CN107887076A - A kind of preparation method of graphene conductive film - Google Patents
A kind of preparation method of graphene conductive film Download PDFInfo
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- CN107887076A CN107887076A CN201711026161.8A CN201711026161A CN107887076A CN 107887076 A CN107887076 A CN 107887076A CN 201711026161 A CN201711026161 A CN 201711026161A CN 107887076 A CN107887076 A CN 107887076A
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract
The invention discloses a kind of preparation method of graphene conductive film, belong to conductive film production technical field.It the described method comprises the following steps：A. deposition nickel film layer deposits nickel film layer on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method；B, graphene oxide film layer is prepared：Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 60~90 DEG C, forms the graphene oxide film layer that thickness is 20~30 μm；C. deposited graphite alkene layer：Using CVD, deposited graphite alkene film layer, the thickness of the graphene film layer are 50~90 μm on graphene oxide layer；D. the semi-finished product for obtaining step C are post-processed and carry out cooling processing, after temperature is down to room temperature, graphene oxide film layer is cleaned with dust technology, surface nickel film layer is removed, is then dried and obtains the graphene conductive film.The present invention has the advantages of production cost is low, efficiency high.
Description
Technical field
The present invention relates to a kind of preparation method of graphene conductive film, belong to conductive film production technical field.
Background technology
With the development of science and technology, society is also more and more to the demand of new material.Material is human civilization progress
With the material base of development in science and technology, the renewal of material makes the life of people, and also there occurs great variety.At present, it is booming new
The transparent and conductive thin-film material of type is in liquid crystal display, touch-screen, smart window, solar cell, microelectronics, information sensing
The device even field such as military project, which is obtained for, to be widely applied, and is being penetrated into other sciemtifec and technical spheres.Due to thin film technique
It is closely related with multiple technologies, thus the scientists of every field are excited to film preparation and its interest of performance.
Conductive film is that a kind of energy is conductive, realizes the film of some specific electric functions, is widely used in display, touches
Touch in the electronic devices such as screen and solar cell.At present, as a kind of transparent and conducting semiconductor material tin indium oxide
(ITO）, it is widely used in film applications always.Transparent lead is prepared by using magnetron sputtering that ITO is deposited over the transparent substrate
Conductive film, transparent base include such as glass and polyethylene terephthalate（PET）Film etc..Because tin indium oxide has height
Electrical conductivity, high thang-kng rate, so as one of main material for preparing conductive film.But tin indium oxide conductive film makes
There is also some shortcomings during, including:(1) indium resource is less, causes price continuous rise so that ITO turns into increasingly high
Expensive material, such as spraying, pulsed laser deposition, plating.And indium oxide has certain toxicity, unreasonable easily cause is recycled
Environmental pollution.（2）Characteristic crisp ITO prevents it from meeting some new opplications (such as flexible flexible display, touch
Screen, organic solar batteries) performance requirement, be not suitable for the production of flexible electronic device of future generation.The two of graphene uniqueness
Crystal structure is tieed up, imparts its unique performance, research finds that graphene has excellent mechanical performance and excellent electrical property
Matter, the electron mobility of graphene is up to 15000cm2v under normal temperature-1s-1, and resistivity is only 10-6Ωcm.Graphene is being permitted
It is many-sided that there is more potential advantages, such as quality, robustness, pliability, chemical stability, infrared light transmission than tin indium oxide
Property and price etc..Therefore graphene is expected to replace tin indium oxide very much, for developing thinner, the conductive faster flexible electronic of speed
Device.
At present, the preparation method of graphene mainly has：Micromechanics stripping method, oxidation-reduction method, chemical vapour deposition technique, have
Machine molecule intercalation method etc..Chemical vapour deposition technique is used by Somani etc. from 2006, with camphanone (camphor) for presoma,
Graphene film is obtained on nickel foil, scientists achieve much obtains grinding for thickness controllable grapheme lamella in different matrix
Study carefully progress.By carrying out chemical etching on metallic matrix, graphene sheet layer is separated and is transferred on another matrix, and this is just
Eliminate complicated machinery or chemical treatment method and obtain the graphene sheet layer of high quality.The state such as South Korea and Japan adopts one after another
Big size graphene transparent conductive film has been prepared in this way, and desired main application fields are in flat-panel screens
On, serve as anode.Such as in new OLED（OLED）On exploitation, OLED has cost low, all solid state, main
Dynamic luminous, brightness height, contrast is high, visual angle is wide, fast response time, thickness of thin, low-voltage direct-current drive, are low in energy consumption, work temperature
Degree scope is wide, the features such as soft screen display can be achieved, and turns into the developing direction of future display technology.
