TW200912017A - Conductive and protective film and method for producing the same - Google Patents
Conductive and protective film and method for producing the same Download PDFInfo
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- TW200912017A TW200912017A TW097114350A TW97114350A TW200912017A TW 200912017 A TW200912017 A TW 200912017A TW 097114350 A TW097114350 A TW 097114350A TW 97114350 A TW97114350 A TW 97114350A TW 200912017 A TW200912017 A TW 200912017A
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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Abstract
Description
200912017 九、發明說明 【發明所屬之技術領域】 本發明係有關具有高硬度和耐磨耗性之導電性類鑽碳 (D L C )保護膜及其製造方法。 【先前技術】 導電性保護膜係爲對於各種構件而言，以導電性被覆 耐久性高的膜，使電極構件等之導電性保護膜耐久性提升 之構成，而以往類鑽碳係根據高硬度和耐磨耗性而使用於 各種構件，但未做爲絕緣性高之導電性被膜所使用，近年 ，開發有幾個方法，但兼具導電性與高硬度•耐磨耗性之 情況係爲困難，而並未有做爲導電性保護膜所利用之構成 〇 另一方面，關於導電性類鑽碳之製造，知道有經由成 膜條件或氮素摻雜而控制類鑽碳（DLC )被膜構造，做爲 導電性表面強化被膜層所使用之技術（專利文獻1 ) ’但 有著硬度下降的問題和導電性亦無法提升之問題，另外’ 做爲關於導電性類鑽碳被膜之其他的提案係有著專利文獻 2，但有導電性與硬度係有做爲反比例之傾向，爲了提升 導電性而必須下降硬度之問題，不適合保護膜之構成’更 加地，亦提案有摻雜具有高毒性之乙硼烷或膦所製作之非 晶形碳膜’但雖表示有其阻抗率至1 χ 1〇8 Ω · cm爲止係下 降者，但有阻抗率依然爲高之不利（專利文獻3 )。 〔專利文獻1〕日本特表平9-508613號公報 200912017 〔專利文獻2〕日本特開2 0 0 4 - 2 1 7 9 7 5號公報 〔專利文獻3〕日本特開平1 - 2 4 5 5 6 2號公報 【發明內容】 〔欲解決發明之課題〕 本發明者們係有鑑於上述之以往技術問題，開發使高 硬度•耐磨耗性與導電性並存之新的導電性類鑽碳保護膜 之製造方法，重覆銳意硏究之結果，發現可得到具有高強 度之新的導電性類鑽碳表面強化被覆層之情況，完成本發 明。 本發明之目的係提供使用特定之成膜方法而兼具高硬 度和耐磨耗性之導電性類鑽碳保護膜及其製造方法。 〔爲解決課題之手段〕 爲了解決上述課題，本發明之導電性保護膜之製造方 法的第1型態，屬於保護基板之導電性保護膜之製造方法 ’其特徵乃使用以特定比例導入碳化氮系原料氣體和硼（ Β)摻雜氣體之混合氣體，將含有特定量的硼（Β)之導 電性類鑽碳被膜，形成於前述基板上者。 本發明之導電性保護膜之製造方法的第2型態，屬於 保護基板之導電性保護膜之製造方法，其特徵乃包含對於 前述基板表面而言，進行經由離子轟擊之前處理的前處理 工程’和於做爲前述前處理之基板表面，將作爲電阻接觸 之中間層，進行成膜處理之中間層形成工程，和使用以特 200912017 定比例導入碳化氫系原料氣體和硼摻雜氣體 將含有特定量的硼之導電性類鑽碳被膜，形 層的表面之類鑽碳被膜形成工程，而經由組 觸之中間層和類鑽碳被膜之情況，更可使導 前述中間層乃理想爲從選自碳（C )， (A g ) ’銦（I η )，鋁（a 1 )，磷（P )， (Ni )，鉻（Cr) ’ ITO ( In2〇3-Sn〇3 )， 石夕（S i )所成的群之一種或二種以上所形成 做爲前述硼（B )摻雜氣體，最佳爲使 甲酯（三甲基硼酸酯），三甲基硼及三乙基 一種或二種以上者。 做爲碳化氫原料氣體，使用選自環己烷 甲烷，丁基苯，甲苯及環戊烷所成的群之一 之氣體種者。 做爲前述類鑽碳被膜之厚度，係理想f 之情況，做爲前述中間層的厚度，係理想爲 〇 前述中間層的形成係如經由電漿CVD 離子化蒸鍍法，蒸鍍法，印刷法或電鍍而進 佳爲濺鍍法，而期望爲經由離子化蒸鍍法而 性類鑽碳被膜者。 將前述導電性類鑽碳被膜之成膜時的前 ，做爲3 5 0。(：以下之情況者爲理想’經由該 板的熱變形等，控制爲最小限度’進而可得 之混合氣體， 成於前述中間 合進行電阻接 電性提升。 金（Au)，銀 鈦（Ti)，鎳 ZnO ， Ti02 及 者。 用選自硼酸三 硼所成的群之 ，苯，乙炔’ 種或二種以上 I 0.005 〜3 //m 0.005 〜10/z m 法，濺鍍法， 行即可，但最 形成前述導電 述基板之溫度 方法，可將基 到耐磨耗性與 -6- 200912017 導電性更優越之類鑽碳被膜者。 本發明之導電性保護膜係經由本發明之導電性保護膜 之製造方法所製造，其特徵乃由兼備硼（B)含有量爲 0.01~5atomic%’且壓痕硬度爲9000〜30000MPa之硬度， 比磨耗率爲1 . 0 X 1 0 _1 9〜1 . 〇 X 1 (Γ 15 m 2 /N之耐磨耗性，及阻抗 率爲Ι.ΟχΙΟ·4〜1_〇χ102Ω .cm之導電性的類鑽碳被膜而成 者’然而’針對在本發明，阻抗率係如經由四點探針法或 四點量測（Van der Pauw)法而測定即可，而本發明之導 電性保護膜係可得到對於針對在酸•鹼溶液或氧化•環園 環境之耐腐蝕性優越之效果。 針對在本發明係爲對於類鑽碳，使用安全氣體之硼酸 三甲酯或三甲基硼等之碳化氫系氣體，摻雜硼（0.01〜5 atomic% )，由以特定的成膜方法而生成導電性類鑽碳之 情況，製作兼備高硬度與耐磨耗性之導電性保護膜之構成 ，另外，根據情況，經由組合進行電阻接觸（接觸電阻低 )之中間層和類鑽碳（DLC )被膜而使用之情況，亦更可 使導電性提升。 發明之效果 如根據本發明，經由使用特定的氣體種而採用根據離 子化蒸鍍法所形成之特定的導電性類鑽碳（DLC )被膜之 情況，或經由組合前述類鑽碳（DLC )被膜，和因應必要 而進行電阻接觸之中間層而使用之情況，可形成做爲導電 性表面強化被膜層，兼備壓痕硬度爲9000〜3 00 00MPa之 200912017 硬度，比磨耗率爲l.〇xl〇-19〜l.〇xl〇_15m2/N之耐磨耗性， 及阻抗率爲1.0 XI 0_4〜1.0 Χίο2 Ω . cm之導電性的類鑽碳（ DLC )被膜，隨之爲作爲各種構件之導電性保護膜而得到 大的效果之構成。 【實施方式】 〔爲了實施發明之最佳型態〕 以下，說明本發明之實施形態，但此等實施形態係爲 例示所示之構成，在不脫離本發明之技術思想，當然可做 各種變更。 本發明之導電性保護膜的製造方法之第1實施形態係 爲如圖1所示，於基板1 0上，形成導電性保護膜12之構 成的導電性保護膜的製造方法，其中，如圖2所示，作爲 對於基板1 〇之前處理，進行離子轟擊，電漿洗淨基材（ 圖2之步驟100)，該離子轟擊係最佳爲經由Ar等之稀 有氣體或混合Η之稀有氣體而進行。 接著，使用以特定比例導入碳化氫系原料氣體和硼摻 雜氣體之混合氣體，將含有特定量的硼之導電性類鑽碳被 膜12，形成於前述基板1〇上者（圖2之步驟102)。 作爲爲了形成前述導電性類鑽碳被膜12之手段，係 知道有離子化蒸鏟法，輝光放電或使用高頻率電漿之電漿 CVD法’經由紫外線激發的光CVD法，微波CVD法，濺 鍍法’電弧放電法等，但最佳爲離子化蒸镀法，針對在本 實施形態係關於使用離子化蒸鍍法之情況，進行說明，然 -8- 200912017 而，針對在離子化蒸鍍法’因使用非平衡電漿而成膜 基板1 〇的溫度係通常爲3 5 0 °C以下，並有將基板1 〇 變形等，作爲最小限度之利點。 作爲實施本發明之導電性保護膜的製造方法之裝 係可使用圖5所示之構造的裝置，針對在圖5，2 0係 電性保護膜的製造裝置’具有真空腔室22，於該真 室2 2之上部’係設置有保持基板1 〇之基板保持部 另外’對於該真空腔室22之下部，係設置有陽極26 絲2 8及硼摻雜氣體導入口 3 0，更加地，對於該真空 22之側壁22a係設置有碳化氫系原料氣體導入口 32 而’碳化氫系原料氣體導入口 32係亦可設置於真空 22之底壁22b或上壁22c。 針對在本發明所適用之離子化蒸鍍法係可將真空 2 2進行減壓（例如，至3 X 1 0 ·3 P a以下進行真空吸引 以低溫進行薄膜形成，利用電將激發而使原料氣體分 於基板1〇’施加負電壓而使膜堆積之方法，具體而 當於前述導電性保護膜之製造裝置20的真空腔室22 以特定比例導入乙炔，苯（C6H6 )氣體或其他碳化氫 料氣體和硼摻雜氣體時，使用熱燈絲28與陽極26而 離子源29 ’經由直流電弧放電電漿，生成碳化氫宿 或所激發之自由基，所生成之碳化氫離子係於偏壓於 之負電壓的基板10，由因應偏壓電壓的能量，產生 而作爲固體化，如圖1所示，含有特定量的硼之導電 鑽碳被膜1 2則形成於基板丨〇上。 時之 的熱 置， 爲導 空腔 24， ，燈 腔室 ，妖 \\ 腔室 腔室 )， 解， 言， 中， 系原 成之 離子 直流 衝突 性類 -9- 200912017 爲了形成前述導電性類鑽碳被膜1 2 ’作爲前述碳化 氫系原料氣體，使用選自環己烷，苯，乙炔’甲院’丁基 苯，甲苯及環戊烷所成的群之一種或二種以上之氣體種者 〇 做爲前述硼摻雜氣體，最佳爲使用選自硼酸5$@ ( 三甲基硼酸酯），三甲基硼及三乙基硼所成的群之一種或 二種以上者，另外，碳化氫系原料氣體與硼摻雜氣體係其 混合比爲1 (碳化氫系原料氣體）：1 (硼摻雜氣體） 〜1 00 : 1之範圍，理想爲最佳使用在2 : 1〜3 0 : 1之範圍 者。 爲了形成前述導電性類鑽碳被膜1 2，理想爲使用離 子化蒸鍍法者’其理由係因可經由燈絲2 8與陽極2 6，可 控制電將條件，可經由基板電壓，控制離子轟擊’由此’ 成爲可保持類鑽碳之構造的同時，使硼活性化之情況。 本發明之導電性保護膜的製造方法之第2實施形態係 爲如圖3所示’於基板1 〇與導電性保護膜12之間，使中 間層11介入存在之構成的導電性保護膜的製造方法，如 圖4所示，首先’與圖2同樣地，作爲對於基板1〇之前 處理’經由Ar等之氣體，進行離子轟擊，將基材，進行 洗淨（圖4之步驟10〇)。 接者’於做爲前述前處理之基板1 〇的表面，成膜形 成進行電阻接觸之中間層n (圖4之步驟1 〇丨），其中間 層1 1 ί系使用Μ自@ ’金’銀，銦，鋁，磷，鈦，鎳，鉻 ,ITO ( In203-Sn〇3 ) , Zn〇，Ti〇2 及矽所成的群之—種 -10- 200912017 或二種以上而成膜形成者，而中間層1 1之形成係 電漿CVD法，濺鍍法，離子化蒸鍍法，蒸鍍法， 或電鍍而進行即可，但最佳爲濺鍍法。 接著，與圖2同樣地，使用以特定比例導入碳 原料氣體和硼摻雜氣體之混合氣體，經由離子化蒸 將含有特定量的硼之導電性類鑽碳被膜12，形成 基板1 〇上者（圖4之步驟1 〇 2 )，如此，經由組 電阻接觸之中間層1 1和類鑽碳被膜1 2之情況，更 電性提升，然而，導電性類鑽碳被膜1 2之形成係 1及圖2之情況同樣，故省略再次之詳細說明。 經由含於作爲前述中間層1 1而使用之上述氣 自碳’金，銀，銦，鋁，磷，鈦，鎳，鉻，ITO ( Sn03 ) ，ZnO，Ti02及矽所成的群之一種或二種以 料而成膜形成之進行電阻接觸之中間層1 1和類鑽 1 2 ’則因電組接觸而可降低控制電力損失者。 經由本發明之導電性保護膜的製造方法，可得 硼含有量爲0.01〜5atomic%，且壓痕硬度爲9000 MPa之硬度，比磨耗率爲ι.οχίο·19〜l.〇xi〇-15m2/N 耗性，及阻抗率爲1.0 xl 〇_4~ 1.0 χΙΟ2 Ω .cm之導電 鑽碳被膜’然而，阻抗率係如經由四點探針法或四 (Van der Pauw )法而測定即可。 作爲適用本發明方法之基板，係無特別限定， 出例如，玻璃基板，S i基板，金屬基板，陶瓷基 料基板及於此等基板，施以各種金屬電鍍（例如， 如經由 印刷法 化氫系 鍍法， 於前述 合進行 可使導 因與圖 體之選 Ιη203- 上的材 碳被膜 到兼備 〜30000 之耐磨 性的類 點量測 但可舉 板，塑 鍍金） -11 - 200912017 之基板等。 實施例 以下舉出實施例，更具體說明本發明，但此等 係因爲爲例示所示之構成，當然並非爲限定所解釋 (實施例1 ) 作爲BU處理，由將A r導入1 4 s c c m，將基板電 2 k V ’陽極電流〇 . 8 A，進行1小時離子轟擊之後， 的實驗條件，於石英玻璃基板上，中間層係未進行 進行硼摻雜，將類鑽碳，作爲1 · 1 8 // m成膜。 實施條件 氣體流量：原料氣體（苯）··硼酸三甲酯= seem200912017 IX. Description of the Invention [Technical Field] The present invention relates to a conductive diamond-like carbon (D L C ) protective film having high hardness and wear resistance and a method for producing the same. [Prior Art] The conductive protective film is a film having high durability by conductive coating for various members, and the conductive protective film such as an electrode member is improved in durability, and the conventional diamond-like carbon is based on high hardness. And it is used for various components, but it is not used as a conductive film with high insulation. In recent years, several methods have been developed, but the combination of conductivity and high hardness and wear resistance is Difficult, but not used as a conductive protective film. On the other hand, regarding the manufacture of conductive diamond-like carbon, it is known to control the diamond-like carbon (DLC) film through film formation conditions or nitrogen doping. The structure used as a conductive surface-strengthening film layer (Patent Document 1) 'But there is a problem that the hardness is lowered and the conductivity cannot be improved, and the other is a proposal for a conductive diamond-like carbon film. There is Patent Document 2, but there is a tendency for conductivity and hardness to be inversely proportional. In order to improve conductivity, the hardness must be lowered, and it is not suitable for the composition of the protective film. It is also proposed to have an amorphous carbon film made of highly toxic diborane or phosphine, but although the impedance is reduced to 1 χ 1 〇 8 Ω · cm, the resistivity is still high. Disadvantages (Patent Document 3). [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-508613 (Publication No. 2) Japanese Patent Application Laid-Open No. Hei 2 0 0 4 - 2 1 7 9 7 5 (Patent Document 3) Japanese Patent Laid-Open No. 1 - 2 4 5 5 In the inventors of the present invention, in order to solve the above-mentioned conventional problems, the present inventors have developed a new conductive diamond-like carbon protection that combines high hardness, wear resistance, and electrical conductivity. As a result of the method for producing a film, it was found that a new conductive diamond-like carbon surface-enhancing coating layer having high strength was obtained, and the present invention was completed. SUMMARY OF THE INVENTION An object of the present invention is to provide a conductive diamond-like carbon protective film which combines high hardness and wear resistance using a specific film forming method, and a method for producing the same. [Means for Solving the Problems] In order to solve the above problems, the first aspect of the method for producing a conductive protective film of the present invention is a method for producing a conductive protective film for protecting a substrate, which is characterized in that a nitrogen carbide is introduced at a specific ratio. A mixed gas of a source gas and a boron (cerium) doping gas, and a conductive diamond-like carbon film containing a specific amount of boron (germanium) is formed on the substrate. A second aspect of the method for producing a conductive protective film of the present invention relates to a method for producing a conductive protective film for protecting a substrate, which comprises a pretreatment process for performing a treatment before ion bombardment on the surface of the substrate. And the intermediate layer forming process as the intermediate layer of the resistive contact, and the intermediate layer forming process of the film forming process, and the introduction of the hydrocarbon-based raw material gas and the boron doping gas in a specific ratio of 200912017 will contain a specific The amount of boron-based conductive diamond-like carbon film, the surface of the layer is shaped like a carbon film, and the intermediate layer and the diamond-like carbon film can be used to guide the intermediate layer. From carbon (C), (A g ) 'indium (I η ), aluminum (a 1 ), phosphorus (P), (Ni), chromium (Cr) 'ITO (In2〇3-Sn〇3), Shi Xi One or more of the groups formed by (S i ) are formed as the boron (B) doping gas, and the methyl ester (trimethyl borate), trimethylboron and triethyl are preferred. One or more. As the hydrocarbon raw material gas, a gas species selected from the group consisting of cyclohexane methane, butylbenzene, toluene and cyclopentane is used. The thickness of the diamond-like carbon film is preferably f. The thickness of the intermediate layer is preferably 〇. The formation of the intermediate layer is performed by plasma CVD, vapor deposition, evaporation, and printing. The method of sputtering or plating is preferably a sputtering method, and it is desirable to be a carbon-coated film by ionization vapor deposition. Before the film formation of the above-mentioned conductive diamond-like carbon film, it is 305. (In the following cases, it is desirable to control the mixture to a minimum by thermal deformation of the plate, etc., and to obtain a mixed gas in the middle of the combination. Gold (Au), silver titanium (Ti) ), nickel ZnO, Ti02 and the group formed by a group selected from triboron borate, benzene, acetylene 'species or two or more I 0.005 ~ 3 / m 0.005 ~ 10 / zm method, sputtering method, line However, the temperature method for forming the substrate of the above-mentioned conductive substrate can be used to obtain a carbon-coated film which is superior in abrasion resistance and conductivity to -6-200912017. The conductive protective film of the present invention is electrically conductive according to the present invention. The method for producing a protective film is characterized in that the boron (B) content is 0.01 to 5 atomic% and the indentation hardness is 9000 to 30000 MPa, and the specific wear rate is 1.0 X X 1 0 _1 9~ 1 . 〇X 1 (Γ 15 m 2 /N wear resistance, and impedance-like Ι.ΟχΙΟ·4~1_〇χ102 Ω.cm conductive diamond-like carbon film is formed by 'but' In the present invention, the impedance ratio may be determined by a four-point probe method or a four-point measurement (Van der Pauw) method. Further, the conductive protective film of the present invention can provide an effect superior to the corrosion resistance in an acid/alkali solution or an oxidation/ring environment. For the purpose of the present invention, for the diamond-like carbon, a safety gas of the top three boric acid is used. A hydrocarbon-based gas such as an ester or trimethylboron is doped with boron (0.01 to 5 atomic%), and is formed into a conductive diamond-like carbon by a specific film formation method, and has high hardness and wear resistance. In addition, when the intermediate layer and the diamond-like carbon (DLC) film which are subjected to electrical resistance contact (low contact resistance) are used in combination, the conductivity can be improved, and the effect of the invention can be improved. According to the present invention, a specific conductive diamond-like carbon (DLC) film formed by an ionization evaporation method is used by using a specific gas species, or by combining the aforementioned diamond-like carbon (DLC) film, and reacting When it is necessary to use the intermediate layer of the resistance contact, it can be formed as a conductive surface-enhanced film layer, and has an indentation hardness of 9000 to 30,000 MPa, and the specific wear rate is 200912017. l. 〇xl〇-19~l.〇xl〇_15m2/N wear resistance, and an impedance of 1.0 XI 0_4~1.0 Χίο2 Ω. cm conductive diamond-like carbon (DLC) film, followed by [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described. However, these embodiments are exemplified. The configuration can be variously changed without departing from the technical idea of the present invention. The first embodiment of the method for producing a conductive protective film of the present invention is a method for producing a conductive protective film having a structure in which a conductive protective film 12 is formed on a substrate 10 as shown in FIG. As shown in Fig. 2, as a treatment for the substrate 1 ,, ion bombardment is performed, and the substrate is plasma-cleaned (step 100 of Fig. 2), and the ion bombardment is preferably performed by a rare gas such as Ar or a rare gas mixed with krypton. get on. Then, a conductive carbon-based carbon film 12 containing a specific amount of boron is formed on the substrate 1 by introducing a mixed gas of a hydrocarbon-based source gas and a boron-doped gas at a specific ratio (step 102 of FIG. 2) ). As a means for forming the above-described conductive diamond-like carbon film 12, it is known that there is an ionized steaming method, a glow discharge or a plasma CVD method using a high-frequency plasma, a photo CVD method by ultraviolet light excitation, a microwave CVD method, and a sputtering method. Although the plating method is the arc discharge method or the like, it is preferably an ionization vapor deposition method. In the present embodiment, the case of