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    • 专利摘要:
    Method for obtaining sheets of graphene. The present invention relates to a process for obtaining sheets of graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide or sheets of mixtures thereof from the powder of said materials. Said sheets are formed by a set of strips, where said strips consist of one to five layers. Said layers are layers of graphene, hexagonal boron nitride, molybdenum disulfide or tungsten disulfide having a monatomic or monomolecular thickness. In addition, the invention relates to a process for coating a surface with sheets of graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide or sheets of mixtures thereof. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2575711A1
    申请号:ES201431974
    申请日:2014-12-31
    公开日:2016-06-30
    发明作者:Manuel Arturo LÓPEZ QUINTELA；Gagik SHMAVON SHMAVONYAN；Carlos VÁZQUEZ VÁZQUEZ
    申请人:Universidade de Santiago de Compostela；
    IPC主号:
    专利说明:

    METHOD FOR OBTAINING GRAPHENE SHEETS 5 FIELD OF THE INVENTION
    The present invention relates to a process for obtaining graphene, boron nitride, molybdenum disulphide, tungsten disulfide or mixing sheets thereof. The invention also describes a method for coating a surface.
    10 with sheets of graphene, boron nitride, molybdenum disulfide, tungsten disulfide or sheets of mixtures thereof. BACKGROUND
    15 Graphite, boron nitride, molybdenum disulfide and tungsten disulfide are known in the state of the art as materials with organized structures in the form of layers at the molecular level with weak bonding forces between said layers. These layers are capable of sliding over each other with small tensile forces. In this text they are called “multilayer materials”.
    20 The most commonly used methods for exfoliation of the most popular multilayer material, graphite in graphene layers, include the use of solvents.
    Janowska's article (Janowska, I, Carbon, 2012, volume 50, pages 3106-3110)
    25 discloses the obtaining of graphene and graphene from a few layers by mechanical ablation of pencil mines that are made of graphite and binders. Said ablation consists not only in the sliding of graphene layers but also in the breaking and separation of layers. This process is done by rubbing the pencil mines against a quartz disk. A graphene sheet is deposited on said quartz disk. He
    The disc is immersed in a bath with a solvent and sonicated to remove graphene sheets from the surface of the quartz. These sheets have an average size of 2 µm. In multilayer sheets, graphene layers with the perfect hexagonal lattice are obtained, others


    with hexagonal lattice with gaps or waves. With this procedure, sheets containing from monolayers to fifty layers are obtained.
    The document by Chabot et al. (Chabot, V. et al., Scientific Reports, 3, Article number: 1378, published on March 12, 2013) describes the production of sheets of few graphene layers, about seven layers, by sonication of graphite powder (5 to 15 µm) with gum arabic.
    Regarding methods that do not use solvents, patent application EP 2567938 A1 describes the coating of a surface with multilayer graphenes, said coating is obtained from the lamination of multilayer graphenes directly on the surface to be coated. The multilayer graphenes that are used are formed by the aggregation of many multilayer graphenes that can have a thickness of from 0.34 to 10 nm. This document explains different methods of lamination of multilayer graphenes. One of said lamination methods consists in causing the multilayer graphenes to rub against the surface that is to be coated where said surface is a metallic surface, paper, vitreous carbon, or sapphire.
    It is not known in the state of the art a process that allows to obtain a sheet of graphene, boron nitride, molybdenum disulfide or tungsten disulfide or a sheet of mixtures thereof that does not use solvents and in which the sheets are easily and economically obtained from the powder of the materials, that is, from graphite powder, boron nitride, molybdenum disulfide or tungsten disulfide. BRIEF DESCRIPTION OF THE INVENTION
    The inventors of the present invention have developed a process for obtaining sheets formed by a web of strips, wherein said strips comprise in turn one to five layers, where each layer is thick of an atom or a molecule of a selected material. from the group consisting of graphene, boron nitride, molybdenum disulfide and tungsten disulfide, where said process comprises frictioning at least one multilayer material powder selected from graphite powder, boron nitride powder, molybdenum disulfide powder or tungsten disulfide powder between two


    substrates On at least one of the substrates, the sheet of strip material of a few layers of the material will be formed. The sheets thus formed are free of waves or gaps. The method comprises frictioning two substrates that have a powder of a multilayer material selected from the group consisting of graphite,
    5 boron nitride, preferably hexagonal boron nitride, molybdenum disulfide, tungsten disulfide and mixture thereof, manually or mechanically, preferably at ambient temperature and pressure conditions.
    The process of the present invention reduces the production costs of these sheets
    10 formed from multilayer materials, in particular decreases the costs of producing sheets formed by graphene layers. It also reduces production time, and avoids the use of chemical reagents, solvents or complicated technological devices. With the technology of the present invention, sheets or materials coated with said sheets can be obtained, which allow the development of applications such as
    15 flexible electronic devices, paper or plastic based electronic devices, transparent electrodes, etc.
    Therefore, in one aspect the present invention relates to a process for obtaining a sheet of graphene, boron nitride, molybdenum disulfide, disulfide
    20 tungsten or a sheet of mixtures thereof; wherein said sheet is formed by a set of strips, where said strips consist of one to five layers of graphene, boron nitride, molybdenum disulfide or tungsten disulfide, where said layers have a monoatomic or monomolecular thickness, and where said procedure comprises:
    25 a) placing powder of at least one multilayer material selected from the group consisting of graphite, boron nitride, molybdenum disulfide and tungsten disulfide, between two solid substrates, and
    b) frictioning the surfaces of said substrates between them and with said powder, said powder being located between them, 30 to form said sheet on the surface of at least one of the solid substrates.


    In a preferred embodiment the method further comprises removing the sheet from the solid substrate on which it has been formed.
    In another aspect the invention relates to a process for coating a substrate with a sheet of graphene, boron nitride, molybdenum disulfide, tungsten disulfide or a sheet of mixtures thereof; wherein said sheet is formed by a set of strips, where said strips consist of one to five layers of graphene, boron nitride, molybdenum disulfide or tungsten disulfide, where said layers have a monoatomic or monomolecular thickness, and where said procedure comprises:
    a) place dust of at least one multilayer material selected from the group that
    It consists of graphite, boron nitride, molybdenum disulfide and tungsten disulfide,
    between two solid substrates, at least one of them being the substrate whose surface
    you want to coat, and
    b) frictioning the surfaces of said substrates between them and with said powder,
    said powder being placed between them, to form the sheet on the surface of the solid substrate to be coated.
    In a preferred embodiment the solid surface of at least one substrate has a roughness of between 0.2 nm and 2 nm, preferably between 0.3 nm and 0.5 nm.
    In one embodiment the two substrates are of the same material and in another embodiment the two substrates are of different material.
    In one embodiment the substrate where the sheet is deposited has a hardness between 4.5 and 10 on the Mohs scale, preferably the substrate where the sheet is deposited has a hardness of at least 7 on the Mohs scale.
    In another embodiment the substrate where the sheet is deposited is selected from: a) inorganic materials, such as, for example,
    (i)  semiconductor materials,
    (ii)  dielectric materials; Y
    (iii) metals; or


    b) other materials selected from the group consisting of plastic, paper and wood.
    In one embodiment the layers are between 5 nm and 50 μm wide.
    In a particular embodiment, the multilayer material powder has an average particle size between 5 nm and 50 μm.
    In a preferred embodiment, the multilayer material powder used as the starting material is graphite powder and the sheet obtained after the process of the present invention is formed by strips of one to five graphene layers where each layer has a
    10 thickness of a carbon atom.
    In a preferred embodiment, the multilayer material powder used as the starting material is crystalline graphite powder and the sheet obtained after the process of the present invention is formed by strips of one to five graphene layers where the layer has a
    15 thickness of a carbon atom.
    In a preferred embodiment, the multilayer material powder used as the starting material is boron nitride powder, preferably boron nitride crystalline powder, more preferably hexagonal boron nitride crystalline powder, and the sheet obtained after the
    The method of the present invention is formed by strips of one to five layers of boron nitride, preferably they are layers of hexagonal boron nitride where layer is the thickness of the molecule of boron nitride, preferably of hexagonal boron nitride.
    In another embodiment, the multilayer material powder used as the starting material is a
    Powder mixture of at least two materials selected from the group consisting of graphite, boron nitride, molybdenum disulfide and tungsten disulfide. In a preferred embodiment, the multilayer material powder used as the starting material is a mixture of graphite powder and boron nitride powder.
    30 In one embodiment, friction is performed manually. In another embodiment the friction is performed mechanically.


    These preferred aspects and embodiments thereof are also further defined in the claims. BRIEF DESCRIPTION OF THE FIGURES
    5 Figure 1. Optical micrograph (5x) of strips of monolayer graphene and few layers (between 2 and 4 layers) on a silicon wafer obtained by friction of graphite powder located between two silicon wafers for 500 circular cycles with a approximate pressure of 200 Pa (pressure made with the fingers of the hand).
    10 Figure 2. SEM images (acronym for Scanning Electron Microscopy) of monolayer graphene nanotyras and few layers on a silicon wafer, said strips obtained by friction of graphite powder located between two silicon wafers during a ) 400 circular cycles or b) 800 circular cycles with an approximate pressure
    15 of 200 Pa (pressure made with the fingers).
    Figure 3. AFM image (acronym for Atomic Force Microscopy) 15 µm x 15 µm (a) and b)), 5 µm x 5 µm (c)) of monolayer and low-layer graphene strips (between 2 and 4 layers) on a silicon wafer, obtained by friction of graphite powder
    20 located between two silicon wafers for 500 circular cycles with an approximate pressure of 200 Pa (pressure made with the fingers of the hand).
    Figure 4. Raman spectrum of strips of monolayer graphene and few layers (between 2 and 4 layers) on a silicon wafer, obtained by friction of graphite powder placed between two wafers for 500 circular cycles with an approximate pressure of 200 Pa (pressure made with the fingers of the hand).
    Figure 5. Optical micrograph (20x) of strips of monolayer graphene and few layers (between 2 and 4 layers) on a silicon wafer, said strips obtained by friction of 30 graphite powder located between two silicon wafers for 200 circular cycles with an approximate pressure of a) 100 Pa (low) and b) 3 kPa (high).


    Figure 6. Optical micrographs (50x) of strips of monolayer graphene and few layers (between 2 and 4 layers) on a silicon wafer, said strips obtained by friction of graphite powder located between two silicon wafers at a pressure of approximately 200 Pa (pressure made with the fingers) and different number of friction cycles: a)
    5 250, b) 500, c) 1000 and d) 2000.
    Figure 7. Optical micrographs a) (5x), b) (100x) of strips of monolayer boron nitride and few layers (between 2 and 4 layers) on a silicon wafer, said strips obtained by friction of nitride powder Boron located between two silicon wafers for 1000
    10 circular friction cycles with an approximate pressure of 200 Pa (pressure made with the fingers).
    Figure 8. Optical micrograph (20x) of graphene and boron nitride strips on a silicon wafer, after 1000 circular cycles of friction for the boron nitride powder and 800 cycles
    15 friction circulars for graphite powder (method 1, example 4).
    Figure 9. Raman spectrum of 1) boron nitride powder; 2) strips of few layers (between 2 and 4 layers) of boron nitride, and; 3) Boron nitride monolayer strips, on a silicon wafer, said strips obtained by 1000 circular cycles of friction with a pressure
    20 approximately 200 Pa (pressure obtained by pressure with the fingers). Figure 10. Monolayer or multilayer graphene strip transferred from the surface of the silicon substrate to another silicon substrate with the surface clean by using adhesive tape commonly referred to as heat or fix paper.
    Figure 11. Intensity-voltage curve (IV) of a) strips of graphene of few layers (between 2 and 4 layers), and b) and c) strips of graphene monolayer on a silicon wafer, said strips obtained by 1000 circular cycles of friction with an approximate pressure of 200 Pa (pressure obtained by pressure with the fingers).
    30 Figure 12. X-ray diffraction of commercial graphite (Gr0n) and ground (Gr3n). According to the Debye-Scherrer equation, from the values of the diffraction peak width at half the maximum intensity (subtracting the instrumental contribution to this peak width),


    the following crystal size values were obtained in each case: Gr0n: 47.1 nm; Gr3n: 19.5 nm.
    Fig. 13. Optical micrographs (a) 20x, b) 100x) of monolayer nano-bands and a few layers of graphene and boron nitride in silicon wafers (finger pressure, approximately 200 Pa), obtained by means of a 50% mixture of graphite powder and boron nitride powder. The number of concentric friction cycles is 800.
    Fig. 14. Optical micrograph (5x) of strips of monolayer graphene, of few layers (between 2 and 4 layers) and multilayer on a silicon wafer obtained by friction of graphite powder located between a silicon wafer and a wafer of mica for 500 circular cycles with an approximate pressure of 200 Pa (pressure made with the fingers of the hand). DETAILED DESCRIPTION OF THE INVENTION
    In the context of the present invention the following terms have the following meanings:
    The term "sheet" refers to a two-dimensional material. Normally the surface of the sheet is continuous, without gaps and without waves. The dimensions of the sheet are obtained in the process and sheets of the desired dimensions can be obtained. The upper limit of the dimensions of the sheet is given by the dimensions of the surface of the substrate it covers during the procedure. In one embodiment the sheet has the same dimension as the surface of the substrate it covers. In another embodiment the sheet partially covers the surface of the substrate. The terms "cover" and "cover" are equivalent in the present invention.
    In this invention the terms "strip" and "strip" are equivalent and refer to a material with a dimension longer than the other. These strips are formed by one to five layers of a material selected from graphene, boron nitride, preferably hexagonal boron nitride, molybdenum disulfide and tungsten disulfide. In particular, due to the nature of graphene and hexagonal boron nitride, its layers are presently


    invention have a monoatomic thickness. The layers of molybdenum disulfide and tungsten disulfide are of molecular thickness. The strips that are forming the sheet can be superimposed and / or crossed or in any relative arrangement between them, for example, organized parallel to the sheet.
    The width of the strips may vary between 5 nm and 50 μm, between 10 nm and 20 μm, between 50 nm and 200 nm, preferably from 55 nm to 180 nm, and more preferably from 60 to 150 nm. Due to their dimensions in the nanometer range they can also be called "nano-bands" or "nano-strips".
    In one embodiment the sheet is formed by strips of the same material. In another embodiment the sheet is formed by strips of different materials, what is called a heterostructure
    or heterolamine. In a preferred embodiment the heterolamine is formed by graphene strips and boron nitride strips, preferably hexagonal boron nitride strips. In another embodiment the heterolamine is formed by graphene strips and molybdenum disulfide strips. In another embodiment the heterolamine is formed by graphene strips and tungsten disulfide strips.
    When the procedure is performed to obtain a heterolamine, the present invention presents two possible methods:
    In a first method, heterolamine is obtained by placing, in step a), powder of at least two multilayer materials selected from the group consisting of graphite, boron nitride (preferably hexagonal boron nitride strips), molybdenum disulfide and tungsten disulfide
    In a second method, heterolamine is obtained by performing the process of the invention using powder of a single multilayer material. After obtaining the sheet of said material, powder of a second multilayer material is located between two solid substrates where at least one comprises the sheet of the first material obtained above.
    In this invention the term "layer" refers to each two-dimensional structure of an atom or molecule of thickness, that is, of monoatomic or monomolecular thickness. For example, a


