CN104528694A - Method for doping and transferring graphene - Google Patents
Method for doping and transferring graphene Download PDFInfo
- Publication number
- CN104528694A CN104528694A CN201410764269.7A CN201410764269A CN104528694A CN 104528694 A CN104528694 A CN 104528694A CN 201410764269 A CN201410764269 A CN 201410764269A CN 104528694 A CN104528694 A CN 104528694A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite structure
- doping
- pressure
- heat treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of graphene production, and particularly relates to a method for doping and transferring graphene. The method comprises the following steps: 1, coating a graphene growing surface with a polymer doping transferring medium; 2, pressing and adhering the graphene coated with the doping transferring medium on the surface of a target substrate to form a composite structure formed by the target substrate, the doping transferring medium, the graphene and the growing substrate sequentially; 3, carrying out pressure-vacuum treatment on the composite structure; 4, heating the composite structure which is subjected to the pressure-vacuum treatment; and 5, separating the heated composite structure to remove the growing substrate in the composite structure. The method has the beneficial effects that the polymer material with a doping effect is selected to serve as a graphene transferring material and a doping material at the same time, the doping stability is improved by utilizing the stability characteristics of polymer, a subsequent graphene doping step is omitted, and the graphene production process is simplified.
Description
Technical field
The present invention relates to Graphene production technical field, particularly relate to a kind of Graphene doping transfer method.
Background technology
Graphene is the two-dimension nano materials found at present in recent years, has numerous excellent properties.Wherein, high transmitance and the carrier mobility of superelevation, make it can be used as brand-new transparent conductive material and enjoy industry member to pay close attention to.
Method prepared by the Graphene mass-producing of existing maturation is chemical Vapor deposition process (CVD).CVD is prepared Graphene and is generally selected opaque metal as growth substrate, such as Copper Foil, nickel foil etc.Will use as transparent conductive material, Graphene must transfer to transparent substrates, and adulterates to reduce sheet resistance to it.Existing adulterating method is take small molecules as doping agent mostly, and such as quadrol, nitric acid, hydrochloro-auric acid etc., make its physical adsorption reach doping object at graphenic surface.Small molecule dopant and Graphene reactive force weak, volatile, cause Graphene sheet resistance constantly to increase in put procedure, seriously limit the practical application of Graphene.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Graphene doping transfer method, while raising Graphene electric performance stablity, simplify production technique.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of Graphene doping transfer method, is characterized in that, comprise the following steps:
Step one, at growing graphene surface coated doping transfer medium;
Step 2, is attached to target substrate on the surface by the Graphene pressing being coated with doping transfer medium obtained, and forms the composite structure be made up of successively target substrate, doping transfer medium, Graphene and growth substrate;
Step 3, carries out pressure process process to described composite structure;
Step 4, carries out heat treated to the composite structure carried out after pressure process process;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate in composite structure.
On the basis of technique scheme, the present invention can also do following improvement.
Further, a kind of polymer doping transfer medium of described step is polymkeric substance containing cyano functional group side base and/or nitro functions side base and/or sulfonate functional groups side base and/or fluorine pendant groups and multipolymer thereof, such as: polyacrylonitrile (PAN) is dissolved in the mixture of dimethyl formamide, the mixture of dissolve with ethanol Nitrocellulose, cyanacrylate and methylmethacrylate copolymer are dissolved in the mixture of ethyl acetate, poly-thereof (PSS) aqueous solution, poly-perfluor-1, 3-dioxol, trifluorochloroethylene one vinylidene fluoride copolymer, poly-perfluoro capryl ethoxyethyl acrylate solution, the butylacetate solution of perfluor nonyl ethoxyethyl acrylate-alkylmethacrylate polymer, perfluor-1, 3-dioxol-vinylidene fluoride copolymer, doping transfer medium perfluor-1, 3-dioxol-trifluoro-ethylene copolymer solution, perfluoro capryl ethoxyethyl acrylate-vinylformic acid norborneol ester copolymer solution etc.
Further, in described step 3, the pressure of pressure process process is 0.5MPa to 15MPa, and vacuum pressure is 0.1Pa to 200Pa.
Further, the pressure range of pressure process process in described step 3 is 2MPa to 8MPa, and vacuum pressure scope is 0.1Pa to 10Pa.
Further, in described step 3, the time of pressure process process is 0.5hr to 5hr.
Further, in described step 3, the pressure process treatment time is 2hr to 3hr.
Further, in described step 4, the temperature of heat treated is 50-200 DEG C, and heating treatment time is 5-400min.
