JP4045684B2 - Organic electroluminescence device - Google Patents
Organic electroluminescence device Download PDFInfo
- Publication number
- JP4045684B2 JP4045684B2 JP05250999A JP5250999A JP4045684B2 JP 4045684 B2 JP4045684 B2 JP 4045684B2 JP 05250999 A JP05250999 A JP 05250999A JP 5250999 A JP5250999 A JP 5250999A JP 4045684 B2 JP4045684 B2 JP 4045684B2
- Authority
- JP
- Japan
- Prior art keywords
- light emitting
- layer
- group
- atom
- emitting layer
- 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.)
- Expired - Lifetime
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- 238000005401 electroluminescence Methods 0.000 title description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 60
- 239000000126 substance Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 150000004696 coordination complex Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 123
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、一対の電極間に発光層または発光層を含む複数層の有機化合物薄層を備えた有機エレクトロルミネセンス素子に関する。
【０００２】
【従来の技術】
近年、情報機器の多様化に伴って、ブラウン管（ＣＲＴ）より低消費電力で薄型の平面表示素子のニーズが高まっている。このような平面表示素子としては液晶、プラズマディスプレイ（ＰＤＰ）等があるが、特に、最近は自己発光型で、表示が鮮明で視野角の広いエレクトロルミネセンス素子が注目されている。ここで、上記エレクトロルミネセンス素子は構成する材料により無機エレクトロルミネセンス素子と有機エレクトロルミネセンス素子に大別することができ、無機エレクトロルミネセンス素子は既に実用化され商品として市販されている。
【０００３】
しかしなから、上記無機エレクトロルミネセンス素子は高電界の印加によって加速された電子が発光中心に衝突して発光するという、いわゆる衝突型励起発光であるため、１００Ｖ以上の高電圧で駆動させる必要がある。このため、周辺機器の高コスト化を招来するという課題を有していた。また、青色発光の良好な発光体がないためフルカラーの表示ができないという課題もあった。
【０００４】
これに対して、有機エレクトロルミネセンス素子は、電極から注入された電荷（正孔および電子）が発光体中で再結合して励起子を生成し、それが発光材料の分子を励起して発光するという、いわゆる注入型発光であるため低電圧で駆動することができる。しかも、有機化合物であるため発光材料の分子構造を容易に変更することができ、任意の発光色を得ることができる。従って、有機エレクトロルミネセンス素子はこれからの表示素子として非常に有望である。
【０００５】
ここで、有機エレクトロルミネセンス素子は正孔輸送層と電子輸送層の２層を備えた素子が、TangとVanSlykeによって提案された（C.W.TangおよびS.A.VanSlyke; Appl. Phys. Lett., 51(1987) 913）。素子の構成は、ガラス基板上に形成した電極、正孔輸送層、電子輸送性発光層、陰極であった。
【０００６】
上記素子では、正孔輸送層が陽極から電子輸送性発光層へ正孔を注入する働きをするとともに、陰極から注入された電子が正孔と再結合することなく陽極へ逃げるのを防ぎ、電子輸送性発光層内へ電子を封じ込める役割を果たしている。このため、この正孔輸送層による電子の封じ込め効果により、従来の単層構造の素子に比べてより効率よく電子と正孔の再結合が起こり、駆動電圧の大幅な低下が可能になった。
【０００７】
また、斎藤らは、２層構造の素子において、電子輸送層だけでなく正孔輸送層も発光層と成り得ることを示した（C.Adachi, T.TsutsuiおよびS.Saito; Appl. Phys. Lett., 55(1989) 1489）。
【０００８】
２層構成の改良として正孔輸送層と電子輸送層の間に有機発光層か挟まれた３層構造の有機エレクトロルミネセンス素子を斎藤らが提案した（C.Adachi, S.Tokito, T.TsutsuiおよびS.Saito; Jpn.J.Appl.Phys.,27(1988) L269）。これは、ガラス基板上に形成した陽極、正孔輸送層、発光層、電子輸送層、陰極からなり、正孔輸送層が電子を発光層に封じ込める働きをするとともに、電子輸送層が正孔を発光層に封じ込める働きをするため発光効率がさらに向上した。
【０００９】
【発明が解決しようとする課題】
このように有機エレクトロルミネセンス素子の発光効率を向上させるために層構成からの改良が行われてきたが、まだまだ発光の高輝度化や高効率化が必要なのが現状である。また、有機エレクトロルミネセンス素子を長時間発光させるためにはより低電圧で低電流密度で発光させることが必要となってくる。
【００１０】
そこで、本発明は上記の点に鑑みて、高輝度で高効率な発光を長期間安定して呈する有機エレクトロルミネセンス素子を提供することを目的とする。
【００１１】
【課題を解決するための手段】
本発明者らは、前記問題点を解決すべく鋭意検討を重ね、特定の金属錯体を用いることで有機エレクトロルミネセンス素子の特性が改善されることを見出し本発明に至った。すなわち本発明は、一対の電極間に発光層または発光層を含む複数の有機化合物薄層を備えた有機エレクトロルミネセンス素子において少なくとも二層が下記化学式［Ｉ］で表される金属錯体を含有することを特徴とする有機エレクトロルミネセンス素子を提供するものである；
【化２】
上記式中、Ｘは酸素原子、硫黄原子または置換基を有する窒素原子を表す。窒素原子に結合する置換基としては、水素原子、メチル基あるいはエチル基等のアルキル基、またはフェニル等のアリール基、またはベンジル基等のアラルキル基等である。好ましくは水素原子、アルキル基、アリール基である。特に好ましくはアルキル基、特にメチル基である。
【００１３】
Ｒ1〜Ｒ6はそれぞれ独立して、水素原子、塩素原子あるいはフッ素原子等のハロゲン原子、クロロメチル基等のハロゲン化アルキル基、メチル基あるいはエチル基等のアルキル基、ベンジル基等のアラルキル基、シアノ基、置換もしくは無置換の芳香族炭化水素基、例えばフェニル基等、または置換もしくは無置換の芳香族複素環基、例えばチエニル基あるいはピロリル基等を表す。芳香族炭化水素基あるいは芳香族複素環基に結合していてもよい置換基としては、メチル基あるいはエチル基等のアルキル基、塩素原子等のハロゲン原子である。Ｒ3とＲ4、Ｒ4とＲ5またはＲ5とＲ6はそれぞれ置換基間で芳香環、ベンゼン環、ナフタレン環等または複素環、フラン環、チオフェン環、インドール環などを形成してもよい。
【００１４】
