JP4321808B2 - 有機エレクトロルミネッセンス素子および表示用パネル - Google Patents
有機エレクトロルミネッセンス素子および表示用パネル Download PDFInfo
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- JP4321808B2 JP4321808B2 JP2003381737A JP2003381737A JP4321808B2 JP 4321808 B2 JP4321808 B2 JP 4321808B2 JP 2003381737 A JP2003381737 A JP 2003381737A JP 2003381737 A JP2003381737 A JP 2003381737A JP 4321808 B2 JP4321808 B2 JP 4321808B2
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- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
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Description
第3の発明は、前記発光材料が、燐光性のイリジウム化合物である上記第2の発明の有機EL素子に関する。
第4の発明は、前記発光層と陰極の間に電子輸送性化合物を含む層が設けられている上記第2または第3の発明の有機EL素子に関する。
第5の発明は、前記発光層と陽極の間に正孔輸送性化合物を含む層が設けられている上記第2または第3の発明の有機EL素子に関する。
第6の発明は、前記発光層と陰極の間に電子輸送性化合物を含む層と、前記発光層と陽極の間に正孔輸送性化合物を含む層が設けられている上記第2または第3の発明の有機EL素子に関する。
第7の発明は、上記第1〜6の発明の何れか1つの有機EL素子を備えていることを特徴とする表示用パネルに関する。
第2の発明によれば、第1の発明の材料に少なくとも1種の発光材料を分散含有させて発光層を形成することで、発光材料の変更により容易に発光色を変更できる有機EL素子を提供することができる。
第3の発明によれば、第2の発明の発光層が第2の発明の発光材料として燐光性のイリジウム化合物を含有することで三重項状態のエネルギーも利用することが可能であって高効率を達成し得る有機EL素子を提供することができる。
Rの例のうち、アルキル基を含む置換基においては、それらは直鎖、分岐または環状のいずれかまたはそれらの組合せであってもよく、直鎖でない場合、例えばイソアミル基、2−エチルヘキシル基、3,7−ジメチルオクチル基、シクロヘキシル基、4−C1〜C12アルキルシクロヘキシル基などが例示される。
で表わされる化合物(式中のAr、R2〜R5は前記定義の通りである)を合成する。該化合物の合成方法は公知の方法(例えば、特許文献1)に従ってよい。次に上記化合物に官能基、例えば、アミノ基、水酸基、メチロール基などのヒドロキシアルキル基、カルボキシル基、スルホニル基、エポキシ基、イソシアネート基などを導入する。次にこれらの官能基と反応する基を有するビニル化合物を用いて、前記化合物にビニル基を導入することにより前記一般式(1)で表わされる本発明の単量体が得られる。上記ビニル基を有する化合物としては、例えば、(メタ)アクリル酸、(メタ)アクリル酸アミド、(メタ)アクリル酸クロライド、(メタ)アクリル酸無水物、ヒドロキシアルキル(メタ)アクリレート、(メタ)アクリル酸グリシジルエーテルなどが挙げられる。この製造例は1例であり、本発明の単量体はその他の方法で製造したものであってもよい。
[本発明の重合体1の合成]
なお、合成例中において用いる測定機器および測定条件を以下に示す。
(1)1H−NMR;ブルッカー社製DRX−500型装置(500MHz)、内部標準物質;テトラメチルシラン、重クロロホルム中で測定
(2)IR;フーリエ変換赤外分光光度計FT/IR−610型装置(日本分光株式会社製)
(3)MASS;日立M−80B(株式会社日立製作所製)
(4)分子量;GPCにより測定(ShodexGPC(K806M)を2本連結)、クロロホルム溶媒でポリスチレンにて換算
1H NMR:1.98(s,3H) 5.40(s,2H) 5.57(s,1H) 7.29−7.36(m,3H) 7.41−7.54(m,8H) 7.67−7.72(m,4H) 7.89−7.93(m,4H) 8.15−8.23(m,4H)。
