CN108203090A - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
- Publication number
- CN108203090A CN108203090A CN201611170148.5A CN201611170148A CN108203090A CN 108203090 A CN108203090 A CN 108203090A CN 201611170148 A CN201611170148 A CN 201611170148A CN 108203090 A CN108203090 A CN 108203090A
- Authority
- CN
- China
- Prior art keywords
- graphene
- film
- preparation
- tube body
- amorphous carbon
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Abstract
The present invention provides a kind of preparation methods of graphene.This method combination cathodic vacuum arc deposition technique, with reference to electron beam evaporation technique, and vacuum annealing process, pass through Optimizing Process Parameters, it deposits to obtain the amorphous carbon-film with high sp3 contents in matrix surface first, then catalyst film is deposited in its surface electronic beam, finally making carbon diffusional precipitation in 450 DEG C~500 DEG C annealing, structure is changed into graphene-structured, so as to form few layer or multi-layer graphene to catalyst film surface.Compared with existing graphene preparation process, present invention process is simple and practicable, and annealing temperature is low, reduces cost；Carbon source used is not gas but solid, the number of plies of graphene can be controlled by controlling the thickness of carbon source, so as to fulfill the controllable preparation of graphene.
Description
Technical field
The present invention relates to the preparation methods that technical field of graphene more particularly to a kind of amorphous carbon are converted to graphene.
Background technology
Graphene is by sp2The tow -dimensions atom with hexagonal honeycomb shape crystal structure that the carbon atom bonding of hydridization forms
Crystal.Graphene is the basic unit for forming carbon nanotube, fullerene and graphite block body material etc..
In 2004, the scientist Novoselov and Geim of Britain et al. obtained independently depositing using micromechanics stripping method
High-quality graphene, and be found that graphene have unique electronic property, so as to started graphene research upsurge.
Graphene has high carrier mobility and thermal conductivity, high light transmittance and good chemical stability etc., in electronic device, thoroughly
The various fields such as prescribed electrode material, energy storage material, functional composite material have broad application prospects.
The preparation method of graphene mainly has mechanical stripping method, silicon carbide epitaxial growth method, graphite oxide reduction method, chemistry
Vapour deposition process etc..Graphene quality prepared by mechanical stripping method is high, simple for process, and size reaches millimeter rank, but party's legal system
The standby time is long, and of high cost, the number of plies and size of graphene are uncontrollable, it is difficult to extensive use；Silicon carbide epitaxial growth method can be prepared
Big size graphene, but silicon carbide is expensive, and preparation condition is harsh, needs ultrahigh vacuum, 1200 DEG C of high temperature or more；Aoxidize stone
There are many graphene defect prepared by black reduction method；That application is most at present is chemical vapour deposition technique (CVD), can realize scale
Metaplasia is long, but the carbon source of this method is carbonaceous gas, needs pyrolytic (900 DEG C~1000 DEG C of temperature), and influence factor compared with
It is more, such as air pressure, flow etc..
Invention content
For the above-mentioned state of the art, the present invention provides a kind of preparation methods of graphene, and this method is simple and practicable, cost
It is low.
The technical scheme is that：A kind of preparation method of graphene, includes the following steps：
Step 1：It is dried after matrix Si surface cleans；
Step 2：Using cathodic vacuum arc precipitation equipment, matrix Si is put into vacuum chamber, target is high purity graphite target,
On matrix Si surfaces, deposition thickness is 2~30nm amorphous carbon-films, and sedimentary condition is：The vacuum degree of thin film deposition vacuum chamber reaches
3.0×10-3For Pa hereinafter, being passed through 15~25sccm of argon gas, 55~60A of arc stream, matrix applies pulsed negative bias -300V~-350V,
330~370KHz of pulse frequency, pulsewidth 0.9~1.2 μ s, 1~10min of sedimentation time；
Step 3：The amorphous carbon-film on matrix Si surfaces is rinsed well with High Purity Nitrogen air gun, then using electron beam evaporation plating skill
Art prepares metal catalytic agent film on amorphous carbon-film surface, and plating conditions are：It is evacuated to 2 × 10-3Pa is hereinafter, electron gun power
8~20W, deposition rate
Step 4：Vacuum annealing furnace is vacuumized, and vacuum degree in stove is made to reach 3.0 × 10-2Pa is hereinafter, warm in raising stove
It spends to after 450~500 DEG C, is put into Si/ amorphous carbons/metal catalyst samples, keep the temperature 15~20min, it is then air-cooled.
