CN1205367A - Electrochemical deposition process and appts. for preparing eka-diamond thin film - Google Patents
Electrochemical deposition process and appts. for preparing eka-diamond thin film Download PDFInfo
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- CN1205367A CN1205367A CN 97111993 CN97111993A CN1205367A CN 1205367 A CN1205367 A CN 1205367A CN 97111993 CN97111993 CN 97111993 CN 97111993 A CN97111993 A CN 97111993A CN 1205367 A CN1205367 A CN 1205367A
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- sedimentation basin
- chromatographic column
- diamond
- anhydrous methanol
- pond
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 10
- 239000010432 diamond Substances 0.000 title claims description 35
- 229910003460 diamond Inorganic materials 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 20
- 239000010409 thin film Substances 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 238000004062 sedimentation Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001802 infusion Methods 0.000 claims description 11
- 238000005137 deposition process Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Abstract
An electrodeposition process for preparing diamond-like membrane features that high-frequency pulse modulated high-voltage DC power supply is used as energy source and mathanol is chosen as electrodepositing solution to prepare said membrane in liquid phase, which is a diamond-like carbon membrane not containing hydrogen and having non-crystal structure. Obtained membrane has a resistivity of 10,000,000 ohm.cm and a microscopic hardness of 12-15 GPa. Its advantages are low deposition temp, uniform filming nature, easily contrallable reaction conditions and simple apparatus.
Description
The present invention relates to functional materials for the electrochemical deposition method and the device thereof of preparation diamond like carbon film.
Diamond all has very application prospects at aspects such as machinery, electronics, optics, acoustics, calorifics.Natural diamond is because storage is few, and the exploitation difficulty costs an arm and a leg, and can not satisfy industrial needs.
Artificially synthesizing diamond all carries out under High Temperature High Pressure at first, and the advantage of this solid phase reaction method is the bortz powder that can obtain near the natural diamond quality.But because reaction needed is at several ten thousand normal atmosphere, carry out more than 2500 ℃, thereby equipment and consumes expensive; And institute's synthetic bortz powder do not combine with substrate, also needs further combined process, limited its application.
People extensively adopt chemical vapour deposition (Chem ical VapourDeposition is called for short CVD) method to prepare diamond thin after the eighties.The advantage of this method is to obtain the higher polycrystalline diamond films of quality, compares with high temperature and high pressure method, and film is combined on the substrate, has enlarged its range of application; But substrate temperature is still very high during film forming, generally about 800～1000 ℃.This makes thermally sensitive electrical element and most of non-metallic material be difficult to serve as the film forming substrate of suitable diamond thin; Simultaneously, so high depositing temperature makes film produce internal stress, causes the bonding strength of film and substrate not high; In addition, the repeatability of preparation and problems such as stability and preparative-scale are still unresolved.These have all greatly limited the practical application of low-pressure vapor phase synthesis of diamond film.
Diamond-like carbon (Diamond-like Carbon or DLC) has a series of premium propertiess very similar to diamond, as high rigidity, high optical transmittance, high resistivity, chemical resistance etc.It also has film-forming temperature low (can reach room temperature) in addition, and area is big, and surface smoothness is good, and prepares characteristics such as difficulty is little.Thereby, at aspects such as optics, electronics, mechanical engineerings great using value is arranged all.
The preparation method of diamond like carbon film comprises chemical vapour deposition and physical vapor deposition.These technology all belong to and are that CVD (Chemical Vapor Deposition) method, its feature are the quasi-diamonds that reaction generates solid phase in gas phase.Adopt these CVD (Chemical Vapor Deposition) method, in general can under lower temperature, obtain the diamond like carbon film of better quality and sedimentation velocity faster.But it also has a significant disadvantages, i.e. deposition reaction need be carried out under vacuum condition, thereby difficult control of reaction conditions, and repeatability is bad, and preparative-scale is restricted.
In general, in liquid phase, adopt electrochemical method to prepare film, obtain the uniform film of quality easily, and easy control of reaction conditions, good reproducibility.But the rarely seen report of the research of diamond synthesis and diamond like carbon film in liquid phase.
People such as Maissel " verify by a large amount of experimental facts in thin-film technique handbook one book that great majority can sedimentary thin-film material also can be synthetic by electrochemical method in liquid phase in gas phase, and vice versa what they showed.For example plate Cu, adopt these two kinds of methods can.Be subjected to the inspiration of this theory, Namba[document 1] (＞1000V) method of the pure ethanolic soln of electrolysis has begun the trial of synthesis of diamond film in liquid phase at first to adopt high-voltage.Yet, from their paper, only there is the result of x-ray photoelectron spectroscopy to show that the main component in the sample is C, there is not other evidence to show that they have obtained diamond or diamond like carbon film.Subsequently, the mixing solutions of people such as Suzuki [document 2] electrolysis ethylene glycol-water, Raman spectrographic result shows that the main component in the sample is the C of graphite phase.Recently, people such as Novikov [document 3] report as ionogen, obtained diamond like carbon film, but they does not provide detailed preparation process condition with the liquid ammonia solution of acetylene.
