JPH1050480A - Light-emitting element and manufacture thereof - Google Patents
Light-emitting element and manufacture thereofInfo
- Publication number
- JPH1050480A JPH1050480A JP9107081A JP10708197A JPH1050480A JP H1050480 A JPH1050480 A JP H1050480A JP 9107081 A JP9107081 A JP 9107081A JP 10708197 A JP10708197 A JP 10708197A JP H1050480 A JPH1050480 A JP H1050480A
- Authority
- JP
- Japan
- Prior art keywords
- light
- rate
- sec
- doping
- deposited
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002019 doping agent Substances 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 9
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 3
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- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical class S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000006617 triphenylamine group Chemical class 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気エネルギーを
光に変換できる素子であって、表示素子、フラットパネ
ルディスプレイ、バックライト、照明、インテリア、標
識、看板、電子写真機などの分野に利用可能な面状発光
体用の発光素子およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an element capable of converting electric energy into light, and is applicable to fields such as display elements, flat panel displays, backlights, lighting, interiors, signs, signboards, and electrophotographic machines. The present invention relates to a light-emitting element for a planar light-emitting body and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】負極から注入された電子と正極から注入
された正孔が両極に挟まれた有機蛍光体内で再結合する
際に発光するという有機積層薄膜発光素子の研究が近年
活発に行われるようになってきた。この素子は、薄型、
低駆動電圧下での高輝度発光、蛍光材料を選ぶことによ
る多色発光が特徴である。2. Description of the Related Art In recent years, research has been actively conducted on organic laminated thin-film light emitting devices in which electrons injected from a negative electrode and holes injected from a positive electrode emit light when they recombine in an organic phosphor sandwiched between both electrodes. It has become. This element is thin,
It features high-luminance light emission under a low driving voltage and multicolor light emission by selecting a fluorescent material.
【０００３】有機積層薄膜素子が高輝度に発光すること
は、コダック社のＣ．Ｗ．Ｔａｎｇらによって初めて示
された（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．５１（１２）
２１，ｐ．９１３，１９８７）。コダック社の研究グル
ープが提示した有機積層薄膜発光素子の代表的な構成
は、ＩＴＯガラス基板上に正孔輸送性のジアミン化合
物、発光層であり、かつ電子輸送層でもあるトリス（８
−ヒドロキシキノリノラト）アルミニウム、そして負極
としてＭｇ：Ａｇを順次設けたものであり、１０Ｖ程度
の駆動電圧で１０００ｃｄ／ｍ2の緑色発光が可能であ
った。現在は、上記の素子構成要素の他に発光層と機能
分離された電子輸送層を設けているものなど構成を変え
ているものもあるが、基本的にはコダック社の構成を踏
襲している。[0003] It is known from Kodak's C.I. W. Tang et al. (Appl. Phys. Lett. 51 (12)
21, p. 913, 1987). A typical configuration of an organic laminated thin-film light-emitting device presented by a research group of Kodak Company is a tris (8), which is a hole-transporting diamine compound, a light-emitting layer, and an electron-transport layer on an ITO glass substrate.
-Hydroxyquinolinolato) aluminum and Mg: Ag as a negative electrode were sequentially provided, and green light emission of 1000 cd / m 2 was possible at a driving voltage of about 10 V. At present, there are also those that have changed configurations such as those that have an electron transport layer that is functionally separated from the light emitting layer in addition to the above-mentioned element components, but basically follow the configuration of Kodak Company .
【０００４】このような素子では電子の供給を促進でき
れば素子特性を向上させることが可能である。電子供給
促進には電子輸送能力の向上、電子注入効率向上、そし
てその両方の三通りの方法が考えられる。例えば、素子
内の電子輸送能力を向上して電子の供給を向上させる例
として、特開平６−３２２３６２号公報を例示すること
ができる。即ち、本公報には１０−ヒドロキシベンゾ
［ｈ］キノリン金属錯体が高い電子輸送能力を持つこと
から、トリス（８−ヒドロキシキノリノラト）アルミニ
ウムを用いた素子より高い素子性能を示すことが示され
ている。しかし、ポリアセチレンやポリピロールのよう
な共役系ポリマーにおいてドーピングによって電気伝導
率が向上することは、周知のことである。In such an element, if the supply of electrons can be promoted, the element characteristics can be improved. There are three ways to promote electron supply: improving electron transport capability, improving electron injection efficiency, and both. For example, JP-A-6-322362 can be exemplified as an example of improving the electron transport capability in the device to improve the supply of electrons. That is, this publication discloses that the 10-hydroxybenzo [h] quinoline metal complex has a higher electron transporting ability, and thus exhibits higher device performance than a device using tris (8-hydroxyquinolinolato) aluminum. ing. However, it is well known that doping improves electrical conductivity in conjugated polymers such as polyacetylene and polypyrrole.
【０００５】一方、電子注入を向上することによる電子
供給促進として、リチウムなどのアルカリ金属、マグネ
シウム、カルシウム、ベリリウムやそれらの合金である
低仕事関数陰電極の使用が好ましいことが、特開昭６０
−１９６９８０号公報、特開昭６３−２６４６９２号公
報、特開平２−１５５９５号公報、特開平２−２３４３
９４号公報、特開平４−２１２２８７号公報などに、ま
た有機物とこれらの金属との共蒸着層の介在による電子
注入向上については、特開平７−２６８３１７号公報
に、また陰電極と有機層の界面剥離を防止する目的で陰
極材料と有機材料のそれぞれの成分が漸増するように共
蒸着する方法が特開平４−１３３２８６号公報に記載さ
れている。On the other hand, in order to promote electron supply by improving electron injection, it is preferable to use a low work function cathode, which is an alkali metal such as lithium, magnesium, calcium, beryllium or an alloy thereof.
-196980, JP-A-63-264692, JP-A-2-15595, JP-A-2-2343
No. 94, Japanese Unexamined Patent Publication No. Hei 4-212287, and the like, and for the improvement of electron injection through the interposition of a co-evaporation layer of an organic substance and these metals, see Japanese Unexamined Patent Publication No. Hei 7-268317. Japanese Patent Application Laid-Open No. 4-133286 discloses a method of co-evaporating the cathode material and the organic material so as to gradually increase the respective components for the purpose of preventing interface separation.
【０００６】[0006]
【発明が解決しようとする課題】本発明に関する発光素
子では、正孔と電子がそれぞれ正極と負極から注入され
て素子内で再結合が起こることによって発光が可能とな
る。しかし、従来技術では、高い電子移動度を示す材料
がなかったために、正孔の注入の方が優勢で素子特性を
十分に発現することができなかった。そこで、前述のよ
うに電子移動度の高い材料を開発したり、電子の注入効
率を上げて素子性能を向上させている。In the light emitting device according to the present invention, holes and electrons are injected from the positive electrode and the negative electrode, respectively, and recombination occurs in the device, thereby enabling light emission. However, in the prior art, since there was no material exhibiting high electron mobility, hole injection was more dominant and device characteristics could not be sufficiently exhibited. Therefore, as described above, a material having a high electron mobility has been developed, and the device performance has been improved by increasing the electron injection efficiency.
【０００７】しかし、本発光素子に適合した電子輸送材
料はかなり限られており、現在最高の特性を示す材料を
用いても電子の供給は不足している。また、前記低仕事
関数電極およびこれらの金属と有機物の混合層は、非常
に活性であるため劣化が激しく、キャッピング層を設け
たり、厳しく封止しないとたちまち素子特性が低下して
しまうし、混合層や合金陰電極においては共蒸着法を用
いるために各成分の制御が困難で工程が複雑であるばか
りか再現性にも乏しかった。本発明は、かかる問題を解
決し、低電力で高輝度発光が可能で安定性の高い素子を
提供することを目的とするものである。However, electron transport materials suitable for the present light emitting device are considerably limited, and even if a material exhibiting the best characteristics is used, supply of electrons is insufficient. In addition, the low work function electrode and the mixed layer of these metals and organic substances are extremely active and thus are greatly deteriorated. If a capping layer is not provided or strictly sealed, device characteristics are immediately deteriorated. In the layer and the alloy negative electrode, since the co-evaporation method is used, it is difficult to control each component, the process is complicated, and the reproducibility is poor. An object of the present invention is to solve such a problem and to provide a highly stable element which can emit light with high luminance at low power.
