TW575681B - Fluorine-doped diamond-like coatings - Google Patents

Description

575681575681

相關申請案前後對只_g 本申請案係1998年8月14曰提出之^ 第0 9/ 1 3 3, 9 5 1號的部分連續申請案，六國專利申請案序號 號第0 9 / 1 33, 9 5 1號係1995年10月3日接而吳國專利一申請案序 案序號第0 8 / 5 3 8, 73 1號之連續申,安出之吴國專利申請 年1 2月5日提出之美國臨時專利卜:V此申請案亦為1 997 號與1 9 97年12月5日提出之美國臨;;第⑽/g 6 7,5 6 7 60/ 0 6 7, 7 5 0號之部分連續申請案。' j申凊案序號苐 有 料 發明範圍 本發明有關基材上之含氟類鑽石塗 關在撓性基材、精確磨利基材與電 料， 手術 更特別的是，其 儀器上之此等塗 發明背景 第。會致使精確邊緣變鈍。例如，刺刀於 之鋼通常先二各易立刻鈍至某種程度。目此剃刀所使用 —種藏鍍金屬塗層，然後塗覆聚四氟乙烯 )主層。雖然PTFE塗層通常為數十至數千埃厚’但是 對於許多產物與工業而言 多刀片與醫療工具只有當其 適用。銳利度係該基材與其 °例如，弟彳刀之邊緣係 大端之曲率半徑形成。人類 $對照。此種基材邊緣通常 k純以保存邊緣精確度。 ’保存銳利邊緣極為重要。許 銳利邊緣保存期間相當長時才 上任何塗料所形成精確邊緣的 由遠刀片自約7 5至約1 〇 〇 〇埃極 頭髮寬度約1 〇 〇微米，以此作 塗覆某些物質，試圖抑制邊緣Relevant applications before and after _g This application is filed on August 14, 1998 ^ Partial serial applications No. 0 9/1 3 3, 9 5 1 and serial number of patent applications in six countries No. 0 9 / No. 1 33, 9 5 No. 1 is the serial application of Wu Guo Patent No. 0 0/5 3 8, 73 1 successively filed on October 3, 1995. Wu Guo Patent Application Year 1 2 U.S. provisional patent filed on May 5: V This application is also U.S. Pro. No. 1 997 and U.S. Pro filed on December 5, 1997;; / g 6 7,5 6 7 60/0 6 7, Partial applications for No. 7 50. 'J Application No. No. Scope of the Invention The scope of the invention The fluorine-containing diamond on the substrate is coated on the flexible substrate, the substrate is precisely ground and the electrical material, and the operation is more special. Tu background of the invention. Can cause dull edges. For example, bayonet steel is usually easily blunt to a certain extent. Currently used for razors-a kind of metallized coating, and then coated with a main layer of polytetrafluoroethylene. Although PTFE coatings are usually tens to thousands of angstroms thick ', for many products and industries multi-blades and medical tools are only applicable if they are applicable. Sharpness is formed by the base material and its edge. For example, the edge of the blade is formed by the radius of curvature of the large end. Human $ control. The edges of such substrates are usually k-pure to preserve edge accuracy. ’Preserving sharp edges is extremely important. Xu sharp edge preservation period is quite long before applying any coating to form the precise edge of the far blade from about 75 to about 1000 angstroms. The hair width is about 1000 microns. Suppress the edges

575681 五、發明說明（2) f質上於第 可以提供連 緣變鈍。 精確邊緣 裂、邊緣破 等因素結合 性提南並造 部分用後抛 範圍等更昂 對於磨利或 較硬材料 终多應用而 使用錯片或 金屬為底 免、硼、石夕 邊緣保存作 料。不過， 已知石夕酸 氣體。不過 料，而且可 特定陶-是 料。不過， 孔，無法提 已嘗試特 一次使用時會自該刀片去除該塗層。充分p 續潤滑作用。不過，PTFE塗層無法避免^確= 純化係因為刀片極尖端之曲率半經增加 龜 碎或斷裂造成邊^有缺口、邊緣材料侵银或此 所致。就剃刀而言，精確邊緣變鈍會致使摩 成使用者的不舒適。然後替代該刀片或是替^ 棄式工具時，，棄整個剃刀。就工業用或^療 貴切割工具而言，精確邊緣工具之鈍化會造成 再次磨利之需求’如此提高成本。 塗料之沉積作用已試圖保存邊緣之完整性。就 言，該塗料亦必須具有優越的熱安定性，即^ 消毒程序（熱壓手術工具）時可耐極高執。 、 質塗料，諸如鋼、鋅、鋁、鉻、鎳、鎘、鈕、 、銅、鎵、銖與其合金之塗料經證實具有精確 用，而且用於許多工業作為銳利邊緣之保護塗 由此等材料之塗料通常僅適用於金屬基材。 鹽為底質塗料於南溫下耐空氣、酸、鹼與數種 ，由；矽酸鹽類製得之塗料並非特別堅固材 能無法對精確邊緣提供適當保護作用。 材料具有對抗腐姓性’而且可作為邊緣保存塗 陶竞易脆而且易受熱衝擊。其通常粗链且多 供所需之低摩擦性。 定硬式類鑽石塗料（DLC s )。不過，塗料不只必575681 V. Description of the invention (2) f can provide the connection to be dull. Precise edge cracks, edge breaks, and other factors are combined to improve the performance and make the part more thrown after use. For sharper or harder materials, multiple applications are often used, and the wrong piece or metal is used as a base. Boron and stone edges are used to save the material. However, oxalic acid gas is known. Unexpected, and can be specific pottery-is expected. However, the holes cannot be lifted. The coating will be removed from the blade when a single use is attempted. Full p Continue lubrication. However, PTFE coatings cannot be avoided. Indeed = purification is caused by chipped or broken edges due to increased curvature at the tip of the blades, cracks in the edges, or intrusion of silver by the edge material. In the case of razors, dulling of the precise edges can cause discomfort to the friction user. When replacing the blade or a disposable tool, discard the entire razor. In the case of industrial or medical expensive cutting tools, the passivation of precision edge tools will cause the need for re-sharpening ', thus increasing costs. Coating deposition has sought to preserve the integrity of the edges. In other words, the coating must also have excellent thermal stability, which means that it can withstand extremely high resistance during sterilization procedures (hot pressing surgical tools). Coatings such as steel, zinc, aluminum, chromium, nickel, cadmium, buttons, copper, gallium, baht and their alloys have proven to be accurate and are used in many industries as protective coatings for sharp edges. Coatings are usually only suitable for metal substrates. Salt-based coatings are resistant to air, acids, alkalis, and several types at south temperatures. Coatings made from silicates are not particularly strong and cannot provide adequate protection for precise edges. The material is resistant to rot, and can be used as an edge preservation coating. Ceramics are brittle and vulnerable to thermal shock. It is usually thick chain and provides the required low friction. Fixed-hard diamond-like coatings (DLCs). But paint does n’t just have to

第7頁 575681 五、發明說明（3) - 須堅硬，而且對於基材之粘附性必須良好。已知DLCs通常 需要中間層將其粘於基材上。就某些物件而言，此種中間 層可能不會產生問題。不過，為保存精確邊緣，所有塗料 之總厚度必須在不知覺狀況下增加邊緣極尖端之極小曲率 半徑。此外，在DLC與基材間沉積中間層之額外方法會提 高製造成本。此對於低成本項目諸如用後拋棄式剃刀與剃 刀刀片而言極為明顯，甚至對於經濟不利。 因此，極需要一種堅固、硬式、高度粘合性、對於溫 度、pH值與化學物質不敏感塗料，其可用於金屬與非金屬 表面，不必塗覆中間層即可保存精確邊緣。 亦需要提供多種具有脫模或不钻塗層物件，諸如锅具、 工業工具或醫療工具，如此清潔該物件時可以容易膠粘殘 留物。不粘塗料包括例如氟碳樹脂，諸如聚四氟乙烯或矽 樹脂。 通常具有不粘塗層之物件包括電手術刀片。在電手術程 序中，電手術儀器係由射頻電壓通電以切割組織及/或經 由燒灼凝結血液。此等儀器通常結合單極或雙極系統中之 導電性刀片。雖然已證貫電手術儀器有利於控制手術期間 之出血，但是該儀器的普遍性問題係組織膠粘於切割表面 上，因此降低切割效率，故需要及早更替切割元件。此問 題解決途徑之一係在該切割元件上塗覆不粘材料，如此經 燒灼組織較不會粘於該元件上。當然，此塗覆材料必須適 於通過電手術電流或至少該塗料必須使電流自該切割表面 通至該組織。Page 7 575681 V. Description of the invention (3)-Must be rigid and must adhere well to the substrate. It is known that DLCs usually require an intermediate layer to adhere them to a substrate. For some objects, this intermediate layer may not cause problems. However, in order to preserve precise edges, the total thickness of all coatings must be increased unconsciously with a very small radius of curvature of the extreme tip of the edge. In addition, the additional method of depositing an intermediate layer between the DLC and the substrate increases manufacturing costs. This is particularly noticeable for low cost items such as disposable razors and razor blades, and is even economically disadvantageous. Therefore, there is a great need for a strong, hard, highly adhesive, temperature-, pH-, and chemical-insensitive coating that can be used on metallic and non-metallic surfaces without the need for an intermediate layer to preserve precise edges. There is also a need to provide a variety of articles with release or non-drilled coatings, such as pots, industrial tools, or medical tools, so that residues can be easily glued when cleaning the article. Non-stick coatings include, for example, fluorocarbon resins such as polytetrafluoroethylene or silicone. Items that typically have a non-stick coating include electrosurgical blades. In an electrosurgical procedure, an electrosurgical instrument is energized by a radio frequency voltage to cut tissue and / or coagulate blood by cauterizing. These instruments often incorporate conductive blades in unipolar or bipolar systems. Although it has been proven that electrosurgical instruments are beneficial for controlling bleeding during surgery, a common problem with this instrument is that the tissue is glued to the cutting surface, which reduces the cutting efficiency and requires early replacement of the cutting elements. One way to solve this problem is to coat the cutting element with a non-stick material so that the cauterized tissue is less likely to stick to the element. Of course, this coating material must be suitable for passing an electrosurgical current or at least the coating must pass current from the cutting surface to the tissue.

575681 五、發明說明（4) - 雖然具有不粘材料之電手術儀器塗料可以改善手術程 序’但是習知塗料材料具有數個缺點。例如’該塗料之導 電率不符合需求、對於基材之粘合性差、於手術期間之使 用條件下容易變鈍，而且重複消毒作業時會產生表面腐蝕 與點狀腐蝕。 < 此外，對於撓性基材上整合被動與主動裝置（諸如電阻 器或電容器）的需求提南。不連績組件之互連技術用途不 適於多層結構、高成本裝配、體積對重量比率不適當、設 備成本大及多重處理步驟。薄膜被動電阻器與電容器之用 途不包括對於焊接互連之需求、促使積體具有多層輸出功 ® 率及良好體積對重量比率。因此，在撓性基材（諸如聚酸 亞胺類或高溫聚合物）上使用介電薄塗層變得愈來愈重 要。積體化電阻器與電容器用於多層晶片模組（MCM)與 FLEX路件是撓性基材上塗料的用途之一。需要一種可用於 . 任何MCM技術（包括倒裝片、表面安裝或直接附裝晶片）之 塗料。 目前來說，電阻器與電容器係製成不連續組件，並由焊 錫與引線接合法安裝。此現象涉及高成本裝配、接合焊錫 用之高成本設備、體積重量比不當及構成多層電路之不相 籲 容性。 本發明有關於克服此等缺點。 發明總結 本發明有關一種包括塗覆含氟類鑽石塗料之物件，其中 該塗料包括一種含碳、矽、氧、氫與氟之類鑽石組合物。575681 V. Description of the Invention (4)-Although the coating of electrosurgical instruments with non-stick materials can improve the procedure, the conventional coating materials have several disadvantages. For example, the conductivity of the coating does not meet the requirements, the adhesion to the substrate is poor, it is easy to dull under the conditions of use during surgery, and surface corrosion and pitting corrosion occur when the disinfection operation is repeated. < In addition, the need for integrating passive and active devices such as resistors or capacitors on flexible substrates is increasing. The use of interconnect technology for non-continuous components is not suitable for multilayer structures, high-cost assembly, inappropriate volume-to-weight ratios, high equipment costs, and multiple processing steps. The use of thin-film passive resistors and capacitors does not include the need for soldered interconnects, the promotion of multilayer output power ® and good volume-to-weight ratio. As a result, the use of thin dielectric coatings on flexible substrates such as polyimides or high-temperature polymers has become increasingly important. Integrated resistors and capacitors for multilayer chip modules (MCMs) and FLEX circuits are one of the applications for coatings on flexible substrates. What is needed is a coating that can be used with any MCM technology, including flip-chip, surface-mount, or direct-attach wafers. Currently, resistors and capacitors are made as discrete components and mounted by solder and wire bonding. This phenomenon involves high-cost assembly, high-cost equipment for soldering, improper volume-to-weight ratio, and incompatibility of multi-layer circuits. The present invention relates to overcoming these disadvantages. Summary of the Invention The present invention relates to an article comprising a coating containing a fluorine-containing diamond coating, wherein the coating comprises a diamond composition containing carbon, silicon, oxygen, hydrogen, and fluorine.

第9頁 575681 五、發明說明（5) - 在具體實例之一中，本發明有關一種塗覆含氟類鑽石塗 料之撓性基材。該塗料包含碳、石夕、氧、氫與氟，而且其 塗覆厚度約0 . 0 5微米至約1 0微米為佳。 另一具體實例中，本發明有關一種塗覆包含碳、矽、 氧、氫與氟之含氟類鑽石塗料的精確磨利基材。 另一具體實例中，本發明有關一種塗覆含氟類鑽石塗料 之電手術儀器。該塗料包含碳、矽、氧、氫與氟。 本發明有關一種塗覆包含碳、石夕、氧、氫、氟以及另一 種摻雜劑之含氟類鑽石塗料的基材。Page 9 575681 V. Description of the Invention (5)-In one of the specific examples, the present invention relates to a flexible substrate coated with a fluorine-containing diamond coating. The coating contains carbon, stone, oxygen, hydrogen, and fluorine, and preferably has a coating thickness of about 0.05 micrometers to about 10 micrometers. In another specific example, the present invention relates to a precision abrasive substrate coated with a fluorine-containing diamond coating comprising carbon, silicon, oxygen, hydrogen, and fluorine. In another embodiment, the present invention relates to an electrosurgical instrument coated with a fluorine-containing diamond coating. The coating contains carbon, silicon, oxygen, hydrogen and fluorine. The present invention relates to a substrate coated with a fluorine-containing diamond coating containing carbon, stone, oxygen, hydrogen, fluorine, and another dopant.

本發明另外有關製造包括塗覆含氟類鑽石塗料基材之物 件，其包括將此基材置於一個真空塗覆室，並以非成簇粒 子束共沉積作用將含碳、矽、氧、氫與氟類鑽石組合物沉 積於該基材上，該非成簇粒子束包括碳、矽、氧、氫與氟 之離子、原子或基團，每種粒子之平均自由路徑超過其來 源與基材生長粒子塗覆表面間之距離。 圖式簡述 圖1係顯示本發明含金屬塗料實例中電阻率對於濃度之 依存度示意圖。The present invention also relates to the manufacture of an object comprising coating a fluorine-containing diamond coating substrate, which comprises placing the substrate in a vacuum coating chamber, and co-depositing the A hydrogen and fluorine diamond composition is deposited on the substrate. The non-clustered particle beam includes carbon, silicon, oxygen, hydrogen and fluorine ions, atoms or groups. The average free path of each particle exceeds its source and substrate. The distance between the coated surfaces of the growing particles. Brief Description of the Drawings Fig. 1 is a schematic diagram showing the dependence of resistivity on concentration in an example of the metal-containing paint of the present invention.

圖2係顯示本發明含金屬塗料實例中電阻率對於溫度之 依存度示意圖。 圖3係該塗料沉積用之沉積室剖面圖。 圖4係使用反射電極沉積塗料用之沉積室剖面圖。 圖5係使用整體位於沉積室内電漿來源之較佳沉積室。 圖6係本發明含氟類鑽石塗料摩擦係數與硬度之p 1 〇 t。Fig. 2 is a graph showing the dependence of resistivity on temperature in an example of the metal-containing paint of the present invention. Figure 3 is a sectional view of a deposition chamber used for the coating deposition. Fig. 4 is a sectional view of a deposition chamber for depositing paint using a reflective electrode. FIG. 5 shows a preferred deposition chamber using plasma sources as a whole. FIG. 6 is p 1 ot of friction coefficient and hardness of the fluorine-containing diamond paint of the present invention.

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第10頁 575681 一丨· ^ 五、發明說明（6) ;度與偏*之圖。 圖9係具有本發明塗能量之圖。 圖1〇係具有本發 刀片放大剖面圖。 圖。 中間層之剃刀刀片放大剖面 圖11係具有塗覆含氟類鑽石余 部之透視圖。 主；、刹刀刀片之剃刀及其頭 發明詳、朮 本發明有關包括塗覆含 \ 明塗料包含碳、矽、氧、t 2、石塗料基材之物件。本發 材上，包括粘合性良好且^與氟。該塗料可塗覆於各種基 利基材與電手術儀器。該冷2應力低之撓性基材、精確磨 為堅硬而且持久。其可^ 土碑具有抗腐蝕與侵蝕性。其極 化學組合物進行所需之電"存。精確邊緣，而且其具有控制該 之最佳性質組合。 回轉或是變更，獲得特定應用 此處所使用及一般所知 區’使基材兩側之覆罢達 確邊緣π係基材之最狹窄 率之小半徑自約2 5垃古、* 曲平R端之極小半徑。已知曲 率半徑自約75埃至約1〇〇〇 Α 木。就極銳利刀片而言，曲 言，尖端半徑可能高達數埃:就其他較不銳利切割工具而 緣。 〜 百微米，不過其仍被視為精確邊 腐钱作用定義為金屬或人 此作用會因酸或鹼存右a "金因環境所致之電化學變質， 腐蝕性視其於活性序列之 ^。一般而言，金屬或合金之 位置而定。腐蝕產物通常呈金屬Page 10 575681 I 丨 · ^ V. Description of the invention (6); Degree and partial * graph. Fig. 9 is a graph showing the coating energy of the present invention. Fig. 10 is an enlarged cross-sectional view of a blade having the present invention. Illustration. Enlarged section of a razor blade in the middle layer Fig. 11 is a perspective view with the remainder of a coated fluorine-containing diamond. The razor and its head of a brake blade. Detailed and technical aspects of the invention The invention relates to an object comprising a coating material containing carbon, silicon, oxygen, t2, and a stone coating substrate. The hair material includes good adhesion and fluorine and fluorine. The coating can be applied to a variety of substrates and electrosurgical instruments. This flexible substrate with low cold stress is precisely ground to be hard and durable. It can be resistant to corrosion and erosion. Its polar chemical composition carries the required electricity. Precise edges, and it has the best combination of properties to control it. Rotate or change to get the specific application. The area used here and generally known is' the smallest radius of the narrowest rate of the π-based substrate overlaid on the sides of the substrate, from about 2 5 Lagoon, * Quping R Extremely small radius. The radius of curvature is known to be from about 75 Angstroms to about 10,000 Å. In the case of extremely sharp blades, the point is that the tip radius can be as high as several angstroms: for other less sharp cutting tools. ~ 100 micron, but it is still considered to be a precise edge-corruption effect. It is defined as metal or human. This effect can be caused by the presence of acids or alkalis. A " electrochemical deterioration caused by the environment due to the corrosivity depends on the active sequence. ^. In general, the location of the metal or alloy depends. Corrosion products are usually metallic

575681 五、發明說明（7) 氧化物或鹵化物形式。此Μ ，府 曝於自、然環境條件以及曝於有：材料；：=非金屬基材 本發明塗料除了保存邊緣與抗腐蝕特：： 當堅固而且對於化學藥劑、 卜：：：相 性，其亦具有熱安定性。 離所致之知蝕具有抗 化卿。本發明塗料對二二塗f不具生物渗透性或 碎機率。此係因為該基材較不會！：例如物理切 料對於各種基材之枯人性 * ;薄蝕裱境之故。該塗 超越習知腐银類鑽；^^^土，因此對於高溫之熱衝擊性 本發明較佳塗料之—包 氧原子安定之類玻璃石夕網=子化學安定之碳網及以 欲受到理論限制，m :成一種非晶相結構。雖然不 或安排，如此形成非大相"意指固態之原子無規結構 度。此耸奋杻Τ ί 圍規律順序，而且無結晶度或粒 模蔟狀物ΐ本發：ί:S埃之簇狀物或順序。無原子規 之非晶相性所，土料之關鍵特徵。簇狀物會破壞該結構 本發明4且可能成為變質之活性核心。 所需電阻；：:'鑽：塗料具有介電性；不過，視特定應用 雜劑以調適並調款^ =塗料可能包含一或多種氟以外之摻 類鑽石塗料，1 黾阻率。因此，本發明有關一種含氟 該摻雜劑網鱼^ f其組合物。此外，矽與氧原子亦可用於 /、其他元素與化合物。575681 5. Description of the invention (7) Oxide or halide form. This M is exposed to natural environmental conditions and is exposed to: materials ;: = non-metallic substrates In addition to the preservation edge and corrosion resistance of the coating of the present invention: When strong and for chemical agents, bu :: phase, its It also has thermal stability. The eclipse caused by separation is resistant. The coating of the present invention has no bio-permeability or fragmentation probability to the second and second coating f. This is because the substrate is less likely! : For example, the human nature of physical cutting of various substrates *; The coating surpasses the conventional rotten silver diamond; ^^^ soil, so for the high temperature thermal shock resistance, the preferred coating of the present invention-glass-stone-containing nets such as oxygen-containing atomic stabilizers = chemically stable carbon nets and Theoretical limits, m: into an amorphous phase structure. Although not or arranged, the formation of non-major phase " means the random structure of the atom in the solid state. This towering order is surrounded by a regular sequence, and there is no crystallinity or particle size. The hair: ί: S 埃 之 群 状 或 效应. Amorphous phase without atomic gauge, the key feature of earth material. Clusters destroy the structure of the invention 4 and may become a metamorphic active core. Required resistance; :: 'Diamond: the coating is dielectric; however, depending on the specific application, the dopant may be adapted and adjusted ^ = the coating may contain one or more diamond-doped coatings other than fluorine, 1 黾 resistivity. Therefore, the present invention relates to a fluorine-containing dopant netfish and its composition. In addition, silicon and oxygen atoms can also be used for other elements and compounds.

