WO2014133029A1 - Procédé pour choisir un dopant, composition de dopant, procédé pour fabriquer un composite nanotube de carbone/dopant, matériau en forme de feuille et composite nanotube de carbone/dopant - Google Patents

Procédé pour choisir un dopant, composition de dopant, procédé pour fabriquer un composite nanotube de carbone/dopant, matériau en forme de feuille et composite nanotube de carbone/dopant Download PDF

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WO2014133029A1
WO2014133029A1 PCT/JP2014/054733 JP2014054733W WO2014133029A1 WO 2014133029 A1 WO2014133029 A1 WO 2014133029A1 JP 2014054733 W JP2014054733 W JP 2014054733W WO 2014133029 A1 WO2014133029 A1 WO 2014133029A1
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dopant
carbon nanotube
group
present
swnt
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PCT/JP2014/054733
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English (en)
Japanese (ja)
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斐之 野々口
壯 河合
賢次 大橋
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国立大学法人奈良先端科学技術大学院大学
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Priority to JP2014560587A priority Critical patent/JP5768299B2/ja
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes
    • H10K85/225—Carbon nanotubes comprising substituents

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  • the present invention relates to a method for selecting a dopant, a dopant composition, a method for producing a carbon nanotube-dopant complex, a sheet-like material, and a carbon nanotube-dopant complex.
  • SWNTs Single-walled carbon nanotubes
  • SWNT The polarity of SWNT (that is, whether SWNT exhibits p-type conductivity or n-type conductivity) can be determined by the sign of the Seebeck coefficient. Many SWNTs exhibit a positive Seebeck coefficient and p-type conductivity (Non-Patent Documents 1 to 4). However, in particular, when a logic circuit or a thermoelectric conversion element is constructed from SWNT, both SWNT showing p-type conductivity (p-type conductive SWNT) and SWNT showing n-type conductivity (n-type conductive SWNT) are used. Is required. For this reason, it is required to convert the p-type conductive SWNT to the n-type conductive SWNT.
  • Non-Patent Document 6 Patent Documents 1, 3, 4 and 5.
  • Non-Patent Documents 5 and 7 disclose that p-type conductive SWNTs can be converted to n-type conductive SWNTs by doping polyethyleneimine into SWNTs.
  • Patent Document 2 discloses (CH 3 ) 3 C— group, (CH 3 ) 2 CH— group, CH 3 CH 2 — group or n-type dopant of channel SWNT in a field effect transistor using SWNT as a channel. It is disclosed to use those having an electron donating group such as a CH 3 — group.
  • Patent Document 6 discloses that nicotinamide and nicotinamide-based compounds can be used as n-type dopants for SWNTs.
  • n-type conductive SWNT for example, chemical vapor deposition (for example, Patent Document 3), heating (for example, Patent Document 6), etc. need to be performed and the operation is not simple. It is not easy to mass produce SWNTs. Therefore, there is a demand for a simpler and more efficient method for producing n-type conductive SWNTs.
  • the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a highly reliable method for selecting an n-type dopant and to provide a simple and efficient method for producing an n-type conductive SWNT. Is to provide.
  • the molecular structure of a ⁇ electron conjugated system includes a group 15 element of the periodic table (for example, nitrogen element, phosphorus element, arsenic element). It was found for the first time that the majority carrier of SWNT changes from a hole to an electron by adsorbing the Lewis base to the SWNT surface via ⁇ - ⁇ stacking. There has never been reported to select a substance that can be used as an n-type dopant from the viewpoint of a Lewis base having both a group 15 element of the periodic table as an electron pair donating site and a ⁇ -electron conjugated molecular structure. The present invention has been completed based on such new findings.
  • a group 15 element of the periodic table for example, nitrogen element, phosphorus element, arsenic element.
  • the method for selecting a dopant according to the present invention is a method for selecting a dopant that changes the Seebeck coefficient of a carbon nanotube
  • the dopant includes a step of selecting the following substance (a) or (b): (A) a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure; (B) A Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the method for producing a carbon nanotube-dopant complex according to the present invention is a method for producing a carbon nanotube-dopant complex, which includes a contact step of bringing a dopant into contact with a carbon nanotube in a liquid.
  • the dopant is a dopant having a HOMO level in the range of ( ⁇ -1) eV or more and ( ⁇ + 0.5) eV or less when the conduction band edge level of the carbon nanotube is ⁇ eV.
  • the carbon nanotubes are brought into contact with the dopant while the carbon nanotubes are sheared and dispersed in a liquid.
  • a dopant According to the method for selecting a dopant according to the present invention, (i) a Lewis acid having both a group 13 element or a group 15 element in the periodic table as an electron pair accepting site and a molecular structure of a ⁇ electron conjugated system, or (Ii) Since a substance serving as a dopant is selected from the viewpoint of a Lewis base having both a group 15 element of the periodic table as an electron pair donating site and a molecular structure of a ⁇ -electron conjugated system, the Seebeck coefficient of the carbon nanotube is changed. The dopant can be selected efficiently with high reliability.
  • the dopant selected by the dopant selection method according to the present invention has a ⁇ -electron conjugated molecular structure, it can be efficiently adsorbed on the surface of SWNT via ⁇ - ⁇ stacking. Therefore, it can be a dopant that donates or accepts electrons to SWNT more efficiently than conventional dopants. Therefore, since the p-type conductive SWNT can be efficiently converted into the n-type conductive SWNT by using such a dopant, there is no need to perform chemical vapor deposition, heating, etc., which are necessary when using a conventional dopant, The n-type conductive SWNT can be easily and efficiently manufactured. Further, by using such a dopant, the n-type conductive SWNT can be easily and efficiently manufactured, and thus the n-type conductive SWNT can be produced in large quantities.
  • the method for producing a carbon nanotube-dopant complex according to the present invention includes a contact step in which a dopant and a carbon nanotube are brought into contact with each other in the liquid.
  • the carbon nanotube is sheared and dispersed in the liquid. While, the carbon nanotube and the dopant are brought into contact. Therefore, the dopant and the carbon nanotube can be brought into sufficient contact.
