CN106683791B - A method of preparing the flexible and transparent conductive electrode for having multi-level metal network - Google Patents

A method of preparing the flexible and transparent conductive electrode for having multi-level metal network Download PDF

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CN106683791B
CN106683791B CN201611186137.6A CN201611186137A CN106683791B CN 106683791 B CN106683791 B CN 106683791B CN 201611186137 A CN201611186137 A CN 201611186137A CN 106683791 B CN106683791 B CN 106683791B
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flexible
transparent conductive
preparing
conductive electrode
level metal
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CN106683791A (en
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霍峰蔚
李麟杰
邹冰花
郑冰
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Nanjing Tech University
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Nanjing Tech University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

The invention discloses a kind of methods preparing the flexible and transparent conductive electrode with multi-level metal network, the uniform spin coating photoresist layer in substrate, after front baking, dimethyl silicone polymer seal and chromium plate is used to be exposed as mask plate successively again, after subjected to development and drying, the conductive metal deposition layer in the flexible substrates again is finally ultrasonically treated and obtains the flexible and transparent conductive electrode with multi-level metal network.Preparation method of the present invention is simple, and the flexible transparent electrode structure novel of preparation is had excellent performance, and can be applied to the research and production of flexible transparent electrode, has far reaching significance to the research and development of flexible electronic device.

Description

A method of preparing the flexible and transparent conductive electrode for having multi-level metal network
Technical field
The present invention relates to the fields such as flexible electronic, sensing more particularly to photoetching technique to be used for field prepared by transparent electrode, More particularly to a kind of method for the flexible and transparent conductive electrode for preparing and having multi-level metal network.
Background technology
Flexible transparent electrode is a kind of important component of flexible electronic device.Flexible electronic device includes flexible sends out Light, flexible display device, flexible solar battery, flexible field-effect transistor, flexible biosensor etc..These are flexible , wearable electronic device by be next-generation consumer electronics product important form.Occur currently on the market soft Property printed electronic device R FID, as market is gradually approved and expands, more and more people put into the pass to flexible electronic Note and research.Photic zone and electrode of the flexible transparent electrode as these flexible electronic devices, flexibility, light transmittance and Electric conductivity is most important to the overall performance of device.Therefore, a kind of flexible transparent electrode of high quality is developed to flexible electronic Development, is especially significantly to the application of light-emitting display device and solar cell.
The material for being presently available for preparing transparent electrode is broadly divided into metal grill, metal-oxide film, graphene, carbon Nanotube, the types such as conducting polymer, by metal grill, metal-oxide film, graphene, the materials such as carbon nanotube are produced on It can be obtained by flexible transparent electrode in flexible and transparent substrate, transparent substrates include mainly the high scores such as PET, PDMS, polyimides Sub- material.Metal has natural advantage as electrode as most typical conductive material, high conductivity, therefore, many to study Personnel are dedicated to studying the preparation that metal material is used for flexible transparent electrode.Due to the opaqueness of metal, metal grill is just At the most important type of the flexible and transparent conductive electrode based on metal material.Most of transparent electrodes based on metal grill All it is that the method for silk-screen printing is first used to obtain lattice, redeposited metal obtains.It is screen printed onto photoetching for example, first passing through Glue-line obtains 5 microns of grid line width, and the pattern that 50 microns of spacing, then deposition is golden on it, is just obtained after stripping Golden grid, if it is be produced in transparent flexible substrates be exactly flexible and transparent metal electrode.But how further to carry The electric conductivity and light transmittance of high this electrode are still the important topic of researcher's concern.
Near field photolithography technology based on PDMS microarrays is a kind of novel nanometer that can reach 100 nanometers or less resolution ratio Patterning techniques, this is technically simple efficiently, of low cost, is not required to large-scale instrument, can be rapid in laboratory, big face Product, inexpensive obtains nano level pattern, and in micro-nano manufacture, there are many applications in the fields such as biochip.
Expensive equipment and harsh working environment are needed compared to traditional ultraviolet photolithographic technology, used near field photolithography PDMS making stamps are simple, of low cost, and can be patterned in arbitrary substrate, therefore in organic electronic, printing electricity Today of son and flexible electronic fast development, near field photolithography technology will play huge effect.The purpose of this patent is to use Near field photolithography technology prepares a kind of novel structure having multi-level metal network, to improve each of flexible transparent electrode Item performance.
Invention content
In view of the deficiencies of the prior art, it is prepared with multi-level metal network the purpose of the present invention is to provide a kind of The method of flexible transparent electrode.Present invention combination near field photolithography technology is easily obtained using metal material, electric property is outstanding, steams The features such as electroplating method maturation and high quality of materials obtained, a kind of simple for process high-performance flexible transparent electrode for preparing of design Method.
The purpose of the present invention can be achieved by the following measures:
A method of the flexible and transparent conductive electrode with multi-level metal network being prepared, the uniform spin coating in substrate Photoresist layer after front baking, then uses dimethyl silicone polymer seal and chromium plate to be exposed as mask plate successively, developed After handling and drying up, then the conductive metal deposition layer in the flexible substrates, it is finally ultrasonically treated and obtains with multi-level metal The flexible and transparent conductive electrode of network.
The multi-level metal network is 1-15 microns by line width, the metal grill and line width that 50-300 microns of spacing It it is 80-400 nanometers, the array of metal lines that spacing is 2-5 microns forms.
The substrate is non-transparent flexible substrate, selected from polyethylene terephthalate (PET), dimethyl silicone polymer (PDMS) any one and in polyimides etc., preferably polyethylene terephthalate or dimethyl silicone polymer.
The dimethyl silicone polymer seal is dimethyl silicone polymer (PDMS) seal with nano-wire array;Institute The chromium plate stated is the chromium plate with grid image.Successively using dimethyl silicone polymer (PDMS) seal with nano-wire array It is exposed as mask plate with the chromium plate with grid image, wherein the size of the nano-wire array of PDMS and chromium plate grid The size of image in multi-level metal network metal wire and metal grill size it is corresponding.It is described that there is nano-wire array Dimethyl silicone polymer (PDMS) seal preferably use following methods prepare:Using traditional photoetching technique, by there is lines The chromium plate of pattern carries out photoetching to oxidation piece substrate, and the silicon chip template of V-type array groove is obtained after wet etching.By poly- two After methylsiloxane (PDMS) monomer mixes in proportion with crosslinking agent and removes bubble removing, that pours into preparation has V-type array The silicon chip template of groove, and be heating and curing in an oven, obtain the polydimethylsiloxanes with nano-wire array after removing template Alkane (PDMS) seal.The mass ratio of dimethyl silicone polymer (PDMS) monomer and crosslinking agent is preferably 10:1.
The conductive metal of the conductive metal layer is at least one in common conductive metal Au, Ag, Cu, Pt, Zn and Fe etc. Kind, preferably Au, Ag or Cu.Method used by conductive metal deposition is heat sink area method, is well known method in field.
The thickness of the conductive metal layer need to be less than the 1/2 of photoresist layer thickness.
The time of the ultrasound is 1~30min, wherein it is preferred that 3~5min.
Compared with prior art, the present invention has had the advantage that:
