JP5494322B2 - CNT wire manufacturing method - Google Patents
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- JP5494322B2 JP5494322B2 JP2010164118A JP2010164118A JP5494322B2 JP 5494322 B2 JP5494322 B2 JP 5494322B2 JP 2010164118 A JP2010164118 A JP 2010164118A JP 2010164118 A JP2010164118 A JP 2010164118A JP 5494322 B2 JP5494322 B2 JP 5494322B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 56
- 239000000758 substrate Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 19
- 238000005259 measurement Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 41
- 229910021393 carbon nanotube Inorganic materials 0.000 description 39
- 239000003054 catalyst Substances 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 238000009987 spinning Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000011088 calibration curve Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Description
本発明は、ＣＮＴ（カーボンナノチューブ）ワイヤの製造方法に関する。 The present invention relates to a method for producing a CNT (carbon nanotube) wire.
カーボンナノチューブ（以下、ＣＮＴとする）は、１９９１年にＮＥＣの飯島氏によって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 nanotube (hereinafter referred to as CNT) is a new carbon material discovered by Mr. Iijima of NEC 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ワイヤが挙げられる。さらに、このＣＮＴワイヤを用いて、ＣＮＴの織布やシートを製造できる。 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. Examples of the CNT aggregate include a CNT wire composed of a plurality of CNTs. Furthermore, using this CNT wire, a woven or sheet of CNT can be manufactured.
ＣＮＴワイヤは、次のように製造できる。まず、基板上にＣＮＴ合成用の金属触媒層を形成し、次に、炭化水素系のガスを炭素源として供給して、化学気相堆積法により、基板上に垂直に配向成長したＣＮＴ膜（複数のＣＮＴから成る膜）を合成する。そして、この膜からＣＮＴ自身が連なった糸を引き出し（紡糸）、必要に応じて撚りをかけ、ＣＮＴからなるワイヤを製造する（特許文献１〜３）。 The CNT wire can be manufactured as follows. First, a metal catalyst layer for CNT synthesis is formed on a substrate. Next, a hydrocarbon-based gas is supplied as a carbon source, and a CNT film vertically aligned and grown on the substrate by chemical vapor deposition ( A film composed of a plurality of CNTs) is synthesized. And the thread | yarn which CNT itself continued from this film | membrane is drawn out (spinning), and it twists as needed, and manufactures the wire which consists of CNT (patent documents 1-3).
上記特許文献１の技術において、金属触媒は、鉄、ニッケル及びコバルトの中から選ばれる少なくとも１種の金属である。また、上記特許文献２の技術において、金属触媒は、鉄、コバルト、ニッケル、鉄合金、コバルト合金、ニッケル合金、鉄酸化物、コバルト酸化物、ニッケル酸化物、またはこれらの組み合わせである。また、上記特許文献３の技術において、金属触媒は、電子ビーム蒸発でシリコンウエハまたはガラスの基板上に堆積させた、厚さ５ｎｍの鉄膜である。 In the technique of Patent Document 1, the metal catalyst is at least one metal selected from iron, nickel, and cobalt. In the technique of Patent Document 2, the metal catalyst is iron, cobalt, nickel, iron alloy, cobalt alloy, nickel alloy, iron oxide, cobalt oxide, nickel oxide, or a combination thereof. In the technique disclosed in Patent Document 3, the metal catalyst is an iron film having a thickness of 5 nm deposited on a silicon wafer or glass substrate by electron beam evaporation.
上記特許文献１〜３を含む従来の技術では、基板上の垂直配向膜から、ＣＮＴが連なった糸を安定して紡糸することができず、ＣＮＴワイヤの生産性や歩留まりが低かった。
本発明は以上の点に鑑みなされたものであり、生産性や歩留まりが高いＣＮＴワイヤの製造方法を提供することを目的とする。
In the conventional techniques including Patent Documents 1 to 3 described above, it is not possible to stably spin a yarn in which CNTs are continuous from a vertical alignment film on a substrate, and the productivity and yield of CNT wires are low.
This invention is made | formed in view of the above point, and it aims at providing the manufacturing method of CNT wire with high productivity and a yield.
本発明のＣＮＴワイヤの製造方法は、表面に、ＦｅとＡｌとの合金の層であるＦｅ−Ａｌ層を有する基板上に、ＣＮＴを複数形成する工程と、複数のＣＮＴの一部を引き出す工程とを有する。本発明のＣＮＴワイヤの製造方法において、蛍光Ｘ線測定に基づき算出した前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌと、蛍光Ｘ線測定に基づき算出した前記Ｆｅ−Ａｌ層の膜厚と、蛍光Ｘ線測定に基づき算出した前記Ｆｅ−Ａｌ層のＦｅ換算での膜厚であるＦｅ膜厚とは、下記の条件１、条件２、及び条件３のうちのいずれかを充足する。
条件１：前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌは、０．５２〜０．７５の範囲にあり、且つ前記Ｆｅ−Ａｌ層の膜厚は、４〜７．９ｎｍの範囲にある。
条件２：前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌは、０．２３〜０．５２の範囲にあり、且つ前記Ｆｅ−Ａｌ層の膜厚は、５．８〜７．９ｎｍの範囲にある。
条件３：前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌは、０．５２以下であり、且つ前記Ｆｅ−Ａｌ層の膜厚は、５．８ｎｍ以下であり、且つ前記Ｆｅ−Ａｌ層のＦｅ膜厚が１．６ｎｍより厚い範囲にある。
The method for producing a CNT wire of the present invention includes a step of forming a plurality of CNTs on a substrate having a Fe—Al layer that is an alloy layer of Fe and Al on the surface , and a step of extracting a part of the plurality of CNTs. And have. In the CNT wire manufacturing method of the present invention, the composition ratio Fe / Al of the Fe—Al layer calculated based on the fluorescent X-ray measurement, the film thickness of the Fe—Al layer calculated based on the fluorescent X-ray measurement, and the fluorescence The Fe film thickness that is the film thickness in terms of Fe of the Fe—Al layer calculated based on the X-ray measurement satisfies one of the following condition 1, condition 2, and condition 3.
Condition 1: The composition ratio Fe / Al of the Fe—Al layer is in the range of 0.52 to 0.75, and the film thickness of the Fe—Al layer is in the range of 4 to 7.9 nm.
Condition 2: The composition ratio Fe / Al of the Fe—Al layer is in the range of 0.23 to 0.52, and the film thickness of the Fe—Al layer is in the range of 5.8 to 7.9 nm. .
Condition 3: The composition ratio Fe / Al of the Fe—Al layer is 0.52 or less, the film thickness of the Fe—Al layer is 5.8 nm or less, and the Fe film of the Fe—Al layer The thickness is in the range thicker than 1.6 nm.
本発明のＣＮＴワイヤの製造方法では、基板上にＣＮＴを複数形成するための触媒として、上述した条件１、条件２、及び条件３のうちのいずれかを充足する組成比及び膜厚のＦｅ−Ａｌ層を用いる。Ｆｅ−Ａｌ層における組成比及び膜厚が、条件１、条件２、及び条件３のうちのいずれかを充足することにより、基板上に複数形成されたＣＮＴを用いてＣＮＴワイヤを製造するときの生産性や歩留まりが高い。 In the method for producing a CNT wire of the present invention, as a catalyst for forming a plurality of CNTs on a substrate, a composition ratio and film thickness satisfying any one of the above-described conditions 1, 2 and 3 are satisfied. An Al layer is used. When the composition ratio and film thickness in the Fe—Al layer satisfy one of Condition 1, Condition 2, and Condition 3, when manufacturing a CNT wire using a plurality of CNTs formed on the substrate Productivity and yield are high.
前記Ｆｅ−Ａｌ層のＦｅ膜厚とは、後述するＦｅ−Ａｌ層のＦｅ換算での膜厚（Ｍ１）を意味する。
前記条件２において、Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌが、０．３０〜０．５２の範囲にあることが好ましい。この範囲にあることにより、ＣＮＴワイヤを製造するときの生産性や歩留まりが一層高い。また、条件２において、Ｆｅ−Ａｌ層の膜厚が５．８〜７．５ｎｍの範囲にあることが好ましい。この範囲にあることにより、ＣＮＴワイヤを製造するときの生産性や歩留まりが一層高い。
The Fe film thickness of the Fe—Al layer means the film thickness (M1) in terms of Fe of the Fe—Al layer described later.
In the condition 2, it is preferable that the composition ratio Fe / Al of the Fe—Al layer is in the range of 0.30 to 0.52. By being in this range, productivity and yield when manufacturing CNT wires are higher. In condition 2, it is preferable that the film thickness of the Fe—Al layer be in the range of 5.8 to 7.5 nm. By being in this range, productivity and yield when manufacturing CNT wires are higher.
本発明のＣＮＴワイヤの製造方法では、予め表面にＦｅ−Ａｌ層が形成された基板を用いてもよいし、製造方法の一部として、基板の表面にＦｅ−Ａｌ層を形成する工程を有していてもよい。 In the CNT wire manufacturing method of the present invention, a substrate having a Fe—Al layer formed on the surface in advance may be used, or as a part of the manufacturing method, there is a step of forming a Fe—Al layer on the surface of the substrate. You may do it.
本発明において、Ｆｅ−Ａｌ層は、例えば、スパッタ又は蒸着により形成することができる。 In the present invention, the Fe—Al layer can be formed, for example, by sputtering or vapor deposition.
本発明の実施形態を説明する。
１．基板の用意
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。
An embodiment of the present invention will be described.
1. Preparation of substrate 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 thereof. 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、金属触媒層を形成した。金属触媒層の形成は、表１に示すように、Ｓ１〜Ｓ２７の２７種類の条件でそれぞれ行った。 Next, a metal catalyst layer was formed on the surface of the substrate (on the thermal oxide film) using a sputtering apparatus. As shown in Table 1, the metal catalyst layer was formed under 27 conditions of S1 to S27.
表１のＳ１〜Ｓ１８、Ｓ２０〜Ｓ２７の条件におけるＦｅ−Ａｌ層の組成比、膜厚は、以下のように算出する。まず、厚み既知のＦｅ層の蛍光Ｘ線測定を行い、Ｆｅ固有のピーク面積強度を求める。これを、複数種類の厚みのＦｅ層についてそれぞれ行い、Ｆｅ膜厚と、Ｆｅ固有のピーク面積強度との検量線を作成しておく。同様に、Ａｌ層についても、Ａｌ膜厚と、蛍光Ｘ線測定スペクトルにおけるＡｌ固有のピーク面積強度との検量線を作成しておく。 The composition ratio and film thickness of the Fe—Al layer under the conditions of S1 to S18 and S20 to S27 in Table 1 are calculated as follows. First, fluorescent X-ray measurement of an Fe layer with a known thickness is performed to determine the peak area intensity unique to Fe. This is performed for each of the Fe layers having a plurality of thicknesses, and a calibration curve between the Fe film thickness and the peak area intensity unique to Fe is prepared. Similarly, for the Al layer, a calibration curve is prepared between the Al film thickness and the peak area intensity unique to Al in the fluorescent X-ray measurement spectrum.
次に、基板上に形成したＦｅ−Ａｌ層の蛍光Ｘ線測定を行う。その測定スペクトルにおいて、Ｆｅ固有のピーク面積強度と、Ａｌ固有のピーク面積強度とをそれぞれ求める。そして、このＦｅ固有のピーク面積強度を、先に作成しておいたＦｅの検量線に当てはめて、Ｆｅ−Ａｌ層のＦｅ換算での膜厚（以下、Ｍ１とする）を算出する。また、Ａｌ固有のピーク面積強度を、先に作成しておいたＡｌの検量線に当てはめて、Ｆｅ−Ａｌ層のＡｌ換算での膜厚（以下、Ｍ２とする）を算出する。このＭ１とＭ２との和を、Ｆｅ−Ａｌ層の膜厚とする。また、Ｍ１／Ｍ２を、Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌとする。 Next, the fluorescent X-ray measurement of the Fe—Al layer formed on the substrate is performed. In the measurement spectrum, the peak area intensity specific to Fe and the peak area intensity specific to Al are obtained. Then, the peak area intensity unique to Fe is applied to the previously prepared calibration curve of Fe, and the film thickness in terms of Fe of the Fe—Al layer (hereinafter referred to as M1) is calculated. Further, the peak area intensity peculiar to Al is applied to the previously prepared Al calibration curve, and the film thickness in terms of Al of the Fe—Al layer (hereinafter referred to as M2) is calculated. The sum of M1 and M2 is the film thickness of the Fe—Al layer. M1 / M2 is the composition ratio Fe / Al of the Fe—Al layer.
表１のＳ１９は、Ｆｅのみから成る層（Ｆｅ層）である。このＦｅ層の膜厚は、以下のように算出する。基板上に形成したＦｅ層の蛍光Ｘ線測定を行う。その測定スペクトルにおいて、Ｆｅ固有のピーク面積強度を求める。そして、このＦｅ固有のピーク面積強度を、先に作成しておいたＦｅの検量線に当てはめて、Ｆｅ層の膜厚を算出する。 S19 in Table 1 is a layer composed only of Fe (Fe layer). The film thickness of this Fe layer is calculated as follows. X-ray fluorescence measurement of the Fe layer formed on the substrate is performed. In the measurement spectrum, the peak area intensity unique to Fe is obtained. Then, the peak area intensity unique to Fe is applied to the previously prepared calibration curve of Fe to calculate the thickness of the Fe layer.
なお、蛍光Ｘ線測定スペクトルからピーク面積強度を求めるときは、ベースラインを引いておき、そのベースラインよりも上の部分の面積を求める。
２．ＣＮＴの合成
Ｓ１〜Ｓ２７の各条件で金属触媒層を形成した基板のそれぞれを用いて、ＣＮＴを合成した。具体的には、以下のようにした。基板を電気炉に挿入し、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。
In addition, when calculating | requiring peak area intensity | strength from a fluorescent X ray measurement spectrum, a base line is drawn and the area of the part above the base line is calculated | required.
2. Synthesis of CNTs CNTs were synthesized using each of the substrates on which the metal catalyst layers were formed under the conditions of S1 to S27. Specifically, it was as follows. The substrate was inserted into an electric furnace, 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、Ｓ１〜Ｓ２７の条件で金属触媒層を形成した基板については、基板上でＣＮＴが合成され、ＣＮＴの垂直配向膜が形成されていた。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いた。また、個々のＣＮＴの直径は１０〜３０ｎｍ程度であり、ＣＮＴの長さは約１００〜３００μmであった。 When the substrate was observed with an electron microscope after the synthesis was completed, CNT was synthesized on the substrate on which the metal catalyst layer was formed under the conditions of S1 to S27, and a vertical alignment film of CNT was formed. One end of the synthesized CNT was fixed to the substrate, and was uniformly oriented in a direction perpendicular to the substrate. Moreover, the diameter of each CNT was about 10-30 nm, and the length of CNT was about 100-300 micrometers.
３．ＣＮＴワイヤの製造試験
ＣＮＴが合成された基板（Ｓ１〜Ｓ２７の条件で金属触媒層を形成した基板）のそれぞれについて、ＣＮＴワイヤの製造試験を行った。具体的には、図１（ａ）に示すように、基板上に配向しているＣＮＴのマトリックスにおいて、基板の端部にあるＣＮＴの束の一端を引出し具でつまみ、ＣＮＴの配向方向とは直交する方向に引出した。このとき、図１（ｂ）〜図１（ｃ）に示すように、ＣＮＴの束が安定して長くつながり、ＣＮＴワイヤが製造できるか（紡糸できるか）否かを試験した。試験は、各条件の基板について、それぞれ、２〜４回行った。
3. CNT Wire Production Test A CNT wire production test was performed on each of the substrates on which CNTs were synthesized (substrates on which a metal catalyst layer was formed under the conditions of S1 to S27). Specifically, as shown in FIG. 1 (a), in the CNT matrix oriented on the substrate, one end of a bundle of CNTs at the end of the substrate is pinched with an extractor, and the orientation direction of the CNT is It was pulled out in the orthogonal direction. At this time, as shown in FIG. 1B to FIG. 1C, it was tested whether a bundle of CNTs was stably and long connected, and a CNT wire could be produced (spun). The test was performed 2 to 4 times for each substrate under each condition.
上記表１に、試験結果を示す。表１の「紡糸可否」において、○は紡糸できたことを表し、×は紡糸できなかったことを表す。また、図２に、Ｓ１〜Ｓ１８、Ｓ２０〜Ｓ２７におけるＦｅ膜厚、及びＡｌ膜厚と、紡糸可否との相関関係を示す。図２において、○は紡糸できたことを表し、○が大きいほど、紡糸できた割合が高いことを表す。また、図２において、×は紡糸できなかったことを表す。また、図３に、紡糸できた場合に製造されたＣＮＴワイヤを示す。図３に示すＣＮＴワイヤは、引き出したＣＮＴの束に撚りを掛け、撚り線にしたものである。 Table 1 shows the test results. In Table 1, “spinnability” indicates that spinning was possible, and x indicates that spinning was not possible. FIG. 2 shows the correlation between the Fe film thickness and the Al film thickness in S1 to S18 and S20 to S27, and whether or not spinning is possible. In FIG. 2, “◯” indicates that spinning has been performed, and the larger “◯” indicates that the proportion of spinning has been higher. In FIG. 2, x indicates that spinning could not be performed. FIG. 3 shows a CNT wire produced when spinning is possible. The CNT wire shown in FIG. 3 is obtained by twisting a bundle of drawn CNTs into a stranded wire.
表１及び図２に示すように、Ｆｅ−Ａｌ層の組成比が０．５２〜０．７５の範囲にあり、且つＦｅ−Ａｌ層の膜厚が７．９ｎｍ以下４ｎｍ以上の範囲にある場合（条件１を充足する場合）に、紡糸できる確率が高かった。 As shown in Table 1 and FIG. 2, when the composition ratio of the Fe—Al layer is in the range of 0.52 to 0.75 and the film thickness of the Fe—Al layer is in the range of 7.9 nm or less and 4 nm or more. The probability of spinning was high (when Condition 1 was satisfied).
また、Ｆｅ−Ａｌ層の組成比が０．２３〜０．５２の範囲にあり、且つＦｅ−Ａｌ層の膜厚が５．８〜７．９ｎｍの範囲にある場合（条件２を充足する場合）に、紡糸できる確率が高かった。 Further, when the composition ratio of the Fe—Al layer is in the range of 0.23 to 0.52 and the thickness of the Fe—Al layer is in the range of 5.8 to 7.9 nm (when the condition 2 is satisfied) ), The probability of spinning was high.
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。
例えば、Ｆｅ−Ａｌ層は蒸着により形成してもよい。
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.
For example, the Fe—Al layer may be formed by vapor deposition.
