CN110234602A - From the graphene transfer method and graphene for sacrificing supporting layer auxiliary - Google Patents
From the graphene transfer method and graphene for sacrificing supporting layer auxiliary Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B32/194—After-treatment
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Abstract
A kind of graphene transfer method from sacrifice supporting layer auxiliary, at least include the following steps: step S01. carries out the multiple coating processing of camphor solution in the graphene surface comprising metallic substrates that chemical vapor deposition method obtains, and the graphene for being coated with the camphor solution is heated, acquisition layer structure is camphor-graphene-metallic substrates lamination；Step S02. performs etching processing to the lamination, removes the metallic substrates, obtains camphor-graphene film；Step S03. starts the cleaning processing the camphor-graphene film, and the cleaned camphor-graphene film is transferred to substrate surface；The removal that step S04. carries out the camphor together with the camphor-graphene film to the substrate that step S03 is handled is handled.This method does not introduce impurity, and the graphene of acquisition is good without supporting layer residual, surface integrity, and graphene can be made to combine closely with target substrate.
Description
It is the invention belongs to technical field of graphene, in particular to a kind of from the graphene transfer method and graphene of sacrificing supporting layer auxiliary.
After the method that is by mechanically pulling off obtains graphene, since it has attracted with unique electric property, mechanical performance, optical property and hot property etc. extensive concern and the research of scientific circles, and very extensive application prospect is shown.These have promising application and specifically include the fields such as photonics, photoelectronics and organic electronics, such as solar battery, light emitting diode, touch screen technology, photoelectricity testing part and the membrane material for the molecule separation in gas or liquid.
Although the scale that graphene may be implemented there are many method so far is combined to; but only chemical vapor deposition growth method (English Chemical Vapor Deposition, abbreviation CVD) is considered as the scale synthetic method of most prospects for commercial application.The seminar that many is engaged in correlative study realized in the pure copper foil of electrochemical polish millimeter to cm range size graphene synthesis, established sizable technical foundation for its scale design for being used for photoelectron and transistor device manufacture view.However, what is grown on copper foil there is large scale and the continuous graphene of large area not to have direct practical application, and needing to be transferred in the dielectric substrate for being widely used in manufacture electronic device just has application value.But how to shift so that it is a very big problem that graphene, which keeps good integrality,.
Graphene is originally found process from separating graphene from graphite by using adhesive tape, this is exactly a kind of transfer process of graphene.Under normal conditions, the transfer of CVD synthesizing graphite alkene can be realized by two kinds of technologies, i.e. dry method transfer and wet process transfer.Up to the present, it is to mediate (supporting layer) with polymethyl methacrylate (PMMA), transfers graphene to such as silica (SiO2), the transfer method in quartz or the dielectric substrates such as plastics it is widely used.
Furthermore, due to the intrinsic rough surface of the graphene grown on metal foil, and the weak engineering properties of the PMMA layer of spin coating, cause to generate some local gaps between graphene and target substrate, and this local gap can have an adverse effect to graphene platelet, because local gap can capture hydrone by van der Waals interaction
And the graphene of transfer is caused to generate destructive slight crack.
Recently, show that certain materials can be used to replace PMMA according to several parts of correlative studys, to avoid the residual contamination on graphene is caused, but be not found the experimental result being consistent.Even if introducing many other polymer such as rosin, black wax etc. still cannot achieve the graphene transfer of flawless and noresidue pollution to substitute PMMA.At present entirely in the transfer method based on chemical etching, removing the polymer film of graphene surface using related reagent later on being transferred to dielectric substrate is one of the significant challenge in graphene transfer techniques
When at present using PMMA as graphene transfer medium, it is difficult to completely remove on the graphene by PMMA after having turned.And the reagent shifted by PMMA polymer or other supporting layers remains on graphene later on being transferred to dielectric substrate, polymeric support layer not only reduces the special performance (electric property as reduced graphene) of graphene, and keeps transfer step more complicated；Other pyrolytic process is also required to be lot more time to remove residue.In addition, the method for existing removal residue such as washing or pyrolysis are not suitable for having the removal of the surface mass of the flexible parent metal of low melting point yet, therefore there are various restrictive conditions in the transfer of graphene in actual operation.
