JP3956434B2 - Aluminate phosphor - Google Patents
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- JP3956434B2 JP3956434B2 JP21638397A JP21638397A JP3956434B2 JP 3956434 B2 JP3956434 B2 JP 3956434B2 JP 21638397 A JP21638397 A JP 21638397A JP 21638397 A JP21638397 A JP 21638397A JP 3956434 B2 JP3956434 B2 JP 3956434B2
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Description
【０００１】
【産業上の利用分野】
本発明は、２価のユーロピウムを付活したアルミン酸塩蛍光体に関する。特に、本発明の蛍光体は、プラズマディスプレイパネルに適したものである。
【０００２】
【従来の技術】
近年、薄形ディスプレイの分野に於いて、フルカラープラズマディスプレイパネルが開発され、実用に供されている。このディスプレイには、比較的狭帯域の発光スペクトル分布を有する青色、緑色、赤色の３種類の蛍光体が使用されている。
【０００３】
このプラズマディスプレイパネルは、Ｘｅなどの稀ガス放電により発生する真空紫外域の紫外線により蛍光体を励起した際に得られる発光を利用して、画像を表示するものである。従って、真空紫外域の紫外線励起による蛍光体の輝度の高いことが、より明るい画面を表示するために必要である。
【０００４】
２価のユーロピウムで付活されたアルミン酸塩蛍光体は、紫外線励起時の発光効率が高く（特公昭５２−２２８３６号公報参照）、３波長域発光形蛍光ランプの青色発光蛍光体として用いられてきた（ＪＯＵＲＮＡＬ ＯＦ ＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬ ＳＯＣＩＥＴＹ １２１（１９７４）１６２７−１６３１）。
この蛍光体は、真空紫外域の１４７ｎｍのＸｅ共鳴放射紫外光による励起によっても発光効率が高いことから、フルカラープラズマディスプレイパネルに用いられている。しかし、この蛍光体を青色成分として用いたフルカラープラズマディスプレイパネルは、従来から実用化されているカラーブラウン管と比較して表示輝度が低いという欠点があった。この問題を解決するために、高輝度の青色蛍光体の開発が望まれている。
【０００５】
【発明が解決しようとする課題】
本発明は、２価のユーロピウムで付活された高輝度のアルミン酸塩蛍光体を提供する事にある。
【０００６】
【課題を解決するための手段】
２価のユーロピウムで付活された前記アルミン酸塩蛍光体に適量のＣａを添加する事によって高輝度の蛍光体が得られる事を見いだし、本発明に至った。すなわち、本発明の要旨は、（ａ）Ｂａ、（ｂ）Ｃａ、（ｃ）Ｅｕ、（ｄ）Ｍｇ、（ｅ）Ａｌを含有するアルミン酸塩蛍光体であって、一般式
【数２】
（Ｂａ１−ｘ−ｙＣａｘＥｕｙ）Ｏ・ＭｇＯ・５Ａｌ２Ｏ３
（式中、ｘ及びｙは、それぞれ０．１≦ｘ≦０．４、０＜ｙ＜１（ただしｘ＋ｙ＜１）の実数を表す）で表されることを特徴とするアルミン酸塩蛍光体に存する。
【０００７】
【作用】
以下、本発明の蛍光体について詳細に説明する。本発明の蛍光体は、（ａ）Ｂａ、（ｂ）Ｃａ、（ｃ）Ｅｕ、（ｄ）Ｍｇ、（ｅ）Ａｌを含有するアルミン酸塩蛍光体であって、一般式
【数３】
（Ｂａ１−ｘ−ｙＣａｘＥｕｙ）Ｏ・ＭｇＯ・５Ａｌ２Ｏ３
（式中、ｘ及びｙは、それぞれ０．１≦ｘ≦０．４、０＜ｙ＜１（ただしｘ＋ｙ＜１）の実数を表す）で表されることを特徴とするアルミン酸塩蛍光体である。尚、本発明において、発光に本質的に寄与するのは一般式に記載した構造であるが、本発明の効果を阻害しない限り一部不純物を含んでいてもよく、その場合、一般式としてはＡｌ２Ｏ３、ＭｇＯの係数のずれとして表すことができる。その場合には上記一般式を（Ｂａ１−ｘ−ｙＣａｘＥｕｙ）Ｏ・ａＭｇＯ・ｂＡｌ２Ｏ３と表示でき、ａは１．１迄であれば十分に本発明の効果が得られると考えられる。
ｂも前記ａの変化に伴い４．９５〜５迄変化する事が考えられる。Ｅｕ量ｙは、結晶構造的には０から１迄可変であるが、発光強度の点から０．０５以上０．５以下が好ましい。
