JPH0864361A - Dispersed electroluminescent element - Google Patents
Dispersed electroluminescent elementInfo
- Publication number
- JPH0864361A JPH0864361A JP6198432A JP19843294A JPH0864361A JP H0864361 A JPH0864361 A JP H0864361A JP 6198432 A JP6198432 A JP 6198432A JP 19843294 A JP19843294 A JP 19843294A JP H0864361 A JPH0864361 A JP H0864361A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- light emitting
- printed
- layer
- emitting layer
- Prior art date
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- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、分散型エレクトロル
ミネッセンス（通常ELと称す）素子の構成に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure of a dispersion type electroluminescence (usually referred to as EL) element.
【０００２】[0002]
【従来の技術】従来、赤色発光の分散型ELの母体材料と
してはZnS が用いられてきた。それらのうち、赤色発光
中心材料としてはMnまたはCuおよびハロゲン化物をドー
プしたものや、SmまたはSmF をドープしたものが研究さ
れてきた。また、別の母体材料としてCaS を用いて、赤
色発光中心としてEuおよびClをドープしたものも研究さ
れている。これら分散型ELや発光材料については蛍光体
同学会編、“蛍光体ハンドブック”、pp.322〜329 、オ
ーム社、1987年刊行や電子情報通信学会編、“先端デバ
イス材料ハンドブック”、pp.449〜454 、オーム社、19
93年刊行に詳細に記載されている。2. Description of the Related Art Heretofore, ZnS has been used as a base material for a red-light-emitting dispersed EL. Among them, as the red emission center material, those doped with Mn or Cu and a halide and those doped with Sm or SmF have been studied. In addition, CaS is used as another base material, and Eu and Cl are doped as red emission centers. About these dispersion type EL and luminescent materials, "Phosphor Handbook", pp.322-329, edited by Phosphor Society, 1987, published by Ohmsha, Inc. and Institute of Electronics, Information and Communication Engineers, "Advanced Device Material Handbook", pp.449 ~ 454, Ohmsha, 19
It is described in detail in 1993.
【０００３】[0003]
【発明が解決しようとする課題】従来技術でMnのみをド
ープしたZnS の発光の中心波長は585nm の橙色発光を示
す。しかし、赤色を得るには色純度が悪く光学フィルタ
を用いて短波長側を除去している。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the prior art, ZnS doped with only Mn emits orange light with a center wavelength of 585 nm. However, in order to obtain a red color, the color purity is poor and the short wavelength side is removed by using an optical filter.
【０００４】また、別の赤色材料としてZnS 中にSmまた
はSmF をドープしたものが用いられている。これらにお
いて、653nm に中心波長をもつ強い発光線の他に、570n
m および610nm に２つの発光線があり、とりわけ570nm
の発光線は赤色の色純度を悪くしている。この材料も赤
色を得るには色純度が悪く光学フィルタを用いて短波長
側を除去する必要がある。As another red material, ZnS doped with Sm or SmF is used. In addition to the strong emission line with a center wavelength of 653 nm,
There are two emission lines at m and 610nm, especially 570nm
The emission line of the red deteriorates the color purity of red. In order to obtain a red color, this material also has poor color purity, and it is necessary to remove the short wavelength side using an optical filter.
【０００５】また、MnをドープしないでCuとあるハロゲ
ン化物を添加し、ZnS のドナー、アクセプタ対を発光中
心として使用しているものもある。この材料はCuのドー
ピング量を変えることでドナー、アクセプタのエネルギ
ー準位を動かすことができ発光波長を可変できるという
利点はあるが、発光の劣化があるという欠点があり、赤
色分散EL材料として実用化されるに至ってはいない。There is also one in which a certain halide such as Cu is added without doping Mn and a ZnS donor / acceptor pair is used as an emission center. This material has the advantage that the energy levels of the donor and acceptor can be moved by changing the doping amount of Cu and the emission wavelength can be changed, but it has the drawback of emission degradation and is practically used as a red dispersion EL material. It hasn't been realized.
