CN104562005B - A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control - Google Patents
A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control Download PDFInfo
- Publication number
- CN104562005B CN104562005B CN201410845545.2A CN201410845545A CN104562005B CN 104562005 B CN104562005 B CN 104562005B CN 201410845545 A CN201410845545 A CN 201410845545A CN 104562005 B CN104562005 B CN 104562005B
- Authority
- CN
- China
- Prior art keywords
- copper foil
- graphene
- growth
- hydrogen peroxide
- control
- 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.)
- Active
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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
Abstract
The invention provides a kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control, it is characterised in that comprises the following steps：Prepare the hydrogen peroxide that mass concentration is 5 30%；By copper foil immersion wherein, copper foil is by hydrogen peroxide oxidation；Then it is used for CVD growth graphene with the pretreated copper foil.Described step 2）In soak time be 5 60s.The method of other control copper foil surface graphene Enhancing Nucleation Densities is compared to, this method is simple and easy to do, it is only necessary to which carrying out hydrogen peroxide dipping to copper foil in advance just can effectively reduce the Enhancing Nucleation Density of copper foil surface graphene.Meanwhile, this method can also be used in combination with other control methods, on the basis of this method, by controlling air rate, gas pressure intensity, copper foil surface roughness, growth temperature etc., can further reduce Enhancing Nucleation Density, improve the monocrystalline size of graphene film.
Description
Technical field
The present invention relates to a kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control, belong to field of material technology.
Background technology
Graphene has excellent electricity, mechanics, optics, thermal property, in electricity device, photoelectric device, radiating element
Had broad prospects Deng field, and the large scale of graphene, high-quality preparation are its wide variety of premises.
Chemical vapor deposition (CVD) method is the means for being most expected to realize graphene film industrialized production, and its reaction is former
Reason is：Copper catalysis decomposes carbon-source gas, and carbon atom forms several nucleating centers in copper foil surface, and final crystal grain is grown up link
Film forming.The quality of graphene is heavily dependent on its monocrystalline size, that is, Enhancing Nucleation Density.Researcher has attempted to respectively
Graphene film of the approach of the kind growth with large single crystal size.While the speed of growth is ensured, the monocrystalline chi of graphene is improved
It is very little, that is, its Enhancing Nucleation Density is reduced, for improving the quality of graphene, promoting the application of graphene to have great importance.
Control graphene includes the air rate of control methane, hydrogen, gas pressure in the method for copper foil surface Enhancing Nucleation Density at present
By force, the methods such as the active position of dioxygen oxidation reduction copper foil surface are passed through under the roughness of copper foil surface, growth temperature and high temperature.
Active this method of position of dioxygen oxidation reduction copper foil surface is passed through under method set out above, particularly high temperature for experiment bar
Part requires very harsh, unfavorable to use industrialized production.
The content of the invention
Technical problem：For the method for the Enhancing Nucleation Density that controls its superficial growth graphene, to solve existing method technique
Complicated, the low problem of the speed of growth, the present invention provides a kind of side of the Enhancing Nucleation Density for the graphene for controlling its superficial growth
Method.
Technical scheme：The method of the Enhancing Nucleation Density of the graphene of its superficial growth of the control of the present invention, including following step
Suddenly：
1）Prepare the hydrogen peroxide that mass concentration is 5-30%；
2）By copper foil immersion wherein, copper foil is by hydrogen peroxide oxidation；
3）Then it is used for CVD growth graphene with the pretreated copper foil.
Described step 2）In soak time be 5-60s.
Preferably,
Described step 1）In hydrogen peroxide mass concentration be 5%.
Described step 2）In soak time be 30s.
Described step 3）CVD growth graphene method it is as follows：By the pretreated copper foil of hydrogen peroxide with do not carry out it is pre-
The copper foil of processing is placed in parallel in growth furnace, and control methane, hydrogen flow is respectively 20 and 100sccm, and mixing pressure is
200pa, 1045 DEG C of growth temperature, growth time 1 minute.
The principle of the method for the Enhancing Nucleation Density of the graphene of its superficial growth of the control of the present invention is as follows：Copper foil surface it is miscellaneous
Matter activity is stronger, is the easy nucleation site of graphene.Dioxygen water pretreatment causes copper foil surface to aoxidize, at high temperature copper foil surface
Oxygen chemically reacted with surface impurity, so as to reduce the density in copper foil surface activated centre, reduce the shape of graphene
Cuclear density.
Beneficial effect：The method of other control copper foil surface graphene Enhancing Nucleation Densities is compared to, this method is simple and easy to do,
Only need to just can effectively reduce the Enhancing Nucleation Density of copper foil surface graphene to copper foil progress hydrogen peroxide dipping in advance.Meanwhile, this
Method can also be used in combination with other control methods, on the basis of this method, by controlling air rate, gas pressure intensity, copper
Paper tinsel surface roughness, growth temperature etc., can further reduce Enhancing Nucleation Density, improve the monocrystalline size of graphene film.
Brief description of the drawings
500 times of light microscopes that Fig. 1 is distributed for the single-layer graphene forming core of the copper foil surface without dioxygen water pretreatment
Picture（Light tone region is single-layer graphene）.
500 times of optics that Fig. 2 is distributed for the single-layer graphene forming core of the copper foil surface by 5% dioxygen water pretreatment 30 seconds
Microscope photograph（Light tone region is single-layer graphene）.
Specific embodiment
Embodiment 1
The method of the Enhancing Nucleation Density of the graphene of its superficial growth of the control of the present invention, comprises the following steps：
1）Compound concentration mass concentration is 5% hydrogen peroxide solution；
2）The copper foil that a piece of thickness is 25 microns is obtained, and is handled 30 seconds in 5% hydrogen peroxide；
3）CVD growth graphene：The pretreated copper foil of hydrogen peroxide and the copper foil that is not pre-processed are placed in parallel in
In growth furnace, control methane, hydrogen flow is respectively 20 and 100sccm, and mixing pressure is 200pa, and 1045 DEG C of growth temperature is raw
1 minute for a long time；
By several minutes of dioxygen water process of the copper foil after growth, observation by light microscope graphene is reused in copper foil surface
Enhancing Nucleation Density.500 times of optical microphotographs that Fig. 1 is distributed for the single-layer graphene forming core of the copper foil surface without dioxygen water pretreatment
Mirror picture（Light tone region is graphene）.Fig. 2 is the single-layer graphene shape of the copper foil surface by 5% dioxygen water pretreatment 30 seconds
500 times of optical microscope pictures of core distribution（Light tone region is graphene）.As can be seen that carrying out dioxygen water logging to copper foil in advance
Bubble just can effectively reduce the Enhancing Nucleation Density of copper foil surface graphene.
Claims (1)
1. a kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control, it is characterised in that comprise the following steps：
1）With producing hydrogen peroxide；
2）By copper foil immersion wherein, copper foil is by hydrogen peroxide oxidation；
3）Then it is used for CVD growth graphene with the pretreated copper foil；
Described step 1）In hydrogen peroxide mass concentration be 5%；
Described step 2）In soak time be 30s；
Described step 3）CVD growth graphene method it is as follows：By the pretreated copper foil of hydrogen peroxide with not pre-processed
Copper foil be placed in parallel in growth furnace, control methane, hydrogen flow is respectively 20 and 100sccm, and mixing pressure is
200pa, 1045 DEG C of growth temperature, growth time 1 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410845545.2A CN104562005B (en) | 2014-12-31 | 2014-12-31 | A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410845545.2A CN104562005B (en) | 2014-12-31 | 2014-12-31 | A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104562005A CN104562005A (en) | 2015-04-29 |
| CN104562005B true CN104562005B (en) | 2017-08-29 |
Family
ID=53079057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410845545.2A Active CN104562005B (en) | 2014-12-31 | 2014-12-31 | A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104562005B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105369347B (en) * | 2015-11-03 | 2018-04-06 | 电子科技大学 | It is a kind of to be nucleated the device and method for preparing large-area graphene monocrystalline by controlling |
| CN106637391A (en) * | 2016-08-15 | 2017-05-10 | 复旦大学 | Method for reducing nucleus density in procedures for synthesizing single-crystal graphene by aid of chemical vapor deposition processes |
| CN110359088A (en) * | 2019-08-07 | 2019-10-22 | 中国电子科技集团公司第四十六研究所 | A kind of large area single crystal graphene growing method |
| CN112921296B (en) * | 2021-01-22 | 2022-05-24 | 东北林业大学 | Method for growing graphene on special-shaped metal substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102833963A (en) * | 2012-09-03 | 2012-12-19 | 高德（无锡）电子有限公司 | Horizontal pre-treatment method for improving copper exposing at bottom of blind drilling hole in soft gold electroplating |
| CN103352210A (en) * | 2013-06-24 | 2013-10-16 | 中国科学院上海微***与信息技术研究所 | Method for visually displaying distribution of CVD (Chemical Vapor Deposition) graphene surface defects on metal substrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475313B (en) * | 2010-09-14 | 2017-05-17 | 应用奈米结构公司 | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
| US9845551B2 (en) * | 2012-07-10 | 2017-12-19 | William Marsh Rice University | Methods for production of single-crystal graphenes |
-
2014
- 2014-12-31 CN CN201410845545.2A patent/CN104562005B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102833963A (en) * | 2012-09-03 | 2012-12-19 | 高德（无锡）电子有限公司 | Horizontal pre-treatment method for improving copper exposing at bottom of blind drilling hole in soft gold electroplating |
| CN103352210A (en) * | 2013-06-24 | 2013-10-16 | 中国科学院上海微***与信息技术研究所 | Method for visually displaying distribution of CVD (Chemical Vapor Deposition) graphene surface defects on metal substrate |
Non-Patent Citations (1)
| Title |
|---|
| 化学气相沉积法制备石墨烯的铜衬底预处理研究;王浪等;《物理学报》;20140723;第63卷(第17期);第176801-1页左栏第2段至176802页左栏第3段，176801-5页左栏第2段至右栏第3段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104562005A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104562005B (en) | A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control | |
| US8932673B2 (en) | Methods of fabricating large-area graphene | |
| CN104159736B (en) | The extensive monolayer of high-quality and multi-layer graphene by means of chemical gaseous phase deposition produce | |
| CN105523546A (en) | Preparation method of three-dimensional graphene | |
| CN104099577B (en) | A kind of preparation method of Graphene | |
| CN102229426B (en) | Preparation method of equiangular hexagonal graphene arranged in single layer sequentially | |
| O'Regan et al. | Recent advances in the growth of germanium nanowires: synthesis, growth dynamics and morphology control | |
| EA200870558A1 (en) | METHODS OF PREPARING POLYCRYSTALLIC SILICON SILICONS OF HIGH DEGREE OF PURITY WITH THE USE OF METAL MEANS-BASIS | |
| CN104085887B (en) | A kind of process for preparing graphenes by chemical vapour deposition | |
| CN108441948A (en) | A kind of preparation method of the micro-nano crystal array of wafer level graphene | |
| US20140256120A1 (en) | Process for Preparing Graphene Based on Metal Film-Assisted Annealing and the Reaction with Cl2 | |
| Cheng et al. | Hydrogen peroxide-assisted hydrothermal synthesis of hierarchical CuO flower-like nanostructures | |
| CN106087051B (en) | The preparation method and its equipment of synchronous growth wafer scale AB stacking bilayer graphene | |
| CN102583337A (en) | Preparation method for graphene material with porous structure | |
| CN108286042A (en) | A kind of number of plies is uniformly and the preparation method of high quality molybdenum disulfide film | |
| CN103145117A (en) | Method for preparing graphene | |
| Wang et al. | Effects of preparation conditions on the growth of ZnO nanorod arrays using aqueous solution method | |
| WO2009038172A1 (en) | Method for forming catalyst layer for carbon nanostructure growth, liquid for catalyst layer formation, and process for producing carbon nanostructure | |
| CN109824038A (en) | A kind of efficient method for eliminating chemical vapour deposition technique graphene fold | |
| CN114933327B (en) | Hydrogen production material and preparation method and application thereof | |
| SG131935A1 (en) | Process for producing biogas | |
| TW201829860A (en) | Crucible and manufacture method thereof, and 4h-sic crystal growth method | |
| JP2012140266A5 (en) | ||
| CN103160929B (en) | The preparation method of a kind of monocrystal AIN nano cone and nanometer sheet | |
| CN103935996A (en) | Method for directly synthesizing graphene by using CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190612 Address after: 225300 East Second Floor, Building 5, 168 Fenghuang West Road, Taizhou City, Jiangsu Province Patentee after: Taizhou Feirongda New Material Technology Co., Ltd. Address before: 225300 Building No. 5, 168 Fenghuang West Road, Taizhou City, Jiangsu Province Co-patentee before: TAIZHOU GRAPHENE RESEARCH AND CHARACTERIZATION PLATFORM CO., LTD. Patentee before: Taizhou Sunano Energy Co., Ltd. Co-patentee before: SUNANO TECHNOLOGY COMPANY |
|
| TR01 | Transfer of patent right |