CN105018896B - Graphene film, preparation method and the usage - Google Patents
Graphene film, preparation method and the usage Download PDFInfo
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- CN105018896B CN105018896B CN201410164177.5A CN201410164177A CN105018896B CN 105018896 B CN105018896 B CN 105018896B CN 201410164177 A CN201410164177 A CN 201410164177A CN 105018896 B CN105018896 B CN 105018896B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000011889 copper foil Substances 0.000 claims abstract description 105
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 29
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000009832 plasma treatment Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- 238000005202 decontamination Methods 0.000 abstract description 2
- 230000003588 decontaminative effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
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Abstract
The present invention relates to a kind of preparation method of graphene film, including：Copper foil blank is handled, then on the copper foil grow graphene film the step of；Wherein, the step of handling copper foil blank includes：（1）After carrying out plasma cleaning decontamination to copper foil blank, then plasma oxide layer processing is carried out to the copper foil blank, i.e., by the use of hydrogen as plasma, to remove the surface oxide layer of copper foil blank；（2）After the copper foil blank for removing oxide layer is carried out into electrochemical polish；（3）Repeat step（1）, to remove the copper foil blank surface oxide layer after polishing, obtain graphene film growth copper foil.Two-step method is used in the plasma treatment process of the present invention, the first step is passed through oxygen and removes greasy filth, second step is passed through hydrogen or other reducibility gas remove oxide layer, the two processes belong to chemical reaction, than the physical reactions efficiency high for being passed through argon gas, processing is more thorough, and effectively copper foil can be avoided to turn to be yellow, to improve the integrality and uniformity of the generation of later stage graphene film.
Description
Technical field
The present invention relates to a kind of graphene film and preparation method thereof, and transparency electrode made of the graphene film.
Background technology
Graphene film, there is the single layer of carbon atom of graphite-structure, it is just only with its since 2004 are found first
Special structure and excellent performance and cause a sensation whole scientific circles.The fast-developing of graphene film is badly in need of realizing extensive mass
Ground preparation structure thickness and the controllable high-quality graphene film of size.The current method for preparing graphene film mainly has following
It is several：（1）Micromechanics stripping method,（2）Crystal epitaxy method,（3）Chemistry redox method,（4）Chemical vapor deposition
（CVD）Method.Wherein CVD is the most frequently used method of current preparation large-area graphene film.CVD refers to reactive material in gas
Chemical reaction generation solid matter occurs under the conditions of state and is deposited on substrate or catalyst surface and then the method that solid material is made.
Wherein copper foil has cheap as substrate, and the graphene film quality of growth is preferable, and the number of plies is relatively easy to control, and is easy to corrosion and turns
The features such as shifting, largely used in current graphene film mass production.Because graphene film is in copper foil surface life
Length belongs to superficial growth mechanism, and therefore, graphene film can replicate the surface state of copper foil, and copper foil surface in growth course
Clean level and activity, important is grown to the forming core of graphene film, then has influence on the matter of graphene film
Amount.At present, in industrialized production, graphene film growth with copper foil still without the perfect earlier stage treatment process of a set of maturation,
It is generally only simple solvent cleaning, the graphene film so to grow out has the disadvantages that：（1）Graphene film defect
More, sheet resistance is higher；（2）Copper foil surface roughness is too high, causes the microstructure of graphene film to be destroyed, in graphene film
Transfer process in cause the breakage of structure；（3）Graphene film growth is uneven, causes sheet resistance and light transmittance skewness
It is even；（4）Copper foil surface cleaning is not thorough enough, and often less cleaning, spot can influence graphite to the spot in fine eyelet and depression
The forming core of alkene film, growth, and the outward appearance and function of graphene film are damaged；（5）The surface-active of copper foil is low, and
Skewness, it is unfavorable for the uniform and stable growth of graphene film.
In laboratory research, relatively good handling process has document [1]：Sun Lei etc. exists《Artificial lens journal》 2012
02 phase of year publishes《Polish the research of graphene controllable growth on copper foil substrate》In the mechanical polishing mentioned and electrochemical polish
Duplex treatment method and document；Document [2]：The Chang Quanhong of Shanghai Normal University in 2012 is in its Master's thesis《Chemical vapor deposition
(CVD) graphene of high quality and its research of performance are grown》In the plasma polishing processes that use nickel substrate.
