JP2005089738A - Carbon nanotube dispersion solution and carbon nanotube dispersion material - Google Patents
Carbon nanotube dispersion solution and carbon nanotube dispersion material Download PDFInfo
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本発明は、共役系重合体が付着したカーボンナノチューブが溶媒中に分散されてなる溶液、及び該溶液より得られるカーボンナノチューブ分散体に関する。 The present invention relates to a solution in which carbon nanotubes to which a conjugated polymer is attached are dispersed in a solvent, and a carbon nanotube dispersion obtained from the solution.
カーボンナノチューブ（以下、ＣＮＴと言う）はナノテクノロジーの有力な素材として、広範な分野で応用の可能性が検討されている。用途としてはトランジスターや顕微鏡用プローブなどのようにＣＮＴの単線を使用する方法と、電子放出電極や燃料電池用電極、あるいはＣＮＴを分散した導電性コンポジットなどのように多数のＣＮＴをまとめてバルクとして使用する方法等がある。単線で使用する場合は、ＣＮＴを溶媒中で超音波を照射した後、電気泳動などで単一に分散しているＣＮＴのみを取り出すなどの方法が用いられる。バルクで用いる場合にはＣＮＴが溶剤やマトリックス材となる材質、例えば重合体の溶液などに良好に分散できることが必須であるが、一般にＣＮＴは溶媒に分散しにくいという問題がある。このためＣＮＴ表面の改質、化学修飾などによって分散性を向上する方法が種々検討されている。 Carbon nanotubes (hereinafter referred to as CNT) are considered as potential materials for nanotechnology, and their application possibilities are being studied in a wide range of fields. Applications include the use of CNT single wires such as transistors and microscope probes, and a large number of CNTs in bulk, such as electron emission electrodes, fuel cell electrodes, or conductive composites with dispersed CNTs. There are methods to use. When using a single wire, after irradiating ultrasonic waves in a solvent with CNTs, a method of taking out only CNTs dispersed in a single manner by electrophoresis or the like is used. When used in bulk, it is essential that CNTs can be well dispersed in a material that serves as a solvent or a matrix material, such as a polymer solution. However, in general, CNTs are difficult to disperse in a solvent. For this reason, various methods for improving the dispersibility by modifying the CNT surface, chemical modification, and the like have been studied.
ＣＮＴの分散性を向上させる方法としては、ＣＮＴをドデシルスルホン酸ナトリウムなどの界面活性剤を含有する水溶液に入れる方法（例えば、特許文献１参照）があるが、ＣＮＴ表面に非導電性の有機物が付着するとＣＮＴの導電性や半導体特性が損なわれる。また、ＣＮＴ表面をコイル状構造のポリマーであるポリ−ｍ−フェニレンビニレン−ｃｏ−ジオクトキシ−ｐ−フェニレンビニレン（ＰｍＰＶ）で覆うことによってＣＮＴの分散性を高める方法（例えば、特許文献２参照）が提案されているが、該ポリマーは共役系が不完全なため、ＣＮＴの導電性や半導体特性を低下する。ＣＮＴとの間で電荷の移動が容易な共役系重合体の溶液にＣＮＴが分散しやすいことを利用して共役系重合体にＣＮＴを分散させる方法も提案されている（例えば、特許文献３参照）が、共役系重合体中で電荷の移動の過程で導電性や半導体特性が低下する。 As a method for improving the dispersibility of CNTs, there is a method of putting CNTs in an aqueous solution containing a surfactant such as sodium dodecyl sulfonate (see, for example, Patent Document 1). If attached, the conductivity and semiconductor characteristics of the CNT are impaired. Further, there is a method for enhancing the dispersibility of CNT by covering the CNT surface with poly-m-phenylene vinylene-co-dioctoxy-p-phenylene vinylene (PmPV) which is a polymer having a coiled structure (for example, see Patent Document 2). Although proposed, the polymer has an incomplete conjugated system, which deteriorates the conductivity and semiconductor properties of the CNT. A method has also been proposed in which CNTs are dispersed in a conjugated polymer by utilizing the fact that CNTs are easily dispersed in a solution of a conjugated polymer that allows easy transfer of charge to and from CNTs (see, for example, Patent Document 3). ), However, the conductivity and semiconductor properties deteriorate in the process of charge transfer in the conjugated polymer.
さらには、ＣＮＴに官能基を付加させる等の方法により表面に化学修飾を施し分散性を付与した上で使用されたものがある（例えば、非特許文献１参照）が、ＣＮＴに化学修飾を施すとＣＮＴを構成するπ共役系が破壊されやすく、ＣＮＴ本来の特性が損なわれる。ＣＮＴを基板上に直接成長させる方法もある（例えば、非特許文献２）が、ＣＮＴの生成には７００℃程度の熱処理が必要となる。
従来の技術では、ＣＮＴの溶液に対する分散性向上をはかるため、ＣＮＴの表面を改質すると本来のＣＮＴの特性、たとえば高導電性や半導体特性が損なわれるという問題が生じていた。そこで本発明は上記問題点を解決すべく、ＣＮＴの高導電性や半導体特性を維持しながら、溶剤への分散性に優れたＣＮＴ、そのＣＮＴを有するＣＮＴ分散溶液、及び該溶液によって得られるＣＮＴ分散体を提供する。 In the conventional technique, in order to improve the dispersibility of the CNT in the solution, there has been a problem that the properties of the original CNT, for example, high conductivity and semiconductor properties are impaired when the surface of the CNT is modified. Therefore, in order to solve the above problems, the present invention maintains CNTs with high conductivity and semiconductor characteristics, and has excellent dispersibility in a solvent, a CNT dispersion solution containing the CNTs, and a CNT obtained by the solution. Provide a dispersion.
上記課題を達成するために、本発明は下記の構成からなる。
（１）カーボンナノチューブと溶媒を有するカーボンナノチューブ分散溶液であって、カーボンナノチューブの少なくとも一部に共役系重合体が付着し、カーボンナノチューブが溶媒中に分散しているカーボンナノチューブ分散溶液。
（２）カーボンナノチューブの少なくとも一部に共役系重合体を付着させる工程と、共役系重合体が付着したカーボンナノチューブを該共役系重合体が可溶な溶媒で洗浄する工程と、上記工程によって得られたカーボンナノチューブを溶媒に溶解させる工程とを有する（１）記載のカーボンナノチューブ分散溶液の製造方法。
（３）上記（１）のカーボンナノチューブ分散溶液を塗布することによって形成されるＣＮＴ分散体である。
In order to achieve the above object, the present invention comprises the following constitution.
(1) A carbon nanotube dispersion solution having carbon nanotubes and a solvent, wherein the conjugated polymer is attached to at least a part of the carbon nanotubes, and the carbon nanotubes are dispersed in the solvent.
(2) A step of attaching a conjugated polymer to at least a part of the carbon nanotubes, a step of washing the carbon nanotubes attached with the conjugated polymer with a solvent in which the conjugated polymer is soluble, and the above steps. And a step of dissolving the obtained carbon nanotubes in a solvent.
(3) A CNT dispersion formed by applying the carbon nanotube dispersion solution of (1) above.
本発明によれば、ＣＮＴを溶液に均一に分散させることができ、そこで得られたＣＮＴ分散溶液を用いることによって、ＣＮＴ自身が本来有する高導電性と優れた半導体特性を持つ分散体を、高温を必要とせず室温で形成することができる。また、本発明によれば、ＣＮＴ分散体の膜厚を均一に形成できることから、ＣＮＴ分散体膜を電子放出源とした電子放出素子を得ることができ、またＣＮＴ分散体の膜厚を薄くすることで、透明導電体を得ることができる。 According to the present invention, CNT can be uniformly dispersed in a solution. By using the obtained CNT dispersion solution, a dispersion having high conductivity inherent in CNT itself and excellent semiconductor characteristics can be obtained at a high temperature. Can be formed at room temperature. Further, according to the present invention, since the film thickness of the CNT dispersion can be formed uniformly, an electron-emitting device using the CNT dispersion film as an electron emission source can be obtained, and the film thickness of the CNT dispersion can be reduced. Thus, a transparent conductor can be obtained.
本発明は、共役系重合体が少なくとも一部に付着したＣＮＴを溶媒に分散することによって均一なＣＮＴ分散溶液ができること、さらには該溶液を基板上に塗布することによって均一なＣＮＴ分散体が得られるものである。なお、本発明では、分散という言葉を用いるが、これはＣＮＴが溶媒中に溶解している現象も含むものである。 In the present invention, a uniform CNT dispersion solution can be obtained by dispersing CNT having a conjugated polymer adhering to at least a part thereof in a solvent, and further, a uniform CNT dispersion can be obtained by coating the solution on a substrate. It is what In the present invention, the term “dispersion” is used, which includes a phenomenon in which CNT is dissolved in a solvent.
