CN105887041B

CN105887041B - A kind of CVD method of inexpensive growing large-area graphene

Info

Publication number: CN105887041B
Application number: CN201510039341.4A
Authority: CN
Inventors: 任文才; 马来鹏; 成会明
Original assignee: Institute of Metal Research of CAS
Current assignee: Deyang Peihua Carbon Material Technology Development Co.,Ltd.; Institute of Metal Research of CAS
Priority date: 2015-01-26
Filing date: 2015-01-26
Publication date: 2018-03-09
Anticipated expiration: 2035-01-26
Also published as: CN105887041A

Abstract

It is specially a kind of using CVD method of the unwashed extruded metal as matrix material low cost growing large-area graphene the present invention relates to the technology of preparing of graphene.This method uses matrix material of the unwashed extruded metal as CVD growth graphene, and the grease of metal surface is remained in after being processed by the use of calendering as the carbon source of growth graphene, is concretely comprised the following steps：(1) using matrix of the unwashed extruded metal as CVD growth graphene, the grease of its remained on surface is as the carbon source for growing graphene；(2) above-mentioned material is directly placed into CVD system to be grown, large-area graphene is formed on its surface.Using the present invention without using additional carbon, preparation cost is reduced, a kind of method that large-area graphene can be produced as low cost.

Description

A kind of CVD method of inexpensive growing large-area graphene

Technical field:

The present invention relates to the technology of preparing of graphene, is specially that one kind uses unwashed extruded metal as matrix material The CVD method of inexpensive growing large-area graphene.

Background technology:

Graphene be by single layer of carbon atom it is tightly packed into bi-dimensional cellular shape crystal structure, be build other dimension raws material of wood-charcoal Expect the basic structural unit of (zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).The unique crystal structure of graphene has it There are excellent electricity, calorifics and mechanical property, such as its electron mobility is up to 200,000cm at room temperature²/ Vs, thermal conductivity are high Up to 5300W/mk, it is expected in multi-functional nanometer electronic device, nesa coating, composite, catalysis material, energy storage material, field The fields such as emissive material, gas sensor and gas storage obtain extensive use.In order to comprehensively utilize the numerous excellent of graphene Characteristic, the preparation method of high-quality graphene are most important.Adhesive tape is used from the seminar of Univ Manchester UK in 2004 After stripping method (or micromechanics stripping method) separates the graphene for obtaining and being stabilized first, the method for graphene is much prepared successively It is developed, including chemical oxidation stripping method, precipitation growth method and chemical vapor deposition (CVD) method.Wherein, CVD is mesh Preceding controllable preparation large area, the main method of high-quality graphene., can by controlling the preparation conditions such as temperature, carbon source and pressure To realize in a variety of substrate material surfaces (metal and nonmetallic) growth graphene.In recent years, the graphene that prepared by CVD is For preparing high performance transparent graphene conductive film, shown extensively by fields such as the photoelectric devices of representative of touch-screen Wealthy application prospect.

At present, existed using CVD growing large-area graphene and prepare the problem of cost is higher.In order to further promote stone The application of black alkene is, it is necessary to which developing reduces the effective way that CVD prepares cost.The CVD growth side of typical large-area graphene Method uses additional carbon, using hydrocarbons such as high-purity methanes as Typical Representative.The typical CVD works of growing large-area graphene Skill needs to consume substantial amounts of gaseous carbon sources, and the cost of the hydrocarbon gas such as high-purity methane is higher.As can be seen that gaseous carbon sources are Through the pith that cost is prepared as large-area graphene.

The content of the invention:

It is an object of the invention to provide a kind of CVD method of inexpensive growing large-area graphene, use are unwashed Matrix material of the extruded metal as CVD growth graphene, directly made using the grease that metal surface is remained in after calendering processing Make a living the carbon source of long graphene, without using additional carbon, so as to reduce preparation cost.

The technical scheme is that：

A kind of CVD method of inexpensive growing large-area graphene, using unwashed extruded metal as CVD growth stone The growing substrate material of black alkene, the grease of metal surface is remained in after being processed by the use of calendering as the carbon source of growth graphene；Tool Body step is as follows：

(1) using matrix of the unwashed extruded metal as CVD growth graphene, the grease of its remained on surface is as life The carbon source of long graphene；

(2) above-mentioned material is directly placed into CVD system to be grown, large-area graphene is formed on its surface.

The CVD method of described inexpensive growing large-area graphene, the extruded metal used for Cu, Ni, Pt, Co, Ir, One of Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta, Cr or two or more alloy or composite.

The CVD method of described inexpensive growing large-area graphene, the growing substrate of graphene for planar structure or For curved-surface structure.

The CVD method of described inexpensive growing large-area graphene, the carbon source of CVD growth growth graphene used is pressure Prolong the lubricant grease used in processing metal process, Main Ingredients and Appearance is hydrocarbon.

The CVD method of described inexpensive growing large-area graphene, the equipment of CVD growth include hot type CVD or waited Gas ions enhancing CVD (PECVD), the technique of CVD growth include low pressure process or atmospheric processes, and the atmosphere of CVD growth is included also Originality atmosphere or inert atmosphere, the mode of heating of CVD growth include electrical heating, sensing heating, irradiated heat or laser heating, The type of cooling of CVD growth is Slow cooling or quick cooling.

The CVD method of described inexpensive growing large-area graphene, the average layer of graphene is formed in growing substrate Number is individual layer, bilayer, few layer or multilayer, the number of plies are less than 50 layers.

The CVD method of described inexpensive growing large-area graphene, in CVD growth, unwashed extruded metal is put Enter and grown in CVD stoves；Furnace chamber is vacuumized first, until pressure is less than 1Pa, then is passed through the hydrogen that flow is 1~500sccm The argon gas of gas and/or 10~2000sccm, and pressure is maintained into 1Pa to normal pressure；By growing substrate surface in 1~30 minute Temperature rise to 800~1000 DEG C, be incubated 1~60 minute；Then cool to room temperature with the furnace, or carry out being quickly cooled to room Temperature, cooling velocity are 10~20 DEG C/sec, complete CVD growth.

The features of the present invention and beneficial effect are：

1. the grease that metal surface is remained in after the direct processing by the use of calendering of the invention is used as the carbon source of growth graphene, nothing Additional carbon, and unwashed extruded metal advantage of lower cost need to be used, therefore the cost of material of CVD growth can be reduced.

2. the method for the present invention can reduce the relevant configuration of CVD system, reduce equipment cost without using additional carbon.

Embodiment:

Below by embodiment, the present invention is described in more detail.

Embodiment 1

Growing substrate material is used as using unskimmed rolled copper foil (25 microns of thickness).Large area copper foil is lain in into quartz Plate surface, it is put into light irradiation formula CVD stoves and is grown.Furnace chamber is vacuumized first, until pressure is less than 1Pa, then is passed through stream The hydrogen for 10sccm is measured, and pressure is maintained into 10Pa；The temperature of copper foil surface is risen to 1000 DEG C in 5 minutes, insulation 5 Cool to room temperature after minute with the furnace, complete CVD growth.Finally, the large-area graphene that individual layer is dominant is formed on the surface of copper foil.

Embodiment 2

It is with the difference of embodiment 1：

Using the PECVD system of Reel-to-reel type, directly growing substrate is used as using coiled rolled copper foil (35 microns of thickness) Material, continuously grown at 300 DEG C, the upper and lower surface of copper foil is respectively formed the large-area graphene that individual layer is dominant.

Embodiment 3

Growing substrate material is used as using unskimmed calendering nickel foil (50 microns of thickness).Large area nickel foil is lain in into quartz Plate surface, it is put into induction heating type CVD stoves and is grown.Furnace chamber is vacuumized first, until pressure is less than 1Pa, then is passed through Flow is 50sccm hydrogen and 200sccm argon gas, until pressure rises to normal pressure；Furnace temperature is risen to 1000 DEG C in 1 minute, Insulation 1 minute；Then nickel foil is carried out being quickly cooled to room temperature, cooling velocity is 15 DEG C/sec, completes CVD growth.Finally, exist Nickel foil surface forms the few layer graphene of large area of high quality.

Embodiment result shows that the inventive method uses matrix of the unwashed extruded metal as CVD growth graphene Material, the grease of metal surface is remained in after being processed by the use of calendering as the carbon source for growing graphene, without using additional carbon, So as to reduce preparation cost.Therefore, can be as a kind of method of low cost production large-area graphene.

Claims

A kind of 1. CVD method of inexpensive growing large-area graphene, it is characterised in that：Using unwashed extruded metal conduct The growing substrate material of CVD growth graphene, the grease that metal surface is remained in after being processed by the use of calendering are used as growth graphene Carbon source；Comprise the following steps that：

(1) using matrix of the unwashed extruded metal as CVD growth graphene, the grease of its remained on surface is as growth stone The carbon source of black alkene；

(2) above-mentioned matrix is directly placed into CVD system to be grown, large-area graphene is formed on its surface.
2. according to the CVD method of the inexpensive growing large-area graphene described in claim 1, it is characterised in that：The pressure of use Prolong metal as one of Cu, Ni, Pt, Co, Ir, Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta, Cr or two or more alloys Or composite.
3. according to the CVD method of the inexpensive growing large-area graphene described in claim 1, it is characterised in that：Graphene Growing substrate is planar structure or is curved-surface structure.
4. according to the CVD method of the inexpensive growing large-area graphene described in claim 1, it is characterised in that：CVD growth institute Carbon source with growth graphene is the lubricant grease used in calendering processing metal process, and Main Ingredients and Appearance is hydrocarbon.
5. according to the CVD method of the inexpensive growing large-area graphene described in claim 1, it is characterised in that：CVD growth Equipment includes hot type CVD or plasma enhanced CVD (PECVD), and the technique of CVD growth includes low pressure process or normal pressure work Skill, the atmosphere of CVD growth include reducing atmosphere or inert atmosphere, and the mode of heating of CVD growth adds including electrical heating, sensing Heat, irradiated heat or laser heating, the type of cooling of CVD growth is Slow cooling or quick cooling.
6. according to the CVD method of the inexpensive growing large-area graphene described in claim 1, it is characterised in that：In growth base The average number of plies that body forms graphene is individual layer, bilayer or multilayer, and the number of plies is less than 50 layers.
7. according to the CVD method of the inexpensive growing large-area graphene described in claim 1, it is characterised in that：CVD growth In, unwashed extruded metal is put into CVD stoves and grown；Furnace chamber is vacuumized first, until pressure is less than 1Pa, then Flow is passed through as 1~500sccm hydrogen and/or 10~2000sccm argon gas, and pressure is maintained into 1Pa to normal pressure；1 The temperature on growing substrate surface is risen to 800~1000 DEG C in~30 minutes, is incubated 1~60 minute；Then room is cooled to the furnace Temperature, or carry out being quickly cooled to room temperature, cooling velocity is 10~20 DEG C/sec, completes CVD growth.