TW585933B - Deposition of highly adhesive diamond-like carbon film by ion beam process - Google Patents

Abstract

A process for depositing diamond-like carbon (DLC) film with low stress and high adhesion on the surface of substrates is disclosed. The substrate is first bombarded with energetic nitrogen ions from an ion source to remove surface contaminants and simultaneously to induce nitrogen functional group on the surface. After bombardment, a highly adhesive nitrogen containing diamond-like carbon film is deposited by introducing hydrocarbon gas into the nitrogen ion beam downstream of the ion source. This process is especially useful for deposition DLC film on optical plastics as a protective coating.

Description

585933 ---MMl 89122059 _ 年月 曰______ 五、發明說明（1) 〜、【發明所屬之技術領域】 本發明係關於一種藉離子束以在一基材上沉積硬化膜 之方法，尤其有關一種在塑膠、金屬、玻璃、陶瓷等基材 上，沉積高附著性類鑽碳膜，形成透明、抗磨耗保護層之 方法。 、【先前技術】585933 --- MMl 89122059 _ year and month ______ 5. Description of the invention (1) ~, [Technical field to which the invention belongs] The present invention relates to a method for depositing a hardened film on a substrate by using an ion beam, and is particularly relevant A method for depositing a high-adhesive diamond-like carbon film on a substrate such as plastic, metal, glass, or ceramic to form a transparent, wear-resistant protective layer. , [Prior art]

在薄膜領域中，類鑽碳膜（Diamond - Like Carbon，簡 寫DLC)已成為近年來被相當看好而且積極開發研究的目 標。DLC和鑽石有許多類似的特性，諸如高硬度、高機械 強度、低磨耗係數、化學惰性等。DLC和鑽石結構一樣含 有sp鍵結，只是不像鑽石具有長範圍的結晶序列，但DLC 比鑽石薄膜更適合應用在不同材料的基材上，蓋因其具有 較低的沉積溫度，更完美的表面平滑度，及可以鐘在複雜 的立體形狀上，所以DLC的工業發展潛力與日倶增，已經 逐步的應用在不同的領域上。In the field of thin films, diamond-like carbon (DLC) has become a very promising and actively developed research target in recent years. DLC and diamond have many similar characteristics, such as high hardness, high mechanical strength, low coefficient of wear, and chemical inertness. DLC contains sp bonds like diamond structure, but unlike diamond, it has a long range of crystalline sequences, but DLC is more suitable for application to different materials than diamond film. The cover has a lower deposition temperature and is more perfect The smoothness of the surface, and the ability to focus on complex three-dimensional shapes, so the industrial development potential of DLC is increasing and it has been gradually applied in different fields.

雖然DLC#有良好的光學特性以及非常優秀的抗磨性 和耐化學侵#性’但目前尚未廣泛的應用在塑膠基材（包 括塑膠鏡片）的保護膜上。主要原因是DLC成膜時會產生高 殘留應力’使得DLC膜和基材間的附著力減弱，尤其是基 材從高溫逐漸降溫時，此現象更為明顯。直次是DLC膜和 塑膠基材的熱膨服係數差異大，在經過埶脹冷縮後，此較Although DLC # has good optical characteristics and very good abrasion resistance and chemical resistance #, it has not been widely used in protective films of plastic substrates (including plastic lenses). The main reason is that the high residual stress generated during DLC film formation reduces the adhesion between the DLC film and the substrate, especially when the substrate is gradually cooled from a high temperature. The direct difference is that the thermal expansion coefficient of DLC film and plastic substrate is very different.

