CN111816365B - Method for transferring conductive polymer onto flexible substrate and flexible electrode - Google Patents

Method for transferring conductive polymer onto flexible substrate and flexible electrode Download PDF

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CN111816365B
CN111816365B CN201910286951.2A CN201910286951A CN111816365B CN 111816365 B CN111816365 B CN 111816365B CN 201910286951 A CN201910286951 A CN 201910286951A CN 111816365 B CN111816365 B CN 111816365B
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conductive polymer
flexible substrate
substrate
flexible
polymer layer
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CN111816365A (en
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李立强
谭子婷
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • H01B13/0026Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124Intrinsically conductive polymers

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Abstract

The invention discloses a method for transferring a conductive polymer onto a flexible substrate and a flexible electrode. The method comprises the following steps: providing a hard substrate having a smooth surface; forming a conductive polymer layer on the surface of the hard substrate; and conformally combining the conductive polymer layer and the flexible substrate to obtain the flexible electrode. The manufacturing method provided by the embodiment of the invention has a simple manufacturing process, and the conductive polymer is compounded on the smooth hard substrate, and then is transferred to the flexible substrate in a transfer mode, so that the conformal compounding of the flexible substrate and the conductive polymer is realized, and the flexible electrode with a wrinkled structure on the surface is further formed.

