JP4940392B2 - Method for producing carbon nanostructured material - Google Patents
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Description
本発明は、フィールドエミッションディスプレイの電子源のカソード電極やテレビの電子銃、エックス線発生源の電子銃、あるいはＳＰＭ（走査型プローブ顕微鏡）用のＳＴＭ（走査型トンネル顕微鏡）やＡＦＭ（原子間力顕微鏡）等の探針、微小な針、もしくはマニュピレータ用プローブに用いられるカーボンナノファイバやカーボンナノチューブであるカーボンナノ構造材の製造方法に関する。 The present invention relates to a cathode electrode of an electron source of a field emission display, an electron gun of a television, an electron gun of an X-ray generation source, or an STM (scanning tunnel microscope) or an AFM (atomic force microscope) for an SPM (scanning probe microscope). ) Or the like, a micro needle, or a carbon nanostructure material that is a carbon nanotube used for a manipulator probe.
フラットパネルディスプレイとして、液晶ディスプレイ（ＬＣＤ）やプラズマディスプレイ（ＰＤＰ）が実用化されているが、近年、これら以外にもフィールドエミッションディスプレイ（ＦＥＤ）が注目されている（例えば、非特許文献１参照。）。 As a flat panel display, a liquid crystal display (LCD) or a plasma display (PDP) has been put into practical use. In recent years, a field emission display (FED) has attracted attention in addition to these (for example, see Non-Patent Document 1). ).
図６は、フィールドエミッションディスプレイの画素を示す概略構成図である。図６に示すように、該ディスプレイの画素は、カーボンナノ構造材のカーボンナノファイバ１０３またはカーボンナノチューブを有するカソード側と、蛍光体１０５を有するアノード側とからなる。画素のカソード側は、ガラス基板１００上にカソード電極（陰極電極）１０１を設け、そのカソード電極１０１上にＦｅ、Ｃｏ、Ｎｉ、Ｐｔ等のいずれかの単膜あるいはそれらを主成分とする合金膜からなる触媒金属膜１０２を成膜して、該触媒金属膜１０２を触媒としてカソード電極１０１上に複数のカーボンナノファイバ１０３を成膜してなっている。画素のアノード側は、カソード電極１０１の前方側に配置したアノード電極（透明電極）１０４上に蛍光体１０５を塗布により設け、該蛍光体１０５上にガラス基板１０６を設けてなっている。カソード側とアノード側とは、カソード電極１０１とアノード電極１０４とが所定の隙間を有するように位置されるとともに、これらの間が所定の真空度に調整されている。 FIG. 6 is a schematic configuration diagram illustrating a pixel of the field emission display. As shown in FIG. 6, the pixel of the display includes a cathode side having carbon nanofibers 103 or carbon nanotubes of a carbon nanostructure material, and an anode side having a phosphor 105. On the cathode side of the pixel, a cathode electrode (cathode electrode) 101 is provided on a glass substrate 100, and a single film of Fe, Co, Ni, Pt or the like or an alloy film containing them as a main component is formed on the cathode electrode 101. A catalytic metal film 102 is formed, and a plurality of carbon nanofibers 103 are formed on the cathode electrode 101 using the catalytic metal film 102 as a catalyst. On the anode side of the pixel, a phosphor 105 is provided on an anode electrode (transparent electrode) 104 disposed on the front side of the cathode electrode 101 by coating, and a glass substrate 106 is provided on the phosphor 105. The cathode side and the anode side are positioned such that the cathode electrode 101 and the anode electrode 104 have a predetermined gap, and the space between them is adjusted to a predetermined degree of vacuum.
このカソード電極１０１とアノード電極１０４との間に電源１０７によって数ｋＶの電圧を印加すると、カーボンナノファイバ１０３の先端部の電界が高くなり、その先端部からトンネル効果で電子が放出され、放出された電子が加速されて前方のアノード電極１０４を通って蛍光材１０５に衝突し、蛍光材１０５を励起して蛍光材に応じた３原色のうちの１色の光を放出し発光する。かくして複数の画素によって３原色の色合いを調整した多用な色の所望の画像を再現する。図中、カーボンナノファイバの等電位面を点線で示す。 When a voltage of several kV is applied between the cathode electrode 101 and the anode electrode 104 by the power source 107, the electric field at the tip of the carbon nanofiber 103 is increased, and electrons are emitted from the tip by the tunnel effect and emitted. The electrons are accelerated and collide with the fluorescent material 105 through the anode electrode 104 in the front, and the fluorescent material 105 is excited to emit light of one of the three primary colors corresponding to the fluorescent material. In this way, a desired image of various colors in which the hues of the three primary colors are adjusted by a plurality of pixels is reproduced. In the figure, the equipotential surface of the carbon nanofiber is indicated by a dotted line.
ところで、カソード電極１０１上の多数本のカーボンナノファイバ１０３は、ファイバ１０３が密集し、ある程度高さが揃っていると、１本１本のファイバ１０３の電界強度が高くても、全体として電界が平滑化されて、個々のファイバ１０３の先端部周囲の等電位面が鋭角にならず、ファイバ１０３の先端部から電子が放出されづらくなる（この現象はシールディング効果と呼ばれている）。また図７に示すように、カーボンナノファイバ１０３の高さが多少異なっていても、ファイバ１０３が密集していると、ファイバ１０３の先端部の等電位面はやはり鋭角にならず、電子が放出されなくなる。またカーボンナノファイバ１０３は、１本１本単独で存在する場合もあるが、概ね複数本のファイバ１０３が束（バンドル状態）になっていることが多く、その場合、図８に示すように、複数本のファイバ１０３が絡まって先端部を形成するので、同様に電界が平滑化され、電子の放出が阻害される。 By the way, the multiple carbon nanofibers 103 on the cathode electrode 101 have a high density of fibers 103 and have a certain level of height. Even if the electric field strength of each fiber 103 is high, the electric field as a whole is large. As a result of the smoothing, the equipotential surface around the tip of each fiber 103 does not become an acute angle, and electrons are not easily emitted from the tip of the fiber 103 (this phenomenon is called the shielding effect). Further, as shown in FIG. 7, even if the heights of the carbon nanofibers 103 are slightly different, if the fibers 103 are densely packed, the equipotential surface at the tip of the fiber 103 does not become an acute angle, and electrons are emitted. It will not be done. In addition, the carbon nanofibers 103 may exist individually one by one, but generally a plurality of fibers 103 are often bundled (bundled state), in which case, as shown in FIG. Since a plurality of fibers 103 are entangled to form the tip portion, the electric field is similarly smoothed and the electron emission is inhibited.
このようなことから、本発明者らは、シリコン基板上にカーボンナノ構造材のカーボンナノファイバあるいはカーボンナノチューブを密集させずに１本１本バラけた疎の状態で得るべく、基板の表面に炭素皮膜を形成し、その炭素皮膜を形成した基板の表面に、図１に示すような成長装置を用いてイオンビームを照射して、炭素皮膜をカーボンナノ構造材に成長させる実験研究を数年前から行っている。 In view of the above, the present inventors have found that carbon nanofibers or carbon nanotubes of a carbon nanostructure material are not densely packed on a silicon substrate, so that carbon nanofibers or carbon nanotubes are separated from each other in a sparse state. Several years ago, an experimental study was conducted to grow a carbon film into a carbon nanostructure material by irradiating the surface of the substrate on which the carbon film was formed with an ion beam using a growth apparatus as shown in FIG. Is going from.
基板には、例えば直径４インチのシリコン基板を使用する。まず、このシリコン基板の表面に、アークイオンプレィティング法により厚さ０．１〜３μｍの炭素皮膜を予め形成して被覆する。その炭素皮膜を形成したシリコン基板を成長装置の基板ステージ３に搭載し、チャンバ５を閉じ、ロータリーポンプ７、ついでターボ分子ポンプ６でチャンバ１内を真空排気し、到達圧力が１×１０-5Ｔｏｒｒ以下に達したところで、マスフローコントローラ８を用いてイオン源２にアルゴンガスを導入し、イオン源２を作動させて、Ａｒイオンを０．３〜５ｋＶの加速電圧で引き出し、２２０μＡ／ｃｍ2程度以上のイオン電流密度でステージ３上の基板の表面にアルゴンイオンを照射する。イオン照射に先立って基板は、加熱ヒータ４で約２００℃まで加熱しておく。カーボンナノファイバの成長が可能な温度範囲は、室温〜１２００℃である。 For example, a silicon substrate having a diameter of 4 inches is used as the substrate. First, a carbon film having a thickness of 0.1 to 3 μm is formed in advance on the surface of the silicon substrate by an arc ion plating method. The silicon substrate on which the carbon film is formed is mounted on the substrate stage 3 of the growth apparatus, the chamber 5 is closed, the inside of the chamber 1 is evacuated by the rotary pump 7 and then the turbo molecular pump 6, and the ultimate pressure is 1 × 10 −5. When reaching below Torr, argon gas is introduced into the ion source 2 using the mass flow controller 8, the ion source 2 is operated, and Ar ions are extracted at an accelerating voltage of 0.3 to 5 kV, about 220 μA / cm 2. The surface of the substrate on the stage 3 is irradiated with argon ions at the above ion current density. Prior to ion irradiation, the substrate is heated to about 200 ° C. by the heater 4. The temperature range in which carbon nanofibers can be grown is from room temperature to 1200 ° C.
上記のイオン照射を１００分間程度行うと、図２に示すように、シリコン基板１０の表面に炭素皮膜からなる多数の微小な円錐状の突起（成長用の突起）１１が形成され、その各突起１１の頂部にナノカーボンが成長し、直径約数ｎｍ〜数１００ｎｍ、長さ０．１μｍ〜１０μｍのカーボンナノファイバ１２が１本ずつ形成される。かくして、基板１０上にカーボンナノファイバ１２を密集させずに１本１ずつバラけた疎の状態で得ることができる。 When the above ion irradiation is performed for about 100 minutes, as shown in FIG. 2, a large number of minute conical projections (growth projections) 11 made of a carbon film are formed on the surface of the silicon substrate 10, and each of the projections. Nanocarbon grows on the top of 11, and carbon nanofibers 12 having a diameter of about several nm to several hundred nm and a length of 0.1 μm to 10 μm are formed one by one. Thus, the carbon nanofibers 12 can be obtained in a sparse state in which the carbon nanofibers 12 are separated from each other without being densely packed on the substrate 10.
またＳＰＭ（走査型プローブ顕微鏡）用のＳＴＭ（走査型トンネル顕微鏡）やＡＦＭ（原子間力顕微鏡）等の探針には、探針用の突起上にカーボンナノファイバを形成して探針を構成することがある。図３のように、基板１０の表面にＳＰＭ用のＳＴＭやＡＦＭ等の探針用の突起１３を間隔を開けて予め多数形成しておき、その状態で基板１０の表面に炭素皮膜を形成し、上記のイオン照射を行うと、微小な成長用の突起１１の形成が、基板１０の平面部でなく、突起１３の頂部上に選択的に起こりやすく、さらにイオン照射を続けると、各突起１１の頂部にナノカーボンが成長する。これにより、基板１０上の探針用の突起１３に細いカーボンナノファイバ１２を１本ずつ形成することができる。 For probes such as STM (Scanning Tunneling Microscope) and AFM (Atomic Force Microscope) for SPM (Scanning Probe Microscope), carbon nanofibers are formed on the probe projections to configure the probe. There are things to do. As shown in FIG. 3, a large number of probe projections 13 such as SPM STM and AFM are formed in advance on the surface of the substrate 10 at intervals, and a carbon film is formed on the surface of the substrate 10 in that state. When the above ion irradiation is performed, the formation of the minute growth projections 11 is likely to occur selectively on the top of the projections 13 instead of the flat portion of the substrate 10. Nanocarbon grows on top of the surface. Thereby, the thin carbon nanofibers 12 can be formed one by one on the probe projection 13 on the substrate 10.
突起１３の大きさは、高さ約０．１〜５０μｍ、底辺の幅約０．０５〜２５μｍである。突起１３を形成するには、基板１０に対し半導体加工法を用いる。具体的には、フォトリソグラフィを用いてマスクを転写した後、シリコン基板であればアルカリ溶液、例えばＫＯＨ（水酸化カリウム）やＴＭＡＨ（tetramethyl ammonium hydroxide（テトラメチル水酸化アンモニウム））溶液でエッチング加工する。他の基板材料においても、ドライエッチングであるＲＩＥ（反応性イオンエッチング）やＩＰＣ（誘導結合型プラズマ）エッチングを用いて、基板上に突起を形成することが可能である。 The protrusion 13 has a height of about 0.1 to 50 μm and a bottom width of about 0.05 to 25 μm. In order to form the protrusion 13, a semiconductor processing method is used for the substrate 10. Specifically, after transferring the mask using photolithography, if it is a silicon substrate, it is etched with an alkaline solution such as KOH (potassium hydroxide) or TMAH (tetramethyl ammonium hydroxide) solution. . With other substrate materials, it is possible to form protrusions on the substrate using dry etching such as RIE (reactive ion etching) or IPC (inductively coupled plasma) etching.
図３において、符号１４は探針を保持する支持部を基板１０から切り離すための貫通孔で、カーボンナノファイバ１２を形成後に貫通孔１４のところで基板１０を切断して、探針用の突起１３を個々に分離するように使用する。分離用の貫通孔１４は、大きさが数十μｍ以上で、突起１３を形成したときと同様にアルカリ溶液またはドライエッチングを用いて基板１０に形成する。
上記したように、基板の表面にアークイオンプレィティング法で成膜した炭素皮膜をカーボンナノファイバの成長用に使用した場合、直径４インチの基板に対し２２０μＡ／ｃｍ2程度以上のイオン電流密度で約１００分のイオン照射を行わなければならず、イオン電流密度が大きい。このため、大型基板にカーボンナノファイバやカーボンナノチューブのカーボンナノ構造材を形成するには、大電流のイオン源が必要となる。 As described above, when a carbon film formed on the surface of the substrate by the arc ion plating method is used for the growth of carbon nanofibers, the ion current density is about 220 μA / cm 2 or more for a substrate having a diameter of 4 inches. Ion irradiation must be performed for about 100 minutes, and the ion current density is large. For this reason, a large current ion source is required to form carbon nanofibers or carbon nanostructures such as carbon nanotubes on a large substrate.
このような問題は、アーク蒸着法やＥＣＲプラズマＣＶＤ法等で成膜した炭素膜からカーボンナノファイバ等のカーボンナノ構造材を成長させる場合にも同様に確認されている。これらの方法で炭素膜を被覆した直径４インチの基板に、イオン電流密度約２２０μＡ／ｃｍ2、照射時間１００分の条件でイオン照射すると、カーボンナノ構造材を成長させることができる。したがって、大型基板にカーボンナノ構造材を形成させるには、同様に、大電流のイオン源が必要である。 Such a problem has also been confirmed in the case where a carbon nanostructure material such as carbon nanofiber is grown from a carbon film formed by an arc deposition method, an ECR plasma CVD method, or the like. When a 4-inch diameter substrate coated with a carbon film by these methods is irradiated with ions under the conditions of an ion current density of about 220 μA / cm 2 and an irradiation time of 100 minutes, a carbon nanostructure material can be grown. Therefore, in order to form a carbon nanostructure material on a large substrate, an ion source with a large current is required as well.
なお、上記のアークイオンプレィティングやアーク蒸着法、ＥＣＲプラズマＣＶＤ法等は、いずれも、非常に緻密で硬い炭素皮膜を得ることができる成膜方法である。このうちアークイオンプレィティング法やアーク蒸着法は、従来、主に工具のコーティングに用いられ、ＥＣＲプラズマＣＶＤ法は、主にハードディスクの保護膜の形成に用いられている。 The arc ion plating, the arc vapor deposition method, the ECR plasma CVD method, and the like are all film forming methods capable of obtaining a very dense and hard carbon film. Of these, the arc ion plating method and the arc vapor deposition method are conventionally mainly used for coating of tools, and the ECR plasma CVD method is mainly used for forming a protective film of a hard disk.
したがって、本発明の課題は、表面に炭素皮膜を形成した基板をイオン照射して、基板の表面に形成された各微小突起の頂部に１本ずつカーボンナノファイバを成長させて、基板上にカーボンナノファイバやカーボンナノチューブであるカーボンナノ構造材をバラけた疎の状態で得るに際し、基板の表面に形成する炭素皮膜を適切なものに選択することによって、低い電流密度のイオン照射によってナノ構造材を疎な状態で成長可能としたカーボンナノ構造材の製造方法を提供することである。 Accordingly, an object of the present invention is to irradiate a substrate having a carbon film on the surface with ions, to grow one carbon nanofiber on the top of each microprotrusion formed on the surface of the substrate, and to form carbon on the substrate. When carbon nanostructure materials such as nanofibers and carbon nanotubes are obtained in a loose and sparse state, by selecting an appropriate carbon film to be formed on the surface of the substrate, the nanostructure material can be obtained by ion irradiation at a low current density. The object is to provide a method for producing a carbon nanostructure material that can be grown in a sparse state.
上記課題を解決するために、本発明のカーボンナノ構造材の製造方法は、基板の表面にアクリロニトリル系、ピッチ系又はフェノール樹脂系の有機ポリマー溶液を塗布し、前記有機ポリマー溶液が塗布された基板を真空加熱炉で加熱処理して、前記基板の表面に炭素皮膜を形成し、前記炭素皮膜が形成された基板の表面に真空槽で、電流密度３０〜１５０μＡ／ｃｍ ２ でイオンビームを照射して、前記基板の表面に形成された多数の突起のそれぞれの頂部にカーボンナノファイバまたはカーボンナノチューブであるカーボンナノ構造材が１本成長した態様で、前記基板の表面にカーボンナノ構造材を形成することを特徴とする。 In order to solve the above-mentioned problems, the method for producing a carbon nanostructure material of the present invention includes applying a acrylonitrile-based, pitch-based or phenolic resin-based organic polymer solution to the surface of a substrate, and the substrate on which the organic polymer solution is applied. Is heated in a vacuum heating furnace to form a carbon film on the surface of the substrate, and the surface of the substrate on which the carbon film is formed is irradiated with an ion beam at a current density of 30 to 150 μA / cm 2 in a vacuum chamber. The carbon nanostructure material is formed on the surface of the substrate in such a manner that one carbon nanostructure material, which is a carbon nanofiber or a carbon nanotube, is grown on the top of each of the many protrusions formed on the surface of the substrate. It is characterized by that.