But there is following defect in two technique documents disclosed above：（1）For the mechanical polishing mentioned in document [1]
It is as follows with electrochemical polish Duplex treatment method, its main weak point：A. it is high to mechanically polish cost, and complex operation is lengthy and tedious, no
It is adapted to industrialized mass production graphene film, meanwhile, the fold of copper foil is easily caused in operating process, is unfavorable for growing big face
The graphene film of product high quality；B. copper foil surface cleaning is not thorough enough, and the spot in fine eyelet and depression is often cleaned not
Arrive, spot can influence the forming core of graphene film, growth, and the outward appearance and function of graphene film are damaged；C. copper foil
Surface-active is low, and activity distribution is uneven, is unfavorable for the uniform and stable growth of graphene film.（2）For in document [2]
The plasma polishing processes used nickel substrate, its main weak point are as follows：A. carried out in document using inert gas argon gas etc.
Ion processing, the spot of nickel substrate surface is removed, the process belongs to physical reactions, for chemical reaction, process consumption
When it is longer, it is less efficient, be not suitable for industrialized mass production；When b. using argon plasma processing copper foil, copper foil is easily sent out
Huang, influence the forming core growth of graphene film；C. plasma polishing reduces unobvious to the roughness of copper foil surface, it is impossible to has
The roll mark and hollow of effect ground leveling copper foil surface, so as to cause the microstructure of graphene film to be destroyed, in graphene film
Transfer process in cause the breakage of structure.
The content of the invention
It is an object of the invention to provide a kind of preparation method of graphene film, the preparation method passes through the processing to copper foil
Solving because the clean level and activity of copper foil surface are low, causes graphene film to grow uneven technical problem.
In order to solve the above-mentioned technical problem, the invention provides a kind of preparation method of graphene film, including：To copper foil
Blank is handled, then on the copper foil grow graphene film the step of；Wherein, the step of handling copper foil blank is wrapped
Include：
（1）After carrying out plasma cleaning decontamination to copper foil blank, then the copper foil blank is carried out at plasma oxide layer
Reason, to improve copper foil surface activity, improve the effect of next step electrochemical polish；
（2）After the copper foil blank for removing oxide layer is carried out into electrochemical polish；
（3）Repeat step（1）, to remove the copper foil blank surface oxide layer after polishing, obtain the graphene film life
Length copper foil.
Further, the step（1）In plasma oxide layer processing method be：By reducibility gas ionization into
The plasma of material with reproducibility, to remove the surface oxide layer of the copper foil blank.
Further, for the surface oxide layer of significantly more efficient removal copper foil blank, the step is carried out（1）Deoxidation
During layer processing, the flow into the reducibility gas of plasma generator is not less than 50sccm, and plasma processing time is not small
In 100S.
Further, for the surface oxide layer of significantly more efficient removal copper foil blank, the step is carried out（3）Plasma
During oxide layer processing, the flow into the reducibility gas of plasma generator is not less than 100sccm, during plasma treatment
Between be not less than 120S.
Further, the step（2）The method of middle electrochemical polish includes：Using remove oxide layer copper foil blank as
Anode is soaked in electrolyte, and energization makes anodic solution；Wherein, the electrolyte includes：Phosphoric acid volumetric concentration 55%-70%, second
The volumetric concentration 2%-5% of the volumetric concentration 5%-10% of alcohol and/or acetone, acetic acid and/or sulfuric acid, remaining is water.
Further, in order to prevent copper foil surface from aoxidizing, the preparation method also includes：To the copper foil base after electrochemical polish
After material is cleaned, inert gas is recycled to dry up the copper foil blank；Or, dried under inert gas shielding.
The reducibility gas is H2、NO、CH4、NH3Deng the one or more in gas.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：
（1）The present invention by plasma cleaning, complete cleaning, effectively improve copper by the inside that can go deep into fine eyelet and depression
The clean level on paper tinsel surface；（2）Copper foil surface roughness can effectively be reduced by electrochemical polish, make the graphene film of growth
Defect is reduced；（3）Plasma is used as by hydrogen, improves copper foil surface activity, and makes activity distribution uniform, promotes graphene
Uniformly and stably forming core grows film；（4）Plasma treatment is finally carried out again, makes the oxide layer removal of copper foil surface more thorough,
And effectively copper foil can be avoided to turn to be yellow, improve the integrality and uniformity of graphene film generation.