  • the dopant is a dopant having a HOMO level in the range of ( ⁇ -1) eV or more and ( ⁇ + 0.5) eV or less when ⁇ eV is the conduction band edge level of the carbon nanotube. It becomes a dopant that changes the Seebeck coefficient of. Therefore, a carbon nanotube-dopant complex can be produced simply and efficiently.
  • FIG. 3 is a view showing Seebeck coefficients of sheet-like SWNT structures obtained in Examples 1 to 3, 5 to 15, 18 to 33, Reference Examples 1 to 3 and Comparative Example 3.
  • FIG. 10 is a diagram showing the electrical conductivity and Seebeck coefficient of the sheet-like SWNT structure obtained in Example 16. It is the figure which showed the relationship between the highest occupied orbital (HOMO) level of each dopant used in the Example, and the Seebeck coefficient of each sheet-like SWNT structure obtained by doping the dopant. is there.
  • HOMO highest occupied orbital
  • the dopant selection method according to the present invention is a method of selecting a dopant that changes the Seebeck coefficient of a carbon nanotube, and includes the following (a) or (b ) Includes a step of selecting a substance (hereinafter referred to as a “selection step”): (A) a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure; (B) A Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the carbon nanotube may have a metal type, semiconductor type or semi-metal type property.
  • the carbon nanotube may have either p-type conductivity or n-type conductivity.
  • the carbon nanotube may be a single wall or a multilayer.
  • the above “Seebeck coefficient” means the ratio of open circuit voltage to the temperature difference between the high-temperature junction and the low-temperature junction of the circuit showing the Seebeck effect (from “Maglow Hill Science and Technology Terminology Dictionary 3rd Edition”). .
  • the Seebeck coefficient can be an index for determining the polarity of the carbon nanotube. Specifically, for example, it can be said that a carbon nanotube having a positive Seebeck coefficient has p-type conductivity. On the other hand, it can be said that the carbon nanotube in which the Seebeck coefficient has a negative value has n-type conductivity.
  • the Seebeck coefficient can be measured using, for example, a Seebeck effect measuring apparatus (manufactured by MMR) used in Examples described later.
  • the Seebeck coefficient is also correlated with the conductivity of the carbon nanotube. Specifically, for example, a carbon nanotube having a large absolute value of the Seebeck coefficient can be said to have higher conductivity than a carbon nanotube having a small absolute value of the Seebeck coefficient.
  • the “conductivity” is represented by conductivity (S / cm; S is the reciprocal of resistance ( ⁇ )). If the conductivity is high, the conductivity is high, and if the conductivity is low, the conductivity is low. .
  • the conductivity can be measured using, for example, Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) used in Examples described later.
  • the above “change Seebeck coefficient” is intended to change the Seebeck coefficient from a positive value to a negative value, or to increase or decrease the absolute value of the Seebeck coefficient. Therefore, the above-mentioned “dopant that changes the Seebeck coefficient of the carbon nanotube” means a dopant that can change the Seebeck coefficient in a carbon nanotube doped with such a dopant from a positive value to a negative value, or such a dopant. Contemplated are dopants that can increase or decrease the absolute value of the Seebeck coefficient in carbon doped carbon nanotubes compared to before doping. In this specification, such a dopant may be simply referred to as a p-type dopant or an n-type dopant.
  • the selection step is a step of selecting a substance corresponding to the substance (a) or (b) as a dopant that changes the Seebeck coefficient of the carbon nanotube.
  • the present inventors adsorbed a Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure on the surface of SWNT via ⁇ - ⁇ stacking, whereby SWNT It has been found for the first time that the majority carriers of the change from holes to electrons. As a result of further earnest studies based on such knowledge, it is used as an n-type dopant in terms of a Lewis base having both a group 15 element of the periodic table as an electron pair donating site and a ⁇ -electron conjugated molecular structure.
  • the selection step in the dopant selection method of the present invention is a step of selecting a substance that can be a dopant that changes the Seebeck coefficient of the carbon nanotube based on this new knowledge. That is, in the selection step in the dopant selection method of the present invention, when a p-type dopant is selected as a dopant that changes the Seebeck coefficient of the carbon nanotube, a substance corresponding to the substance (a) may be selected. On the other hand, when an n-type dopant is selected as a dopant that changes the Seebeck coefficient of the carbon nanotube, a substance corresponding to the substance (b) may be selected.
  • Substance (a) A Lewis acid (substance (a)) containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure will be specifically described.
  • Lewis acid refers to those that receive electron pairs based on the theory of acids and bases based on the exchange of electrons submitted by Lewis. That is, the Lewis acid refers to a substance that functions as an electron pair acceptor.
  • Group 13 element of the periodic table is also referred to as a Group III element.
  • Specific examples of the Periodic Table Group 13 element include boron (B) element, aluminum (Al) element, gallium (Ga) element, indium (In) element, and thallium (Tl) element. Preferably, it is a boron (B) element.
  • the Lewis acid selected in the present invention only needs to contain at least one Group 13 element in the periodic table, but may contain two or more elements. Moreover, one kind of the periodic table group 13 element may be contained alone, or a plurality of kinds may be contained in combination.
  • group 15 element of the periodic table is also referred to as a group V element.
  • Specific examples of the Group 15 element in the periodic table include nitrogen (N) element, phosphorus (P) element, arsenic (As) element, antimony (Sb) element, and bismuth (Bi) element. Nitrogen (N) element and phosphorus (P) element are preferable.
  • the Lewis acid selected in the present invention may contain at least one Group 15 element of the periodic table, but may contain two or more elements. Moreover, one type of the periodic table group 15 element may be contained alone, or a plurality of types may be contained in combination.
  • ⁇ electron conjugated system is a system in which two or more multiple bonds are conjugated, and a system in which multiple bonds of ⁇ electrons interact through a single bond and delocalize.
  • the “molecular structure of the ⁇ -electron conjugated system” is not particularly limited as long as the molecular structure includes the ⁇ -electron conjugated system.
  • an aromatic ring for example, a benzene ring, a 5-membered ring including a ⁇ -electron conjugated system
  • carbon A carbon double bond for example, a carbon-oxygen double bond
  • a heteroaromatic ring for example, a structure in which at least one of six CH bonds contained in a benzene ring is substituted with a nitrogen atom
  • the structure in which at least one of the six CH bonds contained in the benzene ring is substituted with a nitrogen atom means that one to three of the six CH bonds contained in the benzene ring are A structure substituted with a nitrogen atom is preferred.
  • the site substituted by the nitrogen atoms of the six C—H bonds contained in the benzene ring there are no particular limitations on the site substituted by the nitrogen atoms of the six C—H bonds contained in the benzene ring.
  • the heteroaromatic ring may be a 5-membered ring containing a ⁇ -electron conjugated system and a ring structure containing a nitrogen atom or a sulfur atom.
  • the Lewis acid selected in the present invention may contain at least one molecular structure of the ⁇ -electron conjugated system, but may contain two or more.
  • One kind of the molecular structure of the ⁇ -electron conjugated system may be contained alone, or a plurality of kinds may be contained in combination.
  • the Lewis acid selected in the present invention is not particularly limited as long as it is a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure.
  • Specific examples of such Lewis acids include phenylboronic acid, triphenylphosphine oxide, carbazole, 2,6-diphenylpyridine, 1,3,5-triazine, pyrazine, quinoline, triphenylamine, pyridine
  • the present invention is not limited to these.
  • Lewis acid examples include pyrimidine, 9H-carbazo-4-ol, tetracyanoquinodimethane, 9H-carbazo-2-ol, tetrathiafulvalene, imidazole and polyaniline.
  • Lewis base refers to a substance that forms a chemical bond by giving an electron pair to Lewis acid based on the theory of acid / base based on the exchange of electrons submitted by Lewis. That is, the Lewis base refers to a substance that functions as an electron pair donor.
  • the Lewis base selected in the present invention is not particularly limited as long as it is a Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure.
  • Specific examples of such Lewis bases include polyvinylpyrrolidone, polyvinylpyridine, phenanthroline, indole, triphenylphosphine and 1,3-bis (diphenylphosphine) propane. It is not limited to these.
  • Lewis base examples include tris (4-fluorophenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphine).
  • steps other than those described above may be provided, and the contents of the steps other than the above are not limited.
  • a dopant that changes the Seebeck coefficient of a carbon nanotube can be efficiently selected with high reliability.
  • a dopant for changing the Seebeck coefficient of the carbon nanotube as a dopant for changing the Seebeck coefficient of the carbon nanotube, a range of ( ⁇ -1) eV or more ( ⁇ + 0.5) eV or less when the level of the conduction band edge of the carbon nanotube is ⁇ eV.
  • a dopant having a HOMO level of may be selected.
  • a dopant having a HOMO level in the range of a HOMO level 1 eV deeper to a 0.5 eV shallower HOMO level than the level of the conduction band edge of the carbon nanotube may be selected. Good.
  • the dopant that changes the Seebeck coefficient of the carbon nanotube can also be efficiently selected with high reliability by the dopant selection method based on the HOMO level.
  • Examples of the dopant having the HOMO level include the substances (a) and (b) described above.
  • FIG. 5 is a schematic diagram showing an example of the relationship between the conduction band edge level of the carbon nanotube and the HOMO level of the dopant.
  • FIG. 5A shows the band structure of p-type conductive carbon nanotubes.
  • the conduction band edge (bottom of the conduction band) 1 of the carbon nanotube is about ⁇ 4.65 eV. Therefore, based on the dopant selection method based on the HOMO level, a dopant having a HOMO level of ⁇ 5.65 eV to ⁇ 4.15 eV is selected.
  • the HOMO level 2 of the dopant shown in (a) of FIG. 5 is ⁇ 4.85 eV. Therefore, the said dopant is selected as a suitable dopant which changes the Seebeck coefficient of a carbon nanotube.
  • FIG. 5A a defect level exists in the band gap (between the conduction band and the valence band) of the carbon nanotube, and holes (holes) are generated.
  • FIG. 5B electrons of the dopant are supplied to the holes.
  • disappears the remaining electrons which a dopant has are supplied to a conductor end, as shown in (c) of FIG.
  • the carbon nanotubes that were p-type conductivity are changed to n-type conductivity. That is, the Seebeck coefficient of the carbon nanotube changes due to doping. If the HOMO level of the dopant is in the above range, the Seebeck coefficient of the carbon nanotube can be suitably changed by the process shown in FIGS.
  • the level of the conduction band edge of the carbon nanotube is not particularly limited. For example, it is preferably ⁇ 4.8 eV or more and ⁇ 3.0 eV or less, more preferably ⁇ 4.7 eV or more and ⁇ 4.0 eV or less. .
  • a dopant selection method based on the HOMO level when the conduction band edge level of the carbon nanotube is ⁇ 4.8 eV, a HOMO level of ⁇ 5.8 eV to ⁇ 4.3 eV is set. The dopant it has can be selected. Further, when the level of the conduction band edge of the carbon nanotube is ⁇ 3.0 eV, a dopant having a HOMO level of ⁇ 4.0 eV or more and ⁇ 2.5 eV or less can be selected.
  • a dopant having a HOMO level of ⁇ 5.8 eV or more and ⁇ 2.5 eV or less can be selected.
  • Examples of the dopant having a HOMO level of ⁇ 5.8 eV or more and ⁇ 2.5 eV or less include polyvinylpyrrolidone, indole, triphenylphosphine, 1,3-bis (diphenylphosphine) propane, carbazole, triphenylamine, 9H— Carbazo-4-ol, 9H-carbazo-2-ol, tetrathiafulvalene, tris (4-fluorophenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphino) butane, ((phenylphosphinediyl) bis (methylene)) bis (diphenylphosphine), bis (((diphenylphosphino) methyl) (phenylphosphino)) methan
  • the dopant selection method based on the HOMO level when the conduction band edge level of the carbon nanotube is ⁇ 4.7 eV, the HOMO level is ⁇ 5.7 eV or more and ⁇ 4.2 eV or less. A dopant having a position can be selected.
  • the conduction band edge level of the carbon nanotube is ⁇ 4.0 eV, a dopant having a HOMO level of ⁇ 5.0 eV to ⁇ 3.5 eV can be selected.
