CN105018896A - Graphene film as well as preparation method and application thereof - Google Patents
Graphene film as well as preparation method and application thereof Download PDFInfo
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- CN105018896A CN105018896A CN201410164177.5A CN201410164177A CN105018896A CN 105018896 A CN105018896 A CN 105018896A CN 201410164177 A CN201410164177 A CN 201410164177A CN 105018896 A CN105018896 A CN 105018896A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000011889 copper foil Substances 0.000 claims abstract description 107
- 238000000034 method Methods 0.000 claims abstract description 59
- 230000008569 process Effects 0.000 claims abstract description 37
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims description 19
- 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
- 238000012545 processing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
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- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 238000012546 transfer Methods 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
- 230000008859 change Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 150000001721 carbon Chemical group 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a graphene film. The preparation method comprises the following steps: treating a copper foil blank and then growing the graphene film on a copper foil, wherein the step of treating the copper foil blank comprises the following sub-steps: (1) carrying out plasma cleaning on the copper foil blank to remove dirt and then carrying out plasma oxide layer removal treatment on the copper foil blank to remove a surface oxide layer of the copper foil blank, wherein hydrogen is utilized as a plasma; (2) carrying out electrochemical polishing on the copper foil blank from which the oxide layer is removed; (3) repeating the step (1) to remove the surface oxide layer of the polished copper foil blank, thus obtaining the copper foil used for graphene film growth. A two-step method is adopted in the plasma treatment process, oxygen is pumped in to eliminate organic stains in the first step, hydrogen or other reducing gases are pumped in to remove the oxide layer in the second step, the two processes belong to chemical reaction which is more efficient than physical reaction in which argon is pumped in and is more thorough in treatment, and yellowing of the copper foil can be effectively avoided to improve the integrity and uniformity of late graphene film generation.
Description
Technical field
The present invention relates to a kind of graphene film and preparation method thereof, and the transparency electrode that this graphene film is made.
Background technology
Graphene film, has the monolayer carbon atom of graphite-structure, since being found first, has just caused a sensation whole scientific circles with the structure of its uniqueness and excellent performance from 2004.The fast development of graphene film is badly in need of preparing with realizing extensive mass structural thickness and the controlled high-quality graphene film of size.The method preparing graphene film at present mainly contains following several: (1) micromechanics stripping method, (2) crystal epitaxy method, (3) chemistry redox method, (4) chemical vapor deposition (CVD) method.Wherein CVD prepares the most frequently used method of large-area graphene film at present.CVD refers to that reactive material issues biochemical reaction at gaseous condition and generates the method that solid matter is deposited on substrate or catalyst surface and then obtained solid material.Wherein Copper Foil has low price as substrate, and the graphene film quality of growth is better, and the number of plies is more easy to control, is easy to the features such as corrosion transfer, utilizations a large amount of in current graphene film mass production.Because graphene film belongs to surface growth mechanism in copper foil surface growth, therefore, in process of growth, graphene film can copy the condition of surface of Copper Foil, and the clean level of copper foil surface and activity, to the forming core growth important of graphene film, then have influence on the quality of graphene film.At present, in suitability for industrialized production, graphene film growth Copper Foil does not still have the earlier stage treatment process that a set of maturation is perfect, is simple solvent cleaning usually, the graphene film grown out like this has following shortcoming: (1) graphene film defect is many, and sheet resistance is higher; (2) copper foil surface roughness is too high, causes the microtexture of graphene film to be destroyed, causes the breakage of structure in the transfer process of graphene film; (3) graphene film growth is uneven, causes sheet resistance and transmittance skewness; (4) copper foil surface cleaning is thorough not, the spot often less cleaning in fine eyelet and depression, and spot can affect forming core, the growth of graphene film, and damages the outward appearance of graphene film and function; (5) surfactivity of Copper Foil is low, and skewness, be unfavorable for the uniform and stable growth of graphene film.
In laboratory study, reasonable treatment process has document [1]: the mechanical polishing that Sun Lei etc. mention in " artificial lens journal " 2012 02 phase the research of Graphene controllable growth " on the polishing Copper Foil substrate " published and electrochemical etching Duplex treatment method and document; Document [2]: the Chang Quanhong of Shanghai Normal University in 2012 in its Master's thesis " Graphene of chemical vapour deposition (CVD) growing high-quality and the research of performance thereof " to the plasma polishing processes that nickel substrate uses.
But there is following defect in above-mentioned disclosed two sections of technique documents: (1) is for the mechanical polishing mentioned in document [1] and electrochemical etching Duplex treatment method, its main weak point is as follows: a. mechanical polishing cost is high, and complicated operation is lengthy and tedious, be not suitable for industrialized mass production graphene film, simultaneously, easily cause the fold of Copper Foil in operating process, be unfavorable for the high-quality graphene film of growing large-area; B. copper foil surface cleaning is thorough not, the spot often less cleaning in fine eyelet and depression, and spot can affect forming core, the growth of graphene film, and damages the outward appearance of graphene film and function; C. copper foil surface hypoactivity, and activity distribution is uneven, is unfavorable for the uniform and stable growth of graphene film.(2) in document [2] to nickel substrate use plasma polishing processes, its main weak point is as follows: adopt rare gas element argon gas to carry out plasma treatment in a. document, remove the spot of nickel substrate surface, this process belongs to physical reaction, compared to chemical reaction, this process is consuming time longer, and efficiency is lower, is not suitable for industrialized mass production; When b. using argon plasma process Copper Foil, Copper Foil easily turns to be yellow, and affects the forming core growth of graphene film; C. plasma polishing reduces not obvious to the roughness of copper foil surface, effectively can not flatten roll mark and the hollow of copper foil surface, thus cause the microtexture of graphene film to be destroyed, cause the breakage of structure in the transfer process of graphene film.
Summary of the invention
The object of this invention is to provide a kind of preparation method of graphene film, this preparation method by Copper Foil dealt with due to the clean level of copper foil surface and activity low, cause graphene film to grow uneven technical problem.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of graphene film, comprising: Copper Foil blank is processed, then the step of growing graphene film on this Copper Foil; Wherein, the step of Copper Foil blank process is comprised:
(1) after plasma cleaning scrubbing being carried out to Copper Foil blank, then the process of plasma oxide layer is carried out to this Copper Foil blank, to improve copper foil surface activity, improve the effect of next step electrochemical etching;
(2) after the Copper Foil blank except oxide layer being carried out electrochemical etching;
(3) repeating step (1), to remove the Copper Foil blank surface zone of oxidation after polishing, obtains described graphene film growth Copper Foil.
Further, the method for the plasma oxide layer process in described step (1) is: the plasma body becoming to have the material of reductibility by reducing gas ionization, to remove the surface oxide layer of described Copper Foil blank.
Further, in order to more effectively remove the surface oxide layer of Copper Foil blank, when carrying out the oxide layer process of described step (1), the flow entering the reducing gas of plasma generator is not less than 50sccm, and plasma processing time is not less than 100S.
Further, in order to more effectively remove the surface oxide layer of Copper Foil blank, when carrying out the plasma oxide layer process of described step (3), the flow entering the reducing gas of plasma generator is not less than 100sccm, and plasma processing time is not less than 120S.
Further, in described step (2), the method for electrochemical etching comprises: be soaked in electrolytic solution using the Copper Foil blank except oxide layer as anode, and energising makes anode dissolution; Wherein, described electrolytic solution comprises: phosphoric acid volumetric concentration 55%-70%, the volumetric concentration 5%-10% of ethanol and/or acetone, the volumetric concentration 2%-5% of acetic acid and/or sulfuric acid, and all the other are water.
Further, in order to prevent copper foil surface to be oxidized, described preparation method also comprises: after cleaning the Copper Foil blank after electrochemical etching, and recycling rare gas element dries up this Copper Foil blank; Or, dry under protection of inert gas.
