JPH09279140A - Fluorescent substance for excitation with low-energy electron beam and reduction in resistance of the same fluorescent substance - Google Patents
Fluorescent substance for excitation with low-energy electron beam and reduction in resistance of the same fluorescent substanceInfo
- Publication number
- JPH09279140A JPH09279140A JP8086401A JP8640196A JPH09279140A JP H09279140 A JPH09279140 A JP H09279140A JP 8086401 A JP8086401 A JP 8086401A JP 8640196 A JP8640196 A JP 8640196A JP H09279140 A JPH09279140 A JP H09279140A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- low
- electron beam
- fluorescent substance
- beam excitation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、蛍光表示管やフィ
ールドエミッションディスプレイに使用する低速電子線
励起用蛍光体に係わり、特にカラー表示装置に必要な３
原色のうち赤色をカラーブラウン管におけると同程度に
優れた色純度で発光する低速電子線励起用蛍光体、およ
びその蛍光体を低抵抗化する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor for low-speed electron beam excitation used in a fluorescent display tube or a field emission display, and in particular, it is necessary for a color display device.
The present invention relates to a phosphor for low-speed electron beam excitation, which emits red among primary colors with a color purity as excellent as that in a color CRT, and a method for reducing the resistance of the phosphor.
【０００２】[0002]
【従来の技術】低速電子線励起用蛍光体としては、電子
線による蛍光体表面での帯電を生じさせないようにする
ため導電性を有する（低抵抗の）蛍光体が必要であり、
また、従来の低速電子線励起用赤色発光体としては、例
えば、１９８７年にオーム社から発行された「蛍光体ハ
ンドブック」の第３０３頁に記載されている表１に示す
蛍光体がある。2. Description of the Related Art As a phosphor for low-speed electron beam excitation, a phosphor having conductivity (low resistance) is required to prevent charging of the phosphor surface by an electron beam.
Further, as a conventional red light emitting body for low speed electron beam excitation, for example, there is a phosphor shown in Table 1 described on page 303 of "Phosphor Handbook" published by Ohmsha in 1987.
【０００３】[0003]
【表１】 [Table 1]
【０００４】表１において、（ａ）のＳｎＯ2 ：Ｅｕ3+
は、導電性の高いＳｎＯ2 にＥｕ3+イオンの発光中心を
形成した蛍光体である。また、他の二つ（（ｂ）および
（ｃ））は、絶縁性蛍光体（それぞれ、Ｚｎ0.20Ｃｄ
0.60Ｓ：Ａｇ，ＣｌおよびＺｎ 0.30Ｃｄ0.70Ｓ：Ａｇ，
Ｃｌ）にＩｎ2 Ｏ3 の導電性物質を混合して導電性をも
たせた蛍光体である。In Table 1, SnO of (a)Two: Eu3+
Is highly conductive SnOTwoTo Eu3+Ion emission center
It is the formed phosphor. Also, the other two ((b) and
(C) is an insulating phosphor (respectively Zn0.20Cd
0.60S: Ag, Cl and Zn 0.30Cd0.70S: Ag,
Cl) to InTwoOThreeIt also has conductivity by mixing the conductive substances of
It is a fluorescent substance that has been applied.
【０００５】[0005]
【発明が解決しようとする課題】表１に示す従来の低速
電子線励起用赤色発光蛍光体において、（ａ）の蛍光体
は、蛍光体材料自体に導電性材料を使用しているため、
さらに導電性物質を混合する必要はないが、色度座標値
から分かるようにフルカラー表示用赤色蛍光体として
は、（ｂ）の蛍光体より赤色発光の色純度が悪い。ま
た、（ｂ）と（ｃ）の蛍光体の場合、蛍光体材料に導電
性材料が含まれていないため、高価な導電性物質である
Ｉｎ2 Ｏ3 を混合しなければならないので、コスト高に
なり、また微妙な混合工程を必要とし、さらに、公害物
質であるカドミウムを使用しているという問題点もあ
る。さらに、（ｃ）の蛍光体の場合は、現在のカラーブ
ラウン管に使用されているＹ2 Ｏ3 ：Ｅｕ（ｘ＝０．６
４０，ｙ＝０．３３５）あるいはＹ 2 Ｏ2 Ｓ：Ｅｕ（ｘ
＝０．６２３，ｙ＝０．３４２）の赤色蛍光体と比較し
て色純度が悪い。The conventional low speed shown in Table 1
A red light-emitting phosphor for exciting an electron beam, the phosphor of (a)
Uses a conductive material for the phosphor material itself,
It is not necessary to mix conductive material, but chromaticity coordinate value
As you can see, as a red phosphor for full color display
Has a lower color purity of red light emission than the phosphor of (b). Ma
In the case of the phosphors of (b) and (c), the phosphor material is electrically conductive.
Since it does not contain a conductive material, it is an expensive conductive substance.
InTwoOThreeSince it has to be mixed, the cost is high.
