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SURFACE-MODIFIED CARBON MATERIAL, AND METHOD FOR PRODUCING SURFACE-MODIFIED CARBON MATERIAL NEW

外国特許コード F200010033
整理番号 K10514WO
掲載日 2020年1月31日
出願国 世界知的所有権機関(WIPO)
国際出願番号 2019JP010720
国際公開番号 WO 2019168206
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
発明の名称 (英語) SURFACE-MODIFIED CARBON MATERIAL, AND METHOD FOR PRODUCING SURFACE-MODIFIED CARBON MATERIAL NEW
発明の概要(英語) The present invention is a surface-modified carbon material which comprises graphene having a chemical modification group added to the surface thereof, and in which one-dimensional periodicity corresponding to multiple sites for the addition of the chemical modification group can be observed in a Fourier-transformed image of a scanning probe microscopic image of the surface of the graphene. The surface-modified carbon material according to the present invention has a band gap and therefore can be used as a sensor capable of electronically controling an operation or another electronic device.
従来技術、競合技術の概要(英語) BACKGROUND ART
sp2 Is arranged in a honeycomb graphene carbon, its superior electric properties, mechanical properties, optical characteristics and thermal characteristics can be used in various applications has been expected. Graphene, from among high conductivity is used in the electronics field that is being considered. For this reason, the university or a research institute, corporation or the like associated with the graphene in the shape of the study are booming.
And a substance exhibiting metallic graphene, and is a zero band-gap semiconductor. Therefore, as it is of limited use as a material for electronics. However, the band gap in graphene can be introduced into a suitable, high-speed operation at room temperature and the field effect transistor of high performance, small size and high sensitivity to the sensor and enables the use of a molecule.
Therefore, the band gap in graphene is introduced a number of ways have been reported. For example, the doping of the graphene to electrons or holes from the support substrate, by plasma or ion lithography processing of graphene, microfabrication based on the SPM probe, and the chemically active species (carbon sp3) using the introduction of defects by chemical modification and the like.
Among these methods, the application of a chemically modified graphene, graphene to introduce the band gap of the addition, the organic group is added to the graphene electronic or chemical properties of the Fermi level by controlling the surface properties and has the advantage that it becomes possible to control. Chemical modification of graphene therefore been intensively studied.
In addition, chemical modification of graphene plane than that of the edge portion can be more easily chemically modified is known. Is carried out by chemical modification of graphene, the graphene in the plane of the position of application of the number of active chemical species in a portion of the control, to maintain the predetermined order becomes important. This is because, in a predetermined order while keeping the surface portion can be chemically modified, how the movement of the carrier, i.e. the advantages of the control can be realized in some cases is preferable.
First, in Patent Document 1 is, brought into contact with the fluid with the method disclosed in the present invention. In the present invention, the surface of the fluid in contact with the substrate, and the central portion of the at least one of an organic molecule having side arm is provided with a network. Then, silicon, and pyrolytic graphite (HOPG) or the like metal on the surface of the adsorbed molecule network formed as disclosed in the two-dimensional molecular sieve. Fig. 13 to, 6 of the carbon material 102 on the plane of the ring sequence of the basic skeleton of the organic compound 105a and the branch unit 105b to interact with the continuous two-dimensional structure formed according to the 100.
Then, Fig. 14 (a) the prior art according to Patent Document 2 is a schematic cross-sectional view. According to the prior art is Patent Document 2, stainless steel, ceramic or resin or the like for modifying the surface of the substrate 113 to form a carbonaceous film in the invention. That is, in Patent Document 2, sp3 and sp2 carbon atoms is bonded to the surface of the carbon comprising a carbon and an electrolyte membrane (6 112 a planar array of six-membered ring) including a hydrogen atom and an oxygen atom and a functional group, the surface of the carbonaceous film is chemically bonded to the organic component (graft chain 111) is modified with a carbonaceous film 110 has been disclosed.
(B) in Fig. 14 according to the prior art in Patent Document 3 are shown schematically. The electronic device 120 is, on the substrate edge is modified with the graphene film (6 122 a planar array of six-membered ring) serving as a channel, the channel 125 and the source electrode 124 and the drain electrode are electrically joined to have a structure. 120 Is an electronic device, the graphene film to the edge of the detection object detected species adsorption or species functional group bonding with the added 121, the edge of the graphene sensor is configured to be modified. Also, rather than at the edge of the graphene-like carbon material, a planar array surface 6 in the five membered ring on a chemical modification method, the chemical modifying group for a number of attempts have been made. (C) in Fig. 14 the surface of the graphite after chemical modification on a random, chemically modified STM probe are removed from the machine group, the carbon surface is exposed to a desired shape of a photograph showing the method. In this method, referred to as nano-shaving method.
Fig. 15 to, chemically modifying the surface of the carbon material as an NBD is added to the state shown schematically. In this case, the surface of the carbon material is added to a planar array of a 6 membered aryl to aryl group substitution reaction can be formed in a multilayer state in the cascade. As a result, with respect to the carbon material, a large number of chemical modifying group density in the plane of the modified or additional control is not achieved in the position.
In this way, in the conventional method, the addition of chemically active species of the graphene to occur randomly, especially in the plane of the position of application of the control (sp3 carbon position) is that it is virtually impossible. In addition, to precisely control the ratio of modification of the appendages may be difficult. In order to solve such a problem for some studies have been reported.
For example, in Non-Patent Document 1, a single-layer graphene on Ru (0001) to, a metal cyano methyl radical and the graphene due to the interaction, can be selectively added to the position have been reported. However, this method has a cycle (pitch) of the dimensionality cannot be controlled.
In addition, in Non-Patent Document 2, a long-chain alkyl groups having the aryl diazonium salts include an array of self-assembly on the graphene, the electrochemical reduction of aryl radicals can be generated, added to the graphene have been reported to occur. Then, the possibility of periodic modification are discussed.
Non-Patent Document 1 and Non-Patent Document 2 are of the method, an attractive approach for periodic chemical modifications may be made. However, the carbon material both for precise control of chemical surface modification which is far from. In the case where the chemical modifying group is added to the additional position control with high accuracy, and poor control of the rate would be modified.
On the other hand, in non-patent document 3, or on a solid substrate using a chemical reaction in the solution, a graphene nanoribbon (GNR) to the bottom-up method for synthesizing graphene nanoribbons or has been reported. In this method, the design of the appropriate size from the precursor can be obtained the advantage that the graphene or GNR. Therefore, research has been actively performed in recent years the method respectively. However, electronic or magnetic properties are largely dependent on the edge structure, the graphene itself and the strength is increased. In addition, the ribbon width can be broadened to a certain degree or more is impossible.
On the other hand, the organic molecule self-assembly by physical adsorption of a monomolecular film of graphite or graphene is formed using a method of forming a nano pattern on the surface have been reported. For example, in Non-Patent Document 4, at the interface of the graphite and the organic solvent, straight-chain alkanes self-assemble by the lamellar type may be formed of a single molecular film has been reported. However, in this Non-Patent Document 4, while controlling the adding position is performed periodically such as chemical modification is not disclose any concept.
Non-Patent Document 5 and in Non-Patent Document 6, the newly synthesized using derivatives (DBA) annulene 12, physical adsorption of organic molecules in the solid-liquid interface by using the self-assembled monolayer is formed, the surface of the graphite or graphene nano pattern forming methods have been reported in a simple manner. DBA derivative is an organic solvent and the graphite or graphene and the alignment of the molecules at the interface between the formed honeycomb-type STM was confirmed by observation.
In Non-Patent Document 7, Non-Patent Document 5 described above using a technique of Non-Patent Document 6, 6 of the periodic structure of the four-fold symmetry is formed on the graphite after, applying a chemical modification to the experimental results have been reported.
In non-patent document 8, the sputtering method using SiC a method of manufacturing graphene have been reported. In non-patent document 9, a method of forming graphene on a SiO substrate have been reported.
In non-patent document 10, with respect to the graphene, carbon sp3 is introduced into the defect in the case where the one-dimensional periodically, to control the band gap of the graphene that the prediction is calculated for the attempted method.
In non-patent document 11, the surface of the graphene or graphite, 3,5-tert - di (TBD) , or, 4-(NBD) nitrobenzene diazonium chloride is added to the chemical modification methods have been reported. That in Fig.13, added to the surface of the carbon material layer of an aryl group, the probe of STM can be partially removed, to expose the carbon surface of the rectangular area shown in a technique (see Fig. 14 (c)). And the exposed area of the rectangle is used as a template, two molecular self-assembly and pentacontanoic block has been shown a method of forming. In this prior art, the self-assembly on the surface of the carbon material is pentacontanoic, several blocks adjacent to the alignment state may be observed, in a larger area size, are arranged in a mosaic block in. In this way, the non-Patent Document 11 is used by the STM probe and the nano-shaving method, the electronic device can be used, an adduct of a predetermined sequence (the chemical modifying group) is formed in the state was not achieved.
Finally, in Non-Patent Document 12, defects in the graphene by Raman spectrum analysis of the different excitation energy can be quantitatively analyzed and reported.
  • 出願人(英語)
  • ※2012年7月以前掲載分については米国以外のすべての指定国
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • KATHOLIEKE UNIVERSITEIT LEUVEN
  • 発明者(英語)
  • TAHARA Kazukuni
  • TOBE Yoshito
  • ISHIKAWA TORU
  • KUBO Yuki
  • DE FEYTER Steven Willy Nicolas
  • HIRSCH Brandon Edward
  • LI Zhi
国際特許分類(IPC)
指定国 National States: AE AG AL AM AO AT AU AZ BA BB BG BH BN BR BW BY BZ CA CH CL CN CO CR CU CZ DE DJ DK DM DO DZ EC EE EG ES FI GB GD GE GH GM GT HN HR HU ID IL IN IR IS JO JP KE KG KH KN KP KR KW KZ LA LC LK LR LS LU LY MA MD ME MG MK MN MW MX MY MZ NA NG NI NO NZ OM PA PE PG PH PL PT QA RO RS RU RW SA SC SD SE SG SK SL SM ST SV SY TH TJ TM TN TR TT TZ UA UG US UZ VC VN ZA ZM ZW
ARIPO: BW GH GM KE LR LS MW MZ NA RW SD SL SZ TZ UG ZM ZW
EAPO: AM AZ BY KG KZ RU TJ TM
EPO: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
OAPI: BF BJ CF CG CI CM GA GN GQ GW KM ML MR NE SN ST TD TG
参考情報 (研究プロジェクト等) PRESTO Molecular technology and creation of new functions AREA
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