WO2011135924A1 - 金属ナノ粒子配列構造体、その製造装置及びその製造方法 - Google Patents
金属ナノ粒子配列構造体、その製造装置及びその製造方法 Download PDFInfo
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- WO2011135924A1 WO2011135924A1 PCT/JP2011/054965 JP2011054965W WO2011135924A1 WO 2011135924 A1 WO2011135924 A1 WO 2011135924A1 JP 2011054965 W JP2011054965 W JP 2011054965W WO 2011135924 A1 WO2011135924 A1 WO 2011135924A1
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- metal nanoparticle
- nanoparticle array
- array structure
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- substrate
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 402
- 238000004519 manufacturing process Methods 0.000 title claims description 76
- 239000000758 substrate Substances 0.000 claims abstract description 151
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims description 104
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 40
- 239000010931 gold Substances 0.000 claims description 40
- 229910052737 gold Inorganic materials 0.000 claims description 40
- 239000002105 nanoparticle Substances 0.000 claims description 33
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 32
- 239000010409 thin film Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 14
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- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
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- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000034 method Methods 0.000 description 31
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- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 16
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- 239000003054 catalyst Substances 0.000 description 10
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- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 6
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
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- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical group SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
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- 229910000077 silane Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000000054 nanosphere lithography Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 1
- ISPSHPOFLYFIRR-UHFFFAOYSA-N trihexylsilicon Chemical compound CCCCCC[Si](CCCCCC)CCCCCC ISPSHPOFLYFIRR-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B50/00—Methods of creating libraries, e.g. combinatorial synthesis
- C40B50/14—Solid phase synthesis, i.e. wherein one or more library building blocks are bound to a solid support during library creation; Particular methods of cleavage from the solid support
- C40B50/18—Solid phase synthesis, i.e. wherein one or more library building blocks are bound to a solid support during library creation; Particular methods of cleavage from the solid support using a particular method of attachment to the solid support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0147—Film patterning
- B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
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- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B40/00—Libraries per se, e.g. arrays, mixtures
Definitions
- the present invention relates to a metal nanoparticle array structure, a manufacturing apparatus thereof, and a manufacturing method thereof.
- a new function can be developed by integrating materials with nanoscale size. For this reason, the integration technology and the integrated structure are notable technologies and materials.
- metal nanoparticles having a particle diameter of 1 to 100 nm can generate localized light (hereinafter, near-field light) having a size corresponding to the radius. Therefore, a metal nanoparticle array structure having metal nanoarrays arranged two-dimensionally on a substrate with the interval between metal nanoparticles set to 1 to 10 nm is a large electric field or very bright in the gap between the metal nanoparticles. Near-field light can be generated.
- This metal nanoparticle array structure is expected to be applied to optical waveguides, photochemical reaction reactors, optical devices, high-sensitivity sensors, and catalysts. In order to apply to these, it is necessary to use a metal nanoparticle array structure in which the size, shape and interval of the metal nanoparticles are uniform, so the size, shape and interval of the metal nanoparticles are controlled. This is the technical key.
- Non-Patent Documents 1 to 3 nanosphere lithography
- electron beam lithography Non-Patent Document 4
- the lithographic apparatus is expensive and produces a large-scale structure. Is a difficult point.
- Non-Patent Documents 5 to 8 the Langmuller method
- Non-Patent Documents 9 to 10 the Langmuir-Blodgett method
- Non-Patent Document 11 the dip coating method
- Patent Document 1 the Langmuller method
- Patent Document 13 an electrophoresis method
- Patent Document 12 a solvent evaporation method
- these methods do not have a strong immobilization means such as a chemical bond between the metal nanoparticle array structure and the fixed substrate, there is a problem that the metal nanoparticle array structure is easily detached from the fixed substrate. is there.
- Non-Patent Documents 14 to 15 thiol bonds
- CN bonds Non-Patent Document 16
- coordinate bonds Non-Patent Documents 17 to 18
- the coverage is the ratio of the area occupied by the metal nanoparticle array structure within a specific area.
- the present invention has been made to solve such problems of the prior art, and includes a metal nanoparticle array in which a plurality of metal nanoparticles having a uniform size and shape are arranged, and the metal nanoparticles are provided. It is an object of the present invention to provide a metal nanoparticle array structure in which the array is firmly fixed on a substrate by a chemical bond or the like and the metal nanoparticle array has a high coverage, a manufacturing apparatus, and a manufacturing method thereof.
- the present invention provides the following metal nanoparticle array structure, its manufacturing method and manufacturing apparatus.
- the metal nanoparticle array structure according to the present invention includes a substrate, an immobilization layer formed on one surface of the substrate, and a metal nanoparticle array structure formed on one surface of the immobilization layer.
- the metal nanoparticle array is formed such that a plurality of metal nanoparticles are arranged at equal intervals, and the metal nanoparticles are bonded to each other by a modification provided on the surface thereof.
- the metal nanoparticles are immobilized on one surface of the immobilization layer by chemical bonding.
- the metal nanoparticle array structure of the present invention is characterized in that the interval between the metal nanoparticles is 1 to 10 nm.
- the metal nanoparticle array structure of the present invention is characterized in that the metal nanoparticles have a particle size of 1 to 100 nm.
- the metal nanoparticle array structure of the present invention is characterized in that the metal nanoparticles are made of gold.
- the metal nanoparticle array structure of the present invention is characterized in that the modification part is an organic molecule having a thiol group, and the thiol group is bonded to the metal nanoparticle.
- the metal nanoparticle array structure of the present invention is characterized in that the organic molecule of the modification part has an alkyl chain having 6 to 20 carbons.
- the immobilization layer is composed of an organic molecule having at least two thiol groups, and at least one thiol group is disposed on one side and the other side of the immobilization layer, respectively.
- the thiol group on the other side is bonded to the substrate.
- the metal nanoparticle array structure of the present invention is characterized in that the organic molecule of the immobilization layer has an alkyl chain having 6 or more and 20 or less carbon.
- the metal nanoparticle array structure of the present invention is characterized in that the substrate is a conductive substrate.
- the metal nanoparticle array structure of the present invention is characterized in that the substrate is an insulating substrate having a conductive thin film formed on one surface.
- the apparatus for producing a metal nanoparticle array structure includes a liquid tank, a lid that covers the opening of the liquid tank, two electrode portions that can be disposed opposite to each other in the liquid tank, and the two electrodes.
- a liquid level position moving means capable of moving the position of the liquid level of the reaction liquid filling the liquid tank with respect to the electrode unit.
- the metal nanoparticle array structure manufacturing apparatus of the present invention is characterized in that the liquid surface position moving means is a hole provided in the lid and capable of changing an opening diameter.
- the liquid surface position moving means is a lifting portion that can lift one electrode portion of the two electrode portions toward the lid portion.
- the electrode is filled with the reaction liquid and immersed in the reaction liquid.
- a voltage is applied to the two electrode parts from the first step of arranging the electrodes opposite to each other via a wiring to the two electrode parts, and the position of the liquid surface of the reaction liquid with respect to the electrode parts And a second step of forming an organic nanoparticle array on one surface of the one electrode part.
- the method for producing a metal nanoparticle array structure of the present invention is characterized in that the moving speed of the liquid surface of the reaction solution is 0.02 mm / s or less.
- the method for producing a metal nanoparticle array structure of the present invention uses a volatile solvent as the solvent in the first step, and volatilizes the volatile solvent at the time of voltage application in the second step. The position of the liquid surface of the reaction liquid with respect to the electrode part is moved.
- the volatile solvent is water, alcohols, ketones, esters, halogenated solvents, aliphatic hydrocarbons, or aromatic hydrocarbons, or their It is characterized by being any of the mixtures.
- the method for producing a metal nanoparticle array structure of the present invention is characterized in that the volatile solvent contains an inorganic salt, an organic salt, or both.
- the second step when applying a voltage, one of the two electrode portions is pulled up in the direction of the lid, and the electrode portion The position of the liquid level of the reaction liquid with respect to is moved.
- the method for producing a metal nanoparticle array structure of the present invention is characterized by using metal nanoparticles having a particle size of 1 to 100 nm.
- the method for producing a metal nanoparticle array structure of the present invention is characterized by using metal nanoparticles modified with organic molecules.
- a substrate having an immobilization layer is used as one of the two electrode units, and one surface side of the immobilization layer is opposed to the other electrode unit. It is characterized by arranging them.
- the method for producing a metal nanoparticle array structure of the present invention is characterized in that the substrate is made of a conductive substrate.
- the method for producing a metal nanoparticle array structure according to the present invention is characterized in that the substrate comprises an insulating substrate having a conductive thin film formed on one side.
- the method for producing a metal nanoparticle array structure of the present invention is characterized in that a carbon electrode is used as the other electrode part.
- the method for producing a metal nanoparticle array structure of the present invention is characterized in that after the second step, the organic nanoparticle array is annealed in a temperature range of 30 to 80 ° C.
- the metal nanoparticle array structure includes a substrate, an immobilization layer formed on one surface of the substrate, and a metal nanoparticle array structure formed on one surface of the immobilization layer.
- the metal nanoparticle array is formed such that a plurality of metal nanoparticles are arranged at equal intervals, and the metal nanoparticles are joined to each other by a modification provided on the surface thereof. Since the metal nanoparticles are fixed to one surface of the fixed layer by chemical bonds, the distance between the metal nanoparticles is controlled to be constant on the nanoscale and the chemical bonds with the substrate are easily formed.
- the modification part is an organic molecule having a thiol group, and the thiol group is bonded to the metal nanoparticle, so that the metal nanoparticles are firmly bonded to each other.
- the apparatus for producing a metal nanoparticle array structure includes a liquid tank, a lid that covers the opening of the liquid tank, two electrode portions that can be disposed opposite to each other in the liquid tank, and the two electrodes.
- a power supply unit connected to the unit via a wiring, and a configuration including a liquid level position moving means capable of moving the position of the liquid level of the reaction liquid filling the liquid tank relative to the electrode unit,
- a metal with a high coverage that forms a nucleus of two-dimensional arrangement of metal nanoparticles at the gas-liquid interface exposed by moving the liquid surface, and is easily fixed firmly on the substrate by chemical bonding or the like.
- a metal nanoparticle array structure having a nanoparticle array can be provided.
- the reaction liquid is filled in a liquid tank and then completely immersed in the reaction liquid.
- a first step of disposing the two electrode portions opposite to each other, and applying a voltage to the two electrode portions from a power supply portion connected to the two electrode portions via wiring, and a solution of the reaction liquid to the electrode portions And a second step of forming an organic nanoparticle array on one surface of the one electrode portion by moving the position of the surface, so that the charged metal nanoparticles in the reaction solution are applied to the one surface of the electrode portion.
- a metal nanoparticle array structure in which the metal nanoparticle array is firmly fixed on the substrate and has a high coverage is provided by promoting chemical bond formation through electrical movement and electrical interaction. be able to.
- the method for producing a metal nanoparticle array structure of the present invention uses a volatile solvent as the solvent in the first step, and volatilizes the volatile solvent at the time of voltage application in the second step. Since the position of the liquid surface of the reaction liquid with respect to the electrode part is moved, the core of the two-dimensional arrangement of metal nanoparticles is formed around the gas-liquid interface by evaporating the volatile solvent, and the interval between the metal nanoparticles. It is possible to provide a metal nanoparticle array structure in which the metal nanoparticle array having a substantially constant is fixed on the substrate firmly by chemical bonding or the like, and the metal nanoparticle array has a high coverage.
- the second step when applying a voltage, one of the two electrode portions is pulled up in the direction of the lid, and the electrode portion Since the position of the liquid surface of the reaction liquid with respect to the structure is moved, a metal nanoparticle array in which the core of the two-dimensional array of metal nanoparticles is formed around the gas-liquid interface and the interval between the metal nanoparticles is almost constant. It is possible to provide a metal nanoparticle array structure that is firmly fixed on a substrate by chemical bonding or the like and that has a high coverage of the metal nanoparticle array.
- FIG. 1A and 1B are diagrams illustrating an example of a metal nanoparticle array structure according to an embodiment of the present invention, in which FIG. 1A is a plan view, and FIG. 1B is a line AA ′ in FIG. 1 (c) is an enlarged view of a portion B in FIG. 1 (a), and FIG. 1 (d) is an enlarged view of a portion C in FIG. 1 (b).
- FIG.2 (a) is a conceptual diagram of the C section of FIG.1 (d)
- FIG.2 (b) is FIG.1 (a).
- FIG. 1 is an SEM image of the metal nanoparticle array structure of Example 1.
- FIG. 3 is an SEM image of a metal nanoparticle array structure of Example 2.
- 4 is a SEM image of the metal nanoparticle array structure of Example 3.
- FIG. 1 is an SEM image of the metal nanoparticle array structure of Example 1.
- 3 is a small angle scattering spectrum of metal nanoparticle array structures of Examples 1 to 3.
- 3 is an extinction spectrum of metal nanoparticle array structures of Examples 1 to 3. It is an extinction spectrum of the metal nanoparticle arrangement structure of Example 2 and Example 4.
- 10 is a SEM image of the metal nanoparticle array structure of Example 7.
- FIG. 7 is a small angle scattering spectrum of metal nanoparticle array structures of Examples 5 to 7.
- FIG. 7 is an extinction spectrum of metal nanoparticle array structures of Examples 5 to 7. It is an extinction spectrum of the metal nanoparticle arrangement structure of Example 6, Example 8, and Example 9.
- FIG. 5 shows the repeated catalytic activity of the butyl etherification reaction of dimethylphenylsilane using the metal nanoparticle arrangement of Example 2 as a catalyst. It is the temperature dependence in the butyl etherification reaction of dimethylphenylsilane using the metal nanoparticle arrangement
- liquid surface position moving means Fm, particle size, Gm, gap distance (interval), Lm, distance between particles, O, center, Ls, distance between particle substrates, Gs, immobilization layer Thickness
- FIG. 1 and 2 are diagrams showing an example of a metal nanoparticle array structure according to the first embodiment of the present invention, in which FIG. 1 (a) is a plan view and FIG. 1 (b) is a diagram.
- 1A is a cross-sectional view taken along line AA ′ in FIG. 1A
- FIG. 1C is an enlarged view of a portion B in FIG. 1A
- FIG. 1D is a portion C in FIG. FIG.
- the metal nanoparticle array structure 10 has a plurality of metal nanoparticles 4 arrayed on the immobilization layer 2 with regularity. It is roughly structured.
- a plurality of metal nanoparticles 4 arranged with regularity is referred to as metal nanoparticle array 3.
- a region composed of the metal nanoparticle arrays 3 arranged with the same regularity is referred to as a domain portion 8.
- the metal nanoparticles 4 are arranged at equal intervals.
- the metal nanoparticle array structure 10 has regularity on the substrate 1, the immobilization layer 2 formed on the one surface 1a of the substrate 1, and the one surface 2a of the immobilization layer 2. And a metal nanoparticle array 3 in which a plurality of metal nanoparticles 4 are arrayed.
- a conductive substrate can be used as the substrate 1.
- the immobilization layer 2 can be joined firmly and easily.
- a substrate made of a conductive thin film and an insulating substrate may be used as the substrate 1.
- the metal nanoparticle array 3 is formed by arranging the modification part 5 on the surface and arranging the metal nanoparticles 4 having a particle size of Fm.
- the modification part 5 firmly bonds the metal nanoparticles 4 to each other, and the gap distance Gm between the metal nanoparticles 4 and the interparticle distance Lm between the centers O of the adjacent metal nanoparticles 4 are substantially constant. .
- the gap distance Gm of the metal nanoparticles 4 is preferably 1 to 10 nm, and more preferably 1 to 5 nm. Thereby, the metal nanoparticles 4 can be firmly bonded.
- the particle size Fm of the metal nanoparticles 4 is preferably 1 to 100 nm, more preferably 1 to 50 nm. Thereby, the regularity of a metal nanoparticle arrangement
- an immobilization layer 2 having an immobilization layer thickness Gs is formed on the substrate 1.
- Metal nanoparticles 4 are regularly arranged on one surface 2 a of the immobilization layer 2 to form a metal nanoparticle array 3.
- the distance (the distance between the particle substrates) Ls from the one surface 1a of the substrate 1 to the center O of the metal nanoparticles 4 is substantially constant.
- gold is easy to obtain particles having a uniform shape and a uniform particle diameter, and the modified portion 5 such as an organic molecule having a thiol group is easily bonded to the gold.
- the modifying part 5 is preferably an organic molecule having a thiol group such as alkanethiol. This is because the thiol group can be easily bonded to the metal nanoparticles 4 and the metal nanoparticles 4 can be bonded firmly to each other. In particular, when gold nanoparticles are used as the metal nanoparticles 4, the bonding can be made stronger.
- intermolecular interaction between the organic molecules can be used for bonding between the metal nanoparticles 4, and the gap distance Gm between the metal nanoparticles 4 and the adjacent metal nanoparticles 4 can be used.
- the inter-particle distance Lm at the center O can be kept substantially constant.
- the gap distance Gm and the distance Lm between adjacent particles can be controlled.
- the organic molecule of the modifying part 5 has an alkyl chain having 6 to 20 carbons. This is because it is easy to handle and a desired metal nanoparticle array structure can be easily formed.
- the immobilization layer 2 is preferably made of an organic molecule having at least two thiol groups such as alkanedithiol.
- the fixed layer thickness Gs of the fixed layer 2 and the inter-particle distance Ls from the center O of the metal nanoparticle 4 to the one surface 1a of the substrate 1 can be made constant.
- a conductive substrate When a conductive substrate is used as the substrate 1, at least one thiol group of each organic molecule on the other surface 2 b side of the immobilization layer 2 can be firmly bonded to the one surface 1 a of the substrate 1. it can.
- the thiol group of the immobilization layer 2 can be firmly bonded to the conductive thin film.
- At least one thiol group of each organic molecule on the one surface 2a side of the immobilization layer 2 is replaced with an organic molecule in the modified portion 5 of the metal nanoparticle 4 and is firmly bonded to the metal nanoparticle 4 by chemical bonding. Can do.
- the organic molecule of the immobilization layer has an alkyl chain having 6 to 20 carbons. This is because it is easy to handle and a desired metal nanoparticle array structure can be easily formed.
- FIG. 2 is a conceptual diagram showing more specifically the modifying portion 5 and the immobilization layer 2 of FIGS. 1 (c) and 1 (d).
- a plurality of modified portions 5 made of a single-chain alkanethiol (organic molecule) are formed so as to extend outward from the surface of the metal nanoparticles 4 made of gold.
- the thiol group of each alkanethiol is bonded to the metal nanoparticle 4 made of gold.
- the substrate 1 is an insulating substrate 7 having a conductive thin film 6 formed on one surface 7a.
- An immobilization layer 2 is formed on one surface 1 a of the substrate, that is, on the surface of the conductive thin film 6.
- the immobilization layer 2 is composed of a plurality of alkanediols formed substantially perpendicular to the one surface 1 a of the substrate 1. Thereby, the fixing layer thickness Gs of the fixing layer 2 is kept substantially constant.
- At least one thiol group of each organic molecule is disposed on the one surface 2a side of the immobilization layer 2, and another thiol group of each organic molecule disposed on the other surface 2b side of the immobilization layer 2 is the other of the immobilization layer 2. It arrange
- the thiol group on the other surface 2b side is bonded to one surface 1a of the substrate 1, that is, a conductive thin film. Thereby, the immobilization layer 2 is firmly bonded to the substrate 1.
- At least one thiol group of each organic molecule arranged on the one surface 2 a side of the immobilization layer 2 is bonded to the metal nanoparticle 4. Thereby, the metal nanoparticles 4 are firmly bonded to the immobilization layer 2.
- FIG. 3 is a plan view showing another example of the metal nanoparticle array structure according to the embodiment of the present invention.
- the metal nanoparticle array structure 11 includes 11 domain portions 8.
- the closest structure of the metal nanoparticle array 3 is controlled. Ideally, this ordered state is maintained even in the distance from the second proximity position and the third proximity position. In this case, a metal nanoparticle array 3 having a two-dimensional structure of ideal metal nanoparticles 4 shown in FIG. 1 is formed.
- the manufacturing conditions of the metal nanoparticle array are changed, the distant order state of the second proximity position, the third proximity position or more may not be maintained.
- a plurality of domain portions 8 in which an ordered state is maintained may be formed.
- the metal nanoparticle array structure 11 having a plurality of domain portions 8 may be used. Even in this case, a metal nanoparticle array structure having a certain coverage or more can be formed. (Second embodiment of the present invention) Next, the manufacturing apparatus 30 of the metal nanoparticle arrangement
- FIG. 4 is a schematic cross-sectional view showing an example of a metal nanoparticle array structure manufacturing apparatus 30 according to the second embodiment of the present invention.
- the metal nanoparticle array structure manufacturing apparatus 30 includes a liquid tank 23, a lid section 24 that covers the opening 23 c of the liquid tank 23, and an inside 2 d of the liquid tank 23, which are arranged to face each other. It has a schematic configuration having two electrode portions 25, 26 and a power supply portion 28 joined to the two electrode portions 25, 26 via a wiring 27.
- the lid portion 24 is provided with a hole portion 24c having a variable opening diameter d serving as a liquid surface position moving means 39 capable of moving the position of the liquid surface 22a of the reaction liquid 22 filling the liquid tank 23 relative to the electrode portion 25.
- One electrode portion 25 is arranged with one surface 25 a of the substrate 1 facing the other electrode portion 26. Further, the substrate 1 on which the immobilization layer 2 is laminated is used as one electrode portion 25. (Third embodiment of the present invention) Next, the manufacturing method of the metal nanoparticle arrangement structure which is the 3rd Embodiment of this invention is demonstrated.
- the metal nanoparticle 4 is dispersed in a solvent to prepare a reaction liquid, and then the reaction liquid is filled in a liquid tank. From the first step in which the two electrode parts are disposed opposite to each other in the liquid tank so that the two electrode parts are completely immersed in the reaction solution, and from the power supply part connected to the two electrode parts via wiring, A second step of forming an organic nanoparticle array on one surface of one of the two electrode portions by applying a voltage to cause the metal nanoparticles to move in an electric field.
- FIG. 5 is a process diagram showing an example of a method for producing a metal nanoparticle array structure according to an embodiment of the present invention.
- FIG. 5A is a process cross-sectional view at the end of the first process. After the metal nanoparticles 4 are dispersed in the solvent 21 to adjust the reaction liquid 22, the reaction liquid 22 is filled in the liquid tank 23.
- FIG. 5 is a view showing a point in time when two electrode portions 25 and 26 are arranged opposite to the inside 23d of the liquid tank 23 so as to be completely immersed in the reaction liquid 22.
- a volatile solvent is used as the solvent 21.
- the metal nanoparticles 4 are previously covered with a modifying portion 5 made of an organic molecule.
- the substrate 1 on which the immobilization layer 2 is formed is used for one electrode portion 25.
- a conductive substrate is used, and the immobilization layer 2 is disposed toward the other electrode portion 26.
- the liquid level 22 a of the reaction liquid 22 is set at a position where the two electrode portions 25 and 26 are completely immersed in the reaction liquid 22.
- the volatile solvent 21 is preferably water, alcohols, ketones, esters, halogenated solvents, aliphatic hydrocarbons, aromatic hydrocarbons, or a mixture thereof. Thereby, the kinetic and thermodynamic parameters in the formation of the structure of the metal nanoparticles can be controlled.
- the volatile solvent 21 preferably contains an inorganic salt, an organic salt, or both. Thereby, the force received from the electric field in the electrophoresis of metal nanoparticles can be controlled.
- the second step is a step of volatilizing the solvent 21 of the reaction solution 22 while applying a voltage from the power supply 28 to the two electrode portions 25 and 26 and causing a direct current to flow through the reaction solution 22.
- the metal nanoparticles 4 in the reaction liquid 22 are charged, so electric field movement starts, and they begin to gather at one of the electrode portions.
- the metal nanoparticles 4 that are negatively charged are used, they are collected on the anode electrode having the opposite positive potential. Therefore, if one electrode part 25 is used as the anode electrode, the metal nanoparticles 4 gather on the one electrode part 25.
- the substrate (conductive substrate) 1 on which the metal nanoparticle array is to be formed is an anode electrode or a cathode electrode is determined by the charged potential of the metal nanoparticles 4.
- the metal nanoparticles 4 have ion energy consisting of electric field ⁇ movement distance ⁇ charge valence. For this reason, the metal nanoparticles 4 chemisorb onto the substrate (conductive substrate) 1 beyond the energy barrier by ion energy. Without this ion energy, chemical adsorption cannot be performed across the energy barrier, and physical adsorption remains.
- FIG. 5B is a process cross-sectional view in the middle of the second process.
- the space on the lid 24 side from the liquid surface 22a is connected to the outside through the hole 24c of the lid 24, so that the volatile solvent evaporates through the hole 24c.
- the liquid level 22a of the reaction liquid 22 is slightly lowered to expose the lid 24 side of the substrate (conductive substrate) 1 from the liquid level 22a.
- the position of the portion on the one surface of the immobilization layer 2 that is exposed from the liquid level 22a in the vicinity of the liquid level 22a is also lowered.
- the concentration of the metal nanoparticles 4 reaches saturation, and nucleation of the two-dimensional arrangement of the metal nanoparticles 4 in a supersaturated state occurs.
- the coverage of the metal nanoparticle array 3 can be brought to a state close to 100%. Thereby, the metal nanoparticle arrangement
- sequence 3 can be formed with high coverage on the fixed layer 2 on the exposed substrate (conductive substrate) 1.
- the volatilization rate of the volatile solvent 21 is controlled by adjusting the hydrodynamic resistance (viscosity ⁇ length / opening diameter) determined by the opening diameter d and length of the hole 24c and the viscosity of the vapor of the volatile solvent. be able to. Thereby, the descent speed of the liquid level 22a can be controlled.
- the chemical adsorption of the metal nanoparticles 4 on the immobilization layer 2 occurs simultaneously with the nucleation of the two-dimensional array of metal nanoparticles 4.
- ion energy is not too high, there will be sufficient time to meet the energetically stable physical position required for nucleation before chemisorption, and both chemisorption and two-dimensional arrangement are compatible. can do.
- FIG. 5C is a process cross-sectional view at the end of the second process.
- the substrate (conductive substrate) 1 comes out completely above the liquid surface 22 a, and the organic nanoparticle array 3 is formed on the immobilization layer 2 on the substrate (conductive substrate) 1.
- a metal nanoparticle array structure in which the coverage is high and the metal nanoparticles 4 are firmly bonded to the immobilization layer 2 is formed.
- the nanoparticle array 3 on the immobilization layer 2 on the substrate (conductive substrate) 1 may be annealed at about 55 ° C., for example.
- An appropriate annealing temperature varies depending on the type of metal nanoparticles 4 and the type of the immobilization layer 2 used. In the case of gold nanoparticles and alkanedithiol molecules, a suitable annealing temperature is in the range of 40-70 ° C. By changing the metal nanoparticles and the immobilization layer, a suitable annealing temperature is in the range of 30-80 ° C.
- the metal nanoparticles 4 not chemically bonded to the substrate (conductive substrate) 1 can be removed by washing the surface of the substrate (conductive substrate) 1 with running water or ultrasonic cleaning in a suitable solvent. . (Fourth embodiment of the present invention) Next, the manufacturing apparatus 31 of the metal nanoparticle array structure which is the 4th Embodiment of this invention is demonstrated.
- FIG. 6 is a schematic cross-sectional view showing an example of a metal nanoparticle array structure manufacturing apparatus 31 according to the fourth embodiment of the present invention.
- the metal nanoparticle array structure manufacturing apparatus 31 As shown in FIG. 6, the metal nanoparticle array structure manufacturing apparatus 31 according to the fourth embodiment of the present invention is provided with another hole 24d in the lid 24 and the upper part of the other hole 24d.
- the configuration is the same as that of the manufacturing apparatus 30 except that the lifting portion 35 is installed on the upper portion and the supporting wire 36 is provided to connect the lifting portion 35 and the one electrode portion 25.
- the support wire 36 is connected to the lifting portion 35 through another hole 24d, and the one electrode portion 25 can be pulled up in the direction of the lid portion 24 by winding the support wire 36 with the lifting portion 35. It is said that.
- the pulling part 35 functions as a liquid level position moving means 39 that can move the position of the liquid level 22 a of the reaction liquid 22 filling the liquid tank 23 relative to the electrode part 25.
- FIG. 7 is a process diagram showing an example of a method for producing a metal nanoparticle array structure according to the fifth embodiment of the present invention.
- FIG. 7A is a process cross-sectional view at the end of the first process. After adjusting the reaction liquid 22 by dispersing the metal nanoparticles 4 in the solvent 21, the reaction liquid 22 is filled in the liquid tank 23.
- FIG. 5 is a view showing a point in time when two electrode portions 25 and 26 are arranged opposite to the inside 23d of the liquid tank 23 so as to be completely immersed in the reaction liquid 22.
