JP5710089B2 - Green light emitting oxynitride phosphor and light emitting device using the same - Google Patents
Green light emitting oxynitride phosphor and light emitting device using the same Download PDFInfo
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- JP5710089B2 JP5710089B2 JP2007167007A JP2007167007A JP5710089B2 JP 5710089 B2 JP5710089 B2 JP 5710089B2 JP 2007167007 A JP2007167007 A JP 2007167007A JP 2007167007 A JP2007167007 A JP 2007167007A JP 5710089 B2 JP5710089 B2 JP 5710089B2
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- Prior art keywords
- light emitting
- green light
- light
- oxynitride phosphor
- emitting
- Prior art date
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical compound Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 1
- HPNURIVGONRLQI-UHFFFAOYSA-K trifluoroeuropium Chemical compound F[Eu](F)F HPNURIVGONRLQI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本発明は、緑色発光酸窒化物蛍光体、及びそれを用いた発光素子に関する。 The present invention is a green light-emitting oxynitride fluorescent material, a light emitting element using 及 Bisore.
発光ダイオードは、発光効率が良く、鮮やかな色で発光する。そのため各種インジケータや光源として利用されている。
しかし、発光ダイオードは、優れた単色性ピーク波長を有するので、白色系の発光をすることが困難である。
The light emitting diode has high luminous efficiency and emits light with a bright color. Therefore, it is used as various indicators and light sources.
However, since the light emitting diode has an excellent monochromatic peak wavelength, it is difficult to emit white light.
そこで、紫外線発光ダイオードと蛍光物質とを組み合わせ、紫外線発光ダイオードからの光と、その光により励起されて色変換された蛍光物質の発色との混色により白色系の光を生み出す技術が開示されている。
例えば、紫外線発光ダイオードにより青色蛍光体を励起し、その青色励起光によりＹＡＧ系蛍光体を励起する二段階励起により白色光を得る技術がある。
Therefore, a technology is disclosed in which a UV light emitting diode and a fluorescent material are combined, and white light is generated by mixing the light from the UV light emitting diode and the color of the fluorescent material that is excited by the light and converted in color. .
For example, there is a technique for obtaining white light by two-step excitation in which a blue phosphor is excited by an ultraviolet light emitting diode and a YAG phosphor is excited by the blue excitation light.
しかし、このような二段階励起の方式は高発光効率の白色光を得ることは困難である。
そこで、紫外線発光ダイオードと青色、緑色、赤色蛍光体を組み合わせた３波長型の白色発光素子が開発されている。そして、緑色発光蛍光体としては、例えば希土類元素を発光中心に用いた酸化物系蛍光体がある。
However, it is difficult to obtain white light with high luminous efficiency by such a two-stage excitation method.
Therefore, a three-wavelength type white light emitting element in which an ultraviolet light emitting diode and a blue, green, and red phosphor are combined has been developed. An example of the green light emitting phosphor is an oxide phosphor using a rare earth element as a light emission center.
しかし、緑色発光の酸窒化物蛍光体についてはあまり研究・開発されていない。例えば、特許文献１には緑色発光酸窒化物が開示されているが、発光効率が高いものとはいえない。 However, little research and development has been done on green-emitting oxynitride phosphors. For example, Patent Document 1 discloses a green light emitting oxynitride, but it cannot be said that the light emitting efficiency is high.
本発明は、このような課題に鑑みてなされたものであり、発光効率の高い緑色発光酸窒化物蛍光体を提供することを目的とするものである。即ち、紫外線発光ダイオードの高い発光効率の波長領域の光を効率よく吸収して発光する緑色発光酸窒化物蛍光体を提供することを目的とするものである。
さらに、そのような緑色発光酸窒化物蛍光体を用いた高輝度の発光素子を提供することを目的とするものである。
This invention is made | formed in view of such a subject, and it aims at providing the green light emission oxynitride fluorescent substance with high luminous efficiency. That is, an object of the present invention is to provide a green light emitting oxynitride phosphor that efficiently absorbs light in the wavelength region of high light emission efficiency of an ultraviolet light emitting diode and emits light .
Et al is, it is an object to provide a high luminance light emitting device using such a green light-emitting oxynitride phosphor.
上記目的を達成するため、この発明の第１の観点に係る緑色発光酸窒化物蛍光体は、
一般式ＣａｗＥｕａＳｉｘＯｙＮｚ
（ここで、
０．０１≦ａ≦０．２０、
０．８≦ｘ／（ｗ＋ａ）≦０．９、
０＜ｚ／ｙ＜１．０、
１．１≦ｗ／ｘ≦１．２４、
０．５≦ｘ／ｙ≦０．６９、
０．９≦ｘ／ｚ≦１．２）
で表され、緑色帯域の発光波長を有することを特徴とする。
In order to achieve the above object, a green light-emitting oxynitride phosphor according to the first aspect of the present invention includes:
General formula Ca w Eu a Si x O y N z
(here,
0.01 ≦ a ≦ 0.20,
0.8 ≦ x / (w + a) ≦ 0.9,
0 <z / y <1.0,
1.1 ≦ w / x ≦ 1.24
0.5 ≦ x / y ≦ 0.69 ,
0.9 ≦ x / z ≦ 1.2)
It is characterized by having an emission wavelength in the green band.
また、前記緑色発光酸窒化物蛍光体は、波長３００ｎｍ以上４００ｎｍ以下に励起帯を有する、とすることも可能である。 The green luminescent oxynitride phosphor may have an excitation band at a wavelength of 300 nm to 400 nm.
また、上記目的を達成するため、この発明の第２の観点に係る発光素子は、
この発明の第１の観点に係る緑色発光酸窒化物蛍光体と、
蛍光体の励起光源としての紫外線発光ダイオードと、
を有する、ことを特徴とする。
In order to achieve the above object, a light emitting device according to the second aspect of the present invention is
A green light-emitting oxynitride phosphor according to the first aspect of the present invention ;
An ultraviolet light emitting diode as an excitation light source of the phosphor;
It is characterized by having.
また、赤色発光蛍光体と、青色発光蛍光体と、を有するとすることも可能である。 It is also possible to have a red light-emitting phosphor and a blue light-emitting phosphor.
また、前記赤色発光蛍光体は、ＳｒＳ：Ｅｕ、ＣａＳ：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ及びＬａ２Ｏ２Ｓ：Ｅｕのうち少なくともいずれか一つを含有し、
前記青色発光蛍光体は、（Ｂａ，Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｅｕ，Ｍｎ、（Ｂａ，Ｓｒ，Ｃａ，Ｍｇ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ、Ｓｒ５（ＰＯ４）３Ｃｌ：Ｅｕ及びＺｎＳ：Ａｇのうち少なくともいずれか一つを含有する、とすることも可能である。
The red light emitting phosphor contains at least one of SrS: Eu, CaS: Eu, CaAlSiN 3 : Eu, and La 2 O 2 S: Eu,
The blue light-emitting phosphor includes (Ba, Sr) MgAl 10 O 17 : Eu, Mn, (Ba, Sr, Ca, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, Sr 5 (PO 4 ) 3 Cl: It is also possible to contain at least one of Eu and ZnS: Ag.
本発明に係る緑色発光酸窒化物蛍光体は、発光効率が高い。 The green light emitting oxynitride phosphor according to the present invention has high luminous efficiency .
発明者らは鋭意研究を重ねた結果、
一般式Ｍ１ｗＲｅａＭ２ｘＯｙＮｚ
（ここで、
Ｍ１は、第ＩＩ族元素若しくはＳｎを含有する金属、
Ｍ２は、Ｓｎを除く第ＩＶ族元素を含有する金属、
Ｒｅは付活剤であり、
０．０１≦ａ≦０．２０、
０．８≦ｘ／（ｗ＋ａ）≦１．０、
０＜ｚ／ｙ≦１．０）
で表される緑色発光酸窒化物蛍光体が、紫外線発光ダイオードの高い発光効率の波長領域の光を効率よく吸収して発光することを見いだした。
As a result of repeated researches, the inventors
General formula M1 w Re a M2 x O y N z
(here,
M1 is a group II element or a metal containing Sn,
M2 is a metal containing a group IV element excluding Sn,
Re is an activator,
0.01 ≦ a ≦ 0.20,
0.8 ≦ x / (w + a) ≦ 1.0,
0 <z / y ≦ 1.0)
It was found that the green light emitting oxynitride phosphor represented by the above formula efficiently absorbs light in the wavelength region of the high light emitting efficiency of the ultraviolet light emitting diode and emits light.
（実施例１）
実施例１に係る緑色発光酸窒化物蛍光体（組成式Ｃａ８．９７Ｅｕ０．０３Ｓｉ８Ｏ１０Ｎ１０）の励起スペクトルを図１に、発光スペクトルを図２に示す。
図１に示されるように、実施例１に係る緑色発光酸窒化物蛍光体は、波長３００〜４００ｎｍ付近に励起帯がある。約３６０ｎｍに発光ピークがあり、紫外線発光ダイオードに対して効率よく発光する。
また、図２に示されるように、発光スペクトルの発光ピークの半値幅は約５８ｎｍ程度であり、ブロードな発光ピークである。
Example 1
The excitation spectrum of the green light emitting oxynitride phosphor (composition formula Ca 8.97 Eu 0.03 Si 8 O 10 N 10 ) according to Example 1 is shown in FIG. 1, and the emission spectrum is shown in FIG.
As shown in FIG. 1, the green light-emitting oxynitride phosphor according to Example 1 has an excitation band in the vicinity of a wavelength of 300 to 400 nm. There is an emission peak at about 360 nm, and light is emitted efficiently with respect to the ultraviolet light emitting diode.
Further, as shown in FIG. 2, the half-value width of the emission peak of the emission spectrum is about 58 nm, which is a broad emission peak.
