CN104108704A - Graphene transfer method - Google Patents
Graphene transfer method Download PDFInfo
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- CN104108704A CN104108704A CN201410331217.0A CN201410331217A CN104108704A CN 104108704 A CN104108704 A CN 104108704A CN 201410331217 A CN201410331217 A CN 201410331217A CN 104108704 A CN104108704 A CN 104108704A
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- tinsel
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Abstract
The invention discloses a graphene transfer method which comprises the following steps: fixing a burette on an iron frame, placing downwards one face where graphene grows, of a meal foil on the surface of a target substrate, and placing the substrate below the burette to press the metal foil; dropping a FeCl3 solution in the burette above the metal foil, wherein no FeCl3 solution between the graphene and the substrate enters by controlling the amount of the FeCl3 solution flowing out by controlling on-off of the burette; after soaking by a diluted hydrochloric acid solution, repeatedly washing the substrate by deionized water to remove residual Fe<3+> ions; and taking out the cleaned substrate and drying the substrate by an air gun. According to the method disclosed by the invention, a metal catalytic thin film is directly corroded by adopting an inorganic solution by means of a simple burette system. The method has the advantages of simple and convenient operation, low cost, no organic residues, easy implementation of integration of large-area apparatuses and the like.
Description
Technical field
The invention provides a kind of Graphene transfer method of getting involved (comprising organic film and organic solvent etc.) without organism, relate to the new device preparation field of graphene-containing functional unit.
Background technology
Graphene is to be arranged the two dimensional crystal forming by hexagon cellular shape by monolayer carbon atom.It has dirac taper energy band structure, excellent electrical and optical properties, has become a study hotspot of physics, chemistry, biology and material science.The Graphene size that adopts micromechanics stripping method to prepare is little, yields poorly, and has limited its application aspect device.In recent years, people adopt chemical vapour deposition (CVD) method to prepare big area, high-quality graphene on the catalytic films such as Ni or Cu paper tinsel.This Graphene can be transferred in target substrate by the figure art of composition, be prepared for device.Up to now, people have prepared the multiple device taking Graphene as basic functional units, comprise field-effect transistor, solar cell, nano generator, sensor.Use organic materials and the acetone and other organic solvent such as PMMA (polymethylmethacrylate) because the figure art of composition shifts in Graphene process, and organic residue can bring infringement to the performance of grapheme material and device.A kind of Graphene transfer method of getting involved without organism (comprising organic film and organic solvent etc.) of invention is all very important for research or the device application aspect of Graphene basis physical properties.
Summary of the invention
The object of this invention is to provide a kind of new Graphene transfer method of getting involved without organism.
Wherein Graphene used for example, prepares by CVD method in tinsel (: Copper Foil, nickel foil etc.).The scope of tinsel length and width is 0.3cm～10cm, and individual layer or double-layer graphite alkene cover its surface overwhelming majority.
Technical scheme provided by the invention is as follows:
A kind of Graphene transfer method, it is characterized in that, drop-burette is fixed on iron stand have one of Graphene to face down tinsel length and be placed in target substrate surface, substrate is put in to the below of drop-burette, tinsel is flattened to (for example: by other smooth substrates pressures); By the FeCl in drop-burette
3solution drips in tinsel top, the FeCl flowing out by controlling the on-off control of drop-burette
3amount of solution, making does not have FeCl between Graphene and substrate
3solution enters, thereby avoids Fe
3+remain on substrate Graphene sample is produced and polluted.
Preferred:
Described Graphene transfer method, is characterized in that, described tinsel is Copper Foil or nickel foil.
Described Graphene transfer method, is characterized in that, substrate used is solid substrate.
Described Graphene transfer method, is characterized in that, substrate used is silicon chip.
Another kind of Graphene transfer method, is characterized in that, drop-burette is fixed on iron stand, has one of Graphene to face down tinsel length and is placed in target substrate surface, substrate is put in to the below of drop-burette, and tinsel is flattened; By rare HCl and H in drop-burette
2o
2mixed solution etchant solution drips in tinsel top, the etchant solution amount flowing out by controlling the on-off control of drop-burette, and making does not have etchant solution to enter between Graphene and substrate.
