• 专利附录
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    • 专利摘要:
    The present invention comprises a process for producing copper sheets with quasi-monocrystalline structure, and a process for producing high quality graphene using said copper sheets as the catalyst substrate. It also comprises a copper foil for the production of graphene, obtained by the process described in the present invention, which has a quasi-monocrystalline structure. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2593709A1
    申请号:ES201631029
    申请日:2016-07-27
    公开日:2016-12-12
    发明作者:Núria；FERRER CRUSELLAS；Lluis Riera Fontana；Elisabet PRATS ALFONSO；Gemma Gabriel Buguña；Philippe Godignon；Rosa Villa Sanz；José Antonio PADILLA SÁNCHEZ；Fernando ESPIELL ÁLVAREZ；Mercè SEGARRA RUBÍ；María Elena XURIGUERA MARTÍN
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；La Farga Lacambra SA；
    IPC主号:
    专利说明:

    Procedure for obtaining copper sheets as a substrate for the production of high quality graphene
    The present invention relates to a process for manufacturing copper sheets of quasi-monocrystalline structure, as well as their application as a substrate in the manufacture of
    graphene
    10 Background of the invention
    Graphene is a single layer of carbon atoms bonded according to a hexagonal pattern. This material has an extremely high mechanical force, as well as an exceptionally high electronic and thermal conductivity, which makes it an
    15 unique material with potential applications in numerous areas of science (Novoselov et al., Nature 490, 192-200, (2012). The method of obtaining and handling is closely related to the final quality of graphene, which will determine the applications in which it may be used, for example, in the manufacture of transistors (Ruoff, Colombo et al., Seienee 324 (5932), 1312-1314 (2009)).
    The chemical vapor deposition or CVO (Chemical Vapor Deposition) on a catalytic metal substrate is known as one of the most common techniques for obtaining graphene monolayers. In recent years, the catalytic metal substrate of choice has usually been nickel, but this is being progressively replaced by
    25 copper because the latter allows better control over the growth of graphene grains.
    In fact, in the process of chemical vapor deposition, there are numerous parameters that affect the growth of graphene, which are closely related to the
    30 physical properties of graphene obtained. Cai, Ruoff et al., Nano Lett. 11, 3519-3525, (2011), indicate that the most relevant parameters for the manufacture of high quality graphene are the roughness, the presence of grain boundaries, the crystalline orientation of the grains, surface defects, surface contamination and the oxygen content, among others. Pop, Lyding et al., Nano Lett. 11, 4547-4554, (2011), also insist on the huge
    The importance of the orientation of grains in the growth of graphene, and also study the influence of different diffraction planes present in the same copper foil,

    such as (100), (111), (210), (511), (533) OR (632).
    There are numerous documents in the state of the art that describe procedures for the manufacture of copper and its application as a substrate for the growth of graphene. Specifically, the use of some copper and other metal substrates has been described to improve the quality of the graphene obtained on them, and obtain graphene of a larger grain size.
    In US patent application 13 / 930,823 a method of manufacturing graphene is described, which comprises contacting a copper film with a gas, increasing the temperature of said film for a period of 40 minutes to approximately 10,000 C, heating it. at about 10,000 C for a period of about 1 hour, putting said copper film in contact with a carbon-containing gas for about 5 minutes, and cooling it to room temperature to produce a layer of graphene thereon. However, this document does not affect the properties of the copper sheets, but only the production of graphene is described, so the quality of the copper foil and the procedure for its preparation are not taken into account
    Patent US9359212 describes copper sheets of a purity equal to greater than 99.95% by weight for the production of graphene, with an oxygen concentration equal to less than 200 ppm by weight and 60 degrees of brightness in accordance with Japanese regulations JIS Z8741. These copper sheets have an average grain size equal to or greater than 100¡1m, up to a maximum value of 1050¡1m.
    In patent application EP2873744 a method of manufacturing graphene based on a copper sheet as a substrate is described, which comprises several steps: providing hydrogen gas and other carbon-containing gas while placing the hot copper sheet in a predetermined chamber, laminate a transfer sheet on the graphene surface, etch and extract the copper sheet to make graphene while the graphene is transferred to the transfer sheet. This method has a high complexity, and also requires the use of a transfer sheet to transfer graphene to the substrate.
    US9322096 describes a method for obtaining graphene by chemical vapor deposition on a high purity copper surface. This copper surface can be

    obtain by deposition of a layer of high purity copper on a layer of copper of lower purity, by means of techniques such as cathodic deposition, evaporation, electroplating, chemical vapor deposition or other processes of high purity deposition. In addition, the high purity copper layer can be subjected to a heat treatment at a temperature between about 750 ° C and 1000 ° C to increase its grain size and reduce the grain boundary density. However, this method requires two layers of copper, one of low purity and one of high purity.
    Another document of the prior art is patent application JP2013006709, which describes a method of manufacturing copper sheets that are used as substrates for the production of high surface area graphene at low cost. The copper sheets described in this document have a thickness of less than 5 ... 1m, and are obtained by a treatment at 1000 ° C for 1 hour in an atmosphere that contains more than 20% by volume of hydrogen, and the remaining argon volume
    JP5600129 describes a method of producing multilayer graphene over a large area of a metal catalyst substrate. The metallic catalyst, which is an alloy composed mainly of copper and nickel, is heated to a predetermined temperature at which the synthesis of graphene is increased by the action of said catalyst.
    EP2664580 patent application describes copper sheets having 60 degrees of brightness and an average grain size equal to or greater than 200 J.lm, which are obtained by heating at 1000 ° C for 1 hour under an atmosphere containing 20% or more by volume of hydrogen, and the remaining volume of argon. These copper sheets are subsequently used for the manufacture of high-area graphene at low cost. This document includes several examples in which different types of copper sheets, some of them free of oxygen (OF or "oxygen free"), have been used as the starting material for manufacturing the substrates of the invention. In these examples, the maximum grain size achieved with an OF copper sheet by this technique is 1000 J.lm, with low surface roughness values.
    Additionally, monocrystalline copper substrates, without grain limits, with a unique crystalline orientation and without roughness, have high manufacturing costs, and usually have small grain sizes, which makes it difficult to produce large graphene surfaces on them.
    From all of the above, there is a need to develop new copper sheet manufacturing processes with utility in the production of graphene, which allow obtaining copper substrates with large grains, a unique orientation and a very roughness low.
    Detailed description of the invention
    An objective of the present invention is to provide a process for obtaining copper sheets having characteristics suitable for use as a catalyst substrate in the production of high quality graphene.
    Said process includes the production of wire rods from a copper starting material, the subsequent severe cold plastic deformation thereof for obtaining copper with a nanometric or ultra-fine grain size, the cold rolling of said
    15 copper with a grain of nanometric or ultrafine size, and its subsequent heat treatment.
    "Nanometric grain size" means a grain size in microscopic structures equal to or less than 100 nm.
    20 "Ultra-fine grain size" means a grain size in microscopic structures equal to or less than 1 J.Jm.
    By "gigantic grain size" is meant in the present invention a grain size greater than 0.5 cm.
    The parameter URq "is defined according to ISO 4288 as the mean square roughness of the heights made from a profile.
    The parameter USq "is defined according to ISO 25178: 2010 as the average roughness 30 of the heights made from a surface.
    The term "quasi-monocrystalline structure" is well known in the art field to refer to those microscopic structures that lie on the border between monocrystallinity and polycrystallinity, that is, those polycrystalline structures that
    35 have a number of surface grains that are low enough to approximate the behavior and properties of a single crystal, but without being so.
    The term "approximately", as used in the present invention when it precedes a temperature value and refers to it, is intended to designate any temperature value in a range corresponding to ± 10% of its numerical value, preferably a range corresponding to ± 5% of its numerical value, more preferably
    5 a range corresponding to ± 2% of its numerical value, and even more preferably a range corresponding to ± 1% of its numerical value. For example, "approximately 100 ° C" should be interpreted as a range of 90 ° C to 110 ° C, preferably a range of 95 ° C to 105 ° C, more preferably a range of 98 ° C to 102 ° C, and still more preferably a range of 99 ° C to 101 ° C.
    The invention comprises a method of obtaining copper sheets having a quasi-monocrystalline structure, a grain size equal to or greater than 0.5 cm and an orientation in at least 90% of the surface of the grains in a single plane crystallographic selected from (100), (110) or (111) with a maximum disorientation of
    15 15 ° comprising:
    (a) select a copper starting material from the group consisting of OF copper, copper with a maximum content of 1000 ppm regardless of the silver and oxygen content, ETP copper or any copper alloy selected from the
    20 group consisting of: high purity copper alloys with 0.001-0.161% atomic weight of one
    or more elements selected from Zn, Pb, Sn, Ni, Ag, Sb or Ar, described in the
    ES2360718 patent.
