CN103266306A - Method for preparing graphene or ultrathin carbon film by PVD (physical vapor deposition) technique - Google Patents
Method for preparing graphene or ultrathin carbon film by PVD (physical vapor deposition) technique Download PDFInfo
- Publication number
- CN103266306A CN103266306A CN2013101906428A CN201310190642A CN103266306A CN 103266306 A CN103266306 A CN 103266306A CN 2013101906428 A CN2013101906428 A CN 2013101906428A CN 201310190642 A CN201310190642 A CN 201310190642A CN 103266306 A CN103266306 A CN 103266306A
- Authority
- CN
- China
- Prior art keywords
- substrate
- graphene
- ultrathin carbon
- carbon films
- acetylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a method for preparing a graphene or ultrathin carbon film by a PVD (physical vapor deposition) technique, which comprises the following steps: putting a substrate on a substrate rack in a deposition chamber, and carrying out glow cleaning on the substrate surface; introducing an acetylene-argon gas mixture into the gas mixture at 70-100 DEG C in an argon environment under the conditions of vacuum degree 0.5-1 Pa and the substrate voltage bias -200V; opening an anode layer ion source to ionize the gas mixture, wherein the voltage of the anode layer ion source is 300-500V in the ionization process, the acetylene is ionized to generate carbonous cations, and the cations bombards the substrate under the action of an electric field and deposits on the substrate; and after the deposition is finished, annealing under vacuum conditions for 1-2 hours, thereby preparing the graphene or ultrathin carbon film on the substrate surface after the annealing is finished. The method provided by the invention can satisfy the large-scale preparation of uniform-thickness graphene or ultrathin carbon films, and has important industrial application prospects.
Description
Technical field
The present invention relates to a kind ofly prepare the method for Graphene or ultrathin carbon films with the PVD technology, belong to the thin-film material technical field.
Background technology
Carbon is a kind of element that nature extensively distributes, and exists in a variety of forms, and common have graphite, decolorizing carbon and diamond, and the carbon nanotube of discovered in recent years, Graphene etc.Performance between the carbon of different shape has very big-difference, is because carbon can form several stable hydridization forms, just sp but trace it to its cause
1Hydridization, sp
2Hydridization and sp
3Hydridization.Graphene refers to the mono-layer graphite synusia, only has an atomic size thick, by sp
2The carbon atom of hydridization is closely arranged the cellular crystalline structure that forms.C-C in the Graphene is about and is 0.142nm.Three σ keys are arranged in each lattice, connect very firmly, formed stable hexagon shape.Image, Graphene is exactly the crystal by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape, and in addition, except proper single-layer graphene, double-deck and minority layer graphite synusia also is classified as the Graphene category in a broad sense.
Graphene is owing to have good physics strangeness and electrical properties, and very wide in the associated materials application facet prospect of semiconductor function device: Graphene has excellent optical property, and theoretical and experimental result shows that the single-layer graphene light transmission rate is 97.7%; The interference that electronics in the Graphene is subjected to seldom is difficult for scattering takes place when transmitting in Graphene, and mobility can reach 2 * 10
5Cm
2/ (Vs), be about 140 times of silicon electronic mobility.The method for preparing at present Graphene mainly contains (one) solid phase method: as the mechanically peel method, Graphene is separated from highly oriented pyrolytic graphite by the mechanically peel method at first, but this method output is little and the difficult control of size, is only applicable to fundamental research among a small circle; (2) liquid phase method: as oxidation reduction process, ultrasonic dispersion etc., but the Graphene by the preparation of this class methods does not also have crystallization degree high or be difficult to shortcomings such as purifying and transfer; (3) chemical Vapor deposition process: as chemical Vapor deposition process in conjunction with dissolving-liberation method (CVD), this method has bigger advantage at the Graphene of preparation individual layer, but only there is a very little part to separate out the formation Graphene behind the carbon quenching with the dissolving of CVD method, thickness is wayward, and the CVD method needs the high temperature more than 1000 ℃ and can produce waste gas, is unfavorable for energy-conserving and environment-protective; Ion implantation in addition also is to prepare the comparatively effective a kind of method of Graphene at present in conjunction with thermal treatment-cooling liberation method.
Summary of the invention
The invention provides and a kind ofly prepare the method for Graphene or ultrathin carbon films with the PVD technology, solved the deficiency in the background technology, this method can satisfy extensive, the Graphene of thickness homogeneous or the preparation of ultrathin carbon films, has important prospects for commercial application.
Realize that the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind ofly prepare the method for Graphene or ultrathin carbon films with the PVD technology, may further comprise the steps: at first substrate is put on the substrate frame of deposit cavity, aura is carried out on the surface of substrate clean; Afterwards ar gas environment, vacuum tightness 0.5Pa～1 Pa, 70 ℃～100 ℃, substrate bias-50 V～-condition of 200V under, feed the mixed gas of acetylene and argon gas in the deposit cavity; Open anode layer ion source to the mixed gas ionization, the voltage of anode layer ion source is 300～500V during ionization, and acetylene produces after by ionization and contains carbocation, and positively charged ion deposits to the substrate bombardment and at substrate under electric field action; Deposition is finished the back 1～2h that anneals under vacuum condition, annealing temperature is 600～900 ℃, anneals can make Graphene or ultrathin carbon films at matrix surface after finishing.
Adopt cathodic arc ion plating membrane method deposition one deck to play the metal catalytic layer of katalysis on the substrate, metal is Cu or Ni.
The manufacturing process of described metal catalytic layer is as follows: after the aura cleaning of substrate surface is finished, ar gas environment, substrate bias-50 V～-condition of 200V, vacuum tightness 0.1Pa～1Pa under, open multiple arc target, voltage on the metal targets is 20V, electric current is 40～100A, metal generates metal catalytic layer in the substrate surface deposition, and depositing time is 5～10min.
Described substrate is silicon substrate, silica membrane substrate or tinsel.
Described aura cleans: under the condition of ar gas environment, vacuum tightness 2.5Pa, substrate bias-800V, substrate surface is carried out aura clean 20min.
When feeding the mixed gas of acetylene and argon gas in deposit cavity, the flow of acetylene is 10～20sccm, and the flow of argon gas is 60～80sccm.
Graphene or ultrathin carbon films substrate in the process that substrate surface deposits rotates with substrate frame, and rotating speed is 3rmp.
Speed of cooling during annealing is 10 ℃/min.
The present invention adopts hydrogeneous acetylene to rise as carbon source, needs in addition easily to obtain because argon gas is cheap, so adopt argon gas to assist ionization here with the auxiliary ionization of rare gas element.Acetylene gas is the positively charged ion of carbon and hydrogen through the anode layer ion source ionization, and carbon ion is attracted by negative bias, forms Graphene or ultrathin carbon films at substrate, and argon ion can etch away hydrogen in the film to the bombardment of substrate, thereby reduces sp
3The formation of hybrid bond, vacuum annealing under certain condition then, thus high-quality Graphene or ultrathin carbon films obtained, wherein can obtain the ultrathin carbon films of homogeneous in 600 ℃ of annealing of low temperature, 900 ℃ of annealing of high temperature can make Graphene under the katalysis of metal catalyst.
The method for preparing Graphene or ultrathin carbon films with the PVD technology provided by the invention compared with prior art has following advantage: (1) adopts gaseous carbon sources, and the Graphene of preparation or ultrathin carbon films thickness are accurately controlled; (2) little to the substrate shape dimensional requirement, can prepare Graphene or the ultrathin carbon films of extensive homogeneous; (3) but the in-situ deposition metal level as catalyzer; (4) device structure that makes things convenient for preparation (5) the present invention of electron device electrode to use is simple, is easy to control, and industrial prospect is good.In addition, need the high temperature more than 1000 ℃ to come pyrolysis gas different with CVD, adopt anode layer ion source ionization carbon-source gas among the present invention, can under very low temperature, (≤100 ℃) realize deposition, and because ion source ionization level height, carbon source is fully deposited, almost do not have exhaust gas discharging, greatly reduce the consumption of the energy and resource.
Description of drawings
The deposition apparatus structural representation of Fig. 1 for adopting in the embodiments of the invention;
Fig. 2 is the Graphene that makes among the embodiment 1 or the surface topography of ultrathin carbon films;
Fig. 3 is the Graphene for preparing in the various embodiments of the present invention or the Raman spectrum of ultrathin carbon films;
Fig. 4 is the model diagram of the anode layer ion source in the deposition apparatus;
Fig. 5 is the anode layer ion source fundamental diagram in the deposition apparatus;
Among the figure: 1, fire door; 2, anode layer ion source; 3, multi sphere magnetic controlling target; 4, work rest; 5, well heater; 6, bleeding point.
Embodiment
Below in conjunction with specific embodiment the present invention is done detailed specific description.
The deposition apparatus that adopts in following examples all as shown in Figure 1, the deposit cavity of this device is surrounded by the furnace wall, the deposit cavity height is 500-1500mm, diameter is 700-1500mm.The deposit cavity side is provided with fire door 1, to make things convenient for the loading and unloading of substrate.Deposit cavity is provided with bleeding point 6, vacuumizes unit and vacuumizes by 6 pairs of deposit cavities of bleeding point, and vacuumizing unit can be made up of diffusion pump and mechanical pump, also can adopt molecular pump, and highest attainable vacuum can reach 5 * 10
-4Pa.The centre of deposit cavity is well heater 5, heating power 10-30 kilowatt, can improve heating efficiency.An anode layer ion source 2, three multi sphere magnetic controlling targets 3 are installed on the furnace wall.Substrate is contained on the work rest 4, and rotates with work rest 4.This layout increases considerably deposit cavity ionic medium volume density, and workpiece is immersed in the plasma body fully.Prepare Graphene or ultrathin carbon films by the anode layer ion source ionization; Substrate frame negative bias 0～-1000V is adjustable continuously, can rotate, and conveniently prepares extensive Graphene or the ultrathin carbon films of homogeneous continuously; But the well heater preheating substrate at center improves adhesive force, and can regulate depositing temperature; Three multi sphere magnetic controlling targets can be selected different target in-situ deposition middle layer or transition layer as required.
The model diagram of the anode layer ion source that adopts in the deposition apparatus and schematic diagram are as shown in Figures 2 and 3, owing between anode and negative electrode, be provided with high-intensity magnetic field, trap electronics in venting port in magnetic field, and the direction rotation along vertical and paper, the gas that the ionization of vortex electronics is passed through produces plasma body, because the specific charge of ion is low, so can be by the deaeration channel between negative electrode and the anode, along with electrons spread to the main anode district, further ionization positively charged ion, form high-density on the anode top layer, cationic layer as thin as a wafer is discharged from this zone by the positively charged ion of ionization and is also further accelerated by negative electrode, is attracted by negative bias at last.
Carbon source is acetylene gas in following examples of the present invention, and the rare gas element of auxiliary ionization is argon gas, and substrate adopts silicon substrate, silica membrane substrate or tinsel.
Preparation technology in the present embodiment is as follows: at first substrate is put on the substrate frame of deposit cavity, under 70 ℃, the condition of ar gas environment, vacuum tightness 2.5Pa, substrate bias-800V, substrate surface is carried out aura clean 20min; Then under the condition of ar gas environment, substrate bias-200V, feed the mixed gas of acetylene and argon gas in the deposit cavity, air pressure is 0.55Pa, and the flow of acetylene is 10sccm in the mixed gas, and the flow of argon gas is 70sccm; Open anode layer ion source to the mixed gas ionization, voltage is 450V during ionization, anode layer ion source produces the ionization electric current of stable 1.4A, acetylene produces after by ionization and contains carbocation, positively charged ion deposits to the substrate bombardment and at substrate under electric field action, depositing time is 10min, and substrate rotates with substrate frame in the deposition process, and rotating speed is 3rmp.Deposition is finished the back 1h that anneals under vacuum condition, annealing temperature is 600 ℃, and speed of cooling is 10 ℃/min, anneals to be cooled to the ultrathin carbon films that room temperature can make homogeneous at matrix surface after finishing.
The surface topography of the ultrathin carbon films that makes in the present embodiment as shown in Figure 2.
Preparation technology in the present embodiment is as follows: at first substrate is put on the substrate frame of deposit cavity, under 90 ℃, the condition of ar gas environment, vacuum tightness 2.5Pa, substrate bias-800V, substrate surface is carried out aura clean 20min; After the aura cleaning of substrate surface is finished, under the condition of ar gas environment, substrate bias-100V, vacuum tightness 0.7 Pa, open multiple arc target, target is high pure metal copper, voltage on the metal targets is 20V, and electric current is 40A, and metal generates metal catalytic layer in the substrate surface deposition, depositing time is 10min, closes the copper metal targets.Then under the condition of ar gas environment, substrate bias-200V, feed the mixed gas of acetylene and argon gas in the deposit cavity, air pressure is 0.8Pa, and the flow of acetylene is 10sccm in the mixed gas, and the flow of argon gas is 80sccm; Open anode layer ion source to the mixed gas ionization, voltage is 450V during ionization, anode layer ion source produces the ionization electric current of stable 1.0A, acetylene produces after by ionization and contains carbocation, positively charged ion deposits to the substrate bombardment and at substrate under electric field action, depositing time is 10min, and substrate rotates with substrate frame in the deposition process, and rotating speed is 3rmp.Deposition is finished the back 2h that anneals under vacuum condition, annealing temperature is 600 ℃, and speed of cooling is 10 ℃/min, anneals to be cooled to the ultrathin carbon films that room temperature can make homogeneous at matrix surface after finishing.
Preparation technology in the present embodiment is as follows: at first substrate is put on the substrate frame of deposit cavity, under 100 ℃, the condition of ar gas environment, vacuum tightness 2.5Pa, substrate bias-800V, substrate surface is carried out aura clean 20min; After the aura cleaning of substrate surface is finished, under the condition of ar gas environment, substrate bias-200V, vacuum tightness 0.5 Pa, open multiple arc target, target is high-purity metal nickel, voltage on the metal targets is 20V, and electric current is 100A, and metal generates metal catalytic layer in the substrate surface deposition, depositing time is 10min, closes the copper metal targets.Then under the condition of ar gas environment, substrate bias-200V, feed the mixed gas of acetylene and argon gas in the deposit cavity, air pressure is 0.6Pa, and the flow of acetylene is 20sccm in the mixed gas, and the flow of argon gas is 60sccm; Open anode layer ion source to the mixed gas ionization, voltage is 350V during ionization, anode layer ion source produces the ionization electric current of stable 1.0A, acetylene produces after by ionization and contains carbocation, positively charged ion deposits to the substrate bombardment and at substrate under electric field action, depositing time is 10min, and substrate rotates with substrate frame in the deposition process, and rotating speed is 3rmp.Deposition is finished the back 2h that anneals under vacuum condition, annealing temperature is 900 ℃, and speed of cooling is 10 ℃/min, anneals to be cooled to room temperature after finishing and can to make Graphene at matrix surface.
Among the above embodiment 1,2,3 Raman spectrum of prepared graphene or ultrathin carbon films as shown in Figure 3, as can be seen from the figure, embodiment 1 and 2 Raman spectrums have tangible D peak and G peak, but the 2D peak is not obvious, is ultrathin carbon films; Occur tangible 2D peak in the Raman spectrum of embodiment 3, show that this film is Graphene.
Claims (8)
1. one kind prepares the method for Graphene or ultrathin carbon films with the PVD technology, it is characterized in that may further comprise the steps: at first substrate is put on the substrate frame of deposit cavity, aura is carried out on the surface of substrate clean; Afterwards ar gas environment, vacuum tightness 0.5Pa～1 Pa, 70 ℃～100 ℃, substrate bias-50 V～-condition of 200V under, feed the mixed gas of acetylene and argon gas in the deposit cavity; Open anode layer ion source to the mixed gas ionization, the voltage of anode layer ion source is 300～500V during ionization, and acetylene produces after by ionization and contains carbocation, and positively charged ion deposits to the substrate bombardment and at substrate under electric field action; Deposition is finished the back 1～2h that anneals under vacuum condition, annealing temperature is 600～900 ℃, anneals can make Graphene or ultrathin carbon films at matrix surface after finishing.
2. the method for preparing Graphene or ultrathin carbon films according to claim 1 is characterized in that: adopt cathodic arc ion plating membrane method deposition one deck to play the metal catalytic layer of katalysis on the substrate, metal is Cu or Ni.
3. the method for preparing Graphene or ultrathin carbon films according to claim 2, it is characterized in that: the manufacturing process of described metal catalytic layer is as follows: after the aura cleaning of substrate surface is finished, ar gas environment, substrate bias-50 V～-condition of 200V, vacuum tightness 0.1Pa～1Pa under, open multiple arc target, voltage on the metal targets is 20V, electric current is 40～100A, and metal generates metal catalytic layer in the substrate surface deposition, and depositing time is 5～10min.
4. the method for preparing Graphene or ultrathin carbon films according to claim 1 and 2, it is characterized in that: described substrate is silicon substrate, silica membrane substrate or tinsel.
5. the method for preparing Graphene or ultrathin carbon films according to claim 1 is characterized in that: described aura cleans and is: under the condition of ar gas environment, vacuum tightness 2.5Pa, substrate bias-800V, substrate surface is carried out aura clean 20min.
6. the method for preparing Graphene or ultrathin carbon films according to claim 1 is characterized in that: when feeding the mixed gas of acetylene and argon gas in deposit cavity, the flow of acetylene is 10～20sccm, and the flow of argon gas is 60～80sccm.
7. the method for preparing Graphene or ultrathin carbon films according to claim 1, it is characterized in that: Graphene or ultrathin carbon films substrate in the process that substrate surface deposits rotates with substrate frame, and rotating speed is 3rmp.
8. the method for preparing Graphene or ultrathin carbon films according to claim 1, it is characterized in that: the speed of cooling during annealing is 10 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190642.8A CN103266306B (en) | 2013-05-22 | 2013-05-22 | A kind of PVD technology prepares the method for Graphene or ultrathin carbon films |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310190642.8A CN103266306B (en) | 2013-05-22 | 2013-05-22 | A kind of PVD technology prepares the method for Graphene or ultrathin carbon films |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103266306A true CN103266306A (en) | 2013-08-28 |
| CN103266306B CN103266306B (en) | 2015-11-18 |
Family
ID=49009967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310190642.8A Active CN103266306B (en) | 2013-05-22 | 2013-05-22 | A kind of PVD technology prepares the method for Graphene or ultrathin carbon films |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103266306B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741106A (en) * | 2013-12-25 | 2014-04-23 | 西安交通大学 | Ultrathin carbon film prepared with ECR (Electron Cyclotron Resonance) oxygen-argon plasma etching technology and method of preparing ultrathin carbon film |
| CN107298437A (en) * | 2017-08-07 | 2017-10-27 | 深圳市烯谷能源控股有限公司 | A kind of method of PVD method low temperature preparation graphene |
| CN107419220A (en) * | 2016-05-23 | 2017-12-01 | 高雄第科技大学 | Three layers of carbon, metal bi and carbon, metal, carbon manufacture method for being formed at substrate |
| CN111826610A (en) * | 2020-06-30 | 2020-10-27 | 太原理工大学 | Method for preparing graphene at low temperature by using amorphous carbon |
| CN112010292A (en) * | 2020-09-09 | 2020-12-01 | 宁波中冶电子科技有限公司 | Preparation method and application of graphene material |
| CN113151801A (en) * | 2021-03-03 | 2021-07-23 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460638A (en) * | 2003-06-11 | 2003-12-10 | 中国科学院上海微***与信息技术研究所 | Flaky carbon nano tube, preparation method and special equipment |
| CN101550539A (en) * | 2009-05-14 | 2009-10-07 | 中国科学院宁波材料技术与工程研究所 | Method for depositing protection film on the ceramics valve core surface |
| CN101993062A (en) * | 2009-08-18 | 2011-03-30 | 通用汽车环球科技运作公司 | Nanographene layers and particles and lubricants incorporating the same |
| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| WO2012008789A2 (en) * | 2010-07-15 | 2012-01-19 | 성균관대학교산학협력단 | Method for producing graphene at a low temperature, method for direct transfer of graphene using same, and graphene sheet |
| CN102659098A (en) * | 2012-05-21 | 2012-09-12 | 武汉大学 | Equipment and method for preparing graphene |
-
2013
- 2013-05-22 CN CN201310190642.8A patent/CN103266306B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460638A (en) * | 2003-06-11 | 2003-12-10 | 中国科学院上海微***与信息技术研究所 | Flaky carbon nano tube, preparation method and special equipment |
| CN101550539A (en) * | 2009-05-14 | 2009-10-07 | 中国科学院宁波材料技术与工程研究所 | Method for depositing protection film on the ceramics valve core surface |
| CN101993062A (en) * | 2009-08-18 | 2011-03-30 | 通用汽车环球科技运作公司 | Nanographene layers and particles and lubricants incorporating the same |
| CN102260858A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院物理研究所 | Method for directly growing graphine on various substrates |
| WO2012008789A2 (en) * | 2010-07-15 | 2012-01-19 | 성균관대학교산학협력단 | Method for producing graphene at a low temperature, method for direct transfer of graphene using same, and graphene sheet |
| CN102659098A (en) * | 2012-05-21 | 2012-09-12 | 武汉大学 | Equipment and method for preparing graphene |
Non-Patent Citations (2)
| Title |
|---|
| 田民波: "《薄膜技术与薄膜材料》", 31 December 2006, 北京市：清华大学出版社 * |
| 袁小亚: "石墨烯的制备研究进展", 《无机材料学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741106A (en) * | 2013-12-25 | 2014-04-23 | 西安交通大学 | Ultrathin carbon film prepared with ECR (Electron Cyclotron Resonance) oxygen-argon plasma etching technology and method of preparing ultrathin carbon film |
| CN103741106B (en) * | 2013-12-25 | 2016-03-30 | 西安交通大学 | Ultrathin carbon films prepared by ECR oxygen-argon plasma etch technology and method |
| CN107419220A (en) * | 2016-05-23 | 2017-12-01 | 高雄第科技大学 | Three layers of carbon, metal bi and carbon, metal, carbon manufacture method for being formed at substrate |
| CN107298437A (en) * | 2017-08-07 | 2017-10-27 | 深圳市烯谷能源控股有限公司 | A kind of method of PVD method low temperature preparation graphene |
| CN111826610A (en) * | 2020-06-30 | 2020-10-27 | 太原理工大学 | Method for preparing graphene at low temperature by using amorphous carbon |
| CN111826610B (en) * | 2020-06-30 | 2022-11-15 | 太原理工大学 | Method for preparing graphene at low temperature by using amorphous carbon |
| CN112010292A (en) * | 2020-09-09 | 2020-12-01 | 宁波中冶电子科技有限公司 | Preparation method and application of graphene material |
| CN113151801A (en) * | 2021-03-03 | 2021-07-23 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
| CN113151801B (en) * | 2021-03-03 | 2022-12-27 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103266306B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103266306B (en) | A kind of PVD technology prepares the method for Graphene or ultrathin carbon films | |
| CN110797545B (en) | Metal bipolar plate, preparation method thereof and fuel cell | |
| Vizireanu et al. | Plasma techniques for nanostructured carbon materials synthesis. A case study: carbon nanowall growth by low pressure expanding RF plasma | |
| CN105047958B (en) | Graphene composite coating for fuel battery metal pole plate and preparation method thereof | |
| CN108203090B (en) | Preparation method of graphene | |
| CN106129422B (en) | Improve the densification of fuel battery metal double polar plate overlay coating and corrosion resistant method | |
| Chang et al. | Direct plasma deposition of amorphous Si/C nanocomposites as high performance anodes for lithium ion batteries | |
| CN112030133B (en) | Diamond and preparation method and application thereof | |
| CN104495829A (en) | Method for preparing graphene film on low-temperature substrate | |
| JP4868592B2 (en) | Alloy nanoparticle preparation method, alloy thin film preparation method, and coaxial vacuum arc deposition apparatus | |
| TW201418156A (en) | Carbon nanotube growth on copper substrates | |
| CN106756870A (en) | A kind of method that plasma enhanced chemical vapor deposition grows Graphene | |
| CN103114276B (en) | Device for rapidly depositing diamond-like carbon film | |
| CN103708444A (en) | Preparation method and equipment of graphene film | |
| CN104773725A (en) | Method for preparing graphene by using low-temperature plasmas | |
| CN110323270B (en) | Preparation method of graphene conductive film and thin film transistor | |
| CN102074708A (en) | Boron-doping diamond film modification-based PEMFC (Proton Exchange Membrane Fuel Cell) bipolar plate and preparation method thereof | |
| KR20140122114A (en) | Metal separator for fuel cell and manufacturing method of the same | |
| CN115000444B (en) | Multilayer composite carbon coating, preparation method and application thereof, fuel cell bipolar plate and fuel cell | |
| CN110783594A (en) | Metal bipolar plate, preparation method thereof and fuel cell | |
| JP5959990B2 (en) | Graphene film manufacturing apparatus and graphene film manufacturing method | |
| CN104609406A (en) | Method for synthesizing graphene by catalyzing solid carbon source with two-stage process at normal pressure | |
| Kondo et al. | Synthesis of diamond-like carbon films by nanopulse plasma chemical vapor deposition in open air | |
| CN100568454C (en) | Adopt hydrogen doping to prepare the method for semiconductor conducting film at diamond surface | |
| CN101235488A (en) | Technique for forming thin film on substrate equipped outside radio frequency plasma |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |