JP2006249120A - Phosphor for electron-beam-excited light-emitting element - Google Patents

Phosphor for electron-beam-excited light-emitting element Download PDF

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JP2006249120A
JP2006249120A JP2005063454A JP2005063454A JP2006249120A JP 2006249120 A JP2006249120 A JP 2006249120A JP 2005063454 A JP2005063454 A JP 2005063454A JP 2005063454 A JP2005063454 A JP 2005063454A JP 2006249120 A JP2006249120 A JP 2006249120A
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phosphor
electron beam
formula
emitting element
excited light
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Riyouji Sugano
了次 菅野
Noriyuki Sonoyama
範之 園山
Takayoshi Kaihara
隆義 槐原
Susumu Miyazaki
進 宮崎
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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Priority to PCT/JP2006/304369 priority patent/WO2006095732A1/en
Priority to TW095107773A priority patent/TW200636048A/en
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    • H01J2329/20—Luminescent screens characterised by the luminescent material

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphor for an electron-beam-excited light-emitting element capable of suppressing reduction in light-emitting intensity. <P>SOLUTION: The phosphor for an electron-beam-excited light-emitting element comprises a compound represented by the formula: M<SP>1</SP>O-M<SP>2</SP><SB>2</SB>O<SB>3</SB>(wherein M<SP>1</SP>denotes one or more selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; and M<SP>2</SP>denotes one or more selected from the group consisting of Sc, Y, B, Al, Ga, and In) and a rare earth ion Ln (wherein Ln denotes one or more selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, Er, and Tm) as an activator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、蛍光体に関する。さらに詳しくは、電子線励起発光素子用蛍光体に関する。   The present invention relates to a phosphor. More specifically, the present invention relates to a phosphor for an electron beam excited light emitting device.

蛍光体は、ブラウン管（以下「ＣＲＴ」という。）、フィールドエミッションディスプレイ（以下「ＦＥＤ」という。）、表面電界ディスプレイ（以下「ＳＥＤ」という。）、蛍光表示管（以下「ＶＦＤ」という。）等の電子線励起発光素子に用いられている。電子線励起発光素子には、蛍光体の励起源として、電子線が用いられている。電子線励起発光素子用蛍光体としては、例えば、ＺｎＳ：Ｚｎ、ＺｎＳ：Ｃｕ，Ａｌ、ＺｎＳ：Ａｕ,Ａｌ、（Ｚｎ0.9，Ｃｄ0.1）Ｓ：Ａｕ，Ａｌ等の蛍光体が挙げられる（例えば非特許文献１参照。）。 The phosphor is a cathode ray tube (hereinafter referred to as “CRT”), a field emission display (hereinafter referred to as “FED”), a surface electric field display (hereinafter referred to as “SED”), a fluorescent display tube (hereinafter referred to as “VFD”), or the like. It is used for the electron beam excitation light emitting element. In the electron beam excitation light emitting element, an electron beam is used as an excitation source of a phosphor. Examples of phosphors for electron beam-excited light emitting devices include phosphors such as ZnS: Zn, ZnS: Cu, Al, ZnS: Au, Al, (Zn 0.9 , Cd 0.1 ) S: Au, Al (for example, (Refer nonpatent literature 1.).

蛍光体同学会編 蛍光体ハンドブック、第３０７頁（昭和６２年）。Fluorescent material handbook, phosphor handbook, page 307 (1987).

しかしながら、従来の蛍光体は、使用時に蛍光体が分解するためか、蛍光体の発光強度が低下してしまうという問題があった。本発明の目的は、発光強度低下の抑制が可能な電子線励起発光素子用蛍光体を提供することにある。   However, the conventional phosphor has a problem that the emission intensity of the phosphor is lowered because the phosphor is decomposed during use. An object of the present invention is to provide a phosphor for an electron beam-excited light emitting device capable of suppressing a decrease in emission intensity.

本発明者らは、上記の課題を解決すべく蛍光体の組成につき、鋭意研究を重ねた結果、ある特定の化合物に付活剤が含有されてなる蛍光体は、発光強度低下の抑制が可能であり、ＣＲＴ、ＦＥＤ等の電子線励起発光素子に好適に用いることができることを見出し、本発明を完成するに至った。   As a result of intensive studies on the composition of the phosphor to solve the above problems, the present inventors can suppress a decrease in emission intensity of a phosphor containing an activator in a specific compound. Thus, the present invention has been found out that it can be suitably used for an electron beam-excited light-emitting device such as a CRT or FED.