【０００８】
（Ｂａ0.9-x Ｃａx Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の化学組成でＣａ添加量ｘを０〜０．９迄変化させた場合のＣａ添加量と輝度Ｂｒ、色度ｙ、及び発光強度Ｂｒ／ｙの関係をそれぞれ図１、図２、及び図３に示した。青色発光の蛍光体の輝度は、視感度の影響を大きく受けるため、同じ発光効率であっても発光色によって大きく変化する。そこで、発光強度の簡便な評価値としては、輝度Ｂｒをその発光色の色度ｙの値で割った値Ｂｒ／ｙを用いた。図１及び図３に示すように、Ｃａ量ｘは、０．１より少ない量で本発明の効果が見られた事、及び０．５以上にすると輝度が低下する傾向にある事から０＜ｘ≦０．５の範囲が好ましい。また、Ｃａ量ｘが０．３を越えると、図１に示すように、輝度が低下するとともに、発光波長が長波長側にシフトするために図２に示すように色度ｙが高くなり、フルカラープラズマディスプレイパネルに使用した場合にディスプレイの色再現範囲が狭くなってしまうので、０＜ｘ≦０．３の範囲が更に好ましい。
【０００９】
本発明の蛍光体は、次のように合成する事ができる。蛍光体原料として、
（１）酸化バリウム、水酸化バリウム、炭酸バリウム等のバリウム化合物
（２）酸化カルシウム、水酸化カルシウム、炭酸カルシウム等のカルシウム化合物
（３）酸化ユーロピウム、フッ化ユーロピウム等のユーロピウム化合物
（４）酸化マグネシウム、水酸化マグネシウム、炭酸マグネシウム等のマグネシウム化合物
（５）酸化アルミニウム、水酸化アルミニウム等のアルミニウム化合物
を所定量秤量し、フッ化バリウム、フッ化アルミニウム、フッ化マグネシウム等のフラックスを配合し、原料混合物を十分に混合する。これら原料のうち、バリウム源となるバリウム化合物としては炭酸バリウムが最も好ましい。これは酸化バリウムは吸水性が高く、水酸化バリウムは焼成中に水を生じる等、水による悪影響をさけるためである。同様の理由でカルシウム化合物としては炭酸カルシウムが好ましく、マグネシウム化合物としては炭酸マグネシウムが好ましく、アルミニウム化合物としては酸化アルミニウムが好ましい。
【００１０】
又、ユーロピウム化合物としては、酸化ユーロピウムが好ましい。フッ化ユーロピウムはフッ素を生じて炉を損傷させる恐れがある。
そしてフラックスとしてはフッ化アルミニウムが最も好ましい。得られた混合物を坩堝に充填し、還元性雰囲気にて、１２００〜１７００℃で１〜４０時間かけて１回以上焼成する。還元性雰囲気を得る方法として、原料の充填された坩堝をカーボンの充填された坩堝内に埋め込む方法、黒鉛の塊や、ヤシガラ等の炭素物質を原料の充填された坩堝内に入れる方法がある。還元を確実にする為に、更にこれらの坩堝を窒素あるいは窒素水素の雰囲気中で焼成しても良い。又これらの雰囲気に水蒸気が含まれていても良い。この焼成物に分散、水洗、乾燥、篩別などの後処理を行い、本発明の青色発光のアルミン酸塩蛍光体を得る事ができる。
【００１１】
【実施例】
以下、本発明の実施例について説明する。
（実施例１）
ＢａＣＯ3 ０．８ ｍｏｌ
ＣａＣＯ3 ０．１ ｍｏｌ
Ｅｕ2 Ｏ3 ０．０５ ｍｏｌ
３ＭｇＣＯ3 ・Ｍｇ（ＯＨ）2 ０．２５ ｍｏｌ
Ａｌ2 Ｏ3 （アルファタイプ） ５．０ ｍｏｌ
ＡｌＦ3 ０．０１ ｍｏｌ
【００１２】
上記原料を湿式で混合し、乾燥後、坩堝に充填し、更にビーズ炭を入れた坩堝に入れて蓋をして、大気中で最高温度１４５０℃で昇降温時間を含め６時間かけて焼成した。次いで、焼成粉を後処理し、（Ｂａ0.8 Ｃａ0.1 Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の２価のユーロピウム付活青色発光アルミン酸塩蛍光体を得た。この蛍光体の１４７ｎｍ紫外線励起輝度は、比較例１に示すＣａを含まない（Ｂａ0.9 Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の２価のユーロピウム付活青色発光アルミン酸塩蛍光体の１４７ｎｍ紫外線励起輝度Ｂｒを１００とした相対値で１２９であり、色度ｙは０．０７２となり、Ｂｒ／ｙは比較例１の蛍光体のＢｒ／ｙを１００とした相対値で１０８であり、Ｃａを含まない比較例１に比べて輝度Ｂｒと発光強度Ｂｒ／ｙの向上が認められた。
【００１３】
（実施例２〜４）
