TWI298355B - Thin film deposition method and thin film deposition apparatus - Google Patents

Description

1298355 九、發明說明： 【發明所屬之技術領域】 本發明係關於適用於製造光學薄膜、光學元件、光電 疋件、及半導體元件用的薄膜之薄膜形成方法及薄膜形成 表置特別是關於可提昇能與薄膜進行化學反應之活性種 密度而面效率實施電漿處理之薄膜形成方法及薄膜形成事 置。 & L先刖技術】 已知的技術，係在真空容器内用電漿化的反應性氣體 在基板上形成薄膜，將所形成的薄膜予以改質，並進行蝕 刻等的電聚處理。例如，使用濺鍍技術在基板上形成金屬 之不疋全反應物構成之薄膜，使電漿化之反應性氣體與該 不完全反應物構成之薄膜接觸，藉此來形成金屬化合物構 成的薄膜（例如日本特開2001_234338號公報）。 該技術之薄膜形成裝置係設有：用來對基板進行濺鍍 成膜處理之成職縣，及對形成的薄膜進行電漿處理: 反應處理區。在該成膜處理區，設有用來導人非活性氣體 之氣體導入機構1用所導入的非活性氣體，來濺蝕成膜 處理區内之乾’藉此在基板表面形成薄膜。 在成膜處理區形成薄膜後之基板，係搬送至反應處理 :槿在=處理區設有：用來導入反應性氣體之氣體導入 導聚之電漿產生機構，藉由電製產生機構 化等的處理。 電纽，而對基板上的薄膜進行氧 1298355 體係包含：離子、自由基 的電子、離子，可能會造 之反應性氣體的自由基， 以電漿產生機構電漿化之氣 等的活性種。電漿化氣體中所含 成薄膜之損傷，相反地，呈電中性 則大多有助於薄膜之形成。 -般而言，在薄膜形成裝置，若電衆產生機構所產生 之自由基密度越高’由於更多的自由基和基板上的薄膜接 觸’故能更高效率地進行雷婿余田 、 卞l适仃电水處理。然而，習知之薄膜形 成虞置’所產生之自由基密声兀古 w. w签在沒不同，並無法高效率地進行 電漿處理。 本發明之目的係、提供形成方法及薄膜形成裝 置，其藉由提高電聚中反應氣體之自由基密度，而能對薄 膜進行高效率的電漿處理。 【發明内容】 本發明人發現到，藉由對反應處理區積極地導入非活 性氣體，即可提昇反應處理區所產生之電漿密度。 亦即’用以解決上述課題之本發明之薄膜形成方法， 係使用薄膜形成裝置（將該真空容器内的面向電漿產生區 域的壁面用絕緣體被覆）對基體進行薄膜形成；其特徵在 於進行··將真空容器内部維持真空之製程，在配設於該真 空容器之基體搬送機構上保持基體之基體保持製程，對成 膜處理區導入非活性氣體以將靶濺蝕，藉此對該基體進行 成膜處理之成膜處理製程，將該成膜處理後之該基體搬送 至反應處理區之基體搬送製程，對該反應處理區内導入反 應性氣體及非活性氣體以產生電漿，藉此對該成膜處理後 1298355 之該基體進行電漿處理之電漿處理製程；藉由反覆進行該 成膜處理製程及該電漿處理製程來在該基體上形成薄膜。 如此般，依據本發明之薄膜形成方法，不僅對成膜處 理區’亦對反應處理區積極地導入非活性氣體。因此，可 提昇電衆中反應性氣體的自由基密度，而能進行高效率的 電漿處理。 又，由於將該真空容器内的面向電襞產生區域的壁面 用絕緣體被覆，故藉電漿產生機構而產生於電聚中之自由 基或激勵狀態之自由基等活性種，因其與真空容以的t 漿產生區域的壁面反應而消滅的情形可被抑制住。 這時，該非活性氣體較佳為擇自氯、氨、氛、氮 所構成群中之氣體。 山 又，較佳為將該真空容器内的壁面用絕緣體被覆。 =採用這種構成，電聚產生機構所產生之電聚中的 之電Γ產t勵狀態之自由基等的活性種，因與真空容器内 制。生區域之壁面反應而消滅的情形，將可獲得抑 所構：群Γ絕緣體’以擇自熱解氮化删、氧化銘及氧切 所構成群巾之絕緣體為佳。 夕 性氣:之導入該反應處理區之全氣體流量’該非* “机里比較佳為〇·15~0.45的範圍。 密度，能使電漿中反應性氣體的自由基 特θ回。因此能獲得衰減係數較低之良好薄膜。 疋，這時前述流量比以〇. 27為佳。 、1298355 精由抓用這種流量比’能使電漿中反應性氣體的自由 基密度變得特別I因此能獲得衰減係數較低之良 膜。 又，用以解決上述課題之本發明之薄膜形成裝置，係 具備’内部可維持真空之真空容器’配設於該真空容器内、 用來搬送基體之基體搬送機構，形成於該真空容器二、用 來對》亥基體進仃成膜處理之成膜處理區，形成於該真空容 器内、用來對該基體進行電襞處理之反應處理區，藉此來 在該基體上形成薄膜；其特徵在於具備：肖來對該^應處 理區導入反應性氣體之反應性氣體導入機構，用來個別對 該成膜處理區及該反應處理區導人非活性氣體之非活性氣 體導入機構’配設於該成膜處理區、用來藉由該非活性氣 體將乾濺钕以對該基體進行成膜處理之成膜處理機構，配 設於該反應處理區1來在該反應處理區内產生反應性氣 體及非活性氣體之雷锻，驻m > 电水猎此對該成膜處理後的基體進行 電漿處理之電漿產生機肖；將該真空容器内的面向電浆產 生區域的壁面用絕緣體被覆。 如此般，依據本發明之薄膜形成裝置，不僅對成膜處 理區，亦對反應處理區導入非活性氣體。因此，可提昇電 襞中反應性氣體的自由基密度’而能進行高效率的電裝處 理。 又’由於將該真空容器内的面向電漿產生區域的壁面 用絕緣體被覆，故藉電漿產生機構而產生於電漿中之自由 基或激勵狀態之自由基等活性種，因其與真空容器内的電 1298355 漿產生區域& 這時=反應：消減的情形可被抑制住。 存非活性氣俨夕霞 &、 彳土為具備··用以貯 虱體之早一非活性氣體貯存機槿, 該非活性氣俨纩在她姓 械構，用來將貯存於 之第一配管，及導入則述成膜處理區 活性氣體導入：反:：該非活性氣體貯存機構之非 導入别述反應處理區之第二配管。 或者，前述非活性氣體導入機構較佳 存非活性氣俨夕笙.. 為，、備.用以貯 :體之第-非活性氣體貯存機構，用來將貯存於 "ϋ輕氣體貯存機構 、 理區之帛-配以料人料成膜處 吕用以貝丁存非活性氣體之 貯存機構（其盥嗜第一-苍从a —非活f生乳體 ^ ^ ^苐非性軋體貯存機構分開設置），及 用來將射存於該第二非活性氣 巩體貞了存機構之非活性氣體導 入刖述反應處理區之第二配管。 又較佳為，前述反應性氣體導入機構係具備反應性氣 體流量調整機構，其可調整導 斤 登導入則述反應處理區之反應性 乳體流量；且該反應性氣體流量調整機構係具備非活性氣 體流量調整機構’其可調整導入前述反應處理區之非活性 氣體流量。 又，該非活性氣體較佳為擇自氬、氦、氖、氪、氙所 構成群中之氣體。 又，用絕緣體被覆之該真空容器内的壁面，較佳為該 真空容器之内壁面。 又，前述絕緣體，以擇自熱解氮㈣、氧化減氧化石夕所 構成群中之絕緣體為佳。 10 1298355 如此般，藉由在成膜處理區及反應處理區雙方均導入 非活性氣體，將可提昇電漿中反應性氣體的自由基密度， 而能進行高效率的電漿處理。 又，由於將該真空容器内的面向電漿產生區域的壁面 用絕緣體被覆，故藉電漿產生機構而產生於電漿中之自由 基或激勵狀態之自由基等活性種，因其與真空容器内的電 漿產生區域的壁面反應而消滅的情形可被抑制住。 以下將說明本發明之其他特點。 【實施方式】 以下根據圖式來說明本發明之一實施例。以下所說明 之構件、配置等，並非用來限定本發明者，在本發明主旨 之範圍内當然能作各種適當的改變。 圖卜圖2係濺鍍裝置i之說明圖。i係為便於理 解而取局部截面之俯視說明圖，圖2係沿圖i之線 取局部截面之側視說明圖。濺鑛裝置1係本發明的薄膜形1298355 IX. Description of the Invention: [Technical Field] The present invention relates to a film forming method and a film forming table suitable for producing a film for an optical film, an optical element, a photoelectric element, and a semiconductor element, and particularly relates to an improvement A film formation method and a film formation process in which plasma treatment can be carried out by chemically reacting the density of the active species with the film. & L prior art] A known technique is to form a thin film on a substrate by using a plasma-reactive reactive gas in a vacuum vessel, to reform the formed film, and to perform electropolymerization treatment such as etching. For example, a thin film made of a metal-free reaction material is formed on a substrate by a sputtering technique, and a plasma-formed reactive gas is brought into contact with a film composed of the incomplete reactant, thereby forming a thin film composed of a metal compound ( For example, Japanese Patent Laid-Open Publication No. 2001-234338). The film forming apparatus of the present technology is provided with a job-preserving zone for sputtering a substrate into a film, and plasma treatment of the formed film: a reaction treatment zone. In the film forming treatment zone, the gas introduction mechanism 1 for introducing a non-reactive gas is provided with the introduced inert gas to sputter the dryness in the film formation processing zone, thereby forming a film on the surface of the substrate. The substrate after the film formation in the film formation treatment zone is transported to the reaction treatment: 槿 in the treatment zone: a plasma generation mechanism for introducing a gas for introducing a reactive gas into a conduction, and generating a mechanism by electrolysis Processing. The electric button is used to carry out the oxygen on the substrate. The 1298355 system contains: ions, free radicals, electrons, ions, free radicals that may cause reactive gases, and active species such as plasma generated by the plasma generating mechanism. The damage of the film contained in the plasma gas, on the contrary, is electrically neutral and contributes to the formation of the film. In general, in the thin film forming apparatus, if the density of radicals generated by the electricity generation mechanism is higher, "the more free radicals and the film on the substrate are in contact with each other", the thunder and the field can be more efficiently performed. Suitable for electric water treatment. However, the free radicals produced by the conventional film forming device are not different, and the plasma processing cannot be performed efficiently. SUMMARY OF THE INVENTION An object of the present invention is to provide a forming method and a film forming apparatus which can perform high-efficiency plasma processing on a film by increasing the radical density of a reaction gas in electropolymerization. SUMMARY OF THE INVENTION The present inventors have found that by actively introducing a non-active gas into a reaction treatment zone, the plasma density generated in the reaction treatment zone can be increased. In other words, the film forming method of the present invention for solving the above-mentioned problems is formed by forming a film on a substrate by using a film forming apparatus (the wall surface of the vacuum container facing the plasma generating region is formed of an insulator); a process of maintaining a vacuum inside the vacuum container, maintaining a substrate holding process of the substrate on the substrate transfer mechanism disposed in the vacuum container, introducing an inert gas into the film forming processing region to sputter the target, thereby performing the substrate on the substrate a film forming process for forming a film, transferring the substrate after the film forming process to a substrate transfer process in the reaction processing zone, introducing a reactive gas and an inert gas into the reaction zone to generate a plasma, thereby The substrate of 1298355 after the film forming process is subjected to a plasma treatment process of plasma treatment; a film is formed on the substrate by repeating the film forming process and the plasma processing process. As described above, according to the film forming method of the present invention, the inert gas is actively introduced not only to the film forming treatment zone but also to the reaction treatment zone. Therefore, the radical density of the reactive gas in the electric power can be increased, and high-efficiency plasma processing can be performed. Further, since the wall surface facing the electric power generation region in the vacuum container is covered with an insulator, an active species such as a radical generated in the electropolymerization or a radical in an excited state by the plasma generating mechanism is used as the vacuum capacity. The situation in which the wall reaction of the t-slurry generating region is eliminated can be suppressed. In this case, the inert gas is preferably a gas selected from the group consisting of chlorine, ammonia, atmosphere, and nitrogen. Further, it is preferable that the wall surface in the vacuum container is covered with an insulator. With this configuration, the active species such as the radicals generated in the electromotive force generated by the electropolymerization mechanism are internally reacted with the vacuum vessel. In the case where the wall surface of the green zone is destroyed and destroyed, it is preferable that the group Γ insulator is an insulator selected from the group consisting of pyrolytic nitriding, oxidizing, and oxygen cutting.夕气: The total gas flow rate introduced into the reaction treatment zone 'this non-*' is better in the range of 〇·15~0.45. The density can make the free radical of the reactive gas in the plasma θ. A good film with a low attenuation coefficient is obtained. 疋, the aforementioned flow ratio is preferably 〇27. 1298355 Fine-graining this flow ratio can make the radical density of the reactive gas in the plasma special. In addition, the film forming apparatus of the present invention for solving the above-mentioned problems is provided with a "vacuum container capable of maintaining a vacuum inside" disposed in the vacuum container and for transporting the substrate of the substrate. a transporting mechanism formed in the vacuum processing vessel 2, a film forming processing zone for forming a film formation process, and a reaction processing zone formed in the vacuum vessel for electrothermal treatment of the substrate Forming a film on the substrate; and comprising: a reactive gas introduction mechanism for introducing a reactive gas into the treatment zone, for individually guiding the film formation treatment zone and the reaction treatment zone An inert gas introduction mechanism of an inert gas is disposed in the film formation processing zone, and a film formation processing mechanism for performing a film formation treatment on the substrate by dry sputtering of the inert gas is disposed in the reaction treatment Zone 1 to generate reactive gas and inert gas in the reaction treatment zone, in the m > electric water hunting plasma processing machine for the plasma treatment of the film formation process; The wall surface facing the plasma generating region in the vacuum vessel is covered with an insulator. Thus, the film forming apparatus according to the present invention introduces an inert gas not only to the film forming processing zone but also to the reaction processing zone. The radical density of the reactive gas is capable of high-efficiency electrical installation. Further, since the wall surface facing the plasma generation region in the vacuum container is covered with an insulator, it is generated in the plasma by the plasma generating mechanism. Active species such as free radicals or free radicals in the excited state, because they generate a region with the electric 1298355 slurry in the vacuum vessel. At this time, the reaction: the reduction can be suppressed.俨 俨 & & 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 In the introduction, the active gas introduction into the film formation treatment zone is reversed: the non-reactive gas storage mechanism is not introduced into the second pipe of the reaction treatment zone. Alternatively, the inert gas introduction mechanism preferably has an inert gas. For the storage, the first-inactive gas storage mechanism for storage: for storage in the "light gas storage mechanism, the area of the area - with the material film formation" The storage mechanism of the non-reactive gas of Ding Cun (the 盥 第一 - - 苍 a a a — — — — — — — ^ ^ ^ ^ ^ ^ ^ 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开 分开The inert gas of the storage mechanism is introduced into the second pipe of the reaction treatment zone. Further preferably, the reactive gas introduction mechanism includes a reactive gas flow rate adjusting mechanism that adjusts a flow rate of the reactive milk introduced into the reaction treatment zone, and the reactive gas flow rate adjustment mechanism has a non-reactive The active gas flow rate adjusting mechanism 'adjusts the flow rate of the inert gas introduced into the reaction treatment zone. Further, the inert gas is preferably a gas selected from the group consisting of argon, helium, neon, krypton and xenon. Further, the wall surface in the vacuum container covered with the insulator is preferably the inner wall surface of the vacuum container. Further, the insulator is preferably an insulator selected from the group consisting of pyrolytic nitrogen (IV) and oxidized deoxidized oxide. 10 1298355 In this way, by introducing an inert gas into both the film formation treatment zone and the reaction treatment zone, the radical density of the reactive gas in the plasma can be increased, and high-efficiency plasma treatment can be performed. Further, since the wall surface facing the plasma generation region in the vacuum container is covered with an insulator, an active species such as a radical generated in the plasma or a radical in an excited state by the plasma generating mechanism is used as the vacuum container. The situation in which the wall surface of the plasma generating region is destroyed and destroyed can be suppressed. Other features of the invention will be described below. [Embodiment] Hereinafter, an embodiment of the present invention will be described based on the drawings. The members, the arrangements, and the like described below are not intended to limit the invention, and various modifications can be made without departing from the spirit and scope of the invention. Figure 2 is an explanatory view of the sputtering apparatus i. i is a plan view for taking a partial cross section for ease of understanding, and Fig. 2 is a side view showing a partial cross section taken along line i of Fig. i. Sputtering device 1 is a film shape of the present invention

