JP2009196846A - Manufacturing method of thin film made of one-dimensional nano-material, and manufacturing method of electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a thin film of a one-dimensional nano-material having favorable orientation, transparency and conductivity, and a manufacturing method of an electronic device. <P>SOLUTION: A CNT dispersion liquid composed of a surfactant aqueous solution is prepared; its liquid droplet is attached to one end of a nozzle 12, and inflated by making air 16 flow into the other end of the nozzle, to form an air bubble 10 composed of a film containing CNT 22; part of the air bubble is made into contact with the surface of a substrate 14, and the air bubble is inflated by making air flow into the other end of the nozzle, to increase the contact area between the substrate and the air bubble film; after the air bubble is burst, a film on the substrate is washed with water, and dried to form a CNT thin film 20. The CNT is nearly parallelly radially orientated on the substrate surface, and the thin film is cut out together with the substrate with a shape holding one orientation direction. The CNT thin film is used for transparent electrodes in liquid crystal devices, electroluminescence devices, electrochromic devices, field effect transistors, touch panels, solar batteries and the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a thin film made of a one-dimensional nanomaterial such as a carbon nanotube and a method for manufacturing an electronic device.

  Carbon nanotubes (hereinafter abbreviated as CNT) have excellent electrical and mechanical properties, and are expected to be applied in a wide range of fields as potential materials for nanotechnology. It is actively done.

  Conventionally, as a method for producing a CNT thin film, a spray in which a thin film is formed by spraying a liquid in which CNT is dispersed in a solvent such as ethanol using ultrasonic waves onto a substrate using a spray device to evaporate the solvent. The Langmuir Blodget (LB) method for forming a thin film by repeating the operation of spreading a film made of solubilized CNTs on the water surface, immersing the substrate in a direction perpendicular to the water surface and pulling it up, and the solution containing the CNTs on the substrate There are known a coating method for coating on top, a filter method for uniformly depositing CNTs in a solution on a filter and transferring and generating CNTs on a substrate.

  Patent Document 1 entitled “Method for Producing Carbon Nanotube-Containing Film and Carbon Nanotube-Containing Coating” includes the following description.

  In the method for producing a carbon nanotube-containing coating film, the method for producing the carbon nanotube-containing coating film comprises applying a first dispersion containing at least carbon nanotubes and a solvent to a surface of a substrate, The solvent is removed to make the carbon nanotubes into a three-dimensional network structure. Further, a second dispersion containing at least a resin and a solvent is applied thereon, and the second dispersion is made into a three-dimensional network of carbon nanotubes. A method for producing a carbon nanotube-containing coating film, wherein the carbon nanotube-containing coating film is infiltrated into a structure.

  The film of the invention of Patent Document 1 provides excellent conductivity and transparency with a small carbon nanotube content. In a preferred embodiment, the carbon nanotubes are present in the film from about 0.001 to about 1% by weight. Preferably, about 0.01 to about 0.1% of carbon nanotubes are present in the film, so that excellent transparency is obtained and low haze is achieved.

  Patent Document 2 entitled “Method for producing carbon nanotube thin film, method for producing electronic device, method for producing thin film, method for producing structure and method for forming bubbles” has the following description.

  A carbon nanotube dispersion containing a surfactant was prepared, and air bubbles were mixed into it to form bubbles. When these bubbles were deposited on a substrate, compared to the carbon nanotube thin film obtained by the conventional method. It was found that a carbon nanotube thin film that is much more homogeneous and thin can be formed with high film thickness controllability. This is a carbon nanotube thin film formed by depositing carbon nanotubes present in a film made of a carbon nanotube dispersion on the surface of the bubble.

  Non-Patent Document 1 describes the formation of a SWNT array by CVD.

  Non-Patent Document 2 includes (1) preparing a stable and controlled polymer dispersion (epoxy dispersion) of nanowires or nanotubes, and (2) using a circular die to control bubbles with controlled pressure and expansion rate. There is a description of blown-bubble films (BBFs) consisting of the basic steps of expanding the polymer dispersion to expand and (3) transferring the bubbles to the substrate or open frame structure.

Japanese Patent No. 3665969 (Claims (Claim 1), Paragraph 0013) JP 2006-298715 A (paragraph 0006) S. J. Kang et al, “High-performance electronics using dense, perfectly aligned arrays of single-walled carbon”, Nature Nanotechnology, 2, 230-236 (2007) (FABRICATION OF NANOTUBE ARRAYS AND DEVICES) G. Yu et al, “Large-area blown bubble films of aligned nanowires and carbon nanotubes”, Nature Nanotechnology, 2, 372-377 (2007) (pages 372-373, FIG. 1).

  The film formed by the above spray method has many irregularities, and it is difficult to obtain a uniform film, and it is also difficult to control the film thickness. In addition, with the LB method, it has been difficult to obtain a very thin homogeneous carbon nanotube thin film. In the coating method, it is very difficult to mix and stably disperse CNTs in a solvent, and it is easy to aggregate. Therefore, there is a problem that it is difficult to form a uniform conductive film. For this reason, a method of preparing a stable dispersion solution using a dispersant or the like, a method of uniformly forming a film after being dispersed, and the like have been studied. The filter method has a problem that the film forming process is very complicated and contains a large amount of impurities. There is a method of voluntarily adhering CNTs to the substrate using the affinity between the CNTs and the substrate, but this method has a problem that the formation of the conductive film is limited to the silicon substrate. As other methods, there are an electrodeposition method, a method using CVD, and the like, but there is a problem that scale-up is very difficult.

  In Patent Document 1, a thin film using carbon nanotubes (CNT) can be used as a transparent conductive film. However, if the CNTs are only made into a thin film, the CNTs take a random arrangement, so the uniformity as a film is very low, and the conductivity is significantly inferior to a single CNT due to the resistance between the CNTs. .

  In the technique described in Non-Patent Document 1, the orientation is high, but since vapor phase growth is performed in situ, the growth is performed only on a specific substrate, and the quality and density of the CNT itself are low. As a result, the characteristics as a conductive film remain low.

  As a method of forming a CNT film using bubbles, there are techniques described in Patent Document 2 and Non-Patent Document 2, but the technique described in Patent Document 2 is not so high in orientation, and the technique described in Non-Patent Document 2 is used. Then there was a problem of low density. Patent Document 2 and Non-Patent Document 2 do not show data on the light transmittance and surface resistance of the obtained CNT thin film.

  The present invention has been made in order to solve the above-described problems, and its object is to manufacture a thin film that is made of a one-dimensional nanomaterial and has high orientation and transparency and good conductivity, and an electronic device. It is to provide a method for manufacturing an apparatus.

  That is, the present invention includes a first step of preparing a dispersion in which a one-dimensional nanomaterial is dispersed, a second step of attaching droplets of the dispersion to one end of the nozzle, and a gas from the other end of the nozzle. A third step of inflating the droplet to form a bubble made of a film containing the one-dimensional nanomaterial at the one end of the nozzle by allowing the droplet to flow; and bringing a part of the bubble into contact with the surface of the substrate; A fourth step of expanding the bubble by inflowing the gas from the other end of the nozzle to increase the contact area between the substrate and the bubble film; a fifth step of rupturing the bubble; And a sixth step of drying the film to form a thin film, and a method for producing a thin film made of a one-dimensional nanomaterial.

  The present invention also includes a first step of preparing a dispersion in which a one-dimensional nanomaterial is dispersed, a second step of attaching droplets of the dispersion to one end of the nozzle, and a gas from the other end of the nozzle. A third step of inflating the droplet to form a bubble made of a film containing the one-dimensional nanomaterial at the one end of the nozzle by allowing the droplet to flow; and bringing a part of the bubble into contact with the surface of the substrate; A fourth step of expanding the bubble by inflowing the gas from the other end of the nozzle to increase the contact area between the substrate and the bubble film; a fifth step of rupturing the bubble; And a sixth step of drying the film to form a thin film.

  According to the method for manufacturing a thin film of the present invention, a part of the bubbles made of the film containing the one-dimensional nanomaterial is brought into contact with the surface of the substrate, the bubbles are expanded, and the substrate and the bubble film are Since the contact area is increased, the bubble film is formed on the substrate surface and dried to produce the thin film made of the one-dimensional nanomaterial, the orientation is high, the transparency and the conductivity are good, A method for producing a thin film made of a one-dimensional nanomaterial can be provided. Further, the thickness of the thin film made of the one-dimensional nanomaterial is controlled by controlling the concentration of the one-dimensional nanomaterial in the dispersion liquid and / or the contact area between the substrate and the bubble film. Transparency and conductivity can be controlled.

  In addition, according to the method for manufacturing an electronic device of the present invention, a part of the bubbles made of the film containing the one-dimensional nanomaterial is brought into contact with the surface of the substrate, the bubbles are expanded, and the substrate and the bubbles are formed. The contact area with the film is increased, the bubble film is formed on the substrate surface, and the film is dried to form a thin film made of the one-dimensional nanomaterial. Therefore, the orientation is high and the transparency and conductivity are good. In addition, it is possible to provide a method of manufacturing an electronic device having a thin film made of the one-dimensional nanomaterial. Further, the thickness of the thin film made of the one-dimensional nanomaterial is controlled by controlling the concentration of the one-dimensional nanomaterial in the dispersion liquid and / or the contact area between the substrate and the bubble film. The manufacturing method of the electronic device which can control transparency and electroconductivity can be provided.

  The thin film manufacturing method of the present invention preferably includes a seventh step of cutting the thin film together with the substrate in a shape maintaining one orientation direction of the one-dimensional nanomaterial. According to such a configuration, it is possible to manufacture a thin film made of the one-dimensional nanomaterial having high transparency and conductivity and having the orientation aligned in the one direction.

  In the first step, the one-dimensional nanomaterial may be dispersed in an aqueous solution containing a surfactant. According to such a configuration, the active effect of the surfactant can be enhanced using an aqueous solution as a solvent, the dispersion of the one-dimensional material can be improved, and the dispersion solution in which the one-dimensional material is uniformly dispersed can be obtained. Can be prepared.

  Moreover, it is good to set it as the structure which has the process of washing the said film with water following the said 5th process. According to such a configuration, since the surfactant remaining in the film can be removed by washing with water, a thin film made of the one-dimensional nanomaterial having better transparency and conductivity can be manufactured. it can. Note that the step of washing the membrane with water may be performed following the sixth step.

  Further, it is preferable to repeat the first to sixth steps. According to such a configuration, the thickness of the thin film made of the one-dimensional nanomaterial can be controlled by controlling the number of repetitions of the first to sixth steps, and the transparency and conductivity can be controlled. Can be controlled.

  The one-dimensional nanomaterial may be radially oriented substantially parallel to the surface of the substrate. According to such a configuration, the one-dimensional nanomaterial is oriented in a linear direction radially about one point, and thus the one-dimensional nanomaterial has substantially central symmetry in optical characteristics and electrical characteristics. A thin film made of a material can be manufactured.

  In addition, the one-dimensional nanomaterial is preferably conductive. According to such a configuration, since the one-dimensional nanomaterial is radially oriented in the linear direction, a thin film made of the one-dimensional nanomaterial having high conductivity in the linear direction can be manufactured.

  Further, the one-dimensional nanomaterial is preferably a carbon nanotube. According to such a configuration, a highly transparent and conductive thin film made of the one-dimensional nanomaterial can be manufactured.

  In addition, the thickness of the thin film is preferably 100 nm or less. According to such a configuration, since the thin film made of the one-dimensional nanomaterial has high transparency, it can be used for a transparent electrode that requires high transparency.

  Further, the transmittance (the transmittance excluding the substrate) is preferably 90% or more. According to such a configuration, since the thin film made of the one-dimensional nanomaterial has high transparency, it can be used for a transparent electrode that requires high transparency.

  In addition, the surface resistance is preferably 500 Ω / sq or less. According to such a configuration, since the thin film made of the one-dimensional nanomaterial has high conductivity, it can be used for electrodes and wiring (conductive lines) that require high conductivity.

  The substrate is preferably transparent. According to such a configuration, since a thin film having high transparency made of the one-dimensional nanomaterial can be formed on the transparent substrate, a transparent electrode or a wiring (conductive line) is formed, and high transparency It is possible to manufacture a transparent electrode body or a wiring (conductive line) body that requires high performance.

  The substrate is preferably a transparent polymer substrate. According to such a configuration, since the flexible polymer substrate is used, a thin film made of the one-dimensional nanomaterial can be formed thereon, and an electrode or a wiring (conductive line) is formed. It is possible to manufacture an electrode body or a wiring (conductive line) body that is required to have flexibility (flexibility).

  The polymer substrate may be made of any one of reethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), and derivatives thereof. According to such a configuration, the polymer substrate on which the thin film made of the one-dimensional nanomaterial is formed has optical characteristics, electrical characteristics, and mechanical characteristics according to the intended use and usage environment. Accordingly, the material of the polymer substrate can be appropriately selected.

  In the electronic device manufacturing method of the present invention, the thin film may be formed by each of the above-described thin film manufacturing methods. According to such a configuration, an electronic device having the above-described effects obtained by each of the above-described thin film manufacturing methods can be manufactured.

  The thin film has light transmittance and conductivity and is preferably used as a transparent electrode. According to such a structure, since the said thin film has high light transmittance and electroconductivity, it can be used as a transparent electrode of various electronic devices.

  It may be configured as any one of a liquid crystal device, an electroluminescence device, an electrochromic device, a field effect transistor, a touch panel, and a solar cell. According to such a configuration, since the thin film has high transparency and conductivity, various high-performance electronic devices can be provided.

  The thin film is preferably used as a conductive line. According to such a structure, since the said thin film has high transparency and electroconductivity, it can be used as a wiring (conductive line) body of various electronic devices.

  In the method for producing a thin film made of a one-dimensional nanomaterial according to the present invention, a dispersion liquid in which a one-dimensional nanomaterial such as CNT is dispersed in an aqueous solution containing a surfactant is prepared, and droplets of this dispersion liquid are applied to one end of a nozzle. Air bubbles such as air, nitrogen, and oxygen are allowed to flow from the other end of the nozzle to expand the droplets to form a bubble made of a film containing a one-dimensional nanomaterial at one end of the nozzle. A part of the bubble contacts the surface of the substrate. The gas flows in from the other end of the nozzle to expand the bubbles, increase the contact area between the substrate and the bubble film, and after the contact area reaches the desired size, the bubbles are ruptured and formed on the substrate. The film containing the one-dimensional nanomaterial is washed with water, and then, in order to suppress the aggregation of the one-dimensional nanomaterial, it is quickly dried with hot air or the like so as not to disturb the arrangement of the one-dimensional nanomaterial, and is transparent. A thin film made of a one-dimensional nanomaterial is formed. Note that the film including the one-dimensional nanomaterial formed on the substrate may be dried and then washed with water, and the one-dimensional nanomaterial can be prevented from falling off.

  The substrate may be of any material and may be a transparent polymer substrate. The one-dimensional nanomaterial is substantially parallel to the substrate surface and is radially oriented, and a thin film made of the one-dimensional nanomaterial is cut out together with the substrate in a shape maintaining one orientation direction.

  In addition, after forming a thin film made of a one-dimensional nanomaterial in the same manner as described above by masking other areas except a desired area of the substrate on which a thin film made of a one-dimensional nanomaterial is to be formed, The masking can be removed to form a thin film made of a one-dimensional nanomaterial in a desired region of the substrate (masking method). Also in this case, the one-dimensional nanomaterial is substantially parallel to the substrate surface and oriented radially. By masking as described above, a thin film made of a one-dimensional nanomaterial can be formed in a desired shape in a desired region of a member constituting an electronic circuit.

  A thin film made of a one-dimensional nanomaterial is excellent in transparency and conductivity, and can be used as a transparent electrode in a liquid crystal device, an electroluminescence device, an electrochromic device, a field effect transistor, a touch panel, a solar cell, and the like. Further, by etching a transparent conductive film made of a one-dimensional nanomaterial, for example, a CNT transparent conductive film into a desired shape with ozone or ultraviolet light, or masking other regions other than the desired region having a desired shape, By forming a CNT transparent conductive film in a desired shape in a desired region exposed to the outside, it can be used as a transparent electrode of various electronic devices, or as a wiring or electrode terminal as a transparent conductive line of various electronic devices. it can. Thus, the transparent conductive film made of a one-dimensional nanomaterial can also be used as a transparent wiring (conductor line) forming an electronic circuit. Moreover, the thin film which consists of a one-dimensional nanomaterial by the method of this invention can also be used as an antistatic film.

The one-dimensional nanomaterial is preferably conductive, for example, carbon nanotubes, metal nanowires such as Cu, Ag, Au, Ni, Co, and Sn, oxide nanowires such as TiO ₂ , SnO ₂ , and ZnO, Organic nanofibers such as carbon and cellulose.

  Hereinafter, embodiments according to the present invention will be described in detail with reference to the drawings.

Embodiment The case where a thin film according to the present invention is formed on a PET substrate using CNT as an example of a one-dimensional nanomaterial will be described. The CNT thin film can be formed as follows.

  1A and 1B are diagrams illustrating a method of forming a carbon nanotube (CNT) thin film according to an embodiment of the present invention. FIG. 1A is a cross-sectional view illustrating a forming procedure, and FIG. 1A is a perspective view of the procedure (3) in FIG. 1A, and FIG. 1C is a diagram showing the cross-sectional details of the procedure (3) in FIG.

  First, a dispersion liquid in which CNTs 22 are dispersed in an aqueous solution containing a surfactant is prepared. As shown in the procedure (1) of FIG. 1A, the droplet of the dispersion liquid is attached to one end of the nozzle 12 and the droplet 16 is expanded by injecting air 16 from the other end of the nozzle. Bubbles 10 made of a film containing CNTs 22 are formed at one end of the nozzle 12.

  Next, as shown in step (2) of FIG. 1A, a part of the bubble 10 is brought into contact with the surface of the substrate 14 and air 16 is caused to flow from the other end of the nozzle 12 to expand and expand the bubble 10. As shown in step (3) of FIG. 1A, the contact area between the substrate 14 and the bubble 10 is increased, and the bubble 10 is ruptured when the contact area reaches a desired size. As shown in the procedure (4) of (A), the CNT film 20 that forms the bubbles 10 is laminated so as to be transferred to the surface of the substrate 14, and the CNT film 20 including the CNTs 22 is formed on the substrate 14. After the CNT film 20 is washed with water to remove the surfactant, the CNT film 20 is quickly dried with musical notes or the like. After the CNT film 20 is dried, the CNT film 20 may be washed with water to remove the surfactant. In this way, the CNT film 14 having the bulk conductivity of the conductivity of a single CNT can be formed on the substrate 14.

  As described above, a film in which the CNTs 22 are oriented in the direction in which the film of the bubbles 10 is stretched, and the CNTs 22 are radially oriented around approximately one point substantially parallel to the surface of the substrate 14 is formed. Furthermore, if necessary, the same operation as described above can be repeated on the CNT film 20. That is, the lamination of the CNT film 20 forming the bubbles 10 on the substrate 14 can be repeated. The thickness of the CNT film 22 formed on the substrate 14 can be controlled by the size of the contact area between the substrate 14 and the bubble 10 film. Furthermore, the thickness of the CNT film 22 formed on the substrate 14 can be controlled by the concentration of the CNT 22 in the dispersion liquid and / or the number of times the CNT film 20 is laminated on the substrate 14. The transparency and conductivity of the film 22 can be controlled, and the CNT thin film 20 having desired transmittance and conductivity can be formed. For example, the CNT film 20 having a light transmittance of 90% or more at 550 nm excluding the substrate and the CNT film 20 having a surface resistance of 500 Ω / sq or less can be formed.

  As described above, since the CNTs 22 are radially oriented along one direction about one point, the CNT film 14 is cut out together with the PET substrate 14 in a shape that maintains the orientation along the one direction of the CNTs 22. The orientation is composed of CNTs 22 along one direction, and a highly conductive and transparent CNT film / PET can be obtained in the direction along one direction, which is used in various electronic devices described later. For example, the cutting is performed so that the direction along one direction is parallel to the direction in which the current flows, the direction connecting the two electrodes, or the direction of the linear wiring. Further, the obtained CNT film / CNT film on PET can be etched into a desired shape as required by ozone or ultraviolet rays.

  In the CNT thin film manufacturing method described above, the bubbles 12 are formed by moving the nozzle 12, immersing the tip of the nozzle in the CNT dispersion, holding the CNT dispersed droplets at the tip of the nozzle, and inflowing air 16 into the nozzle 12. And bubble size detection, contact of the bubble 10 to the surface of the substrate 14 by the movement of the nozzle 12, expansion of the bubble 10 and detection of the bubble size by the inflow of air 16 into the nozzle 12, burst of the bubble 10, and the surface of the substrate 14 It is possible to easily automate each process such as washing and drying of the laminated CNT film 14 without requiring a complicated mechanism.

  The CNT thin film described above can be formed on any substrate other than the PET substrate. When the thickness of a substrate such as a PET substrate is thin, the substrate is placed on a flat surface such as an SI substrate, for example, using an adhesive that can be easily peeled off by low-temperature heating, and the substrate surface is held flat. A CNT thin film is formed on this.

  By forming the CNT thin film on a transparent electrically insulating substrate, a transparent substrate suitably used in various optical devices can be obtained. Also, by etching the CNT thin film into a desired shape with ozone or ultraviolet light, or by masking other regions except the desired region having the desired shape, the CNT thin film is formed in the desired shape exposed to the outside. By forming, it can be used as a transparent electrode of various electronic devices, a wiring as a conductive line of various electronic devices, or an electrode terminal.

  A CNT dispersion composed of CNT, a surfactant, and a solvent will be described.

  As the CNT, for example, those produced by arc discharge, laser ablation, chemical vapor deposition (CVD) method or the like are used. These CNTs are purified by removing impurities such as amorphous carbon by high-temperature heat treatment, acid treatment with sulfuric acid, hydrochloric acid, nitric acid, hydrogen peroxide, etc., alkali treatment with sodium hydroxide, etc. Use a higher one.

  As the CNT, a single-walled single-wall carbon nanotube (SWCNT), a double-walled double-walled carbon nanotube (DWCNT), a multi-walled multi-walled carbon nanotube (MWCNT), or the like is used. The length of CNT is not particularly limited, but in order to obtain good dispersibility, for example, a length of about 1 μm or less is desirable.

  As the surfactant, an anionic (anionic) surfactant, a cationic (cationic) surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used.

As an anionic surfactant, C ₈ H ₁₇ SO ₃ ^- Na ⁺ , C ₁₀ H ₂₁ SO ₃ ^- Na ⁺ , C ₁₂ H ₂₅ SO ₃ ^- Na ⁺ , C ₁₄ H ₂₉ SO ₃ ^- Na ⁺ , C ₁₆ H ₃₃ SO ₃ ^- Na ⁺ , C ₈ H ₁₇ SO ₄ ^- Na ⁺ , C ₁₀ H ₂₁ SO ₄ ^- Na ⁺ , C ₁₁ H ₂₃ SO ₄ ^- Na ⁺ , C ₁₂ H ₂₅ SO ₄ ^- Na ⁺ , C ₁₂ H ^{_{25 SO 4 - Li +, C}} 12 H 25 SO 4 - K +, (C 12 H 25 SO 4 -) 2 Ca 2 +, C 12 H 25 SO 4 - N (CH 3) 4 +, C 12 H 25 ^{_{SO 4 - N (C 2 H}} 5) 4 +, C 12 H 25 SO 4 - N (C 4 H 9) 4 +, C 13 H 27 SO 4 - Na +, C 14 H 29 SO 4 - Na +, ^{_{C 15 H 31 SO 4 - Na}} +, C 16 H 33 SO 4 - Na +, C 12 H 25 CH (SO 4 - Na +) C 3 H 7, C 10 H 21 CH (SO 4 - Na +) C _{5 H 11, C 13 H 27} CH (CH 3) CH 2 SO 4 - Na +, C 12 H 25 _{CH (C 2 H 5) CH} 2 SO 4 - Na +, C 11 H 23 CH (C 3 H 7) CH 2 SO 4 - Na +, C 10 H 21 CH (C 4 H 9) CH 2 SO 4 - Na ⁺ , C ₁₂ H ₂₅ OC ₂ H ₄ SO ₄ ^- Na ⁺ , C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₂ SO ₄ ^- Na ⁺ , C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₄ SO ₄ ^- Na ⁺ _{, C 8 H 17 OOC (CH} 2) 2 SO 3 - Na +, C 10 H 21 OOC (CH 2) 2 SO 3 - Na +, C 12 H 25 OOC (CH 2) 2 SO 3 - Na +, C _{14 H 29 OOC (CH 2)} 2 SO 3 - Na +, p-n-C 8 H 17 C 6 H 4 SO 3 - Na +, p-n-C 10 H 21 C 6 H 4 SO 3 - Na + _{, p-n-C 12 H} 25 C 6 H 4 SO 3 - Na +, C 7 F 15 COO - K +, C 7 F 15 COO - Na +, (CF 3) 2 CF (CF 2) 4 COO - _{^{Na +, n-C 8 F}} 17 SO 3 - Li + , or the like can be used. .

As cationic surfactants, C ₈ H ₁₇ N (CH ₃ ) ₃ ⁺ Br ⁻ , C ₁₀ H ₂₁ N (CH ₃ ) ₃ ⁺ Br ⁻ , C ₁₂ H ₂₅ N (CH ₃ ) ₃ ⁺ Br ⁻ , C ₁₄ H ₂₉ N (CH ₃ ) ₃ ⁺ Br ⁻ , C ₁₆ H ₃₃ N (CH ₃ ) ₃ ⁺ Br ⁻ , C ₁₂ H ₂₅ Pyr ⁺ Br ⁻ , C ₁₂ H ₂₅ Pyr ⁺ Cl ⁻ , C ₁₂ H ₂₅ Pyr ⁺ Cl ⁻ , C ₁₆ H ₃₃ Pyr ⁺ Cl ⁻ , C ₁₂ H ₂₅ N ⁺ (C ₂ H ₅ ) (CH ₃ ) ₂ Br ⁻ , C ₁₂ H ₂₅ N ⁺ (C ₈ H ₁₇ ) (CH ₃ ) ₂ Br ⁻ , C ₁₄ H ₂₉ N ⁺ (C ₂ H ₅ ) ₃ Br ⁻ , C ₁₄ H ₂₉ N ⁺ (C ₄ H ₉ ) ₃ Br ^{− and the} like can be used.

As amphoteric surfactants, C ₈ H ₁₇ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ , C ₁₀ H ₂₁ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ , C ₁₂ H ₂₅ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ , C ₁₄ H ₂₉ N + (CH ₃ ) ₂ CH ₂ COO ⁻ , C ₁₆ H ₃₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ , C ₁₀ H ₂₁ CH (Pyr ⁺ ) COO ⁻ , C ₁₄ H ₂₉ CH (Pyr ⁺ ) COO ⁻ or the like can be used.

As nonionic surfactants, C ₈ H ₁₇ CHOHCH ₂ OH, C ₁₂ H ₂₅ CHOHCH ₂ CH ₂ OH, C ₈ H ₁₇ (OC ₂ H ₄ ) ₃ OH, C ₁₀ H ₂₁ (OC ₂ H ₄ ) ₄ OH _{, C 11 H 23 (OC 2} H 4) 8 OH, C 12 H 25 (OC 2 H 4) 2 OH, C 12 H 25 (OC 2 H 4) 4 OH, C 12 H 25 (OC 2 H 4) ₆ OH, C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₈ OH, C ₁₃ H ₂₇ (OC ₂ H ₄ ) ₈ OH, C ₁₄ H ₂₉ (OC ₂ H ₄ ) ₈ OH, C ₁₅ H ₃₁ (OC ₂ H _{4) 8 OH, p-t} -C 8 H 17 C 6 H 4 O (C 2 H 4 O) 2 H, p-t-C 8 H 17 C 6 H 4 O (C 2 H 4 O) 8 H N-octyl-β-D-glucoside, n-decyl-β-D-glucoside, and the like can be used.

Among the above surfactants, an anionic surfactant _{CH 3 (CH 2) 10 CH} 2 SO 4 - Na + ( sodium dodecyl sulfate (SDS: Sodium dodecyl sulfate)) be used, dispersion of the CNT However, the present invention is not limited to this, and two or more kinds of the above surfactants can be mixed and used.

  As a solvent for the CNT dispersion liquid, any of an acidic solvent, an alkaline solvent, a neutral solvent, and a mixed solution thereof may be used, but it is preferable to use water in order to enhance the activity effect of the surfactant. .

  The CNT dispersion is prepared by changing the blending ratio depending on the surfactant and the type of CNT. For example, the surfactant is 0.01 to 20% by weight and the CNT is 0.001 to 1% by weight with respect to the solvent. It is preferable to do so.

  By stirring the mixture of CNT, surfactant, and solvent using an ultrasonic wave, a ball mill, a bead mill, a stirrer, or the like, a CNT dispersion liquid in which CNTs are uniformly dispersed can be obtained. In addition, if necessary, for example, 0.0001 to 0.1% by weight of 4-bromobenzene-diazonium-tetrafluoroborate is added to water and added to CNT. Treatment such as chemical modification may be performed.

There is no limitation on the type of substrate on which the CNT thin film is formed, and any of conductive substrates, electrically insulating substrates, and those on which a metal film or an electro-insulating film is formed on the substrate surface can be used. Is not limited to a planar shape, and may be a curved surface having irregularities, and is appropriately selected according to the purpose. In a substrate having a hydrophilic layer such as an oxide film formed on the surface, a CNT thin film is easily formed stably on the hydrophilic layer. For example, a silicon substrate having a SiO ₂ film formed on the surface, A glass substrate or the like is suitable as a substrate for forming a CNT thin film.
Is used.

  The substrate need not be rigid like a glass substrate, and various polymer substrates (polymer substrates) can be used. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PAN), polyethylene naphthalate (PEN) Polyester film such as polybutylene terephthalate (PBT), polypropylene (PP), polyethylene (PE), polyethersulfone (PES), polyimide (PI), polycarbonate (PC), polyarylate (PAR), poly A transparent substrate such as sulfone (PS) can be used.

  The CNT thin film according to the present invention can be used in electronic devices such as solar cells, photoelectric conversion devices, light-emitting devices, display devices, FETs, chemical sensors, and the like. Specifically, for example, photoelectric conversion layers, FETs It can be used as a channel material, a transparent electrode, and a transparent wiring material.

  Any kind of one-dimensional nanomaterial may be used as long as the one-dimensional nanomaterial can be dispersed in a solvent containing a surfactant and can form bubbles composed of a film containing the one-dimensional nanomaterial. . In addition to carbon-based one-dimensional nanomaterials typified by CNTs, other various one-dimensional nanomaterials, molecular nanowires, and other carbon-based materials such as fullerene and other various materials may be used.

  In the method for producing a thin film according to the present invention, by laminating a bubble film containing a one-dimensional nanomaterial on an arbitrary substrate by a simple method, a single-layer thin film having excellent conductivity and transparency, or a laminated film The laminated film in which the light transmittance and the conductivity are controlled by repeating the above can be obtained using a very simple apparatus in the room temperature atmosphere, and the one-dimensional nanomaterial is not deteriorated in the manufacturing process.

  FIG. 2 is a diagram for explaining the conductive characteristics of a carbon nanotube (CNT) thin film and its application to an electronic circuit in the embodiment of the present invention, and FIG. 2 (A) is a schematic diagram for explaining the conductive characteristics of a CNT alignment film. FIG. 2 and FIG. 2B are cross-sectional views for explaining the outline of a back gate type effect transistor using a CNT thin film.

  FIG. 2A is a diagram for explaining an estimation of the conductive characteristics in the axial direction of the high-density alignment film of CNT 32 when the CNTs 32 are connected in two dimensions and arranged on the substrate 31. Resistance values in the length direction per CNT (line resistance), contact resistance between CNTs, length per CNT, metal ratio of CNT components, length and width of CNT alignment film, etc. The transmittance of the CNT alignment film can be estimated from the film thickness and the absorption coefficient of the CNT. For example, the axial line resistance 33 of the CNT 32 is 2,400 Ω / μm, When the inter-contact resistance 34 between the wall surfaces of the CNT 32 is 50,000 Ω, the inter-contact resistance 35 between the tip portions of the CNT 32 is 50,000 Ω (other factors are omitted), etc., the wavelength of the bimolecular CNT thin film is 550 nm. 96% is definitive transmittance, the resistance value between the electrodes 30a, 30b is about 140Omu.

  FIG. 2B shows a schematic configuration of a back gate type effect transistor (FET) using a CNT thin film. In the FET, a gate electrode 45 is laminated on a substrate (PET) 46, for example, the surface of the substrate 46. 45, for example, an insulator layer 44 made of, for example, PMMA (polymethyl methacrylate) or polyimide varnish is laminated, and a source / drain channel 43 made of, for example, an organic semiconductor layer or an inorganic semiconductor layer is laminated on the insulator layer 44. A source electrode 41 and a drain electrode 42 are stacked on the drain channel 43. In such a configuration, when the substrate 46, the gate electrode 45, the insulator layer 44, the source / drain channel 43, the source electrode 41, and the drain electrode 42 are formed of a transparent layer, an optically transparent FET can be realized.

  As the gate electrode 45, the source electrode 41, and the drain electrode 42 in the FET described above, a CNT transparent conductive film can be formed by the above-described masking method using metal CNTs by the method of the present invention. Further, as the source / drain channel 43, a CNT transparent film can be formed by the above-described masking method using a semiconductor CNT by the method of the present invention.

  As described above, the back gate type effect transistor has been described as an example of the FET using the CNT thin film. However, it is needless to say that a well-known top gate type structure can be used. 3A and 3B are diagrams illustrating a touch panel using a transparent conductive film according to an embodiment of the present invention. FIG. 3A is a cross-sectional view, and FIG. 3B is a plan view of the transparent conductive film. It is.

  Usually, the touch panel is placed over an LCD (Liquid Crystal Display) or CRT (Cathode Ray Tube), so that a transmittance of 80% or more is required in the visible light region. The uniformity of the resistance of the film constituting the film is required.

  As shown in FIG. 3A (A1), the transparent touch panel includes a deformable PET substrate (upper substrate) 2a having a transparent conductive film 1a formed as an upper electrode, and an electrically insulating dot spacer 3 on the surface. A transparent conductive film 1b formed with a glass substrate (lower substrate) 2b formed as a lower electrode, and the upper substrate 2a and the lower substrate 2b maintain a slight gap (space) 5 so that both electrodes face each other. They are joined via the electrical insulating layer 4.

  The distance 5 between the upper substrate 2a and the lower substrate 2b is, for example, 100 μm to 300 μm. With respect to this distance 5, the height of the dot spacer 3 is such that the upper electrode and the lower electrode are always in contact with each other to be in the ON state. Is, for example, about 5 μm to 50 μm so as not to affect the image displayed on the panel. In a state where both electrodes are not touched, no current flows because both electrodes are not in contact by the minute dot spacer 3. The lower electrode may be formed of an ITO (indium tin oxide) film.

  As shown in (A2) of FIG. 3A, when the PET substrate 2a side is touched and pressed with a finger or a dedicated pen, the touched portion of the PET substrate 2a is deformed, and the transparent conductive films 1a and 1b come into contact with each other. Electricity flows and a switch action occurs and the input is detected.

  As shown in (B1) to (B4) of FIG. 3B, the transparent conductive films 1a and 1b constituting the upper electrode and the lower electrode are arranged on a continuous planar transparent conductive film and a two-dimensional matrix. It can be set as the transparent conductive film which consists of the made discontinuous microelectrode.

  In the example shown in (B1), (B3), and (B4) of FIG. 3 (B), the contact points of the upper electrode and the lower electrode generated by the deformation of the PET substrate 2a by pressing (the upper electrode and the lower electrode are closed circuit). The position of the above-mentioned microelectrodes forming the above, that is, the pressed position (coordinates) is detected by a reading circuit to which the microelectrodes are connected.

  The example shown in (B2) of FIG. 3 (B) is an analog resistive touch panel, which is pressed by measuring the voltage dividing ratio by the resistance of the transparent conductive films 1a and 1b constituting the upper electrode and the lower electrode, respectively. The detected position (coordinates) is detected.

  Although not shown in FIG. 3, in the example shown in (B4) of FIG. 3B, the fine electrodes 1a arranged in one row in the horizontal direction are formed as thin strip electrodes connected in each row, and arranged in one column in the horizontal direction. The aligned microelectrodes 1b are formed as thin strip electrodes connected to each other, and the strip electrodes constituting the upper electrode and the lower electrode are arranged so as to be orthogonal to each other, and the strip electrodes of the upper electrode and the lower electrode are used as a reading circuit. It is also possible to have a connected matrix structure, and the contact point of the upper and lower electrodes (position where the upper electrode and the lower electrode strip electrode contact to form a closed circuit) generated by pressing is detected by the reading circuit. You can also

  Note that the microelectrodes and strip electrodes can be formed by etching one transparent conductive film.

  The conductive transparent film of the present invention applies a voltage to a liquid crystal sandwiched between transparent substrates on which transparent electrodes are formed, and utilizes a change in light transmittance caused by the orientation of liquid crystal molecules (LCD, It can also be used as a transparent electrode in (not shown).

  The transparent conductive film of the present invention can be used as a transparent electrode in an electrochromic device (not shown). An electrochromic device is an electrochemical redox reaction of an electrochromic compound, which occurs when a voltage is applied between a transparent electrode carrying an electrochromic compound made of an organic or inorganic compound and an electrode facing the transparent electrode. It utilizes the accompanying change in absorption spectrum (electrochromic phenomenon) and is applied to a display device or the like.

  The transparent conductive film of the present invention can be used as a transparent electrode in an electroluminescence device (not shown). An electroluminescent device uses a light emission generated by applying a voltage between two electrodes, in which a light emitter made of an inorganic material such as zinc sulfide or an organic material such as diamine is disposed between two electrodes. And is applied to display devices, lighting devices, and the like.

Furthermore, the transparent conductive film of the present invention can be used as a transparent electrode in a solar cell (not shown), and has a simple structure in which a titanium dioxide layer adsorbing a trace amount of pigment and an electrolyte are sandwiched between two transparent electrodes. In the dye-sensitized solar cell having the above, it can be used as a transparent conductive film for forming an electrode (anode electrode) on the light incident side.
The thin film according to the present invention has low surface resistance, high light transmittance, and excellent electrical and optical characteristics, and can be suitably used for touch panels, electroluminescence devices, electrochromic devices, solar cells, and the like. .

Examples Hereinafter, examples will be described. CNT (single-walled CNT, SWNT) is added to an aqueous solution of SDS (Sodium Dodecyl Sulfate), and an ultrasonic homogenizer is used to perform a homogenization treatment for 10 minutes under the condition of an output of 50 W to prepare a dispersion. A CNT transparent conductive film was prepared by the method described above. In addition, SWNT used the commercial item (Carbon solutions inc., Product model number P3-SWNT) produced by arc discharge, homogenizing.

  FIG. 4 is a diagram showing an example of an SEM image of a carbon nanotube thin film in an example of the present invention. FIG. 4 (A) is 2,500 times, FIG. 4 (B) is 7,000 times, and FIG. C) is 25,000 times, and FIG. 4D is 30,000 times.

  In FIG. 4, a Si wafer was used as a substrate, and a dispersion was prepared by adding 0.1 g / mL of CNTs in a 1% aqueous solution of SDS, and formed by one-time lamination by the method described above. An SEM image of the CNT transparent conductive film is shown, and CNTs oriented along substantially one direction are observed. The CNT transparent conductive film had a thickness of 0 to 10 nm including SDS and a surface resistance of 1 MΩ / □.

  FIG. 5 is a diagram showing an example of an AFM image of the carbon nanotube thin film in the example of the present invention.

  5A and 5B show a left side view using a Si wafer as a substrate, and adding 0.5 g / mL CNTs in a 5% aqueous solution of SDS to this surface to prepare a dispersion. The SEM image of the CNT transparent conductive film formed by one-time lamination by the above-described method is shown. As in FIG. 4, CNTs aligned in substantially one direction are observed. The vertical position of the elongated central view shown in FIGS. 5 (A) and 5 (B) is the height in the left view shown in FIGS. 5 (A) and 5 (B) (that is, perpendicular to the paper surface of the left view). The information on the left is shown by a gray scale bar, with the top of the center figure being the highest and the bottom being the bottom. It shows the lowest. The whitish part in the left view shows a higher place, this place is shown at a higher position in the central figure, and the darker part in the left figure shows a lower place, which is shown in a lower position in the central figure. The upper white portion of the central view shows the highest place in the left view, and the lower black portion shows the lowest place in the left view. The histograms on the right side shown in FIGS. 5 (A) and 5 (B) relatively indicate the area occupied by each density (ie, height) in the left side. When displaying the left figure in color, replacing the gray scale bar in the center figure with a color scale bar, replacing white with red and black with blue makes it easier to understand. By the specific color of the gray scale bar or the color scale bar, it is possible to easily know the rate at which the substance shown in the left figure is exposed to the outside. The thickness of the CNT transparent conductive film shown in FIG. 5 was 0 to 50 nm including SDS, and the surface resistance was 500 kΩ / □.

  FIG. 6 is a diagram showing an example of an AFM image of the carbon nanotube thin film after washing with water in the example of the present invention.

  6A and 6B, the left side view shown in FIG. 6B was obtained by immersing the CNT transparent conductive film produced in the same manner as the example shown in FIG. It is an AFM image of a CNT transparent conductive film. Non-linear ones are CNTs, and those on the particles are surfactants remaining in the CNT transparent conductive film. The central view and the right side view shown in FIGS. 6A and 6B show the same contents as the central view and the right side view shown in FIGS. 5A and 5B, respectively. The CNT transparent conductive film had a thickness of 0 to 5 nm and a surface resistance of 1 kΩ / □.

  FIG. 7 is a diagram showing an example of an optical microscope image of a carbon nanotube thin film in an example of the present invention.

FIG. 7 is an optical microscopic image (magnification is 100 times) of a carbon nanotube thin film formed on a silicon oxide (SiO ₂ ) substrate in which gold is patterned by lithography, and FIG. 7B is formed on the silicon oxide substrate. It is a figure which shows the optical microscope image (magnification is 50 times) of the carbon nanotube thin film.

  FIG. 7 (A) shows a case where 0.2 mg / mL CNT is added to a 1% aqueous solution of SDS on the surface of a silicon substrate to prepare a dispersion, and the CNT transparent layer formed by one-time lamination by the method described above. The SEM image of an electrically conductive film is shown. The CNT transparent conductive film had a thickness of 0 to 20 nm and a surface resistance (including gold) of 5Ω / □.

  FIG. 7 (B) shows a case in which 0.2 mg / mL CNT was added to a 1% aqueous solution of SDS on the surface of a silicon oxide substrate to prepare a dispersion, and CNTs formed by one-time lamination by the method described above. The SEM image of a transparent conductive film is shown. On the surface of the substrate, it is observed that the CNTs are radially oriented in a substantially linear direction about one point. The CNT transparent conductive film had a thickness of 0 to 20 nm and a surface resistance of 1 MΩ / □.

  FIG. 8 is a diagram showing an example of an optical microscope image (magnification is 500 times) of a carbon nanotube thin film formed on a PET substrate in an example of the present invention.

  8 (A) and 8 (B) show a method in which a dispersion is prepared by adding 0.2 mg / mL CNT in a 1% aqueous solution of SDS to the surface of a PET substrate (thickness 250 μm). Shows an SEM image of a CNT transparent conductive film formed by one-time lamination. Similar to the example shown in FIG. 7B, it is observed that the CNTs are radially oriented in a substantially linear direction about one point on the surface of the PET substrate. The CNT transparent conductive film had a thickness of 0 to 20 nm and a surface resistance of 1 MΩ / □.

  FIG. 9 is a diagram showing an example of an absorption spectrum of a carbon nanotube thin film formed on a PET substrate (thickness 250 μm) in an example of the present invention, where the horizontal axis represents wavelength (nm) and the vertical axis represents transmittance. Show. The absorption spectrum includes the absorption of the PET substrate.

  The uppermost curve shown in FIG. 9 is obtained by adding a dispersion of 0.2 mg / mL of CNT in a 1% aqueous solution of SDS, and preparing a dispersion of the CNT transparent conductive film formed by one-time lamination by the method described above. An example of an absorption spectrum is shown. The thickness of the CNT transparent conductive film was about 10 nm, and the surface resistance was 900Ω / □.

  The central curve shown in FIG. 9 shows the absorption of the CNT transparent conductive film formed by one-time lamination by adding 0.2 mg / mL CNT in 1% aqueous solution of SDS to prepare a dispersion. The example of a spectrum is shown, The thickness of the CNT transparent conductive film was about 10 nm, and the surface resistance was 850 Ω / □.

  The lowermost curve shown in FIG. 9 is obtained by adding a dispersion of 0.2 mg / mL CNTs in a 1% aqueous solution of SDS, and preparing a dispersion of the CNT transparent conductive film formed by one-time lamination by the method described above. An example of an absorption spectrum is shown. The thickness of the CNT transparent conductive film was about 10 nm, and the surface resistance was 850Ω / □.

  As shown in FIG. 9, the transmittance is 85% or more at a wavelength of 400 nm or more, and the transmittance is 87% or more at a wavelength of 450 nm or more, indicating a flat absorption spectrum.

  FIG. 10 is a graph showing the relationship between the absorbance of the carbon nanotube thin film and the sheet conductivity in Examples of the present invention, where the horizontal axis represents the absorbance and the vertical axis represents the sheet conductivity (S / sq).

  FIG. 11 is a diagram showing the relationship between the transmittance of the carbon nanotube thin film and the surface resistance in Examples of the present invention, where the horizontal axis represents the transmittance (%) and the vertical axis represents the surface resistance (Ω / sq).

  10 and FIG. 11, 0.2 mg / mL CNT was added to 1% aqueous solution of SDS to prepare a dispersion, and formed on a PET substrate by laminating 1 to 30 times by the method described above. This is data obtained with respect to the CNT transparent conductive film, and the absorbance and transmittance shown on the horizontal axis are values at 550 nm not including the contribution of the PET substrate.

  As shown in FIG. 10, when α is a coefficient, there is a wide range, and a relationship of sheet conductivity (y) = α × absorbance (x) is established between absorbance (x) and sheet conductivity (y). , Α = 0.025. α is a coefficient representing the relationship between absorbance and sheet conductivity, and can be used as a coefficient for evaluating the film quality of the transparent conductive film. This α in the ITO film is about 0.4. When comparing the CNT transparent conductive film and the ITO film having the same sheet conductivity, the absorbance of the CNT transparent conductive film is about 16 times the absorbance of the ITO film, and the same absorbance. When comparing the CNT transparent conductive film with ITO and the ITO film, the sheet conductivity of the CNT transparent conductive film is about 1/16 of the sheet conductivity of the ITO film.

  As shown in FIG. 11, the CNT transparent conductivity having a transmittance at 550 nm of 84% to 90% and a surface resistance of about 1 kΩ / sq, and the transmittance at 550 nm of 90% to 98% and the surface resistance of about (1 to 1). 10) CNT transparent conductivity of kΩ / sq is realized.

  FIG. 12 is a photograph of a carbon nanotube thin film formed on a PET substrate.

  FIG. 12 shows a dispersion prepared by adding CNTs at a concentration of 0.2 mg / mL in a 1% aqueous solution of SDS. By the above-described method, a surface of a PET substrate (4 inch diameter, thickness 250 μm) was formed on 30 The CNT transparent conductive film formed by lamination | stacking of times is shown. The CNT transparent conductive film had a thickness of about 8 nm, a surface resistance of 890 Ω / □, and a transmittance of 91% for incident light having a wavelength of 550 nm.

  As described above, according to the present invention, a transparent conductive film made of a one-dimensional nanomaterial and excellent in transparency and transmittance can be manufactured, and can be applied to transparent electrodes and wiring of various electronic devices. Can do.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the above-mentioned embodiment, Various deformation | transformation based on the technical idea of this invention is possible. For example, the material and thickness of the substrate, the type of surfactant, the material, the type of primary nanomaterial, the concentration of the surfactant and primary nanomaterial in the dispersion solution, etc. are arbitrarily set appropriately as required. can do.

As described above, according to the present invention, there is provided a method for producing a transparent conductive film made of a one-dimensional nanomaterial and having good transparency and transmittance, which can be applied to transparent electrodes and wirings of various electronic devices. be able to.

It is a figure explaining the formation method of a carbon nanotube thin film in an embodiment of the invention. It is a figure explaining the electroconductivity of a carbon nanotube thin film, and the application to an electronic circuit same as the above. It is a figure explaining the touch panel which uses a transparent conductive film same as the above. It is a figure which shows the SEM image of a carbon nanotube thin film same as the above. It is a figure which shows the AFM image of a carbon nanotube thin film same as the above. It is a figure which shows the AFM image of the carbon nanotube thin film after water washing same as the above. It is a figure which shows the optical microscope image of a carbon nanotube thin film same as the above. It is a figure which shows the optical microscope image of the carbon nanotube thin film formed on the PET board | substrate same as the above. It is a figure which shows the absorption spectrum of a carbon nanotube thin film same as the above. It is a figure which shows the relationship between the light absorbency of a carbon nanotube thin film, and sheet electrical conductivity same as the above. It is a figure which shows the relationship between the transmittance | permeability of a carbon nanotube thin film, and surface resistance same as the above. It is a photograph figure of the carbon nanotube thin film formed on the PET board | substrate same as the above.

Explanation of symbols

1a, 1b ... transparent conductive film, 2a ... PET substrate, 2b ... glass substrate, 3 dot spacer,
4 ... Insulating layer, 5 ... Space, 10 ... Bubble, 12 ... Nozzle, 14, 46 ... Substrate, 16 ... Air,
20 ... CNT thin film, 22, 32 ... CNT, 30a, 30b ... electrode, 31 ... substrate,
33 ... Line resistance of CNT, 34 ... Resistance between CNT wall surfaces, 35 ... Resistance between tips of CNT,
41 ... Source electrode, 42 ... Drain electrode, 43 ... Source / drain channel,
44 ... insulator layer, 45 ... gate electrode

Claims (19)

A first step of preparing a dispersion in which a one-dimensional nanomaterial is dispersed;
A second step of attaching droplets of the dispersion to one end of the nozzle;
By injecting a gas from the other end of the nozzle, the droplet is expanded and the 1
A third step of forming a bubble made of a film containing a dimensional nanomaterial at the one end of the nozzle;
A fourth step of increasing a contact area between the substrate and the bubble film by bringing a part of the bubbles into contact with the surface of the substrate, allowing the gas to flow from the other end of the nozzle and expanding the bubbles;
A fifth step of rupturing the bubbles;
And a sixth step of forming the thin film by drying the film on the substrate.   The thin film manufacturing method according to claim 1, further comprising a seventh step of cutting the thin film together with the substrate in a shape that maintains one orientation direction of the one-dimensional nanomaterial.   The method for producing a thin film according to claim 1, wherein, in the first step, the one-dimensional nanomaterial is dispersed in an aqueous solution containing a surfactant.   The manufacturing method of the thin film of Claim 1 which has the process of washing the said film with water following the said 5th process.   The method for producing a thin film according to claim 1, wherein the sixth step is repeated from the first step.   The method for producing a thin film according to claim 1, wherein the one-dimensional nanomaterial is radially oriented substantially parallel to the surface of the substrate.   The method for producing a thin film according to claim 1, wherein the one-dimensional nanomaterial is conductive.   The method for producing a thin film according to claim 7, wherein the one-dimensional nanomaterial is a carbon nanotube.   The manufacturing method of the thin film of Claim 1 whose thickness of the said thin film is 100 nm or less.   The manufacturing method of the thin film of Claim 1 whose transmittance | permeability is 90% or more.   The method for producing a thin film according to claim 1, wherein the surface resistance is 500 Ω / sq or less.   The method for producing a thin film according to claim 1, wherein the substrate is transparent.   The method for producing a thin film according to claim 1, wherein the substrate is a transparent polymer substrate.   The thin film production according to claim 13, wherein the polymer substrate is any one of reethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), and derivatives thereof. Method. A first step of preparing a dispersion in which a one-dimensional nanomaterial is dispersed;
A second step of attaching droplets of the dispersion to one end of the nozzle;
By injecting a gas from the other end of the nozzle, the droplet is expanded and the 1
A third step of forming a bubble made of a film containing a dimensional nanomaterial at the one end of the nozzle;
A fourth step of increasing a contact area between the substrate and the bubble film by bringing a part of the bubbles into contact with the surface of the substrate, allowing the gas to flow from the other end of the nozzle and expanding the bubbles;
A fifth step of rupturing the bubbles;
And a sixth step of drying the film on the substrate to form a thin film.   The method for manufacturing an electronic device according to claim 15, wherein the thin film is formed by the manufacturing method according to claim 2.   The method of manufacturing an electronic device according to claim 15, wherein the thin film has light transmittance and conductivity and is used as a transparent electrode.   The method for manufacturing an electronic device according to claim 15, wherein the method is configured as any one of a liquid crystal device, an electroluminescence device, an electrochromic device, a field effect transistor, a touch panel, and a solar cell.   The method for manufacturing an electronic device according to claim 15, wherein the thin film is used as a conductive line.