WO2021176847A1 - Method for manufacturing metal-filled microstructure - Google Patents

Method for manufacturing metal-filled microstructure Download PDF

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Publication number
WO2021176847A1
WO2021176847A1 PCT/JP2021/000672 JP2021000672W WO2021176847A1 WO 2021176847 A1 WO2021176847 A1 WO 2021176847A1 JP 2021000672 W JP2021000672 W JP 2021000672W WO 2021176847 A1 WO2021176847 A1 WO 2021176847A1
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WIPO (PCT)
Prior art keywords
metal
oxide film
anodic oxide
filled
filled microstructure
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PCT/JP2021/000672
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French (fr)
Japanese (ja)
Inventor
堀田　吉則
Original Assignee
富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN202180017274.XA priority Critical patent/CN115210410A/en
Priority to JP2022505007A priority patent/JP7336584B2/en
Publication of WO2021176847A1 publication Critical patent/WO2021176847A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C25D11/26—Anodisation of refractory metals 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
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32

Definitions

  • the present invention relates to a method for manufacturing a metal-filled microstructure using a valve metal member, and more particularly to a method for manufacturing a metal-filled microstructure having excellent transportability and good insulation performance.
  • 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. Since the anisotropic conductive member can be electrically connected between the electronic component and the circuit board simply by inserting it between the electronic component such as a semiconductor element and the circuit board and pressurizing it, the electronic component such as the semiconductor element can be used. It is widely used as an electrical connection member and an inspection connector for performing functional inspections. In particular, electronic components such as semiconductor elements are significantly downsized.
  • Patent Document 1 is composed of a base material having micropore through holes at a density of 10 million pieces / mm 2 or more, and some of the micropore through holes are filled with a substance other than the material of the base material.
  • a method for manufacturing a microstructure is described.
  • the base material is alumina, and at least (A) an oxide film having micropores is formed on an aluminum substrate by anodization treatment, and (B) the above-mentioned (A).
  • a treatment for removing aluminum from the oxide film obtained by the treatment (C) a treatment for penetrating a part of micropores existing in the oxide film from which aluminum was removed by the above-mentioned (B) treatment, (D) the above-mentioned treatment.
  • the micropores penetrated by the (C) treatment of (C) are filled with a substance other than the oxide film, and (E) the front and back surfaces of the oxide film after the above-mentioned (D) treatment are smoothed by a chemical mechanical polishing treatment.
  • the surface smoothing treatment is performed in this order.
  • the above-mentioned (E) may be carried out after a predetermined time has elapsed, for example, by transportation or the like.
  • the filling portion may be damaged by transportation or the like.
  • the insulation performance of the microstructure may deteriorate due to the influence of the environment between processes.
  • An object of the present invention is to provide a method for manufacturing a metal-filled microstructure which is excellent in transportability and suppresses deterioration of insulation performance.
  • one aspect of the present invention is to form an oxide film having a plurality of pores in a forming region surrounded by a frame portion arranged on the outer edge of the valve metal member, thereby forming the valve metal.
  • the valve metal member is preferably made of aluminum.
  • the oxide film is preferably an anodic oxide film.
  • the anodic oxide film is preferably an Al 2 O 3 film.
  • the metal to be filled in the plurality of pores of the oxide film is preferably copper.
  • the filling step is a step of filling a plurality of pores with metal by forming a metal layer on the surface of the structure, and the filling step is preferably a step of forming a metal layer on a frame portion having a thickness of 100 ⁇ m or less. ..
  • After the holding step it is preferable to have a metal layer removing step of removing the metal layer formed on the surface of the structure.
  • After the metal layer removing step it is preferable to have a surface smoothing treatment step for smoothing the surface of the oxide film.
  • For the smoothing of the surface smoothing treatment step it is preferable to use chemical mechanical polishing, dry etching or grinding.
  • FIG. 5 is a schematic cross-sectional view showing an enlarged area Q of the structure shown in FIG. 7.
  • 6 is a schematic plan view showing an enlarged portion of the metal filling member shown in FIG. 6 corresponding to the region Q of the structure shown in FIG. 7.
  • 6 is a schematic cross-sectional view showing an enlarged portion of the metal filling member shown in FIG. 6 corresponding to the region Q of the structure shown in FIG. 7.
  • the insulating resistance of the oxide film having pores (through holes) fluctuated. Examining the fluctuation of insulation resistance, it was found that it was affected by the storage location and storage time. Even in a warehouse where no special temperature control was performed, the insulation resistance was good during the cold season, and even in the building where the temperature was controlled, the insulation resistance deteriorated irregularly. As a result of diligent studies, we thought that the water content in the oxide film with pores (through holes) might have an effect, not the temperature during storage, and investigated the relationship between the humidity and the insulation performance, especially among the storage conditions. However, it has been found that stable insulation resistance can be obtained by holding the film in a certain humidity range, which led to the present invention. Hereinafter, a method for manufacturing a metal-filled microstructure will be specifically described.
  • FIG. 7 is a plan view of the structure shown in FIG. 5
  • FIG. 8 is a schematic plan view showing an enlarged area Q of the structure shown in FIG. 7
  • FIG. 9 is a schematic plan view showing the area Q of the structure shown in FIG. 7.
  • FIG. 10 is a schematic plan view showing an enlarged portion of the metal filling member shown in FIG. 6 corresponding to the region Q of the structure shown in FIG. 7,
  • FIG. 11 is a schematic plan view showing the metal filling member shown in FIG. , Is an enlarged schematic cross-sectional view showing a portion corresponding to the region Q of the structure shown in FIG. 7.
  • the metal-filled microstructure is obtained by subjecting the surface of the valve metal member to anodizing.
  • the metal-filled microstructure has an insulating substrate made of an anodized film of valve metal.
  • the valve metal is aluminum or the like, but the valve metal is not particularly limited to aluminum, but an anodic oxide film of aluminum will be described as an example as an insulating base material. Therefore, in the following description, an aluminum substrate will be described as an example of the valve metal member. As shown in FIG. 1, an aluminum substrate is prepared as the valve metal member 11. Next, as shown in FIG. 2, the mask 12 is formed only on the outer edge 11b of the surface 11a of the valve metal member 11.
  • the mask 12 is not particularly limited as long as it is electrically insulating, and for example, a known resist film used for forming a semiconductor element can be used.
  • a resist film other than the outer edge 11b of the surface 11a of the valve metal member 11 is removed by a photolithography method, and the outer edge 11b is formed. Only the mask 12 is formed.
  • a resist pen may be used to form a resist film only on the outer edge 11b of the surface 11a of the valve metal member 11.
  • an acid-resistant adhesive resin tape may be attached to the outer edge 11b of the surface 11a of the valve metal member 11 to form the mask 12.
  • the region 11c surrounded by the mask 12 is the region where the anodic oxide film 16 (see FIG. 5) is formed.
  • an anodic oxidation treatment is carried out using the valve metal member 11 as an electrode, and an anodic oxide film forming step of forming the anodic oxide film on the region 11c surrounded by the mask 12 is performed in the valve metal member 11.
  • the anodic oxide film 16 (see FIG. 5) is an insulating base material.
  • the anodic oxide film forming step the anodic oxidation treatment is carried out using the valve metal member 11 as an anode electrode.
  • the valve metal member 11 is anodized, and an anodic oxide film 11d is formed in the region 11c of the valve metal member 11 as shown in FIG.
  • a current may be applied from the back surface side of the valve metal member 11, or a current may be applied from the outer edge 11b side.
  • the valve metal member 11 is used as an electrode as described above, and the region 11c (see FIG. 3) of the valve metal member 11 becomes the forming region of the anodic oxide film 11d, and the valve metal member under the mask 12.
  • Reference numeral 11 is an outer edge 15b (see FIG. 4) and a frame portion 15d (see FIG. 4).
  • the anodic oxide film 11d is formed in the above-mentioned region 11c, but the valve metal member 11 under the mask 12 is not anodized. As described above, all the valve metal members 11 do not become the anodic oxide film 11d, and there is a region where the valve metal member 15 remains even after the anodizing treatment.
  • the frame portion 15d of the valve metal member 15 composed of the valve metal member 15 is arranged on the outer edge 15b of the valve metal member 15.
  • An anodic oxide film 16 (see FIG. 4) is formed in the region 15c surrounded by the frame portion 15d. Since the valve metal member 11 is made of aluminum, an anodic oxide film 16 is formed as an oxide film, and the anodic oxide film 16 is made of an Al 2 O 3 film.
  • the anodic oxide film 11d When the anodic oxide film 11d is formed, there are a plurality of micropores. However, among the plurality of micropores, some micropores do not penetrate in the thickness direction Dt. In addition, there is a barrier layer (not shown) at the bottom of the micropores. Therefore, the barrier layer is removed from the anodic oxide film 11d shown in FIG. 3, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 16 as shown in FIG.
  • an oxide film (anodic oxide film 16) having a plurality of pores (through holes 17) is formed in the region 15c surrounded by the frame portion 15d arranged on the outer edge 15b of the valve metal member 15.
  • a structure 18 having a valve metal member 15 and an oxide film (anodic oxide film 16) is obtained.
  • an anodic oxide film 16 is formed on the surface 15a of the valve metal member 15, and a frame portion 15d is provided around the anodic oxide film 16.
  • the surface 16a of the anodic oxide film 16 and the surface of the frame portion 15d are substantially the same surface.
  • the anodic oxide film forming step shown in FIG. 3 and the step of forming a plurality of through holes 17 extending in the thickness direction Dt shown in FIG. 4 are forming steps for obtaining the structure 18.
  • the aluminum substrate 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 foreign elements; high-purity aluminum is vapor-deposited on low-purity aluminum (for example, a recycled material).
  • 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. When the aluminum purity is in the above range, the regularity of the micropore arrangement is sufficient.
  • the aluminum substrate is not particularly limited as long as it can form an anodic oxide film, and for example, JIS (Japanese Industrial Standards) 1050 material and 1070 material are used.
  • the surface of one side of the aluminum substrate to be anodized is preferably heat-treated, degreased, and mirror-finished in advance.
  • 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.
  • the valve metal specific examples thereof include tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like, in addition to the above-mentioned aluminum.
  • anodizing process For the anodizing treatment, a conventionally known method can be used, but from the viewpoint of increasing the regularity of the micropore arrangement and ensuring the anisotropic conductivity of the metal-filled microstructure, a self-regulating method or a constant voltage treatment can be used. Is preferably used.
  • 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 anodic oxide film having a plurality of micropores has a barrier layer (not shown) at the bottom of the micropores 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 metal M1 is formed at the bottom of the micropores.
  • the hydrogen overvoltage means a 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 hydrogen overvoltage higher than that of aluminum and the value of the hydrogen overvoltage thereof are shown below.
  • the through hole 17 can also be formed by expanding the diameter of the micropore and removing the barrier layer.
  • pore wide processing is used to increase the diameter of the micropores.
  • the pore-wide treatment is a treatment in which the anodic oxide film is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodic oxide film and expand the pore size of the micropores.
  • An aqueous solution of an inorganic acid such as hydrochloric acid or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like can be used.
  • the barrier layer at the bottom of the micropore can also be removed by the pore wide treatment, and by using the sodium hydroxide aqueous solution in the pore wide treatment, the diameter of the micropore is expanded and the barrier layer is removed.
  • the pore-wide treatment cannot form the conductor layer as in the barrier layer removing step. Therefore, after the pore-wide treatment, the conductor layer may be formed by treating again with an aqueous solution containing ions of a metal M1 having a higher hydrogen overvoltage than aluminum, and further, a plurality of steps of treatment with an aqueous solution containing a different metal may be performed. It may be applied to form a conductor layer.
  • a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is carried out.
  • a conductive passage 20 having conductivity is formed as shown in FIG. 6, and the metal filling member 21 is formed.
  • the filling step of filling the metal will be described in detail later.
  • the inside of the plurality of through holes 17 of the anodic oxide film 16 may be filled with metal, but as shown in FIGS.
  • the metal may be filled in the plurality of through holes 17 by forming the metal layer 19 on the frame portion 15d of the above and on the surface 16a of the anodic oxide film 16.
  • a thickness ⁇ (FIGS. 5 and 11) of 100 ⁇ m or less.
  • the lower limit of the thickness ⁇ of the metal layer 19 is, for example, 2 ⁇ m.
  • the thickness ⁇ of the metal layer 19 can be increased by increasing the plating time, for example.
  • the metal layer 19 is formed on the frame portion 15d by filling the metal over the surface 16a of the anodic oxide film 16.
  • the through hole 17 may be filled with metal up to the surface 16a of the anodic oxide film 16 so that the metal layer 19 is not provided.
  • the thickness ⁇ of the metal layer 19 is an average value measured at 10 points by cutting the metal filling member 21 in the thickness direction and observing the cut cross section using an FE-SEM (Field emission-Scanning Electron Microscope). be.
  • the thickness of the bottom portion 15e of the valve metal member 15 is not particularly limited, but is preferably 20 ⁇ m or more, and more preferably 30 to 50 ⁇ m.
  • the thickness of the bottom portion 15e of the valve metal member 15 described above is the same as the thickness ⁇ of the metal layer 19 described above, the metal filling member 21 is cut in the thickness direction, and the cross section of the cut cross section is observed using FE-SEM. It is an average value measured at 10 points.
  • the metal filling member 21 is obtained by the filling step of filling the metal described above. Next, a holding step of exposing the metal filling member 21 to an environment having a relative humidity of 10 to 30% for 24 hours or more is carried out.
  • the holding step is not particularly limited as long as the metal filling member 21 is exposed to an environment having a relative humidity of 10 to 30% for 24 hours or more, and the holding step will be described later.
  • the metal to be filled as a conductive material preferably has electric resistivity is less material 10 3 ⁇ ⁇ cm, and specific examples thereof include gold (Au), silver ( Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn) are preferably exemplified.
  • the conductive substance Cu, Au, Al, and Ni are preferable, Cu and Au are more preferable, and Cu is further preferable, from the viewpoint of electrical conductivity.
  • an electroplating method for filling the inside of the through hole with metal for example, an electroplating method or an electroless plating method can be used.
  • an electroplating method or an electroless plating method it is difficult to selectively deposit (grow) a metal in the pores with a high aspect ratio by a conventionally known electrolytic plating method used for coloring or the like. It is considered that this is because the precipitated metal is consumed in the pores and the plating does not grow even if electrolysis is performed for a certain period of time or longer. Therefore, when the metal is filled by the 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 + 1 V.
  • constant potential electrolysis it is desirable that cyclic voltammetry can be used in combination, and potentiostat devices such as Solartron, BAS, Hokuto Denko, and IVIUM can be used.
  • constant current electrolysis can be used, but it is preferable to set the current value so that the voltage at the time of electrolysis is in the same range as the above-mentioned electrolysis voltage.
  • a normal DC power source can be used, and for example, known devices such as Matsusada Precision Co., Ltd., Takasago Seisakusho Co., Ltd., Kikusui Electronics Co., Ltd., and Texio Technology Co., Ltd. can be used. Further, in the above-mentioned electrolytic plating treatment method, pulse electrolysis, which is commonly used in the plating treatment, can also be used.
  • the plating solution a conventionally known plating solution can be used. Specifically, when precipitating copper, an aqueous solution containing copper sulfate is generally used, but the concentration of copper sulfate is preferably 1 to 300 g / L, preferably 100 to 200 g / L. Is more preferable. Further, the precipitation can be promoted by adding hydrochloric acid to the electrolytic solution. In this case, the hydrochloric acid concentration is preferably 10 to 20 g / L. Further, the plating solution may contain an acid, and the acid concentration thereof is preferably 0.01 to 1 mol / L.
  • Additives may be added to the electrolytic solution, and examples of the additives added to the electrolytic solution include those shown below. In addition, the following actions can be obtained by the additive.
  • an additive it is also possible to add an additive component called a brightener or a smoothing agent.
  • a brightener or a smoothing agent.
  • molecules or ions are adsorbed or precipitated alone to suppress the plating reaction. Saccharin, benzothiazole, thiourea, Janus Green B (JGB), benzelacetone, lead, bismuth and the like have an adhesion inhibitory effect.
  • Typical examples are PEG (polyethylene glycol), polyethylene glycol mono-4-nonylphenyl ether (PEGNPE), polyvinyl alcohol, gelatin and the like.
  • PEG polyethylene glycol
  • PEGNPE polyethylene glycol mono-4-nonylphenyl ether
  • polyvinyl alcohol gelatin and the like.
  • Unsaturated alcohols butynediol, propargyl alcohol, coumarin, etc.
  • NO 3 -, Fe 3 + and the like are representative examples.
  • the surface tension of the plating solution is adjusted to be as low as possible, and the surface tension is preferably 60 mN / m or less, which is lower than that of pure water. Surfactants or organic solvents can also be added to adjust the surface tension.
  • the pH (hydrogen ion index) of the plating solution is preferably adjusted, and the pH is preferably 1 or more.
  • the support 24 is provided on the back surface 16b of the anodic oxide film 16 using the resin base material 22 with respect to the metal filling member 21 as shown in FIG.
  • a functional adsorption film is used as the resin base material 22.
  • Q-chuck registered trademark
  • the support 24 preferably has the same outer shape as the anodic oxide film 16.
  • the support 24 supports the anodic oxide film 16 in a post-process. By attaching the support 24, the handleability is increased.
  • a metal layer removing step of removing the metal layer 19 of the metal filling member 21 is carried out.
  • the metal layer 19 is peeled off using an adhesive tape.
  • the plurality of through holes 17 have a small average diameter of 1 ⁇ m or less, and the metal layer can be easily removed by using an adhesive tape.
  • the metal layer removing step is not particularly limited as long as the metal layer 19 can be removed.
  • a surface smoothing treatment step for smoothing the surface 16a of the anodic oxide film 16 with the metal layer 19 shown in FIG. 13 removed.
  • the smoothing of the surface smoothing process can be done by using chemical mechanical polishing (CMP), dry etching or grinding, or by combining chemical mechanical polishing (CMP), dry etching and grinding. May be good.
  • CMP chemical mechanical polishing
  • different abrasive grains may be combined and polished, and in any method, the finished surface roughness (arithmetic mean roughness Ra (JIS B 0601: 2001)) is 0. It is preferably .02 ⁇ m or less.
  • the amount of polishing and the like can be reduced in the surface smoothing treatment step, and polishing can be easily carried out. As a result, the time required for the surface smoothing treatment can be shortened, and smoothing can be easily performed.
  • the above-mentioned metal layer removing step and surface smoothing treatment step are performed after the holding step.
  • a support member is provided on the back surface of the valve metal member 15 for handling such as transportation.
  • the anodic oxide film 16 and the frame portion 15d are partially removed in the thickness direction Dt, and the above-mentioned filled metal is used as the anode. It may protrude from the surface 16a of the oxide film 16. That is, the conduction path 20 may be projected from the surface 16a of the anodic oxide film 16.
  • the portion where the conduction path 20 protrudes from the surface 16a of the anodic oxide film 16 is referred to as a protruding portion 20a.
  • the step of projecting the filled metal from the surface 16a of the anodic oxide film 16 is called a metal projecting step.
  • an acid aqueous solution or an alkaline aqueous solution that does not dissolve the metal constituting the conduction path 20 but dissolves the anodic oxide film 16, that is, aluminum oxide (Al 2 O 3). Is used.
  • a part of the anodic oxide film 16 is removed by bringing the above-mentioned acid aqueous solution or alkaline aqueous solution into contact with the anodic oxide film 16 having through holes 17 filled with metal.
  • the method of bringing the above-mentioned acid aqueous solution or alkaline aqueous solution into contact with the anodic oxide film 16 is not particularly limited, and examples thereof include a dipping method, a spray method, and a spin processing method. Above all, a processing method using a spin processor is preferable from the viewpoint of uniformity.
  • the spin processor known products such as Sanmasu Semiconductor Industry Co., Ltd., Hitachi High-Technologies Corporation, SCREEN Holdings Co., Ltd., Dainippon Screen, Actes Kyozo Co., Ltd., and Kanamex Co., Ltd. can be used.
  • 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.
  • a phosphoric acid aqueous solution at 50 g / L and 40 ° C., a sodium hydroxide aqueous solution at 0.5 g / L and 30 ° C., or a potassium hydroxide aqueous solution at 0.5 g / L and 30 ° C. 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 further preferably 15 to 60 minutes.
  • the immersion time means the total of each immersion time when the immersion treatment for a short time is repeated.
  • a cleaning treatment may be performed or a neutralization treatment may be performed between the immersion treatments.
  • the metal is only projected from the surface 16a of the anodic oxide film 16, when the produced metal-filled microstructure 32 is used as an anisotropic conductive member, it is pressure-bonded to an object to be adhered such as a wiring board.
  • the metal protrudes from the surface 16a of the anodic oxide film 16 by 10 nm to 1000 nm, and more preferably 50 nm to 500 nm. That is, the amount of protrusion of the protruding portion 20a from the surface 16a is preferably 10 nm to 1000 nm, more preferably 50 nm to 500 nm.
  • the anodic oxide film 16 and the end portion of the conduction path 20 are made flush with each other. After processing, it is preferable to selectively remove the anodic oxide film.
  • heat treatment can be performed for the purpose of reducing the distortion in the conduction path 20 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 heat treatment is preferably carried out at an oxygen concentration of 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.
  • the heat treatment is preferably performed while applying stress to the anodic oxide film 16 for the purpose of straightening.
  • supercritical drying for example, a supercritical washing / drying device (SCRD6, manufactured by Rexxam Co., Ltd.) or the like can be used.
  • handling means holding the anodic oxide film 16 and moving the anodic oxide film 16 for transferring, transporting, and transporting the anodic oxide film 16.
  • "Easy to handle” means that damage to the anodic oxide film 16 can be suppressed when the above-mentioned anodic oxide film 16 is held and when the above-mentioned anodic oxide film 16 is moved. Since it is easy to handle, for example, the filled metal is projected from the surface 16a of the anodic oxide film 16, but damage to the metal can be suppressed.
  • the filled metal protrudes from the surface 16a of the anodic oxide film 16 as shown in FIG. 14, it is preferable to protect the protruding metal, that is, the protruding portion 20a of the conduction path 20. Therefore, as shown in FIG. 15, it is preferable to form the resin layer 26 in which the protruding portion 20a of the conduction path 20 is embedded on the surface 16a of the anodic oxide film 16.
  • the step of providing the resin layer 26 is called a resin layer forming step.
  • the method for producing the metal-filled microstructure may include a resin layer forming step.
  • the resin layer 26 protects the protruding portion 20a of the conduction path 20, and can further improve the transportability of the metal-filled microstructure, making it easier to handle.
  • the resin layer 26 has adhesiveness and imparts adhesiveness.
  • the resin layer 26 can be formed by using, for example, a conventionally known surface protective tape affixing device and a laminator. By providing the resin layer 26, the transportability of the metal-filled microstructure can be improved.
  • the resin material constituting the resin layer 26 include ethylene-based copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin-based resins, acrylic resins, and cellulose-based resins.
  • the above-mentioned resin layer is preferably a film with a peelable adhesive layer, and is adhesive by heat treatment or ultraviolet exposure treatment. It is more preferable that the film has an adhesive layer that is weakened 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 adhesive constituting the adhesive layer include a rubber adhesive, an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, and a polyamide 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 examples 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 included 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; acyl Phosphonate and the like can be mentioned.
  • Examples of commercially available heat-release type resin layers include Intellimar [registered trademark] tapes (manufactured by Nitta Corporation) such as WS5130C02 and WS5130C10; Somatac [registered trademark] TE series (manufactured by SOMAR Corporation); 3198, No. 3198LS, No. 3198M, No. 3198MS, No. 3198H, No. 3195, No. 3196, No. 3195M, No. 3195MS, No. 3195H, No. 3195HS, No. 3195V, No. 3195VS, No. 319Y-4L, No. 319Y-4LS, No. 319Y-4M, No. 319Y-4MS, No. 319Y-4H, No.
  • ELP holders such as ELP DU-300, ELP DU-2385KS, ELP DU-2187G, ELP NBD-3190K, ELP UE-2091J [registered trademark] (Nitto Denko).
  • UV peeling type resin layer include, for example, ELP RF-7232DB and ELP UB-5133D (all manufactured by Nitto Denko Corporation); SP-575B-150, SP-541B-205, SP-537T.
  • Backgrinding tapes such as -160 and SP-537T-230 (both manufactured by Furukawa Electric Co., Ltd.) can be used.
  • the above-mentioned film with an adhesive layer can be attached using a known surface protective tape affixing device and a laminator.
  • a resin composition containing an antioxidant material, a polymer material, a solvent (for example, methyl ethyl ketone, etc.) described later is used on the front surface and the back surface of the anodic oxide film 16.
  • a method of applying to the protruding portion of the conduction path, drying, and firing if necessary can be mentioned.
  • the coating method of the resin composition is not particularly limited, and for example, a gravure coating method, a reverse coating method, a die coating method, a blade coating method, a roll coating method, an air knife coating method, a screen coating method, a bar coating method, a curtain coating method, etc.
  • the drying method after coating is not particularly limited, and for example, a treatment of heating at a temperature of 0 ° C. to 100 ° C. in the atmosphere for several seconds to several tens of minutes, and a temperature of 0 ° C. to 80 ° C. under reduced pressure. Examples include heating for a dozen minutes to several hours.
  • the firing method after drying is not particularly limited because it differs depending on the polymer material used, but when a polyimide resin is used, for example, a treatment of heating at a temperature of 160 ° C. to 240 ° C. for 2 minutes to 60 minutes is performed. When an epoxy resin is used, for example, a treatment of heating at a temperature of 30 ° C. to 80 ° C. for 2 minutes to 60 minutes can be mentioned.
  • the support 24 shown in FIG. 15 is removed from the anodic oxide film 16.
  • the support 24 is removed from the anodic oxide film 16 starting from the resin base material 22.
  • the release layer 27 is laminated on the surface 26a of the resin layer 26.
  • the release layer 27 is a laminate of the support layer 28 and the release agent 29.
  • the release agent 29 is in contact with the resin layer 26. For example, by heating to a predetermined temperature, the adhesive force of the release agent 29 is weakened, and the release layer 27 can be removed.
  • the release agent 29 for example, Riva Alpha (registered trademark) manufactured by Nitto Denko Corporation and Somatac (registered trademark) manufactured by SOMAR Corporation can be used.
  • the support member 31 is attached to the release layer 27 using the double-sided adhesive 30.
  • the support member 31 is arranged to face the support layer 28.
  • the support member 31 has the same outer shape as the anodic oxide film 16.
  • the support member 31 serves as a support in a subsequent process. By attaching the support member 31, the handleability is increased.
  • the configuration of the double-sided adhesive 30 is not particularly limited as long as the support layer 28 of the release layer 27 and the support member 31 can be adhered to each other. Trademark) can be used.
  • the support member 31 supports the anodic oxide film 16 and is made of, for example, a silicon substrate.
  • a ceramic substrate such as SiC, SiC, GaN and alumina (Al 2 O 3 ), a glass substrate, a fiber reinforced plastic substrate, and a metal substrate can be used in addition to the silicon substrate.
  • the fiber reinforced plastic substrate also includes a FR-4 (Flame Retardant Type 4) substrate, which is a printed wiring board.
  • the back surface 16b of the anodic oxide film 16 is polished.
  • the back surface 16b of the anodic oxide film 16 and the end surface (not shown) of the conduction path 20 are flattened to the same surface. Since the polishing of the back surface 16b of the anodic oxide film 16 described above is the same as the surface smoothing treatment step for the surface 16a of the anodic oxide film 16 shown in FIG. 13, detailed description thereof will be omitted.
  • the surface of the back surface 16b of the anodic oxide film 16 having the plurality of conduction paths 20 may be carried out on at least one surface.
  • the reflectance of the front surface 16a and the back surface 16b of the anodic oxide film 16 is measured using a sensor (not shown), respectively, and if the reflectance value is within a predetermined range, polishing is not required. You may move to the next step.
  • the anodic oxide film 16 and the frame portion 15d are partially removed in the thickness direction Dt, and the above-mentioned filled metal is projected from the back surface 16b of the anodic oxide film 16. That is, the conduction path 20 is projected from the back surface 16b of the anodic oxide film 16.
  • the portion where the conduction path 20 protrudes from the back surface 16b of the anodic oxide film 16 is referred to as a protruding portion 20b. Since the step of projecting the filled metal from the back surface 16b of the anodic oxide film 16 is the same as the above-mentioned metal projecting step, detailed description thereof will be omitted.
  • a resin layer 26 in which the protruding portion 20b of the conduction path 20 of the back surface 16b of the anodic oxide film 16 is embedded is formed on the back surface 16b of the anodic oxide film 16.
  • the metal-filled microstructure 32 shown in FIG. 18 can be obtained. Since the method of forming the resin layer 26 in which the protruding portion 20b of the conduction path 20 is embedded is the same as the above-described resin layer forming step, detailed description thereof will be omitted.
  • the frame portion 15d remains on the outer edge of the anodic oxide film 16.
  • the frame portion 15d remaining on the outer edge portion may be removed by a physical method such as melting or grinding.
  • the metal-filled microstructure 32 of the anodic oxide film 16 alone can be obtained. If the valve metal member 15 can be removed without damaging the anodic oxide film 16, it is not limited to melting. Removing the valve metal member 15 such as an aluminum substrate is called a valve metal member removing step. The valve metal member removing step will be described later.
  • the shape of the metal-filled microstructure 32 is, for example, a disk shape, an apparatus used for transporting a semiconductor wafer or the like can be used for transporting the metal-filled microstructure 32, and the metal-filled microstructure 32 can be transported. No special device is required to handle the body 32.
  • the treatment liquid for dissolving the valve metal member 15 is an aluminum substrate
  • a treatment liquid for dissolving the aluminum substrate which is difficult to dissolve the anodic oxide film 16 of aluminum and is easy to dissolve aluminum.