  • the conduction band edge level of the carbon nanotube is ⁇ 4.7 eV or more and ⁇ 4.0 eV or less, it can be said that a dopant having a HOMO level of ⁇ 5.7 eV or more and ⁇ 3.5 eV or less can be selected. .
  • Examples of the dopant having a HOMO level of ⁇ 5.7 eV or more and ⁇ 3.5 eV or less include polyvinylpyrrolidone, indole, triphenylphosphine, carbazole, 9H-carbazo-4-ol, tetrathiafulvalene, tris (4-fluoro Phenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphino) butane, ((phenylphosphinediyl) bis (methylene)) Bis (diphenylphosphine), bis (((diphenylphosphino) methyl) (phenylphosphino)) methane, tris (4-methoxyphenyl) phosphine, bis (diphenylphosphinomethyl) phen
  • the method for producing a carbon nanotube-dopant complex according to the present invention comprises contacting a carbon nanotube with a dopant selected by the above-described method for selecting a dopant of the present invention. It is characterized by including a contacting step.
  • the carbon nanotubes that have undergone the contact process adsorb the dopant, that is, a carbon nanotube-dopant complex.
  • the production method of the present invention may further include a molding step of molding the carbon nanotube-dopant complex into a sheet.
  • steps other than the above may be provided, and the contents of the steps other than the above are not limited.
  • a contact process is a process of forming the composite_body
  • the “method for selecting a dopant of the present invention” and “carbon nanotube” are the same as described in the above section “1. Method for selecting a dopant”, and thus the description thereof is omitted.
  • the method is not particularly limited as long as the carbon nanotube and the dopant can be brought into contact with each other.
  • the carbon nanotube is added to a solution in which the dopant is dissolved and suspended to bring the both into contact with each other in the liquid. it can.
  • the contacting step it is preferable to bring the carbon nanotube and the dopant into contact with each other while dispersing the carbon nanotube in the liquid.
  • the carbon nanotube and the dopant it is preferable to contact the carbon nanotube and the dopant while dispersing the carbon nanotube in the liquid using a homogenizer.
  • a homogenizer By dispersing the carbon nanotubes in the liquid using a homogenizer, the dopant can easily come into contact with the carbon nanotubes. As a result, the dopant and the carbon nanotubes can be sufficiently brought into contact with each other.
  • the “homogenizing device” is not particularly limited as long as it is a device capable of uniformly dispersing carbon nanotubes in a liquid.
  • known means such as a homogenizer or an ultrasonic homogenizer can be used.
  • homogenizer or an ultrasonic homogenizer
  • stir homogenizer when it only describes with “homogenizer”, “stirring homogenizer” is intended.
  • the operating condition of the homogenizer is not particularly limited as long as the carbon nanotubes can be dispersed in the liquid.
  • a dopant solution containing carbon nanotubes is used.
  • the carbon nanotubes can be dispersed in the liquid by suspending at a room temperature (23 ° C.) for 10 minutes at a stirring speed (number of rotations) of 20000 rpm of the homogenizer.
  • the solvent for dissolving the dopant for example, dimethyl sulfoxide, dimethylformamide and the like can be used, but the present invention is not limited thereto.
  • the amount of the dopant to be brought into contact with the carbon nanotube is not particularly limited, but as shown in the examples described later, when the amount of the dopant with respect to the carbon nanotube is increased, it is compared with the Seebeck coefficient of the carbon nanotube before addition of the dopant. Further, the amount of change in Seebeck coefficient in the obtained carbon nanotube-dopant complex tends to increase. Therefore, in order to obtain a doping effect, it is preferable to add 0.001 to 500 mg of dopant per 1 g of carbon nanotubes, more preferably 0.001 to 100 mg of dopant, and 0.001 to 10 mg of dopant. It is particularly preferable to add a dopant.
  • the molding step is a step of molding the carbon nanotubes that have undergone the above contact step into a sheet shape to obtain a sheet-like carbon nanotube-dopant complex.
  • the “sheet shape” is also referred to as a film shape or a film shape. “Molding into a sheet” is intended to mold the obtained carbon nanotube-dopant complex into a film having a thickness of 1 ⁇ m to 1000 ⁇ m.
  • the method of forming the carbon nanotube-dopant complex into a sheet is not particularly limited.
  • the carbon nanotube-dopant complex suspension is subjected to suction filtration using a membrane filter having a pore size of 0.1 to 2 ⁇ m.
  • the obtained film is dried at 50 to 150 ° C. under vacuum for 1 to 24 hours, thereby forming a sheet.
  • the dopant can be sufficiently adsorbed on each carbon nanotube dispersed in the solvent.
  • the sheet-like material in the contact process after the molding process is doped only with carbon nanotubes in the vicinity of the sheet surface. Can be obtained in a uniformly doped sheet-like material. Therefore, for example, there is no possibility that the Seebeck effect is canceled due to the presence of doped n-type carbon nanotubes and undoped p-type carbon nanotubes in the sheet.
  • the dopant selected by the dopant selection method of the present invention has a ⁇ -electron conjugated molecular structure, it can be efficiently adsorbed on the carbon nanotube surface via ⁇ - ⁇ stacking. For this reason, it is possible to donate or accept electrons to the carbon nanotube more efficiently than the conventional dopant.
  • the dopant selected by the dopant selection method of the present invention since the dopant selected by the dopant selection method of the present invention is brought into contact with the carbon nanotube, the carbon nanotube-dopant complex can be produced easily and efficiently. Therefore, according to the production method of the present invention, the Seebeck coefficient of the carbon nanotube can be changed easily and efficiently.
  • a sheet-like material according to the present invention (hereinafter also referred to as “sheet-like material of the present invention”) is characterized by being produced by the above-described method for producing a carbon nanotube-dopant complex according to the present invention.
  • the “method for producing a carbon nanotube-dopant complex according to the present invention” is the same as described in the above section “2. Method for producing a carbon nanotube-dopant complex”, and thus the description thereof is omitted.
  • the sheet material of the present invention is manufactured by the manufacturing method of the present invention, as described above, even the carbon nanotubes in the sheet are uniformly doped. Therefore, for example, there is no possibility that the Seebeck effect is canceled due to the presence of doped n-type carbon nanotubes and undoped p-type carbon nanotubes in the sheet.
  • the dopant composition according to the present invention (hereinafter also referred to as “dopant composition of the present invention”) is a dopant composition for changing the Seebeck coefficient of carbon nanotubes, and at least the dopant composition of the present invention described above. What is necessary is just to contain the dopant selected by the selection method. Note that the “method for selecting a dopant of the present invention” is the same as that described in the section “1. Method for selecting a dopant”, and thus the description thereof is omitted.
  • the dopant selected by the method for selecting a dopant of the present invention is the following substance (a) or (b): (A) a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure; (B) A Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the Lewis base has triphenylphosphine, aniline, benzylamine, polyvinylpyrrolidone, N-methylpyrrolidone, polyaniline, nicotinamide and nicotine described in JP-T-2010-537410 and JP-A-2009-292714. It is preferable to exclude the case where it is an amide compound.
  • Lewis base examples include polyvinyl pyridine, phenanthroline, indole and 1,3-bis (diphenylphosphine) propane.
  • Lewis base examples include tris (4-fluorophenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphine).
  • the dopant is preferably a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the dopant composition of the present invention specifically includes, for example, phenylboronic acid, triphenylphosphine oxide, carbazole, 2,6-diphenylpyridine, 1,3,5-triazine, pyrazine, quinoline, It may contain at least one selected from the group consisting of triphenylamine and pyridine.
  • the Lewis acid include pyrimidine, 9H-carbazo-4-ol, tetracyanoquinodimethane, 9H-carbazo-2-ol, tetrathiafulvalene, imidazole and polyaniline.
  • the dopant composition of the present invention may contain a substance other than the dopant selected by the dopant selection method of the present invention, if necessary. Such a substance is not particularly limited as long as it does not inhibit the function of the dopant. Moreover, the dopant composition of the present invention may contain a plurality of types of dopants.
  • the dopant selected by the dopant selection method of the present invention has a ⁇ -electron conjugated molecular structure, it can be efficiently adsorbed on the carbon nanotube surface via ⁇ - ⁇ stacking. Since the dopant composition of the present invention contains at least the dopant selected by the method for selecting a dopant of the present invention, it donates or accepts electrons to the carbon nanotube more efficiently than the conventional dopant. be able to. Therefore, if the dopant composition of the present invention is used, the Seebeck coefficient of the carbon nanotube can be changed easily and efficiently.
  • the present invention also includes a dopant for changing the Seebeck coefficient of the carbon nanotube, which is selected by the dopant selection method according to the present invention.
  • the carbon nanotube-dopant complex according to the present invention (hereinafter also referred to as “the carbon nanotube-dopant complex of the present invention”) comprises a dopant selected by the above-described method for selecting a dopant of the present invention, and a carbon nanotube. It is characterized by containing.
  • the “method for selecting a dopant of the present invention” and “carbon nanotube” are the same as described in the above section “1. Method for selecting a dopant”, and thus the description thereof is omitted.
  • the dopant selected by the method for selecting a dopant of the present invention is the following substance (a) or (b): (A) a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure; (B) A Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the Lewis base has triphenylphosphine, aniline, benzylamine, polyvinylpyrrolidone, N-methylpyrrolidone, polyaniline, nicotine described in JP-T-2010-537410 and JP-A-2009-292714. Except for the case of amide and nicotinamide compounds, it is preferable.
  • Lewis base examples include polyvinyl pyridine, phenanthroline, indole and 1,3-bis (diphenylphosphine) propane.
  • Lewis base examples include tris (4-fluorophenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphine).
  • the dopant is preferably a Lewis acid containing a group 13 element or a group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the carbon nanotube-dopant complex of the present invention includes, as the above Lewis acid, specifically, for example, phenylboronic acid, triphenylphosphine oxide, carbazole, 2,6-diphenylpyridine, 1,3,5-triazine, pyrazine And at least one selected from the group consisting of quinoline, triphenylamine and pyridine.
  • the Lewis acid include pyrimidine, 9H-carbazo-4-ol, tetracyanoquinodimethane, 9H-carbazo-2-ol, tetrathiafulvalene, imidazole and polyaniline.
  • the dopant content per gram of carbon nanotubes is not particularly limited.
  • the carbon nanotube-dopant composite of the present invention preferably contains 0.001 to 500 mg of dopant per 1 g of carbon nanotube, and 0.01 to 100 mg of dopant. It is more preferably contained, and particularly preferably 0.1 to 10 mg of dopant is contained.
  • the carbon nanotube-dopant complex of the present invention may contain substances other than those described above, and the types of substances other than those described above are not limited.
  • the present invention can also be configured as follows.
  • the method for selecting a dopant according to the present invention is a method for selecting a dopant that changes the Seebeck coefficient of a carbon nanotube,
  • the dopant includes a step of selecting the following substance (a) or (b): (A) a Lewis acid containing a Group 13 element or a Group 15 element in the periodic table and having a ⁇ -electron conjugated molecular structure; (B) A Lewis base containing a group 15 element of the periodic table and having a ⁇ -electron conjugated molecular structure.
  • the Group 13 element of the periodic table may be a boron element.
  • the Group 15 element of the periodic table may be a nitrogen element or a phosphorus element.
  • the molecular structure of the ⁇ -electron conjugated system has a benzene ring, a carbon-carbon double bond, a carbon-oxygen double bond, and six CH bonds contained in the benzene ring. It may be at least one selected from the group consisting of a structure in which at least one is substituted with a nitrogen atom.
  • the method for producing a carbon nanotube-dopant complex according to the present invention is characterized by including a contact step in which the dopant selected by the above-described method for selecting a dopant according to the present invention and a carbon nanotube are brought into contact with each other. .
  • the carbon nanotube and the dopant are preferably brought into contact while dispersing the carbon nanotube in a liquid using a homogenizer.
  • the homogenizer may be a homogenizer or an ultrasonic homogenizer.
  • the method for producing a carbon nanotube-dopant composite according to the present invention may further include a molding step of molding the carbon nanotubes that have undergone the above contact step into a sheet shape.
  • the carbon nanotube may have p-type conductivity or n-type conductivity.
  • the sheet-like material according to the present invention is characterized by being produced by the above-described method for producing a carbon nanotube-dopant complex according to the present invention.
  • the dopant composition according to the present invention is a dopant composition for changing the Seebeck coefficient of a carbon nanotube, At least the dopant selected by the dopant selection method according to the present invention described above is included.
  • the dopant is preferably a Lewis acid containing a periodic table group 13 element or a periodic table group 15 element and having a ⁇ -electron conjugated molecular structure.
  • the carbon nanotube-dopant complex according to the present invention is characterized by containing a dopant selected by the above-described dopant selection method according to the present invention and a carbon nanotube.
  • the dopant is preferably a Lewis acid containing a periodic table group 13 element or a periodic table group 15 element and having a ⁇ -electron conjugated molecular structure.
  • the present invention can also be configured as follows.
  • the molecular structure of the ⁇ electron conjugated system is at least one selected from the group consisting of an aromatic ring, a carbon-carbon double bond, a carbon-oxygen double bond, and a heteroaromatic ring. possible.
  • the method for producing a carbon nanotube-dopant complex according to the present invention may further include a molding step in which the carbon nanotubes that have undergone the above contact step are molded into a sheet shape to obtain a sheet-like carbon nanotube-dopant complex. .
  • the dopant according to the present invention is a dopant for changing the Seebeck coefficient of the carbon nanotube, and is selected by the method for selecting a dopant according to the present invention.
  • the dopant may be a Lewis acid containing a periodic table group 13 element or a periodic table group 15 element and having a ⁇ -electron conjugated molecular structure.
  • the dopant composition according to the present invention is a dopant composition for changing the Seebeck coefficient of a carbon nanotube, and is characterized by containing at least the dopant according to the present invention.
  • the method for producing a carbon nanotube-dopant complex includes a contact step in which a dopant and a carbon nanotube are brought into contact with each other in a liquid.
  • the dopant has a level at a conduction band edge of the carbon nanotube.
  • ⁇ p is a dopant having a HOMO level in the range of ( ⁇ -1) eV or more and ( ⁇ + 0.5) eV or less, and in the contact step, the carbon nanotubes are shear dispersed in the liquid while the carbon nanotubes are sheared and dispersed. It is characterized in that the nanotube is brought into contact with the dopant.
  • Phenylboronic acid was used as the dopant molecule. As shown in FIG. 1A, phenylboronic acid corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • SWNT Single-walled carbon nanotubes
  • the obtained suspension was subjected to suction filtration using a 0.2 mm pore membrane filter, and the obtained membrane was dried under vacuum at 80 ° C. for 12 hours to obtain a sheet-like SWNT structure. .
  • Example 2 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that polyvinylpyrrolidone was used as the dopant molecule. As shown in FIG. 1B, polyvinyl pyrrolidone corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 3 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that polyvinyl pyridine was used as the dopant molecule.
  • polyvinyl pyridine corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 4 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that phenanthroline was used as the dopant molecule. As shown in FIG. 1 (d), phenanthroline corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 5 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that indole was used as the dopant molecule. As shown in FIG. 1E, indole corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 6 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that triphenylphosphine was used as the dopant molecule.
  • triphenylphosphine corresponds to the Lewis base selected by the dopant selection method of this invention.
  • Example 7 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 1,3-bis (diphenylphosphino) propane was used as the dopant molecule. As shown in (g) of FIG. 1, 1,3-bis (diphenylphosphino) propane corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 8 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that triphenylphosphine oxide was used as the dopant molecule.
  • triphenylphosphine oxide corresponds to the Lewis acid selected by the dopant selection method of this invention.
  • Example 9 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that carbazole was used as the dopant molecule. As shown in FIG. 1 (i), carbazole corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 10 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 2,6-diphenylpyridine was used as the dopant molecule. As shown in FIG. 1 (j), 2,6-diphenylpyridine corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 11 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 1,3,5-triazine was used as the dopant molecule. As shown in FIG. 1 (k), 1,3,5-triazine corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 12 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that pyrazine was used as the dopant molecule.
  • pyrazine corresponds to the Lewis acid selected by the dopant selection method of this invention.
  • Example 13 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that quinoline was used as the dopant molecule.
  • quinoline corresponds to the Lewis acid selected by the dopant selection method of this invention.
  • Example 14 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that triphenylamine was used as the dopant molecule. As shown in (n) of FIG. 1, triphenylamine corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 15 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that pyridine was used as the dopant molecule. As shown in FIG. 1 (o), pyridine corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 1 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that polyethyleneimine was used as the dopant molecule. As shown in FIG. 1 (p), polyethyleneimine does not correspond to either a Lewis acid or a Lewis base selected by the dopant selection method of the present invention, but is a substance known as an n-type dopant. Therefore, it was used as a reference.
  • Example 2 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that Tetronic 1107 (BASF) was used as the dopant molecule. As shown in FIG. 1 (q), Tetronic 1107 does not correspond to either the Lewis acid or the Lewis base selected by the dopant selection method of the present invention, but can be easily inferred from Reference Example 1. It was used as a reference because it is a dopant.
  • BASF Tetronic 1107
  • Example 18 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 9H-carbazo-4-ol was used as the dopant molecule. As shown in FIG. 6 (a), 9H-carbazo-4-ol corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 19 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that tetracyanoquinodimethane was used as the dopant molecule. Note that, as shown in FIG. 6B, tetracyanoquinodimethane corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 20 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 9H-carbazo-2-ol was used as the dopant molecule. As shown in FIG. 6C, 9H-carbazo-2-ol corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 21 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that tetrathiafulvalene was used as the dopant molecule. Note that, as shown in FIG. 6D, tetrathiafulvalene corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 22 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that imidazole was used as the dopant molecule.
  • imidazole corresponds to the Lewis acid selected by the dopant selection method of this invention.
  • Example 23 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that polyaniline was used as the dopant molecule. Note that, as shown in FIG. 6 (f), polyaniline corresponds to the Lewis acid selected by the dopant selection method of the present invention.
