JP2008120658A - Aggregative structure of multiwall carbon nanotube - Google Patents

Aggregative structure of multiwall carbon nanotube Download PDF

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JP2008120658A
JP2008120658A JP2006309720A JP2006309720A JP2008120658A JP 2008120658 A JP2008120658 A JP 2008120658A JP 2006309720 A JP2006309720 A JP 2006309720A JP 2006309720 A JP2006309720 A JP 2006309720A JP 2008120658 A JP2008120658 A JP 2008120658A
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walled carbon
carbon nanotubes
carbon nanotube
substrate
aggregate structure
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JP4873413B2 (en
JP2008120658A5 (en
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Takuji Komukai
拓治 小向
Kumiko Yoshihara
久美子 吉原
Tomomoto Yamazaki
智基 山崎
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Sonac KK
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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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aggregative structure of multiwall carbon nanotubes aggregated to an ultra-high dense state. <P>SOLUTION: The aggregative structure of multiwall carbon nanotubes which are grown by an action of a catalyst microparticle on the surface of a substrate is observed as an aggregative structure which has a linearity of shape and an orientation vertical to the surface of the substrate and is aggregated to an ultra-high dense state as shown in SEM images taken by not only a designated magnification but also a higher magnification. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、基板表面上の触媒微粒子の触媒作用で成長する多層カーボンナノチューブの集合構造に関するものであり、特に基板表面上での多層カーボンナノチューブの集合密度に関するものである。   The present invention relates to an aggregate structure of multi-walled carbon nanotubes grown by catalytic action of catalyst fine particles on a substrate surface, and particularly to an aggregate density of multi-walled carbon nanotubes on a substrate surface.

多層カーボンナノチューブは、周知されるように、電子発生能と耐久性に優れ、大画面のフィールドエミッションディスプレイ用の電子発生材料等に有用視され、また、多層カーボンナノチューブは耐食性が高いため、燃料電池の触媒電極層等の耐食性が要求される用途にも適するなど、各種用途が期待されている物質である。   As is well known, multi-walled carbon nanotubes are excellent in electron generating ability and durability, and are regarded as useful as electron-generating materials for large-field field emission displays, and because multi-walled carbon nanotubes have high corrosion resistance, fuel cells It is a substance that is expected to be used in various applications, such as suitable for applications that require corrosion resistance, such as catalyst electrode layers.

このような多層カーボンナノチューブを基板上に成長する製造方法の一つに、基板上に触媒膜を成膜し、熱処理して触媒膜を複数の触媒微粒子からなる触媒構造を得ると共に、この触媒構造上の触媒微粒子にカーボンを含むガスを作用させて触媒微粒子を成長起点として多層カーボンナノチューブを成長させる方法がある。   One of the manufacturing methods for growing such multi-walled carbon nanotubes on a substrate is to form a catalyst film on the substrate and heat-treat to obtain a catalyst structure composed of a plurality of catalyst fine particles. There is a method in which a multi-walled carbon nanotube is grown by causing a gas containing carbon to act on the above catalyst fine particles and using the catalyst fine particles as a growth starting point.

この触媒構造には、触媒微粒子が熱処理中に基板中に拡散して作製されないことを防止するため、基板上にカーボンファイバの成長に対する触媒作用を持たないアルミニウム等の下地膜を成膜し、この下地膜の上に鉄等の触媒膜を成膜してカーボンナノチューブを成長させるものがある（特許文献１参照）。   In this catalyst structure, in order to prevent catalyst fine particles from diffusing into the substrate during the heat treatment, a base film such as aluminum having no catalytic action for the growth of carbon fibers is formed on the substrate. Some have a catalyst film made of iron or the like formed on a base film to grow carbon nanotubes (see Patent Document 1).

しかしながら、上記従来の触媒構造を用いて多層カーボンナノチューブを成長させる場合、多層カーボンナノチューブを基板上に高さ均等で形状の直線性と基板上での垂直配向性とを共に高く制御して成長させ、結果として高密度に成長させることは難しく電子放出用材料として優れた多層カーボンナノチューブを高効率で再現性よく製造することが困難であった。   However, when multi-walled carbon nanotubes are grown using the above-described conventional catalyst structure, the multi-walled carbon nanotubes are grown on the substrate while controlling both the linearity of the shape with a uniform height and the vertical orientation on the substrate. As a result, it was difficult to grow at high density, and it was difficult to produce multi-walled carbon nanotubes excellent as an electron emission material with high efficiency and reproducibility.