以下、本発明について詳述する。本発明においてＣＮＴに付着する重合体は、共役系重合体であることが必要で、さらに好ましくは直鎖状共役系重合体である。ここで直鎖状とは、重合体の骨格構造が安定状態（外力が加わっていない状態）において螺旋構造を取らず、まっすぐ延びているものを意味し、また、共役系重合体とは重合体の骨格の炭素−炭素の結合が１重結合と２重結合が交互に連なっている重合体を意味する。共役系重合体は共役系構造が伸びた構造からなるのでＣＮＴと重合体とでの電荷の移動がスムーズであり、またＣＮＴに付着した重合体以外の重合体が介在しないため、ＣＮＴの高い導電性や半導体特性を効率的に利用できるという特徴がある。本発明のＣＮＴ分散溶液においてＣＮＴの濃度を変えることによって該溶液を塗布した基板の電導性や半導体特性を制御することができる。 Hereinafter, the present invention will be described in detail. In the present invention, the polymer attached to the CNTs needs to be a conjugated polymer, and more preferably a linear conjugated polymer. Here, the straight chain means that the skeleton structure of the polymer does not take a spiral structure in a stable state (a state in which no external force is applied) and extends straight, and the conjugated polymer is a polymer. The polymer in which the carbon-carbon bonds of the skeleton are alternately linked with single bonds and double bonds. Since the conjugated polymer has a structure in which the conjugated structure is extended, the charge transfer between the CNT and the polymer is smooth, and the polymer other than the polymer attached to the CNT does not intervene. Characteristics and efficient use of semiconductor characteristics. By changing the CNT concentration in the CNT dispersion solution of the present invention, the conductivity and semiconductor characteristics of the substrate coated with the solution can be controlled.
共役系重合体としては、ポリチオフェン系重合体、ポリピロール系重合体、ポリアニリン系重合体、ポリアセチレン系重合体、ポリ−ｐ−フェニレン系重合体、ポリ−ｐ−フェニレンビニレン系重合体などが挙げられる。これらの共役系重合体が直鎖状であるためには、ポリチオフェン系重合体、ポリピロール系重合体はそれぞれチオフェン環、ピロール環の２、５位でモノマーユニットがつながる必要がある。また、ポリ−ｐ−フェニレン系重合体、ポリ−ｐ−フェニレンビニレン系重合体ではフェニレン基のパラ位で重合体の骨格がつながっている必要がある。上記重合体は単一のモノマーユニットが並んだものが好ましく用いられるが、異なるモノマーユニットをブロック共重合したもの、ランダム共重合したものも用いられる。また、グラフト重合したものも用いることができる。上記重合体の中でも本発明においては、ポリチオフェン系重合体が特に好ましく使用される。 Examples of the conjugated polymer include a polythiophene polymer, a polypyrrole polymer, a polyaniline polymer, a polyacetylene polymer, a poly-p-phenylene polymer, and a poly-p-phenylene vinylene polymer. In order for these conjugated polymers to be linear, the polythiophene polymer and the polypyrrole polymer need to be connected to monomer units at the 2nd and 5th positions of the thiophene ring and the pyrrole ring, respectively. Further, in the poly-p-phenylene polymer and the poly-p-phenylene vinylene polymer, the polymer skeleton needs to be connected at the para position of the phenylene group. As the polymer, those in which single monomer units are arranged are preferably used, but those obtained by block copolymerization or random copolymerization of different monomer units are also used. Further, graft-polymerized products can also be used. Among the above polymers, a polythiophene polymer is particularly preferably used in the present invention.
ポリチオフェン系重合体とはポリ−チオフェン構造の骨格を持つ重合体に側鎖が付いた構造を有するものである。具体例としては、ポリ−３−メチルチオフェン、ポリ−３−ブチルチオフェン、ポリ−３−ヘキシルチオフェン、ポリ−３−オクチルチオフェン、ポリ−３−ドデシルチオフェンなどのポリ−３−アルキルチオフェン（アルキル基の炭素数は特に制限はないが好ましくは１〜１２）、ポリ−３−メトキシチオフェン、ポリ−３−エトキシチオフェン、ポリ−３−ドデシルオキシチオフェンなどのポリ−３−アルコキシチオフェン（アルコキシ基の炭素数はとくに制限はないが好ましくは１〜１２）、ポリ−３−メトキシ−４−メチルチオフェン、ポリ−３−ドデシルオキシ−４−メチルチオフェンなどのポリ−３−アルコキシ−４−アルキルチオフェン（アルコキシ基およびアルキル基の炭素数は特に制限はないが好ましくは１〜１２）、ポリ−３−チオヘキシルチオフェンやポリ−３−チオドデシルチオフェンなどのポリ−３−チオアルキルチオフェン（アルキル基の炭素数は特に制限はないが好ましくは１〜１２）が挙げられ、１種もしくは２種以上を用いることができる。中でも、ポリ−３−アルキルチオフェン、ポリ−３−アルコキシチオフェンが好ましく、前者としては特にポリ−３−ヘキシルチオフェンが好ましい。好ましい分子量は重量平均分子量で８００〜１０００００である。また、上記重合体は必ずしも高分子量である必要はなく、直鎖状共役系からなるオリゴマーであってもよい。 The polythiophene polymer has a structure in which a side chain is attached to a polymer having a poly-thiophene structure skeleton. Specific examples include poly-3-alkylthiophene (alkyl group) such as poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, poly-3-octylthiophene, poly-3-dodecylthiophene, and the like. The number of carbons in the group is not particularly limited, but preferably 1 to 12), poly-3-alkoxythiophene such as poly-3-methoxythiophene, poly-3-ethoxythiophene, poly-3-dodecyloxythiophene (carbon of alkoxy group) The number is not particularly limited, but preferably 1 to 12), poly-3-alkoxy-4-alkylthiophene (alkoxy) such as poly-3-methoxy-4-methylthiophene, poly-3-dodecyloxy-4-methylthiophene, etc. The carbon number of the group and the alkyl group is not particularly limited, but preferably 1 to 12) Examples include poly-3-thioalkylthiophene such as -3-thiohexylthiophene and poly-3-thiododecylthiophene (the carbon number of the alkyl group is not particularly limited, but preferably 1 to 12). The above can be used. Among these, poly-3-alkylthiophene and poly-3-alkoxythiophene are preferable, and poly-3-hexylthiophene is particularly preferable as the former. A preferred molecular weight is 800 to 100,000 in terms of weight average molecular weight. Further, the polymer need not necessarily have a high molecular weight, and may be an oligomer composed of a linear conjugated system.
ＣＮＴはアーク放電法、化学気相成長法（以下ＣＶＤ法とする）、レーザー・アブレーション法等によって作製されるが、本発明に使用されるＣＮＴはいずれの方法によって得られたものであってもよい。また、ＣＮＴには１枚の炭素膜（グラッフェン・シート）が円筒状に巻かれた単層ＣＮＴ（以下ＳＷＣＮＴと言う）と、２枚のグラッフェン・シートが同心円状に巻かれた２層ＣＮＴ（以下ＤＷＣＮＴと言う）と、複数のグラッフェン・シートが同心円状に巻かれた多層ＣＮＴ（以下ＭＷＣＮＴと言う）とがあり、本発明においてＳＷＣＮＴ、ＤＷＣＮＴ、ＭＷＣＮＴをそれぞれ単体で、もしくは複数を同時に使用できる。特に、ＳＷＣＮＴとＤＷＣＮＴは導電性および半導体特性において優れた性質を持つので好ましく用いることができるが、中でもＳＷＣＮＴが特に好ましく用いられる。 CNTs are produced by arc discharge method, chemical vapor deposition method (hereinafter referred to as CVD method), laser ablation method, etc. The CNTs used in the present invention can be obtained by any method. Good. In addition, a single-walled CNT (hereinafter referred to as SWCNT) in which one carbon film (graphene sheet) is wound in a cylindrical shape, and a two-layer CNT in which two graphene sheets are wound in a concentric circle ( (Hereinafter referred to as DWCNT) and multi-layer CNTs (hereinafter referred to as MWCNT) in which a plurality of graphene sheets are concentrically wound. In the present invention, SWCNT, DWCNT, and MWCNT can be used alone or in combination. . In particular, SWCNT and DWCNT can be preferably used because they have excellent properties in terms of conductivity and semiconductor properties. Among them, SWCNT is particularly preferably used.
ＣＮＴを作製する際には、同時にフラーレンやグラファイト、非晶性炭素が副生産物として生成され、またニッケル、鉄、コバルト、イットリウムなどの触媒金属も残存するので、これらの不純物を除去し精製することが好ましい。不純物の除去には、硝酸、硫酸などによる酸処理とともに超音波処理が有効であり、またフィルターによる分離を併用することは純度を向上させる上でさらに好ましい。本発明で用いられるＣＮＴの直径は特に限定されないが、０．８ｎｍ以上１００ｎｍ以下が好ましく、より好ましくは５０ｎｍ以下、さらに好ましくは１５ｎｍ以下である。 When producing CNTs, fullerene, graphite, and amorphous carbon are produced as by-products at the same time, and catalyst metals such as nickel, iron, cobalt, yttrium, etc. remain, so these impurities are removed and purified. It is preferable. In order to remove impurities, ultrasonic treatment is effective together with acid treatment with nitric acid, sulfuric acid or the like, and it is more preferable to use separation with a filter in combination for improving purity. Although the diameter of CNT used by this invention is not specifically limited, 0.8 nm or more and 100 nm or less are preferable, More preferably, it is 50 nm or less, More preferably, it is 15 nm or less.
また、本発明ではＣＮＴは上記の精製後そのまま使用できるが、塗布膜が半導体として利用される場合には素子電極間の短絡を防ぐために、素子電極間の距離よりも短いＣＮＴを使用することが望ましい。しかし、ＣＮＴは一般には紐状で生成されるので、短繊維状で使用するにはカットすることが望ましい。短繊維へのカットには、硝酸、硫酸などによる酸処理とともに超音波処理が有効であり、またフィルターによる分離を併用することは純度を向上させる上でもさらに好ましい。なお、カットしたＣＮＴだけではなく、あらかじめ短繊維状に作製したＣＮＴも本発明により好ましく使用される。このような短繊維状ＣＮＴは基板上に鉄、コバルトなどの触媒金属を形成し、その表面にＣＶＤ法により７００〜９００℃で炭素化合物を熱分解してＣＮＴを気相成長させることによって基板表面に垂直方向に配向した形状で得られる。このようにして作製された短繊維状ＣＮＴは基板から剥ぎ取るなどの方法で取り出すことができる。また、短繊維状ＣＮＴはポーラスシリコンのようなポーラスな支持体や、アルミナの陽極酸化膜上に触媒金属を担持させ、その表面にＣＮＴをＣＶＤ法にて成長させることもできる。触媒金属を分子内に含む鉄フタロシアニンのような分子を原料とし、アルゴン／水素のガス流中でＣＶＤを行うことによって基板上にＣＮＴを作製する方法でも配向した短繊維状のＣＮＴを作製することもできる。さらには、ＳｉＣ単結晶表面にエピタキシャル成長法によって配向した短繊維状ＣＮＴを得ることもできる。溶液の塗布より得られた分散体が半導体として利用される場合には、ＣＮＴの平均長さは電極間距離によるが、好ましくは２μｍ以下、より好ましくは０．５μｍ以下で使用される。 In the present invention, CNT can be used as it is after the above purification, but when the coating film is used as a semiconductor, in order to prevent a short circuit between the device electrodes, it is possible to use a CNT shorter than the distance between the device electrodes. desirable. However, since CNTs are generally produced in the form of strings, it is desirable to cut them for use in the form of short fibers. In order to cut into short fibers, ultrasonic treatment is effective together with acid treatment with nitric acid, sulfuric acid, etc., and it is more preferable to use separation with a filter in combination for improving purity. In addition, not only the cut CNT but also a CNT prepared in a short fiber shape in advance is preferably used according to the present invention. Such short fibrous CNTs form a catalytic metal such as iron or cobalt on a substrate, and thermally decompose carbon compounds at 700 to 900 ° C. by CVD on the surface thereof to vapor-phase grow the CNTs. It is obtained in a shape oriented in the vertical direction. The short fiber CNTs thus produced can be taken out by a method such as peeling off from the substrate. In addition, the short fibrous CNTs can be obtained by supporting a catalytic metal on a porous support such as porous silicon or an anodic oxide film of alumina and growing the CNTs on the surface by the CVD method. Using oriented molecules such as iron phthalocyanine containing a catalytic metal in the molecule as a raw material and producing CNTs on a substrate by performing CVD in an argon / hydrogen gas flow, producing oriented short fiber CNTs You can also. Furthermore, it is also possible to obtain short fiber CNTs oriented on the SiC single crystal surface by an epitaxial growth method. When the dispersion obtained by applying the solution is used as a semiconductor, the average length of CNT depends on the distance between the electrodes, but is preferably 2 μm or less, more preferably 0.5 μm or less.
本発明で用いられるＣＮＴの直径は特に限定されないが、１ｎｍ以上、１００ｎｍ以下、より好ましくは５０ｎｍ以下が良好に使用される。 Although the diameter of CNT used by this invention is not specifically limited, 1 nm or more and 100 nm or less, More preferably, 50 nm or less is used favorably.
共役系重合体が付着したＣＮＴを溶媒の中に分散させることによって、本発明のＣＮＴの分散溶液を得ることができる。共役系重合体をＣＮＴに付着させる方法としては、共役系重合体とＣＮＴとの間に相互作用があるため、共役系重合体の溶液中にＣＮＴを添加して分散させることによって、少なくともその一部に付着したＣＮＴが溶液中に生成される。該溶液中で共役系重合体をＣＮＴに効率的に付着させるには、ＣＮＴを溶媒中で予め超音波照射下で予備分散した後、共役系重合体を添加し分散させる方法、あるいはＣＮＴと共役系高分子を溶媒に混合した後、超音波照射下で分散する方法、溶融した共役系重合体の中にＣＮＴを添加して分散させる方法等がある。本発明においては、何れの方法でも良いが、中でもＣＮＴを溶媒中で超音波で予備分散しておいた後に共役系重合体を添加する方法や、ＣＮＴと共役系高分子を溶媒に混合した後、超音波照射を行う方法が好ましい。ここで、超音波照射は超音波洗浄機、超音波破砕機などを用いて行うことができる。 By dispersing the CNTs to which the conjugated polymer is adhered in a solvent, the CNT dispersion solution of the present invention can be obtained. As a method of attaching the conjugated polymer to the CNT, since there is an interaction between the conjugated polymer and the CNT, at least one of them can be performed by adding and dispersing the CNT in the conjugated polymer solution. CNT adhering to the part is generated in the solution. In order to efficiently attach the conjugated polymer to the CNT in the solution, the CNT is preliminarily dispersed in a solvent under ultrasonic irradiation, and then the conjugated polymer is added and dispersed, or the CNT is conjugated with the CNT. There are a method in which a polymer is mixed with a solvent and then dispersed under ultrasonic irradiation, a method in which CNT is added and dispersed in a molten conjugated polymer, and the like. In the present invention, any method may be used, but in particular, a method of adding a conjugated polymer after preliminarily dispersing CNT in a solvent in a solvent, or after mixing CNT and a conjugated polymer in a solvent. A method of performing ultrasonic irradiation is preferred. Here, ultrasonic irradiation can be performed using an ultrasonic cleaner, an ultrasonic crusher, or the like.
共役系重合体がＣＮＴの少なくとも一部に付着した状態とは、ＣＮＴ表面の一部、あるいは全部を共役系重合体が被覆した状態を意味する。ＣＮＴを共役系重合体が被覆できるのはそれぞれの共役系構造に由来するπ電子雲が重なることによって相互作用が生じるためと推測される。ＣＮＴが共役系重合体で被覆されているか否かは、該ＣＮＴの反射色が元のＣＮＴの色から共役系重合体の色に近づくことで判別できる。定量的には元素分析によって付着物の存在とＣＮＴに対する付着物の重量比を同定することができる。また共役系重合体が少なくとも一部に付着した状態とは、ＣＮＴの重量を１．０とした時の共役系重合体の重量比率が少なくとも０．１である状態ということもできる。 The state in which the conjugated polymer is attached to at least a part of the CNT means a state in which a part or all of the CNT surface is covered with the conjugated polymer. The reason why the conjugated polymer can be coated with CNT is presumed to be that interaction occurs due to the overlap of π electron clouds derived from the respective conjugated structures. Whether or not CNT is coated with a conjugated polymer can be determined by the fact that the reflected color of the CNT approaches the color of the conjugated polymer from the original CNT color. Quantitatively, the presence of deposits and the weight ratio of deposits to CNTs can be identified by elemental analysis. The state in which the conjugated polymer is attached to at least a part can also be a state in which the weight ratio of the conjugated polymer is at least 0.1 when the weight of CNT is 1.0.
その後、フィルター（好ましくは０．１μｍ径）で上記ＣＮＴを濾過して捕集し、溶媒を用いて該ＣＮＴを十分に洗浄する。この洗浄工程によって、余剰の共役系重合体が除去されて共役系重合体の付着したＣＮＴのみが得られる。ＣＮＴに付着した共役系高分子は該ＣＮＴの溶媒への親和性を高めるのに寄与するが、残存する重合体は付着したもののみに限られるため、本発明によるＣＮＴ分散体はＣＮＴ本来の導電性や半導体特性に近い特性（例えば電界効果型トランジスタに使用した場合には高いキャリア移動度）が得られる。なお、濾過・洗浄後、共役系重合体がＣＮＴの表面に吸着していることは種々の分析法、例えば元素分析、表面分析装置で確認することができる。 Thereafter, the CNTs are filtered and collected with a filter (preferably with a diameter of 0.1 μm), and the CNTs are sufficiently washed with a solvent. By this washing step, excess conjugated polymer is removed, and only CNTs to which the conjugated polymer is attached are obtained. The conjugated polymer adhering to the CNT contributes to increasing the affinity of the CNT to the solvent, but the remaining polymer is limited to only the adhering polymer. And characteristics close to semiconductor characteristics and semiconductor characteristics (for example, high carrier mobility when used in a field effect transistor) can be obtained. In addition, after filtration and washing | cleaning, it can confirm with the various analysis methods, for example, an elemental analysis, a surface analysis apparatus, that the conjugated polymer adsorb | sucks to the surface of CNT.
次に、上記の方法で得られた共役系重合体の付着したＣＮＴを溶媒中に分散させることによってＣＮＴ分散溶液が調製される。ここで溶媒中への分散手段としては撹拌、超音波照射分散、振動分散などの手段から必要に応じて方法を選ぶことができる。 Next, a CNT dispersion solution is prepared by dispersing CNTs attached with the conjugated polymer obtained by the above method in a solvent. Here, as a means for dispersing in the solvent, a method can be selected as necessary from means such as stirring, ultrasonic irradiation dispersion, vibration dispersion and the like.
ＣＮＴ分散溶液の調製に使用される溶媒としては、特に有機溶媒が好ましく用いられ、メタノール、エタノール、ブタノール、トルエン、キシレン、ｏ−クロロフェノール、アセトン、酢酸エチル、エチレングリコール、クロロホルム、クロロベンゼン、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン、γ−ブチロラクトンなどが挙げられるがこれらに限定されるものではなく、必要に応じて溶媒を選ぶことができる。 As the solvent used for the preparation of the CNT dispersion solution, an organic solvent is particularly preferably used. Methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, chloroform, chlorobenzene, dimethylformamide , Dimethyl sulfoxide, N-methylpyrrolidone, γ-butyrolactone and the like, but are not limited thereto, and a solvent can be selected as necessary.
溶媒中のＣＮＴ分散量は必要に応じて定められるが、溶媒１リットル中に１０ｇ以下、１００μｇ以上が好ましく用いられる。 The amount of CNT dispersion in the solvent is determined as necessary, but 10 g or less and 100 μg or more are preferably used in 1 liter of the solvent.
このようにして得られたＣＮＴ分散溶液を基板上に塗布することによって、基板上に導電性や半導体性の機能を付与することができる。塗布方法としては、キャスト法、スピナーによる方法、ディップ法、バーコーター法、滴下法など一般的な方法が可能である。基板としてはガラスやシリコンウエハー、構造材などの無機物のみならず、フィルム、繊維、織物膜、板、紙などに塗布することができる。 By applying the CNT dispersion solution thus obtained on the substrate, it is possible to impart a conductive or semiconducting function on the substrate. As a coating method, general methods such as a casting method, a spinner method, a dipping method, a bar coater method, and a dropping method are possible. The substrate can be applied not only to inorganic substances such as glass, silicon wafers and structural materials, but also to films, fibers, fabric films, boards, papers and the like.
本発明で得られるＣＮＴ分散体を電界効果型トランジスタの半導体層として用いる場合には、絶縁層で覆われたゲート電極上に本発明のＣＮＴ分散溶液をスピナーを用いて塗布し、塗布膜中に残存する溶媒を蒸発させることによってＣＮＴ分散体の半導体層が形成される。このＣＮＴ分散体層の上にソース電極とドレイン電極とを対峙させて形成することによって、電界効果トランジスタ構造が作製される。 When the CNT dispersion obtained in the present invention is used as a semiconductor layer of a field effect transistor, the CNT dispersion solution of the present invention is applied onto a gate electrode covered with an insulating layer using a spinner, A semiconductor layer of the CNT dispersion is formed by evaporating the remaining solvent. A field effect transistor structure is fabricated by forming a source electrode and a drain electrode in opposition to each other on the CNT dispersion layer.
基板上に共役系重合体が付着したＣＮＴ分散体のパターンを形成する場合には、該ＣＮＴが溶媒に溶解しやすいことを利用して感光性レジストを用いてフォトリソグラフィー法によってパターンを形成することが可能である。 When forming a pattern of a CNT dispersion with a conjugated polymer attached on a substrate, the pattern is formed by a photolithography method using a photosensitive resist using the fact that the CNT is easily dissolved in a solvent. Is possible.
上記の方法によって作製されるＣＮＴ分散体の数密度は、溶媒中のＣＮＴ成分量と単位面積当たりの使用塗液量によって決まる。導電性を付与するには数密度が高いほど好ましいが、半導体特性を付与するには、ＣＮＴの数密度はパーコレーションによる伝導パスが形成される密度以下、すなわち１平方ミクロン当たり５００以下、１．０以上であることが好ましい。本発明におけるＣＮＴの分散状態を確認する方法としては種々の顕微鏡観察が用いられるが、ＣＮＴの数密度を調べるには原子間力顕微鏡が好ましく用いられる。 The number density of the CNT dispersion produced by the above method is determined by the amount of the CNT component in the solvent and the amount of coating liquid used per unit area. In order to impart conductivity, the higher the number density, the better. However, in order to impart semiconductor characteristics, the number density of CNTs is less than the density at which a conduction path is formed by percolation, that is, less than 500 per square micron, The above is preferable. Various microscopic observations are used as a method for confirming the dispersion state of CNTs in the present invention, and an atomic force microscope is preferably used for examining the number density of CNTs.
本発明のＣＮＴ分散体を半導体層として用いる場合にはその厚みはＣＮＴ数本以下の厚みになるので透明性が高く、透明な半導体層になる。例えばゲート電極、ソース電極、ドレイン電極の材料をＩＴＯまたはＳｂドープＳｎＯ２または高導電性有機材料などの透明材料を用い、絶縁層もＳｉＯ２や絶縁性ポリマーなどの透明材料を用いることで透明な半導体素子を形成することができる。 When the CNT dispersion of the present invention is used as a semiconductor layer, the thickness is several CNTs or less, so that the transparency is high and a transparent semiconductor layer is obtained. For example, a transparent material such as ITO or Sb-doped SnO 2 or a highly conductive organic material is used for the material of the gate electrode, source electrode, and drain electrode, and the insulating layer is also transparent by using a transparent material such as SiO 2 or an insulating polymer. A semiconductor element can be formed.
本発明で得られるＣＮＴ分散体を導電体として用いる場合には、基板等に塗布されたＣＮＴが互いに接触する程度に高濃度に塗布すると良い。すなわちＣＮＴの１平方ミクロン当たりの数密度が５００より大きければ良い。ＣＮＴ分散液の濃度が低い場合には、塗布膜厚を厚くしたり、塗布回数を増やすなどの方法によって導電体を得ることができ、またＣＮＴ分散液中のＣＮＴ濃度を高くして塗布することによっても導電体を得ることができる。 When the CNT dispersion obtained in the present invention is used as a conductor, the CNT dispersion applied to a substrate or the like is preferably applied at a high concentration so that the CNTs are in contact with each other. That is, it is sufficient that the number density per square micron of CNT is larger than 500. When the concentration of the CNT dispersion is low, the conductor can be obtained by increasing the coating thickness or increasing the number of coatings, and the CNT concentration in the CNT dispersion can be increased. The conductor can also be obtained.