On the basis of above-mentioned graphene film growth copper foil, present invention also offers a kind of graphene film, the stone
Black alkene film is made up of the preparation method of above-mentioned graphene film.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：It is thin by graphene made of the present invention
Film, due to smooth, clean, the active height of copper foil surface, therefore, the graphene film growth grown on the basis of the copper foil is uniformly steady
Fixed, its sheet resistance and light transmittance are evenly distributed.
On the basis of above-mentioned graphene film, a kind of transparency electrode, it is made of described graphene film.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：Pass through the graphene film system of the present invention
The contact resistance of graphene film and semi-conducting material is reduced into transparency electrode, and improves its light transmittance.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, below according to specific embodiment and with reference to accompanying drawing,
The present invention is further detailed explanation, wherein
Fig. 1 is the flow chart of the preparation method of the graphene film growth copper foil of the present invention；
Fig. 2 is surface topography of the copper foil before processing of the present invention under observation by light microscope；
Fig. 3 is the surface topography under observation by light microscope after the copper foil of the present invention is handled；
Fig. 4 is the roughness test result of copper foil before processing copper foil surface；
Fig. 5 is the roughness test result of copper foil surface after copper foil processing；
Fig. 6（a）, Fig. 6（b）, Fig. 6（c）, Fig. 6（d）The copper foil by different disposal technique of respectively same stove growth
Graphene film forming core contrasts.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention is described in detail：
Embodiment 1
The preparation method of the graphene film of the present embodiment, using chemical vapor deposition（CVD）Method, including：To copper
Foil blank is handled, and then Fig. 1 is seen, at the copper foil the copper foil Grown graphene film the step of again
The step of reason, includes：（1）Plasma pretreatment,（2）Electrochemical polish, cleaning,（3）Secondary plasma treatment.Specifically include as
Lower step：
（1）Plasma pretreatment：The processing procedure is carried out in two steps, and first, the copper foil blank cut out is placed in into vacuum
In plasma cleaner, lead to the oxygen of certain flow, carry out first time plasma abatement processing.Active grain in oxygen plasma
Son can go deep into the inside of fine eyelet and depression, thoroughly remove the dirty of copper foil blank surface by chemically reacting, effectively improve
The clean level of copper foil blank surface；The process control process conditions are：Power 400W-500W, the pressure in cleaning cabin
Below 40Pa, oxygen flow 150sccm-200sccm, processing time 100S-250S.Then, plasma cleaner is vacuumized,
The hydrogen of certain flow is then passed to, first time plasma oxide layer is carried out and handles, the active particle in hydrogen plasma leads to
Cross chemical reaction and remove the oxide layer of copper foil blank surface, while can also improve copper foil blank surface activity, improve electricity in next step
The effect of chemical polishing.The process conditions are controlled to be：Power 400W-500W, below the pressure 40Pa in cleaning cabin, hydrogen flowing quantity
50sccm -100sccm, processing time 100S-250S.This step improves the surface-active of copper foil blank, improves electricity in next step
The effect of chemical polishing.The step（1）In, deoxidation can equally be realized as plasma by substituting hydrogen using carbon monoxide
The effect of layer, can also use the mixed gas of carbon monoxide and hydrogen as plasma, i.e. pass through reducibility gas ionization
Into the plasma with reproducibility, to remove the surface oxide layer of the copper foil blank.The phase of this step plasma pretreatment
The data of embodiment are answered referring to table 1.
The data list of the corresponding embodiment of plasma pretreatment described in table 1
（2）Electrochemical polish：The complete copper foil blank of plasma treatment is soaked in electrolytic cell as anode, energization makes sun
Pole is dissolved, so as to reach the effect for reducing copper foil blank surface roughness.The technological parameter is controlled to be：Phosphoric acid volumetric concentration 55%-
70%, urea volumetric concentration 0%-3%, ethanol（Or it is acetone）Volumetric concentration 5%-10%, can to reduce the viscosity of phosphoric acid solution
Blank surface greasy filth is further removed, bubble effectively caused by discharge electrolysis；Acetic acid（Or it is sulfuric acid）Volumetric concentration 2%-
5%, remaining is water.Voltage 10V-25V, electric current 120A-250A, conduction time 30S-240S, 25-40 DEG C of solution temperature；Pass through electricity
Chemical polishing can effectively reduce copper foil blank surface roughness, reduce the graphene film defect of growth.This step electrochemistry
The data of the corresponding embodiment of polishing are referring to table 2.