また、従来の方法にて成長させた多層カーボンナノチューブは触媒金属由来の不純物などを多く含んでおり、これらを除去する工程を経るために多層カーボンナノチューブが劣化したり、除去後にも残存する不純物が多く存在するなどの問題を抱えている。さらに従来の多層カーボンナノチューブ膜は500℃以下にて空気中で熱分解を開始するために、基板上へ膜形成させる工程などプロセス上の加熱工程において劣化が進行するなどの問題を抱えていた。
特開２００１−３０３２５０号公報 In addition, the multi-walled carbon nanotubes grown by the conventional method contain a large amount of impurities derived from the catalytic metal, and the multi-walled carbon nanotubes are deteriorated due to the process of removing these, and there are impurities remaining after the removal. We have problems such as many existing. Furthermore, since the conventional multi-walled carbon nanotube film starts thermal decomposition in the air at 500 ° C. or lower, it has a problem that deterioration proceeds in a heating process in the process such as a film forming process on a substrate.
JP 2001-303250 A

本発明により解決する課題は、形状の直線性と、基板表面上での垂直配向性とが共に高くして高密度でかつほぼ高さ均等な高さで多層カーボンナノチューブを集合させた構造を提供することである。   The problem to be solved by the present invention is to provide a structure in which multi-walled carbon nanotubes are assembled at a high density and a substantially uniform height by improving both the linearity of the shape and the vertical alignment on the substrate surface. It is to be.

本発明に係る多層カーボンナノチューブの集合構造は、基板表面上の触媒微粒子の作用で成長する複数の多層カーボンナノチューブの集合構造であって、上記多層カーボンナノチューブそれぞれが、形状の直線性と基板表面に対する垂直配向性とを備えて５０（mｇ／ｃｍ3）以上の密度で集合していることを特徴とするものである。上記密度は好ましくは９０（mｇ／ｃｍ3）以上である。 The multi-wall carbon nanotube aggregate structure according to the present invention is an aggregate structure of a plurality of multi-wall carbon nanotubes grown by the action of catalyst fine particles on the substrate surface. It is characterized by being gathered at a density of 50 (mg / cm 3 ) or more with vertical orientation. The density is preferably 90 (mg / cm 3 ) or more.

上記多層カーボンナノチューブの形状の直線性と垂直配向性を有して５０（mｇ／ｃｍ3）以上の密度で集合しているため、所定倍率例えば２０Ｋで拡大したＳＥＭ写真等の微細写真でも、さらに倍率を高くして１００Ｋで拡大したＳＥＭ写真等の微細写真でも形状の直線性と垂直配向性とを共に備えていることが観察することができることである。 Since the multi-walled carbon nanotubes have the linearity and vertical orientation of the shape and are assembled at a density of 50 (mg / cm 3 ) or more, even in a microphotograph such as an SEM photograph enlarged at a predetermined magnification, for example, 20K, It can be observed that even a microphotograph such as a SEM photograph enlarged at 100K with a high magnification has both shape linearity and vertical alignment.

このＳＥＭ写真での形状の直線性と基板表面に対する垂直配向性の有無の判定は、低倍率観察で垂直方向に成長していることが確認されている多層カーボンナノチューブにおいて、多層カーボンナノチューブの垂直配向性が十分に確認できる倍率に拡大したＳＥＭ画面上で、例えば１μｍの範囲において、例えば９０％以上の多層カーボンナノチューブに対して、実施する。   In this SEM photograph, the linearity of the shape and the presence / absence of the vertical alignment with respect to the substrate surface were determined based on the vertical alignment of the multi-walled carbon nanotubes in the multi-walled carbon nanotubes that were confirmed to grow vertically by low magnification observation. For example, 90% or more of the multi-walled carbon nanotube is performed in the range of 1 μm on the SEM screen enlarged to a magnification at which the property can be sufficiently confirmed.

好ましくは、上記多層カーボンナノチューブは、最内層の内径が３ｎｍ以上、８ｎｍ以下、より好ましくは４．５ｎｍ以上、７ｎｍ以下であり、かつ、最外層の外径が５ｎｍ以上、３５ｎｍ以下、より好ましくは８ｎｍ以上、２５ｎｍ以下である。   Preferably, in the multi-walled carbon nanotube, the inner diameter of the innermost layer is 3 nm or more and 8 nm or less, more preferably 4.5 nm or more and 7 nm or less, and the outer diameter of the outermost layer is 5 nm or more and 35 nm or less, more preferably It is 8 nm or more and 25 nm or less.

