WO2022138151A1 - 金属充填微細構造体及び金属充填微細構造体の製造方法 - Google Patents

金属充填微細構造体及び金属充填微細構造体の製造方法 Download PDF

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WO2022138151A1
WO2022138151A1 PCT/JP2021/045023 JP2021045023W WO2022138151A1 WO 2022138151 A1 WO2022138151 A1 WO 2022138151A1 JP 2021045023 W JP2021045023 W JP 2021045023W WO 2022138151 A1 WO2022138151 A1 WO 2022138151A1
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Prior art keywords
metal
diameter
insulating film
filled microstructure
metal portion
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English (en)
French (fr)
Japanese (ja)
Inventor
吉則 堀田
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202180086340.9A priority Critical patent/CN116670337A/zh
Priority to JP2022572096A priority patent/JPWO2022138151A1/ja
Publication of WO2022138151A1 publication Critical patent/WO2022138151A1/ja
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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment

Definitions

  • the present invention relates to a metal-filled microstructure having a plurality of conductors penetrating in the thickness direction of the insulating film and provided in a state of being electrically insulated from each other, and a method for manufacturing the metal-filled microstructure, in particular, insulating.
  • the present invention relates to a metal-filled microstructure having a thick film and a method for manufacturing a metal-filled microstructure.
  • a structure in which a plurality of through holes provided in an insulating base material are filled with a conductive substance such as metal is one of the fields that have been attracting attention in nanotechnology in recent years.
  • a conductive substance such as metal
  • an anisotropic conductive member Is expected to be used.
  • An anisotropic conductive member is inserted between an electronic component such as a semiconductor element and a circuit board, and an electrical connection between the electronic component and the circuit board can be obtained simply by pressurizing the electronic component such as a semiconductor element.
  • It is widely used as an electrical connection member, an inspection connector for performing a functional inspection, and the like.
  • electronic components such as semiconductor elements are significantly downsized. Electronic components such as conventional wire bonding methods that directly connect wiring boards, flip chip bonding, thermocompression bonding, etc. may not be able to sufficiently guarantee the stability of electrical connections of electronic components.
  • An idiosyncratic conductive member is attracting attention as a connecting member.
  • Patent Document 1 one surface of an aluminum substrate is anodized, and an anode having a micropore existing in the thickness direction and a barrier layer existing at the bottom of the micropore on one surface of the aluminum substrate.
  • the barrier layer removal step of removing the barrier layer of the anodic oxide film after the anodic oxidation treatment step, and the electrolytic plating treatment after the barrier layer removal step the inside of the micropore is subjected to electrolytic plating treatment.
  • a method for manufacturing a metal-filled microstructure is described, which comprises a metal filling step of filling metal, and a substrate removing step of removing an aluminum substrate to obtain a metal-filled microstructure after the metal filling step.
  • the anodized film of Patent Document 1 is an insulating film.
  • An object of the present invention is to provide a metal-filled microstructure having a thick insulating film and a method for manufacturing a metal-filled microstructure.
  • one aspect of the present invention has an insulating film and a plurality of conductors penetrating in the thickness direction of the insulating film and provided in a state of being electrically insulated from each other.
  • the insulating film has a length of 100 ⁇ m or more in the thickness direction, and the plurality of conductors are each made of metal and are exposed on one surface in the thickness direction and the other surface in the thickness direction of the insulating film.
  • the present invention provides a metal-filled microstructure in which a first metal portion exposed on one surface and a second metal portion exposed on the other surface have different metals.
  • the plurality of conductors have different first diameters of the first metal portion exposed on one surface and second diameters of the second metal portion exposed on the other surface. It is preferable that the first metal part is made of Zn or Ni, and the second metal part is made of Cu.
  • the insulating film is preferably an anodized film.
  • Another aspect of the present invention includes a forming step of filling a plurality of through holes with a metal to form a conductor with respect to an insulating film having a plurality of through holes extending in the thickness direction.
  • the insulating film preferably has a length in the thickness direction of 100 ⁇ m or more.
  • the insulating film is preferably an anodized film.
  • a metal-filled microstructure in which a conductor is formed in a through hole of a thick insulating film. Further, according to the present invention, it is possible to manufacture a metal-filled microstructure by forming a conductor in a through hole of a thick insulating film.
  • FIG. 6 shows a first example of the metal-filled microstructure according to the embodiment of the present invention.
  • the metal-filled microstructure 20 is provided with a plurality of conductors that penetrate the insulating film 14 and the insulating film 14 in the thickness direction Dt and are electrically insulated from each other. It has 16.
  • the plurality of conductors 16 are each made of metal.
  • the plurality of conductors 16 are exposed on one surface of the insulating film 14 in the thickness direction Dt, for example, the back surface 14b, and the other surface in the thickness direction Dt, for example, the surface 14a.
  • the first metal portion 16a exposed on one surface, for example, the back surface 14b, and the second metal portion 16b exposed on the other surface, for example, the surface surface 14a in the thickness direction Dt of the insulating film 14 are configured.
  • the metal to be used is different.
  • the first metal portion 16a is an exposed portion exposed on one surface, for example, the back surface 14b.
  • the second metal portion 16b is an exposed portion exposed on the other surface, for example, the surface 14a.
  • the insulating film 14 has a length in the thickness direction Dt, that is, a thickness of 100 ⁇ m or more. Further, the insulating film 14 has an electrical insulating property, and is composed of, for example, an anodic oxide film 15.
  • the plurality of conductors 16 are arranged on the insulating film 14 in a state of being electrically insulated from each other.
  • the insulating film 14 has a plurality of through holes 12 penetrating in the thickness direction Dt.
  • Conductors 16 are provided in the plurality of through holes 12.
  • the second metal portion 16b is exposed on the surface 14a of the insulating film 14 in the thickness direction Dt.
  • the first metal portion 16a is exposed on the back surface 14b of the insulating film 14 in the thickness direction Dt.
  • the conductor 16 By forming the conductor 16 into a laminated structure having a first metal portion 16a and a second metal portion 16b, even if the thickness ht of the insulating film 14 is thick, the length corresponds to the thickness of the insulating film 14. In addition, the conductor 16 can be lengthened.
  • the fact that the first metal portion 16a is exposed on the front surface 14a means that the end portion of the first metal portion 16a is at least at the position of the back surface 14b of the insulating film 14. For example, the end portion of the first metal portion 16a and the back surface 14b of the insulating film 14 are in a flush state.
  • the fact that the second metal portion 16b is exposed on the surface 14a means that the end portion of the second metal portion 16b is at least at the position of the surface 14a of the insulating film 14. For example, the end portion of the second metal portion 16b and the surface 14a of the insulating film 14 are in a flush state.
  • the first metal portion 16a may protrude from the back surface 14b, or the second metal portion 16b may protrude from the front surface 14a, for example.
  • the protrusion of the conductor 16 from the front surface 14a or the back surface 14b of the insulating film 14 is also included in the above-mentioned exposure.
  • the first metal portion 16a may be recessed with respect to the back surface 14b, or the second metal portion 16b may be recessed with respect to the front surface 14a.
  • the fact that the conductor 16 is recessed with respect to the front surface 14a or the back surface 14b of the insulating film 14 is also included in the above-mentioned exposure.
  • the recessing with respect to the front surface 14a or the back surface 14b of the insulating film 14 means that the tip of the second metal portion 16b is located at a position of a maximum of 1 ⁇ m from the front surface 14a of the insulating film 14 to the back surface 14b side. It means that the tip of the first metal portion 16a is at a position of a maximum of 1 ⁇ m from the back surface 14b of the insulating film 14 to the front surface 14a side.
  • the metal-filled microstructure 20 has anisotropic conductivity in which the conductors 16 are arranged in a state of being electrically insulated from each other.
  • the metal-filled microstructure 20 has conductivity in the thickness direction Dt, but the conductivity in the direction parallel to the surface 14a of the insulating film 14 is sufficiently low.
  • the outer shape of the metal-filled microstructure 20 is not particularly limited, and is, for example, rectangular or circular. The outer shape of the metal-filled microstructure 20 can be shaped according to the application, ease of manufacture, and the like.
  • the insulating film is composed of an anodic oxide film of aluminum. Therefore, in the first example of the method for manufacturing a structure, first, as shown in FIG. 1, an aluminum substrate 10 is prepared. The size and thickness of the aluminum substrate 10 are appropriately determined according to the thickness ht (see FIG. 6) of the insulating film 14 of the finally obtained metal-filled microstructure 20 (see FIG. 6), the apparatus to be processed, and the like. It is a thing.
  • the aluminum substrate 10 is, for example, a rectangular plate material. It should be noted that the present invention is not limited to the aluminum substrate, and a metal substrate capable of forming the insulating film 14 having electrical insulating properties can be used.
  • the surface 10a (see FIG. 1) on one side of the aluminum substrate 10 is anodized.
  • the surface 10a (see FIG. 1) on one side of the aluminum substrate 10 is anodized, and as shown in FIG. 2, the insulating film 14 having a plurality of through holes 12 extending in the thickness direction Dt of the aluminum substrate 10 That is, the anodic oxide film 15 is formed.
  • a barrier layer 13 (see FIG. 2) is present at the bottom of each through hole 12.
  • the above-mentioned anodizing step is called an anodizing treatment step.
  • the insulating film 14 having the plurality of through holes 12 has the barrier layer 13 (see FIG. 2) at the bottom of the through holes 12, but the barrier layer 13 shown in FIG. 2 is removed.
  • an insulating film 14 (see FIG. 3) having a plurality of through holes 12 without the barrier layer 13 is obtained.
  • the step of removing the barrier layer 13 is referred to as a barrier layer removing step.
  • the barrier layer removing step for example, the barrier layer 13 of the insulating film 14 is removed by using an alkaline aqueous solution containing ions of metal M1 having a higher hydrogen overvoltage than aluminum, and the bottom surface 12c of the through hole 12 (see FIG. 3). Is exposed on the aluminum substrate 10.
  • the aluminum substrate 10 can be used as an electrode in the AC electrolytic plating method.
  • the forming step of forming the conductor 16 described above includes a first step of forming the first metal portion 16a and a second step of forming the second metal portion 16b, which are shown below.
  • one surface side of the anodic oxide film 15 which is the insulating film 14 in the thickness direction Dt is formed in the plurality of through holes 12, for example, as shown in FIG. 4, the back surface 14b of the insulating film 14 (FIG. 6) From the side, it is a step of forming the first metal portion 16a by using the AC electrolytic plating method.
  • the aluminum substrate 10 is used as an electrode, and a voltage is modulated in a sinusoidal manner at a predetermined frequency and applied to perform plating from the aluminum substrate 10 side of the insulating film 14.
  • the plating proceeds from the aluminum substrate 10 facing the bottom surface 12c of the through hole 12 as a starting point to form the first metal portion 16a.
  • the first metal portion 16a is formed, for example, to have a length of about 10 ⁇ m in the thickness direction Dt.
  • the first metal portion 16a formed on the bottom surface 12c of the through hole 12 is an exposed portion exposed on the back surface 14b as described above.
  • the second step is a step of forming the second metal portion 16b on the first metal portion 16a of the plurality of through holes 12 by using the DC electrolytic plating method.
  • the second metal portion 16b is formed up to the surface 14a of the insulating film 14.
  • the second metal portion 16b is exposed on the surface 14a of the insulating film 14.
  • the second metal portion 16b is an exposed portion exposed on the surface 14a.
  • the DC electrolytic plating method the aluminum substrate 10 is used as an electrode, and a DC voltage is applied to perform plating from the first metal portion 16a.
  • plating proceeds from the first metal portion 16a as a starting point to form the second metal portion 16b.
  • the length of the second metal portion 16b in the thickness direction Dt is the length obtained by subtracting the length of the first metal portion 16a in the thickness direction Dt from the thickness of the insulating film 14. Therefore, the length of the second metal portion 16b in the thickness direction Dt is determined by the thickness of the insulating film 14 and the length of the first metal portion 16a in the thickness direction Dt.
  • the conductive body 16 is formed, and the conductive body 16 is a laminated structure in which the second metal portion 16b is formed on the first metal portion 16a.
  • the diameter d of the conductor 16 is constant with no change in diameter in the thickness direction Dt.
  • the conductive body 16 is a laminated structure in which the second metal portion 16b is formed on the first metal portion 16a, but the conductive body 16 is limited to the configuration of the first metal portion 16a and the second metal portion 16b.
  • the other metal part may be one, or may have a plurality of different metal parts made of different metals.
  • the other metal portion may be the same metal as any one of the first metal portion 16a and the second metal portion 16b, or may be composed of different metals.
  • the aluminum substrate 10 is removed from the anodic oxide film 15 which is the insulating film 14.
  • the step of removing the aluminum substrate 10 from the anodized film 15 is called a substrate removing step.
  • the surface of the insulating film 14 on the side where the aluminum substrate 10 is provided is the back surface 14b.
  • the metal-filled microstructure 20 shown in FIG. 6 is obtained.
  • the first metal portion 16a is exposed on the back surface 14b of the insulating film 14, and the second metal portion 16b is exposed on the front surface 14a of the insulating film 14.
  • the surface 14a of the insulating film 14 on the side where the aluminum substrate 10 is not provided is partially removed in the thickness direction Dt, and the second metal portion 16b is the surface of the insulating film 14. It may be projected beyond 14a. That is, the conductor 16 may be projected from the surface 14a of the insulating film 14.
  • the step of projecting the conductor 16 from the surface 14a of the insulating film 14 is referred to as a surface metal projecting step.
  • the step of projecting the conductor 16 from the back surface 14b of the insulating film 14 is referred to as a back surface metal projecting step.
  • the above-mentioned front surface metal protrusion step and back surface metal protrusion step may have both steps, but may have one of the front surface metal protrusion step and the back surface metal protrusion step.
  • the front surface metal projecting process and the back surface metal projecting process correspond to the "projection process", and the front surface metal projecting process and the back surface metal projecting process are both projecting processes.
  • FIGS. 7 to 11 are schematic cross-sectional views showing a second example of the method for manufacturing a metal-filled microstructure according to the embodiment of the present invention in order of steps.
  • FIGS. 7 to 11 the same components as those shown in FIGS. 1 to 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • FIG. 11 shows a second example of the metal-filled microstructure according to the embodiment of the present invention.
  • the metal-filled microstructure 20a shown in FIG. 11 is different from the metal-filled microstructure 20 shown in FIG. 6 in that the through hole 12 has a larger diameter, and the other configurations are the same.
  • the plurality of conductors 16 are respectively on one surface, for example, the first diameter d1 of the first metal portion 16a exposed on the back surface 14b, and on the other surface, for example, the surface 14a.
  • the exposed second metal portion 16b is different from the second diameter d2.
  • the first diameter d 1 ⁇ the second diameter d 2 .
  • the enlarged diameter portion 12d of the through hole 12 is, for example, cylindrical, and its side surface is parallel to the thickness direction Dt. For example, if the first diameter d 1 is 60 nm, the second diameter d 2 is 70 nm.
  • the second example of the method for manufacturing a metal-filled microstructure differs from the first example of the method for manufacturing a metal-filled microstructure in that it has a diameter-expanding step for expanding the diameter of the through hole 12.
  • the steps other than the above are the same as in the first example of the method for manufacturing a metal-filled microstructure.
  • the insulating film 14 having a plurality of through holes 12 after the barrier layer removing step shown in FIG. 7 is subjected to the above-mentioned AC electrolytic plating method. As shown in FIG. 8, the first metal portion 16a is formed inside the through hole 12.
  • the step of forming the first metal portion 16a is the first step.
  • the first metal portion 16a has, for example, a length of about 10 ⁇ m in the thickness direction Dt.
  • the insulating film 14 shown in FIG. 7 has the same configuration as the insulating film 14 shown in FIG.
  • a diameter-expanding step of expanding the diameter of the through-hole 12 is carried out for the through-hole 12.
  • the diameter-expanding step is a step of expanding the hole diameter of the region where the first metal portion 16a is not formed in the through hole 12.
  • the diameter-expanding portion 12d is formed in the through hole 12 by the diameter-expanding step.
  • a step 12e is generated by the enlarged diameter portion 12d and the portion 12f on which the first metal portion 16a is formed.
  • the above-mentioned portion 12f is a part of the through hole 12 before the diameter expansion.
  • the pore-wide treatment is a treatment in which the anodized oxide film 15 which is an insulating film 14 is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodized oxide film 15 and expand the pore diameter of the through hole 12.
  • An aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like can be used.
  • a second metal portion 16b is formed on the enlarged diameter portion 12d of the through hole 12 and on the first metal portion 16a by using a DC electrolytic plating method. As a result, the conductor 16 is formed.
  • the formation of the second metal portion 16b described above is the second step.
  • the aluminum substrate 10 is removed from the anodized film 15 to obtain the metal-filled microstructure 20a shown in FIG.
  • one of the above-mentioned front surface metal protrusion step and back surface metal protrusion step may be carried out, or both steps may be carried out. good.
  • the metal-filled microstructure 20a shown in FIG. 11 has a structure in which the conductive body 16 projects from at least one of the front surface 14a and the back surface 14b of the insulating film 14.
  • FIGS. 12 to 14 are schematic cross-sectional views showing a third example of the method for manufacturing a metal-filled microstructure according to the embodiment of the present invention in order of steps.
  • FIGS. 12 to 14 the same components as those shown in FIGS. 7 to 11 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • the metal-filled microstructure obtained in the third example of the method for manufacturing the metal-filled microstructure is the same as the second example of the metal-filled microstructure shown in FIG. 11 above.
  • the third example of the method for manufacturing the metal-filled microstructure differs from the second example of the method for manufacturing the metal-filled microstructure in the timing of carrying out the diameter-expanding step for expanding the through hole.
  • the steps other than the above are the same as the second example of the method for manufacturing the metal-filled microstructure.
  • a third example of the method for manufacturing a metal-filled microstructure is a diameter-expanding step of expanding the diameter of the through-hole 12 with respect to the insulating film 14 having a plurality of through-holes 12 after the barrier layer removing step shown in FIG. To carry out. That is, in the third example of the method for manufacturing the metal-filled microstructure, the through hole 12 is expanded in diameter before the first metal portion 16a is formed on the bottom surface 12c of the through hole 12 (before the first step). ..
  • the diameter-expanding step is a step of expanding the hole diameter of the region where the first metal portion 16a is not formed in the through hole 12. As shown in FIG.
  • the diameter-expanding portion 12d is formed in the through hole 12 by the diameter-expanding step.
  • a first metal portion 16a is formed in the non-expanded portion 12f of the through hole 12 by using an AC electrolytic plating method (first step). ).
  • the enlarged diameter portion 12d creates a step 12e with a region where the first metal portion 16a is formed.
  • the above-mentioned portion 12f is a part of the through hole 12 before the diameter expansion.
  • the length of the portion 12f in the thickness direction Dt is appropriately determined according to, for example, the length of the first metal portion 16a, and is, for example, 10 ⁇ m.
  • a second metal portion 16b is formed on the enlarged diameter portion 12d of the through hole 12 and on the first metal portion 16a by using a DC electrolytic plating method (second step). As a result, the conductor 16 is formed.
  • the aluminum substrate 10 is removed from the anodized film 15 to obtain the metal-filled microstructure 20a shown in FIG.
  • the diameter expanding step is before the first step of forming the first metal portion 16a, or the first step of forming the first metal portion 16a and the second step of forming the second metal portion 16b. It can be carried out between steps.
  • the diameter expansion step between the first step of forming the first metal portion 16a and the second step of forming the second metal portion 16b because the first metal portion 16a is present.
  • the diameter of the enlarged diameter portion 12d of the through hole 12 can be easily controlled as compared with the case where the diameter expanding step is performed before the first step of forming the first metal portion 16a.
  • [Fourth example of metal-filled microstructure] 15 to 18 are schematic cross-sectional views showing a fourth example of the method for manufacturing a metal-filled microstructure according to an embodiment of the present invention in order of steps.
  • FIGS. 15 to 18 the same components as those shown in FIGS. 1 to 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • the metal-filled microstructure 20b shown in FIG. 18 has a different shape of the enlarged diameter portion 12g of the through hole 12 from the metal-filled microstructure 20a shown in FIG. 11, and the other configurations are the metal shown in FIG. It is the same as the filled microstructure 20a.
  • the enlarged diameter portion 12g has a conical trapezoidal shape, and its side surface is inclined with respect to the thickness direction Dt.
  • the pore diameter of the enlarged diameter portion 12g increases from the back surface 14b of the insulating film 14 toward the front surface 14a. Therefore, the plurality of conductors 16 are different from the first diameter d1 of the first metal portion 16a exposed on the back surface 14b and the second diameter d2 of the second metal portion 16b exposed on the front surface 14a.
  • the first diameter d 1 ⁇ the second diameter d 2 . Also in this case, for example, when the first diameter d 1 is 60 nm, the second diameter d 2 is 70 nm.
  • the fourth example of the method for manufacturing the metal-filled microstructure differs from the second example of the method for manufacturing the metal-filled microstructure in that the timing for carrying out the diameter-expanding step for expanding the through hole is different, and further.
  • the shape of the diameter-expanded portion 12g formed in the diameter-expanding step is different, and the other steps are the same as the second example of the method for manufacturing the metal-filled microstructure.
  • the enlarged diameter portion 12g has a conical stand shape.
  • a diameter-expanding step of expanding the diameter of the through-hole 12 is carried out for the insulating film 14 having the plurality of through-holes 12 after the barrier layer removing step shown in FIG. 7.
  • a conical stand-shaped diameter-expanding portion 12g is formed in the through hole 12 by the diameter-expanding step.
  • the diameter of the enlarged diameter portion 12g of the enlarged diameter portion 12g increases from the back surface 14b of the insulating film 14 toward the front surface 14a.
  • a first metal portion 16a is formed in the non-expanded portion 12f of the through hole 12 by using an AC electrolytic plating method (first step).
  • a second metal portion 16b is formed on the enlarged diameter portion 12g of the through hole 12 and on the first metal portion 16a by using a DC electrolytic plating method (second step).
  • the conductor 16 is formed.
  • the aluminum substrate 10 is removed from the anodized film 15 to obtain the metal-filled microstructure 20b shown in FIG.
  • the timing for carrying out the diameter-expanding step for expanding the through hole is before forming the first metal portion 16a (before the first step).
  • the present invention is not limited to this, and as in the second example of the method for manufacturing a metal-filled microstructure, after forming the first metal portion 16a (after the first step) and after the second metal.
  • the diameter expansion step of the through hole 12 may be carried out before forming the portion 16b (before the second step).
  • 19 to 21 are schematic cross-sectional views showing another example of the method for producing an anodized film of the metal-filled microstructure according to the embodiment of the present invention in order of steps.
  • the same components as those shown in FIGS. 1 to 3 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • the aluminum substrate 10 is removed from the aluminum substrate 10 on which the anodic oxide film 15 is formed as the insulating film 14 shown in FIG.
  • an insulating film 14 having a plurality of through holes 12 formed therein is obtained. Since the above-mentioned substrate removing step can be used for removing the aluminum substrate 10, detailed description thereof will be omitted.
  • the through hole 12 of the insulating film 14 is enlarged in diameter, the barrier layer 13 shown in FIG. 19 is removed, and a plurality of through holes 12 penetrating the insulating film 14 in the thickness direction Dt are formed as shown in FIG. do. Since the above-mentioned barrier layer removing step can be used for removing the barrier layer 13, detailed description thereof will be omitted. A pore-wide treatment can also be used to remove the barrier layer 13. The pore wide processing is as described above.
  • a metal layer 30 is formed on the entire surface of the back surface 14b of the insulating film 14 shown in FIG. 20, for example, by using a plating method on the entire surface of the back surface 14b of the insulating film 14 as shown in FIG.
  • the formation of the metal layer 30 is not limited to the plating method, and the metal layer 30 may be formed by, for example, a vapor deposition method or a sputtering method. However, from the viewpoint of the formation time of the metal layer 30, it is preferable to use a plating method having a higher film forming speed than the vapor deposition method and the sputtering method.
  • the metal layer 30 is a member corresponding to the aluminum substrate 10 described above, and is preferably made of the same metal as the aluminum substrate 10.
  • the metal layer 30 can be made of the same metal as the aluminum substrate 10 described above.
  • the metal layer 30 is provided on the back surface 14b side of the insulating film 14.
  • the metal layer 30 covers all the openings on the back surface 14b side of the insulating film 14 of the through hole 12.
  • the plating easily proceeds when the through hole 12 is filled with metal by metal plating, and the first metal portion 16a is easily formed.
  • the first metal portion 16a and the second metal portion 16b are formed inside the through hole 12 of the insulating film 14 as described above to form a conductor. 16 is formed.
  • the insulating film has an electrical insulating property, and is made of, for example, an inorganic material. For example, one having an electrical resistivity of about 10 14 ⁇ ⁇ cm can be used.
  • “consisting of an inorganic material” is a regulation for distinguishing from a polymer material, and is not limited to an insulating base material composed only of an inorganic material, but an inorganic material as a main component (50% by mass). The above).
  • the insulating film is composed of, for example, an anodic oxide film having electrical insulating properties.
  • the insulating film may be made of, for example, a metal oxide, a metal nitride, glass, silicon carbide, ceramics such as silicon nitride, a carbon base material such as diamond-like carbon, polyimide, a composite material thereof, or the like. ..
  • a ceramic material or an inorganic material containing 50% by mass or more of a carbon material may be formed on an organic material having through holes.
  • the length of the insulating film 14 in the thickness direction Dt that is, the thickness ht of the insulating film 14 is 100 ⁇ m or more.
  • the upper limit of the thickness ht of the insulating film 14 is not particularly limited, but is preferably 200 to 250 ⁇ m. When the upper limit of the thickness ht of the insulating film 14 is 200 to 250 ⁇ m, for example, it is suppressed that the processing time of the anodizing treatment becomes long, and further, it is suppressed that the time required for forming the conductor 16 becomes long. To.
  • the thickness ht of the insulating film 14 is obtained by cutting the metal-filled microstructure 20 with a FIB in the thickness direction Dt and taking a surface photograph (magnification of 50,000 times) of the cross section with a field radiation scanning electron microscope (FE-SEM). ) was photographed, and the length corresponding to the thickness of the insulating film 14 was measured at 10 points, which is an average value.
  • FE-SEM field radiation scanning electron microscope
  • the insulating film is composed of, for example, an anodic oxide film having electrical insulating properties.
  • anodic oxide film for example, an aluminum anodic oxide film is used because micropores having a desired average diameter are formed and through holes and conductors are easily formed as described above.
  • the anodic oxide film of aluminum is not limited, and an anodic oxide film of valve metal can be used. Therefore, valve metal is used as the metal substrate.
  • examples of the valve metal include, for example, the above-mentioned aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like.
  • an anodized aluminum film is preferable because it has good dimensional stability and is relatively inexpensive. Therefore, it is preferable to manufacture the structure using an aluminum substrate.
  • the thickness of the anodizing film is the same as the thickness ht of the insulating film 14 described above, and is 100 ⁇ m or more.
  • the upper limit of the thickness of the anodizing film is the same as the thickness ht of the insulating film 14.
  • the metal substrate is used for manufacturing a metal-filled microstructure, and is a substrate for forming an anodized film.
  • a metal substrate on which an anodic oxide film can be formed is used, and a metal substrate composed of the above-mentioned valve metal can be used.
  • an aluminum substrate is used as the metal substrate because it is easy to form an anodized film as the anodized film.
  • the aluminum substrate used to form the insulating film 14 is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and containing a trace amount of a foreign element; low-purity aluminum (for example, for example).
  • the surface on one side on which the anodizing film is formed by the anodizing treatment preferably has an aluminum purity of 99.5% by mass or more, more preferably 99.9% by mass or more, and 99. It is more preferably .99% by mass or more.
  • the aluminum purity is in the above range, the regularity of the arrangement of the micropores formed by the anodizing treatment becomes sufficient. That is, the regularity of the arrangement of the through holes is sufficient.
  • the aluminum substrate is not particularly limited as long as it can form an anodized film, and for example, JIS (Japanese Industrial Standards) 1050 material is used.
  • the surface of one side of the aluminum substrate to be anodized is previously heat-treated, degreased and mirror-finished.
  • the heat treatment, the degreasing treatment, and the mirror finish treatment the same treatments as those described in paragraphs [0044] to [0054] of JP-A-2008-270158 can be applied.
  • the mirror finish treatment before the anodic oxidation treatment is, for example, electrolytic polishing, and for the electrolytic polishing, for example, an electrolytic polishing liquid containing phosphoric acid is used.
  • anodizing process For the anodizing treatment, a conventionally known method can be used, but from the viewpoint of increasing the regularity of the arrangement of micropores, that is, the arrangement of through holes, and ensuring the idiosyncratic conductivity of the metal-filled microstructure. It is preferable to use the self-regulation method or constant voltage processing.
  • the self-regularization method and the constant voltage treatment of the anodizing treatment the same treatments as those described in paragraphs [0056] to [0108] and [FIG. 3] of JP-A-2008-270158 are performed. Can be applied.
  • the treatment time of the anodizing treatment is appropriately determined by the thickness of the anodized film to be formed. When the thickness is as thick as 100 ⁇ m or more, the treatment time of the anodizing treatment becomes long.
  • the method for producing a metal-filled microstructure may include a holding step.
  • the holding step is a voltage of 95% or more and 105% or less of the holding voltage selected from the range of 1 V or more and less than 30% of the voltage in the above-mentioned anodizing treatment step after the above-mentioned anodizing treatment step for a total of 5 minutes or more.
  • This is the process of holding.
  • the holding step is a total of 95% or more and 105% or less of the holding voltage selected from the range of 1 V or more and less than 30% of the voltage in the above-mentioned anodizing treatment step after the above-mentioned anodizing treatment step.
  • This is a step of performing electrolytic treatment for 5 minutes or more.
  • the "voltage in the anodizing treatment” is a voltage applied between the aluminum and the counter electrode, and for example, if the electrolysis time by the anodizing treatment is 30 minutes, the voltage maintained for 30 minutes. The average value.
  • the voltage in the holding step is 5% or more and 25% or less of the voltage in the anodizing process. It is preferably present, and more preferably 5% or more and 20% or less.
  • the total holding time in the holding step is preferably 5 minutes or more and 20 minutes or less, more preferably 5 minutes or more and 15 minutes or less, and 5 minutes or more. It is more preferably 10 minutes or less.
  • the holding time in the holding step may be 5 minutes or more in total, but is preferably 5 minutes or more continuously.
  • the voltage in the holding step may be set by continuously or stepwise reducing the voltage from the voltage in the anodic oxidation treatment step to the voltage in the holding step, but for the reason of further improving the in-plane uniformity, the anodic oxidation treatment is performed. It is preferable to set the voltage to 95% or more and 105% or less of the above-mentioned holding voltage within 1 second after the completion of the step.
  • the above-mentioned holding step can also be performed continuously with the above-mentioned anodizing treatment step, for example, by lowering the electrolytic potential at the end of the above-mentioned anodizing treatment step.
  • the same electrolytic solution and treatment conditions as those of the above-mentioned conventionally known anodizing treatment can be adopted.
  • the anodic oxide film having a plurality of micropores has a barrier layer (not shown) at the bottom of the micropores as described above. As described above, it has a barrier layer removing step of removing the barrier layer.
  • the barrier layer removing step is a step of removing the barrier layer of the anodic oxide film by using, for example, an alkaline aqueous solution containing ions of a metal M1 having a hydrogen overvoltage higher than that of aluminum.
  • the barrier layer removing step described above the barrier layer is removed, and a conductor layer made of the metal M1 is formed at the bottom of the micropores.
  • the hydrogen overvoltage means the voltage required for hydrogen to be generated.
  • the hydrogen overvoltage of aluminum (Al) is ⁇ 1.66 V (Journal of the Chemical Society of Japan, 1982, (8)). , P1305-1313).
  • Metal M1 having a higher hydrogen overvoltage than that of aluminum and the value of the hydrogen overvoltage thereof are shown below.
  • the barrier layer removing step may be a step of removing the barrier layer of the anodized film and exposing a part of the substrate to the bottom of the through hole.
  • the barrier layer removing step is not particularly limited to the above-mentioned method, and for example, the barrier layer is electrochemically dissolved at a potential lower than the potential in the above-mentioned anodizing treatment of the above-mentioned anodizing treatment step.
  • electrolytic removal treatment Method of removing the barrier layer by etching
  • etching removal treatment Method of removing the barrier layer by etching
  • etching removal treatment Method of removing the barrier layer by etching
  • a method of removing the remaining barrier layer by an etching removal treatment a pore wide treatment or the like can be mentioned.
  • the pore wide processing is as described above.
  • the above-mentioned electrolytic removal treatment is not particularly limited as long as it is an electrolytic treatment performed at a potential lower than the potential (electrolytic potential) in the above-mentioned anodic oxidation treatment of the above-mentioned anodic oxidation treatment step.
  • the above-mentioned electrolytic dissolution treatment can be continuously performed with the above-mentioned anodizing treatment, for example, by lowering the electrolytic potential at the end of the above-mentioned anodizing treatment step.
  • the same electrolytic solution and treatment conditions as those of the above-mentioned conventionally known anodizing treatment can be adopted except for the conditions other than the electrolytic potential.
  • the above-mentioned electrolytic removal treatment and the above-mentioned anodizing treatment are continuously performed as described above, it is preferable to perform the treatment using the same electrolytic solution.
  • the electrolytic potential in the above-mentioned electrolysis removal treatment is preferably lowered continuously or stepwise (step-like) to a potential lower than the electrolysis potential in the above-mentioned anodizing treatment.
  • the reduction width (step width) when the electrolytic potential is gradually lowered is preferably 10 V or less, more preferably 5 V or less, and 2 V or less from the viewpoint of the withstand voltage of the barrier layer. It is more preferable to have it.
  • the voltage drop rate when the electrolytic potential is continuously or stepwise lowered is preferably 1 V / sec or less, more preferably 0.5 V / sec or less, and 0.2 V / sec, from the viewpoint of productivity and the like. Seconds or less is more preferable.
  • the above-mentioned etching removal treatment is not particularly limited, but may be a chemical etching treatment that dissolves using an acid aqueous solution or an alkaline aqueous solution, or may be a dry etching treatment.
  • the structure after the above-mentioned anodic oxidation treatment step is immersed in an acid aqueous solution or an alkaline aqueous solution, and the inside of the micropores is filled with the acid aqueous solution or the alkaline aqueous solution, and then anodic oxidation is performed. Only the barrier layer can be selectively dissolved by a method of contacting the surface of the film on the opening side of the micropore with a pH buffer solution or the like.
  • an acid aqueous solution when used, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or oxalic acid, or a mixture thereof.
  • concentration of the aqueous acid solution is preferably 1 to 10% by mass.
  • the temperature of the aqueous acid solution is preferably 15 to 80 ° C, more preferably 20 to 60 ° C, and further preferably 30 to 50 ° C.
  • an alkaline aqueous solution when used, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass.
  • the temperature of the alkaline aqueous solution is preferably 10 to 60 ° C, more preferably 15 to 45 ° C, and further preferably 20 to 35 ° C.
  • 50 g / L, 40 ° C. phosphoric acid aqueous solution, 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution and the like are preferably used. Be done.
  • As the pH buffer solution a buffer solution corresponding to the above-mentioned acid aqueous solution or alkaline aqueous solution can be appropriately used.
  • the immersion time in the acid aqueous solution or the alkaline aqueous solution is preferably 5 to 120 minutes, more preferably 8 to 120 minutes, further preferably 8 to 90 minutes, and 10 to 90 minutes. It is particularly preferable to have it. Of these, 10 to 60 minutes is preferable, and 15 to 60 minutes is more preferable.
  • a first metal portion is formed in a plurality of through holes from one surface side in the thickness direction of the insulating film by using an AC electrolytic plating method. It has 1 step and a 2nd step of forming a 2nd metal part on the 1st metal part of a plurality of through holes by using a DC electrolytic plating method.
  • the first metal part and the second metal part are formed in this order.
  • the first metal part is formed by using the AC electrolytic plating method.
  • the second metal portion is formed by using the DC electrolytic plating method.
  • the first metal portion is formed first when the conductor is formed.
  • the first metal portion serves as a seed layer for forming the second metal portion, and the second metal portion is formed starting from the first metal portion.
  • the first metal portion is not limited to being composed of pure metal, and may be composed of an alloy.
  • the first metal portion is composed of, for example, Zn, Ni, Co, Cr, Sn, Cu, Ag, Au and alloys thereof.
  • the first metal portion is preferably composed of Zn or Ni.
  • the length of the first metal portion 16a is preferably less than 10% of the length of the conductor 16. For example, when the length of the conductor 16 is 100 ⁇ m, the length of the first metal portion 16a is preferably less than 10 ⁇ m. Further, the length of the first metal portion 16a is preferably 2% or more of the length of the conductor 16. For example, when the length of the conductor 16 is 100 ⁇ m, the length of the first metal portion 16a is preferably 2 ⁇ m or more.
  • the second metal portion is formed after the formation of the first metal portion.
  • the second metal portion is formed inside the through hole and on the first metal portion.
  • the second metal portion has a longer length in the thickness direction than the first metal portion. Further, when the through hole has an enlarged diameter, the second metal portion is formed in the enlarged diameter portion.
  • the second metal portion is not limited to being composed of pure metal, and may be composed of an alloy.
  • the second metal portion is composed of, for example, Zn, Ni, Co, Cr, Sn, Cu, Ag, Au and alloys thereof.
  • the second metal portion is preferably made of Cu.
  • the length of the second metal portion 16b is the length obtained by subtracting the length of the first metal portion 16a from the length of the conductor 16, but it is preferably more than 90% of the length of the conductor 16. For example, when the length of the conductor 16 is 100 ⁇ m, the length of the second metal portion 16b is preferably more than 90 ⁇ m. Further, the length of the second metal portion 16b is preferably less than 98% of the length of the conductor 16. For example, when the length of the conductor 16 is 100 ⁇ m, the length of the second metal portion 16b is preferably less than 98 ⁇ m.
  • the metal constituting the first metal portion and the second metal portion is different.
  • the difference between the above-mentioned first metal part and the second metal part is that the constituent elements are different in the case of a single metal when comparing the two metals of the first metal part and the second metal part. It means that the types of are different.
  • the first metal part and the second metal part is an alloy, it means that the types of the elements of the main component are different when the main components having a content of 50% by mass or more are compared.
  • the fact that the two metals are of the same type means that when the two metals are compared, the types of the constituent elements are the same in the case of a single metal.
  • the first metal part and the second metal part are taken out, and the first metal part and the second metal part are fluorescent, respectively.
  • XRF X-ray
  • the above-mentioned first metal portion is formed by using an AC electrolytic plating method.
  • a voltage is modulated in a sinusoidal manner at a predetermined frequency and applied.
  • the waveform at the time of voltage modulation is not limited to a sine wave, and may be, for example, a square wave, a triangular wave, a sawtooth wave, or a reverse sawtooth wave.
  • Ni is used for the first metal portion as the plating solution
  • a nickel (Ni) plating solution obtained by adding water to nickel sulfate (II) and boric acid can be used as the nickel (Ni) plating solution.
  • a small amount of aluminum sulfate may be added (about 0.1 mol) to the nickel (Ni) plating solution.
  • Ni nickel
  • a plating solution obtained by adding zinc sulfate to an aqueous aluminum sulfate solution can be used as the zinc (Zn) plating solution.
  • the processing time by the AC electrolytic plating method is calculated in advance, for example, and the length of the first metal portion in the thickness direction Dt is adjusted.
  • a DC electrolytic plating method is used as a method for forming the above-mentioned second metal portion inside the through hole and on the first metal portion.
  • the second metal portion has a longer length in the thickness direction than the first metal portion. Therefore, the processing time of the second metal portion by the DC electrolytic plating method is calculated in advance, for example, and the length of the second metal portion in the thickness direction is adjusted.
  • the metal when the metal is filled to form the second metal portion by using the DC electrolytic plating method, it is necessary to allow a rest time during pulse electrolysis or constant potential electrolysis.
  • the rest time is required to be 10 seconds or more, preferably 30 to 60 seconds. It is also desirable to add ultrasonic waves to promote the agitation of the electrolyte.
  • the electrolytic voltage is usually 20 V or less, preferably 10 V or less, but it is preferable to measure the precipitation potential of the target metal in the electrolytic solution to be used in advance and perform constant potential electrolysis within the potential of + 1 V.
  • the plating solution contains metal ions, and a conventionally known plating solution is used depending on the metal to be filled.
  • the main component of the solid content is preferably copper sulfate, and for example, a mixed aqueous solution of copper sulfate, sulfuric acid and hydrochloric acid is used.
  • an aqueous solution of copper sulfate is generally used for precipitating copper, but the concentration of copper sulfate is preferably 1 to 300 g / L, more preferably 100 to 200 g / L. preferable.
  • the precipitation can be promoted by adding hydrochloric acid to the plating solution.
  • the hydrochloric acid concentration is preferably 10 to 20 g / L.
  • the main component of the solid content is that the proportion of the electrolytic solution in the solid content is 20% by mass or more, and for example, copper sulfate is contained in the solid content of the electrolytic solution in an amount of 20% by mass or more. That is.
  • the plating solution preferably contains a surfactant.
  • a surfactant known ones can be used.
  • Sodium lauryl sulfate which is conventionally known as a surfactant to be added to the plating solution, can be used as it is.
  • Both ionic (cationic / anionic / bidirectional) and nonionic (nonionic) hydrophilic portions can be used, but the point of avoiding the generation of bubbles on the surface of the object to be plated.
  • a cation beam activator is desirable.
  • the concentration of the surfactant in the plating solution composition is preferably 1% by mass or less.
  • a support may be provided on the insulating film 14, for example.
  • the support preferably has the same outer shape as the insulating film 14. By attaching a support, handleability is increased.
  • Diameter expansion process This is a step of expanding the diameter of the through hole, and the diameter of the through hole is increased by the diameter expansion step.
  • a second metal portion is formed in the diameter-expanded portion expanded by the diameter-expanding step.
  • the diameter expansion step it is preferable to expand the diameter to 110 to 130% with respect to the diameter of the original through hole.
  • the diameter after expansion is preferably 66 to 78 nm.
  • the diameter of the above-mentioned cylindrical enlarged diameter portion 12d (see FIG. 11), that is, the second diameter d 2 (see FIG. 11) is 66 to 78 nm.
  • a chemical etching process or a dry etching process can be used in the diameter expansion step.
  • the chemical etching treatment for example, the insulating film is immersed in a treatment liquid that dissolves the insulating film to form an enlarged diameter portion.
  • the insulating film is an aluminum anodic oxide film
  • an alkaline aqueous solution or an acid aqueous solution is used as the treatment liquid.
  • the dry etching process the insulating film is exposed to a gas that dissolves the insulating film to form an enlarged diameter portion.
  • a Cl 2 / Ar mixed gas is used as the gas.
  • the diameter expansion step may be carried out before the first step or between the first step and the second step.
  • the shape of the enlarged diameter portion is not limited to the above-mentioned cylindrical shape and conical trapezoidal shape, and may be other shapes.
  • the shape of the enlarged diameter portion may be, for example, a shape in which the diameter of the enlarged diameter portion gradually increases from the back surface side of the insulating film toward the front surface.
  • the method of bringing the above-mentioned acid aqueous solution or alkaline aqueous solution into contact with the insulating film 14 is not particularly limited, and examples thereof include a dipping method and a spraying method. Of these, the dipping method is preferable.
  • an aqueous acid solution When an aqueous acid solution is used, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid, or a mixture thereof. Of these, an aqueous solution containing no chromic acid is preferable because it is excellent in safety.
  • the concentration of the aqueous acid solution is preferably 1 to 10% by mass.
  • the temperature of the aqueous acid solution is preferably 25 to 60 ° C.
  • an alkaline aqueous solution it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass.
  • the temperature of the alkaline aqueous solution is preferably 20 to 35 ° C. Specifically, for example, a 50 g / L, 40 ° C. phosphoric acid aqueous solution, a 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, or a 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is preferably used. ..
  • the immersion time in the acid aqueous solution or the alkaline aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and even more preferably 15 to 60 minutes.
  • the soaking time means the total of each soaking time when the soaking treatment for a short time is repeated.
  • a cleaning treatment may be performed between the immersion treatments.
  • the conductor 16 is projected from the front surface 14a or the back surface 14b of the insulating film 14, but the conductor 16 is preferably projected from the front surface 14a or the back surface 14b of the insulating film 14 by 10 nm to 1000 nm, preferably 50 nm to 500 nm. It is more preferable to make it protrude. That is, the amount of protrusion of the protrusion from the front surface 14a and the amount of protrusion of the conductor 16 from the back surface 14b of the protrusion are preferably 10 nm to 1000 nm, more preferably 50 nm to 500 nm, respectively.
  • the cross section of the metal-filled microstructure was observed with an electrolytic discharge scanning electron microscope at a magnification of 20,000 times, and the height of the protrusion of the conductor was measured at 10 points. The average value.
  • the inside of the through hole 12 is filled with a conductive substance such as metal, and then the insulating film 14 and the end portion of the conductive substance such as metal are used. It is preferable to selectively remove the anodic oxide film after processing the anodic oxide film so as to have the same planar shape.
  • heat treatment can be performed for the purpose of reducing the strain in the conductor 16 generated by the metal filling.
  • the heat treatment is preferably carried out in a reducing atmosphere from the viewpoint of suppressing the oxidation of the metal, specifically, the oxygen concentration is preferably 20 Pa or less, and more preferably carried out under vacuum.
  • the vacuum means a state of a space in which at least one of the gas density and the atmospheric pressure is lower than that of the atmosphere. Further, it is preferable that the heat treatment is performed while applying stress to the insulating film 14 for the purpose of straightening.
  • a resin layer may be formed to cover the surface of the insulating film in which the conductor is exposed.
  • the resin layer forming step is a step carried out on the metal-filled microstructure.
  • the resin layer can be provided from the viewpoint of protecting the conductor and further improving the transportability.
  • the resin layer contains a heat-removable adhesive.
  • the resin layer is more preferably a film with an adhesive layer whose adhesiveness is weakened by heat treatment and which can be peeled off.
  • the film with an adhesive layer whose adhesiveness is weakened by the above-mentioned heat treatment and which can be peeled off include a heat-removable resin layer.
  • the method of attaching the above-mentioned film with an adhesive layer is not particularly limited, and the film can be attached using a conventionally known surface protective tape affixing device or laminator. The resin layer will be described below.
  • the metal-filled microstructures 20, 20a, 20b are wound into a roll with the resin layer 34 (see FIG. 23). It may have a winding process.
  • the winding step as shown in FIG. 22, the metal-filled microstructures 20, 20a, and 20b can be supplied in a state of being wound into a roll around the winding core 32.
  • the winding method in the above-mentioned winding step is not particularly limited, and examples thereof include a method of winding on a winding core 32 (see FIG. 22) having a predetermined diameter and a predetermined width. In the roll-shaped state shown in FIG.
  • the resin layer 34 (see FIG. 23) is removed.
  • the metal-filled microstructures 20, 20a, and 20b can be used as the anisotropic conductive member.
  • the production method of the present invention includes a polishing step, a surface smoothing step, a protective film forming treatment, and a washing treatment described in paragraphs [0049] to [0057] of International Publication No. 2015/029881. You may have.
  • the diameter d of the conductor 16 is more preferably 1 ⁇ m or less, further preferably 5 to 500 nm, further preferably 20 to 400 nm, further preferably 40 to 200 nm, and even more preferably 50 to 200 nm. Most preferably, it is 100 nm. Further, when the diameter of the conductor is expanded, the diameter of the conductor differs between one surface and the other surface. For example, the first diameter d 1 of the first metal portion 16a exposed on the back surface 14b and the second diameter d 2 of the second metal portion 16b exposed on the front surface 14a are different from each other, and the first diameter d 1 ⁇ first.
  • the diameter of 2 is d 2 .
  • the second diameter d 2 is 70 nm.
  • the first diameter d 1 is the same as the diameter d of the conductor 16 described above. It is preferable that the second diameter d 2 satisfies the first diameter d 1 ⁇ the second diameter d 2 and is the same as the diameter d of the above-mentioned conductor 16 except for the second diameter d 2.
  • the second diameter d 2 / first diameter d 1 is preferably 110 to 130%.
  • the density of the conductor 16 is preferably 20,000 pieces / mm 2 or more, more preferably 2 million pieces / mm 2 or more, further preferably 10 million pieces / mm 2 or more, and 50 million pieces / mm 2.
  • the number of pieces / mm 2 or more is particularly preferable, and the number of pieces / mm 2 or more is most preferable.
  • the center-to-center distance p (see FIG. 6) of each of the adjacent conductors 16 is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and further preferably 50 nm to 140 nm.
  • the diameter of the through hole 12 is obtained by photographing the surface of the insulating film 14 from directly above at a magnification of 100 to 10000 times using a scanning electron microscope. In the photographed image, at least 20 through holes having an annular shape around them are extracted, the diameters thereof are measured and used as the opening diameter, and the average value of these opening diameters is calculated as the average diameter of the through holes.
  • magnification the magnification in the above-mentioned range can be appropriately selected so that a photographed image capable of extracting 20 or more through holes can be obtained.
  • the maximum value of the distance between the ends of the through hole portion was measured.
  • the shape of the opening of the through hole is not limited to a substantially circular shape, when the shape of the opening is non-circular, the maximum value of the distance between the ends of the through hole portion is set as the opening diameter. Therefore, for example, even in the case of a through hole having a shape in which two or more through holes are integrated, this is regarded as one through hole, and the maximum value of the distance between the ends of the through hole portions is set as the opening diameter. ..
  • the distance between the conductors 16 in the insulating film 14 is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, and even more preferably 20 nm to 60 nm.
  • the insulating film 14 sufficiently functions as an electrically insulating partition wall of the conductive body 16.
  • the distance between the conductors means the width between the adjacent conductors, and the cross section of the metal-filled microstructure is observed with an electrolytic discharge scanning electron microscope at a magnification of 200,000 times, and the adjacent conductors are adjacent to each other. The average value measured at 10 points.
  • the protrusion is a part of the conductor and is columnar.
  • the protruding portion is preferably cylindrical because the contact area with the joining target can be increased.
  • the average length of the protrusion is preferably 30 nm to 500 nm, and the upper limit is more preferably 100 nm or less.
  • the average length of the protruding portion is measured by acquiring a cross-sectional image of the protruding portion using a field emission scanning electron microscope as described above, and measuring the height of the protruding portion at 10 points each based on the cross-sectional image. It is the average value.
  • the metal-filled microstructure is cut in the thickness direction Dt and cut using a field emission scanning electron microscope (FE-SEM). It is an average value obtained by observing the cross section and measuring 10 points corresponding to each size.
  • FE-SEM field emission scanning electron microscope
  • the resin layer is provided on at least one of the front surface and the back surface of the metal-filled microstructure, and protects the exposed conductor.
  • the resin material constituting the above-mentioned resin layer include an ethylene-based copolymer, a polyamide resin, a polyester resin, a polyurethane resin, a polyolefin-based resin, an acrylic resin, and a cellulose-based resin.
  • the above-mentioned resin layer is preferably a film with a peelable adhesive layer, and is adhered by heat treatment or ultraviolet exposure treatment. It is more preferable that the film has an adhesive layer, which has a weak property and can be peeled off.
  • the above-mentioned film with an adhesive layer is not particularly limited, and examples thereof include a heat-peeling type resin layer and an ultraviolet (ultraviolet) peeling type resin layer.
  • the heat-peeling type resin layer has adhesive strength at room temperature and can be easily peeled off only by heating, and most of them mainly use effervescent microcapsules or the like.
  • Specific examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include a rubber-based pressure-sensitive adhesive, an acrylic-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a polyester-based pressure-sensitive adhesive, and a polyamide-based pressure-sensitive adhesive. , Urethane-based pressure-sensitive adhesives, styrene-diene block copolymer-based pressure-sensitive adhesives, and the like.
  • the UV peeling type resin layer has a UV curable adhesive layer, and the adhesive strength is lost by curing, so that the resin layer can be peeled off.
  • the UV curable adhesive layer include a polymer in which a carbon-carbon double bond is introduced into the polymer side chain or the main chain or at the end of the main chain as the base polymer.
  • the base polymer having a carbon-carbon double bond it is preferable to use an acrylic polymer as a basic skeleton. Further, since the acrylic polymer is crosslinked, a polyfunctional monomer or the like can be contained as a monomer component for copolymerization, if necessary.
  • the base polymer having a carbon-carbon double bond can be used alone, but UV curable monomers or oligomers can also be blended. It is preferable to use a photopolymerization initiator in combination with the UV curable adhesive layer in order to cure it by UV irradiation.
  • Photopolymerization initiators include benzoin ether compounds; ketal compounds; aromatic sulfonyl chloride compounds; photoactive oxime compounds; benzophenone compounds; thioxanson compounds; camphorquinone; halogenated ketones; acylphosphinoxide; acyls. Phosphonate and the like can be mentioned.
  • ELP holders such as ELP DU-300, ELP DU-2385KS, ELP DU-2187G, ELP NBD-3190K, and ELP UE-2091J [registered trademark] (Nitto Denko).
  • the present invention is basically configured as described above. Although the metal-filled microstructure and the method for producing the metal-filled microstructure of the present invention have been described in detail above, the present invention is not limited to the above-described embodiment, and various types are described within a range not deviating from the gist of the present invention. Of course, it may be improved or changed.
  • the materials, reagents, amounts of substances and their ratios, operations and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following examples.
  • the metal-filled microstructures of Examples 1 to 9 and the metal-filled microstructures of Comparative Examples 1 to 4 were produced.
  • the metal-filled microstructures of Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated for metal filling uniformity with respect to through holes.
  • the evaluation results of metal filling uniformity are shown in Table 1 below. Hereinafter, the evaluation of metal filling uniformity will be described.
  • ⁇ Metal filling uniformity> The surface of the manufactured metal-filled microstructure was observed using an optical microscope, and the metal-filled microstructure was evaluated according to the evaluation criteria shown below. It should be noted that the part where the metal filling is insufficient becomes the surface of the anodized film and therefore looks white, which was used for the evaluation of the metal filling uniformity. That is, if the conductor is not sufficiently formed, it looks white because it becomes the surface of the anodized film. In the evaluation of the white part that looks white based on the equivalent circle diameter shown in the following evaluation criteria, the white part was visually judged while comparing with the scale bar in the field of view of the optical microscope. Of 1 to 5 according to the following evaluation criteria, 1 and 2 were evaluated as inferior.
  • Evaluation Criteria 5 "Does not meet any of the following evaluation criteria 1 to 4" 4: "The equivalent circle diameter of the white part having the largest equivalent circle diameter in the observation area is 5 ⁇ m or more and less than 10 ⁇ m" 3: "The equivalent circle diameter of the white part having the largest equivalent circle diameter in the observation area is 10 ⁇ m or more and less than 20 ⁇ m" 2: "The equivalent circle diameter of the white part having the largest equivalent circle diameter in the observation area is 20 ⁇ m or more and less than 50 ⁇ m" 1: "The equivalent circle diameter of the white part having the largest equivalent circle diameter in the observation area is 50 ⁇ m or more"
  • Examples 1 to 9 and Comparative Examples 1 to 4 will be described.
  • Examples 1 to 9 and Comparative Examples 1 to 4 in each column of the manufacturing process in Table 1 below, “Yes” is described for the performed process, and “-” is described for the non-implemented process. did.
  • the "diameter expansion process” of the manufacturing process in Table 1 below indicates the diameter expansion process.
  • AC electrolytic plating indicates a first step of forming a first metal portion.
  • DC electrolytic plating indicates a second step of forming a second metal portion.
  • the surface was scraped to an average thickness of 10 mm by a surface mill, kept at 550 ° C for about 5 hours, and when the temperature dropped to 400 ° C, the thickness was 2.7 mm using a hot rolling mill. It was made into a rolled plate. Further, after heat treatment was performed at 500 ° C. using a continuous annealing machine, the thickness was finished to 1.0 mm by cold rolling to obtain an aluminum substrate of JIS (Japanese Industrial Standards) 1050 material. After making this aluminum substrate 1030 mm wide, each of the following treatments was performed.
  • JIS Japanese Industrial Standards
  • the above-mentioned aluminum substrate was subjected to electrolytic polishing treatment using an electrolytic polishing liquid having the following composition under the conditions of a voltage of 25 V, a liquid temperature of 65 ° C., and a liquid flow rate of 3.0 m / min.
  • the cathode was a carbon electrode, and the power source was GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.).
  • the flow velocity of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
  • Electrolytic polishing liquid composition ⁇ 85% by mass phosphoric acid (reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 660 mL ⁇ Pure water 160mL ⁇ Sulfuric acid 150mL ⁇ Ethylene glycol 30mL
  • the aluminum substrate after the electrolytic polishing treatment was subjected to anodizing treatment by a self-regularization method according to the procedure described in JP-A-2007-204802.
  • the aluminum substrate after the electrolytic polishing treatment was subjected to pre-anodizing treatment for 1 hour with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 16 ° C., and a liquid flow rate of 3.0 m / min. ..
  • the pre-anodized aluminum substrate was subjected to a film removal treatment by immersing it in a mixed aqueous solution of 0.2 mol / L chromic anhydride and 0.6 mol / L phosphoric acid (liquid temperature: 50 ° C.) for 12 hours. Then, again, anodizing was performed with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 16 ° C., and a liquid flow rate of 3.0 m / min for a treatment time of 9 hours, and a film thickness of 100 ⁇ m. Anodized film was obtained.
  • the cathode was a stainless steel electrode, and GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.) was used as the power source.
  • a NeoCool BD36 manufactured by Yamato Kagaku Co., Ltd.
  • a pair stirrer PS-100 manufactured by EYELA Tokyo Rika Kikai Co., Ltd. was used as the stirring and heating device.
  • the flow velocity of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
  • etching treatment was carried out using an aqueous sodium hydroxide solution (50 g / l) at 30 ° C. for 150 seconds to remove the barrier layer at the bottom of the through hole of the anodized film.
  • the average thickness of the anodized film after the barrier layer removing step was 100 ⁇ m.
  • the first metal part of Ni was formed by using the AC electrolytic plating method.
  • a nickel (Ni) plating solution having an temperature adjusted to 30 ° C. was used to form the first metal portion of Ni.
  • the nickel (Ni) plating solution is a solution obtained by adding water to 0.2 mol of nickel (II) sulfate and 0.5 mol of boric acid to make the total amount 1 liter.
  • a sine wave having a frequency of 50 Hz was used, the peak voltage was 18 V, and the electrolysis time was 10 minutes.
  • a small amount of aluminum sulfate was added to the nickel (Ni) plating solution (about 0.1 mol). After the AC electrolytic plating was completed, the product was thoroughly washed with water and then subjected to the next step.
  • the second metal portion was then formed by using a DC electrolytic plating method with an aluminum substrate as a cathode and platinum as a cathode. Specifically, by using a copper plating solution having the composition shown below and performing constant current electrolysis, a second metal portion made of copper is laminated inside the through hole and on the first metal portion. A metal-filled microstructure was prepared.
  • a plating apparatus manufactured by Yamamoto Plating Tester Co., Ltd. is used, and a power source (HZ-3000) manufactured by Hokuto Denko Co., Ltd. is used to perform cyclic voltammetry in the plating solution for precipitation. After confirming the potential, the treatment was performed under the conditions shown below.
  • ⁇ Substrate removal process> the aluminum substrate was dissolved and removed by immersing it in a mixed solution of copper chloride / hydrochloric acid to prepare a metal-filled microstructure having an average thickness of 100 ⁇ m.
  • the diameter of the conductors in the prepared metal-filled microstructure was 60 nm
  • the pitch between the conductors was 100 nm
  • the density of the conductors was 57.7 million pieces / mm 2 .
  • Example 2 was produced in the same manner as in Example 1 except that the diameter expansion step was carried out before forming the first metal portion as compared with Example 1.
  • the anodized film after the barrier layer removing step was immersed in an alkaline aqueous solution (KOH 0.1 mol / L) adjusted to a temperature of 25 ° C. The immersion time was 4 minutes.
  • the aluminum hydrate produced by the dissolution accompanying the expansion of the diameter of the through hole was immersed in a 0.5% sulfuric acid aqueous solution adjusted to a temperature of 30 ° C. for 30 seconds for neutralization and removal. After soaking, it was thoroughly washed with running water.
  • Example 3 is different from Example 2 in that the diameter expansion step is carried out after the formation of the first metal portion and before the formation of the second metal portion, and other than that, it is the same as that of Example 2.
  • the diameter expansion step was set to 70 nm.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm
  • the second diameter d 2 on the front surface side was 70 nm.
  • Example 4 was different from Example 1 in that the thickness of the metal-filled microstructure was 200 ⁇ m, and other than that, it was produced in the same manner as in Example 1.
  • the treatment time of the anodized film was set to 25 hours.
  • the diameter of the conductor was 60 nm.
  • Example 5 the diameter of the metal-filled microstructure was set to 200 ⁇ m as compared with Example 1, and the diameter expansion step was carried out after forming the first metal portion and before forming the second metal portion. Other than that, it was produced in the same manner as in Example 1.
  • the treatment time of the anodized film was set to 25 hours.
  • the anodized film after the barrier layer removing step was immersed in an alkaline aqueous solution (KOH 0.1 mol / L) adjusted to a temperature of 25 ° C. The immersion time was 4 minutes.
  • the aluminum hydrate produced by the dissolution accompanying the expansion of the diameter of the through hole was immersed in a 0.5% sulfuric acid aqueous solution adjusted to a temperature of 30 ° C. for 30 seconds for neutralization and removal. After soaking, it was thoroughly washed with running water.
  • the diameter expansion step the diameter after the diameter expansion was set to 70 nm.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm
  • the second diameter d 2 on the front surface side was 70 nm.
  • Example 6 was different from Example 5 in that the thickness of the metal-filled microstructure was 250 ⁇ m, and other than that, it was produced in the same manner as in Example 5.
  • the treatment time of the anodized film was set to 40 hours.
  • the diameter expansion step the diameter after the diameter expansion was set to 70 nm.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm
  • the second diameter d 2 on the front surface side was 70 nm.
  • Example 7 was different from Example 6 in that the first metal portion was formed of Zn, and other than that, it was produced in the same manner as in Example 6.
  • a zinc (Zn) plating solution whose temperature was adjusted to 30 ° C. was used.
  • the zinc (Zn) plating solution is a solution obtained by adding 0.1 mol of zinc sulfate to a 0.1 mol / L aluminum sulfate aqueous solution.
  • a sine wave having a frequency of 50 Hz was used, the peak voltage was 25 V, and the electrolysis time was 5 minutes.
  • the product was thoroughly washed with water and then subjected to the next step.
  • the diameter expansion step the diameter after the diameter expansion was set to 70 nm.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm
  • the second diameter d 2 on the front surface side was 70 nm.
  • Example 8 was produced in the same manner as in Example 5 except that the diameter expansion step was carried out before the formation of the first metal portion as compared with Example 5.
  • the diameter after the diameter expansion was set to 70 nm.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm
  • the second diameter d 2 on the front surface side was 70 nm.
  • Example 9 was produced in the same manner as in Example 6 except that the diameter expansion step was carried out before the formation of the first metal portion as compared with Example 6.
  • the diameter after the diameter expansion was set to 70 nm.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm
  • the second diameter d 2 on the front surface side was 70 nm.
  • Comparative Example 1 In Comparative Example 1, compared to Example 1, the thickness of the metal-filled microstructure was 20 ⁇ m, the first metal portion was not formed by the AC electrolytic plating method, and the treatment time of the anodic oxide film was long. No, other than that, it was prepared in the same manner as in Example 1. In Comparative Example 1, the treatment time of the anodized film was set to 1 hour. The conductor was formed using only the DC electrolytic plating method. In Comparative Example 1, the diameter of the conductor was 60 nm. (Comparative Example 2) Comparative Example 2 was produced in the same manner as in Comparative Example 1 except that the thickness of the metal-filled microstructure was 60 ⁇ m as compared with Comparative Example 1.
  • Comparative Example 2 the treatment time of the anodized film was set to 5 hours.
  • the diameter of the conductor was 60 nm.
  • Comparative Example 3 Comparative Example 3 was produced in the same manner as in Comparative Example 1 except that the thickness of the metal-filled microstructure was 100 ⁇ m as compared with Comparative Example 1.
  • the treatment time of the anodized film was 9 hours.
  • the diameter of the conductor was 60 nm.
  • Comparative Example 4 Comparative Example 4 was produced in the same manner as in Comparative Example 3 except that the diameter-expanding step was carried out before forming the first metal portion as compared with Comparative Example 3.
  • the diameter after the diameter expansion was set to 70 nm by the diameter expansion step.
  • the diameter before the diameter expansion step was 60 nm.
  • the first diameter d 1 on the back surface side of the conductor was 60 nm, and the second diameter d 2 on the front surface side was 70 nm.
  • Example 1 to 9 the metal filling uniformity was excellent as compared with Comparative Examples 1 to 4 even when the thickness of the metal-filled microstructure was 100 ⁇ m or more. That is, a thick metal-filled microstructure could be obtained.
  • Comparative Examples 1 and 2 have a thickness of less than 100 ⁇ m and are thin. In Comparative Examples 3 and 4 having a thickness of 100 ⁇ m, the metal filling uniformity is poor. As described above, in Comparative Examples 1 to 4, it was not possible to obtain a thick metal-filled microstructure. All of Examples 1 to 3 have a thickness of 100 ⁇ m, but Examples 2 and 3 having a diameter-expanding step have further excellent metal filling uniformity.
  • Example 4 the thickness was 200 ⁇ m, but in Examples 5 and 8 having the diameter expansion step, the metal filling uniformity was further excellent.
  • the metals constituting the first metal portion are different, but Ni is more preferable than Zn from the result of metal filling uniformity.

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Publication number Priority date Publication date Assignee Title
US20220165619A1 (en) * 2019-08-16 2022-05-26 Fujifilm Corporation Method for manufacturing structure

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JP2002004083A (ja) * 2000-04-18 2002-01-09 Shinko Electric Ind Co Ltd ヴィアフィリング方法
JP2008021739A (ja) * 2006-07-11 2008-01-31 Shinko Electric Ind Co Ltd 基板の製造方法
JP2008214679A (ja) * 2007-03-01 2008-09-18 Shinko Electric Ind Co Ltd スルーホールの充填方法
JP2012124253A (ja) * 2010-12-07 2012-06-28 Canon Inc 貫通電極基板及びその製造方法
JP2016072449A (ja) * 2014-09-30 2016-05-09 大日本印刷株式会社 導電材充填貫通電極基板及びその製造方法
JP2019147988A (ja) * 2018-02-27 2019-09-05 富士フイルム株式会社 金属膜、構造体、複合材料、金属膜の製造方法、構造体の製造方法、および複合材料の製造方法

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Publication number Priority date Publication date Assignee Title
JP2002004083A (ja) * 2000-04-18 2002-01-09 Shinko Electric Ind Co Ltd ヴィアフィリング方法
JP2008021739A (ja) * 2006-07-11 2008-01-31 Shinko Electric Ind Co Ltd 基板の製造方法
JP2008214679A (ja) * 2007-03-01 2008-09-18 Shinko Electric Ind Co Ltd スルーホールの充填方法
JP2012124253A (ja) * 2010-12-07 2012-06-28 Canon Inc 貫通電極基板及びその製造方法
JP2016072449A (ja) * 2014-09-30 2016-05-09 大日本印刷株式会社 導電材充填貫通電極基板及びその製造方法
JP2019147988A (ja) * 2018-02-27 2019-09-05 富士フイルム株式会社 金属膜、構造体、複合材料、金属膜の製造方法、構造体の製造方法、および複合材料の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220165619A1 (en) * 2019-08-16 2022-05-26 Fujifilm Corporation Method for manufacturing structure
US12002713B2 (en) * 2019-08-16 2024-06-04 Fujifilm Corporation Method for manufacturing structure

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