CN102181843A - Polycrystalline graphene film preparation technique, transparent electrode and preparation of graphene-base device - Google Patents
Polycrystalline graphene film preparation technique, transparent electrode and preparation of graphene-base device Download PDFInfo
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- CN102181843A CN102181843A CN 201110096788 CN201110096788A CN102181843A CN 102181843 A CN102181843 A CN 102181843A CN 201110096788 CN201110096788 CN 201110096788 CN 201110096788 A CN201110096788 A CN 201110096788A CN 102181843 A CN102181843 A CN 102181843A
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Abstract
The invention discloses a polycrystalline graphene film and a preparation technique thereof, and preparation methods of a transparent electrode and an electronic device based on the polycrystalline graphene film. The invention overcomes the defect of high brittleness in the transparent oxide and the defect of low conductivity in the flexible conducting polymer film, is hopeful to become a novel flexible transparent conducting film, and has application potential in organic electroluminescent displays, organic electric storages, organic solar batteries and other photoelectric functional devices.
Description
Technical field
The invention describes the technology of a kind of polycrystalline graphite alkene film, preparation polycrystalline graphite alkene film and based on the transparency electrode of polycrystalline graphite alkene film and the method for electron device.
Background technology
The strong K sea nurse of the peace moral of Britain Univ Manchester UK in 2004 (Andre K. Geim) etc. has been prepared Graphene, and therefore obtained Nobel Prize in physics in 2010, from being found to the acquisition Nobel Prize in physics, only used the only time in 6 years.Graphene has just caused global research boom since coming out.It is having remarkable mechanical property, is the thinnest a kind of in the known materials, and is the most firm hard; Good electric property is arranged, and the speed of at room temperature transmitting electronics is that known conductor kind is the fastest; The structure that also has very special atomic scale can only could be described with relativistic quantum mechanics.
The method for preparing at present Graphene mainly contains following several: the micromechanics partition method, the epitaxy method, heating SiC method, the method for chemical vapour deposition (CVD), and the growth thickness of the control Graphene that the method for use chemical vapour deposition can be held very much and the size of graphene film.Next graphene film is transferred to the graphene film for preparing on other the insulating substrate after preparation on the sheet metal is finished exactly, further processes according to the demand of reality then.In the production of reality, need to use large-area graphene film, yet the preparation of large-area polycrystalline graphite alkene film is very difficult, therefore, needs large-area polycrystalline graphite alkene film and based on the transparency electrode and the electron device of polycrystalline graphite film.
Summary of the invention
A kind of polycrystalline graphite alkene film is disclosed.
The technology of preparation polycrystalline graphite alkene film is also disclosed.
In addition, a kind of transparency electrode and electron device based on polycrystalline graphite alkene film also disclosed.
In case study on implementation, a kind of polycrystalline graphite alkene film is provided, polycrystalline graphite alkene film is meant the continuous film of being made up of the single crystal graphite alkene with identical crystalline phase or different crystalline phases.Wherein, single crystal graphite alkene is meant the structure of the bi-dimensional cellular shape that the planar array by the carbon atom that is combined into hexagonal structure forms.
Polycrystalline graphite alkene film comprises the number of plies between 1 layer to about 300 layers, and Raman D peak intensity compares smaller or equal to about 0.3 with the peak of Raman G peak intensity.
The peak ratio of Raman D band/Raman G band strength can be 0.
The width of polycrystalline graphite alkene film and length can be greatly between the extremely about 3000mm of 1mm.
According to another embodiment, a kind of method for preparing polycrystalline graphite alkene sheet film is provided, described method comprises: form Catalytic Layer, Catalytic Layer comprises monocrystalline or polycrystalline graphite metal catalytic layer; Be arranged on carbonaceous material on the Catalytic Layer or incorporate Catalytic Layer; At least a middle thermal treatment catalyst layer and carbonaceous material in inert atmosphere and reducing atmosphere.
