CN107119316A - A kind of temperature-varying zone liquid bed Direct precipitation grows the preparation method of graphene - Google Patents
A kind of temperature-varying zone liquid bed Direct precipitation grows the preparation method of graphene Download PDFInfo
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- CN107119316A CN107119316A CN201710240979.3A CN201710240979A CN107119316A CN 107119316 A CN107119316 A CN 107119316A CN 201710240979 A CN201710240979 A CN 201710240979A CN 107119316 A CN107119316 A CN 107119316A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 238000001556 precipitation Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 238000005336 cracking Methods 0.000 claims abstract description 27
- 229910021398 atomic carbon Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000007704 transition Effects 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000004781 supercooling Methods 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- -1 graphite alkene Chemical class 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000011833 salt mixture Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Chemical class 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000001996 bearing alloy Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 33
- 230000008018 melting Effects 0.000 description 26
- 238000002844 melting Methods 0.000 description 26
- 239000011135 tin Substances 0.000 description 20
- 229910000846 In alloy Inorganic materials 0.000 description 17
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 17
- 238000007233 catalytic pyrolysis Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of temperature-varying zone liquid bed Direct precipitation grows the preparation method of graphene：I.e. under a shielding gas, the solvent of temperature-varying zone liquid bed is molten state medium, and solute is atomic carbon；The molten state medium is less than one or more material compositions of target substrate fusing point by boiling point higher than carbon cracking temperature and fusing point；During work, molten state is heated to；Alternating temperature is distinguished into relatively-high temperature area, transition temperature-varying zone and relatively low warm area；Relatively-high temperature area molten state media operation temperature is higher than carbon cracking temperature, carbon source is activated cracking in relatively-high temperature area, the atomic carbon formed after cracking is dissolved in molten state medium, and the above-mentioned molten state medium for being dissolved with atomic carbon is cooled by transition temperature-varying zone and relatively low warm area is transported to；In relatively low warm area, molten state media operation temperature is slightly above or equal to the supersaturated Precipitation Temperature of atomic carbon.Graphene can be continuously grown directly upon in target substrate without transfer, superior in quality with graphene film, prepare the characteristics of low cost, efficiency high, few pollution.
Description
Technical field
The present invention relates to field of new material preparation, specifically a kind of temperature-varying zone liquid bed Direct precipitation growth graphene
Preparation method.
Background technology
Graphene be one kind by carbon atom with sp2There is the two dimensional crystal of honeycomb lattice formed by hydridization., English in 2004
The An Deliehaimu and Constantine's Nuo Woxiao loves of University of Manchester of state successfully isolate graphene from graphite,
And therefore obtain Nobel Prize in physics in 2010.
Graphene has excellent performance.First, the specific surface area of graphene is very big, up to 2630m2/g.Secondly, stone
Carbon atom in black alkene is with sp2Mode hydridization, each carbon atom three carbon atoms adjacent thereto form stabilization by σ keys
Carbon-carbon bond, thus make graphene that there is high mechanical property, its Young's modulus is up to 1100GPa, and fracture strength is reachable
130GPa.Again, the pi-electron delocalization in graphene forms big pi bond, and pi-electron can be moved freely, thus graphene have it is excellent
Electric conductivity, its carrier mobility speed may be up to 2 × 105cm2·V-1·S-1, and resistivity only has 10-8Ωm.In addition, stone
Black alkene also has good optical property, thermal property and magnetic performance etc..Therefore, graphene has huge potential application valency
Value, it is considered to be one of contemporary most important new material.
At present, the preparation method of graphene can be divided into method from top to bottom and from bottom to top method, wherein, graphite oxide reduction
Method is the main method in method from top to bottom；Chemical vapor deposition（CVD）Epitaxial growth method is main side from bottom to top in method
Method；The method that bed of molten salt prepares graphene is another method for growing graphene from bottom to top；There is so-called plasma in addition
The method that body non high temperature liquid phase method grows graphene.The subject matter of the above method is：
1st, graphene oxide GO poor performances, defect is more, and pollution is big.Graphene oxide typically uses improved Hummers methods, even if
After the concentrated sulfuric acid, sodium nitrate and potassium permanganate and graphite vigorous reaction, diluted and reduced with hydrogen peroxide, then it is pure by ion exchange
Change, dry, obtain graphene oxide GO.It is general that redox graphene rGO can be obtained as reducing agent using hydrazine.So
The product of preparation necessarily carries substantial amounts of phenolic group and carboxyl, with substantial amounts of defect（10~15%）, lose excellent lead
Electrical property.Defect is more and powdered so that GO mechanical properties are not also high.Stable processing technique is poor, and product structure has not
Certainty, production process uses strong acid and strong oxidizer, and environmental pollution is big, and processing cost is high.
2nd, CVD graphene performance is good, but cost is very high, and production efficiency is extremely low.This method is to be filled with carbon source at high temperature
Gas（Such as methane, ethane, acetylene）, carbon-source gas are decomposed simultaneously forms graphene on substrate.This method can be in substrate
（Such as copper substrate）Upper formation high-quality graphene, but strict, reaction time length, low yield are required to device and working condition
Under, it is with high costs.Particularly, by this method in substrate（Such as copper, nickel, carborundum）The graphene of upper growth is difficult from lining
Shifted on bottom；Generally required during transfer using radical approach such as strong acid burn into high-temperature gasifications, this has resulted in cost height, environment
Pollution is big, and can damage graphene finished product.
Although the 3, bed of molten salt, which prepares the method for graphene, can prepare the graphene of superior performance at lower cost, made
Into graphene be powder, using when generally require to be made after slurry coat film forming, it is necessary to solve it is dispersed, be bonded, solidification
Etc. many technological problemses.Moreover, the graphene number of plies of this method production, the more difficult control such as size and quality also has micro
Sodium, chlorion pickup, it is impossible to obtain high-quality graphene film.
Although the method for plasma non high temperature liquid phase method growth graphene directly can grow graphite in target substrate
Alkene film is without transfer, and performance quality is excellent, but needs to use plasma enhancing, carbon source be activated cracking cost compared with
Atom carbon dissolution amount is less in height, liquid phase medium, and growth control is more difficult.
The content of the invention
The purpose of the present invention aiming at above-mentioned technical problem, propose that a kind of quality of forming film is good, cost is low, efficiency high, dirt
A kind of few temperature-varying zone liquid bed Direct precipitation of dye grows the preparation method of graphene.
A kind of temperature-varying zone liquid bed Direct precipitation of the present invention grows the preparation method of graphene, and it is technically characterized in that：
Under a shielding gas, the solvent of temperature-varying zone liquid bed is molten state medium, and solute is atomic carbon；The molten state medium is high by boiling point
It is less than one or more material compositions of target substrate fusing point in carbon cracking temperature and fusing point；During work, molten state is heated to；Become
Warm area is divided into relatively-high temperature area, transition temperature-varying zone and relatively low warm area；Relatively-high temperature area molten state media operation temperature is higher than carbon
Cracking temperature, carbon source is activated cracking in relatively-high temperature area, and the atomic carbon formed after cracking is dissolved in molten state medium, will be upper
State and be dissolved with the molten state medium of atomic carbon and cool by transition temperature-varying zone and be transported to relatively low warm area；In relatively low warm area,
Molten state media operation temperature is slightly above or equal to the supersaturated Precipitation Temperature of atomic carbon；Target substrate is cooled to supercooled state；Target
Substrate floats or is immersed in liquid bed, and the supersaturated indigenous graphite alkene film of atomic carbon of dissolving is deposited directly in target substrate.
Higher than carbon cracking temperature, fusing point includes metal and conjunction to the boiling point less than the molten state medium of target substrate fusing point
Gold, inorganic salts, alkali, oxide, carbide, nitride, fluoride, mixed ionic liquid；It is preferred that tin, tin alloy, cuprum-nickel-stannum are closed
Gold, low melting point salt-mixture, mixed ionic liquid.
The carbon source at least includes one kind in aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative.
The protective gas is at least one kind in nitrogen, argon gas, hydrogen, ammonia.
Described target substrate refers to directly reach the substrate using target, including high-molecular organic material, metal and conjunction
Gold, inorganic crystal material, unorganic glass body material, ceramic material；It is preferred that PMMA, glass, crystal silicon chip, sapphire.
Further, by continuing relatively-high temperature area carbon source activation cleavage in molten state medium, molten state medium passes through
Cross temperature-varying zone cooling and be transported to relatively low warm area, the step of target substrate is continuously transported is realized so that graphene in relatively low warm area
Film successive sedimentation is in target substrate.
Further, described target substrate is membrane material, and target substrate uses " volume to volume（R2R）" continuous processing side
During formula, heat conducting film is set on target substrate upper strata；Or heat conducting film is set in the intermediate course of two layers of target substrate up and down.
