CN103848416A - Method of modifying graphene film - Google Patents
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- CN103848416A CN103848416A CN201210501642.0A CN201210501642A CN103848416A CN 103848416 A CN103848416 A CN 103848416A CN 201210501642 A CN201210501642 A CN 201210501642A CN 103848416 A CN103848416 A CN 103848416A
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Abstract
The invention provides a method of modifying a graphene film. A metal lining exposed at the domain boundary and flaws of the graphene film is utilized to reduce metal ions in a metal ion solution to obtain metal nanoparticles, thus achieving selective doping modification of the graphene film. Transfer of the doped modified graphene film is achieved by corrosion and transfer processes. According to the method, the metal lining obtained by graphene film growth is adopted as a reductant to reduce the metal ions in the solution without the need of adding a new reductant, thus achieving selective doping modification of the graphene film and avoiding deposition of metal nanoparticles on the complete surface of the graphene film. The method is high in repeatability and is simple, feasible and capable of modifying the graphene film in large scale. The method can accurately calibrate the shape and the size of single crystal domains in a graphene continuous film and can qualitatively improve the electrical performances of the graphene film by changing the concentration of the metal ion solution and the contacting time of the solution with the metal lining.
Description
Technical field
The invention belongs to graphene film materials processing technology field, relate to a kind of method of grapheme modified film.
Background technology
Graphene, claim again mono-layer graphite, the hexagon cellular shape Two-dimensional Inorganic crystalline material being made up of the carbon atom of sp2 hydridization, only has a carbon atomic layer, thickness only has 0.335nm(A. K. Geim, K. S. Novoselov, Nature Materials, 2007,6,183-191), be at present in the world the thinnest nano material, be also the material of the intensity maximum measured up to now.
Graphene possesses a lot of superior performance, for example high electron mobility, high current density, high mechanical strength etc. in theory.Just because of these characteristics, it is acknowledged as manufactures transparent conductive film, high-frequency transistor, hydrogen storage battery, and even the ideal material of unicircuit, has wide market application foreground.
Complete Graphene is made up of multiple domains, but can there is defect in the intersection of the especially adjacent domain in Graphene domain inside of actual preparation, also can be because a variety of causes is introduced defect in subsequent transfer process, these factors have reduced the electrical properties of Graphene to a great extent, need to make up by adulterating method.
The people such as Kim (Ki Kang Kim, Alfonso Reina, Yumeng Shi, Hyesung Park, Lain-Jong Li, Young Hee Lee and Jing Kong, Nanotechnology 2010,21,285205 etc.) adopt nano metal particles to carry out doping research to graphene film, they first transfer to the graphene film of growing in metal substrate in insulating substrate, then make to contact with metal ion solution with the Graphene of insulating substrate, then the spontaneous reduction of metal ion under the effect of solvent, generates nano metal particles and is deposited on Graphene surface.The random Graphene surface that is dispersed in of metal nanoparticle that this method obtains, instead of be optionally entrained in the position of Graphene domain border and defect, thereby the raising of electrical properties to Graphene has certain limitation, but also can introduce surface state on complete Graphene single crystal domains surface, affect the character of grapheme material.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of method of grapheme modified film, the raising of the electrical properties to Graphene when solving the grapheme modified film of prior art has certain limitation and can introduce on complete graphene film single crystal domains surface the problem of surface state.
For achieving the above object and other relevant objects, the invention provides a kind of method of grapheme modified film, described method at least comprises the following steps:
1) metal ion solution is contacted with the graphene film being formed in metal substrate, then dry up described graphene film and metal substrate, obtain being formed on the graphene film in metal substrate and through modifying;
2) on the graphene film obtaining, form organic glue-line after step 1);
3) utilize corrosive fluid to remove described metal substrate, obtain the combination of the graphene film of organic glue-line and process modification;
4) described combination is transferred in target substrate, then removes described organic glue-line, obtain being formed on graphene film in target substrate and through modifying.
Alternatively, be 0.1 ~ 60min the duration of contact in described step 1).
Alternatively, described metal ion solution at least comprises a kind of or several arbitrarily in Ag, Pt, Au metal ion.
Alternatively, described metal substrate at least comprises a kind of or any several alloy in Fe, Co, Ni, Mo, Cu.
Alternatively, described step 2) in form organic glue-line on graphene film surface concrete steps be: first, at the organic glue-line of described graphene film surface spin coating, then under 150 ~ 190 DEG C of conditions, dry.
