200950574 六、發明說明： 【發明所屬之技術領域】 本發明係關於有機EL顯示器及其製造方法，特別係 關於可防止水份從外部環境浸入，可長時間實現優良發光 效率之有機EL顯示器及其製造方法。 【先前技術】 近年，使用自發光型之有機EL元件的有機EL顯示 器的硏究被盛大進行。有機EL顯示器，因可實現在低電 壓下之高電流密度，而被期待實現高發光亮度及發光效率 ，特別係高精細的多色（multicolor)表示，進而期待可 全彩表示之多色（full color)的有機EL顯示器的實用化 〇 彩色顯示器的實用上之重要課題係爲不僅同時具有精 細的彩色表示機能，也具有包含色彩再現性之長期的安定 性。但，對於彩色有機EL顯示器，則有驅動一定期間後 其發光特性（電流-亮度特性）顯著降低之缺點。 造成此發光特性降低之代表性的原因，則係爲暗點之 生成。此暗點係指，發光缺陷點。於驅動時及保存中若材 料進行氧化，暗點之成長則進行’進而擴展至發光面全體 。暗點的發生原因被認爲係，由於元件中的氧或水分’構 成元件之層合材料氧化或凝集所造成者。其生成無論在通 電中、保存中也進行著，特別係被認爲受到，（1)由於 存在於元件周圍的氧或水分而被加速’ （2)被有機層合 -5- 200950574 膜中身爲附著物所存在之氧或水分影響，又，（3)製作 元件時吸附於部件之水分或製造時等之水分的侵入所影響 〇 作爲防止水份浸入此元件内的有機層合膜之手法，以 往’使用金屬罐或玻璃板將元件形成部覆蓋之方法，或倂 用乾燥劑之方法被使用至今，而最近，爲活用有機EL顯 示器的輕量、薄型之特徴，並不使用乾燥劑，而以薄膜覆 蓋之技術受到注目。 作爲此覆蓋所用之保護膜，雖然氮化矽或氮化氧化矽 等被使用著，但爲抑制製膜時對有機發光層的損傷，則有 將製膜面之溫度上昇抑制至少到機發光層之玻璃轉移溫度 以下之必要。因此，半導體製程中所開發的製膜方法並不 適用’而有無法形成具有充份之防濕性之保護膜的課題。 又’作爲有機EL顯示器中保護膜之形成方法，公知 有使用電漿CVD法（例如，參照專利文獻1、2 )。例如 ’專利文獻1中提案，在電極上形成以氮化矽膜爲主的保 護膜，藉由規定氮化膜中之Si-Si鍵結之量而得到良好之 防濕性一事。 [專利文獻1]特開2005-285659號公報（特許請求之 範圍等） [專利文獻2]特開 2007- 1 8425 1號公報（段落[0003] 等） 【發明內容】 -6- 200950574 [發明所欲解決之問題] 近年，熱烈進行著主動驅動型之有機EL顯示器之實 用化，爲了提高數値孔徑，以使用與製作有TFT回路之 基板之相反側將光抽出之上發射（top emission)型構造 爲主。此時，於有機層合膜上，形成透明電極及密封膜。 密封膜之水氣輸送率（Water Vapor Transportation Rate)，一般而言以未滿lxl0_6g/m2/day爲必要。但，對 於此上發射型之有機EL顯示器，若將專利文獻1所開示 之適用於此，就算防濕性上升，因保護膜中有Si-Si鍵結 ，可見光之吸收則變髙。因此，若在透明電極上形成此保 護膜，則有光透過率降低，有機EL元件之發光效率下降 之題。 關於保護膜之種種從以往就一直檢討至今，以往之改 良技術爲彌補有機層合膜之低密著性，以緩和應力作爲其 主要目的之技術或係以提升階段之被覆之技術爲主，以使 充份之光透過性與防水性同時倂存爲其課題者則少。 於此本發明之目的爲提供一種光吸收比率之消光係數 爲小，且，使用防濕性爲高之保護膜，可長時間安定驅動 之有機EL顯示器及其製造方法。 [用以解決課題之手段] 本發明者探討關於以使用CVD (化學汽相沉積法） 所製膜之保護膜之組成，發現膜中之氫元素之含有量與透 濕性有所關聯一事。其結果，找出使保護膜具有特定之氫 -7- 200950574 元素比率，則可解決上述課題一事，而完成了本發明。 即，本發明之有機EL顯示器係爲具備有支持基板、 該支持基板上所形成之含有下部電極、有機層及上部電極 之有機EL元件與該有機EL元件上所形成之保護層之有 機EL顯示器，其特徵爲， 前述保護層係由1層以上之無機膜所構成，該無機膜 之中至少一層爲含有氫之氮化矽膜，且，該氮化矽膜中之 氫之元素比率爲30 at.%以下者。 本發明中，前述氮化矽膜中之矽元素比率係爲3 Oat% 以上 40at%以下，且，氮之元素比率係以 35at%以上 40at%以下爲佳。又，本發明之有機EL顯示器係以具備 有在與前述支持基板之間空有指定間隔後對向配置之密封 基板，由前述支持基板與密封基板相貼合而成者爲佳。本 發明中，構成元素之比率可藉由盧瑟福背散射及彈性反沖 分析法所算出。 又，本發明之有機EL顯示器之製造方法係爲上述本 發明之有機EL顯示器之製造方法，其特徵爲 使前述保護層藉由以單矽烷，氨及氮作爲原料氣體使 用之化學性汽相沈積法形成之際，使相對於單矽烷之氨的 流量比爲 0.5以上1以下，同時使用 27.12 MHz或 40.68MHz之高頻電源進行製膜。 本發明之製造方法中，使前述保護層在前述支持基板 之溫度爲70°C以下之條件下形成爲適宜。 200950574 [發明之效果] 依據本發明，且作爲上述構成，可得到消光係數爲小 ’且’高防濕性保護層，藉此因可減少保護層中水分侵入 路徑’成爲可實現可長時間安定驅動之長壽命的有機EL 顯示器及其製造方法。 【實施方式】 [實施發明之最佳型態] 以下，參考圖面一邊詳細說明關於本發明之適宜之實 施形態。但，以下所表示之例，僅單係爲例示，可利用當 業者之通常的創作能力範圍而適當地將設計變更。 <有機EL顯示器> 圖1表示本發明之有機EL顯示器的一個適當例的模 式剖面圖。如圖示，本發明之有機EL顯示器100係爲， 具備含有支持基板10、與在其上所形成之下部電極11、 有機層12及上部電極13之有機EL元件20、與在其上所 形成之保護層14、與位置在此上方且與支持體10之間隔 開規定距離且對向配置之密封體30，支持基板10與密封 基板30係藉由黏著層15相貼合而成者。本發明之有機 EL顯示器1〇〇中，如後述，藉由使元素比率30at%以下 且含有至少一層之含氫氮化矽膜之保護層14成爲披覆有 機EL元件20者，不會如先前技術般地使光的透過率下 降，而成爲可抑制水份對有機層合膜滲透。 200950574 (支持基板） 做爲支持基板10的材質，可承受對支持基板10上依 序被層合之層11、12、13等之形成中所使用之種種的條 件（例如、所使用之溶劑、溫度等）者則無特別限制。適 宜者爲，使用尺寸安定性優良者。作爲適宜材質之例可舉 出玻璃基板，或聚烯、聚甲基丙烯酸甲酯等之丙烯酸樹脂 ，以聚對酞酸乙二酯之聚酯樹脂、聚碳酸酯樹脂或聚醯亞 胺樹脂所形成之剛直性的樹脂基板。又，作爲其他的適宜 材質之例可舉出聚烯、聚甲基丙烯酸甲酯等丙烯酸樹脂、 聚對酞酸乙二酯等之聚酯樹脂、以聚碳酸酯樹脂或聚醯亞 胺樹脂等所形成之可撓性薄膜。尙，雖無圖示，亦可在支 持基板10上形成濾色器層、薄膜電晶體（TFT，thin film transistor)或平坦化膜等。 (有機EL元件） 本發明之有機EL元件20，如上述般含有下部電極 11、有機層12及上部電極13。 (下部電極） 下部電極11持有對有機層12注入電荷，與外部驅動 回路相連接之機能。下部電極n作爲反射電極運行時之 理想材料可舉出由高反射率之金屬（鋁、銀、鉬、鎢、鎳 或銘等）、或非晶合金（Nip、NiB、CrP或CrB等）所構 成者。又’作爲特別理想之反射電極材料，從可見光中可 -10- 200950574 得到80%以上之反射率之観點來看，可舉出由銀合金所 構成者。例如’可使用銀與8族之鎳、鉚、鉛及鉑之至少 1種之合金，更進一步，由銀與2 A族之鎂及鈣之至少1 種之合金所構成者。 下部電極11作爲透明電極運行時之理想材料可使用 Sn02 ' In2〇3 ' In-Sn 氧化物、In-Zn 氧化物、ZnO 或 Zn- A1氧化物等之導電性金屬氧化物。 (有機層） 有機層12係配置夾於下部電極11與上部電極13之 間，形成發光部中核之層。有機層12爲至少含有有機發 光層，可依據需要含有電洞輸送層、電洞注入層、電子輸 送層及/或電子注入層。有機層12 ’例如，可採用如下述 般之層構成。 (1) 有機發光層 (2) 電洞注入層/有機發光層 (3) 有機發光層/電子注入層 (4) 電洞注入層/有機發光層/電子注入層 (5) 電洞輸送層/有機發光層/電子注入層 (6) 電洞注入層/電洞輸送層/有機發光層/電子注入 層 (7) 電洞注入層/電洞輸送層/有機發光層/電子輸送 層/電子注入層 但，上述（1)〜（7)之各構成中’作爲陽極運行之 -11 - 200950574 電極連接於左側’作爲陰極蓮行之電極連接於右側。 於有機發光層可使用公知材料。作爲得到由藍色到藍 綠色之發光材料’例如’以苯并噻哩系、苯并咪哩系或苯 并噁唑系等之螢光增白劑、金屬螯合化氧鎗鹽化合物（BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic EL display and a method of manufacturing the same, and more particularly to an organic EL display capable of preventing immersion of moisture from an external environment and achieving excellent luminous efficiency for a long period of time and Production method. [Prior Art] In recent years, studies on organic EL displays using self-luminous organic EL elements have been carried out. Organic EL displays are expected to achieve high luminance and luminous efficiency due to their high current density at low voltages, especially high-definition multicolor representations, and are expected to be multi-color in full color (full Practical use of the organic EL display of the color 〇 The practically important subject of the color display is that it not only has a fine color display function at the same time, but also has long-term stability including color reproducibility. However, in the case of a color organic EL display, there is a drawback that the light-emitting characteristics (current-luminance characteristics) are remarkably lowered after a certain period of driving. The representative cause of this decrease in luminescence characteristics is the generation of dark spots. This dark spot refers to the point of illuminating defects. When the material is oxidized during driving and during storage, the growth of dark spots proceeds to further expand to the entire light-emitting surface. The cause of dark spots is believed to be caused by oxidation or agglomeration of the laminate of the components of the oxygen or moisture in the component. The generation is performed regardless of whether it is energized or stored, and it is considered to be particularly affected. (1) It is accelerated by oxygen or moisture existing around the element. (2) Organic lamination -5 - 200950574 (3) The influence of moisture or moisture in the presence of the deposit, and (3) the influence of the moisture adsorbed on the component during the production of the component or the intrusion of moisture during the production, as a means of preventing the moisture from entering the organic laminated film in the component. In the past, a method of covering a component forming portion using a metal can or a glass plate, or a method using a desiccant, has been used until recently, and in order to utilize the lightweight and thin characteristics of an organic EL display, a desiccant is not used. The technology of film covering has attracted attention. As the protective film used for the coating, although tantalum nitride or tantalum nitride oxide is used, in order to suppress damage to the organic light-emitting layer during film formation, the temperature rise of the film-forming surface is suppressed to at least the organic light-emitting layer. The glass transfer temperature is necessary below. Therefore, the film forming method developed in the semiconductor process is not applicable, and there is a problem that a protective film having sufficient moisture resistance cannot be formed. Further, as a method of forming a protective film in an organic EL display, a plasma CVD method is known (for example, refer to Patent Documents 1 and 2). For example, in Patent Document 1, a protective film mainly composed of a tantalum nitride film is formed on an electrode, and a good moisture resistance is obtained by specifying the amount