• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Method of obtaining a graphene functionalized covalently with an organic molecule. The present invention relates to a process for obtaining a graphene functionalized covalently with an organic molecule. The process comprises a first step of forming defects/monatomic vacancies in the crystalline network of graphene which is carried out by gentle bombardment of noble gas ions under ultra high vacuum conditions, and a second step of exposing said surface of graphene a high partial pressure of organic molecule. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2654941A1
    申请号:ES201630971
    申请日:2016-07-15
    公开日:2018-02-15
    发明作者:Rebeca ACEITUNO BUENO；José Ignacio MARTÍNEZ RUIZ；Roberto Fabián LUCCAS；María Francisca LÓPEZ FAGÚNDEZ；Federico MOMPEÁN GARCÍA；Mª Del Mar GARCÍA HERNÁNDEZ；José Ángel MARTÍN GAGO
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    Procedure for obtaining a graphene functionalized covalently with
    an organic molecule
    DESCRIPTION
    The present invention relates to a process for obtaining a graphene functionalized covalently with an organic molecule. The process comprises a first stage of defect / vacancy formation in the crystalline graphene network which is carried out by gentle bombardment of noble gas ions under ultra-high vacuum conditions, and a second stage of exposing said graphene surface at an organic molecule pressure.
    Therefore, we understand that the present invention is within the sector of the electronic and chemical industry, particularly the industry dedicated to the manufacture of electronic devices and sensors.
    STATE OF THE TECHNIQUE
    In recent years, graphene has emerged as a technological revolution by presenting, among others, spectacular conduction and electron transport properties. Among the many properties that characterize it, its chemical inertia stands out, which gives graphene great stability and prevents contaminating molecules from sticking to its surface. However, that graphene has great chemical inertia makes the functionalization of its surface a task of high difficulty.
    It is especially important to become able to functionalize the surface of graphene with certain molecules either to manipulate the electronic properties of graphene or to use said molecules bound to its surface as connectors to couple other molecules with a defined mission, since said Graphene surface functionalization would expand its use in fields such as semiconductor engineering, magnetic materials with an interest in spintronics and the dielectric industry, and materials engineering such as nano-bio-composites with an interest in the variation of their properties plasmonic optics. Particularly, a functionalization of the graphene surface keeping its conduction and electron transport properties intact would increase the
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    technological perspectives of graphene, especially in applications in the field of electronics. Graphene functionalization is expected to be an important step in the development of graphene-based materials with custom electronic properties.
    DESCRIPTION OF THE INVENTION
    The present invention relates to a process for covalently functionalizing the surface of a graphene with an organic molecule. The incorporation of organic molecules on the surface of a graphene allows the electronic and optical properties of graphene to be modulated efficiently and in a controlled manner. The process comprises a first stage of defect / vacancy formation in the crystalline network of a graphene which is carried out by gentle bombardment of noble gas ions under ultra-high vacuum conditions, and a next stage of exposure of said surface of graphene with an organic molecule.
    In the first stage of the process, a density of monoatomic defects / vacancies is created in the crystalline network of a graphene and, in a next stage of the process, organic molecules containing at least one amino group, such as p-aminophenol, they are adsorbed on the surface of said graphene, being bound only those molecules that penetrate the defects of the graphene crystal lattice. Specifically, the organic molecules are covalently anchored to the graphene surface by incorporating the N of the amino group into the vacancies / defects of the graphene crystal lattice. After said functionalization, the conductive properties of the starting crystalline graphene remain intact.
    In a first aspect, the present invention relates to a method of obtaining a functionalized graphene covalent with an organic molecule (from here the process of the invention) comprising the following steps:
    a) bombard the surface of a graphene system and a non-metallic substrate with a beam of noble gas ions at a pressure between 1-10'7 mbar and 1-10'8 mbar for a period of time between 30 s and 120 s,
    where the system formed by graphene and a non-metallic substrate is inside a chamber at an initial pressure less than 1-10'9 mbar,
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    where the energy of the noble gas ions is between 100 eV and 140 eV, and
    b) optionally heat treating the system obtained in step (a) at a temperature between 450 ° C and 550 ° C for a period of between 5 min and 10 min,
    (c) subject the graphene surface of stage (a) or stage (b) to an organic molecule exposure greater than 10 Langmuir,
    In the present invention, "graphene" is understood as that graphene obtained by any of the different current methods of graphene growth such as epitaxial growth in vapor phase (VPE), in liquid phase (LPE), by molecular beams (MBE) or by Metalorganic chemistry by vapor deposition (MOCVD).
    In step (a) of the process, the surface of a system formed by a graphene and a non-metallic substrate is bombarded, that is, the graphene that is covering a non-metallic substrate is bombarded. Among the possible substrates, non-metallic ones are chosen to avoid screening the graphene transport properties.
    In the present invention graphene has been grown on a non-metallic substrate or transferred to a non-metallic substrate. For example, graphene could be grown on a metallic substrate and then transferred to a non-metallic substrate.
    Preferably, the graphene of step (a) is a single layer of graphene (from the English "Single Layer Graphene SLG") which has been obtained by chemical vapor deposition (CVD of the "Chemical Vapor Deposition") on a non-metallic substrate according to Strupinski, W. et al. “Graphene Epitaxy by Chemical Vapor Deposition on SiC.” Nano Lett. 11, 1786-1791 (2011)]
    Preferably, the graphene of step (a) is almost self-supporting / independent graphene (from "quasi free standing QFS-graphene") obtained by interleaving H under the carbon layer (in English "buffer layer") according to Tokarczyk et al. . "Structural investigations of hydrogenated epitaxial graphene grown on 4H-SiC (0001)." Appl. Phys. Lett. 103, 241915 (2013).
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    In the present invention, "noble gas ion beam" means that beam formed by noble gas ions produced by an ion source, selecting the source (gas) and energy of these ions. The noble gases that are considered in The present invention are helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe).
    The process of the invention begins with (a) the bombardment of the surface of a system formed by epitaxial graphene and a nonmetallic substrate with a beam of noble gas ions at a pressure between 1-10 "7 mbar and 1-10 "8 mbar for a period of time between 30 s and 120 s. For this, a graphene system obtained by epitaxial growth on a non-metallic substrate is prepared or prepared and introduced into a chamber that is under ultra-high vacuum conditions, at a pressure less than 1-10 "9 mbar.
    The distance from the source of the noble gas ion beam to the graphene surface depends on the dimensions of the equipment used to carry out the procedure. In a preferred embodiment of the process of the invention, the distance from the source of the beam of said noble gas ions to the graphene surface is between 5 cm and 25 cm. More preferably, the distance is between 8 cm and 15 cm.
    As we have mentioned before, graphene is grown on a non-metallic substrate so as not to screen the transport properties of graphene, preferably the non-metallic substrate is selected from SiC, hBN, MoS2, TiO2 and SiO2.
    On the other hand, step (a), that is, the bombardment of the graphene surface with a beam of noble gas ions, is carried out with the system formed by a graphene and a non-metallic substrate under ultra-high conditions. vacuum, so that said system is inside a vacuum chamber. It is a soft bombardment, that is, the energy of noble gas ions is between 100 eV and 140 eV.
    In a preferred embodiment of the present invention, the noble gas beam of step (a) is argon at a pressure of 1-10 "7 mbar.
    The soft bombardment with noble gas ions of the graphene surface of step (a) induces the formation of defects / vacancies in the graphene crystal lattice; the formation of said graphene is activated for, in a next stage, in the stage
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    (c) of the procedure, covalently anchor organic molecules to the graphene surface.
    During the step (a) of the procedure, the formation of the aforementioned defects can be monitored by measuring the electric current produced in the system formed by a graphene and a non-metallic substrate. In the present invention, the bombardment of step (a) is smooth, the electric current measured in the system is between 1 pA and 2 pA.
    In the present invention, "organic molecule" means any molecule of organic origin that contains at least one amino group in its structure.
    Specifically, with step (a) of the process it is intended to anchor the organic molecules containing at least one amino group to the graphene surface. Anchoring occurs through an N of the amino group in the defects / vacancies that have formed in the graphene crystal lattice.
    Preferably, the organic molecule is selected from p-aminophenol, aminothiophenol and aminobenzoic acid. Note, for example, that p-aminophenol binds to the graphene surface through its amino group and not through its phenol group.
    In step (b) of the process of the invention the system obtained in step (a) is optionally treated thermally at a temperature between 450 ° C and 550 ° C for a period of between 5 min and 10 min, in order of degassing possible remains of noble gas from stage (a) on the graphene surface.
    In step (c) of the process, the surface of the system formed by a graphene and a non-metallic substrate obtained in step (a) or in step (b) of the process, is subjected to an exposure of organic molecules greater than 10 L (Langmuir units), defined below.
    Langmuir is a unit of exposure of a surface and is commonly used in surface physical systems that operate in ultra high vacuum, to define the adsorption of gases from that surface. The Langmuir unit is defined by multiplying the gas pressure by the exposure time. A Langmuir corresponds to an exposure of 10-6 torr (1 torr = 1.33322 mbar) for one second. For example, exposing a surface to a gas pressure of 10-8 torr for 100 seconds is
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    corresponds to 1 L. Another example would be to maintain an oxygen pressure of 2.5 10 "6 torr for 40 seconds resulting in an exposure of 100 L.
    Therefore, in step (c) of the process, the surface of the system formed by a graphene and a non-metallic substrate obtained in step (a) or in step (b) of the process, is subjected to an exposure of organic molecules greater than 10 L (Langmuir units), where 1 L is the product of the multiplication of the pressure of a gas (1.33322-10 "6 mbar) by the exposure time (1s).
    In step (c) of the process the system formed by graphene and a non-metallic substrate, obtained in step (a) or in step (b) of the process, is at room temperature.
    In a preferred embodiment, the process of the invention comprises the following steps:
    a) bombard the surface of a graphene-formed system and a non-metallic substrate with a beam of noble gas ions at a pressure between 1-10 "7 mbar and 1-10" 8 mbar for a period of time between 30 s and 120 s,
    where the system is inside a chamber at an initial pressure at a pressure less than 1-10 "9 mbar,
    where the energy of noble gas ions is between 100 eV and 140 eV,
    b) heat treat the system obtained in step (a) at a temperature between 450 ° C and 550 ° C for a period of between 5 min and 10 min, and
    c) subject the graphene surface bombed from step (b) to an exposure of an organic molecule greater than 10 Langmuir.
    In another preferred embodiment of the process of the present invention, the graphene surface of step (a) has previously been heat treated to degassing possible contaminants that were fisisorbed on said surface. The heat treatment is carried out at a temperature between 200 ° C and 350 ° C for a period of between 10 min and 30 min.
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    Graphene covalently functionalized with an organic molecule that contains at least one amino group has its application in the electronics industry sector, particularly in the industry dedicated to the manufacture of electronic sensors and devices.
    The fact that the conductive properties of graphene remain unchanged after treatment is of special relevance, since the high mobility of carriers at room temperature is of special interest for use as transistors.
    On the other hand, the field effects and the quantum Hall effects of the covalently functionalized graphene of the present invention are important because the carriers travel long distances without colliding with the atoms so that said graphene can be used as part of a spintronic device.
    Finally, the good conductivity and stability of the covalently functionalized graphene of the invention is critical for applications such as electrodes for supercapacitors, and other devices aimed at energy storage. The incorporation of organic molecules on the graphene surface allows the electronic and optical properties of graphene to be modulated efficiently and in a controlled manner.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1 Images of the system surface formed by a graphene and a non-metallic substrate after degassing obtained with a tunnel effect microscope (STM) at two different sizes (see scale of 2 nm (a) and 10 nm (b)).
    FIG. 2 Spectrum obtained by X-ray photoelectronic spectroscopy (XPS) of the graphene sample on SiC after preliminary cleaning performed to degasify and clean the surface.
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    FIG. 3 XPS spectrum of system 1 (a) and system 2 (b).
    FIG. 4 STM images of the defects / vacancies produced in the system after the bombardment with Ar ions to two different sizes (see scale of 2 nm (a) and 3 nm (b)).
    FIG. 5 STM images of defects / vacancies produced in the system after bombardment with Ar ions.
    FIG. 6 STM images of system 1 at three different sizes (see scale of 3 nm (a), 6 nm (b) and 10 nm (c)).
    EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention.
    The graphene system on SiC has been prepared by chemical vapor deposition on a SiC substrate and is inside a chamber with a pressure less than 1-10 "9 mbar.
    First, the surface of the system formed by graphene on SiC is cleaned by degassing the surface of said sample by means of a heat treatment at 300 ° C for 15 min. During preliminary degassing, the pressure inside the vacuum chamber rises considerably indicating that contaminants that were adsorbed on the surface have been desorbed.
    Figure 1 shows the images obtained with a tunneling microscope (in English "scanning tunneling microscope" or STM) at two different sizes (2 nm and 10 nm) corresponding to the system surface after the previous degassing of the surface. These STM images indicate that the surface is clean, concluding that the desorption of pollutants has been carried out correctly.
    Figure 2 shows the spectrum obtained by X-ray photoelectronic spectroscopy (in English "X-ray Photoelectron Spectroscopy") obtained for this system before the bombing, that is, for the graphene surface on degassed SiC. This spectrum indicates that there is no presence of nitrogen on the surface.
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    System 1 is prepared by bombarding with Ar ions using 110-7 mbar and exposing the surface to a flow of p-aminophenol at 10L. Figure 3a shows the XPS spectrum for the graphene surface of system 1, where the presence of nitrogen (N) is observed.
    System 2 corresponds to a system whose surface has been exposed to a flow of p-aminophenol but has not been previously activated by bombardment with Ar ions. Figure 3b shows the XPS spectrum corresponding to this system. This spectrum shows that, when trying to functionalize the graphene surface of system 2, that is, without having carried out the bombardment with Ar ions, p-aminophenol does not anchor to the surface of said graphene.