上記原料を表１に示す各組成式となる割合で混合する以外は実施例１と同じ工程を経ることにより２価のユーロピウム付活青色発光アルミン酸塩蛍光体を得た。このようにして得られた蛍光体の輝度Ｂｒ、色度ｙ、発光強度Ｂｒ／ｙを同じく表１に示した。これらの実施例のいずれについても比較例１に対して輝度Ｂｒの向上が認められた。また、実施例２については発光強度Ｂｒ／ｙの向上も認められた。
【００１４】
（比較例１）
ＢａＣＯ3 ０．９ ｍｏｌ
Ｅｕ2 Ｏ3 ０．０５ ｍｏｌ
３ＭｇＣＯ3 ・Ｍｇ（ＯＨ）2 ０．２５ ｍｏｌ
Ａｌ2 Ｏ3 （アルファタイプ） ５．０ ｍｏｌ
ＡｌＦ3 ０．０１ ｍｏｌ
【００１５】
上記原料を湿式で混合し、乾燥後、坩堝に充填し、更にビーズ炭を入れた坩堝に入れて蓋をして、大気中で最高温度１４５０℃で昇降温時間を含め６時間かけて焼成した。次いで、焼成粉を後処理し、（Ｂａ0.9 Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の２価のユーロピウム付活青色発光アルミン酸塩蛍光体を得た。この蛍光体の１４７ｎｍ紫外線励起輝度Ｂｒを基準値として１００とした。この蛍光体の色度ｙは０．０６０となり、その発光強度Ｂｒ／ｙを基準値として１００とした。
【００１６】
（比較例２）
ＢａＣＯ3 ０．３ ｍｏｌ
ＣａＣＯ3 ０．６ ｍｏｌ
Ｅｕ2 Ｏ3 ０．０５ ｍｏｌ
３ＭｇＣＯ3 ・Ｍｇ（ＯＨ）2 ０．２５ ｍｏｌ
Ａｌ2 Ｏ3 （アルファタイプ） ５．０ ｍｏｌ
ＡｌＦ3 ０．０１ ｍｏｌ
【００１７】
上記原料を湿式で混合し、乾燥後、坩堝に充填し、更にビーズ炭を入れた坩堝に入れて蓋をして、大気中で最高温度１４５０℃で昇降温時間を含め６時間かけて焼成した。次いで、焼成粉を後処理し、（Ｂａ0.3 Ｃａ0.6 Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の２価のユーロピウム付活青色発光アルミン酸塩蛍光体を得た。この蛍光体の１４７ｎｍ紫外線励起輝度は、比較例１の蛍光体の１４７ｎｍ紫外線励起輝度Ｂｒを１００とした相対値で８４であり、色度ｙは０．１０３となり、発光強度Ｂｒ／ｙは比較例１の蛍光体のＢｒ／ｙを１００とした相対値で４９であり、輝度も発光強度も比較例１より低かった。
【００１８】
（比較例３）
ＣａＣＯ3 ０．９ ｍｏｌ
Ｅｕ2 Ｏ3 ０．０５ ｍｏｌ
３ＭｇＣＯ3 ・Ｍｇ（ＯＨ）2 ０．２５ ｍｏｌ
Ａｌ2 Ｏ3 （アルファタイプ） ５．０ ｍｏｌ
ＡｌＦ3 ０．０１ ｍｏｌ
【００１９】
上記原料を湿式で混合し、乾燥後、坩堝に充填し、更にビーズ炭を入れた坩堝に入れて蓋をして、大気中で最高温度１４５０℃で昇降温時間を含め６時間かけて焼成した。次いで、焼成粉を後処理し、（Ｃａ0.9 Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の２価のユーロピウム付活青色発光アルミン酸塩蛍光体を得た。この蛍光体の１４７ｎｍ紫外線励起輝度は、比較例１の蛍光体の１４７ｎｍ紫外線励起輝度Ｂｒを１００とした相対値で７であり、色度ｙは０．１５６となり、発光強度Ｂｒ／ｙは比較例１の蛍光体のＢｒ／ｙを１００とした相対値で３であり、蛍光体としては実用に供せないほど輝度と発光強度が低かった。
【００２０】
【表１】
【発明の効果】
本発明により、２価のユーロピウムを付活した高輝度のアルミン酸塩蛍光体を提供することが可能である。
【図面の簡単な説明】
【図１】図１は、２価のユーロピウムを付活したアルミン酸塩蛍光体において（Ｂａ0.9-x Ｃａx Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の化学組成でＣａ添加量ｘを０〜０．９迄変化させた場合のＣａ添加量と輝度Ｂｒの関係を示す図である。
【図２】図２は、２価のユーロピウムを付活したアルミン酸塩蛍光体へのＣａ添加量２価のユーロピウムを付活したアルミン酸塩蛍光体において（Ｂａ0.9-x Ｃａx Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の化学組成でＣａ添加量ｘを０〜０．９迄変化させた場合のＣａ添加量と色度ｙの関係を示す図である。
