CN105883779B - A kind of scalable process of CVD growth large-area graphene - Google Patents
A kind of scalable process of CVD growth large-area graphene Download PDFInfo
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- CN105883779B CN105883779B CN201510039352.2A CN201510039352A CN105883779B CN 105883779 B CN105883779 B CN 105883779B CN 201510039352 A CN201510039352 A CN 201510039352A CN 105883779 B CN105883779 B CN 105883779B
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Abstract
The present invention relates to the technology of preparing of graphene, specially a kind of scalable process of CVD growth large-area graphene.This method improves the yield of single batch growing large-area graphene by way of using growing substrate to be alternately stacked with solid-phase carbon source in CVD growth.Both are alternately stacked carry out CVD growth, are formed large-area graphene in the upper and lower surface of growing substrate, and reuse solid-phase carbon source by the present invention using the growing substrate of planar structure and the solid-phase carbon source of reusable edible.The mode that growing substrate is alternately stacked with solid-phase carbon source, greatly improved the single batch useful load of growing substrate, and the upper and lower surface for realizing growing substrate grows the large-area graphene of high quality, so as to improve the yield of single batch growth graphene.The high production cost caused by largely consuming high-purity gas phase carbon source can be avoided using the solid-phase carbon source of reusable edible, therefore can be as the scalable process of a kind of low cost, high efficiency production large-area graphene.
Description
Technical field:
It is specially a kind of to be alternately stacked using growing substrate and solid-phase carbon source the present invention relates to the technology of preparing of graphene
The scalable process of the efficient CVD growth large-area graphene of mode.
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, preparing for high-quality graphene are most important.Peeled off from the seminar of Univ Manchester UK in 2004 using adhesive tape
After method (or micromechanics stripping method) separates the graphene for obtaining and being stabilized first, the method for much preparing graphene is sent out successively
Exhibition is got up, including chemical oxidation stripping method, precipitation growth method and chemical vapor deposition (CVD) method.Wherein, CVD method is current
Controllable preparation large area, the main method of high-quality graphene., can be with by controlling the preparation conditions such as temperature, carbon source and pressure
Realize the graphene that large area, high quality are grown in a variety of substrate material surfaces (metal and nonmetallic).In recent years, CVD
The graphene of preparation has been used to prepare high performance transparent graphene conductive film, in the photoelectric device using touch-screen as representative
Wide application prospect has been shown Deng field.In order to further promote the application of graphene, it is necessary to develop CVD growth large area
The scalable process of graphene, largely it can prepare graphene realizing low cost.
At present, the scalable process of CVD growth large-area graphene mainly includes coiled-type growth and volume to volume growth.Before
The growing substrate (such as copper foil) of graphene is carried out static growth by person wound on supporting body surfaces such as quartz ampoules；The latter is using company
The mode of continuousization transmission tinsel carries out dynamic growth.Although two kinds of growth patterns are easily achieved large-scale production, but because
The useful load of growing substrate is relatively low, causes the yield of single batch relatively low.The large-area graphene growing method that in addition, there will be is adopted
With high-purity gas phase carbon source, not only increased production cost, and air flow method is vulnerable to the influence of growing substrate useful load, height dress
The problem of graphene growth is uneven during carrying capacity be present.
The content of the invention:
For above mentioned problem existing for existing CVD preparation methods, it is an object of the invention to provide a kind of inexpensive, efficient
The scalable process of rate CVD growth large-area graphene, by the way of growing substrate and solid-phase carbon source are alternately stacked, improve single
The yield of batch growing large-area graphene, while graphene growth to be present uneven when solving high useful load in the prior art
Problem.
The technical scheme is that：
A kind of scalable process of CVD growth large-area graphene, this method in CVD growth by using growing substrate
The mode being alternately stacked with solid-phase carbon source, using the growing substrate of planar structure and the solid-phase carbon source of reusable edible, it incite somebody to action both
Carry out CVD growth is alternately stacked, so as to form large-area graphene in the upper and lower surface of growing substrate, and reuses solid carbon
Source；Comprise the following steps that：
(1) growing substrate of planar structure is used, uniform solid carbon active layer is formed on its surface；
(2) second layer growing substrate and solid carbon active layer are stacked successively in established solid-phase carbon source layer surface；
(3) repeat the above steps until the growing substrate of the number of plies needed for reaching；
(4) lamination of above-mentioned growing substrate and solid-phase carbon source is put into CVD system to be grown, on the surface of growing substrate
Form graphene；
(5) after CVD growth terminates, the growing substrate that has graphene will be grown and separated with solid-phase carbon source, and by solid carbon
Source is re-used for CVD growth.
The scalable process of described CVD growth large-area graphene, the growing substrate of graphene is Pt, Ni, Cu, Co,
One of Ir, Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta, Cr metal or its alloy or two or more composites；Or
Person, the growing substrate of graphene is titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, tungsten carbide
One of or two or more composites；Or the growing substrate of graphene is Si, SiO2、Al2O3One of semiconductor or two kinds
It is compound above；Or the composite that the growing substrate of graphene is both conductor and semiconductor.
The scalable process of described CVD growth large-area graphene, the alloy of the metal is copper alloy, nickel alloy or
Stainless steel.
The scalable process of described CVD growth large-area graphene, the growing substrate of graphene is planar structure, including
One of film, paillon foil, sheet material are two or more compound.
The scalable process of described CVD growth large-area graphene, solid-phase carbon source material be Carbon Materials, organic matter or its
Its carbon compound, the exclusive use or compound with other materials of solid-phase carbon source material.
The scalable process of described CVD growth large-area graphene, the form of solid-phase carbon source material include continuous put down
Face structure or powder structure, separate and reuse with growing substrate after CVD growth.
The scalable process of described CVD growth 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 scalable process of described CVD growth large-area graphene, graphite is respectively formed in the upper and lower surface of growing substrate
Alkene, the average number of plies of graphene is that individual layer, bilayer, few layer or multilayer, the number of plies are less than 50 layers.
The scalable process of described CVD growth large-area graphene, in CVD growth, furnace chamber is vacuumized first, until
Pressure is less than 1Pa, then is passed through flow and is 1~100sccm hydrogen, and pressure is maintained into 1~500Pa；In 1~30 minute
Furnace temperature is risen to 300-1500 DEG C, is incubated 1~60 minute；Then cool to room temperature with the furnace, or the sample of lamination is carried out soon
Speed is cooled to room temperature, and cooling velocity is 10~20 DEG C/sec, completes CVD growth.
The features of the present invention and beneficial effect are：
1. the present invention greatly improves the single batch of growing substrate by the way of growing substrate and solid-phase carbon source is alternately stacked
Useful load；Meanwhile layer-by-layer growth can realize that the upper and lower surface of growing substrate is respectively formed graphene, the growth of single matrix is imitated
Rate improves twice.Therefore, the yield of single batch CVD growth large-area graphene can be significantly improved.
2. using independent used carbon containing solid phase material as carbon source in the present invention, and by controlling CVD growth condition,
Ensure to reuse carbon source.Therefore, compared to high-purity gas phase carbon source is largely consumed, cost of material significantly reduces.
3. in the present invention, growing substrate is in close contact with solid carbon active layer, on the one hand reduces growing substrate material under high temperature
On the other hand the volatilizing loss of material is advantageous to the heat biography between each layer growing substrate so as to improve the service life of matrix material
Lead, it is ensured that growth temperature is uniformly distributed.
4. in the present invention, growing substrate is planar structure, and with the uniform mutual lamination of solid carbon active layer, after CVD growth
It can still keep growing substrate smooth, therefore be advantageous to improve the integrality of transfer in follow-up graphene transfer process.
Brief description of the drawings:
The scale CVD growth method schematic diagram of Fig. 1 large-area graphenes.
Embodiment:
Below by embodiment and accompanying drawing, the present invention is described in more detail.
Embodiment 1
As shown in figure 1, growing substrate is used as using metal copper foil (25 microns of thickness), using carbon felt (50 microns of thickness) as solid
Phase carbon source.Smooth large area copper foil and carbon felt alternative stacked are stacked, the number of plies is 200 layers.By the copper foil and carbon felt after lamination
It is put into electrically heated CVD stoves and is grown.Furnace chamber is vacuumized first, until pressure is less than 1Pa, then flow is passed through and is
100sccm hydrogen, and pressure is maintained into 50Pa；Furnace temperature is risen to 1000 DEG C in 30 minutes, with stove after being incubated 10 minutes
Room temperature is cooled to, completes CVD growth.The upper and lower surface of copper foil is respectively formed the large area single-layer graphene of high quality, while carbon felt
CVD growth can be re-used for.
Embodiment 2
It is with the difference of embodiment 1：
Using other materials as solid-phase carbon source, including flexible graphite paper, carbon nanotube film, fullerene, carbon black or carbon
SiClx etc.；Grown using atmospheric pressure cvd technique, carrier gas is argon gas.
Embodiment 3
As shown in figure 1, be coated with the quartz plate of nickel film (500 nanometer thickness) as growing substrate using surface, using being soaked with ring
The carbon cloth (200 microns of thickness) of oxygen tree fat is used as solid-phase carbon source.By nickel film/quartz plate and carbon fiber/resin cloth alternative stacked
Stack, the number of plies is 100 layers.The sample of lamination is put into induction heating type CVD stoves and grown.Furnace chamber is vacuumized first,
Until pressure is less than 1Pa, then is passed through flow and is 50sccm hydrogen, and pressure is maintained into 20Pa；By furnace temperature liter in 3 minutes
To 1000 DEG C, 1 minute is incubated；Then the sample of lamination is carried out being quickly cooled to room temperature, cooling velocity is 15 DEG C/sec, is completed
CVD growth.Nickel film surface forms the few layer graphene of large area of high quality, and carbon cloth can be repeated for CVD growth.
Embodiment result shows that the present invention, will using the growing substrate of planar structure and the solid-phase carbon source of reusable edible
Both are alternately stacked carry out CVD growth, greatly improve the single batch useful load of growing substrate, and realize the upper and lower of growing substrate
Surface grows the large-area graphene of high quality, solid-phase carbon source is reused, so as to improve single batch growing large-area stone
The yield of black alkene.Moreover, using the solid-phase carbon source of reusable edible, can avoid caused by largely consuming high-purity gas phase carbon source
High production cost, therefore can be as the scalable process of a kind of low cost, high efficiency production large-area graphene.
Claims (9)
- A kind of 1. scalable process of CVD growth large-area graphene, it is characterised in that：This method in CVD growth by adopting The mode being alternately stacked with growing substrate and solid-phase carbon source, uses the growing substrate of planar structure and the solid carbon of reusable edible Source, both are alternately stacked carry out CVD growth, so as to form large-area graphene in the upper and lower surface of growing substrate, and repeated Use solid-phase carbon source；Comprise the following steps that：(1) growing substrate of planar structure is used, uniform solid carbon active layer is formed on its surface；(2) second layer growing substrate and solid carbon active layer are stacked successively in established solid-phase carbon source layer surface；(3) repeat the above steps until the growing substrate of the number of plies needed for reaching；(4) lamination of above-mentioned growing substrate and solid-phase carbon source is put into CVD system to be grown, formed on the surface of growing substrate Graphene；(5) after CVD growth terminates, the growing substrate that growth has graphene is separated with solid-phase carbon source, and by solid-phase carbon source again It is secondary to be used for CVD growth.
- 2. according to the scalable process of the CVD growth large-area graphene described in claim 1, it is characterised in that：Graphene Growing substrate be one of Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta, Cr metal or its alloy or Two or more composites；Or the growing substrate of graphene be titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, One of ramet, chromium carbide, tungsten carbide or two or more composites；Or the growing substrate of graphene is Si, SiO2、 Al2O3One of semiconductor is two or more compound；Or the composite wood that the growing substrate of graphene is both conductor and semiconductor Material.
- 3. according to the scalable process of the CVD growth large-area graphene described in claim 2, it is characterised in that：The metal Alloy be copper alloy, nickel alloy or stainless steel.
- 4. according to the scalable process of the CVD growth large-area graphene described in claim 1, it is characterised in that：Graphene Growing substrate is planar structure, including one of film, paillon foil, sheet material or two or more compound.
- 5. according to the scalable process of the CVD growth large-area graphene described in claim 1, it is characterised in that：Solid-phase carbon source Material is Carbon Materials or organic matter, and solid-phase carbon source material is used alone or compound with other materials.
- 6. according to the scalable process of the CVD growth large-area graphene described in claim 1, it is characterised in that：Solid-phase carbon source The form of material includes continuous planar structure or powder structure, separates and reuses with growing substrate after CVD growth.
- 7. according to the scalable process of the CVD growth 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.
- 8. according to the scalable process of the CVD growth large-area graphene described in claim 1, it is characterised in that：In growth base The upper and lower surface of body is respectively formed graphene, and the average number of plies of graphene is that individual layer, bilayer, few layer or multilayer, the number of plies are less than 50 layers.
- 9. according to the scalable process of the CVD growth large-area graphene described in claim 1, it is characterised in that：CVD growth In, furnace chamber is vacuumized first, until pressure is less than 1Pa, then is passed through flow and is 1~100sccm hydrogen, and pressure maintained In 1~500Pa；Furnace temperature is risen to 300-1500 DEG C in 1~30 minute, is incubated 1~60 minute；Then room is cooled to the furnace Temperature, or the sample of lamination is carried out being quickly cooled to room temperature, cooling velocity is 10~20 DEG C/sec, completes CVD growth.
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| CN109216496B (en) * | 2018-10-22 | 2020-01-10 | 北京工业大学 | Silicon schottky junction detector for directly growing graphene by applying parylene N film |
| CN109518158B (en) * | 2019-01-04 | 2021-02-09 | 无锡第六元素电子薄膜科技有限公司 | Macroscopic quantity preparation method of graphene film |
| CN110040726A (en) * | 2019-03-13 | 2019-07-23 | 中国科学院金属研究所 | A method of preparing large-area high-quality uniformly a small number of layer graphene films |
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Effective date of registration: 20210220 Address after: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee after: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES Patentee after: Deyang Peihua Carbon Material Technology Development Co.,Ltd. Address before: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee before: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES |