JP2004311184A - Electron transportation material formed of multinucleate phenanthroline derivative, charge control material, and organic luminescent element using them - Google Patents
Electron transportation material formed of multinucleate phenanthroline derivative, charge control material, and organic luminescent element using them Download PDFInfo
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- JP2004311184A JP2004311184A JP2003102333A JP2003102333A JP2004311184A JP 2004311184 A JP2004311184 A JP 2004311184A JP 2003102333 A JP2003102333 A JP 2003102333A JP 2003102333 A JP2003102333 A JP 2003102333A JP 2004311184 A JP2004311184 A JP 2004311184A
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- 239000000463 material Substances 0.000 title claims abstract description 47
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 15
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 230000005525 hole transport Effects 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000891 luminescent agent Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
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- 238000010586 diagram Methods 0.000 description 9
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- 229910052792 caesium Inorganic materials 0.000 description 7
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- VQYDFPFSXHGHOD-UHFFFAOYSA-N 2-[4-(1,10-phenanthrolin-2-yl)phenyl]-1,10-phenanthroline Chemical compound C1=CN=C2C3=NC(C4=CC=C(C=C4)C4=CC=C5C=CC=6C(C5=N4)=NC=CC=6)=CC=C3C=CC2=C1 VQYDFPFSXHGHOD-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 6
- CGYVBVWBGRTQJQ-UHFFFAOYSA-N 8-nitroquinoline-7-carbaldehyde Chemical compound C1=CN=C2C([N+](=O)[O-])=C(C=O)C=CC2=C1 CGYVBVWBGRTQJQ-UHFFFAOYSA-N 0.000 description 5
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- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical group C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 4
- BBHFRDNLNCAAHR-UHFFFAOYSA-N 2-[4-[4-(1,10-phenanthrolin-2-yl)phenyl]phenyl]-1,10-phenanthroline Chemical group C1=CN=C2C3=NC(C4=CC=C(C=C4)C4=CC=C(C=C4)C4=CC=C5C=CC=6C(C5=N4)=NC=CC=6)=CC=C3C=CC2=C1 BBHFRDNLNCAAHR-UHFFFAOYSA-N 0.000 description 4
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- ZZDTVYJYMRSNQL-UHFFFAOYSA-N 7-methyl-8-nitroquinoline Chemical compound C1=CC=NC2=C([N+]([O-])=O)C(C)=CC=C21 ZZDTVYJYMRSNQL-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
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- 0 Cc1cc(-c2ccc(ccc3ccc(*)nc33)c3n2)c(C)cc1-c1nc(c2nc(*)ccc2cc2)c2cc1 Chemical compound Cc1cc(-c2ccc(ccc3ccc(*)nc33)c3n2)c(C)cc1-c1nc(c2nc(*)ccc2cc2)c2cc1 0.000 description 3
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
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- AOTNMHIQKKWTDE-UHFFFAOYSA-N 2-[5-(1,10-phenanthrolin-2-yl)anthracen-1-yl]-1,10-phenanthroline Chemical compound C1=CN=C2C3=NC(C4=C5C=C6C=CC=C(C6=CC5=CC=C4)C4=CC=C5C=CC=6C(C5=N4)=NC=CC=6)=CC=C3C=CC2=C1 AOTNMHIQKKWTDE-UHFFFAOYSA-N 0.000 description 2
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Images
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、フェナントロリン誘導体よりなる電子輸送材料、電荷制御材料およびそれを用いた有機発光素子に関する。
【０００２】
【従来技術】
従来、下記式、
【化７】
【０００３】
しかし、Ａｌｑ３は効率のよい電子輸送材料であるが、このものを使用すると本来緑色の発光材料であるから、緑色に発光する。しかし緑色より短い波長たとえば青色を取り出したい場合にはＡｌｑ３は使用することができない。そこで大きなバンドギャップをもつ下記式
【化８】
【化９】
【０００４】
特に、バソフェナントロリンは、電子の移動度が高いことが知られている（非特許文献１、特許文献３）。また、電子輸送材料にセシウム（Ｃｓ）をドーピングすることにより、低電圧化、高効率化が可能なことが、例えば山形大学、株式会社アイメス、松下電工株式会社から報告されている（非特許文献２、非特許文献３）。さらに、バソクプロインはリン光材料を利用した素子のホールブロック材料としても注目されている。そして、これらいずれの材料においても、エネルギーレベルのＨＯＭＯ（最高占有分子軌道）レベルが大きく、バンドギャップが大きいことが特徴である。
【０００５】
しかしながら、これらのいずれの材料も耐熱性が乏しく、これらの蒸着膜は再結晶化を起こしやすく、例えば一般的な保存温度範囲（−４０℃から８５℃）においてさえ、結晶化による素子特性の劣化が発生する。
【０００６】
【特許文献１】
特開２００１−２９７８８１号公報
【特許文献２】
特開２００１−３１３１７８号公報
【特許文献３】
特開平５−３３１４５９号公報
【非特許文献１】
Ｓｈｉｇｅｋｉ Ｎａｋａ ｅｔ ａｌ．，Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｌｅｔｔｅｒｓ，ｖｏｌ．７６，Ｎｏ．２，ｐ１９７−１９９
【非特許文献２】
Ｊｕｎｊｉ Ｋｉｄｏ ｅｔ ａｌ．，Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｌｅｔｔｅｒｓ，ｖｏｌ．７３，Ｎｏ．２０，ｐ２８６６−２８６８
【非特許文献３】
岸上他 高分子討論会 ｖｏｌ．４９，Ｎｏ．１１（２０００），ｐ３３８５−３３８６
【０００７】
【発明が解決しようとする課題】
本発明の目的は、Ａｌｑ３に優るとも劣らない電子輸送性能を示す新規な電子輸送材料および電荷制御材料ならびにそれを用いた有機発光素子を提供する点にある。
【０００８】
【課題を解決するための手段】
本発明の第１は、下記一般式（Ｉ）
【化１０】
Ｚ（Ｙ）ｎ ……（Ｉ）
〔式中、Ｚは２価または３価の芳香族炭化水素基、および２価または３価の複素環基よりなる群から選ばれた２価または３価の基であり、Ｙは
【化１１】
【化１２】
−ＸＡ
（ＸはＯ、Ｓ、ＳｅおよびＴｅよりなる群から選ばれた元素であり、Ａはアルキル基またはアリール基である）
よりなる群からそれぞれ独立して選ばれた基である。〕
で示される多核型フェナントロリン誘導体よりなることを特徴とする電子輸送材料に関する。
本発明の第２は、下記一般式（Ｉ）
【化１３】
Ｚ（Ｙ）ｎ ……（Ｉ）
〔式中、Ｚは２価または３価の芳香族炭化水素基、および２価または３価の複素環基よりなる群から選ばれた２価または３価の基であり、Ｙは
【化１４】
【化１５】
−ＸＡ
（ＸはＯ、Ｓ、ＳｅおよびＴｅよりなる群から選ばれた元素であり、Ａはアルキル基またはアリール基である）
よりなる群からそれぞれ独立して選ばれた基である。〕
で示される多核型フェナントロリン誘導体よりなることを特徴とする電荷制御材料に関する。
本発明の第３は、請求項１記載の電子輸送材料を含有する層および／または請求項２記載の電荷制御材料を含有する層を持つことを特徴とする有機発光素子に関する。
本発明の第４は、第１電極（陽極）、発光層、第２電極（陰極）を有する有機発光素子であって、発光層が少なくとも正孔輸送性発光剤と請求項１記載の電子輸送材料を含有するものであることを特徴とする有機発光素子に関する。
本発明の第５は、第１電極、発光層、電荷制御層、第２電極を有する有機発光素子であって、電荷制御層が請求項２記載の電荷制御材料を含有するものであることを特徴とする有機発光素子に関する。
本発明の第６は、第１電極、正孔輸送層、発光層、電荷制御層、第２電極を有する有機発光素子であって、電荷制御層が請求項２記載の電荷制御材料を含有するものであることを特徴とする有機発光素子に関する。
本発明の第７は、電荷制御層に隣接した（電荷制御層と第２電極の間）電子輸送層を有するものである請求項５または６記載の有機発光素子に関する。
本発明の第８は、正孔輸送層に隣接した（正孔輸送層と第１電極の間）正孔注入層を有するものである請求項６または７いずれか記載の有機発光素子に関する。
本発明の第９は、前記電荷制御層がアルカリ金属をドーピングしたものである請求項５〜８いずれか記載の有機発光素子に関する。
本発明の第１０は、前記発光層が
（Ａ）少なくとも正孔輸送性発光剤と請求項１記載の電子輸送材料とを含有する成分を分子分散させた層であるか、または、
（Ｂ）少なくとも正孔輸送性発光剤と請求項１記載の電子輸送材料とを含有する成分を分子分散させた層に発光剤をドープしてなる層である
請求項４〜９いずれか記載の有機発光素子に関する。
本発明の第１１は、第１電極が透明基板上にＩＴＯ薄膜を有するものである請求項４〜１０いずれか記載の有機発光素子に関する。
【０００９】
前記一般式（１）で示される化合物において、Ｚが２価の基であり、ｎ＝２の場合の化合物、すなわち２つのフェナントロリン基をもつフェナントロリン誘導体〔下記一般式（ＩＩ）の化合物〕は、下記の反応により製造することができる。なお、以下のＺおよびＲ１〜Ｒ５は請求項で定義したとおりである。
【化１６】
前記一般式（Ｉ）で示される化合物において、Ｚが３価の基であり、ｎ＝３の場合の化合物、すなわち３つのフェナントロリン基をもつフェナントロリン誘導体〔下記一般式（ＩＩＩ）の化合物〕は、下記の反応により製造することができる。
【化１７】
前記製造方法においては、反応溶媒を使用するが、反応溶媒としては一般にアルコールを使用することができ、好ましいアルコールとしては炭素数１〜６のもの、とくに好ましくは炭素数１〜４のものである。
反応補助剤としては、系をアルカリ性にするものを用いることができる。無機材料であれば炭酸や水酸化物などのアルカリ金属塩やアルカリ土類金属類、あるいはアルカリ金属やアルカリ土類金属の水酸塩などを挙げることができ、有機材料としては、アルカリ金属やアルカリ土類金属のアルコラートやアミン化合物を挙げることができる。
本反応は、好ましくは不活性雰囲気下、たとえば窒素、へリウム、ネオン、アルゴンなどの雰囲気下で行うことが好ましいが大気中であっても反応は進行する。
本反応温度は、とくに制限するものではないが、通常５０℃以上、好ましくは使用する溶媒の沸点温度またはその近傍である。反応時間は３〜４８時間、好ましくは１０〜４８時間、とくに好ましくは２０〜３６時間である。
【００１２】
前記Ｚは、２価または３価の芳香族炭化水素基あるいは２価または３価の複素環基であり、前記芳香族炭化水素基としては、芳香族単環基や芳香族多環基である場合のほか、下記（ａ）〜（ｃ）の組み合せからなる基が、−Ｏ−、−Ｓ−、飽和アルキレン、不飽和アルキレンあるいは結合手で結合していてもよい。（ａ）芳香族単環同士が結合している場合、（ｂ）芳香族単環と芳香族多環とが結合している場合（Ｚが３価の場合は、２つが同一で他の１つが異なる場合も含まれる）、（ｃ）芳香族多環同士が結合している場合（同一の芳香族多環同士あるいは異なった多環の組み合せでもよい。またＺが３価の場合は、２つが同一で他の１つが異なる場合も含まれる）。
【００１３】
また、前記複素環基としては、Ｃ以外にＮ、Ｏ、Ｓのいずれかを核構成元素として含む、いわゆる複素環基であればよく、複素環は３〜８員環のいずれであってもよいが、とくに５〜６員環のものが好ましい。複素環基は１個の複素環のみからなるものであってもよいが、１個の複素環と１個またはそれ以上の芳香族環が縮合した形のものであってもよいし、２個以上の複素環が縮合した形のものであってもよい。具体的には、トリアジン型、オキサゾール型、オキサチアジン型、フラン型、フラザン型、イミダゾール型、イミダゾリジン型、イミダゾリン型、クマロン型、クロメン型、インドール型、インドリン型、イソクマロン型、イソキノリン型、シンノリン型、アクリジン型、カルバゾール型などを挙げることができる。
【００１４】
これら芳香族単炭化水素基あるいは複素環基にはそこに結合している水素が前記Ｒ１〜Ｒ５の項で挙げた基で置換されていてもよいことは当然である。
【００１５】
前記本発明に用いる２核型フェナントロリン誘導体〔前記一般式（ＩＩ）で示す化合物である〕および３核型フェナントロリン誘導体〔前記一般式（ＩＩＩ）で示す化合物である〕の具体的化合物を下記表に示す。
表中、Ｚの項における数字は、下記化１８におけるＺ＝１〜Ｚ＝１８までの数字で示されている２価または３価の基であることを示す。結合手のついている位置を特定していないケースにおいては２価の基の場合、第１順位は、パラ位であり、第２順位はメタ位である。また複素環の場合は、その複素原子に対して、５員環の場合２，５−または２，４−位、６員環の場合、２，４−、２，５−または２，６−位である。また３価の基におけるＺ＝４の場合は、通常１，３，６−位であり、Ｚ＝５の場合は、ＣＨ３が１位とすると、通常２，４，５−位である。
【００１６】
【化１８】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
【表１０】
【表１１】
【表１２】
【表１３】
【表１４】
【表１５】
【表１６】
【表１７】
【表１８】
【表１９】
【表２０】
【表２１】
【表２２】
【表２３】
【表２４】
【表２５】
【表２６】
【表２７】
【表２８】
【表２９】
【表３０】
【表３１】
【表３２】
【表３３】
【表３４】
【表３５】
【表３６】
【表３７】
【表３８】
【表３９】
【表４０】
【表４１】
【表４２】
【表４３】
【表４４】
【表４５】
【表４６】
【表４７】
【表４８】
【表４９】
【表５０】
【表５１】
【表５２】
【表５３】
【表５４】
【表５５】
【表５６】
【表５７】
【表５８】
【表５９】
【表６０】
【表６１】
【表６２】
【表６３】
【表６４】
【表６５】
【表６６】
【表６７】
【表６８】
【表６９】
【表７０】
【表７１】
【表７２】
【表７３】
【表７４】
【表７５】
【表７６】
【表７７】
【表７８】
【表７９】
【表８０】
【表８１】
【表８２】
【表８３】
【表８４】
【表８５】
【表８６】
【表８７】
【表８８】
【表８９】
【表９０】
前記表に示す化合物群のうち、一層代表的な化合物を１つ１つ具体的な構造式で示すと下記のとおりである。
【化１９】
【化２０】
【化２１】
【化２２】
【化２３】
【化２４】
【化２５】
【化２６】
【化２７】
【化２８】
【化２９】
【化３０】
【化３１】
【化３２】
【化３３】
【化３４】
【化３５】
【化３６】
【化３７】
【化３８】
【化３９】
【化４０】
【化４１】
【化４２】
【化４３】
【化４４】
【化４５】
本発明の有機発光素子の各層の構成例としては、下記のものを例示することができる。
単層型
第１電極／発光層（１）／第２電極
（注１）発光層（１）としては、
（ａ）正孔輸送性発光剤と本発明の多核型フェナントロリン誘導体を含むものを分子分散させてなる膜または
（ｂ）前記（ａ）に発光剤をドープした膜を用いる。
二層型
（１）第１電極／発光層（１）／電荷制御層／第２電極
（注２）発光層（１）としては、注１記載のものを用いる
（注３）電荷制御層としては、この例も含め、以下に出てくる電荷制御層においても、公知の電荷制御剤のほか、本発明の電荷制御材料も使用できる。また電荷制御層はアルカリ金属をドーピングしたものであってもよい。
（２）第１電極／発光層（２）／電荷制御層／第２電極
（注４）発光層（２）は正孔輸送性発光剤の膜または正孔輸送剤に発光剤をドープした膜。
多層型
（１）第１電極／正孔輸送層／発光層（１）または（２）／電荷制御層
／第２電極（２）第１電極／発光層（１）／電荷制御層／電子輸送層／第２電極
（３）第１電極／正孔注入層／発光層（１）／電荷制御層／第２電極
（４）第１電極／発光層（２）／電荷制御層／電子輸送層／第２電極
（５）第１電極／正孔注入層／発光層（２）／電荷制御層／第２電極
（６）第１電極／正孔輸送層／発光層（１）または（２）／電荷制御層／電子輸送層／第２電極
（７）第１電極／正孔注入層／正孔輸送層／発光層（１）または（２）／電荷制御層／第２電極
（８）第１電極／正孔注入層／発光層（１）または（２）／電荷制御層／電子輸送層／第２電極
（９）第１電極／正孔注入層／正孔輸送層／発光層（１）または（２）／電荷制御層／電子輸送層／第２電極
なお、通常前記第１電極は、ガラス、合成樹脂などの基板上にＩＴＯ膜を形成したものを用い、第２電極としてはＬｉＦとアルミニウムなどの金属とを設けたものを使用するが、これに限定されるものではない。
【０１３５】
【実施例】
以下に合成例、実施例、比較例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。
【０１３６】
合成例１
（１）７−メチル−８−ニトロキノリン（７−Ｍ−８−Ｎｑ）の合成
【化４６】
【０１３７】
（２）７−［（Ｎ，Ｎ−ジメチルアミノ）エテニル］−８−ニトロキノリン（７−ＤＭＥ−８−Ｎｑ）の合成
【化４７】
【０１３８】
（３）８−ニトロ−７−キノリンカルボアルデヒド（８−Ｎ−７−Ｑａ）の合成
【化４８】
【０１３９】
（４）８−アミノ−７−キノリンカルボアルデヒド（８−Ａ−７−Ｑａ）の合成
【化４９】
この粗製オイルはシリカゲルカラムクロマトグラフ（展開溶媒クロロホルム）で精製し目的の８−Ａ−７−Ｑａが１９．６ｇ（１１４ｍｍｏｌ）得られた。収率５９％ 融点８６．０〜８７．０℃
【０１４０】
（５）１，４−ジ（１，１０−フェナントロリン−２−イル）ベンゼン（ＤＰＢ）の合成
【化５０】
【０１４１】
合成例２
４，４′−ジ（１，１０−フェナントロリン−２−イル）ビフェニル（ＤＰＢｉ）の合成