  • the dissolution rate in aluminum is preferably 1 ⁇ m / min or more, more preferably 3 ⁇ m / min or more, and further preferably 5 ⁇ m / min or more.
  • the dissolution rate for the anodized film is preferably 0.1 nm / min or less, more preferably 0.05 nm / min or less, and even more preferably 0.01 nm / min or less.
  • a treatment liquid containing at least one metal compound having a lower ionization tendency than aluminum and having a pH (hydrogen ion index) of 4 or less or 8 or more, and the pH is 3 or less or It is more preferably 9 or more, and further preferably 2 or less or 10 or more.
  • a treatment liquid is based on an acid or alkaline aqueous solution, and is, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, etc.
  • a compound containing a gold compound for example, chloroplatinic acid
  • these fluorides these chlorides and the like.
  • an acid aqueous solution base is preferable, and a chloride blend is preferable.
  • a treatment liquid obtained by blending a hydrochloric acid aqueous solution with mercury chloride (hydrochloric acid / mercury chloride) and a treatment liquid obtained by blending a hydrochloric acid aqueous solution with copper chloride (hydrochloric acid / copper chloride) are preferable from the viewpoint of treatment latitude.
  • the composition of such a treatment liquid is not particularly limited, and for example, a bromine / methanol mixture, a bromine / ethanol mixture, royal water, or the like can be used.
  • the acid or alkali concentration of such a treatment liquid is preferably 0.01 to 10 mol / L, more preferably 0.05 to 5 mol / L.
  • the treatment temperature using such a treatment liquid is preferably ⁇ 10 ° C. to 80 ° C., preferably 0 ° C. to 60 ° C.
  • the above-mentioned valve metal member 15 is dissolved by bringing the valve metal member 15 into contact with the above-mentioned treatment liquid after the above-mentioned metal layer removing step.
  • the contact method is not particularly limited, and examples thereof include a dipping method and a spraying method. Above all, the dipping method is preferable.
  • the contact time at this time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.
  • FIGS. 20 to 24 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. 20 to 24 the same components as those shown in FIG. 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • the second example of the method for manufacturing the metal-filled microstructure is different from the first example of the method for manufacturing the metal-filled microstructure, and the mask 12 is only on the outer edge 11b of the surface 11a of the valve metal member 11 (FIG. 4).
  • the first example of the method for manufacturing a metal-filled microstructure is different in that the mask 13 having the opening 13a is arranged on the outer edge 11b of the surface 11a of the valve metal member 11 instead of forming (see).
  • the metal filling member 21 shown in FIG. 6 and the metal filling microstructure 32 shown in FIGS. 18 and 19 can be obtained.
  • a mask 13 having an opening 13a is arranged on the surface 11a of the valve metal member 11.
  • the mask 13 is installed on the outer edge 11b of the surface 11a of the valve metal member 11.
  • the region 11c corresponding to the opening 13a of the mask 13 is the region where the anodic oxide film 11d (see FIG. 22) is formed.
  • an anodic oxidation treatment is carried out using the valve metal member 11 as an electrode, and an anodic oxide film forming step of forming the anodic oxide film on the region 11c surrounded by the mask 13 is performed in the valve metal member 11. Since the anodic oxide film forming step is the same as the first example of the above-mentioned method for producing a metal-filled microstructure, detailed description thereof will be omitted.
  • the anodic oxide film 11d is formed in the above-mentioned region 11c, but the valve metal member 11 under the mask 13 is not anodized.
  • the mask 13 is separated from the surface 11a of the valve metal member 11.
  • the barrier layer is removed from the anodic oxide film 11d shown in FIG. 23, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 11d as shown in FIG. 24.
  • An anodic oxide film 16 composed of the anodic oxide film 11d is obtained.
  • a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is performed.
  • the metal layer 19 is formed as shown in FIG. It is formed. As a result, the metal filling member 21 shown in FIG. 6 is formed. Since the method for forming the metal layer 19 is the same as that of the first example of the method for manufacturing the metal-filled microstructure described above, detailed description thereof will be omitted.
  • FIGS. 25 to 29 are schematic cross-sectional views showing a third example of the packed microstructure according to the embodiment of the present invention in order of steps.
  • FIGS. 25 to 29 the same components as those shown in FIG. 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • the third example of the method for manufacturing the metal-filled microstructure is anodized in that the entire surface 11a of the valve metal member is anodized as compared with the first example of the method for manufacturing the metal-filled microstructure.
  • the metal-filled member 21 shown in FIG. 6 and FIGS. 18 and 19 are shown in the same manner as in the first example of the method for manufacturing the metal-filled microstructure, except that The metal-filled microstructure 32 shown can be obtained.
  • the valve metal member 11 (see FIG. 1) is prepared as in the first example of the method for manufacturing the metal-filled microstructure.
  • the entire surface 11a of the valve metal member 11 is anodized to form the anodic oxide film 11d (see FIG.
  • the anodic oxide film 16 preferably has a thickness HA of less than 200 ⁇ m. If the thickness HA is less than 200 ⁇ m, it can be considered that the anodic oxide film 16 and the valve metal member 15 are on the same surface.
  • a mask 14 is arranged on the surface 16a of the anodic oxide film 16 in addition to the outer edge 16e of the anodic oxide film 16.
  • the outer edge 16e of the anodic oxide film 16 is dissolved by using a liquid having a property that the anodic oxide film 16 is dissolved and the valve metal member 15 is not dissolved.
  • the bottom portion 15e of the valve metal member 15 is exposed.
  • the mask 14 is not particularly limited as long as it does not dissolve in a liquid having a characteristic that the anodized film 16 dissolves and the valve metal member 15 does not dissolve.
  • a resist film is used. Be done.
  • the resist film used for the mask 14 can be formed by forming a resist film on the entire surface 16a of the anodic oxide film 16 and then removing the resist film on the outer edge 16e of the anodic oxide film 16 by using a photolithography method. ..
  • an acid aqueous solution or an alkaline aqueous solution that dissolves aluminum oxide (Al 2 O 3) is used as the liquid having the property that the anodized film 16 is dissolved and the valve metal member 15 is not dissolved.
  • an acid aqueous solution or an alkaline aqueous solution that dissolves aluminum oxide (Al 2 O 3) is used.
  • Al 2 O 3 Specifically, for example, an aqueous hydrochloric acid solution containing copper chloride is used.
  • the mask 14 is removed from the surface 16a of the anodic oxide film 16.
  • a structure 18 having the valve metal member 15 and the anodic oxide film 16 is obtained.
  • the difference between the surface 16a of the anodic oxide film 16 and the upper surface of the frame portion 15d, that is, the thickness HA of the anodic oxide film 16 is less than 200 ⁇ m. Therefore, the surface 16a of the anodic oxide film 16 and the upper surface of the frame portion 15d are substantially on the same surface. If the mask 14 is a resist film, for example, it can be removed by ashing.
  • a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is performed.
  • a metal layer 19a is formed in the structure 18 by filling the inside of the plurality of through holes 17 of the anodic oxide film 16 with a metal beyond the surface 16a of the anodic oxide film 16. Will be done.
  • the metal filling member 21 is obtained.
  • the metal layer 19a by forming the metal layer 19a, the conductive passage 20 is formed, and the metal filling member 21 is formed.
  • the mask 14 is arranged to dissolve the outer edge 16e of the anodic oxide film 16, but the present invention is not limited to this, and the outer edge 16e of the anodic oxide film 16 may be physically scraped by grinding, laser light, or the like. .. Further, for example, a liquid having a property that the anodic oxide film is dissolved and the valve metal member is not dissolved is sprayed onto the outer edge 16e of the anodic oxide film 16 by using an inkjet method to select the outer edge 16e of the anodic oxide film 16. May be dissolved.
  • FIGS. 30 to 34 are schematic cross-sectional views showing a fourth example of the method for manufacturing a metal-filled microstructure according to the embodiment of the present invention in order of steps.
  • FIGS. 30 to 34 the same components as those shown in FIG. 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
  • the fourth example of the method for manufacturing the metal-filled microstructure has conductivity partially having conductivity on the surface 61a of the insulating support 61 as compared with the first example of the method for manufacturing the metal-filled microstructure.
  • the difference is that the valve metal member 11 is anodized using the electrode body 60 on which the layer 62 is formed.
  • the metal-filled member 21 shown and the metal-filled microstructure 32 shown in FIGS. 18 and 19 can be obtained.
  • a conductive layer 62 having conductivity is partially formed on the surface 61a of the rectangular insulating support 61.
  • the electrode body 60 is prepared.
  • the electrode body 60 is used as an electrode in the anodizing treatment.
  • the conductive layer 62 forms a resist layer 63 on the surface 61a of the insulating support 61, and the resist layer 63 is partially removed by patterning using, for example, a photolithography method.
  • a seed layer (not shown) is formed on the resist layer 63, and the conductive layer 62 is formed by plating.
  • the surfaces of the resist layer 63 and the conductive layer 62 are flattened by a flattening treatment.
  • the conductive layer 62 is formed by plating, the method for forming the conductive layer 62 is not particularly limited.
  • the valve metal member 11 is the anodic oxide film 16 of the metal filling member 21 (see FIG. 33), that is, the thickness of the anodic oxide film, or the anodic oxide film of the finally obtained metal-filled microstructure 32 (see FIG. 34).
  • the size and thickness of the 16 are appropriately determined according to the thickness, the apparatus for processing, and the like.
  • the valve metal member 11 is, for example, a rectangular plate material.
  • an aluminum substrate is used as described above.
  • an aluminum substrate may be prepared, but the valve metal member 11 may be formed on the electrode body 60.
  • an aluminum substrate is formed on the surface 62a of the conductive layer 62 and the surface 63a of the resist layer 63, for example, as the valve metal member 11 by a vapor deposition method.
  • an anodic oxidation treatment is carried out using the conductive layer 62 as an electrode, and an anodic oxide film forming step of forming the valve metal member 11 in the region on the conductive layer 62 on the anodic oxide film is performed.
  • the anodic oxide film is an insulating base material.
  • the anodic oxide film 11d is formed by anodizing the valve metal member 11.
  • the anodic oxidation treatment is carried out using the conductive layer 62 as the electrode of the cathode and the valve metal member 11 as the electrode of the anode.
  • the valve metal member 11 on the conductive layer 62 is anodized, and an anodic oxide film 11d is formed in the region 15c of the valve metal member 15 as shown in FIG.
  • a direct current is applied to the conductive layer 62 by using the extraction electrode.
  • the conductive layer 62 of the electrode body 60 is used as an electrode as described above, and the valve metal member 11 (see FIG. 31) on the conductive layer 62 of the electrode body 60 is formed with the anodic oxide film 11d.
  • the region 11c (see FIG. 31) is formed, and the valve metal member 11 (see FIG. 31) on the resist layer 63 is the outer edge 15b of the valve metal member 15 and becomes the frame portion 15d.
  • the anodic oxide film 11d is formed in the above-mentioned region 11c, but the valve metal member 11 on the resist layer 63 is not anodized.
  • valve metal members 11 do not become the anodic oxide film 11d, and there is a region where the valve metal member 11 remains even after the anodizing treatment.
  • the frame portion 15d of the valve metal member 15 composed of the valve metal member 11 is arranged on the outer edge 15b of the valve metal member 15.
  • An anodic oxide film 11d (see FIG. 32) is formed as the anodic oxide film 16 in the region 15c surrounded by the frame portion 15d.
  • all the valve metal members 11 on the conductive layer 62 can be formed into an anodic oxide film 11d, but by adjusting the anodizing treatment time and the like, a part of the valve metal member 11 on the conductive layer 62 is anodized.
  • valve metal member 15 exists between the conductive layer 62 and the anodic oxide film 16 which is the anodic oxide film. Since the valve metal member 11 is made of aluminum, an anodic oxide film 11d is formed as an oxide film, and the anodic oxide film 11d is made of an Al 2 O 3 film.
  • the anodic oxide film 11d When the anodic oxide film 11d is formed, there are a plurality of micropores. However, among the plurality of micropores, some micropores do not penetrate in the thickness direction Dt. In addition, there is a barrier layer (not shown) at the bottom of the micropores. Therefore, the barrier layer is removed from the anodic oxide film 11d shown in FIG. 32, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 11d as shown in FIG. 33. An anodic oxide film 16 composed of the anodic oxide film 11d is obtained.
  • an anodic oxide film 16 (anodide film) having a plurality of pores (through holes 17) is formed in the region 15c surrounded by the frame portion 15d arranged on the outer edge 15b of the valve metal member 15.
  • a structure 18 having a valve metal member 15 and an anodic oxide film 16 (anodized film) is obtained.
  • an anodic oxide film 16 (anodized film) is formed on the surface 15a of the valve metal member 15, and a frame portion 15d is provided around the anodic oxide film 16.
  • the surface 16a of the anodic oxide film 16 and the upper surface of the frame portion 15d are substantially the same surface.
  • the anodic oxide film forming step shown in FIG. 32 and the step of forming a plurality of through holes 17 extending in the thickness direction Dt shown in FIG. 33 are forming steps for obtaining the structure 18.
  • a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is performed on the structure 18.
  • the above-mentioned metal layer 19 is formed by filling the inside of the plurality of through holes 17 of the anodic oxide film 16 with metal beyond the surface 16a of the anodic oxide film 16 with respect to the structure 18.
  • the metal filling member 21 is obtained.
  • the conductive passage 20 having conductivity is formed. Since the method for forming the metal layer 19 is the same as that of the first example of the method for manufacturing the metal-filled microstructure described above, detailed description thereof will be omitted.
  • the inside of the plurality of through holes 17 of the anodic oxide film 16 is filled with metal, and as shown in FIG. 34, the surface of the structure 18, that is, on the frame portion 15d of the metal filling member 21, and the anodic oxidation.
  • a metal layer 19 on the surface 16a of the film 16, the metal is filled into the plurality of through holes 17.
  • the thickness ⁇ (see FIG. 2) of the portion existing on the frame portion 15d is set to 2 ⁇ m to 100 ⁇ m as described above.
  • the thickness ⁇ of the metal layer 19 can be increased by lengthening the plating time.
  • the metal layer 19 is also formed on the frame portion 15d by filling the metal beyond the surface 16a of the anodic oxide film 16.
  • FIG. 35 is a plan view showing an example of the configuration of the metal-filled microstructure according to the embodiment of the present invention
  • FIG. 36 is a schematic cross-sectional view showing an example of the configuration of the metal-filled microstructure according to the embodiment of the present invention. be.
  • FIG. 36 is a cross-sectional view taken along the line IB-IB of FIG. 35.
  • the anodic oxide film 16 which is an insulating base material, the through hole 17 penetrating the anodic oxide film 16 in the thickness direction Dt, and the through hole 17 It has a plurality of conduction paths 20 made of metal filled in the inside of the above.
  • the plurality of conduction paths 20 are provided in a state of being electrically insulated from each other.
  • the resin layer 26 provided on the front surface 16a and the back surface 16b of the anodic oxide film 16 is provided.
  • the "state of being electrically insulated from each other" means that the conduction paths 20 existing inside the anodic oxide film 16 are sufficiently low in conductivity with each other inside the anodic oxide film 16.
  • the conduction paths 20 are electrically insulated from each other, the conductivity is sufficiently low in the direction x orthogonal to the thickness direction Dt of the anodic oxide film 16, and the conductivity is provided in the thickness direction Dt. It is a member that has orthogonal conductivity.
  • the metal-filled microstructure 32 is arranged so that the thickness direction Dt is aligned with, for example, the stacking direction of the electronic elements described later. As shown in FIGS. 35 and 36, the conduction path 20 is provided so as to penetrate the anodic oxide film 16 in the thickness direction Dt in a state of being electrically insulated from each other.
  • the thickness h of the metal-filled microstructure 32 is, for example, 40 ⁇ m or less. Further, the metal-filled microstructure 32 preferably has a TTV (Total Thickness Variation) of 10 ⁇ m or less. Since the front surface 16a and the back surface 16b of the anodic oxide film 16 are polished, the thickness of the anodic oxide film 16 is thicker than the thickness h of the metal-filled microstructure 32, for example, it exceeds 60 ⁇ m, but is preferably about 40 ⁇ m from the viewpoint of brittleness.
  • the thickness h of the metal-filled microstructure 32 and the thickness of the anodized film 16 are such that the metal-filled microstructure 32 and the anodized film 16 are focused ion beams (FIB) in the thickness direction, respectively.
  • the cross section of the metal-filled microstructure 32 and the anodized film 16 was obtained at a magnification of 200,000 times with an electrolytically-release scanning electron microscope, and the contour shapes of the metal-filled microstructure 32 and the anodized film 16 were obtained and corresponded to the thickness h. It is an average value measured at 10 points for a region.
  • the TTV (Total Thickness Variation) of the metal-filled microstructure 32 is a value obtained by cutting the metal-filled microstructure 32 together with the support member 31 by dicing and observing the cross-sectional shape of the metal-filled microstructure 32. be.
  • the metal-filled microstructure 32 can be used, for example, as an anisotropically conductive member exhibiting anisotropic conductivity.
  • the semiconductor element and the semiconductor element are joined via the metal-filled microstructure 32 to obtain an electronic element in which the semiconductor element and the semiconductor element are electrically connected.
  • the metal-filled microstructure 32 functions as a TSV (Through Silicon Via).
  • an electronic element in which three or more semiconductor elements are electrically connected by using the metal-filled microstructure 32 can also be used. Three-dimensional mounting is possible by using the metal-filled microstructure 32.
  • the number of semiconductor elements to be bonded is not particularly limited, and is appropriately determined according to the function of the electronic element and the performance required for the electronic element.
  • Thermal pressure bonding can be used for bonding with the electronic element.
  • the metal electrode and the protruding portion are easily bonded at a temperature of 250 ° C. or lower, so that the heat effect on the device can be reduced.
  • the size of the electronic element can be reduced and the mounting area can be reduced. Further, by shortening the thickness of the metal-filled microstructure 32, the wiring length between the semiconductor elements can be shortened, the signal delay can be suppressed, and the processing speed of the electronic element can be improved. Power consumption can also be suppressed by shortening the wiring length between semiconductor elements. Since the metal-filled microstructure 32 is polished so that the anodic oxide film 16 and the conduction path 20 are flush with each other on the surface 16a of the anodic oxide film 16 as described above, the shape accuracy is high.
  • the height of the protruding portion 20a of the conduction path 20 can be strictly controlled as described above, the reliability of the electrical connection between the semiconductor element and the semiconductor element is excellent.
  • the metal-filled microstructure 32 is densely packed with metal, it has higher thermal conductivity than the resin material. Not only heat conduction in the vertical direction between connected electrodes and semiconductor elements, but also heat diffusion in the plane direction is large, so it is particularly useful for members that require heat dissipation.
  • the metal-filled microstructure 32 can be used for heat dissipation of a metal base substrate in addition to the above-mentioned semiconductor element, and is also effective for connecting heat dissipation fins. Further, it is very effective for joining a memory or the like, which has a problem of heat retention due to multi-layer connection.
  • Examples of semiconductor elements include logic integrated circuits such as ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), and ASSP (Application Specific Standard Product). Further, for example, a microprocessor such as a CPU (Central Processing Unit) and a GPU (Graphics Processing Unit) can be mentioned. Also, for example, DRAM (Dynamic RandomAccessMemory), HMC (HybridMemoryCube), MRAM (MagnetoresistiveRandomAccessMemory), PCM (Phase-ChangeMemory), ReRAM (ResistanceRandomAccessMemory), FeRAM (FerroelectricRandomAccessMemory) , Memory such as flash memory.
  • ASIC Application Specific Integrated Circuit
  • FPGA Field Programmable Gate Array
  • ASSP Application Specific Standard Product
  • a microprocessor such as a CPU (Central Processing Unit) and a GPU (Graphics Processing Unit) can be mentioned.
  • DRAM Dynamic RandomAccessMe
  • an analog integrated circuit such as an LED (Light Emitting Diode), a power device, a DC (Direct Current) -DC (Direct Current) converter, and an insulated gate bipolar transistor (IGBT) can be mentioned.
  • MEMS Micro Electro Mechanical Systems
  • MEMS Micro Electro Mechanical Systems
  • an acceleration sensor such as an acceleration sensor, a pressure sensor, a vibrator, and a gyro sensor
  • wireless elements such as GPS (Global Positioning System), FM (Frequency Modulation), NFC (Nearfield communication), RFEM (RF Expansion Module), MMIC (MonolithicMicrowaveIntegratedCircuit), WLAN (WirelessLocalAreaNetwork), discrete elements, CMOS (Complementary Metal). Oxide Semiconductor), CMOS image sensor, camera module, Passive device, SAW (Surface Acoustic Wave) filter, RF (Radio Frequency) filter, IPD (Integrated Passive Devices) and the like.
  • SAW Surface Acoustic Wave
  • RF Radio Frequency
  • the semiconductor element may have an element region.
  • the element region is an region in which various element constituent circuits and the like for functioning as an electronic element are formed.
  • a memory circuit such as a flash memory
  • MEMS Micro Electro Mechanical Systems
  • MEMS is, for example, a sensor, an actuator, an antenna, or the like.
  • Sensors include, for example, various sensors such as acceleration, sound, light and the like.
  • the optical sensor is not particularly limited as long as it can detect light, and for example, a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor is used.
  • the electronic element can be a combination of a semiconductor element having a logic circuit and a semiconductor element having a memory circuit.
  • the combination of semiconductor elements in the electronic element may be a combination of a sensor, an actuator, an antenna, or the like, a memory circuit, and a logic circuit.
  • the semiconductor element is composed of, for example, silicon, but is not limited to this, and may be silicon carbide, germanium, gallium arsenide, gallium nitride, or the like.
  • the two wiring layers may be electrically connected by using the metal-filled microstructure 32.
  • the anodic oxide film 16 functions as an insulating base material.
  • the distance between the conduction paths in the anodic oxide film 16 is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, and even more preferably 20 nm to 60 nm. When the distance between the conduction paths in the anodic oxide film 16 is within this range, the anodic oxide film 16 sufficiently functions as an insulating partition wall.
  • the distance between the conduction paths means the width w between the adjacent conduction paths
  • the cross section of the metal-filled microstructure 32 is observed by an electrolytic emission scanning electron microscope at a magnification of 200,000 times and adjacent to each other.
  • the average value of the width between conduction paths measured at 10 points.
  • the average diameter of the pores that is, the average diameter d of the through holes 17 (see FIGS. 35 and 36) is 1 ⁇ m or less, preferably 5 to 500 nm, more preferably 20 to 400 nm, and 40. It is more preferably to 200 nm, and most preferably 50 to 100 nm.
  • the average diameter d of the through hole 17 is 1 ⁇ m or less and is within the above range, a sufficient response can be obtained when an electric signal is passed through the obtained conduction path 20, so that the connector can be used as an inspection connector for electronic components. , Can be used more preferably.
  • the metal layer 19 see FIG.
  • the average diameter d of the through holes 17 is obtained by photographing the surface of the anodic oxide film 16 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 a ring-shaped periphery 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 range can be appropriately selected so that a photographed image capable of extracting 20 or more through holes can be obtained. For the opening diameter, 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
  • 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 portion is set as the opening diameter. ..
  • the plurality of conduction paths 20 are provided in a state of penetrating the anodic oxide film 16 in the thickness direction Dt and being electrically insulated from each other, and are columnar.
  • the conduction path 20 is made of metal.
  • the conduction path 20 may have protrusions protruding from the front surface and the back surface of the anodic oxide film 16, and the protrusions of each conduction path may be embedded in the resin layer.
  • gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni) and the like are preferably exemplified. From the viewpoint of electrical conductivity, copper, gold, aluminum, and nickel are preferable, and copper and gold are more preferable.
  • the protruding portions 20a and 20b of the conduction path 20 are portions where the conduction path 20 protrudes from the front surface 16a and the back surface 16b of the anodic oxide film 16, and are preferably protected by the resin layer 26.
  • the metal-filled microstructure 32 is used as an anisotropic conductive member, the protruding portion is crushed when the anisotropic conductive member and the electrode are electrically connected or physically joined by a method such as crimping.
  • the aspect ratio (height of the protruding portion / diameter of the protruding portion) of the protruding portion of the conductive path is preferably 0.5 or more and less than 50, preferably 0.8, for the reason that sufficient insulation in the plane direction can be ensured. It is more preferably about 20 and even more preferably 1 to 10.
  • the height of the protruding portion of the conduction path is preferably 20 nm or more, more preferably 100 nm to 500 nm.
  • the height of the protruding part of the conduction path is the average obtained by observing the cross section of the anisotropic conductive member with a field emission scanning electron microscope at a magnification of 20,000 times and measuring the height of the protruding part of the conduction path at 10 points.
  • the diameter of the protruding portion of the conduction path is an average value obtained by observing the cross section of the anisotropic conductive member with a field emission scanning electron microscope and measuring the diameter of the protruding portion of the conduction path at 10 points.
  • Density of the conductive paths 20 is preferably at 20,000 / mm 2 or more, more preferably 2,000,000 / mm 2 or more, still more preferably 10,000,000 / mm 2 or more, 50 million
  • the number of pieces / mm 2 or more is particularly preferable, and the number of pieces / mm 2 or more is most preferable.
  • the distance p between the centers of the adjacent conduction paths 20 is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and further preferably 50 nm to 140 nm. preferable.
  • the resin layer 26 is provided on the front surface 16a and the back surface 16b of the anodic oxide film 16, and the protruding portions 20a and 20b of the conduction path 20 are embedded as described above. That is, the resin layer 26 covers the end portion of the conduction path 20 protruding from the anodic oxide film 16 and protects the protruding portions 20a and 20b.
  • the resin layer 26 is formed by the above-mentioned resin layer forming step.
  • the resin layer 26 imparts adhesiveness to the connection target.
  • the resin layer 26 preferably exhibits fluidity in the temperature range of 50 ° C. to 200 ° C. and cures at 200 ° C. or higher.
  • the resin layer 26 is formed by the above-mentioned resin layer forming step, but the composition of the resin layer shown below can also be used.
  • the composition of the resin layer will be described.
  • the resin layer contains a polymer material and may contain an antioxidant material.
  • the polymer material contained in the resin layer is not particularly limited, but the gap between the semiconductor element or the semiconductor wafer and the anisotropic conductive member can be efficiently filled, and the adhesion to the semiconductor element or the semiconductor wafer is further improved.
  • it is preferably a thermosetting resin.
  • the thermosetting resin include epoxy resin, phenol resin, polyimide resin, polyester resin, polyurethane resin, bismaleimide resin, melamine resin, and isocyanate resin.
  • the benzotriazole derivative includes a hydroxyl group, an alkoxy group (for example, methoxy group, ethoxy group, etc.), an amino group, a nitro group, and an alkyl group (for example, a methyl group, an ethyl group, a butyl group, etc.) on the benzene ring of benzotriazole.
  • an alkoxy group for example, methoxy group, ethoxy group, etc.
  • an amino group for example, a nitro group
  • an alkyl group for example, a methyl group, an ethyl group, a butyl group, etc.
  • Substituted benzotriazole having a halogen atom for example, fluorine, chlorine, bromine, iodine, etc.
  • substituted naphthalene triazole the substituted naphthalene bistriazole and the like which have been substituted in the same manner as naphthalene triazole and naphthalene bistriazole can also be mentioned.
  • antioxidant material contained in the resin layer general antioxidants such as higher fatty acids, higher fatty acid copper, phenol compounds, alkanolamines, hydroquinones, copper chelating agents, organic amines, and organic substances are used. Examples include ammonium salts.
  • the content of the antioxidant material contained in the resin layer is not particularly limited, but from the viewpoint of anticorrosion effect, 0.0001% by mass or more is preferable, and 0.001% by mass or more is more preferable with respect to the total mass of the resin layer. Further, for the reason of obtaining an appropriate electric resistance in this joining process, 5.0% by mass or less is preferable, and 2.5% by mass or less is more preferable.
  • the resin layer contains a migration prevention material for the reason that the insulation reliability is further improved by trapping the metal ions and halogen ions that can be contained in the resin layer and the metal ions derived from the semiconductor element and the semiconductor wafer. Is preferable.
  • an ion exchanger for example, an ion exchanger, specifically, a mixture of a cation exchanger and an anion exchanger, or only a cation exchanger can be used.
  • the cation exchanger and the anion exchanger can be appropriately selected from, for example, the inorganic ion exchanger and the organic ion exchanger described later, respectively.
  • inorganic ion exchanger examples include hydrous oxides of metals typified by zirconium hydroxide.
  • zirconium hydroxide As the type of metal, for example, in addition to zirconium, iron, aluminum, tin, titanium, antimony, magnesium, beryllium, indium, chromium, bismuth and the like are known. Of these, the zirconium-based one has the ability to exchange the cations Cu 2+ and Al 3+. In addition, iron-based products also have exchangeability for Ag + and Cu 2+. Similarly, tin-based, titanium-based, and antimony-based ones are cation exchangers. On the other hand, those of bismuth-based, anion Cl - has exchange capacity for.
  • zirconium-based ones exhibit anion exchange ability depending on the conditions.
  • aluminum-based and tin-based ones As other inorganic ion exchangers, compounds such as acid salts of polyvalent metals typified by zirconium phosphate, heteropolylates typified by ammonium molybdrinate, and insoluble ferrocyanides are known. Some of these inorganic ion exchangers are already on the market, and for example, various grades under the trade name IXE of Toagosei Co., Ltd. are known. In addition to synthetic products, natural zeolite or powder of an inorganic ion exchanger such as montmorillonite can also be used.
  • organic ion exchanger examples include crosslinked polystyrene having a sulfonic acid group as a cation exchanger, and those having a carboxylic acid group, a phosphonic acid group or a phosphinic acid group.
  • anion exchanger examples include crosslinked polystyrene having a quaternary ammonium group, a quaternary phosphonium group or a tertiary sulfonium group.
  • inorganic ion exchangers and organic ion exchangers may be appropriately selected in consideration of the types of cations and anions to be captured and the exchange capacity for the ions.
  • the inorganic ion exchanger and the organic ion exchanger may be mixed and used. Since the manufacturing process of the electronic device includes a heating process, an inorganic ion exchanger is preferable.
  • the mixing ratio of the migration prevention material and the above-mentioned polymer material is preferably 10% by mass or less for the migration prevention material and 5% by mass or less for the migration prevention material, for example, from the viewpoint of mechanical strength. It is more preferable, and it is further preferable that the migration prevention material is 2.5% by mass or less. Further, from the viewpoint of suppressing migration when the semiconductor element or semiconductor wafer is bonded to the anisotropic conductive member, the migration prevention material is preferably 0.01% by mass or more.
  • the resin layer may contain an inorganic filler.
  • the inorganic filler is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, fine powdered silicon oxide, vapor phase silica, amorphous silica. , Crystalline silica, molten silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, aluminum nitride, zirconium oxide, yttrium oxide, silicon carbide, silicon nitride and the like.
  • the average particle size of the inorganic filler is larger than the distance between the conduction paths in order to prevent the inorganic filler from entering between the conduction paths and further improve the conduction reliability.
  • the average particle size of the inorganic filler is preferably 30 nm to 10 ⁇ m, more preferably 80 nm to 1 ⁇ m.
  • the average particle size is the primary particle size measured by a laser diffraction / scattering type particle size measuring device (Microtrac MT3300 manufactured by Nikkiso Co., Ltd.) as the average particle size.
  • the resin layer may contain a curing agent.
  • a curing agent When a curing agent is contained, a solid curing agent is not used at room temperature, but a liquid curing agent at room temperature is contained from the viewpoint of suppressing poor bonding with the surface shape of the semiconductor element or semiconductor wafer to be connected. Is more preferable.
  • solid at room temperature means a solid at 25 ° C., for example, a substance having a melting point higher than 25 ° C.
  • the curing agent examples include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives such as 4-methylimidazole, dicyandiamide, tetramethylguanidine, thiourea-added amines, and methyl.
  • aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone
  • aliphatic amines examples include imidazole derivatives such as 4-methylimidazole, dicyandiamide, tetramethylguanidine, thiourea-added amines, and methyl.
  • carboxylic acid anhydrides such as hexahydrophthalic anhydride, carboxylic acid hydrazide, carboxylic acid amides, polyphenol compounds, novolak resins, and polymercaptans. From these curing agents, liquid ones at 25 ° C.
  • the resin layer may contain various additives such as a dispersant, a buffer, and a viscosity regulator, which are generally added to the resin insulating film of a semiconductor package, as long as the characteristics are not impaired.
  • the thickness of the resin layer is preferably larger than the height of the protrusions 20a and 20b of the conduction path 20 and is 1 ⁇ m to 5 ⁇ m.
  • FIG. 37 is a schematic perspective view showing an example of a container used in the holding step of the embodiment of the present invention
  • FIG. 38 is a schematic cross-sectional view showing an example of a storage container of the holding step of the embodiment of the present invention. ..
  • holding is not limited to a stationary state and a stationary state, but also includes movement such as transportation.
  • the metal filling member 21 obtained by filling the plurality of through holes 17 (pores) of the structure 18 (see FIG. 5) with metal by the filling step is relative to each other. It is a process of exposing to an environment with a humidity of 10 to 30% for 24 hours or more.
  • stable insulation resistance can be obtained in the oxide film (anodic oxide film 16) having through holes (pores). If the relative humidity exceeds 40%, the insulation resistance fluctuates and stable insulation resistance cannot be obtained. On the other hand, it is difficult to control the humidity because a dedicated facility is required to maintain the relative humidity below 10%. Further, regarding the holding time, if it is less than 24 hours, the insulation resistance fluctuates and stable insulation resistance cannot be obtained.
  • the storage location and the like are not particularly limited as long as the metal filling member 21 is exposed to an environment having a relative humidity of 10 to 30% for 24 hours or more.
  • the metal filling member 21 is stored and stored in the container 40 shown in FIG. 37.
  • the container 40 has a container body 42 and a lid 44.
  • the opening 42a of the container body 42 is closed by the lid 44, and the container body 42 is sealed.
  • the temperature in the holding step may be 25 ° C. or higher, preferably 40 ° C. to 50 ° C.
  • a shelf (not shown) is provided inside the container 42b, and a plurality of metal filling members 21 are housed in the shelves one by one. If the metal filling members 21 are in contact with each other and laminated, the metal filling members 21 may be damaged when the metal filling members 21 rub against each other due to vibration or the like. Therefore, the metal filling member 21 is described above. It is preferable to store them separately as in. As long as they can be stored one by one, the shelves are not limited to the shelves, and spacers may be used instead of the shelves.
  • the metal filling member 21 has a rectangular shape as described above, and as the container 40, various containers for accommodating the rectangular substrate can be used.
  • the metal filling member 21 has a circular shape similar to the shape of a general semiconductor wafer
  • various containers for accommodating the semiconductor wafer can be used as the container 40.
  • a transfer capacity of a semiconductor wafer can be used, and for example, a front opening unfinded pod (FOUP), a front opening shipping box (FOSB), and the like can be used.
  • FOUP front opening unfinded pod
  • FOSB front opening shipping box
  • a storage container 50 and an adjusting unit 52 that adjusts the temperature and humidity of the inside 50a of the storage container 50 are used.
  • the storage container 50 is provided with a sensor 53 that records changes in the temperature and humidity of the inside 50a
  • the adjusting unit 52 is at least the storage container 50 based on the temperature information and the humidity information from the sensor 53. Adjust the humidity inside 50a.
  • feedback control based on the temperature information and the humidity information from the sensor 53 is used.
  • the adjusting unit 52 is not particularly limited as long as the humidity can be adjusted, for example. Known air conditioning equipment is available. Further, the adjusting unit 52 may be integrated with the storage container 50 or may be a separate body. In the holding process, the environment may be exposed to an environment with a relative humidity of 10 to 30% for 24 hours or more. Therefore, the adjusting unit 52 only needs to have a function of adjusting the temperature, and even a fan that ventilates the inside 50a of the storage container 50. good.
  • the humidity may be adjusted by providing a hygroscopic agent inside the storage container 50 50a, or the hygroscopic agent may be provided in the container 40 and only the temperature may be adjusted by the adjusting unit 52.
  • the sensor 53 is not particularly limited as long as it can measure the temperature and humidity during the storage period, but the temperature information and the humidity information can be recorded in time series together with the time, that is, it is recorded in the time history. It is preferable to be able to do it. Further, the sensor 53 may be a wired type or a wireless type.
  • a plurality of containers 40 are stored in the inner 50a of the storage container 50, and the adjusting unit 52 is operated in the stored state to operate the relative humidity of the metal filling member 21 of the container 40 in the inner 50a of the storage container 50. Is held at 10-40%.
  • the adjusting unit 52 adjusts the inside 50a of the storage container 50 so that the environment has a water content (g / cm 3 ) of 50% or less in absolute humidity at a temperature of 25 ° C.
  • the amount of water (g / cm 3 ) having an absolute humidity of 50% or less at a temperature of 25 ° C. is 11.52 (g / cm 3 ).
  • the humidity of the inside 50a of the storage container 50 can be reduced.
  • the relationship between the temperature, the humidity, and the absolute humidity is stored in the adjusting unit 52, and the water content in the inside 50a of the storage container 50 is obtained based on the temperature information and the humidity information from the sensor 53.
  • the temperature and humidity may be adjusted by the adjusting unit 52 based on the obtained water content.
  • the above-mentioned water content in the inside 50a of the storage container 50 can be adjusted by using a hygroscopic agent as described above.
  • the metal filling member 21 it is also preferable to store the metal filling member 21 under a reduced pressure lower than the atmospheric pressure. As a result, the absolute humidity inside the storage container 50 50a is lowered. From this, it is possible to suppress fluctuations in the insulation resistance of the metal filling member 21, and thus it is possible to suppress deterioration in the performance of the metal filling microstructure. Further, by storing the metal filling member 21 under reduced pressure as described above, oxidation of the protruding portions 20a and 20b of the conduction path 20 can be suppressed, whereby the metal filling member 21 can be joined, for example. , The effect of improving the bonding strength between the semiconductor element and the semiconductor wafer and reducing the bonding resistance with the bonding target can be obtained.
  • the above-mentioned depressurization can be realized by, for example, exhausting the air inside the storage container 50.
  • a vacuum pump such as a rotary pump is provided in the adjusting unit 52, and the inside 50a of the storage container 50 is further provided.
  • the pressure gauge and the pressure sensor are not particularly limited as long as they can measure the pressure lower than the atmospheric pressure, and those used for measuring the pressure in a general vacuum vessel can be appropriately used. be.
  • the above-mentioned pressure reduction means that the pressure is about 0.01 to 0.1 Pa.
  • a plurality of configurations are provided inside 50a of the storage container 50, the present invention is not limited to this, and one may be used.
  • the metal filling member 21 can be stored, and the metal filling member 21 can be transferred while being stored in the storage container 50.
  • the storage state can be managed and the transfer can be performed to the transfer destination.
  • the container 40 is not limited to the storage container 50, and may be stored in the storage bag 54 as shown in FIG. 39, for example.
  • the storage bag 54 is made of, for example, a film having a gas barrier property.
  • a film having gas barrier properties is, for example, a film having low water vapor permeability, which is a known film used for packaging electronic parts, or a gas barrier film used for organic EL (Electro Luminescence), electronic paper, solar cells, and the like. Can be used.
  • the gas barrier property is evaluated by the water vapor permeability, and the water vapor permeability is measured by the Mocon method or the like.
  • the storage bag 54 When the container 40 is stored in the storage bag 54, the storage bag 54 has low water vapor permeability and it is difficult to adjust the internal humidity from the outside. Therefore, it is preferable to provide the hygroscopic agent 55 inside the storage bag 54.
  • the amount of the hygroscopic agent 55 is determined in advance according to the water vapor permeability of the storage bag 54 to be used, the size of the container 40, the storage period, and the like, and the pre-determined amount of the hygroscopic agent 55 is stored in the storage bag 54.
  • the container 40 stored in the storage bag 54 is arranged inside 50a of the storage container 50 and stored as described above.
  • the temperature of the inside 50a of the storage container 50 is adjusted by the adjusting unit 52, the relative temperature of the metal filling member 21 is set to 10 to 40%, and the metal filling member 21 is stored. Even when the container 40 is stored in the storage bag 54, the metal filling member 21 can be stored under reduced pressure by setting the pressure inside 50a of the storage container 50 to be lower than the atmospheric pressure as described above.
  • the container 40 may be provided with the above-mentioned adjusting unit 52 and the sensor 53. Even in this case, the metal filling member 21 can be stored in the same manner as when the container 40 is arranged inside 50a of the storage container 50 described above. As described above, the pressure inside 50a of the storage container 50 is set to a pressure lower than the atmospheric pressure, and the metal filling member 21 can be stored under reduced pressure.
  • the container 40 shown in FIG. 37 is not always necessary.
  • the spacer 56 is arranged on the metal layer 19 of the metal filling member 21.
  • a plurality of metal filling members 21 may be laminated and stored in the storage bag 54.
  • the spacer 56 paper, a resin film, or the like can be used.
  • the spacer 56 may be any one that covers at least the metal layer 19 of the metal filling member 21.
  • the present invention is basically configured as described above. Although the method for producing the metal-filled microstructure of the present invention has been described in detail above, the present invention is not limited to the above-described embodiment, and various improvements or changes have been made without departing from the gist of the present invention. Of course, it is also good.
  • the present invention will be described in more detail with reference to Examples below.
  • the materials, reagents, amounts of substances and their ratios, operations, etc. 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 members of Examples 1 to 9 and Comparative Examples 1 to 3 were produced.
  • the transportability of the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3 was evaluated.
  • the insulation resistance of the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3 was evaluated after ensuring anisotropic conductivity.
  • each evaluation item of transportability and insulation resistance will be described.
  • the temperature and humidity conditions in the transportability test are based on G (+ 23 ° C, humidity 50% RH (relative humidity)) in Table 1 (pretreatment temperature and humidity conditions) of JIS Z 0203: 2000, and are used for the test material. Then, a random vibration test was performed for 180 minutes, and then the same test material was subjected to a flip-up test for 30 minutes. After the above-mentioned test, the metal filling member taken out from the case was visually confirmed, and the result of the one having the worst evaluation level among the multiple pieces transported in the metal filling part was taken as the overall evaluation. Damage to the metal filling part was evaluated according to the following evaluation criteria. The evaluation results of transportability are shown in Table 1 below.
  • the case where the metal layer, which is the metal filling portion, is not scratched was designated as A.
  • the case where the metal layer, which is the metal filling portion, was scratched but did not reach the anodic oxide film was defined as B.
  • the case where the metal layer which is the metal filling portion is scratched and reaches the anodic oxide film is designated as C.
  • Example 1 The metal filling member of Example 1 will be described.
  • Dumplon (registered trademark) tape No. 375 (width 25 mm ⁇ length 50 m) was used.
  • the above-mentioned aluminum substrate was subjected to an electrolytic polishing treatment using an electrolytic polishing liquid having the following composition under the conditions of a voltage of 10 V, a liquid temperature of 65 ° C., and a liquid flow velocity of 3.0 m / min.
  • the treated area of the electrolytic treatment was 0.12 m 2 .
  • the cathode was a carbon electrode, and the power supply 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).
  • the aluminum substrate after the electrolytic polishing treatment was anodized 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 a pre-anodizing treatment for 1 hour with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 45 V, a liquid temperature of 16 ° C., and a liquid flow velocity of 3.0 m / min. ..
  • the pre-anodized aluminum substrate was subjected to a film removal treatment by immersing it in a 0.6 mol / L phosphoric acid aqueous solution (liquid temperature: 40 ° C.) for 0.5 hours. Then, anodizing treatment was performed again with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 45 V, a liquid temperature of 16 ° C., and a liquid flow velocity of 3.0 m / min to partially anodize the surface of the aluminum substrate. To form an anodized film having a thickness of 50 ⁇ m.
  • a structure having an aluminum substrate having a frame portion having a width of 5 mm on the outer edge and an anodic oxide film provided in the frame portion of the aluminum substrate was obtained.
  • Both the pre-anodizing treatment and the re-anodizing treatment were performed with the aluminum substrate masked with a high-adhesive tape.
  • the cathode was a titanium electrode and PAM320-12 (manufactured by Kikusui Electronics Co., Ltd.) was used as the power source.
  • a NeoCool BD36 (manufactured by Yamato Scientific Co., Ltd.) was used as the cooling device, and a pair stirrer PS-100 (manufactured by EYELA Tokyo Rika Kikai Co., Ltd.) was used as the stirring and heating device. Further, the flow velocity of the electrolytic solution was measured using a vortex type flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
  • the anodicated substrate is immersed in ion-exchanged water (50 ° C.) and a solution containing a surfactant (45 ° C.) alternately for 3 minutes each, then poured with ion-exchanged water, and then the barrier layer is removed in a wet state. It was used for processing.
  • a solution prepared by diluting the pretreatment solution "NeutraClean 68" manufactured by Roam & Haas with ion-exchanged water at a ratio of 1: 4 was used.
  • An etching treatment (barrier layer removal treatment) is performed in which the mixture is immersed in a sodium hydroxide solution containing supersaturated metallic zinc maintained at a temperature of 25 ° C.
  • the average diameter of the micropores (pores) present in the anodic oxide film after the barrier layer removing step was 60 nm.
  • the average diameter was calculated as an average value measured at 50 points by taking a surface photograph (magnification: 50,000 times) with an FE-SEM (Field emission-Scanning Electron Microscope).
  • the average thickness of the anodic oxide film after the barrier layer removing step was 40 ⁇ m. That is, the average thickness of the oxide film was 40 ⁇ m.
  • the average thickness of the anodic oxide film is 10 points after cutting the anodic oxide film with FIB (Focused Ion Beam) in the thickness direction and taking a surface photograph (magnification 50,000 times) of the cross section with FE-SEM.
  • the density of micropores present in the anodic oxide film was about 100 million pieces / mm 2 .
  • the density of micropores was measured and calculated by the method described in paragraphs [0168] and [0169] of JP-A-2008-270158.
  • the degree of regularization of the micropores present in the anodic oxide film was 92%. The degree of regularization was calculated by taking a surface photograph (magnification of 20000 times) with an FE-SEM and measuring by the method described in paragraphs [0024] to [0027] of JP-A-2008-270158.
  • the aluminum substrate was used as a cathode and copper was used as a positive electrode for electrolytic plating.
  • copper is filled inside the micropores, and a metal layer made of copper is also formed on the frame portion. A metal-filled member was obtained.
  • the thickness ⁇ of the metal layer on the frame portion was 50 ⁇ m.
  • PAS20-36 manufactured by Kikusui Denshi Kogyo Co., Ltd.
  • PAS20-36 manufactured by Kikusui Denshi Kogyo Co., Ltd.
  • a low-humidity low-temperature constant temperature and humidity controller (PDL-4J)) with 10 manufactured metal filling members laminated, stored in a vinyl chloride case and covered with a lid. Model) Stored in ESPEC CO., LTD.).
  • the inside of the low humidity type low temperature constant temperature and humidity chamber was brought into an environment with a temperature of 40 ° C. and a relative humidity of 20%, and after exposure for 25 hours, the following steps were carried out.
  • Dumplon tape No. 375 manufactured by Nitto Denko KK was used as the adhesive tape.
  • the aluminum substrate was dissolved and removed by immersing it in a 20 mass% mercury chloride aqueous solution (rise) at 20 ° C. for 3 hours to obtain an anodized film as a simple substance.
  • ⁇ Smoothing process> the surface of the anodic oxide film was subjected to CMP (Chemical Mechanical Polishing) treatment, and the surface was polished to smooth the surface.
  • the smoothing step ensures anisotropic conductivity. In this state, the above-mentioned insulation resistance was measured.
  • a polishing device BC-15CN (trade name)) manufactured by MAT was used to polish the surface of the anodized film with an abrasive containing alumina (WA # 8000 (FF) made by Chemet Japan Co., Ltd.).
  • Primary polishing is performed with a solution diluted 4-fold with water), secondary polishing is performed with an abrasive containing silica (manufactured by SA1-1-0 Chemet Japan Co., Ltd.), and the arithmetic average coarseness of the finished product after polishing is performed. (JIS B0601: 2001) was set to 0.005 ⁇ m.
  • Example 2 Example 2 was the same as that of Example 1 except that the holding time was 30 hours as compared with Example 1.
  • Example 3 was the same as that of Example 1 except that the holding time was 40 hours as compared with Example 1.
  • Example 4 was the same as that of Example 1 except that the width of the frame portion was 3 mm as compared with Example 2.
  • a high-adhesive tape was attached so that a frame having a width of 3 mm could be formed around the frame.
  • Example 5 was the same as that of Example 1 except that the thickness of the frame portion was 240 ⁇ m as compared with Example 3.
  • an aluminum substrate having a thickness of 240 ⁇ m was used.
  • Example 6 Example 6 was the same as Example 1 except that the relative humidity was 10% as compared with Example 2.
  • Example 7 was the same as Example 1 except that the relative humidity was 30% as compared with Example 3.
  • Example 8 Example 8 was the same as that of Example 1 except that the average diameter was 40 nm as compared with Example 3.
  • the anodizing treatment was carried out in a 15% aqueous sulfuric acid solution at a voltage of 25 V at a liquid temperature of 3 ° C., and the average diameter was 40 nm.
  • Example 9 Example 9 was the same as Example 1 except that the average diameter was 200 nm as compared with Example 3.
  • the anodizing treatment was carried out with a 0.1 M aqueous phosphoric acid solution at a voltage of 195 V and the liquid temperature was set to 3 ° C., and the average diameter was set to 200 nm.
  • Comparative Example 1 Comparative Example 1 was the same as that of Example 1 except that the holding time was 20 hours as compared with Example 1.
  • Comparative Example 2 Comparative Example 2 was the same as that of Example 1 except that the configuration without the frame portion was different from that of Example 1.
  • an anodic oxide film was formed over the entire surface of the valve metal member to prepare a metal-filled member.
  • Comparative Example 3 Comparative Example 3 was the same as that of Example 1 except that the relative humidity was 40% as compared with Example 1.

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Abstract

Provided is a method for manufacturing a metal-filled microstructure which has excellent conveyance stability and inhibits deterioration of insulation performance. The method for manufacturing a metal-filled microstructure comprises: a formation step in which an oxide film having a plurality of micropores is formed in a formation region surrounded by a frame portion disposed on the outer edge of a valve metal member, thereby obtaining a structure having the valve metal member and the oxide film; a filling step in which the structure is filled with a metal in the plurality of micropores of the oxide film; and a holding step in which a metal-filled member obtained in the filling step by filling the structure with a metal in the plurality of micropores of the oxide film is left for at least 24 hours in an environment having a relative humidity of 10-30%. The plurality of micropores have an average diameter of no larger than 1 μm.

Description

金属充填微細構造体の製造方法Manufacturing method of metal-filled microstructure
　本発明は、バルブ金属部材を用いた金属充填微細構造体の製造方法に関し、特に、搬送性に優れ、かつ絶縁性能化が良好な金属充填微細構造体の製造方法に関する。 The present invention relates to a method for manufacturing a metal-filled microstructure using a valve metal member, and more particularly to a method for manufacturing a metal-filled microstructure having excellent transportability and good insulation performance.
　絶縁性基材に設けられた複数の貫通孔に金属等の導電性物質が充填されてなる構造体は、近年ナノテクノロジーでも注目されている分野のひとつであり、例えば、異方導電性部材としての用途が期待されている。
　異方導電性部材は、半導体素子等の電子部品と回路基板との間に挿入し、加圧するだけで電子部品と回路基板間の電気的接続が得られるため、半導体素子等の電子部品等の電気的接続部材、及び機能検査を行う際の検査用コネクタ等として広く使用されている。
　特に、半導体素子等の電子部品は、ダウンサイジング化が顕著である。従来のワイヤーボンディングのような配線基板を直接接続する方式、フリップチップボンディング、及びサーモコンプレッションボンディング等では、電子部品の電気的な接続の安定性を十分に保証することができないため、電子接続部材として異方導電性部材が注目されている。 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. For example, as an anisotropic conductive member. Is expected to be used.
Since the anisotropic conductive member can be electrically connected between the electronic component and the circuit board simply by inserting it between the electronic component such as a semiconductor element and the circuit board and pressurizing it, the electronic component such as the semiconductor element can be used. It is widely used as an electrical connection member and an inspection connector for performing functional inspections.
In particular, electronic components such as semiconductor elements are significantly downsized. As a method of directly connecting wiring boards such as conventional wire bonding, flip-chip bonding, thermocompression bonding, etc., the stability of electrical connection of electronic components cannot be sufficiently guaranteed, and therefore, as an electronic connection member. An anisotropic conductive member is attracting attention.
　例えば、特許文献１には、１０００万個／ｍｍ2以上の密度でマイクロポア貫通孔を有する基材からなり、一部のマイクロポア貫通孔が、基材の材料以外の物質で充填されている、微細構造体の製造方法が記載されている。特許文献１の微細構造体の製造方法では、基材がアルミナであり、アルミニウム基板に、少なくとも、（Ａ）陽極酸化処理によりマイクロポアを有する酸化皮膜を形成する処理、（Ｂ）上述の（Ａ）処理で得られた酸化皮膜から、アルミニウムを除去する処理、（Ｃ）上述の（Ｂ）処理でアルミニウムが除去された酸化皮膜に存在するマイクロポアの一部を貫通させる処理、（Ｄ）上述の（Ｃ）処理で貫通させたマイクロポア内に、酸化皮膜以外の物質を充填させる処理、（Ｅ）上述の（Ｄ）処理後の酸化皮膜の表面及び裏面を、化学機械研磨処理によって平滑化する表面平滑化処理、をこの順に施している。 For example, Patent Document 1 is composed of a base material having micropore through holes at a density of 10 million pieces / mm 2 or more, and some of the micropore through holes are filled with a substance other than the material of the base material. , A method for manufacturing a microstructure is described. In the method for producing a microstructure of Patent Document 1, the base material is alumina, and at least (A) an oxide film having micropores is formed on an aluminum substrate by anodization treatment, and (B) the above-mentioned (A). ) A treatment for removing aluminum from the oxide film obtained by the treatment, (C) a treatment for penetrating a part of micropores existing in the oxide film from which aluminum was removed by the above-mentioned (B) treatment, (D) the above-mentioned treatment. The micropores penetrated by the (C) treatment of (C) are filled with a substance other than the oxide film, and (E) the front and back surfaces of the oxide film after the above-mentioned (D) treatment are smoothed by a chemical mechanical polishing treatment. The surface smoothing treatment is performed in this order.
特開２０１３－１６７０２３号公報Japanese Unexamined Patent Publication No. 2013-167023
　上述の特許文献１の微細構造体の製造方法では、マイクロポア貫通孔が、基材の材料以外の物質で充填されている微細構造体を得ることができる。上述のように、特許文献１の微細構造体の製造方法では、（Ｄ）貫通させたマイクロポア内に、酸化皮膜以外の物質を充填させる処理と、（Ｅ）上述の（Ｄ）処理後の酸化皮膜の表面及び裏面を、化学機械研磨処理によって平滑化する表面平滑化を実施しているが、上述の（Ｄ）と、上述の（Ｅ）との処理を連続して行わず、上述の（Ｄ）の後、例えば、搬送等により、所定の時間経過後に上述の（Ｅ）を実施することもある。この場合、搬送等により充填部が損傷する可能性がある。また、工程間の環境等の影響を受けて、微細構造体の絶縁性能が劣化することもある。 In the method for producing a microstructure of Patent Document 1 described above, it is possible to obtain a microstructure in which the micropore through-holes are filled with a substance other than the material of the base material. As described above, in the method for producing a microstructure of Patent Document 1, (D) a treatment of filling a penetrating micropore with a substance other than an oxide film, and (E) after the above-mentioned (D) treatment. Although surface smoothing is performed in which the front surface and the back surface of the oxide film are smoothed by a chemical mechanical polishing treatment, the above-mentioned (D) and the above-mentioned (E) are not continuously performed, and the above-mentioned treatment is performed. After (D), the above-mentioned (E) may be carried out after a predetermined time has elapsed, for example, by transportation or the like. In this case, the filling portion may be damaged by transportation or the like. In addition, the insulation performance of the microstructure may deteriorate due to the influence of the environment between processes.
　本発明の目的は、搬送性に優れ、かつ絶縁性能の劣化を抑制した金属充填微細構造体の製造方法を提供することにある。 An object of the present invention is to provide a method for manufacturing a metal-filled microstructure which is excellent in transportability and suppresses deterioration of insulation performance.
　上述の目的を達成するために、本発明の一態様は、バルブ金属部材の外縁に配置されたフレーム部により囲まれる形成領域に、複数の細孔を有する酸化膜を形成することにより、バルブ金属部材と酸化膜とを有する構造体を得る形成工程と、構造体に対して、酸化膜の複数の細孔に金属を充填する充填工程と、充填工程により、構造体に対して、酸化膜の複数の細孔に金属を充填して得られた金属充填部材を、相対湿度１０～３０％の環境に２４時間以上さらす保持工程とを有し、複数の細孔は、平均直径が１μｍ以下である、金属充填微細構造体の製造方法を提供するものである。 In order to achieve the above object, one aspect of the present invention is to form an oxide film having a plurality of pores in a forming region surrounded by a frame portion arranged on the outer edge of the valve metal member, thereby forming the valve metal. A forming step of obtaining a structure having a member and an oxide film, a filling step of filling a plurality of pores of the oxide film with metal for the structure, and a filling step of filling the structure with an oxide film. It has a holding step of exposing a metal-filled member obtained by filling a plurality of pores with metal to an environment with a relative humidity of 10 to 30% for 24 hours or more, and the plurality of pores have an average diameter of 1 μm or less. It provides a method for manufacturing a certain metal-filled microstructure.
　バルブ金属部材は、アルミニウムで構成されていることが好ましい。
　酸化膜は、陽極酸化膜であることが好ましい。
　陽極酸化膜は、Ａｌ２Ｏ３膜であることが好ましい。
　充填工程において、酸化膜の複数の細孔に充填する金属は、銅であることが好ましい。
　充填工程は、構造体の表面に金属層を形成することにより、金属を複数の細孔に充填する工程であり、充填工程は、金属層をフレーム部上に厚み１００μｍ以下に形成することが好ましい。
　保持工程の後、構造体の表面に形成された金属層を除去する金属層除去工程を有することが好ましい。
　金属層除去工程の後、酸化膜の表面を平滑化する表面平滑化処理工程を有することが好ましい。
　表面平滑化処理工程の平滑化は、化学的機械的研磨、ドライエッチング又は研削を用いることが好ましい。 The valve metal member is preferably made of aluminum.
The oxide film is preferably an anodic oxide film.
The anodic oxide film is preferably an Al 2 O 3 film.
In the filling step, the metal to be filled in the plurality of pores of the oxide film is preferably copper.
The filling step is a step of filling a plurality of pores with metal by forming a metal layer on the surface of the structure, and the filling step is preferably a step of forming a metal layer on a frame portion having a thickness of 100 μm or less. ..
After the holding step, it is preferable to have a metal layer removing step of removing the metal layer formed on the surface of the structure.
After the metal layer removing step, it is preferable to have a surface smoothing treatment step for smoothing the surface of the oxide film.
For the smoothing of the surface smoothing treatment step, it is preferable to use chemical mechanical polishing, dry etching or grinding.
