JP4893173B2 - Composition for organic electroluminescent device and organic electroluminescent device - Google Patents
Composition for organic electroluminescent device and organic electroluminescent device Download PDFInfo
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- JP4893173B2 JP4893173B2 JP2006240526A JP2006240526A JP4893173B2 JP 4893173 B2 JP4893173 B2 JP 4893173B2 JP 2006240526 A JP2006240526 A JP 2006240526A JP 2006240526 A JP2006240526 A JP 2006240526A JP 4893173 B2 JP4893173 B2 JP 4893173B2
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- 125000004432 carbon atom Chemical group C* 0.000 description 22
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- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 5
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- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 5
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Images
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- Electroluminescent Light Sources (AREA)
- Indole Compounds (AREA)
Description
本発明は、発光効率が高く、駆動電圧が低く、耐熱性を含めた駆動安定性に優れる有機電界発光素子を湿式製膜法により容易に製造し得る有機電界発光素子用組成物と、この有機電界発光素子用組成物を用いて形成された有機電界発光素子用薄膜及び有機電界発光素子に関するものである。 The present invention relates to a composition for an organic electroluminescence device capable of easily producing an organic electroluminescence device having high luminous efficiency, low driving voltage, and excellent driving stability including heat resistance by a wet film-forming method, and the organic electroluminescence device. The present invention relates to an organic electroluminescent element thin film and an organic electroluminescent element formed using the electroluminescent element composition.
近年、有機薄膜を用いた電界発光素子(有機電界発光素子)の開発が行われている。有機薄膜の形成方法としては、真空蒸着法と湿式製膜法が挙げられる。このうち、湿式製膜法は真空プロセスが要らず、大面積化が容易で、1つの層(塗布液)に様々な機能をもった複数の材料を混合して入れることが容易である等の利点がある。 In recent years, an electroluminescent element (organic electroluminescent element) using an organic thin film has been developed. Examples of the method for forming the organic thin film include a vacuum deposition method and a wet film forming method. Among these, the wet film-forming method does not require a vacuum process, is easy to increase in area, and can easily mix a plurality of materials having various functions into one layer (coating liquid). There are advantages.
湿式製膜法によって形成された発光層の材料としては、ポリ(p−フェニレンビニレン)誘導体やポリフルオレン誘導体等の高分子材料が主に用いられているが、高分子材料には以下のような問題がある。
・高分子材料は重合度や分子量分布を制御することが困難である。
・連続駆動時に末端残基による劣化が起こる。
・材料自体の高純度化が困難で、不純物を含む。
Polymer materials such as poly (p-phenylene vinylene) derivatives and polyfluorene derivatives are mainly used as the material for the light emitting layer formed by the wet film forming method. There's a problem.
・ It is difficult to control the degree of polymerization and molecular weight distribution of polymer materials.
・ Deterioration due to terminal residues occurs during continuous driving.
・ High purity of the material itself is difficult and contains impurities.
上記問題のために、湿式製膜法による素子は、真空蒸着法による素子に比べて駆動安定性に劣り、一部を除いて実用レベルに至っていないのが現状である。 Due to the above-mentioned problems, an element using a wet film forming method is inferior in driving stability to an element using a vacuum vapor deposition method, and has not reached a practical level except for a part.
以上のような問題を解決する試みとして、特許文献1には高分子化合物ではなく、複数の低分子材料(電荷輸送材料、発光材料)を混合して湿式製膜法により形成した有機薄膜を用いた有機電界発光素子が記載されており、正孔輸送性の電荷輸送材料としては、以下に示す、化合物H−1、H−2が用いられている。 As an attempt to solve the above problems, Patent Document 1 uses an organic thin film formed by a wet film-forming method by mixing a plurality of low-molecular materials (charge transport materials, light-emitting materials), not a polymer compound. The organic electroluminescent elements described above are described, and the following compounds H-1 and H-2 are used as the hole transporting charge transporting material.
また、湿式製膜法により形成された複数の低分子材料からなる有機薄膜を用いた有機電界発光素子において、非特許文献1では、素子の発光効率を高めるために、燐光発光を利用した素子が記載され、電荷輸送材料には、以下に示す化合物H−3、H−4が用いられている。 In addition, in an organic electroluminescence device using an organic thin film made of a plurality of low-molecular materials formed by a wet film forming method, Non-Patent Document 1 discloses a device using phosphorescence emission in order to increase the light emission efficiency of the device. The following compounds H-3 and H-4 are used for the charge transport materials described.
しかしながら、上記化合物H−1、H−2、H−3、H−4は溶媒に対する溶解性が低い。このため、クロロホルム等のハロゲン系溶媒を塗布溶媒に用いる必要があるが、ハロゲン系溶媒は環境負荷が大きく、実用上問題がある。さらに、ハロゲン系溶媒中に含まれる不純物により材料を劣化させる可能性が大きいため、ハロゲン系溶媒を用いた湿式製膜法による素子は駆動安定性が十分でないと考えられる。 However, the compounds H-1, H-2, H-3, and H-4 have low solubility in solvents. For this reason, it is necessary to use a halogen-based solvent such as chloroform as a coating solvent, but the halogen-based solvent has a large environmental load and has a practical problem. Furthermore, since there is a high possibility that the material is deteriorated by impurities contained in the halogen-based solvent, it is considered that the device by the wet film forming method using the halogen-based solvent does not have sufficient driving stability.
また、上記化合物H−1、H−2、H−3、H−4はガラス転移温度が低く、特許文献1及び非特許文献1に開示されている素子は耐熱性が十分でないと考えられる。さらに、上記化合物H−1、H−2、H−3、H−4は非常に結晶化しやすく、湿式製膜法では均一な非晶質膜を得ることが困難である。 Moreover, the said compound H-1, H-2, H-3, H-4 has a low glass transition temperature, and it is thought that the element currently disclosed by patent document 1 and nonpatent literature 1 is not enough in heat resistance. Further, the compounds H-1, H-2, H-3, and H-4 are very easily crystallized, and it is difficult to obtain a uniform amorphous film by the wet film forming method.
また、発光材料として燐光発光材料を用いる場合、化合物H−1は三重項励起準位が低いため、化合物H−1と燐光発光材料を含む組成物を用いて形成された有機電界発光素子の発光効率は低いと考えられる。
本発明は、湿式製膜法により形成された層を有する有機電界発光素子であって、該層が結晶化しにくく、発光効率が高く、駆動電圧が低く、耐熱性を含めた駆動安定性に優れる有機電界発光素子を提供することを課題とする。 The present invention is an organic electroluminescent element having a layer formed by a wet film forming method, and the layer is difficult to crystallize, has high luminous efficiency, low driving voltage, and excellent driving stability including heat resistance. It is an object to provide an organic electroluminescent element.
本発明者らは上記課題を解決すべく鋭意検討した結果、湿式製膜法により有機電界発光素子の発光層及び/又は電荷輸送層を形成するために用いられる組成物中に、ある特定の部分構造を有する化合物を含有させることによって、結晶化しにくい膜を形成でき、発光効率が高く、駆動電圧が低く、耐熱性を含めた駆動安定性に優れる、実用性の高い有機電界発光素子を得ることができることを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific part in the composition used for forming the light emitting layer and / or the charge transport layer of the organic electroluminescent device by a wet film forming method. By including a compound having a structure, it is possible to form a film that is difficult to crystallize, to obtain a highly practical organic electroluminescence device that has high luminous efficiency, low driving voltage, and excellent driving stability including heat resistance. The present invention has been found.
本発明の要旨は、下記式(IA)で表される有機化合物、に存する。
本発明の別の要旨は、下記式(IB)で表される有機化合物、に存する。
本発明の有機電界発光素子用組成物に用いられる、上記一般式(I)で表される部分構造と上記一般式(II)で表される部分構造とを有する化合物は、三重項励起準位が高く、高い耐熱性を有し、溶媒への溶解性に優れる。このため、本発明の有機電界発光素子用組成物を使用することにより、湿式製膜法により、結晶化しにくく、熱安定性に優れ、発光特性にも優れた膜を形成することができる。 The compound having the partial structure represented by the general formula (I) and the partial structure represented by the general formula (II) used in the composition for an organic electroluminescence device of the present invention is a triplet excited level. , High heat resistance, and excellent solubility in a solvent. For this reason, by using the composition for organic electroluminescent elements of the present invention, it is possible to form a film that is hardly crystallized, has excellent thermal stability, and has excellent light emitting characteristics by a wet film forming method.
従って、このような本発明の有機電界発光素子用組成物を用いて形成された層を有する有機電界発光素子は、発光効率が高く、駆動電圧が低く、耐熱性を含めた駆動安定性が高い有機電界発光素子である。 Therefore, an organic electroluminescent element having a layer formed using the composition for organic electroluminescent elements of the present invention has high luminous efficiency, low driving voltage, and high driving stability including heat resistance. It is an organic electroluminescent element.
本発明による有機電界発光素子は、フラットパネル・ディスプレイ(例えばOAコンピュータ用や壁掛けテレビ)、車載表示素子、携帯電話表示や面発光体としての特徴を生かした光源(例えば、複写機の光源、液晶ディスプレイや計器類のバックライト光源)、表示板、標識灯への応用が考えられ、その技術的価値は大きいものである。 The organic electroluminescent device according to the present invention is a flat panel display (for example, for OA computers or wall-mounted televisions), an in-vehicle display device, a light source utilizing characteristics as a mobile phone display or a surface light emitter (for example, a light source of a copying machine, a liquid crystal). It can be applied to backlight sources for displays and instruments, display panels, and indicator lights, and its technical value is great.
以下に本発明の有機電界発光素子用組成物、有機電界発光素子用薄膜及び有機電界発光素子の実施の形態を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例(代表例)であり、本発明はその要旨を超えない限り、これらの内容に特定されない。 Hereinafter, embodiments of the composition for organic electroluminescent elements, the thin film for organic electroluminescent elements, and the organic electroluminescent element of the present invention will be described in detail. However, the description of the constituent elements described below is an embodiment of the present invention. The present invention is not specified by these contents unless it exceeds the gist.
〔有機電界発光素子用組成物〕
[電荷輸送材料]
本発明の有機電界発光素子用組成物は、一分子内に部分構造として、下記一般式(I)で表される部分構造(以下「部分構造(I)」と称す場合がある。)と下記一般式(II)で表される部分構造(以下「部分構造(II)」と称す場合がある。)とを有する化合物を、電荷輸送材料として含有することを特徴とする。
[Composition for organic electroluminescence device]
[Charge transport material]
The composition for organic electroluminescent elements of the present invention has a partial structure represented by the following general formula (I) as a partial structure in one molecule (hereinafter sometimes referred to as “partial structure (I)”) and the following. A compound having a partial structure represented by the general formula (II) (hereinafter sometimes referred to as “partial structure (II)”) is contained as a charge transporting material.
[1]構造上の特徴
本発明の有機電界発光素子用組成物に含有される電荷輸送材料(以下、適宜、本発明の電荷輸送材料と呼ぶ)は、N−フェニルカルバゾール構造(部分構造(I))とトリフェニルアミン構造(部分構造(II))とを有するため、優れた電荷(正孔)輸送能を有し、三重項励起準位が高く、高い耐熱性を有し、溶媒への溶解性に優れる。
[1] Structural Features The charge transport material contained in the composition for organic electroluminescent elements of the present invention (hereinafter, appropriately referred to as the charge transport material of the present invention) has an N-phenylcarbazole structure (partial structure (I )) And triphenylamine structure (partial structure (II)), has excellent charge (hole) transport ability, high triplet excitation level, high heat resistance, Excellent solubility.
本発明の電荷輸送材料は、部分構造として、1又は2以上の部分構造(I)と、1又は2以上の部分構造(II)を有する。
より高い耐熱性を有する点で、一分子内に部分構造(I)を2以上有することが好ましい。また、より優れた電荷(正孔)輸送能を有する点で、一分子内に部分構造(II)を2以上有することが好ましい。
本発明の電荷輸送材料は、電荷輸送能及び耐熱性の点から、一分子内の各部分構造の数の比が、部分構造(I):部分構造(II)=1:3〜3:1であることが好ましい。
The charge transport material of the present invention has one or more partial structures (I) and one or more partial structures (II) as partial structures.
It is preferable to have two or more partial structures (I) in one molecule from the viewpoint of higher heat resistance. In addition, it is preferable to have two or more partial structures (II) in one molecule from the viewpoint of more excellent charge (hole) transport ability.
In the charge transport material of the present invention, the ratio of the number of each partial structure in one molecule is partial structure (I): partial structure (II) = 1: 3 to 3: 1 from the viewpoint of charge transport ability and heat resistance. It is preferable that
なお、本発明の有機電界発光素子用組成物は、部分構造(I)と部分構造(II)とが必ずしも独立して存在する必要はない。分子内において、前記一般式(I)の環A〜環Cが、前記一般式(II)の環D〜環Fのいずれかを兼ねても良い。例えば、1つのベンゼン環が環Cと環Dを兼ねても良い。また、下記詳述する、一般式(III)の環G〜I、一般式(IV),(IVa)も同様である。 In the composition for organic electroluminescent elements of the present invention, the partial structure (I) and the partial structure (II) are not necessarily present independently. In the molecule, ring A to ring C in the general formula (I) may also serve as any of the ring D to ring F in the general formula (II). For example, one benzene ring may serve as both ring C and ring D. The same applies to the rings G to I and the general formulas (IV) and (IVa) in the general formula (III) described below.
[2]分子量範囲
本発明の電荷輸送材料の分子量は、通常5000以下、好ましくは4000以下、より好ましくは3000以下であり、また通常400以上、好ましくは500以上、より好ましくは600以上である。
分子量がこの上限値を超えると、不純物の高分子量化によって精製が困難となる場合があり、また分子量がこの下限値を下回ると、ガラス転移温度及び、融点、気化温度などが低下するため、耐熱性が著しく損なわれるおそれがある。
[2] Molecular Weight Range The molecular weight of the charge transport material of the present invention is usually 5000 or less, preferably 4000 or less, more preferably 3000 or less, and usually 400 or more, preferably 500 or more, more preferably 600 or more.
If the molecular weight exceeds this upper limit, purification may be difficult due to the high molecular weight of impurities, and if the molecular weight falls below this lower limit, the glass transition temperature, melting point, vaporization temperature, etc. will decrease. There is a risk that the properties are significantly impaired.
[3]物性
本発明の電荷輸送材料は、通常50℃以上のガラス転移温度を有するが、耐熱性の観点から、ガラス転移温度は80℃以上であることが好ましく、110℃以上であることがさらに好ましい。ガラス転移温度の上限は通常400℃程度である。
本発明の電荷輸送材料は、通常300℃以上、800℃以下の気化温度を有する。
本発明の電荷輸送材料は、ガラス転移温度と気化温度の間に結晶化温度を有さないことが好ましい。
[3] Physical Properties Although the charge transport material of the present invention usually has a glass transition temperature of 50 ° C. or higher, from the viewpoint of heat resistance, the glass transition temperature is preferably 80 ° C. or higher, and preferably 110 ° C. or higher. Further preferred. The upper limit of the glass transition temperature is usually about 400 ° C.
The charge transport material of the present invention usually has a vaporization temperature of 300 ° C. or higher and 800 ° C. or lower.
The charge transport material of the present invention preferably has no crystallization temperature between the glass transition temperature and the vaporization temperature.
[4]環A〜環F
前記一般式(I),(II)における環A〜環Fは各々独立に、任意の置換基を有していてもよいベンゼン環を表す。
環A〜環Fのベンゼン環が有していてもよい任意の置換基として具体的には、次のようなものが挙げられる。
[4] Ring A to Ring F
Rings A to F in the general formulas (I) and (II) each independently represent a benzene ring optionally having an arbitrary substituent.
Specific examples of the optional substituent that the ring A to ring F benzene ring may have include the following.
置換基を有していてもよいアルキル基(好ましくは、炭素数1〜8の直鎖又は分岐のアルキル基であり、例えばメチル、エチル、n−プロピル、2−プロピル、n−ブチル、イソブチル、tert−ブチル基などが挙げられる。)
置換基を有していてもよいアルケニル基(好ましくは、炭素数2〜9のアルケニル基であり、例えばビニル、アリル、1−ブテニル基などが挙げられる。)
置換基を有していてもよいアルキニル基(好ましくは、炭素数2〜9のアルキニル基であり、例えばエチニル、プロパルギル基などが挙げられる。)
置換基を有していてもよいアラルキル基(好ましくは、炭素数7〜15のアラルキル基であり、例えばベンジル基などが挙げられる。)
置換基を有していてもよいアミノ基[好ましくは、置換基を有していてもよい炭素数1〜8のアルキル基を1つ以上有するアルキルアミノ基(例えばメチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ基などが挙げられる。)
置換基を有していてもよい炭素数6〜12の芳香族炭化水素基を有するアリールアミノ基(例えばフェニルアミノ、ジフェニルアミノ、ジトリルアミノ基などが挙げられる。)
置換基を有していてもよい、5又は6員環の芳香族複素環を有するヘテロアリールアミノ基(例えばピリジルアミノ、チエニルアミノ、ジチエニルアミノ基などが挙げられる。)
置換基を有していてもよい、炭素数2〜10のアシル基を有するアシルアミノ基(例えばアセチルアミノ、ベンゾイルアミノ基などが挙げられる。)]
置換基を有していてもよいアルコキシ基(好ましくは、置換基を有していてもよい炭素数1〜8のアルコキシ基であり、例えばメトキシ、エトキシ、ブトキシ基などが挙げられる。)
置換基を有していてもよいアリールオキシ基(好ましくは、炭素数6〜12の芳香族炭化水素基を有するものであり、例えばフェニルオキシ、1−ナフチルオキシ、2−ナフチルオキシ基などが挙げられる。)
置換基を有していてもよいヘテロアリールオキシ基(好ましくは、5又は6員環の芳香族複素環基を有するものであり、例えばピリジルオキシ、チエニルオキシ基などが挙げられる。)
置換基を有していてもよいアシル基(好ましくは、置換基を有していてもよい炭素数2〜10のアシル基であり、例えばホルミル、アセチル、ベンゾイル基などが挙げられる。)
置換基を有していてもよいアルコキシカルボニル基(好ましくは、置換基を有していてもよい炭素数2〜10のアルコキシカルボニル基であり、例えばメトキシカルボニル、エトキシカルボニル基などが挙げられる。)
置換基を有していてもよいアリールオキシカルボニル基(好ましくは、置換基を有していてもよい炭素数7〜13のアリールオキシカルボニル基であり、例えばフェノキシカルボニル基などが挙げられる。)
置換基を有していてもよいアルキルカルボニルオキシ基(好ましくは、置換基を有していてもよい炭素数2〜10のアルキルカルボニルオキシ基であり、例えばアセトキシ基などが挙げられる。)
ハロゲン原子(好ましくは、フッ素原子又は塩素原子が挙げられる。)
カルボキシ基
シアノ基
水酸基
メルカプト基
置換基を有していてもよいアルキルチオ基(好ましくは、炭素数1〜8のアルキルチオ基であり、例えばメチルチオ基、エチルチオ基などが挙げられる。)
置換基を有していてもよいアリールチオ基(好ましくは、炭素数6〜12のアリールチオ基であり、例えばフェニルチオ基、1−ナフチルチオ基などが挙げられる。)
置換基を有していてもよいスルホニル基(例えばメシル基、トシル基などが挙げられる。)
置換基を有していてもよいシリル基(例えばトリメチルシリル基、トリフェニルシリル基などが挙げられる。)
置換基を有していてもよいボリル基(例えばジメシチルボリル基などが挙げられる。)
置換基を有していてもよいホスフィノ基(例えばジフェニルホスフィノ基などが挙げられる。)
置換基を有していてもよい芳香族炭化水素基(例えばベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、フルオランテン環などの、5又は6員環の単環又は2〜5縮合環由来の1価の基が挙げられる。)
置換基を有していてもよい芳香族複素環基(例えばフラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環などの、5又は6員環の単環又は2〜4縮合環由来の1価の基が挙げられる。)
An alkyl group which may have a substituent (preferably a linear or branched alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, and a tert-butyl group.)
An alkenyl group which may have a substituent (preferably an alkenyl group having 2 to 9 carbon atoms, such as vinyl, allyl, 1-butenyl group, etc.).
An alkynyl group which may have a substituent (preferably an alkynyl group having 2 to 9 carbon atoms, such as ethynyl and propargyl groups).
An aralkyl group which may have a substituent (preferably an aralkyl group having 7 to 15 carbon atoms, such as a benzyl group).
An optionally substituted amino group [preferably an alkylamino group having one or more optionally substituted alkyl groups having 1 to 8 carbon atoms (for example, methylamino, dimethylamino, diethylamino, And dibenzylamino group.)
