CN109192359B - Graphene transparent conductive film with rivet structure and preparation method thereof - Google Patents
Graphene transparent conductive film with rivet structure and preparation method thereof Download PDFInfo
- Publication number
- CN109192359B CN109192359B CN201811129760.7A CN201811129760A CN109192359B CN 109192359 B CN109192359 B CN 109192359B CN 201811129760 A CN201811129760 A CN 201811129760A CN 109192359 B CN109192359 B CN 109192359B
- Authority
- CN
- China
- Prior art keywords
- graphene
- transparent conductive
- layer
- conductive film
- film
- 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.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/002—Auxiliary arrangements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention discloses a graphene transparent conductive film with a rivet structure and a preparation method thereof, the graphene transparent conductive film is composed of a transparent conductive nano material and graphene, the transparent conductive nano material with the rivet function is positioned between two layers of graphene, the transparent conductive nano material is connected with discontinuous graphene sheets on the same layer, the graphene sheets between the upper layer and the lower layer are conducted, the upper layer and the lower layer of few-layer graphene are riveted into the continuous conductive film at the maximum probability, the film has the minimum number of graphene layers as much as possible, the maximum film light transmittance is obtained, the raw materials of the film are cheap and easy to obtain, the film is easy to prepare in a large scale, the requirement on a substrate is small, and the film can be prepared on a flexible substrate.
Description
Technical Field
The invention belongs to the field of electronic materials, relates to a graphene transparent conductive film and a preparation method thereof, and particularly relates to a few-layer graphene transparent conductive film with a rivet structure and a preparation method thereof.
Background
The transparent conductive film is widely applied to devices such as solar cells, flat panel displays, touch screens, light emitting diodes and architectural glass curtain walls. Transparent conductive films are mainly classified into four types: a transparent conductive metal film, a transparent conductive oxide film, a non-oxide transparent conductive compound film, and a conductive particle dispersion medium body. The conductive oxide film has the most research and the most application. Indium Tin Oxide (ITO) is currently the most used and best performing transparent conductive thin film material. However, ITO has the disadvantages of resource shortage, high cost, poor flexibility and chemical stability, etc. The graphene has the characteristics of high chemical stability, good flexibility and good conductivity, and has become the most researched candidate material for replacing ITO.
Graphene is a two-dimensional carbon material having a honeycomb structure composed of a single layer of carbon atoms. The graphene has excellent conductivity which is 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.
At present, many methods for producing graphene mainly include a mechanical exfoliation method, a Chemical Vapor Deposition (CVD) method, an epitaxial growth method, a redox method, and the like. The chemical vapor deposition method can prepare large-area few-layer graphene on copper foil, and is widely researched and applied. However, the graphene prepared by the CVD method still has a large number of defects, which results in undesirable conductivity of the graphene. And the manufacturing equipment of the CVD method is expensive, the manufacturing conditions are harsh, and the manufacturing cost of the film is high. The method for preparing the graphene by the redox method has the advantages of low cost, high efficiency, suitability for solution processing and large-scale production and the like. However, a graphene film made of graphene oxide is often discontinuous in a few layers due to the size limitation of graphene oxide itself, and thus the electrical properties are affected. Under the condition of multiple layers, due to mutual superposition and coverage of graphene sheets, although the conductivity is improved, the light transmittance is obviously reduced, and the application requirement of the transparent conductive film cannot be met. On the premise of low cost, how to manufacture a graphene film with high light transmittance and high electric conductivity, which can be produced in a large scale, is a problem to be solved urgently.
Disclosure of Invention
In order to solve the problems that graphene oxide is discontinuous when few layers (namely, no more than 10 layers) of graphene films are formed, and graphene sheets are not conducted, a transparent conductive nano material with a rivet function is introduced, wherein the rivet function means that the material is connected with discontinuous graphene sheets like a rivet, so that the graphene films are kept connected and conducted to conduct. In order to protect the fragile rivet layer and reduce the dosage of the transparent conductive nano material to the minimum as possible, a monomolecular conductive nano material is required to be introduced between the graphene oxides as independently as possible, and different materials are required to be formed into films in a plurality of times instead of the conventional doping mixing. Therefore, the using amount of the rivets is reduced to the maximum extent, the rivets are protected between the two graphene layers, and the stability of the film is improved. In order to ensure sufficient light transmittance of the film, the number of graphene oxide layers is less than 10 (also called few-layer graphene film), preferably 2 to 5.
The following embodiments are provided for achieving the object of the present invention:
in one embodiment, the graphene transparent conductive film comprises no more than 10 graphene layers, and a transparent conductive nano material layer with a rivet function between every two graphene layers, wherein the transparent conductive nano material is a metal oxide, a metal nanowire or a nano carbon material, and connects (connects) discontinuous graphene sheets, preferably, the number of the graphene layers is 2-5, the metal oxide is selected from one or more combinations of ITO, ATO, SnO2, ZnO, AZO, CdO, CdIn2O4, Cd2SnO4, Zn2SnO4, ZnSnO4 and In2O3-ZnO, and the thickness is 5-100 nm; the nano carbon material is a carbon nano tube or a graphene nanoribbon; the metal nano-wire is a metal nano-particle with the thickness of 3-15 nm. The graphene is preferably graphene oxide.
In another embodiment, the present invention provides a method for preparing the graphene transparent conductive thin film of the present invention, comprising the steps of:
(1) introducing graphene oxide layers on a substrate, wherein the number of the graphene oxide layers is not more than 10, preferably 1-5, and more preferably 1-2.
(2) Introducing a transparent conductive nano material layer on the graphene oxide layer;
(3) introduction of graphene oxide layers on transparent conductive nanomaterial layers
(4) Reducing the graphene oxide;
the transparent conductive nano material connects and conducts discontinuous graphene sheets, and particularly connects and conducts the discontinuous graphene sheets on the same layer.
In the method of the present invention, the graphene oxide layer is introduced by one or more methods selected from a soaking method, a printing method, a roll coating method, a blade coating method, a wire bar coating method, a spraying method, a spin coating method and a pulling method; the method for introducing the transparent conductive nano material layer is one or more than two of a soaking method, a printing method, a rolling coating method, a blade coating method, a wire rod coating method, a spraying method, a spin coating method, a pulling method, a chemical vapor deposition method, a physical vapor deposition method, an evaporation coating method and a sputtering coating method; the graphene oxide is reduced by one or more methods selected from a thermal reduction method, a microwave reduction method, a plasma reduction method, a reducing gas reduction method, a catalytic or photocatalytic reduction method, a reducing acid reduction method and a phenol reduction method.
Specifically, the transparent conductive nanomaterial that can be used in the graphene transparent conductive thin film and the preparation method thereof of the present invention is selected from the following: one or a combination of ITO, ATO, SnO2, ZnO, AZO, CdO, CdIn2O4, Cd2SnO4, Zn2SnO4, ZnSnO4 or In2O 3-ZnO; metal nanoparticles of Au, Ag, Pt, Cu, Rh, Pd, Al, Cr and the like with the particle size of 3-15 nm; carbon nanotubes, graphene nanoribbons.
The preparation method of the graphene transparent conductive film comprises the following specific steps:
(1) introducing a graphene oxide layer on a substrate;
(2) introducing a transparent conductive nanomaterial on the first graphene oxide layer;
(3) introducing a graphene oxide layer on the transparent conductive nano material layer;
(4) introducing transparent conductive nano-materials on the second graphene oxide layer;
(5) introducing a graphene oxide layer on the second transparent conductive nano material layer, and repeating alternately in sequence until the number of graphene oxide layers is not more than 10, preferably 1-5, more preferably 1-2;
(6) the graphene oxide is reduced, and the graphene oxide is reduced,
the transparent conductive nano material connects and conducts discontinuous graphene sheets, and particularly connects and conducts the discontinuous graphene sheets on the same layer.
The graphene oxide layer large-scale preparation method is one or more selected from a soaking method, a printing method, a rolling coating method, a blade coating method, a wire bar coating method, a spraying method, a spin coating method and a pulling method. The number of graphene oxide layers on the substrate is 2-5. Because the graphene oxide can form a stable solution in various solvents, the graphene oxide layers with controllable layer number can be formed on the surfaces of various substrates by controlling the properties of the solution.
The introduction method of the rivet layer is one or more than two of a soaking method, a printing method, a rolling coating method, a blade coating method, a wire rod coating method, a spraying method, a spin coating method, a pulling method, a chemical vapor deposition method, a physical vapor deposition method, an evaporation coating method and a sputtering coating method.
The reduction method of the graphene oxide comprises one or more of a thermal reduction method, a microwave reduction method, a plasma reduction method, a reducing gas reduction method, a catalytic or photocatalytic reduction method and a reducing acid or phenol reduction method.
