JP2007001895A - Phosphorescent host compound and organic electroluminescent element using the same - Google Patents
Phosphorescent host compound and organic electroluminescent element using the same Download PDFInfo
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- 0 C*(c1ccc(*(Cc(cc2)cc(c3ccccc33)c2[n]3-c(cc2)c3)c4ccccc4)cc1)c(cc1)ccc1-c1cc(-[n]4c(ccc(CC(c5ccccc5)c5ccc(C6C=C)cc5)c5)c5c5c4cccc5)ccc1-c2c3-c1ccc6cc1 Chemical compound C*(c1ccc(*(Cc(cc2)cc(c3ccccc33)c2[n]3-c(cc2)c3)c4ccccc4)cc1)c(cc1)ccc1-c1cc(-[n]4c(ccc(CC(c5ccccc5)c5ccc(C6C=C)cc5)c5)c5c5c4cccc5)ccc1-c2c3-c1ccc6cc1 0.000 description 4
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1-c1nnc(-c(cc2)ccc2-c2ccccc2)[n]1-c1ccccc1 Chemical compound CC(C)(C)c(cc1)ccc1-c1nnc(-c(cc2)ccc2-c2ccccc2)[n]1-c1ccccc1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 1
- GRHURXATQWWHFR-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1C1=[N]=C(c(cc2)ccc2-c2ccccc2)O1 Chemical compound CC(C)(C)c(cc1)ccc1C1=[N]=C(c(cc2)ccc2-c2ccccc2)O1 GRHURXATQWWHFR-UHFFFAOYSA-N 0.000 description 1
- UKUZZKUITQATNF-UHFFFAOYSA-N c(cc1)ccc1-c1ccc(C2N=C(c(cc3)ccc3-c3ccccc3)N2c2ccccc2)cc1 Chemical compound c(cc1)ccc1-c1ccc(C2N=C(c(cc3)ccc3-c3ccccc3)N2c2ccccc2)cc1 UKUZZKUITQATNF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、燐光ホスト化合物及びそれを用いた有機電界発光素子に関する。 The present invention relates to a phosphorescent host compound and an organic electroluminescence device using the same.
有機電界発光素子は、次世代平面ディスプレイとして注目されており、この有機電界発光素子を用いることにより、例えば、直流低電圧駆動、広視野角、自発光などの特徴を有するフルカラー高解像度ディスプレイの実現が可能となる。そのためには、有機電界発光素子の発光効率をさらに向上させる必要がある。 Organic electroluminescent devices are attracting attention as next-generation flat displays, and by using these organic electroluminescent devices, for example, realization of full-color high-resolution displays with features such as direct current low voltage drive, wide viewing angle, and self-light emission Is possible. For that purpose, it is necessary to further improve the luminous efficiency of the organic electroluminescent element.
従来の有機電界発光素子の発光は、主に蛍光を利用したものであった。すなわち、両電極から電子及びホールを注入すると、それらが対電極に向かい、発光層で再結合して励起子を生成し、その励起子の励起状態が基底状態に戻るときに発光が生じる。この励起状態には、電子スピンの向きが反平行である一重項励起状態と、電子スピンの向きが平行となる三重項励起状態とがあるが、上述した蛍光は、一重項励起状態のみが関与する発光形態である。単純な量子力学的推論から、一重項励起状態と三重項励起状態の生成比率は１：３であるので、蛍光を利用した有機電界発光素子の場合には内部量子効率の最大値は２５％となる。つまり、励起状態の７５％は発光に使用されないことになる。また、外部への取り出し効率（ηｅｘｔ）は、高々２０％程度であるため、蛍光を利用した有機電界発光素子においては、その外部量子効率は２５％×２０％となり、最大５％程度と見積もられる。 The light emission of the conventional organic electroluminescence device mainly uses fluorescence. That is, when electrons and holes are injected from both electrodes, they are directed to the counter electrode, recombined in the light emitting layer to generate excitons, and light emission occurs when the excited state of the excitons returns to the ground state. This excited state includes a singlet excited state in which the direction of electron spin is anti-parallel and a triplet excited state in which the direction of electron spin is parallel, but the above-described fluorescence involves only the singlet excited state. It is a light emission form. From the simple quantum mechanical reasoning, the generation ratio of the singlet excited state and the triplet excited state is 1: 3. Therefore, in the case of an organic electroluminescence device using fluorescence, the maximum value of the internal quantum efficiency is 25%. Become. That is, 75% of the excited state is not used for light emission. Further, since the extraction efficiency (ηext) to the outside is about 20% at the maximum, in the organic electroluminescence device using fluorescence, the external quantum efficiency is 25% × 20%, which is estimated to be about 5% at the maximum. .
このため、外部量子効率をさらに向上させるためには、励起状態のうちの７５％を占める三重項励起状態からの発光、すなわち燐光も利用する必要がある。この利用が可能となれば、外部量子効率を最大２０％まで向上させることができる。 For this reason, in order to further improve the external quantum efficiency, it is necessary to use light emission from a triplet excited state that occupies 75% of the excited state, that is, phosphorescence. If this utilization becomes possible, the external quantum efficiency can be improved up to 20%.
例えば、イリジウム錯体を燐光発光性化合物として使用した有機電界発光素子が提案されている（例えば、非特許文献１参照）。上記燐光発光性化合物は、単独では成膜性が低く、また励起状態の自己消光を起こしてしまうため、通常、高い効率を実現させるため、燐光ホスト化合物中に分散させる。 For example, an organic electroluminescent element using an iridium complex as a phosphorescent compound has been proposed (see, for example, Non-Patent Document 1). The phosphorescent compound alone has low film-forming properties and causes self-quenching in an excited state. Therefore, the phosphorescent compound is usually dispersed in a phosphorescent host compound in order to achieve high efficiency.
このような燐光ホスト化合物としては、これまでにいくつかのカルバゾール誘導体が報告されている。 As such a phosphorescent host compound, several carbazole derivatives have been reported so far.
例えば、４，４’−Ｎ，Ｎ’−ジカルバゾール−ビフェニル（ＣＢＰ、例えば、非特許文献２参照）、３，３’−Ｎ，Ｎ’−ジカルバゾール−ビフェニル（例えば、特許文献１参照）、１，３−ビス（カルバゾール−９−イル）−ベンゼン（ｍＣＰ、例えば、非特許文献２参照）、ジメチル基を置換基として導入したＣＢＰ、すなわち４，４’−Ｎ，Ｎ’−ジカルバゾール−２，２’−ジメチル−ビフェニル（ＣＤＢＰ、例えば、非特許文献３参照）が知られている。 For example, 4,4′-N, N′-dicarbazole-biphenyl (CBP, for example, see Non-Patent Document 2), 3,3′-N, N′-dicarbazole-biphenyl (for example, see Patent Document 1) 1,3-bis (carbazol-9-yl) -benzene (mCP, for example, see Non-Patent Document 2), CBP introduced with a dimethyl group as a substituent, that is, 4,4′-N, N′-dicarbazole -2,2'-Dimethyl-biphenyl (CDBP, for example, refer nonpatent literature 3) is known.
これら低分子系の燐光ホスト化合物は、上述のイリジウム錯体と共に真空蒸着法により成膜される。この真空蒸着法は、低分子系発光材料に対して広く用いられている成膜方法ではあるが、真空設備を必要とすること、大面積になるほど有機薄膜を均一の厚さに成膜することが困難になること等の問題点を有しており、必ずしも大面積パネルの量産に適した方法とはいえない。大面積、量産化に適した素子作製方法として、上述の燐光発光性化合物を高分子系燐光ホスト化合物にドーピングした混合物をスピンコート、インクジェットなどにより成膜する方法が開発されている。この高分子系燐光ホスト化合物としては、ポリビニルカルバゾール（ＰＶＫ）が使用されている。 These low-molecular phosphorescent host compounds are formed into a film by a vacuum deposition method together with the above iridium complex. This vacuum deposition method is a film formation method widely used for low molecular weight light emitting materials, but requires vacuum equipment, and forms an organic thin film with a uniform thickness as the area increases. However, it is not necessarily a method suitable for mass production of large-area panels. As a method for manufacturing an element suitable for large area and mass production, a method of forming a film by spin coating, ink jet or the like of a mixture obtained by doping the above-described phosphorescent compound with a polymer phosphorescent host compound has been developed. Polyvinylcarbazole (PVK) is used as the polymer phosphorescent host compound.
しかし、それらホスト化合物は、有機ＥＬ（エレクトロルミネッセンス）素子に対する実用性が十分でない。例えば、ＣＢＰは薄膜の安定性が低く、均質なアモルファス膜を形成できないことが示されている（例えば、非特許文献４参照）。 However, these host compounds are not sufficiently practical for organic EL (electroluminescence) devices. For example, it has been shown that CBP has low thin film stability and cannot form a homogeneous amorphous film (see, for example, Non-Patent Document 4).
３，３’−Ｎ，Ｎ’−ジカルバゾール−ビフェニルは、成膜性には優れているものの耐熱性に重大な課題を有する。また、ｍＣＰ、ＣＤＢＰは、熱安定性と薄膜安定性が低く、ｍＣＰのガラス転移温度は６５℃しかなく、発光層自体が結晶化する問題点を有する。 Although 3,3'-N, N'-dicarbazole-biphenyl is excellent in film formability, it has a serious problem in heat resistance. Further, mCP and CDBP have low thermal stability and thin film stability, and the glass transition temperature of mCP is only 65 ° C., which causes a problem that the light emitting layer itself is crystallized.
以上の理由から、燐光発光性化合物を用いた有機ＥＬ素子においては、実用化に向けての素子の耐熱性、成膜性、発光効率の両立に大きな課題を抱えている。 For the above reasons, organic EL devices using phosphorescent compounds have major problems in achieving both the heat resistance, film-forming properties, and luminous efficiency of the devices for practical use.
本発明は、上記従来の課題に鑑みなされたものであり、その目的は、高い薄膜安定性と高い熱安定性を有する燐光ホスト材料を提供することであり、しかも発光効率の向上と素子寿命の向上が期待される有機電界発光素子を提供することにある。 The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide a phosphorescent host material having high thin film stability and high thermal stability, and further improving luminous efficiency and device lifetime. An object of the present invention is to provide an organic electroluminescent device expected to be improved.
さらに、上述の従来報告されている低分子系の燐光ホスト材料では困難であった塗布法によっても成膜可能な燐光ホスト材料を提供することにある。 It is another object of the present invention to provide a phosphorescent host material that can be formed by a coating method that has been difficult with the above-described conventionally reported low-molecular phosphorescent host materials.
前記課題を解決するために鋭意検討した結果、本発明を見出したものである。すなわち、本発明の燐光ホスト化合物は、下記一般式（１）または（２）で表される化合物である。 As a result of intensive studies to solve the above problems, the present invention has been found. That is, the phosphorescent host compound of the present invention is a compound represented by the following general formula (1) or (2).
アルキル基は、炭素数１〜８の直鎖、分岐または環状のアルキル基であり、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、シクロヘキシル基、イソプロピル基、ｔｅｒｔ−ブチル基等が例示できる。
The alkyl group is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, cyclohexyl group, isopropyl group. And a tert-butyl group.
アルコキシ基は、炭素数１〜８の直鎖、分岐または環状のアルコキシ基であり、例えば、メトキシ基、エトキシ基、ブトキシ基等が例示できる。 The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group.
Ｒ１，Ｒ２が置換もしくは無置換のフェニル基の場合、その際の置換基としては、前記のアルキル基、アルコキシ基に加え、フェニル基、ビフェニル基、ナフチル基等が挙げられる。 In the case where R 1 and R 2 are substituted or unsubstituted phenyl groups, examples of the substituent include phenyl, biphenyl, and naphthyl groups in addition to the alkyl and alkoxy groups.
また、本発明は、陰極と陽極との間に発光を示す有機層を含む有機電界発光素子であって、前記有機層のうち少なくとも一層が、燐光発光性化合物と前記一般式（１）または（２）で表される燐光ホスト化合物との混合物を含んでなる有機電界発光素子である。 The present invention also provides an organic electroluminescent device comprising an organic layer that emits light between a cathode and an anode, wherein at least one of the organic layers comprises a phosphorescent compound and the general formula (1) or ( An organic electroluminescent device comprising a mixture with the phosphorescent host compound represented by 2).
前記一般式（１）または（２）で表される燐光ホスト化合物は、例えば、下記ルートにより合成可能である。 The phosphorescent host compound represented by the general formula (1) or (2) can be synthesized by, for example, the following route.
以下、合成法について説明する。
Hereinafter, the synthesis method will be described.
燐光ホスト化合物は、前記（１１）または（１３）で表されるフルオレン誘導体と前記（１２）または（１４）で表されるボロン酸誘導体及び塩基の混合物を、テトラキス（トリフェニルホスフィン）パラジウム等のパラジウム触媒存在下にカップリング反応を行うことで合成できる。塩基としては、通常、炭酸ナトリウム、水酸化ナトリウム等の無機塩基、トリエチルアミン等の有機塩基が使用できる。また、反応時間、反応温度は特に制限はないが、例えば、５０〜１２０℃で実施できる。反応終了後、溶媒を除去した後、シリカゲルクロマトグラフィー、再結晶及び昇華等の方法により精製される。 The phosphorescent host compound is a mixture of the fluorene derivative represented by (11) or (13) and the boronic acid derivative represented by (12) or (14) and a base, such as tetrakis (triphenylphosphine) palladium. It can be synthesized by performing a coupling reaction in the presence of a palladium catalyst. As the base, usually, an inorganic base such as sodium carbonate or sodium hydroxide, or an organic base such as triethylamine can be used. The reaction time and reaction temperature are not particularly limited, but can be carried out at 50 to 120 ° C., for example. After completion of the reaction, the solvent is removed and the product is purified by a method such as silica gel chromatography, recrystallization and sublimation.
本発明の燐光ホスト化合物は、下記式（３）−（１０）のいずれかで表される化合物であることが特に好ましい。 The phosphorescent host compound of the present invention is particularly preferably a compound represented by any of the following formulas (3) to (10).
本発明の燐光ホスト化合物は、高い薄膜安定性と、高いガラス転移温度を有することにより熱安定性に優れる。また、本発明の有機電界発光素子は、通常の燐光発光性化合物と本発明の燐光ホスト化合物とを真空蒸着法により成膜しても良いし、また、燐光発光性化合物と本発明の燐光ホスト化合物とを適当な溶媒に溶解させた混合物をスピンコート、インクジェット等の塗布法により成膜しても良い。 The phosphorescent host compound of the present invention is excellent in thermal stability by having high thin film stability and high glass transition temperature. In addition, the organic electroluminescent device of the present invention may be formed by depositing a normal phosphorescent compound and the phosphorescent host compound of the present invention by a vacuum evaporation method, or the phosphorescent compound and the phosphorescent host of the present invention. A mixture in which a compound is dissolved in an appropriate solvent may be formed by a coating method such as spin coating or ink jet.
前記混合物中の燐光発光性化合物の含有率は特に制限はないが、より高い発光効率を得るためには０．１〜２０重量％であり、好ましくは０．５〜１５重量％、特に好ましくは１．０〜１０重量％である。 The content of the phosphorescent compound in the mixture is not particularly limited, but is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably for obtaining higher luminous efficiency. 1.0 to 10% by weight.
以下、本発明の実施の形態を図面に従って説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は、本発明に係る有機電界発光素子の基本構成の断面図である。素子構造は、ＩＴＯ等により構成される陽極１０の上に、ホール輸送層２０が形成され、順次、発光層３０、電子輸送層４０の各薄膜層が形成される。または、発光層３０と電子輸送層４０は混合されていても良い。そして、陽極１０と陰極５０との両電極層間で順次積層された多層構造であり、発光層３０は燐光発光性化合物と燐光ホスト材料からなる。
FIG. 1 is a cross-sectional view of a basic configuration of an organic electroluminescent element according to the present invention. In the element structure, a
上述したホール輸送層２０には、Ｎ，Ｎ’−（Ｎ−フェニル−１−ナフチルアミノ）ビフェニル（ＮＰＢ）のようなベンジジン骨格を有するトリアリールアミン誘導体、またはＰＥＤＯＴ：ＰＳＳ（ポリエチレンジオキシチオフェン−ポリスチレンスルホン酸ドープ体溶液）のような高分子化合物も使用できる。
The
上述した発光層３０に用いられる燐光発光性化合物としては、燐光発光を生じさせる化合物であれば特に制限はないが、イリジウム、白金、オスミウム、パラジウム等の遷移金属錯体である。特に好ましくはイリジウム錯体、白金錯体であり、イリジウム錯体の具体例としては、青色を出すイリジウム（ＩＩＩ）ビス［（４，６−ジフルオロフェニル）ピリジノナト−Ｎ，Ｃ−２’］ピコリネート（ＦＩｒｐｉｃ、化合物（１５））、緑色を出すトリ（２−フェニルピリジナト−Ｎ，Ｃ２）イリジウム（Ｉｒ（ｐｐｙ）３、化合物（１６））のほか（１７）〜（１９）で表される化合物が挙げられる。また、白金錯体としては、化合物（２０）が挙げられる。
The phosphorescent compound used for the
また、陽極１０とホール輸送層２０との間には、ＣｕＰｃやスターバーストアミン型化合物（特開平４−３０８６８８公報参照）を挿入することも好適である。
It is also preferable to insert CuPc or a starburst amine type compound (see Japanese Patent Laid-Open No. 4-308688) between the
本発明による上記一般式（１）または（２）で表される燐光ホスト化合物は、
高い薄膜安定性と高い熱安定性を有する燐光ホスト材料である。また、上述の従来報告されている低分子系の燐光ホスト材料では困難であった塗布法によっても成膜可能な材料である。このことから、有機電界発光素子において、発光効率の向上と素子寿命の向上が期待できる。
The phosphorescent host compound represented by the general formula (1) or (2) according to the present invention is:
It is a phosphorescent host material having high thin film stability and high thermal stability. Further, it is a material that can be formed by a coating method that has been difficult with the above-described conventionally reported low-molecular phosphorescent host materials. From this, in an organic electroluminescent element, improvement in luminous efficiency and improvement in element lifetime can be expected.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
また、合成した化合物の諸物性は、以下に示す方法により測定した。 Further, various physical properties of the synthesized compound were measured by the following methods.
質量分析は、電界脱離質量分析（ＦＤＭＳ）により行った。 Mass spectrometry was performed by field desorption mass spectrometry (FDMS).
１Ｈ−ＮＭＲ，１３Ｃ−ＮＭＲスペクトルは、バリアン社製 Ｇｅｍｉｎｉ２００を用いて測定した。 1 H-NMR and 13 C-NMR spectra were measured using Gemini 200 manufactured by Varian.
ＬＣ純度は、高速液体クロマトグラフィーにて測定した。 LC purity was measured by high performance liquid chromatography.
発光スペクトルは、分光蛍光光度計を用いて測定した。 The emission spectrum was measured using a spectrofluorometer.
有機ＥＬ素子の発光スペクトル及び外部量子効率は、量子効率測定装置を用いて測定した。 The emission spectrum and external quantum efficiency of the organic EL element were measured using a quantum efficiency measuring device.
さらに、薄膜安定性については、以下の実験を行い評価した。 Furthermore, the following experiments were evaluated for thin film stability.
〜薄膜安定性〜
化合物２０ｍｇをトルエン２ｍｌに溶解させた１％溶液を調製し、スピンコート法（回転条件＝１０００ｒｐｍ（１分間）、真空加熱条件＝１００℃（１時間真空加熱）により石英基板上に薄膜を調製し、室温下（１週間）放置して、薄膜の白濁（または凝集）を観察した。
~ Thin film stability ~
A 1% solution in which 20 mg of compound was dissolved in 2 ml of toluene was prepared, and a thin film was prepared on a quartz substrate by spin coating (rotation conditions = 1000 rpm (1 minute), vacuum heating conditions = 100 ° C. (1 hour vacuum heating)). The film was left to stand at room temperature (1 week), and the cloudiness (or aggregation) of the thin film was observed.
合成例１ 化合物（７）の合成
窒素雰囲気下、１００ｍｌの容器中で、９，９−ビス［４−（トリフルオロメタンスルホニルオキシ）フェニル］フルオレン １．２３ｇ（２．０ｍｍｏｌ）をテトラヒドロフラン６ｍｌに溶解させ、２０％炭酸ナトリウム水溶液４．７ｇ、４−（Ｎ−カルバゾリル）フェニルボロン酸（４．２ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（０．０２ｍｍｏｌ）を加えた。６５℃で２時間反応させた後、室温まで冷却し、分液した。有機層を飽和塩化アンモニウム水溶液及び飽和食塩水で洗浄し、減圧下にて溶媒を留去した。残査をシリカゲルクロマトグラフィーに付し、淡黄色粉末１．２７ｇ（収率８４％、ＬＣ純度＝９９．７％）を得た。質量分析（ＦＤＭＳ）から目的物であることを確認した。尚、化合物（７）は融点を示さないガラス転移温度＝１９３℃のアモルファス材料であった。
Synthesis Example 1 Synthesis of Compound (7) Under a nitrogen atmosphere, 1.23 g (2.0 mmol) of 9,9-bis [4- (trifluoromethanesulfonyloxy) phenyl] fluorene was dissolved in 6 ml of tetrahydrofuran in a 100 ml container. Then, 4.7 g of 20% aqueous sodium carbonate solution, 4- (N-carbazolyl) phenylboronic acid (4.2 mmol), and 23 mg (0.02 mmol) of tetrakis (triphenylphosphine) palladium were added. After reacting at 65 ° C. for 2 hours, the mixture was cooled to room temperature and separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated brine, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography to obtain 1.27 g (yield 84%, LC purity = 99.7%) of a pale yellow powder. The product was confirmed by mass spectrometry (FDMS). Compound (7) was an amorphous material having a glass transition temperature of 193 ° C. and having no melting point.
ＦＤＭＳ；８００
１Ｈ−ＮＭＲ（ＣＤＣｌ３）；７．２８−８．１５（ｍ）
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）；１５０．９，１４５．３，１４０．８，１４０．２，１３９．７，１３８．６，１３６．７，１２８．７，１２８．２，１２７．９，１２７．７，１２７．２，１２６．９，１２６．２，１２５．９，１２３．４，１２０．３８，１２０．３３，１２０．０，１０９．８，６５．１５ｐｐｍ
合成例２ 化合物（５）の合成
窒素雰囲気下、１００ｍｌの容器中で、９，９−ビス［４−（トリフルオロメタンスルホニルオキシ）フェニル］−２，７−ビス（９−カルバゾリル）フルオレン １．８８ｇ（２．０ｍｍｏｌ）をテトラヒドロフラン６ｍｌに溶解させ、２０％炭酸ナトリウム水溶液４．７ｇ、フェニルボロン酸０．５１ｇ（４．２ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（０．０２ｍｍｏｌ）を加えた。６５℃で一晩反応させた後、室温まで冷却し、分液した。有機層を飽和塩化アンモニウム水溶液及び飽和食塩水で洗浄し、減圧下にて溶媒を留去した。残査をシリカゲルクロマトグラフィーに付し、淡黄色粉末１．１ｇ（収率６８％、ＬＣ純度＝９９．７％）を得た。質量分析（ＦＤＭＳ）から目的物であることを確認した。尚、化合物（７）は融点を示さないガラス転移温度＝１９３℃のアモルファス材料であった。
FDMS; 800
1 H-NMR (CDCl 3 ); 7.28-8.15 (m)
13 C-NMR (CDCl 3 ); 150.9, 145.3, 140.8, 140.2, 139.7, 138.6, 136.7, 128.7, 128.2, 127.9, 127 7, 127.2, 126.9, 126.2, 125.9, 123.4, 120.38, 120.33, 120.0, 109.8, 65.15 ppm
Synthesis Example 2 Synthesis of Compound (5) In a 100 ml container under a nitrogen atmosphere, 9,9-bis [4- (trifluoromethanesulfonyloxy) phenyl] -2,7-bis (9-carbazolyl) fluorene 1.88 g (2.0 mmol) was dissolved in 6 ml of tetrahydrofuran, and 4.7 g of 20% aqueous sodium carbonate solution, 0.51 g (4.2 mmol) of phenylboronic acid and 23 mg (0.02 mmol) of tetrakis (triphenylphosphine) palladium were added. After reacting overnight at 65 ° C., the mixture was cooled to room temperature and separated. The organic layer was washed with a saturated aqueous ammonium chloride solution and saturated brine, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography to obtain 1.1 g (yield 68%, LC purity = 99.7%) of a pale yellow powder. The product was confirmed by mass spectrometry (FDMS). Compound (7) was an amorphous material having a glass transition temperature of 193 ° C. and having no melting point.
また、ＣＢＰ、化合物（５）及び（７）の蛍光スペクトルを測定し、燐光材料の吸収スペクトルと比較した。その結果を図２に示す。 In addition, the fluorescence spectra of CBP and compounds (5) and (7) were measured and compared with the absorption spectra of phosphorescent materials. The result is shown in FIG.
図２から分かるように、化合物（５）及び（７）の蛍光スペクトルは、ＣＢＰと同等以上に燐光発光材料Ｉｒ（ｐｐｙ）３の吸収スペクトルとの重なりが大きい。これは、化合物（５）及び（７）からのエネルギー移動が効率よく起り得ることを示す。 As can be seen from FIG. 2, the fluorescence spectra of the compounds (5) and (7) have a large overlap with the absorption spectrum of the phosphorescent material Ir (ppy) 3 at least as much as CBP. This indicates that energy transfer from compounds (5) and (7) can occur efficiently.
また、スピンコート膜の薄膜安定性をＣＢＰ，化合物（５）及び（７）で比較した。その結果、化合物（５）及び（７）では、全く白濁が観察されなかったものの、ＣＢＰは薄膜調製直後に斑模様の不均一な薄膜となっており、また結晶化を示す白濁が見られたことから、化合物（５）及び（７）は、従来材料にはない高い薄膜安定性を有していることを示す。 The thin film stability of the spin coat film was compared between CBP and compounds (5) and (7). As a result, in the compounds (5) and (7), although white turbidity was not observed at all, CBP was a nonuniform thin film immediately after the thin film preparation, and white turbidity indicating crystallization was observed. This shows that the compounds (5) and (7) have high thin film stability not found in conventional materials.
実施例１
ガラス基板上にＩＴＯの透明電極を１３０ｎｍ形成し、真空度３×１０−７トールの圧力で、真空蒸着法によりＣｕＰｃを２０ｎｍ、ホール輸送層としてのＮＰＢを３０ｎｍ堆積した。さらに、燐光ホスト材料として上記化合物（５）を３０ｎｍの厚さで形成し、ここにドーパントとして化合物（１６）を８重量％ドープした。
Example 1
A transparent electrode of ITO was formed to 130 nm on a glass substrate, and CuPc was deposited to 20 nm and NPB as a hole transport layer was deposited to 30 nm by a vacuum deposition method at a vacuum degree of 3 × 10 −7 Torr. Further, the compound (5) was formed as a phosphorescent host material with a thickness of 30 nm, and 8% by weight of the compound (16) as a dopant was doped therein.
さらに、電子輸送材として化合物（２４）を３０ｎｍ蒸着した。最後にＬｉＦを０．５ｎｍ、Ａｌを１５０ｎｍ蒸着し、金属電極を形成した。その結果、５２０ｎｍ付近に緑色燐光が観測され、１００ｃｄ／ｍ２時の外部量子効率は８．６％であった。 Furthermore, 30 nm of compound (24) was vapor-deposited as an electron transport material. Finally, LiF was deposited to 0.5 nm and Al was deposited to 150 nm to form a metal electrode. As a result, green phosphorescence was observed in the vicinity of 520 nm, and the external quantum efficiency at 100 cd / m 2 was 8.6%.
実施例２
ガラス基板上にＩＴＯの透明電極を１３０ｎｍ形成し、この透明支持基板をエッチング、洗浄した。このＩＴＯガラス基板上にホール輸送性のＢａｙｔｒｏｎ Ｐ（商品名、ＰＥＤＯＴ：ＰＳＳ溶液（ポリエチレンジオキシチオフェン−ポリスチレンスルホン酸ドープ体）、バイエル社製）をスピンコートした後、１８０℃で１時間乾燥した（膜厚＝５０ｎｍ）。本発明の燐光ホスト化合物（５）２０ｍｇ、燐光発光性化合物（１６）２ｍｇ及び電子輸送材として化合物（２４）５ｍｇを１，２−ジクロロエタン ２．５ｇに溶解して得られた溶液を、スピンコート法によって上記導電性高分子層に塗布した。さらに、真空中で発光層を十分に乾燥させた後、ＬｉＦを０．５ｎｍ、Ａｌを１５０ｎｍ蒸着し、金属電極を形成した。
Example 2
An ITO transparent electrode of 130 nm was formed on a glass substrate, and this transparent support substrate was etched and washed. A hole transportable Baytron P (trade name, PEDOT: PSS solution (polyethylenedioxythiophene-polystyrene sulfonic acid dope), manufactured by Bayer) was spin-coated on the ITO glass substrate and dried at 180 ° C. for 1 hour. (Film thickness = 50 nm). A solution obtained by dissolving 20 mg of the phosphorescent host compound (5) of the present invention, 2 mg of the phosphorescent compound (16) and 5 mg of the compound (24) as an electron transport material in 2.5 g of 1,2-dichloroethane was spin-coated. The conductive polymer layer was applied by the method. Further, after sufficiently evaporating the light emitting layer in a vacuum, LiF was deposited to 0.5 nm and Al was deposited to 150 nm to form a metal electrode.
その結果、５２０ｎｍ付近に緑色発光が観測され、１００ｃｄ／ｍ２時の外部量子効率は８．９％であった。 As a result, green light emission was observed around 520 nm, and the external quantum efficiency at 100 cd / m 2 was 8.9%.
実施例３
化合物（１６）の代わりに化合物（１５）を用いた以外は実施例２と同様の操作を行い、素子を作成した。その結果、４７４ｎｍ付近に青色発光が観測され、１００ｃｄ／ｍ２時の外部量子効率は７．２％であった。
Example 3
A device was fabricated in the same manner as in Example 2 except that the compound (15) was used instead of the compound (16). As a result, blue light emission was observed around 474 nm, and the external quantum efficiency at 100 cd / m 2 was 7.2%.
実施例４
燐光ホスト化合物（５）の代わりに（７）を用いた以外は、実施例２と同様の操作を行い、素子を作成した。その結果、１００ｃｄ／ｍ２時の外部量子効率は９．０％であった。
Example 4
A device was fabricated in the same manner as in Example 2, except that (7) was used instead of the phosphorescent host compound (5). As a result, the external quantum efficiency at 100 cd / m 2 was 9.0%.
Claims (4)
4. An organic electroluminescence device comprising an organic layer that emits light between a cathode and an anode, wherein at least one of the organic layers is a mixture of a phosphorescent compound and the phosphorescent host compound according to claim 1. An organic electroluminescent device comprising:
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