JPH08115673A - Vacuum ultraviolet-excited light-emitting element - Google Patents
Vacuum ultraviolet-excited light-emitting elementInfo
- Publication number
- JPH08115673A JPH08115673A JP6250446A JP25044694A JPH08115673A JP H08115673 A JPH08115673 A JP H08115673A JP 6250446 A JP6250446 A JP 6250446A JP 25044694 A JP25044694 A JP 25044694A JP H08115673 A JPH08115673 A JP H08115673A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- vuv
- light
- excited light
- 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.)
- Pending
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は真空紫外線励起発光素子
に関し，より詳しくは特定の蛍光体を用い、真空紫外線
により励起して発光させる構造を有する真空紫外線励起
発光素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a VUV-excited light-emitting device, and more particularly, to a VUV-excited light-emitting device having a structure in which a specific phosphor is used to excite and emit light by vacuum UV light.
【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。その一例がプラズマデイスプレイパネル（以下「Ｐ
ＤＰ」という。）の開発である。ＰＤＰは多数の狭い放
電空間（以下「表示セル」という。）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ており、各表示セルの内壁には蛍光
体が塗布されており、各表示セルの内部にはＨｅ−Ｘ
ｅ，Ｎｅ−Ｘｅ、Ａｒ等の希ガスが封入されている。電
極に電圧を印加することにより表示セル内に希ガス放電
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
赤、青又は緑に発光する蛍光体を用い、これらをマトリ
ックス状に塗り分けることにより、フルカラーの表示を
行うことが出来る。これがフルカラーＰＤＰである。2. Description of the Related Art In recent years, a VUV-excited light emitting device having a structure in which a phosphor is excited by a VUV emitted from a rare gas discharge to emit light has been actively developed. One example is the Plasma Display Panel (hereinafter “P
"DP". ) Is the development of. A PDP is a display element configured by arranging a large number of narrow discharge spaces (hereinafter referred to as “display cells”) in a matrix. Discharge electrodes are provided in each display cell, and an inner wall of each display cell is provided. Is coated with a phosphor, and He-X is placed inside each display cell.
A rare gas such as e, Ne-Xe, or Ar is enclosed. A rare gas discharge is generated in the display cell by applying a voltage to the electrodes, and vacuum ultraviolet rays are emitted. This vacuum ultraviolet ray excites the phosphor to emit visible light. An image is displayed by the light emission of the phosphor of the display cell at the predetermined position of the display element. Full-color display can be performed by using phosphors that emit red, blue, or green as the phosphors used in each display cell and by applying these phosphors separately in a matrix. This is a full color PDP.
【０００３】ところで、従来、赤色発光蛍光体として
（Y,Gd)BO3:Eu 、緑色発光蛍光体として Zn2SiO4:Mn 、
青色発光蛍光体として BaMgAl14O23:Eu 等を使用したフ
ルカラーＰＤＰが実用化している（日経マイクロデバイ
ス編「フラットパネル・デイスプレイ」、１９９４年、
日経ＢＰ社発行参照）。By the way, conventionally, (Y, Gd) BO 3 : Eu is used as a red light emitting phosphor, and Zn 2 SiO 4 : Mn is used as a green light emitting phosphor.
A full-color PDP using BaMgAl 14 O 23 : Eu or the like as a blue-emitting phosphor has been put to practical use (Nikkei Microdevices Edition, “Flat Panel Display”, 1994,
(See Nikkei BP issue).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、フルカ
ラーＰＤＰの特性を向上させるために、蛍光体の発光効
率及び寿命の向上が望まれており、特に青色発光蛍光体
の BaMgAl14O23:Eu は他の赤色発光蛍光体、緑色発光蛍
光体に比べて発光輝度の経時劣化が大きい上に、発光色
も経時変化するという欠点を持っているため、寿命の向
上が強く望まれている。However, in order to improve the characteristics of the full-color PDP, it is desired to improve the luminous efficiency and life of the phosphor, and in particular, the blue-emitting phosphor BaMgAl 14 O 23 : Eu is not used. As compared with the red light emitting phosphors and the green light emitting phosphors described above, the light emission luminance deteriorates with time and the emission color also changes with time. Therefore, it is strongly desired to improve the lifetime.
