WO2016126208A1 - Délaminage direct par voie sèche sans défauts de graphène déposé par dépôt chimique en phase vapeur à l'aide d'un polymère ferroélectrique polarisé - Google Patents

Délaminage direct par voie sèche sans défauts de graphène déposé par dépôt chimique en phase vapeur à l'aide d'un polymère ferroélectrique polarisé Download PDF

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WO2016126208A1
WO2016126208A1 PCT/SG2016/050057 SG2016050057W WO2016126208A1 WO 2016126208 A1 WO2016126208 A1 WO 2016126208A1 SG 2016050057 W SG2016050057 W SG 2016050057W WO 2016126208 A1 WO2016126208 A1 WO 2016126208A1
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graphene
substrate
ferroelectric polymer
layer
peeling
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PCT/SG2016/050057
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English (en)
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Barbaros ÖZYILMAZ
Iñigo MARTIN FERNANDEZ
Chee Tat TOH
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National University Of Singapore
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Priority to JP2017559270A priority Critical patent/JP6749942B2/ja
Priority to KR1020177024699A priority patent/KR102256000B1/ko
Priority to CN202010984483.9A priority patent/CN112194120B/zh
Priority to CN201680017209.6A priority patent/CN107406258A/zh
Publication of WO2016126208A1 publication Critical patent/WO2016126208A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/246—Vapour deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B32B2262/0238—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2313/00—Elements other than metals
    • B32B2313/04—Carbon
    • 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

Definitions

  • Graphene needs to be transferred from its growth substrate to the device surface because the growth substrate and/or the growth conditions are not compatible with the final device.
  • the main steps in such transfer processes are:
  • FIG. 1 shows a schematic diagram of a substrate/graphene/peeling layer structure, in accordance with the prior art, which includes a peeling layer 100, graphene 1 10 and a substrate 120.
  • the method to release the graphene/transfer layer from the growth substrate strongly affects the residual and defective level of the resulting graphene.
  • the methods can be grouped as wet (chemical etching, (electro-) chemical delamination) or dry (mechanical peeling)
  • a first mechanical peeling method uses pressure and/or temperature to achieve a conformal contact between the graphene and the peeling layer and/or high voltage to induce direct chemical bonding between them. Then, the chemical adhesion of the peeling layer to the graphene will need to be higher than the adhesion of the graphene to its substrate.
  • a second type of mechanical peeling method requires an adhesive layer as the peeling layer. Then, the adhesion of the adhesive layer to the graphene will need to be higher than the adhesion of the graphene to its substrate.
  • Non-uniform strain occurs when the peeling layer does not have a uniform coating over the entire graphene surface or when there is a large change in parameters like temperature and pressure.
  • Non-uniform peeling force is due to practical conditions of the graphene on substrate, where the substrate topography consists of grain boundary and terraces (10-100 ⁇ length dimensions). This changing topography leads to non-uniform peeling force during the peeling.
  • a method to peel the graphene layer from its growth substrate there is provided a method to peel the graphene layer from its growth substrate.
  • Previous methods rely on achieving an adhesion between the graphene and the peeling layer that will be stronger than that of the graphene to its substrate by putting the graphene in contact with a surface that will bond it stronger than the graphene bonds to its substrate.
  • a method in accordance with a version of the invention instead, uses the polarization of a ferroelectric polymer layer to induce stronger adhesion between the graphene and the ferroelectric layer compared to the adhesion between the graphene and its substrate.
  • an article for delamination of a graphene layer from a growth substrate comprises a graphene layer on a growth substrate, and a polarized ferroelectric polymer layer on the graphene layer.
  • the graphene layer is adhered to and sandwiched between the polarized ferroelectric polymer layer and the growth substrate.
  • the polarized ferroelectric polymer layer is arranged and polarized to produce a reduced relative adhesion between the graphene layer and the growth substrate with respect to adhesion between the graphene layer and the polarized ferroelectric polymer layer.
  • the polarized ferroelectric polymer layer may be arranged and polarized to strengthen the adhesion of the ferroelectric polymer layer to the graphene, and the adhesion between the ferroelectric polymer and graphene composite to the substrate.
