Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of cost lower, simple to operate, and can access the transfer method of high-quality graphene film.
The transfer method of graphene film of the present invention is for being media with the electrostatic protection film, through release electrostatic reasonably, realizes the transfer of Graphene between different substrates.
The present invention realizes through following experimental program:
A kind of is the method that media shifts graphene film with the electrostatic protection film; Said method is to utilize the electrostatic adsorption of electrostatic protection film to fit to comprise the Graphene of growth substrates; Then substrate is removed, obtained single-layer graphene/electrostatic protection film combination, at last single-layer graphene/electrostatic protection film combination is fitted on the target substrate; Release electrostatic is removed the electrostatic protection film, obtains the single-layer graphene film;
Said method also can be after obtaining single-layer graphene/electrostatic protection film combination; Replace the electrostatic protection film with single-layer graphene/electrostatic protection film combination, on the new Graphene that comprises substrate, repeat following two steps n-1 time successively: applying Graphene/electrostatic protection film, removal substrate; Thereby prepare n layer graphene film, the value of said n is >=2 integer, for example 2,3,4,5,6 etc.
The method that for example prepares 3 layer graphene films is: utilize the electrostatic adsorption of electrostatic protection film to fit and comprise the Graphene of growth substrates, then substrate is removed, obtain Graphene/electrostatic protection film combination; Then the Graphene that obtains/electrostatic protection film combination being fitted, another comprises the Graphene of growth substrates, once more substrate is removed, and obtains 2 layer graphenes/electrostatic protection film combination; 2 layer graphenes that will obtain then/electrostatic protection film combination is fitted, and another comprises the Graphene of growth substrates, once more substrate is removed, and obtains 3 layer graphenes/electrostatic protection film combination; With after 3 layer graphenes/electrostatic protection film combination fits on the target substrate, behind the removal electrostatic protection film, obtain 3 layer graphene films at last.
The electrostatic protection film has the Electrostatic Absorption ability, can paste smooth body surface, and chemical property is stable, mechanical strength is high, therefore can be used as the transfer medium that " etched the matrix method " shifts Graphene.
The present invention utilizes the Electrostatic Absorption ability of electrostatic protection film, with the electrostatic protection film with firm the sticking in Graphene surface that comprises growth substrates; And after removing described substrate, the Electrostatic Absorption ability of having adsorbed the electrostatic protection film of Graphene does not change, and can continue to fit fully with the Graphene surface that comprises substrate, thereby obtain the combination of multi-layer graphene film/electrostatic protection film.And the process of removal substrate according to the invention does not have particular determination, anyly can the method that growth substrates is removed all be can be used for the present invention.
Preferably, the present invention adopts solvent etching that substrate etching is removed, and transfers on the target substrate after substrate has been corroded; Utilize the method that can reduce Electrostatic Absorption power at last, reach Graphene is transferred to multiple suprabasil purpose.Reduction Electrostatic Absorption power of the present invention purpose be that release electrostatic is removed the static film; Method for reducing Electrostatic Absorption power does not have particular determination; As long as can reach the purpose that release electrostatic is removed the static film; The method of the reduction Electrostatic Absorption that those skilled in the art have the ability to know all can be used for the present invention, removes the method for electrostatic protection film like release electrostatics such as baking, sub-cooled.
That the method that electrostatic protection film provided by the invention shifts Graphene has is easy to use, simple to operate, noresidue, can reuse, save characteristics such as cost.Simultaneously, the method that electrostatic protection film provided by the present invention shifts Graphene can be used for volume to volume (roll-to-roll) technology transfer Graphene, helps the large-scale production of graphene film.Described volume to volume technology is the state of the art, and those skilled in the art have the ability to obtain relevant knowledge.
Particularly, the present invention realizes through following technical scheme, and a kind of is that the method that media shifts graphene film comprises the steps: with the electrostatic protection film
(1) the electrostatic protection film is fitted in the Graphene surface that comprises growth substrates;
(2) remove the described substrate of step (1), obtain single-layer graphene/electrostatic protection film combination;
(3) Graphene/electrostatic protection film combination is fitted on the target substrate, release electrostatic is removed the electrostatic protection film, obtains graphene film;
Wherein, the said Graphene of step (3)/electrostatic protection film is the described single-layer graphene of step (2)/electrostatic protection film.
The present invention utilizes the Electrostatic Absorption ability of electrostatic protection film, with the electrostatic protection film with firm the sticking in Graphene surface that comprises growth substrates.After removing described substrate, the Electrostatic Absorption ability of having adsorbed the electrostatic protection film of Graphene does not change, and can continue to fit fully with the Graphene surface that comprises growth substrates.
Preferably, the optional step (2 ') of carrying out in step (2) back:
The single-layer graphene that (2 ') obtains step (2)/electrostatic protection film combination replaces the described electrostatic protection film of step (1), and repeating step (1) ~ step (2) n-1 time prepares n layer graphene/electrostatic protection film combination; The value of said n is >=2 integer;
Wherein, after step (2), carry out step when (2 '), the said Graphene of step (3)/electrostatic protection film is the described multi-layer graphene of step (2 ')/electrostatic protection film; Said graphene film is the multi-layer graphene film.
The electrostatic protection film is a kind of tack film that those skilled in the art have the ability to know; Material according to the electrostatic protection film is different; It includes but not limited to OPP electrostatic protection film, PE (polyethylene) electrostatic protection film, PET (PETG) electrostatic protection film, PVC (polyvinyl chloride) electrostatic protection film and PP (polypropylene) electrostatic protection film etc.; The present invention does not do special qualification for the material of electrostatic protection film, anyly can all can be used for the present invention through the electrostatic protection film that prior art or new technology obtain.
Preferably; Electrostatic protection film according to the invention is selected from any one in PE (polyethylene) electrostatic protection film, PET (PETG) electrostatic protection film, PVC (polyvinyl chloride) electrostatic protection film and PP (polypropylene) the electrostatic protection film, any one in preferred PET electrostatic protection film, the PVC electrostatic protection film.
The present invention is unqualified to the target substrate that graphene film shifts, and art technology can be selected according to oneself needs and actual conditions arbitrarily.Preferably, target substrate according to the invention is selected from any one among glass, PET, silicon chip, PI (polyimides), PVC, PE, PP, the PS (polystyrene), any one in preferred PP, PE, the silicon chip.
The described Graphene that comprises substrate of step of the present invention (1) is that prior art can prepare, and the preparation method is well known to those skilled in the art, typical case but non-limiting instance has vapour deposition process etc.Step (1) is described to be fitted in the Graphene surface that comprises substrate with the electrostatic protection film and to mean the one side that the electrostatic protection film is fitted in the non-substrate of graphene film; Obtain the combination of electrostatic protection film/Graphene/substrate after applying is accomplished, its structure is followed successively by substrate, Graphene, electrostatic protection film from bottom to top.
The middle method of removing growth substrates of step of the present invention (2) can adopt but be not limited only to the wet etching method.Said wet etching method adopts the growth substrates in electrostatic protection film/Graphene/substrate that etching liquid obtains step (1) to remove, and the selection of etching liquid also should be relevant with the material of substrate.And etching should be those skilled in the art's skills on top of, comprises which kind of etching liquid is which kind of material select, typical case but nonrestrictive etching liquid example has copper chloride, iron chloride, ferric nitrate, nitric acid, hydrogen peroxide-sulfuric acid, ammonia alkali, persulfate etc.The selection of concrete etching liquid and the selection of etch step, those skilled in the art can select according to actual conditions.
Preferably, the said etching liquid of step of the present invention (2) is selected from iron chloride (FeCl
3), ferric nitrate (Fe (NO
3)
3), nitric acid (HNO
3), ammonium persulfate ((NH
4)
2S
2O
8) and potassium peroxydisulfate (K
2S
2O
8) in any a kind or the combination more than at least 2 kinds, said combination is FeCl for example
3/ (NH
4)
2S
2O
8, K
2S
2O
8/ HNO
3, K
2S
2O
8/ (NH
4)
2S
2O
8, HNO
3/ FeCl
3/ HNO
3Deng.
It is technology well-known to those skilled in the art that the said Graphene of step (3)/electrostatic protection film is fitted on the target substrate, and typical case but non-limiting instance have and Graphene/electrostatic protection film combination be transferred on the target substrate baking.Those skilled in the art should understand; Graphene/electrostatic protection film is fitted in the step on the target substrate; The graphene layer of Graphene/electrostatic protection film and target substrate are fitted, and the structure after promptly fitting is target substrate, multilayer (or individual layer) graphene film and electrostatic protection film from bottom to top successively.
Graphene/electrostatic protection film and target substrate need release electrostatic diaphragm static at the interface after fitting, and reduce the electrostatic force between diaphragm and the Graphene, could diaphragm be removed, and obtain the graphene film that needs then.Preferably, the method for the said release electrostatic of step (3) is any one in baking, the sub-cooled.
Preferably; The temperature of said baking is 40 ~ 200 ℃, for example 42 ~ 188 ℃, 51 ~ 173 ℃, 66 ~ 141 ℃, 48 ℃, 89 ℃, 129 ℃, 145 ℃, 160 ℃, 183 ℃, 195 ℃ etc., and preferred 50 ~ 180 ℃; Further preferred 70 ~ 150 ℃, preferred especially 100 ~ 120 ℃.
Preferably; The temperature of said cooling is-210 ~ 0 ℃; For example-210~-5 ℃ ,-200~-10 ℃ ,-164 ~-23 ℃ ,-2 ℃ ,-22 ℃ ,-50 ℃ ,-80 ℃ ,-111 ℃ ,-135 ℃ ,-160 ℃ ,-193 ℃ etc.; Preferably-200 ~-5 ℃, further preferred-160 ~-20 ℃, preferred-100 ~-50 ℃ especially.
Electrostatic protection film provided by the present invention shifts in the method for Graphene, and step (1) and step (3) all relate to " applying " technology.Because the electrostatic protection film itself has tack, the requirement of attaching process does not promptly produce bubble, and if any bubble, the physicochemical property of graphene film especially electric property can receive very big influence.Therefore, can be with the graphene film good fit at the electrostatic protection film, the attaching process method of graphene film good fit on target substrate all be can be used for the present invention.Preferably, step (1) and the described applying method of step (3) they are artificial the stickup, any one during the machine overlay film is pasted, and preferred machine overlay film is pasted.It is equipment well known to those skilled in the art equally that machine pastes the described machine of film, typical case but non-limiting instance has electrostatic protection film make-up machine, laminating machine etc.
Preferably; The overlay film speed that the said machine overlay film of step of the present invention (3) is pasted is 0 ~ 2000mm/min; For example 1 ~ 2000mm/min, 5 ~ 1980mm/min, 150 ~ 2000mm/min, 11mm/min, 80mm/min, 280mm/min, 778mm/min, 1635mm/min, 1880mm/min, 1973mm/min etc.; Preferred 10 ~ 180mm/min, further preferred 20 ~ 150mm/min, preferred especially 30 ~ 140mm/min.
Preferably; The overlay film temperature that the said machine overlay film of step of the present invention (3) is pasted is 0 ~ 200 ℃; For example 1-199 ℃, 18-187 ℃, 50-150 ℃, 2 ℃, 13 ℃, 45 ℃, 89 ℃, 110 ℃, 165 ℃, 189 ℃, 197 ℃ etc.; Preferred 3 ~ 198 ℃, further preferred 20 ~ 80 ℃, preferred especially 40 ~ 70 ℃.
As optimal technical scheme, according to the invention is that the method that media shifts graphene film comprises the steps: with the electrostatic protection film
(1) the electrostatic protection film is fitted in the graphene film surface that comprises growth substrates;
(2) remove the described growth substrates of step (1), obtain single-layer graphene/electrostatic protection film combination;
The single-layer graphene that (2 ') obtains step (2)/electrostatic protection film combination replaces the described electrostatic protection film of step (1), and repeating step (1) ~ step (2) prepares double-layer graphite alkene/electrostatic protection film combination;
(3) Graphene/electrostatic protection film combination is fitted on the target substrate, release electrostatic is removed the electrostatic protection film, obtains graphene film;
Wherein, the said Graphene of step (3)/electrostatic protection film is the described single-layer graphene of step (2)/electrostatic protection film; Said graphene film is a double-layer graphite alkene film.
Those skilled in the art should understand, and the step of preparation single-layer graphene film is step (1), (2), (3), promptly only carry out electrostatic protection film and the applying that comprises the graphene film of growth substrates; And the step of preparation multi-layer graphene film is to carry out step (1), (2), (2 '), (3), promptly carries out repeatedly electrostatic protection film (or electrostatic protection film/Graphene combination) and comprises the applying of the graphene film of growth substrates.And described " repeatedly " can be selected according to actual conditions (like the number of plies of graphene film) for those skilled in the art voluntarily.
