CN107867683A - A kind of transfer method of large-area high-quality graphene - Google Patents
A kind of transfer method of large-area high-quality graphene Download PDFInfo
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- CN107867683A CN107867683A CN201710982373.7A CN201710982373A CN107867683A CN 107867683 A CN107867683 A CN 107867683A CN 201710982373 A CN201710982373 A CN 201710982373A CN 107867683 A CN107867683 A CN 107867683A
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Abstract
The invention discloses a kind of transfer method of large-area high-quality graphene, belong to materials science field.The transfer method comprises the following steps：By graphene/Cu flattenings；The PMMA slurries on even application on a graphene/Cu surface；PMMA graphene/Cu heating will be sprayed, obtained PMMA/ graphenes/Cu；Cu is etched, obtains PMMA/ graphenes；PMMA/ graphenes are cleaned, then clean PMMA/ graphenes are tiled to target substrate, obtain PMMA/ graphenes/target substrate；Normal heating, logical nitrogen and hyperbaric heating are carried out to PMMA/ graphenes/target substrate；With DUV irradiation PMMA/ graphenes/target substrate；PMMA is removed, by graphene/target substrate soaking and washing, nitrogen drying.Graphene corrugationless that present invention transfer obtains, without breakage, realize graphene large area, high quality transfer.
Description
Technical field
The present invention relates to materials science field, and in particular to a kind of transfer method of large-area high-quality graphene.
Background technology
Since graphene in 2004 is found, the research of graphene have received the great attention of countries in the world scientist.
The two-dimensional material that graphene is formed by the carbon atom Close stack of individual layer, there is unique Electronic Performance, can be widely applied to
Prescribed electrode, field-effect transistor, sensor etc., receive the extreme concern of industrial circle.
Controllable preparation high quality, large-area high-quality individual layer, single crystal graphene are the trend of graphene synthesis.Graphene
Main preparation methods have mechanical stripping method, chemical stripping method, SiC epitaxial growth methods, chemical vapor deposition (CVD) method etc., wherein,
CVD has unique advantage in terms of the controllable graphene of large-area high-quality, high quality, the number of plies is prepared.Also, with Cu
The large-area high-quality single-layer graphene synthetic method of most prospect so far is had developed into for the CVD of matrix.
However, the graphene for preparing high quality is the first step of graphene application, to make graphene in application field
It has breakthrough, the transfer techniques of graphene are indispensable process meanses.Because prepare graphene device (electrically conducting transparent
Film, field-effect transistor etc.), it is necessary to transfer them to (such as SiO in corresponding target substrate2, PET etc.), thus shift
The good and bad final performance that will influence device of the graphene arrived, therefore, the development prospect of graphene and the development of its transfer techniques
It is inseparable.But the development of the transfer techniques of graphene is also unsatisfactory at present：In transfer process, graphene is thin
Film easily produces fold, easily damaged bad, graphenic surface has polymer residue etc., and this just limits graphite to a certain extent
The application of alkene and development.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of transfer method of large-area high-quality graphene, this hair
It is bright shift obtain graphene corrugationless, without breakage, realize graphene large area, high quality transfer.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of transfer method of large-area high-quality graphene, comprises the following steps:
(1) between the graphene being grown on copper foil being clipped in into the smooth glass of two panels, roll unit is crossed, makes graphene/Cu
Flattening；
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with certain speed, and in transmit process
PMMA slurries on even application on a graphene/Cu surface；
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, heating-up temperature reaches and (be higher than) PMMA glass
Glass transition temperature, 15-30min is heated, obtains PMMA/ graphenes/Cu；
(4) by the PMMA/ graphenes/Cu face-down contact etching liquid for not spraying PMMA, Cu is etched, obtains PMMA/
Graphene；
(5) the PMMA/ graphenes etched are transferred in cleaning fluid, slowly decline cleaning fluid liquid level, obtain clean
PMMA/ graphenes, then clean PMMA/ graphenes are tiled to target substrate, obtain PMMA/ graphenes/target substrate；
(6) after PMMA/ graphenes/target substrate is dried, it is put into hyperbaric heating case, first normal heating, then passes to
Nitrogen, then hyperbaric heating, remove the micro-bubble between graphene and target substrate；
(7) PMMA/ graphenes/target substrate is irradiated with DUV, irradiation time 1-3h, cracks PMMA, be easy to
PMMA is removed in next step；
(8) the PMMA/ graphenes/target substrate being irradiated by deep UV is fixed on into the PMMA equipped with acetone to remove
Above acetone in device, and the surface for being coated with PMMA is down, heating, produces acetone steam, is dissolved by acetone steam
PMMA；Finally, graphene/target substrate is separately immersed in absolute ethyl alcohol and deionized water, nitrogen drying, that is, shifted
Large-area high-quality, the graphene film of high quality afterwards.
