CN104925803A - Graphene transferring method assisting by friction electrostatic force - Google Patents
Graphene transferring method assisting by friction electrostatic force Download PDFInfo
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- CN104925803A CN104925803A CN201510409379.6A CN201510409379A CN104925803A CN 104925803 A CN104925803 A CN 104925803A CN 201510409379 A CN201510409379 A CN 201510409379A CN 104925803 A CN104925803 A CN 104925803A
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Abstract
The invention relates to a graphene transferring method assisting by friction electrostatic force. The graphene transferring method assisting by the friction electrostatic force is a rapid and lossless transferring technology without assisting of glue. The invention aims at establishing a fast, convenient and high-quality new method for graphene transferring without auxiliary protection of organic polymer. Accumulation electric charge is acquired through the mutual friction of a target substrate and other materials and is used for producing the electrostatic force, the attraction of the electrostatic force on a copper foil substrate growing with graphene is utilized to realize the combination of the graphene and the target substrate, then the copper foil is removed, and transferring of the graphene from a growing substrate to the target substrate is completed. The graphene transferring method assisting by the friction electrostatic force has the advantages that assisting of the organic polymer is not needed, the operation is simple, and the cost is low. The graphene acquired by transferring is integral in structure, clean in surface and can be applied to a solar battery, a photosensor, a luminous diode, a displayer, a touch screen and other electron devices wide, and significant commercial value and practical significance are possessed for improving the performance of a nanometer functional device.
Description
Technical field
The invention belongs to the transfer field of Graphene, relate to quick, the harmless transfer without the need to polymer support of Graphene.
Background technology
Since being produced first from 2004, Graphene has become one of most active study hotspot.Can relation be with due to the two-dirnentional structure of its uniqueness and dirac taper, make it have high carrier mobility (~ 200000cm
2/ Vs), the light transmission (97.7%) of wide spectral, and the ductility (~ 20%) of high intensity (1Tpa) and excellence, therefore adopted widely on the multiple nano functional devices such as high speed integrated circuit, wide spectral photo-detector, biosensor, solar cell, ultracapacitor, lithium ion battery, flexible touch screen, be acknowledged as the nano material with huge applications and through engineering approaches prospect.In existing graphene preparation method, chemical Vapor deposition process (CVD) is considered to the most potential realization and prepares the method for high-quality graphene on a large scale and be widely studied.At the graphene film using CVD method to prepare in the process building graphene nano-device, being transferred in insulating substrate by growth Graphene is on the metallic substrate a necessary step.
Organic polymer secondary transfer becomes because it translates into the advantages such as power Graphene integrity that is high, that obtain is good maximum method that uses at present, but it has the defect that graphenic surface easily leaves organic substance residues simultaneously, cause and adopt the deficiencies such as the Graphene defect of this kind of method transfer is many, doping is serious, mobility is low.Simultaneously because the process of organics removal relates to the processes such as high temperature annealing or organic solvent clean repeatedly more, in the flexible substrate this transfer method not being suitable for Graphene is transferred to organism base, limit the application of Graphene in flexible electronic device.
In order to properly settle the problems referred to above, some transfer methods without the need to polymkeric substance arise at the historic moment.Such as directly shift, impress, volume to volume transfer, high-voltage electric field stripping etc.
(1) directly shift: William Regan etc. proposed a kind of method be transferred directly to by Copper Foil by Graphene on the micro-grid of transmission electron microscope in 2010, first they utilize has the copper foil surface of Graphene to drip aqueous isopropanol in growth, afterwards micro-grid are placed in the solution, after solution evaporation, micro-grid just and Copper Foil be combined togather, afterwards Copper Foil is dissolved the Graphene just obtained on micro-grid surface.Similar method is applied to equally to be transferred in insulating substrate by Graphene, Wei-Hsiang Lin etc. utilized in 2014 the feature that the surface tension of Virahol is less, Virahol is added in the etching liquid of Copper Foil, ensure that Graphene still can not break under the prerequisite not having organic polymer to support, thus Graphene has been transferred in silicon-on-insulator substrate.The method of direct transfer is the improvement in polymkeric substance secondary transfer method, solve the problem of polymer residue, but due to the disappearance of upholder, the meeting that Graphene is difficult to avoid produces the problem of breaking, damaging, translate into power not high, affect its use in subsequent device.
