JPH0673374A - Organic electroluminescent element - Google Patents
Organic electroluminescent elementInfo
- Publication number
- JPH0673374A JPH0673374A JP5106483A JP10648393A JPH0673374A JP H0673374 A JPH0673374 A JP H0673374A JP 5106483 A JP5106483 A JP 5106483A JP 10648393 A JP10648393 A JP 10648393A JP H0673374 A JPH0673374 A JP H0673374A
- Authority
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- Japan
- Prior art keywords
- group
- light emitting
- electron
- emitting layer
- aromatic
- 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.)
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- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機エレクトロルミネッ
センス素子（以下有機ＥＬ素子）に関するものである。
詳しくは、溶媒可溶な共役系高分子を発光材料として用
い、それと共に電子輸送材料を用いた有機ＥＬ素子に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device (hereinafter referred to as an organic EL device).
Specifically, the present invention relates to an organic EL device using a solvent-soluble conjugated polymer as a light emitting material and an electron transporting material together with the light emitting material.
【０００２】[0002]
【従来の技術】従来から用いられている無機エレクトロ
ルミネッセンス素子（以下無機ＥＬ素子）は発光させる
のに高電圧が必要であった。最近、Ｃ．Ｗ．Ｔａｎｇら
は有機蛍光色素を発光層とし、それに電子写真の感光体
等に用いられていた有機電荷輸送化合物を積層した二層
構造を有する有機ＥＬ素子を作製し、発光層のみを有す
るものに比較して低電圧駆動、高効率、高輝度の有機Ｅ
Ｌ素子を実現させた（特開昭５９−１９４３９３号公
報）。有機ＥＬ素子は無機ＥＬ素子に比べ、低電圧駆
動、高輝度に加えて多数の色の発光が容易に得られると
いう特長があることから、 素子構造や有機蛍光色素、有
機電荷輸送化合物について多くの試みが報告されている
〔ジャパニーズ・ジャーナル・オブ・アプライド・フィ
ジックス（Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．）２７
巻、Ｌ２６９（１９８８年）〕、〔ジャーナル・オブ・
アプライド・フィジックス（Ｊ．Ａｐｐｌ．Ｐｈｙ
ｓ．）６５巻、３６１０頁（１９８９年) 〕。これまで
に、発光材料としては低分子量の有機蛍光色素が一般に
用いられており、高分子の発光材料としては、ＷＯ９０
１３１４８号公開明細書、特開平３−１２６７８７号公
報、アプライド・フィジックス・レターズ（Ａｐｐｌ．
Ｐｈｙｓ．Ｌｅｔｔ．) ５８巻、１９８２頁（１９９１
年）、ジャパニーズ・ジャーナル・オブ・アプライド・
フィジックス（Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．）３
０巻、Ｌ１９３８（１９９１年）、同３０巻、Ｌ１９４
１（１９９１年）などで提案されているにすぎなかっ
た。2. Description of the Related Art Conventionally used inorganic electroluminescent elements (hereinafter referred to as inorganic EL elements) require a high voltage to emit light. Recently, C.I. W. Tang et al. Produced an organic EL device having a two-layer structure in which an organic fluorescent dye was used as a light emitting layer, and an organic charge transport compound used in electrophotographic photoreceptors and the like was laminated, and compared with one having only a light emitting layer. Low voltage drive, high efficiency, high brightness organic E
An L element has been realized (Japanese Patent Laid-Open No. 59-194393). Compared with inorganic EL elements, organic EL elements have the advantages of low voltage drive, high brightness, and the ability to easily emit light of multiple colors. Attempts have been reported [Japanese Journal of Applied Physics (Jpn. J. Appl. Phys.) 27.
Vol. L269 (1988)], [Journal of
Applied Physics (J. Appl. Phy
s. ), 65, 3610 (1989)]. So far, a low molecular weight organic fluorescent dye has been generally used as a light emitting material, and WO 90 is used as a polymer light emitting material.
13148, JP-A-3-126787, Applied Physics Letters (Appl.
Phys. Lett. ) 58, 1982 (1991)
Year), Japanese Journal of Applied
Physics (Jpn. J. Appl. Phys.) 3
Volume 0, L1938 (1991), Volume 30, L194
It was only proposed in 1 (1991).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これま
で報告されてきた高分子発光材料を用いた有機ＥＬ素子
は駆動電圧が高く、輝度も必ずしも十分とは言い難いも
のであった。高分子発光材料は熱的に安定であり、また
塗布法により容易に均一性に優れた発光層を形成できる
ことから、それらの長所を生かしながら、より駆動電圧
が低く、高輝度である有機ＥＬ素子が要望されている。However, the organic EL element using the polymer light emitting material reported so far has a high driving voltage and the brightness is not always sufficient. Since the polymer light emitting material is thermally stable and a light emitting layer having excellent uniformity can be easily formed by a coating method, the organic EL device having a lower driving voltage and high brightness can be used while taking advantage of those advantages. Is required.
【０００４】本発明の目的は塗布法により容易に均一性
に優れた発光層を形成できる高分子発光材料を用いた低
電圧駆動、高輝度の有機ＥＬ素子を提供することにあ
る。An object of the present invention is to provide a low-voltage driven, high-brightness organic EL device using a polymer light emitting material which can easily form a light emitting layer having excellent uniformity by a coating method.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、高分子発
光材料を発光層として用いた有機ＥＬ素子の低電圧駆
動、高輝度化を鋭意検討してきた。その結果、高分子発
光材料として、溶媒に可溶な共役系高分子を用い、これ
に電子輸送性化合物を添加したものを発光層として用い
るか、または、高分子発光層と陰極との間に高分子発光
層に隣接して電子輸送性化合物の層を形成することによ
り、高分子発光材料を単独で用いた場合に比べて低電圧
駆動化、高輝度化が実現されることを見い出し本発明に
至った。Means for Solving the Problems The inventors of the present invention have made earnest studies on low voltage driving and high brightness of an organic EL device using a polymer light emitting material as a light emitting layer. As a result, as the polymer light emitting material, a solvent-soluble conjugated polymer was used, and an electron transporting compound added thereto was used as the light emitting layer, or between the polymer light emitting layer and the cathode. It has been found that by forming a layer of an electron transporting compound adjacent to the polymer light emitting layer, lower voltage driving and higher brightness can be realized as compared with the case where the polymer light emitting material is used alone. Came to.
【０００６】すなわち、本発明は、少なくとも一方が透
明または半透明である一対の陽極および陰極からなる電
極間に少なくとも発光層を有する有機エレクトロルミネ
ッセンス素子において、（１）該発光層が下記化３で表
される構造を有し、溶媒可溶な共役系高分子および電子
輸送性化合物を含むこと、あるいは（２）該発光層が下
記化３で表される構造を有し、溶媒可溶な共役系高分子
よりなり、且つ該発光層と陰極の間に該発光層に隣接し
て電子輸送性化合物の層を有することを特徴とする有機
ＥＬ素子を提供することにある。That is, the present invention relates to an organic electroluminescence device having at least a light emitting layer between electrodes composed of a pair of an anode and a cathode, at least one of which is transparent or semitransparent. Containing a solvent-soluble conjugated polymer and an electron-transporting compound having a structure represented by the above, or (2) the light-emitting layer has a structure represented by the following Chemical formula 3 and a solvent-soluble conjugate Another object of the present invention is to provide an organic EL device comprising a polymer and having a layer of an electron transporting compound between the light emitting layer and the cathode and adjacent to the light emitting layer.
【０００７】[0007]
【化３】 （ここでＡｒは、繰り返し単位を示し、芳香族環または
芳香族性複素環に少なくとも１つの炭素数１〜２２のア
ルキル、アルコキシおよびアルキルチオ基ならびに炭素
数６〜２２の芳香族炭化水素基から選ばれた置換基を有
するアリーレン基または芳香族性複素環化合物基であ
り、且つ該芳香族環または芳香族性複素環が隣接する繰
り返し単位の該芳香族環または芳香族性複素環と連続し
たπ電子共役系を形成するものであり、ｎは５以上の整
数である。）[Chemical 3] (Here, Ar represents a repeating unit, and is selected from at least one alkyl, alkoxy and alkylthio group having 1 to 22 carbon atoms and an aromatic hydrocarbon group having 6 to 22 carbon atoms in an aromatic ring or an aromatic heterocycle. An arylene group or an aromatic heterocyclic compound group having a substituted substituent, and the aromatic ring or the aromatic heterocyclic ring has a continuous π with the aromatic ring or the aromatic heterocyclic ring of adjacent repeating units. It forms an electron conjugated system, and n is an integer of 5 or more.)
【０００８】以下、本発明の有機ＥＬ素子について詳細
に説明する。本発明に用いられる共役系高分子は有機Ｅ
Ｌ素子の発光材料として用いられ、その構造は上記化３
で表されるように、少なくとも１つの炭素数１〜２２の
アルキル、アルコキシおよびアルキルチオ基ならびに炭
素数６〜２２の芳香族炭化水素基から選ばれた置換基を
有する芳香族環または芳香族性複素環を繰り返し単位と
し、それらが、隣合う繰り返し単位の芳香族環または芳
香族性複素環の間でπ電子共役系を形成する結合をとお
して５個以上結合しているもので、有機溶媒に可溶であ
れば特に制限はない。The organic EL device of the present invention will be described in detail below. The conjugated polymer used in the present invention is organic E
It is used as a light-emitting material for L devices, and its structure is
As represented by, an aromatic ring or an aromatic heterocycle having at least one alkyl, alkoxy or alkylthio group having 1 to 22 carbon atoms and a substituent selected from an aromatic hydrocarbon group having 6 to 22 carbon atoms. A ring is used as a repeating unit, and five or more of them are bonded to each other through a bond forming an π-electron conjugated system between aromatic rings or aromatic heterocycles of adjacent repeating units. There is no particular limitation as long as it is soluble.
【０００９】Ａｒ基としては炭素数１〜２２のアルキ
ル、アルコキシおよびアルキルチオ基ならびに炭素数６
〜２２の芳香族炭化水素基から選ばれた置換基を有する
ｐ−フェニレン基、ナフタレン−１，４−ジイル基、ナ
フタレン−１，５−ジイル基、ナフタレン−２，６−ジ
イル基，アントラセン−９，１０−ジイル基、２，５−
チエニレン基、アズレン−１，３−ジイル基、カルバゾ
−ル−２，７−ジイル基、カルバゾ−ル−３，６−ジイ
ル基等が例示される。強いエレクトロルミネッセンスを
示す基としてはｐ−フェニレン基、２，５−チエニレン
基、カルバソール−２，７−ジイル基の核置換体が好ま
しく、より好ましくはｐ−フェニレン、２，５−チエニ
レンの核置換体が好ましい。Examples of the Ar group include alkyl, alkoxy and alkylthio groups having 1 to 22 carbon atoms and 6 carbon atoms.
No. 22 to a p-phenylene group having a substituent selected from an aromatic hydrocarbon group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, anthracene- group. 9,10-diyl group, 2,5-
Examples thereof include a thienylene group, an azulene-1,3-diyl group, a carbazol-2,7-diyl group, and a carbazol-3,6-diyl group. As the group exhibiting strong electroluminescence, a nuclear substitution product of p-phenylene group, 2,5-thienylene group, carbazole-2,7-diyl group is preferable, and more preferable is nuclear substitution of p-phenylene or 2,5-thienylene group. The body is preferred.
【００１０】さらに、化３で示される共役系高分子は溶
媒に可溶であることが必須であることから、炭素数１〜
２２のアルキル基、アルコキシ基およびアルキルチオ基
ならびに炭素数６〜２２の芳香族炭化水素基から選ばれ
た基が１個以上核置換していることが必要である。良好
な可溶性を与えるには、置換基の内、少なくともそれら
の一つが炭素数４〜２２のアルキル基、アルコキシ基ま
たはアルキルチオ基であることが好ましい。これらのな
かで成膜性が良好な炭素数４〜２２のアルキル基、アル
コキシ基が特に好ましい。Furthermore, since the conjugated polymer represented by Chemical formula 3 must be soluble in a solvent, it has 1 to 1 carbon atoms.
It is necessary that one or more groups selected from a 22-alkyl group, an alkoxy group, an alkylthio group, and an aromatic hydrocarbon group having 6 to 22 carbon atoms are nuclear-substituted. In order to provide good solubility, at least one of the substituents is preferably an alkyl group having 4 to 22 carbon atoms, an alkoxy group or an alkylthio group. Among these, an alkyl group having 4 to 22 carbon atoms and an alkoxy group, which have good film-forming properties, are particularly preferable.
【００１１】上記炭素数１〜２２のアルキル基として
は、例えば、メチル基、エチル基、プロピル基、ブチル
基、ペンチル基、ヘキシル基、ヘプチル基、オクチル
基、デシル基、ラウリル基、ドデシル基、オクタデシル
基などであり、ペンチル基、ヘキシル基、ヘプチル基が
好ましい。または炭素数１〜２２のアルコキシ基として
は、メトキシ基、エトキシ基、ブトキシ基、ペンチルオ
キシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチ
ルオキシ基、ラウリルオキシ基、ドデシルオキシ基、オ
クタデシルオキシ基などであり、ペンチルオキシ基、ヘ
キシルオキシ基、ヘプチルオキシ基が好ましい。アルキ
ルチオ基としては、メチルチオ基、エチルチオ基、プロ
ピルチオ基、ブチルチオ基、ペンチルチオ基、ヘキシル
チオ基、ヘプチルチオ基、オクチルチオ基、ラウリルチ
オ基、ドデシルチオ基、オクタデシルチオ基などであ
り、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基
が好ましい。芳香族炭化水素基としてはフェニル基、４
- アルコキシフェニル基（アルコキシ基としては例えば
メトキシ基、エトキシ基、ブトキシ基、ペンチルオキシ
基、ヘキシルオキシ基、ヘプチルオキシ基）、４- アル
キルフェニル基（アルキル基としては例えばメトキシ
基、エトキシ基、ブトキシ基、ペンチルオキシ基、ヘキ
シルオキシ基、ヘプチルオキシ基）、１−ナフチル基、
２−ナフチル基が例示される。Examples of the alkyl group having 1 to 22 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, lauryl group, dodecyl group, It is an octadecyl group and the like, and a pentyl group, a hexyl group and a heptyl group are preferable. Or, as the alkoxy group having 1 to 22 carbon atoms, methoxy group, ethoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, lauryloxy group, dodecyloxy group, octadecyloxy group, etc. And a pentyloxy group, a hexyloxy group, and a heptyloxy group are preferable. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a laurylthio group, a dodecylthio group and an octadecylthio group, and a pentylthio group, a hexylthio group, a heptylthio group. Is preferred. Aromatic hydrocarbon groups are phenyl groups, 4
-Alkoxyphenyl group (eg, methoxy group, ethoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group as alkoxy group), 4-alkylphenyl group (eg, methoxy group, ethoxy group, butoxy group as alkyl group) Group, pentyloxy group, hexyloxy group, heptyloxy group), 1-naphthyl group,
A 2-naphthyl group is exemplified.
【００１２】具体的には、下記表１〜６に示す繰り返し
単位をもつ高分子が例示される。（表中の数字は繰り返
し単位中のアルキル基が左記のアルキル基に該当するも
のの繰り返し単位の番号である。）Specific examples include polymers having the repeating units shown in Tables 1 to 6 below. (The numbers in the table are the numbers of repeating units whose alkyl group in the repeating unit corresponds to the alkyl group on the left.)
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【表２】 [Table 2]
【００１５】[0015]
【表３】 [Table 3]
【００１６】[0016]
【表４】 [Table 4]
【００１７】[0017]
【表５】 [Table 5]
【００１８】[0018]
【表６】 [Table 6]
【００１９】これらの共役系高分子化合物の中で高輝度
や製膜性の観点から、上記繰り返し単位の番号で１〜１
０、１１〜２０、９１〜１０５、１７１〜１８０、１８
１〜１９０、２６１〜２７５が好ましく、より好ましく
は、２〜５、１７〜２０、１８６〜１９０である。これ
らの共役系高分子は単独で用いてもよいし、２種類以上
を混合して用いてもよい。また、これらの重合体に対応
するモノマーの２種類以上を混合して重合した共重合体
でもよい。Among these conjugated polymer compounds, from the viewpoint of high brightness and film-forming property, the repeating unit number is from 1 to 1
0, 11-20, 91-105, 171-180, 18
1-190 and 261-275 are preferable, and 2-5, 17-20, and 186-190 are more preferable. These conjugated polymers may be used alone or in combination of two or more. Further, a copolymer obtained by mixing and polymerizing two or more kinds of monomers corresponding to these polymers may be used.
【００２０】化３において、ｎは繰り返し単位の数を表
し、５以上であれば特に限定されないが、余りにも小さ
すぎると均一な膜が得られにくい場合があり、また、余
りに大きすぎても溶解性が低下し、均一に製膜すること
が困難になる場合があるのでｎの範囲は１０以上が好ま
しく、１０〜１００００がより好ましい。In Chemical Formula 3, n represents the number of repeating units and is not particularly limited as long as it is 5 or more. However, if it is too small, it may be difficult to obtain a uniform film, and if it is too large, it may dissolve. Since it may be difficult to uniformly form a film, the range of n is preferably 10 or more, more preferably 10 to 10,000.
【００２１】これらの有機溶媒可溶性の共役系高分子を
用いて溶液から成膜する場合、この溶液を塗布後乾燥に
より溶媒を除去するだけでよく、また、電子輸送性化合
物を混合した場合においても同様な手法が適用でき、製
造上非常に有利である。In the case of forming a film from a solution using these organic solvent-soluble conjugated polymers, it suffices to remove the solvent by coating the solution and then drying it, and also in the case of mixing an electron transporting compound. A similar method can be applied, which is very advantageous in manufacturing.
【００２２】上記化３で示される共役系高分子の合成法
としては特に限定されないが、相当するモノマ−を電解
重合する方法、３価の鉄などの酸化剤で酸化重合する方
法、相当する繰り返し単位のジハロゲン化合物をグリニ
ャ−ル化して重合する反応、同様に０価ニッケル錯体に
より重合させる方法などが例示される。また、これらの
共役系高分子を有機ＥＬ素子の発光層として用いる場
合、その純度が発光特性に影響を与えるため、合成後、
再沈精製、クロマトグラフィーによる分別等の純化処理
をすることが望ましい。The method of synthesizing the conjugated polymer represented by the above chemical formula 3 is not particularly limited, but a method of electrolytically polymerizing a corresponding monomer, a method of oxidatively polymerizing with an oxidizing agent such as trivalent iron, and a corresponding repetition. Examples thereof include a reaction in which a unit dihalogen compound is converted into a Grignard and polymerized, and a method in which the unit is similarly polymerized with a zero-valent nickel complex. Further, when these conjugated polymers are used as a light emitting layer of an organic EL device, the purity thereof affects the light emitting characteristics.
It is desirable to carry out purification treatment such as reprecipitation purification and fractionation by chromatography.
【００２３】本発明に用いられる電子輸送性化合物とし
ては、発光材料として使用する共役系高分子に対して電
子輸送性が高ければ特に限定されないが、例えば、オキ
サジアゾール系化合物、ベンゾキノン系化合物、ナフト
キノン系化合物、アントラキノン系化合物、テトラシア
ノアントラキノジメタン系化合物、ジフェニルジシアノ
エチレン系化合物、ジフェノキノン系化合物等が例示さ
れる。具体的には、特開昭６３−７０２５７、同６３−
１７５８６０号公報、特開平２−１３５３６１、同２−
１３５３５９、同３−１５２１８４号公報に記載されて
いるもの等、公知のものが使用可能であるが、オキサジ
アゾール系化合物、ベンゾキノン系化合物、アントラキ
ノン系化合物が好ましく、特に、２−（４−ビフェニリ
ル）−５−（４−ｔ−ブチルフェニル）−１，３，４−
オキサジアゾール、ベンゾキノン、アントラキノンが好
ましい。これらの電子輸送性化合物は単独で用いてもよ
いし、２種類以上を混合して用いてもよい。The electron transporting compound used in the present invention is not particularly limited as long as it has a high electron transporting property with respect to the conjugated polymer used as the light emitting material. For example, an oxadiazole compound, a benzoquinone compound, Examples thereof include naphthoquinone compounds, anthraquinone compounds, tetracyanoanthraquinodimethane compounds, diphenyldicyanoethylene compounds, diphenoquinone compounds and the like. Specifically, JP-A-63-70257 and JP-A-63-70257
175860, JP-A-2-135361, and JP-A-2-135361.
Known compounds such as those described in 135359 and 3-152184 can be used, but oxadiazole compounds, benzoquinone compounds, and anthraquinone compounds are preferable, and 2- (4-biphenylyl) is particularly preferable. ) -5- (4-T-Butylphenyl) -1,3,4-
Oxadiazole, benzoquinone and anthraquinone are preferred. These electron-transporting compounds may be used alone or in combination of two or more.
【００２４】本発明の有機ＥＬ素子の発光層として、発
光材料として用いられる化３で示される共役系高分子に
電子輸送性化合物を混合して使用する場合、その量は少
なすぎると効果が小さく、多すぎると発光に寄与しない
電流が増加するため、有機ＥＬ素子にした場合、輝度等
の特性が悪くなる。使用する電子輸送性化合物の分子量
によっても異なるが、混合する割合は化３で示される共
役系高分子に対して０. ０１〜４０ｗｔ％が好ましく、
より好ましくは０. １〜３０ｗｔ％、さらに好ましくは
０．１〜１０ｗｔ％である。混合方法としては電子輸送
性化合物と該共役系高分子を同一溶媒に溶解させ、混合
溶液とし、これを塗布する方法が一般的に例示される。When the electron-transporting compound is mixed with the conjugated polymer represented by Chemical formula 3 used as a light-emitting material for the light-emitting layer of the organic EL device of the present invention, if the amount is too small, the effect is small. However, when the amount is too large, the current that does not contribute to light emission increases, and thus when the organic EL element is used, the characteristics such as brightness deteriorate. Although it depends on the molecular weight of the electron-transporting compound used, the mixing ratio is preferably 0.01 to 40 wt% with respect to the conjugated polymer represented by Chemical formula 3,
It is more preferably 0.1 to 30 wt%, and even more preferably 0.1 to 10 wt%. As a mixing method, a method of dissolving the electron-transporting compound and the conjugated polymer in the same solvent to prepare a mixed solution, and coating the mixed solution is generally exemplified.
【００２５】化３で示される共役系高分子を溶解させる
溶媒は製膜できる程度に溶解性があれば、特に制限はな
く、該共役系高分子の種類により最適溶媒は異なるので
適宜選択する。共役系高分子の繰り返し単位中に炭素数
４以上のアルキル基、アルコキシ基またはアルキルチオ
基等の長鎖基が含まれている場合にはクロロホルム、塩
化メチレン、塩化エチレン、４塩化炭素、ジメチルホル
ムアミド、ジメチルアセトアミド、ジメチルスルホキシ
ド、テトラヒドフラン、Ｎ−メチルピロリドン、トルエ
ン、キシレン、プロピレンカ−ボネ−ト等が例示され
る。これらの内で製膜性が良好で、しかも、上記の電子
輸送材料も溶解させる溶媒としてはクロロホルム、トル
エン、テトラヒドロフランが好ましい。The solvent for dissolving the conjugated polymer represented by Chemical formula 3 is not particularly limited as long as it is soluble to the extent that a film can be formed, and the optimum solvent varies depending on the type of the conjugated polymer, and is appropriately selected. When the repeating unit of the conjugated polymer contains a long chain group such as an alkyl group, an alkoxy group or an alkylthio group having 4 or more carbon atoms, chloroform, methylene chloride, ethylene chloride, carbon tetrachloride, dimethylformamide, Examples thereof include dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, N-methylpyrrolidone, toluene, xylene, propylene carbonate and the like. Among these, chloroform, toluene, and tetrahydrofuran are preferable as the solvent that has good film-forming properties and that also dissolves the electron transport material.
【００２６】本発明においては、化３で示される共役系
高分子に、既知の発光材料を分散させたものを発光層と
して用いることも含まれる。発光材料としては特に限定
されないが、例えば、ナフタレン及びその誘導体、アン
トラセン及びその誘導体、ペリレン及びその誘導体、ポ
リメチン系、キサンテン系、クマリン系、シアニン系な
どの色素類、８−ヒドロキシキノリンおよびその誘導体
の金属錯体、芳香族アミン、テトラフェニルシクロペン
タジエン及びその誘導体、テトラフェニルブタジエン及
びその誘導体などを用いることができる。具体的には、
例えば特開昭５７−５１７８１、同５９−１９４３９３
号公報に記載されているもの等、公知のものが使用可能
である。In the present invention, it is also included to use, as a light emitting layer, a substance in which a known light emitting material is dispersed in the conjugated polymer represented by Chemical formula 3. The luminescent material is not particularly limited, and examples thereof include naphthalene and its derivatives, anthracene and its derivatives, perylene and its derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based dyes, 8-hydroxyquinoline and its derivatives. Metal complexes, aromatic amines, tetraphenylcyclopentadiene and its derivatives, tetraphenylbutadiene and its derivatives and the like can be used. In particular,
For example, JP-A-57-51781 and 59-194393.
Known ones such as those described in Japanese Patent Publication can be used.
【００２７】本発明の有機ＥＬ素子の製造について以下
に述べる。陽極および陰極からなる一対の電極で、透明
または半透明な電極としては、ガラス、透明プラスチッ
ク等の透明基板の上に透明または半透明の電極を形成し
たものが用いられる。陽極の材料としては、導電性の金
属酸化物膜、半透明の金属薄膜等が用いられる。具体的
にはインジウム・スズ・オキサイド (ＩＴＯ) 、酸化ス
ズ (ＮＥＳＡ）、Ａｕ、Ｐｔ、Ａｇ、Ｃｕ等が用いられ
る。作製方法としては真空蒸着法、スパッタリング法、
メッキ法などが用いられる。The production of the organic EL device of the present invention will be described below. As a pair of electrodes composed of an anode and a cathode, the transparent or semitransparent electrode is a transparent or semitransparent electrode formed on a transparent substrate such as glass or transparent plastic. A conductive metal oxide film, a semitransparent metal thin film, or the like is used as the material of the anode. Specifically, indium tin oxide (ITO), tin oxide (NESA), Au, Pt, Ag, Cu and the like are used. As a manufacturing method, a vacuum evaporation method, a sputtering method,
A plating method or the like is used.
【００２８】次いで、この陽極上に共役系高分子の発光
層を形成する。成膜方法としては共役系高分子を有機溶
媒に溶解した溶液を使用したスピンコーティング法、キ
ャスティング法、ディッピング法、バーコート法、ロー
ルコート法、スプレー法等の塗布法が例示される。Next, a light emitting layer of a conjugated polymer is formed on this anode. Examples of the film forming method include coating methods such as a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method and a spray method which use a solution in which a conjugated polymer is dissolved in an organic solvent.
【００２９】発光層の膜厚としては０．５ｎｍ〜１０μ
ｍ、好ましくは１ｎｍ〜１μｍである。電流密度を上げ
て発光効率を上げるためには１０〜５００ｎｍの範囲が
好ましい。なお、塗布法により薄膜化した場合には、溶
媒を除去するため、減圧下あるいは不活性雰囲気下、３
０〜２００℃、好ましくは６０〜１００℃の温度で熱処
理することが望ましい。The thickness of the light emitting layer is 0.5 nm to 10 μm.
m, preferably 1 nm to 1 μm. In order to increase the current density and the luminous efficiency, the range of 10 to 500 nm is preferable. In addition, when a thin film is formed by a coating method, in order to remove the solvent, under reduced pressure or in an inert atmosphere, 3
It is desirable to perform heat treatment at a temperature of 0 to 200 ° C, preferably 60 to 100 ° C.
【００３０】次いでこの発光層の上に電子輸送層を形成
する。電子輸送性化合物の成膜方法としては、特に限定
されないが、真空蒸着法、あるいは該化合物を有機溶媒
に溶かした後、スピンコーティング法、キャスティング
法、ディッピング法、バーコート法、ロールコート法、
スプレー法等の塗布法を用いたり、さらに既知の高分子
化合物と電子輸送性化合物とを溶液状態または溶融状態
で混合した後、スピンコーティング法、キャスティング
法、ディッピング法、バーコート法、ロールコート法、
スプレー法等の塗布法を用いて成膜することができる。
混合する既知の高分子化合物としては、特に限定されな
いが、電荷輸送を極度に阻害しないものが好ましく、ま
た、可視光に対する吸収が強くないものが好適に用いら
れる。例えば、ポリ（Ｎ−ビニルカルバゾール）、ポリ
アニリン及びその誘導体、ポリ（ｐ−フェニレンビニレ
ン）及びその誘導体、ポリ（２，５−チエニレンビニレ
ン）及びその誘導体、ポリカーボネート、ポリメタクリ
レート、ポリメチルメタクリレート、ポリスチレンおよ
びポリ塩化ビニル等のビニル系ポリマー、ポリシロキサ
ンなどが例示される。製膜が容易に行なえるという点で
は、塗布法を用いることが好ましい。Next, an electron transport layer is formed on this light emitting layer. The film forming method of the electron transporting compound is not particularly limited, but is a vacuum deposition method, or after dissolving the compound in an organic solvent, a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method,
After using a coating method such as a spray method or further mixing a known polymer compound and an electron transporting compound in a solution state or a molten state, a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method. ,
The film can be formed using a coating method such as a spray method.
The known polymer compound to be mixed is not particularly limited, but a compound that does not extremely disturb charge transport is preferable, and a compound that does not strongly absorb visible light is preferably used. For example, poly (N-vinylcarbazole), polyaniline and its derivatives, poly (p-phenylenevinylene) and its derivatives, poly (2,5-thienylenevinylene) and its derivatives, polycarbonate, polymethacrylate, polymethylmethacrylate, polystyrene. And vinyl polymers such as polyvinyl chloride and polysiloxane. The coating method is preferably used from the viewpoint of easy film formation.
【００３１】電子輸送層の膜厚は、少なくともピンホー
ルが発生しないような厚みが必要であるが、あまり厚い
と素子の抵抗が増加し、高い駆動電圧が必要となり好ま
しくない。したがって、電子輸送層の膜厚は０．５ｎｍ
〜１０μｍ、好ましくは１ｎｍ〜１μｍ、さらに好まし
くは５〜２００ｎｍである。The film thickness of the electron transport layer needs to be at least such that pinholes are not generated, but if it is too thick, the resistance of the device increases and a high driving voltage is required, which is not preferable. Therefore, the thickness of the electron transport layer is 0.5 nm
-10 μm, preferably 1 nm to 1 μm, more preferably 5 to 200 nm.
【００３２】上記は共役系高分子からなる発光層と電子
輸送層を積層して設ける場合について述べたが、共役系
高分子と電子輸送性化合物を含む発光層を形成する場合
は共役系高分子と電子輸送化合物を有機溶媒に溶解した
混合溶液を用いてスピンコーティング法、キャスティン
グ法、ディッピング法、バーコート法、ロールコート
法、スプレー法等の塗布法により成膜する方法が採用さ
れる。膜厚は前記発光層の厚みと同様な範囲である。ま
た、本発明においては、共役系高分子からなる発光層と
共役系高分子と電子輸送性化合物を含む発光層を積層す
ることも可能である。The above has described the case where the light emitting layer made of the conjugated polymer and the electron transport layer are provided in a laminated manner. However, when the light emitting layer containing the conjugated polymer and the electron transporting compound is formed, the conjugated polymer is used. A method of forming a film by a coating method such as a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method, or a spray method using a mixed solution of an electron transport compound and an electron transport compound dissolved in an organic solvent is adopted. The film thickness is in the same range as the thickness of the light emitting layer. In the present invention, it is also possible to stack a light emitting layer made of a conjugated polymer and a light emitting layer containing a conjugated polymer and an electron transporting compound.
【００３３】次いで、発光層が共役系高分子と電子輸送
性化合物との混合層の場合はこの層の上に、また発光層
と電子輸送層が積層されている場合は電子輸送層の上に
電極を設ける。この電極は電子注入陰極となる。その材
料としては、特に限定されないが、イオン化エネルギー
の小さい材料が好ましい。例えば、Ａｌ、Ｉｎ、Ｍｇ、
Ｍｇ−Ａｇ合金、Ｉｎ−Ａｇ合金、Ｍｇ−Ｉｎ合金、Ｃ
ａおよびそれらの合金、Ｌｉおよびそれらの合金、グラ
ファイト薄膜等が用いられる。これら陰極材料のうち空
気中で不安定な材料の場合、保護膜として、例えばＡ
ｌ，Ａｕ，Ａｇ，Ｐｔなどの空気中で安定な材料を更に
陰極材料の上に作成してもよい。陰極の作製方法として
は真空蒸着法、スパッタリング法等公知の方法が用いら
れる。Next, when the light emitting layer is a mixed layer of a conjugated polymer and an electron transporting compound, it is on this layer, and when the light emitting layer and the electron transporting layer are laminated, it is on the electron transporting layer. Provide electrodes. This electrode becomes the electron injection cathode. The material is not particularly limited, but a material having low ionization energy is preferable. For example, Al, In, Mg,
Mg-Ag alloy, In-Ag alloy, Mg-In alloy, C
a and alloys thereof, Li and alloys thereof, graphite thin film and the like are used. In the case of a material that is unstable in air among these cathode materials, a protective film such as A
A material stable in air such as 1, Au, Ag, or Pt may be further formed on the cathode material. As a method for producing the cathode, known methods such as a vacuum vapor deposition method and a sputtering method are used.
【００３４】なお、本発明のＥＬ素子の構造としては、
これまで述べた陽極／発光層（発光材料と電子輸送性化
合物の混合物）／陰極（／は層を積層したことを示
す）、あるいは陽極／発光層／電子輸送層／陰極の構造
以外に、さらに公知の正孔輸送層を積層する場合は陽極
／正孔輸送層／発光層／電子輸送層／陰極、陽極／正孔
輸送層／発光層（発光材料と電子輸送性化合物の混合
物）／陰極の構造が挙げられる。さらに陽極と発光層も
しくは正孔輸送層の間、または陰極と電子輸送層との間
に既知のバッファー層を有する積層構造等をとることも
できる。The structure of the EL device of the present invention is as follows.
In addition to the structure of anode / light-emitting layer (mixture of light-emitting material and electron-transporting compound) / cathode (/ means stacking layers) or anode / light-emitting layer / electron-transporting layer / cathode described above, When laminating a well-known hole transporting layer, it may be formed of anode / hole transporting layer / light emitting layer / electron transporting layer / cathode, anode / hole transporting layer / light emitting layer (mixture of light emitting material and electron transporting compound) / cathode. The structure is mentioned. Further, a laminated structure having a known buffer layer between the anode and the light emitting layer or the hole transporting layer or between the cathode and the electron transporting layer can be adopted.
【００３５】[0035]
【実施例】以下、本発明の実施例を示すが、本発明はこ
れらに限定されるものではない。EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.
【００３６】参考例 〔ポリ（３−ヘキシル−２，５−チエニレン）の合成〕
３−ヘキシルチオフェン１．７ｇをクロロホルムに１０
０ｍｌに溶解させ、これに塩化第２鉄を３−ヘキシルチ
オフェンの４倍当量加え、室温で５時間反応した。反応
後、メタノ−ルを５００ｍｌ加えたところ、緑色の沈澱
が生じた。これを濾過、洗浄後乾燥した。沈澱物は１．
６ｇ得られた。赤外吸収スペクトル、紫外可視吸収スペ
クトルからポリ（３−ヘキシル−２，５−チエニレン）
の構造を確認した。また、ＧＰＣによるポリスチレン換
算の数平均分子量は４３，０００であった。Reference Example [Synthesis of poly (3-hexyl-2,5-thienylene)]
Chloroform was added with 1.7 g of 3-hexylthiophene.
It was dissolved in 0 ml, and ferric chloride was added thereto in an amount of 4 times equivalent of 3-hexylthiophene, and the mixture was reacted at room temperature for 5 hours. After the reaction, 500 ml of methanol was added, and a green precipitate was produced. This was filtered, washed, and dried. The precipitate is 1.
6 g was obtained. From infrared absorption spectrum and UV-visible absorption spectrum, poly (3-hexyl-2,5-thienylene)
The structure of was confirmed. The polystyrene-equivalent number average molecular weight by GPC was 43,000.
【００３７】実施例１ スパッタリングによって、４０ｎｍの厚みでＩＴＯ膜を
付けたガラス基板に、参考例１で得たポリ（３−ヘキシ
ル−２，５−チエニレン）と電子輸送性化合物として２
−（４−ビフェニリル）−５−（４−ｔ−ブチルフェニ
ル）−１，３，４−オキサジアゾール（以下ＰＢＤ）
〔ここでＰＢＤのポリ（３−ヘキシル−２．５−チエニ
レン）に対する混合割合は１. ４ｗｔ％である〕の０．
４ｗｔ％クロロホルム溶液を用い、スピンコートにより
３０ｎｍの厚みで成膜した。次いで、これを減圧下６０
℃で１時間乾燥した後、その上に陰極としてＭｇ―Ａｇ
合金（Ｍｇ：Ａｇは重量比で１０：１）を１５０ｎｍ蒸
着して有機ＥＬ素子を作製した。蒸着のときの真空度は
３×１０-6Ｔｏｒｒ以下であった。この素子に暗室内で
電圧１９Ｖを印加したところ、電流密度６０２ｍＡ／ｃ
ｍ 2 の電流が流れ、輝度４. ５８ｃｄ／ｍ2 の赤色のＥ
Ｌ発光が観察された。輝度は輝度計ＬＳ―１００（ミノ
ルタ（株）製）で測定した。このとき暗室内の明るさは
０. ０１ｃｄ／ｍ2 以下であった。Example 1 An ITO film having a thickness of 40 nm was formed by sputtering.
On the attached glass substrate, the poly (3-hexyl) obtained in Reference Example 1 was added.
(2,5-thienylene) and 2 as an electron-transporting compound
-(4-Biphenylyl) -5- (4-t-butylphenyl)
L) -1,3,4-oxadiazole (hereinafter PBD)
[Where PBD poly (3-hexyl-2.5-thieny
The mixing ratio is 1.4 wt%].
Spin coating using 4wt% chloroform solution
A film having a thickness of 30 nm was formed. Then, this is reduced pressure 60
After drying at ℃ for 1 hour, Mg-Ag as a cathode on it
Alloy (Mg: Ag is 10: 1 by weight) steamed to 150 nm
After that, an organic EL device was produced. The degree of vacuum during vapor deposition
3 x 10-6It was below Torr. This element in a dark room
When a voltage of 19 V was applied, the current density was 602 mA / c
m 2Current flows and the brightness is 4.58 cd / m2 Red E
L emission was observed. Luminance is measured with a luminance meter LS-100 (Mino
Ruta Co., Ltd.). At this time, the brightness in the dark room
0.01 cd / m2 It was below.
【００３８】実施例２ 電子輸送性化合物としてＰＢＤの代わりにアントラキノ
ンを使用した〔ここでアントラキノンのポリ（３−ヘキ
シル−２，５−チエニレン）に対する混合割合は１. ５
ｗｔ％であった〕以外は実施例１と同じ方法で３０ｎｍ
の厚みの発光層をもつ、有機ＥＬ素子を作成した。この
素子を実施例１と同じ方法で輝度を測定したところ、輝
度３. ２２ｃｄ／ｍ2 の赤色のＥＬ発光が観察された。
このとき印加した電圧は１３Ｖであり、６０２ｍＡ／ｃ
ｍ2 の電流が流れた。Example 2 Anthraquinone was used in place of PBD as the electron transporting compound [wherein the mixing ratio of anthraquinone to poly (3-hexyl-2,5-thienylene) was 1.5.
% was the same as in Example 1 except that it was 30 nm.
An organic EL device having a light emitting layer having a thickness of 1 was prepared. When the luminance of this device was measured by the same method as in Example 1, red EL light emission with a luminance of 3.22 cd / m 2 was observed.
The voltage applied at this time was 13 V and was 602 mA / c.
An electric current of m 2 flowed.
【００３９】比較例 ポリ（３−ヘキシル−２，５−チエニレン）に電子輸送
性化合物を混合しない以外は実施例１と同じ方法で３０
ｎｍの厚みの発光層を有する有機ＥＬ素子を作製した。
この素子を実施例１と同じ方法で輝度を測定したとこ
ろ、輝度０. ８３ｃｄ／ｍ2 のＥＬ発光が観察された
が、色は確認できなかった。このとき印加した電圧は１
５Ｖであり、６０２ｍＡ／ｃｍ2 の電流が流れた。Comparative Example The same method as in Example 1 was repeated except that the electron transporting compound was not mixed with poly (3-hexyl-2,5-thienylene).
An organic EL device having a light emitting layer having a thickness of nm was produced.
When the luminance of this element was measured by the same method as in Example 1, EL emission with a luminance of 0.83 cd / m 2 was observed, but no color could be confirmed. The voltage applied at this time is 1
It was 5 V, and a current of 602 mA / cm 2 flowed.
【００４０】[0040]
【発明の効果】以上説明したように、本発明の有機ＥＬ
素子は、従来のものと比較して、低電圧駆動で、しかも
輝度が向上しており、バックライトとしての面状光源、
フラットパネルディスプレイ等の装置としての使用が可
能である。As described above, the organic EL device of the present invention
Compared with the conventional device, the device is driven at a lower voltage and has improved brightness, and a surface light source as a backlight,
It can be used as a device such as a flat panel display.
Claims (2)
一対の陽極および陰極からなる電極間に、少なくとも発
光層を有する有機エレクトロルミネッセンス素子におい
て、該発光層が、下式 【化１】 （ここでＡｒは、繰り返し単位を示し、芳香族環または
芳香族性複素環に少なくとも１つの炭素数１〜２２のア
ルキル、アルコキシおよびアルキルチオ基ならびに炭素
数６〜２２の芳香族炭化水素基から選ばれた置換基を有
するアリーレン基または芳香族性複素環化合物基であ
り、且つ該芳香族環または芳香族性複素環が隣接する繰
り返し単位の該芳香族環または芳香族性複素環と連続し
たπ電子共役系を形成するものであり、ｎは５以上の整
数である。）で表される構造を有し、有機溶媒に可溶な
共役系高分子および電子輸送性化合物を含むことを特徴
とする有機エレクトロルミネッセンス素子。1. An organic electroluminescence device having at least a light emitting layer between a pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or semitransparent, wherein the light emitting layer is represented by the following formula: (Here, Ar represents a repeating unit, and is selected from at least one alkyl, alkoxy and alkylthio group having 1 to 22 carbon atoms and an aromatic hydrocarbon group having 6 to 22 carbon atoms in an aromatic ring or an aromatic heterocycle. An arylene group or an aromatic heterocyclic compound group having a substituted substituent, and the aromatic ring or the aromatic heterocyclic ring has a continuous π with the aromatic ring or the aromatic heterocyclic ring of adjacent repeating units. It forms an electron conjugated system, n is an integer of 5 or more.), And has a structure represented by an organic solvent and contains a conjugated polymer and an electron transporting compound. An organic electroluminescence device that does.
一対の陽極および陰極からなる電極間に少なくとも発光
層を有する有機エレクトロルミネッセンス素子におい
て、該発光層が、下式 【化２】 （ここでＡｒは、繰り返し単位を示し、芳香族環または
芳香族性複素環に少なくとも１つの炭素数１〜２２のア
ルキル、アルコキシおよびアルキルチオ基ならびに炭素
数６〜２２の芳香族炭化水素基から選ばれた置換基を有
するアリーレン基または芳香族性複素環化合物基であ
り、且つ該芳香族環または芳香族性複素環が隣接する繰
り返し単位の該芳香族環または芳香族性複素環と連続し
たπ電子共役系を形成するものであり、ｎは５以上の整
数である。）で表される構造を有し、有機溶媒に可溶な
共役系高分子よりなり、且つ陰極と該発光層との間に、
該発光層に隣接して電子輸送性化合物からなる層を設け
たことを特徴とする有機エレクトロルミネッセンス素
子。2. An organic electroluminescence device having at least a light emitting layer between a pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or semitransparent, wherein the light emitting layer is represented by the following formula: (Here, Ar represents a repeating unit, and is selected from at least one alkyl, alkoxy and alkylthio group having 1 to 22 carbon atoms and an aromatic hydrocarbon group having 6 to 22 carbon atoms in an aromatic ring or an aromatic heterocycle. An arylene group or an aromatic heterocyclic compound group having a substituted substituent, and the aromatic ring or the aromatic heterocyclic ring has a continuous π with the aromatic ring or the aromatic heterocyclic ring of adjacent repeating units. It forms an electron-conjugated system, n is an integer of 5 or more.), Has a structure represented by, and is made of a conjugated polymer that is soluble in an organic solvent, and is composed of a cathode and the light-emitting layer. Between,
An organic electroluminescence device comprising a layer made of an electron transporting compound adjacent to the light emitting layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10648393A JP3362440B2 (en) | 1992-06-24 | 1993-05-07 | Organic electroluminescence device |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-165961 | 1992-06-24 | ||
| JP16596192 | 1992-06-24 | ||
| JP10648393A JP3362440B2 (en) | 1992-06-24 | 1993-05-07 | Organic electroluminescence device |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002178161A Division JP3656618B2 (en) | 1992-06-24 | 2002-06-19 | Organic electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0673374A true JPH0673374A (en) | 1994-03-15 |
| JP3362440B2 JP3362440B2 (en) | 2003-01-07 |
Family
ID=26446600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10648393A Expired - Lifetime JP3362440B2 (en) | 1992-06-24 | 1993-05-07 | Organic electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3362440B2 (en) |
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| JP2004503640A (en) * | 2000-06-12 | 2004-02-05 | マックスデム インコーポレイテッド | Polymer matrix electroluminescent materials and devices |
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