using the ionization vapor deposition method will be described. However, in the case of ionization vapor deposition, In the method of using the unbalanced plasma, the temperature of the substrate 1 is usually 550 ° C or less, and the substrate 1 〇 is deformed as a minimum. As a method of manufacturing the conductive protective film of the present invention, a device having the structure shown in FIG. 5 can be used. With respect to FIG. 5, the manufacturing device of the 20-type electrical protective film has a vacuum chamber 22, and The upper portion of the true chamber 2 2 is provided with a substrate holding portion for holding the substrate 1 另外, and an anode 26 wire 28 and a boron doping gas introduction port 30 are provided for the lower portion of the vacuum chamber 22, and more specifically, The hydrocarbon gas-based raw material gas introduction port 32 is provided in the side wall 22a of the vacuum 22, and the "hydrocarbon-based raw material gas introduction port 32" may be provided in the bottom wall 22b or the upper wall 22c of the vacuum 22. In the ionization vapor deposition method to which the present invention is applied, the vacuum 22 can be reduced in pressure (for example, vacuum drawing is performed at a vacuum of 3 X 1 0 · 3 P a or less to form a film at a low temperature, and the material is excited by electricity. The gas is applied to the substrate 1' to apply a negative voltage to deposit the film. Specifically, the vacuum chamber 22 of the manufacturing device 20 of the conductive protective film is introduced with acetylene, benzene (C6H6) gas or other hydrocarbon in a specific ratio. When the gas and the boron doping gas are used, the hot filament 28 and the anode 26 are used, and the ion source 29' passes through the DC arc discharge plasma to generate a hydrocarbon sink or excited radical, and the generated hydrocarbon ion is biased at The negative voltage substrate 10 is solidified by the energy of the bias voltage, and as shown in FIG. 1, a conductive drill carbon film 12 containing a specific amount of boron is formed on the substrate. Heat setting, for the cavities 24, the lamp chamber, the demon chamber chamber, the solution, the middle, the original ion cavitation class-9- 200912017, in order to form the aforementioned conductive diamond-like carbon Film 1 2 'made The hydrocarbon-based source gas is one or more than one selected from the group consisting of cyclohexane, benzene, acetylene, benzylbenzene, toluene, and cyclopentane. The heterogas is preferably one or more selected from the group consisting of boric acid 5$@ (trimethyl borate), trimethylboron and triethylboron, and further, a hydrocarbon-based material gas. The mixing ratio with the boron-doped gas system is 1 (hydrocarbon-based raw material gas): 1 (boron-doped gas) ~1 00:1 range, ideally used in the range of 2:1~3 0:1 By. In order to form the above-mentioned conductive diamond-like carbon film 12, it is desirable to use ionization vapor deposition method. The reason is that the electric current can be controlled via the filament 28 and the anode 26, and the ion bombardment can be controlled via the substrate voltage. 'This' is a condition in which boron can be activated while maintaining the structure of diamond-like carbon. The second embodiment of the method for producing a conductive protective film of the present invention is a conductive protective film having a structure in which the intermediate layer 11 is interposed between the substrate 1 and the conductive protective film 12 as shown in FIG. As shown in FIG. 4, in the same manner as in FIG. 2, first, as a process before the substrate 1 is processed, ion bombardment is performed via a gas such as Ar, and the substrate is washed (step 10 of FIG. 4). . The interface is formed as the surface of the substrate 1 前 of the pre-treatment described above, and the intermediate layer n for resistive contact is formed by film formation (step 1 图 of FIG. 4), wherein the interlayer 1 1 ί is used from @ '金金' Silver, indium, aluminum, phosphorus, titanium, nickel, chromium, ITO (In203-Sn〇3), Zn〇, Ti〇2, and strontium-------------- 2009-01 or two or more types of film formation However, the formation of the intermediate layer 11 may be performed by a plasma CVD method, a sputtering method, an ionization vapor deposition method, an evaporation method, or electroplating, but it is preferably a sputtering method. Next, in the same manner as in FIG. 2, a mixed gas containing a carbon source gas and a boron doping gas is introduced at a specific ratio, and a conductive diamond-like carbon film 12 containing a specific amount of boron is ion-vaporized to form a substrate 1 . (Step 1 〇 2 of Fig. 4), in this case, the case where the intermediate layer 1 1 and the diamond-like carbon film 12 are contacted via the group resistance are more electrically enhanced, however, the