Preferably, described rolling speed is 2-5cm/min, transfer rate 2-10cm/s.
Preferably, PMMA contents are 1%-3% (w/w) in the PMMA slurries described in step (2), and solvent is ethyl acetate,
Spraying rate is 5-10mL/s.
Preferably, step (4) described etching liquid is 10-12% (w/v) ammonium persulfate aqueous solution, and the etch period is
25-35min。
Preferably, step (5) it is described transfer be specially first by the smooth transfer blade in clean, surface be fixed on an etching,
In cleaning device, will etch, the etching liquid in cleaning device is slowly released, to reduce liquid level, make the smooth patches of graphene/PMMA
On transfer blade, the graphene/PMMA being affixed on transfer blade is taken out；Deionized water is put into toward the etching, in cleaning device again,
The slow oblique cuttings of graphene/PMMA being affixed on transfer blade are entered in deionized water, 60min is soaked, cleans up, obtain clean
Graphene/PMMA.
Preferably, step (5) is described tiles clean graphene/PMMA to being specially to consolidate smooth in target substrate
The target substrate being scheduled on transfer blade is fixed in the cleaning device, opens outlet valve, slowly releases deionized water, reduces liquid
Face, graphene/PMMA is set entirely to be attached in target substrate, room temperature is dried, that is, obtains PMMA/ graphenes/target substrate.
Preferably, the target substrate is polyethylene terephtalate, PEN PEN, gathered
One kind in polyimide PI, glass, silicon chip.
Preferably, the etching, cleaning device include device body, located at intrinsic first gim peg of described device and
The tapping valve external located at described device sheet.
Preferably, step (6) described normal heating heats 10-30min at being specially prior to 40-70 DEG C, is warming up to 100 DEG C
Afterwards, 10-30min is heated at 100 DEG C；The hyperbaric heating is specially 200-500KPa prior to pressure, temperature is 100 DEG C
Lower hyperbaric heating 10-20min, the hyperbaric heating 15-30min at pressure is 200-500KPa, temperature is 120-150 DEG C.
Preferably, step (8) the PMMA removal devices equipped with acetone include device case, described device housing it is interior
Bottom is provided with to heat the heater of acetone, is additionally provided with the relative inner wall of described device housing to described in fixation
Second gim peg of PMMA/ graphenes/target substrate.
In summary, by adopting the above-described technical solution, beneficial effects of the present invention are：
The steps such as the present invention is by flattening, etching, cleaning, hyperbaric heating and DUV irradiate, make graphene and target
Substrate is fully bonded, and PMMA is fully removed totally, finally makes the graphene resistance of transfer smaller and uniform, corrugationless,
Without breakage, graphene large area, high quality transfer are realized.
Brief description of the drawings
Fig. 1 is etching, the structural representation of cleaning device in the embodiment of the present invention 1；
Fig. 2 is the structural representation of PMMA removal devices in the embodiment of the present invention 1；
Fig. 3 is the aisle resistance statistical result histogram for the graphene that the embodiment of the present invention 1 obtains.
In figure, 1- device bodies, the gim pegs of 2- first, 3- tapping valves, 4- transfer blades, 5- etching liquids or cleaning fluid, 6- stones
Black alkene/PMMA, 7- device cases, 8- acetone heaters, the gim pegs of 9- second, 10-PMMA/ graphenes/PET, 11- acetone steam
Vapour.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein " and/or " include one or more phases
The arbitrary and all combination of the Listed Items of pass.
Transfer blade as described below is glass plate.
Embodiment 1
A kind of transfer method of large-area high-quality graphene, comprises the following steps：
(1) using Cu as growth substrate, graphene is prepared with chemical deposition.Cut the 50cm*50cm stone grown
Black alkene/Cu, graphene/Cu is laid on glass clean, that surface is smooth, and graphite is clamped with another block of identical glass
Alkene/Cu.Rolling group is crossed, the speed of rolling is 5cm/min, makes graphene/Cu flattenings.
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with 2cm/s speed, while on conveyer belt
Side is provided with PMMA spraying arrays, and array is sprayed by PMMA slurries even application in graphene/Cu by PMMA in transmit process
A surface on.Wherein, PMMA contents are 1.5% (w/w) in PMMA slurries amount, and solvent is ethyl acetate, spraying rate 10mL/
s。
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, shouldn't be now passed through nitrogen pressurization, add
Heat to the glass transition temperature higher than PMMA is 150 DEG C, continues 15min, PMMA is fitted tightly over graphenic surface, obtain
PMMA/ graphenes/Cu.
(4) PMMA one side is not sprayed on the etching liquid that PMMA/ graphenes/Cu is put into an etching, cleaning device and
Contact etching liquid down, etch Cu, wherein etching liquid be 10% (w/v) ammonium persulfate aqueous solution, etch period 30min,
After copper is etched totally, PMMA/ graphenes are obtained.
(5) the smooth transfer blade in clean, surface is tiltedly inserted and secured in above-mentioned etching, cleaning device, will etch,
Etching liquid in cleaning device is slowly released, and to reduce liquid level, graphene/PMMA is lain flat on transfer blade, is taken out patch
In graphene/PMMA on transfer blade；Deionized water is put into toward the etching, in cleaning device again, will be affixed on transfer blade
The slow oblique cuttings of graphene/PMMA enter in deionized water, soak 60min, clean up, obtain clean graphene/PMMA.
The smooth polyethylene terephthalate (PET) being fixed on transfer blade is fixed on described etch, clearly again
In cleaning device, tapping valve is opened out, slowly releases deionized water, liquid level is reduced, graphene/PMMA is entirely laid in target
In substrate, room temperature is dried, that is, obtains PMMA/ graphenes/PET.
Wherein, the etching, cleaning device are as shown in figure 1, first including device body 1, in device body 1 is solid
Determine bolt 2 and the tapping valve 3 outside device body 1, the transfer blade of smooth surface or be fixed with target substrate poly terephthalic acid
The oblique cutting of transfer blade 4 of glycol ester enters in the device body 1 equipped with etching liquid or cleaning fluid 5, and graphene/PMMA 6 floats on etching
The surface of liquid or cleaning fluid 5.
(6) after PMMA/ graphenes/PET is dried, be put into hyperbaric heating case, first normal heating, heating schedule be prior to
10min is heated at 50 DEG C, after being warming up to 100 DEG C, 10min is heated at 100 DEG C；Nitrogen, then hyperbaric heating are then passed to, it is high
Press heating schedule be prior to pressure be 200KPa, temperature be hyperbaric heating 10min at 100 DEG C, be 200KPa, temperature then at pressure
For hyperbaric heating 30min at 150 DEG C, to remove the micro-bubble between graphene and PET.
Temperature is hyperbaric heating 15-30min at 120-150 DEG C.
(7) PMMA/ graphenes/PET is irradiated with DUV, irradiation time 1h, cracks PMMA, be easy to go in next step
Except PMMA, avoid the PMMA of graphenic surface remaining；
(8) the PMMA/ graphenes/PET being irradiated by deep UV is fixed on the PMMA removal devices equipped with acetone
In acetone above, and be coated with PMMA surface down, heating, produce acetone steam, PMMA is dissolved by acetone steam, with
PMMA is efficiently removed, the removal time is 30min.Finally, graphene/PET is first used into acetone rinsing, then is separately immersed in anhydrous second
In alcohol and deionized water, nitrogen drying, that is, the PET/ graphenes shifted are obtained, the graphene corrugationless of transfer, without breakage, face
Product is 50cm*50cm, realizes the transfer of graphene large area, high quality.
Wherein, the PMMA removal devices equipped with acetone are as shown in Fig. 2 including device case 7, the inner bottom part of device case 7
Provided with acetone heater 8, it is additionally provided with the relative inner wall of device case 7 to the fixation PMMA/ graphenes/PET10
The second gim peg 9, acetone heater 8 start after produce acetone steam 11, to dissolve on PMMA/ graphenes/PET 10
PMMA。
Embodiment 2
A kind of transfer method of large-area high-quality graphene, comprises the following steps：
(1) using Cu as growth substrate, graphene is prepared with chemical deposition.Cut the 50cm*50cm stone grown
Black alkene/Cu, graphene/Cu is laid on glass clean, that surface is smooth, and graphite is clamped with another block of identical glass
Alkene/Cu.Rolling group is crossed, the speed of rolling is 2cm/min, makes graphene/Cu flattenings.
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with 8cm/s speed, while on conveyer belt
Side is provided with PMMA spraying arrays, and array is sprayed by PMMA slurries even application in graphene/Cu by PMMA in transmit process
A surface on.Wherein, PMMA contents are 1% (w/w) in PMMA slurries amount, and solvent is ethyl acetate, spraying rate 5mL/s.
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, shouldn't be now passed through nitrogen pressurization, add
Heat to the glass transition temperature higher than PMMA is 130 DEG C, continues 20min, PMMA is fitted tightly over graphenic surface, obtain
PMMA/ graphenes/Cu.
(4) PMMA one side is not sprayed on the etching liquid that PMMA/ graphenes/Cu is put into an etching, cleaning device and
Contact etching liquid down, etch Cu, wherein etching liquid be 11% (w/v) ammonium persulfate aqueous solution, etch period 35min,
After copper is etched totally, PMMA/ graphenes are obtained.
(5) the smooth transfer blade in clean, surface is fixed in above-mentioned etching, cleaning device, by etching, cleaning device
In etching liquid slowly release, to reduce liquid level, graphene/PMMA is lain flat on transfer blade, take out and be affixed on transfer blade
On graphene/PMMA；Be put into deionized water toward the etching, in cleaning device again, by the graphene being affixed on transfer blade/
The slow oblique cuttings of PMMA enter in deionized water, soak 60min, clean up, obtain clean graphene/PMMA.
The smooth PEN (PEN) being fixed on transfer blade is fixed on the etching, cleaning again
In device, tapping valve is opened out, slowly releases deionized water, liquid level is reduced, graphene/PMMA is entirely laid in target base
On the PEN of bottom, room temperature is dried, that is, obtains PMMA/ graphenes/PEN.
Wherein, the etching, the structure of cleaning device are identical with embodiment 1, no longer repeat herein.
(6) after PMMA/ graphenes/PEN is dried, be put into hyperbaric heating case, first normal heating, heating schedule be prior to
30min is heated at 40 DEG C, after being warming up to 100 DEG C, 30min is heated at 100 DEG C；Nitrogen, then hyperbaric heating are then passed to, it is high
Press heating schedule be prior to pressure be 500KPa, temperature be hyperbaric heating 15min at 100 DEG C, be 200KPa, temperature then at pressure
For hyperbaric heating 30min at 120 DEG C, to remove the micro-bubble between graphene and PEN.
(7) PMMA/ graphenes/PEN is irradiated with DUV, irradiation time 2h, cracks PMMA, be easy to go in next step
Except PMMA, avoid the PMMA of graphenic surface remaining；
(8) the PMMA/ graphenes/PEN being irradiated by deep UV is fixed on the PMMA removal devices equipped with acetone
In acetone above, and be coated with PMMA surface down, heating, produce acetone steam, PMMA is dissolved by acetone steam, with
PMMA is efficiently removed, the removal time is 30min.Finally, graphene/PEN is first used into acetone rinsing, then is separately immersed in anhydrous second
In alcohol and deionized water, nitrogen drying, that is, the graphene/PEN shifted is obtained, the graphene corrugationless of transfer, without breakage, face
Product is 50cm*50cm, realizes the transfer of graphene large area, high quality.
Wherein, the structure of the PMMA removal devices equipped with acetone is identical with embodiment 1, no longer repeats herein.
Embodiment 3
A kind of transfer method of large-area high-quality graphene, comprises the following steps：
(1) using Cu as growth substrate, graphene is prepared with chemical deposition.Cut the 50cm*50cm stone grown
Black alkene/Cu, graphene/Cu is laid on glass clean, that surface is smooth, and graphite is clamped with another block of identical glass
Alkene/Cu.Rolling group is crossed, the speed of rolling is 3cm/min, makes graphene/Cu flattenings.
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with 10cm/s speed, while on conveyer belt
Side is provided with PMMA spraying arrays, and array is sprayed by PMMA slurries even application in graphene/Cu by PMMA in transmit process
A surface on.Wherein, PMMA contents are 3% (w/w) in PMMA slurries amount, and solvent is ethyl acetate, spraying rate 8mL/s.
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, shouldn't be now passed through nitrogen pressurization, add
Heat to the glass transition temperature higher than PMMA is 150 DEG C, continues 30min, PMMA is fitted tightly over graphenic surface, obtain
PMMA/ graphenes/Cu.
(4) PMMA one side is not sprayed on the etching liquid that PMMA/ graphenes/Cu is put into an etching, cleaning device and
Contact etching liquid down, etch Cu, wherein etching liquid be 12% (w/v) ammonium persulfate aqueous solution, etch period 25min,
After copper is etched totally, PMMA/ graphenes are obtained.
(5) the smooth transfer blade in clean, surface is fixed in above-mentioned etching, cleaning device, by etching, cleaning device
In etching liquid slowly release, to reduce liquid level, graphene/PMMA is lain flat on transfer blade, take out and be affixed on transfer blade
On graphene/PMMA；Be put into deionized water toward the etching, in cleaning device again, by the graphene being affixed on transfer blade/
The slow oblique cuttings of PMMA enter in deionized water, soak 60min, clean up, obtain clean graphene/PMMA.
The smooth polyimides (PI) being fixed on transfer blade is fixed in the etching, cleaning device again, opened
Go out tapping valve, slowly release deionized water, reduce liquid level, graphene/PMMA is entirely laid on target substrate PI, room temperature
Dry, that is, obtain PMMA/ graphenes/PI.
Wherein, the etching, the structure of cleaning device are identical with embodiment 1, no longer repeat herein.
(6) after PMMA/ graphenes/PI is dried, be put into hyperbaric heating case, first normal heating, heating schedule be prior to
20min is heated at 70 DEG C, after being warming up to 100 DEG C, 20min is heated at 100 DEG C；Nitrogen, then hyperbaric heating are then passed to, it is high
Press heating schedule be prior to pressure be 300KPa, temperature be hyperbaric heating 10min at 100 DEG C, be 300KPa, temperature then at pressure
For hyperbaric heating 25min at 135 DEG C, to remove the micro-bubble between graphene and PI.
(7) PMMA/ graphenes/PI is irradiated with DUV, irradiation time 3h, cracks PMMA, be easy to go in next step
Except PMMA, avoid the PMMA of graphenic surface remaining；
(8) the PMMA/ graphenes/PI being irradiated by deep UV is fixed in the PMMA removal devices equipped with acetone
Acetone above, and be coated with PMMA surface down, heating, produce acetone steam, PMMA is dissolved by acetone steam, with height
Effect removes PMMA, and the removal time is 30min.Finally, graphene/PI is first used into acetone rinsing, then is separately immersed in absolute ethyl alcohol
In deionized water, nitrogen drying, that is, the graphene/PI shifted is obtained, the graphene corrugationless of transfer, without breakage, area
For 50cm*50cm, the transfer of graphene large area, high quality is realized.
Wherein, the structure of the PMMA removal devices equipped with acetone is identical with embodiment 1, no longer repeats herein.
Embodiment 4
A kind of transfer method of large-area high-quality graphene, comprises the following steps：
(1) using Cu as growth substrate, graphene is prepared with chemical deposition.Cut the 50cm*50cm stone grown
Black alkene/Cu, graphene/Cu is laid on glass clean, that surface is smooth, and graphite is clamped with another block of identical glass
Alkene/Cu.Rolling group is crossed, the speed of rolling is 5cm/min, makes graphene/Cu flattenings.
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with 2cm/s speed, while on conveyer belt
Side is provided with PMMA spraying arrays, and array is sprayed by PMMA slurries even application in graphene/Cu by PMMA in transmit process
A surface on.Wherein, PMMA contents are 1.5% (w/w) in PMMA slurries amount, and solvent is ethyl acetate, spraying rate 10mL/
s。
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, shouldn't be now passed through nitrogen pressurization, add
Heat to the glass transition temperature higher than PMMA is 140 DEG C, continues 18min, PMMA is fitted tightly over graphenic surface, obtain
PMMA/ graphenes/Cu.
(4) PMMA one side is not sprayed on the etching liquid that PMMA/ graphenes/Cu is put into an etching, cleaning device and
Contact etching liquid down, etch Cu, wherein etching liquid be 12% (w/v) ammonium persulfate aqueous solution, etch period 25min,
After copper is etched totally, PMMA/ graphenes are obtained.
(5) the smooth transfer blade in clean, surface is fixed in above-mentioned etching, cleaning device, by etching, cleaning device
In etching liquid slowly release, to reduce liquid level, graphene/PMMA is lain flat on transfer blade, take out and be affixed on transfer blade
On graphene/PMMA；Be put into deionized water toward the etching, in cleaning device again, by the graphene being affixed on transfer blade/
The slow oblique cuttings of PMMA enter in deionized water, soak 60min, clean up, obtain clean graphene/PMMA.
(6) safety glass is cleaned.Safety glass soaks in acetone, is cleaned by ultrasonic 30min.Then safety glass is soaked
In absolute ethyl alcohol, it is cleaned by ultrasonic 30min.Finally rinsed well repeatedly with deionized water.
Clean safety glass is fixed on the etching again, in cleaning device, opens out tapping valve, slowly run out from
Sub- water, reduce liquid level, graphene/PMMA is entirely laid on safety glass, room temperature is dried, that is, obtain PMMA/ graphenes/
Safety glass.
Wherein, the etching, the structure of cleaning device are identical with embodiment 1, no longer repeat herein.
(7) after PMMA/ graphenes/safety glass is dried, it is put into hyperbaric heating case, first normal heating, heating schedule
To heat 10min at prior to 50 DEG C, after being warming up to 100 DEG C, 10min is heated at 100 DEG C；Then pass to nitrogen, then high pressure
Heating, it prior to pressure is 200KPa that hyperbaric heating program, which is, temperature is hyperbaric heating 10min at 100 DEG C, is then at pressure
200KPa, temperature are hyperbaric heating 30min at 150 DEG C, to remove the micro-bubble between graphene and safety glass.
(8) PMMA/ graphenes/safety glass is irradiated with DUV, irradiation time 1h, cracks PMMA, under being easy to
One step removes PMMA, avoids the PMMA of graphenic surface remaining；
(9) the PMMA/ graphenes/safety glass being irradiated by deep UV is fixed on into the PMMA equipped with acetone to remove
Above acetone in device, and the surface for being coated with PMMA is down, heating, produces acetone steam, is dissolved by acetone steam
PMMA, efficiently to remove PMMA, the removal time is 30min.Finally, graphene/safety glass is first used into acetone rinsing, then distinguished
It is immersed in absolute ethyl alcohol and deionized water, nitrogen drying, that is, obtains the graphene/safety glass shifted, the graphite of transfer
Alkene corrugationless, without breakage, area 50cm*50cm, realize the transfer of graphene large area, high quality.
Wherein, the structure of the PMMA removal devices equipped with acetone is identical with embodiment 1, no longer repeats herein.
Embodiment 5
A kind of transfer method of large-area high-quality graphene, comprises the following steps：
(1) using Cu as growth substrate, graphene is prepared with chemical deposition.Cut the 50cm*50cm stone grown
Black alkene/Cu, graphene/Cu is laid on glass clean, that surface is smooth, and graphite is clamped with another block of identical glass
Alkene/Cu.Rolling group is crossed, the speed of rolling is 5cm/min, makes graphene/Cu flattenings.
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with 2cm/s speed, while on conveyer belt
Side is provided with PMMA spraying arrays, and array is sprayed by PMMA slurries even application in graphene/Cu by PMMA in transmit process
A surface on.Wherein, PMMA contents are 1.5% (w/w) in PMMA slurries amount, and solvent is ethyl acetate, spraying rate 10mL/
s。
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, shouldn't be now passed through nitrogen pressurization, add
Heat to the glass transition temperature higher than PMMA is 150 DEG C, continues 18min, PMMA is fitted tightly over graphenic surface, obtain
PMMA/ graphenes/Cu.
(4) PMMA one side is not sprayed on the etching liquid that PMMA/ graphenes/Cu is put into an etching, cleaning device and
Contact etching liquid down, etch Cu, wherein etching liquid be 12% (w/v) ammonium persulfate aqueous solution, etch period 25min,
After copper is etched totally, PMMA/ graphenes are obtained.
(5) the smooth transfer blade in clean, surface is fixed in above-mentioned etching, cleaning device, by etching, cleaning device
In etching liquid slowly release, to reduce liquid level, graphene/PMMA is lain flat on transfer blade, take out and be affixed on transfer blade
On graphene/PMMA；Be put into deionized water toward the etching, in cleaning device again, by the graphene being affixed on transfer blade/
The slow oblique cuttings of PMMA enter in deionized water, soak 60min, clean up, obtain clean graphene/PMMA.
(6) cleaning silicon chip.Silicon chip soaks in acetone, is cleaned by ultrasonic 30min.Then silicon chip is immersed in absolute ethyl alcohol
In, it is cleaned by ultrasonic 30min.Finally rinsed well repeatedly with deionized water.
Clean silicon chip is fixed in the etching, cleaning device again, tapping valve is opened out, slowly releases deionization
Water, liquid level is reduced, graphene/PMMA is entirely laid on silicon chip, room temperature is dried, that is, obtains PMMA/ graphene/silicon pieces.
Wherein, the etching, the structure of cleaning device are identical with embodiment 1, no longer repeat herein.
(7) after PMMA/ graphene/silicon pieces are dried, it is put into hyperbaric heating case, first normal heating, heating schedule is first
10min is heated at 50 DEG C, after being warming up to 100 DEG C, 10min is heated at 100 DEG C；Nitrogen, then hyperbaric heating are then passed to,
It prior to pressure is 200KPa that hyperbaric heating program, which is, temperature is hyperbaric heating 10min at 100 DEG C, is 200KPa, temperature then at pressure
Spend for hyperbaric heating 30min at 150 DEG C, to remove the micro-bubble between graphene and silicon chip.
(8) PMMA/ graphene/silicon pieces are irradiated with DUV, irradiation time 1h, cracks PMMA, be easy in next step
PMMA is removed, avoids the PMMA of graphenic surface remaining；
(9) the PMMA/ graphene/silicon pieces being irradiated by deep UV are fixed on the PMMA removal devices equipped with acetone
In acetone above, and be coated with PMMA surface down, heating, produce acetone steam, PMMA is dissolved by acetone steam, with
PMMA is efficiently removed, the removal time is 30min.Finally, graphene/silicon piece is first used into acetone rinsing, then be separately immersed in anhydrous
In ethanol and deionized water, nitrogen drying obtains the graphene/silicon piece shifted, graphene corrugationless, the nothing of transfer are broken
Damage, area 50cm*50cm, realizes the transfer of graphene large area, high quality.
Wherein, the structure of the PMMA removal devices equipped with acetone is identical with embodiment 1, no longer repeats herein.
Graphene film after the transfer that inventor also obtains to the inventive method is tested as follows：
The PET/ graphenes shifted using the method for the embodiment of the present invention 1 are cut into 5cm × 5cm size (totally 100
Piece), 50 are randomly selected, 1cm × 5cm passage is portrayed as with laser, with universal meter TCH test channel resistance, totally 250 passages
Resistance value, transfer effect is characterized by the size of aisle resistance, the uniformity.Fig. 3 is the histogram of statistical result, it can be seen that
Resistance concentrates on 980-990 Ω.Table 1 is the data using the graphene of the method for the embodiment of the present invention 1 transfer.
Table 1
As can be seen that 980-990 Ω proportions are 42.8% in table 1, and the Ω of resistance average 984.4, variance 9.2%,
Show that the graphene resistance that is transferred out of is smaller and uniform.For the method with the present invention as a comparison, inventor is not also to adopting
The graphene shifted with this method is tested, and table 2 is the data (1cm × 5cm passages for the graphene not shifted using this method
Resistance).
Table 2
| A1 | A2 | A3 | A4 | A5 | |
| Resistance/Ω | 2145.2 | N | 3531.3 | 1581.6 | N |
| B1 | B2 | B3 | B4 | B5 | |
| Resistance/Ω | 2145.2 | N | N | 9027.6 | N |
| C1 | C2 | C3 | C4 | C5 | |
| Resistance/Ω | 14819.4 | N | 6739.3 | 5921.8 | N |
Note：N represents not measure resistance value.
It can be seen from Table 2 that the aisle resistance of the graphene is larger, and it is uneven, show the graphene on passage
It is damaged.Some passages do not measure resistance value, show that the graphene on this passage is completely damaged, cause passage breaking.
Shown by data above, graphene transfer method of the invention can shift the graphene of large area, high quality.
Claims (10)
1. a kind of transfer method of large-area high-quality graphene, it is characterised in that comprise the following steps：
(1) between the graphene being grown on copper foil being clipped in into the smooth glass of two panels, roll unit is crossed, makes graphene/Cu flattenings；
(2) graphene/Cu after flattening is placed on conveyer belt and transmitted with certain speed, and in graphite in transmit process
PMMA slurries on even application on an alkene/Cu surface；
(3) graphene/Cu for having sprayed PMMA is placed on warm table and heated, heating-up temperature is higher than PMMA glass transition temperature
Degree, 15-30min is heated, obtains PMMA/ graphenes/Cu；
(4) by the PMMA/ graphenes/Cu face-down contact etching liquid for not spraying PMMA, Cu is etched, obtains PMMA/ graphite
Alkene；
(5) the PMMA/ graphenes etched are transferred in cleaning fluid, slowly decline cleaning fluid liquid level, obtain clean PMMA/
Graphene, then clean PMMA/ graphenes are tiled to target substrate, obtain PMMA/ graphenes/target substrate；
(6) after PMMA/ graphenes/target substrate is dried, it is put into hyperbaric heating case, first normal heating, then passes to nitrogen,
Hyperbaric heating again, remove the micro-bubble between graphene and target substrate；
(7) PMMA/ graphenes/target substrate is irradiated with DUV, irradiation time 1-3h, cracks PMMA, be easy to next
Step removes PMMA；
(8) the PMMA/ graphenes/target substrate being irradiated by deep UV is fixed on the PMMA removal devices equipped with acetone
In acetone above, and be coated with PMMA surface down, heating, produce acetone steam, PMMA is dissolved by acetone steam；Most
Afterwards, graphene/target substrate is separately immersed in absolute ethyl alcohol and deionized water, nitrogen drying, that is, obtains having shifted big
The graphene film of area and high quality, high quality.
2. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that described rolling speed
Spend for 2-5cm/min, transfer rate 2-10cm/s.
3. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that step (2) is described
PMMA slurries in PMMA contents be 1%-3% (w/w), solvent is ethyl acetate, spraying rate 5-10mL/s.
4. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that step (4) is described
Etching liquid is 10-12% (w/v) ammonium persulfate aqueous solution, and the etch period is 25-35min.
5. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that step (5) is described
Transfer is specially that first the smooth transfer blade in clean, surface is fixed in an etching, cleaning device, by etching, cleaning device
In etching liquid slowly release, to reduce liquid level, graphene/PMMA is lain flat on transfer blade, take out and be affixed on transfer blade
On graphene/PMMA；Be put into deionized water toward the etching, in cleaning device again, by the graphene being affixed on transfer blade/
The slow oblique cuttings of PMMA enter in deionized water, soak 60min, clean up, obtain clean graphene/PMMA.
6. the transfer method of large-area high-quality graphene according to claim 5, it is characterised in that step (5) is described
Clean graphene/PMMA is tiled to being specially to fix the smooth target substrate being fixed on transfer blade in target substrate
In the cleaning device, outlet valve is opened, slowly releases deionized water, liquid level is reduced, graphene/PMMA is entirely attached to
In target substrate, room temperature is dried, that is, obtains PMMA/ graphenes/target substrate.
7. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that the target substrate
For one kind in polyethylene terephtalate, PEN PEN, polyimides PI, glass, silicon chip.
8. the transfer method of the large-area high-quality graphene according to claim 5 or 6, it is characterised in that the etching,
Cleaning device includes device body, located at intrinsic first gim peg of described device and located at the external discharge opeing of described device sheet
Valve.
9. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that step (6) is described
Normal heating be specially prior to 40-70 DEG C at heat 10-30min, after being warming up to 100 DEG C, 10- is heated at 100 DEG C
30min；The hyperbaric heating is specially 200-500KPa prior to pressure, temperature is hyperbaric heating 10-20min at 100 DEG C, then
The hyperbaric heating 15-30min at pressure is 200-500KPa, temperature is 120-150 DEG C.
10. the transfer method of large-area high-quality graphene according to claim 1, it is characterised in that step (8) is described
PMMA removal devices equipped with acetone include device case, and the inner bottom part of described device housing is provided with to heat the heating of acetone
Device, it is additionally provided with the relative inner wall of described device housing to the second solid of the fixation PMMA/ graphenes/target substrate
Determine bolt.
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| CN108609615A (en) * | 2018-07-30 | 2018-10-02 | 合肥工业大学 | A kind of transfer method of uniform graphene film |
| CN110540197A (en) * | 2018-05-29 | 2019-12-06 | 北京石墨烯研究院 | method for cleaning graphene surface by using carbon nano material |
| CN112265985A (en) * | 2020-10-30 | 2021-01-26 | 中国科学院重庆绿色智能技术研究院 | Clean transfer method of wafer-level two-dimensional material |
| CN112978711A (en) * | 2021-03-23 | 2021-06-18 | 北京科技大学 | Method for transferring large-area graphite alkyne film |
| CN113264522A (en) * | 2021-06-21 | 2021-08-17 | 松山湖材料实验室 | Two-dimensional material transfer method |
| EP3936476A1 (en) | 2020-07-08 | 2022-01-12 | Valstybinis Moksliniu Tyrimu Institutas Fiziniu Ir Technologijos Mokslu Centras | Method of polymethylmethacrylate (pmma) removal from a graphene surface by photoexposure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110540197A (en) * | 2018-05-29 | 2019-12-06 | 北京石墨烯研究院 | method for cleaning graphene surface by using carbon nano material |
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| EP3936476A1 (en) | 2020-07-08 | 2022-01-12 | Valstybinis Moksliniu Tyrimu Institutas Fiziniu Ir Technologijos Mokslu Centras | Method of polymethylmethacrylate (pmma) removal from a graphene surface by photoexposure |
| CN112265985A (en) * | 2020-10-30 | 2021-01-26 | 中国科学院重庆绿色智能技术研究院 | Clean transfer method of wafer-level two-dimensional material |
| CN112978711A (en) * | 2021-03-23 | 2021-06-18 | 北京科技大学 | Method for transferring large-area graphite alkyne film |
| CN112978711B (en) * | 2021-03-23 | 2022-07-22 | 北京科技大学 | Method for transferring large-area graphite alkyne film |
| CN113264522A (en) * | 2021-06-21 | 2021-08-17 | 松山湖材料实验室 | Two-dimensional material transfer method |
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