JPH05247460A - Organic electroluminescent device - Google Patents
Organic electroluminescent deviceInfo
- Publication number
- JPH05247460A JPH05247460A JP4300903A JP30090392A JPH05247460A JP H05247460 A JPH05247460 A JP H05247460A JP 4300903 A JP4300903 A JP 4300903A JP 30090392 A JP30090392 A JP 30090392A JP H05247460 A JPH05247460 A JP H05247460A
- Authority
- JP
- Japan
- Prior art keywords
- group
- poly
- light emitting
- phenylene vinylene
- emitting layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Luminescent Compositions (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electroluminescent Light Sources (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、置換ポリ（ｐ−フェニレンビニレン）を発光
材料として用いた有機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, it relates to an organic EL element using substituted poly (p-phenylene vinylene) as a 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は発光させるのに高電圧が必要であ
った。最近、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ＥＬ素子を実現させた（特開昭５
９−１９４３９３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．Ａｐ
ｐｌ．Ｐｈｙｓ．）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、高分子量の発光材料と
しては、ＷＯ９０１３１４８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、１９
８２頁（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 devices require a high voltage to emit light. Recently, Tang et al. Used an organic fluorescent dye as a light emitting layer,
An organic EL device having a two-layer structure in which organic charge transporting compounds used in electrophotographic photoreceptors and the like are laminated is manufactured, and is driven at a lower voltage as compared with one having only a light emitting layer.
A highly efficient and high-luminance organic EL device has been realized (Japanese Patent Laid-Open No. Sho 5)
9-194393). Compared to 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. Therefore, many of the element structures, organic fluorescent dyes, and organic charge transport compounds are used. Attempts have been reported [Japanese Journal of Applied Physics (Jpn. J. Appl.
Phys. ) 27, L269 (1988)], [Journal of Applied Physics (J. Ap.
pl. Phys. ) 65, 3610 (1989)
]. So far, a low molecular weight organic fluorescent dye has been generally used as a light emitting material, and a high molecular weight light emitting material has been disclosed in WO 9013148, Japanese Patent Laid-Open No. 3-130148.
126787, Applied Physics Letters (Appl. Phys. Lett.) Volume 58, 19
It was only proposed on page 82 (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 devices using the polymer light emitting materials that have been reported so far have 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 a higher brightness while taking advantage of those advantages. Is required.
【０００４】本発明の目的は高分子発光材料を発光層と
した低電圧駆動、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-luminance organic EL device having a polymer light emitting material as a light emitting layer.
【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、置換ポリ−ｐ−フェニレンビニレンを用
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 earnestly studied for 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, a substituted poly-p-phenylene vinylene is used as the polymer light emitting material, and a material obtained by adding an electron transporting compound to this is used as the light emitting layer, or a high-molecular weight material is provided between the polymer light emitting layer and the cathode. It was found that by forming a layer of an electron transporting compound adjacent to the molecular light emitting layer, lower voltage driving and higher brightness can be realized as compared with the case where a polymer light emitting material is used alone. Invented.
【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、該発光層が下記化２That is, the present invention provides an organic electroluminescence device having at least a light emitting layer between a pair of electrodes consisting of a pair 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 chemical formula 2.
【０００７】[0007]
【化２】 （式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 はそれぞれ独立に水
素，炭素数１〜２０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６〜２０の芳香族炭化水
素基から選ばれた基を示し、且つ少なくとも一つが炭素
数４〜２０のアルキル基、アルコキシ基またはアルキル
チオ基であり、ｎは５以上の数を表す。）で表される置
換ポリ（ｐ−フェニレンビニレン）と電子輸送性化合物
を含むこと、あるいは該発光層が上記化２で表される置
換ポリ（ｐ−フェニレンビニレン）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
の層を設けることを特徴とする有機ＥＬ素子を提供する
ことにある。[Chemical 2] (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. And at least one is an alkyl group, an alkoxy group or an alkylthio group having 4 to 20 carbon atoms, and n represents a number of 5 or more.), And a substituted poly (p-phenylene vinylene) and an electron. An electron transporting compound containing a transporting compound, or the light emitting layer consisting of a substituted poly (p-phenylene vinylene) represented by the above chemical formula 2, and being adjacent to the light emitting layer between the light emitting layer and the cathode. Another object of the present invention is to provide an organic EL device characterized in that the above layer is provided.
【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上記化２で表わされる
置換ポリ（ｐ−フェニレンビニレン）は溶剤に可溶性の
ものである。ここで、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 はそれぞ
れ独立に水素，炭素数１〜２０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６〜２０の芳
香族炭化水素基から選ばれた基を示し、且つ可溶性を与
えるには、少なくともそれらの一つが炭素数４〜２０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
ことが必要である。これらのなかで成膜性が良好なアル
キル基、アルコキシ基が特に好ましい。ここで、炭素数
１〜２０のアルキル基としては、例えば、メチル基、エ
チル基、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、２−エチル−
ヘキシル基、３−メチル−ブチル基、イソプロピル基な
どであり、ペンチル基、ヘキシル基、ヘプチル基、オク
チル基、デシル基、２−エチル−ヘキシル基、３−メチ
ル−ブチル基が好ましい。または炭素数１〜２０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、デシルオキシ基、ラウリル
オキシ基、２−エチル−ヘキシルオキシ基、３−メチル
−ブトキシ基、イソプルピ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、
オクチルオキシ基、デシルオキシ基、２−エチル−ヘキ
シルオキシ基、３−メチル−ブトキシ基が好ましい。ア
ルキルチオ基としては、メチルチオ基、エチルチオ基、
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、デシルチオ基、ラウリル
チオ基、２−エチル−ヘキシルチオ基、３−メチル−ブ
チルチオ基、イソプルピ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、オクチルチ
オ基、デシルチオ基、２−エチル−ヘキシルチオ基、３
−メチル−ブ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、４-
アルキルフェニル基、１−ナフタレン基、２−ナフタレ
ン基が例示される。The organic EL device of the present invention will be described in detail below. The substituted poly (p-phenylene vinylene) represented by the above chemical formula 2 used in the present invention is soluble in a solvent. Here, R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. At least one of them must be an alkyl group having 4 to 20 carbon atoms, an alkoxy group or an alkylthio group in order to represent a group and to impart solubility. Of these, an alkyl group and an alkoxy group, which have good film-forming properties, are particularly preferable. Here, as the alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, lauryl group, 2-ethyl-
It is a hexyl group, a 3-methyl-butyl group, an isopropyl group or the like, and a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a 2-ethyl-hexyl group and a 3-methyl-butyl group are preferable. Or, as the alkoxy group having 1 to 20 carbon atoms, a methoxy group, an ethoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a lauryloxy group, and a 2-ethyl-hexyloxy group. Group, 3-methyl-butoxy group, isopropyl group, etc., such as pentyloxy group, hexyloxy group, heptyloxy group,
An octyloxy group, a decyloxy group, a 2-ethyl-hexyloxy group and a 3-methyl-butoxy group are preferable. As the alkylthio group, a methylthio group, an ethylthio group,
A butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a decylthio group, a laurylthio group, a 2-ethyl-hexylthio group, a 3-methyl-butylthio group, an isopropyl group, a pentylthio group, a hexylthio group, a heptylthio group, Octylthio group, decylthio group, 2-ethyl-hexylthio group, 3
The -methyl-butylthio group is preferred. As the aromatic hydrocarbon group, a phenyl group, 4-alkoxyphenyl group, 4-
Examples thereof include an alkylphenyl group, a 1-naphthalene group and a 2-naphthalene group.
【０００９】具体的な置換ポリ（ｐ−フェニレンビニレ
ン）としては、ポリ（２，５−ジペンチル−ｐ−フェニ
レンビニレン）、ポリ（２，５−ジヘキシル−ｐ−フェ
ニレンビニレン）、ポリ（２，５−ジヘプチル−ｐ−フ
ェニレンビニレン）、ポリ（２，５−ジオクチル−ｐ−
フェニレンビニレン）、ポリ（２，５−ジデシル−ｐ−
フェニレンビニレン）、ポリ（２，５−ジペンチルオキ
シ−ｐ−フェニレンビニレン）、ポリ（２，５−ジヘキ
シルオキシ−ｐ−フェニレンビニレン）、ポリ（２，５
−ジヘプチルオキシ−ｐ−フェニレンビニレン）、ポリ
（２，５−ジオクチルオキシ−ｐ−フェニレンビニレ
ン）、ポリ（２，５−ジデシルオキシ−ｐ−フェニレン
ビニレン）、ポリ（２，５−ジペンチルチオ−ｐ−フェ
ニレンビニレン）、ポリ（２，５−ジヘキシルチオ−ｐ
−フェニレンビニレン）、ポリ（２，５−ジヘプチルチ
オ−ｐ−フェニレンビニレン）、ポリ（２−メトキシ−
５−ヘプチルオキシ−ｐ−フェニレンビニレン）、ポリ
（２−メトキシ−５−ラウリルオキシ−ｐ−フェニレン
ビニレン）、ポリ（２−メトキシ−５−（２’−エチル
−ヘキシルオキシ）−ｐ−フェニレンビニレン）、ポリ
（２−メトキシ−５−ヘプチルチオ−ｐ−フェニレンビ
ニレン）、ポリ（２−メトキシ−５−ラウリルチオ−ｐ
−フェニレンビニレン）、ポリ（２−メトキシ−５−
（３’−メチル−ブトキシ）−ｐ−フェニレンビニレ
ン）などが例示される。これらの中で、ポリ（２，５−
ジペンチル−ｐ−フェニレンビニレン）、ポリ（２，５
−ジヘキシル−ｐ−フェニレンビニレン）、ポリ（２，
５−ジヘプチル−ｐ−フェニレンビニレン）、ポリ
（２，５−ジオクチル−ｐ−フェニレンビニレン）、ポ
リ（２，５−ジペンチルオキシ−ｐ−フェニレンビニレ
ン）、ポリ（２，５−ジヘキシルオキシ−ｐ−フェニレ
ンビニレン）、ポリ（２，５−ジヘプチルオキシ−ｐ−
フェニレンビニレン）、ポリ（２，５−ジオクチルオキ
シ−ｐ−フェニレンビニレン）、ポリ（２，５−ジデシ
ルオキシ−ｐ−フェニレンビニレン）、ポリ（２−メト
キシ−５−ヘキシルオキシ−ｐ−フェニレンビニレ
ン）、ポリ（２−メトキシ−５−（３’−メチル−ブト
キシ）−ｐ−フェニレンビニレン）が好ましい。これら
の置換ポリ（ｐ−フェニレンビニレン）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。Specific examples of the substituted poly (p-phenylene vinylene) include poly (2,5-dipentyl-p-phenylene vinylene), poly (2,5-dihexyl-p-phenylene vinylene) and poly (2,5). -Diheptyl-p-phenylene vinylene), poly (2,5-dioctyl-p-
Phenylene vinylene), poly (2,5-didecyl-p-
Phenylene vinylene), poly (2,5-dipentyloxy-p-phenylene vinylene), poly (2,5-dihexyloxy-p-phenylene vinylene), poly (2,5
-Diheptyloxy-p-phenylene vinylene), poly (2,5-dioctyloxy-p-phenylene vinylene), poly (2,5-didecyloxy-p-phenylene vinylene), poly (2,5-dipentylthio-p) -Phenylene vinylene), poly (2,5-dihexylthio-p
-Phenylene vinylene), poly (2,5-diheptylthio-p-phenylene vinylene), poly (2-methoxy-
5-heptyloxy-p-phenylene vinylene), poly (2-methoxy-5-lauryloxy-p-phenylene vinylene), poly (2-methoxy-5- (2'-ethyl-hexyloxy) -p-phenylene vinylene) ), Poly (2-methoxy-5-heptylthio-p-phenylenevinylene), poly (2-methoxy-5-laurylthio-p)
-Phenylene vinylene), poly (2-methoxy-5-
(3'-methyl-butoxy) -p-phenylene vinylene) and the like. Among these, poly (2,5-
Dipentyl-p-phenylene vinylene), poly (2,5
-Dihexyl-p-phenylene vinylene), poly (2,
5-diheptyl-p-phenylene vinylene), poly (2,5-dioctyl-p-phenylene vinylene), poly (2,5-dipentyloxy-p-phenylene vinylene), poly (2,5-dihexyloxy-p-) Phenylene vinylene), poly (2,5-diheptyloxy-p-
Phenylene vinylene), poly (2,5-dioctyloxy-p-phenylene vinylene), poly (2,5-didecyloxy-p-phenylene vinylene), poly (2-methoxy-5-hexyloxy-p-phenylene vinylene), Poly (2-methoxy-5- (3'-methyl-butoxy) -p-phenylene vinylene) is preferred. These substituted poly (p-phenylene vinylenes) may be used alone or in combination of two or more.