of Si-Si bonding in the nitride film. [Patent Document 1] JP-A-2005-285659 (The scope of the license request, etc.) [Patent Document 2] JP-A-2007-18445 1 (paragraph [0003], etc.) [Summary of the Invention] -6-200950574 [Invention The problem to be solved] In recent years, the practical use of an organic EL display has been actively carried out. In order to increase the number of apertures, the top side is extracted by using the opposite side of the substrate on which the TFT circuit is fabricated. The type is mainly constructed. At this time, a transparent electrode and a sealing film were formed on the organic laminated film. The Water Vapor Transportation Rate of the sealing film is generally required to be less than lxl0_6g/m2/day. However, when the organic EL display of the above-described emission type is applied to the above-described patent document 1, even if the moisture resistance is increased, the absorption of visible light is deteriorated due to the Si-Si bond in the protective film. Therefore, when the protective film is formed on the transparent electrode, the light transmittance is lowered, and the luminous efficiency of the organic EL element is lowered. The various types of protective films have been reviewed since the past, and the conventional improved technology is mainly to compensate for the low adhesion of the organic laminated film, the technology to alleviate the stress as the main purpose, or the technology to cover the lifting stage, There are few people who have sufficient light transmission and water repellency to coexist. An object of the present invention is to provide an organic EL display which can be driven for a long period of time and a method for producing the same, which is characterized in that the extinction coefficient of the light absorption ratio is small and the protective film having high moisture resistance is used. [Means for Solving the Problem] The inventors of the present invention have found that the composition of the protective film formed by the film formed by CVD (Chemical Vapor Deposition) has been found to be related to the moisture permeability of the film. As a result, it has been found that the protective film has a specific hydrogen ratio of -7 to 200950574, and the above problems can be solved, and the present invention has been completed. In other words, the organic EL display of the present invention is an organic EL display including a support substrate, an organic EL element including a lower electrode, an organic layer, and an upper electrode formed on the support substrate, and a protective layer formed on the organic EL element. The protective layer is composed of one or more inorganic films, at least one of which is a tantalum nitride film containing hydrogen, and an element ratio of hydrogen in the tantalum nitride film is 30. At.% or less. In the present invention, the ratio of the lanthanum element in the tantalum nitride film is from 3 Oat% to 40 at%, and the element ratio of nitrogen is preferably from 35 at% to 40 at%. Further, in the organic EL display of the present invention, it is preferable that the sealing substrate disposed opposite to each other with a predetermined interval between the support substrate and the sealing substrate is bonded to the sealing substrate. In the present invention, the ratio of constituent elements can be calculated by Rutherford backscattering and elastic recoil analysis. Further, the method for producing an organic EL display of the present invention is the above-described method for producing an organic EL display of the present invention, characterized in that the protective layer is chemically vapor deposited by using monodecane, ammonia and nitrogen as source gases. When the method is formed, the flow ratio of ammonia to monodecane is 0.5 or more and 1 or less, and a high frequency power source of 27.12 MHz or 40.68 MHz is used for film formation. In the production method of the present invention, the protective layer is preferably formed under the conditions that the temperature of the support substrate is 70 ° C or lower. 200950574 [Effects of the Invention] According to the present invention, as the above configuration, it is possible to obtain a protective layer having a low extinction coefficient and a high moisture-proof protective layer, thereby making it possible to achieve long-term stability by reducing the moisture intrusion path in the protective layer. Long-life organic EL display driven and method of manufacturing the same. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the drawings. However, the examples shown below are merely exemplified, and the design changes can be appropriately made using the usual range of creative capabilities of the practitioner. <Organic EL Display> Fig. 1 is a schematic cross-sectional view showing a preferred example of the organic EL display of the present invention. As shown in the figure, the organic EL display 100 of the present invention includes an organic EL element 20 including a support substrate 10, and a lower electrode 11, an organic layer 12, and an upper electrode 13 formed thereon, and formed thereon. The protective layer 14 and the sealing body 30 disposed at a predetermined distance from the support 10 and disposed opposite to each other, and the support substrate 10 and the sealing substrate 30 are bonded together by the adhesive layer 15. In the organic EL display of the present invention, as described later, the protective layer 14 containing at least one layer of the hydrogen oxynitride film containing at least one element ratio of 30 at% or less is not coated with the organic EL element 20 as before. The transmittance of light is technically lowered, and the penetration of moisture into the organic laminate film can be suppressed. 200950574 (Support substrate) As a material of the support substrate 10, it is possible to withstand various conditions (for example, solvent used, for use in forming the layers 11, 12, 13 and the like which are sequentially laminated on the support substrate 10. There is no particular limitation on the temperature, etc.) Appropriate for those who use excellent dimensional stability. Examples of suitable materials include a glass substrate, an acrylic resin such as polyene or polymethyl methacrylate, a polyester resin of polyethylene terephthalate, a polycarbonate resin or a polyimide resin. A rigid resin substrate formed. Further, examples of other suitable materials include acrylic resins such as polyene and polymethyl methacrylate, polyester resins such as polyethylene terephthalate, and polycarbonate resins and polyimide resins. The formed flexible film. Further, although not shown, a color filter layer, a thin film transistor (TFT), a planarization film, or the like may be formed on the supporting substrate 10. (Organic EL Element) The organic EL element 20 of the present invention contains the lower electrode 11, the organic layer 12, and the upper electrode 13 as described above. (Lower Electrode) The lower electrode 11 has a function of injecting an electric charge into the organic layer 12 and connecting it to an external