また、Ｆｅ−Ａｌ層のＦｅ換算膜厚は、蛍光Ｘ線測定スペクトルにおける、Ｆｅ固有のピークの高さに基づいて算出することができる。同様に、Ｆｅ−Ａｌ層のＡｌ換算膜厚は、蛍光Ｘ線測定スペクトルにおける、Ａｌ固有のピークの高さに基づいて算出することができる。なお、ピークの高さを求めるときは、蛍光Ｘ線測定スペクトルにベースラインを引いておき、ピークのトップからそのベースラインまでの長さをピークの高さとする。 Further, the Fe equivalent film thickness of the Fe—Al layer can be calculated based on the peak height unique to Fe in the fluorescent X-ray measurement spectrum. Similarly, the Al equivalent film thickness of the Fe—Al layer can be calculated based on the peak height unique to Al in the fluorescent X-ray measurement spectrum. When obtaining the peak height, a base line is drawn on the X-ray fluorescence measurement spectrum, and the length from the peak top to the base line is defined as the peak height.
また、Ｆｅ−Ａｌ層を形成するために用いるスパッタターゲットは、全体として均一な組成のＦｅ−Ａｌ合金であってもよい。この場合、合金におけるＦｅ／Ａｌ比を変化させることにより、Ｆｅ−Ａｌ層の組成比を調整することができる。 The sputter target used for forming the Fe—Al layer may be a Fe—Al alloy having a uniform composition as a whole. In this case, the composition ratio of the Fe—Al layer can be adjusted by changing the Fe / Al ratio in the alloy.
Claims (3)
前記複数のＣＮＴの一部を引き出す工程と、
を有するＣＮＴワイヤの製造方法であって、
蛍光Ｘ線測定に基づき算出した前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌと、蛍光Ｘ線測定に基づき算出した前記Ｆｅ−Ａｌ層の膜厚と、蛍光Ｘ線測定に基づき算出した前記Ｆｅ−Ａｌ層のＦｅ換算での膜厚であるＦｅ膜厚とが、下記の条件１、条件２、及び条件３のうちのいずれかを充足することを特徴とするＣＮＴワイヤの製造方法。
条件１：前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌは、０．５２〜０．７５の範囲にあり、且つ前記Ｆｅ−Ａｌ層の膜厚は、４〜７．９ｎｍの範囲にある。
条件２：前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌは、０．２３〜０．５２の範囲にあり、且つ前記Ｆｅ−Ａｌ層の膜厚は、５．８〜７．９ｎｍの範囲にある。
条件３：前記Ｆｅ−Ａｌ層の組成比Ｆｅ／Ａｌは、０．５２以下であり、且つ前記Ｆｅ−Ａｌ層の膜厚は、５．８ｎｍ以下であり、且つ前記Ｆｅ−Ａｌ層のＦｅ膜厚が１．６ｎｍより厚い範囲にある。 Forming a plurality of CNTs on a substrate having a Fe—Al layer, which is an alloy layer of Fe and Al, on the surface;
Extracting a part of the plurality of CNTs;
A CNT wire manufacturing method comprising:
The composition ratio Fe / Al of the Fe—Al layer calculated based on the fluorescent X-ray measurement, the film thickness of the Fe—Al layer calculated based on the fluorescent X-ray measurement, and the Fe— calculated based on the fluorescent X-ray measurement. A method for producing a CNT wire, wherein the Fe film thickness, which is the film thickness in terms of Fe of the Al layer, satisfies any one of the following conditions 1, 2 and 3.
Condition 1: The composition ratio Fe / Al of the Fe—Al layer is in the range of 0.52 to 0.75, and the film thickness of the Fe—Al layer is in the range of 4 to 7.9 nm.
Condition 2: The composition ratio Fe / Al of the Fe—Al layer is in the range of 0.23 to 0.52, and the film thickness of the Fe—Al layer is in the range of 5.8 to 7.9 nm. .
Condition 3: The composition ratio Fe / Al of the Fe—Al layer is 0.52 or less, the film thickness of the Fe—Al layer is 5.8 nm or less, and the Fe film of the Fe—Al layer The thickness is in the range thicker than 1.6 nm.
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