Further, during the carbon cracking solution modeling, copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum are used
One kind in rhodium is used as catalyst；It is preferred that nickel, nickel-containing alloys.
Further, the molten state medium of liquid bed is subcooled as target substrate, now protective gas.
A kind of temperature-varying zone liquid bed Direct precipitation of the present invention grows the preparation method of graphene, is using solid to existing
The breakthrough for the graphene method that is vapor-deposited on body substrate, is also the improvement that graphene method is prepared to other liquid bed, there is as follows
Three big advantages：
1st, compared with graphene oxide, graphene performance prepared by the present invention is good, and cost is low, pollutes small, efficiency high, ratio of defects ratio
The low several orders of magnitude of graphene oxide, be it is a kind of can be less than graphene oxide cost large-scale production electron level graphene
Method..
2nd, compared with CVD graphene, cost of the present invention is low, efficiency high.Because graphene is grown directly upon aimed thin film
It is upper to shift, the graphene transport difficulties of puzzlement scientific research and engineering technological are solved, cost can be lower than conventional CVD several
The individual order of magnitude, efficiency then has 100,000 times of raising.In addition, liquid phase is compared with gas phase, crystalline quality is good, and long crystalline substance speed is fast.
3rd, compared with molten-salt growth method graphene, performance is excellent, and quality is good, efficiency high, pollutes small.It is different from the product of molten-salt growth method
Graphene powder, the high-quality graphene film for being directly deposited target substrate for preparing of the present invention, without transfer, and can be with
Using " volume to volume（R2R）" continuous production processes, water elution is eliminated except inorganic salts, and the processing step such as filter centrifugation separation is dirty
Dye is smaller.
Plasma enhancing need not be then used compared with plasma non high temperature liquid phase method growth graphene method, into film quality
Amount is more preferable, cost is lower, more efficient.
Therefore, the graphene prepared by a kind of method of temperature-varying zone liquid of the invention bed Direct precipitation growth graphene,
The purpose in target substrate without transfer can be continuously grown directly upon by having reached, superior in quality with graphene film, and cost is low, effect
The characteristics of rate is high, pollution is few.
Embodiment
Embodiment one：
Because the graphene branch problem of growth method is to restrict the principal element that graphene prepares cost and efficiency, and PMMA can be with
Say it is a kind of omnipotent intermediate base bottom.If graphene can be grown directly upon on PMMA, then just actually solve stone
The branch problem of black alkene.
Under nitrogen protection, in relatively-high temperature area, tin-indium alloy is filled in nickel matter container as liquid bed molten state medium,
Wherein tin, indium mass ratio are 8:2, heating melting, which is warming up to after 800 DEG C, is continuously passed through acetylene gas, and acetylene carbon source is activated splitting
Solution, the atomic carbon after cracking is dissolved in molten state medium tin-indium alloy, and nickel container also functions to catalytic pyrolysis and activation；With
The above-mentioned melting tin-indium alloy medium for being dissolved with carbon is transported in the carbonaceous groove of relatively low warm area by pipeline, and alternating temperature is passed through during conveying
Area, is dissolved with the melting tin-indium alloy medium cooling of carbon to 210 DEG C in the pipeline of temperature-varying zone, keeps carbon to separate out shape in unsaturation
State；Medium in relatively low warm area, carbonaceous groove keeps 210 DEG C of operating temperature, meanwhile, two layers of overlapping being wound into a roll is thin
Film, lower floor is PMMA films, and upper strata is copper heat conducting film, cooled and is cooled to 200 DEG C, then moves device by Volume, film is slightly soaked
In the melting tin-indium alloy medium for entering container, and it is set to swim on melting tin-indium alloy dielectric fluid state bed liquid level using buoyancy,
The supercooling temperature of film causes carbon supersaturation precipitation on film of dissolving, so that the deposited graphite on the target substrate film
Alkene film, is then driven by serial roll shaft, winding, finally gives " volume to volume（R2R）" the continuous graphite being grown in PMMA film
Alkene.
The graphene that the above method is obtained is the uniformly continuous of 1~10 atomic layers thickGraphite crystal film。
Embodiment two：
Under nitrogen, argon gas protection, tin metal is filled in relatively-high temperature area, nickel matter container as liquid bed molten state medium,
Heating melting, which is warming up to after 1200 DEG C, is continuously added to polystyrene, and polystyrene carbon source is activated cracking, the atomic carbon after cracking
It is dissolved in molten state medium tin liquor, nickel container also functions to catalytic pyrolysis and activation；With pipeline by the above-mentioned carbon of being dissolved with
Soldering tin is transported in the stainless steel tank of relatively low warm area, by temperature-varying zone during conveying, and carbon is dissolved with the pipeline of temperature-varying zone
Soldering tin be cooled to 400 DEG C, keep carbon in unsaturation precipitation state；Medium in relatively low warm area, stainless steel tank is protected
400 DEG C of operating temperature is held, meanwhile, quartzy plate glass cooled the tin liquor face for being cooled to and melting being placed in after 380 DEG C, and buoyancy makes stone
English plate glass is swum on the tin liquor face of melting, and the supercooling temperature of glass causes carbon supersaturation precipitation on glass of dissolving,
So as to the deposited graphite alkene in the target glass, then by traction, finally give and be continuously grown on quartzy plate glass
Individual layer and few layer graphene film（SLG ＆ FLG）.
The glass that growth has graphene film has extremely good electric conductivity and transparency；Dredged simultaneously because graphene is hydrophobic
The property of oil, or good Nano self-cleaning material；Other graphene film also has reinforcing reinforcement effect and steam to isolate to glass
Effect.
Embodiment three：
As described above, under nitrogen, argon gas protection, filling and being situated between as liquid bed molten state in relatively-high temperature area, nickel matter container
Matter, wherein copper, nickel, tin mass ratio are 3:3:4, heating melting, which is warming up to after 1000 DEG C, is passed through toluene liquid in bottom, carbon source quilt
Activation cleavage, the atomic carbon after cracking is dissolved in molten state medium adonic, and nickel container also functions to catalytic pyrolysis and work
Change is acted on；The above-mentioned melting tin-indium alloy medium for being dissolved with carbon is transported in the carbonaceous groove of relatively low warm area with pipeline, conveyed
When by temperature-varying zone, the melting adonic medium cooling of carbon is dissolved with the pipeline of temperature-varying zone to 420 DEG C, keep carbon non-
Saturation precipitation state；Medium in relatively low warm area, carbonaceous groove keeps 420 DEG C of operating temperature, meanwhile, crystal silicon chip cooled
It is cooled to 400 DEG C of adonic medium liquid levels for being placed in melting, buoyancy makes crystal silicon chip swim in the cuprum-nickel-stannum medium liquid level of melting
On, the supercooling temperature of crystal silicon chip causes carbon supersaturation precipitation on crystal silicon chip of dissolving, so that the shape on the target crystal silicon chip
Into individual layer and few layer graphene film（SLG ＆ FLG）.
Example IV：
As described above, under nitrogen, argon gas protection, tin-indium alloy is filled in relatively-high temperature area, nickel matter container as liquid bed
Molten state medium, wherein tin, indium mass ratio are 8:2, heating melting, which is warming up to after 800 DEG C, is continuously passed through acetylene gas, acetylene carbon
Source is activated cracking, and the atomic carbon after cracking is dissolved in molten state medium tin-indium alloy, nickel container also function to catalytic pyrolysis and
Activation；The above-mentioned melting tin-indium alloy medium for being dissolved with carbon is transported in the carbonaceous groove of relatively low warm area with pipeline, it is defeated
By temperature-varying zone when sending, the melting tin-indium alloy that carbon is dissolved with the pipeline of temperature-varying zone is cooled to 260 DEG C, keeps carbon in unsaturation
Precipitation state；Medium in relatively low warm area, carbonaceous groove keeps 260 DEG C of operating temperature, meanwhile, silica fibre tow winding
In rolls, cooled and be cooled to 230 DEG C, device is then moved by Volume, in the melting tin-indium alloy medium that tow is immersed to container, tow
Supercooling temperature cause dissolving carbon tow surface supersaturation separate out so that the target substrate silica fibre silk on deposit
Graphene, is then driven by serial roll shaft, winding, finally gives the continuous graphene film being grown on silica fibre silk.
Embodiment five：
As described above, under nitrogen, argon gas protection, tin-indium alloy is filled in relatively-high temperature area, nickel matter container as liquid bed
Molten state medium, wherein tin, indium mass ratio are 8:2, heating melting, which is warming up to after 800 DEG C, is continuously passed through acetylene gas, acetylene carbon
Source is activated cracking, and the atomic carbon after cracking is dissolved in molten state medium tin-indium alloy, nickel container also function to catalytic pyrolysis and
Activation；The above-mentioned melting tin-indium alloy medium for being dissolved with carbon is transported in the carbonaceous groove of relatively low warm area with pipeline, it is defeated
By temperature-varying zone when sending, the melting tin-indium alloy medium cooling of carbon is dissolved with the pipeline of temperature-varying zone to 420 DEG C, carbon is kept non-
Saturation precipitation state；Medium in relatively low warm area, carbonaceous groove keeps 420 DEG C of operating temperature, meanwhile, aluminium wire beam is wound into
Volume, cooled and is cooled to 400 DEG C, then moved device by Volume, in the melting tin-indium alloy medium that tow is immersed to container, tow
Supercooling temperature causes the carbon of dissolving in the supersaturation precipitation of tow surface, so that graphene is formed on the target substrate aluminium wire,
Then it is driven, is wound by serial roll shaft, finally gives the continuous graphene film being grown on aluminium wire.
Embodiment six：
As described above, under nitrogen protection, LiCl-AlCl is filled in relatively-high temperature area, nickel matter container3Salt-mixture is used as liquid
Bed molten state medium, wherein LiCl-AlCl3Molar fraction ratio is 1:1, heating melting, which is warming up to after 700 DEG C, is continuously passed through acetylene
Gas, acetylene carbon source is activated cracking, and the atomic carbon after cracking is dissolved in molten state medium LiCl-AlCl3In salt-mixture, nickel holds
Device also functions to catalytic pyrolysis and activation；With pipeline by the above-mentioned melting LiCl-AlCl for being dissolved with carbon3Salt-mixture is transported to phase
To in the carbonaceous groove of low-temperature space, by temperature-varying zone during conveying, the melting LiCl-AlCl of carbon is dissolved with the pipeline of temperature-varying zone3It is mixed
Close salt and be cooled to 160 DEG C, and [bmim] Cl is added at 200 DEG C, form [bmim] Cl-AlCl-LiCl ionic liquids, wherein
[bmim] Cl-AlCl-LiCl molar fractions ratio is 1:1:1, carbon is kept in unsaturation precipitation state；In relatively low warm area, carbonaceous
Medium in groove keeps 160 DEG C of operating temperature, meanwhile, two layers of overlapping film being wound into a roll, lower floor is PMMA films, upper strata
For copper heat conducting film, cooled and be cooled to 150 DEG C, device is then moved by Volume, film is slightly immersed to [bmim] Cl-AlCl- of container
In LiCl ionic liquids, and it is set to swim on [bmim] Cl-AlCl-LiCl ionic liquid liquid levels using buoyancy, the mistake of film
Cold temperature causes carbon supersaturation precipitation on film of dissolving, so that the deposited graphite alkene on the aimed thin film, then passes through
Serial roll shaft transmission, winding finally gives " volume to volume（R2R）" the continuous graphene film being grown in PMMA film.
Embodiment seven：
As described above, under nitrogen, argon gas protection, tin metal is filled in relatively-high temperature area, nickel matter container molten as liquid bed
Melt state medium, heating melting is warming up to after 1200 DEG C is continuously added to edible soybean oil, edible soybean oil carbon source quilt in container bottom
Activation cleavage, the atomic carbon after cracking is dissolved in molten state medium tin liquor, and nickel container also functions to catalytic pyrolysis and activation；
The above-mentioned soldering tin of carbon that is dissolved with is transported in the stainless steel tank of relatively low warm area with pipeline, by temperature-varying zone during conveying,
The soldering tin that carbon is dissolved with the pipeline of temperature-varying zone is cooled to 300 DEG C, keeps carbon in unsaturation precipitation state；In relative low temperature
Area, soldering tin is delivered to a lateral opposite side flowing and the solidification from 300 DEG C of continuous coolings to tin liquor, supercooling temperature in stainless steel tank
Degree causes carbon supersaturation precipitation on solid metallic tin of dissolving, so that the deposited graphite alkene on the target substrate tin, then
Traction, obtains the few layer graphene film being continuously grown on block tin（FLG）；Constantly mended simultaneously in relatively-high temperature area nickel matter container
Addition tin metal is filled to meet quantity-produced requirement.
Claims (9)
1. a kind of temperature-varying zone liquid bed Direct precipitation grows the preparation method of graphene, it is technically characterized in that：In protective gas
Under, the solvent of temperature-varying zone liquid bed is molten state medium, and solute is atomic carbon；The molten state medium cracks temperature by boiling point higher than carbon
Degree and fusing point be less than target substrate fusing point one or more material compositions；During work, molten state is heated to；Alternating temperature is distinguished into phase
To high-temperature region, transition temperature-varying zone and relatively low warm area；Relatively-high temperature area molten state media operation temperature is higher than carbon cracking temperature, carbon
Source is activated cracking in relatively-high temperature area, and the atomic carbon formed after cracking is dissolved in molten state medium, and original is dissolved with by above-mentioned
The molten state medium of sub- carbon cools by transition temperature-varying zone and is transported to relatively low warm area；In relatively low warm area, molten state medium
Operating temperature is slightly above or equal to the supersaturated Precipitation Temperature of atomic carbon；Target substrate is cooled to supercooled state；Target substrate float or
Liquid bed is immersed in, the supersaturated indigenous graphite alkene film of atomic carbon of dissolving is deposited directly in target substrate.
2. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is that fusing point includes metal and alloy, nothing to the boiling point less than the molten state medium of target substrate fusing point higher than carbon cracking temperature
Machine salt, alkali, oxide, carbide, nitride, fluoride, mixed ionic liquid；It is preferred that tin, tin alloy, adonic, low
Fusing point salt-mixture, mixed ionic liquid.
3. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is that the carbon source at least includes one kind in aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative.
4. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is one kind that the protective gas is at least in nitrogen, argon gas, hydrogen, ammonia.
5. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is that described target substrate refers to directly reach the substrate using target, including high-molecular organic material, metal and alloy, nothing
Machine crystalline material, unorganic glass body material, ceramic material；It is preferred that PMMA, glass, crystal silicon chip, sapphire.
6. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is that, by continuing relatively-high temperature area carbon source activation cleavage in molten state medium, molten state medium cools defeated through transition temperature-varying zone
Relatively low warm area is sent to, the step of target substrate is continuously transported is realized in relatively low warm area so that graphene film successive sedimentation is in mesh
Mark in substrate.
7. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is membrane material to be described target substrate, and target substrate uses " volume to volume（R2R）" continuous processing mode when, in target substrate
Upper strata sets heat conducting film；Or heat conducting film is set in the intermediate course of two layers of target substrate up and down.
8. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
During being the carbon cracking solution modeling, made using one kind in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium
For catalyst；It is preferred that nickel, nickel-containing alloys.
9. a kind of temperature-varying zone liquid bed Direct precipitation according to claim 1 grows the preparation method of graphene, its feature
It is the molten state medium of the liquid bed as target substrate, now protective gas supercooling.
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| CN110003689A (en) * | 2019-04-05 | 2019-07-12 | 孙旭阳 | A method of directly growing graphene on carbon black |
| CN110373714A (en) * | 2019-06-03 | 2019-10-25 | 杭州电子科技大学 | A method of quick preparation large size and high quality single-layer graphene at room temperature |
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| CN106365154A (en) * | 2016-08-31 | 2017-02-01 | 孙旭阳 | Preparation method of graphene grown by adopting non-high temperature liquid phase method |
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| CN110003689A (en) * | 2019-04-05 | 2019-07-12 | 孙旭阳 | A method of directly growing graphene on carbon black |
| CN110373714A (en) * | 2019-06-03 | 2019-10-25 | 杭州电子科技大学 | A method of quick preparation large size and high quality single-layer graphene at room temperature |
| CN110527833A (en) * | 2019-07-29 | 2019-12-03 | 孙旭阳 | The method for preparing pure metals using monatomic carbon reduction |
| CN113528821A (en) * | 2019-07-29 | 2021-10-22 | 孙旭阳 | Method for preparing simple substance material by using reduction of monoatomic carbon |
| CN110983287A (en) * | 2019-10-21 | 2020-04-10 | 武汉大学 | Methods for transferring large-area 2D materials |
| CN111439743A (en) * | 2020-01-17 | 2020-07-24 | 北京清烯科技有限公司 | Manufacturing method capable of continuously and stably producing large-area graphene |
| CN111333057A (en) * | 2020-03-08 | 2020-06-26 | 西南交通大学 | Reaction device for preparing graphene and method for preparing graphene |
| CN111333057B (en) * | 2020-03-08 | 2021-10-12 | 西南交通大学 | Reaction device for preparing graphene and method for preparing graphene |
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