TW200823313A - Method of coating carbon film on metal substrate surface at low temperature - Google Patents

Abstract

A method of coating carbon film on metal substrate surface at low temperature that consists the following steps: (a) metal substrate preparation: choosing a metal substrate whose soften temperature is higher than that of the afterward carbon film covering process. (b) catalyst layer pre-coating: pre-coating a catalyst layer of thicker than 0.01μm on the metal substrate surface. (c) carbon film coverage : using chemical vapor deposition process (CVD) to degrade and dehydrogenate carbon raw material at reaction temperature of 300DEG C to 900 DEG C and to coat a carbon film of 0.1 μm to 10 μm thick on the catalyst layer. Through pre-coating a catalyst layer on metal substrate, a highly graphitized and continuity compact carbon layer is prepared under low temperature. This method is suitable in producing metals of high electric conductivity and high corrosion inhibition such as metal diodes of polymeric electrolyte thin film in fuel battery and metal electrode of electrolytic cell.

Description

200823313 IX. Description of the Invention: [Technical Field] The present invention relates to a method for coating a carbon film on a surface of a metal substrate, and more particularly to a method for coating a carbon film on a surface of a metal substrate at a low temperature. Using a general chemical vapor deposition technique at low temperatures, a dense carbon film having high conductivity, high corrosion resistance, high adhesion, and high coverage is grown on the surface of a commonly used metal substrate. [Prior Art]

According to the survey of the Fuji economy of the Japanese private market company (Source: The Economics News, 13th edition, 2006/3/10), the market size of the main parts of fuel cells in 2005 was NT$100 million, which is expected to be 2020. The market size of fuel cell parts will grow rapidly beyond NT$60 billion (the total market size of the fuel Hongchi power generation system will reach NT$320 billion); the fuel cell's bipolar plates account for about 3% of the total cost of parts. %. The results of the survey are also not obvious. The demand for fuel cell vehicles will expand after 2015. The fuel cell market in 2012 will grow rapidly as the price of parts decreases.目4All kinds of fuel cells (high temperature type or low temperature type) bipolar plates (bip〇1w ^ 2 1 or electrolytic cell electrode () electrode commonly used materials include Shang 2 = ink, polymer 7 graphite powder composite, carbon / Carbon composite materials and metal materials, etc., the description of various materials is as follows: · Commercial graphite ^ Commercial graphite is currently used in the development of fuel 'bipolar plate and electrolytic cell electrode material in the fuel mine, ice soil π battery has the longest history of use The prototype of the battery is the best. Because of the graphite bipolar plate and other components, the measured data, reliability analysis 5 200823313 and Ge test and other materials are the most complete, so the conductivity, anti-recording, gas, properties and mechanical properties of graphite It is still used as a technical specification for parts such as bipolar plates. However, due to its complicated process (must be 2〇〇〇~25〇〇.. Reverse sintering, and must be piece by piece, use CNC to turn the precision gas flow path) It is easy to break, so the price of the ten-knife mussels accounts for about 3G% of the cost of fuel cell materials. Therefore, the use of inexpensive and usable alternative materials is the only way to promote fuel cells. 2 · Polymer / graphite Powder composite The graphite composite powder and the polymer composite material are cheaper than the commercial graphite. It is known that the injection flow molding (injeetlGn molding) is used to make the gas flow channel, and it is not necessary to use a CNC lathe, etc., and it will be supplied, warehouse, and the like. It also prepares for the precise processing of gas channels such as polymer electr〇iyte membrane fuel (pEMFc) bipolar plates, which can greatly reduce the cost of materials and processing. The process, and the anti-money and stone: no different 'currently has been the protagonist of the proton exchange membrane fuel cell bipolar plate /; lL kernel because the electrical impedance of the bismuth molecular graphite composite is still higher than the commercial high-energy 2 ink ' Therefore, the important characteristics such as power generation efficiency are still inferior to those of graphite bipolar plate fuel. 'In addition, the gas permeability and mechanical properties of polymer graphite composites are still not good. - People: can be measured and data still needs to be established for a long time, so the polymer Graphite: Whether the composite material is the mainstream of the future 1635 fuel cell bipolar plate is still uncertain 0 ^ · Carbon/carbon composite material has to be repeatedly impregnated and carbonized, so the price is better than commercial stone Cheap, but more expensive to process other materials autumn box Η Zhe recognize a ^ ^ shellfish and graphite are pretty, but nor has a lot to promote the potential. 62008233134 · Metal Materials

