JPH06325873A - Organic thin-film electroluminescent element - Google Patents
Organic thin-film electroluminescent elementInfo
- Publication number
- JPH06325873A JPH06325873A JP5111903A JP11190393A JPH06325873A JP H06325873 A JPH06325873 A JP H06325873A JP 5111903 A JP5111903 A JP 5111903A JP 11190393 A JP11190393 A JP 11190393A JP H06325873 A JPH06325873 A JP H06325873A
- Authority
- JP
- Japan
- Prior art keywords
- light emitting
- thin film
- anode
- aqueous solution
- clear
- 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
- 239000010409 thin film Substances 0.000 title claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 9
- 239000000356 contaminant Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 238000010030 laminating Methods 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005530 etching Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 238000005401 electroluminescence Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930192419 itoside Natural products 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 dope Chemical compound 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QZXNDEONRUSYFB-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]-3-methylaniline Chemical compound CC1=CC=CC(NC=2C=CC(=CC=2)C=2C=CC(N)=CC=2)=C1 QZXNDEONRUSYFB-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 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
- 239000004332 silver Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
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、発光層、陰極の順で構成され、発光表面の均一性に
優れた有機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 electroluminescent device using electroluminescence, that is, electroluminescence. More specifically, it is composed of an anode, a luminescent layer and a cathode in this order, and has excellent uniformity of luminescent surface. The present invention relates to an organic electroluminescence device.
【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。（１）の真
性電界発光型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。（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り、例えば、特開昭 59-
194393号公報及びUSP 4,720,432 に、この発光素子が開
示されている。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、数１
０Ｖ程度の直流電圧で高輝度に発光する。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、発光表面に無数の発
光しない点（ダークスポットと言う）が発生する欠点を
有していた。2. Description of the Related Art An electroluminescence device is an intrinsic electroluminescence device that emits light only in an alternating electric field by exciting a light emitter by local movement of electrons and holes in a light emitting layer due to a difference in light emitting mechanism. And (2) a carrier injection type electroluminescent device that emits light by injecting electrons and holes from an electrode and recombining the electrons and holes in the light emitting layer to excite the light emitter to emit light. The intrinsic electroluminescence type device of (1) generally uses an inorganic compound as a light emitting body, but requires a high AC electric field of 100 V or more for driving, high manufacturing cost, and poor brightness and durability. It has many problems such as being sufficient. In the carrier injection type electroluminescent device of (2), a technique of using a thin film organic compound as a light emitting layer has been developed, and a light emitting device of high brightness can be obtained by driving at a low voltage.
This light emitting device is disclosed in Japanese Patent Publication No. 194393 and USP 4,720,432. Usually, it is an element in which a hole injecting and transporting layer and an electron injecting layer are provided on one side or both sides of the light emitting layer.
It emits light with high brightness at a DC voltage of about 0V. However, the conventional carrier injection type electroluminescent device has a drawback that the carrier injection property is non-uniform, and as a result, countless non-luminous points (called dark spots) occur on the light emitting surface.
【０００３】これらを解決するため、透明電極を形成す
る錫・ドープ・インジウム酸化物薄膜の表面をアルミナ
を成分とする研磨剤で研磨する方法が、特開昭59-19439
3号公報に開示されているが、発光表面に無数の傷跡に
よる発光の濃淡が発生し、さらに、ダークスポットも発
生し、実用的に不十分であった。 さらに、アルゴンプ
ラズマ処理法や高温で焼成する処理方法などが検討され
ている。これらの方法で処理した錫・ドープ・インジウ
ム酸化物薄膜を使用した有機薄膜電界発光素子の発光表
面は、発光初期から、多数のダークスポットと呼ばれる
微小な発光しない点が発生し、時間の経過とともに成長
し大きくなるため、発光表面が微小な大きさで構成され
ている表示装置に於いては致命的な欠点となっていた。In order to solve these problems, a method of polishing the surface of a tin-doped-indium oxide thin film forming a transparent electrode with an abrasive containing alumina as a component is disclosed in JP-A-59-19439.
Although it is disclosed in Japanese Patent Laid-Open No. 3 (1994), the light emitting surface has light and shade of light emission due to numerous scratches, and further dark spots are generated, which is not practically sufficient. Furthermore, an argon plasma treatment method, a treatment method of firing at high temperature, and the like are being studied. On the light emitting surface of the organic thin film electroluminescent device using the tin-doped indium oxide thin film treated by these methods, a large number of dark spots called dark spots do not occur from the initial stage of light emission, and with the passage of time Since the light-emitting surface grows and becomes large, it is a fatal defect in a display device in which the light emitting surface has a minute size.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、前記の従来
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
ることである。本発明者らは、前記目的を達成するため
に透明導電性薄膜表面の処理につき鋭意検討した結果、
透明導電性薄膜表面をアンモニア及び過酸化水素を含む
水溶液で処理することにより、発光表面の均一性に優れ
た有機薄膜電界発光素子を見いだし本発明を完成するに
至った。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 to provide an organic thin film electroluminescent device having excellent light emitting surface uniformity. is there. The present inventors, as a result of intensive studies on the treatment of the transparent conductive thin film surface to achieve the above object,
By treating the surface of the transparent conductive thin film with an aqueous solution containing ammonia and hydrogen peroxide, an organic thin film electroluminescent device having an excellent light emitting surface uniformity was found, and the present invention was completed.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、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於て、陽極
が、ガラス表面に透明導電性薄膜を積層し、該薄膜表面
をアンモニア及び過酸化水素を含む水溶液で処理して得
られる透明電極で構成されることを特徴とする有機薄膜
電界発光素子を提供するものである。That is, the present invention provides an electroluminescent device in which a light emitting layer made of an organic compound is provided between an anode and a cathode, at least one of which is transparent. It is intended to provide an organic thin film electroluminescent device comprising a transparent conductive film obtained by laminating a transparent conductive thin film and treating the thin film surface with an aqueous solution containing ammonia and hydrogen peroxide.
【０００６】以下、本発明を詳細に説明する。本発明に
使用される、ガラス表面に積層される透明導電性薄膜用
材料としては、（１）金属酸化物として、錫・ドープ・
インジウム酸化物（以下ＩＴＯと略す）、アンチモン・
ドープ・スズ酸化物（以下ＡＴＯと略す）、弗素・ドー
プ・スズ酸化物（以下ＦＴＯと略す）、カドミウム・ド
ープ・スズ酸化物（以下ＣＴＯと略す）及びＩｎ、Ａ
ｌ、Ｓｉ等をドープした酸化亜鉛（以下ＺＯと略す）等
があり、（２）金属類として、金及び白金等がある。こ
れらの中で、パターン化するためのエッチング性等より
ＩＴＯがとくに好ましい。また、ガラス表面に積層され
る透明導電薄膜の厚さは、透明性を維持するために、例
えばＩＴＯ薄膜では、３０００Å以下である。The present invention will be described in detail below. The material for the transparent conductive thin film laminated on the glass surface used in the present invention includes (1) metal oxides such as tin, dope,
Indium oxide (hereinafter abbreviated as ITO), antimony
Doped tin oxide (hereinafter referred to as ATO), fluorine-doped tin oxide (hereinafter referred to as FTO), cadmium-doped tin oxide (hereinafter referred to as CTO), and In, A
There are zinc oxide (hereinafter abbreviated as ZO) doped with l, Si and the like, and (2) metals include gold and platinum. Among these, ITO is particularly preferable because of its etching property for patterning. Further, the thickness of the transparent conductive thin film laminated on the glass surface is, for example, an ITO thin film, is 3000 Å or less in order to maintain transparency.
【０００７】本発明の透明電極は、ガラス表面に積層さ
れた透明導電性薄膜表面をアンモニア及び過酸化水素を
含む水溶液で処理すること、さらに超音波処理を併用す
ることを特徴とするものである。透明電極は、一般的
に、透明導電性薄膜をパターン化したものが用いられ、
通常、ガラス表面に積層された透明導電性薄膜に、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
像後、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、得られた透明電極の表面の汚染物質を超音
波洗浄後、アンモニア及び過酸化水素を含む水溶液に入
れ、超音波処理し、蒸留水で水洗後、クリーンな熱風を
吹き付け乾燥し、製造されたものである。The transparent electrode of the present invention is characterized in that the surface of the transparent conductive thin film laminated on the glass surface is treated with an aqueous solution containing ammonia and hydrogen peroxide, and ultrasonic treatment is used in combination. . The transparent electrode is generally a patterned transparent conductive thin film,
Usually, an etching resist such as a dry film is attached to the transparent conductive thin film laminated on the glass surface, developed by a photographic method, etched with aqua regia, etc., and then the etching resist is removed to obtain the surface of the transparent electrode. After the ultrasonic cleaning of the pollutant No. 2, the sample was placed in an aqueous solution containing ammonia and hydrogen peroxide, subjected to ultrasonic treatment, washed with distilled water, dried by blowing clean hot air, and manufactured.
【０００８】本発明のアンモニア及び過酸化水素を含む
水溶液において、アンモニア、過酸化水素及び水の含有
比率は、特に制限はないが、体積比でアンモニア：過酸
化水素：水＝０．１〜２．５：０．１〜２．５：１０の
範囲が好ましい。処理温度としては、特に制限はなく、
水溶液を加熱して用いる方法も可能であるが、一般的
に、過酸化水素の分解等を考慮すると室温付近で処理す
ることが好ましい。また、処理時間は工業的に生産でき
る範囲ならば、特に制限はない。本発明の透明導電性薄
膜表面をアンモニア及び過酸化水素を含む水溶液で処理
する際に、超音波処理を併用することが、発光表面の均
一性を得るために、特に好ましい。超音波処理の周波数
としては、１０ＫHz〜数メガHzの範囲が好ましい。更
に、本発明のアンモニアと過酸化水素を含む水溶液処理
の予備処理として、有機溶剤洗浄、プラズマ処理、焼成
処理、及び紫外線照射処理などを実施することもでき
る。In the aqueous solution containing ammonia and hydrogen peroxide of the present invention, the content ratio of ammonia, hydrogen peroxide and water is not particularly limited, but the volume ratio of ammonia: hydrogen peroxide: water = 0.1-2. The range of 0.5: 0.1 to 2.5: 10 is preferable. The treatment temperature is not particularly limited,
Although it is possible to use a method in which an aqueous solution is heated, it is generally preferable to perform the treatment near room temperature in consideration of decomposition of hydrogen peroxide. The treatment time is not particularly limited as long as it can be industrially produced. When treating the surface of the transparent conductive thin film of the present invention with an aqueous solution containing ammonia and hydrogen peroxide, it is particularly preferable to use ultrasonic treatment together in order to obtain uniformity of the light emitting surface. The frequency of ultrasonic treatment is preferably in the range of 10 KHz to several megaHz. Furthermore, as a pretreatment of the aqueous solution treatment containing ammonia and hydrogen peroxide of the present invention, organic solvent cleaning, plasma treatment, baking treatment, ultraviolet irradiation treatment, and the like can be performed.
【０００９】[0009]
【作用】透明導電性薄膜表面の有機溶剤洗浄やプラズマ
処理操作、或いは高温処理などでは、透明導電性薄膜表
面に付着している微細な汚染粒子の除去や濡れ性の均一
化に効果がないが、本発明のアンモニア及び過酸化水素
を含む水溶液での処理、さらに、これに、超音波処理を
併用することで、表面の有機性の汚染物質は酸化除去さ
れ、表面に付着している微小な汚染粒子も効果的に除去
されるため、従来の方法では成し得なかった濡れ性の均
一性を飛躍的に改良し、これらの原因で発生していた微
小ダークスポットの発生を減少させ、発光表面の均一性
に優れた有機電界発光素子を得ることができる。Operation: Cleaning of the surface of the transparent conductive thin film with an organic solvent, plasma treatment, or high temperature treatment has no effect on removal of fine contaminant particles adhering to the surface of the transparent conductive thin film and uniform wettability. The treatment with the aqueous solution containing ammonia and hydrogen peroxide of the present invention, and the ultrasonic treatment in combination therewith, oxidize and remove the organic pollutants on the surface, and remove minute particles adhering to the surface. Since contaminant particles are also effectively removed, the uniformity of wettability that could not be achieved by conventional methods is dramatically improved, the generation of minute dark spots caused by these causes is reduced, and light emission is reduced. It is possible to obtain an organic electroluminescence device having excellent surface uniformity.
【００１０】[0010]
【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 透明な陽極の作成を以下の方法で行った。ガラス表面に
錫・ドープ・インジウム酸化物（以下ＩＴＯと略す）薄
膜を、２０００Å形成した透明電極用ガラスＩＴＯ基板
（松崎真空社製）上に、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、水洗した後、アセ
トン中で５分間超音波洗浄した。更に、５００゜Ｃのオ
ーブン中で１５分間加熱処理してレジストを除去し、室
温で放置冷却した。次いで、このＩＴＯ基板を３０％過
酸化水素水（過酸化水素含量、３０ｖｏｌ％）１０ｍ
ｌ、２５％アンモニア水（アンモニア含量、２５ｖｏｌ
％）１０ｍｌ及び蒸留水５０ｍｌを用い作成した混合水
溶液中に浸漬して、室温で２分間超音波処理し、洗浄し
た。更に、蒸留水で水洗後、クリーンな熱風を吹き付け
乾燥した。EXAMPLES The present invention will be described in more detail below with reference to examples. Example A transparent anode was prepared by the following method. A dry film type etching resist was laminated on a glass ITO substrate for a transparent electrode (Matsuzaki Vacuum Co., Ltd.) on which a thin film of tin-doped indium oxide (hereinafter abbreviated as ITO) was formed on the glass surface to 2000 liters. Then, after exposure to ultraviolet light through a photomechanical mask, development was performed with trichlorethylene. Glass I with this developed etching resist
The TO substrate was etched with aqua regia. Then, the etching resist was removed with methylene chloride, washed with water, and then ultrasonically washed in acetone for 5 minutes. Further, the resist was removed by heat treatment in an oven at 500 ° C. for 15 minutes, and the mixture was left standing and cooled at room temperature. Next, this ITO substrate was treated with 30% hydrogen peroxide water (hydrogen peroxide content, 30 vol%) 10 m.
1, 25% ammonia water (ammonia content, 25 vol
%) 10 ml and 50 ml of distilled water, and immersed in a mixed aqueous solution prepared, followed by ultrasonic treatment at room temperature for 2 minutes for washing. Furthermore, after washing with distilled water, clean hot air was blown to dry it.
【００１１】以上の方法で処理したＩＴＯ基板を真空蒸
着装置に装着して、８×１０-6torrの真空度で、（１）
正孔注入輸送剤として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と略す）を用い、
（２）電子輸送性発光剤としてオキシンのアルミニウム
錯体（以下Ａｌｑ3と略す）を用い、（３）陰極材料と
してマグネシウムおよび銀を用い、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から、（１）Ｔ
ＰＤを６５０Åの厚さ、（２）Ａｌｑ3を６５０Åの厚
さに順次蒸着し、（３）次いで、マスクを介して共蒸着
陰極としてＭｇとＡｇを２０００Å、さらに、Ａｇを１
００Å、順次蒸着した。得られた素子は、ＩＴＯ側を陽
極とし、金属を陰極として、５ｖの直流電圧をかけたと
ころ、肉眼で緑色の発光が確認できた。また、この素子
は大気中でも作動させることができ、顕微鏡下で発光さ
せて、発光表面を観察した結果、ダークスポットのない
均一性の高い発光表面であることが確認できた。The ITO substrate treated by the above method was mounted in a vacuum vapor deposition apparatus, and a vacuum degree of 8 × 10 -6 torr was applied to (1).
N, N'-diphenyl-N as a hole injecting and transporting agent,
Using N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (hereinafter abbreviated as TPD),
(2) An aluminum complex of oxine (hereinafter abbreviated as Alq3) is used as an electron transporting luminescent agent, (3) magnesium and silver are used as cathode materials, and a resistance heating boat having an independent power supply circuit in a vacuum device is used. (1) T
PD is deposited to a thickness of 650 Å, (2) Alq3 is deposited to a thickness of 650 Å in sequence, (3) Then, Mg and Ag are 2000 Å as a co-deposition cathode through a mask, and Ag is 1
00Å, and vapor deposition was sequentially performed. When a DC voltage of 5 V was applied to the obtained device with the ITO side as the anode and the metal as the cathode, green light emission was confirmed with the naked eye. Moreover, this device can be operated even in the atmosphere, and when it was made to emit light under a microscope and the light emitting surface was observed, it was confirmed that it was a highly uniform light emitting surface without dark spots.
【００１２】比較例 実施例において、ＩＴＯ基板を３０％過酸化水素水１０
ｍｌ、２５％アンモニア水１０ｍｌ及び蒸留水５０ｍｌ
の混合水溶液中に浸漬して、処理しなかった以外は、同
様に行った。得られた素子はＩＴＯ側を陽極とし、５．
５ｖの直流電圧をかけたところ、肉眼で緑色の発光が確
認できた。顕微鏡下で発光させ観察した結果、微小のダ
ークスポットが２５５ヶ／ｍｍ2認められた。Comparative Example In the example, the ITO substrate was replaced with 30% hydrogen peroxide solution 10
ml, 25% ammonia water 10 ml and distilled water 50 ml
The same procedure was performed, except that the sample was immersed in the mixed aqueous solution of 1 above and was not treated. 4. The obtained device has the ITO side as an anode.
When a direct current voltage of 5 v was applied, green light emission was confirmed with the naked eye. As a result of light emission and observation under a microscope, 255 dark spots / mm 2 were observed.
【００１３】[0013]
【発明効果】以上説明したように、本発明によれば、陽
極、発光層及び陰極の順で構成され、発光表面の均一性
に優れた有機電界発光素子を得ることができる。また、
本発明の有機電界発光素子を用いれば、微小なダークス
ポットの発生がなく、寿命が大幅に長期化されるため、
その工業的価値は高いものである。As described above, according to the present invention, it is possible to obtain an organic electroluminescent device which is composed of an anode, a light emitting layer and a cathode in this order and is excellent in the uniformity of the light emitting surface. Also,
By using the organic electroluminescent device of the present invention, there is no generation of minute dark spots, and the life is greatly extended,
Its industrial value is high.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年２月２１日[Submission date] February 21, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】本発明のアンモニア及び過酸化水素を含む
水溶液において、アンモニア、過酸化水素及び水の含有
比率は、特に制限はないが、重量比でアンモニア：過酸
化水素：水＝０．１〜２．５：０．１〜２．５：１０の
範囲が好ましい。処理温度としては、特に制限はなく、
水溶液を加熱して用いる方法も可能であるが、一般的
に、過酸化水素の分解等を考慮すると室温付近で処理す
ることが好ましい。また、処理時間は工業的に生産でき
る範囲ならば、特に制限はない。本発明の透明導電性薄
膜表面をアンモニア及び過酸化水素を含む水溶液で処理
する際に、超音波処理を併用することが、発光表面の均
一性を得るために、特に好ましい。超音波処理の周波数
としては、１０ＫHz〜数メガHzの範囲が好ましい。更
に、本発明のアンモニアと過酸化水素を含む水溶液処理
の予備処理として、有機溶剤洗浄、プラズマ処理、焼成
処理、及び紫外線照射処理などを実施することもでき
る。In the aqueous solution containing ammonia and hydrogen peroxide of the present invention, the content ratio of ammonia, hydrogen peroxide and water is not particularly limited, but the weight ratio is ammonia: hydrogen peroxide: water = 0.1-2. The range of 0.5: 0.1 to 2.5: 10 is preferable. The treatment temperature is not particularly limited,
Although it is possible to use a method in which an aqueous solution is heated, it is generally preferable to perform the treatment near room temperature in consideration of decomposition of hydrogen peroxide. The treatment time is not particularly limited as long as it can be industrially produced. When treating the surface of the transparent conductive thin film of the present invention with an aqueous solution containing ammonia and hydrogen peroxide, it is particularly preferable to use ultrasonic treatment together in order to obtain uniformity of the light emitting surface. The frequency of ultrasonic treatment is preferably in the range of 10 KHz to several megaHz. Furthermore, as a pretreatment of the aqueous solution treatment containing ammonia and hydrogen peroxide of the present invention, organic solvent cleaning, plasma treatment, baking treatment, ultraviolet irradiation treatment, and the like can be performed.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】[0010]
【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 透明な陽極の作成を以下の方法で行った。ガラス表面に
錫・ドープ・インジウム酸化物（以下ＩＴＯと略す）薄
膜を、２０００Å形成した透明電極用ガラスＩＴＯ基板
（松崎真空社製）上に、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、水洗した後、アセ
トン中で５分間超音波洗浄した。更に、５００゜Ｃのオ
ーブン中で１５分間加熱処理してレジストを除去し、室
温で放置冷却した。次いで、このＩＴＯ基板を３０％過
酸化水素水（過酸化水素含量、３０重量％）１０ｍｌ、
２５％アンモニア水（アンモニア含量、２５重量％）１
０ｍｌ及び蒸留水５０ｍｌを用い作成した混合水溶液中
に浸漬して、室温で２分間超音波処理し、洗浄した。更
に、蒸留水で水洗後、クリーンな熱風を吹き付け乾燥し
た。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 A transparent anode was prepared by the following method. A dry film type etching resist was laminated on a glass ITO substrate for a transparent electrode (Matsuzaki Vacuum Co., Ltd.) on which a thin film of tin-doped indium oxide (hereinafter abbreviated as ITO) was formed on the glass surface to 2000 liters. Then, after exposure to ultraviolet light through a photomechanical mask, development was performed with trichlorethylene. Glass I with this developed etching resist
The TO substrate was etched with aqua regia. Then, the etching resist was removed with methylene chloride, washed with water, and then ultrasonically washed in acetone for 5 minutes. Further, the resist was removed by heat treatment in an oven at 500 ° C. for 15 minutes, and the mixture was left standing and cooled at room temperature. Next, this ITO substrate was mixed with 10 ml of 30% hydrogen peroxide solution (hydrogen peroxide content, 30% by weight ),
25% ammonia water (ammonia content, 25% by weight ) 1
It was immersed in a mixed aqueous solution prepared by using 0 ml and 50 ml of distilled water, sonicated at room temperature for 2 minutes, and washed. Furthermore, after washing with distilled water, clean hot air was blown to dry it.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】比較例１ 実施例１において、ＩＴＯ基板を３０％過酸化水素水１
０ｍｌ、２５％アンモニア水１０ｍｌ及び蒸留水５０ｍ
ｌの混合水溶液中に浸漬して、処理しなかった以外は、
同様に行った。得られた素子はＩＴＯ側を陽極とし、
５．５ｖの直流電圧をかけたところ、肉眼で緑色の発光
が確認できた。顕微鏡下で発光させ観察した結果、微小
のダークスポットが２５５ヶ／ｍｍ2認められた。Comparative Example 1 In Example 1 , the ITO substrate was replaced with 30% hydrogen peroxide solution 1
0 ml, 25% ammonia water 10 ml and distilled water 50 m
except that it was immersed in a mixed aqueous solution of 1 and not treated.
I went the same way. The obtained device has the ITO side as an anode,
When a direct current voltage of 5.5 v was applied, green light emission was confirmed with the naked eye. As a result of light emission and observation under a microscope, 255 dark spots / mm 2 were observed.
Claims (1)
の間に、有機化合物からなる発光層を設けた電界発光素
子に於て、陽極が、ガラス表面に透明導電性薄膜を積層
し、該薄膜表面をアンモニア及び過酸化水素を含む水溶
液で処理して得られる透明電極で構成されることを特徴
とする有機薄膜電界発光素子。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 anode has a transparent conductive thin film laminated on a glass surface. An organic thin film electroluminescent device comprising a transparent electrode obtained by treating the surface with an aqueous solution containing ammonia and hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5111903A JPH06325873A (en) | 1993-05-13 | 1993-05-13 | Organic thin-film electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5111903A JPH06325873A (en) | 1993-05-13 | 1993-05-13 | Organic thin-film electroluminescent element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06325873A true JPH06325873A (en) | 1994-11-25 |
Family
ID=14573020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5111903A Pending JPH06325873A (en) | 1993-05-13 | 1993-05-13 | Organic thin-film electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06325873A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6992326B1 (en) | 2004-08-03 | 2006-01-31 | Dupont Displays, Inc. | Electronic device and process for forming same |
| US7166860B2 (en) | 2004-12-30 | 2007-01-23 | E. I. Du Pont De Nemours And Company | Electronic device and process for forming same |
-
1993
- 1993-05-13 JP JP5111903A patent/JPH06325873A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6992326B1 (en) | 2004-08-03 | 2006-01-31 | Dupont Displays, Inc. | Electronic device and process for forming same |
| US7166860B2 (en) | 2004-12-30 | 2007-01-23 | E. I. Du Pont De Nemours And Company | Electronic device and process for forming same |
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