectrum of the second phosphor is 0.5 or more and 0.8 or less.
M a x M b y Al 3 N z : Eu (I)
(In formula (I), M a is at least one element selected from the group consisting of Ca, Sr, Ba and Mg, and M b is at least selected from the group consisting of Li, Na and K. (It is one kind of element, and x, y, and z satisfy 0.5 ≦ x ≦ 1.5, 0.5 ≦ y ≦ 1.2, and 3.5 ≦ z ≦ 4.5, respectively.)
Sr s Ca t Al u Si v N w: Eu (II)
(In the formula (II), s, t, u, v and w are 0.0 ≦ s <1.0, 0.0 <t ≦ 1.0, s + t ≦ 1.0, 0.9 ≦, respectively. u ≦ 1.1, 0.9 ≦ v ≦ 1.1, and 2.5 ≦ w ≦ 3.5 are satisfied.) 前記第一蛍光体の発光スペクトルの半値幅は、４０ｎｍ以上６０ｎｍ以下である請求項１に記載の発光装置。 2. The light emitting device according to claim 1, wherein a half width of an emission spectrum of the first phosphor is 40 nm or more and 60 nm or less. 前記第二蛍光体の発光スペクトルの半値幅は、７０ｎｍ以上１００ｎｍ以下である請求項１又は２に記載の発光装置。   3. The light emitting device according to claim 1, wherein a half width of an emission spectrum of the second phosphor is 70 nm or more and 100 nm or less. 前記式（Ｉ）において、ＭａがＣａ及びＳｒの少なくとも一方を含み、ＭｂがＬｉを含む請求項１から３のいずれか１項に記載の発光装置。 4. The light-emitting device according to claim 1, wherein in the formula (I), M a includes at least one of Ca and Sr, and M b includes Li. 前記式（Ｉ）において、ｘが０．７以上１．２以下である請求項１から４のいずれか１項に記載の発光装置。   5. The light emitting device according to claim 1, wherein in the formula (I), x is 0.7 or more and 1.2 or less. 前記蛍光部材は、樹脂を含み、前記第一蛍光体の含有量が、樹脂１００質量部に対して０．１質量部以上３０質量部以下である請求項１から５のいずれか１項に記載の発光装置。   The said fluorescent member contains resin, and content of said 1st fluorescent substance is 0.1 mass part or more and 30 mass parts or less with respect to 100 mass parts of resin. Light-emitting device. 前記第三蛍光体の含有率は、前記第一蛍光体及び前記第二蛍光体の総含有量に対して５０質量％以上２０００質量％以下である請求項１から６のいずれか１項に記載の発光装置。   The content rate of said 3rd fluorescent substance is 50 to 2000 mass% with respect to the total content of said 1st fluorescent substance and said 2nd fluorescent substance, The any one of Claim 1 to 6 Light-emitting device. 前記第一蛍光体の含有率は、前記第一蛍光体及び前記第二蛍光体の総含有量に対して４０質量％以上７０質量％以下である請求項１から７のいずれか１項に記載の発光装置。   The content rate of said 1st fluorescent substance is 40 to 70 mass% with respect to the total content of said 1st fluorescent substance and said 2nd fluorescent substance, The any one of Claim 1 to 7 Light-emitting device. 前記第三蛍光体の発光スペクトルの半値幅は、９０ｎｍ以上１２５ｎｍ以下である請求項１から８のいずれか１項に記載の発光装置。   9. The light emitting device according to claim 1, wherein a half width of an emission spectrum of the third phosphor is 90 nm or more and 125 nm or less. 前記第三蛍光体が、下記式（IIIａ）又は（IIIｂ）で表される組成を有する蛍光体を１種以上含む請求項１から９のいずれか１項に記載の発光装置。
Ｌｎ３Ａｌ５−ｐＧａｐＯ１２：Ｃｅ （IIIａ）
（式中、ＬｎはＹ、Ｌｕ、Ｇｄ及びＴｂからなる群から選択される少なくとも１種の元素であり、０．０≦ｐ≦３．０を満たす。）
Ｌａ３−ｑＹｑＳｉ６Ｎ１１：Ｃｅ （IIIｂ）
（０．０≦ｑ≦１．５を満たす。） The light emitting device according to any one of claims 1 to 9, wherein the third phosphor includes one or more phosphors having a composition represented by the following formula (IIIa) or (IIIb).
Ln 3 Al 5-p Ga p O 12: Ce (IIIa)
(In the formula, Ln is at least one element selected from the group consisting of Y, Lu, Gd and Tb, and satisfies 0.0 ≦ p ≦ 3.0.)
La 3-q Y q Si 6 N 11: Ce (IIIb)
(0.0 ≦ q ≦ 1.5 is satisfied.) 前記蛍光部材は、４８０ｎｍ以上５４０ｎｍ以下の波長範囲に発光ピーク波長を有する第四蛍光体を含む請求項１から１０のいずれか１項に記載の発光装置。   11. The light emitting device according to claim 1, wherein the fluorescent member includes a fourth phosphor having an emission peak wavelength in a wavelength range of 480 nm or more and 540 nm or less. 前記第四蛍光体の発光スペクトルの半値幅が、４０ｎｍ以上８０ｎｍ以下である請求項１１に記載の発光装置。   The light emitting device according to claim 11, wherein a half width of an emission spectrum of the fourth phosphor is 40 nm or more and 80 nm or less. 前記第四蛍光体が、下記式（IVａ）、（IVｂ）又は（IVｃ）で表される組成を有する蛍光体を１種以上含む請求項１１又は１２に記載の発光装置。
Ｍｃ ８ＭｇＳｉ４Ｏ１６Ｘ２：Ｅｕ （IVａ）
（式中、Ｍｃは、Ｃａ、Ｓｒ及びＢａからなる群から選択される少なくとも１種の元素であり、Ｘは、Ｃｌ、Ｆ及びＢｒからなる群から選択される少なくとも１種の元素である。）
Ｍｄ ４Ａｌ１４Ｏ２５：Ｅｕ （IVｂ）
（式中、Ｍｄは、Ｃａ、Ｓｒ及びＢａからなる群から選択される少なくとも１種の元素である。）
Ｍｅ ２ＳｉＯ４：Ｅｕ （IVｃ）
（式中、ＭｅはＣａ、Ｓｒ、Ｂａ及びＭｇからなる群から選択される少なくとも１種の元素である。） The light emitting device according to claim 11 or 12, wherein the fourth phosphor includes at least one phosphor having a composition represented by the following formula (IVa), (IVb), or (IVc).
M c 8 MgSi 4 O 16 X 2: Eu (IVa)
(Wherein, M c is, Ca, at least one element selected from the group consisting of Sr and Ba, X is at least one element selected from the group consisting of Cl, F and Br .)
M d 4 Al 14 O 25 : Eu (IVb)
(In the formula, M d is at least one element selected from the group consisting of Ca, Sr and Ba.)
M e 2 SiO 4: Eu ( IVc)
(Wherein, M e is at least one element selected from the group consisting of Ca, Sr, Ba and Mg.) 前記蛍光部材では、前記発光素子に近い方から順に、前記第一蛍光体、前記第二蛍光体及び前記第三蛍光体が配置されている請求項１から１０のいずれか１項に記載の発光装置。   The light emission according to any one of claims 1 to 10, wherein in the fluorescent member, the first phosphor, the second phosphor, and the third phosphor are arranged in order from the side closer to the light emitting element. apparatus.
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