Be exactly to adopt chemical gaseous phase depositing process concretely, the carbon atom in the gaseous carbon sources is grown on the Catalytic Layer.Can by with carbonaceous gas by Pintsch process or at a certain temperature by microwave-assisted cracked method deposition or be dissolved into Catalytic Layer.
Wherein gaseous carbon sources comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, gaseous constituent in the organism such as steroide or any carbonaceous gas are as by carbon monoxide, ethane, ethene, ethanol, methane, acetylene, propane, propylene, butane, divinyl, pentane, amylene, cyclopentadiene, hexane, hexanaphthene, benzene, toluene and comprise the gas of selecting in the group that at least a combination in the aforementioned gas forms.Comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
Wherein Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC etc.Comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
Method by thermal treatment, fast cooling prepares the large-area polycrystalline graphene film.
Wherein the anti-method of thermal treatment has: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.
Wherein the ambient pressure during thermal treatment is 10
-10Pa-10
7Between the pa
Wherein the method for fast cooling has: the naturally cooling cooling, remove cooling method of thermal source fast cooling and contact or the like.
Wherein Jiang Wen speed is at 0.1 ℃/min-300 ℃/min.
Heat treatment period and temperature range: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.
Described method can also comprise by using the sour Catalytic Layer of polycrystalline graphite alkene film is handled to remove Catalytic Layer after thermal treatment, so that polycrystalline graphite alkene film is separated with Catalytic Layer.
According to another embodiment of the present invention, adopt the method for physics, the carbon atom in gaseous carbon sources, liquid carbon source or the solid carbon source is grown on the Catalytic Layer.
Wherein the method for physics has: hot evaporation, sputter, electron beam deposition, laser deposition or plasma deposition.
Wherein gaseous carbon sources comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, gaseous constituent in the organism such as steroide or any carbonaceous gas are as by carbon monoxide, ethane, ethene, ethanol, acetylene, methane, propane, propylene, butane, divinyl, pentane, amylene, cyclopentadiene, hexane, hexanaphthene, benzene, toluene and comprise the gas of selecting in the group that at least a combination in the aforementioned gas forms.Comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
Wherein the liquid carbon source comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, liquid in the organism such as steroide or all carbonaceous organism that exists with SOLUTION PROPERTIES, the mixture of the arbitrary combination of inorganics and carbonaceous material thereof.
Wherein solid carbon source comprises: graphite, agraphitic carbon, diamond, soccerballene or carbon nanotube etc.
Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC etc.Comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
And prepare the large-area polycrystalline graphene film by the method for thermal treatment, fast cooling.
Wherein the anti-method of thermal treatment has: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.
Wherein the ambient pressure during thermal treatment is 10
-10Pa-10
7Between the pa
Wherein the method for fast cooling has: the naturally cooling cooling, remove cooling method of thermal source fast cooling and contact or the like.
Wherein Jiang Wen speed is at 0.1 ℃/min-300 ℃/min.
Heat treatment period and temperature range: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.
Described method can also comprise by using acid that polycrystalline graphite alkene film and Catalytic Layer are handled after thermal treatment and remove Catalytic Layer, with polycrystalline graphite alkene film and Catalytic Layer separately.
According to another embodiment of the present invention, immerse Catalytic Layer in the carbonaceous solution or smear carbonaceous organism, thereby make and cover the carbonaceous film of one deck above the Catalytic Layer.
Wherein carbonaceous solution or smear carbonaceous organic material and be meant: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, steroide etc.Comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
Wherein Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC etc.Comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
Method by thermal treatment, fast cooling prepares the large-area polycrystalline graphene film.
Wherein the anti-method of thermal treatment has: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.Carry out thermal treatment by at least a combination that comprises in the aforesaid heating means, and without limits.
Wherein the ambient pressure during thermal treatment is 10
-10Pa-10
7Between the pa
Wherein the method for fast cooling has: the naturally cooling cooling, remove cooling method of thermal source fast cooling and contact or the like.
Wherein Jiang Wen speed is at 0.1 ℃/min-300 ℃/min.
