JP7092306B2 - Carbon material, its manufacturing method and electron emission material - Google Patents

Carbon material, its manufacturing method and electron emission material Download PDF

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JP7092306B2
JP7092306B2 JP2018554991A JP2018554991A JP7092306B2 JP 7092306 B2 JP7092306 B2 JP 7092306B2 JP 2018554991 A JP2018554991 A JP 2018554991A JP 2018554991 A JP2018554991 A JP 2018554991A JP 7092306 B2 JP7092306 B2 JP 7092306B2
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membered ring
carbon material
ring structure
nanotubes
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JPWO2018105559A1 (en
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和幸 田路
義倫 佐藤
洋次 尾本
良憲 佐藤
慧 石丸
浩典 松下
雅士 山本
哲郎 西田
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Stella Chemifa Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems

Description

本発明は、炭素材料、その製造方法及び電子放出材料に関し、より詳細には導電性に優れ、電界電子放出型ディスプレイ（ＦＥＤ）のエミッタや電界効果トランジスタ、陰極線管、電子銃等の電子デバイスへの応用が可能な炭素材料、その製造方法及び電子放出材料に関する。 The present invention relates to a carbon material, a method for producing the same, and an electron emitting material. The present invention relates to a carbon material to which the above can be applied, a method for producing the same, and an electron emission material.

単層カーボンナノチューブ（single-walled carbon nanotubes、以下「ＳＷＣＮＴ」という場合がある。）は炭素原子のみから構成される中空円筒状の炭素材料であり、その特徴的な構造ゆえに優れた機械特性や電気伝導性を示す。また、ＳＷＣＮＴは巻き方（カイラリティ）によって金属型にも半導体型にもなるという特異な性質を備えている。特に、その優れた電気伝導性を活かしてナノ配線や超軽量電線、その他電子デバイスへの応用が期待されているが、未だ実現には至っていない。 Single-walled carbon nanotubes (hereinafter sometimes referred to as "SWCNTs") are hollow cylindrical carbon materials composed only of carbon atoms, and have excellent mechanical properties and electricity due to their characteristic structure. Shows conductivity. Further, SWCNT has a peculiar property that it can be either a metal type or a semiconductor type depending on the winding method (chirality). In particular, it is expected to be applied to nano-wiring, ultra-lightweight electric wires, and other electronic devices by taking advantage of its excellent electrical conductivity, but it has not yet been realized.

その原因の一つとして、ＳＷＣＮＴの合成過程、精製過程又は表面の化学修飾過程等で、その炭素骨格に構造上の欠陥が導入されることが挙げられる。構造上の欠陥は、ＳＷＣＮＴの電気伝導性をはじめとする幾つかの特性の低下又は変化を招来するためである。その結果、構造欠陥を有しないＳＷＣＮＴの研究・開発が進められているが、その合成は困難であるという問題がある。尚、ここでいう構造上の欠陥とは、導入された官能基、ＳＴＷ(Stone-Thrower-Wales)欠陥、炭素原子以外の原子（例えば、水素原子や酸素原子、窒素原子、金属原子等）が存在することによる欠陥、空孔欠陥等を意味する。 One of the causes is that structural defects are introduced into the carbon skeleton in the SWCNT synthesis process, purification process, surface chemical modification process, or the like. Structural defects are due to the deterioration or change of some properties, including the electrical conductivity of SWCNTs. As a result, research and development of SWCNTs having no structural defects are being promoted, but there is a problem that their synthesis is difficult. The structural defects referred to here include introduced functional groups, STW (Stone-Thrower-Wales) defects, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, metal atoms, etc.). It means a defect due to existence, a hole defect, etc.

S.Iijima、 Nature Vol.354、 p.56(1991)S.Iijima, Nature Vol.354, p.56 (1991)

本発明は前記問題点に鑑みなされたものであり、その目的は、電気伝導性に優れた炭素材料、その製造方法及び電子放出材料を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a carbon material having excellent electrical conductivity, a method for producing the same, and an electron emitting material.

本願発明者等は、ＳＷＣＮＴ等の炭素材料を実用化するにあたって、空孔欠陥が発生するのを防止するのではなく、当該空孔欠陥を積極的に利用することで、電気伝導性等の特性の制御が可能になることを見出し、本願発明を完成させるに至った。 In the practical application of carbon materials such as SWCNTs, the inventors of the present application do not prevent the occurrence of pore defects, but positively utilize the pore defects to have characteristics such as electrical conductivity. We have found that it is possible to control the above, and have completed the invention of the present application.

すなわち、本発明の炭素材料は、前記の課題を解決する為に、炭素六員環ネットワークを有する炭素材料であって、前記炭素六員環ネットワーク中に、再配列構造である炭素五員環構造と炭素七員環構造がそれぞれ組み込まれているものであることを特徴とする。 That is, the carbon material of the present invention is a carbon material having a carbon six-membered ring network in order to solve the above-mentioned problems, and has a carbon five-membered ring structure which is an rearrangement structure in the carbon six-membered ring network. It is characterized by incorporating a carbon seven-membered ring structure and a carbon seven-membered ring structure, respectively.

前記の構成に於いて、前記炭素六員環ネットワークを有する炭素材料がカーボンナノチューブであり、前記再配列構造である炭素五員環構造と炭素七員環構造が、前記カーボンナノチューブの少なくとも側面にそれぞれ組み込まれていることが好ましい。 In the above configuration, the carbon material having the carbon six-membered ring network is a carbon nanotube, and the carbon five-membered ring structure and the carbon seven-membered ring structure, which are the rearranged structures, are formed on at least the side surfaces of the carbon nanotubes, respectively. It is preferably incorporated.

前記の構成に於いては、前記カーボンナノチューブが、ジグザグ型単層カーボンナノチューブ、アームチェア型単層カーボンナノチューブ又はキラル型単層カーボンナノチューブであることが好ましい。 In the above configuration, it is preferable that the carbon nanotubes are zigzag type single-walled carbon nanotubes, armchair-type single-walled carbon nanotubes, or chiral-type single-walled carbon nanotubes.

前記の構成に於いては、前記炭素六員環ネットワークを有する炭素材料がグラフェンであることが好ましい。 In the above configuration, it is preferable that the carbon material having the carbon six-membered ring network is graphene.

本発明に係る炭素材料の製造方法は、前記の課題を解決する為に、炭素六員環ネットワークを有する炭素材料に、フッ素含有ガスを含む処理ガスを接触させて、当該炭素材料の表面にフッ素基を導入するフッ素化処理工程と、前記フッ素化処理工程後の炭素材料を、温度４００℃～１５００℃の条件下でアニール処理することにより、前記フッ素基を脱離させて炭素六員環構造に空孔を生じさせ、再配列構造である炭素五員環構造と炭素七員環構造をそれぞれ導入するアニール処理工程とを含むことを特徴とする。 In the method for producing a carbon material according to the present invention, in order to solve the above-mentioned problems, a treatment gas containing a fluorine-containing gas is brought into contact with a carbon material having a carbon six-membered ring network, and fluorine is applied to the surface of the carbon material. The carbon material after the fluorination treatment step for introducing a group and the carbon material after the fluorination treatment step are annealed under the conditions of a temperature of 400 ° C. to 1500 ° C. to desorb the fluorine group to form a carbon six-membered ring structure. It is characterized by including an annealing treatment step of forming a hole in the fluorine and introducing a carbon five-membered ring structure and a carbon seven-membered ring structure, which are rearranged structures, respectively.