上記のような導電体は膜厚が２ｎｍ以上あれば良く、特に膜厚が２ｎｍ〜２００ｎｍの場合には透明性が高く、透明導電体として用いることができる。この範囲の膜厚であれば可視光透過率が５０％Ｔ以上となり、膜厚を２ｎｍ〜１００ｎｍにすることで可視光透過率は８０％Ｔを超え良好な透明導電膜を得ることができる。該透明導電体は膜厚が厚いほど抵抗を小さくできるが、同時に光の透過率が小さくなるので、目的に応じて膜厚を調製すると良い。より低抵抗、高透過率の透明導電体を得るためには、１本の長さがより長いＣＮＴを用いたり、より細いＣＮＴ用いたり、ＣＮＴ分散時に用いる撹拌や超音波照射などの条件をより強力にする方法などが好ましく用いられる。 The conductor as described above only needs to have a film thickness of 2 nm or more. In particular, when the film thickness is 2 nm to 200 nm, the conductor has high transparency and can be used as a transparent conductor. If the film thickness is within this range, the visible light transmittance is 50% T or more. By setting the film thickness to 2 nm to 100 nm, the visible light transmittance exceeds 80% T, and a good transparent conductive film can be obtained. Although the resistance of the transparent conductor can be reduced as the film thickness increases, the light transmittance decreases at the same time. Therefore, the film thickness is preferably adjusted according to the purpose. In order to obtain a transparent conductor having a lower resistance and a higher transmittance, it is necessary to use CNTs with a longer length, use thinner CNTs, or use conditions such as stirring and ultrasonic irradiation used for CNT dispersion. A method of strengthening is preferably used.
ＣＮＴ分散液から導電体を得る他の方法として、ある支持体の上に一度ＣＮＴ分散体膜を形成し、得られた分散体膜を他の支持体に写して形成する方法も用いることができる。例えば、ＣＮＴ分散液を、フィルター上に捕集して堆積したＣＮＴを別の基板上に写して形成する方法や、あるいは、フィルム上に塗布して得られたＣＮＴ分散体膜を別の基板に写して形成する方法などがある。この場合、ＣＮＴ分散体膜の付着したフィルターやフィルムを、別の基板にＣＮＴ分散体膜が付着するように接触させることでＣＮＴ分散体膜を写すことができる。この際フィルターやフィルムはＣＮＴ分散体膜の剥離性の良好なものが好ましく用いられ、ＰＥＴ（ポリエチレンテレフタレート）、ナイロン、ＰＰ（ポリプロピレン）、ＰＴＦＥ（ポリテトラフロオロエチレン）製のものが、より好ましく用いられる。さらにフィルターやフィルムの背面から圧力を加えたり、少量の溶媒を湿潤させることで良好に膜を写して形成することができる。 As another method of obtaining a conductor from a CNT dispersion, a method of forming a CNT dispersion film once on a certain support and copying the obtained dispersion film on another support can also be used. . For example, a method of forming a CNT dispersion liquid by collecting and depositing CNTs deposited on a filter on another substrate, or a CNT dispersion film obtained by coating on a film on another substrate There are methods such as copying and forming. In this case, the CNT dispersion film can be copied by bringing the filter or film to which the CNT dispersion film is attached into contact with another substrate so that the CNT dispersion film is attached. In this case, a filter or film having a good CNT dispersion film peelability is preferably used, and those made of PET (polyethylene terephthalate), nylon, PP (polypropylene), and PTFE (polytetrafluoroethylene) are more preferable. Used. Furthermore, a film can be well copied and formed by applying pressure from the back of the filter or film or moistening a small amount of solvent.
このように膜を写して形成する方法においては、予め必要なパターンを支持体に施しておくことでパターン形成をすることができる。例えばフィルター上にＣＮＴ分散体膜を形成する場合にはフィルターの上面にパターンの型を抜いたフィルムなどを重ねておくことで、所望のパターンを得ることができ、フィルム上にＣＮＴ分散体膜を形成する場合には、別の支持体との間にパターンの型を抜いたフィルムを挟んだり、あるいはＣＮＴ分散液との親和性の異なる材料を用いてパターン形成しておくなどして、所望のパターンを得ることができる。 In such a method of forming a film by copying, the pattern can be formed by applying a necessary pattern to the support in advance. For example, when a CNT dispersion film is formed on a filter, a desired pattern can be obtained by stacking a pattern-extracted film on the upper surface of the filter, and the CNT dispersion film is formed on the film. In the case of forming, a desired pattern may be obtained by sandwiching a film from which a pattern is removed with another support, or by forming a pattern using a material having a different affinity with the CNT dispersion liquid. A pattern can be obtained.
本発明においてはＣＮＴ分散液が非常に均一に分散しているのでフィルター上に捕集したＣＮＴや、フィルム上に塗布したＣＮＴは、面内均一性が高く、これらを転写することで高品質のＣＮＴ分散体膜を得ることができる。 In the present invention, since the CNT dispersion liquid is very uniformly dispersed, the CNT collected on the filter and the CNT coated on the film have high in-plane uniformity, and high quality can be obtained by transferring them. A CNT dispersion film can be obtained.
本発明を用いて得られる導電体は面内の均一性が高く、例えば電子放出素子の電子放出源として好ましく用いることができる。面内均一性を高くできることで面内いずれの箇所においても均一に電界を印加することができ、例えばフィールドエミッションディスプレイにおいては輝度ムラを抑制することができ、高品位な画像を得ることができる。 The conductor obtained by using the present invention has high in-plane uniformity, and can be preferably used, for example, as an electron emission source of an electron emission element. Since the in-plane uniformity can be increased, an electric field can be applied uniformly at any location in the plane. For example, in a field emission display, luminance unevenness can be suppressed, and a high-quality image can be obtained.
本発明で得られたＣＮＴ分散体の各ＣＮＴには共役系高分子が付着しており、一方、共役系高分子は一般にπ電子が移動しやすい構造となっているので、ＣＮＴ間の電荷移動が妨げられず電荷がスムーズに移動できる。もちろん、必要に応じて共役系高分子を剥離してＣＮＴのみの分散構造体とすることも可能である。この方法としては、例えば共役系高分子の熱分解温度とＣＮＴの熱分解温度の間の温度でＣＮＴ分散体を熱処理することによって共役系高分子を除去する方法などが挙げられる。 Conjugated polymers are attached to each CNT of the CNT dispersion obtained in the present invention. On the other hand, conjugated polymers generally have a structure in which π electrons easily move. The charge can move smoothly without being disturbed. Of course, if necessary, the conjugated polymer can be peeled off to form a dispersion structure only of CNTs. Examples of this method include a method of removing the conjugated polymer by heat-treating the CNT dispersion at a temperature between the thermal decomposition temperature of the conjugated polymer and the thermal decomposition temperature of the CNT.
以下、本発明を実施例に基づきさらに具体的に説明する。ただし、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.
実施例１
ＣＮＴ（単層カーボンナノチューブ：サイエンスラボラトリーズ社製、純度９５％）を６ｍｇと、共役系重合体のポリ−３−ヘキシルチオフェン（アルドリッチ社製、分子量：Ｍｗ２００００）を６ｍｇと、クロロホルム３０ｍＬを５０ｍＬのサンプル管に入れ、超音波破砕機（東京理化器械（株）製ＶＣＸ−５０２、出力２５０Ｗ、直接照射）を用いて２０分間超音波照射してＣＮＴの分散を行った。得られたＣＮＴ分散液をポリテトラフルオロエチレン製の０．１μｍ孔フィルター（東洋アドバンテック（株）製）で濾別した後、クロロホルムで洗浄することによって余分な重合体を除去し表面にポリ−３−ヘキシルチオフェンが付着したＣＮＴを得た。ポリ−３−ヘキシルチオフェンのＣＮＴの付着量は元素分析法によって測定した。この時のポリ−３−ヘキシルチオフェンの付着量の重量比率はＣＮＴ１．０に対し０．８９であった。
Example 1
CNT (single-walled carbon nanotube: Science Laboratories, purity 95%) 6 mg, conjugated polymer poly-3-hexylthiophene (Aldrich, molecular weight: Mw 20000) 6 mg, chloroform 30 mL 50 mL sample The CNTs were dispersed by ultrasonic irradiation for 20 minutes using an ultrasonic crusher (VCX-502 manufactured by Tokyo Rika Kikai Co., Ltd., output 250 W, direct irradiation). The obtained CNT dispersion was filtered with a 0.1 μm pore filter (manufactured by Toyo Advantech Co., Ltd.) made of polytetrafluoroethylene, and then washed with chloroform to remove excess polymer and poly-3 on the surface. -CNTs with attached hexylthiophene were obtained. The amount of CNT adhered to poly-3-hexylthiophene was measured by elemental analysis. The weight ratio of the attached amount of poly-3-hexylthiophene at this time was 0.89 with respect to CNT 1.0.
