CN107867682B - Super-strong acid dopant for efficiently doping graphene and doping method - Google Patents
Super-strong acid dopant for efficiently doping graphene and doping method Download PDFInfo
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- CN107867682B CN107867682B CN201610854519.5A CN201610854519A CN107867682B CN 107867682 B CN107867682 B CN 107867682B CN 201610854519 A CN201610854519 A CN 201610854519A CN 107867682 B CN107867682 B CN 107867682B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002019 doping agent Substances 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title claims abstract description 8
- 239000003930 superacid Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- QNDPUZFBWUBSNH-UHFFFAOYSA-I magic acid Chemical compound OS(F)(=O)=O.F[Sb](F)(F)(F)F QNDPUZFBWUBSNH-UHFFFAOYSA-I 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 abstract description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of graphene, in particular to a super acid doping agent for efficiently doping graphene and a doping method. The doping agent is super acid or a mixture containing super acid, and the doping agent is contacted with the intrinsic surface of the untransferred graphene, and then the graphene is doped. The method has the characteristics of high efficiency and stability by adopting super-strong acid doping, and lays a foundation for realizing the application of doped graphene in electronic and optoelectronic devices.
Description
The technical field is as follows:
the invention relates to the field of graphene, in particular to a super acid doping agent for efficiently doping graphene and a doping method.
Background art:
graphene is a novel two-dimensional carbon material having a honeycomb structure and composed of a single layer of carbon atoms, and has excellent electrical conductivity 1.6 times that of copper. The graphene has excellent permeability to near infrared, visible light and ultraviolet light, and the light transmittance of the single-layer graphene reaches 97.7%. The strength of the graphene can reach 130GPa, is more than 100 times that of steel, and has excellent flexibility, thermal stability and chemical stability. Therefore, the graphene can fully exert the advantages of the structure and the performance of the graphene when applied to electronic and optoelectronic devices, and has received great attention.
However, the intrinsic graphene cannot meet the requirements of electronic and optoelectronic devices on the fermi level, resistance and the like, and needs to be doped. Among various doping methods, the use of superacid dopants can significantly increase the carrier concentration of graphene without introducing structural defects, which is a typical method for doping graphene at present. However, the conventional super acid dopants generally have difficulty in achieving both excellent doping effects and high doping stability. Therefore, there is a need to develop a novel super acid dopant capable of efficiently and stably doping graphene.
The invention content is as follows:
the invention aims to provide a super acid doping agent for efficiently doping graphene and a doping method, and the super acid doping agent realizes efficient doping of the graphene by utilizing the characteristic of strong electron interaction between super acid and untransferred graphene.
The technical scheme of the invention is as follows:
a super acid dopant for efficiently doping graphene adopts super acid or a mixture containing super acid.
The super acid dopant of the efficiently doped graphene adopts one or a combination of more than two of a Bronsted super acid, a Lewis super acid, a conjugated Bronsted-Lewis super acid and a solid super acid.
Typical superacids of the efficiently doped graphene superacid dopant include antimony pentafluoride, fluoroantimonic acid, magic acid, carborane acid, and fluorosulfonic acid.
According to the method for doping the super acid dopant for efficiently doping the graphene, the dopant is contacted with the intrinsic surface of the untransferred graphene, and then the graphene is doped.
According to the method for doping the super acid dopant for efficiently doping the graphene, the graphene is prepared by a chemical vapor deposition method, a precipitation method, an epitaxial method, a pyrolysis method, a mechanical stripping method or a chemical stripping method.
According to the doping method of the super acid dopant for efficiently doping the graphene, when a super acid solution is adopted for doping, the molar concentration range of the super acid is 0.1 mM-20M, and the solvent of the solution is water, an organic solvent or a high molecular polymer.
The method for doping the super acid dopant of the efficiently doped graphene comprises one or a combination of more than two of solution soaking, evaporation deposition, chemical vapor deposition, printing, roll coating, blade coating, wire rod coating, spraying, spin coating and lifting.
According to the method for doping the super acid dopant for efficiently doping the graphene, the dopant partially covers the surface of the graphene or forms a continuous film.
The invention has the characteristics and beneficial effects that:
1. the super acid is used as a novel chemical doping agent for doping graphene, and has the outstanding characteristic of good doping effect.
2. The doping method of directly contacting the superacid with the untransferred intrinsic surface of the graphene is adopted, so that the doping effect and stability can be further improved.
The specific implementation mode is as follows:
the present invention will be described in further detail below with reference to examples.
Example 1
In this embodiment, fluoroantimonic acid is used as a dopant of graphene. The single-layer graphene grown on the copper foil by CVD is soaked in a 10mM fluorine antimonic acid aqueous solution for 1 minute. Taking out and drying by using nitrogen, coating polymethyl methacrylate (PMMA) on the surface as a transfer medium, and transferring to the surface of a silicon wafer to finish doping. The average sheet resistance of the doped graphene was 430 ohms/square.
Example 2
The difference from the embodiment 1 is that:
the fluorine antimonic acid is dissolved in polymethyl methacrylate (PMMA) solution, the molar concentration is 20mM, and the fluorine antimonic acid is directly coated on the surface of the single-layer graphene grown on the copper foil by CVD. And then transferring the graphene to the surface of the silicon wafer, and reserving the PMMA layer to finish doping. The average sheet resistance of the doped graphene was 364 ohms/square.