Heat treatment period and temperature range: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.
Described method can also comprise by using acid that polycrystalline graphite film and Catalytic Layer are handled after thermal treatment and removes Catalytic Layer, so that polycrystalline graphite alkene film is separated with Catalytic Layer.
According to another embodiment of the present invention, provide a kind of transparency electrode and electron device that comprises described polycrystalline graphite alkene film.Transparency electrode can shift on flexible substrates or rigid basement.
Description of drawings
By above describing in further detail with reference to the accompanying drawings with other aspect, the exemplary embodiment of feature and advantage, top aspect, feature and advantage with other become more obvious, in the accompanying drawing,
Fig. 1 schematically shows the technology for preparing polycrystalline graphite alkene film according to chemical gaseous phase depositing process;
Fig. 2 schematically shows the technology for preparing polycrystalline graphite alkene film according to physical method;
Fig. 3 schematically shows by Catalytic Layer and immerses in the carbonaceous solution or smear the technology that carbonaceous organic method prepares polycrystalline graphite alkene film;
Fig. 4 schematically shows the Raman spectral curve according to the polycrystalline graphite alkene film of example 1 preparation;
Fig. 5 schematically shows the SEM image according to the polycrystalline graphite alkene film of example 1 preparation.
Fig. 6 schematically shows the transparency electrode according to the polycrystalline graphite alkene film for preparing based on example 1.
Fig. 7 provides is the transmittance of the transparency electrode that become by the film preparation of polycrystalline graphite alkene.
Specific embodiments
Hereinafter, will describe more fully with reference to the accompanying drawing that shows example embodiment is embodiment.
Fig. 1 adopts chemical gaseous phase depositing process, the carbon atom in the gaseous carbon sources is grown on the Catalytic Layer, can by with carbonaceous gas by Pintsch process or at a certain temperature by microwave-assisted cracked method deposition or be dissolved into Catalytic Layer.And prepare the large-area polycrystalline graphene film by the method for thermal treatment, fast cooling.
Wherein gaseous carbon sources comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, gaseous constituent in the organism such as steroide or any carbonaceous gas are as by carbon monoxide, ethane, ethene, ethanol, acetylene, methane, propane, propylene, butane, divinyl, pentane, amylene, cyclopentadiene, hexane, hexanaphthene, benzene, toluene and comprise the gas of selecting in the group that at least a combination in the aforementioned gas forms.Comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
Wherein Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC etc.Comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
Wherein the anti-method of thermal treatment has: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.Perhaps carry out thermal treatment by at least a combination that comprises in the aforesaid heating means, and without limits.Specifically, can or utilize resistance furnace optionally to heat catalyst by radiation heating so that the gaseous carbon sources Pintsch process finally Catalytic Layer on the graphite alkylene.Therefore, grade, realize control polycrystalline graphite alkene film thickness by the gas flow or the gas group of pilot-gas carbon source in the reaction chamber of Catalytic Layer.By thermal treatment, from the carbon atom of carbonaceous material covalent attachment each other, like this by the time after the cooling of foregoing method, on Catalytic Layer, carbon atom can form the plane hexagonal structure to form polycrystalline graphite alkene film.
Wherein the ambient pressure during thermal treatment is 10
-10Pa-10
7Between the pa.The concrete growth air pressure of the polycrystalline graphite alkene film of giving in this example concretely, is 10
5Pa-10
6Between the pa, be in being slightly larger than the gaseous fraction that has shielding gas and reductibility composition of a standard atmospheric pressure, to grow more specifically.
In the technical examples that this method provides, the gaseous carbon sources of using is methane, and shielding gas is an argon gas, and reductive agent is a hydrogen.Wherein the ratio of all gases component is about argon gas: hydrogen: gas methane=400:30:15.