すなわち本発明は、下記の蛍光体および発光素子を提供するものである。
＜１＞式Ｍ1Ｏ・Ｍ2 2Ｏ3（式中のＭ1はＭｇ、Ｃａ、Ｓｒ、ＢａおよびＺｎからなる群より選ばれる１種以上であり、Ｍ2はＳｃ、Ｙ、Ｂ、Ａｌ、ＧａおよびＩｎからなる群より選ばれる１種以上である。）で表される化合物に付活剤として希土類イオンＬｎ（ＬｎはＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｈｏ、Ｄｙ、ＥｒおよびＴｍからなる群より選ばれる１種類以上）を含有されてなることを特徴とする電子線励起発光素子用蛍光体。
＜２＞式（Ｍｇ1-xＭ1 x）Ｏ・（Ｉｎ1-yＭ2 y）2Ｏ3（式中のＭ1およびＭ2は前記と同じ意味を有し、ｘは０以上１未満の範囲であり、ｙは０以上１未満の範囲である。）で表される化合物に付活剤として希土類イオンＬｎ（Ｌｎは前記と同じ意味を有する。）を含有されてなる前記の蛍光体。
＜３＞式（Ｚｎ1-xＭ1 x）Ｏ・（Ｉｎ1-yＭ2 y）2Ｏ3（式中のＭ1およびＭ2は前記と同じ意味を有し、ｘは０以上１未満の範囲であり、ｙは０以上１未満の範囲である。）で表される化合物に付活剤として希土類イオンＬｎ（Ｌｎは前記と同じ意味を有する。）を含有されてなる前記＜１＞記載の蛍光体。
＜４＞前記いずれかに記載の蛍光体を含有してなることを特徴とする電子線励起発光素子。
＜５＞蛍光体の励起源が低速電子線である前記＜４＞記載の電子線励起発光素子。
＜６＞電子線励起発光素子がフィールドエミッションディスプレイであることを特徴とする前記いずれかに記載の蛍光体。
＜７＞電子線励起発光素子が表面電界ディスプレイであることを特徴とする前記いずれかに記載の蛍光体。
＜８＞前記＜６＞記載の蛍光体を含有してなるフィールドエミッションディスプレイ。
＜９＞前記＜７＞記載の蛍光体を含有してなる表面電界ディスプレイ。 That is, the present invention provides the following phosphor and light emitting element.
<1> Formula M 1 O · M 2 2 O 3 (wherein M 1 is one or more selected from the group consisting of Mg, Ca, Sr, Ba and Zn, and M 2 is Sc, Y, B, As an activator, a rare earth ion Ln (Ln is Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, a compound represented by the group consisting of Al, Ga and In). A phosphor for an electron beam-excited light-emitting element, comprising one or more selected from the group consisting of Er and Tm.
<2> Formula (Mg 1-x M 1 x ) O. (In 1-y M 2 y ) 2 O 3 (wherein M 1 and M 2 have the same meaning as above, x is 0 or more and 1) And y is a range of 0 or more and less than 1. The above-mentioned fluorescence obtained by containing rare earth ions Ln (Ln has the same meaning as described above) as an activator in the compound represented by body.
<3> Formula (Zn 1 -x M 1 x ) O. (In 1 -y M 2 y ) 2 O 3 (wherein M 1 and M 2 have the same meaning as above, x is 0 or more and 1) <1, wherein y is a range of 0 or more and less than 1) The rare earth ion Ln (Ln has the same meaning as described above) as an activator is contained in the compound represented by <1. > The phosphor described.
<4> An electron beam-excited light-emitting device comprising the phosphor according to any one of the above.
<5> The electron beam excitation light-emitting device according to <4>, wherein the phosphor excitation source is a low-energy electron beam.
<6> The phosphor according to any one of the above, wherein the electron beam excitation light-emitting device is a field emission display.
<7> The phosphor according to any one of the above, wherein the electron beam excitation light-emitting device is a surface electric field display.
<8> A field emission display comprising the phosphor according to <6>.
<9> A surface electric field display comprising the phosphor according to <7>.

本発明の蛍光体は、発光強度低下の抑制が可能な蛍光体であるため、電子線を励起源とするＣＲＴ、ＦＥＤ等のような電子線励起発光素子に好適に用いることができ、本発明は工業的に極めて有用である。   Since the phosphor of the present invention is a phosphor capable of suppressing a decrease in emission intensity, it can be suitably used for an electron beam excited light emitting device such as a CRT or FED using an electron beam as an excitation source. Is extremely useful industrially.

以下、本発明について説明する。   The present invention will be described below.

本発明の蛍光体は、式（１）
Ｍ1Ｏ・Ｍ2 2Ｏ3・・・（１）
で表される化合物に付活剤が含有されてなる蛍光体である。式（１）のＭ1は２価の金属元素であり、Ｍｇ、Ｃａ、Ｓｒ、ＢａおよびＺｎからなる群より選ばれる１種以上である。また式（１）のＭ2は３価の金属元素であり、Ｓｃ、Ｙ、Ｂ、Ａｌ、ＧａおよびＩｎからなる群より選ばれる１種以上である。付活剤としては、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｈｏ、Ｄｙ、ＥｒおよびＴｍからなる群より選ばれる１種以上を含有する。 The phosphor of the present invention has the formula (1)
M 1 O · M 2 2 O 3 (1)
A phosphor in which an activator is contained in a compound represented by the formula: M 1 in the formula (1) is a divalent metal element and is at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. M 2 in the formula (1) is a trivalent metal element and is at least one selected from the group consisting of Sc, Y, B, Al, Ga, and In. The activator contains one or more selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, Er, and Tm.

式（１）で表される化合物としては、発光強度低下をより抑制する意味で、スピネル型構造を含有することが好ましく、スピネル型構造の中でも正スピネル型構造または逆スピネル型構造を含有することがより好ましい。ここで、スピネル型構造とは、尖晶石（組成はＭｇＡｌ2Ｏ4で表される。）に代表されるＸＹ2Ｏ4型（ＸおよびＹは金属元素を示す。）の結晶構造のことをいう。スピネル型構造において酸素原子は立方最密充填形式に配列しており、その酸素原子で囲まれた空間のうち４個の酸素原子で囲まれる空間にＸが配置されかつ６個の酸素原子で囲まれた空間にＹが配置されるスピネル型構造を正スピネル型構造といい、前記酸素原子で囲まれた空間のうち４個の酸素原子で囲まれる空間にＹが配置されかつ６個の酸素原子で囲まれる空間にＸまたはＹが配置されるスピネル型構造を逆スピネル型構造という。 The compound represented by the formula (1) preferably contains a spinel structure in order to further suppress a decrease in emission intensity, and contains a normal spinel structure or an inverse spinel structure among the spinel structures. Is more preferable. Here, the spinel structure is a crystal structure of XY 2 O 4 type (X and Y represent metal elements) represented by spinel (composition is represented by MgAl 2 O 4 ). Say. In the spinel structure, oxygen atoms are arranged in a cubic close-packed form, and X is arranged in a space surrounded by four oxygen atoms among the spaces surrounded by the oxygen atoms and surrounded by six oxygen atoms. A spinel structure in which Y is arranged in a defined space is called a positive spinel structure, and Y is arranged in a space surrounded by four oxygen atoms and six oxygen atoms are surrounded by the oxygen atoms. A spinel structure in which X or Y is arranged in a space surrounded by is called an inverted spinel structure.

