JPH05347188A - Electroluminescence element - Google Patents
Electroluminescence elementInfo
- Publication number
- JPH05347188A JPH05347188A JP3222386A JP22238691A JPH05347188A JP H05347188 A JPH05347188 A JP H05347188A JP 3222386 A JP3222386 A JP 3222386A JP 22238691 A JP22238691 A JP 22238691A JP H05347188 A JPH05347188 A JP H05347188A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- thin film
- plasma
- ito
- transparent electrode
- 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
- 238000005401 electroluminescence Methods 0.000 title abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000737 periodic effect Effects 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 11
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 239000000356 contaminant Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 5
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 10
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電気的な発光、即ちエレ
クトロルミネセンスを用いた電界発光素子に関し、更に
詳しくは陽極、有機化合物からなる発光層及び陰極の順
で構成される有機薄膜電界発光素子に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroluminescence device using electroluminescence, that is, electroluminescence, and more specifically, an organic thin film electroluminescence comprising an anode, a light emitting layer made of an organic compound and a cathode in this order. It is related to the element.
【０００２】[0002]
【従来の技術】電界発光素子は、その発光機構の違いか
ら（１）発光層内での電子や正孔の局所的な移動により
発光体を励起し、交流電界でのみ発光する真性電界発光
型素子と、（２）電極からの電子と正孔の注入とその発
光層内での再結合により発光体を励起し発光するキャリ
ヤ注入型電界発光素子の２つに分けられる。2. Description of the Related Art An electroluminescence device is an intrinsic electroluminescence type device which (1) excites a light-emitting body by local movement of electrons and holes in a light-emitting layer and emits light only in an AC electric field because of a difference in light-emitting mechanism. The device is divided into (2) a carrier injection type electroluminescent device that injects electrons and holes from an electrode and recombines them in the light emitting layer to excite a light emitting body to emit light.
【０００３】（１）の真性型発光素子は、一般に無機化
合物を発光体とするものであるが，駆動には１００Ｖ以
上の高い交流電界を必要とすること、製造コストが高い
こと、輝度や耐久性も不十分である等多くの問題点を有
している。また（２）のキャリヤ注入型電界発光素子
は、発光層として薄膜状有機化合物を用いる技術が開発
されてから低電圧駆動で高輝度の発光素子が得られるよ
うになった。The intrinsic type light emitting device of (1) generally uses an inorganic compound as a light emitting body, but it requires a high AC electric field of 100 V or more for driving, high manufacturing cost, brightness and durability. There are many problems, such as inferiority. Further, in the carrier injection type electroluminescent device of (2), since a technique of using a thin film organic compound as a light emitting layer was developed, a light emitting device of high brightness can be obtained by driving at a low voltage.
【０００４】これら電界発光素子は、例えば、特開昭 5
9-194393号公報、米国特許明細書4,720,432 号、及びJp
n.Journal of Physics,vol.27,p713〜715 に開示されて
おり、通常、正孔注入輸送層や電子注入層が発光層の片
側あるいは両側に設けられた素子であり１００Ｖ以下の
直流電界で高輝度に発光する。These electroluminescent elements are disclosed in, for example, Japanese Patent Laid-Open No.
9-194393, U.S. Pat.No. 4,720,432, and Jp
n.Journal of Physics, vol.27, p713 to 715, and is usually an element in which a hole injecting and transporting layer and an electron injecting layer are provided on one side or both sides of a light emitting layer, and a DC electric field of 100 V or less is used. It emits high brightness.
【０００５】しかしながら、従来のキャリヤ注入型電界
発光素子は、キャリヤの注入性が不均一であり、その結
果、発光表面に発光輝度の濃淡が発生したり、駆動電圧
が期待通りに低下しない等の欠点を有していた。これら
を解決するために、アルミナの研磨剤で表面を研磨する
方法（特開昭59-194393 号公報）が開示されているが、
発光表面に無数の傷跡による発光の濃淡が発生する欠点
があった。However, in the conventional carrier injection type electroluminescent device, the carrier injecting property is non-uniform, and as a result, light emission brightness varies on the light emitting surface and the driving voltage does not drop as expected. It had drawbacks. To solve these problems, a method of polishing the surface with an alumina abrasive (Japanese Patent Laid-Open No. 59-194393) is disclosed.
There is a drawback that light emission intensity is generated by countless scratches on the light emitting surface.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記従来技
術の実情に鑑みて成されたものであり、その目的は、駆
動電圧の低下と発光表面の均一性に優れた有機薄膜電界
発光素子を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art, and an object thereof is an organic thin film electroluminescent device which is excellent in reduction of driving voltage and uniformity of light emitting surface. To provide.
【０００７】本発明者らは、上記目的を解決するために
錫添加酸化インジジウム（以下ＩＴＯという）薄膜表面
の改良について鋭意検討した結果、ＩＴＯ薄膜表面の濡
れ性が均一に水に濡れる薄膜表面にすることにより、上
記の欠点が解決できることを見い出し本発明を完成する
に至った。The inventors of the present invention have made earnest studies on the improvement of a tin-added indium oxide (hereinafter referred to as ITO) thin film surface in order to solve the above-mentioned object, and as a result, the wettability of the ITO thin film surface was found to be evenly wet with water. By doing so, they have found that the above-mentioned drawbacks can be solved, and completed the present invention.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明によれ
ば、少なくとも一方が透明である陽極と陰極の間に、有
機化合物からなる発光層を設けた電界発光素子におい
て、ガラス表面にＩＴＯ薄膜を形成した透明電極の該Ｉ
ＴＯ薄膜表面が酸素含有気体組成でプラズマ処理されて
なることを特徴とする電界発光素子である。That is, according to the present invention, in an electroluminescent device having a light emitting layer made of an organic compound between an anode and a cathode, at least one of which is transparent, an ITO thin film is formed on a glass surface. I of the formed transparent electrode
The electroluminescent device is characterized in that the surface of the TO thin film is plasma-treated with a gas composition containing oxygen.
【０００９】本発明に用いる電界発光素子とは、例えば
（１）陽極／正孔輸送能を有する化合物／発光機能を有
する電子輸送性有機化合物／陰極、（２）陽極／正孔輸
送能を有する化合物／発光機能を有する有機化合物／電
子輸送能を有する有機化合物／陰極及び前記（１）又は
（２）の各層間に各々の成分で濃度勾配を設けた傾斜構
造層を少なくとも一層積層したものなどが挙げられる。The electroluminescent device used in the present invention is, for example, (1) anode / compound having hole transporting ability / electron transporting organic compound having light emitting function / cathode, (2) having anode / hole transporting ability. Compound / organic compound having a light emitting function / organic compound having an electron transporting ability / cathode and at least one layer of a gradient structure layer having a concentration gradient between the respective layers of the above (1) or (2), etc. Is mentioned.
【００１０】次に本発明の電界発光素子に使用する透明
電極は、ガラス表面に透明性を維持するに必要な約２０
００Å以下のＩＴＯ薄膜を蒸着して透明電極用基板を作
製した後、該基板の所望部分に例えばドライフィルム等
のエッチングレジストを貼り、写真法で現像した後に王
水等でエッチングし、次いでエッチングレジストを除去
して電界発光素子用の透明電極が形成される。Next, the transparent electrode used in the electroluminescent device of the present invention has a thickness of about 20 which is required to maintain transparency on the glass surface.
An ITO thin film having a thickness of 00 Å or less is vapor-deposited to prepare a substrate for a transparent electrode, and then an etching resist such as a dry film is attached to a desired portion of the substrate, developed by a photographic method, and then etched with aqua regia, and then the etching resist. Is removed to form a transparent electrode for the electroluminescent device.
【００１１】しかしこの様にして得られた電界発光素子
用の透明電極は、ＩＴＯ薄膜表面が種々な物質で汚染さ
れており、超音波洗浄を行った後有機溶剤で洗浄され
る。However, in the thus obtained transparent electrode for an electroluminescent device, the surface of the ITO thin film is contaminated with various substances, and after ultrasonic cleaning, it is cleaned with an organic solvent.
