JP6234298B2 - Carbon nanotube production equipment - Google Patents

Carbon nanotube production equipment Download PDF

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JP6234298B2
JP6234298B2 JP2014067313A JP2014067313A JP6234298B2 JP 6234298 B2 JP6234298 B2 JP 6234298B2 JP 2014067313 A JP2014067313 A JP 2014067313A JP 2014067313 A JP2014067313 A JP 2014067313A JP 6234298 B2 JP6234298 B2 JP 6234298B2
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JP2015189619A (en
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杉本　巖生
巖生 杉本
浩史 辰己
浩史 辰己
剣二 石黒
剣二 石黒
浩二 ▲高▼鍋
浩二 ▲高▼鍋
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Hitachi Zosen Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description

本発明は、カーボンナノチューブの製造装置に関する。   The present invention relates to a carbon nanotube production apparatus.

従来より知られている高性能の電池としては、電極において、電解質膜上のカーボンナノチューブの外表面にアモルファス層を成長させたものを採用することにより、より多くの電池触媒を担持させ得るとともに電池触媒がカーボンナノチューブの表面で凝集するのを抑制し、より発電効率を向上させた燃料電池が知られている（例えば、特許文献１参照）。   As a conventionally known high-performance battery, an electrode in which an amorphous layer is grown on the outer surface of the carbon nanotube on the electrolyte membrane can be used to support more battery catalysts and the battery. There is known a fuel cell in which the catalyst is prevented from aggregating on the surface of the carbon nanotube and the power generation efficiency is further improved (for example, see Patent Document 1).

特開２００７−２５７８８６号公報JP 2007-257886 A

従来技術において、カーボンナノチューブの長さ及びアモルファス層の厚みは、供給される原料ガスの濃度により制御されているが、十分高い濃度の原料ガスを供給しても、得られるアモルファス層の厚みによっては、カーボンナノチューブの表面における電池触媒の凝集が抑制されない場合があった。   In the prior art, the length of the carbon nanotube and the thickness of the amorphous layer are controlled by the concentration of the source gas supplied, but even if a sufficiently high concentration of source gas is supplied, depending on the thickness of the resulting amorphous layer In some cases, aggregation of the battery catalyst on the surface of the carbon nanotube is not suppressed.

この問題を解決するためには、例えば、結晶性の高いカーボンナノチューブの成長（いわゆる長さの成長）に適した温度と、カーボンナノチューブの外表面に形成される非晶質のカーボンの成長（いわゆるアモルファス層の成長）に適した温度との２段階でカーボンナノチューブを成長させることで、長さとアモルファス層の厚みとを個別に制御できると思われる。しかし、このようなカーボンナノチューブを連続的に生成する製造装置においては、１つの反応容器内に設けられた、１段階目の成長を行う領域と２段階目の成長を行う領域との間に、長さの成長に適した温度からアモルファス層の成長に適した温度へ遷移させる区間を必要とするが、この区間に誤って原料ガスが流入することによりカーボンナノチューブの長さが余分に伸びてしまい、正確にカーボンナノチューブの長さを制御し得ない場合があると考えられる。   In order to solve this problem, for example, a temperature suitable for growth of carbon nanotubes having high crystallinity (so-called length growth) and growth of amorphous carbon formed on the outer surface of the carbon nanotubes (so-called growth) It seems that the length and the thickness of the amorphous layer can be individually controlled by growing the carbon nanotubes in two stages with a temperature suitable for the growth of the amorphous layer. However, in such a manufacturing apparatus that continuously generates carbon nanotubes, a region provided in one reaction vessel that performs the first-stage growth and a region that performs the second-stage growth, A section is required to transition from a temperature suitable for the growth of the length to a temperature suitable for the growth of the amorphous layer, but the length of the carbon nanotubes is excessively extended due to the material gas flowing into this section by mistake. It is considered that there are cases where the length of the carbon nanotube cannot be accurately controlled.

そこで、本発明は、カーボンナノチューブの長さ及びアモルファス層の厚みを正確に制御し得るカーボンナノチューブの製造装置を提供することを目的とする。   Therefore, an object of the present invention is to provide a carbon nanotube production apparatus capable of accurately controlling the length of a carbon nanotube and the thickness of an amorphous layer.

本発明に係るカーボンナノチューブの製造装置は、表面に触媒が担持されかつ所定方向に移動される基板を導き入れるとともに、前記基板の移動方向に沿って、前記基板表面を第１ＣＶＤ温度に加熱してカーボンナノチューブを所定の長さに成長させる第１ＣＶＤ温度領域と、さらに前記基板表面を前記第１ＣＶＤ温度よりも高い第２ＣＶＤ温度に加熱してカーボンナノチューブの表面にカーボンを付着させる第２ＣＶＤ領域とが設けられた、化学気相成長法を用いてカーボンナノチューブを連続的に生成する減圧の反応容器を有するカーボンナノチューブの製造装置であって、
前記反応容器において、前記第１ＣＶＤ温度領域と前記第２ＣＶＤ温度領域とには、前記基板に前記原料ガスを供給する前記原料ガス供給管に接続されて、前記基板の表面を所定範囲に亘って覆うことで反応空間を制限する第１空間仕切体と第２空間仕切体とがそれぞれ配置され、
前記第１空間仕切体と前記第２空間仕切体との間に熱遮蔽部材が設けられていることを特徴とする。 The carbon nanotube production apparatus according to the present invention introduces a substrate on which a catalyst is supported and is moved in a predetermined direction, and heats the substrate surface to a first CVD temperature along the direction of movement of the substrate. There is provided a first CVD temperature region in which carbon nanotubes are grown to a predetermined length, and a second CVD region in which the substrate surface is heated to a second CVD temperature higher than the first CVD temperature to deposit carbon on the surface of the carbon nanotubes. An apparatus for producing carbon nanotubes having a reduced pressure reaction vessel for continuously producing carbon nanotubes using chemical vapor deposition,
In the reaction vessel, the first CVD temperature region and the second CVD temperature region are connected to the source gas supply pipe for supplying the source gas to the substrate and cover the surface of the substrate over a predetermined range. The first space partition and the second space partition that limit the reaction space by being arranged, respectively,
A heat shielding member is provided between the first space partition and the second space partition.

また、熱遮蔽部材には、セラミックス又は炭化ケイ素が被覆された鋼が用いられることが好ましい。
また、第２ＣＶＤ温度は第１ＣＶＤ温度よりも５０度〜２００度高く設定するとよい。 The heat shielding member is preferably made of steel coated with ceramics or silicon carbide.
The second CVD temperature may be set higher by 50 to 200 degrees than the first CVD temperature.

また、反応容器において、第１空間仕切体よりも基板の移動方向の後方側及び第２空間仕切体よりも前記基板の移動方向の前方側にさらに熱遮蔽部材がそれぞれ設けられることが好ましい。   In the reaction vessel, it is preferable that a heat shielding member is further provided on the rear side in the movement direction of the substrate with respect to the first space partition and on the front side in the movement direction of the substrate with respect to the second space partition.

また、熱遮蔽部材は複数の板材により構成されるとともに、反応容器の壁部に、前記板材間から排出される原料ガスを外部へ排気するガス排気管が接続されていることがより好ましい。   More preferably, the heat shielding member is composed of a plurality of plates, and a gas exhaust pipe for exhausting the raw material gas discharged from between the plates to the outside is connected to the wall portion of the reaction vessel.

本発明のカーボンナノチューブの製造装置によれば、長さの成長に適した温度に加熱された第１ＣＶＤ温度領域と、アモルファス層の成長に適した温度に加熱された第２ＣＶＤ温度領域との間に、熱遮蔽部材を設けることにより、第１ＣＶＤ温度領域と第２ＣＶＤ温度領域との間の熱移動を防ぐとともに、原料ガスの流入を防ぎ、カーボンナノチューブの長さ及びアモルファス層の厚みが正確に制御されたカーボンナノチューブを製造することができる。   According to the carbon nanotube manufacturing apparatus of the present invention, between the first CVD temperature region heated to a temperature suitable for the growth of the length and the second CVD temperature region heated to a temperature suitable for the growth of the amorphous layer. By providing the heat shielding member, the heat transfer between the first CVD temperature region and the second CVD temperature region is prevented, the inflow of the source gas is prevented, and the length of the carbon nanotube and the thickness of the amorphous layer are accurately controlled. Carbon nanotubes can be produced.

本発明の実施例１に係るカーボンナノチューブの製造装置の全体の概略構成を示す側面図である。It is a side view which shows the schematic structure of the whole carbon nanotube manufacturing apparatus which concerns on Example 1 of this invention. 同製造装置の減圧チャンバー内の概略構成を示す斜視図である。It is a perspective view which shows schematic structure in the pressure reduction chamber of the manufacturing apparatus. 同減圧チャンバー内の概略構成を示す縦断面図である。It is a longitudinal cross-sectional view which shows schematic structure in the pressure reduction chamber. 同減圧チャンバー内の熱遮蔽部材及び形成部における部分拡大図である。It is the elements on larger scale in the heat shielding member and formation part in the decompression chamber. 図４に示すＢ−Ｂ断面図である。It is BB sectional drawing shown in FIG. 本発明の実施例２に係るカーボンナノチューブの製造装置の熱遮蔽部材及び形成部における部分拡大図である。It is the elements on larger scale in the heat shielding member and formation part of the manufacturing apparatus of the carbon nanotube which concerns on Example 2 of this invention.

［実施例１］
本発明の実施例１に係るカーボンナノチューブの製造装置について、図１〜図６を用いて説明する。 [Example 1]
A carbon nanotube production apparatus according to Example 1 of the present invention will be described with reference to FIGS.

図２及び図３に示すように、処理用空間部４は、基板２の移動方向に沿って、基板２の温度を所定温度まで上昇させる前処理部１０と、前処理部１０にて所定温度まで上昇した基板２に原料ガスＧ２を供給しながら化学気相成長法（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ ｍｅｔｈｏｄ：ＣＶＤ法）によりカーボンナノチューブ３を形成する形成部２０と、形成部２０にて形成されたカーボンナノチューブ３を有する基板２を導いて基板２の温度を下げる後処理部（冷却部ともいえる。）３０とを備える。処理用空間部４は、基板２の表面温度によって、図３に仮想線にて示すように、前処理部１０に対応する昇温領域Ｘ、形成部２０に対応するＣＶＤ温度領域Ｙ及び後処理部３０に対応する降温領域Ｚに分けられる。減圧チャンバー５の内壁面には断熱材９が設けられている。   As shown in FIGS. 2 and 3, the processing space 4 includes a pre-processing unit 10 that raises the temperature of the substrate 2 to a predetermined temperature along the moving direction of the substrate 2, and a predetermined temperature at the pre-processing unit 10. Forming the carbon nanotube 3 by the chemical vapor deposition method (Chemical Vapor Deposition method: CVD method) while supplying the raw material gas G2 to the substrate 2 that has risen up to, and the carbon nanotube 3 formed in the forming portion 20 And a post-processing unit (also referred to as a cooling unit) 30 for lowering the temperature of the substrate 2. Depending on the surface temperature of the substrate 2, the processing space 4 includes a temperature rising region X corresponding to the preprocessing unit 10, a CVD temperature region Y corresponding to the forming unit 20, and post-processing, as indicated by a virtual line in FIG. It is divided into a temperature fall region Z corresponding to the part 30. A heat insulating material 9 is provided on the inner wall surface of the decompression chamber 5.

まず、前処理部１０は、繰出部６側の減圧チャンバー５内に設けられて、基板２の温度を下手側の形成部２０での加熱温度（ＣＶＤ温度）と同等の温度まで上昇させるための加熱装置を少なくとも１つ具備する。本実施例においては、昇温領域Ｘでは３段階で基板２を昇温させるため、図３に仮想線にて示すように、上流側から下流側に向かって、第１温度領域Ａ１、第２温度領域Ａ２及び第３温度領域Ａ３が設けられている。前処理部１０は、第１温度領域Ａ１に設けられた第１加熱装置１１、第２温度領域Ａ２に設けられた第２加熱装置１２及び第３温度領域Ａ３に設けられた第３加熱装置１３の３つの加熱装置を具備する。第１加熱装置１１、第２加熱装置１２及び第３加熱装置１３の加熱温度は、基板２表面が４５０℃〜６００℃の範囲となるような温度にそれぞれ設定されている。ここで、本実施例においては、基板２表面の温度の計測は、減圧チャンバー５の基板２表面近くに熱電対などの温度計を挿入し、測定された温度から基板２表面の温度を算出することで、加熱装置による加熱温度を維持又は制御している。   First, the pretreatment unit 10 is provided in the decompression chamber 5 on the feeding unit 6 side, and increases the temperature of the substrate 2 to a temperature equivalent to the heating temperature (CVD temperature) in the formation unit 20 on the lower side. At least one heating device is provided. In the present embodiment, since the temperature of the substrate 2 is raised in three stages in the temperature raising region X, the first temperature region A1 and the second temperature are increased from the upstream side to the downstream side as shown by the phantom line in FIG. A temperature region A2 and a third temperature region A3 are provided. The pretreatment unit 10 includes a first heating device 11 provided in the first temperature region A1, a second heating device 12 provided in the second temperature region A2, and a third heating device 13 provided in the third temperature region A3. The three heating devices are provided. The heating temperature of the 1st heating apparatus 11, the 2nd heating apparatus 12, and the 3rd heating apparatus 13 is each set to the temperature from which the board | substrate 2 surface becomes the range of 450 to 600 degreeC. In this embodiment, the temperature of the surface of the substrate 2 is measured by inserting a thermometer such as a thermocouple near the surface of the substrate 2 in the decompression chamber 5 and calculating the temperature of the surface of the substrate 2 from the measured temperature. Thus, the heating temperature by the heating device is maintained or controlled.

そして、前処理部１０は、繰出部６から送出された所定幅の基板２の周囲を覆うとともに基板２を案内するダクト１４を具備する。本実施例においては、図２及び図３に示すように、ダクト１４は断面矩形状で中空のものが用いられており、前処理部１０（昇温領域Ｘ）の前端から後端すなわち第１温度領域Ａ１から第３温度領域Ａ３に亘って延設されている。一般的には、ダクト１４は、図４に示すように、少なくとも基板２が挿入され得る大きさであればよい。なお、本実施例のようにロール・ツー・ロール式の製造装置１においては、基板２の厚みは例えば０．０３ｍｍ〜０．１００ｍｍである。また、図３に示すように、本実施例においては、前処理部１０のダクト１４の上流側の端部は、繰出部６と減圧チャンバー５とを接続する接続部材８内へ突出しており、チャンバー５にはダクト１４が挿入されるための挿入口１５が形成されている。この挿入口１５とダクト１４との間に、前処理部１０内のガス等の接続部材８内への流入を防ぐシール部材として例えばＯ‐リング（オーリング）１６が設けられている。   The pretreatment unit 10 includes a duct 14 that guides the substrate 2 while covering the periphery of the substrate 2 having a predetermined width sent from the feeding unit 6. In this embodiment, as shown in FIGS. 2 and 3, the duct 14 is rectangular in cross section and hollow, and the duct 14 is used from the front end to the rear end, that is, the first end of the pretreatment unit 10 (temperature rising region X). The temperature region A1 extends from the third temperature region A3. In general, as shown in FIG. 4, the duct 14 may have a size that allows at least the substrate 2 to be inserted. In the roll-to-roll manufacturing apparatus 1 as in this embodiment, the thickness of the substrate 2 is, for example, 0.03 mm to 0.100 mm. Further, as shown in FIG. 3, in the present embodiment, the upstream end of the duct 14 of the pretreatment unit 10 protrudes into the connecting member 8 that connects the feeding unit 6 and the decompression chamber 5, An insertion port 15 for inserting the duct 14 is formed in the chamber 5. Between the insertion port 15 and the duct 14, for example, an O-ring (O-ring) 16 is provided as a seal member that prevents the gas in the pretreatment unit 10 from flowing into the connection member 8.

前処理部１０のダクト１４には、繰出部６側から接続部材８を介して前処理用ガスＧ１が供給される。前処理用ガスＧ１としては、例えば、窒素（Ｎ２）やアルゴン（Ａｒ）などの不活性ガスと、基板２表面の触媒を微粒化する水素（Ｈ２）などの微粒化ガスが用いられる。なお、不活性ガスと併せて微粒化ガスを供給しても構わない。 The pretreatment gas G <b> 1 is supplied to the duct 14 of the pretreatment unit 10 from the supply unit 6 side via the connection member 8. As the pretreatment gas G1, for example, an inert gas such as nitrogen (N 2 ) or argon (Ar) and an atomized gas such as hydrogen (H 2 ) that atomizes the catalyst on the surface of the substrate 2 are used. Note that the atomization gas may be supplied together with the inert gas.

本実施例においては、図３及び図４に示すように、前処理部１０と形成部２０との境界近傍に、前処理部１０のダクト１４の下流側の端部が位置している。前処理部１０のダクト１４の下流側の端部には、前処理部１０に供給された前処理用ガスＧ１と形成部２０に供給された原料ガスＧ２（正確には化学反応により発生した原料ガスＧ２の分解成分を含む。以下、原料ガスＧ２及びこの分解成分とを併せて原料ガス等Ｇ４ということがある。）とが混合した混合ガスＧ３を排気するための排気用開口部４０が設けられている。本実施例において、排気用開口部４０は、前処理部１０のダクト１４の上流側の開口端部である。   In the present embodiment, as shown in FIGS. 3 and 4, the downstream end of the duct 14 of the pretreatment unit 10 is located in the vicinity of the boundary between the pretreatment unit 10 and the forming unit 20. At the downstream end of the duct 14 of the pretreatment unit 10, the pretreatment gas G1 supplied to the pretreatment unit 10 and the raw material gas G2 supplied to the forming unit 20 (precisely, the raw material generated by a chemical reaction) An exhaust opening 40 for exhausting the mixed gas G3 mixed with the source gas G2 and the decomposed component may be referred to as source gas G4). It has been. In the present embodiment, the exhaust opening 40 is an opening end on the upstream side of the duct 14 of the pretreatment unit 10.

また、前処理部１０と形成部２０との境界近傍には、原料ガスＧ２をより確実に前処理部１０のダクト１４に流入させないようにするため、排気用開口部４０から排気される混合ガスＧ３を減圧チャンバー５の外へ流出する混合ガス排気管４１と混合ガス排気管４１を接続するための混合ガス排気口４１ａとが設けられている。本実施例においては、図４に示すように、混合ガス排気管４１及び混合ガス排気口４１ａは、減圧チャンバー５の基板２の下方に配置される。   Further, in order to prevent the source gas G2 from flowing into the duct 14 of the pretreatment unit 10 in the vicinity of the boundary between the pretreatment unit 10 and the formation unit 20, the mixed gas exhausted from the exhaust opening 40. A mixed gas exhaust pipe 41 for flowing G3 out of the decompression chamber 5 and a mixed gas exhaust port 41a for connecting the mixed gas exhaust pipe 41 are provided. In the present embodiment, as shown in FIG. 4, the mixed gas exhaust pipe 41 and the mixed gas exhaust port 41 a are disposed below the substrate 2 in the decompression chamber 5.

このように、前処理部１０に設けられたダクト１４に前処理用ガスＧ１を供給することによって、ダクト１４内に形成部２０から原料ガスＧ２が流入することを防ぐことができる。ゆえに、基板２表面の触媒に原料ガスＧ２が接触することを防ぎ、表面に担持された触媒の活性力が損なわれることなく、基板２が形成部２０へ送られるので、カーボンナノチューブ３の生成率が向上する。   In this way, by supplying the pretreatment gas G1 to the duct 14 provided in the pretreatment unit 10, the raw material gas G2 can be prevented from flowing into the duct 14 from the formation unit 20. Therefore, the raw material gas G2 is prevented from coming into contact with the catalyst on the surface of the substrate 2, and the substrate 2 is sent to the forming unit 20 without impairing the activity of the catalyst supported on the surface. Will improve.

前処理部１０が排気用開口部４０を備えることによって、原料ガスＧ２が前処理部１０のダクト１４に流入されることをより確実に防ぎ、カーボンナノチューブ３の生成率を向上させることができる。   When the pretreatment unit 10 includes the exhaust opening 40, the raw material gas G2 can be more reliably prevented from flowing into the duct 14 of the pretreatment unit 10, and the production rate of the carbon nanotubes 3 can be improved.

次に、本発明の要旨となる前処理部１０の下流側に設けられた形成部２０すなわちＣＶＤ温度領域Ｙは、図３及び図４に示すように、基板２の表面が結晶性の高いカーボンナノチューブの成長（いわゆる長さ方向での成長）に適した第１ＣＶＤ温度となるように加熱する第１ＣＶＤ温度領域（第４温度領域）Ａ４と、基板２の表面がカーボンナノチューブの外表面に形成される非晶質のカーボンの成長（いわゆるアモルファス層の成長）に適した第２ＣＶＤ温度となるように加熱する第２ＣＶＤ温度領域（第５温度領域）Ａ５とを備える。具体的には、第１ＣＶＤ温度は６００℃〜７００℃の範囲であることが好ましく、第２ＣＶＤ温度は第１ＣＶＤ温度よりも５０℃〜２００℃高い温度である６５０℃〜９００℃の範囲であることが好ましい。   Next, as shown in FIGS. 3 and 4, the formation portion 20 provided at the downstream side of the pretreatment portion 10 that is the gist of the present invention, that is, the CVD temperature region Y, is a carbon whose surface of the substrate 2 is highly crystalline. A first CVD temperature region (fourth temperature region) A4 that is heated to a first CVD temperature suitable for nanotube growth (so-called growth in the length direction) and the surface of the substrate 2 are formed on the outer surface of the carbon nanotube. And a second CVD temperature region (fifth temperature region) A5 that is heated to a second CVD temperature suitable for the growth of amorphous carbon (so-called amorphous layer growth). Specifically, the first CVD temperature is preferably in the range of 600 ° C to 700 ° C, and the second CVD temperature is in the range of 650 ° C to 900 ° C, which is 50 ° C to 200 ° C higher than the first CVD temperature. Is preferred.

上流側の第１ＣＶＤ温度領域Ａ４には、基板２の下方に設けられた第４加熱装置２５が、下流側の第２ＣＶＤ温度領域Ａ５には、基板２の下方に設けられた第５加熱装置２６がそれぞれ配置されている。第４加熱装置２５及び第５加熱装置２６は、主として基板２を、また減圧チャンバー５内の第１ＣＶＤ温度領域Ａ４と第２ＣＶＤ温度領域Ａ５とを併せて加熱する。   A fourth heating device 25 provided below the substrate 2 is provided in the upstream first CVD temperature region A4, and a fifth heating device 26 provided below the substrate 2 is provided in the downstream second CVD temperature region A5. Are arranged respectively. The fourth heating device 25 and the fifth heating device 26 mainly heat the substrate 2 and the first CVD temperature region A4 and the second CVD temperature region A5 in the decompression chamber 5 together.

形成部２０すなわち第１ＣＶＤ温度領域Ａ４及び第２ＣＶＤ温度領域Ａ５には、図３及び図４に示すように、減圧チャンバー５内にメタン（ＣＨ４）やアセチレン（Ｃ２Ｈ２）などの炭化水素系の原料ガスＧ２を供給するための原料ガス供給管２１と、原料ガス供給管２１を接続するための原料ガス供給口２１ａと、この原料ガス供給管２１に接続されて、基板２の表面を所定範囲に亘って覆うことで、供給された原料ガスＧ２を基板２上で化学反応させカーボンナノチューブ３を生成する反応空間を制限する第１空間仕切体２２Ａ及び第２空間仕切体２２Ｂがそれぞれ備えられる。第１空間仕切体２２Ａにおいては、主としてカーボンナノチューブの長さを制御し、第２空間仕切体２２Ｂにおいては、主としてアモルファス層の厚み（より具体的にはカーボンナノチューブの太さ）を制御する。 As shown in FIGS. 3 and 4, in the forming unit 20, that is, the first CVD temperature region A4 and the second CVD temperature region A5, hydrocarbons such as methane (CH 4 ) and acetylene (C 2 H 2 ) are contained in the decompression chamber 5. The source gas supply pipe 21 for supplying the source gas G2 of the system, the source gas supply port 21a for connecting the source gas supply pipe 21, and the source gas supply pipe 21 are connected to the surface of the substrate 2. A first space partition 22A and a second space partition 22B that limit the reaction space in which the supplied source gas G2 is chemically reacted on the substrate 2 to generate the carbon nanotubes 3 by covering over a predetermined range are provided. It is done. The first space partition 22A mainly controls the length of the carbon nanotubes, and the second space partition 22B mainly controls the thickness of the amorphous layer (more specifically, the thickness of the carbon nanotubes).

空間仕切体２２Ａ，２２Ｂは、図３及び図４に示すように、中空の直方体形状の反応本体部２３と、その下端部に設けられて基板２の移動方向に沿って延びて基板２の周囲を覆い基板２を案内する基板案内用突出部２４とから成る。具体的には、図３及び図４に示すように、基板案内用突出部２４の断面はダクト１４と同一形状にされており、言い換えれば、反応本体部２３にダクト１４が接続された形状をしている。以下、この基板案内用突出部をダクト部２４という。反応本体部２３は、熱伝導性及び熱膨張性の小さい石英ガラス製の５枚の板を各接合部に設けられた段部を係合させて溶接することにより形成されている。また、反応本体部２３は原料ガス供給管２１を接続するための供給管接続口２１ｂを有する。すなわち、原料ガス供給管２１は減圧チャンバー５の原料ガス供給口２１ａに挿通されて供給管接続口２１ｂまで設けられる。なお、本実施例においては、図４に示すように、前処理部１０のダクト１４の開口端部の高さＨ１と、形成部２０のダクト部２４の前処理部１０側（上流側）の開口端部の高さＨ２とは、同一（Ｈ１＝Ｈ２）にされている。   As shown in FIGS. 3 and 4, the space partitions 22 </ b> A and 22 </ b> B are provided in the hollow rectangular parallelepiped reaction main body 23 and the lower end thereof and extend along the moving direction of the substrate 2 to surround the substrate 2. And a substrate guide protrusion 24 for guiding the substrate 2. Specifically, as shown in FIGS. 3 and 4, the cross section of the substrate guiding protrusion 24 has the same shape as the duct 14, in other words, the shape in which the duct 14 is connected to the reaction main body 23. doing. Hereinafter, the board guide protrusion is referred to as a duct portion 24. The reaction main body 23 is formed by welding five plates made of quartz glass having low thermal conductivity and low thermal expansion by engaging the stepped portions provided at each joint. The reaction main body 23 has a supply pipe connection port 21 b for connecting the source gas supply pipe 21. That is, the source gas supply pipe 21 is inserted into the source gas supply port 21a of the decompression chamber 5 and provided to the supply pipe connection port 21b. In this embodiment, as shown in FIG. 4, the height H1 of the opening end of the duct 14 of the pretreatment unit 10 and the pretreatment unit 10 side (upstream side) of the duct unit 24 of the formation unit 20 are illustrated. The height H2 of the opening end is the same (H1 = H2).

このとき、第１ＣＶＤ温度領域Ａ４と第２ＣＶＤ温度領域Ａ５との間で、熱伝導、熱伝達及び輻射などの熱移動が起こると、カーボンナノチューブの長さと太さとを正確に制御することが出来なくなり、生成効率が低下する。そのため、形成部２０は、図４に示すように、第１空間仕切体２２Ａと第２空間仕切体２２Ｂとの間に、熱遮蔽部材２７が設けられている。ここで、製造装置１の構成の簡略化のため、ダクト部２４は第１空間仕切体２２Ａ及び第２空間仕切体２２Ｂとの間においては設けられていない。   At this time, if heat transfer such as heat conduction, heat transfer, and radiation occurs between the first CVD temperature region A4 and the second CVD temperature region A5, the length and thickness of the carbon nanotube cannot be accurately controlled. , Production efficiency decreases. Therefore, as shown in FIG. 4, the formation part 20 is provided with a heat shielding member 27 between the first space partition 22A and the second space partition 22B. Here, in order to simplify the configuration of the manufacturing apparatus 1, the duct portion 24 is not provided between the first space partition 22A and the second space partition 22B.

熱遮蔽部材２７には、第１ＣＶＤ温度及び第２ＣＶＤ温度のような高温に耐え得る材料が用いられ、例えばセラミックスや炭化ケイ素が被膜された鋼などが挙げられる。また、熱遮蔽部材２７の形状は、例えばブロック状、板状、フィルム状などが挙げられるが、具体的には、図４に示すように板状であることが好ましい。以下、この熱遮蔽部材を熱遮蔽板２７という。また、熱遮蔽板２７には、図５に示すように基板２を挿通し得るスリット２７ａが形成されている。このスリット２７ａの幅や高さはダクト部２４の高さや幅と同一にされるのが好ましい。   The heat shielding member 27 is made of a material that can withstand high temperatures such as the first CVD temperature and the second CVD temperature, and examples thereof include ceramics and steel coated with silicon carbide. In addition, examples of the shape of the heat shielding member 27 include a block shape, a plate shape, and a film shape. Specifically, the shape is preferably a plate shape as shown in FIG. Hereinafter, this heat shielding member is referred to as a heat shielding plate 27. Further, the heat shield plate 27 is formed with a slit 27a through which the substrate 2 can be inserted as shown in FIG. The width and height of the slit 27a are preferably the same as the height and width of the duct portion 24.

熱遮蔽板２７は、側方端部及び上方端部をそれぞれ断熱材９に支持されて減圧チャンバー５内に固定されている。具体的には、図４及び図５に示すように、断熱材９に熱遮蔽板２７の数と同じ数だけ溝部を設け、溝部に熱遮蔽板２７が差込まれて固定される。ただし、熱遮蔽板２７の下方端部は開放されている。したがって、熱遮蔽板２７間にはガスが通過し得る隙間が生じている。   The heat shielding plate 27 is fixed in the decompression chamber 5 with the side end portion and the upper end portion being supported by the heat insulating material 9. Specifically, as shown in FIGS. 4 and 5, the heat insulating material 9 is provided with the same number of grooves as the number of the heat shielding plates 27, and the heat shielding plates 27 are inserted and fixed in the grooves. However, the lower end of the heat shielding plate 27 is open. Therefore, a gap is formed between the heat shield plates 27 through which gas can pass.

熱遮蔽板２７の厚さや用いる枚数については、第１ＣＶＤ温度及び第２ＣＶＤ温度の値や、第１空間仕切体２２Ａと第２空間仕切体２２Ｂとの間の間隔の大きさによって適宜決めればよい。特に減圧下では、輻射による熱移動が大きいため、第２ＣＶＤ温度が第１ＣＶＤ温度に影響しないようにするのに十分な枚数の熱遮蔽板２７を設ける必要がある。そのため、例えば、所定区間（例えば２０ｍｍの区間）に所定厚み（例えば５０μｍの厚さ）の熱遮蔽板２７を所定間隔（１ｍｍの間隔）で複数枚並べるような構成にすればよい。具体的には、実施例１においては、１枚につき５０℃の輻射による熱移動の抑制が可能である。   The thickness of the heat shield plate 27 and the number of sheets to be used may be appropriately determined depending on the values of the first CVD temperature and the second CVD temperature and the size of the interval between the first space partition 22A and the second space partition 22B. In particular, since heat transfer due to radiation is large under reduced pressure, it is necessary to provide a sufficient number of heat shielding plates 27 so that the second CVD temperature does not affect the first CVD temperature. Therefore, for example, a configuration may be adopted in which a plurality of heat shielding plates 27 having a predetermined thickness (for example, 50 μm thickness) are arranged in a predetermined section (for example, 20 mm section) at a predetermined interval (1 mm interval). Specifically, in Example 1, it is possible to suppress heat transfer due to radiation at 50 ° C. per sheet.

また、原料ガス供給口２１ａは反応本体部２３の基板２の上方側に設けられるとともに、第１空間仕切体２２Ａ及び第２空間仕切体２２Ｂ内に供給された原料ガス等Ｇ４を減圧チャンバー５の外部に排気するガス排気管２８を接続するためのガス排気口２８ａは減圧チャンバー５の基板２の下方側に設けられる。具体的には、原料ガス等Ｇ４を排出するガス排気口２８ａは、各空間仕切体２２Ａ，２２Ｂに対応して配置されることが好ましいが、本実施例では、製造装置１の構成の簡略化のために、図４に示すように、第１空間仕切体２２Ａに対して配置されるガス排気口２８ａについては混合ガス排気口４１ａが兼用され、ガス排気管２８ａとして、混合ガス排気口４１ａに接続された混合ガス排気管４１が兼用される。また、第２空間仕切体２２Ｂに対しては、減圧チャンバー５において、形成部２０と後処理部３０との境界（ＣＶＤ温度領域Ｙと降温領域Ｚとの境界）であるダクト部２４の下流側端部の真下の位置にガス排気口２８ａが設けられ、ガス排気管２８が接続される。さらに、ガス排気管２８は、第１空間仕切体２２Ａと第２空間仕切体２２Ｂとの間に対応する位置、すなわち熱遮蔽板２７の真下にも設けられることがより好ましい。   The source gas supply port 21 a is provided above the substrate 2 of the reaction main body 23, and the source gas G 4 and the like supplied into the first space partition 22 A and the second space partition 22 B are supplied to the decompression chamber 5. A gas exhaust port 28 a for connecting a gas exhaust pipe 28 for exhausting to the outside is provided on the lower side of the substrate 2 in the decompression chamber 5. Specifically, the gas exhaust port 28a for discharging the source gas G4 or the like is preferably arranged corresponding to each space partition 22A, 22B, but in this embodiment, the configuration of the manufacturing apparatus 1 is simplified. Therefore, as shown in FIG. 4, the mixed gas exhaust port 41a is also used as the gas exhaust port 28a disposed with respect to the first space partition 22A, and the mixed gas exhaust port 41a is connected to the mixed gas exhaust port 41a. The connected mixed gas exhaust pipe 41 is also used. Further, with respect to the second space partition 22 </ b> B, in the decompression chamber 5, the downstream side of the duct portion 24, which is a boundary between the formation unit 20 and the post-processing unit 30 (a boundary between the CVD temperature region Y and the temperature decrease region Z). A gas exhaust port 28a is provided at a position directly below the end, and a gas exhaust pipe 28 is connected thereto. Furthermore, the gas exhaust pipe 28 is more preferably provided at a position corresponding to the space between the first space partition 22A and the second space partition 22B, that is, directly below the heat shield plate 27.

また、形成部２０には、図４に示すように、各空間仕切体２２Ａ，２２Ｂにおけるダクト部２４の内面の基板２表面の上側位置、すなわちダクト部２４の天井の内面に、反応本体部２３から流入する原料ガスＧ２を基板２表面側へ向けるガス偏向部２９が設けられている。具体的にはガス偏向部２９は、図４に示すように、基板２の移動方向に交差する方向（具体的には基板２の幅方向）に延びる複数の突条部材２９であり、これらが基板２の移動方向において所定間隔でもって配置されている。   Further, as shown in FIG. 4, the formation portion 20 has a reaction main body portion 23 on the upper surface of the surface of the substrate 2 on the inner surface of the duct portion 24 in each of the space partitions 22 </ b> A and 22 </ b> B, that is, on the inner surface of the ceiling of the duct portion 24. A gas deflection unit 29 is provided for directing the source gas G2 flowing in from the substrate 2 toward the surface of the substrate 2. Specifically, as shown in FIG. 4, the gas deflection unit 29 is a plurality of protrusion members 29 extending in a direction intersecting the moving direction of the substrate 2 (specifically, the width direction of the substrate 2). They are arranged at a predetermined interval in the moving direction of the substrate 2.

ここまで説明したように、形成部２０において、第１ＣＶＤ温度領域Ａ４と第２ＣＶＤ温度領域Ａ５との間に熱遮蔽板２７が設けられることによって、第１ＣＶＤ温度領域Ａ４と第２ＣＶＤ温度領域Ａ５との間の熱移動を防止することができる。   As described so far, in the formation unit 20, the heat shield plate 27 is provided between the first CVD temperature region A4 and the second CVD temperature region A5, so that the first CVD temperature region A4 and the second CVD temperature region A5 are separated. Heat transfer between them can be prevented.

また、形成部２０において、原料ガス供給口２１ａが基板２の上方側に設けられるとともに、ガス排気口２８ａが基板２の下方側に設けられることによって、原料ガス等Ｇ４は、基板２の下方側から排気されるため、第１空間仕切体２２Ａ及び第２空間仕切体２２Ｂ内における原料ガスＧ２の流れが基板２の上方側から下方側へ向かう方向になる。したがって、原料ガスＧ２が基板２表面の触媒に接触しやすくなり、カーボンナノチューブ３の生成率が向上する。特に、熱遮蔽板２７の真下にガス排気管２８が設けられることによって、例えば第１空間仕切体２２Ａと第２空間仕切体２２Ｂとに供給される原料ガスＧ２の濃度が異なる場合、それぞれの空間仕切体２２Ａ，２２Ｂに供給された原料ガスＧ２が互いに他の空間仕切体へ混入することを抑制することができ、カーボンナノチューブ３の長さや太さをより精密に制御することができる。   Further, in the forming unit 20, the source gas supply port 21 a is provided on the upper side of the substrate 2, and the gas exhaust port 28 a is provided on the lower side of the substrate 2. Therefore, the flow of the source gas G2 in the first space partition 22A and the second space partition 22B is directed from the upper side to the lower side of the substrate 2. Therefore, the source gas G2 is likely to come into contact with the catalyst on the surface of the substrate 2, and the generation rate of the carbon nanotubes 3 is improved. In particular, when the gas exhaust pipe 28 is provided directly below the heat shielding plate 27, for example, when the concentration of the source gas G2 supplied to the first space partition 22A and the second space partition 22B is different, the respective spaces The source gas G2 supplied to the partitions 22A and 22B can be prevented from being mixed with each other, and the length and thickness of the carbon nanotubes 3 can be controlled more precisely.

ダクト部２４の天井の内面にガス偏向部２９が設けられていることによって、ダクト部２４内に流入した原料ガスＧ２をガス偏向部（突条部材）２９に衝突させて、基板２側に向かう原料ガスＧ２の流れを作ることができ、基板２表面の触媒に原料ガスＧ２をより確実に接触させることができるため、カーボンナノチューブ３の生成率が向上する。   By providing the gas deflecting portion 29 on the inner surface of the ceiling of the duct portion 24, the source gas G2 flowing into the duct portion 24 collides with the gas deflecting portion (projection member) 29 and heads toward the substrate 2 side. Since the flow of the raw material gas G2 can be made and the raw material gas G2 can be brought into contact with the catalyst on the surface of the substrate 2 more reliably, the production rate of the carbon nanotubes 3 is improved.

最後に、形成部２０の下流側に設けられた冷却部３０すなわち降温領域Ｚには、図３に示すように、基板２及び生成されたカーボンナノチューブ３（以下、基板２等ということがある。）を形成部２０での第２ＣＶＤ温度から常温へと低下させるための加熱装置を少なくとも１つ具備する。本実施例においては、降温領域Ｚでは、３段階で基板２等を降温させるため、図３に仮想線にて示すように、上流側から下流側に向かって第６温度領域Ａ６、第７温度領域Ａ７及び第８温度領域Ａ８を有する。後処理部３０は、第６温度領域Ａ６に設けられた第６加熱装置３１、第７温度領域Ａ７に設けられた第７加熱装置３２及び第８温度領域Ａ８に設けられた第８加熱装置３３の３つの加熱装置を具備する。第６加熱装置３１、第７加熱装置３２及び第８加熱装置３３の加熱温度は、形成部２０での加熱温度から冷却するにあたって、基板２の熱変形を防ぐため、基板２表面の温度が５００℃〜６００℃を経た後、常温まで徐々に低下するようそれぞれ設定されている。   Finally, in the cooling unit 30 provided on the downstream side of the forming unit 20, that is, the temperature drop region Z, as shown in FIG. 3, the substrate 2 and the generated carbon nanotube 3 (hereinafter referred to as the substrate 2 or the like) may be used. ) At least one heating device for lowering the temperature from the second CVD temperature in the forming unit 20 to room temperature. In the present embodiment, in the temperature lowering region Z, the temperature of the substrate 2 and the like is decreased in three stages. Therefore, as shown by the phantom line in FIG. It has area | region A7 and 8th temperature area A8. The post-processing unit 30 includes a sixth heating device 31 provided in the sixth temperature region A6, a seventh heating device 32 provided in the seventh temperature region A7, and an eighth heating device 33 provided in the eighth temperature region A8. The three heating devices are provided. The heating temperature of the sixth heating device 31, the seventh heating device 32, and the eighth heating device 33 is such that the surface temperature of the substrate 2 is 500 in order to prevent thermal deformation of the substrate 2 when cooling from the heating temperature in the forming unit 20. The temperature is set so as to gradually decrease to room temperature after passing through the temperature of 600C to 600C.

また、本実施例においては、加熱装置としては、前処理部１０、形成部２０及び後処理部３０のいずれにも、発熱体（例えばフィラメント）を石英製の円筒に入れて炭化ケイ素を充填したものを複数本、基板２の移動方向に並べて配置し、それらを電源装置に接続したいわゆる石英管ヒーターが採用されている。   In the present embodiment, as the heating device, a heating element (for example, a filament) is placed in a quartz cylinder and filled with silicon carbide in any of the pretreatment unit 10, the formation unit 20, and the posttreatment unit 30. A so-called quartz tube heater is used in which a plurality of such are arranged in the moving direction of the substrate 2 and connected to a power supply device.

さらに、減圧チャンバー５に外側から冷風を当てたり、減圧チャンバー５の外周に冷却水管を設けたりすることにより、減圧チャンバー５の温度を一定に保つようにしてもよい。このような冷却によって、例えば、Ｏ‐リング１６の温度が一定に維持されるため、シール性能が維持される。その結果、減圧チャンバー５内の圧力を一定に維持することができる。   Furthermore, the temperature of the decompression chamber 5 may be kept constant by applying cold air to the decompression chamber 5 from the outside or providing a cooling water pipe on the outer periphery of the decompression chamber 5. By such cooling, for example, the temperature of the O-ring 16 is kept constant, so that the sealing performance is maintained. As a result, the pressure in the decompression chamber 5 can be kept constant.

以下、本発明の実施例１に係るカーボンナノチューブ３の製造装置１を用いた製造方法について、図１〜図３を用いて説明する。
図１及び図２に示すように、基板２は繰出部６から減圧チャンバー５内の処理用空間部４に導き入れられて巻取部７へと移動される。図３に示すように、処理用空間部４の前処理部１０において、予め基板２表面に触媒が塗布された基板２は、前処理用ガスＧ１が供給されたダクト１４に導き入れられて第１加熱装置１１〜第３加熱装置１３により加熱されることによって、昇温領域Ｘにて昇温されるとともに、基板２表面の触媒が微粒化される。次に、基板２は前処理部１０から形成部２０へ導き入れられて、第１空間仕切体２２Ａの第１反応空間Ｐ１にて第４加熱装置２５により第１ＣＶＤ温度に、また第２空間仕切体２２Ｂの第２反応空間Ｐ２にて第５加熱装置２６により第２ＣＶＤ温度にそれぞれ加熱されながら原料ガスＧ２を基板２上で反応させる。このことにより、第１反応空間Ｐ１では基板２上でカーボンナノチューブ３の長さを成長させ、第２反応空間Ｐ２では基板２上でカーボンナノチューブ３の太さを成長させる。そして、基板２は形成部２０から後処理部３０へ導き入れられて第６加熱装置３１〜第８加熱装置３３により加熱されることによって、基板２及び基板２上に生成されたカーボンナノチューブ３が降温される。このとき、形成部２０において、形成部２０から排出された原料ガス等Ｇ４は、基板２の下方側、特に熱遮蔽板２７の真下に設けられたガス排気管２８を介して減圧チャンバー５の外へ排気されている。 Hereinafter, the manufacturing method using the manufacturing apparatus 1 of the carbon nanotube 3 which concerns on Example 1 of this invention is demonstrated using FIGS. 1-3.
As shown in FIGS. 1 and 2, the substrate 2 is introduced from the feeding unit 6 into the processing space 4 in the decompression chamber 5 and moved to the winding unit 7. As shown in FIG. 3, in the pretreatment unit 10 of the treatment space 4, the substrate 2 having a catalyst applied to the surface of the substrate 2 in advance is introduced into the duct 14 to which the pretreatment gas G1 is supplied. When heated by the first heating device 11 to the third heating device 13, the temperature is raised in the temperature raising region X and the catalyst on the surface of the substrate 2 is atomized. Next, the substrate 2 is introduced from the pretreatment unit 10 to the formation unit 20, and is set to the first CVD temperature by the fourth heating device 25 in the first reaction space P <b> 1 of the first space partition 22 </ b> A and to the second space partition. The source gas G2 is reacted on the substrate 2 while being heated to the second CVD temperature by the fifth heating device 26 in the second reaction space P2 of the body 22B. Accordingly, the length of the carbon nanotube 3 is grown on the substrate 2 in the first reaction space P1, and the thickness of the carbon nanotube 3 is grown on the substrate 2 in the second reaction space P2. The substrate 2 is introduced from the forming unit 20 to the post-processing unit 30 and heated by the sixth heating device 31 to the eighth heating device 33, so that the carbon nanotubes 3 generated on the substrate 2 and the substrate 2 are formed. The temperature is lowered. At this time, in the forming unit 20, the source gas G4 and the like discharged from the forming unit 20 is discharged from the decompression chamber 5 through the gas exhaust pipe 28 provided below the substrate 2, particularly immediately below the heat shielding plate 27. Has been exhausted.

このように、本発明のカーボンナノチューブの製造装置１によれば、カーボンナノチューブ３の長さの成長に適した温度に加熱された第１ＣＶＤ温度領域Ａ４と、カーボンナノチューブ３のアモルファス層の成長に適した温度に加熱された第２ＣＶＤ温度領域Ａ５との間に、熱遮蔽板２７を設けることにより、第１ＣＶＤ温度領域Ａ４と第２ＣＶＤ温度領域Ａ５との間の熱移動を防ぐとともに、互いの温度領域への原料ガスＧ２の混入を防ぎ、カーボンナノチューブの長さ及びアモルファス層の厚みが精密に制御されたカーボンナノチューブを製造することができる。
［実施例２］
実施例２について図６を用いて説明する。実施例１と同一の構成には同一の名称及び符号を付し、説明を省略する。実施例１においては、形成部２０の第１空間仕切体２２Ａと第２空間仕切体２２Ｂとの間に熱遮蔽板２７を設けたが、実施例２においては、さらに第１空間仕切体２２Ａの上流側、より具体的には前処理部１０と形成部２０との境界と、第２空間仕切体２２Ｂよりも下流側、より具体的には形成部２０と後処理部３０との境界とに熱遮蔽板２７をそれぞれ設けた。 Thus, according to the carbon nanotube production apparatus 1 of the present invention, the first CVD temperature region A4 heated to a temperature suitable for the growth of the length of the carbon nanotube 3 and the growth of the amorphous layer of the carbon nanotube 3 are suitable. By providing the heat shielding plate 27 between the second CVD temperature region A5 heated to a predetermined temperature, heat transfer between the first CVD temperature region A4 and the second CVD temperature region A5 is prevented, and the mutual temperature regions It is possible to produce carbon nanotubes in which the raw material gas G2 is prevented from being mixed and the length of the carbon nanotubes and the thickness of the amorphous layer are precisely controlled.
[Example 2]
A second embodiment will be described with reference to FIG. The same components as those in the first embodiment are denoted by the same names and reference numerals, and the description thereof is omitted. In the first embodiment, the heat shielding plate 27 is provided between the first space partition 22A and the second space partition 22B of the forming unit 20, but in the second embodiment, the first space partition 22A is further provided. On the upstream side, more specifically on the boundary between the pre-processing unit 10 and the forming unit 20, and on the downstream side of the second space partition 22 </ b> B, more specifically on the boundary between the forming unit 20 and the post-processing unit 30. A heat shielding plate 27 was provided.

また、図６に示すように、前処理部１０と形成部２０との境界に設けられた熱遮蔽板２７付近にダクト１４の排気用開口部４０を設けるとともに、この熱遮蔽板２７の真下に、混合ガス排気口４１ａ及び混合ガス排気管４１を設けた。そして、形成部２０と後処理部３０との境界に設けられた熱遮蔽板２７の真下に、ガス排気口２８ａ及びガス供給管２８を設けた。なお、製造装置１の構成の簡略化のため、各空間仕切体２２Ａ，２２Ｂにはそれぞれダクト部２４が設けられていない。   Further, as shown in FIG. 6, an exhaust opening 40 of the duct 14 is provided in the vicinity of the heat shielding plate 27 provided at the boundary between the pretreatment unit 10 and the forming unit 20, and immediately below the heat shielding plate 27. The mixed gas exhaust port 41a and the mixed gas exhaust pipe 41 are provided. A gas exhaust port 28 a and a gas supply pipe 28 were provided immediately below the heat shielding plate 27 provided at the boundary between the forming unit 20 and the post-processing unit 30. In addition, in order to simplify the structure of the manufacturing apparatus 1, each space partition 22A, 22B is not provided with the duct part 24, respectively.

第１ＣＶＤ温度領域Ａ４と第２ＣＶＤ温度領域Ａ５との間に加えて、前処理部１０と形成部２０との境界と、形成部２０と後処理部３０との境界とにおいても、熱遮蔽板２７を設けたことによって、前処理部１０で加熱された基板２と第１ＣＶＤ温度に加熱された基板２との間、及び第２ＣＶＤ温度に加熱された基板２と後処理部３０で降温された基板２との間においても、それぞれ熱移動が抑制される。   In addition to between the first CVD temperature region A4 and the second CVD temperature region A5, the heat shielding plate 27 is also formed at the boundary between the pretreatment unit 10 and the formation unit 20 and the boundary between the formation unit 20 and the posttreatment unit 30. Are provided between the substrate 2 heated by the pre-processing unit 10 and the substrate 2 heated to the first CVD temperature, and the substrate 2 heated to the second CVD temperature and the substrate cooled by the post-processing unit 30 Heat transfer is also suppressed between the two.

また、ダクト１４に排気用開口部４０を設けるとともに、前処理部１０と形成部２０との境界に設けられた熱遮蔽板２７の真下に、混合ガス排気口４１ａ及び混合ガス排気管４１を設けることにより、混合ガスＧ３を熱遮蔽板２７間に通してより確実に減圧チャンバー５の外へ排気させることができる。   In addition, an exhaust opening 40 is provided in the duct 14, and a mixed gas exhaust port 41 a and a mixed gas exhaust pipe 41 are provided directly below the heat shielding plate 27 provided at the boundary between the pretreatment unit 10 and the forming unit 20. Thus, the mixed gas G3 can be exhausted out of the decompression chamber 5 through the heat shielding plate 27 more reliably.

そして、形成部２０と後処理部３０との境界に設けられた熱遮蔽板２７の真下に、ガス排気口２８ａ及びガス供給管２８を設けることにより、原料ガス等Ｇ４を熱遮蔽板２７間に通してより確実に減圧チャンバー５の外へ排気させることができる。   Then, by providing a gas exhaust port 28a and a gas supply pipe 28 immediately below the heat shielding plate 27 provided at the boundary between the forming unit 20 and the post-processing unit 30, the source gas G4 and the like are transferred between the heat shielding plates 27. It is possible to evacuate out of the decompression chamber 5 more reliably.

１ カーボンナノチューブの製造装置
２ 基板
３ カーボンナノチューブ
４ 処理用空間部
５ 減圧チャンバー（反応容器）
６ 繰出部
７ 巻取部
１０ 前処理部
１１ 第１加熱装置
１２ 第２加熱装置
１３ 第３加熱装置
１４ ダクト
Ｘ 昇温領域
Ａ１ 第１温度領域
Ａ２ 第２温度領域
Ａ３ 第３温度領域
２０ 形成部
２１ 原料ガス供給管
２２Ａ 第１空間仕切体
２２Ｂ 第２空間仕切体
Ｐ１ 第１反応空間
Ｐ２ 第２反応空間
２３ 反応本体部
２４ 基板案内用突出部（ダクト部）
２５ 第４加熱装置
２６ 第５加熱装置
２７ 熱遮蔽板（熱遮蔽部材）
２８ ガス排気管
２９ ガス偏向部（突条部）
Ｙ ＣＶＤ温度領域
Ａ４ 第１ＣＶＤ温度領域（第４温度領域）
Ａ５ 第２ＣＶＤ温度領域（第５温度領域）
３０ 後処理部
３１ 第６加熱装置
３２ 第７加熱装置
３３ 第８加熱装置
４０ 排気用開口部
４１ 混合ガス排気管
Ｚ 降温領域
Ａ６ 第６温度領域
Ａ７ 第７温度領域
Ａ８ 第８温度領域
Ｇ１ 不活性ガス
Ｇ２ 原料ガス
Ｇ３ 混合ガス
Ｇ４ 原料ガス等 DESCRIPTION OF SYMBOLS 1 Carbon nanotube manufacturing apparatus 2 Substrate 3 Carbon nanotube 4 Processing space 5 Depressurization chamber (reaction vessel)
6 Feeding section 7 Winding section 10 Pretreatment section 11 First heating device 12 Second heating device 13 Third heating device 14 Duct X Temperature rising area A1 First temperature area A2 Second temperature area A3 Third temperature area 20 Forming section 21 Source gas supply pipe 22A 1st space partition 22B 2nd space partition P1 1st reaction space P2 2nd reaction space 23 Reaction main-body part 24 Protrusion part for substrate guidance (duct part)
25 4th heating device 26 5th heating device 27 Heat shielding plate (heat shielding member)
28 Gas exhaust pipe 29 Gas deflection part (projection part)
Y CVD temperature region A4 First CVD temperature region (fourth temperature region)
A5 2nd CVD temperature range (5th temperature range)
30 Post-processing section 31 6th heating device 32 7th heating device 33 8th heating device 40 Exhaust opening 41 Mixed gas exhaust pipe Z Temperature drop region A6 6th temperature region A7 7th temperature region A8 8th temperature region G1 Inactive Gas G2 Raw material gas G3 Mixed gas G4 Raw material gas, etc.

Claims (5)

表面に触媒が担持されかつ所定方向に移動される基板を導き入れるとともに、前記基板の移動方向に沿って、前記基板表面を第１ＣＶＤ温度に加熱してカーボンナノチューブを所定の長さに成長させる第１ＣＶＤ温度領域と、さらに前記基板表面を前記第１ＣＶＤ温度よりも高い第２ＣＶＤ温度に加熱してカーボンナノチューブの表面にカーボンを付着させる第２ＣＶＤ領域とが設けられた、化学気相成長法を用いてカーボンナノチューブを連続的に生成する減圧の反応容器を有するカーボンナノチューブの製造装置であって、
前記反応容器において、前記第１ＣＶＤ温度領域と前記第２ＣＶＤ温度領域とには、前記基板に前記原料ガスを供給する前記原料ガス供給管に接続されて、前記基板の表面を所定範囲に亘って覆うことで反応空間を制限する第１空間仕切体と第２空間仕切体とがそれぞれ配置され、
前記第１空間仕切体と前記第２空間仕切体との間に熱遮蔽部材が設けられていることを特徴とするカーボンナノチューブの製造装置。 A substrate on which a catalyst is supported and which is moved in a predetermined direction is introduced, and a carbon nanotube is grown to a predetermined length by heating the substrate surface to a first CVD temperature along the moving direction of the substrate. Using a chemical vapor deposition method, in which a 1 CVD temperature region and a second CVD region for heating the substrate surface to a second CVD temperature higher than the first CVD temperature to deposit carbon on the surface of the carbon nanotube are provided. An apparatus for producing carbon nanotubes having a reduced-pressure reaction vessel for continuously producing carbon nanotubes,
In the reaction vessel, the first CVD temperature region and the second CVD temperature region are connected to the source gas supply pipe for supplying the source gas to the substrate and cover the surface of the substrate over a predetermined range. The first space partition and the second space partition that limit the reaction space by being arranged, respectively,
A carbon nanotube manufacturing apparatus, wherein a heat shielding member is provided between the first space partition and the second space partition. 熱遮蔽部材には、セラミックス又は炭化ケイ素が被覆された鋼が用いられることを特徴とする請求項１に記載のカーボンナノチューブの製造装置。   The carbon nanotube manufacturing apparatus according to claim 1, wherein the heat shielding member is made of steel coated with ceramics or silicon carbide. 第２ＣＶＤ温度は第１ＣＶＤ温度よりも５０度〜２００度高く設定されたことを特徴とする請求項１又は２に記載のカーボンナノチューブの製造装置。   The apparatus for producing carbon nanotubes according to claim 1 or 2, wherein the second CVD temperature is set to be higher by 50 to 200 degrees than the first CVD temperature. 反応容器において、第１空間仕切体よりも基板の移動方向の後方側及び第２空間仕切体よりも前記基板の移動方向の前方側にさらに熱遮蔽部材がそれぞれ設けられていることを特徴とする請求項１乃至３のいずれか一項に記載のカーボンナノチューブの製造装置。   In the reaction container, a heat shielding member is further provided on the rear side in the movement direction of the substrate with respect to the first space partition and on the front side in the movement direction of the substrate with respect to the second space partition. The carbon nanotube manufacturing apparatus according to any one of claims 1 to 3. 熱遮蔽部材は複数の板材により構成されるとともに、反応容器の壁部に、前記板材間から排出される原料ガスを外部へ排気するガス排気管が接続されていることを特徴とする請求項１乃至４のいずれか一項に記載のカーボンナノチューブの製造装置。   2. The heat shielding member is composed of a plurality of plate members, and a gas exhaust pipe for exhausting the source gas discharged from between the plate members to the outside is connected to a wall portion of the reaction vessel. The manufacturing apparatus of the carbon nanotube as described in any one of thru | or 4.
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