201201622 六、發明說明： 【發明所屬之技術領域】 本發明係關於用在照明器具、液晶背光、各種顯示器 、顯示裝置等之有機電致發光元件。 【先前技術】 過去已知有機EL元件（有機電致發光元件）為面發光 體的代表性物品。 圖5中顯示過去之有機EL元件的一例。此有機元 件係藉由於透光性的基板1的表面上設置透光性的第i電 極2、於此第i電極2上設置含有以有機電致發光材料構成 之有機發光層的有機層3、於此有機層3上設置光反射性之 第2電極4而形成。接著，藉由對第1電極2與第2電極4 之間施加電壓，在有機層3而發出的光通過第1電極2及 基板1而取出至外部。 如此圖示形態的有機EL元件於有機層3發出的光通過 第1電極2與基板1而取出至外部，光因第1電極2與基 板1的折射率差而於界面全反射時，光的提取效率會變二 。對此，從過去以來已有數個提案做為提升光提取效率之 手法。 每^專利文獻1中，記載了於光提取側的基板内部或外 P叹置以散射粒子及稜鏡片（丨ens等形成之光散射部 之有機EL發光裝置。 和既於專利文獻2中’記載了於透明基板上形成有透明樹 曰^透明電極、有機肛層、金屬電極，透明樹脂層在透 極側具有複數個倒半球形狀之有機EL元件。其特徵在 4/34 201201622 於：對於發光時朝向透明基板側之光，倒半球形狀 樹脂層有做為凸透鏡之功能。 此卜亦有&案減低環境光的反射，提高取出 可視性。 <九的 於專利文獻3中，記載了於具有與電力與光學狀 關之轉換層、與此轉換層相關之電極層之構造中， 層朝向外界側的至少—部分’有具有具備蛾眼構造之光 收區域之光利職置。其龍在於：藉由在產生環境光之 反射的金屬電極外部形成峨轉造以抑制反射 發光層之光的對比的降低。 1刺果自 [先前技術文獻] [專利文獻] 專利文獻1日本特開平8-83688號公報 專利文獻2日本特開2004-47383號公報 專利文獻3日本特開2004-258364號公報 【發明内容】 [發明欲解決之課題] 在形成如專利文獻丨之光散射部的情形，認 於前方散射，增加於電極與紐之界面及基板與 \ 面之臨界角以下之光量，而減少了全反射之光量。^是: 其-方面亦散射了原本於光散射部散射之從前面來= 角以内之光’因經散射之光於其它電極反射時有部分二 收’而被認為有無法急劇地增加光的提取量之問題。 又，如專利文獻2之形成具有透鏡功能之情形， 於界面將以臨界角以上之人射的光折射到臨界角以内，9可 5/34 201201622 量。但是另一方面’於具有透鏡功能之構造 及J構W接之層的界面會形成折射率落差。因此，無 法減低僅因與人射角無關之折射率落差所產生之反射，而 認為有無法期望大幅增加光的提取效率之問題。 又’於專利文獻3中，為了降低環境光之反射的目的 而使用魏構造，於此錢EL元件t，因在與光提取側之 相反側之金屬電歸面上形成有她構造，而被認為此構 造無法對提升光提取效率做出貢獻。 本發明有鑑於上述之課題，其目的為提供兼顧高效率 之光提取及提升可視性之有機EL元件。 [用以解決課題之手段] 第-形態係-種有機EL元件’其係包含一對電極 、及具有至少-個有機發光層之有機層，I特徵為在 光提取側之電極的至少—面、或在配置於光提取侧之 基板的至少-面，形成有配列周期為有機發光層所產 生之光的波長以下之微細周期構造，且在將與前述有 機層相反側之中與光提取側的電極鄰接之區域的折 射率設為nl、將前述電極的折射率設為Μ、將與前 述光提取側之電極鄰接之有機層的折料U n3時 ’η1$η2$η3或η2$ηκη3之關係成立。 第二形態係-種有機EL S件，其係、包含—對電極 、及具有至少-個有機發光層之有機層，1特徵為在 光提取侧之電極的至少—面，或在配置於綠取側之 基板的至少-面’形成有配列周期為有機發光層所產 生之光的波長以下之微細周期構造，且在將與前述有 6/34 201201622 機層相反側之中與前述光提取側的電極鄰接之區域 的折射率5又為η ]、將前述電極的折射率設為^ 與前士述光提取側之電極鄰接之有機層的折射率設為 n3 ，η2$η3$η1 或 n3$n2gnl 之關係成立。 '於上述有機el元件中，前述光提取側之電極較佳 為包含具有透光性之樹脂與微細導電性物質。於此情 形，前述微細導電性物質之反射率較料5〇%以上月。 又，前^微細導電性物質較佳為產生異方向性散射者 。又，前述微細導電性物質較佳為銀奈米導線。 p m機el元件中，前述光提取側之電極或配置 2边先提取側之基板，較佳為在表面具有單-或複 固凹部或凸部而形成微細周期構造。一 上述有機EL疋件中，治·、+、止& 詈方^'+.上,β 中則述先柃取側之電極或配 置方；則述先棱取側之基板在表 佳為在俯視之情形， ^ 1次凸。Η父 、同心圓狀、及蜂巢狀中任一 狀 期構造。 形狀配置而形成微細周 [發明效果] 依據本發明，可抑制臨界 提升臨界角以上之入射 Τ之射先的反射，並 境光之反射，可得到兼::=取:率’進-步可減少環 之有機EL元件。“效率之光提取與可視性之提升 【實施方式】 [貫施發明之最佳形態] 以下針對實施本發日;之形料以說明。 7/34 201201622 此右圖機1 關於本發明之有飢元件之層結構之一例 。此有機EL π件係藉由在透光性基板！的表面上設置透光 性第i電極2、於此第丨電極2之表面設置包含由有機電致 發光材料構成之有機發光層的層3、接著在此有機層$之表 面上設置光反射性之第2電極4而形成。接著，藉日由對第】 電極2與第2電極4之間施加電壓，而在有機層3發出的 光:係通過第1電極2及基板丄而取出至外部，圖】之形 態係稱為通過基板1來取出光之底部發射構造之有機虹元 件。第】電極2及第2電極4之中一者之電極為正極則另 -者為陰極，於圖式之形態中，帛】電極2為正極、第2 電極4為陰極。& ’在如此之結構的有機EL元件之情形， 為了解決上述課題，若減低在光提取側配置之基板丨與透 明電極之第1電極2的界面，及基板】與外部之界面續 射率差，則可減低光的反射。又，若藉由於透明電極之第i 電極含有產生光散射之導電性粒子來將臨界角以上之入射 角折射到臨界角以内，則可提升光提取效率。 於此，於圖1之形態中，在係光提取側之電極的第1 電極2之有機層3側的表面上’形成有目㈣周期為有機發 光層所產生光的波長以下、亦即為入射至此電極之光的波 長以下之微細周期構造5。微細周期構造5設置於光提取側 之電極的至少一面即可。因此，不限制於圖式之形態，亦 "T於弟1電極2之基材1側的表面，亦即僅在第1電極2 之基材1側的表面，或是在第1電極2的表面及背面兩面 上形成微細周期構造5。彼等之中，如圖式之形態，在第j 電極2之有機層3側的表面上形成配列周期為有機發光層 8/34 201201622 戶f產生之光之波長以下賴細周期構造5，由提升可視性、 提升光提取效率之觀點來看係較佳。此外，於透明電極之 第1電極含有產生光散射之導電性粒子，由進一步提升光 提取效率之觀點來看係較佳。 圖式之|β例巾’做為微細軸構造5，例示了於電極表 面突出之複數個凸部6以-定間距複數個並排 ，在相鄰之 凸4 6’6間有截面為半圓形之凹部7的微細周期構造5。於 此構造中’配列周期為相鄰之凹部7,7 (或凸部6,6)之中 心間距離。 方'圖1之形⑮中’在與有機層3相反側且與帛i電極2 鄰接的區域即為基板1。又，有機層3通常係以包括有機發 光層之複數個層卿成’㈣成有機層3之魏個層之中 與第1電極2鄰接之層，即做為與設置有微細周期構造$ 之電極鄰接之有機層3a。接著，將基板丨之折射率設為d 、苐1電極2之折射率設為n2、有機層^之折射率設為 n3 ’則在化n3時’ nl“2“3、或似化n3之關係 成立;。又’在將基板i之折射率設為n卜第i電極2之折 射率設為n2、有機層3a之折射率設為n3之情形，在η3‘ nl時’ η2$η3^η卜或化化nl之關係成立^ = 、，如此’藉由在第1電極2的至少—面形成周期為有機 發光層所產生之光的波長以下之微細周期構造5、折射率如 上述之關係，可將基材1及與^電極：鄰接之有機層允 的折射率落差加以傾斜。又’藉由微細周期構造5可^吏環 境光不容易反射。因此’可減少因折射率落差所產生的界 面反射’且可減少環境光之反射，可兼顧光提取之高效率 9/34 201201622 化及可視性之提升。 圖2令顯示本發明之有機紅 。此有機EL元件係藉由规：:、;=其匕範例 電極4、於此第2雷搞4心 表面吕又置光反射性第2 料播出♦士，電参4的表面设置含有以有機電致發井;fef ，成之有機發光層之有機層3 材 透光性第1電極2來形成。接著，藉由=== 電極4之間施加電屋而自有機層3發出^光第2 電極2取出至外部，圖出的先，係通過第1 構造的有;先之稱為頂部發射 電極為正極則另一者即為险° '、、電極4之中一者之 為正極、第2電極4 ^圖式之形態中第】電極2 &元件之情形，為=接者，於如此之構成的有機 却田 為了解決上述課題，若減少透明雷坧紅 敎界面的折射率差，則可減少反射n'外 f之第1電極含有產生光散射之導電_子=2電 上之=角折射至臨界角㈣，可提升光提取效^角以 極2二機ΐ=::，在光提取側電極之與第1電 為有機發光;所;=:=，形成配列周期 =光的波長以下之微細周期構造5。微二==極 置於光提取側之電極的至少-面即可。^ 設 之形態，亦可於第】電極2 限於圖式 :第1電極2之有機層3側的表面:或= :面及为面兩面形成微細周期構造5。其中，由可:： 、提升光提取效率之觀點來看，較佳為如圖式之形態， 10/34 201201622 於暴路方、與第1電極2之有機層3相反側的外部之表面， 开/成配列周期為有機發光層所產生之光的波長以下之微細 周期構造5。 於圖式之範例中，與圖1之情形相同，例示在電極表 面以一定間距並列複數個突出之複數個凸部6，相鄰之凸部 6:6間為錢面半圓形狀之凹部7的微細周期構造5，來做為 U細周期構造5。此構造中，配列周期為相鄰的凹部7,7 ( 或凸部6,6)之中心間距離。 圖2之形態中，在第〗電極2背對有機層3側與之鄰 ，的區域即為外部（空氣層等）。又，有機層3通常係以包 3有機發光層之魏層所縣，贼錢層3之複數層中 與第1電極2鄰接的層，便是設置有微細周期構造5之盘 =鄰接的有機層3a。又，將外部（空氣層等）之折射率 : 將第1包極2之折射率設為n2、將鄰接之有機層 %的折射率設為n3，則在nl“3日寺，nlSn2^3、或α :3之，係成立…在將外部（空氣層等）之折射 的：射二：1電極2之折射率設為以、鄰接之有機層3a η: ί 之情形’在獅時，n2崎η卜或 3 = η2$η1之關係成立。201201622 VI. Description of the Invention: [Technical Field] The present invention relates to an organic electroluminescence element used in lighting fixtures, liquid crystal backlights, various displays, display devices, and the like. [Prior Art] Conventionally, an organic EL element (organic electroluminescence element) has been known as a representative article of a surface light-emitting body. An example of a conventional organic EL element is shown in FIG. The organic element is provided with a light-transmissive i-th electrode 2 on the surface of the light-transmitting substrate 1, and an organic layer 3 containing an organic light-emitting layer made of an organic electroluminescent material on the i-th electrode 2, The organic layer 3 is formed by providing the second electrode 4 having light reflectivity. Then, by applying a voltage between the first electrode 2 and the second electrode 4, the light emitted from the organic layer 3 passes through the first electrode 2 and the substrate 1 and is taken out to the outside. The light emitted from the organic EL device in the organic layer 3 is taken out to the outside through the first electrode 2 and the substrate 1 , and the light is totally reflected at the interface due to the difference in refractive index between the first electrode 2 and the substrate 1 . The extraction efficiency will be two. In this regard, several proposals have been made in the past as a means of improving the efficiency of light extraction. In the above-mentioned Patent Document 1, it is described that an organic EL light-emitting device that scatters particles and a ruthenium (a light-scattering portion formed by 丨ens or the like) inside or outside the substrate on the light extraction side is described in Patent Document 2 An organic EL element having a transparent tree 透明 transparent electrode, an organic anal layer, and a metal electrode formed on a transparent substrate, and having a plurality of inverted hemispherical shapes on the transmissive side is described in 4/34 201201622 When the light is emitted toward the transparent substrate side, the inverted hemispherical resin layer functions as a convex lens. This also reduces the reflection of ambient light and improves the visibility of the extraction. [9] In Patent Document 3, In a structure having an electric-optical-optical conversion layer and an electrode layer associated with the conversion layer, at least a portion of the layer facing the outside side has a gravitational position having a light-receiving region having a moth-eye structure. The dragon is to reduce the contrast of the light of the reflective luminescent layer by forming a ruthenium outside the metal electrode that generates the reflection of the ambient light. 1 刺果自[Previous Technical Literature] [Patent Literature] Japanese Patent Publication No. 2004-258364 (Patent Document) Japanese Patent Application Publication No. 2004-258364 (Summary of the Invention) [Form of the Invention] In the case of the light scattering portion, it is recognized that the front scattering increases the amount of light below the critical angle between the electrode and the interface and the critical angle of the substrate and the surface, and reduces the amount of total reflection light. ^ Yes: The -the side also scatters the original The light scattered by the light scattering portion from the front side to the inside of the angle 'the light of the scattered light is partially diverged when reflected by other electrodes' is considered to have a problem that the amount of light extracted cannot be sharply increased. Further, as in Patent Document 2 The formation of the lens function, the interface will refract light of the person above the critical angle to within the critical angle, 9 can be 5/34 201201622. But on the other hand 'on the structure with lens function and J structure W The interface at the layer forms a refractive index drop. Therefore, it is not possible to reduce the reflection caused by the difference in refractive index irrespective of the angle of incidence of the human, and it is considered that there is a problem that it is not expected to greatly increase the extraction efficiency of light. Further, in Patent Document 3, in order to reduce the reflection of ambient light, a Wei structure is used, and since the EL element t is formed on the metal electric return surface on the opposite side to the light extraction side, In view of the above-mentioned problems, the present invention has been made in view of the above-mentioned problems, and an object thereof is to provide an organic EL device that achieves high-efficiency light extraction and improved visibility. [Means for Solving Problems] - The morphological-organic EL device includes a pair of electrodes and an organic layer having at least one organic light-emitting layer, and the I feature is at least a surface of the electrode on the light extraction side or a substrate disposed on the light extraction side. The at least one surface is formed with a fine periodic structure in which the arrangement period is equal to or less than the wavelength of the light generated by the organic light-emitting layer, and the refractive index of the region adjacent to the electrode on the light extraction side among the opposite side to the organic layer is set to Nl, the relationship between the refractive index of the electrode is Μ, and the relationship between the η1$η2$η3 or η2$ηκη3 of the organic layer of the organic layer adjacent to the electrode on the light extraction side is established. The second embodiment is an organic EL S member, comprising: a counter electrode, and an organic layer having at least one organic light emitting layer, wherein the feature is at least the surface of the electrode on the light extraction side, or is disposed in the green The at least one surface of the substrate on the side of the substrate is formed with a fine periodic structure in which the distribution period is equal to or less than the wavelength of the light generated by the organic light-emitting layer, and is in the opposite side to the aforementioned side having the 6/34 201201622 layer and the aforementioned light extraction side. The refractive index 5 of the region adjacent to the electrode is η], and the refractive index of the electrode is set to be n3, η2$η3$η1 or n3 of the organic layer adjacent to the electrode on the light extraction side of the prelude The relationship of $n2gnl is established. In the above organic EL device, the electrode on the light extraction side preferably contains a light transmissive resin and a fine conductive material. In this case, the reflectance of the fine conductive material is more than 5% by weight. Further, it is preferable that the front fine conductive material is an anisotropic scattering. Further, the fine conductive material is preferably a silver nanowire. In the el device el element, the electrode on the light extraction side or the substrate on the side on which the first extraction side is disposed preferably has a single-or complex recess or a convex portion on the surface to form a fine periodic structure. In the above-mentioned organic EL element, in the case of the treatment, the +, the stop, the square, the electrode, or the arrangement side, the substrate on the side of the first edge is in the table. In the case of looking down, ^ 1 convex. Structure of any of the uncle, concentric, and honeycomb. According to the present invention, it is possible to suppress the reflection of the incident Τ above the critical elevation critical angle and the reflection of the boundary light, and obtain the cum::= take: rate 'in step-step Reduce the organic EL element of the ring. "Efficiency Light Extraction and Visibility Improvement" [Embodiment] [Best Practice for the Invention] The following is a description of the implementation of this publication; 7/34 201201622 This right machine 1 is related to the present invention. An example of the layer structure of the hunger element. The organic EL π element is provided on the surface of the light-transmitting substrate!, and the surface of the second electrode 2 is provided with an organic electroluminescent material. The layer 3 of the organic light-emitting layer is formed by providing the second electrode 4 having light reflectivity on the surface of the organic layer $. Then, a voltage is applied between the first electrode 2 and the second electrode 4 by the day. The light emitted from the organic layer 3 is taken out to the outside through the first electrode 2 and the substrate ,, and the form of the image is referred to as an organic rainbow element that extracts light from the substrate 1 and has a bottom emission structure. The electrode of one of the second electrodes 4 is a positive electrode and the other is a cathode. In the embodiment of the figure, the electrode 2 is a positive electrode and the second electrode 4 is a cathode. & 'Organic EL in such a structure In the case of components, in order to solve the above problems, if the light extraction is reduced The interface between the substrate 丨 disposed on the side and the first electrode 2 of the transparent electrode, and the difference in the transmittance between the substrate and the external interface can reduce the reflection of light. Further, if the ith electrode of the transparent electrode contains light scattering When the conductive particles refract the incident angle above the critical angle to within the critical angle, the light extraction efficiency can be improved. Here, in the embodiment of Fig. 1, the organic layer of the first electrode 2 of the electrode on the light extraction side is obtained. The surface of the third side is formed with a fine period structure 5 in which the period (four) period is equal to or lower than the wavelength of light generated by the organic light-emitting layer, that is, the wavelength of light incident on the electrode. The fine period structure 5 is provided on the electrode on the light extraction side. Therefore, it is not limited to the form of the drawing, and is also the surface of the substrate 1 side of the first electrode 2, that is, only on the surface of the substrate 1 side of the first electrode 2, or The fine periodic structure 5 is formed on both the front surface and the back surface of the first electrode 2. Among them, in the form of a pattern, an organic light-emitting layer 8 is formed on the surface of the organic layer 3 side of the j-th electrode 2 /34 201201622 The wave of light produced by household f It is preferable from the viewpoint of improving visibility and improving light extraction efficiency, and the first electrode of the transparent electrode contains conductive particles that generate light scattering, thereby further improving light extraction efficiency. From the point of view, it is preferable. As shown in the figure, the "β 巾 towel" is a micro-axis structure 5, exemplifying a plurality of convex portions 6 protruding from the surface of the electrode by a plurality of side-by-side spacing, adjacent to the convex portion 4 6' 6 fine periodic structures 5 having concave portions 7 having a semicircular cross section. In this configuration, the 'arrangement period is the distance between the centers of adjacent concave portions 7, 7 (or convex portions 6, 6). In the shape 15 'the area on the opposite side to the organic layer 3 and adjacent to the 帛i electrode 2 is the substrate 1. Further, the organic layer 3 is usually formed by a plurality of layers including the organic light-emitting layer into a 'four' organic layer 3 Among the layers of the Wei layer, the layer adjacent to the first electrode 2 is an organic layer 3a adjacent to the electrode provided with the fine periodic structure $. Next, the refractive index of the substrate 设为 is set to d, the refractive index of the 苐1 electrode 2 is set to n2, and the refractive index of the organic layer is set to n3′. Then, when n3, 'nl“2′3, or n3 The relationship is established; Further, 'the refractive index of the substrate i is n, the refractive index of the i-th electrode 2 is n2, and the refractive index of the organic layer 3a is n3. When η3' nl, η2$η3^η The relationship of nl is established as ^^, and thus, by forming at least the surface of the first electrode 2 with a fine periodic structure 5 having a wavelength equal to or less than the wavelength of light generated by the organic light-emitting layer, the refractive index is as described above. The refractive index difference between the substrate 1 and the electrode: adjacent to the organic layer is inclined. Further, by the fine period structure 5, the ambient light is not easily reflected. Therefore, 'the boundary reflection caused by the difference in refractive index' can be reduced and the reflection of the ambient light can be reduced, and the high efficiency of light extraction can be achieved, and the improvement of visibility and visibility can be achieved. Figure 2 shows the organic red of the present invention. The organic EL element is broadcasted by the gauge::,; = its example electrode 4, and the second surface of the second core is luminescent and reflective, and the surface of the electrode 4 is contained. An organic electrophoretic well; a fef formed of an organic layer 3 of the organic light-emitting layer is translucent to the first electrode 2. Then, the second electrode 2 is emitted from the organic layer 3 by the electric field between the electrodes 4 and taken out to the outside, and the first structure is passed through the first structure; the first is called the top emission electrode. In the case of the positive electrode, the other is the danger ° ', one of the electrodes 4 is the positive electrode, and the second electrode is in the form of the second electrode in the form of the electrode 2 & In order to solve the above problem, the organic field of the composition can reduce the refractive index difference at the interface of the transparent Thunder and red sputum, thereby reducing the conductivity of the first electrode containing the light scattering by the reflection of the n' outer f. The angle is refracted to the critical angle (4), and the light extraction effect angle can be improved by the pole 2 2 ΐ =::, the light is extracted from the side electrode and the first electrode is organic light;; =:=, forming the arrangement period = light A fine period structure 5 below the wavelength. The microsecond== pole is placed on at least the surface of the electrode on the light extraction side. In the form of the first electrode 2, the surface of the first electrode 2 on the side of the organic layer 3: or =: the surface and the surface of the surface may be formed into a fine periodic structure 5. Among them, from the viewpoint of: and improving the light extraction efficiency, it is preferably in the form of a figure, 10/34 201201622 on the outer surface of the edrain side opposite to the organic layer 3 of the first electrode 2, The open/in arrangement period is a fine periodic structure 5 having a wavelength equal to or lower than the wavelength of light generated by the organic light-emitting layer. In the example of the drawing, as in the case of FIG. 1, a plurality of protruding portions 6 protruding in parallel at a certain interval on the surface of the electrode are exemplified, and the adjacent convex portions 6: 6 are recessed portions 7 of a semi-circular shape of a money surface. The fine cycle structure 5 is used as the U fine cycle structure 5. In this configuration, the arrangement period is the distance between the centers of the adjacent recesses 7, 7 (or the projections 6, 6). In the form of Fig. 2, the region adjacent to the side of the organic layer 3 on the side of the electrode 2 is the outside (air layer or the like). Further, the organic layer 3 is usually a layer of a layer 3 organic light-emitting layer, and a layer adjacent to the first electrode 2 in a plurality of layers of the thief money layer 3 is a disk provided with a fine periodic structure 5 = adjacent organic Layer 3a. Further, the refractive index of the outside (air layer or the like): the refractive index of the first cladding 2 is n2, and the refractive index of the adjacent organic layer % is n3, then nl "3日寺, nlSn2^3 , or α : 3 , is established ... in the external (air layer, etc.) refracted: shot 2: 1 the refractive index of the electrode 2 is set to, adjacent to the organic layer 3a η: ί 'in the case of the lion, The relationship between n2 ηη卜 or 3 = η2$η1 holds.
Si之極2的至少一面形成周期為有機發光層 如上下之微細周期構造5,藉由讓折射率為 有可使光發出的外部及與第1電極2鄰接之 率傾斜。因此，可減少因折射率二At least one surface of the Si pole 2 forms an organic light-emitting layer having a fine periodic structure 5 as described above, and the refractive index is such that the outer portion of the light emitted and the first electrode 2 are adjacent to each other. Therefore, the refractive index II can be reduced
可減少環境光之反射，可兼顧光提取之 同效率化射錄讀升。 敬取I 11/34 201201622 此處，微細周期構造5係將以電極 :的===單位結構，予以周期性的配^成= ^此構w亦可為稱為蛾眼構造之奈米級構造 期性的配列突出或.之複㈣雜叙構造。接著，傻 ==造等之微細周期構造5可從入射側於出射側 ί折射補斜’因崎揮紅狀功能。域是說，若在 置微細周期構造5來使折射率傾斜，因減少在界面 之反射而能夠提升光提取效率，又，藉由此微細 ’可^自外部人射至有機此元件之光（環境光）的反射 ，而合易觀看提取之光，可提升可視性。 微細周_造5之配列職係有機發㈣所產生之光 的波長以下。亦即，係以有機發光層發光、且人射至 微細周期構造5之電極的形成有微細周期構造5之面的光 jit射波長）以下之長度間距，配列-定形狀之微 、.福以’來形成微細周期構造5。若配列周期比入射波長大 則無法使折射率傾斜，故微細周期構造5的配朋 射波長以下。X ’此配列周期更佳為可視光等環境光（、來 自外部的光）之波長以下。藉此可確實的減少環境光之反 射。配列周縣為有機發光層所產生之光的波長以下即益 特殊限制，例如可為10〜聊細左右之周期（間距)。’’、、 如上所述，微細周期構造5係在做為光提取側之電極 的第1電極2之表面’以從截面看為凹凸形狀之方式，形 成具有單-個或複數個凹部7或凸部 可規則的配置軸_狀難。 及^ 6 圖3中顯示微細周期構造5之圖案的範例。於圖式之 12/34 201201622 粑例中’顯於第1電極2表面微細周期構造5所形成的 樣子。圖3 (a)為在電極表面呈直線狀地凹人之凹部7 ( 或者突出之凸部6 )以-定間鄉行地複數條並列之條紋狀 之微細周期構造5賊例。圖3 (b)為在電極表面以呈格 子狀地凹人之凹部7 (或者突出之凸部6)所形成之格子狀 微細周期構造5的範例。圖式之職巾，好形狀係為圍 棋盤目狀（以垂直之複數個直線狀凹部7或凸部6為單位 構造所軸的正转幻’亦可為其它格子雜（以長方形 或平打四邊形做為單位構造之形狀）。圖3⑷為在電極表 面呈圓狀地凹人之複數個凹部7(或者突出之凸部6 )以一 定間距呈同w ®狀地配置而成之同㈣狀微細周期構造$ 的範例。於此形態中，藉由凹部7或凸部6所形成之圓的 直徑係自财⑽外_-定量變大。圓形可為正圓亦可 為橢圓。圖3⑷為在電極表面呈正六角形狀地凹入之凹 部7 (或者突出之凸部6)細密充填成蜂巢狀之蜂巢狀微細 ，期構t 5的犯例。像這樣藉由讓微細周期構造$成為預 疋形狀’可減少人射至微細周期構造5之光的反射，在可 進-步效率良好地提取光的同時，可提升可視性。 =中顯示有機EL元件之實施形態的其它實例。此形 == 中板=__8(或者凹形 成在基板1之弟1電極2侧者。於圖式之形熊 造5之關㈣的間距大之凸雜8與凹 =:可為單一個。凸形狀8或者凹形狀9可於= 表面形成點狀，亦可形成錄。又，凸職8與凹形狀^ 13/34 201201622 tb可複合形狀。接著，如p部分之擴大圖的圖4 為有機發光層所產生之光的波側絲成有配列周期 此細周期構造5係以形成在基板i之凹凸开，狀， 面傾斜地配置。如此，藉由在 凸祕對者發光 可進_牛访,„ 在基板1表面形成凹凸形狀， =步減少人射至微細周期構造5之光的反射 同效率之光提取與可視性之提升。 衆顧 ，在元件中，於在光提取側配置有基板1之情形 極t之面，亦即在外部側之表面或第1電 光的、Λ 配__麵發光層所產生之 先的波長町之微細周輯造％在 取效率，亦可提高可視性。接著，在^ ^升光提 期構造5之情形，第”如介叮，板1形成有微細周 有亦可。跡弟1電極2亦可有微細周期構造5,但沒 在於基板1形成時的微細周期構造 電極2時之情形相同。亦即板：面:置 Γ或複數個凹部7或凸部6來形成微細周? =面之情形’凹部7或凸部6可以條紋狀、格子狀 、同心圓狀、及蜂巢狀之任一形狀爽 千狀 周期構造5。 ^狀末予从配置，形成微細 做為基板1者並無_關，可 所形成者。但是，在通過基板！來提取光之=: 用光可以透過之材質。做為基板i之材料// 糸使 ，及無鹼玻璃等硬性透明玻璃板、聚碳酸:=納 甲酸乙二酯等彈性透明塑膠板等。 及聚對本一 14/34 201201622 之表面可為平坦，或者亦可如上述在截面形狀 1早:個或者複數個凸形狀8或凹形狀9。做為在基板i 之表面形成單—個或複數個凸形狀8或凹形狀9之方法， 可舉出使㈣纟域許紅細來直接加It can reduce the reflection of ambient light, and can take into account the same efficiency of the light extraction. Desire I 11/34 201201622 Here, the fine period structure 5 series will be periodically arranged with the unit structure of the electrode: === = ^ This structure w can also be a nano-scale called moth-eye structure The tectonic period is highlighted or the complex (4) hybrid structure. Then, the fine periodic structure 5 of the silly == creation can be refracted from the incident side to the exit side ί. The field is that if the fine periodic structure 5 is placed to tilt the refractive index, the light extraction efficiency can be improved by reducing the reflection at the interface, and the light can be emitted from the external person to the organic component by the microscopic ( The reflection of the ambient light), while the easy to view the extracted light, can improve the visibility. The wavelength of light generated by the micro-weeks of the assigned grades is less than or equal to the wavelength of light produced by the organic hair (4). In other words, the organic light-emitting layer emits light and the length of the light of the surface of the fine periodic structure 5 on the surface of the fine periodic structure 5 is less than or equal to the length of the light, and the shape is slightly smaller. 'To form a fine periodic structure 5. If the arrangement period is larger than the incident wavelength, the refractive index cannot be tilted, so that the fine period structure 5 has a wavelength below the wavelength. This arrangement period of X ′ is preferably equal to or less than the wavelength of ambient light such as visible light (light from the outside). This can reliably reduce the reflection of ambient light. It is a special limitation to the wavelength of the light generated by Zhou County as the organic light-emitting layer, for example, it can be a period (distance) of about 10 minutes. '', as described above, the fine periodic structure 5 is formed such that the surface of the first electrode 2 as the electrode on the light extraction side has a single-number or a plurality of concave portions 7 in a concave-convex shape as viewed in cross section. The convex portion can be arranged in a regular manner. And Fig. 3 shows an example of the pattern of the fine periodic structure 5. In the example of Fig. 12/34 201201622, the 'first electrode 2 surface fine periodic structure 5 is formed. Fig. 3 (a) shows an example of a micro-period structure 5 in which a concave portion 7 (or a protruding convex portion 6) which is linearly recessed on the surface of the electrode is arranged in a plurality of stripes in a row. Fig. 3 (b) is an example of a lattice-like fine periodic structure 5 formed by recessing a person 7 (or a protruding portion 6) in a lattice shape on the surface of the electrode. The figure has a good shape, which is a checkerboard shape (the forward rotation of the axis is formed by a plurality of linear recesses 7 or convex portions 6 in a vertical direction), and may be other lattices (in a rectangular or flattened quadrilateral shape) As a unit structure shape, Fig. 3 (4) is a plurality of concave portions 7 (or protruding convex portions 6) which are concavely formed on the surface of the electrode, and are arranged in the same w ® shape at a certain pitch. An example of the periodic structure $. In this embodiment, the diameter of the circle formed by the concave portion 7 or the convex portion 6 is increased from the outer (10) to the outer diameter. The circular shape may be a perfect circle or an ellipse. Fig. 3(4) is The concave portion 7 (or the protruding convex portion 6) recessed in the shape of a regular hexagon on the surface of the electrode is finely filled into a honeycomb-like honeycomb shape, and the structure of the structure t 5 is made. Thus, by making the fine cycle structure $ The shape 'reduces the reflection of light that is incident on the fine period structure 5, and improves the visibility while efficiently extracting light. The other examples of the embodiment of the organic EL element are shown. = Medium plate = __8 (or concave formed on the side of the electrode 1 of the substrate 1 In the figure, the shape of the bear is 5 (4). The spacing between the teeth 8 and the concave = 8 can be single. The convex shape 8 or the concave shape 9 can be formed into a dot shape on the surface of the surface. , convex position 8 and concave shape ^ 13/34 201201622 tb composite shape. Next, as shown in Fig. 4 of the enlarged view of the p portion, the wave side of the light generated by the organic light-emitting layer has a matching period. The surface of the substrate i is formed so as to be uneven, and the surface is inclined. Thus, by illuminating the target, it is possible to form a concave-convex shape on the surface of the substrate 1, and the step is to reduce the incidence of the human to the fine periodic structure. The reflection of light is the same as the extraction of light and the improvement of visibility. In the component, the surface of the substrate 1 is disposed on the light extraction side, that is, the surface on the outer side or the first electro-optic Λ Λ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The plate 1 may be formed with a fine circumference. The electrode 1 may also have a fine periodic structure 5, but it is not The case where the electrode 1 is formed in the fine period when the plate 1 is formed is the same. That is, the plate: face: a plurality of recesses 7 or protrusions 6 are formed to form a fine circumference? = the case of the face 'the recess 7 or the protrusion 6 may be striped Any of the shape, the lattice shape, the concentric shape, and the honeycomb shape, the shape of the cycle is 5. The shape of the shape is set to be fine, and the substrate is formed as a substrate 1 without being closed. However, The substrate is used to extract light =: material that can be transmitted through light. It is used as the material of the substrate i. / /, and the transparent transparent glass plate such as alkali-free glass, and the transparent transparent plastic such as polycarbonate: = ethylene natriate. The surface of the plate and the like may be flat, or may be as early as the cross-sectional shape 1 as described above: or a plurality of convex shapes 8 or concave shapes 9. As a method of forming a single or a plurality of convex shapes 8 or concave shapes 9 on the surface of the substrate i, it is possible to directly add (4)
法’但不限制於此。 ^ U 基板1之折射率較佳為1.2〜1.8。於圖i之形態中.，基 板1 =折射率設為η】。藉由讓基板丨的折射率在此範圍内 ’可容易的讓上述折射率關係成立。X，於圖2之形態中 ’外=(空氣層）之折射率為nl。通常，空氣之折射率為 丄左右。 光提取側的電極之第！電極2可藉由導電性物質形成 做料電性物質者可可列舉銀、銦_錫氧化物⑽）、銦 古化物=Ζ〇)、錫氧化物、Au等金屬微粒子、導電性 二Γ子性有機材料、含有摻雜物（予體(d〇n〇r)或受 導输輸錢材料（含高 j 2之電㈣x佳係藉純含有透紐之樹脂與微 ΐ 5之光提貝取 =1所形ΐ。於此情形’具有微細周期構 導電性物' ㈣4 ’㈣包含树級讀脂與微細 期橋、告5，\可^了導電性與散射性。亦即’藉由微細周 * =1+的二^、因折射率落差產生之界面反射、及環境 光之反射的同時，藉由酤本 兄 之# 賦予政射性，在電極、及與此電極 ,^ X、層之面的相反面鄰接的區域之間，可散 ，抑制全反射。藉此，可進一步兼顧高效率 之先提取”可視性之提升。χ，藉由以含樹脂之材料來形 15/34 201201622 成電極’可簡單的形成微細周期構造5。 做為微細導電性物質者 亦即，入射至微細周二^佳為反射率5〇%以上者。 為50%以上。於此产^ 5之光的波長中，光的反射率 吸收，賴可兼顧細導電性物質之光的 χ , 文旱之先楗取與可視性之提升。 又微、、，田導電性物質較佳 =即’入射至具有微細周期構造5之電== 性而有散射者。於此情妒，m电從的九U方向 向性散射，可期待#2微細導電性物質藉由產生異方 周期構迭5,在T货,'之光提取效果。亦即，藉由微細 =構0 ’在可減少因折射轉差產生之界面反射 二的同時’藉由賦予異方向性散射性，在電極, =此;=成有有機發光層之面的相 =率==制全反射之光。藉此，可進-步兼顧 ，微二產生異方向性散射 、祕較佳不疋球形狀等沒有異方向性 二 :有異方向性之形狀。例如，若使用長徑與短徑差 大之形狀的金屬奈米粒子、或金屬為奈米尺寸之線 屬奈米導線，便可容易產生異方向性散射。 * 微細導電性物㈣藉由具有導電性之材 =:=:形，較佳為粒徑—，二粒 ，較佳為直徑]〜H)0nm、長寬比】〜1〇〇。粒徑或 長見比若在此範園外’則光提取效率有惡化的可能。粒徑 可使用例如動態光散射光度計(DLS_80〇〇、大塚電子公司= )測定。 x 做為微細導電性物質，可使用導電性奈米粒子、導電 16/34 201201622 性奈米導線’例如較佳使用金屬奈米粒子、金屬奈米導線 。此外，較佳使用反射率高之銀。此外，其中較佳使用銀 奈米導線。於此情形，微細導電性物質為銀奈米導線，可 提高了反射率、產生異方向性散射、減少因折射率落差產 生的界面反射、且可在減少環境光之反射的同時減少在微 . 細導電性物質之吸收，可更有效的抑制在形成有此電極^ - 有機發光層之面、與鄰接相反面之區域之間的反射光。藉 此，可進一步兼顧高效率之光提取與可視性之提升。 微細周期構造5可藉由以光或電子線之光刻或奈米壓 印方法等來形成。特別是奈米壓印為形成奈米級周期構造 之簡便方法。亦即，可藉由將以電子束等加工之具有數十 〜數百nm之凹凸構造的打印板，按壓在形成於基板上之柔 軟光阻薄膜狀電極層、然後剝離來形成凹凸構造圖案。亦 可使用乾式蝕刻取代電子束。或者亦可使用濕式蝕刻法。 打印板(~Stamp)係於Si、Si02等基板上藉由光刻、蝕刻技術 、FIB等電子線直描技術來製作成具有至少一個凹凸部。於 在基板1形成微細周期構造5之情形，此打印板亦可做為 基板1使用。微細周期構造5之凹凸高度（或深度）係例 如可為1〜l〇〇〇nm、或者i — iOOnm、具體而言為1〇nm& 右或50ηηι左右，但不限制於此。 ^配置於光提取側之具有微細周期構造5的電極可藉由 製作形成有圖案之光阻_的方法來形成。例如，可藉由 方疋轉主布、網版印刷、浸潰塗布、模具塗布、澆塗、噴灑 塗布、凹版塗布來形成含導電性物質之樹脂等材料。 做為配置於光提取側之具有微細周期構造5的電極所 17/34 201201622 使用的樹脂者，較佳為使用透光性樹脂。例如 酸樹脂、聚乙稀、聚丙稀、聚對笨二甲酸」二:= 丙烯酸曱醋、聚笨乙稀、聚醚石風、聚芳錯、聚碳酸賴脂 、聚胺基曱酸醋、聚丙稀腈、聚乙稀縮駿、聚酿胺、聚醯 亞胺、酞酸二丙烯酸酯樹脂、纖維素系樹脂、聚氣乙烯、 聚偏二氣乙稀、聚麟乙烯自旨、其它熱可塑性樹脂、2種以 上構成此等樹脂之單體之共聚合體。其中，可較佳的使用 PMMA (聚曱基丙酯）及聚笨㈣。電極中樹脂與 被細導電性物質之含量比係形成電極時的體積比，例如可 =定在導電性物質：樹脂=1 : M : 3G之範圍。藉由讓含 1比在此範圍’可更容易的形成微細周期構造5，提升 取效率。 ^細周期構造5的配列周期為在有機發光 先的波長以下，亦即入射波長以下，微 可為放射線狀、矩形、V字溝狀等各^ 圍，厚雖無特殊限制，但較佳在⑽左右之範 又’配置於光提取側之形成有微 之折射率（η2)通常在u〜2() ^構化5的電極 板]之折射率綱或以®’較佳狀成與基 之折射率以下，難_板丨提取1 此電極入射至基板！之光 j之料，可減少自 率變得更大。 射，使仔自外部提取光之效 有機層3中，做為形成有 如可列舉蒽、萘、芘、并四=:有機EL材料，例 、寇、茈、酞茈 '萘茈、二 18/34 201201622 苯基丁二烯、四笨基丁二烯、香豆素、噁二唑、雙笨并噁 唾琳、雙苯乙稀、環戊二稀、啥琳金屬錯合物、參（8-經基 啥琳）铭錯合物、參（4-曱基-8-啥琳）鋁錯合物、參（5· 笨基-8-喹啉）鋁錯合物' 胺基喹啉金屬錯合物、笨并喹啉 金屬錯合物、三（對聯三苯_4_基）胺、吡喃、喹吖酮 (quinacridone)、紅螢烯(rubrene)、及此等之衍生物、或者、 基-2:5-二（2-噻吩基）吡咯衍生物、二笨乙烯笨衍生物 、苯乙稀衫基衍生物、笨乙雜衍生物、及於分子的一 部分具有此等發紐化合物職紅基的化合物或者高分 子等。又以上述化合物所代表的不僅是源自螢光色素之化 合物’亦可適當使用所謂_光發光材料，例如Ir錯合物 、Os錯合物、Pt錯合物、銪錯合物料發紐料' 或在分 子内具有彼等之化合物或高分子。此等材料可依 選擇使用。 而文〜田 又，於有機層3，除了有機發光層以外，亦可適時設置 正孔注入層（電洞注人層）、正孔傳輸層if 電子傳輸層、電子注人㈣各層。又，電子注人層之此等 層原本即可从以錢㈣製作，但此處係做為有機们 予以說明。 有機層3巾，與形成有微細周期構造5之電極接觸之 曰5又為有機層3a。因此，在有機發光層與電 則是以有機發光較為有機層3a，但在與電極接觸^= 其他層（例如電洞傳輸層）情 曰馮 „<度升y 5亥層（例如電洞僂給 層）係設為有機層3a。接著，將此有機層 n3。有機層3a之折射率〇3屮η1 β 斤耵半。又马 3比ηΙ及η2大者，雖為較佳形 19/34 201201622 態之一 ’然例如折射率n3之範圍可設定在ι·4〜1.8左右。The law 'is not limited to this. ^ U The refractive index of the substrate 1 is preferably from 1.2 to 1.8. In the form of Fig. i, the substrate 1 = the refractive index is set to η]. The above refractive index relationship can be easily established by making the refractive index of the substrate 在 within this range. X, in the form of Fig. 2, the refractive index of 'outer = (air layer) is nl. Usually, the refractive index of air is around 丄. The electrode of the light extraction side is the first! The electrode 2 can be made of a conductive material to form an electrical material, such as silver, indium-tin oxide (10), indium anthracene = yttrium, tin oxide, Au, and the like, and conductive dice. Organic materials, containing dopants (donor (d〇n〇r) or lead-transporting materials (including high-j 2 electric (four) x good system by pure resin containing micro-transparent and micro-purine 5 1 shape. In this case 'has a fine periodic structure conductivity' (4) 4 '(4) contains tree-level reading and micro-stage bridge, 5 5, \ can be conductive and scattering. That is, 'by fine weeks * =1 + 2 ^, the interface reflection due to the difference in refractive index, and the reflection of ambient light, with the enthusiasm of 酤本兄之#, at the electrode, and with this electrode, ^ X, layer Between the adjacent areas of the opposite side of the surface, it can be scattered, and the total reflection can be suppressed. Thereby, the improvement of visibility can be further improved in consideration of high efficiency. χ, by forming a material containing resin into 15/34 201201622 The electrode ' can be simply formed into a fine periodic structure 5. As a fine conductive substance, that is, incident on a fine Tuesday ^ Preferably, the reflectance is 5〇% or more. It is 50% or more. In the wavelength of the light produced by the light, the reflectance of light is absorbed, and the light of the fine conductive material can be taken into consideration. And the improvement of the visibility. The micro-, and, the field conductive material is better = that is, 'incident to the electric power with the fine periodic structure 5 == and there is scattering. In this case, the m-electric direction is from the nine U direction. Sexual scattering, can expect #2 fine conductive material by generating a heterocyclic periodic structure 5, in T goods, 'light extraction effect. That is, by fine = 0' can reduce the occurrence of refraction slip When the interface reflects two, 'by giving the directional scattering property, at the electrode, = this; = the phase of the organic light-emitting layer = the ratio == total reflection light. The micro-two produces an omnidirectional scattering, the secret is preferably a non-spherical shape, and the like, and has no directionality: a shape having a different directionality. For example, if a metal nanoparticle having a large diameter and a short diameter difference is used, or a metal The line of nanometer size is a nanowire, and it is easy to produce anisotropic scattering. * The fine conductive material (4) has Electrical material =: =: shape, preferably particle size -, two particles, preferably diameter] ~ H) 0nm, aspect ratio] ~ 1 〇〇. Particle size or long-term ratio if in this Fanyuan In addition, the light extraction efficiency may be deteriorated. The particle diameter can be measured using, for example, a dynamic light scattering photometer (DLS_80〇〇, Otsuka Electronics Co., Ltd.). x As a fine conductive material, conductive nano particles can be used and conductive. 16/34 201201622 The magnetic nanowire 'for example, metal nano particles and metal nanowires are preferably used. Further, silver having a high reflectance is preferably used. Further, silver nanowires are preferably used. In this case, fine The conductive material is a silver nanowire, which can improve the reflectivity, generate anisotropic scattering, reduce the interfacial reflection caused by the refractive index drop, and reduce the reflection of ambient light while reducing the fine conductive substance. By absorption, it is possible to more effectively suppress the reflected light between the surface on which the electrode-organic light-emitting layer is formed and the region opposite to the adjacent surface. As a result, high-efficiency light extraction and visibility can be further improved. The fine period structure 5 can be formed by photolithography or nanoimprinting method using light or electron lines. In particular, nanoimprinting is an easy way to form a nanoscale periodic structure. In other words, the printed circuit board having a concave-convex structure of several tens to several hundreds of nm processed by an electron beam or the like is pressed against the soft photoresist film electrode layer formed on the substrate, and then peeled off to form a concave-convex structure pattern. Dry etching can also be used instead of the electron beam. Alternatively, a wet etching method can also be used. The printing plate (~Stamp) is formed on a substrate such as Si or SiO 2 by a direct current drawing technique such as photolithography, etching, or FIB to have at least one uneven portion. In the case where the fine periodic structure 5 is formed on the substrate 1, the printing plate can also be used as the substrate 1. The height (or depth) of the concavities and convexities of the fine periodic structure 5 may be, for example, 1 to 1 〇〇〇 nm, or i - iOO nm, specifically, 1 〇 nm & right or 50 ηηι, but is not limited thereto. The electrode having the fine periodic structure 5 disposed on the light extraction side can be formed by a method of forming a patterned photoresist _. For example, a material such as a resin containing a conductive material can be formed by a square roll, a screen printing, a dip coating, a die coating, a cast coating, a spray coating, or a gravure coating. As the resin used for the electrode 17/34 201201622 having the fine periodic structure 5 disposed on the light extraction side, a translucent resin is preferably used. For example, acid resin, polyethylene, polypropylene, poly(p-dibenzoic acid) two: = acrylic acid vinegar, polystyrene, polyether stone, poly aryl, polycarbonate, polyamine phthalic acid, Polyacrylonitrile, Polypropylene, Polyamide, Polyimide, Capric Acid Diacrylate, Cellulose Resin, Polyethylene, Polyethylene Ethylene, Polyvinylidene, Other Heat A plastic resin or a copolymer of two or more kinds of monomers constituting the resins. Among them, PMMA (polypropyl propyl ester) and polystyrene (four) can be preferably used. The volume ratio of the ratio of the resin to the finely conductive substance in the electrode to form the electrode can be, for example, set in the range of the conductive material: resin = 1: M : 3G. The efficiency of the extraction is improved by forming the fine cycle structure 5 with a ratio of 1 in this range'. The arrangement period of the fine period structure 5 is equal to or lower than the wavelength before the organic light emission, that is, below the incident wavelength, and may be a radial shape, a rectangular shape, a V-shaped groove shape or the like, and the thickness is not particularly limited, but is preferably (10) The left and right vanes are also arranged on the light extraction side to form a refractive index (η2) which is usually in the thickness of u~2(). Below the refractive index, it is difficult to extract the plate 1 This electrode is incident on the substrate! The light of j can reduce the self-rate and become larger. In the organic layer 3 which is used for extracting light from the outside, as an example, it can be exemplified by yttrium, naphthalene, anthracene, and tetra-=: organic EL materials, for example, 寇, 茈, 酞茈 'naphthoquinone, II 18/ 34 201201622 Phenyl butadiene, tetraphenyl butadiene, coumarin, oxadiazole, double stupid and sulphur, diphenylethylene, cyclopentadiene, ruthenium metal complex, ginseng (8 - 啥基啥琳) Ming complex, ginseng (4-mercapto-8-啥琳) aluminum complex, ginseng (5· phenyl-8-quinoline) aluminum complex 'aminoquinoline metal a complex, a stupid quinoline metal complex, a tris(p-triphenyl-4-yl)amine, a pyran, a quinacridone, a rubrene, and derivatives thereof, or , a base-2:5-bis(2-thienyl)pyrrole derivative, a distyrene derivative, a styrene derivative, a stupid derivative, and a part of a molecule having such a compound A compound or polymer such as a red base. Further, the compound represented by the above compound is not only a compound derived from a fluorescent pigment, but a so-called photoluminescent material such as an Ir complex, an Os complex, a Pt complex, a ruthenium complex material can also be suitably used. ' Or have their compounds or polymers in the molecule. These materials can be used as appropriate. In addition to the organic light-emitting layer, the organic layer 3 may be provided with a positive hole injection layer (hole injection layer), a positive hole transmission layer if electron transport layer, and an electron injection (4) layer. Moreover, these layers of the electronic injection layer can be produced from the money (4), but they are described here as organic. The organic layer 3, which is in contact with the electrode in which the fine periodic structure 5 is formed, is again an organic layer 3a. Therefore, in the organic light-emitting layer and the electricity, the organic light-emitting layer 3a is organic light-emitting layer, but in contact with the electrode, the other layer (for example, the hole transport layer) is inferior to the surface layer (for example, a hole). The enthalpy layer is set to the organic layer 3a. Next, the organic layer n3 is formed. The refractive index of the organic layer 3a is 〇3屮η1 β 耵 耵 。 。 。 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 大 大 大 大 大 大 大 大/34 201201622 One of the states 'for example, the range of the refractive index n3 can be set to about ι·4~1.8.
It由讓折射率η3在此範圍内，更提升光提取效率。 在與有機層3之第1電極2相反之側，設置有第2電 極4。可使用Α1等做為第2電極4材料，亦可為組合A1 與其它電極材料之積層構造等構成。做為如此之電極材料 組合者，可列舉鹼金屬與A1之積層體、鹼金屬與銀之積層 體、驗金屬之齒化物與AI之積層體、鹼金屬之氧化物與 A1之積層體、驗土類金屬或稀土類金屬與Ai之積層體、此 等金屬類與其它金屬之合金等，具體而言可舉例出例如鈉 、鈉-鉀合金、鋰、鎂等與A1之積層體、鎂_銀混合物、鎂_ 銦混合物、鋁-鐘合金、UF/A1混合物/積層體、A1/A丨处混 合物等。上述列舉之材料及形態僅為範例，並非限制於此 在光自第1電極2側取出之情形，較佳為使用反射性良 好之材料。又’光亦可自兩面（第1電極2側及第2電極4 側二者）取出，於此情形，第2電極4較佳為使用透光性 材料。 做為有機EL元件之製造方法者並無特別限制，可以一 般方法製作。亦即，可藉由適當的塗布法及驗，依序積 層各層於基板1之表面予以形成。最後亦可以密封蓋等密 封。 【實施例】 〔元件之製作〕 (實施例1) 使用無鹼玻璃板做為基板1 (Corning公司製ΓΝ〇 1737 」）。此基板1於波長500nm之折射率（η1)為丨別〜丨53 20/34 201201622 。又，折射率係以SCI公司製之FilmTek來測定（以下之 折射率測定亦相同）。 使用與上述基板1相同者做為打印板用基板 。於此打 印板用基板之表面，以濕式蝕刻法形成如下構造：俯視時 ，係以中心間的間距為約300nm，來配列複數條直線之條 、’’文狀，戴面形狀為寬度（底邊）約2〇〇nm、高度約5〇nm之 三角形（逆V字形）之具有複數個凸部之構造，來製作打 印板。 ^做為於基板1上形成第1電極2用之溶液，係使用將 聚曱基丙烯酸甲酯（PMMA、Aldrich公司製）分散於ιτ〇 示米粒子，谷液（粒控約4〇nm、c.i.Kasei公司製NanoTek ( 。主冊商;f示）ITCW15wt°/〇-G30)而得之i〇wt0/。丙g同溶液，以 體積比成為ITO奈米粒子：PMMA=1 : 8之方式混合而得 者。PMMA為具有性之樹脂。將此溶液藉纟旋轉塗布 法以膜厚成為100nm之方式，塗布在基板1上，加熱至1〇〇 C。藉此製作電極形成層。製得之電極形成層（第丨電極2 )的折射率（n2)於波長500nm為約1.49。 接著，將基板1之形成有電極形成層之面與形成有打 (7板之圖案之面相對，將打印板重疊於基板1上，以$〜 lOMpa之壓力按壓，保持1分鐘後將打印板剝離。藉此， 形成具有以約30〇nm之配列周期並列俯視為以複數個直線 所構成之條紋狀、截面形狀為複數個逆三角形（V字形） 之複數個凹部7的微細周期構造5之第1電極2。此第j電 極2做為正極。又，微細周期構造之配列周期（3O0nm)係 比下面說明之有機發光層所產生之光的波長還小。、 21/34 201201622 處理對Si 第1電極2之面進行5 — 苯基置中，一 著，在有齡# 7之兼作f子籠層之有機發光層。接 蒸鍍以A1(高純度化與 後在電子注入層上藉由真空 之第2電極4。 司製）形成膜厚8〇·、做為陰極 之乾成有各層之基板1於露爾以下 地搬運。-方 封劑塗布者。接著’於^；!備㈣外線硬化樹脂製之密 封蓋以密封劑貼在兵板套相内以將各層包住的方式將密 劑，以密封蓋密封L。上，猎由照射紫外線來硬化密封 細周ttirf結構如圖1之在第1電極2上形成有微 。化之折射率關係為n2<nl<n3之有機EL元件 (實施例2) ’使用將銀奈米粒子(粒徑約 射羊9〇/°以上）與讀A以與實_ !相同之質 22/34 201201622 量比率以溶劑分散而成之銀奈米粒子：pMMA溶液。第！ 電極2之膜厚為K)〇nm。所製作之第】電極2之折射率（ n2)於波長500nm為約U9。除此之外，以與實施例i相 同之方式來得到層結構如圖1之有機El元件。 (實施例3) 做為第1電極2之材料，使用將銀奈米導線（直徑約 „ 5Gnm、長度約5阿、反射率嶋以上）與pMMA以斑實施 例丨相同之質量比率以溶劑分散而成之銀奈米導線:pMMA 溶液。銀奈米導線係依照公開的論文「_她❽⑽邮 and Physics V〇1.m P333-338 “Preparati〇n 〇f Ag 麵她It makes the light extraction efficiency more efficient by letting the refractive index η3 be within this range. The second electrode 4 is provided on the side opposite to the first electrode 2 of the organic layer 3. Α1 or the like can be used as the material of the second electrode 4, or a laminated structure of the combination A1 and other electrode materials. As such a combination of electrode materials, a laminate of an alkali metal and A1, a laminate of an alkali metal and a silver, a laminate of a metal-detecting tooth and an AI, an oxide of an alkali metal, and a laminate of A1 may be cited. A layered body of a metal or rare earth metal and Ai, an alloy of such a metal with another metal, and the like, and specifically, for example, a laminate of sodium, a sodium-potassium alloy, lithium, magnesium, or the like, and magnesium _ Silver mixture, magnesium-indium mixture, aluminum-bell alloy, UF/A1 mixture/laminate, A1/A mixture, and the like. The materials and forms listed above are merely examples, and are not limited thereto. In the case where light is taken out from the side of the first electrode 2, it is preferable to use a material having good reflectivity. Further, the light may be taken out from both sides (both the first electrode 2 side and the second electrode 4 side). In this case, the second electrode 4 is preferably made of a light transmissive material. The method of producing the organic EL element is not particularly limited and can be produced by a general method. That is, each layer can be sequentially formed on the surface of the substrate 1 by an appropriate coating method and inspection. Finally, it is also possible to seal the cover and the like. [Examples] [Production of Element] (Example 1) An alkali-free glass plate was used as the substrate 1 (manufactured by Corning Co., Ltd. 1737). The refractive index (η1) of the substrate 1 at a wavelength of 500 nm is 丨~丨53 20/34 201201622. Further, the refractive index was measured by FilmTek manufactured by SCI Co., Ltd. (the refractive index measurement is also the same below). The same as the substrate 1 described above is used as the substrate for the printing plate. The surface of the substrate for a printing plate is formed by wet etching in such a manner that, in a plan view, the pitch between the centers is about 300 nm, and a plurality of straight lines are arranged, and the shape of the wearing surface is width ( The bottom edge is a structure having a plurality of convex portions having a triangular shape (reverse V-shape) of about 2 〇〇 nm and a height of about 5 〇 nm to fabricate a printing plate. ^ As a solution for forming the first electrode 2 on the substrate 1, a polymethyl methacrylate (PMMA, manufactured by Aldrich Co., Ltd.) was used to disperse the rice particles, and the gluten solution (grain control was about 4 〇 nm, ciKasei company made NanoTek (the main bookmaker; f shows) ITCW15wt ° / 〇 - G30) and got i〇wt0 /. The solution of propylene g and the solution was obtained by mixing ITO nanoparticles with a volume ratio of PMMA = 1:8. PMMA is a reactive resin. This solution was applied onto the substrate 1 by a spin coating method so as to have a film thickness of 100 nm, and heated to 1 〇〇C. Thereby, an electrode formation layer was produced. The refractive index (n2) of the electrode formation layer (the second electrode 2) obtained was about 1.49 at a wavelength of 500 nm. Next, the surface on which the electrode formation layer of the substrate 1 is formed is opposed to the surface on which the pattern of the 7-plate is formed, and the printing plate is superposed on the substrate 1, and pressed with a pressure of $1 to OMpa, and the printing plate is held for 1 minute. By this, a fine periodic structure 5 having a plurality of concave portions 7 having a stripe shape composed of a plurality of straight lines and a plurality of inverse triangular shapes (V-shaped) in a plan view in a plan view of about 30 〇 nm is formed. The first electrode 2. The j-th electrode 2 is used as a positive electrode. Further, the arrangement period of the fine periodic structure (300 nm) is smaller than the wavelength of light generated by the organic light-emitting layer described below. 21/34 201201622 Treatment of Si The surface of the first electrode 2 is centered on a 5-phenyl group, and the organic light-emitting layer that also serves as the f-sub-cavity layer of Age #7 is connected to the vapor deposition plate with A1 (high purity and then borrowed on the electron injection layer). The second electrode 4 of the vacuum is formed into a film thickness of 8 〇·, and the substrate 1 which is dried as a cathode is transported under the above-mentioned Luer 1. The sealant is applied. Then, (4) The sealing cover made of external hardened resin is sealed with the sealant in the arsenal The dense agent is sealed with a sealing cap in a manner of enclosing the layers. The upper portion of the ttirf structure is hardened by irradiation with ultraviolet rays, and the refractive index is formed on the first electrode 2 as shown in FIG. N2<nl<n3 organic EL element (Example 2) 'Use the same ratio of silver/nano particles (particle size about 9 〇/° or more) and read A to the same quality as real -22! Silver nanoparticles dispersed in a solvent: pMMA solution. The thickness of the electrode 2 is K) 〇 nm. The refractive index (n2) of the electrode 2 produced was about U9 at a wavelength of 500 nm. Except for this, an organic EL element having a layer structure as shown in Fig. 1 was obtained in the same manner as in Example i. (Example 3) As a material of the first electrode 2, a silver nanowire (having a diameter of about 5 Gnm, a length of about 5 Å, a reflectance of 嶋 or more) and a pMMA having the same mass ratio as the plaque example were used as a solvent dispersion. Silver nanowire: pMMA solution. Silver nanowire is in accordance with the published paper "_She ❽ (10) post and Physics V〇1.m P333-338 "Preparati〇n 〇f Ag face her
WithhighyiddbyP〇lyolpr〇cess”」而作成者，平均直徑為 50nm、平均長度為5卿。第丄電極2之膜厚為·爪。所 製作之第1電極2之折射率（n2)於波長5〇〇_為約！ 49 。除此之外，以與實施例1相同之方式來得到層結構如圖i 之有機EL元件。 (實施例4) 做為第1電極2之材料，使用將銀奈米導線（直徑約 50nm、長度約5μιη、反射率9〇%以上）與聚笨乙烯（ps) 以與實施例1相同之質量比率以溶劑分散而成之銀奈米導 線：ps溶液。銀奈米導線係依照公開的論文「m收她 Chemistry and Physics vol.114 p333-338 Preparation of Ag nanorods with high yield by polyol process”」而作成者，平 均直徑為jOnm、平均長度為一。聚苯乙稀為具有透光性 之樹脂。第1電極2之膜厚為100nm。所製作之第丨電極2 之折射率（n2)於波長500nm為158。除此之外以與實施 23/34 201201622 例1相同之方式進行，得到層結構如圖丨之折射率關係為 nl<n2<n3之有機El元件。 (實施例5 ) 將實施例1中所使用之打印板使用做為基板1(折射率 η1 = 1·50〜1.53)，於打印板的微細周期構造上直接以與實 施例1相同之方式形成第丨電極2。藉此在第丨電極2^基 板1側的界面上形成微細周期構造5。接著，對基板丨之形 成有第1電極2之面進行5分鐘之uv_〇3處理。其後，將 基板1設置於真空蒸鍍裝置中，以N，N_二苯基屮，队雙（1_ 萘基）-1，Γ-聯笨基_4,4，-二胺（NPB) (eRay公司製）在第 1電極2上形成膜厚4〇nm之電洞傳輸層。除此之外，以與 實施例1相同之方式進行來得到有機元件。 、 (實施例6) 將實施例1中所使用之打印板做為基板〗（折射率nl = 1.50〜1.53)使用，於打印板的微細周期構造上直接以與 實施例1相同之方式形成第]電極2。接著，以與實施例i 相同之方式藉由打印板在第1電極2之表面形成微細周期 構造5。藉此在第1電極2的兩面上形成微細周期構造$。 其後’將基板〗設置在真空蒸鍍裝置中，以N，N_二苯基_n,n_ 雙（1-萘基）-1，1’-聯苯基-4,4，-二胺（NPB) (eRay公司製 )在第1電極2上形成膜厚4〇nm之電洞傳輸層。除此之外 ，以與實施例1相同之方式來得到有機EL>元件。 (實施例7) 將實施例1中所使用之打印板使用做為基板1(折射率 nl== 1.50〜1.53) ’於打印板之凹凸形成側的相反面上形成 24/34 201201622WithhighyiddbyP〇lyolpr〇cess"", the average diameter is 50nm and the average length is 5 qing. The film thickness of the second electrode 2 is a claw. The refractive index (n2) of the first electrode 2 produced is about 5 〇〇 at a wavelength of about !! 49. Except for this, an organic EL element having a layer structure as shown in Fig. 1 was obtained in the same manner as in Example 1. (Example 4) As a material of the first electrode 2, a silver nanowire (having a diameter of about 50 nm, a length of about 5 μm, a reflectance of 9 〇% or more) and a polystyrene (ps) were used in the same manner as in Example 1. Silver nanowires in which the mass ratio is dispersed in a solvent: ps solution. The silver nanowire is made in accordance with the published paper "Chemical and Physics vol. 114 p333-338 Preparation of Ag nanorods with high yield by polyol process", having an average diameter of jOnm and an average length of one. Polystyrene is a light transmissive resin. The film thickness of the first electrode 2 was 100 nm. The refractive index (n2) of the produced second electrode 2 was 158 at a wavelength of 500 nm. Except for this, in the same manner as in Example 1 of the implementation of 23/34 201201622, an organic EL element having a layer structure as shown in Fig. 1 having an index of refraction of nl < n2 < n3 was obtained. (Example 5) The printing plate used in Example 1 was used as the substrate 1 (refractive index η1 = 1·50 to 1.53), and was formed in the same manner as in Example 1 on the fine period structure of the printing plate. Diode electrode 2. Thereby, the fine periodic structure 5 is formed on the interface of the second electrode 2 on the substrate 1 side. Next, the uv_〇3 treatment was performed on the surface of the substrate 丨 on the surface of the first electrode 2 for 5 minutes. Thereafter, the substrate 1 is placed in a vacuum evaporation apparatus, and N,N-diphenylfluorene, bis (1-naphthyl)-1, fluorene-linked phenylene-4,4,-diamine (NPB) (manufactured by eRay Co., Ltd.) A hole transport layer having a film thickness of 4 〇 nm was formed on the first electrode 2. Except for this, an organic element was obtained in the same manner as in Example 1. (Example 6) The printing plate used in Example 1 was used as a substrate (refractive index nl = 1.50 to 1.53), and the micro-period structure of the printing plate was directly formed in the same manner as in Example 1. ] Electrode 2. Next, a fine periodic structure 5 was formed on the surface of the first electrode 2 by the printing plate in the same manner as in the example i. Thereby, a fine periodic structure $ is formed on both surfaces of the first electrode 2. Thereafter, the 'substrate' is placed in a vacuum evaporation apparatus to N,N-diphenyl-n,n_bis(1-naphthyl)-1,1'-biphenyl-4,4,-diamine (NPB) (manufactured by eRay Co., Ltd.) A hole transport layer having a film thickness of 4 〇 nm was formed on the first electrode 2. Except for this, an organic EL> element was obtained in the same manner as in Example 1. (Example 7) The printing plate used in Example 1 was used as the substrate 1 (refractive index nl == 1.50 to 1.53) to form on the opposite side of the uneven surface on which the printing plate was formed. 24/34 201201622
第1電極2。其後，將基板1設置在真空蒸鑛裝置中，以 N，N-二笨基-Ν,Ν-雙（1-萘基）-1，Γ-聯笨基_4,4，_二胺（NpB )(eRay公司製）在第1電極2上形成膜厚斗此爪之電洞傳 輸層。除此之外，以與實施例1相同之方式來得到有機£匕 元件。 (比敉例 於實施例1所使用之玻璃製基板i的表面、鱗IT0膜 (100nm)形成第1電極2。此ΙΤΟ膜於波長5〇〇nm之折 射率為2.0。接著在此第1電極2上藉由與實施例1相同之 材料/方法形成電洞傳輸層、有機發光層、電子注入層、 極（陰極），最後以密封蓋密封。藉此，得到折射率^ nl<n3<n2之有機EL元件。 …、 (比較例2 ) 於實施例1中所使用之玻璃製基板1的表面缝IT0 之⑽nm)形成第丨電極2。接著在第！電極2表 ^例！中所使用之打印板形成微細周期構造。此第 ㈣/方法形錢洞傳輸層 射率關#兔曰1 ^电極（陰極）。藉此，得到才斤 旱關係為nl<n3<n2之有機a元件。 所 (實施例8) 其次，於此基板1以鱼實 ”、、、. 率（n2)約M9之第】心心例1相同之方法形成折射 極2，以實施例1中使用之打印 25/34 201201622 第1電極H、明期構造5之第1電極2。接著’對形成有 聚苯乙烯μ Γ進行uv_〇3處理後’將聚乙稀二氧嚷吩： 只酉义（PEDOT-PSS ) ( Starck-V Tech 公司制厂 (註冊商標)PA测3」、PEDOT : PSS=1 : 6)二旋 ^塗、布，场成料3Gnm之方式塗布，藉由在刚。C燒結 折：f f製作電洞注入層。此電洞注入層於波長500nm之 折射率（n3)為L55。 ^^^與實_ 1相同之方絲電洞注人層之表面 义序7成電洞傳輪層、有機發光層、電 電極4。 論’得到層結構如圖1之在第1電極2上形成微細 周期構U 5之折射率關係為n2<n3<ni之有機此元件。 (實施例9) 做為第1電極2之材料係使用將銀奈米粒子（粒徑約 4旦〇nm、反射率90%以上）與pMMA以與實施例i相同之質 置比率’赌劑分散㈣絲奈綠子：pMMA溶液。第 1電極2之膜厚為⑽邮。所製作之第丨電極2的折射率（ n2)於波長5GGnm為約i.49。除此之外，以與實施例8同 樣的方式來得到層結構如圖】之有機EL元件。 (實施例10) 做為第1電極2之材料係使用將銀奈米導線（直徑約 50nm、長度約5μιη、反射率9〇%以上）與pMMA以與實施 例1相同之胃i比率’以溶劑分散而成之銀奈米導線： PMMA /谷液。銀奈米導線係依照公開的論文「腦⑼业 Chemistry and Physics v〇Ul4 ρ333·338 “preparati〇n 〇fAg 26/34 201201622 讎〇r〇dSWith 吨11 Weld W polyol process”」而作成，平均 直径5〇nm、平均長度5μηι。第1電極2之膜厚為i〇〇nm。 製得之第1電極2的折射率（n2)於波長5〇〇nm為約149 。除此之外，以與實施例8同樣的方式來得到層結構如圖j 之有機EL元件。 (實施例11) 做為第1電極2之材料係使用將銀奈米導線（直徑約 5〇nm、長度約5μιη、反射率90%以上）與聚苯乙烯（PS) 以與實施例1相同之質量比率，以溶劑分散而成之銀奈米 導線·· ps溶液。銀奈米導線係依照公開的論文「Materials Chemistry and Physics vol.114 p333-338 “Preparation of Ag nanorods with high yield by polyol process”」而作成，平均 直徑50nm、平均長度5μιη。聚苯乙烯為具有透光性之樹脂 。第1電極2之膜厚為i〇〇nm。所製作之第丨電極2的折 射率（n2)於波長5〇〇nm為1.58。除此之外，以與實施例 8同樣的方式來得到層結構如圖1之折射率關係為n3<n2 <nl之有機EL元件。 (實施例12 ) 將雙酚A+己二胺溶液藉由旋轉塗布法，以使膜厚成 為100nm之方式塗布於實施例8中所使用之基板1 (樹脂 基板）的表面上，加熱至80°C。於此基板1之表面以實施 例1中所使用的打印板來形成微細周期構造5。 在此基板1 (折射率nl =約1.60)之微細周期構造上 直接以與實施例相同之方式形成第1電極2 (折射率n2 = 約1.49)。藉此在第丨電極2之基板】側的界面上形成微細 27/34 201201622 周期構造5。接著，對基板1形成有第丨電極2之面進行$ 分鐘UV-〇3處理。除此之外，係與實施例8同樣的方式進 行，於第1電極2之表面依序形成電洞注入層（折射率n3 = 1.55)、電洞傳輪層、有機發光層、電子注入層、及第2 電極4。藉此，侍到層結構如圖1之折射率關係為n2<n3 <nl之有機EL元件。 (實施例13) 在實施例12中所製得之具有微細周期構造$之基板i (折射率心約1.60)之微細周期構造上，直接以^實施 例1相同之方式形成第1電極2 (折射率心約！ 接 著，以與實:相同之方法以打印板在第1電極2 _ 上形成微細構造5。藉此在第丨紐2之兩面上形成微 細周期構造5。除此之外，係與實施例8同樣的方式進行， 於第！電椏2之表面依序形成電洞注入層（折射率心⑸ )、電洞傳θ輸層、有機發光層、電子注人層、及第2電極* 。藉此’持到曰結構如圖1之折射率關係為n2<n3<nl之 有機EL元件。 (實施例H) 在實鈔Π2中所製得之具有微細周期構造$之基板工 (折射率G)之凹凸形成側的相反面上形成第1 Γ2==约M9)。除此之外，係跑 :的方：3 = 1 5:、1電極2之表面依序形成電洞注入層 折 ㈣電洞傳輸層、有機發光層、電子注入 層、及第2電極4。藉此，得到声έ士槿石囯7 . 射率關係 π仵除此之外，以與實施例】 28/34 201201622 同樣的方式來得到有機EL元件。 (比較例3) (100邮），形成製基板1的表面賤鑛汀〇膜 射率為2.〇。接著在此第；電極此膜於波長之折 材料/方法依序形成電洞注實施例8相同的 、電子注人層、及第2 _層、電洞傳輸層、有機發光層 得到折射率之關Μ η3<° 4 ’最後以密封蓋密封。藉此， (比=為3<—之有機肛元件。 在實施例8中所使用之樹The first electrode 2. Thereafter, the substrate 1 is placed in a vacuum distillation apparatus, and N,N-diphenyl-anthracene, fluorene-bis(1-naphthyl)-1, fluorene-linked phenylene-4,4,diamine (NpB) (manufactured by eRay Co., Ltd.) forms a hole transport layer of the film thickness on the first electrode 2. Except for this, an organic element was obtained in the same manner as in Example 1. (The first electrode 2 was formed on the surface of the glass substrate i used in Example 1 and the scale IT0 film (100 nm). The refractive index of the ruthenium film at a wavelength of 5 〇〇 nm was 2.0. A hole transport layer, an organic light-emitting layer, an electron injecting layer, a pole (cathode) are formed on the electrode 2 by the same material/method as in Embodiment 1, and finally sealed with a sealing cap. Thereby, a refractive index ^nl <n3< Organic EL element of n2. (Comparative Example 2) The second electrode 2 was formed at (10 nm) of the surface slit IOT of the glass substrate 1 used in Example 1. Then at the first! Electrode 2 table ^ example! The printing plate used in the formation forms a fine periodic structure. This (four) / method shaped money hole transmission layer rate of off # rabbit 曰 1 ^ electrode (cathode). Thereby, an organic a component having a relationship of nl < n3 < n2 is obtained. (Embodiment 8) Next, the substrate 1 is formed with the refractive electrode 2 in the same manner as the core example 1 of the fish ("2", about the M9), and the printing 25 used in the embodiment 1 is used. 34 201201622 The first electrode H of the first electrode H and the bright phase structure 5. Then, after the uv_〇3 treatment of the polystyrene μ 形成 is formed, the polyethylene dioxin: PEDOT- PSS) (Starck-V Tech factory (registered trademark) PA measurement 3", PEDOT: PSS = 1: 6) Two-rotation coating, cloth, field coating 3Gnm coating, by just. C sintering Fold: f f to make a hole injection layer. The refractive index (n3) of the hole injection layer at a wavelength of 500 nm is L55. ^^^ is the same as the real _ 1 square wire hole injection surface of the layer of the correct order 7 into the hole transmission layer, organic light-emitting layer, electrode 4. The obtained layer structure is as shown in Fig. 1. The refractive index relationship of the fine periodic structure U 5 formed on the first electrode 2 is n2 < n3 < ni organic element. (Example 9) As the material of the first electrode 2, silver nanoparticle (particle diameter of about 4 denier nm, reflectance of 90% or more) and pMMA were used in the same ratio as in the example i. Disperse (four) silk greens: pMMA solution. The film thickness of the first electrode 2 is (10). The refractive index (n2) of the produced second electrode 2 was about i.49 at a wavelength of 5 GGnm. Except for this, an organic EL device having a layer structure as shown in Fig. 8 was obtained in the same manner as in Example 8. (Example 10) As the material of the first electrode 2, a silver nanowire (having a diameter of about 50 nm, a length of about 5 μm, a reflectance of 9〇% or more) and a pMMA having the same stomach i ratio as in Example 1 were used. Solvent-dispersed silver nanowire: PMMA / gluten. The silver nanowire is made according to the published paper "The Brain (9) Industry Chemistry and Physics v〇Ul4 ρ333·338 "preparati〇n 〇fAg 26/34 201201622 雠〇r〇dSWith ton 11 Weld W polyol process", the average diameter 5 〇 nm, average length 5 μηι. The film thickness of the first electrode 2 is i 〇〇 nm. The refractive index (n2) of the first electrode 2 obtained was about 149 at a wavelength of 5 〇〇 nm. Except for this, an organic EL device having a layer structure as shown in Fig. j was obtained in the same manner as in Example 8. (Example 11) As the material of the first electrode 2, a silver nanowire (having a diameter of about 5 Å, a length of about 5 μm, a reflectance of 90% or more) and polystyrene (PS) were used in the same manner as in Example 1. The mass ratio of the silver nanowires·· ps solution dispersed in a solvent. The silver nanowires were prepared in accordance with the published paper "Materials Chemistry and Physics vol. 114 p333-338 "Preparation of Ag nanorods with high yield by polyol process", having an average diameter of 50 nm and an average length of 5 μm. Polystyrene is a light transmissive resin. The film thickness of the first electrode 2 is i 〇〇 nm. The refractive index (n2) of the produced second electrode 2 was 1.58 at a wavelength of 5 〇〇 nm. Except for this, in the same manner as in Example 8, an organic EL device having a layer structure as shown in Fig. 1 having a refractive index relationship of n3 < n2 < nl was obtained. (Example 12) The bisphenol A + hexamethylenediamine solution was applied to the surface of the substrate 1 (resin substrate) used in Example 8 by a spin coating method so as to have a film thickness of 100 nm, and heated to 80 °. C. The fine periodic structure 5 was formed on the surface of the substrate 1 by using the printing plate used in Example 1. The first electrode 2 (refractive index n2 = about 1.49) was formed directly in the fine periodic structure of the substrate 1 (refractive index n1 = about 1.60) in the same manner as in the embodiment. Thereby, a fine 27/34 201201622 periodic structure 5 is formed on the interface of the substrate side of the second electrode 2. Next, the surface of the substrate 1 on which the second electrode 2 is formed is subjected to a UV-〇3 treatment for $minute. In the same manner as in the eighth embodiment, a hole injection layer (refractive index n3 = 1.55), a hole transfer layer, an organic light-emitting layer, and an electron injection layer were sequentially formed on the surface of the first electrode 2. And the second electrode 4. Thereby, the organic layer element having the refractive index relationship of n2 < n3 < nl is as shown in Fig. 1. (Example 13) On the fine period structure of the substrate i (refractive index center: about 1.60) having the fine period structure $ obtained in Example 12, the first electrode 2 was formed in the same manner as in Example 1 ( The refractive index center is approximately the same. Next, the fine structure 5 is formed on the first electrode 2 _ by the printing plate in the same manner as in the actual method. Thereby, the fine periodic structure 5 is formed on both surfaces of the second ridge 2 . In the same manner as in the eighth embodiment, a hole injection layer (refractive index core (5)), a hole transmission θ transmission layer, an organic light-emitting layer, an electron injection layer, and the like are sequentially formed on the surface of the second electrode 2 2 electrode*. This is an organic EL element having a refractive index relationship of n2 < n3 < nl as shown in Fig. 1. (Example H) Substrate having a fine period structure of $ in the banknote 2 On the opposite side of the unevenness forming side of the working (refractive index G), the first Γ2 == about M9) is formed. In addition, the side of the system is: 3 = 1 5: The surface of the 1 electrode 2 is sequentially formed with a hole injection layer (4) a hole transport layer, an organic light-emitting layer, an electron injection layer, and a second electrode 4. In this way, an organic EL device was obtained in the same manner as in the example of 28/34 201201622 except that the acoustic relationship was obtained. (Comparative Example 3) (100 Å), the surface of the substrate 1 was formed to have a 贱 〇 film rate of 2. 〇. Then, the electrode is formed in the same manner as the wavelength-folding material/method, and the electron-injecting layer, the second layer, the hole-transporting layer, and the organic light-emitting layer are refractive index. Μ η3<° 4 ' Finally sealed with a sealing cap. Thereby, (ratio = 3 < - organic anal element. The tree used in embodiment 8