It also requires a delicate mixing process,
There is also the problem of using quality cadmium
You. Furthermore, in the case of the phosphor of (c),
Y used for round pipeTwoOThree: Eu (x = 0.6
40, y = 0.335) or Y TwoOTwoS: Eu (x
= 0.623, y = 0.342)
And the color purity is poor.
【０００６】このように、従来の低速電子線励起用蛍光
体において、導電性を有し、しかも現在のカラーブラウ
ン管に使用されているＹ2 Ｏ3 ：Ｅｕ（ｘ＝０．６４
０，ｙ＝０．３３５）、あるいはＹ2 Ｏ2 Ｓ：Ｅｕ（ｘ
＝０．６２３，ｙ＝０．３４２）の赤色蛍光体と同等の
色純度のよい赤色発光をするものはなかった。As described above, Y 2 O 3 : Eu (x = 0.64), which is electrically conductive in the conventional phosphor for low-speed electron beam excitation and is used in the current color cathode ray tube.
0, y = 0.335), or Y 2 O 2 S: Eu (x
= 0.623, y = 0.342), none of them emitted red light with a color purity as good as that of the red phosphor.
【０００７】本発明の第１の目的は、カラーブラウン管
に使用されているＹ2 Ｏ3 ：Ｅｕ（ｘ＝０．６４０，ｙ
＝０．３３５）、あるいはＹ2 Ｏ2 Ｓ：Ｅｕ（ｘ＝０．
６２３，ｙ＝０．３４２）の赤色蛍光体と同等かそれ以
上に色純度のよい色調に赤色発光する低速電子線励起用
蛍光体を提供することにあり、また、本発明の第２の目
的は、その得られた低速電子線励起用蛍光体を低抵抗化
して導電性をもたせるようにする方法を提供することに
ある。The first object of the present invention is to provide Y 2 O 3 : Eu (x = 0.640, y) used in color cathode ray tubes.
= 0.335), or Y 2 O 2 S: Eu (x = 0.
623, y = 0.342), and a second object of the present invention is to provide a phosphor for low-speed electron beam excitation that emits red light in a color tone having a color purity equivalent to or higher than that of the red phosphor. Another object of the present invention is to provide a method for reducing the resistance of the obtained phosphor for low-speed electron beam excitation so as to have conductivity.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するた
め、本発明低速電子線励起用蛍光体は、発光母体材料Ｃ
ｕＡｌＳ2 に、Ｍｎ，Ｚｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，
Ｓｍ，Ｅｕ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎ
ｉ，Ｓｎ，Ｐｂ，Ｆ，Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，
Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｓｃ，Ｙおよ
びＯからなる群から選択した少なくとも１つの元素が発
光中心または付活剤としてドーピングされていることを
特徴とするものである。In order to achieve the above object, the phosphor for low-speed electron beam excitation of the present invention comprises a light-emitting base material C.
uAlS 2 contains Mn, Zn, La, Ce, Pr, Nd,
Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, N
i, Sn, Pb, F, Cl, Br, I, Li, Na,
It is characterized in that at least one element selected from the group consisting of K, Rb, Cs, P, As, Sb, Bi, Sc, Y and O is doped as an emission center or an activator.
【０００９】また、本発明低速電子線励起用蛍光体は、
ＣｕＡｌＳ2 とカルコパイライト系固溶体をつくる物質
を含む発光母体材料としての固溶体に、Ｍｎ，Ｚｎ，Ｌ
ａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄｙ，Ｈ
ｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，Ｃｌ，
Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａｓ，Ｓ
ｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる群から選択した少
なくとも１つの元素が発光中心または付活剤としてドー
ピングされていることを特徴とするものである。Further, the phosphor for low-speed electron beam excitation of the present invention comprises:
Mn, Zn, L is added to a solid solution as a light emitting host material containing CuAlS 2 and a substance that forms a chalcopyrite solid solution.
a, Ce, Pr, Nd, Sm, Eu, Tb, Dy, H
o, Er, Tm, Yb, Ni, Sn, Pb, F, Cl,
Br, I, Li, Na, K, Rb, Cs, P, As, S
It is characterized in that at least one element selected from the group consisting of b, Bi, Sc, Y and O is doped as an emission center or an activator.
【００１０】また、本発明低速電子線励起用蛍光体は、
発光母体材料ＣｕＧａx Ａｌ1-x Ｓ 2 （０＜ｘ＜１）ま
たはＣｕＡｌＳx Ｓｅ2-x （０＜ｘ＜２）に、Ｍｎ，Ｚ
ｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，
Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａ
ｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる群から選択
した少なくとも１つの元素が発光中心または付活剤とし
てドーピングされていることを特徴とするものである。Further, the phosphor for low-speed electron beam excitation of the present invention is
Luminescent material CuGaxAl1-xS Two(0 <x <1)
Or CuAlSxSe2-x(0 <x <2), Mn, Z
n, La, Ce, Pr, Nd, Sm, Eu, Tb, D
y, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl, Br, I, Li, Na, K, Rb, Cs, P, A
selected from the group consisting of s, Sb, Bi, Sc, Y and O
At least one of the selected elements serves as a luminescent center or activator.
It is characterized by being doped.
【００１１】また、本発明低速電子線励起用蛍光体は、
発光母体材料ＣｕＡｌＳ2 に、Ｍｎ，Ｚｎ，Ｌａ，Ｃ
ｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅ
ｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，Ｃｌ，Ｂｒ，
Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａｓ，Ｓｂ，Ｂ
ｉ，Ｓｃ，ＹおよびＯからなる群から選択した少なくと
も１つの元素を含む化合物が発光中心または付活剤とし
てドーピングされていることを特徴とするものである。Further, the phosphor for low-speed electron beam excitation of the present invention comprises
Mn, Zn, La, and C are added to the light emitting host material CuAlS 2.
e, Pr, Nd, Sm, Eu, Tb, Dy, Ho, E
r, Tm, Yb, Ni, Sn, Pb, F, Cl, Br,
I, Li, Na, K, Rb, Cs, P, As, Sb, B
It is characterized in that a compound containing at least one element selected from the group consisting of i, Sc, Y and O is doped as an emission center or an activator.
【００１２】また、本発明低速電子線励起用蛍光体は、
ＣｕＡｌＳ2 とカルコパイライト系固溶体をつくる物質
を含む発光母体材料としての固溶体に、Ｍｎ，Ｚｎ，Ｌ
ａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄｙ，Ｈ
ｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，Ｃｌ，
Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａｓ，Ｓ
ｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる群から選択した少
なくとも１つの元素を含む化合物が発光中心または付活
剤としてドーピングされていることを特徴とするもので
ある。Further, the phosphor for low-speed electron beam excitation of the present invention comprises
Mn, Zn, L is added to a solid solution as a light emitting host material containing CuAlS 2 and a substance that forms a chalcopyrite solid solution.
a, Ce, Pr, Nd, Sm, Eu, Tb, Dy, H
o, Er, Tm, Yb, Ni, Sn, Pb, F, Cl,
Br, I, Li, Na, K, Rb, Cs, P, As, S
It is characterized in that a compound containing at least one element selected from the group consisting of b, Bi, Sc, Y and O is doped as an emission center or an activator.
【００１３】また、本発明低速電子線励起用蛍光体は、
発光母体材料ＣｕＧａx Ａｌ1-x Ｓ 2 （０＜ｘ＜１）ま
たはＣｕＡｌＳx Ｓｅ2-x （０＜ｘ＜２）に、Ｍｎ，Ｚ
ｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，
Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａ
ｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる群から選択
した少なくとも１つの元素を含む化合物が発光中心また
は付活剤としてドーピングされていることを特徴とする
ものである。Further, the phosphor for low-speed electron beam excitation of the present invention comprises:
Luminescent material CuGaxAl1-xS Two(0 <x <1)
Or CuAlSxSe2-x(0 <x <2), Mn, Z
n, La, Ce, Pr, Nd, Sm, Eu, Tb, D
y, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl, Br, I, Li, Na, K, Rb, Cs, P, A
selected from the group consisting of s, Sb, Bi, Sc, Y and O
The compound containing at least one element is
Is characterized as being doped as an activator
Things.
【００１４】また、本発明低速電子線励起用蛍光体を低
抵抗化する方法は、前記低速電子線励起用蛍光体の粉末
を、飽和硫黄雰囲気中において、６００℃以上の温度で
１０〜３０時間加熱するようにしたことを特徴とするも
のである。The method for lowering the resistance of the phosphor for low-speed electron beam excitation according to the present invention is the powder of the phosphor for low-speed electron beam excitation, in a saturated sulfur atmosphere, at a temperature of 600 ° C. or higher for 10 to 30 hours. It is characterized by being heated.
【００１５】[0015]
【発明の実施の形態】以下に添付図面を参照し、実施の
形態に基づいて本発明を詳細に説明する。最初に、本発
明低速電子線励起用蛍光体の合成方法について説明す
る。発光母体材料ＣｕＡｌＳ2 にＭｎを発光中心として
ドーピングした本発明による低速電子線励起用蛍光体を
合成するには、例えば、化学量論比に相当する純度６Ｎ
のＣｕ，Ａｌ，Ｓと０．０１〜１０wt％に相当する高純
度のＭｎあるいはＭｎＳをＢＮるつぼに充填し、１３０
０℃で溶融して合成する。次いで、この合成された多結
晶塊を適当な粉末に粉砕して低抵抗化の処理に供するた
めの低速電子線励起用蛍光体の粉末にする。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments with reference to the accompanying drawings. First, a method for synthesizing the phosphor for low-speed electron beam excitation of the present invention will be described. In order to synthesize the phosphor for low-speed electron beam excitation according to the present invention, which is obtained by doping the light-emitting host material CuAlS 2 with Mn as an emission center, for example, a purity of 6N corresponding to a stoichiometric ratio is used.
Of Cu, Al, and S and 0.01 to 10 wt% of high-purity Mn or MnS in a BN crucible,
Melt at 0 ° C to synthesize. Next, the synthesized polycrystal lump is pulverized into an appropriate powder to obtain a powder of a phosphor for low-speed electron beam excitation for use in a treatment for reducing resistance.