As usual. Metal bipolar plates have been considered as the mainstream of future fuel cell bipolar plates 'because their price is very low, conductivity, mechanical properties and gas in graphite' and suitable for mass production processing, such as gas flow, "forming" However, the corrosion resistance of the metal material is not: the metal materials such as stainless steel, nickel alloy, and alloy are prone to spoil and release metal ions in the strict operating environment of the fuel cell, thereby poisoning the proton conductive membrane (such as DuPont (4) secret (10) and nano-scale platinum catalysts cause life-span problems such as the gradual decline in fuel cell power generation efficiency.

An important topic for graphite replacement materials such as wide metal bipolar plates. Therefore, the metal bipolar plate of the IJ is often coated with a titanium nitride (TiN) coating film having conductivity and resistance. However, the conductivity of TiN is not as good as that of graphite. It is necessary to plate a layer of gold (Au) or # ((1) and other noble inert metal film on the titanium nitride coating film to reduce the contact resistance of the bipolar plate, but it significantly increases the cost and cost. The metal bipolar plates of the outer layer of titanium nitride (or Nitrix/gold) are significantly higher than the original metal substrate, but still not as good as graphite. The service life of graphite bipolar plates is far more than 50 (8). Hours, but the metal substrate coated with titanium nitride/gold has a life of only about 2,000 hours. Therefore, how to improve the corrosion resistance of the metal bipolar plate without degrading its conductivity is indeed a study to improve the resistance of the metal to the surname. It has been used for a long time. In the early days, it was coated with an inert material on the surface of the metal substrate. For example, the inert metal silver (Ag), gold, pat, and (Pd) were placed on the surface of the metal substrate. In addition, # has a high conductivity, suitable for electronic components related applications. However, 'the use of these precious metals will greatly increase the cost of materials. Its: 7 200823313 Although the coated material has excellent resistance to residual characteristics' but does not have good Conductivity, for example Plasma enhanced chemical vapor deposition (PECVD) to coat diamond like carbon film (DLC film) or use high-scoring, sub-coating layer. The technology of growing carbon materials is often used in the production of carbon nanotubes (CNT) powders, carbon nanotube display panels or carbon nanotubes, such as vacuum arc method, using carbon electrodes and nickel powder. The medium is made of carbon nanotube powder, and the array recording metal crucible (thickness only 〇·〇〇3~〇·〇ι # m) is pre-made by the lithography etching technique, and then PECVD 4 'private surface (>900 ° is used) C) Catalytic growth of arrayed carbon nanotube emitter electrodes for use in flat panel applications, etc. There are also methods for depositing nanometer carbon spheres of a multi-layer graphite layer on a substrate by means of an electric clock method. One of the membrane processes is a polymer coating pyrolysis method. First, a specific polymer, such as an organic solution such as acetylenic p〇lymer φ, is coated on a metal surface, and then carbon is obtained by thermal cracking. The coating layer of 90/〇 is used to protect the metal substrate, but the film thickness of the carbon film prepared by this method is thicker than that of the chemical vapor deposition coating film, and the adhesion of the carbon film and the uniformity of the film thickness It is not as good as the chemical vapor deposition process. In addition, the process technology is as follows: firstly, the surface of the aluminum substrate is injection-molded to adhere a gas flow path of a conductive polymer composite, but the composite layer is formed by 4匕^ Because it is not completely airtight, so it can not block the corrosive environment under the condition. Therefore, the aluminum plate substrate must be coated with shellfish inertia or titanium nitride, chromium nitride (CrN), etc. 8 200823313 Layers, the process is more complicated. SUMMARY OF THE INVENTION The present invention is not capable of being carried out at a low temperature, and a carbon film having a conductive property and a high corrosion resistance is applied to the surface of the metal substrate. The object of the present invention is to provide a metal. A method for coating a carbon film on a surface of a substrate at a low temperature, which can coat the surface of the metal substrate at a low temperature, and the carbon film has a south conductivity and a surface resistance. In order to achieve the above object, the method of the present invention for low-temperature carbon film on the surface of a metal substrate comprises the following steps: preparing a metal substrate: using a metal having a softening degree higher than a reaction temperature of a subsequent carbon film coating step Pre-plated catalyst layer: a pre-plated catalyst layer with a thickness exceeding 〇〇1 # m on the surface of the metal substrate; a smectite anti-film • using a chemical vapor deposition (chemicai vap〇r deposition; CVD) process, using The carrier gas feeds the φ carbonaceous raw material into the chemical vapor deposition reaction chamber, and the carbonaceous raw material is cracked and dehydrogenated at a reaction temperature of 300 ° C to 900 ° C, and the thickness of the catalyst layer is coated on the catalyst layer. 〇·1μιη to 1〇μπι carbon film. The specific efficiencies that can be achieved by the present invention include: 1. The corrosion-resistant metal material on the surface of the metal material is more "processable and formable" and "massable" than the ceramic material (including graphite), but its corrosion resistance Inferior metals (Pt, An, Pd, etc.) are not as good as common ceramic materials, and their corrosion resistance is still less than that of highly inert ceramic materials such as graphite. For the technical regulations that are very demanding, the 2008 20081313 field, such as fuel cell metal bipolar plates, does not even allow trace amounts of ions to be ionized and poison the proton conducting membrane and nano-scale platinum catalyst. The stone anti-film will be superior to Titanium Nitride (TiN) & other metal carbides, metal oxides and the like. Therefore, the surface of the metal substrate is covered with an inert carbon film to solve the problem of metal rot. 2. Improve the conductivity of the corrosion-resistant protective carbon film