【０００８】[0008]
【課題を解決するための手段】すなわち本発明は、正極
と負極の間に発光を司る物質が存在し、電気エネルギー
により発光する素子であって、前記発光を司る物質にド
ーパントをドーピングすることにより前記課題を解決で
きる。さらに前記発光を司る物質にドーパントをドーピ
ングする際に意外にも有機層を微量の金属蒸気に晒すだ
けでドーピングできる製造方法を見いだし本発明に至っ
た。That is, the present invention relates to an element which emits light by electric energy, in which a substance responsible for light emission exists between a positive electrode and a negative electrode, and wherein the substance responsible for light emission is doped with a dopant. The above problem can be solved. Furthermore, when doping the substance responsible for light emission with a dopant, surprisingly, the present inventors have found a manufacturing method capable of doping simply by exposing the organic layer to a small amount of metal vapor, and reached the present invention.
【０００９】[0009]
【発明の実施の形態】本発明において正極は、光を取り
出すために透明であればよく、その成分としては、イン
ジウム、錫、金、銀、亜鉛、アルミニウム、クロム、ニ
ッケル、酸素、窒素、水素、アルゴン、炭素から選ばれ
る少なくとも一種類の元素からなることが多いが、ヨウ
化銅、硫化銅などの無機導電性物質、ポリチオフェン、
ポリピロール、ポリアニリンなどの導電性ポリマなど特
に限定されるものでない。本発明において好ましい例と
しては、酸化錫、酸化亜鉛、酸化インジウム、酸化錫イ
ンジウム（ＩＴＯ）があげられるが、パターニング加工
などを施すディスプレイ用途などにおいては、加工性に
優れたＩＴＯが特に好適な例としてあげることができる
が、表面抵抗を下げたり電圧降下抑制のために少量の銀
や金などの金属が含まれていても良く、また、錫、金、
銀、亜鉛、インジウム、アルミニウム、クロム、ニッケ
ルをガイド電極として使用することも可能である。中で
もクロムはブラックマトリックスとガイド電極の両方の
機能を持たせることができることからも好適な金属であ
る。透明電極の抵抗は素子の発光に十分な電流が供給で
きればよいので限定されないが、素子の消費電力の観点
からは低抵抗であることが望ましい。例えば３００Ω／
□以下のＩＴＯ基板であれば素子電極として機能する
が、現在では１０Ω／□程度の基板の供給も可能になっ
ていることから、低抵抗品を使用することが特に望まし
い。ＩＴＯの厚みは抵抗値に合わせて任意に選ぶことが
できるが、通常１００〜３００ｎｍの間で用いられるこ
とが多い。また、ガラス基板はソーダライムガラス、無
アルカリガラスなどが用いられ、また厚みも機械的強度
を保つのに十分な厚みがあればよいので、０．７ｍｍ以
上あれば十分である。ガラスの材質については、ガラス
からの溶出イオンが少ない方がよいので無アルカリガラ
スの方が好ましいが、ＳｉＯ２などのバリアコートを施
したソーダライムガラスも市販されているのでこれを使
用できる。ＩＴＯ膜形成方法は、電子ビーム法、スパッ
タリング法、化学反応法など特に制限を受けるものでは
ない。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the positive electrode only needs to be transparent for extracting light, and its components include indium, tin, gold, silver, zinc, aluminum, chromium, nickel, oxygen, nitrogen and hydrogen. , Argon, often composed of at least one element selected from carbon, copper iodide, inorganic conductive substances such as copper sulfide, polythiophene,
There is no particular limitation on conductive polymers such as polypyrrole and polyaniline. Preferable examples in the present invention include tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO). In display applications where patterning is performed, ITO having excellent workability is particularly preferable. However, it may contain a small amount of metal such as silver or gold to lower the surface resistance or suppress voltage drop, and tin, gold,
Silver, zinc, indium, aluminum, chromium, and nickel can also be used as guide electrodes. Among them, chromium is a suitable metal because it can have both functions of a black matrix and a guide electrode. The resistance of the transparent electrode is not limited as long as a current sufficient for light emission of the element can be supplied, but is preferably low from the viewpoint of power consumption of the element. For example, 300Ω /
If the substrate is the following ITO substrate, it functions as an element electrode. However, it is now possible to supply a substrate of about 10 Ω / □, and it is particularly preferable to use a low-resistance substrate. The thickness of the ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of usually 100 to 300 nm. Further, as the glass substrate, soda lime glass, non-alkali glass or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. As for the material of the glass, non-alkali glass is preferable because it is preferable that the amount of ions eluted from the glass is small. However, soda lime glass provided with a barrier coat such as SiO2 is commercially available and can be used. The method of forming the ITO film is not particularly limited, such as an electron beam method, a sputtering method, and a chemical reaction method.
【００１０】負極は、通常ドーピング層と隣接してお
り、電気伝導性があって電子の注入を実現できるもので
あれば特に限定されない。具体的には、白金、金、銀、
銅、鉄、錫、亜鉛、炭素、パラジウム、クロム、アルミ
ニウム、インジウムなどの金属、またはこれら金属を用
いた合金などが好ましい例として挙げられる。中でも電
極の形成の容易さや安定性を考慮すると銀、アルミニウ
ム、インジウムなどが特に好ましい例として挙げること
ができる。これらの電極の作製法も抵抗加熱、電子線、
スパッタリング、イオンプレーティング、ペーストのコ
ーティングなど導通を取ることができれば特に制限され
ないが、本発明では手軽にできる抵抗加熱蒸着法を使用
している。[0010] The negative electrode is usually adjacent to the doping layer, and is not particularly limited as long as it has electrical conductivity and can realize injection of electrons. Specifically, platinum, gold, silver,
Preferred examples include metals such as copper, iron, tin, zinc, carbon, palladium, chromium, aluminum and indium, and alloys using these metals. Among them, silver, aluminum, indium and the like can be cited as particularly preferable examples in consideration of ease and stability of electrode formation. These electrodes are manufactured by resistance heating, electron beam,
Although there is no particular limitation as long as electrical conduction such as sputtering, ion plating, and paste coating can be achieved, the present invention uses a resistance heating evaporation method that can be easily performed.
【００１１】発光を司る物質とは、１）正孔輸送層／発
光層、２）正孔輸送層／発光層／電子輸送層、３）発光
層／電子輸送層、４）以上の組合わせ物質を一層に混合
した形態、そして、５）発光層単独のいずれであっても
よい。即ち、素子構成としては、上記１）〜３）の多層
積層構造の他に４）５）のように発光材料単独または発
光材料と正孔輸送材料および／または電子輸送材料を含
む層を一層設けるだけでもよい。The substances that control light emission include 1) a hole transport layer / light emitting layer, 2) a hole transport layer / light emitting layer / electron transport layer, 3) a light emitting layer / electron transport layer, and 4) a combination of the above substances. , And 5) the light emitting layer alone. That is, as for the element structure, in addition to the multilayer laminated structure of the above 1) to 3), a single layer containing a light emitting material alone or a light emitting material and a hole transporting material and / or an electron transporting material is provided as in 4) 5). Or just
【００１２】正孔輸送層は正孔輸送材料単独で、あるい
は正孔輸送材料と高分子結着剤により形成され、正孔輸
送材料としてはＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´−ジ
（３−メチルフェニル）−４，４´−ジアミン（ＴＰ
Ｄ）などのトリフェニルアミン類、Ｎ−イソプロピルカ
ルバゾ−ルなどの３級アミン類、ピラゾリン誘導体、ス
チルベン系化合物、ヒドラゾン系化合物、オキサジアゾ
ール誘導体やフタロシアニン誘導体に代表される複素環
化合物、ポリマー系では前記単量体を側鎖に有するポリ
カーボネートやスチレン誘導体、ポリビニルカルバゾー
ル、ポリシランなどが好ましいが特に限定されるもので
はない。これらの正孔輸送材料は、積層型の素子の場
合、単独で正孔輸送層を形成してもよいし、二種類以上
を混合または積層してもよい。例えば、ＩＴＯ透明電極
に正孔輸送材料として、まずフタロシアニンを蒸着して
続いてＴＰＤを積層した正孔輸送層は素子の性能を安定
化するし、ポリビニルカルバゾール中にＴＰＤを分散し
た正孔輸送層を持つ素子は、電圧耐性が向上する。The hole transporting layer is formed of a hole transporting material alone or a hole transporting material and a polymer binder, and the hole transporting material is N, N'-diphenyl-N, N'-di ( 3-methylphenyl) -4,4'-diamine (TP
Triphenylamines such as D), tertiary amines such as N-isopropylcarbazole, pyrazoline derivatives, stilbene compounds, hydrazone compounds, heterocyclic compounds represented by oxadiazole derivatives and phthalocyanine derivatives, polymers In the system, polycarbonate having a monomer in the side chain, a styrene derivative, polyvinyl carbazole, polysilane and the like are preferable, but are not particularly limited. In the case of a stacked element, these hole transport materials may form a single hole transport layer alone, or may be a mixture or stack of two or more. For example, as a hole transport material on an ITO transparent electrode, a phthalocyanine is first deposited and then a TPD is laminated. The hole transport layer stabilizes the performance of the device, and the TPD is dispersed in polyvinyl carbazole. The element having the above has improved voltage resistance.
【００１３】発光材料は主に以前から発光体として知ら
れていたアントラセンやピレン、そして前述のトリス
（８−ヒドロキシキノリノラト）アルミニウムや１０−
ヒドロキシベンゾ［ｈ］キノリン金属錯体の他にも、例
えば、ビススチリルアントラセン誘導体、テトラフェニ
ルブタジエン誘導体、クマリン誘導体、オキサジアゾー
ル誘導体、ジスチリルベンゼン誘導体、ピロロピリジン
誘導体、ペリノン誘導体、シクロペンタジエン誘導体、
オキサジアゾール誘導体、チアジアゾロピリジン誘導
体、ポリマー系では、ポリフェニレンビニレン誘導体、
ポリパラフェニレン誘導体、そして、ポリチオフェン誘
導体などが使用できる。また発光層に添加するドーパン
トとしては、前述のルブレン、キナクリドン誘導体、ジ
アザインダセン誘導体、フェノキサゾン６６０、ＤＣＭ
１、Nile Red、ペリノン、ペリレン、クマリン誘導体な
どがそのまま使用できる。The light-emitting materials are mainly anthracene and pyrene, which have long been known as light emitters, and the aforementioned tris (8-hydroxyquinolinolato) aluminum and 10-
In addition to the hydroxybenzo [h] quinoline metal complex, for example, bisstyrylanthracene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, distyrylbenzene derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives,
Oxadiazole derivatives, thiadiazolopyridine derivatives, in the case of polymer systems, polyphenylenevinylene derivatives,
Polyparaphenylene derivatives and polythiophene derivatives can be used. The dopants to be added to the light emitting layer include the above-mentioned rubrene, quinacridone derivative, diazaindacene derivative, phenoxazone 660, DCM
1, Nile Red, perinone, perylene, coumarin derivatives and the like can be used as they are.
【００１４】電子輸送材料としては、電界を与えられた
電極間において負極からの電子を効率良く輸送すること
が必要で、電子注入効率が高く、注入された電子を効率
良く輸送することが望ましい。そのためには電子親和力
が大きく、しかも電子移動度が大きく、さらに安定性に
優れ、トラップとなる不純物が製造時および使用時に発
生しにくい物質であることが要求される。このような条
件を満たす物質としてトリス（８−ヒドロキシキノリノ
ラト）アルミニウム、ビス（１０−ヒドロキシベンゾ
［ｈ］キノリノラト）ベリリウム、２−（４−ビフェニ
ル）−５−（４−ｔ−ブチルフェニル）−１，３，４−
オキサジアゾール（ｔ−ＢｕＰＢＤ）などのオキサジア
ゾール系誘導体、薄膜安定性を向上させたオキサジアゾ
ール二量体系誘導体の１，３−ビス（４−ｔ−ブチルフ
ェニル−１，３，４−オキサジゾリル）ビフェニレン
（ＯＸＤ−１）、１，３−ビス（４−ｔ−ブチルフェニ
ル−１，３，４−オキサジゾリル）フェニレン（ＯＸＤ
−７）、トリアゾール系誘導体、フェナントロリン系誘
導体などがある。As the electron transporting material, it is necessary to efficiently transport electrons from the negative electrode between the electrodes to which an electric field is applied, and it is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is required that the material has a high electron affinity, a high electron mobility, a high stability, and a small amount of impurities serving as traps during production and use. Materials satisfying such conditions include tris (8-hydroxyquinolinolato) aluminum, bis (10-hydroxybenzo [h] quinolinolato) beryllium, and 2- (4-biphenyl) -5- (4-t-butylphenyl). -1,3,4-
Oxadiazole derivatives such as oxadiazole (t-BuPBD) and oxadiazole dimer derivatives 1,3-bis (4-t-butylphenyl-1,3,4- Oxazizolyl) biphenylene (OXD-1), 1,3-bis (4-t-butylphenyl-1,3,4-oxazizolyl) phenylene (OXD-1)
-7), triazole derivatives, phenanthroline derivatives and the like.
【００１５】以上の正孔輸送層、発光層、電子輸送層に
用いられる材料は単独で各層を形成することができる
が、高分子結着剤としてポリ塩化ビニル、ポリカーボネ
ート、ポリスチレン、ポリ（Ｎ−ビニルカルバゾー
ル）、ポリメチルメタクリレート、ポリブチルメタクリ
レート、ポリエステル、ポリスルフォン、ポリフェニレ
ンオキサイド、ポリブタジエン、炭化水素樹脂、ケトン
樹脂、フェノキシ樹脂、ポリサルフォン、ポリアミド、
エチルセルロース、酢酸ビニル、ＡＢＳ樹脂、ポリウレ
タン樹脂などの溶剤可溶性樹脂や、フェノール樹脂、キ
シレン樹脂、石油樹脂、ユリア樹脂、メラミン樹脂、不
飽和ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、
シリコーン樹脂などの硬化性樹脂などに分散させて用い
ることも可能である。The above materials used for the hole transporting layer, the light emitting layer, and the electron transporting layer can be used alone to form the respective layers. As the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly (N- Vinyl carbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide,
Solvent-soluble resins such as ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin, phenolic resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin,
It is also possible to use the resin dispersed in a curable resin such as a silicone resin.
【００１６】発光を司る物質の形成方法は、抵抗加熱蒸
着、電子ビーム蒸着、スパッタリング、分子積層法、コ
ーティング法など特に限定されるものではないが、通常
は、抵抗加熱蒸着、電子ビーム蒸着が特性面で好まし
い。層の厚みは、発光を司る物質の抵抗値にもよるので
限定することはできないが、経験的には１０〜１０００
ｎｍの間から選ばれる。The method of forming the substance which controls light emission is not particularly limited, such as resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination, and coating method. Preferred in terms of surface. The thickness of the layer cannot be limited because it depends on the resistance value of the substance that controls light emission.
nm.
【００１７】電気エネルギーとは主に直流電流を指す
が、パルス電流や交流電流を用いることも可能である。
電流値および電圧値は特に制限はないが、素子の消費電
力、寿命を考慮するとできるだけ低いエネルギーで最大
の輝度が得られるようにするべきである。Although the electric energy mainly refers to a direct current, a pulse current or an alternating current can also be used.
The current value and the voltage value are not particularly limited. However, in consideration of the power consumption and life of the device, it is necessary to obtain the maximum luminance with the lowest possible energy.
【００１８】本発明において透明な電極とは、可視光の
光線透過率が３０％以上であれば使用に大きな障害はな
いが、理想的には１００％に近い方が好ましい。ＩＴＯ
電極などは８０％以上の光線透過率を示すものもある
が、表面抵抗が低いものは光線透過率が低いものが多い
ので、素子特性とのバランスを取りながら選択する必要
がある。基本的には、透明な電極は可視光全域にわたっ
てほぼ同程度の透過率を持つことが好ましい。これはあ
る特定の波長にのみ吸収のある透明電極を使用した場
合、実際の発光色が透明電極を透過することによって変
化することがあるためである。従って、通常は発光色そ
のままで使用したいので平均的な透過率が必要となる。
但し、色を変えたい場合は積極的に吸収を持たせること
も可能であるが、通常はカラーフィルターや干渉フィル
ターを用いて変色させる方が技術的には容易である。In the present invention, a transparent electrode does not have a major obstacle to use as long as the light transmittance of visible light is 30% or more, but ideally it is preferably close to 100%. ITO
Some electrodes have a light transmittance of 80% or more, but those having a low surface resistance often have a low light transmittance. Therefore, it is necessary to select electrodes while keeping a balance with the element characteristics. Basically, it is preferable that the transparent electrode has substantially the same transmittance over the entire visible light range. This is because when a transparent electrode that absorbs only at a specific wavelength is used, the actual emission color may change due to transmission through the transparent electrode. Therefore, it is usually necessary to use an emitted color as it is, so that an average transmittance is required.
However, if it is desired to change the color, it is possible to positively absorb the color, but it is technically easier to change the color using a color filter or an interference filter.
【００１９】本発明においてドーピングは、共役系ポリ
マーのように素子内の有機層の電気伝導性向上ならびに
キャリア注入を容易ならしめる目的がある。本発明の素
子は、電子輸送材料と正孔輸送材料から成っている。従
って、ドーピングの効果は、正孔輸送能力と電子輸送能
力向上のどちらでも期待できる。しかし、本発明の場合
特に電子輸送能力向上を目的としていることから、電子
輸送層へのドーピングについて具体例を示す。まず、ド
ーピングを行うためにはドーパントが必要であり、電子
輸送層にドーピングするには、ドナー性物質を用いる。
逆に、正孔輸送層にドーピングする場合は、アクセプタ
ー性物質を使用することになる。ドナー性物質は、アル
カリ金属、アルカリ土類金属、アミノ化合物、アンモニ
ア、テトラチアフルバレン誘導体、テトラセレナフルバ
レン誘導体などが挙げられる。中でも真空中で容易に蒸
着できて、有機薄膜の中に拡散しやすいナトリウム、カ
リウム、リチウム、マグネシウム、カルシウム、バリウ
ム、ストロンチウム、サマリウム、アンモニアが好まし
い物質である。ドーピング量には適切値があり、性能発
現のことを考慮するとドーピングされる物質に対して１
０％以下であることが好ましいが、有機物へのダメージ
を考慮すると５％以下がより好ましい。ドーピング量
は、通常ＳＩＭＳなどの測定法を用いて検量補正して定
めることが望ましいが、通常は蒸着時の水晶振動子モニ
ターでの膜厚測定が対比していると考えてよい。即ち、
リチウム金属の場合は電子輸送層の膜厚が３０〜１００
ｎｍの場合、モニター値で３ｎｍ以下、好ましくは１．
５ｎｍ以下、更に好ましくは０．５ｎｍ以下であり、マ
グネシウム金属の場合は、モニター値で５０ｎｍ以下、
好ましくは１０ｎｍ以下、更に好ましくは１ｎｍ以下で
あり、カルシウム金属の場合は、モニター値で３０ｎｍ
以下、好ましくは５ｎｍ以下、更に好ましくは１ｎｍ以
下であり、ナトリウム金属の場合は、モニター値で１０
ｎｍ以下、好ましくは３ｎｍ以下、更に好ましくは１ｎ
ｍ以下であり、カリウム金属の場合は、モニター値で１
０ｎｍ以下、好ましくは３ｎｍ以下、更に好ましくは１
ｎｍ以下であれば前記適切値に入っていると考えてよ
い。蒸着速度も素子の特性に大きく影響するが、素子構
成や金属によって最適な速度が存在する。個々には示さ
ないがこれら最適な蒸着速度を使用することが肝要であ
る。In the present invention, doping has the purpose of improving electric conductivity of an organic layer in a device and facilitating carrier injection like a conjugated polymer. The device of the present invention comprises an electron transporting material and a hole transporting material. Therefore, the effect of doping can be expected in both the hole transport ability and the electron transport ability. However, since the purpose of the present invention is particularly to improve the electron transport ability, a specific example will be given for doping of the electron transport layer. First, a dopant is necessary for doping, and a donor substance is used for doping the electron transport layer.
Conversely, when doping the hole transport layer, an acceptor substance is used. Examples of the donor substance include an alkali metal, an alkaline earth metal, an amino compound, ammonia, a tetrathiafulvalene derivative, and a tetraselenafulvalene derivative. Among them, sodium, potassium, lithium, magnesium, calcium, barium, strontium, samarium, and ammonia, which can be easily deposited in a vacuum and easily diffused into an organic thin film, are preferable substances. There is an appropriate value for the doping amount.
It is preferably 0% or less, but more preferably 5% or less in consideration of damage to organic substances. It is generally desirable that the doping amount is determined by calibration correction using a measurement method such as SIMS, but it can be generally considered that film thickness measurement by a quartz oscillator monitor at the time of vapor deposition is compared. That is,
In the case of lithium metal, the thickness of the electron transport layer is 30 to 100.
In the case of nm, the monitor value is 3 nm or less, preferably 1.
5 nm or less, more preferably 0.5 nm or less, in the case of magnesium metal, the monitor value is 50 nm or less,
It is preferably 10 nm or less, more preferably 1 nm or less. In the case of calcium metal, the monitor value is 30 nm.
Or less, preferably 5 nm or less, more preferably 1 nm or less.
nm or less, preferably 3 nm or less, more preferably 1 n
m, and in the case of potassium metal, the monitor value is 1
0 nm or less, preferably 3 nm or less, more preferably 1 nm or less.
If it is less than nm, it may be considered that the value falls within the above-mentioned appropriate value. The deposition rate also greatly affects the characteristics of the element, but there is an optimum rate depending on the element configuration and metal. It is important to use these optimal deposition rates, not individually shown.
【００２０】陰電極は、ドーピング操作が終了してから
引き続き行われる。これは、素子への電力供給が可能で
あればどの様な材料をも用いることが可能である。この
点で合金を使用する電極に比べて安定な電極材料が使用
できるし、共蒸着をする必要がないために電極の特性も
再現性よく発現できる。具体的には、白金、金、銀、
銅、鉄、アルミニウム、インジウム、パラジウム、クロ
ム、ニッケル、亜鉛、炭素、タンタル、タングステン、
導電性高分子、酸化錫、ＩＴＯまたはこれらの合金が使
用できる。金属の抵抗値や安定性を考慮すると金、銀、
銅、アルミニウムクロムがより好ましい例として挙げる
ことができる。The negative electrode is continuously operated after the doping operation is completed. For this, any material can be used as long as power can be supplied to the element. In this respect, a stable electrode material can be used as compared with an electrode using an alloy, and since there is no need to perform co-evaporation, characteristics of the electrode can be expressed with good reproducibility. Specifically, platinum, gold, silver,
Copper, iron, aluminum, indium, palladium, chromium, nickel, zinc, carbon, tantalum, tungsten,
A conductive polymer, tin oxide, ITO, or an alloy thereof can be used. Considering metal resistance and stability, gold, silver,
Copper and aluminum chromium are more preferable examples.
【００２１】ドーピングされる電子輸送材料としては、
前記のトリス（８−ヒドロキシキノリノラト）アルミニ
ウム（ＩＩＩ）、ビス（１０−ヒドロキシベンゾ［ｈ］
キノリノラト）ベリリウム、２−（４−ビフェニル）−
５−（４−ｔ−ブチルフェニル）−１，３，４−オキサ
ジアゾール（ｔ−ＢｕＰＢＤ）などのオキサジアゾール
系誘導体、薄膜安定性を向上させたオキサジアゾール二
量体系誘導体の１，３−ビス（４−ｔ−ブチルフェニル
−１，３，４−オキサジゾリル）ビフェニレン（ＯＸＤ
−１）、１，３−ビス（４−ｔ−ブチルフェニル−１，
３，４−オキサジゾリル）フェニレン（ＯＸＤ−７）、
トリアゾール系誘導体、フェナントロリン系誘導体など
が挙げられるが、これらの材料は、電子輸送材料である
とともに発光材料として機能する場合もある。つまり、
ＩＴＯ／Ｎ，Ｎ´−ジフェニル−Ｎ，Ｎ´−ジ（３−メ
チルフェニル）−４，４´−ジアミン（ＴＰＤ）／トリ
ス（８−ヒドロキシキノリノラト）アルミニウム（ＩＩ
Ｉ）／リチウム／銀を順次積層した素子では、トリス
（８−ヒドロキシキノリノラト）アルミニウム（ＩＩ
Ｉ）が発光材料であるとともに電子輸送材料としての機
能を果たしている。また、ビス（１０−ヒドロキシベン
ゾ［ｈ］キノリノラト）ベリリウムなども同様の機能を
果たしている。As the electron transporting material to be doped,
Tris (8-hydroxyquinolinolato) aluminum (III), bis (10-hydroxybenzo [h]
Quinolinolato) beryllium, 2- (4-biphenyl)-
Oxadiazole derivatives such as 5- (4-t-butylphenyl) -1,3,4-oxadiazole (t-BuPBD) and oxadiazole dimer derivatives 1,2 having improved thin film stability 3-bis (4-t-butylphenyl-1,3,4-oxadizolyl) biphenylene (OXD
-1), 1,3-bis (4-t-butylphenyl-1,1,
3,4-oxadizolyl) phenylene (OXD-7),
Examples thereof include a triazole derivative and a phenanthroline derivative, and these materials are not only an electron transporting material but also function as a light emitting material in some cases. That is,
ITO / N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diamine (TPD) / tris (8-hydroxyquinolinolato) aluminum (II
In a device in which I) / lithium / silver is sequentially stacked, tris (8-hydroxyquinolinolato) aluminum (II)
I) is a light emitting material and functions as an electron transporting material. Further, bis (10-hydroxybenzo [h] quinolinolato) beryllium and the like also perform the same function.
【００２２】[0022]
【実施例】以下、実施例および比較例をあげて本発明を
説明するが、本発明はこれらの例によって限定されるも
のではない。The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００２３】実施例１ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして１×１０-4Ｐａにまで真空引きした。そし
てアルミナるつぼからＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´
−ジ（３−メチルフェニル）−４，４´−ジアミンを
０．３ｎｍ／秒の速度で１３０ｎｍ蒸着し、続いてタン
タル製クヌーセンセルからトリス（８−ヒドロキシキノ
リノラト）アルミニウム（ＩＩＩ）を同じく０．３ｎｍ
／秒の速度で１００ｎｍ蒸着した。真空中で５×５ｍｍ
角の素子ができるようにマスクをセットした。その後、
タングステンボートから０．１ｎｍ／秒の速度でリチウ
ムを１ｎｍ蒸着してから、０．５ｎｍ／秒の速度で銀を
１５０ｎｍ蒸着した。本素子は、４Ｖで４ｃｄ／ｍ2の
発光が認められ、７Ｖ−１．７５ｍＡで２１３ｃｄ／ｍ
2、１２Ｖ−１９５ｍＡで１６７３０ｃｄ／ｍ2の最高発
光輝度が得られた。Example 1 An ITO glass substrate was cut into a predetermined size, and 12 mm in size was cut out.
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum evaporation machine to evacuate to 1 × 10 −4 Pa. Then, N, N'-diphenyl-N, N 'is obtained from the alumina crucible.
-Di (3-methylphenyl) -4,4'-diamine was deposited at a rate of 0.3 nm / sec to a thickness of 130 nm, followed by tris (8-hydroxyquinolinolato) aluminum (III) from a Knudsen cell made of tantalum. 0.3nm
/ Nm at a rate of / sec. 5 × 5mm in vacuum
A mask was set so that corner elements could be formed. afterwards,
1 nm of lithium was deposited at a rate of 0.1 nm / sec from a tungsten boat, and then 150 nm of silver was deposited at a rate of 0.5 nm / sec. This device emits 4 cd / m 2 at 4 V, and 213 cd / m 2 at 7 V-1.75 mA.
2 , a maximum emission luminance of 16730 cd / m 2 was obtained at 12 V-195 mA.
【００２４】実施例２ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして１×１０-4Ｐａにまで真空引きした。そし
てタンタル製クヌーセンセルから銅フタロシアニンを
０．３ｎｍ／秒の速度で２０ｎｍ、続いてアルミナるつ
ぼからビス（ｍ−メチルフェニルカルバゾール）を０．
３ｎｍ／秒の速度で１００ｎｍ蒸着し、更にタンタル製
クヌーセンセルからトリス（８−ヒドロキシキノリノラ
ト）アルミニウム（ＩＩＩ）を同じく０．３ｎｍ／秒の
速度で１００ｎｍ蒸着した。真空中で５×５ｍｍ角の素
子ができるようにマスクをセットした。その後、タング
ステンボートから０．０５ｎｍ／秒の速度でリチウムを
１．０ｎｍ蒸着してから、０．５ｎｍ／秒の速度でアル
ミニウムを２００ｎｍ蒸着した。本素子は、５．６１Ｖ
で１１５ｃｄ／ｍ2の発光が認められ、７．４２Ｖ−
５．００ｍＡの低電力で１２８９ｃｄ／ｍ2の発光輝度
が得られた。Example 2 An ITO glass substrate was cut into a predetermined size,
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum evaporation machine to evacuate to 1 × 10 −4 Pa. Then, copper phthalocyanine was added at a rate of 0.3 nm / sec to a thickness of 20 nm from a tantalum Knudsen cell, and then bis (m-methylphenylcarbazole) was added to the alumina crucible at a rate of 0.2 nm.
100 nm was deposited at a rate of 3 nm / sec, and tris (8-hydroxyquinolinolato) aluminum (III) was further deposited at a rate of 0.3 nm / sec from a Knudsen cell made of tantalum at a rate of 0.3 nm / sec. The mask was set so that a 5 × 5 mm square element was formed in a vacuum. Thereafter, 1.0 nm of lithium was deposited at a rate of 0.05 nm / sec from a tungsten boat, and then 200 nm of aluminum was deposited at a rate of 0.5 nm / sec. This element is 5.61V
At 115 cd / m 2 , and 7.42 V −
An emission luminance of 1289 cd / m 2 was obtained with a low power of 5.00 mA.
【００２５】実施例３ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして１×１０-4Ｐａにまで真空引きした。そし
てタンタル製クヌーセンセルから銅フタロシアニンを
０．３ｎｍ／秒の速度で２０ｎｍ、続いてアルミナるつ
ぼからビス（ｍ−メチルフェニルカルバゾール）を０．
３ｎｍ／秒の速度で１００ｎｍ蒸着し、更にタンタル製
クヌーセンセルからトリス（８−ヒドロキシキノリノラ
ト）アルミニウム（ＩＩＩ）を同じく０．３ｎｍ／秒の
速度で１００ｎｍ蒸着した。真空中で５×５ｍｍ角の素
子ができるようにマスクをセットした。その後、タング
ステンボートから０．０５ｎｍ／秒の速度でリチウムを
０．５ｎｍ蒸着してから、０．５ｎｍ／秒の速度でアル
ミニウムを２００ｎｍ蒸着した。本素子は、４．９２Ｖ
で１１７ｃｄ／ｍ2の発光が認められ、６．７Ｖ−５．
００ｍＡの低電力で１３７５ｃｄ／ｍ2の発光輝度が得
られた。Example 3 An ITO glass substrate was cut into a predetermined size,
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum evaporation machine to evacuate to 1 × 10 −4 Pa. Then, copper phthalocyanine was added at a rate of 0.3 nm / sec to a thickness of 20 nm from a tantalum Knudsen cell, and then bis (m-methylphenylcarbazole) was added to the alumina crucible at a rate of 0.2 nm.
100 nm was deposited at a rate of 3 nm / sec, and tris (8-hydroxyquinolinolato) aluminum (III) was further deposited at a rate of 0.3 nm / sec from a Knudsen cell made of tantalum at a rate of 0.3 nm / sec. The mask was set so that a 5 × 5 mm square element was formed in a vacuum. Thereafter, 0.5 nm of lithium was deposited at a rate of 0.05 nm / sec from a tungsten boat, and then 200 nm of aluminum was deposited at a rate of 0.5 nm / sec. This element is 4.92V
And emission of 117 cd / m 2 was observed, and 6.7 V-5.
An emission luminance of 1375 cd / m 2 was obtained with a low power of 00 mA.
【００２６】実施例４ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして１×１０-4Ｐａにまで真空引きした。そし
てタンタル製クヌーセンセルから銅フタロシアニンを
０．３ｎｍ／秒の速度で２０ｎｍ、続いてアルミナるつ
ぼからビス（ｍ−メチルフェニルカルバゾール）を０．
３ｎｍ／秒の速度で１００ｎｍ蒸着し、更にタンタル製
クヌーセンセルからトリス（８−ヒドロキシキノリノラ
ト）アルミニウム（ＩＩＩ）を同じく０．３ｎｍ／秒の
速度で１００ｎｍ蒸着した。真空中で５×５ｍｍ角の素
子ができるようにマスクをセットした。その後、タング
ステンボートから０．０５ｎｍ／秒の速度でリチウムを
０．０１ｎｍ蒸着してから、０．５ｎｍ／秒の速度でア
ルミニウムを２００ｎｍ蒸着した。本素子は、５．０１
Ｖで１２０ｃｄ／ｍ2の発光が認められ、６．７８Ｖ−
５．００ｍＡの低電力で１４４８ｃｄ／ｍ2の発光輝度
が得られた。Example 4 An ITO glass substrate was cut into a predetermined size,
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum evaporation machine to evacuate to 1 × 10 −4 Pa. Then, copper phthalocyanine was added at a rate of 0.3 nm / sec to a thickness of 20 nm from a tantalum Knudsen cell, and then bis (m-methylphenylcarbazole) was added to the alumina crucible at a rate of 0.2 nm.
100 nm was deposited at a rate of 3 nm / sec, and tris (8-hydroxyquinolinolato) aluminum (III) was further deposited at a rate of 0.3 nm / sec from a Knudsen cell made of tantalum at a rate of 0.3 nm / sec. The mask was set so that a 5 × 5 mm square element was formed in a vacuum. After that, lithium was vapor-deposited at 0.01 nm from a tungsten boat at a rate of 0.05 nm / sec, and then aluminum was vapor-deposited at 200 nm at a rate of 0.5 nm / sec. This element is 5.01
At 120 V, emission of 120 cd / m 2 was observed, and 6.78 V −
An emission luminance of 1448 cd / m 2 was obtained with a low power of 5.00 mA.
【００２７】実施例５ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして１×１０-4Ｐａにまで真空引きした。そし
てアルミナるつぼからＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´
−ジ（３−メチルフェニル）−４，４´−ジアミンを
０．３ｎｍ／秒の速度で１３０ｎｍ蒸着し、続いてタン
タル製クヌーセンセルからトリス（８−ヒドロキシキノ
リノラト）アルミニウム（ＩＩＩ）を同じく０．３ｎｍ
／秒の速度で１００ｎｍ蒸着した。真空中で５×５ｍｍ
角の素子ができるようにマスクをセットした。その後、
アルミナるつぼから０．１ｎｍ／秒の速度でマグネシウ
ムを１ｎｍ蒸着してから、０．５ｎｍ／秒の速度で銀を
１５０ｎｍ蒸着した。本素子は、４Ｖで３ｃｄ／ｍ2の
発光が認められ、７Ｖ−１．７２ｍＡで１５３ｃｄ／ｍ
2、１３Ｖ−１５５ｍＡで１３２１０ｃｄ／ｍ2の最高発
光輝度が得られた。Example 5 An ITO glass substrate was cut into a predetermined size,
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum evaporation machine to evacuate to 1 × 10 −4 Pa. Then, N, N'-diphenyl-N, N 'is obtained from the alumina crucible.
-Di (3-methylphenyl) -4,4'-diamine was deposited at a rate of 0.3 nm / sec to a thickness of 130 nm, followed by tris (8-hydroxyquinolinolato) aluminum (III) from a Knudsen cell made of tantalum. 0.3nm
/ Nm at a rate of / sec. 5 × 5mm in vacuum
A mask was set so that corner elements could be formed. afterwards,
1 nm of magnesium was deposited at a rate of 0.1 nm / sec from an alumina crucible, and then 150 nm of silver was deposited at a rate of 0.5 nm / sec. This device emits 3 cd / m 2 at 4 V and 153 cd / m 2 at 7 V-1.72 mA.
2. A maximum luminance of 13210 cd / m 2 was obtained at 13 V-155 mA.
【００２８】実施例６ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングして基板を洗浄し
た。ポリビニルカルバゾールのジクロロエタンに溶解し
（濃度８．５ｍｇ／ｇ）、０．５μｍのＰＴＦＥフィル
ターで濾過して溶液を調整した。この溶液からＩＴＯ基
板ディップコーティングでポリビニルカルバゾールを２
０ｎｍ塗布した（引上げ速度５０ｍｍ／分）。この基板
を５×５ｍｍ角の素子ができるようにマスクとともに真
空蒸着機にセットして２×１０-3Ｐａにまで真空引きし
た。そして、タンタル製クヌーセンセルからトリス（８
−ヒドロキシキノリノラト）アルミニウム（ＩＩＩ）を
０．３ｎｍ／秒の速度で１５０ｎｍ蒸着した。そして、
タングステンボートから０．２ｎｍ／秒の速度でナトリ
ウムを１．１ｎｍ蒸着してから、続いてタングステンボ
ートから０．３ｎｍ／秒の速度で銀を１５０ｎｍ蒸着し
た。本素子は、４．５Ｖで２ｃｄ／ｍ2の発光が認めら
れ、８．４Ｖ−２．０ｍＡで１９５ｃｄ／ｍ2、１４．
２Ｖ−１００ｍＡで１１３７０ｃｄ／ｍ2の最高発光輝
度が得られた。Example 6 An ITO glass substrate was cut into a predetermined size, and 12 mm in size.
The substrate was washed by etching so as to leave an ITO band having a width. The solution was dissolved in dichloroethane of polyvinyl carbazole (concentration 8.5 mg / g), and filtered through a 0.5 μm PTFE filter to prepare a solution. From this solution, dip coating of polyvinyl carbazole with ITO substrate
0 nm was applied (pulling speed 50 mm / min). The substrate was set in a vacuum evaporation machine together with a mask so as to form a 5 × 5 mm square element, and the substrate was evacuated to 2 × 10 −3 Pa. And tris (8
-Hydroxyquinolinolato) aluminum (III) was deposited at a rate of 0.3 nm / sec to a thickness of 150 nm. And
1.1 nm of sodium was deposited at a rate of 0.2 nm / sec from a tungsten boat, followed by 150 nm of silver deposited at a rate of 0.3 nm / sec from a tungsten boat. This device emitted light of 2cd / m 2 was observed at 4.5V, 195cd / m 2 at 8.4V-2.0 mA, 14.
The highest emission luminance of 11370 cd / m 2 was obtained at 2 V-100 mA.
【００２９】実施例７ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングして基板を洗浄し
た。この基板を真空蒸着機にセットして２×１０-3Ｐａ
にまで真空引きした。そしてタンタル製クヌーセンセル
からＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´−ジ（３−メチル
フェニル）−４，４´−ジアミンを０．３ｎｍ／秒の速
度で５０ｎｍ蒸着し、続いてタンタル製クヌーセンセル
からトリス（８−ヒドロキシキノリノラト）アルミニウ
ム（ＩＩＩ）を同じく０．３ｎｍ／秒の速度で６０ｎｍ
蒸着した。一度、チャンバーを大気圧に戻し、５×５ｍ
ｍ角の素子ができるようにマスクをセットした。その
後、０．３ｎｍ／秒の速度でカルシウムを１ｎｍ蒸着し
てから、０．３ｎｍ／秒の速度で銀を１５０ｎｍ蒸着し
た。本素子は、４Ｖで発光が認められ、１０Ｖ−１．１
９ｍＡで１３５ｃｄ／ｍ2、１８Ｖ−１２４ｍＡで１３
２３０ｃｄ／ｍ2の最高発光輝度が得られた。Example 7 An ITO glass substrate was cut into a predetermined size, and 12 mm in size.
The substrate was washed by etching so as to leave an ITO band having a width. This substrate is set in a vacuum evaporation machine and 2 × 10 −3 Pa
Was evacuated to. Then, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diamine is vapor-deposited at a rate of 0.3 nm / sec to a thickness of 50 nm from a tantalum Knudsen cell. Tris (8-hydroxyquinolinolato) aluminum (III) was also removed from the cell at a rate of 0.3 nm / sec to 60 nm.
Evaporated. Once the chamber is returned to atmospheric pressure, 5 × 5m
A mask was set so that an m-square element could be formed. After that, 1 nm of calcium was deposited at a rate of 0.3 nm / sec, and then 150 nm of silver was deposited at a rate of 0.3 nm / sec. This device emits light at 4 V, and 10 V-1.1
135 cd / m 2 at 9 mA, 13 at 18 V-124 mA
The highest emission luminance of 230 cd / m 2 was obtained.
【００３０】実施例８ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして２×１０-3Ｐａにまで真空引きした。そし
てタンタル製クヌーセンセルからＮ，Ｎ´−ジフェニル
−Ｎ，Ｎ´−ジ（３−メチルフェニル）−４，４´−ジ
アミンを０．３ｎｍ／秒の速度で５０ｎｍ蒸着し、続い
てタンタル製クヌーセンセルからトリス（８−ヒドロキ
シキノリノラト）アルミニウム（ＩＩＩ）を同じく０．
３ｎｍ／秒の速度で６０ｎｍ蒸着した。一度、チャンバ
ーを大気圧に戻し、薄膜をコーティングした基板をアン
モニア飽和環境下に３分晒した。その後、５×５ｍｍ角
の素子ができるようにマスクをセットして２×１０-3Ｐ
ａにまで真空引きしてから０．３ｎｍ／秒の速度で、
０．３ｎｍ／秒の速度でアルミニウムを５０ｎｍ蒸着し
た。本素子は、５Ｖで発光が認められ、１０Ｖ−２．６
２ｍＡで１１７ｃｄ／ｍ2の発光輝度が得られた。Example 8 An ITO glass substrate was cut into a predetermined size,
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum vapor deposition machine and evacuated to 2 × 10 −3 Pa. Then, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diamine is vapor-deposited at a rate of 0.3 nm / sec to a thickness of 50 nm from a tantalum Knudsen cell. Tris (8-hydroxyquinolinolato) aluminum (III) was also added to the cell from the cell.
60 nm was deposited at a rate of 3 nm / sec. Once the chamber was returned to atmospheric pressure, the substrate coated with the thin film was exposed to an ammonia saturated environment for 3 minutes. After that, a mask is set so that a 5 × 5 mm square element is formed, and 2 × 10 −3 P
After evacuation to a, at a speed of 0.3 nm / sec,
50 nm of aluminum was deposited at a rate of 0.3 nm / sec. This device emits light at 5 V, and 10 V-2.6.
An emission luminance of 117 cd / m 2 was obtained at 2 mA.
【００３１】比較例１（ドーピングのない場合） ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングした。この基板を
洗浄した後にＵＶ−オゾン処理を施してから真空蒸着機
にセットして１×１０-4Ｐａにまで真空引きした。そし
てアルミナるつぼからＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´
−ジ（３−メチルフェニル）−４，４´−ジアミンを
０．３ｎｍ／秒の速度で１３０ｎｍ蒸着し、続いてタン
タル製クヌーセンセルからトリス（８−ヒドロキシキノ
リノラト）アルミニウム（ＩＩＩ）を同じく０．３ｎｍ
／秒の速度で１００ｎｍ蒸着した。真空中で５×５ｍｍ
角の素子ができるようにマスクをセットした。その後、
０．５ｎｍ／秒の速度で銀を１５０ｎｍ蒸着した。本素
子は、６Ｖで２ｃｄ／ｍ2の発光が認められ、１０Ｖ−
３．６３ｍＡで１６０ｃｄ／ｍ2、１６Ｖ−１５０ｍＡ
で２９１０ｃｄ／ｍ2の最高発光輝度が得られた。Comparative Example 1 (without doping) An ITO glass substrate was cut into a predetermined size,
Etching was performed so that an ITO band having a width remained. After washing the substrate, the substrate was subjected to UV-ozone treatment, and then set in a vacuum evaporation machine to evacuate to 1 × 10 −4 Pa. Then, N, N'-diphenyl-N, N 'is obtained from the alumina crucible.
-Di (3-methylphenyl) -4,4'-diamine was deposited at a rate of 0.3 nm / sec to a thickness of 130 nm, followed by tris (8-hydroxyquinolinolato) aluminum (III) from a Knudsen cell made of tantalum. 0.3nm
/ Nm at a rate of / sec. 5 × 5mm in vacuum
A mask was set so that corner elements could be formed. afterwards,
150 nm of silver was deposited at a rate of 0.5 nm / sec. This device emits 2 cd / m 2 at 6 V, and emits 10 V-
160 cd / m 2 at 3.63 mA, 16 V-150 mA
, A maximum emission luminance of 2910 cd / m 2 was obtained.
【００３２】比較例２（ドーピングのない場合） ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングして基板を洗浄し
た。この基板を真空蒸着機にセットして２×１０-3Ｐａ
にまで真空引きした。そしてタンタル製クヌーセンセル
からＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´−ジ（３−メチル
フェニル）−４，４´−ジアミンを０．３ｎｍ／秒の速
度で５０ｎｍ蒸着し、続いてタンタル製クヌーセンセル
からトリス（８−ヒドロキシキノリノラト）アルミニウ
ム（ＩＩＩ）を同じく０．３ｎｍ／秒の速度で６０ｎｍ
蒸着した。一度、チャンバーを大気圧に戻し、５×５ｍ
ｍ角の素子ができるようにマスクをセットした。その
後、０．３ｎｍ／秒の速度でアルミニウムを５０ｎｍ蒸
着した。本素子は、５Ｖで発光が認められ、１２Ｖ−
１．８６ｍＡで１００ｃｄ／ｍ2、１８Ｖ−７５ｍＡで
２３２０ｃｄ／ｍ2の最高発光輝度が得られた。Comparative Example 2 (without doping) An ITO glass substrate was cut into a predetermined size,
The substrate was washed by etching so as to leave an ITO band having a width. This substrate is set in a vacuum evaporation machine and 2 × 10 −3 Pa
Was evacuated to. Then, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diamine is vapor-deposited at a rate of 0.3 nm / sec to a thickness of 50 nm from a tantalum Knudsen cell. Tris (8-hydroxyquinolinolato) aluminum (III) was also removed from the cell at a rate of 0.3 nm / sec to 60 nm.
Evaporated. Once the chamber is returned to atmospheric pressure, 5 × 5m
A mask was set so that an m-square element could be formed. Thereafter, 50 nm of aluminum was deposited at a rate of 0.3 nm / sec. This device emits light at 5 V, and emits light at 12 V-
In 100cd / m 2, 18V-75mA is maximum emission luminance of 2320cd / m 2 was obtained in 1.86MA.
【００３３】比較例３ ＩＴＯガラス基板を所定の大きさに切り出し、１２ｍｍ
幅のＩＴＯ帯が残るようにエッチングして基板を洗浄し
た。ポリビニルカルバゾールのジクロロエタンに溶解し
（濃度８．５ｍｇ／ｇ）、０．５μｍのＰＴＦＥフィル
ターで濾過して溶液を調整した。この溶液からＩＴＯ基
板ディップコーティングでポリビニルカルバゾールを２
０ｎｍ塗布した（引上げ速度５０ｍｍ／分）。この基板
を５×５ｍｍ角の素子ができるようにマスクとともに真
空蒸着機にセットして２×１０-3Ｐａにまで真空引きし
た。そして、タンタル製クヌーセンセルからトリス（８
−ヒドロキシキノリノラト）アルミニウム（ＩＩＩ）を
０．３ｎｍ／秒の速度で１００ｎｍ蒸着した。そして、
タングステンボートから０．２ｎｍ／秒の速度でリチウ
ムを３０ｎｍ蒸着してから、続いてタングステンボート
から０．３ｎｍ／秒の速度で銀を１５０ｎｍ蒸着し、積
層負極を得た。本素子は、１５．９Ｖ−４．０ｍＡで３
６０ｃｄ／ｍ2、１９．７Ｖ−２０ｍＡで１８２０ｃｄ
／ｍ2の最高発光輝度が得られた。Comparative Example 3 An ITO glass substrate was cut into a predetermined size,
The substrate was washed by etching so as to leave an ITO band having a width. The solution was dissolved in dichloroethane of polyvinyl carbazole (concentration 8.5 mg / g), and filtered through a 0.5 μm PTFE filter to prepare a solution. From this solution, dip coating of polyvinyl carbazole with ITO substrate
0 nm was applied (pulling speed 50 mm / min). The substrate was set in a vacuum evaporation machine together with a mask so as to form a 5 × 5 mm square element, and the substrate was evacuated to 2 × 10 −3 Pa. And tris (8
-Hydroxyquinolinolato) aluminum (III) was deposited at a rate of 0.3 nm / sec to a thickness of 100 nm. And
After depositing 30 nm of lithium at a rate of 0.2 nm / sec from a tungsten boat, subsequently depositing 150 nm of silver at a rate of 0.3 nm / sec from a tungsten boat to obtain a laminated negative electrode. This device has 3 at 15.9V-4.0mA.
1820 cd at 60 cd / m 2 , 19.7 V-20 mA
/ M 2 was obtained.
【００３４】参考例（電子輸送層中のドーパントの検
出） ＩＴＯ基板を１×２ｍｍの大きさに切り出し洗浄した。
ＵＶ−オゾン処理を施してから真空蒸着機に固定して１
×１０-4Ｐａにまで真空引きした。そしてアルミナるつ
ぼからＮ，Ｎ´−ジフェニル−Ｎ，Ｎ´−ジ（３−メチ
ルフェニル）−４，４´−ジアミンを０．３ｎｍ／秒の
速度で９０ｎｍ蒸着し、続いてタンタル製クヌーセンセ
ルからトリス（８−ヒドロキシキノリノラト）ガリウム
を同じく０．３ｎｍ／秒の速度で１００ｎｍ蒸着した。
続いて、タングステンボートから０．５ｎｍ／秒の速度
でマグネシウムを５０ｎｍ、そして０．５ｎｍ／秒の速
度でアルミニウムを１５０ｎｍ蒸着した。得られた素子
の陰電極をテープを用いて剥離してすぐにＳＩＭＳ測定
を行った。測定条件は、一次イオン種はＯ２＋、一次イ
オンエネルギー３ｋｅＶ、一次イオン電流５０ｎｍ、ラ
スター領域６００×６００μｍ、ゲート率６０％、分析
領域３６０×３６０μｍ、検出二次イオンは正イオン、
電子スプレー条件０．７ｋＶ−３．０Ａ（Ｆ４．０）、
測定時真空度２×１０-6Ｐａ、Ｈ−Ｑ−Ｈは＃１４であ
る。その結果、電子輸送層であり発光層でもあるトリス
（８−ヒドロキシキノリノラト）ガリウム中へのマグネ
シウムの拡散が認められた。Reference Example (Detection of Dopant in Electron Transport Layer) An ITO substrate was cut into a size of 1 × 2 mm and washed.
After UV-ozone treatment, fix it on a vacuum deposition machine
Vacuum was drawn to × 10 -4 Pa. Then, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diamine was vapor-deposited at a rate of 0.3 nm / sec. From the alumina crucible at a rate of 0.3 nm / sec. Tris (8-hydroxyquinolinolato) gallium was also deposited at a rate of 0.3 nm / sec to a thickness of 100 nm.
Subsequently, 50 nm of magnesium was deposited from the tungsten boat at a rate of 0.5 nm / sec, and 150 nm of aluminum was deposited at a rate of 0.5 nm / sec. SIMS measurement was performed immediately after the negative electrode of the obtained device was peeled off using a tape. The measurement conditions are as follows: primary ion species is O2 +, primary ion energy is 3 keV, primary ion current is 50 nm, raster area is 600 × 600 μm, gate rate is 60%, analysis area is 360 × 360 μm, detected secondary ions are positive ions,
Electrospray conditions 0.7 kV-3.0 A (F4.0),
The degree of vacuum during measurement is 2 × 10 −6 Pa, and HQH is # 14. As a result, diffusion of magnesium into tris (8-hydroxyquinolinolato) gallium, which is both an electron transport layer and a light emitting layer, was observed.
【００３５】[0035]
【発明の効果】本発明は、電気エネルギーの利用効率が
高く長時間の駆動にも安定な発光素子を提供できるもの
である。According to the present invention, it is possible to provide a light-emitting element which has a high use efficiency of electric energy and is stable even when driven for a long time.
Claims (8)
し、電気エネルギーにより発光する素子であって、前記
発光を司る物質にドーパントをドーピングすることを特
徴とする発光素子。1. A light-emitting element in which a substance responsible for light emission exists between a positive electrode and a negative electrode and emits light by electric energy, wherein the substance responsible for light emission is doped with a dopant.
特徴とする請求項１記載の発光素子。2. The light emitting device according to claim 1, wherein the dopant has a donor property.
ム、カリウム、リチウム、マグネシウム、カルシウム、
バリウムおよびアンモニアから選ばれる少なくとも一種
類からなる物質であることを特徴とする請求項２記載の
発光素子。3. The method according to claim 1, wherein the dopant having a donor property is sodium, potassium, lithium, magnesium, calcium,
3. The light-emitting device according to claim 2, wherein the light-emitting device is at least one substance selected from barium and ammonia.
送性を持つことを特徴とする請求項１記載の発光素子。4. The light-emitting element according to claim 1, wherein the doped substance responsible for light emission has an electron-transporting property.
ドーパントのドーピング量が１０％以下であることを特
徴とする請求項１記載の発光素子。5. The light emitting device according to claim 1, wherein the doping amount of the dopant is 10% or less with respect to the substance which controls light emission to be doped.
ドーパントのドーピング量が５％以下であることを特徴
とする請求項１記載の発光素子。6. The light emitting device according to claim 1, wherein the doping amount of the dopant is 5% or less with respect to the substance which controls light emission to be doped.
て陰電極が形成されていることを特徴とする請求項１記
載の発光素子。7. The light emitting device according to claim 1, wherein a negative electrode is formed adjacent to the doped substance which controls light emission.
ピングすることを特徴とする発光素子の製造方法。8. A method for manufacturing a light emitting device, wherein the organic layer is doped by exposing it to a metal vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9107081A JPH1050480A (en) | 1996-04-24 | 1997-04-24 | Light-emitting element and manufacture thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10285196 | 1996-04-24 | ||
| JP8-102851 | 1996-04-24 | ||
| JP9107081A JPH1050480A (en) | 1996-04-24 | 1997-04-24 | Light-emitting element and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1050480A true JPH1050480A (en) | 1998-02-20 |
Family
ID=26443539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9107081A Pending JPH1050480A (en) | 1996-04-24 | 1997-04-24 | Light-emitting element and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1050480A (en) |
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| JP2000196140A (en) * | 1998-12-28 | 2000-07-14 | Sharp Corp | Organic electroluminescence element and fabrication thereof |
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| JP2002141173A (en) * | 2000-08-22 | 2002-05-17 | Semiconductor Energy Lab Co Ltd | Light emitting device |
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| JP2002289360A (en) * | 2001-03-27 | 2002-10-04 | Univ Toyama | Organic electric field light emitting device |
| US6905784B2 (en) * | 2000-08-22 | 2005-06-14 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device |
| WO2006027578A1 (en) * | 2004-09-09 | 2006-03-16 | Stephen Paul Harvey | An illuminatable laminate |
| US7326473B2 (en) | 1998-02-17 | 2008-02-05 | Junji Kido | Organic electroluminescent devices |
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1997
- 1997-04-24 JP JP9107081A patent/JPH1050480A/en active Pending
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|---|---|---|---|---|
| US7326473B2 (en) | 1998-02-17 | 2008-02-05 | Junji Kido | Organic electroluminescent devices |
| US6423429B2 (en) | 1998-03-02 | 2002-07-23 | Junji Kido | Organic electroluminescent devices |
| EP0948063A3 (en) * | 1998-03-02 | 2000-08-23 | Kido, Junji | Organic electroluminescent devices |
| EP0948063A2 (en) * | 1998-03-02 | 1999-10-06 | Kido, Junji | Organic electroluminescent devices |
| JP2000196140A (en) * | 1998-12-28 | 2000-07-14 | Sharp Corp | Organic electroluminescence element and fabrication thereof |
| EP1071144A2 (en) * | 1999-07-23 | 2001-01-24 | Sel Semiconductor Energy Laboratory Co., Ltd. | EL display device and a method of manufacturing the same |
| EP1071144A3 (en) * | 1999-07-23 | 2006-04-26 | Sel Semiconductor Energy Laboratory Co., Ltd. | EL display device and a method of manufacturing the same |
| US7456037B2 (en) | 1999-07-23 | 2008-11-25 | Semiconductor Energy Laboratory Co., Ltd. | EL display device and a method of manufacturing the same |
| JP2002164177A (en) * | 1999-11-29 | 2002-06-07 | Canon Inc | Liquid crystal element |
| JP4717198B2 (en) * | 1999-11-29 | 2011-07-06 | キヤノン株式会社 | Organic electroluminescence device |
| JP2002141173A (en) * | 2000-08-22 | 2002-05-17 | Semiconductor Energy Lab Co Ltd | Light emitting device |
| US6905784B2 (en) * | 2000-08-22 | 2005-06-14 | Semiconductor Energy Laboratory Co., Ltd. | Light emitting device |
| JP2002280184A (en) * | 2001-03-16 | 2002-09-27 | Nippon Seiki Co Ltd | Organic electroluminescent element |
| JP2002289360A (en) * | 2001-03-27 | 2002-10-04 | Univ Toyama | Organic electric field light emitting device |
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