In conclusion by transferring graphene to SiO2Etc. technology in dielectric substrates still have lot of challenges.
Solution to the problem
Graphene transfer step present in the transfer process complexity obtained for current CVD method, the graphene for having supporting layer to remain, can not obtaining large scale, large-area graphene and acquisition have the problems such as breakage, and the present invention provides a kind of graphene transfer method sacrificing supporting layer certainly and assisting.
It is a further object of the invention to provide a kind of graphenes by obtaining from the graphene transfer method for sacrificing supporting layer auxiliary.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of graphene transfer method from sacrifice supporting layer auxiliary, at least includes the following steps:
Step S01. carries out the multiple coating processing of camphor solution in the graphene surface comprising metallic substrates that chemical vapor deposition method obtains, and heats to the graphene for being coated with the camphor solution, obtains layer knot
Structure is camphor-graphene-metallic substrates lamination；
Step S02. performs etching processing to the lamination, removes the metallic substrates, obtains camphor-graphene film；
Step S03. starts the cleaning processing the camphor-graphene film, and the cleaned camphor-graphene film is transferred to substrate surface；
The removal that step S04. carries out the camphor together with the camphor-graphene film to the substrate that step S03 is handled is handled.
Correspondingly, a kind of graphene, the graphene are obtained by above-mentioned from the graphene transfer method for sacrificing supporting layer auxiliary.
Advantageous effect of the invention
Compared with the existing technology; graphene transfer method provided by the invention from sacrifice supporting layer auxiliary; surface does not introduce other new impurity without supporting layer residue yet in graphene transfer process, and the graphene obtained is without destructive slight crack; integrality is good; complete, large scale, the continuous graphene of large area can be obtained, at the same time, this transfer method is convenient and simple; suitable for large-scale production, and the meaning with practical application.
The graphene obtained by the present invention, because of its superficiality N/D, noresidue impurity, size is big, area is big, it is thus possible to show the performance of good graphene.
To the brief description of accompanying drawing
Fig. 1 is process flow diagram of the present invention from the graphene transfer method for sacrificing supporting layer auxiliary；
Fig. 2 is that the embodiment of the present invention 1 is transferred to SiO2The optical microscope image of the graphene of/Si substrate surface；
Fig. 3 is that the embodiment of the present invention 1 is transferred to SiO2The SEM picture of the graphene of/Si substrate surface；
Fig. 4 is that the embodiment of the present invention 1 is transferred to SiO2The another SEM picture of the graphene of/Si substrate surface；
Fig. 5 is that the embodiment of the present invention 1 is transferred to SiO2The Raman spectrum of the graphene of/Si substrate surface.
Inventive embodiments
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, with reference to embodiments, the present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
It is worth noting that, what graphene, graphene film indicated is the same substance in the present invention.Camphor-graphene film namely includes the material of camphor film and graphene film.
Referring to FIG. 1, the present invention provides a kind of graphene transfer method from sacrifice supporting layer auxiliary.
Specifically, the graphene transfer method at least includes the following steps:
Step S01. carries out the multiple coating processing of camphor solution in the graphene surface comprising metallic substrates that chemical vapor deposition method obtains, and the graphene for being coated with the camphor solution is heated, acquisition layer structure is camphor-graphene-metallic substrates lamination；
Step S02. performs etching processing to the lamination, removes the metallic substrates, obtains camphor-graphene film；
Step S03. starts the cleaning processing the camphor-graphene film, and the cleaned camphor-graphene film is transferred to substrate surface；
The removal that step S04. carries out the camphor together with the camphor-graphene film to the substrate that step S03 is handled is handled.
Detailed explanation is done to above-mentioned graphene transfer method below:
The present invention relates to the graphenes to be shifted, it is the graphene obtained using chemical vapour deposition technique, that is to say, that through chemical vapour deposition technique, after metal substrate surface deposits one layer of graphene, transfer object together with metallic substrates, as graphene transfer method of the present invention.
Generally, metallic substrates are copper foil, naturally it is also possible to be other metals other than copper foil, as long as those skilled in the art it is conceivable that other metallic substrates, suitable for the present invention.