【化５１】
【０１４２】
合成例３
１，５−ジ（１，１０−フェナントロリン−２−イル）アントラセン（ＤＰＡ）の合成
【化５２】
【０１４３】
合成例４
１，３，５−トリ（１，１０−フェナントロリン−２−イル）ベンゼン（ＴＰＢ）の合成
【化５３】
【０１４４】
合成例５
２，６−ジ（１，１０−フェナントロリン−２−イル）ピリジン（ＤＰＰ）の合成
【化５４】
【０１４５】
実施例１
本発明の実施例１を図１を参照しながら説明する。
パターニング済みの透明導電膜（ＩＴＯ）３が２００ｎｍ成膜されたガラス基板１を界面活性剤を含む水溶液中に浸漬して超音波洗浄し、純水にてリンスを行った。次にイソプロピルアルコールの超音波洗浄で脱脂洗浄し、紫外線を照射してＵＶオゾン洗浄を行った。〔なお、紫外線オゾン洗浄は、紫外線を使って活性酸素を発生させ、同時に基板表面に付着した有機物を分解、酸化揮発除去する洗浄方法である。実際には、酸素の存在する雰囲気下（この場合は大気雰囲気下）で透明導電膜付ガラス基板に低圧水銀灯により紫外線照射する。照射するのは１８５ｎｍと２５４ｎｍの輝線を含む、紫外線である。１８５ｎｍは空気中の酸素に吸収されオゾンを発生し、２５４ｎｍの光はオゾンに吸収され、活性酸素に分解する。また１８５ｎｍのような短波長紫外線は有機物の結合を切断する。活性酸素の酸化作用と切断の作用により有機物は、酸化、分解、揮発される。〕この基板１を真空チャンバーに設置し、１×１０−６Ｔｏｒｒまで真空排気した。
真空チャンバー内には、有機材料を充填したタンタル性蒸着ボートと所定のパターンで成膜するための金属製薄板マスクを設置しておき、蒸着ボートに電流を流すことにより加熱し、有機材料を蒸発されて成膜をおこなった。最初に正孔注入層５として銅フタロシアニン（以下ＣｕＰｃ）を水晶振動子でモニターしながら２２ｎｍ成膜した。次に正孔輸送層７として下記式
【化５５】
【化５６】
なお、ＤＰＶＢｉに代えてトリス（８−キノリノラト）アルミニウム錯体（Ａｌｑ３）を発光層用の材料として用いると緑色発光層を形成することができる。
【０１４６】
ついで、多核型フェナントロリン誘導体により電荷制御層を形成する。すなわち２核型フェナントロリンとして下記式
【化５７】
【０１４７】
次に陰極を成膜する。上記の真空チャンバーから基板を取り出し、金属成膜用チャンバーに基板を取り付けた。成膜した有機材料の劣化を防止するため、大気に触れることなく真空一貫工程により基板を移動させた。金属成膜用チャンバーには、陰極用材料と陰極パターン用の金属性薄板マスクを設置した。すなわち、基板上に電極の形状に合わせた開口を有するマスクを設け、その上から陰極材料を蒸着した。有機材料と同様に１×１０−６Ｔｏｒｒ（１．３３×１０−４Ｐａ）の真空度において成膜を行った。金属製のチャンバー内において、フッ化リチウム（ＬｉＦ）層１７を０．１ｎｍ成膜した。次いでアルミニウム（Ａｌ）層１９を１００ｎｍ成膜し、陰極２１形成した。Ｌｉは電極の安定化のために用いられ、Ａｌを共蒸着しても良い。
【０１４８】
有機発光素子は水分の影響を受けやすいので、その影響を避けるため、成膜後のガラス基板１を不活性なガス、例えばＮ２ガスで満たされたグローブボックスに移動した。有機発光素子と別のガラス板とを紫外線硬化型接着材を用いて接着しパッケージを形成した。
【０１４９】
ガラス板を張り合せた有機発光素子の陽極３と陰極２１とにＤＣ電源２３を接続した。
このようにして形成した有機発光素子にＤＣ電源２３により電流を流すと、ガラス基板１側からの発光が観測された。より詳細には、陰極２１から注入された電子が電荷制御層１５内を通り青色発光層１１に向かう。一方陽極３から注入された正孔が正孔輸送層５と正孔注入層７を通り青色発光層１１に向かう。青色発光層１１内において、電子と正孔とが会合して励起子が発生する。励起子から青色の波長を有する発光が観測される。発光は、ガラス基板１の正面側（積層構造を設けていない側）から観測される。なお、電荷制御層１５としてイオン化ポテンシャルが高い材料を選択すると、正孔のブロック機能が高くなり、ホールブロック材料として機能する。実施例１においては、電荷制御層１５は、電子輸送機能とホールブロック機能とを有している。
【０１５０】
上記の工程により製造した有機発光素子に関して、正面方向（ガラス基板１の表面の法線方向）から測定した輝度を、ミノルタカメラ社製の輝度測定装置ＣＳ−１００を用いて測定した。電流値、電圧値、輝度とから初期効率を計算した。
【０１５１】
実施例２
基板の種類と基板洗浄法に関しては実施例１の場合と同じである。正孔注入層として銅フタロシアニン（ＣｕＰｃ）を２２ｎｍ成膜した。次に、正孔輸送層としてα−ＮＰＤを３４ｎｍ成膜した。青色発光層としてＤＰＶＢｉを２３ｎｍ成膜した。次いで、電荷制御層として、下記式
【化５８】
【０１５２】
比較例１
次に実施例１および実施例２のよる有機発光素子との比較のために、電荷制御層として本発明の多核型フェナントロリン誘導体に代えて下記式
【化５９】
【０１５３】
比較例２
正孔注入層にＣｕＰｃを２２ｎｍ成膜し、正孔輸送層としてα−ＮＰＤを３４ｎｍ成膜し、青色発光層としてＤＰＶＢｉを２３ｎｍ成膜し、最後に電子輸送層としてトリス（８−ヒドロキシキノリノラト）アルミニウム錯体（Ａｌｑ３）を４７ｎｍ成膜した以外は実施例１を繰り返した。
【０１５４】
＜耐熱性のテスト＞
実施例１および２による有機発光素子と比較例１による有機発光素子とを８５℃の恒温槽中に入れ、耐熱性試験を行った。
図５に示すように、比較例１による有機発光素子においては８５℃の耐熱性試験を開始してから２４時間後には初期と比べて同じ電圧における輝度と効率とが大幅に低下した。すなわち、同じ輝度を得るために必要な電圧は高くなった。
図６に示すように、実施例１による有機発光素子においては８５℃のおける耐熱性試験を開始してから３１３時間経過後であっても輝度の変化はわずかであった。すなわち、同じ輝度を得るのに必要な印加電圧の増加率は、比較例１の場合よりも小さかった。効率も低下したが、比較例１による有機発光素子の場合に比べると低下の割合は小さい。
図７に示すように実施例２による有機発光素子においては８５℃における耐熱性試験を開始してから３１３時間経過後であっても、輝度の変化は非常にわずかであった。すなわち、実施例２による有機発光素子では、電圧の上昇、効率の低下もほとんどなく、初期の特性を維持することがわかる。
Ｂｐｈｅｎ、ＤＰＢおよびＤＰＢｉのそれぞれの電荷制御層材料（または電子輸送層材料）として用いた場合の初期測定（電流密度、輝度および効率）にそれほど大きな差はない。これに対して、耐熱性試験を行った場合には、熱による特性の変化の度合いは、Ｂｐｈｅｎを用いた比較例の有機発光素子が最も大きく、ＤＰＢｉを用いた有機発光素子が最も小さいことがわかる。
なお、比較例２のＡｌｑ３に用いたものは耐熱性の点では左程の差がないが、以下の電気光学特性において差がみられた。
【０１５５】
＜その他の物性のテスト＞
図２から４までに実施例１および実施例２による有機発光素子の初期特性を示す。併せて、比較例１および２による有機発光素子の初期特性も示す。図２は、有機発光素子の電流密度の印加電圧依存性を示す図である。図３は、有機発光素子の輝度の印加電圧依存性を示す図である。図４は、有機発光素子の効率の印加電圧依存性を示す図である。
図２に示すように実施例１および２による有機発光素子の電流密度は、比較例１による有機発光素子と同様に印加電圧２．５Ｖ付近から急激に立ち上がっていることがわかる。実施例１および実施例２による有機発光素子と比較例１による有機発光素子の特性とに大きな違いはない。
図３に示すように、実施例１および２による有機発光素子の輝度は、比較例１による有機発光素子と同様に、印加電圧２．５Ｖ付近から急激に立ち上がっていることがわかる。実施例１および実施例２による有機発光素子と比較例１による有機発光素子の特性上、さほどの違いはない。
図４に示すように、実施例１および２による有機発光素子の効率は、印加電圧２．５Ｖ付近から急激に大きくなることがわかる。印加電圧が３Ｖから４Ｖまでの間においては３．５から４の高い効率を維持している。印加電圧が３Ｖから４Ｖまでの間においては、比較例１による有機発光素子の効率が最も高く、実施例２による有機発光素子、実施例１による有機発光素子の順となっている。
【０１５６】
表９１は、図２から図４までから求められた有機発光素子の電気光学特性をまとめた表である。
【０１５７】
【表９１】
表９１に示すように、実施例１および実施例２による有機発光素子の発光開始電圧（輝度が１ｃｄ／ｍ２における電圧として規定した。）は、比較例１と同様に２．７Ｖである。輝度が３００ｃｄ／ｍ２となる電流密度は、比較例１による有機発光素子においては７．６ｍＡ／ｃｍ２であり、その時の電圧は３．４Ｖである。電流効率は３．９ｃｄ／Ａである。実施例１による有機発光素子においては輝度が３００ｃｄ／ｍ２となる電流密度は８．２ｍＡ／ｃｍ２であり、その時の電圧は３．８Ｖである。電流効率は、３．７ｃｄ／Ａ、電力効率は３．０ｌｍ／Ｗである。実施例２による有機発光素子においては輝度が３００ｃｄ／ｍ２となる電流密度は７．７ｍＡ／ｃｍ２であり、その時の電圧は３．５Ｖである。電流効率は３．９ｃｄ／Ａ、電力効率は３．５ｌｍ／Ｗである。
これらの値に関しても実施例１および２と比較例１との差はほとんどない。一方、実施例１および２と比較例２を対比すると、比較例２のものは電圧が高く電流密度も著しく高いのに電流効率、電力効率は実施例１および２の１／２程度と低いものであった。
【０１５９】
以上、説明したように、電荷制御材料として、代表的な１核型のバソフェナントロリン（Ｂｐｈｅｎ）を用いた場合と本発明の多核型フェナントロリン誘導体に当る１，４−ジ（１，１０−フェナントロリン−２−イル）ベンゼン（ＤＰＢ）や４，４′−ジ（１，１０−フェナントロリン−２−イル）ビフェニル（ＤＰＢｉ）を用いた場合とでは、初期特性にはほとんど差がでないが、耐熱性についてはＤＰＢ又はＤＰＢｉを用いた場合の方がＢｐｈｅｎを用いた場合よりも優れていることがわかる。
また、電子輸送層として、代表的なＡｌｑ３を用いた場合と本発明のＤＰＢやＤＰＢｉを用いた場合とでは耐熱性では左程の差がないが電気光学的特性において、本発明のものが著しい改善効果を示していることが判る。
【０１６０】
実施例３、４、比較例３
実施例１における電荷制御層について、実施例３では、前記１，４−ジ（１，１０−フェナントロリン−２−イル）ベンゼン（ＤＰＢ）とセシウム（Ｃｓ）を共蒸着させて作り、実施例４では、前記４，４′−ジ（１，１０−フェナントロリン−２−イル）ビフェニル（ＤＰＢｉ）とセシウム（Ｃｓ）を共蒸着させて作り、比較例３では前記バソフェナントロリン（ＢＰｈｅｎ）とセシウム（Ｃｓ）を共蒸着して作った以外は、実施例１を繰り返した。