  • the graphene layer may comprise single layer or multilayer graphene (such as between 2 and 10 layers) grown by a chemical vapor deposition-like process on a catalytic substrate such as copper.
  • the catalytic substrate may be other metals, including nickel, platinum or cobalt, or other materials known to catalyze graphene, including germanium.
  • the catalyst may comprise a metal foil or a metal thin film on a further substrate.
  • Graphene may be graphene by other epitaxial methods, such as by heating of silicon carbide.
  • the polarized ferroelectric polymer layer may comprise a fluoropolymer, such as polyvinylidene fluoride or a copolymer of polyvinylidene fluoride.
  • the polarized ferroelectric polymer layer may comprise a thickness of between about 1 nanometer and about 1 millimeter, such as a thickness of between about 100 nanometers and about 2000 nanometers.
  • the polarized ferroelectric polymer layer may comprise a remanent
  • a method of separating a composite from a growth substrate the composite including a ferroelectric polymer layer and a graphene layer, and the graphene layer being adhered to and sandwiched between the ferroelectric polymer layer and the growth substrate.
  • the method comprises (i) polarizing the ferroelectric polymer to produce a reduced relative adhesion between the graphene layer and the growth substrate with respect to adhesion between the graphene layer and the polarized ferroelectric polymer layer; and (ii) peeling the composite to separate the graphene layer from the growth substrate.
  • the ferroelectric polymer may be polarized to generate an attractive force to strengthen the adhesion of the ferroelectric polymer layer to the graphene and the adhesion between the ferroelectric polymer and graphene composite to the substrate.
  • the method may further comprise applying the ferroelectric polymer layer to the graphene layer to form the composite.
  • the method may further comprise transferring the peeled composite to a target substrate by adhering the graphene layer to the target substrate; and may further comprise removing the ferroelectric polymer layer from the graphene layer to leave the graphene layer adhered to the target substrate.
  • the continuity of the graphene layer on the ferroelectric polymer layer after the peeling may be 90% or more of an initial coverage of the graphene layer on the growth substrate, such as 95% or more or such as 99% or more of the initial coverage of the graphene layer on the growth substrate.
  • the composite may further include a secondary substrate adhered to the ferroelectric polymer layer, and the ferroelectric polymer layer may be sandwiched between the secondary substrate and the graphene layer.
  • the method may further comprise transferring the peeled composite to a target substrate by adhering the graphene layer to the target substrate; and releasing the secondary substrate from the ferroelectric polymer layer to leave the ferroelectric polymer layer and the graphene layer adhered to the target substrate; and the ferroelectric polymer layer may be removed from the graphene layer to leave the graphene layer adhered to the target substrate.
  • the polarizing may include applying an external electric field to the polymer layer.
  • the method may further comprise peeling the composite with a peeling force of at least about 85 J/m to separate the composite from the growth substrate.
  • Polarizing the ferroelectric polymer may result in a remanent polarization of the ferroelectric polymer of between about 5 ⁇ / ⁇ 2 3 ⁇ about 10 ⁇ / ⁇ 2 , such as about
  • FIG. 1 is a schematic diagram of a substrate/graphene/peeling layer structure, in accordance with the prior art.
  • FIG. 2 is a schematic diagram of a graphene peeling method in accordance with a version of the invention: the left panel shows graphene on the growth substrate, the center panel shows coating the graphene with a ferroelectric polymer such as polyvinylidene fluoride (herein, "PVDF"); and the right panel shows graphene-PVDF peeling from the graphene growth substrate.
  • PVDF polyvinylidene fluoride
  • FIG. 3 is a schematic diagram illustrating mechanisms for a strong graphene- ferroelectric polymer binding (such as a graphene-PVDF binding), in accordance with a version of the invention: the left panel shows PVDF-induced stronger electrostatic strengthening of the graphene to the ferroelectric film with respect to the strengthening of the graphene to the substrate; and the right panel shows PVDF-graphene atomic scale binding.
  • a strong graphene- ferroelectric polymer binding such as a graphene-PVDF binding
  • FIG. 4 is a set of atomic force microscopy images and cross sections of the roughness of the interfaces of the substrate-graphene-ferroelectric polymer system, in accordance with a version of the invention.
  • the left panel is the height scan of the graphene on the substrate before coating the ferroelectric polymer.
  • the central panel is the height scan of the graphene-polarized ferroelectric polymer after the graphene-ferroelectric polymer has been peeled from the substrate.
  • the right panel shows the cross sections of the substrate- graphene and the graphene-polarized ferroelectric polymer according to the sections on the left and central panels.
  • FIG. 5 is a plot of the adhesion energies between the substrate, graphene and the ferroelectric polymer layer after processing according to a particular example of the invention where the substrate is a copper foil, graphene is one layer of graphene grown by chemical vapor deposition on the copper, and the ferroelectric polymer layer is PVDF.
  • Dotted lines represent the critical adhesion between the polarized ferroelectric polymer layer and graphene composite and the composite, the critical adhesion energy between graphene and the copper substrate when an adhesive with sufficient adhesive strength has been applied onto graphene, and the critical adhesion energy between the ferroelectric polymer layer and graphene when the ferroelectric polymer is not polarized.
  • Experimental data relates to the peeling conditions of the polarized ferroelectric polymer layer and graphene composite from the substrate at different loads.
  • FIG. 6 is a set of photographs showing a comparison of graphene peeling yield using three different graphene peeling techniques.
  • the left panel is a photograph showing results after peeling with a polymer that does not result in a strong enough binding and/or electric field perpendicular to the graphene;
  • the center panel is a photograph showing results after peeling with a ferroelectric polymer which structure has not been processed to form ferroelectric grains and/or these grains have not been aligned according to a field
  • the right panel is a photograph showing results after peeling using a method according to a version of the invention. It can be seen that the technique used for the left panel leaves areas of no graphene 61 and graphene flakes 62; the technique for the center panel leaves areas of no graphene 63 and graphene patches 64; whereas the technique of the right panel, in accordance with a version of the invention, obtains coverage with both both graphene 65 and multilayer graphene 66.
  • FIG. 7 is a set of charts showing a statistical comparison of defects (cracks) after peeling of graphene using a method in accordance with a version of the invention and using a standard state-of-the-art graphene transfer process: the left chart shows the statistical distribution of the cracks according to their areas, and the right chart is a bar graph of the statistics on the total cracked area.
  • FIG. 8 is a schematic diagram showing uses of a direct peeling transfer method in accordance with a version of the invention.
  • Panel (a) shows a graphene/ferroelectric polymer
  • panel (b) shows a graphene-ferroelectric polymer on a substrate, with the graphene facing up
  • panel (c) shows a graphene-ferroelectric polymer on a substrate, with the graphene facing down
  • panel (d) shows graphene on a surface.
  • a version according to the invention provides a method of peeling a graphene layer from its growth substrate. Previous methods rely on achieving an adhesion between the graphene and the peeling layer that will be stronger than that of the graphene to its substrate by putting the graphene in contact with a surface that will bond it stronger than the graphene bonds to its substrate. A method in accordance with a version of the invention, instead, uses the polarization of a ferroelectric polymer layer to induce stronger adhesion between the graphene and the ferroelectric layer compared to the adhesion between the graphene and its substrate.
  • FIG. 2 is a schematic diagram of a graphene peeling method in accordance with a version of the invention.
  • the left panel shows the initial graphene 210 on the growth substrate 220.
  • the center panel shows coating the graphene 210 with a ferroelectric polymer 230, such as polyvinylidene fluoride (here, "PVDF"), with the characteristics that are described below.
  • PVDF polyvinylidene fluoride
  • the right panel shows peeling of the graphene/ferroelectric polymer layer 210/230 from the graphene growth substrate 220.
  • FIG. 3 is a schematic diagram illustrating mechanisms for a strong graphene- ferroelectric polymer binding (such as a graphene-PVDF binding), in accordance with a version of the invention, without wishing to be bound by theory.