【００１０】化２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１０〜３０００
０が好ましく、１０〜１００００がより好ましい。In the chemical formula 2, 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, dissolution will occur. Since it may be difficult to uniformly form a film, the range of n is 10 to 3000.
0 is preferable and 10-10000 is more preferable.
【００１１】これらの有機溶媒可溶性の置換ポリ（ｐ−
フェニレンビニレン）を用いることにより、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。These organic solvent-soluble substituted poly (p-
By using phenylene vinylene), when forming a film from a solution, it is only necessary to remove the solvent by coating this solution and then drying, and the same method can be applied when an electron transporting compound is mixed. It is very advantageous.
【００１２】上記化２で示される置換ポリ（ｐ−フェニ
レンビニレン）の合成法としては特に限定されないが、
例えば特開平１−２５４７３４号公報、特開平１−７９
２１７号公報等に記載されている方法が用いられる。す
なわち、例えば、相当するビス（ハロゲン化メチル）化
合物、より具体的には、例えば、２，５−ジヘプチルオ
キシ−ｐ−キシリレンジブロミドを、キシレン／第三級
ブチルアルコール混合溶媒中、第三級ブトキシカリウム
を用いて重合させる脱ハロゲン化水素法をあげることが
できる。また、相当するホスホニウム塩とアルデヒドと
をリチウムアルコラートを触媒として反応させる方法で
あるＷｉｔｔｉｇ法、相当するスルホニウム塩をアルカ
リ存在下に重合させ、ついで脱スルホニウム塩処理を行
なうスルホニウム塩分解法などが例示される。また、こ
れらの高分子化合物を有機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、クロマトグラフによる分別等の純化処理
をすることが望ましい。The method for synthesizing the substituted poly (p-phenylene vinylene) represented by the above chemical formula 2 is not particularly limited,
For example, JP-A-1-254734 and JP-A-1-79
The method described in Japanese Patent No. 217, etc. is used. That is, for example, a corresponding bis (methyl halide) compound, more specifically, for example, 2,5-diheptyloxy-p-xylylene dibromide, is added to a xylene / tertiary butyl alcohol mixed solvent in a tertiary solvent. An example is a dehydrohalogenation method in which the polymerization is carried out using potassium butoxide. Further, a Wittig method, which is a method of reacting a corresponding phosphonium salt and an aldehyde with a lithium alcoholate as a catalyst, a sulfonium salt decomposition method of polymerizing a corresponding sulfonium salt in the presence of an alkali, and then performing a desulfonium salt treatment are exemplified. . Further, when these polymer compounds are used as a light emitting layer of an organic EL element, the purity thereof affects the light emitting characteristics, and therefore it is desirable to carry out purification treatment such as reprecipitation purification and fractionation by chromatography after the synthesis.
【００１３】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置換ポリ（ｐ−フェニレ
ンビニレン）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、テトラシアノアンス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、フルオレノ
ン系化合物、ジフェノキノン系化合物、８−ヒドロキシ
キノリンおよびその誘導体の金属錯体等が例示される。
具体的には、特開昭６３−７０２５７、同６３−１７５
８６０号公報、特開平２−１３５３６１、同２−１３５
３５９、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、８−ヒドロキシキノリンおよびその誘導体の金
属錯体が好ましく、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、トリス
（８−キノリノール）アルミニウムが好ましい。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。電子輸送性化合物を置換
ポリ（ｐ−フェニレンビニレン）に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、混合する割合は長
鎖基置換ポリ（ｐ−フェニレンビニレン）に対して１〜
４０ｗｔ％が好ましく、より好ましくは２〜３０ｗｔ％
である。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 substituted poly (p-phenylene vinylene) used as a light emitting material. For example, an oxadiazole compound, Examples include benzoquinone compounds, naphthoquinone compounds, anthraquinone compounds, tetracyanoanthraquinodimethane compounds, diphenyldicyanoethylene compounds, fluorenone compounds, diphenoquinone compounds, metal complexes of 8-hydroxyquinoline and its derivatives. ..
Specifically, JP-A-63-70257 and 63-175.
860, JP-A-2-135361 and JP-A-2-135
Known compounds such as those described in JP-A No. 359 and 3-152184 can be used. Metal complexes of oxadiazole compounds, benzoquinone compounds, anthraquinone compounds, 8-hydroxyquinoline and their derivatives. Is preferred, especially 2- (4-biphenylyl)-
5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone and tris (8-quinolinol) aluminum are preferred. These electron transporting compounds may be used alone or in combination of two or more. When the electron-transporting compound is mixed with the substituted poly (p-phenylene vinylene) and used, if the amount is too small, the effect is small, and if it is too large, the current that does not contribute to light emission increases. , Characteristics such as brightness are deteriorated. Depending on the molecular weight of the electron-transporting compound used, the mixing ratio is 1 to the long-chain group-substituted poly (p-phenylene vinylene).
40 wt% is preferable, and more preferably 2 to 30 wt%
Is.
【００１４】本発明においては、化２で示される置換ポ
リ（ｐ−フェニレンビニレン）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５
９−１９４３９３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。The present invention also includes the use of a substituted poly (p-phenylene vinylene) represented by Chemical Formula 2 in which a known light emitting material is dispersed as a light emitting layer. The light emitting material is not particularly limited, and examples thereof include naphthalene derivatives, anthracene and its derivatives, perylene and its derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based dyes, 8-hydroxyquinoline and its metal complexes. , Aromatic amine, tetraphenylcyclopentadiene and its derivative, tetraphenylbutadiene and its derivative and the like can be used. Specifically, for example, JP-A-57-51781 and 5
Known materials such as those described in JP-A-9-194393 can be used.
【００１５】本発明の有機ＥＬ素子の構造について以下
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 structure of the organic EL device of the present invention will be described below. A pair of electrodes consisting of an anode and a cathode. As a transparent or semitransparent electrode, a transparent or semitransparent electrode formed on a transparent substrate such as glass or transparent plastic is used. 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 or the like is used. As a manufacturing method, a vacuum deposition method, a sputtering method,
A plating method or the like is used.
【００１６】次いで、この陽極上に置換ポリ（ｐ−フェ
ニレンビニレン）と電子輸送性化合物を含む発光層を形
成する。成膜方法としてはこれら材料の混合液を使用し
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、ロールコート法等の塗布法また
は真空蒸着法が例示されるが、混合溶液をスピンコーテ
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、ロールコート法等の塗布法により成膜するのが
特に好ましい。Next, a light emitting layer containing a substituted poly (p-phenylene vinylene) and an electron transporting compound is formed on this anode. Examples of the film forming method include 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 vacuum deposition method using a mixed solution of these materials. It is particularly preferable to form the film by a coating method such as a coating method, a casting method, a dipping method, a bar coating method, or a roll coating method.
【００１７】発光層の膜厚としては５Å〜１０μｍ、好
ましくは１０Å〜１μｍである。電流密度を上げて発光
効率を上げるためには１００〜５０００Å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、室温以
上で材料の分解温度以下、具体的には３０〜３３０℃、
好ましくは６０〜３００℃、さらに好ましくは１００〜
２５０℃の温度で熱処理することが望ましい。熱処理す
る時間としては、溶媒を除去するためには少なくとも１
０分以上処理することが好ましく、実用的には１〜２４
時間がより好ましい。The thickness of the light emitting layer is 5Å to 10 μm, preferably 10Å to 1 μm. In order to increase the current density and luminous efficiency, the range of 100 to 5000 Å 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, at room temperature or higher and below the decomposition temperature of the material, specifically 30 to 330 ° C.
Preferably 60 to 300 ° C., more preferably 100 to
Heat treatment at a temperature of 250 ° C. is desirable. The heat treatment time should be at least 1 to remove the solvent.
Treatment for 0 minutes or more is preferable, and practically 1 to 24
Time is more preferred.
【００１８】また、別の態様である発光層が電子輸送性
化合物を含まない場合には上記の成膜方法で発光層を設
け、その上に電子輸送層を形成する。電子輸送層の材料
としては前述の電子輸送性化合物が用いられる。In another embodiment, when the light emitting layer does not contain an electron transporting compound, the light emitting layer is provided by the above film forming method, and the electron transporting layer is formed thereon. As the material of the electron transport layer, the above-mentioned electron transport compound is used.
【００１９】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、粉末状態からの真空蒸着法、あるい
は溶媒に溶かした後の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
ト法等の塗布法、あるいは上記化２の長鎖基置換ポリ
（ｐ−フェニレンビニレン）またはそれとは別の高分子
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
で混合し分散させた後の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
ート法等の塗布法を用いることができる。混合する高分
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、上記
化２の長鎖基置換ポリ（ｐ−フェニレンビニレン）、ポ
リ（ｐ−フェニレンビニレン）、ポリ（２，５−ジメト
キシ−ｐ−フェニレンビニレン）、ポリ（２，５−ジメ
チル−ｐ−フェニレンビニレン）、ポリチオフェン及び
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、ポリ塩化ビ
ニル、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。The film forming method of the electron transporting compound is not particularly limited, but it is a vacuum deposition method from a powder state, or a spin coating method after casting in a solvent, a casting method, a dipping method, a bar coating method, a roll coating method. Or a coating method such as the above long-chain group-substituted poly (p-phenylene vinylene) or a polymer compound other than it and an electron transporting compound are mixed in a solution state or a molten state and dispersed. A coating method such as a spin coating method, a casting method, a dipping method, a bar coating method or a roll coating method can be used. The 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 (p-phenylene vinylene), poly (p-phenylene vinylene), poly (2,5-dimethoxy-p-phenylene vinylene), poly (2,5-dimethyl-p- Phenylene vinylene), polythiophene and its derivatives, poly (2,5-thienylene vinylene) and its derivatives, polycarbonate, polymethacrylate,
Examples include polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like. The coating method is preferably used in terms of easy film formation.
【００２０】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５Å〜１０
μｍ、好ましくは１０Å〜１μｍ、さらに好ましくは５
０〜２０００Åである。The thickness of the electron transport layer is required 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 5Å to 10
μm, preferably 10Å to 1 μm, more preferably 5
It is 0 to 2000Å.
【００２１】次いで、発光層が置換ポリ（ｐ−フェニレ
ンビニレン）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とＡｇの合金（Ｍｇ−Ａｇ
合金と記載することがある）、Ｉｎ−Ａｇ合金、Ｍｇ−
Ｉｎ合金、グラファイト薄膜等が用いられる。これらの
中ではＭｇとＡｇの合金が好ましい。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 substituted poly (p-phenylene vinylene) and an electron transporting compound, it is on this layer, and when the light emitting layer and the electron transporting layer are laminated, electron transporting is carried out. An electrode is provided on the layer. 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, and an alloy of Mg and Ag (Mg-Ag
Alloy)), In-Ag alloy, Mg-
In alloy, graphite thin film, etc. are used. Among these, an alloy of Mg and Ag is preferable. As a method for producing the cathode, known methods such as a vacuum vapor deposition method and a sputtering method are used.
【００２２】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／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、陽極と発光層の間、または陰極と電子
輸送層との間に高分子化合物のバッファー層を有する組
み合わせの構造、すなわち陽極／バッファー層／発光層
／陰極、陽極／バッファー層／発光層／電子輸送層／陰
極、陽極／発光層／バッファー層／陰極、陽極／発光層
／電子輸送層／バッファー層／陰極、陽極／バッファー
層／発光層／バッファー層／陰極、陽極／バッファー層
／発光層／電子輸送層／バッファー層／陰極をとること
もできる。バッファー層に用いる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、ポリチオフェ
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、ポリシラン及びその誘導体などが
例示される。成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。バッファー層の厚みは通常
５Å〜１０μｍ、電流密度を上げて発光効率を上げるた
めには好ましくは１０〜５０００Å、より好ましくは２
０〜１０００Åである。The structure of the EL device of the present invention is as follows.
In addition to the structure of the anode / light-emitting layer / cathode (/ indicates that the layers are laminated) or the structure of the anode / light-emitting layer / electron transport layer / cathode described above, between the anode and the light-emitting layer or between the cathode and the electron transport. Structure of combination having polymer compound buffer layer between layers, ie, anode / buffer layer / light emitting layer / cathode, anode / buffer layer / light emitting layer / electron transport layer / cathode, anode / light emitting layer / buffer layer / Cathode, anode / light emitting layer / electron transport layer / buffer layer / cathode, anode / buffer layer / light emitting layer / buffer layer / cathode, anode / buffer layer / light emitting layer / electron transport layer / buffer layer / cathode .. The polymer compound used for the buffer layer 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. Examples thereof include poly (N-vinylcarbazole), polyaniline and its derivatives, polythiophene and its derivatives, poly (2,5-thienylenevinylene) and its derivatives, polysilane and its derivatives, and the like. The coating method is preferably used from the viewpoint that film formation can be easily performed. The thickness of the buffer layer is usually 5 Å to 10 μm, and preferably 10 to 5,000 Å, more preferably 2 in order to increase the current density and luminous efficiency.
It is 0 to 1000Å.
【００２３】[0023]
【実施例】以下本発明の実施例を示すが、本発明はこれ
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.
【００２４】実施例１ スパッタリングによって、２００Åの厚みでＩＴＯ膜を
付けたガラス基板に、特開平１−７９２１７号公報の実
施例６で２，５−ジヘプチル−ｐ−キシリレンジブロミ
ドの代わりに２，５−ジヘプチルオキシ−ｐ−キシリレ
ンジブロミドを用いて実施例６記載の方法で合成したポ
リ（２，５−ジヘプチルオキシ−ｐ−フェニレンビニレ
ン）〔ゲルパーミエーションクロマトグラフ（ＧＰＣ）
によるポリスチレン換算の数平均重合度約３６０〕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〔ポリ（２，５−ジヘプチルオキシ−ｐ−フェニ
レンビニレン）に対する混合割合は５ｗｔ％〕の０．６
７ｗｔ％トルエン／クロロホルム（３／２重量比）溶液
を用い、スピンコートにより８００Å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、Ｉｎを３０００Å蒸着して、有機
ＥＬ素子を作製した。蒸着のときの真空度は３×１０-6
Ｔｏｒｒ以下であった。この素子に電圧１９．４Ｖを印
加したところ、電流密度２７５ｍＡ／ｃｍ2 の電流が流
れ、輝度１６０．６ｃｄ／ｍ2 のオレンジ色のＥＬ発光
が観察された。また２０ｃｄ／ｍ2 の輝度にするための
電圧は１３．２Ｖであった。Example 1 A glass substrate having an ITO film with a thickness of 200 Å attached by sputtering was replaced with 2,5-diheptyl-p-xylylene dibromide by 2, in Example 6 of JP-A-1-79217. Poly (2,5-diheptyloxy-p-phenylenevinylene) synthesized by the method described in Example 6 using 5-diheptyloxy-p-xylylene dibromide [gel permeation chromatograph (GPC)
Number average degree of polymerization in terms of polystyrene of about 360] and 2- (4-biphenylyl) -5-as an electron transporting compound.
0.6 of (4-t-butylphenyl) -1,3,4-oxadiazole [mixing ratio to poly (2,5-diheptyloxy-p-phenylenevinylene) is 5 wt%]
A 7 wt% toluene / chloroform (3/2 weight ratio) solution was used to form a film with a thickness of 800 Å by spin coating. Then, after drying it under reduced pressure at 60 ° C. for 1 hour,
In addition, 3000 Å of In was vapor-deposited as a cathode to prepare an organic EL device. The degree of vacuum during vapor deposition is 3 × 10 -6
It was below Torr. When a voltage of 19.4 V was applied to this element, a current having a current density of 275 mA / cm 2 was flown, and orange EL light emission with a brightness of 160.6 cd / m 2 was observed. The voltage for achieving a brightness of 20 cd / m 2 was 13.2V.
【００２５】実施例２ ２−（４−ビフェニリル）−５−（４−ｔ−ブチルフェ
ニル）−１，３，４−オキサジアゾールをポリ（２，５
−ジヘプチルオキシ−ｐ−フェニレンビニレン）に対し
て15ｗｔ％とした以外は実施例１と同じ方法で８９０Å
の厚みの発光層を持つ、有機ＥＬ素子を作製した。この
素子に電圧２６．０Ｖを印加したところ、電流密度２１
９ｍＡ／ｃｍ2 の電流が流れ、輝度７１．９ｃｄ／ｍ2
のオレンジ色のＥＬ発光が観察された。また２０ｃｄ／
ｍ2 の輝度にするための電圧は１９．６Ｖであった。Example 2 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole was converted into poly (2,5).
-Diheptyloxy-p-phenylene vinylene) was carried out in the same manner as in Example 1 except that the amount was 890Å.
An organic EL device having a light emitting layer having a thickness of 1 was manufactured. When a voltage of 26.0 V was applied to this element, a current density of 21
A current of 9 mA / cm 2 flows and the brightness is 71.9 cd / m 2.
Orange EL emission was observed. 20 cd /
The voltage for achieving a brightness of m 2 was 19.6V.
【００２６】実施例３ ２−（４−ビフェニリル）−５−（４−ｔ−ブチルフェ
ニル）−１，３，４−オキサジアゾールをポリ（２，５
−ジヘプチルオキシ−ｐ−フェニレンビニレン）に対し
て２．５ｗｔ％とした以外は実施例１と同じ方法で１０
１０Åの厚みの発光層を持つ、有機ＥＬ素子を作製し
た。この素子に電圧１９．４Ｖを印加したところ、電流
密度５６ｍＡ／ｃｍ2 の電流が流れ、輝度４６．８ｃｄ
／ｍ2 のオレンジ色のＥＬ発光が観察された。また２０
ｃｄ／ｍ2 の輝度にするための電圧は１７．５Ｖであっ
た。Example 3 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole was converted into poly (2,5).
-Diheptyloxy-p-phenylene vinylene) was used in the same manner as in Example 1 except that the amount was 2.5 wt%.
An organic EL device having a light emitting layer with a thickness of 10Å was produced. When a voltage of 19.4 V was applied to this element, a current with a current density of 56 mA / cm 2 flowed, and the luminance was 46.8 cd.
An orange EL emission of / m 2 was observed. Again 20
The voltage for achieving a luminance of cd / m 2 was 17.5V.
【００２７】比較例１ ポリ（２，５−ジヘプチルオキシ−ｐ−フェニレンビニ
レン）に２−（４−ビフェニリル）−５−（４−ｔ−ブ
チルフェニル）−１，３，４−オキサジアゾールを混合
しない以外は実施例１と同じ方法で９８０Åの厚みの発
光層を持つ、有機ＥＬ素子を作製した。この素子に電圧
３３．３Ｖを印加したところ、電流密度６１７ｍＡ／ｃ
ｍ2 の電流が流れたが、輝度２６．４ｃｄ／ｍ2 のオレ
ンジ色のＥＬ発光が観察されただけであった。また２０
ｃｄ／ｍ2 の輝度にするための電圧は３２．９Ｖであっ
た。Comparative Example 1 Poly (2,5-diheptyloxy-p-phenylenevinylene) was added to 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole. An organic EL device having a light emitting layer with a thickness of 980Å was produced by the same method as in Example 1 except that the above was not mixed. When a voltage of 33.3 V was applied to this element, the current density was 617 mA / c.
A current of m 2 flowed, but only orange EL emission with a brightness of 26.4 cd / m 2 was observed. Again 20
The voltage for obtaining a brightness of cd / m 2 was 32.9V.
【００２８】実施例４ ポリ（２，５−ジヘプチルオキシ−ｐ−フェニレンビニ
レン）の代わりに、特開平１−７９２１７号公報の実施
例６で２，５−ジヘプチル−ｐ−キシリレンジブロミド
の代わりに２，５−ジヘキシルオキシ−ｐ−キシリレン
ジブロミドを用いて実施例６記載の方法で合成したポリ
（２，５−ジヘキシルオキシ−ｐ−フェニレンビニレ
ン）（ＧＰＣによるポリスチレン換算数平均重合度約１
６０）を用い、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
をポリ（２，５−ジヘキシルオキシ−ｐ−フェニレンビ
ニレン）に対して１０ｗｔ％混合し、溶媒としてクロロ
ホルムを用いた以外は実施例１と同じ方法で１３００Å
の厚みの発光層を持つ、有機ＥＬ素子を作製した。この
素子に電圧２５．０Ｖを印加したところ、電流密度３４
６ｍＡ／ｃｍ2 の電流が流れ、輝度４４．６ｃｄ／ｍ2
のオレンジ色のＥＬ発光が観察された。また２０ｃｄ／
ｍ2 の輝度にするための電圧は２３．５Ｖであった。Example 4 Instead of poly (2,5-diheptyloxy-p-phenylene vinylene), instead of 2,5-diheptyl-p-xylylene dibromide in Example 6 of JP-A-1-79217. Poly (2,5-dihexyloxy-p-phenylene vinylene) synthesized by the method described in Example 6 using 2,5-dihexyloxy-p-xylylene dibromide (polystyrene conversion number average degree of polymerization by GPC of about 1).
60) using 2- (4-biphenylyl) -5- (4-
t-Butylphenyl) -1,3,4-oxadiazole was mixed with poly (2,5-dihexyloxy-p-phenylenevinylene) in an amount of 10 wt% and chloroform was used as a solvent. 1300Å in the same way
An organic EL device having a light emitting layer having a thickness of 1 was manufactured. When a voltage of 25.0 V was applied to this element, a current density of 34
A current of 6 mA / cm 2 flows and the brightness is 44.6 cd / m 2.
Orange EL emission was observed. 20 cd /
The voltage for obtaining a brightness of m 2 was 23.5V.
【００２９】実施例５ ポリ（２，５−ジヘプチルオキシ−ｐ−フェニレンビニ
レン）の代わりに、特開平１−７９２１７号公報の実施
例６で２，５−ジヘプチル−ｐ−キシリレンジブロミド
の代わりに２，５−ジペンチルオキシ−ｐ−キシリレン
ジブロミドを用いて実施例６記載の方法で合成したポリ
（２，５−ジペンチルオキシ−ｐ−フェニレンビニレ
ン）（ＧＰＣによるポリスチレン換算数平均重合度約４
００）を用い、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
をポリ（２，５−ジペンチルオキシ−ｐ−フェニレンビ
ニレン）に対して１０ｗｔ％混合し、溶媒としてクロロ
ホルムを用いた以外は実施例１と同じ方法で１４００Å
の厚みの発光層を持つ、有機ＥＬ素子を作製した。この
素子に電圧２３．３Ｖを印加したところ、電流密度３８
６ｍＡ／ｃｍ2 の電流が流れ、輝度５１．４ｃｄ／ｍ2
のオレンジ色のＥＬ発光が観察された。また２０ｃｄ／
ｍ2 の輝度にするための電圧は２２．５Ｖであった。Example 5 Instead of poly (2,5-diheptyloxy-p-phenylene vinylene), in Example 6 of JP-A-1-79217, instead of 2,5-diheptyl-p-xylylene dibromide Poly (2,5-dipentyloxy-p-phenylene vinylene) synthesized by the method described in Example 6 using 2,5-dipentyloxy-p-xylylene dibromide (polystyrene conversion number average degree of polymerization by GPC of about 4).
00) using 2- (4-biphenylyl) -5- (4-
t-Butylphenyl) -1,3,4-oxadiazole was mixed with poly (2,5-dipentyloxy-p-phenylenevinylene) in an amount of 10 wt% and chloroform was used as a solvent. 1400Å in the same way
An organic EL device having a light emitting layer having a thickness of 1 was manufactured. When a voltage of 23.3 V was applied to this element, a current density of 38
A current of 6 mA / cm 2 flows and the brightness is 51.4 cd / m 2.
Orange EL emission was observed. 20 cd /
The voltage for obtaining a brightness of m 2 was 22.5V.
【００３０】比較例２ ２−（４−ビフェニリル）−５−（４−ｔ−ブチルフェ
ニル）−１，３，４−オキサジアゾールをポリ（２，５
−ジヘプチルオキシ−ｐ−フェニレンビニレン）に対し
て４４．４ｗｔ％混合した以外は実施例１と同じ方法で
２６００Åの厚みの発光層を持つ、有機ＥＬ素子を作製
した。この素子に電圧４０．０Ｖを印加したところ、電
流密度１３６０ｍＡ／ｃｍ2の電流が流れたが、輝度１
３．４ｃｄ／ｍ2 のオレンジ色のＥＬ発光が観察された
だけであった。また電圧を上げると絶縁破壊のため２０
ｃｄ／ｍ2 の輝度にすることができなかった。Comparative Example 2 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole was added to poly (2,5).
-Diheptyloxy-p-phenylene vinylene) was prepared in the same manner as in Example 1 except that 44.4 wt% was mixed with the organic EL device having a light emitting layer having a thickness of 2600 Å. When a voltage of 40.0 V was applied to this element, a current having a current density of 1360 mA / cm 2 flowed, but the brightness was 1
Only an orange EL emission of 3.4 cd / m 2 was observed. Also, if the voltage is increased, insulation breakdown will occur.
It was not possible to obtain a brightness of cd / m 2 .
【００３１】実施例６ スパッタリングによって、２００Åの厚みでＩＴＯ膜を
付けたガラス基板に、実施例１と同様の方法で合成した
ポリ（２，５−ジヘプチルオキシ−ｐ−フェニレンビニ
レン）と電子輸送性化合物としてアントラキノン〔ポリ
（２，５−ジヘプチルオキシ−ｐ−フェニレンビニレン
に対する混合割合は５ｗｔ％〕の０．６７ｗｔ％トルエ
ン／クロロホルム（３／２重量比）溶液を用い、スピン
コートにより１１００Å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、Ｉｎを３０００Å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。この素子に電圧２０．８Ｖを印加したところ、
電流密度１６５．２ｍＡ／ｃｍ 2 の電流が流れ、輝度１
４６ｃｄ／ｍ2 のオレンジ色のＥＬ発光が観察された。
また、２０ｃｄ／ｍ2 の輝度にするための電圧は１６．
８Ｖであった。Example 6 An ITO film having a thickness of 200 Å was formed by sputtering.
It was synthesized on the attached glass substrate in the same manner as in Example 1.
Poly (2,5-diheptyloxy-p-phenylene vinyl
Len) and anthraquinone (poly
(2,5-diheptyloxy-p-phenylene vinylene
The mixing ratio is 5 wt%] of 0.67 wt%
Spin-on / chloroform (3/2 weight ratio) solution
A film having a thickness of 1100Å was formed by coating. Then this
After drying it under reduced pressure at 60 ° C for 1 hour, the cathode and
Then, 3000 Å of In is vapor-deposited to produce an organic EL device.
did. The degree of vacuum during vapor deposition is 3 × 10-6Below Torr
there were. When a voltage of 20.8V was applied to this element,
Current density 165.2 mA / cm 2Current flows, brightness 1
46 cd / m2Orange EL emission was observed.
Also, 20 cd / m2The voltage for making the luminance of 16 is 16.
It was 8V.
【００３２】実施例７ ＩＴＯ膜上にバッファー層としてポリ（２，５−チエニ
レンビニレン）とポリ（ｐ−フェニレンビニレン）の
７：３（重量比）の混合物から成る層をつけた以外は、
発光層、陰極は実施例６と同じ方法で、バッファー層と
発光層の厚さの合計が１５００Åの有機ＥＬ素子を作製
した。ここで、ポリ（２，５−チエニレンビニレン）と
ポリ（ｐ−フェニレンビニレン）の７：３の混合物から
成る層は、特開平１−９２２１号公報の実施例１に記載
の方法で得たポリ（２，５−チエニレンビニレン）（Ｐ
ＴＶ）中間体をＮ，Ｎ−ジメチルホルムアミド（ＤＭ
Ｆ）に溶解してＰＴＶ中間体溶液としたものと、特開昭
５９−１９９７４６号公報の実施例１に記載の方法で合
成したポリ（ｐ−フェニレンビニレン）（ＰＰＶ）中間
体のＢｒ- 塩の水溶液を大量のＮａＢＦ4水溶液に添加
して対イオン（Ｂｒ- ）をＢＦ4 - に交換し、沈澱とし
て回収したＰＰＶ中間体のＢＦ4 - 塩をＤＭＦに溶解し
てＰＰＶ中間体溶液としたものを、熱処理後生成する両
高分子の重量比が７：３となるような割合で混合した溶
液をスピンコートにより成膜し、２００℃で熱処理する
ことにより作成した。この素子に電圧２４．４Ｖを印加
したところ、電流密度７０．８ｍＡ／ｃｍ2の電流が流
れ、輝度１２０ｃｄ／ｍ2 のオレンジ色のＥＬ発光が観
察された。また、２０ｃｄ／ｍ2 の輝度にするための電
圧は１８．２Ｖであった。Example 7 A layer consisting of a mixture of poly (2,5-thienylene vinylene) and poly (p-phenylene vinylene) in a ratio of 7: 3 (weight ratio) was provided as a buffer layer on the ITO film, except that
In the same manner as in Example 6, for the light emitting layer and the cathode, an organic EL device having a total thickness of the buffer layer and the light emitting layer of 1500 Å was prepared. Here, a layer composed of a 7: 3 mixture of poly (2,5-thienylene vinylene) and poly (p-phenylene vinylene) was obtained by the method described in Example 1 of JP-A-1-9221. Poly (2,5-thienylene vinylene) (P
TV) intermediate to N, N-dimethylformamide (DM
F) to obtain a PTV intermediate solution, and a Br - salt of a poly (p-phenylene vinylene) (PPV) intermediate synthesized by the method described in Example 1 of JP-A-59-199746. Was added to a large amount of NaBF 4 aqueous solution to exchange the counter ion (Br − ) for BF 4 −, and the PF 4 − salt of the PPV intermediate recovered as a precipitate was dissolved in DMF to give a PPV intermediate solution. This was prepared by spin-coating a solution prepared by mixing the two polymers in a ratio such that the weight ratio of both polymers produced after the heat treatment was 7: 3, and heat-treating at 200 ° C. When a voltage of 24.4 V was applied to this device, a current having a current density of 70.8 mA / cm 2 flowed, and orange EL light emission with a luminance of 120 cd / m 2 was observed. In addition, the voltage for achieving a brightness of 20 cd / m 2 was 18.2V.
【００３３】実施例８ アントラキノンの代わりにベンゾキノンを混合した以外
は実施例６と同じ方法で６３０Åの厚みの発光層を持
つ、有機ＥＬ素子を作製した。この素子に電圧１８．３
Ｖを印加したところ、電流密度１６３．４ｍＡ／ｃｍ2
の電流が流れ、輝度６３ｃｄ／ｍ2 のオレンジ色のＥＬ
発光が観察された。また、２０ｃｄ／ｍ2の輝度にする
ための電圧は１４．８Ｖであった。Example 8 An organic EL device having a light emitting layer with a thickness of 630 Å was prepared in the same manner as in Example 6 except that benzoquinone was mixed instead of anthraquinone. A voltage of 18.3 is applied to this element.
When V was applied, the current density was 163.4 mA / cm 2
Current flows and the brightness is 63 cd / m 2 orange EL
Luminescence was observed. Further, the voltage for achieving a brightness of 20 cd / m 2 was 14.8V.
【００３４】実施例９ 実施例１と同じ方法でＩＴＯ膜を付けたガラス基板に、
実施例１と同じ方法で合成したポリ（２，５−ジヘプチ
ルオキシ−ｐ−フェニレンビニレン）〔ゲルパーハエー
ションクロマトグラフ（ＧＰＣ）によるポリスチレン換
算の数平均重合度約３６０〕の０．７５ｗｔ％クロロホ
ルム溶液を用い、ディッピングにより成膜した。つい
で、これを減圧下６０℃で１時間乾燥した後、その上に
電子輸送層として、トリス（８−キノリノール）アルミ
ニウムを７００Å蒸着し、ついで陰極として、Ｍｇ−Ａ
ｇ合金（重量比１０：１）を１５００Å、さらにその上
にＡｇを１０００Å蒸着して、有機ＥＬ素子を作製し
た。有機層の厚さは合計９１０Åであった。また、蒸着
のときの真空度はいずれも３×１０-6Ｔｏｒｒ以下であ
った。この素子に電圧１７．８Ｖを印加したところ、電
流密度４２０ｍＡ／ｃｍ2 の電流が流れ、輝度２２９０
ｃｄ／ｍ2 のオレンジ色のＥＬ発光が観察された。発光
スペクトルはポリ（２，５−ジヘプチルオキシ−ｐ−フ
ェニレンビニレン）の蛍光スペクトルと一致した。Example 9 A glass substrate provided with an ITO film in the same manner as in Example 1 was
0.75 wt% of poly (2,5-diheptyloxy-p-phenylene vinylene) synthesized by the same method as in Example 1 [a polystyrene equivalent number average degree of polymerization of about 360 by gel permeation chromatography (GPC)] A chloroform solution was used to form a film by dipping. Then, this was dried under reduced pressure at 60 ° C. for 1 hour, and then 700 Å of tris (8-quinolinol) aluminum was vapor-deposited thereon as an electron transport layer, and then Mg-A was used as a cathode.
1500 g of a g alloy (weight ratio 10: 1) was further deposited on it by 1000 l to prepare an organic EL device. The total thickness of the organic layer was 910Å. The degree of vacuum during vapor deposition was 3 × 10 −6 Torr or less. When a voltage of 17.8 V was applied to this element, a current with a current density of 420 mA / cm 2 flowed, and a luminance of 2290
An orange EL emission of cd / m 2 was observed. The emission spectrum was in agreement with the fluorescence spectrum of poly (2,5-diheptyloxy-p-phenylene vinylene).
【００３５】比較例３ 電子輸送層を設けない以外は、実施例９と同じ方法で有
機ＥＬ素子を作製した。この素子に電圧９．２Ｖを印加
したところ、電流密度５６９ｍＡ／ｃｍ2 の電流が流
れ、輝度１１８９ｃｄ／ｍ2 のオレンジ色のＥＬ発光が
観察された。また、これ以上電圧を上げても輝度は向上
せず、１１．７Ｖで素子の破壊のため発光しなくなっ
た。Comparative Example 3 An organic EL device was manufactured by the same method as in Example 9 except that the electron transport layer was not provided. When a voltage of 9.2 V was applied to this element, a current having a current density of 569 mA / cm 2 was flowed, and orange EL light emission with a luminance of 1189 cd / m 2 was observed. Further, the brightness was not improved even if the voltage was further increased, and the device was destroyed at 11.7 V and no light was emitted.
【００３６】[0036]
【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 conventional devices, 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 (3)
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、該発光層が下記化１ 【化１】 （式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 はそれぞれ独立に水
素，炭素数１〜２０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６〜２０の芳香族炭化水
素基から選ばれた基を示し、且つ少なくとも一つが炭素
数４〜２０のアルキル基、アルコキシ基またはアルキル
チオ基であり、ｎは５以上の数を表す。）で表される置
換ポリ（ｐ−フェニレンビニレン）と電子輸送性化合物
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. In an organic electroluminescence device having at least a light emitting layer between a pair of electrodes consisting of a pair of an anode and a cathode, at least one of which is transparent or semitransparent, the light emitting layer is represented by the following chemical formula 1. (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. And at least one is an alkyl group, an alkoxy group or an alkylthio group having 4 to 20 carbon atoms, and n represents a number of 5 or more.), And a substituted poly (p-phenylene vinylene) and an electron. An organic electroluminescence device comprising a transporting compound.
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、該発光層が化１で表される置換ポリ（ｐ−フェニレ
ンビニレン）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 a substituted poly (p- Phenylene vinylene), and between the cathode and the light emitting layer,
An organic electroluminescence device comprising a layer made of an electron transporting compound adjacent to the light emitting layer.
徴とする請求項１または２記載の有機エレクトロルミネ
ッセンス素子。3. The organic electroluminescence device according to claim 1, wherein the cathode is made of an alloy of Mg and Ag.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30090392A JP3328731B2 (en) | 1991-12-05 | 1992-11-11 | Organic electroluminescence device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32197691 | 1991-12-05 | ||
| JP4-2124 | 1992-01-09 | ||
| JP3-321976 | 1992-01-09 | ||
| JP212492 | 1992-01-09 | ||
| JP30090392A JP3328731B2 (en) | 1991-12-05 | 1992-11-11 | Organic electroluminescence device |
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| JP2002051037A Division JP2002319493A (en) | 1991-12-05 | 2002-02-27 | Organic electroluminescent element |
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Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
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