WO2024002397A1 - Composite hybride pour la préparation de couches conductrices minces, procédé de préparation associé et couche conductrice mince préparée à partir du composite hybride - Google Patents

Composite hybride pour la préparation de couches conductrices minces, procédé de préparation associé et couche conductrice mince préparée à partir du composite hybride Download PDF

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WO2024002397A1
WO2024002397A1 PCT/CZ2022/050059 CZ2022050059W WO2024002397A1 WO 2024002397 A1 WO2024002397 A1 WO 2024002397A1 CZ 2022050059 W CZ2022050059 W CZ 2022050059W WO 2024002397 A1 WO2024002397 A1 WO 2024002397A1
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pyrene
hybrid composite
thin conductive
modified
polyaromatic compound
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PCT/CZ2022/050059
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English (en)
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František JOSEFÍK
Lubomír KUBÁČ
Tomáš SYROVÝ
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Centrum organické chemie, s.r.o.
Univerzita Pardubice
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Priority to PCT/CZ2022/050059 priority Critical patent/WO2024002397A1/fr
Publication of WO2024002397A1 publication Critical patent/WO2024002397A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/04—Nanotubes with a specific amount of walls
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3

Definitions

  • the invention relates to the field of electroactive materials, more particularly to a hybrid composite for preparing thin conductive layers, to a method of preparing thereof, and to a thin conductive layer prepared from this hybrid composite.
  • the flexible and organic electronics field has experienced dynamic development over the last 20 years.
  • Electronic devices produced by printing, coating, sputtering or steaming in a continuous mode, so-called roll-to-roll or R2R feature low production costs and are gradually being applied in various applications.
  • Most of the devices produced in this way use polyethylene-terephthalate film or PET film as a base, on which other functional layers are then gradually applied to create different types of electronic devices.
  • the most common and commercially successful solution is the method where a layer of conductive transparent metal oxides is applied on the PET film by vacuum deposition.
  • ITO tin-doped indium trioxide
  • FTO fluorine-doped indium trioxide
  • Another option is preparing thin conductive layers by depositing carbon nanomaterial.
  • Graphene is a very promising material.
  • the carbon nanomaterial deposited in a 2D arrangement allows the preparation of a transparent conductive layer.
  • the basic deposition technique is vacuum chemical vapor deposition. This technique does not allow to prepare a homogeneous layer without crystal lattice defects, affecting the conductivity of such prepared layer and resulting in local conductivity problems.
  • the growth of graphene single crystals on a single-crystal catalytic substrate is expensive and inefficient from an industrial point of view.
  • Another disadvantage is that graphene films prepared in a such way are limited by the dimensions thereof, and it is practically impossible to talk about continuous production technology.
  • the CNT deposition process in thin conductive layers has a major disadvantage in that they are highly prone to agglomeration, and conventional deposition techniques do not allow the preparation of a homogeneous layer of reproducibly uniform thickness.
  • This disadvantage is solved by the addition of dispersing agents, which, however, reduce the conductivity of the final conductive layer at the same time.
  • Another approach is the oxidation of the carbon nanotube surface to form -OH and -COOH groups. Although these improve dispersibility, the conductivity of the prepared layers is significantly reduced.
  • the CNTs are fiberized by agitation in an acidic medium in the presence of sulfuric, chlorosulfonic, trifluoromethanesulfonic or 4-toluenesulfonic acid so that the pH of the medium is less than 1.
  • the fiberizing is carried out in the presence of polyaromatic molecules, both substituted and unsubstituted, where the number of aromatic units is at least two, and graphene may also be used.
  • the weight ratio of CNTs to polyaromatic molecules ranges from 1 :3 to 3:1.
  • the CNT surface can be achieved to be covered with sulfonated polyaromatic derivatives, forming a so-called TT-TT stacking with the CNTs.
  • the bonds are highly stable and allow efficient dispersion to a high degree and limit the risk of CNT agglomeration.
  • this modification of CNTs did not provide the desired method of preparing conductive mixtures that could be easily deposited on the support substrate surface such as a film, which then carries limitations, particularly in the case of requirements for the production of thin, highly conductive layers as a basis for the subsequent deposition of flexible electronic devices.
  • the object of the invention is to provide such a hybrid composite for the preparation of thin conductive layers, a method of preparing thereof, and thin conductive layers prepared from this hybrid composite, which method of preparation would be inexpensive, wherein the hybrid composite would be recyclable, stable even in a humid environment, and, furthermore, easily deposited on the support substrate surface such as PET film.
  • the hybrid composite prepared by such a method could be used to produce thin, highly conductive layers as a basis for the deposition of flexible electronic devices.
  • a hybrid composite for the preparation of carbon nanomaterial thin films which comprises a carbon nanomaterial and a conducting polymer based on poly(3,4-ethylenedioxythiophene).
  • the carbon nanomaterial is at least one material selected from the group consisting of: single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene particles, graphene oxide particles, nanographite particles, globular carbon nanoparticles.
  • the use of these nanoparticles is preferable particularly because of their high strength and excellent electrical conductivity due to their large specific surface area. It allows the formation of a thin, highly conductive layer.
  • the surface of the carbon nanomaterial is modified with a sulfonated polyaromatic compound based on pyrene, which forms strong ionic bonds with a conductive polymer based on poly (3,4-ethylenedioxothiophene) or PEDOT.
  • the whole system is highly stable due to the formation of strong TT - TT stacking between the carbon nanomaterial and the sulfonated pyrene-based polyaromatic compound and at the same time strong ionic bonds between PEDOT and polyaromatic sulfonated compounds, which can only be broken by the action of strong alkalis or reducing agents.
  • the conductivity of this array combines electron conductivity through electron holes and ionic conductivity.
  • the hybrid composite is further in the form of a stable, electrically conductive film-forming dispersion, in which the weight ratio of the carbon nanomaterial to the sulfonated polyaromatic compound ranges from 1 :10 to 10:1 , and the weight ratio of the carbon nanomaterial surface-modified with the sulfonated polyaromatic compound to the conductive polymer poly(3,4- ethylenedioxythiophene) ranges from 1 :10 to 10:1.
  • a weight ratio is preferable for formulating the film-forming matrix from the prepared hybrid composite. This ratio produces a stable dispersion in aqueous media suitable for preparing high conductivity thin films.
  • stable dispersion is understood to mean an electrically conductive dispersion, stability of which consists in the absence of agglomeration and/or settling of the particles contained in the dispersion. Without the addition of further additives, it is thus possible to prepare a stable electrically conductive dispersion having very good film-forming properties.
  • the sulfonated polyaromatic compound is formed on the surface of carbon nanomaterials during mixing in the presence of chlorosulfonic acid or sulfuric acid, and the polyaromatic compound is selected from the group: pyrene, 1 -pyrenemethylamine, 1 - acetylpyrene, 1 -methylpyrene, 1 -(bromoacetylpyrene), 1 -(bromomethyl)pyrene, 1 - bromopyrene, 1 -pyrenemethanol, 1 -aminopyrene, 1 -hydroxypyrene, 1 -pyrenebutyric acid, 1 - pyrenecarboxylic acid, 1 -pyrenesulfonic acid, benzo[a]pyrene, benzo[e]pyrene, 7- methylbenzo[a]pyrene, dibenzo[a,e]pyrene, dibenzo[a,h]pyrene, dibenzo[a,l
  • the hybrid composite is in the form of a stable aqueous dispersion having a dry solids content of the hybrid composite of from 0.1 to 3.0% by weight.
  • a stable aqueous dispersion is also suitable for preparing very thin conductive films with a thickness of from 100 nm to 100 pm.
  • the object of the invention is a preparation method of the hybrid composite for preparing thin conductive layers.
  • the carbon nanomaterials are firstly surface-modified in presence of sulfuric acid or chlorosulfonic acid with the addition of at least one pyrene-based polyaromatic compound.
  • polymerization of 3,4-ethylenedioxythiophene is performed by oxidative action of ferric chloride and/or ferric sulfate and/or ferric tosylate and/or mixtures of ferric chloride hexahydrate and ammonium persulfate or sodium persulfate. It will cover the modified carbon nanomaterial with a PEDOT layer.
  • an aqueous dispersion of a mixture of surface- modified carbon nanomaterials with a polyaromatic compound and a PEDOT conducting polymer in an aqueous medium is prepared.
  • the hybrid composite is applied on the supporting substrate using a coating method selected from the group consisting of: slot die, curtain coating, spiral bar coating, spray coating, dip coating, screen printing, gravure printing, flexographic printing, microdispensing, and aerosol jet printing.
  • a coating method selected from the group consisting of: slot die, curtain coating, spiral bar coating, spray coating, dip coating, screen printing, gravure printing, flexographic printing, microdispensing, and aerosol jet printing.
  • the object of the invention is a thin conductive layer made by a method according to the present invention.
  • the thin conductive layer has a conductivity of 500 to 2,000 S/cm and a thickness of 100 nm to 100 pm.
  • the conductivity of this grouping combines electron conductivity through electron holes and ionic conductivity.
  • the hybrid composite shows excellent film-forming properties so that the entire mixture can be well deposited on the pre-treated surface.
  • the advantage of the hybrid composite for preparing thin conductive layers and the thin conductive layers prepared from this hybrid composite according to the present invention is that the preparation method is inexpensive, the hybrid composite is recyclable and stable even in a humid environment.
  • Another advantage of the hybrid composite for preparing thin conductive layers is that it can be easily deposited on the supporting substrate surface, such as PET film.
  • Another advantage is that the hybrid composite prepared by such a method can be used to produce thin, highly conductive layers as a basis for the deposition of flexible electronic devices.
  • Example 1 Modification of SWCNT with pyrene at a weight ratio of 1 :5
  • the prepared hybrid composite in the form of a mixture was stirred for another 24 hours at laboratory temperature. After the prescribed time had elapsed, the mixture forming the hybrid composite was poured onto 5 kg of crushed ice and stirred for a further 24 hours. The resulting SWCNT dispersion was filtered and washed with distilled water up to the neutral pH of the filtrate. The filtered sulfonated pyrene modified SWCNTs were transferred as a thick paste into a vial, and the dry matter weight was determined.
  • Example 2 Modification of DWCNT with 1 -pyrenemethylamine at a weight ratio of 1 :1
  • the reaction mixture was stirred for 48 hours at laboratory temperature. After the prescribed time had elapsed, the mixture forming the hybrid composite was poured onto 10 kg of crushed ice and stirred for 24 hours. The resulting MWCNT dispersion was filtered and washed with distilled water up to the neutral pH of the filtrate. The filtered sulfonated pyrene modified MWCNTs were transferred as a thick paste into a vial, and the dry matter weight was determined.
  • Example 4 Modification of graphite with 1 -pyrenemethylamine at a weight ratio of 10:1
  • Example 5 Polymerization of PEDOT on modified SWCNT prepared according to Example 1 at a weight ratio of 1 :10
  • Example 6 Polymerization of PEDOT on modified DWCNT prepared according to Example 2 at a weight ratio of 1 :1
  • Example 7 Polymerization of PEDOT on modified MWCNT prepared according to Example 3 at a weight ratio of 10:1
  • Example 8 Polymerization of PEDOT on modified graphite prepared according to Example 4 at a weight ratio of 5:1
  • the product prepared according to Example 5 was dispersed in 500 mL of distilled water for 12 hours using the ultraturrax. Then, the dispersion was cooled to 5°C and sonicated for 24 hours, while mixing simultaneously using the ultraturrax. After the prescribed time had elapsed, the dry matter weight of the prepared dispersion was determined.
  • Example 10 Preparation of self-supporting conductive film by drying
  • the dispersion prepared according to Example 9, containing 200 mg of modified SWCNTs was poured into a petri dish of 20 cm in diameter. The petri dish was placed in a drying oven and dried at 130°C to a constant weight. After drying, the prepared self-supporting film was peeled off the petri dish. The thickness of the prepared film was measured to be 50 pm, and the electrical resistance was determined to be 0.04 Q. From these data, the conductivity was calculated to be 1 ,100 S/cm. In another exemplary embodiment not shown, the thickness of the thin conductive layer was from 100 nm to 100 pm. In another exemplary embodiment not shown, the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • Example 11 Preparation of self-supporting conductive film by filtration
  • the dispersion prepared according to Example 9, containing 200 mg of modified SWCNTs was poured into a filter bed of 20 cm in diameter. After the distilled water was drawn off, the cake of the filter bed was purged with air for 2 hours. The filter bed and the cake were then placed in a drying oven and dried at 130°C to a constant weight. After drying, the filter cake was peeled off the filter bed. The thickness thereof was measured to be 38 pm, and the electrical resistance was determined to be 0.04 Q. From these data, the conductivity was calculated to be 1 ,450 S/cm. In another exemplary embodiment not shown, the thickness of the thin conductive layer was from 100 nm to 100 pm. In another exemplary embodiment not shown, the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • An ion pair dispersion of poly(3,4-ethylenedithiothiophene) and polystyrene sulfonate, or PEDOT :PSS, with a dry matter content of 3% by weight was used for the printing formulation.
  • a dry matter concentration of 0.1 to 3% by weight was used.
  • An aqueous dispersion of the modified SWCNTs of Example 9 in an amount of 14% by weight was added to the above mixture.
  • a bifunctional 30% glycol and a polyether- based surfactant in an amount of 0.5% by weight were also added to the formulation.
  • the printing formulation was then properly homogenized.
  • the printing formulation was used for printing by screen printing technique on the PET substrate.
  • a coating method selected from the group consisting of slot die, curtain coating, spiral bar coating, spray coating, dip coating, gravure printing, flexographic printing, microdispensing, aerosol jet printing was used.
  • a stencil with 120 fib./cm mesh was used for printing.
  • the thin conductive layers were dried for 15 minutes at 120°C.
  • the given thin conductive layer exhibited an area resistance of 550 Q/square at a thickness of 320 nm.
  • the thickness of the thin conductive layer was from 100 nm to 100 pm.
  • the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • Example 13 Preparation of the printing formulation for screen printing II
  • a base polymer solution based on carboxymethylcellulose, or CMC, at a concentration of 2% by weight was used for the printing formulation.
  • An aqueous dispersion of the modified SWCNTs of Example 9 in an amount of 20% by weight was added to the above mixture.
  • 15% glycol, 10% glycolether and a surfactant based on polyethersiloxane in an amount of 0.25% by weight were added to the said formulation.
  • the printing formulation was then properly homogenized.
  • the printing formulation was used for printing by screen printing technique on the PET substrate.
  • a coating method selected from the group consisting of slot die, curtain coating, spiral bar coating, spray coating, dip coating, gravure printing, flexographic printing, microdispensing, aerosol jet printing was used.
  • a stencil with 120 fib./cm mesh was used for printing. After printing, the thin conductive layers were dried for 15 minutes at 120°C. The given thin conductive layer exhibited an area resistance of 430 Q/square at a thickness of 220 nm. In another exemplary embodiment not shown, the thickness of the thin conductive layer was from 100 nm to 100 pm. In another exemplary embodiment not shown, the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • a base polymer solution based on CMC at a concentration of 1% by weight was used for the printing formulation.
  • An aqueous dispersion of the modified SWCNTs of Example 9 in an amount of 25% by weight was added to the above mixture.
  • 1 % acrylate dispersion, 20% glycol, 10% monofunctional alcohol and a surfactant based on alkoxylated alcohol in the amount of 0.15% by weight were added to the formulation.
  • the printing formulation was then properly homogenized.
  • the printing formulation was used for printing by screen printing technique on the PET substrate.
  • a coating method selected from the group consisting of slot die, curtain coating, spiral bar coating, spray coating, dip coating, gravure printing, flexographic printing, microdispensing, aerosol jet printing was used.
  • a stencil with 120 fib./cm mesh was used for printing. After printing, the thin conductive layers were dried for 15 minutes at 120°C. The given thin conductive layer exhibited an area resistance of 400 Q/square at a thickness of 190 nm. In another exemplary embodiment not shown, the thickness of the thin conductive layer was from 100 nm to 100 pm. In another exemplary embodiment not shown, the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • An ion pair dispersion of poly(3,4-ethylenedithiothiophene) and polystyrene sulfonate, or PEDOT :PSS, with a dry matter content of 3% by weight was used for the printing formulation.
  • a dry matter concentration of 0.1 to 3% by weight was used.
  • An aqueous dispersion of the modified SWCNTs of Example 9 in an amount of 14% by weight was added to the above mixture.
  • a monofunctional 40% glycol and a polyether-based surfactant in an amount of 0.5% by weight were also added to the formulation.
  • a thin conductive layer was stretched with a Bird ruler with a 150-pm slit on the PET substrate.
  • a coating method selected from the group consisting of slot die, curtain coating, spiral bar coating, spray coating, dip coating, gravure printing, flexographic printing, microdispensing, aerosol jet printing was used.
  • the thin conductive layers were dried for 15 minutes at 120°C.
  • the given thin conductive layer exhibited an area resistance of 35 Q/square, at a thickness of 3 pm.
  • the thickness of the thin conductive layer was from 100 nm to 100 pm.
  • the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • An ion pair dispersion of poly(3,4-ethylenedithiothiophene) and polystyrene sulfonate, or PEDOT :PSS, with a dry matter content of 3% by weight was used for the printing formulation.
  • a dry matter concentration of 0.1 to 3% by weight was used.
  • An aqueous dispersion of the modified SWCNTs of Example 9 in an amount of 14% by weight was added to the above mixture.
  • a monofunctional 40% glycol and a polyether-based surfactant in an amount of 0.5% by weight were also added to the formulation.
  • a micrometer stretching ruler with a 1 ,5-mm slit was used to apply the coating to a paper substrate deposited in the R2R mode.
  • the thin conductive layers were dried in a tunnel for 15 minutes in at 120°C.
  • a coating method selected from the group consisting of slot die, curtain coating, spiral bar coating, spray coating, dip coating, gravure printing, flexographic printing, microdispensing, aerosol jet printing was used.
  • the given thin conductive layer exhibited an area resistance of 3 Q/square at a thickness of thin conductive layer of 32 pm.
  • the thickness of the thin conductive layer was from 100 nm to 100 pm.
  • the thin conductive layers exhibited conductivities from 500 to 2,000 S/cm.
  • the hybrid composite for preparing thin conductive layers, the method of preparing thereof, and the thin conductive layer prepared from the hybrid composite according to the present invention can be used to prepare a transparent thin conductive layer on a flexible or rigid substrate using printing and deposition techniques.
  • the thin conductive layer prepared by such a method can be used as a component of electronic devices.

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Abstract

L'invention concerne un composite hybride d'un nanomatériau de carbone à surface modifiée par un composé polyaromatique sulfoné à base de pyrène et d'un polymère conducteur à base de poly(3,4-éthylènedioxythiophène), qui forme une paire d'ions avec le composé polyaromatique sulfoné. Le nanomatériau de carbone est au moins un matériau choisi dans le groupe consistant en les nanotubes de carbone à simple paroi, les nanotubes de carbone multi-parois, les particules de graphène, les particules d'oxyde de graphène, les particules de nanographite, les nanoparticules de carbone globulaire. Le composite hybride se présente sous la forme d'une dispersion filmogène stable, électriquement conductrice, dans laquelle le rapport en poids du nanomatériau de carbone au composé polyaromatique sulfoné est compris dans la plage de 1:10 à 10:1, et le rapport en poids du nanomatériau de carbone à surface modifiée par le composé polyaromatique sulfoné au polymère conducteur poly(3,4-éthylènedioxythiophène) est compris dans la plage de 1:10 à 10:1.
PCT/CZ2022/050059 2022-06-29 2022-06-29 Composite hybride pour la préparation de couches conductrices minces, procédé de préparation associé et couche conductrice mince préparée à partir du composite hybride WO2024002397A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011071295A2 (fr) * 2009-12-07 2011-06-16 Suh Kwang Suck Composite nanotubes de carbone/liquide ionique polymère, et composite nanotubes de carbone/polymère conducteur préparé à l'aide de ce dernier
US20120326093A1 (en) 2011-06-24 2012-12-27 Brewer Science Inc. Highly soluble carbon nanotubes with enhanced conductivity
CZ34652U1 (cs) * 2020-09-30 2020-12-08 Centrum organické chemie s.r.o. Uhlíkový materiál povrchově modifikovaný poly(3,4-ethylendioxothiofenem)
CZ35317U1 (cs) * 2021-05-25 2021-08-17 Západočeská Univerzita V Plzni Senzor pro identifikaci a měření koncentrace amoniaku

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011071295A2 (fr) * 2009-12-07 2011-06-16 Suh Kwang Suck Composite nanotubes de carbone/liquide ionique polymère, et composite nanotubes de carbone/polymère conducteur préparé à l'aide de ce dernier
US20120326093A1 (en) 2011-06-24 2012-12-27 Brewer Science Inc. Highly soluble carbon nanotubes with enhanced conductivity
US20140138588A1 (en) 2011-06-24 2014-05-22 Brewer Science Inc. Highly soluble carbon nanotubes with enhanced conductivity
CZ34652U1 (cs) * 2020-09-30 2020-12-08 Centrum organické chemie s.r.o. Uhlíkový materiál povrchově modifikovaný poly(3,4-ethylendioxothiofenem)
CZ35317U1 (cs) * 2021-05-25 2021-08-17 Západočeská Univerzita V Plzni Senzor pro identifikaci a měření koncentrace amoniaku

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