(2) impress: its principle is utilize bonding force between Graphene from various substrates different, certain " seal " is used first to be pasted from copper foil surface by Graphene, afterwards by " seal " directly by being pressed in target substrate, after " seal " is peeled off, Graphene has just been stayed in target substrate." seal " generally adopts certain organic polymer, because the bonding force of itself and Graphene is between Copper Foil and target substrate, thus completes the transfer of Graphene.The people such as Keun Soo Kim in 2009 just utilize PDMS to be transferred on silicon-on-insulator substrate by growth substrate Ni metal by Graphene as " seal ".Evgeniya H. Lock utilized another kind of organic polymer N-ethylamino-4-azidotetrafluorobenzoate (TFPA-NH in 2011
2) target substrate is modified, increase the bonding force of target substrate and Graphene, afterwards growth there is is the Copper Foil of Graphene directly by being pressed in target substrate, because the reactive force of Graphene and target substrate is stronger, thus Graphene being transferred directly in target substrate.The method operating process of impression is simple, and transfer efficiency is high, but due to " seal " very considerable with the bonding force of Graphene, cause Graphene often can not transfer in target substrate completely, cause the breakage of Graphene, have impact on the integrity of Graphene.
(3) volume to volume transfer: Jong-Hyun Ahn and Byung Hee Hong etc. proposed a kind of more towards the large-area graphene transfer method with suitability for industrialized production and practical application in 2010: volume to volume shifts.They utilize thermal-adhering directly to be combined with target substrate by Graphene in conjunction with the mode of roller bearing pressing, obtain the graphene film on PET substrate afterwards by dissolving Copper Foil.The advantage of this method is the transfer that can complete large-area graphene, and which show the volume to volume transfer that area reaches the graphene film of 30 inches, its working efficiency is obviously better than other Graphene transfer methods existing at present.But because it carries out the substrate material that shifts for applicable employing thermal-adhering, limit it in most of suprabasil application.
(4) high-voltage electric field is peeled off: utilize electric field to receive concern very early to the transfer that the magnetism of Graphene carries out Graphene.Chun-Wei Chen study group utilized highfield to make target substrate surface charging in 2013, attracted Graphene afterwards in target substrate, completed the transfer of Graphene.Chang-Soo Han also adopts the method for similar high-voltage electric field, utilizes electrostatic attraction directly to be attracted by Graphene to have transferred in target substrate.This method be a little that transport velocity is fast, the Graphene quality of transfer is high, but owing to adopting extra high tension electric field, making to shift needs complicated equipment and operating process.
As can be seen here, although it is residual serious that these methods solve graphenic surface in organism secondary transfer method, affect the problem of graphene film quality, but also result in Graphene cracky simultaneously, the Graphene defect that transfer obtains is many, integrity is bad, transfer process is complicated, has certain requirement, be difficult to the shortcomings such as practical application to equipment.
Summary of the invention
The method of the frictional static power secondary transfer graphene film proposed in the present invention is intended to the novel method setting up a kind of quick, convenient, high-quality Graphene transfer without the need for organic polymer auxiliary protection.This method can be summarized as: the heap accumulated charge utilizing target substrate and the mutual friction of other materials phase to obtain produces electrostatic force, utilize electrostatic force to growth have the magnetism of the Copper Foil substrate of Graphene to realize the combination of Graphene and target substrate, and then complete Graphene from growth substrate to target substrate on transfer.The present invention possesses without the need to organic polymer auxiliary, simple to operate, with low cost, shifts the advantages such as the graphene-structured obtained is complete, surface cleaning.Its concrete steps are as follows:
1) target substrate is as rear dry in PET etc. carries out repeated ultrasonic cleaning;
2) make target substrate charged target substrate and other substrates such as phase mutual friction such as glass;
3) growth is had the Copper Foil of Graphene and target substrate to be affixed to merge pressing make it combine firmly;
4) target substrate with Copper Foil is put into 1molL
-1feCl
3to dissolve Copper Foil in solution;
5) take out target substrate, with deionized water, it is repeatedly rinsed, use nitrogen to dry up afterwards, thus obtain the graphene film that is transferred in target substrate.
The present invention possesses following advantage in the transfer of Graphene: 1, working method is easy, and transfer process is simple, utilizes the mutual fricative electrostatic force between substrate can realize the transfer of Graphene; 2, the combination between Graphene and substrate is firm, improves the integrity of the rear graphene film of transfer; 3, assist without the need to organic polymer in process, solve the problem that it remains at graphenic surface, improve the quality of Graphene; 4, transferable graphene film area is large, and transfer efficiency is high; 5, do not relate to the step such as cleaning or high temperature annealing of organic solvent in transfer process, decrease its destruction to Graphene and substrate; 6, be suitable for and multiple easy charged substrate as glass, mica, PET, PI, PTFE etc.; 7, because organic substrate is very easily charged and electric charge not easily runs off, make present method have unique advantage being transferred to by Graphene in the flexible substrate that organism forms, be beneficial to the application of Graphene in flexible nano device; 8, achievement radiating surface is large, and the high-quality graphene film of gained, can be applicable to multiple association area, comprises photo-detector, solar cell, strain gauge and biosensor etc., to the performance improving nano functional device, is of great immediate significance.
Accompanying drawing explanation
Fig. 1 is transfer process schematic diagram a); B) charged substrate has the Copper Foil of Graphene to combine closely with growth; Be transferred to the 2*2cm graphene film c on multiple substrate); PET substrate d) PTFE and PI substrate.
Fig. 2 a) is transferred to graphene optical picture on PTFE; B) the Raman spectrum contrast before and after transfer on PTFE substrate; D) and e) the Raman mapping image of Graphene that obtains of transfer; C) XPS spectrum of graphene film.
Embodiment
Be described in detail to technical scheme of the present invention below in conjunction with example, obviously, described example is only a part very little in the present invention, instead of whole examples.Based on the example in the present invention, those skilled in the art, not making the every other example obtained under creative work prerequisite, belong to the scope of protection of the invention.
example 1: the Graphene of growth on Copper Foil is transferred in PET base by the method utilizing frictional static to shift
(1) cleaning of substrate: be successively placed in deionized water, acetone, Virahol by the PTFE substrate of the PET base of 2.5*2.5cm and 5*3cm, in each solution after the ultrasonic cleaning of each 10 minutes, take out, nitrogen dries up.
(2) substrate is charged: utilize PET base and PTFE substrate phase mutual friction about 20 times, make PET base charged.
(3) charged PET base being placed on growth has on the Copper Foil of Graphene, Copper Foil is combined with PET, firmly presses PET base afterwards, make Copper Foil and PET close contact.
(4) PET base with Copper Foil is placed on 1molL
-1feCl
3in solution, Copper Foil is dissolved gradually, and the Graphene of growth on Copper Foil stay on the pet substrate.
(5) take out PET base, repeatedly rinse with deionized water, dry up afterwards with nitrogen, now Graphene has been transferred in PET base.
example 2: the Graphene of growth on Copper Foil is transferred in PI substrate by the method utilizing frictional static to shift
(1) cleaning of substrate: be successively placed in deionized water, acetone, Virahol by the substrate of glass of the PI substrate of 2.5*2.5cm and 5*3cm, in each solution after the ultrasonic cleaning of each 10 minutes, take out, nitrogen dries up.
(2) substrate is charged: utilize PI substrate and the mutual friction of substrate of glass phase about 20 times, make PI substrate charged.
(3) charged PI substrate being placed on growth has on the Copper Foil of Graphene, and Copper Foil is combined with PI, and firmly pressing PI substrate, makes Copper Foil and PI close contact afterwards.
(4) the PI substrate with Copper Foil is placed on 1molL
-1feCl
3in solution, Copper Foil is dissolved gradually, and the Graphene of growth on Copper Foil is stayed in PI substrate.
(5) take out PI substrate, repeatedly rinse with deionized water, after this dry up with nitrogen, now Graphene has been transferred in PI substrate.
example 3: the Graphene of growth on Copper Foil is transferred on PTFE by the method utilizing frictional static to shift
(1) cleaning of substrate: be successively placed in deionized water, acetone, Virahol by the substrate of glass of the PTFE substrate of 2.5*2.5cm and 5*3cm, in each solution after the ultrasonic cleaning of each 10 minutes, take out, nitrogen dries up.
(2) substrate is charged: utilize PTFE substrate and the mutual friction of substrate of glass phase about 20 times, make PTFE substrate charged.
(3) charged PTFE substrate being placed on growth has on the Copper Foil of Graphene, and Copper Foil is combined with PTFE, and firmly pressing PTFE substrate, makes Copper Foil and PTFE close contact afterwards.
(4) the PTFE substrate with Copper Foil is placed on 1molL
-1feCl
3in solution, Copper Foil is dissolved gradually, and the Graphene of growth on Copper Foil is stayed in PTFE substrate.
(5) take out PTFE substrate, repeatedly rinse with deionized water, after this dry up with nitrogen, now Graphene has been transferred in PTFE substrate.
Claims (4)
1. one kind utilizes frictional static power secondary transfer Graphene method; described the method is without the need for organic polymer auxiliary protection; it is characterized in that; the heap accumulated charge that described method utilizes target substrate and the other materials phase mutual friction such as glass to obtain produces electrostatic force; electrostatic force is utilized to have the magnetism of the growth substrate of Graphene to realize the combination of Graphene and target substrate to growth; remove growth substrate subsequently, complete the transfer of Graphene from growth substrate to target substrate.
2. a kind of method utilizing frictional static power secondary transfer Graphene according to claim 1, it is characterized in that, described method specifically comprises the steps:
1) dry after target substrate being carried out repeated ultrasonic cleaning;
2) target substrate and the other materials such as glass are carried out phase mutual friction, make target substrate charged;
3) growth there are Copper Foil substrate and the mutual secure fit of target substrate of Graphene;
4) target substrate with Copper Foil is put into 1molL
-1feCl
3in solution, dissolve Copper Foil;
5) take out target substrate, with deionized water, it is repeatedly rinsed, use nitrogen to dry up afterwards, thus obtain the graphene film that is transferred in target substrate.
3. a kind of method utilizing frictional static power secondary transfer Graphene according to claim 2, it is characterized in that, described target substrate is easy charged materials.
4. a kind of method utilizing frictional static power secondary transfer Graphene according to claim 3, it is characterized in that, described target substrate is the organic polymers such as PET, PI, PTFE.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435727A (en) * | 2016-11-17 | 2017-02-22 | 北京大学 | Method for preparing high-integrity suspended graphene by clean transfer |
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- 2015-07-13 CN CN201510409379.6A patent/CN104925803A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| DI-YAN WANG ET AL.: "Clean-Lifting Transfer of Large-area Residual-Free Graphene Films", 《ADVANCED MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435727A (en) * | 2016-11-17 | 2017-02-22 | 北京大学 | Method for preparing high-integrity suspended graphene by clean transfer |
| CN106435727B (en) * | 2016-11-17 | 2019-01-01 | 北京大学 | A kind of method that clean transfer prepares the hanging graphene of high integrity degree |
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Application publication date: 20150923 |
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