$ 5頁 585933 < _-——t^J9122059 年月日 倏正__ 五、發明說明（2) 差的附著力無法抵擋膨脹收縮所產生的拉力，因此DLC便 會裂開而剝落。 為增加DLC和基材間的附著力，已有許多方法被研究 發展出來。如核給M.J· Mirtich等人之美國專利第 4 4 9 0 2 2 9號（1 9 8 4年）所揭示者，其為使用雙離子束法沉積 DLC，一支主考夫曼離子源發射碳氫離子束成長薄膜，另 一支次離子源發射氬離子束作為離子助鍍。此法由於柵極 的限制，引出的離子束很小，沉積速率無法達到量產要 求，而且橋極離子源的操作亦十分繁瑣。又如核給F. Μ· Kimock等人之美國專利第519〇8〇7號（1 9 93年）則提出先在 塑膠鏡片上塗佈一層含矽樹脂，然後濺鍍Si〇作為中間層 ，接著以離子束法直接沉積D L C。此法由於塗佈技術的限 制，不適用於大面積基材，而且多段式的製程使得製造成 本提南。又如核給D· A. Ba 1 dwi η等人之美國專利第 561617 9號（199 7年）提案使用無栅極離子源解離碳氫氣體 後，離子束直接沉積DLC。此法是將碳氫氣體直接引入放 電室中解離，使得放電室的陽極很快就鍍上一層絕緣膜， 造成離子源不穩定無法長時間使用。又如核給洪敏雄、洪 丨文進二人之中華民國專利第3 7 0 5 7 1號（1 9 9 9年）提出一種連 續式成長類鑽碳膜的方法，係以電漿輔助化學氣相沉積法 (PECVD)沉積一層具有梯度組成的含矽碳膜在一基材上， 隨後再連續沉積:含矽類鑽碳膜（Si_DLC)或類鑽碳膜。此 法需在基材上加鬲溫，因此不適用於不耐高溫的塑膠基 材0$ 5 pages 585933 < _-—— t ^ J9122059 日 正 __ 5. Explanation of the invention (2) Poor adhesion cannot resist the tensile force generated by expansion and contraction, so the DLC will crack and peel off. In order to increase the adhesion between DLC and the substrate, many methods have been developed. As disclosed in U.S. Patent No. 4 490 0 2 9 (1984) issued to MJ Mirtich et al., Which is a method for depositing DLC using a dual ion beam method, a main Kauffman ion source emits carbon The hydrogen ion beam grows into a thin film, and another secondary ion source emits an argon ion beam as an ion assisted plating. Due to the limitation of the grid, the ion beam extracted by this method is very small, the deposition rate cannot meet the mass production requirements, and the operation of the bridge ion source is very complicated. Another example is U.S. Patent No. 5,198,007 (1989), which was issued to F.K. Kimock et al., And proposed that a plastic lens be coated with a silicon-containing resin first, and then SiO be sputtered as an intermediate layer. DLC was then deposited directly by the ion beam method. Due to the limitation of coating technology, this method is not suitable for large-area substrates, and the multi-stage manufacturing process makes the manufacturing cost more efficient. Another example is U.S. Patent No. 561617 9 (1997) proposed to D. A. Ba 1 dwi et al., Which uses a gateless ion source to dissociate the hydrocarbon gas, and the ion beam directly deposits DLC. In this method, the hydrocarbon gas is directly introduced into the discharge chamber and dissociated, so that the anode of the discharge chamber is quickly plated with an insulating film, which makes the ion source unstable and cannot be used for a long time. Another example is the Republic of China Patent No. 3 705 5 1 (1999), which issued to Hong Minxiong and Hong 丨 Wen Jin. They proposed a continuous growth diamond-like carbon film method, which uses plasma-assisted chemical vapor deposition. A method (PECVD) deposits a silicon-containing carbon film with a gradient composition on a substrate, followed by continuous deposition: a silicon-based diamond-like carbon film (Si_DLC) or a diamond-like carbon film. This method requires heating on the substrate, so it is not suitable for plastic substrates that are not resistant to high temperatures.

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由於上述的原因，使得商業化量產被覆DLC在不同的 材上’達到抗磨耗保護的目的，變得非常困難。因此開 ，一種方法，具備DLC鑛膜製程簡化，適於各種基材，所" 得膜質緊密與附著力強，厚度均勻性佳與特性一致化，以 及適合複雜形狀和大型基材的商業化技術，成為目前迫切 需要有待積極研究的目標。 二、【發明内容】 本發明的主要目的在提供一種沉積高附著性類鑽碳膜 之方法，以解決已有製程技術的問題和缺點。尤其本發明 利用單離子束法（Single Ion Beam Depositor!， SIBD)， 將高附著性類鑽碳膜直接沉積在基材上，不需透過先形成 中間層或添加其他金屬元素的方式，達到緊密結合且具耐 磨i耐蝕的功能。更進一步地，本發明提供一種適於商業 化量產錢膜成品的低成本和有效率的製程，使得金屬或非 金屬基材可以增加表面抗磨性，延長成品壽命。這個方法 尤/、特別適用於光學塑膠基材表面，如塑膠鏡片、壓克力 防4罩等，沉積類鑽碳膜作為保護層，而不影響其原有透 明度。 曰/ ，據本發明方法，首先以清潔劑去除基材表面油潰、 灰塵等污染物；接著將基材放入真空鍍膜腔體中抽氣至所 需的真空度；然後以氮及氬混合離子束轟擊此基材表面， 進一步去除基材表面的氧化物來活化表面，並使基材表面 產生含氮官能基（functional group);隨即再導入碳氫氣Due to the above reasons, it becomes very difficult to commercialize the production of coated DLC on different materials to achieve the purpose of anti-wear protection. Therefore, a method with a simplified DLC ore film manufacturing process is suitable for various substrates, so the film quality is tight and the adhesion is strong, the thickness is uniform and the characteristics are consistent, and it is suitable for the commercialization of complex shapes and large substrates. Technology has become an urgently needed target for active research. 2. Summary of the Invention The main purpose of the present invention is to provide a method for depositing a diamond film with high adhesion type to solve the problems and disadvantages of the existing process technology. In particular, the present invention uses a single ion beam method (Single Ion Beam Depositor !, SIBD) to deposit a highly adherent diamond-like carbon film directly on a substrate without the need to form an intermediate layer or add other metal elements to achieve compactness. Combined with abrasion and corrosion resistance. Furthermore, the present invention provides a low-cost and efficient manufacturing process suitable for commercialized production of finished film, so that metallic or non-metallic substrates can increase surface abrasion resistance and prolong the life of the finished product. This method is particularly suitable for the surface of optical plastic substrates, such as plastic lenses, acrylic anti-covers, etc., and a diamond-like carbon film is deposited as a protective layer without affecting its original transparency. That is, according to the method of the present invention, firstly, the cleaning agent is used to remove pollutants such as oil breaks and dust on the surface of the substrate; then the substrate is put into a vacuum coating chamber and evacuated to the required vacuum degree; and then mixed with nitrogen and argon The ion beam bombards the surface of the substrate, further removes the oxide on the surface of the substrate to activate the surface, and causes the surface of the substrate to generate nitrogen-containing functional groups; and then introduces carbon hydrogen

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案號 89122059 五、發明說明（4) 體於此真空腔體内，即可沉積高附著性 鑽碳膜。 者14及-硬度之含氣類 依本發明方法可解決或減少先前祜供从m 並具有下列優·點： “技術的困難和缺點， (1) 可沉積高附著性及高硬度之含氮類 上，包括金屬及陶竟、玻璃和塑膠等各種基材 (2) 在室溫下即可鍍膜，並且不受基材厚度 '、狀 性的影響。 乂狀和導電 (3 )直接沉積類鑽碳膜於基材上，簡化激 降低成本。 w 了 ^㈣複雜性及 (4)U不但不受基材形狀的限制，並且容易大型化及量 更具體說明，本發明提供一種可於美 沉積高附著性類鐵碳媒之方*，包含先：氮及 束轟擊被處理之基材表面，藉以清&其 虱此s離子 民争、隹一半岫佶箕从主 错以/月除基材表面污染物，並 且更進-步地使基材表面形成含氮之官能基 氫氣體於處理室中以沉積含氮類鑽碳膜於基材：：通= 所需之膜厚為止。由於製程是在室溫下進 明的基材可為金屬、石夕晶片及如玻璃、 χ = 力：和增強薄膜和基材間的鍵結力，，改= ; = : 附著於基材之現象，尤其是基材為塑膠時。 、 適用之塑膠基材為合成高分子有機聚合物， 树脂、聚碳酸醋、聚gtl猫 ^ ^ # 查克力 眾軋類、聚醯胺類、SAN塑膠、ABS塑膠 585933Case No. 89122059 V. Description of the invention (4) If the body is placed in the vacuum cavity, a high-adhesive diamond carbon film can be deposited. The 14-and-hardness gas-containing species according to the present invention can solve or reduce the previous supply and have the following advantages and disadvantages: "Technical difficulties and disadvantages, (1) can deposit nitrogen with high adhesion and high hardness In terms of substrates, various substrates, including metals and ceramics, glass and plastics (2) can be coated at room temperature, and are not affected by the thickness of the substrate's and shape. 乂 and conductive (3) direct deposition Drilling a carbon film on the substrate simplifies and reduces costs. W In addition to the complexity and (4) U, not only is not limited by the shape of the substrate, but also easy to increase in size and quantity. More specifically, the present invention provides a Method for depositing highly adherent iron-like carbon media, including: first, nitrogen and beam bombarded the surface of the treated substrate, in order to clear & Contaminants on the surface of the substrate, and further make the surface of the substrate form a functional hydrogen gas containing nitrogen in the processing chamber to deposit a nitrogen-containing diamond carbon film on the substrate:: pass = the required film thickness. Since the manufacturing process is at room temperature, the substrate can be metal, Shi Xi wafer and glass, χ = : And the bonding force between the reinforced film and the substrate, change =; =: the phenomenon of adhesion to the substrate, especially when the substrate is plastic. 、 Suitable plastic substrate is synthetic high molecular organic polymer, resin, Polycarbonate, polygtl cats ^ ^ # Chuck Lid, Polyamines, SAN Plastic, ABS Plastic 585933

或曱基丙稀酸甲躁、聚碳酸酯、聚氣乙稀等。 @ '【實施方式】 一 實施本發明方法的具體裝置例的示意圖·如第一圖所 =°依照本發明方法，首先將基材S以例如超音波法清 ^ 可有效去除附著於基材表面之如油潰、灰塵等各種污 染物。第二步驟是將基材s放置於真空腔體（鍍膜室Η内的 基板座3上，然後經由真空幫浦系統2將腔體1内抽氣至所 需適當的真空度。幫浦系統2之一例是由低真空幫浦和高 真空幫浦，例如機械幫浦和擴散幫浦所組成。將真空腔體 i抽氣至3χ 1 (Γ5 Torr以下，以確定能去除真空系統中的水 氣和其他雜氣。基板座3在本實施例中為與水平面呈垂 直’但可以藉圖上未表示之調整機構而任意調整其傾斜角 度呈傾斜狀，或是藉同樣未圖示之驅動機構而可行公轉及 /或自轉，來配合各種不同形狀的基材。又，必要時可以 通入冷水以冷卻基板座，降低鍍膜時基材的溫度。 腔内達到所需的真空度後，在室溫下，由離子源4產 生離子束直接森擊基材S的表面。離子源4為無栅極離子源 (Gridless Ion Source)，例如 Hall Current和 End-Hall 離子源（如美國專利第486 2 0 3 2號所載）等，亦可為有柵極 離子源，如ECR離子源、Kaufman離子源、RF離子源等， 將惰性氣體5，如氬氣、氮氣、氙氣等，和含氮的氣體6， 如氮氣、氨氣或胺類等，在腔體1外的混合器7充分混合 後’直接導入離子源4的放電室8中以陽極電壓5 0至1 5 0伏 特產生電漿。離子束的正電荷由中和器（Neutralizer)9Or methyl methacrylate, polycarbonate, polycarbonate, etc. @ '[Embodiment] A schematic diagram of a specific device example for implementing the method of the present invention. As shown in the first figure = ° According to the method of the present invention, the substrate S is firstly cleaned by, for example, the ultrasonic method. ^ It can effectively remove the surface attached to the substrate Such as oil breaks, dust and other pollutants. The second step is to place the substrate s on the substrate holder 3 in the vacuum chamber (coating chamber Η), and then evacuate the inside of the chamber 1 to the appropriate vacuum degree through the vacuum pumping system 2. The pumping system 2 One example is composed of a low vacuum pump and a high vacuum pump, such as a mechanical pump and a diffusion pump. The vacuum chamber i is evacuated to 3χ 1 (Γ5 Torr or less to determine that it can remove water and other gases from the vacuum system. Miscellaneous gas. The substrate holder 3 is perpendicular to the horizontal plane in this embodiment, but can be arbitrarily adjusted to have an inclined angle by an adjustment mechanism not shown in the figure, or can be revolved by a drive mechanism that is also not shown And / or rotation to match substrates of various shapes. In addition, cold water can be passed in to cool the substrate holder if necessary to reduce the temperature of the substrate during coating. After the required vacuum in the chamber is reached, at room temperature, The ion beam generated by the ion source 4 directly strikes the surface of the substrate S. The ion source 4 is a gridless ion source, such as Hall Current and End-Hall ion sources (such as US Patent No. 486 2 0 3 2 No.), etc., can also be Polar ion sources, such as ECR ion source, Kaufman ion source, RF ion source, etc., inert gas 5, such as argon, nitrogen, xenon, etc., and nitrogen-containing gas 6, such as nitrogen, ammonia or amines, etc. The mixer 7 outside the cavity 1 is fully mixed and is then directly introduced into the discharge chamber 8 of the ion source 4 to generate a plasma at an anode voltage of 50 to 150 volts. The positive charge of the ion beam is neutralized by a neutralizer 9

第9頁 585933 五、發明說明（6) 產生電子Page 9 585933 V. Description of the invention (6) Electron generation

案號 891220M λ_ 修正 是絕緣 以是鎢 (Hollow 真空壓 的碰撞 ’也才 轟擊 氣體1 〇， 由氣體分 的路後上 束能量輔 藉由調整 碳膜的含 定。由於 eV，最好 處理，因 〇 經由 的特質。 請的專利 使 可 的 間 量 中和之’使得基材s的電位能保持固定，因此即 基材也能夠進行處理，此點非常重要 絲…電漿橋式仙観㈣心中要空陰中極和159 Cathode)等型式。此時真空腔體1在導入氣體後 =宜保持在3χ 10-3Τ〇ΓΓ以下，使得離子—氣體 =至最低，如此基材S表面的轟擊才有足夠的能 能達到基材與鍍膜之間的高附著力。 離子束12仍維持的情形下，將碳氩 佈产Γι導入：其：烷、乙烯、丙烯、乙炔等，經 m 表面附近或是離子束12行進 使奴虱軋體10與氮離子束12混合，進而以 助的方式，在基材3表面沉積 惰性氣體5和含氮氣體6的二二，類鑽碳膜。 敗量，以調整鑛膜的性f :触可決定類鑽 撞擊在基材表面的離子能量可=子源的穩 為20em 2 00eV，並配合T從數/ eV至數百 此能沉積高附著性、$硬$ 氮離子活化預 间硬度、緻密的薄膜在基材 下列實施例的說明，可以進一牛 這些例子只是作為說明/ '了解本發明 範圍。 用而不疋限制所申Case No. 891220M λ_ The correction is that insulation is tungsten (Hollow vacuum pressure collision) also bombards the gas 10, the energy of the beam after the branch of the gas is assisted by adjusting the carbon film content. Due to eV, it is best to deal with, Because of the characteristics of passing through. The patented patent allows the amount of neutralization to 'allow the potential of the substrate s to be fixed, so that the substrate can also be processed. This is very important. The heart should be empty and yin, and 159 Cathode). At this time, after introducing the gas in the vacuum chamber 1, it should be kept below 3x 10-3T0ΓΓ, so that the ion-gas = to a minimum, so that the bombardment on the surface of the substrate S is sufficient to reach between the substrate and the coating. High adhesion. While the ion beam 12 is still maintained, carbon argon cloth Γι is introduced: it: alkane, ethylene, propylene, acetylene, etc., travels near the m surface or the ion beam 12 to make the lice rolling body 10 and the nitrogen ion beam 12 mixed Further, in a helpful manner, a diamond-like carbon film of inert gas 5 and nitrogen-containing gas 6 is deposited on the surface of the substrate 3. The amount of failure to adjust the properties of the mineral film f: touch can determine the ionic energy of the diamond-like impact on the surface of the substrate can = the stability of the sub-source is 20em 2 00eV, and with T from several / eV to several hundred this can deposit high adhesion The properties, properties, and hardness of the nitrogen-activated pre-interlayer hardness and dense film on the substrate are described in the following examples. These examples can only be used as illustration / 'understand the scope of the present invention. Use without limitation

585933 修正585933 fix

B —-~_ 案號 89122059 五、發明說明（7) 實施例1 : 準備一塊1 Οχ 1 0公分，厚度〇 · 6公分的透明壓克力平 板基材’首先以清潔劑在超音波槽中將此基材清洗，然後 以去離子水沖洗，最後以氮氣吹乾。接著，將壓克力基材 放入不錄鋼製真空腔體中，以擴散幫浦抽氣至3. 〇χ 1〇一6B —- ~ _ Case No. 89122059 V. Description of the invention (7) Example 1: Prepare a transparent acrylic flat substrate of 10 × 10 cm in thickness and 0.6 cm in thickness. 'First use a cleaning agent in the ultrasonic tank. The substrate was washed, rinsed with deionized water, and finally dried with nitrogen. 〇χ 1〇 一 6 Next, the acrylic substrate was placed in a non-recording steel vacuum chamber, and the pump was evacuated to 3. 〇χ 1〇 一 6

Torr’然後使用End-Hall離子源（美國Commonwealth Scientific公司出品，Markn )以氬氣（Ar)3 sccm，氮氣 (N2) 14 seem，陽極電壓100V，電流乜的條件下，產生氮 及氬混合離子束轟擊基材表面5分鐘。氬氣與氮氣在腔體 外混合後，引入離子源的放電室，此時真空壓力成為 7· 4x 10-^ Torr。轟擊結束後，將氮氣流量降至9 sccm， 另將乙快氣體以流量45 seem引入至基材前方2公分處的 氣體分佈環’此時真空壓力成為丨· 5χ 1 〇_4 Torr，陽極電 流5A。以上述的條件沉積1〇分鐘，得到i5〇nm的含氮類鑽 碳膜’在可見光下呈透明棕色。以XPS光譜儀分析鍍膜之 成分可得碳（C)、氮（N)、氧（0)原子濃度百分比分別為 8 5. 6 kt /〇 6.4 At%、8 At%’ 以 3D-profilemete r量得其 應力為1·18 GPa。將已鍍膜之基材以scotch膠帶進行附著 力測試和20%濃鹽水浸泡48小時，以及沸水2分鐘—冰水2 分鐘之冷熱衝擊測試連續5次，鍍膜仍保持完整及良好的 附著性。 另外準備一塊相同規格之透明壓克力平板基材，以傳 統方法（參考美國專利第5 6 1 6 1 7 9號）直接將乙炔氣體通入 585933 < _案號89122059_年月日___ 五、發明說明（8) 離子源裏，在壓克力基材沉積類鑽碳膜做為比較例。以 \ XPS光譜儀分析鍍膜之成分可得碳（C)、氮（N)、氧（0)原子 濃度百分比分別為91. 6 At%、0. 7 At%、7. 7 At%，以3D-profilemeter量得其應力為2.04 GPa。將已鍍膜之基材以 同前述之方法使用Scotch膠帶進行附著力測試，發現膜層 與基材完全剝離。由本發明與傳統方法比較，顯見本發明 對鍍膜附著力有明顯的增強性。 實施例2 : 準備一個外徑6公分，厚度0. 5公分，長度6公分的透 明壓克力圓筒，以同於實施例1的方法清洗乾淨後，放入 真空腔體内，懸吊在離子源前方，以自轉方式旋轉。真空 腔體以擴散幫浦抽氣至6x 10_6 Torr，然後用End-Hal 1離 子源以氬氣2.5 seem ，氮氣13 seem，陽極電壓140V，電 流4. 5 A的條件，產生氮及氬混合離子束轟擊基材表面2 0分 鐘。氬氣與氮氣在腔體外的混合器混合後，引入離子源的 放電室，此時真空壓力為7. 5x 1 0 _5 T 〇 r r。轟擊結束後， 氮氣流量降至6 seem ，乙炔氣體流量50 s c c m引入至基材 前方2 cm處的氣體分佈環，此時真空壓力1. 4x 1 0 一4 T 〇 r r，陽極電流4 . 3 A。以上述的條件沉積1 5分鐘，得到 1 OOnm的類鑽碳膜。以XPS光譜儀分析鍍膜之成分可得碳 (C)、氮（N)、氧（0)原子濃度百分比分別為87· 2 At°/〇、 4. 6At%、8. 2 At%。經以如同實施例1的測試方法測試基 材，鍍膜仍保持完整及良好的附著性。Torr 'then uses an End-Hall ion source (produced by Commonwealth Scientific, USA, Markn) to produce nitrogen and argon mixed ions under the conditions of argon (Ar) 3 sccm, nitrogen (N2) 14 seem, anode voltage 100V, and current krypton. The beam bombarded the surface of the substrate for 5 minutes. After argon and nitrogen were mixed outside the chamber, they were introduced into the discharge chamber of the ion source. At this time, the vacuum pressure became 7.4x 10- ^ Torr. After the bombardment, the nitrogen flow rate was reduced to 9 sccm, and the fast gas was introduced into the gas distribution ring 2 cm in front of the substrate at a flow rate of 45 seem. At this time, the vacuum pressure became 5 × 1 Torr, anode current 5A. Depositing under the above conditions for 10 minutes, a nitrogen-containing diamond carbon film ' of i50 nm was obtained which was transparent brown under visible light. By analyzing the composition of the coating with an XPS spectrometer, the atomic concentration percentages of carbon (C), nitrogen (N), and oxygen (0) were 85.6 kt / 〇6.4 At% and 8 At%, respectively. Measured in 3D-profilemete r Its stress is 1.18 GPa. The coated substrate was tested for adhesion with scotch tape and immersed in 20% concentrated saline for 48 hours, and cold and hot shock tests for 2 minutes from boiling water to 2 minutes from ice water for 5 consecutive times. The coating remained intact and had good adhesion. In addition, a piece of transparent acrylic flat substrate of the same specification was prepared, and the acetylene gas was directly introduced into the 585933 by the traditional method (refer to US Patent No. 5 6 1 6 1 7) < _ case number 89122059_ year month day ___ 5. Description of the invention (8) In the ion source, a diamond-like carbon film is deposited on an acrylic substrate as a comparative example. \ XPS spectrometer analysis of the composition of the coating can be obtained carbon (C), nitrogen (N), oxygen (0) atomic concentration percentages are 91.6 At%, 0.7 At%, 7. 7 At%, with 3D- The profilemeter measured its stress at 2.04 GPa. The coated substrate was tested for adhesion using a Scotch tape in the same manner as above, and it was found that the film layer was completely separated from the substrate. From the comparison between the present invention and the conventional method, it is apparent that the present invention has a significantly enhanced adhesion to the plating film. Example 2: A transparent acrylic cylinder with an outer diameter of 6 cm, a thickness of 0.5 cm, and a length of 6 cm was prepared. After being cleaned in the same manner as in Example 1, it was placed in a vacuum chamber and suspended in a In front of the ion source, it rotates by rotation. The vacuum chamber was evacuated to 6x 10_6 Torr with a diffusion pump, and then the End-Hal 1 ion source was used under the conditions of argon 2.5 seem, nitrogen 13 seem, anode voltage 140V, and current 4.5 A to generate nitrogen and argon mixed ions. The beam bombarded the substrate surface for 20 minutes. After mixing argon with nitrogen in a mixer outside the chamber, the argon gas was introduced into the discharge chamber of the ion source, and the vacuum pressure at this time was 7.5 x 1 0 _5 T 〇 r r. After the bombardment, the nitrogen flow rate decreased to 6 seem, and the acetylene gas flow rate of 50 sccm was introduced to the gas distribution ring 2 cm in front of the substrate. At this time, the vacuum pressure was 1. 4x 1 0 to 4 T 〇rr, and the anode current was 4.3 A. . Depositing under the above conditions for 15 minutes, a diamond-like carbon film of 100 nm was obtained. By analyzing the composition of the coating with an XPS spectrometer, the atomic concentration percentages of carbon (C), nitrogen (N), and oxygen (0) were 87 · 2 At ° / 〇, 4.6 At%, and 8.2 At%, respectively. After the substrate was tested in the same manner as in Example 1, the coating film remained intact and had good adhesion.

第12頁 585933 ---案號89122059_年月日 條正__ 五、發明說明（9) 另外準備一今相同規格之透明壓克力圓筒，以傳統方 法（參考美國專利第56 1 6 1 79號）直接將乙炔氣體通入離子 源裏，在壓克力圓筒沉積類鑽碳膜。將壓克力圓筒自真空 腔取出’錄膜因應力太大而立刻龜裂。由本發明與傳統方 法比較’顯見本發明對鍍膜附著力有明顯的增強性。 實施例3 :Page 12585933 --- Case No. 89122059_year month day article __ V. Description of the invention (9) In addition, prepare a transparent acrylic cylinder of the same specification today, using the traditional method (refer to US Patent No. 56 1 6 No. 1 79) Directly pass acetylene gas into the ion source, and deposit a diamond-like carbon film on the acrylic cylinder. Taking out the acrylic cylinder from the vacuum chamber, the film was cracked immediately because of too much stress. From the comparison of the present invention with the conventional method, it is clear that the present invention has a significantly enhanced adhesion to the plating film. Example 3:

準借一塊6x 2 · 5公分，厚度0 · 1 2公分的鏡面不銹鋼 3 0 4以丙_清潔乾淨後，放入真空腔體内的基板座上，真 空腔體以擴散幫浦抽氣至1〇-6 Torr，然後用End-Hall 離子源以氬氣3 seem，氮氣13 seem，陽極電壓150V，電 流5 A，，件，產生氮及氬混合離子束轟擊基材表面丨〇分 鐘。2氣與氮氣在腔體外的混合器混合後，引入離子源的 放電至此時真空壓力為5. 2x 1〇5 Torr。轟擊結束後， 氮氣流！降至8 seem，陽極電壓降至130V，乙炔氣體流量 45 seem引入至基材前方2公分處的氣體分佈環，此時真空 2力1 · 5x 1 0 4，陽極電流5 A。以上述的條件沉積3 〇分鐘， 得到45 0nm的含氮類鑽碳膜。以xps光譜儀分析鍍膜之Borrow a piece of mirror stainless steel with a thickness of 6x 2 · 5 cm and a thickness of 0 · 1 2 cm 3 0 4 After cleaning, put it on the substrate seat in the vacuum chamber. The vacuum chamber is pumped to 1 with a diffusion pump. 〇-6 Torr, and then use End-Hall ion source to argon 3 seem, nitrogen 13 seem, anode voltage 150V, current 5 A, pieces, to produce a nitrogen and argon mixed ion beam bombarded the surface of the substrate for 0 minutes. After mixing the 2 gas with nitrogen in a mixer outside the chamber, the discharge of the ion source was introduced until the vacuum pressure at this time was 5.2x105 Torr. After the bombardment, the nitrogen flow! The voltage drops to 8 seem, the anode voltage drops to 130V, and the flow of acetylene gas 45 seem is introduced into the gas distribution ring 2 cm in front of the substrate. At this time, the vacuum is 2 forces 1 · 5x 1 0 4 and the anode current is 5 A. Depositing under the above conditions for 30 minutes, a nitrogen-containing diamond-like carbon film of 450 nm was obtained. Analysis of coating by xps spectrometer

可，碳（c)、氮（N)、氧（0)原子濃度百分比分別為、84 9Yes, the carbon (c), nitrogen (N), and oxygen (0) atomic concentration percentages are 84 9

At。 6·6 At/、8.5 At%，以 3D-profilemeter量得 廣力 =·丄V?;經以如同實施例1的方法測試基材，鑛膜: 保持元整及良好的附著性。 另外準備一塊相同規格之不銹鋼基材，以 (參考美國專利第56 1 6 1 79號）直接將乙炔氣體通入4離方子1At. 6.6 At /, 8.5 At%, measured by 3D-profilemeter. Guangli = · 丄 V ?; After testing the substrate in the same way as in Example 1, the mineral film: maintains the integrity and good adhesion. In addition, prepare a stainless steel substrate of the same specification, and directly pass the acetylene gas into the 4 ions (see US Patent No. 56 1 6 1 79) 1

第13頁 585933 _案號 89122059_^_J|_Q_修正_ 五、發明說明（10) 裏，在不銹鋼基材;沉積類鑽碳膜。將已鍍膜之基材以 Scotch#帶進行附著力測試，發現膜層與基材完全剝離。 由本發明與傳統方法比較，顯見本發明對鍍膜附著力有明 顯的增強性。Page 13 585933 _Case No. 89122059 _ ^ _ J | _Q_Amendment__ In the description of the invention (10), on the stainless steel substrate; a diamond-like carbon film is deposited. The coated substrate was tested for adhesion with a Scotch # tape, and it was found that the film layer and the substrate were completely peeled off. Comparing the present invention with the conventional method, it is apparent that the present invention has a significantly enhanced adhesion to the plating film.

實施例1，2，3之結果証明本發明方法不論在塑膠基 材或金屬基材，平面或曲面，皆可沉積高附著性的類鑽碳 膜。由於無栅極離子源具有低能量大電流的特性，因此 鍍膜時可以有非常快的沉積速率，而基材仍能保持低溫。 由於類鑽碳膜擁有良好的抗磨耗性，塑膠鏡片如利用本發 明方法鍍上類鑽碳膜，可以具有和玻璃一樣的抗磨耗性。 本發明方法有很快的沉積速率，因此提供一個經濟的製 程，適合商業化量產的規模。The results of Examples 1, 2, and 3 prove that the method of the present invention can deposit a diamond-like carbon film with high adhesion regardless of whether it is a plastic substrate or a metal substrate, a flat surface or a curved surface. Because the gateless ion source has the characteristics of low energy and large current, it can have a very fast deposition rate while coating, and the substrate can still maintain a low temperature. Because diamond-like carbon film has good abrasion resistance, plastic lenses, if coated with diamond-like carbon film by the method of the present invention, can have the same abrasion resistance as glass. The method of the present invention has a fast deposition rate, and therefore provides an economical process suitable for the scale of commercial mass production.

第14頁 585933 案號 8912£059 年月曰 修正 圖式簡單說明 圖一為適用於本發明方法的離子束鍍膜裝置示意圖 符號說明Page 14 585933 Case number 8912 £ 059 Month Amendment Brief description of the drawing Figure 1 is a schematic diagram of an ion beam coating device suitable for the method of the present invention Symbol description

1 真 空 腔 體 2 幫 浦 系 統 3 基 板 座 S 基 板 4 離 子 源 5 惰 性 氣 體 6 含 氮 氣 體 7 混 合 器 8 放 電 室 9 中 和 器 10 碳 氫 氣 體 11 氣 體 分 佈環 12 離 子 束 第15頁1 Real cavity 2 Pump system 3 Base plate S Base plate 4 Ion source 5 Inert gas 6 Nitrogen-containing gas 7 Mixer 8 Discharge chamber 9 Neutralizer 10 Hydrocarbon gas 11 Gas distribution ring 12 Ion beams Page 15

Claims (1)

585933 《 .....................案號89122059 _年月曰 魅____ 六、申請專利範圍 之組群。 \ · 4 ·根據申請專利範圍第2項之方法，其中該有柵極離子源 係選自Kaufman離子源、ECR離子源、RF離子源、Bucket 離子源等所組成之族群。 5 ·根據申請專利範圍第1項之方法，其中該基材係選自陶 瓷、半導體、玻璃、金屬和塑膠等所組成之族群。 6 .根據申請專利範圍第5項之方法，其中該塑膠是合成有 機聚合物，係選自壓克力樹脂（Acrylics)’聚碳酸酯 (Polycarbonates)，聚 S旨類（Polyesters)’ 聚醯胺類 (Polyamides)、S AN塑膠（Styrene-Acrylonitrile copolymers)、 ABS塑膠 Acrylonitrile-Butadiene-Styrene tepolymers)等所組成之族群。 7·根據申請專利範圍第6項之方法，其中該合成有機聚合 物可以為透明的及非透明的。 8 ·根據申請專利範圍第7項之方法，其中該合成有機聚合 物係選自聚甲基丙烯酸曱酯（Polymethylmethacrylate) 、聚碳酸酯（Polycarbonate)、聚氣乙烯 (Polyvinylchloride)等所組成之族群。585933 "......... Case number 89122059 _year month said charm____ VI. Groups of patent application scope. The method according to item 2 of the scope of patent application, wherein the gated ion source is selected from the group consisting of Kaufman ion source, ECR ion source, RF ion source, Bucket ion source, and the like. 5. The method according to item 1 of the scope of patent application, wherein the substrate is selected from the group consisting of ceramics, semiconductors, glass, metals and plastics. 6. The method according to item 5 of the scope of the patent application, wherein the plastic is a synthetic organic polymer selected from acrylic resins 'Polycarbonates and polyS polyesters' polyamines Group (Polyamides), S AN plastic (Styrene-Acrylonitrile copolymers), ABS plastic Acrylonitrile-Butadiene-Styrene tepolymers) and other groups. 7. The method according to item 6 of the scope of patent application, wherein the synthetic organic polymer may be transparent and non-transparent. 8. The method according to item 7 of the scope of patent application, wherein the synthetic organic polymer is selected from the group consisting of polymethylmethacrylate, polycarbonate, and polyvinylchloride. 第17頁 585933 _案號89122059_年月日__ 六、申請專利範圍 9·根據申請專利輯圍第1項之方法，其中該含氮氣體係選 自氮氣（N2)、氨氣（NH3)和胺類（Amine)等所組成之族 群。 10·根據申請專利範圍第9項之方法，其中該含氮氣是氮 氣。 1 1.根據申請專利範圍第9項之方法，其中該惰性氣體係選 自氬氣、氪氣、氙氣所組之族群。Page 17 585933 _Case No. 89122059_ Year Month Date__ VI. Scope of Patent Application 9. According to the method of patent application No. 1, the nitrogen-containing system is selected from nitrogen (N2), ammonia (NH3) and Amine and other groups. 10. The method according to item 9 of the scope of patent application, wherein the nitrogen-containing gas is nitrogen gas. 1 1. The method according to item 9 of the scope of patent application, wherein the inert gas system is selected from the group consisting of argon, krypton, and xenon. 1 2.根據申請專利範圍第1 1項之方法，其中該惰性氣體是 氬氣。 1 3 ·根據申請專利範圍第1項之方法，其中該基材上之氮 離子束電流密度至少0. 2 mA/cm2，平均動能為20eV至 2 0 0 eV。12 2. The method according to item 11 of the scope of patent application, wherein the inert gas is argon. 1 3 · The method according to item 1 of the scope of patent application, wherein the nitrogen ion beam current density on the substrate is at least 0.2 mA / cm2, and the average kinetic energy is 20eV to 200 eV. 1 4 .根據申請專利範圍第1項之方法，其中該碳氫氣體係選 自曱烷、乙烷、丙烷、乙烯、丙烯、乙炔等和其混合 氣所組成之族群。 1 5.根據申請專利範圍第1 3項之方法，其中該碳氩氣體是 乙快。14. The method according to item 1 of the scope of patent application, wherein the carbon-hydrogen system is selected from the group consisting of pinane, ethane, propane, ethylene, propylene, acetylene, etc., and a mixture thereof. 15. The method according to item 13 of the scope of patent application, wherein the carbon argon gas is acetylene. 第18頁 585933 _案號89122059_年月 六、申請專利範圍 I6.根據申請專利、、範圍第1項之方法， 具有10%至5 0%原子比重的氮原子 a_^_ 其中該含氮類鑽碳膜Page 18 585933 _ Case No. 89122059_ Year 6. Application for patent scope I6. According to the method of application for patent, scope item 1, nitrogen atoms with a specific gravity of 10% to 50% a _ ^ _ where the nitrogen-containing species Drilling carbon film