【０００５】本発明は上記の状況に鑑みてなされたもの
であり、青色発光蛍光体の発光輝度の経時劣化、並びに
発光色の経時変化を抑制した真空紫外線励起発光素子を
提供することを目的とする。The present invention has been made in view of the above circumstances, and an object thereof is to provide a VUV-excited light emitting device in which the deterioration of the emission brightness of the blue light emitting phosphor and the change of the emission color with time are suppressed. To do.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、従来から
使用されているフルカラーＰＤＰ用青色発光蛍光体であ
るバリウムマグネシウムアルミン酸塩蛍光体（BaMgAl14
O23:Eu）の組成について鋭意検討した結果、その組成に
よって蛍光体の寿命特性が大きく変わること、特定組成
のバリウムマグネシウムアルミン酸塩蛍光体を青色発光
蛍光体として用いたＰＤＰは従来の BaMgAl14O23:Eu 蛍
光体を用いたＰＤＰに比べて発光輝度の経時劣化及び発
光色の経時変化の両方が改善されることを見い出し、本
発明を完成した。The inventors of the present invention have found that the barium magnesium aluminate phosphor (BaMgAl 14 ) which is a conventionally used blue light emitting phosphor for a full color PDP.
As a result of diligent study on the composition of O 23 : Eu), the life characteristics of the phosphor are significantly changed depending on the composition, and the PDP using the barium magnesium aluminate phosphor of the specific composition as the blue-emitting phosphor is the conventional BaMgAl 14 The present invention has been completed by finding that both the deterioration of emission luminance with time and the change of emission color with time are improved as compared with a PDP using an O 23 : Eu phosphor.
【０００７】即ち、本発明の真空紫外線励起発光素子
は、真空紫外線領域に放電放射スペクトルを有するガ
ス、真空紫外線励起により発光する蛍光体及び放電電極
を容器に封入してなる真空紫外線励起発光素子におい
て、組成式 Ba1-xEuxMgAl10O17 （但し、ｘは 0.05≦ｘ≦0.5 なる条件を満たす数であ
る）で表されるバリウムマグネシウムアルミン酸塩蛍光
体が用いられていることを特徴とする。That is, the VUV-excited light-emitting device of the present invention is a VUV-excited light-emitting device in which a gas having a discharge radiation spectrum in the VUV region, a phosphor that emits light by VUV excitation, and a discharge electrode are enclosed in a container. The barium magnesium aluminate phosphor represented by the composition formula Ba 1-x Eu x MgAl 10 O 17 (where x is a number satisfying the condition of 0.05 ≦ x ≦ 0.5) is used. And
【０００８】該蛍光体の付活剤である Eu の濃度ｘは、
発光強度の点から 0.05≦ｘ≦0.5なる条件を満たす数で
あることが実用上好ましい以下に、本発明を更に詳細に
説明する。本発明の真空紫外線励起発光素子は、表示セ
ル内に塗布される青色発光蛍光体として、例えば下記の
方法で製造されるバリウムマグネシウムアルミン酸塩蛍
光体を用いる以外は従来の真空紫外線励起発光素子と同
様にして製造される。The concentration x of Eu which is the activator of the phosphor is
From the viewpoint of emission intensity, it is practically preferable that the number satisfies the condition of 0.05 ≦ x ≦ 0.5. Hereinafter, the present invention will be described in more detail. The VUV-excited light-emitting device of the present invention is a conventional VUV-excited light-emitting device except that a barium magnesium aluminate phosphor manufactured by the following method is used as the blue light-emitting phosphor coated in the display cell. It is manufactured in the same manner.
