CN103754864A - Preparation method of graphene film - Google Patents
Preparation method of graphene film Download PDFInfo
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- CN103754864A CN103754864A CN201410000507.7A CN201410000507A CN103754864A CN 103754864 A CN103754864 A CN 103754864A CN 201410000507 A CN201410000507 A CN 201410000507A CN 103754864 A CN103754864 A CN 103754864A
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Abstract
The invention discloses a preparation method of a graphene film. The preparation method comprises the steps: firstly, dissolving polymethyl methacrylate into acetone to obtain a polymethyl methacrylate and acetone liquid; then, dropwise adding the polymethyl methacrylate and acetone liquid on a metal to form a layer of polymethyl methacrylate film; covering a quartz glass slide on the polymethyl methacrylate film; then, simultaneously placing the metal sheet, the polymethyl methacrylate film on the metal sheet and the covered quartz glass slide into a high-temperature annealing furnace with a nitrogen condition, and carrying out high-temperature annealing while controlling the temperature at 800-1000 DEG C, wherein the polymethyl methacrylate is decomposed into a graphene film under the catalytic action of the metal in the metal film, and the graphene film is evaporated at a high temperature and is transferred on the quartz glass slide; and next, naturally cooling to room temperature to obtain a layer of graphene film on the quartz glass slide. The preparation method disclosed by the invention is simple and convenient to implement and capable of transferring graphene under the condition that the graphene is not damaged or polluted.
Description
Technical field
The present invention relates to a kind of preparation method of graphene film, be particularly related to the preparation method of a kind of original position metal catalyzed decomposition, transfer graphene film, be specifically related to utilize in-situ metal to decompose and prepare Graphene, finally by thermal evaporation, Graphene is transferred to target substrate, thereby realize Graphene, without the processing through intermediate, is directly transferred to target substrate.
Background technology
Graphene is as a kind of novel transparent conductive film material, and the transmitance of single-layer graphene visible ray is up to 97.7%, and it has good electroconductibility, snappiness and physical strength simultaneously.Due to its superior electrical and optical properties, it more and more receives the concern of scientific research and engineering Application Areas.It has more application in fields such as micro-nano electron device, electron stored energy device, solar cells at present.
The at present transfer of Graphene mainly concentrates on chemical process, take wet method transfer techniques that polymethylmethacrylate glue or other high molecular polymers be carrier as main.It is mainly on the graphene layer of having grown, to cover polymethylmethacrylate glue as protective layer and the transfer vector of graphene film.Then erode the metal substrate of Graphene bottom, then the graphene layer that covers polymethylmethacrylate glue is transferred in target substrate, utilize organic solution to remove the polymethyl methacrylate layers on Graphene simultaneously.Although this method is convenient to big area, shift Graphene to different substrates, easily damage and pollute graphene film.Though the method can effectively realize the transfer of film, its complex technical process is time-consuming, while especially processing polymethyl methacrylate layers, will use in a large number organic solvent, has not only wasted resource, and can damage human body and environment.
Summary of the invention
The object of the invention is in order to solve above-mentioned Graphene ripple film preparation process complicated, and a large amount of organic solvents that use in preparation process, not only wasted resource, and can the technical problem such as damage and provide a kind of reproducible human body and environment, do not introduce impurity, easy to operate simple Graphene transfer method.
Technical scheme of the present invention
A preparation method for graphene film, specifically comprises the steps:
(1), polymethylmethacrylate is dissolved in acetone soln, formation concentration is 1-5g/L, be preferably the polymethylmethacrylate acetone soln of 3g/L, again polymethylmethacrylate acetone soln being controlled to drop rate is 0.1-1ml/min, being preferably 0.2ml/min drops on sheet metal, form one deck polymethyl methacrylate film, its thickness is preferably 100-500nm;
Described sheet metal is that thickness is 0.1-1mm, is preferably Copper Foil, nickel foil, goldleaf or the silver foil of 0.2mm;
Described sheet metal is used dilute hydrochloric acid and acetone, ethanol, washed with de-ionized water successively, to remove the impurity such as foil surfaces oxide compound and greasy dirt;
Described quartzy slide glass respectively cleans 1-20min successively in supersonic cleaning machine with acetone, ethanol, deionized water, to remove the impurity of quartzy slide surface;
(2), quartzy slide glass is covered on the formed polymethyl methacrylate film of step (1), then by sheet metal and on put into the high-temperature annealing furnace of the nitrogen atmosphere of purity 99.99% together with the quartzy slide glass of one deck polymethyl methacrylate film that forms and covering, control temperature is 800-1000 ℃, be preferably 950 ℃ and maintain 1-120min, during this period, polymethyl methacrylate film generates graphene film by decomposing under the katalysis of metal in sheet metal, the graphene film of gained is evaporated and is transferred to quartzy slide glass, then naturally cool to room temperature, at quartzy slide glass, obtain one deck graphene film,
It is 100-300min that above-mentioned high-temperature annealing furnace is warmed up to 800-1000 ℃ of time used.
