WO2011112589A1 - Transparent electrodes based on graphene and grid hybrid structures - Google Patents
Transparent electrodes based on graphene and grid hybrid structures Download PDFInfo
- Publication number
- WO2011112589A1 WO2011112589A1 PCT/US2011/027556 US2011027556W WO2011112589A1 WO 2011112589 A1 WO2011112589 A1 WO 2011112589A1 US 2011027556 W US2011027556 W US 2011027556W WO 2011112589 A1 WO2011112589 A1 WO 2011112589A1
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- WIPO (PCT)
- Prior art keywords
- graphene
- transparent electrode
- grid structure
- grid
- graphene film
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
- H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
- H01L29/1606—Graphene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/413—Nanosized electrodes, e.g. nanowire electrodes comprising one or a plurality of nanowires
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022491—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of a thin transparent metal layer, e.g. gold
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/83—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising arrangements for extracting the current from the cell, e.g. metal finger grid systems to reduce the serial resistance of transparent electrodes
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
Definitions
- the transparent electrodes of the present invention further comprise a substrate, such as glass, quartz, boron nitride, silicon and polymers (e.g., polyethylene terephthalate (PET)).
- the substrate is beneath the grid structure and the graphene film.
- the grid structure is positioned on a top surface of the substrate, and the graphene film is positioned on a top surface of the grid structure.
- the transparent electrodes of the present invention have transparencies of more than about 70% in a wavelength region between about 400 nm and about 1200 nm (e.g., 550 nm). In more specific embodiments, the transparent electrodes of the present invention have transparencies of more than about 79% in the same wavelength region.
- the transparent electrodes of the present invention provide numerous improved properties over the transparent electrodes of the prior art, especially in terms of transparency, conductivity and sheet resistance.
- the transparent electrodes of the present invention also provide numerous optoelectronic-related applications, including applications in organic photovoltaics, organic light emitting devices, liquid crystal display devices and touch screens.
- FIGURE 1 depicts different arrangements of transparent electrodes, in accordance with specific embodiments of the present invention.
- FIG. 1A depicts transparent electrode 10, where graphene film 12 is on top of grid structure 14 and substrate 16.
- FIG. IB depicts transparent electrode 20, where graphene film 22 is sandwiched between grid structure 24 and substrate 26.
- FIG. 1C depicts a more specific embodiment of the transparent electrode structure shown in FIG. 1A, where the grid structure is a metal grid and the substrate is transparent.
- the metal grids are depicted as the white lines on the substrate.
- the graphene molecular structure and the grid are not to scale wherein the grid spacing is in reality much larger than the graphene lattice size.
- FIGS. ID-IE show more optical images of metal grids on transparent substrates.
- the metal grid is an Au grid
- the transparent substrate is glass.
- the Au grid size is 100 ⁇
- the grid lines have a width of about 10 ⁇ .
- FIGS. 1F-1G show optical microscope images of graphene grown on a copper foil.
- the grain boundaries have sizes of hundreds of ⁇ .
- FIGURE 2 shows an exemplary method of forming a transparent electrode in accordance with some embodiments of the present invention.
- Schemes A1-A4 depict the preparation of the metal grid on a transparent substrate, where Al represents the deposition of metal film (Metal 1) and photoresist on the transparent substrate; A2 depicts photolithography patterning of the grid structure; A3 depicts wet-etching of the metal film; and A4 depicts the removal of the photoresist.
- Al represents the deposition of metal film (Metal 1) and photoresist on the transparent substrate
- A2 depicts photolithography patterning of the grid structure
- A3 depicts wet-etching of the metal film
- A4 depicts the removal of the photoresist.
- Schemes B1-B4 depict the preparation of the graphene film by using a solid carbon source (PMMA), where Bl depicts spin-coating PMMA on a copper foil (Metal 2); B2 depicts growing the graphene film using a solid carbon source; B3 depicts spin-coating a PMMA sacrificial layer on graphene; and B4 depicts wet etching of the copper foil.
- PMMA solid carbon source
- Schemes AB1-AB2 depict the assembly of the hybrid electrode, where ABl depicts the transferring of graphene to the top surface of the metal grid structure; and AB2 depicts the removal of PMMA sacrificial layer by dissolution in acetone.
- FIGURE 3 shows the analysis and comparison of various transparent electrodes.
- FIG. 3A shows transmittance (black axis), sheet resistance (blue axis) and charge carrier density (red axis) of graphene transparent electrodes.
- the orange dots are the hybrid graphene electrodes used in this work.
- the black dots are undoped CVD graphene on the same plane as hybrid graphene.
- the red dots are HNO 3 doped graphene, which matched the calculated results.
- the purple dots are AuCl 3 doped graphene. Since their carrier density is not reported, the data points were placed midway between 10 12 and 10 13 cm "2 .
- FIG. 3B shows transmittance and sheet resistance of the hybrid graphene electrodes compared to commercial transparent electrode materials and previous research results.
- FIG. 3C shows the transmittance of various metal grids and hybrid films. See Table 2 for additional details.
- FIG. 3D shows photos of hybrid graphene films on glass and PET substrates.
- the graphene/copper grid hybrid 200x200x5 ⁇
- the graphene/gold grid hybrid 100x 100x 10 ⁇
- the graphene/copper grid hybrid 100x 100x 10 ⁇
- the bottom photo is a bent graphene/copper grid hybrid electrode on PET.
- FIGURE 4 shows spectroscopic and SEM analyses of the transparent electrodes used in FIG. 3.
- FIG. 4 A shows Raman spectrum of the graphene used in FIG. 3. The spectrum was taken using transferred graphene on Si0 2 surface.
- FIG. 4B shows Raman spectra of the graphene while on the metal grid covered glass.
- the inset image shows the path where the Raman spectra were taken.
- the scale bar in inset is 20 ⁇ .
- FIGS. 4C-4D show SEM images of the hybrid transparent electrode. Graphene covered areas are darker and flat.
- FIGURE 5 shows optical images of various grid structures.
- FIG. 5A shows optical images of Cu grid on glass.
- the Cu grid size is 200 ⁇ , and the grid lines have a width of 5 ⁇ .
- FIG. 5B shows optical images of Al grid on glass.
- the Al grid size is 100 ⁇ , and the grid lines have a width of 10 ⁇ .
- FIG. 5C shows optical images of Cu grid on PET.
- the Cu grid size is 100 ⁇ , and the grid lines have a width of 10 ⁇ .
- FIG. 5D shows optical images of Al grid on PET.
- the Al grid size is 200 ⁇ , and the grid lines have a width of 5 ⁇ .
- FIGURE 6 shows microscope photos of various graphene/metal grid hybrid electrodes. Graphene covers the lower part of all the images, as indicated by the red dashed lines.
- FIG. 6A shows optical microscope images of a graphene/gold grid hybrid electrode on glass.
- the grid size is 100 ⁇
- the grid line width is 10 ⁇ .
- FIG. 6B shows optical microscope images of a graphene/copper grid hybrid electrode on glass.
- the grid size is 200 ⁇ , and the grid line width is 5 ⁇ .
- FIG. 6C shows optical microscope images of a graphene/aluminum grid hybrid electrode on glass.
- the grid size is 200 ⁇ , and the grid line width is 5 ⁇ .
- FIG. 6D shows optical microscope images of a graphene/copper grid on PET.
- the grid size is 200 ⁇ , and the grid line width is 5 ⁇ .
- FIG. 6E shows optical microscope images of graphene/aluminum grid on PET.
- the grid size is 200 ⁇ , and the grid line width is 5 ⁇ .
- the most commonly used transparent electrodes are conducting oxides, such as indium-tin-oxide (ITO) on glass.
- ITO indium-tin-oxide
- OLEDs organic light emitting diodes
- ITO has a brittle nature.
- the indium component of ITO is sometimes being projected as a scarce commodity, and the cost of the overall ITO can limit its field of applications.
- ITO electrodes have limitations in terms of resistance, conductivity, and transparency.
- various ITO electrodes e.g., ITO electrodes with thicknesses of about 160-200 nm
- ITO's do not have identical absorption in the whole visible spectrum region. Consequently, it is desirable to develop more cost efficient transparent electrodes with better transmittance and lower sheet resistance.
- ITO gives about 30 to 100 ⁇ /sq at 90% transparency measured at the often-used standard wavelength of 550 nm.
- the present invention provides improved transparent electrodes and methods of making them.
- the transparent electrodes of the present invention typically comprise: (1) a grid structure; and (2) a graphene film associated with the grid structure.
- the transparent electrodes of the present invention further comprise (3) a substrate, such as a glass.
- the transparent electrodes of the present invention can have various arrangements and embodiments.
- Another aspect of the present invention provides methods of making the aforementioned transparent electrodes. Such methods generally comprise: (1) providing a grid structure; (2) providing a graphene film; and (3) associating the graphene film with the grid structure. In further embodiments, the methods of the present invention also comprise associating the transparent electrode with a substrate. As also discussed in more detail below, the methods of the present invention have many variations.
- Transparent electrodes of the present invention generally comprise: (1) a grid structure; a (2) graphene film; and an optional (3) substrate.
- the aforementioned components can be arranged and associated with each other in different ways.
- each of the above components can consist of different compositions of matter.
- Grid structures in the present invention generally refer to network structures that are capable of delivering electricity.
- a person of ordinary skill in the art will recognize that numerous materials may be used as grid structures.
- Non-limiting examples include metals, carbon nanotubes, graphite, amorphous carbons, metal particles (e.g., metal nanoparticles or metal microparticles) and combinations thereof.
- metals that can be used as grid structures include, without limitation, Au, Pt, Cu, Ag, Al, Ni and combinations thereof.
- one or more of the above-mentioned metals can also be associated with carbon nanotubes, graphite, or amorphous carbons in the grid structures of the present invention.
- carbon nanotubes in grid structures may be associated with one or more surfactants or polymers in order to help with dispersibility.
- the carbon nanotubes may be pristine carbon nanotubes.
- the carbon nantoubes may be functionalized carbon nanotubes.
- the grid structures of the present invention can have numerous arrangements and patterns.
- Non-limiting examples include one or combinations of the following patterns: crossbars, stripes, circles, random, diamonoid, rectangles, spheroid, parallelogram or hatched.
- FIGS. 1A-1E show non-limiting examples of various metal grid structures. More specifically, FIG. 1C shows the grid structure to be a cross-barred metal grid sandwiched between a transparent substrate and a graphene film. Likewise, FIGS. ID-IE show optical images of a transparent electrode with a cross-bar shaped Au grid on a transparent glass with grid sizes of about 100 ⁇ and grid line widths of about 10 ⁇ . A person of ordinary skill in the art can also envision other suitable grid structures with different sizes and lengths.
- the additives may be one or more heteroatoms of B, N, O, Al, Au, P, Si or S.
- the doped additives may include, without limitation, melamine, carboranes, aminoboranes, phosphines, aluminum hydroxides, silanes, polysilanes, polysiloxanes, sulfides, thiols, and combinations thereof.
- the graphene films may be HNO 3 doped and/or AuCl 3 doped.
- graphene films in transparent electrodes only consist of one layer (i.e., a monolayer). In other embodiments, the graphene films consist of multiple layers (e.g., 2- 9 layers or more, but multiple layers may affect transparency).
- graphene films may be made of sprayed graphene particles.
- sprayed graphene particles are disclosed in Zhu et al., "High Throughput Preparation of Large Area Transparent Electrodes Using Non- Functionalized Graphene Nanoribbons," Chem. Mater. 2011, 23, 935-939.
- sprayed graphene particles can be in the form of graphene nanoribbons that were derived from carbon nanotubes. See, e.g., Zhu et al.
- the sprayed graphene particles can be derived from exfoliated graphite, graphene nanoflakes, split carbon nanotubes, or reduced graphene oxide.
- the sprayed graphene particles may cover an entire surface area of a transparent electrode in a uniform manner, such as by the formation of an interlinked network.
- the graphene particles may be scattered throughout a surface area of a transparent electrode to form a non-uniform graphene film.
- the covered surface area can be a top surface of a substrate, a top surface of a grid structure, or other surfaces on transparent electrodes.
- substrates generally refer to support structures for the transparent electrodes of the present invention.
- a person of ordinary skill in the art will also recognize that various substrates may be used with the transparent electrodes of the present invention.
- suitable substrates include glass, quartz, boron nitride, silicon, plastic, polymers (e.g., PET) and combinations thereof.
- the substrates of the present invention are also transparent in order to maintain the transparency of the transparent electrodes.
- the substrate is glass.
- the substrate is PET.
- Other suitable substrates can also be envisioned by persons of ordinary skill in the art.
- the substrates of the present invention can have various shapes and properties. See, e.g, FIGS. 1A-1E.
- the substrate has a non-planar shape.
- the substrate has a planar shape.
- the substrate is flexible at room temperature.
- the substrate is rigid.
- the transparent electrodes of the present invention can have different arrangements.
- the graphene film is positioned on a top surface of a grid structure.
- the grid structure may also be positioned on a top surface of a substrate.
- FIG. 1A depicts the aforementioned "graphene topped” arrangement in transparent electrode 10.
- grid structure 14 is on a top surface of substrate 16
- graphene film 12 is on a top surface of grid structure 14.
- FIG. 1C depicts a more specific example of this "graphene topped" structure, where the grid structure is a metal grid and the substrate is glass.
- the grid structure may be positioned on a top surface of a graphene film.
- the graphene film may also be positioned on a top surface of a substrate.
- FIG. IB depicts the aforementioned "grid topped" structure in transparent electrode 20.
- graphene film 22 is sandwiched between grid structure 24 and substrate 26.
- the different components of the present invention may be adhesively associated with one another.
- adhesive association generally refers to the association of the different components of transparent electrodes by various methods, including fusion, adhesion with a film such as polyurethane, and other forms of direct contact known to persons of ordinary skill in the art.
- the grid structure and the graphene film may be adhesively associated with each other.
- a substrate may be adhesively associated with a grid structure.
- the substrate may be adhesively associated with a grid structure, and the grid structure may be adhesively associated with a graphene film to form the above-mentioned "graphene topped" transparent electrodes in FIGS. 1A and 1C.
- various adhesion layers may be used to adhesively associate the various components of transparent electrodes to the substrate or the graphene film.
- the adhesion layer may include, without limitation, Cr, Ti and/or Ni.
- various methods may also be used to adhesively associate the different transparent electrode components with one another. Such methods sometimes comprise heating the transparent electrodes at high temperatures in the absence of oxygen.
- Additional embodiments of the present invention involve methods of making the above- described transparent electrodes. Such methods generally include: (1) providing a grid structure; (2) providing a graphene film; and (3) associating the graphene film with the grid structure. In additional embodiments, the methods of the present invention may also include associating transparent electrodes with (4) a substrate. In some of such embodiments, the methods may include (a) positioning the grid structure on a top surface of the substrate; and (b) positioning the graphene film on a top surface of the grid structure to form the previously described "graphene topped" transparent electrodes. See FIGS. 1A and 1C.
- the above-mentioned methods may also include an annealing step that adhesively associates the various components of the transparent electrodes to each other.
- the annealing step may include the addition of an adhesion layer to one of the components, as previously described (e.g., addition of an adhesion layer between the substrate and the grid structure).
- the annealing step may include the heat treatment of the transparent electrode.
- the heat treatment occurs in the absence of oxygen.
- the heat treatment includes the treatment of the transparent electrode structure in an H 2 /Ar purged furnace for 30 minutes at about 350 °C.
- grid structures are formed or provided by methods such as evaporation, sputtering, chemical vapor deposition (CVD), inkjet printing, gravure printing, painting, photolithography, electron-beam lithography, soft lithography, stamping, embossing, patterning, and combinations thereof.
- CVD chemical vapor deposition
- inkjet printing gravure printing
- painting photolithography, electron-beam lithography, soft lithography, stamping, embossing, patterning, and combinations thereof.
- a grid structure may be prepared on a transparent substrate (typically glass) by photolithography, inkjet printing, gravure printing or some other patterning technique.
- photolithography with an etching procedure can be utilized.
- CVD or sputtering techniques may be utilized along with a masking technique.
- Other methods of forming grid structures can also be envisioned by persons of ordinary skill in the art.
- the graphene film is formed or provided by the spraying of graphene particles.
- the graphene particles may be sprayed onto a top surface of a grid structure.
- the graphene particles may be sprayed onto a top surface of a substrate.
- the graphene particles to be sprayed can include, without limitation, graphene nanoflakes, graphene nanoribbons, exfoliated graphite, reduced graphene oxide, split carbon nanotubes, and combinations thereof.
- the nanoribbons can be applied as a spray to the substrate or atop the grid. This can further be done with graphene sheets (see former references and disclosure).
- graphene films may be obtained by annealing a carbon source, such as polymethyl methacrylate (PMMA), on a metal catalyst, such as a copper foil.
- a carbon source such as polymethyl methacrylate (PMMA)
- PMMA polymethyl methacrylate
- graphene films may be formed or provided by CVD-based growth on suitable metals (e.g., Ni or Cu). Thereafter, the formed graphene films may be transferred to the metal grid-patterned transparent substrate directly.
- carbon sources that form graphene films may be doped with a doping reagent, such as a heteratom (e.g., BH 3 ).
- the advantages of forming a "graphene topped" structure can include: (1) reducing the possibility of etching graphene when the grid structure is etched; and (2) an easier way to get a large area grid structure.
- FIG. 2 A more specific example of a method of forming a "graphene topped" structure is depicted in FIG. 2.
- the grid structure is a metal grid.
- the substrate is a transparent glass substrate.
- schemes A1-A4 depict the preparation of the metal grid on the transparent glass substrate.
- Al represents the deposition of metal film (Metal 1) and photoresist on the glass substrate.
- the glass surface is first cleaned with acetone and deionized water.
- 3 nm titanium (as an adhesion layer) and 50 nm gold are sputtered or evaporated (thermal or e-beam) on the cleaned glass surface.
- Photoresist is then spin-coated on the gold surface.
- the photoresist is patterned by photolithography. Specifically, gold and titanium are etched away by wet etching to form the metal grid pattern shown in A3. The residual photoresist is then washed away with acetone to form the structure in A4. In addition, the metal grid substrate is rinsed with de-ionized water.
- schemes AB1-AB2 depict the assembly of the transparent electrode.
- ABl depicts the transferring of the graphene film onto the metal grid structure.
- AB2 depicts the removal of the PMMA sacrificial layer by dissolution in a solvent, such as acetone.
- the graphene film may first be transferred to or deposited on a substrate.
- the grid structure may then be patterned on top of the graphene film by photolithography, inkjet printing, or other method as described above.
- the "grid topped" structure may be suitable for robust transparent conducting films.
- the transparent electrodes of the present invention provide many advantages. Such advantages can include, without limitation: (1) low sheet resistance; (2) high transparency; (3) low costs; (4) availability of large fabrication areas; and (5) flexibility. [00105] Low Sheet Resistance
- the sheet resistance of the transparent electrodes of the present invention (depending on the transmittance of the film) can be less than about 500 ⁇ /sq, less than about 100 ⁇ /sq, or less than about 30 ⁇ /sq. In more specific embodiments, the sheet resistance of the transparent electrode structures can be as low as about 25 ⁇ /sq to about 3 ⁇ /sq when the transmittance is not lower than 91% and 79% at 550 nm, respectively. See, e.g., FIG. 3C.
- the transparent electrodes of the present invention can have transparencies of more than about 70%.
- the transparency can be up to 97.7%.
- the transparency is substantially in the visible region between about 400 and about 750 nm in wavelength, and more particularly around 550 nm.
- the transparency is not lower than about 70% at 550 nm, not lower than about 80% at 550 nm, or not lower than about 90% at 550 nm.
- the methods of making the transparent electrodes of the present invention are also cost effective.
- the materials used for the new transparent electrodes are earth- abundant stable elements, which increase their potential usefulness for replacement of indium- tin-oxide (ITO) in many applications.
- metal grids may be formed by normal photolithography techniques or by inkjet printing the precursor solution.
- noble metals Au, Pt and Ag more economically favored metals like Cu, Al and Ni can also be used.
- the methods of the present invention can be easily scaled up to provide larger transparent electrodes. For instance, conventional photolithography can easily be applied on substrates as large as several inches. Likewise, inkjet printing provides the possibility to process transparent electrodes on meter-sized substrates. Furthermore, even though graphene films may be limited to centimeter sizes, the formation of films can also be readily scaled up by using large annealing furnaces. And when applied by spray coating from graphene nanoribbons or graphene pieces, scalability could be even more simple.
- the transparent electrodes of the present invention also display enhanced flexibility. Without being bound by theory, it is envisioned that graphene films used in the transparent electrodes renders the electrodes flexible. Such flexibility can be important for many applications that are disclosed below.
- the transparent electrodes of the present invention can be used as electrodes for optoelectronics applications, such as organic photovoltaics, organic light emitting devices, "smart window” panes, liquid crystal display devices, touch screens, and "head-up” displays in, for example, windscreens, goggles, glasses and visors.
- the transparent electrodes of the present invention may find application in flexible solar cells and organic light emitting diodes (OLEDs).
- n m and ⁇ ⁇ are the majority carrier density and mobility respectively, q is the unit charge and t is the thickness.
- T transmittance
- a transmittance approximately 90% is required. This permits the assembly of up to four layers of graphene to reduce the sheet resistance while maintaining 90% transparency.
- the sheet resistance of four-layered graphene is ⁇ 350 ⁇ /sq, thereby falling 10-fold short of the desired sheet resistance of monolayered graphene.
- transparent electrodes can also be made using a non-transparent material such as metal nanowires or carbon nanotubes.
- a non-transparent material such as metal nanowires or carbon nanotubes.
- PEDOT/PSS poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)
- graphene those materials themselves are opaque.
- the materials can form thin transparent percolation networks. The network can conduct current and leave large empty spaces that render these films transparent.
- the graphene grown on copper or nickel substrates have inevitable defects induced by metal grain boundaries and the transferring techniques.
- the grain size of crystalline copper is typically over 100 ⁇ .
- defects have been found on the grain boundaries, which could be one reason for the high sheet resistance of synthesized graphene films. See FIGS. 1G-1H.
- a suitable grid size ⁇ 100 ⁇
- the transmittance of the hybrid film can be easily adjusted by modulating the metal grid size and gridline width.
- the metal grids are formed on the transparent substrate.
- a graphene film is grown on a copper foil and isolated with a layer of sacrificial PMMA.
- the graphene film is then transferred to the top of the grid, and the sacrificial PMMA layer is removed to form the final hybrid transparent electrodes.
- photolithography with wet-etching was applied to produce the metal grid structure. This procedure has numerous advantages.
- photolithography is a high throughput method with which large substrates can be easily processed.
- the metal grid networks formed by photolithography have minimal contact resistance between grid-lines.
- the graphene film was grown on copper either by using a gas carbon source or solid carbon source.
- the sheet resistance of the hybrid transparent electrode was measured by an Alessi four-point probe. The reported values are based on an average of 20 measurements for each sample.
- the transmittance was measured by a Shimadzu UV-vis-NIR Spectrometer. The results are shown in Table 1.
- the experimental observed mobility of graphene is between 2000 and 10000 cm 2 -V _1 -s _1 .
- the graphene transparent electrodes are made by a scalable method such as chemical vapor deposition, they can reach mobilities of 4000-5000 cm 2 -V _1 -s _1 at room temperature when placed on an insulating substrate. Applicants assume that chemical doping will not change this mobility when the carrier density is smaller than 10 13 cm "2 .
- FIG. 3A Based on Eq. 3 above, the sheet resistance and transmittance of graphene are plotted in FIG. 3A.
- the mesh surface in FIG. 3A could be regarded as the limitation of the present graphene transparent electrode (according to the mobility of 5000 cm 2 V 1 s -1 ).
- the shadowed region under the surface is achievable by present graphene transparent electrodes.
- the previously reported graphene transparent electrode data is plotted in FIG. 3 A as well.
- the most heavily doped material results (red dots in FIG. 3A) approach the calculation limit.
- Other undoped (black dots in FIG. 3A) or doped graphene (purple dots in FIG. 3A) show sheet resistance larger than the theoretical limit at the same transmittance (in the shadow region).
- FIG. 3C The broad absorbance spectra of the graphene/metal grid hybrid film are plotted in FIG. 3C.
- the transmittances of the hybrid film are almost flat in the range of 400-1200 nm, in contrast to ITO, which has a transmittance maximum at 550 nm.
- the additional graphene layer introduced the expected 2 ⁇ 3% loss of transmittance compared with the original metal grid frame.
- the hybrid film adapts to both rigid (glass) and flexible (PET) substrates, rendering it a general purpose transparent conducting electrode materials. See FIG. 3D
- the transparent metal grid/graphene electrode outperformed all commercial and research-based transparent conducting films in the transmittance range of 70-91%.
- the hybrid film is stable under ambient temperature when a suitable metal is used.
- the hybrid film can also be integrated onto a flexible substrate, which renders this hybrid film a general purpose transparent electrode material.
- the size of the Cu grain boundary is one of the guides to design the transparent electrode metal grid size. Starting from any point on the copper foil to travel 100-200 ⁇ , at least one grain boundary will be met. It is likely that graphene grown on this Cu foil will have defects at the Cu grain boundaries. This means that when the graphene is transferred onto a substrate, the current applied to the graphene will cross a defect after travelling 100-200 ⁇ . If the metal grid has a size of 100-200 ⁇ , the chances of the current crossing the graphene defects will be much smaller because the metal grid can bridge the defects.
- the grid mask used in this work is made by DWL66 mask maker. As outlined in
- the films After being developed by MICROPOSIT MF-319 developer (45 s), the films were baked again on a hot-plate (110 C) for 10 min. The second bake is important to obtain defect- free grid structures on the inch-sized samples. The samples were then etched by the Au etchant and then the Ti etchant. The residual photoresist was removed with hot acetone. Optical images of the Au grids are shown in FIGS. ID-IE.
- the procedure for making the Al grid is the same as for the preparation of the Cu grid. However, due to the good adhesion of Al on glass, no adhesion layer was needed. The thickness of Al film was 100 nm. Optical images of the Al grids are shown in FIG. 5B.
- the procedure is similar to the preparation of the Cu grid on glass except for the adhesion layer.
- Al was used as the adhesion layer when the PET substrate was used because Ni has a high melting point and the PET substrate overheated when attempting to deposit Ni with the Edwards evaporator.
- the thickness of the Cu film was 100 nm.
- Optical images of the Cu grids on PET are shown in FIG. 5C.
- Graphene was grown using a recently developed low temperature growth technique with poly(methyl methacrylate) (PMMA) as the carbon source. In some cases, the standard CVD method was applied as well.
- PMMA poly(methyl methacrylate)
- the graphene used in this work had mobilities between 700-2000 cm 2 V-i S-i .
- the wet transfer technique was used to transfer graphene onto the metal grid substrate. In brief, a thin layer of PMMA was spun on the graphene covered copper foil, and then the copper was etched with copper etchant. The floating PMMA passivated graphene was rinsed with water several times and transferred on various metal grid substrates. The sacrificial PMMA was finally removed with an acetone rinse at room temperature. The hybrid transparent electrode was dried in a vacuum oven overnight.
- the monolayer graphene film was almost invisible under the optical microscope. It is necessary to observe the edge of the graphene where the contrast between the covered and the uncovered areas are slightly different.
- the optical microscope images in FIG. 6 show the edges of the graphene on different metal grid substrates.
- Applicants have invented highly transparent, low sheet resistance, flexible, substrate compatible, low cost, and robust transparent electrodes.
- the main properties of the devices are better than or comparable with those of more expensive, nonflexible ITO electrodes.
Abstract
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US13/583,372 US20130048339A1 (en) | 2010-03-08 | 2011-03-08 | Transparent electrodes based on graphene and grid hybrid structures |
EP20110753931 EP2545561A4 (en) | 2010-03-08 | 2011-03-08 | Transparent electrodes based on graphene and grid hybrid structures |
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CN102637801A (en) * | 2011-12-14 | 2012-08-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Light-emitting diode |
WO2013119295A1 (en) * | 2011-11-18 | 2013-08-15 | William Marsh Rice University | Graphene-carbon nanotube hybrid materials and use as electrodes |
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SG183997A1 (en) | 2012-10-30 |
CN103038835A (en) | 2013-04-10 |
KR20130038836A (en) | 2013-04-18 |
JP2013542546A (en) | 2013-11-21 |
US20130048339A1 (en) | 2013-02-28 |
EP2545561A1 (en) | 2013-01-16 |
EP2545561A4 (en) | 2014-05-14 |
WO2011112598A1 (en) | 2011-09-15 |
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