JP6130629B2 - Organic electroluminescence device - Google Patents
Organic electroluminescence device Download PDFInfo
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- JP6130629B2 JP6130629B2 JP2012139962A JP2012139962A JP6130629B2 JP 6130629 B2 JP6130629 B2 JP 6130629B2 JP 2012139962 A JP2012139962 A JP 2012139962A JP 2012139962 A JP2012139962 A JP 2012139962A JP 6130629 B2 JP6130629 B2 JP 6130629B2
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- organic electroluminescent
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- 238000005401 electroluminescence Methods 0.000 title description 15
- 239000010410 layer Substances 0.000 claims description 249
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- 239000011230 binding agent Substances 0.000 claims description 32
- 239000011164 primary particle Substances 0.000 claims description 32
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- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 10
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Description
本発明は、有機層の少なくとも一層が、Ｅｇ（バンドギャップ）が１．３〜２．５ｅＶの化合物からなり、膜厚が０．５ｎｍ以上１０ｎｍ未満のバンドギャップ化合物層である、有機電界発光素子に関する。 The present invention provides an organic electroluminescent device in which at least one organic layer is composed of a compound having an Eg (band gap) of 1.3 to 2.5 eV and a film thickness of 0.5 nm or more and less than 10 nm. About.
有機電界発光素子（以下、「有機ＥＬ素子」と称することもある。）は、基板上に陽極及び陰極からなる一対の電極と、該一対の電極の間に、発光層を含む有機層を有する自発光型の発光装置であり、ディスプレイや照明など種々の用途への応用が期待されている。
有機電界発光素子に拡散層を付加して、内部に閉じ込められた光の一部を取り出すことにより、外部量子効率を高めることが出来ることは知られている。しかし、吸収の強い材料を使用した有機電界発光素子では、その光取出しの効果が低減し、外部量子効率が低下する。特に、有機層導波光（有機層内部に閉じ込められた光）を原資として光取出し量を高める配置の構成したもの（基板と透明電極の間に拡散層を配置したもの）では、外部量子効率の低下が著しい。
高い発光効率を実現することを目的として、光の反射・屈折角の乱れを生じさせる領域を基板と発光層との間に有する有機電界発光素子が提案されている（特許文献１）。そして、該特許文献においては、銅フタロシアニンからなる正孔注入層（１５ｎｍ）を有する有機電界発光素子が記載されている。
また、外部への光の取り出し効率が高い素子を得ることを目的として、発光素子中の層の屈折率と層間距離とを所定の範囲とした有機電界発光素子が提案されている（特許文献２）。そして、該特許文献においては、銅フタロシアニンからなるバッファ層（５ｎｍ）を有する有機電界発光素子が記載されている。
An organic electroluminescent element (hereinafter sometimes referred to as “organic EL element”) has a pair of electrodes including an anode and a cathode on a substrate, and an organic layer including a light emitting layer between the pair of electrodes. It is a self-luminous light emitting device, and is expected to be applied to various uses such as displays and lighting.
It is known that external quantum efficiency can be increased by adding a diffusion layer to an organic electroluminescent device and extracting a part of the light confined inside. However, in an organic electroluminescence device using a material having strong absorption, the light extraction effect is reduced and the external quantum efficiency is lowered. In particular, an organic layer guided light (light confined inside the organic layer) is used as a source to increase the amount of light extraction (with a diffusion layer disposed between the substrate and the transparent electrode). The decline is remarkable.
For the purpose of realizing high luminous efficiency, an organic electroluminescent element has been proposed that has a region between a substrate and a light emitting layer that causes a disturbance of reflection and refraction angle of light (Patent Document 1). And in this patent document, the organic electroluminescent element which has a positive hole injection layer (15 nm) which consists of copper phthalocyanine is described.
Further, for the purpose of obtaining an element with high light extraction efficiency to the outside, an organic electroluminescent element having a refractive index and an interlayer distance in a predetermined range within a light emitting element has been proposed (Patent Document 2). ). And in this patent document, the organic electroluminescent element which has a buffer layer (5 nm) which consists of copper phthalocyanine is described.
しかしながら、特許文献１で使用される正孔注入層は膜厚が大きく、膜厚を調節して高い発光効率が得られることについては何ら記載も示唆もされていない。
また、特許文献２には、光を拡散、散乱する層に使用する光散乱粒子の一次粒子径について特に規定がなく、該一次粒子径を調節することにより高い発光効率が得られることについて何ら記載も示唆もされていない。更に、バッファ層の厚みと有機電界発光素子の性能との関係についても何ら記載されていない。
However, the hole injection layer used in
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。
即ち、本発明は、有機層の少なくとも一層の材料及び膜厚を最適化して導波光の吸収を下げ、光を拡散、散乱する層を用いて拡散層による光取出し量の効率低下を抑制することにより、外部量子効率が高く駆動電圧の低い有機電界発光素子を提供することを目的とする。
An object of the present invention is to solve the above-described problems and achieve the following objects.
That is, the present invention optimizes the material and film thickness of at least one layer of the organic layer to reduce the absorption of guided light, and suppresses the decrease in the efficiency of light extraction by the diffusion layer using a layer that diffuses and scatters light. Accordingly, an object of the present invention is to provide an organic electroluminescent device having high external quantum efficiency and low driving voltage.
本発明者らは前記課題を解決するために鋭意検討し、基板と、光を拡散、散乱する光学層と、透明電極である第１電極と、有機発光層を含む有機層と、第２電極と、がこの順に形成された有機電界発光素子であって、前記光学層は、一次粒子径が０．５μｍ以上の透明な少なくとも１種の光散乱粒子とバインダ成分とを含み、該バインダ成分は前記有機発光層の屈折率以上の屈折率を有し、前記有機層は更にバンドギャップ化合物層を少なくとも一層含み、該バンドギャップ化合物層はＥｇ（バンドギャップ）が１．３〜２．５ｅＶの化合物からなり、膜厚が０．５ｎｍ以上１０ｎｍ未満である、有機電界発光素子を見出した。当該構成を有する有機電界発光素子を採用することにより、素子の高い外部量子効率と低い駆動電圧とを両立させることができることを見出した。
すなわち、前記課題を解決する手段は、以下のとおりである。なお、本明細書において「〜」はその前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
In order to solve the above-mentioned problems, the present inventors have intensively studied, a substrate, an optical layer that diffuses and scatters light, a first electrode that is a transparent electrode, an organic layer that includes an organic light emitting layer, and a second electrode. Are formed in this order, and the optical layer includes at least one transparent light scattering particle having a primary particle diameter of 0.5 μm or more and a binder component, and the binder component is A compound having a refractive index equal to or higher than the refractive index of the organic light emitting layer, the organic layer further including at least one band gap compound layer, and the band gap compound layer having a Eg (band gap) of 1.3 to 2.5 eV And an organic electroluminescence device having a thickness of 0.5 nm or more and less than 10 nm. It has been found that by adopting an organic electroluminescent device having such a configuration, it is possible to achieve both high external quantum efficiency and low driving voltage of the device.
That is, the means for solving the above problems are as follows. In the present specification, “to” indicates a range including the numerical values described before and after the minimum and maximum values, respectively.
〔１〕
基板と、光を拡散、散乱する光学層と、透明電極である第１電極と、有機発光層を含む有機層と、第２電極と、がこの順に形成された有機電界発光素子であって、
光学層は、一次粒子径が０．５μｍ以上の透明な少なくとも１種の光散乱粒子とバインダ成分とを含み、バインダ成分は有機発光層の屈折率以上の屈折率を有し、
有機層は更にバンドギャップ化合物層を少なくとも一層含み、バンドギャップ化合物層はＥｇ（バンドギャップ）が１．３〜２．５ｅＶの化合物からなり、膜厚が０．５ｎｍ以上１０ｎｍ未満である、有機電界発光素子。
〔２〕
バンドギャップ化合物層は膜厚が０．５ｎｍ以上５ｎｍ未満の層である、〔１〕に記載の有機電界発光素子。
〔３〕
バンドギャップ化合物層は膜厚が０．５ｎｍ以上２ｎｍ未満の層である、〔１〕又は〔２〕に記載の有機電界発光素子。
〔４〕
第２電極が銀の反射電極である、〔１〕〜〔３〕のいずれか一項に記載の有機電界発光素子。
〔５〕
バンドギャップ化合物層を形成する化合物がＣｕＰＣ、ＰＴＣＤＡ又はＰＴＣＤＩである、〔１〕〜〔４〕のいずれか一項に記載の有機電界発光素子。
〔６〕
バンドギャップ化合物層が第１電極に隣接する、〔１〕〜〔５〕のいずれか一項に記載の有機電界発光素子。
〔７〕
バインダ成分が一次粒子径が１００ｎｍ以下の粒子を含有する、〔１〕〜〔６〕のいずれか一項に記載の有機電界発光素子。
〔８〕
一次粒子径が１００ｎｍ以下の粒子の屈折率が２．０以上３．０以下である、〔７〕に記載の有機電界発光素子。
〔９〕
バインダ成分の屈折率が１．７以上２．２以下である、〔１〕〜〔８〕のいずれか一項に記載の有機電界発光素子。
〔１０〕
光散乱粒子の屈折率が、バインダ成分の屈折率より低い、〔１〕〜〔９〕のいずれか一項に記載の有機電界発光素子。
[1]
An organic electroluminescent device in which a substrate, an optical layer that diffuses and scatters light, a first electrode that is a transparent electrode, an organic layer that includes an organic light emitting layer, and a second electrode are formed in this order,
The optical layer includes at least one transparent light scattering particle having a primary particle diameter of 0.5 μm or more and a binder component, and the binder component has a refractive index equal to or higher than the refractive index of the organic light emitting layer,
The organic layer further includes at least one band gap compound layer, the band gap compound layer is made of a compound having an Eg (band gap) of 1.3 to 2.5 eV, and has an organic electric field having a thickness of 0.5 nm or more and less than 10 nm. Light emitting element.
[2]
The organic electroluminescence device according to [1], wherein the band gap compound layer is a layer having a thickness of 0.5 nm or more and less than 5 nm.
[3]
The organic electroluminescent element according to [1] or [2], wherein the band gap compound layer is a layer having a thickness of 0.5 nm or more and less than 2 nm.
[4]
The organic electroluminescent element according to any one of [1] to [3], wherein the second electrode is a silver reflective electrode.
[5]
The organic electroluminescent element according to any one of [1] to [4], wherein the compound forming the band gap compound layer is CuPC, PTCDA, or PTCDI.
[6]
The organic electroluminescent element according to any one of [1] to [5], wherein the band gap compound layer is adjacent to the first electrode.
[7]
The organic electroluminescent element according to any one of [1] to [6], wherein the binder component contains particles having a primary particle diameter of 100 nm or less.
[8]
The organic electroluminescent element according to [7], wherein the refractive index of particles having a primary particle diameter of 100 nm or less is 2.0 or more and 3.0 or less.
[9]
The organic electroluminescent element according to any one of [1] to [8], wherein the binder component has a refractive index of 1.7 to 2.2.
[10]
The organic electroluminescent element according to any one of [1] to [9], wherein the refractive index of the light scattering particles is lower than the refractive index of the binder component.
本発明によれば、外部量子効率が高く駆動電圧が低い有機電界発光素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, an organic electroluminescent element with a high external quantum efficiency and a low drive voltage can be provided.
本発明の有機電界発光素子は、基板と、光を拡散、散乱する光学層と、透明電極である第１電極と、有機発光層を含む有機層と、第２電極と、がこの順に形成された有機電界発光素子であって、前記光学層は、一次粒子径が０．５μｍ以上の透明な少なくとも１種の光散乱粒子とバインダ成分とを含み、該バインダ成分は前記有機発光層の屈折率以上の屈折率を有し、前記有機層は更にバンドギャップ化合物層を少なくとも一層含み、該バンドギャップ化合物層はＥｇ（バンドギャップ）が１．３〜２．５ｅＶの化合物からなり、膜厚が０．５ｎｍ以上１０ｎｍ未満である。 In the organic electroluminescent element of the present invention, a substrate, an optical layer that diffuses and scatters light, a first electrode that is a transparent electrode, an organic layer that includes an organic light emitting layer, and a second electrode are formed in this order. An organic electroluminescent element, wherein the optical layer includes at least one transparent light scattering particle having a primary particle diameter of 0.5 μm or more and a binder component, and the binder component is a refractive index of the organic light emitting layer. The organic layer further includes at least one bandgap compound layer, and the bandgap compound layer is made of a compound having an Eg (bandgap) of 1.3 to 2.5 eV and has a film thickness of 0. .5 nm or more and less than 10 nm.
［光学層］
本発明の光学層は光を拡散、散乱する機能を有する層である。そして、該光学層は、一次粒子径が０．５μｍ以上の透明な少なくとも１種の光散乱粒子とバインダ成分とを含み、該バインダ成分は前記有機発光層の屈折率以上の屈折率を有する。
[Optical layer]
The optical layer of the present invention is a layer having a function of diffusing and scattering light. The optical layer includes at least one transparent light scattering particle having a primary particle diameter of 0.5 μm or more and a binder component, and the binder component has a refractive index equal to or higher than the refractive index of the organic light emitting layer.
（光散乱粒子）
光散乱粒子としては、一次粒子径が０．５μｍ以上であって、光を拡散、散乱可能なものであれば特に制限はなく、目的に応じて適宜選択することができ、有機粒子であっても、無機粒子であってもよく、２種以上の粒子を含有していても構わない。
なお、本明細書における光散乱粒子の一次粒子径とは、光散乱粒子１ｇをメタノール２００ｇに分散させ、べックマン・コールタ一株式会社製の「マルチサイザーＩＩ」精密粒度分布測定装置を使用して、光散乱粒子の粒子径の測定を行い、体積基準で平均粒子径となるように算出された一次粒子径である。
(Light scattering particles)
The light scattering particles are not particularly limited as long as the primary particle diameter is 0.5 μm or more and can diffuse and scatter light, and can be appropriately selected according to the purpose. May be inorganic particles, and may contain two or more kinds of particles.
The primary particle size of the light-scattering particles in this specification means that 1 g of light-scattering particles are dispersed in 200 g of methanol, and a “Multisizer II” precision particle size distribution measuring device manufactured by Beckman Coulter, Inc. is used. The particle diameter of the light scattering particles is measured, and the primary particle diameter is calculated so as to be an average particle diameter on a volume basis.
前記有機粒子としては、例えばポリメチルメタクリレート粒子、架橋ポリメチルメタクリレート粒子、アクリル−スチレン共重合体粒子、メラミン粒子、ポリカーボネート粒子、ポリスチレン粒子、架橋ポリスチレン粒子、ポリ塩化ビニル粒子、ベンゾグアナミン−メラミンホルムアルデヒド粒子、などが挙げられる。
前記無機粒子としては、例えばＺｒＯ２、ＴｉＯ２、Ａｌ２Ｏ３、Ｉｎ２Ｏ３、ＺｎＯ、ＳｎＯ２、Ｓｂ２Ｏ３、などが挙げられる。これらの中でも、ＴｉＯ２、ＺｒＯ２、ＺｎＯ、ＳｎＯ２が特に好ましい。
Examples of the organic particles include polymethyl methacrylate particles, crosslinked polymethyl methacrylate particles, acryl-styrene copolymer particles, melamine particles, polycarbonate particles, polystyrene particles, crosslinked polystyrene particles, polyvinyl chloride particles, benzoguanamine-melamine formaldehyde particles, Etc.
Examples of the inorganic particles, for example ZrO 2, TiO 2, Al 2 O 3, In 2 O 3, ZnO,
これらの中でも、前記光散乱粒子としては、耐溶剤性と光学層中の分散性の点で架橋状態の樹脂粒子が好ましく、架橋ポリメチルメタクリレート粒子が特に好ましい。
前記光散乱粒子が、架橋状態の樹脂粒子であることは、溶剤、例えばトルエン中に分散させ、樹脂粒子の溶け難さを見ることで確認することができる。
Among these, the light scattering particles are preferably resin particles in a cross-linked state in terms of solvent resistance and dispersibility in the optical layer, and cross-linked polymethyl methacrylate particles are particularly preferable.
The fact that the light scattering particles are crosslinked resin particles can be confirmed by dispersing in a solvent, for example, toluene and checking the difficulty of dissolution of the resin particles.
光散乱粒子の屈折率は、特に制限はなく、目的に応じて適宜選択することができるが、１．０以上３．０以下が好ましく、１．２以上２．０以下がより好ましく、１．３以上１．７以下が更に好ましい。前記屈折率が、１．０以上３．０以下であると、光拡散（散乱）が強くなりすぎないため、光取り出し効率が向上しやすい。
また、光散乱粒子の屈折率は、後述するバインダ成分の屈折率より低いことが好ましい。
なお、本明細書における光散乱粒子の屈折率は、前記光散乱粒子の原料となる材料を、屈折率測定に使用するエリプソメーターの光源の波長程度の厚さでシリコン基板上に成膜したものを、前記エリプソメーターにより測定した屈折率である。
The refractive index of the light scattering particles is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1.0 or more and 3.0 or less, more preferably 1.2 or more and 2.0 or less. More preferably, it is 3 or more and 1.7 or less. When the refractive index is 1.0 or more and 3.0 or less, light diffusion (scattering) does not become too strong, and thus light extraction efficiency is likely to be improved.
Moreover, it is preferable that the refractive index of light-scattering particle is lower than the refractive index of the binder component mentioned later.
In addition, the refractive index of the light scattering particles in the present specification is obtained by depositing the material that is the raw material of the light scattering particles on a silicon substrate with a thickness of about the wavelength of the light source of an ellipsometer used for refractive index measurement. Is a refractive index measured by the ellipsometer.
前記光散乱粒子の一次粒子径は、０．５μｍ以上１０μｍ以下が好ましく、０．５μｍ以上６μｍ以下がより好ましく、１μｍ以上３μｍ以下が更に好ましい。前記光散乱粒子の一次粒子径が１０μｍ以下であると、光が前方散乱になりにくく、光散乱粒子による光の角度を変換する能力が低下しにくい。
一方で、前記光散乱粒子の一次粒子径が０．５μｍ未満であると、可視光の波長より小さくなり、ミー散乱がレイリー散乱の領域に変化する。これにより、光散乱粒子の散乱効率の波長依存性が大きくなり、有機電界発光装置の色度が変化しやすくなるため好ましくない。また、後方散乱が強くなりすぎ、光取り出し効率が低下してしまう点で好ましくない。
The primary particle size of the light scattering particles is preferably 0.5 μm or more and 10 μm or less, more preferably 0.5 μm or more and 6 μm or less, and further preferably 1 μm or more and 3 μm or less. When the primary particle diameter of the light-scattering particles is 10 μm or less, the light does not easily scatter forward, and the ability to convert the angle of light by the light-scattering particles is unlikely to decrease.
On the other hand, when the primary particle diameter of the light scattering particles is less than 0.5 μm, the wavelength becomes smaller than the wavelength of visible light, and Mie scattering is changed to the Rayleigh scattering region. Thereby, the wavelength dependency of the scattering efficiency of the light scattering particles is increased, and the chromaticity of the organic electroluminescent device is likely to change, which is not preferable. Further, it is not preferable in that the backscattering becomes too strong and the light extraction efficiency is lowered.
光学層における光散乱粒子の含有量は、３０体積％以上６６体積％以下が好ましく、３０体積％以上６０体積％以下がより好ましく、３０体積％以上５５体積％以下が更に好ましい。前記含有量が、３０体積％以上であると、光学層に入射してきた光が光散乱粒子に散乱される確率が高く、光学層の光角度を変換する能力が大きいので、光学層の厚みを大きくしなくても光取り出し効率が向上する。また、前記光学層の厚みを大きくしなくてよいためコスト低減に繋がり、光学層の厚みのバラツキが小さくなり、発光面内の散乱効果にバラツキが生じにくい。一方、前記含有量が、６６体積％以下であると、前記光学層の表面が大きく荒れすぎず、内部にも空洞が生じにくいため、前記光学層の物理的強度が低下しにくい。 The content of light scattering particles in the optical layer is preferably 30% by volume to 66% by volume, more preferably 30% by volume to 60% by volume, and still more preferably 30% by volume to 55% by volume. When the content is 30% by volume or more, there is a high probability that light incident on the optical layer is scattered by the light scattering particles, and the ability to convert the light angle of the optical layer is large. The light extraction efficiency can be improved without increasing the size. Further, since it is not necessary to increase the thickness of the optical layer, the cost is reduced, the variation in the thickness of the optical layer is reduced, and the scattering effect in the light emitting surface is less likely to vary. On the other hand, when the content is 66% by volume or less, the surface of the optical layer is not excessively roughened, and cavities are not easily generated inside, so that the physical strength of the optical layer is hardly lowered.
光学層は、光取り出し効率の観点から、前記樹脂粒子と、光触媒不活性処理した酸化チタン微粒子とを含むことが好ましい。該光触媒不活性処理した酸化チタン微粒子の処理の内容は、後述する一次粒子径が１００ｎｍ以下の粒子に使用されている、光触媒不活性処理した酸化チタン微粒子についてされたものと同様である。 From the viewpoint of light extraction efficiency, the optical layer preferably contains the resin particles and titanium oxide fine particles that have been subjected to photocatalytic inactivation treatment. The details of the treatment of the photocatalyst-inactivated titanium oxide fine particles are the same as those for the photocatalyst-inactivated titanium oxide fine particles used for particles having a primary particle diameter of 100 nm or less, which will be described later.
光学層の膜厚は、散乱性能と製造適性の観点から、１００ｎｍ以上１０μｍ以下であることが好ましく、１００ｎｍ以上７μｍ以下であることがより好ましく、１００ｎｍ以上５μｍ以下であることが更に好ましい。
なお、各層の膜厚は、例えば膜厚を測定する層の一部を切り取り、走査型電子顕微鏡（Ｓ−３４００Ｎ、日立ハイテク株式会社製）で測定して、求めることができる。
The film thickness of the optical layer is preferably 100 nm or more and 10 μm or less, more preferably 100 nm or more and 7 μm or less, and further preferably 100 nm or more and 5 μm or less from the viewpoints of scattering performance and production suitability.
In addition, the film thickness of each layer can be calculated | required, for example by cutting out a part of layer which measures a film thickness, and measuring with a scanning electron microscope (S-3400N, Hitachi High-Tech Corporation make).
〔バインダ成分〕
バインダ成分とは、光学層に含有される成分から光散乱粒子を除いた成分であり、有機発光層の屈折率以上の屈折率を有することを特徴とする。
例えば、光学層が、光散乱粒子と、一次粒子径が１００ｎｍ以下の粒子と、樹脂材料の硬化物とを含有する場合は、バインダ成分とは、前記一次粒子径が１００ｎｍ以下の粒子と前記樹脂材料の硬化物とからなる成分を指す。
前記バインダ成分は、１成分のみにより構成されていてもよく、２成分以上により構成されていてもよい。
前記バインダ成分は、後述する一次粒子径が１００ｎｍ以下の粒子及び樹脂材料の硬化物を含有していることが好ましい。
なお、本明細書におけるバインダ成分の屈折率は、Ｓｉ基板、又は石英基板上に光の波長程度の厚さに前記バインダ成分を成膜し、その成膜した基板上の膜の屈折率をエリプソメーターにて測定した屈折率である。
(Binder component)
The binder component is a component obtained by removing light scattering particles from the component contained in the optical layer, and is characterized by having a refractive index equal to or higher than the refractive index of the organic light emitting layer.
For example, when the optical layer contains light scattering particles, particles having a primary particle size of 100 nm or less, and a cured product of a resin material, the binder component is a particle having the primary particle size of 100 nm or less and the resin. The component which consists of hardened | cured material of material is pointed out.
The binder component may be composed of only one component, or may be composed of two or more components.
The binder component preferably contains particles having a primary particle diameter of 100 nm or less, which will be described later, and a cured product of a resin material.
Note that the refractive index of the binder component in this specification refers to the refractive index of the film on the substrate on which the binder component is formed to a thickness of about the wavelength of light on a Si substrate or a quartz substrate. Refractive index measured with a meter.
本発明において、バインダ成分の屈折率は、光取り出し効率向上の観点から、有機電界発光素子の有機発光層の屈折率以上であり、具体的には、１．７以上２．２以下であることが好ましく、１．７以上２．１以下であることがより好ましく、１．７以上２．０以下であることが更に好ましい。 In the present invention, the refractive index of the binder component is equal to or higher than the refractive index of the organic light emitting layer of the organic electroluminescent element, specifically, 1.7 to 2.2, from the viewpoint of improving light extraction efficiency. Is preferably 1.7 or more and 2.1 or less, more preferably 1.7 or more and 2.0 or less.
（一次粒子径が１００ｎｍ以下の粒子）
本発明においては、バインダ成分は、一次粒子径が１００ｎｍ以下の粒子（以下、「ナノサイズ粒子」、「屈折率制御粒子」と称することもある。）を含有することができる。
本明細書におけるナノサイズ粒子の一次粒子径とは、べックマン・コールタ一株式会社製の「ＤｅｌｓａＴＭ Ｎａｎｏ Ｃ」を使用して、ナノサイズ粒子の粒子径の測定を行い、体積基準で平均粒子径となるように算出された一次粒子径である。
(Particles with a primary particle size of 100 nm or less)
In the present invention, the binder component can contain particles having a primary particle diameter of 100 nm or less (hereinafter, also referred to as “nano-sized particles” or “refractive index control particles”).
In this specification, the primary particle size of the nano-sized particles means that the particle size of the nano-sized particles is measured using “Delsa ™ Nano C” manufactured by Beckman Coulter Co., Ltd. It is a primary particle diameter calculated so that it may become a diameter.
前記ナノサイズ粒子としては、無機微粒子が好ましく、金属酸化物微粒子であり、例えば、アルミニウム、チタニウム、ジルコニウム、アンチモンの酸化物の微粒子が好ましく、屈折率の観点から、酸化チタンの微粒子が特に好ましい。酸化チタン微粒子は、光触媒効果を不活性処理したものであることが好ましい。 The nano-sized particles are preferably inorganic fine particles, and are metal oxide fine particles. For example, fine particles of oxides of aluminum, titanium, zirconium and antimony are preferred, and fine particles of titanium oxide are particularly preferred from the viewpoint of refractive index. The titanium oxide fine particles are preferably those obtained by subjecting the photocatalytic effect to an inert treatment.
−−光触媒不活性処理した酸化チタン微粒子−−
光触媒不活性処理した酸化チタン微粒子は、光触媒活性を有していなければ特に制限はなく、目的に応じて適宜選択することができるが、（１）酸化チタン微粒子表面をアルミナ、シリカ、及びジルコニアの少なくとも１種で被覆した酸化チタン微粒子、（２）前記（１）の被覆した酸化チタン微粒子の被覆表面に樹脂を被覆してなる酸化チタン微粒子などが挙げられる。前記樹脂としては、例えばポリメタクリル酸メチル（ＰＭＭＡ）などが挙げられる。
--Titanium oxide fine particles treated with photocatalytic deactivation--
The titanium oxide fine particles subjected to photocatalytic inactivation treatment are not particularly limited as long as they do not have photocatalytic activity, and can be appropriately selected according to the purpose. (1) The surface of titanium oxide fine particles is made of alumina, silica, and zirconia. Examples include titanium oxide fine particles coated with at least one kind, and (2) titanium oxide fine particles formed by coating a resin on the coated surface of the titanium oxide fine particles coated in (1). Examples of the resin include polymethyl methacrylate (PMMA).
前記光触媒不活性処理した酸化チタン微粒子が、光触媒活性を有さないことの確認は、例えばメチレンブルー法により行うことができる。 Confirmation that the photocatalytically inactivated titanium oxide fine particles do not have photocatalytic activity can be performed by, for example, a methylene blue method.
前記光触媒不活性処理した酸化チタン微粒子における酸化チタン微粒子としては、特に制限はなく、目的に応じて適宜選択することができ、前記結晶構造は、ルチル、ルチル／アナターゼの混晶、アナターゼが主成分であることが好ましく、特にルチル構造が主成分であることが好ましい。
前記酸化チタン微粒子は、酸化チタン以外の金属酸化物を添加して複合化させても構わない。
前記酸化チタン微粒子に複合化させることができる金属酸化物としては、Ｓｎ、Ｚｒ、Ｓｉ、Ｚｎ、及びＡｌから選択される少なくとも１種の金属酸化物が好ましい。
前記金属酸化物のチタンに対する添加量は、１モル％〜４０モル％が好ましく、２モル％〜３５モル％がより好ましく、３モル％〜３０モル％が更に好ましい。
The titanium oxide fine particles in the photocatalyst-inactivated titanium oxide fine particles are not particularly limited and can be appropriately selected according to the purpose. The crystal structure is mainly composed of rutile, a mixed crystal of rutile / anatase, and anatase. It is preferable that the rutile structure is a main component.
The titanium oxide fine particles may be compounded by adding a metal oxide other than titanium oxide.
The metal oxide that can be combined with the titanium oxide fine particles is preferably at least one metal oxide selected from Sn, Zr, Si, Zn, and Al.
The amount of the metal oxide added to titanium is preferably 1 mol% to 40 mol%, more preferably 2 mol% to 35 mol%, still more preferably 3 mol% to 30 mol%.
前記ナノサイズ粒子の一次粒子径は、１ｎｍ以上１００ｎｍ以下であることが好ましく、１ｎｍ以上３０ｎｍ以下が更に好ましく、１ｎｍ以上２５ｎｍ以下が特に好ましく、１ｎｍ以上２０ｎｍ以下が最も好ましい。一次粒子径が、１００ｎｍ以下であれば、分散液が白濁しにくく、沈降が起きにくいため好ましく、１ｎｍ以上であれば、結晶性が高いためアモルファスにならず、経時でゲル化などの変化が起こりにくいため好ましい。 The primary particle size of the nano-sized particles is preferably 1 nm to 100 nm, more preferably 1 nm to 30 nm, particularly preferably 1 nm to 25 nm, and most preferably 1 nm to 20 nm. If the primary particle size is 100 nm or less, it is preferable because the dispersion is less likely to become cloudy and sedimentation is not likely to occur, and if it is 1 nm or more, the crystallinity is high so that it does not become amorphous and changes such as gelation over time It is preferable because it is difficult.
前記ナノサイズ粒子の形状は、特に制限はなく、目的に応じて適宜選択することができるが、例えば、米粒状、球形状、立方体状、紡錘形状、又は不定形状が好ましい。前記ナノサイズ粒子は、１種を単独で用いてもよいが、２種類以上を併用して用いることもできる。 There is no restriction | limiting in particular in the shape of the said nanosized particle, Although it can select suitably according to the objective, For example, a rice grain shape, a spherical shape, a cube shape, a spindle shape, or an indefinite shape is preferable. The nano-sized particles may be used alone or in combination of two or more.
前記ナノサイズ粒子は、光学層の屈折率を高くするために、屈折率が２．０以上３．０以下であることが好ましく、２．２以上３．０以下であることがより好ましく、２．２以上２．８以下が更に好ましく、２．２以上２．６以下が特に好ましい。前記屈折率が、２．０以上であれば、導電性層の屈折率を効果的に高めることができ、前記屈折率が、３．０以下であれば粒子が着色するなどの不都合がないので好ましい。
前記ナノサイズ粒子の屈折率は以下のようにして測定することができる。屈折率が既知の樹脂材料に導電性マトリックスよりも大きな屈折率を有する粒子をドープし、該粒子が分散された樹脂材料をＳｉ基板、又は石英基板上に塗布膜を形成する。前記塗布膜の屈折率をエリプソメーターで測定し、前記塗布膜を構成する樹脂材料と前記粒子の体積分率から、前記粒子の屈折率を求める。
In order to increase the refractive index of the optical layer, the nano-sized particles preferably have a refractive index of 2.0 or more and 3.0 or less, more preferably 2.2 or more and 3.0 or less. 2 or more and 2.8 or less are more preferable, and 2.2 or more and 2.6 or less are particularly preferable. If the refractive index is 2.0 or more, the refractive index of the conductive layer can be effectively increased, and if the refractive index is 3.0 or less, there is no inconvenience such as particle coloring. preferable.
The refractive index of the nano-sized particles can be measured as follows. A resin material having a known refractive index is doped with particles having a refractive index larger than that of the conductive matrix, and a coating film is formed on the Si substrate or the quartz substrate with the resin material in which the particles are dispersed. The refractive index of the coating film is measured with an ellipsometer, and the refractive index of the particles is determined from the resin material constituting the coating film and the volume fraction of the particles.
前記ナノサイズ粒子は、光学層中に、光学層の全体積に対して１０体積％以上５０体積％以下含有されることが好ましく、１５体積％以上５０体積％以下含有されることがより好ましく、２０体積％以上５０体積％以下含有されることが更に好ましい。前記含有量が、１０体積％以上であると、光学層の屈折率を効果的に上げることができ、光取り出し効果が向上するため好ましく、５０体積％以下であると、レイリー散乱が強くならず、光取り出し効果が向上するため好ましい。 The nano-sized particles are preferably contained in the optical layer in an amount of 10% by volume to 50% by volume with respect to the total volume of the optical layer, and more preferably 15% by volume to 50% by volume. More preferably, it is contained in an amount of 20% by volume to 50% by volume. When the content is 10% by volume or more, the refractive index of the optical layer can be effectively increased, and the light extraction effect is improved. When the content is 50% by volume or less, Rayleigh scattering does not increase. It is preferable because the light extraction effect is improved.
（樹脂材料の硬化物）
本発明のバインダ成分は、樹脂材料の硬化物を含有することが好ましい。
前記樹脂材料の硬化物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ラジカル重合性不飽和基｛（メタ）アクリロイルオキシ基、ビニルオキシ基、スチリル基、ビニル基等｝及び／又はカチオン重合性基（エポキシ基、チオエポキシ基、ビニルオキシ基、オキセタニル基等）の官能基を有する樹脂で、例えば、比較的低分子量のポリエステル樹脂、ポリエーテル樹脂、（メタ）アクリル樹脂、エポキシ樹脂、ウレタン樹脂、アルキッド樹脂、スピロアセタール樹脂、ポリブタジエン樹脂、ポリチオールポリエン樹脂、フェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、グアナミン樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、アミノアルキッド樹脂、メラミン−尿素共縮合樹脂、珪素樹脂、ポリシロキサン樹脂などが挙げられる。
(Hardened resin material)
The binder component of the present invention preferably contains a cured product of a resin material.
There is no restriction | limiting in particular as hardened | cured material of the said resin material, According to the objective, it can select suitably, For example, radically polymerizable unsaturated group {(meth) acryloyloxy group, vinyloxy group, styryl group, vinyl group etc. } And / or a resin having a functional group such as a cationic polymerizable group (epoxy group, thioepoxy group, vinyloxy group, oxetanyl group, etc.), for example, a relatively low molecular weight polyester resin, polyether resin, (meth) acrylic resin, Epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, aminoalkyd resin, melamine Urea cocondensation resin, silicon Fat, such as polysiloxane resins.
上記樹脂材料の硬化物は、上記樹脂材料を硬化して得られるものである。樹脂材料を硬化する方法に特に制限はないが、短時間で硬化が可能であり、目的の形状に硬化させる制御が容易であることの理由から、光照射により硬化することが好ましい。 The cured product of the resin material is obtained by curing the resin material. Although there is no restriction | limiting in particular in the method of hardening | curing a resin material, It is preferable to harden | cure by light irradiation from the reason that it can harden | cure in a short time and it is easy to control to harden to the target shape.
また、上記光照射による樹脂材料の硬化には、光重合開始剤を用いることが好ましい。光重合開始剤の種類には特に制限はないが、光照射により、ラジカルもしくは酸を発生する化合物であることが好ましい。前記光重合開始剤は、極大吸収波長が４００ｎｍ以下であることが好ましい。このように吸収波長を紫外線領域にすることにより、取り扱いを白灯下で実施することができる。また、赤外線領域に極大吸収波長を持つ化合物を用いることもできる。 Moreover, it is preferable to use a photoinitiator for hardening of the resin material by the said light irradiation. The type of the photopolymerization initiator is not particularly limited, but is preferably a compound that generates a radical or an acid upon irradiation with light. The photopolymerization initiator preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. A compound having a maximum absorption wavelength in the infrared region can also be used.
光照射の光源は、光重合開始剤の反応する波長（吸収波長）付近であればいずれでもよく、吸収波長が紫外領域の場合、光源として、超高圧、高圧、中圧、低圧の各水銀灯、ケミカルランプ、カーボンアーク灯、メタルハライド灯、キセノン灯、太陽光等が挙げられる。波長３５０ｎｍ〜４２０ｎｍの入手可能な各種レーザー光源をマルチビーム化して照射してもよい。また、吸収波長が赤外領域の場合、光源としてはハロゲンランプ、キセノンランプ、高圧ナトリウムランプが挙げられ、波長７５０ｎｍ〜１，４００ｎｍの入手可能な各種レーザー光源をマルチビーム化して照射してもよい。 The light source for light irradiation may be any wavelength near the wavelength (absorption wavelength) at which the photopolymerization initiator reacts. When the absorption wavelength is in the ultraviolet region, each light source can be an ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamp, A chemical lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, sunlight, etc. are mentioned. Various available laser light sources having a wavelength of 350 nm to 420 nm may be irradiated as a multi-beam. When the absorption wavelength is in the infrared region, examples of the light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 nm to 1,400 nm may be converted into multi-beams for irradiation. .
光照射による光ラジカル重合の場合は、空気又は不活性気体中で行うことができるが、ラジカル重合性モノマーの重合の誘導期を短くするか、又は重合率を十分に高める等のために、できるだけ酸素濃度を少なくした雰囲気とすることが好ましい。前記酸素濃度範囲は０〜１，０００ｐｐｍが好ましく、０〜８００ｐｐｍがより好ましく、０〜６００ｐｐｍが更に好ましい。照射する紫外線の照射強度は、０．１ｍＷ／ｃｍ２〜１００ｍＷ／ｃｍ２が好ましく、塗布膜表面上での光照射量は、１００ｍＪ／ｃｍ２〜１０，０００ｍＪ／ｃｍ２が好ましく、１００ｍＪ／ｃｍ２〜５，０００ｍＪ／ｃｍ２がより好ましく、１００ｍＪ／ｃｍ２〜１，０００ｍＪ／ｃｍ２が特に好ましい。前記光照射量が、１００ｍＪ／ｃｍ２未満であると、光学層が十分に硬化せず、光学層上に他の層を塗布する際に溶解、また、基板洗浄時に崩壊することがある。一方、前記光照射量が、１０，０００ｍＪ／ｃｍ２を超えると、光学層の重合が進み過ぎ表面が黄変し、透過率が低下し、光取り出し効率が低下することがある。また、光照射工程での温度は、１５℃〜７０℃が好ましく、２０℃〜６０℃がより好ましく、２５℃〜５０℃が特に好ましい。前記温度が、１５℃未満であると、光重合による光学層の硬化に時間がかかることがあり、７０℃を超えると、光重合開始剤自体に影響を及ぼし、光重合（硬化）できなくなることがある。
In the case of radical photopolymerization by light irradiation, it can be carried out in air or in an inert gas, but in order to shorten the polymerization induction period of the radically polymerizable monomer or sufficiently increase the polymerization rate, etc. It is preferable that the atmosphere has a reduced oxygen concentration. The oxygen concentration range is preferably 0 to 1,000 ppm, more preferably 0 to 800 ppm, and still more preferably 0 to 600 ppm. Irradiation intensity of ultraviolet irradiation is preferably from 0.1mW / cm 2 ~100mW / cm 2 , irradiation amount on the
［金属電極］
本発明の有機電界発光素子は、第２電極が反射電極であることが好ましい。そして、前記反射電極は、金属電極であることが好ましい。
前記金属電極を構成する材料としては、例えば、アルカリ金属（例えば、Ｌｉ、Ｎａ、Ｋ、Ｃｓ等）、アルカリ土類金属（例えば、Ｍｇ、Ｃａ等）、金、銀、鉛、アルミニウム、ナトリウム−カリウム合金、リチウム−アルミニウム合金、マグネシウム−銀合金、インジウム、及びイッテルビウム等の希土類金属などが挙げられる。これらは、１種単独で使用してもよいが、安定性と電子注入性とを両立させる観点からは、２種以上を好適に併用することができる。これらの中でも、電子注入性の点で、アルカリ金属やアルカリ土類金属が好ましく、保存安定性に優れる点で、アルミニウムを主体とする材料が好ましい。また、発光効率の観点から反射率の高い銀を主体とする材料が好ましい。
アルミニウムを主体とする材料とは、アルミニウム単独、アルミニウムと０．０１質量％〜１０質量％のアルカリ金属又はアルカリ土類金属との合金若しくはこれらの混合物（例えば、リチウム−アルミニウム合金、マグネシウム−アルミニウム合金など）をいう。
銀を主体とする材料とは、銀単独、銀と０．０１質量％〜１０質量％のアルカリ土類金属やその他金属類（例えば、銀とマグネシウム、カルシウムの合金など）の混合物をいう。銀を主体とする材料としては、反射率が高く外部量子効率の向上が期待できることから、銀単独の材料を使用することが好ましい。
[Metal electrode]
In the organic electroluminescent element of the present invention, the second electrode is preferably a reflective electrode. The reflective electrode is preferably a metal electrode.
Examples of the material constituting the metal electrode include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium Examples include potassium alloys, lithium-aluminum alloys, magnesium-silver alloys, indium, and rare earth metals such as ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection. Among these, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injection properties, and materials mainly composed of aluminum are preferable from the viewpoint of excellent storage stability. Further, a material mainly composed of silver having a high reflectance is preferable from the viewpoint of luminous efficiency.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).
The material mainly composed of silver refers to a mixture of silver alone, silver and 0.01% by mass to 10% by mass of an alkaline earth metal or other metals (for example, an alloy of silver, magnesium, calcium, etc.). As the material mainly composed of silver, it is preferable to use a material of silver alone because of its high reflectivity and improvement in external quantum efficiency.
［その他の層］
本発明の有機電界発光素子は、封止缶内に、少なくとも、前記第２電極、前記有機層が封入されていることが好ましく、封止缶内に、前記第１電極、前記第２電極、及び前記有機層が封入されていることがより好ましい。
[Other layers]
In the organic electroluminescent element of the present invention, it is preferable that at least the second electrode and the organic layer are sealed in a sealing can, and the first electrode, the second electrode, More preferably, the organic layer is sealed.
〔有機層〕
前記有機層としては、少なくとも有機発光層とバンドギャップ化合物層とを有する。前記有機発光層以外の機能層としては、正孔輸送層、電子輸送層、正孔ブロック層、電子ブロック層、正孔注入層、電子注入層等の各層が挙げられる。
[Organic layer]
The organic layer has at least an organic light emitting layer and a band gap compound layer. Examples of the functional layer other than the organic light emitting layer include a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, and an electron injection layer.
（バンドギャップ化合物層）
前記バンドギャップ化合物層（以下、「Ｅｇ化合物層」とも称する。）は、Ｅｇ（バンドギャップ）が１．３〜２．５ｅＶの化合物（以下、「バンドギャップ化合物層を形成する化合物」とも称する。）からなり、膜厚が０．５ｎｍ以上１０ｎｍ未満の層である。
バンドギャップ化合物層は電極から正孔を注入しやすくする機能を有し、有機電界発光素子の駆動電圧を低減させる効果を有する層である。
(Band gap compound layer)
The band gap compound layer (hereinafter also referred to as “Eg compound layer”) is also referred to as a compound having an Eg (band gap) of 1.3 to 2.5 eV (hereinafter referred to as “compound forming a band gap compound layer”). And a film thickness of 0.5 nm or more and less than 10 nm.
The band gap compound layer is a layer having a function of facilitating injection of holes from the electrode and having an effect of reducing the driving voltage of the organic electroluminescence device.
ここで、本明細書におけるＥｇとは、下記のとおり求められる。厚さ５０ｎｍの有機材料の膜を真空蒸着法により石英基板上に成膜し、日立ハイテク製分光光度計「Ｕ−３３１０」により紫外線領域から可視光領域までの光の吸収を測定する。吸収スペクトルの山の長波長側の裾野（吸収端）の波長（ｎｍ）をＥｇ（ｅＶ）として求める。
ここで、上記裾野（吸収端）の波長の求め方を、図１により説明する。裾野（吸収端）の波長は、長波側のスペクトルに沿った仮想直線（図１における破線）を引き、吸収０のグランドレベルと重なった位置から求めることができる。
Here, Eg in this specification is calculated | required as follows. A film of an organic material having a thickness of 50 nm is formed on a quartz substrate by a vacuum deposition method, and absorption of light from the ultraviolet region to the visible light region is measured by a spectrophotometer “U-3310” manufactured by Hitachi High-Tech. The wavelength (nm) of the base (absorption edge) on the long wavelength side of the peak of the absorption spectrum is obtained as Eg (eV).
Here, how to determine the wavelength of the base (absorption edge) will be described with reference to FIG. The wavelength at the base (absorption edge) can be obtained from a position where the virtual line along the long-wave side spectrum (broken line in FIG. 1) is overlapped with the ground level where absorption is zero.
例えば、図２に示すＰＴＣＤＡ（３，４，９，１０−Ｐｅｒｙｌｅｎｅｔｅｔｒａｃａｒｂｏｘｙｌｉｃ ３，４：９，１０−ｄｉａｎｈｙｄｒｉｄｅ）の吸収スペクトルにおいては、裾野（吸収端）の波長は５７０ｎｍである。この波長を式Ｅ＝ｈｃ／λによりエネルギーに換算することにより、Ｅｇ＝２．２ｅＶが求まる。 For example, in the absorption spectrum of PTCDA (3,4,9,10-Perylenetetracarboxylic 3,4: 9,10-dianhydride) shown in FIG. 2, the wavelength at the base (absorption edge) is 570 nm. By converting this wavelength into energy by the equation E = hc / λ, Eg = 2.2 eV is obtained.
また、図３に示すＣｕＰｃ（Ｃｏｐｐｅｒ ｐｈｔｈａｌｏｃｙａｎｉｎｅ）の吸収スペクトルにおいては、Ｅｇに対応する吸収スペクトルの山の長波長側の裾野（吸収端）の波長は７７５ｎｍである。この波長を上記のとおりエネルギーに換算することにより、Ｅｇ＝１．６ｅＶが求まる。 Further, in the absorption spectrum of CuPc (Copper phthalocyanine) shown in FIG. 3, the wavelength of the skirt (absorption edge) on the long wavelength side of the peak of the absorption spectrum corresponding to Eg is 775 nm. By converting this wavelength into energy as described above, Eg = 1.6 eV is obtained.
前記バンドギャップ化合物層を形成する化合物のＥｇが１．３〜２．５ｅＶの範囲にあることにより、電極とのエネルギー順位のマッチングと電気伝導性の向上から電極からの正孔注入性が向上し、駆動電圧を抑えることができる。バンドギャップ化合物層を形成する化合物のＥｇが１．３ｅＶ未満であると、電極とのエネルギー順位のマッチングが悪化するため好ましくない。また、バンドギャップ化合物層を形成する化合物のＥｇが２．５ｅＶを超えると、電極とのエネルギー順位のマッチングと電気伝導性が低下するため好ましくない。 When the Eg of the compound forming the band gap compound layer is in the range of 1.3 to 2.5 eV, the hole injection property from the electrode is improved due to the matching of the energy rank with the electrode and the improvement in electrical conductivity. , Driving voltage can be suppressed. If the Eg of the compound forming the bandgap compound layer is less than 1.3 eV, the energy ranking matching with the electrode is deteriorated, which is not preferable. Further, if the Eg of the compound forming the band gap compound layer exceeds 2.5 eV, it is not preferable because the matching of the energy level with the electrode and the electrical conductivity are lowered.
前記バンドギャップ化合物層を形成する化合物は、Ｅｇが１．３〜２．５ｅＶの範囲にあれば特に制限はないが、例えば、ＣｕＰＣ、ＰＴＣＤＡ又はＰＴＣＤＩ（Ｎ，Ｎ’−Ｂｉｓ（２，５−ｄｉ−ｔｅｒｔ−ｂｕｔｙｌｐｈｅｎｙｌ）ｐｅｒｙｌｅｎｅ−３，４：９，１０−ｂｉｓ（ｄｉｃａｒｂｉｍｉｄｅ））を好ましく使用することができる。 The compound for forming the band gap compound layer is not particularly limited as long as Eg is in the range of 1.3 to 2.5 eV. For example, CuPC, PTCDA or PTCDI (N, N′-Bis (2,5- di-tert-butylphenyl) perylene-3, 4: 9, 10-bis (dicarbide)) can be preferably used.
前記バンドギャップ化合物層の膜厚は０．５ｎｍ以上１０ｎｍ未満である。バンドギャップ化合物層の膜厚が０．５ｎｍ未満であると、膜として機能しなくなるため好ましくない。また、バンドギャップ化合物層の膜厚が１０ｎｍ以上であると、光吸収が強くなるため好ましくない。
光吸収低減とバンドギャップ化合物の機能可能な最適な膜厚の観点から、前記バンドギャップ化合物層の膜厚は０．５ｎｍ以上５ｎｍ未満であることが好ましく、０．５ｎｍ以上２ｎｍ未満であることがより好ましい。
The film thickness of the band gap compound layer is 0.5 nm or more and less than 10 nm. When the film thickness of the band gap compound layer is less than 0.5 nm, it does not function as a film, which is not preferable. Further, it is not preferable that the film thickness of the band gap compound layer is 10 nm or more because light absorption becomes strong.
From the viewpoint of the light absorption reduction and the optimum film thickness at which the band gap compound can function, the film thickness of the band gap compound layer is preferably 0.5 nm or more and less than 5 nm, and preferably 0.5 nm or more and less than 2 nm. More preferred.
前記有機層における前記バンドギャップ化合物層の位置には特に制限はないが、金属電極からの正孔注入性が良い性質である観点から、第１電極に隣接していることが好ましい。
また、前記バンドギャップ化合物層は、正孔注入層であることが好ましい。
The position of the band gap compound layer in the organic layer is not particularly limited, but it is preferably adjacent to the first electrode from the viewpoint of good hole injection properties from the metal electrode.
The band gap compound layer is preferably a hole injection layer.
−有機発光層−
前記有機発光層は、電界印加時に、陽極、正孔注入層、又は正孔輸送層から正孔を受け取り、陰極、電子注入層、又は電子輸送層から電子を受け取り、正孔と電子の再結合の場を提供して発光させる機能を有する層である。
前記有機発光層は、発光材料を含む。前記有機発光層は発光材料のみで構成されていてもよいし、ホスト材料と発光材料の混合層でもよい（後者の場合、発光材料を「発光性ドーパント」もしくは「ドーパント」と称する場合がある）。前記発光材料は蛍光発光材料でも燐光発光材料であってもよく、２種以上が混合されていてもよい。ホスト材料は電荷輸送材料が好ましい。ホスト材料は１種であっても２種以上であってもよい。更に、有機発光層中に電荷輸送性を有さず、発光しない材料を含んでいてもよい。
なお、本明細書における有機発光層の屈折率は、Ｓｉ基板、又は石英基板上に光の波長程度の厚さに前記有機発光層を成膜し、その成膜した基板上の膜の屈折率をエリプソメーターにて測定した屈折率である。
-Organic light emitting layer-
The organic light emitting layer receives holes from an anode, a hole injection layer, or a hole transport layer when an electric field is applied, receives electrons from a cathode, an electron injection layer, or an electron transport layer, and recombines holes and electrons. It is a layer having a function of providing light and emitting light.
The organic light emitting layer includes a light emitting material. The organic light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material (in the latter case, the light emitting material may be referred to as “light emitting dopant” or “dopant”). . The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and two or more kinds may be mixed. The host material is preferably a charge transport material. The host material may be one type or two or more types. Furthermore, the organic light emitting layer may include a material that does not have charge transporting properties and does not emit light.
Note that the refractive index of the organic light emitting layer in this specification refers to the refractive index of the film on the substrate on which the organic light emitting layer is formed to a thickness of about the wavelength of light on a Si substrate or a quartz substrate. Is a refractive index measured with an ellipsometer.
前記有機発光層の厚みは、特に制限はなく、目的に応じて適宜選択することができるが、２ｎｍ〜５００ｎｍであるのが好ましく、外部量子効率の観点で、３ｎｍ〜２００ｎｍであるのがより好ましく、５ｎｍ〜１００ｎｍであるのが更に好ましい。また、前記有機発光層は１層であっても二層以上であってもよく、それぞれの層が異なる発光色で発光してもよい。 The thickness of the organic light emitting layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm from the viewpoint of external quantum efficiency. More preferably, it is 5 nm-100 nm. Further, the organic light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.
−−発光材料−−
前記発光材料は、燐光発光材料、蛍光発光材料等のいずれも好適に用いることができる。
前記発光材料は、ホスト化合物との間で、イオン化ポテンシャルの差（ΔＩｐ）と電子親和力の差（ΔＥａ）が、１．２ｅＶ＞△Ｉｐ＞０．２ｅＶ、及び／又は１．２ｅＶ＞△Ｅａ＞０．２ｅＶの関係を満たすドーパントであることが、駆動耐久性の観点で好ましい。
前記発光層中の発光材料は、前記発光層中に一般的に発光層を形成する全化合物質量に対して、０．１質量％〜５０質量％含有されるが、耐久性、外部量子効率の観点から１質量％〜５０質量％含有されることが好ましく、２質量％〜５０質量％含有されることがより好ましい。
--Luminescent material--
As the light emitting material, any of a phosphorescent light emitting material, a fluorescent light emitting material and the like can be suitably used.
The light emitting material has an ionization potential difference (ΔIp) and an electron affinity difference (ΔEa) of 1.2 eV>ΔIp> 0.2 eV and / or 1.2 eV>ΔEa> with the host compound. A dopant satisfying the relationship of 0.2 eV is preferable from the viewpoint of driving durability.
The light emitting material in the light emitting layer is contained in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass generally forming the light emitting layer in the light emitting layer. From the viewpoint, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 50% by mass.
−−−燐光発光材料−−−
前記燐光発光材料としては、一般に、遷移金属原子又はランタノイド原子を含む錯体を挙げることができる。
前記遷移金属原子としては、特に制限はなく、目的に応じて適宜選択することができ、例えばルテニウム、ロジウム、パラジウム、タングステン、レニウム、オスミウム、イリジウム、金、銀、銅、及び白金が挙げられ、より好ましくは、レニウム、イリジウム、及び白金であり、更に好ましくはイリジウム、白金である。
--- Phosphorescent material ---
In general, examples of the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
The transition metal atom is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum. Rhenium, iridium, and platinum are more preferable, and iridium and platinum are more preferable.
前記錯体の配位子としては、例えば、Ｇ．Ｗｉｌｋｉｎｓｏｎ等著，Ｃｏｍｐｒｅｈｅｎｓｉｖｅ Ｃｏｏｒｄｉｎａｔｉｏｎ Ｃｈｅｍｉｓｔｒｙ， Ｐｅｒｇａｍｏｎ Ｐｒｅｓｓ社１９８７年発行、Ｈ．Ｙｅｒｓｉｎ著，「Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ ａｎｄ Ｐｈｏｔｏｐｈｙｓｉｃｓ ｏｆ Ｃｏｏｒｄｉｎａｔｉｏｎ Ｃｏｍｐｏｕｎｄｓ」 Ｓｐｒｉｎｇｅｒ−Ｖｅｒｌａｇ社１９８７年発行、山本明夫著「有機金属化学−基礎と応用−」裳華房社１９８２年発行等に記載の配位子などが挙げられる。 Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .
前記錯体は、化合物中に遷移金属原子を一つ有してもよいし、また、２つ以上有するいわゆる複核錯体であってもよい。異種の金属原子を同時に含有していてもよい。 The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.
これらの中でも、燐光発光材料としては、例えば、ＵＳ６３０３２３８Ｂ１、ＵＳ６０９７１４７、ＷＯ００／５７６７６、ＷＯ００／７０６５５、ＷＯ０１／０８２３０、ＷＯ０１／３９２３４Ａ２、ＷＯ０１／４１５１２Ａ１、ＷＯ０２／０２７１４Ａ２、ＷＯ０２／１５６４５Ａ１、ＷＯ０２／４４１８９Ａ１、ＷＯ０５／１９３７３Ａ２、ＷＯ２００４／１０８８５７Ａ１、ＷＯ２００５／０４２４４４Ａ２、ＷＯ２００５／０４２５５０Ａ１、特開２００１−２４７８５９、特開２００２−３０２６７１、特開２００２−１１７９７８、特開２００３−１３３０７４、特開２００２−２３５０７６、特開２００３−１２３９８２、特開２００２−１７０６８４、ＥＰ１２１１２５７、特開２００２−２２６４９５、特開２００２−２３４８９４、特開２００１−２４７８５９、特開２００１−２９８４７０、特開２００２−１７３６７４、特開２００２−２０３６７８、特開２００２−２０３６７９、特開２００４−３５７７９１、特開２００６−９３５４２、特開２００６−２６１６２３、特開２００６−２５６９９９、特開２００７−１９４６２、特開２００７−８４６３５、特開２００７−９６２５９等の各公報に記載の燐光発光化合物などが挙げられる。これらの中でも、Ｉｒ錯体、Ｐｔ錯体、Ｃｕ錯体、Ｒｅ錯体、Ｗ錯体、Ｒｈ錯体、Ｒｕ錯体、Ｐｄ錯体、Ｏｓ錯体、Ｅｕ錯体、Ｔｂ錯体、Ｇｄ錯体、Ｄｙ錯体、Ｃｅ錯体が好ましく、Ｉｒ錯体、Ｐｔ錯体、又はＲｅ錯体がより好ましく、金属−炭素結合、金属−窒素結合、金属−酸素結合、金属−硫黄結合の少なくとも一つの配位様式を含むＩｒ錯体、Ｐｔ錯体、又はＲｅ錯体が更に好ましく、発光効率、駆動耐久性、色度等の観点で、３座以上の多座配位子を含むＩｒ錯体、Ｐｔ錯体、又はＲｅ錯体が特に好ましい。 Among these, as phosphorescent materials, for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, WO2004 / 108857A1, WO2005 / 042444A2, WO2005 / 042550A1, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-1235076, JP2003-123982, JP2002-170684, EP121257, JP2002-226495, JP2002-2002 34894, JP 2001-247659, JP 2001-298470, JP 2002-173675, JP 2002-203678, JP 2002-203679, JP 2004-357791, JP 2006-93542, JP 2006-261623, Examples thereof include phosphorescent compounds described in JP-A-2006-256999, JP-A-2007-19462, JP-A-2007-84635, JP-A-2007-96259, and the like. Among these, Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex are preferable, and Ir complex , A Pt complex, or a Re complex is more preferable, and an Ir complex, a Pt complex, or a Re complex including at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is further included. In view of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or an Re complex containing a tridentate or higher polydentate ligand is particularly preferable.
前記燐光発光材料の具体例として、以下の化合物を挙げることができるが、これらに限定されるものではない。 Specific examples of the phosphorescent material include the following compounds, but are not limited thereto.
−−−蛍光発光材料−−−
前記蛍光発光材料としては、特に制限はなく、目的に応じて適宜選択することができ、例えばベンゾオキサゾール、ベンゾイミダゾール、ベンゾチアゾール、スチリルベンゼン、ポリフェニル、ジフェニルブタジエン、テトラフェニルブタジエン、ナフタルイミド、クマリン、ピラン、ペリノン、オキサジアゾール、アルダジン、ピリジン、シクロペンタジエン、ビススチリルアントラセン、キナクリドン、ピロロピリジン、チアジアゾロピリジン、シクロペンタジエン、スチリルアミン、芳香族ジメチリディン化合物、縮合多環芳香族化合物（アントラセン、フェナントロリン、ピレン、ペリレン、ルブレン、又はペンタセンなど）、８−キノリノールの金属錯体、ピロメテン錯体や希土類錯体に代表される各種金属錯体、ポリチオフェン、ポリフェニレン、ポリフェニレンビニレン等のポリマー化合物、有機シラン、又はこれらの誘導体などを挙げることができる。
--- Fluorescent material ---
The fluorescent light emitting material is not particularly limited and may be appropriately selected depending on the purpose. For example, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin , Pyran, perinone, oxadiazole, aldazine, pyridine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compound, condensed polycyclic aromatic compound (anthracene, Phenanthroline, pyrene, perylene, rubrene, or pentacene), metal complexes of 8-quinolinol, various metal complexes represented by pyromethene complexes and rare earth complexes, polythiophene Polyphenylene polymer compounds such as polyphenylene vinylene, organic silane, or their derivatives can be mentioned.
−−ホスト材料−−
前記ホスト材料としては、正孔輸送性に優れる正孔輸送性ホスト材料（正孔輸送性ホストと記載する場合がある）及び電子輸送性に優れる電子輸送性ホスト化合物（電子輸送性ホストと記載する場合がある）を用いることができる。
-Host material-
As the host material, a hole-transporting host material having excellent hole-transporting property (may be described as a hole-transporting host) and an electron-transporting host compound having excellent electron-transporting property (described as an electron-transporting host) May be used).
−−−正孔輸送性ホスト材料−−−
前記正孔輸送性ホスト材料としては、例えば、以下の材料を挙げることができる。即ち、ピロール、インドール、カルバゾール、アザインドール、アザカルバゾール、トリアゾール、オキサゾール、オキサジアゾール、ピラゾール、イミダゾール、チオフェン、ポリアリールアルカン、ピラゾリン、ピラゾロン、フェニレンジアミン、アリールアミン、アミノ置換カルコン、スチリルアントラセン、フルオレノン、ヒドラゾン、スチルベン、シラザン、芳香族第三級アミン化合物、スチリルアミン化合物、芳香族ジメチリディン系化合物、ポルフィリン系化合物、ポリシラン系化合物、ポリ（Ｎ−ビニルカルバゾール）、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン等の導電性高分子オリゴマー、有機シラン、カーボン膜、又はそれらの誘導体などが挙げられる。
これらの中でも、インドール誘導体、カルバゾール誘導体、芳香族第三級アミン化合物、チオフェン誘導体、分子内にカルバゾール基を有するものが好ましく、ｔ−ブチル置換カルバゾール基を有する化合物がより好ましい。
--- Hole-transporting host material ---
Examples of the hole transporting host material include the following materials. Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone Hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, thiophene oligomer, Examples thereof include conductive polymer oligomers such as polythiophene, organic silanes, carbon films, or derivatives thereof.
Among these, indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, thiophene derivatives, and those having a carbazole group in the molecule are preferred, and compounds having a t-butyl substituted carbazole group are more preferred.
−−−電子輸送性ホスト材料−−−
前記電子輸送性ホスト材料としては、例えば、ピリジン、ピリミジン、トリアジン、イミダゾール、ピラゾール、トリアゾール、オキサゾール、オキサジアゾール、フルオレノン、アントラキノジメタン、アントロン、ジフェニルキノン、チオピランジオキシド、カルボジイミド、フルオレニリデンメタン、ジスチリルピラジン、フッ素置換芳香族化合物、ナフタレンペリレン等の複素環テトラカルボン酸無水物、フタロシアニン、又はそれらの誘導体（他の環と縮合環を形成してもよい）、８−キノリノール誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾールやベンゾチアゾールを配位子とする金属錯体に代表される各種金属錯体等を挙げることができる。これらの中でも、耐久性の点から金属錯体化合物が好ましく、金属に配位する少なくとも１つの窒素原子又は酸素原子又は硫黄原子を有する配位子をもつ金属錯体がより好ましい。前記金属錯体電子輸送性ホストとしては、例えば特開２００２−２３５０７６号公報、特開２００４−２１４１７９号公報、特開２００４−２２１０６２号公報、特開２００４−２２１０６５号公報、特開２００４−２２１０６８号公報、特開２００４−３２７３１３号公報等に記載の化合物が挙げられる。
---- Electron-transporting host material ---
Examples of the electron transporting host material include pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluoreni Heterocyclic tetracarboxylic anhydrides such as redenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, naphthaleneperylene, phthalocyanines, or derivatives thereof (may form condensed rings with other rings), 8-quinolinol derivatives And various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole or benzothiazole as a ligand. Among these, a metal complex compound is preferable from the viewpoint of durability, and a metal complex having a ligand having at least one nitrogen atom, oxygen atom, or sulfur atom coordinated to a metal is more preferable. Examples of the metal complex electron transporting host include Japanese Patent Application Laid-Open No. 2002-235076, Japanese Patent Application Laid-Open No. 2004-214179, Japanese Patent Application Laid-Open No. 2004-221106, Japanese Patent Application Laid-Open No. 2004-221665, and Japanese Patent Application Laid-Open No. 2004-221068. And compounds described in JP-A No. 2004-327313.
前記正孔輸送性ホスト材料、電子輸送性ホスト材料の具体例として、以下の化合物を挙げることができるが、これらに限定されるものではない。 Specific examples of the hole transporting host material and the electron transporting host material include the following compounds, but are not limited thereto.
−正孔注入層、正孔輸送層−
前記正孔注入層、又は前記正孔輸送層は、陽極又は陽極側の層から正孔を受け取り陰極側に輸送する機能を有する層である。これらの層に用いられる正孔注入材料、正孔輸送材料は、低分子化合物であっても高分子化合物であってもよい。具体的には、ピロール誘導体、カルバゾール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三級アミン化合物、スチリルアミン化合物、芳香族ジメチリディン系化合物、フタロシアニン系化合物、ポルフィリン系化合物、チオフェン誘導体、有機シラン誘導体、カーボン、等を含有する層が好ましい。
-Hole injection layer, hole transport layer-
The hole injection layer or the hole transport layer is a layer having a function of receiving holes from the anode or the layer on the anode side and transporting them to the cathode side. The hole injecting material and hole transporting material used for these layers may be a low molecular compound or a high molecular compound. Specifically, pyrrole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, Etc. are preferred.
前記正孔注入層、又は前記正孔輸送層には、電子受容性ドーパントを含有させることができる。前記正孔注入層、又は正孔輸送層に導入する電子受容性ドーパントとしては、電子受容性で有機化合物を酸化する性質を有すれば、無機化合物でも有機化合物でも使用できる。
具体的には、無機化合物は塩化第二鉄や塩化アルミニウム、塩化ガリウム、塩化インジウム、五塩化アンチモンなどのハロゲン化金属、五酸化バナジウム、及び三酸化モリブデンなどの金属酸化物などが挙げられる。有機化合物の場合は、置換基としてニトロ基、ハロゲン、シアノ基、トリフルオロメチル基などを有する化合物、キノン系化合物、酸無水物系化合物、フラーレンなどを好適に用いることができる。
これらの電子受容性ドーパントは、単独で用いてもよいし、２種以上を用いてもよい。電子受容性ドーパントの使用量は、材料の種類によって異なるが、正孔輸送層材料に対して０．０１質量％〜５０質量％が好ましく、０．０５質量％〜４０質量％が更に好ましく、０．１質量％〜３０質量％が特に好ましい。
The hole injection layer or the hole transport layer may contain an electron accepting dopant. As the electron-accepting dopant introduced into the hole injection layer or the hole transport layer, an inorganic compound or an organic compound can be used as long as it has an electron accepting property and oxidizes an organic compound.
Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide. In the case of an organic compound, a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
These electron-accepting dopants may be used alone or in combination of two or more. The amount of the electron-accepting dopant varies depending on the type of the material, but is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 40% by mass with respect to the hole transport layer material. 1 mass% to 30 mass% is particularly preferable.
前記正孔注入層、又は正孔輸送層は、上述した材料の１種又は２種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。 The hole injection layer or the hole transport layer may have a single layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Also good.
本発明の有機電界発光素子において、前記正孔注入層は、前記バンドギャップ化合物層であることが好ましい。 In the organic electroluminescent element of the present invention, the hole injection layer is preferably the band gap compound layer.
−電子注入層、電子輸送層−
前記電子注入層、又は前記電子輸送層は、陰極又は陰極側の層から電子を受け取り陽極側に輸送する機能を有する層である。これらの層に用いる電子注入材料、電子輸送材料は低分子化合物であっても高分子化合物であってもよい。
具体的には、ピリジン誘導体、キノリン誘導体、ピリミジン誘導体、ピラジン誘導体、フタラジン誘導体、フェナントロリン誘導体、トリアジン誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、フルオレノン誘導体、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド誘導体、フルオレニリデンメタン誘導体、ジスチリルピラジン誘導体、ナフタレン、ペリレン等の芳香環テトラカルボン酸無水物、フタロシアニン誘導体、８−キノリノール誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾールやベンゾチアゾールを配位子とする金属錯体に代表される各種金属錯体、シロールに代表される有機シラン誘導体、等を含有する層が好ましい。
-Electron injection layer, electron transport layer-
The electron injection layer or the electron transport layer is a layer having a function of receiving electrons from the cathode or a layer on the cathode side and transporting them to the anode side. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
Specifically, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, Metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole as ligands, organosilane derivatives represented by siloles Body, the layer containing the like are preferable.
前記電子注入層、又は電子輸送層には、電子供与性ドーパントを含有させることができる。前記電子注入層、又は電子輸送層に導入される電子供与性ドーパントとしては、電子供与性で有機化合物を還元する性質を有していればよく、Ｌｉなどのアルカリ金属、Ｍｇなどのアルカリ土類金属、希土類金属を含む遷移金属や還元性有機化合物などが好適に用いられる。金属としては、特に仕事関数が４．２ｅＶ以下の金属が好適に使用でき、具体的には、Ｌｉ、Ｎａ、Ｋ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｙ、Ｃｓ、Ｌａ、Ｓｍ、Ｇｄ、及びＹｂなどが挙げられる。また、還元性有機化合物としては、例えば、含窒素化合物、含硫黄化合物、含リン化合物などが挙げられる。
これらの電子供与性ドーパントは、単独で用いてもよいし、２種以上を用いてもよい。電子供与性ドーパントの使用量は、材料の種類によって異なるが、電子輸送層材料に対して０．１質量％〜９９質量％が好ましく、１．０質量％〜８０質量％が更に好ましく、２．０質量％〜７０質量％が特に好ましい。
The electron injection layer or the electron transport layer may contain an electron donating dopant. The electron-donating dopant introduced into the electron-injecting layer or the electron-transporting layer is not limited as long as it has an electron-donating property and has a property of reducing an organic compound. Alkali metals such as Li and alkaline earths such as Mg Metals, transition metals including rare earth metals, reducing organic compounds, and the like are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
These electron donating dopants may be used alone or in combination of two or more. Although the usage-amount of an electron-donating dopant changes with kinds of material, 0.1 mass%-99 mass% are preferable with respect to electron carrying layer material, 1.0 mass%-80 mass% are still more preferable. 0 mass%-70 mass% is especially preferable.
前記電子注入層、又は前記電子輸送層は、上述した材料の１種又は２種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。 The electron injection layer or the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.
−正孔ブロック層、電子ブロック層−
前記正孔ブロック層は、陽極側から有機発光層に輸送された正孔が陰極側に通り抜けることを防止する機能を有する層であり、通常、発光層と陰極側で隣接する有機化合物層として設けられる。
一方、前記電子ブロック層は、陰極側から有機発光層に輸送された電子が陽極側に通り抜けることを防止する機能を有する層であり、通常、有機発光層と陽極側で隣接する有機化合物層として設けられる。
前記正孔ブロック層を構成する化合物の例としては、ＢＡｌｑ等のアルミニウム錯体、トリアゾール誘導体、ＢＣＰ等のフェナントロリン誘導体、等が挙げられる。電子ブロック層を構成する化合物の例としては、例えば前述の正孔輸送材料として挙げたものが利用できる。
前記正孔ブロック層及び電子ブロック層の厚みは、１ｎｍ〜５００ｎｍであるのが好ましく、５ｎｍ〜２００ｎｍであるのがより好ましく、１０ｎｍ〜１００ｎｍであるのが更に好ましい。また、前記正孔ブロック層及び電子ブロック層は、上述した材料の１種又は２種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
-Hole blocking layer, electron blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the organic light emitting layer from passing to the cathode side, and is usually provided as an organic compound layer adjacent to the light emitting layer on the cathode side. It is done.
On the other hand, the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the organic light emitting layer from passing to the anode side, and is usually an organic compound layer adjacent to the organic light emitting layer on the anode side. Provided.
Examples of the compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. As an example of the compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be used.
The thickness of the hole blocking layer and the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. The hole blocking layer and the electron blocking layer may have a single-layer structure made of one or more of the materials described above, or a multilayer structure made up of a plurality of layers having the same composition or different compositions. Also good.
−封止缶−
前記封止缶としては、第１電極、第２電極及び有機層を含む有機電界発光素子が封入できる大きさ、形状、構造などを有していれば特に制限はなく、目的に応じて適宜選択することができる。
前記封止缶と第１電極、第２電極及び有機層を含む有機電界発光素子との間の空間には、水分吸収剤又は不活性液体を封入してもよい。
前記水分吸収剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、酸化バリウム、酸化ナトリウム、酸化カリウム、酸化カルシウム、硫酸ナトリウム、硫酸カルシウム、硫酸マグネシウム、五酸化燐、塩化カルシウム、塩化マグネシウム、塩化銅、フッ化セシウム、フッ化ニオブ、臭化カルシウム、臭化バナジウム、モレキュラーシーブ、ゼオライト、酸化マグネシウムなどが挙げられる。
前記不活性液体としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、パラフィン類、流動パラフィン類；パーフルオロアルカン、パーフルオロアミン、パーフルオロエーテル等のフッ素系溶剤；塩素系溶剤、シリコーンオイル類などが挙げられる。
-Sealing can-
The sealing can is not particularly limited as long as it has a size, shape, structure, and the like that can enclose an organic electroluminescent element including the first electrode, the second electrode, and the organic layer, and is appropriately selected according to the purpose. can do.
A moisture absorbent or an inert liquid may be sealed in a space between the sealing can and the organic electroluminescent element including the first electrode, the second electrode, and the organic layer.
The moisture absorbent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, Examples thereof include calcium chloride, magnesium chloride, copper chloride, cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide.
The inert liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paraffins, liquid paraffins; fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether; chlorine System solvents, silicone oils and the like.
前記有機電界発光素子は、フルカラーで表示し得る装置として構成することができる。
前記有機電界発光素子をフルカラータイプのものとする方法としては、例えば「月刊ディスプレイ」、２０００年９月号、３３〜３７ページに記載されているように、色の３原色（青色（Ｂ）、緑色（Ｇ）、赤色（Ｒ））に対応する光をそれぞれ発光する層構造を基板上に配置する３色発光法、白色発光用の層構造による白色発光をカラーフィルタ層を通して３原色に分ける白色法、青色発光用の層構造による青色発光を蛍光色素層を通して赤色（Ｒ）及び緑色（Ｇ）に変換する色変換法、などが知られている。
この場合は、青色（Ｂ）、緑色（Ｇ）、赤色（Ｒ）の画素ごとにレーザーパワー、厚みを適宜調整することが好ましい。
また、上記方法により得られる、異なる発光色の層構造を複数組み合わせて用いることにより、所望の発光色の平面型光源を得ることができる。例えば、青色及び黄色の発光装置を組み合わせた白色発光光源、青色（Ｂ）、緑色（Ｇ）、及び赤色（Ｒ）の有機電界発光素子を組み合わせた白色発光光源、等である。
The organic electroluminescent element can be configured as a device capable of displaying in full color.
As a method of making the organic electroluminescent element of a full color type, for example, as described in “Monthly Display”, September 2000, pages 33 to 37, the three primary colors (blue (B), A three-color light emission method in which a layer structure that emits light corresponding to green (G) and red (R) is arranged on a substrate, a white light that divides white light emission by a layer structure for white light emission into three primary colors through a color filter layer And a color conversion method in which blue light emission by a layer structure for blue light emission is converted into red (R) and green (G) through a fluorescent dye layer are known.
In this case, it is preferable to appropriately adjust the laser power and thickness for each pixel of blue (B), green (G), and red (R).
In addition, a planar light source having a desired emission color can be obtained by using a combination of a plurality of layer structures having different emission colors obtained by the above method. For example, a white light-emitting light source combining blue and yellow light-emitting devices, a white light-emitting light source combining blue (B), green (G), and red (R) organic electroluminescent elements, and the like.
前記有機電界発光素子は、例えば、照明機器、コンピュータ、車載用表示器、野外表示器、家庭用機器、業務用機器、家電用機器、交通関係表示器、時計表示器、カレンダ表示器、ルミネッセントスクリーン、音響機器等をはじめとする各種分野において好適に使用することができる。 The organic electroluminescent element is, for example, a lighting device, a computer, an on-vehicle display, an outdoor display, a home device, a business device, a home appliance, a traffic display, a clock display, a calendar display, a luminescence. It can be suitably used in various fields including cent screens, audio equipment and the like.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。ただし、実施例１及び７を参考例に読み替える。 Examples of the present invention will be described below, but the present invention is not limited to these examples. However, Examples 1 and 7 are replaced with reference examples.
＜有機電界発光素子の作製＞
−平坦化層用塗布材料および光学層用バインダの作成−
酸化チタン分散液（一次粒子径１５ｎｍの酸化チタンのナノ粒子が分散、材料名：酸化チタン分散トルエン、表面修飾された酸化チタンの屈折率：２．４、商品名：高透明性酸化チタンスラリーＨＴＤ−７６０Ｔ（テイカ株式会社製））１８ｇと、樹脂材料（材料名：フルオレン誘導体、商品名：オグソールＥＡ−０２００（大阪ガスケミカル（株）製））５ｇと、トルエン４ｇとを、ローラー、スターラーにより攪拌し、更に超音波により酸化チタンのナノ粒子を樹脂材料に十分に分散させた。
これにより、平坦化層用塗布材料及び光学層用バインダを得た。
<Production of organic electroluminescence device>
-Preparation of coating material for planarization layer and binder for optical layer-
Titanium oxide dispersion (dispersed titanium oxide nanoparticles with a primary particle diameter of 15 nm, material name: titanium oxide-dispersed toluene, refractive index of surface-modified titanium oxide: 2.4, trade name: highly transparent titanium oxide slurry HTD -760T (manufactured by Teika Co., Ltd.)) 18 g, resin material (material name: fluorene derivative, trade name: Ogsol EA-0200 (manufactured by Osaka Gas Chemical Co., Ltd.)), and 4 g of toluene by a roller and a stirrer. The mixture was stirred, and the titanium oxide nanoparticles were sufficiently dispersed in the resin material by ultrasonic waves.
This obtained the coating material for planarization layers, and the binder for optical layers.
−光学層用塗布材料の作製−
先に作成した光学層用バインダ１０ｇに対し、光散乱粒子（一次粒子径１．５μｍの架橋アクリル系粒子、材料名：ＭＸ−１５０（綜研化学（株）製））２．６ｇ及びトルエン溶媒７ｇを添加し、スターラーにて攪拌した。
更に超音波にて光散乱粒子を光学層用バインダに十分に分散させ、さらにスターラー等でよく攪拌することにより、光学層用塗布材料を得た。
光学層用バインダ（上記酸化チタンと上記樹脂材料との分散液）の硬化時の屈折率は１．７８、光散乱粒子の屈折率は１．４９で屈折率差が十分に大きく、薄膜でも光取り出しに十分な拡散を得ることができる。
またトルエンを溶媒としているため、樹脂の粒子は十分な耐溶剤性が必要であるが、その点でも上記材料の組み合わせは溶剤に強く、また経時変化による分散の劣化（凝集等）においても非常に優れている。
-Production of coating material for optical layer-
2.6 g of light scattering particles (cross-linked acrylic particles having a primary particle size of 1.5 μm, material name: MX-150 (manufactured by Soken Chemical Co., Ltd.)) and 7 g of a toluene solvent are used with respect to 10 g of the binder for an optical layer previously prepared. And stirred with a stirrer.
Furthermore, the light-scattering particles were sufficiently dispersed in an optical layer binder with ultrasonic waves, and further stirred well with a stirrer or the like to obtain an optical layer coating material.
The refractive index of the optical layer binder (the dispersion of the titanium oxide and the resin material) upon curing is 1.78, the refractive index of the light scattering particles is 1.49, and the refractive index difference is sufficiently large. Sufficient diffusion can be obtained for removal.
In addition, since toluene is used as a solvent, the resin particles must have sufficient solvent resistance. However, the combination of the above materials is also resistant to the solvent in this respect, and the dispersion deterioration (aggregation, etc.) due to changes with time is also very high. Are better.
−平坦化層３及び光学層２の作製−
上記平坦化層用塗布材料と光学層用塗布材料に重合開始剤（Ｃｉｂａ製ＩＲＧＡＣＵＲＥ８１９）を添加した。
洗浄し、下記の表面処理をしたガラス基板にワイヤーバーを用いて光学層用塗布材料を塗布し、その後、ＵＶ照射（３６５ｎｍ）を１０分間行い硬化させ、光学層（４μｍ）を得た。
上記光学層の上にワイヤーバーを用いて平坦化層用塗布材料を塗布し、ＵＶ照射を行い硬化させ、光学層（４μｍ）／平坦化層（６μｍ）の積層を得た。
-Production of planarization layer 3 and optical layer 2-
A polymerization initiator (IRGACURE819 manufactured by Ciba) was added to the coating material for the flattening layer and the coating material for the optical layer.
An optical layer coating material was applied to a glass substrate that had been cleaned and subjected to the following surface treatment using a wire bar, and then cured by UV irradiation (365 nm) for 10 minutes to obtain an optical layer (4 μm).
A planarizing layer coating material was applied onto the optical layer using a wire bar, and was cured by UV irradiation to obtain an optical layer (4 μm) / planarizing layer (6 μm) stack.
−ガラス基板１の表面処理−
ガラス基板はシランカップリング処理を行い、光学層−ガラス間の密着性を高めた。
-Surface treatment of glass substrate 1-
The glass substrate was subjected to a silane coupling treatment to improve the adhesion between the optical layer and the glass.
−ＩＴＯ電極（第１電極４）の作製−
光学層上に成膜した平坦化層上にスパッタ装置を用いＩＴＯを１００ｎｍ形成した。
-Production of ITO electrode (first electrode 4)-
100 nm of ITO was formed on the planarizing layer formed on the optical layer using a sputtering apparatus.
−有機層５の作製−
前記手法で作成した第１電極上に、真空蒸着装置により、ＣｕＰＣ、ＰＴＣＤＡ、ＰＴＣＤＩ、ＴＰＤ（Ｎ，Ｎ’−Ｂｉｓ（３−ｍｅｔｈｙｌｐｈｅｎｙｌ）−Ｎ，Ｎ’−ｄｉｐｈｅｎｙｌｂｅｎｚｉｄｉｎｅ）又はα−ＮＰＤ（Ｂｉｓ［Ｎ−（１−ｎａｐｈｔｈｙｌ）−Ｎ−ｐｈｅｎｙｌ］ｂｅｎｚｉｄｉｎｅ）をＸｎｍを蒸着し、バンドギャップ化合物層（正孔注入層）を形成した。
その上にα−ＮＰＤを（５０−Ｘ）ｎｍを蒸着し、正孔輸送層を形成した。
その上にｍＣＰ（１，３−Ｂｉｓ（ｃａｒｂａｚｏｌ−９−ｙｌ）ｂｅｎｚｅｎｅ：６０体積％）と発光材料Ａ（４０体積％）を３０ｎｍ共蒸着させ、有機発光層を形成した。
その上にＢＡｌｑ（Ｂｉｓ−（２−ｍｅｔｈｙｌ−８−ｑｕｉｎｏｌｉｎｏｌａｔｏ）−４−（ｐｈｅｎｙｌ−ｐｈｅｎｏｌａｔｅ）−ａｌｕｍｉｎｉｕｍ（ＩＩＩ））を４９ｎｍ蒸着し電子輸送層を形成した。
更にその上にＢＣＰ（２，９−Ｄｉｍｅｔｈｙｌ−４，７−ｄｉｐｈｅｎｙｌ−１，１０−ｐｈｅｎａｎｔｈｒｏｌｉｎｅ）を１ｎｍ蒸着し電子注入層を形成することにより、有機層を得た。
なお、上記Ｘｎｍは、以下の実施例及び比較例におけるＣｕＰＣ、ＰＴＣＤＡ、ＰＴＣＤＩ、ＴＰＤ又はα−ＮＰＤ層（バンドギャップ化合物層）の厚さを表す。
また、得られた有機層において、有機発光層の屈折率は１．７０であった。
-Preparation of organic layer 5-
CuPC, PTCDA, PTCDI, TPD (N, N′-Bis (3-methylphenyl) -N, N′-diphenylbenzidine) or α-NPD (Bis [ N- (1-naphthyl) -N-phenyl] benzidine) was vapor-deposited to form a band gap compound layer (hole injection layer).
(50-X) nm was vapor-deposited (alpha) -NPD on it, and the positive hole transport layer was formed.
On top of that, mCP (1,3-Bis (carbazol-9-yl) benzene: 60% by volume) and a light-emitting material A (40% by volume) were co-evaporated to form an organic light-emitting layer.
On top of that, BAlq (Bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolate) -aluminum (III)) was deposited to 49 nm to form an electron transport layer.
Further, an organic layer was obtained by depositing 1 nm of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) thereon to form an electron injection layer.
Xnm represents the thickness of the CuPC, PTCDA, PTCDI, TPD or α-NPD layer (band gap compound layer) in the following examples and comparative examples.
In the obtained organic layer, the refractive index of the organic light emitting layer was 1.70.
−反射電極（第２電極６）の作製−
上記有機層の上にＬｉＦを０．５ｎｍ蒸着し、その上に第２電極として、アルミニウムを１００ｎｍ、又は、アルミニウムを１．５ｎｍ、Ａｇを１００ｎｍ蒸着した。
-Production of reflective electrode (second electrode 6)-
LiF was vapor-deposited on the organic layer by 0.5 nm, and aluminum was vapor-deposited thereon as a second electrode by 100 nm, or aluminum was vapor-deposited by 1.5 nm and Ag was vapor-deposited by 100 nm.
−封止缶７の作製−
窒素ガス雰囲気中にて乾燥剤を貼り付け、基板との設置面に封止材を塗った封止ガラス缶を用いて、基板の有機層側を封止した。
-Production of sealing can 7-
A desiccant was attached in a nitrogen gas atmosphere, and the organic layer side of the substrate was sealed using a sealing glass can in which a sealing material was applied to the installation surface with the substrate.
［実施例１］
上記の方法により表面処理を行ったガラス基板上に、上記の光学層（４μｍ）及び平坦化層（６μｍ）を形成した。更に平坦化層上に上記の方法により第１電極となるＩＴＯ電極（１００ｎｍ）を形成した。
そして、上記の方法により、第１電極上に有機層を以下のとおり形成した。高真空下でＩＴＯ上にＣｕＰＣを５ｎｍ蒸着し、その上にα−ＮＰＤを４５ｎｍ蒸着した。その上に、ｍＣＰ（６０体積％）と発光材料Ａ（４０体積％）を３０ｎｍ共蒸着した。更にその上に、ＢＡｌｑを４９ｎｍ、ＢＣＰを１ｎｍそれぞれ蒸着した。
更にその上にＬｉＦを０．５ｎｍ、アルミニウムを１００ｎｍ順に蒸着により成膜し、基板を真空から窒素環境下に移動し、上記の方法でガラス缶により封止を行い実施例１の有機電界発光素子を得た。
実施例１並びに下記実施例２〜７及び比較例１〜４、６〜８の有機電界発光素子の構成を表す模式図を図４に示す。
[Example 1]
The optical layer (4 μm) and the planarization layer (6 μm) were formed on the glass substrate that had been surface-treated by the above method. Further, an ITO electrode (100 nm) serving as the first electrode was formed on the planarizing layer by the above method.
And the organic layer was formed on the 1st electrode as follows by said method. CuPC was deposited on ITO by 5 nm under high vacuum, and α-NPD was deposited by 45 nm thereon. On top of this, mCP (60% by volume) and a light emitting material A (40% by volume) were co-evaporated to 30 nm. Further, 49 nm of BAlq and 1 nm of BCP were deposited thereon.
Further, an organic electroluminescent element of Example 1 is formed by depositing LiF in a thickness of 0.5 nm and aluminum in a thickness of 100 nm thereon, moving the substrate from a vacuum to a nitrogen environment, and sealing with a glass can by the above method. Got.
The schematic diagram showing the structure of Example 1 and the organic electroluminescent element of the following Examples 2-7 and Comparative Examples 1-4, 6-8 is shown in FIG.
［実施例２］
ＣｕＰＣの層の厚さを２ｎｍ、α−ＮＰＤの層の厚さを４８ｎｍとした以外は実施例１と同様の操作を行い、実施例２の有機電界発光素子を得た。
[Example 2]
An organic electroluminescence device of Example 2 was obtained in the same manner as in Example 1 except that the thickness of the CuPC layer was 2 nm and the thickness of the α-NPD layer was 48 nm.
［実施例３］
ＣｕＰＣの層の厚さを１ｎｍ、α−ＮＰＤの層の厚さを４９ｎｍとした以外は実施例１と同様の操作を行い、実施例３の有機電界発光素子を得た。
[Example 3]
An organic electroluminescence device of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the CuPC layer was 1 nm and the thickness of the α-NPD layer was 49 nm.
［実施例４］
ＣｕＰＣの層に代えてＰＴＣＤＡの層を２ｎｍ形成した以外は実施例２と同様の操作を行い、実施例４の有機電界発光素子を得た。
[Example 4]
An organic electroluminescence device of Example 4 was obtained in the same manner as in Example 2 except that a 2 nm thick PTCDA layer was formed instead of the CuPC layer.
［実施例５］
ＣｕＰＣの層に代えてＰＴＣＤＩの層を２ｎｍ形成した以外は実施例２と同様の操作を行い、実施例５の有機電界発光素子を得た。
[Example 5]
An organic electroluminescence device of Example 5 was obtained in the same manner as in Example 2 except that a PTCDI layer having a thickness of 2 nm was formed instead of the CuPC layer.
［実施例６］
ＣｕＰＣの層の厚さを１ｎｍ、α−ＮＰＤの層の厚さを４９ｎｍとし、反射電極をアルミニウムからアルミニウム（１．５ｎｍ）／銀（１００ｎｍ）の順に成膜することに変更した以外は実施例１と同様の操作を行い、実施例６の有機電界発光素子を得た。
なお、実施例６において、アルミニウム層はきわめて薄いために光学的には殆ど作用せず、銀層が反射電極として作用する。
[Example 6]
Example except that the thickness of the CuPC layer was 1 nm, the thickness of the α-NPD layer was 49 nm, and the reflective electrode was formed in the order of aluminum (1.5 nm) / silver (100 nm). The same operation as in Example 1 was performed to obtain an organic electroluminescent element of Example 6.
In Example 6, since the aluminum layer is extremely thin, it hardly functions optically, and the silver layer functions as a reflective electrode.
［実施例７］
ＣｕＰＣの層の厚さを９ｎｍ、α−ＮＰＤの層の厚さを４１ｎｍとした以外は実施例１と同様の操作を行い、実施例７の有機電界発光素子を得た。
[Example 7]
An organic electroluminescence device of Example 7 was obtained in the same manner as in Example 1 except that the thickness of the CuPC layer was 9 nm and the thickness of the α-NPD layer was 41 nm.
［比較例１］
ＣｕＰＣの層の厚さを１０ｎｍ、α−ＮＰＤの層の厚さを４０ｎｍとした以外は実施例１と同様の操作を行い、比較例１の有機電界発光素子を得た。
[Comparative Example 1]
An organic electroluminescence device of Comparative Example 1 was obtained in the same manner as in Example 1 except that the thickness of the CuPC layer was 10 nm and the thickness of the α-NPD layer was 40 nm.
［比較例２］
ＣｕＰＣの層の厚さを２０ｎｍ、α−ＮＰＤの層の厚さを３０ｎｍとした以外は実施例１と同様の操作を行い、比較例２の有機電界発光素子を得た。
[Comparative Example 2]
An organic electroluminescence device of Comparative Example 2 was obtained in the same manner as in Example 1 except that the thickness of the CuPC layer was 20 nm and the thickness of the α-NPD layer was 30 nm.
［比較例３］
ＰＴＣＤＡの層の厚さを１０ｎｍ、α−ＮＰＤの層の厚さを４０ｎｍとした以外は実施例１と同様の操作を行い、比較例３の有機電界発光素子を得た。
[Comparative Example 3]
An organic electroluminescence device of Comparative Example 3 was obtained in the same manner as in Example 1 except that the thickness of the PTCDA layer was 10 nm and the thickness of the α-NPD layer was 40 nm.
［比較例４］
ＰＴＣＤIの厚さを１０ｎｍ、α−ＮＰＤの厚さを４０ｎｍとした以外は実施例１と同様の操作を行い、比較例４の有機電界発光素子を得た。
[Comparative Example 4]
The same operation as in Example 1 was performed except that the thickness of PTCDI was 10 nm and the thickness of α-NPD was 40 nm, whereby an organic electroluminescent device of Comparative Example 4 was obtained.
［比較例５］
実施例１の光学層及び平坦化層を、ガラス基板に対してＩＴＯ電極とは反対側に光学層、平坦化層の順に成膜した以外は実施例１と同様の操作を行い、比較例５の有機電界発光素子を得た。
比較例５の有機電界発光素子の構成を表す模式図を図５に示す。
[Comparative Example 5]
Comparative Example 5 was carried out in the same manner as in Example 1, except that the optical layer and the planarizing layer of Example 1 were formed in the order of the optical layer and the planarizing layer on the opposite side of the glass substrate from the ITO electrode. The organic electroluminescent element was obtained.
A schematic diagram showing the structure of the organic electroluminescent element of Comparative Example 5 is shown in FIG.
［比較例６］
ＣｕＰＣの層をＴＰＤの層に変更した以外は比較例１と同様の操作を行い、比較例６の有機電界発光素子を得た。
[Comparative Example 6]
The same operation as in Comparative Example 1 was performed except that the CuPC layer was changed to the TPD layer, whereby an organic electroluminescent element of Comparative Example 6 was obtained.
［比較例７］
ＣｕＰＣの層をα−ＮＰＤの層に変更した以外は実施例１と同様の操作を行い、比較例７の有機電界発光素子を得た。
[Comparative Example 7]
The same operation as in Example 1 was performed except that the CuPC layer was changed to an α-NPD layer, whereby an organic electroluminescence device of Comparative Example 7 was obtained.
［比較例８］
ＣｕＰＣの層の厚さを０．２ｎｍ、α−ＮＰＤの層の厚さを４９．８ｎｍとした以外は実施例１と同様の操作を行い、比較例８の有機電界発光素子を得た。
[Comparative Example 8]
An organic electroluminescent device of Comparative Example 8 was obtained in the same manner as in Example 1 except that the thickness of the CuPC layer was 0.2 nm and the thickness of the α-NPD layer was 49.8 nm.
作製した有機電界発光素子について、以下のようにして、光取り出し効率及び駆動電圧を評価した。 About the produced organic electroluminescent element, light extraction efficiency and drive voltage were evaluated as follows.
＜外部量子効率及び駆動電圧の測定＞
外部量子効率は、浜松ホトニクス製「Ｃ９９２０−１２」を用いて２．５ｍＡ／ｃｍ２の電流を流したときの外部量子効率を読みとったものである。
駆動電圧は、電流２．５ｍＡ／ｃｍ２を流したとき、素子に加わった電圧値を読み取ったものである。
<Measurement of external quantum efficiency and driving voltage>
The external quantum efficiency is obtained by reading the external quantum efficiency when a current of 2.5 mA / cm 2 is passed using “C9920-12” manufactured by Hamamatsu Photonics.
The drive voltage is obtained by reading a voltage value applied to the element when a current of 2.5 mA / cm 2 is passed.
結果を下記表１〜４に記載した。 The results are shown in Tables 1 to 4 below.
表１〜４の結果から、実施例１〜７の有機電界発光素子は、いずれも外部量子効率が高く、駆動電圧が低いことが分かった。
また、実施例３と６とを対比すると、有機電界発光素子の第２電極（反射電極）をアルミニウムから銀に変更することにより、素子の外部量子効率が大幅に上昇することが認められる。これは、銀の反射率がアルミニウムより高いことに起因すると考えられる。
比較例１〜４の有機電界発光素子は、Ｅｇ化合物層の膜厚が１０ｎｍ以上の素子である。このような素子は光吸収の影響のため、外部量子効率の低下が認められる。
比較例５の有機電界発光素子は、光学層の位置が本発明とは異なる素子である。このような素子は有機発光層からの光がＩＴＯよりガラス基板に入射する際、一部の光が屈折率差による全反射の影響を受け、光学層まで進入することが出来ないため、外部量子効率の低下が認められる。
比較例６の有機電界発光素子は、Ｅｇ化合物としてＥｇが本発明の化合物より大きい化合物を用い、更に、Ｅｇ化合物層の膜厚が１０ｎｍ以上の素子である。このような素子は正孔注入性がＥｇ化合物層に比べ劣るため、駆動電圧の上昇が認められる。
比較例７の有機電界発光素子は、Ｅｇ化合物としてＥｇが本発明の化合物より大きい化合物を用いた素子である。このような素子も正孔注入性がＥｇ化合物層に比べ劣るため、駆動電圧の上昇が認められる。
比較例８の有機電界発光素子は、Ｅｇ化合物層の膜厚が０．５ｎｍ未満の素子である。このような素子はＣｕＰＣの厚さが薄く膜として機能せず、正孔注入性が著しく低下したため、駆動電圧の上昇が認められる。
From the results of Tables 1 to 4, it was found that all of the organic electroluminescent elements of Examples 1 to 7 had high external quantum efficiency and low driving voltage.
Further, when Examples 3 and 6 are compared, it is recognized that the external quantum efficiency of the device is significantly increased by changing the second electrode (reflecting electrode) of the organic electroluminescent device from aluminum to silver. This is considered due to the fact that the reflectance of silver is higher than that of aluminum.
The organic electroluminescent elements of Comparative Examples 1 to 4 are elements in which the film thickness of the Eg compound layer is 10 nm or more. Such an element has a decrease in external quantum efficiency due to light absorption.
The organic electroluminescent element of Comparative Example 5 is an element in which the position of the optical layer is different from that of the present invention. In such an element, when light from the organic light emitting layer enters the glass substrate from ITO, some light is affected by total reflection due to the difference in refractive index and cannot enter the optical layer. A decrease in efficiency is observed.
The organic electroluminescent element of Comparative Example 6 is an element in which Eg is larger than the compound of the present invention as the Eg compound, and the film thickness of the Eg compound layer is 10 nm or more. Since such an element is inferior to the Eg compound layer in the hole injection property, an increase in driving voltage is recognized.
The organic electroluminescent device of Comparative Example 7 is a device using a compound in which Eg is larger than the compound of the present invention as the Eg compound. Since such an element is also inferior to the Eg compound layer in the hole injection property, an increase in driving voltage is recognized.
The organic electroluminescent element of Comparative Example 8 is an element in which the film thickness of the Eg compound layer is less than 0.5 nm. In such an element, the CuPC is thin and does not function as a film, and the hole injection property is remarkably lowered, so that an increase in driving voltage is recognized.
１ ガラス基板
２ 光学層
３ 平坦化層
４ 第１電極（透明電極）
５ 有機層
６ 第２電極（反射電極）
７ 封止缶
DESCRIPTION OF
5
7 Sealing can
Claims (9)
前記光学層は、一次粒子径が０．５μｍ以上の透明な少なくとも１種の光散乱粒子とバインダ成分とを含み、前記バインダ成分は前記有機発光層の屈折率以上の屈折率を有し、
前記有機層は更にバンドギャップ化合物層を少なくとも一層含み、
前記バンドギャップ化合物層は前記第１電極に隣接する正孔注入層であり、
前記バンドギャップ化合物層はＥｇ（バンドギャップ）が１．３〜２．５ｅＶ化合物からなり、膜厚が０．５ｎｍ以上２ｎｍ未満である、有機電界発光素子。 An organic electroluminescent device in which a substrate, an optical layer that diffuses and scatters light, a first electrode that is a transparent electrode, an organic layer that includes an organic light emitting layer, and a second electrode are formed in this order,
The optical layer includes at least one transparent light scattering particle having a primary particle size of 0.5 μm or more and a binder component, and the binder component has a refractive index equal to or higher than the refractive index of the organic light emitting layer,
The organic layer further includes at least one band gap compound layer,
The band gap compound layer is a hole injection layer adjacent to the first electrode;
The band gap compound layer is an organic electroluminescent device having an Eg (band gap) of 1.3 to 2.5 eV and a film thickness of 0.5 nm or more and less than 2 nm.
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