CN104261402B - A kind of transfer method of Graphene - Google Patents
A kind of transfer method of Graphene Download PDFInfo
- Publication number
- CN104261402B CN104261402B CN201410555097.2A CN201410555097A CN104261402B CN 104261402 B CN104261402 B CN 104261402B CN 201410555097 A CN201410555097 A CN 201410555097A CN 104261402 B CN104261402 B CN 104261402B
- Authority
- CN
- China
- Prior art keywords
- graphene
- substrate
- present
- transfer
- transfer method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a kind of transfer method of Graphene, comprise the following steps: 1) medium that the substrate depositing Graphene is placed in containing oxidizing substance is processed; 2) by described step 1) deposit the side of Graphene in substrate after process and target substrate bonds; 3) by described step 2) substrate desquamation in the sample that obtains, complete the transfer of Graphene.First the substrate depositing Graphene is placed in Oxidant and processes by method provided by the invention, reduce the interface binding power between Graphene and substrate, thus Graphene is easily come off by substrate surface when making the later stage at the bottom of peeling liner, the integrity of Graphene can not be damaged, transfer to Graphene in target substrate without breakage, and Graphene defect is less.
Description
Technical field
The present invention relates to technical field of graphene preparation, particularly relate to a kind of transfer method of Graphene.
Background technology
Graphene is a kind of is the cancellated carbonaceous novel film material of sexangle by monolayer carbon atomic arrangement.The aspects such as nanometer electronic device, supercomputer, solar cell, lithium ion battery, optoelectron sensor, gene sequencing, noise control can be applied in.Compared to ITO, the advantage of Graphene can do fexible film, can not turn to be yellow because of the interference of light, not by the restriction of natural resources.Therefore graphene film is expected to the equivalent material as the ITO generally used at present, for aspects such as touch panel, flexible liquid crystal panel, solar cell and organic EL illuminatings.
The method preparing graphene film at present has mechanically peel, epitaxy, chemical vapour deposition (CVD), and wherein CVD is topmost preparation method.The carbon source of gas phase is mainly deposited on substrate by CVD, and Graphene will be transferred in required target substrate by the application that will realize Graphene.The Graphene transfer method extensively adopted at present is the surface-coated organic gel at Graphene, etches away substrate, then remove organic gel after oven dry with etching liquid.
Application number be 201310362356.5 Chinese patent disclose a kind of CVD Graphene transfer method, it uses CVD deposited graphite alkene on Copper Foil, then copper foil surface spin coating one deck polymethylmethacrylate (PMMA) solution of Graphene is being deposited, by ammonium persulphate ((NH after its solidification
4)
2s
2o
8) solution corrosion removing Copper Foil, Graphene-PMMA picks up drying by target substrate after cleaning, and then selects organic acid solvent to dissolve PMMA layer, removes graphenic surface further remain PMMA finally by high temperature annealing mode.Etch away substrate with etching liquid, remove the procedure complexity of organic gel after this class coating organic gel, oven dry, and need etching copper, what have also needs dissolving supporter.And corrode in the process of copper and dissolving glue and can produce defect and impurity in Graphene after the transfer, be unfavorable for the application of Graphene after turning.
Summary of the invention
The object of the present invention is to provide a kind of transfer method of Graphene, method provided by the invention is by Graphene by after in substrate-transfer to target substrate, and Graphene is without breakage.
The invention provides a kind of transfer method of Graphene, comprise the following steps:
1) medium that the substrate depositing Graphene is placed in containing oxidizing substance is processed;
2) by described step 1) deposit the side of Graphene in substrate after process and target substrate bonds;
3) by described step 2) substrate desquamation in the sample that obtains, complete the transfer of Graphene.
Preferably, described medium is liquid phase medium and/or gas phase media;
Described liquid phase medium comprises one or more in water, ethanol, acetic acid, benzene and acetone;
Described gas phase media comprises one or more in water vapour, alcohol vapour, acetic acid steam, benzene vapour and acetone steam.