If the metal material coated with the carbon film on the right is used to replace the commercial graphite block (for example, in the energy industry such as 胄M and low 35 fuel cells), the guide rate of the anti-membrane must be greatly increased. Conventionally, the carbon film used in jade industry is often a run-down type diamond-like film, which is electrically an insulator. Therefore, the present invention must increase the degree of graphitization of the carbon film to improve the conductivity of the protective film. Since the process such as the physical germanium deposition method is easy to generate a material structure such as a high resistivity drill film, the pyrolysis type chemical vapor deposition process, the plasma induction process, the PECVD process, and the microwave power are used in the present invention. The degree of graphitization of the k-direction carbon film by plasma chemical vapor deposition. The present invention suitably performs a low-temperature chemical vapor deposition process on the catalyst layer to grow a dense and continuous carbon film, and the material of the carbon film includes a conductive structure such as graphite or #crystalline carbon. The carbon film combines high electrical conductivity with high corrosion resistance. 3. The chemical vapor phase reaction temperature required to reduce the carbon film Generally, the heat treatment temperature of the carbon fiber process and the block graphitization process are above 1000 ° C. If the thousand 铋 铋 古 古 古 it r r r And, the grazing graphite material must even be heated to above 2000 °C and carry out multiple attacks, 兮: moxibustion test - re-infiltration treatment of the 仃 仃 人 person, the present invention uses catalytic thin film technology The carbon film growth temperature can be lowered to below 9 , to perform a carbon film coating process on a metal material which is easy to be softened at a high temperature.利 10 200823313 4 ·Formation of a continuous and dense carbon film The traditional process of producing a highly graphitized carbon fiber, carbon cloth or carbon film 'often must be heated above i, if you want to get close to pure stone'

The material 'requires a force D i 1800t or more' and these materials have voids and pores' cannot form a continuous and dense carbon film. As for the carbon nanotubes and other materials, although they can also have a high degree of graphitization, they are stacked fluffy thin tubular powders, and it is not easy to grow a dense carbon film on the metal surface, so the resistance to the surname is not good. The invention adopts a low-vapor deposition process after pre-plating a specific metal catalyst layer of a proper thickness on the surface of the metal substrate, so that a continuous and resistant south carbon residual carbon film can be grown. [Embodiment] As shown in the first figure, the method of the present invention for coating a carbon film on a surface of a metal substrate at a low temperature comprises the following steps: preparing a metal substrate: a reaction having a softening degree higher than that of a subsequent coated carbon film step The metal is a substrate; since the ideal reaction degree of the carbon film coating step of the present invention is between 300 ° C and 900 ° C, it is necessary to select a metal having a higher softness than the temperature in the process temperature, such as stainless steel. , nickel alloy, flat carbon steel, aluminum alloy, copper alloy and titanium alloy. Pre-plating catalyst layer: pre-plating a catalyst layer with a thickness exceeding 〇〇1 # m on the surface of the metal substrate; in order to grow a high-graphitization private stone anti-film at a lower chemical vapor reaction temperature, it is necessary to use an appropriate Thin film catalyst technology, found that nickel (Ni), gu (c), iron (Fe), platinum (pt), | bar (pd), silver (Ag) and other transition metals and their alloys have a catalytic carbon film "graphite Therefore, after pre-plating such a metal catalyst layer on the surface of the metal substrate, it is remarkable that the thickness of the catalyst layer is significantly reduced in addition to the portion required for the subsequent step of coating the highly graphitized carbon film. :1 When the thickness of the alloy-forming layer is less than 〇.〇1, it is easy to cause the shape of the membrane. When the catalyst is formed by the chemical vapor deposition process, the island-like catalyst particles are not easy to form continuity: := Shape or independent sphere in ~ ' As long as it does not peel off, catalyst 2: The membrane film of the catalyst layer can be used for steaming ore and strontium ore. Process technology. Coating, electroless plating, etc. coated carbon film: using ... phase deposition (― 聪; (d)) process, using carrier gas (coffee p carbon-containing raw materials to send chemical vapor deposition reaction chamber, so that carbon-containing raw materials in reverse shore temperature 3, C to cleavage dechlorination, and coating on the catalyst layer thick: for the addition of i 1 () μιη carbon film; carbon film thickness is too thin to resist rot (four), too thick carbon film is easy to produce The present invention adopts a chemical vapor deposition technique instead of the vapor deposition (PVD) of the material I because the latter is easy to generate a low-conductivity diamond-like structure. The chemical vapor deposition process used in the present invention can be It is a commercially available thermal decomposed chemical vapor deposition, plasma enhanced chemical vapor deposition (PECVD) or microwave chemical vapor deposition (microwave chemical vapor deposition). Vapor deposition, etc. The carbonaceous raw material introduced into the chemical vapor deposition process is a gas, a liquid or a solid having a low-temperature cracking dehydrogenation property, and a gas such as decane (CH4), 12 2008 23313 w(C2H2), ethylene ((iv)), etc. 'Liquid such as methanol (CH0H), E-trans (c2H5〇H), etc. 'Solids such as stone signs, and two must use carrier gas ^10 (...) ^^ Raw materials ^ ^ Φ . .. , in the chemical vapor deposition reaction chamber, the carrier gas used may be argon-helium drop-delivery/arc (Ar), oxygen (He) (ln), or nitrogen (N2), hydrogen ( H), ammonia gas (NH3) and other reducing gases. The ratio of the stone-containing anti-feedstock to the carrier gas of 2 to the field can obtain a better degree of graphitization, ^. y , ^ M mixed gas of acetylene and helium For example, the volume concentration ratio is as small as 0.015 and high to pure C2H2, both of which can be high (〇) carbon film, preferably the volume of acetylene is “》 〇 〇 5 5 5 5 下 下 下 下 下 下 下 下 下In the ± and sub-forms, the R value is the index value of the degree of graphitization measured by the Raman spectrometer. When the R value is zero, the graphitization degree is (10)%. The larger the R value, the more the graphitization degree is. = RD/RG, where RD is the integral of the D-band of the Raman spectrum; and rg is the integral of the G-band of the crying ritual. The above carbonaceous material and carrier gas Although the concentration ratio changes, the total gas partial pressure is still slightly larger than lamm, so these mixed gases flow through the reaction chamber at a constant flow rate in the chemical vapor deposition process. The total working pressure of the chemical vapor deposition process of the present invention is 1X 10-3torr to 760t〇rr, the present invention finds that 'if the vacuum pumping system is used, the total gas pressure of the mixed gas in the reaction chamber is reduced to l0-2_10-3t〇rr (the concentration ratio of the mixed gas is maintained at 13 200823313) ), the reactivity of the carbon film process can be reduced by about 1 〇 (Tc). The carbonaceous material used in the present invention may be mixed with a specific transition metal compound to appropriately change the content of a specific metal element in the carbon film, thereby adjusting the conductivity and mechanical properties of the carbon film. These transition metal compounds may be