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

Description

575681

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 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

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 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.

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.

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.

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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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 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.

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, 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, PF, V,

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 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 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). 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 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).

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.

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

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-

I

iw—IKi

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

/, Other dyes ’and improve the dryness of the coating deposited on the substrate

575681

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]

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 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

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

Page 29 V. Description of the invention (25) A coating with a thickness of 1060 angstroms is formed on the surface.

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 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 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

Page 575681

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 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. 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 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

* Evaluation sample in System 2 Deposition of fluorine-containing diamond paint

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,

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

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

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

Page 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

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).

Page 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

+ + + 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.

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.

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

Page 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

Page 42 575681 V. Description of the invention (38)

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 =

if

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.

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.

Page 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

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.

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 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

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.

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

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

Job 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

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

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).

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 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: ° ^

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.

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

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 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.

Page 55

Claims (1)

575681 ^ prime number 871: 2019, March 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 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 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 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 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 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 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 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 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 Page 65