Alternatively, described organic glue-line at least comprises polymethylmethacrylate or polydimethylsiloxane.
Alternatively, described corrosive fluid at least comprises HNO
3, dense H
2sO
4, FeCl
3, Fe (NO
3)
3, (NH
4)
2s
2o
8or KNO
3in one.
Alternatively, described target substrate at least comprises the one in deielectric-coating, glass, sapphire, PET film or semiconductor material.
Alternatively, in described step 4), shifting described combination to the concrete steps of target substrate is: first in target substrate, make described graphene film and target substrate surface be close together described combination uniform spreading, then under 50 ~ 120 DEG C of conditions, dry.
Alternatively, in affiliated step 4), adopt the organic glue-line described in removal of solvents that removes photoresist, wherein, described in the solvent that removes photoresist at least comprise the one in chloroform, acetic acid, ethyl acetate or acetone.
As mentioned above, the method for a kind of grapheme modified film of the present invention, has following beneficial effect:
First the present invention utilizes in the metal substrate of the domain border of graphene film and fault location exposure the metal ion in metal ion solution is reduced, domain border and fault location at graphene film generate metal nanoparticle, and can not make metal nanoparticle be modified at flawless position, thereby graphene film is realized to selective doping to be modified, and then reach better modification effect, then by corrosion and shifting process, the good graphene film of doping and modification is realized and being shifted, in other words, the present invention shifts after to the first doping and modification of graphene film.The present invention utilizes the metal substrate material of graphene film growth as reductive agent, the metal ion in solution to be reduced, and do not need to introduce new reductive agent, in having realized the grapheme modified film of selective doping, avoid the deposition of metal nanoparticle on complete graphene film surface like this.Repeatability of the present invention is high, simple, can grapheme modified film in enormous quantities; Meanwhile, the present invention can accurate calibration Graphene continuous film in the shape and size of single crystal domains, and can by change metal ion solution concentration and with metal substrate duration of contact qualitative raising graphene film electric property.
Brief description of the drawings
Fig. 1 is shown as the schema of the method for a kind of grapheme modified film of the present invention.
The method that Fig. 2 is shown as a kind of grapheme modified film of the present invention in embodiment mono-through the continuous graphite alkene film transfer of doping and modification to the optical microscope photograph after target substrate.
Method discontinuous graphene film through doping and modification in embodiment bis-that Fig. 3 a and Fig. 3 b are shown as a kind of grapheme modified film of the present invention is transferred to the optical microscope photograph after target substrate.
Embodiment
Below, by specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification sheets.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Refer to Fig. 1 to Fig. 3 b.It should be noted that, the diagram providing in the present embodiment only illustrates basic conception of the present invention in a schematic way, satisfy and only show with assembly relevant in the present invention in graphic but not component count, shape and size drafting while implementing according to reality, when its actual enforcement, kenel, quantity and the ratio of each assembly can be a kind of random change, and its assembly layout kenel also may be more complicated.
In prior art when grapheme modified film, the random graphene film surface that is dispersed in of metal nanoparticle that metal ion solution restores, instead of be optionally entrained in the position of graphene film domain border and defect, thereby the raising of electrical properties to Graphene has certain limitation, but also can introduce surface state on complete graphene film single crystal domains surface, affect the character of grapheme material.
In view of this, the invention provides a kind of method of grapheme modified film, first utilize the metal substrate exposing at domain border and the fault location of graphene film to reduce to the metal ion in metal ion solution, domain border and fault location at graphene film generate metal nanoparticle, and can not make metal nanoparticle be modified at flawless position, thereby graphene film is realized to selective doping to be modified, and then reach better modification effect, then by corrosion and shifting process, the good graphene film of doping and modification is realized and being shifted, in other words, the present invention shifts after to the first doping and modification of graphene film.The present invention utilizes the metal substrate material of graphene film growth as reductive agent, the metal ion in solution to be reduced, and do not need to introduce new reductive agent, in having realized the grapheme modified film of selective doping, avoid the deposition of metal nanoparticle on complete graphene film surface like this.Repeatability of the present invention is high, simple, can grapheme modified film in enormous quantities; Meanwhile, the shape and size that the present invention can accurate calibration graphene film single crystal domains, and can by change metal ion solution concentration and with metal substrate duration of contact qualitative raising graphene film electric property.By elaborating the embodiment of method of a kind of grapheme modified film of the present invention, make those skilled in the art not need creative work can understand the method for a kind of grapheme modified film of the present invention below.
Embodiment mono-
Refer to Fig. 1 to Fig. 2, the invention provides a kind of method of grapheme modified film, described method at least comprises the following steps:
First perform step 1), metal ion solution is contacted with the graphene film being formed in metal substrate, then dry up described graphene film and metal substrate, obtain being formed on the graphene film in metal substrate and through modifying.Wherein, be 0.1 ~ 60min the duration of contact in described step 1); Described metal ion solution at least comprises a kind of or several arbitrarily in Ag, Pt, Au metal ion; Described metal substrate at least comprises a kind of or any several alloy in Fe, Co, Ni, Mo, Cu; The form of described metal substrate is paper tinsel shape, sheet, bulk, plated film or molten state.
It should be noted that, the graphene film being formed in metal substrate in described step 1) is prepared by ordinary method.Preparation method is prepared by vapor phase process, liquid phase method or solid phase method particularly, and wherein to prepare graphene film the most general for vapor phase process.Described vapor phase process comprises chemical Vapor deposition process, plasma reinforced chemical vapour deposition method, flame method or arc discharge method; Wherein, the carbon source passing into while preparing described graphene film is gaseous state, liquid state or solid-state carbon source, while preparing described graphene film, can, at low pressure or normal pressure, under low temperature or hot conditions, carry out.In the present embodiment one, copper (Cu) paper tinsel metal substrate is put into the reaction chamber of chemical gas-phase deposition system, at higher temperature, pass into a certain amount of carbon source and protection gas, on Copper Foil, growth obtains graphene film.
What need to further illustrate is, in execution step 1) also need before first to configure described metal ion solution, be specially: get a certain amount of containing in the metallic compound of Ag, Pt or Au any one or several arbitrarily, be dissolved in the water or other solvent of certain volume, thereby form metal ion solution.In the present embodiment one, described metal ion solution is platinum acid chloride solution (H
2ptCl
6), specific configuration process is: claim 1g solid Platinic chloride, get 5ml hydrochloric acid, be dissolved in 1000ml water, the platinum acid chloride solution obtaining is placed on low-temperature dark in brown bottle and preserves.
Particularly, in the present embodiment one, step 1) is: under normal temperature, platinum acid chloride solution is evenly dropped in the copper substrate that is formed with graphene film, place after 1min, dry up described graphene film and copper substrate by nitrogen gun, obtain being formed on the graphene film in copper substrate and through modifying.
According to chemical equation: H
2ptCl
6+ Cu → Pt+CuCl
2+ H
2↑ known, platinum ion in Platinic chloride is formed pt atom (being nano platinum particle) in the exposed part of copper substrate (being domain border and the fault location of graphene film) by copper reduction, this nano platinum particle is gathered in domain border and the fault location (referring to 1. indication part of arrow in Fig. 2) of graphene film, thereby graphene film is carried out to optionally doping and modification.It is to be noted, the present invention utilizes the metal substrate material of graphene film growth as reductive agent, the metal ion in solution to be reduced, and do not need to introduce new reductive agent, in having realized the grapheme modified film of selective doping, avoid the deposition of metal nanoparticle on complete graphene film surface like this.Meanwhile, the domain border and the fault location that optionally metal nanoparticle are modified at due to the present invention, therefore can accurate calibration Graphene continuous film in the shape and size of single crystal domains.Then perform step 2).
Step 2) in, on the graphene film obtaining, form organic glue-line after step 1).Wherein, the concrete steps that form organic glue-line are: first, at the organic glue-line of described graphene film surface spin coating, then under 150 ~ 190 DEG C of conditions, dry; Described organic glue-line at least comprises polymethylmethacrylate (PMMA) or polydimethylsiloxane (PDMS).
Particularly, in the present embodiment one, step 2) be: suck being formed with the copper substrate of graphene film through modifying and being put on the pallet of sol evenning machine, drip several PMMA on described graphene film surface, rotation 6000rpm, PMMA layer (organic glue-line) thickness that makes to be formed on described graphene film surface is about 200nm, then it is toasted to 3min under 180 DEG C of temperature condition and dries.Then perform step 3).
In step 3), utilize corrosive fluid to remove described metal substrate, obtain the combination of the graphene film of organic glue-line and process modification.Wherein, described corrosive fluid at least comprises HNO
3, dense H
2sO
4, FeCl
3, Fe (NO
3)
3, (NH
4)
2s
2o
8or KNO
3in one.Particularly, in the present embodiment one, graphene film and the copper substrate of drying after organic glue-line are placed on to FeCl
3in etching fluid, to corrode copper catalytic substrate, it should be noted that described organic glue-line (PMMA layer) need to upwards place.When copper catalytic substrate is by FeCl
3after corrosive fluid corrosion, obtain the combination of the graphene film of PMMA layer and process modification.Then perform step 4).
In step 4), described combination is transferred in target substrate, then remove described organic glue-line, obtain being formed on graphene film in target substrate and through modifying, wherein, remove photoresist solvent soaking or the solvent vapo(u)r that removes photoresist of employing removed described organic glue-line, described in the solvent that removes photoresist at least comprise the one in chloroform, acetic acid, ethyl acetate or acetone.In described step 4), shifting described combination to the concrete steps of target substrate is: first in target substrate, make described graphene film and target substrate surface be close together described combination uniform spreading, then under 50 ~ 120 DEG C of conditions, dry; Described target substrate at least comprises the one in deielectric-coating, glass, sapphire, PET film or semiconductor material, wherein, described semiconductor material at least comprises silicon, germanium, gallium arsenide, indium phosphide, gan or its related compound, and described deielectric-coating at least comprises silicon oxide, silicon nitride, silicon oxynitride or hafnia etc.
It should be noted that, owing to having used corrosive fluid, therefore needed described combination to carry out cleaning step to target substrate at the described combination of transfer.Particularly, in the present embodiment one, treat that copper substrate is by FeCl
3after corrosive fluid erodes, proceed in deionized water and clean floating over the graphene film on corrosive fluid surface and the combination of organic glue-line, to remove residual FeCl
3etchant solution, it should be noted that clean time, should ensure described organic glue-line upward and graphene film down.
Particularly, in the present embodiment one, step 4) is: by described combination (graphene film and the PMMA layer) uniform spreading through cleaning step, in target substrate, in embodiment mono-, target substrate is the silicon substrate (Si/SiO that is formed with silica medium film
2substrate), make described graphene film and Si/SiO
2substrate surface is close together, and then dries up by nitrogen gun, thereby described combination is transferred in target substrate; Afterwards, will be transferred to Si/SiO
2described combination on substrate immerses in acetone soln, places 12h and removes the PMMA layer on graphene film surface, obtains being formed on Si/SiO
2graphene film on substrate and through modifying.
Fig. 2 is shown as in embodiment mono-through the continuous graphite alkene film transfer of doping and modification to the optical microscope photograph after target substrate, and wherein scale is of a size of 20 μ m; In Fig. 2,1. arrow represents the Pt particle of doping, and in Fig. 2,2. arrow represents residual PMMA layer organic colloid, and in Fig. 2,3. arrow represents multi-layer graphene.
Find by the measurement to continuous graphite alkene Electrical character after this modification, the resistivity of film significantly declines, and mobility also improves, further verify nano platinum particle improvement to graphene film electrology characteristic to the modification of graphene film domain border and fault location.
First the present invention utilizes in the metal substrate of the domain border of graphene film and fault location exposure the metal ion in metal ion solution is reduced, domain border and fault location at graphene film generate metal nanoparticle, and can not make metal nanoparticle be modified at flawless position, thereby graphene film is realized to selective doping to be modified, and then reach better modification effect, then by corrosion and shifting process, the good graphene film of doping and modification is realized and being shifted, in other words, the present invention shifts after to the first doping and modification of graphene film.The present invention utilizes the metal substrate material of graphene film growth as reductive agent, the metal ion in solution to be reduced, and do not need to introduce new reductive agent, in having realized the grapheme modified film of selective doping, avoid the deposition of metal nanoparticle on complete graphene film surface like this.Repeatability of the present invention is high, simple, can grapheme modified film in enormous quantities; Meanwhile, the present invention can accurate calibration Graphene continuous film in the shape and size of single crystal domains, and can by change metal ion solution concentration and with metal substrate duration of contact qualitative raising graphene film electric property.
Embodiment bis-
Embodiment bis-is basic identical with the technical scheme of embodiment mono-, and difference is only: in embodiment mono-, adorned graphene film is continuous graphene film, and in the present embodiment two, adorned graphene film is discontinuous graphene film.Concrete modification and transfer step are identical with embodiment mono-, are not repeating one by one at this.
In the present embodiment two, modify the position that discontinuous graphene film can more intuitively see that metal nanoparticle is modified.Fig. 3 a and Fig. 3 b are shown as the discontinuous graphene film through doping and modification in embodiment bis-and are transferred to the optical microscope photograph after target substrate, wherein, in Fig. 3 a, be 1min the duration of contact of chloroplatinic acid aqueous solution and graphene film, be 10min the duration of contact of Fig. 3 b chloroplatinic acid aqueous solution and graphene film, and scale size is 20 μ m; In Fig. 3 a arrow 4. and in Fig. 3 b arrow 7. represent that the pt atom being reduced is gathered into nano platinum particle (diameter is 300～800nm), in Fig. 3 a arrow 5. and in Fig. 3 b arrow 8. represent exposed target substrate (Si/SiO out
2substrate), in Fig. 3 a arrow 6. and in Fig. 3 b arrow 9. represent residual PMMA organic colloid.
The time that metal ion solution contacts with graphene film is the time of doping and modification.From Fig. 3 a and Fig. 3 b, when the doping and modification time more in short-term, after copper substrate is corroded, nano platinum particle still can be suspended on the position on graphene film domain border, is suspended on that the nano platinum particle of graphene film domain boundary and other nano platinum particle attract each other and the edge that is gathered in graphene film domain border.Along with doping time constantly extends, the pt atom being reduced increases, and increasing nano platinum particle is further assembled at Graphene grain boundaries, realizes graphene film is further modified.
It is to be noted, the time that change metal ion solution contacts with graphene film should with change metal ion solution relative concentration, all can adjust the speed of the metal nanoparticle gathering of carrying out doping and modification, the concentration time higher or that metal ion solution contacts with graphene film of metal ion solution is longer, the quantity of carrying out the metal nanoparticle gathering of doping and modification gets more and more, within the specific limits, more effective raising by the electric property of grapheme modified film.
In sum, the method of a kind of grapheme modified film of the present invention, first utilize the metal substrate exposing at domain border and the fault location of graphene film to reduce to the metal ion in metal ion solution, domain border and fault location at graphene film generate metal nanoparticle, and can not make metal nanoparticle be modified at flawless position, thereby graphene film is realized to selective doping to be modified, and then reach better modification effect, then by corrosion and shifting process, the good graphene film of doping and modification is realized and being shifted, in other words, the present invention shifts after to the first doping and modification of graphene film.The present invention utilizes the metal substrate material of graphene film growth as reductive agent, the metal ion in solution to be reduced, and do not need to introduce new reductive agent, in having realized the grapheme modified film of selective doping, avoid the deposition of metal nanoparticle on complete graphene film surface like this.Repeatability of the present invention is high, simple, can grapheme modified film in enormous quantities; Meanwhile, the present invention can accurate calibration Graphene continuous film in the shape and size of single crystal domains, and can by change metal ion solution concentration and with metal substrate duration of contact qualitative raising graphene film electric property.So the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (10)
1. a method for grapheme modified film, is characterized in that, described method at least comprises the following steps:
1) metal ion solution is contacted with the graphene film being formed in metal substrate, then dry up described graphene film and metal substrate, obtain being formed on the graphene film in metal substrate and through modifying;
2) on the graphene film obtaining, form organic glue-line after step 1);
3) utilize corrosive fluid to remove described metal substrate, obtain the combination of the graphene film of organic glue-line and process modification;
4) described combination is transferred in target substrate, then removes described organic glue-line, obtain being formed on graphene film in target substrate and through modifying.
2. the method for a kind of grapheme modified film according to claim 1, is characterized in that: be 0.1 ~ 60min the duration of contact in described step 1).
3. the method for a kind of grapheme modified film according to claim 1, is characterized in that: described metal ion solution at least comprises a kind of or several arbitrarily in Ag, Pt, Au metal ion.
4. the method for a kind of grapheme modified film according to claim 1, is characterized in that: described metal substrate at least comprises a kind of or any several alloy in Fe, Co, Ni, Mo, Cu.
5. the method for a kind of grapheme modified film according to claim 1, it is characterized in that: described step 2) in form organic glue-line on graphene film surface concrete steps be: first, at the organic glue-line of described graphene film surface spin coating, then under 150 ~ 190 DEG C of conditions, dry.
6. a kind of method of grapheme modified film according to claim 1 or 5, is characterized in that: described organic glue-line at least comprises polymethylmethacrylate or polydimethylsiloxane.
7. the method for a kind of grapheme modified film according to claim 1, is characterized in that: described corrosive fluid at least comprises HNO
3, dense H
2sO
4, FeCl
3, Fe (NO
3)
3, (NH
4)
2s
2o
8or KNO
3in one.
8. the method for a kind of grapheme modified film according to claim 1, is characterized in that: described target substrate at least comprises the one in deielectric-coating, glass, sapphire, PET film or semiconductor material.
9. the method for a kind of grapheme modified film according to claim 1, it is characterized in that: in described step 4), shifting described combination to the concrete steps of target substrate is: first in target substrate, make described graphene film and target substrate surface be close together described combination uniform spreading, then under 50 ~ 120 DEG C of conditions, dry.
10. the method for a kind of grapheme modified film according to claim 1, it is characterized in that: in affiliated step 4), adopt the organic glue-line described in removal of solvents that removes photoresist, wherein, the solvent that removes photoresist described at least comprises the one in chloroform, acetic acid, ethyl acetate or acetone.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104851787A (en) * | 2015-04-01 | 2015-08-19 | 中国科学院上海微***与信息技术研究所 | Method for improving ohmic contact between metal electrode and graphene |
| CN105239061A (en) * | 2015-09-25 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | Graphene/metal composite thin film and preparation method thereof |
| CN108513570A (en) * | 2015-12-03 | 2018-09-07 | 纳米技术仪器公司 | Graphene film and production method highly conductive and be orientated |
| CN108896621A (en) * | 2018-04-08 | 2018-11-27 | 山东大学 | A kind of ammonia gas sensor and preparation method thereof loading platinum grain |
| CN110957058A (en) * | 2019-12-25 | 2020-04-03 | 陕西科技大学 | Conductive leather and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101872120A (en) * | 2010-07-01 | 2010-10-27 | 北京大学 | Method for preparing patterned graphene |
| CN102351175A (en) * | 2011-11-03 | 2012-02-15 | 东南大学 | High-quality transfer method of graphene prepared by chemical vapor deposition method |
-
2012
- 2012-11-29 CN CN201210501642.0A patent/CN103848416A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101872120A (en) * | 2010-07-01 | 2010-10-27 | 北京大学 | Method for preparing patterned graphene |
| CN102351175A (en) * | 2011-11-03 | 2012-02-15 | 东南大学 | High-quality transfer method of graphene prepared by chemical vapor deposition method |
Non-Patent Citations (2)
| Title |
|---|
| ALBERT GUTES ET AL.: "Single-layer CVD-grown graphene decorated with metal nanoparticles as a promising biosensing platform", 《BIOSENSORS AND BIOELECTRONICS》 * |
| YUANWEN WU ET AL.: "Synthesis of large-area graphene on molybdenum foils by chemical vapor deposition", 《CARBON》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104851787A (en) * | 2015-04-01 | 2015-08-19 | 中国科学院上海微***与信息技术研究所 | Method for improving ohmic contact between metal electrode and graphene |
| CN105239061A (en) * | 2015-09-25 | 2016-01-13 | 中国科学院宁波材料技术与工程研究所 | Graphene/metal composite thin film and preparation method thereof |
| CN108513570A (en) * | 2015-12-03 | 2018-09-07 | 纳米技术仪器公司 | Graphene film and production method highly conductive and be orientated |
| US11469009B2 (en) | 2015-12-03 | 2022-10-11 | Global Graphene Group, Inc. | Production process for highly conducting and oriented graphene film |
| CN108513570B (en) * | 2015-12-03 | 2023-03-03 | 纳米技术仪器公司 | Highly conductive and oriented graphene films and methods of production |
| CN108896621A (en) * | 2018-04-08 | 2018-11-27 | 山东大学 | A kind of ammonia gas sensor and preparation method thereof loading platinum grain |
| CN110957058A (en) * | 2019-12-25 | 2020-04-03 | 陕西科技大学 | Conductive leather and preparation method thereof |
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Application publication date: 20140611 |