CN107086083A - A kind of preparation method of the conductive metal film with flexible substrate - Google Patents
A kind of preparation method of the conductive metal film with flexible substrate Download PDFInfo
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- CN107086083A CN107086083A CN201710272655.8A CN201710272655A CN107086083A CN 107086083 A CN107086083 A CN 107086083A CN 201710272655 A CN201710272655 A CN 201710272655A CN 107086083 A CN107086083 A CN 107086083A
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- graphene
- flexible substrates
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- craquelure
- silver
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- 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
Abstract
The invention discloses a kind of preparation method of the conductive metal film with flexible substrate, the present invention realizes flexible conductive film continuity, large area is produced, greatly shorten the production cycle, increase substantially productivity ratio and reduction production cost, the problem of solving flexible metal network transparent conductive film large area consecutive production, metal nanoparticle growth in situ is on graphene, this mode has lower contact berrier than simply mixing graphene and metal nanoparticle, electronics in metal nanoparticle is more readily migrated on graphene, make that the carrier in graphene becomes is more, graphene has higher carrier mobility in itself simultaneously, the metal nanoparticle formation synergistic enhancing effect of graphene and growth thereon, transparent conductive film prepared by the present invention has more excellent electric conductivity.
Description
Technical field
The present invention relates to conductive material field, and in particular to a kind of preparation side of the conductive metal film with flexible substrate
Method.
Background technology
At present, it is fast with the photoelectric devices such as touch-screen, solar cell, intelligent window and flat-panel monitor and equipment
Speed development, the demand for low resistance, the transparent electrode material of high light transmittance energy is increasing
Transparent conductive film (TCFs) has excellent photoelectric characteristic, but also with lightweight, flexible, non-breakable, ring
Border is friendly, can use the advantages of volume to volume industrializes the continuous mode of production, and it has been widely used, for example：They can by with
In fields such as display, touch panel, solar cells.The film generally comprises transparent substrate, for example：PET etc., in the lining
The coating or film of transparent and electrically conductive are formed on bottom.Transparent conductive film material currently as main flow is tin indium oxide (ITO)
Film, the target for being primarily due to the material is prepared and film-forming process all comparative maturities.
Method prepared by transparent conductive film generally has physics and chemical two methods.Physical method refers to utilize material
Evaporation or when material is by particle bombardment surface atom produce sputtering and transport and deposit, realized in atoms range from
Physical process of the original matter to deposition film.Including：Vacuum vapor deposition method, sputtering method, ion beam deposition, means of electron beam deposition,
PRK vapour deposition method etc..Chemical method refers in the technology of plated film, chemically reacted, by between material from
Body property and chemical reaction realize the growth of film.Including：Chemical reduction method, chemical vapour deposition technique, sol-gel process are high
Temperature is decomposed（Thermal spraying）Method etc..Magnetron sputtering method can prepare the higher film of mass with pulsed laser deposition, but need
Complicated vacuum equipment is wanted, and production efficiency is relatively low, and cost is high, and film forming area is restricted.
The content of the invention
The present invention provides a kind of preparation method of the conductive metal film with flexible substrate, and the present invention realizes flexibility and led
Conductive film continuity, large area production, greatly shorten the production cycle, increase substantially productivity ratio and reduction production cost, solve
The problem of flexible metal network transparent conductive film large area consecutive production, metal nanoparticle growth in situ is in graphene
On, this mode has lower contact berrier, metal nano than simply mixing graphene and metal nanoparticle
Electronics in grain is more readily migrated on graphene, and make that the carrier in graphene becomes is more, while graphene has in itself
Higher carrier mobility, the metal nanoparticle formation synergistic enhancing effect of graphene and growth thereon, institute of the present invention
The transparent conductive film of preparation has more excellent electric conductivity.
