JP2012056804A - β-SIALON AND LIGHT EMITTING DEVICE - Google Patents

β-SIALON AND LIGHT EMITTING DEVICE Download PDF

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JP2012056804A
JP2012056804A JP2010202513A JP2010202513A JP2012056804A JP 2012056804 A JP2012056804 A JP 2012056804A JP 2010202513 A JP2010202513 A JP 2010202513A JP 2010202513 A JP2010202513 A JP 2010202513A JP 2012056804 A JP2012056804 A JP 2012056804A
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sialon
light
chromaticity
light emitting
formula
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Suzuya Yamada
鈴弥 山田
Hideyuki Emoto
秀幸 江本
Hironori Nagasaki
浩徳 長崎
Tomohiro Nomiyama
智宏 野見山
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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Priority to PCT/JP2011/070445 priority patent/WO2012033157A1/en
Priority to TW100132517A priority patent/TWI458806B/en
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Abstract

PROBLEM TO BE SOLVED: To provide an Eu-activated β-sialon and a light emitting device achieving a high emission efficiency.SOLUTION: The Eu-containing β-sialon is represented by formula: SiAlON, and the relationship between the (a) axis lattice constant and the chromaticity x of CIE chromaticity is represented by formula (1): (a) axis lattice constant (Å)≤0.1075×chromaticity x+7.5742. The β-sialon preferably has an average particle diameter D50(μm)/BET diameter (μm) of <1.9, as calculated by the following formula (2): BET diameter (μm)=6/(3.22×BET value (m/g)) and formula (3): D50 (μm)/BET diameter (μm)<1.9.

Description

本発明は、青や紫外の発光ダイオードチップを用いた白色発光ダイオード等の発光装置に利用可能なβ型サイアロン及び発光装置に関する。   The present invention relates to a β-type sialon and a light emitting device that can be used for a light emitting device such as a white light emitting diode using a blue or ultraviolet light emitting diode chip.

β型サイアロンに関して、特許文献１乃至４が開示されている。特許文献１には、第一の加熱工程で生成したβ型サイアロンが記載され、第二の加熱工程を経て酸処理することにより、結晶性を向上させて高輝度の蛍光体を得る技術が記載されている。特許文献２乃至４には、ＬＥＤ、蛍光体ランプなどのβ型サイアロンを用いた発光装置が開示されている。   Patent documents 1 to 4 are disclosed regarding β-type sialon. Patent Document 1 describes β-sialon produced in the first heating step, and describes a technique for obtaining a high-luminance phosphor by improving the crystallinity by acid treatment through the second heating step. Has been. Patent Documents 2 to 4 disclose light-emitting devices using β-sialon such as LEDs and phosphor lamps.

国際公開第２００８／０６２７８１号パンフレットInternational Publication No. 2008/062781 Pamphlet 特開平５−１５２６０９号公報JP-A-5-152609 特開平７−９９３４５号公報JP-A-7-99345 特許第２９２７２７９号公報Japanese Patent No. 2927279

大久保和明、他著、「ＮＢＳ標準蛍光体の量子効率の測定」、照明学会誌、第８３巻、第２号、ｐｐ８７−９３、平成１１年Kazuaki Okubo, et al., “Measurement of Quantum Efficiency of NBS Standard Phosphor”, Journal of the Illuminating Society of Japan, Vol.83, No.2, pp87-93, 1999

従来のβ型サイアロンを用いた蛍光体は、短波長化や狭帯域化を行った場合、発光効率が著しく低くなり、発光特性の再現性が乏しかった。このため、従来のβ型サイアロンを用いた白色ＬＥＤ等の発光装置は十分な輝度を安定して得ることができなかった。   Conventional phosphors using β-sialon have a significantly low luminous efficiency and poor reproducibility of luminous characteristics when the wavelength is reduced or the band is narrowed. For this reason, a conventional light emitting device such as a white LED using β-sialon cannot stably obtain sufficient luminance.

本発明は、上記課題に鑑み、高発光効率を実現できるβ型サイアロン及びβ型サイアロンを用いた発光装置を提供することを目的とする。   In view of the above problems, an object of the present invention is to provide a β-sialon and a light-emitting device using the β-sialon that can realize high luminous efficiency.

本発明は、一般式：Ｓｉ６−ｚＡｌｚＯｚＮ８−ｚで示され、Ｅｕを含有するβ型サイアロンであって、ａ軸格子定数とＣＩＥ色度の色度ｘとの関係が、次の式１を満たす。
ａ軸格子定数（Å）≦０.１０７５×色度ｘ＋７.５７４２ （式１） The present invention is a β-type sialon represented by the general formula: Si 6−z Al z O z N 8−z and containing Eu, wherein the relationship between the a-axis lattice constant and the chromaticity x of CIE chromaticity is The following formula 1 is satisfied.
a-axis lattice constant (Å) ≦ 0.1075 × chromaticity x + 7.5742 (formula 1)

ａ軸格子定数は、β型サイアロンを銅のＫα線を用いた粉末Ｘ線回折測定（以下、ＸＲＤ測定という。）で測定されるものである。   The a-axis lattice constant is measured by powder X-ray diffraction measurement (hereinafter referred to as XRD measurement) of β-type sialon using copper Kα rays.

β型サイアロンは、β型サイアロンのＢＥＴ値から次の式２で計算されるＢＥＴ径とβ型サイアロンをレーザー回折散乱法にて測定した平均粒子径Ｄ５０との関係が、次の式３で表される範囲のものが好ましい。
ＢＥＴ径（μｍ）＝６÷（３．２２×ＢＥＴ値（ｍ２／ｇ）） （式２）
平均粒子径Ｄ５０（μｍ）／ＢＥＴ径（μｍ）＜１．９ （式３） In β-sialon, the relationship between the BET diameter calculated by the following equation 2 from the BET value of β-sialon and the average particle size D50 obtained by measuring the β-sialon by the laser diffraction scattering method is expressed by the following equation 3. Those within the range are preferred.
BET diameter (μm) = 6 ÷ (3.22 × BET value (m 2 / g)) (Formula 2)
Average particle diameter D50 (μm) / BET diameter (μm) <1.9 (Formula 3)

本発明に係る発光装置は、前記β型サイアロンと発光光源とを備えたものである。   A light-emitting device according to the present invention includes the β-sialon and a light-emitting light source.