tetra-titanium ("Π(ΝΗ2)4), tetra-titanized titanium (Tici4), hexa-chemical (m〇(co)6), tungsten hexahydrate (W(C0)) 6), chromium hexacarbonyl (cr(co)6) and other common metal compounds, etc. C> The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way. Embodiment 1 In this embodiment, AISI 304 stainless steel is selected as the metal substrate, and the metal substrate is sputtered with different thicknesses of Ni catalyst layer (0·4μιη to 0·8, followed by thermal 4 decomposing chemical vapor deposition). Method, the time of the heat treatment process: the temperature relationship is as shown in the second figure. First, the tubular chemical vapor deposition furnace draws two to 10 torr, and then rises to 700 °c within 6 minutes, during the period [if necessary Vacuuming the sub-pass into lat argon, argon and flowing out of the reactor at a flow rate of nd cubic ( (d) (nd) cubic centimeter per minute; the reactor is then subjected to a reduction-activation heat treatment for 1 hour under the protective atmosphere of Utm hydrogen, helium gas and The reactor was discharged at a flow rate of 2 〇〇sccm; finally, the reactor was passed through a mixed gas of 3% acetylene and 66 vol% hydrogen at a total pressure of 1 gal, and a chemical vapor deposition process was carried out for 3 hours. After the reaction was completed, the hydrogen was turned off. Fasten with B, and first pass nitrogen gas 〇〇sccm 14 200823313 Dilute the reactive c body to stop the subsequent chemical vapor deposition reaction, and prevent the reactor from being cooled. These drape: pancreas The test piece is measured by the four-point probe method, and the resistance values of the column, the table, the graphite block and the non-recorded carbon film of the non-recorded carbon film are also listed in the table. Comparison. " —Compared test piece resistance value~~~---~Λΐ^ΐΩ/cm2) Stainless steel 7 nickel layer (〇·4μιη) / carbon film (1 ·5μηι ) 4.805 Stainless steel/nickel layer (〇·6μηι ) / carbon film (1 · 5μηι ) 4.901 stainless steel / nickel layer (〇 · 8μιη) / carbon film (1.5μιη) 5.304 4.746 6.220 + stainless steel substrate commercial graphite block from Table 1, the steel coated carbon stainless steel substrate Substrate phase f, increase the thickness of the nickel plating layer, the micro-mountain almost and stainless can retain the high conductive sheet resistance value, but still lower than the commercial graphite block, I, ^ not pound steel plate method on the surface of the stainless steel substrate After the carbon film, it is better to use the conductivity of the present invention than the commercial graphite material. Example 2 15 200823313 This example is a pre-sputtering Ν.4 μηι Νι catalyst layer on an AISI 304 stainless steel substrate, followed by a thermal cracking chemical vapor deposition process, and the Renlu membrane is in 6 different The reaction temperature is deposited (5 〇, rc, 6 〇〇〇 c, 65 〇 ° C, 7 〇〇 ° C, 750 ° C, 8 〇〇. (:), the chemical vapor deposition reaction atmosphere is 60 v〇l The carbon film obtained from the mixture of % acetylene and 4〇v〇1% hydrogen was deposited at a rate of 3 J %. The results of the observation showed that the surface morphology of the carbon film was deeply affected by the reactivity and other chemistry. Under the influence of vapor deposition conditions, when the reactivity is 500 ,, the carbon material deposited on the surface of the stainless steel is loose and not formed. When the degree of reaction rises to 60 (rc, the deposited carbon layer has a flat shape, but is not continuous. The film, microscopically, has a scratched metal surface that is not obscured by the carbon film. When the reactivity is in the range of 650 ° C to 700 ° C, the continuous carbon film is uniformly and evenly grown on the nickel-plated catalyst layer. On the stainless steel test piece. When the degree of reaction is increased to 750 ° C, the carbon film is cracked. When the reaction The degree is as high as 800. (: When the carbon film is peeled off from the stainless steel substrate. Embodiment 3 This embodiment is to use a thermal cracking type chemical vapor deposition method on a two-piece stainless steel substrate, and a piece of stainless steel substrate is splashed in advance. The ruthenium plating layer of the ruthenium coating is 6 ruthenium, and the other stainless steel substrate is not pre-plated with the catalyst layer. The reaction temperature for depositing the carbon film is 70 (rc, the reaction atmosphere is 5 〇v 〇 1% acetylene and 50 vol The mixture of hydrogen gas and carbon film deposition time is 3 hours. Finally, the corrosion rate of the test piece is measured by a constant potential meter, the electrolyte is 〇·5μ16, 200823313 hurricane aqueous solution, the reference electrode is a-, the scanning potential range is - 0.6 v to ^ ^ is extremely Pt, and the polarization curve is as shown in the third figure. “The speed is 1〇·, when the carbon film is directly deposited on the stainless steel substrate (not like 〇, the subsequent chemical vapor deposition process) The grown stone ^! two pores of carbon material are piled up, there is no continuous coating of carbon film, and the acid will infiltrate the carbon under the sputum and contact the steel substrate, so : 圭's wide line shows the typical metallic sexual rot behavior (Taver: for; ltd The surname potential is about WV. Li (4) (4), κλ.Μ (Inductively 〇〇upled plasma Spectr〇meter, ICp. MS) analysis of the metal element content of the A% aqueous solution that has been subjected to the rot (4) test, and the stainless steel substrate is found. Some iron (Fe), chromium, nickel (10) and other elements of the poem H2S〇4 aqueous solution, while the carbon film of the non-rust steel substrate and commercial graphite (Poco AXF_5QCF) are free of metal elements dissolved into the aqueous solution, such as Table 2 shows the content of metal elements in H2S〇4 aqueous solution (unit: ppm)