formation of the conductive diamond-like carbon film 12 is 1 The same as in the case of Fig. 2, the detailed description thereof will be omitted. One of a group consisting of carbon gas, gold, silver, indium, aluminum, phosphorus, titanium, nickel, chromium, ITO (SnO3), ZnO, TiO2, and yttrium used as the intermediate layer 1 1 or The intermediate layer 1 1 and the diamond-like 1 2 ' which are formed by the film formation and which are in contact with the electric resistance can reduce the control power loss due to the contact of the electric group. According to the method for producing a conductive protective film of the present invention, the boron content is 0.01 to 5 atomic%, and the indentation hardness is 9000 MPa, and the specific wear rate is ι.οχίο·19~l.〇xi〇-15m2 /N power consumption, and the impedance is 1.0 xl 〇_4~ 1.0 χΙΟ2 Ω.cm of conductive drill carbon film' However, the impedance rate can be determined by the four-point probe method or the four (Van der Pauw) method. . The substrate to which the method of the present invention is applied is not particularly limited, and for example, a glass substrate, a Si substrate, a metal substrate, a ceramic base substrate, and the like, are subjected to various metal plating (for example, hydrogenation by printing) The plating method can be used to measure the cause and the carbon film on the pattern Ι203- to the wear resistance of the 30,000 to 30000, but the plate can be plated and gold-plated. -11 - 200912017 Substrate, etc. EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples, but these are exemplified by the exemplified embodiments, and of course, not limited to the explanation (Example 1), as a BU process, by introducing A r into 14 sccm, The substrate was electrically charged 2 k V 'anode current 〇. 8 A, and after 1 hour of ion bombardment, the experimental conditions were on the quartz glass substrate, the intermediate layer was not subjected to boron doping, and the diamond-like carbon was used as 1 · 1 8 // m film formation. Conditions of implementation Gas flow rate: raw material gas (benzene) · trimethyl borate = seem
陽極電壓：45V 基板電壓：2 k V 成膜溫度：220°C 在測定上述所形成之導電性類鑽碳（DLC )被 度之時’奈米壓痕法之壓痕硬度係爲14271MPa， 到具有充分之硬度，另外’在進行經由球對盤法 ο η - d i s k t r i b 〇 m e t e r )之磨擦磨耗試驗時，摩擦係數 ，比磨耗量係爲1 . 2 X 1 〇_17m2/N，經由四點探針法 抗率時，阻丨几率係爲.cm，棚含有量f a t 〇 m i c %，另外，關於前述所形成之d L C被膜的耐 實施例 者。 壓作爲 以下述 成模而 3:0.5 膜之硬 並了解 (ball-爲 0.15 測定阻 i 0.95 腐蝕性 -12- 200912017 ，確認到在酸.鹼溶液或氧化•環兀環境’並無性 之情況。 然而，作爲基板並非只有玻璃基板’而針對在 板，金屬基板，陶瓷基板’塑料基板及於此等基板 鍍金之基板，亦進行同樣的實驗’確認到得到同樣 者，另外，在施以其他的電鍍之基板，亦可能。 做爲硼摻雜氣體，使用三甲基硼及三乙基硼， 樣的實驗，確認到得到同樣的結果者。 另外，將離子轟擊之氣體條件，從Ar變更爲 之Ar以外，係進行同樣的實驗，確認到得到同樣 者。 針對在薄膜之硬度試驗，是用以往法之顯微型 度計或壓痕之情況，當從膜厚超過某臨界値時，基 響大，並不知道薄膜本身的硬度，而爲了控制其影 般認爲將押入深度，有必要作爲膜厚之1 〇%以下（ 據基材材質與膜特性），因此，開發奈米壓 Nanoindentation)，成爲可做薄膜之硬度測定，並 2002年，作爲IS014577，做成奈米壓痕之製圖 地擴展認知，而記載於I S Ο 1 4 5 7 7之算出方法係q 度（Indentation Hardness) (HIT)，從投影接觸 最大荷重F表示成下述式（1)。 〔數1〕 ΗΙτ^^ψ- ---(1)Anode voltage: 45V Substrate voltage: 2 k V Film formation temperature: 220 ° C When measuring the degree of conductivity of the above-mentioned conductive diamond-like carbon (DLC), the indentation hardness of the nanoindentation method is 14271 MPa, The friction coefficient and the specific wear amount are 1. 2 X 1 〇_17m2/N, and the four-point probe is obtained when the friction is tested by the ball-to-disk method ο η - disktrib 〇meter. In the case of the needle resistance, the resistance is ., the shed content is fat 〇mic %, and the above-mentioned d LC film is resistant to the examples. The pressure is as follows: 3:0.5 The film is hard and well understood (ball-0.15 measured resistance i 0.95 corrosive -12- 200912017, confirmed in the acid or alkali solution or oxidized However, the same experiment was carried out for the substrate, the metal substrate, the ceramic substrate 'plastic substrate, and the substrate on which the substrate was plated with gold, as the substrate, and the same experiment was performed, and the other was applied. The substrate to be plated is also possible. As a boron-doped gas, trimethylboron and triethylboron were used, and the same result was confirmed. In addition, the gas conditions of ion bombardment were changed from Ar. For the same experiment, it was confirmed that the same experiment was carried out. For the hardness test of the film, the micrometer or the indentation of the conventional method was used, and when the film thickness exceeded a certain critical value, The base sound is large, and the hardness of the film itself is not known. In order to control the shadow, it is considered that the depth of the film is required to be 1% or less of the film thickness (according to the material of the substrate and the film characteristics). Nanoindentation, which is a measure of the hardness of a film, and in 2002, as an image of IS014577, which is made into a map of nanoindentation, the calculation method described in IS Ο 1 4 5 7 7 is q degree ( Indentation Hardness) (HIT), the maximum load F from the projection contact is expressed by the following formula (1). [Number 1] ΗΙτ^^ψ- ---(1)