The content of the invention
It is an object of the invention to provide a kind of preparation method of new graphene conductive film, production cost is low, and energy
The graphene conductive film of large area is produced, disclosure satisfy that the demand of large-scale production.
In order to realize foregoing invention purpose, technical scheme is as follows：
1st, a kind of preparation method of graphene conductive film, comprises the following steps：
A. nickel film layer is deposited
Nickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum：8
×10-5~2 × 10-4Pa, 65~80 DEG C of underlayer temperature.
B, graphene oxide film layer is prepared
Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 60~90 DEG C, forms thickness as 20~30 μm
Graphene oxide film layer；
C. deposited graphite alkene layer
Using CVD on graphene oxide layer deposited graphite alkene film layer, the thickness of the graphene film layer is 50~90 μ
m；
D. post-process
The semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre
Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
In step A, the pressure of the sputtering is 2Pa.
In step C, during the CVD deposited graphite alkene film layer, carbon source is methane, gas H2；The temperature of deposition
Spend for 560~620 DEG C, the pressure of deposition is 1 × 10-4~2 × 10-4Pa。
In step D, the cleaning refers to soak 0.5~1h, dilute nitre to the semi-finished product after cooling with dilute nitric acid solution
The mass concentration of acid is 20~30%.
In step D, the condition of the drying is that 30~40min is dried at 90~110 DEG C.
The light transmittance of graphene conductive film produced by the present invention is 79~83%, assay method：It is purple using U-3010 types
Outside-visible spectrophotometer, using blank slide as reference, the saturating of graphene film is measured in 400-900nm wave-length coverages
Light rate, and the light transmittance of graphene film is used as using the light transmittance at wavelength X=550nm.
The resistance of graphene conductive film produced by the present invention is 1.0~1.5M Ω/sq, assay method：Using SB100A/
The distance between the film resistor, probe of graphene film is 3mm on 2 type four-point probe test slide base materials.
Beneficial effects of the present invention：
Compared with prior art, the present invention breaches the limitation of original technology, realizes a transparent graphene conductive film in reality
The leap that the large scale of small size to the industrial applications of testing interior is applied, there is the advantages of production cost is low, efficiency high, and this
Invention furthermore achieved that obtained conductive film visible light transmittance rate height by further parameter optimization, surface cleaning without
Pollution, pliability is good, and image shows clearly effect, is especially suitable for large-scale production, is expected to substitute traditional inorganic oxide electricity
Pole material ITO, promote the development of graphene conductive film industry, there is preferable economic benefit and social benefit.
Embodiment
Embodiment 1
1st, a kind of preparation method of graphene conductive film, comprises the following steps：
A. nickel film layer is deposited
Nickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum：8
×10-5, 65 DEG C of underlayer temperature.
B, graphene oxide film layer is prepared
Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 60 DEG C, forms the oxidation stone that thickness is 20 μm
Black alkene film layer；
C. deposited graphite alkene layer
Using CVD, deposited graphite alkene film layer, the thickness of the graphene film layer are 50 μm on graphene oxide layer；
D. post-process
The semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre
Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
Embodiment 2
1st, a kind of preparation method of graphene conductive film, comprises the following steps：
A. nickel film layer is deposited
Nickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum： 2
×10-4Pa, 80 DEG C of underlayer temperature.
B, graphene oxide film layer is prepared
Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 90 DEG C, forms the oxidation stone that thickness is 30 μm
Black alkene film layer；
C. deposited graphite alkene layer
Using CVD, deposited graphite alkene film layer, the thickness of the graphene film layer are 90 μm on graphene oxide layer；
D. post-process
The semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre
Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
In step A, the pressure of the sputtering is 2Pa.
In step C, during the CVD deposited graphite alkene film layer, carbon source is methane, gas H2；The temperature of deposition
Spend for 560 DEG C, the pressure of deposition is 1 × 10-4Pa。
In step D, the cleaning refers to soak 0.5h to the semi-finished product after cooling with dilute nitric acid solution, the dust technology
Mass concentration is 20%.
In step D, the condition of the drying is that 30min is dried at 90 DEG C.
Embodiment 3
The present embodiment is on the basis of embodiment 3, and in step C, during the CVD deposited graphite alkene film layer, carbon source is
Methane, gas H2；The temperature of deposition is 580 DEG C, and the pressure of deposition is 1 × 10-4Pa。
Embodiment 4
1st, a kind of preparation method of graphene conductive film, comprises the following steps：
A. nickel film layer is deposited
Nickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum： 2
×10-4Pa, 75 DEG C of underlayer temperature.
B, graphene oxide film layer is prepared
Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 75 DEG C, forms the oxidation stone that thickness is 25 μm
Black alkene film layer；
C. deposited graphite alkene layer
Using CVD, deposited graphite alkene film layer, the thickness of the graphene film layer are 60 μm on graphene oxide layer；
D. post-process
The semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre
Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
In step A, the pressure of the sputtering is 2Pa.
In step C, during the CVD deposited graphite alkene film layer, carbon source is methane, gas H2；The temperature of deposition
Spend for 600 DEG C, the pressure of deposition is 2 × 10-4Pa。
In step D, the cleaning refers to soak 1h, the matter of the dust technology to the semi-finished product after cooling with dilute nitric acid solution
It is 25% to measure concentration.
In step D, the condition of the drying is that 35min is dried at 100 DEG C.
Embodiment 5
1st, a kind of preparation method of graphene conductive film, comprises the following steps：
A. nickel film layer is deposited
Nickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum： 2
×10-4Pa, 80 DEG C of underlayer temperature.
B, graphene oxide film layer is prepared
Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 80 DEG C, forms the oxidation stone that thickness is 30 μm
Black alkene film layer；
C. deposited graphite alkene layer
Using CVD, deposited graphite alkene film layer, the thickness of the graphene film layer are 60 μm on graphene oxide layer；
D. post-process
The semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre
Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
In step A, the pressure of the sputtering is 2Pa.
In step C, during the CVD deposited graphite alkene film layer, carbon source is methane, gas H2；The temperature of deposition
Spend for 620 DEG C, the pressure of deposition is 2 × 10-4Pa。
In step D, the cleaning refers to soak 0.5h to the semi-finished product after cooling with dilute nitric acid solution, the dust technology
Mass concentration is 30%.
In step D, the condition of the drying is that 40min is dried at 110 DEG C.
The light transmittance of graphene conductive film made from the present embodiment is 79%；Resistance is 1.0M Ω/sq.
The assay method of light transmittance：Using U-3010 type ultraviolet-visible spectrophotometers, using blank slide as reference,
The light transmittance of graphene film is measured in 400-900nm wave-length coverages, and stone is used as using the light transmittance at wavelength X=550nm
The light transmittance of black alkene film.
The assay method of resistance：Using graphene film on SB100A/2 type four-point probe test slide base materials
The distance between film resistor, probe is 3mm.
Embodiment 6
1st, a kind of preparation method of graphene conductive film, comprises the following steps：
A. nickel film layer is deposited
Nickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum： 2
×10-4Pa, 80 DEG C of underlayer temperature.
B, graphene oxide film layer is prepared
Graphene oxide water solution is coated with nickel film layer, is dried under the conditions of 85 DEG C, forms the oxidation stone that thickness is 20 μm
Black alkene film layer；
C. deposited graphite alkene layer
Using CVD, deposited graphite alkene film layer, the thickness of the graphene film layer are 50 μm on graphene oxide layer；
D. post-process
The semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre
Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
In step A, the pressure of the sputtering is 2Pa.
In step C, during the CVD deposited graphite alkene film layer, carbon source is methane, gas H2；The temperature of deposition
Spend for 560 DEG C, the pressure of deposition is 1 × 10-4Pa。
In step D, the cleaning refers to soak 1h, the matter of the dust technology to the semi-finished product after cooling with dilute nitric acid solution
It is 20% to measure concentration.
In step D, the condition of the drying is that 30min is dried at 90 DEG C.
The light transmittance of graphene conductive film made from the present embodiment is 83%；Resistance is 1.5M Ω/sq.
The assay method of light transmittance：Using U-3010 type ultraviolet-visible spectrophotometers, using blank slide as reference,
The light transmittance of graphene film is measured in 400-900nm wave-length coverages, and stone is used as using the light transmittance at wavelength X=550nm
The light transmittance of black alkene film.
The assay method of resistance：Using graphene film on SB100A/2 type four-point probe test slide base materials
The distance between film resistor, probe is 3mm.
Claims (5)
- A kind of 1. preparation method of graphene conductive film, it is characterised in that：Comprise the following steps：A. nickel film layer is depositedNickel film layer is deposited on the glass substrate；The method of the deposition nickel film layer is magnetron sputtering method, background vacuum：8 ×10-5~2 × 10-4Pa, 65~80 DEG C of underlayer temperature；B, graphene oxide film layer is preparedGraphene oxide water solution is coated with nickel film layer, is dried under the conditions of 60~90 DEG C, forms thickness as 20~30 μm Graphene oxide film layer；C. deposited graphite alkene layerUsing CVD on graphene oxide layer deposited graphite alkene film layer, the thickness of the graphene film layer is 50~90 μ m；D. post-processThe semi-finished product that step C is obtained carry out cooling processing, after temperature is down to room temperature, by graphene oxide film layer with dilute nitre Acid is cleaned, and is removed surface nickel film layer, is then dried and obtains the graphene conductive film.
- A kind of 2. preparation method of graphene conductive film as claimed in claim 1, it is characterised in that：It is described to splash in step A The pressure penetrated is 2Pa.
- A kind of 3. preparation method of graphene conductive film as claimed in claim 1, it is characterised in that：It is described in step C During CVD deposited graphite alkene film layer, carbon source is methane, gas H2；The temperature of deposition is 560~620 DEG C, deposition Pressure is 1 × 10-4~2 × 10-4Pa。
- A kind of 4. preparation method of graphene conductive film as claimed in claim 1, it is characterised in that：It is described clear in step D Wash and refer to soak the semi-finished product after cooling 0.5~1h with dilute nitric acid solution, the mass concentration of the dust technology is 20~30%.
- A kind of 5. preparation method of graphene conductive film as claimed in claim 1, it is characterised in that：It is described dry in step D Dry condition is that 30~40min is dried at 90~110 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910870A (en) * | 2018-07-20 | 2018-11-30 | 西安交通大学 | A kind of pollution-free shifting process of CVD graphene obtains the laminated film and method of graphene oxide and graphene composite structure |
| CN109748264A (en) * | 2019-01-25 | 2019-05-14 | 复旦大学 | A kind of method of preparing graphene at normal temperature flexible electrode |
| CN112376027A (en) * | 2020-11-13 | 2021-02-19 | 无锡华鑫检测技术有限公司 | Preparation method of graphene oxide metal nanosheet composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710685A (en) * | 2013-12-24 | 2014-04-09 | 同济大学 | Spraying method for directly preparing graphene transparent conducting thin film on flexible substrate |
| CN106082693A (en) * | 2016-06-24 | 2016-11-09 | 成都天航智虹企业管理咨询有限公司 | A kind of method preparing transparent graphene conductive film |
| CN106158145A (en) * | 2016-06-24 | 2016-11-23 | 成都天航智虹企业管理咨询有限公司 | A kind of preparation method of graphene conductive film |
-
2017
- 2017-10-27 CN CN201711026161.8A patent/CN107887076A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710685A (en) * | 2013-12-24 | 2014-04-09 | 同济大学 | Spraying method for directly preparing graphene transparent conducting thin film on flexible substrate |
| CN106082693A (en) * | 2016-06-24 | 2016-11-09 | 成都天航智虹企业管理咨询有限公司 | A kind of method preparing transparent graphene conductive film |
| CN106158145A (en) * | 2016-06-24 | 2016-11-23 | 成都天航智虹企业管理咨询有限公司 | A kind of preparation method of graphene conductive film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910870A (en) * | 2018-07-20 | 2018-11-30 | 西安交通大学 | A kind of pollution-free shifting process of CVD graphene obtains the laminated film and method of graphene oxide and graphene composite structure |
| CN109748264A (en) * | 2019-01-25 | 2019-05-14 | 复旦大学 | A kind of method of preparing graphene at normal temperature flexible electrode |
| CN112376027A (en) * | 2020-11-13 | 2021-02-19 | 无锡华鑫检测技术有限公司 | Preparation method of graphene oxide metal nanosheet composite material |
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