First, the only simple a kind of grid of specification line width of traditional flexible transparent electrode based on metal grill, mostly Number is micron-sized, and light transmittance is different and different with its mesh-density, and prepared by the present invention has multi-level metal grid knot The novel flexible transparent conductive electrode of structure adds nano level metal wire on the basis of original micro-sized metal grid, In the case of smaller on the influence of electrode light transmittance, the electric conductivity of electrode is significantly improved.
Secondly, the present invention has used near field photolithography technology to prepare nano level metal wire, is improved in conventional processes, One-step method, which is made, has both micron order and nano level metal grill, has not only reduced the difficulty for making flexible transparent electrode, but also carry The high electric conductivity of electrode.
Finally, prepared by the present invention has the flexible transparent electrode of multi-level metal network, and preparation method is simple, prepares Mild condition has far reaching significance to further exploitation, the popularization of flexible transparent electrode and flexible electronic.
Description of the drawings
Fig. 1 is that PDMS seals is used to carry out showing for photoetching to the substrate for being coated with positive photoetching rubber shipley1805 as mask plate It is intended to, basal layer herein is PET;
The electron scanning micrograph for the multi-level metal grid that Fig. 2 makes, the material deposited herein are silver;
The electric conductivity comparison diagram of transparent electrode and common metal grill transparent electrode of the Fig. 3 based on multi-level metal grid, Abscissa indicates;
Fig. 4 is under conditions of 5 microns of grids, 400 nano wires, the visible-range light transmittance of the flexible transparent electrode of preparation Curve;
The flexible and transparent conductive electrode based on multi-level metal grid that Fig. 5 makes, substrate is PET;
The flexible and transparent conductive electrode for the metal grill that Fig. 6 comparative examples 2 make;
The flexible and transparent conductive electrode for the metal grill that Fig. 7 comparative examples 3 make.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1:Make the PDMS seals with nano-wire array
Using traditional photoetching technique, photoetching, lines spacing 5 are carried out to oxidation piece substrate by the chromium plate for having line image Micron, can obtain the silicon chip template of V-type array groove after wet etching.
By dimethyl silicone polymer (PDMS) monomer and crosslinking agent (DOW CORNING Sylgard 184) with mass ratio for 10:1 After ratio is uniformly mixed and removes bubble removing, the silicon chip template for having V-type array groove of preparation is poured into, and in 80 DEG C of baking oven Be heating and curing 4h, and flexible mask version (PDMS seals) (the nano-wire array lines with nano-wire array are obtained after removing template 5 microns of spacing), it is used for the preparation of follow-up nano-pattern.
Embodiment 2:Prepare the flexible transparent electrode for having multi-level metal network:
It is first handled with plasma cleaner and cleans flexible substrates polyethylene terephthalate (PET), poly- to benzene The photoresist (shipley1805) of 150 nanometer thickness of spin coating utilizes implementation after front baking on naphthalate (PET) film The PDMS seals prepared in example 1 are 100mw/cm in light intensity2Halogen light source under expose 18s, then carry grid with traditional The chromium plate of (10 microns of line width, 100 microns of spacing) pattern is in 500mw/cm2Ultraviolet source under expose 40s, then use MF319 Developing liquid developing 23s deposits the silver of 45 nanometer thickness, then ultrasound 5 minutes in acetone in substrate, PET bases can be obtained after drying Multi-level metal grid transparent electrode (Fig. 2) on bottom, wherein 10 microns of metal grill line width, 100 microns of spacing, metal sodium rice 200 nanometers of linear array line width, 5 microns of line width.It is 9.8 Ω/sq (Fig. 3) to test its sheet resistance with four probe electrode platforms, than traditional The metal grid electrode of no metal nanometer line array improves 50% or more.Its light transmittance is tested with ultraviolet specrophotometer to exist Up to 83.1% (Fig. 4) under 550nm wavelength.
Embodiment 3:
It is first handled with plasma cleaner and cleans flexible substrates dimethyl silicone polymer (PDMS), in polydimethylsiloxanes The photoresist (shipley1805) of 100 nanometer thickness of spin coating utilizes what is prepared in embodiment 1 after front baking on alkane (PDMS) film PDMS seals are 100mw/cm in light intensity2Halogen light source under expose 20s, then with it is traditional with grid (15 microns of line width, 200 microns of spacing) pattern chromium plate in 500mw/cm2Ultraviolet source under expose 30s, then use MF319 developing liquid developings 18s deposits the silver of 40 nanometer thickness, then ultrasound 4 minutes in acetone in substrate, the multistage in PDMS substrates can be obtained after drying Metal grill transparent electrode.
Comparative example 1
It is first handled with plasma cleaner and cleans flexible substrates polyethylene terephthalate (PET), poly- to benzene The photoresist (shipley1805) of 150 nanometer thickness of spin coating on naphthalate (PET) film, after front baking, with traditional Chromium plate with grid (10 microns of line width, 100 microns of spacing) pattern is in 500mw/cm2Ultraviolet source under expose 40s, then With MF319 developing liquid developing 23s, the silver of 45 nanometer thickness, then ultrasound 5 minutes in acetone are deposited after drying in substrate, can be obtained To transparent electrode.It is 21.5 Ω/sq to test its sheet resistance with four probe electrode platforms.
Comparative example 2
It is first handled with plasma cleaner and cleans flexible substrates polyethylene terephthalate (PET), poly- to benzene The photoresist (shipley1805) of 150 nanometer thickness of spin coating utilizes implementation after front baking on naphthalate (PET) film The PDMS seals prepared in example 1 expose 18s under the halogen light source that light intensity is, then (line width 10 is micro- with traditional grid that carries Rice, 100 microns of spacing) pattern chromium plate in 500mw/cm2Ultraviolet source under expose 40s, then use MF319 developing liquid developings 23s deposits the silver of 100 nanometer thickness, then ultrasound 5 minutes in acetone, because there is the metal of great quantities of spare in substrate after drying It can not be eluted by ultrasound with photoresist, cause electrode transparency very low.As shown in Figure 6.
Comparative example 3
It is first handled with plasma cleaner and cleans flexible substrates polyethylene terephthalate (PET), poly- to benzene The photoresist (shipley1805) of 150 nanometer thickness of spin coating utilizes implementation after front baking on naphthalate (PET) film The PDMS seals prepared in example 1 expose 18s under the halogen light source that light intensity is, then (line width 10 is micro- with traditional grid that carries Rice, 100 microns of spacing) pattern chromium plate in 500mw/cm2Ultraviolet source under expose 40s, then use MF319 developing liquid developings 23s deposits the silver of 45 nanometer thickness, then ultrasound 20 minutes in acetone in substrate, has part metals line to fall off, influence after drying The electric conductivity of electrode.As shown in Figure 7.

