WO2016057109A2 - Conducteurs minces à base de graphène - Google Patents

Conducteurs minces à base de graphène Download PDF

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Publication number
WO2016057109A2
WO2016057109A2 PCT/US2015/044520 US2015044520W WO2016057109A2 WO 2016057109 A2 WO2016057109 A2 WO 2016057109A2 US 2015044520 W US2015044520 W US 2015044520W WO 2016057109 A2 WO2016057109 A2 WO 2016057109A2
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WO
WIPO (PCT)
Prior art keywords
layer
graphene
transparent conductor
graphene sheets
sheets
Prior art date
Application number
PCT/US2015/044520
Other languages
English (en)
Other versions
WO2016057109A3 (fr
Inventor
Michael A. POPE
John S. Lettow
Ilhan A. ASKAY
Original Assignee
Vorbeck Materials Corp.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Vorbeck Materials Corp. filed Critical Vorbeck Materials Corp.
Publication of WO2016057109A2 publication Critical patent/WO2016057109A2/fr
Publication of WO2016057109A3 publication Critical patent/WO2016057109A3/fr

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Classifications

    • 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
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • 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
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties

Definitions

  • the present invention relates generally to conductors and specifically to graphene-based thin transparent conductors and methods of manufacture.
  • a conductor is typically an object or type of material that permits the flow of electrical current in one or more directions.
  • Conductors can be transparent or opaque.
  • Transparent conductors are typically deposited as continuous films by a variety of capital-intensive approaches based on physical vapor deposition, such as carbon vapor deposition in the case of graphene films or electron beam evaporation and ion- beam sputtering in the case of indium tin oxide.
  • FIG. 1 illustrates a schematic of the steps of a method, generally 100, in accordance with an embodiment of the present invention.
  • [0004JFIG. 2 depicts a graph reflecting transmittance of light versus wavelength for coated glass and monolayer embedded polymethylmethacylate, in accordance with an embodiment of the present invention.
  • a conductor is typically an object or type of material that permits the flow of electrical current in one or more directions.
  • Conductors can be transparent or opaque.
  • Transparent conductors are typically deposited as continuous films by a variety of capital-intensive approaches based on physical vapor deposition, such as carbon vapor deposition in the case of graphene films or electron beam evaporation and ion-beam sputtering in the case of indium tin oxide.
  • GTCs graphene-based thin transparent conductors
  • Other embodiments of the present invention seek to provide GTCs that exhibit an enhanced resistance to cracking, peeling, and/or delamination compared to unfilled compositions.
  • Additional embodiments of the present invention seek to provide methods of manufacturing GTCs.
  • GTCs can exhibit a transparency that is at least fifty-percent.
  • the GTCs can exhibit an electrical conductivity of up to 1 ⁇ /square. For example, about 200 kO/square to about 300 kfi/square, about 300 kil/square to about 400 kil/square, about 400 kil/square to about 500 kil/square, about 500 kil/square to about 600 kil/square, about 600 kil/square to about 700 kil/square, about 700 kil/square to about 800 kil/square, about 800 kO/square to about 900 kil/square, and/or about 900 kil/square to about 1 ⁇ / ' square.
  • GTCs can have an electrical conductivity that is any value or range of values that are included in the aforementioned conductivity ranges.
  • GTCs can be formed using a composition (hereinafter “the composition") and embedding material.
  • the composition comprises graphene sheets and other carbon-based nanomateiial (discussed above).
  • the carbon-based nanomateiial can be prepared from a variety of sources, including but not limited to, graphite, graphite oxide or oxidized graphite, vaporized carbon resources.
  • Graphene sheets can be prepared as disclosed in U.S. Patent No. 7,658,901 to Prad'Homme et al, and/or U.S. Patent No. 7,745,528 to Prud'Homme et al., which is herein incorporated by reference.
  • the carbon-based nanomaieriai can have a thickness ranging from about 0,3 nm to about 100 nm, 0.3 nm to about 10 nm, and/or 0.3 nm to about 5 nm, as well as any single thickness value or range of values included within the aforementioned ranges.
  • the nanomateiial preferentially has a thickness or thickness range that promotes the desired amount of transmittable light able to pass through the GTC.
  • the carbon-based nanomaieriai can be in the form of sheets (for example graphene sheets) and/or platelets (for example graphite oxide) having, for example, an oblate shape, and/or high aspect ratio ribbons.
  • the carbon-based nanomaterial can have dimensions ranging from about 5 nm to about 1 nm, or about 10 nm to about 100 ⁇ . The dimension can be any value or range of values included in the
  • the carbon-based nanomaterial can be dispersed in a solvent prior to GTC production.
  • Applicable solvents can include, but are not limited to, water, ammoniated water, water whose pH is adjusted with a suitable base like sodium or potassium hydroxide, water with dissolved urea to disrupted hydrogen bonding, organic solvents, alcohols (such as methanol, ethanol, 1- propanol, isopropanol, 1-butanol, tert-butanol, pentanol, hexanol, etc.), water/alcohol mixtures, esters and carbonates (such as ethylene carbonate, propylene carbonate), dimethylformamide (DMF), acetonitrile, N-methylpyrrolidone, acetonitrile, dimethylsulfoxide (DMSO),
  • Applicable solvents may also include, but are not limited to, distilled or synthetic isoparaffinic hydrocarbons, such as Isopar ® and Norpar ® and Dowanol ® , citrus terpenes and mixtures containing citrus terpenes, such as Purogen ® , Electron, and Positron, terpenes and terpene alcohols (including terpineols, including alpha-terpineol), limonene, aliphatic petroleum distillates, alcohols (such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec- butanol, tert-butanol, pentanols, i-amyl alcohol, hexanols, heptanols, octanols, diacetone alcohol, butyl glycol, etc.), ketones (such as acetano
  • Dispersions can be utilized as is, concentrated, purified, or treated with additional additives. Subsequent to the dispersion formation, the composition, now in a dispersed form, can be coated onto a solid or liquid substrate.
  • solid substrates include glass, mica, quartz, alumina, zirconia, plastics such as polymethylmethacrylate, polycarbonate, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride (i.e., Teflon),
  • the composition can comprise graphene sheets or graphite platelets with a distribution of thicknesses and lateral dimensions spanning ranges noted above.
  • the dispersion can be applied to the air-water interface using a variety of applicable methods, for example, a Langmuir-Blodgett type technique utilizing a suitable solvent, such as a solvent that is immiscible with water and spreads out when a drop is placed on the surface of water.
  • a suitable solvent such as a solvent that is immiscible with water and spreads out when a drop is placed on the surface of water.
  • Applicable solvents can include, but are not limited to volatile organic solvents having a low miscibility with water, such as 1 ,2-dichloroethane, dichloromethane, toluene, dioxane, chloroform, as well the above disclosed solvents.
  • Applicable solvents compatible with the above method also include volatile, miscible solvents, which include, but are not limited to, solvents having the capacity to rapidly spread at the air-water interface, such as methanol, ethanol, isopropanol, 1-propanol and tetrahydrofuran.
  • the resulting film of graphene sheets floating at the air- water interface may subsequently be compressed to a higher density using a suitable method, such as with solid, movable barriers that reduce the interfacial area, convection introduced during deposition of the spreading solvent, directed convection within the water sub-phase, or from the air or gas phase above the film.
  • Applicable methods to induce the convection include, but are not limited to, methods that utilize jets, blowers, fans and/or propellers.
  • the resulting film may be deposited on solvents on which the graphene sheets and/or graphene platelets may float via an inverse Langmuir-Blodgett technique.
  • the resulting film may be convenient to transfer the resulting film to a solid substrate for additional processing utilizing a variety of methods, including but not limited to, dip-coating, stamp transfer, lowering of the air-water interface to pass the level of the substrate to be coated, or raising of the substrate to be coated through the air-water interface.
  • Specific examples include water, mixtures of water with salts, acids, bases or urea, any type of oil, room temperature ionic liquids, mercury, etc.
  • the film can be deposited directly onto an embedding material utilizing other applicable techniques, including, but not limited to, painting, pouring, tape casting, spin casting, solution casting, dip coating, powder coating, by syringe or pipette, spray coating, curtain coating, lamination, co-extrusion, electrospray deposition, ink-jet printing, spin coating, thermal transfer (including laser transfer) methods, doctor blade printing, screen printing, rotary screen printing, gravure printing, lithographic printing, intaglio printing, digital printing, capillary printing, offset printing, electrohydrodynamic (EHD) printing, microprinting, pad printing, tampon printing, stencil printing, Langmuir-Blodgett transfer, wire rod coating, drawing, fiexographic printing, stamping, xerography, microcontact printing, dip pen nanolithography, laser printing, as well as via pen or similar means.
  • other applicable techniques including, painting, pouring, tape casting, spin casting, solution casting, dip coating, powder coating, by syringe or pipet
  • Applicable embedding material include, but is not limited to, polymers and ceramic materials.
  • Applicable polymers include, but are not limited to, thermosets, thermoplastics, non- melt processible polymers, rubbers, elastomers, thermoplastic elastomers, polymer alloys, and copolymers.
  • copolymers refers to polymers derived from two or more monomers. The polymers can be crosslinked, vulcanized, or cured.
  • the aforementioned coating approaches can be used to create a film of graphene sheets comprised of closely spaced, discretely tiled graphene sheets and/or graphene platelets, which may form electrical contacts between adjacent graphene sheets and/or graphene platelets in the film by, for example, touching, overlapping, and/or being in close proximity to promote quantum mechanical tunneling therebetween, which can typically require a proximity of less than 20 nm for significant tunneling currents to flow.
  • the tiled layer of graphene sheets may be significantly free of overlap and, hence, may not form significant multilayers thereof material, although some overlap may be required to establish sufficient electrical contact, in accordance with an embodiment of the present invention.
  • the tiled layer may be comprised of no more than about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%), about 90%) overlapping graphene sheets or graphite platelets.
  • GTCs can allow at least about 50% to about 60%, about 50% to about 70%, about 50% to about 80%. about 60% to about 70%, about 60% to about 80%, and/or about 70% to about 80% of light having a wavelength of about 200 nm to about 800 nm to pass through.
  • GTCs can have a light transmission rate that is any single value or range of values included in the
  • GTCs may be utilized in a variety of applications, including, but not limited to, current collectors or conductive backing in solar cells, transparent electrodes for electrochromic windows, infrared reflectors for solar-control, low emittance windows to improve the thermal efficiency of buildings or vehicles, electrodes for flat-panel displays, transparent top electrodes for photovoltaic cells, defrosting windows (such as for freezers and cockpits), electrochromic mirrors and windows, oven window coatings, static charge dissipation coatings, static charge dissipation coatings, touch-panel controls, electromagnetic shielding, invisible security circuits, and organic light-emitting diodes.
  • GTCs may also be utilized in portable electronics applications, such as touch screens for smart phones, tablets, laptops, desktops, and similar devices. GTCs could be suitable for heated windows for airplanes, spacecraft, cars, buses, trains, boats, as well as other vehicles. GTCs may be utilized in heated flooring, seating, clothing or any other materials where the transparent heater, being transparent, would not be significantly apparent to a consumer making it more esthetically pleasing. GTCs may also be suitable for electrostatic shielding of sensitive materials and could be used in the packaging of circuit boards and other sensitive electronics or on a larger scale to shield the sensitive electronics on, for example, military drones, aircraft, sea craft, and other manned and unmanned vehicles or crafts. Additional applications include, but are not limited to, transparent sensors or resonators. GTCs may be fabricated to be thin and flexible, making them suitable applications requiring flexible conductors and/or electrodes, in particular.
  • the carbon-based nanomaterial can have a thickness of about 0.3 nm to about 5 nm, about 0.3 nm to about 100 nm, about 0.3 nm to about 10 nm, or about 5 nm to about 10 nm, or about 5 nm to about 100 nm.
  • the carbon-based nanomaterial can have a thickness that is any value or range of values included in the aforementioned thickness ranges.
  • the carbon-based nanomaterial can be in the form of sheets or platelets having, for example, an oblate shape, and/or high aspect ratio ribbons.
  • the graphene sheets can have a dimension ranging from about 5 nm to about 1mm, or about 10 nm to about 100 ⁇ .
  • FIG. 1 illustrates schematic steps of a method, generally 100, in accordance with an embodiment of the present invention.
  • Method 100 is a schematic of the GTC fabrication steps, which includes steps I, II, and III.
  • Step I includes a top and side cross-sectional view, views la and lb, respectively, which together depict the deposition of monolayer (hereinafter "ML") 115 on substrate 120.
  • ML 115 includes graphene sheets.
  • ML 115 is deposited on substrate 120 using one of the above mentioned deposition methods (step I).
  • EM embedding material
  • step II embedding material
  • EM 125 is removed from substrate 120 utilizing one or more of the above mentioned removal methods, which now includes ML 115 at least partially embedded therein (step III).
  • the conductive material in the embedded layer is exposed to the outside of the device and can easily be contacted with electrical leads.
  • a non-conductive skin of material typically exists between the conductor and the leads which requires an etching step to directly expose the conductor to the surface to be contacted.
  • the tiles cannot readily be peeled off. Embedding each sheet or platelet in the film prevent their slippage and thus films cannot easily be rubbed off of the surface in contrast to the film prior to embedding, which can be easily removed by rubbing with an oily instrument or ultrasonication in water.
  • a monolayer of the graphene sheets is produced by the rapid thermal exfoliation of graphite oxide (GO) that is prepared by ultrasonicating an appropriate amount of GO in 1 ,2- dichloroethane to yield a suspension comprised of individual graphene flakes and/or graphene platelets.
  • the suspension is subsequently slowly dripped onto the air-water interface, which resulted in a floating film comprised of the graphene sheets.
  • the floating film is compressed at the interface with mechanical barriers until the surface pressure reached a value of 30 mN/m, as measured with a Wilhelmy plate, which results in a densely packed monolayer of the graphene sheets (which is comprised of tiled graphene sheets touching edge-edge).
  • the resulting monolayer film is subsequently transferred to a glass substrate by withdrawing water from the trough that is holding the monolayer film and substrate until the height of the monolayer film is lower than the height of the substrate, which are placed in the water sub-phase prior to deposition.
  • the glass is subsequently removed from the trough and heated on a hotplate at 80°C overnight to eliminate any remaining solvent between the graphene sheets and the substrate.
  • Polymethylmethacylate hereinafter "PMMA”
  • PMMA Polymethylmethacylate
  • 1,2- dichloroethane is dissolved in 1,2- dichloroethane at about 20% to about 40 vol%.
  • the resulting solution is drop casted onto the glass slide coated with the graphene monolayer.
  • FIG. 2 depicts a graph that reflects the transmittance of light versus wavelength for the ML coated glass and the ML embedded PMMA.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne, dans certains modes de réalisation, des conducteurs transparents à base de graphène et des procédés de fabrication associés. Une première couche contenant des feuilles de graphène est formée sur un substrat. La première couche est transférée sur une seconde couche. La première couche comprend des feuilles de graphène. La seconde couche est transférée sur la seconde couche. Les feuilles de graphène sont incrustées dans la seconde couche par voie topique d'une manière qui expose partiellement une face des feuilles de graphène.
PCT/US2015/044520 2014-08-11 2015-08-10 Conducteurs minces à base de graphène WO2016057109A2 (fr)

Applications Claiming Priority (2)

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US201462036083P 2014-08-11 2014-08-11
US62/036,083 2014-08-11

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WO2016057109A3 WO2016057109A3 (fr) 2016-06-02

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017219125A1 (fr) 2016-06-10 2017-12-28 Pope Michael A Procédé et appareil pour la production de films monocouches à grande surface de nanomatériaux dispersés en solution
IT201600069279A1 (it) * 2016-07-04 2018-01-04 Leonardo Spa Elemento strutturale con riscaldatore per un veicolo, metodo di fabbricazione e metodo di funzionamento
WO2021008940A1 (fr) * 2019-07-16 2021-01-21 Paragraf Limited Générateur électrique et procédé de génération d'un courant électrique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7449133B2 (en) * 2006-06-13 2008-11-11 Unidym, Inc. Graphene film as transparent and electrically conducting material
CN102015529B (zh) * 2008-02-28 2014-04-30 巴斯夫欧洲公司 纳米石墨片和组合物
CN102791628B (zh) * 2010-02-19 2016-05-25 创业发展联盟技术有限公司 碳材料及其制造方法
KR20130038836A (ko) * 2010-03-08 2013-04-18 윌리엄 마쉬 라이스 유니버시티 그래핀 및 그리드 하이브리드 구조물에 기초한 투명 전극
WO2013070691A2 (fr) * 2011-11-07 2013-05-16 University Of Cincinnati Composites à base de polyimide chargés de nanofeuilles de graphène et procédés de fabrication de ces composites

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017219125A1 (fr) 2016-06-10 2017-12-28 Pope Michael A Procédé et appareil pour la production de films monocouches à grande surface de nanomatériaux dispersés en solution
CN109689329A (zh) * 2016-06-10 2019-04-26 迈克尔·波珀 产生溶液分散的纳米材料的大面积单层膜的方法和装置
EP3468763A4 (fr) * 2016-06-10 2020-02-12 Michael A. Pope Procédé et appareil pour la production de films monocouches à grande surface de nanomatériaux dispersés en solution
US10875052B2 (en) 2016-06-10 2020-12-29 Michael A. POPE Method and apparatus for producing large-area monolayer films of solution dispersed nanomaterials
CN109689329B (zh) * 2016-06-10 2021-10-19 迈克尔·波珀 产生溶液分散的纳米材料的大面积单层膜的方法和装置
IT201600069279A1 (it) * 2016-07-04 2018-01-04 Leonardo Spa Elemento strutturale con riscaldatore per un veicolo, metodo di fabbricazione e metodo di funzionamento
EP3266710A1 (fr) * 2016-07-04 2018-01-10 LEONARDO S.p.A. Elément structurel avec dispositif de chauffage pour un véhicule, procédé de fabrication et procédé de fonctionnement
WO2021008940A1 (fr) * 2019-07-16 2021-01-21 Paragraf Limited Générateur électrique et procédé de génération d'un courant électrique

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