JP2006253445A - Organic electroluminescence element - Google Patents
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本発明は平面光源、表示等に使用される有機エレクトロルミネッセンス（以下ＥＬと記す）素子に関するものである。 The present invention relates to an organic electroluminescence (hereinafter referred to as EL) element used for a planar light source, display and the like.
有機物質を使用したＥＬ素子は、固体発光型の安価な大面積フルカラー表示素子としての用途が有望視され、多くの開発が行われている。一般にＥＬ素子は、発光層及び該層を挟んだ一対の対向電極から構成されている。 An EL element using an organic substance is considered to be promising for use as an inexpensive large-area full-color display element of a solid light emitting type, and many developments have been made. In general, an EL element is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer.
この素子における発光は次の様な機構に基づくものである。すなわち、両電極間に電界が印加されると陰極側から電子、陽極側から正孔が注入され、これらが発光層において再結合し、エネルギー準位が伝導帯から価電子帯に戻る際にエネルギーを光として放出する
機構である。
The light emission in this element is based on the following mechanism. That is, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. These recombine in the light emitting layer, and the energy level is restored when the energy level returns from the conduction band to the valence band. Is a mechanism that emits light as light.
近年、１０Ｖ以下の低電圧で発光する高い蛍光量子効率を持った有機化合物を含有した薄膜を積層した有機EL素子が報告され、関心を集めている。（ Applied Physics Letters、51巻、913ページ、1987年を参照）この方法では、金属キレート錯体を発光層、アミン系化合物を正孔注入層に使用して高輝度の緑色発光が得られている。６〜７Vの直流電圧で輝度は１００ｃｄ／ｍ2 、最大発光効率は１．５ｌｍ／Ｗを達成し、ほぼ実用領域に近い性能を示している。しかしながら、現在までの有機EL素子は構成の改善により発光強度は改良されているが、未だ十分な発光輝度は有していない。また、繰り返し使用時の安定性に欠けるという重大な問題を有している。
本発明の目的は、発光効率が高く、繰り返し使用時での安定性の優れた有機ＥＬ素子の提供にある。本発明者らが鋭意検討した結果、発光層にド-パントとして一般式［１］で示される発光材料を使用した有機ＥＬ素子は、その発光効率が高く、繰り返し使用時での安定性も優れていることを見出し本発明に至った。 An object of the present invention is to provide an organic EL device having high luminous efficiency and excellent stability during repeated use. As a result of intensive studies by the present inventors, the organic EL device using the light emitting material represented by the general formula [1] as a dopant in the light emitting layer has high luminous efficiency and excellent stability during repeated use. The present invention has been found.
すなわち、本発明は、陽極と陰極とからなる一対の電極間に、発光層または発光層を含む複数層の有機化合物薄膜を形成してなる有機エレクトロルミネッセンス素子において、前記発光層が、ホスト材料50.0〜99.999重量％とドーパント材料0.001〜50.0重量％とからなり、前記ホスト材料が、芳香族３級アミン化合物、金属錯体化合物、複素環化合物、炭素環化合物、および、これらが直接結合で連結した化合物からなる群の少なくとも１つであり、前記ドーパント材料が下記一般式［１］で表される化合物である有機エレクトロルミネッセンス素子に関する。
一般式［１］
General formula [1]
また、本発明は、ホスト材料が、２つ以上のアミノ基を有する芳香族３級アミン化合物である上記有機エレクトロルミネッセンス素子に関する。 The present invention also relates to the above organic electroluminescence device, wherein the host material is an aromatic tertiary amine compound having two or more amino groups.
また、本発明は、ホスト材料が、アルミニウム、亜鉛、銅、ベリリウム、マグネシウムの少なくともいずれかを中心金属とする金属錯体化合物である上記有機エレクトロルミネッセンス素子に関する。 The present invention also relates to the organic electroluminescence device, wherein the host material is a metal complex compound having at least one of aluminum, zinc, copper, beryllium, and magnesium as a central metal.
また、本発明は、ホスト材料が、窒素原子、酸素原子およびまたは硫黄原子を含有する縮合複素環を含む化合物である上記の有機エレクトロルミネッセンス素子に関する。 The present invention also relates to the above organic electroluminescence device, wherein the host material is a compound containing a condensed heterocyclic ring containing a nitrogen atom, an oxygen atom and / or a sulfur atom.
また、本発明は、ホスト材料が、５員環以上の縮合炭素環を含む化合物である上記有機エレクトロルミネッセンス素子に関する。
Moreover, this invention relates to the said organic electroluminescent element whose host material is a compound containing a 5 or more membered condensed carbocyclic ring.
本発明の有機ＥＬ素子用材料を用いて作成した有機ＥＬ素子は、従来に比べて低い駆動電圧で発光し長寿命であるため、壁掛けテレビ等のフラットパネルディスプレイや平面発光体として好適に使用することができ、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等への応用が可能である。 Since the organic EL element produced using the organic EL element material of the present invention emits light at a lower driving voltage and has a longer life than conventional ones, it is preferably used as a flat panel display such as a wall-mounted television or a flat light emitter. It can be applied to light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights.
以下、詳細にわたって本発明を説明する。本発明における一般式［１］で示される化合物のＲ1.〜Ｒ28は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアルコキシ基、置換もしくは未置換のアリール基、置換もしくは未置換のアミノ基を表す。 Hereinafter, the present invention will be described in detail. R 1 to R 28 in the compound represented by the general formula [1] in the present invention are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. A substituted aryl group or a substituted or unsubstituted amino group is represented.
Ｒ1.〜Ｒ28の具体例は、ハロゲン原子としては弗素、塩素、臭素、ヨウ素であり、 Specific examples of R 1 to R 28 are fluorine, chlorine, bromine and iodine as halogen atoms,
置換もしくは未置換のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基等の炭素数１〜２０の未置換直鎖状又は分枝状アルキル基の他、２−フェニルイソプロピル基、トリクロロメチル基、トリフルオロメチル基、ベンジル基、α−フェノキシベンジル基、α，α−ジメチルベンジル基、α，α−メチルフェニルベンジル基、α，α−ジトリフルオロメチルベンジル基、トリフェニルメチル基、α−ベンジルオキシベンジル基等の炭素数１〜２０のアルキル基の置換体があり、 Examples of the substituted or unsubstituted alkyl group include carbon number such as methyl group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, and stearyl group. In addition to 1-20 unsubstituted linear or branched alkyl groups, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, There are substituents of alkyl groups having 1 to 20 carbon atoms such as α, α-methylphenylbenzyl group, α, α-ditrifluoromethylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group,
置換もしくは未置換のアルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基、ｎ−ブトキシ基、ｔ−ブトキシ基、ｎ−オクチルオキシ基、ｔ−オクチルオキシ基等の炭素数１〜２０の未置換アルコキシル基の他、１，１，１−テトラフルオロエトキシ基、フェノキシ基、ベンジルオキシ基、オクチルフェノキシ基等の炭素数１〜２０のアルコキシル基の置換体があり、 As the substituted or unsubstituted alkoxyl group, an unsubstituted C1-C20 such as methoxy group, ethoxy group, propoxy group, n-butoxy group, t-butoxy group, n-octyloxy group, t-octyloxy group, etc. In addition to alkoxyl groups, there are substitutions of C1-C20 alkoxyl groups such as 1,1,1-tetrafluoroethoxy group, phenoxy group, benzyloxy group, octylphenoxy group,
置換もしくは未置換のアリール基としては、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、４−エチルフェニル基、ビフェニル基、４−メチルビフェニル基、４−エチルビフェニル基、４−シクロヘキシルビフェニル基、ターフェニル基、３，５−ジクロロフェニル基、ナフチル基、５−メチルナフチル基、アントリル基、ピレニル基等の芳香族炭素数６〜１８の置換もしくは未置換のアリール基があり、また、アリール基は、窒素原子、酸素原子およびまたは硫黄原子により芳香族炭素原子が置換されていてもよく、 Examples of substituted or unsubstituted aryl groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, biphenyl, 4-methylbiphenyl, 4-ethylbiphenyl. Group, 4-cyclohexylbiphenyl group, terphenyl group, 3,5-dichlorophenyl group, naphthyl group, 5-methylnaphthyl group, anthryl group, pyrenyl group, etc., substituted or unsubstituted aryl groups having 6 to 18 aromatic carbon atoms And the aryl group may have an aromatic carbon atom substituted by a nitrogen atom, an oxygen atom and / or a sulfur atom,
窒素原子、酸素原子およびまたは硫黄原子により芳香族炭素原子が置換されていてもよいアリール基としては、フラニル基、チオフェニル基、ピロール基、ピラニル基、チオピラニル基、ピリジニル基、チアゾリル基、イミダゾール基、ピリミジニル基、ピリジニル基、トリアジニル基、インドリニル基、キノリル基、プリニル基等があり、置換もしくは未置換のアミノ基としては、アミノ基、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、フェニルメチルアミノ基、ジフェニルアミノ基、ジトリルアミノ基、ジベンジルアミノ基等がある。また、隣接する置換基同士で、それぞれ互いに結合して、フェニル基、ナフチル基、アントリル基、ピレニル基等を形成しても良い。 As the aryl group in which the aromatic carbon atom may be substituted by a nitrogen atom, an oxygen atom and / or a sulfur atom, a furanyl group, a thiophenyl group, a pyrrole group, a pyranyl group, a thiopyranyl group, a pyridinyl group, a thiazolyl group, an imidazole group, There are pyrimidinyl group, pyridinyl group, triazinyl group, indolinyl group, quinolyl group, purinyl group, etc., as substituted or unsubstituted amino group, dialkylamino group such as amino group, dimethylamino group, diethylamino group, phenylmethylamino group , Diphenylamino group, ditolylamino group, dibenzylamino group and the like. Further, adjacent substituents may be bonded to each other to form a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, or the like.
本発明における一般式［１］で示される化合物のＸ1 〜Ｘ4 は、それぞれ独立に、Ｏ、Ｓ、Ｃ＝Ｏ、ＳＯ2 、（ＣＨ2 ）ｘ−Ｏ−（ＣＨ2 ）ｙ、置換もしくは未置換のアルキレン基、置換もしくは未置換の脂肪族環残基を表す。ここで、ｘおよびｙは、それぞれ独立に、０〜２０の整数を表すが、ｘ＋ｙ＝０となることはない。
置換または未置換のアルキレン基としては炭素数１〜２０のアルキレン基もしくはその置換体、
置換または未置換の脂肪族環残基としては、シクロペンチル環、シクロヘキシル環、４−メチルシクロヘキシル環、シクロヘプチル環等の炭素数５〜７の脂肪族環の二価の残基が挙げられる。
Ｘ1 〜Ｘ4 の置換アルキレン基又は置換脂肪族環残基の置換基としてはＲ1.〜Ｒ28で示した置換基がある。Ｘ1 〜Ｘ4 の置換アルキレン基として好ましいものは、２−フェニルイソプロピレン基、ジクロロメチレン基、ジフルオロメチレン基、ベンジレン基、α−フェノキシベンジレン基、α，α−ジメチルベンジレン基、α，α−メチルフェニルベンジレン基、ジフェニルメチレン基、α−ベンジルオキシベンジレン基などが挙げられる。
X 1 to X 4 of the compound represented by the general formula [1] in the present invention are each independently O, S, C═O, SO 2 , (CH 2 ) x —O— (CH 2 ) y, substituted Alternatively, it represents an unsubstituted alkylene group or a substituted or unsubstituted aliphatic ring residue. Here, x and y each independently represent an integer of 0 to 20, but x + y = 0 does not occur.
As the substituted or unsubstituted alkylene group, an alkylene group having 1 to 20 carbon atoms or a substituted product thereof,
Examples of the substituted or unsubstituted aliphatic ring residue include divalent residues of an aliphatic ring having 5 to 7 carbon atoms such as a cyclopentyl ring, a cyclohexyl ring, a 4-methylcyclohexyl ring, and a cycloheptyl ring.
Examples of the substituted alkylene group or substituted aliphatic ring residue of X 1 to X 4 include the substituents represented by R 1 to R 28 . Preferred as the substituted alkylene group for X 1 to X 4 are 2-phenylisopropylene group, dichloromethylene group, difluoromethylene group, benzylene group, α-phenoxybenzylene group, α, α-dimethylbenzylene group, α, An α-methylphenylbenzylene group, a diphenylmethylene group, an α-benzyloxybenzylene group, and the like can be given.
上記一般式［１］で表される化合物の内、好ましいものとしては、下記一般式［２］で表される化合物があげられる。 Of the compounds represented by the general formula [1], a compound represented by the following general formula [2] is preferable.
一般式［２］
［式中、Ｒ1.〜Ｒ28、および、Ｘ1 〜Ｘ4 は、一般式［１］のそれらと同じ意味を表す。］ [Wherein R 1 to R 28 and X 1 to X 4 represent the same meaning as those in the general formula [1]. ]
さらに、上記一般式［２］で表される化合物の内、さらに好ましいものとして、下記一般式［３］で表される化合物があげられる。 Furthermore, among the compounds represented by the general formula [2], a compound represented by the following general formula [3] is more preferable.
一般式［３］
［式中、Ｒ1.〜Ｒ28は、一般式［１］のそれらと同じ意味を表す。Ｙ1.〜Ｙ8 は、置換もしくは未置換の炭素数１〜２０のアルキル基、置換もしくは未置換の炭素数６〜１６のアリール基を表す。Ｒ1 〜Ｒ4 もしくはＲ5 〜Ｒ8 は隣接した置換基同士で結合して新たな６員アリール環を形成してもよい。］
ここでいうアルキル基およびアリール基の具体例は、前記のＲ1.〜Ｒ28で記述したアルキル基およびアリール基が挙げられる。
[Wherein R 1 to R 28 represent the same meaning as those in the general formula [1]. Y 1 to Y 8 represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted aryl group having 6 to 16 carbon atoms. R 1 to R 4 or R 5 to R 8 may combine with adjacent substituents to form a new 6-membered aryl ring. ]
Specific examples of the alkyl group and aryl group herein include the alkyl group and aryl group described in the above R 1 to R 28 .
この化合物の中で、一般式［１］〜［３］で表されるような芳香族環を有している置換基を持つ化合物、もしくは一般式［１］〜［３］のＲ1.〜Ｒ28の隣接する置換基同士で芳香族環を形成している化合物は、ガラス転移点や融点が高くなり電界発光時における有機層中、有機層間もしくは、有機層と金属電極間で発生するジュール熱に対する耐性（耐熱性）が向上するので、有機ＥＬ素子の発光材料として使用した場合、高い発光輝度を示し、長時間発光させる際にも有利である。本発明の化合物は、これらの置換基に限定されるものではない。 Among these compounds, compounds having a substituent having an aromatic ring as represented by the general formulas [1] to [3], or R 1 to the general formulas [1] to [3] A compound in which an aromatic ring is formed by adjacent substituents of R 28 has a glass transition point and a high melting point, and a joule generated in an organic layer, an organic layer, or between an organic layer and a metal electrode during electroluminescence. Since resistance to heat (heat resistance) is improved, when used as a light emitting material of an organic EL element, it exhibits high light emission luminance and is advantageous when emitting light for a long time. The compounds of the present invention are not limited to these substituents.
以下に、本発明の一般式［１］〜［３］の化合物の代表例を、表１に具体的に例示するが、本発明は、この代表例に限定されるものではない。 Specific examples of the compounds of the general formulas [1] to [3] of the present invention are specifically illustrated in Table 1 below, but the present invention is not limited to these representative examples.
次に、本発明のホスト材料の芳香族３級アミン化合物の代表例を、表２に具体的に例示するが、本発明は、この代表例に限定されるものではない。なお、芳香族３級アミン化合物は、２つ以上のアミノ基を有することが好ましい。 Next, representative examples of the aromatic tertiary amine compound of the host material of the present invention are specifically illustrated in Table 2, but the present invention is not limited to these representative examples. The aromatic tertiary amine compound preferably has two or more amino groups.
次に、本発明のホスト材料の金属錯体化合物の代表例を、表３に具体的に例示するが、本発明は、この代表例に限定されるものではない。なお、金属錯体化合物は、アルミニウム、亜鉛、銅、ベリリウム、マグネシウムの少なくともいずれかを中心金属とすることが好ましい。 Next, representative examples of the metal complex compound of the host material of the present invention are specifically exemplified in Table 3, but the present invention is not limited to these representative examples. Note that the metal complex compound preferably has at least one of aluminum, zinc, copper, beryllium, and magnesium as a central metal.
次に、本発明のホスト材料の複素環化合物、あるいは、複素環化合物と炭素環化合物とが直接結合で連結した化合物の代表例を、表４に具体的に例示するが、本発明は、この代表例に限定されるものではない。なお、複素環として、窒素原子、酸素原子およびまたは硫黄原子の少なくともいずれかを複素原子とする縮合環を含むが好ましい。 Next, representative examples of the heterocyclic compound of the host material of the present invention, or a compound in which the heterocyclic compound and the carbocyclic compound are connected by a direct bond are specifically exemplified in Table 4, but the present invention is not limited to this. It is not limited to a representative example. The heterocyclic ring preferably includes a condensed ring having at least one of a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom.
次に、本発明のホスト材料の炭素環化合物、あるいは、炭素環化合物と炭素環化合物とが直接結合で連結した化合物の代表例を、表５に具体的に例示するが、本発明は、この代表例に限定されるものではない。なお、炭素環として、５員環以上の縮合炭素環を含む化合物が好ましい。 Next, representative examples of the carbocyclic compound of the host material of the present invention or a compound in which the carbocyclic compound and the carbocyclic compound are connected by a direct bond are specifically exemplified in Table 5. It is not limited to a representative example. In addition, the compound containing a 5-membered or more condensed carbocycle as a carbocycle is preferable.
有機ＥＬ素子は、陽極と陰極間に一層もしくは多層の有機化合物薄膜を形成した素子である。一層型の場合、陽極と陰極との間に発光層を設けている。発光層は、発光材料を含有し、それに加えて陽極から注入した正孔もしくは陰極から注入した電子を発光材料まで輸送させるために正孔注入材料、正孔輸送材料もしくは電子注入材料、電子輸送材料を含有しても良い。電子注入材料とは陰極から電子を注入され得る能力を持つ材料であり、電子輸送材料とは注入された電子を発光層へ輸送する能力を持つ材料である。正孔注入材料とは、陽極から正孔を注入され得る能力を持つ材料であり、正孔輸送材料とは、注入された正孔を発光層へ輸送する能力を持つ材料である。 An organic EL element is an element in which a single-layer or multilayer organic compound thin film is formed between an anode and a cathode. In the case of the single layer type, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and in addition to that, a hole injecting material, a hole transporting material or an electron injecting material, and an electron transporting material for transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. May be contained. The electron injection material is a material having the ability to inject electrons from the cathode, and the electron transport material is a material having the ability to transport the injected electrons to the light emitting layer. The hole injection material is a material having the ability to inject holes from the anode, and the hole transport material is a material having the ability to transport the injected holes to the light emitting layer.
多層型としては、陽極／正孔注入帯域／発光層／陰極、陽極／発光層／電子注入帯域／陰極、陽極／正孔注入帯域／発光層／電子注入帯域／陰極の多層構成で積層した有機ＥＬ素子がある。 As the multilayer type, organic layers laminated in a multilayer structure of anode / hole injection band / light emitting layer / cathode, anode / light emitting layer / electron injection band / cathode, anode / hole injection band / light emitting layer / electron injection band / cathode. There is an EL element.
本発明の一般式［１］で示される化合物は、固体状態において強い蛍光を持つ化合物であり、発光層内におけるドーピング材料として発光層中にて最適の割合でドーピングすることにより、高い発光効率および発光波長の選択が可能である。又、ド-ピング材料には、一般式［１］と共に一般式［１］以外の化合物を用いる事で青から赤色、さらには白色の発光を得ることができる。 The compound represented by the general formula [1] of the present invention is a compound having strong fluorescence in the solid state. By doping at an optimum ratio in the light emitting layer as a doping material in the light emitting layer, high luminous efficiency and The emission wavelength can be selected. In addition, by using a compound other than the general formula [1] together with the general formula [1] as the doping material, light emission of blue to red or even white can be obtained.
発光層には、発光材料およびドーピング材料に加えて、必要があれば正孔注入材料や電子注入材料を使用することもできる。 In addition to the light emitting material and the doping material, if necessary, a hole injection material or an electron injection material can be used for the light emitting layer.
有機ＥＬ素子は、多層構造にすることによりクエンチングによる輝度や寿命の低下を防ぐことができる。また、必要があれば、発光材料、ドーピング材料、キャリア注入を行う正孔注入材料や電子注入材料を二種類以上組み合わせて使用することも出来る。更に、正孔注入層、発光層および電子注入層はそれぞれ二層以上の層構成により形成されていてもよく、正孔もしくは電子が効率よく電極から注入され、効率よく層中で輸送され得る素子構造が選択される。 The organic EL element can prevent a decrease in luminance and lifetime due to quenching by adopting a multilayer structure. If necessary, a light emitting material, a doping material, a hole injecting material for injecting carriers, and an electron injecting material can be used in combination. Furthermore, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed of two or more layers, and an element in which holes or electrons can be efficiently injected from the electrode and efficiently transported in the layer. A structure is selected.
有機ＥＬ素子の陽極に使用される導電性材料としては、4eVより大きな仕事関数を持つものが適しており、炭素、アルミニウム、バナジウム、鉄、コバルト、ニッケル、タングステン、銀、金、白金、パラジウム等およびそれらの合金、ＩＴＯ基板、ＮＥＳＡ基板と
称される酸化スズ、酸化インジウム等の酸化金属、更にはポリチオフェンやポリピロール等の有機導電性樹脂が用いられる。
As the conductive material used for the anode of the organic EL element, a material having a work function larger than 4 eV is suitable, such as carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. Further, alloys thereof, ITO substrates, metal oxides such as tin oxide and indium oxide called NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used.
陰極に使用される導電性材料としては、4eVより小さな仕事関数を持つものが適しており、マグネシウム、カルシウム、錫、鉛、チタニウム、イットリウム、リチウム、ルテニウム、マンガン等およびそれらの合金が用いられる。合金としては、マグネシウム／銀、マグネシウム／インジウム、リチウム／アルミニウム等が代表例として挙げられるが、これらに限定されるものではない。合金の比率は、加熱の温度、雰囲気、真空度により制御され適切な比率が選択される。陽極及び陰極は、必要があれば二層以上の層構成により形成されていても良い。 As the conductive material used for the cathode, a material having a work function smaller than 4 eV is suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, and alloys thereof are used. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the heating temperature, atmosphere, and degree of vacuum, and an appropriate ratio is selected. If necessary, the anode and the cathode may be formed of two or more layers.
有機ＥＬ素子では、効率良く発光させるために、用いられる陽極、陰極のうち少なくとも一方は素子の発光波長領域において十分透明であることが望ましく、基板もまた透明であることが望ましい。透明電極は、上記の導電性材料を使用して、蒸着やスパッタリング等の方法で所定の透光性を確保するように設定する。発光面の電極は、光透過率を10%以上にすることが望ましい。 In the organic EL element, in order to emit light efficiently, at least one of the anode and the cathode used is desirably sufficiently transparent in the light emission wavelength region of the element, and the substrate is also desirably transparent. The transparent electrode is set so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering using the conductive material. The electrode on the light emitting surface preferably has a light transmittance of 10% or more.
本発明に係わる有機ＥＬ素子の各層の形成は、真空蒸着、スパッタリング等の乾式成膜法やスピンコーティング、ディッピング等の湿式成膜法の何れの方法でも適用することができる。膜厚は特に限定されるものではないが、各層は適切な膜厚に設定する必要がある。膜が厚すぎる場合には、一定の光出力を得るために大きな印加電圧が必要になり、その結果として効率が悪くなる。また、膜が薄すぎる場合には、ピンホール等が発生し、電圧を印加しても十分な発光輝度が得られない。通常用いられる膜厚としては５ｎｍから１０μｍの範囲が適しているが、１０ｎｍから０．２μｍの範囲が更に好ましい。 The formation of each layer of the organic EL element according to the present invention can be applied by any of dry film forming methods such as vacuum deposition and sputtering and wet film forming methods such as spin coating and dipping. The film thickness is not particularly limited, but each layer needs to be set to an appropriate film thickness. If the film is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Further, when the film is too thin, pinholes or the like are generated, and sufficient light emission luminance cannot be obtained even when a voltage is applied. The film thickness usually used is in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.
湿式成膜法の場合には、各層を形成する材料をクロロホルム、テトラヒドロフラン、ジオキサン等の適切な溶媒に溶解あるいは分散することにより有機化合物薄膜を形成する。 In the case of the wet film forming method, the organic compound thin film is formed by dissolving or dispersing the material for forming each layer in an appropriate solvent such as chloroform, tetrahydrofuran, dioxane or the like.
乾式あるいは湿式成膜法から調製される何れの薄膜においても、成膜性の向上、ピンホール防止等の目的の為に適切な樹脂あるいは添加剤を使用してもよい。この様な樹脂としては、ポリスチレン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、
ポリウレタン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース等の絶縁性樹脂、ポリ−Ｎ−ビニルカルバゾール、ポリシラン等の光導電性樹脂、ポリチオフェン、ポリピロール等の導電性樹脂を挙げることができる。また、添加剤としては、酸化防止剤、紫外線吸収剤、可塑剤等を挙げることができる。
In any thin film prepared from a dry or wet film forming method, an appropriate resin or additive may be used for the purpose of improving the film forming property and preventing pinholes. Such resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide,
Examples thereof include insulating resins such as polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate and cellulose, photoconductive resins such as poly-N-vinylcarbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
正孔注入材料としては、正孔を注入する能力を持ち、発光層または発光材料に対して優れた正孔注入効果を有し、発光層で生成した励起子の電子注入層または電子注入材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。具体的な例としては、フタロシアニン系化合物、ナフタロシアニン系化合物、ポルフィリン系化合物、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾール、オキサゾール、オキサジアゾール、ヒドラゾン、アシルヒドラゾン、ポリアリールアルカン、スチルベン、ブタジエン、ベンジジン型トリフェニルアミン、スチリルアミン型トリフェニルアミン、ジアミン型トリフェニルアミン等と、それらの誘導体、およびポリビニルカルバゾール、ポリシラン、導電性高分子等の高分子材料等が挙げられるが、これらに限定されるものではない。 As a hole injection material, it has the ability to inject holes, has an excellent hole injection effect for the light emitting layer or light emitting material, and excitons generated in the light emitting layer to the electron injection layer or electron injection material And a compound having an excellent ability to form a thin film. Specific examples include phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazoles, triazoles, imidazoles, imidazolones, imidazolethiones, pyrazolines, pyrazolones, tetrahydroimidazoles, oxazoles, oxadiazoles, hydrazones, acyl hydrazones. , Polyarylalkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers However, it is not limited to these.
電子注入材料としては、電子を注入する能力を持ち、発光層または発光材料に対して優れた電子注入効果を有し、発光層で生成した励起子の正孔注入層または正孔注入材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。例としては、キノリン金属錯体、オキサジアゾール、ベンゾチアゾール金属錯体、ベンゾオキサゾール金属錯体、ベンゾイミダゾール金属錯体、フルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、オキサジアゾール、チアジアゾール、テトラゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等とそれらの誘導体等が挙げられるが、これらに限定されるものではない。 As an electron injection material, it has the ability to inject electrons, has an excellent electron injection effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer are injected into the hole injection layer or the hole injection material. Examples thereof include compounds that prevent migration and have excellent thin film forming ability. Examples include quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxadiazole, thiadiazole, tetrazole, perylene. Examples include tetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and derivatives thereof, but are not limited thereto.
また、正孔注入材料に電子受容性物質、電子注入材料に電子供与性物質を添加することによる増感も可能である。 Further, sensitization by adding an electron accepting substance to the hole injecting material and an electron donating substance to the electron injecting material is also possible.
本発明により得られた有機ＥＬ素子の温度、湿度、雰囲気等に対する安定性の向上の為に素子の表面に保護層を設けたり、シリコンオイル等を封入して素子全体を保護することも可能である。 In order to improve the stability of the organic EL device obtained by the present invention against temperature, humidity, atmosphere, etc., it is possible to provide a protective layer on the surface of the device, or to enclose silicon oil or the like to protect the entire device. is there.
本発明の有機ＥＬ素子からの発光を効率よく取り出すためには、発光を取り出す面の基板の材質が充分透明であることが望ましく、具体的には素子からの発光の発光波長領域における透過率が５０％以上、好ましくは９０％以上であることが望ましい。これら基板は、機械的、熱的強度を有し、透明であれば特に限定されるものではないが、例えば、ガラスの他、ポリエチレン、ポリエーテルスルホン、ポリプロピレン等の透明性ポリマーが推奨される。 In order to efficiently extract light emitted from the organic EL device of the present invention, it is desirable that the substrate material on the surface from which light is extracted is sufficiently transparent. Specifically, the transmittance of light emitted from the device in the light emission wavelength region is high. It is desirable that it is 50% or more, preferably 90% or more. These substrates have mechanical and thermal strength and are not particularly limited as long as they are transparent. For example, in addition to glass, transparent polymers such as polyethylene, polyethersulfone, and polypropylene are recommended.
以上述べたように、本有機ＥＬ素子は、低駆動電圧と高輝度を示す緑色発光素子である。故に、本有機ＥＬ素子は、壁掛けテレビ等のフラットパネルディスプレイや平面発光体として、さらには、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等への応用が考えられる。 As described above, the present organic EL element is a green light emitting element exhibiting a low driving voltage and high luminance. Therefore, this organic EL device can be applied to flat panel displays such as wall-mounted televisions and flat light emitters, as well as light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. Can be considered.
以下、実施例にて本発明を具体的に説明するが、本発明は下記実施例に何ら限定されるものではない。本例では、特に断りのない限り、混合比は全て重量比を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example at all. In this example, all mixing ratios indicate weight ratios unless otherwise specified.
実施例１
厚さ２００ｎｍのＩＴＯ透明電極（陽極）を有するガラス基板を、中性洗剤、アセトン、エタノールを用いて超音波洗浄した。その基板を窒素ガスを用いて乾燥し、さらにＵＶ／オゾン洗浄した後、蒸着装置の基板ホルダーに固定した後、蒸着槽を３×１０-6Ｔｏｒｒに減圧した。まず、ＩＴＯ透明電極上に、４，４’−ビス〔Ｎ−フェニル−Ｎ−（３”−メチルフェニル）アミノ〕ビフェニルを、蒸着速度０．２ｎｍ／sec で７５ｎｍの厚さに蒸着し、正孔輸送層とした。次いで、ホスト化合物として表２の化合物２１と、ド−パント化合物として表１の化合物６を、異なる蒸着源から、蒸着速度０．２ｎｍ／ｓｅｃで５０ｎｍの厚さに共蒸着（重量比１００：０．５）し、発光層とした。次に、トリス（８−キノリノラート）アルミニウムを、蒸着速度０．２ｎｍ／ｓｅｃ で５０ｎｍの厚さに蒸着し、電子輸送層とした。さらにその上に、マグネシウムと銀を、蒸着速度０．２ｎｍ／ｓｅｃで２００ｎｍの厚さに共蒸着（重量比１０：１）して陰極とし、有機エレクトロルミネッセンス素子を作製した。尚、蒸着は、蒸着槽の減圧状態を保ったまま実施した。作製した有機電界発光素子に、直流電圧を印下したところ、最高輝度１０００００ｃｄ／ｍ2 の緑色の発光が確認された。この素子は駆動電圧５Ｖでの輝度が３０００ｃｄ／ｍ2であった。さらに発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命は１万時間以上であった。
Example 1
A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 nm was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further UV / ozone cleaned, fixed to the substrate holder of the vapor deposition apparatus, and then the vapor deposition tank was depressurized to 3 × 10 −6 Torr. First, 4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino] biphenyl was deposited on the ITO transparent electrode to a thickness of 75 nm at a deposition rate of 0.2 nm / sec. Next, the compound 21 of Table 2 as a host compound and the compound 6 of Table 1 as a dopant compound were co-deposited to a thickness of 50 nm from different deposition sources at a deposition rate of 0.2 nm / sec. Next, tris (8-quinolinolato) aluminum was deposited to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron transport layer. Furthermore, magnesium and silver were co-deposited to a thickness of 200 nm at a deposition rate of 0.2 nm / sec (weight ratio 10: 1) to form a cathode to produce an organic electroluminescence device. Steam Was performed while maintaining the vacuum of the tank. The organic electroluminescent element produced, was defeated mark a DC voltage, a green emission maximum luminance 100000cd / m 2 was identified. This element is in driving voltage 5V The luminance was 3000 cd / m 2 , and the half-life when driven at a constant current at an emission luminance of 500 cd / m 2 was 10,000 hours or more.
実施例２〜実施例１８
化合物２１の代わりに表６に示すホスト化合物を用いる以外は、全て実施例１と同様の方法で有機ＥＬ素子を作製した。それぞれの素子に、乾燥雰囲気下、直流電圧を印下したところ、青緑色〜緑の発光が確認された。これらの素子における、最高輝度および駆動電圧５Ｖでの輝度および発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命を併せて表６に示す。これらの素子はいずれも、駆動電圧５Ｖでの輝度が２０００ｃｄ／ｍ2以上であり、発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命は８０００時間以上であった。
Examples 2 to 18
An organic EL device was produced in the same manner as in Example 1 except that the host compound shown in Table 6 was used instead of compound 21. When a direct current voltage was applied to each element in a dry atmosphere, light emission of blue green to green was confirmed. Table 6 shows the half-life when these elements are driven at a constant current at the maximum luminance, the luminance at a driving voltage of 5 V, and the emission luminance of 500 cd / m 2 . All of these elements had a luminance of 2000 cd / m 2 or more at a driving voltage of 5 V, and a half life of 8000 hours or more when driven at a constant current at an emission luminance of 500 cd / m 2 .
実施例１９〜実施例３５
化合物６の代わりに表７に示すド-パント化合物を用いる以外は、全て実施例１と同様の方法で有機ＥＬ素子を作製した。それぞれの素子に、直流電圧を印下したところ、青緑〜緑の発光が確認された。これらの素子における、最高輝度および駆動電圧５Ｖでの輝度および発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命を併せて表７に示す。これらの素子はいずれも、駆動電圧５Ｖでの輝度が２０００ｃｄ／ｍ2以上であり、発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命は８０００時間以上であった。
Examples 19 to 35
An organic EL device was produced in the same manner as in Example 1 except that the dopant compound shown in Table 7 was used instead of compound 6. When direct current voltage was applied to each element, light emission of blue-green to green was confirmed. Table 7 shows the half-life when these elements are driven at a constant current at the maximum luminance, the luminance at a driving voltage of 5 V, and the emission luminance of 500 cd / m 2 . All of these elements had a luminance of 2000 cd / m 2 or more at a driving voltage of 5 V, and a half life of 8000 hours or more when driven at a constant current at an emission luminance of 500 cd / m 2 .
比較例1〜２
化合物６の代わりに表８に示すド-パント化合物を用いる以外は、実施例１と同様の方法で有機ＥＬ素子を作製した。それぞれの素子に、直流電圧を印下したところ、青緑〜緑の発光が確認された。これらの素子における、最高輝度および駆動電圧５Ｖでの輝度および発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命を併せて表8に示す。これらの素子はいずれも、駆動電圧５Ｖでの輝度は５０ｃｄ／ｍ2未満であり、発光輝度５００ｃｄ／ｍ2で定電流駆動したときの半減寿命は１００時間未満であった。
Comparative Examples 1-2
An organic EL device was produced in the same manner as in Example 1 except that the dopant compound shown in Table 8 was used instead of Compound 6. When direct current voltage was applied to each element, light emission of blue-green to green was confirmed. Table 8 shows the half life when these elements were driven at a constant current at the maximum luminance, the luminance at a driving voltage of 5 V, and the emission luminance of 500 cd / m 2 . All of these devices, the luminance of the drive voltage 5V is less than 50 cd / m 2, the half-life when the constant current driving with emission luminance 500 cd / m 2 was less than 100 hours.
以上述べた実施例から明らかなように、本発明の有機ＥＬ素子は低電圧駆動時での発光輝度の向上と長寿命化を達成することが可能である。 As is clear from the above-described embodiments, the organic EL device of the present invention can achieve an improvement in light emission luminance and a longer life when driven at a low voltage.
Claims (5)
一般式［１］
General formula [1]
The organic electroluminescence device according to claim 1, wherein the host material is a compound containing a condensed carbon ring having a 5-membered ring or more.
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