The purity of the high purity graphite target is preferably more than 99.999%.
The cathodic vacuum arc precipitation equipment is the device using cathodic vacuum arc deposition method film.It is described
Cathodic vacuum arc sedimentation be the plasma for generating vacuum arc evaporation source, be attracted to base by negative bias voltage etc.
Body, and on matrix surface formed film a kind of method.Cathodic vacuum arc sedimentation has ionization level height, ion energy
The high, series of advantages such as depositing temperature is low, deposition rate is high, film base junction is got togather.
The cathode vacuum arc source thin film deposition device includes cathodic vacuum arc evaporation source, thin film deposition vacuum
Chamber, vacuum extractor and the gas passage for being passed through inert gas.Wherein, cathodic vacuum arc evaporation source passes through vacuum
Electric arc electric discharge evaporation cathode target, thus generates the plasma containing cathode target material.
In the step 1, as a preferred embodiment, using ultrasonic cleaning matrix Si tables in alcoholic solution
Face.
In the step 2, sp3 contents are higher than in the amorphous carbon-film obtained using cathodic vacuum arc techniques of deposition
80%.
In the step 2, the deposition rate of amorphous carbon-film is preferably 1~3nm/min.
In the step 4, preferred metallic catalyst is copper, nickel etc., and preferred catalyst thickness is 70~100nm.
In order to reduce deposition of macroscopical bulky grain in matrix surface, the roughness of film is reduced, improves surface flatness, is made
To be preferred, the cathode vacuum arc source thin film deposition device further includes Magnetic filtration device part, by tube body and is arranged on tube body
Outer peripheral edge magnetic field generation device composition, tube body include tube body entrance face and tube body exit end face, tube body entrance face with
At least one bend pipe between tube body exit end face, and the angle between the axis of the bend pipe both sides tube body is 135 °.As
Further preferably, direct current positive bias is applied to the bend pipe, which is preferably 5~10V.Utilize the bending magnetic mistake
The roughness Ra of amorphous carbon-film that filter cathodic vacuum arc precipitation equipment deposits is less than 0.2nm.
In conclusion the present invention combines cathodic vacuum arc deposition technique, is moved back with reference to electron beam evaporation technique and vacuum
Ignition technique by Optimizing Process Parameters, deposits to obtain the amorphous carbon-film with high sp3 contents, Ran Houzai first in matrix surface
Catalyst film is deposited in its surface electronic beam, finally makes carbon diffusional precipitation to catalyst film table using annealing heat-treats
Face, structure are changed into graphene-structured, so as to form few layer or multi-layer graphene.With existing graphene preparation process phase
Than the present invention has the advantages that：
(1) it is simple for process, it is at low cost；
(2) carbon source used in is not gas but solid, by the optimization of cathodic vacuum arc precipitation equipment, can improve
The surface flatness of amorphous carbon-film makes its roughness be less than 0.2nm；Also, the deposition speed in cathodic vacuum arc deposition technique
Rate can be down to 1~3nm/min, by the way that deposition rate and carbon film thickness is controlled to can control the number of plies of generation graphene；
(3) by optimizing the technological parameter in cathodic vacuum arc deposition, there is high sp3 contents in amorphous carbon-film, moving back
Annealing temperature in fire processing is relatively low, graphene can be obtained under the low temperature thermal oxidation less than 500 DEG C, compared to CVD method
High temperature more than 1000 DEG C greatly reduces generation temperature, reduces cost, is conducive to push inexpensive, the big face of graphene
The development of long-pending controllable preparation technology.
Description of the drawings
Fig. 1 is the structure diagram of the cathode vacuum arc source thin film deposition device in the embodiment of the present invention 1；
Fig. 2 is along the sectional view of line A-A in Fig. 1；
Fig. 3 is the Raman spectrogram before the sample annealing in the embodiment of the present invention 1；
Fig. 4 is the Raman spectrogram after the sample annealing in the embodiment of the present invention 1；
Fig. 5 is the Raman spectrogram after the sample annealing in comparative example 1.
Specific embodiment
The present invention is described in further detail below in conjunction with attached drawing, embodiment, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Reference numeral in Fig. 1-2 is：Cathode 1, anode 2, bend pipe 3, arc source coil 4 drag lead circle 5, curve coil 6,
Output winding 7, scanning coil 8, permanent magnet 9, palisade baffle 10, threaded rod 11, trigger electrode 12, gas passage 13, pneumatic operated valve
Door 14, observation window 15, insulating washer 16, stainless steel ring 17, stainless steel ring 18, deep bid 19, shallow bid 20, bleeding point 21, bias plasma
Source 22, thin film deposition vacuum chamber 23, gas vent 24, insulating washer 25, stainless steel ring 26, stainless steel ring 27, insulating washer 28, no
Become rusty steel loop 29, stainless steel ring 30, arc source coil DC power supply 31, and the electric arc pulse power 32 is dragged lead circle DC power supply 33, curved
Coil DC power supply 34, output winding DC power supply 35, scanning coil AC power 36, grid bias power supply 37, cathodic vacuum arc
Evaporation source 39, the first bend pipe 40, the second bend pipe 41.
Embodiment 1:
Step 1：Then matrix Si is dried in alcoholic solution with ultrasonic cleaning.
Step 2：Deposited amorphous carbon film
Using cathode vacuum arc source thin film deposition device, the apparatus structure as shown in figs. 1 and 2, including the company of sealing successively
The cathodic vacuum arc evaporation source 39 that connects, Magnetic filtration device part, the thin film deposition vacuum chamber 23 for being equipped with matrix.
Wherein, cathodic vacuum arc evaporation source 39 includes trapezoidal columnar cathode 1, the cylindrical annular coaxial with cathode 1 sun
Pole 2, be arranged between cathode 1 and anode 2 for exciting the operated pneumatic valve 14 of the trigger electrode 12 of electric arc, trigger electrode 12.
In the present embodiment, trigger electrode 12 is a striking needle.The both sides for being placed on cathode 1 coaxial with anode 2 of permanent magnet 9, permanent magnet 9
A threaded rod 11 is connected, the spinning in and out threaded rod 11 can adjust the distance between permanent magnet 9 and cathode 1.The cathode is true
Empty 39 outer peripheral edge of arc evaporation source is provided with arc source coil 4 and coupled arc source coil power supply 31.In addition, the cathode vacuum
Arc evaporation source 39 further includes gas passage 13 and observation window 15.
Magnetic filtration device part includes tube body and is arranged on the magnetic field generation device of tube body outer peripheral edge, and tube body enters including tube body
Mouth end face and tube body exit end face, at least one bend pipe 3 between tube body entrance face and tube body exit end face, and the bend pipe
Angle between the axis of 3 both sides tube bodies is 135 °.The present embodiment middle tube body is the stainless steel elbow 3 with interlayer water cooling, curved
3 circular in cross-section of pipe, bend pipe 3 are made of two parts：The first bend pipe 40 in 135 ° of angles and second in 135 ° of angles curved
Pipe 41, the stainless steel ring 26 in first 40 exit of bend pipe and the stainless steel ring 27 of second 41 inlet of bend pipe pass through felt pad
It is closely coupled to enclose 25.The tube wall of bend pipe is equipped with electromagnetic coil group and the electromagnetic coil power supply for electromagnetic coil group power supply, including
It is located at the output winding for curving coil 6 and be located at tube body exit dragged lead circle 5, be located at tube body bend pipe 3 of tube body inlet
7.It wherein drags lead circle 5 to be connected to drag lead circle DC power supply 33, curves coil 6 and be connected to curve coil DC power supply 34, it is defeated
Go out coil 7 and be connected to output winding DC power supply 35.
Thin film deposition vacuum chamber 23 includes the work rest positioned at central bottom, and 19 He of deep bid that can be revolved round the sun is formed on work rest
On deep bid 19 can rotation shallow bid 20.When carrying out thin film deposition, it would be desirable to the workpiece fixation of deposition film is placed on shallow bid 20,
Shallow bid can be allowed to transfer the uniformity for improving workpiece surface deposition film certainly.To change depositing ions energy, grid bias power supply can be passed through
22 apply certain back bias voltage for workpiece.In addition, thin film deposition vacuum chamber 23 further includes bleeding point 21 and gas vent 24, the pumping
Mouth 21 is connected with the vacuum extractor of cathode vacuum arc source thin film deposition device.
Stainless steel ring 17 on cathodic vacuum arc evaporation source 39 passes through felt pad with the stainless steel ring 18 in elbow inlet
Enclose 16 closely coupled, the stainless steel ring 29 in second 41 exit of bend pipe and the stainless steel rings of 23 inlet of thin film deposition vacuum chamber
30 are closely joined together by insulating washer 28.
Matrix Si is put into shallow bid 20 in vacuum chamber 23, shallow bid rotation, cathode targets 1 are the round stone of purity 99.999%
Black target, when the vacuum in vacuum chamber 23 reaches 3.0 × 10-3Start plated film during below Pa, plating conditions are as follows：
Argon gas 20sccm, arc stream 55A are passed through, the grid bias power supply 37 of bend pipe 3 applies direct current positive bias 8V, bias for bend pipe
Power supply 22 is that matrix application pulsed negative bias size is -350V, and pulse frequency 350KHz, pulsewidth is 1.1 μ s.
The sedimentation time 10min under the plating conditions, deposition obtain film thickness as 10nm.
Step 3：Vacuum coating is put into after matrix Si after above-mentioned deposited amorphous carbon film is rinsed well with High Purity Nitrogen air gun
Room prepares Raney nickel film using electron beam evaporation technique on amorphous carbon-film surface, and plating conditions are：It is evacuated to 2 × 10- 3Hereinafter, setting electron gun power is 10W, deposition rate is PaNickel thickness 100nm.
Step 4：Using vacuum annealing furnace, vacuum degree reaches 3.0 × 10 in stove-2Pa, temperature are put into above-mentioned after reaching 500 DEG C
The matrix Si of depositing catalytic agent film and amorphous carbon-film keeps the temperature 20min, then air-cooled.
To through matrix Si/ amorphous carbon-films made from step 2 and the Si/ amorphous nanocarbon/metals after step 4 heat treatment obtained
The sample surfaces of catalyst film carry out Raman spectrum detection, as a result such as Fig. 3, shown in 4.Carbon film is non-before finding heat treatment by Fig. 3
Brilliant carbon structure uses XPS measuring wherein sp3 contents as 85%；It is found by Fig. 4, after Overheating Treatment, has obtained representing graphene
G peaks and 2D peaks, it was demonstrated that amorphous carbon is changed into graphene.
Comparative example 1：
The present embodiment is the comparative example of embodiment 1.
In the present embodiment, the preparation method of graphene is substantially the same manner as Example 1, except that：Plated film in step 2
Condition is as follows：
Argon gas 2sccm, arc stream 70A are passed through, bend pipe applies direct current positive bias 8V, and matrix applies pulsed negative bias size
For -- 100V, pulse frequency 350KHz, pulsewidth are 1.1 μ s；
2min is deposited under the plating conditions, the film thickness deposited is 10nm.
To through matrix Si/ amorphous carbon-films made from step 2 and the Si/ amorphous nanocarbon/metals after step 4 heat treatment obtained
The sample surfaces of catalyst film carry out Raman spectrum detection.It was found that heat treatment before carbon film be amorphous carbon structure, using XPS measuring its
Middle sp3 contents are 85%；Raman spectrum after Overheating Treatment does not have as shown in figure 5, display only has the D peaks of amorphous carbon and G peaks
2D peaks occur, it was demonstrated that there is no graphene.