【図３】図３は、２価のユーロピウムを付活したアルミン酸塩蛍光体へのＣａ添加量２価のユーロピウムを付活したアルミン酸塩蛍光体において（Ｂａ0.9-x Ｃａx Ｅｕ0.1 ）Ｏ・ＭｇＯ・５Ａｌ2 Ｏ3 の化学組成でＣａ添加量ｘを０〜０．９迄変化させた場合のＣａ添加量と発光強度Ｂｒ／ｙの関係を示す図である。[0001]
[Industrial application fields]
The present invention relates to an aluminate phosphor activated with divalent europium. In particular, the phosphor of the present invention is suitable for a plasma display panel.
[0002]
[Prior art]
In recent years, full-color plasma display panels have been developed and put into practical use in the field of thin displays. This display uses three kinds of phosphors of blue, green, and red having a relatively narrow emission spectrum distribution.
[0003]
This plasma display panel displays an image using light emission obtained when a phosphor is excited by ultraviolet rays in a vacuum ultraviolet region generated by rare gas discharge such as Xe. Accordingly, it is necessary for the phosphor to have high luminance by ultraviolet excitation in the vacuum ultraviolet region in order to display a brighter screen.
[0004]
The aluminate phosphor activated with divalent europium has high luminous efficiency when excited with ultraviolet light (see Japanese Patent Publication No. Sho 52-22836), and is used as a blue light-emitting phosphor of a three-wavelength range fluorescent lamp. (JOURNAL OF ELECTROCHEMICAL SOCIETY 121 (1974) 1627-1631).
This phosphor is used in full-color plasma display panels because of its high luminous efficiency even when excited by Xe resonance radiation ultraviolet light of 147 nm in the vacuum ultraviolet region. However, a full color plasma display panel using this phosphor as a blue component has a drawback that the display luminance is lower than that of a color cathode ray tube that has been put into practical use. In order to solve this problem, development of a high-luminance blue phosphor is desired.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a high-brightness aluminate phosphor activated with divalent europium.
