JP2001123166A - Phosphor for vacuum ultraviolet-excitable luminous element - Google Patents
Phosphor for vacuum ultraviolet-excitable luminous elementInfo
- Publication number
- JP2001123166A JP2001123166A JP30535399A JP30535399A JP2001123166A JP 2001123166 A JP2001123166 A JP 2001123166A JP 30535399 A JP30535399 A JP 30535399A JP 30535399 A JP30535399 A JP 30535399A JP 2001123166 A JP2001123166 A JP 2001123166A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- vacuum ultraviolet
- excitable
- light emitting
- emitting device
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プラズマディスプ
レイパネル（以下「ＰＤＰ」という。）および希ガスラ
ンプなどの真空紫外線励起発光素子に好適な蛍光体およ
びその蛍光体を用いた真空紫外素子に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor suitable for a vacuum ultraviolet ray excited light emitting device such as a plasma display panel (hereinafter referred to as "PDP") and a rare gas lamp, and a vacuum ultraviolet device using the phosphor. It is.
【０００２】[0002]
【従来の技術】近年、希ガス放電により放射される真空
紫外線によって蛍光体を励起して発光させる構造を有す
る真空紫外線励起発光素子の開発が盛んに行われてい
る。その代表例がＰＤＰの開発である。ＰＤＰは画面の
大型化および薄型化が可能なことから、陰極線管（ＣＲ
Ｔ）に代わり得るフラットパネルディスプレイとして注
目されている。ＰＤＰは多数の微小放電空間（以下「表
示セル」と略すことがある）をマトリックス状に配置し
て構成した表示素子であり、各表示セル内には放電電極
が設けられ、各表示セルの内壁には蛍光体が塗布されて
いる。各表示セル内の空間にはＨｅ−Ｘｅ、Ｎｅ−Ｘ
ｅ、Ａｒ等の希ガスが封入されており、放電電極に電圧
を印加することにより、表示セル内で希ガスの放電が起
こり、真空紫外線が放射される。この真空紫外線により
蛍光体が励起され、可視光を発する。表示素子の所定位
置の表示セルの蛍光体の発光によって画像が表示され
る。各表示セルに用いられる蛍光体としてそれぞれ、
青、緑、赤に発光する蛍光体を用い、これらをマトリク
ス状に塗り分けることにより、フルカラーの表示を行う
ことができる。2. Description of the Related Art In recent years, a vacuum ultraviolet ray excited light emitting device having a structure in which a phosphor is excited by vacuum ultraviolet light radiated by rare gas discharge has been actively developed. A typical example is the development of PDPs. Since a PDP can have a large and thin screen, a cathode ray tube (CR)
Attention has been paid to flat panel displays that can replace T). A PDP is a display element in which a large number of minute discharge spaces (hereinafter, may be abbreviated as “display cells”) are arranged in a matrix, and a discharge electrode is provided in each display cell, and an inner wall of each display cell is provided. Is coated with a phosphor. He-Xe, Ne-X
A rare gas such as e or Ar is sealed, and when a voltage is applied to the discharge electrode, discharge of the rare gas occurs in the display cell, and vacuum ultraviolet rays are emitted. The phosphor is excited by the vacuum ultraviolet rays, and emits visible light. An image is displayed by light emission of the phosphor of the display cell at a predetermined position of the display element. As the phosphor used for each display cell,
A full-color display can be performed by using phosphors that emit blue, green, and red, and applying these in a matrix.
【０００３】また、最近では、環境問題から有害な水銀
を低減する傾向にあり、水銀を使用しない希ガスのみの
放電で真空紫外線を放出し蛍光体を励起して発光させる
希ガスランプが注目されている。Recently, there has been a tendency to reduce harmful mercury due to environmental problems, and a rare gas lamp that emits vacuum ultraviolet rays by discharging only a rare gas without using mercury and excites a phosphor to emit light has attracted attention. ing.
【０００４】近年、希ガス放電により放射される真空紫
外線等によって励起して発光させる蛍光体の開発が盛ん
に行われている。例えば、ＰＤＰ用では、青色発光蛍光
体としてはＢａＭｇＡｌ10Ｏ17：Ｅｕ、緑色発光蛍光体
としてＺｎ2ＳｉＯ4：Ｍｎ、赤色発光蛍光体として
（Ｙ，Ｇｄ）ＢＯ3：Ｅｕが実用化されている。しかし
ながら、フルカラーＰＤＰの特性を改良するためには、
蛍光体の輝度、色純度、寿命などの向上が望まれてい
る。In recent years, phosphors that emit light by being excited by vacuum ultraviolet rays or the like radiated by rare gas discharge have been actively developed. For example, for PDPs, BaMgAl 10 O 17 : Eu is used as a blue light emitting phosphor, Zn 2 SiO 4 : Mn is used as a green light emitting phosphor, and (Y, Gd) BO 3 : Eu is used as a red light emitting phosphor. I have. However, in order to improve the characteristics of a full-color PDP,
Improvements in the luminance, color purity, and life of the phosphor have been desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、発光
効率が良好で、ＰＤＰなど真空紫外励起素子用赤色発光
蛍光体およびそれを用いた真空紫外励起素子を提供する
ことにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a red light-emitting phosphor for a vacuum ultraviolet excitation element such as a PDP, which has good luminous efficiency, and a vacuum ultraviolet excitation element using the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、係る状況
下、上記の課題を解決すべく鋭意研究を重ねた結果、Ｇ
ｄ−Ａｌ−ＢＯ3成分系、またはＧｄ−Ｙ−Ａｌ−ＢＯ3
成分系の母体結晶系でＥｕ3+イオンを付活した蛍光体が
有用であることを見い出し、本発明を完成するに至っ
た。Under such circumstances, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result,
d-Al-BO 3 component system, or Gd-Y-Al-BO 3
The present inventors have found that a phosphor in which Eu 3+ ions are activated in a component-based host crystal system is useful, and have completed the present invention.
【０００７】すなわち、本発明は以下の（１）〜（４）
に関するものである。 （１）Ｇｄ、Ａｌ、Ｂ、Ｏからなる化合物基体にＥｕが
添加されることを特徴とする真空紫外線励起発光素子用
蛍光体。 （２）一般式Ｇｄ1‐aＥｕaＡｌ3（ＢＯ3）4（但し、
０．００３≦ａ≦０．５）で表されることを特徴とする
上記（１）記載の真空紫外線励起発光素子用蛍光体。 （３）Ｇｄの０．５乃至９５ｍｏｌ％がＹに置換される
ことを特徴とする上記（１）または（２）記載の真空紫
外線励起発光素子用蛍光体。 （４）上記（１）〜（３）のいずれかに記載の蛍光体を
含有することを特徴とする真空紫外線励起発光素子。That is, the present invention provides the following (1) to (4)
It is about. (1) A phosphor for a VUV-excited light emitting device, wherein Eu is added to a compound substrate composed of Gd, Al, B, and O. (2) General formula Gd 1 -a Eu a Al 3 (BO 3 ) 4 (provided that
0.003 ≦ a ≦ 0.5). The phosphor for a vacuum ultraviolet ray excited light emitting device according to the above (1), wherein (3) The phosphor for a vacuum ultraviolet ray excited light emitting device according to the above (1) or (2), wherein 0.5 to 95 mol% of Gd is substituted by Y. (4) A VUV-excited light-emitting device comprising the phosphor according to any one of (1) to (3).
【０００８】[0008]
【発明の実施の形態】以下に本発明について詳しく説明
する。本発明の真空紫外線励起発光素子用蛍光体は、Ｇ
ｄ、Ａｌ、Ｂ、Ｏからなる化合物基体に付活剤としてＥ
ｕが添加された赤色発光蛍光体であるが、Ｇｄ‐Ａｌ‐
ＢＯ3成分系の母体結晶系において、付活剤としてＥｕ
（Ｅｕ3+イオン）を添加した場合、一般式Ｇｄ1‐aＥｕ
aＡｌ3（ＢＯ3）4（但し、０．００３≦ａ≦０．５）で
表される真空紫外線励起発光素子用蛍光体が好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The phosphor for a VUV-excited light emitting device of the present invention is G
E as an activator for a compound substrate composed of d, Al, B, and O
u-doped red-emitting phosphor, but Gd-Al-
In a BO three- component host crystal system, Eu is used as an activator.
(Eu 3+ ion), the general formula Gd 1 -a Eu
a A phosphor for a VUV-excited light emitting device represented by Al 3 (BO 3 ) 4 (where 0.003 ≦ a ≦ 0.5) is preferable.
【０００９】また、本発明はＧｄの一部をイットリウム
（Ｙ）で置換したＧｄ−Ｙ−Ａｌ−ＢＯ3成分系の母体
結晶系で付活剤としてＥｕ（Ｅｕ3+イオン）を付活した
場合、Ｇｄの０．５乃至９５ｍｏｌ％がＹに置換される
蛍光体が好ましい。Further, the present invention has been activated with Eu (Eu 3+ ions) as an activator in Gd-Y-Al-BO 3 component system of the host crystal system was replaced with yttrium (Y) part of Gd In this case, a phosphor in which 0.5 to 95 mol% of Gd is substituted with Y is preferable.
【００１０】一般式Ｇｄ1‐aＥｕaＡｌ3（ＢＯ3）4にお
いてＧｄの一部をＹに置換した蛍光体では、発光強度の
点から特に該蛍光体の付活剤として有効なＥｕの組成比
ａは０．００３以上０．５以下であることが好ましい。In a phosphor of the general formula Gd 1 -a Eu a Al 3 (BO 3 ) 4 in which a part of Gd is substituted by Y, Eu which is particularly effective as an activator for the phosphor is preferred from the viewpoint of emission intensity. The composition ratio a is preferably 0.003 or more and 0.5 or less.
【００１１】また、本発明は真空紫外励起素子用蛍光体
は、真空紫外域以外の紫外線、Ｘ線および電子線励起の
蛍光体およびそれを用いた素子へも応用可能である。Further, the present invention is also applicable to a phosphor for vacuum ultraviolet excitation elements which is excited by ultraviolet rays, X-rays and electron beams other than the vacuum ultraviolet region, and to an element using the same.
【００１２】本発明に係わる蛍光体の製造方法（合成方
法）は、特に限定されるものではなく、例えば、下記の
ようにそれぞれの蛍光体原料を所定成分組成となるよう
に配合して製造される。アルミニウム原料としては、高
純度（９９．９％以上）のα-アルミナ、γ-アルミナあ
るいは同じく高純度（９９％以上）の水酸化アルミニウ
ム、硝酸塩、ハロゲン化物など、ホウ素原料としては、
高純度の酸化ホウ素、ホウ酸などが使用される。ガドリ
ニウム、イットリウム原料としては、高純度（９９％以
上）の酸化物、あるいは同じく高純度（９９％以上）の
水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩
など高温で分解し酸化物になりうるものが使用できる。The method for producing (synthesizing) the phosphor according to the present invention is not particularly limited. For example, it is produced by blending the respective phosphor raw materials so as to have a predetermined component composition as described below. You. Aluminum raw materials include high-purity (99.9% or more) α-alumina and γ-alumina, and high-purity (99% or more) aluminum hydroxide, nitrate, halide, etc.
High-purity boron oxide, boric acid or the like is used. Gadolinium and yttrium raw materials include high-purity (99% or more) oxides and high-purity (99% or more) hydroxides, carbonates, nitrates, halides, oxalates, etc. Can be used.
【００１３】該蛍光体で発光を生じさせるための付活剤
となるユーロピウムの原料としては、高純度（９９％以
上）の酸化物、あるいは同じく高純度（９９％以上）の
水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩
など高温で分解し酸化物になりうるものが使用できる。As a raw material of europium, which is an activator for causing the phosphor to emit light, a high-purity (99% or more) oxide, a high-purity (99% or more) hydroxide, carbonate Salts, nitrates, halides, oxalates, and the like that can be decomposed at high temperatures to become oxides can be used.
【００１４】これら原料をボールミル、Ｖ型混合機、ま
たは攪拌装置等を用い、混合した後、９００℃から１１
００℃の範囲にて数時間焼成し、蛍光体を得る。原料に
水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩
など高温で分解し酸化物になりうるものが使用した場
合、本焼成の前に、６００℃から８００℃の範囲にて仮
焼することも可能である。このときの焼成雰囲気として
は、特に限定されるものではないが、酸素雰囲気、大気
雰囲気等が好ましい。また、焼成反応を促進するため
に、適量のフラックスを添加してもよい。These materials are mixed using a ball mill, a V-type mixer, or a stirrer, and then mixed at 900 ° C. to 11 ° C.
Firing at a temperature of 00 ° C. for several hours to obtain a phosphor. In the case where materials such as hydroxides, carbonates, nitrates, halides, and oxalates which can be decomposed at high temperatures and become oxides are used as raw materials, calcinate at 600 to 800 ° C. before main firing. It is also possible. The firing atmosphere at this time is not particularly limited, but is preferably an oxygen atmosphere, an air atmosphere, or the like. Also, an appropriate amount of flux may be added to promote the firing reaction.
【００１５】さらに上記方法にて得られた生成物をボー
ルミル、ジェットミル等を用い解砕した後、洗浄する
が、必要に応じ分級する。また、さらに得られた蛍光体
の結晶性を高めるために、必要に応じて再焼成を行う。Further, the product obtained by the above method is pulverized by using a ball mill, a jet mill or the like, and then washed, but classified if necessary. Further, in order to further enhance the crystallinity of the obtained phosphor, re-firing is performed as necessary.
【００１６】以上の発明により、ＰＤＰおよび希ガスラ
ンプなどの真空紫外線励起発光素子に用いると発光強度
が高く、好適な蛍光体が得られる。According to the invention described above, when used in a vacuum ultraviolet ray excited light emitting device such as a PDP and a rare gas lamp, a suitable phosphor can be obtained with high luminous intensity.
【００１７】[0017]
【実施例】次に、本発明を実施例によりさらに詳しく説
明するが、本発明はこれらの実施例に限定されるもので
はない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１８】実施例１ 酸化ガドリニウム（Ｇｄ2Ｏ3）３．６４ｇ、硝酸アルミ
ニウム９水和物［Ａｌ（ＮＯ3）3・９Ｈ2Ｏ］２３．７
７ｇ、酸化ホウ素（Ｂ2Ｏ3）２．９４ｇ、酸化ユーロピ
ウム（Ｅｕ2Ｏ3）０．１９ｇの各蛍光体原料を混合した
後、硝酸を添加し攪拌溶解し、上記蛍光体原料の硝酸水
溶液を得た。得られた硝酸水溶液を加熱・蒸発乾固し、
Ｇｄ、Ｅｕ、Ａｌ、Ｂの混合硝酸塩を得た。得られた混
合硝酸塩をアルミナボートに充填し、空気中で１０００
℃の温度で２４時間焼成した。このようにして、組成式
がＧｄ0.95Ｅｕ0.05Ａｌ3（ＢＯ3）4で表される赤色発
光蛍光体を得た。この蛍光体に、５×１０-2Ｔｏｒｒ以
下の真空層内で、得られた蛍光体にエキシマ１４６ｎｍ
ランプ（ウシオ電機社製）を用いて、紫外線を照射した
ところ、赤色の強い発光を示した。Example 1 3.64 g of gadolinium oxide (Gd 2 O 3 ), aluminum nitrate nonahydrate [Al (NO 3 ) 3 .9H 2 O] 23.7
After mixing 7 g, boron oxide (B 2 O 3 ) 2.94 g, and europium oxide (Eu 2 O 3 ) 0.19 g of each phosphor material, nitric acid was added and dissolved by stirring, and a nitric acid aqueous solution of the phosphor material was added. I got The resulting nitric acid aqueous solution is heated and evaporated to dryness,
A mixed nitrate of Gd, Eu, Al and B was obtained. The obtained mixed nitrate was filled in an alumina boat, and 1000
Firing at a temperature of ° C. for 24 hours In this way, a red-light-emitting phosphor having a composition formula of Gd 0.95 Eu 0.05 Al 3 (BO 3 ) 4 was obtained. The resulting phosphor was applied to an excimer 146 nm in a vacuum layer of 5 × 10 −2 Torr or less.
When irradiated with ultraviolet light using a lamp (manufactured by Ushio Inc.), it emitted strong red light.
【００１９】実施例２ 実施例１と同様の方法で、組成式がＧｄ0.75Ｙ0.2Ｅｕ
0.05Ａｌ3（ＢＯ3）4で表される赤色発光蛍光体を得
た。この蛍光体に、５×１０-2Ｔｏｒｒ以下の真空層内
で、得られた蛍光体にエキシマ１４６ｎｍランプ（ウシ
オ電機社製）を用いて、紫外線を照射したところ、赤色の
強い発光を示した。Example 2 In the same manner as in Example 1, the composition formula was Gd 0.75 Y 0.2 Eu.