Embodiment 2:
Step 1：Matrix is same as Example 1, and processing method is identical with the step 1 in embodiment 1；
Step 2：Deposited amorphous carbon film
It is essentially identical with the step 2 in embodiment 1, except that：Plating conditions in step 2 are as follows：
Argon gas 20sccm, arc stream 60A are passed through, bend pipe applies direct current positive bias 10V, and matrix applies pulsed negative bias size
For -100V, pulse frequency 350KHz, pulsewidth is 1.1 μ s；
8min is deposited under the plating conditions, the film thickness deposited is 15nm.
Step 3：It is identical with the step 3 in embodiment 1；
Step 4：Using vacuum annealing furnace, vacuum degree reaches 3.0 × 10 in stove-2Pa, temperature are put into above-mentioned after reaching 450 DEG C
The matrix Si after catalyst film is deposited, keeps the temperature 20min, it is then air-cooled.
To through matrix Si/ amorphous carbon-films made from step 2 and the Si/ amorphous nanocarbon/metals after step 4 heat treatment obtained
The sample surfaces of catalyst film carry out Raman spectrum detection.It was found that heat treatment before carbon film be amorphous carbon structure, using XPS measuring its
Middle sp3 contents are 80%；After Overheating Treatment, the G peaks of graphene and 2D peaks are obtained representing, it was demonstrated that amorphous carbon is changed into graphite
Alkene.
Embodiment 3:
Step 1：Matrix is same as Example 1, and processing method is identical with the step 1 in embodiment 1；
Step 2：Deposited amorphous carbon film
It is essentially identical with the step 2 in embodiment 1, except that：Plating conditions in step 2 are as follows：It is passed through argon gas
20sccm, arc stream 60A, bend pipe apply direct current positive bias 10V, and matrix applies pulsed negative bias size as -100V, pulse frequency
350KHz, pulsewidth are 1.1 μ s；
10min is deposited under the plating conditions, the film thickness deposited is 20nm.
Step 3：Vacuum coating is put into after matrix Si after above-mentioned deposited amorphous carbon film is rinsed well with High Purity Nitrogen air gun
Room prepares copper catalyst film using electron beam evaporation technique on amorphous carbon-film surface, and plating conditions are：It is evacuated to 2 × 10- 3Hereinafter, setting electron gun power is 20W, deposition rate is PaCopper thickness 100nm.
Step 4：Using vacuum annealing furnace, vacuum degree reaches 3.0 × 10 in stove-2Pa, temperature are put into above-mentioned after reaching 450 DEG C
The matrix Si after catalyst film is deposited, keeps the temperature 15min, it is then air-cooled.
To through matrix Si/ amorphous carbon-films made from step 2 and the Si/ amorphous nanocarbon/metals after step 4 heat treatment obtained
The sample surfaces of catalyst film carry out Raman spectrum detection.It was found that heat treatment before carbon film be amorphous carbon structure, using XPS measuring its
Middle sp3 contents are 80%；After Overheating Treatment, the G peaks of graphene and 2D peaks are obtained representing, it was demonstrated that amorphous carbon is changed into graphite
Alkene.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene, which is characterized in that include the following steps：
Step 1：It is dried after matrix Si surface cleans；
Step 2：Using cathodic vacuum arc precipitation equipment, matrix Si is put into vacuum chamber, target is high purity graphite target, in base
Body Si surfaces deposition thickness is 2~30nm amorphous carbon-films, and sedimentary condition is：The vacuum degree of thin film deposition vacuum chamber reaches 3.0 ×
10-3For Pa hereinafter, being passed through 15~25sccm of argon gas, 55~60A of arc stream, matrix applies pulsed negative bias -300V~-350V, pulse
330~370KHz of frequency, pulsewidth 0.9~1.2 μ s, 1~10min of sedimentation time；
Step 3：The amorphous carbon-film on matrix Si surfaces with High Purity Nitrogen air gun is rinsed well, is then existed using electron beam evaporation technique
Amorphous carbon-film surface prepares metal catalytic agent film, and plating conditions are：It is evacuated to 2 × 10-3Pa hereinafter, electron gun power 8~
20W, deposition rate
Step 4：Vacuum annealing furnace is vacuumized, and vacuum degree in stove is made to reach 3.0 × 10-2Pa is hereinafter, increase in-furnace temperature extremely
After 450~500 DEG C, Si/ amorphous carbons/metal catalyst samples are put into, keep the temperature 15~20min, it is then air-cooled.
