鯉濟部中央樣準局貝工消费合作社印取 83.3.10,000 448243 A7 _____B7_ 五、發明説明（.i ) 背景： 類鑽碳膜（Diamond-Like Carbon)具有高硬 度、耐腐姓性佳、表面平滑、摩擦係數小、膜 敏密度高、電絕緣性佳、熱傳導性佳、生物相 容性佳、抗磨耗性佳、能在低溫下成長等許多 非常優異的性質。因此，類鑽碳膜可應用的領 域也是非常的廣泛，除了在電子元件有很好的 應用之外，在光學元件、醫療器材、及一些抗 磨耗的場合其應用均深具潛力》 一般而言，類鑽碳膜的性質主要和離子撞擊 基板的能量有關，而與所使用礙源種類較沒關 係。因為離子能量是決定膜中氫原子濃度與sp3 含量之重要關鍵。根據不同之成長方法、條件 與所使用的碳源，可合成出兩種不同形式之類 鑽碳膜：含氫類鑽後膜（hydrogenated amorphous carbon (a-c: Η))及含氫量極少或不含氫之類 鑽碳膜（hydrogen-free amorphous carbon (a-C))。對於含氫類鑽碳膜而言，在電漿t所 產生的碳氫化合物離子（CHX+)被加速而穿入 基板表面，其撞擊的能量可將碳-氫鍵打斷而形 成一隨機且高度交鍵的碳網狀結構（random and highly cross-linked carbon network)。如果 離子入射能量太低而無法將碳-氫鍵打斷’則大 ------- 一：一 从相中軸家辟（CNS ) U1GX297公釐） ----------^---4^.------訂--r----線· (請先聞讀背面之注意事項再填寫本萸) 448243 A7 B7 五、發明説明（2 ^ 量的氫^留在膜中，形成一個含氩量極高且大 伤碳都以sp3鍵結為主（多數的碳都與氫產生 鍵結）但此結構類似高分子（p〇ly^er_like)， 其硬度低而沒有實用性。相反的，入射離子能 量足夠问的話’大部份的碳-氫鍵可被打斷而得 到一個含氫量低且鍵角高度扭曲之SP3結構（大 部份的碳僅與碳產生鍵結），此種類鑽碳膜的硬 度非常高’深具工業價值，但確有應力太大， 和基材附著不好而容易刺落的問題。 類鑽碳膜要應用在鋼材上需要克服的間題為 高溫的穩定性需提高和膜與鋼材的附著力需加 (請先閲讀背面之注意事項再填寫本頁 強。品質佳之類鑽碳膜通常可操作在3〇〇-50(TC 間’但若能再提高100至200°C，將可使產品的 可靠性更為增強。至於要增進類鐵碳膜與鋼材 間之附著力，從文獻上歸納及吾人實驗觀察， 4 類鑽碳膜内殘餘的高壓縮應力是造成類鑽碳膜 經濟部中央標準局員工消費合作社印裝 在基板上附著力不好的原因之一。此壓縮應力 來自於類鑽碳膜成長期間，由於離子高能撞擊， 使膜内有扭曲的sp3碳-碳鍵結造成的 本紙張尺度適用中國國家樣準（CNS ) A4规格（210X297公釐） 83.3.10,000 44824:: 經濟部中央標準局員工消費合作杜印裳 Α7 Β7 五、發明説明（3) 第一圖說明了類鑽碳膜内應力釋放的情形’ 由第一圖可以知道膜中内應力的大小以及膜與 基板的黏著力決定整個膜的附著行為。 工業上則是加中間層如氮化鈦、碳化鈦，鍍 上中間層後’再以離子蒸鑛法嫂上類鑽碳膜。 利用以多層膜（mul ti layer coating)的鍵膜方 式比僅鍍單層的效果好，因為利用多層膜做為 中間層有下列幾個特點： (1) 可做為差排（dislocation)移動的屏障層，可缓 和膜的内應力。 (2) 經適當的多層膜組合，可獲得適當的硬度/韌性 比例；因為韌性高則相對硬度就低。 0)能增加鍍層和基板的附著力。 (4)因為有膜層界面的存在，具有偏折（deflectic)n) 裂痕的效果。在鍍膜的過程中因為膜界面之存 在’會使硬膜的裂痕延展受阻、產生偏折或停 止前進而使整體破裂的強度增強；同時在界面 處產生能量偏折，可達到釋放殘留應力的目的。 另外如前所述，經適當的多層膜組合，可 獲得適當的硬度與韌性。若整體硬度太高，則 不耐衝擊；相反的，若韌性太高雖然耐衝擊力 好’但卻硬度不夠而不抗磨耗。所以唯有二者 ____ — ίγ — 本紙張適用中卿家樣準（CNS )八4狀（21GX297公釐） 83. 3.10,000 (請先聞讀背*之注意事項再填寫本頁) -* 4 4 82 4 經濟部中央標準局負工消費合作社印褽 A7 B7 五、發明説明（6 ) 費時間。而本發明人所開發的有機矽氧烷中間 層系統，包括最後一層純類鑽碳層都可在低溫 下鍍膜，且其表現出來的附著力足以與傳統的 氮化鈦、碳化鈦中間層互相抗衡。 類鑽碳本身應力有兩大來源，一是本身的固 有壓縮應力，另外是跟鋼材之同熱膨脹係數所 造成的熱應力，雖然本製程是低溫製程，使用 若是溫度提高，熱應力會顯現出來。本發明人 曾經將本發明方法製得的類鑽碳改質膜置於烘 箱内作溫度升降的實驗（thermal cycle)，於400 °C及常溫下分別維持20分鐘，經過50次週而 復始的循環之後，其硬度及附著力並沒有下降， 顯示我們的類鑽碳改質膜在這情況下並不會因 為熱應力而造成硬度及附著力的下降。本發明 人又將膜加熱到40CTC，維持兩個小時，在對其 作拉曼（Raman)光譜分析，發現光譜並沒有改 變’如第三圖，顯示此膜在400°C的環境下並不 會石墨化，而使膜的結構改變。 '~~ 占— ----------炎-- (請先閾讀背面之注$項再填寫本頁)Printed by the Central Cooperative Bureau of the Ministry of Common Carriage and Boiler Consumer Cooperatives 83.3.10,000 448243 A7 _____B7_ V. Description of the Invention (.i) Background: Diamond-Like Carbon has high hardness, good corrosion resistance, surface It has many excellent properties such as smoothness, small friction coefficient, high film sensitivity density, good electrical insulation, good thermal conductivity, good biocompatibility, good abrasion resistance, and can grow at low temperature. Therefore, the application areas of diamond-like carbon films are also very wide. In addition to good applications in electronic components, their applications have great potential in optical components, medical equipment, and some wear-resistant occasions. The properties of diamond-like carbon films are mainly related to the energy of ions striking the substrate, but have nothing to do with the type of interference source used. Because the ion energy is the key to determine the hydrogen atom concentration and sp3 content in the membrane. According to different growth methods, conditions, and carbon sources used, two different types of diamond carbon films can be synthesized: hydrogenated amorphous carbon (ac: Η) and very little or no hydrogen content Diamond-like carbon film (hydrogen-free amorphous carbon (aC)). For a hydrogen-containing diamond carbon film, the hydrocarbon ions (CHX +) generated in the plasma t are accelerated and penetrate into the surface of the substrate. The impact energy can break the carbon-hydrogen bond to form a random and highly Random and highly cross-linked carbon network. If the ion incident energy is too low to break the carbon-hydrogen bond, then it is large -------- one: one from the phase axis (CNS U1GX297 mm) ---------- ^ --- 4 ^ .------ Order--r ---- line · (Please read the notes on the back before filling in this note) 448243 A7 B7 V. Description of the invention (2 ^ amount of hydrogen ^ Stays in the membrane, forming an extremely high argon content, and the major damage carbons are mainly sp3 bonds (most carbons are bonded with hydrogen), but this structure is similar to a polymer (p〇ly ^ er_like), which Low hardness without practicality. Conversely, if the incident ion energy is sufficient, 'most of the carbon-hydrogen bonds can be broken to obtain a SP3 structure with low hydrogen content and highly distorted bond angles (most of the carbon Only bonding with carbon), this type of diamond carbon film has very high hardness' deep industrial value, but it does have too much stress and poor adhesion to the substrate and easy to fall off. Diamond-like carbon film should be used in The problems that need to be overcome on steel are called the stability of high temperature and the adhesion of the film to the steel. (Please read the precautions on the back before filling out this page. The diamond film with good quality can usually be used. The operation is between 300-50 ° C, but if it can be increased by 100 to 200 ° C, the reliability of the product will be further enhanced. As for improving the adhesion between the ferrous carbon film and the steel, from the literature In summary and our experimental observations, the high residual compressive stress in the type 4 diamond carbon film is one of the reasons for the poor adhesion on the substrate printed by the consumer cooperative of the Central Standards Bureau of the Ministry of Economics of the film-like diamond film. This compressive stress comes from During the growth of the diamond-like carbon film, due to the impact of high-energy ions, the twisted sp3 carbon-carbon bond in the film is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000 44824 :: Du Yinshang A7 B7, Consumer Cooperation of Staff of the Central Bureau of Standards, Ministry of Economic Affairs 5. Explanation of the invention (3) The first picture illustrates the internal stress release of the diamond-like carbon film. The adhesion of the substrate determines the adhesion behavior of the entire film. In industry, an intermediate layer such as titanium nitride and titanium carbide is added, and the intermediate layer is coated with a diamond-like carbon film by ion evaporation. mul ti layer coatin g) The key film method is more effective than only a single layer, because the use of a multilayer film as an intermediate layer has the following characteristics: (1) It can be used as a barrier layer for dislocation movement, which can ease the interior of the film. (2) The