A red light-emitting phosphor represented by 0.05 Al 3 (BO 3 ) 4 was obtained. When this phosphor was irradiated with ultraviolet light in a vacuum layer of 5 × 10 −2 Torr or less using an excimer 146 nm lamp (manufactured by Ushio Inc.), a strong red light emission was obtained. .
【００２０】[0020]
【発明の効果】本発明によれば、ＰＤＰおよび希ガスラ
ンプなどの真空紫外線励起発光素子に用いると発光強度
が高く、好適な蛍光体が得られ、高輝度な真空紫外励起
発光素子が実現でき、工業的に極めて有用である。According to the present invention, when used in a vacuum ultraviolet ray excited light emitting device such as a PDP and a rare gas lamp, a high emission intensity, a suitable phosphor can be obtained, and a high brightness vacuum ultraviolet excited light emitting device can be realized. It is extremely useful industrially.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮崎 進 茨城県つくば市北原６ 住友化学工業株式 会社内 Ｆターム(参考） 4H001 XA05 XA08 XA13 XA63 XA64 YA63 5C040 GG08 KA03 KB03 MA03 5C043 AA02 DD28 EB04 ────────────────────────────────────────────────── ─── Continued on the front page (72) Susumu Miyazaki 6 Kitahara, Tsukuba, Ibaraki Pref.
Claims (4)
Ｅｕが添加されることを特徴とする真空紫外線励起発光
素子用蛍光体。1. A phosphor for a vacuum ultraviolet ray excited light emitting device, wherein Eu is added to a compound substrate composed of Gd, Al, B, and O.
し、０．００３≦ａ≦０．５）で表されることを特徴と
する請求項１記載の真空紫外線励起発光素子用蛍光体。2. The vacuum ultraviolet excitation as claimed in claim 1, wherein the compound is represented by the general formula Gd 1 -a Eu a Al 3 (BO 3 ) 4 (where 0.003 ≦ a ≦ 0.5). Phosphor for light emitting element.
されることを特徴とする請求項１または２記載の真空紫
外線励起発光素子用蛍光体。3. The phosphor for a vacuum ultraviolet ray excited light emitting device according to claim 1, wherein 0.5 to 95 mol% of Gd is substituted by Y.
含有することを特徴とする真空紫外線励起発光素子。4. A VUV-excited light-emitting device comprising the phosphor according to claim 1.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30535399A JP2001123166A (en) | 1999-10-27 | 1999-10-27 | Phosphor for vacuum ultraviolet-excitable luminous element |
| US09/694,034 US6676853B1 (en) | 1999-10-27 | 2000-10-23 | Phosphor for vacuum ultraviolet excitation material |
| KR1020000062496A KR100757720B1 (en) | 1999-10-27 | 2000-10-24 | Phosphor for vacuum ultraviolet excitation material |
| EP00122388A EP1095997B1 (en) | 1999-10-27 | 2000-10-25 | Phosphor for vacuum ultraviolet excitation material |
| TW089122470A TW526260B (en) | 1999-10-27 | 2000-10-25 | Phosphor for vacuum ultraviolet excitation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30535399A JP2001123166A (en) | 1999-10-27 | 1999-10-27 | Phosphor for vacuum ultraviolet-excitable luminous element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001123166A true JP2001123166A (en) | 2001-05-08 |
Family
ID=17944102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30535399A Withdrawn JP2001123166A (en) | 1999-10-27 | 1999-10-27 | Phosphor for vacuum ultraviolet-excitable luminous element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001123166A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003096448A (en) * | 2001-09-27 | 2003-04-03 | Sumitomo Chem Co Ltd | Fluorescent substance for vacuum ultraviolet-excited light-emitting element |
| JP2005133063A (en) * | 2003-10-31 | 2005-05-26 | General Electric Co <Ge> | Phosphor containing boron and metal belonging to groups iiia and iiib |
-
1999
- 1999-10-27 JP JP30535399A patent/JP2001123166A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003096448A (en) * | 2001-09-27 | 2003-04-03 | Sumitomo Chem Co Ltd | Fluorescent substance for vacuum ultraviolet-excited light-emitting element |
| JP2005133063A (en) * | 2003-10-31 | 2005-05-26 | General Electric Co <Ge> | Phosphor containing boron and metal belonging to groups iiia and iiib |
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