セシウム（Ｃｓ）の量は、ＤＰＢ：Ｃｓ、ＤＰＢｉ：Ｃｓ、ＢＰｈｅｎ：Ｃｓがいずれも３：１となるように調整した。
なお、いずれも陰極は厚さ１００ｎｍのＡｌ層を用いた。
【０１６１】
共蒸着法は、真空容器内で複数の蒸着材料を個々に加熱蒸発させ、基板上に成膜させる方法である。この方法を用いると蒸着源ごとに蒸着速度を決定することができ、組成制御が容易に行える。
【０１６２】
実施例３および４の有機発光素子は、比較例３の有機発光素子に較べて耐熱性に優れていることは実施例１および２と比較例１の関係と同様であった。また実施例３および４と比較例３の有機発光素子の電気光学特性を表９２に示す。
【０１６３】
【表９２】
表９１と表９２を比較すると、電荷制御層にＣｓをドーピングした場合でも、Ｃｓをドーピングしていないものとほぼ同様の電気光学特性を得ることができる。
より詳細には、発光開始電圧（輝度は１ｃｄ／ｍ２になる電圧）は２．６から２．７Ｖであり、表９１の値とほぼ同じであった。３００ｃｄ／ｍ２における電流密度は、実施例３および実施例４による有機発光素子の方が実施例１および実施例２による有機発光素子よりも高い電流密度を有する。特に実施例４による有機発光素子における電流密度が高いことがわかる。
【０１６５】
一方、３００ｃｄ／ｍ２を得ることができる印加電圧は、実施例３および実施例４による有機発光素子の方が実施例１および実施例２による有機発光素子よりも低い値を示す。電流効率は実施例３および実施例４による有機発光素子の方が、実施例１および実施例２による有機発光素子よりも低い。これによりアルカリ金属のセシウム（Ｃｓ）をドーピングした電荷制御層を用いることにより、有機発光素子の低電圧動作が可能になることがわかった。
【０１６６】
実施例５
図８に示す有機発光素子は、電荷制御層１５とは別にＡｌｑ３を用いて電子輸送層を形成した場合を例示している。この場合には、図１に示す構造に加えて、例えば、ホールブロック層として機能する厚さ１０ｎｍの電荷制御層１５と陰極２１との間に、厚さ４０ｎｍの電子輸送層２５が形成された構造を有している。電荷制御層１５としては、例えば２核型や３核型のフェナントロリン誘導体を用いることができる。
上記構造を用いると、電子輸送層と電荷制御層（ホールブロック層）とを別個に設けるので、所望の特性を得るための素子構造を設計する際の自由度が増すという利点がある。
【０１６７】
実施例６
パターニング済みの透明導電膜（ＩＴＯ）が２００ｎｍ成膜されたガラス基板を界面活性剤にて超音波洗浄し、純水にてリンスを行った。次にイソプロピルアルコールの超音波洗浄で脱脂洗浄し、紫外線を照射してＵＶオゾン洗浄を行った。この基板を真空チャンバーに設置し、１×１０−６Ｔｏｒｒまで真空排気した。
真空チャンバー内には、有機材料を充填したタンタル性蒸着ボートと所定のパターンで成膜するための金属製薄板マスクを設置しておき、蒸着ボートに電流を流すことにより加熱し、有機材料を蒸発されて成膜をおこなった。最初に正孔注入層として下記式
【化６０】
【化６１】
陰極を成膜するため、金属成膜用チャンバーに基板を移動した。移動の際は有機材料の劣化を防止するため、大気に触れることなく真空一貫で行った。金属成膜用チャンバーには陰極用材料と陰極用パターンの金属製薄板マスクを設置した。有機材料と同様に１×１０−６Ｔｏｒｒの真空度において成膜をおこなった。金属チャンバーでは、セシウム（Ｃｓ）を０．１ｎｍ成膜し、アルミニウム（Ａｌ）を１００ｎｍ成膜し、陰極とした。
有機発光素子デバイスは水分の影響を受けやすいため、成膜したガラス基板を不活性ガスのＮ２を満たしたグローブボックスに移動し、ＵＶ硬化型接着材を塗布した別のガラス板とＵＶ硬化接着し、パッケージした。
ガラス板で貼り合せた有機発光素子デバイスの陽極、陰極にＤＣ電源を接続し電流を印加した。デバイス正面方向の輝度をミノルタカメラ製ＣＳ−１００にて測定し、そのときの電流値、電圧値から初期効率を計算した。
【０１６８】
比較例４
正孔注入層に２−ＴＮＡＴＡを６０ｎｍ成膜、正孔輸送層としてα−ＮＰＤを１２ｎｍ成膜し、赤色発光層としてＡｌｑ３と蛍光性色素材料ＤＣＪＴＢを共蒸着し１６．５ｎｍ成膜し（このときＤＣＪＴＢはＡｌｑ３に対して３．５ｗｔ％の濃度とした。）、最後に電子輸送層としてＡｌｑ３を４０ｎｍ成膜した以外は実施例１を繰り返した。
【０１６９】
実施例６と比較例４の電気光学特性を表９３に示す。
【表９３】
発光スペクトルをみると、図１０に示す比較例４のスペクトルはＤＣＪＴＢの発光に加えて、電子輸送層のＡｌｑ３に由来する５２０ｎｍ付近の発光が見られるのに対し、図９に示す実施例６ではＤＣＪＴＢの発光のみ見られる。また、それぞれの色度にも差が確認された。ＤＰＢを用いた素子の色度は、Ａｌｑ３を用いた素子の色度よりも純粋な赤色の色度に近い値を示した。この色度の差はＡｌｑ３に由来する５２０ｎｍの発光の有無を示唆すると考えられる。このことから、比較例４では、発光領域が発光層および電子輸送層内まで広がっていることが考察され、純粋な赤色の色度が得られていない。それに対し、実施例６に用いた電荷制御材料では、発光領域が発光層内に限定されることで、目的の色度が得られている。これはＤＰＢが電子輸送性に加えてホールブロック性をもつためと考察される。
【０１７０】
【発明の効果】
以上に説明したように、有機発光素子において電子輸送層又はホールブロック層として機能する電荷制御層の材料として多核型フェナントロリン誘導体を用いると、有機発光素子の耐熱性を向上させることができ、有機発光素子の信頼性が向上する。さらに、多核型フェナントロリン誘導体を用いた電荷制御層にアルカリ金属をドーピングすることにより、低い印加電圧でも発光させることができる。
また、電子輸送材料として代表的なＡｌｑ３と比較すると、耐熱性の点では左程の差はないが電流効率および電力効率の点で著しい改善が認められた。
【図面の簡単な説明】
【図１】本発明の実施例１から実施例４までによる有機発光素子の構造を示す断面図である。
【図２】本発明の実施例１および２と比較例１および２による有機発光素子の電流密度の印加電圧依存性を示す図である。
【図３】本発明の実施例１および２と比較例１および２による有機発光素子の輝度の印加電圧依存性を示す図である。
【図４】本発明の実施例１および２と比較例１および２による有機発光素子の電流効率の印加電圧依存性を示す図である。
【図５】本発明の比較例１による有機発光素子の輝度と電流効率との印加電圧依存性を熱処理前と熱処理後で比較した図である。
【図６】本発明の実施例１による有機発光素子の輝度と電流効率との印加電圧依存性を熱処理前と熱処理後で比較した図である。
【図７】本発明の実施例２による有機発光素子の輝度と電流効率との印加電圧依存性を熱処理前と熱処理後で比較した図である。
【図８】本発明の実施例５による有機発光素子の構造を示す断面図である。
【図９】本発明の実施例６の有機発光素子の発光スペクトルである。
【図１０】比較例４の有機発光素子の発光スペクトルである。
【符号の説明】
１ ガラス基板
３ 透明導電膜（陽極）
５ 正孔注入層
７ 正孔輸送層
１１ 青色発光層
１５ 電荷制御層
１７ フッ化リチウム（ＬｉＦ）層
１９ アルミニウム層
２１ 陰極
２３ ＤＣ電源
２５ 電子輸送層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electron transport material and a charge control material comprising a phenanthroline derivative, and an organic light emitting device using the same.
[0002]
[Prior art]
Conventionally, the following formula,
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[0003]
However, Alq 3 Is an efficient electron-transporting material, but emits green light because it is a green light-emitting material when used. However, if you want to extract wavelengths shorter than green, for example, blue, Alq 3 Can not be used. Therefore, the following equation with a large band gap
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[0004]
In particular, it is known that bathophenanthroline has a high electron mobility (
[0005]
However, any of these materials has poor heat resistance, and these vapor-deposited films are liable to be recrystallized. For example, even in a general storage temperature range (−40 ° C. to 85 ° C.), device characteristics are deteriorated due to crystallization. Occurs.
[0006]
[Patent Document 1]
JP 2001-29781 A
[Patent Document 2]
JP 2001-313178 A
[Patent Document 3]
JP-A-5-331459
[Non-patent document 1]
Shigeki Naka et al. , Applied Physics Letters, vol. 76, No. 2, p197-199
[Non-patent document 2]
Junji Kido et al. , Applied Physics Letters, vol. 73, no. 20, p2866-2868
[Non-Patent Document 3]