前記の構成に於いては、前記炭素六員環ネットワークを有する炭素材料としてカーボンナノチューブを用い、前記アニール処理により、前記再配列構造である炭素五員環構造と炭素七員環構造を、前記カーボンナノチューブの側面にそれぞれ導入することが好ましい。 In the above configuration, carbon nanotubes are used as the carbon material having the carbon six-membered ring network, and by the annealing treatment, the carbon five-membered ring structure and the carbon seven-membered ring structure, which are the rearranged structures, are obtained from the carbon. It is preferable to introduce each on the side surface of the nanotube.

前記の構成に於いては、前記カーボンナノチューブとして、ジグザグ型単層カーボンナノチューブ、アームチェア型単層カーボンナノチューブ又はキラル型単層カーボンナノチューブを用いることが好ましい。 In the above configuration, it is preferable to use zigzag type single-walled carbon nanotubes, armchair-type single-walled carbon nanotubes, or chiral-type single-walled carbon nanotubes as the carbon nanotubes.

前記の構成に於いては、前記炭素六員環ネットワークを有する炭素材料としてグラフェンを用いたことが好ましい。 In the above configuration, it is preferable to use graphene as the carbon material having the carbon six-membered ring network.

本発明の炭素材料によれば、これを構成する炭素六員環ネットワーク中には、炭素五員環構造及び炭素七員環構造がそれぞれ組み込まれている。そして、炭素五員環構造及び炭素七員環構造は、本来、空孔欠陥が生じていた部分の炭素原子を再配列させた構造である。そのため、前記構成の炭素材料は、空孔欠陥を有する炭素材料と比較して、電気伝導性の向上を図ることができる。 According to the carbon material of the present invention, a carbon five-membered ring structure and a carbon seven-membered ring structure are incorporated in the carbon six-membered ring network constituting the carbon material, respectively. The carbon five-membered ring structure and the carbon seven-membered ring structure are structures in which the carbon atoms in the portion where the vacancy defect has originally occurred are rearranged. Therefore, the carbon material having the above structure can be improved in electrical conductivity as compared with the carbon material having pore defects.

また、本発明の炭素材料の製造方法によれば、炭素六員環ネットワークを有する炭素材料にフッ素含有ガスを含む処理ガスを接触させることにより、炭素材料の表面にフッ素基を導入してフッ素化処理を行う。次いで、アニール処理を行うことでフッ素基を脱離させ、炭素六員環ネットワークに空孔欠陥を生じさせた後に、当該空孔欠陥部分の炭素原子を再配列させる。これにより、炭素六員環ネットワーク中に再配列構造である炭素五員環構造及び炭素七員環構造が導入され、電気伝導性に優れた炭素材料の製造が可能になる。 Further, according to the method for producing a carbon material of the present invention, a treatment gas containing a fluorine-containing gas is brought into contact with a carbon material having a carbon six-membered ring network to introduce a fluorine group on the surface of the carbon material for fluorination. Perform processing. Then, an annealing treatment is performed to desorb the fluorine group to cause a vacancy defect in the carbon six-membered ring network, and then the carbon atom of the vacancy defect portion is rearranged. As a result, a carbon five-membered ring structure and a carbon seven-membered ring structure, which are rearranged structures, are introduced into the carbon six-membered ring network, and it becomes possible to manufacture a carbon material having excellent electrical conductivity.

単層カーボンナノチューブの構造を概略的に表す部分拡大図であって、同図（ａ）は単層カーボンナノチューブがジグザグ型である場合を表し、同図（ｂ）は当該ジグザグ型の単層カーボンナノチューブに再配列構造が導入された場合を表し、同図（ｃ）は単層カーボンナノチューブがアームチェア型である場合を表し、同図（ｄ）は当該アームチェア型の単層カーボンナノチューブに再配列構造が導入された場合を表す。It is a partially enlarged view which outlines the structure of a single-walled carbon nanotube, FIG. The case where the rearranged structure is introduced into the nanotube is shown, the figure (c) shows the case where the single-walled carbon nanotube is an armchair type, and the figure (d) shows the case where the single-walled carbon nanotube is rearranged into the armchair type single-walled carbon nanotube. Represents the case where an array structure is introduced. 本発明の実施の一形態に係る炭素材料の製造方法を説明するための説明図である。It is explanatory drawing for demonstrating the manufacturing method of the carbon material which concerns on one Embodiment of this invention.

（炭素材料）
本発明の実施の一形態に係る炭素材料について、以下に説明する。
本実施の形態の炭素材料は、炭素六員環ネットワークを有し、さらに炭素六員環ネットワークに再配列構造である炭素五員環構造と炭素七員環構造がそれぞれ組み込まれた構造を有する。炭素骨格である炭素六員環ネットワーク中に、炭素五員環構造及び炭素七員環構造が組み込まれることにより、当該炭素材料の電気伝導性の向上が図れる。(Carbon material)
The carbon material according to the embodiment of the present invention will be described below.
The carbon material of the present embodiment has a carbon six-membered ring network, and further has a structure in which a carbon five-membered ring structure and a carbon seven-membered ring structure, which are rearranged structures, are incorporated into the carbon six-membered ring network, respectively. By incorporating a carbon five-membered ring structure and a carbon seven-membered ring structure into the carbon six-membered ring network, which is a carbon skeleton, the electrical conductivity of the carbon material can be improved.

本発明において「炭素六員環ネットワーク」とは、炭素原子のみで構成される六員環構造（ハニカム構造）を一単位として、当該六員環構造がネットワーク状に結合した炭素骨格を意味する。「炭素六員環ネットワーク」は水素原子及び置換基を含まない骨組みであって、全て炭素原子からなる。また、本発明において「再配列構造」とは、炭素六員環ネットワークに存在していた空孔欠陥部分において、炭素原子を再配列させたことにより形成される構造を意味し、より具体的には炭素五員環構造及び炭素七員環構造をいう。さらに、前記「空孔欠陥」とは、炭素六員環ネットワークにおいて、当該ネットワークを構成する炭素原子の一部が存在せず、構造上の欠陥として空孔が生じた状態を意味する。 In the present invention, the "carbon 6-membered ring network" means a carbon skeleton in which the 6-membered ring structure is bonded in a network shape with the 6-membered ring structure (honeycomb structure) composed of only carbon atoms as one unit. The "carbon six-membered ring network" is a framework that does not contain hydrogen atoms and substituents, and consists entirely of carbon atoms. Further, in the present invention, the "rearrangement structure" means a structure formed by rearranging carbon atoms in the pore defect portion existing in the carbon six-membered ring network, and more specifically. Refers to a carbon five-membered ring structure and a carbon seven-membered ring structure. Further, the "vacancy defect" means a state in which a part of carbon atoms constituting the carbon six-membered ring network does not exist and a hole is generated as a structural defect.

