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Surface-Modified Carbon Material, and Method for Producing Surface-Modified Carbon Material

外国特許コード F210010534
整理番号 K10514WO
掲載日 2021年8月2日
出願国 アメリカ合衆国
出願番号 201916976514
公報番号 20210070616
出願日 平成31年2月28日(2019.2.28)
公報発行日 令和3年3月11日(2021.3.11)
国際出願番号 JP2019010720
国際公開番号 WO2019168206
国際出願日 平成31年2月28日(2019.2.28)
国際公開日 令和元年9月6日(2019.9.6)
優先権データ
  • 特願2018-036704 (2018.3.1) JP
  • 2019JP10720 (2019.2.28) WO
発明の名称 (英語) Surface-Modified Carbon Material, and Method for Producing Surface-Modified Carbon Material
発明の概要(英語) The present invention is a surface-modified carbon material including chemical addends added to the surface of graphene, such that a one-dimensional periodicity corresponding to a large number of addition positions of the chemical addends can be observed in a Fourier-transformed image of a scanning probe microscopic image of the surface of graphene. The surface-modified carbon material of the present invention has a bandgap and therefore can be used as a sensor capable of electronically controlling an operation or another electronic device.
従来技術、競合技術の概要(英語) BACKGROUND ART
Graphene in which sp2 carbons are arranged in a honeycomb shape is expected to be used in various applications because of its excellent electrical properties, mechanical properties, optical properties, and thermal properties. Graphene is considered to be utilized in the electronic field because of its high conductivity. Therefore, graphene related researches thrive in universities, research institutions, and companies and the like.
Graphene is a substance exhibiting a semi-metallic property, and is a zero bandgap semiconductor. Therefore, the application of graphene as it is as an electronic material is limited. However, if a bandgap can be appropriately introduced into graphene, graphene can be utilized for a high-performance field-effect transistor which operates at high speed at room temperature, and a small and highly sensitive molecular sensor.
Therefore, many methods for introducing the bandgap into graphene have been reported. Examples thereof include doping of electrons or holes into graphene from a supporting substrate, lithography processing of graphene with light or ion plasma, microfabrication with an SPM probe, and introduction of defects (spa carbon) by chemical modification using active chemical species.
Among these methods, the chemical modification of graphene has an advantage that the introduction of the bandgap into graphene as well as the electronic or chemical properties of organic groups added to graphene make it possible to control a Fermi level and a surface property. Therefore, the chemical modification of graphene has been actively studied.
It is known that, in the chemical modification of graphene or the like, an edge portion is more likely to be chemically modified than an in-surface portion is chemically modified. In the chemical modification of graphene, it is important to control the addition positions of a large number of active chemical species in the in-surface portion of graphene to maintain a predetermined order property. This is because the in-surface portion can be chemically modified while the predetermined order property is maintained, which preferably provides an advantage that a carrier movement way, that is, control of a current can be realized.
First, International Publication No. WO 2007/118976 discloses an invention relating to a method for bringing a fluid into contact with a substrate. In this invention, on the surface of the fluid brought into contact with the substrate, an organic molecular network having a central part and at least one lateral arm is formed. A two-dimensional molecular sieve formed by adsorbing network molecules onto the surface of silicon, metal, or pyrolytic graphite (HOPG) or the like is disclosed. FIG. 13 shows a two-dimensional structure 100 formed by continuously interacting an organic compound basic framework 105a and an organic compound grafted part 105b with each other on planar alignment of 6-membered rings 102 of a carbon material.
Next, FIG. 14(a) is a schematic cross-sectional view of a related art associated with Japanese Patent Document JP 2009-61725 A. The related art associated with Japanese Patent Document JP 2009-61725 A is an invention in which a modified carbonaceous film is formed on the surface of a substrate 113 made of stainless steel, ceramic, or resin or the like. That is, in Japanese Patent Document JP 2009-61725 A, a modified carbonaceous film 110 is disclosed, which has a carbonaceous film containing sp2-bonded carbon and spa-bonded carbon and a functional group containing hydrogen atoms and oxygen atoms on the surface of the carbonaceous film (planar alignment of 6-membered rings 112), and includes an organic component (graft chain 111) chemically bonded to the surface of the carbonaceous film.
