JP2009137805A - Method for producing carbon nanotube, and substrate on which carbon nanotube has been grown - Google Patents
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本発明は、カーボンナノチューブ（以下、ＣＮＴと称す）の作製方法及びＣＮＴを成長させた基板、特に基板との密着性の高いＣＮＴの作製方法及びＣＮＴを密着性良く成長させた基板に関する。 The present invention relates to a method for producing carbon nanotubes (hereinafter referred to as CNT), a substrate on which CNTs are grown, particularly a method for producing CNTs having high adhesion to the substrates, and a substrate on which CNTs are grown with good adhesion.
ＣＮＴの作製方法には、従来から種々の方法が提案されている。ＣＮＴの作製方法として、基板上にＣＮＴを垂直配向させ、かつ密集成長させた、いわゆるブラシ状ＣＮＴについては、種々の成長方法や、基板技術や、触媒調製方法等が報告されている。しかし、いずれの場合も、成長したＣＮＴが基板表面から容易に剥がれてしまうという共通の問題点がある。ＣＮＴの基板への密着性は非常に弱く、ＣＮＴがエアブローで容易に剥離してしまったり、エアブローで剥離しなくても、ＣＮＴが何かに接触して負荷がかかると剥離してしまうという問題がある。密着性が弱いために、成長させたＣＮＴに負荷がかかる用途には使用できない。 Various methods for producing CNTs have been proposed. As a method for producing CNTs, various growth methods, substrate technologies, catalyst preparation methods, and the like have been reported for so-called brush-like CNTs in which CNTs are vertically aligned and densely grown on a substrate. However, in any case, there is a common problem that the grown CNT easily peels off from the substrate surface. The adhesion of CNTs to the substrate is very weak, and the CNTs can be easily peeled off by air blow, or even if they are not peeled off by air blow, they will peel off if they come into contact with something and a load is applied. There is. Since the adhesion is weak, it cannot be used for applications in which the grown CNT is loaded.
ＣＮＴの密着性を改良することを目的とするＣＮＴ作製方法が知られている（例えば、特許文献１参照）。この作製方法は、基板上に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、次いでＣＮＴを成長せしめた後に、金属膜を溶融させてＣＮＴの下端部分を溶融金属で被覆して固定する方法である。これにより、ＣＮＴと基板との密着性が向上し、ＣＮＴ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、基板に固定されたＣＮＴが作製される。この場合、ＣＮＴ成長後に溶融工程を行うので、プロセス工程が増えるという問題がある。 A CNT manufacturing method for improving the adhesion of CNTs is known (for example, see Patent Document 1). In this production method, a metal film having a melting point higher than the CNT growth temperature is formed on a substrate, a catalyst is provided on the metal film, and then the CNT is grown, and then the metal film is melted to melt the lower end of the CNT. In this method, the portion is covered with a molten metal and fixed. As a result, the adhesion between the CNT and the substrate is improved, and the CNT fixed to the substrate is produced without being peeled off to the extent that the CNT is touched and without being damaged even by a strong impact. In this case, since the melting step is performed after CNT growth, there is a problem that the number of process steps increases.
また、流動気相ＣＶＤ法により極細単層ＣＮＴからなる炭素繊維集合体を製造する際に、２種類の分解温度の異なる炭素源を、所定の割合で用いることによりＣＮＴの直径を制御することが知られている（例えば、特許文献２参照）。この製造方法では、第一の炭素源として、芳香族炭化水素、脂環式炭化水素、長鎖脂肪族炭化水素を用い、第二の炭素源として、不飽和脂肪族炭化水素を用いて、直径の制御された（２．０ｎｍ未満）ＣＮＴからなる炭素繊維集合体を製造しているに過ぎず、基板上にＣＮＴを密着性良く成長せしめるものではない。 In addition, when producing a carbon fiber aggregate composed of ultrafine single-walled CNTs by a fluidized gas phase CVD method, the diameter of the CNTs can be controlled by using two types of carbon sources having different decomposition temperatures at a predetermined ratio. It is known (see, for example, Patent Document 2). In this production method, an aromatic hydrocarbon, an alicyclic hydrocarbon, or a long-chain aliphatic hydrocarbon is used as the first carbon source, and an unsaturated aliphatic hydrocarbon is used as the second carbon source. The carbon fiber aggregates made of CNTs with controlled CNTs (less than 2.0 nm) are merely produced, and the CNTs are not grown on the substrate with good adhesion.
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、基板との密着性に優れたＣＮＴの簡便な作製方法及びこの作製方法によりＣＮＴを密着性良く成長せしめてなる基板を提供することにある。 An object of the present invention is to solve the above-mentioned problems of the prior art, and a simple method for producing CNTs having excellent adhesion to a substrate and a substrate in which CNTs are grown with good adhesion by this production method. It is to provide.
本発明のＣＮＴの作製方法は、基板上にＣＮＴを作製する方法において、ＣＮＴ作製用原料ガスとして、分解温度の異なる少なくとも二種類の炭化水素ガスを好ましくは混合して使用することを特徴とする。 The method for producing CNTs of the present invention is characterized in that, in the method for producing CNTs on a substrate, at least two types of hydrocarbon gases having different decomposition temperatures are preferably used as a raw material gas for producing CNTs. .
本発明によれば、上記したように、原料ガスとして分解温度の異なる少なくとも二種類の炭化水素ガスを混合して使用することによって、ＣＮＴの成長とカーボン薄膜との形成が起こり、作製したＣＮＴと基板との接合箇所を含めた根本部分又は根本部分を含めた全表面が原料ガス由来のカーボン薄膜で覆われ、その結果、基板に対するＣＮＴの密着性が顕著に向上する。使用する炭化水素ガスが１種類の場合、作製したＣＮＴの表面、根本部分をカーボン薄膜で覆うことは難しい。この場合、ＣＮＴ成長温度よりも高温にすることで、ＤＬＣ（ダイアモンド様カーボン）等のカーボン膜になる可能性はあるが、何らかの工夫を加えなければ、通常はアモルファスカーボンとして粉末の堆積物になってしまう。 According to the present invention, as described above, by using a mixture of at least two types of hydrocarbon gases having different decomposition temperatures as a raw material gas, growth of CNT and formation of a carbon thin film occur. The base portion including the joint portion with the substrate or the entire surface including the root portion is covered with the carbon thin film derived from the source gas, and as a result, the adhesion of the CNTs to the substrate is significantly improved. When one type of hydrocarbon gas is used, it is difficult to cover the surface and the base portion of the produced CNT with a carbon thin film. In this case, there is a possibility that it becomes a carbon film such as DLC (diamond-like carbon) by setting the temperature higher than the CNT growth temperature. However, unless some contrivance is added, it usually becomes a powder deposit as amorphous carbon. End up.
上記ＣＮＴ作製方法において、分解温度の異なる少なくとも二種類の炭化水素ガスが分解温度の異なる二種類の炭化水素ガスからなり、低温分解ガスにアセチレン及び高温分解ガスにエチレン若しくはメタン、又は低温分解ガスにエチレン及び高温分解ガスにメタンを使用することを特徴とする。 In the CNT manufacturing method, at least two types of hydrocarbon gases having different decomposition temperatures are composed of two types of hydrocarbon gases having different decomposition temperatures, acetylene as a low temperature decomposition gas, ethylene or methane as a high temperature decomposition gas, or as a low temperature decomposition gas. It is characterized by using methane for ethylene and hot cracked gas.
上記分解温度の異なる少なくとも二種類の炭化水素ガスが分解温度の異なる二種類の炭化水素ガスからなり、低温分解ガスの使用量が、流量（ｓｃｃｍ）基準で、高温分解ガスの使用量の０．０１〜２０％であることが好ましい。その使用量が０．０１％未満であると、十分なＣＮＴの密着性が得られず、また、使用量が２０％を超えると、アモルファスカーボンが生じてしまう。この範囲内の割合で分解温度の異なる二種類のガスを使用すれば、基板上にＣＮＴが密着性良く成長する。 The at least two types of hydrocarbon gases having different cracking temperatures are composed of two types of hydrocarbon gases having different cracking temperatures, and the amount of the low-temperature cracked gas used is 0.0% of the amount of the hot cracked gas used on the basis of the flow rate (sccm). It is preferable that it is 01 to 20%. If the amount used is less than 0.01%, sufficient adhesion of CNTs cannot be obtained, and if the amount used exceeds 20%, amorphous carbon is produced. If two kinds of gases having different decomposition temperatures at a rate within this range are used, CNTs grow on the substrate with good adhesion.
上記炭化水素ガスが、Ｎ２、Ａｒ、Ｈｅ、Ｈ２、及びＮＨ３から選ばれた少なくとも一種類のガスで希釈されていることが好ましい。 The hydrocarbon gas is preferably diluted with at least one gas selected from N 2 , Ar, He, H 2 , and NH 3 .
上記ＣＮＴを、熱ＣＶＤ法、プラズマＣＶＤ法、又は触媒を利用したリモートプラズマＣＶＤ法のようなＣＶＤ法を用いて作製することが好ましい。 It is preferable to produce the CNTs using a CVD method such as a thermal CVD method, a plasma CVD method, or a remote plasma CVD method using a catalyst.
また、本発明のＣＮＴが成長した基板は、上記作製方法により作製された、接合箇所を含めた根本部分又は根本部分を含めた全表面がカーボン薄膜で覆われたＣＮＴを成長させてなる基板である。 In addition, the substrate on which the CNT of the present invention has grown is a substrate formed by the above-described manufacturing method, and is a substrate formed by growing a CNT with a carbon thin film covered on the entire surface including the joint portion or the entire surface including the joint portion. is there.
本発明によれば、基板との密着性の良いＣＮＴを作製することができると共に、ＣＮＴが密着性良く成長した基板を提供できるという効果を奏する。 According to the present invention, it is possible to produce CNTs having good adhesion to a substrate and to provide a substrate on which CNTs are grown with good adhesion.
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の作製方法の一実施の形態によれば、基板上に、例えばスパッタリング法又はＥＢ蒸着法により、金属膜、窒化物膜、及び酸化物膜（例えば、Ａｌ、Ｔｉ、ＴｉＮ、及びＡｌ２Ｏ３膜等）を形成し、次いでスパッタリング法、ＥＢ蒸着法、アークプラズマ蒸着法等により、この金属膜上にＣＮＴ成長用触媒を成膜して触媒付き基板を得、かくして得られた基板上に、分解温度の異なる少なくとも二種類のＣＮＴ作製用原料ガスである炭化水素ガスの混合ガスを供給し、例えば、Ｆｅ触媒を使用した場合、低温分解ガスとしてアセチレン（分解温度：６００〜７５０℃）、高温分解ガスとしてエチレン（分解温度：７５０〜８５０℃）若しくはメタン（分解温度：８５０〜９５０℃）、又は低温分解ガスとしてエチレン、高温分解ガスとしてメタンを供給し、好ましくは、低温分解ガスを、その使用量が、流量基準で、高温分解ガスの使用量の０．０１〜２０％となるような割合で供給し、所定の温度及び圧力で基板上にＣＮＴを作製する。この場合、上記炭化水素ガスとして、Ｎ２、Ａｒ、Ｈｅ、Ｈ２、及びＮＨ３から選ばれた少なくとも一種類のガスで希釈されている炭化水素ガスを用いても良い。 According to an embodiment of the CNT manufacturing method of the present invention, a metal film, a nitride film, and an oxide film (for example, Al, Ti, TiN, and the like) are formed on a substrate by, for example, a sputtering method or an EB deposition method. forming an al 2 O 3 film, etc.), then sputtering, EB evaporation, by arc plasma deposition method and the like, to obtain a catalyst-coated substrate by forming a CNT growth catalyst on the metal film, thus obtained When a mixed gas of hydrocarbon gas, which is at least two kinds of raw material gases for producing CNTs having different decomposition temperatures, is supplied onto a substrate, for example, when an Fe catalyst is used, acetylene (decomposition temperature: 600 to 750) is used as a low temperature decomposition gas. ° C), ethylene as the high temperature cracking gas (decomposition temperature: 750-850 ° C) or methane (cracking temperature: 850-950 ° C), or ethylene as the low temperature cracking gas, high temperature Methane is supplied as a degassing gas, preferably a low-temperature cracked gas is supplied at a rate such that the amount used is 0.01 to 20% of the amount used of the high-temperature cracked gas based on the flow rate, and a predetermined temperature. And CNTs on the substrate with pressure. In this case, as the hydrocarbon gas, a hydrocarbon gas diluted with at least one gas selected from N 2 , Ar, He, H 2 , and NH 3 may be used.
基板としては、例えばシリコン、石英、サファイヤ、金属（例えば、Ｔｉ、Ｃｒ、ＳｉＣ、ＡｌＮ等）からなる基板を使用できる。Ｆｅ、Ｃｏ、Ｎｉ、或いはＳＵＳ（ステンレス）等から選ばれた少なくともどれか一つを含む金属基板なら、これらの金属等が触媒となるので、触媒成膜は必要ない。そのほかのＡｌやＴｉ等の場合はバッファ層だけとなる。 As the substrate, for example, a substrate made of silicon, quartz, sapphire, metal (for example, Ti, Cr, SiC, AlN, etc.) can be used. In the case of a metal substrate including at least one selected from Fe, Co, Ni, SUS (stainless steel) or the like, these metals and the like serve as a catalyst, and thus no catalyst film formation is necessary. In the case of other Al or Ti, only the buffer layer is provided.
触媒としては、公知のＣＮＴ成長用触媒であれば制限なく使用でき、例えばＣｏ、Ｎｉ、及びＦｅから選ばれたいずれか一種、又はこれらの金属の少なくとも一種を含む合金（例えば、Ｎｉ−Ｆｅ合金（アンバー）、ステンレス等）を使用できる。 As the catalyst, any known CNT growth catalyst can be used without limitation. For example, any one selected from Co, Ni, and Fe, or an alloy containing at least one of these metals (for example, a Ni-Fe alloy). (Amber), stainless steel, etc.) can be used.
分解温度の異なる少なくとも二種類のＣＮＴ作製用原料ガスである炭化水素ガスとしては、アセチレンやエチレン等の不飽和炭化水素ガス、メタン等の飽和炭化水素ガス、及びメタノール（分解温度：７５０℃）やエタノール（分解温度：７００℃）等のアルコールを、分解温度に差ができるように適宜組み合わせて使用できる。この場合、炭化水素同士を分解温度に差が出るように適宜組み合わせ、アルコール同士を分解温度に差が出るように適宜組み合わせ、或いは炭化水素とアルコールとを分解温度に差が出るように適宜組み合わせて使用すれば良い。また、三種類以上の炭化水素ガスを用いる場合も、上記分解温度の異なる二種類の炭化水素ガスの場合と同様に、分解温度が相互に異なる炭化水素ガスを適宜選択して組み合わせれば良い。 The hydrocarbon gas that is at least two kinds of raw material gases for producing CNTs having different decomposition temperatures includes unsaturated hydrocarbon gases such as acetylene and ethylene, saturated hydrocarbon gases such as methane, and methanol (decomposition temperature: 750 ° C.) Alcohols such as ethanol (decomposition temperature: 700 ° C.) can be used in appropriate combination so that the decomposition temperature can be varied. In this case, the hydrocarbons are appropriately combined so that the decomposition temperatures differ, the alcohols are appropriately combined so that the decomposition temperatures differ, or the hydrocarbons and alcohols are appropriately combined so that the decomposition temperatures differ. Use it. Also, when three or more kinds of hydrocarbon gases are used, as in the case of the two kinds of hydrocarbon gases having different decomposition temperatures, hydrocarbon gases having different decomposition temperatures may be appropriately selected and combined.
本発明では、例えば、アセチレンとエチレン、アセチレンとメタン、エチレンとメタンとを組み合わせて使用することが好ましい。 In the present invention, for example, acetylene and ethylene, acetylene and methane, or ethylene and methane are preferably used in combination.
低温分解ガスを、その使用量が、流量基準で、高温分解ガスの使用量の０．０１〜２０％となるような割合で基板上に供給してＣＮＴを作製する際に、上記炭化水素ガスとして、Ｎ２、Ａｒ、Ｈｅ、Ｈ２、及びＮＨ３から選ばれた少なくとも一種類のガスで希釈されている炭化水素ガスを用いる場合、低温分解ガスの使用量と高温分解ガスの使用量との割合を、希釈ガスの希釈割合により適宜変動せしめることが好ましい。例えば、流量基準で、低温分解ガスとしてのアセチレン：１〜１０ｓｃｃｍに対し、高温分解ガスとしてのエチレン：５００〜１０００ｓｃｃｍを混合して使用する場合、Ｎ２等の希釈ガス：５０〜１０００ｓｃｃｍで希釈することが好ましい。 When the CNT is produced by supplying the low-temperature cracked gas onto the substrate at a rate such that the amount used is 0.01 to 20% of the amount of the high-temperature cracked gas used on the basis of the flow rate, When using a hydrocarbon gas diluted with at least one gas selected from N 2 , Ar, He, H 2 , and NH 3 , the use amount of the low-temperature cracking gas and the use amount of the high-temperature cracking gas It is preferable to appropriately vary the ratio according to the dilution ratio of the dilution gas. For example, when using acetylene: 1 to 10 sccm as a low-temperature decomposition gas and ethylene: 500 to 1000 sccm as a high-temperature decomposition gas on a flow basis, dilute with a diluent gas such as N 2 : 50 to 1000 sccm. It is preferable.