前記炭素材料としては、炭素原子からなる炭素六員環ネットワークを備えるものであれば特に限定されず、例えば、活性炭、カーボンナノコイル、グラファイト、カーボンブラック、ダイヤモンドライクカーボン、炭素繊維、グラフェン、非晶質カーボン、フラーレン、カーボンナノチューブ等が挙げられる。さらに、このような炭素材料の基本構造を有する類縁体も本発明にかかる炭素材料に含まれる。これらの炭素材料のうち本実施の形態においては、カーボンナノチューブやグラフェン等が好ましい。尚、フラーレンは、炭素六員環構造の他に炭素五員環構造を本来的に有するものであるが、当該炭素五員環構造は炭素六員環ネットワークに存在していた空孔欠陥部分の炭素原子を再配列させたことにより形成されるものではない。従って、本発明にいう再配列構造である炭素五員環構造とは異なる。 The carbon material is not particularly limited as long as it has a carbon six-membered ring network composed of carbon atoms, and is, for example, activated carbon, carbon nanocoils, graphite, carbon black, diamond-like carbon, carbon fibers, graphene, and amorphous. Quality Carbon, fullerene, carbon nanotubes and the like can be mentioned. Further, an analog having such a basic structure of a carbon material is also included in the carbon material according to the present invention. Of these carbon materials, carbon nanotubes, graphene, and the like are preferable in the present embodiment. The fullerene originally has a carbon five-membered ring structure in addition to the carbon six-membered ring structure, and the carbon five-membered ring structure is a defect portion of a hole existing in the carbon six-membered ring network. It is not formed by rearranging the carbon atoms. Therefore, it is different from the carbon five-membered ring structure which is the rearranged structure referred to in the present invention.

炭素材料がカーボンナノチューブである場合、再配列構造である炭素五員環構造及び炭素七員環構造は、当該カーボンナノチューブの少なくとも側面に組み込まれる。カーボンナノチューブの側面に再配列構造である炭素五員環構造及び炭素七員環構造を組み込むことにより、カーボンナノチューブの電気伝導性の向上が図れる。 When the carbon material is a carbon nanotube, the carbon five-membered ring structure and the carbon seven-membered ring structure, which are rearranged structures, are incorporated into at least the side surface of the carbon nanotube. By incorporating a carbon five-membered ring structure and a carbon seven-membered ring structure, which are rearranged structures, on the side surface of the carbon nanotube, the electrical conductivity of the carbon nanotube can be improved.

前記カーボンナノチューブとしては、６角網目のチューブ（グラフェンシート）が１枚の構造である単層カーボンナノチューブ（ＳＷＣＮＴ：Ｓｉｎｇｌｅ Ｗａｌｌ Ｃａｒｂｏｎ Ｎａｎｏｔｕｂｅ）や、多層のグラフェンシートから構成されている多層カーボンナノチューブ（ＭＷＣＮＴ：Ｍａｌｕｔｉ Ｗａｌｌ Ｃａｒｂｏｎ Ｎａｎｏｔｕｂｅ）、フラーレンチューブ、バッキーチューブ、グラファイトフィブリルが挙げられる。 The carbon nanotubes include single-walled carbon nanotubes (SWCNTs: Single Wall Carbon Nanotubes) in which a hexagonal mesh tube (graphene sheet) has a single structure, and multi-walled carbon nanotubes (MWCNTs) composed of multi-walled graphene sheets. : Maluti Wall Carbon Nanotube), full-wallen tube, bucky tube, graphite fibril.

さらに、単層カーボンナノチューブとしては、六員環構造の配列の観点から、ジグザグ型（金属型）単層カーボンナノチューブ、アームチェア型（半導体型）単層カーボンナノチューブ、キラル型単層カーボンナノチューブが挙げられる。 Further, examples of the single-walled carbon nanotubes include zigzag type (metal type) single-walled carbon nanotubes, armchair type (semiconductor type) single-walled carbon nanotubes, and chiral type single-walled carbon nanotubes from the viewpoint of the arrangement of the six-membered ring structure. Be done.

単層カーボンナノチューブがジグザグ型（金属型）である場合、再配列構造が導入される前の単層カーボンナノチューブは、図１（ａ）に示すような炭素六員環ネットワークの構造となっている。このジグザグ型単層カーボンナノチューブの炭素六員環ネットワークに、再配列構造である炭素五員環構造及び炭素七員環構造が導入されると、図１（ｂ）に示す様な構造となる。また、単層カーボンナノチューブがアームチェア型（半導体型）である場合、再配列構造が導入される前の単層カーボンナノチューブは、図１（ｃ）に示すような炭素六員環ネットワークの構造となっている。このアームチェア型単層カーボンナノチューブの炭素六員環ネットワークに、再配列構造である炭素五員環構造及び炭素七員環構造が導入されると、図１（ｄ）に示す様な構造となる。尚、図１は、単層カーボンナノチューブの構造を概略的に表す部分拡大図であって、同図（ａ）は単層カーボンナノチューブがジグザグ型である場合を表し、同図（ｂ）は当該ジグザグ型の単層カーボンナノチューブに再配列構造が導入された場合を表し、同図（ｃ）は単層カーボンナノチューブがアームチェア型である場合を表し、同図（ｄ）は当該アームチェア型の単層カーボンナノチューブに再配列構造が導入された場合を表す。 When the single-walled carbon nanotubes are of the zigzag type (metal type), the single-walled carbon nanotubes before the rearrangement structure is introduced have a structure of a carbon six-membered ring network as shown in FIG. 1 (a). .. When the carbon five-membered ring structure and the carbon seven-membered ring structure, which are rearranged structures, are introduced into the carbon six-membered ring network of the zigzag type single-walled carbon nanotube, the structure is as shown in FIG. 1 (b). When the single-walled carbon nanotubes are of the armchair type (semiconductor type), the single-walled carbon nanotubes before the rearrangement structure is introduced have the structure of the carbon six-membered ring network as shown in FIG. 1 (c). It has become. When the carbon five-membered ring structure and the carbon seven-membered ring structure, which are rearranged structures, are introduced into the carbon six-membered ring network of this armchair-type single-walled carbon nanotube, the structure is as shown in FIG. 1 (d). .. It should be noted that FIG. 1 is a partially enlarged view schematically showing the structure of the single-walled carbon nanotubes, FIG. 1A shows a case where the single-walled carbon nanotubes have a zigzag shape, and FIG. 1B shows the case. The case where the rearrangement structure is introduced into the zigzag type single-walled carbon nanotube is shown, the figure (c) shows the case where the single-walled carbon nanotube is an armchair type, and the figure (d) shows the case of the armchair type. It represents the case where the rearrangement structure is introduced into the single-walled carbon nanotube.

単層カーボンナノチューブは、その末端の一方又は両方が開放された構造であってもよく、あるいは閉鎖された構造であってもよい。閉鎖された構造である場合には、単層カーボンナノチューブの末端に炭素五員環構造が組み込まれる。この場合、その先端形状は炭素五員環構造の数や配置位置に応じて適宜変更可能である。尚、単層カーボンナノチューブの末端を閉鎖した構造とするために導入される炭素五員環構造は、空孔欠陥部分の炭素原子を再配列させて形成されるものではない。従って、本発明にいう再配列構造である炭素五員環構造とは異なる。 The single-walled carbon nanotubes may have a structure in which one or both of the ends thereof are open or closed. In the case of a closed structure, a carbon five-membered ring structure is incorporated at the end of the single-walled carbon nanotube. In this case, the tip shape can be appropriately changed according to the number of carbon five-membered ring structures and the arrangement position. The carbon five-membered ring structure introduced to form the structure in which the ends of the single-walled carbon nanotubes are closed is not formed by rearranging the carbon atoms in the vacancy defect portion. Therefore, it is different from the carbon five-membered ring structure which is the rearranged structure referred to in the present invention.

