CN104562005A - Method for controlling nucleation density of graphene growing on surface - Google Patents

Method for controlling nucleation density of graphene growing on surface Download PDF

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Publication number
CN104562005A
CN104562005A CN201410845545.2A CN201410845545A CN104562005A CN 104562005 A CN104562005 A CN 104562005A CN 201410845545 A CN201410845545 A CN 201410845545A CN 104562005 A CN104562005 A CN 104562005A
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CN
China
Prior art keywords
copper foil
graphene
hydrogen peroxide
nucleation density
controlling
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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.)
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Application number
CN201410845545.2A
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Chinese (zh)
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CN104562005B (en
Inventor
丁荣
梁铮
倪振华
陈玉明
袁文军
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Taizhou Feirongda New Material Technology Co., Ltd.
Original Assignee
Sunano Technology Co
Taizhou Graphene Research And Characterization Platform Co Ltd
TAIZHOU SUNANO ENERGY CO Ltd
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Priority to CN201410845545.2A priority Critical patent/CN104562005B/en
Publication of CN104562005A publication Critical patent/CN104562005A/en
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    • 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 method for controlling nucleation density of graphene growing on the surface. The method is characterized by comprising the following steps: preparing hydrogen peroxide with the mass concentration of 5-30 percent; immersing a copper foil into the hydrogen peroxide to enable the copper foil to be oxidized by the hydrogen peroxide; growing the graphene by the pretreated copper foil by CVD. The immersion time in the step 2) is 5-60 seconds. Compared with other methods for controlling the nucleation density of graphene growing on the surface of the copper foil, the method disclosed by the invention is simple, convenient and feasible; only the copper foil needs to be pre-immersed in the hydrogen peroxide, and the nucleation density of the graphene on the surface of the copper foil can be effectively reduced. Meanwhile, the method can be matched with other control methods for use; on the basis of the method, the nucleation density can be further reduced by controlling a gas mixing ratio, the gas pressure intensity, the roughness of the surface of the copper foil, the growth temperature and the like, and the monocrystal size of a graphene thin film is enlarged.

Description

A kind of method controlling the Enhancing Nucleation Density of its epontic Graphene
Technical field
The present invention relates to a kind of method controlling the Enhancing Nucleation Density of its epontic Graphene, belong to field of material technology.
Background technology
Graphene has excellent electricity, mechanics, optics, thermal property, has broad prospects in fields such as electricity device, photoelectric device, radiating elements, and the preparation of the large size of Graphene, high quality is the prerequisite of its widespread use.
Chemical vapour deposition (CVD) method is the means being expected to realize graphene film suitability for industrialized production most, its reaction principle is: copper catalysis makes carbon-source gas decompose, carbon atom forms several nucleating centers at copper foil surface, and final grain growth links film forming.The quality of Graphene depends on its monocrystalline size, namely Enhancing Nucleation Density to a great extent.Researcher attempts the graphene film that the growth of various approach has large single crystal size always.While the guarantee speed of growth, improve the monocrystalline size of Graphene, namely reduce its Enhancing Nucleation Density, the quality of raising Graphene, the application of promotion Graphene are had great importance.
Current control Graphene the method for copper foil surface Enhancing Nucleation Density comprise control the air rate of methane, hydrogen, gas pressure intensity, the roughness of copper foil surface, growth temperature and high temperature under pass into dioxygen oxidation and reduce the methods such as copper foil surface activity site.This method of dioxygen oxidation reduction copper foil surface activity site is passed into very harsh for requirement for experiment condition, unfavorable suitability for industrialized production under method set forth above, particularly high temperature.
Summary of the invention
technical problem:in order to control the method for the Enhancing Nucleation Density of its surface growth Graphene, to solve the problems such as existing method complex process, the speed of growth be low, the invention provides a kind of method controlling the Enhancing Nucleation Density of its epontic Graphene.
technical scheme:the method of the Enhancing Nucleation Density of its epontic Graphene of control of the present invention, comprises the steps:
1) preparing mass concentration is the hydrogen peroxide of 5-30%;
2) soaked wherein by Copper Foil, Copper Foil is by hydrogen peroxide oxidation;
3) then CVD growing graphene is used for this pretreated Copper Foil.
Described step 2) in soak time be 5-60s.
Preferably,
Hydrogen peroxide mass concentration in described step 1) is 5%.
Described step 2) in soak time be 30s.
The CVD growing graphene method of described step 3) is as follows: by Copper Foil pretreated for hydrogen peroxide with do not carry out pretreated Copper Foil and be placed in parallel in growth furnace, control methane, hydrogen flow and be respectively 20 and 100sccm, mixing pressure is 200pa, growth temperature 1045 DEG C, growth time 1 minute.
The square ratio juris of the Enhancing Nucleation Density of its epontic Graphene of control of the present invention is as follows: the impurity activity of copper foil surface is comparatively strong, is the easy nucleation site of Graphene.Hydrogen peroxide pre-treatment makes copper foil surface be oxidized, at high temperature the oxygen of copper foil surface and surface impurity generation chemical reaction, thus reduces the density in copper foil surface active centre, reduces the Enhancing Nucleation Density of Graphene.
beneficial effect:be compared to the method that other control copper foil surface Graphene Enhancing Nucleation Density, present method is simple and easy to do, only needs to carry out to Copper Foil the Enhancing Nucleation Density that hydrogen peroxide dipping just effectively can reduce copper foil surface Graphene in advance.Meanwhile, present method also can with other control method conbined usage, on the basis of present method, by controlling air rate, gas pressure intensity, copper foil surface roughness, growth temperature etc., Enhancing Nucleation Density can be reduced further, improving the monocrystalline size of graphene film.
Accompanying drawing explanation
Fig. 1 is the 500 times of optical microscope picture (light tone region is single-layer graphene) distributed without the single-layer graphene forming core of the pretreated copper foil surface of hydrogen peroxide.
Fig. 2 is the 500 times of optical microscope picture (light tone region is single-layer graphene) distributed through the single-layer graphene forming core of the 5% hydrogen peroxide pre-treatment copper foil surface of 30 seconds.
Specific embodiment
Embodiment 1
The method of the Enhancing Nucleation Density of its epontic Graphene of control of the present invention, comprises the steps:
1) compound concentration mass concentration is 5% hydrogen peroxide solution;
2) obtain the Copper Foil that a slice thickness is 25 microns, and process 30 seconds in the hydrogen peroxide of 5%;
3) CVD growing graphene: by Copper Foil pretreated for hydrogen peroxide with do not carry out pretreated Copper Foil and be placed in parallel in growth furnace, control methane, hydrogen flow and be respectively 20 and 100sccm, mixing pressure is 200pa, growth temperature 1045 DEG C, growth time 1 minute;
By the Copper Foil hydrogen peroxide process number minute after growth, re-use the Enhancing Nucleation Density of observation by light microscope Graphene at copper foil surface.Fig. 1 is the 500 times of optical microscope picture (light tone region is Graphene) distributed without the single-layer graphene forming core of the pretreated copper foil surface of hydrogen peroxide.Fig. 2 is the 500 times of optical microscope picture (light tone region is Graphene) distributed through the single-layer graphene forming core of the 5% hydrogen peroxide pre-treatment copper foil surface of 30 seconds.Can find out, in advance the Enhancing Nucleation Density that hydrogen peroxide dipping just effectively can reduce copper foil surface Graphene be carried out to Copper Foil.

Claims (4)

1. control a method for the Enhancing Nucleation Density of its epontic Graphene, it is characterized in that, comprise the steps:
1) preparing mass concentration is the hydrogen peroxide of 5-30%;
2) soaked wherein by Copper Foil, Copper Foil is by hydrogen peroxide oxidation;
3) then CVD growing graphene is used for this pretreated Copper Foil,
Described step 2) in soak time be 5-60s.
2. method according to claim 1, is characterized in that, the hydrogen peroxide mass concentration in described step 1) is 5%.
3. method according to claim 1, is characterized in that, described step 2) in soak time be 30s.
4. method according to claim 1, it is characterized in that, the CVD growing graphene method of described step 3) is as follows: by Copper Foil pretreated for hydrogen peroxide with do not carry out pretreated Copper Foil and be placed in parallel in growth furnace, control methane, hydrogen flow and be respectively 20 and 100sccm, mixing pressure is 200pa, growth temperature 1045 DEG C, growth time 1 minute.
CN201410845545.2A 2014-12-31 2014-12-31 A kind of method of the Enhancing Nucleation Density of the graphene of its superficial growth of control Active CN104562005B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105369347A (en) * 2015-11-03 2016-03-02 电子科技大学 Device and method for preparing large-area graphene single crystal by controlling nucleus formation
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
CN112921296A (en) * 2021-01-22 2021-06-08 东北林业大学 Method for growing graphene on special-shaped metal substrate

Citations (4)

* Cited by examiner, † Cited by third party
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
JP2013540683A (en) * 2010-09-14 2013-11-07 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー Glass substrate having grown carbon nanotube and method for producing the same
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JP2013540683A (en) * 2010-09-14 2013-11-07 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー Glass substrate having grown carbon nanotube and method for producing the same
US20140014030A1 (en) * 2012-07-10 2014-01-16 William Marsh Rice University Methods for production of single-crystal graphenes
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

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105369347A (en) * 2015-11-03 2016-03-02 电子科技大学 Device and method for preparing large-area graphene single crystal by controlling nucleus formation
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
CN112921296A (en) * 2021-01-22 2021-06-08 东北林业大学 Method for growing graphene on special-shaped metal substrate
CN112921296B (en) * 2021-01-22 2022-05-24 东北林业大学 Method for growing graphene on special-shaped metal substrate

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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