本発明のβ型サイアロンは、紫外線から可視光の幅広い波長域で励起され、高効率で５２０ｎｍ以上５５０ｎｍ以下の範囲内を主波長として緑色発光するため、緑色の蛍光体として優れている。   The β-sialon of the present invention is excellent as a green phosphor because it is excited in a wide wavelength range from ultraviolet to visible light and emits green light with a high wavelength within a range of 520 nm or more and 550 nm or less with high efficiency.

本発明の発光装置は、前記β型サイアロンを蛍光体として用いるため、発光装置の高輝度化を実現できる。   Since the light emitting device of the present invention uses the β-sialon as a phosphor, the light emitting device can have high luminance.

本発明のβ型サイアロンの製造方法を説明するフロー図である。It is a flow figure explaining the manufacturing method of beta type sialon of the present invention. 本発明の第２の実施形態に係るβ型サイアロンを用いた発光装置の構造を模式的に示した断面図である。It is sectional drawing which showed typically the structure of the light-emitting device using the beta sialon concerning the 2nd Embodiment of this invention.

以下、本発明の実施の形態について図面を用いて詳細に説明する。
（β型サイアロン）
本発明の実施形態に係るβ型サイアロンは、一般式：Ｓｉ６−ＺＡｌＺＯＺＮ８−Ｚで示されるβ型サイアロンをホスト結晶に、発光中心としてＥｕ２＋が固溶されたものである。β型サイアロンは、一般式：Ｓｉ６−ｚＡｌｚＯｚＮ８−ｚ：Ｅｕ（０＜ｚ≦４．２）とも表記される。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(Β-sialon)
The β-type sialon according to the embodiment of the present invention is obtained by solid-dissolving Eu 2+ as a light emission center in a β-type sialon represented by the general formula: Si 6-Z Al Z O Z N 8-Z. is there. The β-type sialon is also expressed as a general formula: Si 6−z Al z O z N 8−z : Eu (0 <z ≦ 4.2).

本発明者等は、β型サイアロンにおける結晶構造及び粉体物性と発光効率の関係を調べた結果、次の式１乃至式３の関係を満たすβ型サイアロンが高い発光効率を示すことを見出した。
ａ軸格子定数（Å）≦０.１０７５×色度ｘ＋７.５７４２ （式１）
ＢＥＴ径（μｍ）＝６÷（３．２２×ＢＥＴ値（ｍ２／ｇ）） （式２）
Ｄ５０（μｍ）／ＢＥＴ径（μｍ）＜１．９ （式３）
ここで、ａ軸格子定数は、β型サイアロンのａ軸の格子定数である。ＢＥＴ値は、比表面積測定法の一つであるＢＥＴ法で求められるβ型サイアロンの比表面積である。Ｄ５０は、体積基準の積算分率における５０％粒径であり、本明細書では、平均粒子径Ｄ５０ともいう。 As a result of investigating the relationship between the crystal structure and powder physical properties of β-sialon and the luminous efficiency, the present inventors have found that β-sialon satisfying the relationship of the following formulas 1 to 3 exhibits high luminous efficiency. .
a-axis lattice constant (Å) ≦ 0.1075 × chromaticity x + 7.5742 (formula 1)
BET diameter (μm) = 6 ÷ (3.22 × BET value (m 2 / g)) (Formula 2)
D50 (μm) / BET diameter (μm) <1.9 (Formula 3)
Here, the a-axis lattice constant is the a-axis lattice constant of β-type sialon. The BET value is the specific surface area of β-sialon determined by the BET method which is one of the specific surface area measurement methods. D50 is a 50% particle size in the volume-based integrated fraction, and is also referred to as an average particle size D50 in this specification.

式１の関係を満たすβ型サイアロンは、電子トラップが減少又は消失して励起電子のエネルギーが有効的に緑色発光に変換され、その結果、発光効率が向上する。   In β-sialon satisfying the relationship of Equation 1, the number of electron traps is reduced or eliminated, and the energy of excited electrons is effectively converted into green light emission. As a result, the light emission efficiency is improved.

式２及び式３の関係を満たさずβ型サイアロンの平均粒子径Ｄ５０／ＢＥＴ径が１．９よりも大きい場合、粒子表面が平滑ではなく励起光がβ型サイアロン蛍光体粒子表面で散乱され、効果的に蛍光を発しないため発光効率が低いことが判明した。   When the average particle diameter D50 / BET diameter of β-type sialon is not larger than 1.9 without satisfying the relationship of Equation 2 and Equation 3, the particle surface is not smooth and the excitation light is scattered on the surface of the β-type sialon phosphor particle, It has been found that the luminous efficiency is low because it does not emit fluorescence effectively.

β型サイアロンにおけるＥｕ含有量は、０．１質量％以上３質量％以下が好ましい。この範囲外では発光強度が低くなる傾向がある。   The Eu content in β-sialon is preferably 0.1% by mass or more and 3% by mass or less. Outside this range, the emission intensity tends to be low.

（β型サイアロンの製造方法）
Ｅｕを含有するβ型サイアロンの製造方法を、図１のフロー図を用いて説明する。
図１に示すように、β型サイアロンの製造方法は、原料粉末を混合して原料混合粉末にする混合工程と、混合工程後の原料混合粉末を焼成してＥｕを固溶したβ型サイアロンを生成する焼成工程と、焼成工程後のβ型サイアロンにアニール処理を行うアニール工程と、アニール工程後のβ型サイアロンに酸処理を行う酸処理工程と、から構成されている。 (Method for producing β-sialon)
A method for producing β-sialon containing Eu will be described with reference to the flowchart of FIG.
As shown in FIG. 1, a β-sialon manufacturing method includes a mixing step in which raw material powders are mixed to form a raw material mixed powder, and a β-sialon in which Eu is solid-solved by firing the raw material mixed powder after the mixing step. It comprises a firing step to be generated, an annealing step for annealing the β-sialon after the firing step, and an acid treatment step for acid-treating the β-sialon after the annealing step.

原料粉末の配合組成に関しては、Ａｌ／Ｏモル比が１.３以下であれば加熱中の粒成長が進行し易く好ましい。Ａｌ／Ｏモル比が１.１以下であるとＢＥＴ径に平均粒子径Ｄ５０が近づくので好ましい。   As for the composition of the raw material powder, it is preferable that the Al / O molar ratio is 1.3 or less because the grain growth during heating is likely to proceed. An Al / O molar ratio of 1.1 or less is preferable because the average particle diameter D50 approaches the BET diameter.

図１には記載しなかったが、ＢＥＴ値及び平均粒子径Ｄ５０の制御のために、酸処理工程の後に、分級処理を実施するのが好ましい。   Although not shown in FIG. 1, in order to control the BET value and the average particle diameter D50, it is preferable to carry out a classification treatment after the acid treatment step.

アニール工程における加熱温度、処理時間、窒素分圧を調整することで、β型サイアロンの分解を押さえ、Ｓｉが発生することなく、前記式１乃至式３の関係を成り立たせる。   By adjusting the heating temperature, processing time, and nitrogen partial pressure in the annealing step, the decomposition of β-sialon is suppressed, and the relations of the expressions 1 to 3 are established without generation of Si.

平均粒子径Ｄ５０は、５μｍ以上３０μｍ以下が好ましく、さらに好ましくは１０μｍ以上２０μｍ以下である。平均粒子径Ｄ５０があまりに小さいと発光効率が低くなり、あまりに大きいと発光装置に用いた場合に分散状態が悪くなる傾向にある。   The average particle diameter D50 is preferably 5 μm or more and 30 μm or less, more preferably 10 μm or more and 20 μm or less. If the average particle diameter D50 is too small, the light emission efficiency is low, and if it is too large, the dispersion state tends to deteriorate when used in a light emitting device.

（発光装置）
本発明のβ型サイアロンを用いた発光装置について、図２を参照しつつ説明する。
発光装置は、発光光源と上述のβ型サイアロンを用いたものであり、図２は発光装置の断面を模式的に示したものである。
図２に示すように、本発明の発光装置１０は、発光光源１２としてのＬＥＤチップと、発光光源１２を搭載する第１のリードフレーム１３と、第２のリードフレーム１４と、発光光源１２と第１のリードフレーム１３とを被覆する波長変換部材１５と、発光光源１２と第２のリードフレーム１４を電気的につなぐボンディングワイヤ１６と、これらを覆う合成樹脂製のキャップ１９で形成されている。波長変換部材１５は、β型サイアロン１８と、β型サイアロン１８を分散しつつ配合した封止樹脂１７とからなる。第１のリードフレーム１３の上部１３ａにはＬＥＤチップ搭載用の凹部１３ｂが設けられている。凹部１３ｂは、その底面から上方に向かって孔径が徐々に拡大する略漏斗形状を有していると共に、凹部１３ｂの内面が反射面となっている。この反射面の底面にＬＥＤチップ１２の下面側の電極がダイボンディングされている。ＬＥＤチップ１２の上面に形成されている他方の電極は、ボンディングワイヤ１６を介して第２のリードフレーム１４の表面と接続されている。 (Light emitting device)
A light-emitting device using the β-sialon of the present invention will be described with reference to FIG.
The light-emitting device uses a light-emitting light source and the β-sialon described above, and FIG. 2 schematically shows a cross section of the light-emitting device.
As shown in FIG. 2, the light emitting device 10 of the present invention includes an LED chip as the light source 12, a first lead frame 13 on which the light source 12 is mounted, a second lead frame 14, and the light source 12. It is formed of a wavelength conversion member 15 that covers the first lead frame 13, a bonding wire 16 that electrically connects the light emitting light source 12 and the second lead frame 14, and a synthetic resin cap 19 that covers them. . The wavelength conversion member 15 includes a β-type sialon 18 and a sealing resin 17 in which the β-type sialon 18 is mixed and dispersed. The upper portion 13a of the first lead frame 13 is provided with a recess 13b for mounting an LED chip. The concave portion 13b has a substantially funnel shape in which the hole diameter gradually increases upward from the bottom surface, and the inner surface of the concave portion 13b is a reflecting surface. An electrode on the lower surface side of the LED chip 12 is die-bonded to the bottom surface of the reflecting surface. The other electrode formed on the upper surface of the LED chip 12 is connected to the surface of the second lead frame 14 via a bonding wire 16.

発光光源１２としては、各種ＬＥＤチップを用いることができ、特に好ましくは、近紫外から青色光の波長として３５０ｎｍ〜５００ｎｍの光を発生するＬＥＤチップである。これらの発光光源１２としては、ＧａＮやＩｎＧａＮなどの窒化物半導体からなるものがあり、組成を調整することにより所定の波長の光を発する発光光源１２となる。   Various LED chips can be used as the light source 12, and an LED chip that generates light having a wavelength of 350 nm to 500 nm as a wavelength of near ultraviolet to blue light is particularly preferable. These light emitting sources 12 include those made of nitride semiconductors such as GaN and InGaN. The light emitting light source 12 emits light having a predetermined wavelength by adjusting the composition.

発光装置１０の波長変換部材５に用いるβ型サイアロンには、他の色を発光する蛍光体を混在させることもできる。他の色を発光する蛍光体としては、α型サイアロン、ＣａＡｌＳｉＮ３、ＹＡＧがあり、これらに固溶される元素としては、ユーロピウム、セリウム、ストロンチウム、カルシウムがある。 The β-type sialon used for the wavelength conversion member 5 of the light emitting device 10 can be mixed with phosphors emitting other colors. Phosphors emitting other colors include α-type sialon, CaAlSiN 3 , and YAG, and elements dissolved in these include europium, cerium, strontium, and calcium.