The data list of the corresponding embodiment of electrochemical polish described in table 2
Cleaning：By the copper foil blank immersion after electrochemical polish in acetone, it is placed in supersonic cleaning machine and is cleaned by ultrasonic
3min-5min, the electrolyte and other spots for remaining in copper foil blank surface are removed, then with deionized water to copper foil blank surface
Cleaning 2-3 times, remove remained on surface liquid, last nitrogen（Or it is the inert gases such as argon gas）Drying, by inert gas to copper foil
Blank is dried up；Or, dried under inert gas shielding, avoid aoxidizing in atmosphere.Wherein it is cleaned by ultrasonic control technique ginseng
Number is：Ultrasonic power 100KW-200KW, supersonic frequency 40KHz.
（3）Secondary plasma treatment：The copper foil blank that nitrogen dries up is again placed in vacuum plasma cleaning machine, is passed through
The oxygen of certain flow, carry out waiting the second secondary ion abatement processes, thoroughly remove the dirty of copper foil blank surface remnants.The process
The process conditions are controlled to be：Power 400W-500W, the pressure 20-25Pa in cleaning cabin, oxygen 100sccm-150sccm, processing
Time 60S-120S.Then, vacuumize, i.e., when pressure is less than 40Pa, be passed through the hydrogen of certain flow, carry out second it is inferior from
Sub- oxide layer processing, the oxide layer of copper foil blank surface is removed, improve copper foil blank surface activity, meanwhile, uniform etc.
In ion atmosphere, activity reaches consistent to copper foil blank surface everywhere, and it is uniformly steady in copper foil blank surface to be advantageous to graphene film
Determine landform nucleus growth.The process control process conditions are：Power 400W-500W, the pressure 20-25Pa in cleaning cabin, hydrogen
100sccm-200sccm, processing time 120S-180S.Wherein, it is passed through hydrogen or other reducibility gas removes oxide layer, than
The physical reactions efficiency high of argon gas is passed through, processing is more thorough, and effectively copper foil can be avoided to turn to be yellow, and improves copper foil surface
Activity, and make activity distribution uniform, promoting graphene film, uniformly and stably forming core grows, and improves the generation of later stage graphene film
Integrality and uniformity.The step（3）In, it can equally use step（1）Reducibility gas realize.
And in step（3）In, it can also directly carry out plasma oxide layer processing.
The data of the corresponding embodiment of this step 2 time plasma treatment are referring to table 3.
The data list of the corresponding embodiment of secondary plasma treatment described in table 3
Embodiment 2
On the basis of the graphene film growth copper foil of embodiment 1, present invention also offers a kind of graphene film,
The graphene film is made up of the preparation method of above-mentioned graphene film, specifically by embodiment 1 described in graphene film
Growth is grown into copper foil.
See Fig. 2 to Fig. 6, the copper foil blank Jing Guo different disposal technique is placed in same diffusion furnace simultaneously, control growth
Technique carries out the growth of CVD graphene film forming core, and obtained copper foil sample is placed in into 150 DEG C of baking 5min on constant temperature heating plate
Afterwards, with metallography microscope sem observation, as a result such as Fig. 6（a）To Fig. 6（d）Shown, whiteness is the graphite in forming core growth in figure
Alkene film crystal grain.By Fig. 6（a）It can be seen that undressed copper foil, graphene film Enhancing Nucleation Density is big, graphene film crystal grain chi
It is very little small, in irregular shape, skewness；Fig. 6（b）, merely through step（2）The copper foil of electrochemical polish, graphene film shape
Cuclear density is smaller, and graphene film crystallite dimension is big, and shape is relatively regular；Fig. 6（c）, merely through step（3）Middle plasma deoxidation
The copper foil of layer processing, graphene film Enhancing Nucleation Density is small, and graphene film crystallite dimension is larger, and regular shape is evenly distributed；Fig. 6
（d）, pass through the step of the present invention（1）、（2）、（3）Obtained copper foil, graphene film Enhancing Nucleation Density further reduce, crystal grain chi
It is very little bigger, regular shape, it is evenly distributed.Therefore, copper foil preprocess method positive effect of the invention, can effectively reduce graphene
The nucleation rate of film, increase graphene film crystallite dimension, and the activity of copper foil surface can be improved, and surface-active is uniformly divided
Cloth, be advantageous to the uniform and stable growth of graphene film.
