JP4706056B2 - Method for converting properties of single-walled carbon nanotube aggregates - Google Patents
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本発明は、単層カーボンナノチューブ集合体が有する半導体的性質を低減させ、金属的性質を増大させる特性変換方法に関するものである。 The present invention relates to a characteristic conversion method for reducing semiconducting properties of a single-walled carbon nanotube aggregate and increasing metallic properties.
単層カーボンナノチューブ（ＳＷＮＴ）は炭素でできた物質であり、炭素の六角員環からなるシート（グラフェンシート）を筒状に巻いた形状をしている。ＳＷＮＴ集合体は、グラフェンシートの巻き方により導電性や光吸収スペクトルが異なるという特異な性質を持ち、将来の機能材料としての応用が期待されている。一方、実際のＳＷＮＴ集合体の中には、電子構造が金属的で、金属的性質を呈するＳＷＮＴ（金属ＳＷＮＴ）と、電子構造が半導体的で、半導体的性質を呈するＳＷＮＴ（半導体ＳＷＮＴ）とが混在する。 A single-walled carbon nanotube (SWNT) is a substance made of carbon, and has a shape in which a sheet (graphene sheet) made of a hexagonal ring of carbon is wound into a cylindrical shape. The SWNT aggregate has a unique property that conductivity and light absorption spectrum differ depending on how the graphene sheet is wound, and is expected to be applied as a functional material in the future. On the other hand, in an actual SWNT aggregate, there are SWNTs (metal SWNTs) whose electronic structure is metallic and exhibits metallic properties, and SWNTs (semiconductor SWNTs) whose electronic structure is semiconducting and exhibits semiconducting properties. Mixed.
現在、ＳＷＮＴは、主にレーザー蒸発法、アーク放電法、及び気相化学蒸着法（ＣＶＤ法）を用いて形成することができ、ＣＶＤ法で生成されたＳＷＮＴが現在は多く市販されている。しかしながら、このような生成技術を用いた場合、上述したＳＷＮＴ集合体中には必然的に金属ＳＷＮＴと半導体ＳＷＮＴとが混在するようになってしまう。このようなＳＷＮＴ集合体の特性は、ＳＷＮＴ集合体に対して種々の応用（例えばＦＥＴ、光学素子、導線、電極、ＦＥＤなど）を考えたとき致命的な欠点となる。 At present, SWNTs can be formed mainly using a laser evaporation method, an arc discharge method, and a vapor phase chemical vapor deposition method (CVD method), and many SWNTs produced by the CVD method are currently commercially available. However, when such a generation technique is used, the SWNT aggregate described above inevitably contains a mixture of metal SWNTs and semiconductor SWNTs. Such a characteristic of the SWNT aggregate becomes a fatal defect when various applications (for example, FET, optical element, conductive wire, electrode, FED, etc.) are considered for the SWNT aggregate.
特に、半導体デバイスに用いるナノ電線の用途では、そのサイズから銅線では十分な電気伝導が確保できず、このため金属単層カーボンナノチューブを用いることが検討されており、かかる観点からもＳＷＮＴ集合体の上述した特性は致命的となっている。 In particular, in the use of nano wires used in semiconductor devices, sufficient electrical conduction cannot be ensured with copper wires because of their size, and therefore, the use of metal single-walled carbon nanotubes has been studied. The above properties are fatal.
上述したような問題に鑑み、現在、ＳＷＮＴ集合体において、金属ＳＷＮＴと半導体ＳＷＮＴとを分離することが大きな課題となっている。例えば、特開２００４−２１０６０８号公報、及びM. Yudasaka et al. Chem. Phys. Lett., 374（2003）pp. 132-136では、光照射によリＳＷＮＴ集合体を構造選択的に除去することが開示されている。これらの技術では、光の波長を選ぶことで半導体ＳＷＮＴ、若しくは金属ＳＷＮＴを選択的に除去するものである。 In view of the problems as described above, at present, it is a big problem to separate the metal SWNT and the semiconductor SWNT in the SWNT aggregate. For example, in JP-A-2004-210608 and M. Yudasaka et al. Chem. Phys. Lett., 374 (2003) pp. 132-136, the SWNT aggregate is selectively removed by light irradiation. It is disclosed. In these techniques, the semiconductor SWNT or the metal SWNT is selectively removed by selecting the wavelength of light.