Useful technique effect of the present invention
The preparation method of a kind of graphene film of the present invention, utilize in-situ metal to decompose and prepare Graphene, finally by thermal evaporation, Graphene is transferred to i.e. quartzy the carrying on glass of target substrate, thereby realizing Graphene is directly transferred on target substrate without the processing through intermediate, do not use any other secondary transfer material, can not introduce new contaminating impurity or destroy the structure of formed Graphene, therefore, this preparation method has easy saving time, nontoxic, can not damage operator.
Accompanying drawing explanation
The Raman spectrum curve of the graphene film of Fig. 1, embodiment 1 gained, wherein a representative is the graphite Raman curve of spectrum generating at copper foil surface, b is after 950 ℃ of high temperature annealings, the graphite Raman curve of spectrum forming in quartzy slide surface;
The Raman spectrum curve of the graphene film of Fig. 2, embodiment 2 gained, wherein a representative is the graphite Raman curve of spectrum generating at copper foil surface, b is after 950 ℃ of high temperature annealings, the graphite Raman curve of spectrum forming in quartzy slide surface;
The Raman spectrum curve of the graphene film of Fig. 3, embodiment 3 gained, wherein a representative is the graphite Raman curve of spectrum generating at copper foil surface, b is after 950 ℃ of high temperature annealings, the graphite Raman curve of spectrum forming in quartzy slide surface.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, but the present embodiment is not limited to the present invention, every employing analog structure of the present invention and similar variation thereof, all should list protection scope of the present invention in.
In various embodiments of the present invention, material therefor is poly-methyl-prop dilute suplhuric acid methyl esters (Tokyo HuaCheng Industry Co., Ltd) and Copper Foil (Chemical Reagent Co., Ltd., Sinopharm Group).
embodiment 1
A preparation method for graphene film, specifically comprises the steps:
(1), polymethylmethacrylate is dissolved in acetone soln, the polymethylmethacrylate acetone soln that formation concentration is 3g/L, it is that 0.2ml/min drops on sheet metal that the polymethylmethacrylate acetone soln that is 3g/L concentration is again controlled drop rate, the polymethyl methacrylate film that formation a layer thickness is 100-500nm;
Described sheet metal is that thickness is the Copper Foil of 0.2mm;
Described sheet metal is used dilute hydrochloric acid and acetone, ethanol, the clear 10min of deionized water successively, to remove the impurity such as foil surfaces oxide compound and greasy dirt;
Described quartzy slide glass respectively cleans 10min successively in supersonic cleaning machine with acetone, ethanol, deionized water, to remove the impurity of quartzy slide surface;
(2), quartzy slide glass is covered on the formed polymethyl methacrylate film of step (1), then by sheet metal and on put into the high-temperature annealing furnace of the nitrogen atmosphere of purity 99.99% together with the quartzy slide glass of one deck polymethyl methacrylate film that forms and covering, control temperature is 950 ℃ and carries out high temperature annealing 1min, During Annealing, under the katalysis of polymethyl methacrylate film metal in sheet metal, decompose and generate graphene film, graphene film is at high temperature evaporated and is transferred on quartzy slide glass, then naturally cool to room temperature, at quartzy slide glass, obtain one deck graphene film.
It is 100min that above-mentioned high-temperature annealing furnace is warmed up to 950 ℃ of times used.
embodiment 2
A preparation method for graphene film, specifically comprises the steps:
(1), polymethylmethacrylate is dissolved in acetone soln, the polymethylmethacrylate acetone soln that formation concentration is 3g/L, it is that 0.2ml/min drops on sheet metal that the polymethylmethacrylate acetone soln that is 3g/L concentration is again controlled drop rate, the polymethyl methacrylate film that formation a layer thickness is 100-500nm;
Described sheet metal is that thickness is the Copper Foil of 0.2mm;
Described sheet metal is used dilute hydrochloric acid and acetone, ethanol, the clear 10min of deionized water successively, to remove the impurity such as foil surfaces oxide compound and greasy dirt;
Described quartzy slide glass respectively cleans 10min successively in supersonic cleaning machine with acetone, ethanol, deionized water, to remove the impurity of quartzy slide surface;
(2), quartzy slide glass is covered on the formed polymethyl methacrylate film of step (1), then by sheet metal and on put into the high-temperature annealing furnace of the nitrogen atmosphere of purity 99.99% together with the quartzy slide glass of one deck polymethyl methacrylate film that forms and covering, control temperature is 950 ℃ and carries out high temperature annealing 60min, During Annealing, under the katalysis of polymethyl methacrylate film metal in sheet metal, decompose and generate graphene film, graphene film is at high temperature evaporated and is transferred on quartzy slide glass, then naturally cool to room temperature, at quartzy slide glass, obtain one deck graphene film.
It is 150min that above-mentioned high-temperature annealing furnace is warmed up to 950 ℃ of times used.
embodiment 3
A preparation method for graphene film, specifically comprises the steps:
(1), polymethylmethacrylate is dissolved in acetone soln, the polymethylmethacrylate acetone soln that formation concentration is 3g/L, it is that 0.2ml/min drops on sheet metal that the polymethylmethacrylate acetone soln that is 3g/L concentration is again controlled drop rate, the polymethyl methacrylate film that formation a layer thickness is 100-500nm;
Described sheet metal is that thickness is the Copper Foil of 0.2mm;
Described sheet metal is used dilute hydrochloric acid and acetone, ethanol, the clear 10min of deionized water successively, to remove the impurity such as foil surfaces oxide compound and greasy dirt;
Described quartzy slide glass respectively cleans 10min successively in supersonic cleaning machine with acetone, ethanol, deionized water, to remove the impurity of quartzy slide surface;
(2), quartzy slide glass is covered on the formed polymethyl methacrylate film of step (1), then by sheet metal and on put into the high-temperature annealing furnace of the nitrogen atmosphere of purity 99.99% together with the quartzy slide glass of one deck polymethyl methacrylate film that forms and covering, control temperature is 950 ℃ and carries out high temperature annealing 120min, During Annealing, under the katalysis of polymethyl methacrylate film metal in sheet metal, decompose and generate graphene film, graphene film is at high temperature evaporated and is transferred on quartzy slide glass, then naturally cool to room temperature, at quartzy slide glass, obtain one deck graphene film.
It is 300min that above-mentioned high-temperature annealing furnace is warmed up to 950 ℃ of times used.
Above-described embodiment 1, embodiment 2, the graphene film of embodiment 3 gained is measured by French HORIBA Jobin-Yvon HR800 type confocal Raman microscopy, its Raman spectrum curve is respectively as Fig. 1, Fig. 2, shown in Fig. 3, Fig. 1, 2, a representative in 3 be the graphite Raman curve of spectrum generating at copper foil surface, b is after 950 ℃ of high temperature annealings, the graphite Raman curve of spectrum forming in quartzy slide surface, from Fig. 1, 2, in 3, can find out Copper Foil, on quartzy slide glass, there is the generation of Graphene, shown thus to have after high temperature Graphene after 950 ℃ of high temperature annealings hydatogenesis on quartzy slide glass.
Foregoing is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. a preparation method for graphene film, is characterized in that specifically comprising the steps:
(1), polymethylmethacrylate is dissolved in acetone soln, the polymethylmethacrylate acetone soln that formation concentration is 1-5g/L, again polymethylmethacrylate acetone soln being controlled to drop rate is that 0.1-1ml/min drops on sheet metal, forms one deck polymethyl methacrylate film;
Described sheet metal is that thickness is Copper Foil, nickel foil, goldleaf or the silver foil of 0.1-1mm;
(2), quartzy slide glass is covered on the formed polymethyl methacrylate film of step (1), then by sheet metal and on put into the high-temperature annealing furnace of the nitrogen atmosphere of purity 99.99% together with the quartzy slide glass of one deck polymethyl methacrylate film that forms and covering, control temperature is 800-1000 ℃ and carries out high temperature annealing 1-120min, then naturally cool to room temperature, on quartzy slide glass, obtain one deck graphene film.
2. preparation method as claimed in claim 1, is characterized in that described sheet metal uses dilute hydrochloric acid and acetone, ethanol, washed with de-ionized water successively, to remove foil surfaces oxide compound and greasy dirt;
Described quartzy slide glass respectively cleans 1-20min successively in supersonic cleaning machine with acetone, ethanol, deionized water.
3. preparation method as claimed in claim 1, is characterized in that the polymethylmethacrylate acetone soln concentration described in step (1) is 3g/L;
The drop rate of polymethylmethacrylate acetone soln is 0.2ml/min;
The polymethyl methacrylate film thickness forming is 100-500nm.
4. preparation method as claimed in claim 3, is characterized in that the middle control of step (2) temperature is 950 ℃ and carries out high temperature annealing.
5. preparation method as claimed in claim 4, is characterized in that it is 100-300min that the high-temperature annealing furnace described in step (2) is warmed up to 950 ℃ of times used.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591162A (en) * | 2014-12-19 | 2015-05-06 | 东华大学 | Preparation method of multi-response graphene/graphite oxide film |
| WO2017025926A1 (en) | 2015-08-11 | 2017-02-16 | Graphenest, S.A. | Method and device for production of graphene or graphene-like materials |
| CN106882792A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院上海微系统与信息技术研究所 | A kind of method of Graphene in dry method transfer metal substrate |
| CN113184835A (en) * | 2021-05-12 | 2021-07-30 | 电子科技大学 | Method for transferring graphene through pressure-assisted evaporation |
| CN113401893A (en) * | 2021-05-24 | 2021-09-17 | 广西师范大学 | Graphene transfer method based on metal silver sacrificial layer |
| CN118501231A (en) * | 2024-07-16 | 2024-08-16 | 天津大学 | PH sensor, preparation method of PH sensor and pH measurement method |
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| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
| CN103172061A (en) * | 2013-04-16 | 2013-06-26 | 北京大学 | Method for growing large-area graphene on insulating substrate |
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2014
- 2014-01-02 CN CN201410000507.7A patent/CN103754864A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259849A (en) * | 2011-06-09 | 2011-11-30 | 无锡第六元素高科技发展有限公司 | Method for preparing graphene by utilizing solid carbon source |
| CN103172061A (en) * | 2013-04-16 | 2013-06-26 | 北京大学 | Method for growing large-area graphene on insulating substrate |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591162A (en) * | 2014-12-19 | 2015-05-06 | 东华大学 | Preparation method of multi-response graphene/graphite oxide film |
| WO2017025926A1 (en) | 2015-08-11 | 2017-02-16 | Graphenest, S.A. | Method and device for production of graphene or graphene-like materials |
| US10843145B2 (en) | 2015-08-11 | 2020-11-24 | Graphenest, S.A. | Method and device for production of graphene or graphene-like materials |
| CN106882792A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院上海微系统与信息技术研究所 | A kind of method of Graphene in dry method transfer metal substrate |
| CN106882792B (en) * | 2015-12-15 | 2019-03-01 | 中国科学院上海微系统与信息技术研究所 | A kind of method that dry method shifts graphene in metal substrate |
| CN113184835A (en) * | 2021-05-12 | 2021-07-30 | 电子科技大学 | Method for transferring graphene through pressure-assisted evaporation |
| CN113401893A (en) * | 2021-05-24 | 2021-09-17 | 广西师范大学 | Graphene transfer method based on metal silver sacrificial layer |
| CN118501231A (en) * | 2024-07-16 | 2024-08-16 | 天津大学 | PH sensor, preparation method of PH sensor and pH measurement method |
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Inventor after: Hong Ruijin Inventor after: Ding Liangliang Inventor after: Song Xiao Inventor after: Zhang Dawei Inventor after: Tao Chunxian Inventor before: Ding Liangliang Inventor before: Hong Ruijin Inventor before: Song Xiao Inventor before: Zhang Dawei Inventor before: Tao Chunxian |
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Free format text: CORRECT: INVENTOR; FROM: DING LIANGLIANG HONG RUIJIN SONG XIAO ZHANG DAWEI TAO CHUNXIAN TO: HONG RUIJIN DING LIANGLIANG SONG XIAO ZHANG DAWEI TAO CHUNXIAN |
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Application publication date: 20140430 |