式（１）で表される化合物が上記の逆スピネル型構造を含有する傾向があるので、本発明の蛍光体は式（２）
（Ｍｇ1-xＭ1 x）Ｏ・（Ｉｎ1-yＭ2 y）2Ｏ3・・・（２）
（式中のＭ1およびＭ2は前記と同じ意味を有し、ｘは０以上１未満の範囲であり、ｙは０以上１未満の範囲である。）
で表される化合物に付活剤としてＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｈｏ、Ｄｙ、ＥｒおよびＴｍからなる群より選ばれる１種以上が含有される蛍光体であることがより好ましい。また、Ｍ1がＣａまたはＭｇであることがさらに好ましい。ここで、式（２）において、ｘは０以上０．４未満の範囲であることが好ましく、０以上０．１以下の範囲であることがより好ましく、さらに好ましくは０である。また、ここで、式（２）において、ｙは０以上０．２以下の範囲であることが好ましく、より好ましくは０である。 Since the compound represented by the formula (1) tends to contain the above inverse spinel structure, the phosphor of the present invention has the formula (2).
(Mg 1 -x M 1 x ) O. (In 1 -y M 2 y ) 2 O 3 (2)
(M 1 and M 2 in the formula have the same meaning as described above, x is in the range of 0 to less than 1, and y is in the range of 0 to less than 1.)
It is more preferable that the phosphor is a phosphor containing at least one selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, Er, and Tm as an activator. . More preferably, M 1 is Ca or Mg. Here, in Formula (2), x is preferably in the range of 0 to less than 0.4, more preferably in the range of 0 to 0.1, and even more preferably 0. Here, in the formula (2), y is preferably in the range of 0 or more and 0.2 or less, more preferably 0.

また、式（１）で表される化合物が上記の正スピネル型構造を含有する傾向があるので、本発明の蛍光体は式（３）
式（Ｚｎ1-xＭ1 x）Ｏ・（Ｉｎ1-yＭ2 y）2Ｏ3・・・（３）
（式中のＭ1およびＭ2は前記と同じ意味を有し、ｘは０以上１未満の範囲であり、ｙは０以上１未満の範囲である。）
で表される化合物に付活剤としてＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｈｏ、Ｄｙ、ＥｒおよびＴｍからなる群より選ばれる１種以上が含有される蛍光体であることがより好ましい。また、Ｍ1がＣａまたはＺｎであることがさらに好ましい。ここで、式（３）において、ｘは０以上０．４未満の範囲であることが好ましく、０以上０．１以下の範囲であることがより好ましく、さらに好ましくは０である。また、ここで、式（３）において、ｙは０以上０．２以下の範囲であることが好ましく、より好ましくは０である。 Further, since the compound represented by the formula (1) tends to contain the positive spinel structure, the phosphor of the present invention has the formula (3).
Formula (Zn 1-x M 1 x ) O. (In 1-y M 2 y ) 2 O 3 (3)
(M 1 and M 2 in the formula have the same meaning as described above, x is in the range of 0 to less than 1, and y is in the range of 0 to less than 1.)
It is more preferable that the phosphor is a phosphor containing at least one selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, Er, and Tm as an activator. . More preferably, M 1 is Ca or Zn. Here, in Formula (3), x is preferably in the range of 0 to less than 0.4, more preferably in the range of 0 to 0.1, and even more preferably 0. Here, in the formula (3), y is preferably in the range of 0 or more and 0.2 or less, more preferably 0.

本発明の蛍光体は、電子線によって励起され発光するため、ＣＲＴ、ＦＥＤ、ＳＥＤ、ＶＦＤ、等の電子線励起発光素子に好ましく用いられる。電子線励起発光素子に用いる蛍光体の励起源である電子線としては、電子の加速電圧が２０ｋＶ〜３０ｋＶである場合の高速電子線、電子の加速電圧が１０ｋＶ以下である場合の低速電子線があるが、本発明の蛍光体は、蛍光体の励起源が低速電子線である電子線励起発光素子により好ましく用いられる。蛍光体の励起源が低速電子線である電子線励起発光素子としては、ＦＥＤ、ＳＥＤが挙げられ、本発明の蛍光体は、ＦＥＤ、ＳＥＤに特に好ましく用いられる。   Since the phosphor of the present invention is excited by an electron beam and emits light, it is preferably used for an electron beam-excited light emitting device such as a CRT, FED, SED, or VFD. The electron beam that is the excitation source of the phosphor used in the electron beam excitation light-emitting device includes a high-speed electron beam when the electron acceleration voltage is 20 kV to 30 kV, and a low-speed electron beam when the electron acceleration voltage is 10 kV or less. However, the phosphor of the present invention is preferably used for an electron beam excited light emitting device in which the excitation source of the phosphor is a slow electron beam. Examples of the electron beam excited light emitting device in which the excitation source of the phosphor is a low-energy electron beam include FED and SED, and the phosphor of the present invention is particularly preferably used for FED and SED.

また本発明の蛍光体を電子線励起発光素子に好ましく用いるためには、本発明の蛍光体は、電気伝導率が１０-5Ｓ・ｃｍ-1以上であることが好ましく、１０-4Ｓ・ｃｍ-1以上であることがより好ましく、さらに好ましくは１０-3Ｓ・ｃｍ-1以上である。ここで、本発明の蛍光体の電気伝導率は、本発明の蛍光体の焼結体の電気伝導率の測定値とする。また、本発明の蛍光体と導電性化合物との混合物を電子線励起発光素子に用いてもよい。導電性化合物としてはＺｎＯ、Ｉｎ2Ｏ3、ＳｎＯ2、ＩＴＯ等が挙げられる。 In order to preferably use the phosphor of the present invention for an electron beam-excited light emitting device, the phosphor of the present invention preferably has an electric conductivity of 10 −5 S · cm −1 or more, preferably 10 −4 S · It is more preferably cm −1 or more, and further preferably 10 −3 S · cm −1 or more. Here, the electrical conductivity of the phosphor of the present invention is a measured value of the electrical conductivity of the sintered body of the phosphor of the present invention. Moreover, you may use the mixture of the fluorescent substance of this invention and an electroconductive compound for an electron beam excitation light emitting element. Examples of the conductive compound include ZnO, In 2 O 3 , SnO 2 and ITO.

次に、本発明の蛍光体を製造する方法について説明する。
本発明の蛍光体は、例えば、次のようにして製造することができる。本発明の蛍光体は、焼成により、式（１）で表される化合物に付活剤としてＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｈｏ、Ｄｙ、ＥｒおよびＴｍからなる群より選ばれる１種以上を含有されてなる蛍光体となる金属化合物混合物を焼成することにより製造することができる。すなわち、対応する金属元素を含有する化合物を所定の組成となるように秤量し混合した後に得られた金属化合物混合物を焼成することにより製造することができる。例えば好ましい組成の一つであるＭｇ 0.995Ｈｏ0.005Ｉｎ2Ｏ4で表される蛍光体は、ＭｇＳＯ4・７Ｈ2Ｏ、ＩｎＣｌ2・４Ｈ2Ｏ、Ｈｏ（ＮＯ3）3・５Ｈ2ＯをＭｇ：Ｈｏ：Ｉｎのモル比が０．９９５：０．００５：２となるように秤量し混合した後に得られる金属化合物混合物を焼成することにより製造することができる。 Next, a method for producing the phosphor of the present invention will be described.
The phosphor of the present invention can be manufactured, for example, as follows. The phosphor of the present invention is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, Er and Tm as an activator for the compound represented by the formula (1) by firing. It can manufacture by baking the metal compound mixture used as the fluorescent substance containing a seed or more. That is, it can be produced by firing a metal compound mixture obtained after weighing and mixing a compound containing a corresponding metal element to have a predetermined composition. For example, a phosphor represented by Mg 0.995 Ho 0.005 In 2 O 4 , which is one of the preferred compositions, includes MgSO 4 · 7H 2 O, InCl 2 · 4H 2 O, and Ho (NO 3 ) 3 · 5H 2 O. It can be manufactured by firing a metal compound mixture obtained after weighing and mixing so that the molar ratio of: Ho: In is 0.995: 0.005: 2.

前記の金属元素を含有する化合物としては、マグネシウム、カルシウム、ストロンチウム、バリウム、亜鉛、スカンジウム、イットリウム、ホウ素、アルミニウム、ガリウム、インジウム、セリウム、プラセオジム、ネオジム、サマリウム、ユウロピウム、テルビウム、ホルミウム、ジスプロシウム、エルビウム、ツリウムの化合物で、例えば、酸化物を用いるか、または水酸化物、炭酸塩、硝酸塩、硫酸塩、ハロゲン化物、シュウ酸塩など高温で分解および／または酸化して酸化物になり得るものを用いることができる。   Examples of the compound containing the metal element include magnesium, calcium, strontium, barium, zinc, scandium, yttrium, boron, aluminum, gallium, indium, cerium, praseodymium, neodymium, samarium, europium, terbium, holmium, dysprosium, and erbium. , Thulium compounds, for example using oxides, or hydroxides, carbonates, nitrates, sulfates, halides, oxalates, etc. that can decompose and / or oxidize at high temperatures to become oxides Can be used.

前記金属元素を含有する化合物の混合には、例えばボールミル、Ｖ型混合機、攪拌機等の通常工業的に用いられている装置を用いることができる。   For the mixing of the compound containing the metal element, for example, a generally industrially used apparatus such as a ball mill, a V-type mixer or a stirrer can be used.

また、前記金属元素を含有する化合物の水溶液と沈殿剤とを混合することにより、金属化合物混合物を得てもよい。この場合、該化合物としては、前記の硝酸塩、ハロゲン化物等が挙げられ、また該沈殿剤としては、アンモニア水、炭酸水素アンモニウム、尿素、シュウ酸、シュウ酸アンモニウム、クエン酸等、水酸化ナトリウム水溶液等が挙げられる。   Moreover, you may obtain a metallic compound mixture by mixing the aqueous solution of the compound containing the said metallic element, and a precipitant. In this case, examples of the compound include the nitrates and halides, and examples of the precipitant include ammonia water, ammonium hydrogen carbonate, urea, oxalic acid, ammonium oxalate, citric acid, and the like, an aqueous sodium hydroxide solution. Etc.

前記金属化合物混合物を、例えば８５０℃〜１８００℃の温度範囲にて１〜１００時間保持して焼成することにより本発明の蛍光体が得られる。金属化合物混合物に水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解および／または酸化して酸化物になりうるものが含有されている場合、焼成の前に、金属化合物混合物を、例えば４００℃以上８５０℃未満の温度範囲で保持して仮焼することにより、酸化物としたり、結晶水を除去することも可能である。また、仮焼後に粉砕を行うこともできる。   For example, the phosphor of the present invention is obtained by firing the metal compound mixture for 1 to 100 hours in a temperature range of 850 ° C. to 1800 ° C., for example. If the metal compound mixture contains hydroxides, carbonates, nitrates, halides, oxalates, etc. that can be decomposed and / or oxidized to form oxides at high temperatures, before firing, the metal compound mixture For example, it is possible to obtain an oxide or to remove crystal water by holding and calcining in a temperature range of 400 ° C. or higher and lower than 850 ° C. Moreover, it can also grind | pulverize after calcination.