FIG. 14(b) schematically shows a related art associated with Japanese Patent Document JP 2012-247189 A. An electronic device 120 has a structure in which an edge-modified graphene film (planar alignment of 6-membered rings 122) on a substrate is used as a channel, and a source electrode 124 and a drain electrode 125 are electrically joined to the channel. In this electronic device 120, a functional group 121 which adsorbs or binds to detected substance species is added to the edge of the graphene film to constitute an edge-modified graphene sensor. A method for chemically modifying not the edge of a carbon material such as graphene but the surface of planar alignment of 6-membered rings also has been attempted for a large number of chemical addends. FIG. 14(c) is a photograph showing a method for randomly and chemically modifying the surface of graphite, and then mechanically removing chemical addends with an STM probe to expose the surface of carbon in a desired shape. This method is called a nanoshaving method.
FIG. 15 schematically shows a condition in which NBD as chemical addends is added to the surface of a carbon material. In this case, a multi-layered state is formed by cascading an aryl radical substitution reaction to an aryl group added to the planar alignment of 6-membered rings on the surface of the carbon material. As a result, high density modification and addition position control in the plane of a large number of chemical addends on the carbon material have not been achieved.
Thus, in the conventional method, the addition of the active chemical species to graphene randomly occurs, which makes it virtually impossible to control the addition position (spa carbon position), particularly, in the surface. It was also difficult to strictly control the modification rate of adducts. Some studies have been reported for solving such problems.
For example, Non-Patent Literature 1: Navarro, J.; Leret, S.; Calleja, F.; Stradi, D.; Black, A.; Bernardo-Gavito, R.; Garnica, M.; Granados, D.; Vazquez de Parga, A. L.; Perez, E. M.; Miranda, R., Organic Covalent Patterning of Nanostructured Graphene with Selectivity at the Atomic Level. Nano Lett. 2016, 16, 355361 (Navarro et. al.), reports that cyanomethyl radicals are regioselectively added to monolayer graphene on Ru(0001) due to an interaction between a metal and graphene. However, this method cannot control dimensionality and a period (pitch).
Non-Patent Literature 2: Xia, Z.; Leonardi, F.; Gobbi, M.; Liu, Y.; Bellani, V.; Liscio, A.; Kovtun, A.; Li, R.; Feng, X.; Orgiu, E.; Samori, P.; Treossi, E.; Palermo, V. Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts. ACS Nano 2016, 10, 7125-7134, (“Xia et. al.”), reports that aryl diazonium salts having a long-chain alkyl group are aligned on graphene by self-assembling, and electrochemically reduced to generate aryl radicals, thereby providing the addition to graphene. The possibility of periodic modification has been discussed.
The methods of Non-Patent Literature 1 (Navarro et. al.) and Non-Patent Literature 2 (Xia et. al.) are attractive approaches to the periodic chemical modification. However, both the methods are far from precise control of chemical surface modification on a carbon material. The highly accurate control of addition positions and the control of a modification rate when chemical addends are added are considered to be insufficient.
In contrast, Non-Patent Literature 3: Cai, J.; Ruffieux, P.; Jaafar, R.; Bieri, M.; Braun, T.; Blankenburg, S.; Muoth, M.; Seitsonen, A. P.; Saleh, M.; Feng, X.; Mullen, K.; Fasel, R. Atomically Precise Bottom-Up Fabrication of Graphene Nanoribbons. Nature 2010, 466, 470-473, (“Cai et. al.”), reports a method for synthesizing nanographene or graphene nanoribbon (GNR) in a bottom-up manner by utilizing a chemical reaction on a solid substrate or in a solution. This method has an advantage that graphene and GNR having an appropriate size can be obtained from a designed precursor. Therefore, research has been actively conducted on this method in recent years. However, their electronic or magnetic properties largely depend on an edge structure, and are largely different from those of graphene itself. It is also impossible to widen a ribbon width beyond a certain extent.
Meanwhile, a method for forming a nano pattern on the surface of graphite or graphene utilizing the formation of a self-assembling unimolecular film by the physical adsorption of organic molecules has been reported.
For example, Non-Patent Literature 4: Rabe, J. P.; Buchholz, S. Commensurability and Mobility in Two-Dimensional Molecular Patterns on Graphite. Science 1991, 253, 424-427, (“Rabe et. al.”), reports that linear alkanes form a lamella type unimolecular film through self-assembly at the interface between an organic solvent and graphite. However, Non-Patent Literature 4 (Rabe et. al.) does not disclose any idea of performing chemical modification while periodically controlling addition positions.