本例中，關於賤鍍的例子，係使用進行磁控錢 鑛裝置i，但並不限於此，也能採用非磁控放電而 極濺鍍等其他公知的濺鍍之濺鍍裝置。 丁 依據本例之濺鍍裝£ i，係藉由錢鑛形成比目的 :很夕的薄膜，接著進行電聚處理’ #由反覆此、 基板上形成目的膜厚之薄膜。本例中，藉由反覆在 鍍及電襞處理來形成膜厚〇.〇1〜l 5nm薄膜之步驟，二乂歲 成目的膜厚之數〜數百nm的薄膜。 可形 1298355 本例之雜裝置i之主要構成要素包含：真空容器u， 將待形成薄膜之基板保持於真空容器n内之基板保持具 13,用來驅動基板保持具13之馬達17，賴壁i2,i6，磁 控㈣電極仏川，中頻交流電源、23,用來產生電聚之 電t產生裝置61。間隔板16相當於本發明之電㈣聚壁， 電聚產生裝置6i相當於本發明之電聚產生機構，基板保 持具13及馬達17相當於本發明之基體搬送機構，磁控滅 鍵電極2U，21b相當於本發明之成臈處理機構。 真空容器"’係公知濺鍍裝置一般所採用之不鏽鋼 製’呈大致長方體形之中空體。真空容器"接地。又直 空容器11的形狀採中空圓柱狀亦可。 〃 基板保持具13係配置於真空容H 11内之大致中央。 基板保持具13形狀呈圓筒壯 t w尚狀，在其外周面保持複數個基 反（圖不）。基板保持具13除圓筒狀外，也能採中空多角 柱狀、圓錐狀。基板保持具13 g 而形成電位浮接狀態。在直空容匕二呈電氣絕緣， 隹八工谷益11内將基板保持具13 之=二圓筒筒方向之中心軸線（參照圖2)朝真空容器η 於直*容二在真空容器11内維持真空狀態下，藉由設 心軸線“中心旋轉。 而使基板保持具η能以中 心軸具13之外周面，在順沿基板保持具η中 軸線ζ的方向(上下方向），以保持既定 數基板（未圖示）整齊排列。本 、…夕 下稱「膜m 不J Τ以基板之溥膜形成面(以 成面」）朝向與基板保持具U的中心轴線2垂 12 1298355 直的方向之方式’用基板保持具13來保持基板。 間隔壁I2,16，係從真空容考 …設。本例之間隔壁…=面朝基板保持 大致長方體，且為不鏽鋼製的構件:、間:== 11之内壁與基板保持具η之間，’且彳… 奋器π之側壁朝基板保持且 、二 12,16被固定成，使間隔壁12 土 夕向辟/丨口 ’之開側面向真空容器1 1 内土側，另一側面向基板保 ^ # α y ^ 乐符具13。又，間隔壁12，16 之基板保持具13側的端部，係 形狀之形狀。 係柄沿基板保持具丨3外周 用來進行賤鍍之成膜處理區2〇，係圍繞真空 的内壁面、間隔壁12、基柘 扳保持具1 3的外周面而形成。 又’用來產生電浆而對基板上薄膜進行電聚處理之反應處 理區60，係圍繞直处交哭、 八工谷态11的内壁面、後述之電漿處理 装置61、間隔壁16、| μ 土板保持具13的外周面而形成。本 例中’相對於直空交哭1 Λ y 八合斋11上之間隔壁12固定位置，間隔 係口定於繞基板保持具丄3中心轴線z旋轉約川度 、置因此成膜處理區20與反應處理區60，係以基 呆持^ 13中心軸線Z為中心形成於偏離90度的位置。 因此#馬達17來轉動驅動基板保持具13時，基板保持 /、13外周面所保持之基板，會在面向成膜處理區之位 置與面向反應處理區6〇的位置間進行搬送。 在真空谷為11之成膜處理區20與反應處理區60之 間連接有排氣用配管，該配管上連接著真空纟i 5，以進 13 1298355 行真空容器11内之排氣。利用該真空泵15及未圖示之控 制器，來調整真空容器11内之真空度。 間隔壁16之面向反應處理區6〇的壁面上，被覆著絕 緣體構成之保護層Pm器U内壁面之面向反應處理 區60的部分’亦被覆著絕緣體構成之保護層p。構成保護 層P之絕緣體，例如可使用熱解氮化删（PBN : pyr〇丨沖c Boron Nitride)、氧化銘（Al2〇3)、氧化石夕（si〇2)、氮化爛（bn) 等。保護層p，可藉由化學氣相成長法（ChemicaiIn the present embodiment, the magnetron ore metering apparatus i is used as an example of the rhodium plating. However, the present invention is not limited thereto, and other known sputtering apparatuses such as non-magnetostatic discharge and polar sputtering may be used. According to the sputtering apparatus of this example, the film is formed by the money ore. The film is formed in the same manner as the film, and then the electropolymerization process is performed. # By repeating this, a film having a desired film thickness is formed on the substrate. In this example, a film having a film thickness of 〇1 to 15 nm is formed by repeating plating and electric galvanizing treatment, and a film having a thickness of from a few hundred to a few hundred nm is formed. Shape 1298355 The main components of the device i of this example include: a vacuum container u, a substrate holder 13 holding the substrate to be formed in the vacuum container n, and a motor 17 for driving the substrate holder 13 I2, i6, magnetic control (four) electrode Xichuan, intermediate frequency AC power supply, 23, used to generate electro-convergence electric t generating device 61. The partition plate 16 corresponds to the electric (four) collecting wall of the present invention, and the electropolymer generating device 6i corresponds to the electropolymer generating mechanism of the present invention, and the substrate holder 13 and the motor 17 correspond to the substrate carrying mechanism of the present invention, and the magnetron extinguishing electrode 2U 21b corresponds to the sputum processing mechanism of the present invention. The vacuum container "' is a hollow body made of stainless steel generally having a substantially rectangular parallelepiped shape. Vacuum container " grounding. Further, the shape of the straight empty container 11 may be a hollow cylindrical shape.基板 The substrate holder 13 is disposed substantially at the center of the vacuum chamber H11. The substrate holder 13 has a cylindrical shape and a plurality of bases on its outer peripheral surface (not shown). In addition to the cylindrical shape, the substrate holder 13 can also adopt a hollow polygonal column shape or a conical shape. The substrate holder 13 g forms a potential floating state. In the straight space, the second is electrically insulated, and the bottom plate of the substrate holder 13 is in the direction of the second cylinder (refer to FIG. 2) toward the vacuum container η in the straight container 2 in the vacuum container 11 In the state of maintaining the vacuum inside, the center axis of the central axis 13 is rotated by the center axis of the center axis, and the direction of the center axis ζ (up and down direction) of the θ is maintained along the substrate to maintain A predetermined number of substrates (not shown) are arranged neatly. This is called "film m is not Τ 溥 溥 形成 」 」 」 」 」 」 」 」 」 」 12 12 12 12 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 In the straight direction, the substrate holder 13 is used to hold the substrate. The partition walls I2, 16 are provided from the vacuum chamber. The partition wall of this example...the surface is substantially rectangular parallelepiped facing the substrate, and is made of stainless steel: between: the inner wall of the ==11 and the substrate holder η, and the side wall of the π is held toward the substrate and And the two 12, 16 are fixed so that the opening side of the partition wall 12 is turned toward the inner side of the vacuum vessel 1 1 and the other side is secured to the substrate by the # α y ^ music symbol 13. Further, the partition walls 12, 16 have end portions on the side of the substrate holder 13 and have a shape. The handle is formed along the outer periphery of the substrate holding member 3 to form a film forming processing region 2 for ruthenium plating, and is formed around the inner wall surface of the vacuum, the partition wall 12, and the outer peripheral surface of the spacer holder 13. Further, the reaction processing zone 60 for generating a plasma and electropolymerizing the film on the substrate is an inner wall surface of the crying, the eight-work valley state 11, a plasma processing apparatus 61, a partition wall 16, which will be described later, | μ The outer peripheral surface of the soil holder 13 is formed. In this example, the partition wall 12 is fixed at a position relative to the straight space, and the spacer is fixed around the central axis z of the substrate holder z3, and is thus formed into a film. The region 20 and the reaction treatment region 60 are formed at a position deviated by 90 degrees centering on the center axis Z of the base. Therefore, when the motor 17 rotates and drives the substrate holder 13, the substrate held by the outer peripheral surface of the substrate holding/, 13 is transported between the position facing the film formation processing area and the position facing the reaction processing area 6A. An exhaust pipe is connected between the film formation processing zone 20 of the vacuum valley 11 and the reaction processing zone 60, and the vacuum 纟i 5 is connected to the pipe to exhaust the exhaust gas in the vacuum vessel 11 in 13 1298355. The degree of vacuum in the vacuum vessel 11 is adjusted by the vacuum pump 15 and a controller (not shown). On the wall surface of the partition wall 16 facing the reaction treatment zone 6〇, the portion ’ facing the reaction treatment zone 60 of the inner wall surface of the protective layer Pm U composed of the insulator is also covered with a protective layer p made of an insulator. As the insulator constituting the protective layer P, for example, pyrolysis nitriding (PBN: pyr 〇丨 c Boron Nitride), oxidized ing (Al 2 〇 3), oxidized stone 〇 (si 〇 2), nitriding rot (bn) Wait. Protective layer p, which can be chemically grown (Chemicai)

Deposition)、蒸鍍法、熱熔喷鍍法等來被覆在間隔壁i6或 真空容器11之内壁面。採用熱解氮化硼的情形，能以利 用化學氣相成長法而之熱分解法來被覆在間隔壁16或真 空容器11之内壁面。 透過配管將質量流量控制器25、26連接於成膜處理區 20。質量流量控制器25,係連接於濺鍍氣體高壓容器27(用 來貯留非活性氣體之非活性氣體貯存機構）；質量流量控 制器26,係連接於反應性氣體高壓容器28(用來貯留反應 性氣體之反應性氣體貯存機構）。非活性氣體與反應性氣 體，係在質量流量控制器25、26的控制下導入成膜處理 區20。可導入成膜處理區2〇之非活性氣體，例如包含氬、 氦、氖、氪、氙等。可導入成膜處理區之反應性氣體， 例如包含氧氣、氮氣、氟、臭氧氣體等等。 在成膜處理區2 0 ’以對向於基板保持具1 3外周面之 方式，於真空容器u壁面上配置有磁控濺鍍電極21a、21b。 該磁控濺鍍電極21 a、21 b，係透過未圖示的絕緣構件固定 1298355 在處於接地電位之真空容器11上。磁控㈣電極21a、21b， 5過文壓S 24連接於中頻交流電源、23，如此即可施加 交場。本例之中頻交流電源23,係用來施加lk~100kHz 之交/μ·電場在磁控濺鍍電極21心上設置靶29心2此。 乾29a、29b的形狀為平板狀，輕心、29b之與基板保持 具13外周面相對向的面，係朝與基板保持具13中心軸線 Z垂直的方向。 又，進行濺鍍之成膜處理區可設置一處，亦可設置複 數處。如® 1之虛線所示，可在真空容器、i i i設置與成 膜處理區20相同的成膜處理區40。例如，可在真空容器 11上設置間隔壁14，在隔著基板保持具13而與成膜處理 區20相對向的位置形成成膜處理區40。在成膜處理區4〇 上，與成膜處理區20同樣地，配置有磁控濺鍍電極41&、 41b。磁控濺鍍電極41a、41b，係透過變壓器44連接於中 頻交流電源43，如此即可施加交流電場。磁控濺鍍電極 41a、41b上設有靶49a、49b。透過配管將質量流量控制 器（流量調整機構）45、46連結於成膜處理區40。質量流 量控制器45，係連接於濺鍍氣體高壓容器47(用來貯留非 活性氣體之非活性氣體貯存機構）；質量流量控制器46， 係連接於反應性氣體高壓容器4吖用來貯留反應性氣體之 反應性氣體貯存機構）。在真空容器11之成膜處理區 與反應處理區60之間，連接有排氣用配管，該配管連接 於真空泵（用來進行真空容器11内的排氣）15，。真空泵15, 可與真空泵15共用。 15 1298355 在對應於反應處理區60之真空容器11内壁面上，形 成有開口。在開口連結電漿產生裝置（電漿產生機構）61。 在反應處理區60 ’係透過質量流量控制器75而連接有配 管（用來將非活性氣體導入非活性氣體貯存機構之非活性 氣體高壓容器77内）。又，質量流量控制器75、非活性氣 體高壓容器77及配管，係構成本發明之非活性氣體導入 機構。而質量流量控制器75，係構成本發明之非活性氣體 流量調節機構。 • 在本實施形態’係將濺鍍氣體高壓容器27(用來將非 活性氣體導入成膜處理區20)與非活性氣體高壓容器77(用 來將非活性氣體導入反應處理區6 〇)分開設置，以對成膜 處理區20及反應處理區6〇分別導入非活性氣體。但並不 限定於這種個別導入機構，例如可在成膜處理區2()及反 應處理區60設置共通非活性氣體貯存機構之單一非活性 氣體高壓容器’而從該非活性氣體高壓容器對成膜處理區 φ 20及反應處理區60分別導入非活性氣體。 又’透過氣量流量控制器76連接有配管（用來將反應 性氣體導入反應性氣體貯存機構之反應性氣體高壓容器78 内）。又，質量流量控制器76、反應性氣體高壓容器78及 配官’係構成本發明之反應性氣體導入機構。而質量流量 控制器76 ’係構成本發明之反應性氣體流量調節機構。 了導入反應處理區6 〇之非活性氣體，例如包含氬、氦、 巩、氪、氙等。可導入反應處理區6〇之反應性氣體，例 如包含氧氣、氮氣、氟、臭氧氣體等等。 1298355 圖3係電漿產生裝置61之說明圖，係電漿產生裝置61 之前視說明圖。圖3同時顯示匹配箱67及高頻電源69。 電漿產生裝置61係具備··板狀之電介質壁63，於同 一平面上形成渦狀之天線65a、65b，用來將天線65a、65b 連接於高頻電源69之導線66，用來將天線65a、65b固定 於電介電壁63之固定具68。天線65a相當於本發明之第 1天線，天線65b相當於本發明之第2天線，固定具68相 當於本發明之天線固定機構。 本例之電介質壁63係石英所形成。電介質壁63除石 英外也能用Αΐβ3等其他陶瓷材料來形成。電介質壁63係 被真空谷器11之突緣11 a和矩形框狀之蓋體1丨b所挾持， 且設置成可封閉真空容器u内壁上的開口（對應於反應處 理區60所形成者）。天線65a與天線65b，係在真空容器 11外側之電介質壁63對應位置，藉固定具68固定工成（參 照圖2、® 3)，以渦形成面朝真空容器丨i内侧的方式彼 此上下(與中心軸線z平行的方向)相鄰。亦即，如圖2、3 所示般’將天、線65a與天、線65b固定成，天線…:天線 65b之渴形成面（電介質壁63)之垂線間保有既定間隔卜 因此’當馬達17使基板保持具13繞中心轴線z旋轉， 基板保持具13外周之基板，將以 ， 心、㈣之渦形成面相對向的方式i行搬送=面與天線 中’由於天…天物固定成鄰亦：，本例 線65a與天、線65b係固定成，在與基板搬送方此、天 向（中心軸線Z之平行方向，本例為上下方向）相鄰父叉的方 17 1298355 本例之固定具68係具備：固定板68a、68b、螺栓68c、 68d。用固定板68a及電介質壁63來挾持天線65a，用固 定板68b及電介質壁63來挾持天線65b，用螺栓68c、68d 將固定板68a、68b鎖緊於蓋體1 lb，藉此來固定住天線65a 與天線65b。 天線6 5 a與天線6 5 b ’係在從局頻電源連到天線6 5 a、 天線65b之導線66 —端，相對高頻電源69形成並聯。天 線65a、65b，係透過匹配箱67(收容有匹配電路）來連接 於高頻電源6 9。如圖3所示，在匹配箱6 7内設有可變電 容器67a、67b。本例中，由於天線65a與天線65b並聯， 以往之匹配電路中匹配用線圈1 67c所達成的作用之全部 或一部分，能用天線65a來取代。因此，匹配箱内之電力 損耗會減少，天線65a與天線65b，能將高頻電源69所供 給的電力有效活用於電漿的產生。同時容易獲得阻抗匹 西己c 在與導線66 —端連接的部分，亦即天線65a與天線65b 之結合部位，係設有伸縮部66a、66b，俾調整天線65a與 天線65b的間隔D。伸縮部66a、66b相當於本發明之位置 調整機構。本例之濺鍍裝置1，當用固定具68來固定天線 65a、65b時，藉由使伸縮部66a、66b進行伸縮，即可調 整天線65a與天線65b在上下方向的間隔D。亦即，將用 固定板68a、68b與電介質壁63來挾持天線65a與天線 之位置加以改變，即可調整間隔D。 圖4係天線65a之截面圖。本例之天線係具備· 18 1298355Deposition, vapor deposition, hot melt spraying, or the like is applied to the partition wall i6 or the inner wall surface of the vacuum vessel 11. In the case of pyrolytic boron nitride, it can be coated on the partition wall 16 or the inner wall surface of the vacuum vessel 11 by a thermal decomposition method using a chemical vapor phase growth method. The mass flow controllers 25, 26 are connected to the film forming processing zone 20 through piping. The mass flow controller 25 is connected to the sputtering gas high pressure vessel 27 (the inert gas storage mechanism for storing the inert gas); the mass flow controller 26 is connected to the reactive gas high pressure vessel 28 (for storing the reaction) Reactive gas storage mechanism for gaseous gases). The inert gas and the reactive gas are introduced into the film forming processing zone 20 under the control of the mass flow controllers 25, 26. The inert gas which can be introduced into the film forming treatment zone 2, for example, contains argon, helium, neon, krypton, xenon, and the like. A reactive gas that can be introduced into the film forming treatment zone, for example, contains oxygen, nitrogen, fluorine, ozone gas, and the like. The magnetron sputtering electrodes 21a and 21b are disposed on the wall surface of the vacuum container u so that the film forming processing region 20' is opposed to the outer peripheral surface of the substrate holder 13. The magnetron sputtering electrodes 21a and 21b are fixed to the vacuum vessel 11 at the ground potential by an insulating member (not shown). The magnetron (four) electrodes 21a, 21b, 5 are connected to the intermediate frequency AC power source 23, so that the field of intersection can be applied. In this example, the intermediate frequency AC power source 23 is used to apply the lk~100 kHz intersection/μ· electric field to set the target 29 core 2 on the core of the magnetron sputtering electrode 21. The shapes of the stems 29a and 29b are flat, and the faces of the center of the substrate holder 13 which are light-centered and 29b are oriented in a direction perpendicular to the central axis Z of the substrate holder 13. Further, the film formation processing zone for performing sputtering may be provided in one place or in plural. As shown by the dashed line of ® 1, the film forming processing zone 40 which is the same as the film forming processing zone 20 can be disposed in the vacuum vessel, i i i . For example, the partition wall 14 may be provided in the vacuum container 11, and the film formation processing region 40 may be formed at a position opposed to the film formation processing region 20 with the substrate holder 13 interposed therebetween. Magnetron sputtering electrodes 41 & 41, 41b are disposed on the film formation processing region 4 in the same manner as the film formation processing region 20. The magnetron sputtering electrodes 41a, 41b are connected to the intermediate frequency AC power source 43 via a transformer 44, so that an alternating electric field can be applied. Targets 49a and 49b are provided on the magnetron sputtering electrodes 41a and 41b. The mass flow controllers (flow rate adjusting mechanisms) 45, 46 are connected to the film forming processing zone 40 through pipes. The mass flow controller 45 is connected to the sputtering gas high pressure vessel 47 (the inert gas storage mechanism for storing the inert gas); the mass flow controller 46 is connected to the reactive gas high pressure vessel 4 for storing the reaction. Reactive gas storage mechanism for gaseous gases). An exhaust pipe is connected between the film forming processing zone of the vacuum vessel 11 and the reaction processing zone 60, and the pipe is connected to a vacuum pump (for exhausting the inside of the vacuum vessel 11) 15. The vacuum pump 15 can be shared with the vacuum pump 15. 15 1298355 An opening is formed in the inner wall surface of the vacuum vessel 11 corresponding to the reaction treatment zone 60. A plasma generating device (plasma generating mechanism) 61 is connected to the opening. In the reaction treatment zone 60', a pipe (a non-reactive gas high-pressure vessel 77 for introducing an inert gas into the inert gas storage means) is connected through the mass flow controller 75. Further, the mass flow controller 75, the inert gas high pressure vessel 77, and the piping constitute the inert gas introduction mechanism of the present invention. The mass flow controller 75 constitutes the inert gas flow rate adjusting mechanism of the present invention. In the present embodiment, the sputtering gas high pressure vessel 27 (for introducing the inert gas into the film forming treatment zone 20) and the inert gas high pressure vessel 77 (for introducing the inert gas into the reaction treatment zone 6) are separated. It is provided to introduce an inert gas to the film formation treatment zone 20 and the reaction treatment zone 6〇, respectively. However, it is not limited to such an individual introduction mechanism, for example, a single inert gas high pressure vessel in which a common inert gas storage mechanism is disposed in the film formation treatment zone 2 () and the reaction treatment zone 60, and is formed from the inert gas high pressure vessel. The membrane treatment zone φ 20 and the reaction treatment zone 60 are each introduced with an inert gas. Further, a pipe (a reactive gas high-pressure vessel 78 for introducing a reactive gas into the reactive gas storage means) is connected to the gas flow rate controller 76. Further, the mass flow controller 76, the reactive gas high pressure vessel 78, and the dispensing unit constitute the reactive gas introducing means of the present invention. The mass flow controller 76' constitutes the reactive gas flow rate adjusting mechanism of the present invention. The inert gas introduced into the reaction treatment zone 6 includes, for example, argon, helium, xenon, krypton, xenon, and the like. A reactive gas which can be introduced into the reaction treatment zone, for example, contains oxygen, nitrogen, fluorine, ozone gas or the like. 1298355 Fig. 3 is an explanatory view of the plasma generating device 61, which is a front view of the plasma generating device 61. FIG. 3 also shows the matching box 67 and the high frequency power source 69. The plasma generating device 61 includes a plate-shaped dielectric wall 63, and forms spiral-shaped antennas 65a and 65b on the same plane for connecting the antennas 65a and 65b to the wires 66 of the high-frequency power source 69 for use in the antenna. The fixtures 68a, 65b are fixed to the fixture 68 of the dielectric wall 63. The antenna 65a corresponds to the first antenna of the present invention, the antenna 65b corresponds to the second antenna of the present invention, and the fixture 68 corresponds to the antenna fixing mechanism of the present invention. The dielectric wall 63 of this example is formed of quartz. The dielectric wall 63 can be formed of other ceramic materials such as Αΐβ3 in addition to stone. The dielectric wall 63 is held by the flange 11a of the vacuum barn 11 and the rectangular frame-like cover 1b, and is provided to close the opening on the inner wall of the vacuum vessel u (corresponding to the formation of the reaction treatment zone 60) . The antenna 65a and the antenna 65b are fixed at a position corresponding to the dielectric wall 63 outside the vacuum vessel 11, and are fixed by a fixing member 68 (refer to Figs. 2 and 3), and the vortex forming faces are directed upward and downward toward the inside of the vacuum container 丨i ( Adjacent to the direction parallel to the central axis z). That is, as shown in Figs. 2 and 3, the sky, the line 65a and the sky 65b are fixed, and the antenna...the antenna 65b has a predetermined interval between the perpendicular lines (the dielectric wall 63). 17, the substrate holder 13 is rotated about the central axis z, and the substrate of the outer periphery of the substrate holder 13 is transported in such a manner that the vortex forming surfaces of the center and the (4) face are opposite each other. In the case of the neighboring line, the line 65a is fixed to the sky and the line 65b, and the side of the parental fork is adjacent to the substrate, and the sky direction (the parallel direction of the central axis Z, in this case, the vertical direction) is adjacent to the parent side. The fixture 68 is provided with fixing plates 68a and 68b and bolts 68c and 68d. The antenna 65a is held by the fixing plate 68a and the dielectric wall 63, the antenna 65b is held by the fixing plate 68b and the dielectric wall 63, and the fixing plates 68a and 68b are locked to the lid 1b by the bolts 68c and 68d, thereby fixing the antenna 65a. Antenna 65a and antenna 65b. The antenna 6 5 a and the antenna 6 5 b ' are connected to the end of the conductor 66 connected to the antenna 65 5 a and the antenna 65 b from the local power source, and are connected in parallel with the high frequency power source 69. The antenna lines 65a and 65b are connected to the high-frequency power source 69 through the matching box 67 (containing the matching circuit). As shown in Fig. 3, variable capacitors 67a, 67b are provided in the matching box 67. In this example, since the antenna 65a is connected in parallel with the antenna 65b, all or part of the functions achieved by the matching coil 1 67c in the conventional matching circuit can be replaced by the antenna 65a. Therefore, the power loss in the matching box is reduced, and the antenna 65a and the antenna 65b can effectively use the power supplied from the high-frequency power source 69 for the generation of plasma. At the same time, it is easy to obtain the portion where the impedance is connected to the end of the wire 66, that is, the joint portion between the antenna 65a and the antenna 65b, and the expansion and contraction portions 66a and 66b are provided to adjust the interval D between the antenna 65a and the antenna 65b. The expansion and contraction portions 66a and 66b correspond to the position adjustment mechanism of the present invention. In the sputtering apparatus 1 of the present embodiment, when the antennas 65a and 65b are fixed by the fixing device 68, the distance D between the antenna 65a and the antenna 65b in the vertical direction can be adjusted by expanding and contracting the expansion and contraction portions 66a and 66b. That is, the position of the antenna 65a and the antenna can be changed by the fixing plates 68a, 68b and the dielectric wall 63, and the interval D can be adjusted. Figure 4 is a cross-sectional view of the antenna 65a. The antenna system of this example is equipped with · 18 1298355