Heat treatment period and temperature range: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.Carry out under the temperature between about more specifically 500 to about 1800 or under the temperature between about 600 to about 1700.When temperature is lower than approximately 300 the time, can not carry out greying fully.On the other hand, when temperature be higher than about 2000 the time carbon can be evaporated.Thermal treatment about 0.001 hour to about 1000 hours, about 0.01 hour to about 50 hours, or about 0.1 hour to about 5 hours.When heat treatment time less than about 0.001 hour between greater than about 1000 hours the time, greying is insufficient, perhaps efficient can reduce.
Can in the thermal treatment first time, carbonaceous material be decomposed,, and form soluble solids in the Catalytic Layer of carbon infiltration with formation carbon by Catalytic Layer.Then, the carbon that is solid-solubilized in the Catalytic Layer can form individual layer or multiwalled polycrystalline graphite alkene film with the surface in Catalytic Layer in the thermal treatment second time under the temperature of the molten limit that is lower than Catalytic Layer.Can be independent, side by side or according to priority carry out thermal treatment for the first time or thermal treatment for the second time, can in inert atmosphere or reducing atmosphere, carry out thermal treatment for the first time and thermal treatment for the second time.
Wherein the method for fast cooling has: the naturally cooling cooling, remove cooling method of thermal source fast cooling and contact or the like.
Wherein Jiang Wen speed is at 0.1 ℃/min-300 ℃/min.About 0.1 ℃ of Jiang Wen speed/min-100 ℃/min more specifically, perhaps 0.1 ℃/min-10 ℃/min.When the speed of cooling during, can not guarantee to obtain polycrystalline graphite alkene film preferably less than about 0.1 ℃/min or greater than about 300 ℃/min.
Described method can also comprise by using acid that polycrystalline graphite alkene film and Catalytic Layer are handled after thermal treatment and removes Catalytic Layer, so that polycrystalline graphite alkene film is separated with Catalytic Layer.
Fig. 2 is the technology that physical method prepares polycrystalline graphite alkene film
Adopt the method for physics, the carbon atom in gaseous carbon sources, liquid carbon source or the solid carbon source is grown on the Catalytic Layer.
Wherein the method for physics has: hot evaporation, sputter, electron beam deposition, laser deposition or plasma deposition.
Wherein gaseous carbon sources comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, gaseous constituent in the organism such as steroide or any carbonaceous gas are as by carbon monoxide, ethane, ethene, ethanol, acetylene, methane, propane, propylene, butane, divinyl, pentane, amylene, cyclopentadiene, hexane, hexanaphthene, benzene, toluene and comprise the gas of selecting in the group that at least a combination in the aforementioned gas forms.Comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
Wherein the liquid carbon source comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, liquid in the organism such as steroide or all carbonaceous organism that exists with SOLUTION PROPERTIES, the mixture of the arbitrary combination of inorganics and carbonaceous material thereof.
Wherein solid carbon source comprises: graphite, agraphitic carbon, diamond, soccerballene or carbon nanotube etc.
Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC etc.Comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
And prepare the large-area polycrystalline graphene film by the method for thermal treatment, fast cooling.
Wherein the anti-method of thermal treatment has: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.Perhaps carry out thermal treatment by at least a combination that comprises in the aforesaid heating means, and without limits.Specifically, can or utilize resistance furnace optionally to heat catalyst by radiation heating so that the gaseous carbon sources Pintsch process finally Catalytic Layer on the graphite alkylene.Therefore, grade, realize control polycrystalline graphite alkene film thickness by the gas flow or the gas group of pilot-gas carbon source in the reaction chamber of Catalytic Layer.By thermal treatment, from the carbon atom of carbonaceous material covalent attachment each other, like this by the time after the cooling of foregoing method, on Catalytic Layer, carbon atom can form the plane hexagonal structure to form polycrystalline graphite alkene film.
Wherein the ambient pressure during thermal treatment is 10
-10Pa-10
7Between the pa
Heat treatment period and temperature range: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.Carry out under the temperature between about more specifically 500 to about 1800 or under the temperature between about 600 to about 1700.When temperature is lower than approximately 300 the time, can not carry out greying fully.On the other hand, when temperature be higher than about 2000 the time carbon can be evaporated.Thermal treatment about 0.001 hour to about 1000 hours, about 0.01 hour to about 50 hours, or about 0.1 hour to about 5 hours.When heat treatment time less than about 0.001 hour between greater than about 1000 hours the time, greying is insufficient, perhaps efficient can reduce.
Can in the thermal treatment first time, carbonaceous material be decomposed,, and form soluble solids in the Catalytic Layer of carbon infiltration with formation carbon by Catalytic Layer.Then, the carbon that is solid-solubilized in the Catalytic Layer can form individual layer or multiwalled polycrystalline graphite alkene film with the surface in Catalytic Layer in the thermal treatment second time under the temperature of the molten limit that is lower than Catalytic Layer.Can be independent, side by side or according to priority carry out thermal treatment for the first time or thermal treatment for the second time, can in inert atmosphere or reducing atmosphere, carry out thermal treatment for the first time and thermal treatment for the second time.
Wherein the method for fast cooling has: the naturally cooling cooling, remove cooling method of thermal source fast cooling and contact or the like.
Wherein Jiang Wen speed is at 0.1 ℃/min-300 ℃/min.About 0.1 ℃ of Jiang Wen speed/min-100 ℃/min more specifically, perhaps 0.1 ℃/min-10 ℃/min.When the speed of cooling during, can not guarantee to obtain polycrystalline graphite alkene film preferably less than about 0.1 ℃/min or greater than about 300 ℃/min.
Described method can also comprise by using acid that polycrystalline graphite alkene film and Catalytic Layer are handled after thermal treatment and removes Catalytic Layer, so that polycrystalline graphite alkene film is separated with Catalytic Layer.
Fig. 3 immerses Catalytic Layer in the carbonaceous solution or smears carbonaceous organism, thereby makes the carbonaceous film of covering one deck above the Catalytic Layer.
Wherein carbonaceous solution or smear carbonaceous organic material and be meant: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, steroide etc.Comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
Wherein Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC etc.Comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
Method by thermal treatment, fast cooling prepares the large-area polycrystalline graphene film.
Wherein the anti-method of thermal treatment has: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.Carry out thermal treatment by at least a combination that comprises in the aforesaid heating means, and without limits.Specifically, can or utilize resistance furnace optionally to heat catalyst by radiation heating, with startup be coated with carbonaceous organism or any material containing carbon Catalytic Layer on the graphite alkylene.Therefore, by control thickness or the dosage that carbonaceous organism or any material containing carbon distribute on Catalytic Layer, realize control to polycrystalline graphite alkene film thickness.By thermal treatment, from the carbon atom of carbonaceous material covalent attachment each other, like this by the time after the cooling of foregoing method, on Catalytic Layer, carbon atom can form the plane hexagonal structure to form polycrystalline graphite alkene film.
Wherein the ambient pressure during thermal treatment is 10
-10Pa-10
7Between the pa.
Heat treatment period and temperature range: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.Carry out under the temperature between about more specifically 500 to about 1800 or under the temperature between about 600 to about 1700.When temperature is lower than approximately 300 the time, can not carry out greying fully.On the other hand, when temperature be higher than about 2000 the time carbon can be evaporated.Thermal treatment about 0.001 hour to about 1000 hours, about 0.01 hour to about 50 hours, or about 0.1 hour to about 5 hours.When heat treatment time less than about 0.001 hour between greater than about 1000 hours the time, greying is insufficient, perhaps efficient can reduce.
Can in the thermal treatment first time, carbonaceous material be decomposed,, and form soluble solids in the Catalytic Layer of carbon infiltration with formation carbon by Catalytic Layer.Then, the carbon that is solid-solubilized in the Catalytic Layer can form individual layer or multiwalled polycrystalline graphite alkene film with the surface in Catalytic Layer in the thermal treatment second time under the temperature of the molten limit that is lower than Catalytic Layer.Can be independent, side by side or according to priority carry out thermal treatment for the first time or thermal treatment for the second time, can in inert atmosphere or reducing atmosphere, carry out thermal treatment for the first time and thermal treatment for the second time.