Another Graphene transfer method, is characterized in that, comprises the steps:
1) above adopt CVD legal system for Graphene in tinsel (Ni or Cu etc.);
2) there is one of Graphene to face down tinsel growth and be placed in target substrate (for example: silicon chip etc.) surface, tinsel is flattened, for example: by other smooth substrates pressures;
3) by be placed in the below of titration system with the substrate of tinsel, make FeCl by drop-burette
3solution flows in tinsel, simultaneously by the FeCl above the spile control Graphene of drop-burette below
3the amount of solution; Ensure that the solution in dropper is communicated with in corrosion process all the time with the solution in tinsel;
4) sample is left standstill, until FeCl
3by its region tinsel corrosion completely, final Graphene can be at FeCl for solution
3under the acting in conjunction of solution gravity and Van der Waals for, adhere to target substrate;
5) for example soak, after (: soak 30 minutes) with dilute hydrochloric acid solution, repeatedly above-mentioned substrate is rinsed with deionized water, remove residual Fe
3+ion; Afterwards the substrate that cleans up is taken out, and it is dried up with air gun.
Preferred:
Described Graphene transfer method, is characterized in that step 3) in, FeCl
3the concentration of solution is 0.01g/ml-1g/ml.
Described Graphene transfer method, is characterized in that step 3) in, FeCl
3the concentration of solution is 0.1g/ml.
Described Graphene transfer method, is characterized in that step 4) in, during sample is left standstill, sample being heated with fast reaction speed, Heating temperature is 70 DEG C, corrode 30 minutes, but temperature can not be higher than 90 DEG C.
Described Graphene transfer method, is characterized in that step 5) in, the concentration of dilute hydrochloric acid solution is 0.01mol/L-2mol/L, preferably 1mol/L.
Compared with prior art, the invention has the beneficial effects as follows:
Get involved without organism, easy and simple to handle, can not residual PMMA or the organic impurity such as acetone, thus avoid the infringement of organic residue to grapheme material quality and device performance.The method is having wide practical use aspect the new device taking Graphene as functional unit.
Brief description of the drawings
Fig. 1 is the Graphene transfer method schematic diagram (taking Copper Foil as example) that the present invention proposes.
Fig. 2 transfers to 300nm SiO by the present invention
2the optical microscope photograph of the Graphene on/Si substrate.
Fig. 3 is the Raman spectrum of the Graphene in Fig. 1.
Embodiment
The present invention adopts the Graphene transfer method of getting involved the directly etching tinsel of (comprising organic film and organic solvent etc.) without organism.As shown in Figure 1, step is as follows for main experimentation:
1) for example, above adopt CVD legal system for Graphene in tinsel (: Cu, Ni etc.).
2) there is one of Graphene to face down tinsel growth and be placed in target substrate (for example: silicon chip etc.) surface, tinsel is flattened, for example: by other smooth substrates pressures.。
3) below of titration system will be placed in the target substrate of tinsel.Make FeCl by drop-burette
3(0.1g/ml) solution flows in tinsel, remains on the FeCl of Graphene top by the spile control of drop-burette below simultaneously
3the amount of solution; Ensure that the solution in dropper is communicated with in corrosion process all the time with the solution in tinsel.
4) sample is left standstill, until FeCl
3solution by its region tinsel corrosion completely.Sample is heated to 70 DEG C therebetween, with fast reaction speed.Heat-processed continues 30 minutes altogether.Final Graphene can be at FeCl
3under the acting in conjunction of solution gravity and Van der Waals for, adhere to target substrate.
5) for example soak, after (: soak 10 minutes) with dilute hydrochloric acid solution (1mol/L), repeatedly above-mentioned substrate is rinsed with deionized water, remove residual Fe
3+ion.Afterwards the substrate that cleans up is taken out, and it is dried up with air gun.