焼成時の雰囲気は、酸化性雰囲気、還元性雰囲気のいずれでもよく、酸化性雰囲気としては大気、酸素を含有する雰囲気等が挙げられ、還元性雰囲気としては水素を０．１〜１００体積％含有する窒素、水素を０．１〜１００体積％含有するアルゴン等を含有する雰囲気等が挙げられる。また仮焼時の雰囲気は、大気等の酸化性雰囲気、還元性雰囲気のいずれでもよい。また、得られる蛍光体の結晶性を高めるために、焼成または仮焼時に金属化合物混合物の中に適量の反応促進剤を存在させてもよい。反応促進剤としては、例えば、ＬｉＦ、ＮａＦ、ＫＦ、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ、Ｌｉ2ＣＯ3、Ｎａ2ＣＯ3、Ｋ2ＣＯ3、ＮａＨＣＯ3、ＮＨ4Ｃｌ、ＮＨ4Ｉなどを挙げることができる。 The atmosphere during firing may be either an oxidizing atmosphere or a reducing atmosphere. Examples of the oxidizing atmosphere include air, an atmosphere containing oxygen, and the reducing atmosphere contains 0.1 to 100% by volume of hydrogen. And an atmosphere containing nitrogen or the like containing 0.1 to 100% by volume of hydrogen. The atmosphere during calcination may be either an oxidizing atmosphere such as air or a reducing atmosphere. In order to increase the crystallinity of the obtained phosphor, an appropriate amount of a reaction accelerator may be present in the metal compound mixture during firing or calcination. Examples of the reaction accelerator include LiF, NaF, KF, LiCl, NaCl, KCl, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , NH 4 Cl, NH 4 I, and the like. it can.

さらに上記方法にて得られる蛍光体を、例えばボールミル、ジェットミル等を用いて粉砕することができる。また、洗浄、分級することができる。また、得られる蛍光体の輝度をさらに向上させるために、焼成を２回以上行うこともできる。   Furthermore, the phosphor obtained by the above method can be pulverized using, for example, a ball mill, a jet mill or the like. It can also be washed and classified. Moreover, in order to further improve the brightness | luminance of the fluorescent substance obtained, baking can also be performed twice or more.

また、本発明の蛍光体を用いてなる電子線励起発光素子の例として、ＦＥＤを挙げてその製造方法について説明する。ＦＥＤの製造方法としては例えば、例えば特開２００３−１９７１３３号公報に開示されているような公知の方法が使用できる。すなわち赤色、緑色、青色のそれぞれの電子線励起発光素子用蛍光体と例えばセルロース系化合物、ポリビニルアルコールのような高分子化合物からなるバインダーおよび有機溶媒とを混合し、蛍光体ペーストを調製する。該蛍光体ペーストを前面板となる陽極ガラス基板上に塗布、乾燥、焼成し、蛍光体膜を形成する。この蛍光体膜が形成された陽極ガラス基板と電界放出源（エミッタ、グリッド）を有する陰極ガラス基板とを重ね合わせて接着し、内部を排気し、真空状態を保つように封じきることで、ＦＥＤを製造することができる。   In addition, as an example of an electron beam excitation light-emitting device using the phosphor of the present invention, a method for manufacturing the FED will be described. As a method for producing the FED, for example, a known method as disclosed in, for example, JP-A-2003-197133 can be used. That is, phosphors for electron beam-excited light emitting elements of red, green, and blue are mixed with a binder made of a polymer compound such as a cellulose compound or polyvinyl alcohol and an organic solvent to prepare a phosphor paste. The phosphor paste is applied onto an anode glass substrate serving as a front plate, dried and fired to form a phosphor film. The anode glass substrate on which the phosphor film is formed and the cathode glass substrate having a field emission source (emitter, grid) are bonded and bonded together, and the inside is evacuated and sealed so as to maintain a vacuum state. Can be manufactured.

以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらによって限定されるものではない。
１．発光特性評価
蛍光体を塗布したガラス基板を真空槽内に配置させ、蛍光体に電子線を照射することにより、蛍光体を発光させ、発光強度を蛍光分光計（Ｏｃｅａｎ Ｏｐｔｉｃｓ社製、装置名：ＵＳＢ−２０００ＦＬ）で測定することにより行なった。
２．電気伝導率算出
蛍光体の電気伝導度を直流四端子法により評価することにより、電気伝導率を算出した。具体的には、蛍光体焼結体の表面の４箇所に電極を取り付け、この電極に導線を接続して、電圧値、電流値、サンプル断面積、電極間距離を室温にて測定し、電気伝導率（単位はＳ・ｃｍ-1）を算出した。
３．耐久性評価
蛍光体を塗布したガラス基板を空気中に１週間静置した後、前記の発光特性評価を行なうことにより行なった。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
1. Evaluation of luminous characteristics A glass substrate coated with a phosphor is placed in a vacuum chamber, and the phosphor is irradiated with an electron beam to cause the phosphor to emit light, and the emission intensity is measured by a fluorescence spectrometer (manufactured by Ocean Optics, device name: (USB-2000FL).
2. Calculation of electric conductivity The electric conductivity was calculated by evaluating the electric conductivity of the phosphor by the DC four-terminal method. Specifically, electrodes are attached to four locations on the surface of the phosphor sintered body, a lead wire is connected to this electrode, and the voltage value, current value, sample cross-sectional area, and interelectrode distance are measured at room temperature. The conductivity (unit: S · cm −1 ) was calculated.
3. Durability Evaluation The glass substrate coated with the phosphor was left in the air for 1 week, and then the light emission characteristics were evaluated as described above.