鋼製之圓管狀本體咅"5ai、被覆本體部表面之銀製的被覆 層㈣。為了降低天線65a之阻抗，天線65a之材質以低 電阻材料為佳。於是’ #用高頻電流會集中於天線表面的 特性，而用低成本、加工容易且低電阻之銅來形成圓管狀 的本體部65ai’並用電阻比銅低之銀被覆於本體部—I的 外側表面而構成被覆層65心。藉由採用此構成，可將天線 65a與天、線65b的高頻阻抗減少，而使電流高效率地流過 天線65a，藉此提高電聚產生效率。天線祝的構成，係 和天線65a同樣地具備銅製本體部65比及銀製被覆層 65b2。當然，也能改變天線65a與天線65b之截面大小（二 ㈤。本例中，伸縮部66a、66b的構成，也能用銅來形成 圓管狀，並在表面被覆銀而構成。 本例之電漿產生裝置61，係調整天線6“與天線6讣 在上下方向的間隔D、天線65a的直徑以、天線的直 徑Rb等後，將天線65a與天線65b固定住，再將反應性 氣體高壓容器78内之反應性氣體，透過f量流量控制器^ 而導入反應處理區60(保持（K1Pa〜1〇Pa左右的真空度）。 然後，從高頻電源69對天線65a與天線65b施加^^6MHz 的電壓，使反應性氣體的電漿在反應處理區6 〇產生既定 的分布，而可以對基板保持具13上之基板進行電滎處理。 本例中，藉由具備並聯的2個天線65a、65b及伸縮部 66a 66b相&於加大1個天線的情形，除能減低匹配箱 67内之匹配電路的電力損耗外，㈣容易獲得阻抗匹配， 而能廣範圍地進行高效率的電漿處理。 19 1298355 又，由於天線65a、65b之本體部㈣、65b】是用低 成本、加工容易、低電阻的銅來形成圓管狀，且被覆層65〜、 6 5b2是用電阻比銅更低的銀爽） 一 尺臥J跟术形成，因此能降低天線65a、 6 5 b之局頻阻抗，可減少雷六p 成電力扣耗而進行高效率的電漿處A steel tubular body 咅"5ai, a silver coating covering the surface of the body (4). In order to reduce the impedance of the antenna 65a, the material of the antenna 65a is preferably a low-resistance material. Therefore, the high-frequency current is concentrated on the surface of the antenna, and the low-cost, easy-to-process and low-resistance copper is used to form the circular tubular body portion 65ai' and is coated with the lower portion of the copper than the copper. The outer surface forms the core of the coating layer 65. By adopting this configuration, the high-frequency impedance of the antenna 65a and the sky 65b can be reduced, and the current can be efficiently flowed through the antenna 65a, thereby improving the efficiency of electropolymerization. Similarly to the antenna 65a, the configuration of the antenna is provided with a copper main body portion 65 and a silver coating layer 65b2. Of course, the cross-sectional size of the antenna 65a and the antenna 65b can be changed (two (five). In this example, the configuration of the elasticized portions 66a and 66b can also be formed by forming a circular tube with copper and coating the surface with silver. The slurry generating device 61 adjusts the distance J between the antenna 6 and the antenna 6A in the vertical direction, the diameter of the antenna 65a, the diameter Rb of the antenna, and the like, and fixes the antenna 65a and the antenna 65b, and then the reactive gas high-pressure container. The reactive gas in 78 is introduced into the reaction processing zone 60 through the f-volume flow controller (maintained (a vacuum of about K1Pa to 1 〇 Pa). Then, the antenna 65a and the antenna 65b are applied from the high-frequency power source 69. The voltage of 6 MHz causes the plasma of the reactive gas to have a predetermined distribution in the reaction processing zone 6 , and the substrate on the substrate holder 13 can be electrically treated. In this example, by providing two antennas 65a in parallel. 65b and the expansion and contraction portion 66a 66b phase & in the case of increasing one antenna, in addition to reducing the power loss of the matching circuit in the matching box 67, (4) easy to obtain impedance matching, and capable of performing high-efficiency electric power in a wide range Pulp treatment. 19 129835 5, the main parts (4) and 65b of the antennas 65a and 65b are formed into a circular tube by copper which is low in cost and easy to process and low in resistance, and the coating layers 65 to 65b2 are made of a lower silver than the copper. A one-foot lying J is formed by the technique, so that the local frequency impedance of the antennas 65a, 6 5 b can be reduced, and the power consumption of the lightning rods can be reduced to perform high-efficiency plasma processing.

” i八咏wa興天線65b在上 :方向的間隔I)，以調整基板保持具13上的基板之電浆分 2由於天線65a之直徑Ra、天線65b之直㈣、天線⑽、 之粗細等也能分別獨立改變，藉由調整天、線-的直 0直仅Rb或粗細等，也能調整電漿分布。 本例中，如圖3所示，壬綠β c： t 、a〜天線65b之整體形狀係 由大小不同的半圓所組成，但天線…與天線 形狀:也能改變成矩形等形狀’藉此來調整電聚的分布。 m’由於將天、線65a與天線65b沿基板搬送方向 ::方向(與中心軸線z平行的方向)排列，且兩者的間 隔此做調整，當必須在美柄、， 、 紅治7 板搬运方向之交又方向（盥中心 平行的方向）進行廣範圍的電漿處理時，㈣㈣ r;“度的分布。例如，像本例般使用旋轉型(car_el 板的配置、濺鍍條件等，基 與位於其中間之薄膜“板保持具13上方之薄膜、 口要採用者膜厚可能會產生偏差。這時， :二=Γ漿產生…1，即可對應於不同膜二 適當_整電漿的密度分布。 个丨j膘；而 本例中，如上述般，係將間隔壁16之面向反 20 1298355 應處理區60的壁面、真空容器u内壁面之面向反應處理 區60的部分’用熱解氮化硼來被覆，藉此使反應處理區6〇 的自由基維持在高密度，使更多自由基和基板上的薄膜接 觸以謀求電漿處理的效率化。亦即，藉由將間隔壁Μ盘 真空容器U的㈣面用化學安定性佳的熱解氮化硼被覆:、 措電漿產生裝置61而產生於反應處理區6〇内之自由基或 激勵狀態之自由基’因其與間隔壁16或真空容器u内壁 面反應而消滅的情形會被抑制住。又，藉由間隔壁Μ，二 將反應處理區60產生之自由基控制成朝向基板保持具^ 的方向。 以下例示出使用上述滅鍍裝置i來進行電聚處理的方 法，亦即’對基板上經濺鍍形成之不完全氧化矽 (SiOJxlU))薄膜進行電漿處理，使該不完全氧化石夕進一 步氧化而形成氧切（Si〇x2(xl<山2))。又，所稱不完全氧 指氧…〇2構成元素的氧有短缺之不 化 石夕 SiOx(x<2) 〇 被美=持=板絲29a、29b配置於賤鑛裝置卜基板 被土板保持具13所保持。分別在磁控 上設置把―。㈣a、29b的材料是採_广 接著，將真空容器u内減壓成既定壓力， 使基板保持具13旋轉4後，/動馬達17 定後，將$膊忐 Α為11内的壓力穩 二成膜處理區20内的壓力調整成。.m 28’_f量流量控制器25、26調整流量"I 咏 咏 天线 antenna 65b is on: the interval I in the direction" to adjust the plasma division of the substrate on the substrate holder 13 due to the diameter Ra of the antenna 65a, the straightness of the antenna 65b, the thickness of the antenna (10), etc. It can also be independently changed, and the plasma distribution can also be adjusted by adjusting the straight line of the sky and the line to the Rb or the thickness. In this example, as shown in Fig. 3, the green β c: t , a ~ antenna The overall shape of 65b is composed of semicircles of different sizes, but the antenna...and the shape of the antenna can also be changed into a shape such as a rectangle, thereby adjusting the distribution of electropolymerization. m' is due to the sky, the line 65a and the antenna 65b along the substrate. The direction of the transport:: the direction (the direction parallel to the central axis z) is arranged, and the interval between the two is adjusted. When it is necessary to move in the direction of the handle of the handle, the red rule, the direction of the transport (the direction parallel to the center) When performing a wide range of plasma treatments, (iv) (iv) r; "degree distribution. For example, as in the case of the present example, the rotation type (the configuration of the car_el plate, the sputtering condition, etc., the film and the film located above the plate holder 13 may be deviated.) 2 = the slurry is produced...1, which corresponds to the density distribution of the different membranes and the whole plasma. In this example, as described above, the partition wall 16 faces the reverse 20 1298355. The wall surface of the region 60 and the portion of the inner wall surface of the vacuum vessel u facing the reaction treatment zone 60 are coated with pyrolytic boron nitride, whereby the radicals in the reaction treatment zone 6 are maintained at a high density, allowing more radicals and The film on the substrate is brought into contact to improve the efficiency of the plasma treatment. That is, the (four) surface of the spacer vacuum chamber U is coated with pyrolytic boron nitride having good chemical stability: The radical generated in the radical or excited state in the reaction treatment zone 6 is suppressed by the reaction with the partition wall 16 or the inner wall surface of the vacuum vessel u. Further, by the partition wall Μ, Free radical control generated by reaction treatment zone 60 The direction of the substrate holder is oriented toward the substrate. The following is a method for performing the electropolymerization process using the above-described deplating device i, that is, a plasma treatment of a film of incompletely cerium oxide (SiOJxlU) formed by sputtering on a substrate. The incomplete oxidized stone is further oxidized to form an oxygen cut (Si〇x2 (xl < mountain 2)). Further, the incomplete oxygen refers to the oxygen of the element 的2, and there is a shortage of oxygen in the element xix (x< 2) 〇 美 美 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The pressure inside the vacuum container u is reduced to a predetermined pressure, and after the substrate holder 13 is rotated 4, the motor 17 is fixed, and the pressure in the film formation chamber 20 is adjusted to be constant. .m 28'_f quantity flow controller 25, 26 adjusts flow