[0006]
[Means for Solving the Problems]
It has been found that a high-luminance phosphor can be obtained by adding an appropriate amount of Ca to the aluminate phosphor activated with divalent europium. That is, the gist of the present invention is an aluminate phosphor containing (a) Ba, (b) Ca, (c) Eu, (d) Mg, (e) Al, which has the general formula:
(Ba 1-xy Ca x Eu y ) O · MgO · 5Al 2 O 3
(Wherein, x and y are each 0.1 ≦ x ≦ 0. 4, 0 <y <1 ( provided that x + y <1) represents a real number) aluminate phosphor to be characterized represented by Exist.
[0007]
[Action]
Hereinafter, the phosphor of the present invention will be described in detail. The phosphor of the present invention is an aluminate phosphor containing (a) Ba, (b) Ca, (c) Eu, (d) Mg, (e) Al, and has the general formula
(Ba 1-xy Ca x Eu y ) O · MgO · 5Al 2 O 3
(Wherein, x and y are each 0.1 ≦ x ≦ 0. 4, 0 <y <1 ( provided that x + y <1) represents a real number) aluminate phosphor to be characterized represented by It is. In the present invention, it is the structure described in the general formula that essentially contributes to light emission, but it may contain a part of impurities as long as the effect of the present invention is not impaired. It can be expressed as a deviation of coefficients of Al 2 O 3 and MgO. In that case, the above general formula can be expressed as (Ba 1-xy Ca x Eu y ) O.aMgO.bAl 2 O 3, and if the value of a is up to 1.1, the effects of the present invention can be obtained sufficiently. it is conceivable that.
It is conceivable that b also changes from 4.95 to 5 with the change of a. The Eu amount y is variable from 0 to 1 in terms of crystal structure, but is preferably 0.05 or more and 0.5 or less from the viewpoint of light emission intensity.
[0008]
(Ba 0.9-x Ca x Eu 0.1 ) O · MgO · 5Al 2 O 3 chemical composition, Ca addition amount and luminance Br, chromaticity y, when the Ca addition amount x is changed from 0 to 0.9, and The relationship of emission intensity Br / y is shown in FIGS. 1, 2 and 3, respectively. Since the luminance of the blue-emitting phosphor is greatly affected by the visibility, it greatly varies depending on the emission color even with the same luminous efficiency. Therefore, as a simple evaluation value of the emission intensity, a value Br / y obtained by dividing the luminance Br by the value of the chromaticity y of the emission color is used. As shown in FIG. 1 and FIG. 3, the Ca amount x is less than 0.1, and the effect of the present invention is observed. A range of x ≦ 0.5 is preferred. If the Ca amount x exceeds 0.3, the luminance decreases as shown in FIG. 1, and the emission wavelength shifts to the long wavelength side, so that the chromaticity y increases as shown in FIG. When used in a full-color plasma display panel, the color reproduction range of the display becomes narrow, so the range of 0 <x ≦ 0.3 is more preferable.
[0009]
The phosphor of the present invention can be synthesized as follows. As a phosphor material,
(1) Barium compounds such as barium oxide, barium hydroxide and barium carbonate (2) Calcium compounds such as calcium oxide, calcium hydroxide and calcium carbonate (3) Europium compounds such as europium oxide and europium fluoride (4) Magnesium oxide Magnesium compounds such as magnesium hydroxide and magnesium carbonate (5) Weigh a predetermined amount of aluminum compounds such as aluminum oxide and aluminum hydroxide, blend fluxes such as barium fluoride, aluminum fluoride and magnesium fluoride, and mix the raw materials Mix thoroughly. Of these raw materials, barium carbonate is most preferred as the barium compound serving as the barium source. This is because barium oxide has a high water absorption property, and barium hydroxide prevents water from being adversely affected by water generation during firing. For the same reason, calcium carbonate is preferable as the calcium compound, magnesium carbonate is preferable as the magnesium compound, and aluminum oxide is preferable as the aluminum compound.
[0010]
As the europium compound, europium oxide is preferable. Europium fluoride can generate fluorine and damage the furnace.