Non-Patent Literature 5: Li, B.; Tahara, K.; Adisoejoso, J.; Vanderlinden, W.; Mali, K. S.; De Gendt, S.; Tobe, Y.; De Feyter, S. Self-Assembled Air-Stable Supramolecular Porous Networks on Graphene. ACS Nano 2013, 7, 10764-10772, (“Li et. al.”), and Non-Patent Literature 6: Tahara, K.; Adisoejoso, J.; Inukai, K.; Lei, S.; Noguchi, A.; Li, B.; Vanderlinden, W.; De Feyter, S.; Tobe, Y. Harnessing by a Diacetylene Unit: a Molecular Design for Porous Two-Dimensional Network Formation at the Liquid/Solid Interface. Chem. Commun. 2014, 50, 2831-2833, (“Tahara et. al.), have reported a method for simply forming a nano pattern on the surface of graphite or graphene utilizing self-assembling unimolecular film formation provided by physical adsorption of organic molecules at a solid-liquid interface using a newly synthesized dehydrobenzo[12]annulene (DBA) derivative. STM observation confirmed that the DBA derivative forms honeycomb-shaped molecular alignment at the interface between an organic solvent and graphite or graphene.
Non-Patent Literature 7: Kazukuni Tahara, Development of Precision Graphene Chemical Modification Technique by Self-Assembly of Reactive Molecules, 95th CSJ's National Meeting holding in spring, Mar. 27, 2015, (Tahara), reports experimental results of forming a 6-fold symmetric periodic structure on graphite utilizing the above technique of Non-Patent Literature 5 (Li et. al.) or Non-Patent Literature 6 (Tahara et. al.), followed by performing chemical modification.
Non-Patent Literature 8: Fuminori Mitsuhashi, Masaya Okada, Yasunori Tateno, Masanori Ueno, Takashi Nakabayashi, Method for Producing Graphene Having Excellent Uniformity for Realizing Transistors Operated in Terahertz Band, July 2017, SEI Technical Review No. 191 53-58, (“Mitsuhashi et. al.”), reports a method for producing graphene utilizing an SiC sputter film forming method. Non-Patent Literature 9: Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric Field Effect in Atomically Thin Carbon Films. Science 2004, 306, 666-669, (“Novoselov et. al.”), reports a method for forming graphene on an SiO substrate.
In Non-Patent Literature 10: Lian, J. X.; Lherbier, A.; Wang L. J.; Charlier, J.-C.; Beljonne, D.; Olivier, Y. Electronic Structure and Charge Transport in Nanostripped Graphene. J. Phys. Chem. C 2016, 120, 20024-20032, (“Lian et. al.”), calculation prediction was attempted for a technique capable of controlling the bandgap of graphene when spa carbon defects are one-dimensional-periodically introduced into graphene.
Non-Patent Literature 11: Greenwood, J.; Phan, T. H.; Fujita, Y.; Li, Z.; Ivasenko, O.; Vanderlinden, W.; Van Gorp, H.; Frederickx, W.; Lu, G.; Tahara, K.; Tobe, Y.; Uji-i H.; Mertens, S. F. L; De Feyter, S. Covalent Modification of Graphene and Graphite Using Diazonium Chemistry: Tunable Grafting and Nanomanipulation. ACS Nano 2015, 5, 5520-5535, (“Greenwood et. al.), reports a method for adding 3,5-di-tert-butylbenzenediazonium chloride (TBD) or 4-nitrobenzenediazonium chloride (NBD) as chemical addends to the surface of graphene or graphite. In FIG. 13, a technique of exposing a carbon surface in a rectangular region by partially removing a layer of aryl groups added to the surface of a carbon material with an STM probe was shown (see FIG. 14(c)). Furthermore, a technique of forming two blocks by causing pentacontane molecules to self-assemble using the exposed rectangular region as a template was shown. In this related art, the pentacontane self-assembling on the surface of the carbon material could be observed to be aligned in several adjacent blocks, but in a larger area size, the blocks were disposed in a mosaic pattern. Thus, Non-Patent Literature 11 (Greenwood et. al.) utilized a nanoshaving method using the STM probe, and did not achieve the formation of adducts (chemical addends) in a predetermined alignment state so that the carbon material could be used in an electronic device.
Finally, Non-Patent Literature 12: Cancado, L. G.; Jorio, A.; Martins Ferreira, E. H.; Stavale, F.; Achete, C. A.; Capaz, R. B.; Moutinho, M. V. O.; Lombardo, A.; Kulmala, T. S.; Ferrari, A. C. Quantifying Defects in Graphene via Raman Spectroscopy at Different Excitation Energies. Nano Lett. 2011, 11, 3190-3196, (“Cancado et. al.”) reports that defects in graphene can be quantitatively analyzed by Raman spectra analysis of different excitation energies.
特許請求の範囲(英語) [claim1]
1. A surface-modified carbon material comprising a large number of chemical addends provided on at least a part of a surface of a carbon material selected from the group consisting of graphene, graphite, a glassy carbon film, and film-like pyrolytic carbon, wherein
a one-dimensional periodicity corresponding to a large number of addition positions of the chemical addends can be observed in a Fourier-transformed image of a scanning probe microscopic image of the surface.

[claim2]
2. The surface-modified carbon material according to claim 1, wherein a pitch corresponding to the one-dimensional periodicity is 2 to 10 nm.

[claim3]
3. The surface-modified carbon material according to claim 1, wherein the carbon material is the graphene, and Id/Ig between intensity Ig of a G band and intensity Id of a D band in Raman spectra of the surface is 0.2 to 5.0.

[claim4]
4. The surface-modified carbon material according to claim 1, wherein the carbon material is the graphite, and Id/Ig of intensity Ig of a G band and intensity Id of a D band in Raman spectra of the surface is 0.01 to 0.11.

[claim5]
5. The surface-modified carbon material according to claim 1, wherein the chemical addend is an aryl group.

[claim6]
6. The surface-modified carbon material according to claim 5, wherein the aryl group is represented by the following formula (1):
wherein: R1, R2, and R3 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group, OR, COOH, SOOH, SOONH2, NO2, COOR, SiR3, H, F, Cl, Br, I, OH, NH2, NHR, NR2, CN, CONHR, or COH (R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a halogen substitution product thereof).

[claim7]
7. An organic compound-carbon material composite comprising: a carbon material; a thin film; and a solvent, wherein: the carbon material is selected from the group consisting of graphene, graphite, a glassy carbon film, and film-like pyrolytic carbon; the thin film is composed of a periodic organic compound assembly; a surface of the carbon material is covered with the thin film; and the solvent is a non-polar organic solvent or a low-polarity organic solvent, and is disposed on the thin film.

[claim8]
8. The organic compound-carbon material composite according to claim 7, wherein the thin film includes the periodic organic compound assembly in which linear alkanes having 15 to 80 carbon atoms or linear alkane derivatives having 10 to 80 carbon atoms are disposed in parallel.

[claim9]
9. The organic compound-carbon material composite according to claim 7, wherein the periodic organic compound assembly has polygonal holes.

[claim10]
10. A method for producing a surface-modified carbon material, the method comprising: a first step of forming a thin film on a surface of a carbon material using an organic compound; and a second step of causing a chemical modification compound to react with the surface of the carbon material using the thin film as a mask, wherein:
the organic compound is a linear alkane having 15 to 80 carbon atoms or a linear alkane derivative having 10 to 80 carbon atoms;
the carbon material is selected from the group consisting of graphene, graphite, a glassy carbon film, and film-like pyrolytic carbon;
in the first step, the organic compound self-assembles on the surface of the carbon material to form a thin film which is a thin film periodic assembly exhibiting a one-dimensional periodicity; and
in the second step, the chemical modification compound is caused to react with the surface of the carbon material at a position of a gap of the periodic assembly.

[claim11]
11. The method for producing a surface-modified carbon material according to claim 10, wherein the linear alkane or the linear alkane derivative is a compound represented by the following formula (2):
wherein: X represents H, CH3, CF3, CH═CH2, C≡CH, an aryl group, F, Cl, Br, I, OH, SH, NH2, COH, or COOH; Y represents CH2, CF2, CH═CH, C≡C, a divalent atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon, O, S, NH, CO, COO, CONH, NHCO, or NHCHX; Z represents H, CH3, an aryl group, OH, SH, NH2, COH, COOH, COOX, CONH, NHCOX, or NHCHX; and n is an integer satisfying a condition in which the number of carbon atoms in the formula (2) is 15 to 80 in the alkane, and 10 to 80 in the alkane derivative.

[claim12]
12. The method for producing a surface-modified carbon material according to claim 10, wherein the thin film is a lamella type unimolecular film.

[claim13]
13. The method for producing a surface-modified carbon material according to claim 10, wherein the chemical modification compound is a compound represented by the following formula (3):
wherein: R1, R2, and R3 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group, OR, COOH, SOOH, SOONH2, NO2, COOR, SiR3, H, F, Cl, Br, I, OH, NH2, NHR, CN, CONHR, or COH (R is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group); and Z is a halogen atom, BF4, BR4, or PF6 (R4 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a halogen substitution product thereof).

[claim14]
14. A method for producing a surface-modified carbon material, the surface-modified carbon material produced by causing a chemical modification compound to electrochemically react with a carbon material using an electrochemical cell including a working electrode, a counter electrode, a reference electrode, and an electrolyte aqueous solution, wherein:
the carbon material is used as the working electrode;
the carbon material is selected from the group consisting of graphene, graphite, a glassy carbon film, and film-like pyrolytic carbon;
an aqueous solution containing the chemical modification compound is used as the electrolyte aqueous solution;
a liquid medium containing a compound exhibiting a periodic self-assembling property is disposed between the working electrode and the electrolyte aqueous solution; and
the electrolyte aqueous solution and the liquid medium are immiscible with each other.

[claim15]
15. The method for producing a surface-modified carbon material according to claim 14, wherein the compound exhibiting a periodic self-assembling property is a linear alkane having 15 to 80 carbon atoms or a linear alkane derivative having 10 to 80 carbon atoms.

[claim16]
16. The method for producing a surface-modified carbon material according to claim 15, wherein the linear alkane or the linear alkane derivative is a compound represented by the following formula (2):
wherein: X represents H, CH3, CF3, CH═CH2, C≡CH, an aryl group, F, Cl, Br, I, OH, SH, NH2, COH, or COOH; Y represents CH2, CF2, CH═CH, a divalent atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon, O, S, NH, CO, COO, CONH, NHCO, or NHCHX; Z represents H, CH3, an aryl group, OH, SH, NH2, COH, COOH, COOX, CONH, NHCOX, or NHCHX; and n is an integer satisfying a condition in which the number of carbon atoms in the formula (2) is 15 to 80 in the alkane, and 10 to 80 in the alkane derivative.

[claim17]
17. The method for producing a surface-modified carbon material according to claim 15, wherein a concentration of the alkane or linear alkane derivative in the liquid medium is 1 μmol/L or more.

[claim18]
18. The method for producing a surface-modified carbon material according to claim 14, wherein the compound exhibiting a periodic self-assembling property is a dehydrobenzo[12]annulene derivative.

[claim19]
19. The method for producing a surface-modified carbon material according to claim 14, wherein the liquid medium is obtained by dissolving the compound exhibiting a periodic self-assembling property in a non-polar organic solvent or a low-polarity organic solvent.

[claim20]
20. The method for producing a surface-modified carbon material according to claim 19, wherein the non-polar organic solvent or the low-polarity organic solvent is a fatty acid, alkyl substituted benzene, an alkane having less than 20 carbon atoms, an alkanol, dialkyl ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[claim21]
21. The method for producing a surface-modified carbon material according to claim 14, wherein a concentration of the chemical modification compound in the electrolyte aqueous solution is 0.2 to 10.0 mmol/L.

[claim22]
22. The method for producing a surface-modified carbon material according to claim 10, wherein the chemical modification compound is a compound represented by the following formula (3):
wherein: R1, R2, and R3 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group, OR, COOH, SOOH, SOONH2, NO2, COOR, SiR3, H, F, Cl, Br, I, OH, NH2, NHR, CN, CONHR, or COH (R is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group); and Z is a halogen atom, BF4, BR4, or PF6 (R4 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a halogen substitution product thereof).

[claim23]
23. A surface-modified carbon material comprising a large number of chemical addends on at least a part of a surface of a carbon material selected from the group consisting of graphene, graphite, a glassy carbon film, and film-like pyrolytic carbon, wherein:
a two-dimensional periodicity corresponding to a large number of addition positions of the chemical addends is provided in a Fourier-transformed image of a scanning probe microscopic image of the surface; and
when the surface is fractionated by one compartment having an area of 5 to 15 nm2, a ratio of the total number of compartments in which the chemical addends are present to the number of all compartments is 70% or more.

[claim24]
24. The surface-modified carbon material according to claim 23, wherein the ratio is 90% or more.

[claim25]
25. A field-effect transistor comprising the surface-modified carbon material according to claim 1.

[claim26]
26. A sensor comprising the surface-modified carbon material according to claim 1.

[claim27]
27. A light emitting device comprising the surface-modified carbon material according to claim 1.

[claim28]
28. A catalyst comprising the surface-modified carbon material according to claim 1.
  • 発明者/出願人(英語)
  • TAHARA KAZUKUNI
  • TOBE YOSHITO
  • ISHIKAWA TORU
  • KUBO YUKI
  • DE FEYTER STEVEN WILLY NICOLAS
  • HIRSCH BRANDON EDWARD
  • LI ZHI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • Katholieke Universiteit Leuven
国際特許分類(IPC)
参考情報 (研究プロジェクト等) PRESTO Molecular technology and creation of new function AREA
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