In addition, do not see again relevant electrochemical deposition method or other in liquid phase the deposition method diamond synthesis or the report of diamond like carbon film.
[document 1] Y.Namba, J.Vac.Sci.Technol.A, 10 (1992) 3368.
[document 2] T.Suzuki, Y.Manita, T.Yamazaki, S.Wada, T.Noma, J.MaterSci, 30 (1995) 2067.
[document 3] V.P.Novikov, V.P.Dymont, Appl.Phys.Lett, 70 (1997) 200.
The present invention adopts electrochemical deposition method synthetic diamond like carbon film in liquid phase, purpose is characteristics of utilizing electrochemical deposition method to have,, film forming low as depositing temperature evenly, good reproducibility, equipment be simple etc., for enlarging the industrial scale of diamond like carbon film, and further enlarge its range of application, certain basis is provided.
The present invention for achieving the above object, following technical scheme is proposed: adopt high purity graphite as anode, negative electrode is a Si sheet to be plated, the high frequency pulse dc high-voltage power supply is an additional power source, voltage is adjustable in 0～2000V scope, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%, high-purity anhydrous methanol is an electric depositing solution, can heat simultaneously and stir electric depositing solution by the magnetic stir bar that is placed on the magnetic force heating stirrer in the solution, and by the temperature control instrumentation amount that links to each other with the magnetic force heating stirrer and the temperature of feedback control deposition process, flow to the flow of chromatographic column by the control of the variable valve on sedimentation basin side-lower chromatographic column port electric depositing solution, with the water that generates in the molecular sieve adsorption deposition process in the chromatographic column, the anhydrous methanol in the chromatographic column is held in the pond by the rising pipe inflow of chromatographic column lower end, the anhydrous methanol that will hold in the pond by infusion pump flows back to sedimentation basin by certain flow more again.It is characterized in that adorning in the sedimentation basin high-purity anhydrous methanol, high purity graphite and substrate to be plated are housed in the anhydrous methanol, sedimentation basin bottom dress has the magnetic force heating stirrer of magnetic stir bar, magnetic stir bar is stretched in the anhydrous methanol in the sedimentation basin, there is an opening below, side of sedimentation basin and is provided with variable valve and is connected with chromatographic column, the chromatographic column below is provided with one and holds the pond, holds between pond and the infusion pump to be connected with tubing, is connected with tubing between infusion pump and the sedimentation basin.
Compared with prior art, advantage of the present invention mainly contains: substrate temperature can be controlled at below 100 ℃, thereby the choice of substrate wide ranges; Since be reflected in the liquid phase and carry out, thus the condition of reaction more easy to control, good reproducibility, and obtain the uniform film of quality easily; The equipment of preparation is simple, more easily reaches the scale and the requirement of suitability for industrialized production.By above-mentioned advantage as seen, the present invention produces high-quality diamond like carbon film for large-scale industrialization and has positive meaning.In addition, owing to all obtain (class) diamond in solid phase and gas phase, therefore synthetic (class) diamond is for the thermodynamics and kinetics theory of development (class) diamond film also and crucial meaning arranged in liquid phase.
Preparation facilities of the present invention is provided by accompanying drawing 1.
Fig. 1 is the device one-piece construction synoptic diagram of preparation diamond like carbon film.
Primary structure is among the figure: sedimentation basin 1, high frequency pulse dc high-voltage power supply 2, graphite 3, substrate to be plated 4, temperature control meter 5, magnetic force heating stirrer 6, sorbent material 7, infusion pump 8, anhydrous methanol 9, variable valve 10, hold pond 11, magnetic stir bar 12, tubing 13, chromatographic column 14.