Ｒ1およびＲ2として好ましい基は、アリール基、置換基を有していてもよいアリール基、または置換基を有していてもよい芳香族複素環基、特にフェニル基、トリル基、クロロフェニル基またはチエニル基であり、Ｒ3〜Ｒ6として好ましい基は水素原子である。
【００１５】
Ｍは亜鉛（Ｚｎ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、マグネシウム（Ｍｇ）、またはジルコニウム（Ｚｒ）などの金属原子を表す。好ましくは亜鉛、マグネシウム、ジルコニウムを表す。
【００１６】
Ｌは、金属原子Ｍに配位する配位子または二重結合で金属原子Ｍに結合する酸素原子を表す。配位子としては、ハロゲン原子、または酸素原子に結合しこの酸素原子を介して金属原子Ｍに配位する水素原子、アルキル基、例えばメチル基、エチル基等、アリール基、例えばフェニル基、ナフチル基、ジフェニル基、フェノキシフェニル基等、複素環式基、例えばキノリン環基等、アラルキル基、例えば、ベンジル基等、カルボニル基、例えばメチルカルボニル基あるいはエチルカルボニル基等のアルキルカルボニル基、フェニルカルボニル基、ナフチルカルボニル基等のアリールカルボニル基、チエニルカルボニル基、ピリジルカルボニル基等のヘテロアリールカルボニル基などが挙げられる。Ｌが二重結合で金属原子Ｍに結合する酸素原子を表す場合、Ｌが２つで１つの酸素原子を表すものとする。
【００１７】
ｍは０から２の整数、ｋは１または２の整数、ｎは１〜３の整数を表す。ｍおよびｎはそれぞれ、金属原子Ｍの価数とｋの値とに関連して決まり、例えば、Ｍが亜鉛やマグネシウムでｋ＝１の場合、ｎは１または２である。ｎ＝２のときｍ＝０であり配位子Ｌを有していないことを表す。Ｍがガリウムでｋ＝１の場合、ｎは１〜３の整数を取り得る。このとき、ｎ＝３であるとｍ＝０となり、配位子Ｌを有していないことを表す。Ｍがジルコニウムでｋ＝１の場合、ｎは１または２である。ｎ＝２のときｍ＝０で配位子Ｌを有していないか、ジルコニウムに二重結合を介して酸素原子が有している（すなわち＞Ｚｒ＝０）ことを表す。なお、金属原子Ｍを２つ有していてもよく、この場合はｋ＝２であり、例えば亜鉛やマグネシウムであれば、ｎ＝３、ｍ＝１などの値を取り得る。
【００１８】
一般式［Ｉ］で表される特定の金属錯体化合物は良好な青色から黄色発光体となる。また、一般式［Ｉ］で表される特定の金属錯体化合物は電子輸送性が良好なため電子輸送材料として電子輸送層、電子注入輸送層、電子注入層などの電子輸送性の電荷輸送層に含有することができる。
【００１９】
一般式［Ｉ］に包含される化合物は、例えば後述する合成例１を参照することにより、類似の化合物を適用し、類似の方法で製造することができる。また一部の化合物は市販品として入手することも可能である。
【００２０】
本発明において使用する一般式［Ｉ］で表される化合物としては、具体的には以下のものが挙げられる。なお下記例示は本発明の金属錯体化合物を制限的に提示しているものでも、またこれらに限定する意図で開示しているものでもない。
【００２１】
【化３】
【化４】
【化５】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
【化１２】
【化１３】
図１〜図４に本発明による有機エレクトロルミネセンス素子を模式的に示した。図１中、（１）は陽極であり、その上に、正孔注入輸送層（２）と有機発光層（３）および陰極（４）が順次積層された構成をとっており、有機発光層（３）に上記一般式［Ｉ］で表される化合物を含有する。
【００３３】
図２において、（１）は陽極であり、その上に、正孔注入輸送層（２）と有機発光層（３）、電子注入輸送層（５）および陰極（４）が順次積層された構成をとっており、有機発光層（３）および／または電子注入輸送層（５）に上記一般式［Ｉ］で表される化合物を含有する。
【００３４】
図３において、（１）は陽極であり、その上に、有機発光層（３）と電子注入輸送層（５）および陰極（４）が順次積層された構成をとっており、電子注入輸送層（５）、または有機発光層（３）および電子注入輸送層（５）の両方に上記一般式［Ｉ］で表される化合物を含有する。
【００３５】
図４において、（１）は陽極であり、その上に、有機発光層（３）および陰極（４）が順次積層された構成をとっており、該有機発光層に有機発光材料（６）と電荷輸送材料（７）が含まれており、該有機発光材料または電荷輸送材料に上記一般式［Ｉ］で表される化合物を使用する。
【００３６】
上記各構成の有機エレクトロルミネセンス素子は陽極（１）と陰極（４）がリード線（８）により接続され、陽極（１）と陰極（４）に電圧を印加することにより有機発光層（３）が発光する。
【００３７】
有機発光層、正孔注入輸送層、電子注入輸送層には、必要があれば公知の発光物質、発光補助材料、キャリア輸送を行なう電荷輸送材料を使用することもできる。
【００３８】
有機エレクトロルミネセンス素子の陽極（１）として使用される導電性物質としては４ｅＶよりも大きい仕事関数を持つものがよく、炭素、アルミニウム、バナジウム、鉄、コバルト、ニッケル、銅、亜鉛、タングステン、銀、錫、金などおよびそれらの合金、酸化錫、酸化インジウム、酸化アンチモン、酸化亜鉛、酸化ジルコニウムなどの金属酸化物およびそれらの複合酸化物などの導電性金属化合物が用いられる。
【００３９】
陰極（４）を形成する金属としては４ｅＶよりも小さい仕事関数をもつものがよく、マグネシウム、カルシウム、チタニウム、イットリウム、リチウム、ガドリニウム、イッテルビウム、ルテニウム、マンガン、それらの合金、およびそれらと他の金属との合金などが用いられる。
陽極および陰極は、必要があれば二層以上の層構成により形成されていてもよい。
【００４０】
有機エレクトロルミネセンス素子においては発光が見られるように、少なくとも陽極（１）あるいは陰極（４）は透明電極にする必要がある。この際、いずれの電極にも透明電極を使用することは可能であるが、透明性をできるだけ高くしたい場合には、陽極を透明電極にすることが好ましい。
【００４１】
透明電極を形成する場合、透明基板上に、上記したような導電性物質を用い、蒸着、スパッタリング等の手段やゾル−ゲル法あるいは樹脂等に分散させて塗布する等の手段を用いて所望の透光性と導電性が確保されるように形成すればよい。
【００４２】
透明基板としては、適度の強度を有し、有機エレクトロルミネセンス素子作製時、蒸着等による熱に悪影響を受けず、透明なものであれば特に限定されないが、係るものを例示すると、ガラス基板、透明な樹脂、例えばポリエチレン、ポリプロピレン、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリエステル等を使用することも可能である。ガラス基板上に透明電極が形成されたものとしてはＩＴＯ、ＮＥＳＡ等の市販品が知られているがこれらを使用してもよい。
【００４３】
本発明の有機エレクトロルミネセンス素子の一例として正孔注入輸送層、有機発光層および電子注入輸送層を用いた場合（図２）を説明する。
まず、上記した陽極（１）上に正孔注入輸送層（２）を形成する。正孔注入輸送層（２）は、正孔輸送材料を蒸着して形成してもよいし、正孔輸送材料を溶解した溶液や適当な樹脂とともに溶解した液をディップコートやスピンコートして形成してもよい。蒸着法で形成する場合、その厚さは通常１〜５００ｎｍであり、塗布法で形成する場合は、５〜１０００ｎｍ程度に形成すればよい。形成する膜厚が厚いほど発光させるための印加電圧を高くする必要があり、発光効率が悪く有機エレクトロルミネセンス素子の劣化を招きやすい。また、膜厚が薄くなると発光効率は良くなるが、ブレイクダウンしやすくなり、有機エレクトロルミネセンス素子の寿命が短くなりやすい。
【００４４】
正孔注入輸送層に用いられる正孔輸送材料としては、公知のものが使用可能で、例えばＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−メチルフェニル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（１−ナフチル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（２−ナフチル）−１，１’−ジフェニル−４，４’−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’，−テトラ（４−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン、Ｎ，Ｎ’−ビス（Ｎ−カルバゾリル）−１，１’−ジフェニル−４，４’−ジアミン、４，４’，４”−トリス（Ｎ−カルバゾリル）トリフェニルアミン、Ｎ，Ｎ’，Ｎ”−トリフェニル−Ｎ，Ｎ’，Ｎ”−トリス（３−メチルフェニル）−１，３，５−トリ（４−アミノフェニル）ベンゼン、４，４’，４”−トリス〔Ｎ，Ｎ’，Ｎ”−トリフェニル−Ｎ，Ｎ’，Ｎ”−トリス（３−メチルフェニル）〕トリフェニルアミンなどを挙げることができる。これらのものは２種以上を混合して使用してもよい。
【００４５】
次に、正孔注入輸送層（２）の上に有機発光層（３）を形成する。有機発光層に上記一般式［Ｉ］で表される化合物を含有させる。あるいは、後述する電子注入輸送層（５）に上記一般式［Ｉ］で表される化合物が用いられる場合は、有機発光層（３）には必ずしもこれらの錯体化合物を含有しなくてよく、従来公知の有機発光材料を用いて有機発光層を形成してもよい。
有機発光層は上記一般式［Ｉ］で表される化合物の単層構成としてもよいし、発光の色、発光の強度等の特性を調整するために多層構成としてもよい。また、２種以上の発光物質を混合したり発光層にルブレンやピレンなどの発光材料をドープしてもよい。
【００４６】
有機発光層（３）は、上記一般式［Ｉ］で表される化合物を蒸着して形成してもよいし、該発光物質を溶解した溶液や適当な樹脂とともに溶解した液をディップコートやスピンコートして形成してもよい。蒸着法で形成する場合、その厚さは、通常１〜５００ｎｍであり、塗布法で形成する場合５〜１０００ｎｍ程度に形成すればよい。形成する膜厚が厚いほど発光させるための印加電圧を高くする必要があり、発光効率が悪くエレクトロルミネセンス素子の劣化を招きやすい。また、膜厚が薄くなると発光効率は良くなるがブレイクダウンしやすくなり電界発光素子の寿命が短くなりやすい。
【００４７】
有機発光層（３）の上に電子注入輸送層（５）を形成する。電子注入輸送層に使用される電子輸送材料としては、公知のものが使用可能で、例えば、２−（４−ビフェニルイル）−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキサジアゾール、２−（１−ナフチル）−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキサジアゾール、１，４−ビス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキサジアゾリル〕｝ベンゼン、１，３−ビス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキサジアゾリル〕｝ベンゼン、４，４’−ビス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキジアゾリル〕｝ビフェニル、２−（４−ビフェニルイル）−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−チアジアゾール、２−（１−ナフチル）−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−チアジアゾール、１，４−ビス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−チアジアゾリル〕｝ベンゼン、１，３−ビス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−チアジアゾリル〕｝ベンゼン、４，４’−ビス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−チアジアゾリル〕｝ビフェニル、２−（４−ビフェニルイル）−１−フェニル−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−トリアゾール、５−（１−ナフチル）−１−フェニル−２−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−トリアゾール、１，４−ビス｛２−〔１−フェニル−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−トリアゾリル〕｝ベンゼン、１，３−ビス｛２−〔１−フェニル−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−トリアゾリル〕｝ベンゼン、４，４’−ビス｛２−〔１−フェニル−５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−トリアゾリル〕｝ビフェニル、１，３，５−トリス｛２−〔５−（４−ｔｅｒｔ−ブチルフェニル）−１，３，４−オキサジアゾリル〕｝ベンゼンなどを挙げることができる。これらのものは、２種以上を混合して使用してもよいし、また、電子注入輸送層として本発明の金属錯体［Ｉ］を単独で用いてもよいし、他のものと混合してもよい。
【００４８】
電子注入輸送層（５）は電子注入輸送材料を蒸着して形成していもよいし、該電子注入輸送材料を溶解した溶液や適当な樹脂とともに溶解した液をディップコートやスピンコートして形成してもよい。蒸着法で形成する場合、その厚さは、通常１〜５００ｎｍであり、塗布法で形成する場合５〜１０００ｎｍ程度に形成すればよい。形成する膜厚が厚いほど発光させるための印加電圧を高くする必要があり、発光効率が悪く有機エレクトロルミネセンス素子の劣化を招きやすい。また、膜厚が薄くなると発光効率は良くなるがブレイクダウンしやすくなり電界発光素子の寿命が短くなりやすい。
【００４９】
次に、電子注入輸送層（５）の上に、前記した陰極（４）を形成し、有機エレクトロルミネセンス素子とする。
【００５０】
以上、陽極（１）上に正孔注入輸送層（２）、有機発光層（３）および、電子注入輸送層（５）、陰極（４）を順次積層して有機エレクトロルミネセンス素子を作製する場合について説明したが、陽極（１）上に有機発光層（３）、電子注入輸送層（５）および陰極（４）を順次積層したり（図３）、陰極（４）上に電子注入輸送層（５）、有機発光層（３）および陽極（１）を順次積層したり、陽極（１）上に正孔注入輸送層（２）、有機発光層（３）および、陰極（４）を順次積層したり（図１）、陰極（４）上に電子注入輸送層（５）、有機発光層（３）および正孔注入輸送層（２）、陽極（１）を順次積層したりしてももちろん構わない。いずれの場合も図２について説明したのと同様にして各層を順次形成すればよい。
【００５１】
また上記各構成において、正孔注入輸送層は、正孔注入機能と正孔輸送機能を分離して、正孔注入層と正孔輸送層の２層構成としても良いし、正孔注入層または正孔輸送層を単独で使用してもよい。電子注入輸送層も、電子注入機能と電子輸送機能を分離して、電子注入層と電子輸送層の２層構成としても良いし、電子注入層または電子輸送層を単独で使用してもよい。電子注入層、電子輸送層に一般式［Ｉ］で表される金属錯体化合物を使用することができる。
【００５２】
図４に示したような単層構成の有機発光層（３）を形成する場合、有機発光材料と電荷輸送材料とを共蒸着法により混合形成してもよいし、有機発光材料と電荷輸送材料とを溶解した溶液や適当な樹脂とともに溶解した液を用いてディップコートやスピンコートすることにより形成してもよい。電荷輸送材料としては上述した電子輸送材料または正孔輸送材料が用いられ、これらは混合して用いてもよいし、同じ輸送性の材料を２種以上混合して用いてもよい。蒸着法で有機発光層を形成する場合、その厚さは通常５〜２００ｎｍであり、塗布法で形成する場合、１０〜５００ｎｍ程度に形成すればよい。塗布法の場合、混合して使用する樹脂としては、ポリビニルカルバゾールやポリビニルアセチレンのような光導電性樹脂を用いると特に良好な特性を得ることができる。
【００５３】
陰極と陽極とにニクロム線、金線、銅線、白金線等の適当なリード線（８）を接続し、両電極間に適当な電圧（Ｖｓ）を印加することにより有機エレクトロルミネセンス素子は発光する。
【００５４】
本発明の有機エレクトロルミネセンス素子は、各種の表示装置、あるいはティスプレイ装置等に適用可能である。以下に実施例を記載し、本発明を説明する。
【００５５】
合成例１（化合物（１）の合成）
合成例１の反応式を下記する。
【化１４】
【００５６】
【００５７】
参考例１
インジウムスズ酸化物被覆ガラスの基板上に正孔注入輸送層としてＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン化合物を蒸着し、厚さ６０ｎｍの薄膜を形成した。
正孔注入輸送層の上に有機発光層として、化合物（１）を蒸着し、６０ｎｍの厚さになるように薄膜を形成した。
有機発光層の上に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着し、２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機エレクトロルミネセンス素子を作製した。
【００５８】
参考例２〜４
参考例１において、化合物（１）を使用する代わりに、化合物（７）、（４８）、化合物（６９）に代えること以外は参考例１と全く同様にして有機エレクトロルミネセンス素子を作製した。
【００５９】
実施例１
インジウムスズ酸化物被覆ガラスの基板上に正孔注入層として、４，４’，４”−トリス〔Ｎ，Ｎ’，Ｎ”−トリフェニル−Ｎ，Ｎ’，Ｎ”−トリス（３−メチルフェニル）〕トリフェニルアミンを蒸着し、厚さ１５ｎｍの薄膜を形成した。次に、正孔注入層の上に、正孔輸送層としてＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミンを蒸着し、厚さ４５ｎｍの薄膜を形成した。
その上に有機発光層として、化合物（６）にルブレンを５重量％ドープさせたものを共蒸着し、３０ｎｍの厚さになるよう薄膜を形成した。
【００６０】
有機発光層上に、電子注入輸送層として化合物（６）を蒸着し、３０ｎｍの厚さになるように薄膜を形成した。
電子注入輸送層上に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着し、２００ｎｍの厚さなるように薄膜を形成した。このようにして、有機エレクトロルミネセンス素子を作製した。
【００６１】
実施例２〜４
実施例１において、化合物（６）を使用する代わりに、化合物（２２）、（３１）、化合物（７８）に代えること以外は実施例１と全く同様にして有機エレクトロルミネセンス素子を作製した。
【００６２】
実施例５
インジウムスズ酸化物被覆ガラスの基板上に正孔注入輸送層として，Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（１−ナフチル）−１，１’−ジフェニル−４，４’−ジアミン化合物を蒸着し、厚さ５５ｎｍの薄膜を形成した。
正孔注入輸送層の上に、有機発光層として、化合物（２１）にルブレンを５重量％ドープしたものを共蒸着し、２０ｎｍの厚さになるように薄膜を形成した。
【００６３】
有機発光層の上に、電子注入輸送層として化合物（２１）を蒸着し、４０ｎｍの厚さになるように薄膜を形成した。
電子注入輸送層の上に、陰極として１０：１の原子比のＭｇおよびＡｇを蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機エレクトロルミネセンス素子を作製した。
【００６４】
実施例６〜８
実施例５において、化合物（２１）使用する代わりに、化合物（３６）、（４９）、（８１）に代えること以外は実施例５と全く同様にして有機エレクトロルミネセンス素子を作製した。
【００６５】
比較例１
インジウムスズ酸化物被覆ガラスの基板上に正孔注入輸送層としてＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−メチルフェニル）−１，１’−ビス（３−メチルフェニル）−４，４’−ジアミン化合物を蒸着し、厚さ６０ｎｍの薄膜を形成した。
正孔注入輸送層の上に有機発光層として、下記構造式の化合物（Ａ）を蒸着し、６０ｎｍの厚さなるように薄膜を形成した。
有機発光層の上に陰極として１０：１の原子比のＭｇおよびＡｇを蒸着により２００ｎｍの厚さになるように薄膜を形成した。このようにして、有機エレクトロルミネセンス素子を作製した。
【化１５】
評価
参考例１〜４、実施例１〜８および比較例１で得られた有機エレクトロルミネセンス素子を、そのガラス基板上の透明電極を陽極として、直流電圧を徐々に印加したときに発光を開始する電圧および、最高発光輝度とその時の電圧を測定した。結果を表１に示す。
また、参考例１で得られた素子を、窒素ガス不活性雰囲気下で初期５ｍＡ／ｃｍ2で連続発光させて、その発光輝度の半減期（輝度が半分になるまでの時間）を測定したところ３００時間であった。
【００６７】
【表１】
表１からわかるように、本発明の有機エレクトロルミネセンス素子は低電圧で発光を開始し、良好な発光輝度を示した。また、本発明の有機エレクトロルミネセンス素子は出力低下が少なく、寿命の長い安定した発光を観測することができた。
本発明の有機エレクトロルミネセンス素子は発光効率、発光輝度の向上と長寿命化を達成するものであり、併せて使用される発光物質、発光補助材料、電荷輸送材料、樹脂、電極材料等および素子作製方法に限定されるものではない。
【００６９】
【発明の効果】
本発明により、有機エレクトロルミネセンス素子に特定の金属錯体を含有させることにより、発光輝度が大きく発光開始電圧が低い、耐久性に優れた有機エレクトロルミネセンス素子を得ることができる。
【図面の簡単な説明】
【図１】 有機エレクトロルミネセンス素子の一構成例の概略構成図。
【図２】 有機エレクトロルミネセンス素子の一構成例の概略構成図。
【図３】 有機エレクトロルミネセンス素子の一構成例の概略構成図。
【図４】 有機エレクトロルミネセンス素子の一構成例の概略構成図。
【符号の説明】
１：陽極
２：正孔注入輸送層
３：有機発光層
４：陰極
５：電子注入輸送層
６：有機発光材料
７：電荷輸送材料
８：リード線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic electroluminescence device comprising a light emitting layer or a plurality of organic compound thin layers including a light emitting layer between a pair of electrodes.
[0002]
[Prior art]
In recent years, with the diversification of information equipment, there is an increasing need for a flat display element that consumes less power than a cathode ray tube (CRT). As such flat display elements, there are liquid crystal, plasma display (PDP) and the like. Recently, self-luminous type electroluminescent elements with a clear display and a wide viewing angle are attracting attention. Here, the electroluminescent element can be roughly classified into an inorganic electroluminescent element and an organic electroluminescent element depending on a material constituting the inorganic electroluminescent element, and the inorganic electroluminescent element has already been put into practical use and is commercially available as a commercial product.
[0003]
However, since the inorganic electroluminescent element is so-called collision-type excitation light emission in which electrons accelerated by application of a high electric field collide with a light emission center to emit light, it is necessary to be driven at a high voltage of 100 V or more. is there. For this reason, there has been a problem of incurring higher costs for peripheral devices. There is also a problem that full color display cannot be performed because there is no illuminant that emits blue light.
[0004]
On the other hand, in organic electroluminescence devices, charges (holes and electrons) injected from the electrodes recombine in the luminescent material to generate excitons, which excite molecules of the luminescent material to emit light. Since it is so-called injection type light emission, it can be driven at a low voltage. And since it is an organic compound, the molecular structure of a luminescent material can be changed easily and arbitrary luminescent colors can be obtained. Therefore, the organic electroluminescence element is very promising as a display element in the future.
[0005]
Here, an organic electroluminescence device having two layers of a hole transport layer and an electron transport layer was proposed by Tang and VanSlyke (CWTang and SAVanSlyke; Appl. Phys. Lett., 51 (1987). 913). The structure of the element was an electrode, a hole transport layer, an electron transporting light emitting layer, and a cathode formed on a glass substrate.
[0006]
In the above element, the hole transport layer functions to inject holes from the anode to the electron transporting light emitting layer, and prevents electrons injected from the cathode from escaping to the anode without recombining with the holes. It plays the role of containing electrons in the transporting light-emitting layer. For this reason, due to the electron confinement effect by the hole transport layer, recombination of electrons and holes occurs more efficiently than the conventional single layer structure device, and the driving voltage can be greatly reduced.
[0007]
Saito et al. Also showed that not only the electron transport layer but also the hole transport layer can be a light-emitting layer in a two-layer device (C. Adachi, T. Tsutsui and S. Saito; Appl. Phys. Lett., 55 (1989) 1489).
[0008]
Saito et al. Proposed a three-layer organic electroluminescent device in which an organic light-emitting layer is sandwiched between a hole-transporting layer and an electron-transporting layer (C. Adachi, S. Tokito, T. Tsutsui and S. Saito; Jpn. J. Appl. Phys., 27 (1988) L269). This consists of an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode formed on a glass substrate. The hole transport layer functions to contain electrons in the light emitting layer, and the electron transport layer contains holes. Luminous efficiency is further improved because it functions to be contained in the light emitting layer.
[0009]
[Problems to be solved by the invention]
As described above, in order to improve the light emission efficiency of the organic electroluminescence element, the layer structure has been improved. However, it is still necessary to increase the luminance and the efficiency of the light emission. In addition, in order to cause the organic electroluminescence element to emit light for a long time, it is necessary to emit light at a lower voltage and a lower current density.
[0010]
Therefore, in view of the above-described points, an object of the present invention is to provide an organic electroluminescence device that stably exhibits light emission with high luminance and high efficiency for a long period of time.
[0011]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies to solve the above problems, and have found that the characteristics of the organic electroluminescence element can be improved by using a specific metal complex, and have reached the present invention. That is, the present invention provides at least an organic electroluminescent device comprising a light emitting layer or a plurality of organic compound thin layers including a light emitting layer between a pair of electrodes.twoAn organic electroluminescent device characterized in that the layer contains a metal complex represented by the following chemical formula [I];
[Chemical formula 2]
In the above formula, X represents an oxygen atom, a sulfur atom or a nitrogen atom having a substituent. Examples of the substituent bonded to the nitrogen atom include a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as phenyl, or an aralkyl group such as benzyl group. Preferably they are a hydrogen atom, an alkyl group, and an aryl group. Particularly preferred is an alkyl group, particularly a methyl group.
[0013]
R1~ R6Are independently a hydrogen atom, a halogen atom such as a chlorine atom or a fluorine atom, a halogenated alkyl group such as a chloromethyl group, an alkyl group such as a methyl group or an ethyl group, an aralkyl group such as a benzyl group, a cyano group, a substituent Alternatively, it represents an unsubstituted aromatic hydrocarbon group such as a phenyl group or a substituted or unsubstituted aromatic heterocyclic group such as a thienyl group or a pyrrolyl group. The substituent which may be bonded to the aromatic hydrocarbon group or the aromatic heterocyclic group is an alkyl group such as a methyl group or an ethyl group, or a halogen atom such as a chlorine atom. RThreeAnd RFour, RFourAnd RFiveOr RFiveAnd R6Each may form an aromatic ring, a benzene ring, a naphthalene ring or the like, or a heterocyclic ring, a furan ring, a thiophene ring, an indole ring, or the like between substituents.
[0014]
R1And R2A preferable group is an aryl group, an aryl group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, particularly a phenyl group, a tolyl group, a chlorophenyl group or a thienyl group. , RThree~ R6A preferable group is a hydrogen atom.
[0015]
M represents a metal atom such as zinc (Zn), aluminum (Al), gallium (Ga), magnesium (Mg), or zirconium (Zr). Preferably, zinc, magnesium, and zirconium are represented.
[0016]
L represents a ligand coordinated to the metal atom M or an oxygen atom bonded to the metal atom M by a double bond. Examples of the ligand include a halogen atom or a hydrogen atom bonded to an oxygen atom and coordinated to the metal atom M through the oxygen atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, or a naphthyl group. Group, diphenyl group, phenoxyphenyl group and the like, heterocyclic group such as quinoline ring group, aralkyl group such as benzyl group, carbonyl group such as alkylcarbonyl group such as methylcarbonyl group or ethylcarbonyl group, phenylcarbonyl group And arylcarbonyl groups such as naphthylcarbonyl group, and heteroarylcarbonyl groups such as thienylcarbonyl group and pyridylcarbonyl group. When L represents an oxygen atom bonded to the metal atom M by a double bond, two L represent one oxygen atom.
[0017]
m represents an integer of 0 to 2, k represents an integer of 1 or 2, and n represents an integer of 1 to 3. m and n are respectively determined in relation to the valence of the metal atom M and the value of k. For example, when M is zinc or magnesium and k = 1, n is 1 or 2. When n = 2, m = 0 and the ligand L is not present. When M is gallium and k = 1, n can take an integer of 1 to 3. At this time, if n = 3, m = 0, indicating that no ligand L is present. When M is zirconium and k = 1, n is 1 or 2. When n = 2, m = 0 and no ligand L is present, or zirconium has an oxygen atom via a double bond (that is,> Zr = 0). Two metal atoms M may be included. In this case, k = 2. For example, when zinc or magnesium is used, values such as n = 3 and m = 1 may be taken.
[0018]
The specific metal complex compound represented by the general formula [I] is a good blue to yellow light emitter. In addition, since the specific metal complex compound represented by the general formula [I] has a good electron transport property, it can be used as an electron transport material such as an electron transport layer, an electron injection transport layer, and an electron injection layer as an electron transport material. Can be contained.
[0019]
The compound included in the general formula [I] can be produced in a similar manner by applying a similar compound by referring to, for example, Synthesis Example 1 described later. Some compounds can also be obtained as commercial products.
[0020]
Specific examples of the compound represented by the general formula [I] used in the present invention include the following. In addition, the following exemplification does not present the metal complex compound of the present invention in a restrictive manner, nor is it disclosed with the intention of limiting to these.
[0021]
[Chemical Formula 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
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1 to 4 schematically show an organic electroluminescent device according to the present invention. In FIG. 1, (1) is an anode, on which a hole injection transport layer (2), an organic light emitting layer (3), and a cathode (4) are sequentially laminated. (3) contains a compound represented by the above general formula [I].
[0033]
In FIG. 2, (1) is an anode, on which a hole injecting and transporting layer (2), an organic light emitting layer (3), an electron injecting and transporting layer (5) and a cathode (4) are sequentially laminated. The organic light emitting layer (3) and / or the electron injecting and transporting layer (5) contains the compound represented by the above general formula [I].
[0034]
In FIG. 3, (1) is an anode, on which an organic light emitting layer (3), an electron injection transport layer (5), and a cathode (4) are sequentially laminated. (5) or both the organic light emitting layer (3) and the electron injecting and transporting layer (5) contain the compound represented by the above general formula [I].
[0035]
In FIG. 4, (1) is an anode, and an organic light emitting layer (3) and a cathode (4) are sequentially laminated thereon, and the organic light emitting material (6) and The charge transport material (7) is contained, and the compound represented by the above general formula [I] is used for the organic light emitting material or the charge transport material.
[0036]
In the organic electroluminescent element having the above-described configuration, the anode (1) and the cathode (4) are connected by the lead wire (8), and a voltage is applied to the anode (1) and the cathode (4), whereby the organic light emitting layer (3 ) Emits light.
[0037]
For the organic light emitting layer, the hole injecting and transporting layer, and the electron injecting and transporting layer, a known light emitting substance, a light emitting auxiliary material, and a charge transporting material for carrying carriers can be used if necessary.
[0038]
As the conductive material used as the anode (1) of the organic electroluminescence element, those having a work function larger than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc, tungsten, silver In addition, conductive metal compounds such as metal oxides such as tin, gold and alloys thereof, tin oxide, indium oxide, antimony oxide, zinc oxide and zirconium oxide, and composite oxides thereof are used.
[0039]
The metal forming the cathode (4) is preferably one having a work function smaller than 4 eV, such as magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, alloys thereof, and other metals. And an alloy thereof are used.
If necessary, the anode and the cathode may be formed of two or more layers.
[0040]
In the organic electroluminescence element, at least the anode (1) or the cathode (4) needs to be a transparent electrode so that light emission can be seen. At this time, it is possible to use a transparent electrode for any of the electrodes. However, when it is desired to make the transparency as high as possible, the anode is preferably a transparent electrode.
[0041]
When forming a transparent electrode, a conductive material such as that described above is used on a transparent substrate, and a desired method using a means such as vapor deposition, sputtering, or a sol-gel method or a method such as coating by dispersing in a resin or the like. What is necessary is just to form so that translucency and electroconductivity may be ensured.
[0042]
The transparent substrate has an appropriate strength, and is not particularly limited as long as it is transparent as long as it is transparent without being adversely affected by heat due to vapor deposition or the like during the production of an organic electroluminescent element. Transparent resins such as polyethylene, polypropylene, polyethersulfone, polyetheretherketone, and polyester can also be used. Commercial products such as ITO and NESA are known as transparent electrodes formed on a glass substrate, but these may be used.
[0043]
The case where a hole injection transport layer, an organic light emitting layer, and an electron injection transport layer are used as an example of the organic electroluminescence device of the present invention (FIG. 2) will be described.
First, a hole injection transport layer (2) is formed on the anode (1) described above. The hole injecting and transporting layer (2) may be formed by depositing a hole transporting material, or by dip coating or spin coating a solution in which the hole transporting material is dissolved or a solution in which an appropriate resin is dissolved. May be. When forming by a vapor deposition method, the thickness is 1-500 nm normally, and when forming by the apply | coating method, what is necessary is just to form to about 5-1000 nm. The thicker the film is formed, the higher the applied voltage for causing light emission, and the lower the light emission efficiency, the more likely the deterioration of the organic electroluminescent element. Further, when the film thickness is reduced, the light emission efficiency is improved, but breakdown is likely to occur, and the life of the organic electroluminescence element is likely to be shortened.
[0044]
As the hole transporting material used for the hole injecting and transporting layer, known materials can be used, for example, N, N′-diphenyl-N, N′-bis (4-methylphenyl) -1,1′-bis. (3-Methylphenyl) -4,4′-diamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-bis (3-methylphenyl) -4,4 '-Diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-diphenyl-4,4'-diamine, N, N'-diphenyl-N, N'- Bis (4-methylphenyl) -1,1′-diphenyl-4,4′-diamine, N, N′-diphenyl-N, N′-bis (1-naphthyl) -1,1′-diphenyl-4, 4'-diamine, N, N'-diphenyl-N, N'-bis (2-naphthyl) 1,1′-diphenyl-4,4′-diamine, N, N, N ′, N ′,-tetra (4-methylphenyl) -1,1′-bis (3-methylphenyl) -4,4 ′ -Diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-bis (3-methylphenyl) -4,4'-diamine, N, N'-bis ( N-carbazolyl) -1,1′-diphenyl-4,4′-diamine, 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, N, N ′, N ″ -triphenyl-N, N ′, N ″ -tris (3-methylphenyl) -1,3,5-tri (4-aminophenyl) benzene, 4,4 ′, 4 ″ -tris [N, N ′, N ″ -triphenyl- N, N ′, N ″ -tris (3-methylphenyl)] triphenylamine Door can be. These may be used as a mixture of two or more.
[0045]
Next, an organic light emitting layer (3) is formed on the hole injection transport layer (2). The organic light emitting layer contains the compound represented by the above general formula [I]. Alternatively, when the compound represented by the above general formula [I] is used for the electron injecting and transporting layer (5) described later, the organic light emitting layer (3) does not necessarily contain these complex compounds. The organic light emitting layer may be formed using a known organic light emitting material.
The organic light emitting layer may have a single layer structure of the compound represented by the above general formula [I], or may have a multilayer structure in order to adjust characteristics such as light emission color and light emission intensity. Further, two or more kinds of light emitting substances may be mixed, or the light emitting layer may be doped with a light emitting material such as rubrene or pyrene.
[0046]
The organic light emitting layer (3) may be formed by vapor-depositing the compound represented by the above general formula [I], or a solution in which the light emitting material is dissolved or a solution in which the light emitting material is dissolved together with an appropriate resin is dip-coated or spin-coated. It may be formed by coating. When forming by a vapor deposition method, the thickness is 1-500 nm normally, and when forming by the apply | coating method, what is necessary is just to form to about 5-1000 nm. The thicker the film is formed, the higher the applied voltage for causing light emission, and the lower the light emission efficiency, the more likely the deterioration of the electroluminescent element. Further, when the film thickness is reduced, the light emission efficiency is improved, but breakdown is likely to occur and the life of the electroluminescent element is likely to be shortened.
[0047]
An electron injecting and transporting layer (5) is formed on the organic light emitting layer (3). As the electron transporting material used for the electron injecting and transporting layer, known materials can be used. For example, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4- Oxadiazole, 2- (1-naphthyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, 1,4-bis {2- [5- (4-tert-butyl) Phenyl) -1,3,4-oxadiazolyl]} benzene, 1,3-bis {2- [5- (4-tert-butylphenyl) -1,3,4-oxadiazolyl]} benzene, 4,4′- Bis {2- [5- (4-tert-butylphenyl) -1,3,4-oxydiazolyl]} biphenyl, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3 , 4-thiadiazole, 2- 1-naphthyl) -5- (4-tert-butylphenyl) -1,3,4-thiadiazole, 1,4-bis {2- [5- (4-tert-butylphenyl) -1,3,4- Thiadiazolyl]} benzene, 1,3-bis {2- [5- (4-tert-butylphenyl) -1,3,4-thiadiazolyl]} benzene, 4,4′-bis {2- [5- (4 -Tert-butylphenyl) -1,3,4-thiadiazolyl]} biphenyl, 2- (4-biphenylyl) -1-phenyl-5- (4-tert-butylphenyl) -1,3,4-triazole, 5- (1-naphthyl) -1-phenyl-2- (4-tert-butylphenyl) -1,3,4-triazole, 1,4-bis {2- [1-phenyl-5- (4-tert -Butylphenyl) -1,3 4-triazolyl]} benzene, 1,3-bis {2- [1-phenyl-5- (4-tert-butylphenyl) -1,3,4-triazolyl]} benzene, 4,4′-bis {2 -[1-phenyl-5- (4-tert-butylphenyl) -1,3,4-triazolyl]} biphenyl, 1,3,5-tris {2- [5- (4-tert-butylphenyl)- 1,3,4-oxadiazolyl]} benzene and the like. These may be used as a mixture of two or more, or the metal complex [I] of the present invention may be used alone as an electron injecting and transporting layer, or may be mixed with other materials. Also good.
[0048]
The electron injecting and transporting layer (5) may be formed by evaporating an electron injecting and transporting material, or formed by dip coating or spin coating a solution in which the electron injecting and transporting material is dissolved or an appropriate resin. May be. When forming by a vapor deposition method, the thickness is 1-500 nm normally, and when forming by the apply | coating method, what is necessary is just to form to about 5-1000 nm. The thicker the film is formed, the higher the applied voltage for causing light emission, and the lower the light emission efficiency, the more likely the deterioration of the organic electroluminescent element. Further, when the film thickness is reduced, the light emission efficiency is improved, but breakdown is likely to occur and the life of the electroluminescent element is likely to be shortened.
[0049]
Next, the above-described cathode (4) is formed on the electron injecting and transporting layer (5) to obtain an organic electroluminescence element.
[0050]
As described above, the hole injecting and transporting layer (2), the organic light emitting layer (3), the electron injecting and transporting layer (5), and the cathode (4) are sequentially laminated on the anode (1) to produce an organic electroluminescence device. As described above, the organic light emitting layer (3), the electron injection transport layer (5) and the cathode (4) are sequentially laminated on the anode (1) (FIG. 3), or the electron injection transport is performed on the cathode (4). The layer (5), the organic light emitting layer (3) and the anode (1) are sequentially laminated, or the hole injection / transport layer (2), the organic light emitting layer (3) and the cathode (4) are formed on the anode (1). The electron injecting and transporting layer (5), the organic light emitting layer (3), the hole injecting and transporting layer (2), and the anode (1) are sequentially laminated on the cathode (4). Of course. In any case, the layers may be formed in the same manner as described with reference to FIG.
[0051]
In each of the above configurations, the hole injection transport layer may have a two-layer configuration of a hole injection layer and a hole transport layer by separating the hole injection function and the hole transport function, The hole transport layer may be used alone. The electron injection / transport layer may have a two-layer structure of an electron injection layer and an electron transport layer by separating the electron injection function and the electron transport function, or the electron injection layer or the electron transport layer may be used alone. The metal complex compound represented by the general formula [I] can be used for the electron injection layer and the electron transport layer.
[0052]
When the organic light emitting layer (3) having a single layer structure as shown in FIG. 4 is formed, the organic light emitting material and the charge transport material may be mixed and formed by a co-evaporation method, or the organic light emitting material and the charge transport material may be formed. May be formed by dip-coating or spin-coating using a solution obtained by dissolving the above and a solution dissolved together with an appropriate resin. As the charge transport material, the above-described electron transport material or hole transport material may be used, and these may be used as a mixture, or two or more of the same transport materials may be used as a mixture. When the organic light emitting layer is formed by a vapor deposition method, the thickness is usually 5 to 200 nm. In the case of the coating method, particularly good characteristics can be obtained when a photoconductive resin such as polyvinyl carbazole or polyvinyl acetylene is used as the resin to be mixed.
[0053]
By connecting an appropriate lead wire (8) such as a nichrome wire, a gold wire, a copper wire, or a platinum wire to the cathode and the anode, and applying an appropriate voltage (Vs) between the two electrodes, the organic electroluminescent device is Emits light.
[0054]
The organic electroluminescence element of the present invention can be applied to various display devices, display devices, and the like. The following examples describe the invention.
[0055]
Synthesis Example 1 (Synthesis of Compound (1))
The reaction formula of Synthesis Example 1 is shown below.
Embedded image
[0056]
[0057]
Reference example 1
N, N′-diphenyl-N, N′-bis (4-methylphenyl) -1,1′-bis (3-methylphenyl) -4 as a hole injection transport layer on a substrate of indium tin oxide-coated glass , 4′-diamine compound was deposited to form a thin film having a thickness of 60 nm.
Compound (1) was deposited as an organic light emitting layer on the hole injecting and transporting layer to form a thin film having a thickness of 60 nm.
On the organic light emitting layer, Mg and Ag with an atomic ratio of 10: 1 were deposited as a cathode to form a thin film having a thickness of 200 nm. In this way, an organic electroluminescence element was produced.
[0058]
Reference example2-4
Reference example1 except that compound (1) is used in place of compound (7), (48) and compound (69).Reference exampleIn the same manner as in No. 1, an organic electroluminescence element was produced.
[0059]
Example1
4,4 ′, 4 ″ -tris [N, N ′, N ″ -triphenyl-N, N ′, N ″ -tris (3-methyl) as a hole injection layer on a substrate of indium tin oxide-coated glass Phenyl)] triphenylamine was deposited to form a thin film having a thickness of 15 nm, and then N, N′-diphenyl-N, N′-bis (3 -Methylphenyl) -1,1'-bis (3-methylphenyl) -4,4'-diamine was evaporated to form a thin film having a thickness of 45 nm.
On top of that, as an organic light emitting layer, a compound (6) doped with 5% by weight of rubrene was co-evaporated to form a thin film having a thickness of 30 nm.
[0060]
On the organic light emitting layer, the compound (6) was deposited as an electron injecting and transporting layer, and a thin film was formed to a thickness of 30 nm.
On the electron injecting and transporting layer, Mg and Ag having an atomic ratio of 10: 1 were deposited as a cathode to form a thin film having a thickness of 200 nm. In this way, an organic electroluminescence element was produced.
[0061]
Example2-4
Example1In Example 1, except that instead of using the compound (6), the compound (22), (31) and the compound (78) are used.1An organic electroluminescence element was produced in exactly the same manner as described above.
[0062]
Example5
N, N′-diphenyl-N, N′-bis (1-naphthyl) -1,1′-diphenyl-4,4′-diamine compound as a hole injection transport layer on a substrate of indium tin oxide-coated glass Was deposited to form a thin film having a thickness of 55 nm.
On the hole injecting and transporting layer, as the organic light emitting layer, a compound (21) doped with 5% by weight of rubrene was co-evaporated to form a thin film having a thickness of 20 nm.
[0063]
On the organic light emitting layer, the compound (21) was deposited as an electron injecting and transporting layer, and a thin film was formed to a thickness of 40 nm.
A thin film was formed on the electron injecting and transporting layer by vapor deposition of Mg and Ag having an atomic ratio of 10: 1 as a cathode to a thickness of 200 nm. In this way, an organic electroluminescence element was produced.
[0064]
Example6-8
Example5In Example 1, except that instead of using the compound (21), the compounds (36), (49) and (81) are used instead.5An organic electroluminescence element was produced in exactly the same manner as described above.
[0065]
Comparative Example 1
N, N′-diphenyl-N, N′-bis (4-methylphenyl) -1,1′-bis (3-methylphenyl) -4 as a hole injection transport layer on a substrate of indium tin oxide-coated glass , 4′-diamine compound was deposited to form a thin film having a thickness of 60 nm.
A compound (A) having the following structural formula was deposited as an organic light emitting layer on the hole injecting and transporting layer to form a thin film having a thickness of 60 nm.
A thin film having a thickness of 200 nm was formed on the organic light-emitting layer by vapor deposition of Mg and Ag having an atomic ratio of 10: 1 as a cathode. In this way, an organic electroluminescence element was produced.
Embedded image
Evaluation
Reference Examples 1-4,Example 18And the organic electroluminescent element obtained in Comparative Example 1 was used, with the transparent electrode on the glass substrate as the anode, the voltage at which light emission starts when a DC voltage is gradually applied, and the maximum light emission luminance and the voltage at that time. It was measured. The results are shown in Table 1.
Also,Reference exampleThe device obtained in 1 was initially 5 mA / cm under an inert atmosphere of nitrogen gas.2When the half-life of the emission luminance (the time until the luminance is reduced to half) was measured, it was 300 hours.
[0067]
[Table 1]
As can be seen from Table 1, the organic electroluminescent device of the present invention started to emit light at a low voltage and exhibited good emission luminance. In addition, the organic electroluminescence device of the present invention was able to observe stable light emission having a long output and little decrease in output.
The organic electroluminescence device of the present invention achieves improvement in light emission efficiency, light emission luminance and long life, and a light emitting material, a light emission auxiliary material, a charge transport material, a resin, an electrode material, and the like used together. The manufacturing method is not limited.
[0069]
【The invention's effect】
According to the present invention, by including a specific metal complex in an organic electroluminescent element, an organic electroluminescent element having a high light emission luminance and a low light emission starting voltage and excellent in durability can be obtained.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a configuration example of an organic electroluminescence element.
FIG. 2 is a schematic configuration diagram of a configuration example of an organic electroluminescence element.
FIG. 3 is a schematic configuration diagram of a configuration example of an organic electroluminescence element.
FIG. 4 is a schematic configuration diagram of a configuration example of an organic electroluminescence element.
[Explanation of symbols]
1: Anode
2: Hole injection transport layer
3: Organic light emitting layer
4: Cathode
5: Electron injection transport layer
6: Organic light emitting material
7: Charge transport material
8: Lead wire
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| JP6009958B2 (en) * | 2013-02-05 | 2016-10-19 | 株式会社日本触媒 | Organometallic complex |
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