本発明によれば、前記有機ポリマー溶液はアクリロニトリル系重合体の溶液であり、前記重合体を基板の表面に塗布し、ついで前記基板を酸素含有雰囲気中で２００〜４００℃の温度で焼成して前記アクリロニトリル系重合体の塗膜を予備酸化処理し、ついで前記基板を不活性雰囲気中で少なくとも１０００℃の温度で焼成することによって前記塗膜を炭化処理して、前記基板の表面に炭素皮膜を形成するようにすることができる。もしくは、前記有機ポリマー溶液はピッチ溶液であり、前記ピッチ系溶液を基板の表面に塗布し、ついで前記基板を不活性ガス雰囲気中で３５０〜４５０℃の温度で加熱して前記ピッチの塗膜を炭化処理することによって、前記基板の表面に炭素皮膜を形成してもよい。あるいは、前記有機ポリマー溶液はレゾール型またはノボラック型のフェノール樹脂溶液であり、前記フェノール樹脂溶液を基板の表面に塗布し、ついで１５０℃の温度で加熱して硬化し、ついで前記基板を不活性雰囲気中で少なくとも１０００℃の温度で焼成することによって前記フェノール樹脂の塗膜を炭化処理して、前記基板の表面に炭素皮膜を形成するようにしてもよい。 According to the present invention, the organic polymer solution is an acrylonitrile-based polymer solution, the polymer is applied to the surface of the substrate, and then the substrate is baked at a temperature of 200 to 400 ° C. in an oxygen-containing atmosphere. The coating film of the acrylonitrile-based polymer is pre-oxidized, and then the coating film is carbonized by baking the substrate at a temperature of at least 1000 ° C. in an inert atmosphere to form a carbon coating on the surface of the substrate. Can be formed. Alternatively, the organic polymer solution is a pitch solution, and the pitch-based solution is applied to the surface of the substrate, and then the substrate is heated in an inert gas atmosphere at a temperature of 350 to 450 ° C. to form a coating film of the pitch. A carbon film may be formed on the surface of the substrate by carbonization treatment. Alternatively, the organic polymer solution is a resol-type or novolac-type phenol resin solution, and the phenol resin solution is applied to the surface of the substrate and then cured by heating at a temperature of 150 ° C., and then the substrate is inerted. In this case, the coating film of the phenol resin may be carbonized by baking at a temperature of at least 1000 ° C. to form a carbon film on the surface of the substrate.
また本発明によれば、炭素皮膜が形成された基板の表面に、真空アーク蒸着源により鉄、コバルト、モリブデン、ニッケル、パラジウムおよび白金のうちの少なくとも１種の原子またはイオンを膜厚１ｎｍ〜３００ｎｍで蒸着した後、もしくは蒸着と同時にイオンビームを照射するようにしてもよい。あるいは、基板表面に真空アーク蒸着源により鉄、コバルト、モリブデン、ニッケル、パラジウムおよび白金のうちの少なくとも１種を０．１〜５０．０原子％含むカーボン混合膜を蒸着した後、もしくは蒸着と同時にイオンビームを照射するようにしてもよい。 Further, according to the present invention, at least one atom or ion of iron, cobalt, molybdenum, nickel, palladium and platinum is deposited on the surface of the substrate on which the carbon film is formed by a vacuum arc deposition source in a film thickness of 1 nm to 300 nm. The ion beam may be irradiated after vapor deposition or simultaneously with vapor deposition. Alternatively, after a carbon mixed film containing 0.1 to 50.0 atomic% of at least one of iron, cobalt, molybdenum, nickel, palladium, and platinum is deposited on the substrate surface by a vacuum arc deposition source, or simultaneously with the deposition. You may make it irradiate an ion beam.
本発明では、炭素皮膜を形成した基板の表面にイオンビームを照射することによってカーボンナノファイバやカーボンナノチューブであるカーボンナノ構造材を形成するに際し、炭素皮膜をポリアクリロニトリル系溶液等の有機ポリマー溶液を用いて形成するので、イオンビームの照射を電流密度を低減して行っても、基板の表面に形成された多数の突起のそれぞれの頂部に１本のカーボンナノ構造材が成長した態様で、基板の表面にカーボンナノ構造材を得ることができる。したがって、大電流のイオン源を用いなくても、大型基板にカーボンナノ構造材を形成させることができる。 In the present invention, when forming a carbon nanostructure material such as carbon nanofiber or carbon nanotube by irradiating the surface of the substrate on which the carbon film is formed with an ion beam, the carbon film is coated with an organic polymer solution such as a polyacrylonitrile-based solution. Even if ion beam irradiation is performed at a reduced current density, a single carbon nanostructure material is grown on top of each of a large number of protrusions formed on the surface of the substrate. A carbon nanostructured material can be obtained on the surface. Therefore, a carbon nanostructure material can be formed on a large substrate without using a large current ion source.
また基板表面に、真空アーク蒸着源により鉄、コバルト、モリブデン、ニッケル、パラジウムおよび白金のうちの少なくとも１種の原子またはイオンを膜厚１ｎｍ〜３００ｎｍで蒸着し、あるいは、これらの金属元素の少なくとも１種を０．１〜５０．０原子％含むカーボン混合膜を蒸着し、蒸着後もしくは蒸着と同時にイオンビームを照射する場合には、金属微粒子によって炭素原子の拡散が制御されるので、基板上への突起の形成速度の速い遅いを調節できることから、突起の形成速度を制御することにより、結果としてカーボンナノ構造材の成長を調節することができ、カーボンナノ構造材の長さ、太さ、数、および密度を制御することができる。 Further, at least one atom or ion of iron, cobalt, molybdenum, nickel, palladium and platinum is deposited on the substrate surface with a film thickness of 1 nm to 300 nm by a vacuum arc deposition source, or at least one of these metal elements. When a carbon mixed film containing 0.1 to 50.0 atomic percent of the seed is deposited and irradiated with an ion beam after the deposition or simultaneously with the deposition, the diffusion of carbon atoms is controlled by the metal fine particles. As a result, the growth of carbon nanostructure material can be controlled by controlling the formation speed of the protrusion, and the length, thickness, number of carbon nanostructure material can be adjusted. , And the density can be controlled.
以下、本発明の実施形態について説明する。本発明は、炭素皮膜が形成された基板の表面に真空槽でイオンビームを照射することによって、基板の表面に形成されたそれぞれの突起の頂部に、カーボンナノ構造材のカーボンナノファイバあるいはカーボンナノチューブを１本ずつ成長させて、基板の表面にカーボンナノ構造材を１本１本バラけた疎な状態で形成するものである。本発明では、そのイオンビーム照射の電流密度を低くしても、基板表面にカーボンナノ構造材を疎な状態で形成させるために、基板表面にアークイオンプレィティングやアーク蒸着法、ＥＣＲプラズマＣＶＤ法によってではなく、有機ポリマー溶液によって炭素皮膜を形成することが大きな特徴である。 Hereinafter, embodiments of the present invention will be described. In the present invention, a carbon nanofiber or carbon nanotube of a carbon nanostructure material is formed on the top of each protrusion formed on the surface of the substrate by irradiating the surface of the substrate on which the carbon film is formed with an ion beam in a vacuum chamber. Are grown one by one to form a carbon nanostructure material in a sparse state on the surface of the substrate. In the present invention, in order to form a carbon nanostructure material in a sparse state on the substrate surface even when the ion beam irradiation current density is lowered, arc ion plating, arc vapor deposition, or ECR plasma CVD is performed on the substrate surface. The main feature is that the carbon film is formed by the organic polymer solution rather than by the above.
本発明において、有機ポリマー溶液としては、炭素繊維等の素材となるものが使用でき、アクリロニトリル系、ピッチ系、フェノール樹脂系の溶液を使用する。 In the present invention, as the organic polymer solution, a material such as carbon fiber can be used , and an acrylonitrile-based, pitch-based, or phenolic resin-based solution is used.
アクリロニトリル系溶液は、アクリロニトリル系重合体を有機溶媒に溶解したもので、紡糸によってアクリル繊維を得ることができる前駆体（プリカーサ）である。アクリロニトリル系重合体としては、アクリロニトリル単量体の繰り返し単位からなるものの他、これと共重合可能なオレフィン単量体とからなる繰り返し単位からなるものであってもよい。アクリロニトリルの製造法としては、いくつかの方法が知られているが、プロピレンとアンモニアとを空気中で酸化的に反応させることにより、メチル基をシアノ基に変換するアンモ酸化法（ソハイオ法）によって、工業的に大量に製造されている。 The acrylonitrile-based solution is a precursor (precursor) in which an acrylonitrile-based polymer is dissolved in an organic solvent and acrylic fibers can be obtained by spinning. The acrylonitrile-based polymer may be composed of a repeating unit composed of a repeating unit of an acrylonitrile monomer or an olefin monomer copolymerizable therewith. There are several known methods for producing acrylonitrile, but by an ammoxidation method (Sohio method) in which a methyl group is converted to a cyano group by oxidative reaction of propylene and ammonia in air. It is manufactured in large quantities industrially.
アクリロニトリルと共重合可能なオレフィン単量体としては、例えばアクリル酸、メタクリル酸およびそれらのエステル、アクリルアミド、酢酸ビニル、スチレン、塩化ビニル、塩化ビニリデン、無水マレイン酸、Ｎ−置換マレインイミド、ブタジエン、イソブレン等を挙げることができる。アクリロニトリル系重合体を溶解する有機溶媒としては、ジメチルホルムアルデヒド、ジメチルアセトアミド、ジメチルスルフォキシド等を好ましく使用することができる。アクリロニトリル系重合体と有機溶媒との割合は、アクリロニトリル系重合体５〜３５重量％に対し有機溶媒９５〜６５重量％とすることが好ましい。 Examples of the olefin monomer copolymerizable with acrylonitrile include acrylic acid, methacrylic acid and esters thereof, acrylamide, vinyl acetate, styrene, vinyl chloride, vinylidene chloride, maleic anhydride, N-substituted maleimide, butadiene, and isobrene. Etc. As the organic solvent for dissolving the acrylonitrile-based polymer, dimethylformaldehyde, dimethylacetamide, dimethylsulfoxide and the like can be preferably used. The ratio of the acrylonitrile polymer and the organic solvent is preferably 95 to 65% by weight of the organic solvent with respect to 5 to 35% by weight of the acrylonitrile polymer.
このアクリロニトリル系溶液を基板の表面に炭化後の膜厚が約０．１〜３μｍとなる量で、滴下法またはスピナー等によって塗布し、ついで基板を加熱炉に入れて酸素含有雰囲気中で２００〜４００℃の温度で３〜４分間焼成し、アクリロニトリルの塗膜を予備酸化処理（耐炎化）する。ついで基板を焼成炉に入れて窒素ガス等の不活性雰囲気中で少なくとも１０００℃の温度で焼成して塗膜を炭化処理し、基板の表面に炭化または黒鉛化した炭素皮膜を得る。 This acrylonitrile-based solution is applied to the surface of the substrate in an amount such that the film thickness after carbonization is about 0.1 to 3 μm by a dropping method or a spinner, and then the substrate is placed in a heating furnace to be 200 to 200 in an oxygen-containing atmosphere. Baking is performed at a temperature of 400 ° C. for 3 to 4 minutes, and the acrylonitrile coating film is pre-oxidized (flame resistance). Next, the substrate is placed in a baking furnace and baked at a temperature of at least 1000 ° C. in an inert atmosphere such as nitrogen gas to carbonize the coating film to obtain a carbonized or carbonized carbon film on the surface of the substrate.
ピッチ系溶液としては、コールタールピッチや石油系ピッチ等が挙げられる。より具体的には、石炭系のコールタール、コールタールピッチ、石炭液化物、石油系のピッチ、例えばＦＣＣオイル、コーカーオイルまたはそれらの蒸留残渣、またはナフタレン、アントラセンを、触媒やホルマリン誘導体で重縮合反応させ製造した芳香族樹脂、あるいはアルキルベンゼンを強酸性触媒下でホルムアルデヒド類を架橋したオリゴマーを加熱−減圧蒸留し製造したピッチを好ましく使用することができる。 Examples of the pitch-based solution include coal tar pitch and petroleum-based pitch. More specifically, coal-based coal tar, coal tar pitch, coal liquefaction, petroleum-based pitch, such as FCC oil, coker oil or their distillation residue, or naphthalene, anthracene are polycondensed with a catalyst or formalin derivative. A pitch produced by heating-vacuum distillation of an aromatic resin produced by reaction or an oligomer obtained by crosslinking formaldehyde with alkylbenzene in a strongly acidic catalyst can be preferably used.
