CN103345979B - A kind of preparation method of graphene conductive film - Google Patents
A kind of preparation method of graphene conductive film Download PDFInfo
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- CN103345979B CN103345979B CN201310263553.1A CN201310263553A CN103345979B CN 103345979 B CN103345979 B CN 103345979B CN 201310263553 A CN201310263553 A CN 201310263553A CN 103345979 B CN103345979 B CN 103345979B
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Abstract
The invention discloses a kind of preparation method of graphene conductive film, belong to technical field of semiconductor material preparation.Described method comprises: utilize chemical gaseous phase depositing process growing graphene in metal foil surface; Electro-deposition method is utilized to have the metal foil surface deposited oxide Graphene of Graphene in growth; The metal forming that deposited graphene oxide is carried out reduction treatment under protection gas and hot conditions, makes graphene oxide be reduced to Graphene.The present invention combines by chemical vapour deposition technique and graphene oxide reduction are prepared Graphene method, in order to prepare graphene conductive film, the graphene film that the method obtains not only good conductivity, light transmittance is high, and cost is low, processing step simple, may be used for large-scale production and prepares transparent graphene conductive film.
Description
Technical field
The present invention relates to technical field of semiconductor material preparation, particularly a kind of preparation method with the large-area graphene conductive film of higher light transmittance.
Background technology
2004, Univ Manchester UK professor Geim prepared Graphene [K.S.Novoselov, A.K.Geim, S.V.Morozov first, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov, Science2004,306,666.].Graphene is by the former molecular six side's honeycomb two-dimensional structures of monolayer carbon.Under graphene film room temperature, native electronic mobility can reach 200000cm
2/ Vs, has excellent electrical properties [K.I.Bolotin, K.J.Sikes, Z.Jiang, M.Klima, G.Fudenberg, J.Hone, P.Kim, H.L.Stormer, SolidStateCommunications2008,146,351.].In addition, Graphene all has high light transmittance in whole visible region, and research finds that the light transmittance of single-layer graphene is close to 97%[R.R.Nair, P.Blake, A.N.Grigorenko, K.S.Novoselov, T.J.Booth, T.Stauber, N.M.R.Peres, A.K.Geim, Science2008,320,1308.], therefore Graphene has huge, potential application performance in touch-screen field.
The suprabasil chemical vapour deposition (CVD) of copper (CVD) is a kind of important method preparing graphene film, and the method not only can realize the preparation of large-area graphene, and obtained Graphene better performances [X.S.Li, W.W.Cai, J.H.An, S.Kim, J.Nah, D.X.Yang, R.Piner, A.Velamakanni, I.Jung, E.Tutuc, S.K.Banerjee, L.Colombo, R.S.Ruoff, Science2009,324,1312.].But what this method obtained is single-layer graphene, its conductivity usually can not meet the demands, and needs to prepare multi-layer graphene film to meet conduction needs by repeatedly shifting, and greatly will increase production cost like this.
It is a kind of preparation method with low cost that Graphene is prepared in graphene oxide reduction, graphene oxide film can adopt roller coating, spraying and electro-deposition method film forming, wherein electro-deposition method has very large advantage in extensive preparation, and it requires that substrate has conductivity.But the Graphene defect that the method obtains is more, make the poor-performing [D.W.Boukhvalov, M.I.Katsnelson, JournaloftheAmericanChemicalSociety2008,130,10697.] of graphene film.
Summary of the invention
In order to solve the problems such as existing multi-layer graphene film preparation production cost is high, defect is many, the invention provides a kind of preparation method of graphene conductive film, the method comprises:
Chemical gaseous phase depositing process growing graphene is utilized in metal foil surface;
Electro-deposition method is utilized to have the metal foil surface deposited oxide Graphene of Graphene in growth, specifically comprise: growth had the metal forming of Graphene to immerse in graphene oxide dispersion as positive electrode, use electric conducting material as negative electrode, direct voltage is applied between positive and negative two electrodes, direct voltage is 2-50V, and electrodeposition time is 0.5-5 minute;
The metal forming that deposited graphene oxide is carried out reduction treatment under protection gas and hot conditions, makes graphene oxide be reduced to Graphene; The reducing condition carrying out reduction treatment under described hot conditions is: temperature is 800-1050 DEG C, and the recovery time is 3-20 minute.
Describedly the growth conditions of chemical gaseous phase depositing process growing graphene is utilized to be in metal foil surface: growth temperature is 900-1070 DEG C, and gases used is CH
4and H
2gaseous mixture, gas flow is respectively 2-50sccm and 5-100sccm, and growth time is 2-30 minute.
Described electric conducting material comprises graphite, platinum and stainless steel.
Described protection gas bag draws together Ar, N
2and H
2in one or more.
Described protection gas is H
2with the gaseous mixture of Ar, gas flow is respectively 1-50sccm and 1-100sccm.
The present invention combines, in order to prepare graphene conductive film by chemical vapour deposition technique (CVD) and graphene oxide reduction are prepared Graphene method.The graphene film that the method obtains not only good conductivity, light transmittance is high, and cost is low, processing step simple, may be used for large-scale production and prepares transparent graphene conductive film.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of the graphene conductive film that the embodiment of the present invention provides;
Fig. 2 is the principle schematic of the electro deposition oxidation Graphene that the embodiment of the present invention provides;
Fig. 3 is the process schematic utilizing the embodiment of the present invention to prepare transparent graphene conductive film;
Fig. 4 is the membrane structure schematic diagram before and after the transparent graphene conductive film copper corrosion of the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
See Fig. 1, embodiments provide a kind of preparation method of graphene conductive film, the method comprises the following steps:
Step 101: utilize chemical gaseous phase depositing process growing graphene in metal foil surface;
In the present embodiment, use Copper Foil as metal foil substrate, utilize chemical vapour deposition (CVD) (CVD) method growing graphene on surfaces of the copper foil, growth temperature is 900-1070 DEG C, and preferably, the present embodiment adopts 1000 DEG C as growth temperature; Gases used is CH
4and H
2gaseous mixture, gas flow is respectively 2-50sccm and 5-100sccm, preferably, the present embodiment adopt CH
4gas flow be 5sccm, H
2gas flow be 10sccm; Growth time is 2-30 minute, and preferably, the present embodiment adopts 10 minutes as growth time;
Step 102: have the Copper Foil of Graphene (being expressed as: copper/Graphene) to immerse in previously prepared graphene oxide dispersion as positive electrode growth, use electric conducting material as negative electrode, direct voltage is applied between positive and negative two electrodes, direct voltage size is 2-50V, electrodeposition time is 0.5-5 minute, electro-deposition method is utilized to have the copper foil surface deposited oxide Graphene of Graphene in growth, as shown in Figure 2;
Graphite oxidation is prepared into graphite oxide, in water, is then adopted ultra-sonic dispersion method to prepare graphene oxide dispersion; The electric conducting material of negative electrode comprises graphite, platinum and stainless steel etc.; Select graphite electrode as negative electrode in the present embodiment, two electrodes are at a distance of 2cm, and two electrodes apply the direct voltage of 10V, and electrodeposition time is 1 minute;
Step 103: copper/Graphene (being expressed as: the copper/graphene/graphene oxide) substrate that deposited graphene oxide is carried out reduction treatment under protection gas and hot conditions, makes graphene oxide be reduced to Graphene;
In actual applications, gas bag is protected to draw together Ar, N
2and H
2in one or more, the temperature of hot conditions is 800-1050 DEG C; In the present embodiment, temperature conditions is 1000 DEG C, and protection gas is by H
2with the mist of Ar composition, wherein H
2be respectively 1-50sccm and 1-100sccm with the gas flow of Ar, preferably, the present embodiment adopts H
2gas flow be the gas flow of 10sccm, Ar be 100sccm, the recovery time is 3-20 minute, and preferably, the present embodiment adopts 5 minutes as the recovery time, makes graphene oxide be reduced to Graphene, and then obtains graphene conductive film.
In concrete production practices, utilize graphene conductive film prepared by the present embodiment, can in different transparent substrates, such as: glass, quartz, PET film etc., prepare transparent graphene conductive film, concrete preparation process is as follows, and as shown in Figure 3: 1) at transparent substrates (for glass) application of adhesive on the surface, adhesive comprises epoxy resin, PDMS and PET etc. (for epoxy resin); CVD growing graphene needs to transfer to other substrate by it from copper foil surface by transfer operation, and because the adhesion between Graphene and substrate is more weak, therefore the breakage of Graphene is serious; Utilize adhesive can increase active force between Graphene and substrate, thus realize the LB rate transfer of Graphene; 2) graphene conductive film prepared by the present embodiment adheres on the glass surface by epoxy resin, is wherein directly contacted with epoxy resin by the graphene oxide layer after thermal reduction; 3) normal temperature places 1 hour after the abundant dry solidification of epoxy resin, substrate of glass is immersed in metallic copper etchant solution, utilizes wet etching to remove copper, as shown in Figure 4; Metallic copper corrosive liquid comprises ferric chloride aqueous solutions, iron nitrate aqueous solution and salpeter solution etc., for ferric chloride aqueous solutions, it is remove Copper Foil in the ferric chloride aqueous solutions of 0.5mol/L that substrate of glass is immersed in concentration, wash repeatedly with deionized water after removing copper completely, glass basic surface is cleaned up, and then obtains the transparent graphene conductive film transferred in substrate of glass.In actual applications, according to used metal foil substrate, the corrosion of metals solution be applicable to should be selected, to reach the effect of corrosion; In addition, also according to selected different transparent substrates, the adhesive adapted with this transparent substrates should be selected, to reach good adhesiving effect.
The embodiment of the present invention combines, in order to prepare graphene conductive film by chemical vapour deposition technique (CVD) and graphene oxide reduction are prepared Graphene method.The method not only can improve conductivity and the light transmittance of graphene film effectively, but also can greatly reduce the damaged degree of Graphene, has the advantage that preparation method is simple, production cost is low and be applicable to large-scale production simultaneously.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a preparation method for graphene conductive film, is characterized in that, comprising:
Chemical gaseous phase depositing process growing graphene is utilized in metal foil surface;
Electro-deposition method is utilized to have the metal foil surface deposited oxide Graphene of Graphene in growth, specifically comprise: growth had the metal forming of Graphene to immerse in graphene oxide dispersion as positive electrode, use electric conducting material as negative electrode, direct voltage is applied between positive and negative two electrodes, direct voltage is 2-50V, and electrodeposition time is 0.5-5 minute;
The metal forming that deposited graphene oxide is carried out reduction treatment under protection gas and hot conditions, makes graphene oxide be reduced to Graphene; The reducing condition carrying out reduction treatment under described hot conditions is: temperature is 800-1050 DEG C, and the recovery time is 3-20 minute.
2. the preparation method of graphene conductive film as claimed in claim 1, is characterized in that, describedly utilizes the growth conditions of chemical gaseous phase depositing process growing graphene to be in metal foil surface: growth temperature is 900-1070 DEG C, and gases used is CH
4and H
2gaseous mixture, gas flow is respectively 2-50sccm and 5-100sccm, and growth time is 2-30 minute.
3. the preparation method of graphene conductive film as claimed in claim 1, it is characterized in that, described electric conducting material comprises graphite, platinum and stainless steel.
4. the preparation method of graphene conductive film as claimed in claim 1, it is characterized in that, described protection gas bag draws together Ar, N
2and H
2in one or more.
5. the preparation method of graphene conductive film as claimed in claim 4, it is characterized in that, described protection gas is H
2with the gaseous mixture of Ar, gas flow is respectively 1-50sccm and 1-100sccm.
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| CN103632771A (en) * | 2013-12-06 | 2014-03-12 | 苏州瑞邦塑胶有限公司 | Manufacturing process of graphene transparent conductive film |
| CN103887013A (en) * | 2013-12-31 | 2014-06-25 | 美特科技(苏州)有限公司 | Production method for copper-coated graphene conductive wire |
| CN104973592B (en) * | 2014-04-11 | 2017-02-08 | 中国科学院上海硅酸盐研究所 | Liquid-phase oriented preparation method of high-electric-conductive and high-heat-conductive graphene film |
| CN104617235A (en) | 2015-02-25 | 2015-05-13 | 京东方科技集团股份有限公司 | Organic electroluminescence display device and manufacturing method thereof as well as display device |
| WO2019100674A1 (en) * | 2017-11-24 | 2019-05-31 | 深圳大学 | Graphene material and sensor for detecting gas component |
| CN109859902B (en) * | 2019-01-14 | 2020-07-28 | 代荣记 | Process for manufacturing bare stranded wire with identification anti-counterfeiting code |
| CN114507791B (en) * | 2022-01-26 | 2022-09-23 | 重庆墨希科技有限公司 | Production method and equipment of graphene metal conductive material |
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| CN103035877A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Graphene/elemental tin combined electrode plate and preparation method of same |
| CN103072978A (en) * | 2013-02-04 | 2013-05-01 | 杭州格蓝丰纳米科技有限公司 | Chemical vapor deposition method for preparing dual-layer graphene |
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| CN102275858A (en) * | 2011-06-20 | 2011-12-14 | 南京航空航天大学 | Graphene-ion exchange polymer electric actuator as well as manufacturing method and application thereof |
| CN103035877A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Graphene/elemental tin combined electrode plate and preparation method of same |
| CN103072978A (en) * | 2013-02-04 | 2013-05-01 | 杭州格蓝丰纳米科技有限公司 | Chemical vapor deposition method for preparing dual-layer graphene |
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