JP5396063B2 - Functional metal composite substrate and manufacturing method thereof - Google Patents

Functional metal composite substrate and manufacturing method thereof Download PDF

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JP5396063B2
JP5396063B2 JP2008276146A JP2008276146A JP5396063B2 JP 5396063 B2 JP5396063 B2 JP 5396063B2 JP 2008276146 A JP2008276146 A JP 2008276146A JP 2008276146 A JP2008276146 A JP 2008276146A JP 5396063 B2 JP5396063 B2 JP 5396063B2
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metal composite
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composite substrate
composite material
thin film
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JP2010099817A (en
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尚志 中西
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独立行政法人物質・材料研究機構
独立行政法人科学技術振興機構
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Description

  The present invention relates to a functional metal composite substrate and a manufacturing method thereof. More specifically, the present invention relates to a functional metal composite substrate that can be controlled from super / high hydrophilicity to super / high water repellency and a method for producing the same.

A technique for forming a self-assembled monolayer (SAM film) in order to control the characteristics of the metal surface is known (see, for example, Non-Patent Document 1). According to Non-Patent Document 1, a long chain alkanethiol (HS (CH 2 ) n X) (n is a natural number and X is a terminal group) is adsorbed from a solution onto a flat gold substrate. A film is formed. For example, when n is 1 or more and X is a carboxyl group, the surface of the gold substrate can be made super hydrophilic. Moreover, when n is 5 or more and X is a methyl group, the surface of the gold substrate can be made water-repellent.

However, according to Non-Patent Document 1, the surface of the gold substrate has not been controlled from super hydrophilicity to super water repellency. Moreover, it is desirable if the functionality can be expressed not only on the flat metal substrate but also on the surface of the metal composite material having various surface morphologies.
Bain et al. Am. Chem. Soc. 1989, 111, 321-335

  In view of the above, an object of the present invention is to provide a functional metal composite substrate in which functionality is expressed on the surface of the metal composite material and a method for manufacturing the same.

  Invention 1 is a functional metal composite substrate comprising a metal composite material and a functional thin film provided on the surface of the metal composite material, wherein the metal composite material is a supramolecular structure having a fractal surface structure. The surface of the shape is flake-shaped, and the functional thin film is either a self-assembled monolayer (SAM film) or a polymer thin film. To do.

  Invention 2 is the functional metal composite substrate according to Invention 1, wherein the functional thin film exhibits a surface free energy lower than a surface free energy of the metal composite material, and the functional metal composite substrate has water repellency. It is characterized by that.

Invention 3 is the functional metal composite substrate according to Invention 2, wherein the SAM film is alkanethiol (CH 3 (CH 2 ) n1-1 SH (n1 ≧ 2)) or fluorine-containing fluorocarbon thiol, The molecular thin film is characterized by being polypropylene.

  The invention 4 is the functional metal composite substrate according to the invention 3, wherein the n1 satisfies n1 ≧ 8.

  Invention 5 is the functional metal composite substrate according to Invention 4, wherein the thickness of the metal composite material is 40 nm or more.

  Invention 6 is the functional metal composite substrate according to invention 1, wherein the functional thin film exhibits a surface free energy higher than the surface free energy of the metal composite material, and the functional metal composite substrate has hydrophilicity. It is characterized by that.

Invention 7 is the functional metal composite substrate according to Invention 6, wherein the SAM film comprises aminoalkanethiol (NH 2 (CH 2 ) n2 SH: n2 ≧ 1), carboxyalkanethiol (COOH (CH 2 ) n3 SH : N3 ≧ 1) and hydroxyalkanethiol (HO (CH 2 ) n4 SH: n4 ≧ 1).

  Invention 8 is the functional metal composite substrate according to Invention 7, wherein the thickness of the metal composite material is 50 nm or more.

Invention 9 is the functional metal composite substrate according to Invention 1, wherein the supramolecular structure has a bilayer structure as a base nano-structure, and the fullerene structure in which fullerene derivatives are organized is organized in a layered manner. The fullerene derivative is represented by the formula (1), the fullerene moiety A represented by the formula (2), the benzene ring bonded to the fullerene moiety, and the 3, 4, and 5 positions of the benzene ring, respectively. First to third substituents R 1 , R 2 and R 3 bonded to

Here, in the formula (1), each of the first and second substituents R 1 and R 2 is an alkyl chain containing at least 20 carbon atoms, and the third substituent R 3 is , A hydrogen atom, or an alkyl chain containing at least 20 carbon atoms, in the formula (2), (Fu) represents a fullerene, X represents a hydrogen atom or a methyl group, The benzene ring is bonded to the nitrogen-containing 5-membered ring of the fullerene site A.

  Invention 10 is a method for producing the functional metal composite substrate according to any one of Inventions 1 to 9, and has a shape of a removal trace-like hole of a supramolecular structure having a fractal surface structure, It comprises a forming step of forming a functional thin film which is either a self-assembled monolayer (SAM film) or a polymer thin film on a metal composite material having a flaky surface.

  Invention 11 is a method according to Invention 10, wherein a metal material is applied on a supramolecular structure having a fractal surface structure prior to the forming step, and the composite material obtained by the application step is provided. A dipping step of dipping the supramolecular organization in a good solvent.

  The functional metal composite substrate according to the present invention can express various functions of the functional thin film in addition to the characteristics of the metal composite material by the functional thin film provided on the surface of the metal composite material. For example, when a functional thin film having various surface free energies is used, a functional metal composite substrate whose surface is controlled from super / high hydrophilicity to super / high water repellency is obtained. Such a functional metal composite substrate capable of exhibiting super water repellency can be used for MEMS / NEMS, catalyst materials, and the like utilizing the metal characteristics of the metal composite material and the porosity based on the flake shape. In addition, the functional metal composite substrate capable of expressing hydrophilicity can be used for an antifouling metal member, an antifogging treatment member, and an antifouling member that are lightened by porosity and have durability.

  The method for producing a functional metal composite substrate according to the present invention only requires forming a functional thin film on the metal composite material. This is advantageous because an existing method for forming a functional thin film can be employed.

  The inventor of the present application has succeeded in creating a porous metal composite material in recent years (Japanese Patent Application No. 2008-199217). The inventor of the present application obtained a porous metal composite material in which the structure of the supramolecular structure was transferred by using the supramolecular structure composed of a specific fullerene derivative as a template, and worked on various applications using this. It is out. The present invention is a result of intensive research aimed at a metal composite material developed by the inventor of the present application in order to develop functionality on the surface of the metal composite material.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the same number is attached | subjected to the same element and the description is abbreviate | omitted. Prior to the embodiment, a metal composite material targeted by the present application will be described in detail.

  FIG. 1 is a schematic view of a metal composite material used in the present invention.

  In FIG. 1, the metal composite material 100 located on the base material 110 is shown. The metal composite material 100 used in the present invention is obtained by structurally transferring the shape of the supramolecular structure 120 to the metal material 130 using the supramolecular structure 120 as a template. Specifically, the metal composite material 100 has a removal trace-like pore shape 140 generated by removing the supramolecular texture 120, thereby being porous. The supramolecular structure 120 has a fractal surface structure (more specifically, as will be described later, the surface of the fullerene structure 160 forming the fractal surface structure of the supramolecular structure 120 has a flaky shape. 150), when the supramolecular organization 120 is removed, the surface of the shape 140 of the removal trace-like hole becomes a flake shape 150 based on the fractal surface structure. Thereby, the specific surface area of the metal composite material 100 becomes large. The left diagram in FIG. 1 shows a state in which the metal material 130 is applied to the monolayer supramolecular organization 120 (also referred to as a composite material in this specification), and the right diagram in FIG. 1 shows the supramolecular organization. The single layer metal composite 100 after the body 120 has been removed is shown.

The supramolecular structure 120 functioning as a template is a fullerene structure 160 in which fullerene derivatives are organized, which has a bilayer structure as a base nano-structure, and is organized in layers. Specifically, the fullerene derivative is represented by the formula (1), the fullerene moiety A represented by the formula (2), and the first to third substituents R 1 , R 2 and R bonded to the fullerene moiety A. 3 is included.

Here, in the formula (1), each of the first and second substituents R 1 and R 2 is an alkyl chain containing at least 20 carbon atoms, and the third substituent R 3 is a hydrogen atom Or an alkyl chain containing at least 20 carbon atoms. If the number of carbon atoms is 20 or more, the resulting supramolecular organization always has a fractal surface structure, so that a porous metal composite material can be obtained. In Formula (2), (Fu) represents a fullerene, X represents a hydrogen atom or a methyl group, and a benzene ring is bonded to the nitrogen-containing five-membered ring of the fullerene moiety A.

Fullerene (Fu) is selected from the group consisting of C 60 , C 70 , C 76 and C 84 . These fullerenes are produced industrially and are available. Preferably, the fullerene is C 60. This, C 60 has a very high Ih symmetry are the most stable and inexpensive, with handling thereof is easy, because chemical modification is easy.

Exemplary alkyl chains of the first to third substituents R 1 , R 2, and R 3 (provided that the third substituent R 3 is not a hydrogen atom) are alkyl (C n H 2n + 1 ), Selected from the group consisting of alkoxyl (OC n H 2n + 1 ) and thioalkyl (SC n H 2n + 1 ). Here, as described above, n ≧ 20 is satisfied.

The bilayer structure formed by the fullerene derivative represented by the formula (1) is assembled to each other by the π-π interaction of the fullerene site A, and the first to third substituents R 1 , R 2 and It is a structure arranged so as to gather together by van der Waals forces of R 3 . A fullerene structure 160 in which fullerene derivatives arranged in a bilayer structure are organized is a structure in which the above-described bilayer structure is randomly organized, and has a flower-like shape having a fractal structure on the surface. The surface of the fullerene structure 160 has a flake shape 150. The supramolecular structure 120 is a fullerene structure 160 organized in a layered manner (the inventor has filed a patent application for details of the structure and characteristics of the supramolecular structure 120 (special Application 2007-148818)).

  The metal material 130 constituting the metal composite material 100 (located in the surface and inside of the supramolecular structure 120 in FIG. 1) is arbitrary as long as it is a metal-based material, but it has semiconductor characteristics, magnetism, and ferroelectricity. From the viewpoint of utilizing characteristics such as a photocatalyst, a metal or a metal oxide is preferable.

More specifically, metals are Ni, Cu and Co that can be used as magnetic materials and magnetic recording media, compound semiconductors such as Al, Si and AlN, and GaN that can be used as semiconductor materials, high reflectivity, and high corrosivity. In addition, AgPd and AgMg having high thermal conductivity, Au having excellent conductivity and workability, and frequently used in industrial applications, and Ti exhibiting high corrosion resistance are included. Among these, Pt, Au, Ni and Ti are preferable because they can be easily manufactured. Metal oxides include TiO 2 that can be used as a photocatalyst, SiO 2 , Al 2 O 3 and MgO that can be used as an insulating coating agent, In 2 O 3 that can be used as a transparent conductive film, ITO, and IZO (InZO). -ZnO) and AZO (Al 2 O 3 -ZnO), and Fe 2 O 3 and Cr 2 O 3 which are substrates for abrasion and polishing abrasives. These metal materials are merely examples, and the metal material 130 of the present invention can be any material that can exhibit metal-based characteristics.

  As shown in FIG. 1, it is preferable to dispose the metal composite material 100 on the substrate 110 because the handling becomes simple. In addition, although the base material 110 is a Si substrate, a quartz substrate, a plastic substrate, mica, a metal etc., for example, it is not limited to these. Moreover, the shape of the base material 110 does not necessarily need to be a flat plate, and is arbitrary, and may be a spherical surface as long as it has a smooth surface to which the supramolecular organization 120 described later is provided.

  Next, an exemplary manufacturing process of the above-described metal composite material 100 will be described. Each step will be described.

  Step S210: The metal material 130 is applied on the supramolecular organization 120. The metal material 130 and the supramolecular organization 120 are as described with reference to FIG. The application of the metal material 130 is performed by a method selected from the group consisting of a physical vapor deposition method, a chemical vapor deposition method, and a liquid phase method. Examples of the physical vapor deposition method include resistance heating, vapor deposition, sputtering, ion plating, MBE, and PLD. Specifically, chemical vapor deposition is CVD, MOCVD, or the like. Examples of the liquid phase method include electrolytic plating, electroless plating, and sol-gel method. Among these, sputtering in the physical vapor deposition method is preferable because the metal material 130 can be applied to the entire supramolecular structure 120 (up to the surface, details, and back side). In this way, a composite material in which the metal material 130 is applied to the supramolecular organization 120 is obtained (the left diagram in FIG. 1).

  Step S220: The composite material obtained in Step S210 is immersed in the good solvent of the supramolecular organization 120. Thereby, the supramolecular organization 120 is removed, only the metal material 130 remains, and the metal composite material 100 is obtained (the right diagram in FIG. 1). The good solvent for the supramolecular organization 120 is selected from the group consisting of chloroform, methylene chloride, toluene and benzene. These are all good solvents for the supramolecular organization 120 and are commercially available. Immersion is performed at room temperature (range of 5 ° C. to 30 ° C.) for at least 30 seconds. If it is shorter than 30 seconds, the supramolecular organization 120 may remain. Subsequent to step S220, the substrate may be washed with ultrapure water and dried.

  As described with reference to FIG. 1, it is preferable that the supramolecular organization 120 is disposed on the substrate 110 because the handling is simple. Next, a process of manufacturing the supramolecular organization 120 and placing it on the substrate 110 will be described.

  Step S310: A fullerene derivative and 1,4-dioxane are mixed. Since the fullerene derivative is the same as the above-mentioned fullerene derivative, it will not be redundantly described. Moreover, the above-mentioned fullerene derivative is produced by, for example, a production method described in Japanese Patent Application Laid-Open No. 2007-137809 by the present inventor. 1,4-Dioxane is a poor solvent at room temperature for fullerene derivatives.

The structure of the supramolecular organization can be controlled by changing the concentration of the fullerene derivative. Specifically, when the concentration of the fullerene derivative is increased (for example, 3 mM), the fullerene structure described below becomes a micro-sized disk, and when the concentration of the fullerene derivative is decreased (for example, 1 mM), the fullerene structure is micrometer. Becomes spherical in size. As described above, the structure of the fullerene structure can be controlled only by adjusting the concentration of the fullerene derivative, and the structure of the supramolecular organization as a template can be controlled. Furthermore, the structure of the supramolecular organization is controlled not only by adjusting the concentration of the fullerene derivative, but also by adjusting the number and / or length of the first to third substituents R 1 , R 2 and R 3 of the fullerene derivative. It can also be achieved by adjusting. In any case, the surface of the fullerene structure has a flake shape, and the supramolecular structure may have a fractal surface structure.

  Step S320: The mixture obtained in Step S310 is heated. By heating, the fullerene derivative can be uniformly dissolved in 1,4-dioxane. In order to make it melt | dissolve uniformly, a heating is performed in the temperature range of 60 to 70 degreeC for 0.5 to 2 hours. Since heating can be performed under mild conditions and in a short time, an expensive apparatus is not required, which is industrially preferable.

  Step S330: Aging the mixture dissolved after heating. As a result, a flower-like fullerene structure 160 is obtained in a self-organized manner. In order to sufficiently self-assemble, aging is performed at room temperature (temperature range of 15 ° C. to 30 ° C.) for 12 hours to 24 hours. In addition, the self-assembled flower-like fullerene structure 160 can be visually observed as a black-brown precipitate (precipitate). Since the yield at this time is 100%, the yield is good and mass production is possible.

  Step S340: Applying a solution containing a precipitate to the substrate 110. As a result, the supramolecular structure 120 in which the fullerene structure 160 is organized in layers on the substrate 110 is obtained. The application to the substrate 110 can employ any method such as a dropping method, a dipping method, a spin coating method, or a water surface spreading film method. The water surface spreading film method is a method in which the solution is spread on the water surface and the supramolecular structure 120 formed at the interface between air and water is applied to the substrate 110 by the pulling method. Such a water surface spreading film method is preferable because a high-quality supramolecular organization 120 is formed in a self-organized manner at the interface between air and water due to the super-water-repellent property of the fractal surface structure that it has. Moreover, there is no restriction | limiting in the magnitude | size of the supramolecular structure | tissue 120 formed, and it enables a large area. The base material 110 is as described with reference to FIG. As described above, through steps S <b> 310 to S <b> 340, the supramolecular organization 120 is manufactured and applied to the substrate 110.

  The inventor of the present application has succeeded in developing functionality on the surface of the metal composite material 100 thus obtained, more specifically, wettability controlled from super / high hydrophilicity to super / high water repellency. .

  FIG. 2 is a schematic view of a functional metal composite substrate according to the present invention.

  In FIG. 2, the functional metal composite substrate 200 located on the base material 110 is shown. The functional composite substrate 200 according to the present invention includes a metal composite material 100 and a functional thin film 210 provided on the surface of the metal composite material 100. The metal composite material 100 is as described above with reference to FIG. The functional thin film 210 is located on the surface of the metal composite material 100 and also in a space in the flake shape 150 of the metal composite material 100. The functional thin film 210 is either a self-assembled monomolecular film (SAM film) or a polymer thin film. In addition, the functional metal composite substrate 200 of this invention may have the base material 110 from the simplicity of handling.

  FIG. 3 is a schematic view showing details of the functional metal composite substrate according to the present invention.

  As shown in FIG. 3A, when a SAM film is selected as the functional thin film 210, the single molecules 310 constituting the SAM film are self-organized in the surface of the metal composite material 100 and in the flakes 150. Arrange in space. More specifically, the sulfur-based molecular functional group (for example, thiol group) of the single molecule 310 and the metal atom of the metal composite material 100 are bonded and regularly arranged in a certain direction, so that the thickness is constant. It is a thin film that is homogeneous and of good quality throughout. Further, since the bonding is stable, the functional thin film 210 does not peel off.

  As shown in FIG. 3B, when a polymer thin film is selected as the functional thin film 210, the polymer 320 constituting the polymer thin film is randomly distributed on the surface of the metal composite material 100 and the space in the flakes 150. Array. Since the polymer 320 is physically positioned on the metal composite material 100 as will be described later, it is difficult to obtain a high-quality thin film as compared with the SAM film. It is advantageous because it can be provided at a low cost, has many types, and has excellent environmental resistance.

  As described above with reference to FIG. 2, by providing the functional thin film 210 on the surface of the metal composite material 100, the functional metal composite substrate 200 exhibits the function of the functional thin film 210. obtain. Furthermore, as schematically shown with reference to FIG. 3, the functional thin film 210 is provided on the metal composite material 100 without filling the flakes 150 of the metal composite material 100, Therefore, in addition to the function of the functional thin film 210, the function of the metal composite material 100 (characteristics derived from metal and characteristics derived from porosity) can be exhibited.

Next, the function exhibited by the functional thin film 210, particularly the wettability will be described in more detail.
(1) Control of water repellency When the functional metal composite substrate 200 according to the present invention has the functional thin film 210 having a surface free energy lower than the surface free energy of the metal composite material 100, the functional metal composite substrate 200 is water repellant. Have The surface free energy of the metal composite material 100 can be easily calculated by contact angle measurement or surface tension measurement using a liquid having a known surface free energy. By appropriately selecting such a functional thin film 210, the wettability of the surface of the functional metal composite substrate 200 can be controlled to water repellency, high water repellency, or even super water repellency. In the present specification, a water contact angle of 90 ° or more is defined as water repellency, 110 ° or more and less than 150 ° is defined as having high water repellency, and 150 ° or greater is defined as having super water repellency.

When a SAM film is employed as the functional thin film 210 that exhibits water repellency, the SAM film is alkanethiol or fluorine-containing fluorocarbon thiol. Alkanethiol is represented by CH 3 (CH 2 ) n1-1 SH, and n1 may be 2 or more. The fluorine-containing fluorocarbon thiol is an arbitrary single molecule in which a fluorine chain is provided at one end of a single molecule and a thiol group is provided at the other end of the single molecule.

  Among them, the SAM film exhibiting high water repellency has n1 of 4 or more and 7 or less in the alkanethiol. Furthermore, it is preferable that the film thickness of the metal composite material 100 is 10 nm or more and less than 40 nm. Thereby, high water repellency can be surely expressed. In this specification, the film thickness of the metal composite material 100 intends the film thickness of the metal material applied in step S210 described above.

Furthermore, the SAM film exhibiting super water repellency has n1 of 8 or more in the alkanethiol. Although the upper limit of n1 is not particularly defined, n1 is preferably 18 or less in order to obtain a good quality SAM film. In addition, the metal composite material 100 preferably has a thickness of 40 nm or more. The upper limit of the film thickness is not particularly defined, but may be set as appropriate according to the application. Examples of the fluorine-containing fluorocarbon thiol that exhibits super water repellency include CF 3 SH (1H, 1H, 2H, 2H-perfluorodecanethiol: CF 3 (CF 2 ) 6 CF 2 CH 2 CH 2 SH). It is preferable from the viewpoint of environmental pollution that high water repellency and super water repellency can be expressed and can be controlled by employing an alkanethiol containing no fluorine.

  As described above, the functional metal composite substrate 200 according to the present invention selects the alkanethiol among the SAM films as the functional thin film 210, and appropriately changes the alkyl chain length and the film thickness of the metal composite material 100, thereby repelling. It can be controlled from aqueous to high water repellency and even super water repellency.

  On the other hand, when a polymer thin film is employed as the functional thin film 210 that exhibits water repellency, a hydrophobic polymer is employed as the polymer thin film. Specific examples of the hydrophobic polymer include polypropylene, polystyrene, polyethylene, polyisopropylene, polybutadiene, polydiethylsiloxane, a fluorine-containing polymer, and a copolymer thereof. Among these, polypropylene can exhibit high water repellency in the functional metal composite substrate 200. It is effective from the viewpoint of environmental pollution that high water repellency can be expressed by employing a polymer thin film that does not contain fluorine.

  In addition, the fluoropolymer can contribute to the development of super water repellency. When a fluorine-containing primer is applied to a smooth substrate surface, although it exhibits high water repellency, it is known that it is difficult to develop super water repellency (see, for example, Ji-Qing Huang et al., J. Biol. Fluorine Chem., 128 (2007), 1469-1477 and Masaya Hikita et al., Langmuir, 2004, 20, 5304-5310). However, as in the present invention, on the metal composite material 100 having the surface of the flaky shape 150 and being porous, the contact area between the substrate and water is extremely limited due to the presence of air in the pores. It is considered that the surface free energy is reduced and the super water repellency can be effectively expressed. Such fluoropolymers include tetrafluoroethylene, chlorotrifluoroethylene, polyfluoroalkyl perfluoroalkyl, and the like.

The functional metal composite substrate 200 controlled from high water repellency to super water repellency according to the present invention has a unique geometric structure based on the flake shape 150 of the metal composite material 100, and the antirust effect of the surface structure thereof. Have Further, if the functional metal composite substrate 200 according to the present invention is used as an electronic material utilizing the metal-based characteristics (conductivity, semiconductivity, magnetism) of the metal composite material 100, an electronic material having high / super water repellency. It becomes. Such an electronic material is suitable for MEMS / NEMS where non-wetting is required. Further, when the metal composite material 100 is platinum or palladium, it is effective as a catalyst material having high / super water repellency utilizing the porosity based on the flake shape 150 of the metal composite material 100.
(2) Control of hydrophilicity When the functional metal composite substrate 200 according to the present invention has the functional thin film 210 having a surface free energy higher than the surface free energy of the metal composite material 100, the functional metal composite substrate 200 is hydrophilic. Have By appropriately selecting such a functional thin film 210, the wettability of the surface of the functional metal composite substrate 200 can be controlled to be hydrophilic, highly hydrophilic, or even superhydrophilic. In the present specification, a contact angle with water of less than 90 ° is defined as hydrophilic, 15 ° to 40 ° or less is defined as highly hydrophilic, and 15 ° or less is defined as being superhydrophilic.

When a SAM film is employed as the functional thin film 210 that exhibits hydrophilicity, the SAM film is composed of aminoalkanethiol (NH 2 (CH 2 ) n2 SH: n2 ≧ 1), carboxyalkanethiol (COOH (CH 2 ) n3 SH : N3 ≧ 1) and hydroxyalkanethiol (HO (CH 2 ) n4 SH: n4 ≧ 1). All of these SAM films have been found to have a surface energy higher than that of the metal composite material 100. Although the upper limit of n2, n3 and n4 is not particularly defined, n2, n3 and n4 are preferably 8 or more and 18 or less from the viewpoint of ease of production of the SAM film. This is because the hydrophobic interaction (van der Waals interaction) between alkyl chains is increased, and a good quality SAM film is easily obtained.

  When expressing high hydrophilicity, among the SAM films, carboxyalkanethiol and hydroxyalkanethiol are preferable. Furthermore, if the film thickness of the metal composite material 100 is set to 20 nm or more and less than 50 nm, the highly hydrophilic metal composite substrate 200 can be obtained with certainty. Carboxyalkanethiol is preferable among the SAM films when developing super hydrophilicity. Furthermore, if the film thickness of the metal composite material 100 is set to 50 nm or more, the super-hydrophilic metal composite substrate 200 can be obtained reliably. The upper limit of the film thickness is not particularly defined, but may be set as appropriate according to the application.

Furthermore, superhydrophilicity may also be achieved by controlling the pH of the carboxyalkanethiol and aminoalkanethiol. By controlling these pH, these ends respectively -COO - and -NH 3 +, and the carry a charge. As a result, superhydrophilicity can be realized by water molecules that are polar molecules and electrostatic interaction between them.

  On the other hand, when a polymer thin film is employed as the functional thin film 210 that exhibits hydrophilicity, a hydrophilic polymer may be employed for the polymer thin film. However, hydrophilic polymers can dissolve in water and peel off from the surface, making them unsuitable for applications that require resistance, but for short-term or experimental applications, This is advantageous because it is simple and inexpensive.

  As described above, the functional metal composite substrate 200 according to the present invention can be changed from hydrophilic to highly hydrophilic by appropriately changing the type of the SAM film / polymer thin film and the film thickness of the metal composite material 100 as the functional thin film 210. Furthermore, super hydrophilicity can be controlled. The functional metal composite substrate 200 controlled from high hydrophilicity to superhydrophilicity according to the present invention is reduced in weight by the porosity based on the flake shape 150 of the metal composite material 100, and has a durable antifouling metal. It is suitable as a member or an antifogging treatment member. Moreover, since it has high / super hydrophilicity, it can be expected as a dirt cleaning member.

  Next, a method for manufacturing the functional metal composite substrate 200 according to the present invention will be described.

  FIG. 4 is a flowchart illustrating the production of the functional metal composite substrate 200 according to the present invention.

  The manufacturing method of the functional metal composite substrate 200 according to the present invention includes a step (S410) of forming the functional thin film 210 on the metal composite material 100 obtained through the above-described step S210.

  When the SAM film described above with reference to FIGS. 2 and 3 is employed as the functional thin film 210, the metal composite material 100 is immersed in a solution containing a single molecule constituting the SAM film for at least 24 hours. Good. As a result, the single molecule is self-assembled so that the metal atoms of the metal composite material 100 and the thiol group of the single molecule are bonded to form a SAM film.

  On the other hand, when the polymer thin film described above with reference to FIG. 2 and FIG. 3 is employed as the functional thin film 210, a solution containing a polymer adjusted to a concentration that does not inhibit the surface morphology of the metal composite material 100 is spinned. What is necessary is just to physically provide on the metal composite material 100 by the coating method, the dripping method, the spray method, or the dip method. Among them, the spin coating method is preferable for obtaining a higher-quality polymer thin film.

  In addition to physically applying the polymer to the metal composite material 100, it is also possible to fix the polymer onto the substrate via a thiol or silane coupling group. As a result, the polymer is chemically bonded to the thiol or silane coupling group bonded to the metal composite material 100, and therefore the strength of the bond between the polymer thin film and the metal composite material 100 compared to physical application such as spin coating. Can be improved. Further, when there is a radical source on the metal composite material 100, the polymer may be subjected to radical polymerization from the surface of the metal composite material 100. Again, this is advantageous because the strength of the polymer thin film can be improved.

  In the above, specific SAM films and polymer thin films are developed as functional thin films that develop from water repellency to high / super water repellency in functional metal composite substrates. However, the present invention is not limited to this.

  Various functions can be expressed by light or heat by using a SAM film or polymer thin film that is responsive to light or heat as a functional thin film. For example, when azobenzenethiol having an azobenzene group is used as a photoresponsive SAM film, wettability can be controlled using photoisomerization with an azobenzene group. In this case, by irradiating the functional metal composite substrate with light, both the functions of high / super water repellency and high / super hydrophilic property can be controlled in one functional metal composite substrate.

  If PEG thiol with polyethylene glycol (PEG) is used as a thermoresponsive SAM film, depending on the temperature, both high / superhydrophobic and high / superhydrophilic properties can be achieved in one functional metal composite substrate. Can control the function.

  In addition, if a polymer having N-isopropylacrylamide (NIPAM) or polyethylene glycol (PEG) is used as the thermoresponsive polymer thin film, one functional metal composite substrate depends on the temperature as in the oligomer thiol. , Both high / superhydrophobic and high / superhydrophilic functions can be controlled.

  Furthermore, the metal composite material of the functional metal composite substrate has a micro-sized porous structure resulting from flakes. A porous structure having such a size is suitable for pores that take in biomolecules such as DNA, proteins or viruses. Therefore, the above-described biomolecules may be fixed in the flaky pores in the metal composite material of the functional metal composite substrate with controlled wettability. Such immobilization of biomolecules is facilitated by the functional thin film having a functional group. Thereby, the biochemical function or the sensor function can be expressed in the functional metal composite substrate together with the control of the wettability, and can be used for the biocompatible substrate.

  As a matter of course, depending on the functional thin film to be selected, it is possible to develop functions other than the control of wettability. For example, in the functional metal composite substrate of the present invention, the above-described biochemical function or sensor function is provided. It may be used alone.

  The present invention will now be described in detail using specific examples, but it should be noted that the present invention is not limited to these examples.

The metal composite material 100 (FIG. 1) in which the metal material 130 (FIG. 1) is Au is made of an Si substrate (manufactured by MEMC Electronic Materials, p-type, mirror-polished wafer) and a TEM grid (a Cu grid provided with a carbon support film). Formed on top. The Si substrate was cleaned with acetone and dried by pure nitrogen gas flow. JP prepared during synthesis fullerene derivative 3,4,5C 20 C 60 1mM become as 1,4-dioxane 4mL based on 2007-137809 JP (step S310).

  Next, the mixture was heated to 70 ° C. using a hot plate and held for 30 minutes (step S320). It was visually confirmed that the fullerene derivative was completely dissolved in 1,4-dioxane. Thereafter, the solution was allowed to cool to room temperature (20 ° C.) and aged (step S330). A blackish brown precipitate was visually confirmed at the bottom of the solution.

The 1,4-dioxane solution containing the precipitate was applied on the Si substrate (or TEM grid) (step S340). Application was carried out by the water surface spreading membrane method. Specifically, water was poured into the container, a 1,4-dioxane solution containing precipitates was spread on the water, and the supramolecular organization 120 was formed at the interface between air and water. Next, the Si substrate (or TEM grid) was immersed in the container in the vertical direction and pulled up (vertical pulling method). Thereby, the supramolecular organization 120 is transferred from the water surface to the surface of the Si substrate (or TEM grid) and applied. After application, the Si substrate (or TEM grid) was naturally dried to remove excess solution. In this way, a substrate (hereinafter referred to as 3,4,5C 20 C 60 / Si substrate (or TEM grid)) provided with the supramolecular organization 120 on the Si substrate (or TEM grid) was obtained. . The precipitate was observed by SEM (manufactured by Philips, XL30). The observation results are shown in FIG.

Then, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, and 60 nm of Au were applied as the metal material 130 on the 3,4,5C 20 C 60 / Si substrate (or TEM grid), respectively (step S210). Au was applied by a JFC-1300 JEOL automatic sputter coater equipped with an MTM-20 film thickness controller. The actual Au film thickness was measured with a QCM film thickness monitor. These are called Au T / 3,4,5C 20 C 60 / Si substrates (or TEM grids). T indicates the film thickness.

Thereafter, the Au T / 3,4,5C 20 C 60 / Si substrate (or TEM grid) was immersed in chloroform for 60 seconds (step S220). A metal composite material Au T / Si substrate (or TEM grid) from which 3,4,5C 20 C 60 was removed was obtained by immersion. SEM observation was performed on the Au 10 / Si substrate and the Au 50 / Si substrate. The observation results are shown in FIGS. 6 and 7 and will be described later.

For au 50 / TEM grids, transmission electron microscope TEM-EDX with an energy dispersive X-ray analyzer (JEM-2100F, JEOL) was performed using composition analysis. The result of element mapping by EDX and the spectrum by EDX are shown in FIGS. 8 and 9, respectively, and will be described later.

  FIG. 5 is a SEM image of the fullerene structure of Example 1.

  The fullerene structure shown in FIG. 5 was a micrometer-sized flower-like sphere, and its surface was confirmed to be a flake shape with wrinkles on the nanometer scale.

6 is a view showing an SEM image of the Au 10 / Si substrate of Example 1. FIG.

7 is a view showing an SEM image of the Au 50 / Si substrate of Example 1. FIG.

FIG. 6 and FIG. 7 both show that the shape in which the flower-like shape is crushed (the shape in which the spherical shape is crushed) is maintained. Moreover, the surface was flaky and it confirmed that it was nano size-submicron size. Since the obtained metal composite material has a flaky surface, it is suggested that the specific surface area is large. Also, it should be noted that comparing the surface roughness of the Au 10 / Si substrate (FIG. 6) and the Au 50 / Si substrate (FIG. 7), the thicker Au 50 / Si substrate is more It can be seen that it has a large surface roughness. Although not shown, when other surface thicknesses were similarly observed by SEM, the surface roughness of T = 10 nm was the smallest, the surface roughness of T = 60 nm was the largest, It was confirmed that the surface roughness increased with the increase. From this, it is suggested that the thickness of the applied metal material contributes to the surface roughness of the obtained metal composite material, and that the larger the metal material thickness, the greater the surface roughness of the metal composite material. To do.

8 is a diagram showing Au mapping by EDX-TEM of the Au 50 / TEM grid of Example 1. FIG.

FIG. 9 is an EDX spectrum obtained by EDX-TEM of the Au 50 / TEM grid of Example 1.

In FIG. 8, the region shown with bright contrast indicates that Au is located. Moreover, according to FIG. 9, the remarkable peak of Au and C was shown. C is not a supramolecular organization (3,4,5C 20 C 60 ) but a carbon support film on a TEM grid. This also shows that a metal composite material made of Au was obtained using the supramolecular organization (3,4,5C 20 C 60 ) as a template.

A functional metal composite substrate 200 (FIG. 2) in which various functional thin films 210 (FIG. 2) are provided on the metal composite material 100 (FIG. 1) made of Au having a film thickness of 50 nm or 60 nm manufactured in Example 1 is manufactured. The dependence of the wettability on the functional thin film was investigated. As the functional thin film 210, an SAM film made of alkanethiol of CH 3 (CH 2 ) n1-1 SH (n1 = 4, 6, 8, 11, and 16), and 1H, 1H, 2H, 2H-perfluorodecanethiol SAM film made of fluorine-containing fluorocarbon thiol, polymer thin film made of polypropylene polymer, SAM film made of NH 2 (CH 2 ) 10 SH aminoalkanethiol, HO (CH 2 ) 10 SH hydroxyalkanethiol, and SAM films made of carboxyalkanethiol of COOH (CH 2 ) 10 SH were used.

A specific manufacturing procedure for forming the SAM film will be described. Au T / Si substrate (T = 50 or 60) was O 3 plasma treated for 2 minutes. This completely removed impurities composed of organic species adhering to the surface. Subsequently, the O 3 plasma-treated Au T / Si substrate was immersed in an ethanol solution containing a single molecule constituting various 2 mM SAM films for 24 hours or more. As a result, a SAM film composed of various single molecules is formed on the metal composite material in a self-organized manner. Thereafter, the Au T / Si substrate on which the SAM film was formed was taken out from the ethanol solution, washed with pure ethanol, and dried with pure nitrogen gas. The various functional metal composite substrates thus obtained are simply referred to as Cn1SH (n1 = 4, 6, 8, 11, and 16), CF3SH, NH2, OH, and COOH.

A specific manufacturing procedure for forming a polymer thin film will be described. Similarly, an Au T / Si substrate (T = 50 or 60) was O 3 plasma treated and spin-coated using a saturated acetone solution containing polypropylene. 0.5 mL of the acetone solution was dropped on the Au T / Si substrate, and the spin coating was performed at a rotation speed of 2400 rpm and a rotation time of 60 seconds. The functional metal composite substrate thus obtained is simply referred to as PPE.

  The functional metal composite substrate having a SAM film was subjected to X-ray photoelectron spectroscopy (XPS) by monochromatic Al—Kα ray excitation. Data was obtained from Kratos Analytical (UK). The results of C11SH and COOH are shown in FIGS. 10 and 11 and will be described later.

  About the functional metal composite substrate which has the various functional thin films 210 obtained, the contact angle with water was measured. The measurement was performed in the atmosphere using a contact angle measurement system G10 apparatus (Kruss, Germany). The results are shown in FIG. In addition, the state of water droplets on C11SH, CF3SH, and COOH was photographed. These results are shown in FIGS.

Figure 10 is a diagram showing an XPS spectrum of S 2p of C11SH of Example 2.

FIG. 11 is a diagram showing an XPS spectrum of S 2p of COOH of Example 2.

According to FIGS. 10 and 11, the peak of the S 2p of C11SH and COOH they are both observed in 161.7eV and 162.8EV. The peak at 161.7 eV was in good agreement with the peak observed when Au and S were bonded and arranged in close packing. The peak of 162.8 eV is attributed to unbound thiol or thiol dissociated from Au during measurement. Although not shown, according to the XPS spectrum of C 1s of C11SH and COOH, C1s peaks were observed in 284.7EV. This indicates C—C bonds due to functional groups on the surface or contaminating carbon. This also, SAM film monomolecular CH 3 -C 10 -SH and COOH-C 10 -SH is bonded to a metal composite material consisting of Au, consisting CH 3 -C 10 -SH and COOH-C 10 -SH It is suggested that each was formed. Although not shown, similar results were obtained for other Cn1SH, CF3SH, NH2 and OH.

  FIG. 12 is a diagram showing the dependence of the contact angle with water on the functional metal composite substrate of Example 2 on the functional thin film species.

  From FIG. 12, it was confirmed that the functional metal composite substrate having a SAM film made of alkanethiol and fluorine-containing fluorocarbon thiol and the functional metal composite substrate having a polymer thin film made of PPE exhibit water repellency. Focusing on the water repellency of the functional metal composite substrate having a SAM film composed of alkanethiol (C4SH, C6SH, C8SH, C11SH and C16SH in FIG. 12), as the alkyl chain of alkanethiol becomes longer (as n1 increases) It can be seen that water repellency increases and super water repellency is obtained. Specifically, when n1 is 4 or more and 7 or less, the functional metal composite substrate has high water repellency, and when n1 is 8 or more, the functional metal composite substrate has super water repellency. This suggests that the control of the degree of water repellency can be adjusted by changing the alkyl chain length in addition to the selection of the type of functional thin film.

  From FIG. 12, it was confirmed that the functional metal composite substrate (PPE) having a polymer thin film made of polypropylene exhibits high water repellency. The degree of water repellency can be changed by changing the selection of the type of polymer.

  It was confirmed that the functional metal composite substrate having a SAM film made of aminoalkanethiol, a SAM film made of hydroxyalkanethiol, and a SAM film made of carboxyalkanethiol each showed hydrophilicity. Even in the case of a metal composite material having the same film thickness (50 nm), the degree of hydrophilicity can be controlled depending on the type of SAM film used. Specifically, the functional metal composite substrate having a SAM film made of hydroxyalkanethiol showed high hydrophilicity, and the functional metal composite substrate having a SAM film made of carboxyalkanethiol showed superhydrophilicity.

  FIG. 13 is a diagram illustrating a state of water droplets on C11SH according to the second embodiment.

  FIG. 14 is a diagram illustrating a state of water droplets on CF3SH according to the second embodiment.

  From FIG. 12, the contact angle in C11SH is 157 ± 1 °, and it can be seen from FIG. 13 that the water droplets on C11SH maintain a substantially spherical shape and are super-water-repellent. From FIG. 12, the contact angle in CF3SH is 170 ± 4 °, and it can be seen from FIG. 14 that the water droplets on CF3SH are almost spherical and are super water-repellent. Fluorine has a very low surface free energy and is known to easily exhibit super water repellency. However, according to the present invention, it can exhibit super / high water repellency even with alkanethiols and polymers that do not contain fluorine. It is advantageous without worrying about environmental pollution.

  FIG. 15 is a diagram illustrating a state of water droplets on COOH according to the second embodiment.

  From FIG. 12, the contact angle in COOH is 11 ± 4 °, and it can be seen from FIG. 15 that the water drops on the COOH are not spherical but are spread in a film shape on the surface of the COOH and are super hydrophilic. .

Using the metal composite material having various thicknesses obtained in Example 1, a functional metal composite substrate 200 (FIG. 2) exhibiting water repellency was manufactured, and the film thickness dependency of water repellency was examined. As the SAM film which is the functional thin film 210 (FIG. 2), a single molecule of CH 3 —C 10 —SH (1-undecanethiol) in which n1 = 11 in CH 3 (CH 2 ) n1-1 SH was used. Since the specific manufacturing procedure is the same as that of Example 2, the description thereof is omitted.

  The contact angle with water was measured for the functional metal composite substrate made of the metal composite material having various thicknesses thus obtained. The results are shown in FIG.

  FIG. 16 is a diagram illustrating the film thickness dependence of the metal composite material of the contact angle with water in the functional metal composite substrate of Example 3.

From FIG. 16, regardless of the film thickness of the metal composite material, the functional metal composite substrate having a SAM film made of CH 3 —C 10 —SH monomolecule has a contact angle of 90 ° or more and exhibits water repellency. It was confirmed. Notably, as the metal composite film thickness increased, the contact angle also increased. Specifically, when the film thickness of the metal composite material is 10 nm or more and less than 40 nm, the contact angle is in the range of 110 ° or more and less than 150 °, the functional metal composite substrate exhibits high water repellency, and the film thickness of the genus composite material is At 40 nm or more, the contact angle was in the range of 150 ° or more, and the functional metal composite substrate exhibited super water repellency.

  This is because the degree of water repellency of the functional metal composite substrate is related to the degree of surface roughness of the metal composite material described with reference to FIGS. That is, when the functional metal composite substrate has low water repellency, the surface roughness of the metal composite material is low (the film thickness of the metal composite material is small), and when the functional metal composite substrate has high water repellency, the metal composite The surface roughness of the material is high (the film thickness of the metal composite material is large). Therefore, in addition to selecting the type of functional thin film and changing the alkyl chain length, the degree of water repellency (from high water repellency to super water repellency) can also be controlled by changing the film thickness of the metal composite material. I confirmed that I can do it.

Using the metal composite material having various thicknesses obtained in Example 1, a functional metal composite substrate 200 (FIG. 2) exhibiting hydrophilicity was manufactured, and the film dependency of water repellency was examined. As the SAM film of the functional thin film 210 (FIG. 2), a single molecule of COOH—C 10 —SH (11-mercapto-undecanoic acid) in which n3 = 10 in COOH (CH 2 ) n3 SH was used. Since the specific manufacturing procedure is the same as that of Example 2, the description thereof is omitted.

  The contact angle with water was measured for the functional metal composite substrate made of the metal composite material having various thicknesses thus obtained. The results are shown in FIG.

  FIG. 17 is a diagram illustrating the film thickness dependence of the metal composite material of the contact angle with water in the functional metal composite substrate of Example 4.

From FIG. 17, the functional metal composite substrate having a SAM film made of COOH-C 10 -SH monomolecule has a contact angle of less than 90 ° and exhibits hydrophilicity regardless of the film thickness of the metal composite material. It was confirmed. Of note, the contact angle decreased as the film thickness of the metal composite increased. Specifically, when the film thickness of the metal composite material is 20 nm or more and less than 50 nm, the contact angle is in the range of more than 15 ° and 40 ° or less, the functional metal composite substrate exhibits high hydrophilicity, and the film thickness of the metal composite material. Is 50 nm or more, the contact angle is in the range of 15 ° or less, and the functional metal composite substrate showed super hydrophilicity.

This is because the degree of hydrophilicity of the functional metal composite substrate is related to the degree of surface roughness of the metal composite material, similar to the degree of water repellency described in Example 3. That is, when the functional metal composite substrate has low hydrophilicity, the surface roughness of the metal composite material is low (the film thickness of the metal composite material is small), and when the functional metal composite substrate has high hydrophilicity, the metal composite material The surface roughness of the material is high (the film thickness of the metal composite material is large). From this, in addition to the selection of the type of functional thin film, the degree of hydrophilicity (from hydrophilic to highly hydrophilic, and even superhydrophilic) can be controlled by changing the film thickness of the metal composite material. confirmed.
<Comparative Example 1>

In Example 1, the surface of the Au 50 / Si substrate having a film thickness of 50 nm was subjected to O 3 plasma treatment, and then the contact angle with water was measured. As a result, it was confirmed to show super hydrophilicity. However, it has been found that as time for exposure to the air elapses, impurities adhere to the surface, the contact angle increases, and the hydrophilicity is impaired. This also shows that the functional metal composite material having the functional thin film according to the present invention is effective because the wettability does not change with time.

  As described above, the functional metal composite substrate according to the present invention is composed of a metal composite material and a functional thin film. Combined with characteristics, it can express various functions. Such a functional metal composite substrate is used as a rust preventive material, MEMS / NEMS, or a catalyst material when high / super water repellency is exhibited, and when it exhibits high / super hydrophilic property, it is an antifouling metal. In addition to the above, when the functional thin film has various functional groups, a functional metal composite substrate having a biochemical function or a sensor function is provided. It can be applied to biocompatible substrates.

Schematic diagram of metal composite material used in the present invention Schematic diagram of functional metal composite substrate according to the present invention Schematic diagram showing details of functional metal composite substrate according to the present invention The figure which shows the flowchart which manufactures the functional metal composite substrate 200 by this invention. The figure which shows the SEM image of the fullerene structure of Example 1. It shows the Au 10 / Si substrate SEM images of Example 1 It shows the Au 50 / Si substrate SEM images of Example 1 It shows a Au mapping by EDX-TEM of Au 50 / TEM grid Example 1 It shows the EDX spectrum by EDX-TEM of Au 50 / TEM grid Example 1 It shows the XPS spectrum of S 2p of C11SH Example 2 The figure which shows the XPS spectrum of S2p of COOH of Example 2 The figure which shows the functional thin film seed | species dependence of the contact angle with water in the functional metal composite substrate of Example 2. The figure which shows the mode of the water drop on C11SH of Example 2. The figure which shows the mode of the water drop on CF3SH of Example 2. The figure which shows the mode of the water drop on COOH of Example 2. The figure which shows the film thickness dependence of the metal composite material of the contact angle with water in the functional metal composite board | substrate of Example 3. FIG. The figure which shows the film thickness dependence of the metal composite material of the contact angle with water in the functional metal composite board | substrate of Example 4. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Metal composite material 110 Base material 120 Supramolecular organization 130 Metal material 140 Shape of removal trace-like hole 150 Flakes 160 Fullerene structure 200 Functional metal composite substrate 210 Functional thin film 310 Monomolecule 320 Polymer

Claims (11)

  1. A functional metal composite substrate,
    A metal composite material, and a functional thin film provided on the surface of the metal composite material,
    The metal composite material has a shape of a removal trace-like hole of a supramolecular organization having a fractal surface structure, and the surface of the shape is flaky,
    The functional metal composite substrate, wherein the functional thin film is either a self-assembled monomolecular film (SAM film) or a polymer thin film.
  2. The functional metal composite substrate according to claim 1,
    The functional thin film has a surface free energy lower than that of the metal composite material, and the functional metal composite substrate has water repellency.
  3. The functional metal composite substrate according to claim 2,
    The SAM film is alkanethiol (CH 3 (CH 2 ) n1-1 SH (n1 ≧ 2)) or fluorine-containing fluorocarbon thiol,
    The functional metal composite substrate, wherein the polymer thin film is polypropylene.
  4. In the functional metal composite substrate according to claim 3,
    The functional metal composite substrate, wherein n1 satisfies n1 ≧ 8.
  5.   The functional metal composite substrate according to claim 4, wherein the metal composite material has a thickness of 40 nm or more.
  6. The functional metal composite substrate according to claim 1,
    The functional thin film has a surface free energy higher than the surface free energy of the metal composite material, and the functional metal composite substrate has hydrophilicity.
  7. In the functional metal composite substrate according to claim 6,
    The SAM film includes aminoalkanethiol (NH 2 (CH 2 ) n2 SH: n2 ≧ 1), carboxyalkanethiol (COOH (CH 2 ) n3 SH: n3 ≧ 1) and hydroxyalkanethiol (HO (CH 2 ) n4. A functional metal composite substrate selected from the group consisting of SH: n4 ≧ 1).
  8.   The functional metal composite substrate according to claim 7, wherein the metal composite material has a thickness of 50 nm or more.
  9. The functional metal composite substrate according to claim 1,
    The supramolecular structure has a bilayer structure as a base nano-structure, and a fullerene structure in which fullerene derivatives are organized is organized in a layered manner,
    The fullerene derivative is represented by the formula (1), the fullerene moiety A represented by the formula (2), the benzene ring bonded to the fullerene moiety, and the third, fourth, and fifth positions bonded to the benzene ring. Including the first to third substituents R 1 , R 2 and R 3 ,
    Here, in the formula (1), each of the first and second substituents R 1 and R 2 is an alkyl chain containing at least 20 carbon atoms,
    Said third substituent R 3 is either a hydrogen atom or an alkyl chain comprising at least 20 carbon atoms,
    In the formula (2), (Fu) represents a fullerene, X represents a hydrogen atom or a methyl group, and the benzene ring is bonded to the nitrogen-containing 5-membered ring of the fullerene moiety A. Metal composite substrate.
  10.   Removal of supramolecular structures having a fractal surface structure The shape of the trace-like pores, and the surface of the shape is a flake-like surface on a self-assembled monolayer (SAM film) or polymer thin film The method for producing a functional metal composite substrate according to claim 1, comprising a forming step of forming any one of the functional thin films.
  11. The method of claim 10, prior to the forming step.
    An application step of applying a metal material on a supramolecular structure having a fractal surface structure;
    A dipping step of dipping the composite material obtained by the applying step in a good solvent of the supramolecular organization.
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