このピッチ系溶液を基板の表面に炭化後の膜厚が約０．１〜３μｍとなる量で塗布し、基板を加熱炉に入れ不活性雰囲気中で２００〜４００℃の温度で１〜６時間焼成してピッチの塗膜を炭化処理し、基板の表面に炭素皮膜を得る。 This pitch-based solution is applied to the surface of the substrate in such an amount that the film thickness after carbonization is about 0.1 to 3 μm, and the substrate is placed in a heating furnace at a temperature of 200 to 400 ° C. in an inert atmosphere for 1 to 6 hours. Baking and carbonizing the pitch coating film to obtain a carbon coating on the surface of the substrate.
フェノール系樹脂溶液としては、レゾール型、ノボラック型のフェノール樹脂を好ましく用いることでき、これらは有機溶媒に溶解して使用する。レゾール樹脂（レゾール型フェノール樹脂）は液状のフェノール樹脂で、水酸化ナトリウム、アンモニアまたは有機アミンのような塩基性触媒（約０．２〜２％）の存在下で、フェノールとホルムアルデヒドをモル比１対１〜２のホルムアルデヒド過剰の条件下で反応することによって得られる。ノボラック樹脂（ノボラック型フェノール樹脂）は、例えばシュウ酸のような酸触媒（約０．２〜２％）の存在下で、フェノールとホルムアルデヒドをモル比１対０．７〜０．９のフェノール過剰の条件下で反応することによって得られる。これらのフェノール樹脂は、アルコール、エーテル、エステル、ケトン、アミド等の有機溶媒に溶解して使用する。好ましくは、メタノール、エタノール、ブタノール、プロパノール等のアルコールがよい。 As the phenolic resin solution, a resol-type or novolac-type phenol resin can be preferably used, and these are used by dissolving in an organic solvent. Resol resin (resole type phenolic resin) is a liquid phenolic resin in which phenol and formaldehyde have a molar ratio of 1 in the presence of a basic catalyst (about 0.2-2%) such as sodium hydroxide, ammonia or organic amine. It is obtained by reacting under conditions of excess formaldehyde to 1-2. A novolak resin (novolak-type phenol resin) is an excess of phenol and formaldehyde in a molar ratio of 1: 0.7 to 0.9 in the presence of an acid catalyst (about 0.2 to 2%) such as oxalic acid. It can be obtained by reacting under the following conditions. These phenol resins are used by being dissolved in an organic solvent such as alcohol, ether, ester, ketone, amide or the like. Preferably, alcohols such as methanol, ethanol, butanol, and propanol are used.
このフェノール系樹脂溶液を基板の表面に炭化後の膜厚が約０．１〜３μｍとなる量で塗布し、基板を加熱炉に入れて１５０℃の温度で加熱してフェノール樹脂の塗膜を硬化し、ついで基板を不活性雰囲気中で少なくとも１０００℃の温度で焼成して塗膜を炭化処理し、基板の表面に炭素皮膜を得る。 The phenolic resin solution is applied to the surface of the substrate in such an amount that the film thickness after carbonization is about 0.1 to 3 μm, and the substrate is placed in a heating furnace and heated at a temperature of 150 ° C. to form a phenolic resin coating film. Then, the substrate is baked at a temperature of at least 1000 ° C. in an inert atmosphere to carbonize the coating to obtain a carbon coating on the surface of the substrate.
基板としてはシリコン基板等を使用することができる。基板の表面に有機ポリマー溶液で炭素皮膜を形成したら、その基板の表面にイオンビームを照射して、基板表面にカーボンナノ構造材を形成させる。本発明では、炭素皮膜を有機ポリマー溶液を用いて形成しているので、イオンビームは低電流密度の照射でよく、低電流密度のイオンビーム照射によって、図２に模式的に示すように、基板１０の表面に炭素皮膜からなる高さ約０．５μｍ〜２μｍの円錐状の微小突起１１が約０．２〜３０μｍの間隔で多数形成され、その各突起１１の頂部から１本ずつカーボンナノファイバ１２が成長して、基板１０の表面にカーボンナノファイバ１２が長さが不揃いで１本１本バラけた疎の状態で形成される。 A silicon substrate or the like can be used as the substrate. After the carbon film is formed with the organic polymer solution on the surface of the substrate, the surface of the substrate is irradiated with an ion beam to form a carbon nanostructure material on the surface of the substrate. In the present invention, since the carbon film is formed using the organic polymer solution, the ion beam may be irradiated with a low current density, and the substrate is formed by the low current density ion beam irradiation as schematically shown in FIG. A large number of conical microprotrusions 11 having a height of about 0.5 μm to 2 μm made of a carbon film are formed on the surface of 10 at intervals of about 0.2 to 30 μm. 12 grows, and carbon nanofibers 12 are formed on the surface of the substrate 10 in a sparse state in which the lengths are not uniform and are separated one by one.
イオン照射の電流密度としては、３０〜１５０μＡ／ｃｍ２、好ましくは５０〜１００μＡ／ｃｍ２程度がよい。照射時間としては、限定するものではないが、３〜１５０分、好ましくは１５〜１００分程度である。 The current density of the ion irradiation, 30~150μA / cm 2, preferably not good about 50~100μA / cm 2. Although it does not limit as irradiation time, It is 3 to 150 minutes, Preferably it is about 15 to 100 minutes.
本発明によれば、基板の表面にイオンビームを照射するに先立って、真空アーク蒸着源により鉄、コバルト、モリブデン、ニッケル、パラジウムおよび白金のうちの少なくとも１種の原子またはイオンを膜厚１ｎｍ〜３００ｎｍで蒸着し、あるいは、これらの金属元素の少なくとも１種を０．１〜５０．０原子％含むカーボン混合膜を蒸着し、この蒸着後もしくは蒸着と同時にイオンビームを照射することができる。これによれば、金属微粒子によって炭素原子の拡散が制御されるので、基板上への突起の形成速度の速い遅いを制御できるので、その形成速度を制御することにより、カーボンナノファイバの成長を調節することができ、カーボンナノファイバの長さ、太さ、数、密度を制御することができる。以上はカーボンナノチューブについても同様である。 According to the present invention, prior to irradiating the surface of the substrate with the ion beam, the vacuum arc deposition source is used to deposit at least one atom or ion of iron, cobalt, molybdenum, nickel, palladium, and platinum in a film thickness of 1 nm to 1 nm. Vapor deposition can be performed at 300 nm, or a carbon mixed film containing 0.1 to 50.0 atomic% of at least one of these metal elements can be deposited, and an ion beam can be irradiated after or at the same time as the deposition. According to this, since the diffusion of carbon atoms is controlled by the metal microparticles, it is possible to control the slow and fast formation of protrusions on the substrate, so the growth of carbon nanofibers can be controlled by controlling the formation speed. The length, thickness, number and density of the carbon nanofibers can be controlled. The same applies to the carbon nanotubes.
図１に、本発明でカーボンナノ構造材の形成に使用する成長装置を示す。図は、チャンバの上下壁および前側を含む周囲壁の一部を除いて示してある。 FIG. 1 shows a growth apparatus used for forming a carbon nanostructure material in the present invention. The figure is shown except for a portion of the surrounding wall including the upper and lower walls and the front side of the chamber.
本成長装置は、アークプラズマガン１と、イオン源２と、基板ステージ３と、加熱ヒータ４とを有するチャンバ５を備え、チャンバ５にはターボ分子ポンプ６と、これに直列接続したロータリーポンプ７とが取付けられ、イオン源２には、ガス導入用マスフローコントローラ８を介して図示しないアルゴンガスボンベが接続されている。アークプラズマガン１とイオン源２とは、中心軸線を基板ステージ３に向けてチャンバ５の対向位置の側壁に４５°の角度で取付けられている。基板ステージ３はチャンバ１の中央下部に設置され、該ステージ４に載せた基板の法線方向にアークプラズマガン１とイオン源２が位置するように、水平に対し±４５°の角度でチルト可能になっている。本発明では、上記したように、基板の表面にポリマー溶液を塗布して炭素皮膜を形成するようになっており、アークプラズマガン１は、炭素皮膜上に蒸着触媒皮膜を形成するアーク蒸着源として使用する。図中、９はイオン源２のアルゴンイオン出口の前方に配置したファラデーカップ（フルエンス測定器）である。 This growth apparatus includes a chamber 5 having an arc plasma gun 1, an ion source 2, a substrate stage 3, and a heater 4. The chamber 5 includes a turbo molecular pump 6 and a rotary pump 7 connected in series to the turbo molecular pump 6. And an argon gas cylinder (not shown) is connected to the ion source 2 via a gas introduction mass flow controller 8. The arc plasma gun 1 and the ion source 2 are attached to the side wall at the opposite position of the chamber 5 at an angle of 45 ° with the central axis directed toward the substrate stage 3. The substrate stage 3 is installed at the lower center of the chamber 1 and can be tilted at an angle of ± 45 ° with respect to the horizontal so that the arc plasma gun 1 and the ion source 2 are positioned in the normal direction of the substrate placed on the stage 4. It has become. In the present invention, as described above, a polymer solution is applied to the surface of the substrate to form a carbon film, and the arc plasma gun 1 serves as an arc vapor deposition source for forming a vapor deposition catalyst film on the carbon film. use. In the figure, 9 is a Faraday cup (fluence measuring device) arranged in front of the argon ion outlet of the ion source 2.
表面に厚さ約０．１〜３μｍの炭素皮膜を形成したシリコン基板を装置１の基板ステージ３に搭載し、チャンバ５を閉じ、ロータリーポンプ７、ついでターボ分子ポンプ６でチャンバ５内を真空排気し、到達圧力が１×１０-5Ｔｏｒｒ以下に達したところで、マスフローコントローラ８を用いてイオン源２にアルゴンガスを導入し、イオン源２を作動させて、Ａｒイオンを０．３〜５ｋＶの加速電圧で引き出し、ステージ３上の加熱ヒータ４で室温〜約１２００℃まで加熱した基板の表面に所定の電流密度でイオンを照射する。これによって、基板の表面にカーボンナノファイバが形成される。 A silicon substrate having a carbon film with a thickness of about 0.1 to 3 μm formed on the surface is mounted on the substrate stage 3 of the apparatus 1, the chamber 5 is closed, and the inside of the chamber 5 is evacuated by the rotary pump 7 and then the turbo molecular pump 6. Then, when the ultimate pressure reaches 1 × 10 −5 Torr or less, argon gas is introduced into the ion source 2 using the mass flow controller 8 and the ion source 2 is operated to make Ar ions 0.3 to 5 kV. The substrate is heated at room temperature to about 1200 ° C. with the heater 4 on the stage 3 and is radiated with ions at a predetermined current density. Thereby, carbon nanofibers are formed on the surface of the substrate.
上記製造方法により製造されたカーボンナノファイバまたはカーボンナノチューブは、フィールドエミッションディスプレイの電子源のカソード電極として、あるいは走査型プローブ顕微鏡用の探針として適用可能である。 The carbon nanofiber or carbon nanotube produced by the above production method can be applied as a cathode electrode of an electron source of a field emission display or a probe for a scanning probe microscope.
フィールドエミッションディスプレイの電子源のカソード電極として用いる場合には、基板上にカーボンナノファイバまたはカーボンナノチューブを密集させずに、１本１本を疎の状態で形成できるため、電子放出効率を著しく向上させることができる。 When used as a cathode electrode of an electron source of a field emission display, each one can be formed in a sparse state without concentrating carbon nanofibers or carbon nanotubes on a substrate, thereby significantly improving electron emission efficiency. be able to.
走査型プローブ顕微鏡用探針としては、シリコン基板上の微小突起に選択的にカーボンナノファイバまたはカーボンナノチューブを成長させることができるため、カーボンナノファイバまたはカーボンナノチューブ探針をバッチ処理で容易に製造することができる。そのため低コスト化が実現できるとともに、従来の接着法とは異なり、突起部より直接成長させることができるため、高耐久性で高アスペクト比の探針が形成可能となる。 As a probe for a scanning probe microscope, carbon nanofibers or carbon nanotubes can be selectively grown on microprojections on a silicon substrate, so that carbon nanofibers or carbon nanotube probes are easily manufactured by batch processing. be able to. Therefore, it is possible to reduce the cost, and unlike the conventional bonding method, it is possible to grow directly from the protruding portion, so that a highly durable and high aspect ratio probe can be formed.
本発明の実施例について説明する。 Examples of the present invention will be described.
実施例１
有機ポリマー溶液として、アクリロニトリル重合体であるレジスト液（クラリアントジャパン（株）製ＡＺ Ｐ１３５０（粘度４．２ｃｐ））を使用し、これを直径４インチのシリコン基板の一方の表面全体にスポイトで滴下し塗布した。この基板を赤外線加熱方式の真空乾燥炉（アルバック理工（株）製ＲＴＡ−６）のチャンバに入れ、ロータリーポンプで真空引きをしながらチャンバ内圧力が１〜２Ｐａになったところで、基板を４５０℃で１５分間焼成した。得られる膜厚を厚くするために、このレジストの塗布と焼成のプロセスを３回繰返して、基板の表面にアクリロニトリルの焼成炭素膜が膜厚約３μｍで形成された。
Example 1
As the organic polymer solution, an acrylonitrile polymer resist solution (AZ P1350 (viscosity: 4.2 cp) manufactured by Clariant Japan Co., Ltd.) is used, and this is dropped onto one whole surface of a 4-inch diameter silicon substrate with a dropper. Applied. This substrate was put into a chamber of an infrared heating type vacuum drying furnace (RTA-6 manufactured by ULVAC-RIKO), and when the pressure in the chamber became 1 to 2 Pa while evacuating with a rotary pump, the substrate was placed at 450 ° C. Baked for 15 minutes. In order to increase the film thickness obtained, this resist coating and baking process was repeated three times to form a baked carbon film of acrylonitrile with a film thickness of about 3 μm on the surface of the substrate.
図１の装置を使用して、アクリロニトリルの炭素皮膜が形成された基板の表面に電流密度約７０μＡ／ｃｍ2で１００分間のイオン照射を行ったところ、基板表面にカーボンナノファイバをバラけた状態で得ることができた。得られた基板表面のカーボンナノファイバのＳＥＭ（走査型電子顕微鏡）写真を図４に示す。 Using the apparatus of FIG. 1, when ion irradiation was performed for 100 minutes at a current density of about 70 μA / cm 2 on the surface of the substrate on which the acrylonitrile carbon film was formed, carbon nanofibers were scattered on the surface of the substrate. I was able to get it. FIG. 4 shows an SEM (scanning electron microscope) photograph of the obtained carbon nanofibers on the surface of the substrate.
実施例２
基板の表面にイオン照射をする前に、基板表面の炭素皮膜上に鉄含有の蒸着皮膜を形成した他は、実施例１と同様にした。その結果、電流密度約７０μＡ／ｃｍ2で１００分間のイオン照射によって、基板の表面に実施例１と同様なカーボンナノファイバを得ることができた。
Example 2
Example 1 was performed except that an iron-containing vapor deposition film was formed on the carbon film on the surface of the substrate before ion irradiation was performed on the surface of the substrate. As a result, carbon nanofibers similar to those in Example 1 could be obtained on the surface of the substrate by ion irradiation for 100 minutes at a current density of about 70 μA / cm 2 .
実施例３
シリコン基板として、図３に示す探針用の突起および分離用の貫通孔を形成した基板を使用した。基板の突起（高さ１５μｍ）を形成した凹凸表面に、実施例１で使用したのと同じレジスト液を１μｍ以下の膜厚で塗布し、実施例１と同様にして焼成して、基板の表面に凹凸を埋めた凹凸のない炭素皮膜を形成した。続いて、基板の炭素皮膜を形成した表面に、鉄を１０原子％含むカーボンの混合膜を蒸着しつつ、電流密度約１００μＡ／ｃｍ2で６０分間のイオン照射を行い、基板上の探針用の突起に、成長用の突起を介してカーボンナノファイバが１本の割りで形成され、より低い電流密度および少ないイオン照射時間で、効率的にカーボンナノファイバを形成することができた。得られた基板表面のカーボンナノファイバのＳＥＭ写真を図５に示す。
Example 3
As the silicon substrate, the substrate in which the probe protrusions and the separation through holes shown in FIG. 3 were formed was used. The same resist solution as used in Example 1 was applied to the uneven surface on which the protrusions (15 μm in height) of the substrate were formed in a film thickness of 1 μm or less, and baked in the same manner as in Example 1 to obtain the surface of the substrate. A carbon film without unevenness was formed by filling the unevenness in the surface. Subsequently, while depositing a carbon mixed film containing 10 atomic% of iron on the surface of the substrate on which the carbon film is formed, ion irradiation is performed for 60 minutes at a current density of about 100 μA / cm 2 for the probe on the substrate. Carbon nanofibers were formed on each of the protrusions by a growth protrusion, and carbon nanofibers could be efficiently formed with a lower current density and a shorter ion irradiation time. An SEM photograph of the carbon nanofibers on the obtained substrate surface is shown in FIG.
なお、イオン照射は、Ａｒイオンに限定されるものではなく、Ｎｅ（ネオン）、Ｘｅ（キセノン）等の希ガスイオン、Ｎ（窒素）、Ｃ（炭素）を含む反応性イオンであってもよい。 The ion irradiation is not limited to Ar ions, and may be reactive ions including rare gas ions such as Ne (neon) and Xe (xenon), N (nitrogen), and C (carbon). .
１ アークプラズマガン ２ イオン源
３ 基板ステージ ４ 加熱ヒータ
５ チャンバ ８ マスフローコントローラ
９ ファラデーカップ １０ 基板
１１ 成長用の突起 １２ カーボンナノファイバ
１３ 探針用の突起
DESCRIPTION OF SYMBOLS 1 Arc plasma gun 2 Ion source 3 Substrate stage 4 Heater 5 Chamber 8 Mass flow controller 9 Faraday cup 10 Substrate 11 Growth protrusion 12 Carbon nanofiber 13 Protrusion for probe
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| JP2012047539A (en) * | 2010-08-25 | 2012-03-08 | Hitachi High-Technologies Corp | Spm probe and light emitting portion inspection apparatus |
| CN102126718B (en) * | 2011-04-07 | 2013-07-17 | 刘剑洪 | Method for preparing carbon nano tubes and carbon micro tubes |
| JP2014234339A (en) * | 2013-06-05 | 2014-12-15 | 日立造船株式会社 | Carbon nanotube sheet and method for producing carbon nanotube sheet |
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