好ましくは上記多層カーボンナノチューブは、層数が３以上、３５以下、より好ましくは５以上、２５以下である。   Preferably, the multi-walled carbon nanotube has 3 or more and 35 or less layers, more preferably 5 or more and 25 or less.

好ましくは、得られた多層カーボンナノチューブは、空気中加熱酸化による重量減開始温度（耐熱性）が５００℃以上である。   Preferably, the obtained multi-walled carbon nanotube has a weight loss starting temperature (heat resistance) due to heat oxidation in air of 500 ° C. or higher.

さらに、空気中における９００℃熱分解後の残渣（不純物）が１％以下と非常に少なくなっている。   Furthermore, the residue (impurities) after pyrolysis at 900 ° C. in the air is very low at 1% or less.

本発明の多層カーボンナノチューブの集合構造では、基板表面上に複数の多層カーボンナノチューブが互いの形状の直線性と垂直配向性とが共に高いために高密度で集合することができ優れた電子放出用材料を提供することができる。   In the multi-walled carbon nanotube assembly structure of the present invention, a plurality of multi-walled carbon nanotubes can be assembled at a high density because of the high linearity and vertical alignment of each other on the substrate surface. Material can be provided.

以下、添付した図面を参照して、本発明の実施の形態に係る多層カーボンナノチューブの集合構造を詳細に説明する。   Hereinafter, an aggregate structure of multi-walled carbon nanotubes according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

図１は、実施の形態の多層カーボンナノチューブの集合を示す。図１を参照して、シリコン基板等の基板１上に触媒作用が無い金属例えばアルミニウムからなる下地膜２を介して触媒作用が有る金属例えば鉄からなる触媒微粒子４１，４２，…，４ｎが形成されている。   FIG. 1 shows an assembly of multi-walled carbon nanotubes according to an embodiment. Referring to FIG. 1, catalyst fine particles 41, 42,..., 4n made of a metal having a catalytic action such as iron are formed on a substrate 1 such as a silicon substrate through a base film 2 made of a metal having no catalytic action such as aluminum. Has been.

この基板１上の触媒微粒子４１，４２，…，４ｎ上には、成長高さがほぼ均等でかつ形状の直線性と基板１への垂直配向性とを持つ多層カーボンナノチューブ５１，５２，…，５ｎが成長している。なお、多層カーボンナノチューブ５１，５２，…，５ｎは総称するときは説明の都合で多層カーボンナノチューブ５と言う場合がある。   On the catalyst fine particles 41, 42,..., 4n on the substrate 1, the multi-walled carbon nanotubes 51, 52,..., Having a substantially uniform growth height, linear shape and vertical alignment with the substrate 1. 5n is growing. The multi-walled carbon nanotubes 51, 52,..., 5n may be collectively referred to as the multi-walled carbon nanotube 5 for convenience of explanation.

なお、この多層カーボンナノチューブ５は、上記した触媒構造を備えた基板１をアセチレン、エチレン、メタン、プロパン、プロピレン等のガス雰囲気中で所定温度例えば７００℃、所定時間例えば１０分間、例えば２００Ｐａの減圧下で加熱する熱ＣＶＤ法を実施したとき、基板１上の触媒微粒子４１，４２，…，４ｎの触媒作用により、成長したものである。   The multi-walled carbon nanotube 5 is formed by depressurizing the substrate 1 having the above catalyst structure in a gas atmosphere such as acetylene, ethylene, methane, propane, propylene, etc. at a predetermined temperature, for example, 700 ° C., for a predetermined time, for example, 10 minutes, for example, 200 Pa. When the thermal CVD method in which heating is performed below is performed, it grows by the catalytic action of the catalyst fine particles 41, 42,..., 4n on the substrate 1.

ここで図２を参照して上記多層カーボンナノチューブ５の形状の直線性と垂直配向性とを説明する。   Here, the linearity and vertical alignment of the shape of the multi-walled carbon nanotube 5 will be described with reference to FIG.

図２（ａ）で示すように、実施の形態で定義する多層カーボンナノチューブ５の形状の直線性は、最小二乗法による直線近似式（ｙ＝ａｘ＋ｂ）で決めることができる。ここで、ａは傾き、ｂは切片であり、これらは実験データから求めることができる。この場合、ばらつき誤差の２乗の和が最小となるよう直線を当てはめる。なお、実験条件を変えて得られた様々なｙの値の変化のうち、どれだけの割合がｙ＝ａｘ＋ｂの直線式で説明できているかを表す指標（決定係数）Ｒ2があり、このＲ2の値が１に近づくほど多層カーボンナノチューブ５の形状がより直線性を有するようになる。 As shown in FIG. 2A, the linearity of the shape of the multi-walled carbon nanotube 5 defined in the embodiment can be determined by a linear approximation formula (y = ax + b) by the least square method. Here, a is a slope and b is an intercept, which can be obtained from experimental data. In this case, a straight line is fitted so that the sum of the squares of the variation errors is minimized. Note that there is an index (determination coefficient) R 2 that indicates how much of the change in the value of y obtained by changing the experimental conditions can be explained by the linear equation y = ax + b. As the value of 2 approaches 1, the shape of the multi-walled carbon nanotube 5 becomes more linear.

また、図２（ｂ）を参照して多層カーボンナノチューブ５の垂直配向性は多層カーボンナノチューブ５の下部基端５ａの位置と上部先端５ｂの位置との基板１表面に沿う水平方向差（Ｐ）と、多層カーボンナノチューブ５の上記下部基端５ａから上部先端５ｂまでの基板１表面からの高さ寸法（Ｑ）として、Ｖ＝Ｑ／Ｐを垂直配向性（Ｖ）とすることができる。多層カーボンナノチューブ５の下部基端５ａの基板表面からの高さはゼロである。そして、上記水平方向差（Ｐ）がゼロに近づくほど多層カーボンナノチューブ５は基板表面に対して垂直配向性をより有するようになる。   In addition, referring to FIG. 2B, the vertical orientation of the multi-walled carbon nanotube 5 is the horizontal difference (P) along the surface of the substrate 1 between the position of the lower base end 5a and the position of the upper end 5b of the multi-walled carbon nanotube 5. As a height dimension (Q) from the surface of the substrate 1 from the lower base end 5a to the upper front end 5b of the multi-walled carbon nanotube 5, V = Q / P can be set as the vertical orientation (V). The height of the lower base end 5a of the multi-walled carbon nanotube 5 from the substrate surface is zero. As the horizontal difference (P) approaches zero, the multi-walled carbon nanotube 5 has more vertical alignment with respect to the substrate surface.

図２（ｃ）を参照して実際のＳＥＭ写真等で多層カーボンナノチューブの形状の直線性と垂直配向性の有無を判定する指標を説明する。図２（ｃ）は多層カーボンナノチューブの集合構造の倍率３０ＫのＳＥＭ写真である。ただし、この判定の指標の説明に用いるＳＥＭ写真の倍率は一例である。また、このＳＥＭ写真中で垂直配向性の判定対象とする多層カーボンナノチューブを分かりやすくするうえでＳＥＭ写真中に記入した点線で示す。   With reference to FIG. 2C, an index for determining the presence / absence of linearity and vertical alignment of the shape of the multi-walled carbon nanotube will be described with an actual SEM photograph or the like. FIG. 2 (c) is an SEM photograph at a magnification of 30K of the aggregate structure of multi-walled carbon nanotubes. However, the magnification of the SEM photograph used for explanation of this determination index is an example. Moreover, in order to make it easy to understand the multi-walled carbon nanotube to be judged for vertical alignment in this SEM photograph, it is indicated by a dotted line written in the SEM photograph.

まず、形状の直線性の指標の場合、低倍率観察で垂直方向に成長していることが確認されている多層カーボンナノチューブを対象とし、その直線性が十分に確認できる倍率（例えば３０Ｋ）に拡大した例えば図２（ｃ）のＳＥＭ写真上の１μｍの範囲において、９０％以上の多層カーボンナノチューブが、決定係数Ｒ2が、０．９７０以上、１．０以下、好ましくは０．９８０超、１．０以下の条件を満たす場合、その多層カーボンナノチューブは形状の直線性を有すると判定することができる。ここで、Ｒ2とは、上記図２（ａ）で説明した、最小二乗法による直線近似式（ｙ＝ａｘ＋ｂ）における決定係数である。 First, in the case of the shape linearity index, the multi-walled carbon nanotubes that have been confirmed to grow in the vertical direction by low-magnification observation are expanded to a magnification (for example, 30K) at which the linearity can be sufficiently confirmed. For example, in the range of 1 μm on the SEM photograph of FIG. 2C, 90% or more of the multi-walled carbon nanotubes have a determination coefficient R 2 of 0.970 or more and 1.0 or less, preferably more than 0.980, When the condition of 0.0 or less is satisfied, it can be determined that the multi-walled carbon nanotube has linearity of shape. Here, R 2 is a determination coefficient in the linear approximation formula (y = ax + b) by the least square method described with reference to FIG.

垂直配向性の指標の場合、形状の直線性と同様、低倍率観察で垂直方向に成長していることが確認されている多層カーボンナノチューブを対象とし、その垂直配向性が十分に確認できる倍率（例えば３０Ｋ）に拡大した例えば図２（ｃ）のＳＥＭ写真上の１μｍの範囲において、９０％以上の多層カーボンナノチューブが、垂直配向性を示すＶが８以上、好ましくは９超の条件を満たす場合、その多層カーボンナノチューブは垂直配向性を有すると判定することができる。   In the case of the vertical alignment index, as with the linearity of the shape, the multi-walled carbon nanotubes that have been confirmed to grow in the vertical direction by low-magnification observation are targets for which the vertical alignment can be sufficiently confirmed ( For example, in the range of 1 μm on the SEM photograph of FIG. 2C expanded to 30 K), for example, 90% or more of the multi-walled carbon nanotubes satisfy the condition that V indicating vertical alignment is 8 or more, preferably more than 9 It can be determined that the multi-walled carbon nanotube has vertical alignment.

また、図２（ｂ）では理論的には多層カーボンナノチューブ５の下部基端５ａと上部先端５ｂで垂直配向性Ｖ＝Ｑ／Ｐとなるが、ＳＥＭ写真を用いた実測での垂直配向性を示すＶにおいては、図２（ｃ）のＳＥＭ写真中において例えば点線で示す多層カーボンナノチューブ５は、上記１μｍの範囲の下限を示す水平方向ラインＬ１と交わる位置ａと、上記１μｍの範囲の上限を示す水平方向ラインＬ２と交わる位置ｂとの水平方向の差がＰであり、多層カーボンナノチューブの両ラインＬ１，Ｌ２の垂直方向の長さが多層カーボンナノチューブの高さ寸法Ｑとなる。そして、Ｖは、ＳＥＭ写真中のＱ、Ｐを実測し、その実測した値からＱ／Ｐを演算することにより得ることができる。   Further, in FIG. 2B, the vertical orientation V = Q / P is theoretically obtained at the lower base end 5a and the upper end 5b of the multi-walled carbon nanotube 5, but the vertical orientation measured in the SEM photograph is shown. In V shown, in the SEM photograph of FIG. 2C, for example, the multi-walled carbon nanotube 5 indicated by a dotted line has a position a that intersects the horizontal line L1 indicating the lower limit of the 1 μm range and the upper limit of the 1 μm range. The horizontal difference from the position b intersecting the horizontal line L2 shown is P, and the vertical length of both lines L1, L2 of the multi-walled carbon nanotube is the height dimension Q of the multi-walled carbon nanotube. V can be obtained by actually measuring Q and P in the SEM photograph and calculating Q / P from the actually measured values.

実施の形態では複数の多層カーボンナノチューブ５が、形状の直線性と、基板表面に対する成長方向の垂直配向性とを備えることにより高密度に集合して成長し電子放出用材料として優れた多層カーボンナノチューブを提供することができる。   In the embodiment, a plurality of multi-walled carbon nanotubes 5 have a shape linearity and a vertical alignment in the growth direction with respect to the substrate surface, so that the multi-walled carbon nanotubes are grown as a high density and excellent as an electron emission material. Can be provided.

図３（ａ）に、基板１をシリコン基板、下地膜２をアルミニウム膜、触媒微粒子４１，４２，…，４ｎを鉄微粒子とし、アセチレンガス雰囲気中で７００℃、１０分間、２００Ｐａの減圧下で加熱する熱ＣＶＤ法の実施により成長した多層カーボンナノチューブ５の倍率２０ｋ（ｋは１０００）のＳＥＭ（走査型電子顕微鏡）写真を示し、図３（ｂ）に、さらに拡大した倍率１００ｋのＳＥＭ写真を示す。   In FIG. 3A, the substrate 1 is a silicon substrate, the base film 2 is an aluminum film, the catalyst fine particles 41, 42,..., 4n are iron fine particles, in an acetylene gas atmosphere at 700 ° C. for 10 minutes under a reduced pressure of 200 Pa. An SEM (scanning electron microscope) photograph of a magnification of 20 k (k is 1000) of the multi-walled carbon nanotube 5 grown by carrying out the thermal CVD method to be heated is shown. FIG. 3B shows a further enlarged SEM photograph of a magnification of 100 k. Show.

これらＳＥＭ写真では、多層カーボンナノチューブ５は図３（ａ）のＳＥＭ写真での観察ではその形状に直線性を有しかつ基板１表面に対する垂直配向性を有していることが示されている。   These SEM photographs show that the multi-walled carbon nanotubes 5 are linear in the shape and perpendicular to the surface of the substrate 1 as observed in the SEM photograph of FIG.

図３（ａ）のＳＥＭ写真で示す多層カーボンナノチューブに符号を付けると、符号５Ａは形状の直線性と垂直配向性とが有る多層カーボンナノチューブであり、符号５Ｂは直線性が無い多層カーボンナノチューブであり、符号５Ｃは垂直配向性が無い多層カーボンナノチューブである。図３（ａ）のＳＥＭ写真中で上記多層カーボンナノチューブ５Ｂ，５Ｃは垂直配向性が無いと見られるがこれは写真撮影時に際して垂直配向性が無くなったものであり実施の形態から除外されるものである。   When the multi-wall carbon nanotubes shown in the SEM photograph of FIG. 3 (a) are labeled, reference numeral 5A is a multi-wall carbon nanotube having linearity and vertical alignment, and reference numeral 5B is a multi-wall carbon nanotube having no linearity. And 5C is a multi-walled carbon nanotube having no vertical alignment. In the SEM photograph of FIG. 3 (a), the multi-walled carbon nanotubes 5B and 5C appear to have no vertical alignment, but this is one that has no vertical alignment at the time of photography and is excluded from the embodiment. It is.

実施の形態では、多層カーボンナノチューブ５ａの形状の直線性と垂直配向性とを共に有する。この場合、多層カーボンナノチューブ５Ａの形状はその全体が直線に近似することができる。また、垂直配向性は基板表面に概ね垂直配向している。   In the embodiment, both the linearity and the vertical alignment of the shape of the multi-walled carbon nanotube 5a are provided. In this case, the overall shape of the multi-walled carbon nanotube 5A can approximate a straight line. In addition, the vertical alignment is generally perpendicular to the substrate surface.

さらに図３（ａ）のＳＥＭ写真を拡大した図３（ｂ）のＳＥＭ写真でも多層カーボンナノチューブ５Ａは形状の直線性、垂直配向性とを共に有していることが示されている。   Further, the SEM photograph of FIG. 3B, which is an enlarged view of the SEM photograph of FIG. 3A, shows that the multi-walled carbon nanotube 5A has both linearity and vertical alignment of the shape.

図３（ｂ）のＳＥＭ写真で示す多層カーボンナノチューブにも上記と同様の符号を付け、多層カーボンナノチューブ５Ｂ，５Ｃは実施の形態から除外する。   The multi-layer carbon nanotubes shown in the SEM photograph of FIG. 3B are also given the same reference numerals as above, and the multi-wall carbon nanotubes 5B and 5C are excluded from the embodiment.

この多層カーボンナノチューブ５の密度を測定すると、９０（mｇ／ｃｍ3）というように高密度であった。これは、ＳＥＭ写真で示す多層カーボンナノチューブ５は形状の直線性と垂直配向性とを共に有する多層カーボンナノチューブが多いからと考えられる。 When the density of the multi-walled carbon nanotube 5 was measured, it was as high as 90 (mg / cm 3 ). This is probably because the multi-walled carbon nanotube 5 shown in the SEM photograph has many multi-walled carbon nanotubes having both linearity and vertical alignment of the shape.

図４（ａ）に上記ＳＥＭ写真で示した多層カーボンナノチューブ５の断面構造のＴＥＭ（透過型電子顕微鏡）写真、図４（ｂ）に図４（ａ）のＳＥＭ写真で示す多層カーボンナノチューブ５の素面構造を示す。このＴＥＭ写真で示すようにこの多層カーボンナノチューブ５は最内層の内径が３ｎｍ以上、８ｎｍ以下であり、かつ、最外層の外径が５ｎｍ以上、３５ｎｍ以下であり、層数が３以上、３５以下、であった。   4A shows a TEM (transmission electron microscope) photograph of the cross-sectional structure of the multi-walled carbon nanotube 5 shown in the SEM photograph, and FIG. 4B shows the multi-wall carbon nanotube 5 shown in the SEM photograph of FIG. 4A. The bare surface structure is shown. As shown in this TEM photograph, this multi-wall carbon nanotube 5 has an inner diameter of the innermost layer of 3 nm or more and 8 nm or less, an outer diameter of the outermost layer of 5 nm or more and 35 nm or less, and a number of layers of 3 or more and 35 or less. ,Met.

ＳＥＭ写真で示した多層カーボンナノチューブ５に対して図６のＴＧ（ＴｈｅｒｍｏＧｒａｖｉｍｅｔｒｙ）曲線による熱分析測定を実施した。   Thermal analysis measurement was performed on the multi-walled carbon nanotube 5 shown in the SEM photograph using a TG (ThermoGravity) curve in FIG.

図６に関して、熱分析測定に用いた装置はエスアイアイ・ナノテクノロジー株式会社製のＥＸＳＴＡＲ６０００ ＴＧ／ＤＴＡであり、熱分析測定条件は空気１００ｍｌ／分雰囲気下、１０℃／分にて９００℃まで昇温後１０分間保持する。   Regarding FIG. 6, the apparatus used for the thermal analysis measurement is EXSTAR6000 TG / DTA manufactured by SII Nano Technology Co., Ltd., and the thermal analysis measurement conditions are increased to 900 ° C. at 10 ° C./min in an atmosphere of 100 ml / min. Hold for 10 minutes after warming.

一般にカーボンは結晶性が低いと加熱に弱く、結晶性が高いと加熱に強くなる。図６において横軸は温度（Ｔ：℃）、縦軸は熱重量変化（ＴＧ：％）である。これは温度を上昇させていきつつ空気雰囲気下で多層カーボンナノチューブ５の重量変化を測定している。図６でＡは従来の多層カーボンナノチューブのＴＧ曲線であり、Ｂは本発明の多層カーボンナノチューブのＴＧ曲線である。従来の多層カーボンナノチューブは結晶性が低いため、ＴＧ曲線Ａで示すように温度が４５０℃付近から分解開始し、６３０℃付近で分解終了した。さらに従来の多層カーボンナノチューブでは残渣Ｃ（６２９．１℃でＴＧ＝６．７％）残った。これは従来の多層カーボンナノチューブが低純度であることを示している。   In general, carbon is weak against heating when the crystallinity is low, and strong against heating when the crystallinity is high. In FIG. 6, the horizontal axis represents temperature (T: ° C.), and the vertical axis represents thermogravimetric change (TG:%). This measures the weight change of the multi-walled carbon nanotubes 5 in an air atmosphere while increasing the temperature. In FIG. 6, A is a TG curve of the conventional multi-walled carbon nanotube, and B is a TG curve of the multi-walled carbon nanotube of the present invention. Since the conventional multi-walled carbon nanotube has low crystallinity, as shown by the TG curve A, the decomposition started at around 450 ° C. and ended at around 630 ° C. Further, in the conventional multi-walled carbon nanotube, residue C (TG = 6.7% at 629.1 ° C.) remained. This indicates that the conventional multi-walled carbon nanotube has low purity.

これに対して本発明の多層カーボンナノチューブ５は、ＴＧ曲線Ｂで示すように温度が６００℃付近から分解開始し、７６０〜７８０℃付近で分解終了して残渣（７６８．３℃でＴＧ＝−０．２％）が残らなかった。これは本発明の多層カーボンナノチューブ５が加熱に強く高結晶性であることを示している。また、分解終了して残渣が残らなかったことから高純度であることを示している。   On the other hand, the multi-walled carbon nanotube 5 of the present invention starts to decompose at a temperature of around 600 ° C. as shown by the TG curve B, ends at around 760 to 780 ° C., and remains (TG = − at 768.3 ° C.). 0.2%) did not remain. This indicates that the multi-walled carbon nanotube 5 of the present invention is highly resistant to heating and highly crystalline. Moreover, since the residue was not left after completion of the decomposition, it indicates high purity.

以上から本発明のカーボンナノチューブ５は高結晶性であることに加えて高純度であることが分かる。   From the above, it can be seen that the carbon nanotube 5 of the present invention has high purity in addition to high crystallinity.

本発明は、上述した実施の形態に限定されるものではなく、特許請求の範囲に記載した範囲内で、種々な変更ないしは変形を含むものである。   The present invention is not limited to the above-described embodiments, and includes various changes or modifications within the scope described in the claims.

図１は本発明の実施の形態に係る多層カーボンナノチューブの集合構造を示す断面イメージ図である。FIG. 1 is a cross-sectional image diagram showing an aggregate structure of multi-walled carbon nanotubes according to an embodiment of the present invention. 図２（ａ）は多層カーボンナノチューブの形状の直線性を説明するための図、図２（ｂ）は多層カーボンナノチューブの基板表面に対する成長方向の垂直配向性を説明するための図、図２（ｃ）は多層カーボンナノチューブの集合構造の倍率３０ＫのＳＥＭ写真である。2A is a diagram for explaining the linearity of the shape of the multi-walled carbon nanotube, FIG. 2B is a diagram for explaining the vertical orientation of the multi-walled carbon nanotube with respect to the substrate surface, and FIG. c) is an SEM photograph of the aggregate structure of multi-walled carbon nanotubes at a magnification of 30K. 図３（ａ）は実施の形態の多層カーボンナノチューブの集合構造の倍率２０ｋのＳＥＭ写真、図３（ｂ）は、実施の形態のカーボンナノチューブの集合構造の倍率１００ｋのＳＥＭ写真である。FIG. 3A is an SEM photograph of the aggregate structure of multi-walled carbon nanotubes of the embodiment at a magnification of 20 k, and FIG. 3B is an SEM photograph of the aggregate structure of the carbon nanotubes of the embodiment at a magnification of 100 k. 図４は実施の形態の多層カーボンナノチューブの集合構造内の１つの多層カーボンナノチューブのＴＥＭ写真である。FIG. 4 is a TEM photograph of one multi-walled carbon nanotube in the aggregate structure of the multi-walled carbon nanotube of the embodiment. 図５は従来の多層カーボンナノチューブと本発明に係る多層カーボンナノチューブとにおける温度変化に対する熱重量変化特性を示す図である。FIG. 5 is a graph showing thermogravimetric change characteristics with respect to temperature change in the conventional multi-walled carbon nanotube and the multi-walled carbon nanotube according to the present invention.

符号の説明Explanation of symbols

１ 基板
２ 下地膜
４１，４２，４ｎ 触媒微粒子
５，５１，５２，５ｎ 多層カーボンナノチューブ 1 Substrate 2 Base film 41, 42, 4n Catalyst fine particles 5, 51, 52, 5n Multi-walled carbon nanotube

Claims (5)

基板表面上の触媒微粒子の作用で成長する複数の多層カーボンナノチューブの集合構造であって、上記多層カーボンナノチューブそれぞれが、形状の直線性と基板表面に対する垂直配向性とを備えて５０（mｇ／ｃｍ3）以上の密度で集合している、ことを特徴とする多層カーボンナノチューブの集合構造。 An aggregate structure of a plurality of multi-walled carbon nanotubes grown by the action of catalyst fine particles on a substrate surface, each of the multi-walled carbon nanotubes having a shape linearity and a vertical orientation with respect to the substrate surface of 50 (mg / cm 3 ) An aggregate structure of multi-walled carbon nanotubes characterized by being aggregated at the above density. 上記多層カーボンナノチューブは、最内層の内径が３ｎｍ以上、８ｎｍ以下であり、かつ、最外層の外径が５ｎｍ以上、３５ｎｍ以下である、ことを特徴とする請求項１に記載の多層カーボンナノチューブの集合構造。   The multi-wall carbon nanotube according to claim 1, wherein the inner diameter of the innermost layer is 3 nm or more and 8 nm or less, and the outer diameter of the outermost layer is 5 nm or more and 35 nm or less. Aggregate structure. 上記多層カーボンナノチューブは、層数が３以上、３５以下である、ことを特徴とする請求項２に記載の多層カーボンナノチューブの集合構造。   The multi-walled carbon nanotube aggregate structure according to claim 2, wherein the number of the multi-walled carbon nanotubes is 3 or more and 35 or less. 上記多層カーボンナノチューブは、空気中における熱分解開始温度が５００℃以上である、ことを特徴とする請求項１に記載の多層カーボンナノチューブの集合構造。   The aggregate structure of multi-walled carbon nanotubes according to claim 1, wherein the multi-walled carbon nanotubes have a thermal decomposition start temperature in air of 500 ° C or higher. 上記多層カーボンナノチューブは、空気中における９００℃熱分解後の残渣が１％以下である、ことを特徴とする請求項１に記載の多層カーボンナノチューブの集合構造。   The aggregate structure of multi-walled carbon nanotubes according to claim 1, wherein the multi-walled carbon nanotubes have a residue of 1% or less after thermal decomposition at 900 ° C in air.
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