AP 能劣化 :S i基 ，施以 的結果 進行同 混合Η 的結果 威氏硬 材的影 響 ，— 但，根 痕法（ 且，在 世界性 '壓痕硬 g A ρ和 -13- 200912017 摩擦磨耗試驗機係配合各用途，摺動方法或測定子部 分的形狀係爲多數，其中最爲一般的方法係爲經由球對盤 之（ball-on-disk tribometer)之磨擦磨耗試驗，測定原理 係於固定於有著剛性的支架之盤狀的試料上，經由既知之 精密秤砣而壓住球體，並且使盤旋轉，將作用於球體與盤 之間的摩擦力，經由支架之水平方向的小彎曲而測定，另 外，測定此時之磨耗痕剖面積，亦可做爲比磨耗量而做比 較者。 離子轟擊試驗之情況，試料之比磨耗量的測定係從磨 耗痕剖面積，經由接下來的式（2 )而算出。 〔數2〕AP can degrade: S i-based, the result of the application is the same as the result of mixing Η 威 硬 硬 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 根 根 根 根 根 根 根The wear tester is used for various purposes, and the shape of the folding method or the measuring sub-portion is mostly. The most common method is the friction-wear test by ball-on-disk tribometer. The disk is fixed on a disk-shaped sample having a rigid support, and the ball is pressed by a known precision scale, and the disk is rotated, and the frictional force acting between the ball and the disk is slightly bent in the horizontal direction of the bracket. In addition, the measurement of the cross-sectional area of the wear scar at this time can be used as a comparison with the wear amount. In the case of the ion bombardment test, the specific wear amount of the sample is measured from the wear scar sectional area, and the following formula. (2) and calculate. [Number 2]
二 ttR.S ~ 2P-L • · (2) 針對在式（2 )，將W作爲試驗片的比磨耗量（m2/N )，將R作爲摺動圓的半徑（m )，將S作爲摺動圓之剖 面積（m2 )，將P作爲荷重（N )，將L作爲摺動距離（ (實施例2) 作爲前處理，由將Ar導入14sccm，將基板電壓作爲 2kV’陽極電流〇.8A，進行1小時離子轟擊之後’以下述 的實驗條件，於石英玻璃基板上，中間層係未進行成模而 進行B摻雜，將類鑽碳，作爲〇.5#m成膜。 -14- 200912017 實施條件 氣體流量：原料氣體（苯）：硼酸三甲酯=2 · 2 : 〇 · 5 seemttR.S ~ 2P-L • (2) For equation (2), use W as the specific wear amount (m2/N) of the test piece, and use R as the radius of the folding circle (m), and take S as The cross-sectional area (m2) of the folding circle, P is used as the load (N), L is used as the folding distance (Example 2) as the pretreatment, and Ar is introduced into 14 sccm, and the substrate voltage is taken as the 2kV' anode current. 8A, after 1 hour of ion bombardment, 'on the quartz glass substrate, the intermediate layer was subjected to B-doping without molding, and the diamond-like carbon was formed as 〇.5#m. - 200912017 Implementation condition Gas flow rate: Raw material gas (benzene): Trimethyl borate = 2 · 2 : 〇· 5 seem
陽極電壓：45V 基板電壓：2kV 成膜溫度：220°C 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲23639MPa’並了解 到具有充分之硬度，另外，在進行經由球對盤法（ballon-disk tribometer) 之摩擦磨耗試驗時 ，摩擦 係數爲 〇·14 ，比磨耗量係爲9.2xl(T18m2/N，經由四點探針法測定阻 抗率時，阻抗率係爲4.2χ10°Ω .cm，硼含有量爲1.3 atomic%，另外，關於前述所形成之DLC被膜的耐腐蝕性 ，確認到在酸·鹼溶液或氧化·環元環境，並無性能劣化 之情況。 (實施例3 ) 作爲刖處理’由將A r導入1 4 s c c m，將基板電壓作爲 2kV，陽極電流0.8A，進行1小時離子轟擊之後，以下述 的實驗條件，於石英玻璃基板上’中間層係未進行成模而 進行B摻雜，將類鑽碳，作爲0.9 # m成膜。 實施條件 氣體流量：原料氣體（苯）：硼酸三甲酯=1.5: n<7 seem -15- 200912017Anode voltage: 45V Substrate voltage: 2kV Film formation temperature: 220 ° C When measuring the hardness of the above-mentioned conductive diamond-like carbon (DLC) film formed, the indentation hardness of the nanoindentation method is 23639 MPa' and understand To have sufficient hardness, and in the friction wear test by ballon-disk tribometer, the friction coefficient is 〇·14, and the specific wear rate is 9.2xl (T18m2/N, via four points When the impedance ratio is measured by the needle method, the impedance ratio is 4.2 χ 10 ° Ω·cm, and the boron content is 1.3 atomic%. Further, the corrosion resistance of the DLC film formed as described above is confirmed to be in the acid/base solution or oxidation. In the ring element environment, there is no performance deterioration. (Example 3) After the ion bombardment was carried out by introducing A r into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A for 1 hour. Experimental conditions, on the quartz glass substrate, the intermediate layer was not doped to perform B-doping, and the diamond-like carbon was formed as a film of 0.9 # m. Conditional gas flow rate: raw material gas (benzene): trimethyl borate = 1.5: n<7 seem -15- 200 912017
陽極電壓：45 VAnode voltage: 45 V
基板電壓：2kVSubstrate voltage: 2kV
