JP2011171005A - Manufacturing method of carbon nanotube electron emission source - Google Patents

Manufacturing method of carbon nanotube electron emission source Download PDF

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JP2011171005A
JP2011171005A JP2010031540A JP2010031540A JP2011171005A JP 2011171005 A JP2011171005 A JP 2011171005A JP 2010031540 A JP2010031540 A JP 2010031540A JP 2010031540 A JP2010031540 A JP 2010031540A JP 2011171005 A JP2011171005 A JP 2011171005A
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carbon nanotube
film
layer
electron emission
substrate
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Yasuhiko Nishi
泰彦 西
Takehiko Nishigaya
健彦 西ヶ谷
Takamine Mukai
敬峰 向井
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JFE Engineering Corp
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JFE Engineering Corp
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<P>PROBLEM TO BE SOLVED: To provide a CNT electron emission source having no unevenness in electron emission and having good nap raising and high nap raising density of a CNT. <P>SOLUTION: The manufacturing method of a carbon nanotube electron emission source is provided with a carbon nanotube layer forming process to form a conductive paste film on a substrate having conductivity and then form a layer including the carbon nanotube of high density on the conductive paste layer, a calcining process to calcine the carbon nanotube layer formed substrate obtained in the above process at 400-500°C, and a nap raising process in which an adhesive tape is stuck on the carbon nanotube layer surface of the substrate calcined in the above process and then this is peeled off and the carbon nanotube layer surface is made to be in a nap-raised condition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、電極基板上にカーボンナノチューブを固着させて電子放出源を製造する方法に関するものである。   The present invention relates to a method of manufacturing an electron emission source by fixing carbon nanotubes on an electrode substrate.

従来、電極基板上にカーボンナノチューブ（ＣＮＴ）を固着させる方法としては、例えば、絶縁基板にカソード導体を被着し、そのカソード導体にカーボンナノチューブを含むペースト材料を塗布してカーボン層を形成し、このペースト状カーボン層に多孔質シート部材を付着、乾燥し、このシート部材を剥離した後、カーボン層を焼成する方法が知られている（特許文献１）。   Conventionally, as a method of fixing carbon nanotubes (CNT) on an electrode substrate, for example, a cathode conductor is attached to an insulating substrate, and a paste material containing carbon nanotubes is applied to the cathode conductor to form a carbon layer, A method is known in which a porous sheet member is attached to the pasty carbon layer, dried, the sheet member is peeled off, and then the carbon layer is fired (Patent Document 1).

ペースト材料としては、例えば、カーボンナノチューブ３％、バインダーとしてエチルセルロース２５％、ベヒクルとしてガラスパウダー５％、溶媒としてテルピネオール６７％よりなるものが用いられ、これを基板に２０ミクロンの厚さでスクリーン印刷し、４００℃で焼成後、粘着テープによる引き剥がしを行っている。この方法で得られた、電極基板上に固着されたカーボンナノチューブのＳＥＭ像を図９のＡとＢに示す。   As the paste material, for example, a material comprising 3% carbon nanotubes, 25% ethyl cellulose as a binder, 5% glass powder as a vehicle, and 67% terpineol as a solvent is screen-printed on a substrate with a thickness of 20 microns. After baking at 400 ° C., peeling with an adhesive tape is performed. 9A and 9B show SEM images of the carbon nanotubes fixed on the electrode substrate obtained by this method.

特許第３４６８７２３号公報Japanese Patent No. 3468723

カーボンナノチューブ（ＣＮＴ）含有ペーストを用いた従来電子放出源製造技術では、粘着テープでペースト膜を引き剥がす場合、引き剥がれる位置が膜の厚さ方向でばらつき、電子放出に班ができる原因となっていた。また、膜を固定するために、ＣＮＴ以外のバインダーやガラス粉末などを混ぜているので相対的にＣＮＴ密度が低下し、引き剥がした表面の電子放出サイト（毛羽立ったＣＮＴ）の密度低下の原因となっていた。さらに、実際に電子放出に寄与するＣＮＴは表面に存在する毛羽立ったＣＮＴのみであるが、従来法では膜内部に埋もれたＣＮＴや粘着テープで除去されたＣＮＴの割合が多く、高価なＣＮＴを無駄に使用せざるを得なかった。   In the conventional electron emission source manufacturing technology using a carbon nanotube (CNT) -containing paste, when the paste film is peeled off with an adhesive tape, the peeled position varies in the thickness direction of the film, which causes the formation of electron emission. It was. Moreover, since the binder and glass powder other than CNT are mixed in order to fix the film, the CNT density is relatively lowered, and the density of the electron emission site (fluffed CNT) on the peeled surface is reduced. It was. Furthermore, the only CNTs that actually contribute to electron emission are the fluffy CNTs present on the surface, but the conventional method has a large proportion of CNTs buried in the film or removed with adhesive tape, and wastes expensive CNTs. I had to use it.

本発明は、上記問題点を解決するべくなされたものであり、膜構造を多層とし、少なくとも、導電性基板への接着性と通電を確保する導電性ペースト層の第１層と、主としてＣＮＴからなり、強度が弱く引き剥がし時に破断面（ＣＮＴが毛羽立った状態で割れた面）を形成するようにしたカーボンナノチューブ濃度を高めた薄い第２層を設けることで、引き剥がれ位置の安定化と平滑化、電子放出サイトとなる毛羽立ったＣＮＴの密度向上、およびＣＮＴ使用量の削減、が達成できることを見出してなされたものである。   The present invention has been made to solve the above problems, and has a multilayer film structure, at least a first layer of a conductive paste layer that secures adhesion to a conductive substrate and energization, and mainly from CNTs. Therefore, by providing a thin second layer with increased carbon nanotube concentration that forms a fractured surface (a surface that is cracked with fluffy CNTs) at the time of peeling, the peeling position is stabilized and smoothed. The present inventors have found that it is possible to achieve the improvement of the density of the fluffy CNT that becomes an electron emission site and the reduction of the amount of CNT used.

すなわち、本発明は、導電性を有する基板に導電性ペースト膜を形成した後、該導電性ペースト膜上にカーボンナノチューブを含む膜を形成するカーボンナノチューブ層形成工程と、前記工程により得られたカーボンナノチューブ層形成基板を４００〜５００℃で焼成する焼成工程と、前記工程で焼成した基板のカーボンナノチューブ層表面に粘着テープを貼り付け、次いで、これを引き剥がすことにより、前記カーボンナノチューブ層表面を起毛状態とする起毛工程とを有することを特徴とするカーボンナノチューブ電子放出源の製造方法、と導電性を有する基板に導電性ペースト膜を形成した後、該導電性ペースト膜上にカーボンナノチューブを含む膜を形成するカーボンナノチューブ層形成工程と、前記工程により得られた基板のカーボンナノチューブ層表面に更に第３層の膜を形成する工程と、前記工程により得られたカーボンナノチューブ層形成基板を４００〜５００℃で焼成する焼成工程と、前記工程で焼成した基板の膜表面に粘着テープを貼り付け、次いで、これを前記第３層の膜とともに引き剥がす方法によりなるものである。   That is, the present invention provides a carbon nanotube layer forming step of forming a conductive paste film on a conductive substrate and then forming a film containing carbon nanotubes on the conductive paste film, and the carbon obtained by the above step. A firing step of firing the nanotube layer-formed substrate at 400 to 500 ° C., and affixing an adhesive tape to the surface of the carbon nanotube layer of the substrate fired in the step, and then peeling the substrate to raise the surface of the carbon nanotube layer A method of manufacturing a carbon nanotube electron emission source, characterized by having a raising step to make a state, and a film containing carbon nanotubes on the conductive paste film after forming a conductive paste film on a conductive substrate A carbon nanotube layer forming step of forming a substrate, and a substrate curve obtained by the step A step of forming a third layer film on the surface of the carbon nanotube layer, a firing step of firing the carbon nanotube layer-formed substrate obtained in the step at 400 to 500 ° C., and a film surface of the substrate fired in the step The adhesive tape is applied and then peeled off together with the third layer film.

本発明の方法では、導電性基板への接着性と通電を確保する第１層とは別に、カーボンナノチューブ濃度を高めた、強度の弱い第２層を設けることにより、引き剥がし時に第２層で破断面を形成するようにし、かつ破断面に現れる毛羽立ったカーボンナノチューブの密度を高めることができる。そうすることにより、電子放出面が平滑で電子放出サイトが増大するので、従来法に比べ電子放出に要する駆動電圧が低くでき、省エネ効果が高くなる。また電子放出量の面分布が均一となるので、例えば電子を蛍光物質に当て光らせる発光デバイスなどに使用すれば性能の高いものとなる。   In the method of the present invention, in addition to the first layer that secures adhesion to the conductive substrate and energization, the second layer having a weak carbon nanotube concentration is provided, and the second layer is peeled off at the time of peeling. It is possible to increase the density of the fuzzy carbon nanotubes that appear on the fracture surface and to form a fracture surface. By doing so, since the electron emission surface is smooth and the number of electron emission sites is increased, the driving voltage required for electron emission can be lowered as compared with the conventional method, and the energy saving effect is enhanced. In addition, since the surface distribution of the amount of emitted electrons is uniform, for example, when used in a light emitting device that irradiates electrons to a fluorescent material, the performance becomes high.

本発明の方法の一例を模式的に説明する図である。It is a figure which illustrates an example of the method of this invention typically. 実施例１の方法を模式的に説明する図である。It is a figure which illustrates the method of Example 1 typically. 実施例１で得られた膜のＳＥＭ像を示す写真である。2 is a photograph showing an SEM image of the film obtained in Example 1. FIG. 実施例３の方法を模式的に説明する図である。It is a figure which illustrates the method of Example 3 typically. 実施例３で得られた膜のＳＥＭ像を示す写真である。4 is a photograph showing an SEM image of the film obtained in Example 3. FIG. 実施例４の方法を模式的に説明する図である。It is a figure which illustrates the method of Example 4 typically. 実施例４で得られた膜のＳＥＭ像を示す写真である。4 is a photograph showing an SEM image of the film obtained in Example 4. FIG. 従来の方法の一例を模式的に説明する図である。It is a figure which illustrates an example of the conventional method typically. 従来法で得られた膜のＳＥＭ像を示す写真である。It is a photograph which shows the SEM image of the film | membrane obtained by the conventional method. 実施例１〜３および従来法で得られた各電子放出源の電界放出特性を示すグラフである。It is a graph which shows the field emission characteristic of Examples 1-3 and each electron emission source obtained by the conventional method. 実施例２の方法を模式的に説明する図である。It is a figure which illustrates the method of Example 2 typically. 実施例２で得られた膜のＳＥＭ像を示す写真である。2 is a photograph showing an SEM image of the film obtained in Example 2. FIG.

本発明の電極基板は、導電性基板であり、表面にＩＴＯ（錫ドープ酸化インジウム）皮膜を有するガラス基板などが利用できる。ＩＴＯ皮膜は薫着等で形成することができ、ＩＴＯ皮膜を有するガラス基板は公知であり、それを本発明の方法に利用できる。   The electrode substrate of the present invention is a conductive substrate, and a glass substrate having an ITO (tin-doped indium oxide) film on the surface can be used. The ITO film can be formed by adhesion or the like, and glass substrates having an ITO film are known and can be used in the method of the present invention.

導電性ペーストは、一般に市販されているような銀、金、銅、アルミなどの金属微粒子やＩＴＯなどの微粒子、またはカーボン材料の微粒子などを含み導電性を確保したものが利用できる。   As the conductive paste, a conductive paste containing metal fine particles such as silver, gold, copper, and aluminum, fine particles such as ITO, or carbon material fine particles that are commercially available can be used.

導電性ペースト膜の厚みは、乾燥厚みで１〜１０μｍ程度でよく、例えば、スクリーン印刷等で膜を形成できる。   The conductive paste film may have a dry thickness of about 1 to 10 μm. For example, the film can be formed by screen printing or the like.

カーボンナノチューブ層は、例えば、高濃度のカーボンナノチューブのペーストを導電性ペースト膜上に直接塗布することによって形成することができる。カーボンナノチューブペーストは、カーボンナノチューブ、バインダー、ベヒクル、溶媒（分散媒）等よりなる。バインダーとしてはエチルセルロースが主に使用される。ベヒクルとしては、ガラスパウダーやインジウムや錫などの低融点金属、または高分子樹脂などが用いられる。そして分散媒としては、テルピネオールやＢＣＡなど比較的沸点の高いものが用いられる。配合比としては、カーボンナノチューブが１０〜５０重量％程度、バインダーが１０〜３０重量％程度、ベヒクルが１〜１０重量％程度、そして溶媒は４０〜８０重量％程度が適当である。カーボンナノチューブ層を導電性ペースト膜の上にスクリーン印刷する場合は、予め基板を１００℃で１０分程加熱しておき、導電性ペーストに含まれる溶媒を蒸発させ、導電性ペーストを乾燥させてからの方がカーボンナノチューブペーストの印刷性が向上する。また、カーボンナノチューブ層として、カーボンナノチューブを溶媒に分散して濾過することによって形成したようなカーボンナノチューブシートを導電性ペースト膜の上に貼り付けることによっても形成できる。この場合は、導電性ペーストが乾燥する前にカーボンナノチューブシートを導電性ペースト膜の上に貼り付けた方が、両者の接合性が向上するので望ましい。さらに、カーボンナノチューブ層には黒鉛あるいは金属の微粉末を含有させることによってカーボンナノチューブ層の破断（ＣＮＴが毛羽立った状態で割れること）を容易に起こすことができる。金属は例えば銀、金、銅、アルミなどの金属微粒子やＩＴＯなどの微粒子を用いることができる。微粉末の粒径は０．１〜２μｍ程度が適しており、カーボンナノチューブ層における含有量は２０重量％以下が良い。カーボンナノチューブ層の厚みは、乾燥厚みで１〜６μｍ程度が良い。   The carbon nanotube layer can be formed, for example, by directly applying a high-concentration carbon nanotube paste onto the conductive paste film. The carbon nanotube paste includes carbon nanotubes, a binder, a vehicle, a solvent (dispersion medium), and the like. Ethyl cellulose is mainly used as the binder. As the vehicle, glass powder, a low melting point metal such as indium or tin, or a polymer resin is used. As the dispersion medium, those having a relatively high boiling point such as terpineol and BCA are used. The mixing ratio is suitably about 10 to 50% by weight of carbon nanotubes, about 10 to 30% by weight of binder, about 1 to 10% by weight of vehicle, and about 40 to 80% by weight of solvent. When the carbon nanotube layer is screen-printed on the conductive paste film, the substrate is previously heated at 100 ° C. for about 10 minutes, the solvent contained in the conductive paste is evaporated, and the conductive paste is dried. This improves the printability of the carbon nanotube paste. Further, the carbon nanotube layer can also be formed by sticking a carbon nanotube sheet formed by dispersing carbon nanotubes in a solvent and filtering on the conductive paste film. In this case, it is desirable to attach the carbon nanotube sheet on the conductive paste film before the conductive paste is dried, because the bonding property between the two is improved. Further, the carbon nanotube layer can be easily broken (CNTs are cracked in a fluffy state) by containing graphite or metal fine powder. As the metal, for example, metal fine particles such as silver, gold, copper, and aluminum and fine particles such as ITO can be used. The particle size of the fine powder is suitably about 0.1 to 2 μm, and the content in the carbon nanotube layer is preferably 20% by weight or less. The thickness of the carbon nanotube layer is preferably about 1 to 6 μm in terms of dry thickness.

さらに、カーボンナノチューブ層の上に第３層の膜（引き剥がし安定膜）を形成することも好ましい。この膜は、後工程である引き剥がし工程において、カーボンナノチューブ層内での破断を安定化するためのものであり、導電性あるいは不導電性ペーストを用いスクリーン印刷で形成することができる。第３層の厚みは、乾燥厚みで５〜２０μｍ程度が良い。   Furthermore, it is also preferable to form a third layer film (a peeling stable film) on the carbon nanotube layer. This film is for stabilizing the breakage in the carbon nanotube layer in the peeling process, which is a subsequent process, and can be formed by screen printing using a conductive or non-conductive paste. The thickness of the third layer is preferably about 5 to 20 μm in terms of dry thickness.

カーボンナノチューブ層を含む膜を形成したら、次いで焼成する。焼成とは、ペースト中の有機成分を炭化させると共に、基板との密着性を強固にするために行う。焼成は大気中で、温度は４００〜５００℃程度で１０〜３０分程度行なえばよい。   Once the film containing the carbon nanotube layer is formed, it is then fired. Firing is performed to carbonize the organic component in the paste and strengthen the adhesion to the substrate. Firing may be performed in air at a temperature of about 400 to 500 ° C. for about 10 to 30 minutes.

焼成後は、そのまま粘着テープの貼り付けと引き剥がしを行い、カーボンナノチューブ層で破断させることによりカーボンナノチューブの起毛した表面を形成する。   After firing, the adhesive tape is applied and peeled off as it is, and the carbon nanotube layer is broken to form a raised surface of the carbon nanotubes.

ＩＴＯ膜を有するガラス基板のＩＴＯ膜上に導電性ペーストとして銀ペーストを５μｍの厚さにスクリーン印刷した。これを１００℃のホットプレートの上に約１０分間置き、溶媒を蒸発させてペーストを乾燥させた。続いて、カーボンナノチューブを１０％含有するカーボンナノチューブペーストを同じく５μｍの厚さにスクリーン印刷した。次いで１００℃のホットプレートの上に約１０分間置き、溶媒を蒸発させてペーストを乾燥させた後、大気中４５０℃で１０分間焼成した。   A silver paste as a conductive paste was screen-printed to a thickness of 5 μm on the ITO film of the glass substrate having the ITO film. This was placed on a hot plate at 100 ° C. for about 10 minutes, and the solvent was evaporated to dry the paste. Subsequently, a carbon nanotube paste containing 10% of carbon nanotubes was similarly screen-printed to a thickness of 5 μm. Next, the paste was dried on a hot plate at 100 ° C. for about 10 minutes to evaporate the solvent, and then baked at 450 ° C. for 10 minutes in the atmosphere.

焼成後は、粘着テープを軽く押し付けて貼り付け、次いで粘着テープを引き剥がしてカーボンナノチューブ電子放出源を得た。   After firing, the pressure-sensitive adhesive tape was lightly pressed and pasted, and then the pressure-sensitive adhesive tape was peeled off to obtain a carbon nanotube electron emission source.

得られたカーボンナノチューブ電子放出源のＳＥＭ像を場所を変えて撮影し、図３に示す像を得た。同図Ａに示すように、引き剥がし面には、カーボンナノチューブ（ＣＮＴ）が密集していることがわかる。このＣＮＴ電子放出源で電流密度１ｍＡ／ｃｍ２の放出電流が得られる平均電界値は２．０Ｖ／μｍであった。 The obtained SEM image of the carbon nanotube electron emission source was photographed at different locations, and the image shown in FIG. 3 was obtained. As shown in FIG. 5A, it can be seen that carbon nanotubes (CNT) are densely packed on the peeling surface. The average electric field value at which an emission current with a current density of 1 mA / cm 2 was obtained with this CNT electron emission source was 2.0 V / μm.

第２層のカーボンナノチューブペーストを印刷し乾燥させるまでは、実施例１と同様に行った。その後、カーボンナノチューブ層表面に、第３層の膜を印刷した。第３層の膜は、第1層の導電性ペーストと同じものを用い、厚さ５μmで印刷した。その後、１００℃のホットプレートの上に約１０分間置き、溶媒を蒸発させてペーストを乾燥させた後、大気中４５０℃で１０分間焼成した。   The same procedure as in Example 1 was performed until the carbon nanotube paste of the second layer was printed and dried. Thereafter, a third layer film was printed on the surface of the carbon nanotube layer. The third layer film was the same as the first layer conductive paste, and was printed with a thickness of 5 μm. Thereafter, the paste was placed on a hot plate at 100 ° C. for about 10 minutes to evaporate the solvent and dried, and then baked at 450 ° C. for 10 minutes in the atmosphere.

得られたカーボンナノチューブ電子放出源のＳＥＭ像を場所を変えて撮影し、図１２を得た。同図Ａに示すように、引き剥がしが安定して行われたことがわかる。このＣＮＴ電子放出源は、電流密度１ｍＡ／ｃｍ２の放出電流が得られる平均電界値は１．６Ｖ／μｍであった。 SEM images of the obtained carbon nanotube electron emission source were taken at different locations, and FIG. 12 was obtained. As shown in FIG. 5A, it can be seen that the peeling was performed stably. This CNT electron emission source had an average electric field value of 1.6 V / μm at which an emission current with a current density of 1 mA / cm 2 was obtained.

ＩＴＯ膜を有するガラス基板のＩＴＯ膜上に導電性ペーストとして銀ペーストを５μｍの厚さにスクリーン印刷した。導電性ペーストを乾燥させる前に、厚さ４μｍのカーボンナノチューブシート（ＣＮＴシート）を軽く押し付けて貼り付けた。次いで１００℃のホットプレートの上に約１０分間置き、溶媒を蒸発させてペーストを乾燥させた。その後は、実施例２と同様に、カーボンナノチューブ層表面に、第３層の膜を印刷し、乾燥後大気中４５０℃で１０分間焼成した。   A silver paste as a conductive paste was screen-printed to a thickness of 5 μm on the ITO film of the glass substrate having the ITO film. Before the conductive paste was dried, a carbon nanotube sheet (CNT sheet) having a thickness of 4 μm was lightly pressed and pasted. The paste was then dried by placing it on a hot plate at 100 ° C. for about 10 minutes to evaporate the solvent. Thereafter, in the same manner as in Example 2, the third layer film was printed on the surface of the carbon nanotube layer, dried, and baked at 450 ° C. for 10 minutes in the air.

得られたカーボンナノチューブ電子放出源のＳＥＭ像を場所を変えて撮影し、図５を得た。同図Ａに示すように、引き剥がしが安定して行われたことがわかる。このＣＮＴ電子放出源は、電流密度１ｍＡ／ｃｍ２の放出電流が得られる平均電界値は１．４Ｖ／μｍであった。 The obtained SEM image of the carbon nanotube electron emission source was taken at different locations, and FIG. 5 was obtained. As shown in FIG. 5A, it can be seen that the peeling was performed stably. This CNT electron emission source had an average electric field value of 1.4 V / μm at which an emission current with a current density of 1 mA / cm 2 was obtained.

用いたカーボンナノチューブシート以外は実施例３と同様に行った。カーボンナノチューブシートは平均粒径１μｍの黒鉛粉を１０％混合した厚さ６μｍのものを用いた。   The same procedure as in Example 3 was performed except for the carbon nanotube sheet used. The carbon nanotube sheet was 6 μm thick with 10% graphite powder having an average particle diameter of 1 μm mixed.

得られたカーボンナノチューブ電子放出源のＳＥＭ像を場所を変えて撮影し、図７を得た。同図Ａに示すように、微粒子の影響で、ＣＮＴシートでの引き剥がしが容易になり、ＣＮＴの起毛が大きくなったことがわかる。このＣＮＴ電子放出源は、電流密度１ｍＡ／ｃｍ２の放出電流が得られる平均電界値は１．２Ｖ／μｍであった。 SEM images of the obtained carbon nanotube electron emission source were taken at different locations, and FIG. 7 was obtained. As shown in FIG. 5A, it can be seen that the CNT sheet is easily peeled off by the influence of the fine particles, and the CNTs are raised. This CNT electron emission source had an average electric field value of 1.2 V / μm at which an emission current with a current density of 1 mA / cm 2 was obtained.

従来例Conventional example

実施例１〜４と同じでＩＴＯ膜を有するガラス基板のＩＴＯ膜上にペーストを２０μｍの厚さにスクリーン印刷した。用いたペーストは、ＣＮＴ３重量％、エチルセルロース（バインダー）２５重量％、ガラスパウダー（ベヒクル）５重量％およびテルピネオール（溶媒）６７重量％よりなるものを用いた。次いで、４００℃で１０分間焼成した。   The paste was screen-printed to a thickness of 20 μm on the ITO film of a glass substrate having the same ITO film as in Examples 1 to 4. The paste used was 3% by weight of CNT, 25% by weight of ethyl cellulose (binder), 5% by weight of glass powder (vehicle) and 67% by weight of terpineol (solvent). Subsequently, it baked for 10 minutes at 400 degreeC.

焼成後は、粘着テープを軽く押し付けて貼り付け、次いで、粘着テープを引き剥がしてカーボンナノチューブ電子放出源を得た。   After firing, the pressure-sensitive adhesive tape was lightly pressed and pasted, and then the pressure-sensitive adhesive tape was peeled off to obtain a carbon nanotube electron emission source.

得られたカーボンナノチューブ電子放出源のＳＥＭ像を場所を変えて撮影し、図９を得た。同図Ａに示すように、引き剥がしの際に班ができ、また、同図Ｂに示すように起毛したＣＮＴが少ないことがわかる。このＣＮＴ電子放出源は、電流密度１ｍＡ／ｃｍ２の放出電流が得られる平均電界値は２．６Ｖ／μｍであった。 SEM images of the obtained carbon nanotube electron emission source were taken at different locations, and FIG. 9 was obtained. As shown in FIG. 5A, it can be seen that a group is formed at the time of peeling, and the raised CNTs are small as shown in FIG. This CNT electron emission source had an average electric field value of 2.6 V / μm at which an emission current with a current density of 1 mA / cm 2 was obtained.

各実施例および従来例で得られたカーボンナノチューブ電子放出源の平均電界と放出電流密度との関係を測定した結果を図１０に示す。   FIG. 10 shows the results of measuring the relationship between the average electric field and the emission current density of the carbon nanotube electron emission sources obtained in the examples and the conventional examples.

本発明で得られるカーボンナノチューブ電子放出源は、電子放出特性にすぐれていることから、電界放出型電子放出素子として、種々の電気機器、電子装置に用いることができる。   Since the carbon nanotube electron emission source obtained by the present invention has excellent electron emission characteristics, it can be used as a field emission type electron emission element in various electric devices and electronic devices.

図１０における■は実施例１、△は実施例２、×は実施例３、◆は従来例をそれぞれ示している。   In FIG. 10, ■ indicates Example 1, Δ indicates Example 2, × indicates Example 3, and ◆ indicates a conventional example.

Claims (3)

導電性を有する基板に導電性ペースト膜を形成した後、該導電性ペースト膜上に高濃度のカーボンナノチューブを含む膜を形成するカーボンナノチューブ層形成工程と、前記工程により得られたカーボンナノチューブ層形成基板を４００〜５００℃で焼成する焼成工程と、前記工程で焼成した基板のカーボンナノチューブ層表面に粘着テープを貼り付け、次いで、これを引き剥がすことにより、前記カーボンナノチューブ層表面を起毛状態とする起毛工程とを有することを特徴とするカーボンナノチューブ電子放出源の製造方法。   After forming a conductive paste film on a conductive substrate, a carbon nanotube layer forming step of forming a film containing a high concentration of carbon nanotubes on the conductive paste film, and forming a carbon nanotube layer obtained by the above steps A baking step of baking the substrate at 400 to 500 ° C., and affixing an adhesive tape on the surface of the carbon nanotube layer of the substrate baked in the step, and then peeling the substrate to bring the surface of the carbon nanotube layer into a raised state A method of manufacturing a carbon nanotube electron emission source. 導電性を有する基板に導電性ペースト膜を形成した後、該導電性ペースト膜上に高濃度のカーボンナノチューブを含む膜を形成するカーボンナノチューブ層形成工程と、前記工程により得られた基板のカーボンナノチューブ層表面に更に第３層の膜を形成する工程と、前記工程により得られたカーボンナノチューブ層形成基板を４００〜５００℃で焼成する焼成工程と、前記工程で焼成した基板の膜表面に粘着テープを貼り付け、次いで、これを前記第３層の膜とともに引き剥がすことにより、前記カーボンナノチューブ層表面を起毛状態とする起毛工程とを有することを特徴とするカーボンナノチューブ電子放出源の製造方法。   A carbon nanotube layer forming step of forming a conductive paste film on a conductive substrate and then forming a film containing high-concentration carbon nanotubes on the conductive paste film, and a carbon nanotube of the substrate obtained by the above step A step of further forming a third layer film on the surface of the layer, a firing step of firing the carbon nanotube layer-formed substrate obtained in the step at 400 to 500 ° C., and an adhesive tape on the film surface of the substrate fired in the step And then raising the surface of the carbon nanotube layer by raising it together with the film of the third layer, thereby producing a carbon nanotube electron emission source. 前記カーボンナノチューブ層をカーボンナノチューブシートまたは、黒鉛あるいは金属の微粉末を含有するシートとすることを特徴とする請求項１または請求項２に記載のカーボンナノチューブ電子放出源の製造方法。   3. The method of manufacturing a carbon nanotube electron emission source according to claim 1, wherein the carbon nanotube layer is a carbon nanotube sheet or a sheet containing fine powder of graphite or metal.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013184832A (en) * 2012-03-06 2013-09-19 Fujitsu Ltd Method of manufacturing carbon nanotube sheet, method of manufacturing semiconductor device, and substrate for forming carbon nanotube

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013184832A (en) * 2012-03-06 2013-09-19 Fujitsu Ltd Method of manufacturing carbon nanotube sheet, method of manufacturing semiconductor device, and substrate for forming carbon nanotube

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