【００１２】更に本発明は、ＩＴＯ薄膜表面の濡れ性が
均一に水に濡れる状態となるよう酸素を含有する気体組
成のプラズマで処理を行う。本発明に使用される酸素を
含有する気体組成としては、例えば空気、酸素とアルゴ
ン、酸素とヘリウム、酸素とネオン、酸素とキセノン、
酸素と窒素、及びこれらの混合気体が挙げられる。Further, according to the present invention, the treatment is performed with plasma having a gas composition containing oxygen so that the wettability of the surface of the ITO thin film is uniformly wet with water. Examples of the oxygen-containing gas composition used in the present invention include air, oxygen and argon, oxygen and helium, oxygen and neon, oxygen and xenon,
Examples include oxygen and nitrogen, and a mixed gas thereof.
【００１３】そして本発明のプラズマ処理においては、
無論、酸素単独でもプラズマ処理効果は十分あるが、酸
素単独では排気装置やプラズマ発生装置及びその他を燃
焼して爆発する危険があり、できるだけ本発明のごとき
混合気体組成を用いることが好ましい。And in the plasma treatment of the present invention,
Of course, oxygen alone has a sufficient plasma treatment effect, but oxygen alone has a risk of exploding by burning an exhaust device, a plasma generator, and the like. Therefore, it is preferable to use the mixed gas composition as in the present invention as much as possible.
【００１４】そして酸素を含有する混合組成中の酸素量
は、多いほど短時間の処理で効果があるが、前記のごと
く爆発を起こす危険があるために、５０容量％以下が好
ましい。特に、空気は安全であり、装置内のガス置換の
必要もないために、安価な処理となり極めて好ましいプ
ラズマ用気体である。The oxygen content in the oxygen-containing mixed composition is more effective in a shorter treatment time as it increases, but it is preferably 50% by volume or less because of the risk of explosion as described above. In particular, air is a very preferable plasma gas because it is safe and does not require replacement of gas in the apparatus, resulting in inexpensive processing.
【００１５】[0015]
【作用】このように透明電極は上記の超音波洗浄や有機
溶剤洗浄操作では、ＩＴＯ薄膜表面の濡れ性は改良され
ないが、本発明の酸素を含有する気体組成のプラズマで
処理することにより、ＩＴＯ薄膜表面の有機性の残留汚
染物質は、酸化除去され、更にＩＴＯ薄膜表面が活性化
されて飛躍的に濡れ性が向上して、透明電極表面は水に
均一に濡れる状態になる。この効果のため、本発明の透
明電極は、該電極上に真空蒸着法やキャステング法等で
有機化合物からなる発光層の薄膜を極めて均一に形成で
き、次いで対電極の金属等も均一に真空蒸着できる。こ
の結果、発光表面の均一性が改良され、キャリヤの注入
性も向上するため、駆動電圧も大幅に低下するものであ
る。As described above, the transparent electrode is not improved in the wettability of the ITO thin film surface by the above ultrasonic cleaning or organic solvent cleaning operation, but the transparent electrode is treated with the oxygen-containing gas composition plasma of the present invention to obtain the ITO. The organic residual contaminants on the thin film surface are oxidized and removed, and further the ITO thin film surface is activated to dramatically improve the wettability, and the transparent electrode surface is uniformly wet with water. Due to this effect, in the transparent electrode of the present invention, a thin film of a light emitting layer made of an organic compound can be formed extremely uniformly on the electrode by a vacuum vapor deposition method, a casting method, or the like. it can. As a result, the uniformity of the light emitting surface is improved and the carrier injection property is also improved, so that the driving voltage is also significantly reduced.
【００１６】[0016]
【実施例】以下、実施例により本発明を更に詳細に説明
する。 実施例１ 透明な陽極として、ガラス表面上に錫添加酸化インジウ
ム物質（ＩＴＯ）２０００Åを形成した透明電極用ガラ
スＩＴＯ薄膜基板（松崎真空社製）を使用して、該基板
上の所望の部分にドライフィルム型エッチングレジスト
をラミネートした。次いで、写真製版用マスクを介して
紫外線露光を行った後にトリクロルエチレンで現像し
た。この現像したエッチングレジストの付いたガラスＩ
ＴＯ薄膜基板を王水でエッチングした。次いで、塩化メ
チレンにてエッチングレジストを除去し、次いで、水洗
乾燥した。得られたこのＩＴＯ薄膜基板表面を濡れ指示
薬で濡れを測定した結果３２の値を示した。更に、ＩＴ
Ｏ薄膜基板はトルエン中で５分間超音波洗浄した。次い
でエタノール中で１分間煮沸後取り出して乾燥窒素ガス
を吹き付け乾燥したＩＴＯ薄膜基板表面の濡れ指数は３
３の値であった。この溶剤洗浄処理したＩＴＯ薄膜基板
は、プラズマ処理装置内にセットして、２torrの空気雰
囲気中で交流プラズマを発生させ５分間処理をした。プ
ラズマ処理したＩＴＯ薄膜基板表面の濡れ指数は５４以
上の値を示し水に完全に濡れた。つぎに正孔注入輸送剤
としては、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−（３−メ
チルフェニル）−１、１’−ビフェニル−４、４’−ジ
アミン（以下ＴＰＤという）を、電子輸送性発光剤とし
ては、オキシンのアルミニウム錯体（以下Ａｌｑ3 とい
う）、陰極材料としては、マグネシウム及び銀を真空装
置内の各々独立した電源回路を有する抵抗加熱ボートに
それぞれ投入して、真空装置内の真空度を３×１０-6to
rrとした。まずＩＴＯ薄膜基板表面にＴＰＤのボードを
加熱して1.0 Å／Sec の一定した蒸着速度で２００Å蒸
着し、正孔輸送能を有する有機化合物層を形成した。更
にＴＰＤは、1.0 Å／Sec の一定した蒸着速度で蒸着を
継続しながらＡＬｑ3 の蒸着を開始した。ＡＬｑ3 の蒸
着速度は、０Å／Sec から徐々に増加させＴＰＤとＡＬ
ｑ3 の成分濃度に勾配を設けて傾斜構造層の部分が９０
Åの製膜時では１０Å／Sec であった。この時点でＴＰ
Ｄの加熱を低下させて傾斜構造層の部分が１００Åの製
膜時でＴＰＤの蒸着を停止した。引続きＡｌｑ3 は、単
独で蒸着を継続して発光機能を有する電子輸送性有機化
合物層を２００Å形成した。次いで、マグネシウムと銀
を共蒸着して２０００Åの陰極を形成した。得られた電
界発光素子は、ＩＴＯ薄膜側を陽極とし上述した陰極に
直流電圧をかけると電圧４ｖで肉眼で緑色の発光が確認
された。また、この電界発光素子は、大気中でも作動さ
せることができて、顕微鏡下で発光させ観察した結果、
均一性の高い発光表面を保持していた。The present invention will be described in more detail with reference to the following examples. Example 1 As a transparent anode, a glass ITO thin film substrate for transparent electrodes (made by Matsuzaki Vacuum Co., Ltd.) in which a tin-containing indium oxide material (ITO) 2000Å was formed on a glass surface was used. A dry film type etching resist was laminated. Then, the film was exposed to ultraviolet light through a photomechanical mask and then developed with trichlorethylene. Glass I with this developed etching resist
The TO thin film substrate was etched with aqua regia. Then, the etching resist was removed with methylene chloride, and then washed with water and dried. The value of 32 was shown as a result of wetting the surface of the obtained ITO thin film substrate with a wetting indicator. Furthermore, IT
The O thin film substrate was ultrasonically cleaned in toluene for 5 minutes. Then, it was boiled in ethanol for 1 minute, taken out, blown with dry nitrogen gas and dried, and the wetting index of the surface of the ITO thin film substrate was 3
It was a value of 3. The ITO thin film substrate subjected to the solvent cleaning treatment was set in a plasma treatment apparatus and treated for 5 minutes by generating AC plasma in an air atmosphere of 2 torr. The plasma-treated ITO thin film substrate surface had a wettability index of 54 or more and was completely wet with water. Next, as the hole injecting / transporting agent, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (hereinafter referred to as TPD) is used as an electron. An aluminum complex of oxine (hereinafter referred to as Alq 3 ) is used as a transportable luminescent agent, and magnesium and silver are charged as cathode materials into a resistance heating boat having an independent power supply circuit in a vacuum device, respectively, and then in a vacuum device. Vacuum degree of 3 × 10 -6 to
It was rr. First, a TPD board was heated on the surface of an ITO thin film substrate and vapor-deposited at 200 Å at a constant vapor deposition rate of 1.0 Å / Sec to form an organic compound layer having a hole transporting ability. Furthermore, TPD started the deposition of ALq 3 while continuing the deposition at a constant deposition rate of 1.0 Å / Sec. The deposition rate of ALq 3 is gradually increased from 0Å / Sec to TPD and AL.
A gradient is provided in the component concentration of q 3 so that the gradient structure layer portion is 90
It was 10Å / Sec at the time of film formation of Å. TP at this point
The heating of D was reduced and the deposition of TPD was stopped at the time of forming a film having a gradient structure layer of 100 liters. Subsequently, Alq 3 was continuously vapor-deposited alone to form an electron-transporting organic compound layer having a light emitting function with a thickness of 200Å. Next, magnesium and silver were co-evaporated to form a 2000 Å cathode. In the obtained electroluminescent device, when the ITO thin film side was used as an anode and a DC voltage was applied to the cathode described above, green light emission was visually confirmed at a voltage of 4 v. In addition, this electroluminescent element can be operated even in the atmosphere, and as a result of observing under a microscope,
It retained a highly uniform light emitting surface.
【００１７】比較例１ 実施例１のＩＴＯ薄膜表面をプラズマ処理しなかった濡
れ指数３３の値を持つ透明電極を用いて実施例１と同様
な操作で電界発光素子を作製した。得られた素子は、Ｉ
ＴＯ薄膜側を陽極として陰極に直流電圧をかけると電圧
８ｖで肉眼で緑色の発光を確認した。顕微鏡下で発光さ
せ観察した結果、発光に濃淡分布があり、且つ発光して
いない部分が認められた。Comparative Example 1 An electroluminescent device was prepared in the same manner as in Example 1 using a transparent electrode having a wetting index of 33, which was obtained by not plasma-treating the ITO thin film surface of Example 1. The obtained device has I
When a direct current voltage was applied to the cathode with the TO thin film side as the anode, green light emission was visually confirmed at a voltage of 8 v. As a result of observing under a microscope for luminescence, there was a density distribution of luminescence, and a part where no luminescence was observed was recognized.
【００１８】比較例２ 実施例１のＩＴＯ薄膜表面をプラズマ処理せずに５００
゜Ｃのオーブン中で１０分間加熱処理した。このＩＴＯ
薄膜の表面濡れ指数は３２の値であった。この透明電極
を用いて実施例１と同様な操作で電界発光素子を作製し
た。得られた素子は、ＩＴＯ薄膜側を陽極として陰極に
直流電圧をかけると電圧８ｖで肉眼で緑色の発光を確認
した。顕微鏡下で発光させ観察した結果、発光に濃淡分
布があり、且つ発光していない部分が認められた。Comparative Example 2 The ITO thin film surface of Example 1 was subjected to 500 without plasma treatment.
Heat treatment was performed in an oven at ° C for 10 minutes. This ITO
The surface wetting index of the thin film was 32. An electroluminescent device was produced by the same operation as in Example 1 using this transparent electrode. When a direct current voltage was applied to the cathode of the obtained device with the ITO thin film side serving as an anode, green light emission was visually confirmed at a voltage of 8 v. As a result of observing under a microscope for luminescence, there was a density distribution of luminescence, and a part where no luminescence was observed was recognized.
【００１９】[0019]
【発明の効果】以上説明したように、本発明によれば高
度の濡れの均一性を有する透明電極を用いて製造された
電界発光素子は、均一発光性とキャリヤ注入性が改良さ
れ、駆動電圧も大幅に改良されるため、その工業的価値
は高いものである。As described above, according to the present invention, an electroluminescent device manufactured by using a transparent electrode having a high degree of uniformity of wetting has improved uniform light emission and carrier injection properties, and a driving voltage. Since it is also greatly improved, its industrial value is high.
フロントページの続き (72)発明者 加藤 和男 東京都町田市旭町３丁目５番１号 電気化 学工業株式会社総合研究所内 (72)発明者 浅井 新一郎 東京都町田市旭町３丁目５番１号 電気化 学工業株式会社総合研究所内Front Page Continuation (72) Inventor Kazuo Kato 3-5-1, Asahimachi, Machida-shi, Tokyo Inside Denka Kagaku Kogyo Co., Ltd. (72) Inventor Shinichiro Asai 3-5-1 Asahimachi, Machida-shi, Tokyo No. Denka Kagaku Kogyo Co., Ltd.
Claims (2)
の間に、有機化合物からなる発光層を設けた電界発光素
子において、ガラス表面に錫添加酸化インジウム薄膜を
形成した透明電極の該錫添加酸化インジウム薄膜表面が
酸素含有気体組成でプラズマ処理されてなることを特徴
とする電界発光素子。1. An electroluminescent device having a light emitting layer made of an organic compound between an anode and a cathode, at least one of which is transparent, wherein the tin-containing indium oxide thin film is formed on a glass surface of the transparent electrode. An electroluminescent device characterized in that the surface of an indium thin film is plasma-treated with a gas composition containing oxygen.
素周期表０族元素との混合物である請求項１記載の電界
発光素子。 【請求項２】酸素含有気体組成が、空気、又は酸素と元
素周期表０族元素との混合物である請求項１記載の電界
発光素子。2. The electroluminescent device according to claim 1, wherein the oxygen-containing gas composition is air or a mixture of oxygen and an element of Group 0 of the periodic table. 2. The electroluminescent device according to claim 1, wherein the oxygen-containing gas composition is air or a mixture of oxygen and an element of Group 0 of the periodic table.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3222386A JPH05347188A (en) | 1991-08-08 | 1991-08-08 | Electroluminescence element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3222386A JPH05347188A (en) | 1991-08-08 | 1991-08-08 | Electroluminescence element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05347188A true JPH05347188A (en) | 1993-12-27 |
Family
ID=16781550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3222386A Pending JPH05347188A (en) | 1991-08-08 | 1991-08-08 | Electroluminescence element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05347188A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10144474A (en) * | 1996-11-15 | 1998-05-29 | Kobe Steel Ltd | Light emitting element having diamond film and plane panel display |
| WO1999048338A1 (en) * | 1998-03-18 | 1999-09-23 | Seiko Epson Corporation | Thin film forming method, display, and color filter |
| JP2001284059A (en) * | 2000-03-29 | 2001-10-12 | Honda Motor Co Ltd | Transparent electrode, organic electroluminescent element, treating device and treating method of transparent electrode |
| JP2003077655A (en) * | 2001-09-04 | 2003-03-14 | Canon Inc | Organic electroluminescent element and manufacturing method therefor |
| JP2003257647A (en) * | 2002-03-05 | 2003-09-12 | Seiko Epson Corp | Organic el device manufacturing apparatus, organic el device, and electronic apparatus |
| JP2003257648A (en) * | 2002-03-05 | 2003-09-12 | Seiko Epson Corp | Surface treating device, organic el device manufacturing apparatus, organic el device, and electronic apparatus |
| JP2003272837A (en) * | 2002-03-13 | 2003-09-26 | Seiko Epson Corp | Surface treatment apparatus, manufacturing method and manufacturing device of organic el device, organic el device, and electronic device |
| US7459722B2 (en) | 2001-02-01 | 2008-12-02 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting element and display device using the element |
| JP2009076290A (en) * | 2007-09-20 | 2009-04-09 | Sekisui Chem Co Ltd | Method of surface treatment |
-
1991
- 1991-08-08 JP JP3222386A patent/JPH05347188A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10144474A (en) * | 1996-11-15 | 1998-05-29 | Kobe Steel Ltd | Light emitting element having diamond film and plane panel display |
| WO1999048338A1 (en) * | 1998-03-18 | 1999-09-23 | Seiko Epson Corporation | Thin film forming method, display, and color filter |
| JPH11271753A (en) * | 1998-03-18 | 1999-10-08 | Seiko Epson Corp | Thin film forming method, display device, and color filter |
| US6967352B2 (en) | 1998-03-18 | 2005-11-22 | Seiko Epson Corporation | Thin film formation method, display, and color filter |
| US6476988B1 (en) | 1998-03-18 | 2002-11-05 | Seiko Epson Corporation | Thin film forming method, display, and color filter |
| US6755983B2 (en) | 1998-03-18 | 2004-06-29 | Seiko Epson Corporation | Thin film formation method, display, and color filter |
| JP2001284059A (en) * | 2000-03-29 | 2001-10-12 | Honda Motor Co Ltd | Transparent electrode, organic electroluminescent element, treating device and treating method of transparent electrode |
| US9219241B2 (en) | 2001-02-01 | 2015-12-22 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting element and display device using the element |
| US7459722B2 (en) | 2001-02-01 | 2008-12-02 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting element and display device using the element |
| US9608224B2 (en) | 2001-02-01 | 2017-03-28 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting element and display device using the element |
| US7858977B2 (en) | 2001-02-01 | 2010-12-28 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting element and display device using the element |
| US8174007B2 (en) | 2001-02-01 | 2012-05-08 | Semiconductor Energy Laboratory Co., Ltd. | Organic light emitting element and display device using the element |
| JP2003077655A (en) * | 2001-09-04 | 2003-03-14 | Canon Inc | Organic electroluminescent element and manufacturing method therefor |
| JP2003257648A (en) * | 2002-03-05 | 2003-09-12 | Seiko Epson Corp | Surface treating device, organic el device manufacturing apparatus, organic el device, and electronic apparatus |
| JP2003257647A (en) * | 2002-03-05 | 2003-09-12 | Seiko Epson Corp | Organic el device manufacturing apparatus, organic el device, and electronic apparatus |
| JP2003272837A (en) * | 2002-03-13 | 2003-09-26 | Seiko Epson Corp | Surface treatment apparatus, manufacturing method and manufacturing device of organic el device, organic el device, and electronic device |
| JP2009076290A (en) * | 2007-09-20 | 2009-04-09 | Sekisui Chem Co Ltd | Method of surface treatment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3704883B2 (en) | Organic electroluminescent device and method for manufacturing the same | |
| US9698386B2 (en) | Functionalization of a substrate | |
| JP2818255B2 (en) | Method for manufacturing organic electroluminescence device | |
| JPH05347188A (en) | Electroluminescence element | |
| JP4810739B2 (en) | Organic electroluminescence device and method for producing the same | |
| JP3531680B2 (en) | Manufacturing method of organic EL device | |
| JP2000068073A (en) | Organic electroluminescent element and its manufacture | |
| KR20150002812A (en) | Functionalization of a substrate | |
| JP4310843B2 (en) | Method for manufacturing organic electroluminescent device | |
| JP2000311869A (en) | Surface modifying method for ito thin film | |
| JP2005158392A (en) | Manufacturing method of organic electroluminescent element and manufacturing device using the same | |
| JP2000133064A (en) | Surface modified ito film, its surface treatment method and charge injection type light emitting element using the same | |
| JPH06325873A (en) | Organic thin-film electroluminescent element | |
| JP2000340367A (en) | Organic electroluminescence element and its manufacture | |
| JP2000133466A (en) | Surface reformed ito film, surface treatment method and charge injection type luminescent element using the same | |
| JP2003264075A (en) | Manufacturing method of organic electroluminescent element | |
| JPH05299174A (en) | Organic thin film type el element | |
| JP2001284059A (en) | Transparent electrode, organic electroluminescent element, treating device and treating method of transparent electrode | |
| JP2005158393A (en) | Manufacturing method of organic electroluminescent element | |
| JP2002237215A (en) | Surface modified transparent conductive film, its surface treatment, and charge injection type light emitting device using the same | |
| JP2001313168A (en) | Organic electroluminescent element and manufacturing method of the same | |
| JP2003249379A (en) | Surface treatment method for transparent conductive film, transparent conductive film with surface modified by using the same, and charge injection luminescence element having surface modified transparent conductive film | |
| JP2005203166A (en) | Plasma treatment method and plasma treatment apparatus | |
| JP4780755B2 (en) | Manufacturing method of organic EL element | |
| JP3172555B2 (en) | Electrode manufacturing method for electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |