WO2015166816A1 - Microstructure métallique - Google Patents

Microstructure métallique Download PDF

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Publication number
WO2015166816A1
WO2015166816A1 PCT/JP2015/061796 JP2015061796W WO2015166816A1 WO 2015166816 A1 WO2015166816 A1 WO 2015166816A1 JP 2015061796 W JP2015061796 W JP 2015061796W WO 2015166816 A1 WO2015166816 A1 WO 2015166816A1
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Prior art keywords
layer
metal
diatom
metal structure
coating
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PCT/JP2015/061796
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English (en)
Japanese (ja)
Inventor
香織 鎌田
貞子 朴
智一 彌田
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国立大学法人東京工業大学
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Priority to JP2016515932A priority Critical patent/JP6108256B2/ja
Publication of WO2015166816A1 publication Critical patent/WO2015166816A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • the present invention relates to a fine metal structure having a predetermined structure with a metal layer.
  • biotemplate technology in which a biological tissue is used as a template (template), and a shape peculiar to the biological tissue is copied as it is. Since the biological tissue has a complicated and orderly shape, according to this biotemplate technology, it is expected that unique properties will be manifested depending on the copied structure shape. In particular, by using microorganisms as living organisms, there is a high possibility that a precise shape of a nano or micrometer scale will be achieved as a structure.
  • Patent Document 1 discloses a case where a fine cyanobacteria is metal-coated.
  • This cyanobacteria has a minute coil shape as a unit structure, and has a predetermined wire diameter, number of turns, pitch, and winding direction.
  • the coil shape is copied as it is.
  • an electroless plating process is used.
  • an absorption characteristic peculiar to the structure can be expressed by assembling an electromagnetic wave shielding (absorbing) body using the acquired structure.
  • metal coating covering a surface of a biological tissue with a metal layer is referred to as “metal coating”.
  • a minute structure obtained by this metal coating is referred to as a “minute metal structure”.
  • Non-Patent Document 1 and Non-Patent Document 2 disclose examples in which fine diatoms are coated with metal.
  • This diatom has minute pores on a predetermined surface as a unit structure.
  • An electroless plating process is used for the two metal coatings.
  • the characteristics of these fine metal structures the relationship between the GHz band frequency of the electromagnetic wave and the dielectric constant and the relationship between the wavelength in the infrared region and the transmittance are disclosed.
  • Non-Patent Document 3 and Non-Patent Document 4 disclose examples in which fine diatoms are coated with metal. Surface shapes similar to those described in Non-Patent Documents 1 and 2 are copied as they are, and a fine metal structure can be obtained. Chemical vapor deposition is used for these two metal coatings. It is disclosed that surface plasmon resonance peculiar to a structure and surface enhanced Raman scattering can be expressed by irradiating light to these fine metal structures.
  • an object of the present invention is to provide a fine metal structure obtained by coating a surface of a biological tissue with a metal layer, which can improve the quality of the metal coating and achieve a precise shape. There is to do.
  • the fine metal structure according to the present invention includes a metal layer that coats the surface of a diatom as a template by plating (that is, metal coating), and forms a predetermined structure with the metal layer.
  • the diatoms may be removed after the metal layer is coated by plating. Further, even after the metal layer is coated, the diatoms may not be removed and may be contained as they are in the fine metal structure.
  • the micro metal structure according to the present invention is characterized in that the predetermined structure has a circular first surface and a circular second surface having the same diameter as the first surface, and the first surface and The second surface is configured to be a hollow disk spaced apart from each other in parallel, and the first surface has a plurality of regularly arranged first pores along a direction from the center to the circumference of the circle. (Claim 1).
  • the hollow disk is constituted by the first and second surfaces being made of a metal layer.
  • This metal layer may be a single layer or a multilayer. Further, these first and second surfaces may be spaced apart from each other in parallel, for example, with a wall and a disk side surface interposed therebetween.
  • the plurality of first pores may be arranged in a row and at equal intervals on a circular first surface radius line, for example. Furthermore, pores may be provided on the second surface or may not be provided.
  • the inventor has clarified that the mode of peeling or aggregation of the metal layer in the metal coating largely depends on the shape of the metal layer. According to the inventor's earnest research, the above-mentioned peeling and aggregation can be suppressed by forming the metal layer so as to have the above-described specific shape. The said structure is based on this knowledge. According to this configuration, in the fine metal structure, the quality of the metal coating can be improved, and a precise shape can be achieved.
  • the second surface is configured such that a plurality of second pores having a diameter larger than that of the first pore are arranged (claims). Item 2).
  • the time for coating the metal layer by the plating treatment is determined by coating the metal layer with the diameter of the first pore or the diameter of the second pore. It is preferable that the setting is made based on the speed, and the plating process is executed based on the set time.
  • the coating time may be set by paying attention to the smaller one of the diameters of the first and second pores.
  • the rate of coating the metal layer is estimated from at least one of the following factors: temperature in the plating bath, pH (hydrogen ion concentration), solid concentration of diatom relative to the plating solution, and metal ion concentration in the plating solution. May be.
  • the metal layer may be made of at least one metal selected from the group consisting of gold, silver, copper, nickel, cobalt, and aluminum. 4).
  • the metal layer includes at least a first layer and a second layer along a direction from the surface of the diatom as the template to the outside, and the metal constituting the first layer is ionized. It is preferable that the metal has a tendency greater than that of the metal constituting the second layer.
  • the first layer since a metal having a higher ionization tendency is used as the first layer, it can serve as a base for the second layer metal. Thereby, it can suppress that the 1st, 2nd layer mutually peels. Therefore, after the first layer is made to follow the biological tissue, a fine shape can be achieved even when the second layer is metal-coated on the first layer. That is, with the second layer of metal alone, the quality of the metal coating can be improved by the above configuration even when it is difficult to follow the coating on the biological tissue.
  • the first layer included in the metal layer may be configured of the nickel, and the second layer included in the metal layer may be configured of the gold (Claim 6).
  • core diatom or aorimuna may be used as the diatom as the template (Claim 7).
  • Core diatom and Aoremuna can be cultured in large quantities with a certain quality in a relatively short period of time. Therefore, according to the said structure, the fine metal structure of an elaborate shape can be obtained stably and in large quantities also including the cultivation process of the diatom as a template.
  • the quality of the metal coating can be improved and a precise shape can be achieved.
  • the fine metal structure according to the embodiment of the present invention is obtained by biotemplate technology. Specifically, diatom is used as a template, and a metal layer is coated on the surface of the diatom by plating. Next, after metal coating, diatoms are removed. Thereby, the shape of the diatom as a template is copied as it is with a predetermined structure of the metal layer. This copied structure becomes the micro metal structure itself.
  • the manufacture of the fine metal structure according to the embodiment of the present invention is mainly constituted by four processes.
  • the processes are “1. Pretreatment process”, “2. First layer formation process”, “3. Second layer formation process”, and “4. Removal process”, respectively.
  • cultured diatoms are pretreated so that the metal coating follows the biological tissue.
  • First layer formation process is to form a first layer (base) by metal-coating pretreated diatom.
  • Second layer forming process is to form a second layer by further metal-coating diatoms metal-coated in the first layer.
  • Removal process is to remove only biological tissues (ie, diatoms) from metal-coated diatoms.
  • core diatom is used as diatom.
  • FIG. 1 is a diagram for explaining the structure of a diatom 10 (core diatomite) as a template.
  • the diatom 10 has a cylindrical shape, and the main component is silicon.
  • the cylindrical diatom 10 includes a top surface 11 and a bottom surface 12.
  • Each of the disks 13 constituting the top surface 11 and the bottom surface 12 has a two-layer structure. This two-layer structure will be described in detail later.
  • the diatom 10 has two disks 13 integrated with each other via a side surface 14, but each disk 13 can be easily disassembled as a separate body.
  • the cylindrical diatom 10 is provided with pores on each surface.
  • the top surface 11, the bottom surface 12, and the side surface 14 are provided with a plurality of pores 11a, pores 12a, and pores 14a penetrating them. These arranged pore groups are arranged with a predetermined regularity.
  • the pores 11 a and the pores 12 a are arranged in a line along the direction from the center toward the circumference. These rows of pores are regularly arranged on the entire top surface 11 and bottom surface 12 along the radial direction (FIG. 1 shows only a part of the pores. .)
  • the pores 11a and the pores 12a are radially arranged from the center toward the circumference.
  • the pores 14a are disposed on the entire side surface 14 (FIG. 1 shows only a part of the pores).
  • FIG. 2 is a diagram showing how the diatom 10 is dismantled.
  • the diatom 10 can be easily disassembled into a top cover including the top surface 11 and a bottom cover including the bottom surface 12 starting from the cylindrical side surface 14.
  • the disks 13 are disassembled as separate bodies one by one on the top surface 11 side and the bottom surface 12 side, respectively, during the manufacturing process of the minute metal structure described later.
  • FIG. 3 is a diagram for explaining the detailed structure of the diatom 10.
  • a first disk 131 and a second disk 132 are provided along the direction from the top surface 11 to the bottom surface 12, respectively. These first and second disks 131 and 132 form a two-layer structure.
  • the first disc 131 and the second disc 132 are provided with a plurality of pores 131a (corresponding to the pore 11a) and a plurality of pores 132a so as to penetrate these.
  • the diameter of the pore 131 a of the first disk 131 is smaller than the diameter of the pore 132 a of the second disk 132.
  • These arranged pore groups are also arranged with a predetermined regularity like the pores 11a and 12a.
  • the pores 131a and the pores 132a are arranged in a line along the direction from the center toward the circumference. These rows of pores are regularly arranged on the entire first disk 131 and second disk 132 so as to follow the radial direction. In other words, in the first disc 131 and the second disc 132, the pores 131a and the pores 132a are radially arranged from the center toward the circumference.
  • the first disk 131 and the second disk 132 are arranged so as to be separated from each other in parallel by interposing a wall 133 having a predetermined height.
  • the wall 133 is configured to have a honeycomb shape as a whole.
  • the wall 133 is configured to surround one of the pores 132a of the second disk 132 with the honeycomb 1 cell. That is, the wall 133 functions as a support column that connects the first disk 131 and the second disk 132. One end of this support column is disposed so as to surround the second disk 132 and one pore 132a. On the other hand, the other end of the column is disposed so as to surround the first disk 131 and the plurality of pores 131a.
  • a structure similar to the relationship between the first disk 131 and the second disk 132 is formed along the direction from the bottom surface 12 toward the top surface 11. That is, in the disk 13 on the bottom surface 12 side, a first disk 131 and a second disk 132 are provided along the direction from the bottom surface 12 to the top surface 11 in the same manner as described above, and each of these is formed so as to penetrate these.
  • a plurality of holes 131a (corresponding to the pores 12a) and a plurality of pores 132a are provided.
  • the top surface 11 and the bottom surface 12 are each composed of two disks 13, and a communication path is formed inside. That is, the pore 131 a of the first disk 131 (the pore 11 a of the top surface 11) communicates with the pore 132 a of the second disk 132. Therefore, the pore 11a on the top surface 11 communicates with the pore 12a on the bottom surface 12 through these pores 131a and 132a. In addition, the space between the first disk 131 and the second disk 132 communicates with the pores 14 a on the side surface 14. Therefore, for example, when the fluid is pressurized outside the diatom 10, the fluid can flow into the internal space of the diatom 10 through the communication portion formed as described above. The above is the description of the structure of the diatom 10.
  • Pretreatment process First, the cultured diatom 10 is collected.
  • a culture medium in accordance with the constituent elements of the diatom 10.
  • the diatom 10 is a core diatom
  • artificial seawater in which the contents of carbon source, nitrogen source and mineral are adjusted, natural seawater, and the like may be used.
  • the fractionation the culture medium and the diatom 10 are separated using a predetermined solid-liquid separation means.
  • the solid-liquid separation means may be suction filtration using a membrane filter, for example.
  • the diatom 10 to be sorted is subjected to a cleaning process. Specifically, the diatom 10 is dispersed and shaken in a solution in which the cleaning agent is adjusted to a predetermined concentration. From there, only the diatom 10 is recovered. The diatom 10 is washed by repeating these several times. Next, the washed diatom 10 is treated with a surfactant. Specifically, diatom 10 is impregnated in a solution in which a surfactant is adjusted to a predetermined concentration. By this treatment, the surfactant also flows into the inner space of the diatom 10.
  • the surface of the diatom 10 (including the outer surface as a columnar shape and the surface forming the internal space (that is, the surface of the first disk 131, the second disk 132, and the wall 133) is also included. See FIG. 4)
  • effective degreasing is performed and a surfactant molecular layer is formed.
  • the stirring method include mechanical stirring using a stirring bar, stirring associated with aeration bubbling, and the like.
  • FIG. 4 is a longitudinal sectional view of the first disk 131 and the second disk 132 for explaining the process of adsorbing the catalyst on the surface of the diatom 10.
  • the catalyst is adsorbed to the diatom 10 treated with the surfactant as described above.
  • the diatom 10 is impregnated in a solution in which a catalyst composed of a palladium-tin complex is adjusted to a predetermined concentration.
  • the palladium-tin complex is uniformly adsorbed on the surface treated with the surfactant.
  • metallic palladium is produced from the adsorbed catalyst.
  • the tin salt is dissolved and the catalyst is reduced as metallic palladium.
  • the surface is covered with metallic palladium.
  • the core of electroless plating metallic palladium
  • the solution for electroless plating can be selected according to the metal species of the first layer.
  • a solution containing nickel ions and dimethylaminoborane is used as this solution.
  • the metal of the first layer 20 is not limited to nickel, but a metal having a large ionization tendency is preferable as compared with a metal forming the second layer described later.
  • the amount of the plating bath solution used for the plating process is preferably adjusted to 1 L with respect to the total surface area of diatom 10 of 100 to 200 cm 2 .
  • FIG. 5 is a longitudinal sectional view of the first disk 131 and the second disk 132 for explaining the process of forming the first layer 20 on the surface of the diatom 10.
  • the coated diatom 10 is impregnated with the electroless plating solution.
  • the solution flows into the passage and space of the diatom 10 described above. For this reason, it contacts with the metal palladium coated.
  • the palladium acts as a catalyst by setting a predetermined condition. Therefore, nickel (ion) in the vicinity of palladium in the solution is reduced by dimethylamine borane. In accordance with this reduction, metallic nickel is uniformly deposited on the palladium surface.
  • FIG. 6 is a view for explaining a mechanism when metallic nickel as the first layer 20 is deposited.
  • the anodic reaction and the cathodic reaction proceed simultaneously.
  • an anodic reaction as shown in the following formula (1), electrons e ⁇ are released from dimethylaminoborane (CH 3 ) 2 NHBH 3 in the solution. This reaction proceeds using the metal palladium as a catalyst at the start.
  • a cathode reaction as shown in the following formulas (2) and (3), emitted electrons e ⁇ are transferred to nickel ions Ni 2+ and hydrogen ions H + in the solution. These are reduced as metal and gas, respectively, and in accordance with this reduction, precipitation of metallic nickel is started.
  • the deposited nickel metal itself acts as a catalyst (electroless plating nucleus). Therefore, new nickel ions Ni 2+ in the solution are reduced by dimethylaminoborane (CH 3 ) 2 NHBH 3 using the precipitated metallic nickel as a catalyst. That is, once metallic nickel is deposited, the following reactions (1), (2), and (3) proceed based on the autocatalytic properties of metallic nickel. As the above reactions progress, in the cathode reaction, nickel boron Ni 2 B is also precipitated as a side reaction as shown in (4) below. Therefore, the material constituting the first layer 20 is metallic nickel containing nickel boron. In this way, metallic nickel is deposited on metallic palladium with a predetermined coating rate.
  • CH 3 dimethylaminoborane
  • FIG. 7 is a diagram for explaining the relationship between the coating thickness of the first layer 20 and the coating time.
  • the coating thickness indicates the length of the layer that extends outward from the surface of the diatom 10 and that is perpendicular to the surface.
  • the coating time indicates the time from the start to the completion of the formation of the first layer 20.
  • the coating time is adjusted in the formation of the first layer 20 so that the pores 131a of the first disk 131 are not blocked by the metal coating. From this viewpoint, the coating thickness of the first layer 20 is set as follows.
  • T1 is set based on D, t, and the following equation (5), where D is the diameter of the pore 131a, t is the coating thickness of the palladium layer, and t1 is the coating thickness of the first layer 20.
  • the covering time is adjusted to be the covering time T1 corresponding to t1 set in this way. t1 ⁇ D / 2-t (5)
  • FIG. 8 is a graph showing the relationship between the coating speed v, the temperature of the solution, and the pH of the solution.
  • the coating rate v increases as the temperature increases and the pH increases. Accordingly, the coating rate v is determined based on the solution temperature, pH, and this relationship.
  • the coating time T1 is set by dividing the set coating thickness t1 at the determined coating speed v. In this way, the coating time T1 is adjusted at the coating speed v (that is, the temperature, pH of the solution, and the relationship of FIG. 78).
  • the first layer 20 of metallic nickel is formed over the entire surface coated with metallic palladium.
  • the electroless plating of metallic nickel follows the biological tissue of core diatom and metal coating is achieved in the first layer 20.
  • the diameter of the pore 131b of the second disk 132 is larger than the diameter D of the pore 131a of the first disk 131. For this reason, as described above, the fine layer 132a is not blocked by the metal coating by setting the coating thickness of the first layer 20 to t1. The above is the description of the first layer formation process.
  • the diatom 10 metal-coated with the first layer 20 is further subjected to electroless plating.
  • the solution for electroless plating can be selected according to the metal species of the second layer 30.
  • a solution containing gold ions for example, an aqueous solution of sodium gold sulfite Na 3 Au (SO 3 ) 2 or an aqueous solution of potassium gold cyanide KAu (CN) 2 ) is used.
  • the metal of the second layer 30 is not limited to gold, but preferably has a smaller ionization tendency than nickel forming the first layer 20.
  • FIG. 9 is a longitudinal sectional view of the first disk 131 and the second disk 132 for explaining the process of forming the second layer 30 on the surface of the diatom 10.
  • the diatom 10 metal-coated with the first layer 20 is impregnated with the electroless plating solution.
  • the solution flows into the passage and space of the diatom 10 described above. For this reason, it contacts the coated first layer 20 (ie, metallic nickel).
  • gold (ions) in the vicinity of the first layer 20 in the solution is reduced by metallic nickel. In accordance with this reduction, gold (metal) is uniformly deposited on the surface of the first layer 20.
  • FIG. 10 is a diagram for explaining a mechanism when gold as the second layer 30 is deposited.
  • the anodic reaction and the cathodic reaction proceed simultaneously.
  • an anodic reaction as shown in the following formula (6), a part of the metallic nickel of the first layer 20 is oxidized and electrons e ⁇ are emitted. This is based on the standard electrode potential (ionization tendency) of nickel being lower (greater) than that of gold.