【０００９】本発明で用いるバリウムマグネシウムアル
ミン酸塩蛍光体は、例えば次のようにして合成すること
ができる。即ち、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、（３）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、及び（４）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、これにフッ化
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、これらの原料混合物を十分に混
合する。得られた原料混合物を坩堝に充填し、還元性雰
囲気中で、１２００〜１７００℃で２〜４０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
料混合物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等がある。還元
性をより確実にするために、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。焼成を終え
た焼成物に分散、水洗、乾燥、篩い分け等の処理を行う
ことによって、本発明で用いる青色発光のバリウムマグ
ネシウムアルミン酸塩蛍光体を得ることができる。The barium magnesium aluminate phosphor used in the present invention can be synthesized, for example, as follows. That is, as a phosphor material, (1) barium compounds such as barium oxide, barium hydroxide and barium carbonate, (2) europium compounds such as europium oxide and europium fluoride, (3) magnesium oxide, magnesium hydroxide and magnesium carbonate. And magnesium compounds (4) and aluminum compounds (4) aluminum oxide, aluminum hydroxide, etc. are weighed in a predetermined amount, and a flux of barium fluoride, aluminum fluoride, magnesium fluoride, etc. is added thereto, and these raw material mixtures are mixed. Mix well. The obtained raw material mixture is filled in a crucible and fired once or more in a reducing atmosphere at 1200 to 1700 ° C. for 2 to 40 hours. As a method of obtaining a reducing atmosphere, a method of embedding a crucible filled with a raw material mixture in a crucible filled with carbon, a method of putting a lump of graphite, or a carbon substance such as coconut husk in a crucible filled with a raw material, etc. is there. In order to ensure the reducibility, these crucibles may be further fired in a nitrogen atmosphere or a nitrogen-hydrogen atmosphere. Water vapor may be contained in these atmospheres. The blue light-emitting barium magnesium aluminate phosphor used in the present invention can be obtained by subjecting the fired product after firing to treatments such as dispersion, washing with water, drying, and sieving.
【００１０】上記の方法で製造したバリウムマグネシウ
ムアルミン酸塩蛍光体を、例えばＰＤＰの表示セルに厚
膜印刷等で塗布し、ベーキングした後、真空紫外線領域
に放電放射スペクトルを有するガス、例えばＨｅ−Ｘ
ｅ，Ｎｅ−Ｘｅ、Ａｒ等の希ガスを数百 Torr 封入する
事で本発明の真空紫外線励起発光素子を製造することが
できる。The barium magnesium aluminate phosphor produced by the above method is applied to a display cell of a PDP, for example, by thick film printing, and after baking, a gas having a discharge radiation spectrum in the vacuum ultraviolet region, such as He-. X
The VUV-excited light-emitting device of the present invention can be manufactured by enclosing a few hundred Torr of rare gas such as e, Ne-Xe, Ar.
【００１１】以下に、実施例により本発明を説明する。The present invention will be described below with reference to examples.
【００１２】[0012]
実施例 BaCO3 ０.９ mol Eu2O3 ０.０５ mol 3MgCO3・Mg(OH)2 ０.２５ mol Al2O3(ガンマタイプ) ５.０ mol AlF3 ０.０１ mol 上記の諸原料を上記の量で混合し、坩堝に充填し、更に
黒鉛を原料の上に乗せ、蓋をして水蒸気を含んだ窒素雰
囲気中で最高温度１４５０℃で、室温からの昇降温時間
を含めて１１時間かけて一次焼成した。Example BaCO 3 0.9 mol Eu 2 O 3 0.05 mol 3 MgCO 3 .Mg (OH) 2 0.25 mol Al 2 O 3 (gamma type) 5.0 mol AlF 3 0.01 mol The above raw materials Was mixed in the above amount, charged in a crucible, graphite was placed on the raw material, the lid was put on, and the maximum temperature was 1450 ° C. in a nitrogen atmosphere containing water vapor. Primary firing was performed over time.
【００１３】次に、黒鉛を除き、焼成粉を粉砕、篩い分
けし、再度坩堝に充填し、蓋をして水蒸気を含んだ窒素
−水素混合雰囲気中で最高温度１４５０℃で、室温から
の昇降温時間を含めて１１時間かけて二次焼成を行っ
た。次いで、焼成粉に対して分散、洗浄、乾燥、篩い分
けの処理を行い、組成式がBa0.9Eu0.1MgAl10O17 で表さ
れる２価のユーロピウム付活青色発光バリウムマグネシ
ウムアルミン酸塩蛍光体を得た。Next, the graphite was removed, the calcined powder was crushed and sieved, the crucible was filled again, the lid was closed, and the temperature was elevated from room temperature at a maximum temperature of 1450 ° C. in a nitrogen-hydrogen mixed atmosphere containing water vapor. Secondary firing was performed for 11 hours including the warm time. Then, the calcined powder is subjected to dispersion, washing, drying, and sieving treatments, and the divalent europium-activated blue-emitting barium magnesium aluminate phosphor whose composition formula is represented by Ba 0.9 Eu 0.1 MgAl 10 O 17 is shown. Got
【００１４】この蛍光体をセルピッチ0.7mm のセルへ厚
膜印刷し、５１５℃で10分間ベーキングして、セル内に
Ｈｅ−Ｘｅ（Ｘｅの含有量１０％）の希ガスを３００ T
orr封入し本発明の真空紫外線励起発光素子を得た。こ
のようにして得た本発明の真空紫外線励起発光素子を１
００μＡの定電流、Duty＝1/60で駆動して発光させ、駆
動開始時の発光色と発光輝度を輝度計（トプコン製ＢＭ
−５）で測定したところ、発光色（ＣＩＥ表色系の色度
座標）はｘ＝０.１２４、ｙ＝０.０８０であり、発光輝
度は２１.６cd/m2 であった。A thick film of this phosphor was printed on a cell having a cell pitch of 0.7 mm and baked at 515 ° C. for 10 minutes, and a He—Xe (Xe content of 10%) rare gas was added to the cell at 300 T.