（実施例１に係る緑色発光酸窒化物蛍光体の製造方法）
原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）と、酸化ケイ素（ＳｉＯ２）と、窒化ケイ素（Ｓｉ３Ｎ４）と、ユーロピウム化合物としての塩化ユーロピウム（ＥｕＣｌ３）と、を準備する。
窒化カルシウム（Ｃａ３Ｎ２）は、アルゴン雰囲気中で原料としてのカルシウムを粉砕し、粉砕したカルシウムを窒素雰囲気中で窒化することにより得る。カルシウムの窒化反応は、６００〜９００℃で、約５〜６時間行う。原料としてのカルシウムはカルシウム単体のものを使用するのが望ましいが、イミド化合物、アミド化合物、酸化カルシウム等のカルシウム化合物を用いることも可能である。
窒化ケイ素（Ｓｉ３Ｎ４）は、アルゴン雰囲気中で原料としてのケイ素を粉砕し、粉砕したケイ素を窒素雰囲気中で窒化することにより得る。ケイ素の窒化反応は、８００〜１２００℃で、約５〜６時間行う。原料としてのケイ素はケイ素単体のものを使用するのが望ましいが、イミド化合物、アミド化合物を用いることも可能である。Ｓｉ（ＮＨ２）２等を使用することができる。
ユーロピウム化合物は、塩化ユーロピウム（ＥｕＣｌ３）やフッ化ユーロピウム（ＥｕＦ３）等であってもよい。また、ユーロピウム化合物はイミド化合物やアミド化合物を用いることも可能である。酸化ユーロピウム（Ｅｕ２Ｏ３）は市販の物を用いることができるが、高純度の物が望ましい。
さらに、加熱処理の際に蛍光体粒子の結晶成長を促進するような添加物であるフラックス材として塩化アンモニウム（ＮＨ４Ｃｌ）を準備する。なお、フラックス材は、フッ化アルミニウム（ＡｌＦ３）等のハロゲン化アンモニウム、ＮａＣＯ３、ＬｉＣＯ３等のアルカリ金属炭酸塩、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ等のアルカリハロゲン化物、ＣａＣｌ３、ＣａＦ２、ＢａＦ２のようなアルカリ土類金属のハロゲン化物、Ｂ２Ｏ３、Ｈ３ＢＯ３、ＮａＢ４Ｏ７のようなホウ酸塩化合物、Ｌｉ３ＰＯ４、ＮＨ４Ｈ２ＰＯ４のようなリン酸塩等が使用できる。
そして、窒化カルシウム（Ｃａ３Ｎ２）は１．０９６０ｇ、酸化ケイ素（ＳｉＯ２）は０．７５１０ｇ、窒化ケイ素（Ｓｉ３Ｎ４）は０．３５０７ｇ、塩化ユーロピウム（ＥｕＣｌ３）は０．０１９２ｇ秤量する。塩化アンモニウム（ＮＨ４Ｃｌ）は０．０３ｇ秤量する。
(Method for producing green luminescent oxynitride phosphor according to Example 1)
As raw material powder, calcium nitride (Ca 3 N 2 ), silicon oxide (SiO 2 ), silicon nitride (Si 3 N 4 ), and europium chloride (EuCl 3 ) as a europium compound are prepared.
Calcium nitride (Ca 3 N 2 ) is obtained by pulverizing calcium as a raw material in an argon atmosphere and nitriding the pulverized calcium in a nitrogen atmosphere. The nitriding reaction of calcium is performed at 600 to 900 ° C. for about 5 to 6 hours. As the raw material calcium, it is desirable to use calcium alone, but calcium compounds such as imide compounds, amide compounds, and calcium oxide can also be used.
Silicon nitride (Si 3 N 4 ) is obtained by pulverizing silicon as a raw material in an argon atmosphere and nitriding the pulverized silicon in a nitrogen atmosphere. The nitridation reaction of silicon is performed at 800 to 1200 ° C. for about 5 to 6 hours. It is desirable to use silicon as a raw material, but it is also possible to use an imide compound or an amide compound. Si (NH 2 ) 2 or the like can be used.
The europium compound may be europium chloride (EuCl 3 ), europium fluoride (EuF 3 ), or the like. As the europium compound, an imide compound or an amide compound can be used. As europium oxide (Eu 2 O 3 ), a commercially available product can be used, but a highly pure product is desirable.
Further, ammonium chloride (NH 4 Cl) is prepared as a flux material that is an additive that promotes crystal growth of the phosphor particles during the heat treatment. Note that the flux material, an ammonium halide such as aluminum fluoride (AlF 3), NaCO 3, LiCO 3 alkali metal carbonate such as, LiCl, NaCl, alkali halides KCl, etc., CaCl 3, CaF 2, BaF 2 Alkaline earth metal halides such as B 2 O 3 , H 3 BO 3 , borate compounds such as NaB 4 O 7 , Li 3 PO 4 , phosphates such as NH 4 H 2 PO 4 Etc. can be used.
Then, 1.0960 g of calcium nitride (Ca 3 N 2 ), 0.7510 g of silicon oxide (SiO 2 ), 0.3507 g of silicon nitride (Si 3 N 4 ), and 0.0192 g of europium chloride (EuCl 3 ) are weighed. To do. 0.03 g of ammonium chloride (NH 4 Cl) is weighed.
これら原料粉末を、瑪瑙製若しくはアルミナ製乳鉢にて、１５分間粉砕混合する。このような乾式の混合では、湿式の混合と比較して有機溶媒を乾燥させる工程がない点で有利である。 These raw material powders are pulverized and mixed for 15 minutes in a smoked or alumina mortar. Such dry mixing is advantageous in that there is no step of drying the organic solvent as compared with wet mixing.
次に、得られた原料粉末を、窒化ホウ素坩堝に充填し、電気炉にセットする。なお、得られた原料粉末は、アルミナ坩堝やアルミナトレイ、カーボン坩堝やカーボントレイ、窒化ホウ素トレイ等の耐熱容器に充填することも可能である。
そして、アンモニア雰囲気下で焼成する。なお、水素−窒素を混合させた還ガス元雰囲気中で焼成することも可能であり、さらには一酸化炭素気流中で焼成することも可能である。
Next, the obtained raw material powder is filled in a boron nitride crucible and set in an electric furnace. The obtained raw material powder can be filled in a heat-resistant container such as an alumina crucible, an alumina tray, a carbon crucible, a carbon tray, or a boron nitride tray.
Then, firing is performed in an ammonia atmosphere. It is also possible to fire in a return gas source atmosphere in which hydrogen-nitrogen is mixed, and it is also possible to fire in a carbon monoxide stream.
焼成する場合における圧力は１．１気圧である。焼成する場合における圧力は、１．００〜１．５０気圧が良い。圧力が１．００気圧より低いと反応が十分に促進されない可能性があるからであり、一方、圧力が１．５０気圧よりも高いと窒素ガスを閉じこめる容器を頑丈にする必要がありそのため製造装置が高価な物になる可能性があるからである。焼成する場合の圧力は、より好ましくは１．０２〜１．３気圧、さらに好ましくは１．０５〜１．２気圧にすると良い。 The pressure when firing is 1.1 atm. The pressure when firing is preferably 1.00 to 1.50 atm. This is because if the pressure is lower than 1.00 atm, the reaction may not be sufficiently promoted. On the other hand, if the pressure is higher than 1.50 atm, it is necessary to make the container for confining nitrogen gas sturdy, and thus the manufacturing apparatus. This is because there is a possibility that becomes expensive. The pressure for firing is more preferably 1.02 to 1.3 atm, and even more preferably 1.05 to 1.2 atm.
焼成温度は１３５０℃である。焼成温度は、１０００℃〜１４００℃が良い。焼成温度が１０００℃よりも小さいと反応の進行度が遅くて反応に時間がかかるおそれがあるからであり、一方、焼成温度が１４００℃よりも大きいと予期せぬ副反応が生じるおそれがあるからである。焼成する温度は、より好ましくは１１００〜１３５０℃が良い。 The firing temperature is 1350 ° C. The firing temperature is preferably 1000 ° C to 1400 ° C. This is because if the calcination temperature is lower than 1000 ° C., the progress of the reaction is slow and the reaction may take a long time. On the other hand, if the calcination temperature is higher than 1400 ° C., an unexpected side reaction may occur. It is. The firing temperature is more preferably 1100 to 1350 ° C.
焼成時間は３時間である。焼成時間は、３〜１０時間で焼成するのが好ましい。
焼成が終了すると、徐々に冷却し、そして得られた焼成物を粉砕し混合する。これにより実施例１に係る緑色発光酸窒化物蛍光体（組成式Ｃａ８．９７Ｅｕ０．０３Ｓｉ８Ｏ１０Ｎ１０）を得ることができる。その後さらに得られた緑色発光酸窒化物蛍光体をさらに再焼成することも可能である。
The firing time is 3 hours. The firing time is preferably 3 to 10 hours.
When the calcination is completed, the mixture is gradually cooled, and the obtained baked product is pulverized and mixed. Thereby, the green light emitting oxynitride phosphor (compositional formula Ca 8.97 Eu 0.03 Si 8 O 10 N 10 ) according to Example 1 can be obtained. Thereafter, the obtained green light-emitting oxynitride phosphor can be further refired.
なお、得られた緑色発光酸窒化物蛍光体は、平均粒子径が２０〜２２０μｍ、特に８０〜１６０μｍのものである。平均粒子径が２２０μｍを超えると、蛍光体の均一な分散が得られなくなるおそれがあり、また、他の蛍光体と併用した場合、色むらが起こるおそれがあるからである。一方、平均粒子径が２０μｍより小さいと、かえって強度が低下するおそれがあるからである。 The obtained green light-emitting oxynitride phosphor has an average particle size of 20 to 220 μm, particularly 80 to 160 μm. If the average particle diameter exceeds 220 μm, uniform dispersion of the phosphor may not be obtained, and color unevenness may occur when used in combination with other phosphors. On the other hand, if the average particle size is smaller than 20 μm, the strength may be lowered.
（実施例２〜５）
実施例２に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３Ｏ３．６Ｎ３．６である。実施例３に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３Ｏ４．５Ｎ３．０である。実施例４に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３Ｏ５．４Ｎ２．４である。実施例５に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３Ｏ６．０Ｎ２．０である。
(Examples 2 to 5)
The green light-emitting oxynitride phosphor according to Example 2 has the composition formula Ca 2.97 Eu 0.03 Si 3 O 3.6 N 3.6 . The green light-emitting oxynitride phosphor according to Example 3 has the composition formula Ca 2.97 Eu 0.03 Si 3 O 4.5 N 3.0 . The green light-emitting oxynitride phosphor according to Example 4 has the composition formula Ca 2.97 Eu 0.03 Si 3 O 5.4 N 2.4 . The green light-emitting oxynitride phosphor according to Example 5 has the composition formula Ca 2.97 Eu 0.03 Si 3 O 6.0 N 2.0 .
実施例２に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．３７１１ｇ、酸化ケイ素（ＳｉＯ２）を１．０３１１ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．５３５０ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７３９ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 The green light-emitting oxynitride phosphor according to Example 2 has 1.3711 g of calcium nitride (Ca 3 N 2 ), 1.0311 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) as a raw material powder. 0.5350 g, europium chloride (EuCl 3 ) 0.0739 g, and ammonium chloride (NH 4 Cl) 0.03 g. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例３に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．３５３１ｇ、酸化ケイ素（ＳｉＯ２）を１．２７２０ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．３３００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７２９ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 3, as raw material powder, 1.3531 g of calcium nitride (Ca 3 N 2 ), 1.2720 g of silicon oxide (SiO 2 ), silicon nitride (Si 3 N 4 ) 0.3300 g, europium chloride (EuCl 3 ) 0.0729 g, and ammonium chloride (NH 4 Cl) 0.03 g. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例４に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．３３２６ｇ、酸化ケイ素（ＳｉＯ２）を１．５０３３ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．１３００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７１８ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 4, 1.3326 g of calcium nitride (Ca 3 N 2 ), 1.50333 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) are used as raw material powders. 0.1300 g, europium chloride (EuCl 3 ) 0.0718 g, and ammonium chloride (NH 4 Cl) 0.03 g. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例５に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．３１６４ｇ、酸化ケイ素（ＳｉＯ２）を１．６５００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７０９ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 5, 1.3164 g of calcium nitride (Ca 3 N 2 ), 1.6500 g of silicon oxide (SiO 2 ), and 0 of europium chloride (EuCl 3 ) are used as raw powders. 0.0709 g and 0.03 g of ammonium chloride (NH 4 Cl) are weighed. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例２〜５に係る緑色発光酸窒化物蛍光体の励起スペクトルを図３に示す。また、実施例２〜５に係る緑色発光酸窒化物蛍光体の発光スペクトルを図４に示す。
図３に示されるように、実施例２〜５に係る緑色発光酸窒化物蛍光体は、波長３００〜４００ｎｍ付近に励起帯がある。
実施例２に係る緑色発光酸窒化物蛍光体は３５０ｎｍに近い位置に発光ピークがあり、実施例３に係る緑色発光酸窒化物蛍光体は３４０ｎｍに近い位置に発光ピークがあり、実施例４に係る緑色発光酸窒化物蛍光体は３４０ｎｍに近い位置に発光ピークがあり、実施例５に係る緑色発光酸窒化物蛍光体は３３０ｎｍに近い位置に発光ピークがあり、実施例２〜５に係る緑色発光酸窒化物蛍光体は紫外線発光ダイオードに対して効率よく発光する。
また、図４に示されるように、実施例２に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約９７ｎｍ程度であり、実施例３に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約１０７ｎｍ程度であり、実施例４に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約１０３ｎｍ程度であり、実施例５に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約１０３ｎｍ程度であり、いずれもブロードな発光ピークである。なお、実施例２に係る緑色発光酸窒化物蛍光体は、やや青緑色に発光する一方、実施例３に係る緑色発光酸窒化物蛍光体は、やや黄緑色に発光する。
The excitation spectrum of the green light emitting oxynitride phosphor according to Examples 2 to 5 is shown in FIG. Moreover, the emission spectrum of the green light emission oxynitride fluorescent substance which concerns on Examples 2-5 is shown in FIG.
As shown in FIG. 3, the green light-emitting oxynitride phosphors according to Examples 2 to 5 have an excitation band in the vicinity of a wavelength of 300 to 400 nm.
The green light emitting oxynitride phosphor according to Example 2 has a light emission peak at a position close to 350 nm, and the green light emitting oxynitride phosphor according to Example 3 has a light emission peak at a position close to 340 nm. The green light-emitting oxynitride phosphor has a light emission peak at a position close to 340 nm, the green light-emitting oxynitride phosphor according to Example 5 has a light emission peak at a position close to 330 nm, and the green light emission according to Examples 2-5. The luminescent oxynitride phosphor emits light efficiently with respect to the ultraviolet light emitting diode.
As shown in FIG. 4, the green light-emitting oxynitride phosphor according to Example 2 has a half-value width of the emission peak of the emission spectrum of about 97 nm, and the green light-emitting oxynitride fluorescence according to Example 3 The half-width of the emission peak of the emission spectrum is about 107 nm, and the half-width of the emission peak of the emission spectrum of the green light-emitting oxynitride phosphor according to Example 4 is about 103 nm. The green light emitting oxynitride phosphor according to the present invention has a broad emission peak with a full width at half maximum of an emission peak of about 103 nm. The green light-emitting oxynitride phosphor according to Example 2 emits a little blue-green, while the green light-emitting oxynitride phosphor according to Example 3 emits a little yellow-green.
（実施例６〜８）
実施例６に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．７Ｏ３．４Ｎ３．４である。実施例７に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．７Ｏ３．９Ｎ３．０である。実施例８に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．７Ｏ４．８Ｎ２．４である。
(Examples 6 to 8)
The green light-emitting oxynitride phosphor according to Example 6 has the composition formula Ca 2.97 Eu 0.03 Si 2.7 O 3.4 N 3.4 . The green light-emitting oxynitride phosphor according to Example 7 has the composition formula Ca 2.97 Eu 0.03 Si 2.7 O 3.9 N 3.0 . The green light-emitting oxynitride phosphor according to Example 8 has the composition formula Ca 2.97 Eu 0.03 Si 2.7 O 4.8 N 2.4 .
実施例６係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．４４７２ｇ、酸化ケイ素（ＳｉＯ２）を１．０１５８ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．４８００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７８０ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 6, 1.4472 g of calcium nitride (Ca 3 N 2 ), 1.0158 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) are used as raw material powders. 0.4800 g, 0.0780 g of europium chloride (EuCl 3 ), and 0.03 g of ammonium chloride (NH 4 Cl) are weighed. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例７に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．４３５１ｇ、酸化ケイ素（ＳｉＯ２）を１．１６９２ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．３５００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７７３ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 7, 1.4351 g of calcium nitride (Ca 3 N 2 ), 1.1692 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) are used as raw material powders. 0.3500 g, europium chloride (EuCl 3 ) 0.0773 g, and ammonium chloride (NH 4 Cl) 0.03 g. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例８に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．４１４６ｇ、酸化ケイ素（ＳｉＯ２）を１．４１８５ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．１３８０ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７６２ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 The green light-emitting oxynitride phosphor according to Example 8 has 1.4146 g of calcium nitride (Ca 3 N 2 ), 1.4185 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) as a raw material powder. 0.1380 g, europium chloride (EuCl 3 ) 0.0762 g, and ammonium chloride (NH 4 Cl) 0.03 g. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例６〜８に係る緑色発光酸窒化物蛍光体の励起スペクトルを図５に示す。また、実施例６〜８に係る緑色発光酸窒化物蛍光体の発光スペクトルを図６に示す。
図５に示されるように、実施例６〜８に係る緑色発光酸窒化物蛍光体は、波長３００〜４００ｎｍ付近に励起帯がある。
実施例６に係る緑色発光酸窒化物蛍光体は３６０ｎｍに近い位置に発光ピークがあり、実施例７に係る緑色発光酸窒化物蛍光体は３４０ｎｍに近い位置に発光ピークがあり、実施例８に係る緑色発光酸窒化物蛍光体は３３０ｎｍに近い位置に発光ピークがあり、実施例６〜８に係る緑色発光酸窒化物蛍光体は紫外線発光ダイオードに対して効率よく発光する。
また、図６に示されるように、実施例６に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約８３ｎｍ程度であり、実施例７に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約９７ｎｍ程度であり、実施例８に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約１００ｎｍ程度であり、いずれもブロードな発光ピークである。なお、実施例６に係る緑色発光酸窒化物蛍光体は、やや青緑色に発光する一方、実施例８に係る緑色発光酸窒化物蛍光体は、やや黄緑色に発光する。
The excitation spectrum of the green light emitting oxynitride phosphor according to Examples 6 to 8 is shown in FIG. Moreover, the emission spectrum of the green light emission oxynitride fluorescent substance which concerns on Examples 6-8 is shown in FIG.
As shown in FIG. 5, the green light-emitting oxynitride phosphors according to Examples 6 to 8 have an excitation band in the vicinity of a wavelength of 300 to 400 nm.
The green light emitting oxynitride phosphor according to Example 6 has an emission peak at a position close to 360 nm, and the green light emitting oxynitride phosphor according to Example 7 has an emission peak at a position close to 340 nm. The green light emitting oxynitride phosphor has a light emission peak at a position close to 330 nm, and the green light emitting oxynitride phosphors according to Examples 6 to 8 emit light efficiently with respect to the ultraviolet light emitting diode.
Further, as shown in FIG. 6, the green light-emitting oxynitride phosphor according to Example 6 has a half-value width of an emission peak of an emission spectrum of about 83 nm, and the green light-emitting oxynitride fluorescent material according to Example 7 The half-width of the emission peak of the emission spectrum is about 97 nm, and the green emission oxynitride phosphor according to Example 8 has a half-width of the emission peak of the emission spectrum of about 100 nm. Emission peak. Note that the green light-emitting oxynitride phosphor according to Example 6 emits a little blue-green, while the green light-emitting oxynitride phosphor according to Example 8 emits a little yellow-green.
（実施例９〜１１）
実施例９に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ３．１Ｎ３．１である。実施例１０に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．２Ｎ２．４である。実施例１１に係る緑色発光酸窒化物蛍光体は、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０である。
(Examples 9 to 11)
The green light-emitting oxynitride phosphor according to Example 9 has the composition formula Ca 2.97 Eu 0.03 Si 2.4 O 3.1 N 3.1 . The green light-emitting oxynitride phosphor according to Example 10 has the composition formula Ca 2.97 Eu 0.03 Si 2.4 O 4.2 N 2.4 . The green light-emitting oxynitride phosphor according to Example 11 has the composition formula Ca 2.97 Eu 0.03 Si 2.4 O 4.8 N 2.0 .
実施例９に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．５３７６ｇ、酸化ケイ素（ＳｉＯ２）を１．００２２ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．４２００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０８２９ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 The green light-emitting oxynitride phosphor according to Example 9 includes 1.5376 g of calcium nitride (Ca 3 N 2 ), 1.0022 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) as raw material powders. 0.4200 g, europium chloride (EuCl 3 ) 0.0829 g, and ammonium chloride (NH 4 Cl) 0.03 g. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例１０係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．４８６４ｇ、酸化ケイ素（ＳｉＯ２）を１．３０４２ｇ、窒化ケイ素（Ｓｉ３Ｎ４）を０．１４５０ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０８０１ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 10, 1.4864 g of calcium nitride (Ca 3 N 2 ), 1.3042 g of silicon oxide (SiO 2 ), and silicon nitride (Si 3 N 4 ) are used as raw material powders. 0.1450 g, 0.0801 g of europium chloride (EuCl 3 ), and 0.03 g of ammonium chloride (NH 4 Cl) are weighed. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例１１に係る緑色発光酸窒化物蛍光体は、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）を１．４７５９ｇ、酸化ケイ素（ＳｉＯ２）を１．４８００ｇ、塩化ユーロピウム（ＥｕＣｌ３）を０．０７９５ｇ、塩化アンモニウム（ＮＨ４Ｃｌ）を０．０３ｇ秤量する。そしてこれら原料粉末を粉砕混合し、窒化ホウ素坩堝に充填してアンモニア雰囲気下で焼成し、焼成後は徐冷して得られた焼成物を粉砕混合して得た。 In the green light-emitting oxynitride phosphor according to Example 11, 1.4759 g of calcium nitride (Ca 3 N 2 ), 1.4800 g of silicon oxide (SiO 2 ), and 0 of europium chloride (EuCl 3 ) were used as raw powders. 0.095 g and 0.03 g of ammonium chloride (NH 4 Cl) are weighed. These raw material powders were pulverized and mixed, filled into a boron nitride crucible and fired in an ammonia atmosphere. After firing, the fired product obtained by gradual cooling was ground and mixed.
実施例９〜１１に係る緑色発光酸窒化物蛍光体の励起スペクトルを図７に示す。また、実施例９〜１１に係る緑色発光酸窒化物蛍光体の発光スペクトルを図８に示す。
図７に示されるように、実施例９〜１１に係る緑色発光酸窒化物蛍光体は、波長３００〜４００ｎｍ付近に励起帯がある。
実施例９に係る緑色発光酸窒化物蛍光体は３６０ｎｍに近い位置に発光ピークがあり、実施例１０に係る緑色発光酸窒化物蛍光体は３４０ｎｍに近い位置に発光ピークがあり、実施例１１に係る緑色発光酸窒化物蛍光体は３４０ｎｍに近い位置に発光ピークがあり、実施例９〜１１に係る緑色発光酸窒化物蛍光体は紫外線発光ダイオードに対して効率よく発光する。
また、図８に示されるように、実施例９に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約６０ｎｍ程度であり、実施例１０に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約１００ｎｍ程度であり、実施例１１に係る緑色発光酸窒化物蛍光体は、発光スペクトルの発光ピークの半値幅は約１００ｎｍ程度であり、いずれもブロードな発光ピークである。なお、実施例９に係る緑色発光酸窒化物蛍光体は、やや青緑色に発光する。
The excitation spectrum of the green light emitting oxynitride phosphor according to Examples 9 to 11 is shown in FIG. Moreover, the emission spectrum of the green light emission oxynitride fluorescent substance which concerns on Examples 9-11 is shown in FIG.
As shown in FIG. 7, the green light-emitting oxynitride phosphors according to Examples 9 to 11 have an excitation band in the vicinity of a wavelength of 300 to 400 nm.
The green light-emitting oxynitride phosphor according to Example 9 has an emission peak at a position close to 360 nm, and the green light-emitting oxynitride phosphor according to Example 10 has an emission peak at a position close to 340 nm. The green light-emitting oxynitride phosphor has a light emission peak at a position close to 340 nm, and the green light-emitting oxynitride phosphors according to Examples 9 to 11 emit light efficiently with respect to the ultraviolet light-emitting diode.
Further, as shown in FIG. 8, the green light-emitting oxynitride phosphor according to Example 9 has a half-value width of the emission peak of the emission spectrum of about 60 nm, and the green light-emitting oxynitride fluorescence according to Example 10 The half-width of the emission peak of the emission spectrum is about 100 nm, and the half-width of the emission peak of the emission spectrum of the green light emitting oxynitride phosphor according to Example 11 is about 100 nm. Emission peak. Note that the green light emitting oxynitride phosphor according to Example 9 emits light blue-green light.
次に、表１に、上述した実施例１〜１１における蛍光体組成式を一覧として示す。 Next, Table 1 shows a list of phosphor composition formulas in Examples 1 to 11 described above.
次に、表２に実施例１〜１１における蛍光体組成式の組成比、及び、ｘ／（ｗ＋ａ）及びｚ／ｙを示す。 Next, Table 2 shows the composition ratios of the phosphor composition formulas in Examples 1 to 11, and x / (w + a) and z / y.
（緑色発光酸窒化物蛍光体を用いた発光素子）
図９は、本実施例に係る緑色発光酸窒化物蛍光体を用いた発光素子１１１の断面図である。発光素子１１１は、前面に透明基板１０１を備える。また、発光素子１１１は、ドーム状に形成された透明樹脂１０３の内側に発光ダイオード１０５を配置する。
透明樹脂１０３は、エポキシ樹脂、ウレタン樹脂、シリコン樹脂、ポリスチレン樹脂、ポリビニル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、等で構成される。なお、シリコン樹脂若しくはエポキシ樹脂を透明樹脂１０３として用いる方が、蛍光体粉の分散性が良い。
(Light-emitting device using green light-emitting oxynitride phosphor)
FIG. 9 is a cross-sectional view of a light emitting device 111 using the green light emitting oxynitride phosphor according to this example. The light emitting element 111 includes a
The
蛍光体の粉を透明樹脂中に分散させる場合、蛍光体粉と透明樹脂との合計に対するその蛍光体粉の重量割合は、通常０．１〜２０重量％、好ましくは０．３〜１５重量％である。この範囲よりも蛍光体が多すぎると蛍光体粉の凝集により発光効率が低下することがあるからであり、一方、少なすぎると今度は樹脂による光の吸収や散乱のため発光効率が低下することがあるからである。透明樹脂中には、色斑（ムラ）を防止するため増量剤を添加してもよい。
発光ダイオード１０５は紫外線発光ダイオードＩｎＧａＮまたはＧａＮが用いられている。
When the phosphor powder is dispersed in the transparent resin, the weight ratio of the phosphor powder to the total of the phosphor powder and the transparent resin is usually 0.1 to 20% by weight, preferably 0.3 to 15% by weight. It is. If there is too much phosphor within this range, the luminous efficiency may decrease due to aggregation of the phosphor powder. On the other hand, if it is too small, the luminous efficiency will decrease due to light absorption and scattering by the resin. Because there is. In the transparent resin, a bulking agent may be added to prevent color spots (unevenness).
The
透明樹脂１０３にはそれぞれ赤、緑、青色発光の三種類の蛍光体粉末１０２を混入してあり、透明樹脂の表面はミラー１０４として作用するようにミラー加工を施してある。赤色発光蛍光体にはＳｒＳ：Ｅｕを用いる。青色発光蛍光体にはＳｒ５（ＰＯ４）３Ｃｌ：Ｅｕを用いる。そして、緑色発光酸窒化物蛍光体にはＣａ８．９７Ｅｕ０．０３Ｓｉ８Ｏ１０Ｎ１０を用いる。
赤、緑、青色の各色発光の蛍光体はその紫外線発光ダイオード１０５に励起されて、これにより透明基板１０１から白色光が放射される。そのため、発光素子１１１は白色発光素子である。
The
The phosphors that emit red, green, and blue light are excited by the ultraviolet
なお、透明樹脂１０３に拡散剤を含有させることにより、紫外線発光ダイオード１０５からの指向性を緩和させて視野角をさらに増大させることも可能である。拡散剤としては、チタン酸バリウム、酸化チタン、酸化アルミニウム、酸化ケイ素等を用いることができる。さらに透明樹脂１０３はドーム状に形成されるが、これを所望の形状に形成することにより、紫外線発光ダイオード１０５からの発光を収束させたり拡散させたり等のレンズ効果をもたらすことが可能である。
In addition, by including a diffusing agent in the
（その他の実施形態）
なお、本実施例に係る発光素子は、暖色系や寒色系等の色調の光を発光する発光素子としてもよい。勿論、緑色単色の発光素子としてもよい。
(Other embodiments)
The light emitting element according to this embodiment may be a light emitting element that emits light of a color tone such as a warm color or a cold color. Of course, a green light-emitting element may be used.
上述の実施例では、組成式Ｃａ８．９７Ｅｕ０．０３Ｓｉ８．０Ｏ１０Ｎ１０（実施例１）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６（実施例２）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ４．５Ｎ３．０（実施例３）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ５．４Ｎ２．４（実施例４）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ６．０Ｎ２．０（実施例５）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．７Ｏ３．４Ｎ３．４（実施例６）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．７Ｏ３．９Ｎ３．０（実施例７）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．７Ｏ４．８Ｎ２．４（実施例８）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ３．１Ｎ３．１（実施例９）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．２Ｎ２．４（実施例１０）、組成式Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０（実施例１１）の緑色発光酸窒化物蛍光体について、紫外線発光ダイオードに対して効率よく発光することを示した。 In the above-described examples, the composition formula Ca 8.97 Eu 0.03 Si 8.0 O 10 N 10 (Example 1), the composition formula Ca 2.97 Eu 0.03 Si 3.0 O 3.6 N 3 .6 (Example 2), composition formula Ca 2.97 Eu 0.03 Si 3.0 O 4.5 N 3.0 (Example 3), composition formula Ca 2.97 Eu 0.03 Si 3.0 O 5.4 N 2.4 (Example 4), compositional formula Ca 2.97 Eu 0.03 Si 3.0 O 6.0 N 2.0 (Example 5), compositional formula Ca 2.97 Eu 0 .03 Si 2.7 O 3.4 N 3.4 (Example 6), composition formula Ca 2.97 Eu 0.03 Si 2.7 O 3.9 N 3.0 (Example 7), composition formula Ca 2.97 Eu 0.03 Si 2.7 O 4.8 N 2.4 (Example 8), composition formula Ca 2.97 Eu 0.03 Si 2 .4 O 3.1 N 3.1 (Example 9), compositional formula Ca 2.97 Eu 0.03 Si 2.4 O 4.2 N 2.4 (Example 10), compositional formula Ca 2.97 The green light emitting oxynitride phosphor of Eu 0.03 Si 2.4 O 4.8 N 2.0 (Example 11) was shown to emit light efficiently with respect to the ultraviolet light emitting diode.
同様に、（Ｃａ２．９７Ｅｕ０．０３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｅｕ０．０３Ｚｒ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｅｕ０．０３Ｔｉ３．０Ｏ３．６Ｎ３．６）、（Ｂａ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｂａ２．９７Ｅｕ０．０３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｂａ２．９７Ｅｕ０．０３Ｚｒ３．０Ｏ３．６Ｎ３．６）、（Ｂａ２．９７Ｅｕ０．０３Ｔｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｒ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｒ２．９７Ｅｕ０．０３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｓｒ２．９７Ｅｕ０．０３Ｚｒ３．０Ｏ３．６Ｎ３．６）、（Ｓｒ２．９７Ｅｕ０．０３Ｔｉ３．０Ｏ３．６Ｎ３．６）、（Ｍｇ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｍｇ２．９７Ｅｕ０．０３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｍｇ２．９７Ｅｕ０．０３Ｚｒ３．０Ｏ３．６Ｎ３．６）、（Ｍｇ２．９７Ｅｕ０．０３Ｔｉ３．０Ｏ３．６Ｎ３．６）、（Ｚｎ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｚｎ２．９７Ｅｕ０．０３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｚｎ２．９７Ｅｕ０．０３Ｚｒ３．０Ｏ３．６Ｎ３．６）、（Ｚｎ２．９７Ｅｕ０．０３Ｔｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｎ２．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｎ２．９７Ｅｕ０．０３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｓｎ２．９７Ｅｕ０．０３Ｚｒ３．０Ｏ３．６Ｎ３．６）、（Ｓｎ２．９７Ｅｕ０．０３Ｔｉ３．０Ｏ３．６Ｎ３．６）等についても、紫外線発光ダイオードに対して効率よく発光する。
Similarly, (Ca 2.97 Eu 0.03 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.97 Eu 0.03 Zr 3.0 O 3.6 N 3.6 ), ( Ca 2.97 Eu 0.03 Ti 3.0 O 3.6 N 3.6 ), (Ba 2.97 Eu 0.03 Si 3.0 O 3.6 N 3.6 ), (Ba 2.97 Eu 0.03 Ge 3.0 O 3.6 N 3.6 ), (Ba 2.97 Eu 0.03 Zr 3.0 O 3.6 N 3.6 ), (Ba 2.97 Eu 0.03 Ti 3.0 O 3.6 N 3.6 ), (Sr 2.97 Eu 0.03 Si 3.0 O 3.6 N 3.6 ), (Sr 2.97 Eu 0.03 Ge 3.0 O 3.6 N 3.6), (Sr 2.97 Eu 0.03 Zr 3.0 O 3.6 N 3.6), (Sr 2.97 Eu 0.03 T 3.0 O 3.6 N 3.6), ( Mg 2.97 Eu 0.03 Si 3.0 O 3.6 N 3.6), (Mg 2.97 Eu 0.03 Ge 3.0 O 3.6 N 3.6 ), (Mg 2.97 Eu 0.03 Zr 3.0 O 3.6 N 3.6 ), (Mg 2.97 Eu 0.03 Ti 3.0 O 3.6 N 3.6 ), (Zn 2.97 Eu 0.03 Si 3.0 O 3.6 N 3.6 ), (Zn 2.97 Eu 0.03 Ge 3.0 O 3.6 N 3.6 ) (Zn 2.97 Eu 0.03 Zr 3.0 O 3.6 N 3.6 ), (Zn 2.97 Eu 0.03 Ti 3.0 O 3.6 N 3.6 ), (Sn 2 .97 Eu 0.03 Si 3.0 O 3.6 N 3.6), (Sn 2.97 Eu 0.03 Ge 3.0 O 3.6 N 3.6), (
また、（Ｃａ２．９７Ｅｕ０．０３Ｇｅ２．４Ｏ４．８Ｎ２．０）、（Ｃａ２．９７Ｅｕ０．０３Ｚｒ２．４Ｏ４．８Ｎ２．０）、（Ｃａ２．９７Ｅｕ０．０３Ｔｉ２．４Ｏ４．８Ｎ２．０）、（Ｂａ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０）、（Ｂａ２．９７Ｅｕ０．０３Ｇｅ２．４Ｏ４．８Ｎ２．０）、（Ｂａ２．９７Ｅｕ０．０３Ｚｒ２．４Ｏ４．８Ｎ２．０）、（Ｂａ２．９７Ｅｕ０．０３Ｔｉ２．４Ｏ４．８Ｎ２．０）、（Ｓｒ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０）、（Ｓｒ２．９７Ｅｕ０．０３Ｇｅ２．４Ｏ４．８Ｎ２．０）、（Ｓｒ２．９７Ｅｕ０．０３Ｚｒ２．４Ｏ４．８Ｎ２．０）、（Ｓｒ２．９７Ｅｕ０．０３Ｔｉ２．４Ｏ４．８Ｎ２．０）、（Ｍｇ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０）、（Ｍｇ２．９７Ｅｕ０．０３Ｇｅ２．４Ｏ４．８Ｎ２．０）、（Ｍｇ２．９７Ｅｕ０．０３Ｚｒ２．４Ｏ４．８Ｎ２．０）、（Ｍｇ２．９７Ｅｕ０．０３Ｔｉ２．４Ｏ４．８Ｎ２．０）、（Ｚｎ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０）、（Ｚｎ２．９７Ｅｕ０．０３Ｇｅ２．４Ｏ４．８Ｎ２．０）、（Ｚｎ２．９７Ｅｕ０．０３Ｚｒ２．４Ｏ４．８Ｎ２．０）、（Ｚｎ２．９７Ｅｕ０．０３Ｔｉ２．４Ｏ４．８Ｎ２．０）、（Ｓｎ２．９７Ｅｕ０．０３Ｓｉ２．４Ｏ４．８Ｎ２．０）、（Ｓｎ２．９７Ｅｕ０．０３Ｇｅ２．４Ｏ４．８Ｎ２．０）、（Ｓｎ２．９７Ｅｕ０．０３Ｚｒ２．４Ｏ４．８Ｎ２．０）、（Ｓｎ２．９７Ｅｕ０．０３Ｔｉ２．４Ｏ４．８Ｎ２．０）等についても、紫外線発光ダイオードに対して効率よく発光する。
Moreover, (Ca 2.97 Eu 0.03 Ge 2.4 O 4.8 N 2.0 ), (Ca 2.97 Eu 0.03 Zr 2.4 O 4.8 N 2.0 ), (Ca 2.97 Eu 0.03 Ti 2.4 O 4.8 N 2.0 ), (Ba 2.97 Eu 0.03 Si 2.4 O 4.8 N 2.0 ), (Ba 2.97 Eu 0.03 Ge 2.4 O 4.8 N 2.0 ), (Ba 2.97 Eu 0.03 Zr 2.4 O 4.8 N 2.0 ), (Ba 2.97 Eu 0.03 Ti 2.4 O 4.8 N 2.0 ), (Sr 2.97 Eu 0.03 Si 2.4 O 4.8 N 2.0 ), (Sr 2.97 Eu 0.03 Ge 2.4 O 4.8 N 2.0), (Sr 2.97 Eu 0.03 Zr 2.4 O 4.8 N 2.0), (Sr 2.97 Eu 0.03 Ti .4 O 4.8 N 2.0), ( Mg 2.97 Eu 0.03 Si 2.4 O 4.8 N 2.0), (Mg 2.97 Eu 0.03 Ge 2.4 O 4 .8 N 2.0 ), (Mg 2.97 Eu 0.03 Zr 2.4 O 4.8 N 2.0 ), (Mg 2.97 Eu 0.03 Ti 2.4 O 4.8 N 2 0.0 ), (Zn 2.97 Eu 0.03 Si 2.4 O 4.8 N 2.0 ), (Zn 2.97 Eu 0.03 Ge 2.4 O 4.8 N 2.0 ), (Zn 2.97 Eu 0.03 Zr 2.4 O 4.8 N 2.0 ), (Zn 2.97 Eu 0.03 Ti 2.4 O 4.8 N 2.0 ), (Sn 2. 97 Eu 0.03 Si 2.4 O 4.8 N 2.0), (Sn 2.97 Eu 0.03 Ge 2.4 O 4.8 N 2.0), (
また、（Ｃａ２．９９Ｅｕ０．０１Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９５Ｅｕ０．０５Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９３Ｅｕ０．０７Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９０Ｅｕ０．１０Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．８７Ｅｕ０．１３Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．８５Ｅｕ０．１５Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．８３Ｅｕ０．１７Ｇｅ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．８０Ｅｕ０．２０Ｇｅ３．０Ｏ３．６Ｎ３．６）等についても、紫外線発光ダイオードに対して効率よく発光する。 Moreover, (Ca 2.99 Eu 0.01 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.95 Eu 0.05 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.93 Eu 0.07 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.90 Eu 0.10 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.87 Eu 0.13 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.85 Eu 0.15 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.83 Eu 0.17 Ge 3.0 O 3.6 N 3.6 ), (Ca 2.80 Eu 0.20 Ge 3.0 O 3.6 N 3.6 ) and the like also emit light efficiently with respect to the ultraviolet light emitting diode.
また、付活剤はＥｕについて示したものであるが、付活剤がＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｍｎ、Ｂｉ、Ｓｂであっても本実施例に係る緑色発光酸窒化物蛍光体は紫外線発光ダイオードに対して効率よく発光する。
例えば、（Ｃａ２．９７Ｌａ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｃｅ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｐｒ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｎｄ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｓｍ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｇｄ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｔｂ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｄｙ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｈｏ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｅｒ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｔｍ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｙｂ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｌｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｍｎ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｂｉ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｓｂ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）等についても、紫外線発光ダイオードに対して効率よく発光する。
Further, the activator is shown for Eu, but the activator is La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Bi, Sb. Even so, the green light emitting oxynitride phosphor according to the present embodiment emits light efficiently with respect to the ultraviolet light emitting diode.
For example, (Ca 2.97 La 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Ce 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Pr 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Nd 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Sm 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Gd 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Tb 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Dy 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Ho 0.03 Si 3.0 O 3.6 N 3.6), (Ca 2.97 Er 0.03 Si 3.0 O 3.6 N 3.6), (Ca 2.97 Tm 0.03 S 3.0 O 3.6 N 3.6), ( Ca 2.97 Yb 0.03 Si 3.0 O 3.6 N 3.6), (Ca 2.97 Lu 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Mn 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Bi 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Sb 0.03 Si 3.0 O 3.6 N 3.6 ) and the like also emit light efficiently with respect to the ultraviolet light emitting diode.
また、Ｍ１とＭ２は、複数の金属を含有することも可能である。例えば、（Ｂａ１．０Ｃａ１．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｒ１．０Ｃａ１．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｎ１．０Ｃａ１．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．０Ｇｅ１．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．０Ｚｒ１．０Ｏ３．６Ｎ３．６）、（Ｃａ２．９７Ｅｕ０．０３Ｓｉ２．０Ｔｉ１．０Ｏ３．６Ｎ３．６）、（Ｂａ１．０Ｓｒ１．０Ｃａ０．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｒ１．０Ｍｇ１．０Ｃａ１．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｓｎ１．０Ｚｎ１．０Ｃａ１．９７Ｅｕ０．０３Ｓｉ３．０Ｏ３．６Ｎ３．６）、（Ｂａ１．０Ｓｒ１．０Ｃａ０．９７Ｅｕ０．０３Ｓｉ２．０Ｇｅ１．０Ｏ３．６Ｎ３．６）、（Ｓｒ１．０Ｍｇ１．０Ｃａ１．９７Ｅｕ０．０３Ｓｉ２．０Ｚｒ１．０Ｏ３．６Ｎ３．６）等についても、紫外線発光ダイオードに対して効率よく発光する。 M1 and M2 can also contain a plurality of metals. For example, (Ba 1.0 Ca 1.97 Eu 0.03 Si 3.0 O 3.6 N 3.6 ), (Sr 1.0 Ca 1.97 Eu 0.03 Si 3.0 O 3.6) N 3.6 ), (Sn 1.0 Ca 1.97 Eu 0.03 Si 3.0 O 3.6 N 3.6 ), (Ca 2.97 Eu 0.03 Si 2.0 Ge 1.0 O 3.6 N 3.6 ), (Ca 2.97 Eu 0.03 Si 2.0 Zr 1.0 O 3.6 N 3.6 ), (Ca 2.97 Eu 0.03 Si 2.0 Ti 1.0 O 3.6 N 3.6 ), (Ba 1.0 Sr 1.0 Ca 0.97 Eu 0.03 Si 3.0 O 3.6 N 3.6 ), (Sr 1.0 mg 1.0 Ca 1.97 Eu 0.03 Si 3.0 O 3.6 N 3.6), (Sn 1.0 Zn 1.0 Ca 1.97 Eu .03 Si 3.0 O 3.6 N 3.6) , (Ba 1.0 Sr 1.0 Ca 0.97 Eu 0.03 Si 2.0 Ge 1.0 O 3.6 N 3.6) , (Sr 1.0 Mg 1.0 Ca 1.97 Eu 0.03 Si 2.0 Zr 1.0 O 3.6 N 3.6 ) and the like also emit light efficiently with respect to the ultraviolet light emitting diode.
また、上述の実施例では、原料粉末として、窒化カルシウム（Ｃａ３Ｎ２）と、酸化ケイ素（ＳｉＯ２）と、窒化ケイ素（Ｓｉ３Ｎ４）と、塩化ユーロピウム（ＥｕＣｌ３）と、を混合させた。もっとも、本発明に係る緑色発光酸窒化物蛍光体はかかる実施例に限定されない。カルシウム化合物としては、炭酸カルシウム（ＣａＣＯ３）、亜塩素酸カルシウム（Ｃａ（ＣｌＯ２）２）、亜硫酸カルシウム（ＣａＳＯ３）、亜リン酸カルシウム（ＣａＰＨＯ３）、アルミノケイ酸一カルシウム（ＣａＯ・Ａｌ２Ｏ３）、過塩素酸カルシウム（Ｃａ（ＣｌＯ４）２）等を用いることも可能である。
また、原料粉末として、カルシウム化合物の代わりに、炭酸バリウム（ＢａＣＯ３）や硫酸バリウム（ＢａＳＯ４）、塩化バリウム（ＢａＣｌ２）、硝酸バリウム（ＢａＮＯ３）、水酸化バリウム（Ｂａ（ＯＨ）２）、過酸化バリウム等のバリウム化合物を用いることも可能である。
また、原料粉末として、カルシウム化合物の代わりに、炭酸ストロンチウム（ＳｒＣＯ３）や硫酸ストロンチウム（ＳｒＳＯ４）、臭化ストロンチウム（ＳｒＢｒ）等のストロンチウム化合物を用いることも可能である。
さらには、これらのカルシウム化合物、ストロンチウム化合物及びバリウム化合物を混合して用いることも可能である。
また、原料粉末として、カルシウム化合物の代わりに、炭酸マグネシウム（ＭｇＣＯ３）や硫酸マグネシウム（ＭｇＳＯ４）、臭化マグネシウム（ＭｇＢｒ２）等のマグネシウム化合物を用いることも可能である。
また、原料粉末として、カルシウム化合物の代わりに、塩化亜鉛（ＺｎＣｌ２）、炭酸亜鉛（ＺｎＣＯ３）、硫酸亜鉛（ＺｎＳＯ４）、臭化亜鉛（ＺｎＢｒ２）等の亜鉛化合物を用いることも可能である。
また、原料粉末として、カルシウム化合物の代わりに、塩化スズ（ＳｎＣｌ２）、硫酸スズ（ＳｎＳＯ４）等のスズ化合物を用いることも可能である。
さらには、これらのカルシウム化合物、バリウム化合物、ストロンチウム化合物、マグネシウム化合物、亜鉛化合物及びスズ化合物を混合して用いることも可能である。
In the above-described embodiment, calcium nitride (Ca 3 N 2 ), silicon oxide (SiO 2 ), silicon nitride (Si 3 N 4 ), and europium chloride (EuCl 3 ) are mixed as the raw material powder. I let you. But the green light emission oxynitride fluorescent substance which concerns on this invention is not limited to this Example. Examples of calcium compounds include calcium carbonate (CaCO 3 ), calcium chlorite (Ca (ClO 2 ) 2 ), calcium sulfite (CaSO 3 ), calcium phosphite (CaHO 3 ), monocalcium aluminosilicate (CaO · Al 2 O 3). ), Calcium perchlorate (Ca (ClO 4 ) 2 ), or the like can also be used.
In addition, as a raw material powder, instead of a calcium compound, barium carbonate (BaCO 3 ), barium sulfate (BaSO 4 ), barium chloride (BaCl 2 ), barium nitrate (BaNO 3 ), barium hydroxide (Ba (OH) 2 ) It is also possible to use barium compounds such as barium peroxide.
Moreover, it is also possible to use strontium compounds such as strontium carbonate (SrCO 3 ), strontium sulfate (SrSO 4 ), and strontium bromide (SrBr) instead of the calcium compound as the raw material powder.
Furthermore, these calcium compounds, strontium compounds, and barium compounds can be mixed and used.
As the raw material powder, magnesium compounds such as magnesium carbonate (MgCO 3 ), magnesium sulfate (MgSO 4 ), and magnesium bromide (MgBr 2 ) can be used instead of the calcium compound.
In addition, zinc compounds such as zinc chloride (ZnCl 2 ), zinc carbonate (ZnCO 3 ), zinc sulfate (ZnSO 4 ), and zinc bromide (ZnBr 2 ) can be used as the raw material powder instead of the calcium compound. is there.
Moreover, it is also possible to use tin compounds such as tin chloride (SnCl 2 ) and tin sulfate (SnSO 4 ) instead of the calcium compound as the raw material powder.