The flux is most preferably aluminum fluoride. The obtained mixture is filled in a crucible and baked once or more at 1200 to 1700 ° C. over 1 to 40 hours in a reducing atmosphere. As a method for obtaining a reducing atmosphere, there are a method of embedding a crucible filled with a raw material in a crucible filled with carbon, and a method of putting a carbon substance such as a lump of graphite or coconut shell into a crucible filled with the raw material. In order to ensure the reduction, these crucibles may be further fired in an atmosphere of nitrogen or nitrogen hydrogen. Moreover, water vapor may be contained in these atmospheres. The fired product can be subjected to post-treatments such as dispersion, washing, drying and sieving to obtain the blue-emitting aluminate phosphor of the present invention.
[0011]
【Example】
Examples of the present invention will be described below.
Example 1
BaCO 3 0.8 mol
CaCO 3 0.1 mol
Eu 2 O 3 0.05 mol
3MgCO 3 .Mg (OH) 2 0.25 mol
Al 2 O 3 (alpha type) 5.0 mol
AlF 3 0.01 mol
[0012]
The above raw materials are mixed in a wet manner, dried, filled into a crucible, placed in a crucible containing bead charcoal, capped, and baked in the atmosphere at a maximum temperature of 1450 ° C. for 6 hours including a temperature rise and fall time. . Next, the calcined powder was post-treated to obtain a (Ba 0.8 Ca 0.1 Eu 0.1 ) O · MgO · 5Al 2 O 3 divalent europium-activated blue light-emitting aluminate phosphor. The 147 nm ultraviolet excitation brightness of this phosphor is 147 nm ultraviolet of the divalent europium activated blue light-emitting aluminate phosphor of (Ba 0.9 Eu 0.1 ) O.MgO.5Al 2 O 3 not containing Ca shown in Comparative Example 1. The relative value when the excitation brightness Br is 100 is 129, the chromaticity y is 0.072, the Br / y is 108 when the Br / y of the phosphor of Comparative Example 1 is 100, and Ca is Improvement in luminance Br and emission intensity Br / y was recognized as compared with Comparative Example 1 which did not contain.
[0013]
(Examples 2 to 4)
A divalent europium-activated blue light-emitting aluminate phosphor was obtained by going through the same steps as in Example 1 except that the raw materials were mixed in proportions corresponding to the composition formulas shown in Table 1. The brightness Br, chromaticity y, and emission intensity Br / y of the phosphor thus obtained are also shown in Table 1. In any of these examples, an improvement in luminance Br was recognized with respect to Comparative Example 1. In Example 2, an improvement in the emission intensity Br / y was also observed.
[0014]
(Comparative Example 1)
BaCO 3 0.9 mol
Eu 2 O 3 0.05 mol
3MgCO 3 .Mg (OH) 2 0.25 mol
Al 2 O 3 (alpha type) 5.0 mol
AlF 3 0.01 mol
[0015]
The above raw materials are mixed in a wet manner, dried, filled into a crucible, placed in a crucible containing bead charcoal, capped, and baked in the atmosphere at a maximum temperature of 1450 ° C. for 6 hours including a temperature rise and fall time. . Next, the calcined powder was post-treated to obtain a bivalent europium-activated blue light-emitting aluminate phosphor of (Ba 0.9 Eu 0.1 ) O · MgO · 5Al 2 O 3 . The 147 nm ultraviolet excitation luminance Br of this phosphor was set to 100 as a reference value. The chromaticity y of this phosphor was 0.060, and the emission intensity Br / y was set to 100 as a reference value.
[0016]
(Comparative Example 2)
BaCO 3 0.3 mol
CaCO 3 0.6 mol
Eu 2 O 3 0.05 mol
3MgCO 3 .Mg (OH) 2 0.25 mol
Al 2 O 3 (alpha type) 5.0 mol
AlF 3 0.01 mol
[0017]
The above raw materials are mixed in a wet manner, dried, filled into a crucible, placed in a crucible containing bead charcoal, capped, and baked in the atmosphere at a maximum temperature of 1450 ° C. for 6 hours including a temperature rise and fall time. . Next, the fired powder was post-processed to obtain a bivalent europium-activated blue light-emitting aluminate phosphor of (Ba 0.3 Ca 0.6 Eu 0.1 ) O.MgO.5Al 2 O 3 . The 147 nm ultraviolet excitation luminance of this phosphor is 84 as a relative value with the 147 nm ultraviolet excitation luminance Br of the phosphor of Comparative Example 1 being 100, the chromaticity y is 0.103, and the emission intensity Br / y is Comparative Example. The relative value of Br / y of phosphor No. 1 with respect to 100 was 49, and the luminance and emission intensity were lower than those of Comparative Example 1.