【０００６】また、別の赤色材料として母体材料にCaS
を用いて、発光中心にEuとClをドープしたものがある。
この材料は、655nm 付近を中心波長とするブロードな赤
色発光を示すが、化学的に不安定という欠点があり、赤
色分散EL材料として実用化されていない。As another red material, CaS is used as a base material.
There is a luminescent center doped with Eu and Cl.
This material has a broad red emission centered around 655 nm, but has the drawback of being chemically unstable and has not been put to practical use as a red dispersion EL material.
【０００７】そこで本発明の目的は、理想的な赤色であ
るCRT 用蛍光体Y2O3S : Euの色度座標ｘ＝0.62、ｙ＝0.
35とほぼ同等の色純度の良い発光が得られ、ZnS : M や
ZnS: SmおよびZnS : SmF などで必要とされた光学フィ
ルタが不要であり、化学的にも安定性がある分散型エレ
クトロルミネッセンス素子を提供せんとするものであ
る。Therefore, an object of the present invention is to provide an ideal red CRT phosphor Y 2 O 3 S: Eu with chromaticity coordinates x = 0.62, y = 0.
Emissions with good color purity similar to 35 are obtained, and ZnS: M and
It is an object of the present invention to provide a dispersion-type electroluminescent device which does not require an optical filter required for ZnS: Sm and ZnS: SmF and is chemically stable.
【０００８】[0008]
【課題を解決するための手段】その目的を達成するため
の本発明分散型エレクトロルミネッセンス素子は、背面
電極と透明導電性フィルムで発光層と誘電体層とを挟
み、前記背面電極上に印刷された誘電体層を設け、当該
誘電体層上に印刷された発光層を設ける構造の分散型エ
レクトロルミネッセンス素子において、母体材料として
のCuAlS2に添加材料としてのMnを添加混合した蛍光体粉
末を、所定の有機バインダに分散させたものを印刷すべ
き前記発光層の印刷材料とし、赤色発光を得ることがで
きるよう構成したことを特徴とするものである。In order to achieve the object, a dispersion type electroluminescence device of the present invention has a back electrode, a transparent conductive film sandwiching a light emitting layer and a dielectric layer, and is printed on the back electrode. In the dispersion type electroluminescence element having a structure in which a dielectric layer is provided, and a light emitting layer printed on the dielectric layer is provided, a phosphor powder obtained by adding and mixing Mn as an additive material to CuAlS 2 as a base material, It is characterized in that a substance dispersed in a predetermined organic binder is used as a printing material for the light emitting layer to be printed, and red light emission is obtained.
【０００９】また、本発明分散型エレクトロルミネッセ
ンス素子の製造方法は、背面電極と透明導電性フィルム
で発光層と誘電体層とを挟み、前記背面電極上に印刷さ
れた誘電体層を設け、当該誘電体層上に印刷された発光
層を設けて分散型エレクトロルミネッセンス素子を製作
するにあたり、印刷すべき前記発光層の印刷材料を製作
する方法が、高純度に精製されたCuAlS2粉末に0.01〜10
wt％に相当する高純度のMn粉末を混合する手順と、この
混合粉末を石英ボートに入れH2S ガス雰囲気中で加熱焼
成してCuAlS2：Mn蛍光体粉末を得る手順と、高誘電率有
機バインダ粉末を用意し、10〜40％濃度になるよう有機
溶剤を加え、攪拌機で透明溶液になるまで完全溶解させ
る手順と、この溶解物に前記CuAlS2：Mnの蛍光体粉末を
混合する手順とを含むことを特徴とするものである。Further, the method for manufacturing a dispersed electroluminescent device according to the present invention is such that a back electrode and a transparent conductive film sandwich a light emitting layer and a dielectric layer, and a printed dielectric layer is provided on the back electrode. In producing a dispersion type electroluminescence device by providing a printed light emitting layer on the dielectric layer, a method of producing a printing material of the light emitting layer to be printed, CuAlS 2 powder purified to high purity 0.01 ~ Ten
A procedure for mixing high-purity Mn powder corresponding to wt%, a procedure for obtaining the CuAlS 2 : Mn phosphor powder by placing the mixed powder in a quartz boat and heating and firing in a H 2 S gas atmosphere, and a high dielectric constant Prepare an organic binder powder, add an organic solvent to a concentration of 10-40%, a procedure to completely dissolve until a transparent solution with a stirrer, and a procedure to mix the CuAlS 2 : Mn phosphor powder to this solution It is characterized by including and.
【００１０】[0010]
【実施例】CuAlS2 : Mn の蛍光体は高誘電率バインダに
埋め込まれ、EL電極間に挟み込むことで構成される。EL
電極間に電場を印加することでMn発光センタの励起→基
底状態を繰り返して発光する。図２は、CuAlS2 : Mn の
分散型EL素子で得られた赤色発光のELスペクトルであ
る。このスペクトルの色度座標はｘ＝0.65、ｙ＝0.35で
あり、CRT 蛍光体Y2O2S: Euの赤色色度座標ｘ＝0.62、
ｙ＝0.35とほぼ同等の色純度の良い発光が得られてい
る。図１に本発明に係る分散型エレクトロルミネッセン
ス素子構成例の断面図を示すが、本発明はこの実施例に
限定されることはなく、発明の要旨内で各種の変形、変
更の可能なことは自明である。EXAMPLE A CuAlS 2 : Mn phosphor is embedded in a high dielectric constant binder and sandwiched between EL electrodes. EL
By applying an electric field between the electrodes, the Mn emission center is excited and the ground state is repeatedly emitted. FIG. 2 is an EL spectrum of red emission obtained by the CuAlS 2 : Mn dispersion EL device. The chromaticity coordinates of this spectrum are x = 0.65 and y = 0.35, and the red chromaticity coordinates of the CRT phosphor Y 2 O 2 S: Eu are x = 0.62,
Light emission with good color purity almost equal to y = 0.35 was obtained. FIG. 1 shows a cross-sectional view of a constitutional example of a distributed electroluminescent element according to the present invention, but the present invention is not limited to this embodiment, and various modifications and changes are possible within the scope of the invention. It is self-explanatory.
【００１１】本発明に係る分散型エレクトロルミネッセ
ンス素子の基本構成は、背面電極となるアルミシート６
と透明導電性フィルム３で発光層４と誘電体層５を挟み
込んだ構成である。この基本構成に防湿性や機械的強度
を持たせるために、セルを吸湿フィルム２，７でつつ
み、さらに防湿フィルム１，８でくるんでいる。The basic structure of the dispersion type electroluminescence element according to the present invention is the aluminum sheet 6 serving as the back electrode.
And the transparent conductive film 3 sandwiches the light emitting layer 4 and the dielectric layer 5. In order to impart moisture resistance and mechanical strength to this basic structure, the cells are wrapped with moisture absorbing films 2 and 7, and further wrapped with moisture preventing films 1 and 8.
【００１２】これが製作手順は、まず、背面電極となる
アルミシート６の上に誘電体層５を印刷し、このシート
を乾燥機で十分乾燥させた後、誘電体層５の上に発光層
４を印刷し同様に乾燥機で十分乾燥させる。次に、透明
導電性フィルム３と上述の手順で作成した層４，５，６
とをゴムロールラミネータまたは加熱プレス機を用いて
圧着し、接着剤コーティングされている吸湿フィルム２
を透明導電性フィルム３の上に、もう一枚の吸湿フィル
ム７をアルミシート６の下に敷く。最後に接着剤コーテ
ィングされた防湿フィルム１，８の間に上で得られた層
２〜７の各層を挟み込んでラミネータに通して封止す
る。The manufacturing procedure is as follows. First, the dielectric layer 5 is printed on the aluminum sheet 6 serving as a back electrode, and the sheet is sufficiently dried by a dryer, and then the light emitting layer 4 is formed on the dielectric layer 5. Is printed and similarly dried sufficiently in a dryer. Next, the transparent conductive film 3 and the layers 4, 5, 6 prepared by the above-mentioned procedure.
Moisture-absorbing film 2 coated with adhesive using a rubber roll laminator or a heat press machine.
Is laid on the transparent conductive film 3, and another moisture absorbing film 7 is laid under the aluminum sheet 6. Finally, the layers 2 to 7 obtained above are sandwiched between the moisture-proof films 1 and 8 coated with an adhesive, and the layers are passed through a laminator for sealing.
【００１３】次に先に述べたEL発光層４の製作方法の１
例について説明する。まず、高純度に精製されたCuAlS2
粉末に0.01〜10wt％に相当する高純度のMn粉末を混合す
る。この混合粉末を石英ボートに入れ、H2S ガス雰囲気
中で約1000℃にて約６時間加熱焼成してCuAlS2 : Mn の
蛍光体粉末を得る。Next, one of the manufacturing methods of the EL light emitting layer 4 described above
An example will be described. First, highly purified CuAlS 2
The powder is mixed with 0.01 to 10 wt% of high-purity Mn powder. This mixed powder is put in a quartz boat and heated and baked at about 1000 ° C. for about 6 hours in a H 2 S gas atmosphere to obtain a phosphor powder of CuAlS 2 : Mn.
【００１４】次に、高誘電率有機バインダ粉末を用意
し、10〜40％の濃度になるように有機溶剤を加えて攪拌
機で透明溶液になるまで完全溶解し、この溶解物にCuAl
S2 :Mnの蛍光体粉末を混合し、よく混ぜることで発光層
４の印刷材料を得ることができる。Next, a high-dielectric-constant organic binder powder is prepared, an organic solvent is added so as to have a concentration of 10 to 40%, and the mixture is completely dissolved by a stirrer until it becomes a transparent solution.
A printing material for the light emitting layer 4 can be obtained by mixing S 2 : Mn phosphor powder and mixing well.
【００１５】以上は発光中心としてMnのみをドーピング
したものであるが、Mnの他に併せて、元素La, Ce, Pr,
Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl,Br, I, Li, Na, K, Pb, Cs, P, As, Sb, Bi, Sc, Y
およびO の少なくともいずれか１つの元素または当該
少なくともいずれか１つの元素を含む化合物をドープし
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。The above is the case where only Mn is doped as the emission center, but in addition to Mn, the elements La, Ce, Pr,
Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Ni, Sn, Pb, F,
Cl, Br, I, Li, Na, K, Pb, Cs, P, As, Sb, Bi, Sc, Y
It is also possible to dope at least any one element of O and O 2 or a compound containing the at least one element to use as an emission center or an activator.
【００１６】また、発光母体材料としてCuAlS2のみでは
なく、CuAlS2とカルコパライト系固溶体をつくる他の物
質を含む固溶体、例えば、CuGax Al1-x S2（０＜ｘ＜
１）やCuAl Sx Se2-x （０＜ｘ＜２）を使用してもよ
い。Further, not only CuAlS 2 as a luminescent material but also a solid solution containing CuAlS 2 and another substance that forms a chalcopyrite solid solution, for example, CuGa x Al 1-x S 2 (0 <x <
1) or CuAl S x Se 2-x (0 <x <2) may be used.
【００１７】さらにこの発明は、一般に広く研究されて
いる交流駆動の分散型EL素子に適用するのが好適である
が、直流駆動の分散型EL素子に適用することも可能であ
り、さらにまた説明してきた発光層は分散型EL素子のみ
ならず薄膜EL素子の発光層にも使用できることを付記し
ておく。Furthermore, the present invention is preferably applied to an AC-driven distributed EL element which has been widely studied, but it is also applicable to a DC-driven distributed EL element, and will be described. It should be noted that the light emitting layer that has been used can be used not only for the dispersion type EL element but also for the light emitting layer of a thin film EL element.
【００１８】[0018]
【発明の効果】本発明に係るCuAlS2 : Mn 発光層は632n
m に発光の中心波長を持ち、理想的な赤色の発光波長で
あるCRT 用蛍光体Y2O2S : Euとほぼ同等の色純度が得ら
れ、従来の赤色分散EL材料で色純度を増すために必要と
された短波長側を除去する光学フィルタも不要となり、
この材料自身化学的に安定性も良いので安定した赤色発
光を有する分散型EL素子が得られるようになった。The CuAlS 2 : Mn light emitting layer according to the present invention is 632n
It has a central wavelength of light emission at m, and it has almost the same color purity as the CRT phosphor Y 2 O 2 S: Eu, which is an ideal red emission wavelength, and increases the color purity with conventional red dispersion EL materials. The optical filter that removes the short wavelength side that was necessary for
Since this material itself has good chemical stability, it has become possible to obtain a dispersion type EL device having stable red light emission.
【図１】本発明に係る分散型エレクトロルミネッセンス
素子構成例の断面図である。FIG. 1 is a cross-sectional view of a configuration example of a distributed electroluminescent element according to the present invention.
【図２】本発明に係る分散型EL素子で得られた発光スペ
クトルである。FIG. 2 is an emission spectrum obtained by the dispersion type EL device according to the present invention.
１，８ 防湿フィルム ２，７ 吸湿フィルム ３ 透明導電性フィルム ４ 発光層 ５ 誘電体層 ６ アルミシート 1,8 Moisture proof film 2,7 Moisture absorption film 3 Transparent conductive film 4 Light emitting layer 5 Dielectric layer 6 Aluminum sheet
───────────────────────────────────────────────────── フロントページの続き (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 (72) Inventor Katsuaki Sato 1087-169 Kamio Aso, Aso-ku, Kawasaki-shi, Kanagawa
Claims (4)
と誘電体層とを挟み、前記背面電極上に印刷された誘電
体層を設け、当該誘電体層上に印刷された発光層を設け
る構造の分散型エレクトロルミネッセンス素子におい
て、母体材料としてのCuAlS2に発光中心材料としてのMn
を添加混合した蛍光体粉末を、所定の有機バインダに分
散させたものを印刷すべき前記発光層の印刷材料とし、
赤色発光を得ることができるよう構成したことを特徴と
する分散型エレクトロルミネッセンス素子。1. A back electrode and a transparent conductive film sandwich a light emitting layer and a dielectric layer, a printed dielectric layer is provided on the back electrode, and a printed light emitting layer is provided on the dielectric layer. In a dispersed electroluminescent device with a structure, CuAlS 2 as a base material and Mn as an emission center material
The phosphor powder mixed and mixed, as a printing material of the light emitting layer to be printed what is dispersed in a predetermined organic binder,
A dispersive electroluminescent device, characterized in that it is configured to obtain red light emission.
元素La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Y
b, Ni, Sn, Pb, F, Cl, Br, I, Li, Na, K, Rb, Cs, P,
As, Sb, Bi, Sc, Y およびO の少なくともいずれか１
つの元素または当該少なくともいずれか１つの元素を含
んだ化合物を有することを特徴とする請求項1 記載の分
散型エレクトロルミネッセンス素子。2. As the additive material, in addition to Mn,
Elements La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Y
b, Ni, Sn, Pb, F, Cl, Br, I, Li, Na, K, Rb, Cs, P,
At least one of As, Sb, Bi, Sc, Y and O 1
2. The dispersed electroluminescence device according to claim 1, comprising one element or a compound containing at least one of the elements.
ライト系固溶体をつくる化合物を使用したことを特徴と
する請求項１または２記載の分散型エレクトロルミネッ
センス素子。3. The dispersion type electroluminescence device according to claim 1, wherein CuAlS 2 and a compound forming a chalcopyrite solid solution are used as the base material.
と誘電体層とを挟み、前記背面電極上に印刷された誘電
体層を設け、当該誘電体層上に印刷された発光層を設け
て分散型エレクトロルミネッセンス素子を製作するにあ
たり、印刷すべき前記発光層の印刷材料を製作する方法
が、高純度に精製されたCuAlS2粉末に0.01〜10wt％に相
当する高純度のMn粉末を混合する手順と、この混合粉末
を石英ボートに入れH2S ガス雰囲気中で加熱焼成してCu
AlS2：Mn蛍光体粉末を得る手順と、高誘電率有機バイン
ダ粉末を用意し、10〜40％濃度になるよう有機溶剤を加
え、攪拌機で透明溶液になるまで完全溶解させる手順
と、この溶解物に前記CuAlS2：Mnの蛍光体粉末を混合す
る手順とを含むことを特徴とする分散型エレクトロルミ
ネッセンス素子の製作方法。4. A back electrode and a transparent conductive film sandwiching a light emitting layer and a dielectric layer, a printed dielectric layer is provided on the back electrode, and a printed light emitting layer is provided on the dielectric layer. In producing a dispersion type electroluminescence device, a method of producing a printing material for the light emitting layer to be printed is to mix CuAlS 2 powder purified to high purity with high purity Mn powder equivalent to 0.01 to 10 wt%. And the mixed powder is put in a quartz boat and heated and baked in a H 2 S gas atmosphere to form Cu.
AlS 2 : Mn phosphor powder procedure, high-dielectric constant organic binder powder prepared, add organic solvent to a concentration of 10 ~ 40%, complete dissolution with a stirrer until a transparent solution, and this dissolution And a step of mixing the above-mentioned CuAlS 2 : Mn phosphor powder with an object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19843294A JP3474643B2 (en) | 1994-08-23 | 1994-08-23 | Dispersion type electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19843294A JP3474643B2 (en) | 1994-08-23 | 1994-08-23 | Dispersion type electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0864361A true JPH0864361A (en) | 1996-03-08 |
| JP3474643B2 JP3474643B2 (en) | 2003-12-08 |
Family
ID=16390995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19843294A Expired - Fee Related JP3474643B2 (en) | 1994-08-23 | 1994-08-23 | Dispersion type electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3474643B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09279140A (en) * | 1996-04-09 | 1997-10-28 | Nippon Hoso Kyokai <Nhk> | Fluorescent substance for excitation with low-energy electron beam and reduction in resistance of the same fluorescent substance |
| WO2007099882A1 (en) * | 2006-03-03 | 2007-09-07 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting element, light emitting device and electronic device |
| US7622744B2 (en) | 2006-03-03 | 2009-11-24 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting material, light emitting element, light emitting device and electronic device |
| US8017037B2 (en) | 2007-03-26 | 2011-09-13 | Nec Lighting, Ltd | Fluorescent substance and light emitting device using the same |
-
1994
- 1994-08-23 JP JP19843294A patent/JP3474643B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09279140A (en) * | 1996-04-09 | 1997-10-28 | Nippon Hoso Kyokai <Nhk> | Fluorescent substance for excitation with low-energy electron beam and reduction in resistance of the same fluorescent substance |
| WO2007099882A1 (en) * | 2006-03-03 | 2007-09-07 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting element, light emitting device and electronic device |
| US7622744B2 (en) | 2006-03-03 | 2009-11-24 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting material, light emitting element, light emitting device and electronic device |
| US8017037B2 (en) | 2007-03-26 | 2011-09-13 | Nec Lighting, Ltd | Fluorescent substance and light emitting device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3474643B2 (en) | 2003-12-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |