JP2015074585A - Method for producing carbon nanotube - Google Patents
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Abstract
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本発明は、カーボンナノチューブの製造方法に関する。 The present invention relates to a method for producing carbon nanotubes.
カーボンナノチューブ（以下、ＣＮＴと略記することがある）は、軽量であり、機械的強度及び導電性に優れているので、高強度材料や高導電材料として用いることが検討されている。前記ＣＮＴは、前記高強度材料又は前記高導電材料として用いるために、高品質且つ長尺で細径であることが必要とされ、細径とするためには単層ＣＮＴであることが望まれる。 Since carbon nanotubes (hereinafter sometimes abbreviated as CNT) are lightweight and excellent in mechanical strength and conductivity, use as a high-strength material or a high-conductivity material has been studied. In order to use the CNT as the high-strength material or the high-conductivity material, it is necessary to have a high quality, long, and small diameter. .
従来、前記ＣＮＴを、高密度且つ一方向に配向した集合体として製造する製造方法が提案されている。前記ＣＮＴの製造方法として、例えば、金属触媒の存在下で化学気相成長（以下、ＣＶＤと略記することがある）法によりＣＮＴを成長させる際に、反応雰囲気に微量の水蒸気を添加する方法が知られている（例えば、特許文献１参照）。 Conventionally, a manufacturing method has been proposed in which the CNTs are manufactured as a high-density and unidirectionally oriented aggregate. As a method for producing the CNT, for example, there is a method of adding a small amount of water vapor to the reaction atmosphere when growing the CNT by chemical vapor deposition (hereinafter sometimes abbreviated as CVD) in the presence of a metal catalyst. It is known (see, for example, Patent Document 1).
前記製造方法によれば、基板上に垂直に配向した単層ＣＮＴ集合体を得ることができる。前記製造方法では、さらに、前記単層ＣＮＴ集合体を液体に晒したのち、乾燥することにより高密度化することができ、０．２〜１．５ｇ／ｃｍ３の重量密度を有する単層ＣＮＴ集合体を得ることができるとされている。 According to the manufacturing method, a single-walled CNT aggregate oriented vertically on the substrate can be obtained. In the manufacturing method, the single-walled CNT aggregate having a weight density of 0.2 to 1.5 g / cm 3 can be further densified by exposing the single-walled CNT aggregate to a liquid and then drying. It is said that an aggregate can be obtained.
また、前記ＣＮＴの製造方法として、パルスアークプラズマによって基板上に粒子状触媒を堆積させた後、プラズマＣＶＤ法によりＣＮＴを成長させる方法が知られている（例えば、特許文献２参照）。前記製造方法によれば、前記基板上に高密度の二層ＣＮＴを得ることができるとされている。 Further, as a method for producing the CNT, a method is known in which a particulate catalyst is deposited on a substrate by pulsed arc plasma, and then the CNT is grown by a plasma CVD method (see, for example, Patent Document 2). According to the manufacturing method, high-density double-walled CNTs can be obtained on the substrate.
しかしながら、ＣＶＤ法によりＣＮＴを成長させる際に反応雰囲気に微量の水蒸気を添加する方法では、高密度の単層ＣＮＴ集合体を得るために、得られた単層ＣＮＴ集合体を液体に晒し、さらに乾燥するという後処理を行わねばならないという不都合がある。 However, in the method of adding a small amount of water vapor to the reaction atmosphere when growing CNTs by the CVD method, in order to obtain a high-density single-walled CNT aggregate, the obtained single-walled CNT aggregate is exposed to a liquid, There is an inconvenience that a post-treatment of drying must be performed.
また、パルスアークプラズマによって基板上に粒子状触媒を堆積させた後、プラズマＣＶＤ法によりＣＮＴを成長させる方法では、得られるＣＮＴが二層ＣＮＴとなり細径のＣＮＴを得ることが難しいという不都合がある。 In addition, the method of growing CNTs by plasma CVD after depositing a particulate catalyst on a substrate by pulsed arc plasma has the disadvantage that it is difficult to obtain small-diameter CNTs because the resulting CNTs become double-walled CNTs. .
そこで、本発明は、前記不都合を解決するために、後処理を要することなく、高密度且つ一方向に配向した単層ＣＮＴ集合体を得ることができるＣＮＴの製造方法を提供することを目的とする。 Accordingly, an object of the present invention is to provide a CNT manufacturing method capable of obtaining a single-walled CNT aggregate oriented in a high density and in one direction without requiring post-treatment in order to solve the above-described disadvantages. To do.
かかる目的を達成するために、本発明は、処理室内にカーボンナノチューブの原料となる気体を流通すると共に、該処理室内を所定の圧力に減圧し、該処理室内に保持された触媒担持基板上に化学気相成長法によりカーボンナノチューブを成長させるカーボンナノチューブの製造方法において、該触媒担持基板の触媒が担持されている面上に成長するカーボンナノチューブに対し、該カーボンナノチューブの成長方向に対向する方向に押圧力を加えることを特徴とする。 In order to achieve such an object, the present invention circulates a gas as a raw material for carbon nanotubes in a processing chamber and depressurizes the processing chamber to a predetermined pressure on a catalyst-carrying substrate held in the processing chamber. In the carbon nanotube production method of growing carbon nanotubes by chemical vapor deposition, the carbon nanotubes grown on the catalyst-carrying surface of the catalyst-carrying substrate are in a direction opposite to the growth direction of the carbon nanotubes. A pressing force is applied.
本発明のカーボンナノチューブ（ＣＮＴ）の製造方法では、処理室内にＣＮＴの原料となる気体を流通すると共に、該処理室内を所定の圧力に減圧し、該処理室内に保持された触媒担持基板上に化学気相成長（ＣＶＤ）法によりＣＮＴを成長させる。このようにすることにより、前記原料となる気体から供給される炭素源により、前記触媒担持基板上に多数の単層ＣＮＴを密集し且つ垂直に配向した状態で成長させることができる。 In the carbon nanotube (CNT) manufacturing method of the present invention, a gas serving as a CNT raw material is circulated in a processing chamber, and the processing chamber is depressurized to a predetermined pressure on a catalyst-carrying substrate held in the processing chamber. CNTs are grown by chemical vapor deposition (CVD). By doing so, it is possible to grow a large number of single-walled CNTs densely and vertically oriented on the catalyst-carrying substrate by the carbon source supplied from the gas as the raw material.
ところが、本発明者らの検討によれば、前記単層ＣＮＴは自由に成長させると、密集した単層ＣＮＴが長尺化することにより、その根元の触媒粒子に対する前記炭素源の供給が阻害されやすくなることが判明した。また、前記単層ＣＮＴは自由に成長させると、個々の単層ＣＮＴの成長速度が異なるために、成長速度の大きい単層ＣＮＴが成長速度の小さい単層ＣＮＴを、前記触媒担持基板から触媒ごと引き抜いてしまうおそれがあることが判明した。この結果、前記単層ＣＮＴを自由に成長させたのでは、高密度の単層ＣＮＴ集合体を得ることができない。 However, according to the study by the present inventors, when the single-walled CNTs are grown freely, the dense single-walled CNTs are elongated, thereby inhibiting the supply of the carbon source to the base catalyst particles. It turned out to be easier. Further, when the single-walled CNTs are grown freely, the growth rates of the individual single-walled CNTs are different. Therefore, the single-walled CNTs having a high growth rate are transferred from the catalyst-supporting substrate to the catalyst. It turns out that there is a risk of pulling out. As a result, if the single-walled CNTs are grown freely, a high-density single-walled CNT aggregate cannot be obtained.
そこで、本発明のＣＮＴの製造方法では、前記触媒担持基板の触媒が担持されている面上に成長するＣＮＴに対し、該ＣＮＴの成長方向に対向する方向に押圧力を加えることにより、該ＣＮＴの成長速度を制御する。 Therefore, in the CNT production method of the present invention, a pressure is applied to the CNT growing on the surface of the catalyst carrying substrate on which the catalyst is carried, in a direction opposite to the growth direction of the CNT. To control the growth rate.
前記押圧力を加えると、個々の単層ＣＮＴの成長速度を制御して均一化することができ、単層ＣＮＴの長尺化に伴って前記触媒粒子に対する前記炭素源の供給が阻害される現象を緩和することができる。また、前記押圧力を加えて、個々の単層ＣＮＴの成長速度を制御して均一化することにより、一部の単層ＣＮＴが他の単層ＣＮＴに引き抜かれることを防止することができる。従って、本発明のＣＮＴの製造方法によれば、後処理を必要とすることなく、直接前記触媒担持基板上に高密度且つ垂直に配向した単層ＣＮＴ集合体を得ることができる。 When the pressing force is applied, the growth rate of individual single-walled CNTs can be controlled and uniformized, and the supply of the carbon source to the catalyst particles is hindered as the single-walled CNTs become longer Can be relaxed. Further, by applying the pressing force to control and uniformize the growth rate of each single-walled CNT, it is possible to prevent some of the single-walled CNTs from being pulled out by other single-walled CNTs. Therefore, according to the method for producing CNTs of the present invention, a single-walled CNT aggregate can be obtained that is directly oriented at high density and vertically on the catalyst-carrying substrate without requiring post-treatment.
本発明のＣＮＴの製造方法では、例えば、前記触媒担持基板から下方に向かって前記ＣＮＴを成長させるときに、下方から該ＣＮＴに当接される当接部材により前記押圧力を加えることができる。前記触媒担持基板から下方に向かって前記ＣＮＴを成長させるときには、該触媒担持基板が自重により該ＣＮＴを前記当接部材に押圧する。そこで、前記ＣＮＴには前記当接部材から前記押圧に対する反力が作用することとなり、該反力が該ＣＮＴの成長方向に対向する方向に加えられる前記押圧力となる。 In the CNT manufacturing method of the present invention, for example, when the CNT is grown downward from the catalyst-carrying substrate, the pressing force can be applied by a contact member that contacts the CNT from below. When growing the CNTs downward from the catalyst-carrying substrate, the catalyst-carrying substrate presses the CNTs against the contact member by its own weight. Therefore, a reaction force against the pressing acts on the CNT from the contact member, and the reaction force becomes the pressing force applied in a direction opposite to the growth direction of the CNT.
また、本発明のＣＮＴの製造方法では、前記触媒担持基板から上方に向かって前記ＣＮＴを成長させるときに、上方から該ＣＮＴに当接される当接部材により前記押圧力を加えるようにしてもよい。前記触媒担持基板から上方に向かって前記ＣＮＴを成長させるときには、前記当接部材の自重が該ＣＮＴの成長方向に対向する方向に加えられる前記押圧力となる。 Further, in the CNT manufacturing method of the present invention, when the CNT is grown upward from the catalyst-carrying substrate, the pressing force is applied by a contact member that contacts the CNT from above. Good. When growing the CNTs upward from the catalyst-carrying substrate, the weight of the contact member becomes the pressing force applied in a direction opposite to the growth direction of the CNTs.
また、本発明のＣＮＴの製造方法において、前記ＣＶＤ法はどのような方法によるものであってもよいが、例えば、アンテナ型プラズマＣＶＤ法を用いることができる。前記アンテナ型プラズマＣＶＤ法では、前記処理室の天面にアンテナを備え、該アンテナの下方に保持されている前記触媒担持基板に対して、該アンテナの先端からプラズマを発生させることにより該触媒担持基板上にＣＮＴを成長させる。 In the CNT manufacturing method of the present invention, the CVD method may be any method, but for example, an antenna type plasma CVD method can be used. In the antenna type plasma CVD method, an antenna is provided on the top surface of the processing chamber, and the catalyst is supported by generating plasma from the tip of the antenna with respect to the catalyst supporting substrate held below the antenna. CNTs are grown on the substrate.
本発明のＣＮＴの製造方法において、前記アンテナ型プラズマＣＶＤ法を用いる場合、前記触媒担持基板は、基材と、該基材の一方の表面に形成され該基材と触媒材料との反応を防止する反応防止層と、該反応防止層上に形成され該触媒材料を担持する触媒担持層と、該触媒担持層上に形成され該触媒担持層に含まれる該触媒材料を分散させる分散層とを備えることが好ましい。前記構成を備える前記触媒担持基板によれば、より長尺の単層ＣＮＴを得ることができる。 In the CNT manufacturing method of the present invention, when the antenna type plasma CVD method is used, the catalyst-supporting substrate is formed on one surface of the base material and the base material to prevent a reaction between the base material and the catalyst material. A reaction preventing layer, a catalyst supporting layer formed on the reaction supporting layer and supporting the catalyst material, and a dispersion layer formed on the catalyst supporting layer and dispersing the catalyst material contained in the catalyst supporting layer. It is preferable to provide. According to the catalyst-carrying substrate having the above configuration, a longer single-walled CNT can be obtained.
また、本発明のＣＮＴの製造方法において、前記アンテナ型プラズマＣＶＤ法を用いる場合、前記触媒担持基板は、前記アンテナと反対側の面に触媒を担持することが好ましい。前記触媒担持基板が、前記アンテナと反対側の面に触媒を担持することにより、該触媒担持基板及び該触媒担持基板上に成長する単層ＣＮＴが前記プラズマにより攻撃されることを避けることができる。 In the CNT manufacturing method of the present invention, when the antenna type plasma CVD method is used, it is preferable that the catalyst supporting substrate supports a catalyst on a surface opposite to the antenna. Since the catalyst-carrying substrate carries the catalyst on the surface opposite to the antenna, it can be avoided that the catalyst-carrying substrate and the single-walled CNT growing on the catalyst-carrying substrate are attacked by the plasma. .
次に、添付の図面を参照しながら本発明の実施の形態についてさらに詳しく説明する。 Next, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.
本実施形態のＣＮＴの製造方法は、化学気相成長（ＣＶＤ）法により、触媒担持基板上にＣＮＴ集合体を成長させる方法である。前記ＣＶＤ法は、熱ＣＶＤ法、プラズマＣＶＤ法等のどのようなＣＶＤ法であってもよく、例えば、アンテナ型（先端放電型）プラズマＣＶＤ法を用いることができる。 The CNT manufacturing method of this embodiment is a method of growing a CNT aggregate on a catalyst-carrying substrate by chemical vapor deposition (CVD). The CVD method may be any CVD method such as a thermal CVD method or a plasma CVD method. For example, an antenna type (tip discharge type) plasma CVD method can be used.
前記アンテナ型プラズマＣＶＤ法は、例えば、図１に示すアンテナ型プラズマＣＶＤ装置１を用いて実施することができる。アンテナ型プラズマＣＶＤ装置１は、箱形のチャンバー（処理室）２を備え、天井部にＣＮＴの原料となる気体（以下、原料ガスと略記する）を導入する原料ガス導入部３を備える。また、底部側面にはチャンバー２内のガスを排出するガス排出部４を備えており、ガス排出部４は例えば図示しない真空ポンプに接続されている。 The antenna type plasma CVD method can be performed using, for example, an antenna type plasma CVD apparatus 1 shown in FIG. The antenna type plasma CVD apparatus 1 includes a box-shaped chamber (processing chamber) 2, and includes a source gas introduction unit 3 that introduces a gas (hereinafter abbreviated as source gas) serving as a source of CNTs into the ceiling. A gas discharge part 4 for discharging the gas in the chamber 2 is provided on the bottom side surface, and the gas discharge part 4 is connected to a vacuum pump (not shown), for example.
チャンバー２の天井部には、マイクロ波導波管５及びアンテナ６が備えられており、マイクロ波導波管５により所定の周波数（例えば２．４５ＧＨｚ）のマイクロ波を印加することによりアンテナ６の先端部６ａにプラズマを集中発生させるようになっている。この結果、先端部６ａの周囲にプラズマ発生領域７が形成される。 A microwave waveguide 5 and an antenna 6 are provided on the ceiling of the chamber 2, and a microwave having a predetermined frequency (for example, 2.45 GHz) is applied by the microwave waveguide 5, so that the tip of the antenna 6 is provided. Plasma is concentratedly generated on 6a. As a result, a plasma generation region 7 is formed around the tip portion 6a.
チャンバー２内には、マイクロ波導波管５に対向する位置に基板保持部８が上下動自在に設けられており、基板保持部８上に触媒担持基板９が載置されている。アンテナ型プラズマＣＶＤ装置１では、基板保持部８を上下動させることにより、アンテナ６の先端部６ａと触媒担持基板９との距離ｄを調整するようになっている。 In the chamber 2, a substrate holding portion 8 is provided at a position facing the microwave waveguide 5 so as to be movable up and down, and a catalyst carrying substrate 9 is placed on the substrate holding portion 8. In the antenna type plasma CVD apparatus 1, the distance d between the tip 6 a of the antenna 6 and the catalyst carrying substrate 9 is adjusted by moving the substrate holding portion 8 up and down.
触媒担持基板９は、図２に示すように、基材１１と、基材１１上に形成された反応防止層１２と、反応防止層１２上に形成された触媒担持層１３と、触媒担持層１３上に形成された分散層１４とから構成されている。基材１１に用いることができる材料としては、シリコン、ガラス、溶融石英、耐熱セラミックス、耐熱鋼板等を挙げることができる。 As shown in FIG. 2, the catalyst-carrying substrate 9 includes a base material 11, a reaction prevention layer 12 formed on the base material 11, a catalyst support layer 13 formed on the reaction prevention layer 12, and a catalyst support layer. 13 and a dispersion layer 14 formed on 13. Examples of materials that can be used for the substrate 11 include silicon, glass, fused quartz, heat-resistant ceramics, and heat-resistant steel plates.
反応防止層１２は、基材１１と触媒担持層１３との反応を防止して触媒担持層１３に所定量の触媒材料を確保すると共に、該触媒材料から形成される触媒微粒子を所定の形態に維持する機能を備える。反応防止層１２は、前記機能を備えるために、例えばＡｌ２Ｏ３により、５〜５００ｎｍの範囲の厚さ、例えば５０ｎｍの厚さに形成されることが好ましい。 The reaction preventing layer 12 prevents a reaction between the base material 11 and the catalyst supporting layer 13 to secure a predetermined amount of catalyst material in the catalyst supporting layer 13 and also makes catalyst fine particles formed from the catalyst material into a predetermined form. It has the function to maintain. In order to provide the above function, the reaction preventing layer 12 is preferably formed of, for example, Al 2 O 3 to a thickness in the range of 5 to 500 nm, for example, 50 nm.
触媒担持層１３は、例えばＦｅにより、０．０２５〜３ｎｍの範囲の厚さ、例えば０．５ｎｍの厚さに形成されることが好ましい。分散層１４は、触媒担持層１３の触媒材料から形成される触媒微粒子を安定して分散させると共に、該触媒微粒子の径を所望の大きさに規定する機能を備える。分散層１４は、前記機能を備えるために、例えばＡｌ２Ｏ３により、０．０２５〜３ｎｍの範囲の厚さ、例えば１．０ｎｍの厚さに形成されることが好ましい。 The catalyst support layer 13 is preferably formed of, for example, Fe and has a thickness in the range of 0.025 to 3 nm, for example, 0.5 nm. The dispersion layer 14 has a function of stably dispersing the catalyst fine particles formed from the catalyst material of the catalyst support layer 13 and defining the diameter of the catalyst fine particles to a desired size. In order to provide the function, the dispersion layer 14 is preferably formed of, for example, Al 2 O 3 to a thickness in the range of 0.025 to 3 nm, for example, 1.0 nm.
本実施形態の製造方法では、チャンバー２内にＣＮＴの原料となる気体を流通すると共に、チャンバー２内を所定の圧力に減圧し、触媒担持基板９上にプラズマＣＶＤ法によりＣＮＴを成長させる。このとき、前記ＣＮＴに対し、その成長方向に対向する方向に押圧力を加える。 In the manufacturing method of the present embodiment, a gas serving as a CNT raw material is circulated in the chamber 2, and the inside of the chamber 2 is reduced to a predetermined pressure, and CNTs are grown on the catalyst supporting substrate 9 by plasma CVD. At this time, a pressing force is applied to the CNT in a direction opposite to the growth direction.
前記ＣＮＴの原料となる気体としては、例えばメタン、アセチレン等の炭化水素の気体を、水素等のキャリアガスと共に用いることができる。また、チャンバー２内は、１３３３〜２６６６６Ｐａ（１０〜２００Ｔｏｒｒ）、例えば１３３３０Ｐａ（１００Ｔｏｒｒ）の圧力に減圧する。 As the gas used as the raw material of the CNT, for example, a hydrocarbon gas such as methane or acetylene can be used together with a carrier gas such as hydrogen. The inside of the chamber 2 is depressurized to a pressure of 1333 to 26666 Pa (10 to 200 Torr), for example, 13330 Pa (100 Torr).
前記押圧力を加える手段として、本実施形態の製造方法では、例えば触媒担持基板９から下方に向かってＣＮＴを成長させるときに、下方からＣＮＴに当接される当接部材を用いることができる。 As the means for applying the pressing force, in the manufacturing method of the present embodiment, for example, when growing CNTs downward from the catalyst-carrying substrate 9, a contact member that contacts the CNTs from below can be used.
触媒担持基板９から下方に向かってＣＮＴを成長させるときには、図１に示す基板保持部８に代えて、図３に示す基板保持手段２１を用いる。基板保持手段２１は、アンテナ６と反対側に触媒担持基板９を保持するＭｏ製基板保持部材２２と、Ｍｏ製基板保持部材２２の下方から触媒担持基板９に当接される石英製当接部材２３と、石英製当接部材２３を下方から支持する石英製支持部材２４とを備える。 When growing CNTs downward from the catalyst-carrying substrate 9, a substrate holding means 21 shown in FIG. 3 is used instead of the substrate holding portion 8 shown in FIG. The substrate holding means 21 includes a Mo substrate holding member 22 that holds the catalyst supporting substrate 9 on the side opposite to the antenna 6, and a quartz contact member that contacts the catalyst supporting substrate 9 from below the Mo substrate holding member 22. 23 and a quartz support member 24 that supports the quartz contact member 23 from below.
Ｍｏ製基板保持部材２２は、アンテナ６と反対側に凹部２２ａを備え、触媒担持基板９は凹部２２ａに収容されて保持される。このとき、触媒担持基板９は、触媒担持層１３が基材１１に対しＭｏ製基板保持部材２２と反対側に位置するように配置され、即ちアンテナ６と反対側に触媒を保持している。尚、図３では、触媒担持基板９の反応防止層１２及び分散層１４を省略して示している。 The Mo substrate holding member 22 includes a recess 22a on the side opposite to the antenna 6, and the catalyst carrying substrate 9 is accommodated and held in the recess 22a. At this time, the catalyst-carrying substrate 9 is arranged so that the catalyst-carrying layer 13 is located on the opposite side of the Mo substrate holding member 22 with respect to the base material 11, that is, holding the catalyst on the opposite side to the antenna 6. In FIG. 3, the reaction preventing layer 12 and the dispersion layer 14 of the catalyst carrying substrate 9 are omitted.
石英製当接部材２３は、第１の円筒状部材２５と、第１の円筒状部材２５より小径の第２の円筒状部材２６とが同心円状に積層されており、第２の円筒状部材２６は第１の円筒状部材２５に対しＭｏ製基板保持部材２２と反対側に配設されている。また、円筒状部材２５，２６の中央には軸方向に沿って貫通孔２７が設けられている。石英製支持部材２４は、第２の円筒状部材２６よりさらに小径の石英管からなり、第１の円筒状部材２５のＭｏ製基板保持部材２２と反対側の底面において、第２の円筒状部材２６の外周側に配置されている。 The quartz contact member 23 is formed by concentrically stacking a first cylindrical member 25 and a second cylindrical member 26 having a smaller diameter than the first cylindrical member 25, and the second cylindrical member. 26 is arranged on the opposite side to the Mo substrate holding member 22 with respect to the first cylindrical member 25. A through hole 27 is provided in the center of the cylindrical members 25 and 26 along the axial direction. The quartz support member 24 is made of a quartz tube having a smaller diameter than the second cylindrical member 26, and the second cylindrical member is formed on the bottom surface of the first cylindrical member 25 opposite to the Mo substrate holding member 22. 26 is arranged on the outer peripheral side.
基板保持手段２１によれば、前記アンテナ型プラズマＣＶＤ法により、触媒担持基板９と第１の円筒状部材２５との間に単層ＣＮＴが成長し、単層ＣＮＴ集合体２８，２９が形成される。尚、図３の構成では、当初、触媒担持基板９と第１の円筒状部材２５とが密着しているが、実際には両者はその表面にμｍオーダー以下の微小な凹凸を備えており、両者の間には該凹凸により微小な間隙が形成されている。該間隙は、炭素原子に対しては十分に大きな間隙であり、この結果、触媒担持基板９と第１の円筒状部材２５との間に単層ＣＮＴが成長することができる。 According to the substrate holding means 21, single-walled CNTs are grown between the catalyst-carrying substrate 9 and the first cylindrical member 25 by the antenna type plasma CVD method, and single-walled CNT aggregates 28 and 29 are formed. The In the configuration of FIG. 3, the catalyst carrying substrate 9 and the first cylindrical member 25 are in close contact with each other at first, but actually both have fine irregularities of the order of μm or less on the surface, A minute gap is formed between the two by the unevenness. The gap is a sufficiently large gap for carbon atoms, and as a result, a single-walled CNT can grow between the catalyst-carrying substrate 9 and the first cylindrical member 25.
このとき、アンテナ６と触媒担持基板９との間にはＭｏ製基板保持部材２２が介在しているので、触媒担持基板９と単層ＣＮＴ集合体２８，２９とは、アンテナ６に発生するプラズマに対しＭｏ製基板保持部材２２により保護されることとなる。この結果、触媒担持基板９と単層ＣＮＴ集合体２８，２９とは、前記プラズマの攻撃を避けることができ、前記単層ＣＮＴの成長が妨げられることがない。 At this time, since the Mo substrate holding member 22 is interposed between the antenna 6 and the catalyst carrying substrate 9, the catalyst carrying substrate 9 and the single-walled CNT aggregates 28 and 29 are connected to the plasma generated in the antenna 6. On the other hand, it will be protected by the Mo substrate holding member 22. As a result, the catalyst-carrying substrate 9 and the single-walled CNT aggregates 28 and 29 can avoid the attack of the plasma, and the growth of the single-walled CNT is not hindered.
また、前記単層ＣＮＴは触媒担持基板９から第１の円筒状部材２５に向かって成長するが、このときＭｏ製基板保持部材２２と触媒担持基板９とはその自重により該単層ＣＮＴを第１の円筒状部材２５に押圧する。そこで、前記単層ＣＮＴには第１の円筒状部材２５から前記押圧に対する反力が作用することとなり、該反力が該単層ＣＮＴの成長方向に対向する方向に加えられる押圧力となる。 The single-walled CNT grows from the catalyst-carrying substrate 9 toward the first cylindrical member 25. At this time, the Mo-made substrate holding member 22 and the catalyst-carrying substrate 9 form the first-walled CNT by the self-weight. 1 cylindrical member 25 is pressed. Therefore, a reaction force against the pressing acts on the single-walled CNT from the first cylindrical member 25, and the reaction force becomes a pressing force applied in a direction opposite to the growth direction of the single-walled CNT.