（炭素材料の製造方法）
次に、本実施の形態に係る炭素材料の製造方法について、図２に基づき以下に説明する。図２は、前記炭素材料の製造方法を説明するための説明図である。(Manufacturing method of carbon material)
Next, a method for producing a carbon material according to the present embodiment will be described below with reference to FIG. FIG. 2 is an explanatory diagram for explaining a method for producing the carbon material.

図２に示すように、本実施の形態の炭素材料の製造方法は、炭素材料のフッ素化処理工程と、フッ素化処理後の炭素材料をアニール処理するアニール処理工程とを少なくとも有する。 As shown in FIG. 2, the method for producing a carbon material according to the present embodiment includes at least a fluorination treatment step for the carbon material and an annealing treatment step for annealing the carbon material after the fluorination treatment.

前記フッ素化処理工程は、炭素材料に少なくともフッ素含有ガスを含む処理ガスを接触させることにより、気相中でその表面をフッ素化処理する工程である。例えば、図２に示すように、炭素材料が単層カーボンナノチューブ１１である場合、本工程は単層カーボンナノチューブ１１の表面に炭素－フッ素結合によるフッ素基１２を導入するものである。本工程は、例えば、炭素六角網面のエッジ部分に水酸基、カルボニル基又はカルボキシル基等の含酸素官能基を付与する酸化処理とは異なり、炭素材料にダメージを与えたり分解させる等の構造欠陥を生じさせることなく、その表面をフッ素化することができる。 The fluorination treatment step is a step of fluorinating the surface of the carbon material in the gas phase by contacting the carbon material with a treatment gas containing at least a fluorine-containing gas. For example, as shown in FIG. 2, when the carbon material is a single-walled carbon nanotube 11, this step introduces a fluorine group 12 by a carbon-fluorine bond on the surface of the single-walled carbon nanotube 11. This step is different from the oxidation treatment in which, for example, an oxygen-containing functional group such as a hydroxyl group, a carbonyl group or a carboxyl group is imparted to the edge portion of the carbon hexagonal network surface, and structural defects such as damage or decomposition of the carbon material are caused. The surface can be fluorinated without causing it.

前記処理ガスとしては、全体積に対し０．０１～１００ｖｏｌ％、好ましくは０．１～８０ｖｏｌ％、より好ましくは１～５０ｖｏｌ％のフッ素含有ガスを含むものが用いられる。フッ素含有ガスの濃度を０．０１ｖｏｌ％以上にすることにより、炭素材料表面のフッ素化が不十分となるのを防止することができる。 As the treatment gas, a gas containing 0.01 to 100 vol%, preferably 0.1 to 80 vol%, more preferably 1 to 50 vol% of fluorine-containing gas with respect to the total volume is used. By setting the concentration of the fluorine-containing gas to 0.01 vol% or more, it is possible to prevent insufficient fluorination of the surface of the carbon material.

前記フッ素含有ガスとはフッ素原子を含む気体を意味し、本実施の形態に於いてはフッ素原子を含むものであれば特に限定されない。前記フッ素含有ガスとしては、例えば、フッ素（Ｆ２）、フッ化水素（ＨＦ）、三フッ化塩素（ＣｌＦ３）、四フッ化硫黄（ＳＦ４）、三フッ化ホウ素（ＢＦ３）、三フッ化窒素（ＮＦ３）、フッ化カルボニル（ＣＯＦ２）等が挙げられる。これらは単独で、又は二種以上を混合して用いてもよい。The fluorine-containing gas means a gas containing a fluorine atom, and is not particularly limited as long as it contains a fluorine atom in the present embodiment. Examples of the fluorine-containing gas include fluorine (F 2 ), hydrogen fluoride (HF), chlorine trifluoride (ClF 3 ), sulfur tetrafluoride (SF 4 ), boron trifluoride (BF 3 ), and three. Examples thereof include nitrogen fluoride (NF 3 ) and carbonyl fluoride (COF 2 ). These may be used alone or in admixture of two or more.

前記処理ガスには不活性ガスが含まれていてもよい。不活性ガスとしては特に限定されないが、フッ素含有ガスと反応して炭素材料のフッ素化処理に悪影響を与えるもの、炭素材料と反応して悪影響を与えるもの、及び当該悪影響を与える不純物を含むものは好ましくない。具体的には、例えば、窒素、アルゴン、ヘリウム、ネオン、クリプトン、キセノン等が挙げられる。これらは単独で、又は２種以上を混合して用いることができる。また、不活性ガスの純度としては特に限定されないが、当該悪影響を与える不純物については１００ｐｐｍ以下であることが好ましく、１０ｐｐｍ以下であることがより好ましく、１ｐｐｍ以下であることが特に好ましい。 The treated gas may contain an inert gas. The inert gas is not particularly limited, but a gas that reacts with a fluorine-containing gas and adversely affects the fluorination treatment of the carbon material, a gas that reacts with the carbon material and has an adverse effect, and a gas containing impurities that have such an adverse effect are used. Not preferred. Specific examples thereof include nitrogen, argon, helium, neon, krypton, xenon and the like. These can be used alone or in combination of two or more. The purity of the inert gas is not particularly limited, but the impurities having an adverse effect are preferably 100 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less.

尚、前記処理ガス中には酸素原子を含むガスを含まないことが好ましい。酸素原子を含むガスを含有させることにより、炭素材料の表面に水酸基やカルボキシル基等が導入され、炭素材料に大きなダメージを与える場合があるからである。尚、酸素原子を含むガスとは、酸素ガスや硝酸ガスを意味する。 It is preferable that the treated gas does not contain a gas containing an oxygen atom. This is because the inclusion of a gas containing an oxygen atom introduces a hydroxyl group, a carboxyl group, or the like on the surface of the carbon material, which may cause great damage to the carbon material. The gas containing an oxygen atom means oxygen gas or nitric acid gas.

処理ガスの接触方法としては特に限定されず、例えば、処理ガスのフロー下で、又は密閉状態にした容器内の、当該処理ガスの雰囲気下で、炭素材料に接触させることにより行うことができる。 The contact method of the processing gas is not particularly limited, and for example, it can be carried out by contacting the carbon material under the flow of the processing gas or in the atmosphere of the processing gas in a closed container.

前記フッ素化処理を行う際の処理温度は特に限定されないが、好ましくは０℃～１５００℃の範囲内であり、より好ましくは０℃～８００℃、さらに好ましくは０℃～６００℃である。処理温度を０℃以上にすることにより、フッ素化処理の促進が図られる。その一方、処理温度を１５００℃以下にすることにより、炭素材料表面へのフッ素基の導入に伴って発生する炭素骨格への欠陥が過度に増大するのを抑制し、炭素骨格の過度の破壊及び炭素材料の機械的強度が減少するのを防止することができる。さらに、炭素材料に熱変形が生じるのを防止し、歩留まりの低下を抑制することができる。 The treatment temperature at the time of performing the fluorination treatment is not particularly limited, but is preferably in the range of 0 ° C to 1500 ° C, more preferably 0 ° C to 800 ° C, and further preferably 0 ° C to 600 ° C. By setting the treatment temperature to 0 ° C. or higher, the fluorination treatment can be promoted. On the other hand, by setting the treatment temperature to 1500 ° C. or lower, it is possible to suppress excessive increase in defects in the carbon skeleton generated by the introduction of fluorine groups on the surface of the carbon material, resulting in excessive destruction of the carbon skeleton and excessive destruction of the carbon skeleton. It is possible to prevent the mechanical strength of the carbon material from decreasing. Further, it is possible to prevent thermal deformation of the carbon material and suppress a decrease in yield.

前記フッ素化処理の処理時間（反応時間）は特に限定されないが、１秒～２４時間の範囲内であり、好ましくは１秒～１２時間、より好ましくは1秒～９時間である。処理時間を１秒以上にすることにより、炭素材料表面のフッ素化を十分なものにすることができる。その一方、処理時間を２４時間以下にすることにより、製造時間の長期化による製造効率の低下を防止することができる。 The treatment time (reaction time) of the fluorination treatment is not particularly limited, but is in the range of 1 second to 24 hours, preferably 1 second to 12 hours, and more preferably 1 second to 9 hours. By setting the treatment time to 1 second or more, the fluorination of the surface of the carbon material can be sufficiently sufficient. On the other hand, by setting the processing time to 24 hours or less, it is possible to prevent a decrease in production efficiency due to a long production time.

フッ素化処理を行う際の圧力条件としては特に限定されず、常圧下、加圧下又は減圧下で行うことができる。経済上・安全上の観点からは、常圧下で行うのが好ましい。フッ素化処理を行うための反応容器としては特に限定されず、固定床、流動床等の従来公知のものを採用することができる。 The pressure conditions for performing the fluorination treatment are not particularly limited, and the fluorination treatment can be performed under normal pressure, pressure, or reduced pressure. From the viewpoint of economy and safety, it is preferable to carry out under normal pressure. The reaction vessel for performing the fluorination treatment is not particularly limited, and conventionally known ones such as a fixed bed and a fluidized bed can be adopted.

炭素材料に対する処理ガスの接触方法としては特に限定されず、例えば、当該処理ガスのフロー下で接触させることができる。 The method of contacting the treated gas with the carbon material is not particularly limited, and for example, the contact can be made under the flow of the treated gas.

前記アニール処理工程は、フッ素化処理工程後の炭素材料を所定の温度で加熱する工程である。例えば、図２に示す単層カーボンナノチューブ１１の場合、先ず、当該単層カーボンナノチューブ１１の表面に導入されたフッ素基１２を脱離させて炭素六員環構造に空孔欠陥１３を生じさせる。その後、空孔欠陥１３における炭素原子を再配列させ、炭素五員環構造１４及び炭素七員環構造１５を導入する。 The annealing treatment step is a step of heating the carbon material after the fluorination treatment step at a predetermined temperature. For example, in the case of the single-walled carbon nanotube 11 shown in FIG. 2, first, the fluorine group 12 introduced on the surface of the single-walled carbon nanotube 11 is desorbed to cause a pore defect 13 in the carbon six-membered ring structure. After that, the carbon atoms in the pore defect 13 are rearranged, and the carbon five-membered ring structure 14 and the carbon seven-membered ring structure 15 are introduced.

アニール処理を行う際の処理温度は４００℃～１５００℃の範囲内であり、好ましくは６００℃～１５００℃、より好ましくは８００℃～１５００℃である。アニール処理の温度を４００℃以上にすることにより、フッ素基を十分に脱離させ、再配列構造の生成を促進することができる。その一方、アニール処理の温度を１５００℃以下にすることにより、炭素六員環ネットワークに新たな構造上の欠陥が過度に導入されるのを抑制し、炭素骨格の過度の破壊及び炭素材料の機械的強度が減少するのを防止することができる。さらに、炭素材料に熱変形が生じるのを防止し、歩留まりの低下を抑制することができる。 The treatment temperature at the time of performing the annealing treatment is in the range of 400 ° C. to 1500 ° C., preferably 600 ° C. to 1500 ° C., and more preferably 800 ° C. to 1500 ° C. By setting the temperature of the annealing treatment to 400 ° C. or higher, the fluorine group can be sufficiently desorbed and the formation of the rearranged structure can be promoted. On the other hand, by lowering the annealing temperature to 1500 ° C or lower, it is possible to prevent excessive introduction of new structural defects into the carbon six-membered ring network, resulting in excessive destruction of the carbon skeleton and mechanical use of carbon materials. It is possible to prevent the target strength from decreasing. Further, it is possible to prevent thermal deformation of the carbon material and suppress a decrease in yield.

前記アニール処理を行う際の処理時間は特に限定されないが、１秒～２４時間の範囲内であり、好ましくは１秒～１２時間、より好ましくは１秒～９時間である。処理時間を１秒以上にすることにより、フッ素基を十分に脱離させ、再配列構造の生成を促進することが可能になる。その一方、処理時間を２４時間以下にすることにより、炭素材料の劣化を防止することができる。 The treatment time for performing the annealing treatment is not particularly limited, but is in the range of 1 second to 24 hours, preferably 1 second to 12 hours, and more preferably 1 second to 9 hours. By setting the treatment time to 1 second or more, it becomes possible to sufficiently desorb the fluorine group and promote the formation of the rearranged structure. On the other hand, by setting the treatment time to 24 hours or less, deterioration of the carbon material can be prevented.

前記アニール処理を行う際の圧力条件としては特に限定されないが、大気圧に対し減圧下又は高真空下で行うことが好ましい。圧力条件を大気圧よりも減圧下にすることにより、フッ素基の脱離による空孔欠陥の生成を促進することができる。尚、大気圧とは、大気の標準状態近傍における圧力（標準大気圧）のことを意味し、大気の標準状態とは、約２５℃近傍の温度、絶対圧で１０１ｋＰａ近傍の大気圧条件のことを意味する。さらに、前記「大気圧」には標準大気圧に対し僅かに陽圧又は陰圧の場合も含む。 The pressure conditions for performing the annealing treatment are not particularly limited, but are preferably performed under reduced pressure or high vacuum with respect to atmospheric pressure. By setting the pressure condition to be lower than the atmospheric pressure, it is possible to promote the formation of pore defects due to the desorption of fluorine groups. The atmospheric pressure means the pressure near the standard state of the atmosphere (standard atmospheric pressure), and the standard state of the atmosphere is the atmospheric pressure condition of about 25 ° C. and the absolute pressure of about 101 kPa. Means. Further, the above-mentioned "atmospheric pressure" includes the case where the pressure is slightly positive or negative with respect to the standard atmospheric pressure.

また、アニール処理工程は、炭素材料からフッ素基を脱離させて空孔欠陥を生じさせる段階と、その後、炭素原子を再配列させて再配列構造を導入する段階とで、それぞれ処理条件を異ならせてもよい。 Further, in the annealing treatment step, the treatment conditions are different between the step of desorbing the fluorine group from the carbon material to cause a pore defect and the step of rearranging the carbon atoms to introduce the rearranged structure. You may let me.