次いで、該ＣＮＴにクロロホルム１５０ｍＬを加え、超音波洗浄機（井内盛栄堂（株）製ＵＳ−２、出力１２０Ｗ、間接照射）を用いて１時間超音波分散することによって、共役系重合体が付着したＣＮＴが均一に分散したＣＮＴ分散クロロホルム溶液（ＣＮＴ濃度０．０４ｇ／Ｌ）が得られた。 Next, 150 mL of chloroform is added to the CNT, and the conjugated polymer is adhered by ultrasonically dispersing for 1 hour using an ultrasonic cleaner (US-2 manufactured by Iuchi Seieido Co., Ltd., output 120 W, indirect irradiation). A CNT-dispersed chloroform solution (CNT concentration 0.04 g / L) in which the produced CNTs were uniformly dispersed was obtained.
実施例２
実施例１で得られた分散溶液０．０５ｍＬを、シリコンウエハー上にある周縁部を粘着テープでマスクした５ｍｍ角の部分に滴下し、風乾した。粘着テープを除去し、塗布されたＣＮＴをＡＦＭを用いて観察した（図１参照）。表面にポリ−３−ヘキシルチオフェンが付着したＣＮＴが良好に分散した状態で基板に付着しており、そのＣＮＴの数密度は約３個／μｍ２であった。
Example 2
0.05 mL of the dispersion solution obtained in Example 1 was dropped onto a 5 mm square portion in which the peripheral portion on the silicon wafer was masked with an adhesive tape, and air-dried. The adhesive tape was removed, and the applied CNTs were observed using AFM (see FIG. 1). The CNTs with poly-3-hexylthiophene attached to the surface adhered to the substrate in a well dispersed state, and the number density of the CNTs was about 3 / μm 2 .
実施例３
ＣＮＴの分散を、超音波破砕機の代わりに超音波洗浄機を用いて２時間分散した以外は実施例１と同じ操作を行った。シリコン基板上に塗布されたＣＮＴをＡＦＭで観察したところ、表面にポリ−３−ヘキシルチオフェンが付着したＣＮＴが良好に分散した状態で基板に付着していた。
Example 3
The same operation as in Example 1 was performed except that the dispersion of CNT was dispersed for 2 hours using an ultrasonic cleaner instead of the ultrasonic crusher. When the CNT coated on the silicon substrate was observed with an AFM, the CNT with poly-3-hexylthiophene adhered to the surface was adhered to the substrate in a well dispersed state.
実施例４
実施例１のポリ−３−ヘキシルチオフェンの代わりにポリ−３−ブチルチオフェンを用いた以外は、実施例１と同様にＣＮＴの分散溶液を調整した結果、ＣＮＴが均一に分散した分散溶液が得られた。
Example 4
Except that poly-3-butylthiophene was used instead of poly-3-hexylthiophene in Example 1, a CNT dispersion solution was prepared in the same manner as in Example 1 to obtain a dispersion solution in which CNTs were uniformly dispersed. It was.
比較例１
実施例１の超音波破砕機によるＣＮＴの分散時に、ポリ−３−ヘキシルチオフェンを用いなかった以外は実施例１と同じ操作を行った。０．１μｍ孔フィルターでろ別したＣＮＴをクロロホルム中に入れ、超音波洗浄機で分散を試みたが、ＣＮＴは分散せず、沈殿した。
Comparative Example 1
The same operation as in Example 1 was performed except that poly-3-hexylthiophene was not used during the dispersion of CNTs by the ultrasonic crusher of Example 1. CNT filtered with a 0.1 μm pore filter was placed in chloroform and dispersion was attempted with an ultrasonic cleaner, but CNT did not disperse but precipitated.
実施例５
図２の模式断面図に示すような電界効果型トランジスタ（ＦＥＴ）を作製した。
基板としてＳｉＯ２膜（膜厚３００ｎｍ）（４０）付きのアンチモンドープシリコンウエハー（抵抗率０．０２Ωｃｍ以下）（５０）を用いた。ここで、シリコンウエハーは基板であると同時に、ゲート電極（６０）であり、熱酸化膜は絶縁層となる。次にフォトリソグラフィー技術および真空蒸着法を用いて櫛型状のソース電極（３０）およびドレイン電極（２０）を形成した。ここで両電極の電極材には金を用いた。また、両櫛形電極の幅（チャネル幅）は５０ｃｍ、電極の間隔（チャネル長）は２０μｍ、電極の高さは４０ｎｍとした。これらをＦＥＴ基板と称する。またここで用いたフォトリソグラフィー技術および真空蒸着法は一般的に用いられている条件等で行った。
Example 5
A field effect transistor (FET) as shown in the schematic cross-sectional view of FIG. 2 was produced.
As a substrate, an antimony-doped silicon wafer (resistivity 0.02 Ωcm or less) (50) with a SiO 2 film (film thickness 300 nm) (40) was used. Here, the silicon wafer is a substrate and at the same time the gate electrode (60), and the thermal oxide film is an insulating layer. Next, a comb-shaped source electrode (30) and a drain electrode (20) were formed using a photolithography technique and a vacuum deposition method. Here, gold was used for the electrode material of both electrodes. The width of both comb electrodes (channel width) was 50 cm, the distance between the electrodes (channel length) was 20 μm, and the height of the electrodes was 40 nm. These are called FET substrates. The photolithography technique and the vacuum deposition method used here were performed under generally used conditions.
次に、半導体層（１０）として用いる有機高分子半導体で被覆された単層ＣＮＴ（以下、ＳＷＣＮＴと言う）の塗液を以下の方法で調整した。 Next, a coating solution of single-walled CNT (hereinafter referred to as SWCNT) coated with an organic polymer semiconductor used as the semiconductor layer (10) was prepared by the following method.
ＳＷＣＮＴ０．３ｍｇを、有機高分子半導体であるポリ−３−ヘキシルチオフェン（以下Ｐ３ＨＴと略す）（アルドリッチ社製）０．３ｍｇを溶解した３０ｍＬのクロロホルムの中に加え、氷冷しながら超音波ホモジナイザー（ＳＯＮＩＣＳ社製ＶＣＸ−５００）を用いて出力２５０Ｗで３０分間超音波攪拌してＳＷＣＮＴ分散液を得た。得られたＳＷＣＮＴ分散液に、Ｐ３ＨＴ３０ｍｇを加え、超音波洗浄機（井内盛栄堂（株）製ＵＳ−２、出力１２０Ｗ）を用いて３０分間超音波攪拌することによりＳＷＣＮＴをＰ３ＨＴで被覆した。 Add 0.3 mg of SWCNT to 30 mL of chloroform in which 0.3 mg of poly-3-hexylthiophene (hereinafter abbreviated as P3HT) (Aldrich), which is an organic polymer semiconductor, is dissolved, and an ultrasonic homogenizer ( SONICS VCX-500) was used for ultrasonic stirring at an output of 250 W for 30 minutes to obtain a SWCNT dispersion. To the obtained SWCNT dispersion, 30 mg of P3HT was added, and the SWCNT was coated with P3HT by ultrasonic stirring for 30 minutes using an ultrasonic cleaner (US-2 manufactured by Iuchi Seieido Co., Ltd., output 120 W).
次いで余剰のＰ３ＨＴを除去すべく、該分散液を公称０．１μｍ孔径のＰＴＦＥ製オムニポアメンブレン（アドバンテック（株）製）を用い、Ｐ３ＨＴコートＳＷＣＮＴの濾別を行った。フィルター上に堆積したＰ３ＨＴでコートされたＳＷＣＮＴをクロロホルム３０ｍＬで２度洗浄した後、Ｐ３ＨＴでコートされたＳＷＣＮＴをフィルターごと３０ｍＬのクロロホルムの中に入れ、超音波洗浄機を用いて超音波照射することによって再びＰ３ＨＴでコートされたＳＷＣＮＴを分散し、これを塗液とした。 Subsequently, in order to remove excess P3HT, the dispersion was subjected to filtration of P3HT-coated SWCNTs using a PTFE omnipore membrane (Advantech Co., Ltd.) having a nominal pore size of 0.1 μm. After SWCNT coated with P3HT deposited on the filter is washed twice with 30 mL of chloroform, the SWCNT coated with P3HT is put into 30 mL of chloroform together with the filter, and ultrasonically irradiated using an ultrasonic cleaner. Then, SWCNT coated with P3HT was dispersed again to obtain a coating solution.
該塗液を前述の基板上に滴下しスピンコート法（ミカサ製スピンコーター１Ｈ−Ｄ３、回転速度１０００ｒｐｍ）により膜厚５ｎｍの薄膜を形成した。該基板に引き出し電極用の銀線を取りつけた後、７０℃の真空乾燥機中に３０分間静置し、ＦＥＴ素子を形成した。この素子のゲート電極に電圧を印加しながらドレイン・ソース間の電圧電流特性を測定した。この時の移動度は０．１７ｃｍ２／Ｖ・ｓｅｃであった。 The coating solution was dropped on the above-mentioned substrate, and a thin film having a thickness of 5 nm was formed by a spin coating method (Mikasa spin coater 1H-D3, rotation speed 1000 rpm). After attaching a silver wire for the lead electrode to the substrate, it was left to stand in a vacuum dryer at 70 ° C. for 30 minutes to form an FET element. The voltage-current characteristics between the drain and the source were measured while applying a voltage to the gate electrode of this element. The mobility at this time was 0.17 cm 2 / V · sec.
比較例２
ＳＷＣＮＴ０．２ｍｇを、有機高分子半導体であるＰ３ＨＴ０．２ｍｇを溶解した１０ｍＬのクロロホルムの中に加え、氷冷しながら超音波ホモジナイザー（ＳＯＮＩＣＳ社製ＶＣＸ−５００）を用いて出力２５０Ｗで３０分間超音波攪拌してＳＷＣＮＴ分散液を得た。
Comparative Example 2
Add SWCNT 0.2mg into 10mL chloroform dissolved organic polymer semiconductor P3HT 0.2mg, and use ultrasonic homogenizer (SONX VCX-500) for 30 minutes while cooling with ice. Stirring to obtain a SWCNT dispersion.
得られたＳＷＣＮＴ分散液に、Ｐ３ＨＴ５０ｍｇを加え、超音波洗浄機（井内盛栄堂製ＵＳ−２、出力１２０Ｗ）を用いて３０分間超音波攪拌することによりＳＷＣＮＴが分散したＰ３ＨＴ溶液を得た。この溶液を実施例５と同様のＦＥＴ基板上に滴下しスピンコート法（回転速度１０００ｒｐｍ）により膜厚４０ｎｍの薄膜を形成した。該基板に引き出し電極用の銀線を取りつけた後、７０℃の真空乾燥機中に３０分間静置し、ＦＥＴ素子を形成した。この素子のゲート電極に電圧を印加しながらドレイン・ソース間の電圧電流特性を測定した。この時の移動度は２．５４×１０−３ｃｍ２／Ｖ・ｓｅｃであった。 50 mg of P3HT was added to the obtained SWCNT dispersion, and a P3HT solution in which SWCNTs were dispersed was obtained by ultrasonically stirring for 30 minutes using an ultrasonic washer (US-2 manufactured by Iuchi Seieido, output 120 W). This solution was dropped on the same FET substrate as in Example 5, and a thin film having a thickness of 40 nm was formed by spin coating (rotation speed: 1000 rpm). After attaching a silver wire for the lead electrode to the substrate, it was left to stand in a vacuum dryer at 70 ° C. for 30 minutes to form an FET element. The voltage-current characteristics between the drain and the source were measured while applying a voltage to the gate electrode of this element. The mobility at this time was 2.54 × 10 −3 cm 2 / V · sec.
実施例６
実施例１と同様の方法を用いて、ＣＮＴ表面にポリ−３−ヘキシルチオフェンが付着したＣＮＴを調製したが、超音波洗浄機を用いてＣＮＴを分散するときに加えるクロロホルムの量を１５０ｍＬから６ｍＬに減らし、ＣＮＴ濃度１ｇ／Ｌの共役系重合体が付着したＣＮＴの均一分散液を得た。
Example 6
A CNT with poly-3-hexylthiophene attached to the CNT surface was prepared using the same method as in Example 1, but the amount of chloroform added when dispersing the CNT using an ultrasonic cleaner was changed from 150 mL to 6 mL. To obtain a uniform dispersion of CNTs to which a conjugated polymer having a CNT concentration of 1 g / L was adhered.
次いで得られたＣＮＴ分散液０．３ｍＬを、３ｃｍ角のガラス基板上に滴下し、基板の端に設けた厚み５０μｍの粘着テープをスペーサーとしてブレードキャストした。溶媒が揮発した後、ＣＮＴ分散体膜が得られた。得られたＣＮＴ分散体膜を、紫外可視分光光度計（（株）島津製作所製、MultiSpec-1500）を用いて透過率を測定したところ、５００ｎｍの波長で８０％Ｔであった。次にＣＮＴ分散体膜上に銀ペースト（藤倉化成（株）製、ドータイトＤ−５００（商品名）を用いて、幅１ｃｍ、間隔１ｃｍの対抗電極を作製し、電極間の抵抗から表面抵抗値を求めたところ、８００Ω／□であった。 Next, 0.3 mL of the obtained CNT dispersion was dropped onto a 3 cm square glass substrate, and blade casted using an adhesive tape with a thickness of 50 μm provided at the edge of the substrate as a spacer. After the solvent was volatilized, a CNT dispersion film was obtained. When the transmittance of the obtained CNT dispersion film was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, MultiSpec-1500), it was 80% T at a wavelength of 500 nm. Next, using a silver paste (made by Fujikura Kasei Co., Ltd., Dotite D-500 (trade name) on the CNT dispersion film, a counter electrode having a width of 1 cm and an interval of 1 cm was prepared. Was found to be 800Ω / □.
比較例３
比較例１で調製したＣＮＴをＣＮＴ濃度１ｇ／Ｌになるようにクロロホルム量を調整し、マグネチックスターラーで撹拌しながら液をスポイト中に０．３ｍＬ秤取った。該液０．３ｍＬを、３ｃｍ角のガラス基板上に滴下し、基板の端に設けた厚み５０μｍの粘着テープをスペーサーとしてブレードキャストした。溶媒が揮発した後、ＣＮＴ膜面を目視観察したところ、ＣＮＴは凝集しており、黒色の斑点が多数観察された。
Comparative Example 3
The amount of chloroform was adjusted so that the CNT prepared in Comparative Example 1 had a CNT concentration of 1 g / L, and 0.3 mL of the liquid was weighed into a dropper while stirring with a magnetic stirrer. 0.3 mL of the liquid was dropped onto a 3 cm square glass substrate, and blade casted using an adhesive tape having a thickness of 50 μm provided at the edge of the substrate as a spacer. When the CNT film surface was visually observed after the solvent was volatilized, the CNTs were agglomerated and many black spots were observed.
実施例７
実施例１と同様の方法を用いて、ＣＮＴ表面にポリ−３−ヘキシルチオフェンが付着したＣＮＴを調製したが、超音波洗浄機を用いてＣＮＴを分散するときに加えるクロロホルムの量を１５０ｍＬから６０ｍＬに減らし、ＣＮＴ濃度０．１ｇ／Ｌの共役系重合体が付着したＣＮＴの均一分散液を得た。
Example 7
A CNT with poly-3-hexylthiophene attached to the CNT surface was prepared using the same method as in Example 1, but the amount of chloroform added when dispersing the CNT using an ultrasonic cleaner was changed from 150 mL to 60 mL. To obtain a uniform CNT dispersion with a conjugated polymer having a CNT concentration of 0.1 g / L.
次いで、得られたＣＮＴ分散液０．１ｍＬを直径２０ｍｍの銀電極上に滴下して溶媒を乾燥し、さらに滴下と乾燥を５回くりかえして、ＣＮＴ分散体膜を得た。なお、銀電極はガラス基板上に銀ペーストを塗布・焼成して形成したものであり、銀電極の周囲には高さ１００μｍ、線幅５０μｍの円形のスペーサー用隔壁をガラスペーストを塗布・焼成して予め形成しておいた。次いでＣＮＴ分散体膜付き銀電極基板と、もう１枚の銀電極付きガラス基板とを、封着ペーストを用い５３０℃で焼成することによって貼り合わせ、脱気孔から真空排気して内圧を１×１０−５Ｐａにすることで、電子放出素子評価用基板Ａを得た。 Next, 0.1 mL of the obtained CNT dispersion liquid was dropped on a silver electrode having a diameter of 20 mm, the solvent was dried, and dropping and drying were repeated 5 times to obtain a CNT dispersion film. The silver electrode is formed by applying and baking a silver paste on a glass substrate. A circular partition wall for a spacer having a height of 100 μm and a line width of 50 μm is applied and fired around the silver electrode. Previously formed. Next, the silver electrode substrate with a CNT dispersion film and another glass substrate with a silver electrode were bonded together by baking at 530 ° C. using a sealing paste, and the internal pressure was reduced to 1 × 10 by evacuating from the deaeration holes. The substrate A for electron-emitting device evaluation was obtained by setting it to -5 Pa.
電子放出素子評価用基板Ａの対向電極間に電圧を印加し、電流値を測定した。徐々に電圧を上げていったところ、エミッション電流が観察され、ターンオン電界は３．８Ｖ／μｍであった。 A voltage was applied between the counter electrodes of the electron-emitting device evaluation substrate A, and the current value was measured. As the voltage was gradually increased, an emission current was observed, and the turn-on electric field was 3.8 V / μm.
実施例８
実施例７で作製したＣＮＴ分散体膜付きの銀電極基板に、ＩＴＯ電極上に厚み１０μｍの蛍光体層を設けた基板を、封着ペーストを用いて貼り合わせ、脱気孔から真空排気して内部圧を１×１０−５Ｐａにすることで、電子放出素子評価用基板Ｂを得た。なお蛍光体粉末は化成オプトニクス（株）製ＣＲＴ用グリーン蛍光体Ｐ２２を用いた。電子放出素子評価用基板Ｂの対向電極間に電圧を５００Ｖ印加したところ、ＣＮＴからの電界放出によって蛍光体がほぼ均一に発光した。
Example 8
The silver electrode substrate with the CNT dispersion film produced in Example 7 was bonded to a substrate having a phosphor layer having a thickness of 10 μm on the ITO electrode using a sealing paste, and the inside was evacuated from the deaeration holes. The substrate B for electron-emitting device evaluation was obtained by setting the pressure to 1 × 10 −5 Pa. The phosphor powder used was CRT green phosphor P22 manufactured by Kasei Optonix. When a voltage of 500 V was applied between the counter electrodes of the electron emission element evaluation substrate B, the phosphors emitted light almost uniformly by field emission from the CNTs.
実施例９
実施例７と同様の方法を用いて、ＣＮＴ表面にポリ−３−ヘキシルチオフェンが付着したＣＮＴを調製し、ＣＮＴ濃度０．１ｇ／Ｌの共役系重合体が付着したＣＮＴの均一分散液を得た。次いで、得られたＣＮＴ分散液１ｍＬを、直径１３ｍｍのポリテトラフルオロエチレン製の０．１μｍ孔フィルターを用いて濾別捕集し、フィルター上にＣＮＴ分散体膜を得た。ＣＮＴ分散体膜の堆積したフィルターをＣＮＴ面が挟まれるようにして直径２０ｍｍの銀電極上に載せ、ＰＥＴフィルムを介してフィルターに押圧をかけた。次いでフィルターを剥がしたところ銀電極上にＣＮＴ分散体膜が形成された。得られたＣＮＴ分散体膜の厚みをレーザー顕微鏡（（株）キーエンス製ＶＦ−７５１０）を用いて測定したところ０．９〜１μｍであり、非常に均一な膜厚であった。こうして作製したＣＮＴ分散体膜付きの銀電極基板に、ＩＴＯ電極上に厚み１０μｍの蛍光体層を設けた基板を、封着ペーストを用いて貼り合わせ、脱気孔から真空排気して内圧を１×１０−５Ｐａにすることで、電子放出素子評価用基板Ｃを得た。電子放出素子評価用基板Ｃの対向電極間に電圧を５００Ｖ印加したところ、ＣＮＴからの電界放出によって蛍光体がほぼ均一に発光した。
Example 9
Using the same method as in Example 7, CNTs with poly-3-hexylthiophene attached to the CNT surface were prepared, and a uniform dispersion of CNTs with a conjugated polymer with a CNT concentration of 0.1 g / L was obtained. It was. Subsequently, 1 mL of the obtained CNT dispersion was collected by filtration using a 0.1 μm pore filter made of polytetrafluoroethylene having a diameter of 13 mm, and a CNT dispersion film was obtained on the filter. The filter on which the CNT dispersion film was deposited was placed on a silver electrode having a diameter of 20 mm so that the CNT surface was sandwiched, and the filter was pressed through a PET film. Next, when the filter was removed, a CNT dispersion film was formed on the silver electrode. When the thickness of the obtained CNT dispersion film was measured using a laser microscope (VF-7510 manufactured by Keyence Corporation), it was 0.9 to 1 μm, which was a very uniform film thickness. A silver electrode substrate with a CNT dispersion film produced in this way was bonded to a substrate having a phosphor layer with a thickness of 10 μm on an ITO electrode using a sealing paste, and the internal pressure was reduced to 1 × by evacuating from the deaeration holes. The substrate C for electron-emitting device evaluation was obtained by setting it as 10 <-5> Pa. When a voltage of 500 V was applied between the counter electrodes of the electron-emitting device evaluation substrate C, the phosphors emitted light almost uniformly by field emission from the CNTs.
比較例４
比較例１で調製したＣＮＴをＣＮＴ濃度０．１ｇ／Ｌになるようにクロロホルム量を調整し、ＣＮＴ含有溶液を作製した。この溶液をマグネチックスターラーで撹拌しながらスポイト中に１ｍＬ秤取った。採取した溶液１ｍＬを、直径１３ｍｍのポリテトラフルオロエチレン製の０．１μｍ孔フィルターを用いて濾別捕集し、フィルター上にＣＮＴ膜を得た。該ＣＮＴ分散体膜の堆積したフィルターをＣＮＴ面が挟まれるようにして直径２０ｍｍの銀電極上に載せ、ＰＥＴフィルムを介してフィルターに押圧をかけた。次いでフィルターを剥がしたところ銀電極上にＣＮＴ膜が形成された。ＣＮＴ膜の厚みをレーザー顕微鏡を用いて測定したところ０．５〜１．５μｍであり、膜厚ムラが非常に大きかった。こうして作製したＣＮＴ膜付きの銀電極基板に、ＩＴＯ電極上に厚み１０μｍの蛍光体層を設けた基板を、封着ペーストを用いて貼り合わせ、脱気孔から真空排気して内圧を１×１０−５Ｐａにすることで、電子放出素子評価用基板Ｄを得た。電子放出素子評価用基板Ｄの対向電極間に電圧を５００Ｖ印加したところ、ＣＮＴからの電界放出によって蛍光体の一部が点状に発光したが、均一に発光しなかった。
Comparative Example 4
The amount of chloroform was adjusted so that the CNT prepared in Comparative Example 1 had a CNT concentration of 0.1 g / L to prepare a CNT-containing solution. 1 mL of this solution was weighed into a dropper while stirring with a magnetic stirrer. 1 mL of the collected solution was collected by filtration using a 0.1 μm pore filter made of polytetrafluoroethylene having a diameter of 13 mm, and a CNT film was obtained on the filter. The filter on which the CNT dispersion film was deposited was placed on a silver electrode having a diameter of 20 mm so that the CNT surface was sandwiched, and the filter was pressed through a PET film. Next, when the filter was peeled off, a CNT film was formed on the silver electrode. When the thickness of the CNT film was measured using a laser microscope, it was 0.5 to 1.5 μm, and the film thickness unevenness was very large. A silver electrode substrate with a CNT film prepared in this manner was bonded to a substrate having a 10 μm thick phosphor layer on an ITO electrode using a sealing paste, and the internal pressure was reduced to 1 × 10 − by evacuating from the deaeration holes. By setting the pressure to 5 Pa, an electron-emitting device evaluation substrate D was obtained. When a voltage of 500 V was applied between the counter electrodes of the substrate for electron-emitting device evaluation D, a part of the phosphor emitted point-like light by field emission from the CNT, but it did not emit uniformly.
用途としてはトランジスターや顕微鏡用プローブなどのようにＣＮＴの単線を使用する方法と、電子放出電極や燃料電池用電極、あるいはＣＮＴを分散した導電性コンポジットなどのように多数のＣＮＴをまとめてバルクとして使用する方法等がある。 Applications include the use of CNT single wires such as transistors and microscope probes, and a large number of CNTs in bulk, such as electron emission electrodes, fuel cell electrodes, or conductive composites with dispersed CNTs. There are methods to use.
１０ 半導体層
２０ ドレイン電極
３０ ソース電極
４０ ＳｉＯ２膜
５０ シリコンウエハー
６０ ゲート電極（シリコンウエハー）
10 Semiconductor layer 20 Drain electrode 30 Source electrode 40 SiO 2 film 50 Silicon wafer 60 Gate electrode (silicon wafer)
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