Stainless steel not steel / nickel (〇·6μιη) / carbon (1 ·5μηι ) ink POCO AXF-5QCF ... Cr

1.725 nil nil *Inductive electrospinning spectrometer has been unable to detect the spectral information of this element. If the stainless steel substrate is first plated with a 0.6# m nickel catalyst layer, then proceed to 17 200823313 for chemical vapor deposition process (ie test piece) Ss/06#mNi/c) will produce a dense and dense carbon film. The polarization curve has no typical metal rot behavior: the corrosion potential does not exist, and its reaction current is very weak, only .1〇 The level of A/Cm2, the current value is constant at any low or high potential. This signal is the current generated by the adsorption and desorption reaction of hydrogen ions on the surface of the carbon film, not caused by the metal rot. Analysis of the completed surname test ^ H2so4 water soluble &; found that no metal ions dissolved in the residual liquid, showing that the carbon film is not penetrated by the rot money, the coverage of the stainless steel surface to maintain continuity and compact Sex. This polarization curve is similar to the polarization curve of commercial graphite block (waste brand poco, model AXF_5QCF). In the scanning potential range to + i lin, i Leifa Μ + #, 匕 _ ^ eight book values are also close The temple setting shows that the %I of the surface of the test piece has almost the same corrosion resistance as graphite. Embodiment 4 • In this embodiment, a nickel catalyst layer of different film thickness (〇4_i Ο.-) is pre-splashed on a commercially available carbon steel (by -4. wt% C) substrate, and then heat is applied. In the pyrolysis chemical vapor deposition process, the reaction temperature of the carbon film is 85 〇, the deposition time is 3 hours, and the reaction atmosphere is a carbon film obtained by mixing gases of different ratios of methyl and 2 gas and f: 3⁄4 and argon. The test piece was measured by Raman spectrometer (R嶋nspectr〇mete〇), and the degree of graphitization of the carbon film of the chemical vapor deposition process parameter was shown (the effect of r is very large, as shown in Table 3. The data in Table 3 It is known that the atmosphere of the reaction gas and the thickness of the catalyst bond layer 18 200823313 degree influence the degree of graphitization of the carbon film is very large, and the mixed gas of methane and hydrogen is better than the mixed gas of the system of argon and argon. Small), the preferred gas mixing ratio is 33% f burning & 67% hydrogen, the R value measured on the test piece is close to the order (〇〇6~〇1〇), the degree of graphitization of the carbon film is known. Nearly 100% 〇 Table 3. Depositing carbon films on nickel layers of different thicknesses and using Raman spectroscopy Measured in graphitization processes Tang (p / Gu, C: rfc no value), the reaction temperature was 85 (TC, the reaction time was 3 hours

Test piece vol%) 5〇CH4-50 Ar 33 CH4-67 Ar 33 CH4-67 H2 5〇CH4_50 Ar 33 CH4-67 Ar 11^CIV67 1.11 1.01 0.06 1.06 0.80 0.10 Carbon steel / nickel (0.4//m) / Carbon (15//m) Carbon steel/recorded (〇·4// m) / carbon (15// m) Carbon steel / nickel (0.4/zrn) / carbon (l5//m) Carbon steel / nickel (io #m) /carbon (15#m) carbon steel / nickel (1·〇# m) / carbon (15# melon)

: ΓΤ ~~ ~_\L u ^The integral degree of the Raman spectrum is the integral sound of the G-band of the crying spectrum, the stone of the membrane is like the life & mountain, the lower the R value is the carbon 胲The degree of graphitization is more, when the R value is 100% graphitized. When the carbon film is close to the gas source of the growing carbon film, the test piece showing a thick graphite layer in the carbon film is displayed (1·0/Ζ when using a mixture of decane and argon gas) The measured R value can be increased to more than 1 · ,, and the structure of the amorphous carbon is increased, while the nickel touch 19 200823313 m Nl ) is also superior to the thinner test piece of the nickel catalyst layer (0 4 / 4 m N. From the present embodiment, it can be explained that the carbon film having a high degree of graphitization can be produced by the finalization of the chemical vapor deposition process parameters, thereby improving electrical properties such as electrical conductivity and contact resistance of the film. After optimizing the composition ratio of the reaction gas, a carbon film close to 100% graphitization can be obtained (that is, the R value is close to zero value). [Simple description of the drawing] $ - The figure is a flow chart of the present invention. 2 is a heat treatment flow chart of the first embodiment of the present invention. The second figure is a polarization curve of the third embodiment of the present invention. [Description of main component symbols]

Claims (1)