また、アニール処理工程後の炭素材料について、電気伝導性の向上の観点からはフッ素基が残存していないことが望ましいが、例えば、当該炭素材料の溶媒への分散性の向上等の機能を付与したい場合には、電気伝導性への影響を及ぼさない範囲でフッ素基が残存していてもよい。 Further, it is desirable that no fluorine group remains in the carbon material after the annealing treatment step from the viewpoint of improving the electric conductivity, but for example, it is provided with a function of improving the dispersibility of the carbon material in the solvent. If this is the case, fluorine groups may remain within a range that does not affect the electrical conductivity.

以上より、本実施の形態の製造方法であると、炭素六員環ネットワーク中に、再配列構造である五員環構造及び七員環構造が組み込まれた炭素材料を製造することができる。これにより、本実施の形態においては、空孔欠陥を有する従来の炭素材料と比較して、電気伝導性に優れた炭素材料を製造することができる。 From the above, according to the manufacturing method of the present embodiment, it is possible to manufacture a carbon material in which a five-membered ring structure and a seven-membered ring structure, which are rearranged structures, are incorporated in a carbon six-membered ring network. Thereby, in the present embodiment, it is possible to produce a carbon material having excellent electrical conductivity as compared with the conventional carbon material having a pore defect.

尚、炭素材料の電気伝導性は、例えば、大気圧下における電気伝導率（Ｓ／ｍ）に対して減圧下での電気伝導率（Ｓ／ｍ）が１０％以上向上していることが好ましく、好ましくは２０％以上、より好ましくは４０％以上である。 As for the electrical conductivity of the carbon material, for example, it is preferable that the electrical conductivity (S / m) under reduced pressure is improved by 10% or more with respect to the electrical conductivity (S / m) under atmospheric pressure. It is preferably 20% or more, more preferably 40% or more.

（電子放出材料）
本実施の形態の炭素材料は、例えば、電子放出材料として利用可能である。電子放出材料は電界電子放出型ディスプレイ（ＦＥＤ）のエミッタ、電界効果トランジスタ、陰極線管、電子銃等に適用することができる。(Electron emission material)
The carbon material of this embodiment can be used as, for example, an electron emitting material. The electron emitting material can be applied to an emitter of a field electron emission display (FED), a field effect transistor, a cathode ray tube, an electron gun and the like.

（その他）
本実施の形態においては、フッ素化処理工程後にアニール処理工程を行う態様について説明した。但し、本発明はこの態様に限定されるものではなく、例えば、フッ素化処理とアニール処理を１つの工程中に同時に行ってもよい。これにより、炭素材料の製造時間の短縮化が図れる。尚、フッ素化処理とアニール処理を同時に行う場合の処理条件については、前述の通りである。(others)
In the present embodiment, an embodiment in which the annealing treatment step is performed after the fluorination treatment step has been described. However, the present invention is not limited to this aspect, and for example, the fluorination treatment and the annealing treatment may be performed simultaneously in one step. As a result, the manufacturing time of the carbon material can be shortened. The treatment conditions when the fluorination treatment and the annealing treatment are performed at the same time are as described above.

（実施例１）
ＰＴＦＥ（ポリテトラフルオロエチレン）容器（容量５ｍＬ）に、アームチェア型（半導体型）の単層カーボンナノチューブ１０ｍｇを導入し、本容器を電解研磨されたＳＵＳ３１６Ｌ製チャンバー（容量３０ｍＬ）に設置した。単層カーボンナノチューブとしては、両端が閉鎖された構造のものを用いた。更に、チャンバー内を、窒素ガスの気流（２０ｍＬ／ｍｉｎ）下で、４℃／ｍｉｎの昇温速度で２５０℃まで昇温した後、温度２５０℃で１時間の恒温処理を行った。(Example 1)
An armchair-type (semiconductor-type) single-walled carbon nanotube (10 mg) was introduced into a PTFE (polytetrafluoroethylene) container (capacity: 5 mL), and this container was placed in an electropolished SUS316L chamber (capacity: 30 mL). As the single-walled carbon nanotubes, those having a structure in which both ends were closed were used. Further, the inside of the chamber was heated to 250 ° C. at a heating rate of 4 ° C./min under a stream of nitrogen gas (20 mL / min), and then subjected to constant temperature treatment at a temperature of 250 ° C. for 1 hour.

次に、チャンバー内を処理ガスに真空置換し、流量２５ｍＬ／ｍｉｎで処理ガスを流して、フッ素化処理をした。フッ素化処理の処理時間は４時間とした。また、処理ガスとしては、フッ素（Ｆ２）ガスと窒素ガスの混合ガスを用いた。さらに、フッ素ガスの濃度は処理ガスの全体積に対し２０ｖｏｌ％とした。フッ素化処理後、チャンバー内を窒素ガスに真空置換し、窒素気流（２０ｍＬ／ｍｉｎ）の下、室温まで放冷し、その後、チャンバーからフッ素化処理後の単層カーボンナノチューブを取り出した。Next, the inside of the chamber was vacuum-replaced with a treatment gas, and the treatment gas was flowed at a flow rate of 25 mL / min for fluorination treatment. The treatment time for the fluorination treatment was 4 hours. As the treatment gas, a mixed gas of fluorine (F 2 ) gas and nitrogen gas was used. Further, the concentration of fluorine gas was set to 20 vol% with respect to the total volume of the treated gas. After the fluorination treatment, the inside of the chamber was vacuum-replaced with nitrogen gas, allowed to cool to room temperature under a nitrogen stream (20 mL / min), and then the fluorinated single-walled carbon nanotubes were taken out from the chamber.

次に、アルミナ容器にフッ素化処理後の単層カーボンナノチューブを入れ、本容器を電気管状炉内に設置して真空アニール処理を行った。すなわち、電気管状炉内を１．０×１０－５Ｐａまで真空引きし、当該圧力条件下で、昇温速度３．５℃／ｍｉｎにて、４５０℃まで昇温させた。昇温後、４５０℃で１時間の恒温処理を行った。この４５０℃までの昇温と、４５０℃・１時間での高温処理とにより、単層カーボンナノチューブからフッ素基を脱離させ、空孔欠陥を生成させた。続いて、前記圧力条件下で、昇温速度２．５℃／ｍｉｎにて、１２００℃まで昇温させた。昇温後、温度１２００℃で３時間の恒温処理を行った。この１２００℃までの昇温と、１２００℃・３時間での高温処理とにより、単層カーボンナノチューブに生成させた空孔欠陥における炭素原子を再配列させて再配列構造を導入した。その後、電気管状炉内を室温まで放冷した後、チャンバー内を窒素ガスに置換し、本実施例に係る単層カーボンナノチューブを製造した。Next, the fluorinated single-walled carbon nanotubes were placed in an alumina container, and this container was placed in an electric tube furnace to perform vacuum annealing treatment. That is, the inside of the electric tube furnace was evacuated to 1.0 × 10-5 Pa, and the temperature was raised to 450 ° C. at a heating rate of 3.5 ° C./min under the pressure conditions. After the temperature was raised, a constant temperature treatment was performed at 450 ° C. for 1 hour. By the temperature rise to 450 ° C. and the high temperature treatment at 450 ° C. for 1 hour, the fluorine group was desorbed from the single-walled carbon nanotubes, and pore defects were generated. Subsequently, the temperature was raised to 1200 ° C. at a heating rate of 2.5 ° C./min under the pressure conditions. After the temperature was raised, a constant temperature treatment was performed at a temperature of 1200 ° C. for 3 hours. By the temperature rise to 1200 ° C. and the high temperature treatment at 1200 ° C. for 3 hours, the carbon atoms in the pore defects generated in the single-walled carbon nanotubes were rearranged to introduce an rearranged structure. Then, after allowing the inside of the electric tube furnace to cool to room temperature, the inside of the chamber was replaced with nitrogen gas to produce single-walled carbon nanotubes according to this example.

（比較例１）
本比較例においては、アームチェア型（半導体型）の単層カーボンナノチューブに対し、フッ素化処理を行わず真空アニール処理のみを行った。それ以外は、実施例１と同様にして本比較例に係る単層カーボンナノチューブを製造した。尚、単層カーボンナノチューブとしては、両端が閉鎖された構造のものを用いた。(Comparative Example 1)
In this comparative example, the armchair type (semiconductor type) single-walled carbon nanotubes were subjected to only vacuum annealing treatment without fluorination treatment. Other than that, the single-walled carbon nanotubes according to this comparative example were produced in the same manner as in Example 1. As the single-walled carbon nanotubes, those having a structure in which both ends were closed were used.

（元素分析）
処理前の単層カーボンナノチューブ、並びに実施例１及び比較例１に係る単層カーボンナノチューブのそれぞれについて、Ｘ線光電子分光法（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製、商品名：Ｋ－Ａｌｐｈａ）を用いて元素分析を行った。(Elemental analysis)
Elemental analysis of each of the single-walled carbon nanotubes before treatment and the single-walled carbon nanotubes according to Example 1 and Comparative Example 1 using X-ray photoelectron spectroscopy (manufactured by Thermo Fisher Scientific, trade name: K-Alpha). Was done.

（電気伝導性の評価） (Evaluation of electrical conductivity)

＜大気下での導電率測定＞
処理前の単層カーボンナノチューブ、並びに実施例１及び比較例１に係る単層カーボンナノチューブのそれぞれについて、５ｍｇを５０ｍＬのエタノール中に入れ、１５分間の超音波処理を実施して分散液を調製した。その後、分散液を減圧濾過し、縦１ｃｍ×横１ｃｍ×厚さ０．５ｍｍの薄膜サンプルを作製した。<Measurement of conductivity in the atmosphere>
For each of the single-walled carbon nanotubes before the treatment and the single-walled carbon nanotubes according to Example 1 and Comparative Example 1, 5 mg was placed in 50 mL of ethanol and ultrasonically treated for 15 minutes to prepare a dispersion. .. Then, the dispersion was filtered under reduced pressure to prepare a thin film sample having a length of 1 cm, a width of 1 cm, and a thickness of 0.5 mm.

続いて、それぞれの薄膜サンプルの四隅に金電極が当接するように取り付け、さらに各金電極からリード線を試料ホルダーに取り付けた。そして、４端子法により各薄膜サンプルの比抵抗を測定し、電気伝導率を算出した。測定は、大気圧下、気温２５℃、相対湿度３５％の条件で行った。測定の結果を下記表１に示す。 Subsequently, the gold electrodes were attached to the four corners of each thin film sample so as to be in contact with each other, and the lead wires from each gold electrode were attached to the sample holder. Then, the specific resistance of each thin film sample was measured by the 4-terminal method, and the electrical resistivity was calculated. The measurement was performed under atmospheric pressure, a temperature of 25 ° C., and a relative humidity of 35%. The measurement results are shown in Table 1 below.

＜真空下における導電率測定＞
また、前記薄膜サンプルの減圧下での導電率について、４端子法により測定を行った。すなわち、各薄膜サンプルの四隅に金電極が当接するように取り付け、さらに各金電極からリード線を試料ホルダーに取り付けた。続いて、各薄膜サンプルを備えた試料ホルダーをそれぞれチャンバー内に入れ、ロータリーポンプでチャンバー内を１．０×１０－５Ｐａまで真空引きした。その後、チャンバー内を減圧条件下で３００℃にて加熱処理し、薄膜サンプルに吸着している酸素原子を除去した。続いて、減圧条件下でチャンバー内を室温まで冷却し、４端子法により各薄膜サンプルの比抵抗を測定し、電気伝導率を算出した。測定は、圧力１．０×１０－５Ｐａの下、気温２５℃、相対湿度３５％の条件で行った。測定の結果を下記表１に示す。<Measurement of conductivity under vacuum>
Further, the conductivity of the thin film sample under reduced pressure was measured by the 4-terminal method. That is, the gold electrodes were attached to the four corners of each thin film sample so as to be in contact with each other, and the lead wires from the gold electrodes were attached to the sample holder. Subsequently, a sample holder equipped with each thin film sample was placed in each chamber, and the inside of the chamber was evacuated to 1.0 × 10-5 Pa with a rotary pump. Then, the inside of the chamber was heat-treated at 300 ° C. under reduced pressure conditions to remove oxygen atoms adsorbed on the thin film sample. Subsequently, the inside of the chamber was cooled to room temperature under reduced pressure conditions, the specific resistance of each thin film sample was measured by the 4-terminal method, and the electrical resistivity was calculated. The measurement was carried out under the conditions of a pressure of 1.0 × 10-5 Pa, a temperature of 25 ° C., and a relative humidity of 35%. The measurement results are shown in Table 1 below.

Figure 0007092306000001
Figure 0007092306000001

（結果）
表１から分かる通り、処理前及び比較例１の単層カーボンナノチューブの場合、大気圧下における比抵抗は減圧下における比抵抗と比べ小さい値となっており、大気圧下での導電率が高いことがわかる。一方、本実施例の単層カーボンナノチューブでは、大気圧下における比抵抗が減圧下における比抵抗よりも高い値となっており、減圧下において電気伝導率が４５％以上向上していることが確認された。(result)
As can be seen from Table 1, in the case of the single-walled carbon nanotubes before treatment and in Comparative Example 1, the specific resistance under atmospheric pressure is smaller than the specific resistance under reduced pressure, and the conductivity under atmospheric pressure is high. You can see that. On the other hand, in the single-walled carbon nanotubes of this example, the specific resistance under atmospheric pressure is higher than the specific resistance under reduced pressure, and it is confirmed that the electrical resistivity is improved by 45% or more under reduced pressure. Was done.

また、元素分析の結果、処理前、実施例１及び比較例１の各単層カーボンナノチューブのいずれにおいてもフッ素原子は検出されなかった（フッ素原子の原子組成百分率０ａｔ％）。このうち、実施例１に係る単層カーボンナノチューブについては、大気圧下の比抵抗と減圧下の比抵抗の値の変化がフッ素基の存在によるものではないことが確認された。その結果、実施例１の単層カーボンナノチューブにおいては、再配列構造である炭素五員環構造と炭素七員環構造が導入されていることが示された。

In addition, as a result of elemental analysis, no fluorine atom was detected in any of the single-walled carbon nanotubes of Example 1 and Comparative Example 1 before the treatment (atomic composition percentage of fluorine atom was 0 at%). Of these, regarding the single-walled carbon nanotubes according to Example 1, it was confirmed that the changes in the resistivity under atmospheric pressure and the resistivity under reduced pressure were not due to the presence of fluorine groups. As a result, it was shown that the carbon five-membered ring structure and the carbon seven-membered ring structure, which are rearranged structures, were introduced into the single-walled carbon nanotubes of Example 1.