成膜溫度：3 2 0 °C 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲1 7 869MPa，並了解 到具有充分之硬度，另外，在進行經由球對盤法（ballon-disk tribometer) 之磨 擦磨耗 試驗時 ，摩擦 係數爲 0.18 ，比磨耗量係爲 Κ5χ10_17πι2/Ν，經由四點探針法測定阻 抗率時，阻抗率係爲1.8 X 1(^ Ω · cm，硼含有量爲 2.8 atomic%，另外，關於前述所形成之DLC被膜的耐腐蝕性 ，確認到在酸•鹼溶液或氧化•環元環境，並無性能劣化 之情況。 (實施例4) 作爲前處理’由將Ar導入14Sccm，將基板電壓作爲 2k V，陽極電流0.8 A，進行1小時離子轟擊，之後，於氧 化鋁基板上，經由濺鍍法，將〇 1 A m之T i中間層，進行 成膜，以下述之實驗條件，之後將進行B摻雜之導電性類 鑽碳，作爲〇 . 8 /z m成膜。 實施條件 氣體流量：原料氣體（苯）：硼酸三甲酯=2.2 : 0.5 seemFilm formation temperature: 3 2 0 °C When the hardness of the conductive diamond-like carbon (DLC) film formed above was measured, the indentation hardness of the nanoindentation method was 1 7 869 MPa, and it was found to be sufficient. Hardness, in addition, when the frictional abrasion test by a ballon-disk tribometer is performed, the friction coefficient is 0.18, the specific wear amount is Κ5χ10_17πι2/Ν, and the impedance ratio is measured by the four-point probe method. It is 1.8 X 1 (^ Ω · cm, the boron content is 2.8 atomic%, and the corrosion resistance of the DLC film formed as described above is confirmed to have no performance in an acid/alkali solution or an oxidation/ring environment. (Example 4) As a pretreatment, by introducing Ar into 14 Sccm, the substrate voltage was 2 k V and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, and then, on the alumina substrate, by sputtering, The intermediate layer of T 1 m1 A m was formed into a film, and then B-doped conductive diamond-like carbon was formed as a film of 〇. 8 /zm under the following experimental conditions. Conditional gas flow rate: raw material gas (Benzene): Trimethyl borate = 2.2: 0.5 seem
陽極電壓：45VAnode voltage: 45V
基板電壓：2kV -16 - 200912017Substrate voltage: 2kV -16 - 200912017
成膜溫度：200°C 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲2 1 983 MPa，並了解 到具有充分之硬度，另外，在進行經由球對盤法（ballon-disk tribometer) 之磨 擦磨耗 試驗時 ，摩擦 係數爲 0.15 ，比磨耗量係爲1.2xl(T17m2/N，經由四點探針法測定阻 抗率時，阻抗率係爲5.76χ1(Γ3Ω .cm，硼含有量爲1.3 atomic%，另外，關於前述所形成之DLC被膜的耐腐蝕性 ，確認到在酸•鹼溶液或氧化•環元環境，並無性能劣化 之情況。 做爲硼摻雜氣體，使用三甲基硼及三乙基硼，進行同 樣的實驗，確認到得到同樣的結果者。 另外，作爲中間層，經由濺鍍法，形成各厚度0.1 // m 之碳，金，銀，銦，鋁，磷，鈦，鎳，鉻，Ζ η Ο，T i Ο 2及 矽層，進行同樣的實驗，確認到得到同樣的結果者。 另外，將離子轟擊之氣體條件，從Ar變更爲混合η 之Ar以外，係進行同樣的實驗，確認到得到同樣的結果 者。 (實施例5 ) 作爲前處理，由將Ar導入14sccm，將基板電壓作爲 2kV，陽極電流0.8A，進行1小時離子轟擊之後，以下述 的實驗條件，於石英玻璃基板上，中間層係未進行成模而 進行硼摻雜，將類鑽碳，作爲〇.3vm成膜。 -17- 200912017 實施條件 氣體流量：原料氣體（苯）：硼酸三甲酯=1.86: 〇_7 seem 陽極電壓：70V 基板電壓：4kV 成膜溫度：3 2 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲11291MPa，並了解 到具有充分之硬度，另外，在進行經由球對盤法（ballon-disk tribometer) 之磨擦磨耗 試驗時 ，摩擦 係數爲 0.16 ，比磨耗量係爲4.6xl(T18m2/N，經由四點探針法測定阻 抗率時，阻抗率係爲4.9x10_2 Ω . cm，硼含有量爲2.1 at 〇 m i c %，另外，關於前述所形成之D L C被膜的耐腐蝕性 ，確認到在酸•鹼溶液或氧化•環元環境，並無性能劣化 之情況。 (實施例6 ) 作爲前處理，由將Ar導入Mseem，將基板電壞作爲 2kV，陽極電流0.SA，進行1小時離子轟擊之後’以卞述 的實驗條件，於石英玻璃基板上，經由濺鍍法，將〇 . iFilm formation temperature: 200 ° C When measuring the hardness of the above-mentioned conductive diamond-like carbon (DLC) film formed, the indentation hardness of the nanoindentation method was 2 1 983 MPa, and it was found that the hardness was sufficient. Further, when the abrasion abrasion test by a ballon-disk tribometer was performed, the friction coefficient was 0.15, and the specific wear amount was 1.2 x 1 (T17 m 2 /N, when the impedance ratio was measured by the four-point probe method. The impedance ratio is 5.76 χ1 (Γ3 Ω·cm, and the boron content is 1.3 atomic%. Further, regarding the corrosion resistance of the DLC film formed as described above, it is confirmed that there is no performance in an acid/alkali solution or an oxidation/ring element environment. In the case of deterioration, the same experiment was carried out using trimethylboron and triethylboron as the boron-doped gas, and the same result was obtained. Further, as the intermediate layer, each thickness was 0.1 by sputtering. // m of carbon, gold, silver, indium, aluminum, phosphorus, titanium, nickel, chromium, Ζ η Ο, T i Ο 2 and 矽 layer, perform the same experiment and confirm that the same result is obtained. Gas conditions for ion bombardment, changing from Ar to mixed η The same experiment was carried out except for Ar, and it was confirmed that the same result was obtained. (Example 5) As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour. Under the following experimental conditions, on the quartz glass substrate, the intermediate layer was subjected to boron doping without molding, and the diamond-like carbon was formed as 〇.3 vm. -17- 200912017 Conditional gas flow rate: raw material gas (benzene ): Trimethyl borate = 1.86: 〇 _7 seem Anode voltage: 70 V Substrate voltage: 4 kV Film formation temperature: 3 2 When measuring the hardness of the above-mentioned conductive diamond-like carbon (DLC) film formed, the nano pressure The indentation hardness of the trace method was 11291 MPa, and it was found that the hardness was sufficient. In addition, when the abrasion abrasion test by a ballon-disk tribometer was performed, the friction coefficient was 0.16, and the specific abrasion amount was 4.6. Xl (T18m2/N, when the impedance ratio is measured by the four-point probe method, the impedance ratio is 4.9×10 2 Ω·cm, the boron content is 2.1 at 〇mic %, and the corrosion resistance of the formed DLC film is also obtained.It was confirmed that there was no deterioration in performance in the acid/alkali solution or the oxidation/ring environment. (Example 6) As a pretreatment, Ar was introduced into Mseem, and the substrate was electrically damaged as 2 kV and the anode current was 0.1 SA. After 1 hour of ion bombardment, the experimental conditions described above were carried out on a quartz glass substrate by sputtering.
Mm 之Ti中間層，進行成膜之後，以下述之實驗條件，轉進 行B摻雜之導電性類鑽碳，作爲〇. 3 5 /z m成膜。 實施條件 氣體流量：原料氣體（苯）：硼酸三甲酯=1·5: -18- 200912017 seemAfter the film formation of the Ti intermediate layer of Mm, the B-doped conductive diamond-like carbon was transferred to the film of 〇. 3 5 /z m under the following experimental conditions. Conditions of implementation Gas flow: raw material gas (benzene): trimethyl borate = 1 5: -18- 200912017 seem
陽極電壓：45 VAnode voltage: 45 V
基板電壓：3kVSubstrate voltage: 3kV
成膜溫度：2 0 0 °C 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲95 3 OMPa，並了解到 具有充分之硬度，另外，在進行經由球對盤法（ball-on-disk tribometer) 之磨 擦磨耗 試驗時 ，摩擦 係數爲 0.15 ， 比磨耗量係爲3.7 xlO·18 m2/N，經由四點探針法測定阻抗 率時，阻抗率係爲 2·〇χ10_4 Ω · cm，硼含有量爲 2.8 a t 〇 m i c %，另外，關於前述所形成之D L C被膜的耐腐蝕性 ，確認到在酸•鹼溶液或氧化•環元環境，並無性能劣化 之情況。 (實施例7 ) 作爲前處理，由將Ar導入14sccm ’將基板電壓作爲 2kV，陽極電流0.8 A，進行1小時離子轟擊之後，以下述 的實驗條件，於石英玻璃基板上，經由濺鍍法’將〇 _ 1 # m 之ΙΤ0中間層，進行成膜之後，以下述之實驗條件，將進 行B摻雜之導電性類鑽碳，作爲0 · 3 // m成膜。 實施條件 氣體流量：原料氣體（苯）：硼酸三甲酯=1.5: 0.7 seemFilm formation temperature: 200 ° C When the hardness of the conductive diamond-like carbon (DLC) film formed above was measured, the indentation hardness of the nanoindentation method was 95 3 OMPa, and it was found to be sufficient. Hardness, in addition, when performing a frictional abrasion test by a ball-on-disk tribometer, the friction coefficient was 0.15, and the specific abrasion amount was 3.7 x 10 · 18 m 2 /N, which was measured by a four-point probe method. In the case of the resistivity, the impedance ratio is 2·〇χ10_4 Ω·cm, and the boron content is 2.8 at 〇mic %. Further, the corrosion resistance of the DLC film formed as described above is confirmed to be in the acid/alkali solution or oxidation. In the ring environment, there is no performance degradation. (Example 7) As a pretreatment, after introducing Ar into 14 sccm', the substrate voltage was 2 kV, and the anode current was 0.8 A, and ion bombardment was performed for 1 hour, and then on the quartz glass substrate by sputtering method under the following experimental conditions. After the intermediate layer of ΙΤ1 1 m was formed into a film, the B-doped conductive diamond-like carbon was formed as a film of 0 · 3 // m under the following experimental conditions. Conditions of implementation Gas flow: raw material gas (benzene): trimethyl borate = 1.5: 0.7 seem
陽極電壓：4 5 V -19- 200912017Anode voltage: 4 5 V -19- 200912017
基板電壓：3kV 成膜溫度：20CTC 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲98 67MPa ,並了解到 具有充分之硬度’另外’在進行經由球對盤法（b a 11 - on-disk tribometer) 之磨 擦磨耗 試驗時 ，摩擦係數爲 〇.16 ， 比磨耗量係爲3_6xl(T18m2/N，經由四點探針法測定阻抗 率時，阻抗率係爲 2·4χ1〇_4Ω .cm，硼含有量爲 2.8 a t 〇 m i c %，另外，關於前述所形成之D L C被膜的耐腐蝕性 ，確認到在酸•鹼溶液或氧化•環元環境，並無性能劣化 之情況。 (比較例1 ) 作爲前處理’由將Ar導入14sccm，將基板電壓作爲 2 k V，陽極電流0 · 8 A ’進行1小時離子蠢擊之後，於氧化 鋁基板上，將未摻雜硼之類鑽碳薄膜，作爲1 · 1 // m成膜 〇 實施條件Substrate voltage: 3kV Film formation temperature: 20CTC When the hardness of the conductive diamond-like carbon (DLC) film formed above was measured, the indentation hardness of the nanoindentation method was 98 67 MPa, and it was found that the hardness was sufficient. 'Other' In the frictional abrasion test by the ball 11 - on-disk tribometer, the friction coefficient was 〇.16, and the specific wear was 3_6xl (T18m2/N, measured by the four-point probe method). In the case of the impedance ratio, the impedance ratio is 2·4χ1〇_4 Ω·cm, and the boron content is 2.8 at 〇mic %. Further, the corrosion resistance of the DLC film formed as described above is confirmed to be in the acid or alkali solution or oxidation. • In the ring element environment, there is no performance deterioration. (Comparative Example 1) As a pretreatment, after introducing Ar into 14 sccm, the substrate voltage is 2 k V, and the anode current is 0 · 8 A '1 hour, the ion is strayed. On the alumina substrate, a carbon film of undoped boron is used as a condition for forming a film of 1 · 1 / m
氣體流量：原料氣體（苯）3SCcm 陽極電壓：45 V 基板電壓：2 k V 在測定上述所形成之導電性類鑽碳（DLC )被膜之硬 度之時，奈米壓痕法之壓痕硬度係爲23211 MPa，並了解 到具有充分之硬度，另外，在進行經由球對盤法（ball- -20- 200912017 on-disk tribometer)之磨擦磨耗試驗時，摩擦系數爲0.11 ，比磨耗量係爲5.0xl(T18m2/N，經由四點探針法測定阻 抗率時，阻抗率係爲2·7χ ΙΟ3 Ω _ cm。 【圖式簡單說明】 〔圖1〕係爲表示本發明之導電性保護膜之第1實施 型態的擴大剖面說明圖。 〔圖2〕係爲表示經由本發明之導電性保護膜之第1 實施型態而被覆基板表面情況之工程順序之一例的流程圖 〇 〔圖3〕係爲表示本發明之導電性保護膜之第2實施 型態的擴大剖面說明圖。 〔圖4〕係爲表示經由本發明之導電性保護膜之第2 實施型態而被覆基板表面情況之工程順序之一例的流程圖 〇 〔圖5〕係爲表示形成本發明之導電性保護膜的導電 性保護膜之製造裝置之一例槪略說明圖。 【主要元件符號說明】 1 〇 :基板 1 1 :中間層 1 2 :導電性D L C被膜 20 :導電性保護膜製造裝置 22 :真空腔室 -21 - 200912017 22a :側壁 22b :底壁 22c :上壁 2 4 ·基板支撑部 2 6 :陽極 2 8 :燈絲 2 9 :離子源 3 0 :硼摻雜氣體導入口 3 2 :碳化氫系原料氣體導入口 -22-Gas flow rate: raw material gas (benzene) 3SCcm Anode voltage: 45 V Substrate voltage: 2 k V Indentation hardness of the nanoindentation method when measuring the hardness of the above-mentioned conductive diamond-like carbon (DLC) film formed It is 23211 MPa, and it is known that it has sufficient hardness. In addition, when the frictional abrasion test by ball-to-disk tribometer is performed, the friction coefficient is 0.11 and the specific wear rate is 5.0. Xl (T18m2/N, when the impedance ratio is measured by the four-point probe method, the impedance ratio is 2·7 χ 3 Ω _ cm. [Brief Description] FIG. 1 is a view showing the conductive protective film of the present invention. Fig. 2 is a flow chart showing an example of the engineering procedure for coating the surface of the substrate by the first embodiment of the conductive protective film of the present invention (Fig. 3). It is an enlarged cross-sectional explanatory view showing the second embodiment of the conductive protective film of the present invention. [Fig. 4] is a view showing the condition of coating the surface of the substrate by the second embodiment of the conductive protective film of the present invention. Process of one of the sequences FIG. 5 is a schematic view showing an example of a manufacturing apparatus for forming a conductive protective film of the conductive protective film of the present invention. [Description of Main Element Symbols] 1 〇: Substrate 1 1 : Intermediate layer 1 2 : Conductive DLC film 20: Conductive protective film manufacturing apparatus 22: vacuum chamber-21 - 200912017 22a: side wall 22b: bottom wall 22c: upper wall 2 4 · substrate supporting portion 2 6 : anode 2 8 : filament 2 9 : ion Source 3 0 : boron doping gas introduction port 3 2 : hydrocarbon-based material gas introduction port -22-
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