実施例１
Ｍｇ0.995Ｈｏ0.005Ｉｎ2Ｏ4
ＭｇＳＯ4・７Ｈ2Ｏ、Ｈｏ（ＮＯ3）3・５Ｈ2Ｏ、ＩｎＣｌ2・４Ｈ2Ｏの各原料をＭｇ：Ｈｏ：Ｉｎのモル比が０．９９５：０．００５：２となるように秤量後、これらと蒸留水とを混合し３０分攪拌して得られた溶液と、等量のＮａＯＨ水溶液とを混合することにより沈殿を発生させ、沈殿をろ過、洗浄後、１２０℃で乾燥させることにより金属化合物混合物を得た。得られた金属化合物混合物を大気中８００℃で１２時間保持して仮焼した後、粉砕し得られた仮焼品を直径８ｍｍのペレットに成型し、空気中１４００℃で２４時間焼成することにより組成式がＭｇ0.995Ｈｏ0.005Ｉｎ2Ｏ4で表される蛍光体１からなる焼結体を得た。該焼結体の電気伝導率は０．５Ｓ・ｃｍ-1であった。また該焼結体を粉砕して得られた蛍光体１が塗布されたガラス基板を真空槽内に設置し、加速電圧が３ｋＶの電子線を照射すると、緑色に発光した。また、蛍光体１につき耐久性評価を行なったところ、発光強度は低下しなかった。 Example 1
Mg 0.995 Ho 0.005 In 2 O 4
Each raw material of MgSO 4 · 7H 2 O, Ho (NO 3 ) 3 · 5H 2 O and InCl 2 · 4H 2 O is adjusted so that the molar ratio of Mg: Ho: In is 0.995: 0.005: 2. After weighing, these and distilled water are mixed and stirred for 30 minutes, and an equal amount of NaOH aqueous solution is mixed to generate a precipitate. The precipitate is filtered, washed, and dried at 120 ° C. As a result, a metal compound mixture was obtained. The obtained metal compound mixture was calcined by holding at 800 ° C. for 12 hours in the air, and then the calcined product obtained by pulverization was formed into pellets having a diameter of 8 mm and fired at 1400 ° C. in air for 24 hours. A sintered body made of phosphor 1 having a composition formula represented by Mg 0.995 Ho 0.005 In 2 O 4 was obtained. The sintered body had an electric conductivity of 0.5 S · cm −1 . Further, when a glass substrate coated with the phosphor 1 obtained by pulverizing the sintered body was placed in a vacuum chamber and irradiated with an electron beam having an acceleration voltage of 3 kV, it emitted green light. Further, when the durability of the phosphor 1 was evaluated, the emission intensity did not decrease.

実施例２
Ｍｇ0.995Ｓｍ0.005Ｉｎ2Ｏ4
ＭｇＳＯ4・７Ｈ2Ｏ、Ｓｍ（ＮＯ3）3・６Ｈ2Ｏ、ＩｎＣｌ2・４Ｈ2Ｏの各原料をＭｇ：Ｓｍ：Ｉｎのモル比が０．９９５：０．００５：２となるように秤量後、これらと蒸留水とを混合し３０分攪拌して得られた溶液と、等量のＮａＯＨ水溶液とを混合することにより沈殿を発生させ、沈殿をろ過、洗浄後、１２０℃で乾燥させることにより金属化合物混合物を得た。得られた金属化合物混合物を大気中８００℃で１２時間保持して仮焼した後、粉砕し得られた仮焼品を直径８ｍｍのペレットに成型し、空気中１４００℃で２４時間焼成することにより組成式がＭｇ0.995Ｓｍ0.005Ｉｎ2Ｏ4で表される蛍光体２からなる焼結体を得た。該焼結体の電気伝導率は０．６Ｓ・ｃｍ-1であった。また該焼結体を粉砕して得られた蛍光体２が塗布されたガラス基板を真空槽内に設置し、加速電圧が３ｋＶの電子線を照射すると、橙色に発光した。また、蛍光体２につき耐久性評価を行なったところ、発光強度は低下しなかった。 Example 2
Mg 0.995 Sm 0.005 In 2 O 4
The raw materials of MgSO 4 .7H 2 O, Sm (NO 3 ) 3 .6H 2 O, and InCl 2 .4H 2 O are adjusted so that the molar ratio of Mg: Sm: In is 0.995: 0.005: 2. After weighing, these and distilled water are mixed and stirred for 30 minutes, and an equal amount of NaOH aqueous solution is mixed to generate a precipitate. The precipitate is filtered, washed, and dried at 120 ° C. As a result, a metal compound mixture was obtained. The obtained metal compound mixture was calcined by holding at 800 ° C. for 12 hours in the air, and then the calcined product obtained by pulverization was formed into pellets having a diameter of 8 mm and fired at 1400 ° C. in air for 24 hours. A sintered body made of phosphor 2 whose composition formula is represented by Mg 0.995 Sm 0.005 In 2 O 4 was obtained. The sintered body had an electric conductivity of 0.6 S · cm −1 . Further, when a glass substrate coated with the phosphor 2 obtained by pulverizing the sintered body was placed in a vacuum chamber and irradiated with an electron beam having an acceleration voltage of 3 kV, it emitted orange light. Moreover, when durability evaluation was performed about the fluorescent substance 2, the emitted light intensity did not fall.

実施例３
（Ｍｇ0.8Ｃａ0.2）0.995Ｈｏ0.005Ｉｎ2Ｏ4
ＭｇＳＯ4・７Ｈ2Ｏ、ＣａＣｌ2、Ｈｏ（ＮＯ3）3・５Ｈ2Ｏ、ＩｎＣｌ2・４Ｈ2Ｏの各原料をＭｇ：Ｃａ：Ｈｏ：Ｉｎのモル比が０．７９６：０．１９９：０．００５：２となるように秤量後、これらと蒸留水とを混合し３０分攪拌して得られた溶液と、等量のＮａＯＨ水溶液とを混合することにより沈殿を発生させ、沈殿をろ過、洗浄後、１２０℃で乾燥させることにより金属化合物混合物を得た。得られた金属化合物混合物を、大気中８００℃で１２時間保持して仮焼した後、粉砕し得られた仮焼品を直径８ｍｍのペレットに成型し、空気中１４００℃で２４時間焼成することにより組成式が（Ｍｇ0.8Ｃａ0.2）0.995Ｈｏ0.005Ｉｎ2Ｏ4で表される蛍光体３からなる焼結体を得た。該焼結体の電気伝導率は０．３Ｓ・ｃｍ-1であった。また該焼結体を粉砕して得られた蛍光体３が塗布されたガラス基板を真空槽内に設置し、加速電圧が３ｋＶの電子線を照射すると、緑色に発光した。また、蛍光体３につき耐久性評価を行なったところ、発光強度は低下しなかった。 Example 3
(Mg 0.8 Ca 0.2 ) 0.995 Ho 0.005 In 2 O 4
Each raw material of MgSO 4 · 7H 2 O, CaCl 2 , Ho (NO 3 ) 3 · 5H 2 O and InCl 2 · 4H 2 O has a molar ratio of Mg: Ca: Ho: In of 0.796: 0.199: After weighing to 0.005: 2, these are mixed with distilled water and stirred for 30 minutes, and an equivalent amount of NaOH aqueous solution is mixed to generate precipitate, and the precipitate is filtered. After washing, the mixture was dried at 120 ° C. to obtain a metal compound mixture. The obtained metal compound mixture is calcined by holding at 800 ° C. for 12 hours in the atmosphere, and then the calcined product obtained by pulverization is formed into a pellet having a diameter of 8 mm and fired at 1400 ° C. in air for 24 hours. Thus, a sintered body made of the phosphor 3 whose composition formula is represented by (Mg 0.8 Ca 0.2 ) 0.995 Ho 0.005 In 2 O 4 was obtained. The sintered body had an electric conductivity of 0.3 S · cm −1 . When a glass substrate coated with the phosphor 3 obtained by pulverizing the sintered body was placed in a vacuum chamber and irradiated with an electron beam having an acceleration voltage of 3 kV, it emitted green light. Moreover, when durability evaluation was performed about the fluorescent substance 3, the emitted light intensity did not fall.

実施例４
（Ｚｎ0.8Ｃａ0.2）0.995Ｈｏ0.005Ｉｎ2Ｏ4
ＺｎＣｌ2、ＣａＣｌ2、Ｈｏ（ＮＯ3）3・５Ｈ2Ｏ、ＩｎＣｌ2・４Ｈ2Ｏの各原料をＺｎ：Ｃａ：Ｈｏ：Ｉｎのモル比が０．７９６：０．１９９：０．００５：２となるように秤量後、これらと蒸留水とを混合し３０分攪拌して得られた溶液と、等量のＮａＯＨ水溶液とを混合することにより沈殿を発生させ、沈殿をろ過、洗浄後、１２０℃で乾燥させることにより金属化合物混合物を得た。得られた金属化合物混合物を、大気中８００℃で１２時間保持して仮焼した後、粉砕し得られた仮焼品を直径８ｍｍのペレットに成型し、空気中１４００℃で２４時間焼成することにより組成式が（Ｚｎ0.8Ｃａ0.2）0.995Ｈｏ0.005Ｉｎ2Ｏ4で表される蛍光体４からなる焼結体を得た。該焼結体の電気伝導率は０．５Ｓ・ｃｍ-1であった。また該焼結体を粉砕して得られた蛍光体４が塗布されたガラス基板を真空槽内に設置し、加速電圧が３ｋＶの電子線を照射すると、緑色に発光した。また、蛍光体４につき耐久性評価を行なったところ、発光強度は低下しなかった。 Example 4
(Zn 0.8 Ca 0.2 ) 0.995 Ho 0.005 In 2 O 4
Each of ZnCl 2 , CaCl 2 , Ho (NO 3 ) 3 .5H 2 O and InCl 2 .4H 2 O has a Zn: Ca: Ho: In molar ratio of 0.796: 0.199: 0.005: After weighing so that it becomes 2, precipitates are generated by mixing these and distilled water and stirring for 30 minutes, and an equal amount of NaOH aqueous solution, and the precipitate is filtered, washed, A metal compound mixture was obtained by drying at 120 ° C. The obtained metal compound mixture is calcined by holding at 800 ° C. for 12 hours in the atmosphere, and then the calcined product obtained by pulverization is formed into a pellet having a diameter of 8 mm and fired at 1400 ° C. in air for 24 hours. Thus, a sintered body made of the phosphor 4 whose composition formula is represented by (Zn 0.8 Ca 0.2 ) 0.995 Ho 0.005 In 2 O 4 was obtained. The sintered body had an electric conductivity of 0.5 S · cm −1 . Further, when a glass substrate coated with the phosphor 4 obtained by pulverizing the sintered body was placed in a vacuum chamber and irradiated with an electron beam having an acceleration voltage of 3 kV, it emitted green light. Moreover, when durability evaluation was performed about the fluorescent substance 4, emitted light intensity did not fall.

実施例５
Ｚｎ0.995Ｈｏ0.005Ｇａ2Ｏ4
ＺｎＯ、Ｈｏ（ＮＯ3）3・５Ｈ2Ｏ、Ｇａ2Ｏ3の各原料をＺｎ：Ｈｏ：Ｇａのモル比が０．９９５：０．００５：２となるように秤量後、これらを、メタノールを媒体とした湿式ボールミルにより混合し、得られたスラリーを乾燥し、金属化合物混合物を得た。得られた金属化合物混合物を、大気中８００℃で１２時間保持して仮焼した後、粉砕し得られた仮焼品を直径８ｍｍのペレットに成型し、空気中１４００℃で２４時間焼成後、さらに１００％Ｈ2雰囲気中６００℃で１０時間焼成することにより組成式がＺｎ0.995Ｈｏ0.005Ｇａ2Ｏ4で表される蛍光体５からなる焼結体を得た。該焼結体蛍光体５の電気伝導率は３．７×１０-3Ｓ・ｃｍ-1であった。また該焼結体を粉砕して得られた蛍光体５が塗布されたガラス基板を真空槽内に設置し、加速電圧が３ｋＶの電子線を照射すると、赤紫色に発光した。また、蛍光体５につき耐久性評価を行なったところ、発光強度は低下しなかった。 Example 5
Zn 0.995 Ho 0.005 Ga 2 O 4
ZnO, Ho (NO 3 ) 3 .5H 2 O, and Ga 2 O 3 were weighed so that the molar ratio of Zn: Ho: Ga was 0.995: 0.005: 2, and these were then added to methanol. Was mixed by a wet ball mill using as a medium, and the resulting slurry was dried to obtain a metal compound mixture. The obtained metal compound mixture was calcined by holding at 800 ° C. for 12 hours in the air, and then the calcined product obtained by pulverization was formed into pellets having a diameter of 8 mm, and after firing at 1400 ° C. in air for 24 hours, further composition formula by firing 100% H 2 at 600 ° C. in an atmosphere for 10 hours to obtain a sintered body made of a phosphor 5, represented by Zn 0.995 Ho 0.005 Ga 2 O 4 . The sintered phosphor 5 had an electric conductivity of 3.7 × 10 −3 S · cm −1 . Further, when a glass substrate coated with the phosphor 5 obtained by pulverizing the sintered body was placed in a vacuum chamber and irradiated with an electron beam having an acceleration voltage of 3 kV, it emitted reddish purple light. Moreover, when durability evaluation was performed about the fluorescent substance 5, the emitted light intensity did not fall.

Claims (9)

式Ｍ1Ｏ・Ｍ2 2Ｏ3（式中のＭ1はＭｇ、Ｃａ、Ｓｒ、ＢａおよびＺｎからなる群より選ばれる１種以上であり、Ｍ2はＳｃ、Ｙ、Ｂ、Ａｌ、ＧａおよびＩｎからなる群より選ばれる１種以上である。）で表される化合物に付活剤としてＬｎ（ただしＬｎはＣｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｈｏ、Ｄｙ、ＥｒおよびＴｍからなる群より選ばれる１種以上である。）が含有されてなることを特徴とする電子線励起発光素子用蛍光体。 Formula M 1 O · M 2 2 O 3 (wherein M 1 is at least one selected from the group consisting of Mg, Ca, Sr, Ba and Zn, and M 2 is Sc, Y, B, Al, Ga) And Ln (wherein Ln is Ce, Pr, Nd, Sm, Eu, Tb, Ho, Dy, Er, and Tm) as an activator for the compound represented by the formula: A phosphor for an electron beam-excited light-emitting element, which is at least one selected from the group consisting of: 式（Ｍｇ1-xＭ1 x）Ｏ・（Ｉｎ1-yＭ2 y）2Ｏ3（式中のＭ1およびＭ2は前記と同じ意味を有し、ｘは０以上１未満の範囲であり、ｙは０以上１未満の範囲である。）で表される化合物に付活剤としてＬｎ（ただしＬｎは前記と同じ意味を有する。）が含有されてなる請求項１記載の蛍光体。 Formula (Mg 1 -x M 1 x ) O. (In 1 -y M 2 y ) 2 O 3 (wherein M 1 and M 2 have the same meaning as above, and x is a range of 0 or more and less than 1) The phosphor according to claim 1, wherein y is in the range of 0 or more and less than 1, Ln (where Ln has the same meaning as described above) is contained as an activator. . 式（Ｚｎ1-xＭ1 x）Ｏ・（Ｉｎ1-yＭ2 y）2Ｏ3（式中のＭ1およびＭ2は前記と同じ意味を有し、ｘは０以上１未満の範囲であり、ｙは０以上１未満の範囲である。）で表される化合物に付活剤としてＬｎ（ただしＬｎは前記と同じ意味を有する。）が含有されてなる請求項１記載の蛍光体。 Formula (Zn 1 -x M 1 x ) O. (In 1 -y M 2 y ) 2 O 3 (wherein M 1 and M 2 have the same meaning as above, and x is a range from 0 to less than 1) The phosphor according to claim 1, wherein y is in the range of 0 or more and less than 1, Ln (where Ln has the same meaning as described above) is contained as an activator. . 請求項１〜３のいずれかに記載の蛍光体を含有してなることを特徴とする電子線励起発光素子。   An electron beam-excited light-emitting device comprising the phosphor according to claim 1. 蛍光体の励起源が低速電子線である請求項４記載の電子線励起発光素子。   The electron beam excitation light-emitting device according to claim 4, wherein the excitation source of the phosphor is a low-energy electron beam. 電子線励起発光素子がフィールドエミッションディスプレイであることを特徴とする請求項１〜３のいずれかに記載の蛍光体。   The phosphor according to claim 1, wherein the electron beam excitation light-emitting element is a field emission display. 電子線励起発光素子が表面電界ディスプレイであることを特徴とする請求項１〜３のいずれかに記載の蛍光体。   The phosphor according to any one of claims 1 to 3, wherein the electron beam excitation light-emitting element is a surface electric field display. 請求項６記載の蛍光体を含有してなるフィールドエミッションディスプレイ。   A field emission display comprising the phosphor according to claim 6. 請求項７記載の蛍光体を含有してなる表面電界ディスプレイ。   A surface electric field display comprising the phosphor according to claim 7.
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