Further, in described step 4, heat treatment temperature is 80-130 DEG C, and heating treatment time is 30-60min.
The invention has the beneficial effects as follows: select the macromolecular material with doping effect simultaneously as Graphene transferred material and dopant material, high molecular stability feature is utilized to improve stably-doped property, save follow-up Graphene doping step, simplify Graphene production technique.
Accompanying drawing explanation
Fig. 1 is flow chart of steps of the present invention;
Fig. 2 is the structural representation of composite structure described in the present invention.
In accompanying drawing, the list of parts representated by each label is as follows:
1, target substrate, 2, doping transfer medium, 3, Graphene, 4, growth substrate 4.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment one
The present embodiment comprises the following steps:
Step one, is dissolved in dimethyl formamide by polyacrylonitrile (PAN), coats growing graphene 3 surface by roller painting;
Step 2, will be coated with Graphene and the PET base pressing of polyacrylonitrile, form the composite structure of PET/PAN/ Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 0.5MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 50 DEG C, and heating treatment time is 400min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment two
The present embodiment comprises the following steps:
Step one, dissolve with ethanol Nitrocellulose, is coated on growing graphene 3 surface;
Step 2, is attached to target substrate PET1 on the surface by Graphene 3 pressing being coated with Nitrocellulose 2 obtained, and forms the composite structure of PET/ Nitrocellulose/Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 15MPa, and vacuum pressure is 200Pa, and the time of pressure process process is 0.5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 50 DEG C, and heating treatment time is 400min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment three
The present embodiment comprises the following steps:
Step one, is dissolved in ethyl acetate by cyanacrylate and methylmethacrylate copolymer, is coated on growing graphene 3 surface;
Step 2, Graphene 3 pressing being coated with cyanacrylate and methylmethacrylate copolymer 2 obtained is attached to target substrate PET1 on the surface, forms the composite structure of the composite structure of PET/ cyanacrylate multipolymer/Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 0.5MPa, and vacuum pressure is 200Pa, and the time of pressure process process is 3hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 50 DEG C, and heating treatment time is 400min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment four
The present embodiment comprises the following steps:
Step one, gathers thereof (PSS) aqueous solution in growing graphene 3 surface coated;
Step 2, is attached to target substrate PET1 on the surface by Graphene 3 pressing being coated with doping transfer medium PSS obtained, forms the composite structure of PET/PSS/ Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 15MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 0.5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 50 DEG C, and heating treatment time is 400min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment five
The present embodiment comprises the following steps:
Step one, gathers perfluor-1,3-dioxol as doping transfer medium 2 in growing graphene 3 surface coated;
Step 2, is attached to target substrate PET1 on the surface by Graphene 3 pressing being coated with poly-perfluor-1,3-dioxol obtained, and forms the composite structure that PET/ gathers the composite structure of perfluor-1,3-dioxol/Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 15MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 2hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 50 DEG C, and heating treatment time is 400min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment six
The present embodiment comprises the following steps:
Step one, at growing graphene 3 surface coated trifluorochloroethylene one vinylidene fluoride copolymer doping transfer medium 2;
Step 2, is attached to target substrate 1 on the surface by Graphene 3 pressing being coated with trifluorochloroethylene one vinylidene fluoride copolymer doping transfer medium 2 obtained, forms the composite structure of PET/ trifluorochloroethylene one vinylidene fluoride copolymer/Graphene/growth substrate
Step 3, carries out pressure process process to described composite structure, and pressure is 0.5MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 200 DEG C, and heating treatment time is 5min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment seven
The present embodiment comprises the following steps:
Step one, gathers perfluoro capryl ethoxyethyl acrylate solution in growing graphene 3 surface coated;
Step 2, has Graphene 3 pressing of poly-perfluoro capryl ethoxyethyl acrylate solution to be attached to target substrate 1 on the surface by the surface coated obtained, form the composite structure that PET/ gathers perfluoro capryl ethoxyethyl acrylate/Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 0.5MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 200 DEG C, and heating treatment time is 5min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment eight
The present embodiment comprises the following steps:
Step one, at the butylacetate solution of growing graphene 3 surface coated perfluor nonyl ethoxyethyl acrylate-alkylmethacrylate polymer;
