JP4491894B2 - Organic electroluminescence display element and method for manufacturing the same - Google Patents
Organic electroluminescence display element and method for manufacturing the same Download PDFInfo
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- JP4491894B2 JP4491894B2 JP2000039657A JP2000039657A JP4491894B2 JP 4491894 B2 JP4491894 B2 JP 4491894B2 JP 2000039657 A JP2000039657 A JP 2000039657A JP 2000039657 A JP2000039657 A JP 2000039657A JP 4491894 B2 JP4491894 B2 JP 4491894B2
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Images
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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
Description
【０００１】
【発明の属する技術分野】
本発明は、表示装置としての発光型ディスプレイであり、フラットパネルディスプレイの一つである有機ＥＬ表示素子およびその有機ＥＬ表示素子の製造方法に関する。
【０００２】
【従来の技術】
有機エレクトロルミネッセンス表示素子（以下、有機ＥＬ表示素子という。）は、自己発光型であるため、これを用いたディスプレイは高輝度、高視野角を示すという特徴があり、かつ低電圧で駆動し得る。
【０００３】
有機ＥＬ表示素子は、互いに対向する陽極電極と陰極電極の間に有機物を挟持する構造体であり、有機物はさらに発光層、正孔注入層／発光層、発光層／電子注入層、正孔注入層／発光層／電子注入層のような積層体か、正孔注入材料と電子注入材料のうち少なくとも一つと発光材料とを混合した構造になっている。
【０００４】
有機ＥＬ表示素子の発光材料や正孔注入材料、電子注入材料である有機物及び有機物上に設けられる電極（陰極）ラインを大気露出させたままにしておくと、これらは大気中の水分、酸素等によって劣化する。大気中の水分、酸素等の影響により、例えば、有機物と電極との界面で剥離が生じたり、構成材料が変質してしまったりする。この結果、非発光領域が生じたり、所定の品質の発光が維持できなくなったりする。
【０００５】
この問題を解決する方法として、特開平５−３６４７５号公報、特開平５−８９９５９号公報、特開平７−１６９５６７号公報等に記載されているように、窒素雰囲気または、その他の不活性ガス雰囲気中で有機ＥＬ表示素子を覆う気密ケース等を密着固定して大気中の水分、酸素等を遮断する技術が知られている。
【０００６】
しかし、大気中の水分、酸素等を完全に遮断するために、気密ケースは金属、またはガラスで形成され、有機ＥＬ表示素子の厚み、重量の約１／２〜１／３をしめる。その為、有機ＥＬ表示素子をさらに薄型化、軽量化する場合、前記の有機ＥＬ表示素子を覆う気密ケース等が障害となる。
【０００７】
また、特開平４−７３８８６号公報に記載されているように、有機ＥＬ表示素子の上に、蒸着やスパッタ法でポリブタジエンなどの有機物やＳｉＯ2 などの無機物の保護膜を設ける方法があるが、ピンホールやクラックなどの欠陥が存在する為、十分な封止とはいえなかった。
【０００８】
【発明が解決しようとする課題】
本発明は、これらの問題点を解決するためになされたものであり、封止不良を改善することで、大気中の水分や酸素等の影響を極力除外し、経時劣化が少なく、初期性能を長時間維持できる長寿命の薄型で軽量の有機ＥＬ表示素子とその製造方法を提供するものである。
【０００９】
【課題を解決するための手段】
本発明において上記目的を達成するために、まず、請求項１においては、基板上の少なくとも一方が透明または半透明の電極及び対向電極間に有機発光層を挟持し、有機発光層及び対向電極を覆う封止層を有する有機エレクトロルミネッセンス表示素子において、前記封止層が、無機物からなる第一封止層と、第一封止層上に形成された金属アルコキシドからなる第二封止層と、第二封止層上に形成された無機物からなる第三封止層と、第三封止層上に形成された金属アルコキシドからなる第四封止層と、を少なくとも有することを特徴とした有機エレクトロルミネッセンス表示素子を提供する。
また、請求項２においては、基板上の少なくとも一方が透明または半透明の電極及び対向電極間に有機発光層を挟持し、有機発光層及び対向電極を覆う封止層が、無機物からなる第一封止層と、第一封止層上に形成された金属アルコキシドからなる第二封止層と、第二封止層上に形成された無機物からなる第三封止層と、第三封止層上に形成された金属アルコキシドからなる第四封止層と、を少なくとも有することを特徴とする有機エレクトロルミネッセンス表示素子の製造方法であって、少なくとも、金属アルコキシドからなる封止層を真空中で成膜する工程を特徴とする有機エレクトロルミネッセンス表示素子の製造方法を提供する。
【００１０】
【発明の実施の形態】
以下、本発明の有機ＥＬ表示素子の一例を、基板上の電極が陽極、対向電極が陰極となる場合の製造工程に従って詳細に説明する。
【００１１】
まず、透光性絶縁体の基板上にスパッタリング法等により透明電極層を形成し、フォトリソグラフィー法及びウェットエッチング法で透明電極層をパターニングし、複数のライン状の電極（陽極）を形成する。
【００１２】
本発明における基板としては、石英基板、ガラス基板、プラスチック基板等が使用できる。
【００１３】
本発明における複数の電極（陽極）の材料としては、ＩＴＯ（インジウムスズ複合酸化物）やインジウム亜鉛複合酸化物、亜鉛アルミニウム複合酸化物等の透明電極材料が使用できる。
【００１４】
なお、抵抗を下げるために陽極には銅、クロム、アルミニウム、チタン等の金属もしくはこれらの積層物を補助電極として部分的に併設させることができる。また、陽極上に短絡防止用の絶縁層を形成する必要は無いが、絶縁層が無いことに限定するものではない。
【００１５】
本発明における有機発光層は、蛍光物質を含む単層構造、あるいは多層構造で形成することができる。
【００１６】
多層膜で形成する場合の有機発光層の構成例は、正孔注入輸送層／電子輸送性発光層または正孔輸送性発光層／電子輸送層からなる２層構成や正孔注入輸送層／発光層／電子輸送層からなる３層構成等がある。さらにより多層で形成することも可能であり、各層を基板上に順に形成する。
【００１７】
正孔注入輸送層材料の例としては、銅フタロシアニン、テトラ（ｔ−ブチル）銅フタロシアニン等の金属フタロシアニン類及び無金属フタロシアニン類、キナクリドン化合物、１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）シクロヘキサン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジ（１−ナフチル）−Ｎ，Ｎ’−ジフフェニル−１，１’−ビフェニル−４，４’−ジアミン等の芳香族アミン系低分子正孔注入輸送層や、その他既存の正孔輸送材料の中から選ぶことができる。
【００１８】
発光材料の例としては、９，１０−ジアリールアントラセン誘導体、ピレン、コロネン、ペリレン、ルブレン、１，１，４，４−テトラフェニルブタジエン、トリス（８−キノリノラート）アルミニウム錯体、トリス（４−メチル−８キノリノラート）アルミニウム錯体、ビス（８−キノリノラート）亜鉛錯体、トリス（４−メチル−５−トリフルオロメチル−８−キノリノラート）アルミニウム錯体、トリス（４−メチル−５−シアノ−８−キノリノラート）アルミニウム錯体、ビス（２−メチル−５−トリフルオロメチル−８−キノリノラート）［４−（４−シアノフェニル）フェノラート］アルミニウム錯体、ビス（２−メチル−５−シアノ−８−キノリノラート）［４−（４−シアノフェニル）フェノラート］アルミニウム錯体、トリス（８−キノリノラート）スカンジウム錯体、ビス〔８−（パラ−トシル）アミノキノリン〕亜鉛錯体及びカドミウム錯体、１，２，３，４−テトラフェニルシクロペンタジエン、ペンタフェニルシクロペンタジエン、ポリ−２，５−ジヘプチルオキシ−パラ−フェニレンビニレン、クマリン系蛍光体、ペリレン系蛍光体、ピラン系蛍光体、アンスロン系蛍光体、ポルフィリン系蛍光体、キナクリドン系蛍光体、Ｎ，Ｎ’−ジアルキル置換キナクリドン系蛍光体、ナフタルイミド系蛍光体、Ｎ，Ｎ’−ジアリール置換ピロロピロール系蛍光体等が挙げられ、これらを単独、または他の低分子材料や高分子材料と混合して用いることができる。
【００１９】
電子輸送材料の例としては、２−（４−ビフィニルイル）−５−（４−ｔ−ブチルフェニル）−１，３，４−オキサジアゾール、及び浜田らの合成したオキサジアゾール誘導体（日本化学会誌、１５４０頁、１９９１年）やビス（１０−ヒドロキシベンゾ［ｈ］キノリノラート）ベリリウム錯体、特開平７−９０２６０号で述べられているトリアゾール化合物等が挙げられる。
【００２０】
低分子系の有機発光層は真空蒸着法により形成することができる。低分子系の有機発光層の膜厚は、単層または積層により形成する場合においても１μｍ以下であり、好ましくは５０〜１５０ｎｍである。
【００２１】
また有機発光層には、ポリパラフェニレンビニレン、ポリ（２−メトキシー５―（２’エチルエキソキシ）―１、４−パラフェニレンビニレン、ポリ（３−アルキルチオフェン）、ポリ（９，９−ジアルキシルフルオレン）、ポリ（パラフェニレン）などの共役高分子系やポリ（Ｎ−ビニルカルバゾール）、２，５−ビス（５−ｔ−ブチル−２，５−ベンゾオキサゾイル）チオフェン、ジンク ビス−ベンゾチアゾール フェノレイトなどの高分子分散系など公知の高分子材料を使用できる。高分子系の有機発光層は、真空蒸着法または上記高分子材料をＮ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド、プロピレンカーボネート、γ−ブチロラクトンなどの有機溶媒や水に溶かした後、スピンコート法、キャスティング法、ディッピング法、バーコート法、ロールコート法、グラビアコート法、マイクログラビア法などの塗布法によって形成することができる。高分子系の有機発光層の膜厚は、１ｎｍ〜１０μｍ、好ましくは１０ｎｍ〜１μｍである。
【００２２】
対向電極（陰極）の材料としては電子注入効率の高い物質を用いる。具体的にはＭｇ，Ａｌ，Ｙｂ等の金属単体を用いたり、有機発光層と接する界面にＬｉや酸化Ｌｉ，ＬｉＦ等の化合物を１ｎｍ程度挟んで、安定性・導電性の高いＡｌやＣｕを積層して用いる。
【００２３】
または電子注入効率と安定性を両立させるため、低仕事関数であるＬｉ，Ｍｇ，Ｃａ，Ｓｒ，Ｌａ，Ｃｅ，Ｅｒ，Ｅｕ，Ｓｃ，Ｙ，Ｙｂ等の金属１種以上と、安定なＡｇ，Ａｌ，Ｃｕ等の金属元素との合金系が用いられる。具体的にはＭｇＡｇ，ＡｌＬｉ，ＣｕＬｉ等の合金が使用できる。
【００２４】
対向電極（陰極）の形成方法は、材料に応じて、真空蒸着法、電子ビーム蒸着法、スパッタリング法などを用いることができる。対向電極の厚さは、１０ｎｍ〜１μｍ程度が望ましい。
【００２５】
その後、有機発光層や対向電極の大気中の水分、酸素による劣化を抑制するため、第一封止層、第二封止層を順次形成する。まず、有機発光層及び対向電極を完全に第一封止層で被覆する。第一封止層は水蒸気バリア性及び／または酸素バリア性を有する無機物で構成される。
【００２６】
また第一封止層は、前記無機物の多層構造としてもよく、この際には、第一層を絶縁性の物質とすれば、第二層以降はマグネシウム、アルミニウム、チタン、銀などの金属単体または、合金としてもよく、例えばＧｅＯ／Ａｌ／ＧｅＯなどの多層構造を用いることができる。
【００２７】
第一封止層の形成方法は、材料に応じて、真空蒸着法、スパッタリング法、ＣＶＤ法などを用いることができる。封止の厚さは、水蒸気バリア性及び／または酸素バリア性が十分にあれば制限は無いが、好ましくは０．１μｍ〜１０μｍ程度が望ましい。
【００２８】
次に、第一封止層のみではピンホール、クラックなどの欠陥が存在し、十分な封止とはいえないため、第一封止層上に第二封止層を積層し第一封止層並びに有機発光層及び対向電極を完全に第二封止層で被覆する。無機物からなる第一封止層と、金属アルコキシドあるいは前記金属アルコキシドの加水分解物あるいはそれらの混合物からなる第二封止層を順次積層してなることにより、第二封止層が第一封止層に生じるピンホール、クラックなどの欠陥を充填、補強する。その為、第一封止層と第二封止層からなる封止層の構造が、緻密に形成され、高いガスバリア性を示し、かつ耐湿性も有する。
【００２９】
本発明で用いられる金属アルコキシドは、テトラエトキシシラン〔Ｓｉ（ＯＣ2 Ｈ5 ）4 〕、トリイソプロポキシアルミニウム〔Ａｌ（Ｏ−２’−Ｃ3 Ｈ7 ）3 〕などの一般式、
Ｍ（ＯＲ）n
（Ｍ：Ｓｉ、Ｔｉ、Ａｌ、Ｚｒ等の金属、Ｒ：ＣＨ3 、Ｃ2 Ｈ5 等のアルキル基）で表せるものである。
【００３０】
第二封止層の形成は、金属アルコキシド、その加水分解物、あるいはそれらの混合物を含む水溶液、あるいは水／アルコール混合溶液を主剤とするコーティング剤を、アルゴンガスなどの不活性ガスや、窒素雰囲気中で、ディッピング法、ロールコーティング法、スクリーン印刷法、スプレー法などの従来公知の手段で塗布する事ができるが、コーティング剤中の水分に、有機物および陰極が汚染される恐れがある。そこでコーティング剤を使用せず形成する方法として、真空プロセスである、真空蒸着法、ＣＶＤ法などを用いることができる。第二封止層の厚さは、第一封止層のピンホール、クラックなどの欠陥を十分に埋めることができるのであれば制限は無いが、好ましくは、０．１μｍ〜１０μｍ程度が望ましい。
【００３１】
なお、上記記載の材料及び形成方法を用い、基板上の電極が陰極、対向電極が陽極となる有機ＥＬ表示素子の製造も可能である。また、よりバリア性を向上させるために、上記記載の封止層に第三封止層、第四封止層としてそれぞれ上記記載の第一封止層、第二封止層と同様の膜を積層して封止層をより多層にしてもよい。さらに、上記記載の封止層をＡｌ、Ｆｅ、Ｎｉ、Ｚｎ等の金属及びそれらの合金、ガラス、セラミック等の無機物、アクリル系、フッ素系、ポリカーボーネート系、ポリエステル、ポリアミド、ポリスチレン、ポリエチレン、ポリプロピレン等の樹脂の蒸着膜からなる保護層で被覆してもよい。
【００３２】
【実施例】
［実施例１］
本発明の実施例を図１に従って説明する。
まず、ガラスからなる基板１上にスパッタリング法で陽極としてＩＴＯ膜を形成した。さらに、透明性と導電性を向上させるために、空気中２３０℃で１時間加熱処理を行い、ＩＴＯ膜を結晶化した。
【００３３】
次に、フォトリソグラフィー法及びウェットエッチング法によってＩＴＯ膜をパターンニングし、電極２を形成した。
【００３４】
次に有機発光層３として銅フタロシアニン、Ｎ，Ｎ’−ジ（１−ナフチル）−Ｎ，Ｎ’−ジフェニル−１，１’−ビフェニル−４，４’−ジアミン、トリス（８−キノリノラート）アルミニウム錯体を順に、１０ｎｍ、４０ｎｍ、５０ｎｍの膜厚で真空蒸着し、次に対向電極（陰極）４としてＭｇＡｇを基板回転しながら二元共蒸着した。
【００３５】
次に、対向電極４上に第一封止層５としてＳｉＯ2 、Ａｌ、ＳｉＯ2 、Ａｌを順に２００ｎｍ、２００ｎｍ、２００ｎｍ、２００ｎｍ、の膜厚で真空蒸着した。
【００３６】
次に、第一封止層５上に第二封止層６としてテトラエトキシシラン〔Ｓｉ（ＯＣ2 Ｈ5 ）4 〕を２００ｎｍの膜厚で真空蒸着した。得られた有機ＥＬ表示素子はダークスポットの拡大は観察されず、初期輝度３００ｃｄ／ｍ2 で半減寿命５５００時間であった。
【００３７】
［比較例１］
第二封止層を設けなかったこと以外は実施例１と同様にして有機ＥＬ表示素子を作製した。得られた有機ＥＬ表示素子は、ダークスポットの拡大が観察され、表示品質が若干悪くなった。初期輝度３００ｃｄ／ｍ2 で半減寿命１０００時間であった。
【００３８】
［比較例２］
実施例１と同様な工程で作製した有機ＥＬ表示素子で第一封止層及び第二封止層を成膜せずに、単に対向電極（陰極）を真空蒸着した。得られた有機ＥＬ表示素子はダークスポットの拡大が観察され、表示品質が著しく悪くなった。初期輝度３００ｃｄ／ｍ2 で半減寿命７０時間であった。
【００３９】
【発明の効果】
本発明によれば、第二封止層によって前記第一封止層を被覆し、第一封止層に存在するピンホール、クラックなどの欠陥を埋めることにより、水分や外気等の影響を極力除外し、経時劣化が少なく、初期性能を長時間維持できる長寿命の有機ＥＬ表示素子とその製造方法を提供することができる。
【００４０】
【図面の簡単な説明】
【図１】本発明の有機ＥＬ表示素子の一例の断面の構造を示す説明図である。
【図２】従来の有機ＥＬ表示素子の一例の断面の構造を示す説明図である。
【符号の説明】
１ 基板
２ 電極（陽極）
３ 有機発光層
４ 対向電極（陰極）
５ 第一封止層
６ 第二封止層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic EL display element that is a light-emitting display as a display device and is one of flat panel displays, and a method for manufacturing the organic EL display element.
[0002]
[Prior art]
Since an organic electroluminescence display element (hereinafter referred to as an organic EL display element) is a self-luminous type, a display using the organic electroluminescence display element has a feature of exhibiting high luminance and a high viewing angle, and can be driven at a low voltage. .
[0003]
The organic EL display element is a structure in which an organic substance is sandwiched between an anode electrode and a cathode electrode facing each other, and the organic substance further includes a light emitting layer, a hole injection layer / light emitting layer, a light emitting layer / electron injection layer, a hole injection. A layered body such as a layer / a light emitting layer / an electron injection layer, or a structure in which a light emitting material is mixed with at least one of a hole injection material and an electron injection material.
[0004]
When the organic EL display element light emitting material, hole injecting material, organic material that is an electron injecting material, and the electrode (cathode) line provided on the organic material are left exposed to the atmosphere, they are exposed to atmospheric moisture, oxygen, etc. Deteriorated by Due to the influence of moisture, oxygen, etc. in the atmosphere, for example, peeling occurs at the interface between the organic substance and the electrode, or the constituent material is altered. As a result, a non-light emitting region is generated, or light emission of a predetermined quality cannot be maintained.
[0005]
As a method for solving this problem, as described in JP-A-5-36475, JP-A-5-89959, JP-A-7-169567, etc., a nitrogen atmosphere or other inert gas atmosphere Among them, a technique for blocking moisture, oxygen, etc. in the atmosphere by tightly fixing an airtight case or the like covering an organic EL display element is known.
[0006]
However, in order to completely block moisture, oxygen, etc. in the atmosphere, the hermetic case is formed of metal or glass, which is about 1/2 to 1/3 of the thickness and weight of the organic EL display element. Therefore, when the organic EL display element is further reduced in thickness and weight, an airtight case that covers the organic EL display element becomes an obstacle.
[0007]
Further, as described in JP-A-4-73886, there is a method of providing a protective film of an organic substance such as polybutadiene or an inorganic substance such as SiO 2 on the organic EL display element by vapor deposition or sputtering. Due to the presence of defects such as pinholes and cracks, the sealing was not sufficient.
[0008]
[Problems to be solved by the invention]
The present invention has been made to solve these problems, and by improving sealing defects, the influence of moisture, oxygen, etc. in the atmosphere is eliminated as much as possible, there is little deterioration over time, and initial performance is improved. The present invention provides a thin and light-weight organic EL display element that can be maintained for a long time and a method for manufacturing the same.
[0009]
[Means for Solving the Problems]
In order to achieve the above object in the present invention, first, in
According to a second aspect of the present invention, the organic light emitting layer is sandwiched between at least one of the transparent and translucent electrode and the counter electrode on the substrate, and the sealing layer covering the organic light emitting layer and the counter electrode is made of an inorganic substance. A sealing layer, a second sealing layer made of a metal alkoxide formed on the first sealing layer, a third sealing layer made of an inorganic material formed on the second sealing layer, and a third sealing A fourth sealing layer made of a metal alkoxide formed on the layer, and a method for producing an organic electroluminescence display element, comprising at least a sealing layer made of a metal alkoxide in a vacuum Provided is a method for producing an organic electroluminescence display element characterized by a film forming step.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an example of the organic EL display element of the present invention will be described in detail according to a manufacturing process in a case where an electrode on a substrate is an anode and a counter electrode is a cathode.
[0011]
First, a transparent electrode layer is formed on a light-transmitting insulator substrate by sputtering or the like, and the transparent electrode layer is patterned by photolithography and wet etching to form a plurality of line-shaped electrodes (anodes).