To achieve these goals, the invention provides a kind of preparation side of the conductive metal film with flexible substrate
Method, this method comprises the following steps：
（1）Prepare the PET flexible substrates with Craquelure of carbon nano-tube modification
Coiled PET flexible substrate blowings, continuous conveying flexible substrate pass sequentially through prerinse, air-dry, atmospheric plasma it is clear
Wash, be coated with cracking liquid and heating, cracking liquid selects egg gel, and egg gel proportioning is egg and water volume ratio scope
For 1:1-2, forms Craquelure on flexible substrates, that is, the PET flexible substrates with Craquelure is made, the width of Craquelure is 2-
5 microns, in course of conveying, according to the Tensity size of PET flexible substrates, the tension force and speed of PET flexible substrates are adjusted
Section realizes PET flexible substrates constant speed and identical tension, and after the PET flexible substrates with Craquelure are made, to PET tortoises
The flexible substrate in crack is corrected, winding；
The cleaning agent that the prerinse is used can be hydrogen peroxide or alcohol etc., and effect is removed on PET flexible substrates surface
Dust, particle；
The atmospheric plasma is cleaned for PET flexible substrates surface to be cleaned, is modified and activated；
（2）Prepare metal conductive paste
Graphene oxide and metal salt are added solution is formed in reproducibility solvent, chosen ethylene glycol and be used as reproducibility agent, nitric acid
Silver is used as metal salt, wherein graphene oxide quality：The quality of silver element in silver nitrate：Quality=1 of ethylene glycol:（50-80）:
（200-300）.The solution of formation is heated at high temperature, silver ion directly will form silver in surface of graphene oxide in-situ reducing
Nano particle, simultaneous oxidation graphene also can be further reduced into graphene；In above-mentioned course of reaction, it can be suitably added
Surfactant prevents particle agglomeration；Graphene/silver nano-grain the compound for reacting generation is collected by centrifugation；
Viscosity modifier and solvent will be added in above-mentioned graphene/silver nano-grain compound, selected viscosity modifier is modification
Epoxy resin, selected solvent is dipropylene glycol methyl ether, and mechanical mixing is carried out afterwards, the electrocondution slurry after mixing is placed into 45
Deaeration is handled in -50 DEG C of vacuum drying oven, and the mass percent of dipropylene glycol methyl ether is 63-65% in final slurry, and graphene/
The mass percent of silver nano-grain compound is 8-10%, and surplus is epoxy resin, obtains metal conductive paste；
（3）Metal conductive paste is coated in the above-mentioned PET flexible substrates with Craquelure with coating method, is in temperature
15-20min is heated under conditions of 150-170 DEG C, transparent metal conductive film is produced.
Embodiment
Embodiment one
Coiled PET flexible substrate blowings, continuous conveying flexible substrate pass sequentially through prerinse, air-dry, atmospheric plasma it is clear
Wash, be coated with cracking liquid and heating, cracking liquid selects egg gel, and egg gel proportioning is egg and water volume ratio scope
For 1:1, Craquelure is formed on flexible substrates, that is, the PET flexible substrates with Craquelure is made, the width of Craquelure is 2-5
Micron, in course of conveying, according to the Tensity size of PET flexible substrates, the tension force and speed of PET flexible substrates are adjusted
PET flexible substrates constant speed and identical tension are realized, and after the PET flexible substrates with Craquelure are made, to being cracked with PET
The flexible substrate of seam is corrected, winding；The cleaning agent that the prerinse is used can be hydrogen peroxide or alcohol etc., and effect is to remove
Dust, particle on PET flexible substrates surface；The atmospheric plasma cleans clear for being carried out to PET flexible substrates surface
Clean, modified and activation.
Graphene oxide and metal salt are added solution are formed in reproducibility solvent, choose ethylene glycol as reproducibility agent,
Silver nitrate is used as metal salt, wherein graphene oxide quality：The quality of silver element in silver nitrate：Quality=1 of ethylene glycol:50:
200.The solution of formation is heated at high temperature, silver ion will be directly in surface of graphene oxide in-situ reducing formation silver nanoparticle
Grain, simultaneous oxidation graphene also can be further reduced into graphene；In above-mentioned course of reaction, surface work can be suitably added
Property agent prevents particle agglomeration；Graphene/silver nano-grain the compound for reacting generation is collected by centrifugation.
Viscosity modifier and solvent will be added in above-mentioned graphene/silver nano-grain compound, selected viscosity modifier is
Modified epoxy, selected solvent is dipropylene glycol methyl ether, and mechanical mixing is carried out afterwards, the electrocondution slurry after mixing is placed into
Enter deaeration in 45 DEG C of vacuum drying oven to handle, the mass percent of dipropylene glycol methyl ether is 63%, graphene/silver in final slurry
The mass percent of nano-particle complex is 8%, and surplus is epoxy resin, obtains metal conductive paste.
Metal conductive paste is coated in the above-mentioned PET flexible substrates with Craquelure with coating method, is in temperature
15min is heated under conditions of 150 DEG C, transparent metal conductive film is produced.
Embodiment two
Coiled PET flexible substrate blowings, continuous conveying flexible substrate pass sequentially through prerinse, air-dry, atmospheric plasma it is clear
Wash, be coated with cracking liquid and heating, cracking liquid selects egg gel, and egg gel proportioning is egg and water volume ratio scope
For 1:2, Craquelure is formed on flexible substrates, that is, the PET flexible substrates with Craquelure is made, the width of Craquelure is 2-5
Micron, in course of conveying, according to the Tensity size of PET flexible substrates, the tension force and speed of PET flexible substrates are adjusted
PET flexible substrates constant speed and identical tension are realized, and after the PET flexible substrates with Craquelure are made, to being cracked with PET
The flexible substrate of seam is corrected, winding；The cleaning agent that the prerinse is used can be hydrogen peroxide or alcohol etc., and effect is to remove
Dust, particle on PET flexible substrates surface；The atmospheric plasma cleans clear for being carried out to PET flexible substrates surface
Clean, modified and activation.
Graphene oxide and metal salt are added solution are formed in reproducibility solvent, choose ethylene glycol as reproducibility agent,
Silver nitrate is used as metal salt, wherein graphene oxide quality：The quality of silver element in silver nitrate：Quality=1 of ethylene glycol: 80:
300.The solution of formation is heated at high temperature, silver ion will be directly in surface of graphene oxide in-situ reducing formation silver nanoparticle
Grain, simultaneous oxidation graphene also can be further reduced into graphene；In above-mentioned course of reaction, surface work can be suitably added
Property agent prevents particle agglomeration；Graphene/silver nano-grain the compound for reacting generation is collected by centrifugation.
Viscosity modifier and solvent will be added in above-mentioned graphene/silver nano-grain compound, selected viscosity modifier is
Modified epoxy, selected solvent is dipropylene glycol methyl ether, and mechanical mixing is carried out afterwards, the electrocondution slurry after mixing is placed into
Enter deaeration in 50 DEG C of vacuum drying oven to handle, the mass percent of dipropylene glycol methyl ether is 65%, graphene/silver in final slurry
The mass percent of nano-particle complex is 10%, and surplus is epoxy resin, obtains metal conductive paste.
Metal conductive paste is coated in the above-mentioned PET flexible substrates with Craquelure with coating method, is in temperature
20min is heated under conditions of 170 DEG C, transparent metal conductive film is produced.
It is described above, only it is presently preferred embodiments of the present invention, any limitation is not done to the present invention, it is every according to invention skill
Any simple modification, change and equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (1)
1. a kind of preparation method of the conductive metal film with flexible substrate, this method comprises the following steps：
（1）Prepare the PET flexible substrates with Craquelure of carbon nano-tube modification
Coiled PET flexible substrate blowings, continuous conveying flexible substrate pass sequentially through prerinse, air-dry, atmospheric plasma it is clear
Wash, be coated with cracking liquid and heating, cracking liquid selects egg gel, and egg gel proportioning is egg and water volume ratio scope
For 1:1-2, forms Craquelure on flexible substrates, that is, the PET flexible substrates with Craquelure is made, the width of Craquelure is 2-
5 microns, in course of conveying, according to the Tensity size of PET flexible substrates, the tension force and speed of PET flexible substrates are adjusted
Section realizes PET flexible substrates constant speed and identical tension, and after the PET flexible substrates with Craquelure are made, to PET tortoises
The flexible substrate in crack is corrected, winding；
The cleaning agent that the prerinse is used can be hydrogen peroxide or alcohol etc., and effect is removed on PET flexible substrates surface
Dust, particle；
The atmospheric plasma is cleaned for PET flexible substrates surface to be cleaned, is modified and activated；
（2）Prepare metal conductive paste
Graphene oxide and metal salt are added solution is formed in reproducibility solvent, chosen ethylene glycol and be used as reproducibility agent, nitric acid
Silver is used as metal salt, wherein graphene oxide quality：The quality of silver element in silver nitrate：Quality=1 of ethylene glycol:（50-80）:
（200-300）,
The solution of formation is heated at high temperature, silver ion will be directly in surface of graphene oxide in-situ reducing formation silver nanoparticle
Grain, simultaneous oxidation graphene also can be further reduced into graphene；In above-mentioned course of reaction, surface work can be suitably added
Property agent prevents particle agglomeration；Graphene/silver nano-grain the compound for reacting generation is collected by centrifugation；
Viscosity modifier and solvent will be added in above-mentioned graphene/silver nano-grain compound, selected viscosity modifier is modification
Epoxy resin, selected solvent is dipropylene glycol methyl ether, and mechanical mixing is carried out afterwards, the electrocondution slurry after mixing is placed into 45
Deaeration is handled in -50 DEG C of vacuum drying oven, and the mass percent of dipropylene glycol methyl ether is 63-65% in final slurry, and graphene/
The mass percent of silver nano-grain compound is 8-10%, and surplus is epoxy resin, obtains metal conductive paste；
（3）Metal conductive paste is coated in the above-mentioned PET flexible substrates with Craquelure with coating method, is in temperature
15-20min is heated under conditions of 150-170 DEG C, transparent metal conductive film is produced.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336091A (en) * | 2018-10-11 | 2019-02-15 | 华南协同创新研究院 | A kind of graphene growth in situ silver nanowires hydridization conductive material and its preparation method and application |
| CN109706339A (en) * | 2018-12-29 | 2019-05-03 | 赛福纳米科技(徐州)有限公司 | The preparation method of silver-plated carbon nanometer tube-graphene composite material |
| WO2022077525A1 (en) * | 2020-10-13 | 2022-04-21 | 江苏仕邦柔性电子研究院有限公司 | Method for manufacturing flexible electronic device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531304A (en) * | 2013-09-18 | 2014-01-22 | 天津工业大学 | Method for quickly preparing large-area carbon nanometer tube flexible transparent conductive thin films and improving electric conductibility of thin films |
| KR20160111944A (en) * | 2014-01-22 | 2016-09-27 | 도요보 가부시키가이샤 | Conductive paste for laser etching, conductive thin film and conductive laminate |
| CN106244989A (en) * | 2016-07-26 | 2016-12-21 | 华南师范大学 | Produce the method and apparatus of flexible micro-nano metalolic network transparent conductive film continuously |
| CN106373664A (en) * | 2015-07-23 | 2017-02-01 | 北京华纳高科科技有限公司 | Preparation method and product of high-performance metal grid transparent conductive film |
-
2017
- 2017-04-24 CN CN201710272655.8A patent/CN107086083A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531304A (en) * | 2013-09-18 | 2014-01-22 | 天津工业大学 | Method for quickly preparing large-area carbon nanometer tube flexible transparent conductive thin films and improving electric conductibility of thin films |
| KR20160111944A (en) * | 2014-01-22 | 2016-09-27 | 도요보 가부시키가이샤 | Conductive paste for laser etching, conductive thin film and conductive laminate |
| CN106373664A (en) * | 2015-07-23 | 2017-02-01 | 北京华纳高科科技有限公司 | Preparation method and product of high-performance metal grid transparent conductive film |
| CN106244989A (en) * | 2016-07-26 | 2016-12-21 | 华南师范大学 | Produce the method and apparatus of flexible micro-nano metalolic network transparent conductive film continuously |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336091A (en) * | 2018-10-11 | 2019-02-15 | 华南协同创新研究院 | A kind of graphene growth in situ silver nanowires hydridization conductive material and its preparation method and application |
| CN109706339A (en) * | 2018-12-29 | 2019-05-03 | 赛福纳米科技(徐州)有限公司 | The preparation method of silver-plated carbon nanometer tube-graphene composite material |
| WO2022077525A1 (en) * | 2020-10-13 | 2022-04-21 | 江苏仕邦柔性电子研究院有限公司 | Method for manufacturing flexible electronic device |
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Application publication date: 20170822 |