JP3848584B2 - Method for producing carbon nanotube - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、カーボンナノチューブの製造方法に関する。本発明により製造されたカーボンナノチューブは特定の構造を有し、例えば、半導体的な材料、即ち、電子材料、電子源、エネルギー源等に広く利用される。
【０００２】
【従来の技術】
カーボンナノチューブは、２次元のグラフェンシートを筒状に巻いた構造を有する。この巻き方によってカイラリティーが決まり、（ａ）アームチェア型構造、（ｂ）ジグザグ型構造、（ｃ）カイラル型構造の３種類に分類される。（ａ）アームチェア型構造は、２次元のグラフェンシートの（０，０）面を（１，１）面方向に重ねて巻いて筒状にした形状であり、金属的な性質を示す。一方、（ｂ）ジグザグ型構造は、（０，０）面を（１，０）面方向に重ねて巻いて筒状にした形状である。更に、（ｃ）カイラル型構造は、（０，０）面を（１，０）面方向と（１，１）面方向との間の方向に重ねて巻いて筒状にした形状である。これら幾何学的構造の違いによって、電子状態が異なり、（ａ）アームチェア型構造は金属的な性質を、（ｂ）ジグザグ型構造及び（ｃ）カイラル型構造は、いずれも半導体的な性質を示す。
近年、電子デバイス等の電子材料分野、電界放出型電子源及びフラットパネルディスプレイ等の電子源分野、水素貯蔵及びナノボンベ等のエネルギー分野等への応用のために半導体的な性質を示すカーボンナノチューブを選択的に得る方法が求められている。また、特定の構造を有するカーボンナノチューブを選択的に得るだけでなく、カーボンナノチューブの径のばらつきの度合いが小さく、比較的揃ったカーボンナノチューブ膜を得ることができれば、各応用分野において、一層有用で高性能な製品を提供可能であると予想される。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、特定の構造、即ちジグザグ型構造を主として有し、カーボンナノチューブのチューブ径の揃った、即ち、チューブ径のばらつきの度合いが小さいカーボンナノチューブの製造方法を提供することである。
【０００４】
【課題を解決するための手段】
本発明のカーボンナノチューブの製造方法は、真空下で加熱する際の加熱条件を限定するものであり、チューブ径の揃ったジグザグ型構造のカーボンナノチューブを均一に且つ効率的に製造するものである。即ち、真空下でＳｉＣを、該ＳｉＣが分解して該ＳｉＣの表面から珪素原子が失われる温度に加熱することにより、該ＳｉＣから珪素原子を除去して、ジグザグ型構造のカーボンナノチューブを製造する方法であって、上記加熱の昇温速度が１〜３０℃／分とするものである。
【０００５】
上記方法により得られるジグザグ型構造のカーボンナノチューブは、全体に対して８０％以上であるものとすることができ、カイラル型構造のカーボンナノチューブを含むものとすることができる。尚、アームチェア型構造のカーボンナノチューブは含まないものとすることができる。
【０００６】
【発明の効果】
本製造方法によると、チューブ径の揃ったジグザグ型構造のみのカーボンナノチューブを得ることができ、これを利用した各種応用製品は安定した性能を発揮すると考えられる。また、本製造方法では、更にカイラル型構造を含むものも得ることができる。尚、金属的な性質を示すアームチェア型構造のカーボンナノチューブは製造されない。
【０００７】
【発明の実施の形態】
本発明を更に詳しく説明する。
上記カーボンナノチューブを得るために用いるＳｉＣとしては特に限定されないが、結晶形はα−ＳｉＣでもβ−ＳｉＣでもいずれでもよい。また、単結晶でも多結晶でもよい。ウィスカー（ひげ状結晶）であってもよい。更に、多孔質であってもよい。多孔質の場合、気孔率等も特に限定されない。また、気孔の形状も球状であっても不規則なものであってもよく、閉じた気孔でも外部と通じた気孔であってもよい。更に、焼結体であってもよい。ＳｉＣの形状も板状（円形、四角形、Ｌ形等）、線状（直線、曲線等）、塊状（立方体、直方体、球形、略球形等）等特に限定されない。
【０００８】
上記ＳｉＣは、真空下で加熱される。好ましい真空度は、１０−１〜１０−１０Ｔｏｒｒであり、より好ましくは１０−２〜１０−９Ｔｏｒｒ、更に好ましくは１０−４〜１０−７Ｔｏｒｒである。また、加熱温度は、加熱条件に関わらず、通常、１，４００℃以上とすることでジグザグ型構造のカーボンナノチューブを得ることができる。しかし、加熱条件を更に詳しく検討した結果、以下のような方法とすることによってジグザグ型構造のカーボンナノチューブがより選択的に得られること、更に、チューブ径の揃った、即ち、チューブ径のばらつきの度合いが小さいカーボンナノチューブを得られることが分かった。
即ち、その加熱条件は、昇温速度を１〜３０℃／分とするものであり、好ましくは１〜１０℃／分である。昇温速度をこの範囲とすることにより、ジグザグ型構造のカーボンナノチューブを選択的に得ることができ、チューブ径をより揃えることができる。昇温速度が大きすぎると、カイラル型構造のカーボンナノチューブが混在し、チューブ径のばらつきの度合いが大きくなる傾向にある。
【０００９】
また、チューブ径のばらつきの度合いが小さいジグザグ型構造のカーボンナノチューブを得るための好ましい加熱条件は、常温付近から６００〜８００℃まで昇温する第１加熱段階、続いて１，１００〜１，３００℃まで昇温する第２加熱段階、更に１，４００℃以上、好ましくは１，４００〜１，９００℃に昇温する第３加熱段階を備えるものである。尚、上記第１加熱段階及び上記第２加熱段階は、各昇温が終了した時点の温度で一定時間保持されるものであってもよいし、それぞれそのまま次の段階に進んでもよい。
【００１０】
上記第１加熱段階の昇温によって達した温度で保持する場合の保持時間は、好ましくは１〜１０時間、より好ましくは３〜７時間である。また、上記第２加熱段階の昇温によって達した温度で保持する場合の保持時間は、好ましくは１分〜１，５００時間、より好ましくは１〜１，０００時間である。上記第３加熱段階の昇温によって達した温度で保持する場合の保持時間は、好ましくは１分〜１，５００時間、より好ましくは３分〜１，２００時間、更に好ましくは５分〜１，０００時間、特に好ましくは１０分〜８００時間である。加熱温度が高すぎると、ＳｉＣから珪素原子が失われる速度が大きくなることがある。また、カーボンナノチューブが不規則な方向に成長し、チューブ径が不均一になることがある。更には、チューブ形成に関与しないカーボンによってグラファイト層が形成されることがある。
【００１１】
また、ジグザグ型構造のカーボンナノチューブを安定して成長させるために、上記第２加熱段階の好ましい昇温速度は５０℃／分以下であり、より好ましくは０．０１〜４５℃／分、更に好ましくは０．０５〜４０℃／分、特に好ましくは０．１〜３５℃／分である。上記第２加熱段階の昇温速度が大きすぎるとジグザグ型構造を有するカーボンナノチューブの割合が小さくなる傾向がある。上記第２加熱段階は、カーボンナノチューブ形成の初期段階、即ちＳｉＣの分解の初期段階に相当する熱処理であり、上記範囲の昇温速度は、均一なチューブ径を有するカーボンナノチューブを形成するために重要な半球状のカーボンナノキャップ（図４参照）が、形状を乱すことなく生成するための重要な条件になる。
更に、上記第１加熱段階及び第３加熱段階の昇温速度は特に限定されず、それぞれ、目的の温度に達するまでに一定であっても、段階的に変化するものであってもよい。上記第１加熱段階の平均昇温速度は、好ましくは０．１〜５０℃／分、更に好ましくは０．５〜４５℃／分であり、上記第３加熱段階の平均昇温速度は好ましくは１〜４０℃／分、更に好ましくは３〜３５℃／分である。
上記ＳｉＣを加熱する手段としては特に限定されず、電気炉、レーザービーム照射、直接通電加熱、赤外線照射加熱等の手段によることができる。
【００１２】
また、加熱終了後、降温されるが、その方法は特に限定されない。降温手段の例としては、一定速度で常温まで冷却する方法、上記目的の加熱温度より低い温度で一定時間保持した後冷却する方法等が挙げられる。冷却する手段は特に限定されない。
これらの条件をうまく組み合わせることにより、ジグザグ型構造を主とするカーボンナノチューブを選択的に得ることが容易となる。
【００１３】
上記のようにして得られるカーボンナノチューブのうち、ジグザグ型構造を有するカーボンナノチューブの割合は、全体に対して、好ましくは８０％以上（１００％を含む）、より好ましくは８５％以上（１００％を含む）、更に好ましくは９０％以上（１００％を含む）であり、特に好ましくは９５％以上（１００％を含む）である。ジグザグ型構造以外のものが含まれる場合、それはカイラル型構造である。
尚、カーボンナノチューブの構造は、電子線回折像により容易に同定することができる。
【００１４】
また、得られるカーボンナノチューブの平均径は、通常、１〜１０ｎｍであり、より好ましくは１〜８ｎｍ、更に好ましくは１〜６ｎｍである。製造条件をうまく設定することにより、分布の小さい、即ちばらつきの小さいチューブ径を有するカーボンナノチューブを得ることができる。
更に、上記条件によると、単層構造のカーボンナノチューブを得ることもできる。
【００１５】
【実施例】
以下に実施例を挙げて本発明を具体的に説明する。
縦１ｍｍ、横４ｍｍ、高さ０．２ｍｍのα−ＳｉＣ単結晶を試料とし、その表面を平滑化処理した。このＳｉＣ単結晶を、カーボンヒーターを備える高温炉に入れ、真空度５×１０−９Ｔｏｒｒに排気しながら、常温から昇温速度１℃／分で１，４００℃まで加熱し、この温度を１６８時間保持した。その後、降温速度７℃／分で１，０００℃まで冷却し、常温まで放冷した。この熱処理により、カーボンナノチューブを製造した。このカーボンナノチューブを透過型電子顕微鏡で観察したところ、カーボンナノチューブの集合体が試料に対して垂直方向に配列した連続膜であることが確認できた。また、トプコン社製００２Ｂ型電子顕微鏡を用い、加速電圧２００ｋＶの条件でカーボンナノチューブの電子線回折像（図１）を得た。図１より、（１００）反射がシャープに観察され、それらの相対的位置関係より、カーボンナノチューブがジグザグ型構造であることが分かった。
次に、膜状に得られたカーボンナノチューブについて、一定長さのチューブ径を有するカーボンナノチューブの分布を調べた。また、一定数の層を有するカーボンナノチューブの数を以下の方法で数えた。カーボンナノチューブをＳｉＣ単結晶本体側から研削しカーボンナノチューブ断面が得られるような薄片を得て、透過型電子顕微鏡（ＴＥＭ）を用いて、倍率６００万倍で撮影し、視野角２０ｃｍ×３０ｃｍの写真を得た。この写真を用いて各カーボンナノチューブの平均径を測定し、その長さを有する個数を数えた。層の数は、各カーボンナノチューブについて測定し、その層の数を有する個数を数えた。それぞれの結果を図２及び図３に示す。尚、図２は計測されたチューブ径が最大数を示したチューブの数を１００として表した。
図２より、カーボンナノチューブのチューブ径に着目すると、３．５〜４ｎｍにピークを有する分布であり、ばらつきの度合いが小さいことが分かる。また、図３より、層の数について見ると、２層のものが多く、３層のものを加えると大半を占めており、図２に示すチューブ径と良く対応していることが分かる。
【００１６】
尚、本発明は上記実施例に限定されるものではなく、本発明の範囲内で種々変更した実施例とすることができる。
例えば、ＳｉＣの分解を促進するために、系内にＣＯガス、ＣＯ２ガス、フッ素ガス、ＣＦ４ガス、酸素ガス、水蒸気等のガスを導入して加熱処理することができる。この場合、系内の真空度が低下することがあるが、ＳｉＣの分解速度が劣るようなことはない。
【図面の簡単な説明】
【図１】 実施例で得られたカーボンナノチューブの電子線回折像写真を示す説明図である。
【図２】 実施例において得られたカーボンナノチューブの平均径と個数の関係を示すグラフである。
【図３】 実施例において得られたカーボンナノチューブの層数と個数の関係を示すグラフである。
【図４】 カーボンナノキャップ（矢印の部分）が生成し始めた様子を示す説明図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing carbon nanotubes. The carbon nanotubes produced by the present invention have a specific structure and are widely used, for example, as semiconductor materials, that is, electronic materials, electron sources, energy sources, and the like.
[0002]
[Prior art]
The carbon nanotube has a structure in which a two-dimensional graphene sheet is wound in a cylindrical shape. The chirality is determined by this winding method, and is classified into three types: (a) armchair structure, (b) zigzag structure, and (c) chiral structure. (A) The armchair type structure is a cylindrical shape in which the (0,0) plane of a two-dimensional graphene sheet is overlapped and wound in the (1,1) plane direction, and exhibits metallic properties. On the other hand, the (b) zigzag structure has a cylindrical shape in which the (0,0) plane is overlapped and wound in the (1,0) plane direction. Furthermore, (c) the chiral structure has a cylindrical shape in which the (0,0) plane is overlapped and wound in a direction between the (1,0) plane direction and the (1,1) plane direction. Due to these geometrical structures, the electronic state differs, and (a) the armchair structure has metallic properties, and (b) the zigzag structure and (c) chiral structure both have semiconducting properties. Show.
In recent years, carbon nanotubes with semiconducting properties have been selected for applications in the field of electronic materials such as electronic devices, the field of electron sources such as field emission electron sources and flat panel displays, and the field of energy such as hydrogen storage and nanobombs. There is a need for a method that can be obtained. In addition to selectively obtaining carbon nanotubes having a specific structure, it would be more useful in each application field if a carbon nanotube film having a relatively small diameter variation and a relatively uniform carbon nanotube film could be obtained. It is expected that high-performance products can be provided.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a carbon nanotube mainly having a specific structure, that is, a zigzag structure and having a uniform tube diameter of the carbon nanotube, that is, a small degree of variation in the tube diameter.
[0004]
[Means for Solving the Problems]
The method for producing carbon nanotubes of the present invention limits the heating conditions when heating under vacuum, and uniformly and efficiently produces carbon nanotubes having a zigzag structure with a uniform tube diameter. That is, by heating SiC under vacuum to a temperature at which the SiC is decomposed and silicon atoms are lost from the surface of the SiC, the silicon atoms are removed from the SiC to produce a carbon nanotube having a zigzag structure. It is a method, Comprising: The temperature increase rate of the said heating shall be 1-30 degrees C / min.
[0005]
The carbon nanotubes having a zigzag structure obtained by the above method can be 80% or more of the whole, and can include carbon nanotubes having a chiral structure. Note that the carbon nanotubes having an armchair structure may not be included.
[0006]
【The invention's effect】
According to this production method, carbon nanotubes having only a zigzag structure with a uniform tube diameter can be obtained, and various application products using this can be considered to exhibit stable performance. Moreover, in this manufacturing method, what contains a chiral type structure can also be obtained. In addition, the carbon nanotube of the armchair type structure which shows a metallic property is not manufactured.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in more detail.
Although it does not specifically limit as SiC used in order to obtain the said carbon nanotube, Any (alpha) -SiC or (beta) -SiC may be sufficient as a crystal form. Further, it may be single crystal or polycrystal. It may be a whisker. Furthermore, it may be porous. In the case of a porous material, the porosity and the like are not particularly limited. The shape of the pores may be spherical or irregular, and may be closed pores or pores communicating with the outside. Further, it may be a sintered body. The shape of SiC is not particularly limited, such as a plate shape (circular, quadrangular, L-shaped, etc.), a linear shape (straight line, curved line, etc.), or a massive shape (cube, rectangular parallelepiped, spherical, substantially spherical, etc.)
[0008]
The SiC is heated under vacuum. A preferable degree of vacuum is 10 −1 to 10 −10 Torr, more preferably 10 −2 to 10 −9 Torr, and still more preferably 10 −4 to 10 −7 Torr. In addition, regardless of the heating conditions, the carbon nanotube having a zigzag structure can be usually obtained by setting the heating temperature to 1,400 ° C. or higher. However, as a result of examining the heating conditions in more detail, it is possible to more selectively obtain carbon nanotubes having a zigzag structure by adopting the following method, and furthermore, the tube diameters are uniform, that is, the variation in tube diameters. It was found that a carbon nanotube with a small degree can be obtained.
That is, the heating conditions are such that the rate of temperature rise is 1 to 30 ° C./min, and preferably 1 to 10 ° C./min. By setting the heating rate within this range, carbon nanotubes having a zigzag structure can be selectively obtained, and the tube diameters can be made more uniform. If the rate of temperature rise is too high, carbon nanotubes with a chiral structure are mixed, and the degree of variation in tube diameter tends to increase.
[0009]
In addition, a preferable heating condition for obtaining a carbon nanotube having a zigzag structure with a small degree of variation in tube diameter is a first heating stage in which the temperature is raised from near room temperature to 600 to 800 ° C., and subsequently 1,100 to 1,300. A second heating stage for raising the temperature to 1 ° C., and further a third heating stage for raising the temperature to 1,400 ° C. or higher, preferably 1,400 to 1,900 ° C. The first heating stage and the second heating stage may be held for a certain period of time at the temperature at which each temperature increase is completed, or may proceed to the next stage as they are.
[0010]
The holding time in the case of holding at the temperature reached by the temperature increase in the first heating stage is preferably 1 to 10 hours, more preferably 3 to 7 hours. Moreover, the holding time in the case of holding at the temperature reached by the temperature increase in the second heating stage is preferably 1 minute to 1,500 hours, more preferably 1 to 1,000 hours. The holding time in the case of holding at the temperature reached by the temperature increase in the third heating stage is preferably 1 minute to 1,500 hours, more preferably 3 minutes to 1,200 hours, still more preferably 5 minutes to 1, 000 hours, particularly preferably 10 minutes to 800 hours. If the heating temperature is too high, the rate at which silicon atoms are lost from SiC may increase. In addition, carbon nanotubes may grow in irregular directions, and the tube diameter may become non-uniform. Furthermore, a graphite layer may be formed by carbon that is not involved in tube formation.
[0011]
In addition, in order to stably grow the carbon nanotubes having a zigzag structure, a preferable temperature increase rate in the second heating step is 50 ° C./min or less, more preferably 0.01 to 45 ° C./min, and still more preferably. Is 0.05 to 40 ° C./min, particularly preferably 0.1 to 35 ° C./min. If the rate of temperature increase in the second heating stage is too large, the proportion of carbon nanotubes having a zigzag structure tends to be small. The second heating stage is a heat treatment corresponding to an initial stage of carbon nanotube formation, that is, an initial stage of SiC decomposition, and the temperature increase rate in the above range is important for forming carbon nanotubes having a uniform tube diameter. A hemispherical carbon nanocap (see FIG. 4) is an important condition for generating the carbon nanocap without disturbing its shape.
Further, the rate of temperature increase in the first heating stage and the third heating stage is not particularly limited, and may be constant or change in stages until reaching the target temperature. The average heating rate in the first heating stage is preferably 0.1 to 50 ° C./min, more preferably 0.5 to 45 ° C./min, and the average heating rate in the third heating stage is preferably 1-40 ° C./min, more preferably 3-35 ° C./min.
The means for heating SiC is not particularly limited, and may be a means such as an electric furnace, laser beam irradiation, direct current heating, infrared irradiation heating and the like.
[0012]
Further, the temperature is lowered after the heating is completed, but the method is not particularly limited. Examples of the temperature lowering means include a method of cooling to room temperature at a constant rate, a method of cooling after holding for a certain time at a temperature lower than the above-mentioned target heating temperature, and the like. The means for cooling is not particularly limited.
By combining these conditions well, it becomes easy to selectively obtain carbon nanotubes mainly having a zigzag structure.
[0013]
Of the carbon nanotubes obtained as described above, the proportion of carbon nanotubes having a zigzag structure is preferably 80% or more (including 100%), more preferably 85% or more (100% More preferably 90% or more (including 100%), and particularly preferably 95% or more (including 100%). If anything other than a zigzag structure is included, it is a chiral structure.
The structure of the carbon nanotube can be easily identified by an electron beam diffraction image.
[0014]
Moreover, the average diameter of the carbon nanotube obtained is 1-10 nm normally, More preferably, it is 1-8 nm, More preferably, it is 1-6 nm. By setting production conditions well, carbon nanotubes having a tube diameter with a small distribution, that is, a small variation can be obtained.
Furthermore, according to the above conditions, carbon nanotubes having a single-layer structure can also be obtained.
[0015]
【Example】
The present invention will be specifically described below with reference to examples.
An α-SiC single crystal having a length of 1 mm, a width of 4 mm, and a height of 0.2 mm was used as a sample, and the surface thereof was smoothed. This SiC single crystal was placed in a high temperature furnace equipped with a carbon heater and heated from room temperature to 1,400 ° C. at a temperature rising rate of 1 ° C./min while exhausting to a vacuum degree of 5 × 10 −9 Torr. Held for hours. Then, it cooled to 1,000 degreeC with the temperature-fall rate of 7 degree-C / min, and stood to cool to normal temperature. Carbon nanotubes were produced by this heat treatment. When the carbon nanotubes were observed with a transmission electron microscope, it was confirmed that the aggregate of carbon nanotubes was a continuous film arranged in a direction perpendicular to the sample. Further, an electron beam diffraction image (FIG. 1) of the carbon nanotube was obtained under the condition of an acceleration voltage of 200 kV using a Topcon 002B electron microscope. From FIG. 1, (100) reflection was observed sharply, and it was found from the relative positional relationship between them that the carbon nanotubes have a zigzag structure.
Next, regarding the carbon nanotubes obtained in a film shape, the distribution of carbon nanotubes having a certain length of tube diameter was examined. Further, the number of carbon nanotubes having a certain number of layers was counted by the following method. A carbon nanotube is ground from the SiC single crystal main body side to obtain a thin piece from which a cross section of the carbon nanotube can be obtained. Got. Using this photograph, the average diameter of each carbon nanotube was measured, and the number having the length was counted. The number of layers was measured for each carbon nanotube, and the number having the number of layers was counted. The respective results are shown in FIGS. In FIG. 2, the number of tubes in which the measured tube diameter showed the maximum number was represented as 100.
From FIG. 2, focusing on the tube diameter of the carbon nanotube, it can be seen that the distribution has a peak at 3.5 to 4 nm and the degree of variation is small. Further, from the view of the number of layers, it can be seen from FIG. 3 that there are many two-layered layers, and most of the three-layered ones occupy the most, and correspond well with the tube diameter shown in FIG.
[0016]
In addition, this invention is not limited to the said Example, It can be set as the Example variously changed within the scope of the present invention.
For example, in order to promote the decomposition of SiC, heat treatment can be performed by introducing a gas such as CO gas, CO 2 gas, fluorine gas, CF 4 gas, oxygen gas, or water vapor into the system. In this case, the degree of vacuum in the system may decrease, but the decomposition rate of SiC does not deteriorate.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing an electron diffraction image photograph of a carbon nanotube obtained in an example.
FIG. 2 is a graph showing the relationship between the average diameter and the number of carbon nanotubes obtained in the examples.
FIG. 3 is a graph showing the relationship between the number of carbon nanotubes and the number of carbon nanotubes obtained in Examples.
FIG. 4 is an explanatory diagram showing a state in which carbon nanocaps (arrow portions) have started to be generated.
Claims (4)
上記加熱の昇温速度が１〜３０℃／分であることを特徴とするカーボンナノチューブの製造方法。In a method of producing a carbon nanotube having a zigzag structure by removing SiC from the SiC by heating the SiC under vacuum to a temperature at which the SiC decomposes and silicon atoms are lost from the surface of the SiC. There,
A method for producing a carbon nanotube, wherein the heating rate of the heating is 1 to 30 ° C./min.
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