An arylamino group having an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent (for example, phenylamino, diphenylamino, ditolylamino group, etc.).
A heteroarylamino group having a 5- or 6-membered aromatic heterocyclic ring which may have a substituent (for example, pyridylamino, thienylamino, dithienylamino group, etc.).
An acylamino group having an acyl group having 2 to 10 carbon atoms which may have a substituent (for example, acetylamino, benzoylamino group, etc.)]
An alkoxy group that may have a substituent (preferably an alkoxy group having 1 to 8 carbon atoms that may have a substituent, such as methoxy, ethoxy, and butoxy groups).
An aryloxy group which may have a substituent (preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy and 2-naphthyloxy groups) )
A heteroaryloxy group which may have a substituent (preferably has a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyloxy and thienyloxy group).
An acyl group which may have a substituent (preferably an acyl group having 2 to 10 carbon atoms which may have a substituent, such as formyl, acetyl and benzoyl groups).
An alkoxycarbonyl group which may have a substituent (preferably an alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent, such as methoxycarbonyl and ethoxycarbonyl groups).
An aryloxycarbonyl group which may have a substituent (preferably an aryloxycarbonyl group having 7 to 13 carbon atoms which may have a substituent, such as a phenoxycarbonyl group).
An alkylcarbonyloxy group which may have a substituent (preferably an alkylcarbonyloxy group having 2 to 10 carbon atoms which may have a substituent, such as an acetoxy group).
A halogen atom (preferably a fluorine atom or a chlorine atom)
Carboxy group Cyano group Hydroxyl group Mercapto group Alkylthio group which may have a substituent (preferably an alkylthio group having 1 to 8 carbon atoms, such as methylthio group and ethylthio group).
An arylthio group which may have a substituent (preferably an arylthio group having 6 to 12 carbon atoms, such as a phenylthio group and a 1-naphthylthio group).
A sulfonyl group which may have a substituent (for example, a mesyl group, a tosyl group, etc.).
A silyl group which may have a substituent (for example, a trimethylsilyl group, a triphenylsilyl group, etc.).
An optionally substituted boryl group (eg, a dimesitylboryl group).
A phosphino group which may have a substituent (for example, a diphenylphosphino group).
An aromatic hydrocarbon group which may have a substituent (for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, etc. And monovalent groups derived from 5- or 6-membered monocyclic rings or 2 to 5 condensed rings.)
An aromatic heterocyclic group which may have a substituent (for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo) Imidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, Monovalent groups derived from 5- or 6-membered monocyclic or 2-4 condensed rings such as pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, benzimidazole ring, perimidine ring, quinazoline ring Can be mentioned.)
上記置換基がさらに置換基を有する場合、その置換基としては、上記例示置換基が挙げられる。 When the said substituent further has a substituent, the said exemplary substituent is mentioned as the substituent.
電気化学的耐久性を向上させる観点及び耐熱性を向上させる観点からは、環A〜環Fのベンゼン環の置換基としては、置換基を有していてもよい芳香族炭化水素基が好ましく、より好ましくは置換基を有していてもよいフェニル基であり、さらに好ましくは無置換のフェニル基、或いは1又は2置換のフェニル基である(ただし、この数は、一般式(I),(II)における環A〜環Fは置換基として含めていない数である。)。 From the viewpoint of improving electrochemical durability and improving heat resistance, the substituent of the benzene ring of ring A to ring F is preferably an aromatic hydrocarbon group which may have a substituent, More preferred is an optionally substituted phenyl group, and further preferred is an unsubstituted phenyl group or a mono- or di-substituted phenyl group (however, this number is defined by the general formula (I), ( Ring A to ring F in II) are numbers not included as substituents.
溶解性及び非晶質性をさらに向上させる観点からは、環A〜環Fのベンゼン環の置換基としては、置換基を有していてもよいアルキル基が好ましく、より好ましくはメチル基、エチル基、n−プロピル基、2−プロピル基、n−ブチル基、イソブチル基、tert−ブチル基、さらに好ましくはメチル基、エチル基である。 From the viewpoint of further improving the solubility and the amorphousness, the substituent of the benzene ring of ring A to ring F is preferably an alkyl group which may have a substituent, more preferably a methyl group or ethyl group. Group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, more preferably methyl group or ethyl group.
[5]特に好ましい部分構造
電気的な一電子酸化と中和の繰返しに対する耐久性を向上させるためには、一般式(II)で表されるトリフェニルアミン部分骨格における環D,E,Fには、それぞれ、トリフェニルアミン部分骨格の中心にあるN原子に対してp−位に任意の置換基(好ましい置換基の例は、環A〜Fの好ましい置換基の例と同一である)を有しているのが好ましい。特に、該トリフェニルアミン部分骨格は、下記一般式(III)で表されるトリス(4−ビフェニル)アミン骨格をなしていることが、最も好ましい。
[5] Particularly preferred partial structure In order to improve durability against repeated electrical one-electron oxidation and neutralization, the ring D, E, F in the triphenylamine partial skeleton represented by the general formula (II) Each has an optional substituent in the p-position with respect to the N atom at the center of the triphenylamine partial skeleton (examples of preferred substituents are the same as examples of preferred substituents of rings A to F). It is preferable to have it. In particular, the triphenylamine partial skeleton is most preferably a tris (4-biphenyl) amine skeleton represented by the following general formula (III).
なお、一般式(III)において、環G〜環Iは置換基を有しても良く、該置換基としては、上記環A〜環Fの置換基として例示したものが挙げられる。ただし、環D〜環Fは、高い電荷輸送能を有する点では上記一般式(III)に示される以外の置換基を有していないことが好ましいが、高い溶解性を有するという点では、置換基を有することが好ましい。さらに、一般式(III)中の、環H、環Iあるいは環Gは、それぞれが結合する環E、環Fあるいは環Dの結合位置に対して、メタ位に、カルバゾール環が結合していることが好ましい。特に、環H、環I、環Gのすべてが、該メタ位にカルバゾール環が結合していることが好ましい。 In general formula (III), ring G to ring I may have a substituent, and examples of the substituent include those exemplified as the substituents of ring A to ring F above. However, the ring D to the ring F preferably have no substituent other than that shown in the general formula (III) in terms of having a high charge transporting ability, but in terms of having high solubility, It preferably has a group. Further, in general formula (III), ring H, ring I or ring G has a carbazole ring bonded to the meta position with respect to the bonding position of ring E, ring F or ring D to which they are bonded. It is preferable. In particular, it is preferable that all of ring H, ring I, and ring G have a carbazole ring bonded to the meta position.
また、溶媒への溶解性をさらに向上させるためには、本発明の電荷輸送材料は、分子内に下記一般式(IV)で表されるm−フェニレン基を有することが好ましく、特に、m−フェニレン基の2,4,5,6−位は水素原子であること(即ち、このm−フェニレン基の2個の結合手以外の炭素は置換基を有さないこと)が、さらに好ましい。 In order to further improve the solubility in a solvent, the charge transport material of the present invention preferably has an m-phenylene group represented by the following general formula (IV) in the molecule, and particularly m- More preferably, the 2,4,5,6-position of the phenylene group is a hydrogen atom (that is, carbons other than the two bonds of the m-phenylene group have no substituent).
本発明の電荷輸送材料は、特に、上記一般式(IV)で表されるm−フェニレン基を分子内に2以上有することが好ましく、3以上、10以下有することがさらに好ましい。m−フェニレン基を過度に多く有すると耐熱性が低下するおそれがある。 In particular, the charge transport material of the present invention preferably has 2 or more m-phenylene groups represented by the above general formula (IV) in the molecule, and more preferably 3 or more and 10 or less. When it has too many m-phenylene groups, there exists a possibility that heat resistance may fall.
また、耐熱性と溶媒への溶解性とを、ともに向上させるためには、上記m−フェニレン基がカルバゾール環と結合していることが好ましく、特に、本発明の電荷輸送材料は、分子内に下記一般式(IVa)で表される3−(N−カルバゾリル)フェニル基を有することが、最も好ましい。該3−(N−カルバゾリル)フェニル基は、置換基を有していてもよいが、無置換であることが好ましい。 In order to improve both the heat resistance and the solubility in a solvent, the m-phenylene group is preferably bonded to a carbazole ring. In particular, the charge transport material of the present invention has an intramolecular structure. Most preferably, it has a 3- (N-carbazolyl) phenyl group represented by the following general formula (IVa). The 3- (N-carbazolyl) phenyl group may have a substituent, but is preferably unsubstituted.
また、耐熱性を低下させる原因となることから、本発明の電荷輸送材料は、炭素数が2以上の脂肪族炭化水素基を有さないことが好ましい。また、電気化学的安定性の低下及び三重項励起準位の低下の原因となるおそれがあることから、本発明の電荷輸送材料は、窒素原子以外のヘテロ原子を含む基を含まないことが好ましい。特に、本発明の電荷輸送材料は、ベンゼン環、ヘテロ原子として窒素原子を有する芳香族複素環、及び窒素原子からなる群から選ばれる部分構造のみから構成される化合物であることが最も好ましい。 Moreover, since it becomes a cause to reduce heat resistance, it is preferable that the charge transport material of the present invention does not have an aliphatic hydrocarbon group having 2 or more carbon atoms. In addition, the charge transport material of the present invention preferably does not contain a group containing a hetero atom other than a nitrogen atom because it may cause a decrease in electrochemical stability and a decrease in triplet excited level. . In particular, the charge transport material of the present invention is most preferably a compound composed only of a partial structure selected from the group consisting of a benzene ring, an aromatic heterocycle having a nitrogen atom as a hetero atom, and a nitrogen atom.
なお、ベンゼン環、ヘテロ原子として窒素原子を有する芳香族複素環、及び窒素原子からなる群から選ばれる部分構造のみから構成される化合物とは、ベンゼン環、ヘテロ原子として窒素原子を有する芳香族複素環、及び窒素原子からなる群から選ばれる、環あるいは原子のみが結合してなる化合物をいう。すなわち、アルキル基、アルコキシ基、アリールオキシ基などは該化合物中には含まれない。 In addition, a compound composed only of a benzene ring, an aromatic heterocycle having a nitrogen atom as a heteroatom, and a partial structure selected from the group consisting of nitrogen atoms is an aromatic heterocycle having a nitrogen atom as a benzene ring and a heteroatom. A compound formed by bonding only a ring or an atom selected from the group consisting of a ring and a nitrogen atom. That is, an alkyl group, an alkoxy group, an aryloxy group and the like are not included in the compound.
[6]例示
以下に、本発明の電荷輸送材料として好ましい具体的な例を示すが、本発明はこれらに限定されるものではない。
[6] Illustrative Examples Hereinafter, preferred specific examples of the charge transport material of the present invention will be shown, but the present invention is not limited thereto.
上記電荷輸送材料の中でも、下記式(IA)で表される化合物および下記式(IB)で表される化合物は新規化合物である。溶解性、耐熱性、電気化学的安定性の全てにおいて、良好な物性を示すことから、本発明に使用される電荷輸送材料は、下記式(IA)で表される化合物および/または下記式(IB)で表される化合物を含むことが特に好ましい。 Among the charge transport materials, a compound represented by the following formula (IA) and a compound represented by the following formula (IB) are novel compounds. Since all of solubility, heat resistance, and electrochemical stability exhibit good physical properties, the charge transport material used in the present invention is a compound represented by the following formula (IA) and / or the following formula ( It is particularly preferred to include a compound represented by IB).
また、下記式(IA)で表される化合物および下記式(IB)で表される化合物は、有機電界発光素子に含有されることが好ましく、該化合物は真空蒸着法や湿式製膜法により通常公知の方法により、有機電界発光素子のいずれかの層に含有される。 In addition, the compound represented by the following formula (IA) and the compound represented by the following formula (IB) are preferably contained in an organic electroluminescent device, and the compound is usually obtained by a vacuum deposition method or a wet film forming method. It contains in any layer of an organic electroluminescent element by a well-known method.
なお、下記式(IA)で表される化合物および下記式(IB)で表される化合物は、有機電界発光素子の他、電子写真感光体、光電変換素子、有機太陽電池、有機整流素子等に好適に使用できる。 In addition, the compound represented by the following formula (IA) and the compound represented by the following formula (IB) are used for an electrophotographic photosensitive member, a photoelectric conversion element, an organic solar cell, an organic rectifying element, etc. in addition to an organic electroluminescent element. It can be used suitably.
[溶媒]
本発明の有機電界発光素子用組成物はさらに溶媒を含むことが好ましい。
本発明の有機電界発光素子用組成物に含まれる溶媒としては、上述の本発明の電荷輸送材料等の溶質が良好に溶解する溶媒であれば特に限定されない。
[solvent]
It is preferable that the composition for organic electroluminescent elements of the present invention further contains a solvent.
The solvent contained in the composition for organic electroluminescent elements of the present invention is not particularly limited as long as the solute such as the above-described charge transport material of the present invention dissolves well.
本発明の電荷輸送材料は溶解性が高いため、種々の溶媒が適用可能である。例えば、トルエン、キシレン、メチシレン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素;クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化芳香族炭化水素;1,2−ジメトキシベンゼン、1,3−ジメトキシベンゼン、アニソール、フェネトール、2−メトキシトルエン、3−メトキシトルエン、4−メトキシトルエン、2,3−ジメチルアニソール、2,4−ジメチルアニソール等の芳香族エーテル;酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n−ブチル等の芳香族エステル;シクロヘキサノン、シクロオクタノン等の脂環を有するケトン;メチルエチルケトン、ジブチルケトン等の脂肪族ケトン;メチルエチルケトン、シクロヘキサノール、シクロオクタノール等の脂環を有するアルコール;ブタノール、ヘキサノール等の脂肪族アルコール;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール−1−モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル;酢酸エチル、酢酸n−ブチル、乳酸エチル、乳酸n−ブチル等の脂肪族エステル等が利用できる。これらのうち、水の溶解度が低い点、容易には変質しない点で、トルエン、キシレン、メチシレン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素が好ましい。 Since the charge transport material of the present invention has high solubility, various solvents can be applied. For example, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene and tetralin; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and anisole , Phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic esters such as ethyl, propyl benzoate and n-butyl benzoate; ketones having an alicyclic ring such as cyclohexanone and cyclooctanone; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; methyl ethyl ketone and cyclohexano Alcohol having an alicyclic ring such as ruthenium or cyclooctanol; Aliphatic alcohol such as butanol or hexanol; Aliphatic ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate (PGMEA); Ethyl acetate In addition, aliphatic esters such as n-butyl acetate, ethyl lactate, and n-butyl lactate can be used. Of these, aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, tetralin and the like are preferable in that they have low water solubility and are not easily altered.
有機電界発光素子には、陰極等の水分により著しく劣化する材料が多く使用されているため、組成物中の水分の存在は、乾燥後の膜中に水分が残留し、素子の特性を低下させる可能性が考えられ好ましくない。 Since organic electroluminescent devices use many materials such as cathodes that deteriorate significantly due to moisture, the presence of moisture in the composition causes moisture to remain in the dried film, degrading the device characteristics. The possibility is considered and it is not preferable.
組成物中の水分量を低減する方法としては、例えば、蒸留や乾燥剤の使用などにより溶媒を予め脱水する、窒素ガスシール、水の溶解度が低い溶媒を使用する等が挙げられる。なかでも、水の溶解度が低い溶媒を使用する場合は、湿式製膜工程中に、溶液膜が大気中の水分を吸収して白化する現象を防ぐことができるため好ましい。この様な観点からは、本実施の形態が適用される有機電界発光素子用組成物は、例えば、25℃における水の溶解度が1重量%以下、好ましくは0.1重量%以下である溶媒を、組成物中10重量%以上含有することが好ましい。 Examples of the method for reducing the amount of water in the composition include dehydration of the solvent in advance by distillation or use of a desiccant, nitrogen gas sealing, use of a solvent with low water solubility, and the like. In particular, it is preferable to use a solvent having low water solubility because the solution film can prevent whitening by absorbing moisture in the atmosphere during the wet film forming process. From such a viewpoint, the composition for organic electroluminescent elements to which the present embodiment is applied includes, for example, a solvent having a water solubility at 25 ° C. of 1% by weight or less, preferably 0.1% by weight or less. It is preferable to contain 10% by weight or more in the composition.
また、湿式製膜時における組成物からの溶媒蒸発による、製膜安定性の低下を低減するためには、有機電界発光素子用組成物の溶媒として、沸点が100℃以上、好ましくは沸点が150℃以上、より好ましくは沸点が200℃以上の溶媒を用いることが効果的である。また、より均一な膜を得るためには、製膜直後の液膜から溶媒が適当な速度で蒸発することが必要で、このためには通常沸点80℃以上、好ましくは沸点100℃以上、より好ましくは沸点120℃以上で、通常沸点270℃未満、好ましくは沸点250℃未満、より好ましくは沸点230℃未満の溶媒を用いることが有効である。 Further, in order to reduce a decrease in film formation stability due to solvent evaporation from the composition during wet film formation, the boiling point is 100 ° C. or higher, preferably 150 ° C. as a solvent for the composition for organic electroluminescent elements. It is effective to use a solvent having a boiling point of 200 ° C. or higher, more preferably 200 ° C. or higher. In order to obtain a more uniform film, it is necessary for the solvent to evaporate from the liquid film immediately after film formation at an appropriate rate. For this purpose, the boiling point is usually 80 ° C. or higher, preferably 100 ° C. or higher. It is effective to use a solvent having a boiling point of 120 ° C. or higher, usually a boiling point of less than 270 ° C., preferably a boiling point of less than 250 ° C., more preferably a boiling point of less than 230 ° C.
上述の条件、即ち溶質の溶解性、蒸発速度、水の溶解度の条件を満足する溶媒を単独で用いても良いが、すべての条件を満たす溶媒が選定できない場合は、2種類以上の溶媒を混合して用いることもできる。 A solvent that satisfies the above-mentioned conditions, ie, solute solubility, evaporation rate, and water solubility conditions, may be used alone. However, if a solvent that satisfies all of the conditions cannot be selected, two or more solvents may be mixed. It can also be used.
[発光材料]
本発明の有機電界発光素子用組成物は、発光材料を含有することが好ましい。
発光材料とは、本発明の有機電界発光素子用組成物において、主として発光する成分を指し、有機ELデバイスにおけるドーパント成分に当たる。該有機電界発光素子用組成物から発せられる光量(単位:cd/m2)の内、通常10〜100%、好ましくは20〜100%、より好ましくは50〜100%、最も好ましくは80〜100%が、ある成分材料からの発光と同定される場合、それを発光材料と定義する。
[Luminescent material]
The composition for organic electroluminescent elements of the present invention preferably contains a luminescent material.
A luminescent material refers to the component which mainly light-emits in the composition for organic electroluminescent elements of this invention, and corresponds to the dopant component in an organic EL device. Of the amount of light (unit: cd / m 2 ) emitted from the composition for organic electroluminescent elements, it is usually 10 to 100%, preferably 20 to 100%, more preferably 50 to 100%, and most preferably 80 to 100%. If% is identified as luminescence from a component material, it is defined as the luminescent material.
発光材料としては、任意の公知材料を適用可能であり、蛍光発光材料あるいは燐光発光材料を単独若しくは複数を混合して使用できるが、内部量子効率の観点から、好ましくは、燐光発光材料である。 As the luminescent material, any known material can be applied, and a fluorescent luminescent material or a phosphorescent luminescent material can be used alone or in combination. A phosphorescent luminescent material is preferable from the viewpoint of internal quantum efficiency.
尚、溶媒への溶解性を向上させる目的で、発光材料分子の対称性や剛性を低下させたり、あるいはアルキル基などの親油性置換基を導入したりすることも、重要である。 For the purpose of improving the solubility in a solvent, it is also important to reduce the symmetry and rigidity of the light emitting material molecule or to introduce a lipophilic substituent such as an alkyl group.
青色発光を与える蛍光色素としては、ペリレン、ピレン、アントラセン、クマリン、p−ビス(2−フェニルエテニル)ベンゼン及びそれらの誘導体等が挙げられる。緑色蛍光色素としては、キナクリドン誘導体、クマリン誘導体等が挙げられる。黄色蛍光色素としては、ルブレン、ペリミドン誘導体等が挙げられる。赤色蛍光色素としては、DCM系化合物、ベンゾピラン誘導体、ローダミン誘導体、ベンゾチオキサンテン誘導体、アザベンゾチオキサンテン等が挙げられる。 Examples of fluorescent dyes that emit blue light include perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof. Examples of the green fluorescent dye include quinacridone derivatives and coumarin derivatives. Examples of yellow fluorescent dyes include rubrene and perimidone derivatives. Examples of red fluorescent dyes include DCM compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, azabenzothioxanthene and the like.
燐光発光材料としては、例えば周期表7ないし11族から選ばれる金属を含む有機金属錯体が挙げられる。 Examples of the phosphorescent material include organometallic complexes containing a metal selected from Groups 7 to 11 of the periodic table.
周期表7ないし11族から選ばれる金属を含む燐光性有機金属錯体における金属として好ましくは、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金、金等が挙げられる。これらの有機金属錯体として、好ましくは下記一般式(V)又は下記一般式(VI)で表される化合物が挙げられる。
ML(q−j)L’j (V)
(一般式(V)中、Mは金属を表し、qは上記金属の価数を表す。また、L及びL’は二座配位子を表す。jは0、1又は2を表す。)
Preferred examples of the metal in the phosphorescent organometallic complex containing a metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Preferred examples of these organometallic complexes include compounds represented by the following general formula (V) or the following general formula (VI).
ML (q−j) L ′ j (V)
(In general formula (V), M represents a metal, q represents the valence of the metal, L and L ′ represent a bidentate ligand, and j represents 0, 1 or 2.)
以下、まず、一般式(V)で表される化合物について説明する。
一般式(V)中、Mは任意の金属を表し、好ましいものの具体例としては、周期表7ないし11族から選ばれる金属として前述した金属が挙げられる。
また、一般式(V)中の二座配位子L及びL’は、それぞれ、以下の部分構造を有する配位子を示す。
Hereinafter, the compound represented by the general formula (V) will be described first.
In the general formula (V), M represents an arbitrary metal, and specific examples of preferable ones include the metals described above as the metal selected from Groups 7 to 11 of the periodic table.
Moreover, the bidentate ligands L and L ′ in the general formula (V) each represent a ligand having the following partial structure.
L’として、錯体の安定性の観点から、特に好ましくは、下記のものが挙げられる。
上記L,L’の部分構造において、環A1は、芳香族炭化水素基又は芳香族複素環基を表し、これらは置換基を有していてもよい。また、環A2は、含窒素芳香族複素環基を表し、これらは置換基を有していてもよい。 In the partial structures of L and L ′, the ring A1 represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and these may have a substituent. Ring A2 represents a nitrogen-containing aromatic heterocyclic group, and these may have a substituent.
環A1,A2が置換基を有する場合、好ましい置換基としては、フッ素原子等のハロゲン原子;メチル基、エチル基等のアルキル基;ビニル基等のアルケニル基;メトキシカルボニル基、エトキシカルボニル基等のアルコキシカルボニル基;メトキシ基、エトキシ基等のアルコキシ基;フェノキシ基、ベンジルオキシ基などのアリールオキシ基;ジメチルアミノ基、ジエチルアミノ基等のジアルキルアミノ基;ジフェニルアミノ基等のジアリールアミノ基;カルバゾリル基;アセチル基等のアシル基;トリフルオロメチル基等のハロアルキル基;シアノ基;フェニル基、ナフチル基、フェナンチル基等の芳香族炭化水素基等が挙げられる。 When the rings A1 and A2 have a substituent, preferred substituents include halogen atoms such as fluorine atoms; alkyl groups such as methyl groups and ethyl groups; alkenyl groups such as vinyl groups; methoxycarbonyl groups and ethoxycarbonyl groups. Alkoxycarbonyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups and benzyloxy groups; dialkylamino groups such as dimethylamino groups and diethylamino groups; diarylamino groups such as diphenylamino groups; carbazolyl groups; An acyl group such as an acetyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group; an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, and a phenanthyl group.
一般式(V)で表される化合物として、さらに好ましくは、下記一般式(Va)、(Vb)、(Vc)で表される化合物が挙げられる。 More preferable examples of the compound represented by the general formula (V) include compounds represented by the following general formulas (Va), (Vb), and (Vc).
上記一般式(Va)、(Vb)、(Vc)において、環A1及び環A1’の基としては、好ましくは、例えばフェニル基、ビフェニル基、ナフチル基、アントリル基、チエニル基、フリル基、ベンゾチエニル基、ベンゾフリル基、ピリジル基、キノリル基、イソキノリル基、カルバゾリル基等が挙げられる。 In the general formulas (Va), (Vb), and (Vc), the group of the ring A1 and the ring A1 ′ is preferably a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a thienyl group, a furyl group, a benzo group, for example. Examples include thienyl group, benzofuryl group, pyridyl group, quinolyl group, isoquinolyl group, carbazolyl group and the like.
また、環A2、環A2’の基としては、好ましくは、例えばピリジル基、ピリミジル基、ピラジル基、トリアジル基、ベンゾチアゾール基、ベンゾオキサゾール基、ベンゾイミダゾール基、キノリル基、イソキノリル基、キノキサリル基、フェナントリジル基等が挙げられる。 In addition, the group of ring A2 and ring A2 ′ is preferably a pyridyl group, pyrimidyl group, pyrazyl group, triazyl group, benzothiazole group, benzoxazole group, benzimidazole group, quinolyl group, isoquinolyl group, quinoxalyl group, A phenanthridyl group and the like can be mentioned.
さらに、一般式(Va)、(Vb)、(Vc)で表される化合物が有していてもよい置換基としては、フッ素原子等のハロゲン原子;メチル基、エチル基等のアルキル基;ビニル基等のアルケニル基;メトキシカルボニル基、エトキシカルボニル基等のアルコキシカルボニル基;メトキシ基、エトキシ基等のアルコキシ基;フェノキシ基、ベンジルオキシ基などのアリールオキシ基;ジメチルアミノ基、ジエチルアミノ基等のジアルキルアミノ基;ジフェニルアミノ基等のジアリールアミノ基;カルバゾリル基;アセチル基等のアシル基;トリフルオロメチル基等のハロアルキル基;シアノ基等が挙げられる。 Furthermore, the substituents that the compounds represented by the general formulas (Va), (Vb), and (Vc) may have include a halogen atom such as a fluorine atom; an alkyl group such as a methyl group and an ethyl group; vinyl Alkenyl groups such as methoxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups and benzyloxy groups; dialkyls such as dimethylamino groups and diethylamino groups An amino group; a diarylamino group such as a diphenylamino group; a carbazolyl group; an acyl group such as an acetyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group;
上記置換基がアルキル基である場合は、その炭素数は通常1以上6以下である。さらに、置換基がアルケニル基である場合は、その炭素数は通常2以上6以下である。また、置換基がアルコキシカルボニル基である場合は、その炭素数は通常2以上6以下である。さらに、置換基がアルコキシ基である場合は、その炭素数は通常1以上6以下である。また、置換基がアリールオキシ基である場合は、その炭素数は通常6以上14以下である。さらに、置換基がジアルキルアミノ基である場合は、その炭素数は通常2以上24以下である。また、置換基がジアリールアミノ基である場合は、その炭素数は通常12以上28以下である。さらに、置換基がアシル基である場合は、その炭素数は通常1以上14以下である。また、置換基がハロアルキル基である場合は、その炭素数は通常1以上12以下である。 When the said substituent is an alkyl group, the carbon number is 1 or more and 6 or less normally. Furthermore, when the substituent is an alkenyl group, the carbon number is usually 2 or more and 6 or less. When the substituent is an alkoxycarbonyl group, the carbon number is usually 2 or more and 6 or less. Further, when the substituent is an alkoxy group, the carbon number is usually 1 or more and 6 or less. Moreover, when a substituent is an aryloxy group, the carbon number is 6 or more and 14 or less normally. Furthermore, when the substituent is a dialkylamino group, the carbon number is usually 2 or more and 24 or less. Further, when the substituent is a diarylamino group, the carbon number is usually 12 or more and 28 or less. Furthermore, when the substituent is an acyl group, the carbon number is usually 1 or more and 14 or less. Moreover, when a substituent is a haloalkyl group, the carbon number is 1 or more and 12 or less normally.
なお、これら置換基は互いに連結して環を形成してもよい。具体例としては、環A1が有する置換基と環A2が有する置換基とが結合するか、又は、環A1’が有する置換基と環A2’が有する置換基とが結合するかして、一つの縮合環を形成してもよい。このような縮合環基としては、7,8−ベンゾキノリン基等が挙げられる。 These substituents may be connected to each other to form a ring. As a specific example, a substituent of the ring A1 and a substituent of the ring A2 are bonded, or a substituent of the ring A1 ′ and a substituent of the ring A2 ′ are bonded. Two fused rings may be formed. Examples of such a condensed ring group include a 7,8-benzoquinoline group.
中でも、環A1、環A1’、環A2及び環A2’の置換基として、より好ましくはアルキル基、アルコキシ基、芳香族炭化水素基、シアノ基、ハロゲン原子、ハロアルキル基、ジアリールアミノ基、カルバゾリル基が挙げられる。 Among them, as a substituent for ring A1, ring A1 ′, ring A2 and ring A2 ′, an alkyl group, alkoxy group, aromatic hydrocarbon group, cyano group, halogen atom, haloalkyl group, diarylamino group, carbazolyl group are more preferable. Is mentioned.
また、一般式(Va)、(Vb)、(Vc)におけるMa,Mb,Mcとして好ましくは、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金又は金が挙げられる。 In general formula (Va), (Vb), preferably as M a, M b, M c in (Vc), ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold.
上記一般式(V)、(Va)、(Vb)又は(Vc)で示される有機金属錯体の具体例を以下に示すが、下記の化合物に限定されるものではない(以下において、Phはフェニル基を表す。)。 Specific examples of the organometallic complex represented by the general formula (V), (Va), (Vb) or (Vc) are shown below, but are not limited to the following compounds (in the following, Ph is phenyl Represents a group).
上記一般式(V)、(Va)、(Vb)、(Vc)で表される有機金属錯体の中でも、特に、配位子L及び/又はL’として2−アリールピリジン系配位子、即ち、2−アリールピリジン、これに任意の置換基が結合したもの、及び、これに任意の基が縮合してなるものを有する化合物が好ましい。 Among the organometallic complexes represented by the general formulas (V), (Va), (Vb), and (Vc), in particular, as the ligand L and / or L ′, a 2-arylpyridine-based ligand, , 2-arylpyridine, compounds having an arbitrary substituent bonded thereto, and compounds formed by condensing an arbitrary group thereto are preferable.
次に、前記一般式(VI)で表される化合物について説明する。
一般式(VI)中、Mdは金属を表し、具体例としては、周期表7ないし11族から選ばれる金属として前述した金属が挙げられる。中でも好ましくは、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金又は金が挙げられ、特に好ましくは、白金、パラジウム等の2価の金属が挙げられる。
Next, the compound represented by the general formula (VI) will be described.
In the general formula (VI), M d represents a metal, and specific examples thereof include the metals described above as the metal selected from Groups 7 to 11 of the periodic table. Among these, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold is preferable, and divalent metals such as platinum and palladium are particularly preferable.
また、一般式(VI)において、R92及びR93は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アルケニル基、シアノ基、アミノ基、アシル基、アルコキシカルボニル基、カルボキシル基、アルコキシ基、アルキルアミノ基、アラルキルアミノ基、ハロアルキル基、水酸基、アリールオキシ基、芳香族炭化水素基又は芳香族複素環基を表す。 In the general formula (VI), R 92 and R 93 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, or a carboxyl group. Represents an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group.
さらに、Tが炭素の場合、R94及びR95は、それぞれ独立に、R92及びR93と同様の例示物で表される置換基を表す。また、前述の如く、Tが窒素の場合はR94及びR95は無い。 Further, when T is carbon, R 94 and R 95 each independently represent a substituent represented by the same examples as R 92 and R 93 . Further, as described above, when T is nitrogen, R 94 and R 95 are absent.
また、R92〜R95はさらに置換基を有していてもよい。この場合のさらに有していてもよい置換基には特に制限はなく、任意の基を置換基とすることができる。
さらに、R92〜R95は互いに連結して環を形成してもよく、この環がさらに任意の置換基を有していてもよい。
R 92 to R 95 may further have a substituent. In this case, the substituent which may further be present is not particularly limited, and any group can be used as the substituent.
Furthermore, R 92 to R 95 may be connected to each other to form a ring, and this ring may further have an arbitrary substituent.
一般式(VI)で表される有機金属錯体の具体例(T−1,T−10〜T−15)を以下に示すが、下記の例示化合物に限定されるものではない。なお、以下において、Meはメチル基を表し、Etはエチル基を表す。 Specific examples (T-1, T-10 to T-15) of the organometallic complex represented by the general formula (VI) are shown below, but are not limited to the following exemplified compounds. In the following, Me represents a methyl group, and Et represents an ethyl group.
また、有機金属錯体としては、WO2005/019373号公報に記載の化合物も使用することができる。 Moreover, as an organometallic complex, the compounds described in WO2005 / 019373 can also be used.
[その他の成分]
本発明の有機電界発光素子用組成物中には、前述した溶媒及び発光材料以外にも、必要に応じて、各種の他の溶媒を含んでいてもよい。このような他の溶媒としては、例えば、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等のアミド類、ジメチルスルホキシド等が挙げられる。
また、レベリング剤や消泡剤等の各種添加剤を含んでいてもよい。
[Other ingredients]
In the composition for organic electroluminescent elements of the present invention, various other solvents may be included as necessary in addition to the above-described solvent and light emitting material. Examples of such other solvents include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl sulfoxide.
Moreover, various additives, such as a leveling agent and an antifoamer, may be included.
また、2層以上の層を湿式製膜法により積層する際に、これらの層が相溶することを防ぐため、製膜後に硬化させて不溶化させる目的で光硬化性樹脂や、熱硬化性樹脂を含有させておくこともできる。 In addition, when two or more layers are laminated by a wet film-forming method, in order to prevent these layers from being compatible with each other, a photo-curing resin or a thermosetting resin is used for the purpose of curing and insolubilizing after film formation. Can also be contained.
[有機電界発光素子用組成物中の材料濃度と配合比]
本発明の有機電界発光素子用組成物中の電荷輸送材料、発光材料及び必要に応じて添加可能な成分(レベリング剤など)などの固形分濃度は、通常0.01重量%以上、好ましくは0.05重量%以上、より好ましくは0.1重量%以上、さらに好ましくは0.5重量%以上、最も好ましくは1重量%以上であり、通常80重量%以下、好ましくは50重量%以下、より好ましくは40重量%以下、さらに好ましくは30重量%以下、最も好ましくは20重量%以下である。この濃度が下限を下回ると、薄膜を形成する場合、厚膜を形成するのが困難となり、上限を超えると、薄膜を形成するのが困難となる。
[Material concentration and blending ratio in composition for organic electroluminescence device]
The solid content concentration of the charge transport material, the luminescent material, and components (leveling agents, etc.) that can be added as necessary in the composition for organic electroluminescent elements of the present invention is usually 0.01% by weight or more, preferably 0. 0.05% by weight or more, more preferably 0.1% by weight or more, more preferably 0.5% by weight or more, most preferably 1% by weight or more, and usually 80% by weight or less, preferably 50% by weight or less, more It is preferably 40% by weight or less, more preferably 30% by weight or less, and most preferably 20% by weight or less. When this concentration is below the lower limit, it is difficult to form a thick film when forming a thin film, and when it exceeds the upper limit, it is difficult to form a thin film.
また、本発明の有機電界発光素子用組成物において、発光材料/電荷輸送材料の重量混合比は、通常、0.1/99.9以上であり、より好ましくは0.5/99.5以上であり、さらに好ましくは1/99以上であり、最も好ましくは2/98以上で、通常、50/50以下であり、より好ましくは40/60以下であり、さらに好ましくは30/70以下であり、最も好ましくは20/80以下である。この比が下限を下回ったり、上限を超えたりすると、著しく発光効率が低下するおそれがある。 In the composition for organic electroluminescent elements of the present invention, the weight mixing ratio of the light emitting material / charge transporting material is usually 0.1 / 99.9 or more, more preferably 0.5 / 99.5 or more. More preferably, it is 1/99 or more, most preferably 2/98 or more, usually 50/50 or less, more preferably 40/60 or less, and further preferably 30/70 or less. Most preferably, it is 20/80 or less. If this ratio falls below the lower limit or exceeds the upper limit, the luminous efficiency may be significantly reduced.
[有機電界発光素子用組成物の調製方法]
本発明の有機電界発光素子用組成物は、電荷輸送材料、発光材料、及び必要に応じて添加可能なレベリング剤や消泡剤等の各種添加剤よりなる溶質を、適当な溶媒に溶解させることにより調製される。溶解工程に要する時間を短縮するため、及び組成物中の溶質濃度を均一に保つため、通常、液を撹拌しながら溶質を溶解させる。溶解工程は常温で行ってもよいが、溶解速度が遅い場合は加熱して溶解させることもできる。溶解工程終了後、必要に応じて、フィルタリング等の濾過工程を経由してもよい。
[Method for Preparing Composition for Organic Electroluminescent Device]
The composition for an organic electroluminescent device of the present invention is obtained by dissolving a solute comprising a charge transport material, a light emitting material, and various additives such as a leveling agent and an antifoaming agent that can be added as necessary in an appropriate solvent. It is prepared by. In order to shorten the time required for the dissolution step and to keep the solute concentration in the composition uniform, the solute is usually dissolved while stirring the liquid. The dissolution step may be performed at room temperature, but when the dissolution rate is slow, it can be heated and dissolved. After completion of the dissolution step, a filtration step such as filtering may be performed as necessary.
[有機電界発光素子用組成物の性状、物性等]
(水分濃度)
本発明の有機電界発光素子用組成物を用いた湿式製膜法により層形成して有機電界発光素子を製造する場合、用いる有機電界発光素子用組成物に水分が存在すると、形成された膜に水分が混入して膜の均一性が損なわれるため、本発明の有機電界発光素子用組成物中の水分含有量はできるだけ少ない方が好ましい。また一般に、有機電界発光素子は、陰極等の水分により著しく劣化する材料が多く使用されているため、有機電界発光素子用組成物中に水分が存在した場合、乾燥後の膜中に水分が残留し、素子の特性を低下させる可能性が考えられ好ましくない。
[Properties, physical properties, etc. of composition for organic electroluminescence device]
(Moisture concentration)
In the case of producing an organic electroluminescent device by forming a layer by a wet film forming method using the composition for organic electroluminescent device of the present invention, if water is present in the composition for organic electroluminescent device to be used, Since moisture is mixed and the uniformity of the film is impaired, the water content in the composition for organic electroluminescent elements of the present invention is preferably as low as possible. In general, since organic electroluminescent devices use many materials such as cathodes that deteriorate significantly due to moisture, when moisture is present in the composition for organic electroluminescent devices, moisture remains in the dried film. However, there is a possibility of deteriorating the characteristics of the element, which is not preferable.
具体的には、本発明の有機電界発光素子用組成物中に含まれる水分量は、通常1重量%以下、好ましくは0.1重量%以下、より好ましくは0.01重量%以下である。 Specifically, the amount of water contained in the composition for organic electroluminescent elements of the present invention is usually 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.01% by weight or less.
有機電界発光素子用組成物中の水分濃度の測定方法としては、日本工業規格「化学製品の水分測定法」(JIS K0068:2001)に記載の方法が好ましく、例えば、カールフィッシャー試薬法(JIS K0211−1348)等により分析することができる。 As a method for measuring the moisture concentration in the composition for organic electroluminescent elements, the method described in Japanese Industrial Standard “Method for Measuring Moisture of Chemical Products” (JIS K0068: 2001) is preferable. For example, the Karl Fischer reagent method (JIS K0211). -1348) and the like.
(均一性)
本発明の有機電界発光素子用組成物は、湿式製膜プロセスでの安定性、例えば、インクジェット製膜法におけるノズルからの吐出安定性を高めるためには、常温で均一な液状であることが好ましい。常温で均一な液状とは、組成物が均一相からなる液体であり、かつ組成物中に粒径0.1μm以上の粒子成分を含有しないことをいう。
(Uniformity)
The composition for organic electroluminescent elements of the present invention is preferably in a uniform liquid state at room temperature in order to enhance stability in a wet film forming process, for example, ejection stability from a nozzle in an ink jet film forming method. . The uniform liquid at normal temperature means that the composition is a liquid composed of a uniform phase and does not contain a particle component having a particle size of 0.1 μm or more in the composition.
(物性)
本発明の有機電界発光素子用組成物の粘度については、極端に低粘度の場合は、例えば製膜工程における過度の液膜流動による塗面不均一、インクジェット製膜におけるノズル吐出不良等が起こりやすくなり、極端に高粘度の場合は、インクジェット製膜におけるノズル目詰まり等が起こりやすくなる。このため、本発明の組成物の25℃における粘度は、通常2mPa・s以上、好ましくは3mPa・s以上、より好ましくは5mPa・s以上であり、通常1000mPa・s以下、好ましくは100mPa・s以下、より好ましくは50mPa・s以下である。
(Physical properties)
Regarding the viscosity of the composition for organic electroluminescent elements of the present invention, in the case of extremely low viscosity, for example, coating surface non-uniformity due to excessive liquid film flow in the film forming process, nozzle ejection failure in ink jet film formation, etc. are likely to occur. In the case of extremely high viscosity, nozzle clogging or the like in ink jet film formation tends to occur. For this reason, the viscosity at 25 ° C. of the composition of the present invention is usually 2 mPa · s or more, preferably 3 mPa · s or more, more preferably 5 mPa · s or more, and usually 1000 mPa · s or less, preferably 100 mPa · s or less. More preferably, it is 50 mPa · s or less.
また、本発明の有機電界発光素子用組成物の表面張力が高い場合は、基板に対する製膜用液の濡れ性が低下する、液膜のレベリング性が悪く、乾燥時の製膜面乱れが起こりやすくなる等の問題が発生するため、本発明の組成物の20℃における表面張力は、通常50mN/m未満、好ましくは40mN/m未満である。 In addition, when the surface tension of the composition for organic electroluminescent elements of the present invention is high, the wettability of the liquid for film formation with respect to the substrate is lowered, the leveling property of the liquid film is poor, and the film formation surface is disturbed during drying. Since the problem of becoming easy occurs, the surface tension at 20 ° C. of the composition of the present invention is usually less than 50 mN / m, preferably less than 40 mN / m.
さらに、本発明の有機電界発光素子用組成物の蒸気圧が高い場合は、溶媒の蒸発による溶質濃度の変化等の問題が起こりやすくなる。このため、本発明の組成物の25℃における蒸気圧は、通常50mmHg以下、好ましくは10mmHg以下、より好ましくは1mmHg以下である。 Furthermore, when the vapor pressure of the composition for organic electroluminescent elements of the present invention is high, problems such as changes in solute concentration due to evaporation of the solvent tend to occur. For this reason, the vapor pressure at 25 ° C. of the composition of the present invention is usually 50 mmHg or less, preferably 10 mmHg or less, more preferably 1 mmHg or less.
[有機電界発光素子用組成物の保存方法]
本発明の有機電界発光素子用組成物は、紫外線の透過を防ぐことのできる容器、例えば、褐色ガラス瓶等に充填し、密栓して保管することが好ましい。保管温度は、通常−30℃以上、好ましくは0℃以上で、通常35℃以下、好ましくは25℃以下である。
[Method for Preserving Composition for Organic Electroluminescent Device]
The composition for an organic electroluminescent element of the present invention is preferably filled in a container capable of preventing the transmission of ultraviolet rays, for example, a brown glass bottle, and sealed and stored. The storage temperature is usually −30 ° C. or higher, preferably 0 ° C. or higher, and usually 35 ° C. or lower, preferably 25 ° C. or lower.
〔有機電界発光素子用薄膜〕
本発明の有機電界発光素子用組成物を用いて湿式製膜法により形成された本発明の有機電界発光素子用薄膜は、結晶化しにくく、発光特性、耐熱性に優れた膜であり、通常有機電界発光素子の陰極と陽極との間の層として使用される。
[Thin film for organic electroluminescence device]
The thin film for an organic electroluminescent device of the present invention formed by a wet film-forming method using the composition for an organic electroluminescent device of the present invention is a film that is difficult to crystallize, has excellent luminescent properties and heat resistance, and is usually organic. Used as a layer between the cathode and anode of the electroluminescent device.
ここで、湿式製膜法とは、溶媒を含む組成物を、スピンコート法、スプレーコート法、ディップコート法、ダイコート法、フレキソ印刷法、スクリーン印刷法、インクジェット法を用いて製膜することを言う。 Here, the wet film forming method refers to forming a composition containing a solvent using a spin coating method, a spray coating method, a dip coating method, a die coating method, a flexographic printing method, a screen printing method, and an inkjet method. To tell.
本発明の有機電界発光素子用薄膜の膜厚は用途に応じて適宜決定され、例えば、有機電界発光素子の発光層であれば、後述の如く、通常10nm以上、好ましくは20nm以上で、通常300nm以下、好ましくは200nm以下、或いは、通常30nm以上、好ましくは50nm以上、通常500nm以下、好ましくは300nm以下である。 The film thickness of the thin film for organic electroluminescent elements of the present invention is appropriately determined depending on the application. For example, in the case of a light emitting layer of an organic electroluminescent element, as described later, it is usually 10 nm or more, preferably 20 nm or more, usually 300 nm. Below, it is preferably 200 nm or less, or usually 30 nm or more, preferably 50 nm or more, usually 500 nm or less, preferably 300 nm or less.
〔有機電界発光素子〕
本発明の有機電界発光素子は、基板上に少なくとも陽極、陰極及びこれらの両極間に設けられた発光層を有するものであって、本発明の有機電界発光素子用組成物を用いて湿式製膜法により形成された層を有することを特徴とする。該湿式製膜法により形成された層は、該発光層であることが好ましい。
[Organic electroluminescence device]
The organic electroluminescent device of the present invention has at least an anode, a cathode, and a light emitting layer provided between both electrodes on a substrate, and is wet-formed using the composition for organic electroluminescent devices of the present invention. It has the layer formed by the method. The layer formed by the wet film forming method is preferably the light emitting layer.
図1〜6は本発明の有機電界発光素子に好適な構造例を示す断面の模式図であり、図1において、1は基板、2は陽極、3は正孔注入層、4は発光層、5は電子注入層、6は陰極を各々表す。 1 to 6 are schematic cross-sectional views showing structural examples suitable for the organic electroluminescent device of the present invention. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a light emitting layer, 5 represents an electron injection layer, and 6 represents a cathode.
[1]基板
基板1は有機電界発光素子の支持体となるものであり、石英やガラスの板、金属板や金属箔、プラスチックフィルムやシートなどが用いられる。特にガラス板や、ポリエステル、ポリメタクリレート、ポリカーボネート、ポリスルホンなどの透明な合成樹脂の板が好ましい。合成樹脂基板を使用する場合にはガスバリア性に留意する必要がある。基板のガスバリア性が小さすぎると、基板を通過した外気により有機電界発光素子が劣化することがあるので好ましくない。このため、合成樹脂基板の少なくとも片面に緻密なシリコン酸化膜等を設けてガスバリア性を確保する方法も好ましい方法の一つである。
[1] Substrate The substrate 1 serves as a support for the organic electroluminescent element, and quartz or glass plates, metal plates, metal foils, plastic films, sheets, and the like are used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescent element may be deteriorated by the outside air that has passed through the substrate, which is not preferable. For this reason, a method of providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also a preferable method.
[2]陽極
基板1上には陽極2が設けられる。陽極2は発光層側の層(正孔注入層3又は発光層4など)への正孔注入の役割を果たすものである。
[2] Anode An anode 2 is provided on the substrate 1. The anode 2 plays a role of hole injection into a layer on the light emitting layer side (such as the hole injection layer 3 or the light emitting layer 4).
この陽極2は、通常、アルミニウム、金、銀、ニッケル、パラジウム、白金等の金属、インジウム及び/又はスズの酸化物などの金属酸化物、ヨウ化銅などのハロゲン化金属、カーボンブラック、或いは、ポリ(3−メチルチオフェン)、ポリピロール、ポリアニリン等の導電性高分子などにより構成される。 This anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or A conductive polymer such as poly (3-methylthiophene), polypyrrole, or polyaniline is used.
陽極2の形成は通常、スパッタリング法、真空蒸着法などにより行われることが多い。また、銀などの金属微粒子、ヨウ化銅などの微粒子、カーボンブラック、導電性の金属酸化物微粒子、導電性高分子微粉末などを用いて陽極を形成する場合には、適当なバインダー樹脂溶液に分散させて、基板1上に塗布することにより陽極2を形成することもできる。さらに、導電性高分子の場合は、電解重合により直接基板1上に薄膜を形成したり、基板1上に導電性高分子を塗布して陽極2を形成することもできる(Appl.Phys.Lett.,60巻,2711頁,1992年)。 In general, the anode 2 is often formed by sputtering, vacuum deposition, or the like. In addition, when forming an anode using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, or conductive polymer fine powder, an appropriate binder resin solution is used. The anode 2 can also be formed by dispersing and coating the substrate 1. Further, in the case of a conductive polymer, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Appl. Phys. Lett. 60, 2711, 1992).
陽極2は通常は単層構造であるが、所望により複数の材料からなる積層構造とすること
も可能である。
The anode 2 usually has a single-layer structure, but it can also have a laminated structure made of a plurality of materials if desired.
陽極2の厚みは、必要とする透明性により異なる。透明性が必要とされる場合は、可視光の透過率を、通常60%以上、好ましくは80%以上とすることが望ましい。この場合、陽極の厚みは通常5nm以上、好ましくは10nm以上であり、また通常1000nm以下、好ましくは500nm以下程度である。不透明でよい場合は陽極2の厚みは任意であり、陽極2は基板1と同一でもよい。また、さらには上記の陽極2の上に異なる導電材料を積層することも可能である。 The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably about 500 nm or less. When it may be opaque, the thickness of the anode 2 is arbitrary, and the anode 2 may be the same as the substrate 1. Furthermore, it is also possible to laminate different conductive materials on the anode 2 described above.
陽極に付着した不純物を除去し、イオン化ポテンシャルを調整して正孔注入性を向上させることを目的に、陽極表面を紫外線(UV)/オゾン処理したり、酸素プラズマ、アルゴンプラズマ処理したりすることは好ましい。 The surface of the anode is treated with ultraviolet (UV) / ozone, oxygen plasma, or argon plasma for the purpose of removing impurities adhering to the anode and adjusting the ionization potential to improve hole injection. Is preferred.
[3]正孔注入層
正孔注入層3は陽極2から発光層4へ正孔を輸送する層であるため、正孔注入層3には正孔輸送性化合物を含むことが好ましい。
[3] Hole Injection Layer Since the hole injection layer 3 is a layer that transports holes from the anode 2 to the light emitting layer 4, the hole injection layer 3 preferably contains a hole transporting compound.
正孔注入層3では、電気的に中性の化合物から電子が一つ除かれたカチオンラジカルが、近傍の電気的に中性な化合物から一電子を受容することによって、正孔が移動する。素子非通電時の正孔注入層3にカチオンラジカル化合物が含まれない場合は、通電時に、正孔輸送性化合物が陽極2に電子を与えることにより正孔輸送性化合物のカチオンラジカルが生成し、このカチオンラジカルと電気的に中性な正孔輸送性化合物との間で電子の授受が行われることにより正孔を輸送する。 In the hole injection layer 3, a cation radical obtained by removing one electron from an electrically neutral compound accepts one electron from a nearby electrically neutral compound, whereby holes move. When the cation radical compound is not included in the hole injection layer 3 when the element is not energized, the cation radical of the hole transport compound is generated when the hole transport compound gives electrons to the anode 2 during energization, Holes are transported by transferring electrons between the cation radical and an electrically neutral hole transporting compound.
正孔注入層3にカチオンラジカル化合物が含まれると、陽極2による酸化によって生成する以上の濃度で正孔輸送に必要なカチオンラジカルが存在することになり、正孔輸送性能が向上するため、正孔注入層3にカチオンラジカル化合物を含むことが好ましい。カチオンラジカル化合物の近傍に電気的に中性な正孔輸送性化合物が存在すると、電子の受け渡しがスムーズに行われるため、正孔注入層3にカチオンラジカル化合物と正孔輸送性化合物とを含むことがさらに好ましい。 When the hole injection layer 3 contains a cation radical compound, cation radicals necessary for hole transport are present at a concentration higher than that generated by oxidation by the anode 2, and the hole transport performance is improved. It is preferable that the hole injection layer 3 contains a cation radical compound. When an electrically neutral hole transporting compound is present in the vicinity of the cation radical compound, electrons are transferred smoothly, so that the hole injection layer 3 contains a cation radical compound and a hole transporting compound. Is more preferable.
ここで、カチオンラジカル化合物とは、正孔輸送性化合物から一電子取り除いた化学種であるカチオンラジカルと、対アニオンからなるイオン化合物であり、移動しやすい正孔(フリーキャリア)を既に有している。 Here, the cation radical compound is a cation radical that is a chemical species obtained by removing one electron from a hole transporting compound, and an ionic compound composed of a counter anion, and already has holes (free carriers) that are easy to move. Yes.
また、正孔輸送性化合物に電子受容性化合物を混合することによって、正孔輸送性化合物から電子受容性化合物への一電子移動が起こり、上述のカチオンラジカル化合物が生成する。このため、正孔注入層3に正孔輸送性化合物と電子受容性化合物とを含むことが好ましい。 Further, by mixing an electron-accepting compound with the hole-transporting compound, one-electron transfer from the hole-transporting compound to the electron-accepting compound occurs, and the above-described cation radical compound is generated. For this reason, it is preferable that the hole injection layer 3 contains a hole transporting compound and an electron accepting compound.
以上の好ましい材料についてまとめると、正孔注入層3に正孔輸送性化合物を含むことが好ましく、正孔輸送性化合物と電子受容性化合物とを含むことがさらに好ましい。また、正孔注入層3にカチオンラジカル化合物を含むことが好ましく、カチオンラジカル化合物と正孔輸送性化合物とを含むことがさらに好ましい。 Summarizing the above preferred materials, the hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. The hole injection layer 3 preferably contains a cation radical compound, and more preferably contains a cation radical compound and a hole transporting compound.
さらに、必要に応じて、正孔注入層3には電荷のトラップになりにくいバインダー樹脂や、塗布性改良剤を含んでいてもよい。 Furthermore, the hole injection layer 3 may contain a binder resin that does not easily trap charges and a coating property improving agent as necessary.
但し、正孔注入層3として、電子受容性化合物のみを湿式製膜法によって陽極2上に製膜し、その上から直接、本発明の有機電界発光素子用組成物を塗布、積層することも可能である。この場合、本発明の有機電界発光素子用組成物の一部が電子受容性化合物と相互作用することによって、正孔注入性に優れた層が形成される。 However, as the hole injection layer 3, only the electron-accepting compound is formed on the anode 2 by a wet film forming method, and the organic electroluminescent element composition of the present invention is directly applied and laminated thereon. Is possible. In this case, when a part of the composition for organic electroluminescent elements of the present invention interacts with the electron accepting compound, a layer excellent in hole injecting property is formed.
(正孔輸送性化合物)
正孔輸送性化合物としては、4.5eV〜6.0eVのイオン化ポテンシャルを有する化合物が好ましい。
(Hole transporting compound)
As the hole transporting compound, a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable.
正孔輸送性化合物の例としては、本発明の電荷輸送材料の他、芳香族アミン化合物、フタロシアニン誘導体、ポルフィリン誘導体、オリゴチオフェン誘導体、ポリチオフェン誘導体等が挙げられる。中でも非晶質性、可視光の透過率の点から、芳香族アミン化合物が好ましい。 Examples of the hole transporting compound include an aromatic amine compound, a phthalocyanine derivative, a porphyrin derivative, an oligothiophene derivative, a polythiophene derivative and the like in addition to the charge transport material of the present invention. Of these, aromatic amine compounds are preferred from the viewpoints of amorphousness and visible light transmittance.
芳香族アミン化合物の中でも、特に、本発明の電荷輸送材料などの芳香族三級アミン化合物が好ましい。ここで、芳香族三級アミン化合物とは、芳香族三級アミン構造を有する化合物であって、芳香族三級アミン由来の基を有する化合物も含む。 Among the aromatic amine compounds, aromatic tertiary amine compounds such as the charge transport material of the present invention are particularly preferable. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.
芳香族三級アミン化合物の種類は特に制限されないが、表面平滑化効果の点から、重量平均分子量が1000以上、1000000以下の高分子化合物(繰り返し単位が連なる重合型有機化合物)がさらに好ましい。 The type of the aromatic tertiary amine compound is not particularly limited, but a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymerizable organic compound in which repeating units are linked) is more preferable from the viewpoint of the surface smoothing effect.
芳香族三級アミン高分子化合物の好ましい例として、下記一般式(VII)で表される繰り返し単位を有する高分子化合物が挙げられる。 Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following general formula (VII).
Ar21〜Ar25及びAr31〜Ar41としては、任意の芳香族炭化水素環又は芳香族複素環由来の、1価又は2価の基が適用可能である。これらは各々同一であっても、互いに異なっていてもよい。また、任意の置換基を有していてもよい。 As Ar 21 to Ar 25 and Ar 31 to Ar 41 , any monovalent or divalent group derived from any aromatic hydrocarbon ring or aromatic heterocyclic ring is applicable. These may be the same or different from each other. Moreover, you may have arbitrary substituents.
その芳香族炭化水素環としては、5又は6員環の単環又は2〜5縮合環が挙げられる。具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などが挙げられる。 Examples of the aromatic hydrocarbon ring include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring. Specific examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
また、その芳香族複素環としては、5又は6員環の単環又は2〜4縮合環が挙げられる。具体例としては、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などが挙げられる。 The aromatic heterocycle includes a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, Thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring , Synoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
また、Ar23〜Ar25、Ar31〜Ar35、Ar37〜Ar40としては、上に例示した1種類又は2種類以上の芳香族炭化水素環及び/又は芳香族複素環由来の2価の基を2つ以上連結して用いることもできる。 Moreover, as Ar < 23 > -Ar < 25 >, Ar < 31 > -Ar < 35 >, Ar < 37 > -Ar < 40 >, the bivalent origin derived from the 1 type or 2 or more types of aromatic hydrocarbon ring and / or aromatic heterocycle which were illustrated above is shown. Two or more groups may be linked and used.
Ar21〜Ar41の芳香族炭化水素環及び/又は芳香族複素環由来の基は、さらに置換基を有していてもよい。置換基の分子量としては、通常400以下、中でも250以下程度が好ましい。置換基の種類は特に制限されないが、例としては、次の置換基群Wから選ばれる1種又は2種以上が挙げられる。 The group derived from the aromatic hydrocarbon ring and / or aromatic heterocycle of Ar 21 to Ar 41 may further have a substituent. The molecular weight of the substituent is usually 400 or less, preferably about 250 or less. The type of the substituent is not particularly limited, and examples thereof include one or more selected from the following substituent group W.
[置換基群W]
メチル基、エチル基等の、炭素数が通常1以上、通常10以下、好ましくは8以下のアルキル基;ビニル基等の、炭素数が通常2以上、通常11以下、好ましくは5以下のアルケニル基;エチニル基等の、炭素数が通常2以上、通常11以下、好ましくは5以下のアルキニル基;メトキシ基、エトキシ基等の、炭素数が通常1以上、通常10以下、好ましくは6以下のアルコキシ基;フェノキシ基、ナフトキシ基、ピリジルオキシ基等の、炭素数が通常4以上、好ましくは5以上、通常25以下、好ましくは14以下のアリールオキシ基;メトキシカルボニル基、エトキシカルボニル基等の、炭素数が通常2以上、通常11以下、好ましくは7以下のアルコキシカルボニル基;ジメチルアミノ基、ジエチルアミノ基等の、炭素数が通常2以上、通常20以下、好ましくは12以下のジアルキルアミノ基;ジフェニルアミノ基、ジトリルアミノ基、N−カルバゾリル基等の、炭素数が通常10以上、好ましくは12以上、通常30以下、好ましくは22以下のジアリールアミノ基;フェニルメチルアミノ基等の、炭素数が通常6以上、好ましくは7以上、通常25以下、好ましくは17以下のアリールアルキルアミノ基;アセチル基、ベンゾイル基等の、炭素数が通常2以上、通常10以下、好ましくは7以下のアシル基;フッ素原子、塩素原子等のハロゲン原子;トリフルオロメチル基等の、炭素数が通常1以上、通常8以下、好ましくは4以下のハロアルキル基;メチルチオ基、エチルチオ基等の、炭素数が通常1以上、通常10以下、好ましくは6以下のアルキルチオ基;フェニルチオ基、ナフチルチオ基、ピリジルチオ基等の、炭素数が通常4以上、好ましくは5以上、通常25以下、好ましくは14以下のアリールチオ基;トリメチルシリル基、トリフェニルシリル基等の、炭素数が通常2以上、好ましくは3以上、通常33以下、好ましくは26以下のシリル基;トリメチルシロキシ基、トリフェニルシロキシ基等の、炭素数が通常2以上、好ましくは3以上、通常33以下、好ましくは26以下のシロキシ基;シアノ基;フェニル基、ナフチル基等の、炭素数が通常6以上、通常30以下、好ましくは18以下の芳香族炭化水素環基;チエニル基、ピリジル基等の、炭素数が通常3以上、好ましくは4以上、通常28以下、好ましくは17以下の芳香族複素環基。
[Substituent group W]
An alkyl group having usually 1 or more, usually 10 or less, preferably 8 or less, such as a methyl group or an ethyl group; an alkenyl group having 2 or more, usually 11 or less, preferably 5 or less carbon atoms, such as a vinyl group. An alkynyl group having usually 2 or more, usually 11 or less, preferably 5 or less, such as an ethynyl group; an alkoxy having a carbon number of usually 1 or more, usually 10 or less, preferably 6 or less, such as a methoxy group or an ethoxy group; A group; an aryloxy group such as a phenoxy group, a naphthoxy group, a pyridyloxy group, etc., usually 4 or more, preferably 5 or more, usually 25 or less, preferably 14 or less; a carbon such as a methoxycarbonyl group or an ethoxycarbonyl group An alkoxycarbonyl group having a number of usually 2 or more, usually 11 or less, preferably 7 or less; a dimethylamino group, a diethylamino group or the like, and usually having 2 or more carbon atoms Usually 20 or less, preferably 12 or less dialkylamino group; diphenylamino group, ditolylamino group, N-carbazolyl group, etc., and usually diarylamino having 10 or more carbon atoms, preferably 12 or more, usually 30 or less, preferably 22 or less Group: an arylalkylamino group having 6 or more carbon atoms, preferably 7 or more, usually 25 or less, preferably 17 or less, such as a phenylmethylamino group; an acetyl group, a benzoyl group or the like, and usually having 2 or more carbon atoms, Usually an acyl group of 10 or less, preferably 7 or less; a halogen atom such as a fluorine atom or a chlorine atom; a haloalkyl group having a carbon number of usually 1 or more, usually 8 or less, preferably 4 or less, such as a trifluoromethyl group; An alkylthio group having 1 to 10 carbon atoms, preferably 6 or less, preferably 6 or less; An arylthio group having usually 4 or more, preferably 5 or more, usually 25 or less, preferably 14 or less, such as a ruthio group, a naphthylthio group, or a pyridylthio group; Or more, preferably 3 or more, usually 33 or less, preferably 26 or less silyl group; trimethylsiloxy group, triphenylsiloxy group, etc., the carbon number is usually 2 or more, preferably 3 or more, usually 33 or less, preferably 26 or less. A siloxy group; a cyano group; an aromatic hydrocarbon ring group having usually 6 or more, usually 30 or less, preferably 18 or less, such as a phenyl group or a naphthyl group; a carbon number such as a thienyl group or a pyridyl group. An aromatic heterocyclic group of 3 or more, preferably 4 or more, usually 28 or less, preferably 17 or less.
Ar21、Ar22としては、高分子化合物の溶解性、耐熱性、正孔注入・輸送性の点から、ベンゼン環、ナフタレン環、フェナントレン環、チオフェン環、ピリジン環由来の1価の基が好ましく、フェニル基、ナフチル基がさらに好ましい。 Ar 21 and Ar 22 are preferably monovalent groups derived from a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, or a pyridine ring from the viewpoint of the solubility, heat resistance, and hole injection / transport properties of the polymer compound. More preferred are a phenyl group and a naphthyl group.
また、Ar23〜Ar25としては、耐熱性、酸化還元電位を含めた正孔注入・輸送性の点から、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環由来の2価の基が好ましく、フェニレン基、ビフェニレン基、ナフチレン基がさらに好ましい。 Ar 23 to Ar 25 are preferably divalent groups derived from a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring from the viewpoint of heat resistance and hole injection / transport properties including redox potential. A group, a biphenylene group, and a naphthylene group are more preferable.
R31、R32としては、水素原子又は任意の置換基が適用可能である。これらは互いに同一であってもよく、異なっていてもよい。置換基の種類は、特に制限されないが、適用可能な置換基を例示するならば、アルキル基、アルケニル基、アルキニル基、アルコキシ基、シリル基、シロキシ基、芳香族炭化水素基、芳香族複素環基、ハロゲン原子が挙げられる。これらの具体例としては、前記の置換基群Wにおいて例示した各基が挙げられる。 As R 31 and R 32 , a hydrogen atom or an arbitrary substituent is applicable. These may be the same or different from each other. The type of the substituent is not particularly limited, and examples of applicable substituents include alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, silyl groups, siloxy groups, aromatic hydrocarbon groups, aromatic heterocyclic rings. Group and halogen atom. Specific examples thereof include the groups exemplified in the above substituent group W.
一般式(VII)で表される繰り返し単位を有する芳香族三級アミン高分子化合物の具体例としては、WO2005/089024号に記載のものが挙げられ、その好適例も同様であり、例えば下記構造式で表される化合物(PB−1)が挙げられるが、何らそれらに限定されるものではない。 Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the general formula (VII) include those described in WO 2005/089024, and suitable examples thereof are also the same. Although the compound (PB-1) represented by a formula is mentioned, it is not limited to them at all.
他の芳香族三級アミン高分子化合物の好ましい例として、下記一般式(VIII)及び/又は一般式(IX)で表される繰り返し単位を含む高分子化合物が挙げられる。 Preferable examples of other aromatic tertiary amine polymer compounds include polymer compounds containing a repeating unit represented by the following general formula (VIII) and / or general formula (IX).
Ar45,Ar47,Ar48及びAr44、Ar46の具体例、好ましい例、有していてもよい置換基の例及び好ましい置換基の例は、それぞれ、Ar21,Ar22及びAr23〜Ar25と同様である。R41〜R43はとして好ましくは水素原子又は[置換基群W]に記載されている置換基であり、さらに好ましくは、水素原子、アルキル基、アルコキシ基、アミノ基、芳香族炭化水素基、芳香族炭化水素基である。 Specific examples of Ar 45 , Ar 47 , Ar 48 and Ar 44 , Ar 46 , preferred examples, examples of substituents that may be included, and examples of preferred substituents are Ar 21 , Ar 22 and Ar 23 to Ar respectively. Same as Ar 25 . R 41 to R 43 are preferably a hydrogen atom or a substituent described in [Substituent group W], and more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aromatic hydrocarbon group, It is an aromatic hydrocarbon group.
一般式(VIII)及び/又は(IX)で表される繰り返し単位を含む芳香族三級アミン高分子化合物の具体例としては、WO2005/089024号に記載のものが挙げられ、その好適例も同様であるが、何らそれらに限定されるものではない。 Specific examples of the aromatic tertiary amine polymer compound containing a repeating unit represented by the general formula (VIII) and / or (IX) include those described in WO 2005/089024, and preferred examples thereof are also the same. However, it is not limited to them.
また、湿式製膜法により正孔注入層を形成する場合には、種々の溶媒に溶解し易い正孔輸送性化合物が好ましい。芳香族三級アミン化合物としては、例えば、ビナフチル系化合物(特開2004−014187)及び非対称1,4−フェニレンジアミン化合物(特開2004−026732)が好ましい。 Moreover, when forming a positive hole injection layer with a wet film forming method, the positive hole transport compound which is easy to melt | dissolve in a various solvent is preferable. As the aromatic tertiary amine compound, for example, a binaphthyl compound (Japanese Patent Laid-Open No. 2004-014187) and an asymmetric 1,4-phenylenediamine compound (Japanese Patent Laid-Open No. 2004-026732) are preferable.
また、従来、有機電界発光素子における正孔注入・輸送性の薄膜精製材料として利用されてきた芳香族アミン化合物の中から、種々の溶媒に溶解し易い化合物を適宜選択してもよい。正孔注入層の正孔輸送性化合物に適用可能な芳香族アミン化合物としては、例えば、有機電界発光素子における正孔注入・輸送性の層形成材料として利用されてきた、従来公知の化合物が挙げられる。例えば、1,1−ビス(4−ジ−p−トリルアミノフェニル)シクロヘキサン等の3級芳香族アミンユニットを連結した芳香族ジアミン化合物(特開昭59−194393号公報);4,4’−ビス[N−(1−ナフチル)−N−フェニルアミノ]ビフェニルで代表される2個以上の3級アミンを含み2個以上の縮合芳香族環が窒素原子に置換した芳香族アミン化合物(特開平5−234681号公報);トリフェニルベンゼンの誘導体でスターバースト構造を有する芳香族トリアミン化合物(米国特許第4,923,774号);N,N’−ジフェニル−N,N’−ビス(3−メチルフェニル)ビフェニル−4,4’−ジアミン等の芳香族ジアミン化合物(米国特許第4,764,625号);α,α,α’,α’−テトラメチル−α,α’−ビス(4−ジ(p−トリル)アミノフェニル)−p−キシレン(特開平3−269084号公報);分子全体として立体的に非対称なトリフェニルアミン誘導体(特開平4−129271号公報);ピレニル基に芳香族ジアミノ基が複数個置換した化合物(特開平4−175395号公報);エチレン基で3級芳香族アミンユニットを連結した芳香族ジアミン化合物(特開平4−264189号公報);スチリル構造を有する芳香族ジアミン(特開平4−290851号公報);チオフェン基で芳香族3級アミンユニットを連結した化合物(特開平4−304466号公報);スターバースト型芳香族トリアミン化合物(特開平4−308688号公報);ベンジルフェニル化合物(特開平4−364153号公報);フルオレン基で3級アミンを連結した化合物(特開平5−25473号公報);トリアミン化合物(特開平5−239455号公報);ビスジピリジルアミノビフェニル(特開平5−320634号公報);N,N,N−トリフェニルアミン誘導体(特開平6−1972号公報);フェノキサジン構造を有する芳香族ジアミン(特開平7−138562号公報);ジアミノフェニルフェナントリジン誘導体(特開平7−252474号公報);ヒドラゾン化合物(特開平2−311591号公報);シラザン化合物(米国特許第4,950,950号公報);シラナミン誘導体(特開平6−49079号公報);ホスファミン誘導体(特開平6−25659号公報);キナクリドン化合物等が挙げられる。これらの芳香族アミン化合物は、必要に応じて2種以上を混合して用いてもよい。 In addition, compounds that are easily dissolved in various solvents may be appropriately selected from aromatic amine compounds that have been conventionally used as a hole injection / transport thin film purification material in organic electroluminescence devices. Examples of the aromatic amine compound applicable to the hole-transporting compound of the hole-injecting layer include conventionally known compounds that have been utilized as a hole-injecting / transporting layer-forming material in organic electroluminescence devices. It is done. For example, an aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked (JP 59-194393 A); 4,4′- An aromatic amine compound containing two or more tertiary amines represented by bis [N- (1-naphthyl) -N-phenylamino] biphenyl and having two or more condensed aromatic rings substituted with nitrogen atoms No. 5-23481); an aromatic triamine compound having a starburst structure as a derivative of triphenylbenzene (US Pat. No. 4,923,774); N, N′-diphenyl-N, N′-bis (3- Aromatic diamine compounds such as methylphenyl) biphenyl-4,4′-diamine (US Pat. No. 4,764,625); α, α, α ′, α′-tetramethyl-α, α′- (4-di (p-tolyl) aminophenyl) -p-xylene (Japanese Patent Laid-Open No. 3-269084); sterically asymmetric triphenylamine derivative as a whole molecule (Japanese Patent Laid-Open No. 4-129271); pyrenyl A compound in which a plurality of aromatic diamino groups are substituted on the group (Japanese Patent Laid-Open No. 4-175395); an aromatic diamine compound in which a tertiary aromatic amine unit is linked with an ethylene group (Japanese Patent Laid-Open No. 4-264189); a styryl structure An aromatic diamine having a thiophene group (JP-A-4-290851); a compound in which an aromatic tertiary amine unit is linked by a thiophene group (JP-A-4-304466); a starburst type aromatic triamine compound (JP-A-4-30481) 308688); benzylphenyl compound (Japanese Patent Laid-Open No. 4-364153); Compounds in which thiones are linked (JP-A-5-25473); triamine compounds (JP-A-5-239455); bisdipyridylaminobiphenyl (JP-A-5-320634); N, N, N-triphenylamine Derivatives (JP-A-6-1972); Aromatic diamines having a phenoxazine structure (JP-A-7-138562); Diaminophenylphenanthridine derivatives (JP-A-7-252474); 2-311591); silazane compounds (US Pat. No. 4,950,950); silanamine derivatives (JP-A-6-49079); phosphamine derivatives (JP-A-6-25659); quinacridone compounds, etc. Can be mentioned. These aromatic amine compounds may be used in combination of two or more as required.
また、正孔注入層の正孔輸送性化合物に適用可能なフタロシアニン誘導体又はポルフィリン誘導体の好ましい具体例としては、ポルフィリン、5,10,15,20−テトラフェニル−21H,23H−ポルフィリン、5,10,15,20−テトラフェニル−21H,23H−ポルフィリンコバルト(II)、5,10,15,20−テトラフェニル−21H,23H−ポルフィリン銅(II)、5,10,15,20−テトラフェニル−21H,23H−ポルフィリン亜鉛(II)、5,10,15,20−テトラフェニル−21H,23H−ポルフィリンバナジウム(IV)オキシド、5,10,15,20−テトラ(4−ピリジル)−21H,23H−ポルフィリン、29H,31H−フタロシアニン銅(II)、フタロシアニン亜鉛(II)、フタロシアニンチタン、フタロシアニンオキシドマグネシウム、フタロシアニン鉛、フタロシアニン銅(II)、4,4’,4”,4'''−テトラアザ−29H,31H−フタロシアニン等が挙げられる。 Preferred specific examples of the phthalocyanine derivative or porphyrin derivative applicable to the hole transporting compound of the hole injection layer include porphyrin, 5,10,15,20-tetraphenyl-21H, 23H-porphyrin, 5,10 , 15,20-tetraphenyl-21H, 23H-porphyrin cobalt (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin copper (II), 5,10,15,20-tetraphenyl- 21H, 23H-porphyrin zinc (II), 5,10,15,20-tetraphenyl-21H, 23H-porphyrin vanadium (IV) oxide, 5,10,15,20-tetra (4-pyridyl) -21H, 23H -Porphyrin, 29H, 31H-phthalocyanine copper (II), phthalocyanine zinc (II), lid Cyanine titanium, phthalocyanine oxide magnesium, phthalocyanine lead, phthalocyanine copper (II), 4,4 ', 4 ", 4' '' - tetraaza-29H, 31H-phthalocyanine, and the like.
また、正孔注入層の正孔輸送性化合物として適用可能なオリゴチオフェン誘導体の好ましい具体例としては、α−ターチオフェンとその誘導体、α−セキシチオフェンとその誘導体、ナフタレン環を含有するオリゴチオフェン誘導体(特開平6−256341)等が挙げられる。 Further, preferred specific examples of the oligothiophene derivative applicable as the hole transporting compound of the hole injection layer include α-terthiophene and its derivatives, α-sexithiophene and its derivatives, and oligothiophene containing a naphthalene ring. Derivatives (JP-A-6-256341) and the like.
また、本発明における正孔輸送性化合物として適用可能なポリチオフェン誘導体の好ましい具体例としては、ポリ(3,4−エチレンジオキシチオフェン)(PEDOT)、ポリ(3−ヘキシルチオフェン)等が挙げられる。 Further, preferred specific examples of the polythiophene derivative applicable as the hole transporting compound in the present invention include poly (3,4-ethylenedioxythiophene) (PEDOT), poly (3-hexylthiophene) and the like.
なお、これらの正孔輸送性化合物の分子量は、高分子化合物(繰り返し単位が連なる重合性化合物)の場合を除いて、通常9000以下、好ましくは5000以下、また、通常200以上、好ましくは400以上の範囲である。正孔輸送性化合物の分子量が高過ぎると合成及び精製が困難であり好ましくない一方で、分子量が低過ぎると耐熱性が低くなるおそれがありやはり好ましくない。 The molecular weight of these hole transporting compounds is usually 9000 or less, preferably 5000 or less, and usually 200 or more, preferably 400 or more, except in the case of a polymer compound (a polymerizable compound in which repeating units are continuous). Range. If the molecular weight of the hole-transporting compound is too high, synthesis and purification are difficult and not preferable. On the other hand, if the molecular weight is too low, the heat resistance may be lowered, which is also not preferable.
正孔注入層の材料として用いられる正孔輸送性化合物は、このような化合物のうち何れか1種を単独で含有していてもよく、2種以上を含有していてもよい。2種以上の正孔輸送性化合物を含有する場合、その組み合わせは任意であるが、芳香族三級アミン高分子化合物1種又は2種以上と、その他の正孔輸送性化合物1種又は2種以上とを併用するのが好ましい。 The hole transporting compound used as the material for the hole injection layer may contain any one of these compounds alone, or may contain two or more. In the case of containing two or more kinds of hole transporting compounds, the combination is arbitrary, but one or more kinds of aromatic tertiary amine polymer compounds and one or two kinds of other hole transporting compounds. It is preferable to use the above together.
(電子受容性化合物)
電子受容性化合物とは、酸化力を有し、上述の正孔輸送性化合物から一電子受容する能力を有する化合物が好ましく、具体的には、電子親和力が4eV以上である化合物が好ましく、5eV以上の化合物である化合物がさらに好ましい。
(Electron-accepting compound)
The electron-accepting compound is preferably a compound having an oxidizing power and the ability to accept one electron from the above-described hole transporting compound, specifically, a compound having an electron affinity of 4 eV or more is preferable, and 5 eV or more. The compound which is the compound of these is further more preferable.
例としては、4−イソプロピル−4’−メチルジフェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボラート等の有機基の置換したオニウム塩、塩化鉄(III)(特開平11−251067)、ペルオキソ二硫酸アンモニウム等の高原子価の無機化合物、テトラシアノエチレン等のシアノ化合物、トリス(ペンタフルオロフェニル)ボラン(特開2003−31365)等の芳香族ホウ素化合物、フラーレン誘導体、ヨウ素等が挙げられる。 Examples include onium salts substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, iron (III) chloride (JP-A-11-251067), ammonium peroxodisulfate and the like. Examples thereof include valent inorganic compounds, cyano compounds such as tetracyanoethylene, aromatic boron compounds such as tris (pentafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365), fullerene derivatives, iodine and the like.
上記の化合物のうち、強い酸化力を有する点で有機基の置換したオニウム塩、高原子価の無機化合物が好ましく、種々の溶媒に可溶で湿式塗布に適用可能である点で有機基の置換したオニウム塩、シアノ化合物、芳香族ホウ素化合物が好ましい。 Of the above compounds, onium salts substituted with organic groups and high valent inorganic compounds are preferred because of their strong oxidizing power, and organic groups are substituted because they are soluble in various solvents and applicable to wet coating. Preferred are onium salts, cyano compounds, and aromatic boron compounds.
電子受容性化合物として好適な有機基の置換したオニウム塩、シアノ化合物、芳香族ホウ素化合物の具体例としては、WO2005/089024号に記載のものが挙げられ、その好適例も同様であり、例えば下記構造式で表される化合物(A−2)が挙げられるが、何らそれらに限定されるものではない。 Specific examples of the onium salt substituted with an organic group, cyano compound, and aromatic boron compound suitable as an electron-accepting compound include those described in WO 2005/089024, and the preferred examples thereof are also the same. Although the compound (A-2) represented by Structural Formula is mentioned, it is not limited to them at all.
(カチオンラジカル化合物)
カチオンラジカル化合物とは、正孔輸送性化合物から一電子取り除いた化学種であるカチオンラジカルと、対アニオンからなるイオン化合物である。但し、カチオンラジカルが正孔輸送性の高分子化合物由来である場合、カチオンラジカルは高分子化合物の繰り返し単位から一電子取り除いた構造となる。
(Cation radical compound)
The cation radical compound is an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion. However, when the cation radical is derived from a hole transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
カチオンラジカルは、正孔輸送性化合物に前述した化合物から一電子取り除いた化学種であることが好ましく、正孔輸送性化合物としてさらに好ましい化合物から一電子取り除いた化学種であることが非晶質性、可視光の透過率、耐熱性、溶解性などの点からさらに好ましい。 The cation radical is preferably a chemical species obtained by removing one electron from the aforementioned compound in the hole transporting compound, and is preferably a chemical species obtained by removing one electron from a compound more preferable as the hole transporting compound. From the viewpoints of visible light transmittance, heat resistance, solubility, and the like.
カチオンラジカル化合物は、前述の正孔輸送性化合物と電子受容性化合物を混合することにより生成させることができる。即ち、前述の正孔輸送性化合物と電子受容性化合物を混合することにより、正孔輸送性化合物から電子受容性化合物へと電子移動が起こり、正孔輸送性化合物のカチオンラジカルと対アニオンからなるカチオンイオン化合物が生成する。 The cation radical compound can be generated by mixing the hole transporting compound and the electron accepting compound. That is, by mixing the hole transporting compound and the electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the cation radical and the counter anion of the hole transporting compound are included. A cation ion compound is formed.
PEDOT/PSS(Adv.Mater.,2000年,12巻,481頁)やエメラルジン塩酸塩(J.Phys.Chem.,1990年,94巻,7716頁)等の高分子化合物由来のカチオンラジカル化合物は、酸化重合(脱水素重合)、即ち、モノマーを酸性溶液中で、ペルオキソ二硫酸塩等を用いて化学的に、又は、電気化学的に酸化することによっても生成する。この酸化重合(脱水素重合)の場合、モノマーが酸化されることにより、高分子化されるとともに、酸性溶液由来のアニオンを対アニオンとする、高分子の繰り返し単位から一電子取り除かれたカチオンラジカルが生成する。 Cation radical compounds derived from polymer compounds such as PEDOT / PSS (Adv. Mater., 2000, 12, 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, 94, 7716) It is also produced by oxidative polymerization (dehydrogenation polymerization), that is, by oxidizing the monomer chemically or electrochemically with peroxodisulfate in an acidic solution. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is oxidized to be polymerized, and the cation radical is formed by removing one electron from the repeating unit of the polymer with an anion derived from an acidic solution as a counter anion. Produces.
正孔注入層3は、湿式製膜法又は真空蒸着法により陽極2上に形成される。 The hole injection layer 3 is formed on the anode 2 by a wet film forming method or a vacuum deposition method.
陽極2として一般的に用いられるITO(インジウム・スズ酸化物)は、その表面粗さが10nm程度の粗さ(Ra)を有するのに加えて、局所的に突起を有することが多く、短絡欠陥を生じ易いという問題があった。陽極2の上に形成される正孔注入層3は湿式製膜法により形成することは、真空蒸着法より形成する場合と比較して、これら陽極表面の凹凸に起因する、素子の欠陥の発生を低減する利点を有する。 ITO (indium tin oxide), which is generally used as the anode 2, has a surface roughness of about 10 nm (Ra) and, in addition, often has protrusions locally, resulting in short-circuit defects. There was a problem that it was easy to produce. When the hole injection layer 3 formed on the anode 2 is formed by the wet film forming method, the generation of device defects due to the unevenness of the surface of the anode as compared with the case of forming by the vacuum deposition method. Has the advantage of reducing.
湿式製膜法による層形成の場合は、前述した各材料(正孔輸送性化合物、電子受容性化合物、カチオンラジカル化合物)の1種又は2種以上の所定量を、必要により電荷のトラップにならないバインダー樹脂や塗布性改良剤を添加して、溶媒に溶解させて、塗布溶液を調製し、スピンコート、スプレーコート、ディップコート、ダイコート、フレキソ印刷、スクリーン印刷、インクジェット法等の湿式製膜法により陽極上に塗布し、乾燥して、正孔注入層3を形成させる。 In the case of layer formation by a wet film-forming method, a predetermined amount of one or more of the aforementioned materials (hole transporting compound, electron accepting compound, cation radical compound) is not trapped as necessary. Add binder resin and coatability improver, dissolve in solvent, prepare coating solution, by wet film forming method such as spin coating, spray coating, dip coating, die coating, flexographic printing, screen printing, inkjet method etc. It is applied on the anode and dried to form the hole injection layer 3.
湿式製膜法による層形成のために用いられる溶媒としては、前述の各材料(正孔輸送性化合物、電子受容性化合物、カチオンラジカル化合物)を溶解することが可能な溶媒であれば、その種類は特に限定されないが、正孔注入層に用いられる各材料(正孔輸送性化合物、電子受容性化合物、カチオンラジカル化合物)を失活させる恐れのある、失活物質又は失活物質を発生させるものを含まないものが好ましい。 As the solvent used for the layer formation by the wet film forming method, any solvent can be used as long as it can dissolve the above-mentioned materials (hole transporting compound, electron accepting compound, cation radical compound). Is not particularly limited, but generates a deactivating substance or deactivating substance that may deactivate each material (hole transporting compound, electron accepting compound, cation radical compound) used in the hole injection layer The thing which does not contain is preferable.
これらの条件を満たす好ましい溶媒としては、例えば、エーテル系溶媒及びエステル系溶媒が挙げられる。具体的には、エーテル系溶媒としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール−1−モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル;1,2−ジメトキシベンゼン、1,3−ジメトキシベンゼン、アニソール、フェネトール、2−メトキシトルエン、3−メトキシトルエン、4−メトキシトルエン、2,3−ジメチルアニソール、2,4−ジメチルアニソール等の芳香族エーテル等が挙げられる。エステル系溶媒としては、例えば、酢酸エチル、酢酸n−ブチル、乳酸エチル、乳酸n−ブチル等の脂肪族エステル;酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n−ブチル等の芳香族エステル等が挙げられる。これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で用いてもよい。 Preferable solvents that satisfy these conditions include, for example, ether solvents and ester solvents. Specifically, examples of the ether solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1, 3 -Aromatic ethers such as dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and the like. Examples of ester solvents include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid. Examples include aromatic esters such as n-butyl. Any one of these may be used alone, or two or more may be used in any combination and ratio.
上述のエーテル系溶媒及びエステル系溶媒以外に使用可能な溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等のアミド系溶媒、ジメチルスルホキシド等が挙げられる。これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で用いてもよい。また、これらの溶媒のうち1種又は2種以上を、上述のエーテル系溶媒及びエステル系溶媒のうち1種又は2種以上と組み合わせて用いてもよい。特に、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒は、電子受容性化合物及びカチオンラジカル化合物を溶解する能力が低いため、エーテル系溶媒及びエステル系溶媒と混合して用いることが好ましい。 Examples of usable solvents other than the ether solvents and ester solvents described above include aromatic hydrocarbon solvents such as benzene, toluene and xylene, amides such as N, N-dimethylformamide and N, N-dimethylacetamide. System solvents, dimethyl sulfoxide and the like. Any one of these may be used alone, or two or more may be used in any combination and ratio. Moreover, you may use 1 type, or 2 or more types among these solvents in combination with 1 type or 2 or more types among the above-mentioned ether solvent and ester solvent. In particular, aromatic hydrocarbon solvents such as benzene, toluene, and xylene have a low ability to dissolve electron accepting compounds and cation radical compounds, and are therefore preferably used in a mixture with ether solvents and ester solvents.
塗布溶液中における溶媒の濃度は、通常10重量%以上、好ましくは30重量%以上、より好ましくは50%重量以上、また、通常99.999重量%以下、好ましくは99.99重量%以下、さらに好ましくは99.9重量%以下の範囲である。なお、2種以上の溶媒を混合して用いる場合には、これらの溶媒の合計がこの範囲を満たすようにする。 The concentration of the solvent in the coating solution is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, and usually 99.999% by weight or less, preferably 99.99% by weight or less. Preferably it is the range of 99.9 weight% or less. When two or more kinds of solvents are mixed and used, the total of these solvents is set to satisfy this range.
真空蒸着法による層形成の場合には、前述した各材料(正孔輸送性化合物、電子受容性化合物、カチオンラジカル化合物)の1種又は2種以上を真空容器内に設置されたるつぼに入れ(2種以上材料を用いる場合は各々のるつぼに入れ)、真空容器内を適当な真空ポンプで10−4Pa程度まで排気した後、るつぼを加熱して(2種以上材料を用いる場合は各々のるつぼを加熱して)、蒸発量を制御して蒸発させ(2種以上材料を用いる場合はそれぞれ独立に蒸発量を制御して蒸発させ)、るつぼと向き合って置かれた基板の陽極上に正孔注入層を形成させる。なお、2種以上の材料を用いる場合は、それらの混合物をるつぼに入れ、加熱し蒸発させて正孔注入層形成に用いることもできる。 In the case of forming a layer by vacuum deposition, one or more of the aforementioned materials (hole transporting compound, electron accepting compound, cation radical compound) are put in a crucible installed in a vacuum vessel ( When two or more materials are used, put them in each crucible), and after evacuating the inside of the vacuum vessel to about 10 −4 Pa with an appropriate vacuum pump, heat the crucible (if using two or more materials, each Heat the crucible) and evaporate by controlling the amount of evaporation (if more than one material is used, evaporate by controlling the amount of evaporation independently) and place it positively on the anode of the substrate placed facing the crucible A hole injection layer is formed. In addition, when using 2 or more types of materials, they can also be put into a crucible, can be heated and evaporated, and can be used for hole injection layer formation.
このようにして形成される正孔注入層3の膜厚は、通常5nm以上、好ましくは10nm以上、また、通常1000nm以下、好ましくは500nm以下の範囲である。
なお、正孔注入層3は、図6に示す如く、これを省略しても良い。
The film thickness of the hole injection layer 3 thus formed is usually in the range of 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
The hole injection layer 3 may be omitted as shown in FIG.
[4]発光層
正孔注入層3の上には通常発光層4が設けられる。発光層4は例えば前述の発光材料を含む層であり、電界を与えられた電極間において、陽極2から正孔注入層3を通じて注入された正孔と、陰極6から電子輸送層5を通じて注入された電子との再結合により励起されて、主たる発光源となる層である。発光層4は発光材料(ドーパント)と1種又は2種以上のホスト材料を含むことが好ましく、発光層4は本発明の電荷輸送材料をホスト材料として含むことがさらに好ましく、真空蒸着法で形成しても良いが、本発明の有機電界発光素子用組成物を用い、湿式製膜法によって作製された層であることが特に好ましい。
[4] Light-Emitting Layer A normal light-emitting layer 4 is provided on the hole injection layer 3. The light emitting layer 4 is, for example, a layer containing the above-described light emitting material. Between the electrodes to which an electric field is applied, holes injected from the anode 2 through the hole injection layer 3 and from the cathode 6 through the electron transport layer 5 are injected. It is a layer that is excited by recombination with other electrons and becomes the main light emitting source. The light-emitting layer 4 preferably contains a light-emitting material (dopant) and one or more host materials, and the light-emitting layer 4 more preferably contains the charge transport material of the present invention as a host material, and is formed by a vacuum deposition method. However, it is particularly preferable that the layer be prepared by a wet film-forming method using the composition for organic electroluminescent elements of the present invention.
ここで、湿式製膜法とは、前述の如く、溶媒を含む組成物を、スピンコート、スプレーコート、ディップコート、ダイコート、フレキソ印刷、スクリーン印刷、インクジェット法等により製膜するものである。 Here, as described above, the wet film forming method is a method in which a composition containing a solvent is formed by spin coating, spray coating, dip coating, die coating, flexographic printing, screen printing, an inkjet method, or the like.
なお、発光層4は、本発明の性能を損なわない範囲で、他の材料、成分を含んでいてもよい。 In addition, the light emitting layer 4 may contain other materials and components as long as the performance of the present invention is not impaired.
一般に有機電界発光素子において、同じ材料を用いた場合、電極間の膜厚が薄い方が、実効電界が大きくなる為、注入される電流が多くなるので、駆動電圧は低下する。その為、電極間の総膜厚は薄い方が、有機電界発光素子の駆動電圧は低下するが、あまりに薄いと、ITO等の電極に起因する突起により短絡が発生する為、ある程度の膜厚が必要となる。 In general, when the same material is used in the organic electroluminescent element, the thinner the film thickness between the electrodes, the larger the effective electric field, so that the injected current increases, so the driving voltage decreases. For this reason, the driving voltage of the organic electroluminescence device decreases when the total film thickness between the electrodes is thin, but if it is too thin, a short circuit occurs due to the protrusion caused by the electrode such as ITO. Necessary.
本発明においては、発光層4以外に、正孔注入層3及び後述の電子輸送層5等の有機層を有する場合、発光層4と正孔注入層3や電子輸送層5等の他の有機層とを合わせた総膜厚は通常30nm以上、好ましくは50nm以上であり、さらに好ましくは100nm以上で、通常1000nm以下、好ましくは500nm以下であり、さらに好ましくは300nm以下である。また、発光層4以外の正孔注入層3や後述の電子注入層5の導電性が高い場合、発光層4に注入される電荷量が増加する為、例えば正孔注入層3の膜厚を厚くして発光層4の膜厚を薄くし、総膜厚をある程度の膜厚を維持したまま駆動電圧を下げることも可能である。 In the present invention, in addition to the light emitting layer 4, when the organic layer such as the hole injection layer 3 and the electron transport layer 5 described later is provided, the light emitting layer 4 and other organic materials such as the hole injection layer 3 and the electron transport layer 5 are used. The total film thickness combined with the layer is usually 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more, usually 1000 nm or less, preferably 500 nm or less, and more preferably 300 nm or less. In addition, when the conductivity of the hole injection layer 3 other than the light emitting layer 4 and the electron injection layer 5 described later is high, the amount of charge injected into the light emitting layer 4 increases. It is also possible to reduce the drive voltage while increasing the thickness to reduce the thickness of the light emitting layer 4 and maintaining the total thickness to some extent.
よって、発光層4の膜厚は、通常10nm以上、好ましくは20nm以上で、通常300nm以下、好ましくは200nm以下である。なお、本発明の素子が、陽極及び陰極の両極間に、発光層4のみを有する場合の発光層4の膜厚は、通常30nm以上、好ましくは50nm以上、通常500nm以下、好ましくは300nm以下である。 Therefore, the thickness of the light emitting layer 4 is usually 10 nm or more, preferably 20 nm or more, and usually 300 nm or less, preferably 200 nm or less. When the element of the present invention has only the light emitting layer 4 between the anode and the cathode, the thickness of the light emitting layer 4 is usually 30 nm or more, preferably 50 nm or more, usually 500 nm or less, preferably 300 nm or less. is there.
[5]電子注入層
電子注入層5は陰極6から注入された電子を効率よく発光層4へ注入する役割を果たす。電子注入を効率よく行うには、電子注入層5を形成する材料は、仕事関数の低い金属が好ましく、ナトリウムやセシウム等のアルカリ金属、バリウムやカルシウムなどのアルカリ土類金属が用いられる。
電子注入層5の膜厚は0.1〜5nmが好ましい。
[5] Electron Injection Layer The electron injection layer 5 plays a role of efficiently injecting electrons injected from the cathode 6 into the light emitting layer 4. In order to perform electron injection efficiently, the material for forming the electron injection layer 5 is preferably a metal having a low work function, and alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium are used.
The film thickness of the electron injection layer 5 is preferably 0.1 to 5 nm.
また、陰極6と発光層4又は後述の電子輸送層8との界面にLiF、MgF2、Li2O、Cs2CO3等の極薄絶縁膜(0.1〜5nm)を挿入することも、素子の効率を向上させる有効な方法である(Appl.Phys.Lett.,70巻,152頁,1997年;特開平10−74586号公報;IEEETrans.Electron.Devices,44巻,1245頁,1997年;SID 04 Digest,154頁)。 Also, an ultrathin insulating film (0.1 to 5 nm) such as LiF, MgF 2 , Li 2 O, Cs 2 CO 3 may be inserted at the interface between the cathode 6 and the light emitting layer 4 or the electron transport layer 8 described later. This is an effective method for improving the efficiency of the device (Appl. Phys. Lett., 70, 152, 1997; JP-A-10-74586; IEEE Trans. Electron. Devices, 44, 1245, 1997). Year; SID 04 Digest, p. 154).
さらに、後述するバソフェナントロリン等の含窒素複素環化合物や8−ヒドロキシキノリンのアルミニウム錯体などの金属錯体に代表される有機電子輸送材料に、ナトリウム、カリウム、セシウム、リチウム、ルビジウム等のアルカリ金属をドープする(特開平10−270171号公報、特開2002−100478号公報、特開2002−100482号公報などに記載)ことにより、電子注入・輸送性が向上し優れた膜質を両立させることが可能となるため好ましい。この場合の膜厚は通常5nm以上、好ましくは10nm以上で、通常200nm以下、好ましくは100nm以下である。 Furthermore, organic metal transport materials represented by metal complexes such as nitrogen-containing heterocyclic compounds such as bathophenanthroline and aluminum complexes of 8-hydroxyquinoline described later are doped with alkali metals such as sodium, potassium, cesium, lithium and rubidium. (Described in JP-A-10-270171, JP-A 2002-1000047, JP-A 2002-1000048, and the like) makes it possible to improve electron injection / transport properties and achieve excellent film quality. Therefore, it is preferable. The film thickness in this case is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
電子注入層5は、発光層4と同様にして湿式製膜法、或いは真空蒸着法により発光層4上に積層することにより形成される。真空蒸着法の場合には、真空容器内に設置されたるつぼ又は金属ボートに蒸着源を入れ、真空容器内を適当な真空ポンプで10−4Pa程度にまで排気した後、るつぼ又は金属ボートを加熱して蒸発させ、るつぼ又は金属ボートと向き合って置かれた基板上に電子注入層を形成する。 The electron injection layer 5 is formed by laminating on the light emitting layer 4 by a wet film forming method or a vacuum deposition method in the same manner as the light emitting layer 4. In the case of the vacuum vapor deposition method, the vapor deposition source is put in a crucible or metal boat installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 −4 Pa with an appropriate vacuum pump, and then the crucible or metal boat is Evaporate by heating to form an electron injection layer on the substrate placed facing the crucible or metal boat.
アルカリ金属の蒸着は、クロム酸アルカリ金属と還元剤をニクロムに充填したアルカリ金属ディスペンサーを用いて行う。このディスペンサーを真空容器内で加熱することにより、クロム酸アルカリ金属が還元されてアルカリ金属が蒸発される。有機電子輸送材料とアルカリ金属とを共蒸着する場合は、有機電子輸送材料を真空容器内に設置されたるつぼに入れ、真空容器内を適当な真空ポンプで10−4Pa程度にまで排気した後、各々のるつぼ及びディスペンサーを同時に加熱して蒸発させ、るつぼ及びディスペンサーと向き合って置かれた基板上に電子注入層を形成する。 The alkali metal is deposited using an alkali metal dispenser in which nichrome is filled with an alkali metal chromate and a reducing agent. By heating the dispenser in a vacuum container, the alkali metal chromate is reduced and the alkali metal is evaporated. In the case of co-evaporating the organic electron transport material and the alkali metal, the organic electron transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 −4 Pa with a suitable vacuum pump. Each crucible and dispenser are simultaneously heated and evaporated to form an electron injection layer on the substrate placed facing the crucible and dispenser.
このとき、電子注入層5の膜厚方向において均一に共蒸着されるが、膜厚方向において濃度分布があっても構わない。
なお、電子注入層5は、図5,6に示す如く、これを省略しても良い。
At this time, co-evaporation is uniformly performed in the film thickness direction of the electron injection layer 5, but there may be a concentration distribution in the film thickness direction.
The electron injection layer 5 may be omitted as shown in FIGS.
[6]陰極
陰極6は、発光層側の層(電子注入層5又は発光層4など)に電子を注入する役割を果たす。陰極6として用いられる材料は、前記陽極2に使用される材料を用いることが可能であるが、効率よく電子注入を行うには、仕事関数の低い金属が好ましく、スズ、マグネシウム、インジウム、カルシウム、アルミニウム、銀等の適当な金属又はそれらの合金が用いられる。具体例としては、マグネシウム−銀合金、マグネシウム−インジウム合金、アルミニウム−リチウム合金等の低仕事関数合金電極が挙げられる。
[6] Cathode The cathode 6 plays a role of injecting electrons into a layer on the light emitting layer side (such as the electron injection layer 5 or the light emitting layer 4). The material used for the cathode 6 can be the material used for the anode 2, but a metal having a low work function is preferable for efficient electron injection, such as tin, magnesium, indium, calcium, A suitable metal such as aluminum or silver or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
陰極6の膜厚は通常、陽極2と同様である。低仕事関数金属から成る陰極を保護する目的で、この上にさらに、仕事関数が高く大気に対して安定な金属層を積層することは素子の安定性を増す。この目的のために、アルミニウム、銀、銅、ニッケル、クロム、金、白金等の金属が使われる。 The film thickness of the cathode 6 is usually the same as that of the anode 2. For the purpose of protecting the cathode made of a low work function metal, further laminating a metal layer having a high work function and stable to the atmosphere on the cathode increases the stability of the device. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used.
[7]その他の構成層
以上、図1に示す層構成の素子を中心に説明してきたが、本発明の有機電界発光素子における陽極2及び陰極6と発光層4との間には、その性能を損なわない限り、上記説明にある層の他にも、任意の層を有していてもよく、また発光層4以外の任意の層を省略してもよい。
[7] Other Constituent Layers While the description has been made centering on the element having the layer structure shown in FIG. In addition to the layers described above, any layer may be included, and any layer other than the light emitting layer 4 may be omitted.
有してもよい層としては例えば、電子輸送層7が挙げられる。電子輸送層7は素子の発光効率をさらに向上させることを目的として、図2に示す如く、発光層4と電子注入層5との間に設けられる。 Examples of the layer that may be included include the electron transport layer 7. The electron transport layer 7 is provided between the light emitting layer 4 and the electron injection layer 5 as shown in FIG. 2 for the purpose of further improving the light emission efficiency of the device.
電子輸送層7は、電界を与えられた電極間において陰極6から注入された電子を効率よく発光層4の方向に輸送することができる化合物より形成される。電子輸送層7に用いられる電子輸送性化合物としては、陰極6又は電子注入層5からの電子注入効率が高く、かつ、高い電子移動度を有し注入された電子を効率よく輸送することができる化合物であることが必要である。
このような条件を満たす材料としては、8−ヒドロキシキノリンのアルミニウム錯体などの金属錯体(特開昭59−194393号公報)、10−ヒドロキシベンゾ[h]キノリンの金属錯体、オキサジアゾール誘導体、ジスチリルビフェニル誘導体、シロール誘導体、3−又は5−ヒドロキシフラボン金属錯体、ベンズオキサゾール金属錯体、ベンゾチアゾール金属錯体、トリスベンズイミダゾリルベンゼン(米国特許第5,645,948号)、キノキサリン化合物(特開平6−207169号公報)、フェナントロリン誘導体(特開平5−331459号公報)、2−t−ブチル−9,10−N,N’−ジシアノアントラキノンジイミン、n型水素化非晶質炭化シリコン、n型硫化亜鉛、n型セレン化亜鉛などが挙げられる。
The electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 6 between electrodes to which an electric field is applied in the direction of the light emitting layer 4. As the electron transporting compound used for the electron transport layer 7, the electron injection efficiency from the cathode 6 or the electron injection layer 5 is high, and the injected electrons can be efficiently transported with high electron mobility. It must be a compound.
Materials satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives, Styryl biphenyl derivative, silole derivative, 3- or 5-hydroxyflavone metal complex, benzoxazole metal complex, benzothiazole metal complex, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compound No. 207169), phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type sulfide Examples include zinc and n-type zinc selenide.
電子輸送層7の膜厚は、通常下限は1nm、好ましくは5nm程度であり、上限は通常300nm、好ましくは100nm程度である。 The lower limit of the thickness of the electron transport layer 7 is usually 1 nm, preferably about 5 nm, and the upper limit is usually about 300 nm, preferably about 100 nm.
電子輸送層7は、正孔注入層3と同様にして湿式製膜法、或いは真空蒸着法により発光層4上に積層することにより形成される。通常は、真空蒸着法が用いられる。 The electron transport layer 7 is formed by laminating on the light emitting layer 4 by a wet film forming method or a vacuum deposition method in the same manner as the hole injection layer 3. Usually, a vacuum deposition method is used.
また、特に、発光物質として燐光材料を用いたり、青色発光材料を用いたりする場合、図3に示す如く、正孔阻止層8を設けることも効果的である。正孔阻止層8は正孔と電子を発光層4内に閉じこめて、発光効率を向上させる機能を有する。即ち、正孔阻止層8は、発光層4から移動してくる正孔が電子輸送層7に到達するのを阻止することで、発光層4内で電子との再結合確率を増やし、生成した励起子を発光層4内に閉じこめる役割と、電子輸送層8から注入された電子を効率よく発光層4の方向に輸送する役割がある。 In particular, when a phosphorescent material or a blue light emitting material is used as the light emitting substance, it is also effective to provide the hole blocking layer 8 as shown in FIG. The hole blocking layer 8 has a function of confining holes and electrons in the light emitting layer 4 and improving luminous efficiency. That is, the hole blocking layer 8 is generated by blocking the holes moving from the light emitting layer 4 from reaching the electron transport layer 7, thereby increasing the recombination probability with electrons in the light emitting layer 4. There is a role of confining excitons in the light emitting layer 4 and a role of efficiently transporting electrons injected from the electron transport layer 8 toward the light emitting layer 4.
正孔阻止層8は、陽極2から移動してくる正孔を陰極6に到達するのを阻止する役割と、陰極6から注入された電子を率よく発光層4の方向に輸送することができる化合物により、発光層4の上に、発光層4の陰極6側の界面に接するように積層形成される。 The hole blocking layer 8 prevents the holes moving from the anode 2 from reaching the cathode 6 and can efficiently transport the electrons injected from the cathode 6 toward the light emitting layer 4. The compound is laminated on the light emitting layer 4 so as to be in contact with the interface of the light emitting layer 4 on the cathode 6 side.
正孔阻止層8を構成する材料に求められる物性としては、電子移動度が高く正孔移動度が低いこと、エネルギーギャップ(HOMO、LUMOの差)が大きいこと、励起三重項準位(T1)が高いことが挙げられる。 The physical properties required for the material constituting the hole blocking layer 8 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.
このような条件を満たす正孔阻止層材料としては、ビス(2−メチル−8−キノリノラト)(フェノラト)アルミニウム、ビス(2−メチル−8−キノリノラト)(トリフェニルシラノラト)アルミニウム等の混合配位子錯体、ビス(2−メチル−8−キノラト)アルミニウム−μ−オキソ−ビス−(2−メチル−8−キノリラト)アルミニウム二核金属錯体等の金属錯体、ジスチリルビフェニル誘導体等のスチリル化合物(特開平11−242996)、3−(4−ビフェニルイル)−4−フェニル−5(4−tert−ブチルフェニル)−1,2,4−トリアゾール等のトリアゾール誘導体(特開平7−41759号公報)、バソクプロイン等のフェナントロリン誘導体(特開平10−79297号公報)が挙げられる。 Examples of the hole blocking layer material satisfying such conditions include mixed arrangements of bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like. Ligand complexes, metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, styryl compounds such as distyrylbiphenyl derivatives ( JP-A-11-242996), triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (JP-A-7-41759) And phenanthroline derivatives such as bathocuproine (Japanese Patent Laid-Open No. 10-79297).
さらに、WO2005/022962号公報に記載の2,4,6位が置換されたピリジン環を少なくとも1個有する化合物も正孔阻止材料として好ましい。 Furthermore, a compound having at least one pyridine ring substituted at the 2,4,6-positions described in WO2005 / 022962 is also preferable as the hole blocking material.
正孔阻止層8の膜厚は、通常0.3nm以上、好ましくは0.5nm以上で、通常100nm以下、好ましくは50nm以下である。 The film thickness of the hole blocking layer 8 is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.
正孔阻止層8も正孔注入層3と同様の方法で形成することができるが、通常は真空蒸着法が用いられる。 The hole blocking layer 8 can also be formed by the same method as the hole injection layer 3, but a vacuum deposition method is usually used.
電子輸送層7及び正孔阻止層8は必要に応じて、適宜設ければよく、1)電子輸送層のみ、2)正孔阻止層のみ、3)正孔阻止層/電子輸送層の積層、4)用いない、等、用法がある。 The electron transport layer 7 and the hole blocking layer 8 may be appropriately provided as necessary. 1) Only the electron transport layer, 2) Only the hole blocking layer, 3) Stack of hole blocking layer / electron transport layer, 4) There are usages such as not using.
正孔阻止層8と同様の目的で、図4に示す如く、正孔注入層3と発光層4の間に電子阻止層9を設けることも効果的である。電子阻止層9は、発光層4から移動してくる電子が正孔注入層3に到達するのを阻止することで、発光層4内で正孔との再結合確率を増やし、生成した励起子を発光層4内に閉じこめる役割と、正孔注入層3から注入された正孔を効率よく発光層4の方向に輸送する役割がある。 For the same purpose as the hole blocking layer 8, it is also effective to provide an electron blocking layer 9 between the hole injection layer 3 and the light emitting layer 4 as shown in FIG. The electron blocking layer 9 increases the probability of recombination with holes in the light emitting layer 4 by blocking the electrons moving from the light emitting layer 4 from reaching the hole injection layer 3, thereby generating excitons generated. Has a role of confining the light in the light emitting layer 4 and a role of efficiently transporting holes injected from the hole injection layer 3 in the direction of the light emitting layer 4.
電子阻止層9に求められる特性としては、正孔輸送性が高く、エネルギーギャップ(HOMO、LUMOの差)が大きいこと、励起三重項準位(T1)が高いことが挙げられる。また、発光層4を湿式製膜法で形成する場合、電子阻止層9も湿式製膜法で形成することが、素子製造が容易となるため、好ましい。 The characteristics required for the electron blocking layer 9 include high hole transportability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Further, when the light emitting layer 4 is formed by a wet film forming method, it is preferable that the electron blocking layer 9 is also formed by a wet film forming method because the device manufacturing becomes easy.
このため、電子阻止層9も湿式製膜適合性を有することが好ましく、このような電子阻止層9に用いられる材料としては、本発明の電荷輸送材料の他、F8−TFBに代表されるジオクチルフルオレンとトリフェニルアミンの共重合体(WO2004/084260号公報記載)等が挙げられる。 For this reason, it is preferable that the electron blocking layer 9 also has wet film forming compatibility, and examples of the material used for such an electron blocking layer 9 include dioctyl typified by F8-TFB in addition to the charge transport material of the present invention. And a copolymer of fluorene and triphenylamine (described in WO 2004/084260).
なお、図1とは逆の構造、即ち、基板1上に陰極6、電子注入層5、発光層4、正孔注入層3、陽極2の順に積層することも可能であり、既述したように少なくとも一方が透明性の高い2枚の基板の間に本発明の有機電界発光素子を設けることも可能である。同様に、図2〜図6に示した前記各層構成とは逆の構造に積層することも可能である。 The structure opposite to that shown in FIG. 1, that is, the cathode 6, the electron injection layer 5, the light emitting layer 4, the hole injection layer 3, and the anode 2 can be laminated on the substrate 1 in this order. It is also possible to provide the organic electroluminescent element of the present invention between two substrates, at least one of which is highly transparent. Similarly, it is also possible to laminate | stack to the structure opposite to the said each layer structure shown in FIGS.
さらには、図1に示す層構成を複数段重ねた構造(発光ユニットを複数積層させた構造)とすることも可能である。その際には段間(発光ユニット間)の界面層(陽極がITO、陰極がAlの場合はその2層)の代わりに、例えばV2O5等を電荷発生層(CGL)として用いると段間の障壁が少なくなり、発光効率・駆動電圧の観点からより好ましい。 Further, a structure in which a plurality of layers shown in FIG. 1 are stacked (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, instead of the interfacial layer (between the light emitting units) (when the anode is ITO and the cathode is Al, the two layers), for example, V 2 O 5 is used as the charge generation layer (CGL). This is more preferable from the viewpoint of luminous efficiency and driving voltage.
本発明は、有機電界発光素子が、単一の素子、アレイ状に配置された構造からなる素子、陽極と陰極がX−Yマトリックス状に配置された構造のいずれにおいても適用することができる。 The present invention can be applied to any of an organic electroluminescent element having a single element, an element having a structure arranged in an array, and a structure having an anode and a cathode arranged in an XY matrix.
次に、本発明を実施例によってさらに具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例の記載に限定されるものではない。
なお、以下において、ガラス転移温度はDSC測定により、気化温度はTG−DTA測定により、融点はDSC測定又はTG−DTA測定によりそれぞれ求めた。
EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.
In the following, the glass transition temperature was determined by DSC measurement, the vaporization temperature was determined by TG-DTA measurement, and the melting point was determined by DSC measurement or TG-DTA measurement.
[実施例1:本発明の電荷輸送材料(I−A)の合成及び溶解度測定]
窒素気流中、カルバゾール(12.0g)、m−ジブロモベンゼン(25.4g)、銅粉末(4.56g)、炭酸カリウム(11.9g)、及びテトラグライム(17ml)を、200℃に加熱下、8時間撹拌し、室温まで放冷した。反応終了後、反応液にクロロホルムを加え、不溶物を濾別した。濾液に含まれるクロロホルムを減圧留去し、シリカゲルカラムクロマトグラフィーで精製した。減圧乾燥することにより、目的物1(12.7g、収率55%)を無色粘調液体として得た。 In a nitrogen stream, carbazole (12.0 g), m-dibromobenzene (25.4 g), copper powder (4.56 g), potassium carbonate (11.9 g), and tetraglyme (17 ml) were heated to 200 ° C. The mixture was stirred for 8 hours and allowed to cool to room temperature. After completion of the reaction, chloroform was added to the reaction solution, and insoluble matters were separated by filtration. Chloroform contained in the filtrate was distilled off under reduced pressure and purified by silica gel column chromatography. By drying under reduced pressure, the target product 1 (12.7 g, yield 55%) was obtained as a colorless viscous liquid.
窒素気流中、目的物1(12.7g)、ビス(ピナコラートジボロン)(13.0g)、酢酸カリウム(13.2g)、及び無水ジメチルスルホキシド(200ml)を、60℃に加熱下、15分間撹拌し、[1,1’−ビス(ジフェニルホスフィノ)フェロセン]ジクロロパラジウム(II)ジクロロメタン錯体(0.965g)を加え、80℃に加熱下、8時間撹拌した。室温まで放冷した後、反応液に水(500ml)、及びトルエン(600ml)を加え、攪拌した。水層をトルエンで2回再抽出した後、有機層を合わせ、硫酸マグネシウム及び活性白土を加えた。硫酸マグネシウム及び活性白土を濾別し、トルエンを減圧留去した。析出した結晶を冷メタノールで洗浄し、減圧乾燥することにより、目的物2(12.4g、収率85%)を白色結晶として得た。 In a nitrogen stream, the target compound 1 (12.7 g), bis (pinacolatodiboron) (13.0 g), potassium acetate (13.2 g), and anhydrous dimethyl sulfoxide (200 ml) were heated to 60 ° C. under the conditions of 15 The mixture was stirred for 1 min, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (0.965 g) was added, and the mixture was stirred for 8 hours while heating at 80 ° C. After allowing to cool to room temperature, water (500 ml) and toluene (600 ml) were added to the reaction solution and stirred. The aqueous layer was re-extracted twice with toluene, the organic layers were combined, and magnesium sulfate and activated clay were added. Magnesium sulfate and activated clay were separated by filtration, and toluene was distilled off under reduced pressure. The precipitated crystals were washed with cold methanol and dried under reduced pressure to give the intended product 2 (12.4 g, yield 85%) as white crystals.
窒素気流中、トリス(4−ブロモフェニル)アミン(0.904g)、目的物2(2.91g)、炭酸ナトリウム(1.49g)、トルエン(45ml)、エタノール(5ml)、及び水(15ml)の混合物に、テトラキス(トリフェニルフォスフィン)パラジウム(0.13g)を投入し、80℃に加熱下、10時間撹拌した。得られた溶液に水(100ml)を加えてから、トルエン(100ml)で抽出後、有機層に無水硫酸マグネシウム、活性白土を加えて、撹拌後、濾過、濃縮して得られた固形分を、シリカゲルカラムクロマトグラフィーで精製し、次いで酢酸エチルで洗浄し、減圧乾燥することにより、目的物3(本発明の電荷輸送材料(I−A))(1.12g)を得た。
DEI−MS m/z=968(M+)
このものの気化温度は576℃、融点は検出されず、ガラス転移温度は159℃であった。
Tris (4-bromophenyl) amine (0.904 g), target product 2 (2.91 g), sodium carbonate (1.49 g), toluene (45 ml), ethanol (5 ml), and water (15 ml) in a nitrogen stream To the mixture, tetrakis (triphenylphosphine) palladium (0.13 g) was added, and the mixture was stirred at 80 ° C. for 10 hours. Water (100 ml) was added to the resulting solution, and after extraction with toluene (100 ml), anhydrous magnesium sulfate and activated clay were added to the organic layer, and after stirring, the solid content obtained by filtration and concentration was The product was purified by silica gel column chromatography, then washed with ethyl acetate, and dried under reduced pressure to obtain the intended product 3 (charge transporting material (IA) of the present invention) (1.12 g).
DEI-MS m / z = 968 (M + )
The vaporization temperature of this product was 576 ° C., the melting point was not detected, and the glass transition temperature was 159 ° C.
この本発明の電荷輸送材料(I−A)のトルエンへの溶解度を調べ、その結果を表1に表した。表1に表す如く、電荷輸送材料(I−A)はトルエンに対して高い溶解性を示した。 The solubility of the charge transport material (IA) of the present invention in toluene was examined, and the results are shown in Table 1. As shown in Table 1, the charge transport material (IA) showed high solubility in toluene.
[実施例2:本発明の電荷輸送材料(I−B)の合成及び溶解度測定]
窒素気流中、−60〜−65℃のエタノールバスで冷却しながら、目的物1(9.06g)の無水テトラヒドロフラン(400ml)溶液に、1.54Mノルマルブチルリチウムのノルマルヘキサン溶液(27.4ml)を7分間かけて滴下した後、40分間撹拌した。その後、室温下で2.2時間撹拌した後、1N塩酸水溶液(45ml)を加え、更に30分間撹拌した。得られた溶液から減圧下でテトラヒドロフランを留去してから、ジエチルエーテル(400ml)、及び飽和食塩水(100ml)を加えて、振り混ぜた後、有機層を分取し、これを飽和食塩水で洗った。得られた有機層に無水硫酸マグネシウム、及び活性白土を加えて、撹拌後、濾過、濃縮した。得られた固形分を、水およびノルマルヘキサンで懸濁洗浄後、エタノール−ノルマルヘキサンからの再沈殿にて精製し、目的物4(4.03g)を得た。 While cooling with an ethanol bath at −60 to −65 ° C. in a nitrogen stream, a solution of target 1 (9.06 g) in anhydrous tetrahydrofuran (400 ml) was added with a normal hexane solution of 1.54 M normal butyl lithium (27.4 ml). Was added dropwise over 7 minutes, followed by stirring for 40 minutes. Thereafter, the mixture was stirred at room temperature for 2.2 hours, 1N aqueous hydrochloric acid solution (45 ml) was added, and the mixture was further stirred for 30 minutes. Tetrahydrofuran was distilled off from the resulting solution under reduced pressure, diethyl ether (400 ml) and saturated brine (100 ml) were added, and the mixture was shaken and the organic layer was separated. Washed with. Anhydrous magnesium sulfate and activated clay were added to the obtained organic layer, and after stirring, filtered and concentrated. The obtained solid was suspended and washed with water and normal hexane, and then purified by reprecipitation from ethanol-normal hexane to obtain the desired product 4 (4.03 g).
室温で、1−ブロモ−3−ヨードベンゼン(22.2g,78.5mmol)、及び目的物4(18.8g,65.43mmol)のトルエン(288mL)溶液とエタノール(72mL)の混合溶液に2M−炭酸ナトリウム水溶液(144mL)を加え、系内を窒素置換した。ここに、テトラキストリフェニルホスフィンパラジウム(0)(1.51g,1.3mmol)を加え、反応混合物を還流させながら3時間半攪拌した。反応混合物を水(100mL)に注ぎ、塩化メチレン(50mL×2回)で抽出後、無水硫酸マグネシウムで乾燥させ、溶媒を減圧下に留去した。残渣をシリカゲルカラムクロマトグラフィーに処し、目的物5(21.9g、84%)を得た。 At room temperature, 2M was added to a mixed solution of 1-bromo-3-iodobenzene (22.2 g, 78.5 mmol) and the target compound 4 (18.8 g, 65.43 mmol) in toluene (288 mL) and ethanol (72 mL). -Aqueous sodium carbonate (144 mL) was added, and the system was replaced with nitrogen. Tetrakistriphenylphosphine palladium (0) (1.51 g, 1.3 mmol) was added thereto, and the reaction mixture was stirred for 3 hours and a half while being refluxed. The reaction mixture was poured into water (100 mL), extracted with methylene chloride (50 mL × 2), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the intended product 5 (21.9 g, 84%).
窒素気流下、マグネシウム(0.73g,30mmol)のテトラヒドロフラン(10mL)懸濁液にヨウ素の小片を加えてマグネシウムを活性化させた後、目的物5(8g,20.1mmol)のテトラヒドロフラン(20mL)溶液をテトラヒドロフランが緩やかに還流するように滴下した。滴下終了後、反応混合物を30分間還流させ、ドライアイス−アセトンバスを用いて−78℃まで冷却し、トリメトキシボラン(6.23g,60mmol)のテトラヒドロフラン(10mL)溶液を温度が−60℃を超えないように滴下した。滴下終了後、−78℃で30分間攪拌し、徐々に室温まで温度を上昇させ、室温で3時間攪拌した。反応混合物を水(100mL)に注ぎ、濃塩酸でpH=1とした後、酢酸エチル(50mL×3回)で抽出した。有機層を無水硫酸マグネシウムで乾燥させ、溶媒を減圧下に留去した。残渣をシリカゲルカラムクロマトグラフィーに処し、目的物6(6.70g、92%)を得た。 Under a nitrogen stream, a small piece of iodine was added to a suspension of magnesium (0.73 g, 30 mmol) in tetrahydrofuran (10 mL) to activate the magnesium, and then the target product 5 (8 g, 20.1 mmol) in tetrahydrofuran (20 mL). The solution was added dropwise so that tetrahydrofuran slowly refluxed. After completion of the dropwise addition, the reaction mixture was refluxed for 30 minutes, cooled to −78 ° C. using a dry ice-acetone bath, and a tetrahydrofuran (10 mL) solution of trimethoxyborane (6.23 g, 60 mmol) was cooled to −60 ° C. It was dripped so that it might not exceed. After completion of dropping, the mixture was stirred at −78 ° C. for 30 minutes, gradually raised to room temperature, and stirred at room temperature for 3 hours. The reaction mixture was poured into water (100 mL), adjusted to pH = 1 with concentrated hydrochloric acid, and extracted with ethyl acetate (50 mL × 3 times). The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the intended product 6 (6.70 g, 92%).
目的物6(3.6g,10mmol)、及びトリス(4−ブロモフェニル)アミン(1.4g,2.9mmol)のジメトキシエタン溶液(100mL)に2M−炭酸ナトリウム水溶液(20mL)を加え5分間窒素でバブリングし、その後反応系内を窒素で置換した。ここへテトラキストリフェニルホスフィンパラジウム(0)(577mg,0.5mmol)を加え、8時間加熱還流した。反応終了後、反応混合物を室温まで冷却し、水(200mL)に注ぎ塩化メチレン(50mL×3回)で抽出後、無水硫酸マグネシウムで乾燥し、減圧下に溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィーに処し、目的物7(I−B)(0.94g、27%)を得た。
DEI−MS m/z=1196(M+)
このものの気化温度は581℃、融点は検出されず、ガラス転移温度は141℃であった。
2M sodium carbonate aqueous solution (20 mL) was added to a dimethoxyethane solution (100 mL) of the target product 6 (3.6 g, 10 mmol) and tris (4-bromophenyl) amine (1.4 g, 2.9 mmol), and nitrogen was added for 5 minutes. Then, the reaction system was purged with nitrogen. Tetrakistriphenylphosphine palladium (0) (577 mg, 0.5 mmol) was added here, and it heated and refluxed for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, poured into water (200 mL), extracted with methylene chloride (50 mL × 3 times), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the intended product 7 (IB) (0.94 g, 27%).
DEI-MS m / z = 1196 (M + )
The vaporization temperature of this product was 581 ° C., the melting point was not detected, and the glass transition temperature was 141 ° C.
この本発明の電荷輸送材料(I−B)のトルエンへの溶解度を調べ、その結果を表1に表した。表1に表す如く、電荷輸送材料(I−B)はトルエンに対して高い溶解性を示した。 The solubility of the charge transport material (IB) of the present invention in toluene was examined, and the results are shown in Table 1. As shown in Table 1, the charge transport material (IB) showed high solubility in toluene.
[比較例1:比較例化合物(X−A)の溶解度測定]
以下に示す比較例化合物(X−A)のトルエンへの溶解度を調べ、その結果を表1に表した。表1に表す如く、比較例化合物(X−A)のトルエンに対する溶解性は低かった。なお、比較例化合物(X−A)のガラス転移温度は69℃であった。
[Comparative Example 1: Solubility Measurement of Comparative Compound (X-A)]
The solubility of the comparative compound (X-A) shown below in toluene was examined, and the results are shown in Table 1. As shown in Table 1, the solubility of the comparative compound (X-A) in toluene was low. In addition, the glass transition temperature of the comparative compound (X-A) was 69 ° C.
[実施例3:電荷輸送材料(I−A)を有する本発明の有機電界発光素子用組成物を用いた有機電解発光素子の製造・評価]
図3に示す構造を有する有機電界発光素子を以下の方法で作製した。
ガラス基板1の上にインジウム・スズ酸化物(ITO)透明導電膜を150nm堆積したもの(スパッター成膜品;シート抵抗15Ω)を通常のフォトリソグラフィ技術と塩酸エッチングを用いて2mm幅のストライプにパターニングして陽極2を形成した。パターン形成したITO基板を、アセトンによる超音波洗浄、純水による水洗、イソプロピルアルコールによる超音波洗浄の順で洗浄後、窒素ブローで乾燥させ、最後に紫外線オゾン洗浄を行った。
[Example 3: Production and evaluation of organic electroluminescence device using composition for organic electroluminescence device of the present invention having charge transport material (IA)]
An organic electroluminescent element having the structure shown in FIG. 3 was produced by the following method.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate 1 having a thickness of 150 nm (sputtered film; sheet resistance 15 Ω) is patterned into a 2 mm wide stripe using normal photolithography and hydrochloric acid etching. Thus, an anode 2 was formed. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, then dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.
次いで、正孔注入層3を以下のように湿式製膜法によって形成した。正孔注入層3の材料として、下記に示す構造式の芳香族アミノ基を有する非共役系高分子化合物(PB−1(重量平均分子量:29400,数平均分子量:12600))と下記に示す構造式の電子受容性化合物(A−2)とを用い、下記の条件でスピンコートした。 Next, the hole injection layer 3 was formed by a wet film forming method as follows. As a material for the hole injection layer 3, a non-conjugated polymer compound (PB-1 (weight average molecular weight: 29400, number average molecular weight: 12600)) having an aromatic amino group having the structural formula shown below and the structure shown below Using the electron-accepting compound (A-2) of the formula, spin coating was performed under the following conditions.
スピンコート条件
溶媒 安息香酸エチル
塗布液濃度 PB−1 2.0重量%
A−2 0.4重量%
スピナ回転数 1500rpm
スピナ回転時間 30秒
乾燥条件 230℃×15分
上記のスピンコートにより膜厚30nmの均一な薄膜が形成された。
Spin coating conditions Solvent Ethyl benzoate Coating solution concentration PB-1 2.0% by weight
A-2 0.4% by weight
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions 230 ° C. × 15 minutes A uniform thin film having a thickness of 30 nm was formed by the above spin coating.
続いて、発光層4を以下のように湿式製膜法によって形成した。発光層4の材料として、実施例1で合成した下記に示す構造式の本発明の電荷輸送材料(I−A)を、下記に示す構造式のイリジウム錯体(D−2)と共に溶媒としてトルエンを用いた有機電界発光素子用組成物を調製し、この有機電界発光素子用組成物を用いて下記の条件でスピンコートした。 Then, the light emitting layer 4 was formed by the wet film forming method as follows. As a material for the light-emitting layer 4, the charge transport material (IA) of the present invention having the following structural formula synthesized in Example 1 is used as a solvent together with the iridium complex (D-2) having the structural formula shown below as a solvent. The composition for organic electroluminescent elements used was prepared, and spin-coated under the following conditions using this composition for organic electroluminescent elements.
スピンコート条件
溶媒 トルエン
組成物中濃度 I−A 2.0重量%
D−2 0.1重量%
スピナ回転数 1500rpm
スピナ回転時間 30秒
乾燥条件 80℃×60分(減圧下)
上記のスピンコートにより膜厚60nmの均一な薄膜が形成された。
Spin coating conditions Solvent Toluene Concentration in composition IA 2.0% by weight
D-2 0.1% by weight
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions 80 ° C x 60 minutes (under reduced pressure)
A uniform thin film having a thickness of 60 nm was formed by the above spin coating.
次に、正孔阻止層8として下記に示すピリジン誘導体(HB−1)をるつぼ温度251〜252℃として、蒸着速度0.045〜0.055nm/秒で5nmの膜厚で積層した。蒸着時の真空度は2.1〜2.4×10−4Pa(約1.6〜1.8×10−6Torr)であった。 Next, a pyridine derivative (HB-1) shown below as the hole blocking layer 8 was laminated at a crucible temperature of 251 to 252 ° C. with a deposition rate of 0.045 to 0.055 nm / second and a film thickness of 5 nm. The degree of vacuum during the deposition was 2.1 to 2.4 × 10 −4 Pa (about 1.6 to 1.8 × 10 −6 Torr).
次に、正孔阻止層8の上に、電子輸送層7として下記に示すアルミニウムの8−ヒドロキシキノリン錯体(ET−1)を同様にして蒸着した。この時のアルミニウムの8−ヒドロキシキノリン錯体のるつぼ温度は222〜239℃の範囲で制御し、蒸着時の真空度は1.7〜2.0×10−4Pa(約1.3〜1.5×10−6Torr)、蒸着速度は0.1nm/秒で膜厚は30nmとした。 Next, an aluminum 8-hydroxyquinoline complex (ET-1) shown below was deposited as an electron transport layer 7 on the hole blocking layer 8 in the same manner. At this time, the crucible temperature of the aluminum 8-hydroxyquinoline complex is controlled in the range of 222 to 239 ° C., and the degree of vacuum during the deposition is 1.7 to 2.0 × 10 −4 Pa (about 1.3 to 1. 5 × 10 −6 Torr), the deposition rate was 0.1 nm / second, and the film thickness was 30 nm.
上記の正孔阻止層8及び電子輸送層7を真空蒸着する時の基板温度は室温に保持した。
ここで、電子輸送層7までの蒸着を行った素子を一度前記真空蒸着装置内より大気中に取り出して、陰極蒸着用のマスクとして2mm幅のストライプ状シャドーマスクを、陽極2のITOストライプとは直交するように素子に密着させて、別の真空蒸着装置内に設置して有機層と同様にして装置内の真空度が2.3×10−6Torr(約3.0×10−4Pa)以下になるまで排気した。
The substrate temperature during vacuum deposition of the hole blocking layer 8 and the electron transport layer 7 was kept at room temperature.
Here, the element that has been deposited up to the electron transport layer 7 is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide striped shadow mask is used as a cathode deposition mask. In close contact with the element so as to be orthogonal to each other, it is installed in another vacuum deposition apparatus, and the degree of vacuum in the apparatus is 2.3 × 10 −6 Torr (about 3.0 × 10 −4 Pa) in the same manner as the organic layer. ) Exhaust until below.
次に、電子輸送層7の上に、電子注入層5として、フッ化リチウム(LiF)を、モリブデンボートを用いて、蒸着速度0.015nm/秒、真空度2.5×10−6Torr(約3.3×10−4Pa)で、0.5nmの膜厚で電子輸送層7の上に成膜した。 Next, on the electron transport layer 7, lithium fluoride (LiF) is used as the electron injection layer 5, using a molybdenum boat, a deposition rate of 0.015 nm / second, a degree of vacuum of 2.5 × 10 −6 Torr ( The film was formed on the electron transport layer 7 with a film thickness of 0.5 nm at about 3.3 × 10 −4 Pa).
次に、電子注入層5の上に、陰極6として、アルミニウムをモリブデンボートにより加熱して、蒸着速度0.5〜3.0nm/秒、真空度3.3〜7.5×10−6Torr(約4.4〜10.0×10−4Pa)で製膜して膜厚80nmのアルミニウム層を形成して陰極6を完成させた。
以上の電子注入層5、陰極6の蒸着時の基板温度は室温に保持した。
Next, aluminum is heated as a cathode 6 on the electron injection layer 5 by a molybdenum boat, a deposition rate of 0.5 to 3.0 nm / second, and a degree of vacuum of 3.3 to 7.5 × 10 −6 Torr. The cathode 6 was completed by forming a film at about 4.4 to 10.0 × 10 −4 Pa and forming an aluminum layer with a thickness of 80 nm.
The substrate temperature at the time of vapor deposition of the electron injection layer 5 and the cathode 6 was kept at room temperature.
以上の様にして、2mm×2mmのサイズの発光面積部分を有する有機電界発光素子が得られた。この素子の発光特性は以下の通りである。
輝度/電流:20.0[cd/A](@100cd/m2)
電圧:7.3[V](@100cd/m2)
発光効率:8.7[1m/W](@100cd/m2)
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. The light emission characteristics of this element are as follows.
Luminance / current: 20.0 [cd / A] (@ 100 cd / m 2 )
Voltage: 7.3 [V] (@ 100 cd / m 2 )
Luminous efficiency: 8.7 [1 m / W] (@ 100 cd / m 2 )
素子の発光スペクトルの極大波長は518nmであり、イリジウム錯体(D−2)からのものと同定された。色度はCIE(x,y)=(0.333,0.614)であった。 The maximum wavelength of the emission spectrum of the device was 518 nm, which was identified as that from the iridium complex (D-2). The chromaticity was CIE (x, y) = (0.333, 0.614).
この結果から、本発明の電荷輸送材料(I−A)をホスト材料として用いた有機電界発光素子は、電荷輸送材料(I−A)が電荷輸送性に優れ、容易には結晶化しないため、均一な発光が得られ、発光効率が高く、低い電圧で駆動可能であることが確認された。 From this result, the organic electroluminescent device using the charge transport material (IA) of the present invention as a host material is excellent in charge transportability and is not easily crystallized. It was confirmed that uniform light emission was obtained, the light emission efficiency was high, and the device could be driven at a low voltage.
[実施例4:電荷輸送材料(I−B)を有する本発明の有機電界発光素子用組成物を用いた有機電解発光素子の製造・評価]
正孔注入層3の材料として、(PB−1)に代えて下記に示す構造式の芳香族アミノ基を有する高分子化合物(PB−2)(重量平均分子量:26500,数平均分子量:12000))と前記電子受容性化合物(A−2)とを用い、下記の条件でスピンコートしたこと、および、発光層4の材料として、(I−A)に代えて(I−B)を、上記イリジウム錯体(D−2)と共に用い、下記の条件でスピンコートした以外は、実施例3と同様にして有機電界発光素子を作製した。
As a material for the hole injection layer 3, instead of (PB-1), a polymer compound (PB-2) having an aromatic amino group having the structural formula shown below (weight average molecular weight: 26500, number average molecular weight: 12000) ) And the electron-accepting compound (A-2), and (IB) instead of (IA) as a material of the light-emitting layer 4 by spin coating under the following conditions, An organic electroluminescent element was produced in the same manner as in Example 3 except that it was used together with the iridium complex (D-2) and spin-coated under the following conditions.
スピンコート条件
溶媒 安息香酸エチル
塗布液濃度 PB−2 2.0重量%
A−2 0.4重量%
スピナ回転数 2000rpm
スピナ回転時間 30秒
乾燥条件 230℃×3時間
上記のスピンコートにより膜厚30nmの均一な薄膜(正孔注入層)が形成された。
Spin coating conditions Solvent Ethyl benzoate Coating solution concentration PB-2 2.0% by weight
A-2 0.4% by weight
Spinner speed 2000rpm
Spinner rotation time 30 seconds Drying condition 230 ° C. × 3 hours A uniform thin film (hole injection layer) having a film thickness of 30 nm was formed by the above spin coating.
スピンコート条件
溶媒 キシレン
塗布液濃度 I−B 2.0重量%
D−2 0.1重量%
スピナ回転数 1500rpm
スピナ回転時間 30秒
乾燥条件 130℃×60分(減圧下)
上記のスピンコートにより膜厚40nmの均一な薄膜(発光層)が形成された。
Spin coating conditions Solvent Xylene Coating solution concentration IB 2.0% by weight
D-2 0.1% by weight
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions 130 ° C x 60 minutes (under reduced pressure)
A uniform thin film (light emitting layer) having a film thickness of 40 nm was formed by the above spin coating.
この素子の発光特性は以下の通りである。
輝度/電流:14.7[cd/A](@100cd/m2)
電圧:7.4[V](@100cd/m2)
発光効率:6.3[1m/W](@100cd/m2)
The light emission characteristics of this element are as follows.
Luminance / current: 14.7 [cd / A] (@ 100 cd / m 2 )
Voltage: 7.4 [V] (@ 100 cd / m 2 )
Luminous efficiency: 6.3 [1 m / W] (@ 100 cd / m 2 )
素子の発光スペクトルの極大波長は514.0nmであり、イリジウム錯体(D−2)からのものと同定された。色度はCIE(x,y)=(0.344,0.601)であった。 The maximum wavelength of the emission spectrum of the device was 514.0 nm, which was identified as that from the iridium complex (D-2). The chromaticity was CIE (x, y) = (0.344, 0.601).
[実施例5:電荷輸送材料(I−A)を有する本発明の有機電界発光素子用組成物を用いた有機電解発光素子の製造・評価]
発光層4の材料として、(I−A)に代えて、下記(I−A)と下記(E−3)とを前記イリジウム錯体(D−2)と共に用い、下記の条件でスピンコートした以外は、実施例3と同様にして有機電界発光素子を作製した。
As the material of the light emitting layer 4, instead of (IA), the following (IA) and the following (E-3) are used together with the iridium complex (D-2) and spin-coated under the following conditions: Produced an organic electroluminescent element in the same manner as in Example 3.
スピンコート条件
溶媒 キシレン
塗布液濃度 I−A 1.5重量%
E−3 1.5重量%
D−2 0.15重量%
スピナ回転数 1500rpm
スピナ回転時間 30秒
乾燥条件 130℃×60分(減圧下)
Spin coating conditions Solvent Xylene Coating solution concentration IA 1.5% by weight
E-3 1.5% by weight
D-2 0.15 wt%
Spinner speed 1500rpm
Spinner rotation time 30 seconds Drying conditions 130 ° C x 60 minutes (under reduced pressure)
この素子の発光特性は以下の通りである。
輝度/電流:27.4[cd/A](@100cd/m2)
電圧:6.6[V](@100cd/m2)
発光効率:13.1[1m/W](@100cd/m2)
The light emission characteristics of this element are as follows.
Luminance / current: 27.4 [cd / A] (@ 100 cd / m 2 )
Voltage: 6.6 [V] (@ 100 cd / m 2 )
Luminous efficiency: 13.1 [1 m / W] (@ 100 cd / m 2 )
素子の発光スペクトルの極大波長は514nmであり、イリジウム錯体(D−2)からのものと同定された。色度はCIE(x,y)=(0.312,0.623)であった。 The maximum wavelength of the emission spectrum of the device was 514 nm, which was identified as from the iridium complex (D-2). The chromaticity was CIE (x, y) = (0.312, 0.623).
[比較例2:比較化合物(X−A)を用いた有機電解発光素子の製造・評価]
発光層4の材料として、(I−A)に代えて下記に示す構造式の比較化合物(X−A)を前記(E−3)と前記イリジウム錯体(D−2)と共に用いた以外は、実施例5と同様にして有機電界発光素子を作製した。
As a material for the light-emitting layer 4, a comparative compound (X-A) having the structural formula shown below was used together with (E-3) and the iridium complex (D-2) instead of (IA). An organic electroluminescent element was produced in the same manner as in Example 5.
この素子の発光特性は以下の通りである。
輝度/電流:21.9[cd/A](@100cd/m2)
電圧:8.0[V](@100cd/m2)
発光効率:8.0[1m/W](@100cd/m2)
The light emission characteristics of this element are as follows.
Luminance / current: 21.9 [cd / A] (@ 100 cd / m 2 )
Voltage: 8.0 [V] (@ 100 cd / m 2 )
Luminous efficiency: 8.0 [1 m / W] (@ 100 cd / m 2 )
素子の発光スペクトルの極大波長は511.5nmであり、イリジウム錯体(D−2)からのものと同定された。色度はCIE(x,y)=(0.303,0.622)であった。 The maximum wavelength of the emission spectrum of the device was 511.5 nm, which was identified as from the iridium complex (D-2). The chromaticity was CIE (x, y) = (0.303, 0.622).
表2に、実施例5と比較例2で作製した素子の100cd/m2時における電流効率、駆動電圧、および初期輝度1000cd/m2として定電流駆動を行った際の規格化輝度半減寿命をまとめた。 Table 2 shows the normalized luminance half-life when the device manufactured in Example 5 and Comparative Example 2 is driven at constant current with current efficiency at 100 cd / m 2 , driving voltage, and initial luminance of 1000 cd / m 2. Summarized.
表2の結果から、本発明の有機化合物、および有機電界発光素子用組成物を用いて作製された素子は発光効率が高く、長寿命であることがわかる。 From the results in Table 2, it can be seen that the device produced using the organic compound of the present invention and the composition for organic electroluminescence device has high luminous efficiency and long life.
1 基板
2 陽極
3 正孔注入層
4 発光層
5 電子注入層
6 陰極
7 電子輸送層
8 正孔阻止層
9 電子阻止層
DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Light emitting layer 5 Electron injection layer 6 Cathode 7 Electron transport layer 8 Hole blocking layer 9 Electron blocking layer
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