  • Example 24 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that tris (4-fluorophenyl) phosphine was used as the dopant molecule. As shown in FIG. 6 (g), tris (4-fluorophenyl) phosphine corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 25 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 1,2-bis (diphenylphosphino) ethane was used as the dopant molecule. As shown in FIG. 6 (h), 1,2-bis (diphenylphosphino) ethane corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 26 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that diphenylphosphine was used as the dopant molecule.
  • diphenylphosphine corresponds to the Lewis base selected by the dopant selection method of this invention.
  • Example 27 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that tris (4-chlorophenyl) phosphine was used as the dopant molecule. As shown in FIG. 6 (j), tris (4-chlorophenyl) phosphine corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 28 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that 1,4-bis (diphenylphosphino) butane was used as the dopant molecule. As shown in FIG. 7A, 1,4-bis (diphenylphosphino) butane corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 29 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that ((phenylphosphinediyl) bis (methylene)) bis (diphenylphosphine) was used as the dopant molecule. As shown in FIG. 7B, ((phenylphosphinediyl) bis (methylene)) bis (diphenylphosphine) corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 30 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that bis (((diphenylphosphino) methyl) (phenylphosphino)) methane was used as the dopant molecule. As shown in FIG. 7C, bis (((diphenylphosphino) methyl) (phenylphosphino)) methane corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 31 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that tris (4-methoxyphenyl) phosphine was used as the dopant molecule. Note that, as shown in FIG. 7D, tris (4-methoxyphenyl) phosphine corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 32 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that bis (diphenylphosphinomethyl) phenylphosphine was used as the dopant molecule. Note that, as shown in FIG. 7E, bis (diphenylphosphinomethyl) phenylphosphine corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 33 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that tris (4-methoxy-3,5-dimethylphenyl) phosphine was used as the dopant molecule. As shown in FIG. 7 (f), tris (4-methoxy-3,5-dimethylphenyl) phosphine corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • Example 34 A sheet-like SWNT structure was obtained in the same manner as in Example 1 except that pyrimidine was used as the dopant molecule.
  • pyrimidine corresponds to the Lewis acid selected by the dopant selection method of this invention.
  • FIG. 7 (g) shows neutral benzyl viologen.
  • the reduced benzyl viologen does not correspond to either the Lewis acid or the Lewis base selected by the dopant selection method of the present invention, but was used as a reference because it is a known substance as an n-type dopant.
  • FIG. 2 is a diagram showing the Seebeck coefficient of the sheet-like SWNT structures obtained in Examples 1 to 3, 5 to 15, 18 to 33, Reference Examples 1 to 3 and Comparative Example 3.
  • the polarity of carbon nanotubes can be determined by the sign of the Seebeck coefficient. Since the SWNT structure of Comparative Example 1 exhibited a positive Seebeck coefficient of approximately 40 ⁇ V / K, it was determined to be p-type conductive. Further, the SWNT structure of Comparative Example 3 exhibited a positive Seebeck coefficient of approximately 49.35 ⁇ V / K, and thus was determined to be p-type conductivity.
  • the Lewis bases tris (4-fluorophenyl) phosphine (Example 24), 1,2-bis (diphenylphosphino) ethane (Example 25), diphenylphosphine (Example 26), tris (4-chlorophenyl) ) Phosphine (Example 27), 1,4-bis (diphenylphosphino) butane (Example 28), ((phenylphosphinediyl) bis (methylene)) bis (diphenylphosphine) (Example 29), bis (( (Diphenylphosphino) methyl) (phenylphosphino)) methane (Example 30), tris (4-methoxyphenyl) phosphine (Example 31), bis (diphenylphosphinomethyl) phenylphosphine (Example 32), and Tris (4-methoxy-3,5-dimethylphenyl) phosphine
  • the value of the Seebeck coefficient of the SWNT structure can be changed from positive to negative by using the Lewis base selected by the dopant selection method of the present invention as a dopant. Further, it was confirmed that the absolute value of the Seebeck coefficient can be changed by using the Lewis base selected by the dopant selection method of the present invention as a dopant as compared with an untreated SWNT structure which is not doped. .
  • Lewis acids such as phenylboronic acid (Example 1), triphenylphosphine oxide (Example 8), carbazole (Example 9), 2,6-diphenylpyridine (Example 10), 1,3,5-
  • phenylboronic acid Example 1
  • triphenylphosphine oxide Example 8
  • carbazole Example 9
  • 2,6-diphenylpyridine Example 10
  • 1,3,5- When triazine (Example 11), pyrazine (Example 12), quinoline (Example 13), triphenylamine (Example 14) or pyridine (Example 15) is used as a dopant, the SWNT structure is positive. These SWNT structures were found to be p-type conductive.
  • Lewis acids 9H-carbazo-4-ol (Example 18), tetracyanoquinodimethane (Example 19), 9H-carbazo-2-ol (Example 20), tetrathiafulvalene (Example 21) ), Imidazole (Example 22), and polyaniline (Example 23) are also used as dopants, the SWNT structures provide a positive Seebeck coefficient, and these SWNT structures are p-type conductive. It was revealed.
  • the SWNT structure of Comparative Example 1 exhibits a positive Seebeck coefficient of approximately 40 ⁇ V / K, whereas when phenylboronic acid (Example 1) is used as a dopant, the SWNT structure Showed a positive Seebeck coefficient of approximately 56 ⁇ V / K.
  • the SWNT structure exhibited a positive Seebeck coefficient of approximately 52.3 ⁇ V / K.
  • the SWNT structure exhibited a positive Seebeck coefficient of approximately 41.7 ⁇ V / K.
  • the SWNT structure exhibited a positive Seebeck coefficient of approximately 40.9 ⁇ V / K.
  • Example 16 A sheet-like SWNT structure was obtained in the same manner as in Example 6 except that the dopant concentration was changed to 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt%, respectively.
  • the electrical conductivity and Seebeck coefficient of each SWNT structure obtained in Example 16 were evaluated.
  • the electrical conductivity was evaluated using Loresta GP (manufactured by Mitsubishi Chemical Analytech), and the Seebeck coefficient was evaluated using a Seebeck effect measuring device (manufactured by MMR).
  • the SWNT structure of Comparative Example 1 was used.
  • FIG. 3 is a diagram showing the conductivity and Seebeck coefficient of the sheet-like SWNT structure obtained in Example 16.
  • the circle in the figure represents the conductivity (see the left axis of the graph pointed to by the left arrow in the figure), and the square represents the Seebeck coefficient (see the right axis of the graph pointed to by the right arrow in the figure).
  • the value of the Seebeck coefficient changed from positive to negative as the concentration of triphenylphosphine added as a dopant increased. Further, as the concentration of triphenylphosphine increased, the value of the Seebeck coefficient tended to become smaller (the absolute value of the Seebeck coefficient became larger).
  • Example 17 Example 1 was used except that 1,3-bis (diphenylphosphino) propane was used as the dopant molecule and the concentration of 1,3-bis (diphenylphosphino) propane in the dopant solution was changed to 0.1% by weight. Thus, a sheet-like SWNT structure was obtained.
  • SWNT single-walled carbon nanotube
  • 1,3-bis (diphenylphosphino) propane corresponds to the Lewis base selected by the dopant selection method of the present invention.
  • SWNT single-walled carbon nanotubes
  • the obtained sheet-like SWNT structure was immersed in dimethyl sulfoxide (10 mL) in which 0.1% by weight of 1,3-bis (diphenylphosphino) propane was dissolved for 10 minutes at 23 ° C.
  • the SWNT structure was doped.
  • the SWNT is subjected to doping treatment and then molded into a sheet shape. Therefore, even the carbon nanotubes inside the sheet are uniformly doped. A shaped material can be obtained. For this reason, there is no possibility that the Seebeck effect is offset by the presence of doped n-type carbon nanotubes and undoped p-type carbon nanotubes in the sheet.
  • Example 3 Reference Example 3 and Comparative Example 3, only the conductivity and Seebeck coefficient were shown. Moreover, Example 34 showed only the HOMO level.
  • region especially enclosed with the dotted line in FIG. 4 can be used conveniently as an n-type dopant.
  • the conduction band edge level of the carbon nanotube is ⁇ 4.8 eV or more and ⁇ 3.0 eV or less, polyvinylpyrrolidone or indole having a HOMO level of ⁇ 5.8 eV or more and ⁇ 2.5 eV or less , Triphenylphosphine, 1,3-bis (diphenylphosphine) propane, carbazole, triphenylamine, 9H-carbazo-4-ol, 9H-carbazo-2-ol, tetrathiafulvalene, tris (4-fluorophenyl) phosphine 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphino) butane, ((phenylphosphinediyl) bis (methylene)) bis (diphenyl) Phosphin
  • the level of the conduction band edge of the carbon nanotube is ⁇ 4.7 eV or more and ⁇ 4.0 eV or less, polyvinylpyrrolidone, indole having a HOMO level of ⁇ 5.7 eV or more and ⁇ 3.5 eV or less, Triphenylphosphine, carbazole, 9H-carbazo-4-ol, tetrathiafulvalene, tris (4-fluorophenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphine, tris (4-chlorophenyl) phosphine, 1,4-bis (diphenylphosphino) butane, ((phenylphosphinediyl) bis (methylene)) bis (diphenylphosphine), bis (((diphenylphosphino) methyl) (phenylphosphino)) methane, tris (4
  • carbon nanotubes can be a tool for building various devices such as field effect transistors and thermoelectric conversion elements
  • the present invention can be used in various industries using carbon nanotubes.

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Abstract

　La présente invention concerne un procédé hautement fiable pour choisir un dopant. Ce procédé de sélection d'un dopant par la variation du coefficient de Seebeck d'un nanotube de carbone comprend une étape de sélection d'une substance (a) ou (b), où (a) est un acide de Lewis contenant un élément du groupe 13 ou 15 du tableau périodique et présentant une structure moléculaire d'un système conjugué à électrons π et (b) est une base de Lewis contenant un élément du groupe 15 du tableau périodique et présentant une structure moléculaire à électrons π.
PCT/JP2014/054733 2013-02-28 2014-02-26 Procédé pour choisir un dopant, composition de dopant, procédé pour fabriquer un composite nanotube de carbone/dopant, matériau en forme de feuille et composite nanotube de carbone/dopant WO2014133029A1 (fr)

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WO2015198980A1 (fr) * 2014-06-26 2015-12-30 国立大学法人奈良先端科学技術大学院大学 Composite de composition de dopant de nanomatériau, composition de dopant, et procédé de fabrication de composite de composition de dopant de nanomatériau
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JP2016157942A (ja) * 2015-02-23 2016-09-01 国立大学法人 奈良先端科学技術大学院大学 カーボンナノチューブ−ドーパント組成物複合体の製造方法およびカーボンナノチューブ−ドーパント組成物複合体
JP2016195213A (ja) * 2015-04-01 2016-11-17 株式会社日本触媒 導電性材料及びそれを用いた熱電変換素子、熱電変換装置
WO2017002935A1 (fr) * 2015-07-01 2017-01-05 国立大学法人九州大学 MATÉRIAU SEMI-CONDUCTEUR, PROCÉDÉ DE FABRICATION DE MATÉRIAU SEMI-CONDUCTEUR, COMBINAISON D'UN MATÉRIAU SEMI-CONDUCTEUR DU TYPE n ET D'UN MATÉRIAU SEMI-CONDUCTEUR DU TYPE p, PROCÉDÉ DE FABRICATION DE MATÉRIAU SEMI-CONDUCTEUR COMPOSITE, MATÉRIAU SEMI-CONDUCTEUR COMPOSITE, ET DISPOSITIF
WO2017038831A1 (fr) * 2015-09-04 2017-03-09 浩明 中弥 Élément de conversion thermoélectrique et module de conversion thermoélectrique
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WO2017085078A1 (fr) * 2015-11-16 2017-05-26 Osram Oled Gmbh Composant électronique organique, utilisation d'un dopant p pour un matériau matriciel
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