JP2005231966A - Inorganic porous thin film where carbon nanotubes are formed in the pores, laminated body, and manufacturing method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an inorganic porous thin film where a large number of pores with a required shape are arranged in a single layer and carbon nanotubes are selectively grown in the pores, a laminated body made of the same, and a method for manufacturing the inorganic porous thin film. <P>SOLUTION: The inorganic porous thin film 10 has a large number of pores 5 having an opening 1 with a nearly circular shape and an inner peripheral face 3 with a nearly spherical shape and carbon nanotubes 6 are formed in the pores 5. The pores 5 are arranged in the single layer along the flat surface of the thin film 10. The average diameter d1 of the openings 1 is 30-3,000 nm and the average distance between the centers of the neighboring pores d2 is 100-230% of the average diameter d1 of the openings 1. The thickness of the film d3 is 30-100% of the average diameter d1 of the openings 1. The average diameter of the carbon nanotubes 6 is 0.4-50 nm and the average length is 10-1,000 nm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an inorganic porous thin film in which carbon nanotubes are selectively formed in pores, a laminate using the same, and a method for producing the inorganic porous thin film.

  Self-organization is one of the bottom-up pattern formation methods, and is a powerful method for realizing mass production using nanotechnology.

In recent years, research on a display field emission display (FED) has been promoted as an alternative to a cathode ray tube (CRT). As such research, research on cathode panels using carbon nanotubes (CNT) as an electron gun is known (for example, see Non-Patent Documents 1 and 2), and carbon nanotubes are selectively grown in a certain region. Research (for example, see Non-Patent Document 3) is known.
Saihachi Hachihachi, Itoh Toshiharu, “The Fundamentals of Carbon Nanotubes”, Corona, 1998, p. 185-192 Hirohiko Murakami, “Development of nano carbon materials for FED”, Metals, 2002, Vol. 72, No. 9 Yongyuan Yang, Shaoming Huang, Huizu He, Albert WH Mau, and Liming Dai .: “Patterned Growth of Well-Aligned Carbon Nanotubes: A Photolithographic Approach”; J. Am. Chem. Soc. 1999, 121; p.10832-10833

  However, when the insulating film of the cathode substrate by the etching described in the above publication is prepared, the number of steps is large, and the carbon nanotubes of the electron gun that are selectively grown in the pores of the cathode substrate have not been obtained.

  Accordingly, an object of the present invention is to provide an inorganic porous thin film in which carbon nanotubes are selectively grown in a large number of pores having a predetermined shape, a laminate using the same, and a method for producing the inorganic porous thin film. is there.

  The present inventors coated metal fine particles serving as a catalyst for forming carbon nanotubes on a substrate, containing inorganic ultrafine particles and organic fine particles having a predetermined particle diameter as solid components thereon, and having a total solid content concentration of By applying a sol-like coating liquid within a predetermined range and further using a CVD method, a large number of holes having a predetermined shape are arranged in one layer, and carbon nanotubes are selectively grown in the holes. The inventors have found that a porous thin film can be obtained, and have completed the present invention.

  That is, the inorganic porous thin film of the present invention is an inorganic porous thin film having a large number of holes having an approximately circular opening and a substantially spherical inner peripheral surface, and carbon nanotubes are formed in the holes. The holes are arranged in one layer in the plane direction of the thin film, the average diameter of the openings is 30 to 3000 nm, and the average distance between the centers of the adjacent openings is 100 of the average diameter of the openings. -230% in length, and the film thickness is 30-100% of the average diameter of the openings, the average diameter of carbon nanotubes is 0.4-50 nm, and the average length is 10-1000 nm It is characterized by being.

  An inorganic porous thin film in which carbon nanotubes are formed in such holes is particularly suitable as an electron gun for an FED or an electron microscope using carbon nanotubes because a large number of holes having a predetermined shape are arranged in one layer. Is preferred.

  The inorganic porous thin film preferably has an average depth of the holes of 50 to 100% of the film thickness. Furthermore, the average length of the carbon nanotubes is preferably 10 to 100% of the average depth of the holes.

  The laminate of the present invention comprises a substrate and an inorganic porous thin film in which carbon nanotubes are formed in the holes of the present invention formed on at least one surface of the substrate. It is.

The present invention also supplies a first sol-like coating liquid in which metal fine particles having an average particle diameter of 0.4 to 50 nm are dispersed in a first dispersion medium on a substrate, and the supplied first sol-like coating liquid is supplied. A first coating step of arranging the metal fine particles on the substrate by removing at least a part of the first dispersion medium from a working liquid;
A second sol coating liquid in which inorganic ultrafine particles having an average particle diameter of 3 to 50 nm and organic fine particles having an average particle diameter of 30 to 3000 nm are dispersed in a second dispersion medium (provided that the organic fine particles are inorganic ultrafine particles). The average particle diameter is larger than that of the fine particles.), The total solid content concentration is 0.1 to 20% by mass, and the content of the organic fine particles is 20 to 1000 parts by mass with respect to 100 parts by mass of the inorganic ultrafine particles. The sol-like coating liquid 2 is supplied onto the substrate, and the metal fine particles are arranged by removing at least a part of the second dispersion medium from the supplied second sol-like coating liquid. A second coating step for forming a gel-like thin film in which the organic fine particles are arranged in a single layer on the substrate and the inorganic ultrafine particles are arranged between the organic fine particles;
The obtained gel-like thin film is brought into contact with a thermal decomposition product of a gaseous carbon-containing compound at 600 to 1200 ° C., thereby removing the organic fine particles to obtain an inorganic porous thin film, and observing carbon nanotubes in the pores. A phase growth step;
The manufacturing method of the inorganic porous thin film characterized by including this is provided. By this production method, an inorganic porous thin film in which carbon nanotubes are formed in the pores of the present invention can be obtained.

  Further, in this manufacturing method, the fine metal particles are selected from the group consisting of transition metal elements, rare earth metal elements, oxides of transition metal elements, oxides of rare earth metal elements, and composite metal compounds composed of a plurality of metal elements. It is preferably composed of at least one.

  In this production method, it is preferable that the inorganic ultrafine particles are made of silica and / or the organic fine particles are made of a polymer.

  In this production method, the carbon-containing compound is preferably a hydrocarbon or an alcohol.

  According to the present invention, it is possible to obtain an inorganic porous thin film in which a large number of holes having a predetermined shape are arranged in one layer in a predetermined pattern and carbon nanotubes are formed in the holes, and a laminate using the same. It is possible to provide a method for producing the inorganic porous thin film. Such an inorganic porous thin film is particularly suitable as a photonic crystal, a low reflection treatment on the glass surface, an FED using a carbon nanotube, an electron gun for an electron microscope, or the like.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or equivalent elements will be denoted by the same reference numerals, and redundant description will be omitted. Moreover, the dimension in drawing does not necessarily correspond with an actual dimension.

(Inorganic porous thin film, laminate using the same)
FIG. 1 is a perspective view of a “laminated body including an inorganic porous thin film in which carbon nanotubes are formed in holes” according to the embodiment, and FIG. 2 is a cross-sectional view taken along line II-II in FIG.

  First, the inorganic porous thin film 10 will be described. The inorganic porous thin film 10 shown in FIGS. 1 and 2 is formed on a substrate 20. The inorganic porous thin film 10 is an inorganic porous thin film 10 having a large number of holes 5 in which the opening 1 has a substantially circular shape and the inner peripheral surface 3 has a substantially spherical shape, and the holes 5 are planes of the inorganic porous thin film 10. The average diameter d1 of the openings 1 is 30 to 3000 nm, and the average distance d2 between the centers of the adjacent openings 1 is 100 to 230% of the average diameter d1 of the openings 1. And the film thickness d3 is 30 to 100% of the average diameter d1 of the openings 1.

  Although the inorganic porous thin film 10 can be produced by a method for producing an inorganic porous thin film, which will be described later, inorganic ultrafine particles are used as the raw material. Such inorganic ultrafine particles include metals such as aluminum, titanium and nickel; inorganic oxides such as silica (silicon dioxide), alumina (aluminum oxide), titania (titanium oxide), niobium oxide and cerium oxide, or nitriding It is preferably at least one of inorganic ultrafine particles composed of inorganic nitrides such as silicon, aluminum nitride and titanium nitride. Among the fine particles made of such a material, inorganic ultra fine particles made of an inorganic oxide are preferable, and inorganic ultra fine particles made of silica are more preferable.

  The average particle size of the inorganic ultrafine particles is preferably 3 to 50 nm, more preferably 3 to 20 nm, still more preferably 3 to 15 nm, and particularly preferably 3 to 10 nm. If the average particle size of the inorganic ultrafine particles is less than 3 nm, it is difficult to produce the inorganic ultrafine particles, so that it is difficult to produce the inorganic porous thin film, and if it exceeds 50 nm, it is difficult to form the pores 5 having the above shape. This makes it difficult to produce an inorganic porous thin film.

  The average particle diameter of the inorganic ultrafine particles can be determined by a transmission electron microscope (TEM) method. In addition, the inorganic porous thin film 10 is preferably substantially composed of the above-described raw materials and inorganic materials that are constituents thereof, but may contain less than 10% organic material.

  As described above, the shape of the hole 5 in the inorganic porous thin film 10 is such that the opening 1 is substantially circular and the inner peripheral surface 3 is substantially spherical. In such a shape, substantially spherical organic fine particles are dispersed at a predetermined interval in a precursor of an inorganic porous thin film (gel thin film in the method for producing an inorganic porous thin film of the present invention) at a predetermined interval. The organic fine particles can be formed by removing by baking. In addition, the opening part 1 is a substantially circular edge part of the hole 5 in the inorganic porous thin film 10 surface, as shown in FIG.

  The average diameter d1 of the opening 1 is 30 to 3000 nm, preferably 40 to 1700 nm, and more preferably 100 to 1000 nm. The average diameter d1 basically corresponds to the average particle diameter of the organic fine particles serving as a template for the holes 5 and firing is performed in a state where the organic fine particles are arranged in a line. It is possible to obtain an inorganic porous thin film arranged in the form (FIG. 2).

  Moreover, as for the inorganic porous thin film 10, the average distance d2 between the centers of the adjacent openings 1 is 100 to 230% of the average diameter d1 of the openings 1, and is 100 to 180%. Is more preferable, and the length is further preferably 120 to 160%. When the average distance d2 is less than 100%, the adjacent portions of the hole and the adjacent hole are connected. On the other hand, if the average distance d2 is longer than 230% of the average diameter d1, the arrangement of the openings 1 becomes irregular.

  Here, the center of the opening 1 means the center when the outline of the opening 1 is a perfect circle. Further, when the contour of the opening 1 is a shape deformed from a perfect circle, the center of the opening 1 is the center of gravity of the shape (when assuming a plate-like body having the same contour as the opening 1 and a uniform density) The position corresponding to the center of gravity of the plate-like body.

  The inorganic porous thin film 10 has a thickness d3 of 30 to 100% of the average diameter d1 of the openings 1 and preferably 50 to 80% of the average diameter d1. If the film thickness d3 is less than 30% of the average diameter d1, the film does not serve as a hole, and if it is more than 100% of the average diameter d1, there is a possibility that a large crack will occur in the thin film. .

  The average pore depth d4 in the inorganic porous thin film 10 is preferably 50 to 100% of the film thickness d3, and more preferably 70 to 100% of the film thickness d3. If the average depth d4 of the holes is less than 50% of the film thickness d3, it becomes one of the factors that cause cracks in the thin film.

  The carbon nanotubes 6 are selectively present in the holes 5 and have an average diameter of 0.4 to 50 nm and an average length of 10 to 1000 nm. The average length is preferably 10 to 100% of the average depth d4 of the holes 5.

  Next, a laminated body is demonstrated. A laminated body 100 according to the embodiment shown in FIGS. 1 and 2 includes a substrate 20 and the inorganic porous thin film 10 formed on at least one surface of the substrate 20. .

  As the substrate 20 in the stacked body 100, a flat substrate made of glass, quartz, silicon, aluminum, or the like can be used. The shape of such a substrate is not particularly limited, but is a disk-shaped substrate having a diameter of 10-90 mm, a thickness of 0.2-3.0 mm, or a square substrate having a side of 50-300 mm, 0 A substrate thickness of 2 to 3.0 mm is preferred.

  The inorganic porous thin film 10 described above and the laminate 100 using the same are particularly suitable as an electron gun for an FED using a carbon nanotube, an electron microscope, or the like.

(Inorganic porous thin film manufacturing method)
Hereinafter, the manufacturing method of an inorganic porous thin film is demonstrated.
The inorganic porous thin film and laminate in which carbon nanotubes are formed in the above-described pores can be obtained by the following method for producing an inorganic porous thin film according to the embodiment. That is, a first sol-like coating liquid in which metal fine particles having an average particle size of 0.4 to 50 nm are dispersed in a first dispersion medium is supplied onto a substrate, and the supplied first sol-like coating liquid is used. By removing at least a part of the first dispersion medium, a first coating step for arranging the metal fine particles on the substrate, inorganic ultrafine particles having an average particle size of 3 to 50 nm, and an average particle size of 30 A second sol-like coating liquid in which organic fine particles of ˜3000 nm are dispersed in a second dispersion medium (provided that the organic fine particles have a larger average particle size than the inorganic ultrafine particles), and the total solid content. Supplying a second sol-like coating liquid having a concentration of 0.1 to 20% by mass and a content of the organic fine particles of 20 to 1000 parts by mass with respect to 100 parts by mass of the inorganic ultrafine particles on the substrate; The second dispersion from the supplied second sol coating liquid By removing at least a part of the second layer, a gel-like thin film in which the organic fine particles are arranged in a single layer and the inorganic ultrafine particles are arranged between the organic fine particles is formed on the substrate on which the metal fine particles are arranged. The above-mentioned coating process and the obtained gel-like thin film are brought into contact with a thermal decomposition product of a gaseous carbon-containing compound at 600 to 1200 ° C., thereby removing the organic fine particles to obtain an inorganic porous thin film, and pores And can be manufactured by a method including a step of vapor-phase growing carbon nanotubes therein.

  First, a first sol-like coating liquid (hereinafter referred to as coating liquid I) in which metal fine particles used in this production method are dispersed in a dispersion medium will be described.

  The metal fine particles serve as a catalyst for forming carbon nanotubes. As the metal fine particles, fine particles comprising at least one selected from the group consisting of transition metal elements, rare earth metal elements, oxides of transition metal elements, oxides of rare earth metal elements, and composite metal compounds composed of a plurality of metal elements It is preferable that As the transition metal element, iron, cobalt, nickel, platinum, gold, silver, copper, manganese, rhodium, and palladium are preferable, and iron, cobalt, and nickel are more preferable. As the rare earth element, yttrium, lutetium, and gadolinium are preferable.

  The average particle diameter of the metal fine particles is 0.4 to 50 nm, and more preferably 1 to 20 nm. When the average particle diameter is less than 0.4 nm, carbon nanotubes do not grow, and when the average particle diameter exceeds 50 nm, single-wall carbon nanotubes having excellent field emission characteristics are hardly formed.

  Regarding the kind of the first dispersion medium used in the coating liquid I, water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ethylene glycol, diethylene glycol and ethylene glycol monoethyl ether Ethylene glycols such as acetone; Ketones such as acetone and methyl ethyl ketone; Amides such as dimethylformamide; Aromatic hydrocarbons such as benzene, toluene, xylene; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, etc. The solution which mixed at least 1 or more types of these is mentioned. Among these, alcohols, ethylene glycols, ketones, amides, aromatic hydrocarbons or aliphatic hydrocarbons are preferable, and aromatic hydrocarbons and aliphatic hydrocarbons are most preferable. preferable.

  Further, the coating liquid I may contain a surfactant or the like in order to improve the dispersibility of the metal fine particles in addition to the above components.

  In the coating liquid I, the total solid content concentration is preferably 0.1 to 10% by mass, more preferably 0.2 to 5 parts by mass, and further preferably 0.5 to 3 parts by mass. preferable. When the total solid content concentration is less than 0.1% by mass, the formation of carbon nanotubes is difficult to start, and even if it exceeds 10% by mass, the effect of metal fine particles as a catalyst is hardly expected.

  Examples of the coating method of the coating liquid I include a spin coater, a capillary coater, a gravure coater, and a die coater. When the supply means is a spin coater, the maximum rotational speed at the time of supply (coating) is preferably 1000 to 8000 rpm, more preferably 1500 to 8000 rpm, and further preferably 2000 to 8000 rpm. . Moreover, when a supply means is a gravure coater or a die coater, it is preferable that the film formation rate at the time of supply (at the time of coating) is 1-1000 mm / s, and it is more preferable that it is 5-100 mm / s.

  The removal of the first dispersion medium from the coating liquid I can be carried out by a known drying method. When a spin coater is used as a supply means, the coating liquid is rotated for a while after coating. By continuing, the dispersion medium can be removed. Here, at least a part of the first dispersion medium may be removed, but it is preferable to remove all of the first dispersion medium.

  Next, a second sol coating liquid (hereinafter referred to as coating liquid II) in which inorganic ultrafine particles and organic fine particles used in this production method are dispersed in a dispersion medium will be described. The coating liquid II contains inorganic ultrafine particles and organic fine particles as a solid content, and the total solid content concentration in the coating liquid II is 0.1 to 20% by mass, more preferably 0.2 to 10%. It is mass%, More preferably, it is 0.5-10 mass%. If the total solid content concentration is less than 0.1% by mass, it is difficult to produce an inorganic porous thin film because the concentration is too low. If the total solid content concentration exceeds 20% by mass, organic fine particles are arranged in multiple layers. Production becomes difficult.

  As the inorganic ultrafine particles, those similar to the inorganic ultrafine particles described in the description of the inorganic porous thin film can be used.

  The organic fine particles are preferably composed of polymers such as polystyrene, styrene-butadiene copolymer, polyvinyltoluene, styrene-divinylbenzene copolymer, vinyltoluene-t-butylstyrene copolymer, polymethacrylate and polyacrylate. More preferred are those made of polystyrene, styrene-butadiene copolymer, or styrene-divinylbenzene copolymer.

  The average particle diameter of the organic fine particles is 30 to 3000 nm. The average particle diameter of the organic fine particles is preferably 40 to 1700 nm, and more preferably 100 to 1000 nm. When the average particle size is less than 30 nm, it is difficult to produce particles having a uniform particle size, and thus it is difficult to produce an inorganic porous thin film. On the other hand, when the thickness exceeds 3000 nm, it is difficult to produce particles having a uniform particle diameter, and thus it is difficult to produce an inorganic porous thin film. The average particle diameter of the organic fine particles can be determined by a transmission electron microscope (TEM) method.

  The coating liquid II contains 20 to 1000 parts by mass of the organic fine particles with respect to 100 parts by mass of the inorganic ultrafine particles. The content of the organic fine particles with respect to 100 parts by mass of the inorganic ultrafine particles is preferably 25 to 600 parts by mass, and more preferably 25 to 400 parts by mass. When the content of the organic fine particles with respect to 100 parts by mass of the inorganic ultrafine particles is less than 20 parts by mass, the organic fine particles are not arranged in a predetermined pattern, making it difficult to produce the inorganic porous thin film of the present invention. Since a sufficient amount of inorganic ultrafine particles do not exist between the organic fine particles, the inorganic porous thin film of the present invention becomes difficult.

  The second dispersion medium used in the coating liquid II includes alcohols such as methanol, ethanol, 1-propanol, 2-propanol and butanol; ethylene glycol such as ethylene glycol, diethylene glycol and ethylene glycol monoethyl ether. Ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide or an aqueous solution obtained by mixing at least one of them, and water. Among these, water, alcohol or a mixed solvent of water and alcohol is preferable, and water or a mixed solvent of water and alcohol is most preferable.

  In addition to the above components, the coating liquid II contains a solution stabilizer such as a surfactant, and alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane. Also good.

  Next, each process of the manufacturing method of an inorganic porous thin film is demonstrated, referring drawings. 3A to 3E are process diagrams of the method for manufacturing an inorganic porous thin film according to the embodiment. FIG. 3A is a cross-sectional view showing a state where the “coating liquid I” 46 in which the metal fine particles 42 are dispersed in the first dispersion medium 44 is supplied onto the substrate 20.

  As the substrate, a substrate described in the description of the stacked body, that is, a flat substrate made of glass, quartz, silicon, aluminum, or the like can be used.

  As a result of the removal of the first dispersion medium 44, a layer 40 in which metal fine particles 42 are arranged is formed on the substrate 20 as shown in FIG.

  FIG. 3C shows a state in which “Coating Liquid II” 28 in which the organic fine particles 22 and the inorganic ultrafine particles 24 are dispersed in the second dispersion medium 26 is supplied onto the substrate 20 on which the metal fine particles are arranged. It is sectional drawing. In FIG. 3C, the organic fine particles 22 present in the second dispersion medium 26 are arranged on a single layer on the substrate 20, and a plurality of inorganic ultrafine particles 24 are present between the organic fine particles 22.

  As a result of the removal of the second dispersion medium 26, as shown in FIG. 3D, the gel thin film 30 in which the organic fine particles 22 are arranged in one layer and the inorganic ultrafine particles 24 are arranged between the organic fine particles 22 is formed on the substrate 20. Formed on top.

  By bringing the gel-like thin film 30 formed in this way into contact with a thermal decomposition product of a gaseous carbon-containing compound at 600 to 1200 ° C., the organic fine particles 22 are thermally decomposed and removed, and between the organic fine particles 22 It is considered that a plurality of inorganic fine particles 24 present in the substrate are integrated by sintering or the like to form the inorganic porous thin film 10 and carbon nanotubes are selectively grown in the pores. In this case, it is presumed that the organic fine particles 22 function as a template for forming holes, and holes are formed corresponding to the arrangement state and particle size of the organic fine particles 22 in the gel thin film 30.

  FIG. 3 (e) is a cross-sectional view showing a laminate 100 including the inorganic porous thin film 10 in which carbon nanotubes are formed in the pores on the substrate 20. A laminated body 100 shown in FIG. 3 (e) is provided with an inorganic porous thin film 10 having a large number of holes 5 on a substrate 20, in which the opening 1 is substantially circular and the inner peripheral surface 3 is substantially spherical. is there.

Next, the process of growing the carbon nanotubes by heating the gel-like thin film will be described.
The temperature range for heating the gel-like thin film is preferably 600 to 1200 ° C, more preferably 700 to 1000 ° C. If a suitable example is shown for every board | substrate to be used, when using quartz as a board | substrate, 600-1200 degreeC (preferably 700-1000 degreeC, Furthermore, 750-950 degreeC), When using glass as a board | substrate, 600- 700 ° C., and 600 to 700 ° C. when silicon is used as the substrate. If the firing temperature is less than the lower limit, carbon nanotubes are not sufficiently generated. On the other hand, if the firing temperature exceeds the upper limit, the substrate tends to soften and it becomes difficult to form an inorganic porous thin film.

  Carbon-containing compounds brought into contact with the gel-like thin film include saturated aliphatic hydrocarbons such as methane, ethane, propane, and butane; unsaturated aliphatic hydrocarbons such as ethylene, acetylene, propylene, 1-butene, and 2-butene. An aromatic hydrocarbon such as benzene, toluene and xylene; and a mixture of one or more kinds of alcohols such as methanol, ethanol and propanol is desirable.

  The method for decomposing the gaseous carbon-containing compound is preferably an arc discharge method, a laser ablation method, a thermal CVD method or a plasma CVD method.

  The inorganic porous thin film manufacturing method can improve the lack of practicality of the conventional vertical deposition method (coating speed, productivity, etc.), which has a low coating speed, and can provide a large area in a large amount in a short time. It makes it possible to produce an inorganic porous thin film.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following Examples.

(Example 1)
First, a quartz substrate (made by Isetec Co., Ltd.) having a diameter of 15 mmΦ and a thickness of 1.1 mm was immersed in a chrome mixed acid solution to remove stains on the substrate surface. This substrate was washed with distilled water until the chromium mixed acid solution was completely removed, and dried at room temperature.

  Next, a coating liquid I (dispersion medium, hexane) containing 1% by mass of iron-platinum composite particles having a particle diameter of 3 nm with dodecanethiol coordinated to the surface as a solid content was prepared. A glass substrate that has been cleaned and dried is mounted on a spin coater (manufactured by Active, model number: ACT-300D), and an autopipette (manufactured by Eppendorf, model number: Eppendorf reference 4910, 10 to 100 μL) is placed on the glass substrate. After using the coating solution I for 100 μL, it was rotated at a rotational speed of 3000 rpm for 3 minutes. As a result, the coating liquid I was uniformly coated on the glass substrate and dried.

  Further, the coating liquid containing 0.25% by mass of inorganic ultrafine particles having a particle size of 5 nm and 0.5% by mass of organic fine particles having a particle size of 178 nm as a solid content and having a total solid concentration of 0.75% by mass. II was prepared using a sample preparation plastic container. In addition, silica particles (CATALOID manufactured by Catalytic Chemicals, model number: SI-550) were used as the inorganic ultrafine particles, and polystyrene latex particles (STADEX manufactured by JSR, model number: SC-017-S) were used as the organic fine particles. Moreover, this coating liquid II contained 200 mass parts of organic fine particles with respect to 100 mass parts of inorganic ultrafine particles.

  The glass substrate coated with the coating liquid I was mounted on the spin coater, and 100 μL of the coating liquid II was placed on the glass substrate using an autopipette, and then rotated at a rotational speed of 2000 rpm for 5 minutes. As a result, the coating liquid II could be uniformly applied on a glass substrate and dried, thereby obtaining a substrate on which a gel-like thin film was formed.

A substrate having the gel-like thin film is formed placed in a CVD apparatus, the pressure was reduced to 5.0 × 10 ^-1 Pa at the pump, nitrogen flowing rate 10 cm ³ / min (standard state), and up to 800 ° C. under a stream of nitrogen The temperature rose. Thereafter, the gas was switched to methane, and it was allowed to flow at 100 cm ³ / min (standard state) at 800 ° C. for 10 minutes. Thereafter, nitrogen was flowed again at a flow rate of 10 cm ³ / min (standard state), and the resultant was cooled to room temperature to obtain a substrate with an inorganic porous thin film in which carbon nanotubes were formed in the pores.

  In order to investigate the structure of this inorganic porous thin film, it was observed with a high resolution scanning electron microscope (manufactured by Hitachi, Ltd., model number: S-900), and an SEM photograph shown in FIG. 4 was obtained. As a result, it was confirmed that a large number of holes having a predetermined shape were arranged in a single layer in a predetermined pattern on the substrate, and an inorganic porous thin film in which carbon nanotubes were selectively formed in the holes was formed. The average diameter of the openings of the obtained inorganic porous thin film was 160 nm, the average distance between the centers of the openings was 200 nm, and the film thickness was 80 nm. The average length of the carbon nanotubes in the pores was 50 nm, and the average diameter was 12 nm.

It is a perspective view of the layered product concerning an embodiment. It is sectional drawing along the II-II line of the laminated body of FIG. It is process drawing of the manufacturing method of the inorganic porous thin film which concerns on embodiment, (a) is sectional drawing which shows the state with which the coating liquid I was supplied on the board | substrate, (b) is the coating supplied on the board | substrate. Sectional drawing which shows the state from which the dispersion medium was removed from the liquid I, (c) is sectional drawing which shows the state in which the coating liquid II was supplied on the board | substrate, (d) is the coating liquid II supplied on the board | substrate. Sectional drawing which shows the state from which the dispersion medium was removed from, (e) is sectional drawing which shows the laminated body finally obtained. 2 is a SEM photograph (magnification: 25000 times) showing a part of the inorganic porous thin film of Example 1.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Opening part, 3 ... Inner peripheral surface, 5 ... Hole, 6 ... Carbon nanotube, 10 ... Inorganic porous thin film, 20 ... Substrate, 22 ... Organic fine particle, 24 ... inorganic ultrafine particles, 26 ... second dispersion medium, 28 ... coating liquid II, 30 ... gel-like thin film, 40 ... metal fine particle layer, 42 ... metal fine particles, 44 ... first dispersion medium, 46 ... coating liquid I, 100 ... laminate, d1 ... average diameter of openings, d2 ... average distance between centers of openings, d3 ... Film thickness, d4 ... Average depth of holes.

Claims (9)

The inorganic porous thin film in which the opening has a substantially circular shape and the inner peripheral surface has a large number of holes having a substantially spherical shape, and carbon nanotubes are formed in the holes,
The holes are arranged in one layer in the plane direction of the thin film, the average diameter of the openings is 30 to 3000 nm, and the average distance between the centers of the adjacent openings is 100 to 230 of the average diameter of the openings. % And the film thickness is 30-100% of the average diameter of the openings,
An inorganic porous thin film, wherein the carbon nanotube has an average diameter of 0.4 to 50 nm and an average length of 10 to 1000 nm.   The inorganic porous thin film according to claim 1, wherein an average depth of the holes is 50 to 100% of the film thickness.   The inorganic porous thin film according to claim 1 or 2, wherein an average length of the carbon nanotubes is 10 to 100% of an average depth of the pores.   A laminate comprising: a substrate; and the inorganic porous thin film according to any one of claims 1 to 3 formed on at least one surface of the substrate. A first sol-like coating liquid in which metal fine particles having an average particle size of 0.4 to 50 nm are dispersed in a first dispersion medium is supplied onto the substrate, and the first sol-like coating liquid is supplied with the first sol-like coating liquid. A first coating step of arranging the metal fine particles on the substrate by removing at least a part of the one dispersion medium;
A second sol coating liquid in which inorganic ultrafine particles having an average particle diameter of 3 to 50 nm and organic fine particles having an average particle diameter of 30 to 3000 nm are dispersed in a second dispersion medium (provided that the organic fine particles are inorganic ultrafine particles). The average particle diameter is larger than that of the fine particles.), The total solid content concentration is 0.1 to 20% by mass, and the content of the organic fine particles is 20 to 1000 parts by mass with respect to 100 parts by mass of the inorganic ultrafine particles. The sol-like coating liquid 2 is supplied onto the substrate, and the metal fine particles are arranged by removing at least a part of the second dispersion medium from the supplied second sol-like coating liquid. A second coating step for forming a gel-like thin film in which the organic fine particles are arranged in a single layer on the substrate and the inorganic ultrafine particles are arranged between the organic fine particles;
The obtained gel-like thin film is brought into contact with a thermal decomposition product of a gaseous carbon-containing compound at 600 to 1200 ° C., thereby removing the organic fine particles to obtain an inorganic porous thin film, and observing carbon nanotubes in the pores. A phase growth step;
The manufacturing method of the inorganic porous thin film characterized by including.   The metal fine particles comprise at least one selected from the group consisting of transition metal elements, rare earth metal elements, oxides of transition metal elements, oxides of rare earth metal elements, and composite metal compounds composed of a plurality of metal elements. The method for producing an inorganic porous thin film according to claim 5, wherein:   The method for producing an inorganic porous thin film according to claim 5 or 6, wherein the inorganic ultrafine particles are made of silica.   The method for producing an inorganic porous thin film according to any one of claims 5 to 7, wherein the organic fine particles are made of a polymer.   The method for producing an inorganic porous thin film according to any one of claims 5 to 8, wherein the carbon-containing compound is a hydrocarbon or an alcohol.

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