[0012]
As the substrate in the present invention, a quartz substrate, a glass substrate, a plastic substrate, or the like can be used.
[0013]
As a material for the plurality of electrodes (anodes) in the present invention, transparent electrode materials such as ITO (indium tin composite oxide), indium zinc composite oxide, and zinc aluminum composite oxide can be used.
[0014]
In order to reduce the resistance, a metal such as copper, chromium, aluminum, titanium, or a laminate thereof can be partially provided on the anode as an auxiliary electrode. Moreover, although it is not necessary to form the insulating layer for short circuit prevention on an anode, it does not limit to not having an insulating layer.
[0015]
The organic light emitting layer in the present invention can be formed in a single layer structure containing a fluorescent material or a multilayer structure.
[0016]
Examples of the organic light emitting layer in the case of forming a multilayer film include a hole injection transport layer / electron transport light emitting layer or a two layer structure comprising a hole transport light emitting layer / electron transport layer and a hole injection transport layer / light emission. There is a three-layer structure composed of a layer / electron transport layer. Further, it is possible to form a multilayer, and each layer is formed on the substrate in order.
[0017]
Examples of the hole injecting and transporting layer material include metal phthalocyanines such as copper phthalocyanine and tetra (t-butyl) copper phthalocyanine, and metal-free phthalocyanines, quinacridone compounds, 1,1-bis (4-di-p-tolylamino) Phenyl) cyclohexane, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N′-di (1-naphthyl)- It can be selected from aromatic amine-based low molecular hole injection transport layers such as N, N′-diphphenyl-1,1′-biphenyl-4,4′-diamine and other existing hole transport materials.
[0018]
Examples of the light-emitting material include 9,10-diarylanthracene derivatives, pyrene, coronene, perylene, rubrene, 1,1,4,4-tetraphenylbutadiene, tris (8-quinolinolato) aluminum complex, tris (4-methyl- 8quinolinolato) aluminum complex, bis (8-quinolinolato) zinc complex, tris (4-methyl-5-trifluoromethyl-8-quinolinolato) aluminum complex, tris (4-methyl-5-cyano-8-quinolinolato) aluminum complex Bis (2-methyl-5-trifluoromethyl-8-quinolinolato) [4- (4-cyanophenyl) phenolate] aluminum complex, bis (2-methyl-5-cyano-8-quinolinolato) [4- (4 -Cyanophenyl) phenolate] aluminum complex, Su (8-quinolinolato) scandium complex, bis [8- (para-tosyl) aminoquinoline] zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, poly-2,5 -Diheptyloxy-para-phenylene vinylene, coumarin phosphor, perylene phosphor, pyran phosphor, anthrone phosphor, porphyrin phosphor, quinacridone phosphor, N, N'-dialkyl-substituted quinacridone fluorescence Body, naphthalimide-based phosphor, N, N′-diaryl-substituted pyrrolopyrrole-based phosphor, etc., and these can be used alone or mixed with other low-molecular materials or polymer materials.
[0019]
Examples of electron transport materials include 2- (4-bifinylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole and oxadiazole derivatives synthesized by Hamada et al. Journal, page 1540, 1991), bis (10-hydroxybenzo [h] quinolinolato) beryllium complex, triazole compounds described in JP-A-7-90260, and the like.
[0020]
The low molecular organic light emitting layer can be formed by a vacuum deposition method. The film thickness of the low molecular weight organic light-emitting layer is 1 μm or less, preferably 50 to 150 nm, even when formed by a single layer or a stacked layer.
[0021]
In addition, the organic light-emitting layer includes polyparaphenylene vinylene, poly (2-methoxy-5- (2′ethylexoxy) -1,4-paraphenylene vinylene, poly (3-alkylthiophene), poly (9,9-diaxylfluorene). ), Conjugated polymer systems such as poly (paraphenylene), poly (N-vinylcarbazole), 2,5-bis (5-t-butyl-2,5-benzoxazoyl) thiophene, zinc bis-benzothiazole phenolate A known polymer material such as a polymer dispersion system such as a polymer dispersion can be used for the polymer-based organic light-emitting layer, such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, propylene. After dissolving in an organic solvent such as carbonate or γ-butyrolactone or water, spin coating, cast It can be formed by a coating method such as a coating method, a dipping method, a bar coating method, a roll coating method, a gravure coating method, a micro gravure method, etc. The film thickness of the polymer organic light emitting layer is 1 nm to 10 μm, preferably 10 nm to 1 μm.
[0022]
As the material of the counter electrode (cathode), a substance having high electron injection efficiency is used. Specifically, a single metal such as Mg, Al, or Yb is used, or a compound such as Li, oxidized Li, or LiF is sandwiched by about 1 nm at the interface in contact with the organic light emitting layer, and Al or Cu having high stability and conductivity is placed. Laminated and used.
[0023]
Alternatively, in order to achieve both electron injection efficiency and stability, one or more metals such as Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, and Yb, which are low work functions, and stable Ag, An alloy system with a metal element such as Al or Cu is used. Specifically, alloys such as MgAg, AlLi, and CuLi can be used.
[0024]
As a method for forming the counter electrode (cathode), a vacuum evaporation method, an electron beam evaporation method, a sputtering method, or the like can be used depending on the material. The thickness of the counter electrode is desirably about 10 nm to 1 μm.
[0025]
Thereafter, a first sealing layer and a second sealing layer are sequentially formed in order to suppress deterioration of the organic light emitting layer and the counter electrode due to moisture and oxygen in the atmosphere. First, the organic light emitting layer and the counter electrode are completely covered with the first sealing layer. The first sealing layer is made of an inorganic material having a water vapor barrier property and / or an oxygen barrier property.
[0026]
The first sealing layer may have a multilayer structure of the inorganic material. In this case, if the first layer is made of an insulating material, the second and subsequent layers are simple metals such as magnesium, aluminum, titanium, and silver. Alternatively, an alloy may be used, and for example, a multilayer structure such as GeO / Al / GeO can be used.
[0027]
As a method for forming the first sealing layer, a vacuum deposition method, a sputtering method, a CVD method, or the like can be used depending on the material. The thickness of the sealing is not limited as long as the water vapor barrier property and / or the oxygen barrier property are sufficient, but preferably about 0.1 μm to 10 μm.
[0028]
Next, since there are defects such as pinholes and cracks in the first sealing layer alone and it cannot be said that the sealing is sufficient, the second sealing layer is laminated on the first sealing layer. The layer, the organic light emitting layer and the counter electrode are completely covered with the second sealing layer. A first sealing layer made of an inorganic material and a second sealing layer made of a metal alkoxide, a hydrolyzate of the metal alkoxide, or a mixture thereof are sequentially laminated so that the second sealing layer becomes the first sealing layer. Fill and reinforce defects such as pinholes and cracks generated in the layer. Therefore, the structure of the sealing layer composed of the first sealing layer and the second sealing layer is densely formed, exhibits high gas barrier properties, and has moisture resistance.
[0029]
The metal alkoxide used in the present invention has a general formula such as tetraethoxysilane [Si (OC 2 H 5 ) 4 ], triisopropoxy aluminum [Al (O-2′-C 3 H 7 ) 3 ],
M (OR) n
(M: metal such as Si, Ti, Al and Zr, R: alkyl group such as CH 3 and C 2 H 5 ).
[0030]
The second sealing layer is formed by coating a metal alkoxide, a hydrolyzate thereof, an aqueous solution containing a mixture thereof, or a coating agent mainly composed of a water / alcohol mixed solution with an inert gas such as argon gas or a nitrogen atmosphere. Among them, it can be applied by a conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method, etc., but there is a possibility that the organic substance and the cathode are contaminated by moisture in the coating agent. Therefore, as a method of forming without using a coating agent, a vacuum process such as a vacuum deposition method or a CVD method can be used. The thickness of the second sealing layer is not limited as long as defects such as pinholes and cracks in the first sealing layer can be sufficiently filled, but it is preferably about 0.1 μm to 10 μm.
[0031]
In addition, it is possible to manufacture an organic EL display element using the materials and the forming method described above, in which the electrode on the substrate is a cathode and the counter electrode is an anode. Further, in order to further improve the barrier property, the same sealing film as the first sealing layer and the second sealing layer described above are used as the third sealing layer and the fourth sealing layer, respectively. It may be laminated to make the sealing layer more multilayer. Furthermore, the sealing layer described above is made of metals such as Al, Fe, Ni, Zn and alloys thereof, inorganic materials such as glass and ceramics, acrylic, fluorine, polycarbonate, polyester, polyamide, polystyrene, polyethylene, You may coat | cover with the protective layer which consists of vapor deposition films of resin, such as a polypropylene.
[0032]
【Example】
[Example 1]
An embodiment of the present invention will be described with reference to FIG.
First, an ITO film was formed as an anode on a
[0033]
Next, the ITO film was patterned by a photolithography method and a wet etching method to form an
[0034]
Next, copper phthalocyanine, N, N′-di (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine, tris (8-quinolinolato) aluminum as the organic
[0035]
Next, SiO 2 , Al, SiO 2 , and Al were vacuum-deposited in order of 200 nm, 200 nm, 200 nm, and 200 nm as the
[0036]
Next, tetraethoxysilane [Si (OC 2 H 5 ) 4 ] as a second sealing layer 6 was vacuum deposited on the
[0037]
[Comparative Example 1]
An organic EL display element was produced in the same manner as in Example 1 except that the second sealing layer was not provided. In the obtained organic EL display element, dark spot expansion was observed, and the display quality was slightly deteriorated. The initial luminance was 300 cd / m 2 and the half life was 1000 hours.
[0038]
[Comparative Example 2]
A counter electrode (cathode) was simply vacuum-deposited without forming the first sealing layer and the second sealing layer in the organic EL display device produced in the same process as in Example 1. In the obtained organic EL display element, dark spots were observed to expand, and the display quality was remarkably deteriorated. The initial luminance was 300 cd / m 2 and the half life was 70 hours.
[0039]
【The invention's effect】
According to the present invention, the first sealing layer is covered with the second sealing layer, and defects such as pinholes and cracks existing in the first sealing layer are filled, thereby minimizing the influence of moisture and outside air. It is possible to provide a long-life organic EL display element that can be excluded, has little deterioration over time, and can maintain initial performance for a long time, and a method for manufacturing the same.
[0040]
[Brief description of the drawings]
FIG. 1 is an explanatory view showing a cross-sectional structure of an example of an organic EL display element of the present invention.
FIG. 2 is an explanatory view showing a cross-sectional structure of an example of a conventional organic EL display element.
[Explanation of symbols]
1
3 Organic
5 First sealing layer 6 Second sealing layer
Claims (2)
少なくとも、金属アルコキシドからなる封止層を真空中で成膜する工程を特徴とする有機エレクトロルミネッセンス表示素子の製造方法。An organic light-emitting layer is sandwiched between at least one of a transparent or translucent electrode and a counter electrode on the substrate, and a sealing layer covering the organic light-emitting layer and the counter electrode includes a first sealing layer made of an inorganic material and a first sealing layer. A second sealing layer made of a metal alkoxide formed on the stopper layer, a third sealing layer made of an inorganic material formed on the second sealing layer, and a metal alkoxide formed on the third sealing layer A method for producing an organic electroluminescence display element comprising at least a fourth sealing layer comprising:
The manufacturing method of the organic electroluminescent display element characterized by forming the sealing layer which consists of a metal alkoxide at least in a vacuum.
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| CN101882668B (en) | 2002-12-19 | 2012-05-09 | 株式会社半导体能源研究所 | Display device |
| SG142140A1 (en) | 2003-06-27 | 2008-05-28 | Semiconductor Energy Lab | Display device and method of manufacturing thereof |
| JP2005056587A (en) * | 2003-08-01 | 2005-03-03 | Toyota Industries Corp | El device and manufacturing method thereof |
| JP2006244943A (en) * | 2005-03-07 | 2006-09-14 | Aitesu:Kk | Organic el element and its manufacturing method |
| US20080138538A1 (en) * | 2006-12-06 | 2008-06-12 | General Electric Company | Barrier layer, composite article comprising the same, electroactive device, and method |
| JP5566208B2 (en) * | 2010-07-14 | 2014-08-06 | 株式会社ジャパンディスプレイ | Display device |
| KR101801291B1 (en) * | 2011-10-06 | 2017-11-27 | 엘지디스플레이 주식회사 | Organic electroluminescent diode |
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| JPH07169567A (en) * | 1993-12-16 | 1995-07-04 | Idemitsu Kosan Co Ltd | Organic el element |
| JP2000323273A (en) * | 1999-05-07 | 2000-11-24 | Dainippon Printing Co Ltd | Electroluminescent element |
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| JPH07169567A (en) * | 1993-12-16 | 1995-07-04 | Idemitsu Kosan Co Ltd | Organic el element |
| JP2000323273A (en) * | 1999-05-07 | 2000-11-24 | Dainippon Printing Co Ltd | Electroluminescent element |
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