CN105668559A - Method for preparing graphene films on multiple substrates in batch - Google Patents
Method for preparing graphene films on multiple substrates in batch Download PDFInfo
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- CN105668559A CN105668559A CN201610063713.1A CN201610063713A CN105668559A CN 105668559 A CN105668559 A CN 105668559A CN 201610063713 A CN201610063713 A CN 201610063713A CN 105668559 A CN105668559 A CN 105668559A
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- graphene
- carbon source
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
Abstract
The invention provides a method for preparing graphene films on multiple substrates in batch. The method comprises steps as follows: high-temperature annealing on substrates: the substrates are coated with carbon sources; solidification of the carbon sources: the stacked metal substrates are put in a CVD (chemical vapor deposition) reaction cavity, carbon atoms of solid-state carbon sources are recombined at the decomposition temperature, graphene nucleation is performed, carbon source molecules are diffused to the whole metal substrates, the graphene films are formed on the multiple substrates and cooled, and the graphene films are prepared. The multiple substrates are stacked for growth of the graphene films, and a clamp structure required for batch preparation of graphene is omitted; graphene is grown at the low temperature, the heating and cooling time is shortened, energy consumption is reduced, and the method has the advantage of industrialization; the cost of gas carbon sources and hydrogen used in a conventional CVD method are saved in the growth process; the number of layers of graphene films can be controlled according to the coating quantity of the carbon sources.
Description
Technical field
The present invention relates to the preparing technical field of graphene film, particularly relate to the method that the many substrates of a kind of batch prepare graphene film.
Background technology
Graphene is the hexagonal honey comb structure that carbon atom forms based on sp2 hydridization, the two dimensional crystal of only one atomic layers thick. 2004, AndreGeim and KonstantinNovoselov et al. found the single-layer graphene of stable existence, also obtained 2010 years Nobel Prizes in physics because of its initiative work in Graphene. In recent years, Graphene all shows many stem-winding performances and potential application prospect in fields such as microelectronics, quantum physics, material, chemistry, has attracted the extensive concern of scientific circles and industrial quarters. Graphene has the power of excellence, heat, the character such as optical, electrical. Electron mobility under Graphene room temperature, more than 15000cm2/V s, exceedes CNT and silicon crystal, and resistivity only about 10-6Ω cm, lower than copper or silver, is the material that resistivity is minimum in the world at present. And its all band light transmittance up to 97.7% is that other conductive materials are difficult to be equal to.
In recent years, Graphene all shows many stem-winding performances and potential application prospect in fields such as microelectronics, quantum physics, material, chemistry, has attracted the extensive concern of scientific circles and industrial quarters. At present, industrial commonly used chemical vapour deposition (CVD) (CVD) method is as the method for preparation large-area graphene, but the method for batch preparation is all difficult to break through, the carrier relying on various clamp structure is prepared multi-disc Graphene simultaneously and is considerably increased again overall load, reduce sample size, cause that production efficiency is low, and the graphene film uniformity prepared is bad, the number of plies is difficult to control to, thus causing that the overall electric property of graphene film is well below theoretical value.
The patent document that publication number is CN104131266 discloses a kind of method and similar device that can prepare thin-film material in batches, can be deposited on substrate by the method or the method such as spraying plating batch carries out the preparation of graphene film, but the method needs to rely on method for designing and the device of Double-side Heating, this clamp structure is complicated, and required graphene growth temperature is higher, the obtained graphene film number of plies is less, the problem that two-sided many substrates at high temperature easily exist interlayer adhesion.
Summary of the invention
In order to overcome the deficiency in above-mentioned background technology, the invention provides the method that the many substrates of a kind of batch prepare graphene film, the method step is as follows:
(1) substrate high annealing: be annealed metallic substrates processing more than 30min at temperature 900 DEG C-1050 DEG C, and be cooled to room temperature;
(2) coating carbon source: one layer of carbon source solution of coating on the metallic substrate, and dry solution to solidifying;
(3) setting-out product: the metallic substrates scribbling solid-state carbon source is cut into the size of applicable CVD reaction cavity size, and stacked in layers is good;
(4) Graphene nucleation: putting in CVD reaction cavity in the lump by the multiple layer metal substrate scribbling carbon source, temperature is increased to the decomposition temperature of carbon source, and carbon atom reconfigures, enters Graphene nucleation stage;
(5) thin film growth: carbon source molecule diffuses in whole metallic substrates, spreads and continues epitaxial growth around Graphene nucleus, form graphene film;
(6) cooling: substrate and Graphene are cooled, completes the preparation of graphene film.
Metallic substrates involved in the present invention can be the alloy of a kind of in Cu, Ru, Ni, Ir, Pt etc. or two kinds.
Carbon source solution involved in the present invention can be the polymeric carbon source of hydrocarbon or hydrocarbon oxygen, i.e. the copolymer of polyacrylate, polymethacrylates, polyacrylate and polymethacrylates or polyethers, polyester, polyolefin etc.
The number of plies of the involved in the present invention metallic substrates scribbling solid-state carbon source is any number of plies in monolayer or 2～100 layers.
The method that the many substrates of a kind of batch disclosed in this invention prepare graphene film, adopts the solid-state carbon source on many substrates to prepare Graphene in batches, MULTILAYER SUBSTRATE can dense accumulation, eliminate many substrates and prepare necessary clamp structure; Accurate control carbon source concentration, by the number of plies of carbon source coating weight control graphene film, eliminates the cost of gaseous carbon sources and hydrogen in existing CVD method in growth course; Reduce graphene growth temperature, make carbon atom spread generation graphene film at the temperature of 400～500 DEG C, decrease heating and cooling time and energy loss, there is industrialization advantage.
Accompanying drawing explanation
Fig. 1 is the techniqueflow chart of method for preparing graphene membrane involved in the present invention.
Fig. 2 has to be coated with the schematic diagram that the Copper Foil of uniform PMMA is stacked, and wherein, 1 is carbon source coating, and 2 is metallic substrates.
Fig. 3 is the square resistance scattergram that on Copper Foil, the Graphene of growth is transferred on PET.
Detailed description of the invention
Embodiment 1
Present embodiments providing the method that the many substrates of a kind of batch prepare graphene film, the techniqueflow of the method is as it is shown in figure 1, include metallic substrates annealing, coating solid-state carbon source, solidifies carbon source, and many substrates are stacked, carbon source decomposes nucleation, graphene growth film forming and cooling procedure, specifically comprises the following steps that
(1) substrate high annealing: being placed in CVD reaction chamber by the Copper Foil of 10cm × 20cm, pressure is set to normal pressure, at H2Flow is under the atmosphere of 100sccm, and temperature is annealed at 1050 DEG C, and then temperature is cooled to room temperature by time 30～40min.
(2) coating carbon source: smooth for every Copper Foil after high annealing is placed on Si sheet, the PMMA solution of spin coating 10%, whirl coating rotating speed 3000r/m, 50 seconds time. Cu/PMMA/Si is heated to 110 DEG C, dries PMMA solution and make it solidify in 20 minutes, form solid-state carbon source.
(3) setting-out product: the Copper Foil scribbling solid-state carbon source is cut into Copper Foil 2 structure scribbling solid-state carbon source 1 of some 5cm × 5cm sizes, as in figure 2 it is shown, scribble Copper Foil 2 build stack of solid-state carbon source 1 by 20 together, are positioned in CVD reaction chamber in the lump.
(4) Graphene nucleation: passing into argon 100sccm and hydrogen 20sccm in CVD reaction chamber, adjustment cavity temperature is normal pressure, regulates reaction chamber temperature to 500 DEG C, keeps growth 20 minutes, makes carbon source molecular breakdown be binned on Copper Foil nucleation.
(5) thin film growth: after nucleation again, carbon atom diffuses to whole Copper Foil substrate 2, forms graphene film.
(6) cooling: finally stop heating, and keep, in argon 100sccm and hydrogen 20sccm gaseous mixture, temperature is rapidly decreased to room temperature, complete the preparation of graphene film.
Graphene film obtained by the present embodiment transfers to the square resistance scattergram on PET as shown in Figure 3.
Embodiment 2
Present embodiments providing the method that the many substrates of a kind of batch prepare graphene film, the techniqueflow of the method is as it is shown in figure 1, include metallic substrates annealing, coating solid-state carbon source, solidifies carbon source, and many substrates are stacked, carbon source decomposes nucleation, graphene growth film forming and cooling procedure, specifically comprises the following steps that
(1) substrate high annealing: being placed in CVD reaction chamber by the nickel foil of 10cm × 20cm, pressure is set to normal pressure, at H2Flow is under the atmosphere of 100sccm, and temperature is annealed at 1200 DEG C, and then temperature is cooled to room temperature by time 30～40min.
(2) coating carbon source: smooth for every nickel foil after high annealing is placed on Si sheet, the PMMA solution of spin coating 2%, whirl coating rotating speed 3000r/m, 50 seconds time. Ni/PMMA/Si is heated to 110 DEG C, dries PMMA solution and make it solidify in 20 minutes, form solid-state carbon source.
(3) setting-out product: the nickel foil scribbling solid-state carbon source is cut into nickel foil 2 structure scribbling solid-state carbon source 1 of some 5cm × 5cm sizes, as in figure 2 it is shown, scribble nickel foil 2 build stack of solid-state carbon source 1 by 10 together, are positioned in CVD reaction chamber in the lump.
(4) Graphene nucleation: passing into argon 50sccm and hydrogen 10sccm in CVD reaction chamber, adjustment cavity temperature is normal pressure, regulates reaction chamber temperature to 500 DEG C, keeps growth 20 minutes, makes carbon source molecular breakdown be binned on nickel foil nucleation.
(5) thin film growth: after nucleation again, carbon atom diffuses to whole nickel foil substrate 2, forms graphene film.
(6) cooling: finally stop heating, and keep, in argon 50sccm and hydrogen 10sccm gaseous mixture, temperature is rapidly decreased to room temperature, complete the preparation of graphene film.
Claims (4)
1. the method that the many substrates of batch prepare graphene film, it is characterised in that the method step is as follows:
(1) substrate high annealing: be annealed metallic substrates processing more than 30min at temperature 900 DEG C-1050 DEG C, and be cooled to room temperature;
(2) coating carbon source: one layer of carbon source solution of coating on the metallic substrate, and dry solution to solidifying;
(3) setting-out product: the metallic substrates scribbling solid-state carbon source is cut into the size of applicable CVD reaction cavity size, and stacked in layers is good;
(4) Graphene nucleation: putting in CVD reaction cavity in the lump by the multiple layer metal substrate scribbling carbon source, temperature is increased to the decomposition temperature of carbon source, and carbon atom reconfigures, enters Graphene nucleation stage;
(5) thin film growth: carbon source molecule diffuses in whole metallic substrates, spreads and continues epitaxial growth around Graphene nucleus, form graphene film;
(6) cooling: substrate and Graphene are cooled, completes the preparation of graphene film.
2. method according to claim 1, it is characterised in that described metallic substrates can be the alloy of a kind of in Cu, Ru, Ni, Ir, Pt etc. or two kinds.
3. method according to claim 1, it is characterized in that, described carbon source solution can be the polymeric carbon source of hydrocarbon or hydrocarbon oxygen, i.e. the copolymer of polyacrylate, polymethacrylates, polyacrylate and polymethacrylates or polyethers, polyester, polyolefin etc.
4. method according to claim 1, it is characterised in that described in scribble solid-state carbon source the number of plies of metallic substrates be any number of plies in monolayer or 2～100 layers.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109183145A (en) * | 2018-11-19 | 2019-01-11 | 绍兴文理学院 | A method of preparing FePC monocrystal thin films on graphene-based bottom |
| CN109950131A (en) * | 2019-02-28 | 2019-06-28 | 天津大学 | Using nonpolar crystal face SiC as the single-layer graphene of substrate and method for controllable growth |
| CN111072022A (en) * | 2019-12-11 | 2020-04-28 | 中国科学院上海微系统与信息技术研究所 | Preparation method of graphite film |
| WO2020172863A1 (en) * | 2019-02-28 | 2020-09-03 | 天津大学 | Single-layer graphene having nonpolar crystal plane sic as substrate and controllable growth method |
| CN111874893A (en) * | 2020-01-20 | 2020-11-03 | 烯旺新材料科技股份有限公司 | Graphene flexible composite layer and preparation method and application thereof |
| CN112265984A (en) * | 2020-10-30 | 2021-01-26 | 中国科学院重庆绿色智能技术研究院 | Method for preparing high-quality graphene in batches in situ and product thereof |
| CN113030054A (en) * | 2021-03-24 | 2021-06-25 | 太原理工大学 | Hollow multilayer film for gas concentration detection and preparation method thereof |
| CN113249793A (en) * | 2021-04-26 | 2021-08-13 | 深圳大学 | Transition metal chalcogenide single crystal and method for producing same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109183145A (en) * | 2018-11-19 | 2019-01-11 | 绍兴文理学院 | A method of preparing FePC monocrystal thin films on graphene-based bottom |
| CN109950131A (en) * | 2019-02-28 | 2019-06-28 | 天津大学 | Using nonpolar crystal face SiC as the single-layer graphene of substrate and method for controllable growth |
| WO2020172863A1 (en) * | 2019-02-28 | 2020-09-03 | 天津大学 | Single-layer graphene having nonpolar crystal plane sic as substrate and controllable growth method |
| CN111072022A (en) * | 2019-12-11 | 2020-04-28 | 中国科学院上海微系统与信息技术研究所 | Preparation method of graphite film |
| CN111874893A (en) * | 2020-01-20 | 2020-11-03 | 烯旺新材料科技股份有限公司 | Graphene flexible composite layer and preparation method and application thereof |
| CN112265984A (en) * | 2020-10-30 | 2021-01-26 | 中国科学院重庆绿色智能技术研究院 | Method for preparing high-quality graphene in batches in situ and product thereof |
| CN113030054A (en) * | 2021-03-24 | 2021-06-25 | 太原理工大学 | Hollow multilayer film for gas concentration detection and preparation method thereof |
| CN113030054B (en) * | 2021-03-24 | 2024-01-30 | 太原理工大学 | Hollow multilayer film for detecting gas concentration and preparation method thereof |
| CN113249793A (en) * | 2021-04-26 | 2021-08-13 | 深圳大学 | Transition metal chalcogenide single crystal and method for producing same |
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Application publication date: 20160615 |