- a volatile solvent is used as the solvent 21.
- the metal nanoparticles 4 are previously covered with a modifying portion 5 made of an organic molecule.
- the substrate 1 on which the immobilization layer 2 is formed is used for one electrode portion 25.
- a conductive substrate is used, and the immobilization layer 2 is disposed toward the other electrode portion 26.
- the liquid level 22 a of the reaction liquid 22 is set at a position where the two electrode portions 25 and 26 are completely immersed in the reaction liquid 22.
- a voltage is applied from the power source 28 to the two electrode portions 25 and 26 to cause a direct current to flow through the reaction liquid 22, and the support wire 36 is wound up by the lifting portion 35, thereby covering one electrode portion 25.
- This is a step of pulling up in the direction of the portion 24.
- the metal nanoparticles 4 in the reaction liquid 22 are charged, so electric field movement starts, and they begin to gather at one of the electrode portions.
- the metal nanoparticles 4 that are negatively charged are used, they are collected on the anode electrode having the opposite positive potential. Therefore, if one electrode part 25 is used as the anode electrode, the metal nanoparticles 4 gather on the one electrode part 25.
- the substrate (conductive substrate) 1 on which the metal nanoparticle array is to be formed is an anode electrode or a cathode electrode is determined by the charged potential of the metal nanoparticles 4.
- the metal nanoparticles 4 have ion energy consisting of electric field ⁇ movement distance ⁇ charge valence. Due to this ion energy, the metal nanoparticles 4 are chemically adsorbed on the substrate (conductive substrate) 1 beyond the energy barrier. Without this ion energy, chemical adsorption cannot be performed across the energy barrier, and physical adsorption remains.
- FIG. 7B is a process cross-sectional view in the middle of the second process.
- the electrode portion 25 is pulled up in the direction of the lid portion 24 by the pulling portion 35 to expose the lid portion 24 side of the substrate (conductive substrate) 1 from the liquid surface 22a.
- the position of the surface portion (gas-liquid interface 29) of the immobilization layer 2 on the substrate (conductive substrate) 1 with which the liquid surface 22a of the reaction liquid 22 is in contact also decreases. .
- the concentration of the metal nanoparticles 4 reaches saturation due to the evaporation of the solvent generated in the vicinity of the gas-liquid interface 29, and nucleation of the two-dimensional array of the metal nanoparticles 4 in a supersaturated state occurs.
- the coverage of the metal nanoparticle array 3 can be made close to 100%. Thereby, the metal nanoparticle arrangement
- the pulling speed can be adjusted and controlled by the pulling unit 35.
- the chemical adsorption of the metal nanoparticles 4 on the immobilization layer 2 occurs simultaneously with the nucleation of the two-dimensional array of metal nanoparticles 4.
- ion energy is not too high, there will be sufficient time to meet the energetically stable physical position required for nucleation before chemisorption, and both chemisorption and two-dimensional arrangement are compatible. can do.
- FIG. 7C is a process cross-sectional view at the end of the second process.
- the substrate (conductive substrate) 1 comes out completely above the liquid surface 22 a, and the organic nanoparticle array 3 is formed on the immobilization layer 2 on the substrate (conductive substrate) 1.
- a metal nanoparticle array structure in which the coverage is high and the metal nanoparticles 4 are firmly bonded to the immobilization layer 2 is formed.
- the metal nanoparticles 4 can be firmly bonded to the immobilization layer 2.
- Metal nanoparticle array structures 10 and 11 include a substrate 1, an immobilization layer 2 formed on one surface 1 a of the substrate 1, and a metal nanoparticle formed on one surface 2 a of the immobilization layer 2.
- the metal nanoparticle array 3 can be controlled to be constant and can easily form a chemical bond with the substrate 1, and has a plurality of metal nanoparticles 4 having the same size and shape. Chemical bonding of particle array 3 In firmly fixed on the substrate 1, and may increase the coverage of the metal nanoparticle array 3.
- the metal nanoparticle array structures 10 and 11 have a configuration in which the interval between the metal nanoparticles 4 is 1 to 10 nm, the metal nanoparticles 4 can be firmly bonded to each other.
- the metal nanoparticle array structures 10 and 11 according to the embodiment of the present invention have a configuration in which the particle diameter of the metal nanoparticles 4 is 1 to 100 nm, high regularity of the metal nanoparticle array can be secured, and Even if the area is large, a high coverage can be obtained.
- the metal nanoparticles 4 are made of gold, not only the metal nanoparticles 4 having a uniform shape and a uniform particle diameter can be easily obtained, Further, the modification part 5 such as an organic molecule having a thiol group can be easily joined to the metal nanoparticle 4.
- the modified part 5 is an organic molecule having a thiol group, and the thiol group is bonded to the metal nanoparticle 4. Bonding to each other and bonding to the fixing layer 2 can be strengthened.
- the metal nanoparticle array structures 10 and 11 according to the embodiment of the present invention have a structure in which the organic molecules of the modified portion 5 have an alkyl chain having 6 or more and 20 or less carbon, it is easy to handle and a desired metal A nanoparticle array structure can be easily formed.
- the immobilization layer 2 is made of an organic molecule having at least two thiol groups, and at least one of the immobilization layer on one surface side and the other surface side, respectively. Since two thiol groups are arranged and the thiol group on the other surface side is bonded to the substrate 1, the metal nanoparticle array structure 10 is firmly fixed to the substrate 1 by covalent bonding.
- the metal nanoparticle array structures 10 and 11 according to the embodiment of the present invention have a configuration in which the organic molecules of the immobilization layer 2 have an alkyl chain having 6 to 20 carbon atoms, There is no mechanical behavior and it is stably immobilized as on the solid surface.
- the substrate 1 is a conductive substrate, at least one thiol group of each organic molecule of the immobilization layer 2 is provided on one surface of the substrate 1. It can be firmly joined to la.
- the substrate 1 is composed of the insulating substrate 7 having the conductive thin film 6 formed on one surface, the immobilization layer is formed on the conductive thin film 6. 2 thiol groups can be firmly bonded.
- the metal nanoparticle array structure manufacturing apparatus 30 can be disposed so as to face the liquid tank 23, the lid portion 24 covering the opening 23 c of the liquid tank 23, and the inside 23 d of the liquid tank 23.
- the liquid surface 22a of the reaction liquid 22 filling the liquid tank 23 with respect to the electrode part 25.
- the electrode part 25 has a power source part 28 connected to the two electrode parts 25 and 26 via a wiring 27. Since the liquid surface position moving means 39 that can move the position is provided, the position of the liquid surface 22a of the reaction liquid 22 with respect to the electrode portion 25 is moved at a predetermined speed, so that a portion on one surface of the immobilization layer 2 is obtained.
- the portion exposed from the liquid surface 22a in the vicinity of the liquid surface 22a (the gas-liquid interface portion 29) is gradually exposed, and the metal nanoparticle array 3 is formed with a high coverage in the vicinity of the gas-liquid interface portion 29. Can do.
- the metal nanoparticle array structure manufacturing apparatus 30 has a configuration in which the liquid surface position moving means 39 is provided in the lid 24 and is a hole 24c capable of changing the opening diameter.
- the moving speed of the position of the liquid surface 22a of the reaction liquid 22 relative to the electrode part 25 can be controlled, and the gas-liquid interface part 29 is gradually exposed to In the vicinity of the interface portion 29, the metal nanoparticle array 3 can be formed with high coverage.
- the liquid surface position moving means 39 can pull up one of the two electrode portions 25, 26 in the direction of the lid portion 24. Therefore, the moving speed of the position of the liquid surface 22a of the reaction liquid 22 relative to the electrode part 25 can be controlled by pulling up the substrate 1 at a predetermined pulling speed.
- the metal nanoparticle array 3 can be formed with high coverage in the vicinity of the gas-liquid interface portion 29 by gradually exposing.
- the reaction liquid 22 is filled in the liquid tank 23 and the reaction liquid 22 is obtained.
- a voltage is applied to the two electrode portions 25 and 26 from the first step of arranging the two electrode portions 25 and 26 soaked in the opposite direction, and the power supply portion 28 connected to the two electrode portions 25 and 26 via the wiring 27.
- the metal nanoparticle array structure manufacturing method according to the embodiment of the present invention has a configuration in which the moving speed of the position of the liquid surface 22a of the reaction liquid 22 with respect to the electrode part 25 is 0.02 mm / s or less, the gas-liquid interface part. 29 is gradually exposed, and the coverage of the metal nanoparticle array 3 can be increased.
- the metal nanoparticle array structure manufacturing method uses a volatile solvent as the solvent 21 in the first step, and volatilizes the volatile solvent in the second step when a voltage is applied. Due to the configuration, the position of the liquid surface 22a of the reaction liquid 22 with respect to the electrode part 25 is moved to gradually expose the gas-liquid interface part 29, and the metal nanoparticle array 3 is formed with high coverage in the vicinity of the gas-liquid interface part 29. can do.
- the volatile solvent is water, alcohols, ketones, esters, halogenated solvents, aliphatic hydrocarbons, or aromatic hydrocarbons, Or since it is the structure which is either of those mixtures, the kinetic and thermodynamic parameter in organization of the metal nanoparticle 4 can be controlled by changing the kind of solvent.
- the volatile solvent includes an inorganic salt, an organic salt, or both
- the force that the metal nanoparticle 4 receives from an electric field in electrophoresis. Can be controlled.
- the manufacturing method of the metal nanoparticle array structure according to the embodiment of the present invention is the second step, and when applying a voltage, the electrode part 25 of the two electrode parts 25 and 26 is moved in the direction of the lid part 24. Therefore, the position of the liquid surface 22a of the reaction liquid 22 with respect to the electrode part 25 is moved to form a two-dimensional array of metal nanoparticles at the gas-liquid interface part 29, and the metal nanoparticle array 3 is formed. It can be formed with high coverage.
- the method for producing a metal nanoparticle array structure uses metal nanoparticles having a particle diameter of 1 to 100 nm, so that high regularity of the metal nanoparticle array can be secured, and Even if the area is large, a high coverage can be obtained.
- the gap distance Gm of the metal nanoparticles 4 can be made constant.
- the method for producing a metal nanoparticle array structure uses a substrate provided in the immobilization layer 2 as one electrode portion 25 of the two electrode portions 25 and 26. Since one surface side is arranged to face the other electrode part 26, an electric field can be uniformly applied to one surface 2a of the immobilization layer 2, and a metal nanoparticle array structure can be manufactured efficiently.
- the substrate 1 is composed of a conductive substrate
- the immobilization layer 2 can be firmly bonded, and the metal nanoparticle array structure can be manufactured efficiently.
- the substrate 1 is composed of the insulating substrate 7 in which the conductive thin film 6 is formed on the one surface 7a side.
- the metal nanoparticle array structure can be efficiently manufactured.
- the manufacturing method of the metal nanoparticle array structure which is an embodiment of the present invention uses a carbon electrode as the other electrode part 26, an electric field can be efficiently applied to the two electrode parts 25 and 26, and the metal nanoparticle can be efficiently applied.
- a particle array structure can be produced.
- the metal nanoparticle array structure manufacturing method according to the embodiment of the present invention is configured to anneal the organic nanoparticle array 3 formed on one electrode portion 25 in a temperature range of 30 to 80 ° C. after the second step. Further, the bonding strength between the substrate 1 and the immobilization layer 2 and the bonding between the immobilization layer 2 and the metal nanoparticles 4 can be further increased.
- the metal nanoparticle array structure, the manufacturing apparatus, and the manufacturing method thereof according to the embodiment of the present invention are not limited to the above-described embodiment, and are implemented with various modifications within the scope of the technical idea of the present invention. be able to. Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.
- Example 1 Provides for producing metal nanoparticle array structure> First, gold nanoparticles having a particle size Fm of 9 to 10 nm were prepared.
- HEX hexanethiol molecules
- a conductive thin film made of gold was formed on a glass substrate (substrate size: 15 mm ⁇ 15 mm).
- the surface of the gold thin film was modified with 1,6 hexanedithiol to form an immobilization layer.
- a glass substrate on which an immobilization layer and a gold thin film were formed as one electrode part was disposed, and a carbon electrode was used as another electrode part, and these were completely immersed in the reaction solution.
- the immobilization layer was disposed toward the carbon electrode, and the distance between the two electrode portions was 1.2 mm.
- a lid was attached so as to cover the opening of the liquid tank, and the diameter of the hole provided in the lid was adjusted.
- a voltage of 1.0 V was applied using a gold thin film as a cathode and a carbon electrode as an anode, and the mixture was left at room temperature and normal pressure (1 atm, 25 ° C.) for 2 hours.
- Example 2 A metal nanoparticle array structure was formed in the same manner as in Example 1 except that dodecanethiol (DOD) was used instead of the hexanethiol molecule.
- Example 3 A metal nanoparticle array structure was formed in the same manner as in Example 1 except that hexadecanethiol (HEXD) was used instead of the hexanethiol molecule.
- Example 4 A metal nanoparticle array structure was formed in the same manner as in Example 2 except that metal nanoparticles having a particle size Fm of 29 to 30 nm were used.
- Example 5 Example 1 except that a transparent conductive metal oxide ITO substrate (InTiO) was used instead of providing a conductive thin film made of gold (hereinafter referred to as a gold thin film) on a glass substrate (substrate size 15 mm ⁇ 15 mm).
- a metal nanoparticle array structure was formed.
- the ITO substrate used is an EL specification manufactured by Geomatic Co., Ltd., and the conductivity is 10 ⁇ / ⁇ .
- Example 6 A metal nanoparticle array structure was formed in the same manner as in Example 5 except that dodecanethiol (DOD) was used instead of the hexanethiol molecule.
- Example 7 A metal nanoparticle array structure was formed in the same manner as in Example 5 except that hexadecanethiol (HEXD) was used instead of the hexanethiol molecule.
- Example 2 The surface of the transparent conductive metal oxide ITO substrate (InTiO) was modified with 1,6-hexanedithiol to form an immobilization layer.
- Example 8 A metal nanoparticle array structure was formed in the same manner as in Example 6 except that metal nanoparticles having a particle size Fm of 29 to 30 nm were used.
- Example 9 A metal nanoparticle array structure was formed in the same manner as in Example 6 except that metal nanoparticles having a particle size Fm of 49 to 50 nm were used.
- ⁇ Evaluation of metal nanoparticle array structure> 8 to 10 are SEM photographs of the metal nanoparticle array structures of Examples 1 to 3.
- FIG. 14 is an SEM photograph of the metal nanoparticle array structure of Example 7. FIG. Although defects were partially observed, a metal nanoparticle array composed of metal nanoparticles arranged at equal intervals was formed with high coverage.
- FIG. 8 is analyzed, and in the metal nanoparticle arrangement of Example 1, the particle size Fm of the gold nanoparticles is 9 nm, the distance Lm between the metal nanoparticles is 10.6 nm, and the gap distance Gm between the metal nanoparticles is 1.6 nm. Met. The coverage was 58%.
- the gold nanoparticles have a particle size Fm of 9 nm, a distance Lm between the metal nanoparticles of 11.4 nm, and a gap distance Gm between the metal nanoparticles of 2.4 nm. Met.
- the coverage of the metal nanoparticle array was 95% or more. This coverage was achieved over almost the entire area of the substrate size 15 mm ⁇ 15 mm.
- FIG. 10 is analyzed, and in the metal nanoparticle arrangement of Example 3, the particle size Fm of the gold nanoparticles is 9 nm, the distance Lm between the metal nanoparticles is 11.9 nm, and the gap distance Gm between the metal nanoparticles is 2.9 nm. Met. The coverage was 82%.
- the gold nanoparticles have a particle size Fm of 9.0 nm, a metal nanoparticle distance Lm of 11.9 nm, and a gap distance Gm between the metal nanoparticles of 2; .9 nm.
- the coverage was 92%.
- FIG. 11 shows the measurement results of the small angle scattering spectra of the metal nanoparticle array structures of Examples 1 to 3.
- FIG. 15 shows the measurement results of the small-angle scattering spectra of the metal nanoparticle array structures of Examples 5 to 7.
- FIG. 16 shows the measurement results of the small-angle scattering spectra of Example 6, Example 8, and Example 9. Spectral peaks were observed at almost the same positions.
- the gap distance Gm between the gold nanoparticle particles can be controlled by the selection of the modifying molecule, and in particular, it has been demonstrated that the carbon number of the alkanethiol molecule is proportional to the gap distance Gm between the particles. It will be. From the results of FIG. 16, it was found that the interparticle distances were 10.7 nm, 31.4 nm, and 50.6 nm for the particle diameters Fm of 10 nm, 30 nm, and 50 nm, respectively.
- gap distance Gm between the gold nanoparticle particles can be controlled by the particle size Fm, and the results of the scanning microscope were separately verified.
- FIG. 12 is a graph showing the measurement results of the extinction spectrum of the metal nanoparticle array structures of Examples 1 to 3, and showing the dependence of the frequency of local plasmon resonance on the gap distance Gm between particles.
- FIG. 17 shows the measurement results of the extinction spectrum of the metal nanoparticle array structures of Examples 5 to 7.
- FIG. 13 is a graph showing the measurement results of the extinction spectrum of the metal nanoparticle array structures of Example 2 and Example 4, and showing the dependence of the frequency of local plasmon resonance on the particle diameter Fm.
- FIG. 18 is a graph showing the extinction spectrum measurement results of the metal nanoparticle array structures of Example 6, Example 8, and Example 9, and showing the frequency dependence of local plasmon resonance frequency on the particle diameter Fm.
- the metal nanoparticle array structure of Comparative Example 1 remained only 18%. On the other hand, 71% of the metal nanoparticle array structure of Example 1 remained.
- the catalytic reaction is performed by immersing the metal nanoparticle array of Example 2 in a solution in which silane is dissolved in alcohol, and stirring the solution with a stir bar, and after a certain time, the reaction yield of the product by gas chromatography I confirmed.
- Non-patent Document 20 a reaction requiring a high temperature of 100 ° C.
- reaction proceeds even with tert-butanol, which has hardly progressed with conventional metal nanoparticles, indicating the high catalytic activity of the array of metal nanoparticles according to the present invention.
- the alkanethiol molecular layer covering the surface of the metal nanoparticles has a function of taking up the alcohol substrate as a hydrophobic reaction space.
- FIG. 23 shows the temperature dependence of the catalytic activity for dimethylphenylsilane in the solvent 1-butanol. Since it has a temperature dependency that has a peak at around 25 ° C., it is considered that dimethylphenylsilane is taken into a hydrophobic space composed of an alkyl group that is a modifying molecule of metal nanoparticles. Therefore, it has high catalytic activity even at a low temperature of about 25 ° C.
- the metal nanoparticle array structure of the present invention has a very strong electromagnetic field on the surface of the structure by causing a strong interaction between localized surface plasmons between gold nanoparticles closely arranged at intervals of several nanometers. Can be generated. Since these plasmon coupling phenomena can be easily caused by ordinary light irradiation, they can be used for optical waveguides, photochemical reaction reactors, optical devices, high-sensitivity sensors, catalysts, and the like. In addition, the metal nanoparticle array structure of the present invention can change the wavelength of the localized plasmon freely by changing the size of the metal nanoparticles and the alkyl chain length of the surface modification molecule. It is possible to fabricate a structure rich in.
- the substrate uptake ability can be controlled by changing the alkyl chain length of the surface modification molecule. It can be used as a catalyst and high-sensitivity sensor utilizing the characteristics of particles. Furthermore, in the present invention, since the metal nanoparticle array structure can be produced on a large area with a high coverage, unlike the conventional metal nanoparticle array of only a small region, it has a size suitable for human real life. Various devices can be provided.
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Abstract
Description
以下、添付図面を参照しながら、本発明の第1の実施形態である金属ナノ粒子配列構造体を説明する。
(本発明の第2の実施形態)
次に、本発明の第2の実施形態である金属ナノ粒子配列構造体の製造装置30を説明する。
(本発明の第3の実施形態)
次に、本発明の第3の実施形態である金属ナノ粒子配列構造体の製造方法を説明する。
(本発明の第4の実施形態)
次に、本発明の第4の実施形態である金属ナノ粒子配列構造体の製造装置31を説明する。
(本発明の第5の実施形態)
次に、本発明の第5の実施形態である金属ナノ粒子配列構造体の製造方法を説明する。
<金属ナノ粒子配列構造体の製造プロセス>
まず、粒径Fmが9~10nmの金ナノ粒子を用意した。
(実施例2)
ヘキサンチオール分子の代わりに、ドデカンチオール(DOD)を用いた他は実施例1と同様にして、金属ナノ粒子配列構造体を形成した。
(実施例3)
ヘキサンチオール分子の代わりに、ヘキサデカンチオール(HEXD)を用いた他は実施例1と同様にして、金属ナノ粒子配列構造体を形成した。
(比較例1)
ガラス基板(基板の大きさ15mm×15mm)上に金からなる導電性薄膜(以下、金薄膜)を形成した後、金薄膜の表面を1,6ヘキサンジチオールによって修飾して、固定化層を形成した。
(実施例4)
粒径Fmが29~30nmの金属ナノ粒子を用いた他は実施例2と同様にして、金属ナノ粒子配列構造体を形成した。
(実施例5)
ガラス基板(基板の大きさ15mm×15mm)上に金からなる導電性薄膜(以下、金薄膜)を設ける代わりに透明導電性金属酸化物のITO基板(InTiO)を用いた他は実施例1と同様にして、金属ナノ粒子配列構造体を形成した。用いたITO基板はジオマテック社製のEL仕様のもので、導電性は10Ω/□である。
(実施例6)
ヘキサンチオール分子の代わりに、ドデカンチオール(DOD)を用いた他は実施例5と同様にして、金属ナノ粒子配列構造体を形成した。
(実施例7)
ヘキサンチオール分子の代わりに、ヘキサデカンチオール(HEXD)を用いた他は実施例5と同様にして、金属ナノ粒子配列構造体を形成した。
(比較例2)
透明導電性金属酸化物のITO基板(InTiO)の表面を1,6ヘキサンジチオールによって修飾して、固定化層を形成した。
(実施例8)
粒径Fmが29~30nmの金属ナノ粒子を用いた他は実施例6と同様にして、金属ナノ粒子配列構造体を形成した。
(実施例9)
粒径Fmが49~50nmの金属ナノ粒子を用いた他は実施例6と同様にして、金属ナノ粒子配列構造体を形成した。
<金属ナノ粒子配列構造体の評価>
図8~10は、実施例1~3の金属ナノ粒子配列構造体のSEM写真である。図14は、実施例7の金属ナノ粒子配列構造体のSEM写真である。部分的に欠陥が見られるが、等間隔に配置された金属ナノ粒子からなる金属ナノ粒子配列が被覆率高く形成されていた。
図16の結果より、10nm、30nm、50nmの粒径Fmに対して粒子間距離がそれぞれ、10.7nm、31.4nm、50.6nmであることが分かった。
(触媒効果の評価)
実施例2の金属ナノ粒子配列の触媒効果を、図19に示すシランとアルコールを用いたシリルエーテル化反応を使って確かめた。
Claims (26)
- 基板と、
前記基板の一面に形成された固定化層と、
前記固定化層の一面に形成された金属ナノ粒子配列と、を有する金属ナノ粒子配列構造体であって、
前記金属ナノ粒子配列は、複数の金属ナノ粒子が等間隔となるように配列されてなり、
前記金属ナノ粒子同士は、その表面に備えられた修飾部により互いに接合されるとともに、前記金属ナノ粒子が前記固定化層の一面に化学結合により固定化されていることを特徴とする金属ナノ粒子配列構造体。 - 前記金属ナノ粒子の間隔が1~10nmであることを特徴とする請求項1に記載の金属ナノ粒子配列構造体。
- 前記金属ナノ粒子の粒径が1~100nmであることを特徴とする請求項1又は2に記載の金属ナノ粒子配列構造体。
- 前記金属ナノ粒子が金からなることを特徴とする請求項1~3のいずれか1項に記載の金属ナノ粒子配列構造体。
- 前記修飾部がチオール基を有する有機分子であり、前記チオール基が前記金属ナノ粒子に接合されていることを特徴とする請求項1~4のいずれか1項に記載の金属ナノ粒子配列構造体。
- 前記修飾部の有機分子が6以上20以下の炭素を備えたアルキル鎖を有していることを特徴とする請求項5に記載の金属ナノ粒子配列構造体。
- 前記固定化層が少なくとも2つのチオール基を有する有機分子からなり、前記固定化層の一面側と他面側にそれぞれ少なくとも1つのチオール基が配置されており、
前記他面側のチオール基が前記基板に接合されていることを特徴とする請求項1~6のいずれか1項に記載の金属ナノ粒子配列構造体。 - 前記固定化層の有機分子が6以上20以下の炭素を備えたアルキル鎖を有していることを特徴とする請求項7に記載の金属ナノ粒子配列構造体。
- 前記基板が、導電性基板であることを特徴とする請求項1~8のいずれか1項に記載の金属ナノ粒子配列構造体。
- 前記基板が、一面に導電性薄膜が形成されてなる絶縁性基板からなることを特徴とする請求項1~8のいずれか1項に記載の金属ナノ粒子配列構造体。
- 液槽と、
前記液槽の開口部を覆う蓋部と、
前記液槽の内部に対向配置可能な2つの電極部と、
前記2つの電極部に配線を介して接続された電源部と、を有し、
前記液槽に満たす反応液の液面の前記電極部に対する位置を移動可能な液面位置移動手段が備えられていることを特徴とする金属ナノ粒子配列構造体の製造装置。 - 前記液面位置移動手段が、前記蓋部に設けられ、開口径を変えることが可能な孔部であることを特徴とする請求項11に記載の金属ナノ粒子配列構造体の製造装置。
- 前記液面位置移動手段が、前記2つの電極部のうちの一の電極部を前記蓋部方向に引き上げ可能とする引き上げ部であることを特徴とする請求項11又は12に記載の金属ナノ粒子配列構造体の製造装置。
- 金属ナノ粒子を溶媒に分散して反応液を調整した後、前記反応液を液槽に満たし、前記反応液に浸漬させた2つの電極部を対向配置させる第1工程と、
前記2つの電極部に配線を介して接続した電源部から、前記2つの電極部に電圧を印加するとともに、前記電極部に対する前記反応液の液面の位置を移動させて、前記一の電極部の一面に有機ナノ粒子配列を形成する第2工程と、を有することを特徴とする金属ナノ粒子配列構造体の製造方法。 - 前記電極部に対する前記反応液の液面の位置の移動速度が0.02mm/s以下であることを特徴とする請求項14に記載の金属ナノ粒子配列構造体の製造方法。
- 第1工程で、前記溶媒として揮発性溶媒を用いるとともに、
第2工程で、電圧の印加の際に前記揮発性溶媒を揮発させて、前記電極部に対する前記反応液の液面の位置を移動させることを特徴とする請求項14又は15に記載の金属ナノ粒子配列構造体の製造方法。 - 前記揮発性溶媒が水、アルコール類、ケトン類、エステル類、ハロゲン系溶媒、脂肪族炭化水素類、または芳香族炭化水素類、あるいはそれらの混合物のいずれかであることを特徴とする請求項16に記載の金属ナノ粒子配列構造体の製造方法。
- 前記揮発性溶媒が、無機塩、有機塩、あるいはその両方を含むことを特徴とする請求項16又は17に記載の金属ナノ粒子配列構造体の製造方法。
- 第2工程で、電圧の印加の際に、前記2つの電極部のうちの一の電極部を前記蓋部方向に引き上げて、前記電極部に対する前記反応液の液面の位置を移動させることを特徴とする請求項14~18のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 粒径が1~100nmである金属ナノ粒子を用いることを特徴とする請求項14~19のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 有機分子によって修飾された金属ナノ粒子を用いることを特徴とする請求項14~20のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 2つの電極部のうちの一の電極部として固定化層を備えた基板を用い、前記固定化層の一面側を他の電極部に対向させて配置することを特徴とする請求項14~21のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 前記基板が導電性基板からなることを特徴とする請求項14~22のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 前記基板が、一面側に導電性薄膜が形成されてなる絶縁性基板からなることを特徴とする請求項14~23のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 前記他の電極部として炭素電極を用いることを特徴とする請求項14~24のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
- 第2工程後、前記有機ナノ粒子配列を30~80℃の温度範囲でアニール処理することを特徴とする請求項14~25のいずれか1項に記載の金属ナノ粒子配列構造体の製造方法。
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JP2020108913A (ja) * | 2018-12-31 | 2020-07-16 | パロ アルト リサーチ センター インコーポレイテッド | 微小物体を操作するためのマイクロアセンブラシステム |
WO2023089990A1 (ja) * | 2021-11-19 | 2023-05-25 | ソニーグループ株式会社 | 構造体および構造体の製造方法ならびに前駆体組成物 |
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