Description

Method for transferring conductive polymer onto flexible substrate and flexible electrode
Technical Field
The invention relates to a flexible electrode, in particular to a method for transferring a conductive polymer onto a flexible substrate and the flexible electrode, and belongs to the technical field of micro-nano electronics and devices.
Background
Flexible electronic devices are an increasingly important field combining electronic components with various fields, and wearable devices, bio-implantable devices and other devices play an increasingly important role in the development of the human society, and the demand is increasing. For example, detection of bioelectric signals, interactive systems for man-machine interaction, even providing easy treatment, etc. The flexible electrode is used as a necessary basis for connecting all electronic elements to form a flexible electronic product, and plays a key role in the fields of flexible transistors, sensors, friction nano-generators and the like. Therefore, the electrode with the characteristics of stretchability, microstructure, modification, good biocompatibility, easy preparation and the like is receiving wide attention.
Flexible electrodes are mainly prepared in two ways. One of the methods is to construct a stretchable structure on a flexible substrate, which carries a conductive material with composite rigidity or certain flexibility. These stretchable structures include: a "wave" geometry, a serpentine interconnect structure, or a percolation network structure. The other focus is on the preparation of novel stretchable conductive nano materials, including carbon nanotubes, graphene, conductive polymers and their composites and new materials. The flexible electrode using the conductive polymer as the conductive layer is difficult to be combined to a flexible substrate in the preparation process and difficult to be combined conformally on the flexible substrate with a microstructure on the surface. In the prior art, a liquid conductive polymer is generally compounded on a flexible substrate through processes such as spin coating, spray coating, drop coating and the like, but a solvent of a part of the conductive polymer is incompatible with the flexible substrate and even has a corrosive effect, and conformal compounding on the flexible substrate with a microstructure is more difficult to perform, so that how to compound the conductive polymer on the flexible substrate conformally is still one of the technical problems to be solved in the industry.
Disclosure of Invention
It is a primary object of the present invention to provide a method of transferring a conductive polymer onto a flexible substrate and a flexible electrode, thereby overcoming the deficiencies of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
an embodiment of the present invention provides a method for transferring a conductive polymer onto a flexible substrate, including:
providing a hard substrate having a smooth surface;
forming a conductive polymer layer on the surface of the hard substrate;
and conformally combining the conductive polymer layer and the flexible substrate to obtain the flexible electrode.
Further, the manufacturing method specifically comprises the following steps: and attaching the flexible substrate and the conductive polymer layer, and then separating the composite of the flexible substrate and the conductive polymer layer from the hard substrate.
Further, the method specifically comprises the following steps: bonding a flexible substrate and a conductive polymer layer, modifying a bonding interface of the flexible substrate and the conductive polymer layer by using a modifying agent at least under a vacuum condition, and then separating the composite from the hard substrate; the modifier is capable of reacting with the constituent material of the flexible substrate and the conductive polymer.
Preferably, the surface modifier includes any one or a combination of two or more of perfluorotriethylsilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltrimethoxysilane, but is not limited thereto.
Preferably, the time of the modification treatment is 1-300 min.
Preferably, the amount of the modifier is 1 to 10000. mu.l.
Further, the method specifically comprises the following steps: applying a precursor of a flexible substrate onto the conductive polymer layer, thereafter curing the precursor of the flexible substrate to form a flexible substrate, and separating the composite of the flexible substrate and the conductive polymer layer from the rigid substrate.
Further, the method further comprises the following steps: and respectively combining the two opposite side surfaces of the flexible substrate with a conductive polymer layer to obtain the flexible electrode.
Further, a microstructure is provided at least on the surface of the flexible substrate bonded to the conductive polymer layer.
Preferably, the microstructure includes a plurality of parallel or irregularly arranged fold structures.
Further, the hard substrate is made of any one of a silicon wafer, a silicon wafer containing an oxide layer, glass and acrylic; but is not limited thereto.
Preferably, the conductive polymer includes any one or a combination of two or more of polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene ethylene, and polydiyne, but is not limited thereto.
Preferably, the material of the flexible substrate includes one or more of polydimethylsiloxane film, polyacrylate, polyvinylidene fluoride, polystyrene, polyamide, polyimide, silicone rubber, chloroprene rubber, epoxy resin, thermoplastic polyurethane, polyacrylate, polyvinylidene fluoride, ethylene propylene rubber, fluororubber, styrene thermoplastic elastomer, olefin thermoplastic elastomer, diene thermoplastic elastomer, vinyl chloride thermoplastic elastomer, polyamide thermoplastic elastomer, thermoplastic vulcanizate, natural rubber, styrene butadiene rubber, isoprene rubber, polyethylene terephthalate, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer And are not limited thereto.
The embodiment of the invention also provides a flexible electrode prepared by the method for transferring the conductive polymer onto the flexible substrate.
The embodiment of the invention also provides a flexible electrode which comprises a flexible substrate and a conductive polymer layer, wherein the conductive polymer layer is conformally combined on the surface of the flexible substrate.
Furthermore, the two opposite side surfaces of the flexible substrate are respectively combined with a conductive polymer layer.
Further, a microstructure is provided at least on the surface of the flexible substrate bonded to the conductive polymer layer.
Preferably, the microstructure includes a plurality of parallel or irregularly arranged fold structures.
Compared with the prior art, the method provided by the embodiment of the invention has simple process flow, and the conductive polymer is compounded on the smooth hard substrate firstly, and then is transferred to the flexible substrate in a transfer mode, so that the conformal compounding of the flexible substrate and the conductive polymer is realized, and a plurality of parallel or irregularly arranged fold structures are formed on the surface.
Drawings
FIG. 1 is a schematic diagram of a process flow for manufacturing a flexible electrode according to an exemplary embodiment of the present invention;
fig. 2 is an AFM image of wrinkles formed on a surface of a conductive polymer layer conformally bonded to a flexible substrate in an exemplary embodiment of the invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
Specifically, the method for transferring the conductive polymer onto the flexible substrate can comprise the following steps:
1) providing a hard substrate with a smooth surface, and carrying out hydrophilic treatment such as oxygen plasma treatment, ultraviolet treatment or acidification on the hard substrate;
2) compounding a conductive polymer on the smooth surface of the hard substrate by processes of spin coating, spray coating, drop coating, chemical synthesis and the like, and drying to form a conductive polymer layer;
3) directly attaching the flexible substrate to the conductive polymer layer, or compounding the flexible substrate on the surface of the conductive polymer layer by adopting modes of spin coating, drip coating and the like to form a flexible substrate precursor, and curing the flexible substrate precursor at a certain temperature to form the flexible substrate;
4) modifying the bonding interface of the flexible substrate and the conductive polymer layer by adopting a modifying agent under a vacuum condition, wherein the modifying agent can be reacted and bonded with the composition material of the flexible substrate and the conductive polymer.
5) And lifting the composite of the flexible substrate and the conductive polymer layer, and stripping the conductive polymer layer from the surface of the hard substrate to form the flexible electrode.
The surface of the flexible substrate is provided with a microstructure, and the microstructure comprises a plurality of parallel or irregularly arranged fold structures. Due to the fact that elastic moduli of the flexible substrate and the conductive polymer layer are not consistent, the flexible substrate is slightly deformed in the process of lifting the flexible substrate and the conductive polymer layer from the hard substrate, residual stress is generated between the flexible substrate and the conductive polymer layer, and the residual stress causes formation of a microstructure.
Specifically, the manufacturing method further comprises: the conductive polymer layers are formed on the two opposite side surfaces of the same flexible substrate by adopting the method, and the flexible electrode is a sandwich structure with the flexible substrate positioned between the two conductive polymer layers.
Example 1
1) Sample plasma pair of 0.1-80cm2The silicon wafer is subjected to oxygen plasma treatment, followed by spin-coating with polyacetylene (1-10000. mu.L), and drying (20-200 ℃ C.) on a flat heating stage to form a polyacetyleneAn acetylene film; wherein, the time of oxygen plasma treatment is 1-600s, the power is 10-500W, and the pressure is 1-500 Pa; the spin coating conditions were: rotation speed 500-: 1-180 s;
2) attaching a polydimethylsiloxane film (PDMS film) with the thickness of 10-10000 μm to a silicon chip on which a polyacetylene film is formed, and modifying by adopting (3-mercaptopropyl) trimethoxysilane under a vacuum condition; the time of the modification treatment is 1-300 min. Preferably, the (3-mercaptopropyl) trimethoxysilane is used in an amount of 1 to 10000. mu.l.
3) And finally, after the PDMS film is uncovered, the elastic modulus between the surface of the polyacetylene film and the PDMS film is inconsistent, and a microstructure is formed on the surface of the PDMS film, wherein the microstructure comprises a plurality of fold structures which are arranged in parallel or irregularly.
Example 2
Applying a precursor of a flexible substrate on the surface of the conductive polymer layer:
1) sample plasma pair of 0.1-80cm2Performing oxygen plasma treatment (or ultraviolet treatment and acidification treatment) on the glass substrate, spin-coating polyphenylene ethylene (1-10000 mu L), and drying on a flat heating table (20-200 ℃) to form a polyphenylene ethylene film; wherein, the time of oxygen plasma treatment is 1-600s, the power is 10-500W, and the pressure is 1-500 Pa; the spin coating conditions were: rotation speed 500-: 1-180 s;
2) spin coating 1-30ml polyvinylidene fluoride precursor on a glass substrate formed with a polyphenylene ethylene film, and curing under vacuum condition to form a polyvinylidene fluoride film (i.e. a flexible substrate), wherein the spin coating condition of the polyvinylidene fluoride precursor is as follows: rotation speed 500-: 1-180 s; curing conditions are as follows: the temperature is 20-150 ℃, and the time is 10-600minutes
3) Adopting 3-aminopropyl triethoxysilane (APTES) to make modification treatment under the vacuum condition; the time of the modification treatment is 1-300 min; preferably, the 3-aminopropyltriethoxysilane is used in an amount of 1. mu.l to 10000. mu.l.
4) And finally, after the polyvinylidene fluoride membrane is lifted, the elastic modulus of the surface of the conductive polymer layer is inconsistent with that of the polyvinylidene fluoride membrane, and a microstructure is formed on the surface of the polyvinylidene fluoride membrane and comprises a plurality of fold structures which are arranged in parallel or irregularly.
Example 3
Arranging conductive polymer layers on the surfaces of both sides of the flexible substrate;
attaching a flexible substrate, such as a Styrene Butadiene Rubber (SBR) film with the thickness of 10-10000 μm, to an acrylic substrate coated with polypyrrole, modifying the flexible substrate by using a modifier under a vacuum condition, then lifting the SBR film, immediately attaching the back of the SBR film to another acrylic substrate coated with polypyrrole, modifying the Styrene Butadiene Rubber (SBR) film by using the modifier under the vacuum condition, and then lifting the SBR film to form a polypyrrole film-styrene butadiene rubber film-polypyrrole film sandwich electrode with a wrinkled microstructure on both sides of the SBR film. Specifically, the method comprises the following steps:
1) for 0.1-80cm2Performing oxygen plasma treatment on an acrylic substrate, spin-coating polypyrrole (1-10000 mu L), and drying on a flat heating table (20-200 ℃) to form a polypyrrole film; wherein, the time of oxygen plasma treatment is 1-600s, the power is 10-500W, and the pressure is 1-500 Pa; the spin coating conditions were: rotation speed 500-: 1-180 s;
2) attaching a Styrene Butadiene Rubber (SBR) film with the thickness of 10-10000 mu m to an acrylic substrate on which a polypyrrole film is formed, and modifying by adopting 3-aminopropyltrimethoxysilane under a vacuum condition; the time of the modification treatment is 1-300 min. Preferably, the 3-aminopropyl trimethoxy silane is used in an amount of 1. mu.l to 10000. mu.l.
3) And finally, after the Styrene Butadiene Rubber (SBR) film is uncovered, the elastic modulus between the surface of the polypyrrole film and the Styrene Butadiene Rubber (SBR) film is inconsistent, and a microstructure is formed on the surface of the Styrene Butadiene Rubber (SBR) film and comprises a plurality of parallel or irregularly arranged fold structures.
4) And then attaching the back of the removed Styrene Butadiene Rubber (SBR) film to an acrylic substrate with a polypyrrole film formed on the other surface, and modifying under the same conditions as those in 2).
5) And (3) uncovering the Styrene Butadiene Rubber (SBR) film again, and forming a polypyrrole film-styrene butadiene rubber film-polypyrrole film sandwich electrode with a fold microstructure on both sides of the SBR film.
In the embodiment, a method for transferring the conductive polymer twice is adopted, and the materials and the sizes of the hard substrate, the conductive polymer and the modifier adopted in the process of transferring the conductive polymer twice can be the same or different.
Compared with the method for directly compounding the conductive polymer layer on the flexible substrate, the method utilizes reactants which can react with the flexible substrate and the conductive polymer, such as (3-mercaptopropyl) trimethoxysilane (MPTMS) and the like, to easily transfer the conductive polymer compounded on the hard substrate to the flexible substrate, and simultaneously can form the conductive polymer layer with a plurality of parallel or irregularly arranged fold structures on the flexible substrate.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (8)

1. A method of transferring a conductive polymer onto a flexible substrate, comprising:
providing a hard substrate having a smooth surface;
forming a conductive polymer layer on the surface of the hard substrate;
applying a precursor of a flexible substrate onto the conductive polymer layer, followed by curing the precursor of the flexible substrate to form a flexible substrate, thereby the conductive polymer layer is combined with the flexible substrate in a conformal way, and the combination interface of the flexible substrate and the conductive polymer layer is modified by a modifier at least under the vacuum condition, the modifier can react and combine with the composition material of the flexible substrate and the conductive polymer, and comprises any one or the combination of more than two of perfluoro-triethylsilyl, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and the like, the time of the modification treatment is 1-300min, and the dosage of the modifier is 1-10000 ul;
and separating the composite of the flexible substrate and the conductive polymer layer from the hard substrate to obtain the flexible electrode.
2. The method of claim 1, further comprising: and respectively combining the two opposite side surfaces of the flexible substrate with a conductive polymer layer to obtain the flexible electrode.
3. The method of claim 1, wherein: microstructures are disposed on at least a surface of the flexible substrate that is bonded to the conductive polymer layer.
4. The method of claim 3, wherein: the microstructure comprises a plurality of parallel or irregularly arranged fold structures.
5. The method of claim 1, wherein: the hard substrate is made of any one of a silicon wafer, a silicon wafer containing an oxide layer, glass and acrylic.
6. The method of claim 1, wherein: the conductive polymer comprises any one or the combination of more than two of polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene ethylene and polydiyne.
7. The method of claim 1, wherein: the flexible substrate is made of polydimethylsiloxane film, polyacrylate, polyvinylidene fluoride, polystyrene, polyamide, polyimide, silicon rubber, chloroprene rubber, epoxy resin and thermoplastic polyurethane, the thermoplastic elastomer composition is characterized by comprising at least one of polyacrylate, polyvinylidene fluoride, ethylene propylene rubber, fluororubber, styrene thermoplastic elastomer, olefin thermoplastic elastomer, diene thermoplastic elastomer, vinyl chloride thermoplastic elastomer, polyamide thermoplastic elastomer, thermoplastic vulcanizate, natural rubber, styrene butadiene rubber, isoprene rubber, polyethylene terephthalate, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer, or a combination of two or more thereof.
8. A flexible electrode made by the method of transferring a conductive polymer onto a flexible substrate of any one of claims 1-7.
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CN114171257B (en) * 2021-12-13 2022-09-02 西安交通大学 Flexible transparent electrode and preparation method thereof

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