Example 3
The difference from the embodiment 1 is that:
magic acid is used as a doping agent to dope the graphene nanoplatelets prepared by a pyrolysis method, a mechanical stripping method or a chemical stripping method. And (3) placing the graphene on the surface of the initial substrate above a magic acid solution at 50 ℃, doping the graphene by using volatile matters of the magic acid, and doping for 30 minutes. Graphene does not need to be transferred to the surface of a new substrate after doping.
Example 4
The difference from the embodiment 1 is that:
in this embodiment, the doped single-layer graphene/silicon wafer is used as a substrate, and a polymer polymethyl methacrylate (PMMA) is used as a transfer medium to transfer the second layer doped graphene to the surface thereof. And repeating the steps to obtain the interlayer doped 3-layer graphene film. After doping, the average sheet resistance of the graphene is 110 ohm/square.
Example 5
The difference from the embodiment 1 is that:
in this embodiment, an EVA transparent adhesive film is used as a transfer medium, and is attached to the surface of the doped large-area graphene/copper foil coil in a roll-to-roll hot pressing manner. The graphene film is used as a negative electrode for electrolyzing water, and the graphene is transferred to the surface of the EVA transparent adhesive film by a roll-to-roll electrolytic gas bubbling stripping method. The average sheet resistance after doping was 510 ohms/square.
The example results show that the super acid can be used as a novel dopant for efficiently doping graphene. The graphene can be doped after the super acid is contacted with the intrinsic surface of the graphene, and the doped graphene can be transferred to the surfaces of different substrates. The doping agent is suitable for doping different layers of graphene on different substrates, thereby laying a foundation for the application of doped graphene in electronic and optoelectronic devices.
Claims (5)
1. A method for doping a superacid dopant for efficiently doping graphene is characterized by comprising the following steps: the doping agent adopts super acid or a mixture containing super acid, and the doping agent partially covers the surface of the graphene or forms a continuous film;
contacting a dopant with the intrinsic surface of untransferred graphene, and doping the graphene;
when the solution of the super acid is adopted for doping, the molar concentration range of the super acid is 0.1 mM-20M, and the solvent of the solution is water, an organic solvent or a high molecular polymer.
2. The method for doping the super acid dopant for efficiently doping graphene according to claim 1, wherein: the super acid is one or the combination of more than two of a Bronsted super acid, a Lewis super acid, a conjugate Bronsted-Lewis super acid and a solid super acid.
3. The method for doping the superacid dopant for efficiently doping graphene according to claim 1 or 2, wherein: typical superacids include antimony pentafluoride, fluoroantimonic acid, magic acid, carborane acid, fluorosulfonic acid.
4. The method for doping the super acid dopant for efficiently doping graphene according to claim 1, wherein: the graphene is prepared by a chemical vapor deposition method, a precipitation method, an epitaxial method, a pyrolysis method, a mechanical stripping method or a chemical stripping method.
5. The method for doping the super acid dopant for efficiently doping graphene according to claim 1, wherein: the method for forming the dopant layer on the surface of the graphene comprises one or more of solution soaking, evaporation deposition, chemical vapor deposition, printing, roll coating, blade coating, wire bar coating, spray coating, spin coating and pulling.
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| CN201610854519.5A CN107867682B (en) | 2016-09-27 | 2016-09-27 | Super-strong acid dopant for efficiently doping graphene and doping method |
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| CN107867682B true CN107867682B (en) | 2021-03-26 |
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| CN110643076A (en) * | 2019-08-14 | 2020-01-03 | 浙江海洋大学 | Preparation method of transparent substrate film of flexible electronic device |
| CN110963484A (en) * | 2019-12-23 | 2020-04-07 | 中国科学院长春光学精密机械与物理研究所 | Doping layer-assisted large-area high-quality graphene nondestructive transfer method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409177A (en) * | 2014-11-28 | 2015-03-11 | 中国科学院金属研究所 | Large-scale preparation method for stably-doped large-area graphene transparent conductive films |
| CN104528698A (en) * | 2014-12-22 | 2015-04-22 | 重庆墨希科技有限公司 | Stable doping method for graphene |
| CN105366667A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing doped graphene from supercritical fluid |
| CN105836739A (en) * | 2016-05-12 | 2016-08-10 | 安徽大学 | Preparation method of multi-element doped graphene quantum dots |
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| US9534319B2 (en) * | 2009-02-19 | 2017-01-03 | William Marsh Rice University | Dissolution of graphite, graphite and graphene nanoribbons in superacid solutions and manipulation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409177A (en) * | 2014-11-28 | 2015-03-11 | 中国科学院金属研究所 | Large-scale preparation method for stably-doped large-area graphene transparent conductive films |
| CN104528698A (en) * | 2014-12-22 | 2015-04-22 | 重庆墨希科技有限公司 | Stable doping method for graphene |
| CN105366667A (en) * | 2015-11-04 | 2016-03-02 | 福建翔丰华新能源材料有限公司 | Method for preparing doped graphene from supercritical fluid |
| CN105836739A (en) * | 2016-05-12 | 2016-08-10 | 安徽大学 | Preparation method of multi-element doped graphene quantum dots |
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