The method that electrostatic protection film of the present invention shifts Graphene is: the electrostatic absorption principle that utilizes electrostatic protection film 1; Electrostatic protection film 1 and the Graphene that comprises substrate 32 are fitted, and (structure is as shown in Figure 2; Fig. 2 is the structural representation of the combination of the said electrostatic protection film/Graphene of step of the present invention (1)/substrate); After this substrate 3 is carried out etching; The electrostatic protection film 1 that has adsorbed Graphene 2 is had the substrate attaching of Graphene again with superficial growth, repeat etch step, electrostatic protection film and the target substrate that will adsorb individual layer, Graphene two-layer or more multilayer are at last fitted; Remove the electrostatic protection film through methods such as baking, sub-cooled then, realized utilizing the electrostatic protection film to shift the purpose of multi-layer graphene.Fig. 1 is the process flow diagram that electrostatic protection film shown in the present shifts Graphene.
Two of the object of the invention provides a kind of graphene film, and said graphene film is prepared by method of the present invention.
Preferably, the number of plies of the graphene film that the method for the invention prepares >=1, for example 1,2,3,4,5,8,9 etc., preferred >=2, further preferred 2 ~ 5.
Preferably, when the number of plies of graphene film was 2, the square resistance of said graphene film was 301.7 ~ 498.1 Ω/.
Three of the object of the invention provides a kind of purposes of graphene film according to the invention; Said graphene film is used for energy and stores active material; Be preferred for Chu Qing, lithium ion battery, ultracapacitor or fuel cell, and nanometer electronic device, high-frequency circuit, photon sensor, the order-checking of gene electronics and minimizing noise.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention overcome the employing organic gel shift damaged, not easy to operate easily in the Graphene process, shortcomings such as residue, easy pollution are arranged, have easy to operate, technology is simple, cost is low, no cull, characteristics such as can reuse.
(2) method provided by the invention can be used for volume to volume technology transfer Graphene, and technology is simple, helps the large-scale production of graphene film.
(3) noresidue behind the removal electrostatic protection film does not have any pollution to Graphene, can not influence the transport performance of carrier.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
(1) utilizes Copper Foil to prepare graphene film through vapour deposition process, have the Copper Foil of Graphene to be clipped between two blocks of glass, apply certain power and make that the Copper Foil film surface is smooth, fold is few long as substrate; There is the Copper Foil of Graphene to fit fully with long PP electrostatic protection film through laminating machine, overlay film speed 10mm/min, the overlay film temperature is a room temperature;
(2) have the combination of the Copper Foil of Graphene to put into the ammonium persulfate solution etching electrostatic protection film/length, one of electrostatic protection film faces up, and one of Copper Foil faces down; Behind the 10min, adopt the surface of deionized water and ethanol cleaning Copper Foil, same method, twice of continuous wash; Etching 3h, Copper Foil is removed fully; Then Graphene/electrostatic protection film is taken out from ammonium persulfate solution,, dry under the room temperature with the surface of deionized water and alcohol flushing Graphene/electrostatic protection film;
(2 '), the operation of repeating step (1) ~ (2) formed double-layer graphite alkene/electrostatic protection film combination with the electrostatic protection film described in Graphene/electrostatic protection film combination step of replacing (1);
(3) utilize laminating machine that double-layer graphite alkene/electrostatic protection film combination and PET are fitted fully, the overlay film rotating speed is 10mm/min, and the overlay film temperature is 30 ℃, and the electrostatic protection film is removed in 40 ℃ of bakings then, obtains double-layer graphite alkene film.
Performance test:
The square resistance of resultant double-layer graphite alkene film is 401.6 Ω/.
Embodiment 2:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
(1) prepare the graphene film that Copper Foil is a substrate through vapour deposition process, have the Copper Foil of Graphene to make the Copper Foil film very smooth through the laminating machine roll extrusion with long, overlay film speed is 200mm/min; Adopt film coating technique, PET electrostatic protection film is fitted to length to be had on the Graphene Copper Foil; Overlay film speed is 200mm/min, and the overlay film temperature is a room temperature;
(2) there is the combination of the Copper Foil of Graphene to put into the ferric chloride solution etching with long the electrostatic protection film, behind the 10min, adopts the surface of deionized water and washed with methanol Copper Foil, same method, twice of continuous wash; Etching 3h, Copper Foil is removed fully; Then Graphene/electrostatic protection film is taken out from ferric chloride solution, with the surface of deionized water and washed with methanol Graphene/electrostatic protection film, 40 ℃ of oven dry;
(2 '), the operation of repeating step (1) ~ (2) formed double-layer graphite alkene/electrostatic protection film combination with the electrostatic protection film described in Graphene/electrostatic protection film combination step of replacing (1);
(3) double-layer graphite alkene/electrostatic protection film is attached on the substrate of glass fully, under 100 ℃ baking condition, removes the electrostatic protection film, obtain double-layer graphite alkene film.
Performance test:
The square resistance of resultant double-layer graphite alkene film is 301.7 Ω/.
Embodiment 3:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
(1) prepare the graphene film that nickel foil is a substrate through vapour deposition process, have the Copper Foil of Graphene to make the nickel foil film very smooth through the laminating machine roll extrusion with long, overlay film speed is 1000mm/min; Adopt film coating technique, PVC electrostatic protection film is fitted to length to be had on the Graphene nickel foil; Wherein, overlay film speed is 1000mm/min;
(2) the iron nitrate solution etching that has the combination of the nickel foil of Graphene to put into electrostatic protection film and length; Behind the 10min, adopt the surface of deionized water and washed with methanol nickel foil, same method, twice of continuous wash; Etching 3h, nickel foil is removed fully; Then Graphene/electrostatic protection film is taken out from ferric chloride solution, with the surface of deionized water and washed with methanol Graphene/electrostatic protection film, 60 ℃ of oven dry;
(2 '), the operation of repeating step (1) ~ (2) formed double-layer graphite alkene/electrostatic protection film combination with the electrostatic protection film described in Graphene/electrostatic protection film combination step of replacing (1);
(3) on being attached to double-layer graphite alkene/electrostatic protection film at the bottom of the silicon wafer-based fully at last, under 150 ℃ baking condition, remove the electrostatic protection film, obtain double-layer graphite alkene film.
Performance test:
The square resistance of resultant double-layer graphite alkene film is 332.5 Ω/.
Embodiment 4:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
Step (1)-(2 ') is with identical among the embodiment 2;
(3) utilize laminating machine that double-layer graphite alkene/electrostatic protection film and PI are fitted fully, under-210 ℃ condition, remove the electrostatic protection film, obtain double-layer graphite alkene film.
Performance test:
The square resistance of resultant double-layer graphite alkene film is 498.1 Ω/.
Embodiment 5:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
Step (1)-(2 ') is with identical among the embodiment 2.
(3) utilize laminating machine that double-layer graphite alkene/electrostatic protection film and PI are fitted fully, under 0 ℃ condition, remove the electrostatic protection film.
The square resistance of resultant double-layer graphite alkene is 442.9 Ω/.
Embodiment 6:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
Step (1)-(2) are with identical among the embodiment 2.
The operation of (2 ') repeating step (1) and (2) 2 times forms three layer graphenes/electrostatic protection film combination;
(3) three layer graphenes/electrostatic protection film is attached on the substrate of glass fully, under-196 ℃ condition, removes the electrostatic protection film.
Performance test:
The square resistance of resultant three layer graphene films is 208.3 Ω/.
Embodiment 7:
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
Step (1)-(2) are with identical among the embodiment 2.
The operation of (2 ') repeating step (1) and (2) 5 times forms six layer graphenes/electrostatic protection film combination;
(3) six layer graphenes/electrostatic protection film is attached on the substrate of glass fully, under-123 ℃ condition, removes the electrostatic protection film.
Performance test:
The square resistance of resultant six layer graphene films is 60.5 Ω/.
Embodiment 8
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
Step (1)-(2) are with identical among the embodiment 2, but the overlay film speed of step (1) is 1mm/min, and the overlay film temperature is 200 ℃.
The operation of (2 ') repeating step (1) and (2) 2 times forms three layer graphenes/electrostatic protection film combination;
(3) six layer graphenes/electrostatic protection film is attached on the substrate of glass fully, overlay film speed is 1mm/min, and the overlay film temperature is 200 ℃; Under 200 ℃ baking condition, remove the electrostatic protection film, obtain three layer graphene films.
Performance test:
The square resistance of resultant three layer graphene films is 130.5 Ω/.
Embodiment 9
A kind of method that adopts the electrostatic protection film to shift multi-layer graphene may further comprise the steps:
Step (1)-(2) are with identical among the embodiment 2, but the overlay film speed of step (1) is 2000mm/min, and the overlay film temperature is 0 ℃.
The operation of (2 ') repeating step (1) and (2) 5 times forms six layer graphenes/electrostatic protection film combination;
(3) six layer graphenes/electrostatic protection film is attached on the substrate of glass fully, overlay film speed is 2000mm/min,, the overlay film temperature is 0 ℃; Under-210 ℃ condition, remove the electrostatic protection film., obtain six layer graphene films.
Performance test:
The square resistance of resultant six layer graphene films is 55.2 Ω/.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.