Claims (10)

炭素六員環ネットワークを有する炭素材料であって、
前記炭素六員環ネットワーク中に、再配列構造である炭素五員環構造と炭素七員環構造がそれぞれ組み込まれており、
前記炭素材料の炭素骨格中に窒素原子が存在しておらず、
前記炭素材料の表面には炭素－フッ素結合によるフッ素基が存在している炭素材料。 A carbon material with a carbon six-membered ring network,
A carbon five-membered ring structure and a carbon seven-membered ring structure, which are rearranged structures, are incorporated into the carbon six-membered ring network, respectively .
Nitrogen atoms are not present in the carbon skeleton of the carbon material,
A carbon material in which a fluorine group due to a carbon-fluorine bond is present on the surface of the carbon material. 前記炭素六員環ネットワークを有する炭素材料がカーボンナノチューブであり、
前記再配列構造である炭素五員環構造と炭素七員環構造が、前記カーボンナノチューブの少なくとも側面にそれぞれ組み込まれている請求項１に記載の炭素材料。 The carbon material having the carbon six-membered ring network is a carbon nanotube.
The carbon material according to claim 1, wherein the carbon five-membered ring structure and the carbon seven-membered ring structure, which are the rearranged structures, are incorporated in at least the side surfaces of the carbon nanotubes, respectively. 前記カーボンナノチューブが、ジグザグ型単層カーボンナノチューブ、アームチェア型単層カーボンナノチューブ又はキラル型単層カーボンナノチューブである請求項２に記載の炭素材料。 The carbon material according to claim 2, wherein the carbon nanotubes are zigzag type single-walled carbon nanotubes, armchair-type single-walled carbon nanotubes, or chiral-type single-walled carbon nanotubes. 前記炭素六員環ネットワークを有する炭素材料がグラフェンである請求項１に記載の炭素材料。 The carbon material according to claim 1, wherein the carbon material having the carbon six-membered ring network is graphene. 炭素六員環ネットワークを有する炭素材料に、フッ素含有ガスを含む処理ガスを接触させて、当該炭素材料の表面に炭素－フッ素結合によるフッ素基を導入するフッ素化処理工程と、
前記フッ素化処理工程後の炭素材料を、大気圧に対し減圧又は高真空下に於いて、処理温度４００℃～１５００℃、処理時間１秒～２４時間の処理条件下でアニール処理することにより、前記フッ素基を脱離させて炭素六員環構造に空孔を生じさせ、再配列構造である炭素五員環構造と炭素七員環構造をそれぞれ導入するアニール処理工程とを含み、
前記アニール処理工程は、前記フッ素化処理工程後の炭素材料に於ける炭素骨格中の炭素原子が窒素原子に置換されて前記窒素原子が導入されることがないように、前記処理条件の範囲内で行われる炭素材料の製造方法。 A fluorination treatment step in which a treatment gas containing a fluorine-containing gas is brought into contact with a carbon material having a carbon six-membered ring network to introduce a fluorine group by a carbon-fluorine bond on the surface of the carbon material.
By annealing the carbon material after the fluorination treatment step under reduced pressure or high vacuum with respect to atmospheric pressure under treatment conditions of a treatment temperature of 400 ° C. to 1500 ° C. and a treatment time of 1 second to 24 hours . It includes an annealing step of desorbing the fluorine group to form a hole in the carbon 6-membered ring structure and introducing a carbon 5-membered ring structure and a carbon 7-membered ring structure, which are rearranged structures, respectively.
The annealing treatment step is within the range of the treatment conditions so that the carbon atom in the carbon skeleton in the carbon material after the fluorination treatment step is not replaced with the nitrogen atom and the nitrogen atom is not introduced. Method of manufacturing carbon material performed in . 前記アニール処理工程は、窒素原子が存在しない雰囲気下で行われる請求項５に記載の炭素材料の製造方法。 The method for producing a carbon material according to claim 5, wherein the annealing treatment step is performed in an atmosphere in which nitrogen atoms do not exist. 前記炭素六員環ネットワークを有する炭素材料としてカーボンナノチューブを用い、
前記アニール処理により、前記再配列構造である炭素五員環構造と炭素七員環構造を、前記カーボンナノチューブの側面にそれぞれ導入する請求項５又は６に記載の炭素材料の製造方法。 Using carbon nanotubes as the carbon material having the carbon six-membered ring network,
The method for producing a carbon material according to claim 5 or 6, wherein the carbon five-membered ring structure and the carbon seven-membered ring structure, which are the rearranged structures, are introduced into the side surfaces of the carbon nanotubes by the annealing treatment. 前記カーボンナノチューブとして、ジグザグ型単層カーボンナノチューブ、アームチェア型単層カーボンナノチューブ又はキラル型単層カーボンナノチューブを用いる請求項７に記載の炭素材料の製造方法。 The method for producing a carbon material according to claim 7, wherein the carbon nanotubes are zigzag type single-walled carbon nanotubes, armchair-type single-walled carbon nanotubes, or chiral-type single-walled carbon nanotubes. 前記炭素六員環ネットワークを有する炭素材料としてグラフェンを用いた請求項５又は６に記載の炭素材料の製造方法。 The method for producing a carbon material according to claim 5 or 6, wherein graphene is used as the carbon material having the carbon six-membered ring network. 請求項１～４の何れか１項に記載の炭素材料を含む電子放出材料。 An electron emitting material containing the carbon material according to any one of claims 1 to 4 .
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004352608A (en) 2003-05-28 2004-12-16 Samsung Corning Co Ltd Method for dispersing carbon nano-structure
WO2010074000A1 (en) 2008-12-24 2010-07-01 国立大学法人東北大学 Dispersion of carbon material and process for producing same
JP2013075783A (en) 2011-09-30 2013-04-25 Mitsubishi Materials Corp Fluorinated carbon nanofiber, method for producing the same and application thereof
JP2013529176A (en) 2010-06-10 2013-07-18 ザ・ユニバーシティ・オブ・マンチェスター Functionalized graphene
JP2014533973A (en) 2011-09-23 2014-12-18 パルティ、ヨーラム Gas exchange device comprising a nanotube and an artificial lung
JP2016113364A (en) 2014-12-16 2016-06-23 国立大学法人東北大学 Nitrogen-containing carbon material and method for producing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004352608A (en) 2003-05-28 2004-12-16 Samsung Corning Co Ltd Method for dispersing carbon nano-structure
WO2010074000A1 (en) 2008-12-24 2010-07-01 国立大学法人東北大学 Dispersion of carbon material and process for producing same
JP2013529176A (en) 2010-06-10 2013-07-18 ザ・ユニバーシティ・オブ・マンチェスター Functionalized graphene
JP2014533973A (en) 2011-09-23 2014-12-18 パルティ、ヨーラム Gas exchange device comprising a nanotube and an artificial lung
JP2013075783A (en) 2011-09-30 2013-04-25 Mitsubishi Materials Corp Fluorinated carbon nanofiber, method for producing the same and application thereof
JP2016113364A (en) 2014-12-16 2016-06-23 国立大学法人東北大学 Nitrogen-containing carbon material and method for producing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
溝口 則幸，Ston-ｗales欠陥をもつアームチェア炭素ナノチューブのHOMO-LUMOギャップのチューブ長依存性，ケモインフォマティクス討論会予稿集，日本，2011年11月06日，Ｐ６

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