appropriate hardness / toughness ratio can be obtained through proper multilayer film combination; because the toughness is high, the relative hardness is low. 0) It can increase the adhesion between the coating and the substrate. (4) Because of the interface of the film layer Existence, it has the effect of deflectic n) cracks. During the coating process, because of the existence of the film interface, the crack extension of the hard film will be blocked, deflection will occur, or the advancement will stop, which will increase the strength of the overall fracture; Energy deflection is generated at the interface, which can achieve the purpose of releasing residual stress. In addition, as described above, appropriate hardness and toughness can be obtained by combining appropriate multilayer films. If the overall hardness is too high, it will not be resistant to impact; on the contrary, if the toughness is too high, although the impact resistance is good ', the hardness will be insufficient but not resistant to abrasion. So there are only two of them ____ — ίγ — This paper is suitable for Zhongqing Family Sample Standard (CNS) Eighty Four (21GX297 mm) 83. 3.10,000 (Please read the notes on the back * before filling this page)- * 4 4 82 4 A7 B7, a consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, A7 B7 V. Description of the invention (6) Time-consuming. The organosilicon interlayer system developed by the present inventor, including the last pure diamond-like carbon layer, can be coated at a low temperature, and the adhesion shown is sufficient to interact with the traditional titanium nitride and titanium carbide intermediate layers. contend. There are two major sources of stress in diamond-like carbon. One is its inherent compressive stress, and the other is the thermal stress caused by the same thermal expansion coefficient as steel. Although this process is a low temperature process, if the temperature is increased, the thermal stress will appear. The inventor once placed the diamond-like carbon modified film prepared by the method of the present invention in an oven for a temperature cycle experiment (thermal cycle), and maintained it at 400 ° C and normal temperature for 20 minutes each. After 50 cycles of repeated cycles , Its hardness and adhesion have not decreased, showing that our diamond-like carbon modified film in this case will not cause a decrease in hardness and adhesion due to thermal stress. The inventor heated the film to 40CTC and maintained it for two hours. After performing Raman spectrum analysis on the film, it was found that the spectrum did not change. As shown in the third figure, the film was not exposed to 400 ° C It will be graphitized and the structure of the film will be changed. '~~ account----------- Yan-(please read the note $ on the back before filling this page)
，-IT 綉 本紙張尺度適用中國國家揉準（CNS } A4规格（210X297公釐） 83 3-10,000 4482 4 經濟部中央標準局員工消費合作社印裝 Α7 Β7 五、發明説明（7 ) 雖然氮化鈦、氮化碳可以耐到更高溫，但是 本發明方法製得的類鑽碳改質膜其製程簡單且 製程溫度低就是一大優點’又其有絕佳的化學 惰性’故在有酸、鹼的環境裡，將是TiN、TiC 其保護能力所不能灰，而確是類鑽碳膜（類鑽 碳改質膜）能勝任的》因此本發明人認為此製 程將有其競爭性及進步性。 2.發明創作說明： 有機矽氧烷類鑽碳改質膜作為單一中間層或 多層漸進中間層的製備： 本發明人將有機矽氧烷化合物（例如HMDSO， hexamethyldisiloxane ’（CH3)3Si-〇-Si(CH3)3) 及甲烷以各種不同比例，在電漿中解離。首先 我們先鍵單一有機石夕氧院層於鋼材上來探討其 附著行為，在此採用電容式電漿離子蒸鑛法， 在基板載體處通以高週電源（RF)，再與接地的 真空腔體壁產生電容釋放電而將工作氣體解 離’其離子再藉由高週波（RF)的自我偏壓（seif bias)得到能量而直接轟擊基板。如第一圖說 明了類鑽碳膜内應力釋放的情形。 -(d ' 本紙張尺度逍用中囲固家標準（CNS > Α4規格（210X297公釐） 83.3.10,000 I--------^---l·-- <請先閲讀背面之注意事項再填寫本頁) 訂 4482 4 3 A7 B7 經濟部中央標率局員工消費合作社印裝 五、發明説明£ 8) 本發明因參與改質的物質（例如龍DSO)與甲 烷在氣相中充分混合，再由鍵能的大小分析得 知，有機矽氧烷化合物中的矽氧（si_〇)鍵能 最大。 推測有機矽氧烧化合物中的矽氧官能基 (Si-0-Si)結構在電漿中將比較不容易被破 壞，所以機矽氧烧化合物的功用能在 膜中提供矽氧官能基（Si-O-Sl··)，因此矽氧官 能基（Si-Ο-Si)的分佈將是以分子級的大小分 散於膜中，也經由紅外線光譜儀（IR)得以確 認此一現象。我們在類錢碳中加入矽氧官能基 (Si-0-Si)能增加整體類鑽碳膜的於鋼材上的 附著性’最佳的條件下，其臨界荷重可高達5〇 牛頓以上。且其硬度也相當高，在適當的比例 下其硬度可高達21·75χ 109帕（pa)。 因有機石夕氧烧中間層有其絕佳的硬度及附著 力’本發明人利用前述漸進詹的優點，以不同 比例的有機矽氧烷化合物當多層漸進層，最後 在鍍上純的類鑽碳膜，同樣採用如第二圖的電 容式電漿離子蒸鍵法，在基板載體處通以高週 電源（RF)’再與接地的真空腔體壁產生電容釋 放電而將工作氣體解離，其離子再藉由高週波 (RF )的自我偏壓（sel f bias )得到能量而直 接轟擊基板。此時的工作氣體是各種不同比例 m"ir (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度逍用中國固家標率（CMS ) AA规格（2丨0父297公瘦） 83. 3.10,000 448243 A7 ____B7________ 五、發明説明（f) t ^ . 的有機矽氧烷化合物及甲烷，連續的改變以 形成層與層之間的性質不會有劇烈的改變的漸 進層’再在最上面以純的曱烷鍍上純的類鑽碳 薄膜。此漸進層系統也有不錯的附著力。 3.實施例詳細說明： 以下以實施例詳細說明本發明之技術特徵先 對單一的有機矽氧烷中間層做探討。 對經過熱處理JIS系列冷作模具合金工具鋼 (SKD11)上以電容式電漿離子蒸鍍法蒸鍍有機 矽氧化合物中間層。為了增加底材對硬膜的支 撐度’所以在必須還要加強底材的硬度，因此 在在鍵膜之前需先將鋼材的表面進行氮化處 理，鋼材的硬度在氮化處理完後其硬度值約u X 109 帕（pa)。 • jis系列冷作模具合金工具鋼SKD11(高碳高 鉻鋼）。其組成如下： SKD1 ί ---r--h------裝------'1T------绣 > (請先閲讀背面之注項再填寫本頁) 經濟部中央榡準局舅工消費合作社印裝 元素（Element) C 比例 1.4-1.6 (Amount(wt%) Μ Μη (Jr， -IT embroidery paper size is applicable to Chinese national standard (CNS) A4 size (210X297mm) 83 3-10,000 4482 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) Titanium and carbon nitride can withstand higher temperatures, but the diamond-like carbon modified film prepared by the method of the present invention has a simple process and a low process temperature, which is a great advantage, and it has excellent chemical inertness. In an alkaline environment, TiN and TiC cannot be protected by ash, but diamond-like carbon film (diamond-like carbon modified film) is competent. Therefore, the inventor believes that this process will have its competitiveness and progress 2. Inventive creation description: Preparation of organosilicon diamond modified carbon film as a single intermediate layer or multiple progressive intermediate layers: The present inventors applied organic silicone compounds (such as HMDSO, hexamethyldisiloxane '(CH3) 3Si- 〇-Si (CH3) 3) and methane are dissociated in the plasma in various proportions. First, we first bond a single organic stone layer to the steel to discuss its adhesion behavior. Here, a capacitive plasma ionization is used. Law, in The plate carrier is connected with a high-frequency power supply (RF), and then a capacitor is generated with the grounded vacuum cavity wall to release the electricity and dissociate the working gas. The ions are then obtained by the high-frequency (RF) self-biasing. And directly bombard the substrate. As shown in the first figure, the stress-releasing situation of the diamond-like carbon film is shown.-(D 'This paper size is not suitable for use in the standard (CNS > A4 specification (210X297 mm) 83.3.10,000 I -------- ^ --- l ·-< Please read the notes on the back before filling out this page) Order 4482 4 3 A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Note £ 8) In the present invention, because the substance involved in the modification (such as Dragon DSO) and methane are sufficiently mixed in the gas phase, and the size of the bond energy is analyzed, it is known that the silicon oxygen (si_〇) in the organosiloxane compound The bond energy is the largest. It is speculated that the siloxane functional group (Si-0-Si) structure in the organosilicon compound will not be easily destroyed in the plasma, so the function of the organosilicon compound can provide silicon oxygen in the film. Functional groups (Si-O-Sl · ·), so the distribution of siloxane functional groups (Si-O-Si) will be at the molecular level Dispersed in the film, this phenomenon has also been confirmed by infrared spectrometer (IR). We add silicon oxygen functional group (Si-0-Si) to the money-like carbon to increase the adhesion of the overall diamond-like carbon film to steel. 'Under the best conditions, its critical load can be as high as 50 Newtons or more and its hardness is quite high. Under the proper ratio, its hardness can be as high as 21 · 75χ 109 Pa (pa). The organic layer is burned with oxygen. Has its excellent hardness and adhesion 'The inventors took advantage of the aforementioned progressive Zhan, using different proportions of organosiloxane compounds as multiple progressive layers, and finally coated a pure diamond-like carbon film, likewise using the second The capacitive plasma ion-bonding method shown in the figure uses a high-frequency power supply (RF) 'on the substrate carrier to generate a capacitive discharge from the grounded vacuum cavity wall to dissociate the working gas. RF) self-bias (sel f bias) gets energy and directly bombards the substrate. The working gas at this time is a variety of different ratios (please read the precautions on the back before filling out this page) This paper standard uses the Chinese solid standard (CMS) AA specification (2 丨 0 parent 297 male thin) 83. 3.10,000 448243 A7 ____B7________ V. Description of the invention (f) t ^. The organosiloxane compound and methane are continuously changed to form a progressive layer with no change in properties between layers. A pure diamond-like carbon film is plated on top with pure pinane. This progressive layer system also has good adhesion. 3. Detailed description of the embodiments: The technical features of the present invention will be described in detail in the following embodiments. First, a single organosiloxane intermediate layer will be discussed. An organic silicon oxide intermediate layer was deposited on a heat-treated JIS series cold work die alloy tool steel (SKD11) by a capacitive plasma ion evaporation method. In order to increase the support of the substrate to the hard film, it is necessary to strengthen the hardness of the substrate. Therefore, the surface of the steel must be nitrided before the key film. The hardness of the steel after the nitriding is completed The value is approximately u X 109 Pa (pa). • jis series cold work die alloy tool steel SKD11 (high carbon high chromium steel). Its composition is as follows: SKD1 ί --- r--h ------ install -------- '1T ------ embroidery> (Please read the note on the back before filling this page) Element Consumer C, Central Consumers' Union, Ministry of Economic Affairs, 1.4-1.6 (Amount (wt%) Μ Μη (Jr