Kishigami et al. Polymer Symposium Vol. 49, no. 11 (2000), p3385-3386
[0007]
[Problems to be solved by the invention]
The object of the present invention is to provide Alq 3 Another object of the present invention is to provide a novel electron transport material and a charge control material exhibiting an electron transport performance not less than that of an organic light emitting device and an organic light emitting device using the same.
[0008]
[Means for Solving the Problems]
A first aspect of the present invention is to provide the following general formula (I)
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Z (Y) n ...... (I)
[Wherein, Z is a divalent or trivalent group selected from the group consisting of a divalent or trivalent aromatic hydrocarbon group and a divalent or trivalent heterocyclic group, and Y is
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-XA
(X is an element selected from the group consisting of O, S, Se and Te, and A is an alkyl group or an aryl group)
Groups independently selected from the group consisting of ]
And a polynuclear phenanthroline derivative represented by the formula:
In the second aspect of the present invention, the following general formula (I)
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Z (Y) n ...... (I)
[Wherein, Z is a divalent or trivalent group selected from the group consisting of a divalent or trivalent aromatic hydrocarbon group and a divalent or trivalent heterocyclic group, and Y is
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-XA
(X is an element selected from the group consisting of O, S, Se and Te, and A is an alkyl group or an aryl group)
Groups independently selected from the group consisting of ]
And a charge control material comprising a polynuclear phenanthroline derivative represented by the formula:
A third aspect of the present invention relates to an organic light-emitting device having a layer containing the electron transport material according to
A fourth aspect of the present invention is an organic light-emitting device having a first electrode (anode), a light-emitting layer, and a second electrode (cathode), wherein the light-emitting layer is at least a hole-transporting luminescent agent and the electron transport according to
A fifth aspect of the present invention is an organic light emitting device having a first electrode, a light emitting layer, a charge control layer, and a second electrode, wherein the charge control layer contains the charge control material according to
A sixth aspect of the present invention is an organic light emitting device having a first electrode, a hole transport layer, a light emitting layer, a charge control layer, and a second electrode, wherein the charge control layer contains the charge control material according to
A seventh aspect of the present invention relates to the organic light-emitting device according to
An eighth aspect of the present invention relates to the organic light-emitting device according to any one of
The ninth aspect of the present invention relates to the organic light emitting device according to any one of
A tenth aspect of the present invention is that the light emitting layer is
(A) a layer in which a component containing at least a hole transporting luminescent agent and the electron transporting material according to
(B) a layer obtained by doping a luminescent agent into a layer in which a component containing at least a hole transporting luminescent agent and the electron transporting material according to
An organic light-emitting device according to any one of
An eleventh aspect of the present invention relates to the organic light-emitting device according to any one of
[0009]
In the compound represented by the general formula (1), a compound in which Z is a divalent group and n = 2, that is, a phenanthroline derivative having two phenanthroline groups [compound of the following general formula (II)] It can be produced by the following reaction. The following Z and R 1 ~ R 5 Is as defined in the claims.
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In the compound represented by the general formula (I), a compound in which Z is a trivalent group and n = 3, that is, a phenanthroline derivative having three phenanthroline groups [compound of the following general formula (III)] It can be produced by the following reaction.
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In the production method, a reaction solvent is used, and as the reaction solvent, an alcohol can be generally used, and a preferable alcohol has 1 to 6 carbon atoms, and particularly preferably has 1 to 4 carbon atoms. .
As the reaction aid, those which make the system alkaline can be used. Examples of the inorganic material include alkali metal salts such as carbonic acid and hydroxide, alkaline earth metals, and alkali metal and alkaline earth metal hydroxides. Examples of the organic material include alkali metals and alkali metals. Examples include earth metal alcoholates and amine compounds.
This reaction is preferably performed in an inert atmosphere, for example, in an atmosphere of nitrogen, helium, neon, argon or the like, but the reaction proceeds even in the air.
The reaction temperature is not particularly limited, but is usually 50 ° C. or higher, preferably at or near the boiling point of the solvent used. The reaction time is 3 to 48 hours, preferably 10 to 48 hours, particularly preferably 20 to 36 hours.
[0012]
Z is a divalent or trivalent aromatic hydrocarbon group or a divalent or trivalent heterocyclic group, and the aromatic hydrocarbon group is an aromatic monocyclic group or an aromatic polycyclic group. In addition to the case, a group consisting of a combination of the following (a) to (c) may be bonded to -O-, -S-, a saturated alkylene, an unsaturated alkylene, or a bond. (A) when the aromatic monocycles are bonded to each other; (b) when the aromatic monocycle is bonded to the aromatic polycycle (when Z is trivalent, two are the same and the other 1 (C) when aromatic polycycles are bonded to each other (the same aromatic polycycles may be combined or different polycycles may be combined. When Z is trivalent, 2 One is the same and the other is different).
[0013]
The heterocyclic group may be any so-called heterocyclic group containing any of N, O, and S as a core constituent element in addition to C, and the heterocyclic ring may be any of a 3- to 8-membered ring. Good, but a 5- or 6-membered ring is particularly preferred. The heterocyclic group may be composed of only one heterocyclic ring, but may be a condensed form of one heterocyclic ring and one or more aromatic rings, or two The above heterocyclic ring may be in a condensed form. Specifically, triazine type, oxazole type, oxathiazine type, furan type, furazane type, imidazole type, imidazolidine type, imidazoline type, coumarone type, chromene type, indole type, indoline type, isocoumarone type, isoquinoline type, cinnoline type , Acridine type, carbazole type and the like.
[0014]
The hydrogen bonded to the aromatic monohydrocarbon group or heterocyclic group is represented by R 1 ~ R 5 Of course may be substituted with the groups listed in the section.
[0015]
Specific compounds of the binuclear phenanthroline derivative [the compound represented by the general formula (II)] and the trinuclear phenanthroline derivative [the compound represented by the general formula (III)] used in the present invention are shown in the following table. Show.
In the table, the number in the Z section indicates that the group is a divalent or trivalent group represented by a number from Z = 1 to Z = 18 in Chemical Formula 18 below. In the case where the position where the bond is attached is not specified, in the case of a divalent group, the first rank is the para rank and the second rank is the meta rank. In the case of a heterocyclic ring, it is 2,5- or 2,4-position in the case of a 5-membered ring, and 2,4-, 2,5- or 2,6- in the case of a 6-membered ring, with respect to the hetero atom. Rank. In addition, when Z = 4 in the trivalent group, it is usually at the 1,3,6-position, and when Z = 5, CH is 3 Is usually the 2,4,5-position.
[0016]
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[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
[Table 13]
[Table 14]
[Table 15]
[Table 16]
[Table 17]
[Table 18]
[Table 19]
[Table 20]
[Table 21]
[Table 22]
[Table 23]
[Table 24]
[Table 25]
[Table 26]
[Table 27]
[Table 28]
[Table 29]
[Table 30]
[Table 31]
[Table 32]
[Table 33]
[Table 34]
[Table 35]
[Table 36]
[Table 37]
[Table 38]
[Table 39]
[Table 40]
[Table 41]
[Table 42]
[Table 43]
[Table 44]
[Table 45]
[Table 46]
[Table 47]
[Table 48]
[Table 49]
[Table 50]
[Table 51]
[Table 52]
[Table 53]
[Table 54]
[Table 55]
[Table 56]
[Table 57]
[Table 58]
[Table 59]
[Table 60]
[Table 61]
[Table 62]
[Table 63]
[Table 64]
[Table 65]
[Table 66]
[Table 67]
[Table 68]
[Table 69]
[Table 70]
[Table 71]
[Table 72]
[Table 73]
[Table 74]
[Table 75]
[Table 76]
[Table 77]
[Table 78]
[Table 79]
[Table 80]
[Table 81]
[Table 82]
[Table 83]
[Table 84]
[Table 85]
[Table 86]
[Table 87]
[Table 88]
[Table 89]
[Table 90]
Among the compound groups shown in the above table, more typical compounds are shown below by specific structural formulas one by one.
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Examples of the configuration of each layer of the organic light emitting device of the present invention include the following.
Single layer type
First electrode / light-emitting layer (1) / second electrode
(Note 1) As the light emitting layer (1),
(A) a film comprising a molecule containing a hole-transporting luminescent agent and a polynuclear phenanthroline derivative of the present invention, or
(B) A film obtained by doping the luminescent agent in (a) is used.
Two-layer type
(1) First electrode / light-emitting layer (1) / charge control layer / second electrode
(Note 2) As the light emitting layer (1), those described in
(Note 3) As the charge control layer, including this example, the charge control layer of the present invention can be used in the charge control layer described below, in addition to a known charge control agent. The charge control layer may be one doped with an alkali metal.
(2) First electrode / light-emitting layer (2) / charge control layer / second electrode
(Note 4) The light-emitting layer (2) is a film of a hole-transporting light-emitting agent or a film obtained by doping a hole-transporting agent with a light-emitting agent.
Multi-layer type
(1) First electrode / hole transport layer / light emitting layer (1) or (2) / charge control layer
/ Second electrode (2) first electrode / light emitting layer (1) / charge control layer / electron transport layer / second electrode
(3) First electrode / hole injection layer / light emitting layer (1) / charge control layer / second electrode
(4) First electrode / light-emitting layer (2) / charge control layer / electron transport layer / second electrode
(5) First electrode / hole injection layer / light emitting layer (2) / charge control layer / second electrode
(6) First electrode / hole transport layer / light emitting layer (1) or (2) / charge control layer / electron transport layer / second electrode
(7) First electrode / hole injection layer / hole transport layer / light emitting layer (1) or (2) / charge control layer / second electrode
(8) First electrode / hole injection layer / light emitting layer (1) or (2) / charge control layer / electron transport layer / second electrode
(9) First electrode / hole injection layer / hole transport layer / light emitting layer (1) or (2) / charge control layer / electron transport layer / second electrode
Normally, the first electrode is formed by forming an ITO film on a substrate such as glass or synthetic resin, and the second electrode is formed by providing LiF and a metal such as aluminum. It is not limited.
[0135]
【Example】
Hereinafter, the present invention will be described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto.
[0136]
Synthesis Example 1
(1) Synthesis of 7-methyl-8-nitroquinoline (7-M-8-Nq)
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[0137]
(2) Synthesis of 7-[(N, N-dimethylamino) ethenyl] -8-nitroquinoline (7-DME-8-Nq)
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[0138]
(3) Synthesis of 8-nitro-7-quinolinecarbaldehyde (8-N-7-Qa)
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[0139]
(4) Synthesis of 8-amino-7-quinolinecarbaldehyde (8-A-7-Qa)
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This crude oil was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 19.6 g (114 mmol) of the target 8-A-7-Qa. Yield 59% Melting point 86.0-87.0 ° C
[0140]
(5) Synthesis of 1,4-di (1,10-phenanthroline-2-yl) benzene (DPB)
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[0141]
Synthesis Example 2
Synthesis of 4,4'-di (1,10-phenanthroline-2-yl) biphenyl (DPBi)
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[0142]
Synthesis Example 3
Synthesis of 1,5-di (1,10-phenanthroline-2-yl) anthracene (DPA)
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[0143]
Synthesis Example 4
Synthesis of 1,3,5-tri (1,10-phenanthroline-2-yl) benzene (TPB)
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[0144]
Synthesis Example 5
Synthesis of 2,6-di (1,10-phenanthroline-2-yl) pyridine (DPP)
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[0145]
Example 1
The
In the vacuum chamber, a tantalum evaporation boat filled with an organic material and a thin metal mask for forming a film in a predetermined pattern are installed, and heating is performed by passing a current through the evaporation boat to evaporate the organic material. Then, a film was formed. First, copper phthalocyanine (hereinafter referred to as CuPc) was deposited as a
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Note that a tris (8-quinolinolato) aluminum complex (Alq 3 ) Can be used as a material for a light emitting layer to form a green light emitting layer.
[0146]
Next, a charge control layer is formed with a polynuclear phenanthroline derivative. That is, as a dinuclear phenanthroline, the following formula
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[0147]
Next, a cathode is formed. The substrate was taken out of the above-mentioned vacuum chamber, and the substrate was attached to the metal film forming chamber. In order to prevent the deterioration of the formed organic material, the substrate was moved by an integrated vacuum process without being exposed to the atmosphere. The metal film forming chamber was provided with a cathode material and a metal thin plate mask for a cathode pattern. That is, a mask having an opening conforming to the shape of the electrode was provided on the substrate, and a cathode material was vapor-deposited thereon. 1 × 10 as well as organic materials -6 Torr (1.33 × 10 -4 The film was formed at a degree of vacuum of Pa). In a metal chamber, a lithium fluoride (LiF)
[0148]
Since the organic light emitting element is easily affected by moisture, in order to avoid the influence, the
[0149]
A
When a current was applied to the organic light emitting device formed in this manner by the
[0150]
With respect to the organic light emitting device manufactured by the above process, the luminance measured from the front direction (the normal direction of the surface of the glass substrate 1) was measured using a luminance measuring device CS-100 manufactured by Minolta Camera Co., Ltd. The initial efficiency was calculated from the current value, the voltage value, and the luminance.
[0151]
Example 2
The type of the substrate and the substrate cleaning method are the same as those in the first embodiment. Copper phthalocyanine (CuPc) was deposited to a thickness of 22 nm as a hole injection layer. Next, α-NPD was deposited to a thickness of 34 nm as a hole transport layer. DPVBi was deposited to a thickness of 23 nm as a blue light emitting layer. Next, as a charge control layer, the following formula
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[0152]
Comparative Example 1
Next, for comparison with the organic light-emitting devices of Examples 1 and 2, the following formula was used in place of the polynuclear phenanthroline derivative of the present invention as a charge control layer.
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[0153]
Comparative Example 2
A film of CuPc is formed to a thickness of 22 nm on the hole injection layer, a film of α-NPD is formed to a thickness of 34 nm as a hole transport layer, a film of DPVBi is formed to a thickness of 23 nm as a blue light-emitting layer, and finally, tris (8-hydroxyquinolino) is formed as an electron transport layer. (Rat) aluminum complex (Alq 3 Example 1 was repeated except that a) was formed to a thickness of 47 nm.
[0154]
<Heat resistance test>
The organic light emitting devices according to Examples 1 and 2 and the organic light emitting device according to Comparative Example 1 were placed in a thermostat at 85 ° C. and subjected to a heat resistance test.
As shown in FIG. 5, in the organic light emitting device according to Comparative Example 1, the luminance and the efficiency at the same voltage were significantly reduced 24 hours after the start of the heat resistance test at 85 ° C., compared with the initial stage. That is, the voltage required to obtain the same luminance was increased.
As shown in FIG. 6, in the organic light emitting device according to Example 1, a change in luminance was slight even after 313 hours had passed since the start of the heat resistance test at 85 ° C. That is, the rate of increase of the applied voltage required to obtain the same luminance was smaller than that of Comparative Example 1. Although the efficiency also decreased, the rate of decrease was smaller than that of the organic light emitting device according to Comparative Example 1.
As shown in FIG. 7, in the organic light emitting device according to Example 2, the change in luminance was very small even after 313 hours had passed since the start of the heat resistance test at 85 ° C. That is, it can be seen that the organic light emitting device according to Example 2 hardly increases the voltage and decreases the efficiency, and maintains the initial characteristics.
There is no significant difference in the initial measurements (current density, brightness and efficiency) when Bphen, DPB and DPBi are used as charge control layer materials (or electron transport layer materials), respectively. On the other hand, when the heat resistance test was performed, the degree of change in the characteristics due to heat was the largest for the organic light-emitting device of the comparative example using Bphen and the smallest for the organic light-emitting device using DPBi. Understand.
In addition, Alq of Comparative Example 2 3 Although there was no difference in heat resistance with the one used in the above, there was a difference in the following electro-optical characteristics.
[0155]
<Test of other physical properties>
2 to 4 show the initial characteristics of the organic light emitting devices according to the first and second embodiments. In addition, initial characteristics of the organic light emitting devices according to Comparative Examples 1 and 2 are also shown. FIG. 2 is a diagram showing the applied voltage dependence of the current density of the organic light emitting device. FIG. 3 is a diagram illustrating the applied voltage dependency of the luminance of the organic light emitting device. FIG. 4 is a diagram showing the applied voltage dependence of the efficiency of the organic light emitting device.
As shown in FIG. 2, it can be seen that the current density of the organic light emitting devices according to Examples 1 and 2 sharply rises from around an applied voltage of 2.5 V, similarly to the organic light emitting device according to Comparative Example 1. There is no significant difference between the characteristics of the organic light emitting devices according to Example 1 and Example 2 and the organic light emitting device according to Comparative Example 1.
As shown in FIG. 3, it can be seen that the luminance of the organic light emitting devices according to Examples 1 and 2 sharply rises from around an applied voltage of 2.5 V, similarly to the organic light emitting device according to Comparative Example 1. The characteristics of the organic light emitting devices according to Example 1 and Example 2 and the organic light emitting device according to Comparative Example 1 are not so different.
As shown in FIG. 4, it can be seen that the efficiency of the organic light emitting devices according to Examples 1 and 2 sharply increases near the applied voltage of 2.5 V. When the applied voltage is between 3 V and 4 V, a high efficiency of 3.5 to 4 is maintained. When the applied voltage is between 3 V and 4 V, the efficiency of the organic light emitting device according to Comparative Example 1 is the highest, and the order of the organic light emitting device according to Example 2 and the organic light emitting device according to Example 1 is in that order.
[0156]
Table 91 is a table summarizing the electro-optical characteristics of the organic light-emitting device obtained from FIGS. 2 to 4.
[0157]
[Table 91]
As shown in Table 91, the light emission starting voltage (the luminance is 1 cd / m2) of the organic light emitting devices according to the first and second examples. 2 The voltage was defined as ) Is 2.7 V as in Comparative Example 1. Brightness is 300 cd / m 2 Is 7.6 mA / cm in the organic light emitting device according to Comparative Example 1. 2 And the voltage at that time is 3.4V. The current efficiency is 3.9 cd / A. In the organic light emitting device according to Example 1, the luminance was 300 cd / m. 2 Is 8.2 mA / cm 2 And the voltage at that time is 3.8V. The current efficiency is 3.7 cd / A and the power efficiency is 3.0 lm / W. In the organic light emitting device according to Example 2, the luminance was 300 cd / m. 2 Is 7.7 mA / cm 2 And the voltage at that time is 3.5V. The current efficiency is 3.9 cd / A and the power efficiency is 3.5 lm / W.
Also with respect to these values, there is almost no difference between Examples 1 and 2 and Comparative Example 1. On the other hand, comparing Examples 1 and 2 with Comparative Example 2, Comparative Example 2 has a high voltage and a very high current density, but the current efficiency and the power efficiency are as low as about 1/2 of Examples 1 and 2. Met.
[0159]
As described above, the case where a typical mononuclear type bathophenanthroline (Bphen) is used as the charge control material and the case where the 1,4-di (1,10-phenanthroline-) corresponding to the polynuclear type phenanthroline derivative of the present invention are used. Although the initial characteristics are almost the same as those using 2-yl) benzene (DPB) or 4,4'-di (1,10-phenanthroline-2-yl) biphenyl (DPBi), the heat resistance is poor. It can be seen that the case where DPB or DPBi is used is superior to the case where Bphen is used.
In addition, as an electron transport layer, a typical Alq 3 Although there is no difference in the heat resistance between the case of using the present invention and the case of using the DPB or DPBi of the present invention, it can be seen that the present invention shows a remarkable improvement in electro-optical characteristics.
[0160]
Examples 3, 4 and Comparative Example 3
In Example 3, the charge control layer in Example 1 was prepared by co-evaporating the 1,4-di (1,10-phenanthroline-2-yl) benzene (DPB) and cesium (Cs). Then, the above 4,4'-di (1,10-phenanthroline-2-yl) biphenyl (DPBi) and cesium (Cs) are co-evaporated, and in Comparative Example 3, the bathophenanthroline (BPhen) and cesium (Cs) are produced. Example 1 was repeated except that the above was made by co-evaporation.
The amount of cesium (Cs) was adjusted so that DPB: Cs, DPBi: Cs, and BPhen: Cs were all 3: 1.
In each case, an Al layer having a thickness of 100 nm was used as a cathode.
[0161]
The co-evaporation method is a method in which a plurality of evaporation materials are individually heated and evaporated in a vacuum vessel to form a film on a substrate. With this method, the deposition rate can be determined for each deposition source, and composition control can be easily performed.
[0162]
The organic light-emitting devices of Examples 3 and 4 were superior to the organic light-emitting device of Comparative Example 3 in heat resistance, similar to the relationship between Examples 1 and 2 and Comparative Example 1. Table 92 shows electro-optical characteristics of the organic light-emitting devices of Examples 3 and 4 and Comparative Example 3.
[0163]
[Table 92]
Comparing Table 91 and Table 92, even when the charge control layer is doped with Cs, it is possible to obtain almost the same electro-optical characteristics as those obtained when Cs is not doped.
More specifically, the light emission start voltage (the luminance is 1 cd / m 2 Is 2.6 to 2.7 V, which is almost the same as the value in Table 91. 300 cd / m 2 , The organic light emitting devices according to Examples 3 and 4 have a higher current density than the organic light emitting devices according to Examples 1 and 2. In particular, the current density of the organic light emitting device according to Example 4 is high.
[0165]
On the other hand, 300 cd / m 2 Is lower in the organic light emitting devices according to Examples 3 and 4 than in the organic light emitting devices according to Examples 1 and 2. The current efficiency of the organic light emitting devices according to Examples 3 and 4 is lower than that of the organic light emitting devices according to Examples 1 and 2. Thus, it was found that the use of the charge control layer doped with the alkali metal cesium (Cs) enabled low-voltage operation of the organic light-emitting device.
[0166]
Example 5
The organic light emitting device shown in FIG. 3 The case where the electron transport layer is formed using is described. In this case, in addition to the structure shown in FIG. 1, for example, an
When the above structure is used, since the electron transport layer and the charge control layer (hole blocking layer) are separately provided, there is an advantage that the degree of freedom in designing an element structure for obtaining desired characteristics is increased.
[0167]
Example 6
A glass substrate on which a patterned transparent conductive film (ITO) having a thickness of 200 nm was formed was ultrasonically cleaned with a surfactant, and rinsed with pure water. Next, degrease cleaning was performed by ultrasonic cleaning of isopropyl alcohol, and UV ozone cleaning was performed by irradiating ultraviolet rays. This substrate was placed in a vacuum chamber and 1 × 10 -6 Evacuated to Torr.
In the vacuum chamber, a tantalum evaporation boat filled with an organic material and a thin metal mask for forming a film in a predetermined pattern are installed, and heating is performed by passing a current through the evaporation boat to evaporate the organic material. Then, a film was formed. First, as a hole injection layer, the following formula
Embedded image
Embedded image
The substrate was moved to a metal deposition chamber to form a cathode. In order to prevent the organic material from deteriorating during the transfer, the transfer was performed in a vacuum without contacting the atmosphere. A metal thin film mask having a cathode material and a cathode pattern was provided in the metal film forming chamber. 1 × 10 as well as organic materials -6 The film was formed at a degree of vacuum of Torr. In the metal chamber, cesium (Cs) was deposited to a thickness of 0.1 nm, and aluminum (Al) was deposited to a thickness of 100 nm to form a cathode.
Since the organic light emitting device is easily affected by moisture, the formed glass substrate is replaced with an inert gas N2. 2 Then, it was moved to a glove box filled with and cured by UV curing with another glass plate coated with a UV curing adhesive, and packaged.
A DC power supply was connected to the anode and the cathode of the organic light emitting device bonded together with a glass plate, and a current was applied. The luminance in the front direction of the device was measured with a CS-100 manufactured by Minolta Camera, and the initial efficiency was calculated from the current value and voltage value at that time.
[0168]
Comparative Example 4
A 2-TNATA film is formed to a thickness of 60 nm on the hole injection layer, an α-NPD is formed to a thickness of 12 nm as the hole transport layer, and Alq is formed as a red light emitting layer. 3 And a fluorescent dye material DCJTB are co-evaporated to form a film of 16.5 nm (in this case, DCJTB is Alq 3 With respect to the concentration of 3.5 wt%. ), And finally, Alq as the electron transport layer 3 Example 1 was repeated except that was formed to a thickness of 40 nm.
[0169]
Table 93 shows the electro-optical characteristics of Example 6 and Comparative Example 4.
[Table 93]
Looking at the emission spectrum, the spectrum of Comparative Example 4 shown in FIG. 10 shows that the electron transport layer Alq 3 In contrast to this, in the sixth embodiment shown in FIG. 9, only the emission of DCJTB is observed, while the emission around 520 nm derived from is observed. Also, a difference was confirmed in each chromaticity. The chromaticity of a device using DPB is Alq 3 The value was closer to the chromaticity of pure red than the chromaticity of the device using. This difference in chromaticity is Alq 3 It is considered to indicate the presence or absence of 520 nm light emission derived from. From this, in Comparative Example 4, it was considered that the light emitting region was extended to the inside of the light emitting layer and the electron transport layer, and pure red chromaticity was not obtained. On the other hand, in the charge control material used in Example 6, the target chromaticity was obtained by limiting the light emitting region within the light emitting layer. This is considered because DPB has a hole blocking property in addition to the electron transporting property.
[0170]
【The invention's effect】
As described above, when a polynuclear phenanthroline derivative is used as a material of a charge control layer that functions as an electron transport layer or a hole blocking layer in an organic light-emitting element, the heat resistance of the organic light-emitting element can be improved, The reliability of the device is improved. Further, by doping the charge control layer using a polynuclear phenanthroline derivative with an alkali metal, light can be emitted even at a low applied voltage.
In addition, Alq, which is a typical electron transport material, 3 As compared with, there was no significant difference in terms of heat resistance, but significant improvements in current efficiency and power efficiency were observed.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating a structure of an organic light emitting device according to Examples 1 to 4 of the present invention.
FIG. 2 is a diagram showing the applied voltage dependence of the current density of the organic light emitting devices according to Examples 1 and 2 of the present invention and Comparative Examples 1 and 2.
FIG. 3 is a diagram showing the applied voltage dependence of the luminance of the organic light emitting devices according to Examples 1 and 2 of the present invention and Comparative Examples 1 and 2.
FIG. 4 is a diagram showing the applied voltage dependence of the current efficiency of the organic light emitting devices according to Examples 1 and 2 of the present invention and Comparative Examples 1 and 2.
FIG. 5 is a diagram comparing the applied voltage dependence of luminance and current efficiency of an organic light emitting device according to Comparative Example 1 of the present invention before and after heat treatment.
FIG. 6 is a diagram comparing the applied voltage dependence of luminance and current efficiency of an organic light emitting device according to Example 1 of the present invention before and after heat treatment.
FIG. 7 is a diagram comparing the applied voltage dependence of luminance and current efficiency of an organic light emitting device according to Example 2 of the present invention before and after heat treatment.
FIG. 8 is a cross-sectional view illustrating a structure of an organic light emitting device according to a fifth embodiment of the present invention.
FIG. 9 is an emission spectrum of the organic light emitting device of Example 6 of the present invention.
FIG. 10 is an emission spectrum of the organic light emitting device of Comparative Example 4.
[Explanation of symbols]
1 Glass substrate
3 Transparent conductive film (anode)
5 hole injection layer
7 hole transport layer
11 Blue light emitting layer
15 Charge control layer
17 Lithium fluoride (LiF) layer
19 Aluminum layer
21 cathode
23 DC power supply
25 Electron transport layer
Claims (11)
よりなる群からそれぞれ独立して選ばれた基である。〕
で示される多核型フェナントロリン誘導体よりなることを特徴とする電子輸送材料。The following general formula (I)
Groups independently selected from the group consisting of ]
An electron transporting material comprising a polynuclear phenanthroline derivative represented by the formula:
よりなる群からそれぞれ独立して選ばれた基である。〕
で示される多核型フェナントロリン誘導体よりなることを特徴とする電荷制御材料。The following general formula (I)
Groups independently selected from the group consisting of ]
A charge control material comprising a polynuclear phenanthroline derivative represented by the formula:
（Ａ）少なくとも正孔輸送性発光剤と請求項１記載の電子輸送材料とを含有する成分を分子分散させた層であるか、または、
（Ｂ）少なくとも正孔輸送性発光剤と請求項１記載の電子輸送材料とを含有する成分を分子分散させた層に発光剤をドープしてなる層である
請求項４〜９いずれか記載の有機発光素子。The light emitting layer is a layer in which a component containing (A) at least a hole transporting light emitting agent and the electron transporting material according to claim 1 is molecularly dispersed, or
(B) A layer obtained by doping a luminescent agent into a layer in which a component containing at least a hole transporting luminescent agent and the electron transporting material according to claim 1 is molecularly dispersed. Organic light emitting device.
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