Preferably, described oxidizing substance comprises one or more in gaseous oxygen voltinism material, solid oxygen voltinism material and liquid oxygen voltinism material;
Described gaseous oxygen voltinism material comprises one or more in oxygen, sulfurous gas, chlorine and hydrogenchloride;
Described solid oxygen voltinism medium comprises one or more in potassium permanganate, Sodium Nitrite, clorox and sodium perchlorate;
Described liquid oxygen voltinism material comprise in hydrogen peroxide, phenol, toluene, acetaldehyde one or more.
Preferably, described oxidizing substance mass percent is in media as well 0.01% ~ 50%.
Preferably, described oxidizing substance mass percent is in media as well 0.1% ~ 10%.
Preferably, described step 1) in process temperature be 0 DEG C ~ 100 DEG C.
Preferably, described step 1) in process time be 0.1h ~ 24h.
Preferably, described step 2) in be bonded as electrostatic bonding, colloid bonding or Van der Waals force bonding.
Preferably, described step 3) be specially: adopt mechanically peel, acid solution process or electrochemical treatment, by described step 2) substrate in the sample that obtains is separated with the target substrate being bonded with Graphene, completes the transfer of Graphene.
Preferably, the acid solution adopted in described acid solution process comprises hydrochloric acid soln, sulphuric acid soln or salpeter solution;
The mass concentration of described acid solution is 0.1% ~ 15%.
Preferably, the process of described electrochemical treatment is specially:
There is provided noble electrode, the substrate in the substrate be bonded together and target substrate and apply the voltage of 0.1V ~ 5V between described noble electrode, carry out the electrochemical treatment of 0.1h ~ 5h.
The invention provides a kind of transfer method of Graphene, first the medium that the substrate depositing Graphene is placed in containing oxidizing substance is processed, reduce the interface binding power between Graphene and substrate, thus Graphene is easily come off by substrate surface when making the later stage at the bottom of peeling liner, the integrity of Graphene can not be damaged, transfer to Graphene in target substrate without breakage, and Graphene defect is less.Experimental result of the present invention shows, in the embodiment of the present invention, Raman spectrum detection is carried out in the optional position transferring to the Graphene in target substrate, and the Raman spectrum consistent degree obtained is higher, and less at 1350 displacement place D peak intensities, illustrates that Graphene defect is very little.
Accompanying drawing explanation
Fig. 1 is the schema of Graphene transfer method in the embodiment of the present invention;
Fig. 2 transfers to Si-SiO in the embodiment of the present invention 1
2the picture of Graphene on matrix;
Fig. 3 transfers to Si-SiO in the embodiment of the present invention 1
2the Raman collection of illustrative plates of Graphene on matrix.
Embodiment
The invention provides a kind of transfer method of Graphene, comprise the following steps:
1) medium that the substrate depositing Graphene is placed in containing oxidizing substance is processed;
2) by described step 1) deposit the side of Graphene in substrate after process and target substrate bonds;
3) by described step 2) substrate desquamation in the sample that obtains, complete the transfer of Graphene.
First the medium that the substrate depositing Graphene is placed in containing oxidizing substance processes by method provided by the invention, reduce the interface binding power between Graphene and substrate, thus Graphene is easily come off by substrate surface when making the later stage at the bottom of peeling liner, the integrity of Graphene can not be damaged, transfer to Graphene in target substrate without breakage, and Graphene defect is less.
The medium that the substrate depositing Graphene is placed in containing oxidizing substance processes by the present invention.The method of the present invention to described deposition does not have special restriction, adopts the method for preparing graphene through chemical vapor deposition well known to those skilled in the art, at deposited on substrates Graphene.In the present invention, the preferable alloy substrate of described substrate, concrete, described metal substrate is preferably selected from one or more the alloy in copper, iron, nickel, carbon, cobalt, gold, platinum, aluminium, molybdenum, ruthenium, tantalum, titanium, tungsten, chromium, magnesium and manganese, is more preferably Copper Foil, aluminium foil or goldleaf.
The shape that the present invention deposits the substrate of Graphene to described and size do not have special restriction, and those skilled in the art can be cut into arbitrary shape and size as required, as cut out as 2cm × 2cm size.
The substrate depositing Graphene is placed in the medium containing oxidizing substance by the present invention, and the consumption of the present invention to described medium does not have special restriction, can deposit the substrate of Graphene described in submergence.In the present invention, described medium is liquid phase medium and/or gas phase media; In the present invention, described liquid phase medium preferably includes one or more in water, ethanol, acetic acid, benzene and acetone; Described gas phase media preferably includes one or more in water vapour, alcohol vapour, acetic acid steam, benzene vapour and acetone steam.The kind of the present invention to described water does not have special restriction, can be deionized water, can be tap water yet.
In the present invention, be dissolved with oxidizing substance in described medium, described oxidizing substance comprises one or more in gaseous oxygen voltinism material, solid oxygen voltinism material and liquid oxygen voltinism material.In the present invention, described gaseous oxygen voltinism material preferably includes one or more in oxygen, ozone, sulfurous gas, chlorine and hydrogenchloride; Described solid oxygen voltinism medium preferably includes one or more in potassium permanganate, Sodium Nitrite, clorox and sodium perchlorate; Described liquid oxygen voltinism material preferably include in hydrogen peroxide, phenol, toluene and acetaldehyde one or more.
In the present invention, described gaseous oxygen voltinism material and/or the liquid oxygen voltinism material most high-content in liquid phase medium is its saturation solubility in media as well.
In the present invention, the mass percent of described solid oxidated material in liquid phase medium is preferably 0.01% ~ 50%, is more preferably 0.1% ~ 10%, most preferably is 0.5% ~ 8%; In an embodiment of the present invention, concrete, when described solid oxygen voltinism material comprises potassium permanganate, the mass percent of described potassium permanganate in liquid phase medium is preferably 0.1% ~ 0.5%; When described solid-state liquid phase substance comprises Sodium Nitrite, the mass percent of described Sodium Nitrite in liquid phase medium is preferably 0.1% ~ 10%, is more preferably 0.5% ~ 8%; When described solid oxygen voltinism material comprises clorox, the mass percent of described clorox in liquid phase medium is preferably 0.1% ~ 2.0%, is more preferably 0.5% ~ 1.5%; When described solid oxygen voltinism material comprises sodium perchlorate, the mass percent of described sodium perchlorate in liquid phase medium is preferably 0.1% ~ 5.0%, is more preferably 0.5% ~ 3%.
In the present invention, described medium of working as is preferably gas phase media, when described oxidizing substance is preferably gaseous oxygen voltinism material, 0.01% ~ 50% is preferably at the mass percent of described gaseous oxygen voltinism material in described gas phase media, be more preferably 0.1% ~ 10%, most preferably be 0.5% ~ 8%.
The substrate depositing Graphene processes by the present invention in containing the medium of oxidizing substance, is preferably placed in by the substrate depositing Graphene described containing after the medium of oxidizing substance, leaves standstill and carry out oxide treatment.
In the present invention, when described medium is preferably liquid phase medium, described in deposit Graphene substrate described containing the liquid phase medium of oxidizing substance in the temperature that processes be preferably 0 DEG C ~ 100 DEG C, be more preferably 35 DEG C ~ 90 DEG C, most preferably be 40 DEG C ~ 80 DEG C.In the present invention, when described medium is preferably gas phase media, described in deposit Graphene substrate in the described boiling temperature being preferably greater than corresponding medium containing the treatment temp in the gas phase media of oxidizing substance.In the present invention, described in deposit Graphene substrate described containing the medium of oxidizing substance in time of processing be preferably 0.1h ~ 24h, be more preferably 2h ~ 15h, most preferably be 4h ~ 10h.
The substrate depositing Graphene described in completing described containing the oxide treatment in the medium of oxidizing substance after, the substrate after described oxide treatment is preferably taken out containing in the medium of oxidizing substance by described by the present invention; When described medium is preferably liquid phase medium, the substrate after described oxide treatment is by described containing after removal in the medium of oxidizing substance, and the present invention preferably removes the liquid phase medium on described process back substrate surface; Preferably the substrate after described process is hung in vacuum drying oven and carry out drying.In the present invention, the temperature of described drying is preferably 30 DEG C; The time of described drying is preferably 3min ~ 10min, is more preferably 5min ~ 7min.