Furthermore, these calcium compounds, barium compounds, strontium compounds, magnesium compounds, zinc compounds, and tin compounds can be mixed and used.
また、酸化ケイ素（ＳｉＯ２）の代わりに、一酸化ゲルマニウム（ＧｅＯ）や二酸化ゲルマニウム（ＧｅＯ２）、酸化ジルコニウム（ＺｒＯ２）、酸化チタン（ＴｉＯ２）を用いることもできる。さらには、これらの酸化物を混合して用いることも可能である。 Further, germanium monoxide (GeO), germanium dioxide (GeO 2 ), zirconium oxide (ZrO 2 ), or titanium oxide (TiO 2 ) can be used instead of silicon oxide (SiO 2 ). Furthermore, it is also possible to use a mixture of these oxides.
また、窒化ケイ素（Ｓｉ３Ｎ４）の代わりに、窒化ゲルマニウム（Ｇｅ３Ｎ４）、窒化ジルコニウム（ＺｒＮ）、窒化チタン（ＴｉＮ）を用いることもできる。さらには、これらの窒化物を混合して用いることも可能である。 Further, germanium nitride (Ge 3 N 4 ), zirconium nitride (ZrN), and titanium nitride (TiN) can be used instead of silicon nitride (Si 3 N 4 ). Furthermore, it is also possible to use a mixture of these nitrides.
上述の実施例では、付活剤として塩化ユーロピウム（ＥｕＣｌ３）を用いた。もっともこれに限定されない。塩化ランタン、硝酸ランタン、硝酸セリウム、塩化セリウム、硝酸第１セリウムアンモニウム、硝酸２アンモニウムセリウム、酸化プラセオジム、塩化プラセオジム、塩化ネオジム、酸化ネオジム、塩化サマリウム、塩化ガドリニウム、酸化ガドリニウム、塩化テルビウム、酸化テルビウム、塩化ジスプロシウム、酸化ジスプロシウム、塩化ホルミニウム、酸化ホルミニウム、酸化エルビウム、塩化ツリウム、酸化ツリウム、酸化イッテルビウム、塩化イッテルビウム、酸化ルテチウム、塩化マンガン、硝酸マンガン、硫酸マンガン、炭酸マンガン、硫酸ビスマス、酸化ビスマス、水酸化ビスマス、三塩化アンチモン、五酸化アンチモン、三酸化アンチモン、硫酸アンチモン等を用いることができる。 In the above examples, europium chloride (EuCl 3 ) was used as an activator. However, it is not limited to this. Lanthanum chloride, lanthanum nitrate, cerium nitrate, cerium chloride, ceric ammonium nitrate, diammonium cerium nitrate, praseodymium oxide, praseodymium chloride, neodymium chloride, neodymium oxide, samarium chloride, gadolinium chloride, gadolinium oxide, terbium chloride, terbium oxide, Dysprosium chloride, dysprosium oxide, holmium chloride, holmium oxide, erbium oxide, thulium chloride, thulium oxide, ytterbium oxide, ytterbium chloride, lutetium oxide, manganese chloride, manganese nitrate, manganese sulfate, manganese carbonate, bismuth sulfate, bismuth oxide, hydroxide Bismuth, antimony trichloride, antimony pentoxide, antimony trioxide, antimony sulfate, and the like can be used.
上述の実施例に係る発光素子１１１では、赤色発光蛍光体にはＳｒＳ：Ｅｕを、青色発光蛍光体にはＳｒ５（ＰＯ４）３Ｃｌ：Ｅｕを、緑色発光酸窒化物蛍光体にはＣａ８．９７Ｅｕ０．０３Ｓｉ８Ｏ１０Ｎ１０を用いた。
もっとも、これに限定されない。赤色発光蛍光体には、ＣａＳ：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ及びＬａ２Ｏ２Ｓ：Ｅｕ等を用いることができる。また、青色発光蛍光体は、（Ｂａ，Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｅｕ，Ｍｎ、（Ｂａ，Ｓｒ，Ｃａ，Ｍｇ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ及びＺｎＳ：Ａｇ等を用いることができる。さらに、緑色発光酸窒化物蛍光体には、本実施例に係る種々の緑色発光酸窒化物蛍光体を用いることができる。
In the light emitting device 111 according to the above-described embodiment, SrS: Eu is used for the red light emitting phosphor, Sr 5 (PO 4 ) 3 Cl: Eu is used for the blue light emitting phosphor, and Ca is used for the green light emitting oxynitride phosphor. 8.97 Eu 0.03 Si 8 O 10 N 10 was used.
However, it is not limited to this. As the red light emitting phosphor, CaS: Eu, CaAlSiN 3 : Eu, La 2 O 2 S: Eu, or the like can be used. As the blue light emitting phosphor , (Ba, Sr) MgAl 10 O 17 : Eu, Mn, (Ba, Sr, Ca, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, ZnS: Ag, or the like may be used. it can. Furthermore, various green light emitting oxynitride phosphors according to the present embodiment can be used as the green light emitting oxynitride phosphor.
さらに、発光素子１１１では、本実施例に係る緑色発光酸窒化物蛍光体に加えて、以下に示す緑色発光酸窒化物蛍光体を混合して使用することも可能である。例えば、ＢａＭｇ２Ａｌ１６Ｏ２７：Ｅｕ、ＭｎやＢａＭｇＡｌ１０Ｏ１７：Ｅｕ、Ｍｎで表されるユーロピウム付活アルミン酸塩蛍光体、（ＭｇＣａＳｒＢａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕで表されるユーロピウム付活アルカリ土類シリコンオキシナイトライド系蛍光体、Ｂａ２ＳｉＯ４：Ｅｕで表されるユーロピウム付活アルカリ土類金属珪酸塩系蛍光体等を、本実施例に係る緑色発光酸窒化物蛍光体に加えて使用することも可能である。 Furthermore, in the light emitting element 111, in addition to the green light emitting oxynitride phosphor according to the present embodiment, the following green light emitting oxynitride phosphor can be mixed and used. For example, europium-activated aluminate phosphor represented by BaMg 2 Al 16 O 27 : Eu, Mn, BaMgAl 10 O 17 : Eu, Mn, europium represented by (MgCaSrBa) Si 2 O 2 N 2 : Eu Activated alkaline earth silicon oxynitride phosphor, europium activated alkaline earth metal silicate phosphor represented by Ba 2 SiO 4 : Eu, etc., green light emitting oxynitride phosphor according to this example It is also possible to use it in addition to.
上述の実施例では、原料粉末を乾式で混合した。もっとも湿式で混合することも可能である。湿式で混合するためにアセトン、ＩＰＡ（イソプロピルアルコール）、エタノール等の有機溶媒を用いる。水で混合することも可能であるが、有機溶媒を用いることが好ましい。アセトン等の有機溶媒と秤量した原料とに、さらにジルコニアボールを加えて、セラミックス製ボールミルに入れ、１２時間混合する。混合時間は１時間以上２４時間以下の範囲で行うことが好ましい。混合が終了するとジルコニアボールを篩により分離させ、その後、有機溶媒を乾燥させ、原料粉末を得る。なお、カルシウム化合物としての窒化カルシウム（Ｃａ３Ｎ２）は乾式混合の時のみ使用可能であるため、炭酸カルシウム（ＣａＣＯ３）、亜塩素酸カルシウム（Ｃａ（ＣｌＯ２）２）等の他のカルシウム化合物を用いる。 In the above-described examples, the raw material powders were mixed by a dry method. It is also possible to mix in a wet manner. An organic solvent such as acetone, IPA (isopropyl alcohol) or ethanol is used for wet mixing. Although mixing with water is possible, it is preferable to use an organic solvent. A zirconia ball is further added to an organic solvent such as acetone and the weighed raw material, and the mixture is placed in a ceramic ball mill and mixed for 12 hours. The mixing time is preferably in the range of 1 hour to 24 hours. When mixing is completed, the zirconia balls are separated by a sieve, and then the organic solvent is dried to obtain a raw material powder. Since calcium nitride (Ca 3 N 2 ) as a calcium compound can be used only during dry mixing, other calcium such as calcium carbonate (CaCO 3 ), calcium chlorite (Ca (ClO 2 ) 2 ), etc. Use compounds.
上述の実施例では、紫外線発光ダイオードとしてＩｎＧａＮまたはＧａＮが用いられた。もっともこれに限定されない。発光素子を形成するための発光ダイオードとしては、ＩｎＡｌＧａＮ、ＡｌＧａＮ、ＢＡｌＧａＮ、ＢＩｎＡｌＧａＮ等を用いることが可能である。 In the above embodiment, InGaN or GaN is used as the ultraviolet light emitting diode. However, it is not limited to this. As a light emitting diode for forming a light emitting element, InAlGaN, AlGaN, BAlGaN, BInAlGaN, or the like can be used.
本実施例に係る緑色発光酸窒化物蛍光体の製造方法において、あらかじめ、窒化ケイ素（Ｓｉ３Ｎ４）と酸化ケイ素（ＳｉＯ２）を０．９ＭＰａの圧力下で反応させてＳｉ−Ｏ−Ｎ系前駆体を合成し、その後に、窒化カルシウム（Ｃａ３Ｎ２）と塩化ユーロピウム（ＥｕＣｌ３）とを混合させて原料粉末を得て、その原料粉末を焼成することも可能である。
原料に窒化ケイ素（Ｓｉ３Ｎ４）を用いる場合、１３００℃以上の高温で焼成すると窒化ケイ素（Ｓｉ３Ｎ４）の分解飛散する場合がある。窒化ケイ素（Ｓｉ３Ｎ４）が分解飛散すると、目的とする組成の蛍光体を得ることが困難であり、高純度な緑色発光酸窒化物蛍光体が得られない可能性がある。そこで、窒化ケイ素（Ｓｉ３Ｎ４）の分解飛散による蛍光体純度の低下を抑制するために、あらかじめ（Ｓｉ３Ｎ４）と酸化ケイ素（ＳｉＯ２）を０．９ＭＰａの圧力下で反応させてＳｉ−Ｏ−Ｎ系前駆体を合成するのである。
In the method for producing a green light-emitting oxynitride phosphor according to the present example, silicon nitride (Si 3 N 4 ) and silicon oxide (SiO 2 ) are reacted in advance under a pressure of 0.9 MPa to obtain Si—O—N. It is also possible to synthesize a system precursor, and then mix calcium nitride (Ca 3 N 2 ) and europium chloride (EuCl 3 ) to obtain a raw material powder, and to fire the raw material powder.