  • a cathode reaction as shown in the following formula (7), electrons e ⁇ emitted to gold ions Au 3+ are delivered.
  • FIG. 11 is a diagram for explaining the relationship between the coating thickness of the second layer 30 and the coating time.
  • the coating time indicates the time from the start to the completion of the formation of the second layer 30.
  • the coating time is adjusted so that the pores 131a of the first disk 131 are not blocked by the metal coating.
  • t2 is set based on the above D, t, t1, and the following equation (8).
  • the covering time is adjusted to be the covering time T2 corresponding to t2 set in this way.
  • the coating thickness t2 and the coating time T2 of the second layer 30 are set in consideration of the amount of the first layer 20 to elute. Is preferred. t2 ⁇ D / 2 ⁇ (t + t1) (8)
  • the gold second layer 30 is formed over the entire surface covered with the first layer 20.
  • the electroless plating of gold follows the biological tissue of the diatom 10 (core diatomaceous earth), and metal coating is achieved in the second layer 30.
  • the pore 132a of the second disk 132 is not blocked by the metal coating by setting the coating thickness of the second layer 30 to t2. The above is the description of the second layer formation process.
  • Removal process will be described. As described above, only the portion corresponding to the diatom 10 is removed from the diatom 10 that is metal-coated with the first layer 20 and the second layer 30. That is, a structure composed of only the metal layer is obtained by the removal process.
  • an aqueous solution exhibiting alkalinity for example, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution
  • a predetermined concentration for example, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution
  • FIG. 12 is a longitudinal sectional view of the first disk 131 and the second disk 132 for explaining the process for removing the diatom 10.
  • the diatom 10 metal-coated with the first layer 20 and the second layer 30 is impregnated with the solution for removal.
  • silicon derived from the diatom 10 is eluted into the solution by heating at a predetermined temperature and a predetermined time.
  • the portion occupied by the diatom 10 inside the metal layer becomes a space.
  • the optical transmittance of the minute metal structure 40 can be improved as compared with that before the diatom 10 is removed.
  • FIG. 13 is a bird's-eye view from the first surface 41 side of the minute metal structure 40 according to the embodiment of the present invention.
  • the fine metal structure 40 is a part of the structure obtained through the above-described four processes.
  • the minute metal structure 40 includes a part corresponding to the first disk 131 and the second disk 132, and only a part corresponding to the wall 133 and the side surface 14 connecting them from the structure in which the entire diatom 10 is coated with metal. Extracted.
  • the micro metal structure 40 has a circular first surface 41 and a circular second surface 42 having the same diameter as the first surface 41.
  • a plurality of first pores 41a are regularly arranged on the first surface 41 along a direction from the center of the circle toward the circumference.
  • the first pore 41a corresponds to the pore 131a of the first disk 131.
  • On the second surface 42 a plurality of second pores 42a having a diameter larger than that of the first pore 41a are disposed.
  • the second pore 42 a corresponds to the pore 132 a of the second disk 132.
  • FIG. 14 is a vertical cross-sectional view of the fine metal structure 40 according to the embodiment of the present invention.
  • the first surface 41 and the second surface 42 are spaced apart from each other in parallel with an interval corresponding to the height of the wall 133.
  • the minute metal structure 40 is a hollow disk including the hollow portion 43.
  • the 1st layer 20 and the 2nd layer 30 are formed along the direction which goes outside from the surface of diatom 10 as a template. That is, the first layer 20 functions as a base for the second layer 30.
  • the metal layers are configured to have the above-described specific shape.
  • suppression of peeling and aggregation of the metal layer can be achieved, and the quality of the metal coating can be improved in the fine metal structure 40.
  • a precise shape can be achieved.
  • the minute metal structure 40 manufactured in this way is constituted by a metal coating on the whole or part of the diatom 10.
  • This fine metal structure 40 has the transmission and absorption characteristics of electromagnetic waves derived from the pore arrangement. For this reason, the minute metal structure 40 can be applied to a polarizer, a Cavity Strong Coupling, or the like.
  • the transmission / absorption characteristics described above may be expressed by suspending / dispersing the fine metal structure 40 in a liquid medium. Since the pore diameter itself of the fine metal structure 40 and the permeability of the medium into the pores can be estimated, for example, average plasmon characteristics can be obtained.
  • the first layer 20 nickel having a high ionization tendency is used for the first layer 20, and gold having a low ionization tendency is used for the second layer 30.
  • the first layer 20 can be the base of the second layer 30. Thereby, it can suppress that the 1st, 2nd layers 20 and 30 mutually peel.
  • the gold alone of the second layer 30 makes it difficult to follow the coating with respect to the diatom 10, but the quality of the metal coating can be improved by the configuration of the fine metal structure 40 described above.
  • core diatom can be cultured in large quantities with a certain quality in a relatively short period of time. Therefore, including a diatom 10 culturing process as a template, a fine metal structure having a precise shape can be obtained stably and in large quantities.
  • a diatom 10 culturing process as a template, a fine metal structure having a precise shape can be obtained stably and in large quantities.
  • nickel and gold were used as the metals of the first and second layers 20 and 30, respectively.
  • the metals of the first and second layers 20 and 30 were selected from the group of silver, copper, cobalt, and aluminum Two types may be used. In this case, it is preferable to select the first and second layers 20 and 30 so that the metal ionization tendency of the first layer 20 is larger than that of the second layer 30.
  • the second layer formation process may be configured as follows.
  • a solution containing copper ions and formaldehyde is used as a solution for electroless plating.
  • the diatom 10 metal-coated with the first layer 20 is impregnated with the electroless plating solution.
  • the solution flows into the passage and space of the diatom 10 described above. For this reason, it contacts the coated first layer 20 (ie, metallic nickel).
  • the metallic nickel acts as a catalyst by setting a predetermined condition. Accordingly, copper (ions) in the vicinity of the first layer 20 in the solution is reduced by formaldehyde. According to this reduction, metallic copper is uniformly deposited on the surface of the first layer 20.
  • FIG. 15 is a view for explaining a mechanism when metallic copper as the second layer 30 is deposited.
  • the anodic reaction and the cathodic reaction proceed simultaneously.
  • an anodic reaction as shown in the following formula (9)
  • a part of the metallic nickel in the first layer 20 is eluted and electrons e ⁇ are emitted. This is based on the standard electrode potential (ionization tendency) of nickel being lower (larger) than that of copper.
  • a cathode reaction as shown in the following formula (10), electrons e ⁇ released to copper ions Cu 2+ are delivered.
  • core diatom is used as the diatom 10 as a template, but instead, for example, aoremuna may be used.
  • Aeolymna can also be cultured in a large amount with a constant quality in a relatively short period of time, like the above-mentioned core diatom. Therefore, this also includes a cultivation process of the diatom 10 as a template, and a fine metal structure having a fine shape can be obtained stably and in large quantities.
  • the diatom 10 as a template has been removed through the removal process, this process may be omitted. That is, 3. Even after the second layer 30 is coated in the second layer forming process, the diatom 10 may not be removed and may be contained in the fine metal structure 40 as it is. This is based on the fact that when the optical distance corresponding to the distance between the first disk 131 and the second disk 132 is short, the transmittance is sufficiently large even if the diatom 10 is contained as it is. According to this, since one process is omitted, the fine metal structure 40 can be manufactured more easily as an entire process.
  • the second layer 30 is directly formed on the surface of the first layer 20. That is, 3.
  • the gold of the second layer 30 was deposited using the nickel of the first layer 20.
  • the surface of the first layer 20 may be further covered with metallic palladium.
  • the formation of the second layer 30 may be started after the metal palladium coating is completed.
  • this metal palladium functions as a catalyst, and reduction of gold ion and precipitation of gold (metal) are achieved. For this reason, the elution of nickel in the first layer 20 can be further suppressed.
  • the coating thicknesses t1 and t2 of the first layer 20 and the second layer 30 are set in consideration of the coating thickness of the metal palladium so that the pores 131a are not blocked.
  • Table 1, Table 2, Table 3, and Table 4 show the above-mentioned “1. Pretreatment process”, “2. First layer formation process”, “3. Second layer formation process”, and “4. Removal process”. Is a table showing the details of each.
  • the “step” indicates a solution treatment with respect to core diatomaceous earth.
  • core diatomaceous earth was dispersed in the solution with a predetermined temperature and holding time. Stirring was continued with a stirrer during dispersion into the solution. After completion of each step, each solid matter was filtered with a filter cloth and washed with pure water at the time of filtration. Then, it advanced to the next process.
  • “Chemicals” indicates the substance name or product name of the chemical dissolved in the solution in each step.
  • “Concentration” is the concentration of the chemical in the solution.
  • the solvent was pure water.
  • “Processing conditions” indicate the temperature and holding time for solution processing.
  • Pre-processing process will be described with reference to Table 1.
  • a culture solution containing diatom core diatomaceous earth
  • a 500 to 700 mesh filter cloth was used for filtration.
  • About 2 mg of diatom as a solid substance was dispersed in 10 mL of distilled water in a 50 mL beaker.
  • 10 mL of pipe unish (trademark, manufactured by Johnson Co., Ltd.) was added as a washing liquid, and the beaker was shaken and stirred, and then allowed to stand for 30 minutes.
  • This solution was filtered again to collect a solid, and then dispersed in distilled water. After this collection and dispersion were repeated 5 times, the washed core diatom was stored in a solution of distilled water and ethanol in a ratio of 1: 1.
  • FIG. 16 is an SEM image showing the entire core diatom after the cleaning treatment.
  • FIG. 17 is an SEM image showing an enlarged view of the core diatom.
  • an EDX-SEM composed of a silicon drift detector EDAX APOLLO (Ametech Co., Ltd.) and an ultra-high resolution field emission scanning electron microscope SU8020 (Hitachi High Technologies Co., Ltd.) was used. It was confirmed that the core diatom had a cylindrical shape. It was confirmed that pores having a small diameter (corresponding to the first pores) exist in the portion corresponding to the first surface of the core diatom. The pores had an average diameter of about 209 nm.
  • pores having a large diameter were present at the site corresponding to the second surface of the core diatom.
  • the pores had an average diameter of approximately 1171 nm. These average diameters are average values of the measured values of each diameter when the number of observed pores is 20.
  • FIG. 18 is a graph showing an EDX spectrum corresponding to the imaged SEM image.
  • the same EDX-SEM as described above was used, and the probe current was “high” and the scanning condition was 1 minute. It was confirmed that the core diatom was composed of silica. In other words, it was confirmed that any metal was not coated on the core diatom before plating.
  • OPC-370 Condy Clean MA (trademark, manufactured by Okuno Pharmaceutical Co., Ltd.) with a concentration of 50 mL / L was added to 10 mL of the stored solution. did. At this time, the etal content of the solution was replaced with distilled water. The chemicals were added to the solution so that the total liquid volume was 500 mL. It should be noted that the total liquid amount was 500 mL in the subsequent chemical additions.
  • the amount of core diatomite in the solution was adjusted to about 0.15 mg, and the concentration of the solid substance was set to about 0.30 mg / L (solution).
  • the average value of the specific surface area of this core mussel was 3 ⁇ 10 5 cm 2 / g. Therefore, the total surface area of the core diatom is 100 cm 2 with respect to 1 L of the solution (including the solution for the plating bath). In each subsequent process, the amount of the core diatom is maintained.
  • OPC-50 inducer A having a concentration of 25 mL / L
  • OPC-50 inducer C having a concentration of 25 mL / L (trademark, manufactured by Okuno Pharmaceutical Co., Ltd.) are applied to the above-mentioned core treated diatom ) Was added as pH 12.
  • OPC-150 Cryster MU (trademark, manufactured by Okuno Pharmaceutical Co., Ltd.) having a concentration of 75 mL / L was added to the core adsorbent treated with the catalyst.
  • Second layer formation process will be described with reference to Table 2.
  • the activated core myrium is 90 mL / L of top chemialloy 66-MLF, 15 mL / L of top chemialloy 66-1LF, and 60 mL / L of top chemialloy 66-2LF. (Trademark, manufactured by Okuno Pharmaceutical Co., Ltd.) was added at pH 6.5.
  • FIG. 19 is a graph defining the relationship between the nickel coating rate (nm / min) and the temperature (° C.) in the nickel plating process.
  • This graph is created by previously obtaining the coating speed corresponding to each temperature and plotting the data. That is, this graph corresponds to that described in FIG.
  • the conditions in this plot are that the total surface area of core diatom is 100 cm 2 / L (solution) and the pH is 6.5.
  • the coating speed is 60 nm / min.
  • the predicted value of the coating thickness was set to 60 nm based on the average value of each pore diameter that can be read from FIG. 16 and the above equation (5). Based on this set coating thickness and coating speed, the coating time was adjusted to 1 minute.
  • FIG. 20 is an SEM image showing the entire fine metal structure after the nickel plating process.
  • FIG. 21 is an SEM image showing an enlarged view of the fine metal structure.
  • SEM For imaging by SEM, the same EDX-SEM as that used after the cleaning process was used. In this fine metal structure, it was confirmed that the metal coating satisfactorily followed the shape of the above-mentioned core diatomaceous earth.
  • Small pores (corresponding to the first pores) had an average diameter of approximately 53 nm.
  • the pores having a large diameter (corresponding to the second pores) had an average diameter of approximately 1412 nm.
  • the value larger than the average diameter measured from the SEM image after a washing process was shown. This is due to variations in the pore diameter of core diatomaceous earth, and does not grow due to the connection of the pores or the like during nickel metal coating. This variation was about ⁇ 150 nm as a deviation.
  • FIG. 22 is a graph showing an EDX spectrum corresponding to the imaged SEM image.
  • the spectrum was acquired using the same EDX-SEM and conditions as described above. It was confirmed that this fine metal structure was composed of silica and nickel. That is, it was confirmed that nickel was coated on the core diatom by nickel plating treatment.
  • NC gold HS II (trademark, Kojima Chemical Co., Ltd.) having a concentration of 2.0 g / L (only in this table indicates the concentration of the solution with respect to the mass of the metal (Au)) is applied to the activated core myrtle. (Made by company) was added.
  • FIG. 23 is a graph that defines the relationship between the gold coating rate (nm / min) and the temperature (° C.) in the gold plating process.
  • This graph is created by previously obtaining the coating speed corresponding to each temperature and plotting the data. That is, this graph corresponds to that described in FIG.
  • the conditions in this plot are that the total surface area of core diatom is 100 cm 2 / L (solution) and the pH is 8.5.
  • the coating speed is 5 nm / min.
  • the predicted value of the coating thickness is set to 100 nm based on the average value of each pore diameter that can be read from FIG.
  • the coating thickness of the nickel plating, the above equation (8), and the elution amount of the nickel layer. did. Based on the set coating thickness and coating speed, the coating time was adjusted to 20 minutes. In addition, the coating thickness of this setting is larger than the diameter of the 2nd pore after a nickel plating process.
  • the nickel layer coated with metal is eluted. Depending on the amount of elution, the nickel coating thickness decreases and the pores expand. For this reason, there is a margin for preventing the pores from being blocked, and even when the coating thickness is set to this value, the pores can be blocked.
  • FIG. 24 is an SEM image showing the entire fine metal structure after the gold plating process.
  • FIG. 25 is an SEM image showing an enlarged view of the fine metal structure.
  • the pores with a small diameter (corresponding to the first pores) had an average diameter of approximately 126 nm.
  • the pores having a large diameter (corresponding to the second pores) had an average diameter of about 1200 nm.
  • the value larger than the average diameter measured from the SEM image after a nickel plating process was shown. This is because nickel elution erosion occurs and the nickel coating thickness is reduced, and the pore diameter does not grow due to the connection of the pores when gold is coated with metal.
  • FIG. 26 is a graph showing an EDX spectrum corresponding to the imaged SEM image.
  • the spectrum was acquired using the same EDX-SEM and conditions as described above. It was confirmed that this fine metal structure was composed of silica, nickel, and gold. That is, it was confirmed that gold was coated on the nickel layer by gold plating.
  • Removal Process will be described with reference to Table 4.
  • sodium hydroxide having a concentration of 0.10 mol / L was added to the above-described core plating treated with gold plating. After completing these processes, it was washed and dried to obtain a fine metal structure.
  • peeling and aggregation of the metal layer were suppressed, and high-quality metal coating was confirmed.
  • a fine shape derived from the shape of the core diatom was achieved.
  • FIG. 27 is a diagram showing optical characteristics when the fine metal structure obtained by the above process is used as a hole array.
  • what is added as “hole” is a spectrum when the above-described fine metal structure is used.
  • the transmittance locally increased at 450 nm and 670 nm.
  • a transmittance of 1.5% was confirmed at 670 nm.
  • the fine metal structure of the present invention is obtained on the basis of coating a metal layer on the surface of a biological tissue, thereby improving the quality of the metal coating and achieving a precise shape.
  • This fine metal structure is industrially useful because it can be applied to large-scale radio wave absorbers, cavity resonators, and the like.

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Abstract

Le problème décrit par l'invention est d'obtenir une forme délicate dans une microstructure métallique obtenue sur la base du recouvrement de la surface de tissu d'organisme avec une couche métallique. La solution selon l'invention porte sur une algue qui est utilisée comme matrice lors de la fabrication d'une microstructure métallique et sa surface est recouverte de métal dans un processus de placage. Une structure formée avec des couches métalliques (20, 30) a une première surface circulaire (41) et une seconde surface circulaire (42) de même diamètre que le diamètre de la première surface et est constituée pour former un disque creux, la première surface (41) et la seconde surface (42) étant séparées l'une de l'autre en parallèle avec un espace entre elles. Une pluralité de premiers pores (41a) sont disposés régulièrement sur la première surface le long d'une direction (41) allant du centre dans la forme circulaire vers sa périphérie. La microstructure métallique étant constituée ainsi, la qualité du recouvrement métallique peut être améliorée et une forme délicate peut être obtenue.
PCT/JP2015/061796 2014-04-30 2015-04-17 Microstructure métallique WO2015166816A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010123130A1 (fr) * 2009-04-22 2010-10-28 国立大学法人東京工業大学 Fine structure hélicoïdale, son procédé de fabrication et matière de blindage vis-à-vis des ondes électriques ou d'absorption des ondes électriques à l'aide de la fine structure hélicoïdale

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010123130A1 (fr) * 2009-04-22 2010-10-28 国立大学法人東京工業大学 Fine structure hélicoïdale, son procédé de fabrication et matière de blindage vis-à-vis des ondes électriques ou d'absorption des ondes électriques à l'aide de la fine structure hélicoïdale
JP2013150003A (ja) * 2009-04-22 2013-08-01 Tokyo Institute Of Technology 微小螺旋構造体と微小螺旋構造体を用いた電波遮蔽または吸収体

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