JP4684053B2 - Method for producing carbon nanotube and method for fixing the same - Google Patents
Method for producing carbon nanotube and method for fixing the same Download PDFInfo
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- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 73
- 238000000034 method Methods 0.000 title claims description 26
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
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Description
本発明は、カーボンナノチューブの作製方法及びその固定方法に関し、特に基板上に密着して固定されたカーボンナノチューブの作製方法及び基板上にカーボンナノチューブを固定する方法に関する。 The present invention relates to a method for producing a carbon nanotube and a method for fixing the carbon nanotube, and more particularly, to a method for producing a carbon nanotube which is closely fixed on a substrate and a method for fixing the carbon nanotube on the substrate.
カーボンナノチューブ(本明細書中では、以下、「ＣＮＴ」と称す)の作製方法には、従来から様々な方法が提案されている。これらの方法に従って基板上にＣＮＴを直接成長させた場合、ＣＮＴと基板との密着性は低く、通常は、手で触れたり、風を吹き付けるだけで基板上からＣＮＴが剥がれてしまう。また、印刷法等で基板上にＣＮＴ液を塗布してＣＮＴを形成した場合も、粘着テープを貼り付けて引っ張ると簡単に剥がれてしまう。そのため、直接ＣＮＴに接触したり、ＣＮＴから強い電子放出や放電を起こさせると、基板からＣＮＴが取れてしまい、大電流の電子放出用途や、放電に曝される用途や、ＣＮＴとの接触がある用途には使用できないのが現状である。 Various methods have been proposed for producing carbon nanotubes (hereinafter referred to as “CNT” in the present specification). When CNTs are directly grown on a substrate according to these methods, the adhesion between the CNTs and the substrate is low, and usually the CNTs are peeled off from the substrate simply by touching with a hand or blowing wind. In addition, even when a CNT solution is applied on a substrate by a printing method or the like to form CNTs, they are easily peeled off when an adhesive tape is attached and pulled. For this reason, if the CNT is directly contacted or if strong electron emission or discharge is caused from the CNT, the CNT can be removed from the substrate, and there are applications of high current electron emission, exposure to discharge, and contact with the CNT. Currently, it cannot be used for certain purposes.
従って、１本ないし数本のＣＮＴを用いてデバイスを作製する際には、もう一度リソ工程を行い、金等を蒸着せしめて固定する方法が提案され(例えば、非特許文献１参照)、また、束のＣＮＴを用いる場合には、ＴｉＮ等のバッファー層で密着性を上げようとすることが提案されている(例えば、非特許文献２参照)。 Therefore, when producing a device using one or several CNTs, a method is proposed in which a litho process is performed once again and gold or the like is deposited and fixed (for example, see Non-Patent Document 1). In the case of using a bundle of CNTs, it has been proposed to increase the adhesion with a buffer layer such as TiN (see Non-Patent Document 2, for example).
また、電子放出源を、ＣＮＴを導電性物質に埋め込んでなる積層体を用い、加工処理して得る技術も提案されている(例えば、特許文献１参照)。
上記従来技術の場合、ＣＮＴの固定のためには追加の工程が必要であるという問題があり、また、バッファー層を用いて固定しても、やはり密着性が乏しく、触れると剥がれてしまうと共に、接触抵抗が増加するという問題がある。 In the case of the above prior art, there is a problem that an additional step is required for fixing CNT, and even if it is fixed using a buffer layer, the adhesion is still poor, and it will peel off when touched, There is a problem that the contact resistance increases.
そこで、本発明の課題は、上述の従来技術の問題点を解決することにあり、ＣＮＴと基板との密着性を向上させ、基板表面に触れた程度では剥がれず、さらに強めの衝撃にも密着性が損なわれず、また、導電性も熱伝導性も良く、接触抵抗も減少するＣＮＴの作製方法及びその固定方法を提供することにある。 Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, improve the adhesion between the CNT and the substrate, and do not peel off to the extent that it touches the substrate surface. It is an object of the present invention to provide a method for producing CNT and a method for fixing the same, in which the properties are not impaired, the conductivity and heat conductivity are good, and the contact resistance is reduced.
本発明の固定されたＣＮＴの作製方法は、基板上にカーボンナノチューブを成長させる際に、基板上にカーボンナノチューブ成長温度より高い融点を有する金属の膜を形成し、この金属膜の上に触媒を設けた基板を用い、この基板上に原料ガスを供給してカーボンナノチューブを成長させ、次いで金属膜をカーボンナノチューブ成長温度より高い温度で溶融させ、カーボンナノチューブの下端部分をこの溶融金属で被覆し、固定することを特徴とする。 In the method for producing a fixed CNT of the present invention, when carbon nanotubes are grown on a substrate, a metal film having a melting point higher than the carbon nanotube growth temperature is formed on the substrate, and a catalyst is formed on the metal film. Using the provided substrate, a raw material gas is supplied onto this substrate to grow carbon nanotubes, then the metal film is melted at a temperature higher than the carbon nanotube growth temperature, and the lower end portion of the carbon nanotubes is covered with this molten metal, It is fixed.
このようなプロセスを経ることにより、ＣＮＴと基板との密着性が向上する。すなわち、ＣＮＴ成長後に、その下端部分を溶融金属で被覆し、固定することで、ＣＮＴと基板とを強く密着させることができる。本発明の方法によれば、基板表面に触れた程度では、ＣＮＴは剥がれず、また、導電性、熱伝導性も良く、接触抵抗も低いので、ＣＮＴの特性を損なわないという利点がある。 Through such a process, the adhesion between the CNT and the substrate is improved. That is, after the CNT growth, the lower end portion thereof is covered with a molten metal and fixed, whereby the CNT and the substrate can be strongly adhered. According to the method of the present invention, the CNTs are not peeled off to the extent that they are touched on the substrate surface, and have the advantages that the properties of the CNTs are not impaired because they have good conductivity and thermal conductivity and low contact resistance.
上記溶融金属で被覆されたＣＮＴの下端部分の長さは、成長したＣＮＴの長さの１／３以下であれば良い。この被覆された下端部分の長さが１／３を超えると、ＣＮＴを金属で固定したときに、被覆されるＣＮＴ表面が多くなりすぎ、その結果、ＣＮＴの特性がこの被覆金属の特性により阻害される。この被覆された下端部分の長さの下限は１０ｎｍ程度であり、これより短いとＣＮＴを十分に固定することができない。 The length of the lower end portion of the CNT covered with the molten metal may be 1/3 or less of the length of the grown CNT. If the length of the coated lower end portion exceeds 1/3, when the CNT is fixed with metal, the surface of the coated CNT becomes too large, and as a result, the properties of the CNT are hindered by the properties of the coated metal. Is done. The lower limit of the length of the coated lower end portion is about 10 nm, and if it is shorter than this, the CNTs cannot be sufficiently fixed.
また、上記金属膜は、５μｍ以下の膜厚を有するものである。膜厚が５μｍを超えると、ＣＮＴを金属で固定したときに、金属がこのＣＮＴの上方表面まで覆ってしまい、その結果、ＣＮＴの特性がこの金属の特性により阻害される。また、膜厚の下限は、ＣＮＴの長さに依存し、長い場合だと多少厚めの方がよいが、いずれにしろＣＮＴを固定することができる値に適宜設定すれば良い。 The metal film has a thickness of 5 μm or less. When the film thickness exceeds 5 μm, when the CNT is fixed with a metal, the metal covers the upper surface of the CNT, and as a result, the characteristics of the CNT are hindered by the characteristics of the metal. Further, the lower limit of the film thickness depends on the length of the CNT, and if it is long, it is better to make it slightly thicker, but in any case, it may be set appropriately to a value that can fix the CNT.
基板上に形成される金属膜は、Ａｌ、Ｓｂ、Ｍｇ、Ａｕ、Ａｇ、Ｃｕ、及びこれらの金属の少なくとも１種を含む合金から選ばれた金属からなる膜であることが望ましい。この金属膜を構成する金属は上記選ばれた金属の１つ又は２つ以上の金属であればよい。 The metal film formed on the substrate is desirably a film made of a metal selected from Al, Sb, Mg, Au, Ag, Cu, and an alloy containing at least one of these metals. The metal constituting the metal film may be one or more than one of the above selected metals.
カーボンナノチューブ成長温度は、４００〜１２００℃であることが望ましく、このカーボンナノチューブは、熱ＣＶＤ法、プラズマＣＶＤ法、又はリモートプラズマＣＶＤ法により成長させることができる。この成長温度が４００℃未満であるとＣＮＴが十分に成長できず、また、上限の温度に関しては、固定のための金属の融点近傍になると金属が溶融、或いはマイグレートして触媒金属を覆ってしまい、ＣＮＴが成長しなくなるか又は成長したＣＮＴを覆ってしまうので、使用する金属の種類に応じて適宜設定すればよい。 The carbon nanotube growth temperature is desirably 400 to 1200 ° C., and the carbon nanotubes can be grown by a thermal CVD method, a plasma CVD method, or a remote plasma CVD method. If the growth temperature is less than 400 ° C., the CNTs cannot be grown sufficiently, and the upper limit of the temperature is close to the melting point of the metal for fixation, and the metal melts or migrates to cover the catalyst metal. As a result, the CNT does not grow or covers the grown CNT, so that the CNT may be appropriately set according to the type of metal used.
本発明で用いる触媒は、Ｆｅ、Ｃｏ、Ｎｉ及びこれら金属の少なくとも１種を含む合金から選ばれたものであり、ＥＢ蒸着法、抵抗加熱蒸着法、又はスパッタ法により上記金属膜上に成膜され得る。また、この触媒は、湿式の塗布法により金属膜上に微粒子形成されていても良い。 The catalyst used in the present invention is selected from Fe, Co, Ni, and an alloy containing at least one of these metals, and is formed on the metal film by EB vapor deposition, resistance heating vapor deposition, or sputtering. Can be done. The catalyst may be formed into fine particles on the metal film by a wet coating method.
本発明においては、金属膜を６００〜１５００℃で溶融させて、成長したカーボンナノチューブの下端部分の所定の部分を被覆する。６００℃未満であるとカーボンナノチューブを十分に固定できず、また、上限の温度に関しては、固定のための金属の融点を大きく超えると、この金属により、カーボンナノチューブ表面がその所定部分を超えて覆われてしまうため、好ましくない。 In the present invention, the metal film is melted at 600 to 1500 ° C. to cover a predetermined portion of the lower end portion of the grown carbon nanotube. If the temperature is lower than 600 ° C., the carbon nanotubes cannot be sufficiently fixed, and the upper limit of the temperature exceeds the melting point of the metal for fixing, and the metal covers the surface of the carbon nanotubes beyond its predetermined portion. It is not preferable because it is broken.
本発明の別の固定されたカーボンナノチューブの作製方法は、基板上にカーボンナノチューブを成長させる際に、カーボンナノチューブ成長温度より高い融点を有する金属からなる基板を用い、この金属基板上に触媒を成膜又は微粒子化形成して設けた後、この金属基板上に原料ガスを供給してカーボンナノチューブを成長させ、次いで該金属基板の表面部分を該カーボンナノチューブ成長温度より高い温度で溶融させ、カーボンナノチューブの下端部分をこの溶融金属で被覆し、固定することを特徴とする。 In another method for producing a fixed carbon nanotube of the present invention, when a carbon nanotube is grown on a substrate, a substrate made of a metal having a melting point higher than the carbon nanotube growth temperature is used, and a catalyst is formed on the metal substrate. After the film or fine particles are formed, a raw material gas is supplied onto the metal substrate to grow carbon nanotubes, and then the surface portion of the metal substrate is melted at a temperature higher than the carbon nanotube growth temperature. The lower end portion of this is covered with this molten metal and fixed.
この別の発明においては、溶融金属で被覆されたカーボンナノチューブの下端部分の長さは、成長したカーボンナノチューブの長さの１／３以下である。金属基板は、Ａｌ、Ｓｂ、Ｍｇ、Ａｕ、Ａｇ、Ｃｕ、及びこれらの金属の少なくとも１種を含む合金から選ばれた金属からなる基板である。この基板を構成する金属は上記選ばれた金属の１つ又は２つ以上の金属であればよい。カーボンナノチューブ成長温度は、４００〜１２００℃であり、カーボンナノチューブを、熱ＣＶＤ法、プラズマＣＶＤ法、リモートプラズマＣＶＤ法により成長させることができる。触媒は、Ｆｅ、Ｃｏ、Ｎｉ及びこれら金属の少なくとも１種を含む合金から選ばれたものであって、ＥＢ蒸着法、抵抗加熱蒸着法、スパッタ法により金属基板上に成膜されているか、又は湿式の塗布法により金属基板上に微粒子形成されている。また、金属基板表面部分を６００〜１５００℃で溶融させることによりカーボンナノチューブの下端部分の所定の部分を固定する。この温度範囲に関しては上記した通りである。 In this another invention, the length of the lower end portion of the carbon nanotube covered with the molten metal is 1/3 or less of the length of the grown carbon nanotube. The metal substrate is a substrate made of a metal selected from Al, Sb, Mg, Au, Ag, Cu, and an alloy containing at least one of these metals. The metal constituting this substrate may be one or more than one of the above selected metals. The carbon nanotube growth temperature is 400 to 1200 ° C., and the carbon nanotubes can be grown by a thermal CVD method, a plasma CVD method, or a remote plasma CVD method. The catalyst is selected from Fe, Co, Ni, and an alloy containing at least one of these metals, and is formed on a metal substrate by EB vapor deposition, resistance heating vapor deposition, or sputtering, or Fine particles are formed on the metal substrate by a wet coating method. Moreover, the predetermined part of the lower end part of a carbon nanotube is fixed by melting a metal substrate surface part at 600-1500 degreeC. This temperature range is as described above.
本発明のカーボンナノチューブの固定方法は、基板上にカーボンナノチューブを成長させる際に、基板上にカーボンナノチューブ成長温度より高い融点を有する金属の膜を形成し、この金属膜の上に触媒を設けた基板を用いるか、又はカーボンナノチューブ成長温度より高い融点を有する金属からなる金属基板の上に触媒を設けた基板を用い、この基板上に原料ガスを供給してカーボンナノチューブを成長させ、次いで該金属膜又は該金属基板の表面部分をカーボンナノチューブ成長温度より高い温度で溶融させ、カーボンナノチューブの下端部分をこの溶融金属で被覆し、固定することを特徴とする。 In the carbon nanotube fixing method of the present invention, when carbon nanotubes are grown on a substrate, a metal film having a melting point higher than the carbon nanotube growth temperature is formed on the substrate, and a catalyst is provided on the metal film. A substrate is used, or a substrate provided with a catalyst on a metal substrate made of a metal having a melting point higher than the carbon nanotube growth temperature is used, and a raw material gas is supplied onto this substrate to grow carbon nanotubes, and then the metal The surface portion of the film or the metal substrate is melted at a temperature higher than the carbon nanotube growth temperature, and the lower end portion of the carbon nanotube is covered with the molten metal and fixed.
本発明によれば、ＣＮＴ成長後に、その下端部分を溶融金属で被覆し、固定することにより、ＣＮＴと基板との密着性を向上させ、基板表面に触れた程度では剥がれず、さらに強めの衝撃にも密着性が損なわれず、また、導電性も熱伝導性も良く、接触抵抗も低い固定されたＣＮＴを提供できるという効果を奏する。 According to the present invention, after the growth of CNT, the lower end portion thereof is coated with a molten metal and fixed, thereby improving the adhesion between the CNT and the substrate. In addition, there is an effect that it is possible to provide a fixed CNT which is not impaired in adhesion, has good conductivity and thermal conductivity, and has low contact resistance.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明のＣＮＴの作製方法によれば、ＣＮＴ成長温度より高い融点を有する金属の膜を形成し、この金属膜の上に触媒を設けた基板上にＣＮＴ作製用原料ガスを供給して、所定の温度で基板上にＣＮＴを成長させた後、成長したＣＮＴの下に存在させてある金属膜を溶融させ、この溶融金属によりＣＮＴの下端部分の所定の範囲を被覆し、ＣＮＴを基板に固定して、基板とＣＮＴとを密着させる。 According to the CNT production method of the present invention, a metal film having a melting point higher than the CNT growth temperature is formed, and a CNT production source gas is supplied onto a substrate provided with a catalyst on the metal film. After growing CNTs on the substrate at a temperature of, the metal film existing under the grown CNTs is melted, and this molten metal covers a predetermined range of the lower end portion of the CNTs, and the CNTs are fixed to the substrate. Then, the substrate and the CNT are brought into close contact with each other.
本発明によれば、ＣＮＴの成長を妨げないために、ＣＮＴ成長後に金属膜を溶融させる必要があるので、この金属としては、ＣＮＴ成長温度より融点が高い金属を用いることが必要である。 According to the present invention, since the metal film needs to be melted after CNT growth in order not to hinder the growth of CNT, it is necessary to use a metal having a melting point higher than the CNT growth temperature.
ＣＮＴと基板との間に設ける金属膜は、成長したＣＮＴの長さの、一般に１／３以下、好ましくは１／１０以下、より好ましくは１／１００以下の下端部分を被覆するような量の金属を用いて形成する。溶融金属で被覆されたＣＮＴの下端部分の長さが１／３を超えると、上記したように、ＣＮＴの特性がこの金属の特性により阻害される。また、ＣＮＴを十分に基板に固定するためには、この被覆された下端部分の長さの下限は、好ましくは１０ｎｍ程度である。 The metal film provided between the CNT and the substrate is of an amount that covers the lower end portion of the grown CNT, which is generally 1/3 or less, preferably 1/10 or less, more preferably 1/100 or less. It is formed using metal. When the length of the lower end portion of the CNT covered with the molten metal exceeds 1/3, the characteristics of the CNT are hindered by the characteristics of the metal as described above. Further, in order to sufficiently fix the CNT to the substrate, the lower limit of the length of the coated lower end portion is preferably about 10 nm.
また、この金属膜の膜厚は、実用的観点から、一般に５μｍ以下とすれば良い。この膜厚が厚すぎると、上記したように、ＣＮＴの特性がこの金属の特性により阻害される。ＣＮＴを十分に固定するためには、この膜厚の下限は、好ましくは１０ｎｍ程度である。 The thickness of the metal film is generally 5 μm or less from a practical viewpoint. If this film thickness is too thick, as described above, the properties of the CNT are hindered by the properties of the metal. In order to sufficiently fix CNTs, the lower limit of the film thickness is preferably about 10 nm.
上記触媒調製方法及びＣＮＴの成長方法における原材料及びプロセス条件は、特に限定されるわけではなく、既知の材料及びプロセス条件を全て使用することができる。例えば、ＣＮＴ作製プロセスとしては、熱ＣＶＤ法、プラズマＣＶＤ法、リモートプラズマＣＶＤ法等が挙げられ、ＣＮＴ作製用原料ガスとしては、アセチレンやメタン等の炭化水素、一酸化炭素、エタノール等のアルコールが挙げられ、ＣＮＴ成長温度は４００〜１２００℃程度及び圧力は１〜７６０Ｔｏｒｒ程度である。また、触媒としては、Ｆｅ、Ｃｏ、Ｎｉ及びこれら金属の少なくとも１種を含む合金等が挙げられる。この触媒は、膜として設けても微粒子化して設けても良く、例えば、ＥＢ蒸着法、抵抗加熱蒸着法、スパッタ法や湿式の塗布法により調製され得る。 The raw materials and process conditions in the catalyst preparation method and the CNT growth method are not particularly limited, and all known materials and process conditions can be used. For example, the CNT production process includes a thermal CVD method, a plasma CVD method, a remote plasma CVD method, and the like. Examples of the source gas for CNT production include hydrocarbons such as acetylene and methane, and alcohols such as carbon monoxide and ethanol. The CNT growth temperature is about 400 to 1200 ° C., and the pressure is about 1 to 760 Torr. Examples of the catalyst include Fe, Co, Ni, and alloys containing at least one of these metals. This catalyst may be provided as a film or in the form of fine particles, and can be prepared, for example, by EB vapor deposition, resistance heating vapor deposition, sputtering, or wet coating.
本発明によれば、基板として、例えば、シリコン基板や、石英、ガラス板、グラファイト板等を用いることができる。この基板上に上記ＣＮＴ固定用の金属膜を、例えばＥＢ蒸着法、スパッタリング法、又はメッキ法等で、既知のプロセス条件に基づき形成した後、形成された金属膜上に既知のＣＮＴ成長用触媒を成膜又は微粒子化形成して、ＣＮＴ成長用基板を作製する。その後、上記固定用金属の融点より低い温度、好ましくはこの金属原子のマイグレーションが起こる温度より低い温度でＣＮＴの成長を行う。ＣＮＴの成長後、この金属の融点まで或いはそれ以上まで昇温させ、ＣＮＴの所定の下端部分を溶融した金属で被覆し、固定する。 According to the present invention, for example, a silicon substrate, quartz, a glass plate, a graphite plate, or the like can be used as the substrate. After the metal film for fixing the CNTs is formed on the substrate by, for example, an EB vapor deposition method, a sputtering method, or a plating method based on known process conditions, a known CNT growth catalyst is formed on the formed metal film. Is formed or formed into fine particles to produce a substrate for CNT growth. Thereafter, CNTs are grown at a temperature lower than the melting point of the fixing metal, preferably at a temperature lower than the temperature at which metal atom migration occurs. After the growth of the CNTs, the temperature is raised to the melting point of the metal or higher, and a predetermined lower end portion of the CNT is coated with the molten metal and fixed.
基板として、上記ＣＮＴ固定用の金属、例えばＡｌ、Ｓｂ、Ｍｇ、Ａｕ、Ａｇ、Ｃｕ、及びこれらの金属の少なくとも１種を含む合金等からなる金属基板を用いることもできる。この場合には、この金属基板上に触媒を成膜するか或いは微粒子化形成した後、金属基板の融点より低い温度、好ましくはこの金属原子のマイグレーションが起こる温度より低い温度でＣＮＴの成長を行う。ＣＮＴの成長後、この基板を構成する金属の融点まで或いはそれ以上まで昇温させ、ＣＮＴの所定の下端部分を溶融した金属で被覆し、固定する。この際、金属基板の表面部分が溶融するように、昇温、降温の速度と保持温度と保持時間とを適宜調整する。これは、金属基板を溶融させすぎると、ＣＮＴ表面の所定部分以上が覆われてしまい、上記したような問題が生じるからである。反対に、溶融程度が少ないと、ＣＮＴを満足に固定することができない。 As the substrate, a metal substrate made of the above-mentioned metal for fixing CNT, such as Al, Sb, Mg, Au, Ag, Cu, and an alloy containing at least one of these metals, can also be used. In this case, after the catalyst is formed on the metal substrate or formed into fine particles, the CNTs are grown at a temperature lower than the melting point of the metal substrate, preferably lower than the temperature at which migration of the metal atoms occurs. . After the growth of the CNTs, the temperature is raised to the melting point of the metal constituting the substrate or higher, and a predetermined lower end portion of the CNT is covered with the molten metal and fixed. At this time, the rate of temperature increase / decrease, the holding temperature, and the holding time are appropriately adjusted so that the surface portion of the metal substrate is melted. This is because, if the metal substrate is melted too much, a predetermined part or more of the CNT surface is covered, and the above-described problems occur. On the other hand, if the degree of melting is small, the CNTs cannot be satisfactorily fixed.
以下、実施例を挙げて本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
基板としてシリコン(１００)基板、触媒としてＦｅ、ＣＮＴ成長用反応ガスとしてアセチレンを用い、以下のプロセスに従ってＣＮＴを作製した。 CNTs were produced according to the following process using a silicon (100) substrate as a substrate, Fe as a catalyst, and acetylene as a reactive gas for CNT growth.
成膜室内に載置したシリコン基板上にアルミニウム(融点：６６０℃)をＥＢ蒸着により１μｍ程度の膜厚で成膜した後、そのアルミニウム膜上にＦｅ触媒を成膜した。次いで、成膜室内に、１気圧の圧力下、１Ｌ／ｍｉｎの窒素ガスを導入し、６００℃まで昇温させ、アセチレンを３００ｃｃ／ｍｉｎで３０秒間流して、基板上にＣＮＴを成長せしめた(長さ：１０μｍ)。その後、真空排気してから、７５０℃まで昇温させて、アルミニウムを溶融せしめ、ＣＮＴの下端部分を１０ｎｍ程度被覆せしめた。かくして得られたＣＮＴの固定された基板の断面ＳＥＭ写真を図１に示す。図１から明らかなように、基板上に垂直に密集して成長したブラシ状のＣＮＴがその下端部分が固定されて形成されていることが分かる。このＣＮＴは、テープテストによれば１ｋＧ／ｃｍ２以上の強度を有し、手で触れても剥がれず、密着性が良いことが確認できた。また、導電性も熱伝導性も良く、接触抵抗も低いことが確認された。 After depositing aluminum (melting point: 660 ° C.) to a thickness of about 1 μm on the silicon substrate placed in the deposition chamber by EB vapor deposition, an Fe catalyst was deposited on the aluminum film. Next, 1 L / min of nitrogen gas was introduced into the film formation chamber under a pressure of 1 atm, the temperature was raised to 600 ° C., and acetylene was allowed to flow at 300 cc / min for 30 seconds to grow CNTs on the substrate ( Length: 10 μm). Then, after evacuating, it heated up to 750 degreeC, the aluminum was melted, and the lower end part of CNT was coat | covered about 10 nm. A cross-sectional SEM photograph of the CNT-fixed substrate thus obtained is shown in FIG. As is clear from FIG. 1, it can be seen that brush-like CNTs that are densely grown vertically on the substrate are formed with their lower end portions fixed. According to the tape test, this CNT had a strength of 1 kG / cm 2 or more, and even if it was touched by hand, it was confirmed that the adhesion was good. Further, it was confirmed that the conductivity and heat conductivity were good and the contact resistance was low.
アルミニウム板上にＦｅ触媒を５ｎｍの膜厚でＥＢ蒸着により成膜して得た基板を使用したことを除いて、実施例１と同条件でＣＮＴの成長を実施した。基板上に成長したＣＮＴの長さは３０μｍであった。真空排気後、６００℃から７５０℃まで１分間で昇温して、この温度に１０秒間保持し、次いで降温した。この場合、アルミニウム板の表面が溶融してＣＮＴの下端部分が１０ｎｍ程度被覆された。かくして得られたＣＮＴの固定された基板の断面ＳＥＭ写真を図２に示す。図２から明らかなように、基板上に垂直に密集して成長したブラシ状のＣＮＴが形成されていることが分かる。このＣＮＴは、テープテストによれば１ｋＧ／ｃｍ２以上の強度を有し、粘着テープを貼って、引っ張った程度では剥がすことができず、強固にアルミニウム板と結合していることが確認できた。また、導電性も熱伝導性も良く、接触抵抗も低いことが確認された。 CNTs were grown under the same conditions as in Example 1 except that a substrate obtained by depositing an Fe catalyst with a thickness of 5 nm on an aluminum plate by EB deposition was used. The length of the CNT grown on the substrate was 30 μm. After evacuation, the temperature was raised from 600 ° C. to 750 ° C. over 1 minute, held at this temperature for 10 seconds, and then lowered. In this case, the surface of the aluminum plate was melted and the lower end portion of the CNT was covered with about 10 nm. A cross-sectional SEM photograph of the CNT-fixed substrate thus obtained is shown in FIG. As is apparent from FIG. 2, it can be seen that brush-like CNTs that grow densely vertically on the substrate are formed. According to the tape test, this CNT had a strength of 1 kG / cm 2 or more, and it was confirmed that the CNT was firmly bonded to the aluminum plate without being peeled to the extent that the adhesive tape was applied and pulled. . Further, it was confirmed that the conductivity and heat conductivity were good and the contact resistance was low.
実施例１と同じシリコン基板上に、Ｃｕを用いて、ＥＢ蒸着により１μｍ成膜した。次いで、実施例１と同様の条件で、触媒を形成し、そしてＣＮＴの成長を実施した。基板上に成長したＣＮＴの長さは、５０μｍであった。次いで、真空中、１１００℃で１秒、１０秒、１００秒、及び３００秒の間、金属膜を溶融し、ＣＮＴを基板上に固定した。かくして得られたＣＮＴは、実施例１と同様の形態を有し、上記各溶融時間に応じて、それぞれ、ＣＮＴの長さの１／１０００、１／１００、１／１０、及び１／３をＣｕが被覆し、実施例１の場合と同様の強度を示すことが確認できた。また、導電性も熱伝導性も良く、接触抵抗も低いことが確認された。 A 1 μm film was formed on the same silicon substrate as in Example 1 by EB deposition using Cu. Next, under the same conditions as in Example 1, a catalyst was formed and CNT growth was performed. The length of the CNT grown on the substrate was 50 μm. Next, the metal film was melted at 1100 ° C. for 1 second, 10 seconds, 100 seconds, and 300 seconds in vacuum to fix the CNTs on the substrate. The CNT thus obtained has the same form as in Example 1, and 1/1000, 1/100, 1/10, and 1/3 of the length of the CNT, respectively, according to each melting time. It was confirmed that Cu was coated and showed the same strength as in Example 1. Further, it was confirmed that the conductivity and heat conductivity were good and the contact resistance was low.
実施例１と同じシリコン基板上に、Ｃｕを用いて、ＥＢ蒸着により１０ｎｍ、１００ｎｍ、５００ｎｍ及び１μｍの膜厚を有するＣｕ膜を形成した。次いで、実施例１と同様の条件で、触媒を形成し、そしてＣＮＴの成長を実施した。基板上に成長したＣＮＴの長さは５０μｍであった。次いで、１１００℃、３００秒という条件で金属膜を溶融し、ＣＮＴを基板上に固定した。かくして得られたＣＮＴは、上記各膜厚に応じて、それぞれ、金属で被覆された下端部分の長さが成長したＣＮＴの長さの１／５００、１／５０、１／１０、及び１／３であり、また、実施例１と同様の形態を有し、同様の強度を示すことが確認できた。また、導電性も熱伝導性も良く、接触抵抗も低いことが確認された。 On the same silicon substrate as in Example 1, Cu was used to form Cu films having thicknesses of 10 nm, 100 nm, 500 nm, and 1 μm by EB vapor deposition. Next, under the same conditions as in Example 1, a catalyst was formed and CNT growth was performed. The length of the CNT grown on the substrate was 50 μm. Next, the metal film was melted under the conditions of 1100 ° C. and 300 seconds, and the CNTs were fixed on the substrate. The CNTs thus obtained were 1/500, 1/50, 1/10, and 1/500 of the length of the grown CNTs, with the length of the lower end portion coated with metal being increased according to each film thickness. 3 and the same form as in Example 1 and the same strength was confirmed. Further, it was confirmed that the conductivity and heat conductivity were good and the contact resistance was low.
本発明によれば、ＣＮＴと基板との密着性を向上させ、基板表面に触れた程度では剥がれず、さらに強めの衝撃にも密着性が損なわれず、また、導電性も熱伝導性も良く、接触抵抗も低いＣＮＴを提供できる。そのため、これまで用途が限られていたＣＮＴを、直接接触させるような用途や、強い気流などが加わるような用途に使用することができる。従って、本発明は、ＣＮＴを使用する産業分野で有効に利用できる。 According to the present invention, the adhesion between the CNT and the substrate is improved, it does not peel off to the extent that it touches the substrate surface, the adhesion is not impaired even by a stronger impact, and the conductivity and heat conductivity are good, CNTs with low contact resistance can be provided. Therefore, it can be used for applications in which CNTs, which have been limited in use so far, are in direct contact with each other or where a strong air current is applied. Therefore, the present invention can be effectively used in industrial fields that use CNTs.
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