従って、前記単層ＣＮＴは、第１の円筒状部材２５が当接されている部分では成長速度が制御される一方、第１の円筒状部材２５が当接されていない貫通孔２７の内部では成長速度が制御されることなく自由に成長する。この結果、第１の円筒状部材２５が当接されている部分に成長する単層ＣＮＴ集合体２８は高密度となり、貫通孔２７の内部に成長する単層ＣＮＴ集合体２９は長尺ではあるが、単層ＣＮＴ集合体２８に比較して密度が低くなる。 Therefore, the growth rate of the single-walled CNT is controlled in the portion where the first cylindrical member 25 is in contact, while in the through hole 27 where the first cylindrical member 25 is not in contact. It grows freely without the growth rate being controlled. As a result, the single-walled CNT aggregate 28 that grows in the portion with which the first cylindrical member 25 is in contact has a high density, and the single-walled CNT aggregate 29 that grows inside the through hole 27 is long. However, the density is lower than that of the single-walled CNT aggregate 28.
また、前記押圧力を加える手段として、触媒担持基板９から上方に向かってＣＮＴを成長させるときには、上方からＣＮＴに当接される当接部材を用いることもできる。 Further, as means for applying the pressing force, when growing CNTs upward from the catalyst-carrying substrate 9, a contact member that contacts the CNTs from above can be used.
触媒担持基板９から上方に向かってＣＮＴを成長させるときには、図４に示すように、触媒担持基板９はステンレス製の基板保持部８上に保持され、触媒担持層１３が基材１１に対しアンテナ６方向に位置するように配置される。また、触媒担持基板９上には、当接部材として、例えば質量１ｇのステンレス板３１が載置される。尚、図４では、触媒担持基板９の反応防止層１２及び分散層１４を省略して示している。 When growing CNTs upward from the catalyst-carrying substrate 9, as shown in FIG. 4, the catalyst-carrying substrate 9 is held on a stainless steel substrate holding unit 8, and the catalyst-carrying layer 13 is an antenna with respect to the base material 11. It arrange | positions so that it may be located in 6 directions. Further, on the catalyst carrying substrate 9, for example, a stainless steel plate 31 having a mass of 1 g is placed as a contact member. In FIG. 4, the reaction preventing layer 12 and the dispersion layer 14 of the catalyst carrying substrate 9 are omitted.
そこで、前記アンテナ型プラズマＣＶＤ法により、触媒担持基板９とステンレス板３１との間に単層ＣＮＴが成長すると、ステンレス板３１が上方から該単層ＣＮＴに当接されることとなる。この結果、ステンレス板３１が、単層ＣＮＴ集合体３２が形成される際に、前記単層ＣＮＴの成長方向に対向する方向に加えられる押圧力となる。 Therefore, when single-walled CNT grows between the catalyst-carrying substrate 9 and the stainless steel plate 31 by the antenna type plasma CVD method, the stainless steel plate 31 comes into contact with the single-walled CNT from above. As a result, when the single-walled CNT aggregate 32 is formed, the stainless steel plate 31 becomes a pressing force applied in a direction opposite to the growth direction of the single-walled CNT.
尚、図４の構成では、当初、触媒担持基板９とステンレス板３１とは密着しているが、実際には両者はその表面にμｍオーダー以下の微小な凹凸を備えており、両者の間には該凹凸により微小な間隙が形成されている。該間隙は、炭素原子に対しては十分に大きな間隙であり、この結果、触媒担持基板９とステンレス板３１との間に単層ＣＮＴが成長することができる。 In the configuration of FIG. 4, the catalyst support substrate 9 and the stainless steel plate 31 are in close contact with each other at first, but actually both have fine irregularities of the order of μm or less on the surface, and between them, A minute gap is formed by the unevenness. The gap is a sufficiently large gap for carbon atoms, and as a result, single-walled CNT can grow between the catalyst-carrying substrate 9 and the stainless steel plate 31.
また、基板保持部８には万力等の係止部材３３を立設し、ある程度単層ＣＮＴが成長するとステンレス板３１が係止部材３３に係止され、該単層ＣＮＴにさらに大きな押圧力が加えられるようにしてもよい。 Further, the substrate holding portion 8 is provided with a locking member 33 such as a vise, and when the single-walled CNT grows to some extent, the stainless steel plate 31 is locked to the locking member 33, and a larger pressing force is applied to the single-walled CNT. May be added.
次に、本発明の実施例及び比較例を示す。 Next, examples and comparative examples of the present invention are shown.
〔実施例１及び比較例１〕
本実施例では、図１に示すアンテナ型プラズマＣＶＤ装置１において、基板保持部８に代えて、図３に示す基板保持手段２１を用いて単層ＣＮＴ集合体２８，２９を製造した。図３に示すアンテナ６の先端部６ａと、Ｍｏ製基板保持部材２２との距離は、５０ｍｍとした。
[Example 1 and Comparative Example 1]
In this example, single-walled CNT aggregates 28 and 29 were manufactured using the substrate holding means 21 shown in FIG. 3 in place of the substrate holding portion 8 in the antenna type plasma CVD apparatus 1 shown in FIG. The distance between the tip 6a of the antenna 6 shown in FIG. 3 and the Mo substrate holding member 22 was 50 mm.
また、基板保持手段２１に保持される触媒担持基板９として、図２に示す構成において、シリコンからなる基材１１と、Ａｌからなる反応防止層１２と、Ｆｅからなる触媒担持層１３と、Ａｌからなる分散層１４とを備えるものを用いた。触媒担持基板９において、反応防止層１２は５０ｎｍの厚さを備え、触媒担持層１３は０．５ｎｍの厚さを備え、分散層１４は１．０ｎｍの厚さを備えている。 Further, as the catalyst supporting substrate 9 held by the substrate holding means 21, in the configuration shown in FIG. 2, the base material 11 made of silicon, the reaction preventing layer 12 made of Al, the catalyst supporting layer 13 made of Fe, and Al What was provided with the dispersion layer 14 which consists of was used. In the catalyst supporting substrate 9, the reaction preventing layer 12 has a thickness of 50 nm, the catalyst supporting layer 13 has a thickness of 0.5 nm, and the dispersion layer 14 has a thickness of 1.0 nm.
次に、原料ガス導入部３から原料ガスとしてのメタンとキャリアガスとしての水素との混合ガスをＣＨ４：Ｈ２＝１０：９０の容積比で供給しつつ、ガス排出部４からチャンバー２内のガスを排出し、チャンバー２内の圧力を７９９９Ｐａ（６０Ｔｏｒｒ）に保持した。この状態で、チャンバー２内部の温度を７００℃とし、マイクロ波導波管５により２．４５ＧＨｚのマイクロ波を１２０Ｗの出力で印加することによりアンテナ６の先端部６ａに５時間に亘ってプラズマを発生させ、ＣＮＴを合成した。 Next, while supplying a mixed gas of methane as the source gas and hydrogen as the carrier gas from the source gas introduction unit 3 at a volume ratio of CH 4 : H 2 = 10: 90, the gas exhaust unit 4 enters the chamber 2 The pressure in the chamber 2 was maintained at 7999 Pa (60 Torr). In this state, the temperature inside the chamber 2 is set to 700 ° C., and a microwave of 2.45 GHz is applied by the microwave waveguide 5 at an output of 120 W to generate plasma at the tip 6a of the antenna 6 for 5 hours. CNTs were synthesized.
このとき、第１の円筒状部材２５が当接されている部分に形成された単層ＣＮＴ集合体２８（実施例１）と、貫通孔２７の内部に形成された単層ＣＮＴ集合体２９（比較例１）との透過型電子顕微鏡写真を図５に示す。図５から、単層ＣＮＴ集合体２８，２９は触媒担持基板９に対し、垂直に配向していることが明らかである。 At this time, the single-walled CNT aggregate 28 (Example 1) formed in the portion with which the first cylindrical member 25 is in contact, and the single-walled CNT aggregate 29 formed in the through hole 27 ( A transmission electron micrograph of Comparative Example 1) is shown in FIG. From FIG. 5, it is clear that the single-walled CNT aggregates 28 and 29 are oriented perpendicular to the catalyst-carrying substrate 9.
また、第１の円筒状部材２５が当接されている部分に形成された単層ＣＮＴ集合体２８の拡大図を図６（ａ）に、単層ＣＮＴ集合体２８のラマンスペクトルを図６（ｂ）に示す。また、貫通孔２７の内部に形成された単層ＣＮＴ集合体２９の拡大図を図７（ａ）に、単層ＣＮＴ集合体２９のラマンスペクトルを図７（ｂ）に示す。 Further, FIG. 6A is an enlarged view of the single-walled CNT aggregate 28 formed in the portion where the first cylindrical member 25 is in contact, and FIG. 6A shows the Raman spectrum of the single-walled CNT aggregate 28. Shown in b). An enlarged view of the single-walled CNT aggregate 29 formed inside the through hole 27 is shown in FIG. 7A, and a Raman spectrum of the single-walled CNT aggregate 29 is shown in FIG. 7B.
次に、図５〜７から明らかになった単層ＣＮＴ集合体２８，２９の物性について表１に示す。 Next, Table 1 shows the physical properties of the single-walled CNT aggregates 28 and 29 clarified from FIGS.
表１から、第１の円筒状部材２５が当接されている部分で単層ＣＮＴの成長方向に対向する方向に押圧力が加えられることにより合成された単層ＣＮＴ集合体２８は、貫通孔２７の内部で該押圧力が加えられることなく合成された単層ＣＮＴ集合体２９に比較して、高密度になっていることが明らかである。また、単層ＣＮＴ集合体２８は、単層ＣＮＴ集合体２９に比較してＧ／Ｄ比が大であり、ＣＮＴとしてより欠陥の少ない優れた品質を備えていることが明らかである。 From Table 1, the single-walled CNT aggregate 28 synthesized by applying a pressing force in a direction opposite to the growth direction of the single-walled CNT at the portion where the first cylindrical member 25 is in contact with It is clear that the density is higher than that of the single-walled CNT aggregate 29 synthesized without applying the pressing force inside the unit 27. In addition, it is clear that the single-walled CNT aggregate 28 has a higher G / D ratio than the single-walled CNT aggregate 29 and has excellent quality with fewer defects as CNTs.
尚、Ｇ／Ｄ比とは、単層ＣＮＴにおける結晶品質を定量化する指標であり、ラマンスペクトルにより１５９０ｃｍ−１付近に得られるＧピークと、１３５０ｃｍ−１付近に得られるＤピークと強度比によって示される値である。 Note that the G / D ratio is an index to quantify the crystal quality in the monolayer CNT, a G peak obtained in the vicinity of 1590 cm -1 by Raman spectrum, the D peak and the intensity ratio obtained around 1350 cm -1 The value shown.
〔実施例２及び比較例２〕
本実施例では、図１に示すアンテナ型プラズマＣＶＤ装置１において、図４に示す基板保持部８を用いた以外は、実施例１と全く同一にして単層ＣＮＴ集合体を製造した。
[Example 2 and Comparative Example 2]
In this example, a single-walled CNT aggregate was produced in the same manner as in Example 1 except that the substrate holding unit 8 shown in FIG. 4 was used in the antenna type plasma CVD apparatus 1 shown in FIG.
また、本比較例では、図４に示す基板保持部８において、ステンレス板３１を用いない以外は前記実施例と全く同一にして単層ＣＮＴ集合体を製造した。 Further, in this comparative example, a single-walled CNT aggregate was manufactured in the same manner as in the above example except that the stainless steel plate 31 was not used in the substrate holding portion 8 shown in FIG.
図４に示す基板保持部８において、ステンレス板３１を用いた場合を実施例２、ステンレス板３１を用いない場合を比較例２として、それぞれの単層ＣＮＴ集合体の物性について表２に示す。 Table 2 shows the physical properties of each single-walled CNT aggregate in Example 2 when the stainless steel plate 31 is used in the substrate holder 8 shown in FIG. 4 and Comparative Example 2 when the stainless steel plate 31 is not used.
表２から、単層ＣＮＴ上にステンレス板３１が当接されて、該単層ＣＮＴの成長方向に対向する方向に押圧力が加えられることにより合成された実施例２の単層ＣＮＴ集合体は、ステンレス板３１により該押圧力が加えられることなく合成された比較例２の単層ＣＮＴ集合体に比較して高密度になっていることが明らかである。 From Table 2, the single-walled CNT aggregate of Example 2 synthesized by contacting the stainless steel plate 31 on the single-walled CNT and applying a pressing force in a direction opposite to the growth direction of the single-walled CNT is as follows. It is clear that the density is higher than that of the single-walled CNT aggregate of Comparative Example 2 synthesized without applying the pressing force by the stainless steel plate 31.
１…アンテナ型プラズマＣＶＤ装置、 ２…チャンバー、 ６…アンテナ、 ８…基板保持部、 ９…触媒担持基板、 １１…基材、 １２…反応防止層、 １３…触媒担持層、 １４…分散層、 ２１…基板保持手段、 ２３…石英製当接部材、 ３１…ステンレス板。 DESCRIPTION OF SYMBOLS 1 ... Antenna type plasma CVD apparatus, 2 ... Chamber, 6 ... Antenna, 8 ... Substrate holding part, 9 ... Catalyst support substrate, 11 ... Base material, 12 ... Reaction prevention layer, 13 ... Catalyst support layer, 14 ... Dispersion layer, 21 ... Substrate holding means, 23 ... Quartz contact member, 31 ... Stainless steel plate.
Claims (6)
該触媒担持基板の触媒が担持されている面上に成長するカーボンナノチューブに対し、該カーボンナノチューブの成長方向に対向する方向に押圧力を加えることを特徴とするカーボンナノチューブの製造方法。 Carbon that circulates a gas as a carbon nanotube raw material in the processing chamber, decompresses the processing chamber to a predetermined pressure, and grows the carbon nanotube on the catalyst supporting substrate held in the processing chamber by chemical vapor deposition In the method for producing nanotubes,
A method for producing a carbon nanotube, comprising applying a pressing force to a carbon nanotube growing on a surface of the catalyst carrying substrate on which a catalyst is carried, in a direction opposite to the growth direction of the carbon nanotube.
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|---|---|---|---|---|
| JP2005247644A (en) * | 2004-03-04 | 2005-09-15 | Keio Gijuku | Carbon nanotube manufacturing method and manufacturing apparatus |
| JP2006036593A (en) * | 2004-07-27 | 2006-02-09 | Univ Waseda | Single-walled carbon nanotube manufacturing method and manufacturing apparatus thereof |
| US20080292835A1 (en) * | 2006-08-30 | 2008-11-27 | Lawrence Pan | Methods for forming freestanding nanotube objects and objects so formed |
| WO2011025000A1 (en) * | 2009-08-31 | 2011-03-03 | 本田技研工業株式会社 | Oriented carbon nanotube manufacturing method |
| JP2012106921A (en) * | 2010-11-16 | 2012-06-07 | Waseda Univ | Method for producing carbon nanotube |
| JP2012184145A (en) * | 2011-03-07 | 2012-09-27 | Honda Motor Co Ltd | Substrate for carbon nanotube growth, method of manufacturing the same, and method of manufacturing oriented carbon nanotube |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005247644A (en) * | 2004-03-04 | 2005-09-15 | Keio Gijuku | Carbon nanotube manufacturing method and manufacturing apparatus |
| JP2006036593A (en) * | 2004-07-27 | 2006-02-09 | Univ Waseda | Single-walled carbon nanotube manufacturing method and manufacturing apparatus thereof |
| US20080292835A1 (en) * | 2006-08-30 | 2008-11-27 | Lawrence Pan | Methods for forming freestanding nanotube objects and objects so formed |
| WO2011025000A1 (en) * | 2009-08-31 | 2011-03-03 | 本田技研工業株式会社 | Oriented carbon nanotube manufacturing method |
| JP2012106921A (en) * | 2010-11-16 | 2012-06-07 | Waseda Univ | Method for producing carbon nanotube |
| JP2012184145A (en) * | 2011-03-07 | 2012-09-27 | Honda Motor Co Ltd | Substrate for carbon nanotube growth, method of manufacturing the same, and method of manufacturing oriented carbon nanotube |
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