[0018]
(Comparative Example 3)
CaCO 3 0.9 mol
Eu 2 O 3 0.05 mol
3MgCO 3 .Mg (OH) 2 0.25 mol
Al 2 O 3 (alpha type) 5.0 mol
AlF 3 0.01 mol
[0019]
The above raw materials are mixed in a wet manner, dried, filled into a crucible, placed in a crucible containing bead charcoal, capped, and baked in the atmosphere at a maximum temperature of 1450 ° C. for 6 hours including a temperature rise and fall time. . Next, the calcined powder was post-treated to obtain a bivalent europium-activated blue light-emitting aluminate phosphor of (Ca 0.9 Eu 0.1 ) O · MgO · 5Al 2 O 3 . The phosphor-excited luminance at 147 nm of this phosphor is 7 as a relative value with the 147-nm ultraviolet-excited luminance Br of the phosphor of Comparative Example 1 being 100, the chromaticity y is 0.156, and the emission intensity Br / y is Comparative Example. The relative value of Br / y of phosphor No. 1 was 3, and the luminance and emission intensity were so low that the phosphor could not be put to practical use.
[0020]
[Table 1]
【The invention's effect】
According to the present invention, it is possible to provide a high-brightness aluminate phosphor activated with divalent europium.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram of (Ba 0.9-x Ca x Eu 0.1 ) O · MgO · 5Al 2 O 3 with a chemical composition of (Ba 0.9-x Ca x Eu 0.1 ) in an aluminate phosphor activated with divalent europium. It is a figure which shows the relationship between Ca addition amount and the brightness | luminance Br at the time of changing to -0.9.
FIG. 2 shows the amount of Ca added to a divalent europium-activated aluminate phosphor in a divalent europium-activated aluminate phosphor (Ba 0.9-x Ca x Eu 0.1 ). the O · MgO · 5Al 2 O 3 in the chemical composition Ca addition amount x is a diagram showing the relationship between addition amount of Ca and the chromaticity y in the case of changing up from 0 to 0.9.
FIG. 3 shows the amount of Ca added to a divalent europium-activated aluminate phosphor in an aluminate phosphor activated with divalent europium (Ba 0.9-x Ca x Eu 0.1 ). the O · MgO · 5Al 2 O 3 in the chemical composition Ca addition amount x is a diagram showing the addition amount of Ca and the relationship of luminous intensity Br / y in the case of changing up from 0 to 0.9.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21638397A JP3956434B2 (en) | 1997-06-03 | 1997-08-11 | Aluminate phosphor |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-144995 | 1997-06-03 | ||
| JP14499597 | 1997-06-03 | ||
| JP21638397A JP3956434B2 (en) | 1997-06-03 | 1997-08-11 | Aluminate phosphor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1150049A JPH1150049A (en) | 1999-02-23 |
| JP3956434B2 true JP3956434B2 (en) | 2007-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21638397A Expired - Lifetime JP3956434B2 (en) | 1997-06-03 | 1997-08-11 | Aluminate phosphor |
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| JP (1) | JP3956434B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001220582A (en) * | 1999-11-30 | 2001-08-14 | Sumitomo Chem Co Ltd | Preparation process of aluminate phosphor |
| JP2002275464A (en) * | 2001-03-21 | 2002-09-25 | Kasei Optonix Co Ltd | Aluminate fluorescent substance, fluorescent paste composition and vacuum ultraviolet ray-excited light- emitting element |
| JP4899275B2 (en) * | 2001-08-31 | 2012-03-21 | 東レ株式会社 | Phosphor and phosphor paste |
| US8731792B2 (en) * | 2011-09-23 | 2014-05-20 | GM Global Technology Operations LLC | System and method for estimating hydraulic pressure within and controlling a dry dual clutch transmission |
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