JP4133655B2 - Method for producing nanocarbon material and method for producing wiring structure - Google Patents
Method for producing nanocarbon material and method for producing wiring structure Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Description
本発明は、カーボンナノチューブ等のナノカーボン材料の製造方法、及びナノカーボン材料を配線に用いた配線構造の製造方法に関する。 The present invention relates to a method for producing a nanocarbon material such as a carbon nanotube, and a method for producing a wiring structure using the nanocarbon material for wiring.
近年、いわゆるカーボンナノチューブ等のナノカーボン材料が注目されている。これらのナノカーボン材料は従来の炭素材料であるグラファイトやダイヤモンドと異なる物性を有しているため、電極の電子放出源、伝導性膜、電池電極等への応用が期待されている。また、ナノカーボン材料は配線用途としても適していると考えられる。上記カーボンナノチューブ等のナノカーボンの製造（合成）方法としては、気相合成法やアーク放電法が知られている。 In recent years, nanocarbon materials such as so-called carbon nanotubes have attracted attention. Since these nanocarbon materials have physical properties different from those of conventional carbon materials such as graphite and diamond, they are expected to be applied to electrode electron emission sources, conductive films, battery electrodes, and the like. Nanocarbon materials are also considered suitable for wiring applications. As methods for producing (synthesizing) nanocarbons such as the above-mentioned carbon nanotubes, a gas phase synthesis method and an arc discharge method are known.
一方、上記ナノカーボン材料とは異なるが、新規なカーボン材料としてダイヤモンドライクカーボン（ＤＬＣ）やカーボン膜が研究されている。従来、このＤＬＣやカーボン膜は蒸着法（ＣＶＤ、ＰＶＤ）によって一般に製造されてきたが、最近、電解析出による製造方法が提案されている（例えば、非特許文献１、２参照）。 On the other hand, diamond-like carbon (DLC) and carbon films have been studied as new carbon materials, although they are different from the nanocarbon materials. Conventionally, the DLC and the carbon film have been generally manufactured by a vapor deposition method (CVD, PVD), but recently, a manufacturing method by electrolytic deposition has been proposed (for example, see Non-Patent Documents 1 and 2).
しかしながら、カーボンナノチューブ等のナノカーボン材料を電気化学的に製造する技術については、全く検討されていない。そして、カーボンナノチューブを気相合成するには約５５０℃の温度が必要とされるため、製造コストが大となったり、カーボンナノチューブの応用分野が制限されるという問題がある。例えばカーボンナノチューブを回路基板上に直接形成させて配線に用いようとする場合、回路基板の耐熱温度が低いために上記気相合成法を適用することは困難である。
本発明は上記の課題を解決するためになされたものであり、装置が簡易で、低温で製造が可能なナノカーボン材料の製造方法、及び配線構造の製造方法の提供を目的とする。
However, a technique for electrochemically producing nanocarbon materials such as carbon nanotubes has not been studied at all. In addition, since a temperature of about 550 ° C. is required to synthesize carbon nanotubes in a gas phase, there are problems that the manufacturing cost is increased and the application field of carbon nanotubes is limited. For example, when carbon nanotubes are directly formed on a circuit board and used for wiring, it is difficult to apply the gas phase synthesis method because the heat resistant temperature of the circuit board is low.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for producing a nanocarbon material that can be produced at a low temperature with a simple apparatus and a method for producing a wiring structure.
本発明者らは種々検討した結果、所定の陰極及び電解液を用いることで、ナノカーボン材料を電気分解によって、装置が簡易で、従来より低温（例えば常温）で製造できることを見出した。つまり、上記した目的を達成するために、本発明のナノカーボン材料の製造方法は、触媒金属が不均一に形成された半導体を陰極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属の表面にナノカーボン材料を形成させることを特徴とする。 As a result of various studies, the present inventors have found that by using a predetermined cathode and an electrolytic solution, the nanocarbon material can be produced by electrolysis at a lower temperature (for example, room temperature) than before, with a simple apparatus. That is, in order to achieve the above-described object, the method for producing a nanocarbon material of the present invention uses a semiconductor in which a catalytic metal is heterogeneously formed as a cathode, and performs electrolysis in an electrolytic solution containing an organic solvent. A nanocarbon material is formed on the surface of the catalyst metal.
また、本発明のナノカーボン材料の製造方法は、触媒金属のイオンを含む電解液中で半導体を陰極として電気分解し、該半導体の表面に前記触媒金属を不均一に形成させる工程と、前記触媒金属が不均一に形成された半導体を陰極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属の表面にナノカーボン材料を形成させる工程とを有することを特徴とする。 The method for producing a nanocarbon material of the present invention includes a step of electrolyzing a semiconductor as a cathode in an electrolytic solution containing catalyst metal ions, and forming the catalyst metal unevenly on a surface of the semiconductor; And a step of forming a nanocarbon material on the surface of the catalyst metal by electrolysis in an electrolyte containing an organic solvent using a semiconductor in which a metal is unevenly formed as a cathode.
さらに、本発明のナノカーボン材料の製造方法は、半導体の表面に形成された触媒金属をエッチングし、該半導体の表面に前記触媒金属を不均一に形成させる工程と、前記触媒金属が不均一に形成された半導体を陰極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属の表面にナノカーボン材料を形成させる工程とを有することを特徴とする。 Furthermore, the method for producing a nanocarbon material of the present invention includes a step of etching a catalyst metal formed on a semiconductor surface to form the catalyst metal non-uniformly on the surface of the semiconductor, and the catalyst metal non-uniformly formed. And forming a nanocarbon material on the surface of the catalyst metal by electrolysis in an electrolytic solution containing an organic solvent using the formed semiconductor as a cathode.
本発明の配線構造の製造方法は、配線形成位置の両端にそれぞれ突状に形成された触媒金属を陰極及び／又は陽極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属間にナノカーボン材料を配線として形成させることを特徴とする。 The method for manufacturing a wiring structure according to the present invention is characterized in that the catalytic metal is formed as a cathode and / or an anode on both ends of the wiring forming position, and electrolyzed in an electrolytic solution containing an organic solvent. It is characterized in that a nanocarbon material is formed as a wiring in between.
本発明のナノカーボン材料の製造方法によれば、電気分解法という簡易な方法により、装置が簡易で、かつ従来より低温（例えば常温）でナノカーボン材料を製造することができ、特にカーボンナノチューブやカーボンナノワイヤー等の繊維状のナノカーボン材料の製造に適している。 According to the method for producing a nanocarbon material of the present invention, the nanocarbon material can be produced at a lower temperature (for example, room temperature) than the conventional apparatus by a simple method called an electrolysis method. Suitable for the production of fibrous nanocarbon materials such as carbon nanowires.
以下、本発明に係るナノカーボン材料の製造方法の実施の形態について説明する。
本発明に係るナノカーボン材料の製造方法は、触媒金属が不均一に形成された半導体を陰極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属の表面にナノカーボン材料を形成させるものである。
Hereinafter, embodiments of the method for producing a nanocarbon material according to the present invention will be described.
The method for producing a nanocarbon material according to the present invention uses a semiconductor in which a catalytic metal is heterogeneously formed as a cathode and electrolyzes it in an electrolytic solution containing an organic solvent, whereby the nanocarbon material is formed on the surface of the catalytic metal. It is to be formed.
本発明により製造されるナノカーボン材料とは、０．１ｎｍ程度〜数１００ｎｍのサイズの構造体からなるカーボン材料をいい、例えばカーボンナノチューブ（直径が０．１ｎｍ〜数１０ｎｍの管状繊維状物が例示される）、カーボンナノワイヤー（直径が数１００ｎｍの中実の繊維状物が例示される）、カーボンオニオン（直径が数ｎｍ〜数１００ｎｍでタマネギ状に黒鉛層が数１０〜数１００層積層した球状微粒子が例示される）、カーボンナノワイヤーの放射状集合体（カーボンナノワイヤが多数放射状に束ねられ、花のように拡がったもの）が挙げられる。特に、本発明は、カーボンナノチューブやカーボンナノワイヤー等、細長く繊維状の材料の製造に適している。 The nanocarbon material produced according to the present invention refers to a carbon material composed of a structure having a size of about 0.1 nm to several hundred nm, such as a carbon nanotube (a tubular fibrous material having a diameter of 0.1 nm to several tens of nm). Carbon nanowires (examples are solid fibrous materials having a diameter of several hundreds of nanometers), carbon onions (diameters of several nanometers to several hundreds of nanometers, and several to several hundreds of graphite layers laminated in an onion shape) Spherical fine particles are exemplified), and a radial aggregate of carbon nanowires (a large number of carbon nanowires are radially bundled and spread like a flower). In particular, the present invention is suitable for producing elongated and fibrous materials such as carbon nanotubes and carbon nanowires.
陰極に用いる半導体としては、シリコンが入手しやすく好ましいが、この他にゲルマニウム等の半導体や、高抵抗の金属を用いることができる。又、シリコンを用いる場合は、不純物がドーピングされたものを用いると、電気抵抗が低くなるので好ましい。 As a semiconductor used for the cathode, silicon is preferable because it is easily available, but in addition to this, a semiconductor such as germanium or a metal having high resistance can be used. In addition, when silicon is used, it is preferable to use a material doped with impurities since the electric resistance is lowered.
この半導体の表面には触媒金属が不均一に形成しているが、ここでいう不均一形成とは半導体表面に例えば島状、粒状に分散して形成することをいい、触媒金属の形成部分が半導体に比べて導電性が高いために、電流がこの触媒金属の形成部分に集中し、電解液中の有機溶媒の炭素原子がこの形成部分を核として電析するものと考えられる。触媒金属は導電性を有するものであれば何でもよいが、例えばＮｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｃｕ、Ｚｎを例示することができる。好ましくはＮｉ、Ｃｏ、Ｆｅがよく、特にＮｉが最も好ましく、次にＣｏ、Ｆｅの順で好ましい。触媒金属は、半導体の表面に数ｎｍ〜数１０ｎｍ、好ましくは１０ｎｍ程度の厚みで形成させるのが好ましい。なお、複数種類の触媒金属（例えばＮｉとＦｅ）やこれらの合金を１つの半導体上に形成させてもよい。 The catalyst metal is unevenly formed on the surface of the semiconductor, but the term “nonuniform formation” as used herein means that the semiconductor surface is dispersed, for example, in the form of islands and grains. Since the conductivity is higher than that of a semiconductor, it is considered that the current concentrates on the formation part of the catalyst metal, and the carbon atoms of the organic solvent in the electrolytic solution are electrodeposited using the formation part as a nucleus. The catalyst metal may be anything as long as it has conductivity, and examples thereof include Ni, Co, Fe, Al, Cu, and Zn. Ni, Co, and Fe are preferred, and Ni is most preferred, followed by Co and Fe in this order. The catalytic metal is preferably formed on the surface of the semiconductor with a thickness of several nm to several tens of nm, preferably about 10 nm. A plurality of types of catalyst metals (for example, Ni and Fe) and alloys thereof may be formed on one semiconductor.
半導体表面に不均一形成された個々の島状（又は粒状）の触媒金属の大きさは、その表面に主に形成されるナノカーボン材料の種類を決めると考えられる。例えば、個々の触媒金属の大きさ（径）を０．１〜数１０ｎｍ、好ましくは０．１〜１０ｎｍ、より好ましくは０．１〜０．５ｎｍとすると、主にカーボンナノチューブが製造される。これは、いわゆるエッジ効果により触媒金属の縁部に電解電流が集中して該縁部に炭素が電析し、一方で触媒金属の中心部には電析し難くなり、管状のカーボンナノチューブが成長することが考えられる。また、例えば、個々の触媒金属の大きさ（径）を数１００ｎｍ、好ましくは１００〜２００ｎｍとすると、主にカーボンナノワイヤーが製造される。このようにすると、径が大きくなるためにエッジ効果は生じず触媒金属の表面全体に電解電流が流れ、触媒金属の表面全体に炭素が電析し、中実のカーボンカーボンナノワイヤーが成長することが考えられる。なお、種々の大きさ（径）の触媒金属が半導体表面に存在する場合、その径に応じて各種のナノカーボン材料が形成される。 The size of each island-shaped (or granular) catalyst metal formed nonuniformly on the semiconductor surface is considered to determine the type of nanocarbon material mainly formed on the surface. For example, when the size (diameter) of each catalytic metal is 0.1 to several tens of nm, preferably 0.1 to 10 nm, more preferably 0.1 to 0.5 nm, carbon nanotubes are mainly produced. This is because the electrolysis current concentrates on the edge of the catalytic metal due to the so-called edge effect, and carbon deposits on the edge, while it becomes difficult to deposit on the central part of the catalytic metal, and tubular carbon nanotubes grow. It is possible to do. For example, when the size (diameter) of each catalyst metal is several 100 nm, preferably 100 to 200 nm, carbon nanowires are mainly produced. When this is done, the edge effect does not occur due to the large diameter, electrolysis current flows over the entire surface of the catalytic metal, carbon deposits on the entire surface of the catalytic metal, and solid carbon carbon nanowires grow. Can be considered. In addition, when catalyst metals of various sizes (diameters) are present on the semiconductor surface, various nanocarbon materials are formed according to the diameters.
半導体表面に触媒金属を不均一に形成させる方法としては、例えば触媒金属のイオンを含む電解液中で半導体を陰極として電気分解し、半導体の表面に前記触媒金属を不均一に電析させる方法がある。この場合、電解液中の触媒金属イオン濃度を低くしたり、低電流密度で電解することにより、触媒金属を不均一形成させることができる。この場合、溶液中に溶解している金属イオンが全て基板表面(片面)に堆積したとすると、その膜厚が１０ｎｍ程度になるような分量だけ、金属イオンを電解液に溶解すればよい。従って、電解液の量に応じて濃度が異なるので、上記条件に沿うよう適宜調整する。電解液としては、例えば上記触媒金属の硝酸塩（硝酸ニッケル、硝酸コバルト、硝酸第１鉄等）をアルコール（例えばエチルアルコール）に溶解したものを用いることができる。 As a method for forming the catalyst metal non-uniformly on the semiconductor surface, for example, there is a method of electrolyzing the semiconductor as a cathode in an electrolytic solution containing ions of the catalyst metal and depositing the catalyst metal non-uniformly on the surface of the semiconductor. is there. In this case, the catalyst metal can be formed non-uniformly by lowering the catalyst metal ion concentration in the electrolytic solution or by performing electrolysis at a low current density. In this case, if all the metal ions dissolved in the solution are deposited on the substrate surface (one side), the metal ions may be dissolved in the electrolytic solution in such an amount that the film thickness is about 10 nm. Accordingly, the concentration varies depending on the amount of the electrolytic solution, so that the concentration is appropriately adjusted to meet the above conditions. As the electrolytic solution, for example, a solution obtained by dissolving a nitrate (eg, nickel nitrate, cobalt nitrate, ferrous nitrate) of the catalyst metal in an alcohol (eg, ethyl alcohol) can be used.
半導体表面に触媒金属を不均一に形成させる他の方法としては、半導体の表面に触媒金属を形成し、この触媒金属をエッチングする方法がある。この場合、例えば半導体の表面にＮｉ等の触媒金属をスパッタリングにより所定厚み形成し、これをエッチングガス（例えばアンモニアガス）中に置くことで、Ｎｉが部分的にエッチング除去される。 As another method for forming the catalyst metal unevenly on the semiconductor surface, there is a method of forming the catalyst metal on the surface of the semiconductor and etching the catalyst metal. In this case, for example, a catalyst metal such as Ni is formed on the surface of the semiconductor by sputtering to a predetermined thickness, and this is placed in an etching gas (for example, ammonia gas), whereby Ni is partially removed by etching.
不均一に形成された個々の触媒金属の大きさ（径）を制御する方法としては、上記電析の場合は、電解液中の金属イオンの量を多くすることで触媒金属を大きな粒とすることができる。上記エッチングの場合は、エッチング温度が高く、時間が長い方が触媒金属が小さな粒となる。なお、いずれの場合も通常、触媒金属の大きさはかなり広範囲に分布し、大きい粒の粒径は数μｍ、小さい粒の粒径は数ｎｍであることが多い。 As a method for controlling the size (diameter) of each catalyst metal formed unevenly, in the case of the above electrodeposition, the catalyst metal is made into large particles by increasing the amount of metal ions in the electrolytic solution. be able to. In the case of the above etching, the catalyst metal becomes smaller particles when the etching temperature is higher and the time is longer. In either case, the size of the catalyst metal is usually distributed over a fairly wide range, and the particle size of large particles is often several μm, and the particle size of small particles is often several nm.
電解液に含まれる有機溶媒としては特に制限はないが、アルコール、ニトリル、ベンゼン、キシレンを例示することができ、好ましくはメタノールやエタノール等のアルコールや、メタンにトリルやエタンニトリル（アセトニトリル）等の脂肪族ニトリルがよい。電解液は有機溶媒単体であってもよく、又、複数種類の有機溶媒を混合したものであってもよく、さらに、有機溶媒に水、電導助剤等を加えたものでもよい。 Although there is no restriction | limiting in particular as an organic solvent contained in electrolyte solution, Alcohol, a nitrile, benzene, xylene can be illustrated, Preferably alcohol, such as methanol and ethanol, Toluyl, ethane nitrile (acetonitrile), etc. to methane Aliphatic nitriles are preferred. The electrolytic solution may be a single organic solvent, may be a mixture of a plurality of types of organic solvents, or may be a solution obtained by adding water, a conductive aid or the like to an organic solvent.
本発明は上記電解液を電気分解するものであり、陽極としては特に制限されないが、例えばカーボン電極、各種の不溶性陽極等を用いることができる。又、電解条件も特に制限されないが、例えば１〜数１０ｍＡ／ｃｍ２、好ましくは２〜６ｍＡ／ｃｍ２の電流密度で直流電解すればよい。電解電圧（陰極と陽極間の電圧）は、電極間距離、電解液の電気電導度に応じて変化するが、好ましくは０．１ｋＶ〜数１０ｋＶ、より好ましくは０．１〜５ｋＶとする。電解電圧をこのように高くすることで、有機溶媒中の炭素原子がアニオンとなって電析し易くなる可能性がある。又、交番電解してもよく、この場合は陰極と陽極のいずれか、好ましくは両方に上記半導体を用いればよい。なお、電解温度も特に制限はなく、電解液が沸騰しない温度、例えば室温〜５０℃程度とすればよい。電解による発熱を防止するため、適宜電解液を冷却してもよい。電解時間は電解条件によって変化するが、例えば１〜１０時間程度電解すればよい。 In the present invention, the electrolytic solution is electrolyzed, and the anode is not particularly limited. For example, a carbon electrode, various insoluble anodes, and the like can be used. Although not particularly limited electrolysis conditions, for example, to several 10 mA / cm 2, preferably it may be direct electrolysis at a current density of 2~6mA / cm 2. The electrolytic voltage (voltage between the cathode and the anode) varies depending on the distance between the electrodes and the electric conductivity of the electrolytic solution, but is preferably 0.1 kV to several tens kV, more preferably 0.1 to 5 kV. By increasing the electrolysis voltage in this way, carbon atoms in the organic solvent may become anions and may be easily electrodeposited. Alternatively, alternating electrolysis may be performed. In this case, the above semiconductor may be used for either the cathode or the anode, preferably both. The electrolysis temperature is not particularly limited, and may be a temperature at which the electrolytic solution does not boil, for example, about room temperature to 50 ° C. In order to prevent heat generation due to electrolysis, the electrolytic solution may be appropriately cooled. Although electrolysis time changes with electrolysis conditions, it may suffice, for example for about 1 to 10 hours.
電気分解を行うには、例えば図１に示す電解装置を用いることができる。この図において、電解装置１０は、電解槽２、マグネチックスターラ３、半導体基板からなる陰極４、陽極６、温度計７、ＤＣ電源８を備えている。電解槽２内には有機溶媒を含む電解液が入っている。陰極４のうち陽極６との対向面には触媒金属４ａが不均一に形成されている。そして、電解により、有機溶媒中の炭素原子が触媒金属４ａ上に電析し、陽極６側へ成長してゆく。 For the electrolysis, for example, an electrolysis apparatus shown in FIG. 1 can be used. In this figure, an electrolysis apparatus 10 includes an electrolytic cell 2, a magnetic stirrer 3, a cathode 4 made of a semiconductor substrate, an anode 6, a thermometer 7, and a DC power source 8. The electrolytic bath 2 contains an electrolytic solution containing an organic solvent. A catalyst metal 4 a is formed unevenly on the surface of the cathode 4 facing the anode 6. Then, carbon atoms in the organic solvent are electrodeposited on the catalyst metal 4a by electrolysis and grow to the anode 6 side.
ところで、電析したナノカーボン材料は、例えば触媒金属から機械的方法で剥いで回収してもよい。又、触媒金属を内包したナノカーボン材料や、触媒金属が底部に形成されたナノカーボン材料を得ることができる。また、半導体上に電析したままで使用してもよい。 By the way, the electrodeposited nanocarbon material may be separated from the catalyst metal by a mechanical method and recovered. Moreover, the nanocarbon material which included the catalyst metal, and the nanocarbon material in which the catalyst metal was formed in the bottom part can be obtained. Moreover, you may use it, depositing on a semiconductor.
図２、３に、ナノカーボン材料が電析する態様を模式的に示す。図２において、半導体基板４０の表面に触媒金属４０ａが島状に形成され、既に述べたエッジ効果により触媒金属４０ａの縁部から陽極側（図の上方向）に向かってナノカーボン材料が成長し、管状のカーボンナノチューブが形成されている。又、図３においては、半導体基板４１の表面に触媒金属４１ａが島状に形成され、この場合は触媒金属４０ａの表面全体（側面を含む）にナノカーボン材料が電析し、触媒金属を内包したカーボンオニオンが形成されている。 2 and 3 schematically show how the nanocarbon material is electrodeposited. In FIG. 2, the catalyst metal 40a is formed in an island shape on the surface of the semiconductor substrate 40, and the nanocarbon material grows from the edge of the catalyst metal 40a toward the anode side (upward in the figure) by the edge effect described above. Tubular carbon nanotubes are formed. In FIG. 3, the catalyst metal 41a is formed in an island shape on the surface of the semiconductor substrate 41. In this case, the nanocarbon material is electrodeposited on the entire surface (including side surfaces) of the catalyst metal 40a, and the catalyst metal is included. Carbon onions are formed.
次に、本発明の配線構造の製造方法の一実施形態について説明する。本発明の配線構造の製造方法は、上記ナノカーボン材料の製造方法と同様な手順により行われるが、陰極及び陽極として、配線形成位置の両端にそれぞれ突状に形成された触媒金属を用いる点が上記方法と異なっている。そして、本発明の配線構造の製造方法においては、陰極及び陽極となる触媒金属間にナノカーボン材料を配線として形成させるものであるが、これについて図４を参照して説明する。 Next, an embodiment of a method for manufacturing a wiring structure according to the present invention will be described. The method for producing a wiring structure of the present invention is performed by the same procedure as the method for producing the nanocarbon material, except that a catalytic metal formed in a protruding shape at both ends of the wiring forming position is used as the cathode and the anode. Different from the above method. And in the manufacturing method of the wiring structure of this invention, nanocarbon material is formed as wiring between the catalyst metals used as a cathode and an anode, and this is demonstrated with reference to FIG.
図４において、２つの回路基板１００、１０１の表面にはそれぞれ配線パターン２００、２０１が形成されている（図４（ａ））。いま、配線パターン２００の端部（右端）と、配線パターン２０１の端部（左端）とを配線して接続したいとする。この場合、まず配線形成位置の両端となる、配線パターン２００の端部（右端）と配線パターン２０１の端部（左端）とに、それぞれ触媒金属からなる突部２００ａ、２０１ａを予め形成しておく。次に、少なくとも突部２００ａ、２０１ａを含む上記配線形成位置が、有機溶媒を含む電解液に浸漬（又は接触）するようにする。この場合、各回路基板１００、１０１全体を上記電解液に浸漬してもよく、又、上記配線形成位置のみが電解液に浸漬されるような電解セルを用いてもよい。 In FIG. 4, wiring patterns 200 and 201 are formed on the surfaces of two circuit boards 100 and 101, respectively (FIG. 4A). Now, it is assumed that the end portion (right end) of the wiring pattern 200 and the end portion (left end) of the wiring pattern 201 are to be wired and connected. In this case, first, protrusions 200a and 201a made of a catalyst metal are formed in advance on the end (right end) of the wiring pattern 200 and the end (left end) of the wiring pattern 201, which are both ends of the wiring formation position, respectively. . Next, the wiring formation position including at least the protrusions 200a and 201a is immersed (or contacted) with an electrolytic solution containing an organic solvent. In this case, the entire circuit boards 100 and 101 may be immersed in the electrolytic solution, or an electrolytic cell in which only the wiring forming position is immersed in the electrolytic solution may be used.
そして、この状態で突部２００ａ、２０１ａをそれぞれ陰極，陽極（いずれが陰極であってもよいがこの実施形態では仮に突部２００ａを陰極とする）として電気分解すると、突部２００ａに電析したナノカーボン材料が、突部２０１ａ側に向かって成長し、やがてナノカーボン材料は突部２０１ａに接続する。このようにして、突部２００ａ、２０１ａ間にナノカーボン材料が配線３００として形成される（図４（ｂ））。なお、電気分解は直流電解でもよく、又、交番電解でもよい。なお、実際には、突部２００ａが配線パターン２００と導通し、突部２０１ａが配線パターン２０１と導通しているので、電源を各配線パターン２００、２０１に接続して電解すればよい。なお、直流電解を行う場合、アノード側の突部には、不溶性の金属やカーボン材料を電極として形成するのが好ましい。 In this state, the projections 200a and 201a are electrolyzed as the cathode and the anode, respectively (which may be a cathode, but in this embodiment, the projection 200a is assumed to be a cathode). The nanocarbon material grows toward the protrusion 201a, and the nanocarbon material eventually connects to the protrusion 201a. In this way, the nanocarbon material is formed as the wiring 300 between the protrusions 200a and 201a (FIG. 4B). The electrolysis may be direct current electrolysis or alternating electrolysis. Actually, since the protrusion 200a is electrically connected to the wiring pattern 200 and the protrusion 201a is electrically connected to the wiring pattern 201, a power source may be connected to each of the wiring patterns 200 and 201 for electrolysis. When direct current electrolysis is performed, it is preferable to form an insoluble metal or carbon material as an electrode on the projection on the anode side.
突部２００ａ、２０１ａの大きさ（径）は、上記したナノカーボン材料の製造方法における触媒金属の大きさ（径）と同等でよく、径を制御することにより、ナノカーボン材料の種類も変化する点についても、上記したナノカーボン材料の製造方法の場合と同様である。突部２００ａ、２０１ａの高さは、例えば数ｎｍ〜数１０ｎｍとすればよい。要は、突部２００ａ、２０１ａに電流が集中すればよい。 The size (diameter) of the protrusions 200a and 201a may be equal to the size (diameter) of the catalytic metal in the above-described method for producing a nanocarbon material, and the type of the nanocarbon material also changes by controlling the diameter. This is also the same as in the above-described method for producing a nanocarbon material. The height of the protrusions 200a and 201a may be several nm to several tens of nm, for example. In short, it suffices if the current concentrates on the protrusions 200a and 201a.
次に、本発明の配線構造の製造方法の他の実施形態について、図５を参照して説明する。図５において、配線パターン２１０には突部２１０ａが形成され、配線パターン２１１には突部２１１ａが形成されている。いま、配線パターン２１０、２１１を対向させ、突部２１０ａと突部２１１ａの間を配線したいとする。なお、この図において、配線パターン２１０は配線パターン２１１の上側に位置し、突部２１０ａは突部２１１ａの延長線上にあるものとする。 Next, another embodiment of the method for manufacturing a wiring structure of the present invention will be described with reference to FIG. In FIG. 5, a protrusion 210 a is formed on the wiring pattern 210, and a protrusion 211 a is formed on the wiring pattern 211. Now, it is assumed that the wiring patterns 210 and 211 are opposed to each other and the wiring between the protruding portion 210a and the protruding portion 211a is to be wired. In this figure, it is assumed that the wiring pattern 210 is located above the wiring pattern 211 and the protrusion 210a is on an extension line of the protrusion 211a.
そして、少なくとも突部２１０ａと突部２１１ａの間に上記電解液を満たした状態で、電源を各配線パターン２１０、２１１に接続して電解すると、上記図４の場合と同様に、突部２１０ａと突部２１１ａの間にナノカーボン材料が配線３０１として形成される。なお、突部２１０ａが突部２１１ａの延長線からある程度ずれていても、ナノカーボン材料が配線として形成される。 When the electrolytic solution is filled between at least the protrusions 210a and the protrusions 211a and a power source is connected to the wiring patterns 210 and 211 and electrolysis is performed, as in the case of FIG. A nanocarbon material is formed as the wiring 301 between the protrusions 211a. Note that the nanocarbon material is formed as the wiring even if the protrusion 210a is displaced to some extent from the extension line of the protrusion 211a.
以上のように、本発明の配線構造の製造方法によれば、ナノカーボン材料を用いて常温等の低温で配線ができ、また、従来は極めて困難であった微細な配線を簡易に行うことができる。すなわち、配線形成位置における突状部に電流が集中するので、配線したい部分に選択的にナノカーボン材料を電析させて配線として形成できる。 As described above, according to the method for manufacturing a wiring structure of the present invention, it is possible to perform wiring at a low temperature such as room temperature using a nanocarbon material, and it is possible to easily perform fine wiring that has been extremely difficult in the past. it can. That is, current concentrates on the projecting portion at the wiring forming position, so that the nanocarbon material can be selectively deposited on the portion to be wired to form a wiring.
次に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.
１．半導体基板表面への触媒金属の形成
ｐ型のシリコン結晶からなる半導体基板（抵抗率：０．５Ωｃｍ、電極面積５０ｍｍ２）の表面に、スパッタリングによって厚み３０ｎｍのＮｉを形成した後、アンモニアガス雰囲気（１３．３３ｋＰａ、８００℃）に１０分間置いた。これにより、Ｎｉが部分的にエッチング除去されて粒状のＮｉが残存した半導体基板が得られた。Ｎｉが不均一に形成された半導体基板をＳＥＭ（走査型電子顕微鏡）で撮影した像を図６に示す。図の白い部分が粒状のＮｉであり、０．１〜０．５μｍ程度の大きさ（径）の粒状Ｎｉが主に見られるが、さらに倍率を高くしたSEM像で数１０ｎｍ粒径の粒状Ｎｉも確認した（不図示）。このエッチング法により作製した半導体基板を基板１とする。
1. Formation of catalytic metal on semiconductor substrate surface After forming Ni of 30 nm thickness by sputtering on the surface of a semiconductor substrate made of p-type silicon crystal (resistivity: 0.5 Ωcm, electrode area 50 mm 2 ), an ammonia gas atmosphere ( (13.33 kPa, 800 ° C.) for 10 minutes. As a result, a semiconductor substrate in which Ni was partially removed by etching and granular Ni remained was obtained. The image which image | photographed the semiconductor substrate in which Ni was formed unevenly with SEM (scanning electron microscope) is shown in FIG. The white part of the figure is granular Ni, and granular Ni having a size (diameter) of about 0.1 to 0.5 μm is mainly seen, but a granular Ni having a particle size of several tens of nm in a SEM image with a higher magnification. Was also confirmed (not shown). A semiconductor substrate manufactured by this etching method is a substrate 1.
２．電気分解による陰極への電析
前記図１に示した電解装置を準備した。陰極には上記基板１を用いた。陽極には５ｍｍ外径のカーボン棒を用いた。そして、電解液としてメタンニトリル（純度 99.5 vol%,試薬特級）５０ｍＬを用い、電流密度４ｍＡ／ｃｍ２、電極間距離５ｍｍ、電解電圧１ｋＶ、電解液量５０ｍＬで電解を行い、陰極表面に電析物を得た。電解は室温で行ったが、電解後も液温度は２〜３℃しか上昇しなかった。
2. Electrodeposition on the cathode by electrolysis The electrolytic apparatus shown in FIG. 1 was prepared. The substrate 1 was used as the cathode. A carbon rod having an outer diameter of 5 mm was used for the anode. Then, 50 mL of methane nitrile (purity 99.5 vol%, reagent grade) is used as the electrolytic solution, electrolysis is performed at a current density of 4 mA / cm 2 , a distance between electrodes of 5 mm, an electrolytic voltage of 1 kV, and an electrolytic solution amount of 50 mL, and electrodeposited on the cathode surface I got a thing. Although electrolysis was performed at room temperature, the liquid temperature rose only by 2 to 3 ° C. even after electrolysis.
この実施例では、下記の電解液により上記半導体基板へのＮｉの不均一析出と、ナノカーボン材料の電析とを同時に行った。
まず、硝酸Ｎｉ４．４×１０−２ｍｇをエタノール（純度 99.5 vol%,試薬特級）２．５ｍＬに溶かした後、これをエタノール５０ｍＬに溶かして電解液を作製した。この電解液中で、上記電解装置を用い、上記半導体基板を陰極とし、上記カーボン棒を陽極として、上記実施例１と同一の電解条件で電解し、陰極表面に電析物を得た。電解時間は８時間とした。この電解では、初期にＮｉが半導体基板上に粒状に析出し、次にＮｉ粒上にナノカーボン材料が電析したものと考えられる。
In this example, non-uniform deposition of Ni on the semiconductor substrate and electrodeposition of the nanocarbon material were simultaneously performed with the following electrolyte solution.
First, nitric acid Ni 4.4 × 10 −2 mg was dissolved in ethanol (purity 99.5 vol%, reagent special grade) 2.5 mL, and then dissolved in ethanol 50 mL to prepare an electrolytic solution. In this electrolytic solution, electrolysis was performed on the surface of the cathode using the above electrolysis apparatus, electrolysis under the same electrolysis conditions as in Example 1, using the semiconductor substrate as a cathode and the carbon rod as an anode. The electrolysis time was 8 hours. In this electrolysis, it is considered that Ni was first deposited in a granular form on the semiconductor substrate, and then the nanocarbon material was electrodeposited on the Ni grains.
比較例
基板として、Ｎｉを形成させずに上記半導体基板を用いたことと、電解液としてエタノールを用いたことの他は、上記実施例１とまったく同様にして電解を行い、陰極表面に電析物を得た。
Comparative Example Electrolysis was performed in exactly the same manner as in Example 1 except that the semiconductor substrate was used without forming Ni as a substrate and ethanol was used as the electrolytic solution. I got a thing.
各実施例及び比較例で得られた電析物の同定を次の方法で行った。まず、電析物が得られた陰極のＳＥＭ（走査型電子顕微鏡：日本電子製 JSM-5600 (電子線15kV)）測定を行い、また、電析物のＴＥＭ（透過型電子顕微鏡：日本電子製 JEM-2010F (電子線200kV)）測定を行った。また、上記ＳＥＭ測定と同じ測定領域におけるＥＤＳ(Energy
dispersive spectroscopy：エネルギー分散型Ｘ線分光装置、オックスフォード製 Link ISIS (電子線15kV))測定を行った。結果は図７〜図１８、及び表１にまとめた通りである。
The electrodeposits obtained in each Example and Comparative Example were identified by the following method. First, SEM (scanning electron microscope: JSM-5600 (electron beam 15 kV)) of the cathode from which the deposit was obtained was measured, and the TEM (transmission electron microscope: manufactured by JEOL) of the deposit. JEM-2010F (electron beam 200 kV)) measurement was performed. In addition, EDS (Energy
dispersive spectroscopy: An energy dispersive X-ray spectrometer, Oxford Link ISIS (electron beam 15 kV)) was measured. The results are as summarized in FIGS. 7 to 18 and Table 1.
まず、図７は、実施例２における電析後の基板表面のＳＥＭ像であり、図８は図７の部分拡大ＳＥＭ像であり、図９は図８の部分拡大ＳＥＭ像であり、図１０は図９の部分拡大ＳＥＭ像である。各図中、白い部分が析出物を示し、黒い部分はアモルファス的カーボン膜の堆積物を示す。この析出物は半導体基板の所定部分を核としてスパイク状（針状）に成長していることがわかる。 First, FIG. 7 is a SEM image of the substrate surface after electrodeposition in Example 2, FIG. 8 is a partially enlarged SEM image of FIG. 7, FIG. 9 is a partially enlarged SEM image of FIG. Fig. 10 is a partially enlarged SEM image of Fig. 9. In each figure, white portions indicate precipitates, and black portions indicate deposits of an amorphous carbon film. It can be seen that this precipitate grows in a spike shape (needle shape) with a predetermined portion of the semiconductor substrate as a nucleus.
図１１は、実施例２における電析後の基板表面の別の場所のＳＥＭ像であり、図１２は図１１の部分拡大ＳＥＭ像である。各図中、白い部分が析出物を示し、この析出物は繊維状に成長していることがわかる。さらに、上記各図７，１１の測定試料と同一の測定領域について、ＥＤＸにより元素分析を行ったところ、各図の白い部分が炭素であることが判明した。以上の図７〜図１２より、実施例２においては直径約１００ｎｍで繊維状の炭素構造物が生成していることがわかり、これはカーボンナノワイヤであるということができる。 FIG. 11 is an SEM image of another location on the substrate surface after electrodeposition in Example 2, and FIG. 12 is a partially enlarged SEM image of FIG. In each figure, a white part shows the deposit and it turns out that this deposit is growing in the fiber form. Furthermore, when elemental analysis was performed by EDX on the same measurement region as the measurement sample in each of FIGS. 7 and 11, it was found that the white portion of each figure was carbon. From FIG. 7 to FIG. 12, it can be seen that in Example 2, a fibrous carbon structure having a diameter of about 100 nm was generated, which can be said to be a carbon nanowire.
図１３は、実施例２における電析物のＴＥＭ像である。この図において、直径が１０〜２０ｎｍ程度で、黒鉛層が多数積層したタマネギ状の炭素構造体が生成していることがわかる。また、上記ＥＤＸ分析の結果からこの構造体の組成は炭素であり、これらのことから、この析出物はカーボンオニオンであると同定することができる。 FIG. 13 is a TEM image of the electrodeposit in Example 2. In this figure, it can be seen that an onion-like carbon structure having a diameter of about 10 to 20 nm and a large number of graphite layers is formed. Moreover, the composition of this structure is carbon from the results of the above EDX analysis, and from these facts, this precipitate can be identified as carbon onion.
図１４は、実施例２における電析物のうち、図１３と別の測定領域におけるＴＥＭ像であり、図１５は図１４の部分拡大ＴＥＭ像である。図１５によれば、この繊維状の析出物は、黒鉛層が多数積層しており、また芯部は空洞であることがわかる。そして、図１５によれば、各黒鉛層の層間隔はおよそ０．３３〜０．３６ｎｍで、外径約３０ｎｍ、内径約２ｎｍであると読み取れた。通常、カーボンナノチューブの層間隔は０．３４ｎｍといわれており、これより、この析出物はカーボンナノチューブであると同定することができる。 14 is a TEM image in a measurement region different from that of FIG. 13 among the electrodeposits in Example 2, and FIG. 15 is a partially enlarged TEM image of FIG. According to FIG. 15, it is understood that the fibrous precipitate has a large number of graphite layers laminated and the core is a cavity. According to FIG. 15, it was read that the interval between the graphite layers was about 0.33 to 0.36 nm, the outer diameter was about 30 nm, and the inner diameter was about 2 nm. Usually, the layer interval of carbon nanotubes is said to be 0.34 nm, and this precipitate can be identified as carbon nanotubes.
図１６は、実施例１における電析後の基板表面のＳＥＭ像であり、図の中央部やや右よりの部分には、Ｎｉを核としてスパイク状の電析物が見られる。この電析物もＥＤＸによれば炭素からなることが判明したので、カーボンナノワイヤであると考えられる。 FIG. 16 is an SEM image of the substrate surface after electrodeposition in Example 1, and spike-like electrodeposits with Ni as the nucleus are seen in the center part and a part from the right side of the figure. Since this electrodeposit was also found to be composed of carbon according to EDX, it is considered to be a carbon nanowire.
図１７は、比較例における電析後の基板表面のＳＥＭ像である。図の白い部分と黒い部分は、いずれもアモルファス的カーボン膜であり、膜厚の相違（膜表面の凹凸）により、白い部分と黒い部分が撮影されたと考えられる。また、図１８は、図１７の部分拡大ＳＥＭ像である。膜状物が基板表面のほぼ全面に析出したが、カーボンナノチューブやカーボンナノワイヤー等の繊維状の炭素材料は見られなかった。なお、この膜状物のラマン分光を行ったところ、ダイヤモンド的カーボンに見られるようなシャープな信号は観測されなかったため、これはアモルファス構造のカーボン膜であると考えられる。 FIG. 17 is an SEM image of the substrate surface after electrodeposition in the comparative example. The white part and the black part in the figure are both amorphous carbon films, and it is considered that the white part and the black part were photographed due to the difference in film thickness (unevenness on the film surface). FIG. 18 is a partially enlarged SEM image of FIG. Although the film-like material was deposited on almost the entire surface of the substrate, fibrous carbon materials such as carbon nanotubes and carbon nanowires were not found. When this film-like material was subjected to Raman spectroscopy, a sharp signal as seen in diamond-like carbon was not observed, which is considered to be an amorphous carbon film.
以上の結果を表１にまとめる。 The results are summarized in Table 1.
表１から明らかなように、実施例１、２の場合、カーボンナノチューブ、カーボンナノワイヤーや、カーボンオニオンが得られた。一方、比較例の場合、アモルファス構造の炭素膜層が得られたが、カーボンナノチューブやカーボンナノワイヤーが得られなかった。 As apparent from Table 1, in the case of Examples 1 and 2, carbon nanotubes, carbon nanowires, and carbon onions were obtained. On the other hand, in the case of the comparative example, a carbon film layer having an amorphous structure was obtained, but carbon nanotubes and carbon nanowires were not obtained.
２ 電解槽
４ 陰極（半導体）
４ａ 触媒金属
６ 陽極
８ ＤＣ電源
１０ 電解装置
2 Electrolyzer 4 Cathode (semiconductor)
4a Catalytic metal 6 Anode 8 DC power supply 10 Electrolyzer
Claims (4)
前記触媒金属が不均一に形成された半導体を陰極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属の表面にナノカーボン材料を形成させる工程と
を有することを特徴とするナノカーボン材料の製造方法。 Electrolyzing a semiconductor as a cathode in an electrolytic solution containing catalyst metal ions, and forming the catalyst metal non-uniformly on the surface of the semiconductor; and
A step of forming a nanocarbon material on the surface of the catalytic metal by electrolyzing the semiconductor in which the catalytic metal is heterogeneously formed as a cathode and in an electrolytic solution containing an organic solvent. A method for producing a nanocarbon material.
前記触媒金属が不均一に形成された半導体を陰極とし、有機溶媒を含む電解液中で電気分解することにより、前記触媒金属の表面にナノカーボン材料を形成させる工程と
を有することを特徴とするナノカーボン材料の製造方法。 Etching the catalyst metal formed on the surface of the semiconductor, and forming the catalyst metal non-uniformly on the surface of the semiconductor;
A step of forming a nanocarbon material on the surface of the catalytic metal by electrolyzing the semiconductor in which the catalytic metal is heterogeneously formed as a cathode and in an electrolytic solution containing an organic solvent. A method for producing a nanocarbon material.
A catalyst metal formed in a protruding shape at both ends of the wiring formation position is used as a cathode and / or anode, and electrolysis is performed in an electrolyte containing an organic solvent, thereby forming a nanocarbon material between the catalyst metals as a wiring. A method of manufacturing a wiring structure characterized by the above.
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| JP2003270361A JP4133655B2 (en) | 2003-07-02 | 2003-07-02 | Method for producing nanocarbon material and method for producing wiring structure |
| PCT/JP2003/016831 WO2005003409A1 (en) | 2003-07-02 | 2003-12-25 | Method for producing nanocarbon material and method for manufacturing wiring structure |
| CA002530976A CA2530976A1 (en) | 2003-07-02 | 2003-12-25 | Method for producing nanocarbon material and method for manufacturing wiring structure |
| US10/563,018 US20060163077A1 (en) | 2003-07-02 | 2003-12-25 | Method for producing nanocarbon material and method for manufacturing wiring structure |
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| JP2003270361A JP4133655B2 (en) | 2003-07-02 | 2003-07-02 | Method for producing nanocarbon material and method for producing wiring structure |
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| JP4133655B2 true JP4133655B2 (en) | 2008-08-13 |
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| JP (1) | JP4133655B2 (en) |
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| JP4625955B2 (en) * | 2005-08-23 | 2011-02-02 | 国立大学法人電気通信大学 | Carbon tube and carbon tube manufacturing method |
| TWI363367B (en) * | 2007-12-26 | 2012-05-01 | Tatung Co | Composite field emission source and method of fabricating the same |
| JPWO2011111791A1 (en) * | 2010-03-11 | 2013-06-27 | 国立大学法人北海道大学 | Method for producing carbon nanotube |
| US9075148B2 (en) * | 2011-03-22 | 2015-07-07 | Savannah River Nuclear Solutions, Llc | Nano structural anodes for radiation detectors |
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| JP3713561B2 (en) * | 2001-06-26 | 2005-11-09 | 独立行政法人科学技術振興機構 | Method for synthesizing highly aligned aligned carbon nanotubes using organic liquid and apparatus for synthesizing the same |
| JP2003115259A (en) * | 2001-10-03 | 2003-04-18 | Sony Corp | Electron emitting device and manufacturing method for it, cold cathode field electron emitting element and manufacturing method for it, cold cathode field electron emitting display device and manufacturing method for it, and method for etching thin film |
| JP4691648B2 (en) * | 2002-03-08 | 2011-06-01 | 独立行政法人情報通信研究機構 | Conductive nanowire manufacturing apparatus and manufacturing method |
| JP3877302B2 (en) * | 2002-06-24 | 2007-02-07 | 本田技研工業株式会社 | Method for forming carbon nanotube |
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| JP2005023408A (en) | 2005-01-27 |
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