KR19990073590A - Massive synthesis of highly purified carbon nanotubes using plasma enhanced chemical vapor deposition. - Google Patents
Massive synthesis of highly purified carbon nanotubes using plasma enhanced chemical vapor deposition. Download PDFInfo
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- KR19990073590A KR19990073590A KR1019990030697A KR19990030697A KR19990073590A KR 19990073590 A KR19990073590 A KR 19990073590A KR 1019990030697 A KR1019990030697 A KR 1019990030697A KR 19990030697 A KR19990030697 A KR 19990030697A KR 19990073590 A KR19990073590 A KR 19990073590A
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Abstract
본 발명은 플라즈마화학기상증착법을 사용하여 고순도 탄소나노튜브를 대면적 기판위에서 합성시키는 방법으로써, 특히 탄소나노튜브를 기판에 수직방향으로 정렬시켜 대량으로 합성시키는 방법에 관한 것이다.The present invention relates to a method for synthesizing high-purity carbon nanotubes on a large area substrate using plasma chemical vapor deposition, and more particularly, to a method for synthesizing carbon nanotubes in a vertical direction on a substrate in large quantities.
본 발명에 따른 탄소나노튜브의 합성은 대면적 글라스 기판위에 전이금속막을 증착시킨 후, 플라즈마를 이용하여 저온에서 상기 전이금속막의 표면을 암모니아가스로 식각시켜 상기 전이금속막의 표면에 미세한 그레인을 형성시킨 후, 상기 미세한 그레인위에 350 - 650℃ 범위의 온도에서 플라즈마에너지를 이용하여 아세틸렌가스 등의 탄화가스를 반응시켜, 상기 전이금속막위에 탄소나노튜브를 수직방향으로 정렬시켜 성장시킨다. 본 발명에 의한 탄소나노튜브는 기존의 전기방전법 또는 레이저증착법 또는 열화학기상증착법으로 성장시킨 탄소나노튜브에 비해서 저온에서 대면적 기판위에 고순도의 탄소나노튜브를 수직방향으로 정렬시켜 합성하는 것이 가능하기 때문에 기존의 글라스기판을 사용하여 대면적으로 고순도의 탄소나노튜브를 대량으로 합성할 수 있는 장점이 있다.In the synthesis of carbon nanotubes according to the present invention, after depositing a transition metal film on a large-area glass substrate, the surface of the transition metal film is etched with ammonia gas at low temperature using plasma to form fine grains on the surface of the transition metal film. Thereafter, carbon dioxide tubes such as acetylene gas are reacted with plasma energy at a temperature in the range of 350 to 650 ° C. on the fine grains, and the carbon nanotubes are vertically aligned on the transition metal film to grow. Carbon nanotubes according to the present invention can be synthesized by aligning high-purity carbon nanotubes vertically on a large-area substrate at low temperature, compared to conventional carbon nanotubes grown by electric discharge, laser deposition, or thermochemical vapor deposition. Therefore, there is an advantage that a large amount of high-purity carbon nanotubes can be synthesized using a conventional glass substrate.
Description
본 발명은 플라즈마 화학기상증착법을 사용하여 대면적 기판위에서 고순도 탄소나노튜브를 저온에서 대량으로 합성하는 방법을 제공하는데 있다.The present invention provides a method for synthesizing a large amount of high-purity carbon nanotubes on a large-area substrate at low temperature by using plasma chemical vapor deposition.