21 1298355 鑛用非活性氣體（氬氣）與反應性氣體（氧氣）導入成膜h 區20内’而將成膜處理區2〇内調整成可進行濺鍍的琿:理 接著，由中頻交流電源23，透過變壓器24而對^ 賤鍍電極2la、21b施加頻率η咖z的交流電壓: 在靶29a、29b產生交流電場。因此，在某時點，靶^ 成為陰極（負極）而靶29b成為陽極（正極）。在另一時點a 當交流方向改變時，靶29b變成陰極(負極)，靶Μ”:變 成陽極（正極）。如此般，藉由使一對靶29&amp;、2此交、' 變成陽極與陰極，即產生電漿，而對陰極上的靶進行濺鍍。 當濺鍍進行中，陽極上可能會附著有非導電性或低導 電性的氧化秒（SW2)，當該陽極因交流電場而轉變成 陰極時，t將這些氧切（Si〇x(M2m兹，而使乾表面恢 復原來的清淨狀態。 人 藉由使一對靶29a、29b交替地變成陽極與陰極，可持 績獲得穩定的陽極電位狀態，可防止電漿電位（通常大致等 於陽極電位）的改變，而在基板的膜形成面安定地形成矽或 不元全氧化石夕（SiOxl(xl&lt;2))構成之薄膜。 又，成膜處理區20所形成之薄膜組成，藉由調整導入 成膜處理區20之氧氣流量、或控制基板保持具13之旋轉 速度，可調整成矽（Si)、氧化矽（Si〇2)、或不完全氧化矽 (SiOxl(xl&lt;2))。 在成膜處理區20内，當基板之膜形成面上形成矽或不 疋全氧化矽（SiOxl(xl〈2))構成的薄膜後，藉由旋轉基板保 持具13,將基板從面向成膜處理區2〇的位置搬送至面向 22 1298355 反應處理區6 0的位置。 在反應處理區60内，除從反應性氣體高壓容器78導 入反應性氣體（氧氣）外，也從非活性氣體高壓容器77導 入非活性氣體（例如氬氣）。接著，對天線65a、65b施加 13.56MHz之高頻電壓，藉由電漿產生裝置61使反應處^ 區6〇内產生電漿。反應處理區60之壓力維持於ο,。〗 然後，旋轉基板保持具丨3，當形成有薄膜（由矽或不 完全氧化矽（SiOxl(xl&lt;2))構成）的基板搬送至面向反應處 理區60的位置時，在反應處理區6〇内，係藉由電漿處理 而使矽或不完全氧化矽（Si〇xi(xl&lt;2))構成的薄膜進行氧化 反應。亦即，藉由因電漿處理裝χ 61而在反應處理區 内產生的氧氣電聚，使矽或不完全氧化矽（Si〇xi(xl&lt;2))進 行氧化反應，而轉換成所要組成之不完全氧化矽 (SiOx2(xl&lt;x2&lt;2))或氧化石夕。 經由以上過程，而製作出所要組成之氧化矽（si〇x(x&lt;2)) 薄膜。藉由重複以上過程’可將薄膜予以積層而製;乍出所 要膜厚的薄膜。 . 〃特別是，在本例中，除了反應性氣體外，亦將非活性 氣體導入反應處理@ 60。反應處理區6〇内導入之非活性 氣體比例，可依反應處理區60的形狀、反應處理區6〇的 壓力、天線65a、65b之放電條件、非活性氣體及反應性氣 體的種類等’來決定其最適當的比例。例^相對於反應 性軋體與非活性氣體的合計流量，係卩27%左右的流量來 導入非活性氣體。 23 1298355 如此般，除了反應性氣體外，亦將非活性氣體導入反 應處理區60，因此可提高電漿中反應性氣體的自由基相對 密度。其效果顯示於圖5〜7。圖5〜7所說明的實驗結果， 係針對將反應性氣體之氧氣、非活性氣體之氬氣導入後進 行實驗的情形。 圖5係顯示反應處理區60所產生之電漿中氧原子與氧 離子的比例，其中，係將對反應處理區6〇僅導入氧氣的 情形、與混合氧氣及氬氣來導入的情形兩者作比較。圖5 之橫軸代表高頻電源69所施加的電力，縱軸代表發光強 度比。又，發光強度比，係以發光分光法（〇ptiealEmissiQn21 1298355 Mine inert gas (argon) and reactive gas (oxygen) are introduced into film h zone 20' and the film forming treatment zone 2〇 is adjusted to be sputterable: then, by intermediate frequency The AC power source 23 applies an AC voltage of a frequency η to the 贱 plating electrodes 21a and 21b through the transformer 24: an AC electric field is generated in the targets 29a and 29b. Therefore, at a certain point, the target becomes a cathode (negative electrode) and the target 29b becomes an anode (positive electrode). At another time point a, when the alternating current direction is changed, the target 29b becomes a cathode (negative electrode), and the target Μ" becomes an anode (positive electrode). Thus, by making a pair of targets 29 & , that is, the plasma is generated, and the target on the cathode is sputtered. When the sputtering is in progress, a non-conductive or low-conductivity oxidized second (SW2) may be attached to the anode, and the anode is transformed by the alternating electric field. When the cathode is formed, t cuts these oxygens (Si〇x (M2m), and restores the dry surface to the original clean state. By making the pair of targets 29a and 29b alternately become anodes and cathodes, the performance can be stabilized. The anode potential state prevents a change in the plasma potential (generally substantially equal to the anode potential), and forms a film of ruthenium or a non-perovskite (SiOxl (xl &lt; 2)) on the film formation surface of the substrate. The film composition formed by the film formation processing zone 20 can be adjusted into bismuth (Si) and bismuth oxide (Si 〇 2) by adjusting the oxygen flow rate introduced into the film formation processing zone 20 or controlling the rotation speed of the substrate holder 13. Or incompletely yttrium oxide (SiOxl (xl &lt; 2)). In the film formation processing region 20, after forming a film made of yttrium or not yttrium oxide (SiOxl (xl<2)) on the film formation surface of the substrate, the substrate is processed from the surface by rotating the substrate holder 13. The position of the zone 2 is transported to a position facing the reaction zone 60 of 22 1298355. In the reaction treatment zone 60, in addition to the introduction of a reactive gas (oxygen) from the reactive gas high pressure vessel 78, it is also from the inert gas high pressure vessel 77. An inert gas (e.g., argon gas) is introduced. Then, a high frequency voltage of 13.56 MHz is applied to the antennas 65a and 65b, and plasma is generated in the reaction chamber 6 by the plasma generating device 61. The pressure of the reaction processing region 60 Then, the substrate holding member 3 is rotated, and when a substrate on which a thin film (made of yttrium or incomplete yttrium oxide (SiOx1 (xl &lt; 2))) is formed is transported to a position facing the reaction processing region 60, In the reaction treatment zone 6 ,, a film composed of yttrium or incomplete yttrium oxide (Si〇xi (xl &lt; 2)) is subjected to oxidation treatment by plasma treatment, that is, by processing by plasma treatment 61 and the oxygen generated in the reaction treatment zone is electropolymerized矽 or incomplete yttrium oxide (Si〇xi(xl&lt;2)) is oxidized and converted into incomplete yttrium oxide (SiOx2(xl&lt;x2&lt;2)) or oxidized stone of the desired composition. A thin film of yttrium oxide (si〇x(x&lt;2)) to be formed is prepared. The film can be laminated by repeating the above process; the film of the desired film thickness is taken out. 〃 In particular, in this example In addition to the reactive gas, the inert gas is also introduced into the reaction treatment @ 60. The proportion of the inert gas introduced into the reaction zone 6 can be determined according to the shape of the reaction treatment zone 60, the pressure of the reaction treatment zone 6 、, and the antenna 65a. The discharge condition of 65b, the type of inert gas and reactive gas, etc.' determine the most appropriate ratio. In the example, a flow rate of about 27% is introduced with respect to the total flow rate of the reactive rolled body and the inert gas to introduce an inert gas. 23 1298355 In this way, in addition to the reactive gas, the inert gas is introduced into the reaction treatment zone 60, so that the relative density of the radicals of the reactive gas in the plasma can be increased. The effects are shown in Figures 5-7. The experimental results described in Figs. 5 to 7 are for the case where an oxygen gas of a reactive gas or an inert gas of argon gas is introduced and the experiment is carried out. Fig. 5 is a view showing the ratio of oxygen atoms to oxygen ions in the plasma generated in the reaction treatment zone 60, in which both the case where only oxygen is introduced into the reaction treatment zone 6 and the case where oxygen and argon are introduced are introduced. compared to. The horizontal axis of Fig. 5 represents the electric power applied by the high-frequency power source 69, and the vertical axis represents the luminous intensity ratio. In addition, the luminous intensity ratio is based on luminescence spectroscopy (〇ptiealEmissiQn

Spectroscopy)測定電漿中激勵狀態的氧自由基，而測定氧 離子的發光強度。從圖5可看出，相較於對反應處理區6〇 僅導入15〇SCCm氧氣的情形，將氧氣與氬氣混合導入的情 形（導入llOsccm氧氣、4〇SCCm氬氣的情形，亦即，相對 於氧氣與氬氣之合計流量，以27%左右的流量導入氮氣的 情形），後者激勵狀態的氧自由基密度較高。又，流量單位 之seem ’係代表0°C、latm下每1分鐘的流量，其等於 cm3/min ° 圖6之實驗結果，係針對在反應處理區6〇混合導入氧 氣與氬氣（導入llOsccm氧氣、40sccm氬氣）的情形，以發 光分光法測定電漿中激勵狀態的氧自由基與氧離子的發光 強度結果。圖7係顯示相對於圖6結果之比較例，係針對 在反應處理區60未導入鼠氣而僅導入氧氣（導入 氧氣）的情形，以發光分光法測定電漿中激勵狀態的氧自由 24 1298355 基與氧離子的發光強度結果。 圖6、7之橫軸代表高頻電源69所施加的電力，縱車由 代表發光強度比。將圖6、7的結果做比較可知，相較於 未導入氬氣僅導入氧氣的情形，當混合導入氧氣與氯氣 時’後者氧自由基之發光強度較強，故其氧自由基的密度 較高。 如此般，藉由對反應處理區同時導入氧氣及氬氣，會 赉生氧自由基密度變高的現象，其理由可能是因為氬氣有 容易活性化的傾向。 亦即，氬氣與氧氣容易發生衝撞，透過該衝撞，活性 化的氬會對氧賦予激勵能量，而容易產生氧自由基或激勵 狀態的氧自由基。 因此，相較於對反應處理區僅導入氧氣的情形，藉由 混合適當比例的氬氣，可使所產生之氧自由 而進行更高效率的電漿處理。 ^ 一其次，針對導入反應處理區之氧氣流量比對氧原子與 氧離子的比例、衰減係數的影響進行實驗。實驗條件，係 ::頻電源軛力口 4.0Kw的電力，並以成膜速度〇·4請/似 進仃虱化鈮（Nb2〇5)的成膜，形成最終膜厚為50〇nm的薄 膜。 漿中I 12 :不出’導入反應處理區6〇之氧氣流量比對電 。3有之氧原子與氧離子的比例、衰減係婁文k的影響。 二曰^之也、軸代表著，相對於導入反應處理區60之全氣體 &quot;置（氧氣及氬氣之合計流量），氧氣的流量比（02/Ar+〇2)及 25 1298355 氬氣的流量比（Ar/Ar+〇2)。圖12左側的縱軸代表氧原子與 氧離子的發光強度比，右側縱軸代表衰減係數。發光強度 比係依前述發光分光法來測定。關於衰減係數让，當光學 常數（複折射率）為N、折射率為„時，係依N=n+ik的關係 所代表的數值。 根據圖12的結果可知，在氬氣流量比約0.15〜0.45的 範圍，衰減係數會急劇減少至約2〇χ1〇_4以下。因此，在 此範圍内’能製作低衰減係數之良好薄膜。特別是，當氬 氣流量比在約0.20〜〇.35的範圍，衰減係數k進一步降低 至約0.8x10-4以下’故更佳。當氬氣流量比為ο.”時， 由於衰減係數最小故更佳。 本例中，由於將絕緣體如前述般被覆於間隔壁16、真 空容器11内壁面之面向反應處理區60的部分，因此能使 反應處理區60之電漿中的氧自由基密度維持於高水準。 *圖8之實驗結果，係針對改變保護層p(用來被覆真空 :盗11内壁面之面向反應處理區6〇的部分)構成成分的 情形，以發光分光法測定存在於電漿中之激勵狀態氧自由 基的發光強度之結果。目8之橫軸代表高頻電源69所施 加的電力’縱軸代表發光強度比。 如圖8所示，相較於未設置保護層p的情形（圖8中「不 鏽鋼」之實驗結果），以熱解氮化侧（觸）、氧化銘⑴也）、 虱化矽（si〇2)構成的保護層p來被覆間隔壁16時，後者氧 自由基之發光強度強，可知其氧自由基密度較高。特別是， 以熱解氮化_N)構成的保護層p來被覆間隔壁Μ的情 26 1298355 形’其氧自由基的發光強度最強。 圖9顯示反應處理區所產生之電漿中之氧自由基的 流量密度’其中’係對以熱解氮化硼（PBN)被覆間隔壁16 與真空容器11的情形、與未被覆的情形兩者做比較。本 實驗例中，作為以熱解氮化硼（PBN)被覆間隔壁16與真空 容器11的情形，係在間隔壁16之面向反應處理區6〇側、 及真空容器11内壁面之被間隔壁16包圍之面向反應處理 區60的部分，被覆熱解氮化硼。Spectroscopy measures the oxygen radicals in the excited state of the plasma and determines the luminescence intensity of the oxygen ions. As can be seen from Fig. 5, in the case where only 15 〇SCCm of oxygen is introduced into the reaction treatment zone, oxygen is mixed with argon gas (in the case of introducing OLEDs of oxygen, 4 〇SCCm of argon gas, that is, The introduction of nitrogen gas at a flow rate of about 27% with respect to the total flow rate of oxygen and argon is high, and the density of oxygen radicals in the excited state is high. In addition, the seem ' of the flow unit represents the flow rate per minute at 0 ° C and lamat, which is equal to cm 3 /min °. The experimental results of Figure 6 are for the introduction of oxygen and argon in the reaction treatment zone 6 (introduction of llOsccm) In the case of oxygen, 40 sccm argon, the luminescence intensity results of oxygen radicals and oxygen ions in the excited state in the plasma were measured by luminescence spectrometry. Fig. 7 is a view showing a comparative example with respect to the results of Fig. 6 for measuring the oxygen state of the excited state in the plasma by the luminescence spectrometry in the case where only the introduction of oxygen (introduction of oxygen) into the reaction treatment zone 60 without introducing the mouse gas 24 1298355 The result of the luminescence intensity of the base and oxygen ions. The horizontal axis of Figs. 6 and 7 represents the electric power applied by the high-frequency power source 69, and the vertical car represents the luminous intensity ratio. Comparing the results of Figs. 6 and 7, it can be seen that compared with the case where only oxygen is introduced without introducing argon gas, when the oxygen and chlorine gas are mixed and introduced, the latter has a stronger luminescence intensity, so the density of oxygen radicals is higher. high. In this manner, the simultaneous introduction of oxygen and argon into the reaction treatment zone causes a phenomenon in which the density of oxygen radicals increases, which may be because argon tends to be easily activated. That is, argon gas and oxygen gas are likely to collide, and by this collision, the activated argon imparts excitation energy to oxygen, and oxygen radicals or oxygen radicals in an excited state are easily generated. Therefore, the generated oxygen can be freely subjected to a more efficient plasma treatment by mixing an appropriate proportion of argon gas than in the case where only oxygen is introduced into the reaction treatment zone. ^ First, experiments were conducted on the effect of oxygen flow rate on the ratio of oxygen atoms to oxygen ions and the attenuation coefficient. The experimental conditions are as follows: the power of the yoke of the frequency power supply is 4.0 Kw, and the film formation speed is 〇·4 please/like the film formation of Nb2〇5, and the final film thickness is 50〇nm. film. I 12 in the slurry: no oxygen flow rate into the reaction treatment zone 6 对. 3 The ratio of oxygen atoms to oxygen ions and the attenuation system are affected by k. Also, the axis represents the total gas &quot; (the total flow of oxygen and argon), the flow ratio of oxygen (02/Ar + 〇 2) and 25 1298355 argon relative to the introduction of the reaction treatment zone 60. Flow ratio (Ar/Ar+〇2). The vertical axis on the left side of Fig. 12 represents the luminous intensity ratio of oxygen atoms to oxygen ions, and the right vertical axis represents the attenuation coefficient. The luminous intensity ratio was measured by the aforementioned luminescence spectrometry. Regarding the attenuation coefficient, when the optical constant (complex refractive index) is N and the refractive index is „, it is a value represented by the relationship of N=n+ik. According to the results of Fig. 12, the argon flow ratio is about 0.15. In the range of ~0.45, the attenuation coefficient will be drastically reduced to less than about 2〇χ1〇_4. Therefore, in this range, a good film with a low attenuation coefficient can be produced. Especially, when the argon flow ratio is about 0.20~〇. The range of 35, the attenuation coefficient k is further lowered to about 0.8x10-4 or less, so it is more preferable. When the argon flow ratio is ο.", it is more preferable because the attenuation coefficient is the smallest. In this example, since the insulator is coated on the partition wall 16 and the portion of the inner wall surface of the vacuum vessel 11 facing the reaction treatment zone 60 as described above, the oxygen radical density in the plasma of the reaction treatment zone 60 can be maintained at a high level. . * The experimental results in Fig. 8 are for the case where the protective layer p (used to cover the vacuum: the portion of the inner wall surface of the thief 11 facing the reaction treatment zone 6 )) is composed of components, and the excitation existing in the plasma is measured by luminescence spectroscopy. The result of the luminescence intensity of the state oxygen radical. The horizontal axis of the head 8 represents the power applied by the high-frequency power source 69. The vertical axis represents the luminous intensity ratio. As shown in Fig. 8, compared with the case where the protective layer p is not provided (the experimental result of "stainless steel" in Fig. 8), the pyrolysis nitride side (touch), the oxide (1) also, and the bismuth (si) 2) When the protective layer p is formed to cover the partition walls 16, the latter has a high luminous intensity of oxygen radicals, and it is understood that the oxygen radical density is high. In particular, the protective layer p composed of pyrolytic nitridation_N) is coated with a partition wall ’ 26 1298355. The luminescent intensity of the oxygen radical is the strongest. Fig. 9 is a view showing the flow density of oxygen radicals in the plasma generated in the reaction treatment zone, where the pair is in the case where the partition wall 16 and the vacuum vessel 11 are coated with pyrolytic boron nitride (PBN), and the case where they are not covered. Compare it. In the present experimental example, as the partition wall 16 and the vacuum vessel 11 are coated with pyrolytic boron nitride (PBN), the partition wall 16 faces the reaction treatment zone 6〇 side, and the partition wall of the inner wall surface of the vacuum vessel 11 is partitioned. The portion of the 16 surrounding the reaction treatment zone 60 is coated with pyrolytic boron nitride.

圖9之橫軸代表導入反應處理區6〇之氧氣流量，縱軸 代表反應處理區60所產生之電漿中之氧自由基流量密度。 又，圖9縱軸所示之氧自由基流量密度值，係代表絕對流 量密度值。絕對流量密度值由銀薄膜的氧化程度而求得。 亦即，以基板保持具13來保持形成有銀薄膜之基板，根 據反應處理區60中之電漿處理前後薄膜的重量改變來測 量銀的氧化程度，根據該氧化程度來計算絕對流量密度 值。從圖9可看出，當用熱解氮化硼被覆間隔壁16與真 空容器11的情形，氧自由基的流量密度較高。 以上是針對製作所要組成的氧化矽（Si〇x(M2)薄膜做 說明，但不僅設置_個而設置複數個濺鍍用成膜處理區來 進行濺鍍處理時，可反覆積層不同組成的薄^_目^ 薄膜。例如’像上述般，在麟裳置U置成膜處理區40, 使用銳_作為乾49a、49b。以相同於製作氧切薄膜時 的方法’纟氧化矽薄膜上形成所要組成之氧化鈮 ⑽0把2·5))薄膜。接著，進行成膜處㈣20之濺鐘、 27 1298355 反應處理區60之電漿處理造成的氧化、成膜處理區40之 滅鍍、反應處理區6G《電漿處理造成的氧化，反覆進行 前述步驟’即可反覆積層所要組成的氧化石夕（叫㈣）薄 膜與氧化鈮（Nb0y(成.5))薄膜而形成目的薄膜。 特別是，在本例中，藉由使用具備電漿產生裝置61之 濺鍍裝置1，T製作出緻密且品質良好的高性能薄膜。其 效果顯示於圖1 0、圖11。 圖圖11係顯示形成氧化石夕（以〇2)與氧化銳⑽也） 多層薄膜時之薄膜透過率。目1〇的實驗結果，係取代濺 鍵裝置1之電漿產生裝置61而使用習知電漿產生裝置161 來形成氧化石卜氧化銳多層薄膜的情形；目11的實驗結果， 係使用本例之電漿產生裝置6丨來形成氧化秒—氧化銳多層 薄膜的h形。目i 〇、圖i i之橫軸代表測定波長，縱轴代 表透過率。 ^用‘知電漿產生裝置1 61的情形，係以高頻電源1 6 9 她加、5:5KW 電壓，並以 SiO2 = 0.3nm/s、Nb2〇5 = 〇.2nra/S 的 速度成膜。然後，依Si02層、Nb2〇5層的順序反覆積 層 人，製作出總物理膜厚94 0nra的薄膜。結果可製作 出，於測定波長65〇nm下衰減係數k=1〇〇xl〇—5之薄膜（圖 10)。 'The horizontal axis of Fig. 9 represents the oxygen flow rate introduced into the reaction treatment zone 6,, and the vertical axis represents the oxygen radical flow density in the plasma generated by the reaction treatment zone 60. Further, the oxygen radical flow density value shown on the vertical axis of Fig. 9 represents the absolute flow density value. The absolute flow density value is determined by the degree of oxidation of the silver film. That is, the substrate on which the silver thin film is formed is held by the substrate holder 13, and the degree of oxidation of the silver is measured according to the change in weight of the film before and after the plasma treatment in the reaction treatment zone 60, and the absolute flow density value is calculated based on the degree of oxidation. As can be seen from Fig. 9, when the partition wall 16 and the vacuum vessel 11 are coated with pyrolytic boron nitride, the flow density of oxygen radicals is high. The above is a description of the yttrium oxide (M2) film to be formed in the production process. However, when a plurality of sputtering film forming processing regions are provided for the sputtering process, the thin layers of different compositions may be laminated. ^_目^ Film. For example, as described above, in the film forming treatment zone 40, the sharp film is used as the dry film 49a, 49b. The same method as in the case of producing the oxygen-cut film is formed on the ruthenium oxide film. The yttrium oxide (10) 0 to be composed of 2·5)) film. Next, the oxidation at the film formation (4) 20, the oxidation treatment by the plasma treatment of the reaction treatment zone 60, the deplating of the film formation treatment zone 40, the oxidation of the reaction treatment zone 6G "plasma treatment", and the above steps are repeated. 'The oxide film of the oxidized stone (called (4)) and the film of yttrium oxide (Nb0y (.5)) to be formed can be repeatedly formed to form the target film. In particular, in this example, a dense and high-quality high-performance film is produced by using the sputtering apparatus 1 having the plasma generating device 61. The effect is shown in Fig. 10 and Fig. 11. Figure 11 is a graph showing the film transmittance when forming a multilayer film of oxidized stone (by 〇2) and oxidized sharp (10). The result of the experiment is to replace the plasma generating device 61 of the sputtering device 1 and use the conventional plasma generating device 161 to form an oxide oxide multilayer film; the experimental result of the object 11 is to use this example. The plasma generating device 6 is formed to form an h-shape of the oxidized second-oxidation sharp multilayer film. The horizontal axis of the figure i i represents the measurement wavelength, and the vertical axis represents the transmittance. ^In the case of 'Knife-electrical plasma generating device 1 61, the high-frequency power supply is used to increase the voltage of SiO2 = 0.3nm/s and Nb2〇5 = 〇.2nra/S. membrane. Then, the laminate was laminated in the order of the SiO 2 layer and the Nb 2 〇 5 layer to prepare a film having a total physical film thickness of 94 0 nra. As a result, a film having an attenuation coefficient of k = 1 〇〇 xl 〇 -5 at a measurement wavelength of 65 Å was produced (Fig. 10). '

Xp 方面’使用本例的具備電漿產生裝置6丨之濺鐘裝 置 的^开^ ’係以高頻電源69施加4· OKw電壓，並以 2 5nm/s、Nb205 = 〇. 4nm/s的速度進行成膜。並依si〇2 層、ΝΜ5層的順序反覆積㉟38次，製作出總物理膜厚In the Xp aspect, the voltage of the oscillating clock device of the present embodiment is applied with a high-frequency power source 69, and the voltage of 4·OKw is applied at 25 nm/s, and Nb205 = 〇. 4 nm/s. The film is formed at a speed. And according to the order of si〇2 layer and ΝΜ5 layer, 3538 times, the total physical film thickness is produced.

28 1298355 3242nra的薄膜。結果可萝作φ 禾J I作出，於測定波長65〇nm下衰減 係數k = 5xl0 — 5之薄膜（圖u)。 . 如此般，從結果(使用本例的具備電聚產生裝置61之 ' 錢裝置1來形成氧切-氧化銳多層薄膜的情形）可明顯 •看出’只要使用本例的濺鑛裝置1進行電漿處理來製作薄 媒，即可製作出低衰減係數（吸收係數）之良好薄膜。 又，關於衰減係數k，當光學常數（複折射率）為N、折 射率為n時，係依N=n+ik的關係所代表的數值。 以上所說明的實施形態，例如能做下述⑷〜⑴般的變 化。又將（a)〜⑴予以適當地組合亦可。 (a) 在上述實施形態，作為電漿產生機構，如圖1〜圖3 所示，係採用將天線65a、65b固定於板狀電介質壁63而 成之感應耦合型（平板型）電漿產生機構，但本發明也適用 於採用其他型式的電漿產生機構之薄膜形成裝置。亦即， 就异採用具備感應耦合型（平板型）以外的電漿產生機構而 φ 成的薄膜形成裝置時，藉由將絕緣體被覆於真空容器工工 内壁面之面向反應處理區60的部分、及電漿會聚壁，即 可和上述實施形態同樣地，藉電漿產生機構而產生於電漿 中之自由基或激勵狀態之自由基，因其與真空容器内壁面 戈電桌會5^壁的壁面反應而消滅的情形會被抑制住。作為 感應耦合型（平板型）以外的電漿產生機構，例如可列舉平 行平板型（二極放電型）、ECR(電子迴旋加速器共振）型、磁 控型、螺旋波型、感應耦合型（圓筒型）等等。 (b) 上述實施形態中，作為薄膜形成裝置的例子，係針 29 1298355 對,锻製置作說明，但本發明也適用於其他型式的薄膜形 成裝置。作為薄膜形成裝置’例如也可以是使用電漿進行 蝕2之蝕刻裝置、使用電漿進行CVD之CVD裝置等等。又， 也月b適用於使用電聚進行塑膠表面處理之表面處理裝置。 、（C)在上述實施形態，係採用所謂旋轉型濺鍍裝置，但 並不限於此。本發明也能適用於使基板面向電漿產生區域 來搬送之其他丨賤链裝置。 口 (d)在上述實施形態，係在間隔壁16之面向反應處理 品 的土面上、及真空容器11内壁面之面向反應處理區 60的部分，形成絕緣體構成的保護層p，但在其他部分也 月匕I成、、δ緣體構成的保護層p。例如，除間隔壁1 6之面向 反應處理區6G的壁面，也能在間隔壁16之其他部分被覆 絕緣體。藉此，能儘量避免自由基與間隔Μ 16反應所造 成之自由基減少。又，除在真空容器u内壁面之面向反 應處理區60的部分，也能在真空容器11内壁面之其他部 分、例如内壁面全體上被覆絕緣體。藉此，能儘量避免自 由基與真空容器U内壁面反應所造成之自由基減少。又 在間隔壁12上被覆絕緣體亦可。 (e)上述實施形態中，係用固定板68a、68b與電介質 壁63來挟持天線65a、65b，並用螺栓68〇、㈣來將固定 板_、6813固定於蓋體111}，藉此來固定天線6^、6^， 但只要將天線65a、65b固定成能調整間@ D，#然也能採 用其他做法。例如，事先將天線65a固定在固定板6。， 將天線65b固定在固定板68b，並在蓋體nb設置能使螺 30 1298355 栓68c、68d上下滑動的長孔。然後 又，口上下方向滑動固定 板68a、68b來選定間隔並以所要的p卩 所要的間隔°將螺栓68c、 68d鎖緊，而將固定板68a、68b定位在28 1298355 3242nra film. The result can be obtained as a film having a coefficient of attenuation k = 5x10 - 5 at a measurement wavelength of 65 〇 nm (Fig. u). In this way, from the result (in the case of using the 'money device 1 having the electropolymerization device 61 of this example to form the oxygen-cut-oxidation sharp multilayer film), it can be clearly seen that 'as long as the sputtering apparatus 1 of this example is used Plasma treatment to produce a thin medium produces a good film with a low attenuation coefficient (absorption coefficient). Further, regarding the attenuation coefficient k, when the optical constant (complex refractive index) is N and the refractive index is n, it is a value represented by the relationship of N = n + ik. The embodiment described above can be changed, for example, in the following (4) to (1). Further, (a) to (1) may be combined as appropriate. (a) In the above embodiment, as the plasma generating mechanism, as shown in Figs. 1 to 3, an inductive coupling type (flat plate type) plasma in which the antennas 65a and 65b are fixed to the plate dielectric wall 63 is used. Mechanism, but the present invention is also applicable to a film forming apparatus using other types of plasma generating mechanisms. In other words, when a thin film forming apparatus having a plasma generating mechanism other than the inductive coupling type (flat type) is used, the insulator is coated on the portion of the inner surface of the vacuum container that faces the reaction processing region 60, And the plasma can be gathered, and the free radical or the excited state free radical generated in the plasma can be generated by the plasma generating mechanism in the same manner as in the above embodiment, because it is connected to the inner wall of the vacuum vessel. The situation in which the wall reaction is eliminated will be suppressed. Examples of the plasma generating mechanism other than the inductive coupling type (flat plate type) include a parallel plate type (dipole discharge type), an ECR (electron cyclotron resonance type) type, a magnetron type, a spiral wave type, and an inductive coupling type (circle). Cartridge type and so on. (b) In the above embodiment, as a thin film forming apparatus, the knitting is described with respect to the knitting needle 29 1298355. However, the present invention is also applicable to other types of thin film forming apparatuses. As the thin film forming apparatus, for example, an etching apparatus using plasma etching 2, a CVD apparatus using plasma for CVD, or the like may be used. Also, the month b is suitable for a surface treatment apparatus for performing plastic surface treatment using electropolymerization. (C) In the above embodiment, a so-called rotary sputtering device is used, but the invention is not limited thereto. The present invention is also applicable to other chain-linking devices that transport substrates to the plasma generating region. In the above embodiment, the port (d) is formed as a protective layer p made of an insulator on the surface of the partition wall 16 facing the reaction-treated product and the portion of the inner wall surface of the vacuum vessel 11 facing the reaction treatment zone 60. The protective layer p composed of a part of the moon and the δ edge. For example, in addition to the wall surface of the partition wall 16 facing the reaction treatment zone 6G, the insulator can be covered in other portions of the partition wall 16. Thereby, the radical reduction caused by the reaction of the radical and the spacer Μ 16 can be avoided as much as possible. Further, in addition to the portion of the inner wall surface of the vacuum vessel u facing the reaction treatment zone 60, the insulator can be covered on the other portion of the inner wall surface of the vacuum vessel 11, for example, the entire inner wall surface. Thereby, the radical reduction caused by the reaction between the free radical and the inner wall surface of the vacuum vessel U can be avoided as much as possible. Further, the partition wall 12 may be covered with an insulator. (e) In the above embodiment, the antennas 65a and 65b are held by the fixing plates 68a and 68b and the dielectric wall 63, and the fixing plates _ and 6813 are fixed to the lid 111 by bolts 68 and (4), thereby fixing them. The antennas 6^, 6^, but the antennas 65a, 65b can be fixed to adjust the interval @ D, # other can also be used. For example, the antenna 65a is fixed to the fixed plate 6 in advance. The antenna 65b is fixed to the fixing plate 68b, and a long hole which can slide the screw 30 1298355 bolts 68c and 68d up and down is provided in the lid body nb. Then, the fixing plates 68a, 68b are slid in the up and down direction to select the interval and lock the bolts 68c, 68d at the desired interval of the desired p, and the fixing plates 68a, 68b are positioned at

甘盈® lib上下方向 之固定位置。 U (f)在上述實施形態，天線65a本體部65〜係由銅構成， 被覆層65a2係由銀構成，但只要本體部叫係由低成本加 工容易且低電阻的材料構成、電流集中之被覆層叫係由 電阻比本體部65ai低的材料構成即可，當然亦可採用其他 組合。例如’本體部65ai可由紹或銘銅合金構成，被覆層 65心係由銅、金構成。天線65b之本體部65\、被覆層 也能做同樣的改變。又，天線65a、65b也能分別由:同材2 料構成。 (g) 在上述實施形態，對反應處理區6〇導入的反應性 氣體是使用氧氣’但也能導入臭氧、一氧化二氮（N2〇)等的 氧化性氣體、氮等的氮化性氣體、甲烷等的碳化性氣體、 氧、四氟化碳（CFO等的氟化性氣體等等，而可將本發明運 用於氧化處理以外之電漿處理。 (h) 在上述實施形態，靶29a、29b的材料是採用石夕， 乾49a、49b的材料是採用銳，但並不限於此，也能採用其 等的氧化物。也能採用鋁（A1)、鈦（Ti)、鍅（Zr)、錫（sn)、 鉻（Cr)、鈕（Ta)、碲（Te)、鐵（Fe)、鎂（Mg)、铪（Hf)、鎳鉻 (Ni_Cr)、銦錫（In-Sn)等的金屬。也能採用這些金屬的化合 物，例如 A1203、Ti02、Zr02、Ta205、ΗίΌ2 等。當然，把 29a、29b、49a、49b的材料完全相同也可以。 31 1298355 使用廷些靶時，藉由反應處理區60之電漿處理，可製 作出· Al2〇3、Ti〇2、Zr〇2、Ta2〇5、si〇2、Nb2〇5、、 琴2等的光學膜或絕緣膜，lT〇等的導電膜，Fe2〇3等的 磁性膜，TiN、CrN、丁iC 等的超硬膜。Ti02、Zr〇2、Ta2〇5、 2 Nb2〇5等的絕緣性金屬化合物，由於濺鍍速度比金 屬（Ti、Zr、Si)慢报多而生產性不佳，因此使用本發明之薄 膜形成裂置來進行電漿處理特別有效。 (1)在上述實施形態，靶29a、29b的材料相同，靶49a、 49b的材料相同，但 、 一妹用不冋材料也可以。使用同一金屬 構成的革巴時，如上诫私 _ 叙’猎由濺鍍可在基板上形成單一金 屬的不完全反應物，者你 田使用不同的金屬靶時，可在基板上 形成合金的不完全反應物。 、、、示上所述，依本發明 ^ Θ之溥膜形成方法及薄膜形成裝置， 可咼效率地進行電漿處理。 【圖式簡單說明】 圖1係本發明的薄艇 明圖 寻勝形成裝置之取局部截面之俯視說 圖 明圖 係本毛月的薄m形成裝置之取局部截面之側視說 圖3係電漿產生機槿 %攝之說明圖。 圖4係天線的截面圖。 圖5係顯示電聚中 例 乳原子與氧離子比例之實驗結果 圖 係”、、員不電|中激勵狀態的氧自由基、與氧離子的 κ 32 1298355 發光強度之實驗結果例。 圖7係顯示電漿中激勵狀態的氧自由基、與氧離子 發光強度之實驗結果例。 、 勵狀態的氧自由基發光強度之實 圖8係顯示電漿中激 驗結果例。 例 圖9係顯示電漿中氧自由基的流量密度之實 驗結果Gan Ying® lib fixed position in the up and down direction. U (f) In the above embodiment, the main body portion 65 to the antenna 65a is made of copper, and the coating layer 65a2 is made of silver. However, the main body portion is made of a material which is easy to process at low cost and has low resistance, and is coated with current concentration. The layer may be formed of a material having a lower electric resistance than the main body portion 65ai, and other combinations may of course be employed. For example, the body portion 65ai may be made of Shao or Ming copper alloy, and the core of the coating layer 65 may be made of copper or gold. The body portion 65\ of the antenna 65b and the coating layer can be similarly changed. Further, the antennas 65a and 65b can also be composed of the same material. (g) In the above embodiment, the reactive gas introduced into the reaction treatment zone 6 is oxygen gas, but an oxidizing gas such as ozone or nitrous oxide (N2〇) or a nitriding gas such as nitrogen can be introduced. The carbonization gas such as methane, oxygen, carbon tetrafluoride (fluorinated gas such as CFO, etc.) can be applied to plasma treatment other than oxidation treatment. (h) In the above embodiment, the target 29a The material of 29b is Shi Xi, and the materials of dry 49a and 49b are sharp, but it is not limited thereto, and the oxides thereof can also be used. Aluminum (A1), titanium (Ti), and niobium (Zr can also be used. ), tin (sn), chromium (Cr), button (Ta), bismuth (Te), iron (Fe), magnesium (Mg), hafnium (Hf), nickel chromium (Ni_Cr), indium tin (In-Sn) Metals such as A1203, Ti02, Zr02, Ta205, ΗίΌ2, etc. Of course, the materials of 29a, 29b, 49a, and 49b may be identical. 31 1298355 When using some targets, By the plasma treatment of the reaction treatment zone 60, Al2〇3, Ti〇2, Zr〇2, Ta2〇5, si〇2, Nb2〇5, Qin 2, etc. can be produced. Optical film or insulating film, conductive film such as lT〇, magnetic film such as Fe2〇3, super hard film such as TiN, CrN, butadiene, etc. Insulation of Ti02, Zr〇2, Ta2〇5, 2 Nb2〇5, etc. Since the metal plating compound has a slower rate of sputtering than the metal (Ti, Zr, Si) and has poor productivity, it is particularly effective to form a crack by using the film of the present invention to perform plasma treatment. (1) In the above embodiment The materials of the targets 29a and 29b are the same, and the materials of the targets 49a and 49b are the same, but it is also possible to use a material of the same material. When using the same metal to form the leather, the above-mentioned smuggling can be performed on the substrate by sputtering. Forming an incomplete reactant of a single metal, and when the field uses a different metal target, an incomplete reactant of the alloy may be formed on the substrate. The method for forming the tantalum film according to the present invention is as described above. And the film forming device can perform plasma processing efficiently. [Simplified illustration of the drawing] Fig. 1 is a plan view showing a partial cross section of the thin boat clear drawing forming device of the present invention. The side view of the partial section of the m-forming device is shown in Figure 3. Fig. 4 is a cross-sectional view of the antenna. Fig. 5 is a diagram showing the experimental results of the ratio of the milk atom to the oxygen ion in the electropolymerization, and the oxygen free in the excited state. Examples of experimental results of luminescence intensity of κ 32 1298355 with oxygen ions. Fig. 7 shows an example of experimental results of oxygen radicals and oxygen ion luminescence intensity in an excited state in plasma. Figure 8 shows an example of the results of the experiments in the plasma. Example Figure 9 shows the experimental results of the flow density of oxygen radicals in the plasma.

圖1〇顯不的實驗結果例，係針對 ^ ^ „ 了 4木用習知電漿產生機 構來开y成虱化矽、氧化鈮組成的多 日潯臈之透過率測定結 果。 圖11顯示的實驗結果例，係針對 τ *木用本發明雷％吝&amp; 機構來形成氧切、氧化隸成的 水產生 於果。 ㈢溥膜之透過率測定 固 i不蔣士 -広 υυ之氧氣流量比，： 對電水中乳原子與氧離子之比例、衰 r Μ 成係數k產生的影響 【主要70件代表符號】 11…真空容器 1 la…突緣 lib…蓋體 12、14、16···間隔壁 13…基板保持具 15、15’…真空泵 1 7…馬達 20、40…成膜處理區 21a、21b、41a、41b…磁控濺錢電極 33 1298355 23、 43···中頻交流電源 24、 44···變壓器 25、 26、45、46、75、76···質量流量控制器 27、 47…濺鍍氣體高壓容器 28、 48、78…反應性氣體高壓容器 29a、29b、49a、49b…革巴 60…反應處理區 61、161…電漿產生裝置 63…電介質壁 6 5 a、6 5 b…天線 65ai、65b:…本體部 65a2、65b2…被覆層 66…導線 6 6 a、6 6 b…伸縮部 6 7…匹配箱 67a、67b…可變電容器 68…固定具 68a、68b…固定板 68c、68d…螺栓 69、169…高頻電源 77…非活性氣體高壓容器 1 6 7 c…匹配用線圈 D···天線彼此之間隔 P…保護層The results of the experimental results shown in Fig. 1 are based on the results of the transmittance measurement of the multi-day 铌 composition of the 木 虱 铌 铌 铌 铌 铌 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The experimental results are based on the τ* wood using the Ray%吝&amp; mechanism of the present invention to form oxygen-cut and oxidized water. (3) Determination of the transmittance of the ruthenium film Flow ratio, the effect of the ratio of the milk atom to the oxygen ion in the electro-hydraulic water and the decay coefficient k [main 70 symbols] 11...vacuum container 1 la... flange lib... cover 12, 14, 16· · partition wall 13... substrate holder 15, 15'... vacuum pump 1 7... motor 20, 40... film forming processing area 21a, 21b, 41a, 41b... magnetically controlled splash electrode 33 1298355 23, 43··· intermediate frequency AC power supply 24, 44···Transformer 25, 26, 45, 46, 75, 76··· Mass flow controllers 27, 47... Sputter gas high pressure vessels 28, 48, 78... Reactive gas high pressure vessels 29a, 29b 49a, 49b...grain 60...reaction processing zone 61,161...plasma generating device 63...dielectric wall 6 5 a, 6 5 b... antenna 65ai, 65b: ... body portion 65a2, 65b2 ... coating layer 66 ... wire 6 6 a, 6 6 b ... expansion and contraction portion 6 7 ... matching box 67a, 67b ... variable capacitor 68 ... fixture 68a 68b...fixing plates 68c, 68d...bolts 69,169...high frequency power source 77...inactive gas high pressure container 1 6 7 c...matching coil D···interval of antennas P...protective layer

Ra···天線65a的直徑 34 1298355Ra···the diameter of the antenna 65a 34 1298355

Rb…天線65b的直徑 Z…基板保持具之中心軸線Rb...the diameter of the antenna 65b Z...the central axis of the substrate holder

3535

Claims (1)

1298355 2006年7月 專利申請案第94117842號申請專利範圍替換本 十、申請專利範圍： 1、一種薄膜形成方法，係使用薄膜形成裝置（將該真 空容器内的面向電漿產生區域的壁面用絕緣體被覆）對基 體進行薄膜形成；其特徵在於進行： 將真空容器内部維持真空之製程， 在配設於該真空容器之基體搬送機構上保持基體之基 體保持製程， 對成膜處理區導入非活性氣體以將靶 基體進行成膜處理之錢處理製程， 稭此❹ 將該成膜處理後之該基體搬送至反應處理區之基體搬 入反應性氣體及非活性氣體以產 理後之該基體進行電漿處理之電 對該反應處理區内導 生電漿，藉此對該成膜處 漿處理製程， 令A = 仃5亥成膜處理製程及該電漿處理製程來在 巧基體上形成薄膜。 ％ 2 '如中請專利範圍第 db ^ ^ 币1貝之/專膜幵》成方法，其中，該 非活性氣體為擇自氩、氦、^ ^忒 &quot; 夙、虱、氙所構成群中之氣體。 3、如申請專利範 絕緣體1擇自 項之薄膜形成方法，其中，該 遐係擇自熱解氮化爛 之絕緣體。 〜u %汉虱化矽所構成群中 如申睛專利蔚圖哲 對於導入w各項之薄膜形成方法，其中，和 量比為0.15〜〇.45的範圍，該非活性氣體之法 36 1298355 5、 如申請專利範圍第4項之薄膜形成方法，其中，节 流量比為〇· 27。 μ 6、 一種薄膜形成裝置，係具備：内部可維持真空之真 空容器，配設於該真空容器内、用來搬送基體之基=搬送 機構，形成於該真空容器内、用來對該基體進行成膜處理 之成膜處理區，形成於該真空容器内、用來對該基體進行 電漿處理之反應處理區，藉此來在基體上形成薄膜； 其特徵在於具備： 用來對該反應處理區導入反應性氣體之反應性氣體導 入機構， 用來個別對該成膜處理區及該反應處理區導入非活性 氣體之非活性氣體導入機構， 配設於該成膜處理區、用來藉由該非活性氣體將粗錢 蝕以對該基體進行成膜處理之成膜處理機構， 配設於該反應處理區、用來在該反應處理區内產生反 應性氣體及非活性氣體之電漿，藉此對該成膜處理後的基 體進行電漿處理之電漿產生機構； 將该真空谷器内的面向電浆產生區域的壁面用絕緣體被 覆。 7、如申請專利範圍第6項之薄膜形成裝置，其中， 該非活性氣體導入機構具備： 用以貯存非活性氣體之單一的非活性氣體貯存機構， 用來將貯存於該非活性氣體貯存機構之非活性氣體導 入該成膜處理區之第一配管，及 37 .1298355 用來將貯存於該非活性氣體貯存機構之非活性氣體導 入#亥反應處理區之第二配管。 8、如申請專利範圍第6項之薄膜形成裝置，其中，該 非活性氣體導入機構具備： 用以貯存非活性氣體之第一非活性氣體貯存機構； 用來將貯存於該第一非活性氣體貯存機構之非活性氣 體導入該成膜處理區之第一配管；1298355 Patent Application No. 94117842, July 2006 Patent Application No. 119, the scope of the patent application: 1. A film forming method using a film forming device (an insulator for a wall surface facing the plasma generating region in the vacuum container) Coating a film for forming a substrate; and performing the process of: maintaining a vacuum inside the vacuum container, maintaining a substrate holding process of the substrate on the substrate transfer mechanism disposed in the vacuum container, and introducing an inert gas into the film forming processing region The substrate treatment process of the target substrate is carried out, and the substrate after the film formation process is transferred to the substrate of the reaction treatment zone to carry in a reactive gas and an inert gas to perform plasma treatment on the substrate after the processing. The treated electricity conducts the plasma in the reaction treatment zone, thereby performing the film forming sizing treatment process, and the A = 仃5 hai film forming process and the plasma processing process to form a film on the slab. % 2 'For example, the patent scope is db ^ ^ 1 lb / / Membrane 幵", wherein the non-reactive gas is selected from the group consisting of argon, helium, ^^忒&quot; 夙, 虱, 氙Gas. 3. The method for forming a film according to the patent application of the invention, wherein the lanthanum is selected from the insulator of pyrolytic nitriding. 〜u % 虱 虱 矽 如 如 如 如 如 如 如 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 薄膜 薄膜 薄膜 薄膜 薄膜The film forming method of claim 4, wherein the throttle ratio is 〇·27. μ 6. A film forming apparatus comprising: a vacuum container in which a vacuum can be maintained inside, and a base for transporting a substrate in the vacuum container; a transfer mechanism formed in the vacuum container for performing the substrate a film forming treatment zone formed by a film forming process, a reaction processing zone formed in the vacuum vessel for plasma treatment of the substrate, thereby forming a film on the substrate; and characterized by: a reactive gas introduction mechanism for introducing a reactive gas into the region, and an inert gas introduction mechanism for introducing an inert gas into the film formation processing region and the reaction treatment region, and disposed in the film formation processing region for The non-reactive gas is a film forming treatment mechanism for performing a film forming treatment on the substrate, and is disposed in the reaction treatment zone for generating a reactive gas and an inert gas in the reaction treatment zone. The plasma generating mechanism that performs the plasma treatment on the substrate after the film formation process; and the wall surface facing the plasma generating region in the vacuum bar is covered with an insulator. 7. The film forming apparatus of claim 6, wherein the inert gas introduction mechanism comprises: a single inert gas storage mechanism for storing an inert gas for storing the non-reactive gas storage mechanism The active gas is introduced into the first pipe of the film forming treatment zone, and 37.1298355 is used to introduce the inert gas stored in the inert gas storage mechanism into the second pipe of the #海反应处理区. 8. The film forming apparatus of claim 6, wherein the inert gas introduction mechanism comprises: a first inert gas storage mechanism for storing an inert gas; and a storage device for storing the first inert gas Introducing a non-reactive gas of the mechanism into the first pipe of the film forming processing zone; 用以貯存非活性氣體之第二非活性氣體貯存機構，其 與該第一非活性氣體貯存機構分開設置；及 用來將貯存於該第二非活性氣體貯存機構之非活性氣 體導入該反應處理區之第二配管。 如曱清專利範圍第 反應性氣體導入機構係具備反應性氣體流量調整機構，其 可調整導入該反應處理區之反應性氣體流量； 且該反應性氣體流量調整機構係具備 ^ 两非活性氣體流量 調整機構，其可調整導入該反應處理區 曰 L•之非活性氣體流 〇 任—項之薄膜形成 氦、氖、氪、氙所 1 0、如申請專利範圍第6至9項中 裝置’其中’該非活性氣體為擇自氬、 構成群中之氣體。 11、如申請專利範圍第6項之薄膜形成裝置，其中， 用該絕緣體被覆之該真空容器内的壁面， 1系該真空容器之 12、如申請專利範圍第6項之薄膜形成裝置，其中 38 1298355 該絕緣體，係擇自熱解氮化硼、氧化鋁及氧化矽所構成群 中之絕緣體。 十一、圖式： 如次頁a second inert gas storage mechanism for storing an inert gas, which is disposed separately from the first inert gas storage mechanism; and for introducing an inert gas stored in the second inert gas storage mechanism into the reaction process The second piping of the area. For example, the reactive gas introduction mechanism of the patent scope includes a reactive gas flow rate adjusting mechanism that adjusts the flow rate of the reactive gas introduced into the reaction treatment zone; and the reactive gas flow rate adjustment mechanism has two inert gas flow rates An adjustment mechanism capable of adjusting a film formed into an inert gas stream of the reaction treatment zone 氦L• 氦, 氖, 氪, 氙, 10, as in the device of the scope of claims 6 to 9 'The inert gas is a gas selected from the group consisting of argon. 11. The film forming apparatus of claim 6, wherein the wall surface of the vacuum container covered with the insulator, 1 is the vacuum container 12, and the film forming apparatus of claim 6 of the patent scope, wherein 38 1298355 The insulator is selected from the group consisting of pyrolytic boron nitride, aluminum oxide and yttrium oxide. XI. Schema: as the next page 3939