2. the preparation method of graphene as described in claim 1, which is characterized in that in the step 1, in alcoholic solution
With ultrasonic cleaning matrix Si surfaces.
3. the preparation method of graphene as described in claim 1, which is characterized in that in the step 2, high purity graphite target
Purity is more than 99.999%.
4. the preparation method of graphene as described in claim 1, which is characterized in that in the step 4, metallic catalyst is
Copper or nickel.
5. the preparation method of graphene as described in claim 1, which is characterized in that in the step 4, catalyst film is thick
It spends for 70~100nm.
6. the preparation method of graphene as described in claim 1, which is characterized in that in the step 2, amorphous carbon-film sinks
Product rate is 1~3nm/min.
7. the preparation method of the graphene as described in any claim in claim 1 to 6, which is characterized in that described the moon
Pole vacuum arc source film deposition apparatus includes Magnetic filtration device part, is generated by tube body and the magnetic field for being arranged on tube body outer peripheral edge
Device forms, and tube body includes tube body entrance face and tube body exit end face, between tube body entrance face and tube body exit end face extremely
Bend pipe there are one few, and the angle between the axis of the bend pipe both sides tube body is 135 °.
8. the preparation method of graphene as claimed in claim 7, which is characterized in that apply to the Magnetic filtration device part straight
Flow 5~10V of positive bias.
9. the preparation method of graphene as claimed in claim 8, which is characterized in that in the step 2, utilize cathode vacuum
Sp3 contents are higher than 80% in the amorphous carbon-film that arc deposited technology deposits.
10. the preparation method of graphene as claimed in claim 8, which is characterized in that in the step 4, amorphous carbon-film
Roughness Ra is less than 0.2nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611170148.5A CN108203090B (en) | 2016-12-16 | 2016-12-16 | Preparation method of graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611170148.5A CN108203090B (en) | 2016-12-16 | 2016-12-16 | Preparation method of graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108203090A true CN108203090A (en) | 2018-06-26 |
| CN108203090B CN108203090B (en) | 2021-03-26 |
Family
ID=62601627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611170148.5A Active CN108203090B (en) | 2016-12-16 | 2016-12-16 | Preparation method of graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108203090B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358189A (en) * | 2018-01-03 | 2018-08-03 | 中国科学院电工研究所 | A method of preparing graphene |
| CN109136842A (en) * | 2018-08-22 | 2019-01-04 | 中国科学院宁波材料技术与工程研究所 | graphene film and preparation method thereof |
| CN110205589A (en) * | 2019-07-12 | 2019-09-06 | 江苏徐工工程机械研究院有限公司 | A kind of pulse carbon ion excitation source apparatus |
| CN110371948A (en) * | 2019-07-23 | 2019-10-25 | 中国科学院福建物质结构研究所 | A kind of Novel Carbon Nanomaterials and its preparation method and application |
| WO2020187743A1 (en) * | 2019-03-15 | 2020-09-24 | Nanofilm Technologies International Pte Ltd | Improved cathode arc source |
| CN111892040A (en) * | 2020-08-24 | 2020-11-06 | 江苏清大际光新材料有限公司 | Method for preparing graphene by arc process |
| CN115458729A (en) * | 2022-10-28 | 2022-12-09 | 天津普兰能源科技有限公司 | Graphene-coated silicon material, and electric arc preparation method and application thereof |
| EP4079431A4 (en) * | 2020-04-24 | 2023-04-26 | Sumitomo Electric Hardmetal Corp. | Cutting tool |
| US11903116B2 (en) | 2020-06-19 | 2024-02-13 | Nanofilm Technologies International Limited | Cathode arc source, filters thereof and method of filtering macroparticles |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100021708A1 (en) * | 2008-04-14 | 2010-01-28 | Massachusetts Institute Of Technology | Large-Area Single- and Few-Layer Graphene on Arbitrary Substrates |
| CN101792895A (en) * | 2010-03-25 | 2010-08-04 | 中国科学院宁波材料技术与工程研究所 | Cathodic vacuum arc source film depositing device and method for depositing film |
| CN102505114A (en) * | 2012-01-03 | 2012-06-20 | 西安电子科技大学 | Preparation method of graphene on SiC substrate based on Ni film-aided annealing |
| CN102774065A (en) * | 2012-06-01 | 2012-11-14 | 中国科学院宁波材料技术与工程研究所 | Amorphous carbon film with graphene structure and preparation method thereof |
| CN102963883A (en) * | 2012-10-22 | 2013-03-13 | 武汉大学 | Method for preparing graphene |
| CN103172404A (en) * | 2013-04-05 | 2013-06-26 | 浙江理工大学 | Three-dimensional metal-graphene composite substrate and preparation method thereof |
| KR101438027B1 (en) * | 2013-01-16 | 2014-09-04 | 한국과학기술연구원 | Method of preparing high quality graphene using acr discharge and high quality graphene using the same |
| CN105645389A (en) * | 2015-12-30 | 2016-06-08 | 成都新柯力化工科技有限公司 | Method for preparing graphene from amorphous carbon |
| CN105801918A (en) * | 2016-03-24 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Cellulose/graphene oxide composite film and preparing method thereof |
| CN105887166A (en) * | 2015-01-12 | 2016-08-24 | 刘艳娇 | Preparation method for thermoelectrical thin film with nano nickel loaded on graphene |
-
2016
- 2016-12-16 CN CN201611170148.5A patent/CN108203090B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100021708A1 (en) * | 2008-04-14 | 2010-01-28 | Massachusetts Institute Of Technology | Large-Area Single- and Few-Layer Graphene on Arbitrary Substrates |
| CN101792895A (en) * | 2010-03-25 | 2010-08-04 | 中国科学院宁波材料技术与工程研究所 | Cathodic vacuum arc source film depositing device and method for depositing film |
| CN102505114A (en) * | 2012-01-03 | 2012-06-20 | 西安电子科技大学 | Preparation method of graphene on SiC substrate based on Ni film-aided annealing |
| CN102774065A (en) * | 2012-06-01 | 2012-11-14 | 中国科学院宁波材料技术与工程研究所 | Amorphous carbon film with graphene structure and preparation method thereof |
| CN102963883A (en) * | 2012-10-22 | 2013-03-13 | 武汉大学 | Method for preparing graphene |
| KR101438027B1 (en) * | 2013-01-16 | 2014-09-04 | 한국과학기술연구원 | Method of preparing high quality graphene using acr discharge and high quality graphene using the same |
| CN103172404A (en) * | 2013-04-05 | 2013-06-26 | 浙江理工大学 | Three-dimensional metal-graphene composite substrate and preparation method thereof |
| CN105887166A (en) * | 2015-01-12 | 2016-08-24 | 刘艳娇 | Preparation method for thermoelectrical thin film with nano nickel loaded on graphene |
| CN105645389A (en) * | 2015-12-30 | 2016-06-08 | 成都新柯力化工科技有限公司 | Method for preparing graphene from amorphous carbon |
| CN105801918A (en) * | 2016-03-24 | 2016-07-27 | 中国科学院宁波材料技术与工程研究所 | Cellulose/graphene oxide composite film and preparing method thereof |
Non-Patent Citations (12)
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358189A (en) * | 2018-01-03 | 2018-08-03 | 中国科学院电工研究所 | A method of preparing graphene |
| CN109136842A (en) * | 2018-08-22 | 2019-01-04 | 中国科学院宁波材料技术与工程研究所 | graphene film and preparation method thereof |
| WO2020187743A1 (en) * | 2019-03-15 | 2020-09-24 | Nanofilm Technologies International Pte Ltd | Improved cathode arc source |
| US11926890B2 (en) | 2019-03-15 | 2024-03-12 | Nanofilm Technologies International Limited | Cathode arc source |
| CN110205589A (en) * | 2019-07-12 | 2019-09-06 | 江苏徐工工程机械研究院有限公司 | A kind of pulse carbon ion excitation source apparatus |