ＣＮＴ作製方法としては、既知のＣＶＤ法であれば特に制限なく使用でき、例えば、熱ＣＶＤ法、プラズマＣＶＤ法、又は触媒を利用したリモートプラズマＣＶＤ法等によるＣＶＤ法を用いることができる。熱ＣＶＤ法、又はリモートプラズマＣＶＤ法を用いることが好ましく、特に密着性の高いＣＮＴを作製するには熱ＣＶＤ法がより好ましい。このリモートプラズマＣＶＤ法とは、プラズマ中で原料ガスをイオン種やラジカル種に分解し、この分解されて得られた原料ガス中のイオン種を取り除いて、ラジカル種を原料としてＣＮＴ成長を行う方法である。上記ＣＶＤ法によりＣＮＴを作製するためのプロセス条件は、特に制限されず、公知のプロセス条件であれば良い。 As a CNT manufacturing method, any known CVD method can be used without particular limitation. For example, a CVD method such as a thermal CVD method, a plasma CVD method, or a remote plasma CVD method using a catalyst can be used. The thermal CVD method or the remote plasma CVD method is preferably used, and the thermal CVD method is more preferable for producing CNTs having particularly high adhesion. This remote plasma CVD method is a method in which source gas is decomposed into ion species and radical species in plasma, and ion species in the source gas obtained by the decomposition are removed, and CNT growth is performed using radical species as a raw material. It is. The process conditions for producing CNTs by the CVD method are not particularly limited, and may be known process conditions.
本発明のＣＮＴ作製方法は、上記したように、ＣＮＴを成長できる公知のプロセス条件で実施できる。この場合、最低でも低温分解ガスのみでＣＮＴを成長できるように、バッファ層と触媒層の種類と膜厚の組み合わせを適宜選択する必要があり、好ましくは高温分解ガスでもＣＮＴを成長できることが良い。低温分解ガスによるＣＮＴ成長温度（６００〜７５０℃）と高温分解ガスによるＣＮＴ成長温度（７５０〜９５０℃）との間の温度でＣＮＴ成長を行う。この場合、好ましくは、高温分解ガスによるＣＮＴ成長温度より１０℃〜１００℃低いことが良い。１０℃未満であると、アモルファスカーボンが生成しやすくなり、１００℃を超えると、密着性が十分に得られない。また、ＣＮＴの成長時間は高温分解ガスによるＣＮＴ成長時間にあわせるようにすることが好ましい。 As described above, the CNT production method of the present invention can be carried out under known process conditions capable of growing CNTs. In this case, it is necessary to appropriately select a combination of the type and film thickness of the buffer layer and the catalyst layer so that the CNT can be grown only with the low-temperature decomposition gas, and preferably the CNT can be grown with the high-temperature decomposition gas. CNT growth is performed at a temperature between the CNT growth temperature (600 to 750 ° C.) using the low temperature decomposition gas and the CNT growth temperature (750 to 950 ° C.) using the high temperature decomposition gas. In this case, the temperature is preferably lower by 10 ° C. to 100 ° C. than the CNT growth temperature by the high-temperature decomposition gas. When the temperature is less than 10 ° C., amorphous carbon is easily generated, and when the temperature exceeds 100 ° C., sufficient adhesion cannot be obtained. The CNT growth time is preferably matched to the CNT growth time by the high-temperature decomposition gas.
本発明によれば、上記したように、分解温度の異なる少なくとも二種類の炭化水素ガスを混合して使用することによって、ＣＮＴ成長とカーボン薄膜との形成が起こり、作製したＣＮＴと基板との接合箇所を含めた根本部分又は根本部分を含めた全表面が原料ガス由来のカーボン薄膜で覆われる。このように根本部分を覆う場合は、低温（例えば、７５０〜８００℃）で成長させる場合やエチレン量が少ない場合、また、全体を覆う場合は、高温（例えば、８００〜９００℃）で成長させた場合やエチレン量がアセチレンに対して多い場合である。アセチレンとエチレンとを使用する場合は、高温分解ガスのエチレンが、覆うカーボンを作製する。 According to the present invention, as described above, by using a mixture of at least two types of hydrocarbon gases having different decomposition temperatures, CNT growth and carbon thin film formation occur, and the produced CNT is bonded to the substrate. The root portion including the portion or the entire surface including the root portion is covered with the carbon thin film derived from the source gas. Thus, when covering the root part, when growing at a low temperature (for example, 750 to 800 ° C.), when the amount of ethylene is small, or when covering the whole, it is grown at a high temperature (for example, 800 to 900 ° C.). Or the amount of ethylene is larger than that of acetylene. In the case of using acetylene and ethylene, carbon which is covered with ethylene of a high-temperature decomposition gas is produced.
希釈ガスの使用量に関しては、炭化水素ガスの種類及び使用量やその他のプロセス条件により異なるが、例えば、アセチレン：１０ｓｃｃｍ、エチレン：１０００ｓｃｃｍの場合、一般にＮ２ガスを５００ｓｃｃｍにしても密着性の良いＣＮＴが得られるが、３００ｓｃｃｍにすると、アモルファスカーボンが堆積しやすくなる。Ｎ２ガス量が多くなるにつれて、ＣＮＴの長さが短くなっていき、多くしすぎるとＣＮＴは成長しなくなる。これは、ＣＮＴ成長のための炭素供給量が炭化水素ガスの分圧に依存しているためである。例えば、アセチレンとＮ２との反応の場合、アセチレンに対してＮ２ガスを増やしていくと、アセチレン：１０ｓｃｃｍ、Ｎ２ガス：２０００ｓｃｃｍではＣＮＴは成長しない。 The amount of dilution gas used varies depending on the type and amount of hydrocarbon gas used and other process conditions. For example, in the case of acetylene: 10 sccm and ethylene: 1000 sccm, generally N 2 gas is set to 500 sccm, and adhesion is good. CNT can be obtained, but when it is 300 sccm, amorphous carbon is easily deposited. As the amount of N 2 gas increases, the length of the CNTs decreases. If the amount of N 2 gas is excessive, the CNTs do not grow. This is because the carbon supply amount for CNT growth depends on the partial pressure of the hydrocarbon gas. For example, in the case of a reaction between acetylene and N 2 , if N 2 gas is increased with respect to acetylene, CNT does not grow at acetylene: 10 sccm and N 2 gas: 2000 sccm.
以下に実施例を挙げて、本発明を具体的に説明する。 The present invention will be specifically described below with reference to examples.
成膜室にシリコン基板を載置し、スパッタリング法により、シリコン基板上にバッファ層としてのＡｌ膜を２０ｎｍの厚みに形成し、このＡｌ膜上に触媒としてアンバー合金を成膜した。次いで、成膜室内に１ａｔｍの圧力下、Ｎ２ガス：１０００ｓｃｃｍを導入し、上記のようにして得られた触媒付き基板を８００℃まで昇温せしめた。この圧力及び温度を維持したまま、成膜室内にアセチレン：１０ｓｃｃｍ及びエチレン：１０００ｓｃｃｍを導入してＣＮＴの成長を開始した。２０分間成長を続けた後、成膜室内を排気し、降温せしめ、基板を取り出した。かくして得られたＣＮＴが成長した基板の断面ＳＥＭ写真を図１に示す。 A silicon substrate was placed in the deposition chamber, and an Al film as a buffer layer was formed to a thickness of 20 nm on the silicon substrate by sputtering, and an amber alloy was formed as a catalyst on the Al film. Next, N 2 gas: 1000 sccm was introduced into the film formation chamber under a pressure of 1 atm, and the substrate with catalyst obtained as described above was heated to 800 ° C. While maintaining this pressure and temperature, acetylene: 10 sccm and ethylene: 1000 sccm were introduced into the deposition chamber to start the growth of CNTs. After continuing the growth for 20 minutes, the film formation chamber was evacuated, the temperature was lowered, and the substrate was taken out. A cross-sectional SEM photograph of the substrate on which the CNT thus obtained has grown is shown in FIG.
図１から明らかなように、基板上に、１００μｍ程度の長さを持ち、垂直に密集して配向しているブラシ状ＣＮＴが作製されていた。このＣＮＴは、手で触れても基板から剥がれることもなく、また、ＣＮＴに市販の粘着テープを貼って、引っ張った程度では剥がれることもなかった。このＣＮＴは、目視では黒色をしているが、サンプルステージが銀色になっており、ＤＬＣ（ダイアモンド様カーボン）からなるカーボン薄膜がステージ部分に形成されていることが確認できた。このサンプルステージは、石英の板の上にＳｉＣが載っており、その上に基板が載せられる。石英やＳｉＣにカーボン膜が生成していることからＣＮＴにもカーボン膜が生成しているものと判断する。また、触媒膜があると、低温でＤＬＣ等のカーボン膜ができるため、ステージ等よりは容易にＣＮＴの根本部分の触媒がある部分がカーボン膜で覆われる。 As is apparent from FIG. 1, brush-like CNTs having a length of about 100 μm and densely aligned vertically were produced on the substrate. The CNTs were not peeled off from the substrate even when they were touched by hand. Also, the CNTs were not peeled off when a commercially available adhesive tape was applied to the CNTs and pulled. Although this CNT is visually black, the sample stage is silver, and it was confirmed that a carbon thin film made of DLC (diamond-like carbon) was formed on the stage portion. In this sample stage, SiC is placed on a quartz plate, and a substrate is placed thereon. Since a carbon film is formed on quartz or SiC, it is determined that a carbon film is also formed on CNT. In addition, since a carbon film such as DLC can be formed at a low temperature when the catalyst film is present, a part having the catalyst at the base part of CNT is more easily covered with the carbon film than a stage or the like.
実施例１におけるＮ２ガス、アセチレン、及びエチレンの量を、以下のように変えて、実施例１のＣＮＴ成長プロセスを繰り返した。
（１）Ｎ２ガス：１０００ｓｃｃｍ、アセチレン：０．１ｓｃｃｍ、及びエチレン：１０００ｓｃｃｍのように、アセチレンをエチレンの０．０１％とした場合、成長したＣＮＴの密着性は、実施例１の場合の密着性と比べて若干劣るものの、通常より十分に高く、ＣＮＴに触れても基板から剥がれなかった。
The CNT growth process of Example 1 was repeated with the amounts of N 2 gas, acetylene, and ethylene in Example 1 changed as follows.
(1) When N 2 gas: 1000 sccm, acetylene: 0.1 sccm, and ethylene: 1000 sccm, when acetylene is 0.01% of ethylene, the adhesion of the grown CNT is the same as in Example 1. Although it was slightly inferior to the properties, it was sufficiently higher than usual, and even if it touched CNT, it did not peel from the substrate.
（２）Ｎ２ガス：１０００ｓｃｃｍ、アセチレン：１ｓｃｃｍ、及びエチレン：１０００ｓｃｃｍのように、アセチレンをエチレンの０．１％とした場合、成長したＣＮＴの密着性は、実施例１の場合の密着性と同程度であった。 (2) When acetylene is 0.1% of ethylene, such as N 2 gas: 1000 sccm, acetylene: 1 sccm, and ethylene: 1000 sccm, the adhesion of the grown CNT is the same as that of Example 1 It was about the same.
（３）Ｎ２ガス：１０００ｓｃｃｍ、アセチレン：２００ｓｃｃｍ、及びエチレン：１０００ｓｃｃｍのように、アセチレンをエチレンの２０％とした場合、成長したＣＮＴの密着性は、実施例１の場合の密着性と同程度であった。 (3) When acetylene is 20% of ethylene, such as N 2 gas: 1000 sccm, acetylene: 200 sccm, and ethylene: 1000 sccm, the adhesion of the grown CNT is about the same as that in Example 1 Met.
以上から、低温分解ガスの使用量が、流量基準で、高温分解ガスの使用量の０．０１〜２０％である場合に、高い密着性が得られたことが分かる。 From the above, it can be seen that high adhesion was obtained when the amount of low-temperature cracked gas used was 0.01 to 20% of the amount of high-temperature cracked gas used on a flow rate basis.
実施例１において、触媒としてＮｉを成膜し、成膜室内にアセチレン：０．１、１、１００、２００ｓｃｃｍを導入したことを除いて実施例１記載のプロセスを繰り返して、ＣＮＴを作製した。かくして得られたＣＮＴの成長した基板の断面ＳＥＭ写真から、図１と同様に、基板上に１００μｍ程度の長さを持ち、垂直に密集して配向しているブラシ状ＣＮＴが作製されていたことが確認できた。このＣＮＴは、実施例１の場合と同様に、手で触れても基板から剥がれることもなく、また、ＣＮＴに市販の粘着テープを貼って、引っ張った程度では剥がれることもなかった。また、実施例１と同様に、カーボン薄膜がステージ部分に形成されていることが確認できた。 In Example 1, Ni was formed as a catalyst, and CNTs were produced by repeating the process described in Example 1 except that acetylene: 0.1, 1, 100, and 200 sccm were introduced into the film formation chamber. From the cross-sectional SEM photograph of the CNT-grown substrate thus obtained, a brush-like CNT having a length of about 100 μm and vertically densely aligned was produced on the substrate, as in FIG. Was confirmed. As in Example 1, this CNT was not peeled off from the substrate even when it was touched by hand, and it was not peeled off when a commercially available adhesive tape was applied to the CNT and pulled. Further, as in Example 1, it was confirmed that the carbon thin film was formed on the stage portion.
実施例１におけるＮ２ガス、アセチレン、及びエチレンの代わりに、Ｎ２ガス：２０００ｓｓｃｍ、アセチレン：１０ｓｃｃｍ、エチレン：５００ｓｃｃｍ、及びメタン：５５００ｓｃｃｍを用いて、実施例１のＣＮＴ成長プロセスを繰り返した。但し、８５０℃で２０分成長せしめた。 The CNT growth process of Example 1 was repeated using N 2 gas: 2000 sscm, acetylene: 10 sccm, ethylene: 500 sccm, and methane: 5500 sccm instead of N 2 gas, acetylene, and ethylene in Example 1. However, it was grown at 850 ° C. for 20 minutes.
かくして得られたＣＮＴは十分密着性が高かった。但し、三種類のガスを使用する場合は、その使用量のバランスが難しく、アセチレンを５０ｓｃｃｍにすると、アモルファスカーボンが堆積し、アセチレンを１ｓｃｃｍにすると、得られたＣＮＴの密着性は劣り、基板から容易に剥がれてしまう。
（比較例１）
The CNT thus obtained had sufficiently high adhesion. However, when using three kinds of gases, it is difficult to balance the amount of use, and when acetylene is 50 sccm, amorphous carbon is deposited, and when acetylene is 1 sccm, the adhesion of the obtained CNT is inferior. It easily peels off.
(Comparative Example 1)
成膜室内にアセチレンのみ又はエチレンのみを導入したことを除いて、実施例１記載のプロセスを繰り返して、ＣＮＴを作製した。得られたＣＮＴに対して手で触れたところ、両者とも、容易に基板から剥がれた。
（比較例２）
CNTs were produced by repeating the process described in Example 1 except that only acetylene or ethylene was introduced into the film formation chamber. When the obtained CNT was touched by hand, both were easily peeled off from the substrate.
(Comparative Example 2)
実施例１におけるＮ２ガス、アセチレン、及びエチレンの代わりに、（１）Ｎ２ガス：１０００ｓｓｃｍ、アセチレン：０．１ｓｃｃｍ、及びエチレン：２０００ｓｃｃｍのように、アセチレンをエチレンの０．００５％としたガス、また、（２）Ｎ２ガス：１０００ｓｓｃｍ、アセチレン：３００ｓｃｃｍ、及びエチレン：１０００ｓｃｃｍのように、アセチレンをエチレンの３０％としたガスを用いて、実施例１のＣＮＴ成長プロセスを繰り返した。 Instead of N 2 gas, acetylene, and ethylene in Example 1, (1) N 2 gas: 1000 sscm, acetylene: 0.1 sccm, and ethylene: 2000 sccm, a gas in which acetylene is 0.005% of ethylene In addition, the CNT growth process of Example 1 was repeated using a gas in which acetylene was 30% of ethylene, such as (2) N 2 gas: 1000 sscm, acetylene: 300 sccm, and ethylene: 1000 sccm.
かくして得られたＣＮＴは、上記（１）の場合、手で触れたところ、容易に基板から剥がれ、また、上記（２）の場合、密着性は良く、手で触れても基板から剥がれなかったが、ＣＮＴ上にアモルファスカーボンが堆積していた。このアモルファスカーボンが堆積している状態の基板の断面ＳＥＭ写真を図２に示す。 The CNT thus obtained was easily peeled off from the substrate when touched by hand in the case of (1), and in the case of (2), the adhesion was good and did not peel from the substrate even when touched by hand. However, amorphous carbon was deposited on the CNT. A cross-sectional SEM photograph of the substrate on which the amorphous carbon is deposited is shown in FIG.
本発明によれば、ブラシ状に密集して垂直に配向成長したＣＮＴは基板から剥離し難いいので、半導体装置分野や、ＣＮＴが物理的に接触するような分野、例えばウェハートランスファーの滑り止めや、水路の内壁保護や接触抵抗の低減用等の分野で利用可能である。 According to the present invention, CNTs that are densely packed in a brush shape and vertically oriented and grown are difficult to peel off from the substrate. Therefore, in the field of semiconductor devices, fields where CNTs physically contact, for example, anti-slip of wafer transfer, It can be used in fields such as protecting the inner walls of waterways and reducing contact resistance.
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