After enclosing in orr, a VUV-excited light emitting device of the present invention was obtained. The VUV-excited light-emitting device of the present invention thus obtained is
It is driven with a constant current of 00 μA and Duty = 1/60 to emit light, and the emission color and emission brightness at the start of driving are measured with a luminance meter (Topcon BM
As a result of measurement in -5), the emission color (chromaticity coordinate of CIE color system) was x = 0.124, y = 0.080, and the emission luminance was 21.6 cd / m 2 .
【００１５】これとは別に、得られた真空紫外線励起発
光素子を上記条件で連続駆動させ、フォトトランジスタ
を用いて発光出力の経時変化を測定した。図１に本実施
例で得られた真空紫外線励起発光素子の駆動時間と発光
出力（相対値）との相関を示す。発光出力が半分になる
までの駆動時間は１０９１分であった。また、駆動開始
から１８１７分後の発光色を測定したところ、ｘ＝０.
１３１、ｙ＝０.０９５であり、発光色は駆動開始時と
１８１７時間後とで大きな変化はなかった。Separately from this, the obtained VUV-excited light-emitting device was continuously driven under the above conditions, and the change with time of the light emission output was measured using a phototransistor. FIG. 1 shows the correlation between the drive time and the emission output (relative value) of the VUV-excited light emitting device obtained in this example. The driving time until the emission output was halved was 1091 minutes. In addition, when the emission color was measured 1817 minutes after the start of driving, x = 0.
131, y = 0.095, and the luminescent color did not significantly change between the start of driving and 1817 hours later.
【００１６】比較例 BaCO3 ０.９ mol Eu2O3 ０.０５ mol 3MgCO3・Mg(OH)2 ０.２５ mol Al2O3(ガンマタイプ) ７.０ mol AlF3 ０.０１４ mol 上記の諸原料を上記の量（即ち、化学量論的に組成式 B
a0.9Eu0.1MgAl14O23で表される混合比）で用いる以外は
実施例と同様にして処理して２価のユーロピウム付活青
色発光バリウムマグネシウムアルミン酸塩蛍光体を得
た。Comparative Example BaCO 3 0.9 mol Eu 2 O 3 0.05 mol 3 MgCO 3 .Mg (OH) 2 0.25 mol Al 2 O 3 (gamma type) 7.0 mol AlF 3 0.014 mol The raw materials in the above amount (that is, stoichiometrically in the composition formula B
A divalent europium-activated blue light emitting barium magnesium aluminate phosphor was obtained by treating in the same manner as in Example except that the mixture ratio was represented by a 0.9 Eu 0.1 MgAl 14 O 23 ).
【００１７】このようにして得た蛍光体を用いる以外は
実施例と同様にして真空紫外線励起発光素子を製造し
た。このようにして得た比較例の真空紫外線励起発光素
子を、実施例の真空紫外線励起発光素子の場合と同様に
して駆動し、発光させ、駆動開始時の発光色と発光輝度
を測定したところ、発光色（ＣＩＥ表色系の色度座標）
はｘ＝０.１３０、ｙ＝０.０９３であり、発光輝度は２
２.１cd/m2 であった。A VUV-excited light emitting device was manufactured in the same manner as in Example except that the phosphor thus obtained was used. The vacuum ultraviolet ray excited light emitting device of the comparative example thus obtained was driven in the same manner as in the case of the vacuum ultraviolet ray excited light emitting device of the example to emit light, and the emission color and emission luminance at the start of driving were measured, Emission color (chromaticity coordinates of CIE color system)
Is x = 0.130, y = 0.093, and the emission brightness is 2
It was 2.1 cd / m 2 .