本発明に係る発光装置１０は、発光光源１２とβ型サイアロン１８、その他の蛍光体とを組み合わせることによって、様々の波長の光、すなわち様々な色を発光させることができる。５２０ｎｍ以上５５０ｎｍ以下の範囲の波長にピークを持つ緑色を発光させる場合には、β型サイアロン１８単体と発光光源１２として３５０ｎｍ以上５００ｎｍ以下の波長を有する近紫外光や可視光を照射すれば良い。さらに波長６００ｎｍ以上７００ｎｍ以下の赤色発光蛍光体、青色発光蛍光体、黄色発光蛍光体又は橙発光蛍光体の単体又は混合体とを組み合わせることによって、白色光やいわゆる電球色などを、適宜発光させることができる。   The light emitting device 10 according to the present invention can emit light of various wavelengths, that is, various colors, by combining the light emitting light source 12, the β-type sialon 18 and other phosphors. In the case of emitting green light having a peak at a wavelength in the range of 520 nm to 550 nm, near ultraviolet light or visible light having a wavelength of 350 nm to 500 nm may be irradiated as the β-type sialon 18 alone and the light source 12. Further, white light or a so-called light bulb color is appropriately emitted by combining a single or mixture of a red light emitting phosphor, a blue light emitting phosphor, a yellow light emitting phosphor, or an orange light emitting phosphor having a wavelength of 600 nm to 700 nm. Can do.

本発明の発光装置１０は、β型サイアロン１８の発光強度が高いため、高い発光強度を有する。さらに、β型サイアロン１８の有する熱的にも化学的にも安定である特徴を反映して、本発明の発光装置１０は、高温で使用しても輝度低下が小さく、長寿命である。   The light emitting device 10 of the present invention has a high emission intensity because the β-sialon 18 has a high emission intensity. Further, reflecting the feature of the β-sialon 18 that is thermally and chemically stable, the light emitting device 10 of the present invention has a small luminance drop and a long life even when used at a high temperature.

以下、本発明の実施例についてさらに詳細に説明する。
＜混合工程＞
原料粉末として、α型窒化ケイ素粉末（宇部興産社製ＳＮ−Ｅ１０グレード、酸素含有量１．１７質量％、β相含有量４．５質量％）、窒化アルミニウム粉末（トクヤマ社製Ｆグレード、酸素含有量０．８４質量％）、酸化アルミニウム粉末（大明化学社製ＴＭ−ＤＡＲグレード）、酸化ユーロピウム粉末（信越化学工業社製ＲＵグレード）を用いた。原料粉末中のＡｌ量から計算したｚ値が０．２５、酸化ユーロピウム粉末以外の酸素量から計算したｚ値が０．２５、酸化ユーロピウム粉末を０．２９モル％となるように配合し、１ｋｇの原料混合物粉末を得た。この時Ａｌ／Ｏモル比は１．０であった。
次に、上記原料粉末をロッキングミキサー（愛知電機社製、ＲＭ−１０）を用いて６０分乾式で混合し、更に目開き１５０μｍのステンレス製篩を全通させ、蛍光体焼成用の原料混合粉末を得た。 Hereinafter, examples of the present invention will be described in more detail.
<Mixing process>
As raw material powder, α-type silicon nitride powder (SN-E10 grade made by Ube Industries, oxygen content 1.17 mass%, β phase content 4.5 mass%), aluminum nitride powder (F grade, oxygen produced by Tokuyama Corporation) Content 0.84% by mass), aluminum oxide powder (TM-DAR grade, manufactured by Daimei Chemical Co., Ltd.) and europium oxide powder (RU grade, manufactured by Shin-Etsu Chemical Co., Ltd.) were used. The z value calculated from the amount of Al in the raw material powder is 0.25, the z value calculated from the amount of oxygen other than the europium oxide powder is 0.25, and the europium oxide powder is blended so as to be 0.29 mol%. The raw material mixture powder was obtained. At this time, the Al / O molar ratio was 1.0.
Next, the above raw material powder is mixed for 60 minutes using a rocking mixer (manufactured by Aichi Electric Co., Ltd., RM-10), and is further passed through a stainless steel sieve having an opening of 150 μm. Got.

＜焼成工程＞
原料混合粉末を、容積０．７リットルの窒化ホウ素製容器（電気化学工業社製Ｎ−１グレード）に充填し、カーボンヒーターの電気炉にて、０．９ＭＰａの加圧窒素雰囲気中、２０００℃で１５時間の焼成を行った。得られた合成物は、緩く凝集した塊状であるので軽度の解砕を行った後、目開き１５０μｍの篩を通して粉末状のβ型サイアロンを得た。 <Baking process>
The raw material mixed powder is filled in a boron nitride container (N-1 grade manufactured by Denki Kagaku Kogyo Co., Ltd.) having a volume of 0.7 liter, and is 2,000 ° C. in a pressurized nitrogen atmosphere of 0.9 MPa in an electric furnace of a carbon heater. Then, baking was performed for 15 hours. Since the obtained composite was a loosely agglomerated lump, after mild crushing, powdery β-sialon was obtained through a sieve having an opening of 150 μm.

＜分級工程＞
得られたβ型サイアロンを音速ジェット粉砕機（日本ニューマチック工業社製ＰＪＭ−８０ＳＰ）で粒度の調整を行い、さらに水中分級処理によって５μｍ以下の微粉を除去した後、乾燥を行った。 <Classification process>
The obtained β-sialon was adjusted in particle size with a sonic jet pulverizer (PJM-80SP manufactured by Nippon Pneumatic Kogyo Co., Ltd.), and after removing fine particles of 5 μm or less by an underwater classification treatment, drying was performed.

＜アニール工程＞
分級工程を経たβ型サイアロンを円筒型窒化ホウ素製容器（電気化学工業社製Ｎ−１グレード）に充填し、カーボンヒーターの電気炉で大気圧のアルゴン雰囲気中、１４５０℃で８時間の加熱処理を行った。得られた粉末は、焼結に伴う収縮はなく、加熱前とほとんど同じ性状であり、目開き４５μｍの篩を全て通過した。篩を通過したβ型サイアロンに対し、ＸＲＤ測定によって結晶相の同定を行った。ＸＲＤ測定の結果、実施例１のβ型サイアロンは単相からなるという結果を得たが、微量のＳｉが検出された。 <Annealing process>
Β-sialon after the classification process is filled into a cylindrical boron nitride container (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.), and heated at 1450 ° C. for 8 hours in an argon atmosphere at atmospheric pressure in an electric furnace of a carbon heater. Went. The obtained powder did not shrink due to sintering, had almost the same properties as before heating, and passed through a sieve having an opening of 45 μm. The crystalline phase was identified by XRD measurement for β-sialon that passed through the sieve. As a result of XRD measurement, it was obtained that the β-sialon of Example 1 was composed of a single phase, but a trace amount of Si was detected.

＜酸処理工程＞
アニール工程を経たβ型サイアロンを、５０％フッ化水素酸と７０％硝酸の１：１混酸中に浸した後、水洗及び乾燥して実施例１のβ型サイアロンを得た。 <Acid treatment process>
The β-sialon after the annealing step was immersed in a 1: 1 mixed acid of 50% hydrofluoric acid and 70% nitric acid, then washed with water and dried to obtain the β-sialon of Example 1.

＜評価＞
実施例１のβ型サイアロンの評価について表１を参照しつつ詳細に説明する。

Figure 2012056804
<Evaluation>
The evaluation of the β-type sialon of Example 1 will be described in detail with reference to Table 1.
Figure 2012056804

実施例１のβ型サイアロンは、ＸＲＤ測定の結果、ａ軸格子定数は７．６１０３Å、ｃ軸格子定数は２．９１２１Åであり、β型サイアロン以外の結晶からのピークは検出されなかった。 As a result of XRD measurement, the β-type sialon of Example 1 had an a-axis lattice constant of 7.6103 Å and a c-axis lattice constant of 2.9121 、, and no peaks from crystals other than β-type sialon were detected.

実施例１のβ型サイアロンの蛍光スペクトルを、分光蛍光光度計（日立ハイテクノロジーズ社製、Ｆ４５００）を用いて測定した。４５５ｎｍの青色光を励起光として蛍光スペクトルのピーク波長の高さを測定した。同一条件で測定した化成オプト社製ＹＡＧ：Ｃｅ蛍光体（Ｐ４６−Ｙ３）のピーク波長の高さに対する相対値を発光ピーク強度として求めた。励起光には、分光したキセノンランプ光源を使用した。実施例１のβ型サイアロンの発光ピーク強度は２０１％であった。   The fluorescence spectrum of β-sialon of Example 1 was measured using a spectrofluorometer (manufactured by Hitachi High-Technologies Corporation, F4500). The height of the peak wavelength of the fluorescence spectrum was measured using 455 nm blue light as excitation light. The relative value with respect to the height of the peak wavelength of YAG: Ce phosphor (P46-Y3) manufactured by Kasei Opto Co., Ltd., measured under the same conditions, was determined as the emission peak intensity. A spectral xenon lamp light source was used as the excitation light. The emission peak intensity of the β-sialon of Example 1 was 201%.

実施例１のβ型サイアロンのＣＩＥ色度は、瞬間マルチ測光システム（大塚電子社製ＭＣＰＤ−７０００）にて積分球を用い、４５５ｎｍの励起に対する蛍光を集光した全光束の蛍光スペクトル測定を行って求めた。測定方法は、非特許文献１に準じて行った。実施例１のβ型サイアロンのＣＩＥ色度は、色度ｘ＝０．３５３、色度ｙ＝０．６２５であった。   The CIE chromaticity of the β-type sialon of Example 1 was measured using the instantaneous sphere photometry system (MCPD-7000, manufactured by Otsuka Electronics Co., Ltd.) using an integrating sphere to measure the fluorescence spectrum of the total luminous flux that focused the fluorescence for excitation at 455 nm. Asked. The measurement method was performed according to Non-Patent Document 1. The CIE chromaticity of the β-sialon of Example 1 was chromaticity x = 0.353 and chromaticity y = 0.625.

色度ｘ＝０．３５３から、式１式の右辺は７．６１２１であった。実施例１のβ型サイアロンのａ軸格子定数は、７．６１０３であり、次に示すように、式１の関係を満たしていた。
ａ軸格子定数（Å）≦ ０.１０７５×０．３５３＋７.５７４２ （式１）
７．６１０３≦７．６１２１ From the chromaticity x = 0.353, the right side of Formula 1 was 7.6121. The a-axis lattice constant of the β-type sialon of Example 1 was 7.6103, and the relationship of Formula 1 was satisfied as shown below.
a-axis lattice constant (Å) ≦ 0.1075 × 0.353 + 7.5742 (Formula 1)
7.6103 ≦ 7.6121

レーザー散乱法による粒度分布測定から得られたβ型サイアロンの平均粒径Ｄ５０は８．５μｍであり、Ｄ１０は４．８μｍ、Ｄ９０は１３．４μｍであった。Ｄ１０、Ｄ９０は、体積基準の積算分率での１０％粒径、９０粒径である。
The average particle diameter D50 of β-sialon obtained from the particle size distribution measurement by the laser scattering method was 8.5 μm, D10 was 4.8 μm, and D90 was 13.4 μm. D10 and D90 are a 10% particle size and a 90 particle size at an integrated fraction based on volume.