The graphene transparent conductive film adopts transparent nano conductive materials to connect discontinuous graphene sheets on the same layer, conducts the graphene sheets between the upper layer and the lower layer, rivets few-layer graphene on the upper layer and the lower layer into the continuous conductive film (see figure 1) at the maximum probability, enables the film to have the number of graphene sheets as few as possible, and obtains the maximum film light transmittance. The raw materials of the film are cheap and easy to obtain, the film is easy to prepare on a large scale, the requirement on the substrate is low, and the film can be prepared on a flexible substrate. Compared with the graphene film prepared by adopting a single-sheet superposition method in the prior art, the graphene transparent conductive film has better permeability, transparency and conductivity.
Drawings
Fig. 1 is a schematic structural diagram of a graphene transparent conductive film having a rivet structure according to the present invention.
Detailed Description
The following examples are merely exemplary for further understanding and illustrating the nature of the invention, and are not intended to limit the scope of the invention in any way.
Example 1 graphene transparent conductive film having rivet structure
Common glass is used as a substrate, ATO is used as a rivet material, and graphene oxide is used. Treating the surface of the glass with H2 plasma for 10min to obtain hydrophilic glass surface. Graphene oxide with an average area of 100um2 was dissolved in deionized water to obtain a 1mg/ml graphene oxide aqueous solution. And centrifuging the graphene aqueous solution at low speed of 1000r/min and 3000r/min to remove agglomeration and graphite oxide impurities. And forming 1 to 5 graphene oxide layers on the surface of the hydrophilic glass by using a spin coating method. Silane coupling agent is used as dispersing agent to obtain well-dispersed ATO dispersion liquid (ATO content is 1%), ATO average grain size is 20nm, and a rivet layer is introduced on graphene oxide by a spin coating method. A graphene oxide layer is formed on the rivet layer also using a spin coating method. And drying the obtained film at 80 ℃ for 2 hours, and reducing the film for 20s at 550 ℃ to obtain the transparent conductive film. The sheet resistance was 1050 ohm/square and the average transmittance in the visible region was 90.2%.
Example 2 graphene transparent conductive film having rivet structure
The method is characterized in that a PET flexible material is used as a substrate, a carbon nano tube is used as a rivet material, and NH3 plasma is used as a reducing agent to reduce graphene oxide. The PET substrate was treated with a mixed solution of ammonia, hydrogen peroxide and water to obtain a hydrophilic surface. Graphene oxide with an average area of 100um2 was dissolved in deionized water to obtain a 1mg/ml graphene oxide aqueous solution. And standing and precipitating the graphene aqueous solution for 7 days to remove the impurities of the agglomerated graphene and the oxidized graphene. And mixing the graphene oxide solution with n-butanol in a ratio of 1:5 to obtain a solution A. And dropwise adding the solution A into deionized water to obtain a Langmuir-Blodgett film of graphene oxide, and vertically pulling to obtain 1-2 layers of graphene oxide films on a PET substrate. DMF ultrasonically disperses carbon nanotubes with the pipe diameter of 20nm, and a rivet layer is introduced by a spin-coating method. A graphene oxide layer is formed on the rivet layer, also using the L-B method. And drying the obtained film at 80 ℃ for 2 hours, and reducing the film for 10min by using NH3 plasma to obtain the transparent conductive film. The sheet resistance was 600 ohm/square and the average transmittance in the visible region was 86.7%.
Example 3
Common glass is used as a substrate, ATO is used as a rivet material, and DMF is used for dispersing and reducing graphene oxide to manufacture the graphene film. Treating the surface of the glass with H2 plasma for 10min to obtain hydrophilic glass surface. And (3) dispersing reduced graphene oxide with the average area of 100um2 in DMF, and performing ultrasonic dispersion for 1 hour to obtain a stable dispersion liquid. And forming a graphene layer on the surface of the hydrophilic glass by using a spin coating method. Silane coupling agent is used as dispersing agent to obtain well-dispersed ATO dispersion liquid (ATO content is 1%), ATO average grain size is 20nm, and a rivet layer is introduced on graphene oxide by a spin coating method. A graphene oxide layer is formed on the rivet layer also using a spin coating method. And drying the obtained film at 80 ℃ for 2 hours to obtain the transparent conductive film.
In the method of example 3, it is difficult to obtain an electrically conductive thin film, and even when a plurality of layers of graphene are stacked by spin coating several times, it is difficult to form a continuous graphene thin film on the surface of the substrate. This is probably because graphene lacks oxygen-containing groups, and cannot repel each other from sheet to sheet by electrostatic repulsion to form a monolayer-laid film on the substrate surface, and tends to agglomerate and accumulate in space.
The above embodiments are merely exemplary, and simple addition, subtraction or replacement without departing from the spirit of the present invention is also within the scope of the present invention.
Claims (6)
1. A graphene transparent conductive film is characterized by comprising no more than 10 graphene layers, wherein each graphene layer comprises a plurality of discontinuous graphene sheets, a transparent conductive nano material layer with a rivet structure is arranged between every two graphene layers, the discontinuous graphene sheets are connected, the transparent conductive nano material is a metal oxide, a metal nanowire or a nano carbon material, and the graphene transparent conductive film comprises the following preparation processes:
(1) introducing a graphene oxide layer on a substrate;
(2) introducing a transparent conductive nano material layer on the graphene oxide layer;
(3) introducing a graphene oxide layer on the transparent conductive nano material layer;
(4) reducing the graphene oxide;
wherein the nano-carbon material is a graphene nanoribbon.
2. The conductive film of claim 1, wherein the graphene layer is 1-5 layers.
3. The conductive film of claim 1, wherein the metal oxide is selected from the group consisting of ITO, ATO, SnO2, ZnO, AZO, CdO, CdIn2O4, Cd2SnO4, Zn2SnO4, ZnSnO4, and In2O3 — ZnO In combination of one or more thereof, and has a thickness of 5 to 100 nm.
4. The conductive film of claim 1, wherein the graphene oxide layer is introduced by a method selected from one or more of dipping, printing, roll coating, blade coating, wire bar coating, spray coating, spin coating, and pulling.
5. The conductive film of claim 1, wherein the transparent conductive nanomaterial layer is introduced by a method selected from one or more of dipping, printing, roll coating, blade coating, wire bar coating, spray coating, spin coating, pulling, chemical vapor deposition, physical vapor deposition, evaporation coating, and sputter coating.
6. The conductive film according to claim 1, wherein the graphene oxide is reduced by a method selected from one or more of a thermal reduction method, a microwave reduction method, a plasma reduction method, a reducing gas reduction method, a photocatalytic reduction method, a reducing acid reduction method, and a phenol reduction method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811129760.7A CN109192359B (en) | 2018-09-27 | 2018-09-27 | Graphene transparent conductive film with rivet structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811129760.7A CN109192359B (en) | 2018-09-27 | 2018-09-27 | Graphene transparent conductive film with rivet structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109192359A CN109192359A (en) | 2019-01-11 |
| CN109192359B true CN109192359B (en) | 2020-07-07 |
Family
ID=64906503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811129760.7A Active CN109192359B (en) | 2018-09-27 | 2018-09-27 | Graphene transparent conductive film with rivet structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109192359B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110289172A (en) * | 2019-07-03 | 2019-09-27 | 曲靖贝塔科技有限公司 | Graphene-cadmium oxide dye-sensitized solar cell working electrode preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202799224U (en) * | 2012-09-28 | 2013-03-13 | 江苏物联网研究发展中心 | Transparent electric heating film based on graphene |
| CN103794265A (en) * | 2014-02-26 | 2014-05-14 | 无锡格菲电子薄膜科技有限公司 | Composite material of graphene and nanowires and preparation method thereof |
| CN204087181U (en) * | 2014-05-20 | 2015-01-07 | 深圳市航泰光电有限公司 | A kind of layer structure of grapheme capacitive touch screen |
| CN104882223A (en) * | 2015-04-27 | 2015-09-02 | 国家纳米科学中心 | Oxidized graphene/silver nanowire composite transparent conducting thin film and preparation method thereof |
| KR20160102783A (en) * | 2015-02-23 | 2016-08-31 | 한국교통대학교산학협력단 | Method for preparing flexible transparent conductive film and flexible transparent conductive film manufactured thereby |
| CN107342401A (en) * | 2017-06-02 | 2017-11-10 | 深圳启辰新能源科技有限公司 | Multi-functional film layer carbon coated/sulphur composite positive pole of conducting polymer/ionomer/graphene and preparation method thereof |
-
2018
- 2018-09-27 CN CN201811129760.7A patent/CN109192359B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202799224U (en) * | 2012-09-28 | 2013-03-13 | 江苏物联网研究发展中心 | Transparent electric heating film based on graphene |
| CN103794265A (en) * | 2014-02-26 | 2014-05-14 | 无锡格菲电子薄膜科技有限公司 | Composite material of graphene and nanowires and preparation method thereof |
| CN204087181U (en) * | 2014-05-20 | 2015-01-07 | 深圳市航泰光电有限公司 | A kind of layer structure of grapheme capacitive touch screen |
| KR20160102783A (en) * | 2015-02-23 | 2016-08-31 | 한국교통대학교산학협력단 | Method for preparing flexible transparent conductive film and flexible transparent conductive film manufactured thereby |
| CN104882223A (en) * | 2015-04-27 | 2015-09-02 | 国家纳米科学中心 | Oxidized graphene/silver nanowire composite transparent conducting thin film and preparation method thereof |
| CN107342401A (en) * | 2017-06-02 | 2017-11-10 | 深圳启辰新能源科技有限公司 | Multi-functional film layer carbon coated/sulphur composite positive pole of conducting polymer/ionomer/graphene and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109192359A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11037693B2 (en) | Graphene oxide-metal nanowire transparent conductive film | |
| JP6291027B2 (en) | Ultrasonic spray coating of conductive transparent films with bonded graphene and conductive nanofilaments | |
| Tien et al. | The production of graphene nanosheets decorated with silver nanoparticles for use in transparent, conductive films | |
| WO2018036428A1 (en) | Metal nanowire-oxidation-resistant material combined transparent conductive film and preparation therefor | |
| Xue et al. | Facile synthesis of silver nanowires with different aspect ratios and used as high-performance flexible transparent electrodes | |
| US8871296B2 (en) | Method for producing conducting and transparent films from combined graphene and conductive nano filaments | |
| Zheng et al. | Field emission from a composite of graphene sheets and ZnO nanowires | |
| Ding et al. | Enhancement of field emission and photoluminescence properties of graphene-SnO2 composite nanostructures | |
| Chu et al. | Fabrication of sintering-free flexible copper nanowire/polymer composite transparent electrodes with enhanced chemical and mechanical stability | |
| EP2402285B1 (en) | Method for fabricating composite material comprising nano carbon and metal or ceramic | |
| CN102391737A (en) | Water-solubility silver nanowire writing ink and preparation method thereof as well as using method thereof | |
| He et al. | Silver-decorated reduced graphene oxides as novel building blocks for transparent conductive films | |
| KR20130122429A (en) | Hybrid electrode using ag nanowire and graphene and manufacturing method of the same | |
| CN106611627A (en) | High-quality carbon nanotube transparent conductive film, preparation method thereof and applications | |
| KR101341508B1 (en) | Transparent Conductive Nano Particle of Core-Shell Structure and Ink Including the Same | |
| Wang et al. | Facile synthesis of ultralong and thin copper nanowires and its application to high-performance flexible transparent conductive electrodes | |
| Nayeri et al. | Surface structure and field emission properties of cost effectively synthesized zinc oxide nanowire/multiwalled carbon nanotube heterojunction arrays | |
| Suriani et al. | Synthesis, transfer and application of graphene as a transparent conductive film: a review | |
| Wang et al. | Printable inorganic nanomaterials for flexible transparent electrodes: from synthesis to application | |
| KR102591112B1 (en) | Population of metal oxide nanosheets, preparation method thereof, and elelctrical conductor and elecronic device including the same | |
| CN109192359B (en) | Graphene transparent conductive film with rivet structure and preparation method thereof | |
| Koo et al. | Effect of hybrid nanoinks on solution-based Sn-doped In2O3 films under low-temperature microwave annealing | |
| Bu et al. | A highly conductive and transparent solution processed AZO/MWCNT nanocomposite | |
| He et al. | Growth of vertical MoS2 nanosheets on carbon materials by chemical vapor deposition: Influence of substrates | |
| US20170040089A1 (en) | Methods of preparing conductors, conductors prepared therefrom, and electronic devices including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201015 Address after: 401329 Chongqing Jiulongpo District Feng Sheng Road No. 27 of No. 3 Patentee after: Chongqing Xinhe Qiyue Technology Co.,Ltd. Address before: 401329 Fengsheng Road, Jiulongpo District, Chongqing Patentee before: CHONGQING YONGYANG OPTOELECTRONIC Co.,Ltd. |