第12頁 此等其他摻、碳、矽、氧、氫與其他摻雜劑。 渡金屬與非舍 d可為週期表Ib〜Vl lb與VI I I族任一種過 575681 五、發明說明（8) 雖然該摻雜劑以導電薄膜為佳 屬摻雜劑作為選擇性摻雜劑。此外亦可結合一種非金 3、’、σ :非導電性捧雜劑。此等非導:要介電塗料時，亦 包性兀素，其可反應製得一種非導命摻雜劑可能包括導 性塗料時’可使用導電性元素與化：化合物。需要導電 因此，根據本發明，較佳塗料可:作為摻雜劑。 種玻壤狀31—0網以及選擇性包括一 it —種d/H網、一 認為這兩種或三種網之無規互穿作ς他摻雜劑網。一般 石塗料中已發現各方向不均勻強产^供本發明含氟類鑽 :女定而且具有獨特之化學、顧、：：广類鑽石塗料 /。即使於金屬濃度高達5G%時仍可避\ :、超導性質結 電子光譜、化學分析用之電子二=二=物形成（使用 線吸收細微結構光譜（（EXAF鱼 °a A)、延伸X射 (FTIR)證實）。此 質、〇Uner變化紅外線光譜 度以及”拉斗 貝亦可視所選用摻雜劑盥、、麓 Ϊ料= :極廣範圍内變化。如前述、二 特電、光學盥豆他固能性質月J 了以賦予该塗料獨 抗性。 /、，、 口心性貝及所需機械溫度、硬度與化學 就撓性基材而言，若情況需要，較佳其他摻雜劑 、Ge、Te、0、Mo、W、Ta、Nb、pd、ir、pi、νΊ e Λ ◦、Mg、Mn、Nl、Tl、Zr、Cr、Re、Hf、Cu、A1、 與Au，以Ti及W為佳。 就精確磨利邊緣基材而言，特別適於抗腐蝕含金屬塗料 575681 五、發明說明（9) - 之較佳其他摻雜劑之元素為B、Si、Ge、Te、〇、M〇、W、 Ta 、Nb 、Pd 、 Ir 、Pt 、V 、Fe 、Co 、Mg 、Μη 、Ni 、Ti 、Page 12 These other dopants, carbon, silicon, oxygen, hydrogen and other dopants. The transition metal and the non-d d may be any one of the Periodic Table Ib ~ Vl lb and VI I Group I. 575681 V. Description of the Invention (8) Although the dopant is preferably a conductive thin film as a selective dopant. In addition, a non-gold 3 ', σ: non-conductive dopant can also be combined. These non-conducting: when dielectric coatings are required, they also contain insoluble elements, which can be reacted to produce a non-conducting dopant, which may include conductive coatings. 'Electrically conductive compounds and compounds can be used. Need to be conductive Therefore, according to the present invention, a preferred coating can be used as a dopant. A glassy-like 31-0 network and optionally includes an it-d / H network, a random interpenetration of these two or three networks, and a dopant network. General stone coatings have been found to have uneven and strong yields in various directions. ^ For the fluorine-containing diamonds of the present invention, they are unique and have unique chemistry, chemistry, and broad-type diamond coatings. Can be avoided even when the metal concentration is as high as 5G% :: superconducting junction electron spectroscopy, electron two for chemical analysis = two = substance formation (using linear absorption fine structure spectrum ((EXAF fish ° a A), extended X (FTIR) confirmation. This quality, 〇Uner changes the infrared spectrum and "Dumper can also be used depending on the selected dopant toilet, piping material =: a wide range of changes. As mentioned above, two special electric, optical toilet The solid energy properties of Dota are given in order to give the coating unique resistance. / 、、、 Oral shellfish and the required mechanical temperature, hardness and chemistry For flexible substrates, if necessary, other dopants are preferred , Ge, Te, 0, Mo, W, Ta, Nb, pd, ir, pi, νΊ e Λ ◦, Mg, Mn, Nl, Tl, Zr, Cr, Re, Hf, Cu, A1, and Au, starting with Ti and W are preferred. As far as the sharp-edged edge substrate is concerned, it is particularly suitable for anti-corrosion metal-containing coatings. 575681 V. Description of the invention (9)-The elements of other dopants are B, Si, Ge, Te , 〇, M〇, W, Ta, Nb, Pd, Ir, Pt, V, Fe, Co, Mg, Mη, Ni, Ti,

Zr 、Cr 、Re 、Hf 、Cu 、A1 、N 、Ag 與Au ，以W 、Cr 、Zr 、丁i 及Hf為佳。可作為摻雜劑之較佳化合物包括TiN、BN、 AIN、ZrN 與 CrN，以 TiN 與 ZrN 最佳。 就電手術儀器而言，較佳其他摻雜劑元素為B、L 1、Zr, Cr, Re, Hf, Cu, A1, N, Ag, and Au, preferably W, Cr, Zr, Ding, and Hf. Preferred compounds that can be used as dopants include TiN, BN, AIN, ZrN and CrN, with TiN and ZrN being the most preferred. For electrosurgical instruments, the preferred other dopant elements are B, L 1,

Na 、 Si 、 Ge 、 Te 、〇、Mo 、 W 、 Ta 、 Nb 、 Pd 、 Ir 、 Ρΐ 、 V 、Na, Si, Ge, Te, 〇, Mo, W, Ta, Nb, Pd, Ir, PF, V,

Fe、C〇、Mg、Mn、Ni、Ti、Zr、Cr、Re、Hf、Cu、A1、 N、A g及A u，以W、C r、Z r、T i與H f最佳。較佳摻雜劑包括 TiN 、BN 、A1N 、ZrN 與CrN ，以TiN 、A1N 與CrN 最佳。 可以改變該含氟類鑽石塗料之電性質以獲得自約1 0_2至 約1 015歐姆-厘米之最適電阻率，同時保存該塗料之性質。 於低溫下觀察到特定三種網毫微複合網轉換成超導狀態而 且無電阻率。 該含氟類鑽石塗料之碳含量大於該塗料約4 0原子％為 佳，例如自約40至約98原子％，自約50至約98原子％更佳。 該含氟類鑽石塗料之氟含量為該碳濃度至少約1原子％，高 達約4 0原子％。雖然該塗料理論上不使用氫製備，但是氫 含量為該碳濃度至少約1原子％，高達約4 0原子％。該矽、 氧與摻雜劑（若存在摻雜劑的話）之總和大於該塗料組合物 約2原子％。於較佳具體實例中，碳原子對矽原子之比率自 約4 : 1至約9 : 1 ，碳原子對氟原子之比率自約1 . 1 : 1至約 2 .5:1 ，碳原子對氫原子之比率自約1 . 1 : 1至約2. 5 : 1 ，矽 原子至氧原子之比率自約0. 6 : 1至約1 . 7 : 1，摻雜劑對於碳Fe, Co, Mg, Mn, Ni, Ti, Zr, Cr, Re, Hf, Cu, A1, N, Ag, and Au are preferably W, Cr, Zr, Ti, and Hf. Preferred dopants include TiN, BN, A1N, ZrN and CrN, with TiN, A1N and CrN being the best. The electrical properties of the fluorine-containing diamond coating can be changed to obtain an optimum resistivity from about 10_2 to about 1015 ohm-cm, while preserving the properties of the coating. It was observed at low temperatures that certain three types of femtocomposite meshes were converted to a superconducting state without resistivity. The carbon content of the fluorine-containing diamond coating is preferably greater than about 40 atomic% of the coating, for example, from about 40 to about 98 atomic%, and more preferably from about 50 to about 98 atomic%. The fluorine content of the fluorine-containing diamond coating is at least about 1 atomic% and up to about 40 atomic% of the carbon concentration. Although the coating is theoretically prepared without using hydrogen, the hydrogen content is at least about 1 atomic% and up to about 40 atomic% of the carbon concentration. The total of the silicon, oxygen, and dopant (if present) is greater than about 2 atomic percent of the coating composition. In a preferred embodiment, the ratio of carbon atoms to silicon atoms is from about 4: 1 to about 9: 1, and the ratio of carbon atoms to fluorine atoms is from about 1.1: 1 to about 2.5: 1. The ratio of hydrogen atoms is from about 1.1: 1 to about 2.5: 1, the ratio of silicon atoms to oxygen atoms is from about 0.6: 1 to about 1.7: 1, and the dopant for carbon

575681 五、發明說明（ίο) _ 原子之比率自約0 : 1至約1. 5 : 1。此具體實例用於撓性基材 為佳。其他較佳具體實例中，碳原子對矽原子之比率自約 2 : 1至約8 ·· 1，氫原子對碳原子之比率自約0. 0 1 : 1至約0 . 4 : 1，而矽原子至氧原子之比率自約0 . 5 : 1至約3 : 1 ，摻雜劑 對於碳原子之比率自約0 . 1 : 1至約1 . 5 : 1。因此，就此塗料 中每1份數碳而言，存在自約0 . 0 1至約0 . 4份數氫，自約 0 · 1 2 5至約0 · 5份數矽及自約0 · 0 3 7 5至約1 . 0份數氧。此種 組合物中若存在摻雜劑，就每1份數碳而言，存在自約 0. 01至約1. 5摻雜劑，其視欲賦予該含金屬塗料之特徵而 定。此具體實例用於精確磨利基材及電手術儀器為佳。 該含氟類鑽石塗料之密度自约1. 8至約2. 1克/立方厘 米。其餘空間為直徑自約0 . 2 8至約0 . 3 5毫微米之毫微孔無 規網。該毫微孔網不會形成簇狀物或微孔。然後可以添加 摻雜劑調適該含氟類鑽石塗料之性質。該摻雜劑以無規方 式填滿該毫微孔網，於特定摻雜劑濃度下（甚至於高達5 0 原子％之濃度）最後形成無簇狀物或微結晶顆粒之另外一個 網。濃度低於約1 0原子％時，該摻雜劑會以個別原子形式 分佈於該類鑽石基質之毫微孔中。藉由控制摻雜劑濃度可 以控制此似無規結構當中介於摻雜劑原子間之平均距離。 當該摻雜劑元素或化合物之相對濃度到達約2 0 - 2 5原子％ 時，該摻雜劑形成含氟類鑽石塗料中之第三個網。 本發明之含氟類鑽石塗料尤其適用於製造撓性基材上之 電阻器與電容器。該塗料不僅可與MCM處理整合，亦可賦 予良好性能-良好體積對重量比率，其可以照相片版印刷575681 V. Description of the Invention (ίο) _ The atomic ratio is from about 0: 1 to about 1.5: 1. This specific example is preferably used for a flexible substrate. In other preferred embodiments, the ratio of carbon atoms to silicon atoms is from about 2: 1 to about 8.5 · 1. The ratio of hydrogen atoms to carbon atoms is from about 0.0 1 to 1 to about 0.4 to 1, and The ratio of silicon atoms to oxygen atoms is from about 0.5: 1 to about 3: 1, and the ratio of dopants to carbon atoms is from about 0.1: 1 to about 1.5: 1. Therefore, for each part of carbon in this coating, from about 0.01 to about 0.4 parts of hydrogen, from about 0. 125 to about 0.5 parts of silicon and from about 0 to 0 3 7 5 to about 1.0 parts of oxygen. If a dopant is present in such a composition, there are from about 0.01 to about 1.5 dopants per 1 part of carbon, depending on the characteristics to be imparted to the metal-containing coating. This specific example is better for precision grinding of substrates and electrosurgical instruments. The density of the fluorine-containing diamond coating is from about 1.8 to about 2.1 g / cm3. The remaining space is a random network of nanopores with a diameter from about 0.28 to about 0.35 nanometers. The nanoporous network does not form clusters or micropores. A dopant can then be added to adjust the properties of the fluorine-containing diamond coating. The dopant fills the nanoporous network in a random manner, and at a specific dopant concentration (even up to a concentration of 50 atomic%) finally forms another network without clusters or microcrystalline particles. At concentrations below about 10 atomic%, the dopant will be distributed as individual atoms in the nanopores of the diamond matrix. By controlling the dopant concentration, the average distance between dopant atoms in this pseudo-random structure can be controlled. When the relative concentration of the dopant element or compound reaches about 20 to 25 atomic%, the dopant forms a third network in the fluorine-containing diamond coating. The fluorine-containing diamond coating of the present invention is particularly suitable for manufacturing resistors and capacitors on flexible substrates. The coating is not only integrated with the MCM process, but also gives good performance-good volume to weight ratio, which can be printed on photographic plates

L:\56\56197.PTD 第 15 頁 575681 五、發明說明（π) — 術製圖，而且具有多層輸出功率。該碳、矽、氫、氧、氟 與選擇性其他摻雜劑以及該塗料之厚度與製圖方式均可依 特定裝置重要性而作調適。該塗料可沉積於多種基材上， 尤其是聚合薄膜，諸如具有良好粘合性與低薄膜應力之親 水或疏水熱塑性聚合物，其Tg大於約1 〇〇 °c為佳，其Tg大 於約1 5 0 °C更佳。該聚合薄膜選自包括聚醯亞胺、聚酯 類、poly therm ide類、聚醯胺-醯亞胺類、聚對苯二曱酸 伸乙酯類、Kapton (DE州威明頓之杜邦公司）、My lar (D E州威明頓之杜邦公司）、u 11 e m (P i 11 s f i e 1 d，M A之通 用電器公司）與Tori on (Amoco Performance ProductsL: \ 56 \ 56197.PTD Page 15 575681 V. Description of the Invention (π) — technical drawing, and it has multiple layers of output power. The carbon, silicon, hydrogen, oxygen, fluorine, and other optional dopants, as well as the thickness and drawing method of the coating can be adjusted according to the importance of the specific device. The coating can be deposited on a variety of substrates, especially polymeric films, such as hydrophilic or hydrophobic thermoplastic polymers with good adhesion and low film stress, preferably having a Tg greater than about 1000 ° c and a Tg greater than about 1 5 0 ° C is better. The polymer film is selected from the group consisting of polyimide, polyester, poly therm ide, polyamidide-imide, polyethylene terephthalate, and Kapton (DuPont, Wilmington, DE) , My lar (DuPont of Wilmington, DE), u 11 em (P i 11 sfie 1 d, General Electric Company of MA) and Tori on (Amoco Performance Products

Alpharetta，GA)。其調適該類、鑽石塗料中金屬摻雜劑數 里與氣含里之月匕力使其可以相容地塗覆於各種捷性'美材 料上。 土材 本發明含氟類鑽石塗料亦特別適用於精癌磨 〜 如剃刀刀片類。具體實例之一中，圖9顯示具—儀态’諸 尖端2 4之剃刀刀片1 8放大剖面圖，其尖端给费精&確磨利 類鑽石塗料。圖9中，基材20(即鋼剃刀刀二）设^^發明含氟 氟類鑽石塗料21。聚氟乙烯（PTFE) 22之薄冷/後一種含 氟類鑽石塗料21上。 Λ &冗積於該含 圖1 0顯示具有精媒磨利尖端2 4之經塗覆刀片1 已塗覆中間層23之基材20。然後該中間層23涂费9^其包括 石塗料21，最後塗覆PTFE塗料22。該中^=復含氣類鑽 J /f Ιηχ _ ^ g 矽、碳化矽、釩、钽、鈮、鉬與其合金“ ’、自 材料可以單獨使用或與彼此併用。該中門思 9 此寻 间層之沉積厚度自Alpharetta, GA). It adjusts the metal dopant strength of this type of diamond coatings to a few months and gas to make it compatible to apply on a variety of short-lived 'beauty materials. Earth material The fluorine-containing diamond coating of the present invention is also particularly suitable for fine cancer grinding ~ such as razor blades. In one of the specific examples, Fig. 9 shows an enlarged sectional view of a razor blade 18 with a tip "4", the tip of which is a fine diamond-like paint. In FIG. 9, the base material 20 (namely, the second steel razor blade) is provided with the fluorine-containing fluorine-based diamond paint 21 of the present invention. A thin cold / polyvinyl fluoride (PTFE) 22 coating on the latter fluorine-containing diamond coating 21. Λ & redundant in this figure Fig. 10 shows a coated substrate 1 with a fine media sharpened tip 2 4 and a substrate 20 coated with an intermediate layer 23. The intermediate layer 23 is then coated with a coating 9 including a stone coating 21 and finally a PTFE coating 22. The middle ^ = complex gas drill J / f Ιηχ _ ^ g silicon, silicon carbide, vanadium, tantalum, niobium, molybdenum and their alloys ", the materials can be used alone or in combination with each other. The Zhong Mensi 9 Interlayer thickness

575681 五、發明說明（12) 約5 0至約5 0 0埃。該P T F E之沉積厚度自約丨〇埃至約1 Q 〇 〇 埃，自約2 5至約7 5埃為佳。 具體實例之一中，將該刀片裝配於剃刀上。圖丨丨顯示圖 片1 8裝於用仗抛棄式剌刀2 5之裝配頭2 6上。該頭之 開口 27可以使碎屑通過刮鬍平面。因此，已知本發明塗覆 t類鑽石塗料刀片可製成各種刀片，諸如替換式雙鋒或 早鋒刀片’或與剃刀組結合之刀片。 本發明保存精確邊緣之含氟類鑽石塗料有許多用途，包 用於容易腐謂或侵钱及鈍化之金屬與 餐呈ς ^ τ術儀器、剃刀刀[工業與非工業工具、 4/、、刀子、小刀、與任何精確磨利基材。 如鑽石塗料尤其適合作為電手術儀 UL 1 9 7,9 6 2與第5,54 9，_號所述之電 手術刀片」此寻專利係以提及的方式併入本文中。 此外，该含氟類鑽石塗料涂舜 鉗、腹腔鏡儀哭、t4主復/、他裝置，諸如雙極 管。 “用拓架與生物醫療裝置，諸如導尿 已計畫使用單層或多屑相 基準）含氟類鑽石塗料製^敗冋或，不同（以化學藥劑含量為 鑽石塗料可與包含其他摻：:性質。例如，含氟類 石塗料層壓製得所需性質^ θ "屬或非金屬）之含氟類鑽 為改善粘合性，習用類575681 V. Description of the invention (12) About 50 to about 500 Angstroms. The deposition thickness of the P T F E is from about 10 Angstroms to about 1 Q Angstroms, and preferably from about 25 to about 75 Angstroms. In one specific example, the blade is mounted on a razor. Figure 丨 丨 shows picture 1 8 mounted on the assembly head 2 6 of the disposable trowel 25. The head opening 27 allows debris to pass through the shaving surface. Therefore, it is known that the present invention can be made into a variety of blades, such as a replaceable double-edged or early-edged blade 'or a blade combined with a razor set. The fluorine-containing diamond coating for preserving precise edges of the present invention has many uses, including metal and food products that are easy to rot or invade money and passivation. Τ τ surgical instruments, razors [industrial and non-industrial tools, 4 /, Knives, knives, and any precision sharpened substrate. For example, diamond coatings are particularly suitable as electrosurgical devices described in UL 1 9 7, 9 6 2 and No. 5,54 9, _. This patent is incorporated herein by reference. In addition, the fluorine-containing diamond paint is coated with pliers, laparoscopy, t4 main and / or other devices, such as bipolars. "Using extensions and biomedical devices, such as urinary catheterization, it is planned to use single-layer or multi-chip-based diamond coatings made of fluorine-containing diamond coatings, or different (based on chemical content, diamond coatings can be mixed with other containing: : Properties. For example, the fluorine-containing stone coating layer is pressed to obtain the desired properties ^ θ " of or non-metallic).

塗層間通常具有一中間層鑽（DLC")塗料在該基材與DLC 之適用厚度。若DLC塗層、岛斥不過，此中間層限制DLC塗層 3 ^厚則會發生剝離現象。令人驚 575681 五、發明說明（13) "的疋本^月含氟類鑽石塗料極佳，故不需要ψ 1厚 因此，該塗料材料可以塗得較厚不會自該基：Π:% 含氟類鑽石塗料可以塗覆較厚層之能力係該s i〜0網 ^ 力低所致，據信可以對塗覆該含氣 ,δ 較佳抗脚。若情況需要，可：;1':二 Ζ塗料。該含氣類鑽石塗料之調整力亦編：= 塗料與該中間層具有良好钻合性，該含氣鼠4鑽石 有一種摻雜劑，使其與該中間層相Α塗料可含 最適。逐漸改變特定摻雜劑以及該；=巧與枯合性 種”調整作用"。不包含摻雜劑時，該可以完成此 有不同性質。除了改變化學組成之外，改變y石 '塗料亦具 達成改變含氟類鑽石塗料之性質，苴 π =積條件亦可 不受限於溫度與壓力。因此，該含激：：：條件包括但 地貼在含金屬與含非金屬基材上。颁鑽主料可以良好 除了粘合性優良之外，無其他摻 於精確磨利基材與撓性基材時，且右=士 ^务明塗料塗覆 電常數、低表面能以及水接觸角電強度、低介 塗料介電強度超過1 MV/厘米，而^ 其他摻雜劑之 =之介電常數極低，低至約2. 5。 °涂门&4MV/厘米。該塗 能，低至約19. 6達因/厘米。該涂：主料具有極低表面 :。1。。該塗料之水接觸角度度大，大 有疏水性。 Ύ M使撓性基材表面具 該塗料塗覆於撓性基材時具有啦 生。該塗料之介電常數使溫度範；早：中之良好熱安定 阁保持在-173 °C〜177亡。 第18頁 575681 發明說明（14) 。亥;度乾圍包括軍事溫度範圍-25 t：至125 。 前=2發明電手術儀器而言，該含氟類鑽石塗料包含一種 ㉟被/、他彳乡4劑為佳。此種塗料形成阻抗自約1至約1 〇 〇 〇 ^ 乂之物件為佳，該塗料之電阻率自約1 〇_2至約丨〇1S歐姆一 =米。用於此等儀器之塗料表面能自約1 9至約2 9達因/厘 =為彳土 ’自約2 4至約2 6達因/厘米最佳。該塗料之水接觸 角度自約80。至約1〇1。為佳。 #其中存在以氧安定之玻璃狀矽，以避免高溫時生長石黑 ^，以及避免含金屬塗料中形成金屬蔟狀物，並減少涂二 使：ί i ί:s此加強與該基材之直接枯合性。此顯；复 吏本务明έ氟類鑽石塗料對於基材材料之粘合性較，、 二亥含氟類鑽石塗料中所發現之低内在應力有助於择加复 ::蝕性。塗料不僅不可腐蝕劑起反應'，而且亦必；作工 :種屏蔽層，避免該腐蝕劑與受保護基材接觸。習用丄為 ;:經常具有南度内在應力，因此會形成針孔及 】！古因本發明含氟類鑽石塗料中之應力相對較低之故 其〉又有孔，因此可以抗化學藥劑侵襲與參透。低之故， =發明含敦類鑽石塗料之溫度安定性遠 材料。結晶鑽石於大約1丨〇 〇。〇下仍 白用頒鑽石 始發生石墨化作用。石英在1 47 0 1 2右2 f此情況下開 在高達1 7 0 0 °C下具有短期熱安定性。習用^ =熱安定性， 薄膜於石墨化作用之前僅於約60 ~非合金類鑽石 似薄膜之熱安定性更差。相對狀態。合金 料在125CTC下具有長期安定性，在2〇〇/ S虱頬鑽石塗 卜具有短期安定The coating layer usually has a suitable thickness of the intermediate layer drill (DLC) coating on the substrate and the DLC. If the DLC coating and the island are not repelled, this intermediate layer will limit the thickness of the DLC coating to a thickness of 3 则会, which will cause peeling. Amazing 575681 V. Description of the invention (13) " The fluorocarbon diamond coating of this month is excellent, so it does not need ψ 1 thick. Therefore, the coating material can be coated thicker and will not be from the base: Π: % The ability of fluorine-containing diamond coatings to coat thicker layers is due to the low strength of the si ~ 0 mesh. It is believed that δ is better resistant to feet. If the situation requires, you can:; 1 ': 二 Z coating. The adjustment power of the gas-containing diamond coating is also edited: = The coating has good drillability with the intermediate layer, and the gas-containing rat 4 diamond has a dopant, so that it can be optimally contained in the phase A coating. Gradually change the specific dopant and the "adjusting effect" of "special and cumulative species". When dopants are not included, this can be done with different properties. In addition to changing the chemical composition, changing the Y's coating also In order to change the properties of fluorine-containing diamond coatings, the 苴 π = product condition can also be not limited to temperature and pressure. Therefore, the stimulus :: conditions include but are affixed to metal-containing and non-metal-containing substrates. The main material of the drill can be good. In addition to excellent adhesion, there is no other material blended with precision ground and flexible substrates, and the right = Shi Mingming coating coating electrical constant, low surface energy and water contact angle. Strength, the dielectric strength of low-dielectric coatings exceeds 1 MV / cm, and the dielectric constant of ^ of other dopants = is extremely low, as low as about 2.5. ° Paint door & 4MV / cm. The coating energy, low To about 19.6 dyne / cm. The coating: The main material has an extremely low surface: 1. The coating has a large water contact angle and is highly hydrophobic. Ύ M makes the surface of the flexible substrate with the coating It has a good effect when applied to a flexible substrate. The dielectric constant of the coating makes the temperature range; early: moderately good The thermal stability chamber is maintained at -173 ° C ~ 177 deaths. Page 18 575681 Description of the invention (14). Hai; Dugan Wai includes military temperature range -25 t: to 125. Former = 2 invention of electrical surgical instruments, the Fluorine-based diamond coatings preferably contain a quilt / 4 other agents. It is preferred that such coatings form objects having an impedance of from about 1 to about 1 000 ^ 乂, and the resistivity of the coating is from about 1 〇_ 2 to about 丨 〇1S ohm = meter. The coating surface energy used for these instruments is from about 19 to about 29 dyne / centimeter = for soil 'from about 24 to about 26 dyne / cm. The water contact angle of the coating is from about 80. to about 101. It is better. #The presence of glassy silicon stabilized with oxygen, to avoid the growth of stone black at high temperature ^, and to avoid the formation of metal hafnium in metallic coatings Material, and reduce the number of coatings: ί i ί: s This strengthens the direct desiccation with the substrate. This is obvious; the principle of the compound is that the fluorine-based diamond coatings have better adhesion to the substrate material, The low intrinsic stress found in Erhai fluorine-containing diamond coatings can help to add :: corrosion. The coating is not only non-corrosive to react, but also necessary; work : A kind of shielding layer to avoid the contact of the corrosive agent with the protected substrate. The customary 丄 is: often has internal stresses in the south, so pinholes are formed and the stress is relatively low in the ancient fluorine-containing diamond coatings of the present invention The reason is that it has holes, so it can resist the invasion and penetration of chemical agents. The low reason = the invention of a temperature-stabilizing material with a diamond-containing coating. Crystal diamonds are still used for free at about 1 丨 00. Diamonds begin to graphitize. Quartz has a short-term thermal stability at 1 47 0 1 2 right 2 f. In this case, it has short-term thermal stability at temperatures up to 1700 ° C. Conventional ^ = thermal stability. At about 60 ~, the non-alloy diamond-like film has worse thermal stability. Relative state. The alloy material has long-term stability at 125CTC and short-term stability at 200 / S louse diamond coating.

第19頁 575681 五、發明說明（15) — 性。因此本發明塗料之熱安定性超過結晶鑽石之熱安定 性，同時保有非晶相類鑽石狀態。 在約6 0 0 °C至約1 0 0 0 °C範圍内，該含氟類鑽石塗料材料 之碳基質化學鍵部分自sp3改變成sp2。惟其仍然保有一般 結構與其”類鑽石”性質。相對地，在相同條件下，習用 DLC會石墨化而且失去其類鑽石性質。此外，在4 0 0 °C至 5 0 0 °C範圍（以43 0 °C為佳）時，觀察到逆向退火，因此sp3 對s ρ2比率提南。因為石墨碳之導電性南於D L C，所以抑制 碳之石墨化作用對於保存介電性質極為重要。因此，該含 氟類鑽石塗料之熱安定性使本發明介電塗料具有明顯優於 DLC塗料之優點。 〜 本發明含氟類鑽石塗料之其他優點是其硬度與持久性。 該含氟類鑽石塗料（尤其是含金屬塗料）結合高度微硬度與 彈性，因此本發明含氟類鑽石塗料之微硬度自約5至約 32GPa 。 本發明亦包括一種製造塗覆含氟類鑽石塗料基材之方 法。該方法包括將此基材置於一個真空塗覆室，並以非成 簇粒子束共沉積作用將含碳、矽、氧、氫與氟類鑽石組合 物沉積於該基材上，該非成簇粒子束包括碳、矽、氧、氫 與氟之離子、原子或基團，每種粒子之平均自由路徑超過 其來源與基材生長粒子塗覆表面間之距離。 更特別的是，本發明含氟類鑽石塗料可以經由離子、原 子或適當元素基團之非成蕉束的共沉積作用合成，其中每 種粒子之平均自由路徑超過其來源與生長粒子塗覆表面間Page 19 575681 V. Description of the Invention (15) — Sex. Therefore, the thermal stability of the coating of the present invention exceeds the thermal stability of crystalline diamond, while maintaining the amorphous phase diamond-like state. In the range of about 600 ° C to about 100 ° C, the carbon matrix chemical bond portion of the fluorine-containing diamond coating material was changed from sp3 to sp2. However, it still retains its general structure and its "diamond-like" nature. In contrast, under the same conditions, conventional DLC will graphitize and lose its diamond-like properties. In addition, in the range of 400 ° C to 500 ° C (preferably 43 ° C), reverse annealing is observed, so the ratio of sp3 to s ρ2 is raised to the south. Since the conductivity of graphitic carbon is lower than D L C, inhibiting the graphitization of carbon is extremely important to preserve the dielectric properties. Therefore, the thermal stability of the fluorine-containing diamond coating makes the dielectric coating of the present invention significantly superior to the DLC coating. ~ Another advantage of the fluorine-containing diamond coating of the present invention is its hardness and durability. The fluorine-containing diamond coating (especially metal-containing coating) combines high micro hardness and elasticity, so the micro hardness of the fluorine-containing diamond coating of the present invention is from about 5 to about 32 GPa. The present invention also includes a method for manufacturing a substrate for coating a fluorine-containing diamond paint. The method includes placing the substrate in a vacuum coating chamber, and depositing a carbon-, silicon-, oxygen-, hydrogen-, and fluorine-containing diamond composition on the substrate by non-clustered particle beam co-deposition. The non-clustered The particle beam includes ions, atoms, or groups of carbon, silicon, oxygen, hydrogen, and fluorine, and the average free path of each particle exceeds the distance between its source and the coated surface of the substrate growing particles. More specifically, the fluorine-containing diamond coatings of the present invention can be synthesized via the co-deposition of non-banana bundles of ionic, atomic, or appropriate element groups, where the average free path of each particle exceeds its source and growing particle coating surface between

第20頁 575681 五、發明說明（16) 之距離，而且各束包含 — 聚管中藉由電漿放電心：規；…粒子。可以在電 粒子製得含碳粒子束，#脸=工至中之问壓電％分離帶電 至少50%含碳粒子之動:二、導至該基材上。 該基材之溫度必須不能約1〇〇電子伏特。成長期間 % 兩於 5 0 0 °c。 圖5顯示用於塗覆沉籍 先質入口系統i 3包括二處：二塗覆室的較佳具體實例。 經由該多孔陶兗材料注^ &官與一個多孔陶瓷材料3， 該先質可為任何適：=質… 物。有機石夕化合物是c、H 〇針先質之化合 機石夕化合物為液態聚：氣佳先質。較佳有 聚-3, 3, 3-三氣丙基甲么丙"基石夕氣烧。特佳之先質是 合物。 鼠内土曱基矽氧烷-(50%)二甲基矽氧烷共聚 合：ί埶：22先:括入：系統13經由該室基板11與該室結 料之美匕笔阻加熱鎢絲4。欲塗覆含氟類鑽石塗 1之基材5貼附在基材座6上。 一 (DC或RF)。實^ μ冲捉1八&材偏屋 ^Μ 、不上，5亥乐統係使用正常真空泵抽程序向下 燥允氣位於入口7之閘控閥（未顯示出來），並以乾 止：然後開；該,？，直到該，到達大氣壓力為 他敬至門9，亚使用任何可能方法（彈筈失、虫萝 置-個圓筒ϊ:;νν 座之設計方式係備其亦可放 約中央驅動l n未顯示出來），於操作時該圓筒樣本以大 輪心1 〇的轴及其自身的軸（與轴]0垂直）兩個方 五 向 發明說明（17) ____ 旋轉。如此，該圓筒的軸可总 承載基材時，關閉該室門，/、軸1 0垂直。 该系統壓力降至至少1 Q~5至1 私空遠室’並開啟閘控閥使 圍。達到上述基本壓力時，麵托耳，此為系統基本壓力範 制器將氬氣導入該室，直到今由一個針狀閥或質量流量控 為止，約1-3x1 04為佳。於此^室壓力到達約5xl〇-5至lxl 及電磁鐵電源。該燈絲兩泣4開啟燈絲電流、燈絲偏壓 或陰極）之電流。該燈 '、過熱陰極（亦稱為該燈絲 % ^ (與接地相較大約〜丨5 〇伏’、‘加於該燈絲之固定浮動 基板或接地間測得之電济。 電聚電流係於該燈絲與該 板11之電子的電場。該:磁此電壓提供移動該燈絲射至基 其產生磁場’該磁場使兩鐵電源提供談電磁鐵電流’使 徑長度’並且改盖帝子了子路徑變成螺旋狀，增加電子路 撞機率。該基材電;^蒸發所產生蒸氣分子間之碰 開啟此等電源會ί;：!:時開啟。 材。所需清潔期間之後，=虱電漿，其係用以沉積前之基 有1至1 〇個矽原子。較扦 '始供應先質。此等先質可能具 敦丙基甲基矽氧烷—（5〇ί)處係氟聚矽氧，以聚—3,3,3-三 =以熱燈絲加熱之微孔。狀；：=J烷共聚合物尤佳。使 導入活性電漿區。哼先柄^瓦或金屬分配器將該先質直接 體可為惰性（以氬作為進貝料之其他氣體混合，此等其他氣 限於曱烷、乙炔盥丁 r 武脰）及活性氣體，包括但不受 該先質碎裂及離子化Γ〜熱燈絲光子與射出電子會導致 575681 五、發明說明（18) 一 間之壓力差異所致。當先質流與該室之蒸發作用已呈安 定，關閉該氬氣流。該經離子化先質蒸氣形成一種安定電 漿，因為該基材偏壓之故，該電聚之離子加速移向該基材 座。因此，發生含氟薄膜之沉積作用。 亦可使用液體-療氣輸送糸統將先質導入該糸統’在已 知領域中該輸送系統係由流動控制器、加熱器與分配器組 成。該液體-蒸氣輸送系統係真空技術領域中習知之慣用 現成組件。將該先質貯存於一個貯存器，並輸送至一個閃 蒸器。將該先質閃蒸成蒸氣。使用質量流量控制器精確控 制該先質蒸氣之流速。可使用諸如氬等混合氣體促進先質 之蒸發作用，不過此舉並非必要作法。在液體輸送系統實 例中，電子來源可能是與該先質輸送系統分離之熱燈絲。 以機械性泵唧作用向下初步處理，隨後以高度真空泵泵 唧達到高度真空。該泵可為擴散泵、渦輪分子泵、低溫泵 或真空技術領域中習知之其他高度真空泵。 本發明方法中可以分批方法少量沉積該塗料。此實例 中，該基材安裝在位於沉積室内之基材座上，將該室抽 空，進行沉積作用，並使該室通風，然後移去經塗覆基 材。 就較大量而言，本發明方法可於空氣-空氣系統中進 行。此種空氣-空氣系統可由清潔、運送至沉積室之零件 及該基材座上之機械/自動機械承載零件組成。然後，將 該基材座送至一個負載-鎖室中，幹著送入該沉積室並進 行塗覆作用。塗覆之後，將該基材座自沉積室移至負載-Page 20 575681 V. The description of the invention (16), and each beam contains — the plasma discharge core in the polytube: gauge;… particles. Beams of carbon-containing particles can be made in electric particles, # face = piezoelectricity% separation and charging of at least 50% of carbon-containing particles: Second, lead to the substrate. The temperature of the substrate must not be about 100 electron volts. The growth period% is less than 50 ° C. Fig. 5 shows a preferred specific example of the coating precursor system i 3 for coating: the two coating chambers. Through the porous ceramic material and the porous ceramic material 3, the precursor can be any suitable: = quality ... The organic stone compound is a compound of c and H 0 precursors. The organic stone compound is a liquid poly: qi good precursor. Preferred is poly-3, 3, 3-tris-propyl-propyl-molybdenum " A particularly good precursor is a compound. Copolymerization of muscarinic siloxanes- (50%) dimethylsilane: 埶: 22 first: enclosed: system 13 heating the tungsten wire through the dagger of the chamber substrate 11 and the chamber material. 4. A substrate 5 to be coated with a fluorine-containing diamond coating 1 is attached to a substrate holder 6. One (DC or RF). Actually, ^ μ Chongchou 18 and the material partial house ^ M, not on, 5 Haile system uses a normal vacuum pumping procedure to dry down the gate valve (not shown) at the inlet 7 and stop. : Then open; should ,? Until that time, when the atmospheric pressure is reached, he respects Gate 9, and Ya uses any possible method (impeachment loss, insect pest-a cylinder ϊ:; νν The design of the seat is such that it can also release the central drive (Shown), during the operation, the cylindrical sample is rotated around the axis of the large wheel center 10 and its own axis (vertical to the axis) 0 in two directions and five directions (17) ____ rotation. In this way, when the axis of the cylinder can always carry the substrate, the chamber door is closed, and the axis 10 is vertical. The pressure of the system is reduced to at least 1 Q ~ 5 to 1 private air room 'and the gate valve is opened to surround. When the above basic pressure is reached, face the ears. This is the system basic pressure regulator that introduces argon into the chamber. Until now, it is controlled by a needle valve or mass flow control, preferably about 1-3x104. Here the chamber pressure reaches about 5x10-5 to lxl and the electromagnet power supply. The filament bleeds 4 to turn on the filament current, filament bias or cathode) current. The lamp ', the overheated cathode (also known as the filament% ^ (approximately ~ 50 volts compared to ground), the electricity measured on a fixed floating substrate or ground connected to the filament. The electric field of the filament and the electrons of the plate 11. The: This voltage provides the magnetic field to move the filament to the base to generate a magnetic field. The magnetic field causes the two iron power sources to provide the electromagnet current and the length of the diameter. The path becomes a spiral, increasing the probability of collision with the electronic circuit. The substrate is electrically charged; the collision between vapor molecules generated by evaporation turns on these power sources; :: is turned on. Material. After the required cleaning period, = lice plasma It is used to deposit 1 to 10 silicon atoms before the deposition of the base. The precursor is supplied more than this. These precursors may have propylmethylsiloxane-(5〇ί) fluoropoly Siloxane, poly-3,3,3-three = micropores heated by hot filament. Shape:: = J-alkane copolymer is particularly preferred. It is introduced into the active plasma area. Humming shank ^ tile or metal distributor The precursor may be inert (mixed with other gases using argon as the feedstock, these other gases are limited to pinane and acetylene) r Wu 脰) and active gas, including but not subject to the fragmentation and ionization of the precursor, ~ hot filament photons and emitted electrons will cause 575681 V. Description of the invention (18) The pressure difference between the first mass flow and The evaporation of the chamber has stabilized, and the argon gas flow is turned off. The ionized precursor vapor forms a stable plasma. Because the substrate is biased, the ionized ion accelerates to the substrate seat. Therefore The deposition of the fluorine-containing film occurs. The precursor can also be introduced into the system using a liquid-therapy gas delivery system. In the known art, the delivery system consists of a flow controller, a heater, and a dispenser. The liquid -The steam delivery system is a customary off-the-shelf component known in the vacuum technology field. The precursor is stored in a reservoir and transferred to a flasher. The precursor is flashed into steam. The mass flow controller is used to precisely control the precursor The velocity of the mass vapor. A mixed gas such as argon can be used to promote the evaporation of the precursor, but this is not necessary. In the case of a liquid delivery system, the electron source may be transported with the precursor. To send the hot filament separated from the system. It is initially treated downwards by mechanical pumping, and then reaches a high vacuum with a high vacuum pump. The pump can be a diffusion pump, a turbo molecular pump, a cryopump or other heights known in the vacuum technology field. Vacuum pump. The coating can be deposited in small batches in the method of the present invention. In this example, the substrate is mounted on a substrate holder located in a deposition chamber, the chamber is evacuated, the deposition is effected, and the chamber is ventilated, and then moved The coated substrate is removed. For larger amounts, the method of the present invention can be performed in an air-air system. Such an air-air system can be cleaned and transported to the deposition chamber by parts and mechanical / automatic on the substrate holder It is composed of mechanical load-bearing parts. Then, the substrate holder is sent to a load-lock chamber, dried into the deposition chamber and coated. After coating, the substrate holder is moved from the deposition chamber to the load-

II

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575681 發明說明（19) 鎖 其 曰 取 為 表 光 圍 使 仟 子 源 液 緣 以 導 束 增 子 離 進 烴 至，然彳交移至空氣中。該欲塗覆基材位於基材座上或是 他處理情況時當中可以旋轉、傾斜或者定向或是控制。 該基材安置於基材座期間可以旋轉、傾斜及振動。對於 小化教子或碎屑累積及基材表面污染而言，以垂直定向 佳。以低度湍動真空泵唧抽空該沉積室，使沉積在基材 面之粒子與碎屑最小。 亦2藉由輝光放電清潔作用完成氬離子清潔作用。在輝 放兒清潔作用中，導入氬氣直到該室壓力在1 托耳範 内為止。輝光放電係以⑽或叱進行。此放電作用中，巳可 =自=0. 03至約5. 〇仔伏之基材偏壓。RF頻率在 赫執圍内。 土以υ 亦7使用沉積塗覆領域中習知之其他離子來源產生離 Λ來源包括但不受限於高夫曼（Kaufmann)型離子丈 體=㈣F平行板。可使用由高夫曼離子來源與J質 。j I不統組成之沉積系統將此等塗料沉積於精確、參 :=惰性氣體或先質氣體操作該高夫曼離子來=。 二=體知作該高夫曼離子來源，並分別將該先質:辟 力^沉積室為佳。該高夫曼離子來源係以充分高戶^ = 加。哕二f，，如此會產生造成堅硬類鑽石塗料之抟擊 束力π ‘ = Ϊ，離子來源可以在400至1 5 0 0伏範圍内之帝 子名k电壓刼作’在8 〇 0至1 2 0 0伏範圍内為佳。除， 導入少細氣體(諸如氧氣 污毕水q冻作用。已發現該離子清潔方法可以575681 Description of the invention (19) It is taken as the surface light to make the source liquid edge of the radon source to introduce hydrocarbons to the beam, and then the radon is transferred to the air. The substrate to be coated can be rotated, tilted, orientated, or controlled during the processing of the substrate or other processing conditions. The substrate can be rotated, tilted and vibrated while being placed in the substrate holder. For miniaturization or debris accumulation and substrate surface contamination, vertical orientation is preferred. The deposition chamber was evacuated with a low-turbulence vacuum pump to minimize particles and debris deposited on the substrate surface. Also, the argon ion cleaning effect is completed by the glow discharge cleaning effect. During radioactive cleaning, argon is introduced until the pressure in the chamber is within 1 Torr. Glow discharge is performed with ⑽ or 叱. In this discharge, the substrate bias can be from 0.03 to about 5.0 volts. The RF frequency is within Hertz. The ion source also uses other ion sources known in the field of deposition coating to generate ion sources. Λ sources include, but are not limited to, Kaufmann-type ion beams = ㈣F parallel plates. Can be used with Guffman ion sources and J mass. The deposition system of j I is not uniform. The coatings are deposited on a precise, reference: = inert gas or precursor gas to operate the Guffman ion. Two = body is known as the source of the Guffman ion, and the precursor: Bili ^ deposition chamber is better. The Guffman ion source is sufficiently high ^ = plus.哕 2f, this will produce a striking beam force π '= 造成 which causes a hard diamond-like coating, the ion source can be operated in the range of 400 to 1 500 volts, and the voltage of the emperor's name can be adjusted to' 800 to It is better to be in the range of 1 200 volts. In addition, the introduction of less fine gases (such as oxygen to pollute the water and the freezing effect). It has been found that this ion cleaning method can

/、他π染物’並改善沉積於基材上之塗料的枯I/, Other dyes ’and improve the dryness of the coating deposited on the substrate

575681575681

劑材料之共沉積㈣。氬氣产Η私 流至磁控管，並於達到基本壓力之後 =礼机開始 濺鍍清潔該基材時，使用快門12 ^ s δ。經由 完成時，開快門12並以所需能= =作用 作用可於塗料沉積開始時、塗覆沉積期間、。此 或間歇性於塗覆沉積期間進行，進 "知之後 構與细合物而定。II由作用Dc或RF ，' ς =料結 (金屬、陶竟、合金等）用於共沉積作，。了將各類材料 參考圖3，該塗料之生長條件如下。沉積室 超柳托耳，電漿產生活性區〜2之壓力在自約"力:可 約5. OxlO-2托耳範圍内。該基材溫度不可超過約2⑽至 =絲溫度在約21 00至約2 9 5 0。〇範圍内。該陰極燈: 自約70至約130安培，通過該燈絲之電壓自約2〇至之 30伏。接地電壓自約70至約13〇伏，該電聚電流自約〇 5·勺 約20.0安培。該基材座之電壓自約〇.工至約5· 〇仟伏，所^ 含碳與含Si物質之動能分別在自約100至約12〇〇電子伏有 範圍内與自約25至約3 0 0電子伏特範圍内。該金屬束係: 游離原子或單原子離子組成。該金屬原子/離子之動能 超過約25電子伏特。先質流速自約〇· 5至約5· 〇立方厘&米〆 小時，該塗料之生長速度自約〇.丨至約2·〇微米/小時。/、 大部分操作之較佳操作範圍係··壓力約卜3χ1 〇_5托耳， 電聚電流約1安培，燈絲電流自約6 〇至約7 5安谇，灵材洛 壓自約6 0 0至約1 0 0 0伏DC ’或是RF模式之約1〇;瓦^向】Co-deposition of agent materials. The argon gas flowed privately to the magnetron, and after the base pressure was reached = the etiquette started sputtering to clean the substrate, using a shutter of 12 ^ s δ. Upon completion, the shutter 12 is opened and the required energy = = the effect is available at the beginning of the coating deposition, during the coating deposition, and the like. This may be performed intermittently during the coating deposition, depending on the structure and composition. II by the role of Dc or RF, '= = material junction (metal, ceramic, alloy, etc.) for co-deposition. In order to refer to various materials in Figure 3, the growth conditions of the coating are as follows. Deposition chamber Super willow tor, plasma generates active area ~ 2 pressure is within the range of " force: may be about 5. OxlO-2 Torr range. The substrate temperature must not exceed about 2 ° F to = filament temperature is from about 2100 to about 2950. 〇range. The cathode lamp: from about 70 to about 130 amps, and the voltage across the filament from about 20 to 30 volts. The ground voltage is from about 70 to about 130 volts, and the galvanic current is from about 0.05 to about 20.0 amps. The voltage of the substrate holder is from about 0.1 to about 5.0 volts, and the kinetic energy of the carbon-containing and Si-containing substances ranges from about 100 to about 12,000 electron volts and from about 25 to about Within 3 0 0 electron volts. The metal beam system: composed of free atoms or monoatomic ions. The kinetic energy of the metal atom / ion exceeds about 25 electron volts. The precursor flow rate is from about 0.5 to about 5.0 cubic centimeters per hour and the growth rate of the coating is from about 0.1 to about 2.0 microns / hour. / 、 The preferred operating range for most operations is: · pressure job 3χ1 0-5 Torr, electro-condensation current of about 1 amp, filament current from about 60 to about 7 5 amps, and spiritual material pressure from about 6 0 0 to about 1 0 0 0 volt DC 'or about 10 in the RF mode; Watt direction]

五、發明說明（21) 率°RF模式之較佳頻率自約90至約3〇〇仟赫。較佳磁控管 電源視該塗料所需之材料、組合物與結構種類而土定。工吕 另—個較佳具體實例中，較佳方法使用位於三2兩將其 中之電漿放電，如圖3所示，言亥電焚能量密度高於約】水& Kwh/克—碳原子。於真空室中以高壓電場吸取雨韧 亚將其置於該基材上。該基材座之電位自約〜/ 仟伏為佳，1· 0+/ —〇. 2仟伏最佳，“之頻率化π圍、约〇 〇至約25百萬赫，RF之頻率變化範圍自約=圍自約 電漿管中碳m之射出電子比㈣ 仔赫。 0. 5至約1. 5個電子。 粒子射出自約 可以下列方法任何—者或苴组人 蒸發作用；2)離子濺鍍作及^s摻雜劑束··；[)熱 含摻雜劑束導至生長塗料 、束。經由真空室將該 子間碰撞。將基材置於鄰^艟=排除沉積室本身之粒 上，其可確使其以兩個旋轉方=二材座（例如，一個桶） 或離子束射出之開口鱼^ :疋轉，該相鄰室係由原子 或者，電漿產生作用；包如圖3所示。 >几積方法期間通常對該基材土至:進行（圖5)。該 外部加熱基材。 C或射頻電位。不需要自 上述沉積含氟類鑽石塗料、 ▲ 鍍矽與氧氣作為s i與〇之先質 適^^化包括使用經濺 來源，使用SlH4與含氧氣體作 ：口悲s1〇2作為。與〇的 標的物、氫與氟碳氣體作為C^ '的來源，使用石墨 聚矽氧化合物作為F、C、H、、、；；來源，使用含金屬氟 、。與金屬來源，使用金屬 575681 五、發明說明（22) 有械化合物作為金屬來源、 H、S4〇之來源，使用機铲：氟聚矽氧化合物作為C、F、 、义鑽石炭愈氫或烴左 質，使用氟有機石夕作為氣先二了 $ 2 ，作為碳與氫之先 積作用亦可以RF電容偶人访^ 5 ，、 可组合。該塗覆沉 ^ ^ ^ 0敌電（CCD)進行。 該氟聚矽氧或其他先質可r 一*八 或金屬分配器或前述液體蒸氣注射***之，^微孔狀陶竟 可與其他氣體混合，諸如金 ¥入。該先質 或與活性氣體混合，包紅/ σ作為進料氣體， 以達到沉積壓力，該壓， ^ 乙块與丁烧， 用單-板構造或平行以常托貼耳範“。可以使 上。然後施加RF或PDC電壓 〇 土 '附於此等板之一 率在1〇〇仟赫至1〇〇百萬赫〜。/〜電容RF放電實例中，RF頻 型：天線置於該室内部以進行放電作用大 :錄鋼或其他習知本技藝材料製成。可於 復保護塗料（諸如瓷）以防止濺鍍。 天、.泉表面上主 就沉積作用或非導電性基材（諸如 插士4 ^ , , LT _ 丨*^叨5，可使用一 去’其中中性基團流自高電壓標的物反射出來，並射 j材上]0圖4所概示。該方法使用之沉積作用與圖3所 不者相似，不過使用反射電極產生中性束。此方法可以消 除充電及/或生長期間快速粒子在基材上銜擊所致之基材 表面彳員害。 較佳沉積超 專介電塗層之方法包括經由真空室進行離子 撞擊（例如，能量範圍自約3 〇至約1 5 0電子伏特之Ar+或κ+) 其中該真空室已經以蒸氣回填（大約3x1 〇-4托耳）。此方法V. Description of the invention (21) The preferred frequency of the RF mode is from about 90 to about 300 MHz. The preferred magnetron power source depends on the materials, composition and structure of the coating. In another preferred embodiment, the preferred method uses a plasma discharge located at 322, as shown in Figure 3, and the energy density of Yanhai is higher than approximately] water & Kwh / g—carbon atom. Urania was absorbed by a high-voltage electric field in a vacuum chamber and placed on the substrate. The potential of the substrate seat is preferably from about ~ / 仟 volts, and 1 · 0 + / -0.2 仟 volts is the best. The frequency of π ranges from about 0.00 to about 25 megahertz, and the frequency of RF changes. The range from about = the ratio of the emitted electrons around the carbon m in the plasma tube is more than 0.5 A. 0.5 to about 1.5 electrons. The particles can be emitted from about 1 or any of the following methods to evaporate; 2 ) Ion sputtering and ^ s dopant beams; [] The hot dopant-containing beams are led to the growth coatings and beams. The sub-collisions are collided via the vacuum chamber. The substrate is placed adjacent to ^ 艟 = exclusion deposition On the grain of the chamber itself, it can be sure that it has two rotating sides = two-piece base (for example, a barrel) or an opening fish emitted by an ion beam ^: 疋 turn, the adjacent chamber is generated by atoms or plasma The effect is shown in Figure 3. > The substrate is usually subjected to: (Figure 5). The externally heated substrate. C or radio frequency potential. No need to deposit fluorine-containing diamond coatings from the above. ▲ ▲ Silver plating and oxygen are used as the precursors of si and 〇 ^^ including the use of splash sources, using SlH4 and oxygen-containing gas as: sorrow s102 as the standard. Materials, hydrogen, and fluorocarbon gases are used as sources of C ^ ', and graphite polysilicon compounds are used as F, C, H ,,, ;; sources are metal-containing fluorine, and metal sources are used, 575681. V. Description of the invention (22) Organic compounds are used as the source of metal, H, S40. Use of mechanical shovel: fluoropolysiloxane as C, F, ,, diamond diamond carbon hydrogen or hydrocarbon left, use fluoroorganic stone as gas first Two $ 2, as the pre-product of carbon and hydrogen can also be accessed by RF capacitor puppet ^ 5, can be combined. The coating Shen ^ ^ ^ 0 enemy electricity (CCD). The fluoropolysiloxane or other first The microporous ceramic can be mixed with other gases, such as gold ¥. The precursor or mixed with active gas, including red / σ as input Feed gas to reach the deposition pressure, which is ^ B block and sintered, using a single-plate construction or parallel to the conventional support. Can make on. Then apply RF or PDC voltage 〇 土 attached to one of these boards at a rate of 100Hz to 100MHz ~. / ~ In the example of capacitor RF discharge, the RF frequency type: the antenna is placed inside the room to perform the discharge effect: made of steel or other materials known to the art. Protective coatings (such as porcelain) can be used to prevent sputtering. On the surface of the spring, the main deposition or non-conductive substrates (such as Jushi 4 ^,, LT _ 丨 * ^ 5 can be used to reflect the neutral group flow from the high-voltage target , And shot on the material] 0 as shown in Figure 4. The deposition used in this method is similar to that shown in Figure 3, but using a reflective electrode to generate a neutral beam. This method can eliminate rapid particles during charging and / or growth during growth. Damage to the surface of the substrate caused by impact on the substrate. A preferred method of depositing the ultra-special dielectric coating includes ion impact via a vacuum chamber (for example, an energy range from about 30 to about 150 electron volts). Ar + or κ +) where the vacuum chamber has been backfilled with vapor (approximately 3x1 0-4 Torr). This method

575681 五、發明說明（23) 使得塗料本身安— ~ 隧道距離控制最長 X被吸收基團電荷文 沉積本發明塗料之 崚％次 用。 另種适擇性方法係RF電衮 另一較佳具I#奋彳 ·电作 法，其另外包：：：中 發明有闕-種製造電 金屬塗料，^ 種類鑽石含碳、矽、氡器、方 亚如貫施例丨8所述在該 辽、氣、&方 另一較佳具I#者γ丨士 積塗料上萝；、氟輿 法ml…例中’本發明有關n二成圖型。 另-較佳具體實例心L積塗料上製圆 法，i另外命k &明有關一種萝袢卞圖梨c 石々卜 匕括沉積一種金屬下層電極、电容器之大 :今；、氧與氣塗料，i沉積-個經；a?積〜種含嚷 =屬：層電極可為諸如Tl、Ai、c二圖上層金屬電極。 5技藝中習知其他電極材料。上 =、Ta、Ti/pt/丁i ^、Ai、Cu、Pt、pd 材料可為Au、 藝習知之簡易屏蔽或平版印電極材料。本技 之製圖作用。 乂進行上層金屬電極 根據本發明方法可以沉積極均勻且盔 類鑽石塗層。言亥沉積塗層之厚度不無理論,超薄介電含氟 乂Γ!^、 可製得原子規模複合塗層，塗声产产通常 …:自米=約10微米範圍内。就電手術儀 曰；度在自約〇. 5微米至約5微米為宜，較 2微米至約3微米。就撓性基材而言，該'SJ冗二約 〇料0=5^米至10微来。適於保護銳利邊緣之含氧類鑽石塗 ::二冗積厚度視該基材性質而定。極小之銳利刀片僅需 要自約5宅微米至約150毫微来之塗詹。其他物件♦要夕保575681 V. Description of the invention (23) Make the coating itself safe— ~ The tunnel distance is controlled to be the longest. The charge of the absorbed group is used to deposit 崚% of the coating of the invention. Another alternative method is RF electric power. Another preferred method is I # Fen · electric method, which additionally includes ::: Invented 阙-a kind of electrical metal coatings, ^ types of diamonds containing carbon, silicon, iron Fang Ya, as described in Example 丨 8, on the other side of the Liaoning, Qi, & Fang who has better I #, Shiji paint; Fluorine method ml ... In the example, the present invention is related to the second image. type. Another-preferred specific example: the method of making a circle on the product of L-products, i. In addition, k & Ming is related to a kind of lacquer, pear, c, stone, dagger, etc., which deposits a metal lower electrode, a capacitor: now; oxygen and gas Coating, i deposition-a warp; a? Product ~ species containing 嚷 = genus: layer electrodes can be upper metal electrodes such as Tl, Ai, c two pictures. 5 know other electrode materials in the art. The material of upper =, Ta, Ti / pt / butyl, ^, Ai, Cu, Pt, pd can be Au, a simple shielding or lithographic electrode material known in the art. The drawing function of this technique.乂 Performing the upper metal electrode According to the method of the present invention, an extremely uniform and helmet-like diamond coating can be deposited. The thickness of the deposited coating is not without theory. Ultra-thin dielectric fluorine-containing 乂 Γ! ^ Can be used to produce atomic-scale composite coatings. The coating production is usually…: from meters = about 10 microns. As for the electrosurgical instrument, the degree is preferably from about 0.5 microns to about 5 microns, more than 2 microns to about 3 microns. As far as flexible substrates are concerned, the 'SJ' is about 0 to 5 μm to 10 μm. Oxygen-based diamond coatings suitable for protecting sharp edges :: Two redundant thicknesses depend on the nature of the substrate. Very small sharp blades need only be coated from about 5 nanometers to about 150 nanometers. Other items

第28頁 575681 五、發明說明（24) 護性含氟類鑽石塗料為數微 述塗料可以沉積於經選擇之 要沉積於中間層上，其厚度 約2 0毫微米至約1 2微米為佳 米（微米）厚。因此，本發明上 精確磨利基材，或是若j青況需 自約5毫微米至約1 2微米，自 ，該厚度僅視經塗覆精確磨利 基材所需應用而定。 下列實施例係用於進一步說明本發明，其不對本發明構 成限制。 實施例 實施例1 - 於剃刀刀片上沉積含氟類鑽石塗料 在一組2 0 0 0個剃刀刀片兩 剃刀刀片裝於一個鋼製固定 源（該刀片與該束保持平行） 侧塗覆含氟類鑽石塗料。將該 器L並該刀片邊緣朝向沉積來 。於1 · 8 X 1 0_4托耳壓力、 1 · 0 - 1 · 1安培電漿電流及6 3 0伏之DC基材偏壓下進行沉積作 用。該沉積作用進行44分鐘。於電漿管開動與關閉期間使 用快門遮蔽該基材。沉積速率為0 . 1 3微米/小時，該試驗 對朝向沉積束之平坦刀片表面上沉積厚度為9 2 0埃（0. 0 9 2 微米）塗層。刀片最末端之厚度大約3 0 0 - 5 0 0埃。 實施例2 - 於剃刀刀片上沉積含氟類鑽石塗料（沉積時間 十二分鐘） 在一組2 0 0 0個剃刀刀片兩侧塗覆含氟類鑽石塗料。將該 剃刀刀片裝於一個鋼製固定器，並該刀片邊緣朝向沉積來 源（該刀片與該束保持平行）。於1. 5 X 1 0—4托耳壓力、0 · 5 安培電漿電流及5 7 0伏之DC基材偏壓下進行沉積作用。該 沉積作用進行1 2分鐘，沉積速率為0. 5微米/小時。於平坦Page 28 575681 V. Description of the invention (24) Protective fluorine-containing diamond paint is a micro coating. The paint can be deposited on the intermediate layer selected to have a thickness of about 20 nm to about 12 microns. (Microns) thick. Therefore, in the present invention, if the substrate is precisely ground, or if the condition needs to be from about 5 nm to about 12 microns, the thickness depends only on the application required to coat the precisely ground substrate. The following examples are provided to further illustrate the present invention and are not intended to limit the present invention. EXAMPLES Example 1-Deposition of a fluorine-containing diamond coating on a razor blade. A set of 2000 razor blades. Two razor blades are mounted on a steel fixed source (the blades are kept parallel to the beam). The side is coated with fluorine. Diamond-like coating. Place the device L and the blade edge toward the deposit. Deposition was performed at a pressure of 1 · 8 X 1 0_4 Torr, a current of 1 · 0-1 · 1 Amp, and a DC substrate bias of 63 volts. This deposition was performed for 44 minutes. A shutter is used to shield the substrate during the start and close of the plasma tube. With a deposition rate of 0.13 micrometers / hour, this test deposits a thickness of 920 angstroms (0.092 micrometers) on the surface of a flat blade facing the deposition beam. The thickness of the extreme end of the blade is about 300-500 angstroms. Example 2-Deposition of fluorine-containing diamond paint on razor blades (deposition time of twelve minutes) A group of 2000 razor blades were coated with fluorine-containing diamond paint on both sides. Install the razor blade in a steel holder with the blade edge facing the source of the deposition (the blade is parallel to the beam). Deposition was performed at 1.5 X 1 0-4 Torr pressure, 0.5 Amp plasma current, and a DC substrate bias of 570 volts. The deposition was performed for 12 minutes, and the deposition rate was 0.5 micron / hour. Yu Ping

第29頁 五、發明說明（25) 表面上形成1 0 6 0埃厚之塗層。Page 29 V. Description of the invention (25) A coating with a thickness of 1060 angstroms is formed on the surface.

Gpa，其係以毫微刻紋 劑之含氟類鑽石塗 至5 5 0埃該塗層所顯示 9 片尖端之塗層厚度約350 測量。 文度為6 · 魁 在"他刀片上塗覆含氟類 另外摻％谷 DO /A r- ' '^料，盆於下列室條件下 ▲雜鈦。RF偏壓頻率為2〇〇 ”不卜夕J至惊仟卜 剐向功率為赫，基材偏壓為350伏， 手為b5至瓦，鈦摻雜I白]n 上形成750埃厚之塗声。古0至20〇/°。於平坦表面 GPa。 子心土廣以笔说刻紋測量之塗層硬度為4. 5 羊毛刮理詁，醅 复於^ ί貫施例1 一3程序塗覆之刀片進行試驗，將該刀片 _徼供士，並刮理該毛氈30次（刮除長度6吋）。在光縱 王里於Γ下觀祭刮理丽後之刀片邊緣。結果顯示該塗料於刮 命j k對於刀片邊緣之粘合性良好。 ΠΙ 薄膜上沉積含氟類鑽石塗料 氣^環己院中超音波清潔2x2見方之Kapton 薄膜，以氮 二 無並t褒於24忖之基材座上。於丙酮、氣化曱稀、曱 职☆ β凉$夕、玻璃、碟鋼、不銹鋼與裸露氧化鋁基材之對 最，’以氮氣吹乾並且亦將其裝於基材座上。該室抽空至 乾终壓力8χ1〇_5托耳。將氬氣導入該室，使其壓力升至1〇-2 今耳。以母分鐘7轉旋轉該基材。使用R F基材偏壓，並將 特1爲壓驟升至3 5 0伏。在上述條件下，以氬離子钱刻該基 5分鐘。清潔15分鐘之後，將壓力降至至3. 8x10-4托Gpa, which is coated with a nano-grain-containing fluorine-containing diamond to 550 angstroms. The coating has a thickness of about 350 measured on the 9 tips. The degree of text is 6. Kui coated with "fluoride" on his blades, and mixed with %% DO / A r-'^ materials, pots under the following chamber conditions ▲ mixed titanium. The RF bias frequency is 200 ”, and the power in the direction is from 1500 to 500 ohms. The substrate bias voltage is 350 volts, the hand is b5 to watts, and the titanium is doped with titanium. Coating sound. Ancient 0 to 20 ° / °. On a flat surface GPa. The hardness of the coating measured by Zi Xintuo by pen engraving is 4.5. The wool is scraped, and it is restored in ^ 贯 例 1 一 3 The coated blade was tested by the procedure. The blade was applied to the blade, and the felt was scraped 30 times (scraping length 6 inches). The edge of the blade after scraping was viewed at Γ under the vertical king. It shows that the coating has good adhesion to the edge of the blade. ΠΙ Fluorine-containing diamond coating gas is deposited on the film ^ Kapton film of 2x2 square ultrasonic cleaning in Houjiyuan, with nitrogen and no t 24 to 24 Substrate holder. For acetone, gasification, thinning, ☆ β cooler, glass, plate steel, stainless steel and bare alumina substrate, the best, 'dry with nitrogen and install it on the substrate Seat. The chamber is evacuated to a final dry pressure of 8x10-5 Torr. Argon gas is introduced into the chamber to increase the pressure to 10-2 present ears. The substrate is rotated at 7 revolutions per minute. 8x10- Using an RF substrate bias, and the pressure was raised to 3 50 volts. Under the above conditions, the base was engraved with argon ion money for 5 minutes. After 15 minutes of cleaning, the pressure was reduced to 3. 8x10- 4 tray

575681 五、發明說明（26) =°對三極電漿管急速施加電 將聚〜3, 3, 3 —三默而其审装功一產生丨· 〇A之電漿電流。 聚人拍7古 - 土 土、夕氣烧~(5〇%)二甲美石夕 二口物直接導人該電漿。在甲基夕减共 枯合性塗芦。以』上形成〇.5微米厚之高度 枓所顯示之表面能量為2〇. 4達 f δ氟頒鑽石塗 測量該塗料之介電性質。該含氣類厘鑽未二㈣ 於1，厘米。該含敦類鑽石条：:員鑽石塗枓之介電強度大 實施例6 -於令凰/μπι'+ 土抖之水接觸角度為91。。 -——化Ultem 薄腹卜…拉人一 卜认 屬 薄膜安 上。於丙酮、氯化曱稀、甲@ t ^ 于之基材座 銹鋼與裸露氧化鋁基材之對照組，=^々破璃、碳鋼、不 裝於基材座上。以快門屏蔽該基材。二，：：5亚且亦將其 8x101托耳。對三極電衆管速施加電壓'產1至最終壓力 電流。將聚-3, 3, 3-三氟丙基甲美 丨· 0A之電漿 氧烧共聚合物直接導入該電霞 '二烧八—=)二甲基石夕 後，將屋力升至2χ1〇-4托耳。以每進;女定作用之 除該基材快門。使用RF偏壓，刀1 =轉έ亥基材。移 伏。在上述條件下進行含氟類=升至， 於基材薄膜上形成0. 3微米厚之古戶占、八貝用1 5 ’刀釦。 角度測量方法測量，該含氟畔之^度枯合性塗層。以接觸 Λ 22 S η / Γ- i / '輪石塗料所顯不之表面能量 ΐ。.节ί Λ :對/石夕基材測量該塗料之介電性 ΐ鑽：：亂通鑽石主料之介電強度大於2MV/厘米。該含氟 六員鑽石塗料之水接觸角度為8 1 5。。575681 V. Description of the invention (26) = ° Rapid application of electricity to the three-pole plasma tube will converge ~ 3, 3, 3-three silent and its trial and installation work will generate a plasma current of 丨 · 〇A. Jurenpai 7 Ancients-Earth, Earth, and Qiqi Burning ~ (50%) Dijia Meishixi Two objects directly lead to the plasma. Co-resistance coated reed on methyl eve. With a height of 0.5 micrometers formed on the surface, the surface energy shown was 2.4 to f δ Fluorine Diamond Coating. The dielectric properties of the coating were measured. The gas-bearing centrifugal drill is less than 1 cm. The diamond-containing diamond bar: The dielectric strength of the coated diamond is large. Example 6-The water contact angle of Yu Linghuang / μπι '+ soil shaking is 91. . -—— Ultem Thin belly ... Pull people a. I think it belongs to the film. In the substrate base of acetone, osmium chloride, and a @ t ^ The control group of rust steel and bare alumina substrate = ^ 々 broken glass, carbon steel, not mounted on the substrate base. The substrate is shielded with a shutter. Second: :: 5 and also 8x101 Torr. A voltage is applied to the triode electric tube to generate 1 to the final pressure current. After introducing the plasma oxygen-fired copolymer of poly-3, 3, 3-trifluoropropyl methylamine 丨 · 0A directly into the Denxia 'Dishao Ba — =) dimethyl stone, the roof force was raised to 2χ1〇-4 Torr. Take every advance; the role of the female is divided by the substrate shutter. Using RF bias, knife 1 = turn the substrate. Ambient. Under the above-mentioned conditions, the fluorine-containing type was raised to, and a 0.3 μm-thick Furuto-chan, Babe with a 15 'knife buckle was formed on the substrate film. The angle measurement method measures the degree of desiccant coating on the fluorine-containing side. With contact Λ 22 S η / Γ- i / 'Surface energy 轮 which is not shown by the wheel stone coating. Section Λ: Measure the dielectric properties of the coating on / Shi Xi substrate. Countersink :: The dielectric strength of the chaotic diamond main material is greater than 2MV / cm. The water contact angle of the fluorine-containing six-member diamond coating was 8 1 5. .

575681 五、發明說明（27) _ " '一' - 金屬化m 石塗料 將2x2見方之金屬化Kapton薄膜安裝於24吋之基材座 上。於丙酮、氯化甲烯、甲烷中清潔矽、玻璃、碳土丄 裸露氧化銘基材之對照組，並以氮氣吹乾。該 ”：將安裝於基材座…快門屏蔽該基材。該室：空、 家、、、壓力8x10。托耳。對三極電漿管速施 UA。之電浆電流。將聚_3,3,3—三氣丙基甲基；；貌產生 -(50%)二曱基矽氧烷共聚合物直接導入該電漿。 鐘安定作用之後，將麼力升至2χ1〇—4托耳。以每分鐘丁 基材快門。*謂偏壓，並將基材偏虔 用6分鐘。該室通風；類鑽石塗料沉積作 # ^ 至逋風至大虱壓力。倒裝該金屬化Kapt〇n 土 如此可以塗覆未經塗覆一侧。以相同方式塗覆苐〜 =^金屬化Kapton基材薄膜兩侧形成〇. 1 5微米厚 。=塗：；以接觸角度測量方法測量，該含氣類匕 二：曰:：；表：能量為2〇. 9達因/厘米。使用對照矽基 大於1MV/厘米。該含^ =旗έ貺類鑽石塗料之介電強度 實施例8 -於全屬各!鑽石塗料之水接觸角度為93。。 將直徑四对之今属儿^ — 氣化曱稀、曱院ί;::”：24对基材座上。於丙詞、 化銘基材之對日“且 夕、玻璃、碳鋼、不鎮鋼與裸露氣 於基材座上，二：：氮氣吹乾。該對照樣本亦將安襄 8渺托耳。對三極/Λ該基材。該室抽空至最終壓力 包水官速施加電壓，產生丨.〇 Α之電榮575681 V. Description of the invention (27) _ " 'A'-Metallized m stone coatings 2x2 square metallized Kapton film is mounted on a 24-inch substrate holder. Clean the control group of silicon, glass, and carbonaceous earth in acetone, methyl chloride, and methane. The exposed control group was exposed to nitrogen and blown dry. This ": will be installed on the substrate holder ... The shutter shields the substrate. The chamber: empty, home ,, pressure 8x10. Torr. Quickly apply UA to the three-pole plasma tube. , 3,3-trifluoropropylmethyl ;; appearance produced-(50%) difluorenyl siloxane copolymer was directly introduced into the plasma. After Zhong Anding action, the force was raised to 2 × 10-4 Torr Ears. Ding the substrate shutter per minute. * It is biased, and the substrate is biased for 6 minutes. The room is ventilated; diamond-like paint is deposited as # ^ to the wind to the big lice pressure. Flip the metalized Kapt〇n The soil can be coated on the uncoated side in the same way. 苐 ~ = ^ metallized Kapton substrate film is formed on both sides of 0.1 5 microns thick. = Coating: measured by contact angle measurement method, the containing Gas type dagger II: Said ::; Table: Energy is 20.9 dyne / cm. Use a control silicon based greater than 1MV / cm. The dielectric strength of the coating containing ^ = flag-shaped diamond coatings Example 8- All belong to each! The diamond coating has a water contact angle of 93. The diameter of four pairs of this is a child ^ — gasification, thin, 曱; ί :: ": 24 pairs of substrate holders. Yu Cing, Hua Ming Substrate's Opposition to Japan, "Qi Xi, glass, carbon steel, non-steel steel and bare gas on the substrate seat, two :: nitrogen blow dry. This control sample will also be Anxiang 8 Mitol For the three poles / Λ the substrate. The chamber is evacuated to the final pressure of water pressure to apply a voltage to produce 丨 .〇Α's electric glory

第32頁 575681Page 575681

Γ二。將聚一3, 3, 3—三氟丙基甲基矽氧烷-（50%)二甲臬矽 :烷共聚合物直接導入該電漿。進行15分鐘安定作：之 力升至2X10 4托耳。以每分鐘7轉旋轉該基材。移 除違基材快門。使用RF偏壓，並將基材偏壓驟升至1〇8 伏。在；^述條件下進行含氟類鑽石塗料沉積作用1 8分鐘。 於基材薄膜上形成〇 · 2 1微米厚之高度粘合性塗層。以接觸 角度測量方法測量，該含氟類鑽石塗料所顯示之表面能量 為2 2達因/厘米。該金屬化矽上之含氟類鑽石塗料的介電 強度大於3. 8MV/厘米。 ％ -比較}碳二_...矽二氫與氧之塗料外包含I之 塗料 〜 此實施例有關比較含碳、矽、氫與氧之塗料及另外包含 氟之塗料。 可以使用具有兩個試驗狀態（系統1與2 )之圓盤上之針式 (POD)摩擦計（Spire公司）測定經塗覆與未經塗覆材料之數 種摩擦性質。此等性質包括··摩擦係數（C0F )、耐久性與 财磨係數。 進行例行評估之前，先進行一系列重複性試驗。試驗條 件列於下表1。此系列5式驗係於周圍環境條件下進行。塗 覆之前’將三片p 一 S i晶圓切成十（1 0 )個1" X 1π樣本。在單 一回合（# 6 5 7 )期間對所有樣本塗覆如美國專利第 5, 3 5 2, 4 9 3號所述之不含氟類鑽石塗料。使用一種聚苯基 甲基石夕氧统先質（Ge lest公司）沉積不含氟類鑽石塗料。該 樣i之為1.619微米。塗覆之後，將該樣本置於—個Γ 二。 Two. The poly-3,3,3-trifluoropropylmethylsiloxane- (50%) dimethylsilicone: ane copolymer was directly introduced into the plasma. Perform stabilization for 15 minutes: the force rises to 2X10 4 Torr. The substrate was rotated at 7 revolutions per minute. Remove the offending substrate shutter. RF bias was used and the substrate bias was ramped up to 108 volts. Under the conditions described above, the fluorine-containing diamond coating was deposited for 18 minutes. A highly adhesive coating with a thickness of 0.21 micron was formed on the substrate film. Measured by the contact angle measurement method, the surface energy shown by the fluorine-containing diamond coating was 22 dyne / cm. The dielectric strength of the fluorine-containing diamond coating on the metallized silicon is greater than 3.8MV / cm. % -Comparison} Carbon di _... Paint containing silicon dihydrogen and oxygen. Coatings containing I ~ This example is a comparison of coatings containing carbon, silicon, hydrogen and oxygen, and coatings containing fluorine. Several types of frictional properties of coated and uncoated materials can be measured using a needle-on-disk (POD) tribometer (Spire) on a disc with two test states (Systems 1 and 2). These properties include the coefficient of friction (C0F), durability, and coefficient of friction. Prior to the routine assessment, a series of repetitive tests is performed. The test conditions are listed in Table 1 below. This series of type 5 tests is performed under ambient conditions. Before coating ', three p-Si wafers were cut into ten (1 0) 1 " X 1π samples. All samples were coated during a single round (# 6 5 7) with a fluorine-free diamond coating as described in US Patent No. 5, 3, 5, 2, 93. A polyphenylmethanite precursor (Ge lest) was used to deposit a fluorine-free diamond coating. The i was 1.619 microns. After coating, place the sample in a

575681 五、發明說明（29) _ — ________ =潔容器，並置於周圍環境條件下8小時。以膠册 驗測量粘合性，並在2個樣本上進行。所有H拉扯試 性均極良好。 、灯所頁男、例中之粘合 表1 ·塗覆條件575681 V. Description of the invention (29) _ — ________ = Clean the container and place it in the surrounding environment for 8 hours. Adhesion was measured by a glue book test and performed on 2 samples. All H pull tests were very good. Table 1-Coating conditions

^^J8J H，於一個POD摩擦計中負載5N、每分鐘22 5轉 ，〇轉進行摩擦試驗。該球/針為1 /4"碳化擊/，/ :滑作用。該SPlre摩擦試驗器有兩個完全獨】之而:無 I除了ff與fh之外，所有樣本均於系心中進行1手 顯不於下表2。系統1之平均摩檫係數（c〇F )為〇 · 1 7，:果 平均C0F為〇· 08。一般認為該差異為校準誤差。’丁'統2^^ J8J H. A POD friction meter was loaded with 5N at 22 5 revolutions per minute and 0 revolutions for the friction test. The ball / needle is 1/4 " carbonized strike /, /: slip effect. The SPlre friction tester has two completely independent]: In addition to all the samples except ff and fh, all samples were performed in the heart with 1 hand, which is not shown in Table 2 below. The average friction coefficient (coF) of System 1 was 0.17, and the average COF was 0.08. This difference is generally considered to be a calibration error.丁丁 统 2

575681 五、發明說明（30) 表2 .重複性試驗結果 — 磨損痕跡爾mm2) SAMPLE# COF A B C D 標準差 變異係數 磨損速率 (mmTNm) & 0.17 3.80E-06 3.04Er06 1.28&06 574E-06 1.85E-06 53% 6.94&08 fb 0.17 2.49E-06 4.33E-06 5.01E-06 4.12E-06 1.07E-06 27% 7.97&08 fc 0.17 1.67E-06 4.96E-06 1.86E-06 9.85E-06 177E-06 75% 4.74&08 fd 0.17 2.99E-06 4.82E-06 1.95&06 2.48E-06 1.24E-06 41% 6.12E-08 fe 0.16 3.77E-06 5.39E-06 6.76E-06 5.32E-06 1.22E-06 23% 1.06E-07 fg 0.18 3.14E-06 5.66E-06 4.11E-06 2.78E-06 1.29E-06 33% 7.85&08 ft 0.09* 6.19&06 3.83E-06 4.84E-06 4.16E-06 1.04E-O6 22% 9.52Er08 ff 0.08* 2.07&06 2.49Er06 1.93&06 3.05E-06 5.02&06 21% 4.77&08575681 V. Description of the invention (30) Table 2. Repeatability test results—wear marks mm2) SAMPLE # COF ABCD standard deviation coefficient of variation wear rate (mmTNm) & 0.17 3.80E-06 3.04Er06 1.28 & 06 574E-06 1.85E-06 53% 6.94 & 08 fb 0.17 2.49E-06 4.33E-06 5.01E-06 4.12E-06 1.07E-06 27% 7.97 & 08 fc 0.17 1.67E-06 4.96E-06 1.86E -06 9.85E-06 177E-06 75% 4.74 & 08 fd 0.17 2.99E-06 4.82E-06 1.95 & 06 2.48E-06 1.24E-06 41% 6.12E-08 fe 0.16 3.77E-06 5.39 E-06 6.76E-06 5.32E-06 1.22E-06 23% 1.06E-07 fg 0.18 3.14E-06 5.66E-06 4.11E-06 2.78E-06 1.29E-06 33% 7.85 & 08 ft 0.09 * 6.19 & 06 3.83E-06 4.84E-06 4.16E-06 1.04E-O6 22% 9.52Er08 ff 0.08 * 2.07 & 06 2.49Er06 1.93 & 06 3.05E-06 5.02 & 06 21% 4.77 & 08

*於系統2之評估樣本 沉積含氟類鑽石塗料* Evaluation sample in System 2 Deposition of fluorine-containing diamond paint

其次，於將含氧類鑽石塗料沉積於基材上。使用熱燈絲 促進電漿化學蒸氣沉積法（PACVD)沉積該含氟類鑽石塗 料。已發現市售含氟有機矽為底質先質（尤其是聚-3, 3, 3-三氟丙基曱基矽氧烷-(50%)二曱基矽氧烷共聚合物 (G e 1 e s t公司，T u 1 1 y t 〇 w η， P A )可以製得高度钻合性薄 膜’其表面能量極低（〜2 0達因/厘米）而且具有抗結冰性 質。完成數回合沉積作用。在諸如矽、碳鋼、不銹鋼、Second, the oxygen-containing diamond coating is deposited on a substrate. Hot filament promoted plasma chemical vapor deposition (PACVD) deposition of the fluorine-containing diamond coating. Commercially available fluorinated organosilicons have been found as substrate precursors (especially poly-3, 3, 3-trifluoropropylfluorenylsiloxane- (50%) difluorenylsiloxane copolymer (G e 1 est company, Tu 1 1 yt 〇w η, PA) can produce highly drill-through films with extremely low surface energy (~ 20 dyne / cm) and anti-icing properties. Complete several rounds of deposition .In products such as silicon, carbon steel, stainless steel,

第35頁 575681 五、發明說明（31) |g "Teflon 氟碳聚合物及鈦基材上進行塗覆作用。下表 3列出該樣本塗覆時作用使用之參數與條件。 表3 .含氟類鑽石塗料塗覆條件Page 35 575681 V. Description of the invention (31) | g " Teflon fluorocarbon polymer and titanium substrate for coating. The following table 3 lists the parameters and conditions used in the application of this sample. Table 3. Coating conditions for fluorine-containing diamond coatings

作業# 壓力 χΐσ4 先質 偏壓 負載/DC 電源 燈絲 偏壓 電漿 電流 沈積 時間 (分鐘） 先質流速 (1UPM= 0.12cotein) 托耳 伏 瓦 伏 安培 UPM 695 2.26 FMS-123 500.0 131.0 150 0.49 180 0.90 696 2.24 FMS-123 600.0 181.0 1-50 0.53 180 LOO 697 2.01 FMS-123 700.0 236.0 150 0.51 180 098 698 2.14 FMS-221 500.0 135.0 150 0.49 120 1.22 699 2.11 FMS-221 600.0 183.0 150 0.49 120 0.97 700 2.03 FMS - 221 700.0 239.0 150 0.52 120 0.97 701 2.01 FMS-123 600.0 185.0 150 0.49 180 1.01 FMS-123 ··液態聚-3,3,3-三氟丙基-曱基矽氧烷 FSM-221 :液態聚-3,3,3-三氟丙基-曱基矽氧烷-(50%) 二曱基矽氧烷共聚合物Job # Pressure χΐσ4 Precursor bias load / DC power filament bias plasma current deposition time (minutes) Precursor flow rate (1UPM = 0.12cotein) Torv volt ampere UPM 695 2.26 FMS-123 500.0 131.0 150 0.49 180 0.90 696 2.24 FMS-123 600.0 181.0 1-50 0.53 180 LOO 697 2.01 FMS-123 700.0 236.0 150 0.51 180 098 698 2.14 FMS-221 500.0 135.0 150 0.49 120 1.22 699 2.11 FMS-221 600.0 183.0 150 0.49 120 0.97 700 2.03 FMS -221 700.0 239.0 150 0.52 120 0.97 701 2.01 FMS-123 600.0 185.0 150 0.49 180 1.01 FMS-123 ·· Liquid poly-3,3,3-trifluoropropyl-fluorenylsiloxane FSM-221: Liquid poly- 3,3,3-trifluoropropyl-fluorenylsiloxane- (50%) difluorenylsiloxane copolymer

第36頁 575681 五、發明說明（32) 表4.塗料性質 作業# 矽厚度微米 玻璃厚度微米 矽沈積速率 微米/小時 玻璃沈積速率 微米/小時 695 0.806 0.844 0.269 0.281 696 0.860 0.908 0.287 0.303 697 0.934 0.983 0.311 0.328 698 0.651 0.678 0.326 0.339 699 0.682 0.542 0.341 0.271 700 0.673 0.708 0.337 0.354 701 0.846 0.935 0.282 0.312 抗結冰貫驗 在含氟類鑽石塗料與不含類鑽石塗料（DLN)上進行定量 結冰試驗。 將一滴自來水置於DLN與塗覆含氟類鑽石塗料Si晶圓 上。將該樣本置於冷凍自（2 8 °F) 1小時使該水液滴結凍。 移開該樣本並移除該液滴。記錄移除該樣本所需之努力。 該冷凍液滴很容易自含氟類鑽石塗料表面滑落。相對地， 該冷凍液滴與DLN粘合得非常好，最後熔融。此外，將塗 覆含氟類鑽石塗層樣本浸於水中，可以清楚地顯示水極容 易滑過該含氟類鑽石塗層，自水中取出該塗層時，殘留的Page 36 575681 V. Description of the invention (32) Table 4. Coating properties operation # Silicon thickness micro glass thickness micro silicon deposition rate micro / hour glass deposition rate micro / hour 695 0.806 0.844 0.269 0.281 696 0.860 0.908 0.287 0.303 697 0.934 0.983 0.311 0.328 698 0.651 0.678 0.326 0.339 699 0.682 0.542 0.341 0.271 700 0.673 0.708 0.337 0.354 701 0.846 0.935 0.282 0.312 Anti-icing pass The quantitative icing test is performed on fluorine-containing diamond coatings and diamond-free coatings (DLN). A drop of tap water was placed on the DLN and Si-coated wafer with fluorine-containing diamond coating. The sample was frozen at (28 ° F) for 1 hour to freeze the water droplets. Remove the sample and remove the droplet. Document the effort required to remove the sample. The frozen droplets easily slip off the surface of the fluorine-containing diamond coating. In contrast, the frozen droplets adhered very well to DLN and eventually melted. In addition, immersing a sample containing a fluorine-containing diamond coating in water can clearly show that water easily slips through the fluorine-containing diamond coating. When the coating is removed from water, the residual

第37頁 575681 五、發明說明（33) 水均形成珠狀（接觸角度大）。 ' 實施例1 0 - 含氟類鑽石塗料之特徵 下表5表示氟化薄膜之評估結果。用以測量塗料之條件 如上述實施例9所述。 表5 .含氟類鑽石塗料之薄膜性質 樣本 厚度 最大硬度 彈性模數 應力 (微米） (GPa) (GPa) (MPa) 695d 0.806 10.5 86.3 -233 696e 0.860 11.0 " 90.8 -262 697e 0.692 10.2 79.7 *** 698d 0.651 12.3 90.0 -228 699f 0.682 12.1 88.0 -459 770d 0.673 11.4 99.0 -174 701d 0.846 11.0 90.8 -256Page 37 575681 V. Description of the invention (33) Water forms beads (large contact angle). '' Example 10-Characteristics of fluorinated diamond coatings Table 5 below shows the evaluation results of fluorinated films. The conditions for measuring the paint are as described in Example 9 above. Table 5. Film properties of fluorine-containing diamond coatings. Sample thickness Maximum hardness Modulus stress (μm) (GPa) (GPa) (MPa) 695d 0.806 10.5 86.3 -233 696e 0.860 11.0 " 90.8 -262 697e 0.692 10.2 79.7 * ** 698d 0.651 12.3 90.0 -228 699f 0.682 12.1 88.0 -459 770d 0.673 11.4 99.0 -174 701d 0.846 11.0 90.8 -256

第38頁 575681 五、發明說明（34) 基材材料（即矽、丁e f 1〇η ϋ石山取人 錄鋼、碳鋼及銘）枯合得極佳反ς δμ物、聚乙稀、鈦、不 有低，力與高彈性模數組合。此性能之故’該塗料具 導性能的重要指標。，多塗料容易因應力 ?(張力或壓縮應力)大致使其無法： _ ，°Λ 3鼠類鑽石塗料極為平滑，而且可以複窜美 面形態在摩擦係數、物及破裂機制ϊ t >貞極為重大角色，因此需要原本平滑薄膜。 ~羞-覆含氧類材之圓盤上之針 以圓盤上之針式（POD)試驗測定經塗覆基材之摩擦性 質。POD極適於試驗未塗覆部分與塗覆其他塗料之定標性 能。該試驗在負載5N、每分鐘225轉、無潤滑而且於周圍 環境（相對濕度3 0-5 0%)下進行。該球是1/4"碳化鎢。表6 總結矽上塗料之摩擦係數（平均值）與耐磨係數。 因為矽（1 00 )原子平滑、極硬1 3· 3 GPa)而且經常被 使用’所以選用矽（1 0 0 )進行試驗。與鋁（H = 〇 · 1至1 Gpa)或 軟鋼（H = 3至4 GPa)相較，矽顯得相當硬。矽表面變形並非 此等試驗中Hertz i an壓力所致。嘗試施加1〇N負載，但是 除了 一個實例之外，其餘實例中塗料均在低於3，〇 〇 〇轉之 後破裂。因為该塗料厚度小於1微米，施加1 〇 N壓力過大。 施加5 N負載時，除了兩個塗料實例之外，其餘均未破裂。 貫例之一當中’例如2 s 1 0 6 9 9 e ’塗料之殘留應力比最低應 力塗料高2倍（2X)。Page 38 575681 V. Description of the invention (34) The base material (ie, silicon, but ef 1〇η, Shih Tse Shan taken from the recorded steel, carbon steel and inscriptions) is very good combination of δμ, polyethylene, titanium No combination of low, force and high elastic modulus. The reason for this performance 'is an important indicator of the conductive performance of the coating. Many coatings are easy to be stressed due to stress (tensile or compressive stress), which generally makes them unable to: _, ° Λ 3 rat diamond coatings are extremely smooth, and can reshape the beauty surface in terms of friction coefficient, material and fracture mechanism ϊ t > Extremely important role, so an otherwise smooth film is required. ~ Shame-Needle on Disc Covered with Oxygen-Based Materials The needle-on-disk (POD) test was used to determine the friction properties of the coated substrate. POD is very suitable for testing the calibration performance of uncoated parts and other coatings. The test was performed under a load of 5N, 225 revolutions per minute, without lubrication, and in the surrounding environment (relative humidity 30-50%). The ball is 1/4 " tungsten carbide. Table 6 summarizes the friction coefficient (average value) and wear resistance coefficient of coatings on silicon. Because silicon (100) atoms are smooth, extremely hard (1.3 GPa), and are often used ', silicon (100) is selected for testing. Compared to aluminum (H = 0 · 1 to 1 Gpa) or mild steel (H = 3 to 4 GPa), silicon appears to be quite hard. The silicon surface deformation was not caused by Hertz i an pressure in these tests. An attempt was made to apply a load of 10 N, but with the exception of one example, the coating cracked after less than 3,000 revolutions. Because the coating thickness is less than 1 micron, applying a pressure of 100 N is excessive. When a 5 N load was applied, it was not cracked except for the two coating examples. In one of the examples, the residual stress of the coating such as 2 s 1 0 6 9 9 e is 2 times higher than that of the lowest-stress coating (2X).

第39頁 575681 五、發明說明（35) 表6 .含氟類鑽石塗料之摩擦係數與财磨係數 樣本 轉數 摩擦係數(COF) 对磨係數 695d 10,000 0.157 4.48xl0'8 696e 10,000 0.161 3.09x1 Ο·8 697e 5,113 +++ +++ 698d 10,000 0.124 1.83χ10'7 699f 221 +++ +++ 700d 10,000 0.162 4.56χ10'8 701d 15,000 0.163 8.80χ10"δPage 39 575681 V. Description of invention (35) Table 6. Friction coefficient and financial coefficient of fluorine-containing diamond coatings Sample rotation coefficient of friction coefficient (COF) Anti-friction coefficient 695d 10,000 0.157 4.48xl0'8 696e 10,000 0.161 3.09x1 Ο 8 697e 5,113 +++ +++ 698d 10,000 0.124 1.83χ10'7 699f 221 +++ +++ 700d 10,000 0.162 4.56χ10'8 701d 15,000 0.163 8.80χ10 " δ

+ + +試驗期間薄膜破裂 最低耐磨係數為3 . 0 9 X1 0—8 m m3 / N m，比D L N的耐磨係數 (平均5 X 1 0-8 mm3 /Nm)良好。耐磨係數與硬度之關係及硬度 與含氟類鑽石塗料之偏壓關係顯示於圖6與7。+ + + The minimum abrasion resistance of the film during the test is 3.09 X1 0-8 m m3 / N m, which is better than D L N (average 5 X 1 0-8 mm3 / Nm). The relationship between wear coefficient and hardness and the bias relationship between hardness and fluorine-containing diamond coatings are shown in Figures 6 and 7.

實施例1 2 ~~測量含氣類鑽石塗料之元素原子濃度 如上述實施例9製造一個含氟類鑽石塗料樣本。欲測定 之樣本具有如下表7所示之下列原子濃度，其以重量％計。Example 1 2 ~~ Measurement of elemental atomic concentration of gas-containing diamond coatings A sample of fluorine-containing diamond coatings was prepared as in Example 9 above. The sample to be measured has the following atomic concentrations shown in Table 7 below, which are in% by weight.

第40頁 575681 五、發明說明（36) 表7原子濃度（重量％ ) 深度(埃） Η C 〇 F Si At W 密度 <2650 19.5 38.4 14.0 14.0 14.0 0.05 0.02 9.33E22 2650-3000 19.5 38.4 14.0 14.0 14.0 0.05 0.04 9.33E22 3000-3400 19.5 38.4 14.0 14.0 14.0 0.05 0.01 9.33E22 3400-3850 19.5 38.4 14.0 14.0 14.0 0.05 0.02 9.33E22 >3850 — — — — 100 — — 5.00E22 實施例1 3 - 製造另外包含金屬摻雜劑之含氟類鑽石塗料 如上述實施例9製造含氟類鑽石塗料。然後該塗料摻雜 鈦與鋁，使電阻率自1 e + 1 6改變至1 e - 0 1歐姆-厘米。不必 測量精確的原子百分比。表8顯示數種含氟類鑽石塗料之 表面能量，其中伽瑪c是臨界表面能量，伽瑪d是表面能量 之分散分量，伽瑪p是表面能量之極性分量。該塗料之阻Page 40 575681 V. Description of the invention (36) Table 7 Atomic concentration (wt%) Depth (Angstrom) Η COF Si At W Density < 2650 19.5 38.4 14.0 14.0 14.0 0.05 0.02 9.33E22 2650-3000 19.5 38.4 14.0 14.0 14.0 0.05 0.04 9.33E22 3000-3400 19.5 38.4 14.0 14.0 14.0 0.05 0.01 9.33E22 3400-3850 19.5 38.4 14.0 14.0 14.0 0.05 0.02 9.33E22 > 3850 — — — — 100 — — 5.00E22 Example 1 3-Manufacture additional metals The fluorine-containing diamond coating material of the dopant is the same as that in Example 9 above to produce a fluorine-containing diamond coating material. The coating was then doped with titanium and aluminum, changing the resistivity from 1 e + 16 to 1 e-0 1 ohm-cm. It is not necessary to measure the exact atomic percentage. Table 8 shows the surface energy of several types of fluorine-containing diamond paints, where gamma c is the critical surface energy, gamma d is the dispersed component of the surface energy, and gamma p is the polar component of the surface energy. The resistance of the coating

第41頁 575681 五、發明說明（37) 表8 ·含氟類鑽石塗料之表面能量 樣本 塗料組合物 伽瑪c (達因/厘米） 伽瑪p (達因/厘米） 伽瑪d (達因/厘米） 30580 Ti:F-DLN 25.6 8.3 26.7 30581 Ti:F-DLN 23.9 8.3 27.3 30582 Ti:F-DLN 24.4 8.7 24.8 30583 Ti:F-DLN 23.2 7.6 27.4 30584 Ti:F-DLN 21.9 6.2 25.3 30585 Ti:F-DLN 24.2 6.0 27.5 30591 Ti:F-DLN 25.8 13.3 26.5 30618 Ti:F-DLN 22.1 - 6.9 25.2 30620 Ti:F-DLN 23.0 9 24.7 30625 Ti:F-DLN 23.2 10.2 25.0 30627 A1:F-DLN 19.7 4.4 24.7 30628 A1:F-DLN 24.6 3.2 25.7 30631 Tr.F-DLN 21.2 6.3 26 30638 Ti:F-DLN 22.3 30641 Ti:F-DLN 22.5 5.2 25.2 30645 Ti:F-DLN 20.9 6.3 30646 Ti:F-DLN 22.7 3.7 30658 Ti:F-DLN 27 19.2 25.7 30659 Ti:F-DLN 20.4 19.2 25.7Page 41 575681 5. Description of the invention (37) Table 8 · Surface energy sample coating composition of fluorine-containing diamond coatings Gamma c (dyne / cm) Gamma p (dyne / cm) Gamma d (dyne / Cm) 30580 Ti: F-DLN 25.6 8.3 26.7 30581 Ti: F-DLN 23.9 8.3 27.3 30582 Ti: F-DLN 24.4 8.7 24.8 30583 Ti: F-DLN 23.2 7.6 27.4 30584 Ti: F-DLN 21.9 6.2 25.3 30585 Ti : F-DLN 24.2 6.0 27.5 30591 Ti: F-DLN 25.8 13.3 26.5 30618 Ti: F-DLN 22.1-6.9 25.2 30620 Ti: F-DLN 23.0 9 24.7 30625 Ti: F-DLN 23.2 10.2 25.0 30627 A1: F-DLN 19.7 4.4 24.7 30628 A1: F-DLN 24.6 3.2 25.7 30631 Tr.F-DLN 21.2 6.3 26 30638 Ti: F-DLN 22.3 30641 Ti: F-DLN 22.5 5.2 25.2 30645 Ti: F-DLN 20.9 6.3 30646 Ti: F- DLN 22.7 3.7 30658 Ti: F-DLN 27 19.2 25.7 30659 Ti: F-DLN 20.4 19.2 25.7

第42頁 575681 五、發明說明（38)Page 42 575681 V. Description of the invention (38)

jr===- - 樣本 1 _ — 阻抗(歐姆） 30682 >lk 30618 4k 30620 17M 5裒境安定性 將沉積於石夕晶圓（ι"χ3")之Tl_DLN塗料（樣本編號： 1 =42與3si 0 64 1 )置於瘵氣壓熱元件中。該塗料曝於25〇 性。分鐘。未觀察到塗料剝落及而且塗料仍保有抗刮 多塗料之表面能^ 並=如上述實施例9製得之含氟類鑽石塗料表面能量， 並將其示於圖8。 异台只曰 ^疋l界表面此罝（lmN/m等於丨達因/厘 7^疋表面旎量之分散分量， 是表 量，而了。二h + 。狀刀里rP疋表面月匕里之極性分 電絕在緣體—金屬(MIM)多層結構進行電阻率與介 是-連續㉟，ΐ::Γ=ϊ基材上製造嶋。金屬底層 0.2至0.5微米間，而同笔極。底層電極的厚度介於 A1、Cr、Ta 41〇與：：控管藏鍍法沉積。因為諸如 定電阻接觸H所^ 該含氣類鑽石 '塗料形成安 所W使用此等金屬。在底層電極上=jr ===--Sample 1 _ — Impedance (ohms) 30682 > lk 30618 4k 30620 17M 5 The stability of the environment will be deposited on the Tl_DLN coating of Shixi wafer (ι " χ3 ") (sample number: 1 = 42 And 3si 0 64 1) placed in a krypton pressure heating element. The coating was exposed to 25 °. minute. No peeling of the coating is observed and the coating still retains the surface energy of the scratch-resistant coating. The surface energy of the fluorine-containing diamond coating prepared as in Example 9 above is shown in FIG. 8. The difference is that the surface of the surface of lm 疋 lm (lmN / m is equal to 丨 dyne / centimeter 7 疋 疋 旎 旎 The amount of surface 表 dispersion is a gauge, and the two. H +. The shape of the knife rP 疋 surface moon dagger The polarized electricity in the insulating layer is insulated in the edge-metal (MIM) multilayer structure for resistivity and interstitial ㉟, ㉟ :: Γ = ϊ made on the substrate. The metal substrate is between 0.2 and 0.5 microns, and the same pen The thickness of the bottom electrode is between A1, Cr, Ta 41〇 and :: Controlled deposit deposition method. Because, for example, the constant resistance contacts H, the gas-containing diamond 'coating is used to form an alloy, and these metals are used. On the electrode =

ifif

m ^貝 弟43頁 575681 五、發明說明（39) 無其他摻雜劑之介電含氟類鑽石塗層作為具有疏水性質之 介電塗層。該含氟類鑽石塗層厚度為0 . 0 9至0 . 5 2微米。在 該含氟類鑽石塗料製成銀點作為頂層電極。m ^ Page 43 575681 V. Description of the Invention (39) A dielectric fluorine-containing diamond coating without other dopants is used as a dielectric coating with hydrophobic properties. The fluorine-containing diamond coating has a thickness of 0.09 to 0.52 micrometers. Silver dots were made on this fluorine-containing diamond paint as the top electrode.

使用銀塗料附裝電極線，並使之乾燥1 0至3 0分鐘。以 6517 Keithly靜電計及Keithly 8002a型試驗固定器 (Keithly 儀器公司，克里夫蘭，OH)進行含氟類鑽石塗料 電容結構之電流-電壓（I -V )試驗。6 5 1 7型是具有多種測量 能力之6又1/2 -數位式靜電計/南電阻糸統，其可測量包括 外部溫度、外部相對濕度、電阻率、電壓與電流。該靜電 計具有毫微微安培敏感度與内建1 0 0 0伏源極。6 5 1 7型可以 自動安裝"偏壓測量π順序，其中施加試驗電壓一段預定時 間使電流達到平衡。於平衡狀態時，可以所需電壓進行該 測量作用。該試驗固定器是測量表面與體積電阻率用之保 護試驗固定器，其設計為可承受6 5 1 7型靜電計/高電阻系 統之測量能力。8 0 0 2 a型可以測量高達1 015歐姆之電阻。由 5伏正常電壓之電流-電壓測量該含氟類鑽石塗料電阻率。 將洩漏電流繪成遞增之施加電壓的函數以測定該含氟類鑽 石塗料之破裂特徵。就樣本而言，將重複進行電阻率測量 8次並且平均之。表1 0列出一些在此程式下沉積之含氧類 鑽石塗料電阻率及其對應厚度與電阻率變化％。Use silver paint to attach the electrode wire and allow it to dry for 10 to 30 minutes. A 6517 Keithly electrometer and a Keithly Model 8002a test fixture (Keithly Instruments Corporation, Cleveland, OH) were used for the current-voltage (I-V) test of the capacitor structure for fluorine-containing diamond coatings. Type 6 5 1 7 is a 6 1 / 2-digit electrometer / south resistance system with multiple measurement capabilities. It can measure external temperature, external relative humidity, resistivity, voltage and current. The electrometer has femto-amp sensitivity and a built-in 100 volt source. Type 6 5 1 7 can be automatically installed " bias measurement π sequence, where the test voltage is applied for a predetermined period of time to make the current reach equilibrium. In equilibrium, the measurement can be performed with the required voltage. This test fixture is a protection test fixture for measuring surface and volume resistivity. It is designed to withstand the measurement capabilities of Type 6 5 17 electrometer / high resistance system. 8 0 0 2 a can measure resistance up to 1 015 ohms. The resistivity of the fluorine-containing diamond coating was measured by a current-voltage of 5 volt normal voltage. The leakage current is plotted as a function of increasing applied voltage to determine the fracture characteristics of the fluorinated diamond coating. For the sample, the resistivity measurement will be repeated 8 times and averaged. Table 10 lists the resistivity of some oxygen-containing diamond coatings deposited under this program and their corresponding thickness and% change in resistivity.

第44頁 575681 五、發明說明（40) 表1 0 ·使用Μ I Μ結構之含氟類鑽石塗料電阻率 作業編號 薄膜厚度，微米 電阻率，歐姆-厘米 變化％ 645 0.14 1.25E+15 1.92 646 0.09 1.37E+15 0.82 653 0.45 8.06E+06 0.46 654 0.19 7.25E+11 2.89 655 0.16 2.58E+13 0.64 711 0.22 1.74E+15 0.98 717 0.26 2.28 马+14 1.73Page 44 575681 V. Description of the invention (40) Table 1 0 · Fluorine-containing diamond coatings using Μ I Μ structure resistivity job number film thickness, micron resistivity, change in ohm-cm% 645 0.14 1.25E + 15 1.92 646 0.09 1.37E + 15 0.82 653 0.45 8.06E + 06 0.46 654 0.19 7.25E + 11 2.89 655 0.16 2.58E + 13 0.64 711 0.22 1.74E + 15 0.98 717 0.26 2.28 Horse + 14 1.73

大部分塗料之電阻率高於1 01G歐姆-厘米。部分塗料之電 阻率在1015歐姆-厘采範圍内。所有高電阻率薄膜亦具有疏 水性，其水接觸角度介於85至94 °間。僅有一種塗料（作 業編號6 5 3 )之電阻率在1 06歐姆-厘米範圍内。此特殊塗料 係於正常條件以外之沉積條件沉積，試圖使其電阻率落在 1 01Q歐姆-厘米範圍内。 介電強度係由上述電流-電壓測量方法測量。該測量方 法在0. 7 9至3. 1 4平方毫米範圍内之樣本面積上進行。在樣 本上進行多次測量使資料具有一致性。表1 1列出一些在此 程式下沉積之含氟類鑽石塗料介電強度及其對應厚度與測 量面積。The resistivity of most coatings is higher than 101 Gohm-cm. The resistivity of some coatings is in the range of 1015 ohm-min. All high-resistivity films are also hydrophobic, with water contact angles between 85 and 94 °. Only one coating (job number 6 5 3) has a resistivity in the range of 106 ohm-cm. This special coating was deposited under deposition conditions other than normal conditions in an attempt to keep its resistivity in the range of 101 Q ohm-cm. The dielectric strength is measured by the above-mentioned current-voltage measurement method. The measurement method is performed on a sample area in a range of 0.79 to 3.14 square millimeters. Multiple measurements were made on the sample to make the data consistent. Table 1 1 lists the dielectric strength of some fluorine-containing diamond coatings deposited under this procedure and their corresponding thicknesses and measured areas.

第45頁 575681 五、發明說明（41) 表1 1 ·使用Μ I Μ結構之也介電強度 作業 薄膜厚度 介電強度 編號 (微米） 面積(mm2) Vbr(MV/cm) 面積(mm2) Vbr(MV/cm) 645 0.14 646 0.09 3.14 1.07 653 0.45 3.14 0.40 654 0.19 3.14 0.68 655 0.16 0.78 6.31 3.14 3.19 711 0.22 1.77 4.60 717 0.26 3.14 2.92 這六種用以試驗介電強度之塗料中，其中四種塗料之介 電強度高於1MV/厘米。這四種塗料中，樣本6 5 5與71 1顯示 之介電強度在2.9至4.5 Μ V/厘米範圍内。不過，樣本655 亦顯示介電強度對於測量面積之依存度。此現象可歸因於 該塗料上之瑕疵，諸如針孔或粒子。 厚度在0. 1 5至0 · 2 1微米範圍内之含氟類鑽石塗料在稍大 面積（1 0平方毫米）中測量所得到之介電強度高達3. 8 ΜV/ 厘米，損耗因數低至0 · 0 0 4 0。該塗料之介電常數約為 3. 5，其係以電容測量測定。電容測定亦顯示該含氟類鑽 石塗料具有熱安定性，其於-1 7 3 °C至+ 1 7 7 °C溫度範圍内之 變化小於1. 5%。Page 45 575681 V. Description of the invention (41) Table 1 1 · Dielectric strength operation film thickness using dielectric structure of Μ Μ Structure number (micron) Area (mm2) Vbr (MV / cm) Area (mm2) Vbr (MV / cm) 645 0.14 646 0.09 3.14 1.07 653 0.45 3.14 0.40 654 0.19 3.14 0.68 655 0.16 0.78 6.31 3.14 3.19 711 0.22 1.77 4.60 717 0.26 3.14 2.92 Of the six paints used to test dielectric strength, four of them Its dielectric strength is higher than 1MV / cm. Of these four coatings, samples 6 5 5 and 71 1 showed dielectric strengths in the range of 2.9 to 4.5 MV / cm. However, sample 655 also shows the dependence of dielectric strength on the measured area. This phenomenon can be attributed to imperfections in the coating, such as pinholes or particles. The dielectric strength of the fluorine-containing diamond coating with a thickness in the range of 0.1 5 to 0 · 21 micrometers measured in a slightly larger area (10 square millimeters) is as high as 3.8 MV / cm, and the loss factor is as low as 0 · 0 0 4 0. The dielectric constant of this coating is about 3.5, which is determined by capacitance measurement. Capacitance measurements also show that the fluorine-containing diamond coating has thermal stability, and the change in the temperature range of -17 3 ° C to + 1 7 7 ° C is less than 1.5%.

575681 五、發明說明（42) 實施例1 6 - 測量含氟類鑽石塗料之表面能量/水接觸角度 評估該含氟類鑽石塗料之表面能量與水接觸角度。就特 定應用而言，該塗料必須具有疏水性。疏水性條件係該含 氟類鑽石塗料之能量極低且水接觸角度極大。本發明人寫 出平衡在水液滴上作用之力量： rs 二 rsi + ri cos θ 此外，表面能量（τ )係由兩個分散分量組成，換言之極性 分量（τρ)與分散量（rd)組成。因此， r = rp + rd575681 V. Description of the invention (42) Example 16 6-Measure surface energy / water contact angle of fluorine-containing diamond coatings Evaluate the surface energy-water contact angle of the fluorine-containing diamond coatings. For specific applications, the coating must be hydrophobic. The hydrophobic condition is that the fluorine-containing diamond coating has very low energy and a large water contact angle. The inventors wrote the force of equilibrium acting on water droplets: rs rsi + ri cos θ In addition, the surface energy (τ) is composed of two dispersed components, in other words, the polar component (τρ) and the dispersed amount (rd) . Therefore, r = rp + rd

於紐約州立大學水牛城分校進行表面能量與接觸角度測 量。 表1 2列出含氟類鑽石塗料之接觸角度與表面能量值。測 得之表面能量與水接觸角度範圍為20. 4至24. 4達因/厘米 與8 3 °至9 8 ° 。此處提出之所有水角度資料誤差為 土 1 ^ 。此外，當容易且精確測量接觸角度時，水角度之 測量顯示該塗料之疏水性質為例外情況。水液滴以對稱方 式凝結成珠，如此使水液滴周圍的接觸角度一樣。Surface energy and contact angle measurements were taken at the State University of New York at Buffalo. Table 12 lists the contact angles and surface energy values of fluorine-containing diamond coatings. The measured surface energy and water contact angle ranged from 20.4 to 24.4 dyne / cm and 8 3 ° to 98 °. All water angle data errors presented here are soil 1 ^. In addition, when the contact angle is easily and accurately measured, the measurement of the water angle shows that the coating's hydrophobic nature is an exception. The water droplets condense into beads in a symmetrical manner so that the contact angle around the water droplets is the same.

第47頁 575681 五、發明說明（43) 表1 2.含氟類鑽石塗料之表面能量與水接觸角度 作業 編號 厚度 微米 表面能量(γ) 達因/厘米 極性分量(γρ) 達因/厘米 水角度 645 0.14 20.9 6.3 85 646 0.09 22.7 3.7 94 653 0.45 24.2 4.3 95 654 0.19 21.2 2.7 98 657 20.4 4.0 91 672 0.35 23.9 6.2 83 674 0.35 21.7 2.9 97 675 0.19 23.0 6.7 83 676 0.15 20.9 4.8 93 711 0.22 22.9 5.5 85 713 0.27 24.4 5.8 89 表面能量之極性分量（T P )顯示出與水接觸角度極密切 相關。獲得之極性分量範圍為2 . 7至6 . 7達因/厘米。 實施例1 7 - 測量含氟類鑽石塗料與聚合性基材之相容性 溫度相容性 將含氟類鑽石塗料塗覆於裸露Kapton極薄膜片、金屬化 K a p t ο η、金屬化U 11 e m、R y ΐ ο η基材上。以低溫進行沉積作 用時，於沉積期間此等基材均無受損。此證明用於聚合性 基材之含氟類鑽石塗料沉積方法的溫度相容性。 粘合性Page 47 575681 5. Description of the invention (43) Table 1 2. Surface energy and water contact angle of fluorine-containing diamond coatings Operation number Thickness Micron surface energy (γ) Dyne / cm Polarity component (γρ) Dyne / cm water Angle 645 0.14 20.9 6.3 85 646 0.09 22.7 3.7 94 653 0.45 24.2 4.3 95 654 0.19 21.2 2.7 98 657 20.4 4.0 91 672 0.35 23.9 6.2 83 674 0.35 21.7 2.9 97 675 0.19 23.0 6.7 83 676 0.15 20.9 4.8 93 711 0.22 22.9 5.5 85 713 0.27 24.4 5.8 89 The polar component (TP) of the surface energy appears to be very closely related to the angle of water contact. The obtained polar components ranged from 2.7 to 6.7 dyne / cm. Example 17 7-Measuring the compatibility of fluorine-containing diamond coatings with polymerizable substrates Temperature compatibility The fluorine-containing diamond coatings were applied to bare Kapton polar film sheets, metallized K apt η, metallized U 11 em, R y ο ο η on the substrate. When deposited at low temperatures, these substrates were not damaged during the deposition. This demonstrates the temperature compatibility of the fluorine-containing diamond coating deposition method for polymerizable substrates. Adhesion

第48頁 575681 五、發明說明（44) 每個沉積作業中，在矽與玻璃對照樣本上進行ASTM粘合 性試驗。部分钻合試驗亦在金屬化K a p t ο η樣本上進行。此 等試驗提供粘合性效能之定量分等。使用ASTM試驗D 3 3 5 9 - 8 7進行含氟類鑽石塗料之粘合性試驗。該粘合性試 驗係於所有沉積作業回合之對照樣本上進行。在矽與玻璃 對照樣本上之粘合性試驗結果列於表1 3。 表1 3.含氟類鑽石塗料之對照矽與玻璃樣本粘合性與薄 膜應力Page 48 575681 V. Description of the Invention (44) In each deposition operation, an ASTM adhesion test was performed on a silicon and glass control sample. Partial drill-in tests were also performed on metallized Ka p t ο η samples. These tests provide quantitative grading of adhesion performance. ASTM test D 3 3 5 9-8 7 was used to test the adhesion of fluorine-containing diamond coatings. The adhesion test was performed on control samples for all rounds of the deposition operation. The results of the adhesion tests on silicon and glass control samples are shown in Table 13. Table 1 3. Comparison of silicon and glass sample adhesion and film stress of fluorine-containing diamond coatings

作業編號 粘合性 壓縮應力，MPa 645 良好 - -40 646 良好 653 玻璃-差 654 差 -375 657 良好 672 良好 -321 674 良好 -282 675 玻璃差 -326 676 良好 711 良好 -325 713 良好 -319 718 良好 -97 719 良好 -384Job number Adhesive compressive stress, MPa 645 Good--40 646 Good 653 Glass-Poor 654 Poor -375 657 Good 672 Good-321 674 Good-282 675 Glass Poor-326 676 Good 711 Good-325 713 Good-319 718 Good-97 719 Good-384

第49頁 575681 Λν '、工 -料上製圖 列二離子钱刻研究含氣類鑽石塗料之韻岁作用 刻含氟類鑽石塗料之為h 土丁K域到作用。可以 當功率低時，添加氧僅有=括：：CF勢。 時，添加氧之效果變大百效果。功率水準 度為32瓦/平方厘米）於】Π二準為⑽瓦（適當功率密 率。不添加氧時，該含氟員.SCcm時發生最大蝕刻速 同條件下之二氧化石夕U類鑽石塗料之餘刻速率相當於相 研九不同線寬幾何j見 ^ 良好解析度。 、"見為1 · 5微米時可以達到極 研究該含氟類鑽石塗斜於^ ^ 速率。所有情況中該含氟類鑽】：;1與光阻灰令之蝕刻 梯狀。此顯示可以選擇性韻刻含=之後亦未觀察到階 蝕刻金屬及去除光阻之蝕 I' '石塗料，而且用以 ^料。 予著劑不會影響含氣類鑽石 於異丙醇中超音诂、、主、'钞TT^片 離子水中去除污垢與其他粗大污^手術刀片，I在去 該樣本約30分鐘。將該刀片安掌二:。於室溫空氣中乾燥 。該固定器固定在直徑30· 48厘、^固定螺旋之鋁固定 =式固定器。將矽（1〇〇)與破墦樣=(丨2吋）之不鑄鋼行 定器旁。以清潔該電手術刀片之 裝在該電手術刀片固 該樣本為2· 54厘米X 2· 54厘米。二方法清潔此等樣本。 __ 。括〜個較長的砂樣本 頁 第50 575681 五、發明說明（46) (7 · 6 2厘米χ 2 · 5 4厘米）以測量應力。將該不銹鋼固定器裝 於1米χ 1米X 1米不銹鋼真空室中。以一個魯特送風機、 ，械性泵及兩個擴散泵將該真空室之壓力抽至5 · 〇 χ 1 〇 一 6 笔巴之基本壓力。以每分鐘7轉旋轉該樣本以加強沉積均 S度。以氬輝光放電進一步清潔該基材。於該真空室繼續 來^氯氣，直到其壓力達到2·〇Χ10-4毫巴為止。其次，以 期間&大電流電源之7 5 · 1安培交流電加熱鎢燈絲。此作業 真空室邊燈絲溫度超過2 1 〇 〇。(：。在該燈絲與呈接地電位之 電源。t 加15。伏（直流電）偏壓。使用分離之直流電 電源、上Ϊ S二Ϊ 5 f子，並產生氬電聚放電。在燈絲偏壓 315伏之射頻H11.04安培。對該電手術刀片施加 料1 5分鐘結束時，關斤對该笔手術刀片濺鍍1 5分 矽二鴣燈絲與偏壓保掊二虱虱並開始沉積含氟類鑽石塗 貌蒸氣（液態冬3 3 3啟丄並於該室導入約〇.〇4sccm之 妨/、，3〜三氣丙基甲美’石''二氟丙基甲基矽氧烷或液態聚 Ϊ)。樣，力保持2基以 風 於該室内冷卻3〇分爹毛巴。，沉積作用進行90分 樣本與，到大氣壓力“；。」二氣導入該室使該室通 料。7本。觀察該電手 先巴為止。自固定器取下 利鋼二電手術刀片上之含C片與樣本兩側之深黑色塗 樣本该塗料上來回作業弗頌鑽石塗料具有抗磨性。以銳 ^ 上夠得之厚度分別為。該塗料並未剝落。在矽與玻璃 • · 3 6 7微米與1 · 6 9 8微米。在矽與 575681 五、發明說明P.49 575681 Λν ', drawing on the material-Column two ion money engraving studies on the rhyme effect of gas-containing diamond coatings Engraving the fluorine-containing diamond coatings is the h-Ting K domain. Yes When the power is low, oxygen is added only = = :: CF potential. As time goes on, the effect of adding oxygen becomes large. The power level is 32 watts per square centimeter) and the second standard is ⑽ watts (appropriate power density. When no oxygen is added, the fluorine-containing member. SCcm has the maximum etching rate under the same conditions. The diamond coating's remaining cutting rate is equivalent to that of the different line width geometries of KENKEN. See good resolution. When the value is 1.5 μm, it is possible to achieve extremely high rates. The fluorine-containing diamond coating has an oblique rate of ^ ^. In all cases The fluorine-containing diamond] :; 1 and the photoresist gray etched ladder-like etch. This display can be selectively engraved containing == no step etching metal and photoresist removal I '' stone coating, and For preservatives, the pre-injection agent will not affect the removal of dirt and other coarse dirt in the ionized water of sonicated, main, and banknotes in isopropanol by isopropyl alcohol. ^ Surgical blades, I will remove about 30 of the sample. Minutes. The blade is placed in the palm of the hand: Dry in the air at room temperature. The holder is fixed at 30.48 cm in diameter and fixed with a fixed aluminum screw. The holder is silicon (100) and broken. = (丨 2 inch) next to the uncast steel row fixture. To clean the electric surgical blade, install it on the electric surgical blade The sample is 2.54 cm X 2.54 cm. Two methods to clean these samples. __. Include ~ long sand sample page 50 575681 5. Description of the invention (46) (7 · 6 2 cm χ 2 · 54 cm) to measure the stress. The stainless steel holder was installed in a stainless steel vacuum chamber of 1 meter x 1 meter X 1 meter. The pressure of the vacuum chamber was evacuated by a Lutte blower, mechanical pump, and two diffusion pumps. Up to 5 · 0χ 1 06 basic pressure of the pen. Rotate the sample at 7 revolutions per minute to enhance the deposition uniformity. Clean the substrate further with an argon glow discharge. Continue to ^ chlorine gas in the vacuum chamber until The pressure reaches 2.0 × 10-4 mbar. Secondly, the tungsten filament is heated with a period of 75.1 ampere AC power of a high-current power supply. The temperature of the filament at the side of the vacuum chamber exceeds 2 100. (:. The filament is connected to a power source at ground potential. T is added with a voltage of 15. volts (DC). A separate DC power source is used, and the S Ϊ 5 子 is used to generate an argon polycondensation discharge. A 315 volt RF is applied to the filament H11.04 Amp. At the end of 15 minutes of applying the material to the electrosurgical blade Guan Jin sputtered the surgical blade with a 15-minute silicon difluoride filament and a bias-protected diploid lice and began to deposit fluorine-containing diamond-coated vapor (liquid winter 3 3 3 was opened and introduced into the room for about 0. 〇4sccm //, 3 ~ tris-propyl-metamethene 'stone', difluoropropylmethylsiloxane or liquid polyfluorene). In the same way, keep 2 bases in the room to cool the air for 30 minutes. Maoba., The sedimentation was performed for 90 minutes and the atmospheric pressure ";" Two gases were introduced into the chamber to make the chamber pass. 7. Observe the electric hand before the ba. Remove the Ligang Second Electric Surgery from the fixture. The blade containing C on the blade and the dark black coated samples on both sides of the sample. This coating is frost-resistant and has abrasion resistance. The thicknesses that can be obtained with sharp ^ are respectively. The coating did not peel off. In silicon and glass • 3 6 7 microns and 1 6 9 8 microns. In Silicon and 575681 V. Invention Description

玻 璃樣本上計算之沉積速率分別為〇 · 9丨丨微来/小士 1.1 32微米/小時。以毫微鑑定器在矽與玻璃樣本:2 塗料微硬度與彈性模數分別為12.4〇?&及1 04 6GPa 自 7. 62厘米X 2. 54厘米矽樣本之曲率上測量應力。該應力為 - 6 3 6 MPa(壓縮）。The calculated deposition rates on the glass samples were 0.9 · micron / min 1.1 1.1 micron / hour. The stress was measured on the silicon and glass samples using a nanometer appraiser: 2 coatings with microhardness and modulus of elasticity of 12.40 ° and 1.04 GPa from 7.62 cm x 2.54 cm silicon samples. The stress is-6 3 6 MPa (compressed).

將另外包含一種金屬摻雜劑之含氟類鑽石塗料（如實施 例1 3所述）塗覆於電手術刀片上。 較佳之其他金屬摻雜劑為鈦。此具體實例中，以磁控管 共濺鍍作用將鈦導入含氟類鑽；^塗料。 一 電阻率⑷微歐姆-厘求）以傳導射頻能量之疋生物種相容有^金刀 屬。 沉積作用之前，該電手術刀片於溫和清潔劑與異丙醇中 各以超音波清潔1 5分鐘。在每個步驟之間，該刀片於去離 子水中清洗1 5分鐘以去除任何殘留物。該刀片於空氣中乾 燥約20分鐘。將經清潔刀片裝在一個基材台上。該基材台 於/儿積期間偏置。使用丨〇 〇 — 3 〇 〇仟赫之射頻產生器施加介 於300-800伏之DC偏壓。 該刀片裝於塗覆系統之後，將該室抽真空至1χ1〇4托 耳。該方法順序如下。將氬導入該室，而且其主要作為濺 鍍氣體。該氬氣之流速通常為每分鐘16標準立方厘米 〔seem)。總氣體壓力介於1χ1 〇_4至ιχ1 托耳。偏置該基材 台。其次，開始鈦之濺鍍。使用直流電（DC)或脈衝直流電An electrosurgical blade was coated with a fluorine-containing diamond coating material (as described in Example 13), which additionally contained a metal dopant. A preferred other metal dopant is titanium. In this specific example, titanium is introduced into a fluorine-containing diamond by co-sputtering with a magnetron; ^ coating. (1) resistivity (microohm-requirement) The species that are compatible with conducting radio frequency energy are ^ Gold knife. Prior to deposition, the electrosurgical blade was ultrasonically cleaned in mild detergent and isopropyl alcohol for 15 minutes each. Between each step, the blade was rinsed in deionized water for 15 minutes to remove any residue. The blade was dried in the air for about 20 minutes. The cleaned blade is mounted on a substrate table. The substrate table is biased during the product period. A DC bias voltage of 300-800 volts was applied using a RF generator of 〇〇〇－３０００５ 仟. After the blade was installed in the coating system, the chamber was evacuated to 1 x 104 Torr. The method sequence is as follows. Argon was introduced into the chamber, and it was mainly used as a sputtering gas. The flow rate of the argon gas is usually 16 standard cubic centimeters per minute (seem). The total gas pressure is between 1x1 0_4 and ιx1 Torr. Offset the substrate table. Next, titanium sputtering was started. Use direct current (DC) or pulsed direct current

575681 五、發明說明（48) (PDC)產生器使該磁控管標的鈦偏離。該磁控管功率為 1，5 0 0瓦。數秒鐘之後，開始進行熱燈絲三極管放電:以 60赫電源（14伏DC及90安培）將鎢燈絲加熱至白熱化。對該 燈絲施加150伏DC偏壓以產生電漿放電。起初，氬被離子" 化。不過，將經氟化矽氧烷先質-液態聚-3,3, 3-三氟丙基 曱基矽氧烷-（50%)二甲基矽氧烷（eFMS_221，Gelest pA) 導入室中。離子化該經氟化先質，並容積輝光放電埴充爷 ϋ： ° ^575681 V. Description of the invention (48) (PDC) generator deviates the titanium of the magnetron target. The magnetron has a power of 1,500 watts. After a few seconds, the hot-filament triode began to discharge: the tungsten filament was heated to whiteness with a 60-Hz power supply (14 volts DC and 90 amps). A 150 volt DC bias was applied to the filament to generate a plasma discharge. Initially, argon was ionized. However, the fluorinated siloxane precursor-liquid poly-3,3,3-trifluoropropylfluorenylsiloxane- (50%) dimethylsiloxane (eFMS_221, Gelest pA) was introduced into the chamber . The fluorinated precursor is ionized and volumetric glow discharge is performed. 埴: ° ^

1 〇 干赫時，此等塗料之代表性阻抗自5 〇至2 〇 〇歐姆。其 表面此里保持低度水準，在25至29 mN/m。於25 mN/m時可 以達到最適切割性能。該資料示於表丨4。The representative impedance of these coatings is from 50 to 2000 ohms at 10 Hz. The surface here remains at a low level, between 25 and 29 mN / m. Optimal cutting performance can be achieved at 25 mN / m. The information is shown in Table 丨 4.

第53頁 575681 五、發明說明（49) 表1 4.電手術刀片上之低阻抗、低表面能量、含氟類鑽 石塗料Page 53 575681 V. Description of the invention (49) Table 1 4. Low resistance, low surface energy, fluorine-containing diamond coatings on electric surgical blades

塗覆 作業# 水接觸角度 (度） 伽瑪 (mN/m) 伽瑪ρ (mN/m) 伽瑪d (mN/m) 阻抗 (歐姆） 1039 77 29 8 29 81.33 1023 82 27 8 28 39.08 1022 77 28 9 30 32.83 1021 88 28 5 28 13.50 1020 91 25 4 26 29.33 1019 88 27 5 - 28 30.42 1018 87 27 6 30 120.58 1016 88 28 6 28 108 1015 87 25 6 29 52 1014 91 26 6 28 196.58 1013 88 27 6 28 101.17 伽瑪=複合表面游離能量 伽瑪p =複合表面游離能量之極性分量 伽瑪d =複合表面游離能量之分散分量 阻抗：於1 0 0仟赫測量 上述方法之其他具體實例為無燈絲放電。此作用可以使Coating operation # Water contact angle (degrees) Gamma (mN / m) Gamma ρ (mN / m) Gamma d (mN / m) Impedance (ohm) 1039 77 29 8 29 81.33 1023 82 27 8 28 39.08 1022 77 28 9 30 32.83 1021 88 28 5 28 13.50 1020 91 25 4 26 29.33 1019 88 27 5-28 30.42 1018 87 27 6 30 120.58 1016 88 28 6 28 108 1015 87 25 6 29 52 1014 91 26 6 28 196.58 1013 88 27 6 28 101.17 Gamma = free energy of composite surface Gamma p = polar component of free energy of composite surface Gamma d = dispersed component of free energy of composite surface Impedance: Other specific examples of the above method measured at 100 Hz Filament discharge. This effect can make

苐54頁 575681 五、發明說明（50) 用一中空電極、電容偶合射頻、誘導偶合射頻或微波電漿 放電。可以使用熱蒸發或C-束蒸發進行鈦之摻雜作用。此 外，可以使用含鈦矽氧烷。 雖然已為了說明目的詳述本發明，但是此等細節僅用於 該目的，在不違背下列申請專利範圍所定義之本發明精神 與範圍之下，熟知本技藝者可以製得諸多變化。苐 Page 54 575681 5. Description of the invention (50) Use a hollow electrode, capacitor-coupled RF, induced-coupled RF or microwave plasma to discharge. Titanium doping can be performed using thermal evaporation or C-beam evaporation. In addition, titanium-containing siloxane can be used. Although the present invention has been described in detail for illustrative purposes, these details are only used for this purpose, and many variations can be made by those skilled in the art without departing from the spirit and scope of the present invention as defined by the following patent application scope.

第55頁Page 55

Claims (1)

575681 ^素號 871:2019,3 月 曰575681 ^ prime number 871: 2019, March 夺 六、申請專利範圍 1. 一種包含塗覆含氟塗料基材之物件，其中該塗料包括 一種含碳、石夕、氧、氫與氟之類鑽石組合物，其中該碳含 有sp3鍵，且其中該塗料具有自5至32 GPa之硬度及自19達 因/厘米至29達因/厘米之表面能量。 2 .如申請專利範圍第1項之物件 性基材。 3. 如申請專利範圍第2項之物件 種聚合性薄膜。 4. 如申請專利範圍第3項之物件 自包括聚醯亞胺、聚酯、polythermide 類與聚對苯二甲酸伸乙酯薄膜。 5 .如申請專利範圍第4項之物件，其中該含氟塗料另外 包括一種其他摻雜劑。 6 .如申請專利範圍第5項之物件，其中該其他摻雜劑選 自包括週期表Ib-VIIb與VIII族元素。 7.如申請專利範圍第6項之物件，其中該其他摻雜劑選 自包括B 、Si 、Ge 、Te 、0 、M〇、W 、 P t、V、Fe、Co、Mg、Mn、Ni、Ti Cu、A1、N、Ag 與Au ° 8 .如申請專利範圍第7項之物件： 鈦。 9 .如申請專利範圍第2項之物件 度自0 . 0 0 5微米至1 0微米。 1 0 .如申請專利範圍第2項之物件 其中該基材是一種撓 其中該撓性基材是一 其中該聚合性薄膜選 聚醯胺-醯亞胺 Ta Z r Nb Cr Pd Re Ir Hf 其中該其他摻雜劑為 其中該含氟塗料之厚 ’其中該碳、氮 矽Claim 6. Scope of patent application 1. An object comprising a substrate coated with a fluorine-containing coating, wherein the coating comprises a diamond composition containing carbon, stone, oxygen, hydrogen, and fluorine, wherein the carbon contains sp3 bonds, and The coating has a hardness from 5 to 32 GPa and a surface energy from 19 dyne / cm to 29 dyne / cm. 2. Object-like substrates as described in item 1 of the patent application. 3. As for the item of the scope of patent application, it is a kind of polymer film. 4. Items such as item 3 of the patent application include polyimide, polyester, polythermide and polyethylene terephthalate films. 5. The article according to item 4 of the patent application, wherein the fluorine-containing coating further includes an additional dopant. 6. The article of claim 5 in which the other dopant is selected from the group consisting of Periodic Table Ib-VIIb and Group VIII elements. 7. The article as claimed in item 6, wherein the other dopant is selected from the group consisting of B, Si, Ge, Te, 0, M0, W, Pt, V, Fe, Co, Mg, Mn, Ni , Ti Cu, A1, N, Ag, and Au ° 8. Such as the object of the scope of patent application: Titanium. 9. The degree of the item in the second patent application range is from 0.05 micron to 10 micron. 10. The article according to item 2 of the patent application, wherein the substrate is a flexible substrate, wherein the flexible substrate is a polymerized film selected from polyamidoamine-amidoimine Ta Z r Nb Cr Pd Re Ir Hf where The other dopant is the thickness of the fluorine-containing coating, wherein the carbon and nitrogen silicon O:\56\56197-920926.ptc 第57頁 575681 案號 87120193 fV年" 月 曰 修正 六、申請專利範圍 氧與氟係得自具有自1至1 0個矽原子有機矽氧烷分解作 用。 1 1.如申請專利範圍第1 0項之物件，其中該有機矽氧烷 是聚三氟丙基甲基矽氧烷。 1 2.如申請專利範圍第1 0項之物件，其中該有機矽氧烷 是聚-3, 3 ,3 -三氟丙基甲基矽氧烷-(50%)二甲基矽氧烷共 聚合物。 1 3.如申請專利範圍第2項之物件，其中該含氟塗料之碳 含量自40重量％至98重量％。 1 4.如申請專利範圍第2項之物件，其中該含氟塗料之碳 對矽重量比率自4 : 1至9 : 1 。 1 5.如申請專利範圍第2項之物件，其中該含氟塗料之矽 對氧重量比率自0 · 6 ·· 1至1 · 7 ·· 1。 1 6.如申請專利範圍第2項之物件，其中該含氟塗料之碳 含量至少為該含氟塗料40原子％，氫含量高達該碳之40原 子％，矽、氧與摻雜劑之總和大於該塗料2原子％。 1 7.如申請專利範圍第2項之物件，其中該含氟塗料之介 電強度自1MV/厘米至4MV/厘米。 1 8.如申請專利範圍第2項之物件，其中該含氟塗料之電 阻率自1 014歐姆-厘米至10_2歐姆-厘米。 1 9 .如申請專利範圍第2項之物件，其中該含氟塗料之表 面能量自19. 5達因/厘米至26達因/厘米。 2 0 .如申請專利範圍第2項之物件，其中該含氟塗料之水 接觸角度自8 0 °至1 0 1 ° 。O: \ 56 \ 56197-920926.ptc Page 57 575681 Case No. 87120193 fV " Month Amendment VI. Patent Application Scope Oxygen and Fluorine are derived from organosilicon decomposition with 1 to 10 silicon atoms . 1 1. The article according to item 10 of the scope of patent application, wherein the organosiloxane is polytrifluoropropylmethylsiloxane. 1 2. The article according to item 10 of the patent application scope, wherein the organosiloxane is poly-3,3,3-trifluoropropylmethylsiloxane- (50%) dimethylsiloxane polymer. 1 3. The article according to item 2 of the patent application scope, wherein the carbon content of the fluorine-containing coating is from 40% by weight to 98% by weight. 1 4. The article according to item 2 of the patent application scope, wherein the carbon to silicon weight ratio of the fluorine-containing coating is from 4: 1 to 9: 1. 1 5. The article according to item 2 of the scope of patent application, wherein the weight ratio of silicon to oxygen of the fluorine-containing coating is from 0 · 6 ·· 1 to 1 · 7 · · 1. 1 6. The article according to item 2 of the scope of patent application, wherein the carbon content of the fluorine-containing coating is at least 40 atomic% of the fluorine-containing coating, the hydrogen content is up to 40 atomic% of the carbon, and the total of silicon, oxygen and dopant More than 2 atomic% of the coating. 1 7. The article according to item 2 of the patent application scope, wherein the dielectric strength of the fluorine-containing coating is from 1MV / cm to 4MV / cm. 1 8. The article according to item 2 of the patent application range, wherein the resistivity of the fluorine-containing coating is from 1,014 ohm-cm to 10_2 ohm-cm. 19. The item according to item 2 of the patent application range, wherein the surface energy of the fluorine-containing coating is from 19.5 dyne / cm to 26 dyne / cm. 20. The article according to item 2 of the patent application range, wherein the water contact angle of the fluorine-containing coating is from 80 ° to 101 °. O:\56\56197-920926.ptc 第58頁 575681 案號 87120193 Q 月 修正 々、申請專利範圍 2 1 .如申請專利範圍第1項之物件，其中該基材是一種精 確磨利基材。 2 2.如申請專利範圍第2 1項之物件，其中該精確磨利基 材包括一種金屬。 精確磨利基 基材係選自 基材是一種 含氟塗料另 其他摻雜劑 其他掺雜劑 、P d、I r、 Re 、 Hf 、 含氟塗料沉 塗料沉積在 含氟塗料直 2 3 .如申請專利範圍第2 1項之物件，其中該 材包括一種非金屬。 2 4.如申請專利範圍第2 1項之物件，其中該 包括工業工具、電手術儀器、刀類與剃刀。 2 5 .如申請專利範圍第2 4項之物件，其中該 剃刀刀片。 2 6 .如申請專利範圍第2 1項之物件，其中該 外包括一種其他摻雜劑。 2 7 .如申請專利範圍第2 6項之物件，其中該 係選自週期表11)-¥1113與¥111族元素。 2 8 .如申請專利範圍第2 7項之物件，其中該 選自包括B 、Si 、Ge、Te 、0、M〇、W 、丁 a 、Nb P t、V、Fe、C〇、Mg、Mn、Ni、Ti、Zr、Cr、 Cu、A 1、N、Ag 與Au o 2 9 .如申請專利範圍第2 1項之物件，其中該 積在該基材之厚度自5毫微米至1 2微米。 3 0 .如申請專利範圍第2 1項之物件，其中該 該基材之厚度自5毫微米至1 5 0毫微米。 3 1 .如申請專利範圍第2 1項之物件，其中該 接沉積於該基材上，其中無中間層。O: \ 56 \ 56197-920926.ptc P.58 575681 Case No. 87120193 Q month Amendment 々 、 Application scope of patent 2 1. For the item of scope 1 of patent application, the substrate is a precision ground substrate. 2 2. The article of claim 21 in the scope of patent application, wherein the precision ground substrate comprises a metal. The precision ground substrate is selected from the group consisting of a fluorine-containing coating and other dopants. Other dopants, P d, Ir, Re, Hf, fluorine-containing coatings, and coatings are deposited on the fluorine-containing coatings. For example, the article 21 in the scope of patent application, wherein the material includes a non-metal. 2 4. The items according to item 21 of the patent application scope, which include industrial tools, electrosurgical instruments, knives and razors. 25. The article of claim 24, wherein the razor blade. 26. The article in the scope of patent application No. 21, wherein the object includes an other dopant. 27. The item according to item 26 of the scope of patent application, wherein the system is selected from the 11)-¥ 1113 and ¥ 111 elements of the periodic table. 28. The item according to item 27 of the scope of patent application, wherein the item is selected from the group consisting of B, Si, Ge, Te, 0, M0, W, Ding a, Nb Pt, V, Fe, C0, Mg, Mn, Ni, Ti, Zr, Cr, Cu, A1, N, Ag, and Au o 2 9. The article in the scope of patent application No. 21, wherein the thickness of the substrate is from 5 nm to 1 2 microns. 30. The article according to item 21 of the patent application range, wherein the thickness of the substrate is from 5 nm to 150 nm. 31. The article according to item 21 of the patent application scope, wherein the contact is deposited on the substrate without an intermediate layer therein. O:\56\56197-920926.ptc 第59頁 575681 案號 87120193 月 修正 六、申請專利範圍 3 2.如申請專利範圍第2 1項之物件，其中該碳、氫、 矽、氧與氟係得自具有自1至1 0個矽原子有機矽氧烷分解 作用。 3 3.如申請專利範圍第3 2項之物件，其中該有機矽氧烷 是聚三氟丙基甲基矽氧烷。 3 4.如申請專利範圍第3 2項之物件，其中該有機矽氧烷 是聚-3, 3, 3 -三氟丙基甲基矽氧烷-(50%)二曱基矽氧烷共 聚合物。 其中該含氟塗料之 其中該含氟塗料之 其中該含氟塗料之 其中該含氟塗料之 3 5 .如申請專利範圍第2 1項之物件 碳含量自40重量％至98重量％。 3 6 .如申請專利範圍第2 1項之物件 碳對矽重量比率自2 : 1至8 : 1。 3 7.如申請專利範圍第2 1項之物件 矽對氧重量比率自0 . 5 : 1至3 : 1。 3 8 .如申請專利範圍第2 1項之物件 碳含量至少為該含氟塗料40原子％，氫含量高達該碳之40 原子％，矽、氧與摻雜劑之總和大於該塗料2原子％。 3 9 .如申請專利範圍第2 1項之物件，其中該含氟塗料之 電阻率自1014歐姆-厘米至10_2歐姆-厘米。 4 0 .如申請專利範圍第2 1項之物件，其中該含氟塗料之 表面能量自19. 5達因/厘米至26達因/厘米。 4 1 .如申請專利範圍第2 1項之物件，其中該含氟塗料之 水接觸角度自8 0 °至1 0 1 ° 。 4 2 .如申請專利範圍第1項之物件，其中該基材是一種電O: \ 56 \ 56197-920926.ptc Page 59 575681 Case No. 87120193 Amendment VI. Patent application scope 3 2. For the item of patent application scope item 21, where the carbon, hydrogen, silicon, oxygen and fluorine are Derived from organosiloxanes with decomposition from 1 to 10 silicon atoms. 3 3. The article according to item 32 of the scope of patent application, wherein the organosiloxane is polytrifluoropropylmethylsiloxane. 3 4. The article according to item 32 of the scope of patent application, wherein the organosiloxane is poly-3, 3, 3 -trifluoropropylmethylsiloxane- (50%) difluorenylsiloxane polymer. Among them, the fluorine-containing coating material, among which the fluorine-containing coating material, among which the fluorine-containing coating material, wherein the fluorine-containing coating material is 35. Such as the object of the scope of patent application No. 21, the carbon content is from 40% by weight to 98% by weight. 36. Articles in the scope of patent application No. 21 Carbon to silicon weight ratio from 2: 1 to 8: 1. 3 7. The article according to item 21 of the scope of patent application The weight ratio of silicon to oxygen is from 0.5: 1 to 3: 1. 38. If the item in the scope of patent application No. 21 has a carbon content of at least 40 atomic% of the fluorine-containing coating, a hydrogen content of up to 40 atomic% of the carbon, and the total of silicon, oxygen and dopant is greater than 2 atomic% of the coating. . 39. The article according to item 21 of the patent application range, wherein the specific resistance of the fluorine-containing coating is from 1014 ohm-cm to 10_2 ohm-cm. 40. The article according to item 21 of the patent application range, wherein the surface energy of the fluorine-containing coating is from 19.5 dyne / cm to 26 dyne / cm. 41. The item according to item 21 of the patent application range, wherein the water contact angle of the fluorine-containing coating is from 80 ° to 101 °. 4 2. The article according to item 1 of the patent application scope, wherein the substrate is an electric O:\56\56197-920926.ptc 第60頁 575681 _案號87120193 ❻碑 月 曰 修正_ 六、申請專利範圍 厂 手術儀器。 4 3.如申請專利範圍第4 2項之物件，其中該電手術儀器 係選自包括電手術刀片、雙極鉗、腹腔鏡儀器、牙醫用托 架與生物醫療裝置。 4 4.如申請專利範圍第4 2項之物件，其中該電手術儀器 是一種精確磨利基材。 4 5 .如申請專利範圍第4 2項之物件，其中該含氟塗料另 外包含一種其他掺雜劑。 4 6 .如申請專利範圍第4 5項之物件，其中該其他摻雜劑 係選自週期表lb-VI lb與VI I I族元素。 4 7.如申請專利範圍第4 6項之物件，其中該其他摻雜劑 係選自包括 B、Li、Na、Si、Ge、Te、0、Mo、W、Ta、 Nb 、Pd 、Ir 、Pt、V 、Fe 、Co 、Mg 、Mn 、Ni 、Ti 、Zr 、 Cr 、Re 、Hf 、Cu 、A1 、N 、Ag 、Au 、TiN 、BN 、A1N 、ZrN 與 CrN ° 4 8 .如申請專利範圍第4 2項之物件，其中該含氟塗料沉 積厚度自0 . 5微米至5微米。 4 9.如申請專利範圍第4 2項之物件，其中該含氟塗料之 沉積厚度自2微米至3微米。 5 0 .如申請專利範圍第4 2項之物件，其中該碳、氫、 矽、氧與氟係得自具有自1至1 0個矽原子有機矽氧烷分解 作用。 5 1 .如申請專利範圍第5 0項之物件，其中該有機矽氧烷 是聚三氟丙基甲基矽氧烷。O: \ 56 \ 56197-920926.ptc Page 60 575681 _Case No. 87120193 Stele Month Month Revision_ VI. Patent Application Scope Plant Surgical Instruments. 4 3. The item according to item 42 of the patent application scope, wherein the electrosurgical instrument is selected from the group consisting of an electrosurgical blade, bipolar forceps, a laparoscopic instrument, a dentist bracket, and a biomedical device. 4 4. The article according to item 42 of the patent application scope, wherein the electrosurgical instrument is a precision ground material. 4 5. The article according to item 42 of the patent application scope, wherein the fluorine-containing coating further comprises an other dopant. 46. The article according to item 45 of the scope of patent application, wherein the other dopants are selected from the periodic table lb-VI lb and group VI I I elements. 4 7. The article according to item 46 of the patent application scope, wherein the other dopant is selected from the group consisting of B, Li, Na, Si, Ge, Te, 0, Mo, W, Ta, Nb, Pd, Ir, Pt, V, Fe, Co, Mg, Mn, Ni, Ti, Zr, Cr, Re, Hf, Cu, A1, N, Ag, Au, TiN, BN, A1N, ZrN and CrN ° 48. The article of scope 42, wherein the fluorine-containing coating is deposited from a thickness of 0.5 micrometers to 5 micrometers. 49 9. The article according to item 42 of the scope of patent application, wherein the thickness of the fluorine-containing coating is from 2 micrometers to 3 micrometers. 50. The article according to item 42 of the scope of the patent application, wherein the carbon, hydrogen, silicon, oxygen and fluorine are derived from an organosiloxane with a decomposition function of 1 to 10 silicon atoms. 51. The article according to claim 50 in the scope of patent application, wherein the organosiloxane is polytrifluoropropylmethylsiloxane. O:\56\56197-920926.ptc 第61頁 575681 _案號 87120193 年 月 日__ 六、申請專利範圍 5 2.如申請專利範圍第5 0項之物件，其中該有機矽氧烷 是聚-3, 3, 3 -三氟丙基甲基矽氧烷-(50%)二甲基矽氧烷共 聚合物。 5 3.如申請專利範圍第4 2項之物件，其中該含氟塗料之 碳含量自40重量％至98重量？/〇。 5 4.如申請專利範圍第4 2項之物件，其中該含氟塗料之 碳對石夕重量比率自2 : 1至8 : 1。 5 5 .如申請專利範圍第4 2項之物件，其中該含氟塗料之 矽對氧重量比率自0 . 5 : 1至3 : 1。 5 6.如申請專利範圍第4 2項之物件，其中該含氟塗料之 碳含量至少為該含氟塗料40原子％，氫含量高達該碳之40 原子％，矽、氧與摻雜劑之總和大於該塗料2原子％。 5 7.如申請專利範圍第4 2項之物件，其中該含氟塗料之 阻抗自1歐姆至1 0 0 0歐姆。 5 8.如申請專利範圍第4 2項之物件，其中該含氟塗料之 電阻率自10歐姆-厘米至1015歐姆-厘米。 5 9.如申請專利範圍第4 2項之物件，其中該含氟塗料之 水接觸角度自8 0 °至1 0 1 ° 。 6 0 . —種製造塗覆含氟類鑽石塗料基材之方法，包括： 將該基材置於一真空塗覆室；且 以非成簇粒子束共沉積作用將含碳、矽、氧、氫與氟類 鑽石組合物沉積於該基材上，且其中該塗料具有自5至3 2 GPa之硬度及自19達因/厘米至29達因/厘米之表面能量， 該非成簇粒子束包括碳、矽、氧、氫與氟之離子、原子或O: \ 56 \ 56197-920926.ptc Page 61 575681 _ Case No. 87120193 __ Sixth, the scope of patent application 5 2. If the object of the scope of patent application No. 50, where the organosiloxane is a polymer -3, 3, 3 -trifluoropropylmethylsiloxane- (50%) dimethylsiloxane copolymer. 5 3. If the article in the scope of patent application No. 42, the carbon content of the fluorine-containing coating is from 40% by weight to 98% by weight? / 〇. 5 4. The article according to item 42 of the scope of patent application, wherein the carbon to stone weight ratio of the fluorine-containing coating is from 2: 1 to 8: 1. 55. The article according to item 42 of the patent application range, wherein the weight ratio of silicon to oxygen of the fluorine-containing coating is from 0.5: 1 to 3: 1. 5 6. The article according to item 42 of the patent application scope, wherein the carbon content of the fluorine-containing coating is at least 40 atomic% of the fluorine-containing coating, the hydrogen content is up to 40 atomic% of the carbon, and the content of silicon, oxygen and dopants The sum is greater than 2 atomic% of the coating. 5 7. The article according to item 42 of the patent application scope, wherein the impedance of the fluorine-containing coating is from 1 ohm to 100 ohm. 5 8. The article according to item 42 of the patent application range, wherein the specific resistance of the fluorine-containing coating is from 10 ohm-cm to 1015 ohm-cm. 5 9. The article according to item 42 of the scope of patent application, wherein the water contact angle of the fluorine-containing coating is from 80 ° to 101 °. 60. A method for manufacturing a coated substrate containing fluorine-containing diamond coatings, comprising: placing the substrate in a vacuum coating chamber; and co-depositing carbon, silicon, oxygen, A hydrogen and fluorine diamond composition is deposited on the substrate, and wherein the coating has a hardness from 5 to 3 2 GPa and a surface energy from 19 dyne / cm to 29 dyne / cm. The non-clustered particle beam includes Carbon, silicon, oxygen, hydrogen and fluorine ions, atoms or O:\56\56197-920926.ptc 第62頁 575681 案號 87120193 曰 修正 六、申請專利範圍 基團，每種粒子之平均自由路徑超過其來源與基材生長粒 子塗覆表面間之距離。 6 1 .如申請專利範圍第6 0項之方法，其中該基材是一種 撓性基材。 6 2.如申請專利範圍第6 1項之方法，另外包括在該撓性 基材上沉積厚度自0 . 0 0 5微米至1 0微米之塗料。 6 3.如申請專利範圍第6 0項之方法，其中該基材是一種 精確磨利基材。 6 4.如申請專利範圍第6 3項之方法，其中該含氟塗料沉 積於該精確磨利基材上之厚度自5毫微米至1 2微米。 6 5 .如申請專利範圍第6 3項之方法，其中該含氟塗料沉 積於該精確磨利基材上之厚度自5毫微米至1 5 0毫微米。 6 6 .如申請專利範圍第6 0項之方法，其中該基材是一種 電手術儀器。 另外包括在該含就 其中該其他摻雜劑 6 7 .如申請專利範圍第6 0項之方法 塗料上沉積一種其他摻雜劑。 6 8 .如申請專利範圍第6 7項之方法 係選自週期表lb-VI lb與VI I I族元素。 6 9 .如申請專利範圍第6 8項之方法，其中該其他摻雜劑 係選自包括B、Li、Na、Si、Ge、Te、0、Mo、W、Ta、 Nb、Pd、Ir、Pt、V、Fe、Co、Mg、Mn、Ni、Ti、Zr、 Cr、Re、Hf、（:u、Al、N、Ag、Au、TiN、BN、A1N、ZrN 與 CrN 〇 7 〇 .如申請專利範圍第6 0項之方法，其中該碳、氫、O: \ 56 \ 56197-920926.ptc page 62 575681 case number 87120193 said amendment 6. Scope of patent application Group, the average free path of each particle exceeds the distance between its source and the coated surface of the substrate growing particles. 61. The method of claim 60, wherein the substrate is a flexible substrate. 6 2. The method according to item 61 of the patent application scope, further comprising depositing a coating having a thickness of from 0.05 micrometers to 10 micrometers on the flexible substrate. 6 3. The method of claim 60 in the scope of patent application, wherein the substrate is a precision ground substrate. 64. The method according to item 63 of the scope of patent application, wherein the thickness of the fluorine-containing coating deposited on the precision abrasive substrate is from 5 nm to 12 μm. 65. The method according to item 63 of the scope of patent application, wherein the thickness of the fluorine-containing coating deposited on the precisely ground substrate is from 5 nm to 150 nm. 66. The method of claim 60, wherein the substrate is an electrosurgical instrument. It also includes depositing an additional dopant on the coating containing the other dopant 67. The method of item 60 of the scope of patent application. 68. The method according to item 67 of the scope of patent application is selected from the elements of the periodic table lb-VI lb and VI I I group. 69. The method of claim 68, wherein the other dopant is selected from the group consisting of B, Li, Na, Si, Ge, Te, 0, Mo, W, Ta, Nb, Pd, Ir, Pt, V, Fe, Co, Mg, Mn, Ni, Ti, Zr, Cr, Re, Hf, (: u, Al, N, Ag, Au, TiN, BN, A1N, ZrN and CrN 〇7 〇. The method of applying for the scope of patent No. 60, wherein the carbon, hydrogen, O:\56\56197-920926.ptc 第63頁 575681 _案號87120193 今巧7月 曰 修正_ 六、申請專利範圍 矽、氧與氟係得自具有自1至1 0個矽原子有機矽氧烷 分解作用。 7 1.如申請專利範圍第7 0項之方法，其中該有機矽氧烷 是聚三氟丙基甲基矽氧烷。 7 2.如申請專利範圍第7 0項之方法，其中該有機矽氧烷 是聚-3, 3, 3 -三氟丙基甲基矽氧烷-（50%)二甲基矽氧烷共 聚合物。 7 3.如申請專利範圍第6 0項之方法，其中該含氟塗料之 碳含量自40重量％至98重量％。 7 4.如申請專利範圍第6 0項之方法，其中該含氟塗料之 碳對矽重量比率自2 : 1至8 : 1。 7 5.如申請專利範圍第6 0項之方法，其中該含氟塗料之 碳對矽重量比率自4 ·· 1至9 : 1。 7 6 .如申請專利範圍第6 0項之方法，其中該含氟塗料之 矽對氧重量比率自0.5:1至3:1。 7 7.如申請專利範圍第6 0項之方法，其中該含氟塗料之 矽對氧重量比率自0 . 6 : 1至1. 7 : 1。 7 8.如申請專利範圍第6 0項之方法，其中該類鑽石固態 材料之碳含量大於該含氟類鑽石塗料4 0原子％，該氫含量 高達該竣之4 0原子％，矽、氧與摻雜劑之總和大於該含氟 類鑽石塗料2原子％。 7 9 .如申請專利範圍第6 0項之方法，其中該含氟類鑽石 塗料之介電強度自1MV/厘米至4MV/厘米。 8 〇 .如申請專利範圍第6 0項之方法，其中該含氟塗料之O: \ 56 \ 56197-920926.ptc page 63 575681 _ case number 87120193 amended in July of this year _ 6, the scope of patent application silicon, oxygen and fluorine are derived from organic silicon oxide with 1 to 10 silicon atoms Alkane decomposition. 7 1. The method according to item 70 of the scope of patent application, wherein the organosiloxane is polytrifluoropropylmethylsiloxane. 7 2. The method according to item 70 of the scope of patent application, wherein the organosiloxane is poly-3,3,3-trifluoropropylmethylsiloxane- (50%) dimethylsiloxane polymer. 7 3. The method according to item 60 of the patent application range, wherein the carbon content of the fluorine-containing coating is from 40% by weight to 98% by weight. 7 4. The method according to item 60 of the patent application range, wherein the carbon to silicon weight ratio of the fluorine-containing coating is from 2: 1 to 8: 1. 7 5. The method according to item 60 of the patent application range, wherein the carbon to silicon weight ratio of the fluorine-containing coating is from 4 ·· 1 to 9: 1. 76. The method according to item 60 of the patent application range, wherein the weight ratio of silicon to oxygen of the fluorine-containing coating is from 0.5: 1 to 3: 1. 7 7. The method according to item 60 of the scope of patent application, wherein the weight ratio of silicon to oxygen of the fluorine-containing coating is from 0.6: 1 to 1.7: 1. 7 8. The method according to item 60 of the scope of patent application, wherein the carbon content of this type of diamond solid material is greater than 40 atomic% of the fluorine-containing diamond coating, and the hydrogen content is as high as 40 atomic%, silicon, oxygen The sum with the dopant is greater than 2 atomic% of the fluorine-containing diamond coating. 79. The method of claim 60 in the scope of patent application, wherein the dielectric strength of the fluorine-containing diamond coating is from 1 MV / cm to 4 MV / cm. 80. The method of claim 60 in the scope of patent application, wherein the fluorine-containing coating is O:\56\56197-920926.ptc 第64頁 575681 _案號87120193 年j月 曰 修正_ 六、申請專利範圍 電阻率自1014歐姆-厘米至10-2歐姆/厘米。 8 1 .如申請專利範圍第6 0項之方法，其中該含氟塗料之 表面能量自19. 5達因/厘米至26達因/厘米。 8 2 .如申請專利範圍第6 0項之方法，其中該含氟塗料之 水接觸角度自8 0 °至1 0 1 ° 。 8 3 .如申請專利範圍第6 7項之方法，另外包括： 於有助於形成電阻器條件下在該經沉積含氟類鑽石塗料 上製成圖案。 8 4.如申請專利範圍第6 0項之方法，另外包括： 在該含氟類鑽石塗料下方沉積一金屬底層電極； 沉積頂層電極；以及 於有助於形成電阻器條件下在該經沉積頂層金屬上製成 圖案。O: \ 56 \ 56197-920926.ptc Page 64 575681 _Case No. 87120193 J. Amendment_ VI. Patent Application Range The resistivity ranges from 1014 ohm-cm to 10-2 ohm / cm. 81. The method of claim 60, wherein the surface energy of the fluorine-containing coating is from 19.5 dyne / cm to 26 dyne / cm. 8 2. The method according to item 60 of the scope of patent application, wherein the water contact angle of the fluorine-containing coating is from 80 ° to 101 °. 83. The method of claim 67, further comprising: making a pattern on the deposited fluorine-containing diamond coating under conditions that contribute to the formation of the resistor. 84. The method of claim 60, further comprising: depositing a metal bottom electrode under the fluorine-containing diamond coating; depositing a top electrode; and depositing the top layer under conditions that help form a resistor Patterned on metal. O:\56\56197-920926.ptc 第65頁O: \ 56 \ 56197-920926.ptc Page 65