【００１８】これとは別に、得られた比較例の真空紫外
線励起発光素子を連続駆動させ、フォトトランジスタを
用い、上記実施例と同様にして発光輝度の経時変化を測
定した。図１に本比較例で得られた真空紫外線励起発光
素子の駆動時間と発光出力（相対値）との相関を示す。
発光出力が半分になるまでの駆動時間は４６０分であ
り、実施例の真空紫外線励起発光素子に比べ半分以下の
時間であった。また、駆動開始から１２３１分後の発光
色を測定したところ、ｘ＝０.１８１、ｙ＝０.１６９で
あり、駆動開始初期に比べて発光色が大きく変化してい
た。Separately from this, the obtained VUV-excited light-emitting device of Comparative Example was continuously driven, and a change in emission luminance with time was measured using a phototransistor in the same manner as in the above example. FIG. 1 shows the correlation between the driving time and the emission output (relative value) of the VUV-excited light emitting device obtained in this comparative example.
The driving time until the emission output was halved was 460 minutes, which was less than half the driving time of the VUV-excited light emitting device of the example. Further, when the emission color was measured 1231 minutes after the start of driving, x = 0.181 and y = 0.169 were found, and the emission color was largely changed compared to the initial stage of starting the driving.
【００１９】[0019]
【発明の効果】本発明によれば、経時的な発光輝度の低
下並びに発光色の変化の少ない真空紫外線励起発光素子
が得られ、従来のものに比べて寿命特性の良好なカラー
ＰＤＰを提供することが可能である。According to the present invention, it is possible to obtain a VUV-excited light-emitting device in which a decrease in emission luminance with time and a change in emission color are small, and a color PDP having a better life characteristic than the conventional one is provided. It is possible.
【図１】本発明の真空紫外線励起発光素子と従来の真空
紫外線励起発光素子の発光輝度の経時変化を例示するグ
ラフである。FIG. 1 is a graph illustrating changes over time in the emission brightness of a VUV-excited light emitting device of the present invention and a conventional VUV-excited light emitting device.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小池 純郎 東京都世田谷区砧一丁目10番11号 日本放 送協会 放送技術研究所内 (72)発明者 村上 由紀夫 東京都世田谷区砧一丁目10番11号 日本放 送協会 放送技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junro Koike 1-10-11 Kinuta, Setagaya-ku, Tokyo Inside the broadcasting technology research institute of Japan Broadcasting Corporation (72) Inventor Yukio Murakami 1-10-11 Kinuta, Setagaya-ku, Tokyo No. Japan Broadcasting Corporation Broadcasting Technology Research Institute
Claims (1)
有するガス、真空紫外線励起により発光する蛍光体及び
放電電極を容器に封入してなる真空紫外線励起発光素子
において、組成式 Ba1-xEuxMgAl10O17 （但し、ｘは 0.05≦ｘ≦0.5 なる条件を満たす数であ
る）で表されるバリウムマグネシウムアルミン酸塩蛍光
体が用いられていることを特徴とする真空紫外線励起発
光素子。1. A VUV-excited light-emitting device in which a gas having a discharge radiation spectrum in the VUV region, a phosphor that emits light when excited by VUV, and a discharge electrode are enclosed in a container, wherein the composition formula Ba 1-x Eu x MgAl is used. A vacuum-ultraviolet-excited light-emitting device comprising a barium magnesium aluminate phosphor represented by 10 O 17 (where x is a number satisfying the condition of 0.05 ≦ x ≦ 0.5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6250446A JPH08115673A (en) | 1994-10-17 | 1994-10-17 | Vacuum ultraviolet-excited light-emitting element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6250446A JPH08115673A (en) | 1994-10-17 | 1994-10-17 | Vacuum ultraviolet-excited light-emitting element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08115673A true JPH08115673A (en) | 1996-05-07 |
Family
ID=17208000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6250446A Pending JPH08115673A (en) | 1994-10-17 | 1994-10-17 | Vacuum ultraviolet-excited light-emitting element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08115673A (en) |
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1994
- 1994-10-17 JP JP6250446A patent/JPH08115673A/en active Pending
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