Step 2, Graphene 3 pressing being coated with doping transfer medium perfluor nonyl ethoxyethyl acrylate-alkylmethacrylate polymer 2 obtained is attached to target substrate PET1 on the surface, forms the composite structure of PET/ perfluor nonyl ethoxyethyl acrylate-alkylmethacrylate polymer/Graphene/growth substrate
Step 3, carries out pressure process process to described composite structure, and pressure is 15MPa, and vacuum pressure is 200Pa, and the time of pressure process process is 0.5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 200 DEG C, and heating treatment time is 5min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment nine
The present embodiment comprises the following steps:
Step one, at growing graphene 3 surface coated doping transfer medium perfluor-1,3-dioxol-vinylidene fluoride copolymer;
Step 2, is attached to target substrate 1 on the surface by Graphene 3 pressing being coated with doping transfer medium 2 obtained, forms the composite structure of PET/ perfluor-1,3-dioxol-vinylidene fluoride copolymer/Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 0.5MPa, and vacuum pressure is 200Pa, and the time of pressure process process is 3hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 200 DEG C, and heating treatment time is 5min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment ten
The present embodiment comprises the following steps:
Step one, at growing graphene 3 surface coated doping transfer medium perfluor-1,3-dioxol-trifluoro-ethylene copolymer solution;
Step 2, is attached to target substrate 1 on the surface by Graphene 3 pressing being coated with doping transfer medium 2 obtained, forms the composite structure of PET/ perfluor-1,3-dioxol-trifluoro-ethylene copolymer/Graphene/growth substrate;
Step 3, carries out pressure process process to described composite structure, and pressure is 15MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 0.5hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 200 DEG C, and heating treatment time is 5min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
Embodiment 11
The present embodiment comprises the following steps:
Step one, at growing graphene 3 surface coated doping transfer medium perfluoro capryl ethoxyethyl acrylate-vinylformic acid norborneol ester copolymer solution;
Step 2, is attached to target substrate 1 on the surface by Graphene 3 pressing being coated with doping transfer medium 2 obtained, forms the composite structure of PET/ perfluoro capryl ethoxyethyl acrylate-vinylformic acid norborneol ester copolymer/Graphene/growth substrate; The composite structure be made up of successively target substrate 1, doping transfer medium 2, Graphene 3 and growth substrate 4;
Step 3, carries out pressure process process to described composite structure, and pressure is 15MPa, and vacuum pressure is 0.1Pa, and the time of pressure process process is 2hr;
Step 4, carries out heat treated to the composite structure carried out after pressure process process, and the temperature of heat treated is 200 DEG C, and heating treatment time is 5min;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate 4 in composite structure.
The present invention selects the macromolecular material with doping effect simultaneously as Graphene 3 transferred material and dopant material, utilizes high molecular stability feature to improve stably-doped property, saves follow-up Graphene 3 and to adulterate step, simplify Graphene 3 production technique.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a Graphene doping transfer method, is characterized in that, comprise the following steps:
Step one, at growing graphene surface coated polymer doping transfer medium (2);
Step 2, the Graphene pressing being coated with doping transfer medium obtained is attached to target substrate on the surface, forms the composite structure be made up of successively target substrate (1), doping transfer medium (2), Graphene (3) and growth substrate (4);
Step 3, carries out pressure process process to described composite structure;
Step 4, carries out heat treated to the composite structure carried out after pressure process process;
Step 5, carries out separating treatment to the composite structure after heat treated, separates the growth substrate (4) in composite structure.
2. a kind of Graphene doping transfer method according to claim 1, it is characterized in that, polymer doping transfer medium (2) in described step one is the polymkeric substance and the multipolymer thereof that contain cyano functional group side base and/or nitro functions side base and/or sulfonate functional groups side base and/or fluorine pendant groups.
3. a kind of Graphene doping transfer method according to claim 1, it is characterized in that, in described step 3, the pressure of pressure process process is 0.5MPa to 15MPa, and vacuum pressure is 0.1Pa to 200Pa.
4. a kind of Graphene doping transfer method according to claim 1, it is characterized in that, the pressure range of pressure process process in described step 3 is 2MPa to 8MPa, and vacuum pressure scope is 0.1Pa to 10Pa.
5. a kind of Graphene doping transfer method according to claim 1, it is characterized in that, the treatment time of pressure process process in described step 3 is 0.5hr to 5hr.
6. a kind of Graphene doping transfer method according to claim 1, it is characterized in that, the treatment time of pressure process process in described step 3 is 2hr to 3hr.
7. a kind of Graphene doping transfer method according to any one of claim 1 to 6, it is characterized in that, in described step 4, the temperature of heat treated is 50-200 DEG C, and heating treatment time is 5-400min.