After in the described medium containing oxidizing substance, oxide treatment completes, the side and target substrate that deposit Graphene in the substrate after the process obtained bond by the present invention.In the present invention, described target substrate can be conductor matrix, also can be semiconductor substrate, can also be insulator matrix; In the present invention, described conductor matrix preferably includes a kind of simple substance matrix in copper, iron, nickel, carbon, cobalt, gold, platinum, aluminium, molybdenum, ruthenium, tantalum, titanium, tungsten, chromium, magnesium, manganese or two or more alloy substrates; The material of described semiconductor substrate preferably includes germanium, silicon, gallium arsenide, phosphatization potassium, gan, gallium aluminum arsenide, gallium arsenic phosphide, tin arsenic, sulphur arsenic, Vanadium Pentoxide in FLAKES-Vanadium Pentoxide in FLAKES or boron nitride; The material of described insulating body preferably includes one or both of polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyvinyl alcohol (PVA), Polyurethane Thermoplastic Elastomer rubber (TPU), polystyrene (PS), ethylene-vinyl acetate copolymer (EVA), polydimethylsiloxane (PDMS) and polymethylmethacrylate (PMMA).The source of the present invention to described target substrate does not have special restriction, adopts the commercial goods of above-mentioned target substrate well known to those skilled in the art.
In the present invention, described bonding is preferably electrostatic bonding, colloid bonding, non-setting adhesive bonding or Van der Waals force bonding.The method of the present invention to described colloid bonding and non-setting adhesive bonding does not have special restriction, adopts the technical scheme that colloid well known to those skilled in the art bonds and non-setting adhesive bonds.In the present invention, when adopting electrostatic bonding to be bondd in the side of Graphene in substrate and target substrate, described target substrate is preferably electrostatic film, and described electrostatic bonding preferably specifically comprises:
The side of Graphene in substrate after process is adsorbed on electrostatic film, flattens through rubber roll.
In the present invention, the adsorptive power of described electrostatic film is preferably 2gf/25mm ~ 8gf/25mm, is more preferably 3gf/25mm ~ 7gf/25mm, most preferably is 4gf/25mm ~ 6gf/25mm.
In the present invention, described Van der Waals force bonding preferably specifically comprises: after smooth target substrate ultrasonic cleaning, bond with the side depositing Graphene in the substrate after described process; Again the sample obtained is flattened through rubber roll.The method of the present invention to described ultrasonic cleaning does not have special restriction, adopts the technical scheme of ultrasonic cleaning well known to those skilled in the art.
After completing the bonding of described process back substrate and target substrate, described metal substrate is peeled off by the present invention, and complete the transfer of Graphene, Graphene is transferred in target substrate by metal substrate.In the present invention, described stripping is preferably mechanically peel, acid solution process or electrochemical reaction.In the present invention, substrate can manually be torn by described mechanically peel.In the present invention, described acid solution process preferably specifically comprises:
The substrate be bonded together and target substrate are dipped in acid solution and process, substrate separates with Graphene.
In the present invention, described acid solution is preferably one or more in hydrochloric acid, sulfuric acid and nitric acid; The mass concentration of described acid solution is preferably 0.1% ~ 15%, is more preferably 0.5% ~ 13%, most preferably is 1% ~ 10%.The present invention preferably carries out described acid solution process at ambient temperature, and in the present invention, the time of described acid solution process is preferably 5h ~ 8h, is more preferably 6h ~ 7h.
In the present invention, described electrochemical reaction is preferably specially:
Noble electrode is provided;
Substrate in the substrate be bonded together and target substrate and apply the voltage of 0.1V ~ 5V between noble electrode, carries out the electrochemical treatment of 0.1h ~ 5h.
In the present invention, described noble electrode is preferably platinum wire electrode or Graphite Electrodes.The present invention, using the substrate in the substrate be bonded together and target substrate as electrode, applies voltage between described substrate and noble electrode, carries out electrochemical treatment, realizes the stripping of substrate.In the present invention, described voltage is preferably 0.1V ~ 5V, is more preferably 0.1V ~ 0.5V, most preferably is 0.2V ~ 0.4V; Describedly execute the alive time and be preferably 0.1h ~ 5h, be more preferably 0.5h ~ 3h, most preferably be 0.5h ~ 1h.
See the schematic flow sheet that Fig. 1, Fig. 1 are the Graphene transfer that the embodiment of the present invention adopts.As seen from Figure 1, embodiments of the invention adopt CVD at Grown Graphene; Oxide treatment is carried out by growing the medium having the substrate of Graphene to be placed in containing oxidizing substance; The side and target substrate that are attached with Graphene in substrate after described oxide treatment are bondd; At the bottom of last peeling liner, realize Graphene by substrate to the transfer in target substrate.
The invention provides a kind of transfer method of Graphene, comprise the following steps: 1) medium that the substrate depositing Graphene is placed in containing oxidizing substance is processed; 2) by described step 1) deposit the side of Graphene in substrate after process and target substrate bonds; 3) by described step 2) substrate desquamation in the sample that obtains, complete the transfer of Graphene.First the medium that the substrate depositing Graphene is placed in containing oxidizing substance processes by method provided by the invention, reduce the interface binding power between Graphene and substrate, thus Graphene is easily come off by substrate surface when making the later stage at the bottom of peeling liner, the integrity of Graphene can not be damaged, transfer to Graphene in target substrate without breakage, and Graphene defect is less.Experimental result of the present invention shows, in the embodiment of the present invention, Raman spectrum detection is carried out in the optional position transferring to the Graphene in target substrate, and the Raman spectrum consistent degree obtained is higher, and less at 1350 displacement place D peak intensities, illustrates that Graphene defect is very little.
And, adopt method provided by the invention to shift Graphene, impurity can not be introduced in Graphene, make the Graphene after shifting remain higher purity; And remaining substrate can also be recycled again, save resource.
In addition, method steps provided by the invention is few, simple to operate.
In order to further illustrate the present invention, being described in detail below in conjunction with the transfer method of embodiment to Graphene provided by the invention, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
1) the Copper Foil substrate depositing Graphene is put into deionized water, under temperature 40 DEG C of conditions (now the solubleness of oxygen in water is 6.4 mg/litre), heating 4h; Sample is taken out from water, drying treatment;
2) AB glue is mixed according to working instructions, get AB mixed solution and drop in PET film; By step 1) Graphene side is attached to PET film in the sample that obtains glue face flattens, be placed in vacuum drying oven 40 DEG C of dry 24h;
3) direct hand is by step 3) Copper Foil in the sample that obtains tears, and Graphene is transferred in PET film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 2
1) the Copper Foil substrate depositing Graphene is put into deionized water, under temperature 40 DEG C of conditions (now the solubleness of oxygen in water is 6.4 mg/litre), heating 4h; Sample is taken out from water, drying treatment;
2) AB glue is mixed according to corresponding proportion, get appropriate mixed solution and drop in PET film; By step 1) Graphene side is attached to PET film in the sample that obtains glue face flattens, be placed in vacuum drying oven 40 DEG C of dry 24h;
3) using 2) in sample as an electrode, graphite is as another electrode, and apply the voltage of 0.5V, being immersed in hydrochloric acid mass percent is 5h in the hydrochloric acid of 1%, and Copper Foil is separated with the PET being bonded with Graphene, and Graphene is transferred in PET film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 3
1) the Copper Foil substrate depositing Graphene is put into deionized water, under temperature 40 DEG C of conditions (now the solubleness of oxygen in water is 6.4 mg/litre), heating 4h; Sample is taken out from water, drying treatment;
2) voltage applying 20KV on PET makes it to bring electrostatic;
3) the Graphene face on substrate is fitted on the PET of above-mentioned static electrification, flattens through rubber roll;
4) direct hand is by step 3) Copper Foil in the sample that obtains tears, and Graphene is transferred in PET film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil;
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 4
1) will deposit in the Copper Foil substrate deionized water of Graphene, 50 DEG C (now the solubleness of oxygen in water is 5.4 mg/litre), heating 3h; Sample is taken out from water, drying treatment;
2) in step 1) Graphene side presses one deck to be adsorbed with adsorptive power in the sample that obtains to be 2gf/25mmPE electrostatic film, to flatten through rubber roll;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken on PE electrostatic film by Copper Foil;
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 5
1) the Copper Foil substrate depositing Graphene being placed on mass concentration is in the hydrogen peroxide of 0.01%, at 80 DEG C, and heating 20h; Sample is taken out from hydrogen peroxide, drying treatment;
2) in step 1) Graphene side to press one deck to be adsorbed with adsorptive power in the sample that obtains be 2gf/25mmPE electrostatic film;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged
Embodiment 6
1) the Copper Foil substrate depositing Graphene being placed on mass concentration is in the hydrogen peroxide of 0.1%, at 60 DEG C, and heating 10h; Sample is taken out from hydrogen peroxide, drying treatment;
2) in step 1) Graphene side to press one deck to be adsorbed with adsorptive power in the sample that obtains be 2gf/25mmPE electrostatic film;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged
Embodiment 7
1) the Copper Foil substrate depositing Graphene being placed on mass concentration is in the hydrogen peroxide of 10%, at 40 DEG C, and heating 5h; Sample is taken out from hydrogen peroxide, drying treatment;
2) in step 1) Graphene side to press one deck to be adsorbed with adsorptive power in the sample that obtains be 2gf/25mmPE electrostatic film;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged
Embodiment 8
1) the Copper Foil substrate depositing Graphene is placed on mass concentration be in the sodium perchlorate solution of 0.1% in, at 40 DEG C, heating 15h; Sample is taken out from solution, drying treatment;
2) in step 1) Graphene side to press one deck to be adsorbed with adsorptive power in the sample that obtains be 2gf/25mmPE electrostatic film;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged
Embodiment 9
1) the Copper Foil substrate depositing Graphene is placed on mass concentration be in the sodium perchlorate solution of 1% in, at 60 DEG C, heating 10h; Sample is taken out from solution, drying treatment;
2) in step 1) Graphene side to press one deck to be adsorbed with adsorptive power in the sample that obtains be 2gf/25mmPE electrostatic film;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged
Embodiment 10
1) the Copper Foil substrate depositing Graphene is placed on mass concentration be in the sodium perchlorate solution of 10% in, at 40 DEG C, heating 2h; Sample is taken out from solution, drying treatment;
2) AB glue is mixed according to corresponding proportion, get appropriate mixed solution and drop in PET film; By step 1) Graphene side is attached to PET film in the sample that obtains glue face flattens, be placed in vacuum drying oven 40 DEG C of dry 24h;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 11
1) the Copper Foil substrate depositing Graphene being placed on mass concentration is in the oxygenous water vapour of 0.1%, at 100 DEG C, and heating 2h; Sample is taken out from solution, drying treatment;
2) AB glue is mixed according to corresponding proportion, get appropriate mixed solution and drop in PET film; By step 1) Graphene side is attached to PET film in the sample that obtains glue face flattens, be placed in vacuum drying oven 40 DEG C of dry 24h;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 12
1) the Copper Foil substrate depositing Graphene being placed on mass concentration is in the oxygenous water vapour of 1%, at 100 DEG C, and heating 1h; Sample is taken out from solution, drying treatment;
2) AB glue is mixed according to corresponding proportion, get appropriate mixed solution and drop in PET film; By step 1) Graphene side is attached to PET film in the sample that obtains glue face flattens, be placed in vacuum drying oven 40 DEG C of dry 24h;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
Embodiment 13
1) the Copper Foil substrate depositing Graphene being placed on mass concentration is in the oxygenous water vapour of 10%, at 100 DEG C, and heating 0.5h; Sample is taken out from solution, drying treatment;
2) AB glue is mixed according to corresponding proportion, get appropriate mixed solution and drop in PET film; By step 1) Graphene side is attached to PET film in the sample that obtains glue face flattens, be placed in vacuum drying oven 40 DEG C of dry 24h;
3) manually by step 2) Copper Foil obtained in sample tears off, realizes the transfer of Graphene to PE electrostatic film.
The present invention is transferred to the Graphene macroscopically intact unbroken in PET film by Copper Foil.
The present invention carries out Raman (Raman) spectral detection by shifting the Graphene that obtains, can find out in the Raman spectrogram obtained, and be that the honeybee intensity at 1350 D peaks, place is very little in displacement, this illustrates that the defect shifting the Graphene obtained is very little; And the present invention carries out Raman spectrum detection to shifting different point on the Graphene that obtains at random, and result can both obtain more consistent Raman spectrogram, and after this also illustrates Graphene transfer, thing is damaged.
As seen from the above embodiment, first the medium that the substrate depositing Graphene is placed in containing oxidizing substance processes by method provided by the invention, reduce the interface binding power between Graphene and substrate, thus Graphene is easily come off by substrate surface when making the later stage at the bottom of peeling liner, the integrity of Graphene can not be damaged, transfer to Graphene in target substrate without breakage, and Graphene defect is less.Experimental result of the present invention shows, in the embodiment of the present invention, Raman spectrum detection is carried out in the optional position transferring to the Graphene in target substrate, and the Raman spectrum consistent degree obtained is higher, and less at 1350 displacement place D peak intensities, illustrates that Graphene defect is very little.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a transfer method for Graphene, comprises the following steps:
1) medium that the substrate depositing Graphene is placed in containing oxidizing substance is processed;
2) by described step 1) deposit the side of Graphene in substrate after process and target substrate bonds;
3) by described step 2) substrate desquamation in the sample that obtains, complete the transfer of Graphene; Described medium is liquid phase medium and/or gas phase media;
Described liquid phase medium comprises one or more in water, ethanol, acetic acid, benzene and acetone;
Described gas phase media comprises one or more in water vapour, alcohol vapour, acetic acid steam, benzene vapour and acetone steam; Described oxidizing substance comprises one or more in gaseous oxygen voltinism material, solid oxygen voltinism material and liquid oxygen voltinism material;
Described gaseous oxygen voltinism material comprises one or more in oxygen, ozone, sulfurous gas, chlorine and hydrogenchloride;
Described solid oxygen voltinism medium comprises one or more in potassium permanganate, Sodium Nitrite, clorox and sodium perchlorate;
Described liquid oxygen voltinism material comprise in hydrogen peroxide, phenol, toluene and acetaldehyde one or more; Described oxidizing substance mass percent is in media as well 0.01% ~ 50%.
2. transfer method according to claim 1, is characterized in that, described oxidizing substance
Mass percent is in media as well 0.1% ~ 10%.
3. transfer method according to claim 1, is characterized in that, described step 1) in process temperature be 0 DEG C ~ 100 DEG C.
4. transfer method according to claim 1, is characterized in that, described step 1) in process time be 0.1h ~ 24h.
5. transfer method according to claim 1, is characterized in that, described step 2) in be bonded as electrostatic bonding, colloid bonding or Van der Waals force bonding.
6. transfer method according to claim 1, is characterized in that, described step 3) be specially:
Adopt mechanically peel, acid solution process or electrochemical treatment, by described step 2) substrate desquamation in the sample that obtains, complete the transfer of Graphene.
7. transfer method according to claim 6, is characterized in that, the acid solution adopted in described acid solution process comprises hydrochloric acid soln, sulphuric acid soln or salpeter solution;
The mass concentration of described acid solution is 0.1% ~ 15%.
8. transfer method according to claim 6, is characterized in that, the process of described electrochemical treatment is specially:
Noble electrode is provided, be bonded together and substrate in target substrate and apply the voltage of 0.1V ~ 5V between described noble electrode, carry out the electrochemical treatment of 0.1h ~ 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410555097.2A CN104261402B (en) | 2014-10-17 | 2014-10-17 | A kind of transfer method of Graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410555097.2A CN104261402B (en) | 2014-10-17 | 2014-10-17 | A kind of transfer method of Graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104261402A CN104261402A (en) | 2015-01-07 |
| CN104261402B true CN104261402B (en) | 2016-03-02 |
Family
ID=52153032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410555097.2A Active CN104261402B (en) | 2014-10-17 | 2014-10-17 | A kind of transfer method of Graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104261402B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105000551A (en) * | 2015-07-08 | 2015-10-28 | 合肥工业大学 | Large-area graphene seamless transferring method |
| CN107098339A (en) * | 2016-02-19 | 2017-08-29 | 常州国成新材料科技有限公司 | A kind of method for shifting graphene |
| CN106340598A (en) * | 2016-11-10 | 2017-01-18 | 过冬 | Preparation method of OLED composite electrode material |
| CN106676472A (en) * | 2016-12-16 | 2017-05-17 | 桂林电子科技大学 | Method for transferring ITO thin film |
| CN106986334A (en) * | 2017-04-28 | 2017-07-28 | 宁波柔碳电子科技有限公司 | The transfer method and system of a kind of graphene film |
| CN109133174B (en) * | 2018-08-21 | 2021-03-16 | 中国地质大学（北京） | Two-dimensional material transfer method, two-dimensional material and application thereof |
| CN110562968A (en) * | 2019-10-22 | 2019-12-13 | 杭州联芳科技有限公司 | liquid-phase substrate graphene precipitation separation method |
| CN114394589B (en) * | 2022-02-15 | 2023-06-30 | 浙江大学 | Method for transferring strain graphene on silicon substrate containing oxide layer |
| CN114823975A (en) * | 2022-04-20 | 2022-07-29 | 深圳市新旗滨科技有限公司 | Flexible thin-film solar cell and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072976B (en) * | 2012-12-28 | 2015-01-14 | 同济大学 | Transfer method of graphene or oxidized graphene thin film |
-
2014
- 2014-10-17 CN CN201410555097.2A patent/CN104261402B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104261402A (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104261402B (en) | A kind of transfer method of Graphene | |
| US9840024B2 (en) | Method for the fabrication and transfer of graphene | |
| KR101829095B1 (en) | Methods of nondestructively delaminating graphene from a metal substrate | |
| CN103922327B (en) | A kind of big area can't harm the method for transfer graphene film | |
| EP2690198B1 (en) | Apparatus and graphene device manufacturing method using the apparatus | |
| CN102719877A (en) | Low-cost lossless transfer method of graphene | |
| CN102719803A (en) | Method for preparing and transferring graphene transparent film | |
| CN103224231A (en) | Transfer method of graphite film | |
| US20140238873A1 (en) | Modified bubbling transfer method for graphene delamination | |
| CN107098339A (en) | A kind of method for shifting graphene | |
| TW201116606A (en) | Method and an apparatus for transferring carbonaceous material layer | |
| CN104876211A (en) | Method for preparing graphene by rotationally shearing in electric field environment | |
| CN103280541B (en) | A kind of process preparing flexible device and flexible substrate on CVD Graphene | |
| CN103641108B (en) | A kind of N-methyl-N-morpholine oxide prepares the method for graphene oxide | |
| CN102180463A (en) | Method for reducing sheet resistance of graphene thin film | |
| CN104860307A (en) | Nondestructive transferring method of graphene film | |
| CN107867681A (en) | A kind of method of electrochemical gas bubbling transfer large-area graphene | |
| CN104108704A (en) | Graphene transfer method | |
| KR20110065971A (en) | Method of fabricating graphene oxide | |
| CN104157560A (en) | Preparation method of graphene electrode | |
| CN103361068B (en) | A kind of Metal foil substrate graphene etching liquid and lithographic method thereof | |
| CN204558500U (en) | Flexible hetero-junction thin-film solar cell | |
| CN104890312A (en) | Method of protecting graphene layer on substrate and graphene composite | |
| CN107761070A (en) | A kind of method for improving electrochemical gas intercalation and peeling off transfer graphene speed | |
| CN107791614A (en) | The preparation of graphene composite film and its processing technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181126 Address after: 315201 No. 1818, Zhong Guan Xi Road, Zhuang City Street, Zhenhai District, Ningbo, Zhejiang. Patentee after: Ningbo soft carbon Electronic Technology Co., Ltd. Address before: 315201 No. 1219 Zhongguan West Road, Zhenhai District, Ningbo City, Zhejiang Province Patentee before: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien |
|
| TR01 | Transfer of patent right |