| CN110205589B (en) * | 2019-07-12 | 2023-12-08 | 江苏徐工工程机械研究院有限公司 | Pulse carbon ion excitation source device |
| CN110371948A (en) * | 2019-07-23 | 2019-10-25 | 中国科学院福建物质结构研究所 | A kind of Novel Carbon Nanomaterials and its preparation method and application |
| CN110371948B (en) * | 2019-07-23 | 2023-02-10 | 中国科学院福建物质结构研究所 | Carbon nano material and preparation method and application thereof |
| EP4079431A4 (en) * | 2020-04-24 | 2023-04-26 | Sumitomo Electric Hardmetal Corp. | Cutting tool |
| US11903116B2 (en) | 2020-06-19 | 2024-02-13 | Nanofilm Technologies International Limited | Cathode arc source, filters thereof and method of filtering macroparticles |
| CN111892040A (en) * | 2020-08-24 | 2020-11-06 | 江苏清大际光新材料有限公司 | Method for preparing graphene by arc process |
| CN115458729B (en) * | 2022-10-28 | 2023-03-24 | 天津普兰能源科技有限公司 | Graphene-coated silicon material, and electric arc preparation method and application thereof |
| CN115458729A (en) * | 2022-10-28 | 2022-12-09 | 天津普兰能源科技有限公司 | Graphene-coated silicon material, and electric arc preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108203090B (en) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108203090A (en) | A kind of preparation method of graphene | |
| CN108677144B (en) | Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film | |
| CN100560793C (en) | A kind of method for preparing nano composite diamond coating | |
| CN109778136B (en) | Method for preparing diamond-like coating by adopting thermionic plasma technology | |
| CN100460555C (en) | Equipment and method for low temperature depositing high-quality decorative film by electric arc ion plating | |
| EP2148939A1 (en) | Vacuum treatment unit and vacuum treatment process | |
| CN104141109B (en) | Method for in-situ synthesis of composite TiC-DLC coating on surface of titanium | |
| CN113293331B (en) | High-entropy alloy surface carbide/diamond coating and preparation method thereof | |
| JP2010174310A (en) | Method of producing diamond-like carbon membrane | |
| US10480057B2 (en) | Apparatus and a method for plating an Nd—Fe—B magnet | |
| Wu et al. | Effects of bias voltage and gas pressure on orientation and microstructure of iridium coating by double glow plasma | |
| CN109082647B (en) | Preparation method of DLC protective film on aluminum alloy surface | |
| CN103266306A (en) | Method for preparing graphene or ultrathin carbon film by PVD (physical vapor deposition) technique | |
| JP2010209446A (en) | Plasma cvd apparatus | |
| CN102409291A (en) | Method and device for preparing diamond film doped with ultrafine nano-structural metal particles | |
| CN114703452A (en) | CoCrFeNi high-entropy alloy doped amorphous carbon film and preparation method thereof | |
| CN102719788B (en) | Plasma omnibearing ion deposition equipment | |
| CN105200390A (en) | Method for restraining secondary electron emission by directly depositing nano-graphene | |
| CN113265642A (en) | Method for depositing diamond-like carbon film on inner wall surface of metal cylinder (or tube) with large length-diameter ratio | |
| CN107002228B (en) | plasma treatment and reactor for thermochemical treatment of the surface of metal pieces | |
| CN105220122B (en) | Has the magnetic control sputtering device of high power pulse ion source | |
| CN106555175A (en) | A kind of high-density plasma reinforced chemical vapor deposition apparatus | |
| CN203700496U (en) | Device for coating diamond-like carbon films | |
| CN111826610B (en) | Method for preparing graphene at low temperature by using amorphous carbon | |
| JP5360603B2 (en) | Method for producing amorphous carbon-coated member |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |