JP2007005784A - Organic el device - Google Patents
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Abstract
Description
本発明は、光を上面電極から取り出すトップエミッション型有機ＥＬ素子（ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｔ ｄｅｖｉｃｅ）に於ける高効率化及び長寿命化に関する。 The present invention relates to high efficiency and long life in a top emission type organic EL device that extracts light from a top electrode.
現在、有機ＥＬ素子を表示素子として用いる表示装置を実用化する研究開発が盛んに行われている。 Currently, research and development for practical use of display devices using organic EL elements as display elements are being actively conducted.
特に、基板とは反対側に在る上面電極から光を取り出すトップエミッション型有機ＥＬ素子は、ＴＦＴ（ｔｈｉｎ ｆｉｌｍ ｔｒａｎｓｉｓｔｏｒ）を用いたアクティブマトリクス型表示装置に用いた場合、基板側の下面電極から光を取り出すボトムエミッション型有機ＥＬ素子に比較し、ＴＦＴマトリクスに依る遮光がない為、開口率を大きくすることでき、表示装置の高輝度化、及び、長寿命化の点で有利である。 In particular, a top emission type organic EL element that extracts light from the upper surface electrode on the side opposite to the substrate is used to emit light from the lower surface electrode on the substrate side when used in an active matrix display device using a TFT (Thin Film Transistor). Compared with a bottom emission type organic EL element that takes out the light, there is no light shielding due to the TFT matrix, so that the aperture ratio can be increased, which is advantageous in terms of increasing the brightness and extending the life of the display device.
図３は従来の技術に依るボトムエミッション型有機ＥＬ素子を表す要部切断側面図であり、図に於いて、１は透明基板、２は透明電極からなる陽極、３は発光層（図示せず）を含む有機層、４は陰極をそれぞれ示している。 FIG. 3 is a cut-away side view of a principal part showing a bottom emission type organic EL device according to the prior art. In the figure, 1 is a transparent substrate, 2 is an anode made of a transparent electrode, and 3 is a light emitting layer (not shown). ) And 4 are cathodes.
図３のボトムエミッション型有機ＥＬ素子に於いては、有機層３に含まれる発光層からの光は陽極２を通して透明基板１から取り出す構成になっている（例えば、非特許文献１を参照。）。 In the bottom emission type organic EL device of FIG. 3, light from the light emitting layer included in the organic layer 3 is extracted from the transparent substrate 1 through the anode 2 (see, for example, Non-Patent Document 1). .
このボトムエミッション型有機ＥＬ素子は、一般的に、透明基板１としてはガラスを、透明電極からなる陽極２としてはＩＴＯ（ｉｎｄｉｕｍ ｔｉｎ ｏｘｉｄｅ）を、陰極４にはＡｌをそれぞれ用い、そして、陰極４から有機層３へ良好に電子注入を行う為、陰極４に於ける有機層３側の表面にＬｉＦからなる電子注入層を設けたＬｉＦ／Ａｌ陰極を用いることもある。 This bottom emission type organic EL element generally uses glass as the transparent substrate 1, ITO (indium tin oxide) as the anode 2 made of a transparent electrode, Al as the cathode 4, and the cathode 4. In order to perform good electron injection to the organic layer 3, a LiF / Al cathode having an electron injection layer made of LiF on the surface of the cathode 4 on the organic layer 3 side may be used.
図４は従来の技術に依るトップエミッション型有機ＥＬ素子を表す要部切断側面図であり、図に於いて、１１は絶縁性基板、１２は陽極、１３は発光層（図示せず）を含む有機層、１４は光透過性電極からなる陰極をそれぞれ示している。 FIG. 4 is a cut-away side view of a principal part showing a top emission type organic EL device according to the prior art. In FIG. 4, 11 is an insulating substrate, 12 is an anode, and 13 is a light emitting layer (not shown). An organic layer 14 indicates a cathode made of a light transmissive electrode.
図４のトップエミッション型有機ＥＬ素子に於いては、有機層１３に含まれる発光層からの光は光透過性電極からなる陰極１４から取り出す構成になっている。 In the top emission type organic EL device of FIG. 4, light from the light emitting layer included in the organic layer 13 is extracted from the cathode 14 formed of a light transmissive electrode.
このトップエミッション型有機ＥＬ素子は、一般的に、陰極１４としては例えばＩＴＯ等の透明電極を用いるのであるが、Ｍｇ薄膜やＡｇ薄膜のような光半透過性電極を用い、陽極１２にＰｔ、Ａｕ、Ｃｒのような光反射性電極を用いた場合、陰極１４及び陽極１２間で発生する多重干渉に依って、微小空洞共振器（マイクロキャビティ）効果で、発光スペクトルがボトムエミッション型有機ＥＬ素子に比較して急峻となり、色純度が向上するとされている（例えば、特許文献１を参照。）。 In this top emission type organic EL element, a transparent electrode such as ITO is generally used as the cathode 14, but a light translucent electrode such as an Mg thin film or an Ag thin film is used, and Pt, When a light reflective electrode such as Au or Cr is used, the emission spectrum is a bottom emission type organic EL element due to the microcavity effect due to multiple interference generated between the cathode 14 and the anode 12. It is said that the color purity is improved as compared to (see, for example, Patent Document 1).
更に、陽極１２として光反射率が高いＡｇ或いはＡｌなどの金属を用いることで発光効率の向上が期待できるが、ＡｇやＡｌから直接に有機層１３に正孔注入することは困難であって、有機ＥＬ素子の動作電圧上昇を引き起こす。 Furthermore, the use of a metal such as Ag or Al having a high light reflectance as the anode 12 can be expected to improve the luminous efficiency, but it is difficult to inject holes directly from the Ag or Al into the organic layer 13, This increases the operating voltage of the organic EL element.
そこで、トップエミッション型有機ＥＬ素子に於ける正孔注入を改善する為の手段として、陽極をＡｌ−Ｃｕ／Ｎｉ／ＮｉＯx ／Ｖ2 Ｏ5 で構成すること（例えば、特許文献２を参照。）、Ａｇ／ＩＴＯで構成すること（例えば、特許文献３を参照。）、Ａｌ／Ｎｉで構成すること（例えば、非特許文献２を参照。）などが知られている。 Therefore, as a means for improving hole injection in the top emission type organic EL element, the anode is composed of Al—Cu / Ni / NiO x / V 2 O 5 (see, for example, Patent Document 2). ), Ag / ITO (for example, see Patent Document 3), and Al / Ni (for example, see Non-Patent Document 2) are known.
また、陽極にＡｇを、そして、正孔注入層にＣＦx 及びＭｏＯx を、更に、陰極の光半透過性電極にはＡｇ薄膜をそれぞれ用い、また、有機層厚を最適化することにより、色純度だけでなく、発光効率も従来のボトムエミッション型有機ＥＬ素子に比較して向上することが開示されている（例えば、特許文献４を参照。）。 Further, Ag is used for the anode, CF x and MoO x are used for the hole injection layer, an Ag thin film is used for the light semi-transmissive electrode of the cathode, and the organic layer thickness is optimized, It is disclosed that not only the color purity but also the light emission efficiency is improved as compared with the conventional bottom emission type organic EL element (for example, see Patent Document 4).
尚、Ａｇ薄膜を陰極に用いる技術としては、電子注入層ＬｉＦと陰極Ａｇ薄膜間に層厚０．６ｎｍのＡｌ超薄膜を挿入することにより良好な電圧−電流密度特性を示すことが報告されている（例えば、特許文献５を参照。）。 As a technique using an Ag thin film as a cathode, it has been reported that a good voltage-current density characteristic is exhibited by inserting an Al ultrathin film having a layer thickness of 0.6 nm between the electron injection layer LiF and the cathode Ag thin film. (For example, refer to Patent Document 5).
前記したように微小空洞共振器（マイクロキャビティ）効果を利用したトップエミッション型有機ＥＬ素子では、色純度、発光効率が向上し、高輝度・高発光効率・高色再現性をもつアクティブマトリクス型表示装置の実現が可能であるとされている。 As described above, the top emission type organic EL device utilizing the microcavity effect improves the color purity and light emission efficiency, and has an active matrix display with high luminance, high light emission efficiency, and high color reproducibility. It is said that the device can be realized.
然しながら、本発明者の知見に依れば、トップエミッション型有機ＥＬ素子の寿命特性については問題があり、実用化するに充分な程度の寿命を実現した旨の報告は未だなされていない。特に、非特許文献２に開示されている陽極にＡｌ／Ｎｉの構成を用いた素子では寿命特性が悪い。
本発明では、陽極に光高反射金属を用いたトップエミッション型有機ＥＬ素子に於け寿命特性を簡単な手段を適用して向上させようとする。 In the present invention, it is intended to improve the life characteristics of a top emission type organic EL device using a highly reflective metal for the anode by applying simple means.
本発明の課題は、以下の有機ＥＬ素子によって達成された。
＜１＞ 基板上に少なくとも光反射性陽極、正孔注入層、正孔輸送層、発光層、電子輸送層、光透過性陰極が順次積層された有機ＥＬ素子に於いて、前記正孔注入層の前記光反射性陽極側に金属酸化物がドープされてなることを特徴とする有機ＥＬ素子。
＜２＞ ドープする金属酸化物が酸化バナジウム（Ｖ2 Ｏ5 ）又は酸化モリブデン（ＭｏＯ3 ）であることを特徴とする＜１＞項に記載の有機ＥＬ素子。
＜３＞ 前記光反射性陽極がＡｌ或いはＡｌ合金からなることを特徴とする＜１＞或いは＜２＞項に記載の有機ＥＬ素子。
＜４＞ 前記光反射性陽極と前記正孔注入層との間に仕事関数が４．３ｅＶ以上の金属、或いはその金属酸化物を有する陽極バッファー層が介挿されてなることを特徴とする＜１＞乃至＜３＞の何れか１項に記載の有機ＥＬ素子。
＜５＞ 前記光反射性陽極がＵＶオゾン或いはＯ2 プラズマで表面処理されてなることを特徴とする＜１＞乃至＜４＞の何れか１項に記載の有機ＥＬ素子。
＜６＞ 前記陽極バッファー層がＵＶオゾン或いはＯ2 プラズマで表面処理されてなることを特徴とする＜４＞或いは＜５＞に記載の有機ＥＬ素子。
＜７＞ 前記ドープされた金属酸化物が前記正孔注入層の前記正孔輸送層側に存在しないことを特徴とする＜１＞乃至＜６＞の何れか１項に記載の有機ＥＬ素子。
＜８＞ 前記光透過性陰極がＡｇ或いはＡｇ合金からなる光半透過性陰極であることを特徴とする＜１＞乃至＜７＞の何れか１項に記載の有機ＥＬ素子。
＜９＞ 前記Ａｇ或いはＡｇ合金からなる光半透過性陰極と前記電子輸送層との間にアルカリ金属化合物及び層厚が０．５ｎｍ〜３ｎｍのＡｌ薄膜からなる電子注入層が介挿されてなることを特徴とする＜８＞に記載の有機ＥＬ素子。
＜１０＞ 前記Ａｇ或いはＡｇ合金からなる光半透過性陰極上に硫化亜鉛（ＺｎＳ）からなるキャッピング層が積層されてなることを特徴とする＜８＞或いは＜９＞に記載の有機ＥＬ素子。
＜１１＞ 前記基板がフレキシブル基板であることを特徴とする＜１＞乃至＜１０＞の何れか１項に記載の有機ＥＬ素子。
The object of the present invention has been achieved by the following organic EL device.
<1> In an organic EL device in which at least a light reflective anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a light transmissive cathode are sequentially laminated on a substrate, the hole injection layer An organic EL device, wherein a metal oxide is doped on the light reflective anode side.
<2> The organic EL device according to <1>, wherein the metal oxide to be doped is vanadium oxide (V 2 O 5 ) or molybdenum oxide (MoO 3 ).
<3> The organic EL device according to <1> or <2>, wherein the light reflective anode is made of Al or an Al alloy.
<4> A metal having a work function of 4.3 eV or more, or an anode buffer layer having the metal oxide is interposed between the light reflective anode and the hole injection layer. The organic EL device according to any one of 1> to <3>.
<5> The organic EL device according to any one of <1> to <4>, wherein the light reflective anode is surface-treated with UV ozone or O 2 plasma.
<6> The organic EL device according to <4> or <5>, wherein the anode buffer layer is surface-treated with UV ozone or O 2 plasma.
<7> The organic EL device according to any one of <1> to <6>, wherein the doped metal oxide does not exist on the hole transport layer side of the hole injection layer.
<8> The organic EL device according to any one of <1> to <7>, wherein the light transmissive cathode is a light semi-transmissive cathode made of Ag or an Ag alloy.
<9> An alkali metal compound and an electron injection layer made of an Al thin film having a layer thickness of 0.5 nm to 3 nm are interposed between the light translucent cathode made of Ag or an Ag alloy and the electron transport layer. The organic EL element as described in <8> characterized by the above-mentioned.
<10> The organic EL device according to <8> or <9>, wherein a capping layer made of zinc sulfide (ZnS) is laminated on the light translucent cathode made of Ag or an Ag alloy.
<11> The organic EL element according to any one of <1> to <10>, wherein the substrate is a flexible substrate.
本発明の有機ＥＬ素子に於いては、基板上に少なくとも光反射性陽極、正孔注入層、正孔輸送層、発光層、電子輸送層、光透過性陰極が順次積層された有機ＥＬ素子に於いて、前記正孔注入層の前記光反射性陽極側に金属酸化物がドープされてなることが基本になっている。好ましくは、本発明における正孔注入層は、金属酸化物をドープして含有する第一正孔注入層及び金属酸化物を実質的に含有しない第二正孔注入層の積層体である。前記第一正孔注入層は前記光反射性陽極に接し、前記第二正孔注入層は前記正孔輸送層に接して配される。 In the organic EL device of the present invention, an organic EL device in which at least a light reflective anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a light transmissive cathode are sequentially laminated on a substrate. However, it is fundamental that a metal oxide is doped on the light reflective anode side of the hole injection layer. Preferably, the hole injection layer in the present invention is a laminate of a first hole injection layer containing a metal oxide doped and a second hole injection layer substantially free of a metal oxide. The first hole injection layer is in contact with the light reflective anode, and the second hole injection layer is in contact with the hole transport layer.
有機膜である正孔注入層中にドープされる金属酸化物は、酸化バナジウム（Ｖ2 Ｏ5 ）或いは酸化モリブデン（ＭｏＯ3 ）が好ましく、また、光反射性陽極には、Ａｌ又はＡｌ−ＮｄなどのＡｌ合金が好ましく、更にまた、陽極バッファー層としては、酸化モリブデン、酸化バナジウム、酸化ニッケル（ＮｉＯ）、モリブデン（Ｍｏ）、ニッケル（Ｎｉ）等から選択して良いが、特に、酸化モリブデンが好ましい。 The metal oxide doped in the hole injection layer which is an organic film is preferably vanadium oxide (V 2 O 5 ) or molybdenum oxide (MoO 3 ), and Al or Al—Nd is used for the light reflective anode. Further, an Al alloy such as, for example, is preferable, and the anode buffer layer may be selected from molybdenum oxide, vanadium oxide, nickel oxide (NiO), molybdenum (Mo), nickel (Ni), and the like. preferable.
前記手段を採ることに依り、トップエミッション型有機ＥＬ素子を長寿命化することができ、また、光反射性陽極として光反射率は高いが寿命特性が悪いとされているＡｌ或いはＡｌ合金を用いることが可能となって高効率化することができ、更にまた、Ａｌ等の光反射性陽極と正孔注入層との間に仕事関数が４．３ｅＶ以上の金属またはその金属酸化物からなる陽極バッファー層を介挿することで動作電圧を低電圧化することができる。従って、全体として広い色再現範囲をもち、長寿命、高効率、低動作電圧であるトップエミッション型有機ＥＬ素子を実現することができる。 By adopting the above means, it is possible to extend the life of the top emission type organic EL element, and use Al or Al alloy, which has high light reflectivity but poor life characteristics, as the light reflective anode. In addition, the anode made of a metal having a work function of 4.3 eV or more or a metal oxide thereof is provided between the light reflective anode such as Al and the hole injection layer. The operating voltage can be lowered by interposing the buffer layer. Accordingly, it is possible to realize a top emission type organic EL element having a wide color reproduction range as a whole, having a long life, high efficiency, and low operating voltage.
図１は本発明に依る一実施の形態を説明する為の有機ＥＬ素子を表す要部切断側面図であり、図に於いて、２１は基板、２２は光反射性陽極、２３は陽極バッファー層、２４は正孔注入層、２５は正孔注入層２４を構成する第一正孔注入層、２６は正孔注入層を構成する第二正孔注入層、２７は正孔輸送層、２８は発光層、２９は電子輸送層、３０は光透過性陰極、３１はキャッピング層をそれぞれ示している。 FIG. 1 is a cut-away side view of an essential part showing an organic EL device for explaining an embodiment according to the present invention. In the figure, 21 is a substrate, 22 is a light-reflective anode, and 23 is an anode buffer layer. , 24 is a hole injection layer, 25 is a first hole injection layer constituting the hole injection layer 24, 26 is a second hole injection layer constituting the hole injection layer, 27 is a hole transport layer, and 28 is The light emitting layer, 29 is an electron transport layer, 30 is a light transmitting cathode, and 31 is a capping layer.
図示の有機ＥＬ素子に於いて、基板２１には、ガラス或いは石英等の透明性絶縁基板、ＰＥＴ等のフレキシブル基板、Ｓｉ等の半導体基板、又は、それら基板上にＴＦＴのようなスイッチング素子をマトリスクス状に形成した有機ＥＬ素子のオンオフ制御回路を作製した基板を用いてよい。基板２１にフレキシブル基板を用いた場合、可撓性があり機器の筐体上の曲面に配置できるフレキシブルディスプレイが可能となる。
フレキシブル基板としては、特開２００２−８２６２７に開示されている様に、ステンレス、Ｆｅ、Ａｌ、Ｎｉ、Ｃｏ、Ｃｕやこれらの合金等からなるフィルム状金属基板、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＰＥＳ（ポリエーテルスルホン）、ＰＯ（ポリオレフィン）等からなるフィルム状プラスチック基板、或いは当該フィルム状プラスチック基板表面にガスバリア層を設けたもの等を用いることができる。
In the illustrated organic EL element, the substrate 21 is made of a transparent insulating substrate such as glass or quartz, a flexible substrate such as PET, a semiconductor substrate such as Si, or a switching element such as a TFT on the substrate. A substrate on which an on / off control circuit for an organic EL element formed in a shape is manufactured may be used. When a flexible substrate is used as the substrate 21, a flexible display that is flexible and can be arranged on a curved surface on the casing of the device is possible.
As a flexible substrate, as disclosed in JP-A-2002-82627, a film-like metal substrate made of stainless steel, Fe, Al, Ni, Co, Cu, or an alloy thereof, PET (polyethylene terephthalate), PEN (polyethylene) A film-like plastic substrate made of naphthalate), PES (polyethersulfone), PO (polyolefin), or the like, or a film-like plastic substrate surface provided with a gas barrier layer can be used.
光反射性陽極２２には、Ａｌ或いはＡｌ−ＮｄなどのＡｌ合金、Ａｇ或いはＡｇ合金、Ｍｏ、Ｃｒ等が用いられる。
尚、従来陽極として使用されているＩＴＯは可撓性に乏しく、脆く割れやすいという特徴があり（フレキシブル基板への印刷技術、Ｐ．８４、東レリサーチセンター）、フレキシブルディスプレイには不適であるが、上記の金属および金属合金を上述フレキシブル基板上に光反射性陽極として用いることにより、可撓性に富み、割れにくい理想的なフレキシブルディスプレイが可能となる。
For the light reflective anode 22, Al alloy such as Al or Al—Nd, Ag or Ag alloy, Mo, Cr, or the like is used.
In addition, ITO conventionally used as an anode has a characteristic that it is poor in flexibility, is brittle and easily broken (printing technology on a flexible substrate, P.84, Toray Research Center), and is not suitable for a flexible display. By using the above metal and metal alloy as a light-reflective anode on the above-mentioned flexible substrate, an ideal flexible display which is rich in flexibility and hardly broken is possible.
正孔注入層２４には、ＨＯＭＯ（最高被占準位）が高い、即ち、イオン化ポテンシャルが小さい材料、代表的なものとして例えば銅フタロシアニン（ＣｕＰｃ）、スターバースト型アミンであるｍ−ＭＴＤＡＴＡ、２−ＴＮＡＴＡ等が用いられる。 The hole injection layer 24 is made of a material having a high HOMO (highest occupied level), that is, a low ionization potential, typically copper phthalocyanine (CuPc), m-MTDATA, which is a starburst amine, -TNATA or the like is used.
第一正孔注入層２５には、上記正孔注入層２４に酸化バナジウム（Ｖ2 Ｏ5 ）又は酸化モリブデン（ＭｏＯ3 ）等の金属酸化物をドープすることで構成されている。金属酸化物をドープする量は、好ましくは正孔注入材料に対して１０質量％以上６０質量％以下である。より好ましくは正孔注入材料に対して２０質量％以上５０質量％以下である。 The first hole injection layer 25 is configured by doping the hole injection layer 24 with a metal oxide such as vanadium oxide (V 2 O 5 ) or molybdenum oxide (MoO 3 ). The amount doped with the metal oxide is preferably 10% by mass or more and 60% by mass or less with respect to the hole injection material. More preferably, it is 20 mass% or more and 50 mass% or less with respect to hole injection material.
第二正孔注入層２６は、正孔注入層２４自体、Ｆ４−ＴＣＮＱ、或いは、上記金属酸化物をドープした正孔注入層を用いる。 As the second hole injection layer 26, the hole injection layer 24 itself, F4-TCNQ, or a hole injection layer doped with the metal oxide is used.
正孔輸送層２７も正孔注入層２４と同様にＨＯＭＯが高い、即ち、イオン化ポテンシャルが小さい材料が用いられ、代表的なものとしては、ＴＰＤ、α−ＮＰＤ等がある。 The hole transport layer 27 is also made of a material having a high HOMO, that is, a low ionization potential, like the hole injection layer 24. Typical examples include TPD and α-NPD.
発光層２８には、Ａｌｑ３、ＢＡｌｑ２等の金属錯体系材料、ＰＺ１０、ＥＭ２等の色素系材料等を使用するか、或いは、ルブレン、ｔ（ｄｔａ）ｐｙ（１，３，６，８−ｔｅｔｒａ（Ｎ，Ｎ−ｄｉ−４−ｔｏｌｙｌａｍｉｎｏ）ｐｙｒｅｎｅ）、ｔｂｐｐｙ（１，３，６，８−テトラ（４−ビフェニル）ピレン）等の色素をＡｌｑ３、ＣＢＰ等のホスト材にドーピングしたものを使用することができる。 For the light emitting layer 28, a metal complex material such as Alq3 or BAlq2, a pigment material such as PZ10 or EM2, or the like, or rubrene, t (dta) py (1,3,6,8-tetra ( N, N-di-4-tolylamino) pyrene), tbppy (1,3,6,8-tetra (4-biphenyl) pyrene) or the like doped with a host material such as Alq3 or CBP Can do.
電子輸送層２９には、光透過性陰極３０からの電子注入障壁を小さくする為にＬＵＭＯが低い材料が用いられ、代表的なものとしては、Ａｌｑ３、ＢＣＰ等が挙げられる。これらの電子輸送材料にＬｉ、Ｃｓ等の仕事関数が小さい金属をドープすると光透過性陰極３０から電子注入を行う際の障壁が小さくなる。 A material having a low LUMO is used for the electron transport layer 29 in order to reduce the electron injection barrier from the light-transmitting cathode 30, and representative examples include Alq3 and BCP. When these electron transport materials are doped with a metal having a small work function such as Li or Cs, the barrier when electrons are injected from the light-transmissive cathode 30 is reduced.
光透過性陰極３０には、層厚が１０ｎｍ〜４０ｎｍのＡｇ又はＭｇ−Ａｇ等のＡｇ合金が用いられ、また、光透過性陰極３０から電子輸送層２９への電子注入を良好にする為、光透過性陰極３０と電子輸送層２９との間に層厚が０．１ｎｍ〜５ｎｍのＬｉＦ等のアルカリフッ化物からなる電子注入層を介在させることができ、更に、アルカリフッ化物上には層厚が０．２ｎｍ〜３．０ｎｍ程度のＡｌ層を設けることが好ましい。 For the light transmissive cathode 30, an Ag alloy such as Ag or Mg—Ag having a layer thickness of 10 nm to 40 nm is used, and in order to improve electron injection from the light transmissive cathode 30 to the electron transport layer 29, An electron injection layer made of an alkali fluoride such as LiF having a layer thickness of 0.1 nm to 5 nm can be interposed between the light-transmitting cathode 30 and the electron transport layer 29. Further, a layer is formed on the alkali fluoride. It is preferable to provide an Al layer having a thickness of about 0.2 nm to 3.0 nm.
光透過性陰極３０として光半透過電極を用いることにより、光反射性陽極２２と光半透過性である陰極３０との間で多重干渉による微小空洞共振器（マイクロキャビティ）効果を生成させることで発光スペクトルの色純度が良くなる。 By using a light transflective electrode as the light transmissive cathode 30, a microcavity effect caused by multiple interference is generated between the light reflective anode 22 and the light semitransmissive cathode 30. The color purity of the emission spectrum is improved.
更にまた、必須ではないが、光透過性陰極３０上にはキャッピング層３１を形成することが好ましい。キャッピング層３１は光透過性陰極３０の光透過率を向上させる効果があり、屈折率が大きい材料を用いると良く、例えば、ＩＴＯ、ＴｉＯ2 、ＭｇＯ等の高屈材料を用いることができるのであるが、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ等の亜鉛化合物が高屈折で且つ真空蒸着で成膜できる旨の利点がある。尚、光透過性陰極３０にはＩＴＯに代表される透明電極を用いても良い。 Furthermore, although not essential, it is preferable to form a capping layer 31 on the light-transmissive cathode 30. The capping layer 31 has an effect of improving the light transmittance of the light-transmitting cathode 30, and a material having a large refractive index is preferably used. For example, a highly flexible material such as ITO, TiO 2 , or MgO can be used. However, there is an advantage that a zinc compound such as ZnS, ZnSe, ZnTe or the like has high refraction and can be formed by vacuum deposition. A transparent electrode typified by ITO may be used for the light transmissive cathode 30.
前記説明した構成に加えて、より好ましい構成としては、光反射性陽極２２と第一正孔注入層２５との間に陽極バッファー層２３を介挿することが好ましく、その陽極バッファー層２３としては、仕事関数が４．３ｅＶ以上の金属、或いは、その金属酸化物からなる材料が用いられる。そして、当該材料には、酸化モリブデン（ＭｏＯ3 ）、酸化バナジウム（Ｖ2 Ｏ5 ）、酸化ニッケル（ＮｉＯ）、モリブデン（Ｍｏ）、ニッケル（Ｎｉ）等から採用して良いが、ＭｏＯ3 が最も好ましい。尚、陽極バッファー層２３の層厚は光反射性陽極２２の反射率を損ないよう０．５ｎｍ〜１０ｎｍが好ましい。 In addition to the configuration described above, as a more preferable configuration, an anode buffer layer 23 is preferably interposed between the light reflective anode 22 and the first hole injection layer 25. As the anode buffer layer 23, Further, a metal having a work function of 4.3 eV or more, or a material made of a metal oxide thereof is used. Then, the said material, molybdenum oxide (MoO 3), vanadium oxide (V 2 O 5), nickel oxide (NiO), molybdenum (Mo), may be employed nickel (Ni) or the like, is MoO 3 most preferable. The layer thickness of the anode buffer layer 23 is preferably 0.5 nm to 10 nm so as to impair the reflectance of the light reflective anode 22.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
実施例１
（１） 純水→アセトン→純水→ＩＰＡの順に各１５分間の超音波洗浄を行ったガラス基板上にＷフィラメントを用いて光反射性陽極を構成する厚さ６０ｎｍのＡｌ膜を成膜した。その後、基板表面をＵＶオゾンで２０分の処理を行なった。
Example 1
(1) An Al film having a thickness of 60 nm constituting a light reflective anode was formed on a glass substrate that had been subjected to ultrasonic cleaning for 15 minutes each in the order of pure water → acetone → pure water → IPA. . Thereafter, the substrate surface was treated with UV ozone for 20 minutes.
（２） 次に、Ａｌからなる光反射性陽極上にＴａからなるボートを用いて２−ＴＮＡＴＡ（４，４’，４”−トリス（２−ナフチルフェニルアミノ) トリフェニルアミン) 、Ｍｏからなるボートを用いて酸化バナジウム（Ｖ2 Ｏ5 ）をＶ2 Ｏ5 のドープ濃度が３３質量％となるように且つ層厚が２０ｎｍとなるように真空蒸着法に依る共蒸着を行って第一正孔注入層を形成する。 (2) Next, using a boat made of Ta on a light reflective anode made of Al, made of 2-TNATA (4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine) and Mo Using a boat, co-evaporation of vanadium oxide (V 2 O 5 ) by a vacuum deposition method was performed so that the V 2 O 5 doping concentration was 33% by mass and the layer thickness was 20 nm. A hole injection layer is formed.
（３） 次に、Ｔａからなるボートを用いて正孔注入層２−ＴＮＡＴＡと、同じくＴａからなるボートを用いてＦ４−ＴＣＮＱとをＦ４−ＴＣＮＱ（２，３，５，６−ｔｅｔｒａｆｌｕｏｒｏ−７，７，８，８−ｔｅｔｒａｃｙａｎｏｑｕｉｎｏｄｉｍｅｔｈａｎｅ）のドープ濃度が０．１質量％となるように且つ層厚が１６５ｎｍとなるように真空蒸着法に依る共蒸着を行って第二正孔注入層を形成する。 (3) Next, a hole injection layer 2-TNATA is used using a boat made of Ta, and F4-TCNQ is converted into F4-TCNQ (2, 3, 5, 6-tetrafluor-7 using a boat made of Ta. , 7,8,8-tetracyanoquinodimethane) to form a second hole injection layer by co-evaporation using a vacuum deposition method so that the doping concentration is 0.1 mass% and the layer thickness is 165 nm. .
（４） 次に、Ｔａからなるボートを用いてＮＰＤ（Ｎ，Ｎ’−ジナフチル−Ｎ，Ｎ’−ジフェニル−〔１，１’−ビフェニル〕−４，４’−ジアミン）を層厚が１０ｎｍとなるように成膜して正孔輸送層を形成する。 (4) Next, using a boat made of Ta, the layer thickness of NPD (N, N′-dinaphthyl-N, N′-diphenyl- [1,1′-biphenyl] -4,4′-diamine) is 10 nm. A hole transport layer is formed by forming a film so that
（５） 次に、Ｔａからなるボートを用いてｔ（ｄｔａ）ｐｙ（１，３，６，８−ｔｅｔｒａ（Ｎ，Ｎ−ｄｉ−４−ｔｏｌｙｌａｍｉｎｏ）ｐｙｒｅｎｅ）とＡｌｑ３（トリス（８−キノリノラト）アルミニウム）とをｔ（ｄｔａ）ｐｙのドープ濃度が１質量％となるように且つ層厚が３０ｎｍとなるように真空蒸着法に依る共蒸着を行って発光層を形成する。 (5) Next, using a boat made of Ta, t (dta) py (1,3,6,8-tetra (N, N-di-4-tolyamino) pyrene) and Alq3 (Tris (8-quinolinolato) The light emitting layer is formed by performing co-evaporation with aluminum so that the doping concentration of t (dta) py is 1% by mass and the layer thickness is 30 nm.
（６） 次に、Ａｌｑ３をＴａからなるボートを用いて層厚が２０ｎｍとなるように成膜して電子輸送層を形成する。 (6) Next, an electron transport layer is formed by depositing Alq3 using a boat made of Ta so as to have a layer thickness of 20 nm.
（７） 次に、Ｍｏからなるボートを用いてＬｉＦを０．５ｎｍの厚さに、そして、Ｗフィラメントを用いてＡｌを１．５ｎｍの厚さにそれぞれ真空蒸着法にて成膜して電子注入層を形成する。 (7) Next, LiF is formed to a thickness of 0.5 nm using a boat made of Mo, and Al is formed to a thickness of 1.5 nm using a W filament by a vacuum evaporation method. An injection layer is formed.
（８） 次に、Ｍｏからなるボートを用いてＡｇを１５ｎｍの厚さに成膜して陰極を形成し、次に、Ｍｏからなるボートを用いて前記Ａｇからなる陰極上にＺｎＳを２５ｎｍの厚さに成膜してキャッピング層を形成してトップエミッション型有機ＥＬ素子を作製し、最後に、ガラス基板を用いて露点温度−６０℃以下の乾燥窒素雰囲気下でＵＶ接着材にて封止した。 (8) Next, using a boat made of Mo, Ag is formed to a thickness of 15 nm to form a cathode, and then using a boat made of Mo, ZnS is deposited on the cathode made of Ag to a thickness of 25 nm. A top emission type organic EL device is formed by forming a capping layer to a thickness, and finally sealed with a UV adhesive using a glass substrate in a dry nitrogen atmosphere with a dew point temperature of −60 ° C. or lower. did.
実施例２
実施例１と相違するところは、Ａｌからなる光反射性陽極を形成した後、その上にＷフィラメントを用いて陽極バッファー層である厚さ１ｎｍのＮｉを真空蒸着法を適用して成膜し、その後、基板表面をＵＶオゾンで２０分間の処理を行なう点にある。従って、正孔注入層はＡｌ上でなくＮｉ上に形成されることになる。
Example 2
The difference from Example 1 is that after forming a light-reflective anode made of Al, a 1 nm thick Ni film serving as an anode buffer layer is formed thereon by applying a vacuum deposition method using a W filament. Thereafter, the substrate surface is treated with UV ozone for 20 minutes. Therefore, the hole injection layer is formed not on Al but on Ni.
実施例３
実施例１及び実施例２と相違するところは、Ａｌからなる光反射性陽極を形成した後、その上にＭｏからなるボートを用いて陽極バッファー層である厚さ２ｎｍのＭｏＯ3 を真空蒸着法を適用して成膜する点、及び、第二正孔注入層の層厚が１６５ｎｍでなく１７０ｎｍにした点にある。尚、当然のことながら、正孔注入層はＡｌやＮｉの上でなく、ＭｏＯ3 上に形成されることになる。
Example 3
The difference from Example 1 and Example 2 is that after a light reflective anode made of Al is formed, MoO 3 having a thickness of 2 nm as an anode buffer layer is vacuum-deposited thereon using a boat made of Mo. And the thickness of the second hole injection layer is 170 nm instead of 165 nm. As a matter of course, the hole injection layer is not formed on Al or Ni but on MoO 3 .
実施例４
実施例３と相違するところは、陽極バッファー層であるＭｏＯ3 上に成膜される第一正孔注入層として２−ＴＮＡＴＡとＶ2 Ｏ5 を用いる代わりに２−ＴＮＡＴＡとＭｏＯ3 をドープ量が２−ＴＮＡＴＡとに対して３０質量％となるように変更して共蒸着した点にある。
Example 4
Where different from the third embodiment, the doping amount of 2-TNATA and MoO 3 instead of using 2-TNATA and V 2 O 5 as the first hole injection layer to be deposited on the MoO 3 is an anode buffer layer However, it changed to become 30 mass% with respect to 2-TNATA, and is in the point co-deposited.
（比較例１）
前記本発明の実施例と相違するところは、表面をＵＶオゾンで２０分間の処理を行なったＮｉからなる陽極バッファー層上にＴａからなるボートを用いて第二正孔注入層である２−ＴＮＡＴＡ、及び、同じくＴａからなるボートを用いてＦ４−ＴＣＮＱをＦ４−ＴＣＮＱのドープ濃度が０．１質量％となるように層厚１８５ｎｍまで共蒸着した点にある。
(Comparative Example 1)
The difference from the embodiment of the present invention is that 2-TNATA is a second hole injection layer using a boat made of Ta on an anode buffer layer made of Ni whose surface has been treated with UV ozone for 20 minutes. In addition, F4-TCNQ is co-deposited to a layer thickness of 185 nm so that the doping concentration of F4-TCNQ is 0.1% by mass using a boat made of Ta.
（比較例２）
純水→アセトン→純水→ＩＰＡの各１５分超音波洗浄を行った陽極ＩＴＯ付きガラス基板表面をＵＶオゾンで２０分処理した。次に、ＩＴＯ上にＴａボートを用いて第二正孔注入層である２−ＴＮＡＴＡとＴａボートを用いてＦ４−ＴＣＮＱとをＦ４−ＴＣＮＱのドープ濃度が０．１質量％となるように層厚１８５ｎｍまで真空蒸着に依り共蒸着を行なった。次に、正孔輸送層ＮＰＤをＴａボートを用いて１０ｎｍの厚さに成膜した。更に、ｔ（ｄｔａ）ｐｙとＡｌｑ３とをそれぞれＴａボートを用いてｔ（ｄｔａ）ｐｙのドープ濃度が１質量％となるように共蒸着を行い、層厚３０ｎｍの発光層を成膜した。次に、電子輸送層としてＡｌｑ３をＴａボートを用いて層厚２０ｎｍ成膜した。次に、電子注入層としてＭｏボートを用いてＬｉＦを０．５ｎｍの厚さに真空蒸着法を適用して成膜した。次に、Ｗフィラメントを用いて陰極Ａｌを８０ｎｍの厚さに真空蒸着法を適用して成膜し、ボトムエミッション型有機ＥＬ素子を作製した。最後に、ガラス基板を用いて露点温度−６０Ｃ°以下の乾燥窒素雰囲気下でＵＶ接着材にて封止を行った。
(Comparative Example 2)
The surface of the glass substrate with anode ITO that was subjected to ultrasonic cleaning for 15 minutes each of pure water → acetone → pure water → IPA was treated with UV ozone for 20 minutes. Next, a layer of 2-TNATA, which is a second hole injection layer, is formed on ITO using a Ta boat and F4-TCNQ using a Ta boat so that the doping concentration of F4-TCNQ is 0.1% by mass. Co-evaporation was performed by vacuum deposition up to a thickness of 185 nm. Next, a hole transport layer NPD was formed to a thickness of 10 nm using a Ta boat. Further, t (dta) py and Alq3 were co-deposited using a Ta boat so that the doping concentration of t (dta) py was 1% by mass to form a light emitting layer having a layer thickness of 30 nm. Next, Alq3 was deposited as an electron transport layer with a thickness of 20 nm using a Ta boat. Next, using an Mo boat as an electron injection layer, LiF was formed to a thickness of 0.5 nm by applying a vacuum deposition method. Next, cathode Al was formed into a film with a thickness of 80 nm using a W filament by applying a vacuum evaporation method, and a bottom emission type organic EL device was produced. Finally, sealing was performed with a UV adhesive in a dry nitrogen atmosphere having a dew point temperature of −60 C ° or less using a glass substrate.
（比較例３）
比較例２と同様なボトムエミッション型有機ＥＬ素子であるが、そのＩＴＯ上に形成する正孔注入層が本発明の実施例、例えば、実施例１と同じ構成になっている。即ち、実施例１と同じく、第一の正孔注入層及び第二の正孔注入層を備えている。
(Comparative Example 3)
Although it is a bottom emission type organic EL element similar to Comparative Example 2, the hole injection layer formed on the ITO has the same configuration as that of the example of the present invention, for example, Example 1. That is, as in Example 1, the first hole injection layer and the second hole injection layer are provided.
前記説明した実施例１〜４及び比較例１〜３の各素子構成を纏めて表１に示し、また、それらの各素子の駆動電流１５ｍＡ／ｃｍ２とした場合の素子特性を表２に示してある。 Wherein collectively the elements configuration of Examples 1 to 4 and Comparative Examples 1 to 3 described in Table 1, also shows the device characteristics when the drive current 15 mA / cm 2 of their respective elements shown in Table 2 It is.
これらの有機ＥＬ素子は全て緑色の発光を行うものであり、図２には駆動電流を１５ｍＡ／ｃｍ２とした場合に於ける素子の輝度劣化を表している。 All of these organic EL elements emit green light, and FIG. 2 shows the luminance degradation of the elements when the drive current is 15 mA / cm 2 .
比較例１は従来技術に依って陽極および正孔注入層を構成したトップエミッション型有機ＥＬ素子であり、そして、比較例２は従来技術によるボトムエミッション型有機ＥＬ素子である。比較例１の素子では、Ａｌからなる反射性陽極とＡｇからなる光半透過陰極を用いることによって、前述の微小空洞共振器（マイクロキャビティ）効果により、発光スペクトルが急峻となり、色純度が向上し、更には発光効率も向上することが確認されている。然しながら、輝度半減時間は比較例２の素子の１０００時間に対し、比較例１の素子では６５時間であって、素子寿命は極端に悪くなっている。然しながら、本発明に依る実施例１の素子では、比較例１の高色純度、高発光効率を維持しながら、輝度半減時間が２３００時間と大幅に改善されている。これは、比較例２の素子に対しても２．３倍の値である。実施例２に於いても、高色純度、高発光効率を維持しながら、輝度半減時間が比較例２と同等の１０００時間まで改善されている。実施例３及び４に於いては、陽極バッファー層にＭｏＯ3 を導入することにより、実施例１と同等の輝度半減時間が得られ、しかも、駆動電圧は低電圧化し、発光効率は向上している。陽極にＩＴＯを用いた比較例２と比較例３とでは輝度半減時間に差は見られなかった。 Comparative Example 1 is a top emission type organic EL element in which an anode and a hole injection layer are configured according to the conventional technique, and Comparative Example 2 is a bottom emission type organic EL element according to the conventional technique. In the element of Comparative Example 1, by using the reflective anode made of Al and the light semi-transmissive cathode made of Ag, the emission spectrum becomes steep and the color purity is improved by the above-described microcavity effect. Furthermore, it has been confirmed that the luminous efficiency is also improved. However, the luminance half time is 65 hours for the element of Comparative Example 1 as compared to 1000 hours for the element of Comparative Example 2, and the element life is extremely deteriorated. However, in the device of Example 1 according to the present invention, the luminance half-life is significantly improved to 2300 hours while maintaining the high color purity and high light emission efficiency of Comparative Example 1. This is 2.3 times the value of the element of Comparative Example 2. In Example 2, the luminance half-life is improved to 1000 hours, which is the same as that of Comparative Example 2, while maintaining high color purity and high luminous efficiency. In Examples 3 and 4, by introducing MoO 3 into the anode buffer layer, a luminance half time equivalent to that in Example 1 can be obtained, and the driving voltage is lowered and the luminous efficiency is improved. Yes. There was no difference in brightness half-life between Comparative Example 2 and Comparative Example 3 using ITO as the anode.
実施例５
（１） 純水→アセトン→純水→ＩＰＡの順に各１５分の超音波洗浄を行ったガラス基板上にＷフィラメントを用いて光反射性陽極を構成する厚さ６０ｎｍのＡｌ膜を真空蒸着法にて成膜した。その後、基板表面をＵＶオゾンで２０分の処理を行った。
Example 5
(1) A 60 nm thick Al film constituting a light-reflective anode using a W filament on a glass substrate that has been subjected to ultrasonic cleaning for 15 minutes each in the order of pure water → acetone → pure water → IPA by vacuum deposition The film was formed. Thereafter, the substrate surface was treated with UV ozone for 20 minutes.
（２） 次に、Ａｌからなる光反射性陽極上にＭｏからなるボートを用いてＭｏＯ3 からなる陽極バッファー層を厚さが２ｎｍとなるように真空蒸着法にて成膜した。 (2) Next, an anode buffer layer made of MoO 3 was formed on the light-reflecting anode made of Al by a vacuum vapor deposition method so that the thickness was 2 nm using a boat made of Mo.
（３） 次に、ＭｏＯ3 からなる陽極バッファー層上にＴａボートを用いて２−ＴＮＡＴＡとＭｏボートを用いて酸化モリブデン（ＭｏＯ3 ）とをＭｏＯ3 ドープ濃度が３０質量％となるように且つ層厚が２０ｎｍとなるように真空蒸着法に依る共蒸着を行って正孔注入層を形成する。 (3) Next, a Ta boat is used on the anode buffer layer made of MoO 3 and 2-TNATA and Mo boat are used to add molybdenum oxide (MoO 3 ) so that the MoO 3 doping concentration becomes 30% by mass. The hole injection layer is formed by performing co-evaporation by a vacuum deposition method so that the layer thickness becomes 20 nm.
（４） 次に、Ｔａからなるボートを用いて２−ＴＮＡＴＡと、同じくＴａからなるボートを用いてＦ４−ＴＣＮＱとをＦ４−ＴＣＮＱのドープ濃度が０．１質量％となるように且つ層厚が１７０ｎｍとなるように真空蒸着法に依る共蒸着を行って正孔注入層を形成する。 (4) Next, 2-TNATA is used using a boat made of Ta, and F4-TCNQ is similarly used using a boat made of Ta so that the doping concentration of F4-TCNQ is 0.1% by mass and the layer thickness is The hole injection layer is formed by performing co-evaporation by a vacuum deposition method so that the thickness becomes 170 nm.
（５） 次に、Ｔａからなるボートを用いてＮＰＤを層厚が１０ｎｍとなるように成膜して正孔輸送層を形成した。 (5) Next, a hole transport layer was formed by depositing NPD so as to have a layer thickness of 10 nm using a boat made of Ta.
（６） 次に、Ｔａからなるボートを用いてｔ（ｄｔａ）ｐｙとＡｌｑ３とをｔ（ｄｔａ）ｐｙのドープ濃度が１質量％となるように且つ層厚が３０ｎｍとなるように真空蒸着法に依る共蒸着を行って発光層を形成する。 (6) Next, using a boat made of Ta, a vacuum deposition method of t (dta) py and Alq3 so that the doping concentration of t (dta) py is 1% by mass and the layer thickness is 30 nm. The light emitting layer is formed by performing co-evaporation according to the above.
（７） 次に、Ｔａからなるボートを用いてＡｌｑ３を層厚が２０ｎｍとなるように成膜して電子輸送層を形成する。 (7) Next, using a boat made of Ta, Alq3 is formed to a thickness of 20 nm to form an electron transport layer.
（８） 次に、Ｍｏからなるボートを用いてＬｉＦを０．５ｎｍの厚さに、そして、Ｗフィラメントを用いてＡｌを１．５ｎｍの厚さにそれぞれ真空蒸着法にて成膜して電子注入層を形成する。 (8) Next, LiF is formed to a thickness of 0.5 nm using a boat made of Mo, and Al is formed to a thickness of 1.5 nm using a W filament by a vacuum evaporation method. An injection layer is formed.
（９） 次に、Ｍｏからなるボートを用いてＡｇを１５ｎｍの厚さに成膜して陰極を形成し、次に、Ｍｏからなるボートを用いて前記Ａｇからなる陰極上にＺｎＳを２５ｎｍの厚さに成膜してキャッピング層を形成してトップエミッション型有機ＥＬ素子を作製し、最後に、ガラス基板を用いて露点温度−６０Ｃ°以下の乾燥窒素雰囲気下でＵＶ接着材にて封止した。 (9) Next, using a boat made of Mo, Ag is formed to a thickness of 15 nm to form a cathode, and then using a boat made of Mo, ZnS is deposited on the cathode made of Ag to a thickness of 25 nm. A top emission type organic EL element is formed by forming a capping layer by forming a thickness, and finally sealed with a UV adhesive in a dry nitrogen atmosphere having a dew point temperature of −60 ° C. or lower using a glass substrate. did.
実施例６
実施例５と相違するところは、Ａｌからなる光反射性陽極を形成した後、基板表面を出力２００Ｗ、Ｏ2 流量０．２ｓｃｃｍとした酸素プラズマを適用して１分間の処理を行う点にある。
Example 6
The difference from Example 5 is that after forming a light-reflective anode made of Al, the substrate surface is subjected to treatment for 1 minute by applying oxygen plasma with an output of 200 W and an O 2 flow rate of 0.2 sccm. .
実施例７
実施例５と相違するところは、スパッタ法を適用することに依り、ガラス基板に層厚が１００ｎｍであるＡｌ−Ｎｄからなる光反射性陽極を形成し、次いで、実施例５と同様に超音波洗浄を行い、次いで、実施例６と同様にプラズマ処理を行い、次いで、実施例４と同様にＭｏＯ3 からなる陽極バッファー層を形成するのであるが、その陽極バッファー層は、当然、Ａｌ−Ｎｄからなる光反射性陽極上に形成される。そして、ＭｏＯ3 からなる陽極バッファー層上には２−ＴＮＡＴＡ及びＭｏＯ3 をＭｏＯ3 のドープ濃度が３０質量％となるように真空蒸着法にて共蒸着して正孔注入層とする点にある。
Example 7
The difference from Example 5 is that a light-reflective anode made of Al—Nd having a layer thickness of 100 nm is formed on a glass substrate by applying a sputtering method, and then ultrasonic waves are applied as in Example 5. After cleaning, plasma treatment is performed in the same manner as in Example 6, and then an anode buffer layer made of MoO 3 is formed in the same manner as in Example 4. Naturally, the anode buffer layer is made of Al—Nd. Formed on a light reflective anode. Then, the anode buffer layer consisting of MoO 3 lies in that the 2-TNATA and were co-deposited by vacuum deposition MoO 3 as the doping concentration of MoO 3 is 30 wt% HIL .
実施例８
実施例５と相違するところは、スパッタ法を適用することに依り、ガラス基板に層厚が１００ｎｍであるＡｌ−Ｎｄ膜と層厚が１５ｎｍであるＭｏ膜の積層構造からなる光反射性陽極を形成してから実施例５と同様に超音波洗浄し、且つ、実施例６と同様にプラズマ処理する点、そして、Ａｌ−Ｎｄ／Ｍｏからなる光反射性陽極上には、Ｔａからなるボートを用いて２−ＴＮＡＴＡと、Ｍｏからなるボートを用いて酸化バナジウム（Ｖ2 Ｏ5 ）とをＶ2 Ｏ5 のドープ濃度が３３質量％となるように且つ層厚が２０ｎｍとなるように真空蒸着法により共蒸着を行って第一正孔注入層を形成する点にある。尚、第一正孔注入層に積層する第二正孔注入層の形成については実施例５乃至実施例７と変わりない。
Example 8
The difference from Example 5 is that a light reflective anode comprising a laminated structure of an Al—Nd film having a layer thickness of 100 nm and a Mo film having a layer thickness of 15 nm is applied to a glass substrate by applying a sputtering method. After the formation, ultrasonic cleaning is performed in the same manner as in Example 5, and plasma treatment is performed in the same manner as in Example 6. On the light-reflective anode made of Al—Nd / Mo, a boat made of Ta is placed. Using 2-TNATA and a boat made of Mo, Vanadium oxide (V 2 O 5 ) is vacuum-deposited so that the V 2 O 5 doping concentration is 33% by mass and the layer thickness is 20 nm. The point is that co-evaporation is performed by the method to form the first hole injection layer. The formation of the second hole injection layer laminated on the first hole injection layer is the same as in Examples 5 to 7.
以上説明した実施例５〜８の各素子構成を纏めて表３に示し、また、それらの各素子の駆動電流を１５ｍＡ／ｃｍ２とした場合の素子特性を表４に示してある。 The element configurations of Examples 5 to 8 described above are collectively shown in Table 3, and the element characteristics when the drive current of each element is 15 mA / cm 2 are shown in Table 4.
これらの有機ＥＬ素子はすべて緑色の発光を行うものであり、Ａｌからなる光反射性陽極の表面をＵＶオゾン処理した実施例５及びＯ2 プラズマ処理した実施例６は共に実施例４と同様に高色純度、高発光効率、高寿命を示した。また、陽極にＡｌ−Ｎｄを用いた実施例７に於いても、実施例４と同様に高色純度、高発光効率を示し、輝度半減時間も比較例２を上回った。また、陽極にＭｏを用いた実施例８では、Ｍｏからなる光反射性陽極の反射率はＡｌに比較して低下するので発光効率は他の実施例より減少するが、輝度半減時間は比較例を上回った。 All of these organic EL elements emit green light, and both the Example 5 in which the surface of the light-reflecting anode made of Al was treated with UV ozone and the Example 6 in which O 2 plasma was treated were the same as in Example 4. It showed high color purity, high luminous efficiency, and long life. Further, in Example 7 using Al—Nd as the anode, high color purity and high luminous efficiency were exhibited as in Example 4, and the luminance half-life exceeded that of Comparative Example 2. In Example 8 using Mo for the anode, the reflectance of the light reflective anode made of Mo is lower than that of Al, so that the luminous efficiency is lower than that of the other examples. Exceeded.
実施例９
実施例６において、基板をガラス基板から両面にＳｉＮｘからなるガスバリア膜が配されたＰＥＴからなるフレキシブル基板に変更し、かつ封止をＵＶ接着材による封止からスパッタ法で形成したＳｉＮｘからなる封止膜に変更し、その他は実施例６と同様にして有機ＥＬ素子を作製した。
実施例９で作製した素子は、実施例６と同程度の発光特性を示し、また良い可撓性も示した。
Example 9
In Example 6, the substrate is changed from a glass substrate to a flexible substrate made of PET in which a gas barrier film made of SiNx is arranged on both sides, and the sealing is made of a sealing material made of SiNx formed by sputtering from sealing with a UV adhesive. The organic EL element was produced in the same manner as in Example 6 except that the film was changed to the stop film.
The device produced in Example 9 showed the same light emission characteristics as Example 6, and also showed good flexibility.
本発明に於いては、前記説明した実施の形態を含め、多くの形態で実施することができる。 The present invention can be implemented in many forms including the above-described embodiment.
２１ 基板
２２ 光反射性陽極
２３ 陽極バッファー層
２４ 正孔注入層
２５ 正孔注入層２４を構成する第一正孔注入層
２６ 正孔注入層を構成する第二正孔注入層
２７ 正孔輸送層
２８ 発光層
２９ 電子輸送層
３０ 光透過性陰極
３１ キャッピング層
21 substrate 22 light reflective anode 23 anode buffer layer 24 hole injection layer 25 first hole injection layer 26 constituting hole injection layer 24 second hole injection layer 27 constituting hole injection layer hole transport layer 28 Light-emitting layer 29 Electron transport layer 30 Light transmissive cathode 31 Capping layer
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