【００１６】また、さらに高品質の結晶を得るために、
上記得られた低速電子線励起用蛍光体の多結晶粉末を石
英アンプルに封入してヨウ素による化学輸送法によって
結晶成長させて単結晶を作製し、これを適当な粉末に粉
砕する。このようにして得られた多結晶粉末を酸などで
粉末表面をエッチングして粒径を整え、蛍光体粉末とし
て使用できるようにするか、あるいは、上記の方法で母
体材料だけを合成し、これに０．０１〜１０wt％に相当
する高純度のＭｎあるいはＭｎＳを混合し、Ｈ 2 Ｓガス
雰囲気中にて、１０００℃程度で６時間ほど焼成して発
光中心を形成し、その後、上記の方法によって粒径など
を整えて蛍光体粉末とする。In order to obtain higher quality crystals,
The obtained polycrystalline powder of the phosphor for low-speed electron beam excitation was used as a stone.
Encapsulate in an English ampoule and use a chemical transport method using iodine
A single crystal is made by growing the crystal and powdered into an appropriate powder.
Crush. The polycrystalline powder thus obtained is treated with an acid or the like.
The surface of the powder is etched to adjust the particle size to make phosphor powder.
Can be used by using the
Synthesize only body material, equivalent to 0.01-10 wt%
Mixed with high purity Mn or MnS TwoS gas
Fired by firing in an atmosphere at about 1000 ° C for about 6 hours
Form the optical center and then the particle size etc. by the above method
To prepare phosphor powder.
【００１７】以上においてはＭｎのみを発光中心として
ドーピングした場合であるが、元素Ｍｎのほかに、元素
Ｚｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，
Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａ
ｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯのうちから少なくと
も１つの元素、または、これらの元素のうちから少なく
とも１つの元素を含む化合物をドーピングして発光中心
または付活剤として使用することも可能である。In the above description, only Mn is doped as an emission center, but in addition to the element Mn, the elements Zn, La, Ce, Pr, Nd, Sm, Eu, Tb, D.
y, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl, Br, I, Li, Na, K, Rb, Cs, P, A
It is also possible to dope at least one element of s, Sb, Bi, Sc, Y and O or a compound containing at least one element of these elements and use it as a luminescent center or activator. Is.
【００１８】また、発光母体材料としても上述のＣｕＡ
ｌＳ2 のみでなく、ＣｕＡｌＳ2 とカルコパイライト系
固溶体をつくる他の物質を含む固溶体、例えばＣｕＧａ
x Ａｌ1-x Ｓ2 （０＜ｘ＜１）やＣｕＡｌＳx Ｓｅ2-x
（０＜ｘ＜２）を使用することも可能である。The above-mentioned CuA is also used as the light-emitting base material.
Not only 1S 2 , but also a solid solution containing CuAlS 2 and other substances that form a chalcopyrite-based solid solution, for example, CuGa
x Al 1-x S 2 (0 <x <1) and CuAlS x Se 2-x
It is also possible to use (0 <x <2).
【００１９】以上により得られた低速電子線励起用蛍光
体の粉末を本発明により低抵抗化する方法としては、上
記合成され、粉末化された蛍光体粉末を、さらに飽和硫
黄雰囲気中において６００℃以上の温度で１０〜３０時
間の範囲内で加熱処理を施す。この飽和硫黄雰囲気中で
の加熱処理により、蛍光体粉末の抵抗率は１０4 〜１０
6 のオーダーで急激に低抵抗化される。As a method for reducing the resistance of the phosphor for low-speed electron beam excitation obtained as described above according to the present invention, the phosphor powder thus synthesized and powdered is further heated at 600 ° C. in a saturated sulfur atmosphere. The heat treatment is performed at the above temperature for 10 to 30 hours. By the heat treatment in this saturated sulfur atmosphere, the resistivity of the phosphor powder is 10 4 to 10 4.
The resistance is drastically reduced on the order of 6 .
【００２０】本発明によって得られた低速電子線励起用
蛍光体（特に、Ｍｎ2+イオンの発光中心をもつＣｕＡｌ
Ｓ2 赤色発光蛍光体の場合）のカソードルミネッセンス
（ＣＬ）スペクトルの測定結果を図１に示す。同図か
ら、この蛍光体は赤色の波長６３５ｎｍに発光ピークを
有していることが分かる。The phosphor for low-speed electron beam excitation obtained by the present invention (in particular, CuAl having an emission center of Mn 2+ ion)
FIG. 1 shows the measurement result of the cathode luminescence (CL) spectrum of the S 2 red light emitting phosphor). From this figure, it can be seen that this phosphor has an emission peak at a red wavelength of 635 nm.
【００２１】図２は、上記本発明によるＭｎ2+イオンの
発光中心をもつＣｕＡｌＳ2 赤色発光蛍光体の発光色度
を、カラーブラウン管（ＣＲＴ）の発光色度とともに色
度図上に示している。同図から分かるように、本発明に
よる赤色発光蛍光体の発光色度座標値は、ｘ＝０．６６
４，ｙ＝０．３３６であり、この色調は、同時に示され
ているカラーブラウン管のＹ2 Ｏ3 ：Ｅｕ（ｘ＝０．６
４０，ｙ＝０．３３５）、あるいはＹ2 Ｏ2 Ｓ：Ｅｕ
（ｘ＝０．６２３，ｙ＝０．３４２）の赤色蛍光体と同
じかそれ以上に色純度の優れた赤色発光である。従っ
て、本発明による赤色発光を蛍光表示管やフィールドエ
ミッションディスプレイなどの表示装置に使用するとカ
ラーブラウン管と同等の色再現が可能となる。FIG. 2 shows the emission chromaticity of the CuAlS 2 red-emitting phosphor having the emission center of Mn 2+ ions according to the present invention on the chromaticity diagram together with the emission chromaticity of a color cathode ray tube (CRT). . As can be seen from the figure, the emission chromaticity coordinate value of the red light emitting phosphor according to the present invention is x = 0.66.
4, y = 0.336, and this color tone corresponds to Y 2 O 3 : Eu (x = 0.6) of the color CRT shown at the same time.
40, y = 0.335), or Y 2 O 2 S: Eu
It emits red light with the same or better color purity than the red phosphor of (x = 0.623, y = 0.342). Therefore, when the red light emission according to the present invention is used for a display device such as a fluorescent display tube or a field emission display, color reproduction equivalent to that of a color CRT becomes possible.
【００２２】また、上記本発明による蛍光体を低抵抗化
する方法によって得られた蛍光体の導電率は１．０Ω・
ｃｍ以下であった。The conductivity of the phosphor obtained by the method of reducing the resistance of the phosphor according to the present invention is 1.0 Ω.
cm or less.
【００２３】以上によって得られた本発明による赤色蛍
光体を、蛍光表示管やフィールドエミッションディスプ
レイ表示装置の蛍光面に塗布し、陰極からの１ｋＶ以下
の低速度電子線を照射することによって色純度の高い赤
色発光を得ることができる。The red phosphor according to the present invention obtained as described above is applied to the phosphor screen of a fluorescent display tube or a field emission display device, and irradiated with a low-velocity electron beam of 1 kV or less from the cathode to obtain color purity. High red emission can be obtained.
【００２４】[0024]
【発明の効果】本発明によれば、現在のカラーブラウン
管の赤色発光と同等以上の色純度をもって発光する表示
装置、例えば蛍光表示管やフィールドエミッションディ
スプレイ表示装置に使用するための低速電子線励起用の
赤色蛍光体を得ることができる。According to the present invention, for low-speed electron beam excitation for use in a display device that emits light with a color purity equal to or higher than the red light emission of the current color cathode ray tube, such as a fluorescent display tube or a field emission display display device. Can be obtained.
【００２５】また、本発明の蛍光体を低抵抗化する方法
によって、本発明低速電子線励起用蛍光体を低抵抗化
し、１．０Ω・ｃｍ以下の導電性をもたせるようにする
ことができるため、従来のように蛍光体に導電性物質を
混合するなどしなくても電子線による蛍光体表面の帯電
を防止することができる。このため、高価な導電物質を
使用する必要がなくなり、微妙な導電物質の混合工程を
省略することができる。Further, by the method for reducing the resistance of the phosphor of the present invention, the phosphor for low-speed electron beam excitation of the present invention can be made to have a low resistance and have a conductivity of 1.0 Ω · cm or less. It is possible to prevent the surface of the phosphor from being charged by an electron beam without mixing a conductive substance into the phosphor as in the conventional case. Therefore, it is not necessary to use an expensive conductive material, and a subtle mixing step of the conductive material can be omitted.
【００２６】さらにまた、本発明においては蛍光体粉末
を低速電子線励起用に適合するよう低抵抗化させる方法
が、飽和硫黄雰囲気中での熱処理法であるため、著しく
簡便に所望の導電性を有する蛍光体を製造することが可
能となる。Furthermore, in the present invention, the method of lowering the resistance of the phosphor powder so as to be suitable for low-speed electron beam excitation is a heat treatment method in a saturated sulfur atmosphere, so that the desired conductivity can be remarkably easily obtained. It becomes possible to manufacture the fluorescent substance which has.
【図１】Ｍｎ2+イオンの発光中心をもつ本発明によるＣ
ｕＡｌＳ2 赤色発光蛍光体のカソードルミネッセンスス
ペクトルを示している。FIG. 1 C according to the invention with an emission center of Mn 2+ ions.
4 shows a cathodoluminescence spectrum of a uAlS 2 red-emitting phosphor.
【図２】Ｍｎ2+イオンの発光中心をもつ本発明によるＣ
ｕＡｌＳ2 赤色蛍光体の色度座標位置を示す色度図を示
している。FIG. 2 C according to the invention with an emission center of Mn 2+ ions.
4 shows a chromaticity diagram showing the chromaticity coordinate position of the uAlS 2 red phosphor.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｊ 29/20 Ｈ０１Ｊ 29/20 31/12 31/12 Ｃ 31/15 31/15 Ｅ (72)発明者 佐藤 勝昭 神奈川県川崎市麻生区上麻生1087−169─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication location H01J 29/20 H01J 29/20 31/12 31/12 C 31/15 31/15 E (72) Inventor Katsuaki Sato 1087-169 Kamio, Aso-ku, Kawasaki-shi, Kanagawa
Claims (7)
ｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，
Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａ
ｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる群から選択
した少なくとも１つの元素が発光中心または付活剤とし
てドーピングされていることを特徴とする低速電子線励
起用蛍光体。1. A light-emitting base material CuAlS 2 containing Mn, Z
n, La, Ce, Pr, Nd, Sm, Eu, Tb, D
y, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl, Br, I, Li, Na, K, Rb, Cs, P, A
At least one element selected from the group consisting of s, Sb, Bi, Sc, Y and O is doped as an emission center or an activator, and a phosphor for low-speed electron beam excitation.
体をつくる物質を含む発光母体材料としての固溶体に、
Ｍｎ，Ｚｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔ
ｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐ
ｂ，Ｆ，Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃ
ｓ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる
群から選択した少なくとも１つの元素が発光中心または
付活剤としてドーピングされていることを特徴とする低
速電子線励起用蛍光体。2. A solid solution as a light-emitting host material containing CuAlS 2 and a substance forming a chalcopyrite solid solution,
Mn, Zn, La, Ce, Pr, Nd, Sm, Eu, T
b, Dy, Ho, Er, Tm, Yb, Ni, Sn, P
b, F, Cl, Br, I, Li, Na, K, Rb, C
At least one element selected from the group consisting of s, P, As, Sb, Bi, Sc, Y and O is doped as a luminescent center or an activator, and is a phosphor for slow electron beam excitation.
2 （０＜ｘ＜１）またはＣｕＡｌＳx Ｓｅ2-x （０＜ｘ
＜２）に、Ｍｎ，Ｚｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓ
ｍ，Ｅｕ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎ
ｉ，Ｓｎ，Ｐｂ，Ｆ，Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，
Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｓｃ，Ｙおよ
びＯからなる群から選択した少なくとも１つの元素が発
光中心または付活剤としてドーピングされていることを
特徴とする低速電子線励起用蛍光体。3. Luminescent material CuGa x Al 1-x S
2 (0 <x <1) or CuAlS x Se 2-x (0 <x
<2), Mn, Zn, La, Ce, Pr, Nd, S
m, Eu, Tb, Dy, Ho, Er, Tm, Yb, N
i, Sn, Pb, F, Cl, Br, I, Li, Na,
Slow electron beam excitation characterized in that at least one element selected from the group consisting of K, Rb, Cs, P, As, Sb, Bi, Sc, Y and O is doped as an emission center or activator. For phosphor.
ｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐｂ，Ｆ，
Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａ
ｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる群から選択
した少なくとも１つの元素を含む化合物が発光中心また
は付活剤としてドーピングされていることを特徴とする
低速電子線励起用蛍光体。4. A light-emitting host material CuAlS 2 containing Mn, Z
n, La, Ce, Pr, Nd, Sm, Eu, Tb, D
y, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl, Br, I, Li, Na, K, Rb, Cs, P, A
A phosphor for low-speed electron beam excitation, wherein a compound containing at least one element selected from the group consisting of s, Sb, Bi, Sc, Y and O is doped as an emission center or an activator.
体をつくる物質を含む発光母体材料としての固溶体に、
Ｍｎ，Ｚｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔ
ｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎｉ，Ｓｎ，Ｐ
ｂ，Ｆ，Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，Ｋ，Ｒｂ，Ｃ
ｓ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｓｃ，ＹおよびＯからなる
群から選択した少なくとも１つの元素を含む化合物が発
光中心または付活剤としてドーピングされていることを
特徴とする低速電子線励起用蛍光体。5. A solid solution as a light-emitting host material containing CuAlS 2 and a substance forming a chalcopyrite solid solution,
Mn, Zn, La, Ce, Pr, Nd, Sm, Eu, T
b, Dy, Ho, Er, Tm, Yb, Ni, Sn, P
b, F, Cl, Br, I, Li, Na, K, Rb, C
For slow electron beam excitation, characterized in that a compound containing at least one element selected from the group consisting of s, P, As, Sb, Bi, Sc, Y and O is doped as an emission center or an activator. Phosphor.
2 （０＜ｘ＜１）またはＣｕＡｌＳx Ｓｅ2-x （０＜ｘ
＜２）に、Ｍｎ，Ｚｎ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓ
ｍ，Ｅｕ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｎ
ｉ，Ｓｎ，Ｐｂ，Ｆ，Ｃｌ，Ｂｒ，Ｉ，Ｌｉ，Ｎａ，
Ｋ，Ｒｂ，Ｃｓ，Ｐ，Ａｓ，Ｓｂ，Ｂｉ，Ｓｃ，Ｙおよ
びＯからなる群から選択した少なくとも１つの元素を含
む化合物が発光中心または付活剤としてドーピングされ
ていることを特徴とする低速電子線励起用蛍光体。6. Luminescent material CuGa x Al 1-x S
2 (0 <x <1) or CuAlS x Se 2-x (0 <x
<2), Mn, Zn, La, Ce, Pr, Nd, S
m, Eu, Tb, Dy, Ho, Er, Tm, Yb, N
i, Sn, Pb, F, Cl, Br, I, Li, Na,
A low speed characterized by being doped with a compound containing at least one element selected from the group consisting of K, Rb, Cs, P, As, Sb, Bi, Sc, Y and O as an emission center or an activator. Phosphor for electron beam excitation.
低速電子線励起用蛍光体を低抵抗化する方法であって、
前記低速電子線励起用蛍光体の粉末を、飽和硫黄雰囲気
中において、６００℃以上の温度で１０〜３０時間加熱
するようにしたことを特徴とする低速電子線励起用蛍光
体を低抵抗化する方法。7. A method for reducing the resistance of the phosphor for low-speed electron beam excitation according to claim 1, the method comprising:
The powder of the phosphor for low-speed electron beam excitation is heated at a temperature of 600 ° C. or higher for 10 to 30 hours in a saturated sulfur atmosphere to reduce the resistance of the phosphor for low-speed electron beam excitation. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08640196A JP3686159B2 (en) | 1996-04-09 | 1996-04-09 | Phosphor for low-energy electron beam excitation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08640196A JP3686159B2 (en) | 1996-04-09 | 1996-04-09 | Phosphor for low-energy electron beam excitation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09279140A true JPH09279140A (en) | 1997-10-28 |
| JP3686159B2 JP3686159B2 (en) | 2005-08-24 |
Family
ID=13885854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08640196A Expired - Fee Related JP3686159B2 (en) | 1996-04-09 | 1996-04-09 | Phosphor for low-energy electron beam excitation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3686159B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2389959A (en) * | 2002-06-19 | 2003-12-24 | Univ Dundee | Field emission device |
| JP2010215873A (en) * | 2009-03-19 | 2010-09-30 | Nec Lighting Ltd | Fluorescent body, method of manufacturing fluorescent body, and light-emitting apparatus |
| US8017037B2 (en) * | 2007-03-26 | 2011-09-13 | Nec Lighting, Ltd | Fluorescent substance and light emitting device using the same |
| US8070984B2 (en) | 2004-06-10 | 2011-12-06 | Seoul Semiconductor Co., Ltd. | Luminescent material |
| CN103421493A (en) * | 2012-05-16 | 2013-12-04 | 海洋王照明科技股份有限公司 | Europium doped sulfo copper aluminate luminescent thin film and preparation method and application thereof |
| US8847254B2 (en) | 2005-12-15 | 2014-09-30 | Seoul Semiconductor Co., Ltd. | Light emitting device |
| US8900482B2 (en) | 2004-06-10 | 2014-12-02 | Seoul Semiconductor Co., Ltd. | Light emitting device |
| US9312246B2 (en) | 2006-03-31 | 2016-04-12 | Seoul Semiconductor Co., Ltd. | Light emitting device and lighting system having the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101790541B1 (en) | 2016-02-05 | 2017-10-26 | 한국화학연구원 | Tin or Bismuth doped metal nitride-based red phosphors and light emitting device containing the same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63223085A (en) * | 1987-03-11 | 1988-09-16 | Kanegafuchi Chem Ind Co Ltd | Production of zinc sulfide fluorescent substance thin film |
| JPH02269185A (en) * | 1989-04-10 | 1990-11-02 | Sharp Corp | Luminescent material |
| JPH05179242A (en) * | 1991-12-26 | 1993-07-20 | Futaba Corp | Luminescent material |
| JPH05275331A (en) * | 1992-03-26 | 1993-10-22 | Matsushita Electric Ind Co Ltd | Manufacture of chalocopyrite thin film and solar cell |
| JPH0689075A (en) * | 1992-09-09 | 1994-03-29 | Matsushita Electric Ind Co Ltd | Production of display device and fluorescent screen used therein |
| JPH0864361A (en) * | 1994-08-23 | 1996-03-08 | Nippon Hoso Kyokai <Nhk> | Dispersed electroluminescent element |
| WO1996009353A1 (en) * | 1994-09-20 | 1996-03-28 | Hitachi, Ltd. | Phosphor, and cathode-ray tube and display using the same |
-
1996
- 1996-04-09 JP JP08640196A patent/JP3686159B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63223085A (en) * | 1987-03-11 | 1988-09-16 | Kanegafuchi Chem Ind Co Ltd | Production of zinc sulfide fluorescent substance thin film |
| JPH02269185A (en) * | 1989-04-10 | 1990-11-02 | Sharp Corp | Luminescent material |
| JPH05179242A (en) * | 1991-12-26 | 1993-07-20 | Futaba Corp | Luminescent material |
| JPH05275331A (en) * | 1992-03-26 | 1993-10-22 | Matsushita Electric Ind Co Ltd | Manufacture of chalocopyrite thin film and solar cell |
| JPH0689075A (en) * | 1992-09-09 | 1994-03-29 | Matsushita Electric Ind Co Ltd | Production of display device and fluorescent screen used therein |
| JPH0864361A (en) * | 1994-08-23 | 1996-03-08 | Nippon Hoso Kyokai <Nhk> | Dispersed electroluminescent element |
| WO1996009353A1 (en) * | 1994-09-20 | 1996-03-28 | Hitachi, Ltd. | Phosphor, and cathode-ray tube and display using the same |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2389959A (en) * | 2002-06-19 | 2003-12-24 | Univ Dundee | Field emission device |
| GB2389959B (en) * | 2002-06-19 | 2006-06-14 | Univ Dundee | Improved field emission device |