The present invention specifies as follows:
This preparation diamond like carbon film electrochemical deposition method and device thereof adopt high purity graphite 3 as anode, negative electrode is substrate 4Si to be plated, high frequency pulse dc high-voltage power supply 2 is an additional power source, voltage is adjustable in 0～2000V scope, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%, high-purity anhydrous methanol is an electric depositing solution, can heat simultaneously and stir electric depositing solutions by the magnetic stir bar 12 that is placed on the magnetic force heating stirrer 6 in the solution, and measure and the temperature of feedback control deposition process by the temperature control meter that links to each other with the magnetic force heating stirrer 5, control the flow that electric depositing solution flows to chromatographic column 14 by the variable valve on the sedimentation basin 1 side-lower chromatographic column port, with the water that generates in the 7 absorption deposition process of the adsorbent of molecular sieve in the chromatographic column.The anhydrous methanol in the chromatographic column is held in the pond by the rising pipe inflow of chromatographic column lower end, the anhydrous methanol that will hold in the pond by infusion pump 8 flows back to sedimentation basin by certain flow more again.It is characterized in that adorning in the sedimentation basin high-purity anhydrous methanol, high purity graphite and substrate to be plated are housed in the anhydrous methanol, sedimentation basin bottom dress has the magnetic force heating stirrer of magnetic stir bar, magnetic stir bar is stretched in the anhydrous methanol 9 in the sedimentation basin, there is an opening below, side of sedimentation basin and is provided with variable valve 10 and is connected with chromatographic column, the chromatographic column below is provided with one and holds the pond, holds to be connected with tubing 13 between pond 11 and the infusion pump, is connected with tubing between infusion pump and the sedimentation basin.
The present invention adopts electrochemical deposition method to synthesize diamond like carbon film, and gordian technique is choosing of electric depositing solution and deposition process parameters.Under structure of matter guide of theory, consider methyl alcohol (CH
3OH) has big specific inductivity, CH under the noble potential effect
3The OH molecule in electrode surface polarization distortion, forms active points easily; On the other hand, noble potential makes electrode surface form the activation lattice point of many high energy.Active points is adsorbed on the activation lattice point of these high energy, and electrochemical reaction takes place, and generates diamond like carbon film.Therefore, we select methyl alcohol as electric depositing solution, and the employing monocrystalline silicon piece is a substrate, provide energy with high-frequency impulse modulation DC high-voltage power supply, and concrete processing parameter is (deposition apparatus is seen accompanying drawing).
Distance between electrodes is 10mm, 50～60 ℃ of depositing temperatures, voltage across poles 1000～2000V, pulse-repetition 5～10KHz, pulse duty factor 80%.
In addition, before deposition, need carry out surface preparation earlier as the Si sheet of substrate.Substrate is placed on earlier in the hydrofluoric acid solution and soaked 30 minutes, to remove the SiO on surface
2Deng oxide compound.In methanol solution, use ultrasonication 20 minutes then, remove the impurity on surface.
For the strength of solution in the sedimentation basin is kept evenly, adopt magnetic force heating stirrer stirred solution, agitator can heat simultaneously, and by the temperature control meter feedback that is attached thereto and the temperature in the control solution.
Simultaneously, in deposition process, because the carbonaceous component in the solution constantly deposits to substrate surface, and generates water, so the carbon concentration in the solution is changing.In order to keep concentration constant, we have opened an osculum below sedimentation basin, from the sorbent material drying of effusive solution through chromatographic column shown in the drawings here, in the container of the high-pure anhydrous methanol solution of Sheng below flowing to, make methyl alcohol wherein flow back to sedimentation basin by certain flow (with flow to the identical flow of chromatographic column from sedimentation basin) by infusion pump.It is constant to guarantee so on the one hand in the sedimentation basin that the concentration of methanol solution remains, and methanol solution can be recycled.
Deposition results shows that the settling of silicon chip surface is not hydrogenous diamond-like carbon film (by Raman, X-photoelectron spectrum and infrared spectrum) with non-crystal structure, has certain resistance to chemical attack ability, and its resistivity is 10
7Ω .cm magnitude is between microhardness 12～15GPa.
Claims (2)
1. electrochemical deposition method for preparing diamond like carbon film, it is characterized in that adopting high purity graphite as anode, negative electrode is a Si sheet to be plated, the high frequency pulse dc high-voltage power supply is an additional power source, voltage is adjustable in 0～2000V scope, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%, high-purity anhydrous methanol is an electric depositing solution, can heat simultaneously and stir electric depositing solution by the magnetic stir bar that is placed on the magnetic force heating stirrer in the solution, and by the temperature control instrumentation amount that links to each other with the magnetic force heating stirrer and the temperature of feedback control deposition process, flow to the flow of chromatographic column by the control of the variable valve on sedimentation basin side-lower chromatographic column port electric depositing solution, with the water that generates in the molecular sieve adsorption deposition process in the chromatographic column, the anhydrous methanol in the chromatographic column is held in the pond by the rising pipe inflow of chromatographic column lower end, the anhydrous methanol that will hold in the pond by infusion pump flows back to sedimentation basin by certain flow more again.
2. device that is used to prepare diamond like carbon film, it is characterized in that adorning in the sedimentation basin high-purity anhydrous methanol, high purity graphite and substrate to be plated are housed in the anhydrous methanol, sedimentation basin bottom dress has the magnetic force heating stirrer of magnetic stir bar, magnetic stir bar is stretched in the anhydrous methanol in the sedimentation basin, there is an opening below, side of sedimentation basin and is provided with variable valve and is connected with chromatographic column, the chromatographic column below is provided with one and holds the pond, hold between pond and the infusion pump and be connected with tubing, be connected with tubing between infusion pump and the sedimentation basin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111993A CN1049931C (en) | 1997-07-10 | 1997-07-10 | Electrochemical deposition process and appts. for preparing eka-diamond thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111993A CN1049931C (en) | 1997-07-10 | 1997-07-10 | Electrochemical deposition process and appts. for preparing eka-diamond thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1205367A true CN1205367A (en) | 1999-01-20 |
| CN1049931C CN1049931C (en) | 2000-03-01 |
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| CN97111993A Expired - Fee Related CN1049931C (en) | 1997-07-10 | 1997-07-10 | Electrochemical deposition process and appts. for preparing eka-diamond thin film |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381882B (en) * | 2008-03-28 | 2010-06-23 | 北京化工大学 | Method for preparing diamond-like film by low voltage liquid phase electrodeposit |
| CN102605413A (en) * | 2012-03-21 | 2012-07-25 | 大连理工大学 | Hydrothermal-electrochemical method for preparing diamond film |
| CN103924286A (en) * | 2014-03-12 | 2014-07-16 | 张家港市港威超声电子有限公司 | High-efficiency extracting machine of artificial diamond |
| CN105332028A (en) * | 2015-11-10 | 2016-02-17 | 上海应用技术学院 | Method for establishing diamond-like film on surface of metal by electrolyzing organic matter |
| CN110306226A (en) * | 2019-07-25 | 2019-10-08 | 常州大学 | The method of electro-deposition carbon film in supercritical carbon dioxide |
| CN110875482A (en) * | 2018-08-29 | 2020-03-10 | 北京科技大学 | Method for preparing carbon film on surface of stainless steel bipolar plate by using graphite as carbon source |
| CN112877560A (en) * | 2021-01-12 | 2021-06-01 | 江西离子型稀土工程技术研究有限公司 | Diamond/copper composite material and preparation method thereof |
| CN113430612A (en) * | 2021-06-23 | 2021-09-24 | 哈尔滨工程大学 | Method for rapidly preparing diamond-like carbon film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465353C (en) * | 2004-12-24 | 2009-03-04 | 中国科学院兰州化学物理研究所 | Method for preparing composite film of carbon similar to generic diamond containing Nano granules of silicon dioxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1020158C (en) * | 1987-12-22 | 1993-03-24 | 昆明物理研究所 | Method for coating diamond-like carbon film on infrared lens of germanium and silicon |
| DE69105764T2 (en) * | 1990-01-29 | 1995-04-27 | Bausch & Lomb | Process for evaporating a diamond-like film on a low-melting substrate. |
-
1997
- 1997-07-10 CN CN97111993A patent/CN1049931C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381882B (en) * | 2008-03-28 | 2010-06-23 | 北京化工大学 | Method for preparing diamond-like film by low voltage liquid phase electrodeposit |
| CN102605413A (en) * | 2012-03-21 | 2012-07-25 | 大连理工大学 | Hydrothermal-electrochemical method for preparing diamond film |
| CN102605413B (en) * | 2012-03-21 | 2014-06-11 | 大连理工大学 | Hydrothermal-electrochemical method for preparing diamond film |
| CN103924286A (en) * | 2014-03-12 | 2014-07-16 | 张家港市港威超声电子有限公司 | High-efficiency extracting machine of artificial diamond |
| CN105332028A (en) * | 2015-11-10 | 2016-02-17 | 上海应用技术学院 | Method for establishing diamond-like film on surface of metal by electrolyzing organic matter |
| CN110875482A (en) * | 2018-08-29 | 2020-03-10 | 北京科技大学 | Method for preparing carbon film on surface of stainless steel bipolar plate by using graphite as carbon source |
| CN110306226A (en) * | 2019-07-25 | 2019-10-08 | 常州大学 | The method of electro-deposition carbon film in supercritical carbon dioxide |
| CN112877560A (en) * | 2021-01-12 | 2021-06-01 | 江西离子型稀土工程技术研究有限公司 | Diamond/copper composite material and preparation method thereof |
| CN112877560B (en) * | 2021-01-12 | 2022-02-08 | 江西离子型稀土工程技术研究有限公司 | Diamond/copper composite material and preparation method thereof |
| CN113430612A (en) * | 2021-06-23 | 2021-09-24 | 哈尔滨工程大学 | Method for rapidly preparing diamond-like carbon film |
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| Publication number | Publication date |
|---|---|
| CN1049931C (en) | 2000-03-01 |
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