And in order to enable obtain graphene surface it is relatively flat, before chemical vapor deposition graphene, need to metallic substrates carry out electrochemical polishing treatment.For example copper foil is polished using electrochemistry, so that copper foil surface is flat and smooth, smooth graphene film is obtained convenient for deposition, reduces the surface defect of graphene.
In some embodiments, before coating camphor solution, it is also necessary to carry out planarization process to the graphene that chemical vapour deposition technique obtains.Because while the graphene together with metallic substrates that chemical vapor deposition obtains is relatively flat, and still, when metallic substrates are taken out together with graphene in chemically gaseous phase deposition stove, metallic substrates
More wrinkle can be generated, in order to enable metallic substrates keep having uniformly good contact with graphene sedimentary, graphene-metallic substrates can be placed in the surface of a strata ethylene terephthalate (PET), then a strata ethylene terephthalate is covered again, it forms graphene-metallic substrates and is located in the middle sandwich structure, then using glass bar or equipment roll-in PET/ graphene-metallic substrates/PET composite layer of other club shaped structures, the wrinkle of metallic substrates is decreased or even eliminated, so that graphene sedimentary is adjacent to metallic substrates.
And in order to enable metallic substrates quickly etch, before coating camphor solution, the oxygen plasma etch metallic substrates back side can be used (back side here refers to the surface for not depositing graphene).By oxygen plasma etch, so that metallic substrates can be etched quickly in etching liquid, shorten etch period.
Preferably, the solvent of the camphor solution in step S01 is chlorobenzene, and chlorobenzene is good with camphor compatibility, and during heating, chlorobenzene is readily volatilized, when chlorobenzene volatilizees, camphor due to having weaker adhesiveness is easy that weak binding occurs and forms thin film on the surface of graphene with graphene.And camphor has the transparency and the characteristics such as brittleness is weak, and since it is easy to happen distillation, it does not need any solvent and can be realized from graphene surface thoroughly to remove, this is not completely identical as transfer supporting layer as conventional PMMA and other polymers, and it can guarantee supporting layer of the graphene surface without other impurities introducing, noresidue, moreover it is possible to ensure the integrality of graphene.
It is further preferred that the mass concentration of camphor solution is 30~100%, concentration is too low, and the formation of camphor film is more difficult.It is worth noting that, the mass concentration ratio of camphor solution of the present invention, refers to Solute mass and solvent volume ratio, namely such as 3g camphor is dissolved in 10mL chlorobenzene, the mass concentration so obtained is that 30%, 10g camphor is dissolved in the chlorobenzene of 10mL, then obtained mass concentration is 100%.
And in order to obtain camphor film in homogeneous thickness, the coating of camphor solution generally uses spin coating mode, and multiple spin coating.It such as can be triple spin coatings, it may be assumed that first with the revolving speed spin coating about 30s of 1000rpm, be heated to 132~150 DEG C, heat preservation 2min or so is cooled to room temperature immediately；Again with the revolving speed spin coating about 60s of 2500rpm, continue to be heated to 132~150 DEG C, heat preservation 2min or so, finally again with the revolving speed spin coating about 60s of 2500rpm, continues to be heated to 132~150 DEG C, heat preservation 2min or so.Heating and thermal insulation after each spin coating, main purpose are so that camphor and graphene generate close and stronger adhesiveness, while but also chlorobenzene solvent rapid evaporation, is convenient for camphor film forming.
Step S02 due to camphor-graphene film light transmittance with higher, is visually not easy to find, therefore can use white-light illuminating, so that camphor tree to when layer structure is that camphor-graphene-metallic substrates lamination performs etching
Brain-graphene film occurs projection and generates shade, to facilitate the camphor-graphene film identified after etching metallic substrates.
Since camphor-graphene film itself is relatively transparent, and there is hydrophobicity, after metallic substrates are etched, camphor-graphene film constantly floats in aqueous etching liquid, one inconvenient identification, two inconvenient shift from etching liquid, in order to facilitate identifying and shift cleaning, before etching, the camphor layer surface that spin coating obtains can be attached to using colorful adhesive tape, processing can not only guarantee that camphor-graphene film is unfolded naturally in etching liquid in this way, and it is also easy to be found, and facilitate transfer, also ensure that camphor-graphene film does not crack or pin hole in the process of cleaning.
In cleaning, needs for camphor-graphene film to be transferred in cleaning solution, remain in camphor-graphene film surface etching liquid to wash.Since camphor-graphene film is inconvenient to shift, by the way of dipping, by dipping, graphene can be avoided, fold even breakage occurs.And if being pasted with colorful adhesive tape in camphor layer surface, colorful adhesive tape can be clamped at multiple positions simultaneously be transferred in cleaning solution to realize.
Preferably, the cleaning solution used in the present invention is deionized water or ethyl alcohol, and deionized water and ethyl alcohol will not introduce impurity, and readily volatilized after cleaning.
, can be repeated multiple times when being cleaned using cleaning solution, when can't detect the ingredient of etching liquid when until cleaning solution is taken to be detected, it can stop cleaning, such as when metallic substrates are copper foil, the etching liquid generally selected is the FeCl of 0.03wt%2Solution can stop cleaning when detecting in cleaning solution without ferrous ion or chloride ion.The impurity such as the metal ion mainly avoided in etching liquid residual is cleaned multiple times on the surface of graphene.
After terminating cleaning, camphor-graphene film is transferred to new substrate surface, is paved, room temperature stands the removal that camphor can be realized, and can also be placed in drying box and dry, in drying course, camphor distillation, colorful adhesive tape does not contact directly with graphene, therefore falls off naturally.
Preferably, the drying temperature of drying box is 40~100 DEG C, at such a temperature, can make camphor rapid sublimation.
Certainly, if it is the removal in order to faster realize camphor, new substrate can also be connected to and be heated to 210~250 DEG C together, so that camphor melts, removed rapidly.Camphor has reached fusing point at 210~250 DEG C, can quickly remove, and leaves the graphene for being layered on substrate surface, and this method is known as the annealing of camphor.It when using annealing, needs before colorful adhesive tape melts, takes out rapidly, colorful adhesive tape is avoided to melt and pollute graphene surface.
Preferably, the substrate in step S03, can be general substrate, is also possible to dielectric substrate.If need to obtain complete, large scale, large area graphene, then use general substrate, and if it is dielectric substrate in order to which graphene is laid on dielectric substrate surface, is then directlyed adopt, to avoid breakage occurs when being laid with graphene with dielectric substrate again.When graphene is laid on dielectric substrate surface, strong adhesive attraction occurs with dielectric substrate, it is not easy to it is torn from dielectric substrate surface, therefore, the process that this process can regard graphene as and dielectric substrate bonds.Dielectric substrate after in conjunction with graphene can be used for the production of other devices.Such as it can be used in opto-electronic device, for example as the electrode material of photoelectric device.And since method of the present invention is not comprising organic reagent processing, so can be used for preparing transparent flexible electrode when the dielectric substrate for being coated with graphene obtained using the method for the present invention is if it is flexible plastic substrate and apply in flexible electronic device.
Preferably, dielectric substrate is any one of silica, silicon, silica/silicon, quartz, glass, plastics.
Graphene transfer method of the present invention from sacrifice supporting layer auxiliary, it is removed without using the supporting layer to graphene such as organic solvent, and in graphene transfer process surface without supporting layer residue, other new impurity are not introduced yet, and the graphene obtained is without destructive slight crack, integrality is good, can obtain complete, large scale, the continuous graphene of large area.At the same time, this transfer method is convenient and simple, is suitable for large-scale production, and the meaning with practical application.
The graphene that transfer method of the invention obtains, because of its superficiality N/D, noresidue impurity, size is big, area is big, it is thus possible to show the performance of good graphene.
Further, the present invention also provides a kind of opto-electronic device, this opto-electronic device includes substrate and the graphene for being attached to the substrate surface.Wherein, what graphene provided through the invention is transferred to the substrate surface from the graphene transfer method for sacrificing supporting layer auxiliary.That is, the graphene of this opto-electronic device is obtained using CVD method, is then transferred to substrate surface using transfer method of the invention, the graphene for being attached to the substrate surface being achieved in that is without destructive slight crack, integrality is good, and size is big, area is big and continuity is good.
Preferably, the substrate that opto-electronic device is related to is dielectric substrate.The dielectric substrate is any one of silica, quartz, plastics, silicon, silica/silicon.
Further, the present invention also provides a kind of transistor device, this transistor device includes substrate and attachment
In the graphene of the substrate surface.Wherein, what graphene provided through the invention is transferred to the substrate surface from the graphene transfer method for sacrificing supporting layer auxiliary.That is, the graphene of this transistor device is obtained using CVD method, is then transferred to substrate surface using transfer method of the invention, the graphene for being attached to the substrate surface being achieved in that is without destructive slight crack, integrality is good, and size is big, area is big and continuity is good.The graphene transfer method from sacrifice supporting layer auxiliary that embodiment provides in order to better illustrate the present invention, further explains below by multiple embodiments.
Embodiment 1
1.CVD method grows graphene
(1) is in phosphoric acid and the electrolyte solution of ethylene glycol volume ratio 3: 1, with the commercially available copper foil of bias electrobrightening (98% purity, 25 μm thick, Alfa Aesar#46565) 30min of 2V.
(2) is then successively cleaned with copper foil of the second alcohol and water to polishing repeatedly, to ensure the electroless residue of copper foil surface；Finally single-layer graphene growth will be carried out in the copper foil merging low pressure CVD system of electrobrightening.
(3) copper foil is placed in the thermal center (-tre) of the long-tube quartz furnace of 4 inch diameters by, and tube furnace is deaerated to reaching 7 × 10-2The initial growth pressure of support.First at 950 DEG C, 50sccm H2, under the conditions of 1 support of pipe pressure, copper foil annealing is handled into 60min；20sccm methane is then passed to, continuous single-layer graphene 30min is grown under the pipe pressure of 2 supports.
2. graphene shifts
(1) carries out planarization process to the copper-base graphite alkene of CVD growth, copper-base graphite alkene is placed in the surface of one layer of PET sheet, one layer of PET sheet is covered on copper-base graphite alkene surface simultaneously, then using glass bar in the repeated multiple times roll-in in PET sheet surface, so that graphene is smooth with copper foil and is mutually adjacent to.
(2) the camphor solution (chlorobenzene is solvent) that concentration is 70% (7g/10mL) is spin-coated on graphene/copper foil and forms camphor film as transfer supporting layer.Continue 30s at revolving speed 1000rpm, graphene/copper foil thin layer after coating camphor solution need to heat 1min at 150 DEG C, and then continue 60s under revolving speed 2500rpm, and 150 DEG C of heating 1min can be obtained camphor film three times repeatedly.Camphor has waxy, the formation transparent membrane after coating to copper-base graphite alkene；Then graphene/copper foil is placed on flat PET and covers graphene/copper foil edge using adhesive tape.
(3) 0.03wt%FeCl is used2Solution etches copper foil substrate forms the graphene/camphor thin layer for floating on etching solution surface.The container for filling etching solution is placed on blank sheet of paper, while being compared using bright white light, is made
The film cast shadow on etching solution surface is to be easily viewed.
(4) graphene taken out from etching liquid/camphor thin layer is rinsed with deionized water, to avoid metal-doped in graphene or camphor thin layer surface.
(5) graphene/camphor film that deionized water was cleaned is dipped and is transferred to SiO2On/Si substrate, and it is stored in 2~4h in drying box.
SiO is covered on using what optical microscopy, scanning electron microscope, four probe systems, Raman spectrum analysis obtained2The graphene of/Si substrate.
As it is clear from fig. 2 that optical microscopy shows in SiO2There are graphenes in/Si substrate.
And show the graphene of transfer in SiO from the SEM image of Fig. 3, Fig. 42There is a wide range of continuity, there are insignificant pin hole, the method that can be shifted by two or more layers graphene is eliminated the effects of the act for partial region on/Si substrate.It can be seen that graphene is in SiO2There is good continuity on/Si substrate.
Sheet resistance is measured by using four probe systems, it was found that: when by primary transfer, the resistance of graphene film is in 350~500 Ω/section sq, after the transfer of multiple graphene, the resistance of graphene film is reduced to 80~120 Ω/section sq, it is seen that the conductivity of sample is significantly improved.
From the Raman Characterization of Fig. 5 it is found that G characteristic peak and 2D characteristic peak is presented in characterization result, and camphor is without significantly comparing peak.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, and any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all be included in the protection scope of the present invention.
Claims (15)
- A kind of graphene transfer method from sacrifice supporting layer auxiliary, it is characterised in that: at least include the following steps:Step S01. carries out the multiple coating processing of camphor solution in the graphene surface comprising metallic substrates that chemical vapor deposition method obtains, and the graphene for being coated with the camphor solution is heated, acquisition layer structure is camphor-graphene-metallic substrates lamination；Step S02. performs etching processing to the lamination, removes the metallic substrates, obtains camphor-graphene film；Step S03. starts the cleaning processing the camphor-graphene film, and the cleaned camphor-graphene film is transferred to substrate surface；The removal that step S04. carries out the camphor together with the camphor-graphene film to the substrate that step S03 is handled is handled.
- Graphene transfer method as described in claim 1 from sacrifice supporting layer auxiliary, it is characterised in that: the solvent of the camphor solution is chlorobenzene, and the mass concentration of the camphor solution is 30%~100%.
- As claim 1~2 is described in any item from the graphene transfer method for sacrificing supporting layer auxiliary, it is characterised in that: the temperature of the heat treatment is 132~150 DEG C.
- Graphene transfer method as described in claim 1 from sacrifice supporting layer auxiliary, it is characterised in that: the coating method is spin coating.
- As claim 1~2 is described in any item from the graphene transfer method for sacrificing supporting layer auxiliary, it is characterised in that: the substrate is dielectric substrate.
- Graphene transfer method as claimed in claim 5 from sacrifice supporting layer auxiliary, it is characterised in that: the material of the dielectric substrate is any one of silica, silicon, silica/silicon, quartz, glass, plastics.
- Certainly the graphene transfer method as described in claim 1 for sacrificing supporting layer auxiliary, it is characterised in that: the removal processing mode of the camphor is to be dried or make annealing treatment.
- Graphene transfer method as claimed in claim 7 from sacrifice supporting layer auxiliary, it is characterised in that: the temperature of the annealing is 210~250 DEG C.
- The graphene transfer method assisted from sacrifice supporting layer as described in weighing and require 7, it is characterised in that: the mode of the drying process is 40~100 DEG C of processing in drying box.
- Graphene transfer method as described in claim 1 from sacrifice supporting layer auxiliary, it is characterised in that: the cleaning solution that the cleaning treatment uses is deionized water or ethyl alcohol.
- As claim 1~2 is described in any item from the graphene transfer method for sacrificing supporting layer auxiliary, it is characterised in that: further include carrying out the gluing treatment of colorful adhesive tape on the camphor surface after step S01 processing.
- A kind of graphene, it is characterised in that: the graphene is obtained by as claimed in any one of claims 1 to 11 from the graphene transfer method for sacrificing supporting layer auxiliary.
- A kind of opto-electronic device, it is characterised in that: the opto-electronic device includes substrate and the graphene for being attached to the substrate surface, and the graphene is transferred to the substrate surface using the described in any item transfer methods of claim 1~11.
- Opto-electronic device as claimed in claim 13, it is characterised in that: the substrate is any one of silica, quartz, plastics, silicon, silica/silicon.
- A kind of transistor device, it is characterised in that: the transistor device includes substrate and the graphene for being attached to the substrate surface, and the graphene is transferred to the substrate surface using the described in any item transfer methods of claim 1~11.
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| CN111254414A (en) * | 2020-01-21 | 2020-06-09 | 西安工程大学 | Preparation and transfer method of flexible graphene-based silicon nanowire heterojunction |
| CN114538429A (en) * | 2022-04-19 | 2022-05-27 | 深圳前海石墨烯产业有限公司 | Graphene transfer method based on metal chromium sacrificial layer |
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