Embodiment 3
A kind of transparency electrode on the basis of embodiment 2, it uses described graphene film to be made.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, it can also be made on the basis of the above description
Its various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
Among the obvious changes or variations that bright spirit is extended out is still in protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of graphene film, it is characterised in that including：Copper foil blank is handled, then in the copper foil The step of upper growth graphene film；Wherein, the step of handling copper foil blank includes：（1）Plasma pretreatment：The processing procedure is carried out in two steps, first, by the copper foil blank cut out be placed in vacuum etc. from In sub- cleaning machine, lead to the oxygen of certain flow, carry out first time plasma abatement processing；Then, plasma cleaner is taken out very Sky, the hydrogen of certain flow is then passed to, carry out the processing of first time plasma oxide layer；（2）The copper foil blank for removing oxide layer is subjected to electrochemical polish；（3）Plasma oxide layer processing is carried out again, the copper foil blank surface oxide layer after polishing is removed, to obtain the stone Black alkene film growth copper foil.
- 2. preparation method according to claim 1, it is characterised in that the step（1）And step（3）In plasma go Oxide layer processing method be：By reducibility gas ionization into the plasma with reproducibility, to remove the copper foil base The surface oxide layer of material.
- 3. preparation method according to claim 2, it is characterised in that carry out the step（1）Oxide layer processing when, Flow into the reducibility gas of plasma generator is not less than 50sccm, and plasma processing time is no less than 100s.
- 4. preparation method according to claim 2, it is characterised in that carry out the step（3）Plasma oxide layer During processing, the flow into the reducibility gas of plasma generator is not less than 100sccm, and plasma processing time is no less than 120s 。
- 5. according to the preparation method described in one of claim 1-4, it is characterised in that the step（2）Middle electrochemical polish Method includes：The copper foil blank for removing oxide layer is soaked in electrolyte as anode, energization makes anodic solution；Wherein, The electrolyte includes：The volumetric concentration 5%-10% of phosphoric acid volumetric concentration 55%-70%, ethanol and/or acetone, acetic acid and/or sulphur The volumetric concentration 2%-5% of acid, remaining is water.
- 6. preparation method according to claim 5, it is characterised in that the preparation method also includes：To electrochemical polish After copper foil blank afterwards is cleaned, inert gas is recycled to dry up the copper foil blank；Or, under inert gas shielding Drying.
- 7. a kind of graphene film, it is characterised in that the graphene film is thin as the graphene described in one of claim 1-4 The preparation method of film is made.
- 8. a kind of transparency electrode, it is characterised in that be made of graphene film as claimed in claim 7.
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| CN107282547A (en) * | 2016-03-30 | 2017-10-24 | 东莞新科技术研究开发有限公司 | The cleaning method of electronic component |
| CN110079784A (en) * | 2018-01-26 | 2019-08-02 | 中车工业研究院有限公司 | The preparation method and copper-base graphite alkene composite material of copper-base graphite alkene composite material |
| CN110453280B (en) * | 2018-05-08 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Preparation method of high-quality wafer-level graphene single crystal |
| CN109616404A (en) * | 2018-12-26 | 2019-04-12 | 中芯集成电路（宁波）有限公司 | The surface treatment method of Shooting Technique is carried out for device wafers |
| CN112921389B (en) * | 2019-12-06 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | Electrochemical polishing solution for copper foil surface pretreatment and application thereof |
| CN115007522A (en) * | 2021-03-06 | 2022-09-06 | 东莞市峰谷纳米科技有限公司 | Surface cleaning oxidation method |
| CN115478237B (en) * | 2022-09-14 | 2024-02-02 | 浙江东南新材科技有限公司 | Hot dip galvanized steel coil and production process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193224A (en) * | 2013-04-17 | 2013-07-10 | 苏州大学 | Method for preparing graphene film on nonmetallic substrate at low temperature |
| CN103553029A (en) * | 2013-10-31 | 2014-02-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
-
2014
- 2014-04-22 CN CN201410164177.5A patent/CN105018896B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193224A (en) * | 2013-04-17 | 2013-07-10 | 苏州大学 | Method for preparing graphene film on nonmetallic substrate at low temperature |
| CN103553029A (en) * | 2013-10-31 | 2014-02-05 | 中国科学院上海微***与信息技术研究所 | Method for preparing vertical graphene-based thermal material |
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