JP2009239180A - Organic electroluminescent device - Google Patents
Organic electroluminescent device Download PDFInfo
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- JP2009239180A JP2009239180A JP2008086244A JP2008086244A JP2009239180A JP 2009239180 A JP2009239180 A JP 2009239180A JP 2008086244 A JP2008086244 A JP 2008086244A JP 2008086244 A JP2008086244 A JP 2008086244A JP 2009239180 A JP2009239180 A JP 2009239180A
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- Prior art keywords
- light
- layer
- light emitting
- compound
- emitting layer
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Images
Abstract
Description
本発明は、有機エレクトロルミネッセンス素子、およびその製造方法、バックライト並びに液晶表示装置に関する。 The present invention relates to an organic electroluminescence element, a manufacturing method thereof, a backlight, and a liquid crystal display device.
液晶表示装置は、液晶セルと、液晶セルに電場を生じさせる一対の電極と、液晶セルを挟んで配置される一対の偏光板と、該一対の偏光板の一方に光を照射するバックライトとを含んで構成される。バックライトから放射された光は、１枚目の偏光板（一対の偏光板の一方）を通り、さらに液晶セルを通って２枚目の偏光板（一対の偏光板の他方）に入射する。液晶セルを透過する光は、液晶セルに生じる電場に応じて偏光の向きが変わり、２枚目の偏光板に入射する際の偏光の向きに応じて偏光板を透過するか、または偏光板で遮られる。液晶表示装置では、液晶セルにかける電場を制御することで、２枚目の偏光板を透過する光を制御し、画像情報を表示している。 The liquid crystal display device includes a liquid crystal cell, a pair of electrodes that generate an electric field in the liquid crystal cell, a pair of polarizing plates arranged with the liquid crystal cell sandwiched therebetween, and a backlight that irradiates one of the pair of polarizing plates with light. It is comprised including. The light emitted from the backlight passes through the first polarizing plate (one of the pair of polarizing plates), and further enters the second polarizing plate (the other of the pair of polarizing plates) through the liquid crystal cell. The direction of polarization of light transmitted through the liquid crystal cell changes depending on the electric field generated in the liquid crystal cell, and passes through the polarizing plate according to the direction of polarized light when entering the second polarizing plate, or by the polarizing plate. Blocked. In the liquid crystal display device, by controlling the electric field applied to the liquid crystal cell, the light transmitted through the second polarizing plate is controlled to display image information.
通常のバックライトから放射される光は無偏光である。偏光板は所定の方向に偏光する光のみを通すので、バックライトから放射される光の大部分が１枚目の偏光板で遮られ、有効に利用されておらず、このことが消費電力の高くなる原因の一つとなっている。そこで一方向に偏光した光を多く発する光源を用いることで、１枚目の偏光板で遮られる光の割合を低減し、多くの光を有効に利用する技術が提案されている。このような光源の一つとして有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子という場合がある。）を利用することが考えられている。 Light emitted from a normal backlight is unpolarized. Since the polarizing plate allows only light polarized in a predetermined direction to pass, most of the light emitted from the backlight is blocked by the first polarizing plate and is not used effectively. It is one of the causes of the increase. Therefore, a technique has been proposed in which a light source that emits a large amount of light polarized in one direction is used to reduce the proportion of light blocked by the first polarizing plate and to effectively use a large amount of light. As one of such light sources, it is considered to use an organic electroluminescence element (hereinafter sometimes referred to as an organic EL element).
通常の有機ＥＬ素子は、一対の電極と、この電極間に位置する発光層とを含んで構成される。有機ＥＬ素子に電圧を印加すると、陰極から電子が注入されるとともに、陽極から正孔が注入され、これら電子と正孔とが発光層で結合することによって発光する。通常の有機ＥＬ素子から取出される光は無偏光であるが、一軸配向した部材で発光層を構成することで、偏光光を発する有機ＥＬ素子が提案されている。 A normal organic EL element includes a pair of electrodes and a light emitting layer positioned between the electrodes. When a voltage is applied to the organic EL element, electrons are injected from the cathode, holes are injected from the anode, and light is emitted by combining these electrons and holes in the light emitting layer. Although light extracted from a normal organic EL element is non-polarized light, an organic EL element that emits polarized light has been proposed by forming a light emitting layer with a uniaxially oriented member.
従来の技術では配向膜上に発光層を形成することで、発光層を構成する化合物を一軸配向している。具体的にはラビングした膜を配向膜として用いたり、一軸配向した部材で構成した膜を配向膜として用いている（例えば特許文献１参照）。このような偏光発光する有機ＥＬ素子を光源に用いることで偏光板による光の損失を低減している。 In the conventional technique, the compound constituting the light emitting layer is uniaxially oriented by forming the light emitting layer on the alignment film. Specifically, a rubbed film is used as the alignment film, or a film formed of a uniaxially oriented member is used as the alignment film (see, for example, Patent Document 1). By using such an organic EL element that emits polarized light as a light source, light loss due to the polarizing plate is reduced.
例えばラビリング処理を施す際には、膜を物理的に削ることになるので、膜および他の層に損傷を与えるおそれがあり、さらにラビング処理を行うと微小な粉塵が生じるので、この粉塵に起因して短絡の生じるおそれがあり、信頼性の高い有機ＥＬ素子を製造することができない。また一軸配向した部材で構成した膜を配向膜として用いた場合には、前述したラビング処理を行う場合の問題が生じないが、ラビングを施した配向膜を用いた場合に比べると発光層を構成する部材が高度に配向せず、偏光度合いの高い偏光光を発する有機ＥＬ素子を実現することが難しい。 For example, when the rubbing process is performed, the film is physically scraped, which may damage the film and other layers. Further, when the rubbing process is performed, minute dust is generated. As a result, a short circuit may occur, and a highly reliable organic EL element cannot be manufactured. In addition, when a film composed of uniaxially oriented members is used as the alignment film, there is no problem in performing the rubbing process described above, but the light emitting layer is configured as compared with the case where the rubbing alignment film is used. It is difficult to realize an organic EL element that emits polarized light with a high degree of polarization because the member to be oriented is not highly oriented.
従って本発明の目的は、偏光度合いの高い光を発する有機エレクトロルミネッセンス素子、およびおよびその製造方法、バックライト並びに液晶表示装置を提供することである。 Accordingly, an object of the present invention is to provide an organic electroluminescence element that emits light having a high degree of polarization, a manufacturing method thereof, a backlight, and a liquid crystal display device.
本発明は、一対の電極と、該一対の電極の間に位置する発光層とを含む有機エレクトロルミネッセンス素子であって、
前記発光層が、光を照射することで少なくとも一部が一軸配向した光配向性化合物と、発光する有機化合物とを含んで構成されることを特徴とする有機エレクトロルミネッセンス素子である。
The present invention is an organic electroluminescence device comprising a pair of electrodes and a light emitting layer located between the pair of electrodes,
The organic light-emitting device is characterized in that the light-emitting layer includes a photo-alignment compound that is at least partially uniaxially aligned by irradiation with light and an organic compound that emits light.
また本発明は、前記発光層の一部を構成する前記有機化合物の一部が、前記光配向性化合物の配向に伴って一軸配向した液晶性化合物であることを特徴とする有機エレクトロルミネッセンス素子である。 Further, the present invention provides the organic electroluminescent device, wherein a part of the organic compound constituting a part of the light emitting layer is a liquid crystalline compound uniaxially aligned with the alignment of the photoalignable compound. is there.
また本発明は、前記一対の電極の間に位置し、前記発光層に接して設けられる機能層をさらに含み、
該機能層は、光を照射することで少なくとも一部が一軸配向した光配向性化合物を含んで構成されることを特徴とする有機エレクトロルミネッセンス素子である。
The present invention further includes a functional layer located between the pair of electrodes and provided in contact with the light emitting layer,
The functional layer is an organic electroluminescence device characterized in that it includes a photo-alignment compound that is at least partially uniaxially aligned by irradiation with light.
また本発明は、前記機能層が、正孔注入層であることを特徴とする有機エレクトロルミネッセンス素子である。 Moreover, this invention is an organic electroluminescent element characterized by the said functional layer being a positive hole injection layer.
また本発明は、前記機能層が、正孔輸送層であることを特徴とする有機エレクトロルミネッセンス素子である。 Moreover, this invention is an organic electroluminescent element characterized by the said functional layer being a positive hole transport layer.
また本発明は、前記機能層が、電子ブロック層であることを特徴とする有機エレクトロルミネッセンス素子である。 Moreover, this invention is an organic electroluminescent element characterized by the said functional layer being an electronic block layer.
また本発明は、前記発光層が、白色を発光することを特徴とする有機エレクトロルミネッセンス素子である。 Moreover, this invention is an organic electroluminescent element characterized by the said light emitting layer light-emitting white.
また本発明は、前記有機エレクトロルミネッセンス素子を備えるバックライトである。 Moreover, this invention is a backlight provided with the said organic electroluminescent element.
また本発明は、前記バックライトを備える液晶表示装置である。 Moreover, this invention is a liquid crystal display device provided with the said backlight.
また本発明は、一対の電極と、該一対の電極の間に位置する発光層とを含む有機エレクトロルミネッセンス素子の製造方法であって、
一対の電極のうちの一方の電極を形成する工程と、
発光層を形成する工程と、
一対の電極のうちの他方の電極を形成する工程とを含み、
発光層を形成する工程では、
光を照射することで配向する光配向性化合物と、発光する液晶性化合物とを含む塗布液を用いた塗布法により発光層用膜を形成し、
該発光層用膜に光を照射することで光配向性化合物および前記液晶性化合物の少なくとも一部を一軸配向させることを特徴とする有機エレクトロルミネッセンス素子の製造方法である。
Further, the present invention is a method for producing an organic electroluminescence element comprising a pair of electrodes and a light emitting layer located between the pair of electrodes,
Forming one of the pair of electrodes;
Forming a light emitting layer;
Forming the other electrode of the pair of electrodes,
In the step of forming the light emitting layer,
A light emitting layer film is formed by a coating method using a coating liquid containing a photoalignable compound that is aligned by irradiation with light and a liquid crystal compound that emits light,
A method for producing an organic electroluminescence device, wherein at least a part of a photoalignment compound and the liquid crystal compound is uniaxially oriented by irradiating the light emitting layer film with light.
また本発明は、前記発光層を形成する工程の前に、前記発光層用膜が表面上に形成される機能層を形成する工程をさらに含み、
機能層を形成する工程では、
液晶性化合物と、光を照射することで配向する光配向性化合物を含む塗布液を用いた塗布法により機能層用膜を形成し、
該機能層用膜に光を照射することで前記光配向性化合物の少なくとも一部を一軸配向させることを特徴とする前記有機エレクトロルミネッセンス素子の製造方法である。
The present invention further includes a step of forming a functional layer on the surface of which the light emitting layer film is formed before the step of forming the light emitting layer.
In the process of forming the functional layer,
A functional layer film is formed by a coating method using a liquid crystal compound and a coating liquid containing a photo-alignment compound that is aligned by irradiation with light,
The method for producing an organic electroluminescent element, wherein at least a part of the photoalignable compound is uniaxially oriented by irradiating the functional layer film with light.
発光層を構成する化合物を直接的に配向させるので、配向膜を用いて間接的に化合物を配向させる場合に比べて配向の度合いを高くすることができ、これによって偏光度合いの高い光を発する有機エレクトロルミネッセンス素子を実現することができる。 Since the compound constituting the light-emitting layer is directly oriented, the degree of orientation can be increased compared to the case where the compound is oriented indirectly using an orientation film, and thus organic light that emits light with a high degree of polarization. An electroluminescent element can be realized.
また光を照射することで化合物を配向させるので、物理的な損傷や粉塵が生じるラビリングなどを施す必要がなくなり、信頼性の高い有機エレクトロルミネッセンス素子を実現することができる。 In addition, since the compound is oriented by irradiating light, it is not necessary to perform physical damage or dusting that generates dust, and a highly reliable organic electroluminescence element can be realized.
図１は、本発明の実施の一形態の有機ＥＬ素子１を模式的に示す図である。本実施の形態の有機ＥＬ素子１は、一対の電極（以下、第１電極２および第２電極３という場合がある。）と、該一対の電極２，３の間に位置する発光層４とを含んで構成される。前記発光層４は、光を照射することで少なくとも一部が一軸配向した光配向性化合物と、発光する有機化合物とを含んで構成される。 FIG. 1 is a diagram schematically showing an organic EL element 1 according to an embodiment of the present invention. The organic EL element 1 of the present embodiment includes a pair of electrodes (hereinafter sometimes referred to as a first electrode 2 and a second electrode 3) and a light emitting layer 4 positioned between the pair of electrodes 2 and 3. It is comprised including. The light-emitting layer 4 includes a photo-alignment compound that is at least partially uniaxially aligned by irradiating light and an organic compound that emits light.
なお第１電極２と第２電極３との間には、一層の発光層４に限らずに、複数の発光層、及び／又は発光層とは異なる１または複数の層を設けてもよい。本実施の形態の有機ＥＬ素子１は、第１電極２と発光層４との間に正孔注入層５が設けられ、基板６、第１電極２、正孔注入層５、発光層４、第２電極３がこの順に接して積層されて構成される。 In addition, between the 1st electrode 2 and the 2nd electrode 3, you may provide not only the light emitting layer 4 of one layer but a several light emitting layer and / or 1 or several layer different from a light emitting layer. In the organic EL element 1 of the present embodiment, a hole injection layer 5 is provided between the first electrode 2 and the light emitting layer 4, and the substrate 6, the first electrode 2, the hole injection layer 5, the light emitting layer 4, The second electrode 3 is configured to be stacked in contact with each other in this order.
本実施の形態における第１電極２は陽極として機能し、第２電極３は陰極として機能する。また本実施の形態における２電極２および基板６は透光性を示し、第２電極３は可視光を反射する部材で構成される。したがって発光層４から第１電極２に向けて放射される光は、第１電極２および基板６を通って外に取出される。また発光層４から第２電極３に向けて放射される光は、第２電極３で反射され、第１電極２および基板６を通って外に取出される。すなわち本実施の形態の有機ＥＬ素子１は、基板６から光が取出されるボトムエミッション型の素子である。有機ＥＬ素子は、さらに封止膜または封止板などで封止される。なお変形例として第１電極を陰極とし、第２電極を陽極とするボトムエミッション型の有機ＥＬ素子を構成してもよく、また第２電極に透光性を示す電極を用いて第２電極側からも光を取出す両面発光の有機ＥＬ素子を構成してもよく、さらには第１電極に光を反射する電極を用い、第２電極に透光性を示す電極を用いて、基板ではなく第２電極から光を取出すトップエミッション型の有機ＥＬ素子を構成してもよい。 In the present embodiment, the first electrode 2 functions as an anode, and the second electrode 3 functions as a cathode. In addition, the two electrodes 2 and the substrate 6 in the present embodiment show translucency, and the second electrode 3 is made of a member that reflects visible light. Therefore, the light emitted from the light emitting layer 4 toward the first electrode 2 is taken out through the first electrode 2 and the substrate 6. The light emitted from the light emitting layer 4 toward the second electrode 3 is reflected by the second electrode 3 and taken out through the first electrode 2 and the substrate 6. That is, the organic EL element 1 of the present embodiment is a bottom emission type element in which light is extracted from the substrate 6. The organic EL element is further sealed with a sealing film or a sealing plate. As a modification, a bottom emission type organic EL element in which the first electrode is a cathode and the second electrode is an anode may be configured, and the second electrode side is formed by using a translucent electrode for the second electrode. Alternatively, a double-sided organic EL element that extracts light from the substrate may be configured. Furthermore, an electrode that reflects light is used for the first electrode, and a light-transmitting electrode is used for the second electrode, so that the first electrode is used instead of the substrate. You may comprise the top emission type organic EL element which takes out light from two electrodes.
本実施の形態の有機ＥＬ素子１は、発光層４の一部を構成する光配向性化合物の少なくとも一部が一軸配向しているので、光配向性化合物の配向方向に応じて、取出される光が偏光している。 The organic EL element 1 of the present embodiment is taken out according to the orientation direction of the photoalignment compound because at least a part of the photoalignment compound constituting a part of the light emitting layer 4 is uniaxially oriented. The light is polarized.
また発光層４の一部を構成する前記有機化合物の一部が、前記光配向性化合物の配向に伴って一軸配向した液晶性化合物であることが好ましい。この液晶性化合物は、後述する発光材料に相当し、該発光材料が光配向性化合物の配向方向と同じ方向に一軸配向していることが好ましい。このように光配向性化合物に加えて、光を発する液晶性化合物が光配向性化合物と同じ向きに配向することで、偏光度合いの高い光を発する有機ＥＬ素子１を実現することができる。ここで偏光度合いの高い光とは、取出される光のうちで所定の方向に偏光する光の割合が高い光を表す。 Moreover, it is preferable that a part of the organic compound constituting a part of the light emitting layer 4 is a liquid crystalline compound that is uniaxially aligned with the alignment of the photoalignable compound. This liquid crystalline compound corresponds to a light emitting material described later, and the light emitting material is preferably uniaxially aligned in the same direction as the alignment direction of the photoalignable compound. Thus, in addition to the photo-alignment compound, the liquid crystal compound that emits light is aligned in the same direction as the photo-alignment compound, whereby the organic EL element 1 that emits light with a high degree of polarization can be realized. Here, light having a high degree of polarization represents light having a high ratio of light polarized in a predetermined direction among extracted light.
前記一対の電極の間に位置し、前記発光層に接して設けられる機能層（本実施の形態では正孔注入層）は、光を照射することで少なくとも一部が一軸配向した光配向性化合物（本実施の形態では、後述する正孔注入材料）を含んで構成されることが好ましい。 A functional layer (hole injection layer in the present embodiment) located between the pair of electrodes and in contact with the light-emitting layer is a photo-alignment compound that is at least partially uniaxially aligned by irradiation with light. (In this embodiment, it is preferable to include a hole injection material described later).
後述するように発光層４が表面上に形成される層（本実施の形態では正孔注入層）を構成する化合物が所定の方向に配向していると、該層が配向膜として機能するので、単に光照射だけで発光層４中の化合物を配向する場合に比べて、配向度合いのより高い発光層４を構成することができる。これによって偏光度合いのより高い光を発する有機ＥＬ素子１を実現することができる。 As will be described later, if the compound constituting the layer on which the light emitting layer 4 is formed (hole injection layer in this embodiment) is oriented in a predetermined direction, the layer functions as an orientation film. The light emitting layer 4 having a higher degree of orientation can be formed as compared with the case where the compound in the light emitting layer 4 is oriented simply by light irradiation. Accordingly, the organic EL element 1 that emits light having a higher degree of polarization can be realized.
以下、本実施の形態の有機ＥＬ素子１の構成および製造方法について説明する。本実施の形態の有機ＥＬ素子の製造方法は、一対の電極のうちの一方の電極（第１電極２）を形成する工程と、発光層４を形成する工程と、一対の電極のうちの他方の電極（第２電極３）を形成する工程とを含み、発光層４を形成する工程では、光を照射することで配向する光配向性化合物と、発光する液晶性化合物とを含む塗布液を用いた塗布法により発光層用膜を形成し、該発光層薄膜に光を照射することで光配向性化合物および前記液晶性化合物の少なくとも一部を一軸配向させる。 Hereinafter, the structure and manufacturing method of the organic EL element 1 of this Embodiment are demonstrated. The manufacturing method of the organic EL element of the present embodiment includes a step of forming one electrode (first electrode 2) of the pair of electrodes, a step of forming the light emitting layer 4, and the other of the pair of electrodes. The step of forming the electrode (second electrode 3), and in the step of forming the light emitting layer 4, a coating liquid containing a photoalignable compound that is aligned by irradiation with light and a liquid crystal compound that emits light. A film for a light emitting layer is formed by the coating method used, and at least a part of the photoalignment compound and the liquid crystalline compound is uniaxially aligned by irradiating the light emitting layer thin film with light.
さらに本実施の形態の有機ＥＬ素子の製造方法では、前記発光層を形成する工程の前に、前記発光層薄膜が表面上に形成される機能層を形成する工程をさらに含み、機能層を形成する工程では、光を照射することで配向する光配向性化合物を含む塗布液を用いた塗布法により機能層薄膜を形成し、該機能層薄膜に光を照射することで光配向性化合物の少なくとも一部を一軸配向させることが好ましい。 Furthermore, in the method for manufacturing the organic EL element of the present embodiment, before the step of forming the light emitting layer, the method further includes the step of forming a functional layer on which the light emitting layer thin film is formed, and forming the functional layer In the step of forming, a functional layer thin film is formed by a coating method using a coating liquid containing a photoalignment compound that is aligned by irradiating light, and at least the photoalignment compound is irradiated by irradiating the functional layer thin film with light. It is preferable that a part is uniaxially oriented.
＜基板＞
基板は、可視光領域の光の透過率が高く、また有機ＥＬ素子を形成する工程において変化しないものが好適に用いられ、リジッド板でも、フレキシブル板でもよく、例えばガラス板、プラスチック板、高分子フィルムおよびシリコン板、並びにこれらを積層した積層板などが好適に用いられる。プラスチック板や高分子フィルムを構成する樹脂としては、例えば発光層４および正孔注入層５などを後述する塗布法で成膜する際に使用される塗布液に溶解しないものが好ましい。具体的には、低密度または高密度のポリエチレン、エチレン−プロピレン共重合体、エチレン−ブテン共重合体、エチレン−ヘキセン共重合体、エチレン−オクテン共重合体、エチレン−ノルボルネン共重合体、エチレン−ドモン共重合体、ポリプロピレン、エチレン−酢酸ビニル共重合体、エチレン−メチルメタクリレート共重合体、アイオノマー樹脂などのポリオレフィン系樹脂；ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル系樹脂；ナイロン−６、ナイロン−６，６、メタキシレンジアミン−アジピン酸縮重合体；ポリメチルメタクリルイミドなどのアミド系樹脂；ポリメチルメタクリレートなどのアクリル系樹脂；ポリスチレン、スチレン−アクリロニトリル共重合体、スチレン−アクリロニトリル−ブタジエン共重合体、ポリアクリロニトリルなどのスチレン−アクリロニトリル系樹脂；トリ酢酸セルロース、ジ酢酸セルロースなどの疎水化セルロース系樹脂；ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリテトラフルオロエチレンなどのハロゲン含有樹脂；ポリビニルアルコール、エチレン−ビニルアルコール共重合体、セルロース誘導体などの水素結合性樹脂；ポリカーボネート樹脂、ポリサルホン樹脂、ポリエーテルサルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンオキシド樹脂、ポリメチレンオキシド樹脂、ポリアリレート樹脂、液晶樹脂などのエンジニアリングプラスチック系樹脂などが挙げられる。
<Board>
A substrate having a high light transmittance in the visible light region and having no change in the process of forming the organic EL element is preferably used. The substrate may be a rigid plate or a flexible plate, for example, a glass plate, a plastic plate, a polymer A film, a silicon plate, and a laminated plate obtained by laminating these are preferably used. As the resin constituting the plastic plate or the polymer film, for example, a resin that does not dissolve in the coating solution used when the light emitting layer 4 and the hole injection layer 5 are formed by the coating method described later is preferable. Specifically, low density or high density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-norbornene copolymer, ethylene- Polyolefin resins such as domon copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; nylon-6 , Nylon-6,6, metaxylenediamine-adipic acid condensation polymer; amide resin such as polymethylmethacrylamide; acrylic resin such as polymethylmethacrylate; polystyrene, styrene-acrylonitrile copolymer Styrene-acrylonitrile resins such as styrene-acrylonitrile-butadiene copolymer and polyacrylonitrile; Hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate; Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene Halogen-containing resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, hydrogen bonding resins such as cellulose derivatives; polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene Examples include engineering plastic resins such as oxide resins, polyarylate resins, and liquid crystal resins.
作製プロセスでの耐熱性が基板には求められるので、上述の樹脂の中でもガラス転移点Ｔｇが、１５０℃以上の樹脂が好ましく、１８０℃以上の樹脂がより好ましく、２００℃以上の樹脂がさらに好ましい。 Since the substrate is required to have heat resistance in the production process, among the above resins, a glass transition point Tg of 150 ° C. or higher is preferable, 180 ° C. or higher is more preferable, and 200 ° C. or higher is more preferable. .
なお前述したトップエミッション型の有機ＥＬ素子では、基板から光が取出されないので透明の基板である必要がなく、透光性の基板でも不透光性の基板でもよい。 Note that the above-described top emission type organic EL element does not need to be a transparent substrate because light is not extracted from the substrate, and may be a translucent substrate or an opaque substrate.
＜第１電極＞
本実施の形態の第１電極２は、透光性および導電性を示す薄膜によって実現され、例えば金属酸化物膜および金属薄膜などによって構成される。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、インジウムスズ酸化物（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ：略称ＩＴＯ）、インジウム亜鉛酸化物（Ｉｎｄｉｕｍ Ｚｉｎｃ Ｏｘｉｄｅ：略称ＩＺＯ）、金、白金、銀、銅などの薄膜を挙げることができ、ＩＴＯ、ＩＺＯ、酸化スズなどの薄膜が好ましい。また第１電極２として、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体などの有機の透明導電膜を用いてもよい。第１電極２の厚みは、光透過性と導電性とを考慮して適宜設定することができ、一般的には１０ｎｍ〜１０μｍ程度であり、好ましくは２０ｎｍ〜１μｍ、さらに好ましくは５０ｎｍ〜５００ｎｍである。なお第１電極側から光を取出さない場合には、第１電極は不透明な陽極で実現されてもよい。
<First electrode>
The first electrode 2 of the present embodiment is realized by a thin film exhibiting translucency and conductivity, and is configured by, for example, a metal oxide film and a metal thin film. Specifically, thin films of indium oxide, zinc oxide, tin oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, and the like A thin film of ITO, IZO, tin oxide or the like is preferable. Further, as the first electrode 2, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. The thickness of the first electrode 2 can be appropriately set in consideration of light transmittance and conductivity, and is generally about 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there. When light is not extracted from the first electrode side, the first electrode may be realized by an opaque anode.
第１電極の形成方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法等が挙げられる。 Examples of the method for forming the first electrode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
＜正孔注入層＞
正孔注入層は、前述したように、好ましくは光を照射することで少なくとも一部が一軸配向した光配向性化合物を含んで構成される。正孔注入層は、光配向性化合物に加えて、正孔注入機能を有する正孔注入材料をさらに含んで構成される。
<Hole injection layer>
As described above, the hole injection layer preferably includes a photo-alignment compound that is at least partially uniaxially aligned by irradiation with light. The hole injection layer further includes a hole injection material having a hole injection function in addition to the photo-alignment compound.
正孔注入材料としては、フェニルアミン系、スターバースト型アミン系、フタロシアニン系、酸化バナジウム、酸化モリブデン、酸化ルテニウム、酸化アルミニウム等の酸化物、アモルファスカーボン、ポリアニリン、ポリチオフェン誘導体などが挙げられる。 Examples of the hole injection material include phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, and polythiophene derivatives.
本実施の形態の光配向性化合物は、光を照射することで配向する化合物であり、分子中に光異性化基、光二量化形成基、若しくは光分解する化学構造を有する低分子または高分子であって、公知の化合物を適宜用いることができ、市販品が入手可能である。光異性化基としては例えばアゾベンゼンが用いられ、光二量化形成基としては例えばシンナモイル基を有する化合物、クマリン、およびＪ．Ｐｈｏｔｏｐｏｌｙｍｅｒ Ｓｃｉ． Ｔｅｃｈ．，１１，１８７（１９９８）やＩＤＷ．， ８９（１９９９）に記載されているようなカルコン基を有する化合物などが好適に用いられ、光分解する化学構造を有する化合物としては、耐熱性、機械的強度の点でポリイミドが好適に用いられる。光配向性化合物は、これらの中でも、シンナモイル基やカルコン基を有する化合物が好ましい。正孔注入層を形成する工程では、まず例えば正孔注入機能を有する正孔注入材料と、光配向性化合物とを含む塗布液を用いた塗布法により機能層薄膜（正孔注入層用膜）を形成する。さらに、光配向性化合物が液晶性を示す化合物であると、配向性がより高まるので好ましい。 The photo-alignment compound of the present embodiment is a compound that is aligned by irradiating light, and is a low molecule or polymer having a photoisomerization group, a photodimerization group, or a photolytic chemical structure in the molecule. Thus, known compounds can be used as appropriate, and commercially available products are available. As the photoisomerization group, for example, azobenzene is used, and as the photodimerization group, for example, a compound having a cinnamoyl group, coumarin, and J. Org. Photopolymer Sci. Tech. 11, 187 (1998) and IDW. , 89 (1999), a compound having a chalcone group is preferably used, and a polyimide having a chemical structure capable of photolysis is preferably used in terms of heat resistance and mechanical strength. . Among these, the compound having a cinnamoyl group or a chalcone group is preferable as the photoalignment compound. In the step of forming the hole injection layer, first, a functional layer thin film (hole injection layer film) is formed by a coating method using a coating liquid containing a hole injection material having a hole injection function and a photo-alignment compound, for example. Form. Furthermore, it is preferable that the photo-alignment compound is a compound exhibiting liquid crystallinity because the alignment is further enhanced.
正孔注入層用の塗布液は、溶液でも乳濁液でもよい。正孔注入層用の塗布液の溶媒は、正孔注入材料および光配向性化合物を溶解する液体であればよく、また分散媒は、正孔注入材料および光配向性化合物を均質に分散可能な液体であればよい。溶媒としては、例えばクロロホルム、塩化メチレン、ジクロロエタン等の塩素系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン等の芳香族炭化水素系溶媒、アセトン、メチルエチルケトン等のケトン系溶媒、酢酸エチル、酢酸ブチル、エチルセルソルブアセテート等のエステル系溶媒、および水を挙げることができる。 The coating solution for the hole injection layer may be a solution or an emulsion. The solvent of the coating liquid for the hole injection layer may be any liquid that dissolves the hole injection material and the photo-alignment compound, and the dispersion medium can uniformly disperse the hole injection material and the photo-alignment compound. Any liquid may be used. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate and butyl acetate. And ester solvents such as ethyl cellosolve acetate and water.
塗布法としては、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイアーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、インクジェットプリント法等を挙げることができる。 As the coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, An offset printing method, an inkjet printing method, etc. can be mentioned.
次に、塗布法によって成膜された機能層薄膜（正孔注入層用膜）に光を照射することで光配向性化合物の少なくとも一部を一軸配向させて、正孔注入層を形成する。照射する光には、一方向に直線偏光した紫外線、または電子線等が用いられ、紫外線が好適に用いられる。 Next, the functional layer thin film (hole injection layer film) formed by the coating method is irradiated with light so that at least a part of the photo-alignment compound is uniaxially aligned to form a hole injection layer. As the irradiation light, ultraviolet rays linearly polarized in one direction, electron beams, or the like is used, and ultraviolet rays are preferably used.
例えば一方向に直線偏光した紫外線（ＵＶ）を機能層薄膜（正孔注入層用膜）に照射すると、光配向性化合物が所定の方向に配向し、配向膜として機能する正孔注入層が形成される。 For example, when the functional layer thin film (hole injection layer film) is irradiated with ultraviolet light (UV) linearly polarized in one direction, the photo-alignment compound is aligned in a predetermined direction, and a hole injection layer that functions as an alignment film is formed. Is done.
＜発光層＞
発光層は、光を照射することで少なくとも一部が一軸配向した光配向性化合物と、発光する有機化合物とを含んで構成され、該発光する有機化合物（以下、発光材料という場合がある）は、蛍光及び／又は燐光を光する有機物、若しくは該有機物と、ドーパントとを含んで構成される。ドーパントは、たとえば発光効率の向上や発光波長を変化させるなどの目的で付加される。発光材料は、低分子化合物または高分子化合物のいずれでもよく、液晶性を示す材料が好ましい。発光層を構成する発光材料としては、例えば以下のものを挙げることができる。発光層は、白色を発光することが好ましい。
<Light emitting layer>
The light emitting layer is configured to include a photoalignable compound that is at least partially uniaxially aligned by irradiation with light and an organic compound that emits light, and the organic compound that emits light (hereinafter sometimes referred to as a light emitting material) is , An organic substance that emits fluorescence and / or phosphorescence, or the organic substance and a dopant. The dopant is added for the purpose of, for example, improving luminous efficiency or changing the emission wavelength. The light emitting material may be either a low molecular compound or a high molecular compound, and a material exhibiting liquid crystallinity is preferable. Examples of the light emitting material constituting the light emitting layer include the following. The light emitting layer preferably emits white light.
色素系の発光材料としては、例えば、シクロペンダミン誘導体、テトラフェニルブタジエン誘導体化合物、トリフェニルアミン誘導体、オキサジアゾール誘導体、ピラゾロキノリン誘導体、ジスチリルベンゼン誘導体、ジスチリルアリーレン誘導体、ピロール誘導体、チオフェン環化合物、ピリジン環化合物、ペリノン誘導体、ペリレン誘導体、オリゴチオフェン誘導体、トリフマニルアミン誘導体、オキサジアゾールダイマー、ピラゾリンダイマーなどが挙げられる。 Examples of dye-based light emitting materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophenes. Examples thereof include a ring compound, a pyridine ring compound, a perinone derivative, a perylene derivative, an oligothiophene derivative, a trifumanylamine derivative, an oxadiazole dimer, and a pyrazoline dimer.
金属錯体系の発光材料としては、中心金属に、Ａｌ、Ｚｎ、Ｂｅなど、またはＴｂ、Ｅｕ、Ｄｙなどの希土類金属を有し、配位子に、オキサジアゾール、チアジアゾール、フェニルピリジン、フェニルベンゾイミダゾール、キノリン構造などを有する金属錯体を挙げることができ、例えば、イリジウム錯体、白金錯体等の三重項励起状態からの発光を有する金属錯体、アルミキノリノール錯体、ベンゾキノリノールベリリウム錯体、ベンゾオキサゾリル亜鉛錯体、ベンゾチアゾール亜鉛錯体、アゾメチル亜鉛錯体、ポルフィリン亜鉛錯体、ユーロピウム錯体などを挙げることができる。 The metal complex-based light emitting material includes Al, Zn, Be or the like as a central metal, or a rare earth metal such as Tb, Eu, or Dy, and oxadiazole, thiadiazole, phenylpyridine, or phenylbenzo as ligands. Examples include metal complexes having imidazole and quinoline structures, such as iridium complexes, platinum complexes, and other metal complexes that emit light from triplet excited states, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, and benzoxazolyl zinc. Examples include complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes.
高分子系の発光材料としては、ポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリパラフェニレン誘導体、ポリシラン誘導体、ポリアセチレン誘導体、ポリフルオレン誘導体、およびポリビニルカルバゾール誘導体など、並びに上記色素系の発光材料や金属錯体系の発光材料を高分子化したものなどが挙げられる。 Examples of polymer-based light-emitting materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, and polyvinylcarbazole derivatives, and the above-described dye-based light-emitting materials and metal complex systems. And a material obtained by polymerizing the light emitting material.
上記発光材料のうち、青色に発光する材料としては、ジスチリルアリーレン誘導体、オキサジアゾール誘導体、およびそれらの重合体、ポリビニルカルバゾール誘導体、ポリパラフェニレン誘導体、ポリフルオレン誘導体などを挙げることができる。なかでも高分子材料のポリビニルカルバゾール誘導体、ポリパラフェニレン誘導体やポリフルオレン誘導体などが好ましい。 Among the above light-emitting materials, examples of materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives. Of these, polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.
また、緑色に発光する材料としては、キナクリドン誘導体、クマリン誘導体、およびそれらの重合体、ポリパラフェニレンビニレン誘導体、ポリフルオレン誘導体などを挙げることができる。なかでも高分子材料のポリパラフェニレンビニレン誘導体、ポリフルオレン誘導体などが好ましい。 Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.
また、赤色に発光する材料としては、クマリン誘導体、チオフェン環化合物、およびそれらの重合体、ポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリフルオレン誘導体などを挙げることが出来る。なかでも高分子材料のポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリフルオレン誘導体などが好ましい。 Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Among these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.
ドーパント材料としては、例えば、ペリレン誘導体、クマリン誘導体、ルブレン誘導体、キナクリドン誘導体、スクアリウム誘導体、ポルフィリン誘導体、スチリル系色素、テトラセン誘導体、ピラゾロン誘導体、デカシクレン、フェノキサゾンなどを挙げることができる。 Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like.
液晶性を示す発光材料の具体的な一例としては、例えばＭａｃｒｏｍｏｌｅｃｕｌｅｓ２００３，３６、３４５７−３４６４、Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．２００６，８９，１２１９２０、Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ｂ１０７，４８８７（２００３）、日本化学会春季年会３Ｇ７−４０、Ｐｒｏｃ．ＳＰＩＥ２００５，５９６３，５９３６０Ｃに記載される液晶性発光材料が挙げられる。 Specific examples of the light-emitting material exhibiting liquid crystallinity include, for example, Macromolecules 2003, 36, 3457-3464, Appl. Phys. Lett. 2006, 89, 121920, J. MoI. Phys. Chem. B107, 4887 (2003), Chemical Society of Japan Spring Annual Meeting 3G7-40, Proc. Examples thereof include liquid crystal luminescent materials described in SPIE 2005, 5963, and 59360C.
以上の発光材料のうちで配向し易い材料という観点からは、室温から５０度の領域に液晶性を有するものが好ましい。なお、このような発光層の厚さは、通常約２ｎｍ〜２０００ｎｍである。 Of these light emitting materials, those having liquid crystallinity in a region from room temperature to 50 degrees are preferable from the viewpoint of easily aligning materials. In addition, the thickness of such a light emitting layer is usually about 2 nm-2000 nm.
発光層に用いられる光配向性化合物には、例えば正孔注入層に用いられる前述した光配向性化合物を用いることができ、これらの中でもシンナモイル基やカルコン基を有する化合物が光配向性の観点から好ましい。 As the photoalignable compound used in the light emitting layer, for example, the above-described photoalignable compound used in the hole injection layer can be used, and among these, compounds having a cinnamoyl group or a chalcone group are from the viewpoint of photoalignment. preferable.
発光層を形成する工程では、まず例えば発光層となる液晶性化合物（発光材料）および光配向性化合物を含む塗布液を用いた塗布法により発光層用膜を形成する。 In the step of forming the light emitting layer, first, for example, a film for the light emitting layer is formed by a coating method using a coating liquid containing a liquid crystal compound (light emitting material) to be the light emitting layer and a photoalignment compound.
発光層用の塗布液は、溶液でも乳濁液でもよい。発光層用の塗布液の溶媒は、液晶性化合物（発光材料）および光配向性化合物を溶解する液体であればよく、例えば正孔注入層用の塗布液の溶媒として挙げた溶媒を適宜用いることができ、また分散媒は、液晶性化合物（発光材料）および光配向性化合物を均質に分散可能な液体であればよい。 The coating solution for the light emitting layer may be a solution or an emulsion. The solvent of the coating liquid for the light emitting layer may be any liquid that dissolves the liquid crystalline compound (light emitting material) and the photoalignment compound. For example, the solvent mentioned as the solvent for the coating liquid for the hole injection layer is appropriately used. The dispersion medium may be any liquid that can uniformly disperse the liquid crystal compound (light emitting material) and the photo-alignment compound.
塗布法としては、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイアーバーコート法、ディップコート法、スリットコート法、キャピラリーコート法、スプレーコート法、ノズルコート法などのコート法、グラビア印刷法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、反転印刷法、インクジェットプリント法などを挙げることができる。パターン形成や多色の塗分けが容易であるという点で、グラビア印刷法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、反転印刷法、インクジェットプリント法などの塗布法が好ましい。また、昇華性の低分子化合物の場合には、真空蒸着法を用いることができる。さらには、レーザーによる転写や熱転写などの方法によって、所望するところのみに発光層を形成することもできる。 As the coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, Examples thereof include a coating method such as a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method. A coating method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method is preferable in that pattern formation and multicolor coating are easy. In the case of a sublimable low molecular compound, a vacuum deposition method can be used. Furthermore, the light emitting layer can be formed only at a desired place by a method such as laser transfer or thermal transfer.
次に、塗布法によって成膜された発光層用膜に光を照射することで液晶性化合物および光配向性化合物の少なくとも一部を一軸配向させて、発光層を形成する。照射する光には、一方向に直線偏光した紫外線、または電子線等が用いられ、紫外線が好適に用いられる。なお、発光層用膜に照射する光の偏光方向は、前述した正孔注入層用膜に照射した光の偏光方向と同じである。 Next, the light emitting layer film formed by a coating method is irradiated with light so that at least a part of the liquid crystalline compound and the photoalignable compound is uniaxially aligned to form a light emitting layer. As the irradiation light, ultraviolet rays linearly polarized in one direction, electron beams, or the like is used, and ultraviolet rays are preferably used. In addition, the polarization direction of the light irradiated to the light emitting layer film is the same as the polarization direction of the light irradiated to the hole injection layer film described above.
例えば一方向に直線偏光した紫外線（ＵＶ）を発光層用膜に照射すると、光配向性化合物が所定の方向に配向し、さらに該光配向性化合物の配向に追随して液晶性化合物（発光材料）が配向し、液晶性化合物および光配向性化合物の少なくとも一部が一軸配向した発光層が形成される。また正孔注入層が配向膜として機能するので、このような正孔注入層に接して発光層を形成することで、発光層を構成する化合物をより高度に配向させることができる。 For example, when the light emitting layer film is irradiated with ultraviolet light (UV) linearly polarized in one direction, the photo-alignment compound is aligned in a predetermined direction, and the liquid crystal compound (light-emitting material) is further followed by the alignment of the photo-alignment compound. ) Are aligned, and a light emitting layer in which at least a part of the liquid crystalline compound and the photoalignable compound is uniaxially aligned is formed. In addition, since the hole injection layer functions as an alignment film, the compound constituting the light emitting layer can be more highly oriented by forming the light emitting layer in contact with the hole injection layer.
＜第２電極＞
第２電極は、本実施の形態では陰極として機能し、このような第２電極の材料としては、仕事関数が小さく、発光層への電子注入が容易な材料が好ましく、また電気伝導度の高い材料が好ましい。具体的には、アルカリ金属、アルカリ土類金属、遷移金属およびＩＩＩ−Ｂ族金属などの金属を用いることができ、さらに具体的にはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウムなどの金属、または上記金属のうち２つ以上の合金、またはそれらのうち１つ以上と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫のうち１つ以上との合金、またはグラファイト若しくはグラファイト層間化合物などが用いられる。合金の例としては、マグネシウム−銀合金、マグネシウム−インジウム合金、マグネシウム−アルミニウム合金、インジウム−銀合金、リチウム−アルミニウム合金、リチウム−マグネシウム合金、リチウム−インジウム合金、カルシウム−アルミニウム合金などが挙げられる。なお透明な電極で第２電極を構成する場合には、第２電極は例えば上記の材料から成る薄膜と、導電性金属酸化物や導電性有機物などから成る薄膜とを積層した積層体で構成される。
<Second electrode>
The second electrode functions as a cathode in this embodiment, and the material of the second electrode is preferably a material having a low work function and easy electron injection into the light emitting layer, and has high electrical conductivity. Material is preferred. Specifically, metals such as alkali metals, alkaline earth metals, transition metals, and Group III-B metals can be used, and more specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium A metal such as strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, or an alloy of two or more of the above metals, or one or more of them, An alloy with one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or a graphite intercalation compound is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. In the case where the second electrode is constituted by a transparent electrode, the second electrode is constituted by a laminated body in which, for example, a thin film made of the above-described material and a thin film made of a conductive metal oxide or a conductive organic material are stacked. The
以上説明したように、ラビング処理などを施すことなく、光配向性化合物および液晶性化合物の少なくとも一部が配向した発光層を非接触で形成することができる。また配向膜として機能する正孔注入層を非接触で形成し、さらにこの正孔注入層に接して発光層を形成するので、発光層を構成する光配向性化合物および液晶性化合物をより高度に配向させることができる。このように物理的な損傷や粉塵が生じるラビリング処理などを必要とすることなく、発光層を構成する光配向性化合物および液晶性化合物を非接触で配向させることができるので、信頼性の高い有機ＥＬ素子を実現することができる。 As described above, the light emitting layer in which at least a part of the photo-alignment compound and the liquid crystal compound is aligned can be formed in a non-contact manner without performing a rubbing treatment or the like. In addition, a hole injection layer that functions as an alignment film is formed in a non-contact manner, and a light-emitting layer is formed in contact with the hole injection layer, so that the photo-alignment compound and liquid crystal compound constituting the light-emitting layer can be further enhanced. Can be oriented. Since the photo-alignment compound and the liquid crystal compound constituting the light-emitting layer can be aligned in a non-contact manner without the need for a physical damage or a rubbing treatment that generates dust, the organic layer is highly reliable. An EL element can be realized.
また、光を照射することで配向し、かつ発光する化合物を発光材料として用いたとしても、一軸配向した発光層を形成することもできるが、本実施の形態では、光配向化合物と発光材料とを用いることで一軸配向した発光層を実現している。光を照射することで配向し、かつ発光するという２つの機能を兼ね備える化合物を合成するためには、技術的な困難を伴うが、これに比べて本実施の形態では光配向性化合物と発光材料との組合せを見出すだけなので、一軸配向した発光層を容易に形成することができるとともに、設計の自由度が増す。なお本実施の形態では光配向材料を用いればよく、光を照射することで配向する発光材料を用いてもよい。 Further, even when a compound that emits light and is aligned and emits light is used as a light emitting material, a uniaxially oriented light emitting layer can be formed. Is used to realize a uniaxially oriented light emitting layer. In order to synthesize a compound that has two functions of aligning and emitting light by irradiating light, it involves technical difficulties, but in this embodiment, the photo-alignable compound and the light-emitting material are compared. Thus, a uniaxially oriented light emitting layer can be easily formed and the degree of freedom in design is increased. Note that a photo-alignment material may be used in this embodiment mode, and a light-emitting material that is aligned by light irradiation may be used.
なお発光層及び／又は正孔注入層に光配向性化合物を混入することで、発光効率が低下する可能性は否定できず、無偏光を発する有機ＥＬ素子よりも発光効率が低下することもありうる。しかしながら本実施の形態の有機ＥＬ素子は直線偏光を放出するのであり、従って放出される光の大部分が偏光板を通過して有効に利用されるので、光配向性化合物を混入することで発光効率が低下したとしても、偏光板を通した後の有効に利用される光の効率を比較すると、無偏光を発する通常の有機ＥＬ素子に比べて効率が高くなる。例えば無偏光では偏光板を通過することで光強度が５０程度％低下するが、仮に本実施の形態の有機ＥＬ素子から放出される光が１００％偏光板を通過すると仮定すると、光配向性化合物を混入することに起因する発光効率の低下が５０％未満であれば、有効に利用される光の発光効率を比較すると、無偏光を発する通常の有機ＥＬ素子に比べて効率が高くなる。 In addition, the possibility that the light emission efficiency is reduced by mixing the photo-alignment compound in the light emitting layer and / or the hole injection layer cannot be denied, and the light emission efficiency may be lower than that of the organic EL element emitting non-polarized light. sell. However, the organic EL element of the present embodiment emits linearly polarized light, and therefore most of the emitted light passes through the polarizing plate and is effectively used. Therefore, light is emitted by mixing the photo-alignment compound. Even if the efficiency is reduced, the efficiency of light that is effectively used after passing through the polarizing plate is higher than that of a normal organic EL element that emits non-polarized light. For example, in the case of non-polarized light, the light intensity decreases by about 50% by passing through the polarizing plate. However, assuming that light emitted from the organic EL element of the present embodiment passes through the polarizing plate 100%, the photo-alignment compound If the decrease in the light emission efficiency due to the mixing of light is less than 50%, the light emission efficiency of light that is used effectively is higher than that of a normal organic EL element that emits non-polarized light.
なお本実施の形態では正孔注入層を配向膜として用いたが、配向膜として機能しない正孔注入層を用いてもよく、このような正孔注入層は、光配向性化合物を含まなくてもよく、また正孔注入層を形成する工程において前述した光を照射する工程を省略できる。また正孔注入層を設けることなく、第１電極に接して発光層を形成してもよい。このように配向膜上に発光層を形成しなくとも、前述したように光を照射することで発光層を構成する光配向化合物および発光材料の少なくとも一部を一軸配向することができる。 In this embodiment, the hole injection layer is used as an alignment film. However, a hole injection layer that does not function as an alignment film may be used, and such a hole injection layer does not include a photo-alignment compound. In addition, the step of irradiating light described above in the step of forming the hole injection layer can be omitted. Further, the light emitting layer may be formed in contact with the first electrode without providing the hole injection layer. As described above, at least a part of the photo-alignment compound and the light-emitting material constituting the light-emitting layer can be uniaxially aligned by irradiating light as described above without forming the light-emitting layer on the alignment film.
本実施の形態の有機ＥＬ素子１は、第１電極２と第２電極３との間に正孔注入層５と発光層４とが配置されるが、有機ＥＬ素子１の構成は図１に示す構成に限らない。以下に有機ＥＬ素子の第１電極と第２電極との間の素子構成の一例について説明する。なお第１電極および第２電極は、光の取出される側に配置される電極が少なくとも透明であればよく、一方を陽極、他方を陰極として用いればよいので、以下の説明では陽極および陰極のうちのいずれか一方を第１電極とし、他方を第２電極として、第１電極および第２電極の極性を特定せずに素子構成の一例を説明する。 In the organic EL element 1 of the present embodiment, the hole injection layer 5 and the light emitting layer 4 are disposed between the first electrode 2 and the second electrode 3, and the configuration of the organic EL element 1 is shown in FIG. It is not restricted to the structure shown. Hereinafter, an example of the element configuration between the first electrode and the second electrode of the organic EL element will be described. The first electrode and the second electrode may be at least transparent as long as the electrodes arranged on the light extraction side are used, and one of them may be used as an anode and the other as a cathode. An example of the element configuration will be described without specifying the polarities of the first electrode and the second electrode, with one of these being the first electrode and the other being the second electrode.
前述したように陽極と陰極との間には、少なくとも一層の発光層が設けられていればよく、陽極と陰極との間には複数の発光層、及び／又は発光層とは異なる１または複数の層を設けてもよい。 As described above, it is sufficient that at least one light emitting layer is provided between the anode and the cathode, and a plurality of light emitting layers and / or one or more different from the light emitting layers are provided between the anode and the cathode. These layers may be provided.
陰極と発光層との間に設けられる層としては、電子注入層、電子輸送層、正孔ブロック層などが挙げられる。陰極と発光層との間に、電子注入層と電子輸送層との両方の層が設けられる場合、陰極に近い側に位置する層を電子注入層といい、発光層に近い側に位置する層を電子輸送層という。 Examples of the layer provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer. When both the electron injection layer and the electron transport layer are provided between the cathode and the light emitting layer, the layer located on the side close to the cathode is called the electron injection layer, and the layer located on the side close to the light emitting layer Is called an electron transport layer.
電子注入層は、陰極からの電子注入効率を改善する機能を有する層である。電子輸送層は、陰極、または電子注入層、若しくは陰極により近い電子輸送層からの電子注入を改善する機能を有する層である。正孔ブロック層は、正孔の輸送を堰き止める機能を有する層である。なお電子注入層または電子輸送層が、正孔ブロック層を兼ねる場合がある。 The electron injection layer is a layer having a function of improving electron injection efficiency from the cathode. The electron transport layer is a layer having a function of improving electron injection from the cathode, the electron injection layer, or the electron transport layer closer to the cathode. The hole blocking layer is a layer having a function of blocking hole transport. Note that the electron injection layer or the electron transport layer may also serve as the hole blocking layer.
陽極と発光層との間に設ける層としては、正孔注入層、正孔輸送層、電子ブロック層等が挙げられる。陽極と発光層との間に、正孔注入層と正孔輸送層との両方が設けられる場合、陽極に近い側に位置する層を正孔注入層といい、発光層に近い側に位置する層を正孔輸送層という。なお正孔注入層、正孔輸送層、電子ブロック層は、光を照射することで少なくとも一部が一軸配向した光配向性化合物を含んで構成される機能層であることが好ましく、特に正孔注入層、正孔輸送層、電子ブロック層のうちで、発光層に接して配置される層が、前記機能層であることが好ましい。 Examples of the layer provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer. When both the hole injection layer and the hole transport layer are provided between the anode and the light emitting layer, the layer located on the side close to the anode is called the hole injection layer, and is located on the side close to the light emitting layer. The layer is referred to as a hole transport layer. Note that the hole injection layer, the hole transport layer, and the electron blocking layer are preferably functional layers including a photo-alignment compound that is at least partially uniaxially aligned by light irradiation. Of the injection layer, the hole transport layer, and the electron blocking layer, the layer disposed in contact with the light emitting layer is preferably the functional layer.
正孔注入層は、陽極からの正孔注入効率を改善する機能を有する層である。正孔輸送層は、陽極または正孔注入層、若しくは陽極により近い正孔輸送層からの正孔注入を改善する機能を有する層である。電子ブロック層は、電子の輸送を堰き止める機能を有する層である。正孔注入層または正孔輸送層が、電子ブロック層を兼ねることがある。 The hole injection layer is a layer having a function of improving hole injection efficiency from the anode. The hole transport layer is a layer having a function of improving hole injection from the anode, the hole injection layer, or the hole transport layer closer to the anode. The electron blocking layer is a layer having a function of blocking electron transport. The hole injection layer or the hole transport layer may also serve as the electron block layer.
なお、電子注入層および正孔注入層を総称して電荷注入層ということがあり、電子輸送層および正孔輸送層を総称して電荷輸送層ということがある。 The electron injection layer and the hole injection layer are sometimes collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer are sometimes collectively referred to as a charge transport layer.
有機ＥＬ素子のとりうる層構成の具体的な一例を以下に示す。
ａ）陽極／正孔輸送層／発光層／陰極
ｂ）陽極／発光層／電子輸送層／陰極
ｃ）陽極／正孔輸送層／発光層／電子輸送層／陰極
ｄ）陽極／電荷注入層／発光層／陰極
ｅ）陽極／発光層／電荷注入層／陰極
ｆ）陽極／電荷注入層／発光層／電荷注入層／陰極
ｇ）陽極／電荷注入層／正孔輸送層／発光層／陰極
ｈ）陽極／正孔輸送層／発光層／電荷注入層／陰極
ｉ）陽極／電荷注入層／正孔輸送層／発光層／電荷注入層／陰極
ｊ）陽極／電荷注入層／発光層／電荷輸送層／陰極
ｋ）陽極／発光層／電子輸送層／電荷注入層／陰極
ｌ）陽極／電荷注入層／発光層／電子輸送層／電荷注入層／陰極
ｍ）陽極／電荷注入層／正孔輸送層／発光層／電荷輸送層／陰極
ｎ）陽極／正孔輸送層／発光層／電子輸送層／電荷注入層／陰極
ｏ）陽極／電荷注入層／正孔輸送層／発光層／電子輸送層／電荷注入層／陰極
（ここで、記号「／」は、この記号「／」を挟む２つの層が隣接して積層されることを示す。以下同じ。）
また、本実施の形態の有機ＥＬ素子は、２層以上の発光層を有していてもよい。２層の発光層を有する有機ＥＬ素子の具体例としては、
ｐ）陽極／電荷注入層／正孔輸送層／発光層／電子輸送層／電荷注入層／電極／電荷注入層／正孔輸送層／発光層／電子輸送層／電荷注入層／陰極
の層構成を有するものが挙げられる。
A specific example of the layer structure that the organic EL element can take is shown below.
a) Anode / hole transport layer / light emitting layer / cathode b) Anode / light emitting layer / electron transport layer / cathode c) Anode / hole transport layer / light emitting layer / electron transport layer / cathode d) Anode / charge injection layer / Emissive layer / cathode e) anode / emission layer / charge injection layer / cathode f) anode / charge injection layer / emission layer / charge injection layer / cathode g) anode / charge injection layer / hole transport layer / emission layer / cathode h ) Anode / hole transport layer / light emitting layer / charge injection layer / cathode i) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode j) Anode / charge injection layer / light emitting layer / charge transport Layer / cathode k) anode / light emitting layer / electron transport layer / charge injection layer / cathode l) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / hole transport Layer / light emitting layer / charge transport layer / cathode n) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode o) anode / charge injection layer / Hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode (Here, the symbol “/” indicates that two layers sandwiching the symbol “/” are adjacently stacked. The same applies hereinafter.) )
Further, the organic EL element of the present embodiment may have two or more light emitting layers. As a specific example of an organic EL element having two light emitting layers,
p) Layer structure of anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / electrode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode The thing which has is mentioned.
また、３層以上の発光層を有する有機ＥＬ素子としては、（電極／電荷注入層／正孔輸送層／発光層／電子輸送層／電荷注入層）を一つの繰り返し単位とすると、
ｑ）陽極／電荷注入層／正孔輸送層／発光層／電子輸送層／電荷注入層／繰り返し単位／繰り返し単位／・・・／陰極
のように、２つ以上の繰り返し単位を含む層構成を有するものが挙げられる。
In addition, as an organic EL device having three or more light emitting layers, (electrode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer) as one repeating unit,
q) Layer structure including two or more repeating units such as anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / repeat unit / repeat unit /. The thing which has.
上記層構成ｐおよびｑにおいて、陽極、陰極、発光層以外の各層は必要に応じて削除することができる。 In the layer structures p and q, each layer other than the anode, the cathode, and the light emitting layer can be deleted as necessary.
基板６から光を取出すボトムエミッション型の有機ＥＬ素子では、発光層を基準にして、基板６側に配置される層を全て透明な層で構成する。また後述するように発光層を基準にして基板とは反対側から光を取出すいわゆるトップエミッション型の有機ＥＬ素子では、発光層を基準にして、基板とは反対側に配置される層を全て透明な層で構成する。 In the bottom emission type organic EL element that extracts light from the substrate 6, the layers disposed on the substrate 6 side are all formed of a transparent layer with reference to the light emitting layer. As will be described later, in a so-called top emission type organic EL device that extracts light from the side opposite to the substrate with respect to the light emitting layer, all layers disposed on the side opposite to the substrate are transparent with respect to the light emitting layer. It is composed of various layers.
有機ＥＬ素子は、さらに電極との密着性向上や、電極からの電荷注入の改善のために、電極に隣接して膜厚が２ｎｍ以下の絶縁層を設けてもよく、また、界面の密着性向上や混合の防止等のために、隣接する前記各層の界面に薄いバッファー層を挿入してもよい。 The organic EL element may be further provided with an insulating layer having a film thickness of 2 nm or less adjacent to the electrode in order to improve the adhesion with the electrode or improve the charge injection from the electrode. In order to improve or prevent mixing, a thin buffer layer may be inserted at the interface between adjacent layers.
以下、各層の具体的な構成について説明する。なお発光層４および正孔注入層５については、前述したので重複する説明を省略する。また、陽極及び／又は陰極には、それぞれ前述した第１電極または第２電極を適宜用いることができるので重複する説明を省略する。 Hereinafter, a specific configuration of each layer will be described. Since the light-emitting layer 4 and the hole injection layer 5 have been described above, redundant description will be omitted. Moreover, since the first electrode or the second electrode described above can be used as appropriate for the anode and / or the cathode, respectively, the duplicated explanation is omitted.
＜正孔輸送層＞
正孔輸送層を構成する正孔輸送材料としては、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミンを有するポリシロキサン誘導体、ピラゾリン誘導体、アリールアミン誘導体、スチルベン誘導体、トリフェニルジアミン誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリピロール若しくはその誘導体、ポリ（ｐ−フェニレンビニレン）若しくはその誘導体、又はポリ（２，５−チエニレンビニレン）若しくはその誘導体などが挙げられる。
<Hole transport layer>
As the hole transport material constituting the hole transport layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, Triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylene vinylene) or And derivatives thereof.
これらの正孔輸送材料の中で、正孔輸送材料としては、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミン化合物基を有するポリシロキサン誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリ（ｐ−フェニレンビニレン）若しくはその誘導体、又はポリ（２，５−チエニレンビニレン）若しくはその誘導体等の高分子の正孔輸送材料が好ましく、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミンを有するポリシロキサン誘導体などがさらに好ましい。低分子の正孔輸送材料の場合には、高分子バインダーに分散させて用いることが好ましい。 Among these hole transport materials, as the hole transport material, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, polyarylamine or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferable, and polyvinyl More preferred are carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, and the like. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.
正孔輸送層の成膜方法としては、低分子の正孔輸送材料では、高分子バインダーとの混合溶液からの成膜による方法を挙げることができ、高分子の正孔輸送材料では、溶液からの成膜による方法を挙げることができる。 As a film formation method for the hole transport layer, a low molecular hole transport material can be formed by a film formation from a mixed solution with a polymer binder. A polymer hole transport material can be formed from a solution. There can be mentioned a method by film formation.
正孔輸送層に発光層が接して積層される場合、該正孔輸送層が配向膜として機能することが好ましい。このような正孔輸送層としては、光を照射することで少なくとも一部が一軸配向した光配向性化合物を含んで構成されることが好ましい。 When the light-emitting layer is laminated in contact with the hole transport layer, the hole transport layer preferably functions as an alignment film. Such a hole transport layer preferably includes a photo-alignment compound that is at least partially uniaxially aligned by irradiating light.
光配向性化合物には、例えば発光層および正孔注入層に用いられる光配向性化合物として挙げた光配向性化合物を適宜用いることができる。さらに、光配向性化合物が液晶性を示す化合物であると、配向性がより高まるので好ましい。 As the photo-alignment compound, for example, the photo-alignment compounds mentioned as the photo-alignment compounds used for the light emitting layer and the hole injection layer can be appropriately used. Furthermore, it is preferable that the photo-alignment compound is a compound exhibiting liquid crystallinity because the alignment is further enhanced.
正孔輸送層を製造する工程では、まず例えば光配向性化合物と正孔輸送材料とを含む塗布液を用いた塗布法により機能性薄膜（正孔輸送層用膜）を形成する。 In the step of manufacturing the hole transport layer, first, a functional thin film (hole transport layer film) is formed by, for example, a coating method using a coating liquid containing a photo-alignment compound and a hole transport material.
正孔輸送層用の塗布液は、溶液でも乳濁液でもよい。正孔輸送層用の塗布液の溶媒は、正孔輸送材料および光配向性化合物を溶解する液体であればよく、例えば正孔注入層用の塗布液の溶媒として挙げた溶媒を適宜用いることができ、また分散媒は、正孔輸送材料および光配向性化合物を均質に分散可能な液体であればよい。 The coating liquid for the hole transport layer may be a solution or an emulsion. The solvent of the coating liquid for the hole transport layer may be a liquid that dissolves the hole transport material and the photo-alignment compound. For example, the solvents mentioned as the solvent for the coating liquid for the hole injection layer may be appropriately used. The dispersion medium can be any liquid that can uniformly disperse the hole transport material and the photo-alignment compound.
塗布法としては、前述した正孔注入層および発光層の形成に用いられる塗布法として挙げた塗布法を適宜用いることができる。 As the coating method, the coating methods mentioned as the coating method used for forming the hole injection layer and the light emitting layer described above can be appropriately used.
次に、塗布法によって成膜された正孔輸送層用膜に光を照射することで光配向性化合物の少なくとも一部を一軸配向させて、正孔輸送層を形成する。この方法は、前述した正孔注入層用膜に光を照射する工程と同じなので説明を省略する。 Next, the hole transport layer is formed by irradiating light to the hole transport layer film formed by a coating method so that at least a part of the photo-alignment compound is uniaxially aligned. Since this method is the same as the step of irradiating light to the hole injection layer film described above, description thereof is omitted.
混合する高分子バインダーとしては、電荷輸送を極度に阻害しないものが好ましく、また可視光に対する吸収が弱いものが好適に用いられる。該高分子バインダーとしては、ポリカーボネート、ポリアクリレート、ポリメチルアクリレート、ポリメチルメタクリレート、ポリスチレン、ポリ塩化ビニル、ポリシロキサンなどが挙げられる。 As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those having low absorption of visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
なお正孔輸送層は、光配向性化合物を含まなくてもよく、この場合には正孔輸送層を形成する工程において前述した光を照射する工程を省略できる。 Note that the hole transport layer does not need to contain a photo-alignment compound, and in this case, the step of irradiating light described above in the step of forming the hole transport layer can be omitted.
正孔輸送層の膜厚としては、用いる材料によって最適値が異なり、駆動電圧と発光効率が適度な値となるように選択され、少なくともピンホールが発生しないような厚さが必要であり、厚すぎると、素子の駆動電圧が高くなり好ましくない。従って、正孔輸送層の膜厚としては、例えば１ｎｍ〜１μｍであり、好ましくは２ｎｍ〜５００ｎｍであり、さらに好ましくは５ｎｍ〜２００ｎｍである。 The film thickness of the hole transport layer differs depending on the material used, and is selected so that the drive voltage and the light emission efficiency are appropriate, and at least a thickness that does not cause pin holes is required. If it is too high, the driving voltage of the element becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
＜電子ブロック層＞
電子ブロック層は、前述したように電子の輸送を堰き止める機能を有する層であり、例えば正孔注入層と発光層とを有する素子構成の場合には、該正孔注入層と発光層との間に設けられる層（通常、正孔輸送層）を意味する。
<Electronic block layer>
As described above, the electron blocking layer is a layer having a function of blocking electron transport. For example, in the case of an element configuration having a hole injection layer and a light emitting layer, the electron block layer includes a hole injection layer and a light emitting layer. It means a layer (usually a hole transport layer) provided between them.
電子ブロック層を備える有機ＥＬ素子の層構成の具体的な一例を以下のｑ）〜ｔ）に示す。
ｑ）陽極／電子ブロック層／発光層／陰極
ｒ）陽極／正孔輸送層／電子ブロック層／発光層／陰極
ｓ）陽極／電子ブロック層／発光層／電子輸送層／陰極
ｔ）陽極／正孔輸送層／電子ブロック層／発光層／電子輸送層／陰極
電子ブロックを構成する電子ブロック材料としては、ポリビニルカルバゾール若しくはその誘導体、側鎖若しくは主鎖に芳香族アミンを有するポリアリーレン誘導体、アリールアミン誘導体、トリフェニルジアミン誘導体などの、芳香族アミンを含むポリマーが例示される。
Specific examples of the layer structure of the organic EL device including the electron block layer are shown in the following q) to t).
q) anode / electron blocking layer / light emitting layer / cathode r) anode / hole transport layer / electron blocking layer / light emitting layer / cathode s) anode / electron blocking layer / light emitting layer / electron transport layer / cathode t) anode / positive Hole transport layer / electron block layer / light emitting layer / electron transport layer / cathode As the electron block material constituting the electron block, polyvinylcarbazole or its derivative, polyarylene derivative having aromatic amine in the side chain or main chain, arylamine Examples thereof include polymers containing aromatic amines such as derivatives and triphenyldiamine derivatives.
電子ブロック層の成膜の方法に制限はないが、例えば高分子材料を用いる場合においては溶液からの成膜による方法が例示される。 The method for forming the electron blocking layer is not limited. For example, when a polymer material is used, a method using film formation from a solution is exemplified.
電子ブロック層に発光層が接して積層される場合、該電子ブロック層が配向膜として機能することが好ましい。このような電子ブロック層としては、光を照射することで少なくとも一部が一軸配向した光配向性化合物を含んで構成されることが好ましい。 When the light-emitting layer is laminated in contact with the electron block layer, the electron block layer preferably functions as an alignment film. Such an electron blocking layer is preferably configured to include a photoalignment compound that is at least partially uniaxially aligned by irradiation with light.
光配向性化合物には、例えば発光層および正孔注入層、正孔輸送層に用いられる光配向性化合物として挙げた光配向性化合物を適宜用いることができる。さらに、光配向性化合物が液晶性を示す化合物であると、配向性がより高まるので好ましい。 As the photo-alignment compound, for example, the photo-alignment compounds mentioned as the photo-alignment compounds used in the light emitting layer, the hole injection layer, and the hole transport layer can be appropriately used. Furthermore, it is preferable that the photo-alignment compound is a compound exhibiting liquid crystallinity because the alignment is further enhanced.
電子ブロック層を製造する工程では、まず例えば光配向性化合物と電子ブロック材料とを含む塗布液を用いた塗布法により機能性薄膜（電子ブロック層用膜）を形成する。 In the step of manufacturing the electron block layer, first, a functional thin film (film for electron block layer) is formed by a coating method using a coating liquid containing, for example, a photoalignment compound and an electron block material.
電子ブロック層用の塗布液は、溶液でも乳濁液でもよい。電子ブロック層用の塗布液の溶媒は、電子ブロック材料および光配向性化合物を溶解する液体であればよく、例えば電子ブロック層用の塗布液の溶媒として挙げた溶媒を適宜用いることができ、また分散媒は、電子ブロック材料および光配向性化合物を均質に分散可能な液体であればよい。 The coating solution for the electronic block layer may be a solution or an emulsion. The solvent of the coating liquid for the electron block layer may be any liquid that dissolves the electron block material and the photo-alignment compound. For example, the solvents mentioned as the solvent for the coating liquid for the electron block layer can be appropriately used. The dispersion medium may be a liquid that can uniformly disperse the electron block material and the photoalignment compound.
塗布法としては、前述した電子ブロック層および発光層の形成に用いられる塗布法として挙げた塗布法を適宜用いることができる。 As the coating method, the coating methods mentioned as the coating method used for forming the electron blocking layer and the light emitting layer described above can be used as appropriate.
次に、塗布法によって成膜された電子ブロック層用膜に光を照射することで光配向性化合物の少なくとも一部を一軸配向させて、電子ブロック層を形成する。この方法は、前述した正孔注入層用膜に光を照射する工程と同じなので説明を省略する。 Next, at least a part of the photo-alignment compound is uniaxially oriented by irradiating light to the electron blocking layer film formed by a coating method, thereby forming an electron blocking layer. Since this method is the same as the step of irradiating light to the hole injection layer film described above, description thereof is omitted.
また、電子ブロック層用の塗布液は、高分子バインダーとの混合溶液でもよい。混合する高分子バインダーとしては、電子ブロック機能を極度に阻害しないものが好ましく、また可視光に対する吸収が弱いものが好適に用いられる。該高分子バインダーとしては、ポリカーボネート、ポリアクリレート、ポリメチルアクリレート、ポリメチルメタクリレート、ポリスチレン、ポリ塩化ビニル、ポリシロキサンなどが挙げられる。 The coating solution for the electronic block layer may be a mixed solution with a polymer binder. As the polymer binder to be mixed, those not extremely disturbing the electronic block function are preferable, and those having weak absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
なお電子ブロック層は、光配向性化合物を含まなくてもよく、この場合には電子ブロック層を形成する工程において前述した光を照射する工程を省略できる。 Note that the electron blocking layer may not include a photoalignment compound, and in this case, the step of irradiating light described above in the step of forming the electron blocking layer can be omitted.
電子ブロック層の膜厚としては、用いる材料によって最適値が異なり、駆動電圧と発光効率が適度な値となるように選択され、少なくともピンホールが発生しないような厚さが必要であり、厚すぎると、素子の駆動電圧が高くなり好ましくない。従って、電子ブロック層の膜厚としては、例えば１ｎｍ〜５００μｍであり、好ましくは２ｎｍ〜２００ｎｍであり、さらに好ましくは５ｎｍ〜１００ｎｍである。 The film thickness of the electron block layer varies depending on the material used, and is selected so that the drive voltage and the light emission efficiency are appropriate. At least a thickness that does not cause pinholes is necessary, and is too thick. In such a case, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron blocking layer is, for example, 1 nm to 500 μm, preferably 2 nm to 200 nm, and more preferably 5 nm to 100 nm.
＜電子注入層＞
電子注入層を構成する電子注入材料としては、発光層の種類に応じて、アルカリ金属、アルカリ土類金属、または前記金属を１種類以上含む合金、または前記金属の酸化物、ハロゲン化物および炭酸化物、または前記物質の混合物などが挙げられる。アルカリ金属またはその酸化物、ハロゲン化物、炭酸化物としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、酸化リチウム、フッ化リチウム、酸化ナトリウム、フッ化ナトリウム、酸化カリウム、フッ化カリウム、酸化ルビジウム、フッ化ルビジウム、酸化セシウム、フッ化セシウム、炭酸リチウム等が挙げられる。また、アルカリ土類金属またはその酸化物、ハロゲン化物、炭酸化物の例としては、マグネシウム、カルシウム、バリウム、ストロンチウム、酸化マグネシウム、フッ化マグネシウム、酸化カルシウム、フッ化カルシウム、酸化バリウム、フッ化バリウム、酸化ストロンチウム、フッ化ストロンチウム、炭酸マグネシウム等が挙げられる。電子注入層は、２層以上を積層した積層体であってもよい。積層体の具体例としては、ＬｉＦ／Ｃａなどが挙げられる。電子注入層は、蒸着法、スパッタリング法、印刷法等によって形成される。電子注入層の膜厚としては、１ｎｍ〜１μｍ程度が好ましい。
<Electron injection layer>
Depending on the type of the light emitting layer, the electron injecting material constituting the electron injecting layer may be an alkali metal, an alkaline earth metal, an alloy containing one or more of the metals, or an oxide, halide or carbonate of the metal. Or a mixture of the aforementioned substances. Alkali metals or their oxides, halides and carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, rubidium oxide, fluorine. Examples thereof include rubidium chloride, cesium oxide, cesium fluoride, and lithium carbonate. Examples of alkaline earth metals or oxides, halides and carbonates thereof include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, barium fluoride, Examples include strontium oxide, strontium fluoride, and magnesium carbonate. The electron injection layer may be a laminate in which two or more layers are laminated. Specific examples of the laminate include LiF / Ca. The electron injection layer is formed by vapor deposition, sputtering, printing, or the like. The thickness of the electron injection layer is preferably about 1 nm to 1 μm.
＜電子輸送層＞
電子輸送層を構成する電子輸送材料としては、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアンスラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、又は８−ヒドロキシキノリン若しくはその誘導体の金属錯体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体等を挙げることができる。
<Electron transport layer>
As an electron transport material constituting the electron transport layer, an oxadiazole derivative, anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, Fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like can be given.
これらのうち、電子輸送材料としては、オキサジアゾール誘導体、ベンゾキノン若しくはその誘導体、アントラキノン若しくはその誘導体、又は８−ヒドロキシキノリン若しくはその誘導体の金属錯体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体が好ましく、２−（４−ビフェニリル）−５−（４−ｔ−ブチルフェニル）−１，３，４−オキサジアゾール、ベンゾキノン、アントラキノン、トリス（８−キノリノール）アルミニウム、ポリキノリンがさらに好ましい。 Among these, as an electron transport material, an oxadiazole derivative, benzoquinone or a derivative thereof, anthraquinone or a derivative thereof, a metal complex of 8-hydroxyquinoline or a derivative thereof, a polyquinoline or a derivative thereof, a polyquinoxaline or a derivative thereof, a polyfluorene Or a derivative thereof is preferable, and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are further included. preferable.
前述の実施の形態の有機ＥＬ素子１を用いることによって、有機ＥＬ素子を備える照明装置、または有機ＥＬ素子を複数備える表示装置を実現することができる。 By using the organic EL element 1 of the above-described embodiment, a lighting device including the organic EL element or a display device including a plurality of organic EL elements can be realized.
本実施の形態の有機ＥＬ素子は、照明装置、面状光源、セグメント表示装置およびドットマトリックス表示装置の光源、並びに液晶表示装置のバックライトとして用いることができ、本実施の形態の有機ＥＬ素子は直線偏光光を発するので、特に液晶表示装置のバックライトとして好適に用いられる。 The organic EL element of this embodiment can be used as a backlight of a lighting device, a planar light source, a segment display device and a dot matrix display device, and a liquid crystal display device. The organic EL element of this embodiment Since it emits linearly polarized light, it is particularly suitably used as a backlight of a liquid crystal display device.
本実施の形態の有機ＥＬ素子を面状光源として用いる場合には、例えば面状の陽極と陰極とを積層方向の一方から見て重なり合うように配置すればよい。またセグメント表示装置の光源として所定のパターンで発光する有機ＥＬ素子を構成するには、光を通す窓が所定のパターンで形成されたマスクを前記面状光源の表面に設置する方法、消光すべき部位の有機物層を極端に厚く形成して実質的に非発光とする方法、陽極および陰極のうちの少なくともいずれか一方の電極を所定のパターンで形成する方法がある。これらの方法で所定のパターンで発光する有機ＥＬ素子を形成するとともに、いくつかの電極に対して選択的に電圧を印加できるように配線を施すことによって、数字や文字、簡単な記号などを表示可能なセグメントタイプ表示装置を実現することができる。ドットマトリックス表示装置の光源とするためには、陽極と陰極とをそれぞれストライプ状に形成して、積層方向の一方からみて互いに直交するように配置すればよい。部分カラー表示、マルチカラー表示が可能なドットマトリックス表示装置を実現するためには、発光色の異なる複数の種類の発光材料を塗り分ける方法、並びにカラーフィルターおよび蛍光変換フィルターなどを用いる方法を用いればよい。ドットマトリックス表示装置は、パッシブ駆動してもよく、ＴＦＴなどと組合せてアクティブ駆動してもよい。これらの表示装置は、コンピュータ、テレビ、携帯端末、携帯電話、カーナビゲーション、ビデオカメラのビューファインダーなどの表示装置として用いることができる。 When the organic EL element of the present embodiment is used as a planar light source, for example, a planar anode and a cathode may be arranged so as to overlap each other when viewed from one side in the stacking direction. Further, in order to construct an organic EL element that emits light in a predetermined pattern as a light source of a segment display device, a method of installing a mask in which a light transmitting window is formed in a predetermined pattern on the surface of the planar light source, should be quenched There are a method in which the organic layer of the part is formed extremely thick to make it substantially non-light-emitting, and a method in which at least one of the anode and the cathode is formed in a predetermined pattern. By using these methods to form organic EL elements that emit light in a predetermined pattern, wiring is applied so that voltages can be selectively applied to several electrodes, thereby displaying numbers, letters, simple symbols, etc. A possible segment type display device can be realized. In order to use the light source of the dot matrix display device, the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other when viewed from one side in the stacking direction. In order to realize a dot matrix display device capable of partial color display and multi-color display, a method of separately coating a plurality of types of light emitting materials having different emission colors and a method using a color filter, a fluorescence conversion filter, and the like are used. Good. The dot matrix display device may be driven passively or may be actively driven in combination with a TFT or the like. These display devices can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.
さらに、前記面状光源は、自発光薄型であり、液晶表示装置のバックライト、あるいは面状の照明装置として好適に用いることができる。また、フレキシブルな基板を用いれば、曲面状の光源や表示装置としても使用できる。 Further, the planar light source is self-luminous and thin, and can be suitably used as a backlight of a liquid crystal display device or a planar illumination device. If a flexible substrate is used, it can be used as a curved light source or display device.
バックライトは、面状に形成した本実施の形態の有機ＥＬ素子と、例えば拡散板とを積層させて構成される。また液晶表示装置は、液晶セルと、液晶セルに電場をかける一対の電極と、液晶セルを挟んで配置される一対の偏光板と、該一対の偏光板の一方に光を照射する前記バックライトとを含んで構成される。なお偏光度合いの高い有機ＥＬ素子を用いる場合には、一対の偏光板のうち、バックライト側の偏光板を省略してもよい。前述したように本実施の形態の有機ＥＬ素子は、所定の方向に偏光した光を発するので、バックライトから放出される光も偏光した光であり、このようなバックライトを液晶表示装置に用いると、偏光板での光の損失を低減することができる。これによって消費電力の低い液晶表示装置を実現することができる。 The backlight is configured by laminating the organic EL element of the present embodiment formed in a planar shape and, for example, a diffusion plate. The liquid crystal display device includes a liquid crystal cell, a pair of electrodes for applying an electric field to the liquid crystal cell, a pair of polarizing plates arranged with the liquid crystal cell interposed therebetween, and the backlight for irradiating one of the pair of polarizing plates with light. It is comprised including. In the case of using an organic EL element having a high degree of polarization, the polarizing plate on the backlight side may be omitted from the pair of polarizing plates. As described above, since the organic EL element of the present embodiment emits light polarized in a predetermined direction, the light emitted from the backlight is also polarized light, and such a backlight is used for a liquid crystal display device. And the loss of the light in a polarizing plate can be reduced. As a result, a liquid crystal display device with low power consumption can be realized.
（実施例１）
基板／陽極（ＩＴＯ薄膜）／正孔注入層／電子ブロック層／発光層／陰極の層構成を有する有機ＥＬ素子を作製した。
Example 1
An organic EL device having a layer structure of substrate / anode (ITO thin film) / hole injection layer / electron blocking layer / light emitting layer / cathode was produced.
＜電子ブロック材料の合成例＞
まず攪拌翼、バッフル、長さ調整可能な窒素導入管、冷却管、および温度計を備えるセパラブルフラスコに２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン１５８．２９重量部と、ビス−（４−ブロモフェニル）−４−（１−メチルプロピル）−ベンゼンアミン１３６．１１重量部と、トリカプリルメチルアンモニウムクロリド（ヘンケル社製 Ａｌｉｑｕａｔ ３３６）２７重量部と、トルエン１８００重量部とを仕込み、窒素導入管から窒素を導入しながら、攪拌下９０℃まで昇温した。酢酸パラジウム（ＩＩ）０．０６６重量部と、トリ（ｏ−トルイル）ホスフィン０．４５重量部とを加えた後、１７．５％炭酸ナトリウム水溶液５７３重量部を１時間かけて滴下した。滴下終了後、窒素導入管を液面より引き上げ、還流下７時間保温した後、フェニルホウ酸３．６重量部を加え、１４時間還流下保温し、室温まで冷却した。反応液水層を除いた後、反応液油層をトルエンで希釈し、３％酢酸水溶液、イオン交換水で洗浄した。分液油層にＮ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物１３重量部を加え４時間攪拌した後、活性アルミナとシリカゲルとの混合カラムに通液し、トルエンを通液してカラムを洗浄した。濾液および洗液を混合した後、メタノールに滴下して、ポリマーを沈殿させた。得られたポリマー沈殿を濾別し、メタノールで沈殿を洗浄した後、真空乾燥機でポリマーを乾燥させ、ポリマー１９２重量部を得た。得られたポリマーを高分子化合物１とよぶ。高分子化合物１のポリスチレン換算重量平均分子量は、３．７×１０5であり、数平均分子量は８．９×１０4あった。
<Synthesis example of electronic block material>
First, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9- was added to a separable flask equipped with a stirring blade, a baffle, a length-adjustable nitrogen inlet tube, a cooling tube, and a thermometer. 158.29 parts by weight of dioctylfluorene, 136.11 parts by weight of bis- (4-bromophenyl) -4- (1-methylpropyl) -benzenamine, 27 weights of tricaprylmethylammonium chloride (Aliquat 336 manufactured by Henkel) And 1800 parts by weight of toluene were charged, and the temperature was raised to 90 ° C. with stirring while introducing nitrogen from a nitrogen introduction tube. After adding 0.066 parts by weight of palladium (II) acetate and 0.45 parts by weight of tri (o-toluyl) phosphine, 573 parts by weight of a 17.5% aqueous sodium carbonate solution was added dropwise over 1 hour. After completion of the dropwise addition, the nitrogen inlet tube was lifted from the liquid surface and kept under reflux for 7 hours, then 3.6 parts by weight of phenylboric acid was added, kept under reflux for 14 hours, and cooled to room temperature. After removing the reaction solution aqueous layer, the reaction solution oil layer was diluted with toluene and washed with 3% acetic acid aqueous solution and ion-exchanged water. After adding 13 parts by weight of sodium N, N-diethyldithiocarbamate trihydrate to the separated oil layer and stirring for 4 hours, the solution was passed through a mixed column of activated alumina and silica gel, and toluene was passed through to wash the column. did. The filtrate and washings were mixed and then added dropwise to methanol to precipitate the polymer. The obtained polymer precipitate was separated by filtration, washed with methanol, and then dried with a vacuum dryer to obtain 192 parts by weight of polymer. The resulting polymer is referred to as polymer compound 1. The polymer compound 1 had a polystyrene equivalent weight average molecular weight of 3.7 × 10 5 and a number average molecular weight of 8.9 × 10 4 .
（ＧＰＣ分析法）
ポリスチレン換算重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により求めた。ＧＰＣの検量線の作成にはポリマーラボラトリーズ社製標準ポリスチレンを使用した。測定する重合体は、約０．０２重量％の濃度になるようテトラヒドロフランに溶解させ、ＧＰＣに１０μＬ注入した。ＧＰＣ装置は島津製作所製ＬＣ−１０ＡＤｖｐを用いた。カラムは、ポリマーラボラトリーズ社製ＰＬｇｅｌ １０μm ＭＩＸＥＤ−Ｂカラム（３００×７．５ｍｍ）を２本直列に接続して用い、移動相としてテトラヒドロフランを２５℃、１．０ｍＬ／ｍｉｎの流速で流した。検出器にＵＶ検出器を用い、２２８ｎｍの吸光度を測定した。
(GPC analysis method)
The polystyrene equivalent weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (GPC). Standard polystyrene made by Polymer Laboratories was used to prepare a GPC calibration curve. The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.02% by weight, and 10 μL was injected into GPC. The GPC apparatus used was LC-10ADvp manufactured by Shimadzu Corporation. As the column, two PLgel 10 μm MIXED-B columns (300 × 7.5 mm) manufactured by Polymer Laboratories were used in series, and tetrahydrofuran was flowed at 25 ° C. and a flow rate of 1.0 mL / min as a mobile phase. Absorbance at 228 nm was measured using a UV detector as the detector.
＜基板の作製＞
５×５ｃｍガラス基板（屈折率１．５２）上に、１２０℃に加熱しながら、５ｃｍ×２ｃｍの帯状に３００ｎｍの膜厚のＩＴＯ（屈折率２．０）薄膜をスパッタ成膜（ＤＣスパッタ法、成膜圧力０．２５Ｐａ、パワー０．２５ｋＷ）した（透明電極の形成）。その後オーブン中において２００℃で４０分間アニール処理をした。基板を５０℃の強アルカリ性洗剤、冷水、５０℃の温水を用いて順次超音波洗浄し、５０℃の温水から引き上げ、さらにオーブン中で乾燥した。その後２０分間ＵＶオゾン洗浄を行った。
<Production of substrate>
On a 5 × 5 cm glass substrate (refractive index 1.52), an ITO (refractive index 2.0) thin film having a thickness of 300 nm is sputter-deposited (DC sputtering method) in a 5 cm × 2 cm band while heating to 120 ° C. (Film formation pressure 0.25 Pa, power 0.25 kW) (transparent electrode formation). Thereafter, annealing was performed in an oven at 200 ° C. for 40 minutes. The substrate was sequentially subjected to ultrasonic cleaning using a 50 ° C. strong alkaline detergent, cold water and 50 ° C. warm water, pulled up from the 50 ° C. warm water, and further dried in an oven. Thereafter, UV ozone cleaning was performed for 20 minutes.
＜ＥＬ素子の作製＞
ポリ（３，４）エチレンジオキシチオフェン／ポリスチレンスルホン酸（スタルク社製、商品名：ＡＩ４０８３）の懸濁液を０．４５μｍ径のフィルターを用いてろ過した液を、上記で作製した洗浄済基板上にスピンコートにより塗布し、膜厚が６５ｎｍの薄膜を形成した。大気雰囲気下においてホットプレート上で、２００℃で１５分間熱処理し、正孔注入層を形成した。次いで、上記で合成した高分子化合物１を０．４質量％の割合でトルエンに溶解し、電子ブロック層用の塗布液を作製した。次に正孔注入層が形成された基板上に電子ブロック層用の塗布液をスピンコートによって塗布し、膜厚が２０ｎｍの薄膜を形成した。その後、窒素雰囲気下においてホットプレート上で２００℃、２０分間熱処理し、電子ブロック層を形成した。次に白色発光材料（サメイション製ＷＰ１３３０）を０．８質量％の割合でトルエンに溶解し、さらにカルコン系光配向性化合物（ＲＯＬＩＣ社製、商品名：ＬＰＰＦ３０１ＣＰ）を白色発光材料１に対して重量比で２０％の割合で添加し、発光層用の塗布液を作製した。次に正孔注入層が形成された基板上に発光層用の塗布液をスピンコートによって塗布し、膜厚が８０ｎｍの薄膜を形成した。その後、偏光ＵＶ（波長２８０−３３０ｎｍ）を照射し、窒素雰囲気下のホットプレート上で１３０℃、３０分間熱処理し、発光層を形成した。偏光ＵＶは、ＧＳ ＵＶ ＳＹＳＴＥＭ（入江製作所株式会社製）のＵＶ照射機とＵＶ偏光フィルター２５．０ｍｍφ（エドモント オプティックス・ジャパン株式会社製）を用いた。発光層が形成された基板を真空蒸着機に導入し、ＩＴＯ薄膜のパターンに直交するように陰極としてＢａ、Ａｌをそれぞれ、１０ｎｍ、１００ｎｍの厚みで５×２ｃｍの帯状に順次蒸着し、陰極を形成した。陰極形成時の真空度が１×１０-4Ｐａ以下に到達した後に金属の蒸着を開始した。最後に、不活性ガス中で、ＩＴＯ薄膜と陰極が直交する部分を中心にガラス板で覆い、さらに４辺を光硬化樹脂で覆った後に、ＵＶ照射して光硬化樹脂を硬化させ、有機ＥＬ発光素子を作製した。
<Production of EL element>
A cleaned substrate prepared as described above is obtained by filtering a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (trade name: AI4083, manufactured by Starck Co., Ltd.) using a 0.45 μm filter. A thin film having a film thickness of 65 nm was formed by spin coating. Heat treatment was performed at 200 ° C. for 15 minutes on a hot plate in an air atmosphere to form a hole injection layer. Next, the polymer compound 1 synthesized above was dissolved in toluene at a ratio of 0.4% by mass to prepare a coating solution for an electronic block layer. Next, a coating solution for an electron blocking layer was applied by spin coating on the substrate on which the hole injection layer was formed to form a thin film having a thickness of 20 nm. Then, it heat-processed for 20 minutes at 200 degreeC on the hotplate in nitrogen atmosphere, and formed the electronic block layer. Next, a white light emitting material (WP1330 manufactured by Summation) was dissolved in toluene at a ratio of 0.8% by mass, and the chalcone-based photo-alignment compound (trade name: LPPF301CP) manufactured by ROLIC was weighted with respect to the white light emitting material 1. The coating solution for the light emitting layer was prepared by adding at a ratio of 20%. Next, the light emitting layer coating solution was applied by spin coating on the substrate on which the hole injection layer was formed, to form a thin film having a thickness of 80 nm. Then, polarized UV (wavelength 280-330nm) was irradiated, and it heat-processed for 30 minutes at 130 degreeC on the hotplate in nitrogen atmosphere, and formed the light emitting layer. As the polarized UV, a UV irradiation machine of GS UV SYSTEM (manufactured by Irie Manufacturing Co., Ltd.) and a UV polarizing filter 25.0 mmφ (manufactured by Edmont Optics Japan Co., Ltd.) were used. The substrate on which the light emitting layer is formed is introduced into a vacuum vapor deposition machine, and Ba and Al are sequentially deposited as a cathode in a thickness of 5 × 2 cm with a thickness of 10 nm and 100 nm so as to be orthogonal to the ITO thin film pattern. Formed. After the degree of vacuum at the time of forming the cathode reached 1 × 10 −4 Pa or less, metal deposition was started. Finally, in an inert gas, the glass thin plate and the cathode are covered with a glass plate at the center, and the four sides are covered with a photo-curing resin, and then UV irradiation is performed to cure the photo-curing resin. A light emitting element was manufactured.
（実施例２）
＜ＥＬ素子の作製＞
ポリ（３，４）エチレンジオキシチオフェン／ポリスチレンスルホン酸（スタルク社製、商品名：ＡＩ４０８３）の懸濁液を０．４５μｍ径のフィルターを用いてろ過した液を、上記実施例１で作製した洗浄済基板上にスピンコートにより塗布し、膜厚が６５ｎｍの薄膜を形成した。大気雰囲気下においてホットプレート上で、２００℃で１５分間熱処理し、正孔注入層を形成した。次いで、次いで、上記で合成した高分子化合物１を０．４質量％の割合でトルエンに溶解し、さらにカルコン系光配向性化合物（ＲＯＬＩＣ社製、商品名：ＬＰＰＦ３０１ＣＰ）を高分子化合物１に対して重量比で２０％の割合で添加して、電子ブロック層用の塗布液を作成した。次に正孔注入層が形成された基板上に電子ブロック層用の塗布液をスピンコートによって塗布し、膜厚が２０ｎｍの薄膜を形成した。その後、偏光ＵＶ（波長２８０−３３０ｎｍ）を照射し、窒素雰囲気下においてホットプレート上で２００℃、２０分間熱処理し、電子ブロック層を形成した。次に白色発光材料（サメイション製ＷＰ１３３０）を０．８質量％の割合でトルエンに溶解し、さらにカルコン系光配向性化合物（ＲＯＬＩＣ社製、商品名：ＬＰＰＦ３０１ＣＰ）を白色発光材料１に対して重量比で２０％の割合で添加し、発光層用の塗布液を作製した。次に正孔注入層が形成された基板上に発光層用の塗布液をスピンコートによって塗布し、膜厚が８０ｎｍの薄膜を形成した。その後、偏光ＵＶ（波長２８０−３３０ｎｍ）を照射し、窒素雰囲気下のホットプレート上で１３０℃、３０分間熱処理し、発光層を形成した。偏光ＵＶは、ＧＳ ＵＶ ＳＹＳＴＥＭ（入江製作所株式会社製）のＵＶ照射機とＵＶ偏光フィルター２５．０ｍｍφ（エドモント オプティックス・ジャパン株式会社製）を用いた。発光層が形成された基板を真空蒸着機に導入し、ＩＴＯ薄膜のパターンに直交するように陰極としてＢａ、Ａｌをそれぞれ、１０ｎｍ、１００ｎｍの厚みで５×２ｃｍの帯状に順次蒸着し、陰極を形成した。陰極形成時の真空度が１×１０-4Ｐａ以下に到達した後に金属の蒸着を開始した。最後に、不活性ガス中で、ＩＴＯ薄膜と陰極が直交する部分を中心にガラス板で覆い、さらに４辺を光硬化樹脂で覆った後に、ＵＶ照射して光硬化樹脂を硬化させ、有機ＥＬ発光素子を作製した。
(Example 2)
<Production of EL element>
A liquid obtained by filtering a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Starck, trade name: AI4083) using a 0.45 μm filter was prepared in Example 1 above. A thin film having a film thickness of 65 nm was formed on the cleaned substrate by spin coating. Heat treatment was performed at 200 ° C. for 15 minutes on a hot plate in an air atmosphere to form a hole injection layer. Subsequently, the polymer compound 1 synthesized above was dissolved in toluene at a ratio of 0.4% by mass, and a chalcone photo-alignment compound (trade name: LPPF301CP) manufactured by ROLIC was added to the polymer compound 1. And added at a ratio of 20% by weight to prepare a coating solution for the electronic block layer. Next, a coating solution for an electron blocking layer was applied by spin coating on the substrate on which the hole injection layer was formed to form a thin film having a thickness of 20 nm. Then, polarized UV (wavelength 280-330 nm) was irradiated and heat-treated at 200 ° C. for 20 minutes on a hot plate in a nitrogen atmosphere to form an electron blocking layer. Next, a white light emitting material (WP1330 manufactured by Summation) was dissolved in toluene at a ratio of 0.8% by mass, and the chalcone-based photo-alignment compound (trade name: LPPF301CP) manufactured by ROLIC was weighted with respect to the white light emitting material 1. The coating solution for the light emitting layer was prepared by adding at a ratio of 20%. Next, the light emitting layer coating solution was applied by spin coating on the substrate on which the hole injection layer was formed, to form a thin film having a thickness of 80 nm. Then, polarized UV (wavelength 280-330nm) was irradiated, and it heat-processed for 30 minutes at 130 degreeC on the hotplate in nitrogen atmosphere, and formed the light emitting layer. As the polarized UV, a UV irradiation machine of GS UV SYSTEM (manufactured by Irie Manufacturing Co., Ltd.) and a UV polarizing filter 25.0 mmφ (manufactured by Edmont Optics Japan Co., Ltd.) were used. The substrate on which the light emitting layer is formed is introduced into a vacuum vapor deposition machine, and Ba and Al are sequentially deposited as a cathode in a thickness of 5 × 2 cm with a thickness of 10 nm and 100 nm so as to be orthogonal to the ITO thin film pattern. Formed. After the degree of vacuum at the time of forming the cathode reached 1 × 10 −4 Pa or less, metal deposition was started. Finally, in an inert gas, the glass thin plate and the cathode are covered with a glass plate at the center, and the four sides are covered with a photo-curing resin, and then UV irradiation is performed to cure the photo-curing resin. A light emitting element was manufactured.
（実施例３）
＜ＥＬ素子の作製＞
ポリ（３，４）エチレンジオキシチオフェン／ポリスチレンスルホン酸（スタルク社製、商品名：ＡＩ４０８３）の懸濁液を０．４５μｍ径のフィルターを用いてろ過した液を、上記実施例１で作製した洗浄済基板上にスピンコートにより塗布し、膜厚が６５ｎｍの薄膜を形成した。大気雰囲気下においてホットプレート上で、２００℃で１５分間熱処理し、正孔注入層を形成した。次いで、上記で合成した高分子化合物１を０．４質量％の割合でトルエンに溶解し、電子ブロック層用の塗布液を作製した。次に正孔注入層が形成された基板上に電子ブロック層用の塗布液をスピンコートによって塗布し、膜厚が２０ｎｍの薄膜を形成した。その後、窒素雰囲気下においてホットプレート上で２００℃、２０分間熱処理し、電子ブロック層を形成した。次に白色発光材料（サメイション製ＷＰ１３３０）を０．８質量％の割合でトルエンに溶解し、さらにカルコン系光配向性化合物（ＲＯＬＩＣ社製、商品名：ＬＣＰＣＢ４８３ＣＰ）を白色発光材料１に対して重量比で２０％の割合で添加し、発光層用の塗布液を作製した。次に正孔注入層が形成された基板上に発光層用の塗布液をスピンコートによって塗布し、膜厚が８０ｎｍの薄膜を形成した。その後、偏光ＵＶ（波長２８０−３３０ｎｍ）を照射し、窒素雰囲気下のホットプレート上で１３０℃、３０分間熱処理し、発光層を形成した。偏光ＵＶは、ＧＳ ＵＶ ＳＹＳＴＥＭ（入江製作所株式会社製）のＵＶ照射機とＵＶ偏光フィルター２５．０ｍｍφ（エドモント オプティックス・ジャパン株式会社製）を用いた。発光層が形成された基板を真空蒸着機に導入し、ＩＴＯ薄膜のパターンに直交するように陰極としてＢａ、Ａｌをそれぞれ、１０ｎｍ、１００ｎｍの厚みで５×２ｃｍの帯状に順次蒸着し、陰極を形成した。陰極形成時の真空度が１×１０-4Ｐａ以下に到達した後に金属の蒸着を開始した。最後に、不活性ガス中で、ＩＴＯ薄膜と陰極が直交する部分を中心にガラス板で覆い、さらに４辺を光硬化樹脂で覆った後に、ＵＶ照射して光硬化樹脂を硬化させ、有機ＥＬ発光素子を作製した。
(Example 3)
<Production of EL element>
A liquid obtained by filtering a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Starck, trade name: AI4083) using a 0.45 μm filter was prepared in Example 1 above. A thin film having a film thickness of 65 nm was formed on the cleaned substrate by spin coating. Heat treatment was performed at 200 ° C. for 15 minutes on a hot plate in an air atmosphere to form a hole injection layer. Next, the polymer compound 1 synthesized above was dissolved in toluene at a ratio of 0.4% by mass to prepare a coating solution for an electronic block layer. Next, a coating solution for an electron blocking layer was applied by spin coating on the substrate on which the hole injection layer was formed to form a thin film having a thickness of 20 nm. Then, it heat-processed for 20 minutes at 200 degreeC on the hotplate in nitrogen atmosphere, and formed the electronic block layer. Next, a white light emitting material (WP1330 manufactured by Summation) was dissolved in toluene at a ratio of 0.8% by mass, and the chalcone-based photo-alignment compound (product name: LCPCB483CP) manufactured by ROLIC was weighted with respect to the white light emitting material 1. The coating solution for the light emitting layer was prepared by adding at a ratio of 20%. Next, the light emitting layer coating solution was applied by spin coating onto the substrate on which the hole injection layer was formed, to form a thin film having a thickness of 80 nm. Then, polarized UV (wavelength 280-330nm) was irradiated, and it heat-processed for 30 minutes at 130 degreeC on the hotplate in nitrogen atmosphere, and formed the light emitting layer. As the polarized UV, a UV irradiation machine of GS UV SYSTEM (manufactured by Irie Manufacturing Co., Ltd.) and a UV polarizing filter 25.0 mmφ (manufactured by Edmont Optics Japan Co., Ltd.) were used. The substrate on which the light emitting layer is formed is introduced into a vacuum vapor deposition machine, and Ba and Al are sequentially deposited as a cathode in a thickness of 5 × 2 cm with a thickness of 10 nm and 100 nm so as to be orthogonal to the ITO thin film pattern. Formed. After the degree of vacuum at the time of forming the cathode reached 1 × 10 −4 Pa or less, metal deposition was started. Finally, in an inert gas, the ITO thin film and the cathode are orthogonally covered with a glass plate, and the four sides are covered with a photo-curing resin, followed by UV irradiation to cure the photo-curing resin. A light emitting element was manufactured.
（実施例４）
＜ＥＬ素子の作製＞
ポリ（３，４）エチレンジオキシチオフェン／ポリスチレンスルホン酸（スタルク社製、商品名：ＡＩ４０８３）の懸濁液を０．４５μｍ径のフィルターを用いてろ過した液を、上記実施例１で作製した洗浄済基板上にスピンコートにより塗布し、膜厚が６５ｎｍの薄膜を形成した。大気雰囲気下においてホットプレート上で、２００℃で１５分間熱処理し、正孔注入層を形成した。次いで、次いで、上記で合成した高分子化合物１を０．４質量％の割合でトルエンに溶解し、さらにカルコン系光配向性化合物（ＲＯＬＩＣ社製、商品名：ＬＣＰＣＢ４８３ＣＰ）を高分子化合物１に対して重量比で２０％の割合で添加して、電子ブロック層用の塗布液を作成した。次に正孔注入層が形成された基板上に電子ブロック層用の塗布液をスピンコートによって塗布し、膜厚が２０ｎｍの薄膜を形成した。その後、偏光ＵＶ（波長２８０−３３０ｎｍ）を照射し、窒素雰囲気下においてホットプレート上で２００℃、２０分間熱処理し、電子ブロック層を形成した。偏光ＵＶは、ＧＳ ＵＶ ＳＹＳＴＥＭ（入江製作所株式会社製）のＵＶ照射機とＵＶ偏光フィルター２５．０ｍｍφ（エドモント オプティックス・ジャパン株式会社製）を用いた。次に白色発光材料（サメイション製ＷＰ１３３０）を０．８質量％の割合でトルエンに溶解し、さらにカルコン系光配向性化合物（ＲＯＬＩＣ社製、商品名：ＬＣＰＣＢ４８３ＣＰ）を白色発光材料１に対して重量比で２０％の割合で添加し、発光層用の塗布液を作製した。次に正孔注入層が形成された基板上に発光層用の塗布液をスピンコートによって塗布し、膜厚が８０ｎｍの薄膜を形成した。その後、偏光ＵＶ（波長２８０−３３０ｎｍ）を照射し、窒素雰囲気下のホットプレート上で１３０℃、３０分間熱処理し、発光層を形成した。発光層が形成された基板を真空蒸着機に導入し、ＩＴＯ薄膜のパターンに直交するように陰極としてＢａ、Ａｌをそれぞれ、１０ｎｍ、１００ｎｍの厚みで５×２ｃｍの帯状に順次蒸着し、陰極を形成した。陰極形成時の真空度が１×１０-4Ｐａ以下に到達した後に金属の蒸着を開始した。最後に、不活性ガス中で、ＩＴＯ薄膜と陰極が直交する部分を中心にガラス板で覆い、さらに４辺を光硬化樹脂で覆った後に、ＵＶ照射して光硬化樹脂を硬化させ、有機ＥＬ発光素子を作製した。
Example 4
<Production of EL element>
A liquid obtained by filtering a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Starck, trade name: AI4083) using a 0.45 μm filter was prepared in Example 1 above. A thin film having a film thickness of 65 nm was formed on the cleaned substrate by spin coating. Heat treatment was performed at 200 ° C. for 15 minutes on a hot plate in an air atmosphere to form a hole injection layer. Next, the polymer compound 1 synthesized above was dissolved in toluene at a ratio of 0.4% by mass, and a chalcone-based photoalignment compound (trade name: LCPCB483CP, manufactured by ROLIC) was further added to the polymer compound 1. And added at a ratio of 20% by weight to prepare a coating solution for the electronic block layer. Next, a coating solution for an electron blocking layer was applied by spin coating on the substrate on which the hole injection layer was formed to form a thin film having a thickness of 20 nm. Then, polarized UV (wavelength 280-330 nm) was irradiated and heat-treated at 200 ° C. for 20 minutes on a hot plate in a nitrogen atmosphere to form an electron blocking layer. As the polarized UV, a UV irradiation machine of GS UV SYSTEM (manufactured by Irie Manufacturing Co., Ltd.) and a UV polarizing filter 25.0 mmφ (manufactured by Edmont Optics Japan Co., Ltd.) were used. Next, a white light emitting material (WP1330 manufactured by Summation) is dissolved in toluene at a ratio of 0.8% by mass, and the chalcone-based photo-alignment compound (trade name: LCPCB483CP, manufactured by ROLIC) is added to the white light emitting material 1 by weight. The coating solution for the light emitting layer was prepared by adding at a ratio of 20%. Next, the light emitting layer coating solution was applied by spin coating on the substrate on which the hole injection layer was formed, to form a thin film having a thickness of 80 nm. Then, polarized UV (wavelength 280-330nm) was irradiated, and it heat-processed for 30 minutes at 130 degreeC on the hotplate in nitrogen atmosphere, and formed the light emitting layer. The substrate on which the light emitting layer is formed is introduced into a vacuum vapor deposition machine, and Ba and Al are sequentially deposited as a cathode in a thickness of 5 × 2 cm with a thickness of 10 nm and 100 nm so as to be orthogonal to the ITO thin film pattern. Formed. After the degree of vacuum at the time of forming the cathode reached 1 × 10 −4 Pa or less, metal deposition was started. Finally, in an inert gas, the glass thin plate and the cathode are covered with a glass plate at the center, and the four sides are covered with a photo-curing resin, and then UV irradiation is performed to cure the photo-curing resin. A light emitting element was manufactured.
（比較例１）
＜ＥＬ素子の作製＞
ポリ（３，４）エチレンジオキシチオフェン／ポリスチレンスルホン酸（スタルク社製、商品名：ＡＩ４０８３）の懸濁液を０．４５μｍ径のフィルターを用いてろ過した液を、上記実施例１で作製した洗浄済基板上にスピンコートにより塗布し、膜厚が６５ｎｍの薄膜を形成した。大気雰囲気下においてホットプレート上で、２００℃で１５分間熱処理し、正孔注入層を形成した。次いで、上記で合成した高分子化合物１を０．４質量％の割合でトルエンに溶解し、電子ブロック層用の塗布液を作製した。次に正孔注入層が形成された基板上に電子ブロック層用の塗布液をスピンコートによって塗布し、膜厚が２０ｎｍの薄膜を形成した。その後、窒素雰囲気下においてホットプレート上で２００℃、２０分間熱処理し、電子ブロック層を形成した。次に白色発光材料（サメイション製ＷＰ１３３０）を０．８質量％の割合でトルエンに溶解して発光層用の塗布液を作製した。次に正孔注入層が形成された基板上に発光層用の塗布液をスピンコートによって塗布し、膜厚が８０ｎｍの薄膜を形成した。その後、窒素雰囲気下のホットプレート上で１３０℃、３０分間熱処理し、発光層を形成した。発光層が形成された基板を真空蒸着機に導入し、ＩＴＯ薄膜のパターンに直交するように陰極としてＢａ、Ａｌをそれぞれ、１０ｎｍ、１００ｎｍの厚みで５×２ｃｍの帯状に順次蒸着し、陰極を形成した。陰極形成時の真空度が１×１０−４Ｐａ以下に到達した後に金属の蒸着を開始した。最後に、不活性ガス中で、ＩＴＯ薄膜と陰極が直交する部分を中心にガラス板で覆い、さらに４辺を光硬化樹脂で覆った後に、ＵＶ照射して光硬化樹脂を硬化させ、有機ＥＬ発光素子を作製した。
(Comparative Example 1)
<Production of EL element>
A liquid obtained by filtering a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Starck, trade name: AI4083) using a 0.45 μm filter was prepared in Example 1 above. A thin film having a film thickness of 65 nm was formed on the cleaned substrate by spin coating. Heat treatment was performed at 200 ° C. for 15 minutes on a hot plate in an air atmosphere to form a hole injection layer. Next, the polymer compound 1 synthesized above was dissolved in toluene at a ratio of 0.4% by mass to prepare a coating solution for an electronic block layer. Next, a coating solution for an electron blocking layer was applied by spin coating on the substrate on which the hole injection layer was formed to form a thin film having a thickness of 20 nm. Then, it heat-processed for 20 minutes at 200 degreeC on the hotplate in nitrogen atmosphere, and formed the electronic block layer. Next, a white light-emitting material (WP 1330 manufactured by Summation) was dissolved in toluene at a ratio of 0.8% by mass to prepare a coating solution for the light-emitting layer. Next, the light emitting layer coating solution was applied by spin coating onto the substrate on which the hole injection layer was formed, to form a thin film having a thickness of 80 nm. Then, it heat-processed for 30 minutes at 130 degreeC on the hotplate in nitrogen atmosphere, and formed the light emitting layer. The substrate on which the light emitting layer is formed is introduced into a vacuum vapor deposition machine, and Ba and Al are sequentially deposited as a cathode in a thickness of 5 × 2 cm with a thickness of 10 nm and 100 nm so as to be orthogonal to the ITO thin film pattern. Formed. After the degree of vacuum reached 1 × 10 −4 Pa or less when forming the cathode, metal deposition was started. Finally, in an inert gas, the glass thin plate and the cathode are covered with a glass plate at the center, and the four sides are covered with a photo-curing resin, and then UV irradiation is performed to cure the photo-curing resin. A light emitting element was manufactured.
＜有機ＥＬ素子の発光特性の評価＞
比較例１で作製した有機ＥＬ素子を発光させた光は無偏光であるのに対して、実施例１〜４で作製した有機ＥＬ素子を発光させた光は偏光光であることを観察した。発光層の配向性の高さから、偏光の程度は、実施例４＞実施例３＞実施例２＞実施例１の順になる。
<Evaluation of light emission characteristics of organic EL element>
It was observed that the light emitted from the organic EL element produced in Comparative Example 1 was non-polarized, whereas the light produced from the organic EL element produced in Examples 1 to 4 was polarized light. From the high orientation of the light emitting layer, the degree of polarization is in the order of Example 4> Example 3> Example 2> Example 1.
１ 有機ＥＬ素子
２ 第１電極
３ 第２電極
４ 発光層
５ 正孔注入層
６ 基板
DESCRIPTION OF SYMBOLS 1 Organic EL element 2 1st electrode 3 2nd electrode 4 Light emitting layer 5 Hole injection layer 6 Substrate
Claims (11)
前記発光層が、光を照射することで少なくとも一部が一軸配向した光配向性化合物と、発光する有機化合物とを含んで構成されることを特徴とする有機エレクトロルミネッセンス素子。 An organic electroluminescence device comprising a pair of electrodes and a light emitting layer located between the pair of electrodes,
The organic light-emitting device, wherein the light-emitting layer includes a photo-alignment compound that is at least partially uniaxially aligned when irradiated with light and an organic compound that emits light.
該機能層は、光を照射することで少なくとも一部が一軸配向した光配向性化合物を含んで構成されることを特徴とする請求項１または２記載の有機エレクトロルミネッセンス素子。 It further includes a functional layer located between the pair of electrodes and provided in contact with the light emitting layer,
3. The organic electroluminescence device according to claim 1, wherein the functional layer includes a photo-alignment compound that is at least partially uniaxially aligned by irradiation with light.
一対の電極のうちの一方の電極を形成する工程と、
発光層を形成する工程と、
一対の電極のうちの他方の電極を形成する工程とを含み、
発光層を形成する工程では、
光を照射することで配向する光配向性化合物と、発光する液晶性化合物とを含む塗布液を用いた塗布法により発光層用膜を形成し、
該発光層用膜に光を照射することで光配向性化合物および前記液晶性化合物の少なくとも一部を一軸配向させることを特徴とする有機エレクトロルミネッセンス素子の製造方法。 A method for producing an organic electroluminescent element comprising a pair of electrodes and a light emitting layer located between the pair of electrodes,
Forming one of the pair of electrodes;
Forming a light emitting layer;
Forming the other electrode of the pair of electrodes,
In the step of forming the light emitting layer,
A light emitting layer film is formed by a coating method using a coating liquid containing a photoalignable compound that is aligned by irradiation with light and a liquid crystal compound that emits light,
A method for producing an organic electroluminescence device, wherein at least a part of a photoalignment compound and the liquid crystal compound is uniaxially aligned by irradiating the light emitting layer film with light.
機能層を形成する工程では、
液晶性化合物と、光を照射することで配向する光配向性化合物を含む塗布液を用いた塗布法により機能層用膜を形成し、
該機能層用膜に光を照射することで前記光配向性化合物の少なくとも一部を一軸配向させることを特徴とする請求項１０記載の有機エレクトロルミネッセンス素子の製造方法。 Before the step of forming the light emitting layer, the method further includes a step of forming a functional layer on which the light emitting layer film is formed,
In the process of forming the functional layer,
A functional layer film is formed by a coating method using a liquid crystal compound and a coating liquid containing a photo-alignment compound that is aligned by irradiation with light,
The method for producing an organic electroluminescence device according to claim 10, wherein at least a part of the photo-alignment compound is uniaxially oriented by irradiating the functional layer film with light.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005531618A (en) * | 2002-07-01 | 2005-10-20 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Polymerizable, luminescent compounds and mixtures, luminescent polymer materials and their use |
| JP2005302641A (en) * | 2004-04-15 | 2005-10-27 | Seiko Epson Corp | Organic electroluminescent element, its manufacturing method, and electronic device |
| JP2006060198A (en) * | 2004-07-23 | 2006-03-02 | Konica Minolta Holdings Inc | Organic electroluminescent element, display and illuminating device |
-
2008
- 2008-03-28 JP JP2008086244A patent/JP2009239180A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005531618A (en) * | 2002-07-01 | 2005-10-20 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Polymerizable, luminescent compounds and mixtures, luminescent polymer materials and their use |
| JP2005302641A (en) * | 2004-04-15 | 2005-10-27 | Seiko Epson Corp | Organic electroluminescent element, its manufacturing method, and electronic device |
| JP2006060198A (en) * | 2004-07-23 | 2006-03-02 | Konica Minolta Holdings Inc | Organic electroluminescent element, display and illuminating device |
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