また、Z. Chen et al. Nano Lett., 3（2003）pp. 1245-1249には、臭素と半導体ＳＷＮＴ、金属ＳＷＮＴとの相互作用の違いを利用して、最終的に遠心分離で金属ＳＷＮＴをより選択的に沈殿させて得、前記半導体ＳＷＮＴを選択的に除去する方法が開示されている。さらに、R. Krupke et al. Science, 301（2003）pp. 344-347では、ＳＷＮＴを界面活性剤で孤立させ、電気泳動法を用いて金属ＳＷＮＴを選択的に電極間に配向させることにより、半導体ＳＷＮＴを選択的に除去することが開示されている。 In addition, Z. Chen et al. Nano Lett., 3 (2003) pp. 1245-1249 uses the difference in interaction between bromine and semiconductor SWNTs and metal SWNTs, and finally the metal SWNTs by centrifugation. Has been disclosed to selectively remove the semiconductor SWNT. Furthermore, in R. Krupke et al. Science, 301 (2003) pp. 344-347, by isolating SWNTs with a surfactant and selectively orienting metal SWNTs between electrodes using electrophoresis, It is disclosed that the semiconductor SWNT is selectively removed.
しかしながら、上記いずれの方法においても、ＳＷＮＴ集合体より半導体ＳＷＮＴを効率的に十分な割合で選択的に除去し、金属ＳＷＮＴを十分に高い割合で残存させるには至っていない。 However, in any of the above-described methods, the semiconductor SWNTs are efficiently and selectively removed from the SWNT aggregate at a sufficient rate, and the metal SWNTs are not left at a sufficiently high rate.
本発明は、ＳＷＮＴ集合体から半導体ＳＷＮＴを効率的に十分な割合で選択的に除去し、金属ＳＷＮＴを十分に高い割合で、簡易に残存させることができる新規な方法を提供することを目的とする。 An object of the present invention is to provide a novel method capable of efficiently removing semiconductor SWNTs from SWNT aggregates efficiently and at a sufficient rate and easily leaving metal SWNTs at a sufficiently high rate. To do.
上記目的を達成すべく、本発明は、
単層カーボンナノチューブ集合体に対して酸化処理を施す工程を具え、前記単層カーボンナノチューブ集合体の半導体的性質を呈するカーボンナノチューブを選択的に酸化してその機能を消滅せしめ、前記単層カーボンチューブ集合体における金属的性質を呈するカーボンナノチューブの割合を増大させることを特徴とする、単層カーボンナノチューブ集合体の特性変換方法に関する。
In order to achieve the above object, the present invention provides:
A step of oxidizing the single-walled carbon nanotube aggregate to selectively oxidize the carbon nanotubes exhibiting the semiconducting properties of the single-walled carbon nanotube aggregate to eliminate their functions, and the single-walled carbon tube The present invention relates to a method for converting characteristics of a single-walled carbon nanotube aggregate, wherein the proportion of carbon nanotubes exhibiting metallic properties in the aggregate is increased.
本発明者らは、上記目的を達成すべく鋭意検討を実施した。その結果、単層カーボンナノチューブ（ＳＷＮＴ）集合体に酸化処理を施し、その諸条件、例えば酸化時間、温度及び使用する酸化剤の種類などを適宜に制御し、選択することにより、半導体的性質を有するＳＷＮＴ（半導体ＳＷＮＴ）が選択的に酸化され、その機能が消滅するようになり、前記半導体ＳＷＮＴが実質的に選択除去されるようになり、前記ＳＷＮＴ集合体中での金属的性質を有するＳＷＮＴ（金属ＳＷＮＴ）の割合が相対的に増大することを見出した。 The inventors of the present invention have intensively studied to achieve the above object. As a result, by subjecting single-walled carbon nanotube (SWNT) aggregates to oxidation treatment, various conditions such as oxidation time, temperature and type of oxidant to be used are appropriately controlled and selected, so that semiconductor properties can be selected. SWNTs (semiconductor SWNTs) are selectively oxidized and their functions disappear, the semiconductor SWNTs are substantially selectively removed, and SWNTs having metallic properties in the SWNT aggregate It has been found that the ratio of (metal SWNT) is relatively increased.
したがって、前記ＳＷＮＴ集合体は、全体として金属的な性質を呈するようになり、ＦＥＴ、光学素子、導線、電極、ＦＥＤなどの種々の用途に適用することができるようになり、さらには、従来困難であったナノ電線の実現も可能となる。 Therefore, the SWNT aggregate exhibits metallic properties as a whole, and can be applied to various uses such as FETs, optical elements, conductive wires, electrodes, FEDs, and is difficult in the past. It is also possible to realize nanowires that were
なお、前記酸化処理は、所定の酸化剤を用い、これを含む雰囲気下にＳＷＮＴ集合体を配置することによって実施することができる。この際、必要に応じて、前記雰囲気を加熱することもできる。 In addition, the said oxidation process can be implemented by arrange | positioning a SWNT aggregate | assembly in the atmosphere containing this using a predetermined | prescribed oxidizing agent. Under the present circumstances, the said atmosphere can also be heated as needed.
また、本発明の好ましい態様においては、ＳＷＮＴ集合体中に含まれる金属触媒などの触媒成分を除去する工程を含む。さらには、ＳＷＮＴ集合体中に含まれるＳＷＮＴ構成以外の炭素不純物を除去する工程を含む。ＳＷＮＴ集合体内にこのような残留触媒成分や炭素不純物が含まれていると、半導体ＳＷＮＴを酸化させてその機能を生ぜしめ、実質的に選択除去するようにしても、残留触媒成分や炭素不純物などの影響によって、前記ＳＷＮＴ集合体内での金属的性質の発現が低下してしまう場合がある。したがって、本発明の好ましい態様に従って、残留触媒成分や炭素不純物を除去することが好ましい。 Moreover, in the preferable aspect of this invention, the process of removing catalyst components, such as a metal catalyst contained in a SWNT aggregate | assembly, is included. Furthermore, it includes a step of removing carbon impurities other than the SWNT structure contained in the SWNT aggregate. If such a residual catalyst component or carbon impurity is contained in the SWNT assembly, the semiconductor SWNT is oxidized to generate its function, and even if it is substantially selectively removed, the residual catalyst component, carbon impurity, etc. As a result, the expression of metallic properties in the SWNT aggregate may be reduced. Therefore, it is preferable to remove residual catalyst components and carbon impurities in accordance with a preferred embodiment of the present invention.
以上説明したように、本発明によれば、ＳＷＮＴ集合体から半導体ＳＷＮＴを効率的に十分な割合で選択的に除去し、金属ＳＷＮＴを十分に高い割合で、簡易に残存させることができる新規な方法を提供することができる。したがって、前記ＳＷＮＴ集合体は、ＦＥＴ、光学素子、導線、電極、ＦＥＤなどの種々の用途に適用することができるようになり、さらには、従来困難であったナノ電線の実現も可能となる。 As described above, according to the present invention, the semiconductor SWNT can be selectively removed from the SWNT aggregate efficiently and at a sufficient rate, and the metal SWNT can be easily left at a sufficiently high rate. A method can be provided. Therefore, the SWNT aggregate can be applied to various uses such as FETs, optical elements, conducting wires, electrodes, FEDs, and further, nanowires that have been difficult in the past can be realized.
以下、本発明の詳細、その他の特徴及び利点について、発明を実施するための最良の形態に基づいて説明する。 Hereinafter, details of the present invention, other features and advantages will be described based on the best mode for carrying out the invention.
本発明の特性変換方法においては、最初に単層カーボンナノチューブ（ＳＷＮＴ）集合体を準備し、このＳＷＮＴ集合体に対して酸化処理を施す。酸化処理は、好ましくは酸化剤を用い、この酸化剤を含む雰囲気中に前記ＳＷＮＴ集合体を配置することによって実施する。 In the property conversion method of the present invention, a single-walled carbon nanotube (SWNT) aggregate is first prepared, and the SWNT aggregate is subjected to oxidation treatment. The oxidation treatment is preferably performed by using an oxidizing agent and placing the SWNT aggregate in an atmosphere containing the oxidizing agent.
前記酸化剤としては、本発明の目的を実現できる限りにおいて、あらゆる種類のものを用いることができるが、好ましくは過酸化水素を用いる。これによって、前記ＳＷＮＴ集合体の内、半導体ＳＷＮＴのみを効率的に酸化させることができ、金属ＳＷＮＴの残存割合を効率的に増大させて、本発明の目的をより効果的に実現することができるようになる。 As the oxidizing agent, any kind can be used as long as the object of the present invention can be realized, but hydrogen peroxide is preferably used. As a result, only the semiconductor SWNT in the SWNT aggregate can be efficiently oxidized, and the remaining ratio of the metal SWNT can be efficiently increased, thereby realizing the object of the present invention more effectively. It becomes like this.
前記酸化剤が室温で固体状であれば、前記ＳＷＮＴ集合体に前記酸化剤を直接接触させる、あるいは前記酸化剤を所定の溶媒中に溶解させることによって溶液とし、この溶液に対して所定時間浸漬させることによって酸化処理を行うことができる。さらに、前記酸化剤が室温で液体状であれば、ＳＷＮＴ集合体を前記酸化剤中に直接浸漬させる、あるいは希釈させた酸化剤中に浸漬させることによって酸化処理を行うことができる。また、前記酸化剤が室温で気体状であれば、ＳＷＮＴ集合体を前記酸化剤を含む気体雰囲気中に配置することによって行う。 If the oxidant is solid at room temperature, the SWNT aggregate is brought into direct contact with the oxidant, or the oxidant is dissolved in a predetermined solvent to form a solution and immersed in the solution for a predetermined time. By performing this, oxidation treatment can be performed. Furthermore, if the oxidizing agent is liquid at room temperature, the oxidation treatment can be performed by immersing the SWNT aggregate directly in the oxidizing agent or by immersing it in a diluted oxidizing agent. Further, if the oxidizing agent is gaseous at room temperature, the SWNT aggregate is placed in a gas atmosphere containing the oxidizing agent.
過酸化水素は、室温において液体であるため、上記液体状の酸化剤を用いた場合の酸化処理操作に従って酸化処理を行う。 Since hydrogen peroxide is a liquid at room temperature, the oxidation treatment is performed according to the oxidation treatment operation in the case of using the liquid oxidant.
また、本発明においては、上述した酸化処理に加えて、ＳＷＮＴ集合体に含まれる金属触媒などの触媒成分を除去し、ＳＷＮＴを構成する以外の炭素不純物を除去することが好ましい。このような残留触媒や炭素不純物がＳＷＮＴ集合体内に含まれていると、半導体ＳＷＮＴを酸化させてその機能を生ぜしめ、実質的に選択除去するようにしても、残留触媒成分や炭素不純物などの影響によって、前記ＳＷＮＴ集合体内での金属的性質の発現が低下してしまう場合がある。 In the present invention, in addition to the oxidation treatment described above, it is preferable to remove catalyst components such as a metal catalyst contained in the SWNT aggregate to remove carbon impurities other than those constituting the SWNT. If such a residual catalyst or carbon impurity is contained in the SWNT aggregate, the semiconductor SWNT is oxidized to produce its function, and even if it is substantially selectively removed, the residual catalyst component, carbon impurity, etc. Due to the influence, the expression of metallic properties in the SWNT aggregate may be reduced.
残留した金属触媒を除去するに際しては、塩酸や硫酸などの酸を用いて溶解除去する。また、炭素不純物を除去するに際しては、酸素含有雰囲気中で燃焼させて除去することができる。 When removing the remaining metal catalyst, it is dissolved and removed using an acid such as hydrochloric acid or sulfuric acid. Moreover, when removing carbon impurities, it can be removed by burning in an oxygen-containing atmosphere.
上述した操作に供するＳＷＮＴ集合体は公知の方法によって製造することができ、例えばレーザ蒸着法、アーク放電法、及びＣＶＤ法などを用いて製造することができる。 The SWNT aggregate subjected to the above-described operation can be manufactured by a known method, for example, using a laser vapor deposition method, an arc discharge method, a CVD method, or the like.
最初に、ＣＮＩ社より購入したＳＷＮＴ集合体を準備した。このＳＷＮＴ集合体は、鉄触媒に高温で一酸化炭素ガスを接触させ、熱分解させてＳＷＮＴ集合体を作製する、熱ＣＶＤ法を利用したＨｉＰｃｏ法（High pressure carbon monoxide method）によって得られるものである。 First, a SWNT assembly purchased from CNI was prepared. This SWNT aggregate is obtained by the HiPco method (High pressure carbon monoxide method) using a thermal CVD method in which a carbon monoxide gas is brought into contact with an iron catalyst at a high temperature and thermally decomposed to produce a SWNT aggregate. is there.
次いで、前記ＳＷＮＴ集合体（ＳＷＮＴ１）を、３００℃に保持された空気中に約３０分間配置し、混入している鉄微粒子（鉄触媒）の周りの炭素物質を燃焼させた。次いで、前記ＳＷＮＴを塩酸の中に分散させ、混入している鉄微粒子を塩酸溶液中に溶解させた。この後、鉄微粒子が溶解した塩酸溶液をメンブレンフィルタでろ過することで、前記メンブレンフィルタ上に鉄微粒子を除去したＳＷＮＴだけを残存させ、回収した（ＳＷＮＴ２）。 Next, the SWNT aggregate (SWNT1) was placed in air kept at 300 ° C. for about 30 minutes, and the carbon material around the iron fine particles (iron catalyst) mixed therein was burned. Next, the SWNTs were dispersed in hydrochloric acid, and the mixed iron fine particles were dissolved in a hydrochloric acid solution. Thereafter, the hydrochloric acid solution in which the iron fine particles were dissolved was filtered through a membrane filter, so that only the SWNTs from which the iron fine particles had been removed remained on the membrane filter and recovered (SWNT2).
次いで、回収したＳＷＮＴ２の４ｍｇを、濃度３０％の過酸化水素水溶液３０ｍＬの中で１時間ほど超音波分散させた。次いで、得られたＳＷＮＴ分散液を９０℃に加熱し、過酸化水素によるＳＷＮＴ２の酸化を促進させた。約５２分間、過酸化水素による酸化処理を実施した後、前記分散液を室温まで冷却し、塩酸溶液中に分散させて、残っている鉄微粒子を再度除去した。その後、得られたＳＷＮＴ分散液をろ過することにより、最終的なＳＷＮＴ集合体（ＳＷＮＴ３）を得た。 Next, 4 mg of the recovered SWNT2 was ultrasonically dispersed in 30 mL of a 30% aqueous hydrogen peroxide solution for about 1 hour. Next, the obtained SWNT dispersion was heated to 90 ° C. to promote the oxidation of SWNT2 with hydrogen peroxide. After an oxidation treatment with hydrogen peroxide for about 52 minutes, the dispersion was cooled to room temperature and dispersed in a hydrochloric acid solution, and the remaining iron fine particles were removed again. Then, the final SWNT aggregate (SWNT3) was obtained by filtering the obtained SWNT dispersion.
図１は、上述した酸化処理過程にある３つのＳＷＮＴ（ＳＷＮＴ１〜３）の光吸収スペクトルである。この図において、ＳＷＮＴ１及び２の、０．５ｅＶから１．２５ｅＶの間に現れている吸収ピークは、半導体ＳＷＮＴのヴァンホーベ特異点（vHS）間の光学遷移に対応しており、１．９６ｅＶから２．６ｅＶの間に現れる吸収ピークが、金属ＳＷＮＴのvHS間の光学遷移に対応している。ＳＷＮＴ３の、０．５ｅＶから１ｅＶの間に現れている吸収ピークは、半導体ＳＷＮＴのvHS間の光学遷移に対応しており、１．７ｅＶから２．６ｅＶの間に現れる吸収ピークが、金属ＳＷＮＴのvHS間の光学遷移に対応している。
FIG. 1 is a light absorption spectrum of three SWNTs (
図１から明らかなように、ＳＷＮＴ１及び２に比べ、ＳＷＮＴ３の金属ＳＷＮＴにおけるvHS間の光学遷移が半導体ＳＷＮＴのvHS間の光学遷移に比べて増加していることがわかる。つまりＳＷＮＴ３における金属ＳＷＮＴの存在する割合が増えていることを示している。これはＳＷＮＴ２を過酸化水素で処理することでＳＷＮＴ２の中の半導体ＳＷＮＴを選択的に除去できたことを示している。 As is apparent from FIG. 1, it can be seen that the optical transition between vHS in SWNT3 metal SWNT is larger than that in SWNT1 and 2, compared with the optical transition between vHS in semiconductor SWNT. That is, it shows that the proportion of the metal SWNT in SWNT3 is increasing. This indicates that the semiconductor SWNT in the SWNT2 can be selectively removed by treating the SWNT2 with hydrogen peroxide.
以上、本発明を具体例を挙げながら詳細に説明してきたが、本発明は上記内容に限定されるものではなく、本発明の範疇を逸脱しない限りにおいてあらゆる変形や変更が可能である。 The present invention has been described in detail with specific examples. However, the present invention is not limited to the above contents, and various modifications and changes can be made without departing from the scope of the present invention.
Claims (6)
6. The method for converting characteristics of a single-walled carbon nanotube aggregate according to claim 5, wherein the carbon impurities are removed by burning in an oxygen-containing atmosphere.
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| JP5215672B2 (en) | 2005-03-04 | 2013-06-19 | ノースウェスタン ユニバーシティ | Separation of carbon nanotubes by density gradient |
| JP4292299B2 (en) * | 2005-04-01 | 2009-07-08 | 国立大学法人東北大学 | Tubular nanocarbon and method for producing tubular nanocarbon |
| CN101600650B (en) | 2006-08-30 | 2015-04-29 | 西北大学 | Monodisperse single-walled carbon nanotube populations and related methods for providing same |
| JP4953444B2 (en) * | 2007-07-10 | 2012-06-13 | 独立行政法人産業技術総合研究所 | Carbon nanotube thin film |
| KR20100063091A (en) | 2007-08-29 | 2010-06-10 | 노쓰웨스턴유니버시티 | Transparent electrical conductors prepared from sorted carbon nanotubes and methods of preparing same |
| CN101450797B (en) * | 2007-11-29 | 2013-05-08 | 索尼株式会社 | Method for processing carbon nanotube, carbon nanotube and carbon nanotube element |
| CN100569637C (en) | 2007-11-30 | 2009-12-16 | 北京大学 | A kind of method for preparing semi-conductive single-walled carbon nanotubes |
| JP2016135725A (en) * | 2015-01-23 | 2016-07-28 | 国立研究開発法人産業技術総合研究所 | Method for eluting and recovering carbon nanotube |
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| JP2003121892A (en) * | 2001-10-18 | 2003-04-23 | National Institute Of Advanced Industrial & Technology | Optical element and method for manufacturing the same |
| JP2004210608A (en) * | 2003-01-06 | 2004-07-29 | Japan Science & Technology Agency | Method of selecting carbon nanotube structure by light irradiation |
| JP2004290793A (en) * | 2003-03-26 | 2004-10-21 | Nissan Motor Co Ltd | Hydrogen occluding material and its manufacturing method, hydrogen occluding body, hydrogen storage apparatus and fuel cell vehicle |
| JP2004352512A (en) * | 2003-05-27 | 2004-12-16 | Univ Nagoya | Method for producing carbon nanotube, and carbon nanotube-containing composition |
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| JP2003121892A (en) * | 2001-10-18 | 2003-04-23 | National Institute Of Advanced Industrial & Technology | Optical element and method for manufacturing the same |
| JP2004210608A (en) * | 2003-01-06 | 2004-07-29 | Japan Science & Technology Agency | Method of selecting carbon nanotube structure by light irradiation |
| JP2004290793A (en) * | 2003-03-26 | 2004-10-21 | Nissan Motor Co Ltd | Hydrogen occluding material and its manufacturing method, hydrogen occluding body, hydrogen storage apparatus and fuel cell vehicle |
| JP2004352512A (en) * | 2003-05-27 | 2004-12-16 | Univ Nagoya | Method for producing carbon nanotube, and carbon nanotube-containing composition |
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