1248123 九、發明說明： 【發明所屬之技術領域】 本發明係-義鑽碳薄膜去除方法及製成品，此方法 係將一經表面被覆類鑽碳薄膜處理後之構件，浸泡於氯化 氮水溶液中，可將構件表面之類鑽碳薄膜完全去除。成為 一種在不傷及構件表面的情況下，能有效將類鑽碳薄膜去 除之方法，提供產業界之應用價值高及降低生產過程中所 導致之損失。 【先前技術】 利用表面處理技術被覆功能性薄膜以進行材料表面改 質，已廣為應用在半導體產業、光電產業、模具產業、機 械加工業、工具機業、運動休閒產品、營建和廚浴業。 自然界中最硬的鑽石，也能藉由鍍臈技術被覆在物件 表面，形成鑽石膜或類鑽碳薄膜。類鑽碳薄膜由於具備碳 的sp3鍵結與印2鍵結，因而包含了許多特性如高硬度、低 摩擦、高化學鈍性、高熱傳等。類鑽碳膜多樣化的性質使 其能應用於不同領域。其中，類鑽碳薄膜因具有高硬度、 低導電性、低摩擦係數、低化學親和力等性質，由於這此 !248123 優越特性之組合，使得轉碳賴被覆技術之制相當廣 泛。 類鑽碳薄膜之組織為非結晶（n〇n—crystalline)組 織，同時具* sp2#口 Sp3鍵結之碳膜。其又可分為含氫麵 石反薄膜（a-c:H)與不含氫類鑽碳薄膜（a—c)。含氫類鑽碳 薄膜-般湖碳魏_解方絲合成，如㈣輔助化學 汽相/儿積法（PECVD )、熱燈絲化學汽相沉積法 (Hot-Filament OT))或雷射沉積法（Laser Ablasi〇n); 而不含氫類鑽碳薄膜則採用磁控濺射法（Magnetron Sputtering)- Electron Beam Evaporation) 或陰極電弧電漿蒸鍍法（CathQdic Arc Evaporation)等。 如中華民國專利公告號420723，該發明係有關於一種 形成無氫類鑽碳膜之方法，其中厚度約為丨到議冑微⑽9) 米的類鑽韻沈積在—塊樣本基板或場效發射轉列上， 繼之與含有氟氣的糊電漿曝接;其中在後—步驟裡，鑛層 内含有的麟域起的化學侧反觸去除；其中藉以形 成無氫類鑽碳朗步驟可重複進行，藉而獲得财的類鑽 碳膜厚度。 1248123 如中華民國專利公告號448243，該發明係有關於一種 製備類鑽碳臈與鋼材間高附著力的中間層的方法，尤其是 才曰利用以含有機矽氧烷化合物蒸鍍中間層以提高類鑽碳膜 披覆於鋼材上的附著力的方法。此中間層所含有的矽氧官 能基可以加強類鑽碳膜與鋼材基板間的黏著力。而且藉著 氣相的矽氧烷化物和甲烷比例的逐漸改變，可形成一漸進 的中間層’進一步加強類鑽碳膜與鋼材間的附著力。該發 明之漸進層的製程為低溫製程，其可與最外層的類鑽碳膜 的低溫製程相匹配，與工業高溫製程比較，該發明較具競 爭力。 如中華民國專利公告號495553，該發明係採用陰極電 孤蒸鑛方式沈積類鑽碳膜的製備方法，此種方法乃是利用 CAE金屬離子的高離子能量激發真空室中碳氫氣體之裂解 反應而沉積高硬度、高潤滑性之類鑽碳膜，該發明所製備 之類鑽碳膜由於内含金屬成分而具有良好之韌性，另外沉 積類鑽碳膜之前可藉同一金屬弧源以CAE製程先行沉積一 層或多層之金屬、金屬氮化物或金屬碳化物介層以強化類 鑽碳膜之附著性，再通入碳氫氣體與金屬弧源電漿產生碳 氫氣體之裂解反應而沈積類鑽碳膜。 Ϊ248123 如中華民國專利公告號585933,該發明揭示一種沉積 低應力和高附著性類鑽碳膜的方法。首先自離子源引出氮 離子束轟擊基材表面，以去除基材表面污染物並在基材表 面形成含氮官能基，隨即再導入碳氫氣體於氮離子束行進 路徑上，來沉積高附著性含氮類鑽碳膜。該發明方法特別 適用於光學瓣基材沉細鑽賴，作為魏賴膜之用。 由上述已公告之中華民國專利，目前僅有類鑽碳薄膜 之製備方法之發明，肖無有醜鑽碳細去除方法及製成 品之專利，故本發明對產業界可說是非常重要，對相關的 研究亦為先驅。 目前製備類鑽碳_的過財，f遭著性不佳而 導致構件表面之點或面的局部剝落，並產生不良品之構 件，其原因包括類鑽碳_本身之高誠力、前處理清洗 製程缺失或真空腔體内粉鮮因素所造成。 由於類鑽碳薄膜具有高硬度、低摩擦係數與低化學親 和力等，使不良品構件表面上之類鑽碳薄膜需經由乾、濕 喷沙法才能將其自構件表面上去除。射沙法去除類鑽碳 薄膜的同時亦對構件表面產生破壞性的損傷，其對具高精 1248123 密度、低表面粗糙度與具銳角之構件將無法適用 ’而易導 致商譽之損失。 本發明類鑽碳薄膜去除方法及製成品，在不傷及構件 之情況下’有效地完成表面處理的工作，至目前為止，除 了本發明外，國内尚無相關的發明出現。 【發明内容】 本發明類鑽碳薄膜去除方法及製成品，係將經表面被 覆處理-層麵碳_之構件，在室溫下，浸泡於化學溶 液中’經過-段時間，可將構件表面之賴碳薄膜完全去 除。此化學溶液可蝕刻構件表面之類鑽碳薄膜。 上述之化學溶液可為氯化氫水溶液。 另外，亦可選用催化劑以控制反應之速度。該催化劑可 為硝酸，經發明人實驗測試發現，在化學溶液中在加入硝酸 可以有效增加類鑽碳薄膜去除之退膜速率。 本發明具有以下之優點··（1)退膜時間短、成本低及 具產業應用價值。（2)原構件尺寸精度不變。（3)去除類 鑽石反薄膜後之構件，經拋光後再被覆類鑽碳薄膜，光澤度 1248123 佳0 本發明與目前表面處理業界所採用之喷沙法，比較後 明顯發現，去除賴韻職之構縣面具有較低之表面 粗趟度【請參閱第3圖】與光澤度【請參閱第4圖】。 【實施方式】 為達成上述之目的與功效，本發明類鑽碳薄膜去除方 法及製成品，是以化學溶液浸泡構件後，去除構件表面之 類鑽碳細；絲麵碳薄職讀件，麵光後可再被 覆類鑽碳_，在本發明帽取容綠得之氯化氫水溶液 作為實施用的化學溶液。 本發明類鑽碳薄膜去除方法及製成品，【請參閱第^ 圖】，其去除步驟為： a·準備溶液：該化學溶液為濃度1% ~37%之氣化氫 水溶液。 b·置入構件：將欲去除類鑽碳薄膜之構件置入氯化 氫水溶液。 1248123 薄膜去除·視構件之膜厚於適當時間後取出 全去除之構件。 之完 藉 由上述方法在不傷及構件表面的情訂，去 表面之類鑽碳薄膜。 、本發明_碳_去除方法，其去除後再重新披覆牛驟為【請參閱第2圖】： 夕 準備溶液··該化學溶液為濃度 水溶液。 1%〜37%之氯化氫 b·置入構件：將欲去除類鑽碳薄膜之構件置入氯化 氫水溶液。 ' 薄膜去除：視構件之膜厚於適當時間後 全去除之構件。 取出之完 d·構件拋光：將已去除類鑽碳薄膜之構件表面予 拋光處理。 以 1248123 e·再彼覆薄膜：將已拋光之構件視需要再予以彼覆 類鑽碳薄膜。 如此可將已適當去除原先之類鑽碳薄膜之構件、再拋 光、再予以披覆一層類鑽碳薄膜而成為新品。該去除類鑽 石厌薄膜後之新構件表面具有較低之表面粗縫度而具有良好 之光澤度，能有效提高新構件之品質。 以下是本發明之一實施例，其實施條件及相關資料與 數據如下： (1) 構件基材· SUS304不鑛^鋼。 (2) 基材測試面積：3公分（cm) X 2公分（cm) (3) 薄膜類型：類鑽碳薄膜。 (4) 薄膜厚度：2微米（pm)。 (5) 化學溶液：濃度15 %之氯化氫水溶液。 12 1248123 (6) 水溶液容積：500亳升（ml)。 (7) 水溶液溫度：攝氏〇度〜1〇〇度 (8) 容器：可耐強酸。 實施方式： 將表面被覆類鑽碳薄膜之構件，浸泡於5〇〇毫升（mi) 之濃度1%〜37%之氯化氫水溶液。 試驗結果： 經過1分鐘至4小時浸泡處理，構件表面之被覆類鑽 奴薄膜，已完全去除【請參閱第5圖】。溶液溫度會影響退 膜速率，如在相同濃度下，如15%，退膜速率於25°C時約 〇· 5微米（卵）/小時（hr)，1〇〇。〇時約〇· 5微米（//m) /分鐘（min)。其在室溫下（約25°C)最佳濃度範圍在12 〜18%。在這個溫度及濃度配合下浸泡退膜，直到退除完畢 均不會傷害到構件表面。 本發明類鑽碳薄膜去除方法及製成品之優點很多，例 如所使用之氯化氫水溶液容易取得，經加以調配至適當濃 13 1248123 度。氯化氫水溶液可以在室溫下操作，亦可不需要再經過 加熱或其他之複雜程序’避免許多潛伏之工安問題。 此外’欲去除類鑽奴薄膜之構件，也不需要擔心會影 響原來的尺寸精度，非常適合複雜造型之構件。可以省略 準備其他加工知序之成本，像是研磨、铁削等，便可直接 進行去除構件表面之類鑽碳薄膜。因未使用機械加工法去 除構件表面之類鑽碳薄膜，也不會有殘留應力產生。殘留 應力容易使成品發生翹曲變形現象，影響產品的精度及強 度要求，且對於後續的接著、塗裝等加工都將造成不良影 響。對於透明光學應用產品，也會因殘留應力造成光散射， 影響到產品的光學特性。 另外，欲去除已鍍膜之膜厚，可以依需求調配退膜速 率比，對時間就是成本的產業界而言，是非常經濟且實用 的方法。去除構件表面之類鑽碳薄膜再予以拋光，接著再 重新披覆-躺鑽碳_成騎品。該她_碳薄膜後 之新構件表面具有較低之表面粗糙度，而具有良好之光澤 度，能有效提高新構件外觀之品質 除上述之步驟外，本發明亦可配合適當之催化劑以控 1248123 制反應之速度。該催化劑可為硝酸(HN〇3)，經發明人實驗測 武發現’在化學溶液中在加入硝酸(HN〇3)可以有效增加類鑽 碳薄膜去除之賴速率；其_數據整理如下： 氣化氫水 溶液 (HC1) 硝酸(HNOd 時間 退膜速率（//m (min) hr)1248123 IX. Description of the Invention: [Technical Field] The present invention is a method for removing a carbon film from a diamond, and a finished product, which is obtained by immersing a member treated with a surface-coated diamond-like carbon film in an aqueous solution of nitrogen chloride. The carbon film on the surface of the component can be completely removed. It is a method to effectively remove the diamond-like carbon film without damaging the surface of the component, providing high industrial application value and reducing the loss caused by the production process. [Prior Art] Surface treatment technology is used to coat functional films for surface modification. It has been widely used in semiconductor industry, optoelectronic industry, mold industry, machinery processing industry, machine tool industry, sports and leisure products, construction and kitchen bath industry. . The hardest diamond in nature can also be coated on the surface of objects by rhodium plating to form a diamond film or a diamond-like carbon film. The diamond-like carbon film contains many properties such as high hardness, low friction, high chemical bluntness, and high heat transfer due to the carbon sp3 bond and the bond 2 bond. The diverse nature of diamond-like carbon films allows them to be used in different fields. Among them, the diamond-like carbon film has high hardness, low electrical conductivity, low friction coefficient, low chemical affinity and the like. Due to the combination of the superior characteristics of the 248123, the carbon-coated coating technology is quite extensive. The structure of the diamond-like carbon film is a non-crystalline (n〇n-crystalline) structure with a carbon film of * sp2# sp3 bonded. It can be further divided into a hydrogen-containing reverse stone film (a-c:H) and a hydrogen-free diamond-free carbon film (a-c). Hydrogen-like diamond carbon film-like lake carbon Wei_solution square wire synthesis, such as (4) auxiliary chemical vapor phase / pediatric method (PECVD), hot filament chemical vapor deposition (Hot-Filament OT) or laser deposition (Laser Ablasi〇n); and the hydrogen-free carbon film is magnetron sputtering (Electron Beam Sputtering) - Electron Beam Evaporation or CathQdic Arc Evaporation. For example, the Republic of China Patent Publication No. 420723, the invention relates to a method for forming a hydrogen-free diamond-like carbon film, wherein a thickness of about 丨 to 胄 胄 (10) 9) meters is deposited on a sample substrate or field effect emission. The transition is followed by exposure to a paste plasma containing fluorine gas; wherein in the latter step, the chemical side of the forest layer is removed by a chemical side; wherein the hydrogen-free diamond-forming step can be formed. Repeatedly, to obtain the diamond-like carbon film thickness of the money. 1248123 For example, the Republic of China Patent Publication No. 448243, the invention relates to a method for preparing an intermediate layer having high adhesion between a diamond-like carbon crucible and a steel material, in particular, using an intermediate layer deposited by a machine containing a helium oxide compound to improve A method of adhering a carbon-coated carbon film to a steel. The oxygen-containing functional group contained in the intermediate layer can enhance the adhesion between the diamond-like carbon film and the steel substrate. Moreover, by the gradual change of the ratio of the oxyalkylate and the methane in the gas phase, a progressive intermediate layer can be formed to further enhance the adhesion between the diamond-like carbon film and the steel. The progressive process of the invention is a low temperature process that matches the low temperature process of the outermost diamond-like carbon film, which is more competitive than industrial high temperature processes. For example, the Republic of China Patent Publication No. 495553, the invention is a method for preparing a diamond-like carbon film deposited by a cathode electric singe-steaming method, which utilizes high ion energy of CAE metal ions to excite a cleavage reaction of hydrocarbon gas in a vacuum chamber. The carbon film prepared by the invention has high toughness and high lubricity. The carbon film prepared by the invention has good toughness due to the inclusion of metal components, and the same metal arc source can be used in the CAE process before depositing the diamond-like carbon film. First deposit one or more layers of metal, metal nitride or metal carbide interlayer to enhance the adhesion of the diamond-like carbon film, and then pass through the cracking reaction of hydrocarbon gas and metal arc source plasma to generate hydrocarbon gas to deposit the diamond. Carbon film. Ϊ 248123, for example, the Republic of China Patent Publication No. 585933, which discloses a method of depositing a low stress and high adhesion diamond-like carbon film. First, a nitrogen ion beam is extracted from the ion source to bombard the surface of the substrate to remove contaminants on the surface of the substrate and form a nitrogen-containing functional group on the surface of the substrate, and then introduce a hydrocarbon gas on the path of the nitrogen ion beam to deposit high adhesion. Nitrogen-containing diamond carbon film. The method of the invention is particularly suitable for use in an optical valve substrate, as a Wei Lai film. According to the above-mentioned announced Republic of China patent, there is only the invention of the preparation method of the diamond-like carbon film, the invention of the ugly carbon removal method and the patent of the finished product, so the invention can be said to be very important to the industry, Related research is also a pioneer. At present, the preparation of diamond-like carbon has been used to cause partial peeling of points or surfaces on the surface of the component, and the components of the defective product are produced. The reasons include the high-strength force of the diamond-like carbon itself and the pre-treatment cleaning process. Defective or caused by powdery factors in the vacuum chamber. Due to the high hardness, low friction coefficient and low chemical affinity of the diamond-like carbon film, the carbon-coated film on the surface of the defective component needs to be removed from the surface of the component by dry and wet sandblasting. The sand-blasting method removes the diamond-like carbon film and also causes destructive damage to the surface of the component. It will not be applicable to components with high precision 1248123 density, low surface roughness and sharp angles, which may lead to loss of goodwill. The diamond-like carbon film removing method and the finished product of the present invention can effectively perform the surface treatment without damaging the member. Up to now, in addition to the present invention, there has been no related invention in the country. SUMMARY OF THE INVENTION The method and the finished product for the diamond-like carbon film of the present invention are characterized in that the surface is coated and treated with a layer of carbon, and immersed in a chemical solution at room temperature for a period of time. The carbon film was completely removed. This chemical solution etches a carbon-coated film such as a surface of a member. The above chemical solution may be an aqueous hydrogen chloride solution. Alternatively, a catalyst may be employed to control the rate of the reaction. The catalyst can be nitric acid. It has been found by experiments by the inventors that the addition of nitric acid in a chemical solution can effectively increase the rate of film removal of the diamond-like carbon film. The invention has the following advantages: (1) short filming time, low cost and industrial application value. (2) The original component dimensional accuracy is unchanged. (3) After removing the diamond-like reverse film, after polishing, the diamond-like carbon film is coated, and the gloss is 1248123. The invention is compared with the sandblasting method adopted by the surface treatment industry at present, and it is obvious that the Lai Yun job is removed. The county has a low surface roughness [see Figure 3] and gloss [see Figure 4]. [Embodiment] In order to achieve the above object and effect, the method and the finished product for the diamond-like carbon film of the present invention are obtained by soaking the member with a chemical solution, and removing the carbon-like fine carbon on the surface of the member; After the light, the diamond-like carbon can be further coated, and the aqueous hydrogen chloride solution obtained by taking the green color in the cap of the present invention is used as a chemical solution for the implementation. The method for removing diamond-like carbon film of the present invention and the finished product, [please refer to the figure], the removal steps are as follows: a. Preparation solution: The chemical solution is a hydrogenated hydrogen solution having a concentration of 1% to 37%. b. Inserting member: A member for removing the diamond-like carbon film is placed in an aqueous hydrogen chloride solution. 1248123 Film removal · The film thickness of the component is taken out after a suitable time to remove the fully removed component. After the above method, the carbon film is drilled on the surface without damaging the surface of the member. In the present invention, the carbon_removal method is carried out, and the bovine powder is re-coated after the removal (see Fig. 2): 夕 Preparation of the solution · The chemical solution is a concentrated aqueous solution. 1% to 37% of hydrogen chloride b. Inserting member: A member for removing a diamond-like carbon film is placed in an aqueous hydrogen chloride solution. 'Film removal: A component that is completely removed after the appropriate thickness of the film. Finished out d. Component polishing: The surface of the component from which the diamond-like carbon film has been removed is polished. The film is coated with 1248123 e. The polished component is coated with a carbon film as needed. In this way, a member that has been properly removed from the original carbon-thin film can be re-polishing and then coated with a diamond-like carbon film to become a new product. The surface of the new component after removing the diamond-like film has a low surface roughness and a good gloss, and can effectively improve the quality of the new component. The following is an embodiment of the present invention, and the implementation conditions and related materials and data are as follows: (1) Component substrate SUS304 non-mineral steel. (2) Substrate test area: 3 cm (cm) X 2 cm (cm) (3) Film type: diamond-like carbon film. (4) Film thickness: 2 microns (pm). (5) Chemical solution: a 15% aqueous solution of hydrogen chloride. 12 1248123 (6) Aqueous solution volume: 500 liters (ml). (7) Aqueous solution temperature: Celsius to ~1 degree (8) Container: Resistant to strong acid. Embodiment: A member coated with a diamond-like carbon film on a surface was immersed in an aqueous solution of hydrogen chloride having a concentration of 1% to 37% at a concentration of 5 milliliters (mi). Test results: After 1 minute to 4 hours of immersion treatment, the coated film of the surface of the component has been completely removed [see Figure 5]. The temperature of the solution affects the rate of de-filming, such as at the same concentration, such as 15%, and the rate of film detachment is about 5 μm (egg) per hour (hr) at 25 ° C, 1 〇〇. When the time is about 5 μm (//m) / minute (min). It has an optimum concentration range of 12 to 18% at room temperature (about 25 ° C). Soaking the film at this temperature and concentration will not damage the surface of the component until it is removed. The diamond-like carbon film removal method and the finished product of the present invention have many advantages. For example, the aqueous hydrogen chloride solution used is easily obtained, and is formulated to an appropriate concentration of 13 1248123 degrees. The aqueous hydrogen chloride solution can be operated at room temperature or without the need for heating or other complicated procedures to avoid many latent safety problems. In addition, the components that want to remove the diamond-like film do not need to worry about the original dimensional accuracy, which is very suitable for complex modeling components. It is possible to omit the cost of preparing other processing orders, such as grinding, iron cutting, etc., and directly remove the carbon-coated film such as the surface of the component. Since the machining method is used to remove the carbon film of the surface of the component, no residual stress is generated. Residual stress tends to cause warpage of the finished product, affecting the accuracy and strength requirements of the product, and will have adverse effects on subsequent processing such as subsequent coating. For transparent optical applications, light scattering is also caused by residual stress, which affects the optical properties of the product. In addition, in order to remove the film thickness of the coated film, it is possible to adjust the filming rate ratio as required, which is a very economical and practical method for the industry where time is a cost. The carbon film is removed from the surface of the component and then polished, and then re-coated - lying carbon. The surface of the new component after the carbon film has a low surface roughness, and has a good gloss, which can effectively improve the quality of the appearance of the new component. In addition to the above steps, the present invention can also be combined with a suitable catalyst to control 1248123. The speed of the reaction. The catalyst can be nitric acid (HN〇3). It has been found by the inventors that 'the addition of nitric acid (HN〇3) in the chemical solution can effectively increase the rate of diamond-like carbon film removal; its data is as follows: Aqueous hydrogen solution (HC1) nitric acid (HNOd time release rate (//m (min) hr)
•所以加入硝酸濃度可在1〜70%都有效果 2·且由退膜速率，確實加入硝酸⑽〇3)是可促進反應。• Therefore, the concentration of nitric acid added can be effective at 1 to 70%. 2. And the rate of de-filming is indeed added to nitric acid (10) 〇 3) to promote the reaction.
…上述本發_鑽韻膜去除方法及製成品之使用及 貫知例4本發明較佳實施例之一，並非用以揭限本發明 之特被’舉凡利用本發明相關之技術手段、創設原理之再 創作’均應屬本發明之創設目的及申料利範圍之内。 杂综上所述，本發明類鑽碳薄膜去除方法及製成品，確 。達至J實細之功效，完全符合發明專利之申請要件，爰 依法向鈞局提呈本案發明專利之申請，敬祈鈞局暨貴 審查委員惠予審理，並早日賜准本案之發明專利，實感德 便。 15 1248123 【圖式簡單說明】 第1圖：本發明類鑽碳薄膜去除方法及製成品之去除步驟 示意圖。 第2圖：本發明類鑽碳薄膜去除方法及製成品之去除後再 重新披覆步驟示意圖。 第3圖：本發明類鑽碳薄膜去除方法及製成品之構件表面 粗糙度。 第4圖：本發明類鑽碳薄膜去除方法及製成品之構件表面 光澤度。 第5圖：本發明類鑽碳薄膜去除方法及製成品之構件表面 去除被覆之類鑽碳薄膜前後示意圖。 16 1248123 【主要元件符號說明】The above-mentioned present invention is a method for removing the film and the use of the finished product and a known example of the present invention. The re-creation of the principle should be within the scope of the creation of the invention and the scope of the application. In summary, the method and the finished product of the diamond-like carbon film of the present invention are confirmed. The effect of reaching the fineness of J is in full compliance with the application requirements of the invention patent, and the application for the invention patent of the case is submitted to the bureau in accordance with the law, and the examination and approval of the member of the examination committee will be granted, and the invention patent of the case will be granted as soon as possible. Real sense of virtue. 15 1248123 [Simple description of the drawings] Fig. 1 is a schematic view showing the removal method of the diamond-like carbon film of the present invention and the removal steps of the finished product. Fig. 2 is a schematic view showing the removal method of the diamond-like carbon film of the present invention and the step of re-coating after the removal of the finished product. Fig. 3 is a view showing the method for removing a carbon-like film of the present invention and the surface roughness of the member of the finished product. Fig. 4 is a view showing the method for removing a carbon-like film of the present invention and the surface gloss of the member of the finished product. Fig. 5 is a schematic view showing the method for removing the carbon-like film of the present invention and the surface of the member of the finished product before and after removing the carbon-coated film such as the coated carbon film. 16 1248123 [Main component symbol description]
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