Claims (9)

1. a kind of method preparing the flexible and transparent conductive electrode with multi-level metal network, it is characterised in that:In substrate Upper uniform spin coating photoresist layer after front baking, then uses dimethyl silicone polymer seal and chromium plate to be carried out as mask plate successively Exposure, after subjected to development and drying, then the conductive metal deposition layer in the substrate, it is finally ultrasonically treated and obtains with more The flexible and transparent conductive electrode of grade metal mesh structure;
The multi-level metal network is 1-15 microns by line width, and the metal grill and line width that 50-300 microns of spacing are 80-400 nanometers, the array of metal lines that spacing is 2-5 microns forms.
2. the method according to claim 1 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The substrate is non-transparent flexible substrate, selected from polyethylene terephthalate, dimethyl silicone polymer and is gathered Any one in acid imide.
3. the method according to claim 2 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The substrate is polyethylene terephthalate or dimethyl silicone polymer.
4. the method according to claim 1 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The dimethyl silicone polymer seal is the dimethyl silicone polymer seal with nano-wire array;Described Chromium plate is the chromium plate with grid image.
5. the method according to claim 1 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The conductive metal of the conductive metal layer is at least one of Au, Ag, Cu, Pt, Zn and Fe.
6. the method according to claim 5 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The conductive metal of the conductive metal layer is Au, Ag or Cu.
7. the method according to claim 1 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The thickness of the conductive metal layer need to be less than the 1/2 of the photoresist layer thickness.
8. the method according to claim 1 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The time of the ultrasound is 1 ~ 30 min.
9. the method according to claim 8 for preparing the flexible and transparent conductive electrode with multi-level metal network, It is characterized in that:The time of the ultrasound is 3 ~ 5 min.
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CN108565214B (en) * 2018-04-09 2020-09-25 大连理工大学 Method for preparing silicon groove by PDMS masking technology
CN109686699B (en) * 2018-12-25 2021-03-23 Tcl华星光电技术有限公司 Metal transparent electrode and preparation method thereof
CN110265178A (en) * 2019-07-01 2019-09-20 深圳技术大学 A kind of preparation method of flexible transparent conducting film
CN110565123B (en) * 2019-08-28 2021-06-08 清华大学 Manufacturing method and device of transferable transparent flexible breathable antenna
CN112951485B (en) * 2021-01-26 2022-10-18 青岛理工大学 Metal grid stretchable transparent electrode with shell-core structure, and preparation method and application thereof
CN113077937B (en) * 2021-03-25 2022-11-04 惠州深格光电科技有限公司 Processing technology of flexible transparent conductive film
CN114283994B (en) * 2021-11-23 2023-05-09 华中科技大学 Embedded metal grid flexible electrode film and preparation method and application thereof

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