When silicon nitride (Si 3 N 4 ) is used as a raw material, silicon nitride (Si 3 N 4 ) may be decomposed and scattered when fired at a high temperature of 1300 ° C. or higher. When silicon nitride (Si 3 N 4 ) decomposes and disperses, it is difficult to obtain a phosphor having the target composition, and a high-purity green light-emitting oxynitride phosphor may not be obtained. Therefore, in order to suppress a decrease in phosphor purity due to decomposition and scattering of silicon nitride (Si 3 N 4 ), (Si 3 N 4 ) and silicon oxide (SiO 2 ) are reacted in advance under a pressure of 0.9 MPa. A Si—O—N precursor is synthesized.
１０１ 透明基板
１０２ 三種類の蛍光体粉末
１０３ 透明樹脂
１０４ ミラー
１０５ 発光ダイオード
１１１ 実施例に係る発光素子
DESCRIPTION OF
Claims (5)
（ここで、
０．０１≦ａ≦０．２０、
０．８≦ｘ／（ｗ＋ａ）≦０．９、
０＜ｚ／ｙ＜１．０、
１．１≦ｗ／ｘ≦１．２４、
０．５≦ｘ／ｙ≦０．６９、
０．９≦ｘ／ｚ≦１．２）
で表され、緑色帯域の発光波長を有することを特徴とする、緑色発光酸窒化物蛍光体。 General formula Ca w Eu a Si x O y N z
(here,
0.01 ≦ a ≦ 0.20,
0.8 ≦ x / (w + a) ≦ 0.9,
0 <z / y <1.0,
1.1 ≦ w / x ≦ 1.24
0.5 ≦ x / y ≦ 0.69 ,
0.9 ≦ x / z ≦ 1.2)
A green light emitting oxynitride phosphor represented by the formula (1) and having a light emission wavelength in the green band.
ことを特徴とする請求項１に記載の緑色発光酸窒化物蛍光体。 The green light emitting oxynitride phosphor has an excitation band at a wavelength of 300 nm to 400 nm,
The green light-emitting oxynitride phosphor according to claim 1.
蛍光体の励起光源としての紫外線発光ダイオードと、
を有することを特徴とする発光素子。 The green light-emitting oxynitride phosphor according to claim 1 or 2,
An ultraviolet light emitting diode as an excitation light source of the phosphor;
A light-emitting element including:
を有することを特徴とする請求項３記載の発光素子。 A red-emitting phosphor, a blue-emitting phosphor,
The light emitting device according to claim 3, wherein:
前記青色発光蛍光体は、（Ｂａ，Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｅｕ，Ｍｎ、（Ｂａ，Ｓｒ，Ｃａ，Ｍｇ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ、Ｓｒ５（ＰＯ４）３Ｃｌ：Ｅｕ及びＺｎＳ：Ａｇのうち少なくともいずれか一つを含有する、
ことを特徴とする請求項４記載の発光素子。 The red light-emitting phosphor contains at least one of SrS: Eu, CaS: Eu, CaAlSiN 3 : Eu, and La 2 O 2 S: Eu,
The blue light-emitting phosphor includes (Ba, Sr) MgAl 10 O 17 : Eu, Mn, (Ba, Sr, Ca, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, Sr 5 (PO 4 ) 3 Cl: Eu and ZnS: containing at least one of Ag:
The light-emitting element according to claim 4.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007167007A JP5710089B2 (en) | 2007-06-25 | 2007-06-25 | Green light emitting oxynitride phosphor and light emitting device using the same |
| TW097122124A TW200904946A (en) | 2007-06-25 | 2008-06-13 | Green light-emitting fluorescent substance, method of manufacturing the same and light-emitting device using the same |
| KR1020080059739A KR20080114561A (en) | 2007-06-25 | 2008-06-24 | Green light-emitting fluorescent substance, method of manufacturing the same and light-emitting device using the same |
| CN2008101306057A CN101333440B (en) | 2007-06-25 | 2008-06-25 | Green light-emission fluorescent material, manufacturing method thereof and lighting device using same |
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| JP2007167007A JP5710089B2 (en) | 2007-06-25 | 2007-06-25 | Green light emitting oxynitride phosphor and light emitting device using the same |
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| JP2013207617A Division JP2013256675A (en) | 2013-10-02 | 2013-10-02 | Green emission oxynitride phosphor |
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| JP5710089B2 true JP5710089B2 (en) | 2015-04-30 |
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| JP (1) | JP5710089B2 (en) |
| KR (1) | KR20080114561A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI404240B (en) * | 2009-02-06 | 2013-08-01 | Everlight Electronics Co Ltd | Colorful light-emitting apparatus |
| JP5515141B2 (en) * | 2009-03-16 | 2014-06-11 | Ｎｅｃライティング株式会社 | Phosphor and fluorescent lamp |
| JP5515142B2 (en) * | 2009-03-16 | 2014-06-11 | Ｎｅｃライティング株式会社 | Phosphor and fluorescent lamp |
| WO2011019191A2 (en) * | 2009-08-10 | 2011-02-17 | 엘지이노텍주식회사 | Phosphor, preparation method thereof, and white light emitting device |
| KR101163902B1 (en) | 2010-08-10 | 2012-07-09 | 엘지이노텍 주식회사 | Light emitting device |
| US9909058B2 (en) | 2009-09-02 | 2018-03-06 | Lg Innotek Co., Ltd. | Phosphor, phosphor manufacturing method, and white light emitting device |
| TWI456027B (en) * | 2010-03-03 | 2014-10-11 | Hitachi Ltd | Closed material sheet with wavelength conversion material and solar cell using the same |
| KR101441485B1 (en) * | 2013-09-17 | 2014-09-17 | 한국과학기술연구원 | Green-emitting upconversion nanophosphor and synthesis method thereof |
| JP2013256675A (en) * | 2013-10-02 | 2013-12-26 | Nec Lighting Ltd | Green emission oxynitride phosphor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0790263A (en) * | 1993-09-28 | 1995-04-04 | Toshiba Corp | Fluorescent material for color picture tube and production thereof |
| JP2000212556A (en) * | 1998-11-19 | 2000-08-02 | Ohara Inc | Luminous phosphor, and luminous fluorescent powder, and their production |
| JP3609365B2 (en) * | 2001-10-19 | 2005-01-12 | 株式会社東芝 | Semiconductor light emitting device |
| EP1413618A1 (en) * | 2002-09-24 | 2004-04-28 | Osram Opto Semiconductors GmbH | Luminescent material, especially for LED application |
| AU2003263562A1 (en) * | 2002-10-14 | 2004-05-04 | Koninklijke Philips Electronics N.V. | Light-emitting device comprising an eu(ii)-activated phosphor |
| JP4415548B2 (en) * | 2002-10-16 | 2010-02-17 | 日亜化学工業株式会社 | Light emitting device using oxynitride phosphor |
| JP4466447B2 (en) * | 2002-10-16 | 2010-05-26 | 日亜化学工業株式会社 | Oxynitride phosphor |
| JP4806889B2 (en) * | 2003-09-05 | 2011-11-02 | 日亜化学工業株式会社 | Light source device and illumination device |
| JP4524468B2 (en) * | 2004-05-14 | 2010-08-18 | Ｄｏｗａエレクトロニクス株式会社 | Phosphor, method for producing the same, light source using the phosphor, and LED |
| EP2360225B1 (en) * | 2004-09-22 | 2013-06-26 | National Institute for Materials Science | Phosphor, production method thereof and light emitting instrument |
| JP4988181B2 (en) * | 2004-09-29 | 2012-08-01 | 昭和電工株式会社 | Oxynitride phosphor and method for producing the same |
| JP4798335B2 (en) * | 2004-12-20 | 2011-10-19 | Ｄｏｗａエレクトロニクス株式会社 | Phosphor and light source using phosphor |
| WO2006093298A1 (en) * | 2005-03-04 | 2006-09-08 | Dowa Electronics Materials Co., Ltd. | Fluorescent substance and process for producing the same, and light emitting device using said fluorescent substance |
| KR100682874B1 (en) * | 2005-05-02 | 2007-02-15 | 삼성전기주식회사 | White light emitting device |
| JP4215046B2 (en) * | 2005-11-24 | 2009-01-28 | 日亜化学工業株式会社 | Nitride phosphor and light emitting device using the same |
| WO2007088966A1 (en) * | 2006-02-02 | 2007-08-09 | Mitsubishi Chemical Corporation | Complex oxynitride phosphor, light-emitting device using same, image display, illuminating device, phosphor-containing composition and complex oxynitride |
| CN101473015A (en) * | 2006-06-22 | 2009-07-01 | 皇家飞利浦电子股份有限公司 | Low-pressure gas discharge lamp |
| JP2008095091A (en) * | 2006-09-15 | 2008-04-24 | Mitsubishi Chemicals Corp | Fluorescent substance and its production method, fluorescent substance containing composition, light emitting device, image display device, and illuminating device |
| DE102007022566A1 (en) * | 2007-05-14 | 2008-11-20 | Merck Patent Gmbh | Lighting unit consisting of discharge lamp, LEDs and conversion lamps |
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| Publication number | Publication date |
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| JP2009001760A (en) | 2009-01-08 |
| KR20080114561A (en) | 2008-12-31 |
| CN101333440A (en) | 2008-12-31 |
| CN101333440B (en) | 2013-04-24 |
| TW200904946A (en) | 2009-02-01 |
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