3,042cm-1芳香族C−H伸縮(CBPユニット由来)、2,946cm-1アルカンC−H伸縮(高分子主鎖由来)、1,726cm-1飽和脂肪族エステルC=O伸縮、1,503cm-1n芳香族C=C伸縮(CBPユニット由来)、1,200〜1,100cm-1飽和脂肪族エステルC−O伸縮、746cm-1多環芳香族C−H面外変角振動(CBPユニット由来)、722cm-1多環芳香族C−H面外変角振動(CBPユニット由来)。ポリスチレン換算の数平均分子量は約10,000であった。
200mlコルベンに窒素気流下、前記本発明の単量体Aを3.2g(5.5mmol)、スチレンを0.5g(4.8mmol)、トルエンを80ml仕込んだ。温水浴にて80℃まで加熱し、アゾビスイソブチロニトリル0.15g(0.9mmol)を投入した。5時間攪拌し重合反応させた。反応終了後放冷し、その反応液をアセトン中に滴下した。析出した沈殿物をろ別し、アセトンにより洗浄し、下記式で表わされる重合体を2.0g得た。得られた重合体を重合体2と呼ぶ。
3,100〜3,000cm-1芳香族C−H伸縮(CBPユニット、スチレンユニット由来)、2,922cm-1アルカンC−H伸縮(高分子主鎖由来)、1,725cm-1飽和脂肪族エステルC=O伸縮、1,503cm-1芳香族C=C伸縮(CBPユニット、スチレンユニット由来)、1,200〜1,100cm-1飽和脂肪族エステルC−O伸縮、746cm-1多環芳香族C−H面外変角振動(CBPユニット由来)、723cm-1多環芳香族C-H面外変角振動(CBPユニット由来)、699cm-1単環芳香族C−H面外変角振動(スチレンユニット由来)。ポリスチレン換算の数平均分子量は約7,000であった。
重合体1はクロロホルム、1,2−ジクロロエタン、テトラヒドロフランに1質量%以上で可溶であった。重合体2はトルエン、クロロホルム、1,2−ジクロロエタン、テトラヒドロフランに1質量%以上で可溶であった。また、重合体1および2は、前記のいずれの溶媒からも、ドーピングやバインダー混入を施すことなく、スピンコートによりガラス基板上に均一な薄膜を形成することが可能であった。
上記で得られた重合体1および2の薄膜、および比較参照物としてのCBPの薄膜について、仕事関数および電子親和力を測定した。なお、CBPの薄膜は真空蒸着方法により成膜した。仕事関数は理研計器製の大気中紫外線光電子分析装置AC−1を用いて求めた。電子親和力は上記の方法を用いて求めた仕事関数値と、島津製作所製の紫外可視吸収スペクトル測定装置MPC−3100を用いて測定した吸収スペクトルの長波長側最末端値から算出したバンドギャップ値から算出した。
[有機EL素子の作製]
ガラス基板上にITOの透明導電性膜が成膜された基板を所望の形状にパターニングした後、洗浄およびUV/オゾン処理を施した。次いで、ポリ−3,4−エチレンジオキシチオフェン/ポリスチレンスルフォネート水分散液(略称PEDOT/PSS、商品名Baytron TP CH8000、バイエル社)を洗浄基板上に滴下し、スピンコートした。その後200℃のホットプレート上で15分加熱乾燥することにより、80nmの正孔輸送層を形成した。
・重合体1 19重量部
・Ir(ppy)3 1重量部
・テトラヒドロフラン 1313重量部
この素子の輝度はトプコン社製輝度計BM−8を用いて測定した。また、発光スペクトルはトプコン社製分光放射計SR−2を用いて測定した。発光スペクトルを図5に示す。この素子は印加電圧9Vで発光開始して、20Vで約100cd/m2の輝度で発光した。最高発光効率は約7.5cd/Aに達した。
[有機EL素子の作製]
実施例1における重合体1に代えて重合体2を用い、他は実施例1と同様にして、実施例1と同様の発光特性を有する本発明の有機EL素子を得た。この素子は印加電圧8Vで発光を開始して、20Vで約1000cd/m2の輝度で発光した。最高発光効率は約10cd/Aに達した。
また、本発明に係る表示用パネルは、本発明に係る高発光効率な有機EL素子を備えるため、高発光効率な表示用パネルである。
Claims (7)
- 前記式で表わされる単量体単位を少なくとも1個含む重合体を少なくとも1種含有する層が、少なくとも1種の発光材料を分散含有する発光層である請求項1に記載の有機エレクトロルミネッセンス素子。
- 前記発光材料が、燐光性のイリジウム化合物である請求項2に記載の有機エレクトロルミネッセンス素子。
- 前記発光層と陰極の間に電子輸送性化合物を含む層が設けられている請求項2または3に記載の有機エレクトロルミネッセンス素子。
- 前記発光層と陽極の間に正孔輸送性化合物を含む層が設けられている請求項2または3に記載の有機エレクトロルミネッセンス素子。
- 前記発光層と陰極の間に電子輸送性化合物を含む層と、前記発光層と陽極の間に正孔輸送性化合物を含む層が設けられている請求項2または3に記載の有機エレクトロルミネッセンス素子。