実施例１のβ型サイアロンのＢＥＴをガス吸着法により測定し、ＢＥＴ多点解析により求めたＢＥＴ値は、０．２５ｍ２/ｇであった。このＢＥＴ値から前記式２でＢＥＴ径を計算すると７．５μｍであり、式３でのＤ５０（μｍ）／ＢＥＴ径（μｍ）は、１．１４であった。 The BET value of β-sialon of Example 1 was measured by a gas adsorption method, and the BET value determined by BET multipoint analysis was 0.25 m 2 / g. The BET diameter calculated from the BET value according to the above formula 2 was 7.5 μm, and the D50 (μm) / BET diameter (μm) in the formula 3 was 1.14.

実施例２のβ型サイアロンは、実施例１での分級工程中の水中分級処理を、１０μｍ以下の微粉を除去する水中分級処理とした以外は、実施例１と同様に製造したものである。
ＸＲＤ測定の結果、実施例２のβ型サイアロンのａ軸格子定数は７．６１２０８Å、ｃ軸格子定数は２．９１２７３Åであり、β型サイアロン以外の回折ピークは検出されず、発光ピーク強度は２２８％であり、ＣＩＥ色度は、色度ｘ＝０．３６３、色度ｙ＝０．６１８であった。 The β type sialon of Example 2 was produced in the same manner as in Example 1 except that the water classification process in the classification process in Example 1 was changed to the water classification process to remove fine particles of 10 μm or less.
As a result of the XRD measurement, the β-type sialon of Example 2 has an a-axis lattice constant of 7.61208 Å and a c-axis lattice constant of 2.9127Å, a diffraction peak other than the β-type sialon is not detected, and the emission peak intensity is 228. The CIE chromaticity was chromaticity x = 0.363 and chromaticity y = 0.618.

色度ｘ＝０．３６３から、式１の右辺は７．６１３２であり、実施例２のβ型サイアロンのａ軸格子定数の値は７．６１２０８であり、次に示すように式１の関係を満たしていた。
ａ軸格子定数（Å）≦０.１０７５×０．３６３＋７.５７４２
７．６１２０８≦７．６１３２ From the chromaticity x = 0.363, the right side of Equation 1 is 7.6132, the value of the a-axis lattice constant of the β-type sialon of Example 2 is 7.61208, and the relationship of Equation 1 is as follows: Was met.
a-axis lattice constant (Å) ≦ 0.1075 × 0.363 + 7.5742
7.61208 ≦ 7.6132

実施例２のβ型サイアロンの平均粒径Ｄ５０は１４．７μｍであり、Ｄ１０は７．９８μｍ、Ｄ９０は１４．７μｍであり、ＢＥＴ値は０．１９３ｍ２/ｇ、ＢＥＴ径は９．７μｍ、Ｄ５０（μｍ）／ＢＥＴ径（μｍ）は１．５２であった。 The average particle diameter D50 of β-sialon of Example 2 is 14.7 μm, D10 is 7.98 μm, D90 is 14.7 μm, the BET value is 0.193 m 2 / g, the BET diameter is 9.7 μm, D50 (μm) / BET diameter (μm) was 1.52.

実施例３のβ型サイアロンは、実施例１の分級工程中の水中分級処理を、１５μｍ以下の微粉を除去する水中分級処理にした以外は、実施例１と同様に製造したものである。
ＸＲＤ測定の結果、実施例３のβ型サイアロンのａ軸格子定数は７．６１１９Å、ｃ軸格子定数は２．９１３５Åであり、β型サイアロン以外の回折ピークは検出されなかった。発光ピーク強度は２３３％であり、ＣＩＥ色度は、色度ｘ＝０．３６５、色度ｙ＝０．６１５であった。 The β-sialon of Example 3 was produced in the same manner as in Example 1 except that the water classification process in the classification process of Example 1 was changed to an underwater classification process to remove fine powder of 15 μm or less.
As a result of the XRD measurement, the β-type sialon of Example 3 had an a-axis lattice constant of 7.6119Å and a c-axis lattice constant of 2.9135 、, and no diffraction peaks other than β-type sialon were detected. The emission peak intensity was 233%, and the CIE chromaticity was chromaticity x = 0.365 and chromaticity y = 0.615.

色度ｘ＝０．３６５から、式１の右辺は７．６１３４であり、実施例３のβ型サイアロンのａ軸格子定数の値は７．６１１９であり、次に示すように式１の関係を満たしていた。
ａ軸格子定数（Å）≦０.１０７５×０．３６５＋７.５７４２
７．６１１９≦７．６１３４ From the chromaticity x = 0.365, the right side of Equation 1 is 7.6134, and the value of the a-axis lattice constant of the β-type sialon of Example 3 is 7.6119. Was met.
a-axis lattice constant (Å) ≦ 0.1075 × 0.365 + 7.5742
7.6119 ≦ 7.6134

実施例３のβ型サイアロンの平均粒径Ｄ５０は１４．８μｍであり、Ｄ１０は８．４μｍ、Ｄ９０は２５．５μｍであり、ＢＥＴ値は０．２３５ｍ２/ｇ、ＢＥＴ径は７．９μｍ、Ｄ５０（μｍ）／ＢＥＴ径（μｍ）は、１．８７であった。 The average particle diameter D50 of β-sialon of Example 3 is 14.8 μm, D10 is 8.4 μm, D90 is 25.5 μm, the BET value is 0.235 m 2 / g, the BET diameter is 7.9 μm, D50 (μm) / BET diameter (μm) was 1.87.

