201229303 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種成膜裝置及成膜方法。 本申請案係主張於2010年10月8日在日本提出申請 的特願20 1 0-2289 1 7號爲基準的優先權，且於此處援用其 內容。 【先前技術】 阻氣性薄膜可使用作爲適合於包裝飲食品、化妝品、 清潔劑之物品的容器。近年來，提案在塑膠薄膜等之基材 薄膜之一面上形成氧化矽、氮化矽、氧氮化矽、氧化鋁等 之無機化合物的薄膜所形成的阻氣性薄膜。 使該無機化合物之薄膜在塑膠基材表面上成膜的方法 ，已知有真空蒸鍍法、濺鍍法、離子鍍著法等之物理氣相 成長法（PVD )、減壓化學氣相成長法、電漿化學氣相成 長法等之化學氣相成長法（CVD)。 而且，使用該成膜方法所製造的阻氣性薄膜，例如於 曰本特開平4-89236號公報（專利文獻1)中揭示，在塑 膠基材表面上設置由藉由蒸鍍所形成的2層以上之矽氧化 物膜所成的積層蒸鑛膜層之阻氣性薄膜。 〔習知技術文獻〕 [專利文獻1]日本特開平4-89236號公報 【發明內容】 201229303 然而，使用上述專利文 性薄膜，雖可作爲可滿足如 包裝容器之阻氣性較低的物 EL元件或有機薄膜太陽能 氣性薄膜時，就阻氣性而言 而且，如上述專利文獻 彎曲時，會有對氧氣或水蒸 如於可撓性液晶顯示裝置被 使用的阻氣性薄膜，就薄膜 分。 本發明係有鑑於上述情 阻氣性，且可製造即使於薄 氣性降低情形的阻氣性積層 ，以提供一種可有效地製造 膜方法爲目的》 爲解決上述課題時，本 薄膜之成膜裝置，其特徵爲 空室；在前述真空室內供應 屬化合物及與該有機金屬化 體的氣體供應裝置；配置於 前述一對電極施加交流電力 電漿產生用電源；與切換控 漿產生用電源中任何一者或 與前述反應氣體反應，產生 獻1中記載的成膜方法之阻氣 飮食品、化妝品、清潔劑等之 品用阻氣性薄膜，惟作爲有機 電池等之電子裝置之包裝用阻 不爲充分。 1記載的阻氣性薄膜，於使其 氣而言之阻氣性降低的問題， 要求耐彎曲性的顯示裝置中所 被彎曲時之阻氣性而言不爲充 形者，·以提供一種具有充分的 膜被彎曲時，仍可充分抑制阻 薄膜之成膜裝置爲目的。另外 該物性之阻氣性積層薄膜的成 發明係提供一種在基材上形成 具有於內部收容前述基材之真 含有前述薄膜之原料的有機金 合物反應的反應氣體之成膜氣 前述真空室內之一對電極；對 且產生前述成膜氣體之電漿的 制前述氣體供應裝置及前述電 兩者且使前述有機金屬化合物 形成前述有機金屬化合物之含201229303 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a film forming apparatus and a film forming method. This application claims priority on the basis of Japanese Patent Application No. 20 1 0-2289 No. 17 filed on October 8, 2010 in Japan, and its contents are hereby incorporated by reference. [Prior Art] The gas barrier film can be used as a container suitable for packaging articles for foods, cosmetics, and detergents. In recent years, it has been proposed to form a gas barrier film formed of a film of an inorganic compound such as cerium oxide, cerium nitride, cerium oxynitride or aluminum oxide on one surface of a substrate film such as a plastic film. A method of forming a film of the inorganic compound on the surface of a plastic substrate is known as a physical vapor phase growth method (PVD) such as a vacuum deposition method, a sputtering method, or an ion plating method, and a decompression chemical vapor growth method. Chemical vapor phase growth (CVD) methods such as plasma and plasma chemical vapor growth. In the gas barrier film produced by the film formation method, for example, it is disclosed in JP-A-4-89236 (Patent Document 1) that a surface formed of a vapor deposition is provided on the surface of a plastic substrate. A gas barrier film of a layered vaporized film layer formed by a tantalum oxide film or more. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 4-89236-A-201229303 However, the above-mentioned patented film can be used as an EL which can satisfy a gas barrier property such as a packaging container. In the case of a component or an organic thin film solar gas film, in terms of gas barrier properties, and when the above-mentioned patent documents are bent, there is a gas barrier film which is used for vaporizing oxygen or water as in a flexible liquid crystal display device. Minute. In view of the above-described gas barrier properties, it is possible to produce a gas barrier layer which is capable of efficiently producing a film even in the case where the gas permeability is lowered, in order to provide a method for efficiently producing a film. The device is characterized in that it is an empty chamber; a compound and a gas supply device for the organic metallized body are supplied in the vacuum chamber; and a power source for generating an alternating current power plasma is disposed in the pair of electrodes; and a power source for switching and controlling plasma generation Any one of them may react with the reaction gas to produce a gas barrier film for gas barrier foods, cosmetics, detergents, and the like which are described in the film forming method of the first embodiment, but is used as a packaging resistor for an electronic device such as an organic battery. Not enough. The gas barrier film described in the first aspect has a problem that the gas barrier property of the gas is lowered, and the gas barrier property when the bending resistance is required to be bent is not sufficient. When a sufficient film is bent, the film forming apparatus of the resist film can be sufficiently suppressed. In addition, the invention of the gas barrier laminated film of the physical property provides a film forming gas in which a reaction gas having an organic gold compound reaction for containing the raw material of the substrate in the substrate is formed on the substrate. a counter electrode; the gas supply device and the electric device for generating the plasma of the film forming gas; and the organometallic compound is formed into the organometallic compound
-6- S 201229303 金屬元素或半金屬元素且不含碳的化合物之第1反應條件 ，及使前述有機金屬化合物與前述反應氣體反應，產生形 成前述有機金屬化合物之含碳與金屬元素或半金屬元素的 含碳化合物之第2反應條件的控制部之第1成膜裝置（稱 爲「第1實施形態」）。 於該說明書及申請專利範圍中，「有機金屬化合物」 之「金屬」係包含金屬元素及半金屬元素》 此外，本說明書中所使用的一些用語及表現的定義如 下所述。 「真空室」係爲使內部形成減壓狀態（較佳者爲接近 真空之減壓狀態）時之容器。通常，藉由運作設置於反應 室之真空幫浦，在反應室內製作減壓環境（較佳者爲接近 真空之減壓環境）。 「基材」係於形成膜時作爲該膜之支持體的物體。 「成膜氣體」係含有以形成膜之原料的原料氣體作爲 必須要素之氣體’視其所需尙含有與原料氣體反應形成化 合物之反應氣體，或不含於所形成的膜中，惟爲賦予產生 電漿或提高膜質等之補助氣體。 「原料氣體」係作爲膜之主成分的材料供應源之氣體 。例如’形成SiOx膜時，以HMDSO、TEOS、矽烷等之含-6- S 201229303 a first reaction condition of a metal element or a semimetal element and a carbon-free compound, and reacting the organometallic compound with the reaction gas to produce a carbon-containing metal element or a semi-metal forming the organometallic compound The first film forming apparatus (referred to as "first embodiment") of the control unit of the second reaction condition of the carbonaceous compound of the element. In the scope of this specification and the patent application, the "metal" of "organometallic compound" contains metal elements and semi-metal elements. In addition, some terms and expressions used in this specification are as follows. The "vacuum chamber" is a container in which the inside is decompressed (preferably in a reduced pressure state close to vacuum). Usually, a vacuum-reducing environment (preferably a vacuum-reduced environment close to vacuum) is produced in the reaction chamber by operating a vacuum pump provided in the reaction chamber. The "substrate" is an object that serves as a support for the film when the film is formed. The "film-forming gas" is a gas containing a material gas which is a raw material for forming a film as a necessary element, and contains a reaction gas which reacts with a material gas to form a compound, or is not contained in the formed film, but is imparted thereto. A chemical gas or a supplementary gas that enhances the film quality. "Material gas" is a gas supply source that is a main component of the film. For example, when forming an SiOx film, it is contained in HMDSO, TEOS, decane, etc.
Si的氣體爲原料氣體。 「反應氣體」係與原料氣體反應，加入所形成的膜中 之氣體，例如形成SiOx膜時，相當於氧氣（〇2)。 而且’於本說明書中’有關薄膜所使用的表現「不含 201229303 碳」，係指表示有關該薄膜藉由進行XPS縱深分析（ depth profile)測定所作成的自該薄膜之膜厚方向上的該 薄膜表面之距離、與相對於構成薄膜之原子的合計量而言 碳原子量的比例（碳之原子比）之關係的碳分布曲線中， 碳含量爲1 at%。此處，有關上述碳分布曲線，「構成薄 膜之原子的合計量」係指構成薄膜之原子的合計數，「碳 原子之量」係指碳原子之數。另外，單位「at%」係「原 子％」之簡稱。 於本發明中，前述控制部係以於前述第1反應條件中 ，在前述成膜氣體中包含由前述有機金屬化合物與前述反 應氣體產生前述不含碳之化合物的反應·時之當量以上的前 述反應氣體，其次，於前述第2反應條件中·，在前述成膜 氣體中包含產生前述不含碳之化合物的反應時之未達當量 的前述反應氣體，控制前述氣體供應裝置的方式所構成爲 宜。 於本發明中，前述控制部以對前述氣體供應裝置而言 ，於切換前述第1反應條件與前述2反應條件時，可連續 變化前述成膜氣體中所含的前述反應氣體之量所構成爲宜 〇 於本發明中，前述控制部以於前述第1反應條件中施 加發生產生前述不含碳之化合物的強度之前述電漿的交流 電力，其次，於前述第2反應條件中施加發生產生前述含 碳化合物之強度的前述電漿的交流電力，控制前述電漿產 生用電源之方式所構成爲宜。 -8- 201229303 於本發明中，前述控制部以對前述電漿產生用電源而 言，於切換前述第1反應條件與前述第2反應條件時，爲 可連續變化前述交流電力之電力量的方式所構成爲宜。 此外，本發明係提供一種成膜裝置，其係連續搬送長 尺狀基材且在前述基材上連續成膜的成膜裝置，其特徵爲 具有：在內部收容前述基材之真空室，於前述真空室內連 續搬送前述基材之搬送手段，在部分與被搬送的前述基材 重疊的空間中產生放電電漿的電漿產生手段，及沿著前述 空間之前述基材的搬送方向，在數處產生磁場的該空間內 使電漿強度不同的磁場產生手段；且前述搬送手段於前述 空間內一邊保持前述基材平坦且.同時搬送前述基材之方式 所構成的第2成膜裝置（稱爲「第2實施形態」）。 此外，本發明係提供一種在基材上形成薄膜之成膜方 法，其特徵爲具有由前述薄膜之原料的有機金屬化合物及 與該有機金屬化合物反應的反應氣體產生形成前述有機金 屬化合物之含金屬元素或半金屬元素且不含碳之化合物的 反應中，使用當量以上之前述反應的氣體，來進行電漿 CVD的第1步驟；及產生前述不含碳之化合物的反應中， 使用未達當量之前述反應氣體，來進行產生形成前述有機 金屬化合物之碳與含金屬元素或半金屬元素之含碳化合物 的電漿CVD之第2步驟的第1成膜方法。 而且，本發明係提供一種在基材上形成薄膜的成膜方 法，其特徵爲具有：發生產生由前述薄膜之原料的有機金 屬化合物及與該有機金屬化合物反應的反應氣體產生形成 201229303 前述有機金屬化合物的含金屬元素或半金屬元素且不含碳 之化合物的強度之放電電漿，以進行電漿CVD的第1步 驟；及發生產生形成前述有機金屬化合物之含有碳及金屬 元素或半金屬元素之含碳化合物的強度之放電電漿，以進 行電漿CVD的第2步驟之第2成膜方法。 另外，本發明係提供一種一邊連續搬送長尺狀基材， 同時藉由電漿CVD法在前述基材上連續成膜的成膜方法 ，其特徵爲：沿著前述基材之搬送方向進行電漿放電，使 放電電漿在空間內之強度不同，且使搬送經平坦保持的前 述基材與前述放電電漿之強度所變化的空間重疊之步驟的 第3成膜方法。 〔發明效果〕 藉由本發明，可提供具有充分的阻氣性，且可製造即 使使薄膜被彎曲時，仍可充分抑制阻氣性降低情形的阻氣 性積層薄膜之成膜裝置及成膜方法。 【實施方式】 〔爲實施發明之形態〕 [第1實施形態] 於下述中，參照第1圖〜第5圖，說明有關本發明第 1實施形態之成膜裝置。而且，下述之全部圖面中，爲容 易觀察圖面時，適當地改變各構成要素之尺寸或比例等。 於下述之說明中，使用本實施形態之成膜裝置1 000， -10- 201229303 在基材上形成具有阻氣性之薄膜，以製造阻氣性積層薄膜 ，首先，說明有關目的之阻氣性積層薄膜，且說明有關爲 製造阻氣性積層薄膜時使用的本實施形態之成膜裝置。 <阻氣性積層薄膜> 第1圖係表示以本實施形態之成膜裝置製造的阻氣性 積層薄膜1之典型圖。本實施形態之阻氣性積層薄膜1， 係在基材2之表面上形成具有阻氣性的薄膜3者，全體形 成具有阻氣性之薄膜。 (基材） 以本實施形態之成膜裝置所製造的阻氣性積層薄膜1 ，藉由在基材2之一面上形成薄膜3而製得。 本實施形態中所使用的基材2，例如由樹脂或含有樹 脂之複合材料所形成的薄膜。該薄膜可具有透光性，亦可 爲不透明。 該基材2所使用的樹脂，例如聚對苯二甲酸乙二酯（ PET )、聚萘二甲酸乙二酯（PEN )等之聚酯系樹脂；聚 乙烯（PE)、聚丙烯（PP)、環狀聚烯烴等之聚烯烴系樹 脂、聚醯胺系樹脂、聚碳酸酯系樹脂、聚苯乙烯系樹脂、 聚乙烯醇系樹脂、乙烯-醋酸乙烯酯共聚物之皂化物、聚 丙烯腈系樹脂、縮醛系樹脂、聚醯亞胺系樹脂、芳族聚醯 胺系樹脂、或組合2種以上構成此等樹脂之聚合物之重復 單位的共聚物等。而且，含有樹脂之複合材料，例如聚二 -11 - 201229303 甲基矽氧烷、聚倍半矽氧烷等之聚矽氧樹脂、玻璃複合基 板、玻璃環氧基板等。於此等之樹脂中，就耐熱性及線膨 脹率高而言，以聚酯系樹脂、聚烯烴系樹脂、玻璃複合基 板、玻璃環氧基板較佳。而且，此等之樹脂可單獨1種或 組合2種以上使用。 基材2就與形成的薄膜之密接性而言，亦可實施爲使 其表面活性化的表面活性處理。該表面活性處理，例如電 暈處理 '電漿處理、火焰處理。 (薄膜） 藉由本實施形態之成膜裝置所製造的薄膜3，.係賦予 基材2具有阻氣性的層，在基材2之至少一面上形成。薄 膜3係含有不同組成之複數層。圖中，薄膜3係表示與第 1層3a與第2層3b交互積層的3層構造。 第 1 層 3a 係具有於 SiOxCy ( 0<x<2，0<y<2，x + y 与 2 )時，y#〇所示之接近Si 02之組成。對此而言，第2層 3b 係具有於 SiOxCy ( 0<x<2 > 0<y<2，x + y = 2 )時 ’ y 关〇 ’ 以Si02-yCy表示之組成。第2層3b不爲均勻的組成，於 表示自膜厚方向上該層表面之距離、與相對於矽原子、氧 原子及碳原子之合計量而言碳原子量的比例（碳之原子比 )的關係之碳分布曲線中，滿足全部下述條件（i )及（ii )° 首先，（i )第2層3b係碳分布曲線具有至少1個之 極値。The gas of Si is a raw material gas. The "reaction gas" is reacted with a material gas, and a gas added to the formed film, for example, when forming an SiOx film, corresponds to oxygen (?2). Further, 'in this specification', the performance of the film used "excluding 201229303 carbon" means that the film is formed from the film thickness direction of the film by performing XPS depth profile measurement. The carbon content in the relationship between the distance between the surface of the film and the ratio of the atomic weight of carbon atoms (the atomic ratio of carbon) to the total amount of atoms constituting the film is 1 at%. Here, regarding the carbon distribution curve, "the total amount of atoms constituting the film" means the total number of atoms constituting the film, and the "amount of carbon atoms" means the number of carbon atoms. In addition, the unit "at%" is an abbreviation of "atomic%". In the above-described first reaction condition, the control unit includes the above-mentioned equivalent amount of the reaction time when the organometallic compound and the reaction gas generate the carbon-free compound in the film formation gas. In the second reaction condition, the reaction gas contains a reaction gas that does not reach an equivalent amount in the reaction for generating the carbon-free compound, and the gas supply device is controlled to be configured as should. In the above aspect of the invention, the gas supply device is configured to continuously change the amount of the reaction gas contained in the film forming gas when the first reaction condition and the two reaction conditions are switched. In the present invention, the control unit applies an alternating current power of the plasma in which the strength of the carbon-free compound is generated to the first reaction condition, and secondly, the application occurs in the second reaction condition. The AC power of the plasma of the strength of the carbon-containing compound is preferably configured to control the power source for generating the plasma. In the present invention, the control unit is configured to continuously change the amount of electric power of the alternating current power when switching the first reaction condition and the second reaction condition to the plasma generating power source. It is suitable. Moreover, the present invention provides a film forming apparatus which continuously transports a long-sized base material and continuously forms a film on the base material, and has a vacuum chamber in which the substrate is housed inside. The conveying means for continuously conveying the substrate in the vacuum chamber, the plasma generating means for generating the discharge plasma in a space partially overlapping the transferred substrate, and the conveying direction of the substrate along the space a magnetic field generating means for causing different plasma strengths in the space where the magnetic field is generated; and the second film forming means configured to hold the substrate while the substrate is flat and to transport the substrate in the space It is "the second embodiment"). Furthermore, the present invention provides a film forming method for forming a thin film on a substrate, characterized in that the organometallic compound having a raw material of the thin film and a reaction gas reacted with the organic metal compound generate a metal containing the organometallic compound. In the reaction of an element or a semimetal element and a compound containing no carbon, the first step of plasma CVD is carried out using a gas having an equivalent amount or more of the above reaction; and the reaction for producing the aforementioned compound containing no carbon is used. The first film forming method of the second step of plasma CVD in which the carbon of the organometallic compound and the carbon-containing compound containing a metal element or a semimetal element are generated is formed as the reaction gas. Furthermore, the present invention provides a film forming method for forming a thin film on a substrate, characterized in that the organic metal compound which generates a raw material of the thin film and a reaction gas which reacts with the organic metal compound are generated to form the organic metal of 201229303. a discharge plasma containing a metal element or a semimetal element and having no strength of a carbon compound to perform a first step of plasma CVD; and a carbon-containing metal element or a semi-metal element which generates the aforementioned organometallic compound The discharge plasma of the strength of the carbon-containing compound is subjected to the second film formation method of the second step of the plasma CVD. Further, the present invention provides a film forming method for continuously forming a long-sized base material while continuously forming a film on the substrate by a plasma CVD method, which is characterized in that electricity is carried along the transport direction of the substrate. The slurry discharge is a third film forming method in which the strength of the discharge plasma is different in the space, and the step of transporting the substrate held by the flatness and the space in which the strength of the discharge plasma changes is changed. [Effect of the Invention] According to the present invention, it is possible to provide a film forming apparatus and a film forming method for a gas barrier layered film which can sufficiently suppress a decrease in gas barrier properties even when a film is bent even when the film is bent. . [Embodiment] [Form of the Invention] [First Embodiment] A film forming apparatus according to a first embodiment of the present invention will be described below with reference to Figs. 1 to 5 . Further, in all of the following drawings, when the drawing surface is easily observed, the size, ratio, and the like of each constituent element are appropriately changed. In the following description, a film having a gas barrier property is formed on a substrate by using the film forming apparatus 1 000, -10- 201229303 of the present embodiment to produce a gas barrier laminated film. First, the gas barrier for the purpose is explained. The film-forming apparatus of this embodiment used for producing a gas barrier laminated film is described. <Gas barrier laminated film> Fig. 1 is a view showing a typical example of the gas barrier laminated film 1 produced by the film forming apparatus of the present embodiment. In the gas barrier laminate film 1 of the present embodiment, a gas barrier film 3 is formed on the surface of the substrate 2, and a film having gas barrier properties is formed as a whole. (Substrate) The gas barrier laminated film 1 produced by the film forming apparatus of the present embodiment is obtained by forming the film 3 on one surface of the substrate 2. The substrate 2 used in the present embodiment is, for example, a film formed of a resin or a composite material containing a resin. The film may be light transmissive or opaque. The resin used for the substrate 2 is, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); polyethylene (PE) or polypropylene (PP). A polyolefin resin such as a cyclic polyolefin, a polyamide resin, a polycarbonate resin, a polystyrene resin, a polyvinyl alcohol resin, a saponified product of an ethylene-vinyl acetate copolymer, or a polyacrylonitrile. A resin, an acetal resin, a polyamidene resin, an aromatic polyamine resin, or a copolymer of two or more types of repeating units constituting the polymer of the resins. Further, the resin-containing composite material is, for example, a polyfluorene resin such as polydiphenyl-11-201229303 methyloxirane or polysesquioxane, a glass composite substrate, a glass epoxy substrate or the like. Among these resins, polyester resins, polyolefin resins, glass composite substrates, and glass epoxy substrates are preferred in terms of high heat resistance and high linear expansion ratio. Further, these resins may be used alone or in combination of two or more. The substrate 2 may be subjected to a surface active treatment for activating the surface of the formed film. This surface treatment treatment, such as corona treatment, "plasma treatment, flame treatment. (Film) The film 3 produced by the film forming apparatus of the present embodiment is provided with a gas barrier layer on the substrate 2, and is formed on at least one surface of the substrate 2. The film 3 series contains a plurality of layers of different compositions. In the figure, the film 3 is a three-layer structure in which the first layer 3a and the second layer 3b are alternately laminated. The first layer 3a has a composition close to Si 02 as shown by y#〇 when SiOxCy (0&0<x<2,0<y<2>2, x + y and 2). In this regard, the second layer 3b has a composition represented by SiO 2 -yCy when SiO x Cy ( 0 < x < 2 > 0 < y < 2, x + y = 2 ). The second layer 3b is not a uniform composition, and represents a ratio of the distance from the surface of the layer in the film thickness direction to the ratio of the amount of carbon atoms (atomic ratio of carbon) to the total amount of germanium atoms, oxygen atoms, and carbon atoms. In the carbon distribution curve of the relationship, all of the following conditions (i) and (ii) are satisfied. First, (i) the second layer 3b-based carbon distribution curve has at least one pole.
S -12- 201229303 於本說明書中，碳分布曲線等、薄膜之元素分布曲線 的極大値，係指變化自薄膜3之表面的距離時，元素之原 子比値由增加變爲減少時之點且較該點之元素的原子比値 ，自該點朝薄膜3之膜厚方向上薄膜3之表面的距離再變 化20nm之位置的元素之原子比値減少1 at%之點。另外， 於本說明書中，上述元素分布曲線之極小値，係指變化自 薄膜3之表面的距離時，元素之原子比値由減少變爲增加 時之點，且自該點朝薄膜3之膜厚方向之薄膜3的表面之 距離再變化20nm之位置的元素之原子比値較自該點之元 素的原子比値增加1 at %以上時之點。 此外，（ii )第2層3b係第2層3b內之碳的原子比 之最大値與最小値的差爲5%以上（即（碳之原子比的最大 値）-(碳之原子比的最小値）25%)。 於該第2層3b中，碳之原子比之最大値及最小値的 差之絕對値以6at%以上較佳，以7at%以上更佳。前述絕 對値未達5at%時，使所得的阻氣性積層薄膜1被彎曲時 ，薄膜3容易破損，同時使阻氣性積層薄膜1被彎曲時之 阻氣性變得不充分。 此處，碳分布曲線係藉由倂用X光線光電子分光法（ XPS: Xray Photoelectron Spectroscopy)之測定與氬氣等 之稀有氣體離子濺鍍，以使試料內部露出且順序進行表面 組成分析，換言之，藉由XP S縱深分析測定而作成。藉由 該XP S縱深分析測定所得的分布曲線，例如可以碳之原子 比（單位：at% )爲縱軸，以蝕刻時間（濺鍍時間）爲橫 -13- 201229303 軸而作成。而且，於該以蝕刻時間爲橫軸之元素的分布曲 線中，由於蝕刻時間與膜厚方向之薄膜3的膜厚方向、自 薄膜3之表面的距離有關，可採用自測定XPS縱深分析測 定時所採用的蝕刻速度與蝕刻時間的關係求得的自薄膜3 之表面的距離作爲「自薄膜3之膜厚方向上薄膜3之表面 的距離」。另外，該XPS縱深分析測定時所採用的濺鍍法 ，以採用使用氬氣（ΑΓ+)作爲蝕刻離子種之稀有氣體離 子濺鍍法，且使其蝕刻速度爲〇.〇5nm/sec(Si02熱氧化膜 換算値）較佳。 第2圖係表示第2層3b之碳分布曲線之典型圖。於 表示自層表面的距離之橫軸中，沒有具體的距離，使用第 1層3a、第2層3b、薄膜3之各符號表苹_。圖中所示之組 成的第2層3b，具有1個極大値，碳原子之最大値與最小 値的差超過5 %。 而且，第1層3a係於碳分布曲線中，碳含量爲lat% 以下，形成不含碳之層。 此外，於本實施形態中，就全體形成均勻且具有優異 的阻氣性之薄膜3而言，以薄膜3於膜面方向（平行於薄 膜3之表面的方向）實質上一樣較佳。於本說明書中，薄 膜3於膜面方向中實質上一樣，係指有關藉由XPS縱深分 析測定之薄膜3的膜面之任意2個測定處，作成碳分布曲 線時，具有於其任意的2個測定處所得的碳分布曲線之極 値數相同，各碳分布曲線中碳之原子比的最大値及最小値 之差的絕對値，可互相相同或具有5 at%以內之差。 -14- 201229303 此外，於本實施形態中，前述碳分布曲線以實質上連 續較佳。於本說明書中，碳分布曲線實質上連續係指不含 碳分布曲線中碳之原子比沒有連續變化的部分，具體而言 ，由蝕刻速度與蝕刻時間所求得的薄膜3中至少1層自膜 厚方向之該層表面的距離（X、單位：nm)、與碳之原子 比（C、單位：at% )之關係中，以滿足下述數式（F1 ): 所示之條件較佳。 | dC/d X | g 1 ...(FI) 另外，薄膜3之厚度以5nm〜3000nm之範圍較佳， 以10nm〜2000nm之範圍更佳，以lOOnm〜2000nm之範圍 最佳。薄膜3之厚度未達前述下限値時，會有阻氧氣性、 阻水蒸氣性等之阻氣性不佳的傾向，另外，超過前述上限 値時，由於因彎曲而使薄膜3容易破損，於被彎曲時會有 阻氣性容易降低的傾向》 以本實施形態之成膜裝置1 000製造的阻氣性積層薄 膜1，由於不含碳原子之第1層3a不僅具有高阻氣性，同 時含碳原子之第2層3b較第1層3a更爲柔軟、可彎曲， 故展現耐彎曲性。因此，阻氣性積層薄膜1，全體可發揮 優異的阻氣性及耐彎曲性》 <成膜裝置> 第3圖係表示本實施形態之成膜裝置1 000之典型圖 。本實施形態之成膜裝置1〇〇〇，係具備真空室11、配置 於真空室11內之載負基材2之載置台12、在載置台12之 -15- 201229303 上方且與載置台12對向配置的一對電極13、連接於電極 13之電漿產生用電源14、與於電極13中在沒有與載置台 1 2對向之側所配置的磁場產生部1 5。 而且，在真空室11內設置爲供應各種成膜氣體之氣 體供應管16、與在氣體供應管16上經由配管16a所連接 的氣體供應裝置17。另外，在真空室Π中適當設置設於 真空室11之天井的真空幫浦18、與排氣口（圖中省略） 〇 然後，在電漿產生用電源14及氣體供應裝置17中， 連接控制驅動電漿產生用電源14及氣體供應裝置17的控 制部100 。 其次，於該裝置中藉由電漿產生用電源14，可在電極 1 3與載置台1 2間之空間中產生自氣體供應管1 6所供應的 成膜氣體之電漿，使用產生的電漿進行電漿CVD成膜。 於下述中，順序說明有關各構成。 載置台12係載置基材2者，惟亦可具備在內部使基 材2加熱時之加熱手段。 一對電極13係具有板狀的形狀，且以一面與載置台 12對向的方式配置於真空室11內之高度方向的一定位置 。自連接於電極13之電漿產生用電源14之一對電極13 上，例如藉由施加高周波電力，在此等電極13之間及周 邊的空間產生電場，產生自氣體供應管16所供應的成膜 氣體之電漿》 磁場產生部15,係具有使載置台12側之極性交互反S -12- 201229303 In the present specification, the maximum 値 of the elemental distribution curve of the film, such as the carbon distribution curve, refers to the point at which the atomic ratio 元素 of the element changes from decreasing to decreasing when the distance from the surface of the film 3 is changed. The atomic ratio 元素 of the element at this point is reduced by 1 at% from the point where the distance from the surface of the film 3 in the film thickness direction of the film 3 is further changed by 20 nm. In addition, in the present specification, the minimum distribution of the elemental distribution curve refers to the point at which the atomic ratio 元素 of the element changes from decreasing to increasing when the distance from the surface of the film 3 is changed, and the film from the point toward the film 3 The distance between the surface of the film 3 in the thick direction and the atomic ratio 元素 of the element at the position of 20 nm is increased by 1 at% or more from the atomic ratio 元素 of the element at the point. Further, (ii) the difference between the maximum 値 and the minimum 原子 of the atomic ratio of carbon in the second layer 3b of the second layer 3b is 5% or more (that is, (the maximum 値 of the atomic ratio of carbon) - (atomic ratio of carbon) Minimum 値) 25%). In the second layer 3b, the absolute enthalpy of the difference between the maximum enthalpy and the minimum enthalpy of carbon is preferably 6 at% or more, more preferably 7 at% or more. When the above-mentioned gas barrier laminate film 1 is bent, the film 3 is easily broken, and the gas barrier properties when the gas barrier laminate film 1 is bent are insufficient. Here, the carbon distribution curve is measured by X-ray photoelectron spectroscopy (XS Photo X-ray Photoelectron Spectroscopy) and rare gas ion sputtering such as argon gas to expose the inside of the sample and sequentially perform surface composition analysis, in other words, It was prepared by XP S depth analysis and measurement. The distribution curve obtained by the XP S depth analysis can be prepared, for example, by taking the atomic ratio of carbon (unit: at%) as the vertical axis and the etching time (sputtering time) as the horizontal -13 - 201229303 axis. Further, in the distribution curve of the element having the etching time as the horizontal axis, since the etching time is related to the film thickness direction of the film 3 in the film thickness direction and the distance from the surface of the film 3, it can be measured by the self-measurement XPS depth analysis. The distance from the surface of the film 3 obtained by the relationship between the etching rate and the etching time used is "the distance from the surface of the film 3 in the film thickness direction of the film 3". In addition, the sputtering method used in the XPS depth analysis measurement uses a rare gas ion sputtering method using argon gas (ΑΓ+) as an etching ion species, and the etching rate is 〇. 5 nm/sec (SiO 2 ). Thermal oxide film conversion 値) is preferred. Fig. 2 is a typical view showing the carbon distribution curve of the second layer 3b. In the horizontal axis indicating the distance from the surface of the layer, there is no specific distance, and the symbol _ of the first layer 3a, the second layer 3b, and the film 3 is used. The second layer 3b of the composition shown in the figure has one maximum enthalpy, and the difference between the maximum enthalpy of carbon atoms and the minimum enthalpy is more than 5%. Further, the first layer 3a is formed in a carbon distribution curve and has a carbon content of lat% or less to form a layer containing no carbon. Further, in the present embodiment, the film 3 which is uniform in overall formation and has excellent gas barrier properties is substantially the same in the film surface direction (direction parallel to the surface of the film 3). In the present specification, the film 3 is substantially the same in the film surface direction, and refers to any two measurement portions of the film surface of the film 3 measured by XPS depth analysis, and has a carbon distribution curve. The carbon distribution curve obtained at the measurement site has the same number of turns, and the absolute enthalpy of the difference between the maximum enthalpy and the minimum enthalpy of the atomic ratio of carbon in each carbon distribution curve may be identical to each other or have a difference within 5 at%. Further, in the present embodiment, the carbon distribution curve is preferably continuously continuous. In the present specification, the carbon distribution curve substantially continuously means a portion which does not have a continuous change in the atomic ratio of carbon in the carbon distribution curve, specifically, at least one layer of the film 3 obtained by the etching rate and the etching time. In the relationship between the distance (X, unit: nm) of the surface of the layer in the film thickness direction and the atomic ratio with carbon (C, unit: at%), it is preferable to satisfy the following formula (F1): . dC/d X | g 1 (FI) Further, the thickness of the film 3 is preferably in the range of 5 nm to 3000 nm, more preferably in the range of 10 nm to 2000 nm, and most preferably in the range of 100 nm to 2000 nm. When the thickness of the film 3 is less than the lower limit 値, the gas barrier properties such as oxygen barrier properties and water vapor barrier properties tend to be poor, and when the thickness exceeds the upper limit 値, the film 3 is easily broken due to bending. In the gas barrier layered film 1 manufactured by the film forming apparatus 1 000 of the present embodiment, the first layer 3a containing no carbon atoms not only has high gas barrier properties, but also has a high gas barrier property. The second layer 3b containing carbon atoms is softer and more bendable than the first layer 3a, and thus exhibits bending resistance. Therefore, the gas barrier laminate film 1 exhibits excellent gas barrier properties and bending resistance as a whole. <Film forming apparatus> Fig. 3 is a typical view of the film forming apparatus 1 000 of the present embodiment. The film forming apparatus 1 of the present embodiment includes a vacuum chamber 11 and a mounting table 12 on which the negative substrate 2 is placed in the vacuum chamber 11, above the -15-201229303 of the mounting table 12, and the mounting table 12 The pair of electrodes 13 disposed in the opposing direction, the plasma generating power source 14 connected to the electrode 13, and the magnetic field generating portion 15 disposed on the side of the electrode 13 that is not opposed to the mounting table 12 are disposed. Further, a gas supply pipe 16 for supplying various film forming gases and a gas supply device 17 connected to the gas supply pipe 16 via a pipe 16a are provided in the vacuum chamber 11. Further, in the vacuum chamber 适当, the vacuum pump 18 provided in the patio of the vacuum chamber 11 and the exhaust port (omitted from the drawing) are appropriately disposed, and then, in the plasma generating power source 14 and the gas supply device 17, the connection control is performed. The plasma generating power source 14 and the control unit 100 of the gas supply device 17 are driven. Next, in the apparatus, by the plasma generating power source 14, the plasma of the film forming gas supplied from the gas supply pipe 16 can be generated in the space between the electrode 13 and the mounting table 12, and the generated electricity can be used. The slurry was subjected to plasma CVD to form a film. In the following, the respective configurations will be described in order. The mounting table 12 is a substrate on which the substrate 2 is placed, but may be provided with a heating means for heating the substrate 2 inside. The pair of electrodes 13 have a plate shape and are disposed at a constant position in the height direction of the vacuum chamber 11 so as to face the mounting table 12 on one side. From one of the counter electrode 13 of the plasma generating power source 14 connected to the electrode 13, for example, by applying high-frequency power, an electric field is generated between the electrodes 13 and the space around the electrode 13, and the supply from the gas supply pipe 16 is generated. Plasma of Membrane Gas The magnetic field generating unit 15 has a polarity opposite to the side of the mounting table 12
S -16- 201229303 轉所配列的複數個磁石15a，與使複數個（圖中有3個） 之磁石15a磁黏的連接構件15b。藉由磁場產生部15，在 載置台12與電極13間之空間形成磁場。圖係表示藉由磁 場產生部1 5所形成的磁力線LM之典型例。 藉由對電極13施加而產生的放電電漿之強度，由於 視磁場產生部15所形成磁場之強度而不同，形成電漿強 的區域之強電漿區域AR1，與電漿弱的區域之弱電漿區域 AR2。磁場之強度，可藉由改變磁場產生部15之磁石15a 之數、或磁石15 a間之間隔（圖中以符號L表示）、磁石 15a之高度（圖中以符號Η表示），形成企求的磁場。 例如，於圖中所示之3個磁石1 5 a中，兩端之磁石 15a較中央者更低，可使用遠離電極13的磁場產生部15 而且，直至到達經產生的電漿到達基材2爲止，爲使 電漿擴散時，使電漿強度平均化，使用在基材2上大約均 勻強度的電漿予以成膜。 氣體供應管16,係具有於一對電極13之下方，以橫 斷真空室U之方式延伸之管狀形狀自複數個所設置的開 口部供應電漿CVD之原料氣體等之成膜氣體。 氣體供應裝置17係具有儲藏成膜氣體（原料氣體、 反應氣體、載體氣體）之桶，或控制構成成膜氣體之各氣 體供應量的閥等，且在真空室Π內供應適當量的成膜氣 aatl 體。 原料氣體爲有機金屬化合物，可視形成的阻障膜之材 -17- 201229303 質而定予以適當選擇使用》 原料氣體例如可使用含有矽之有機矽 該有機矽化合物例如六甲基二矽氧: 1，1,3,3-四甲基二矽氧烷、乙烯基三甲基 烷、六甲基二矽烷、甲基矽烷、二甲基砂 、二乙基矽烷、丙基矽烷、苯基矽烷、乙 烷、乙烯基三甲氧基矽烷、四甲氧基矽院 、苯基三甲氧基矽烷、甲基三乙氧基矽烷 氧烷、二甲基二矽胺烷、三甲基二矽胺烷 烷、五甲基二矽胺烷、六甲基二矽胺烷。 化合物中，就化合物之取得性或所得的阻 而言，以HMDSO、1，1,3,3-四甲基二矽氧 此等之有機矽化合物，可單獨1種或2種 另外，除上述有機矽化合物外，亦可使用 料氣體作爲形成阻障膜的矽源》 除原料氣體外，使用反應氣體作爲成 氣體可適當選擇使用與原料氣體反應，產 含的金屬元素或半金屬元素與氧化物、氮 的化合物之氣體。爲形成氧化物時之反應 用氧氣、臭氧。而且，爲形成氮化物時之 可使用氮氣、銨。此等之反應氣體，可單 上組合使用，例如形成氧氮化物時，可組 之反應氣體與形成氮化物時之反應氣體使 爲將反應氣體供應給真空室時，視其 化合物。 院（HMDSO)、 矽烷、四甲基矽 烷、三甲基矽烷 烯基三乙氧基矽 、四乙氧基矽烷 、八甲基環四矽 、四甲基二矽胺 於此等之有機矽 障膜之阻氣性等 烷較佳。而且， 以上組合使用。 含有單矽烷之原 膜氣體。該反應 生原料氣體中所 化物等之不含碳 氣體，例如可使 反應氣體，例如 獨1種或2種以 合形成氧化物時 用。 所需亦可使用載 -18-S -16 - 201229303 The plurality of magnets 15a arranged in the rotation and the connecting member 15b which magnetically adheres a plurality of (three in the figure) magnets 15a. The magnetic field generating unit 15 forms a magnetic field in the space between the mounting table 12 and the electrode 13. The figure shows a typical example of the magnetic lines of force LM formed by the magnetic field generating portion 15. The intensity of the discharge plasma generated by the application of the counter electrode 13 differs depending on the strength of the magnetic field formed by the magnetic field generating portion 15, forming a strong plasma region AR1 in a region where the plasma is strong, and a weak plasma in a region where the plasma is weak. Area AR2. The strength of the magnetic field can be changed by changing the number of magnets 15a of the magnetic field generating portion 15 or the interval between the magnets 15a (indicated by the symbol L in the figure) and the height of the magnet 15a (indicated by the symbol Η in the figure). magnetic field. For example, in the three magnets 15 a shown in the figure, the magnets 15a at both ends are lower than the center, and the magnetic field generating portion 15 far from the electrode 13 can be used and until the generated plasma reaches the substrate 2 Heretofore, in order to diffuse the plasma, the plasma strength is averaged, and a plasma having a uniform strength on the substrate 2 is used for film formation. The gas supply pipe 16 is provided with a film forming gas such as a raw material gas of plasma CVD from a plurality of provided opening portions in a tubular shape extending downward from the pair of electrodes 13 so as to traverse the vacuum chamber U. The gas supply device 17 has a barrel for storing a film forming gas (a material gas, a reaction gas, a carrier gas), a valve for controlling the supply amount of each gas constituting the film forming gas, and the like, and supplies an appropriate amount of film forming in the vacuum chamber. Gas aatl body. The material gas is an organometallic compound, which can be appropriately selected depending on the material of the barrier film to be formed. -17- 201229303. For the material gas, for example, an organic cerium compound containing cerium, such as hexamethyldioxane, can be used: , 1,3,3-tetramethyldioxane, vinyltrimethylalkane, hexamethyldioxane, methyl decane, dimethyl sand, diethyl decane, propyl decane, phenyl decane, Ethane, vinyltrimethoxydecane, tetramethoxy fluorene, phenyltrimethoxydecane, methyltriethoxystanaloxane, dimethyldioxane, trimethyldiaminedane , pentamethyldiamine, hexamethyldioxane. In the compound, the organic ruthenium compound such as HMDSO or 1,1,3,3-tetramethyldioxane may be used alone or in combination with respect to the availability of the compound or the obtained resistance, in addition to the above. In addition to the organic ruthenium compound, a gas can be used as a source of the barrier film. In addition to the source gas, the reaction gas can be used as a gas to selectively react with the source gas to produce a metal element or a semimetal element and oxidize. a gas of a compound of nitrogen or nitrogen. The reaction for the formation of oxides uses oxygen and ozone. Further, nitrogen or ammonium may be used for the formation of a nitride. These reaction gases may be used in combination, for example, when an oxynitride is formed, the reaction gas which can be formed and the reaction gas when the nitride is formed are regarded as a compound when the reaction gas is supplied to the vacuum chamber. Institute (HMDSO), decane, tetramethyl decane, trimethyl nonalkenyl triethoxy fluorene, tetraethoxy decane, octamethylcyclotetradecyl, tetramethyl dimethylamine, etc. An alkane such as a gas barrier property of the film is preferred. Moreover, the above combinations are used. An original membrane gas containing monodecane. The carbon-free gas such as the compound in the raw material gas can be used, for example, when the reaction gas is used alone or in combination to form an oxide. Can also be used if required -18-
S 201229303 體氣體作爲部分成膜氣體。另外，爲 其所需亦可使用放電用氣體作爲部分 體及放電用氣體，可使用適當使用習 氣、氬氣、氖氣、氙氣等之稀有氣體 真空幫浦1 8係爲控制真空室1 1 時使用。真空室11內之壓力，可視 定予以適當調整，惟載置基材2附 5 0Pa較佳。視抑制氣相反應爲目的而 爲低壓電漿CVD法時，通常爲Ο.ΙΡϊ 產生裝置之電極桶的電力，可視原料 內之壓力等而定予以適當調整，以〇. 控制部1 〇〇係輸出控制使電漿產 供應裝置1 7驅動時之控制信號。 第4圖係說明控制部100之典型 部100包含輸入部101、連接輸入部 連接計算部102之信號輸出部103及 輸出部101係將電漿產生用電源 I7之運轉條件輸入計算部102之輸入 源1 4或氣體供應裝置1 7之運轉條件 成的薄膜之厚度、使用的基板X之種 等而改變，故適當指定運轉條件。 計算部102係使用自輸入部101 作成電漿產生用電源14及氣體供應| 且供應給信號輸出部103。 產生電漿放電時，視 成膜氣體。該載體氣 知者，例如可使用氨 ;氫氣。 內之壓力（真空度） 原料氣體之種類等而 近之壓力以 O.lPa〜 定，以電漿CVD作 i〜10Pa。而且，電獎 氣體之種類或真空室 1〜1 OkW較佳。 生用電源14及氣體 圖。如圖所示，控制 1 0 1之計算部1 0 2、 記憶部104。 1 4或氣體供應裝置 裝置。電漿產生用電 ，由於視基板X上形 類、成膜氣體之組成 所輸入的運轉條件， :置17之控制信號， -19- 201229303 信號輸出部1 03係將以計算部1 02所作成的控制信號 各輸出給電漿產生用電源14及氣體供應裝置17之控制信 號的中介面（interface )。 此外’亦可自輸入部101輸入電漿產生用電源14及 氣體供應裝置17之運轉條件，有關詳細的運轉條件，亦 可預先以査表（lookup table)等之形式記憶於記憶部1〇4 中’輸入被記億的運轉條件與相關的指定資訊。例如亦可 以輸入「條件1」時，引用對應於記憶部1 04中記憶的條 件1之運轉條件’輸入「條件2」時，引用對應於記憶部 104中記憶的條件2之運轉條件的方式，輸入代用的資訊 。藉此，可簡化運轉條件之輸入作業。 (成膜步驟） 其次，使用該成膜裝置，說明有關製造第1圖所示之 阻氣性積層薄膜1時之反應步驟。此處，說明使用 HMDSO與氧氣之混合氣體作爲成膜氣體。 第1係表示控制氣體供應裝置1 7以製造阻氣性積層 薄膜1。此時，於電漿產生用電源14中，可以一定的電力 量使成膜氣體完全變成電漿之程度的電力供應給電極13 之方式，自控制部1 00輸出控制信號。另外，於氣體供應 裝置17中，製造第1層3a與第2層3b時，以改變 HMDSO與氧氣之混合比例的方式，輸出控制的控制信號 。改變成膜氣體之混合比例時，例如藉由控制控制各氣體 之供應量之閥的開度予以進行。S 201229303 Body gas as part of the film forming gas. In addition, it is also possible to use a gas for discharge as a partial body and a gas for discharge, and it is possible to use a rare gas vacuum pump 18 using a conventional gas, argon gas, helium gas, helium gas or the like as the control vacuum chamber 1 1 use. The pressure in the vacuum chamber 11 can be appropriately adjusted as appropriate, but it is preferable to mount the substrate 2 with 50 Pa. When the low-pressure plasma CVD method is used for the purpose of suppressing the gas phase reaction, the electric power of the electrode barrel of the apparatus is usually adjusted according to the pressure in the raw material, etc., so that the control unit 1 〇〇 The output control controls the control signal when the plasma supply device 17 is driven. 4 is a diagram showing that the exemplary unit 100 of the control unit 100 includes the input unit 101, the signal output unit 103 connected to the input unit connection calculation unit 102, and the output unit 101. The operation conditions of the plasma generation power source I7 are input to the calculation unit 102. The source 14 or the thickness of the film formed by the operating conditions of the gas supply device 17 is changed depending on the type of the substrate X to be used, and the operating conditions are appropriately specified. The calculation unit 102 is configured to generate the plasma generation power source 14 and the gas supply source from the input unit 101 and supply the signal to the signal output unit 103. When a plasma discharge is generated, a film forming gas is regarded. The carrier is known, for example, ammonia; hydrogen. The pressure inside (vacuum degree), the type of the raw material gas, etc., the pressure is approximately O.lPa~, and the plasma CVD is i~10Pa. Further, the type of the electric prize gas or the vacuum chamber 1 to 1 OkW is preferable. Raw power supply 14 and gas map. As shown in the figure, the calculation unit 1 0 2 of the 1 0 1 is controlled, and the memory unit 104 is controlled. 1 4 or gas supply device. The electricity generated by the plasma is due to the operating conditions input on the composition of the substrate X and the composition of the film forming gas. The control signal of the 17 is set, and the signal output unit 193-201229303 is made by the calculating unit 102. The control signals are each output to an interface of the control signals of the plasma generating power source 14 and the gas supply device 17. Further, the operating conditions of the plasma generating power source 14 and the gas supply device 17 may be input from the input unit 101, and the detailed operating conditions may be memorized in the memory unit 1〇4 in the form of a lookup table or the like. 'Enter the operating conditions associated with the billion and the specified information. For example, when "condition 1" is input, the operation condition "input "condition 2" corresponding to the condition 1 stored in the memory unit 104 is referred to, and the operation condition corresponding to the condition 2 stored in the memory unit 104 is referred to. Enter the proxy information. Thereby, the input operation of the operating conditions can be simplified. (Film Forming Step) Next, a reaction step in the case of producing the gas barrier layered film 1 shown in Fig. 1 will be described using the film forming apparatus. Here, a mixed gas of HMDSO and oxygen is used as a film forming gas. The first system is shown to control the gas supply device 17 to produce the gas barrier laminate film 1. At this time, in the plasma generating power source 14, a control signal is output from the control unit 100 so that the electric power of the film forming gas to be completely plasma can be supplied to the electrode 13 with a constant amount of electric power. Further, in the gas supply device 17, when the first layer 3a and the second layer 3b are produced, a control signal for control is output so as to change the mixing ratio of HMDSO and oxygen. When the mixing ratio of the film forming gas is changed, it is carried out, for example, by controlling the opening degree of the valve for controlling the supply amount of each gas.
-20- S 201229303 首先，第1層3a之成膜步驟’係以化學論量產生 HMD SO完全被氧化的氧含率之方式’自控制部1〇〇輸出 控制成膜氣體之混合比例的控制信號給供應裝置1 7。例如 以氧氣爲HMDSO之12倍的方式，控制此等氣體之混合比 例，將此等氣體供應給真空室11。使用該混合比例之成膜 氣體時，於電漿CVD之過程中，由於藉由下述式1所示 之反應產生Si 02，可形成第1層3a。 [化1] (CH3) 6S i 2〇+1 202—6C02+9H20+2 S i 〇2 …（1) 其次，第2層3b之成膜步驟，係以化學論量產生 HMDSO沒有完全被氧化氧氣不足下的氧含率的方式，自 控制部1 〇〇輸出控制成膜氣體之混合比例的控制信號給供 應裝置17。具體而言，以氧氣未達HMDSO之12倍的方 式，控制此等氣體之混合比例，將此等氣體供應給真空室 11° 另外，成膜氣體之混合比例，係於第2層3b之成膜 步驟中’使氧含率連續下降後，再連續上昇，直至氧氣變 爲HMDSO之12倍爲止予以變化。當氧氣變爲HMDSO之 12倍時，完成第2層3b之成膜》 使用該混合比例之成膜氣體時，於電漿CVD之過程 中’由於藉由下述式2所示之反應產生含碳化合物之 SiOxCy，可形成第2層3b。式2係表示氧氣爲HMDSO之 9倍時之反應式。 -21 - 201229303 [化2] (CH3) 6S i 20+90广4C02+9H20+2S i OC " (2) 第2係表示控制電漿產生用電源1 4以製造阻氣性積 層薄膜1。此時，於氣體供應裝置17中，輸出產生化學論 量之HMDSO完全被氧化的氧含量以一定的混合比例供應 成膜氣體之控制信號。 另外，電漿產生用電源14係於製造第1層3a與第2 層3b時，以改變電力來產生電漿的方式，自控制部1〇〇 輸出控制信號。 首先，第1層3a之成膜步驟，係以供應產生HMD SO 完全被氧化的電力之方式，自控制部1 〇〇輸出控制信號給 電漿產生用電源14。此時，由於於電漿CVD之過程中， 產生完全氧化，藉由下述式1所示之反應產生Si 02，可形 成第1層3a。 其次，第2層3b之成膜步驟’係以供應產生HMDSO 沒有完全被氧化之電力（例如第1層3a於成膜時之電力 的一半）之方式，自控制部1〇〇輸出控制信號給電漿產生 用電源14。另外，所供應的電力於第2層3b之成膜步驟 中，連續下降後，再連續上昇，直至供應產生HMDSO完 全氧化的電力爲止予以變化◊直至產生HMDSO完全氧化 的電力爲止，增加供應電力時*完成第2層3b之成膜。 此時，於電漿CVD之過程中，例如由於可藉由下述 式2所示之反應產生SiOxCy，形成第2層3b。 此外，亦可控制氣體供應裝置1 7與電漿產生用電源 -22- 201229303 14雨者，以製造阻氣性積層薄膜1。此時，可藉由上述式 1，2所示之反應，形成第1層3a、第2層3b。 如上述之成膜裝置1 000，由於控制部1〇〇爲控制運轉 條件進行成膜，具有充分的阻氣性，且即使薄膜被彎曲時 ，仍可製造可充分控制阻氣性降低情形的阻氣性積層薄膜 1 ° 而且，本實施形態係說明於薄膜3上以合計爲3層的 方式積層第1層3a與第2層3b，惟不受此等所限制。藉 由重複上述之成膜步驟，例如第5圖所示，可製造具有另 外重複積層第1層3a與第2層3b (圖中合計爲5層）的 薄膜3之阻氣性積層薄膜1。 爲該薄膜3時，複數層之第2層3b之組成，可相同 或不相同。而且，具備2層以上之該薄膜3時，可於基材 2之一表面上形成該薄膜3，亦可於基材2之兩表面上形 成。 [第2實施形態] 第6圖係本發明第2實施形態之成膜裝置2000的說 明圖。本實施形態之成膜裝置2000，係具有部分與第1實 施形態之成膜裝置1 〇〇〇共通的構成。而且，於本實施形 態中，與第1實施形態共通的構成要素以相同符號表示， 且省略此等構成要素之詳細說明。 第6圖所示之成膜裝置2000，係可搬送長尺狀基材2 ，同時在搬送過程中連續成膜。於下述中，順序說明。 -23- 201229303 成膜裝置2000，係具有搬送捲取成輥狀之長尺狀基材 2的輥（搬送手段）21、搬送基材2之搬送輥（搬送手段 )22，23、與捲取基材2之捲取輥（搬送手段）24。基材2 係以沒有被彎曲、平坦的狀態搬送載置台12之上方，於 搬送載置台12之上方的過程中，連續進行電漿CVD成膜 〇 電極13係設置於載置台12之下方且面向載置台12, 磁場產生部15係於電極13中設置於沒有與載置台12對 向之側。氣體供應管1 6係以於載置台1 2之上方，橫斷真 空室11之方式延伸、設置。電極13與電漿產生用電源14 ，係構成本發明之電漿產生手段。 該電極13例如藉由施加一定強度之高周波電力，在 電極13之間及周邊之空間產生電場，產生自氣體供應管 16供應的成膜氣體之電漿。成膜氣體例如以氧氣爲 HMDSO之9倍至12倍的方式予以控制。 此時，視藉由磁場產生部15所形成的磁場之強度而 定，產生不同強度的放電電漿，且於載置台12之上方形 成電漿強的區域之強電漿區域AR1，與電漿弱的區域之弱 電漿區域AR2。強電漿區域AR1，由於藉由下述式1所示 之反應產生 Si02，形成第1層3a。另外，弱電漿區域 AR2，由於藉由下述式2所示之反應產生SiOxCy，形成第 2 層 3 b 〇 基材2係以通過該所形成的強電漿區域AR1與弱電漿 區域AR2附近的方式予以搬送。在基板2上以於搬送過程 -24--20- S 201229303 First, the film formation step of the first layer 3a is controlled by chemically increasing the oxygen content of the HMD SO completely oxidized. Controlling the mixing ratio of the film forming gas from the control unit 1〇〇 output The signal is supplied to the supply device 17. For example, in a manner in which oxygen is 12 times that of HMDSO, the mixing ratio of these gases is controlled, and these gases are supplied to the vacuum chamber 11. When the film forming gas of this mixing ratio is used, the first layer 3a can be formed by the generation of Si 02 by the reaction shown in the following formula 1 during the plasma CVD. [Chemical Formula 1] (CH3) 6S i 2〇+1 202—6C02+9H20+2 S i 〇2 (1) Next, the film formation step of the second layer 3b is chemically generated to produce HMDSO which is not completely oxidized. The control unit 1 outputs a control signal for controlling the mixing ratio of the film forming gas to the supply device 17 in such a manner that the oxygen content is insufficient under oxygen. Specifically, the mixing ratio of the gases is controlled so that the oxygen does not reach 12 times of the HMDSO, and the gas is supplied to the vacuum chamber at 11°. Further, the mixing ratio of the film forming gas is formed in the second layer 3b. In the membrane step, 'the oxygen content is continuously decreased, and then continuously rises until the oxygen becomes 12 times of HMDSO. When the oxygen becomes 12 times of the HMDSO, the film formation of the second layer 3b is completed. When the film forming gas of the mixing ratio is used, during the plasma CVD, the content is caused by the reaction shown by the following formula 2 The SiOxCy of the carbon compound forms the second layer 3b. Formula 2 shows a reaction formula when oxygen is 9 times that of HMDSO. -21 - 201229303 [CH2] 6S i 20+90 广 4C02+9H20+2S i OC " (2) The second system indicates that the plasma generating power source 1 is controlled to manufacture the gas barrier laminated film 1. At this time, in the gas supply device 17, a control signal for supplying a film forming gas at a certain mixing ratio is generated by outputting a chemically sized HMDSO completely oxidized oxygen content. Further, the plasma generating power source 14 is configured to output a control signal from the control unit 1A when the first layer 3a and the second layer 3b are manufactured, and the plasma is generated by changing the electric power. First, the film forming step of the first layer 3a is output from the control unit 1 to the plasma generating power source 14 so as to supply electric power for generating the HMD SO to be completely oxidized. At this time, since complete oxidation occurs during the plasma CVD, Si 2 is produced by the reaction shown in the following formula 1, and the first layer 3a can be formed. Next, the film forming step of the second layer 3b is to supply a control signal from the control unit 1 to supply electric power which is not completely oxidized by the HMDSO (for example, half of the electric power of the first layer 3a at the time of film formation). The plasma generating power source 14 is used. In addition, the supplied electric power is continuously decreased in the film forming step of the second layer 3b, and then continuously rises until the electric power for generating complete oxidation of the HMDSO is supplied until the electric power of the HMDSO is completely oxidized, and when the electric power is increased. * Complete the film formation of the second layer 3b. At this time, in the course of plasma CVD, for example, SiOxCy can be produced by the reaction shown in the following formula 2 to form the second layer 3b. Further, it is also possible to control the gas supply device 17 and the plasma generating power source -22-201229303 14 to manufacture the gas barrier laminated film 1. At this time, the first layer 3a and the second layer 3b can be formed by the reaction shown in the above formulas 1 and 2. In the film forming apparatus 1 000 described above, since the control unit 1 is formed to control the operating conditions, it has sufficient gas barrier properties, and even when the film is bent, it is possible to manufacture a resistor capable of sufficiently controlling the gas barrier property. In the present embodiment, the first layer 3a and the second layer 3b are laminated on the film 3 so as to have a total of three layers, but are not limited thereto. By repeating the above-described film forming step, for example, as shown in Fig. 5, the gas barrier layered film 1 having the film 3 of the first layer 3a and the second layer 3b (total of 5 layers in total) which are repeatedly laminated can be produced. In the case of the film 3, the composition of the second layer 3b of the plurality of layers may be the same or different. Further, when two or more layers of the film 3 are provided, the film 3 may be formed on one surface of the substrate 2 or may be formed on both surfaces of the substrate 2. [Second Embodiment] Fig. 6 is an explanatory view showing a film forming apparatus 2000 according to a second embodiment of the present invention. The film forming apparatus 2000 of the present embodiment has a configuration partially in common with the film forming apparatus 1 of the first embodiment. In the present embodiment, constituent elements common to the first embodiment are denoted by the same reference numerals, and detailed description of these constituent elements will be omitted. The film forming apparatus 2000 shown in Fig. 6 is capable of transporting the long-sized base material 2 while continuously forming a film during the conveyance. In the following, the order is explained. -23-201229303 The film forming apparatus 2000 is a roll (transport means) 21 for transporting the long-sized base material 2 wound into a roll shape, and a transfer roller (transport means) 22, 23 for transporting the substrate 2, and winding The winding roller (transport means) 24 of the substrate 2. The substrate 2 is placed above the transfer table 12 in a state where it is not bent and flat, and is continuously subjected to plasma CVD film formation. The electrode 13 is provided below the mounting table 12 and facing the upper side of the transfer stage 12 The stage 12 and the magnetic field generating unit 15 are provided on the side of the electrode 13 that is not opposed to the stage 12 . The gas supply pipe 16 is extended and disposed so as to traverse the vacuum chamber 11 above the mounting table 1 2 . The electrode 13 and the plasma generating power source 14 constitute the plasma generating means of the present invention. The electrode 13 generates an electric field in a space between and around the electrodes 13 by applying a high-frequency power of a certain intensity, for example, and generates a plasma of a film-forming gas supplied from the gas supply pipe 16. The film forming gas is controlled, for example, in such a manner that oxygen is 9 times to 12 times that of HMDSO. At this time, depending on the strength of the magnetic field formed by the magnetic field generating portion 15, the discharge plasma of different strength is generated, and the strong plasma region AR1 in the region where the plasma is strong is formed above the mounting table 12, and the plasma is weak. The weak plasma region AR2 of the region. In the strong plasma region AR1, the first layer 3a is formed by generating SiO 2 by the reaction shown in the following formula 1. Further, in the weak plasma region AR2, SiOxCy is generated by the reaction shown in the following formula 2, and the second layer 3b 〇 base material 2 is formed to pass the strong plasma region AR1 and the vicinity of the weak plasma region AR2. Transfer it. On the substrate 2 for the transfer process -24-
S 201229303 中各電漿區域AR1，AR2所產生的反應爲基準，連續進行 成膜。換言之，如第7圖所示，於搬送基材2之過程中， 通過強電漿區域AR1時形成第1層3a，通過弱電漿區域 AR2時形成第2層3b。然後，爲使強電漿區域AR1與弱 電漿區域AR2交互通過時，伴隨搬送，同時以使第1層 3a與第2層3b予以相互形成、積層，形成阻氣性積層薄 膜1。 圖中係表示有4個強電漿區域AR1，3個弱電漿區域 AR2。因此，使用本實施形態之成膜裝置2 000時，所形成 的阻氣性積層薄膜1，係形成交互合計有7層之第1層3a 與第2層3b之構成者。 如上述之成膜裝置2 000，係一邊搬送長尺狀基材2, 同時通過電漿強度不同的複數個區域，在各電漿區域 AR1，AR2成膜。因此，可容易製造具有充分的阻氣性，且 即使被彎曲時，仍可充分抑制阻氣性降低情形之長尺狀阻 氣性積層薄膜1。 而且，成膜裝置2000於以輥對輥的方式使薄膜3成 膜時，可使長尺狀基材2以平坦的狀態連續形成薄膜3。 以使基材2被彎曲的狀態形成薄膜3時，於所形成的阻氣 性積層薄膜平坦地延伸時，由於薄膜內部具有殘留應力， 容易導致破損。然而，以本實施形態之成膜裝置2 0 0 0所 形成的阻氣性積層薄膜，不需擔心該現象。而且，可容易 地大量製造更局品質的阻氣性積層薄膜。 以上，參照附加圖面且說明有關本發明之適合的實施 -25- 201229303 形態例，惟本發明不受此等所限制。於上述例中所示之各 構成構件的各種形狀或組合等爲一例，在不脫離本發明主 旨之範圍內，可以設計要求等爲基準，作各種變更。 〔產業上之利用價値〕 本發明係提供一種可製造具有充分的阻氣性，且即使 使薄膜被彎曲時，仍可充分抑制阻氣性降低情形之阻氣性 積層薄膜之成膜裝置及成膜方法，在產業上極爲有用。 【圖式簡單說明】 [第1圖]係表示以本發明之一實施形態的成膜裝置所 製造的積層薄膜例之典型圖。 [第2圖]係表示阻氣性積層薄膜之碳分布曲線例之圖 〇 [第3圖]係表示本發明第1實施形態之成膜裝置的典 型圖。 [第4圖]係說明控制部之典型圖。 [第5圖]係表示以本發明一實施形態之成膜裝置所製 造的積層薄膜之變形例的典型圖。 [第6圖]係表示本發明第2實施形態之成膜裝置的典 型圖。 [第7圖]係表示上述第2實施形態之成膜裝置的成膜 形態的典型圖。The reaction generated by each of the plasma regions AR1 and AR2 in S 201229303 is based on the standard, and film formation is continuously performed. In other words, as shown in Fig. 7, in the process of transporting the substrate 2, the first layer 3a is formed when passing through the strong plasma region AR1, and the second layer 3b is formed when passing through the weak plasma region AR2. Then, in order to allow the strong plasma region AR1 and the weak plasma region AR2 to pass through each other, the first layer 3a and the second layer 3b are formed and laminated to each other, and the gas barrier layered film 1 is formed. In the figure, there are four strong plasma regions AR1 and three weak plasma regions AR2. Therefore, when the film forming apparatus 2000 of the present embodiment is used, the gas barrier laminated film 1 formed is formed by a total of seven layers of the first layer 3a and the second layer 3b. In the film forming apparatus 2000 described above, the long-sized base material 2 is conveyed while forming a film in each of the plasma regions AR1 and AR2 by a plurality of regions having different plasma strengths. Therefore, it is possible to easily produce the long-sized gas barrier laminate film 1 which has sufficient gas barrier properties and can sufficiently suppress the gas barrier properties from being lowered even when it is bent. Further, when the film forming apparatus 2000 forms the film 3 by the roll-to-roll method, the long-sized base material 2 can be continuously formed into the film 3 in a flat state. When the film 3 is formed in a state in which the substrate 2 is bent, when the gas barrier laminated film formed is flatly stretched, residual stress is likely to occur inside the film, which is liable to cause breakage. However, the gas barrier layered film formed by the film forming apparatus 2000 of the present embodiment does not need to be worried about this phenomenon. Moreover, it is easy to mass-produce a gas permeable laminated film of a higher quality. The embodiment of the present invention is described above with reference to the additional drawings, and the present invention is not limited thereto. The various shapes, combinations, and the like of the respective constituent members shown in the above examples are merely examples, and various modifications can be made without departing from the scope of the present invention. [Industrial Applicability 値] The present invention provides a film forming apparatus and a film forming apparatus for a gas barrier laminated film which can sufficiently reduce the gas barrier properties even when the film is bent. The membrane method is extremely useful in the industry. [Brief Description of the Drawings] [Fig. 1] is a typical view showing an example of a laminated film produced by a film forming apparatus according to an embodiment of the present invention. [Fig. 2] Fig. 3 is a view showing an example of a carbon distribution curve of a gas barrier layered film. Fig. 3 is a view showing a film forming apparatus according to a first embodiment of the present invention. [Fig. 4] is a typical diagram illustrating a control unit. [Fig. 5] Fig. 5 is a typical view showing a modification of the laminated film produced by the film forming apparatus according to the embodiment of the present invention. [Fig. 6] Fig. 6 is a view showing a typical example of a film forming apparatus according to a second embodiment of the present invention. [Fig. 7] Fig. 7 is a typical view showing a film formation form of the film formation apparatus of the second embodiment.
-26- S 201229303 【主要元件符號說明】 2 :基材 3 :薄膜 11 :真空室 1 3 :電極 14:電漿產生用電源 1 5 :磁場產生部（磁場產生手段） 1 7 :氣體供應裝置 21:送出輥（搬送手段） 22、23:搬送輥（搬送手段） 24 :捲取輥（搬送手段） 1 〇 〇 :控制部 1 000、2000 :成膜裝置 -27--26- S 201229303 [Description of main component symbols] 2: Substrate 3: Film 11: Vacuum chamber 1 3: Electrode 14: Power source for plasma generation 1 5: Magnetic field generating unit (Magnetic field generating means) 1 7 : Gas supply device 21: delivery roller (transport means) 22, 23: transport roller (transport means) 24: take-up roller (transport means) 1 〇〇: control unit 1 000, 2000: film forming device -27-