    alloys of Cu 5N ("five-nines coopet ') of 99.999% purity comprising
    At least one element selected from the group consisting of 5-800 mg / Kg Pb, 10-100 mglKg Sb, 5-1000 mglKg Ag, 5-700 mglKg Pb, 20-500 mglKg Zn, 1-25 mglKg Cd, 1 -30 mglKg Bi, 10-400 mglKg Fe, 1-15 mglKg S and 15-500 mglKg Ni, described in US6103188, and 4N ("four-nines cooper") alloys of 99.99% purity which understand
    At least one element selected from the group consisting of 5-800 mg / Kg Pb, 10-100 mglKg Sb, 5-1000 mglKg Ag, 5-700 mglKg Pb, 20-500 mglKg Zn, 1-25 mglKg Cd, 1 -30 mglKg Bi, 10-400 mglKg Fe, 1-15 mglKg S and 15-500 mglKg Ni, described in ES2159225.
    (b) produce copper wire rods 8 to 23 mm in diameter from the starting material selected in step (a) by a method selected between casting

    Continuous billet-shaped with hot rolling or ascending vertical casting,
    (C) subject the wire rods obtained in step (b) to a severe cold plastic deformation process to obtain copper with nanometric grain size
    or ultrathin,
    (d) cold rolling the material obtained in step (c) with a total deformation equal to or greater than 95%, and
    (and) thermally treating the sheet obtained in step (d) at a temperature between approximately 700 ° C and 10700 C for a time equal to or greater than 30 minutes in an atmosphere comprising a volume of hydrogen equal to or less than 8%, and the volume remaining from a gas or gas mixture selected from the group consisting of argon, nitrogen or mixtures of argon and nitrogen.
    The copper material used as a starting product in step (a) to carry out the process of obtaining the copper sheets of the invention is selected from the group consisting of, but not limited to: OF or oxygen free copper ("oxygen free" or C1 0200 according to ASTM standard classification), copper with a maximum content of 1000 ppm regardless of the content of silver and oxygen, copper ETP or tenacious electrolytic ("electrolytictough-pitch" or C11000 according to ASTM standard classification ) or any copper alloy selected from the group consisting of:
    High purity copper alloys with 0.001-0.161% atomic weight of one or more elements selected from Zn, Pb, Sn, Ni, Ag, Sb or Ar, described in patent ES2360718. Five-nines cooper alloys of 99.999% purity comprising at least one element selected from the group consisting of 5-800 mg / kg Pb, 10-100 mg / kg Sb, 5-1000 mg / Kg Ag, 5-700 mg / Kg Pb, 20-500 mg / Kg Zn, 1-25 mg / Kg Cd, 1-30 mg / Kg Bi, 10-400 mg / Kg Fe, 1-15 mg / Kg S and 15-500 mg / Kg Ni, described in US6103188, and 99.99% pure 4N ("four-nines cooper") alloys comprising at least one element selected from the group consisting of 5-800 mg / kg Pb, 10-100 mg / kg Sb, 5-1000 mg / kg Ag, 5-700 mg / kg Pb, 20-500 mg / kg Zn, 1-25 mg / kg Cd, 1-30 mg / Kg Bi, 10-400 mg / Kg Fe, 1-15 mg / Kg S and 15-500 mg / Kg Ni, described in patent ES2159225.

    Preferably, the copper material used as a starting product in step (a) is selected from the group consisting of OF or oxygen free copper ("oxygen free ~ or C1 0200 according to ASTM standard classification), copper with a maximum content of 1000 ppm regardless of the content in silver and oxygen or ETP copper or tenacious electrolytic ("electrolytictough-pitch" or C11 000 according to ASTM standard classification).
    Severe cold plastic deformation of copper wire rods obtained in stage (b) can be carried out in various ways, taking into account that the selection of the method used is especially important since the objective of this stage is to obtain Copper with a nanometric or ultra-fine grain size. Preferably, said stage of severe cold plastic deformation (c) will be carried out by an angular channel extrusion process widely known in the industrial sector as the Conform ™ process (as described, for example, in US3765216).
    The Conform ™ process, known in the state of the art for more than 40 years, allows the manufacture of profiles and tubes of non-ferrous metals at an industrial level, and basically comprises the following stages: a filament-shaped metal is introduced, wire rod or similar in a groove arranged on the circumference of a rotating friction wheel; said wheel drives the metal into a containment space of a containment block that engages in the groove and seals the groove; The rotation of the friction wheel produces high temperatures and high pressures in the containment space, which plastically deform the metal; said metal can be extruded through a forming nozzle
    or row, and finally a tube is solidified to form a profile.
    More preferably, the stage of severe cold plastic deformation (c) will be carried out by the Conform ™ process using a row of the same dimensions as the copper wire rod. This allows to obtain a product after this stage with the same dimensions but with a micrometric or nanometric grain size. In an even more preferred embodiment, step (c) will be carried out by the Conform ™ process using a row with square-rectangular geometry. This geometry allows obtaining square-rectangular plates suitable for making the final deformations necessary in the subsequent cold rolling.
    The cold rolling of the material obtained in step (c) is carried out with a total deformation equal to greater than 95%, preferably with a total deformation equal to greater than 97%, and more preferably with a total deformation equal to greater than 99%. .

    In addition, the reduction steps for deformation should be 10% of
    reduction at least at each step, or at least 25 ~ m reduction at each step. Said deformation is preferably carried out with an ultra-polished roller mill with a hardness of 2000 to 4000 HV, a minimum roughness of 50 nm, a minimum roller diameter of 400 mm and a rolling speed of at least 5 rpm. In this way, it is possible to reduce the roughness of the final copper sheet obtained significantly. By way of illustration but not limitation, said ultra-polished rollers can be coated by an aluminum and titanium nitride (TiAIN) with a hardness of 3700 HV and a coefficient of friction of 0.5 or by a diamond-type carbon coating (DLC or "diamond-like coating") with a hardness of 2700 HV and a coefficient of friction of 0.1-0.01.
    Optionally, the process for obtaining the copper sheets of the present invention may comprise an additional heat treatment step prior to step (e), which comprises treating the sample obtained in step (d) at a temperature between about 200 ° and 700 ° C for a period of time between 1 and 10 minutes under an atmosphere comprising a volume of hydrogen equal to or less than 8%, and the remaining volume of a gas or gas mixture selected from the group consisting of argon , nitrogen or mixtures of argon and nitrogen.
    Step (e) of the process comprises a final heat treatment at a temperature between approximately 700 ° C and 1070 ° C for an equal time greater than 30 minutes in an atmosphere comprising a volume of hydrogen equal to less than 8% and a volume remaining from a gas or gas mixture selected from the group consisting of argon, nitrogen or mixtures of argon and nitrogen.
    In a preferred embodiment, the invention comprises a method of obtaining copper sheets having a quasi-monocrystalline structure, a grain size equal to or greater than 0.5 cm, an orientation of the entire surface of the grains in a single plane crystallographic selected from (100), (110) or (111) with a maximum disorientation of 15 ° comprising:
    (a) select a copper starting material from the group consisting of OF copper, copper with a maximum content of 1000 ppm regardless of the silver and oxygen content, ETP copper or any copper alloy selected from the group formed by:
    high purity copper alloys with 0.001-0.161% atomic weight of one
    or more elements selected from Zn, Pb, Sn, Ni, Ag, Sb or Ar, described in the
    ES2360718 patent.
    5N ("five-nines cooper") Cu alloys of 99.999% purity comprising
    At least one element selected from the group consisting of 5-800 mg / Kg Pb, 10-100 mglKg Sb, 5-1000 mglKg Ag, 5-700 mglKg Pb, 20-500 mglKg Zn, 1-25 mglKg Cd, 1 -30 mglKg Bi, 10-400 mglKg Fe, 1-15 mglKg S and 15-500 mglKg Ni,
    described in US6103188, and 99.99% pure 4N ("four-nines cooper") alloys comprising
    At least one element selected from the group consisting of 5-800 mg / Kg Pb, 10-100 mglKg Sb, 5-1000 mglKg Ag, 5-700 mglKg Pb, 20-500 mglKg Zn, 1-25 mglKg Cd, 1 -30 mglKg Bi, 10-400 mglKg Fe, 1-15 mglKg S and 15-500 mglKg Ni, described in ES2159225.
    (b) produce copper wire rods 8 to 23 mm in diameter from this material
    15 copper batch by a method selected from continuous casting in the form of billet with hot rolling or ascending vertical casting,
    (c) subject the wire rods obtained in step (b) to a severe cold plastic deformation process to obtain copper with nanometric grain size
    or ultrathin,
    20 (d) cold rolling the material obtained in step (c) with a total deformation equal to or greater than 95%, and
    (e) thermally treating the sheet obtained in step (d) at a temperature between approximately 700cC and 1070cC for a time equal to or greater than 30 minutes in an atmosphere comprising a volume of hydrogen
    25 or less than 8% and a remaining volume of a gas or gas mixture selected from the group consisting of argon, nitrogen or mixtures of argon and nitrogen.
    Preferably, the copper material used as a starting product in step (a) of
    30 This preferred embodiment is selected from the group consisting of OF or oxygen-free copper ("oxygen free" or C10200 according to ASTM standard classification), copper with a maximum content of 1000 ppm regardless of the silver and oxygen content or ETP or tenacious electrolytic copper ("e / ectro / ytic-tough-pitch" or C11000 according to ASTM standard classification).

    Another aspect of the invention relates to the copper foil obtained by the process of the invention.
    The crystallographic orientation of the copper grains in the spatial plane is an aspect of utmost importance for the correct growth of graphene. It is known in the state of the art that a single crystallographic orientation allows the continuous growth of graphene grains with the same characteristics, since a change of orientation attached to a grain boundary can cause differentiated growth between graphene grains. The crystallographic orientations present in the grains of the copper sheets obtained by the process of the invention are (100), (110) or (111), with a maximum disorientation of 15 °, depending on the thermomechanical treatments performed.
    The person skilled in the art is aware that it is necessary to optimize the process parameters for obtaining the copper sheet with quasi-crystalline structure of the invention having a single crystallographic plane selected from (100), (110) or (111) with a maximum disorientation of 15 °. The skilled person knows how to adjust the parameters in order to obtain the desired crystallographic plane.
    On the other hand, the disorientation interval between crystallographic planes between 0 ° and 15 ° does not respond to an arbitrary selection, but rather it is a specific interval where graphene has been shown to grow with higher quality. This disorientation interval has been set in relation to the gigantic granules and the manufacturing process of the copper foil.
    The copper foil of the invention has a quasi-monocrystalline structure, a grain size equal to greater than 0.5 cm and a crystallographic orientation in at least 90% of the surface of the grains in a single crystallographic plane selected from (100 ), (110) or
    (111) with a maximum disorientation of 15 °.
    Preferably, the copper foil of the invention has a quasi-monocrystalline structure, a grain size equal to or greater than 0.5 cm and a crystallographic orientation of the entire surface of the grains in a single crystallographic plane selected from (100), (110 ) or (111) with a maximum disorientation of 15 °.
    Additionally, the copper foil of the present invention, which has a quasi-monocrystalline structure, a grain size equal to or greater than 0.5 cm and an orientation

    Crystallographic on at least 90% of the surface of the grains in a single crystallographic plane selected from (100), (110) or (111) with a maximum disorientation of 15 °, has a quadratic average roughness (Rq) of less than 30 nm, preferably a quadratic average roughness of 3 to 10 nm within the grains.
    The effect of the planarity of the sample and the low roughness allow a correct growth of graphene. The fact that the copper sheets of the invention have a grain size greater than 0.5 cm implies a reduction in the number of grain boundaries, and therefore, a reduction in graphene growth obstacles, which It means a lower generation of defects during graphene growth.
    The copper sheets of the present invention have a thickness between 50 and 300 µm, more preferably between 100 and 200 µm. These thickness values represent an important technical advantage when these sheets are used for the production of graphene, both in the growth stage on the copper sheet, and in the subsequent separation stage of this metallic substrate, since they guarantee the planarity of the copper substrate In addition, when said separation is carried out by electrochemical delamination, instead of by chemical attack of copper. which is one of the most common techniques in this area and in which one usually works with a thickness of between 12 and 50 ~ m, a greater sheet thickness facilitates the handling of the material, while maintaining the optimum characteristics of the substrate metallic to achieve excellent graphene growth, such as low roughness, sample planarity or absence of surface defects.
    Another aspect of the invention comprises the application of the copper sheets of the invention as a catalyst substrate for the production of high quality graphene. The process for obtaining graphene of the invention is based on the method of chemical vapor deposition or evo ("Chemical Vapor Oeposition ') on a metal substrate, which in this case will be the copper sheets of the present invention. For this purpose , for example, standard CVO equipment, CVO equipment that allows rapid temperature ramps ("Rapid Thermal CVO") or plasma activated evo equipment ("Plasma enhanced CVO") can be used.
    In one embodiment, the process of producing graphene on the copper sheets of the present invention by chemical vapor deposition comprises:
    (to) Clean the copper foil by means of a chemical bath of acetic acid / deionized water / acetone water deionized / isopropyl alcohol,
    (b) inject the gases selected from the group consisting of: 50% argon by volume, 100% argon by volume, 50% diluted hydrogen by volume in argon
    or methane / hydrogen / argon in a proportion 30%: 30%: 40% by volume respectively, and let the gases act on the surface of the copper foil
    5 obtained after step (a) to obtain graphene layers with a grain size equal to or greater than 1mm,
    (C) deposit a protective polymer on the graphene created in step (b),
    (d) of electrochemically laminating the copper sheet coated by the polymer and the graphene produced,
    10 (e) transfer the sheet formed by the polymer and graphene onto the substrate on which it is desired to be applied, and
    (f) remove the protective polymer with a solvent to obtain graphene grains on the substrate.
    Preferably, the protective polymer used in step (c) is selected from polymethylmethacrylate (PMMA) or polydimethylsiloxane (PDMS). More preferably, the protective polymer used is polymethylmethacrylate (PMMA).
    The substrates on which the sheet formed by the polymer and graphene is transferred in the
    The stage (e) of the procedure is usually employed in this field of the art. By way of non-limiting example, some of the substrates are silicon oxide, polyimides, polymers of cyclic olefins (COP or "cyclo-olefin polymef"), copolymers of cyclic olefins (CaC or "Cyclic Olefin Copolymef"), polyethylene tereflalate (PET or "polyethylene terephta / ate") or SU-8 polymer.
    In a preferred embodiment, step (b) of the process for obtaining graphene from the copper sheets of the invention comprises the following sub-stages:
    30 (i) increase the temperature of the copper foil obtained in step (a) to approximately 700 ° C under argon,
    (ii) maintain the temperature at 700 ° C for 10 minutes under a 50% diluted hydrogen atmosphere in argon,
    (iii) increase the temperature to approximately 880 ° C with a ramp of
    35 equal temperature exceeding approximately 50 ° C / minute under hydrogen atmosphere diluted at 50% by volume in argon,
    (iv) maintain the temperature at approximately 880 ° C for 5 minutes while injecting methane / hydrogen / argon in a proportion 30%: 30%: 40% by volume respectively.
    5 Step (b), and more preferably, the sub-stages (i) - (iv), are of particular importancein the procedure since they allow to obtain graphene layers with excellent qualitywith grain size equal to greater than 1 mm.
    In another preferred embodiment, the protective polymer used in step (e) is polymethylmethacrylate (PMMA), and step (b) of the process for obtaining graphene from the copper sheets of the invention comprises the following sub-stages:
    (i) increase the temperature of the copper foil obtained in step (a) to approximately 70QoC under an argon atmosphere,
    15 (ii) maintain the temperature at approximately 700 ° C for 10 minutes under an atmosphere of hydrogen diluted at 50% by volume in argon,
    (iii) increase the temperature to approximately 880 ° C with a ramp of temperature equal to or greater than approximately 50 ° C / minute under an atmosphere of hydrogen diluted to 50% by volume in argon
    20 (iv) maintain the temperature at approximately 880 ° C for 5 minutes while injecting methane / hydrogen / argon in a proportion 30%: 30%: 40% by volume respectively.
    Through the use of copper sheets of quasi-monocrystalline structure of the present
    In the invention, it is possible to obtain large graphene surfaces of high quality and more continuously, which allows the formation of larger and more uniform grain sizes. These characteristics are crucial for the various applications of graphene, such as in the area of transparent electrodes, fiber optics, sensors or hydrogen storage.
    Throughout the description and the claims, the word "comprises" and the variations of the word are not intended to exclude other technical characteristics, additives, components or steps. The objects, advantages and additional features of the invention will be apparent to those skilled in the art after analysis of the description, or
    35 can learn from the examples of the invention. The following examples and drawings are provided by way of illustration and are not intended to be limiting of the

    present invention Additionally, the invention covers all possible combinations of
    the particular and preferred embodiments of this document.
    Brief description of the drawings
    FIG. 1. Difractogram of a commercial copper foil (25 ~ m thick, annealed,99.8% (metal base »corresponding to Example 4 of the invention.FIG. 2. Difractogram of a quasi-crystalline copper foil of the present invention
    corresponding to Example 4.FIG. 3. Schematic representation of the orientation of the grains present in aCommercial copper foil (25 ... Jm thick, annealed, 99.8% (metal base »withseveral crystallographic planes.FIG. 4. Schematic representation of the orientation of the grains present in acopper sheet according to the invention with a single crystallographic plane.
    Examples
    Example 1: Obtaining copper foil of the invention from copper wire rod with a total impurity content of a maximum of 1000 ppm, regardless of the silver and oxygen content
    It starts from a copper wire rod with a total impurity content of a maximum of 1000 ppm, regardless of the silver and oxygen content, and undergoes a severe deformation process through the ConformTM angular channel extrusion process, obtaining finally a plate with rectangular section 50 mm wide and 6 mm thick. A cold rolling of 98.3% of total deformation is then carried out, obtaining a final thickness of 1 00 ~ m. The reduction steps for deformation are of
    25 ~ m reduction in each step (total 236 steps). The final heat treatment to achieve gigantic grain sizes is carried out in an atmosphere of 5% by volume of hydrogen and 95% of argon. The temperature used is 1070 oC for 60 minutes.
    Roughness: R.q 6 nm Grain size: 3.5 cm
    Orientation: (100)
    Graphene quality: excellent Example 2:
    Obtaining copper sheet of the invention from a copper plate OF
    It starts from an 8 mm thick copper plate and a treatment is carried out
    5 thermal annealing for 5 hours at 400 oC. A cold rolling of 97.5% of total deformation is then carried out, obtaining a final thickness of 200 IJm. The reduction steps for the deformation suppose a 10% reduction in each step (total 34 steps). The final heat treatment to obtain gigantic grains is carried out in an atmosphere of 5% by volume of hydrogen and 95% of argon. The temperature used is 800 oC
    10 for 90 minutes. Roughness: Rq 5 nm Grain size: 1.5 cm Orientation: (100) Graphene quality: excellent
    Example 3: Comparative study of the roughness of copper sheets of the invention and commercial copper sheets
    20 Table I shows the results of the roughness analysis (Rq and Sq) of copper sheets produced by the invention from OF copper of 25 IJm thickness, and commercial copper sheets (25 IJm thickness, subjected to annealing , 99.8% (metal base. ”The results show that the copper sheets of the invention have an average roughness approximately 20 times lower than that of the commercial sheets.

    Table I
    Cu Invention Commercial Cu
    R, (nm) Sq (nm)R, (nm) Sq (nm)
    Sample 1 Sample 2 Sample 3 Sample 4 4 9 5 8 5 9 5 8141 164 80 94 97 105 115 123
    Example 4:
    5 Comparative study of the orientation of quasi-monocrystalline copper sheets of the invention and commercial copper sheets
    A comparative experiment of the orientation of the quasi-monocrystalline copper sheets of the invention and commercial copper sheets has been performed from the study of
    10 its X-ray diffraction patterns.
    As seen in FIG. 1, the X-ray diffraction pattern of the commercial copper foil (25 ~ m thick, annealed, 99.8% (metal base)) shows the existence of various orientations in the grains, as represented in a way
    15 schematic in FIG. 3. On the contrary, as seen in FIG. 2, only a crystallographic peak is observed for the copper foil of the invention, which shows that it has only one orientation (100), as schematically represented in FIG. Four.
    权利要求:
    Claims (14)
    [1]
    1. Procedure for obtaining copper sheets characterized in that it comprises:
    (to) select a copper starting material from the group consisting of OF copper, copper with a maximum content of 1000 ppm regardless of the silver and oxygen or ETP copper content,
    (b) produce copper wire rods 8 to 23 mm in diameter from the starting material selected in step (a) by a method selected from continuous billet casting with hot rolling or ascending vertical casting,
    (C) subject the wire rods obtained in step (b) to a severe cold plastic deformation process to obtain copper with nanometric grain size
    or ultrathin,
    (d) cold rolling the material obtained in step (c) with a total deformation equal to or greater than 95%, and
    (and) thermally treating the sheet obtained in step (d) at a temperature between approximately 7000e and 10700e for a time equal to or greater than 30 minutes in an atmosphere comprising a volume of hydrogen equal to or less than 8%, and the remaining volume of a gas or mixture of gases selected from the group consisting of argon, nitrogen or mixtures of argon and nitrogen,
    from which copper sheets are obtained that have a quasi-monocrystalline structure, a grain size equal to or greater than 0.5 cm and an orientation in at least 90% of the surface of the grains in a single crystallographic plane selected from (100 ), (110) or (111) with a maximum disorientation of 15 °.