| US7304420B2 (en) | 2002-06-19 | 2007-12-04 | The University Court Of The University Of Dundee | Field emission device |
| US8900482B2 (en) | 2004-06-10 | 2014-12-02 | Seoul Semiconductor Co., Ltd. | Light emitting device |
| US8883040B2 (en) | 2004-06-10 | 2014-11-11 | Seoul Semiconductor Co., Ltd. | Luminescent material |
| US8070984B2 (en) | 2004-06-10 | 2011-12-06 | Seoul Semiconductor Co., Ltd. | Luminescent material |
| US8070983B2 (en) | 2004-06-10 | 2011-12-06 | Seoul Semiconductor Co., Ltd. | Luminescent material |
| AT508302B1 (en) * | 2004-06-10 | 2012-09-15 | Seoul Semiconductor Co Ltd | LUMINESCENT MATERIAL |
| US8847254B2 (en) | 2005-12-15 | 2014-09-30 | Seoul Semiconductor Co., Ltd. | Light emitting device |
| US9312246B2 (en) | 2006-03-31 | 2016-04-12 | Seoul Semiconductor Co., Ltd. | Light emitting device and lighting system having the same |
| US9576939B2 (en) | 2006-03-31 | 2017-02-21 | Seoul Semiconductor Co., Ltd. | Light emitting device and lighting system having the same |
| US11322484B2 (en) | 2006-03-31 | 2022-05-03 | Seoul Semiconductor Co., Ltd. | Light emitting device and lighting system having the same |
| US8017037B2 (en) * | 2007-03-26 | 2011-09-13 | Nec Lighting, Ltd | Fluorescent substance and light emitting device using the same |
| JP2010215873A (en) * | 2009-03-19 | 2010-09-30 | Nec Lighting Ltd | Fluorescent body, method of manufacturing fluorescent body, and light-emitting apparatus |
| CN103421493A (en) * | 2012-05-16 | 2013-12-04 | 海洋王照明科技股份有限公司 | Europium doped sulfo copper aluminate luminescent thin film and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3686159B2 (en) | 2005-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peters et al. | Luminescence and Structural Properties of Thiogallate Phosphors Ce+ 3 and Eu+ 2‐Activated Phosphors. Part I | |
| WO2007105370A1 (en) | Phosphor for display and field emission display | |
| JP2000073053A (en) | Phosphor and cathode-ray tube using the same | |
| JP3686159B2 (en) | Phosphor for low-energy electron beam excitation | |
| US3970582A (en) | Alpha barium zinc cadmium sulfide phosphors and method | |
| JPH09291279A (en) | Powdery fluorescent substance and its production | |
| KR101496959B1 (en) | Red-emitting phosphors with highly enhanced luminescent efficiency and their preparation methods | |
| KR100285274B1 (en) | A green fluorescent body based gadolinium aluminate and process for preparing them | |
| KR100364494B1 (en) | A red fluorescent body based on gadolinium oxide and methods of preparing the same | |
| KR100285273B1 (en) | A green fluorescent body based Zn2SiO4 and process for preparing them | |
| JP2944596B2 (en) | Method for manufacturing fluorescent display device excited by slow electron beam | |
| EP1607461A1 (en) | Green light emitting phosphor for low voltage/high current density and field emissiion type display including the same | |
| KR100424864B1 (en) | Process for preparing GdOBr green phosphor | |
| KR930005691B1 (en) | Red-luminous phosphor | |
| KR20000008650A (en) | Method for preparing red fluorescent substance made of yttrium oxide derivatives | |
| JP2004197044A (en) | Silicate fluorescent material, method for producing the same and ultra-violet light-excited light-emitting element | |
| JPH0345690A (en) | Phosphor and cathode ray tube made by using it | |
| JP2001064639A (en) | Blue fluorescent substance for low voltage and its production | |
| KR100369709B1 (en) | Preparation of the red phosphor of gadolinium oxides with two type in structure | |
| Langley et al. | Blue cathodoluminescence from tantalum zinc oxide | |
| JP5386092B2 (en) | Method for producing oxide phosphor | |
| JPH10140150A (en) | Phosphor and production of phosphor | |
| KR930006480B1 (en) | Crt | |
| TWI261613B (en) | Phosphor formulations for low voltage and manufacturing methods thereof | |
| CN101962546A (en) | Luminescent material and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041201 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041214 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050208 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050510 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050602 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050208 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090610 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100610 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110610 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |