CN105883779A - Method for large-scale CVD growth of graphene - Google Patents
Method for large-scale CVD growth of graphene Download PDFInfo
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- CN105883779A CN105883779A CN201510039352.2A CN201510039352A CN105883779A CN 105883779 A CN105883779 A CN 105883779A CN 201510039352 A CN201510039352 A CN 201510039352A CN 105883779 A CN105883779 A CN 105883779A
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Abstract
The invention relates to a preparation technology of graphene, in particular to a method for large-scale CVD growth of graphene. According to the method, the mode of alternatively stacking a growth matrix and a solid-phase carbon source is adopted in CVD growth to increase the yield of graphene grown on a large scale in single batches. The growth matrix of a planar structure and the recyclable solid-phase carbon source are utilized and alternatively stacked for CVD growth, large-scale graphene is formed on the upper and lower surfaces of the growth matrix, and the solid-phase carbon source is recycled. Through the mode of alternatively stacking the growth matrix and the solid-phase carbon source, the single-batch loading capacity of the growth matrix is greatly increased, and large-scale high-quality graphene is grown on the upper and lower surfaces of the growth matrix, so that the yield of graphene grown in single batches is increased. High production cost caused by high consumption of a high-purity gas-phase carbon source can be avoided by adopting the recyclable solid-phase carbon source, and thus the method can serve as a low-cost and high-efficiency method for large-scale production of graphene.
Description
Technical field:
The present invention relates to the technology of preparing of Graphene, be specially one and use growing substrate and solid-phase carbon source to replace heap
The scalable process of folded mode efficient CVD growth large-area graphene.
Background technology:
Graphene is by the bi-dimensional cellular shape crystal structure of the tightly packed one-tenth of monolayer carbon atom, is to build other dimensions
The basic structural unit of Carbon Materials (zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).Graphene is unique
Crystal structure make it have electricity, calorifics and the mechanical property of excellence, such as: under room temperature, its electron mobility is high
Reach 200,000cm2/ V s, thermal conductivity is up to 5300W/m k, it is expected at multi-functional nanometer electronic device, transparent lead
Electrolemma, composite, catalysis material, energy storage material, field emmision material, gas sensor and gas storage etc.
Field obtains extensively application.In order to comprehensively utilize numerous excellent specific properties of Graphene, the preparation of high-quality graphene
Most important.(or micromechanics peels off to use adhesive tape stripping method from the seminar of Univ Manchester UK in 2004
Method) first separate obtain stable existence Graphene after, the method much preparing Graphene is developed successively,
Including chemical oxidation stripping method, separate out growth method and chemical gaseous phase deposition (CVD) method.Wherein, CVD side
Method is current controlled preparation large area, the main method of high-quality graphene.By controlling temperature, carbon source and pressure
The preparation conditions such as power, it is possible to achieve multiple substrate material surface (metal and nonmetal) grow large area,
High-quality Graphene.In recent years, it is saturating that the Graphene that prepared by CVD has been used to prepare high performance Graphene
Bright conductive film, has shown wide application prospect in fields such as the photoelectric devices with touch screen as representative.For
The application of further promotion Graphene, needs to develop the scalable process of CVD growth large-area graphene,
Graphene can be prepared in a large number realizing low cost.
At present, the scalable process of CVD growth large-area graphene mainly includes that coiled-type growth and volume to volume are raw
Long.The growing substrate (such as Copper Foil) of Graphene is wound on the supporting body surface such as quartz ampoule and carries out static state by the former
Growth；The mode that the latter uses serialization to transmit tinsel carries out dynamic growth.Although two kinds of growth patterns are easy
In accomplishing scale production, but because the useful load of growing substrate is relatively low, the yield causing single batch is relatively low.This
Outward, existing large-area graphene growing method all uses high-purity gas phase carbon source, the production cost not only increased,
And air flow method is vulnerable to the impact of growing substrate useful load, there is graphene growth during high useful load uneven
Problem.
Summary of the invention:
The problems referred to above existed for existing CVD preparation method, it is an object of the invention to provide a kind of low one-tenth
Basis, the scalable process of high efficiency CVD growth large-area graphene, use growing substrate to hand over solid-phase carbon source
For the mode of stacking, improve the yield of single batch growing large-area Graphene, solve high dress in prior art simultaneously
The problem that graphene growth is uneven is there is during carrying capacity.
The technical scheme is that
The scalable process of a kind of CVD growth large-area graphene, the method is by using in CVD growth
The mode that growing substrate and solid-phase carbon source are alternately stacked, uses the growing substrate of planar structure and reusable edible
Both are alternately stacked and carry out CVD growth by solid-phase carbon source, thus are formed greatly in the upper and lower surface of growing substrate
Area graphite alkene, and reuse solid-phase carbon source；Specifically comprise the following steps that
(1) use the growing substrate of planar structure, form uniform solid carbon active layer on its surface；
(2) second layer growing substrate and solid carbon active layer are stacked successively on established solid carbon active layer surface；
(3) repeat the above steps is until reaching the growing substrate of the required number of plies；
(4) lamination of above-mentioned growing substrate with solid-phase carbon source is put into CVD system to grow, at growth base
The surface of body forms Graphene；
(5) after CVD growth terminates, growth have the growing substrate of Graphene separate with solid-phase carbon source, and
Solid-phase 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, Ir, Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta, Cr metal or its conjunction
One of gold or two or more composites；Or, the growing substrate of Graphene is titanium carbide, molybdenum carbide, carbon
Change one of zirconium, vanadium carbide, niobium carbide, ramet, chromium carbide, tungsten carbide or two or more composites；
Or, the growing substrate of Graphene is Si, SiO2、Al2O3One of quasiconductor or two or more compound；Or,
The growing substrate of Graphene is the composite of conductor and quasiconductor.
The scalable process of described CVD growth large-area graphene, the alloy of described metal be copper alloy,
Nickel alloy or rustless steel.
The scalable process of described CVD growth large-area graphene, the growing substrate of Graphene is planar junction
Structure, including one of thin film, paillon foil, sheet material or two or more compound.
The scalable process of described CVD growth large-area graphene, solid-phase carbon source material is Carbon Materials, has
Machine thing or other carbon compound, solid-phase carbon source material be used alone or with other Material cladding.
The scalable process of described CVD growth large-area graphene, the form of solid-phase carbon source material includes even
Continuous planar structure or powder structure, separate with growing substrate after CVD growth and reuse.
The scalable process of described CVD growth large-area graphene, the equipment of CVD growth includes heating
Type CVD or plasma enhanced CVD (PECVD), the technique of CVD growth includes low pressure process or normal pressure
Technique, the atmosphere of CVD growth includes reducing atmosphere or inert atmosphere, and the mode of heating of CVD growth includes
Electrical heating, sensing heating, irradiated heat or LASER HEATING, the type of cooling of CVD growth is Slow cooling or fast
Quickly cooling is but.
The scalable process of described CVD growth large-area graphene, the equal shape of upper and lower surface at growing substrate
Becoming Graphene, the average number of plies of Graphene is monolayer, bilayer, few layer or multilamellar, and the number of plies is less than 50 layers.
The scalable process of described CVD growth large-area graphene, in CVD growth, first by furnace chamber
Evacuation, until pressure is less than 1Pa, then is passed through the hydrogen that flow is 1～100sccm, and is maintained by pressure
1～500Pa；In 1～30 minute, furnace temperature is risen to 300-1500 DEG C, be incubated 1～60 minute；Then with stove
Being cooled to room temperature, or the sample of lamination is quickly cooled to room temperature, rate of cooling is 10～20 DEG C/sec,
Complete CVD growth.
The feature of the present invention and providing the benefit that:
1. the present invention uses the mode being alternately stacked growing substrate with solid-phase carbon source, and the list of growing substrate is greatly improved
Batch load amount；Meanwhile, layer-by-layer growth can realize the upper and lower surface of growing substrate and be respectively formed Graphene, will be single
The growth efficiency of one matrix improves twice.Therefore, it can significantly improve single batch CVD growth large area graphite
The yield of alkene.
2. the present invention use independent used carbon containing solid phase material as carbon source and raw by controlling CVD
Elongate member, it is ensured that reuse carbon source.Therefore, consuming high-purity gas phase carbon source compared to a large amount of, cost of material shows
Write and reduce.
3. in the present invention, growing substrate is in close contact with solid carbon active layer, on the one hand decreases growth base under high temperature
The volatilizing loss of body material thus improve the service life of matrix material, be on the other hand conducive to each layer growth matrix
Between conduction of heat, 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, CVD
Growing substrate still can be kept after growth smooth, therefore be conducive to improving transfer in follow-up Graphene transfer process
Integrity.
Accompanying drawing illustrates:
Fig. 1. the scale CVD growth method schematic diagram of large-area graphene.
Detailed description of the invention:
Below by embodiment and accompanying drawing, the present invention is described in more detail.
Embodiment 1
As it is shown in figure 1, use metal copper foil (25 microns of thickness) as growing substrate, use carbon felt (50 microns
Thick) as solid-phase carbon source.Smooth large area Copper Foil and carbon felt alternative stacked being stacked, the number of plies is 200 layers.
Copper Foil after lamination and carbon felt are put in electrically heated CVD stove and grows.First by furnace chamber evacuation,
Until pressure is less than 1Pa, then it is passed through the hydrogen that flow is 100sccm, and pressure is maintained 50Pa；30
In minute, furnace temperature is risen to 1000 DEG C, cool to room temperature with the furnace after being incubated 10 minutes, complete CVD growth.Copper
The upper and lower surface of paper tinsel is respectively formed high-quality large area single-layer graphene, and carbon felt can be re-used for CVD life simultaneously
Long.
Embodiment 2
It is with the difference of embodiment 1:
Use other material as solid-phase carbon source, including flexible graphite paper, carbon nanotube film, fullerene, charcoal
Black or carborundum etc.；Using atmospheric pressure cvd technique to grow, carrier gas is argon.
Embodiment 3
As it is shown in figure 1, use surface to be coated with the quartz plate of nickel film (500 nanometer thickness) as growing substrate, adopt
With being soaked with the carbon cloth (200 microns of thickness) of epoxy resin as solid-phase carbon source.By fine to nickel film/quartz plate and carbon
Dimension/resin cloth alternative stacked is stacked, and the number of plies is 100 layers.The sample of lamination is put into induction heating type CVD stove
In grow.First by furnace chamber evacuation, until pressure is less than 1Pa, then it is passed through the hydrogen that flow is 50sccm
Gas, and pressure is maintained 20Pa；In 3 minutes, furnace temperature is risen to 1000 DEG C, be incubated 1 minute；The most right
The sample of lamination carries out being quickly cooled to room temperature, and rate of cooling is 15 DEG C/sec, completes CVD growth.Nickel film table
Face forms the few layer graphene of high-quality large area, and carbon cloth can be repeated for CVD growth.
Embodiment result shows, the present invention uses the growing substrate of planar structure and the solid-phase carbon source of reusable edible,
Both are alternately stacked and carry out CVD growth, the single batch load amount of growing substrate is greatly improved, and achieves
The upper and lower surface of growing substrate all grows high-quality large-area graphene, reuses solid-phase carbon source, thus
Improve the yield of single batch growing large-area Graphene.And, use the solid-phase carbon source of reusable edible, permissible
Avoid consuming, because of a large amount of, the high production cost that high-purity gas phase carbon source causes, therefore can as a kind of low cost, efficiently
Rate produces the scalable process of large-area graphene.
Claims (9)
1. the scalable process of a CVD growth large-area graphene, it is characterised in that: the method is passed through
The mode using growing substrate to be alternately stacked with solid-phase carbon source in CVD growth, uses the growing substrate of planar structure
With the solid-phase carbon source of reusable edible, both are alternately stacked and carry out CVD growth, thus at growing substrate
Upper and lower surface forms large-area graphene, and reuses solid-phase carbon source；Specifically comprise the following steps that
(1) use the growing substrate of planar structure, form uniform solid carbon active layer on its surface；
(2) second layer growing substrate and solid carbon active layer are stacked successively on established solid carbon active layer surface；
(3) repeat the above steps is until reaching the growing substrate of the required number of plies；
(4) lamination of above-mentioned growing substrate with solid-phase carbon source is put into CVD system to grow, at growth base
The surface of body forms Graphene；
(5) after CVD growth terminates, growth have the growing substrate of Graphene separate with solid-phase carbon source, and
Solid-phase carbon source is re-used for CVD growth.
2., according to the scalable process of the CVD growth large-area graphene described in claim 1, its feature exists
In: the growing substrate of Graphene is Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo, W, Ti,
One of Zr, V, Nb, Ta, Cr metal or its alloy or two or more composites；Or, Graphene
Growing substrate is titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide, carbonization
One of tungsten or two or more composites；Or, the growing substrate of Graphene is Si, SiO2、Al2O3Partly lead
One of body or two or more compound；Or, the growing substrate of Graphene is the composite wood of conductor and quasiconductor
Material.
3., according to the scalable process of the CVD growth large-area graphene described in claim 2, its feature exists
In: the alloy of described metal is copper alloy, nickel alloy or rustless steel.
4., according to the scalable process of the CVD growth large-area graphene described in claim 1, its feature exists
In: the growing substrate of Graphene is planar structure, including one of thin 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, its feature exists
In: solid-phase carbon source material is Carbon Materials, Organic substance or other carbon compound, and solid-phase carbon source material individually makes
With or with other Material cladding.
6., according to the scalable process of the CVD growth large-area graphene described in claim 1, its feature exists
In: the form of solid-phase carbon source material includes continuous print planar structure or powder structure, with life after CVD growth
Long matrix separates and reuses.
7., according to the scalable process of the CVD growth large-area graphene described in claim 1, its feature exists
In: the equipment of CVD growth includes hot type CVD or plasma enhanced CVD (PECVD), CVD
The technique of growth includes low pressure process or atmospheric processes, and the atmosphere of CVD growth includes reducing atmosphere or indifferent gas
Atmosphere, the mode of heating of CVD growth includes electrical heating, sensing heating, irradiated heat or LASER HEATING, CVD
The type of cooling of growth is Slow cooling or quickly cools down.
8., according to the scalable process of the CVD growth large-area graphene described in claim 1, its feature exists
In: the upper and lower surface at growing substrate is respectively formed Graphene, and the average number of plies of Graphene is monolayer, bilayer, lacks
Layer or multilamellar, the number of plies is less than 50 layers.
9., according to the scalable process of the CVD growth large-area graphene described in claim 1, its feature exists
In: in CVD growth, first by furnace chamber evacuation, until pressure is less than 1Pa, then be passed through flow be 1～
The hydrogen of 100sccm, and pressure is maintained 1～500Pa；In 1～30 minute, furnace temperature is risen to 300-1500
DEG C, it is incubated 1～60 minute；Then cool to room temperature with the furnace, or the sample of lamination is quickly cooled to
Room temperature, rate of cooling is 10～20 DEG C/sec, completes CVD growth.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106672947A (en) * | 2016-12-28 | 2017-05-17 | 江苏中亚新材料股份有限公司 | Preparation method of multilayered graphene with ultrahigh conductivity |
| CN109216496A (en) * | 2018-10-22 | 2019-01-15 | 北京工业大学 | The silicon Schotty PIN Junction detector PIN of graphene is directly grown using Parylene N thin film |
| CN109518158A (en) * | 2019-01-04 | 2019-03-26 | 无锡第六元素电子薄膜科技有限公司 | A kind of graphene film magnanimity preparation method |
| 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 |
| CN114774856A (en) * | 2022-04-28 | 2022-07-22 | 常州二维碳素科技股份有限公司 | Preparation method of graphene heat-conducting film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672947A (en) * | 2016-12-28 | 2017-05-17 | 江苏中亚新材料股份有限公司 | Preparation method of multilayered graphene with ultrahigh conductivity |
| CN109216496A (en) * | 2018-10-22 | 2019-01-15 | 北京工业大学 | The silicon Schotty PIN Junction detector PIN of graphene is directly grown using Parylene N thin film |
| 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 |
| CN109518158A (en) * | 2019-01-04 | 2019-03-26 | 无锡第六元素电子薄膜科技有限公司 | A kind of graphene film magnanimity preparation method |
| 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 |
| CN114774856A (en) * | 2022-04-28 | 2022-07-22 | 常州二维碳素科技股份有限公司 | Preparation method of graphene heat-conducting film |
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