8. a kind of Graphene doping transfer method according to any one of claim 6 to 7, it is characterized in that, in described step 4, the temperature of heat treated is 80-130 DEG C, and heating treatment time is 30-60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764269.7A CN104528694B (en) | 2014-12-12 | 2014-12-12 | A kind of Graphene doping transfer method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410764269.7A CN104528694B (en) | 2014-12-12 | 2014-12-12 | A kind of Graphene doping transfer method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104528694A true CN104528694A (en) | 2015-04-22 |
| CN104528694B CN104528694B (en) | 2016-07-06 |
Family
ID=52844389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410764269.7A Active CN104528694B (en) | 2014-12-12 | 2014-12-12 | A kind of Graphene doping transfer method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104528694B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101027A (en) * | 2017-12-29 | 2018-06-01 | 重庆墨希科技有限公司 | Large area CVD graphenes adulterate transfer method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN103288077A (en) * | 2013-06-28 | 2013-09-11 | 重庆墨希科技有限公司 | Method for rapidly and nondestructively transferring graphene |
| CN103332680A (en) * | 2013-06-28 | 2013-10-02 | 重庆墨希科技有限公司 | Transferable graphene film and transfer method thereof |
| US20140166496A1 (en) * | 2012-12-14 | 2014-06-19 | Chung-Shan Institute Of Science And Technology | Method for producing shaped graphene sheets |
-
2014
- 2014-12-12 CN CN201410764269.7A patent/CN104528694B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| US20140166496A1 (en) * | 2012-12-14 | 2014-06-19 | Chung-Shan Institute Of Science And Technology | Method for producing shaped graphene sheets |
| CN103288077A (en) * | 2013-06-28 | 2013-09-11 | 重庆墨希科技有限公司 | Method for rapidly and nondestructively transferring graphene |
| CN103332680A (en) * | 2013-06-28 | 2013-10-02 | 重庆墨希科技有限公司 | Transferable graphene film and transfer method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101027A (en) * | 2017-12-29 | 2018-06-01 | 重庆墨希科技有限公司 | Large area CVD graphenes adulterate transfer method |
| CN108101027B (en) * | 2017-12-29 | 2020-01-31 | 重庆墨希科技有限公司 | Large-area CVD graphene doping transfer method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104528694B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5869627B2 (en) | Method for producing transparent conductive film and transparent conductive film produced thereby | |
| CN104085143B (en) | Preparation method and the product of Graphene composite guide hotting mask | |
| CN103449420B (en) | High-quality graphene dispersion method and film preparation method | |
| CN103531304B (en) | A kind of quick preparation large area carbon nano tube flexible transparent conductive film and the method for improving its electric conductivity | |
| CN109251636B (en) | Preparation process of high-light-transmittance aqueous conductive coating | |
| CN102718408A (en) | Method for preparing gas-sensitive film | |
| CN104240798A (en) | Transparent conductive film and preparation method thereof | |
| CN109181498B (en) | Environment-friendly coating for electronic products | |
| CN103436138A (en) | Stable and transparent super-hydrophobic or super-amphiphobic coating as well as preparation method and application thereof | |
| CN105206352B (en) | Graphene transparent conductive film and preparation method thereof | |
| JP2016535918A (en) | Electrode having excellent light transmittance, method for producing electrode having excellent light transmittance, and electronic device including electrode having excellent light transmittance | |
| CN107556797B (en) | preparation method of graphene/polyaniline composite material anticorrosive paint auxiliary agent | |
| WO2018040954A1 (en) | Preparation of pet/nano silver wire transparent conductive film by illumination sintering | |
| CN104992781A (en) | Preparation method for graphene-based three-element composite material | |
| CN102543476A (en) | Graphene counter electrode for dye-sensitized solar cell and manufacturing method of graphene counter electrode | |
| CN104465993A (en) | Carbon-based composite transparent electrode and manufacturing method thereof | |
| CN104528694A (en) | Method for doping and transferring graphene | |
| JP6173475B2 (en) | Metal-deposited thin film, its production intermediate, and related production method | |
| CN111999359B (en) | Graphene-based transparent conductive film electrode and preparation method and application thereof | |
| CN113231278A (en) | Preparation method of carbon-coated foil for lithium ion battery | |
| CN104658731A (en) | Method for reducing square resistance of graphene film by stably doping | |
| Liu et al. | Electrostatic assembly of ultraviolet-curable cellulose-coated silver nanowires as transparent electrodes for nanogenerator | |
| CN105776882B (en) | A kind of preparation method of ito thin film | |
| CN104264146A (en) | Functionalized graphene-based transparent conductive heat-conducting film and preparation method thereof | |
| CN102850572B (en) | Preparation method for super-hydrophobic polypropylene film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |