JP5045891B2 - Boron-doped carbon nanotube and method for producing the same - Google Patents
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本発明は、ホウ素ドープカーボンナノチューブとその製造方法に関する。 The present invention relates to a boron-doped carbon nanotube and a method for producing the same.
特許文献1から3に示されているように、アーク法でホウ素を含むカーボンロッドを用いてホウ素ドープカーボンナノチューブを合成する方法や、カーボンナノチューブにホウ素を蒸着して2000度以上の高温反応により、ホウ素ドープカーボンナノチューブを合成することは知られていた。
これらの従来手法は、いずれも通常では使用しない高温度にてカーボンナノチューブを処理する必要があるので、カーボンナノチューブに欠陥が入り易く、目的の場所に成長させる選択成長が難しいなど各種の問題が生じていた。また、ホウ素濃度の制御や単層多層および直径の制御なども困難であった。また、合成装置も通常は使用しない2000℃以上の高温に耐えうるものとしなければならず、通常では使用しない特殊な構成を必要とするという問題があった。
また、マイクロ波プラズマCVDを使って、ホウ素ドープカーボンナノチューブを合成することが非特許文献1に示されているが、マイクロ波プラズマCVD装置は、高周波電源などを使うので、装置が複雑であるとともに、プラズマで反応させるのでかなり反応温度は高いという問題があった。
None of these conventional methods require the carbon nanotubes to be processed at a high temperature, which is not normally used, so that various problems occur, such as the carbon nanotubes being prone to defects and difficult to selectively grow at the desired location. It was. In addition, it is difficult to control the boron concentration, single layer multilayer and diameter. Also, the synthesizer must be able to withstand a high temperature of 2000 ° C. or higher that is not normally used, and there is a problem that a special configuration that is not normally used is required.
Further, Non-Patent Document 1 shows that boron-doped carbon nanotubes are synthesized using microwave plasma CVD. However, since the microwave plasma CVD apparatus uses a high-frequency power source, the apparatus is complicated. The reaction temperature is quite high because of the plasma reaction.
本発明は、このような実情に鑑み、従来には得られない高品質のホウ素ドープカーボンナノチューブを提供するとともに、通常の化学気相成長法により、カーボンナノチューブにホウ素をドープする製法を提供することを目的とする。 In view of such circumstances, the present invention provides a high-quality boron-doped carbon nanotube that cannot be obtained in the past, and a method for doping boron into a carbon nanotube by an ordinary chemical vapor deposition method. With the goal.
発明1のホウ素ドープカーボンナノチューブの製造方法は、混合ガスが、炭素を含有する液体有機溶媒にホウ素含有物を溶解させた溶液の蒸気であることを特徴とする。
The method for producing a boron-doped carbon nanotube of the invention 1 is characterized in that the mixed gas is a vapor of a solution obtained by dissolving a boron-containing material in a liquid organic solvent containing carbon .
本発明1により、従来には得られなかったカイラリティーに依存しない高い電気伝導率のカーボンナノチューブを提供することができた。
具体的には、極低温(0.6K)まで、従来にはない高い電気伝導率を保つことが可能になった。
According to the present invention 1, it was possible to provide a carbon nanotube having high electrical conductivity that does not depend on chirality, which has not been obtained conventionally.
Specifically, it has become possible to maintain a high electrical conductivity that has not been achieved until now at extremely low temperatures (0.6 K).
本発明1により、上記のような特性をもつホウ素ドープカーボンナノチューブを製造するに当たり、従来に比べ著しく低温で合成でき、装置そのものの耐熱性は、通常の化学気相成長法に用いる電気炉あるいはそれと同程度であれば足り、製造が容易になった。
According to the present invention 1 , when producing boron-doped carbon nanotubes having the above-described characteristics, the boron-doped carbon nanotubes can be synthesized at a significantly lower temperature than conventional ones, and the heat resistance of the apparatus itself is the electric furnace used in a normal chemical vapor deposition method or the same. The same level is sufficient, and manufacturing is easy.
さらに、ホウ素含有物と炭素含有物との混合割合、ガス圧及び温度等の調整により、ドープされるホウ素の濃度制御、電気伝導度を調整することが可能である。
また触媒によって生成されるカーボンナノチューブの種類(単層カーボンナノチューブ、多層カーボンナノチューブの別、さらにはその直径)を調整することも可能である。
Furthermore, it is possible to adjust the concentration control of boron to be doped and the electric conductivity by adjusting the mixing ratio of the boron-containing material and the carbon-containing material, the gas pressure, the temperature, and the like.
It is also possible to adjust the type of carbon nanotubes produced by the catalyst (single-walled carbon nanotubes, multi-walled carbon nanotubes, and their diameter).
また、発明1では、ガスではなく液体を供給することになるので、操作時の取り扱いが容易であり安全でもある。 Further, in the first aspect , since liquid is supplied instead of gas, handling during operation is easy and safe.
1、以下の実施例では基材に触媒であるFe2O3ナノ粒子を塗布したSi基板を用いたが、これに限らず以下のような基材を用いることが可能である。
それ故に、チャンバー内の空間が十分に大きい場合は、大面積にカーボンナノチューブを成長できることも可能であり、この種カーボンナノチューブの大量生産に路を開くものでもある。
1. In the following examples, a Si substrate having a base material coated with Fe 2 O 3 nanoparticles as a catalyst was used. However, the present invention is not limited to this, and the following base materials can be used.
Therefore, when the space in the chamber is sufficiently large, it is possible to grow carbon nanotubes in a large area, and this opens the way for mass production of such carbon nanotubes.
ホウ素含有物を溶解する溶媒としては、実施例に示すメタノールの他に、化学気相成長の反応温度で分解し、分子構造に炭素原子を有するためカーボンナノチューブを成長させることが可能である以下に示すものが使用できる。
エタノールやプロパノール、アセトンなどの有機材料。
メタンやブタン、プロパン、ペンタン、ヘキサンなどの炭素を含むガス。
ベンゼン環を有する有機材料も含め、CとHとOから構成されている有機物。
As a solvent for dissolving the boron-containing material, in addition to methanol shown in the examples, it can be decomposed at the reaction temperature of chemical vapor deposition and has carbon atoms in its molecular structure. The ones shown can be used.
Organic materials such as ethanol, propanol, and acetone.
Gas containing carbon such as methane, butane, propane, pentane and hexane.
Organic materials composed of C, H, and O, including organic materials having a benzene ring.
ホウ素化合物としては、ホウ酸の他、化学気相成長の反応温度で分解する以下のものが使用可能である。
例えば、酸化ホウ素B2O3、カルボラン酸HCB11Cl11、三フッ化ホウ素BF3、水素化ホウ素ナトリウムBH4Na、テトラフルオロホウ酸HBF4、二ホウ化マグネシウムB2Mg、ホウ酸H3BO3、ボラジンB3H6N3、モノボランBH3、ジボランB2H6やトリメチルボロンなど、ホウ素を含むガス。
このうち固体のホウ素化合物は、先に挙げた炭素原子を含有する有機溶媒に溶解可能であり、加熱によりホウ素原子を含有する炭素原料ガスとして石英管内に導入可能である。
ホウ素原子含有ガスについては、そのまま炭素原子を含有するガスとともに石英管内に導入可能である。
As the boron compound, besides boric acid, the following compounds that decompose at the reaction temperature of chemical vapor deposition can be used.
For example, boron oxide B 2 O 3 , carborane acid HCB 11 C 11 1 , boron trifluoride BF 3 , sodium borohydride BH 4 Na, tetrafluoroborate HBF 4 , magnesium diboride B 2 Mg, borate H 3 Gas containing boron, such as BO 3 , borazine B 3 H 6 N 3 , monoborane BH 3 , diborane B 2 H 6 and trimethylboron.
Among these, the solid boron compound can be dissolved in the organic solvent containing carbon atoms mentioned above, and can be introduced into the quartz tube as a carbon source gas containing boron atoms by heating.
The boron atom-containing gas can be introduced into the quartz tube together with the gas containing carbon atoms as it is.
Fe2O3ナノ粒子の粒径に応じて、多層カーボンナノチューブおよび単層カーボンナノチューブを作り分けられ、カーボンナノチューブの直径も制御することが出来る。
カーボンナノチューブの直径は、用いるFe2O3ナノ粒子の粒径に近い直径になる。そのため、粒径が大きな場合には、多層カーボンナノチューブが出来易く、粒径が小さな場合には単層カーボンナノチューブが出来易い。
Multi-walled carbon nanotubes and single-walled carbon nanotubes can be made according to the particle diameter of Fe 2 O 3 nanoparticles, and the diameter of the carbon nanotubes can also be controlled.
The diameter of the carbon nanotube is close to the particle diameter of the Fe 2 O 3 nanoparticles used. Therefore, when the particle size is large, multi-walled carbon nanotubes are easily formed, and when the particle size is small, single-walled carbon nanotubes are easily formed.
化学気相成長の加熱装置に、今回は電気炉を用いたが、800度程度まで温度が上がれば、加熱装置には何を用いても良い。
Although an electric furnace was used for the chemical vapor deposition heating device this time, any heating device may be used as long as the temperature rises to about 800 degrees.
図1にホウ素ドープカーボンナノチューブの合成装置を示す。合成装置内の石英管内部に設置した基板上にホウ素ドープした多層カーボンナノチューブの合成を行った。
基板には、触媒である(平均粒径50nm)のFe2O3ナノ粒子を塗布したSi基板を用いた。
原料には、炭素源としてメタノール、ホウ素源としてホウ酸を用いた。ホウ酸は、メタノールに良く溶解するのでこの組み合わせを用いた。ホウ酸は0から2.0atm%まで表2のように変化させたが、実験No.1を除きホウ素ドープカーボンナノチューブが得られた。
FIG. 1 shows an apparatus for synthesizing boron-doped carbon nanotubes. A multi-walled carbon nanotube doped with boron was synthesized on a substrate placed inside a quartz tube in the synthesizer.
As the substrate, a Si substrate coated with Fe 2 O 3 nanoparticles having an average particle diameter of 50 nm as a catalyst was used.
As raw materials, methanol was used as a carbon source, and boric acid was used as a boron source. This combination was used because boric acid dissolves well in methanol. Boric acid was changed from 0 to 2.0 atm% as shown in Table 2, except for Experiment No. 1, boron-doped carbon nanotubes were obtained.
ホウ素含有炭素源の入った容器は、温浴中に設置する。温浴は適切な蒸気圧が得られる温度に設定するが、今回は34℃付近が最適であった。原料にガスを用いた場合、温浴の変わりに、フロー制御装置を用いる。
基板設置後、バルブ1を開いて石英管内部を真空ポンプにより排気する。温度を約730℃まで加温したのち、バルブ2を開いて石英管内へホウ素含有炭素ガスをフローさせる。フロー中の石英管内の圧力は、バルブ1、2により調節するが、今回は、200Torr前後が適当であった。フローを12時間行うことで長さが数十μmのカーボンナノチューブが得られた。また、成長時間を長くすることで、更に長いカーボンナノチューブを成長させることが可能である。成長後は、バルブ2を閉じてフローを停止させる。一方、バルブ1を開き、石英管内を排気し、温度を下げる。
The container containing the boron-containing carbon source is placed in a warm bath. The temperature of the warm bath is set at a temperature that provides an appropriate vapor pressure, but this time around 34 ° C. was optimal. When gas is used as a raw material, a flow control device is used instead of a warm bath.
After installing the substrate, the valve 1 is opened and the quartz tube is evacuated by a vacuum pump. After heating the temperature to about 730 ° C., the valve 2 is opened to allow boron-containing carbon gas to flow into the quartz tube. The pressure in the quartz tube during the flow is adjusted by valves 1 and 2, but this time around 200 Torr was appropriate. A carbon nanotube having a length of several tens of μm was obtained by performing the flow for 12 hours. Further, it is possible to grow longer carbon nanotubes by lengthening the growth time. After the growth, the valve 2 is closed to stop the flow. On the other hand, the valve 1 is opened, the quartz tube is exhausted, and the temperature is lowered.
基板をジクロロエタンの中に浸漬し、超音波洗浄器にかけることによって、触媒やアモルファスグラファイトなどの不純物、もしくは絡み合った他のカーボンナノチューブから分離する。 The substrate is immersed in dichloroethane and subjected to an ultrasonic cleaner to separate it from impurities such as catalyst and amorphous graphite, or other entangled carbon nanotubes.
このようにして得られたホウ素ドープカーボンナノチューブの温度と電気抵抗の関係を電子線描画装置を用いたリフトオフ法により、四本のAu/Ti電極を一本のカーボンナノチューブ上に作製し、四端子法による電気抵抗の温度変化を液体He冷却装置内で測定した。表3の通りの結果を得た。図3はこの表3に基づき作成したグラフである。
ナノ配線、SPMの探針、電子放出デバイス、燃料電池、透明電極、伝導性フィルム、伝導性プラスチック、伝導性繊維などの応用には、電気伝導率の高いホウ素ドープカーボンナノチューブが好ましい。 For applications such as nanowiring, SPM probes, electron emission devices, fuel cells, transparent electrodes, conductive films, conductive plastics, and conductive fibers, boron-doped carbon nanotubes with high electrical conductivity are preferred.
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