- 前記請求項1〜6のいずれか1項に記載の有機エレクトロルミネッセンス素子を備えていることを特徴とする表示用パネル。
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US10/984,355 US8084935B2 (en) | 2003-11-11 | 2004-11-09 | Organic electroluminescent element and display panel using said element |
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JP4994688B2 (ja) * | 2006-03-27 | 2012-08-08 | 昭和電工株式会社 | キャリア輸送性および燐光発光性を有する化合物を用いた有機発光素子 |
JP2011503286A (ja) * | 2007-11-06 | 2011-01-27 | エイチシーエフ パートナーズ リミテッド パートナーシップ | 電子装置における使用のためのホール輸送ポリマー |
CN102349171A (zh) * | 2009-03-09 | 2012-02-08 | 昭和电工株式会社 | 有机发光元件材料、以及有机发光元件和其制造方法 |
DE102009023154A1 (de) * | 2009-05-29 | 2011-06-16 | Merck Patent Gmbh | Zusammensetzung, enthaltend mindestens eine Emitterverbindung und mindestens ein Polymer mit konjugationsunterbrechenden Einheiten |
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JP5724731B2 (ja) * | 2011-08-01 | 2015-05-27 | 富士ゼロックス株式会社 | 有機電界発光素子及び表示媒体 |
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FR2757525B1 (fr) | 1996-12-24 | 1999-03-26 | Thomson Csf | Polymeres injecteurs de trous photopolymerisables et application en visualisation |
JP3447945B2 (ja) | 1998-02-26 | 2003-09-16 | 沖電気工業株式会社 | 発光材料およびこれを用いた有機el素子 |
JP4026740B2 (ja) * | 2000-09-29 | 2007-12-26 | 富士フイルム株式会社 | 有機発光素子材料及びそれを用いた有機発光素子 |
JP2002124389A (ja) | 2000-10-16 | 2002-04-26 | Jsr Corp | 有機エレクトロルミネッセンス素子 |
JP2002302516A (ja) | 2001-04-03 | 2002-10-18 | Fuji Photo Film Co Ltd | 新規ポリマーおよびそれを用いた発光素子 |
US7250226B2 (en) * | 2001-08-31 | 2007-07-31 | Nippon Hoso Kyokai | Phosphorescent compound, a phosphorescent composition and an organic light-emitting device |
JP4140323B2 (ja) * | 2001-09-19 | 2008-08-27 | 富士ゼロックス株式会社 | 有機電界発光素子 |
GB0204989D0 (en) * | 2002-03-04 | 2002-04-17 | Opsys Ltd | Phosphorescent compositions and organic light emitting devices containing them |
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JP4225043B2 (ja) * | 2002-12-03 | 2009-02-18 | コニカミノルタホールディングス株式会社 | 有機エレクトロルミネッセンス素子、その製造方法、表示装置、照明装置及び光源 |
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