（比較例１）
比較例１は、アニール工程を経ずに製造したものである。それ以外は実施例１と同様に製造した。
比較例１のβ型サイアロンでは、ＸＲＤ測定の結果、β型サイアロンと第二相としての２θ＝３３〜３８°付近に複数の微小な回折線が観察された。その中で最も高い回折線強度はβ型サイアロンの（１０１）面の回折線強度に対して１％以下であった。ａ軸格子定数は７．６１２０Å、ｃ軸格子定数は２．９１３５Åであった。
比較例１では発光ピーク強度は１２３％であり、ＣＩＥ色度は、色度ｘ＝０．３３８、色度ｙ＝０．６３７であり、色度ｘ＝０．３３８から式１の右辺を計算すると、７．６１０５であり、ａ軸格子定数の値（７．６１２Å）より小さかった。他の値は、表１に示すとおりである。 (Comparative Example 1)
Comparative Example 1 was manufactured without going through an annealing step. Other than that was manufactured similarly to Example 1.
In the β-type sialon of Comparative Example 1, as a result of XRD measurement, a plurality of minute diffraction lines were observed in the vicinity of 2θ = 33 to 38 ° as the β-type sialon and the second phase. Among them, the highest diffraction line intensity was 1% or less with respect to the diffraction line intensity of the (101) plane of β-sialon. The a-axis lattice constant was 7.6120 and the c-axis lattice constant was 2.9135.
In Comparative Example 1, the emission peak intensity is 123%, the CIE chromaticity is chromaticity x = 0.338, chromaticity y = 0.638, and the right side of Equation 1 is calculated from chromaticity x = 0.338. Then, it was 7.6105, which was smaller than the value of the a-axis lattice constant (7.612 Å). Other values are as shown in Table 1.

（比較例２）
比較例２は、原料粉中のＡｌ量から計算したｚ値が０．２５、酸化ユーロピウム粉末以外の酸素量から計算したｚ値が０．２２、酸化ユーロピウム粉末を０．２９モル％となるように配合し、実施例１の水中分級処理を、２０μｍ以下の微粉を除去する水中分級処理とした以外は、実施例１と同様のものである。
比較例２のβ型サイアロンでは、ＸＲＤ測定の結果、サイアロン以外のピークは検出されなかった。ａ軸格子定数は７．６１０５Å、ｃ軸格子定数は２．９１２２Åであった。発光ピーク強度は１９９％であり、ＣＩＥ色度は、色度ｘ＝０．３６、色度ｙ＝０．６１８であり、他の値は、表１に示すとおりであった。色度ｘ＝０．３６から、式１の右辺を計算すると、７．６１０３となり、式１の関係を満たしていなかった。 (Comparative Example 2)
In Comparative Example 2, the z value calculated from the amount of Al in the raw material powder is 0.25, the z value calculated from the amount of oxygen other than the europium oxide powder is 0.22, and the europium oxide powder is 0.29 mol%. The same procedure as in Example 1 is applied except that the water classification treatment in Example 1 is changed to the water classification treatment to remove fine powder of 20 μm or less.
In the β-sialon of Comparative Example 2, as a result of XRD measurement, no peak other than sialon was detected. The a-axis lattice constant was 7.6105 Å, and the c-axis lattice constant was 2.9122 Å. The emission peak intensity was 199%, the CIE chromaticity was chromaticity x = 0.36, the chromaticity y = 0.618, and the other values were as shown in Table 1. When the right side of Equation 1 was calculated from chromaticity x = 0.36, it was 7.6103, and the relationship of Equation 1 was not satisfied.

表１に示すように、実施例１〜３のβ型サイアロンは、何れも式１、式２及び式３の関係を満たし、比較例１及び２のβ型サイアロンに比べて高い発光ピーク強度を示した。   As shown in Table 1, the β-sialons of Examples 1 to 3 all satisfy the relationships of Formulas 1, 2 and 3, and have a higher emission peak intensity than the β-sialons of Comparative Examples 1 and 2. Indicated.

実施例４は、実施例１のβ型サイアロンを用いた発光装置である。以下、図２を参照して詳細に説明する。
発光装置１０は、発光光源１２としてのＬＥＤチップと、この発光光源１２に導通された第１のリードフレーム１３と、第１のリードフレーム１３の近傍に取り付けられた第２のリードフレーム１４と、発光光源１２と第２のリードフレーム１４とを導通させるボンディングワイヤ１６とを有し、発光光源１２は、第１のリードフレーム１３の凹部１３ｂの中に配置され、この凹部１３ｂ内に充填された波長変換部材１５に覆われている。波長変換部材１５は、β型サイアロン１８を配合した封止樹脂１７を有し、発光装置１０の上面は、合成樹脂製のキャップ１９に覆われている。図２の符号１３ａは、第１のリードフレーム１３の上部である。 Example 4 is a light emitting device using the β-sialon of Example 1. Hereinafter, this will be described in detail with reference to FIG.
The light-emitting device 10 includes an LED chip as the light-emitting light source 12, a first lead frame 13 conducted to the light-emitting light source 12, a second lead frame 14 attached in the vicinity of the first lead frame 13, It has a bonding wire 16 for conducting the light emitting light source 12 and the second lead frame 14, and the light emitting light source 12 is disposed in the concave portion 13b of the first lead frame 13 and filled in the concave portion 13b. The wavelength conversion member 15 is covered. The wavelength conversion member 15 has a sealing resin 17 in which β-sialon 18 is blended, and the upper surface of the light emitting device 10 is covered with a synthetic resin cap 19. Reference numeral 13 a in FIG. 2 is an upper portion of the first lead frame 13.

波長変換部材１５は、予め個別にシランカップリング剤（信越シリコーン社製ＫＢＥ４０２）でシランカップリング処理したβ型サイアロン１８を、封止樹脂１７としてのエポキシ樹脂（サンユレック社製ＮＬＤ−ＳＬ−２１０１）に混練して作製した。発光光源１２は、発光波長４５０ｎｍの青色ＬＥＤチップを用いた。β型サイアロン１８は、実施例１のβ型サイアロンと、Ｃａ０．６６Ｅｕ０．０４Ｓｉ９．９Ａｌ２．１Ｏ０．７Ｎ１５．３の組成を持つＣａ−α型サイアロン：Ｅｕ蛍光体との混合体である。Ｃａ−α型サイアロン：Ｅｕの発光ピーク波長は５８５ｎｍである。 The wavelength converting member 15 is an epoxy resin (NLD-SL-2101 manufactured by Sanyu Rec Co., Ltd.) as a sealing resin 17 of β-sialon 18 that has been individually treated with a silane coupling agent (KBE402 manufactured by Shin-Etsu Silicone Co., Ltd.) in advance. And kneaded. As the light emission source 12, a blue LED chip having an emission wavelength of 450 nm was used. The β-type sialon 18 is composed of the β-type sialon of Example 1 and a Ca-α-type sialon having a composition of Ca 0.66 Eu 0.04 Si 9.9 Al 2.1 O 0.7 N 15.3 : Eu It is a mixture with a phosphor. Ca-α type sialon: Eu has an emission peak wavelength of 585 nm.