    [2]
    2. The method according to claim 1, characterized in that the copper sheets have a quasi-monocrystalline structure, have a grain size equal to or greater than 0.5 cm and an orientation of the entire surface of the grains in a single crystallographic plane selected from (100), (110) or (111) with a maximum disorientation of 15 °.
    [3]
    3. The method according to any of claims 1-2, characterized in that the severe cold plastic deformation of step (c) is carried out by the Conform ™ angular channel extrusion process.
    The method according to any of claims 1-3, characterized in that the cold rolling of step (d) is carried out with a total deformation equal to or greater than 95%.
    [5]
    5. The method according to any of claims 1-4, characterized
    10 because the cold rolling of step (d) is carried out with a total deformation equal to or greater than 97%.
    [6]
    6. The method according to any of claims 1-5, characterized
    because the cold rolling of step (d) is carried out with a total deformation equal to or greater than 99%.
    [7]
    7. The method according to any of claims 1-6, characterized in that during the cold rolling of step (d) a reduction of at least 10% is carried out at each step or 25¡1m of reduction in each step.
    [8]
    8. Copper foil characterized in that it has a quasi-monocrystalline structure, a grain size equal to greater than 0.5 cm and a crystallographic orientation in at least 90% of the surface of the grains in a single crystallographic plane selected from (100 ), (110) or (111) with a maximum disorientation of 15 °.
    [9]
    9. Copper foil according to claim 8 characterized in that it has a crystallographic orientation of the entire surface of the grains in a single crystallographic plane selected from (100), (110) or (111) with a maximum disorientation of 15 °.
    [10]
    10. Copper foil according to any of claims 8-9 characterized in that it has a quadratic average roughness (Rq) of less than 30 nm.
    [11]
    eleven. Copper foil according to any of claims 8-10 characterized in that it has a quadratic mean roughness (Rq) of 3 to 10 nm inside the grains.
    [12]
    12. Copper foil according to any of claims 8-11 characterized in that it has a thickness between 50 and 300 iJm.
    [13]
    13. Copper sheet according to any of claims 8-12 characterized in that it has a thickness between 100 and 200 iJm.
    [14]
    14. Method of producing graphene on the copper sheets of claims 8-1 3 by chemical vapor deposition characterized in that it comprises:
    (to) clean the copper foil using a chemical bath of acetic acid / deionized water / acetone / deionized water / isopropyl alcohol,
    (b) inject the gases selected from the group consisting of: 50% argon by volume, 100% argon by volume, 50% diluted hydrogen by volume in argon
    15 or methane / hydrogen / argon in a proportion 30%: 30%: 40% by volume respectively, and let the gases act on the surface of the copper foil obtained after step (a) to obtain graphene layers with a size of grain equal to more than 1mm,
    (c) deposit a protective polymer on the graphene created in step (b),
    20 (d) electrochemically laminating the copper sheet coated by the polymer and the graphene produced,
    (e) transfer the sheet formed by the polymer and graphene onto the substrate on which it is desired to be applied, and
    (f) remove the protective polymer with a solvent to obtain graphene grains on the substrate.
    [15]
    15. Method according to claim 14, characterized in that step (b) comprises the following sub-stages:
    30 (i) increase the temperature of the copper foil obtained in step (a) to approximately 70Qee under an argon atmosphere,
    (ii) maintain the temperature at approximately 700e for 10 minutes under a 50% volume diluted hydrogen atmosphere in argon,
    (iii) increase the temperature to approximately 880 ° C with a ramp of
    35 equal temperature exceeding approximately 50 ° C / minute under hydrogen atmosphere diluted at 50% by volume in argon,
    (iv) maintain the temperature at approximately 880 ° C for 5 minutes while injecting methane / hydrogen / argon in a proportion 30%: 30%: 40% by volume respectively.
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    同族专利:
    公开号 | 公开日
    ES2593709B1|2017-11-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2011111932A2|2010-03-09|2011-09-15|Unist Academy-Industry Research Corporation|Method for manufacturing graphene, transparent electrode and active layer comprising the same, and display, electronic device, optoelectronic device, battery, solar cell, and dye-sensitized solar cell including the electrode and the active layer|
    WO2013081302A1|2011-11-29|2013-06-06|Samsung Techwin Co., Ltd|Thin metal film for synthesizinggraphene and graphene manufacturing method using the same|
    US20150361584A1|2014-06-13|2015-12-17|Jx Nippon Mining & Metals Corporation|Rolled copper foil for producing two-dimensional hexagonal lattice compound and method of producing two-dimensional hexagonal lattice compound|
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