WO2010064699A1 - 微粒子構造体/基体複合部材及びその製造方法 - Google Patents
微粒子構造体/基体複合部材及びその製造方法 Download PDFInfo
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- WO2010064699A1 WO2010064699A1 PCT/JP2009/070379 JP2009070379W WO2010064699A1 WO 2010064699 A1 WO2010064699 A1 WO 2010064699A1 JP 2009070379 W JP2009070379 W JP 2009070379W WO 2010064699 A1 WO2010064699 A1 WO 2010064699A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0042—Assembling discrete nanostructures into nanostructural devices
- B82B3/0047—Bonding two or more elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
Definitions
- the present invention relates to a fine particle structure / substrate composite member in which an aggregate of fine particles such as nanoparticles forms a microstructure such as a three-dimensional raised structure on a substrate, and a method for manufacturing the same.
- nanoparticles As a material that satisfies this requirement, fine particles having a size of about several nanometers, so-called nanoparticles, are attracting attention. In order to express the characteristics of being nanoparticles more effectively, it is important that the nanoparticles do not aggregate with each other, and each one exists individually and has good dispersibility.
- a size of 1 nm to less than 1 ⁇ m, typically several nanometers to several tens of nanometers is called a nanosize, and a member having a nanosize size is prefixed, for example, a nanoparticle. I will call it with the word “nano”.
- the characteristics of materials and devices made of nanoparticles may be determined by the properties of individual particles themselves, but the properties of the materials and the arrangement of particles bound to the surface of the particles and the structure and size of the aggregates of the particles In many cases, it greatly affects the performance of the system and contributes to effective performance improvement.
- the distance between the fine particles is an important factor that affects the characteristics.
- the sensor is advantageous in that the collision frequency between the sensing substance in the liquid phase or the gas phase and the nanoparticles is advantageous, and in the catalyst, the collision frequency between the reactant and the nanoparticles is large. This structure is considered advantageous.
- the arrangement of the nanotubes is directly determined by the arrangement of the metal fine particles (see, for example, JP-A-2003-183012). ).
- top-down microfabrication techniques such as lithography and probe drawing are effective. For example, by forming a fine pattern such as a self-assembled film on the substrate itself so that it has surfaces with different interactions with fine particles, and then fixing the fine particle layer only to surfaces with strong interactions, It is possible to selectively arrange fine particles in the region.
- Top-down microfabrication techniques such as lithography and probe drawing are excellent in that a fine pattern can be reliably produced with good reproducibility, but there is a problem that requires a large-scale apparatus.
- the bottom-up approach is advantageous in that a nano-sized fine pattern can be produced at low cost, but reliability such as durability of the mold is a problem.
- a conventional method for forming a fine pattern is the same as that used for fine processing of semiconductors. Therefore, it is basically a method suitable for forming a fine pattern of a two-dimensional nanoparticle assembly on a smooth substrate, and is used to produce a three-dimensional microstructure such as a hollow structure. Not suitable for.
- these methods are applied as a method for forming a fine pattern of a fine particle aggregate, since the fine particles are fused with each other when heated to a high temperature, a method that requires a step of heating to a high temperature is used. It is not possible.
- the present invention has been made in view of such circumstances, and the object thereof is a fine particle structure in which an aggregate of fine particles such as nanoparticles forms a microstructure such as a three-dimensional raised structure on a substrate. / To provide a substrate composite member and a method for producing the same, which does not require a step of heating to a high temperature.
- the present invention Providing a substrate having a smooth surface; Forming a fine particle layer in which fine particles are closely arranged along the surface; By binding specific molecules to the fine particles, the fine particle layer is changed to a fine particle assembly layer composed of the fine particles to which the specific molecules are bonded, By increasing the center-to-center distance between the adjacent fine particles, to generate a three-dimensional microstructure in which the fine particle assembly layer is raised from the surface in a part of the region, Or Reducing the center-to-center distance between the adjacent fine particles, thereby generating a fine structure in which the fine particle aggregate layer is missing in a partial region of the surface, and the substrate is exposed in the missing part;
- the present invention relates to a method for producing a fine particle structure / substrate composite member having
- a substrate having a smooth surface In a fine particle layer in which fine particles are closely arranged along the surface, a specific molecule is bonded to the fine particles, Whether the three-dimensional microstructure in which the layer is raised from the surface is formed in a part of the region by increasing the center-to-center distance between the adjacent fine particles, Or Any one of a layer where a part of the surface is missing due to a decrease in the center-to-center distance between the adjacent fine particles, and a microstructure in which the base is exposed in the missing part is formed. And a fine particle structure / substrate composite member having a fine particle aggregate layer composed of the fine particles to which the specific molecules are bonded.
- the method for producing a fine particle structure / substrate composite member of the present invention first, Providing a substrate having a smooth surface; Forming a fine particle layer in which fine particles are closely arranged along the surface.
- the surface of the substrate needs to be so smooth that adjacent fine particles can sufficiently contact each other.
- the fine particle layer is changed to a fine particle aggregate layer composed of the fine particles having the specific molecules bonded to the surface thereof.
- the center-to-center distance between the adjacent fine particles in the fine particle assembly layer changes according to the molecular length of the specific molecule.
- the surface area of the fine particle assembly layer is larger than the surface area of the fine particle layer. . Since the fine particle assembly layer is disposed on the surface of the substrate having the same area as the fine particle layer, stress is generated. As a result, the fine particle aggregate layer rises from the surface in a part of the region so as to eliminate the stress, and a three-dimensional microstructure is spontaneously formed.
- the surface area of the microparticle assembly layer is smaller than the surface area of the microparticle layer.
- the fine particle aggregate layer cannot cover the entire surface of the substrate having the same area as the fine particle layer, and the fine particle aggregate layer is missing in a partial region of the surface. A microstructure in which the substrate is exposed is spontaneously formed.
- the fine particle assembly layer can be removed from the substrate surface by a very simple process.
- a raised three-dimensional microstructure or a microstructure in which the substrate is exposed at the missing portion of the particle assembly layer can be spontaneously formed in the particle assembly layer.
- the size and shape of the three-dimensional microstructure and the missing part are the size and particle size distribution of the fine particles, the thickness of the fine particle layer, the structure (length, bulkiness, etc.) and flexibility of the special molecule, It varies depending on various conditions such as a treatment for chemically modifying the surface of the substrate in advance. Therefore, various microstructures can be formed on the surface of the substrate by a combination of these conditions.
- the fine particle structure / substrate composite member of the present invention is a fine particle structure / substrate composite member that can be easily produced by the method for producing a fine particle structure / substrate composite member of the present invention.