実施例５は、実施例４の「実施例１のβ型サイアロン」を「実施例３のβ型サイアロン」に変更した以外は、実施例４と同様のものである。   Example 5 is the same as Example 4 except that “β-sialon of Example 1” in Example 4 is changed to “β-sialon of Example 3.”

（比較例３）
比較例３の発光装置は、実施例４の「実施例１のβ型サイアロン」を「比較例１のβ型サイアロン」に変更した以外は、実施例４と同様のものである。 (Comparative Example 3)
The light emitting device of Comparative Example 3 is the same as that of Example 4 except that “β-sialon of Example 1” in Example 4 is changed to “β-sialon of Comparative Example 1”.

（比較例４）
比較例４の発光装置は、実施例４の「実施例１のβ型サイアロン」を「比較例２のβ型サイアロン」に変更した以外は、実施例４と同様のものである。 (Comparative Example 4)
The light emitting device of Comparative Example 4 is the same as that of Example 4 except that “β-sialon of Example 1” in Example 4 is changed to “β-sialon of Comparative Example 2”.

実施例４、５及び比較例３、４の発光装置１０を同一通電条件で発光させ、輝度計により同一条件下での中心照度及びＣＩＥ色度（ＣＩＥ１９３１）を測定した。色度座標（ｘ、ｙ）が（０．３１、０．３２）の白色発光装置で中心照度を比較した。実施例４、５、比較例１、２の発光装置１０の明るさは、比較例３の発光装置の明るさを基準にすると、それぞれ、実施例４では１２５％、実施例５では１３６％、比較例３では１００％、比較例４では１１７％であった。   The light emitting devices 10 of Examples 4 and 5 and Comparative Examples 3 and 4 were caused to emit light under the same energization conditions, and the central illuminance and CIE chromaticity (CIE 1931) under the same conditions were measured with a luminance meter. The central illuminance was compared with a white light emitting device having chromaticity coordinates (x, y) of (0.31, 0.32). The brightness of the light emitting devices 10 of Examples 4 and 5 and Comparative Examples 1 and 2 is 125% in Example 4 and 136% in Example 5 with respect to the brightness of the light emitting device of Comparative Example 3, respectively. In Comparative Example 3, it was 100%, and in Comparative Example 4, it was 117%.

本発明の実施例のβ型サイアロンは、３５０〜５００ｎｍの波長の光を発する紫外ＬＥＤチップまたは青色ＬＥＤチップを励起光として、強度の高い緑色を発光させることができる。このため、上記実施例のβ型サイアロンに加えて他色発光する別の蛍光体を組み合わせて用いることで、発光特性の良好な白色ＬＥＤを実現できる。   The β-sialon according to the embodiment of the present invention can emit high-intensity green light using an ultraviolet LED chip or a blue LED chip emitting light with a wavelength of 350 to 500 nm as excitation light. For this reason, a white LED having good light emission characteristics can be realized by using in combination with another phosphor that emits light of other colors in addition to the β-sialon of the above embodiment.

１０：発光装置
１２：発光光源
１３：第１のリードフレーム
１３ａ：第１のリードフレームの上部
１３ｂ：第１のリードフレームの凹部
１４：第２のリードフレーム
１５：波長変換部材
１６：ボンディングワイヤ
１７：封止樹脂
１８：β型サイアロン
１９：キャップ 10: light emitting device 12: light emitting light source 13: first lead frame 13a: upper portion 13b of the first lead frame: concave portion 14 of the first lead frame 14: second lead frame 15: wavelength conversion member 16: bonding wire 17 : Sealing resin 18: β-type sialon 19: Cap

Claims (3)

一般式：Ｓｉ６−ｚＡｌｚＯｚＮ８−ｚで示されＥｕを固溶したβ型サイアロンであって、
ａ軸格子定数とＣＩＥ色度の色度ｘとの関係が、次の式１で表されるβ型サイアロン。
ａ軸格子定数（Å）≦０.１０７５×色度ｘ＋７．５７４２ （式１） A β-type sialon represented by the general formula: Si 6-z Al z O z N 8-z in which Eu is dissolved,
β-sialon in which the relationship between the a-axis lattice constant and the chromaticity x of the CIE chromaticity is expressed by the following formula 1.
a-axis lattice constant (Å) ≦ 0.1075 × chromaticity x + 7.5742 (formula 1) 前記β型サイアロンのＢＥＴ値から次の式２で計算されるＢＥＴ径と、前記β型サイアロンをレーザー回折散乱法にて測定した平均粒子径Ｄ５０との関係が、次の式３で表される請求項１記載のβ型サイアロン。
ＢＥＴ径（μｍ）＝６÷（３．２２×ＢＥＴ値（ｍ２／ｇ）） （式２）
Ｄ５０（μｍ）／ＢＥＴ径（μｍ）＜１．９ （式３） The relationship between the BET diameter calculated from the BET value of the β-type sialon by the following formula 2 and the average particle size D50 obtained by measuring the β-type sialon by a laser diffraction scattering method is expressed by the following formula 3. The β-type sialon according to claim 1.
BET diameter (μm) = 6 ÷ (3.22 × BET value (m 2 / g)) (Formula 2)
D50 (μm) / BET diameter (μm) <1.9 (Formula 3) 請求項１又は２に記載のβ型サイアロンと、発光光源とを備える発光装置。   A light-emitting device comprising the β-sialon according to claim 1 or 2 and a light-emitting light source.
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