Described reducing gas is H
2,nO, CH
4, NH
3deng one or more in gas.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) the present invention is by plasma cleaning, and the inside going deep into fine eyelet and depression completes cleaning, effectively improves the clean level of copper foil surface; (2) can effectively reduce copper foil surface roughness by electrochemical etching, the graphene film defect of growth is reduced; (3) by hydrogen as plasma body, improve copper foil surface active, and make activity distribution even, impel graphene film forming core growth uniformly and stably; (4) finally carry out plasma treatment again, the zone of oxidation of copper foil surface is removed more thorough, and can effectively avoid Copper Foil to turn to be yellow, improve integrity and the homogeneity of graphene film generation.
On the basis of above-mentioned graphene film growth Copper Foil, present invention also offers a kind of graphene film, this graphene film is made up of the preparation method of above-mentioned graphene film.
Technique scheme of the present invention has the following advantages compared to existing technology: the graphene film made by the present invention, because copper foil surface is smooth, clean, activity is high, therefore, the graphene film growth that this Copper Foil basis grows is uniform and stable, and its sheet resistance and transmittance are evenly distributed.
On the basis of above-mentioned graphene film, a kind of transparency electrode, the graphene film described in employing is made.
Technique scheme of the present invention has the following advantages compared to existing technology: make by graphene film of the present invention the contact resistance that transparency electrode reduces graphene film and semiconductor material, and improve its transmittance.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below basis specific embodiment and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the schema of the preparation method of graphene film growth Copper Foil of the present invention;
Fig. 2 is the surface topography before Copper Foil process of the present invention under observation by light microscope;
Fig. 3 is the surface topography after Copper Foil process of the present invention under observation by light microscope;
Fig. 4 is the roughness test result of copper foil surface before Copper Foil process;
Fig. 5 is the roughness test result of copper foil surface after Copper Foil process;
Fig. 6 (a), Fig. 6 (b), Fig. 6 (c), Fig. 6 (d) are respectively the graphene film forming core contrast of the Copper Foil through different treatment technique of same stove growth.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail:
Embodiment 1
The preparation method of the graphene film of the present embodiment, adopt chemical vapor deposition (CVD) method, comprising: Copper Foil blank is processed, and then in the step of this Copper Foil Grown graphene film, see Fig. 1, the step that this Copper Foil processes is comprised: (1) plasma pretreatment, (2) electrochemical etching, cleaning, (3) secondary plasma treatment.Specifically comprise the steps:
(1) plasma pretreatment: this treating processes is carried out in two steps, first, is placed in vacuum plasma cleaning machine by the Copper Foil blank cut out, and the oxygen of logical certain flow, carries out first time plasma abatement process.Active particle in oxygen plasma can go deep into the inside of fine eyelet and depression, thoroughly removes the dirty of Copper Foil blank surface by chemical reaction, effectively improves the clean level of Copper Foil blank surface; These process control processing condition are: power 400W-500W, below the pressure 40Pa in cleaning cabin, oxygen flow 150sccm-200sccm, treatment time 100S-250S.Then, plasma cleaner is vacuumized, then the hydrogen of certain flow is passed into, carry out first time plasma oxide layer process, active particle in hydrogen plasma is by the zone of oxidation of chemical reaction removing Copper Foil blank surface, also can improve Copper Foil blank surface active simultaneously, improve the effect of next step electrochemical etching.Controlling Technology condition is: power 400W-500W, below the pressure 40Pa in cleaning cabin, hydrogen flowing quantity 50sccm-100sccm, treatment time 100S-250S.This step improves the surfactivity of Copper Foil blank, improve the effect of next step electrochemical etching.In this step (1), carbon monoxide is used to substitute hydrogen can realize oxide layer equally effect as plasma body, also the mixed gas of carbon monoxide and hydrogen can be used as plasma body, namely, become to have the plasma body of reductibility by reducing gas ionization, to remove the surface oxide layer of described Copper Foil blank.The data of the corresponding embodiment of this step plasma pretreatment are see table 1.
The data list of the corresponding embodiment of plasma pretreatment described in table 1
(2) electrochemical etching: be soaked in electrolyzer as anode using Copper Foil blank complete for plasma treatment, energising makes anode dissolution, thus reaches the effect reducing Copper Foil blank surface roughness.Controlling Technology parameter is: phosphoric acid volumetric concentration 55%-70%, urea volumetric concentration 0%-3%, ethanol (or being acetone) volumetric concentration 5%-10%, to reduce the viscosity of phosphoric acid solution, blank surface greasy filth can be removed further, effectively discharge the bubble that electrolysis produces; Acetic acid (or being sulfuric acid) volumetric concentration 2%-5%, all the other are water.Voltage 10V-25V, electric current 120A-250A, conduction time 30S-240S, solution temperature 25-40 DEG C; Effectively can reduce Copper Foil blank surface roughness by electrochemical etching, the graphene film defect of growth is reduced.The data of the corresponding embodiment of this step electrochemical etching are see table 2.
The data list of the corresponding embodiment of electrochemical etching described in table 2
Cleaning: the Copper Foil blank after electrochemical etching is soaked in acetone, be placed in ultrasonic cleaning 3min-5min in supersonic cleaning machine, removing remains in electrolytic solution and other spots of Copper Foil blank surface, with deionized water, Copper Foil blank surface is cleaned 2-3 time again, removing remained on surface liquid, last nitrogen (or being the rare gas elementes such as argon gas) dries up, and is dried up Copper Foil blank by rare gas element; Or, dry under protection of inert gas, avoid being oxidized in atmosphere.Wherein ultrasonic cleaning Controlling Technology parameter is: ultrasonic power 100KW-200KW, ultrasonic frequency 40KHz.
(3) secondary plasma treatment: the Copper Foil blank dried up by nitrogen is placed in vacuum plasma cleaning machine again, passes into the oxygen of certain flow, carries out abatement processes such as ion such as second time such as grade, thoroughly removes the dirty of Copper Foil blank surface remnants.These process control processing condition are: power 400W-500W, the pressure 20-25Pa in cleaning cabin, oxygen 100sccm-150sccm, treatment time 60S-120S.Then, vacuumize, namely when pressure is less than 40Pa, pass into the hydrogen of certain flow, carry out the process of second time plasma oxide layer, the zone of oxidation of removing Copper Foil blank surface, improve Copper Foil blank surface active, meanwhile, in uniform plasma atmosphere, Copper Foil blank surface everywhere activity reaches consistent, is conducive to graphene film in the forming core growth uniformly and stably of Copper Foil blank surface.These process control processing condition are: power 400W-500W, the pressure 20-25Pa in cleaning cabin, hydrogen 100sccm-200sccm, treatment time 120S-180S.Wherein, pass into hydrogen or other reducing gas except oxide layer, higher than the physical reaction efficiency passing into argon gas, process more thorough, and can effectively avoid Copper Foil to turn to be yellow, and improve copper foil surface activity, and make activity distribution even, impel graphene film forming core growth uniformly and stably, improve integrity and the homogeneity of later stage graphene film generation.In this step (3), the reducing gas of step (1) can be adopted equally to realize.
And in step (3), also can directly carry out the process of plasma oxide layer.
The data of the corresponding embodiment of this step 2 time plasma treatment are see 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, this graphene film is made up of the preparation method of above-mentioned graphene film, and concrete is grown into by the graphene film growth Copper Foil described in embodiment 1.
See Fig. 2 to Fig. 6, Copper Foil blank through different treatment technique is placed in same diffusion furnace simultaneously, control growth technique and carry out the growth of CVD graphene film forming core, after the copper foil sample obtained being placed on constant temperature heating plate 150 DEG C of baking 5min, use metallography microscope sem observation, result is as shown in Fig. 6 (a) to Fig. 6 (d), and in figure, white mass is the graphene film crystal grain in forming core growth.From Fig. 6 (a), undressed Copper Foil, graphene film Enhancing Nucleation Density is large, and graphene film grain-size is little, out-of-shape, skewness; Fig. 6 (b), merely through the Copper Foil of step (2) electrochemical etching, graphene film Enhancing Nucleation Density is less, and graphene film grain-size is large, and shape is more regular; Fig. 6 (c), merely through the Copper Foil of plasma oxide layer process in step (3), graphene film Enhancing Nucleation Density is little, and graphene film grain-size is comparatively large, and regular shape is evenly distributed; Fig. 6 (d), the Copper Foil obtained by step of the present invention (1), (2), (3), graphene film Enhancing Nucleation Density reduces further, and grain-size is larger, and regular shape, is evenly distributed.Therefore, Copper Foil pretreatment process successful of the present invention, effectively can reduce the nucleation rate of graphene film, increase graphene film grain-size, and the activity of copper foil surface can be improved, and surfactivity is uniformly distributed, be conducive to the uniform and stable growth of graphene film.
Embodiment 3
A kind of transparency electrode on embodiment 2 basis, it adopts described graphene film to make.
Obviously, above-described embodiment is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And these belong to spirit institute's apparent change of extending out of the present invention or change and are still among protection scope of the present invention.
Claims (8)
1. a preparation method for graphene film, is characterized in that comprising: process Copper Foil blank, then the step of growing graphene film on this Copper Foil; Wherein, the step that Copper Foil blank processes is comprised:
(1) after plasma cleaning scrubbing being carried out to Copper Foil blank, then the process of plasma oxide layer is carried out to this Copper Foil blank;
(2) the Copper Foil blank except oxide layer is carried out electrochemical etching;
(3) again carry out the process of plasma oxide layer, the Copper Foil blank surface zone of oxidation after removing polishing, to obtain described graphene film growth Copper Foil.
2. preparation method according to claim 1, it is characterized in that, described step (1) with the method for the plasma oxide layer process in step (3) is: the plasma body becoming to have reductibility by reducing gas ionization, to remove the surface oxide layer of described Copper Foil blank.
3. preparation method according to claim 2, is characterized in that, when carrying out the oxide layer process of described step (1), the flow entering the reducing 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, is characterized in that, when carrying out the plasma oxide layer process of described step (3), the flow entering the reducing gas of plasma generator is not less than 100sccm, and plasma processing time is no less than 120S.
5. according to the preparation method one of claim 1-4 Suo Shu, it is characterized in that, in described step (2), the method for electrochemical etching comprises: be soaked in electrolytic solution using the Copper Foil blank except oxide layer as anode, and energising makes anode dissolution; Wherein, described electrolytic solution comprises: phosphoric acid volumetric concentration 55%-70%, the volumetric concentration 5%-10% of ethanol and/or acetone, the volumetric concentration 2%-5% of acetic acid and/or sulfuric acid, and all the other are water.
6. preparation method according to claim 5, is characterized in that, described preparation method also comprises: after cleaning the Copper Foil blank after electrochemical etching, and recycling rare gas element dries up this Copper Foil blank; Or, dry under protection of inert gas.
7. a graphene film, is characterized in that, described graphene film is made up of the preparation method of the graphene film one of claim 1-4 Suo Shu.
8. a transparency electrode, is characterized in that, adopts graphene film as claimed in claim 7 to make.
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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 |
| 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 |
| 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 |
| CN110453280A (en) * | 2018-05-08 | 2019-11-15 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of high quality wafer level graphene monocrystalline |
| CN112921389A (en) * | 2019-12-06 | 2021-06-08 | 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 |
| CN115478237A (en) * | 2022-09-14 | 2022-12-16 | 浙江东南新材科技有限公司 | Hot-dip galvanized steel coil and production process thereof |
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