  • a method according to a version of the invention uses the polarization of a ferroelectric polymer layer on the graphene to increase its adhesion to the graphene. Polarizing the ferroelectric polymer layer also increases the adhesion of the polarized ferroelectric polymer layer and graphene composite to the substrate. Polarizing the ferroelectric polymer layer also weakens the adhesion of the graphene to the substrate with respect to the adhesion of the graphene to the polarized ferroelectric polymer layer.
  • the coating of the graphene 310 with the ferroelectric polymer 330 is made to ensure a uniform interface that results in an atomically precise strong binding that limits the non-uniformities in the peeling process that may prevent the graphene from suffering stresses during the process. Therefore, the graphene may be prevented from mechanical damage.
  • the interface between the graphene 310 and the ferroelectric layer 330 is also engineered to reverse their low adhesion energies in order to achieve a binding energy that enables the peeling of graphene.
  • -Fluoropolymers have inherently weak attraction force, with Teflon being used for non-stick surface as an example.
  • -Ferroelectric polymers being fluoropolymers, they are the ideal material for strong van der Waals adhesion strength based on the Fluorine-Pi bond interactions with graphene, once the molecules are oriented accordingly.
  • the Fluorine-Pi intermolecular bond has a stronger attraction force between graphene/ferroelectric, enabling the mechanical peeling of graphene from the growth substrate.
  • the mechanical strength between the ferroelectric polymer and the graphene may not be strong and/or uniform enough at sites such as grain boundaries or copper terraces and, therefore cracks may happen during the transfer even though graphene is peeled.
  • graphene may be grown by a chemical vapor deposition (CVD) on a copper foil substrate.
  • the copper foil may be cleaned by, but not limited to, solvents to remove residues from its surface before placing it inside the growth chamber.
  • the growth process may include an annealing step where a gas such as hydrogen will be flown at a temperature around the growth temperature, that is, around 1000°C.
  • a hydrocarbon such as methane will be flown, maybe together with hydrogen to promote the growth of the graphene.
  • the chamber will be cooled down and the copper foil with the graphene on its surfaces will be taken out.
  • the graphene may be formed as a single layer or also as multiple layers according to types of growth substrate or conditions inside the synthesizing chamber.
  • SiC can be used to grow graphene.
  • the substrate will be annealed at a temperature that will sublimate the Si atoms at the surface of the SiC and will promote the recrystallization of the C atoms to form one layer or multilayers of graphene.
  • the graphene is coated with a solution of the ferroelectric polymer in a dry environment.
  • Processes such as, but not limited to spin-coating, Langmuir Blodgett, dip coating, slot die, bar coating, doctor blade or wire coating, may be used to form such coating.
  • a PVDF may be dissolved in dimethyl formamide (DMF) and this solution can be later coated on the graphene.
  • DMF dimethyl formamide
  • the graphene substrate/graphene can be coated with a PVDF thin film by spin coating.
  • Spin coating of a 10% solution of PVDF in DMF at 2000 rpm may result in the coating of a 500 nm thick film.
  • the substrate may need to be annealed previously to evaporate the water molecules on the graphene in order to achieve a graphene polymer interface to be free of water residues.
  • the coating may need to be completed in a dry environment for the polymer layer to be free of defects from water molecule trapping between its molecules.
  • the film may be annealed to evaporate the solvent and to recrystallize the polymer chains into grains.
  • the annealing temperature should be below the melting temperature of the polymer to promote the formation of the ferroelectric phase.
  • a 500 nm thick layer of PVDF film may be annealed at 135°C between 1 minute and 24 hours.
  • the resulting thin film polymer layer may be 1 nanometer to 1 millimeter thick, such as a thickness of between about 100 nanometers and about 2000 nanometers.
  • the dipoles in the ferroelectric polymer film may be aligned perpendicular to the graphene by applying an electric field across the film.
  • the field can be applied by a method such as, but not limited to, using external electrodes to apply a voltage across them or by ionizing the surface of the polymer.
  • annealing and polarization may be done in a single process.
  • polarizing a ferroelectric polymer may include applying an external electric field to the polymer layer, such as an external electric field comprising an electric field strength of between about 50 V/ ⁇ and about 500 V/ ⁇ ; and electrically polarizing a ferroelectric polymer may include ionizing the polymer's surface, such as ionizing at a voltage of between about 1 kV/cm and about 10 kV/cm.
  • the direction of polarization is preferred such that the Fluorine atoms of the ferroelectric polymer are aligned towards the graphene surface.
  • a field on the order of 100 ⁇ / ⁇ may be required to align the dipoles.
  • the dipoles in a PVDF film around 500 nm thick may be aligned by ionizing the surface of the polymer at a voltage of 6 kV/cm.
  • the polarized ferroelectric polymer layer may comprise a remanent
  • peeling of graphene/ferroelectric polymer from the growth substrate can be completed by applying a peeling force
  • peeling forces of at least about 85 J/m 2 result in a reliable defect-free peeling (see FIG. 5). Higher peeling forces may also result in a reliable peeling.
  • the critical force for the peeling of graphene that is, the lowest force for the peeling of graphene to occur, is equal to or below 85 J/m 2 .
  • Peeling forces below the critical force may result in cracks in graphene. However, a reliable defect free peeling at smaller forces may still be possible with sufficient control of the force applied or a sufficiently high peeling energy.
  • Peeling may be completed by a process such as, but not limited to, manual peeling and rolling a material that will attach to the PVDF (or the graphene substrate) stronger than the critical adhesion energies at the substrate-graphene-polymer interfaces.
  • the ferroelectric polymer may be thick enough to enable direct manual fast peeling of the copper foil from the ferroelectric
  • additional supports such as polymer foils, epoxies or tapes may be attached either to the graphene substrate, to the ferroelectric polymer or to both of them to ease the peeling. In these cases the binding of the additional supports to either of the surfaces will have to be stronger than the adhesion of the graphene to its substrate.
  • the support may be a thermal release tape with an adhesive strength of 3.7 N/20 mm (see FIG.5).
  • the adhesive strength between the tape and the polarized ferroelectric layer increases with peeling velocity and this needs to be at least 0.15 m/s to peel graphene from the substrate with adhesion strength of 85 J/m 2 .
  • Graphene peeling is unsuccessful at insufficient peeling velocity since the thermal release tape does not adhere sufficiently to the polarized ferroelectric layer to induce graphene peeling, i.e. the ferroelectric layer and the graphene remain on the copper foil.
  • the transfer process may be completed simultaneously on both sides of the substrate to peel the graphene on each of the surfaces.
  • a method in accordance with a version of the invention is compatible with the patterning of the graphene and/or the ferroelectric layer prior to the peeling of the composite from the substrate.
  • the benefits of the peeling method may only apply to the unpattemed graphene/ferroelectric polymer composite. For example, if an area of the initial composite was removed from the substrate prior to the peeling, that area will not be peeled.
  • the continuity of the graphene after peeling is a parameter that can be used to validate a method of peeling of graphene, since any mechanical defect (crack) in the graphene layer will degrade irreversibly the properties of the peeled graphene.
  • FIG. 6 compares the yield in the peeling of graphene by various techniques.
  • FIG. 7 is a set of charts showing a statistical comparison of defects (cracks) after peeling of graphene using a method in accordance with a version of the invention and using a standard graphene transfer process: the left chart shows the statistical distribution of the cracks according to their areas, and the right chart is a bar graph of the statistics on the total cracked area.
  • a stack of multilayers up to 10 multilayers, or more, can be peeled together with the main graphene layer.
  • These graphene multilayers are inherent to the graphene growth method.
  • the darker spots in the optical image of the right panel of FIG. 6 correspond to the multilayers of graphene that peeled together with the continuous graphene layer.
  • FIG. 8 is a schematic diagram showing uses of a direct peeling transfer method in accordance with a version of the invention.
  • panel (a) of FIG. 8 shows a graphene/ferroelectric polymer 810/830
  • panel (b) of FIG. 8 shows a graphene-ferroelectric polymer 810/830 on a transfer substrate 840, with the graphene 810 facing up
  • panel (c) of FIG. 8 shows a graphene-ferroelectric polymer 810/830 on a target substrate 850, with the graphene 810 facing down
  • panel (d) of FIG. 8 shows graphene 810 on a target surface 850.
  • the exemplary method of panel (a) of FIG. 8 may result in a continuous composite material.
  • the graphene 810 has a low sheet resistance because of the doping from the PVDF film 830. Electrostatic doping (by PVDF) is stable overtime, in contrast with other doping methodologies
  • PVDF graphene 810 is free of residues, its continuity is >99%
  • the exemplary method of panel (b) of FIG. 8 may result in a continuous composite material on top of a substrate, the graphene 810 facing up.
  • the graphene 810 has a low sheet resistance because of the doping from the PVDF film 830. Electrostatic doping (by PVDF) is stable overtime, in contrast with other doping methodologies
  • PVDF graphene 810 is free of residues, its continuity is >99%
  • Processing for this may be:
  • a second substrate (also called a transfer substrate) 840 on the polarized ferroelectric layer 830 (second substrate/ferroelectric/graphene/substrate), for example, but not limited to, a polyethylene terephthalate (PET) foil.
  • the second substrate 840 preferably is in intimate contact with the ferroelectric film 830.
  • An adhesive strength between the substrate 840 and the ferroelectric film 830 of 85 J/m 2 or higher enables the peeling of the graphene 810 without the second substrate 840 releasing from the ferroelectric film 830.
  • peeling velocity may be unrestricted.
  • the critical adhesion strength may be achieved by peeling at a high velocity because adhesion between at the interface will depend on this parameter.
  • the exemplary method of panel (c) of FIG. 8 may result in a continuous composite material on top of a substrate, the graphene 810 facing the target substrate.
  • the graphene 810 has a low sheet resistance because of the doping from the PVDF film 830. Electrostatic doping (by PVDF) is stable overtime, in contrast with other doping methodologies
  • PVDF graphene 810 is free of residues, its continuity is >99%
  • Processing for this may be:
  • [00120] -Forming the ferroelectric polymer layer 830 on the graphene 810 as described in the previous examples. [00121] -Attaching a second substrate 840 (not shown in panel (c)) on the polarized ferroelectric polymer layer 830 (second substrate/ferroelectric/graphene/substrate).
  • the second substrate 840 is compatible with the peeling of the graphene 810 in the next step of the processing and may be released later on.
  • An example of the second substrate 840 is thermal release tape.
  • the second substrate 840 has to be in intimate contact with the ferroelectric film 830.
  • the support may be a thermal release tape with an adhesive strength of 3.7 N/20 mm (see FIG.5).
  • the adhesive strength between the tape and the polarized ferroelectric layer increases with peeling velocity and this needs to be at least 0.15 m/s to peel graphene from the substrate with adhesion strength of 85 J/m .
  • Graphene peeling is unsuccessful at insufficient peeling velocity since the thermal release tape does not adhere sufficiently to the polarized ferroelectric layer to induce graphene peeling, i.e. the ferroelectric layer and the graphene remain on the copper foil
  • the exemplary method of panel (d) of FIG. 8 may result in a continuous graphene
  • [00135] Applying the second substrate/ferroelectric polymer/graphene stack on a third substrate (target substrate) 850. As described in the example above.
  • the ferroelectric polymer layer 830 (see panels (a) through (c)).
  • the polymer may be removed in a solvent to the ferroelectric polymer, for example, acetone or dimethyl formamide may be used to dissolve the polymer if this was PVDF. Additional solvent cleaning may be utilized to remove residues from the solvents used to dissolve the polymer.
  • the sample may be annealed at a temperature and atmosphere that will remove the polymer film, its residues or the residues from the solvent cleaning step when the annealing conditions will be compatible with the substrate/graphene stack. For example, when the substrate is a silicon/silicon oxide wafer, the stack may be annealed in an argon and hydrogen atmosphere at 350°C
  • a method in accordance with a version of the invention involves no chemicals for the release of the graphene from the graphene substrate
  • the graphene can be applied onto a substrate without any
  • a method in accordance with a version of the invention is a single-step and is performed fast
  • the fastest transfer process reported uses the electrochemical delamination method which transfers at a rate of ⁇ lmm/s.
  • a method in accordance with a version of the invention is not limited in speed. Peeling according to a version of the invention occurs at velocities of 0.15 m/s and above, for example in the range of about 0.5 m/s, thereby enabling truly fast transfer.
  • PVDF van der Waals and polarization induced interactions, not by any chemical absorption/interaction.
  • the polarized ferroelectric polymer layer is arranged and polarized to produce a reduced relative adhesion between the graphene layer and the growth substrate with respect to adhesion between the graphene layer and the polarized ferroelectric polymer layer.
  • the polarized ferroelectric polymer layer may be arranged and polarized to strengthen the adhesion of the ferroelectric polymer layer to the graphene, and the adhesion between the ferroelectric polymer and graphene composite to the substrate.
  • a method in accordance with a version of the invention has experimentally demonstrated statistical data over the peeling of graphene over an area that is significant to large area CVD graphene. Other reported mechanical peeling processes have not been able to validate their methods over such CVD graphene areas.
  • a method in accordance with a version of the invention has no need of melting any of the polymeric materials in the process.
  • graphene is single layer or multilayer graphene (for example, between 2 and 10 layers), preferably grown, for example, by a chemical vapor deposition-like process on a catalytic substrate such as copper.
  • the catalytic substrate may be other metals, including nickel, platinum or cobalt, or other materials known to catalyze graphene, including germanium.
  • the catalyst may comprise a metal foil or a metal thin film on a further substrate.
  • Graphene may be graphene by other epitaxial methods, such as by heating of silicon carbide.
  • substrate refers to the substrate graphene is grown on and may include, for example, a copper foil or film and any other materials known to be catalytic to graphene growth. Substrate may also refer to the secondary substrate used to peel the polarized ferroelectric polymer film and graphene composite from the substrate, as described above, and to enable the transfer of the composite to a target substrate. Target substrate refers to the substrate that the graphene is to be transferred to.
  • a "ferroelectric polymer” is a polymer that can be processed for it to show ferroelectric characteristics, that is, that it will maintain a permanent electric polarization that can be reversed, or switched, in an external electric field.
  • Ferroelectric polymers are fluoropolymers. Examples of ferroelectric polymers are polyvinylidene fluoride, PVDF, and its co-polymers.
  • One such co-polymer is poly[(vinylidenefluoride-co- trifluoroethylene], P(VDF-TrFE).

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Abstract

La présente invention concerne un procédé de pelage d'une couche de graphène à partir de son substrat de croissance qui consiste à utiliser le champ électrostatique d'une couche ferroélectrique polarisée pour produire une adhérence relative réduite entre la couche de graphène et le substrat de croissance par rapport à l'adhérence entre la couche de graphène et la couche de polymère ferroélectrique polarisé. L'invention concerne également des articles apparentés et des techniques pour le délaminage d'une couche de graphène à partir d'un substrat de croissance.
PCT/SG2016/050057 2015-02-03 2016-02-03 Délaminage direct par voie sèche sans défauts de graphène déposé par dépôt chimique en phase vapeur à l'aide d'un polymère ferroélectrique polarisé WO2016126208A1 (fr)

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GB2570127A (en) * 2018-01-11 2019-07-17 Paragraf Ltd A method of making graphene structures and devices
GB2570127B (en) * 2018-01-11 2022-06-22 Paragraf Ltd A method of making graphene structures
WO2020113174A1 (fr) * 2018-11-30 2020-06-04 The Research Foundation For The State University Of New York Procédé pour transférer du graphène émanant de substrats métalliques
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WO2022086449A1 (fr) * 2020-10-22 2022-04-28 National University Of Singapore Photodétecteur à polymère ferroélectrique, points quantiques et graphène
WO2022191782A1 (fr) * 2021-03-12 2022-09-15 National University Of Singapore Composite multicouche

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