Embodiment 1
The present invention for example, without the organic film material (: PMMA etc.) of using in conventional Graphene tranfer system (the figure art of composition), can will (for example: silicon chip directly transfer to other solid substrate surfaces at the Graphene of the upper growth of tinsel (Ni or Cu etc.), quartz plate, PET etc.) on.
As shown in Figure 1, taking Copper Foil as example, transfer process is as follows:
There is the Copper Foil of Graphene to be positioned over target substrate surface growth, make to face down with one of Graphene; By FeCl
3solution (0.1g/ml) drips in Copper Foil middle part by drop-burette; After copper is corroded completely, Graphene under the gravity of solution and the acting in conjunction of Van der Waals for will with solid substrate surface tight adhesion; Use afterwards dilute hydrochloric acid solution (1mol/L) and deionized water to clean sample, can in target substrate, obtain clean Graphene.
The method compare traditional transfer method have easy and simple to handle, without the organic materials such as PMMA, acetone, thus can residual organic impurity etc. advantage.
Fig. 2 transfers to 300nm SiO by the present invention
2the optical microscope photograph of the Graphene on/Si substrate.201 regions, figure top are the substrate that does not have Graphene to cover, and 202 regions, below are Graphene.
Fig. 3 is the Raman spectrum of the Graphene in Fig. 1.It is made up of two main peaks: G peak and 2D peak.The ratio at 2D peak and G peak is approximately 2, and the individual layer characteristic of this Graphene has been described.In addition, the D peak relevant to Graphene defect a little less than, illustrate that this Graphene quality is better.
Table 1 is the hall measurement data such as square resistance that adopt the Graphene that obtains of the present invention.
The hall measurement result of the Graphene after table 1. adopts the present invention to shift.Wherein, the mobility of sample is up to 941cm
2/ Vs.Show to shift rear Graphene and still there is good electrology characteristic.
Claims (10)
1. a Graphene transfer method, is characterized in that, drop-burette is fixed on iron stand, has one of Graphene to face down tinsel length and is placed in target substrate surface, substrate is put in to the below of drop-burette, and tinsel is flattened; By the FeCl in drop-burette
3solution drips in tinsel top, the FeCl flowing out by controlling the on-off control of drop-burette
3amount of solution, making does not have FeCl between Graphene and substrate
3solution enters.
2. Graphene transfer method as claimed in claim 1, is characterized in that, described tinsel is Copper Foil or nickel foil.
3. Graphene transfer method as claimed in claim 1, is characterized in that, substrate used is solid substrate.
4. Graphene transfer method as claimed in claim 1, is characterized in that, substrate used is silicon chip.
5. a Graphene transfer method, is characterized in that, drop-burette is fixed on iron stand, has one of Graphene to face down tinsel length and is placed in target substrate surface, substrate is put in to the below of drop-burette, and tinsel is flattened; By rare HCl and H in drop-burette
2o
2mixed solution etchant solution drips in tinsel top, the etchant solution amount flowing out by controlling the on-off control of drop-burette, and making does not have etchant solution to enter between Graphene and substrate.
6. a Graphene transfer method, is characterized in that, comprises the steps:
1) in tinsel, adopt CVD legal system for Graphene;
2) having one of Graphene to face down tinsel growth is placed in target substrate surface, tinsel is flattened;
3) by be placed in the below of titration system with the substrate of tinsel, make FeCl by drop-burette
3solution flows in tinsel, simultaneously by the FeCl above the spile control Graphene of drop-burette below
3the amount of solution; Ensure that the solution in dropper is communicated with in corrosion process all the time with the solution in tinsel;
4) sample is left standstill, until FeCl
3by its region tinsel corrosion completely, final Graphene can be at FeCl for solution
3under the acting in conjunction of solution gravity and Van der Waals for, adhere to target substrate;
5) after soaking with dilute hydrochloric acid solution, repeatedly above-mentioned substrate is rinsed with deionized water, remove residual Fe
3+ion; Afterwards the substrate that cleans up is taken out, and it is dried up with air gun.
7. Graphene transfer method as claimed in claim 6, is characterized in that step 3) in, FeCl
3the concentration of solution is 0.01g/ml-1g/ml.
8. Graphene transfer method as claimed in claim 6, is characterized in that step 3) in, FeCl
3the concentration of solution is 0.1g/ml.
9. Graphene transfer method as claimed in claim 6, is characterized in that step 4) in, during sample is left standstill, sample being heated with fast reaction speed, Heating temperature is 70 DEG C.
10. Graphene transfer method as claimed in claim 6, is characterized in that step 5) in, the concentration of dilute hydrochloric acid solution is 0.01mol/L-2mol/L.
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| CN104108704B CN104108704B (en) | 2016-01-20 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140083A (en) * | 2015-06-24 | 2015-12-09 | 中国科学院生物物理研究所 | Preparation method of grid of transmission electron microscope |
| CN105321808A (en) * | 2015-07-30 | 2016-02-10 | 中国电子科技集团公司第五十五研究所 | CVD graphene FET device manufacturing method capable of avoiding organic pollution |
| CN107311158A (en) * | 2017-06-24 | 2017-11-03 | 南昌航空大学 | A kind of method that graphene film is prepared on Ni-based and other substrates are transferred to |
| CN114852999A (en) * | 2022-04-27 | 2022-08-05 | 云南大学 | Method for transferring graphene |
| CN115650219A (en) * | 2022-10-08 | 2023-01-31 | 复旦大学 | Transfer method of CVD graphene |
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| US20110308717A1 (en) * | 2010-06-17 | 2011-12-22 | Samsung Techwin Co., Ltd. | Method of transferring graphene |
| CN102616769A (en) * | 2012-03-19 | 2012-08-01 | 浙江大学 | Direct graphene film transfer method |
| CN103342472A (en) * | 2013-07-11 | 2013-10-09 | 常州二维碳素科技有限公司 | Method for transferring graphene film |
| US20140166197A1 (en) * | 2012-12-19 | 2014-06-19 | National Taiwan Normal University | Method for transferring graphene layer |
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2014
- 2014-07-11 CN CN201410331217.0A patent/CN104108704B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110308717A1 (en) * | 2010-06-17 | 2011-12-22 | Samsung Techwin Co., Ltd. | Method of transferring graphene |
| CN102616769A (en) * | 2012-03-19 | 2012-08-01 | 浙江大学 | Direct graphene film transfer method |
| US20140166197A1 (en) * | 2012-12-19 | 2014-06-19 | National Taiwan Normal University | Method for transferring graphene layer |
| CN103342472A (en) * | 2013-07-11 | 2013-10-09 | 常州二维碳素科技有限公司 | Method for transferring graphene film |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140083A (en) * | 2015-06-24 | 2015-12-09 | 中国科学院生物物理研究所 | Preparation method of grid of transmission electron microscope |
| CN105321808A (en) * | 2015-07-30 | 2016-02-10 | 中国电子科技集团公司第五十五研究所 | CVD graphene FET device manufacturing method capable of avoiding organic pollution |
| CN105321808B (en) * | 2015-07-30 | 2018-09-28 | 中国电子科技集团公司第五十五研究所 | A kind of CVD graphene FET device manufacturing methods of avoidable organic contamination |
| CN107311158A (en) * | 2017-06-24 | 2017-11-03 | 南昌航空大学 | A kind of method that graphene film is prepared on Ni-based and other substrates are transferred to |
| CN107311158B (en) * | 2017-06-24 | 2019-11-08 | 南昌航空大学 | A method of it preparing graphene film on Ni-based and is transferred to other substrates |
| CN114852999A (en) * | 2022-04-27 | 2022-08-05 | 云南大学 | Method for transferring graphene |
| CN114852999B (en) * | 2022-04-27 | 2024-04-05 | 云南大学 | Method for transferring graphene |
| CN115650219A (en) * | 2022-10-08 | 2023-01-31 | 复旦大学 | Transfer method of CVD graphene |
| CN115650219B (en) * | 2022-10-08 | 2024-04-16 | 复旦大学 | Transfer method of CVD graphene |
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| CN104108704B (en) | 2016-01-20 |
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