祺（lOOnm)，形成第丨雷朽 、表面濺鍍ITO .. 取弟1電極2。接著在第1畲杌〇 >七二 =實齡π t所如之打_彡級 ，之折射率(n2)於波長則―約=造： 1電極2之I·，丨、/也说& ί要者在此第 /、κ把例8相同的材料/方、土 > — 電，入層:電洞傳輪層、有機發光層、電子注入 =電2 此’得到折射率之關係為一 <‘有二 〔測定〕 料有機EL元件施加霞，⑽準方㈣ 光的提取效率）。接著，對實施例1〜7， ^ 之Ίί 4 ·玄./从a « 。卞外以比較例1 餘里子效率做為基準（1.0)之情形之量子效率比。又，對 广:8〜U ’計算以比較例3之量子效率做為基準㈤ )之情形之量子效率比。 〔結果〕 結果示於表1及表2。 29/34 201201622 .由表1可發現，實施例1〜7之元件與未形成具有包含 導電性微粒子之微細周期構造5的電極之比較例丨、及折射 率之關係為nl<n3<n2之比較例2相比’確認了光的提取 效率有所提升。接著，實施例1〜7之元件抑制了環境光之 反射’發光更為易視。又，將使用反射率高之銀做為導電 =物質之實施例2〜3的it件與實施例1相比，4認了光的 提Ϊ效ί有所提升。接著，將使用銀奈米導線做為導電性 物貝之貝化例3之元件與實施例2相比，確認了光之提取 效^有所提升。又’在第1電極2之兩界面具有微細周期 5之貫施例6，與僅在一邊的界面有微細周期構造$之 汽知例1及5相比’進一步的抑制了環境光之反射而更容 易看到發光。 又，由表2可發現，實施例8〜i4之元件與未形成具 有包含導電性微粒子之微細周期構造5的電極之比較例3 及折射率之關係為n3 < n 1〈 n2之比較例4相比，確認了 光的提取效率有所提升。接著，實施例8〜14之元件抑制 了％境光之反射’發光更為易視。又’將使用反射率高的 銀來做為導電性物質之實施例9〜1〇之元件與實施例8相 比’確s忍了光的提取效率有所提升。接著，將使用銀奈米 導線做為導電性物質之實施例10之元件與實施例9相比， 確認了光的提取效率有所提升。又，在第1電極2之兩界 面具有微細周期構造5之實施例13，與僅在-邊的界面具 有U細周期構造5之實施例8相比，進一步的抑制了環境 光之反射而更容易看到發光。 30/34 201201622 表1 微細周期構造 (界面） 電極形成材料 折射率関係 量子效率比 實施例1 第1電極/有機層 1TO奈米粒子 ΡΜΜΑ η2<η 1 <η3 1·3倍 實施例2 第1電極/有機層 銀奈米粒子 ΡΜΜΑ n2<nl<n3 1·4倍 實施例3 第1電極/有機層 銀奈米導線 ΡΜΜΑ η2<η 1 <η3 1.5倍 實施例4 第1電極/有機層 銀奈米導線 聚笨乙烯 η1<η2<η3 1·3倍 實施例5 基板/第1電極 1ΤΟ奈米粒子 ΡΜΜΑ η2<η1<η3 1.3倍 實施例6 基板/第丨電極、 苐1電極/有機層 ΙΤΟ奈米粒子 ΡΜΜΑ η2<η1<η3 1.3倍 實施例7 基板/外部 ΙΤΟ奈米粒子 ΡΜΜΑ η2<η1<π3 1.2倍 比較例1 無 ΠΌ膜 η1<η3<η2 1.0倍 比較例2 第1電極/有機層 ΙΤΟ膜 η1<η3<η2 1.0倍 表2 微細周期構造 (界面） 電極形成材料 折射率関係 量子效率比 實施例8 第1電極/有機層 ΙΤΟ奈米粒子 ΡΜΜΑ n2<n3<nl 1.2倍 實施例9 第1電極/有機層 銀奈米粒子 ΡΜΜΑ n2<n3<nl 1.3倍 實施例10 第1電極/有機層 銀奈米導線 ΡΜΜΑ n2<n3<nl ί·4倍 實施例11 第1電極/有機層 銀奈米導線 聚笨乙烯 n3<n2<nl 1.3倍 實施例12 基板/第丨電極 ΙΤΟ奈米粒子 ΡΜΜΑ n2<n3<nl 1.2倍 實施例13 基板/第丨電極、 第1電極/有機層 ΙΤΟ奈米粒子 ΡΜΜΑ n2<n3<nl 1.2倍 實施例14 基板/外部 1ΤΟ奈米粒子 ΡΜΜΑ η2<η3<η1 1.2倍 比較例3 無 1ΤΟ膜 η3<η1<η2 1.0倍 比較例4 第1電極/有機層 ΠΌ膜 η3<η1<η2 1.0倍 31/34 201201622 【圖式簡單說明】 圖1為顯示本發明之有機El _ 意截面圖。 疋件實施形態之範例的示 圖2為顯示本發明之有η 〜 的示意截面圖。 疋件實施形態之其它範例 圆Ma)〜（d)為說 態之其它範例的透視圖。林發明之有機EL元件實施形 (di不本發明之有機el元件實施形態之其它範例， ⑷為不讀關、（bu⑷的部分擴大圖。 ，5為顯示習知的有機乱元件之範例的示意截面圖。 L王要元件符號說明】 1 基板 第1電極 3a有機層 第2電極 微細周期構造 凸部 凹部 凸形狀 凹形狀 32/34祺 (lOOnm), forming the first thunder, surface sputtering ITO.. take the brother 1 electrode 2. Then, in the first 畲杌〇> 七======================================================================================== & ί In this case, /, κ, the same material / square, soil > - electricity, into the layer: hole transmission layer, organic light-emitting layer, electron injection = electricity 2 this 'received refractive index The relationship is one <'there is two [measurement] material organic EL element application Xia, (10) quasi-square (four) light extraction efficiency). Next, for the examples 1 to 7, ^ Ί ί 4 · Xuan. / from a «. The quantum efficiency ratio of the case where the efficiency of the lining of Comparative Example 1 is taken as the reference (1.0). Further, the quantum efficiency ratio in the case where the width: 8 to U ' is calculated as the reference (5) of Comparative Example 3 is calculated. [Results] The results are shown in Tables 1 and 2. 29/34 201201622. It can be seen from Table 1 that the relationship between the elements of Examples 1 to 7 and the electrode in which the fine periodic structure 5 having the conductive fine particles is not formed, and the refractive index are nl < n3 < n2 In Comparative Example 2, it was confirmed that the extraction efficiency of light was improved. Next, the elements of Examples 1 to 7 suppressed the reflection of ambient light. Further, in the case of the examples 2 to 3 in which silver having a high reflectance was used as the conductive material, the effect of the light recognition was improved. Next, the element using the silver nanowire as the conductive material of Example 3 was compared with that of Example 2, and it was confirmed that the light extraction effect was improved. Further, the sixth embodiment having the fine period 5 at the interface between the first electrodes 2 and the second embodiment has a micro-period structure of only one of the interfaces, and the reflection of the ambient light is further suppressed. It is easier to see the glow. Further, from Table 2, it can be found that the relationship between the elements of Examples 8 to i4 and the electrode 3 in which the electrode having the fine periodic structure 5 containing the conductive fine particles is not formed and the refractive index is n3 < n 1 < n2 Compared with 4, it was confirmed that the extraction efficiency of light was improved. Next, the elements of Examples 8 to 14 suppressed the reflection of % light, which was easier to see. Further, the elements of Examples 9 to 1 which use silver having a high reflectance as a conductive material are improved in comparison with Example 8 to ensure that the extraction efficiency of light is improved. Next, the element of Example 10 using a silver nanowire as a conductive material was confirmed to have an improved light extraction efficiency as compared with Example 9. Further, in the thirteenth embodiment having the fine periodic structure 5 at the interface between the first electrodes 2, the reflection of the ambient light is further suppressed as compared with the eighth embodiment having the U-fine periodic structure 5 only at the interface of the side. It is easy to see the light. 30/34 201201622 Table 1 Fine period structure (interface) Electrode forming material refractive index relationship quantum efficiency ratio Example 1 First electrode/organic layer 1TO nanoparticle ΡΜΜΑ η2 < η 1 < η3 1·3 times Example 2 1 electrode/organic layer silver nanoparticle ΡΜΜΑ n2 <nl<n3 1-4 times Example 3 1st electrode/organic layer silver nanowire ΡΜΜΑ η2<η 1 <η3 1.5 times Example 4 1st electrode/organic Layer silver nanowire polystyrene η1 <η2<η3 1·3 times Example 5 Substrate/first electrode 1 ΤΟ nanoparticle ΡΜΜΑ η2 < η1 < η 3 1.3 times Example 6 Substrate / 丨 electrode, 苐 1 electrode / Organic layer ΙΤΟ nanoparticle ΡΜΜΑ η2 < η1 < η3 1.3 times Example 7 Substrate/external ΙΤΟ nanoparticle ΡΜΜΑ η2 < η1 < π 3 1.2 times Comparative Example 1 No ruthenium film η1 < η3 < η 2 1.0 times Comparative Example 2 1 Electrode/organic layer tantalum film η1 <η3<η2 1.0 times Table 2 Fine period structure (interface) Electrode-forming material refractive index relationship quantum efficiency ratio Example 8 First electrode/organic layer ΙΤΟ nanoparticle ΡΜΜΑ n2<n3<nl 1.2 Times Example 9 First electrode/organic layer silver nanoparticles ΡΜΜΑ n2<n3<nl 1.3 times Example 10 First electrode/organic layer silver nanowire ΡΜΜΑn2<n3<nl ί·4 times Example 11 First electrode /organic layer silver nanowire polystyrene n3<n2<nl 1.3 times Example 12 substrate/second electrode ΙΤΟ nanoparticle ΡΜΜΑ n2<n3<nl 1.2 times Example 13 substrate/third electrode, first electrode/ Organic layer ΙΤΟ nanoparticle ΡΜΜΑ n2 < n3 < nl 1.2 times Example 14 Substrate/external 1 ΤΟ nanoparticle ΡΜΜΑ η2 < η3 < η1 1.2 times Comparative Example 3 No 1 ΤΟ film η3 < η1 < η 2 1.0 times Comparative Example 4 1 Electrode/organic layer tantalum film η3<η1<η2 1.0 times 31/34 201201622 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the organic El _ of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 2 is a schematic cross-sectional view showing η 〜 of the present invention. Other examples of the embodiment of the device Circles Ma) to (d) are perspective views of other examples of the state. The organic EL element implementation form of the invention (di is not another example of the embodiment of the organic EL element of the present invention, (4) is a non-reading, (a partial enlarged view of bu(4).) 5 is an illustration showing an example of a conventional organic chaotic element. Cross-sectional view. L king element description: 1 substrate first electrode 3a organic layer second electrode fine period structure convex portion concave portion convex shape concave shape 32/34