Wherein the method for fast cooling has: the naturally cooling cooling, remove cooling method of thermal source fast cooling and contact or the like.
Wherein Jiang Wen speed is at 0.1 ℃/min-300 ℃/min.About 0.1 ℃ of Jiang Wen speed/min-100 ℃/min more specifically, perhaps 0.1 ℃/min-10 ℃/min.When the speed of cooling during, can not guarantee to obtain polycrystalline graphite alkene film preferably less than about 0.1 ℃/min or greater than about 300 ℃/min.
Described method can also comprise by using acid that polycrystalline graphite alkene film and Catalytic Layer are handled after thermal treatment and removes Catalytic Layer, so that polycrystalline graphite alkene film is separated with Catalytic Layer.
Fig. 4 is by the Raman spectral curve of the polycrystalline graphite alkene film of chemical Vapor deposition process preparation.
Can use Raman spectrum to discern thickness, specifically, determine the thickness of polycrystalline graphite alkene film by the ratio of G peak and 2D peak intensity by polycrystalline graphite alkene film.The G peak in the Raman spectrum of the Graphene that provides and the ratio of 2D peak intensity are about 0.3, and the zone of Raman spectrum representative is the graphene film of individual layer.
Discern by what polycrystalline structure caused by the existence at D peak and to be formed on lacking on the graphene film.D peak in the Raman spectrum is represented to have defective in the Graphene, and the D peak get intensity be considered to Graphene in the quantity of defective proportional.D peak in the Raman spectrum of the Graphene that provides is very weak, and the defective that shows the graphene film in this zone seldom is of high quality.
Fig. 5 is by the SEM figure of the polycrystalline graphite alkene film of chemical Vapor deposition process preparation.
Can use SEM to discern by polycrystalline graphite alkene film, specifically, the fold by graphene film and the pattern of crystal boundary are determined the thickness or the quality of polycrystalline graphite alkene film.
What Fig. 6 provided is the transparency electrode that is become by the film preparation of polycrystalline graphite alkene.
The surface resistivity that records this transparency electrode is about 190 Ω/.
Fig. 7 provides is the transmittance of the transparency electrode that become by the film preparation of polycrystalline graphite alkene.
Claims (18)
1. the preparation method of a polycrystalline graphite alkene film is characterized in that adopting chemical vapour deposition or physical method that carbon atom is discharged from gas (liquid) or solid carbon source and is grown in Catalytic Layer and forms polycrystalline graphite alkene film.
2. polycrystalline graphite alkene film as claimed in claim 1 is meant the continuous film of being made up of the single crystal graphite alkene with identical crystalline phase or different crystalline phases, it is characterized in that single crystal graphite alkene is meant the structure of the bi-dimensional cellular shape that the planar array by the carbon atom that is combined into hexagonal structure forms.
3. polycrystalline graphite alkene film as claimed in claim 1 is characterized in that polycrystalline graphite alkene film comprises the layer of the number of plies between about 1 layer to 300 layers.
4. polycrystalline graphite alkene film as claimed in claim 1 is characterized in that the width of polycrystalline graphite alkene film and length are all between 1mm to 3000mm.
5. polycrystalline graphite alkene film as claimed in claim 1, the size that it is characterized in that contained single crystal particle in the polycrystalline graphite alkene film is between 1nm-1000 m.
6. the preparation method's of a polycrystalline graphite alkene film detailed process:
(1) adopts chemical gaseous phase depositing process, the carbon atom in the gaseous carbon sources is grown on the Catalytic Layer, and prepares the large-area polycrystalline graphene film by the method for thermal treatment, fast cooling;
(2) method of employing physics is grown in the carbon atom in gaseous carbon sources, liquid carbon source or the solid carbon source on the Catalytic Layer, and prepares the large-area polycrystalline graphene film by the method for thermal treatment, fast cooling; (3) Catalytic Layer is immersed in the carbonaceous solution or smear carbonaceous organism, thereby cover the carbonaceous film of one deck above the Catalytic Layer that is, the method by thermal treatment, fast cooling prepares the large-area polycrystalline graphene film.
7. method as claimed in claim 6 is characterized in that gaseous carbon sources comprises: all carbonaceous gases are concretely by carbon monoxide, ethane, ethene, ethanol, acetylene, propane, propylene, butane, divinyl, pentane, methane, amylene, cyclopentadiene, hexane, hexanaphthene, benzene, toluene and comprise the gas of selecting in the group that at least a combination in the aforementioned gas forms.
8. method as claimed in claim 6 is characterized in that the liquid carbon source comprises: the mixture of the arbitrary combination of all carbonaceous organism, inorganics and carbonaceous materials thereof that exist with SOLUTION PROPERTIES.
9. method as claimed in claim 6 is characterized in that solid carbon source comprises: graphite, agraphitic carbon, diamond, soccerballene or carbon nanotube.
10. method as claimed in claim 6, it is characterized in that carbonaceous organic material comprises: alkane, naphthenic hydrocarbon, alkene, alkynes, aromatic hydrocarbons, alcohol phenol, ether, aldehyde ketone, carboxylic phenol, the carboxylic amphyl, unsaturated carboxylic acid and substituted carboxylic acid, amine, nitro-compound, diazonium compound, aromatic diazonium salt, azo-compound, triazo-compound, sulfocompound, P contained compound, silicoorganic compound, the pyrroles, furans and thiophene, indoles, contain heteroatomic five-membered ring more than two, pyridine, quinoline and isoquinoline 99.9, oxygen containing hexa-member heterocycle, the hexa-member heterocycle that contains two above nitrogen heteroatoms, monose, oligose, polysaccharide, the acid of ammonia stem, polypeptide, protein, nucleic acid, lipoidis, terpenoid, steroides etc. comprise at least a combination in the aforementioned organism and comprise aforementioned organic one or more combination.
11. method as claimed in claim 6 is characterized in that Catalytic Layer comprises: from by Ni. Co. Fe. Pt. Au. Al. Cr. Cu .Mg. Mn. Mo. Rh. Si. Ta. Ti. W. U. V. Zr.TiC.Rc.Hfc.LaB
6.SiO
2.Al
2O
3.SiC, comprise at least a combination in aforementioned metal or the compound and comprise aforementioned metal or compound at least a alloy composition Catalytic Layer.
12. method as claimed in claim 6, the ambient pressure when it is characterized in that thermal treatment is 10
-10Pa-10
7Between the pa.
13. method as claimed in claim 6 is characterized in that physical method comprises: hot evaporation, sputter, electron beam deposition, laser deposition or plasma deposition.
14. method as claimed in claim 6 is characterized in that the method that heats comprises: infrared heating, electromagnetism heating, microwave heating, resistance furnace, induction heating, radiation heating, laser, plasma body, surface phasmon or the like.
15. method as claimed in claim 6 is characterized in that thermal treatment temp and time comprises: carry out time between the thermal treatment 0.001 hour to 1000 hours in the temperature between 300 ° of C to 2000 ° of C.
16. method as claimed in claim 6 is characterized in that fast cooling comprises: 0.1 ℃/min-300 ℃/min, wherein newspaper is drawn together and is directly gone out and use contact process to reduce thermal source to reduce heat source temperature fast.
17. want 6 described methods as right, it is characterized in that also comprising by after thermal treatment, using acid that polycrystalline graphite alkene sheet film Catalytic Layer is handled removing Catalytic Layer, and this method obtain the transparency electrode of polycrystalline graphite alkene film.
18. want the transparency electrode of the polycrystalline graphite alkene film of 6 described methods preparation as right, it is characterized in that parameter is: the transmittance of polycrystalline graphite alkene film is between 60 ℅-98 ℅, and electric conductivity is between 1 Ω/-5000 Ω/.
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