Mo re 0.15- 0.35 0.3-0.6 11-13 0.3Ό6 Balance 一S — 83.3.10,000 本紙張尺度逋用中國國家梂準(CNS ) A4規格（297公董〆 4482 4 A7 B7 五、發明説明（10) •氮化製程條件如下： 氮化製程 實驗參數 系統 N N 壓力（Chamber 7 7 流量比例（Flow 1 1 總流量（Total gas 5 5 基板溫度 5 5 基板偏壓 7 7 時間（Time (Hr)) 2 2 以下為本發明人以各種不同製程條件，分別 於氮化鋼材與無氮化鋼材上链類鐵碳改質膜， 其膜的臨界荷重及硬度值。 1、製程條件：甲烷/有機矽氧烷化合物（HMDS0)与 100% ，製程壓力維持在1·9χ10—2托（torr)， 高週波功率為100瓦，鍍膜厚度〇.35em。 結果：於無氛化鋼的臨界荷重：与0牛頓 於氮化鋼的臨界荷重：与0牛頓 硬度：5· 8x 109 帕（pa) 以ESCA分析膜的元素組成如下表： (請先«請背面之注意事項再填寫本頁) 訂 經濟部中央榇準局負工消費合作社印裝 元素 原子組成比例 C 92.18% 0 3. 39% Si 4. 43% 本紙張尺度適用中固國家標準（CNS ) A4規格（210X297公釐） 83.110,000 4 2 8 4 4Mo re 0.15- 0.35 0.3-0.6 11-13 0.3Ό6 Balance One S — 83.3.10,000 This paper size adopts China National Standard (CNS) A4 specification (297 public directors〆 4482 4 A7 B7 V. Description of the invention (10) • Nitriding process conditions are as follows: Nitriding process experimental parameter system NN Pressure (Chamber 7 7 Flow ratio (Flow 1 1 Total flow (Total gas 5 5 Substrate temperature 5 5 Substrate bias 7 7 Time (Hr)) 2 2 The following is the inventor's critical load and hardness value of iron-carbon modified film coated on nitrided steel and non-nitrided steel by various process conditions. 1. Process conditions: methane / organosiloxane Compound (HMDS0) and 100%, the process pressure is maintained at 1.9x10-2 torr, the high-frequency power is 100 watts, and the thickness of the coating is 0.35em. Result: The critical load in non-weathered steel: with 0 Newtons at Critical Load of Nitrided Steel: and 0 Newton Hardness: 5 · 8x 109 Pa (pa) The elemental composition of the membrane analyzed by ESCA is as follows: (please «please note on the back before filling out this page). Atomic composition of printed elements Proportion C 92.18% 0 3. 39% Si 4. 43% This paper size is applicable to the China National Solid Standard (CNS) A4 specification (210X297 mm) 83.110,000 4 2 8 4 4
經濟部中央標準局貝工消費合作社印裝 A7 ___B7 發明説明（11) 2、製程條件：甲烷/有機矽氧烷化合物（HMDSO) =90 % ，製程壓力維持在l_9xl〇-2托（t〇rr )，高 週波功率為100瓦，鍍膜厚度0.35 "ffl。 結果：於無氮化鋼的臨界荷重：与〇牛頓 於氮化鋼的臨界荷重：与〇牛頓 硬度：2.42x 1〇9 帕（pa) 以ESCA分析膜的元素組成如下表： 元素 原子組成比例 C 69.58% ~~ 0 21. 1¾ Si 9:32% 3、製程條件：甲燒/有機矽氧炫化合物（hmjjso ) = 87 % ，製程壓力維持在1· 9χ 1〇-2托（t〇rr)，高 週波功率為1〇〇瓦，鍍膜厚度0.35/zme 結果：於無氮化鋼的臨界荷重：31.8牛頓 於氮化鋼的臨界荷重：35. 5牛頓 硬度：10.8x 1〇9 帕（pa) 以ESCA分析膜的元素組成如下表： 元素 原子組成 C ~~57. 18% 0 28. 2% Si —14· 本紙張又度適用中國國家標準（> A4規格（210X297公釐） U3 (請先聞讀背面之注意事項再填寫本頁) ••5Ϊ -梦Printed by A7 ___B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs (11) 2. Process conditions: methane / organosiloxane compound (HMDSO) = 90%, process pressure maintained at l_9xl0-2 Torr (t〇rr) ), High frequency power is 100 watts, coating thickness is 0.35 " ffl. Result: Critical load on non-nitrided steel: and 0 Newton. Critical load on nitrided steel: and 0 Newton hardness: 2.42 × 109 Pa (pa) The elemental composition of the membrane analyzed by ESCA is as follows: Elemental atomic composition ratio C 69.58% ~~ 0 21. 1¾ Si 9: 32% 3. Process conditions: methylbenzene / organosilicon oxygen compound (hmjjso) = 87%, and the process pressure is maintained at 1.9 × 1〇-2 Torr (t〇rr). ), High-frequency power is 100 watts, coating thickness is 0.35 / zme. Results: Critical load on non-nitrided steel: 31.8 Newton. Critical load on nitrided steel: 35.5 Newton hardness: 10.8 × 109 Pa ( pa) The elemental composition of the membrane analyzed by ESCA is as follows: Elemental atomic composition C ~~ 57. 18% 0 28. 2% Si —14 · This paper is also applicable to Chinese national standards (> A4 specification (210X297 mm) U3 (Please read the notes on the back before filling out this page) •• 5Ϊ-梦
81 3.10,000 A7 B7 五、發明説明（θ 4、製程條件：甲烷/有機矽氧烷化合物（HMDSO) =81 % ，製程壓力維持在1. 9x 10_2托（torr)，高 週波功率為100瓦，鍍膜厚度0.35/zm» 結果：於無氮化鋼的臨界荷重：28. 7牛頓 於氮化鋼的臨界荷重.：大於50牛頓 硬度：1. 65x 109 帕（pa) 以ESCA分析膜的元素組成如1表： 元素 原子組成比例 C 59. 4% 0 25.55% Si 15. 05% (請先»讀背面之注意Ϋ項再填寫本頁) 裝· 訂 經濟部中央標準局—工消費合作社印製 5、製程條件：甲烷/有機矽氧烷化合物（HMDS0) =68 % ，製程壓力维持在1· 9x 10_2托（torr)，高 週波功率為100瓦，鍍膜厚度0,35只瓜。 結果：於無氮化鋼的臨界荷重：26.8牛頓 於氮化鋼的臨界荷重：大於50牛頓 硬度·· 1. 85x 109 帕（pa) 以ESCA分析膜的元素組成如下表： 元素 原子組成比例 C 60.39% 0 21.54% Si 18.07% 11 — 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 83. 3.10,000 4 4 8<ς； Α7 Β7 五、 :甲烷/有機矽氧烷化合物（HMDSO) =56 % ’製程壓力維持在l_9x 1〇-2托 (torr)，高週波功率為ι〇〇瓦， 鍍膜厚度0. 35em。 結果：於無氮化鋼的臨界荷重：23· 1牛頓 於氮化鋼的臨界荷重：32. 9牛頓 硬度：21_ 75x 109 帕（pa) 以ESCA分析膜的元素組成如下-表： 元素 原子組成比例 C 55.12% 0 22.93% ' Si 21.95¾ 經濟部中央楳準局貝工消费合作社印裝 第四圖（Νο·4)、（Νο.5)為上述實驗條件4、 5的紅外線光譜圖，從圖中可以看到28〇〇_ 3000cm—1的碳氫鍵結（C-H)，1570 cur〗附近的 碳碳雙鍵（C=C)，，lOOO-iioo cnfi的矽氧矽鍵 結（Si-0-Si )，及800 cm-1附近的碳矽鍵結 (Si-C)，此為膜中的主要鍵結，因其他實驗條 件的紅外線光譜圖均大同小異，就定性上而言， 膜的主要鍵結並沒有因氣體成分不同而改變， 故只附上兩張紅外線光譜圖代表之。 第五圖（a)'(b)、（c)為上述實驗樣件1、4、 δ的刮痕測試，在光學顯微鏡下的觀察結果，由 第五圖（b )可以觀察到，鑽石頭荷重達到5〇 /2-· 本紙張尺度適用中國國家標率（CNS ) A4規格（21〇χ：297公楚 83. 3.10,000 III —ί. I . 1n n Lrn I n n i n ^ I —i *ϋ II 終 I (請先聞讀背面之注意事項再填寫本頁} 4 4 經濟部中央標準局員工消費合作社印裝 A7 B7 五、發明説明（u) 牛頓，而膜仍良好的附著於基版上，顯示其優異 的附著行為。 第六圖（a)、（b)為上述條件4、6的微硬度 測試’於原子力顯微鏡（AFM )下觀察的結果， 其硬度質分別為1·65χ 109帕（pa)及21.75x 109 帕（pa)。 本發明之漸進層的設計主要也是以上述有機 矽氧化合物中間層為基礎，連續的改變有機矽 氧烷化合物的比例，以形成層與層之間的性質 不會有劇烈的改變的漸進層，其中每一層的製 程條件、氣體比例、臨界荷重及硬度如上述製 程條件1、2、3、4、5、6 ;再在最上面以純的 甲烷鍍上純的類鑽碳薄膜。 此類鑽探薄膜的製程條件為：在真空系統中通 以純CH4，壓力4·4χ 10.Horr，高週波功率j 〇〇 瓦’平板式電漿，鍍膜厚度為〇.35jfZm。 第七圖為此漸進層系統的示意圖，其臨界荷重 為22. 4牛頓硬度31x 1〇9帕（pa)。 圖式說明： 第一圖：類鑽碳膜内應力釋放示意圖。 第二圖：電容式電漿離子蒸鍍系統圖。 /3 — 私紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） 83.3.10,000 il· - ·= -l·— - - i ^^1 I - I !» Hr (請先《讀背面之注意事項再填寫本頁) ^432 A7 B7 五、發明説明（is) 第三圖：作拉曼（Raman)光譜分析圖 第四圖：紅外線光譜圖。 第五圖：刮痕測試光學顯微鏡照片。 第六圖：微硬度測試原子力顯微鏡照片 第七圖：此漸進層系統的示意圖。 -----------參------'1T---------ΓΪ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印繁 本紙張尺度適用中國國家標準（CNS > Α4規格（210X297公釐） 83.110,00081 3.10,000 A7 B7 V. Description of the invention (θ 4, Process conditions: methane / organosiloxane compound (HMDSO) = 81%, process pressure maintained at 1. 9x 10_2 Torr, high cycle power of 100 watts , Coating thickness 0.35 / zm »Result: Critical load on non-nitrided steel: 28.7 Newtons on critical load of nitrided steel .: More than 50 Newton Hardness: 1. 65x 109 Pa (pa) Analysis of elements of the film by ESCA The composition is as shown in Table 1. Element atomic composition ratio C 59.4% 0 25.55% Si 15. 05% (please first read the note on the back before filling out this page) Process 5. Process conditions: methane / organosiloxane compound (HMDS0) = 68%, process pressure maintained at 1.9x 10_2 torr, high-frequency power of 100 watts, and coating thickness of 0,35 melons. Results: Critical load for non-nitrided steel: 26.8 Newtons. Critical load for nitrided steel: greater than 50 Newtons hardness · 1. 85x 109 Pa (pa) The elemental composition of the membrane analyzed by ESCA is as follows: Elemental atomic composition ratio C 60.39% 0 21.54% Si 18.07% 11 — This paper size applies to the Chinese national standard (CNS ) A4 size (210X297 mm) 83. 3.10,000 4 4 8 < ς A7 Β7 5 .: Methane / organosiloxane compound (HMDSO) = 56% 'The process pressure is maintained at l_9x 1〇-2 Torr (torr ), High-frequency power is ιοwatt, coating thickness is 0.35em. Result: critical load on non-nitrided steel: 23.1 Newton critical load on nitrided steel: 32.9 Newton hardness: 21_ 75x 109 Pa (Pa) The elemental composition of the membrane analyzed by ESCA is as follows: Table: Elemental atomic composition ratio C 55.12% 0 22.93% 'Si 21.95¾ The fourth picture (No. 4), Νο.5) is the infrared spectrum of the experimental conditions 4 and 5 above. From the figure, you can see the hydrocarbon bond (CH) of 2800_3000cm-1, and the carbon-carbon double bond near 1570 cur (C = C), 100-iioo cnfi's silicon-oxygen-silicon bond (Si-0-Si), and carbon-silicon bond (Si-C) near 800 cm-1. This is the main bond in the film. The infrared spectra of the experimental conditions are all similar. In terms of qualitative analysis, the main bonds of the film have not changed due to different gas components, so only two infrared rays are attached. The fifth graph (a) '(b), (c) is the scratch test of the above-mentioned experimental samples 1, 4, and δ. The observation results under an optical microscope can be obtained from the fifth graph (b). It is observed that the diamond head load reaches 5〇 / 2- · This paper size is applicable to China National Standards (CNS) A4 specifications (21〇χ: 297 Gongchu 83. 3.10,000 III — ί. I. 1n n Lrn I nnin ^ I —i * ϋ II Final I (Please read the notes on the back before filling out this page} 4 4 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 5. Invention Description (u) Newton, and the film is still good Adheres to the base plate, showing its excellent adhesion behavior. The sixth graphs (a) and (b) are the results of the micro hardness test of conditions 4 and 6 above, which were observed under an atomic force microscope (AFM). The hardness properties were 1.65 × 109 Pa and 21.75x 109 Pa, respectively. (Pa). The design of the progressive layer of the present invention is also mainly based on the above-mentioned organic silicon oxide intermediate layer, and continuously changes the proportion of the organic silicon oxide compound to form a progressive layer that does not have drastic changes in properties between layers. The process conditions, gas ratio, critical load, and hardness of each layer are as described in the above process conditions 1, 2, 3, 4, 5, 6, and a pure diamond-like carbon film is coated with pure methane on the top. The process conditions for this type of drilling film are: pure CH4 in a vacuum system, pressure 4 · 4χ 10.Horr, high cycle power j 00 watts' flat plasma, and the coating thickness is 0.35jfZm. The seventh diagram is a schematic diagram of the progressive layer system whose critical load is 22.4 Newton hardness 31x109 Pa (pa). Schematic description: Figure 1: Schematic diagram of stress release in diamond-like carbon film. Figure 2: Capacitive plasma ion evaporation system. / 3 — Private paper size applies to China National Standard (CNS) A4 (210X297 mm) 83.3.10,000 il ·-· = -l · —--i ^^ 1 I-I! »Hr (Please read" Note on the back, please fill in this page again) ^ 432 A7 B7 V. Description of the invention (is) The third picture: Raman spectrum analysis diagram The fourth picture: infrared spectrum diagram. Fifth Figure: Scratch Test Optical Micrograph. Figure 6: Atomic force microscope photo of micro hardness test Figure 7: Schematic diagram of this progressive layer system. ----------- See ------ '1T --------- ΓΪ (Please read the notes on the back before filling this page) Consumption cooperatives printed and printed on this paper are in accordance with Chinese national standards (CNS > Α4 size (210X297 mm) 83.110,000