- the fine particle aggregate layer when the three-dimensional microstructure formed by the fine particle aggregate layer protruding from the surface is formed, the fine particle aggregate layer has a large surface area, and the fine particle aggregate layer and Since there are a large number of minute hollow structures between the base and the substrate, the surface of the fine particle assembly layer such as conductivity and surface wettability can be selected by appropriately selecting the material of the fine particles and / or the special molecules.
- the fine particle aggregate layer can be used as a member that utilizes the surface of the fine particle aggregate layer or the hollow structure as a reaction field, such as a member that utilizes physical properties, a sensor, or a catalyst device. Further, when the fine particle aggregate layer is missing in a partial region of the surface, and the base is exposed in the missing part, it is used as a member that exhibits the function of the base only in the missing part. be able to.
- FIG. 5 is a conceptual diagram showing a cross section of another example of the fine particle structure / substrate composite member.
- FIG. 6 is a conceptual diagram showing a cross section of still another example of the fine particle structure / substrate composite member. It is a schematic sectional drawing which shows the flow of the manufacturing process of a fine particle structure / base
- FIG. 6 is a structural formula showing an example of a substituted molecule used for producing a fine particle structure / substrate composite member.
- FIG. 6 is a structural formula showing an example of a post-treatment process of a substituted molecule added to the production process of the fine particle structure / substrate composite member.
- An observation image (a, b) of the fine particle assembly layer obtained in Example 1 of the present invention by a scanning electron microscope (SEM) and an observation image (c) of an atomic force microscope (AFM) of a three-dimensional raised structure is there.
- FIG. 4 is an SEM observation image (a) of another fine particle assembly layer and an AFM observation image (b) of a three-dimensional raised structure. It is the SEM observation image (a) of the fine particle aggregate layer obtained in Example 2 of the present invention, and the SEM observation image (b) of the cross section of the three-dimensional raised structure. It is a SEM observation image of a fine particle layer and various fine particle aggregate layers obtained in Example 3 of the present invention. It is a SEM observation image of a fine particle layer and a fine particle aggregate layer obtained in Example 4 of the present invention.
- fine particles coated with protective film molecules that prevent aggregation or fusion of the fine particles are used as the fine particles, and the protective film molecules are replaced with the specific molecules. It is better to replace it.
- the fine particles are usually coated with a protective film molecule or a film made of a surface modifier for modifying the surface of the fine particles is formed. Used.
- the surface modifier is also regarded as a protective film molecule in a broad sense, and is included in the protective film molecule. Note that the protective film molecules are not necessarily required when the fine particles do not aggregate or fuse even if they are not coated with the protective film molecules.
- nanoparticles having a particle size of nano size it is preferable to use nanoparticles having a particle size of nano size. Since nanoparticles have a very large surface area per unit mass, reactions on the surface can be performed efficiently, and the performance of sensors, electrodes, catalysts, and the like can be improved. In addition, due to a unique property called the quantum size effect due to size, application to novel sensors, optical materials, electronic materials, battery materials, catalysts, and the like is also expected. Note that, in this specification, the size of 1 nm to less than 1 ⁇ m, typically several nanometers to several tens of nanometers is referred to as nanosize, and a member having a nanosize size is, for example, a nanoparticle. Thus, we will call it with the prefix “nano”.
- a molecule having a cyano group-CN, a seranyl group-SeH, a terranyl group-TeH, or a phosphino group -PR 1 R 2 (R 1 and R 2 are H or an organic group) may be used. As will be described later, these functional groups exhibit a strong binding force to various fine particles.
- the fine particles and the functional molecules have conductivity.
- the fine particle aggregate layer in which the three-dimensional microstructure is formed is preferably used as an electrode.
- the functional molecule is a fluorine-containing molecule, and the fine particle aggregate layer forms a super water-repellent surface.
- the fine particles and / or the functional molecules have a catalytic function, and the fine particle aggregate layer in which the three-dimensional microstructure is formed preferably functions as a catalyst.
- the substrate is an electrode
- the fine particles and the functional molecule are not conductive
- the electrode is exposed at the missing portion.
- a structure in which the electrode is exposed in the missing portion can be easily produced without using a method such as lithography.
- Such a structure in which a large number of microelectrodes are arranged on the surface can be used as a microelectrode array.
- the substance supply rate from the solution to the electrode can be increased as compared with a normal electrode in which no microstructure is formed.
- the microelectrode array is used, for example, highly sensitive electrochemical measurement can be performed, so that the microelectrode array can be used as an electrode for microanalysis.
- the fine particle layer may be formed by a coating method, a printing method, a Langmuir-Blodget method, a stamp method, a casting method, a lift-off method, or a dipping method.
- FIGS. 1A and 1B are conceptual diagrams showing a cross section of an example of a fine particle structure / substrate composite member based on the present embodiment, and FIG. It is a conceptual diagram which shows the cross section of 4.
- FIG. FIG. 1 shows a case where the fine particle layer 4 is a single layer, and the fine particle assembly layer 6a or 6b formed from the fine particle layer 4 is also a single layer.
- the fine particles 2 are arranged on the substrate 1 with the surface covered with the protective film molecules 3. This is because the nano-sized fine particles 2 have a strong tendency to aggregate with each other to form an aggregate. Therefore, in order to prevent aggregation and fusion of the fine particles 2, the fine particles 2 are usually coated with the protective film molecules 3 or a surface modifier for modifying the surface of the fine particles 2.
- a film in which a film made of is formed is used. In the present embodiment, the case where the surface modifier is regarded as the protective film molecule 3 in a broad sense and the protective film composed of the protective film molecule 3 is formed on the surface of the fine particle 2 will be described.
- the surface of the substrate 1 needs to be so smooth that the adjacent fine particles 2 in the fine particle layer 4 can sufficiently contact each other.
- the fine particles 2 covered with the protective film molecules 3 are densely arranged along the surface of the substrate 1, for example, in a close-packed state or a state close to the close-packed state. Therefore, the distance between the two adjacent fine particles 2 in the fine particle layer 4 (the shortest distance between the surfaces of the two adjacent fine particles 2) is the protection formed on the surface of the two fine particles 2 by the protective film molecules 3. It is approximately equal to the total thickness of the films (twice the thickness of each protective film). Therefore, by appropriately selecting the molecular length of the protective film molecules 3, the interval between the adjacent fine particles 2 can be appropriately controlled.
- the fine particle layer 4 thus prepared is caused to act by the substitution molecule 5 as the specific molecule, the protective film molecule 3 is substituted by the substitution molecule 5, and the fine particle layer 4 is a fine particle composed of the fine particles 2 to which the substitution molecule 5 is bonded.
- the three-dimensional raised structure 7 or the missing portion 8 is generated in the fine particle aggregate layer 6.
- the substituted molecule 5 needs to have at least one binding site with the fine particle 2.
- FIGS. 1A and 1B show a case where the substituted molecules 5 a and 5 b have one binding site with the fine particle 2.
- the substituted molecule 5 is bonded to the fine particle 2 at this binding site, and is bonded to the end of the substituted molecule 5 bonded to the adjacent fine particle 2 by an intermolecular force at another end.
- (A) of FIG. 1 is a case where the molecular length of the substituted molecule 5a is generally longer than the molecular length of the protective film molecule 3.
- the distance between the fine particles 2 is expanded by the long substitution molecules 5a entering between the adjacent fine particles 2, and the distance between the centers of the fine particles 2 in the fine particle assembly layer 6a is the same as that of the fine particles 2 in the fine particle layer 4. Greater than the distance between the centers. Therefore, the surface area of the fine particle aggregate layer 6 a is also larger than the surface area of the original fine particle layer 4.
- the fine particle assembly layer 6a When the fine particle assembly layer 6a is disposed on the substrate 1 having the same area as the fine particle layer 4, it is necessary to take a three-dimensional shape in which a part of the fine particle assembly layer 6a that cannot be stored on the plane partially rises. Absent. As a result, a three-dimensional three-dimensional raised structure 7 such as a donut shape, a circular shape, or a honeycomb shape is spontaneously formed.
- FIG. 1B generally shows the case where the molecular length of the substitution molecule 5 b is shorter than the molecular length of the protective film molecule 3.
- the short substitution molecules 5b occupy between the adjacent fine particles 2, the interval between the fine particles is reduced.
- the distance between the centers of the fine particles in the fine particle assembly layer 6b is smaller than the distance between the centers of the fine particles in the fine particle layer 4, and the surface area of the fine particle assembly layer 6b is also larger than the surface area of the original fine particle layer 4.
- the fine particle aggregate layer 6b cannot cover the entire surface of the substrate 1 having the same area as the fine particle layer 4, and the fine particle aggregate layer 6b is missing in a partial region of the surface.
- a missing portion 8 such as a partial crack or a gap occurs in each part of the fine particle aggregate layer 6b, and a microstructure in which the substrate 1 is exposed is spontaneously formed in the missing portion 8.
- FIG. 2 (c) and 2 (d) are conceptual diagrams showing a cross section of another example of the fine particle structure / substrate composite member according to the present embodiment.
- (C) and (d) of FIG. 2 show a case where the substituted molecules 5 c and 5 d have two binding sites with the fine particles 2. In this case, some of the substituted molecules 5 bind to the fine particles 2 at one of the binding sites, and bind to the adjacent fine particles 2 at the other binding site. As described above, when the substituted molecule 5 is bonded to the fine particle 2 so as to bridge between the two fine particles, it is mechanically stronger and more stable than the case where there is one binding site. 6 is formed. 2 shows a case where the fine particle layer 4 is a single layer and the fine particle aggregate layer 6c or 6d formed from this is also a single layer, as in FIG.
- the molecular length of the substitution molecule 5c is generally longer than the length of the molecular length of the protective film molecule 3 (interval between the adjacent fine particles 2 in the fine particle layer 4).
- the distance between the fine particles 2 is expanded by the long substitution molecules 5 c entering between the adjacent fine particles 2, and the distance between the centers of the fine particles 2 in the fine particle assembly layer 6 c is the same as that of the fine particles 2 in the fine particle layer 4. Greater than the distance between the centers.
- a part of the fine particle aggregate layer 6c partially rises, and a three-dimensional three-dimensional raised structure 7 such as a donut shape, a circular shape, or a honeycomb shape is spontaneously formed.
- (d) of FIG. 2 is a case where the molecular length of the substituted molecule 5d is generally shorter than the length of twice the molecular length of the protective film molecule 3.
- the short substitution molecules 5d occupy between the adjacent fine particles 2, the distance between the fine particles is reduced, and the distance between the centers of the fine particles 2 in the fine particle assembly layer 6d is between the centers of the fine particles 2 in the fine particle layer 4.
- the fine particle aggregate layer 6d cannot cover the entire surface of the substrate 1 having the same area as the fine particle layer 4, and the fine particle aggregate layer 6d is missing in a partial region of the surface.
- a missing portion 8 such as a partial crack or a gap is generated in each of the positions 6d, and a microstructure in which the substrate 1 is exposed is spontaneously formed in the missing portion 8.
- the protective film molecule 3 when substituted using octanedithiol, it is considered that the change in the interval between adjacent fine particles is the smallest.
- the missing portion 8 is formed in the fine particle aggregate layer 6d as shown in FIG. 2D, and when 8 ⁇ n ( ⁇ 20), As shown in (c) of FIG. 2, the three-dimensional raised structure 7 is formed in the fine particle aggregate layer 6c.
- FIG. 3 is a conceptual diagram showing a cross section of still another example of the fine particle structure / substrate composite member based on the present embodiment.
- 3 (y) shows a cross section of the fine particle layer 4e
- FIG. 3 (e) shows a cross section of the fine particle aggregate layer 6e.
- the fine particle layer 4e has a multilayer structure in which a plurality of fine particles 2 are laminated
- the fine particle assembly layer 6e formed from the fine particle layer 4e also has a multilayer structure.
- FIG. 3 shows an example in which the substituted molecule 5e has one binding site with the fine particle 2 as in the example shown in FIG. In the case where the substituted molecule 5 has two or more binding sites with the fine particles 2, it may be considered to be the same as in the case of FIG. 2 showing an example of a single layer.
- the formed microstructure is roughly divided into two depending on the length of the molecular length of the substitution molecule 5 and the molecular length of the protective film molecule 3. . That is, when the molecular length of the substitution molecule 5e is longer than that of the protective film molecule 3, as shown in FIG. 3, a part of the fine particle assembly layer 6e is partially raised, A three-dimensional three-dimensional raised structure 7 such as a circular shape or a honeycomb shape is formed.
- the fine particle layer 4 is a multilayer film, the multilayer film needs to be thin enough to allow a necessary amount of the substitution molecules 5 to penetrate from the surface of the fine particle layer 4 to the lowest layer (in contact with the substrate 1). It is.
- the missing portion 8 such as a partial crack or a gap is generally present at various positions of the fine particle assembly layer 6.
- the substrate 1 is exposed at this location.
- any material of metal, semiconductor, and insulator can be selected as appropriate.
- the surface of the substrate 1 needs to be so smooth that adjacent fine particles 2 in the fine particle layer 4 can sufficiently contact each other.
- the three-dimensional raised structure 7 and the missing portion 8 of the fine particle assembly layer 6 are caused by the displacement of the fine particles 2 on the surface of the substrate 1 when the protective film molecules 3 of the fine particles 2 are replaced by the replacement molecules 5. It is formed. Therefore, a substrate in which an interaction that is so strong that the fine particles 2 cannot be displaced on the substrate is generated between the fine particles 2 cannot be used as the substrate 1.
- the three-dimensional raised structure 7 and the missing portion 8 change depending on the strength of the interaction between the substrate 1 and the fine particles 2 or the protective film molecules 3 and the substitution molecules 5. Therefore, by patterning the surface of the substrate 1 into two or more types of regions having different properties, the fine particle assembly layer 6 having different three-dimensional raised structures 7 or missing portions 8 can be formed in each region. .
- the fine particles 2 are nanoparticles having a diameter of about 100 nm or less.
- the material of the fine particles 2 can be appropriately selected from any of metal, semiconductor, and insulator depending on the properties of the fine particle assembly layer 6 to be formed.
- the conductivity is reduced when the diameter is reduced to an extent that exhibits a quantum size effect. It is necessary to use fine particles 2 having a diameter of about 5 nm or more.
- the protective film molecule 3 and the surface modifier are suitable for being replaced by the substitution molecule 5, it is necessary that the strength of binding to the fine particles 2 is weaker than the strength of the substitution molecules 5 binding to the fine particles 2. .
- the functional group that the substituted molecule 5 has as a binding site with the fine particle 2 is, for example, sulfanyl group —SH, disulfide group —SS—, selenol group —SeH, tellurol group —TeH, amino group —NH 2 , phosphino group.
- R 1 R 2 (wherein R 1 and R 2 are hydrogen atoms or organic groups), cyano group —CN, thioisocyanide group —SCN, isocyano group —NC, carboxyl group —COOH, and the like.
- Au -SCN Au, Ag, Pt, Pd, Cu
- Fe -NC Au, Ag, Pt, Pd -COOH ... Au, Ag, TiO 2 , ZnO, In 2 O 3, NiO, VO 2, SnO 2
- Molecules having these functional groups and chemically adsorbed on the fine particles 2 can also be used as the protective film molecules 3 or the surface modifier.
- the binding force of the protective film molecule 3 or the surface modifier to the fine particles 2 is weaker than the strength of the binding molecules 5 to be bonded later to the fine particles 2 so as not to inhibit the substitution reaction by the substituted molecules 5. It is necessary.
- the fine particle 2 is a gold fine particle
- a molecule having an amino group —NH 2 or a phosphino group —PR 1 R 2 is replaced with a molecule having a sulfanyl group.
- a molecule having an amino group or a phosphino group can be used as the protective film molecule 3
- a molecule having a sulfanyl group can be used as the substitution molecule 5.
- the fine particle aggregate layer 6 when the three-dimensional raised structure 7 in which the fine particle aggregate layer 6 is raised from the surface of the substrate 1 is formed, the fine particle aggregate layer 6 has a large surface area. In addition, a large number of minute hollow structures exist between the fine particle assembly layer 6 and the substrate 1.
- the material of the fine particles 2 and / or the substituted molecules 5 it can be used as a member that utilizes the surface physical properties of the fine particle assembly layer 6 such as conductivity and surface wettability.
- the electrical conductivity of the fine particle assembly layer 6 can be controlled by the material and size of the fine particles 2 and the type and length of the substituted molecules 5 to be bonded. Therefore, a surface having a desired antistatic effect can be obtained by using the fine particle aggregate layer 6.
- the fine particles 2 are made of metal and the substituted molecules 5 bonded to the fine particles 2 are molecules having high electric conductivity such as conjugated molecules, the electric conductivity of the fine particle assembly layer 6 is also high.
- the fine particle aggregate layer 6 on which the raised structure 7 is formed can be applied as an electrode having a large surface area.
- the wettability of the surface of the fine particle assembly layer 6 can be controlled by the nature of the substituted molecules 5. Therefore, a surface having desired wettability can be obtained by using the fine particle aggregate layer 6.
- the water repellency of the solid surface is determined by the surface free energy and the surface microstructure. For example, a fluorine-containing molecule having a large surface energy is used as the substitution molecule 5 and the three-dimensional raised structure 7 is formed. A super water-repellent surface can be obtained.
- the surface of the fine particle assembly layer 6 having a large surface area, such as a sensor or a catalyst device, or between the fine particle assembly layer 6 and the substrate 1 can be used.
- the formed hollow structure By making the formed hollow structure function as a chemical reaction field with high reaction efficiency, it can be used as a member to be used.
- the fine particle structure / substrate composite member By functioning as a chemical reaction field with high reaction efficiency, the fine particle structure / substrate composite member can be used as a high-performance chemical reaction reactor.
- the catalytic chemical reaction can proceed in the above reaction field, and the fine particle structure / substrate composite member can function as a catalytic reaction device. it can.
- a molecule that acts as a catalyst can be added and bonded to the fine particles 2 or the like.
- an enzyme can also be used as the substituted molecule 5 having catalytic activity or an additional molecule to be added.
- the fine particle assembly layer 6 is missing in a partial region of the surface of the substrate 1, and the substrate 1 is exposed in the missing portion 8.
- a substrate made of a material having high electrical conductivity is used as the substrate 1, and this is used as an electrode.
- the electrode is nano-sized. A partially exposed structure in width can be formed.
- FIG. 4 is a schematic cross-sectional view showing a flow of a manufacturing process of a fine particle structure / substrate composite member having a three-dimensional raised structure based on the present embodiment.
- a clean substrate 1 such as a silicon substrate having a mirror-finished surface and a thermal oxide film formed on the surface is prepared.
- a dispersion 11 is prepared by dispersing the fine particles 2 in an appropriate solvent with the surface covered with the protective film molecules 3.
- the solvent is not particularly limited, and for example, toluene, cyclohexane, chloroform or the like is used.
- a fine particle layer 4 composed of the fine particles 2 covered with the protective film molecules 3 is formed on the substrate 1 using the dispersion liquid 11.
- a method for forming the fine particle layer 4 is not particularly limited, and a coating method, a printing method, a Langmuir-Blodget method (LB method), a stamp method, a casting method, a lift-off method, an immersion method, or the like is appropriately used.
- a dispersion liquid 11 in which metal fine particles 2 coated with a protective film molecule 3 are dispersed in a solvent such as toluene or chloroform is spread on a static water surface, and then the solvent is evaporated to form a protective film molecule 3.
- a fine particle layer made of metal fine particles 2 coated with is formed on the water surface.
- the fine particle layer is transferred onto the substrate 1 disposed below the water surface by a water surface descent method or the like.
- the LB method has an advantage that the film thickness can be easily controlled by the concentration and amount of the dispersion 11 developed on the water surface, the surface pressure, etc., and a single layer film of the fine particles 2 covered with the protective film molecules 3 is formed. Is also possible.
- a fine particle film composed of fine particles 2 covered with protective film molecules 3 is formed on a solid surface or water surface by a casting method or an LB method.
- the fine particle film is once transferred onto the surface of a transfer medium made of polydimethylsiloxane and the like, and the transfer medium is pressed onto the substrate 1 like a stamp, and the fine particle layer 4 is disposed on the surface of the substrate 1.
- the solvent is evaporated, and the fine particle layer 4 composed of the fine particles 2 covered with the protective film molecules 3 is directly formed on the substrate 1.
- the method for disposing the dispersion liquid 11 on the substrate 1 is not particularly limited, but a cast coater method, a spray coater method, a spin coat method, or the like can be used as a coating method, and an ink jet printing method or a screen printing method can be used as a printing method. Further, an offset printing method, a gravure printing method, or the like can be used. In the casting method, the dispersion 11 is dropped on the substrate 1 and the solvent is gradually evaporated.
- the substrate 1 is immersed in the dispersion 11 for several minutes to several hours, and then the solvent is evaporated.
- a photoresist layer is formed by patterning on the substrate 1 by lithography or the like in advance, a fine particle layer is formed on the entire surface of the substrate 1 including the photoresist layer, and then the photoresist layer is deposited thereon.
- the patterned fine particle layer is obtained by removing together with the fine particle layer and selectively leaving the fine particle layer directly deposited on the substrate 1.
- the substrate 1 on which the fine particle layer 4 composed of the fine particles 2 covered with the protective film molecules 3 is contacted with a solution or gas containing the substitution molecules 5.
- the protective film molecules 3 are replaced by the replacement molecules 5a.
- the distance between the fine particles 2 changes, and the fine particle aggregate layer 6a having the three-dimensional raised structure 7 is formed.
- the protective film molecule 3 is used for the purpose of preventing the fusion and aggregation of the fine particles 2. Therefore, when the fine particles 2 are fine particles that do not aggregate and aggregate with each other and cause fusion or aggregation, it is not necessary to use the protective film molecules 3. In this case, since the special molecule does not need to be displaced by replacing the protective film molecule 3 previously bonded to the fine particle 2, the selection of the special molecule becomes easier (the bond that binds to the fine particle 2). (There is no restriction that the force needs to be stronger than the protective film molecule 3 that binds to the fine particles 2 first.)
- FIG. 5 is a structural formula showing an example of the substituted molecule 5 used for producing the fine particle structure / substrate composite member of the present embodiment.
- Substitution molecules A and B shown in FIGS. 5A and 5B are examples of substitution molecules having one sulfanyl group —SH as a binding site for binding to the fine particles 2.
- a substituted molecule C shown in FIG. 5C is an example of a substituted molecule having two sulfanyl groups as binding sites for binding to the fine particles 2.
- substitution molecules A and B have only one binding site that binds to the microparticles 2, they bind to the microparticles 2 at one end (binding site) of the molecules in the microparticle assembly layer 6, and at the other end, It binds to the end of the substituted molecule bound to the adjacent fine particle 2 by intermolecular force or the like.
- the mechanical strength of the three-dimensional raised structure 7 is weak as compared with the case of binding to the fine particles 2 so as to bridge between the two fine particles at both ends of the molecule like the substituted molecule C. .
- Such a substituted molecule has the same mechanical strength as a substituted molecule having two binding sites if the other end functions as a linking group that connects the substituted molecules with each other through a chemical bond.
- a three-dimensional raised structure can be formed.
- the other end of the substituted molecules A and B is a terpyridyl group that can be a ligand of an organometallic complex.
- the central metal ion necessary for forming the complex structure is supplemented, the complex structure is formed between the adjacent substituted molecules 5, and the substituted molecules 5 can be connected by chemical bonds (for example, JP 2008-200811A). No. 153257).
- FIG. 6 is a structural formula showing a post-processing step of the substituted molecule 5 added to the fine particle structure / substrate composite member manufacturing step shown in FIG. 4 in order to form the complex structure.
- the substrate 1 is immersed in an ethanol solution containing central metal ions.
- the substituted molecule A or B in which the ligand is a terpyridyl group Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Ru 2+, etc. are supplemented as central metal ions, A bisterpyridyl complex is formed and the fine particles 2 are crosslinked.
- the fine particle assembly layer 6 is formed in a donut shape, a circular shape, or a honeycomb shape by a very simple process of causing the substitution molecules 5 to act on the fine particle layer 4 formed on the substrate 1. It is possible to form on the substrate 1 a three-dimensional microstructure that bulges or the like, or a microstructure that has a nano-sized crack or gap.
- the fine particle assembly layer described in the embodiment is manufactured on the surface of various substrates, and the fine particle assembly layer and the three-dimensional layer are formed using a scanning electron microscope (SEM) and an atomic force microscope (AFM). The result of observing the raised structure will be described.
- SEM scanning electron microscope
- AFM atomic force microscope
- gold fine particles having a diameter estimated from a scanning electron microscope observation image of 4.7 ⁇ 1.1 nm were used as the fine particles 2.
- an alkylamine having a molecular length of about 0.6 nm was used as the protective film molecule 3
- gold fine particles 2 covered with the protective film 3 having a thickness of about 0.6 nm were used.
- Example 1 the fine particle assembly layer 6 was formed on the surface of the silicon substrate on which the thermal oxide film was formed.
- a silicon substrate having a mirror-finished surface and a thermal oxide film formed on the surface was prepared as the substrate 1.
- a fine particle film composed of the fine particles 2 coated with the protective film molecules 3 was produced by the Langmuir Blodget (LB) method.
- the gold fine particles 2 coated with the protective film molecules 3 were dispersed in toluene at a concentration of 30% by mass. After 20 ⁇ L of this dispersion was cast onto the water surface with a pipette, toluene was evaporated to form a fine particle film composed of the fine particles 2 covered with the protective film molecules 3 on the water surface.
- the 30% by mass is a mass percentage including the protective film molecules, and the main component is due to the mass of the gold fine particles.
- the fine particle film was transferred onto the silicon substrate 1 to obtain a fine particle layer 4e composed of the fine particles 2 covered with the protective film molecules 3.
- the substrate 1 on which the fine particle layer 4 was formed was immersed in this solution for a predetermined time. Thereafter, it was taken out and washed with methanol. By this treatment, the protective film molecules 3 are replaced by the replacement molecules A, and the fine particle aggregate layer 6e having the three-dimensional raised structure 7 is generated.
- FIG. 7 (a) and 7 (b) are SEM observation images of the fine particle assembly layer 6e obtained as described above.
- FIG. 7A shows the case where the immersion time is 2 hours
- FIG. 7B shows the case where the immersion time is 18 hours.
- the molecular length of the substituted molecule A is about 1.8 nm, which is larger than the thickness of the protective film (molecular length of the protective film molecule) of about 0.6 nm.
- Example 1 is an example in which the molecular length of the substitution molecule 5 e shown in FIG. 3 is longer than the molecular length of the protective film molecule 3.
- the interval between the fine particles 2 is expanded by the long substitution molecules 5e that enter between the adjacent fine particles 2.
- the distance between the centers of the fine particles 2 in the fine particle assembly layer 6 e is larger than the distance between the centers of the fine particles 2 in the fine particle layer 4. Therefore, the surface area of the fine particle aggregate layer 6 e is also larger than the surface area of the original fine particle layer 4.
- a three-dimensional shape in which a part of the fine particle assembly layer 6e that does not fit on the plane partially rises must be taken.
- a three-dimensional raised structure 7 such as a donut shape, a circular shape, or a honeycomb shape is formed.
- FIG. 7C is an AFM observation image of the three-dimensional raised structure 7 raised in a donut shape.
- the height of the three-dimensional raised structure 7 is about 5 ⁇ m.
- FIG. 8 shows an SEM observation image (a) and an AFM observation image (b) of the fine particle aggregate layer 6e having the three-dimensional raised structure 7 raised in a honeycomb shape obtained under the same conditions. From the AFM observation image, it was found that the height of the three-dimensional raised structure 7 raised like a honeycomb was about 5 to 10 ⁇ m.
- the conditions for making the donut-like structure shown in FIG. 7 and the honeycomb-like structure shown in FIG. 8 completely unknown are unknown.
- the donut-like structure is formed relatively anywhere on the substrate, whereas the honeycomb-like structure tends to be formed in the central portion of the substrate. Further, although there is some difference in the immersion time at which each structure can be easily formed, it is impossible to control so that one structure is necessarily generated only by adjusting the immersion time.
- Example 2 the fine particle aggregate layer 6e was formed on the surface of the silicon substrate patterned into the region where the gold layer was formed and the region where the thermal oxide film was exposed.
- a silicon substrate having a mirror-finished surface and a thermal oxide film formed on the surface was prepared.
- Gold was vapor-deposited on a part of the surface of the silicon substrate by a vacuum deposition method, and the surface of the silicon substrate was patterned into a region where the gold layer was disposed and a region where the thermal oxide film was exposed. This silicon substrate was used as the substrate 1.
- a fine particle film composed of the fine particles 2 covered with the protective film molecules 3 was produced by the LB method. That is, after 15 ⁇ L of the above dispersion was cast onto the water surface with a pipette, the solvent was evaporated to form a fine particle film composed of the fine particles 2 coated with the protective film molecules 3 on the water surface.
- this fine particle film was transferred onto the silicon substrate 1 to obtain a fine particle layer 4 composed of the fine particles 2 covered with the protective film molecules 3.
- the fine particle film was disposed so as to extend over both the region where the gold layer was formed and the region where the thermal oxide film was exposed.
- Example 2 the substrate 1 on which the fine particle layer 4 was formed was immersed in a methanol solution of the substituted molecule A for 22 hours. Thereafter, it was taken out and washed with methanol. By this step, the protective film molecules 3 are replaced by the replacement molecules A, and the fine particle aggregate layer 6e having the three-dimensional raised structure 7 is generated.
- FIG. 9 is an SEM observation image of the fine particle aggregate layer 6e obtained as described above.
- the fine particle aggregate layer 6e having the three-dimensional raised structure 7 raised in a substantially circular shape was formed.
- the fine particle aggregate layer 6e having the three-dimensional raised structure 7 raised in a more complicated shape is formed.
- FIG. 9 is an observation image obtained by dividing the substrate 1 on which the fine particle aggregate layer 6e is formed by the region where the thermal oxide film is exposed and observing the cross section with an SEM. It can be seen that the fine particle aggregate layer 6e is raised and the three-dimensional raised structure 7 having a hollow structure is formed.
- Example 3 various self-assembled monolayers were formed on the surface of a mica substrate having a gold layer formed on the entire surface, and a fine particle assembly layer 6e was formed on the monolayer.
- the formed self-assembled monolayer is (A) 1,10-decanedithiol, (B) 4-sulfanylpyridine, (C) A monomolecular film of three kinds of molecules, 2-nitro-4-trifluoromethylbenzene-1-thiol. These three substrates were each referred to as a substrate 1.
- a fine particle film composed of the fine particles 2 covered with the protective film molecules 3 was produced by the LB method. That is, after 15 ⁇ L of the above dispersion was cast onto the water surface with a pipette, the solvent was evaporated to form a fine particle film composed of the fine particles 2 coated with the protective film molecules 3 on the water surface.
- the fine particle film was transferred onto the silicon substrate 1 to obtain a fine particle layer 4e composed of the fine particles 2 covered with the protective film molecules 3.
- Example 2 the substrate 1 on which the fine particle layer 4e was formed was immersed in a methanol solution of the substituted molecule A for 22 hours. Thereafter, it was taken out and washed with methanol. By this step, the protective film molecules 3 are replaced by the replacement molecules A, and the fine particle aggregate layer 6e having the three-dimensional raised structure 7 is generated.
- (X) in FIG. 10 is an SEM observation image of the fine particle layer 4e composed of the fine particles 2 covered with the protective film molecules 3 before being substituted with the substitution molecules A.
- 10 (a) to 10 (c) the protective film molecule 3 of the fine particle layer 4 formed on the self-assembled monomolecular film of (a) to (c) above is replaced with the replacement molecule A. It is the observation image which observed the fine particle aggregate layer 6e after by SEM.
- the brightly observed part is a raised part.
- a mesh-like ridge structure is generated
- a linear ridge structure extending slightly while being curved is generated.
- the raised portion has a large width, and a raised structure in which the upper part is cleaved is generated.
- the unevenness of the raised structure is formed in the fine particle assembly layer 6 e by the substitution with the substitution molecule A.
- These three-dimensional raised structures 7 differ depending on the type of the underlying self-assembled monolayer. This indicates that the shape of the three-dimensional raised structure 7 can be controlled by the type of molecules constituting the monomolecular film (type of terminal functional group).
- Example 4 a fine particle assembly layer was formed on a cleaved mica substrate having a thickness of about 0.1 mm.
- the mica substrate was prepared as the substrate 1.
- a fine particle film composed of the fine particles 2 covered with the protective film molecules 3 was produced by the LB method.
- the gold fine particles 2 coated with the protective film molecules 3 were dispersed in cyclohexane at a concentration of 2% by mass. After 60 ⁇ L of this dispersion was cast onto the water surface with a pipette, the solvent was evaporated, and a fine particle film composed of the fine particles 2 covered with the protective film molecules 3 was formed on the water surface.
- the fine particle film was transferred onto a mica (mica) substrate 1 to obtain a fine particle layer 4e composed of fine particles 2 covered with protective film molecules 3.
- the substituted molecule 5 As the substituted molecule 5, the substituted molecule C (see FIG. 4C; butanedithiol) was dissolved in methanol at a concentration of 1 mM. The substrate 1 on which the fine particle layer 4e was formed was immersed in this solution for 84 hours. Thereafter, it was taken out and washed with methanol. By this treatment, the protective film molecules 3 are replaced by the replacement molecules C, and a fine particle aggregate layer having the missing portion 8 is formed.
- FIG. 11 is an SEM observation image of the fine particle layer 4e composed of the fine particles 2 covered with the protective film molecules 3 before being substituted with the substitution molecules C.
- FIG. 11A is an observation image obtained by observing the fine particle assembly layer with an SEM after the protective film molecules 3 of the fine particle layer 4e are replaced with the replacement molecules C.
- the molecular length of the substituted molecule C is about 0.6 nm, which is smaller than the distance of about 1.2 nm between the adjacent fine particles 2 in the fine particle layer 4e.
- Example 4 is an example in which the molecular length of the substitution molecule 5 having binding sites at both ends is shorter than the length twice the molecular length of the protective film molecule 3.
- the distance between the fine particles 2 is reduced by the short substituent molecules C entering between the adjacent fine particles 2.
- the distance between the centers of the fine particles 2 in the fine particle assembly layer is smaller than the distance between the centers of the fine particles 2 in the fine particle layer 4e. Therefore, the surface area of the fine particle assembly layer is also smaller than the surface area of the original fine particle layer 4e. For this reason, the fine particle aggregate layer cannot cover the same substrate area as the fine particle layer 4e, and partial cracks or gaps are formed in various places of the fine particle aggregate layer, and the substrate 1 is exposed at this place. To do.
- the observation image of the fine particle assembly layer after substitution with the substitution molecule C ((a) in FIG. 11)
- the observation image ((x) in FIG. 11) of the fine particle layer 4e before substitution with the substitution molecule C is obtained.
- missing portions such as partial cracks and gaps occurring in various parts of the fine particle assembly layer 6 are observed as dark regions.
- a fine particle aggregate layer having a characteristic three-dimensional microstructure can be easily produced without using lithography or the like.
- This fine particle structure / substrate composite member having a three-dimensional microstructure is used as an electronic material such as a new sensor, an electrochemical material such as an electrode, and a catalyst depending on the material and size of the fine particle and the material of the substrate. Is possible.
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Abstract
Description
滑らかな表面を有する基体を用意する工程と、
微粒子が前記表面に沿って密に並んでいる微粒子層を形成する工程と、
前記微粒子に特定の分子を結合させることによって、前記特定の分子が結合した前記微粒子からなる微粒子集合体層に前記微粒子層を変化させ、
隣り合う前記微粒子間の中心間距離を増加させることによって、一部の領域に前記微粒子集合体層が前記表面から***してなる三次元微小構造を生成させるか、
又は、
隣り合う前記微粒子間の中心間距離を減少させることによって、前記表面の一部の領域において前記微粒子集合体層が欠落し、この欠落部において前記基体が露出している微小構造を生成させる
工程と
を有する、微粒子構造体/基体複合部材の製造方法に係わるものである。
滑らかな表面を有する基体と、
前記表面に沿って微粒子が密に並んでいる微粒子層において、前記微粒子に特定の分子が結合することによって生じ、
隣り合う前記微粒子間の中心間距離が増加することによって、一部の領域に層が前記表面から***してなる三次元微小構造が形成されているか、
又は、
隣り合う前記微粒子間の中心間距離が減少することによって、前記表面の一部の領域において層が欠落し、この欠落部において前記基体が露出している微小構造が形成されているかのいずれか一方である、前記特定の分子が結合した前記微粒子からなる微粒子集合体層と
を有する、微粒子構造体/基体複合部材に係わるものである。
滑らかな表面を有する基体を用意する工程と、
微粒子が前記表面に沿って密に並んでいる微粒子層を形成する工程と
を行う。前記基体の前記表面は、隣り合う前記微粒子同士が互いに十分に接触できる程度に滑らかであることが必要である。次に、このように準備された前記微粒子層に特定の分子を作用させることによって、前記微粒子層を、表面に前記特定の分子が結合した前記微粒子からなる微粒子集合体層に変化させる。このとき、前記特定の分子の分子長に応じて、前記微粒子集合体層において隣り合う前記微粒子間の中心間距離が変化する。
PbS、PbSe、PbTe、InP、InAs、InSb、GaP、
GaAs、GaSb、ZnS、ZnSe、ZnTe、CdS、CdSe、
CdTe
-S-S-…Au、Ag、Pt、Pd、Cu、Fe、SnS、SnSe、SnTe、
PbS、PbSe、PbTe、InP、InAs、InSb、GaP、
GaAs、GaSb、ZnS、ZnSe、ZnTe、CdS、CdSe、
CdTe
-SeH …Au、Ag、Pt、Pd、Cu、Fe、SnS、SnSe、SnTe、
PbS、PbSe、PbTe、InP、InAs、InSb、GaP、
GaAs、GaSb、ZnS、ZnSe、ZnTe、CdS、CdSe、
CdTe
-TeH …Au、Ag、Pt、Pd、Cu、Fe、SnS、SnSe、SnTe、
PbS、PbSe、PbTe、InP、InAs、InSb、GaP、
GaAs、GaSb、ZnS、ZnSe、ZnTe、CdS、CdSe、
CdTe
-NH2 …Au、Ag、Pt、Pd、Cu、Fe、SnS、SnSe、SnTe、
PbS、PbSe、PbTe、InP、InAs、InSb、GaP、
GaAs、GaSb、ZnS、ZnSe、ZnTe、CdS、CdSe、
CdTe、TiO2、ZnO、In2O3、NiO、VO2、SnO2
-PR1R2…Au、Pd、Pt、Rh、Ni、TiO2、ZnO、In2O3、
NiO、VO2、SnO2
-CN …Au
-SCN …Au、Ag、Pt、Pd、Cu、Fe
-NC …Au、Ag、Pt、Pd
-COOH…Au、Ag、TiO2、ZnO、In2O3、NiO、VO2、SnO2
(a)1,10-デカンジチオール、
(b)4-スルファニルピリジン、
(c)2-ニトロ-4-トリフルオロメチルベンゼン-1-チオール
の3種類の分子の単分子膜である。この3つの基板をそれぞれ基板1とした。
Claims (16)
- 滑らかな表面を有する基体を用意する工程と、
微粒子が前記表面に沿って密に並んでいる微粒子層を形成する工程と、
前記微粒子に特定の分子を結合させることによって、前記特定の分子が結合した前記微粒子からなる微粒子集合体層に前記微粒子層を変化させ、
隣り合う前記微粒子間の中心間距離を増加させることによって、一部の領域に前記微粒子集合体層が前記表面から***してなる三次元微小構造を生成させるか、
又は、
隣り合う前記微粒子間の中心間距離を減少させることによって、前記表面の一部の領域において前記微粒子集合体層が欠落し、この欠落部において前記基体が露出している微小構造を生成させる
工程と
を有する、微粒子構造体/基体複合部材の製造方法。 - 前記微粒子として、微粒子同士の凝集又は融着を防止する保護膜分子で被覆した微粒子を用い、この保護膜分子を前記特定の分子で置換する、請求項1に記載した微粒子構造体/基体複合部材の製造方法。
- 前記微粒子として、粒子径がナノサイズであるナノ粒子を用いる、請求項1に記載した微粒子構造体/基体複合部材の製造方法。
- 前記特定の分子として、前記微粒子に結合する結合部位としてスルファニル基-SH、ジスルファニル基-S-S-、イソシアノ基-NC、チオシアナト基-SCN、カルボキシル基-COOH、アミノ基-NH2、シアノ基-CN、セラニル基-SeH、テラニル基-TeH、又はホスフィノ基-PR1R2(R1およびR2はHまたは有機基)を有する分子を用いる、請求項1に記載した微粒子構造体/基体複合部材の製造方法。
- 前記特定の分子として機能性分子を用いる、請求項1に記載した微粒子構造体/基体複合部材の製造方法。
- 前記微粒子層を塗布法、印刷法、ラングミュア-ブロジェット法、スタンプ法、キャスティング法、リフトオフ法、又は浸漬法によって形成する、請求項1に記載した微粒子構造体/基体複合部材の製造方法。
- 滑らかな表面を有する基体と、
前記表面に沿って微粒子が密に並んでいる微粒子層において、前記微粒子に特定の分子が結合することによって生じ、
隣り合う前記微粒子間の中心間距離が増加することによって、一部の領域に層が前記表面から***してなる三次元微小構造が形成されているか、
又は、
隣り合う前記微粒子間の中心間距離が減少することによって、前記表面の一部の領域において層が欠落し、この欠落部において前記基体が露出している微小構造が形成されているか
のいずれか一方である、前記特定の分子が結合した前記微粒子からなる微粒子集合体層と
を有する、微粒子構造体/基体複合部材。 - 前記微粒子層において前記微粒子は微粒子同士の凝集又は融着を防止する保護膜分子で被覆されており、この保護膜分子が前記特定の分子で置換されている、請求項7に記載した微粒子構造体/基体複合部材。
- 前記微粒子が、粒子径がナノサイズのナノ粒子である、請求項7に記載した微粒子構造体/基体複合部材。
- 前記特定の分子が、前記微粒子に結合する結合部位としてスルファニル基-SH、ジスルファニル基-S-S-、イソシアノ基-NC、チオシアナト基-SCN、カルボキシル基-COOH、アミノ基-NH2、シアノ基-CN、セラニル基-SeH、テラニル基-TeH、又はホスフィノ基-PR1R2(R1およびR2はHまたは有機基)を有する分子である、請求項7に記載した微粒子構造体/基体複合部材。
- 前記特定の分子が機能性分子である、請求項7に記載した微粒子構造体/基体複合部材。
- 前記微粒子及び前記機能性分子が導電性を有する、請求項11に記載した微粒子構造体/基体複合部材。
- 前記三次元微小構造が形成されている前記微粒子集合体層が電極として用いられる、請求項12に記載した微粒子構造体/基体複合部材。
- 前記機能性分子がフッ素含有分子であって、前記微粒子集合体層が超撥水性表面を形成している、請求項11に記載した微粒子構造体/基体複合部材。
- 前記微粒子及び/又は前記機能性分子が触媒機能を有し、前記三次元微小構造が形成されている前記微粒子集合体層が触媒として機能する、請求項11に記載した微粒子構造体/基体複合部材。
- 前記基体が電極であり、前記微粒子及び前記機能性分子に導電性がなく、前記欠落部において前記電極が露出している、請求項7に記載した微粒子構造体/基体複合部材。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09830465A EP2354086A1 (en) | 2008-12-04 | 2009-12-04 | Fine-particle structure/substrate composite member and process for producing same |
SG2011039286A SG171863A1 (en) | 2008-12-04 | 2009-12-04 | Fine-particle structure/substrate composite member and method for producing same |
CN200980154409.6A CN102282095B (zh) | 2008-12-04 | 2009-12-04 | 微细颗粒结构/基材复合部件及其生产方法 |
US13/131,342 US8859449B2 (en) | 2008-12-04 | 2009-12-04 | Fine-particle structure/substrate composite member and method for producing same |
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JP2008309445A JP2010131700A (ja) | 2008-12-04 | 2008-12-04 | 微粒子構造体/基体複合部材及びその製造方法 |
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EP (1) | EP2354086A1 (ja) |
JP (1) | JP2010131700A (ja) |
KR (1) | KR20110089853A (ja) |
CN (1) | CN102282095B (ja) |
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JP2011100779A (ja) * | 2009-11-04 | 2011-05-19 | V Technology Co Ltd | 半導体装置及びその製造方法 |
JP5857767B2 (ja) * | 2012-02-02 | 2016-02-10 | 東レ株式会社 | 積層基板 |
CN111122022B (zh) * | 2019-12-30 | 2023-08-15 | 浙江清华柔性电子技术研究院 | 功能薄膜及其制备方法、柔性压力传感器及其制备方法 |
CN111122021B (zh) * | 2019-12-30 | 2023-08-15 | 浙江清华柔性电子技术研究院 | 柔性复合薄膜及制备方法、柔性压力传感器及制备方法 |
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US20110230336A1 (en) | 2011-09-22 |
SG171863A1 (en) | 2011-07-28 |
CN102282095B (zh) | 2014-04-23 |
KR20110089853A (ko) | 2011-08-09 |
US8859449B2 (en) | 2014-10-14 |
JP2010131700A (ja) | 2010-06-17 |
EP2354086A1 (en) | 2011-08-10 |
CN102282095A (zh) | 2011-12-14 |
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