본 발명은 플라즈마 화학기상증착법을 사용하여 저온에서 탄소나노튜브를 대량으로 합성하는 방법에 관한 것으로써, 특히 대면적 기판위에 증착된 전이금속막위에 수직방향으로 정렬된 탄소나노튜브를 합성하는 방법에 관한 것이다. 근래에 탄소나노튜브 합성에 관한 여러 가지 방법이 제안되었는데, 전기방전법이나 레이저증착법은 탄소나노튜브의 합성수율이 비교적 낮고, 나노튜브의 직경이나 길이를 조절하기가 어렵우며, 또한 합성과정에서 탄소나노튜브이외에도 비정질상태의 탄소덩어리들이 동시에 다량으로 생성되기 때문에 반드시 복잡한 정제과정을 수반하기 때문에 대량생산에 어려움이 많다. 한편 최근에 제안된 열화학기상증착법은 탄소나노튜브를 대면적으로 합성하는 것이 가능하고 고품질의 탄소나노튜브를 합성할 수 있는 장점이 있지만 탄소나노튜브를 합성하기 위한 온도가 높아서 글라스기판을 이용하는 소자에 응용하기에 부적합한 문제점을 가지고 있다.The present invention relates to a method for synthesizing a large amount of carbon nanotubes at a low temperature using plasma chemical vapor deposition, in particular to a method for synthesizing carbon nanotubes vertically aligned on a transition metal film deposited on a large area substrate. It is about. Recently, various methods for synthesizing carbon nanotubes have been proposed. The electric discharge method and the laser deposition method have relatively low yields of carbon nanotubes, and it is difficult to control the diameter and length of the nanotubes. In addition to nanotubes, a large amount of amorphous carbon masses are produced at the same time, which is difficult to mass-produce because it necessarily involves complicated purification processes. On the other hand, the recently proposed thermochemical vapor deposition method can synthesize carbon nanotubes in a large area and can synthesize high quality carbon nanotubes. However, since the temperature for synthesizing carbon nanotubes is high, a device using a glass substrate is used. It has a problem that is not suitable for application.
본 발명은 상기 문제점을 해결하기 위하여 창출한 것으로써, 대면적 기판위에 전이금속막을 증착시킨 후, 상기 전이금속막위에 저온에서 플라즈마화학기상증착법을 사용하여 탄소나노튜브를 합성시키는 방법에 관한 것으로써, 특히 기판에 수직인 방향으로 정렬된 고순도의 탄소나노튜브를 대량으로 합성하는 방법에 관한 것이다. 본 발명은 종래의 다공질 물질이나 다공질 기판을 사용하는 대신에 대면적 글라스기판위에 전이금속막을 증착시킨 후, 플라즈마에너지를 이용하여 암모니아가스로 상기 전이금속막의 표면을 식각시켜 표면에 미세한 그레인을 형성시킨 다음, 역시 저온에서 플라즈마화학기상증착법으로 아세틸렌 등의 탄화가스를 분해시켜 상기 전이금속막의 그레인위에 수직방향으로 정렬된 고순도 탄소나노튜브를 합성시킨 후, 이어서 암모니아가스 또는 수소가스를 반응챔버로 공급한 후 RF-power를 인가하여 상기 탄소나노튜브의 끝부분에 존재하는 전이금속 덩어리와 탄소나노튜브의 표면에 존재하는 탄소파티클을 깨끗하게 제거시킴으로써 고순도의 탄소나노튜브를 합성하는 방법에 관한 것이다.The present invention has been made to solve the above problems, and relates to a method of synthesizing carbon nanotubes by depositing a transition metal film on a large-area substrate and then using plasma chemical vapor deposition at a low temperature on the transition metal film. In particular, the present invention relates to a method for synthesizing a large amount of high-purity carbon nanotubes aligned in a direction perpendicular to the substrate. According to the present invention, instead of using a conventional porous material or a porous substrate, a transition metal film is deposited on a large area glass substrate, and then the surface of the transition metal film is etched with ammonia gas using plasma energy to form fine grains on the surface. Next, carbonaceous gases such as acetylene were decomposed by plasma chemical vapor deposition at low temperature to synthesize high-purity carbon nanotubes arranged vertically on the grains of the transition metal film, and then ammonia gas or hydrogen gas was supplied to the reaction chamber. The present invention relates to a method for synthesizing carbon nanotubes having high purity by applying RF-power to cleanly remove the transition metal lumps and carbon particles present on the surface of the carbon nanotubes.
도 1은 본 발명에 따른 플라즈마 화학기상증착법으로 탄소나노튜브를 대량합성하기 위한 장치의 구조도이다.1 is a structural diagram of a device for mass synthesis of carbon nanotubes by the plasma chemical vapor deposition method according to the present invention.
상기 목적을 달성하기 위한 본 발명에 따른 플라즈마화학기상증착법에 의한 탄소나노튜브의 대량합성은, 대면적 글라스기판(1)위에 코발트 또는 철 또는 코발트-니켈 합금 등의 전이금속막(2)을 열증착법이나 스퍼터링법을 사용하여 약 50 - 200 nm 증착시키고 나서, 플라즈마 화학기상증착기의 반응챔버내부로 상기 전이금속막(2)을 집어넣은 후, 350 - 650 ℃ 온도범위에서 상기 반응챔버내부로 암모니아가스를 80 - 400 sccm 범위로 공급하여 챔버의 압력을 0.1 - 수십 Torr 정도의 저압으로 유지하고 100 - 600 W 정도의 RF-power를 10 - 30 min 동안 인가하여 상기 전이금속막(2)의 표면을 식각시켜 표면에 미세한 그레인을 형성시킨 후, 상기 플라즈마 화학기상증착장치의 반응챔버의 온도를 350 - 650 ℃ 범위로 조절하여 아세틸렌가스, 메탄가스, 프로판가스, 또는 에틸렌가스등의 탄화가스를 20 - 200 sccm 범위로 공급하여 챔버의 압력을 0.1 - 수십 Torr 정도로 유지시킨 다음, 100 - 600 W 정도의 RF-power를 10 - 60 min 동안 인가하여 상기 전이금속막(2) 표면의 미세한 그레인위에 수직방향으로 정렬된 탄소나노튜브(3)를 합성시킨다. 이어서 상기 탄소나노튜브(3)의 끝부분에 존재하는 전이금속 덩어리와 탄소나노튜브의 표면에 존재하는 탄소파티클을 제거하기 위하여 350 - 650 ℃ 온도범위에서 상기 반응챔버내부로 암모니아가스를 80 - 400 sccm 범위로 공급하여 챔버의 압력을 0.1 - 수십 Torr 정도의 저압으로 유지하고 100 - 600 W 정도의 RF-power를 10 - 30 min 동안 인가하여 상기 탄소나노튜브(3)의 끝부분에 존재하는 전이금속 덩어리와 탄소나노튜브의 표면에 존재하는 탄소파티클을 깨끗하게 제거시킨다.The mass synthesis of carbon nanotubes by the plasma chemical vapor deposition method according to the present invention for achieving the above object, heat the transition metal film (2) such as cobalt or iron or cobalt-nickel alloy on the large-area glass substrate (1) After deposition of about 50-200 nm by vapor deposition or sputtering, the transition metal film 2 was inserted into the reaction chamber of the plasma chemical vapor deposition machine, and then ammonia was introduced into the reaction chamber at a temperature range of 350-650 ° C. The gas is supplied in the range of 80-400 sccm to maintain the chamber pressure at a low pressure of about 0.1-several tens of Torr and the RF-power of about 100-600 W is applied for 10-30 min to provide a surface of the transition metal film (2). After etching to form fine grains on the surface, by adjusting the temperature of the reaction chamber of the plasma chemical vapor deposition apparatus in the range of 350-650 ℃ acetylene gas, methane gas, propane gas, or ethylene By supplying carbonized gas such as carbon in the range of 20-200 sccm, the pressure of the chamber is maintained at about 0.1-several tens of Torr, and then the transition metal film (2) is applied with an RF-power of about 100-600 W for 10-60 min. The carbon nanotubes 3 vertically aligned on the fine grain of the surface are synthesized. Subsequently, in order to remove the transition metal mass present at the end of the carbon nanotubes 3 and the carbon particles present on the surface of the carbon nanotubes, ammonia gas was introduced into the reaction chamber at a temperature range of 350-650 ° C., 80-400. It is supplied in the sccm range to maintain the chamber pressure at a low pressure of about 0.1 to several tens of torr, and a transition existing at the end of the carbon nanotubes (3) by applying RF power of about 100 to 600 W for 10 to 30 min. The carbon particles present on the surface of the metal mass and the carbon nanotubes are cleanly removed.
상술한 바와 같이 본 발명에 따른 플라즈마 화학기상증착법에 의한 탄소나노튜브의 합성은 기존의 전기방전법이나 레이저증착법에 비해서 저온에서 탄소나노튜브의 합성이 가능하고, 탄소나노튜브의 수율이 훨씬 높으며, 탄소나노튜브의 반경이나 길이를 조절하기가 쉬우며, 고순도의 탄소나노튜브 합성이 가능하기 때문에 복잡한 정제과정이 불필요하고 대면적 기판에서 합성이 가능하다. 또한 기존의 열분해법이나 열화학기상증착법에 비해서 저온에서 합성이 가능하기 때문에 글라스기판위에서 탄소나노튜브의 대량합성에 유리한 장점이 있다.As described above, the synthesis of carbon nanotubes by the plasma chemical vapor deposition method according to the present invention enables the synthesis of carbon nanotubes at low temperature, and the yield of carbon nanotubes is much higher than that of conventional electric discharge or laser deposition methods. It is easy to control the radius and length of carbon nanotubes, and it is possible to synthesize high-purity carbon nanotubes, which eliminates the need for complicated purification processes and enables synthesis on large-area substrates. In addition, since it can be synthesized at a low temperature compared to the conventional pyrolysis method or thermochemical vapor deposition method, there is an advantage in the mass synthesis of carbon nanotubes on the glass substrate.
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Cited By (6)
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KR20010088087A (en) * | 2000-03-10 | 2001-09-26 | 장 진 | Selective deposition method of carbon nanotubes |
KR100371161B1 (en) * | 1999-12-18 | 2003-02-07 | 엘지전자 주식회사 | Fabricating method of field emission device |
KR100377630B1 (en) * | 2000-09-25 | 2003-03-26 | 엘지전자 주식회사 | Selective excluding method of Carbon Nanotube having various characteristics |
KR100385633B1 (en) * | 2000-09-08 | 2003-05-27 | 학교법인 포항공과대학교 | Method of preparing a carbon nanotube under a vapor-phase condition |
KR100513713B1 (en) * | 2000-05-12 | 2005-09-07 | 삼성에스디아이 주식회사 | Growth method for vertically aligned carbon nanotubes by changing the morphologies of a transition metal thin films |
KR100571803B1 (en) * | 2002-05-03 | 2006-04-17 | 삼성전자주식회사 | Semiconductor carbon nano tube functionalized by hydrogen, electronic device and method of fabrication thereof |
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US6878361B2 (en) | 2001-07-10 | 2005-04-12 | Battelle Memorial Institute | Production of stable aqueous dispersions of carbon nanotubes |
US6896864B2 (en) | 2001-07-10 | 2005-05-24 | Battelle Memorial Institute | Spatial localization of dispersed single walled carbon nanotubes into useful structures |
KR20030028296A (en) * | 2001-09-28 | 2003-04-08 | 학교법인 한양학원 | Plasma enhanced chemical vapor deposition apparatus and method of producing a cabon nanotube using the same |
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JP2973352B2 (en) * | 1995-07-10 | 1999-11-08 | 科学技術振興事業団 | How to make graphite fiber |
JP3441923B2 (en) * | 1997-06-18 | 2003-09-02 | キヤノン株式会社 | Manufacturing method of carbon nanotube |
JPH11116218A (en) * | 1997-10-17 | 1999-04-27 | Osaka Gas Co Ltd | Production of single layered nanotube |
JPH11139821A (en) * | 1997-11-06 | 1999-05-25 | Natl Inst For Res In Inorg Mater | Production of multicomponent nanotube |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100371161B1 (en) * | 1999-12-18 | 2003-02-07 | 엘지전자 주식회사 | Fabricating method of field emission device |
KR20010088087A (en) * | 2000-03-10 | 2001-09-26 | 장 진 | Selective deposition method of carbon nanotubes |
KR100513713B1 (en) * | 2000-05-12 | 2005-09-07 | 삼성에스디아이 주식회사 | Growth method for vertically aligned carbon nanotubes by changing the morphologies of a transition metal thin films |
KR100385633B1 (en) * | 2000-09-08 | 2003-05-27 | 학교법인 포항공과대학교 | Method of preparing a carbon nanotube under a vapor-phase condition |
KR100377630B1 (en) * | 2000-09-25 | 2003-03-26 | 엘지전자 주식회사 | Selective excluding method of Carbon Nanotube having various characteristics |
KR100571803B1 (en) * | 2002-05-03 | 2006-04-17 | 삼성전자주식회사 | Semiconductor carbon nano tube functionalized by hydrogen, electronic device and method of fabrication thereof |
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