JP5644537B2 - Carbon nanotube aggregate and method for producing the same - Google Patents
Carbon nanotube aggregate and method for producing the same Download PDFInfo
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本発明は、多数のカーボンナノチューブからなる紡績糸やシートであるカーボンナノチューブ集合体、及び、カーボンナノチューブ集合体の製造方法に関するものである。 The present invention relates to a carbon nanotube aggregate that is a spun yarn or sheet composed of a large number of carbon nanotubes, and a method for producing the carbon nanotube aggregate.
カーボンナノチューブ（以下ＣＮＴと記すことがある）は、１９９１年に発見された新しい炭素材料である。このＣＮＴは、炭素原子がｓｐ２結合した六員環のネットワークを有する黒鉛シートが円筒状に閉じた構造を有する、直径数ｎｍ〜数十ｎｍのチューブ状の炭素素材である。 Carbon nanotubes (hereinafter sometimes referred to as CNT) are new carbon materials discovered in 1991. This CNT is a tubular carbon material having a diameter of several nanometers to several tens of nanometers having a structure in which a graphite sheet having a six-membered ring network in which carbon atoms are sp2 bonded is cylindrically closed.
ＣＮＴは非常に安定した化学構造を有し、ＣＮＴを構成する六方格子の螺旋度によって、良導体にも半導体にもなるなど、様々な特性を有することが確認されている。また、ＣＮＴは、電気的特性、熱伝導性、及び機械的強度に優れており、これらの特徴を活かして、現在では、熱機器分野、電気、電子機器分野などへの応用研究が盛んに行われている。 CNT has a very stable chemical structure, and it has been confirmed that it has various characteristics such as being a good conductor and a semiconductor depending on the helical degree of the hexagonal lattice constituting the CNT. In addition, CNTs are excellent in electrical characteristics, thermal conductivity, and mechanical strength. Utilizing these characteristics, CNTs are currently actively researched in the fields of thermal equipment, electricity, and electronic equipment. It has been broken.
ＣＮＴは、上記のとおり、微細な構造を有するため、そのままでは、取り扱い性や加工性が悪い。このため、肉眼で確認しながら取り扱うことが可能な大きさのＣＮＴの集合体を製造することが試みられている。このＣＮＴの集合体としては、例えば、複数のＣＮＴから成るＣＮＴ紡績糸が挙げられる。さらに、このＣＮＴ紡績糸を用いて、ＣＮＴの織布やシートを製造することができる。（特許文献１〜５参照）
これらの従来技術としては、例えば図１０（ａ）に示す様に、基板上にＣＮＴを合成するＦｅやＣｏ等の触媒金属を用意し、化学気相合成法によって基板に垂直に配向したＣＮＴからなる膜、詳しくは立設されたＣＴＮが密集して平面状に広がるＣＮＴ垂直配向膜を作製し、その膜から紡績することにより紡績糸を製造する方法が知られている。
Since CNT has a fine structure as described above, handling and workability are poor as it is. For this reason, attempts have been made to produce an aggregate of CNTs that can be handled with the naked eye. An example of the aggregate of CNTs is a CNT spun yarn composed of a plurality of CNTs. Furthermore, using this CNT spun yarn, a CNT woven fabric or sheet can be produced. (See Patent Documents 1 to 5)
As these prior arts, for example, as shown in FIG. 10A, a catalyst metal such as Fe or Co for synthesizing CNTs is prepared on a substrate, and the CNTs are aligned perpendicularly to the substrate by a chemical vapor synthesis method. In particular, there is known a method for producing a spun yarn by producing a CNT vertical alignment film in which the standing CTNs are densely spread and spread in a planar shape, and spinning from the film.
しかしながら、上述した従来技術では、図１０（ｂ）に示す様に、ＣＮＴは合成初期には方向が乱れた状態で成長を開始し、その後、（基板面には垂直方向しか自由度が無いため）基板の垂直方向に成長するので、下記の様な問題があった。 However, in the above-described prior art, as shown in FIG. 10 (b), CNT starts growing in a disordered direction at the initial stage of synthesis, and thereafter (because the substrate surface has a degree of freedom only in the vertical direction). ) Since it grows in the vertical direction of the substrate, there were the following problems.
即ち、ＣＮＴが密集して成長したＣＮＴ垂直配向膜の上部（図１１（ａ）参照）は、その中間部（図１１（ｂ）参照）に比べて、方向が乱れた結晶欠陥の多いＣＮＴから構成されており、一部にはＣＮＴ先端成長により先端部に触媒金属を含んだもの、さらには、成長初期に基板から剥がれた触媒金属も付着している（図１１（ａ）の左下の写真参照）。なお、図１１は、倍率３万倍の電子顕微鏡写真であり、このうち、図１１（ａ）の左下の写真は要部を３０万倍に拡大した電子顕微鏡写真である。 That is, the upper part of the CNT vertical alignment film (see FIG. 11A) where CNTs are densely grown grows from a CNT with many crystal defects whose directions are disordered compared to the middle part (see FIG. 11B). Some of them contain catalyst metal at the tip due to CNT tip growth, and further, catalyst metal that has been peeled off from the substrate in the early stage of growth is attached (lower left photo in FIG. 11A). reference). FIG. 11 is an electron micrograph at a magnification of 30,000 times. Of these, the lower left photo in FIG. 11 (a) is an electron micrograph in which the main part is magnified 300,000 times.
そのため、この様な構造のＣＮＴ垂直配向膜から製造したＣＮＴ紡績糸には、触媒金属が混ざるとともに欠陥の多いＣＮＴ部位を含んでおり、その結果、このＣＮＴ紡績糸で各種の製品（例えばＣＮＴ紡績糸で編んだ織布など）を製造した場合には、熱伝導性や電気伝導度が所望の特性とは異なるという問題や、機械的強度が低下するという問題があった。 For this reason, the CNT spun yarn produced from the CNT vertical alignment film having such a structure contains a CNT portion having a lot of defects as well as mixed with a catalytic metal. As a result, various products (for example, CNT spun yarn) When a woven fabric knitted with yarn is manufactured, there are problems that thermal conductivity and electrical conductivity are different from desired characteristics, and mechanical strength is lowered.
本発明は、前記課題を解決するためになされたものであり、その目的は、触媒金属の含有を抑制し、結晶性の高い部位のＣＮＴから構成されるＣＮＴ集合体及びその製造方法を提供することにある。 The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a CNT aggregate composed of CNTs having a high crystallinity and containing a catalytic metal, and a method for producing the same. There is.
（１）請求項１の発明は、化学気相合成法によって、基板表面にＣＮＴ垂直配向膜を形成し、そのＣＮＴ垂直配向膜からＣＮＴ集合体を製造する方法において、前記ＣＮＴ集合体は、多数のＣＮＴにより形成されたＣＮＴ紡績糸又はＣＮＴシートであり、前記ＣＮＴ垂直配向膜を形成した後に、気相エッチングによって、前記ＣＮＴ垂直配向膜の上部を除去することを特徴とする。 (1) The invention according to claim 1, by chemical vapor phase synthesis, the CNT vertical alignment film formed on the substrate surface, a method of manufacturing a CNT aggregate from the CNT vertical alignment film, the CNT aggregate, many A CNT spun yarn or a CNT sheet formed of CNT, wherein the upper part of the CNT vertical alignment film is removed by vapor phase etching after the CNT vertical alignment film is formed.
本発明は、基板上に形成したＣＮＴ垂直配向膜の上部を気相エッチングによって除去するので、ＣＮＴ垂直配向膜の上部の結晶欠陥を多く含む部分のＣＮＴや、先端に触媒金属を含む部分のＣＮＴ、さらには、ＣＮＴ垂直配向膜の上部に付着した触媒金属を効果的に除去することができる。 In the present invention, the upper part of the CNT vertical alignment film formed on the substrate is removed by gas phase etching, so that the CNT in the part containing many crystal defects on the upper part of the CNT vertical alignment film and the CNT in the part containing the catalyst metal at the tip. Furthermore, the catalyst metal adhering to the upper part of the CNT vertical alignment film can be effectively removed.
従って、この欠陥の多い上部が除去されたＣＮＴ垂直配向膜には、触媒金属が殆ど含まれず、しかもＣＮＴの形状（向きや太さ）が揃ったものとなるので、ＣＮＴ垂直配向膜から、（多数のＣＮＴが紡績によって形成された）ＣＮＴ紡績糸や（多数のＣＮＴがシート状に配置された）ＣＮＴシートであるＣＮＴ集合体を製造すると、所望の熱伝導性や電気伝導度を得ることができるとともに、高い機械的強度も得ることができる。
なお、ＣＮＴ紡績糸から織布などを製造することができる。
Therefore, the CNT vertical alignment film top is removed lot of this defect, the catalytic metal is not included little, yet since those having a uniform shape of the CNT (orientation and thickness), the CNT vertical alignment film ( When a CNT aggregate, which is a CNT spun yarn (a large number of CNTs are formed by spinning) or a CNT sheet (a large number of CNTs are arranged in a sheet form) , desired thermal conductivity and electrical conductivity can be obtained. In addition, high mechanical strength can be obtained.
In addition, a woven fabric etc. can be manufactured from a CNT spun yarn.
（２）請求項２の発明では、前記気相エッチングの際に、前記基板上の前記ＣＮＴ垂直配向膜を下方、斜め下方、又は横方向に向けて配置することを特徴とする。
本発明では、ＣＮＴ垂直配向膜を下方や斜め下方や横方向に向けるので、ＣＮＴ垂直配向膜の上部を気相エッチングによって除去した際に、除去した部分に付着していた触媒金属を、重力によって効果的に下方に脱落させることができる。
(2) The invention of claim 2 is characterized in that the CNT vertical alignment film on the substrate is disposed downward, obliquely downward, or laterally during the vapor phase etching.
In the present invention, since the CNT vertical alignment film is directed downward, obliquely downward, or laterally, when the upper portion of the CNT vertical alignment film is removed by gas phase etching, the catalyst metal adhering to the removed portion is removed by gravity. It can drop off effectively.
これにより、気相エッチングの際に、触媒金属がＣＮＴ垂直配向膜に再付着することを防止できる。
（３）請求項３の発明では、前記ＣＮＴ垂直配向膜を構成するＣＮＴの先端を開口する程度に、前記気相エッチングを行うことを特徴とする。
Thereby, it is possible to prevent the catalyst metal from reattaching to the CNT vertical alignment film during the vapor phase etching.
(3) The invention of claim 3 is characterized in that the vapor phase etching is performed to such an extent that the tips of the CNTs constituting the CNT vertical alignment film are opened.
ＣＮＴは中空の糸状体であるので、基板からＣＮＴを分離する際には、ＣＮＴの基板側の端部が開口する。従って、本発明の様に、気相エッチングにより先端側を開口する場合には、基板からＣＮＴを分離する際に、ＣＮＴの両側が開口した中空のパイプ状にすることができる。 Since the CNT is a hollow filamentous body, when the CNT is separated from the substrate, the end of the CNT on the substrate side opens. Therefore, when the front end side is opened by vapor-phase etching as in the present invention, when separating the CNT from the substrate, it can be formed into a hollow pipe shape in which both sides of the CNT are opened.
従って、この両端が開口したＣＮＴを用いて（例えばＣＮＴ紡績糸の様な）ＣＮＴ集合体を製造する場合には、ＣＮＴ集合体の（有効に利用できる）表面積を大きくすることができる。 Therefore, when a CNT aggregate (such as a CNT spun yarn) is produced using CNTs having both ends opened, the surface area (effectively usable) of the CNT aggregate can be increased.
なお、この（有効に利用できる）表面積とは、例えばＣＮＴ集合体を吸着剤やキャパシタ電極として利用する場合の様に、ＣＮＴの内側や外側に気体や液体を導入して反応を行う場合に、実質的に導入や排出される気体や液体に接触できる表面積である。つまり、一方のみが開口しているＣＮＴの場合には、細径なチューブの内側に気体や液体は殆ど流れ込まないので、実質的には、ＣＮＴの外側表面が有効に利用できる表面積となる。 The surface area (which can be used effectively) is, for example, when a reaction is performed by introducing a gas or a liquid inside or outside the CNT, such as when the CNT aggregate is used as an adsorbent or a capacitor electrode. It is the surface area that can substantially contact the gas or liquid introduced or discharged. That is, in the case of a CNT that is open only on one side, almost no gas or liquid flows into the inside of the thin tube, so that the outer surface of the CNT effectively becomes a surface area that can be used effectively.
また、ＣＮＴの先端が開口する程度としては、ＣＮＴ垂直配向膜の表面からＣＮＴ直径長さ以上除去すればよく、この程度除去すれば、ＣＮＴ垂直配向膜における各ＣＮＴの上部は、通常、８０％以上開口する。なお、開口の程度としては、多いほど良いが、９０％以上が好ましい。 Further, the extent to which the tip of the CNT is opened may be removed from the surface of the CNT vertical alignment film by a length equal to or longer than the CNT diameter length. Open above. Note that the degree of opening is preferably as large as possible, but 90% or more is preferable.
（４）請求項４の発明では、前記気相エッチングは、酸素プラズマによるエッチングであることを特徴とする。
本発明は、好ましい気相エッチングを例示したものである。本発明者らの実験によれば、酸素プラズマによるエッチングでＣＮＴ垂直配向膜集合体の上部を除去したものから、好適にＣＮＴ紡績糸を製造することができた。
(4) The invention of claim 4 is characterized in that the gas phase etching is etching by oxygen plasma.
The present invention illustrates a preferred vapor phase etch. According to the experiments by the present inventors, CNT spun yarns could be suitably produced from those obtained by removing the upper part of the CNT vertical alignment film aggregate by etching with oxygen plasma.
なお、酸素プラズマによるエッチング以外の方法としては、例えば酸素雰囲気下での紫外線照射やレーザー光線による切断が考えられる。
（５）請求項５の発明では、前記ＣＮＴ垂直配向膜の平面方向における端部から、前記多数のＣＮＴを前記平面方向に沿って引き出すことにより、前記ＣＮＴ集合体を形成することを特徴とする。
As a method other than etching using oxygen plasma, for example, ultraviolet irradiation in an oxygen atmosphere or cutting with a laser beam can be considered.
(5) The invention of claim 5 is characterized in that the CNT aggregate is formed by pulling out the CNTs along the planar direction from an end in the planar direction of the CNT vertical alignment film. .
この製造方法によって、ＣＮＴ紡績糸又はＣＮＴシートを製造することができる。
（６）請求項６の発明は、多数のＣＮＴが密集した集合体であるＣＮＴ集合体において、前記ＣＮＴ集合体は、多数のＣＮＴにより形成されたＣＮＴ紡績糸又はＣＮＴシートであり、前記カーボンナノチューブは、軸方向の両端が開口した構造を有することを特徴とする。
By this production method, a CNT spun yarn or a CNT sheet can be produced.
(6) The invention of claim 6 is a CNT aggregate that is an aggregate in which a large number of CNTs are densely packed, wherein the CNT aggregate is a CNT spun yarn or a CNT sheet formed by a large number of CNTs, and the carbon nanotubes Has a structure in which both ends in the axial direction are open.
本発明のＣＮＴ集合体は、両端が開口したＣＮＴが集合したものであるので、その（有効に利用できる）表面積は、従来の（先端側が閉塞した）ＣＮＴからなるＣＮＴ集合体より大きい。 Since the CNT aggregate of the present invention is a collection of CNTs that are open at both ends, the surface area (which can be used effectively) is larger than that of conventional CNT aggregates (closed at the tip side).
従って、この様な構造のＣＮＴ集合体は、有効な表面積が多いので、気体の吸着や電荷の蓄積が増大する効果がある。
ここで、ＣＮＴ集合体を構成するＣＮＴは、全てのＣＮＴの両端が開口していることが望ましいが、両端が開口しているＣＮＴの割合は、少なくとも８０％以上、更に好ましくは９０％以上であればよい。
Accordingly, since the CNT aggregate having such a structure has a large effective surface area, there is an effect of increasing gas adsorption and charge accumulation.
Here, the CNTs constituting the CNT aggregate are desirably open at both ends of all CNTs, but the ratio of CNTs open at both ends is at least 80% or more, more preferably 90% or more. I just need it.
なお、このＣＮＴ集合体として、ＣＮＴの軸方向が所定方向（特に一定方向）に揃ったものが好ましい。例えばＣＮＴ紡績糸においては、各ＣＮＴは螺旋方向に撚る方向が揃っており、ＣＮＴ紡績糸全体としては、軸方向に揃っている。 In addition, as this CNT aggregate, one in which the axial direction of the CNTs is aligned in a predetermined direction (particularly a constant direction) is preferable. For example, in a CNT spun yarn, the CNTs are twisted in the spiral direction, and the entire CNT spun yarn is aligned in the axial direction.
（７）請求項７の発明では、前記ＣＮＴ集合体は、前記請求項２〜５のいずれか１項に記載の製造方法により製造されたものであることを特徴とする。 (7) In the invention of claim 7, wherein the CNT aggregate, you wherein those produced by the production method according to any one of claims 2-5.
次に、本発明のＣＮＴ集合体及びその製造方法ついて、図面に基づいて説明する。 Next, the CNT aggregate of the present invention and the manufacturing method thereof will be described with reference to the drawings.
ここでは、ＣＮＴが多数集合したＣＮＴ集合体としてＣＮＴ紡績糸を例に挙げて説明する。
ａ）以下に、本実施例のＣＮＴ紡績糸の製造方法について説明する。
Here, a CNT spun yarn will be described as an example of a CNT aggregate in which a large number of CNTs are aggregated.
a) Hereinafter, a method for producing the CNT spun yarn of this example will be described.
(1)＜ＣＮＴを形成するための基板を作製する工程＞
まず、直径６インチ、厚さ６５０μｍのＰ型シリコン基板を熱酸化して、その表面に厚さ１００ｎｍの酸化膜を形成した。酸化膜の厚みは、走査型電子顕微鏡を用いて測定した。
(1) <Process for producing a substrate for forming CNT>
First, a P-type silicon substrate having a diameter of 6 inches and a thickness of 650 μm was thermally oxidized to form an oxide film having a thickness of 100 nm on the surface. The thickness of the oxide film was measured using a scanning electron microscope.
次に、スパッタリング装置を用いて、基板の表面（熱酸化膜上）に、Ｆｅ−Ａｌからなる触媒金属層を形成した。例えば、組成比Ｆｅ／Ａｌ＝０．５８のＦｅ−Ａｌ（合金）からなる膜厚が３．０ｎｍの触媒金属層を形成した。 Next, a catalytic metal layer made of Fe—Al was formed on the surface of the substrate (on the thermal oxide film) using a sputtering apparatus. For example, a catalytic metal layer having a film thickness of 3.0 nm made of Fe—Al (alloy) with a composition ratio of Fe / Al = 0.58 was formed.
なお、この触媒金属層の形成の際には、特願２０１０−１６４１１８号に開示されているように、例えばＡｌのターゲットの上にＦｅのターゲットを乗せ、それらの面積比を変えることにより、Ｆｅ−Ａｌ層の組成比を調整した。また、膜厚は、スパッタリングの実施時間により調整した。 In forming the catalyst metal layer, as disclosed in Japanese Patent Application No. 2010-164118, for example, an Fe target is placed on an Al target, and the area ratio thereof is changed, thereby changing Fe area. -The composition ratio of the Al layer was adjusted. The film thickness was adjusted according to the sputtering time.
(2)＜触媒金属層を形成した基板上にＣＮＴを形成する工程＞
まず、触媒金属層を形成した基板を電気炉（図示せず）に挿入し、電気炉内に、水蒸気、アルゴン、及び水素を流した。アルゴンの流量は３００ｃｃ／ｍｉｎとし、水素の流量は５０ｃｃ／ｍｉｎとし、水蒸気の流量は、電気炉から出たＡｒガス中に占める水蒸気濃度が６０ｐｐｍとなる量とした。
(2) <Step of forming CNTs on a substrate on which a catalytic metal layer is formed>
First, the substrate on which the catalytic metal layer was formed was inserted into an electric furnace (not shown), and water vapor, argon, and hydrogen were allowed to flow through the electric furnace. The flow rate of argon was 300 cc / min, the flow rate of hydrogen was 50 cc / min, and the flow rate of water vapor was such that the water vapor concentration in the Ar gas from the electric furnace was 60 ppm.
その状態で電気炉内を昇温してゆき、ＣＮＴ合成温度（７００℃）に達した後、電気炉内にエチレンガスを１０ｃｃ／ｍｉｎの流量で流し、基板上にＣＮＴを合成した。合成時間は１０分間とした。 In this state, the temperature in the electric furnace was raised, and after reaching the CNT synthesis temperature (700 ° C.), ethylene gas was flowed into the electric furnace at a flow rate of 10 cc / min to synthesize CNTs on the substrate. The synthesis time was 10 minutes.
合成終了後、電子顕微鏡で基板上を観察したところ、基板上にて全面にわたりＣＮＴが合成され、ＣＮＴ垂直配向膜が形成されていることが確認できた。つまり、合成されたＣＮＴは、その一端が基板に固定されており、基板に対して垂直方向に均一に配向して、全体として膜状となっていた。 After completion of the synthesis, the surface of the substrate was observed with an electron microscope, and it was confirmed that CNT was synthesized over the entire surface of the substrate and a CNT vertical alignment film was formed. That is, one end of the synthesized CNT was fixed to the substrate, and the CNT was uniformly oriented in the vertical direction with respect to the substrate to form a film as a whole.
また、個々のＣＮＴの直径は１０〜３０ｎｍ程度であり、ＣＮＴの長さはほぼ揃っており平均で約２００μｍであった。なお、ＣＮＴの長さは、約１００〜８００μｍの範囲で、合成時間等により適宜調節が可能である。 Moreover, the diameter of each CNT was about 10-30 nm, and the length of CNT was substantially uniform and it was about 200 micrometers on average. In addition, the length of CNT can be suitably adjusted with the synthesis time etc. in the range of about 100-800 micrometers.
このＣＮＴ垂直配向膜は、前記図１１（ａ）の写真及び図１（ａ）に模式的に示す様に、その上部のＣＮＴの方向は乱れており、上部の各所に触媒金属が含まれていた。
(3)＜ＣＮＴ垂直配向膜のエッチングの工程＞
次に、上述した様にして形成されたＣＮＴ垂直配向膜の上部を、酸素プラズマエッチング（気相エッチング：ドライエッチング）により除去した。
As shown schematically in the photograph of FIG. 11 (a) and FIG. 1 (a), this CNT vertical alignment film is disordered in the direction of the CNTs on the top, and contains catalytic metals in various places on the top. It was.
(3) <CNT vertical alignment film etching process>
Next, the upper part of the CNT vertical alignment film formed as described above was removed by oxygen plasma etching (vapor phase etching: dry etching).
具体的には、ＣＮＴ垂直配向膜が形成された基板を、図２に示す様に、酸素プラズマエッチング装置（日立ハイテクノジーズ製プラズマクリーナＭ１０２０）１の反応室３内に入れた。このとき、ＣＮＴ垂直配向膜が下方に向く様に配置した。 Specifically, the substrate on which the CNT vertical alignment film was formed was placed in a reaction chamber 3 of an oxygen plasma etching apparatus (Plasma Cleaner M1020 manufactured by Hitachi High-Technologies) 1 as shown in FIG. At this time, the CNT vertical alignment film was disposed so as to face downward.
そして、酸素プラズマエッチング装置１の反応室３内を真空状態とした後に、アルゴンで２０体積％に希釈した酸素を流し、真空度を１０ｍｔｏｒｒとした後、１３．５６ＭＨｚの周波数で、３００Ｗのマイクロ波を投入し、４分間エッチングを行った。 Then, after the inside of the reaction chamber 3 of the oxygen plasma etching apparatus 1 is evacuated, oxygen diluted to 20% by volume with argon is flowed, the degree of vacuum is 10 mtorr, and a microwave of 300 W at a frequency of 13.56 MHz. And etching was performed for 4 minutes.
この酸素プラズマエッチングによって、ＣＮＴの上部（先端部分）では、ＣＮＴを構成するカーボンと酸素とが反応してＣＯやＣＯ2の気体となって揮散する。
これにより、図１（ｂ）に模式的に示す様に、ＣＮＴ垂直配向膜の上部が２０μｍ程度除去された。このＣＮＴ垂直配向膜の上部を上方から撮影した写真を図３に示すが、ＣＮＴ垂直配向膜の上部のＣＮＴの乱れた部分（欠陥部分）がきれいに除去されていた。なお、図３は倍率５千倍の電子顕微鏡写真であり、このうち、図３の左下の写真は要部を１０万倍に拡大した電子顕微鏡写真である。
By this oxygen plasma etching, carbon and oxygen constituting the CNT react with each other and volatilize as CO or CO 2 gas at the upper portion (tip portion) of the CNT.
Thereby, as schematically shown in FIG. 1B, about 20 μm of the upper portion of the CNT vertical alignment film was removed. A photograph of the upper part of the CNT vertical alignment film taken from above is shown in FIG. 3. The CNT disordered part (defect part) on the upper part of the CNT vertical alignment film was clearly removed. Note that FIG. 3 is an electron micrograph at a magnification of 5,000 times. Among these, the lower left photo in FIG.
そして、このＣＮＴの上部の揮散によって、ＣＮＴに保持されていた触媒金属は脱落することになるが、上述した様に、ＣＮＴ垂直配向膜は下方に向いているので、触媒金属は重力によって下方に落下して、ＣＮＴ垂直配向膜から好適に取り除かれる。 The catalytic metal held on the CNTs drops off due to the volatilization of the upper part of the CNTs. However, as described above, since the CNT vertical alignment film faces downward, the catalytic metals move downward due to gravity. It falls and is suitably removed from the CNT vertical alignment film.
また、各ＣＮＴは、図４（ａ）に示す様に、先端が閉じた中空の糸状体であるので、その先端が酸素プラズマエッチングによって除去されることにより、図４（ｂ）に示す様に、先端が開口した状態となる。なお、後述する様に、ＣＮＴが基板から分離することにより、図４（ｃ）に示す様に、ＣＮＴは、先端側と後端側の両側が開口したパイプ状となる。 Further, each CNT is a hollow filamentous body having a closed tip as shown in FIG. 4A, so that the tip is removed by oxygen plasma etching, as shown in FIG. 4B. The tip is open. As will be described later, when the CNTs are separated from the substrate, the CNTs are formed in a pipe shape that is open at both the front end side and the rear end side, as shown in FIG.
(4)＜ＣＮＴ紡績糸の形成工程＞
次に、図５及び図６に示すように、基板上のＣＮＴ垂直配向膜の端部（基板に沿った帯状の端部）に粘着テープを貼り付けて、ＣＮＴを基板表面に沿って引き出すとともに、１方向に回転させることにより、図７に示す様な多数のＣＮＴが撚りあわされたＣＮＴ紡績糸を作製した。なお、図５は、倍率１万倍の電子顕微鏡写真である。
(4) <CNT spinning yarn forming process>
Next, as shown in FIGS. 5 and 6, an adhesive tape is applied to the end of the CNT vertical alignment film on the substrate (a strip-shaped end along the substrate), and the CNT is pulled out along the substrate surface. By rotating in one direction, a CNT spun yarn in which many CNTs were twisted as shown in FIG. 7 was produced. FIG. 5 is an electron micrograph at a magnification of 10,000.
この様にして作製されたＣＮＴ紡績糸においては、各ＣＮＴは同様な方向（捻られながら螺旋状に伸びている方向）に伸びているので、その両端の開口も同様な方向に沿って開口していることになる。 In the CNT spun yarn produced in this way, each CNT extends in the same direction (the direction extending in a spiral while being twisted), so the openings at both ends also open along the same direction. Will be.
その後、特許第４００３４７６号公報に記載の様に、ＣＮＴ紡績糸の形態を安定化する処理を行った。具体的には、ＣＮＴ紡績糸に、例えばエタノール等の有機溶媒を加えた後に、自然乾燥させた。 Thereafter, as described in Japanese Patent No. 4003476, a treatment for stabilizing the form of the CNT spun yarn was performed. Specifically, an organic solvent such as ethanol was added to the CNT spun yarn and then naturally dried.
これによって、形態が安定したＣＮＴ紡績糸が得られた。
ｂ）この様に、本実施例では、基板上に形成したＣＮＴ垂直配向膜の上部を気相エッチングによって除去するので、ＣＮＴ垂直配向膜の上部の結晶欠陥を多く含むＣＮＴ部分や、ＣＮＴ垂直配向膜の上部に付着した触媒金属を効果的に除去することができる。
As a result, a CNT spun yarn having a stable form was obtained.
b) As described above, in this embodiment, since the upper part of the CNT vertical alignment film formed on the substrate is removed by vapor phase etching, the CNT portion including many crystal defects on the CNT vertical alignment film, and the CNT vertical alignment The catalytic metal adhering to the upper part of the membrane can be effectively removed.
従って、この上部が除去されたＣＮＴ垂直配向膜には、触媒金属が殆ど含まれず、しかも結晶性の良いＣＮＴからなるので、ＣＮＴ垂直配向膜からＣＮＴ紡績糸を製造すると、所望の熱伝導性や電気伝導度を得ることができるとともに、高い機械的強度も得ることができる。 Accordingly, the CNT vertical alignment film from which the upper portion is removed contains almost no catalytic metal and is made of CNT having good crystallinity. Therefore, when a CNT spun yarn is manufactured from the CNT vertical alignment film, desired thermal conductivity and Electrical conductivity can be obtained, and high mechanical strength can also be obtained.
また、本実施例では、酸素プラズマエッチングの際に、基板をＣＮＴ垂直配向膜を下方に向けて配置するので、ＣＮＴ垂直配向膜の上部に付着していた触媒金属を効果的に下方に脱落させることができる。これにより、触媒金属がＣＮＴ垂直配向膜に再付着することを防止できる。 In this embodiment, the substrate is placed with the CNT vertical alignment film facing downward during the oxygen plasma etching, so that the catalytic metal adhering to the upper part of the CNT vertical alignment film is effectively dropped downward. be able to. This can prevent the catalyst metal from reattaching to the CNT vertical alignment film.
更に、本実施例では、酸素プラズマエッチングによって、ＣＮＴ垂直配向膜の上部を除去することにより、各ＣＮＴの先端を開口するので、ＣＮＴ垂直配向膜からＣＮＴを分離する際に、ＣＮＴの両側が開口したパイプ状にすることができる。 Further, in this embodiment, the top of each CNT is opened by removing the upper part of the CNT vertical alignment film by oxygen plasma etching, so that both sides of the CNT are opened when separating the CNT from the CNT vertical alignment film. It can be made into a pipe shape.
従って、この両端が開口したパイプ状のＣＮＴを用いてＣＮＴ紡績糸を製造する場合には、ＣＮＴ紡績糸の（有効に利用できる）表面積を大きくすることができる。この有効な表面積が大きなＣＮＴ紡績糸を用いて例えば織布等の製品を製造すると、ガス吸着量や電荷の蓄積量を増大できる利点がある。 Therefore, when producing CNT spun yarn using the pipe-like CNT having both ends opened, the surface area (effectively usable) of the CNT spun yarn can be increased. When a product such as a woven fabric is manufactured using the CNT spun yarn having a large effective surface area, there is an advantage that the gas adsorption amount and the charge accumulation amount can be increased.
次に、実施例２について説明するが、前記実施例１と同様な内容の説明は省略する。
本実施例は、ＣＮＴ集合体としてＣＮＴシートを製造する方法に関するものである。
本実施例では、基板上にＣＮＴ垂直配向膜を形成するまでは、前記実施例１と同様である。
Next, the second embodiment will be described, but the description of the same contents as the first embodiment will be omitted.
The present embodiment relates to a method for producing a CNT sheet as a CNT aggregate.
This example is the same as Example 1 until the CNT vertical alignment film is formed on the substrate.
その後、図８（ａ）に示す様に、基板上のＣＮＴ垂直配向膜の端部に粘着テープを貼り付けて、ＣＮＴを基板表面に沿ってシート状に引き出し、ＣＮＴシートを作製した。
更に、図８（ｂ）に示す様に、ＣＮＴシートの一方の側に基板フィルムを貼り付けて、ＣＮＴ積層シートを作製した。
Thereafter, as shown in FIG. 8A, an adhesive tape was attached to the end of the CNT vertical alignment film on the substrate, and the CNTs were drawn out into a sheet shape along the substrate surface to produce a CNT sheet.
Furthermore, as shown in FIG. 8B, a substrate film was attached to one side of the CNT sheet to produce a CNT laminated sheet.
本実施例でも、前記実施例１と同様な効果を奏する。
尚、本発明は前記実施例になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。
This embodiment also has the same effect as that of the first embodiment.
Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes without departing from the scope of the present invention.
（１）例えば、前記実施例では、反応室内において、ＣＮＴ垂直配向膜を下方に向くように配置したが、図９（ａ）に示す様に、ＣＮＴ垂直配向膜を横方向（水平方向）に向くように配置してもよい。また、図９（ｂ）に示す様に、ＣＮＴ垂直配向膜を斜め下方に向くように配置してよい。 (1) For example, in the above-described embodiment, the CNT vertical alignment film is arranged in the reaction chamber so as to face downward. However, as shown in FIG. 9A, the CNT vertical alignment film is arranged in the horizontal direction (horizontal direction). You may arrange so that it may face. Further, as shown in FIG. 9B, the CNT vertical alignment film may be disposed so as to face obliquely downward.
（２）前記実施例では、気相エッチングとして、酸素プラズマエッチングを例に挙げたが、それ以外に、例えば酸素を含む雰囲気下で紫外線による酸化を用いてもよいし、レーザー光線を用いて切断しても良い。 (2) In the above-described embodiment, oxygen plasma etching is used as an example of vapor phase etching. However, for example, oxidation by ultraviolet rays may be used in an atmosphere containing oxygen, or cutting may be performed using a laser beam. May be.
１…酸素プラズマエッチング装置
３…反応室
1 ... oxygen plasma etching equipment 3 ... reaction chamber
Claims (7)
前記カーボンナノチューブ集合体は、多数のカーボンナノチューブにより形成されたカーボンナノチューブ紡績糸又はカーボンナノチューブシートであり、
前記カーボンナノチューブ垂直配向膜を形成した後に、気相エッチングによって、前記カーボンナノチューブ垂直配向膜の上部を除去することを特徴とするカーボンナノチューブ集合体の製造方法。 In a method of forming a carbon nanotube vertical alignment film on a substrate surface by a chemical vapor synthesis method and producing a carbon nanotube aggregate from the carbon nanotube vertical alignment film,
The carbon nanotube aggregate is a carbon nanotube spun yarn or a carbon nanotube sheet formed of a large number of carbon nanotubes,
After forming the carbon nanotube vertical alignment film, the upper part of the carbon nanotube vertical alignment film is removed by vapor-phase etching, and the carbon nanotube aggregate manufacturing method is characterized by the following.
前記カーボンナノチューブ集合体は、多数のカーボンナノチューブにより形成されたカーボンナノチューブ紡績糸又はカーボンナノチューブシートであり、
前記カーボンナノチューブは、軸方向の両端が開口した構造を有することを特徴とするカーボンナノチューブ集合体。 In an aggregate of carbon nanotubes, which is an aggregate in which a large number of carbon nanotubes are densely packed,
The carbon nanotube aggregate is a carbon nanotube spun yarn or a carbon nanotube sheet formed of a large number of carbon nanotubes,
The carbon nanotube aggregate has a structure in which both ends in the axial direction are open.
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