driving circuit. An ideal material for operating the lower electrode n as a reflective electrode is a metal having high reflectivity (aluminum, silver, molybdenum, tungsten, nickel, or the like) or an amorphous alloy (Nip, NiB, CrP, CrB, etc.). Constitute. Further, as a particularly preferable reflective electrode material, a silver alloy can be used as a reflection of 80% or more of visible light in the visible light. For example, it is possible to use an alloy of at least one of silver, a group of nickel, riveted, lead, and platinum, and further, an alloy of at least one of silver and a magnesium of Group 2A and calcium. As the material for the operation of the lower electrode 11 as a transparent electrode, a conductive metal oxide such as Sn02 'In2〇3' In-Sn oxide, In-Zn oxide, ZnO or Zn-Al oxide can be used. (Organic layer) The organic layer 12 is disposed between the lower electrode 11 and the upper electrode 13 to form a layer of a core in the light-emitting portion. The organic layer 12 contains at least an organic light-emitting layer, and may contain a hole transport layer, a hole injection layer, an electron transport layer, and/or an electron injection layer as needed. The organic layer 12' can be formed, for example, as described below. (1) Organic light-emitting layer (2) Hole injection layer/organic light-emitting layer (3) Organic light-emitting layer/electron injection layer (4) Hole injection layer/organic light-emitting layer/electron injection layer (5) Hole transport layer/ Organic light-emitting layer/electron injection layer (6) Hole injection layer/hole transport layer/organic light-emitting layer/electron injection layer (7) Hole injection layer/hole transport layer/organic light-emitting layer/electron transport layer/electron injection The layer, however, in each of the above configurations (1) to (7), -11 - 200950574, which is operated as an anode, is connected to the left side, and the electrode as a cathode is connected to the right side. A known material can be used for the organic light-emitting layer. As a fluorescent whitening agent or a metal chelate oxysulfide compound which obtains a blue to blue-green luminescent material, for example, a benzothiazepine, a benzopyrene or a benzoxazole system (
Alqs (三（8-羥基喹啉）鋁）所代表之鋁錯合物等）、苯 乙烯基苯系化合物（4,4’_雙（二苯乙烯）聯苯（〇ρνΒί) 等）、芳香族dimethylidine系化合物、縮合芳香環化合 物、環集合化合物、或卟啉（porphyrin )系化合物等爲佳 〇 又’藉由添加摻雜物於主體化合物中，也可形成發出 各種波長領域之光之有機發光層。此種場合，作爲主體化 合物可使用聯苯乙嫌系化合物' N，N’-二节基-Ν,Ν’-二苯 聯苯基胺（TPD )、或Alq3。另一方面，作爲摻雜物，可 使用茈（青紫色）、香豆素6(青色）、喹吖啶酮系化合 物（青綠色〜綠色）、紅熒烯（黃色）、4-二氰基亞甲基-2-(p-二甲基胺基苯乙烯基）-6-甲基-4H-吡喃（DCM、紅 色）、或鉛八乙基卟啉錯合物（PtOEP、紅色）等。 對於電洞輸送層可使用具有三芳胺部分構造、咔嗖部 分構造、或噁二嗖部分構造之材料。例如使用丁？0、〇1-NPD、MTDAPB ( 〇，m-，p-)、或 m-MTDATA 爲佳。 對於電洞注入層，可使用酞青素類（包含銅酞青素等 )、或陰丹士林系化合物等之材料。 對於電子輸送層，可使用如 AU3之鋁錯合物 '如 PBD或TPOB之噁二唑衍生物、如TAZ之三唑衍生物、 -12- 200950574 三嗪衍生物、苯喹喔啉類、或如BMT-2T之噻吩衍生物等 材料。 對於電子注入層，可使用如Alq3之鋁錯合物、或擒 雜了鹼金屬或鹼土類金屬之鋁之羥基唾啉錯合物等之材料 〇 有機層1 2，雖可由如以上之各層所形成，但與此些 之層有所區別的係，在有機層12與上部電極13之間，可 更進一步任意選擇形成提高電子注入效率用之緩衝層（無 圖示）。作爲緩衝層可使用鹼金屬、鹼土類金屬或此些之 合金、或稀土金屬或此些之氟化物等之電子注入性材料。 又，於有機層12上，爲了緩和上部電極13形成時之損傷 ，可形成Mg Ag等所構成緩和損傷層（無圖示）也爲理想 (上部電極） 上部電極13作爲反射電極運行之場合及作爲透明電 極運行之任一場合時，可使用與下部電極11同樣之材料 而形成。 又，上部電極13之透過率，爲了使由來自機層12發 光從上方取出之機能成爲具有實際效果者，相對於波長 400〜8 0Onm之光以成爲50%以上爲佳，在相同條件中以 成爲8 5 %以上爲更佳。 (保護層） -13- 200950574 保護層14係由1層以上之無機膜所構成，其中至少 1層係爲含氫之氮化矽膜。本發明中，使氮化矽膜中之氫 之元素比率爲30at%以下，例如，成爲25〜29at%係爲重要 。藉由使氫之元素比率在30at%以下，可成防濕性優良之 氮化矽膜，可得到本發明所期望之效果。恰好適宜的做法 係，更進一步，藉由使氮化矽膜中之矽元素比率介於 30at%以上40at°/。以下，氮之元素比率在35at%以上40at% 以下、可得到更加良好之防濕性。尙，氮化矽膜中之各構 成元素之比率可使用盧瑟福背散射及彈性反沖分析法進行 算出。此氮化矽膜之元素組成，在氫、矽及氮之合計量下 實質的會成爲100 at%，但由於膜中會有非蓄意地混入雜 質之場合，也有將此微量之雜質作爲殘存部份加入計算而 成爲100at%之場合。 滿足上述本發明之元素比率的保護層14，如後述， 可藉由調整CVD法等中製膜條件而得到。保護層14，包 含滿足上述元素比率之氮化矽膜，可由複數之層所形成， 例如，藉由改變製膜條件，改變元素比率所形成之氮化矽 膜，或可成爲與氧化氮化矽膜之層合膜。 (黏著層） 黏著層15係爲了將支持基板1〇與密封基板30(於 圖1所示之例中，密封基板30上濾色器等之層合體16所 形成者）相貼合而被使用。作爲理想之黏著層1 5 ’例如 ，可舉出由UV (紫外線）硬化型黏著劑等所構成者。作 -14- 200950574 爲其他理想之黏著層1 5，對上述UV硬化型黏著劑，加入 爲制定支持基板10與密封基板30之間的距離之要素，例 如，可舉出使含有玻璃珠等之間隔物粒子者。 (密封基板） 作爲理想之密封基板30，例如，可舉出玻璃基板、 SUS罐、A1罐等之金屬密封基板，或聚烯，聚甲基丙烯 酸甲酯等之丙烯酸樹脂、聚對酞酸乙二酯等之聚酯樹脂、 聚碳酸酯樹脂或以聚醯亞胺樹脂所形成之剛直性之樹脂基 板。又，作爲其他理想之密封基板30之例，可舉出聚烯 、聚甲基丙烯酸甲酯等丙烯酸樹脂、聚對酞酸乙二酯等聚 酯樹脂、聚碳酸酯樹脂、或以聚醯亞胺樹脂等所形成之可 撓性薄膜。又，作爲密封基板30，使用透明基材，如圖 示，形成濾色器等之層合體16、光轉換層（無圖示）亦 可 〇 (濾色器等之層合體） 濾色器等之層合體16中含有濾色器與色彩轉換層。 濾色器係只使所希望之波長領域中之光透過之層。當濾色 器係與層合體16之色彩轉換層之層合構造之場合，在色 彩轉換層可使波長分佈被改變之光的色純度提升之面上十 分有效。作爲濾色器，例如，可舉出使用 Fujifilm Electronics Materials (股）製之彩色馬賽克等之市面販 售之液晶用濾色器材料者。 -15- 200950574 (光轉換層） 光轉換層係爲轉換色彩用之含有螢光色素之層，亦可 含有基體樹脂。此層係爲對由有機EL元件20所射出之 光進行改變波長分佈，爲了方出不同波長領域之光之層。 在此，構成光轉換層之螢光色素係爲將所希望之波長領域 (例如，紅色、綠色或藍色）之光射出之色素。 作爲吸收從青色到青藍色領域之光，發出紅色領域之 螢光之螢光色素，例如可舉出玫瑰紅B、玫瑰紅6G、玫 瑰紅3B、玫瑰紅101、玫瑰紅110、硫代玫瑰紅、鹼性紫 11、鹸性紅2等之玫瑰紅系色素、花青系色素' 1-乙基-2-〔4-(p-二甲基胺苯基）-1,3-丁二烯〕-過氯酸吡啶鹽 (吡啶1)等之吡啶系色素、或噁嗪系色素。更進一步， 各種染料（直接染料、酸性染料、鹽基性染料、分散染料 等），只要具有螢光性就可使用。 相對於此，作爲吸收藍色至青藍色領域之光，發出綠 色領域之螢光之螢光色素，例如可舉出3- ( 2’-苯并噻唑 基）-7-二乙基胺香豆素（香豆素6 ) 、3-(2’-苯並咪唑 基）-7-二乙基胺香豆素（香豆素7 ) 、3-(2’-N-甲基苯 並咪唑基）-7-二乙基胺香豆素（香豆素30) 、2,3,5,6- 1H，4H-四氫-8-三氟甲基喹嗪（9,9a，l-gh)香豆素（香豆 素153)等香豆素系色素，或香豆素色素系染料之鹼性黃 51’更進一進，溶劑黃11、溶劑黃116等之萘二甲醯亞 胺系色素等。更進一步，各種染料（直接染料、酸性染料 -16- 200950574 、鹽基性染料、分散染料等）只要有螢光性就可使用。 又，作爲構成光轉換層之基體樹脂，可使用丙烯酸樹 脂或各種之聚矽氧聚合物，或可代替此些者之各種。例如 ，可使用直鏈型聚矽氧聚合物及變性樹脂型聚矽氧聚合物 〇 如以上所示之圖1之例，雖爲具備單一之發光部之有 機EL顯示器100之例，但本發明之有機EL顯示器並非 侷限於此等者，也可使其成爲具備獨立且控制複數之發光 部者。例如可舉出，使下部電極及上部電極之兩方爲由複 數之帶狀電極所構成之電極群，使構成下部電極之帶狀電 極之延伸方向與構成上部電極之帶狀電極的延在方向相交 差，使有機層介在於此些電極間之例。此些例就係所謂的 被動矩陣驅動之有機EL顯示器。尙，於此種場合時，使 上述交差形態爲垂直形式，就從可構成表示任意之畫像及 /或文字之顯示器之觀點來看係爲理想。 作爲具備有複數之發光部之其他例，也可舉出使於基 板上所形成之由複數之薄膜電晶體構成之轉換元件與由1 對1連接之複數部分構成之下部電極，與作爲共通電極而 運行之一體型之透明電極之間介有有機層之例。此種之例 ，就係所謂的主動矩陣驅動之有機EL顯示器。 猶，於被動矩陣驅動及主動矩陣驅動之任一場合中， 形成由複數之電極構成下部電極之場合時，也可使用絕緣 性氧化物（SiOx、Ti02、Zr02、A10x等）、或絕緣性氮化 物（A1NX、SiNx等）、高分子材料等，在複數之電極之 -17- 200950574 間隙形成絕緣膜。 又，如圖1所示之例，係爲了實現單色表币之顯不器 ，但本發明並不侷限於此種例，也包含多色表示之顯示器 。實現多色表示之顯示器之場合時，使使如圖1所示之有 機EL元件20、藉由光轉換層及濾色器等之由層合體16 所構成之單元存在有3種類，除了同時使各單元中之包含 於光轉換層及層合體16之色彩轉換層爲紅色、綠色、及 藍色之色彩轉換層，使包含於層合體16之濾色器與各單 元之色彩轉換層相對應，將該當3種類之單元相組合成爲 像素。 <有機EL顯示器之製造方法> 製造如圖1所示之有機EL顯示器時，可採用以下之 各形成步驟。 (有機EL元件形成步驟） 〔下部電極形成步驟〕 於支持基板10上形成下部電極11之步驟。使用高反 射率金屬之場合時，可使用運用電阻加熱或電子束加熱之 蒸氣沉積、濺鍍法。蒸氣沉積之場合時，1.0 XI (T4Pa以下 之製膜壓力中，可使製膜速率爲0.1〜10nm/秒。相對於此 ’濺鍍法’例如，使用DC核磁子濺鍍法等之場合時，作 爲濺鍍氣體使用Ar等之惰性氣體，可爲0.1〜2.OPa程度 之製膜壓力。於蒸氣沉積及濺鍍法之任一中，使形成環境 -18- 200950574 爲真空，就以可實現與隣接之層優良密接性之面上爲理想 〔有機層形成步驟〕 於下部電極11上形成有機層12之步驟。作爲有機層 12,可將有機發光層，與任意所選之電洞輸送層、電洞注 入層、電子輸送層及電子注入層，按照所制定之順序，使 用運用電阻加熱或電子束加熱之蒸氣沉積來加以形成。尙 且’構成有機層15之各層爲了實現各自所希望之特性以 足夠膜厚形成係非常重要的。構成有機層12之各層之膜 厚，使有機發光層爲2~50nm、電洞輸送層爲2~50nm、電 洞注入層爲2〜200nm、電子輸送層爲2〜50nm、電子注入 層爲2~50nm爲佳。 又，有機層12與上部電極13之間任意選擇性形成的 緩衝層，可藉由使用電阻加熱或電子束加熱之蒸氣沉積而 形成，其膜厚，考慮驅動電壓及透明性，以成爲1 〇nm以 下爲佳。 〔上部電極形成步驟〕 於有機層12之上部形成上部電極13之步驟。上部電 極13可使用濺鍍法、蒸氣沉積法而形成。例如，作爲濺 鍍氣體，可使用Ar等之惰性氣體，在0.1〜2.OPa左右的 製膜壓力中，使用DC核磁子濺鍍法等。此時，爲防止有 機層12之劣化，以不直接將標的上部所形成之電漿照射 -19- 200950574 於直接有機層12上爲佳。 〔保護層形成步驟〕 在上部電極13上形成保護層14之步驟。保護層μ ，如前述般， 由至少含有1層之含氫氮化矽膜之1層以上之無機膜 所構成，可使用CVD法、特別係電漿CVD法形成。 爲了製造滿足本發明之條件之氮化矽膜用的良好條件 ，爲如以下。作爲原料氣體使用單矽烷、氨及氮，相對於 單矽烷使氨之流量比爲0.5以上1以下。又，可使壓力爲 10〜200Pa左右，使用27.12MHz或40·68ΜΗζ之高頻電源 。可使電力密度爲O.lW/cm2〜2W/cm2。藉由在此條件下進 行製膜，可得到具有優良防濕性之氮化矽膜。又，爲防止 形成時於電漿中基板溫度之上昇，將此時之支持基板之溫 度控制在70°C以下爲佳。 (密封構造形成步驟） 〔密封體形成步驟〕 在密封基板30上，依據需要，形成濾色器等之層合 體16(濾色器及色彩轉換層）。濾色器等之層合體16’ 可藉由公知之層合法，即，旋轉塗佈法、輥塗佈法、鑄造 法、浸塗法等，塗佈各層之材料後，可藉由用光微影法等 圖案化而形成。於此些公知的形成方法中’特別係’作爲 濾色器層之形成條件，因其形成方法已有被建立’藉由旋 -20- 200950574 轉塗佈法塗佈後，以藉由光微影法之形成方法爲佳。猶， 於一個透明基板30上形成複數種類之濾色器等之色彩微 調部之場合時’藉由使複數種類類之色彩微調部形成矩陣 狀，可實現全彩表示。 〔光轉換層形成步驟〕 在密封基板30上，依據需要’形成光轉換層之步驟 。使用複數種類之色彩轉換色素形成光轉換層之場合時， 也可將複數種類之色彩轉換色素依所定之比率予先混合， 得到將此與基體樹脂混合後之預備混合物，使用該當預備 混合物進行蒸氣沉積。又或係，也可將含有色彩轉換色素 之基體樹脂之複數種類配置於另一個加熱部位，將含有各 別之色彩轉換色素之樹脂於別的地方加熱進行共沉積。特 別係，複數種類之色彩轉換色素之間，蒸氣沉積速度及/ 或蒸氣壓等之特性有大差異之場合時，進行共沉積一事係 爲有利的。 另外，在光轉換層上，將全體被覆之鈍化膜任意選擇 性形成之場合時，可使用如電漿CVD之方法。特別係， 防止光轉換層劣化之觀點上來看，與100°C以下之基板溫 度中進行製膜爲佳。 〔形成將支持基板與密封基板相貼合之步驟〕 如圖1所示般，使用黏著層15將支持基板1〇與密封 基板30相貼合之步驟。貼合之條件，可使用公知的各種 -21 - 200950574 黏接方法。爲了減低對有機層12之熱的影響’選擇使用 倂用了紫外線硬化與熱硬化之環氧樹脂系爲佳。藉由以上 ，可得如圖1所示之本發明之有機EL顯示器1〇〇。 [實施例] 以下，將本發明以實施例進行詳細說明，實際證明本 案發明之效果。 (實施例1 ) 本實施例係爲製作上發射型之有機EL顯示器（像素 數2χ2(僅紅色）、像素幅度0.3 mm)。 作爲支持基板10使用了融合玻璃（CORNING製 1737玻璃、5〇χ5〇χ1.1mm)。在此支持基板10上，使用 濺鍍法使膜厚l〇〇nm之Ag膜沉積，藉由光微影法進行圖 型化，形成寬度〇.3mm之帶狀之下部電極11。 接著，將形成有下部電極11之支持基板10設置於電 阻加熱蒸氣沉積裝置内，使用光罩在下部電極11上沉積 膜厚1.5 nm之Li，形成陰極緩衝層。接下來，使用電阻 加熱蒸氣沉積裝置，使電子輸送層/有機EL層/電洞輸送 層/電洞注入層之4層依順序沉積，得到有機層12。製膜 時之真空槽内壓設爲lxl(T4Pa。構成有機層15之各層則 以0.1 nm/s之蒸氣沉積速度沉積。作爲電子輸送層，形成 了膜厚20nm之Alq3(三（8-羥基喹啉）鋁），作爲有機 EL層形成了膜厚30nm之DPVBi。又，作爲電洞輸送層 -22- 200950574 形成了膜厚l〇nm之α-NPD，作爲電洞注入層形成了膜厚 lOOnm之銅酞青素。 然後，使膜厚5nm之MgAg沉積，形成了透明電極形 成時之緩和損傷層。將製膜了有機層12之層合體在不損 傷真空之情況下移動至對向濺鍍裝置。配置金屬光罩使膜 厚lOOrim之IZO沉積，與下部電極11之條帶朝垂直方向 延伸，形成了寬度〇.3mm之帶形狀透明上部電極13。 接著，將形成了上部電極13之支持基板10搬送至電 漿CVD反應腔，使用單矽烷氣體及氨氣體，在上部電極 13上將氮化矽膜製膜，得到保護層14。氮流量爲2公升/ 分，單矽烷氣體與氨氣體之流量比爲1: 0.7，製膜壓力爲 lOOPa，27.12MHz之高頻電源之電力爲lkW，支持基板之 溫度爲40°C。藉由以上，得到由下部電極11/有機層12/ 上部電極13所構成，在上部有保護層14形成之有機EL 元件20。 將所得之保護層14之組成藉由盧瑟福背散射及彈性 反沖分析法進行分析。此時Si、N、Η之組成比各自分別 爲 3 4 at % > 3 8 at % ' 2 8at%° 另一方面，於透明基板（密封基板）30塗佈紅色濾 器材料（C R 7 0 0 1、F uj ifilm Electroni c s Materials 製）， 在相當於有機EL元件20之發光部之位置上，形成了 〇.5mm X 0.5mm之尺寸之膜厚爲1.5μπι的紅色減色器層。 接著，將形成了濾色器層之層合體搬送至電阻加熱蒸 氣沉積裝置，製作了含有香豆素6及DCM-2之光轉換層 -23- 200950574 。藉由將香豆素6及DCM-2在蒸氣沉積裝置内之别個坦 堝中加熱之共沉積，形成了膜厚3 0 Onm之光轉換層。此 時，使香豆素6之蒸氣沉積速度成爲〇.3nm/s、DCM-2 之蒸氣沉積速度成爲0.005nm/s，控制了個別之坩堝之加 熱溫度。本實施例之光轉換層，以總構成分子數作爲基準 ，香豆素6與DCM-2之莫耳比爲49 : 1。 接著，形成有有機EL元件20之支持基板10，與形 成有濾色器層之透明基板30搬入於在氧濃度5ppm以下 ，水分濃度5ppm以下之貼合裝置内，於形成有紅色濾色 器層之密封基板30之外側，使用環氧系紫外線硬化型黏 著劑使黏著層15滴下形成。將含有有機EL元件20之支 持基板10使其對向配置於紅色濾色器層，在裝置内約減 壓至l〇Pa後，將有機EL元件20之發光部與紅色濾色器 層之位置對齊，將兩層合體相貼合，使裝置内還原至大氣 壓力。 接著，使用光罩單只將黏著層15進行照射紫外線使 其假硬化，放入加熱爐經過1時間在80 °C中加熱後，經過 3〇分鐘在爐内使其自然冷卻。其後，將貼合體從裝置內 取出，得到有機EL顯示器。 (比較例1 ) 作爲保護層之形成條件，除了使單矽烷氣體與氨氣體 之流量比成爲1: 1.1，製膜壓力爲lOOPa，27.12MHz之 高頻電源之電力爲lkW，使支持基板之溫度成爲40°C以 -24- 200950574 外，其它皆與實施例1同樣進行製作了有機EL顯示器。 將保護層之組成藉由盧瑟福背散射及彈性反沖分析法 進行分析。此時，Si、N、Η之組成比各自分別爲29 at% 、3 8 at % ' 3 3at% ° (比較例2) 作爲保護層之形成條件，除了使單矽烷氣體與氨氣體 之流量比成爲1:0.4，製膜壓力爲l〇〇Pa，2 7.12MHz之 高頻電源之電力爲lkW，使支持基板之溫度成爲40°C以 外，其它皆與實施例1同樣進行製作了有機EL顯示器。 將保護層之組成藉由盧瑟福背散射及彈性反沖分析法 進行分析。此時，Si、N、Η之組成比各自分別爲42at% 、3 1 at% ' 2 7at%。 關於如以上般所形成之實施例及比較例之有機EL顯 示器，在60°C、90RH%之環境下，於電流密度0.1A/cm2 使其連續驅動，測量了電壓及亮度。將亮度除以電流値後 所得之値作爲發光效率進行算出，將初期之發光效率作爲 1時，將1 000小時中之發光效率之保持率如以下述之表1 所示。 [表1] 效率之 維持率 備註 實施例1 0.8 - 比較例1 0.4 比較例2 0.3 因保護膜的光吸收而發光效率低 -25- 200950574 從上述表1之結果可得知，在滿足本發明之條件之各 實施例中，可得到發光效率之維持率中係爲優良之結果。 如此般可得知，本案發明之範圍内之實施例中可得到壽命 特性優良之結果，脫離本案發明之範圍之各比較例中其壽 命爲短。此結果被認爲係，在比較例中，因爲從保護層有 水分滲入的關係。 接著，將氮化矽膜之製膜條件變更成如下述表2中所 示般，對所得之氮化矽膜之防濕性進行了評價。如下述表 2中所示作爲其它之製膜條件，使成爲支持基板之溫度 50°C、電力密度〇.5W/cm2、製膜壓力lOOPa、氮流量2L/ 分。防濕性之評價係以，在l〇〇nm厚之Ca膜上將各保護 層以3μιη厚度形成，藉由以95°C 50RH%之恆溫槽中置放 1 000小時後之Ca膜之非變質部之面積比進行比較。將其 結果於下述之表2中合倂表示。 尙且，所得之氮化矽膜中之元素比率，H，Si，N及 殘存部份（係由原料氣體中之雜質或製膜腔體材質、清洗 氣體所混入者，未滿〇.5at%)之合計量爲lOOat%。又， 下述表中之流量之單位「seem」係爲，於〇°C、1氣壓下 所規格化之流量單位「standard cc/min」。Alqs (aluminum complex represented by tris(8-hydroxyquinoline)aluminum), etc., styrylbenzene compound (4,4'-bis(stilbene)biphenyl (〇ρνΒί), etc.), aromatic A dimethylidine compound, a condensed aromatic ring compound, a ring assembly compound, or a porphyrin compound is preferable, and by adding a dopant to the host compound, it is also possible to form an organic light emitting light in various wavelength domains. Light-emitting layer. In this case, as the host compound, a biphenyl phthalate compound 'N,N'-di-blocky-fluorene, fluorene tert-phenylene diphenyl phenylamine (TPD) or Alq3 can be used. On the other hand, as the dopant, cerium (cyan), coumarin 6 (cyan), quinacridone-based compound (cyan~green), rubrene (yellow), 4-dicyano group can be used. Methylene-2-(p-dimethylaminostyryl)-6-methyl-4H-pyran (DCM, red), or lead octaethyl porphyrin complex (PtOEP, red), etc. . For the hole transport layer, a material having a triarylamine partial structure, a ruthenium partial structure, or a dioxin partial structure can be used. For example, use Ding? 0, 〇1-NPD, MTDAPB (〇, m-, p-), or m-MTDATA is preferred. For the hole injection layer, materials such as anthracycline (including copper anthraquinone) or an indanthrene compound can be used. For the electron transport layer, an aluminum complex such as AU3 such as an oxadiazole derivative of PBD or TPOB, a triazole derivative such as TAZ, a -12-200950574 triazine derivative, a quinquinoxaline, or Such as BMT-2T thiophene derivatives and other materials. For the electron injecting layer, a material such as an aluminum complex of Alq3 or a hydroxyparamorphe complex of aluminum doped with an alkali metal or an alkaline earth metal may be used, and the organic layer 12 may be used, for example, in the above layers. Although formed separately from the above layers, a buffer layer (not shown) for improving the electron injection efficiency can be further arbitrarily selected between the organic layer 12 and the upper electrode 13. As the buffer layer, an electron injecting material such as an alkali metal, an alkaline earth metal or an alloy thereof, or a rare earth metal or a fluoride such as these can be used. Further, in order to alleviate the damage in the formation of the upper electrode 13 on the organic layer 12, it is preferable to form a buffer layer (not shown) made of Mg Ag or the like (ideal electrode), and the upper electrode 13 is operated as a reflective electrode. When any of the transparent electrodes is operated, it can be formed using the same material as the lower electrode 11. Further, the transmittance of the upper electrode 13 is preferably 50% or more with respect to the wavelength of 400 to 80 nm in order to make the function of taking out the light from the machine layer 12 from above, and the transmittance is 50% or more. It is better to be 85% or more. (Protective layer) -13- 200950574 The protective layer 14 is composed of one or more inorganic films, at least one of which is a hydrogen-containing tantalum nitride film. In the present invention, it is important that the element ratio of hydrogen in the tantalum nitride film is 30 at% or less, for example, 25 to 29 at%. By setting the element ratio of hydrogen to 30 at% or less, a tantalum nitride film excellent in moisture resistance can be obtained, and the desired effects of the present invention can be obtained. It is just a matter of course, further, by making the ratio of germanium in the tantalum nitride film between 30 at% and 40 at. Hereinafter, the element ratio of nitrogen is 35 at% or more and 40 at% or less, and more excellent moisture resistance can be obtained. The ratio of each constituent element in the tantalum nitride film can be calculated using Rutherford backscattering and elastic backlash analysis. The elemental composition of the tantalum nitride film is substantially 100 at% in the total amount of hydrogen, helium and nitrogen. However, since there is an unintentional mixing of impurities in the film, the trace impurity is also used as a residual portion. The case where the calculation is added to become 100 at%. The protective layer 14 which satisfies the element ratio of the present invention described above can be obtained by adjusting the film formation conditions in the CVD method or the like as will be described later. The protective layer 14 includes a tantalum nitride film satisfying the above element ratio, and may be formed of a plurality of layers, for example, a tantalum nitride film formed by changing an element ratio by changing a film formation condition, or may be a tantalum niobium oxide nitride Laminated film of film. (Adhesive layer) The adhesive layer 15 is used in order to bond the support substrate 1 and the sealing substrate 30 (in the example shown in FIG. 1 , the laminated body 16 such as a color filter on the sealing substrate 30). . The ideal adhesive layer 15 5 ' is exemplified by a UV (ultraviolet) curing adhesive or the like. In the above-mentioned UV-curable adhesive, the element for setting the distance between the support substrate 10 and the sealing substrate 30 is added to the above-mentioned UV-curable adhesive, and examples thereof include glass beads and the like. Spacer particles. (Sealing substrate) The sealing substrate 30 is preferably a metal sealing substrate such as a glass substrate, an SUS can or an A1 can, or an acrylic resin such as polyalkylene or polymethyl methacrylate or a polyparaben. A polyester resin such as a diester, a polycarbonate resin or a rigid resin substrate formed of a polyimide resin. Further, examples of other preferable sealing substrates 30 include acrylic resins such as polyene and polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polycarbonate resins, or polyphthalamides. A flexible film formed of an amine resin or the like. Further, as the sealing substrate 30, a transparent substrate is used, and as shown in the drawing, a laminate 16 such as a color filter or a light conversion layer (not shown) may be used (a laminate of a color filter or the like), a color filter, or the like. The laminate 16 contains a color filter and a color conversion layer. A color filter is a layer that only transmits light in a desired wavelength region. In the case where the color filter is laminated to the color conversion layer of the laminate 16, the color conversion layer is effective in enhancing the color purity of the light whose wavelength distribution is changed. As the color filter, for example, a commercially available color filter material for liquid crystals such as a color mosaic made of Fujifilm Electronics Materials can be used. -15- 200950574 (Light Conversion Layer) The light conversion layer is a layer containing a fluorescent pigment for color conversion, and may also contain a matrix resin. This layer is a layer which changes the wavelength distribution of the light emitted from the organic EL element 20 in order to emit light of different wavelength domains. Here, the fluorescent dye constituting the light conversion layer is a dye that emits light of a desired wavelength region (for example, red, green, or blue). As a fluorescent pigment that absorbs light from the cyan to the cyan field and emits red light, for example, rose red B, rose red 6G, rose red 3B, rose red 101, rose red 110, thio rose Red, alkaline purple 11, rosy red 2, etc. rose red pigment, cyanine pigment ' 1-ethyl-2-[4-(p-dimethylaminophenyl)-1,3-butane a pyridine-based dye such as a pyridine-perchloric acid pyridinium salt (pyridine 1) or an oxazine-based dye. Further, various dyes (direct dyes, acid dyes, base-based dyes, disperse dyes, and the like) can be used as long as they have fluorescence properties. On the other hand, as a light-absorbing pigment that emits fluorescence in the green region as light that absorbs the blue to cyan field, for example, 3-( 2'-benzothiazolyl)-7-diethylamine is exemplified. Beanin (coumarin 6 ), 3-(2'-benzimidazolyl)-7-diethylamine coumarin (coumarin 7 ), 3-(2'-N-methylbenzimidazole Base)-7-diethylamine coumarin (coumarin 30), 2,3,5,6- 1H,4H-tetrahydro-8-trifluoromethylquinazine (9,9a,l-gh Coumarin (coumarin 153) and other coumarin pigments, or coumarin pigment dyes, basic yellow 51', further, solvent yellow 11, solvent yellow 116, etc. Pigments, etc. Further, various dyes (direct dyes, acid dyes -16-200950574, salt-based dyes, disperse dyes, etc.) can be used as long as they have fluorescence properties. Further, as the base resin constituting the light conversion layer, an acrylic resin or various polyoxyl polymers may be used, or various of them may be used. For example, a linear polyoxyl polymer and a denatured resin polyoxyl polymer can be used. As an example of FIG. 1 shown above, the organic EL display 100 having a single light-emitting portion is exemplified, but the present invention The organic EL display is not limited to these, and it may be a light-emitting unit that has independent and controls a plurality of light-emitting units. For example, both the lower electrode and the upper electrode are an electrode group composed of a plurality of strip electrodes, and the extending direction of the strip electrode constituting the lower electrode and the extending direction of the strip electrode constituting the upper electrode are exemplified. The difference is that the organic layer is interposed between the electrodes. These examples are so-called passive matrix driven organic EL displays. In other cases, it is preferable to make the above-described cross-sectional form a vertical form from the viewpoint of forming a display indicating an arbitrary image and/or character. As another example of the light-emitting portion having a plurality of light-emitting portions, a conversion element composed of a plurality of thin film transistors formed on a substrate and a plurality of portions connected by a one-to-one portion may be used as a common electrode, and a common electrode may be used. An example of an organic layer is interposed between transparent electrodes of one type. Such an example is a so-called active matrix driven organic EL display. In any case where the lower electrode is formed by a plurality of electrodes in either the passive matrix drive or the active matrix drive, an insulating oxide (SiOx, TiO 2 , Zr02, A10x, etc.) or insulating nitrogen may be used. A compound (A1NX, SiNx, etc.), a polymer material, or the like, an insulating film is formed in a gap between -17 and 200950574 of a plurality of electrodes. Further, as an example shown in Fig. 1, in order to realize the display of a monochrome currency, the present invention is not limited to such an example, and includes a display of a multicolor display. When a display of a multi-color display is realized, there are three types of cells including the organic EL element 20 shown in FIG. 1 and the laminated body 16 such as a light conversion layer and a color filter, and at the same time, The color conversion layers included in the light conversion layer and the laminate 16 in each unit are red, green, and blue color conversion layers, so that the color filters included in the laminate 16 correspond to the color conversion layers of the respective units. The three types of cells are combined into a pixel. <Manufacturing Method of Organic EL Display> When manufacturing an organic EL display as shown in Fig. 1, the following respective forming steps can be employed. (Organic EL Element Forming Step) [Lower Electrode Forming Step] The lower electrode 11 is formed on the support substrate 10. When using a high-reflectivity metal, vapor deposition or sputtering using resistance heating or electron beam heating can be used. In the case of vapor deposition, 1.0 XI (the film formation rate below T4Pa can be 0.1 to 10 nm/sec. For the case of the 'sputter method', for example, when a DC nuclear magnetic sputtering method is used, etc. As the sputtering gas, an inert gas such as Ar can be used, and the film forming pressure can be 0.1 to 2. OPa. In any of the vapor deposition and sputtering methods, the formation environment -18-200950574 can be vacuumed. The surface which achieves excellent adhesion to the adjacent layer is ideal [organic layer forming step]. The organic layer 12 is formed on the lower electrode 11. As the organic layer 12, the organic light-emitting layer can be transported to any selected hole. The layer, the hole injection layer, the electron transport layer, and the electron injection layer are formed by vapor deposition using resistance heating or electron beam heating in the order determined, and the layers constituting the organic layer 15 are desired in order to achieve each. It is very important that the characteristics are formed in a sufficient film thickness. The thickness of each layer constituting the organic layer 12 is 2 to 50 nm for the organic light-emitting layer, 2 to 50 nm for the hole transport layer, and 2 to 200 nm for the hole injection layer, and electrons. Transport layer is 2 Preferably, the electron injecting layer is 2 to 50 nm, and the buffer layer which is selectively formed between the organic layer 12 and the upper electrode 13 can be formed by vapor deposition using electric resistance heating or electron beam heating. Thickness, in consideration of driving voltage and transparency, preferably 1 〇 nm or less. [Upper electrode forming step] The upper electrode 13 is formed on the upper portion of the organic layer 12. The upper electrode 13 can be formed by sputtering or vapor deposition. For example, as the sputtering gas, an inert gas such as Ar can be used, and a DC nuclear magnetic particle sputtering method or the like is used in a film forming pressure of about 0.1 to 2. OPa. In this case, in order to prevent deterioration of the organic layer 12, It is preferred that the plasma formed on the upper portion of the target is not directly irradiated on the direct organic layer 12. [Protective layer forming step] The step of forming the protective layer 14 on the upper electrode 13. The protective layer μ, as described above It is composed of one or more inorganic films containing at least one layer of a hafnium hydroxide-containing film, and can be formed by a CVD method or a special plasma CVD method for producing a tantalum nitride film satisfying the conditions of the present invention. good The content of the material is as follows. Monooxane, ammonia, and nitrogen are used as the material gas, and the flow ratio of ammonia to monoterpene is 0.5 or more and 1 or less. Further, the pressure can be about 10 to 200 Pa, and 27.12 MHz or 40·68 使用 can be used. The high-frequency power source can have a power density of 0.1 W/cm 2 to 2 W/cm 2 . By forming a film under such conditions, a tantalum nitride film having excellent moisture resistance can be obtained. It is preferable that the temperature of the substrate in the plasma is controlled to be 70 ° C or less. (Sealing structure forming step) [Sealing body forming step] On the sealing substrate 30, a color filter is formed as needed. The laminate 16 (color filter and color conversion layer). The laminate 16' of a color filter or the like can be coated by a known lamination method, that is, a spin coating method, a roll coating method, a casting method, a dip coating method, or the like, after coating the materials of the respective layers, The patterning method is formed by patterning. In the above-mentioned known forming methods, 'special line' is used as a forming condition of the color filter layer, since the forming method thereof has been established 'after coating by spin--20-200950574 transfer coating method, by light micro- The method of forming the shadow method is better. In the case where a plurality of color fine adjustment portions such as color filters are formed on one transparent substrate 30, the full color display can be realized by forming a plurality of types of color fine adjustment portions into a matrix. [Light Conversion Layer Forming Step] A step of forming a light conversion layer on the sealing substrate 30 as needed. When a plurality of types of color conversion pigments are used to form the light conversion layer, a plurality of types of color conversion pigments may be preliminarily mixed according to a predetermined ratio to obtain a preliminary mixture which is mixed with the matrix resin, and the preliminary mixture is used for vaporization. Deposition. Alternatively, a plurality of types of the matrix resin containing the color conversion dye may be disposed in another heating portion, and the resin containing the respective color conversion dyes may be heated and co-deposited elsewhere. In particular, when a plurality of types of color-converting dyes have large differences in characteristics such as vapor deposition rate and/or vapor pressure, it is advantageous to carry out co-deposition. Further, in the case where the entire coated passivation film is arbitrarily selectively formed on the light conversion layer, a method such as plasma CVD can be used. In particular, from the viewpoint of preventing deterioration of the light conversion layer, it is preferable to form a film with a substrate temperature of 100 ° C or lower. [Step of Forming Bonding Substrate to Sealing Substrate] As shown in Fig. 1, the supporting substrate 1A and the sealing substrate 30 are bonded together by using the adhesive layer 15. For the bonding conditions, various known -21 - 200950574 bonding methods can be used. In order to reduce the influence on the heat of the organic layer 12, it is preferable to use an epoxy resin which is cured by ultraviolet curing and heat curing. From the above, the organic EL display 1 of the present invention as shown in Fig. 1 can be obtained. [Examples] Hereinafter, the present invention will be described in detail by way of examples, and the effects of the present invention are actually proved. (Embodiment 1) This embodiment is an organic emission type EL display (pixel number 2 χ 2 (red only), pixel width 0.3 mm). As the support substrate 10, fused glass (1737 glass manufactured by CORNING, 5 〇χ 5 〇χ 1.1 mm) was used. On the support substrate 10, an Ag film having a film thickness of 10 nm was deposited by sputtering, and patterned by photolithography to form a strip-shaped lower electrode 11 having a width of 〇3 mm. Next, the support substrate 10 on which the lower electrode 11 was formed was placed in a resistance heating vapor deposition apparatus, and Li having a film thickness of 1.5 nm was deposited on the lower electrode 11 using a photomask to form a cathode buffer layer. Next, four layers of the electron transport layer/organic EL layer/hole transport layer/hole injection layer are sequentially deposited using a resistance heating vapor deposition apparatus to obtain an organic layer 12. The pressure in the vacuum chamber at the time of film formation was set to lxl (T4Pa. The layers constituting the organic layer 15 were deposited at a vapor deposition rate of 0.1 nm/s. As the electron transport layer, Alq3 having a film thickness of 20 nm was formed (tris(8-hydroxyl) Quinoline) aluminum, a DPVBi having a thickness of 30 nm was formed as an organic EL layer, and α-NPD having a thickness of 10 nm was formed as a hole transport layer 22-200950574, and a film thickness was formed as a hole injection layer. Then, the MgAg of 5 nm is deposited, and the damaged layer is formed when the transparent electrode is formed. The laminate of the organic layer 12 is formed to move to the opposite side without damaging the vacuum. A plating apparatus is provided with a metal mask to deposit IZO of a film thickness of 100 μm, and a strip extending from the lower electrode 11 in a vertical direction to form a strip-shaped transparent upper electrode 13 having a width of 〇3 mm. Next, an upper electrode 13 is formed. The support substrate 10 is transferred to a plasma CVD reaction chamber, and a tantalum nitride film is formed on the upper electrode 13 by using a monodecane gas and an ammonia gas to obtain a protective layer 14. The nitrogen flow rate is 2 liter/min, monodecane gas and ammonia. Gas flow ratio is 1: 0.7, film pressure For lOOPa, the power of the high frequency power supply of 27.12 MHz is lkW, and the temperature of the supporting substrate is 40 ° C. By the above, the lower electrode 11 / the organic layer 12 / the upper electrode 13 are formed, and the protective layer 14 is formed at the upper portion. The organic EL element 20. The composition of the obtained protective layer 14 is analyzed by Rutherford backscattering and elastic recoil analysis. At this time, the composition ratios of Si, N, and yttrium are respectively 3 4 at % > 3 8 at % ' 2 8 at %° On the other hand, a red filter material (CR 7 0 0 1 , manufactured by Fujifilm Electroni cs Materials) is applied to the transparent substrate (sealing substrate) 30 to emit light corresponding to the organic EL element 20 At the position of the portion, a red color reducer layer having a thickness of 1.5 μm was formed in a size of 55 mm x 0.5 mm. Next, the laminate in which the color filter layer was formed was transferred to a resistance heating vapor deposition apparatus to prepare a containing layer. The light conversion layer of coumarin 6 and DCM-2 -23- 200950574. The film thickness is formed by co-depositing coumarin 6 and DCM-2 in another canon in a vapor deposition apparatus. Onm light conversion layer. At this time, the vapor deposition rate of coumarin 6 is made into The vapor deposition rate of 33 nm/s and DCM-2 was 0.005 nm/s, and the heating temperature of each of the crucibles was controlled. The light conversion layer of this example was based on the total number of constituent molecules, and coumarin 6 and The molar ratio of the DCM-2 is 49: 1. Next, the support substrate 10 on which the organic EL element 20 is formed is placed on the transparent substrate 30 on which the color filter layer is formed, and is placed in an oxygen concentration of 5 ppm or less and a water concentration of 5 ppm or less. In the bonding apparatus, the adhesive layer 15 was dropped on the outside of the sealing substrate 30 on which the red color filter layer was formed, using an epoxy-based ultraviolet curable adhesive. The support substrate 10 including the organic EL element 20 is disposed opposite to the red color filter layer, and after decompressing the device to about 100 Pa, the position of the light-emitting portion of the organic EL element 20 and the red color filter layer is set. Align the two layers to fit the inside of the device to atmospheric pressure. Next, the adhesive layer 15 was irradiated with ultraviolet rays by a photomask to be pseudo-hardened, and placed in a heating furnace for heating at 80 ° C for 1 hour, and then naturally cooled in a furnace for 3 minutes. Thereafter, the bonded body was taken out from the apparatus to obtain an organic EL display. (Comparative Example 1) As a condition for forming the protective layer, the ratio of the flow rate of the monodecane gas to the ammonia gas was 1:1.1, the film forming pressure was 100 Pa, and the power of the high frequency power source of 27.12 MHz was lkW, so that the temperature of the supporting substrate was maintained. An organic EL display was produced in the same manner as in Example 1 except that the temperature was 40 ° C to -24 - 200950574. The composition of the protective layer was analyzed by Rutherford backscattering and elastic recoil analysis. At this time, the composition ratios of Si, N, and yttrium were respectively 29 at% and 3 8 at % ' 3 3 at% ° (Comparative Example 2) as the formation conditions of the protective layer, except that the flow rate of monodecane gas and ammonia gas was compared. The organic EL display was produced in the same manner as in Example 1 except that the film formation pressure was 1 〇〇Pa, the power of the high-frequency power source of 2 7.12 MHz was lkW, and the temperature of the support substrate was 40 ° C. . The composition of the protective layer was analyzed by Rutherford backscattering and elastic recoil analysis. At this time, the composition ratios of Si, N, and yttrium were respectively 42 at% and 3 1 at% '27 at%. The organic EL display of the examples and the comparative examples formed as described above was continuously driven at a current density of 0.1 A/cm 2 in an environment of 60 ° C and 90 RH %, and voltage and luminance were measured. The enthalpy obtained by dividing the luminance by the current 値 was calculated as the luminous efficiency, and when the initial luminous efficiency was 1, the retention of the luminous efficiency in 1,000 hours was as shown in Table 1 below. [Table 1] Maintenance rate of efficiency Remarks Example 1 0.8 - Comparative Example 1 0.4 Comparative Example 2 0.3 Low luminous efficiency due to light absorption of a protective film - 25 - 200950574 From the results of Table 1 above, it is understood that the present invention is satisfied. In each of the examples, the results of the improvement in the luminous efficiency were excellent. As can be seen from the above, in the examples within the scope of the invention of the present invention, the life characteristics were excellent, and the lifespan was short in each comparative example which deviated from the scope of the invention. This result is considered to be because, in the comparative example, there is a relationship of moisture infiltration from the protective layer. Next, the film formation conditions of the tantalum nitride film were changed to have the moisture resistance of the obtained tantalum nitride film as shown in Table 2 below. As other film forming conditions as shown in the following Table 2, the temperature of the supporting substrate was 50 ° C, the power density was 5 5 W / cm 2 , the film forming pressure was 100 Pa, and the nitrogen flow rate was 2 L / min. The moisture resistance was evaluated by forming each protective layer at a thickness of 3 μm on a 10 μm thick Ca film, and placing the film at a temperature of 95° C. and 50 RH% for 1 000 hours. The area ratio of the metamorphic part is compared. The results are shown in the following Table 2. Further, the ratio of the elements in the obtained tantalum nitride film, H, Si, N and the remaining portion (which is mixed by the impurity in the material gas or the material of the film cavity or the cleaning gas, is less than .5 at%) The total amount of the measurement is 100%%. In addition, the unit "seem" of the flow rate in the following table is the standard flow rate unit "standard cc/min" at 〇 ° C and 1 atm.
-26 200950574 [表2] \ 製膜條件 膜中之 膜中之 Η比率 (at%) 1000小時後 之非變質部 之面積比(％) SfflU流量 (scan) NH3流量 (scan) NH3/S1H4 流量比 電源頻率 (MHz) 元素比 N/(N+Si) 實驗例 1 100 20 0.2 27.12 0.187 32.7 25 (有光吸收） 實驗例 2 100 30 0.3 27.12 0.295 27.5 30 (有光吸收） 實驗例 3 100 40 0.4 27.12 0.427 273 75 實驗例 4 100 50 0.5 27.12 0.504 27.8 90 實驗例 5 100 60 0.6 27.12 0.518 28.7 92 實驗例 6 100 70 0.7 27.12 0.531 28.1 95 實驗例 7 100 80 0.8 27.12 0.538 27.9 96 實驗例 8 100 90 0.9 27.12 0.544 28.3 93 實驗例 9 100 100 1 27.12 0.556 28.4 90 實驗例 10 100 110 1.1 27.12 0.568 32.9 80 實驗例 11 100 80 0.8 40.38 0.540 27.8 96 實驗例 12 100 70 0.7 13.56 0.458 36.2 25 實驗例 13 100 80 0.8 13.56 0.473 36.1 30 實驗例 14 100 90 0.9 13.56 0.490 38.2 25 如上述表2中所示般，氨氣體（NH3 )流量比50sccm -27- 200950574 還低之場合時，膜中之含氮量爲小。又，變的比40sccm 還低時，可見光之吸收變的顯著可見。此領域中之氮化矽 膜被認爲係，並無形成均質之膜，而混在有SiN鍵結、 SiH鍵結、SiSi鍵結之狀態。又，Ca膜之小孔產生數爲 多，變質部之面積變大。由此可判斷，膜之防濕性爲低。 NH3流量爲50sccm〜lOOsccm之場合時，膜中之含氮 量接近於氮化矽膜之化學量論比，膜中之含氫量爲不滿 3 Oat%。又，Ca膜之小孔產生數也爲少，變質部之面積變 小。 另一方面，若NH3流量超過lOOsccm時，膜中之含 氮量也增加，氫之含有量也增加。又，Ca膜之小孔數增 加，變質部之面積增加。此事被認爲係由於膜中之NH鍵 結增加所造成。 猶，此些膜之應力之任一皆爲±5 OMPa以内，已確認 就算於上部電極上形成，也不會發生膜剝離一事。 從此些結果中可確認，膜中之含氫量爲30at%未満之 場合時，特別係，含矽量爲30〜40at%、氮之含有量爲 3 5〜40at%之場合時，可得到高防濕性之膜。而此相等於身 爲原料氣體之單矽烷與氨氣體之流量比爲0.5以上1以下 之場合。 又，若將電源頻率變更爲40.68MHz之場合時雖也可 得到良好之氮化矽膜，但若將頻率變更爲13.56MHz時， 可發現膜中之含氮量降低，氫比率上昇超過30at%之現象 。而此被認爲係因爲反應室内中之氨氣體並沒有被充份分 -28- 200950574 解，而變得難以進入膜中所至。 [產業上之利用可能性] 藉由本發明’可提升曾爲以往之問題的有機EL顯示 器之壽命特性。因此，本發明之有機EL顯示器，可實現 在長期間下優良之發光效率。故，本發明，於近年來，在 要求有更高發光效率有機EL顯示器之開發之狀況下中， 可以說係有希望之技術。 【圖式簡單說明】 ' [圖Π表示本發明之有機EL顯示器之一例之模式的 ' 剖面圖。 【主要元件符號說明】 10 :支持基板 1 1 :下部電極 12 :有機層 13 :上部電極 14 :保護層 15 :黏著層 16:濾色器等之層合體 20 :有機EL元件 3 0 :密封基板 100 :有機EL顯示器 〆 -29 --26 200950574 [Table 2] \ The ratio of the ruthenium in the film in the film forming condition (at%) The area ratio of the non-metamorphizing portion after 1000 hours (%) SfflU flow rate (scan) NH3 flow rate (scan) NH3/S1H4 flow rate Specific power frequency (MHz) Element ratio N/(N+Si) Experimental Example 1 100 20 0.2 27.12 0.187 32.7 25 (with light absorption) Experimental Example 2 100 30 0.3 27.12 0.295 27.5 30 (with light absorption) Experimental Example 3 100 40 0.4 27.12 0.427 273 75 Experimental Example 4 100 50 0.5 27.12 0.504 27.8 90 Experimental Example 5 100 60 0.6 27.12 0.518 28.7 92 Experimental Example 6 100 70 0.7 27.12 0.531 28.1 95 Experimental Example 7 100 80 0.8 27.12 0.538 27.9 96 Experimental Example 8 100 90 0.9 27.12 0.544 28.3 93 Experimental Example 9 100 100 1 27.12 0.556 28.4 90 Experimental Example 10 100 110 1.1 27.12 0.568 32.9 80 Experimental Example 11 100 80 0.8 40.38 0.540 27.8 96 Experimental Example 12 100 70 0.7 13.56 0.458 36.2 25 Experimental Example 13 100 80 0.8 13.56 0.473 36.1 30 Experimental Example 14 100 90 0.9 13.56 0.490 38.2 25 As shown in Table 2 above, when the ammonia gas (NH3) flow rate is lower than 50sccm -27- 200950574, the nitrogen content in the film is small. . Further, when the change is lower than 40 sccm, the absorption of visible light is remarkably visible. The tantalum nitride film in this field is considered to be a film which does not form a homogeneous film, and is mixed in a state of SiN bonding, SiH bonding, and SiSi bonding. Further, the number of pores generated in the Ca film is large, and the area of the metamorphic portion is increased. From this, it can be judged that the moisture resistance of the film is low. When the NH3 flow rate is 50 sccm to lOOsccm, the nitrogen content in the film is close to the stoichiometric ratio of the tantalum nitride film, and the hydrogen content in the film is less than 3 Oat%. Further, the number of pores generated in the Ca film is small, and the area of the metamorphic portion is small. On the other hand, when the NH3 flow rate exceeds 100 sccm, the amount of nitrogen contained in the film also increases, and the content of hydrogen also increases. Further, the number of small holes in the Ca film increases, and the area of the metamorphic portion increases. This matter is believed to be caused by an increase in NH bonds in the film. In any case, any of the stresses of these films is within ±5 OMPa, and it has been confirmed that even if formed on the upper electrode, film peeling does not occur. From these results, it was confirmed that when the amount of hydrogen contained in the film was 30 at%, particularly when the amount of cerium was 30 to 40 at% and the content of nitrogen was 3 5 to 40 at%, high Moisture resistant film. This is equivalent to the case where the flow ratio of the monodecane to the ammonia gas as the material gas is 0.5 or more and 1 or less. Further, when the power supply frequency is changed to 40.68 MHz, a good tantalum nitride film can be obtained. However, when the frequency is changed to 13.56 MHz, the nitrogen content in the film is lowered, and the hydrogen ratio is increased by more than 30 at%. The phenomenon. This is considered to be because the ammonia gas in the reaction chamber is not fully resolved by the solution, and it becomes difficult to enter the membrane. [Industrial Applicability] By the present invention, the life characteristics of an organic EL display which has been a problem in the past can be improved. Therefore, the organic EL display of the present invention can achieve excellent luminous efficiency over a long period of time. Therefore, the present invention can be said to be a promising technique in recent years in the development of an organic EL display requiring higher luminous efficiency. [Simplified Description of the Drawings] ' [The figure shows a sectional view of a mode of an example of the organic EL display of the present invention. [Description of main component symbols] 10: Support substrate 1 1 : Lower electrode 12 : Organic layer 13 : Upper electrode 14 : Protective layer 15 : Adhesive layer 16 : Laminated body of color filter or the like 20 : Organic EL element 3 0 : Sealed substrate 100: Organic EL Display 〆-29 -