200823313 X. Patent application scope: 1 · A method for coating a carbon film on a surface of a metal substrate at a low temperature, comprising the steps of: preparing a metal substrate: selecting a metal having a softening degree higher than a reaction temperature of the subsequent carbon film step a substrate; a pre-plated catalyst layer; a catalyst layer having a thickness of more than m on the surface of the metal substrate; a coated carbon film: using a chemical vapor deposition (CVD) process, using a carrier gas The carbonaceous raw material is sent to the chemical vapor deposition reaction chamber, and the carbonaceous raw material is cracked and dehydrogenated at a reaction temperature of 300 ° C to 900 ° C, and the thickness of the catalyst layer is Ο.ΙμίΉ to ΙΟμιη Carbon film. [2] The method of claim 1, wherein the chemical vapor deposition process is a decomposed chemical vapor deposition process, as described in claim i. The method wherein the chemical vapor deposition process is plasma enhanced chemical vapor deposition o 4 · the method of claim i, wherein the chemical vapor deposition process system It is a microwave chemical vapor deposition. 5. The method of claim 1, wherein the metal substrate is selected from the group consisting of stainless steel, nickel alloy, flat carbon steel, aluminum alloy, steel alloy, and titanium alloy. 21 200823313 The material of the second layer of the patent application is selected from (4) (NiWi (c^ = two of the catalyst palladium (P〇, deduction, ), iron (Fe), surface (Pt), 7 · / ( Group of Ag) and its alloys. σ Application for the scope of the first layer of pre-mineralization is vapor deposition. μ method 'in which the catalyst 8 is as described in claim 1 of the patent scope, 1φ layer pre- The plating method is ruthenium plating. The catalyst 9 in #, as described in the first paragraph of the patent application scope, and the # layer pre-clock method are electric money. "The method, wherein the catalyst 10. If applying for a patent The range i-th layer blue mode is no electricity I 11 · As described in the patent application scope, the hydrogen reduction and activation catalyst layer is carried out in the pot before the step (4). 12 · If the patent application scope is 1 The method described in the above, wherein the carbonaceous material: is selected from the group consisting of a burnt (ch4), an acetylene (c2h2), an ethylene (4) H4), a methyl (CH30H), an ethanol (c2H5〇h), a stone insect. A group consisting of a rat and a camphor. The method of claim 1, wherein the carrier gas system is selected from the group consisting of盏/ττ, 卜, 虱 虱 (Ar), helium (He), nitrogen (ν2), hydrogen (Η2), ammonia & (then 3) and their mixed gases. 1 4 · If the scope of patent application is 1 The method according to the invention, wherein a transition metal compound is mixed in the carbonaceous raw material, and the transition metal compound is selected from titanium tetrachloride (T^NH2) 4), titanium tetrachloride (TiCl4), and molybdenum hexahydrate. (Mo(CO)6), tungsten hexahydrate (w(c〇)6) or chromium hexacarbonyl (Cr(c〇)6). 22 200823313 , 1 5 · as described in item i of the patent application The method wherein the total working pressure of the gas phase of the gas phase is from k... gas (4) to 76 〇t〇rr. The method of claim 2, wherein the carrier gas system is hydrogen. The method of claim 16, wherein the carbonaceous material is a methane. 1 8 · The method of claim 7, wherein the volume concentration ratio of xenon to hydrogen is 33. % A burnt with 67% chlorine. 9 As described in the patent scope of item 18, the straight-through coating of the carbon film step 浐 _ _, A, the preferred reaction temperature is 800 C 90 〇 °c. 2 〇 · The method of claim 1 g of the metal substrate is stainless steel. 2 1 The method of the catalyst layer according to the method of claim 20 is nickel. 2 · The carbonaceous raw material described in item i6 of the patent application scope is acetylene. No. 3, as in the case of the acetylene and hydrogen described in Item 2 of the scope of the patent application, the ratio of the elongation is 0·01 5 To 15 rooms. ^ 4 (6) The method described in claim 23, the optimum reaction temperature for the money film step is shouting to 75 吖. The method of the whole genus 1: Sun 1 ° patent application range No. 24 to the substrate is stainless steel. 6. The material of the de-catalytic layer is nickel as described in claim 25 of the patent application. Among them, one of them is 23 of them.