    The images obtained with a tunnel effect microscope shown in Figure 4, at two different sizes (2 nm and 3 nm), correspond to the surface of system 1 and show the formation of defects / vacancies on the surface thereof. Figure 5 shows the peculiar shape of the vacancies / defects presenting an appearance of 3-axis irradiation, typical of these defects.
    Figure 6 shows the STM images obtained for the system 1 at three different sizes (3 nm, 6 nm and 10 nm). It is observed how the appearance of the structures on the surface is different from the images of figures 4 and 5. The The height of the nanostructures observed are larger, indicating the anchoring of the p-aminophenol molecule on the graphene surface.
    权利要求:
    Claims (8)
    [1]
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    1. A method of obtaining a functionalized graphene covalent with an organic molecule comprising the following steps:
    a) bombard the surface of a graphene system and a non-metallic substrate, with a beam of noble gas ions at a pressure of between 110-7 mbar and 110-8 mbar for a period of time between 30 s and 120 s ,
    where the system is inside a chamber at an initial pressure of less than 110-9 mbar,
    where the energy of noble gas ions is between 100 eV and 140 eV,
    b) optionally heat treating the system obtained in step (a) at a temperature between 450 ° C and 550 ° C for a period of between 5 min and 10 min, and
    c) subject the graphene surface of stage (a) or stage (b) to an organic molecule exposure greater than 10 Langmuir.
    [2]
    2. The method according to claim 1, wherein, in step (a), the distance from the source of the beam of said noble gas ions to the graphene surface is between 5 cm and 25 cm.
    [3]
    3. The method according to claim 2, wherein, in step (a), the distance from the source of the beam of said noble gas ions to the graphene surface is between 8 cm and 15 cm.
    [4]
    4. The method according to any of claims 1 to 3, wherein the nonmetallic substrate is selected from SiC, hBN, MoS2, TiO2 and SiO2.
    [5]
    5. The method according to any of claims 1 to 4, wherein the noble gas beam of step (a) is argon at a pressure of 110-7 mbar.
    [6]
    6. The process according to any one of claims 1 to 5, wherein the organic molecule of step (c) is selected from p-aminophenol, aminothiophenol and aminobenzoic acid.
    [7]
    7. The method according to any of claims 1 to 6, comprising the following steps:
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    a) bombard the surface of a graphene-formed system and a non-metallic substrate with a beam of noble gas ions at a pressure between 110-7 mbar and 110-8 mbar for a period of time between 30 s and 120 s,
    where the system is inside a chamber at an initial pressure of less than 1 • 10-9 mbar,
    where the energy of noble gas ions is between 100 eV and 140 eV,
    b) heat treat the system obtained in step (a) at a temperature between 450 ° C and 550 ° C for a period of between 5 min and 10 min, and
    c) subject the graphene surface bombed from step (b) to an exposure of an organic molecule greater than 10 Langmuir.
    [8]
    8. The method according to any of claims 1 to 7, wherein the graphene surface of step (a) has previously been heat treated at a temperature between 200 ° C and 350 ° C for a period of between 10 min and 30 min.
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    同族专利:
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    EP3486214A1|2019-05-22|
    ES2654941B1|2018-11-21|
    EP3486214B1|2021-03-31|
    ES2870651T3|2021-10-27|
    WO2018011453A1|2018-01-18|
    PL3486214T3|2021-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2005050757A2|2002-12-09|2005-06-02|Rensselaer Polytechnic Institute|Nanotube-organic photoelectric conversion devices and methods of making same|CN110681860B|2019-09-09|2020-12-22|厦门大学|Graphene oxide coated metal composite nano with Raman signal and preparation method and application thereof|
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    ES201630971A|ES2654941B1|2016-07-15|2016-07-15|PROCEDURE FOR OBTAINING A FUNCTIONALIZED GRAPHENE COVALENTLY WITH AN ORGANIC MOLECULE|ES201630971A| ES2654941B1|2016-07-15|2016-07-15|PROCEDURE FOR OBTAINING A FUNCTIONALIZED GRAPHENE COVALENTLY WITH AN ORGANIC MOLECULE|
    PCT/ES2017/070518| WO2018011453A1|2016-07-15|2017-07-17|Method for obtaining a graphene covalently functionalised with an organic molecule|
    PL17827054T| PL3486214T3|2016-07-15|2017-07-17|Method for obtaining a graphene covalently functionalised with an organic molecule|
    EP17827054.2A| EP3486214B1|2016-07-15|2017-07-17|Method for obtaining a graphene covalently functionalised with an organic molecule|
    ES17827054T| ES2870651T3|2016-07-15|2017-07-17|Procedure for obtaining a covalent functionalized graphene with an organic molecule|
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