    graphene layer refers to a layer with a thickness of a carbon atom and correspondsto the thickness of a single layer of graphene.
    The strips may comprise one, two, three, four or five layers, which in this inventionit refers to "few layers" strips.
    The term "multilayer" in this invention refers to more than 5 layers.The width of the layers can vary from 5 nm to 50 μm, between 10 nm and 20 μm,preferably from 50 nm to up to 200 nm, preferably from 55 nm to up to180 nm, and more preferably from 60 to 150 nm.
    In a preferred embodiment the sheet is formed by strips and these in turn by layers ofgraphene Graphene is a substance formed of pure carbon, with atoms arranged inregular hexagonal pattern on a sheet of a thick atom. The terms "sheet" and "layer"they can be used equivalently in the present invention. In the present invention,a sheet formed by strips of one to five layers of graphene is called “sheet ofgraphene ”, and a strip formed by one to five layers of graphene are called“ strip ofgraphene. "
    In another embodiment the sheet is formed by strips and these in turn by layers of nitride ofhexagonal boron. Hexagonal Boron Nitride has a hexagonal structure whereNitrogen and boron atoms are linked by covalent bonds in the same plane. So byFor example, the thickness of a layer of hexagonal boron nitride is atomic in nature.In another embodiment the sheet is formed by strips and these in turn by disulfide layersMolybdenum In molybdenum disulfide, molybdenum has a sphere ofPrismatic trigonal coordination to which sulfur atoms bind, and each atom ofsulfur binds pyramidal to three molybdenum atoms, forming a structurelaminar where molybdenum atoms are among the sulfur atoms. Thislaminar structure is what this invention refers to when referring to a layer ofmolybdenum disulfide.
    In another embodiment the sheet is formed by strips and these in turn by disulfide layersof tungsten (or also called tungsten disulfide). Tungsten disulfide too


    It has a laminar structure that is what this invention refers to when referring to a layer.
    The terms "thickness" and "thickness" are used interchangeably in this invention to indicate the smallest of the dimensions of the layer or sheet. The "thickness" or "thickness" of the strips is defined in number of layers. The expression "place the dust" means to place, place, place or place the powder of the multilayer material between the substrates.
    The mass or amount of powder to be used depends on the surface area of at least one substrate on which the sheet is to be formed.
    In a preferred embodiment the amount of multilayer starting material powder is between 0.25 ng / mm2 and 5 ng / mm2. In another embodiment, between 0.5 ng / mm2 and 2.5 ng / mm2 are used. In another embodiment, at least 0.75 ng / mm 2 of powder is used. In another embodiment at least 1 ng / mm2 is used. By ng / mm2 is meant ng of powder per mm2 of surface area of substrate on which the sheet is to be formed.
    By way of illustration, in the examples of the present invention, pre-cut silicon wafers are used in square fragments of 10mm side (surface = 100mm2). Therefore, if 25 ng of graphite powder was used in one example, the mass per unit area used was 25 ng / 100mm2 = 0.25 ng / mm2. It is noteworthy that, due to the loss of material during the friction process, it is always convenient to put more quantity than the theoretical amount necessary to form a graphene monolayer covering the entire surface. Said theoretical amount is calculated in the state of the art. According to this calculation, one gram of graphene (monolayer) theoretically covers 2630 m2 of surface area (2630 m2 / gr, see eg B. Kuchta et al. Journal of American Chemical Society, 2012, 134, 15130-15137).
    The term "powder" refers to "multilayer material powder" and preferably refers to crystalline powder. In turn, the crystalline powder can be polycrystalline or monocrystalline. Therefore, in one embodiment the powder is polycrystalline. In another embodiment the powder is monocrystalline. The powder is constituted by what can be called grains,


    dust particles or nanoparticles, so when this invention refers to "the size of the powder" it means "the size of the grains, particles or nanoparticles of the powder". In this invention, the terms grains, particles and nanoparticles of dust may be equivalent, since the grains or particles have a size in the range of nm, where
    5 said range in this invention is defined between 5 nm and 500 nm, said particles or grains are considered nanoparticles.
    In one embodiment the powder size of the multilayer material is between 50 µm and 5 nm. In another embodiment, the powder of the multilayer material has a size between 20 µm and 10 nm. In
    In another embodiment the powder of the multilayer material has a size between 10 µm and 20 nm, and in another embodiment it is between 50 µm and 50 nm, preferably from 55 nm to 180 nm, and more preferably from 60 to 150 nm. In any of these embodiments, the multilayer material powder may be crystalline powder.
    The methods for measuring the size of the crystalline domain are known in the state of the art. For example, the Scherrer formula can be used from the values of X-ray diffraction. A particle of crystalline powder can consist of a single crystalline domain or several, so the crystalline domain size is the minimum size of the material. The size of the crystalline domain is between 5 nm and 200 nm, preferably between
    10 nm and 60 nm, and more preferably between 15 nm and 60 nm.
    In a preferred embodiment graphite powder is used. Normally, the particles or grains of commercial graphite powder have a size with an upper limit of 50 µm, since they are passed through a sieve of this size. Said particles or dust grains of
    Graphite can be the result of the aggregation of several smaller particles or nanoparticles.
    On the other hand, in one embodiment the crystalline domain of graphite is between 5 nm and 200 nm, in another embodiment it is between 10 nm and 60 nm, and preferably of
    30 approximately 50 nm. The particles or grains of crystalline graphite powder may be the result of the aggregation of several particles or nanoparticles.


    Both graphite powder and crystalline graphite powder can be ground to obtain smaller particle sizes.
    The size of these grains / particles / nanoparticles in the crystalline graphite powder is
    5 can be measured by X-ray diffraction. A particle of graphite powder can consist of a single crystalline domain or several, so the crystalline domain size is the minimum size of the material, that is, the graphite powder particles can have sizes up to 5 nm.
    10 Therefore, in one embodiment the size of the graphite powder is between 50 µm and 5 nm. In another embodiment, the size of the graphite powder is between 50 µm and 10 nm. In another embodiment the size of the graphite powder is between 50 µm and 15 nm. In another embodiment the size of the graphite powder is between 50 µm and 50 nm.
    In another particular embodiment, the graphite powder is high-order pyrolytic graphite (known in the art by its acronym in English: HOPG).
    In another embodiment, boron nitride powder is used. In one embodiment, commercial boron nitride powder sieved with a 10 µm sieve is used. In one embodiment the crystalline domain size 20 is between 50-200 nm, in another embodiment the crystalline domain size is between 100-200 nm and more preferably between 150-180 nm. Boron nitride powder can be ground to decrease its size. In one embodiment, the size of the boron nitride powder is between 50 µm and 5 nm. In another embodiment the size of the boron nitride powder is between 50 µm and 10 nm, preferably between 50 µm and 50
    25 nm and more preferably between 10 µm and 100 nm.
    The process of the present invention does not employ solvents.
    The "substrate" of the present invention is solid. The terms "solid substrate" and "substrate" are
    30 employed interchangeably in this text. In one embodiment the two solid substrates between which the multilayer material powder is placed are of different material. In another preferred embodiment, the two solid substrates between which the material powder is located


    Multilayer are of the same material. The substrates can be formed by the followingmaterials:a) inorganic materials, such as
    (i) semiconductor materials,5 (ii) dielectric materials;
    (iii) metals; orb) other materials.
    In a preferred embodiment, the substrate on which the sheet is formed is inorganic.
    In one embodiment at least one substrate is formed by a semiconductor material. In a preferred embodiment the semiconductor material is selected from the group consisting of silicon and silicon carbide. In one embodiment at least one substrate is formed of silicon crystal.
    In one embodiment at least one substrate is formed of a dielectric material. In a preferred embodiment the dielectric material is selected from the group consisting of ceramics, mica and glass. The ceramic materials can be of the oxide, non-oxide or compound type. In a preferred embodiment the ceramic material is porcelain. In a
    In particular, the ceramic material is of the oxide type, preferably of transition metal metal oxide. In a particular embodiment the ceramic material is of the oxide type and is selected from alumina, beryllium oxide, cerium oxide, zinc oxide and zirconia (also called zirconium dioxide).
    In one embodiment at least one substrate is formed of a metallic (metal) material, where the metal can be cobalt, copper, silver, gold, iron, platinum or palladium, preferably cobalt.
    In another embodiment at least one substrate is formed by another material other than the inorganic materials described above selected from the group consisting of plastic, paper and wood.


    The original surface of the substrate on which the sheet is to be formed with the process of the invention has a roughness of between 0.2 and 2 nm, preferably less than 1 nm, preferably between 0.3 nm and 0.5 nm , and more preferably less than 0.5 nm. The surface is preferably flat.
    The substrate can have any hardness, for example greater than 1 on the Mohs scale. In a preferred embodiment, the substrate has a hardness of between 4.5 and 10 on the Mohs scale. In a more preferred embodiment, the substrate has a hardness of at least 7 on the Mohs scale.
    The thickness of the substrate is irrelevant to the present invention. The surface area of the substrate is relevant to calculate the amount of powder necessary to obtain a sheet of material formed by strips of between 1 and 5 layers.
    In a preferred embodiment at least one substrate is a silicon crystal wafer. In another preferred embodiment, the two substrates are silicon crystal wafers.
    Friction between the surfaces of the substrates can be performed in any direction, for example circular, linear, forming triangles, squares, etc. and at any angle to the earth's surface, vertically or horizontally.
    It doesn't take much force to make the pressure. For example, the pressure of two fingers of the same hand (for example, thumb and index finger) on the substrates when performing the friction movement manually is sufficient to obtain the sheets of the present invention. That is, the minimum pressure could have a value of about 0.1 kPa (100 Pa), which is what is known that the fingers can do. In one embodiment, friction is performed manually. In another embodiment the friction is performed mechanically.
    Friction is performed in several friction cycles. A "friction cycle" is defined as the friction movement that is performed between the substrates to return to an initial position and that is repeated consecutively. The number of repetitions or cycles depends on the following characteristics:


     The pressure or force applied during friction: The pressure and the number of cycles are inversely proportional.
    o In a particular embodiment where friction is done manually, that is, between 0.1 kPa and 1 kPa, loose strips with 20-50 cycles can be obtained, but to obtain the sheets of the invention between 400 and 1000 cycles are necessary , preferably more than 500 cycles.
    o In a particular embodiment where friction is done mechanically, for example, with a pressure between 1.1 kPa and 500 kPa, few cycles are needed to obtain the sheets of the invention, preferably less than 100 cycles, more preferably less than 50 cycles
     The powder size of multilayer material: In an embodiment in which silicon substrates are used, friction is performed manually and the graphite powder is between 50 nm and 50 µm in size, the number of cycles may vary from 10 to 2000 cycles respectively.
     The amount of dust and the hardness of the substrate. The amount of dust calculated according to the surface area is used, as previously mentioned. It is noted that in the case that high hardness substrates are used, that is, substrates with a hardness greater than 4, preferably greater than 4.5 on the Mohs scale, for example silicon having a hardness of 7 in The Mohs scale, if more multilayer material dust is added, is not as important as the excess dust will fall from the substrates during the friction process. However, when substrates of low hardness are used, that is to say a hardness less than 4 on the Mohs scale, for example mica that has a hardness of 2.8 on the Mohs scale, the use of the minimum amount of dust in relation to the substrate surface, it is essential to prevent dust agglomerations from forming on the substrate. In addition, when using low hardness substrates it is preferable to use low friction pressures, preferably 200 Pa or less.
     The speed of friction cycles. From the examples made, the researchers consider that the increase in friction velocity could have an effect similar to that of the increase in pressure, that is, increasing the friction speed increases the number of strips per cycle of


    friction and decreases the number of cycles needed. In addition, there seems to be another similarity, and that is that when two silicon substrates are used and the speed and / or pressure is greatly increased, the friction cycles necessary to obtain the sheets cannot be performed since during the friction the two sheets formed in each
    5 one of the substrates tend to bind, thus blocking friction. The preferred friction speed is between 5 and 100 cm / s, in another embodiment the friction speed is between 10 and 50 cm / s. In another embodiment the friction speed is between 10 and 30 cm / s. These speeds are approximate and are calculated for substrates with a surface area of 1 cm2.
    In a preferred embodiment, in the process a step c) is further carried out comprising removing the sheet obtained after step b) on the at least one solid substrate on which said sheet has been formed. Said step c) can be performed by any transfer method known in the art, preferably by the method known in
    15 the technique of adhesive tape (hot or fixed paper) (see example 6).
    As used herein, the term "approximately" means a slight variation of the specified value, preferably within 10 percent of the specified value. However, the term "approximately" may mean a greater tolerance of variation depending on, for example, the experimental technique used. The expert understands said variations of a specified value and these are within the context of the present invention. In addition, to provide a more concise description, some of the quantitative expressions provided herein do not qualify with the term "approximately." It is understood that, whether or not it is used in a manner
    25 explicitly the term "approximately", each quantity given herein is intended to refer to the actual given value, and also intends to refer to the approximation of such value since it would be reasonably deducted based on common experience in the art, including equivalents and approximations due to experimental and / or measurement conditions for such given value.
    These preferred aspects and embodiments thereof are also further defined in the claims.


    In order to facilitate the understanding of the preceding ideas, some examples of the experimental procedures and embodiments of the present invention are described below. These examples are merely illustrative. EXAMPLES Example 1. Influence of friction on the formation of graphene nano-bands and sheets obtained by the process of the present invention
    At least 200 ng (2 ng / mm2) of graphite powder (crystalline domain size = 19.5 nm, obtained by a grinding process) or crystalline domain size powder = 47.1 nm (Merck commercial quality) )) between 2 silicon wafers (average roughness of 0.5 nm at 15 microns and hardness 7 on the Mohs scale). Silicon wafers have a silicon dioxide layer of less than 5nm. The silicon wafers of the examples are silicon wafers of 4 inches in diameter pre-cut into square fragments of 10mm side (surface = 100 mm2) (specifically, they are sold pre-cut into 55 fragments). Therefore, the dust concentration per unit area is 200ng / 100mm2 = 2 ng / mm2. Friction is performed manually concentrically with different friction cycles: 250 (Fig. 6a), 400 (Fig. 2a), 500 (Fig. 1 and 6b), 800 (Fig. 2b), 1000 (Fig. 6c) and 2000 (Fig. 6d) and also with different pressure applied during friction: 100 Pa (Fig. 5a), 200 Pa (Fig. 1-4 and 6) and 3 kPa (Fig. 5b). Fig. 2a shows that in the case of few friction cycles (400 or less) graphite points are formed on the silicon wafer, as well as multilayer or low-layer graphene nano-bands (<5) (see also Fig 6a). As the number of friction cycles increases, the graphite points disappear and the number of graphene nanobands increases (Fig. 2b and Figure 6a and 6b). After 500 cycles of friction or more, only monolayer or low-layer graphene sheets are obtained (Fig. 1). Figures 1 to 3 show the formation on silicon wafers of monolayer and low-layer nano-bands (Fig. 2a and 3) and sheets (Fig. 1 and Fig. 2b), which can be differentiated by optical microscopy (Fig. 1, 5 and 6), scanning electron microscopy (Fig. 2), atomic force microscopy (Fig. 3), Raman spectroscopy (Fig. 4) and electrical characterization (curves IV, Fig. 11). These results confirm that the formation of graphene nano-bands and sheets depends on the number of friction cycles.


    Example 2. Influence of the pressure applied on the formation of graphene nano-bands obtained by the process of the present invention
    In Fig. 5 it is shown that the appearance of monolayer graphene nano-bands and few layers (<5) on the silicon wafers depends on the pressure applied during friction. In the case of small pressures applied manually (approx. 200 Pa) mainly graphite points and a few graphene nano-bands are obtained on the silicon wafer (Fig. 5 a). By increasing the applied pressure (approx. 3 kPa) and for the same number of friction cycles, the amount of graphite points decreases and graphene nano-bands are formed mainly on the silicon wafer (Fig. 5b). These results confirm that the number (density) of the nanobands depends on the pressure applied. Therefore, the number of graphene nanobands depends on both the number of friction cycles and the pressure applied to the friction.
    Example 3. Influence of friction cycles and pressure applied on the formation of boron nitride nano-bands obtained by the process of the present invention
    At least 200 ng (200ng / 100mm2 = 2 ng / mm2) of hexagonal boron nitride powder (crystalline domain size = 184nm, commercial Goodfellow quality) are placed between two silicon wafers (10 mm side (surface = 100 mm2), roughness roughly = 0.5 nm in 15 microns; hardness on the Mohs scale = 7) with a silicon dioxide layer with a thickness of less than 5nm and 1000 friction cycles are performed manually. Fig. 7 shows that boron nitride nano-bands, both monolayer and a few layers, are formed on the silicon wafer. These single-layer boron nitride nano-bands (monolayer), few layers (between 2 and 4 layers) or multilayer can be differentiated by optical microscopy (Fig. 7) and Raman spectroscopy (Fig. 9). The characteristics of boron nitride nano-bands depends, as with graphene nano-bands, on the pressure applied and the number of friction cycles. Therefore, these results confirm that this technology is universal and allows to obtain nano-bands and sheets of graphene, boron nitride and any other two-dimensional material.
    Example 4. Formation of nano-bands of different two-dimensional atomic materials in the same silicon wafer obtained by the process of the present invention

    Method 1
    At least 200 ng (2 ng / mm2) of hexagonal boron nitride powder (crystalline domain size = 184nm, commercial Goodfellow quality) is placed between two silicon wafers (10mm side (surface = 100 mm2), roughness rough = 0.5 nm in 15 microns; hardness on the Mohs scale = 7) with a silicon dioxide layer with a thickness of less than 5 nm and 1000 friction cycles are performed manually. After the formation of these boron nitride nanobands, the friction cycles are stopped and 200 ng (2 ng / mm2) (or more) of graphite powder (obtained by milling the Merck commercial product; crystalline domain size) is placed = 19.5nm) on the silicon wafer containing the boron nitride nano-bands. The manual friction process is continued (800 cycles). As a result, both boron nitride and graphene nano-bands are obtained on the same silicon wafer (Fig. 8). In Fig. 8 the graphene and boron nitride nano-bands are shown on a silicon wafer (pressure applied with the fingers, approximately 200 Pa). The number of concentric friction cycles is 1000 for boron nitride and 800 for graphite powder.
    Method 2
    A 50% homogeneous mixture of hexagonal boron nitride powder (Goodfellow commercial quality; crystalline domain size = 184 nm) and graphite powder (obtained by milling the Merck commercial product; crystalline domain size = 19.5 is made nm). This mixture is placed between two silicon wafers (roughness = 0.5 nm in 15 microns; hardness on the Mohs scale = 7) with a layer of silicon dioxide with thickness less than 5 nm and 800 friction cycles are performed manually . As a result, nano-bands of boron nitride and graphene are obtained together (Figure 13). Figure 13 shows graphene and boron nitride nano-bands on a silicon wafer. The number of friction cycles is 800. Friction is performed in a 50% mixture of hexagonal boron nitride powder and graphite powder. These results confirm that the methodology proposed in the present invention allows to obtain nano-bands of different two-dimensional atomic materials in the same substrate.
    Example 5. Formation of heterostructures and supernets of different 2D atomic materials obtained by the process of the present invention
    After obtaining graphene nano-bands and the subsequent friction of hexagonal boron nitride powder on the same silicon wafer by the process herein


    In this invention, the formation of mixed graphene / boron nitride nanostructures is observed in the crossing areas between graphene and boron nitride nano-bands (Figures 8 and 13). Therefore, it is clear that by continuously repeating the friction process with powders of different two-dimensional atomic materials,
    5 heterostructures in the crossing areas between nano-bands. It is possible to obtain sheets of different two-dimensional atomic materials on a graphene sheet (Figure 1) by subsequent friction with other pulverulent materials, forming two-dimensional atomic material surfaces consisting of several sheets of graphene, boron nitride or other atomic materials
    10 two-dimensional.
    Example 6. Transfer of nano-bands of 2D atomic materials obtained by the process of the present invention from one substrate to another.
    The nano-bands obtained on silicon wafers can be removed from the wafer by using adhesive tape (heat). To do this, the adhesive tape sticks on the wafer surface
    15 silicon containing nano-bands and removed from the surface. During this process, the nano-bands stick to the adhesive tape. After the adhesive tape is glued on the clean surface of another silicon wafer, it is observed that graphene nano-bands are transferred to this second silicon wafer. Fig. 10 shows monolayer graphene nano-bands transferred from the
    20 silicon wafer surface to another clean surface (silicon or other material) by using adhesive tape. These results confirm that it is possible to transfer nano-bands of graphene or other two-dimensional atomic material obtained by the process described in this invention from a silicon surface to another substrate by the use of adhesive tape.
    Example 7. Procedure using substrates of different material: silicon and mica At least 200 ng (2 ng / mm2) of graphite powder (crystalline domain size = 19.5 nm, obtained by a grinding process) or powder are placed of crystalline domain size = 47.1 nm (Merck commercial quality)) between 1 silicon wafer (average roughness of 0.5 nm at 15 microns and hardness 7 on the Mohs scale) and a mica disk (Muscovite grade V1, 9.5 mm
    30 diameter and hardness 2.8 on the Mohs scale). The silicon wafer has a silicon dioxide layer of less than 5nm.


    Therefore, the dust concentration per unit area is 200ng / 100mm2 = 2 ng / mm2. Friction is performed manually concentrically with different friction cycles: 250, 400, 500 (Fig. 13), 800, 1000. In Figure 13 you can see strips of graphene monolayer and few layers (between 2
    5 and 4 layers), as well as some multilayer strip. Multilayer strips are eliminated by increasing the number of friction cycles.

    权利要求:
    Claims (14)
    [1]
    1. Procedure for obtaining a sheet of graphene, boron nitride, molybdenum disulfide, tungsten disulfide or a sheet of mixtures thereof; wherein said sheet is formed by a set of strips, where said strips consist of one to five
    5 layers of graphene, boron nitride, molybdenum disulfide or tungsten disulfide, where said layers have a monoatomic or monomolecular thickness, and where said process comprises:
    a) placing powder of at least one multilayer material selected from the group consisting of graphite, boron nitride, molybdenum disulfide and tungsten disulfide, between two
    10 solid substrates, and
    b) frictioning the surfaces of said substrates between them and with said powder, said powder being located between them,
    to form said sheet on the surface of at least one of the solid substrates.
    Method according to claim 1 further comprising a step c) comprising removing the sheet obtained after step b) on the surface of the at least one of the solid substrates on which said sheet has been formed.
    [3]
    3. Procedure for coating a substrate with a sheet of graphene, boron nitride, molybdenum disulfide, tungsten disulfide or a sheet of mixtures of
    20 themselves; wherein said sheet is formed by a set of strips, where said strips consist of one to five layers of graphene, boron nitride, molybdenum disulfide
    or of tungsten disulfide, where said layers have a monoatomic or monomolecular thickness, and where said process comprises:
    a) place dust of at least one multilayer material selected from the group consisting of
    25 in graphite, boron nitride, molybdenum disulfide and tungsten disulfide, between two solid substrates, at least one of them being the substrate whose surface is to be coated, and
    b) frictioning the surfaces of said substrates between them and with said powder, said powder being located between them,

    to form the sheet on the surface of the solid substrate to be coated.
    [4]
    Four. Method according to any of the preceding claims wherein at least one of the solid substrates has a roughness of between 0.2 nm and 2 nm.
    [5]
    5. Method according to any of the preceding claims wherein the two
    5 solid substrates between which the powder of multilayer material is placed are of the same material or are of different material.
    [6]
    6. Method according to any of the preceding claims wherein at least one of the solid substrates has a hardness of between 4.5 and 10 on the Mohs scale.
    [7]
    7. Method according to any of the preceding claims wherein at least one of 10 solid substrates is a material selected from the group consisting of:
    a) inorganic materials, selected from the group consisting of
    (i)  semiconductor materials,
    (ii)  dielectric materials; Y
    (iii) metals; or
    15 b) other materials selected from the group consisting of plastic, paper and wood.
    [8]
    8. Process according to claim 7 wherein the solid substrate is a semiconductor material selected from the group consisting of silicon and silicon carbide.
    [9]
    9. Process according to claim 7 wherein the solid substrate on which the
    20 sheet is an inorganic metal material selected from the group consisting of cobalt, copper, silver, gold, iron, platinum and palladium.
    [10]
    10. Method according to any of the preceding claims wherein the strips and / or layers are between 5 nm and 50 μm wide.
    [11]
    11. Method according to any of the preceding claims wherein the powder of multilayer material has an average particle size between 5 nm and 50 μm.

    [12]
    12. Method according to any of the preceding claims wherein the graphene sheet is formed by a web of strips, wherein said strips in turn comprise one, two, three, four or five layers of graphene monoatomic thickness.
    [13]
    13. Method according to any of the preceding claims wherein the powder of multilayer material is graphite powder.
    [14]
    14. Process according to any of claims 1-11 wherein the multilayer material powder is a powder mixture of at least two materials selected from the group consisting of graphite, boron nitride, molybdenum disulfide and tungsten disulfide.
    [15]
    fifteen. Method according to any of the preceding claims where they are used
    10 between 0.25 and 5 nanograms of powder per mm2 of surface area of the substrate on which a sheet is to be formed.

    DRAWINGS
    Fig. 1
    Fig. 2

     Fig. 3
    28

    Fig. 4
    Fig. 5

    Fig. 6
    Fig. 7

    Fig. 8
    Fig. 9

    Fig. 10
    Fig. 11

    Fig. 12

    Fig. 13
    Fig. 14
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    同族专利:
    公开号 | 公开日
    WO2016107942A1|2016-07-07|
    ES2575711B2|2016-11-03|
    US10968104B2|2021-04-06|
    EP3246286A1|2017-11-22|
    US20190152783A1|2019-05-23|
    EP3246286A4|2018-12-12|
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    TWI517774B|2011-02-09|2016-01-11|創業發展聯盟技術有限公司|Method of producing multilayer graphene-laminated substrate|
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    US20140205796A1|2013-01-18|2014-07-24|International Business Machines Corporation|Method of forming graphene nanomesh|
    US11103837B1|2013-03-15|2021-08-31|The Government Of The United States Of America, As Represented By The Secretary Of The Navy|Nanoporous graphene membranes|CN106475573B|2016-11-01|2018-05-04|河北大学|A kind of preparation and application using graphene as the monatomic two-dimensional material of the metal of substrate|
    GB2589356A|2019-11-28|2021-06-02|Univ Exeter|Van der Waals heterostructures|
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