CN110875108A - Preparation method of metal grid type transparent electrode - Google Patents
Preparation method of metal grid type transparent electrode Download PDFInfo
- Publication number
- CN110875108A CN110875108A CN201911202241.3A CN201911202241A CN110875108A CN 110875108 A CN110875108 A CN 110875108A CN 201911202241 A CN201911202241 A CN 201911202241A CN 110875108 A CN110875108 A CN 110875108A
- Authority
- CN
- China
- Prior art keywords
- transparent electrode
- metal
- film
- solvent
- spin
- 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.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention discloses a preparation method of a metal grid transparent electrode, which is characterized in that two polymers are dissolved in a first solvent according to a certain weight ratio to prepare a solution with the concentration of 1mg/mL-500mg/mL, and the solution is spin-coated on the surface of a metal film to prepare a film. A second solvent is used to selectively remove one of the polymers to form a grid pattern. And removing the uncovered metal surface by using an etching method, and removing the spin-coating film to obtain the metal grid transparent electrode. The obtained metal grid transparent electrode has micron-scale line width. The transmittance is 60-90%, and the sheet resistance is 1-1000 omega/sq.
Description
Technical Field
The invention relates to the technical field of electrode preparation methods, in particular to a preparation method of a metal grid type transparent electrode.
Background
Transparent electrodes are indispensable components in modern photoelectric devices, and have been widely applied in the fields of solar cells, light emitting diodes, touch screens, intelligent glass and the like. The commercialized transparent electrode material is an Indium Tin Oxide (ITO) compound, and has the problems of high brittleness and high cost. Transparent electrode materials replacing ITO include graphene, carbon nanotubes, conductive polymers, ultra-thin metal films, and metal mesh transparent electrodes.
The single-layer graphene has good conductivity. But the preparation of single-layer, large-area and high-quality graphene is a difficult point. The carbon nano tube has higher contact resistance when being used for preparing the transparent electrode, so that the electric conductivity is poor. Conductive polymers have good light transmission properties but poor electrical conductivity. The metal mesh transparent electrode is a typical representative of a new generation of transparent electrodes. The light-transmitting material utilizes the good conductivity of metal and realizes the light-transmitting performance through the hollowed-out patterns. Silver has the highest conductivity of all metals, but at a higher cost. Copper has the second highest conductivity and costs about 1% of ITO. Therefore, the copper grid transparent electrode has a very wide application prospect.
In the metal grid preparation method, spin coating or spray coating of the metal wire is simpler. However, the degree of wire aggregation of the resulting metal mesh is not easily controlled, the wires overlap each other, the surface roughness is high, and an additional welding (welding) step is generally required. The second concept is the template method, which uses various templates to realize the final metal grid pattern. The template method can be divided into an additive method and a subtractive method according to the mechanism. The additive method is to perform metallization on the basis of a template, and realize final patterns by combining transfer (transfer) or lift-off (lift-off). The metal grid with the same pattern as the electrospinning film can be formed by using the electrospinning film as a template and combining metal evaporation. The metal trench transparent electrodes can be prepared by transferring a metal grid pattern onto a substrate (Nature Nanotechnology, 2013, 8, 421). The pattern inversion scheme forms mesh grooves on the substrate in advance, and prepares metal mesh transparent electrodes in combination with metallization and stripping of the sacrificial layer (Advanced materials technologies, 2016, 1, 1600095). A typical example of the subtractive method is an etching method. The electrostatic spinning film is used as a template to be attached to the surface of the continuous metal film, and the part which is not shielded by the mask is removed by wet etching or dry etching to form a metal grid (ACS Nano, 2014,4782 and ACS Nano, 2015,9, 2502).
Realizing continuous mesh patterns is a key problem for preparing metal mesh transparent electrodes. Various methods have been used to address this problem, including electrostatic spinning templates (ACS Nano, 2014,4782), self-crazing templates (advanced materials Technologies, 2016, 1, 1600095), and breathing pattern templates (2016,8, 11122). In addition, phase separation of the polymer can also form various network patterns, for example, Nano line width patterns can be prepared by using phase separation of polystyrene-polymethylmethacrylate block copolymer in combination with photolithography (ACS Nano, 2015,9, 7506). But the cost of photolithography is high.
Disclosure of Invention
The invention aims to solve the problems that: the invention provides a preparation method of a metal grid type transparent electrode, wherein the net-shaped pattern is realized by spin-coating a polymer. The spin-coating film generates continuous network stripes by selecting the polymer category, the solvent type, the solution concentration, the spin-coating speed and the spin-coating time. And (4) taking the net-shaped stripes as a template, and combining an etching process to obtain the final metal grid transparent electrode. The method has the characteristics of low cost and rapid molding.
The technical scheme provided by the invention for solving the problems is as follows: a preparation method of a metal grid type transparent electrode comprises the steps of dissolving two polymers in a solvent 1 according to a certain weight ratio to prepare a solution with the concentration of 1mg/mL-500mg/mL, and spin-coating the solution on the surface of a metal film to prepare a film; selectively removing a polymer with a solvent 2 to form a grid pattern; removing the unmasked metal surface by an etching method, and removing the spin-coating film to obtain a metal grid transparent electrode;
the solvent 1 is one of tetrahydrofuran, cyclohexane, chloroform, acetone, N-dimethylformamide, ethanol, toluene, dichloromethane and ethyl acetate;
the polymer is two of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl formal, polystyrene, polycaprolactone, polymethyl methacrylate, polybutyl methacrylate, polyacrylonitrile-polystyrene copolymer and polystyrene-polymethyl methacrylate copolymer;
the solvent 2 is one of tetrahydrofuran, cyclohexane, chloroform, acetone, N-dimethylformamide, ethanol, toluene, dichloromethane, ethyl acetate, acetic acid and cyclohexanone.
Preferably, the polymer has a weight average molecular weight of between 1 and 200 ten thousand.
Preferably, the etching method is wet etching.
Compared with the prior art, the invention has the advantages that: the invention selects two polymers with weight average molecular weight of 1-200 ten thousand to be dissolved in a solvent 1 according to a certain weight ratio to prepare a solution with the concentration of 1mg/mL-500 mg/mL. The solution is spin-coated on the surface of the metal film at the spin-coating speed of 200-6000rpm for 10-100 s. Then, one polymer is selectively removed by a solvent 2 to form a polymer pattern on the metal thin film. And removing the metal surface which is not shielded by wet etching, and removing the polymer pattern to obtain the final metal grid transparent electrode. The metal grid transparent electrode prepared by the invention has the metal wire line width of 1-100 microns. The transmittance is 60-90%, and the sheet resistance is 1-1000 omega/sq. The metal grid transparent electrode prepared by the invention is observed by an optical microscope, and the line width of the grid metal line is known to be changed between 1 micron and 100 microns. Compared with the existing preparation method of the metal grid transparent electrode, the preparation method has the advantages of simple preparation process and low cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic diagram of the steps of the present invention.
FIG. 2 is an optical microscope photograph of a polymer film of the present invention.
FIG. 3 is an optical microscope photograph of the metal mesh transparent electrode of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Example 1
0.5g of PVB having a weight average molecular weight of 9 ten thousand and 0.5g of PVP having a weight average molecular weight of 130 ten thousand were dissolved in 20mL of absolute ethanol, and a homogeneous solution was obtained by magnetic stirring and ultrasonic dispersion. The solution is spin-coated on the surface of a copper film (the copper film is attached to polyethylene terephthalate (PET)), the rotating speed is 3000rpm, and the time is 30s, so that the phase-separated film is obtained. And selectively removing PVP by using deionized water to obtain a PVB mesh pattern. And etching the unmasked copper by using a ferric chloride solution to obtain the copper grid transparent electrode.
Example 2
0.3g of PVB having a weight average molecular weight of 9 ten thousand and 0.5g of PS having a weight average molecular weight of 20 ten thousand were dissolved in 20mL of ethyl acetate, and a homogeneous solution was obtained by magnetic stirring and ultrasonic dispersion. The solution is coated on the surface of a copper film (the copper film is attached to PET) in a spin mode, the rotating speed is 1000rpm, and the time is 90 seconds, so that the phase separation thin film is obtained. PS was selectively removed with toluene to obtain a PVB mesh pattern. And etching the unmasked copper by using an ammonium persulfate solution to obtain the copper grid transparent electrode.
Example 3
0.5g of PAN having a weight average molecular weight of 20 ten thousand and 0.3g of PMMA having a weight average molecular weight of 10 ten thousand were dissolved in 20mL of chloroform, and a homogeneous solution was obtained by magnetic stirring and ultrasonic dispersion. The solution is spin-coated on the surface of a copper film (the copper film is attached to PET), the rotating speed is 2000rpm, and the time is 60s, so that the phase-separated thin film is obtained. The PAN was selectively removed with DMF to give PMMA mesh pattern. And etching the unmasked copper by using a hydrogen peroxide solution to obtain the copper grid transparent electrode.
Example 4
0.3g of PMMA having a weight average molecular weight of 5 ten thousand and 0.3g of PS having a weight average molecular weight of 10 ten thousand were dissolved in 20mL of chloroform, and a homogeneous solution was obtained by magnetic stirring and ultrasonic dispersion. The solution is spin-coated on the surface of a copper film (the copper film is attached to PET), the rotating speed is 3000rpm, and the time is 15s, so that the phase separation thin film is obtained. Selectively removing PMMA by using acetone to obtain a PS mesh pattern. And etching the unmasked copper by using a hydrogen peroxide solution to obtain the copper grid transparent electrode.
Example 5
0.5g of PAN having a weight average molecular weight of 20 ten thousand and 0.3g of PMMA having a weight average molecular weight of 10 ten thousand were dissolved in 20mL of tetrahydrofuran, and a homogeneous solution was obtained by magnetic stirring and ultrasonic dispersion. The solution is spin-coated on the surface of a copper film (the copper film is attached to PET), the rotating speed is 1000rpm, and the time is 15s, so that the phase separation thin film is obtained. Selectively removing PMMA by using acetone to obtain a PAN reticular pattern. And etching the unmasked copper by using an ammonium persulfate solution to obtain the copper grid transparent electrode.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (3)
1. A preparation method of a metal grid type transparent electrode is characterized by comprising the following steps: dissolving two polymers in a solvent 1 according to a certain weight ratio to prepare a solution with the concentration of 1mg/mL-500mg/mL, and spin-coating the solution on the surface of a metal film to prepare a film; selectively removing a polymer with a solvent 2 to form a grid pattern; removing the unmasked metal surface by an etching method, and removing the spin-coating film to obtain a metal grid transparent electrode;
the solvent 1 is one of tetrahydrofuran, cyclohexane, chloroform, acetone, N-dimethylformamide, ethanol, toluene, dichloromethane and ethyl acetate;
the polymer is two of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl formal, polystyrene, polycaprolactone, polymethyl methacrylate, polybutyl methacrylate, polyacrylonitrile-polystyrene copolymer and polystyrene-polymethyl methacrylate copolymer;
the solvent 2 is one of tetrahydrofuran, cyclohexane, chloroform, acetone, N-dimethylformamide, ethanol, toluene, dichloromethane, ethyl acetate, acetic acid and cyclohexanone.
2. The method for preparing a metal mesh-type transparent electrode according to claim 1, wherein: the weight average molecular weight of the polymer is between 1 and 200 ten thousand.
3. The method for preparing a metal mesh-type transparent electrode according to claim 1, wherein: the etching method is wet etching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911202241.3A CN110875108A (en) | 2019-11-29 | 2019-11-29 | Preparation method of metal grid type transparent electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911202241.3A CN110875108A (en) | 2019-11-29 | 2019-11-29 | Preparation method of metal grid type transparent electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110875108A true CN110875108A (en) | 2020-03-10 |
Family
ID=69717350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911202241.3A Pending CN110875108A (en) | 2019-11-29 | 2019-11-29 | Preparation method of metal grid type transparent electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110875108A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112281302A (en) * | 2020-10-20 | 2021-01-29 | 西安工程大学 | Mask method electrostatic spinning integrated copper conductive film layer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090107953A1 (en) * | 2007-10-29 | 2009-04-30 | International Business Machines Corporation | Methods for forming surface features using self-assembling masks |
| US20090214823A1 (en) * | 2008-02-22 | 2009-08-27 | International Business Machines Corporation | Methods for aligning polymer films and related structures |
| CN102983065A (en) * | 2011-09-06 | 2013-03-20 | 中芯国际集成电路制造(北京)有限公司 | Forming method for pattern, mask pattern and manufacture method for semiconductor component |
| KR20170050164A (en) * | 2015-10-29 | 2017-05-11 | 한국과학기술원 | Metal grid-Silver nanowire mixed transparent electrodes and the preparation method of metal grid using polymeric nanofiber mask |
| CN107381498A (en) * | 2016-05-17 | 2017-11-24 | 边捷 | A kind of sheet liquid phase nanometer grain preparation method |
-
2019
- 2019-11-29 CN CN201911202241.3A patent/CN110875108A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090107953A1 (en) * | 2007-10-29 | 2009-04-30 | International Business Machines Corporation | Methods for forming surface features using self-assembling masks |
| US20090214823A1 (en) * | 2008-02-22 | 2009-08-27 | International Business Machines Corporation | Methods for aligning polymer films and related structures |
| CN102983065A (en) * | 2011-09-06 | 2013-03-20 | 中芯国际集成电路制造(北京)有限公司 | Forming method for pattern, mask pattern and manufacture method for semiconductor component |
| KR20170050164A (en) * | 2015-10-29 | 2017-05-11 | 한국과학기술원 | Metal grid-Silver nanowire mixed transparent electrodes and the preparation method of metal grid using polymeric nanofiber mask |
| CN107381498A (en) * | 2016-05-17 | 2017-11-24 | 边捷 | A kind of sheet liquid phase nanometer grain preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112281302A (en) * | 2020-10-20 | 2021-01-29 | 西安工程大学 | Mask method electrostatic spinning integrated copper conductive film layer and preparation method thereof |
| CN112281302B (en) * | 2020-10-20 | 2022-09-09 | 西安工程大学 | Mask method electrostatic spinning integrated copper conductive film layer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106782769B (en) | Flexible and transparent conductive laminated film of low roughness low square resistance and preparation method thereof | |
| Fuh et al. | Pattern transfer of aligned metal nano/microwires as flexible transparent electrodes using an electrospun nanofiber template | |
| CN100472696C (en) | Fabrication method of field emitter electrode | |
| CN102391737B (en) | Water-solubility silver nanowire writing ink and preparation method thereof as well as using method thereof | |
| Jiang et al. | Facile preparation of Cu/Ag core/shell electrospun nanofibers as highly stable and flexible transparent conductive electrodes for optoelectronic devices | |
| US10535792B2 (en) | Transparent conductor and preparation method for same | |
| CN103213350B (en) | Transparent conductive film and preparation method thereof | |
| KR20120021451A (en) | Method for manufacturing transparent conductive layer and transparent conductive layer manufactured by the method | |
| JP2009205924A (en) | Transparent conductive film, transparent conductive member, and silver nano wire dispersion solution and manufacturing method of transparent conductive film | |
| WO2013004667A1 (en) | Transparent conductive multilayer electrode and associated manufacturing process | |
| CN107154283B (en) | Electromigration-resistant silver nanowire composite film and preparation method thereof | |
| JP6599245B2 (en) | Transparent conductive film containing silver nanowires | |
| JP6598692B2 (en) | Composition comprising silver nanowires | |
| CN112562888B (en) | Preparation method of silver nanowire solution and preparation method of transparent conductive film | |
| CN109080281B (en) | Method for preparing flexible transparent conductive film based on wetting substrate fine ink-jet printing | |
| Singh et al. | An embedded-PVA@ Ag nanofiber network for ultra-smooth, high performance transparent conducting electrodes | |
| CN107481801B (en) | A kind of preparation method of silver nanowires grid transparent electrode | |
| CN112614627B (en) | Flexible transparent electrode with high conductive coverage rate and preparation method thereof | |
| JP2017022095A (en) | Conductive film and manufacturing method therefor | |
| WO2011023498A1 (en) | Doping of carbon nanotube films for the fabrication of transparent electrodes | |
| CN110875108A (en) | Preparation method of metal grid type transparent electrode | |
| CN104813498A (en) | Transparent electrode and associated production method | |
| Liu et al. | A crack templated copper network film as a transparent conductive film and its application in organic light-emitting diode | |
| CN103985433A (en) | Carbon nano-tube conductive thin film and manufacturing method thereof | |
| CN105702319A (en) | Bending-resistant transparent copper sulfide conducting film and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200310 |
|
| WD01 | Invention patent application deemed withdrawn after publication |