　本発明によれば、搬送性に優れ、かつ絶縁性能の劣化を抑制した金属充填微細構造体の製造方法を得ることができる。 According to the present invention, it is possible to obtain a method for producing a metal-filled microstructure having excellent transportability and suppressing deterioration of insulation performance.
本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 図５に示す構造体の平面図である。It is a top view of the structure shown in FIG. 図７に示す構造体の領域Ｑを拡大して示す模式的平面図である。It is a schematic plan view which shows the area Q of the structure shown in FIG. 7 enlarged. 図７に示す構造体の領域Ｑを拡大して示す模式的断面図である。FIG. 5 is a schematic cross-sectional view showing an enlarged area Q of the structure shown in FIG. 7. 図６に示す金属充填部材について、図７に示す構造体の領域Ｑに相当する部分を拡大して示す模式的平面図である。6 is a schematic plan view showing an enlarged portion of the metal filling member shown in FIG. 6 corresponding to the region Q of the structure shown in FIG. 7. 図６に示す金属充填部材について、図７に示す構造体の領域Ｑに相当する部分を拡大して示す模式的断面図である。6 is a schematic cross-sectional view showing an enlarged portion of the metal filling member shown in FIG. 6 corresponding to the region Q of the structure shown in FIG. 7. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 1st example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第２の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第２の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第２の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第２の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第２の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 2nd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第３の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第３の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第３の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第３の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第３の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 3rd example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第４の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 4th example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第４の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 4th example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第４の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 4th example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第４の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 4th example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の製造方法の第４の例の一工程を示す模式的断面図である。It is a schematic cross-sectional view which shows one step of the 4th example of the manufacturing method of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の構成の一例を示す平面図である。It is a top view which shows an example of the structure of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の金属充填微細構造体の構成の一例を示す模式的断面図である。It is a schematic cross-sectional view which shows an example of the structure of the metal-filled microstructure of the embodiment of this invention. 本発明の実施形態の保持工程に用いられる容器の一例を示す模式的斜視図である。It is a schematic perspective view which shows an example of the container used for the holding process of embodiment of this invention. 本発明の実施形態の保持工程に用いられる収納容器の一例を示す模式的断面図である。It is a schematic cross-sectional view which shows an example of the storage container used for the holding process of embodiment of this invention. 本発明の実施形態の保持工程に用いられる収納袋の一例を示す模式的斜視図である。It is a schematic perspective view which shows an example of the storage bag used for the holding process of embodiment of this invention. 本発明の実施形態の保持工程に用いられる容器の他の例を示す模式図である。It is a schematic diagram which shows another example of the container used for the holding process of embodiment of this invention. 本発明の実施形態の保持工程に用いられる収納形態の一例を示す模式的斜視図である。It is a schematic perspective view which shows an example of the storage form used for the holding process of embodiment of this invention.
　以下に、添付の図面に示す好適実施形態に基づいて、本発明の金属充填微細構造体の製造方法を詳細に説明する。
　なお、以下に説明する図は、本発明を説明するための例示的なものであり、以下に示す図に本発明が限定されるものではない。
　なお、以下において数値範囲を示す「～」とは両側に記載された数値を含む。例えば、εａが数値αｂ～数値βｃとは、εａの範囲は数値αｂと数値βｃを含む範囲であり、数学記号で示せばαｂ≦εａ≦βｃである。
　「直交」等の角度は、特に記載がなければ、該当する技術分野で一般的に許容される誤差範囲を含む。また、湿度及び時間について、特に記載がなければ、該当する技術分野で一般的に許容される誤差範囲を含む。 Hereinafter, the method for producing the metal-filled microstructure of the present invention will be described in detail based on the preferred embodiments shown in the accompanying drawings.
It should be noted that the figures described below are exemplary for explaining the present invention, and the present invention is not limited to the figures shown below.
In the following, "-" indicating the numerical range includes the numerical values described on both sides. For example, when ε a is a numerical value α b to a numerical value β c , the range of ε a is a range including the numerical value α b and the numerical value β c , and in mathematical symbols, α b ≤ ε a ≤ β c .
Angles such as "orthogonal" include error ranges generally tolerated in the art in question, unless otherwise stated. Also, unless otherwise specified, humidity and time include error ranges generally acceptable in the relevant technical field.
　金属充填微細構造体に関し、細孔（貫通孔）を有する酸化膜は絶縁抵抗が変動した。絶縁抵抗の変動について調べると保管場所、及び保管時期により影響を受けていたことが判明した。特別な温度調節を行わない倉庫内でも寒期は、絶縁抵抗が良好であったり、温度調節を実施している建屋内でも絶縁抵抗が不定期に悪化する等の挙動が見られた。
　鋭意検討した結果、保管中の温度ではなく、細孔（貫通孔）を有する酸化膜中の水分が影響するのではないかと考え、保管条件のうち特に、湿度について絶縁性能との関係を調べたところ、ある湿度の範囲で保持することにより、安定した絶縁抵抗が得られることがわかり本発明に至った。以下、金属充填微細構造体の製造方法について具体的に説明する。 Regarding the metal-filled microstructure, the insulating resistance of the oxide film having pores (through holes) fluctuated. Examining the fluctuation of insulation resistance, it was found that it was affected by the storage location and storage time. Even in a warehouse where no special temperature control was performed, the insulation resistance was good during the cold season, and even in the building where the temperature was controlled, the insulation resistance deteriorated irregularly.
As a result of diligent studies, we thought that the water content in the oxide film with pores (through holes) might have an effect, not the temperature during storage, and investigated the relationship between the humidity and the insulation performance, especially among the storage conditions. However, it has been found that stable insulation resistance can be obtained by holding the film in a certain humidity range, which led to the present invention. Hereinafter, a method for manufacturing a metal-filled microstructure will be specifically described.
［金属充填微細構造体の製造方法の第１の例］
　図１～図６、及び図１２～図１９は、本発明の実施形態の金属充填微細構造体の製造方法の第１の例の一例を工程順に示す模式的断面図である。図７は図５に示す構造体の平面図であり、図８は図７に示す構造体の領域Ｑを拡大して示す模式的平面図であり、図９は図７に示す構造体の領域Ｑを拡大して示す模式的断面図である。また、図１０は図６に示す金属充填部材について、図７に示す構造体の領域Ｑに相当する部分を拡大して示す模式的平面図であり、図１１は図６に示す金属充填部材について、図７に示す構造体の領域Ｑに相当する部分を拡大して示す模式的断面図である。 [First example of a method for manufacturing a metal-filled microstructure]
1 to 6 and 12 to 19 are schematic cross-sectional views showing an example of a first example of the method for producing a metal-filled microstructure according to an embodiment of the present invention in order of steps. 7 is a plan view of the structure shown in FIG. 5, FIG. 8 is a schematic plan view showing an enlarged area Q of the structure shown in FIG. 7, and FIG. 9 is a schematic plan view showing the area Q of the structure shown in FIG. 7. It is a schematic cross-sectional view which shows Q enlarged. Further, FIG. 10 is a schematic plan view showing an enlarged portion of the metal filling member shown in FIG. 6 corresponding to the region Q of the structure shown in FIG. 7, and FIG. 11 is a schematic plan view showing the metal filling member shown in FIG. , Is an enlarged schematic cross-sectional view showing a portion corresponding to the region Q of the structure shown in FIG. 7.
　金属充填微細構造体は、バルブ金属部材の表面に陽極酸化処理を施して得られるものである。金属充填微細構造体は、バルブ金属の陽極酸化膜からなる絶縁性基材を有するものである。バルブ金属はアルミニウム等であるが、アルミニウムに特に限定されるものではないが、絶縁性基材として、アルミニウムの陽極酸化膜を例に説明する。このため、以下の説明では、バルブ金属部材としてアルミニウム基板を例にして説明する。
　図１に示すように、バルブ金属部材１１として、アルミニウム基板を用意する。
　次に、図２に示すように、バルブ金属部材１１の表面１１ａの外縁１１ｂにだけ、マスク１２を形成する。マスク１２は、電気的に絶縁なものであれば、特に限定されるものではなく、例えば、半導体素子の形成に用いられる公知のレジスト膜を用いることができる。マスク１２は、例えば、バルブ金属部材１１の表面１１ａ全面にレジスト膜を形成した後、フォトリソグラフィ法を用いて、バルブ金属部材１１の表面１１ａの外縁１１ｂ以外のレジスト膜を除去し、外縁１１ｂにだけマスク１２を形成する。これ以外に、マスク１２として、例えば、レジストペンを用いて、バルブ金属部材１１の表面１１ａの外縁１１ｂにだけレジスト膜を形成してもよい。更には、耐酸性を有する粘着性樹脂テープをバルブ金属部材１１の表面１１ａの外縁１１ｂに貼り付けてマスク１２としてもよい。
　バルブ金属部材１１の表面１１ａのうち、マスク１２で囲まれた領域１１ｃが陽極酸化膜１６（図５参照）の形成領域である。 The metal-filled microstructure is obtained by subjecting the surface of the valve metal member to anodizing. The metal-filled microstructure has an insulating substrate made of an anodized film of valve metal. The valve metal is aluminum or the like, but the valve metal is not particularly limited to aluminum, but an anodic oxide film of aluminum will be described as an example as an insulating base material. Therefore, in the following description, an aluminum substrate will be described as an example of the valve metal member.
As shown in FIG. 1, an aluminum substrate is prepared as the valve metal member 11.
Next, as shown in FIG. 2, the mask 12 is formed only on the outer edge 11b of the surface 11a of the valve metal member 11. The mask 12 is not particularly limited as long as it is electrically insulating, and for example, a known resist film used for forming a semiconductor element can be used. For the mask 12, for example, after forming a resist film on the entire surface 11a of the valve metal member 11, a resist film other than the outer edge 11b of the surface 11a of the valve metal member 11 is removed by a photolithography method, and the outer edge 11b is formed. Only the mask 12 is formed. Alternatively, as the mask 12, for example, a resist pen may be used to form a resist film only on the outer edge 11b of the surface 11a of the valve metal member 11. Further, an acid-resistant adhesive resin tape may be attached to the outer edge 11b of the surface 11a of the valve metal member 11 to form the mask 12.
Of the surface 11a of the valve metal member 11, the region 11c surrounded by the mask 12 is the region where the anodic oxide film 16 (see FIG. 5) is formed.
　次に、バルブ金属部材１１を電極とした陽極酸化処理を実施し、バルブ金属部材１１のうち、マスク１２で囲まれた領域１１ｃに陽極酸化膜に形成する陽極酸化膜形成工程を行う。なお、陽極酸化膜１６（図５参照）は絶縁性基材である。
　陽極酸化膜形成工程では、バルブ金属部材１１を陽極の電極として、陽極酸化処理を実施する。これにより、バルブ金属部材１１が陽極酸化されて、図３に示すようにバルブ金属部材１１の領域１１ｃに陽極酸化膜１１ｄが形成される。陽極酸化処理において、例えば、バルブ金属部材１１の裏面側から電流を印加してもよく、外縁１１ｂ側から電流を印加してもよい。 Next, an anodic oxidation treatment is carried out using the valve metal member 11 as an electrode, and an anodic oxide film forming step of forming the anodic oxide film on the region 11c surrounded by the mask 12 is performed in the valve metal member 11. The anodic oxide film 16 (see FIG. 5) is an insulating base material.
In the anodic oxide film forming step, the anodic oxidation treatment is carried out using the valve metal member 11 as an anode electrode. As a result, the valve metal member 11 is anodized, and an anodic oxide film 11d is formed in the region 11c of the valve metal member 11 as shown in FIG. In the anodizing treatment, for example, a current may be applied from the back surface side of the valve metal member 11, or a current may be applied from the outer edge 11b side.
　陽極酸化処理では、上述のようにバルブ金属部材１１を電極として用いており、バルブ金属部材１１の領域１１ｃ（図３参照）が陽極酸化膜１１ｄの形成領域となり、マスク１２の下のバルブ金属部材１１（図２参照）が、外縁１５ｂ（図４参照）であり、フレーム部１５ｄ（図４参照）になる。
　上述の領域１１ｃに陽極酸化膜１１ｄが形成されるが、マスク１２下のバルブ金属部材１１は陽極酸化されない。このように、バルブ金属部材１１が全て陽極酸化膜１１ｄにならず、陽極酸化処理後でもバルブ金属部材１５のままの領域がある。これにより、バルブ金属部材１５の外縁１５ｂに、バルブ金属部材１５で構成された、バルブ金属部材１５のフレーム部１５ｄが配置される。フレーム部１５ｄより囲まれる領域１５ｃに陽極酸化膜１６（図４参照）が形成される。
　なお、バルブ金属部材１１がアルミニウムで構成されているため、酸化膜として、陽極酸化膜１６が形成され、陽極酸化膜１６はＡｌ２Ｏ３膜で構成される。 In the anodizing treatment, the valve metal member 11 is used as an electrode as described above, and the region 11c (see FIG. 3) of the valve metal member 11 becomes the forming region of the anodic oxide film 11d, and the valve metal member under the mask 12. Reference numeral 11 (see FIG. 2) is an outer edge 15b (see FIG. 4) and a frame portion 15d (see FIG. 4).
The anodic oxide film 11d is formed in the above-mentioned region 11c, but the valve metal member 11 under the mask 12 is not anodized. As described above, all the valve metal members 11 do not become the anodic oxide film 11d, and there is a region where the valve metal member 15 remains even after the anodizing treatment. As a result, the frame portion 15d of the valve metal member 15 composed of the valve metal member 15 is arranged on the outer edge 15b of the valve metal member 15. An anodic oxide film 16 (see FIG. 4) is formed in the region 15c surrounded by the frame portion 15d.
Since the valve metal member 11 is made of aluminum, an anodic oxide film 16 is formed as an oxide film, and the anodic oxide film 16 is made of an Al 2 O 3 film.
　陽極酸化膜１１ｄは形成した時点で、複数のマイクロポアが存在する。しかしながら、複数のマイクロポアのうち、厚み方向Ｄｔに貫通していないマイクロポアもある。また、マイクロポアの底部にはバリア層（図示せず）が存在する。このため、図３に示す陽極酸化膜１１ｄに対して、バリア層を除去して、図４に示すように、陽極酸化膜１６に、厚み方向Ｄｔに延在する貫通孔１７を複数形成する。 When the anodic oxide film 11d is formed, there are a plurality of micropores. However, among the plurality of micropores, some micropores do not penetrate in the thickness direction Dt. In addition, there is a barrier layer (not shown) at the bottom of the micropores. Therefore, the barrier layer is removed from the anodic oxide film 11d shown in FIG. 3, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 16 as shown in FIG.
　以上の工程により、バルブ金属部材１５の外縁１５ｂに配置されたフレーム部１５ｄで囲まれる領域１５ｃに、複数の細孔（貫通孔１７）を有する酸化膜（陽極酸化膜１６）を形成することにより、バルブ金属部材１５と、酸化膜（陽極酸化膜１６）とを有する構造体１８を得る。例えば、図７及び図８に示すように、バルブ金属部材１５の表面１５ａに、陽極酸化膜１６が形成され、陽極酸化膜１６の周囲にフレーム部１５ｄがある。また、図９に示すように、陽極酸化膜１６の表面１６ａと、フレーム部１５ｄの表面とは、略同一面である。
　上述のように、図３に示す陽極酸化膜形成工程と、図４に示す、厚み方向Ｄｔに延在する貫通孔１７を複数形成する工程とが、構造体１８を得る形成工程である。 By the above steps, an oxide film (anodic oxide film 16) having a plurality of pores (through holes 17) is formed in the region 15c surrounded by the frame portion 15d arranged on the outer edge 15b of the valve metal member 15. , A structure 18 having a valve metal member 15 and an oxide film (anodic oxide film 16) is obtained. For example, as shown in FIGS. 7 and 8, an anodic oxide film 16 is formed on the surface 15a of the valve metal member 15, and a frame portion 15d is provided around the anodic oxide film 16. Further, as shown in FIG. 9, the surface 16a of the anodic oxide film 16 and the surface of the frame portion 15d are substantially the same surface.
As described above, the anodic oxide film forming step shown in FIG. 3 and the step of forming a plurality of through holes 17 extending in the thickness direction Dt shown in FIG. 4 are forming steps for obtaining the structure 18.
〔アルミニウム基板〕
　アルミニウム基板は、特に限定されず、その具体例としては、純アルミニウム板；アルミニウムを主成分とし微量の異元素を含む合金板；低純度のアルミニウム（例えば、リサイクル材料）に高純度アルミニウムを蒸着させた基板；シリコンウエハ、石英、ガラス等の表面に蒸着、スパッタ等の方法により高純度アルミニウムを被覆させた基板；アルミニウムをラミネートした樹脂基板；等が挙げられる。 [Aluminum substrate]
The aluminum substrate 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 foreign elements; high-purity aluminum is vapor-deposited on low-purity aluminum (for example, a recycled material). A substrate; a substrate obtained by coating the surface of a silicon wafer, quartz, glass or the like with high-purity aluminum by a method such as vapor deposition or sputtering; a resin substrate laminated with aluminum; and the like.
　アルミニウム基板のうち、陽極酸化処理により陽極酸化膜を形成する片側の表面は、アルミニウム純度が、９９．５質量％以上であることが好ましく、９９．９質量％以上であるのがより好ましく、９９．９９質量％以上であるのが更に好ましい。アルミニウム純度が上述の範囲であると、マイクロポア配列の規則性が十分となる。
　アルミニウム基板は、陽極酸化膜を形成することができれば、特に限定されるものでなく、例えば、ＪＩＳ（Japanese Industrial Standards）　１０５０材、及び１０７０材が用いられる。 Of the aluminum substrate, 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. When the aluminum purity is in the above range, the regularity of the micropore arrangement is sufficient.
The aluminum substrate is not particularly limited as long as it can form an anodic oxide film, and for example, JIS (Japanese Industrial Standards) 1050 material and 1070 material are used.
　アルミニウム基板のうち陽極酸化処理される片側の表面は、予め熱処理、脱脂処理及び鏡面仕上げ処理が施されていることが好ましい。
　ここで、熱処理、脱脂処理及び鏡面仕上げ処理については、特開２００８－２７０１５８号公報の［００４４］～［００５４］段落に記載された各処理と同様の処理を施すことができる。
　陽極酸化処理の前の鏡面仕上げ処理は、例えば、電解研磨であり、電解研磨には、例えば、リン酸を含有する電解研磨液が用いられる。
　ここで、バルブ金属としては、具体的には、例えば、上述のアルミニウム以外に、タンタル、ニオブ、チタン、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス、アンチモン等が挙げられる。 The surface of one side of the aluminum substrate to be anodized is preferably heat-treated, degreased, and mirror-finished in advance.
Here, regarding 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 performed.
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.
Here, as the valve metal, specific examples thereof include tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like, in addition to the above-mentioned aluminum.
〔陽極酸化処理工程〕
　陽極酸化処理は、従来公知の方法を用いることができるが、マイクロポア配列の規則性を高くし、金属充填微細構造体の異方導電性を担保する観点から、自己規則化法又は定電圧処理を用いることが好ましい。
　ここで、陽極酸化処理の自己規則化法及び定電圧処理については、特開２００８－２７０１５８号公報の［００５６］～［０１０８］段落及び［図３］に記載された各処理と同様の処理を施すことができる。 [Anodizing process]
For the anodizing treatment, a conventionally known method can be used, but from the viewpoint of increasing the regularity of the micropore arrangement and ensuring the anisotropic conductivity of the metal-filled microstructure, a self-regulating method or a constant voltage treatment can be used. Is preferably used.
Here, regarding 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.
　複数のマイクロポアを有する陽極酸化膜には、上述のようにマイクロポアの底部にバリア層（図示せず）が存在する。このバリア層を除去するバリア層除去工程を有する。 The anodic oxide film having a plurality of micropores has a barrier layer (not shown) at the bottom of the micropores as described above. It has a barrier layer removing step of removing the barrier layer.
〔バリア層除去工程〕
　バリア層除去工程は、例えば、アルミニウムよりも水素過電圧の高い金属Ｍ１のイオンを含むアルカリ水溶液を用いて、陽極酸化膜のバリア層を除去する工程である。
　上述のバリア層除去工程により、バリア層が除去され、かつ、マイクロポアの底部に、金属Ｍ１からなる導電体層が形成されることになる。
　ここで、水素過電圧（hydrogen overvoltage）とは、水素が発生するのに必要な電圧をいい、例えば、アルミニウム（Ａｌ）の水素過電圧は－１．６６Ｖである（日本化学会誌，１９８２、（８），ｐ１３０５－１３１３）。なお、アルミニウムの水素過電圧よりも高い金属Ｍ１の例及びその水素過電圧の値を以下に示す。
　＜金属Ｍ１及び水素（１Ｎ Ｈ2ＳＯ4）過電圧＞
　・白金（Ｐｔ）：０．００Ｖ
　・金（Ａｕ）：０．０２Ｖ
　・銀（Ａｇ）：０．０８Ｖ
　・ニッケル（Ｎｉ）：０．２１Ｖ
　・銅（Ｃｕ）：０．２３Ｖ
　・錫（Ｓｎ）：０．５３Ｖ
　・亜鉛（Ｚｎ）：０．７０Ｖ [Barrier layer removal process]
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.
By the barrier layer removing step described above, the barrier layer is removed and a conductor layer made of metal M1 is formed at the bottom of the micropores.
Here, the hydrogen overvoltage means a voltage required for hydrogen to be generated. For example, the hydrogen overvoltage of aluminum (Al) is −1.66 V (Journal of the Chemical Society of Japan, 1982, (8)). , P1305-1313). An example of the metal M1 having a hydrogen overvoltage higher than that of aluminum and the value of the hydrogen overvoltage thereof are shown below.
<Metal M1 and hydrogen (1NH 2 SO 4 ) overvoltage>
-Platinum (Pt): 0.00V
-Gold (Au): 0.02V
-Silver (Ag): 0.08V
-Nickel (Ni): 0.21V
-Copper (Cu): 0.23V
-Tin (Sn): 0.53V
-Zinc (Zn): 0.70V
　貫通孔１７（細孔）は、マイクロポアを拡径し、かつバリア層を除去して形成することもできる。この場合、マイクロポアの拡径には、ポアワイド処理が用いられる。ポアワイド処理は、陽極酸化膜を、酸水溶液又はアルカリ水溶液に浸漬させることにより、陽極酸化膜を溶解させ、マイクロポアの孔径を拡大する処理である、ポアワイド処理には、硫酸、リン酸、硝酸、塩酸等の無機酸又はこれらの混合物の水溶液、又は水酸化ナトリウム、水酸化カリウム及び水酸化リチウム等の水溶液を用いることができる。
　なお、ポアワイド処理でも、マイクロポアの底部のバリア層を除去することができ、ポアワイド処理において水酸化ナトリウム水溶液を用いることにより、マイクロポアが拡径され、かつバリア層が除去される。
　ポアワイド処理は、バリア層除去工程と同様に、導電体層を形成することができない。このため、ポアワイド処理後、改めてアルミニウムよりも水素過電圧の高い金属Ｍ１のイオンを含む水溶液を用いて処理して導電体層を形成してもよく、更に異なる金属を含む水溶液で複数段階の処理を施して導電体層を形成してもよい。 The through hole 17 (pore) can also be formed by expanding the diameter of the micropore and removing the barrier layer. In this case, pore wide processing is used to increase the diameter of the micropores. The pore-wide treatment is a treatment in which the anodic oxide film is immersed in an acid aqueous solution or an alkaline aqueous solution to dissolve the anodic oxide film and expand the pore size of the micropores. An aqueous solution of an inorganic acid such as hydrochloric acid or a mixture thereof, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like can be used.
The barrier layer at the bottom of the micropore can also be removed by the pore wide treatment, and by using the sodium hydroxide aqueous solution in the pore wide treatment, the diameter of the micropore is expanded and the barrier layer is removed.
The pore-wide treatment cannot form the conductor layer as in the barrier layer removing step. Therefore, after the pore-wide treatment, the conductor layer may be formed by treating again with an aqueous solution containing ions of a metal M1 having a higher hydrogen overvoltage than aluminum, and further, a plurality of steps of treatment with an aqueous solution containing a different metal may be performed. It may be applied to form a conductor layer.
　次に、図４の状態からマスク１２を外す（図５参照）。そして、図５に示す構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７に、金属を充填する充填工程を実施する。構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７の内部に金属を充填することにより、図６に示すように、導電性を有する導通路２０が形成され、金属充填部材２１を得る。なお、金属を充填する充填工程は、後に詳細に説明する。
　充填工程では、陽極酸化膜１６の複数の貫通孔１７の内部に金属を充填すればよいが、図５、図１０及び図１１に示すように、構造体１８の表面、すなわち、金属充填部材２１のフレーム部１５ｄ上及び陽極酸化膜１６の表面１６ａ上に、金属層１９を形成することにより、金属を複数の貫通孔１７に充填してもよい。この場合、フレーム部１５ｄ上に金属層１９を、厚みδ（図５及び図１１）１００μｍ以下に形成することが好ましい。金属層１９の厚みδの下限値としては、例えば、２μｍである。
　金属層１９の厚みδが２～１００μｍであれば、導通路２０が保護され、金属充填部材２１の搬送時に、陽極酸化膜１６、及び導通路２０等の損傷が抑制される。なお、金属層１９の厚みδは、例えば、めっき時間を長くすることにより、厚くすることができる。充填工程では、陽極酸化膜１６の表面１６ａを超えて、金属を充填することにより、フレーム部１５ｄ上に金属層１９が形成される。
　充填工程では、陽極酸化膜１６の表面１６ａ迄、貫通孔１７内に金属を充填して、金属層１９を設けない工程としてもよい。 Next, the mask 12 is removed from the state shown in FIG. 4 (see FIG. 5). Then, for the structure 18 shown in FIG. 5, a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is carried out. By filling the inside of the plurality of through holes 17 of the anodic oxide film 16 with respect to the structure 18, a conductive passage 20 having conductivity is formed as shown in FIG. 6, and the metal filling member 21 is formed. obtain. The filling step of filling the metal will be described in detail later.
In the filling step, the inside of the plurality of through holes 17 of the anodic oxide film 16 may be filled with metal, but as shown in FIGS. 5, 10 and 11, the surface of the structure 18, that is, the metal filling member 21 The metal may be filled in the plurality of through holes 17 by forming the metal layer 19 on the frame portion 15d of the above and on the surface 16a of the anodic oxide film 16. In this case, it is preferable to form the metal layer 19 on the frame portion 15d with a thickness δ (FIGS. 5 and 11) of 100 μm or less. The lower limit of the thickness δ of the metal layer 19 is, for example, 2 μm.
When the thickness δ of the metal layer 19 is 2 to 100 μm, the conduction path 20 is protected, and damage to the anodic oxide film 16 and the conduction path 20 is suppressed during transportation of the metal filling member 21. The thickness δ of the metal layer 19 can be increased by increasing the plating time, for example. In the filling step, the metal layer 19 is formed on the frame portion 15d by filling the metal over the surface 16a of the anodic oxide film 16.
In the filling step, the through hole 17 may be filled with metal up to the surface 16a of the anodic oxide film 16 so that the metal layer 19 is not provided.
　金属層１９の厚みδは、金属充填部材２１を厚み方向に対して切断し、ＦＥ－ＳＥＭ（Field emission - Scanning Electron Microscope）を用いて切断断面の断面観察を行い、１０点測定した平均値である。
　また、バルブ金属部材１５の底部１５ｅの厚み、特に限定されるものではないが、２０μｍ以上あることが好ましく、３０～５０μｍであることが更に好ましい。
　上述のバルブ金属部材１５の底部１５ｅの厚みは、上述の金属層１９の厚みδと同じく、金属充填部材２１を厚み方向に対して切断し、ＦＥ－ＳＥＭを用いて切断断面の断面観察を行い、１０点測定した平均値である。 The thickness δ of the metal layer 19 is an average value measured at 10 points by cutting the metal filling member 21 in the thickness direction and observing the cut cross section using an FE-SEM (Field emission-Scanning Electron Microscope). be.
The thickness of the bottom portion 15e of the valve metal member 15 is not particularly limited, but is preferably 20 μm or more, and more preferably 30 to 50 μm.
The thickness of the bottom portion 15e of the valve metal member 15 described above is the same as the thickness δ of the metal layer 19 described above, the metal filling member 21 is cut in the thickness direction, and the cross section of the cut cross section is observed using FE-SEM. It is an average value measured at 10 points.
　上述の金属を充填する充填工程により、金属充填部材２１が得られる。次に、金属充填部材２１を、相対湿度１０～３０％の環境に２４時間以上さらす保持工程を実施する。保持工程については、金属充填部材２１を、相対湿度１０～３０％の環境に２４時間以上さらす工程であれば、その工程は特に限定されるものではなく、保持工程については後に説明する。 The metal filling member 21 is obtained by the filling step of filling the metal described above. Next, a holding step of exposing the metal filling member 21 to an environment having a relative humidity of 10 to 30% for 24 hours or more is carried out. The holding step is not particularly limited as long as the metal filling member 21 is exposed to an environment having a relative humidity of 10 to 30% for 24 hours or more, and the holding step will be described later.
〔充填工程〕
　＜充填される金属＞
　上述の貫通孔１７の内部に、導電性物質として充填される金属は、電気抵抗率が１０3Ω・ｃｍ以下の材料であることが好ましく、その具体例としては、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、ニッケル（Ｎｉ）、及び亜鉛（Ｚｎ）が好適に例示される。
　なお、導電性物質としては、電気伝導性の観点から、Ｃｕ、Ａｕ、Ａｌ、Ｎｉが好ましく、Ｃｕ、Ａｕがより好ましく、Ｃｕが更に好ましい。 [Filling process]
<Metal to be filled>
Inside the above-mentioned through hole 17, the metal to be filled as a conductive material preferably has electric resistivity is less material 10 3 Ω · cm, and specific examples thereof include gold (Au), silver ( Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn) are preferably exemplified.
As the conductive substance, Cu, Au, Al, and Ni are preferable, Cu and Au are more preferable, and Cu is further preferable, from the viewpoint of electrical conductivity.
　＜充填方法＞
　貫通孔の内部に金属を充填する電解めっき処理方法としては、例えば、電解めっき法又は無電解めっき法を用いることができる。
　ここで、着色等に用いられる従来公知の電解めっき法では、選択的に孔中に金属を高アスペクトで析出（成長）させることは困難である。これは、析出金属が孔内で消費され一定時間以上電解を行なってもめっきが成長しないためと考えられる。
　そのため、電解めっき法により金属を充填する場合は、パルス電解又は定電位電解の際に休止時間をもうける必要がある。休止時間は、１０秒以上必要で、３０～６０秒であることが好ましい。
　また、電解液のかくはんを促進するため、超音波を加えることも望ましい。 <Filling method>
As an electroplating method for filling the inside of the through hole with metal, for example, an electroplating method or an electroless plating method can be used.
Here, it is difficult to selectively deposit (grow) a metal in the pores with a high aspect ratio by a conventionally known electrolytic plating method used for coloring or the like. It is considered that this is because the precipitated metal is consumed in the pores and the plating does not grow even if electrolysis is performed for a certain period of time or longer.
Therefore, when the metal is filled by the 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.
　更に、電解電圧は、通常２０Ｖ以下であって望ましくは１０Ｖ以下であるが、使用する電解液における目的金属の析出電位を予め測定し、その電位＋１Ｖ以内で定電位電解を行なうことが好ましい。なお、定電位電解を行なう際には、サイクリックボルタンメトリを併用できるものが望ましく、Ｓｏｌａｒｔｒｏｎ社、ＢＡＳ株式会社、北斗電工株式会社、ＩＶＩＵＭ社等のポテンショスタット装置を用いることができる。
　上述の電解めっき処理方法では、定電流電解を用いることも可能であるが、電解時の電圧が上述の電解電圧と同じ範囲になるよう電流値を設定することが好ましい。この場合、通常の直流電源を利用することができ、例えば、松定プレシジョン株式会社、株式会社高砂製作所、菊水電子工業株式会社、株式会社テクシオテクノロジー等の公知の装置を用いることができる。また、上述の電解めっき処理方法では、めっき処理で常用されるパルス電解を用いることもできる。 Further, 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 + 1 V. When performing constant potential electrolysis, it is desirable that cyclic voltammetry can be used in combination, and potentiostat devices such as Solartron, BAS, Hokuto Denko, and IVIUM can be used.
In the above-mentioned electroplating method, constant current electrolysis can be used, but it is preferable to set the current value so that the voltage at the time of electrolysis is in the same range as the above-mentioned electrolysis voltage. In this case, a normal DC power source can be used, and for example, known devices such as Matsusada Precision Co., Ltd., Takasago Seisakusho Co., Ltd., Kikusui Electronics Co., Ltd., and Texio Technology Co., Ltd. can be used. Further, in the above-mentioned electrolytic plating treatment method, pulse electrolysis, which is commonly used in the plating treatment, can also be used.
　めっき液は、従来公知のめっき液を用いることができる。
　具体的には、銅を析出させる場合には硫酸銅を含む水溶液が一般的に用いられるが、硫酸銅の濃度は、１～３００ｇ／Ｌであることが好ましく、１００～２００ｇ／Ｌであるのがより好ましい。また、電解液中に塩酸を添加すると析出を促進することができる。この場合、塩酸濃度は１０～２０ｇ／Ｌであることが好ましい。
　また、めっき液は酸を含んでいてもよく、その酸濃度は０．０１～１ｍｏｌ／Ｌであることが好ましい。 As the plating solution, a conventionally known plating solution can be used.
Specifically, when precipitating copper, an aqueous solution containing copper sulfate is generally used, but the concentration of copper sulfate is preferably 1 to 300 g / L, preferably 100 to 200 g / L. Is more preferable. Further, the precipitation can be promoted by adding hydrochloric acid to the electrolytic solution. In this case, the hydrochloric acid concentration is preferably 10 to 20 g / L.
Further, the plating solution may contain an acid, and the acid concentration thereof is preferably 0.01 to 1 mol / L.
　電解液は添加剤を添加してもよく、電解液に添加する添加剤としては、例えば、以下に示すものがある。また、添加剤により、以下に示す作用が得られる。
　添加剤としては、光沢剤、平滑化剤と呼ばれる添加成分を添加することも可能である。付着抑制作用では、分子又はイオンが単独で吸着又は析出し、めっき反応を抑制する。サッカリン、ベンゾチアゾール、チオ尿素、ヤヌスグリーンＢ（ＪＧＢ）、ベンゼルアセトン、鉛、ビスマス等が付着抑制作用を有するものに該当する。
　界面錯形成作用では、表面吸着した微量の錯体形成イオンが、金属イオンに配位してイオンブリッジ又はエレクトロブリッジを形成することにより析出反応を促進する。塩化物イオン、ＣＮ－、ＳＣＮ－、硫黄系化合物（チオ尿素、３，３´－ジチオビス（１－プロパンスルホン酸）二ナトリウム（ＳＰＳ）、ジメルカプトチアゾール（ＤＭＴＤ）等）、ホウ酸、シュウ酸、マロン酸等がこれに当たると考えられている。
　皮膜形成作用では、界面活性剤あるいは高分子が、めっき表面にマイルドに付着して皮膜を形成し、めっき反応を抑制する。ＰＥＧ（ポリエチレングリコール）、ポリエチレングリコールモノ－４－ノニルフェニルエーテル（ＰＥＧＮＰＥ）、ポリビニルアルコール、ゼラチン等が代表例である。
　電解消耗機構では、分子又はイオンがめっき表面で迅速に電解還元され、その反応はそれらの分子又はイオンの表面への拡散輸送によって律速される。これにより、めっきの表面形状の凹凸が小さくなる。不飽和アルコール（ブチンジオール、プロパルギルアルコール、クマリン等）、ＮＯ３ －、Ｆｅ３ ＋等が代表例である。
　また、めっき液は、表面張力を調整しできるだけ低くすることも好ましく、表面張力としては、純水よりも低い６０ｍＮ／ｍ以下にすることが好ましい。表面張力の調整のために界面活性剤又は有機溶媒を添加することもできる。
　めっき液は、ｐＨ（水素イオン指数）を調整することが好ましく、ｐＨは１以上であることが望ましい。 Additives may be added to the electrolytic solution, and examples of the additives added to the electrolytic solution include those shown below. In addition, the following actions can be obtained by the additive.
As an additive, it is also possible to add an additive component called a brightener or a smoothing agent. In the adhesion suppressing action, molecules or ions are adsorbed or precipitated alone to suppress the plating reaction. Saccharin, benzothiazole, thiourea, Janus Green B (JGB), benzelacetone, lead, bismuth and the like have an adhesion inhibitory effect.
In the interfacial complex formation action, a small amount of complex-forming ions adsorbed on the surface coordinate with metal ions to form an ion bridge or an electrobridge, thereby promoting a precipitation reaction. Chloride ion, CN -, SCN -, sulfur compounds (thiourea, 3,3'-dithiobis (1-propane sulfonic acid) disodium (SPS), dimercaptothiazoles (DMTD), etc.), boric acid, oxalic acid , Malonic acid, etc. are considered to correspond to this.
In the film-forming action, the surfactant or polymer mildly adheres to the plating surface to form a film and suppresses the plating reaction. Typical examples are PEG (polyethylene glycol), polyethylene glycol mono-4-nonylphenyl ether (PEGNPE), polyvinyl alcohol, gelatin and the like.
In the electrolytic consumption mechanism, molecules or ions are rapidly electrolytically reduced on the plating surface, and the reaction is rate-determined by diffusion transport of those molecules or ions to the surface. As a result, the unevenness of the surface shape of the plating is reduced. Unsaturated alcohols (butynediol, propargyl alcohol, coumarin, etc.), NO 3 -, Fe 3 + and the like are representative examples.
Further, it is preferable that the surface tension of the plating solution is adjusted to be as low as possible, and the surface tension is preferably 60 mN / m or less, which is lower than that of pure water. Surfactants or organic solvents can also be added to adjust the surface tension.
The pH (hydrogen ion index) of the plating solution is preferably adjusted, and the pH is preferably 1 or more.
　なお、金を析出させる場合、テトラクロロ金の硫酸溶液を用い、交流電解でめっきを行なうのが望ましい。
　また、無電解めっき法では、アスペクトの高い貫通孔からなる孔中に金属を完全に充填には長時間を要するので、電解めっき法を用いて貫通孔に金属を充填することが望ましい。 When depositing gold, it is desirable to use a sulfuric acid solution of tetrachloroauric acid and perform plating by AC electrolysis.
Further, in the electroless plating method, it takes a long time to completely fill the holes composed of through holes having a high aspect, so it is desirable to fill the through holes with metal by using the electrolytic plating method.
　保持工程の後、金属充填部材２１に対して、図１２に示すように、樹脂基材２２を用いて、陽極酸化膜１６の裏面１６ｂに支持体２４を設ける。
　樹脂基材２２は、例えば、機能性吸着フィルムが用いられる。機能性吸着フィルムとしては、Ｑ－ｃｈｕｃｋ（登録商標）（丸石産業株式会社製）等を使用することができる。
　支持体２４は、陽極酸化膜１６と同じ外形状であることが好ましい。支持体２４は、後工程で陽極酸化膜１６を支持する。支持体２４を取り付けることにより、取扱い性が増す。 After the holding step, the support 24 is provided on the back surface 16b of the anodic oxide film 16 using the resin base material 22 with respect to the metal filling member 21 as shown in FIG.
As the resin base material 22, for example, a functional adsorption film is used. As the functional adsorption film, Q-chuck (registered trademark) (manufactured by Maruishi Sangyo Co., Ltd.) or the like can be used.
The support 24 preferably has the same outer shape as the anodic oxide film 16. The support 24 supports the anodic oxide film 16 in a post-process. By attaching the support 24, the handleability is increased.
　次に、図１３に示すように、例えば、金属充填部材２１の金属層１９を除去する金属層除去工程を実施する。金属層除去工程では、例えば、粘着テープを用いて金属層１９を剥離する。複数の貫通孔１７は平均直径が１μｍ以下と小さく、粘着テープを用いて、金属層を容易に除去できる。
　なお、金属層除去工程は、金属層１９を除去できれば、その方法については特に限定されるものではない。 Next, as shown in FIG. 13, for example, a metal layer removing step of removing the metal layer 19 of the metal filling member 21 is carried out. In the metal layer removing step, for example, the metal layer 19 is peeled off using an adhesive tape. The plurality of through holes 17 have a small average diameter of 1 μm or less, and the metal layer can be easily removed by using an adhesive tape.
The metal layer removing step is not particularly limited as long as the metal layer 19 can be removed.
　図１３に示す金属層１９が除去された状態で、陽極酸化膜１６の表面１６ａを平滑化する表面平滑化処理工程を有することが好ましい。表面平滑化処理工程の平滑化は、化学的機械的研磨（ＣＭＰ）、ドライエッチング又は研削を用いることができ、また、化学的機械的研磨（ＣＭＰ）、ドライエッチング及び研削を組み合わせて平滑化してもよい。化学的機械的研磨（ＣＭＰ）を行う場合、異なる砥粒を組み合わせて研磨してもよく、いずれの方法においても、仕上がりの表面粗さ（算術平均粗さＲａ（ＪＩＳ　Ｂ　０６０１：２００１）は０．０２μｍ以下にすることが好ましい。
　金属層除去工程の後に、表面平滑化処理工程を実施することにより、表面平滑化処理工程において、研磨量等を少なくすることができ、研磨を容易に実施できる。これにより、表面平滑化処理に要する時間を短縮でき、かつ容易に平滑化できる。
　上述の金属層除去工程と表面平滑化処理工程とは、保持工程後になされる。上述の金属層除去工程及び表面平滑化処理工程は、バルブ金属部材１５の裏面に、搬送等のハンドリングのために、支持部材が設けられている。 It is preferable to have a surface smoothing treatment step for smoothing the surface 16a of the anodic oxide film 16 with the metal layer 19 shown in FIG. 13 removed. The smoothing of the surface smoothing process can be done by using chemical mechanical polishing (CMP), dry etching or grinding, or by combining chemical mechanical polishing (CMP), dry etching and grinding. May be good. When performing chemical mechanical polishing (CMP), different abrasive grains may be combined and polished, and in any method, the finished surface roughness (arithmetic mean roughness Ra (JIS B 0601: 2001)) is 0. It is preferably .02 μm or less.
By carrying out the surface smoothing treatment step after the metal layer removing step, the amount of polishing and the like can be reduced in the surface smoothing treatment step, and polishing can be easily carried out. As a result, the time required for the surface smoothing treatment can be shortened, and smoothing can be easily performed.
The above-mentioned metal layer removing step and surface smoothing treatment step are performed after the holding step. In the metal layer removing step and the surface smoothing treatment step described above, a support member is provided on the back surface of the valve metal member 15 for handling such as transportation.
　表面平滑化処理工程の後、図１４に示すように、支持体２４が取り付けられた形態で、陽極酸化膜１６及びフレーム部１５ｄを厚み方向Ｄｔに一部除去し、上述の充填した金属を陽極酸化膜１６の表面１６ａよりも突出させてもよい。すなわち、導通路２０を陽極酸化膜１６の表面１６ａから突出させてもよい。陽極酸化膜１６の表面１６ａから導通路２０が突出した部分を突出部２０ａという。上述の充填した金属を陽極酸化膜１６の表面１６ａよりも突出させる工程のことを金属突出工程という。 After the surface smoothing treatment step, as shown in FIG. 14, in the form in which the support 24 is attached, the anodic oxide film 16 and the frame portion 15d are partially removed in the thickness direction Dt, and the above-mentioned filled metal is used as the anode. It may protrude from the surface 16a of the oxide film 16. That is, the conduction path 20 may be projected from the surface 16a of the anodic oxide film 16. The portion where the conduction path 20 protrudes from the surface 16a of the anodic oxide film 16 is referred to as a protruding portion 20a. The step of projecting the filled metal from the surface 16a of the anodic oxide film 16 is called a metal projecting step.
〔金属突出工程〕
　上述の陽極酸化膜１６の一部除去には、例えば、導通路２０を構成する金属を溶解せず、陽極酸化膜１６、すなわち、酸化アルミニウム（Ａｌ２Ｏ３）を溶解する酸水溶液又はアルカリ水溶液が用いられる。上述の酸水溶液又はアルカリ水溶液を、金属が充填された貫通孔１７を有する陽極酸化膜１６を接触させることにより、陽極酸化膜１６を一部除去する。上述の酸水溶液又はアルカリ水溶液を陽極酸化膜１６に接触させる方法は、特に限定されず、例えば、浸漬法、スプレー法及びスピンプロセシング法等が挙げられる。中でも均一性の観点からスピンプロセッサーを用いた処理方法が好ましい。スピンプロセッサーとしては、三益半導体工業株式会社、株式会社日立ハイテクノロジーズ、株式会社SCREENホールディングス、大日本スクリーン、アクテス京三株式会社、株式会社カナメックス等の公知の製品を用いることができる。 [Metal protrusion process]
For the partial removal of the anodic oxide film 16 described above, for example, an acid aqueous solution or an alkaline aqueous solution that does not dissolve the metal constituting the conduction path 20 but dissolves the anodic oxide film 16, that is, aluminum oxide (Al 2 O 3). Is used. A part of the anodic oxide film 16 is removed by bringing the above-mentioned acid aqueous solution or alkaline aqueous solution into contact with the anodic oxide film 16 having through holes 17 filled with metal. The method of bringing the above-mentioned acid aqueous solution or alkaline aqueous solution into contact with the anodic oxide film 16 is not particularly limited, and examples thereof include a dipping method, a spray method, and a spin processing method. Above all, a processing method using a spin processor is preferable from the viewpoint of uniformity. As the spin processor, known products such as Sanmasu Semiconductor Industry Co., Ltd., Hitachi High-Technologies Corporation, SCREEN Holdings Co., Ltd., Dainippon Screen, Actes Kyozo Co., Ltd., and Kanamex Co., Ltd. can be used.
　酸水溶液を用いる場合は、硫酸、リン酸、硝酸及び塩酸等の無機酸又はこれらの混合物の水溶液を用いることが好ましい。中でもクロム酸を含有しない水溶液が安全性に優れる点で好ましい。酸水溶液の濃度は１～１０質量％であることが好ましい。酸水溶液の温度は、２５～６０℃であることが好ましい。
　また、アルカリ水溶液を用いる場合は、水酸化ナトリウム、水酸化カリウム及び水酸化リチウムからなる群から選ばれる少なくとも一つのアルカリの水溶液を用いることが好ましい。アルカリ水溶液の濃度は０．１～５質量％であることが好ましい。アルカリ水溶液の温度は、２０～３５℃であることが好ましい。
　具体的には、例えば、５０ｇ／Ｌ、４０℃のリン酸水溶液、０．５ｇ／Ｌ、３０℃の水酸化ナトリウム水溶液又は０．５ｇ／Ｌ、３０℃の水酸化カリウム水溶液が好適に用いられる。 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.
When an alkaline aqueous solution is 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 20 to 35 ° C.
Specifically, for example, a phosphoric acid aqueous solution at 50 g / L and 40 ° C., a sodium hydroxide aqueous solution at 0.5 g / L and 30 ° C., or a potassium hydroxide aqueous solution at 0.5 g / L and 30 ° C. is preferably used. ..
　酸水溶液又はアルカリ水溶液への浸漬時間は、８～１２０分であることが好ましく、１０～９０分であるのがより好ましく、１５～６０分であるのが更に好ましい。ここで、浸漬時間は、短時間の浸漬処理を繰り返した場合には、各浸漬時間の合計をいう。なお、各浸漬処理の間には、洗浄処理を施してもよく、また、中和処理を施してもよい。 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 further preferably 15 to 60 minutes. Here, the immersion time means the total of each immersion time when the immersion treatment for a short time is repeated. A cleaning treatment may be performed or a neutralization treatment may be performed between the immersion treatments.
　また、金属を陽極酸化膜１６の表面１６ａより突出させる程度であるが、作製される金属充填微細構造体３２を異方導電性部材として用いた際に、配線基板等の被接着物との圧着性が良好となる理由から、金属を陽極酸化膜１６の表面１６ａよりも１０ｎｍ～１０００ｎｍ突出させることが好ましく、５０ｎｍ～５００ｎｍ突出させることがより好ましい。すなわち、突出部２０ａの表面１６ａからの突出量は１０ｎｍ～１０００ｎｍが好ましく、より好ましくは５０ｎｍ～５００ｎｍである。 Further, although the metal is only projected from the surface 16a of the anodic oxide film 16, when the produced metal-filled microstructure 32 is used as an anisotropic conductive member, it is pressure-bonded to an object to be adhered such as a wiring board. For the reason that the properties are good, it is preferable that the metal protrudes from the surface 16a of the anodic oxide film 16 by 10 nm to 1000 nm, and more preferably 50 nm to 500 nm. That is, the amount of protrusion of the protruding portion 20a from the surface 16a is preferably 10 nm to 1000 nm, more preferably 50 nm to 500 nm.
　導通路２０の突出部２０ａの高さを厳密に制御する場合は、貫通孔１７の内部に金属を充填した後、陽極酸化膜１６と導通路２０の端部とを同一平面状になるように加工した後、陽極酸化膜を選択的に除去することが好ましい。
　また、上述の金属の充填後、又は金属突出工程の後に、金属の充填に伴い発生した導通路２０内の歪みを軽減する目的で、加熱処理を施すことができる。
　加熱処理は、金属の酸化を抑制する観点から還元性雰囲気で施すことが好ましく、具体的には、酸素濃度が２０Ｐａ以下で行うことが好ましく、真空下で行うことがより好ましい。ここで、真空とは、大気よりも、気体密度及び気圧のうち、少なくとも一方が低い空間の状態をいう。
　また、加熱処理は、矯正の目的で、陽極酸化膜１６に応力を加えながら行うことが好ましい。
　また、乾燥時の水の表面張力による突出部同士の収束を抑制するために、超臨界乾燥を施すことが好ましい。超臨界乾燥には、例えば、超臨界洗浄乾燥装置(ＳＣＲＤ６、株式会社レクザム社製)等を用いることができる。 When strictly controlling the height of the protruding portion 20a of the conduction path 20, after filling the inside of the through hole 17 with metal, the anodic oxide film 16 and the end portion of the conduction path 20 are made flush with each other. After processing, it is preferable to selectively remove the anodic oxide film.
Further, after the above-mentioned metal filling or after the metal projecting step, heat treatment can be performed for the purpose of reducing the distortion in the conduction path 20 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 heat treatment is preferably carried out at an oxygen concentration of 20 Pa or less, and more preferably carried out under vacuum. Here, 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, the heat treatment is preferably performed while applying stress to the anodic oxide film 16 for the purpose of straightening.
Further, it is preferable to perform supercritical drying in order to suppress the convergence of the protrusions due to the surface tension of water during drying. For supercritical drying, for example, a supercritical washing / drying device (SCRD6, manufactured by Rexxam Co., Ltd.) or the like can be used.
　陽極酸化膜１６に支持体２４を用けることにより、陽極酸化膜１６単体を取扱うことに比して陽極酸化膜１６の損傷を抑制することができ、取扱いが容易になる。
　ここで、取扱いとは、陽極酸化膜１６を保持すること、ならびに陽極酸化膜１６の移送、搬送及び運搬等の陽極酸化膜１６を移動させることをいう。取扱いが容易とは、上述の陽極酸化膜１６の保持の際、及び上述の陽極酸化膜１６の移動の際に、陽極酸化膜１６の損傷等を抑制できることをいう。取扱いが容易であることにより、例えば、充填した金属を陽極酸化膜１６の表面１６ａよりも突出させるが、この金属の損傷を抑制することができる。 By using the support 24 on the anodic oxide film 16, damage to the anodic oxide film 16 can be suppressed as compared with handling the anodic oxide film 16 alone, and the handling becomes easier.
Here, handling means holding the anodic oxide film 16 and moving the anodic oxide film 16 for transferring, transporting, and transporting the anodic oxide film 16. "Easy to handle" means that damage to the anodic oxide film 16 can be suppressed when the above-mentioned anodic oxide film 16 is held and when the above-mentioned anodic oxide film 16 is moved. Since it is easy to handle, for example, the filled metal is projected from the surface 16a of the anodic oxide film 16, but damage to the metal can be suppressed.
　図１４に示すように充填した金属が陽極酸化膜１６の表面１６ａよりも突出しているため、突出した金属、すなわち、導通路２０の突出部２０ａを保護することが好ましい。このため、図１５に示すように導通路２０の突出部２０ａが埋設する樹脂層２６を、陽極酸化膜１６の表面１６ａに形成することが好ましい。樹脂層２６を設ける工程を樹脂層形成工程という。金属充填微細構造体の製造方法には樹脂層形成工程が含まれてもよい。 Since the filled metal protrudes from the surface 16a of the anodic oxide film 16 as shown in FIG. 14, it is preferable to protect the protruding metal, that is, the protruding portion 20a of the conduction path 20. Therefore, as shown in FIG. 15, it is preferable to form the resin layer 26 in which the protruding portion 20a of the conduction path 20 is embedded on the surface 16a of the anodic oxide film 16. The step of providing the resin layer 26 is called a resin layer forming step. The method for producing the metal-filled microstructure may include a resin layer forming step.
　樹脂層２６により、導通路２０の突出部２０ａが保護され、金属充填微細構造体の搬送性をより向上させることができ、より取扱いが容易になる。樹脂層２６は粘着性を備えるものであり、接着性を付与するものである。
　樹脂層２６は、例えば、従来公知の表面保護テープ貼付装置及びラミネーターを用いて形成することができる。樹脂層２６を設けることにより、金属充填微細構造体の搬送性を向上させることができる。 The resin layer 26 protects the protruding portion 20a of the conduction path 20, and can further improve the transportability of the metal-filled microstructure, making it easier to handle. The resin layer 26 has adhesiveness and imparts adhesiveness.
The resin layer 26 can be formed by using, for example, a conventionally known surface protective tape affixing device and a laminator. By providing the resin layer 26, the transportability of the metal-filled microstructure can be improved.
〔樹脂層形成工程〕
　樹脂層２６を構成する樹脂材料としては、具体的には、例えば、エチレン系共重合体、ポリアミド樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリオレフィン系樹脂、アクリル系樹脂、及びセルロース系樹脂等を挙げることができるが、搬送性の観点と、異方導電性部材として使用しやすくする観点から、上述の樹脂層は、剥離可能な粘着層付きフィルムであることが好ましく、加熱処理又は紫外線露光処理により粘着性が弱くなり、剥離可能となる粘着層付きフィルムであるのがより好ましい。 [Resin layer forming process]
Specific examples of the resin material constituting the resin layer 26 include ethylene-based copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin-based resins, acrylic resins, and cellulose-based resins. However, from the viewpoint of transportability and ease of use as an anisotropic conductive member, the above-mentioned resin layer is preferably a film with a peelable adhesive layer, and is adhesive by heat treatment or ultraviolet exposure treatment. It is more preferable that the film has an adhesive layer that is weakened and can be peeled off.
　上述の粘着層付きフィルムは特に限定されず、熱剥離型の樹脂層、及び紫外線（ultraviolet：ＵＶ）剥離型の樹脂層等が挙げられる。
　ここで、熱剥離型の樹脂層は、常温では粘着力があり、加熱するだけで容易に剥離可能なもので、主に発泡性のマイクロカプセル等を用いたものが多い。
　また、粘着層を構成する粘着剤としては、具体的には、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン－ジエンブロック共重合体系粘着剤等が挙げられる。
　また、ＵＶ剥離型の樹脂層は、ＵＶ硬化型の接着層を有するもので硬化により粘着力が失われて剥離可能になるというものである。 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.
Here, 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 adhesive constituting the adhesive layer include a rubber adhesive, an acrylic adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, and a polyamide adhesive. , Urethane-based pressure-sensitive adhesives, styrene-diene block copolymer-based pressure-sensitive adhesives, and the like.
Further, 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.
　ＵＶ硬化型の接着層としては、ベースポリマーに、炭素－炭素二重結合をポリマー側鎖又は主鎖中もしくは主鎖末端に導入したポリマー等が挙げられる。炭素－炭素二重結合を有するベースポリマーとしては、アクリル系ポリマーを基本骨格とすることが好ましい。
　更に、アクリル系ポリマーは、架橋させるため、多官能性モノマー等も、必要に応じて共重合用モノマー成分として含むことができる。
　炭素－炭素二重結合を有するベースポリマーは単独で使用することができるが、ＵＶ硬化性のモノマー又はオリゴマーを配合することもできる。
　ＵＶ硬化型の接着層は、ＵＶ照射により硬化させるために光重合開始剤を併用することが好ましい。光重合開始剤としては、ベンゾインエーテル系化合物；ケタール系化合物；芳香族スルホニルクロリド系化合物；光活性オキシム系化合物；ベンゾフェノン系化合物；チオキサンソン系化合物；カンファーキノン；ハロゲン化ケトン；アシルホスフィノキシド；アシルホスフォナート等が挙げられる。 Examples of 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. As 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 included 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; acyl Phosphonate and the like can be mentioned.
　熱剥離型の樹脂層の市販品としては、例えば、ＷＳ５１３０Ｃ０２、ＷＳ５１３０Ｃ１０等のインテリマー〔登録商標〕テープ（ニッタ株式会社製）；ソマタック〔登録商標〕ＴＥシリーズ（ソマール株式会製）；Ｎｏ．３１９８、Ｎｏ．３１９８ＬＳ、Ｎｏ．３１９８Ｍ、Ｎｏ．３１９８ＭＳ、Ｎｏ．３１９８Ｈ、Ｎｏ．３１９５、Ｎｏ．３１９６、Ｎｏ．３１９５Ｍ、Ｎｏ．３１９５ＭＳ、Ｎｏ．３１９５Ｈ、Ｎｏ．３１９５ＨＳ、Ｎｏ．３１９５Ｖ、Ｎｏ．３１９５ＶＳ、Ｎｏ．３１９Ｙ－４Ｌ、Ｎｏ．３１９Ｙ－４ＬＳ、Ｎｏ．３１９Ｙ－４Ｍ、Ｎｏ．３１９Ｙ－４ＭＳ、Ｎｏ．３１９Ｙ－４Ｈ、Ｎｏ．３１９Ｙ－４ＨＳ、Ｎｏ．３１９Ｙ－４ＬＳＣ、Ｎｏ．３１９３５ＭＳ、Ｎｏ．３１９３５ＨＳ、Ｎｏ．３１９３Ｍ、Ｎｏ．３１９３ＭＳ等のリバアルファ〔登録商標〕シリーズ（日東電工株式会社製）；等が挙げられる。 Examples of commercially available heat-release type resin layers include Intellimar [registered trademark] tapes (manufactured by Nitta Corporation) such as WS5130C02 and WS5130C10; Somatac [registered trademark] TE series (manufactured by SOMAR Corporation); 3198, No. 3198LS, No. 3198M, No. 3198MS, No. 3198H, No. 3195, No. 3196, No. 3195M, No. 3195MS, No. 3195H, No. 3195HS, No. 3195V, No. 3195VS, No. 319Y-4L, No. 319Y-4LS, No. 319Y-4M, No. 319Y-4MS, No. 319Y-4H, No. 319Y-4HS, No. 319Y-4LSC, No. 31935MS, No. 31935HS, No. 3193M, No. Riva Alpha [registered trademark] series (manufactured by Nitto Denko KK) such as 3193MS; etc.
　ＵＶ剥離型の樹脂層の市販品としては、例えば、ＥＬＰ ＤＵ－３００、ＥＬＰ ＤＵ－２３８５ＫＳ、ＥＬＰ ＤＵ－２１８７Ｇ、ＥＬＰ ＮＢＤ－３１９０Ｋ、ＥＬＰ ＵＥ－２０９１Ｊ等のエレップホルダー〔登録商標〕（日東電工株式会社製）；Ａｄｗｉｌｌ Ｄ－２１０、Ａｄｗｉｌｌ Ｄ－２０３、Ａｄｗｉｌｌ Ｄ－２０２、Ａｄｗｉｌｌ Ｄ－１７５、Ａｄｗｉｌｌ Ｄ－６７５（いずれもリンテック株式会社製）；スミライト〔登録商標〕ＦＬＳのＮ８０００シリーズ（住友ベークライト株式会社製）；ＵＣ３５３ＥＰ－１１０（古河電気工業株式会社製）；等のダイシングテープを利用することができる。その他、ＵＶ剥離型の樹脂層の市販品としては、例えば、ＥＬＰ ＲＦ－７２３２ＤＢ、ＥＬＰ ＵＢ－５１３３Ｄ（いずれも日東電工株式会社製）；ＳＰ－５７５Ｂ－１５０、ＳＰ－５４１Ｂ－２０５、ＳＰ－５３７Ｔ－１６０、ＳＰ－５３７Ｔ－２３０（いずれも古河電気工業株式会社製）；等のバックグラインドテープを利用することができる。
　上述の粘着層付きフィルムは、公知の表面保護テープ貼付装置及びラミネーターを用いて貼り付けることができる。 Commercially available products of the UV peeling type resin layer include, for example, ELP holders such as ELP DU-300, ELP DU-2385KS, ELP DU-2187G, ELP NBD-3190K, ELP UE-2091J [registered trademark] (Nitto Denko). (Made by Lintec Corporation); Adwill D-210, Adwill D-203, Adwill D-202, Adwill D-175, Adwill D-675 (all manufactured by Lintec Corporation); Sumilite (registered trademark) FLS N8000 series (Sumitomo Bakelite) (Manufactured by Furukawa Electric Co., Ltd.); UC353EP-110 (manufactured by Furukawa Electric Co., Ltd.); Other commercially available products of the UV peeling type resin layer include, for example, ELP RF-7232DB and ELP UB-5133D (all manufactured by Nitto Denko Corporation); SP-575B-150, SP-541B-205, SP-537T. Backgrinding tapes such as -160 and SP-537T-230 (both manufactured by Furukawa Electric Co., Ltd.) can be used.
The above-mentioned film with an adhesive layer can be attached using a known surface protective tape affixing device and a laminator.
　樹脂層２６の形成方法としては、上述の方法以外に、例えば、後述の酸化防止材料、高分子材料、溶媒（例えば、メチルエチルケトン等）等を含有する樹脂組成物を陽極酸化膜１６の表面及び裏面ならびに導通路の突出部に塗布し、乾燥させ、必要に応じて焼成する方法等が挙げられる。
　樹脂組成物の塗布方法は特に限定されず、例えば、グラビアコート法、リバースコート法、ダイコート法、ブレードコート法、ロールコート法、エアナイフコート法、スクリーンコート法、バーコート法、及びカーテンコート法等の従来公知のコーティング方法が使用できる。
　また、塗布後の乾燥方法は特に限定されず、例えば、大気下において０℃～１００℃の温度で、数秒～数十分間、加熱する処理、減圧下において０℃～８０℃の温度で、十数分～数時間、加熱する処理等が挙げられる。
　また、乾燥後の焼成方法は、使用する高分子材料により異なるため特に限定されないが、ポリイミド樹脂を用いる場合には、例えば、１６０℃～２４０℃の温度で２分間～６０分間加熱する処理等が挙げられ、エポキシ樹脂を用いる場合には、例えば、３０℃～８０℃の温度で２分間～６０分間加熱する処理等が挙げられる。 As a method for forming the resin layer 26, in addition to the above-mentioned method, for example, a resin composition containing an antioxidant material, a polymer material, a solvent (for example, methyl ethyl ketone, etc.) described later is used on the front surface and the back surface of the anodic oxide film 16. In addition, a method of applying to the protruding portion of the conduction path, drying, and firing if necessary can be mentioned.
The coating method of the resin composition is not particularly limited, and for example, a gravure coating method, a reverse coating method, a die coating method, a blade coating method, a roll coating method, an air knife coating method, a screen coating method, a bar coating method, a curtain coating method, etc. Conventionally known coating methods can be used.
The drying method after coating is not particularly limited, and for example, a treatment of heating at a temperature of 0 ° C. to 100 ° C. in the atmosphere for several seconds to several tens of minutes, and a temperature of 0 ° C. to 80 ° C. under reduced pressure. Examples include heating for a dozen minutes to several hours.
The firing method after drying is not particularly limited because it differs depending on the polymer material used, but when a polyimide resin is used, for example, a treatment of heating at a temperature of 160 ° C. to 240 ° C. for 2 minutes to 60 minutes is performed. When an epoxy resin is used, for example, a treatment of heating at a temperature of 30 ° C. to 80 ° C. for 2 minutes to 60 minutes can be mentioned.
　次に、図１５に示す支持体２４を陽極酸化膜１６から取り除く。この場合、樹脂基材２２を起点として支持体２４を陽極酸化膜１６から取り除く。
　次に、図１６に示すように、樹脂層２６の表面２６ａに剥離層２７を積層する。剥離層２７は、支持層２８と剥離剤２９が積層されたものである。剥離剤２９が樹脂層２６に接している。例えば、予め定められた温度に加熱することで、剥離剤２９の接着力が弱まり、剥離層２７を取り除くことができる。
　剥離剤２９には、例えば、日東電工社製リバアルファ（登録商標）及びソマール株式会社製ソマタック（登録商標）等を用いることができる。 Next, the support 24 shown in FIG. 15 is removed from the anodic oxide film 16. In this case, the support 24 is removed from the anodic oxide film 16 starting from the resin base material 22.
Next, as shown in FIG. 16, the release layer 27 is laminated on the surface 26a of the resin layer 26. The release layer 27 is a laminate of the support layer 28 and the release agent 29. The release agent 29 is in contact with the resin layer 26. For example, by heating to a predetermined temperature, the adhesive force of the release agent 29 is weakened, and the release layer 27 can be removed.
As the release agent 29, for example, Riva Alpha (registered trademark) manufactured by Nitto Denko Corporation and Somatac (registered trademark) manufactured by SOMAR Corporation can be used.
　次に、両面粘着剤３０を用いて、剥離層２７に、例えば、支持部材３１を取り付ける。支持部材３１は支持層２８に対向して配置される。支持部材３１は、陽極酸化膜１６と同じ外形状である。支持部材３１は、後工程で支持体の役割を果たす。支持部材３１を取り付けることにより、取扱い性が増す。
　両面粘着剤３０は、剥離層２７の支持層２８と支持部材３１とを接着することができれば、その構成は特に限定されるものではなく、例えば、日東電工社製の両面タイプのリバアルファ（登録商標）を用いることができる。 Next, for example, the support member 31 is attached to the release layer 27 using the double-sided adhesive 30. The support member 31 is arranged to face the support layer 28. The support member 31 has the same outer shape as the anodic oxide film 16. The support member 31 serves as a support in a subsequent process. By attaching the support member 31, the handleability is increased.
The configuration of the double-sided adhesive 30 is not particularly limited as long as the support layer 28 of the release layer 27 and the support member 31 can be adhered to each other. Trademark) can be used.
　支持部材３１は、陽極酸化膜１６を支持するものであり、例えば、シリコン基板で構成されている。支持部材３１としては、シリコン基板以外に、例えば、ＳｉＣ、ＳｉＮ、ＧａＮ及びアルミナ（Ａｌ２Ｏ３）等のセラミックス基板、ガラス基板、繊維強化プラスティック基板、ならびに金属基板を用いることができる。繊維強化プラスティック基板には、プリント配線基板であるＦＲ－４（Flame Retardant Type 4）基板等も含まれる。 The support member 31 supports the anodic oxide film 16 and is made of, for example, a silicon substrate. As the support member 31, for example, a ceramic substrate such as SiC, SiC, GaN and alumina (Al 2 O 3 ), a glass substrate, a fiber reinforced plastic substrate, and a metal substrate can be used in addition to the silicon substrate. The fiber reinforced plastic substrate also includes a FR-4 (Flame Retardant Type 4) substrate, which is a printed wiring board.
　次に、陽極酸化膜１６の裏面１６ｂを研磨する。陽極酸化膜１６の裏面１６ｂの研磨では、陽極酸化膜１６の裏面１６ｂと導通路２０の端面（図示せず）とが、同一面となる状態まで平坦化する。上述の陽極酸化膜１６の裏面１６ｂの研磨は、上述の図１３に示す陽極酸化膜１６の表面１６ａに対してした表面平滑化処理工程と同じであるため、その詳細な説明は省略する。 Next, the back surface 16b of the anodic oxide film 16 is polished. In polishing the back surface 16b of the anodic oxide film 16, the back surface 16b of the anodic oxide film 16 and the end surface (not shown) of the conduction path 20 are flattened to the same surface. Since the polishing of the back surface 16b of the anodic oxide film 16 described above is the same as the surface smoothing treatment step for the surface 16a of the anodic oxide film 16 shown in FIG. 13, detailed description thereof will be omitted.
　上述のように、複数の導通路２０を有する陽極酸化膜１６の表面１６ａに対して表面平滑化処理工程を実施した後、複数の導通路２０を有する陽極酸化膜１６の裏面１６ｂに対して表面平滑化処理工程を実施したが、少なくとも一方の面に上述の表面平滑化処理工程を実施すればよい。
　例えば、陽極酸化膜１６の表面１６ａ及び裏面１６ｂを、それぞれセンサ（図示せず）を用いて反射率を計測し、反射率の値が、予め定められた範囲にあれば研磨をすることなく、次の工程に移行するようにしてもよい。 As described above, after performing the surface smoothing treatment step on the surface 16a of the anodic oxide film 16 having the plurality of conduction paths 20, the surface of the back surface 16b of the anodic oxide film 16 having the plurality of conduction paths 20 Although the smoothing treatment step has been carried out, the above-mentioned surface smoothing treatment step may be carried out on at least one surface.
For example, the reflectance of the front surface 16a and the back surface 16b of the anodic oxide film 16 is measured using a sensor (not shown), respectively, and if the reflectance value is within a predetermined range, polishing is not required. You may move to the next step.
　次に、図１７に示すように、陽極酸化膜１６及びフレーム部１５ｄを厚み方向Ｄｔに一部除去し、上述の充填した金属を陽極酸化膜１６の裏面１６ｂよりも突出させる。すなわち、導通路２０を陽極酸化膜１６の裏面１６ｂから突出させる。陽極酸化膜１６の裏面１６ｂから導通路２０が突出した部分を突出部２０ｂという。
　上述の充填した金属を陽極酸化膜１６の裏面１６ｂよりも突出させる工程は、上述の金属突出工程と同じであるため、その詳細な説明は省略する。 Next, as shown in FIG. 17, the anodic oxide film 16 and the frame portion 15d are partially removed in the thickness direction Dt, and the above-mentioned filled metal is projected from the back surface 16b of the anodic oxide film 16. That is, the conduction path 20 is projected from the back surface 16b of the anodic oxide film 16. The portion where the conduction path 20 protrudes from the back surface 16b of the anodic oxide film 16 is referred to as a protruding portion 20b.
Since the step of projecting the filled metal from the back surface 16b of the anodic oxide film 16 is the same as the above-mentioned metal projecting step, detailed description thereof will be omitted.
　次に、図１８に示すように、陽極酸化膜１６の裏面１６ｂの導通路２０の突出部２０ｂが埋設する樹脂層２６を、陽極酸化膜１６の裏面１６ｂに形成する。これにより、図１８に示す金属充填微細構造体３２を得ることができる。
　なお、導通路２０の突出部２０ｂが埋設する樹脂層２６の形成方法は、上述の樹脂層形成工程と同じであるため、その詳細な説明は省略する。 Next, as shown in FIG. 18, a resin layer 26 in which the protruding portion 20b of the conduction path 20 of the back surface 16b of the anodic oxide film 16 is embedded is formed on the back surface 16b of the anodic oxide film 16. As a result, the metal-filled microstructure 32 shown in FIG. 18 can be obtained.
Since the method of forming the resin layer 26 in which the protruding portion 20b of the conduction path 20 is embedded is the same as the above-described resin layer forming step, detailed description thereof will be omitted.
　図１８に示すように、陽極酸化膜１６の両面に樹脂層２６が形成された状態で、陽極酸化膜１６外縁部にフレーム部１５ｄが残存している。この外縁部に残存したフレーム部１５ｄを、溶解、又は研削等の物理的な方法を用いて除去してもよい。これにより、図１９に示すように、陽極酸化膜１６単体の金属充填微細構造体３２を得ることができる。なお、陽極酸化膜１６を破損等することなく、バルブ金属部材１５を取り除くことができれば、溶解に限定されるものではない。アルミニウム基板等のバルブ金属部材１５を取り除くことをバルブ金属部材除去工程という。バルブ金属部材除去工程については後に説明する。
　金属充填微細構造体３２の形状が、例えば、円板状であれば、金属充填微細構造体３２の搬送に、半導体ウエハの搬送等に利用される装置を利用することができ、金属充填微細構造体３２の取扱いに特別な装置は不要である。 As shown in FIG. 18, with the resin layers 26 formed on both sides of the anodic oxide film 16, the frame portion 15d remains on the outer edge of the anodic oxide film 16. The frame portion 15d remaining on the outer edge portion may be removed by a physical method such as melting or grinding. As a result, as shown in FIG. 19, the metal-filled microstructure 32 of the anodic oxide film 16 alone can be obtained. If the valve metal member 15 can be removed without damaging the anodic oxide film 16, it is not limited to melting. Removing the valve metal member 15 such as an aluminum substrate is called a valve metal member removing step. The valve metal member removing step will be described later.
If the shape of the metal-filled microstructure 32 is, for example, a disk shape, an apparatus used for transporting a semiconductor wafer or the like can be used for transporting the metal-filled microstructure 32, and the metal-filled microstructure 32 can be transported. No special device is required to handle the body 32.
〔バルブ金属部材除去工程〕
　バルブ金属部材１５を溶解する処理液は、アルミニウム基板の場合、アルミニウム基板の溶解は、アルミニウムの陽極酸化膜１６を溶解しにくく、アルミニウムを溶解しやすい処理液を用いることが好ましい。アルミニウムに対する溶解速度が、１μｍ／分以上であることが好ましく、３μｍ／分以上であるのがより好ましく、５μｍ／分以上であるのが更に好ましい。同様に、陽極酸化膜に対する溶解速度が、０．１ｎｍ／分以下となることが好ましく、０．０５ｎｍ／分以下となるのがより好ましく、０．０１ｎｍ／分以下となるのが更に好ましい。 [Valve metal member removal process]
When the treatment liquid for dissolving the valve metal member 15 is an aluminum substrate, it is preferable to use a treatment liquid for dissolving the aluminum substrate, which is difficult to dissolve the anodic oxide film 16 of aluminum and is easy to dissolve aluminum. The dissolution rate in aluminum is preferably 1 μm / min or more, more preferably 3 μm / min or more, and further preferably 5 μm / min or more. Similarly, the dissolution rate for the anodized film is preferably 0.1 nm / min or less, more preferably 0.05 nm / min or less, and even more preferably 0.01 nm / min or less.
　具体的には、アルミよりもイオン化傾向の低い金属化合物を少なくとも１種含み、かつ、ｐＨ（水素イオン指数）が４以下又は８以上となる処理液であることが好ましく、そのｐＨが３以下又は９以上であるのがより好ましく、２以下又は１０以上であるのが更に好ましい。
　このような処理液としては、酸又はアルカリ水溶液をベースとし、例えば、マンガン、亜鉛、クロム、鉄、カドミウム、コバルト、ニッケル、スズ、鉛、アンチモン、ビスマス、銅、水銀、銀、パラジウム、白金、金の化合物（例えば、塩化白金酸）、これらのフッ化物、これらの塩化物等を配合したものであることが好ましい。
　中でも、酸水溶液ベースが好ましく、塩化物をブレンドすることが好ましい。
　特に、塩酸水溶液に塩化水銀をブレンドした処理液（塩酸／塩化水銀）、塩酸水溶液に塩化銅をブレンドした処理液（塩酸／塩化銅）が、処理ラチチュードの観点から好ましい。
　なお、このような処理液の組成は特に限定されず、例えば、臭素／メタノール混合物、臭素／エタノール混合物、王水等を用いることができる。 Specifically, it is preferably a treatment liquid containing at least one metal compound having a lower ionization tendency than aluminum and having a pH (hydrogen ion index) of 4 or less or 8 or more, and the pH is 3 or less or It is more preferably 9 or more, and further preferably 2 or less or 10 or more.
Such a treatment liquid is based on an acid or alkaline aqueous solution, and is, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, etc. It is preferably a compound containing a gold compound (for example, chloroplatinic acid), these fluorides, these chlorides and the like.
Of these, an acid aqueous solution base is preferable, and a chloride blend is preferable.
In particular, a treatment liquid obtained by blending a hydrochloric acid aqueous solution with mercury chloride (hydrochloric acid / mercury chloride) and a treatment liquid obtained by blending a hydrochloric acid aqueous solution with copper chloride (hydrochloric acid / copper chloride) are preferable from the viewpoint of treatment latitude.
The composition of such a treatment liquid is not particularly limited, and for example, a bromine / methanol mixture, a bromine / ethanol mixture, royal water, or the like can be used.
　また、このような処理液の酸又はアルカリ濃度は、０．０１～１０ｍｏｌ／Ｌが好ましく、０．０５～５ｍｏｌ／Ｌがより好ましい。
　更に、このような処理液を用いた処理温度は、－１０℃～８０℃が好ましく、０℃～６０℃が好ましい。 The acid or alkali concentration of such a treatment liquid is preferably 0.01 to 10 mol / L, more preferably 0.05 to 5 mol / L.
Further, the treatment temperature using such a treatment liquid is preferably −10 ° C. to 80 ° C., preferably 0 ° C. to 60 ° C.
　また、上述のバルブ金属部材１５の溶解は、上述の金属層除去工程後に、バルブ金属部材１５を上述の処理液に接触させることにより行う。接触させる方法は、特に限定されず、例えば、浸漬法、スプレー法が挙げられる。中でも、浸漬法が好ましい。このときの接触時間としては、１０秒～５時間が好ましく、１分～３時間がより好ましい。 Further, the above-mentioned valve metal member 15 is dissolved by bringing the valve metal member 15 into contact with the above-mentioned treatment liquid after the above-mentioned metal layer removing step. The contact method is not particularly limited, and examples thereof include a dipping method and a spraying method. Above all, the dipping method is preferable. The contact time at this time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.
［金属充填微細構造体の製造方法の第２の例］
　図２０～図２４は本発明の実施形態の金属充填微細構造体の製造方法の第２の例を工程順に示す模式的断面図である。なお、図２０～図２４において、図６に示す構成と同一構成物には、同一符号を付して、その詳細な説明は省略する。 [Second example of a method for manufacturing a metal-filled microstructure]
20 to 24 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. In FIGS. 20 to 24, the same components as those shown in FIG. 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
　金属充填微細構造体の製造方法の第２の例は、金属充填微細構造体の製造方法の第１の例に比して、バルブ金属部材１１の表面１１ａの外縁１１ｂにだけマスク１２（図４参照）を形成するのではなく、開口１３ａを有するマスク１３をバルブ金属部材１１の表面１１ａの外縁１１ｂに配置する点が異なり、それ以外は、金属充填微細構造体の製造方法の第１の例と同様にして、図６に示す金属充填部材２１ならびに図１８及び図１９に示す金属充填微細構造体３２を得ることができる。
　図２０に示すように、バルブ金属部材１１の表面１１ａ上に、開口１３ａを有するマスク１３を配置する。次に、図２１に示すように、バルブ金属部材１１の表面１１ａの外縁１１ｂにマスク１３を設置する。このとき、バルブ金属部材１１の表面１１ａにおいて、マスク１３の開口１３ａに相当する領域１１ｃが陽極酸化膜１１ｄ（図２２参照）の形成領域である。
　次に、バルブ金属部材１１を電極とした陽極酸化処理を実施し、バルブ金属部材１１のうち、マスク１３で囲まれた領域１１ｃに陽極酸化膜に形成する陽極酸化膜形成工程を行う。陽極酸化膜形成工程は、上述の金属充填微細構造体の製造方法の第１の例と同じであるため、その詳細な説明は省略する。陽極酸化膜形成工程では、上述の領域１１ｃに陽極酸化膜１１ｄが形成されるが、マスク１３下のバルブ金属部材１１は陽極酸化されない。 The second example of the method for manufacturing the metal-filled microstructure is different from the first example of the method for manufacturing the metal-filled microstructure, and the mask 12 is only on the outer edge 11b of the surface 11a of the valve metal member 11 (FIG. 4). The first example of the method for manufacturing a metal-filled microstructure is different in that the mask 13 having the opening 13a is arranged on the outer edge 11b of the surface 11a of the valve metal member 11 instead of forming (see). In the same manner as above, the metal filling member 21 shown in FIG. 6 and the metal filling microstructure 32 shown in FIGS. 18 and 19 can be obtained.
As shown in FIG. 20, a mask 13 having an opening 13a is arranged on the surface 11a of the valve metal member 11. Next, as shown in FIG. 21, the mask 13 is installed on the outer edge 11b of the surface 11a of the valve metal member 11. At this time, on the surface 11a of the valve metal member 11, the region 11c corresponding to the opening 13a of the mask 13 is the region where the anodic oxide film 11d (see FIG. 22) is formed.
Next, an anodic oxidation treatment is carried out using the valve metal member 11 as an electrode, and an anodic oxide film forming step of forming the anodic oxide film on the region 11c surrounded by the mask 13 is performed in the valve metal member 11. Since the anodic oxide film forming step is the same as the first example of the above-mentioned method for producing a metal-filled microstructure, detailed description thereof will be omitted. In the anodic oxide film forming step, the anodic oxide film 11d is formed in the above-mentioned region 11c, but the valve metal member 11 under the mask 13 is not anodized.
　陽極酸化処理後、図２３に示すように、マスク１３を、バルブ金属部材１１の表面１１ａから離す。次に、図２３に示す陽極酸化膜１１ｄに対して、バリア層を除去して、陽極酸化膜１１ｄに、図２４に示すように、厚み方向Ｄｔに延在する貫通孔１７を複数形成し、陽極酸化膜１１ｄで構成された陽極酸化膜１６を得る。
　次に、図２４に示す構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７に、金属を充填する充填工程を実施する。構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７の内部に、陽極酸化膜１６の表面１６ａを超えて金属を充填することにより、上述の図６に示すように金属層１９が形成される。これにより、図６に示す金属充填部材２１が形成される。金属層１９の形成方法は、上述の金属充填微細構造体の製造方法の第１の例と同じであるため、その詳細な説明は省略する。 After the anodizing treatment, as shown in FIG. 23, the mask 13 is separated from the surface 11a of the valve metal member 11. Next, the barrier layer is removed from the anodic oxide film 11d shown in FIG. 23, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 11d as shown in FIG. 24. An anodic oxide film 16 composed of the anodic oxide film 11d is obtained.
Next, for the structure 18 shown in FIG. 24, a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is performed. By filling the inside of the plurality of through holes 17 of the anodic oxide film 16 with metal beyond the surface 16a of the anodic oxide film 16 with respect to the structure 18, the metal layer 19 is formed as shown in FIG. It is formed. As a result, the metal filling member 21 shown in FIG. 6 is formed. Since the method for forming the metal layer 19 is the same as that of the first example of the method for manufacturing the metal-filled microstructure described above, detailed description thereof will be omitted.
［金属充填微細構造体の製造方法の第３の例］
　図２５～図２９は本発明の実施形態の充填微細構造体の第３の例を工程順に示す模式的断面図である。なお、図２５～図２９において、図６に示す構成と同一構成物には、同一符号を付して、その詳細な説明は省略する。 [Third example of a method for manufacturing a metal-filled microstructure]
25 to 29 are schematic cross-sectional views showing a third example of the packed microstructure according to the embodiment of the present invention in order of steps. In FIGS. 25 to 29, the same components as those shown in FIG. 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
　金属充填微細構造体の製造方法の第３の例は、金属充填微細構造体の製造方法の第１の例に比して、バルブ金属部材の表面１１ａ全面を陽極酸化処理する点、陽極酸化膜を除去してフレーム部を形成する点が異なり、それ以外は、金属充填微細構造体の製造方法の第１の例と同様にして、図６に示す金属充填部材２１ならびに図１８及び図１９に示す金属充填微細構造体３２を得ることができる。
　金属充填微細構造体の製造方法の第３の例では、金属充填微細構造体の製造方法の第１の例と同様に、バルブ金属部材１１（図１参照）を用意する。次に、バルブ金属部材１１の表面１１ａ全面を陽極酸化処理し、バルブ金属部材１１の底部１１ｅ（図３参照）を残して陽極酸化膜１１ｄ（図３参照）を形成する。更に陽極酸化膜１１ｄに対して、バリア層を除去して、陽極酸化膜１１ｄに、図２５に示すように、厚み方向Ｄｔに延在する貫通孔１７を複数形成し、陽極酸化膜で構成された陽極酸化膜１６を得る。陽極酸化膜１６の下方にバルブ金属部材１１（図３参照）の一部である底部１１ｅ（図３参照）が残存しており、底部１１ｅがバルブ金属部材１５の底部１５ｅ（図２５参照）である。陽極酸化膜１６は厚みＨＡが２００μｍ未満であることが好ましい。厚みＨＡが２００μｍ未満であれば、陽極酸化膜１６とバルブ金属部材１５とが同一面にあるとみなすことができる。 The third example of the method for manufacturing the metal-filled microstructure is anodized in that the entire surface 11a of the valve metal member is anodized as compared with the first example of the method for manufacturing the metal-filled microstructure. The metal-filled member 21 shown in FIG. 6 and FIGS. 18 and 19 are shown in the same manner as in the first example of the method for manufacturing the metal-filled microstructure, except that The metal-filled microstructure 32 shown can be obtained.
In the third example of the method for manufacturing the metal-filled microstructure, the valve metal member 11 (see FIG. 1) is prepared as in the first example of the method for manufacturing the metal-filled microstructure. Next, the entire surface 11a of the valve metal member 11 is anodized to form the anodic oxide film 11d (see FIG. 3), leaving the bottom 11e (see FIG. 3) of the valve metal member 11. Further, the barrier layer is removed from the anodic oxide film 11d, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 11d as shown in FIG. 25, and the anodic oxide film is formed. Anodized film 16 is obtained. The bottom portion 11e (see FIG. 3), which is a part of the valve metal member 11 (see FIG. 3), remains below the anodic oxide film 16, and the bottom portion 11e is the bottom portion 15e (see FIG. 25) of the valve metal member 15. be. The anodic oxide film 16 preferably has a thickness HA of less than 200 μm. If the thickness HA is less than 200 μm, it can be considered that the anodic oxide film 16 and the valve metal member 15 are on the same surface.
　次に、図２６に示すように、陽極酸化膜１６の表面１６ａに、陽極酸化膜１６の外縁１６ｅ以外にマスク１４を配置する。この状態で、陽極酸化膜１６が溶解し、かつバルブ金属部材１５が溶解しない特性を有する液体を用いて、陽極酸化膜１６の外縁１６ｅを溶解する。これにより、図２７に示すように、バルブ金属部材１５の底部１５ｅが露出する。
　なお、マスク１４は、陽極酸化膜１６が溶解し、かつバルブ金属部材１５が溶解しない特性を有する液体に対して溶解しないものであれば、特に限定されるものではなく、例えば、レジスト膜が用いられる。マスク１４に用いるレジスト膜は、陽極酸化膜１６の表面１６ａ全面にレジスト膜を形成した後、フォトリソグラフィ法を用いて、陽極酸化膜１６の外縁１６ｅのレジスト膜を除去して形成することができる。
　上述の陽極酸化膜１６が溶解し、かつバルブ金属部材１５が溶解しない特性を有する液体としては、酸化アルミニウム（Ａｌ２Ｏ３）を溶解する酸水溶液又はアルカリ水溶液が用いられる。具体的には、例えば、塩化銅を含む塩酸水溶液が用いられる。 Next, as shown in FIG. 26, a mask 14 is arranged on the surface 16a of the anodic oxide film 16 in addition to the outer edge 16e of the anodic oxide film 16. In this state, the outer edge 16e of the anodic oxide film 16 is dissolved by using a liquid having a property that the anodic oxide film 16 is dissolved and the valve metal member 15 is not dissolved. As a result, as shown in FIG. 27, the bottom portion 15e of the valve metal member 15 is exposed.
The mask 14 is not particularly limited as long as it does not dissolve in a liquid having a characteristic that the anodized film 16 dissolves and the valve metal member 15 does not dissolve. For example, a resist film is used. Be done. The resist film used for the mask 14 can be formed by forming a resist film on the entire surface 16a of the anodic oxide film 16 and then removing the resist film on the outer edge 16e of the anodic oxide film 16 by using a photolithography method. ..
As the liquid having the property that the anodized film 16 is dissolved and the valve metal member 15 is not dissolved, an acid aqueous solution or an alkaline aqueous solution that dissolves aluminum oxide (Al 2 O 3) is used. Specifically, for example, an aqueous hydrochloric acid solution containing copper chloride is used.
　次に、図２８に示すように、陽極酸化膜１６の表面１６ａからマスク１４を除去する。これにより、バルブ金属部材１５と、陽極酸化膜１６とを有する構造体１８を得る。
　陽極酸化膜１６の表面１６ａと、フレーム部１５ｄの上面との差、すなわち、陽極酸化膜１６の厚みＨＡは２００μｍ未満である。このため、陽極酸化膜１６の表面１６ａと、フレーム部１５ｄの上面とは略同一面にある。
　なお、マスク１４は、例えば、レジスト膜であれば、アッシングを用いて除去することができる。 Next, as shown in FIG. 28, the mask 14 is removed from the surface 16a of the anodic oxide film 16. As a result, a structure 18 having the valve metal member 15 and the anodic oxide film 16 is obtained.
The difference between the surface 16a of the anodic oxide film 16 and the upper surface of the frame portion 15d, that is, the thickness HA of the anodic oxide film 16 is less than 200 μm. Therefore, the surface 16a of the anodic oxide film 16 and the upper surface of the frame portion 15d are substantially on the same surface.
If the mask 14 is a resist film, for example, it can be removed by ashing.
　次に、図２８に示す構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７に、金属を充填する充填工程を実施する。構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７の内部に、陽極酸化膜１６の表面１６ａを超えて金属を充填することにより、図２９に示すように、金属層１９ａが形成される。これにより、金属充填部材２１を得る。このとき、金属層１９ａを形成することにより、導電性を有する導通路２０が形成されて、金属充填部材２１が形成される。金属層１９ａの形成方法は、上述の金属充填微細構造体の製造方法の第１の例の金属層１９の形成方法と同じであるため、その詳細な説明は省略する。
　なお、マスク１４を配置して陽極酸化膜１６の外縁１６ｅを溶解したが、これに限定されるものではなく、陽極酸化膜１６の外縁１６ｅを、研削又はレーザー光等により物理的に削りとってもよい。また、陽極酸化膜１６の外縁１６ｅに、例えば、陽極酸化膜が溶解し、かつバルブ金属部材が溶解しない特性を有する液体を、インクジェット法を用いて吹き付けて、陽極酸化膜１６の外縁１６ｅを選択的に溶解させてもよい。 Next, for the structure 18 shown in FIG. 28, a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is performed. As shown in FIG. 29, a metal layer 19a is formed in the structure 18 by filling the inside of the plurality of through holes 17 of the anodic oxide film 16 with a metal beyond the surface 16a of the anodic oxide film 16. Will be done. As a result, the metal filling member 21 is obtained. At this time, by forming the metal layer 19a, the conductive passage 20 is formed, and the metal filling member 21 is formed. Since the method for forming the metal layer 19a is the same as the method for forming the metal layer 19 in the first example of the method for manufacturing the metal-filled microstructure described above, detailed description thereof will be omitted.
The mask 14 is arranged to dissolve the outer edge 16e of the anodic oxide film 16, but the present invention is not limited to this, and the outer edge 16e of the anodic oxide film 16 may be physically scraped by grinding, laser light, or the like. .. Further, for example, a liquid having a property that the anodic oxide film is dissolved and the valve metal member is not dissolved is sprayed onto the outer edge 16e of the anodic oxide film 16 by using an inkjet method to select the outer edge 16e of the anodic oxide film 16. May be dissolved.
［金属充填微細構造体の製造方法の第４の例］
　図３０～図３４は本発明の実施形態の金属充填微細構造体の製造方法の第４の例を工程順に示す模式的断面図である。なお、図３０～図３４において、図６に示す構成と同一構成物には、同一符号を付して、その詳細な説明は省略する。 [Fourth example of a method for manufacturing a metal-filled microstructure]
30 to 34 are schematic cross-sectional views showing a fourth example of the method for manufacturing a metal-filled microstructure according to the embodiment of the present invention in order of steps. In FIGS. 30 to 34, the same components as those shown in FIG. 6 are designated by the same reference numerals, and detailed description thereof will be omitted.
　金属充填微細構造体の製造方法の第４の例は、金属充填微細構造体の製造方法の第１の例に比して、絶縁支持体６１の表面６１ａに部分的に、導電性を有する導電層６２が形成された電極体６０を用いてバルブ金属部材１１を陽極酸化処理する点が異なり、それ以外は、金属充填微細構造体の製造方法の第１の例と同様にして、図６に示す金属充填部材２１ならびに図１８及び図１９に示す金属充填微細構造体３２を得ることができる。 The fourth example of the method for manufacturing the metal-filled microstructure has conductivity partially having conductivity on the surface 61a of the insulating support 61 as compared with the first example of the method for manufacturing the metal-filled microstructure. The difference is that the valve metal member 11 is anodized using the electrode body 60 on which the layer 62 is formed. The metal-filled member 21 shown and the metal-filled microstructure 32 shown in FIGS. 18 and 19 can be obtained.
　金属充填微細構造体の製造方法の第４の例では、図３０に示すように、まず、矩形状の絶縁支持体６１の表面６１ａに部分的に、導電性を有する導電層６２が形成された電極体６０を用意する。電極体６０は、陽極酸化処理の際の電極として用いるものである。
　導電層６２は、絶縁支持体６１の表面６１ａにレジスト層６３を形成し、例えば、フォトリソグラフィ法を用いたパターニングにより、部分的にレジスト層６３を取り除く。次に、例えば、レジスト層６３上にシード層（図示せず）を形成し、めっきにより導電層６２を形成する。導電層６２を形成する際、平坦化処理により、レジスト層６３と導電層６２との表面を平坦にする。なお、導電層６２は、めっきにより形成したが、導電層６２の形成方法は、特に限定されるものではない。 In the fourth example of the method for manufacturing a metal-filled microstructure, first, as shown in FIG. 30, a conductive layer 62 having conductivity is partially formed on the surface 61a of the rectangular insulating support 61. The electrode body 60 is prepared. The electrode body 60 is used as an electrode in the anodizing treatment.
The conductive layer 62 forms a resist layer 63 on the surface 61a of the insulating support 61, and the resist layer 63 is partially removed by patterning using, for example, a photolithography method. Next, for example, a seed layer (not shown) is formed on the resist layer 63, and the conductive layer 62 is formed by plating. When the conductive layer 62 is formed, the surfaces of the resist layer 63 and the conductive layer 62 are flattened by a flattening treatment. Although the conductive layer 62 is formed by plating, the method for forming the conductive layer 62 is not particularly limited.
　次に、図３１に示すように、電極体６０の導電層６２を覆うバルブ金属部材１１を設ける。バルブ金属部材１１は、金属充填部材２１の陽極酸化膜１６（図３３参照）、すなわち、陽極酸化膜の厚み、又は最終的に得られる金属充填微細構造体３２（図３４参照）の陽極酸化膜１６の厚み、加工する装置等に応じて大きさ及び厚みが適宜決定されるものである。バルブ金属部材１１は、例えば、矩形状の板材である。
　バルブ金属部材１１としては、上述のようにアルミニウム基板が用いられる。
　なお、バルブ金属部材１１は、例えば、アルミニウム基板を用意してもよいが、電極体６０上にバルブ金属部材１１を形成してもよい。この場合、バルブ金属層形成工程では、例えば、導電層６２の表面６２ａとレジスト層６３の表面６３ａに、例えば、蒸着法によりバルブ金属部材１１として、アルミニウム基板を形成する。 Next, as shown in FIG. 31, a valve metal member 11 that covers the conductive layer 62 of the electrode body 60 is provided. The valve metal member 11 is the anodic oxide film 16 of the metal filling member 21 (see FIG. 33), that is, the thickness of the anodic oxide film, or the anodic oxide film of the finally obtained metal-filled microstructure 32 (see FIG. 34). The size and thickness of the 16 are appropriately determined according to the thickness, the apparatus for processing, and the like. The valve metal member 11 is, for example, a rectangular plate material.
As the valve metal member 11, an aluminum substrate is used as described above.
As the valve metal member 11, for example, an aluminum substrate may be prepared, but the valve metal member 11 may be formed on the electrode body 60. In this case, in the valve metal layer forming step, an aluminum substrate is formed on the surface 62a of the conductive layer 62 and the surface 63a of the resist layer 63, for example, as the valve metal member 11 by a vapor deposition method.
　次に、導電層６２を電極とした陽極酸化処理を実施し、バルブ金属部材１１のうち、導電層６２上の領域のバルブ金属部材１１を陽極酸化膜に形成する陽極酸化膜形成工程を行う。なお、陽極酸化膜は絶縁性基材である。バルブ金属部材１１を陽極酸化処理することにより陽極酸化膜１１ｄが形成される。
　陽極酸化膜形成工程では、導電層６２を陰極の電極とし、バルブ金属部材１１を陽極の電極として、陽極酸化処理を実施する。これにより、導電層６２上のバルブ金属部材１１が陽極酸化されて、図３２に示すようにバルブ金属部材１５の領域１５ｃに陽極酸化膜１１ｄが形成される。陽極酸化処理において、例えば、導電層６２に引出し電極が設けられていれば、引出し電極を利用して導電層６２に直流電流を印加する。 Next, an anodic oxidation treatment is carried out using the conductive layer 62 as an electrode, and an anodic oxide film forming step of forming the valve metal member 11 in the region on the conductive layer 62 on the anodic oxide film is performed. The anodic oxide film is an insulating base material. The anodic oxide film 11d is formed by anodizing the valve metal member 11.
In the anodic oxide film forming step, the anodic oxidation treatment is carried out using the conductive layer 62 as the electrode of the cathode and the valve metal member 11 as the electrode of the anode. As a result, the valve metal member 11 on the conductive layer 62 is anodized, and an anodic oxide film 11d is formed in the region 15c of the valve metal member 15 as shown in FIG. In the anodizing treatment, for example, if the conductive layer 62 is provided with an extraction electrode, a direct current is applied to the conductive layer 62 by using the extraction electrode.
　陽極酸化処理では、上述のように電極体６０の導電層６２を電極として用いており、電極体６０の導電層６２上のバルブ金属部材１１（図３１参照）が、陽極酸化膜１１ｄが形成される領域１１ｃ（図３１参照）となり、レジスト層６３上のバルブ金属部材１１（図３１参照）がバルブ金属部材１５の外縁１５ｂであり、フレーム部１５ｄになる。
　上述の領域１１ｃに陽極酸化膜１１ｄが形成されるが、レジスト層６３上のバルブ金属部材１１は陽極酸化されない。このように、バルブ金属部材１１が全て陽極酸化膜１１ｄにならず、陽極酸化処理後でもバルブ金属部材１１のままの領域がある。これにより、バルブ金属部材１５の外縁１５ｂに、バルブ金属部材１１で構成された、バルブ金属部材１５のフレーム部１５ｄが配置される。フレーム部１５ｄより囲まれる領域１５ｃに陽極酸化膜１６として、陽極酸化膜１１ｄ（図３２参照）が形成される。
　陽極酸化処理では、導電層６２上のバルブ金属部材１１は全て陽極酸化膜１１ｄにできるが、陽極酸化処理時間等を調整することにより、導電層６２上のバルブ金属部材１１の一部を陽極酸化膜１１ｄに形成することができる。図３２では導電層６２と、陽極酸化膜である陽極酸化膜１６との間にバルブ金属部材１５が存在する。
　なお、バルブ金属部材１１がアルミニウムで構成されているため、酸化膜として、陽極酸化膜１１ｄが形成され、陽極酸化膜１１ｄはＡｌ２Ｏ３膜で構成される。 In the anodizing treatment, the conductive layer 62 of the electrode body 60 is used as an electrode as described above, and the valve metal member 11 (see FIG. 31) on the conductive layer 62 of the electrode body 60 is formed with the anodic oxide film 11d. The region 11c (see FIG. 31) is formed, and the valve metal member 11 (see FIG. 31) on the resist layer 63 is the outer edge 15b of the valve metal member 15 and becomes the frame portion 15d.
The anodic oxide film 11d is formed in the above-mentioned region 11c, but the valve metal member 11 on the resist layer 63 is not anodized. As described above, all the valve metal members 11 do not become the anodic oxide film 11d, and there is a region where the valve metal member 11 remains even after the anodizing treatment. As a result, the frame portion 15d of the valve metal member 15 composed of the valve metal member 11 is arranged on the outer edge 15b of the valve metal member 15. An anodic oxide film 11d (see FIG. 32) is formed as the anodic oxide film 16 in the region 15c surrounded by the frame portion 15d.
In the anodizing treatment, all the valve metal members 11 on the conductive layer 62 can be formed into an anodic oxide film 11d, but by adjusting the anodizing treatment time and the like, a part of the valve metal member 11 on the conductive layer 62 is anodized. It can be formed on the membrane 11d. In FIG. 32, the valve metal member 15 exists between the conductive layer 62 and the anodic oxide film 16 which is the anodic oxide film.
Since the valve metal member 11 is made of aluminum, an anodic oxide film 11d is formed as an oxide film, and the anodic oxide film 11d is made of an Al 2 O 3 film.
　陽極酸化膜１１ｄは形成した時点で、複数のマイクロポアが存在する。しかしながら、複数のマイクロポアのうち、厚み方向Ｄｔに貫通していないマイクロポアもある。また、マイクロポアの底部にはバリア層（図示せず）が存在する。このため、図３２に示す陽極酸化膜１１ｄに対して、バリア層を除去して、陽極酸化膜１１ｄに、図３３に示すように、厚み方向Ｄｔに延在する貫通孔１７を複数形成し、陽極酸化膜１１ｄで構成された陽極酸化膜１６を得る。 When the anodic oxide film 11d is formed, there are a plurality of micropores. However, among the plurality of micropores, some micropores do not penetrate in the thickness direction Dt. In addition, there is a barrier layer (not shown) at the bottom of the micropores. Therefore, the barrier layer is removed from the anodic oxide film 11d shown in FIG. 32, and a plurality of through holes 17 extending in the thickness direction Dt are formed in the anodic oxide film 11d as shown in FIG. 33. An anodic oxide film 16 composed of the anodic oxide film 11d is obtained.
　以上の工程により、バルブ金属部材１５の外縁１５ｂに配置されたフレーム部１５ｄで囲まれる領域１５ｃに、複数の細孔（貫通孔１７）を有する陽極酸化膜１６（陽極酸化膜）を形成することにより、バルブ金属部材１５と、陽極酸化膜１６（陽極酸化膜）とを有する構造体１８を得る。例えば、図３３に示すように、バルブ金属部材１５の表面１５ａに、陽極酸化膜１６（陽極酸化膜）が形成され、陽極酸化膜１６の周囲にフレーム部１５ｄがある。また、図示はしないが陽極酸化膜１６の表面１６ａと、フレーム部１５ｄの上面とは、略同一面である。
　上述のように、図３２に示す陽極酸化膜形成工程と、図３３に示す、厚み方向Ｄｔに延在する貫通孔１７を複数形成する工程とが、構造体１８を得る形成工程である。 Through the above steps, an anodic oxide film 16 (anodide film) having a plurality of pores (through holes 17) is formed in the region 15c surrounded by the frame portion 15d arranged on the outer edge 15b of the valve metal member 15. A structure 18 having a valve metal member 15 and an anodic oxide film 16 (anodized film) is obtained. For example, as shown in FIG. 33, an anodic oxide film 16 (anodized film) is formed on the surface 15a of the valve metal member 15, and a frame portion 15d is provided around the anodic oxide film 16. Although not shown, the surface 16a of the anodic oxide film 16 and the upper surface of the frame portion 15d are substantially the same surface.
As described above, the anodic oxide film forming step shown in FIG. 32 and the step of forming a plurality of through holes 17 extending in the thickness direction Dt shown in FIG. 33 are forming steps for obtaining the structure 18.
　次に、図３４に示すように、構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７に、金属を充填する充填工程を実施する。構造体１８に対して、陽極酸化膜１６の複数の貫通孔１７の内部に、陽極酸化膜１６の表面１６ａを超えて金属を充填することにより、上述の金属層１９が形成される。これにより、金属充填部材２１を得る。このとき、金属層１９を形成することにより、導電性を有する導通路２０が形成される。金属層１９の形成方法は、上述の金属充填微細構造体の製造方法の第１の例と同じであるため、その詳細な説明は省略する。
　充填工程では、陽極酸化膜１６の複数の貫通孔１７の内部に金属を充填し、かつ図３４に示すように、構造体１８の表面、すなわち、金属充填部材２１のフレーム部１５ｄ上及び陽極酸化膜１６の表面１６ａ上に、金属層１９を形成することにより、金属を複数の貫通孔１７に充填する。この場合、金属層１９では、上述のようにフレーム部１５ｄ上に存在する部分の厚みδ（図２参照）を２μｍ～１００μｍとする。
　なお、例えば、めっき時間を長くすることにより、金属層１９の厚みδを厚くすることができる。充填工程では、陽極酸化膜１６の表面１６ａを超えて、金属を充填することにより、フレーム部１５ｄ上にも金属層１９が形成される。
　以下、金属充填微細構造体の構成の一例について説明する。 Next, as shown in FIG. 34, a filling step of filling the plurality of through holes 17 of the anodic oxide film 16 with metal is performed on the structure 18. The above-mentioned metal layer 19 is formed by filling the inside of the plurality of through holes 17 of the anodic oxide film 16 with metal beyond the surface 16a of the anodic oxide film 16 with respect to the structure 18. As a result, the metal filling member 21 is obtained. At this time, by forming the metal layer 19, the conductive passage 20 having conductivity is formed. Since the method for forming the metal layer 19 is the same as that of the first example of the method for manufacturing the metal-filled microstructure described above, detailed description thereof will be omitted.
In the filling step, the inside of the plurality of through holes 17 of the anodic oxide film 16 is filled with metal, and as shown in FIG. 34, the surface of the structure 18, that is, on the frame portion 15d of the metal filling member 21, and the anodic oxidation. By forming a metal layer 19 on the surface 16a of the film 16, the metal is filled into the plurality of through holes 17. In this case, in the metal layer 19, the thickness δ (see FIG. 2) of the portion existing on the frame portion 15d is set to 2 μm to 100 μm as described above.
For example, the thickness δ of the metal layer 19 can be increased by lengthening the plating time. In the filling step, the metal layer 19 is also formed on the frame portion 15d by filling the metal beyond the surface 16a of the anodic oxide film 16.
Hereinafter, an example of the configuration of the metal-filled microstructure will be described.
［金属充填微細構造体の構成の一例］
　図３５は本発明の実施形態の金属充填微細構造体の構成の一例を示す平面図であり、図３６は本発明の実施形態の金属充填微細構造体の構成の一例を示す模式的断面図である。図３６は図３５の切断面線ＩＢ－ＩＢ断面図である。 [Example of configuration of metal-filled microstructure]
FIG. 35 is a plan view showing an example of the configuration of the metal-filled microstructure according to the embodiment of the present invention, and FIG. 36 is a schematic cross-sectional view showing an example of the configuration of the metal-filled microstructure according to the embodiment of the present invention. be. FIG. 36 is a cross-sectional view taken along the line IB-IB of FIG. 35.
　図３５及び図３６に示す金属充填微細構造体３２は、上述のように絶縁性基材である陽極酸化膜１６と、陽極酸化膜１６の厚み方向Ｄｔに貫通した貫通孔１７と、貫通孔１７の内部に充填された金属で構成された複数の導通路２０とを有する。複数の導通路２０は、互いに電気的に絶縁された状態で設けられている。更に、例えば、陽極酸化膜１６の表面１６ａ及び裏面１６ｂに設けられた樹脂層２６を具備する。
　ここで、「互いに電気的に絶縁された状態」とは、陽極酸化膜１６の内部に存在している各導通路２０が陽極酸化膜１６の内部において互いに導通性が十分に低い状態であることを意味する。
　金属充填微細構造体３２は、導通路２０が互いに電気的に絶縁されており、陽極酸化膜１６の厚み方向Ｄｔと直交する方向ｘには導電性が十分に低く、厚み方向Ｄｔに導電性を有する、異方導電性を示す部材である。金属充填微細構造体３２は厚み方向Ｄｔを、例えば、後述の電子素子の積層方向に一致させて配置される。
　導通路２０は、図３５及び図３６に示すように、互いに電気的に絶縁された状態で陽極酸化膜１６を厚み方向Ｄｔに貫通して設けられている。 In the metal-filled microstructure 32 shown in FIGS. 35 and 36, as described above, the anodic oxide film 16 which is an insulating base material, the through hole 17 penetrating the anodic oxide film 16 in the thickness direction Dt, and the through hole 17 It has a plurality of conduction paths 20 made of metal filled in the inside of the above. The plurality of conduction paths 20 are provided in a state of being electrically insulated from each other. Further, for example, the resin layer 26 provided on the front surface 16a and the back surface 16b of the anodic oxide film 16 is provided.
Here, the "state of being electrically insulated from each other" means that the conduction paths 20 existing inside the anodic oxide film 16 are sufficiently low in conductivity with each other inside the anodic oxide film 16. Means.
In the metal-filled microstructure 32, the conduction paths 20 are electrically insulated from each other, the conductivity is sufficiently low in the direction x orthogonal to the thickness direction Dt of the anodic oxide film 16, and the conductivity is provided in the thickness direction Dt. It is a member that has orthogonal conductivity. The metal-filled microstructure 32 is arranged so that the thickness direction Dt is aligned with, for example, the stacking direction of the electronic elements described later.
As shown in FIGS. 35 and 36, the conduction path 20 is provided so as to penetrate the anodic oxide film 16 in the thickness direction Dt in a state of being electrically insulated from each other.
　金属充填微細構造体３２の厚みｈは、例えば、４０μｍ以下である。また、金属充填微細構造体３２は、ＴＴＶ（Total Thickness Variation）が１０μｍ以下であることが好ましい。陽極酸化膜１６は表面１６ａと裏面１６ｂが研磨されるため厚みとしては、金属充填微細構造体３２の厚みｈよりも厚く、例えば、６０μｍを超えるが脆性の観点から４０μｍ程度が好ましい。 The thickness h of the metal-filled microstructure 32 is, for example, 40 μm or less. Further, the metal-filled microstructure 32 preferably has a TTV (Total Thickness Variation) of 10 μm or less. Since the front surface 16a and the back surface 16b of the anodic oxide film 16 are polished, the thickness of the anodic oxide film 16 is thicker than the thickness h of the metal-filled microstructure 32, for example, it exceeds 60 μm, but is preferably about 40 μm from the viewpoint of brittleness.
　ここで、金属充填微細構造体３２の厚みｈ及び陽極酸化膜１６の厚みは、金属充填微細構造体３２及び陽極酸化膜１６を、それぞれ厚み方向に対して集束イオンビーム（Focused Ion Beam：ＦＩＢ）で切削加工し、その断面を電解放出形走査型電子顕微鏡により２０万倍の倍率で観察し、金属充填微細構造体３２及び陽極酸化膜１６の輪郭形状を、それぞれ取得し、厚みｈに相当する領域について１０点測定した平均値のことである。
　また、金属充填微細構造体３２のＴＴＶ（Total Thickness Variation）は、金属充填微細構造体３２をダイシングで支持部材３１ごと切断し、金属充填微細構造体３２の断面形状を観察して求めた値である。 Here, the thickness h of the metal-filled microstructure 32 and the thickness of the anodized film 16 are such that the metal-filled microstructure 32 and the anodized film 16 are focused ion beams (FIB) in the thickness direction, respectively. The cross section of the metal-filled microstructure 32 and the anodized film 16 was obtained at a magnification of 200,000 times with an electrolytically-release scanning electron microscope, and the contour shapes of the metal-filled microstructure 32 and the anodized film 16 were obtained and corresponded to the thickness h. It is an average value measured at 10 points for a region.
Further, the TTV (Total Thickness Variation) of the metal-filled microstructure 32 is a value obtained by cutting the metal-filled microstructure 32 together with the support member 31 by dicing and observing the cross-sectional shape of the metal-filled microstructure 32. be.
　金属充填微細構造体３２は、例えば、異方導電性を示す異方導電性部材として利用することができる。この場合、半導体素子と半導体素子とを、金属充填微細構造体３２を介して接合して、半導体素子と半導体素子とを電気的に接続した電子素子を得ることができる。電子素子において、金属充填微細構造体３２はＴＳＶ（Through Silicon Via）の機能を果たす。
　これ以外に、金属充填微細構造体３２を用いて３つ以上の半導体素子を電気的に接続した電子素子とすることもできる。金属充填微細構造体３２を用いることで３次元実装ができる。なお、半導体素子を接合する数は、特に限定されるものではなく、電子素子の機能、及び電子素子に要求される性能に応じて適宜決定されるものである。
　電子素子との接合は熱加圧接合を用いることができる。還元性雰囲気下で接合させれば、温度２５０℃以下で容易に金属電極と突出部が接合されるので、デバイスへの熱影響を小さくすることができる。 The metal-filled microstructure 32 can be used, for example, as an anisotropically conductive member exhibiting anisotropic conductivity. In this case, the semiconductor element and the semiconductor element are joined via the metal-filled microstructure 32 to obtain an electronic element in which the semiconductor element and the semiconductor element are electrically connected. In the electronic device, the metal-filled microstructure 32 functions as a TSV (Through Silicon Via).
In addition to this, an electronic element in which three or more semiconductor elements are electrically connected by using the metal-filled microstructure 32 can also be used. Three-dimensional mounting is possible by using the metal-filled microstructure 32. The number of semiconductor elements to be bonded is not particularly limited, and is appropriately determined according to the function of the electronic element and the performance required for the electronic element.
Thermal pressure bonding can be used for bonding with the electronic element. When bonded in a reducing atmosphere, the metal electrode and the protruding portion are easily bonded at a temperature of 250 ° C. or lower, so that the heat effect on the device can be reduced.
　金属充填微細構造体３２を用いることにより、電子素子の大きさを小さくでき実装面積を小さくできる。また、金属充填微細構造体３２の厚みを短くすることにより、半導体素子間の配線長を短くでき、信号の遅延を抑制し、電子素子の処理速度を向上させることができる。半導体素子間の配線長を短くすることで消費電力も抑制することができる。
　金属充填微細構造体３２は、上述のように陽極酸化膜１６と導通路２０とが、陽極酸化膜１６の表面１６ａで同一面の状態になるように研磨しているため、形状精度が高く、また、上述のように導通路２０の突出部２０ａの高さを厳密に制御することができるため、半導体素子と半導体素子との電気的な接続の信頼性が優れる。
　また、金属充填微細構造体３２は金属が密に充填されているため、樹脂材料に比べ熱伝導性が高い。接続した電極間、半導体素子間の上下方向の熱伝導はもちろん、平面方向への熱拡散も大きいため、放熱が必要な部材に特に有用である。金属充填微細構造体３２は、上述の半導体素子以外にメタルベース基板の放熱等にも用いることができ、放熱フィンの接続にも有効である。また、多層接続による熱のこもりが問題とされるメモリ等の接合には非常に有効である。 By using the metal-filled microstructure 32, the size of the electronic element can be reduced and the mounting area can be reduced. Further, by shortening the thickness of the metal-filled microstructure 32, the wiring length between the semiconductor elements can be shortened, the signal delay can be suppressed, and the processing speed of the electronic element can be improved. Power consumption can also be suppressed by shortening the wiring length between semiconductor elements.
Since the metal-filled microstructure 32 is polished so that the anodic oxide film 16 and the conduction path 20 are flush with each other on the surface 16a of the anodic oxide film 16 as described above, the shape accuracy is high. Further, since the height of the protruding portion 20a of the conduction path 20 can be strictly controlled as described above, the reliability of the electrical connection between the semiconductor element and the semiconductor element is excellent.
Further, since the metal-filled microstructure 32 is densely packed with metal, it has higher thermal conductivity than the resin material. Not only heat conduction in the vertical direction between connected electrodes and semiconductor elements, but also heat diffusion in the plane direction is large, so it is particularly useful for members that require heat dissipation. The metal-filled microstructure 32 can be used for heat dissipation of a metal base substrate in addition to the above-mentioned semiconductor element, and is also effective for connecting heat dissipation fins. Further, it is very effective for joining a memory or the like, which has a problem of heat retention due to multi-layer connection.
　半導体素子としては、例えば、ＡＳＩＣ（Application Specific Integrated Circuit）、ＦＰＧＡ（Field Programmable Gate Array）、ＡＳＳＰ（Application Specific Standard Product）等のロジック集積回路が挙げられる。また、例えば、ＣＰＵ（Central Processing Unit）、ＧＰＵ（Graphics Processing Unit）等のマイクロプロセッサが挙げられる。また、例えば、ＤＲＡＭ（Dynamic Random Access Memory）、ＨＭＣ（Hybrid Memory Cube）、ＭＲＡＭ（Magnetoresistive Random Access Memory）、ＰＣＭ（Phase-Change Memory）、ＲｅＲＡＭ（Resistance Random Access Memory）、ＦｅＲＡＭ（Ferroelectric Random Access Memory）、フラッシュメモリ等のメモリが挙げられる。また、例えば、ＬＥＤ（Light Emitting Diode）、パワーデバイス、ＤＣ（Direct Current）－ＤＣ（Direct Current）コンバータ、絶縁ゲートバイポーラトランジスタ（Insulated Gate Bipolar Transistor：ＩＧＢＴ）等のアナログ集積回路が挙げられる。また、例えば、加速度センサ、圧力センサ、振動子、ジャイロセンサ等のＭＥＭＳ（Micro Electro Mechanical Systems）が挙げられる。また、例えば、ＧＰＳ（Global Positioning System）、ＦＭ（Frequency Modulation）、ＮＦＣ（Nearfieldcommunication）、ＲＦＥＭ（RF Expansion Module）、ＭＭＩＣ（MonolithicMicrowaveIntegratedCircuit）、ＷＬＡＮ（WirelessLocalAreaNetwork）等のワイヤレス素子、ディスクリート素子、ＣＭＯＳ（Complementary Metal Oxide Semiconductor）、ＣＭＯＳイメージセンサー、カメラモジュール、Passiveデバイス、ＳＡＷ（Surface Acoustic Wave）フィルタ、ＲＦ（Radio Frequency）フィルタ、ＩＰＤ（Integrated Passive Devices）等が挙げられる。 Examples of semiconductor elements include logic integrated circuits such as ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), and ASSP (Application Specific Standard Product). Further, for example, a microprocessor such as a CPU (Central Processing Unit) and a GPU (Graphics Processing Unit) can be mentioned. Also, for example, DRAM (Dynamic RandomAccessMemory), HMC (HybridMemoryCube), MRAM (MagnetoresistiveRandomAccessMemory), PCM (Phase-ChangeMemory), ReRAM (ResistanceRandomAccessMemory), FeRAM (FerroelectricRandomAccessMemory) , Memory such as flash memory. Further, for example, an analog integrated circuit such as an LED (Light Emitting Diode), a power device, a DC (Direct Current) -DC (Direct Current) converter, and an insulated gate bipolar transistor (IGBT) can be mentioned. Further, for example, MEMS (Micro Electro Mechanical Systems) such as an acceleration sensor, a pressure sensor, a vibrator, and a gyro sensor can be mentioned. Further, for example, wireless elements such as GPS (Global Positioning System), FM (Frequency Modulation), NFC (Nearfield communication), RFEM (RF Expansion Module), MMIC (MonolithicMicrowaveIntegratedCircuit), WLAN (WirelessLocalAreaNetwork), discrete elements, CMOS (Complementary Metal). Oxide Semiconductor), CMOS image sensor, camera module, Passive device, SAW (Surface Acoustic Wave) filter, RF (Radio Frequency) filter, IPD (Integrated Passive Devices) and the like.
　また、半導体素子は素子領域を有するものでもよく。素子領域は電子素子として機能するための各種の素子構成回路等が形成された領域である。素子領域には、例えば、フラッシュメモリ等のようなメモリ回路、マイクロプロセッサ及びＦＰＧＡ（field-programmable gate array）等のような論理回路が形成された領域、無線タグ等の通信モジュールならびに配線が形成された領域がある。素子領域には、これ以外にＭＥＭＳ（Micro Electro Mechanical Systems）が形成されてもよい。ＭＥＭＳとは、例えば、センサ、アクチュエーター及びアンテナ等である。センサには、例えば、加速度、音、光等の各種のセンサが含まれる。光センサは、光を検出することができれば、特に限定されるものではなく、例えば、ＣＣＤ（Charge Coupled Device）イメージセンサー又はＣＭＯＳ（Complementary Metal Oxide Semiconductor）イメージセンサーが用いられる。 Further, the semiconductor element may have an element region. The element region is an region in which various element constituent circuits and the like for functioning as an electronic element are formed. In the element area, for example, a memory circuit such as a flash memory, an area in which a microprocessor and a logic circuit such as an FPGA (field-programmable gate array) are formed, a communication module such as a wireless tag, and wiring are formed. There is an area. In addition to this, MEMS (Micro Electro Mechanical Systems) may be formed in the element region. MEMS is, for example, a sensor, an actuator, an antenna, or the like. Sensors include, for example, various sensors such as acceleration, sound, light and the like. The optical sensor is not particularly limited as long as it can detect light, and for example, a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor is used.
　電子素子において達成する機能に応じて半導体素子が適宜選択される。例えば、電子素子では、論理回路を有する半導体素子と、メモリ回路を有する半導体素子の組合せとすることができる。また、電子素子における半導体素子の組合せとしては、センサ、アクチュエーター及びアンテナ等と、メモリ回路と論理回路との組み合わせでもよい。
　半導体素子は、例えば、シリコンで構成されるが、これに限定されるものではなく、炭化ケイ素、ゲルマニウム、ガリウムヒ素又は窒化ガリウム等であってもよい。
　また、半導体素子以外に、金属充填微細構造体３２を用いて、２つの配線層を電気的に接続してもよい。 A semiconductor device is appropriately selected according to the function to be achieved in the electronic device. For example, the electronic element can be a combination of a semiconductor element having a logic circuit and a semiconductor element having a memory circuit. The combination of semiconductor elements in the electronic element may be a combination of a sensor, an actuator, an antenna, or the like, a memory circuit, and a logic circuit.
The semiconductor element is composed of, for example, silicon, but is not limited to this, and may be silicon carbide, germanium, gallium arsenide, gallium nitride, or the like.
Further, in addition to the semiconductor element, the two wiring layers may be electrically connected by using the metal-filled microstructure 32.
　以下、金属充填微細構造体３２の構成についてより具体的に説明する。
〔陽極酸化膜〕
　陽極酸化膜１６は絶縁性基材として機能するものである。陽極酸化膜１６における各導通路の間隔は、５ｎｍ～８００ｎｍであることが好ましく、１０ｎｍ～２００ｎｍであることがより好ましく、２０ｎｍ～６０ｎｍであることが更に好ましい。陽極酸化膜１６における各導通路の間隔がこの範囲であると、陽極酸化膜１６が絶縁性の隔壁として十分に機能する。
　ここで、各導通路の間隔とは、隣接する導通路間の幅ｗをいい、金属充填微細構造体３２の断面を電解放出形走査型電子顕微鏡により２０万倍の倍率で観察し、隣接する導通路間の幅を１０点で測定した平均値をいう。 Hereinafter, the configuration of the metal-filled microstructure 32 will be described in more detail.
[Anodized film]
The anodic oxide film 16 functions as an insulating base material. The distance between the conduction paths in the anodic oxide film 16 is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, and even more preferably 20 nm to 60 nm. When the distance between the conduction paths in the anodic oxide film 16 is within this range, the anodic oxide film 16 sufficiently functions as an insulating partition wall.
Here, the distance between the conduction paths means the width w between the adjacent conduction paths, and the cross section of the metal-filled microstructure 32 is observed by an electrolytic emission scanning electron microscope at a magnification of 200,000 times and adjacent to each other. The average value of the width between conduction paths measured at 10 points.
　＜細孔の平均直径＞
　細孔の平均直径、すなわち、貫通孔１７の平均直径ｄ（図３５、図３６参照）は、１μｍ以下であり、５～５００ｎｍであることが好ましく、２０～４００ｎｍであることがより好ましく、４０～２００ｎｍであることが更に好ましく、５０～１００ｎｍであることが最も好ましい。貫通孔１７の平均直径ｄが１μｍ以下であり、上述の範囲であると、得られる導通路２０に電気信号を流した際に十分な応答が得ることができるため、電子部品の検査用コネクタとして、より好適に用いることができる。また、貫通孔１７の平均直径ｄが１μｍ以下であると、金属層１９（図６参照）を容易に除去できる。
　貫通孔１７の平均直径ｄは、走査型電子顕微鏡を用いて陽極酸化膜１６の表面を真上から倍率１００～１００００倍で撮影し撮影画像を得る。撮影画像において、周囲が環状に連なっている貫通孔を少なくとも２０個抽出し、その直径を測定し開口径とし、これら開口径の平均値を貫通孔の平均直径として算出する。
　なお、倍率は、貫通孔を２０個以上抽出できる撮影画像が得られるように上述した範囲の倍率を適宜選択することができる。また、開口径は、貫通孔部分の端部間の距離の最大値を測定した。すなわち、貫通孔の開口部の形状は略円形状に限定はされないので、開口部の形状が非円形状の場合には、貫通孔部分の端部間の距離の最大値を開口径とする。従って、例えば、２以上の貫通孔が一体化したような形状の貫通孔の場合にも、これを１つの貫通孔とみなし、貫通孔部分の端部間の距離の最大値を開口径とする。 <Average diameter of pores>
The average diameter of the pores, that is, the average diameter d of the through holes 17 (see FIGS. 35 and 36) is 1 μm or less, preferably 5 to 500 nm, more preferably 20 to 400 nm, and 40. It is more preferably to 200 nm, and most preferably 50 to 100 nm. When the average diameter d of the through hole 17 is 1 μm or less and is within the above range, a sufficient response can be obtained when an electric signal is passed through the obtained conduction path 20, so that the connector can be used as an inspection connector for electronic components. , Can be used more preferably. Further, when the average diameter d of the through holes 17 is 1 μm or less, the metal layer 19 (see FIG. 6) can be easily removed.
The average diameter d of the through holes 17 is obtained by photographing the surface of the anodic oxide film 16 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 a ring-shaped periphery 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.
As the magnification, the magnification in the above range can be appropriately selected so that a photographed image capable of extracting 20 or more through holes can be obtained. For the opening diameter, the maximum value of the distance between the ends of the through hole portion was measured. That is, since the shape of the opening of the through hole is not limited to a substantially circular shape, when the shape of the opening is a non-circular shape, 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 portion is set as the opening diameter. ..
　〔導通路〕
　複数の導通路２０は、上述のように、陽極酸化膜１６の厚み方向Ｄｔに貫通し、互いに電気的に絶縁された状態で設けられており、柱状である。導通路２０は、金属で構成されている。導通路２０は、陽極酸化膜１６の表面及び裏面から突出した突出部を有しており、かつ、各導通路の突出部が樹脂層に埋設されていてもよい。
　導通路を構成する金属の具体例としては、金（Ａｕ）、銀（Ａｇ）、銅（Ｃｕ）、アルミニウム（Ａｌ）、マグネシウム（Ｍｇ）、及びニッケル（Ｎｉ）等が好適に例示される。電気伝導性の観点から、銅、金、アルミニウム、及びニッケルが好ましく、銅及び金がより好ましい。 [Conduction path]
As described above, the plurality of conduction paths 20 are provided in a state of penetrating the anodic oxide film 16 in the thickness direction Dt and being electrically insulated from each other, and are columnar. The conduction path 20 is made of metal. The conduction path 20 may have protrusions protruding from the front surface and the back surface of the anodic oxide film 16, and the protrusions of each conduction path may be embedded in the resin layer.
As specific examples of the metal constituting the conduction path, gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni) and the like are preferably exemplified. From the viewpoint of electrical conductivity, copper, gold, aluminum, and nickel are preferable, and copper and gold are more preferable.
　＜突出部＞
　導通路２０の突出部２０ａ、２０ｂは、導通路２０が陽極酸化膜１６の表面１６ａ及び裏面１６ｂから突出した部分であり、樹脂層２６で保護されていることが好ましい。
　金属充填微細構造体３２を異方導電性部材として利用した場合に、異方導電性部材と電極とを圧着等の手法により電気的接続、又は物理的に接合する際、突出部が潰れた場合の面方向の絶縁性を十分に確保できる理由から、導通路の突出部のアスペクト比（突出部の高さ／突出部の直径）が０．５以上５０未満であることが好ましく、０．８～２０であることがより好ましく、１～１０であることが更に好ましい。 <Protruding part>
The protruding portions 20a and 20b of the conduction path 20 are portions where the conduction path 20 protrudes from the front surface 16a and the back surface 16b of the anodic oxide film 16, and are preferably protected by the resin layer 26.
When the metal-filled microstructure 32 is used as an anisotropic conductive member, the protruding portion is crushed when the anisotropic conductive member and the electrode are electrically connected or physically joined by a method such as crimping. The aspect ratio (height of the protruding portion / diameter of the protruding portion) of the protruding portion of the conductive path is preferably 0.5 or more and less than 50, preferably 0.8, for the reason that sufficient insulation in the plane direction can be ensured. It is more preferably about 20 and even more preferably 1 to 10.
　また、接続対象の半導体素子又は半導体ウエハの表面形状に追従する観点から、導通路の突出部の高さは、２０ｎｍ以上であることが好ましく、より好ましくは１００ｎｍ～５００ｎｍである。
　導通路の突出部の高さは、異方導電性部材の断面を電解放出形走査型電子顕微鏡により２万倍の倍率で観察し、導通路の突出部の高さを１０点で測定した平均値をいう。
　導通路の突出部の直径は、異方導電性部材の断面を電解放出形走査型電子顕微鏡により観察し、導通路の突出部の直径を１０点で測定した平均値をいう。 Further, from the viewpoint of following the surface shape of the semiconductor element or the semiconductor wafer to be connected, the height of the protruding portion of the conduction path is preferably 20 nm or more, more preferably 100 nm to 500 nm.
The height of the protruding part of the conduction path is the average obtained by observing the cross section of the anisotropic conductive member with a field emission scanning electron microscope at a magnification of 20,000 times and measuring the height of the protruding part of the conduction path at 10 points. The value.
The diameter of the protruding portion of the conduction path is an average value obtained by observing the cross section of the anisotropic conductive member with a field emission scanning electron microscope and measuring the diameter of the protruding portion of the conduction path at 10 points.
　＜他の形状＞
　導通路２０の密度は、２万個／ｍｍ2以上であることが好ましく、２００万個／ｍｍ2以上であることがより好ましく、１０００万個／ｍｍ2以上であることが更に好ましく、５０００万個／ｍｍ2以上であることが特に好ましく、１億個／ｍｍ2以上であることが最も好ましい。
　更に、隣接する各導通路２０の中心間距離ｐ（図３５及び図３６参照）は、２０ｎｍ～５００ｎｍであることが好ましく、４０ｎｍ～２００ｎｍであることがより好ましく、５０ｎｍ～１４０ｎｍであることが更に好ましい。 <Other shapes>
Density of the conductive paths 20 is preferably at 20,000 / mm 2 or more, more preferably 2,000,000 / mm 2 or more, still more preferably 10,000,000 / mm 2 or more, 50 million The number of pieces / mm 2 or more is particularly preferable, and the number of pieces / mm 2 or more is most preferable.
Further, the distance p between the centers of the adjacent conduction paths 20 (see FIGS. 35 and 36) is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and further preferably 50 nm to 140 nm. preferable.
　〔樹脂層〕
　上述のように、樹脂層２６は、陽極酸化膜１６の表面１６ａと裏面１６ｂに設けられ、上述のように導通路２０の突出部２０ａ、２０ｂを埋設するものである。すなわち、樹脂層２６は陽極酸化膜１６から突出した導通路２０の端部を被覆し、突出部２０ａ、２０ｂを保護する。
　樹脂層２６は、上述の樹脂層形成工程により形成されるものである。樹脂層２６は接続対象に対して接着性を付与するものである。樹脂層２６は、例えば、５０℃～２００℃の温度範囲で流動性を示し、２００℃以上で硬化するものであることが好ましい。
　樹脂層２６は、上述の樹脂層形成工程により形成されるものであるが、以下に示す、樹脂層の組成を用いることもできる。以下、樹脂層の組成について説明する。例えば、樹脂層は、高分子材料を含有するものであり、酸化防止材料を含んでもよい。 [Resin layer]
As described above, the resin layer 26 is provided on the front surface 16a and the back surface 16b of the anodic oxide film 16, and the protruding portions 20a and 20b of the conduction path 20 are embedded as described above. That is, the resin layer 26 covers the end portion of the conduction path 20 protruding from the anodic oxide film 16 and protects the protruding portions 20a and 20b.
The resin layer 26 is formed by the above-mentioned resin layer forming step. The resin layer 26 imparts adhesiveness to the connection target. The resin layer 26 preferably exhibits fluidity in the temperature range of 50 ° C. to 200 ° C. and cures at 200 ° C. or higher.
The resin layer 26 is formed by the above-mentioned resin layer forming step, but the composition of the resin layer shown below can also be used. Hereinafter, the composition of the resin layer will be described. For example, the resin layer contains a polymer material and may contain an antioxidant material.
　＜高分子材料＞
　樹脂層に含まれる高分子材料としては特に限定されないが、半導体素子又は半導体ウエハと異方導電性部材との隙間を効率よく埋めることができ、半導体素子又は半導体ウエハとの密着性がより高くなる理由から、熱硬化性樹脂であることが好ましい。
　熱硬化性樹脂としては、具体的には、例えば、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、ポリエステル樹脂、ポリウレタン樹脂、ビスマレイミド樹脂、メラミン樹脂、イソシアネート系樹脂等が挙げられる。
　なかでも、絶縁信頼性がより向上し、耐薬品性に優れる理由から、ポリイミド樹脂及び／又はエポキシ樹脂を用いるのが好ましい。 <Polymer material>
The polymer material contained in the resin layer is not particularly limited, but the gap between the semiconductor element or the semiconductor wafer and the anisotropic conductive member can be efficiently filled, and the adhesion to the semiconductor element or the semiconductor wafer is further improved. For this reason, it is preferably a thermosetting resin.
Specific examples of the thermosetting resin include epoxy resin, phenol resin, polyimide resin, polyester resin, polyurethane resin, bismaleimide resin, melamine resin, and isocyanate resin.
Among them, it is preferable to use a polyimide resin and / or an epoxy resin because the insulation reliability is further improved and the chemical resistance is excellent.
　＜酸化防止材料＞
　樹脂層に含まれる酸化防止材料としては、具体的には、例えば、１，２，３，４－テトラゾール、５－アミノ－１，２，３，４－テトラゾール、５－メチル－１，２，３，４－テトラゾール、１Ｈ－テトラゾール－５－酢酸、１Ｈ－テトラゾール－５－コハク酸、１，２，３－トリアゾール、４－アミノ－１，２，３－トリアゾール、４，５－ジアミノ－１，２，３－トリアゾール、４－カルボキシ－１Ｈ－１，２，３－トリアゾール、４，５－ジカルボキシ－１Ｈ－１，２，３－トリアゾール、１Ｈ－１，２，３－トリアゾール－４－酢酸、４－カルボキシ－５－カルボキシメチル－１Ｈ－１，２，３－トリアゾール、１，２，４－トリアゾール、３－アミノ－１，２，４－トリアゾール、３，５－ジアミノ－１，２，４－トリアゾール、３－カルボキシ－１，２，４－トリアゾール、３，５－ジカルボキシ－１，２，４－トリアゾール、１，２，４－トリアゾール－３－酢酸、１Ｈ－ベンゾトリアゾール、１Ｈ－ベンゾトリアゾール－５－カルボン酸、ベンゾフロキサン、２，１，３－ベンゾチアゾール、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、カテコール、ｏ－アミノフェノール、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、メラミン、及びこれらの誘導体が挙げられる。
　これらのうち、ベンゾトリアゾール及びその誘導体が好ましい。
　ベンゾトリアゾール誘導体としては、ベンゾトリアゾールのベンゼン環に、ヒドロキシル基、アルコキシ基（例えば、メトキシ基、エトキシ基等）、アミノ基、ニトロ基、アルキル基（例えば、メチル基、エチル基、ブチル基等）、ハロゲン原子（例えば、フッ素、塩素、臭素、ヨウ素等）等を有する置換ベンゾトリアゾールが挙げられる。また、ナフタレントリアゾール、ナフタレンビストリアゾール、と同様に置換された置換ナフタレントリアゾール、置換ナフタレンビストリアゾール等も挙げることができる。 <Antioxidant material>
Specific examples of the antioxidant material contained in the resin layer include 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2, 3,4-tetrazole, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-succinic acid, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1 , 2,3-Triazole, 4-carboxy-1H-1,2,3-triazole, 4,5-dicarboxy-1H-1,2,3-triazole, 1H-1,2,3-triazole-4- Acetic acid, 4-carboxy-5-carboxymethyl-1H-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2 , 4-triazole, 3-carboxy-1,2,4-triazole, 3,5-dicarboxy-1,2,4-triazole, 1,2,4-triazole-3-acetic acid, 1H-benzotriazole, 1H -Benzotriazole-5-carboxylic acid, benzofloxane, 2,1,3-benzothiazole, o-phenylenediamine, m-phenylenediamine, catechol, o-aminophenol, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole , 2-Mercaptobenzoxazole, melamine, and derivatives thereof.
Of these, benzotriazole and its derivatives are preferable.
The benzotriazole derivative includes a hydroxyl group, an alkoxy group (for example, methoxy group, ethoxy group, etc.), an amino group, a nitro group, and an alkyl group (for example, a methyl group, an ethyl group, a butyl group, etc.) on the benzene ring of benzotriazole. , Substituted benzotriazole having a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.) and the like. Moreover, the substituted naphthalene triazole, the substituted naphthalene bistriazole and the like which have been substituted in the same manner as naphthalene triazole and naphthalene bistriazole can also be mentioned.
　また、樹脂層に含まれる酸化防止材料の他の例としては、一般的な酸化防止剤である、高級脂肪酸、高級脂肪酸銅、フェノール化合物、アルカノールアミン、ハイドロキノン類、銅キレート剤、有機アミン、有機アンモニウム塩等が挙げられる。 In addition, as another example of the antioxidant material contained in the resin layer, general antioxidants such as higher fatty acids, higher fatty acid copper, phenol compounds, alkanolamines, hydroquinones, copper chelating agents, organic amines, and organic substances are used. Examples include ammonium salts.
　樹脂層に含まれる酸化防止材料の含有量は特に限定されないが、防食効果の観点から、樹脂層の全質量に対して０．０００１質量％以上が好ましく、０．００１質量％以上がより好ましい。また、本接合プロセスにおいて適切な電気抵抗を得る理由から、５．０質量％以下が好ましく、２．５質量％以下がより好ましい。 The content of the antioxidant material contained in the resin layer is not particularly limited, but from the viewpoint of anticorrosion effect, 0.0001% by mass or more is preferable, and 0.001% by mass or more is more preferable with respect to the total mass of the resin layer. Further, for the reason of obtaining an appropriate electric resistance in this joining process, 5.0% by mass or less is preferable, and 2.5% by mass or less is more preferable.
　＜マイグレーション防止材料＞
　樹脂層は、樹脂層に含有し得る金属イオン、ハロゲンイオン、ならびに半導体素子及び半導体ウエハに由来する金属イオンをトラップすることによって絶縁信頼性がより向上する理由から、マイグレーション防止材料を含有しているのが好ましい。 <Migration prevention material>
The resin layer contains a migration prevention material for the reason that the insulation reliability is further improved by trapping the metal ions and halogen ions that can be contained in the resin layer and the metal ions derived from the semiconductor element and the semiconductor wafer. Is preferable.
　マイグレーション防止材料としては、例えば、イオン交換体、具体的には、陽イオン交換体と陰イオン交換体との混合物、又は、陽イオン交換体のみを使用することができる。
　ここで、陽イオン交換体及び陰イオン交換体は、それぞれ、例えば、後述する無機イオン交換体及び有機イオン交換体の中から適宜選択することができる。 As the migration prevention material, for example, an ion exchanger, specifically, a mixture of a cation exchanger and an anion exchanger, or only a cation exchanger can be used.
Here, the cation exchanger and the anion exchanger can be appropriately selected from, for example, the inorganic ion exchanger and the organic ion exchanger described later, respectively.
　（無機イオン交換体）
　無機イオン交換体としては、例えば、含水酸化ジルコニウムに代表される金属の含水酸化物が挙げられる。
　金属の種類としては、例えば、ジルコニウムのほか、鉄、アルミニウム、錫、チタン、アンチモン、マグネシウム、ベリリウム、インジウム、クロム、ビスマス等が知られている。
　これらの中でジルコニウム系のものは、陽イオンのＣｕ2+、Ａｌ3+について交換能を有している。また、鉄系のものについても、Ａｇ+、Ｃｕ2+について交換能を有している。同様に、錫系、チタン系、アンチモン系のものは、陽イオン交換体である。
　一方、ビスマス系のものは、陰イオンのＣｌ-について交換能を有している。
　また、ジルコニウム系のものは条件によっては陰イオンの交換能を示す。アルミニウム系、錫系のものも同様である。
　これら以外の無機イオン交換体としては、リン酸ジルコニウムに代表される多価金属の酸性塩、モリブドリン酸アンモニウムに代表されるヘテロポリ酸塩、不溶性フェロシアン化物等の合成物が知られている。
　これらの無機イオン交換体の一部は既に市販されており、例えば、東亞合成株式会社の商品名イグゼ「ＩＸＥ」における各種のグレードが知られている。
　なお、合成品のほか、天然物のゼオライト、又はモンモリロン石のような無機イオン交換体の粉末も使用可能である。 (Inorganic ion exchanger)
Examples of the inorganic ion exchanger include hydrous oxides of metals typified by zirconium hydroxide.
As the type of metal, for example, in addition to zirconium, iron, aluminum, tin, titanium, antimony, magnesium, beryllium, indium, chromium, bismuth and the like are known.
Of these, the zirconium-based one has the ability to exchange the cations Cu 2+ and Al 3+. In addition, iron-based products also have exchangeability for Ag + and Cu 2+. Similarly, tin-based, titanium-based, and antimony-based ones are cation exchangers.
On the other hand, those of bismuth-based, anion Cl - has exchange capacity for.
In addition, zirconium-based ones exhibit anion exchange ability depending on the conditions. The same applies to aluminum-based and tin-based ones.
As other inorganic ion exchangers, compounds such as acid salts of polyvalent metals typified by zirconium phosphate, heteropolylates typified by ammonium molybdrinate, and insoluble ferrocyanides are known.
Some of these inorganic ion exchangers are already on the market, and for example, various grades under the trade name IXE of Toagosei Co., Ltd. are known.
In addition to synthetic products, natural zeolite or powder of an inorganic ion exchanger such as montmorillonite can also be used.
　（有機イオン交換体）
　有機イオン交換体には、陽イオン交換体としてスルホン酸基を有する架橋ポリスチレンが挙げられ、そのほかカルボン酸基、ホスホン酸基又はホスフィン酸基を有するものも挙げられる。
　また、陰イオン交換体として四級アンモニウム基、四級ホスホニウム基又は三級スルホニウム基を有する架橋ポリスチレンが挙げられる。 (Organic ion exchanger)
Examples of the organic ion exchanger include crosslinked polystyrene having a sulfonic acid group as a cation exchanger, and those having a carboxylic acid group, a phosphonic acid group or a phosphinic acid group.
Further, examples of the anion exchanger include crosslinked polystyrene having a quaternary ammonium group, a quaternary phosphonium group or a tertiary sulfonium group.
　これらの無機イオン交換体及び有機イオン交換体は、捕捉したい陽イオン、陰イオンの種類、そのイオンについての交換容量を考慮して適宜選択すればよい。勿論、無機イオン交換体と有機イオン交換体とを混合して使用してもよいことはいうまでもない。
　電子素子の製造工程では加熱するプロセスを含むため、無機イオン交換体が好ましい。 These inorganic ion exchangers and organic ion exchangers may be appropriately selected in consideration of the types of cations and anions to be captured and the exchange capacity for the ions. Of course, it goes without saying that the inorganic ion exchanger and the organic ion exchanger may be mixed and used.
Since the manufacturing process of the electronic device includes a heating process, an inorganic ion exchanger is preferable.
　また、マイグレーション防止材料と上述した高分子材料との混合比は、例えば、機械的強度の観点から、マイグレーション防止材料を１０質量％以下とすることが好ましく、マイグレーション防止材料を５質量％以下とすることがより好ましく、更にマイグレーション防止材料を２．５質量％以下とすることが更に好ましい。また、半導体素子又は半導体ウエハと異方導電性部材とを接合した際のマイグレーションを抑制する観点から、マイグレーション防止材料を０．０１質量％以上とすることが好ましい。 Further, the mixing ratio of the migration prevention material and the above-mentioned polymer material is preferably 10% by mass or less for the migration prevention material and 5% by mass or less for the migration prevention material, for example, from the viewpoint of mechanical strength. It is more preferable, and it is further preferable that the migration prevention material is 2.5% by mass or less. Further, from the viewpoint of suppressing migration when the semiconductor element or semiconductor wafer is bonded to the anisotropic conductive member, the migration prevention material is preferably 0.01% by mass or more.
　＜無機充填剤＞
　樹脂層は、無機充填剤を含有していてもよい。
　無機充填剤としては特に制限はなく、公知のものの中から適宜選択することができ、例えば、カオリン、硫酸バリウム、チタン酸バリウム、酸化ケイ素粉、微粉状酸化ケイ素、気相法シリカ、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、マイカ、窒化アルミニウム、酸化ジルコニウム、酸化イットリウム、炭化ケイ素、窒化ケイ素等が挙げられる。 <Inorganic filler>
The resin layer may contain an inorganic filler.
The inorganic filler is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, fine powdered silicon oxide, vapor phase silica, amorphous silica. , Crystalline silica, molten silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, aluminum nitride, zirconium oxide, yttrium oxide, silicon carbide, silicon nitride and the like.
　導通路間に無機充填剤が入ることを防ぎ、導通信頼性がより向上する理由から、無機充填剤の平均粒子径が、各導通路の間隔よりも大きいことが好ましい。
　無機充填剤の平均粒子径は、３０ｎｍ～１０μｍであることが好ましく、８０ｎｍ～１μｍであることがより好ましい。
　ここで、平均粒子径は、レーザー回折散乱式粒子径測定装置(日機装株式会社製マイクロトラックＭＴ３３００)で測定される、一次粒子径を平均粒子径とする。 It is preferable that the average particle size of the inorganic filler is larger than the distance between the conduction paths in order to prevent the inorganic filler from entering between the conduction paths and further improve the conduction reliability.
The average particle size of the inorganic filler is preferably 30 nm to 10 μm, more preferably 80 nm to 1 μm.
Here, the average particle size is the primary particle size measured by a laser diffraction / scattering type particle size measuring device (Microtrac MT3300 manufactured by Nikkiso Co., Ltd.) as the average particle size.
　＜硬化剤＞
　樹脂層は、硬化剤を含有していてもよい。
　硬化剤を含有する場合、接続対象の半導体素子又は半導体ウエハの表面形状との接合不良を抑制する観点から、常温で固体の硬化剤を用いず、常温で液体の硬化剤を含有しているのがより好ましい。
　ここで、「常温で固体」とは、２５℃で固体であることをいい、例えば、融点が２５℃より高い温度である物質をいう。 <Hardener>
The resin layer may contain a curing agent.
When a curing agent is contained, a solid curing agent is not used at room temperature, but a liquid curing agent at room temperature is contained from the viewpoint of suppressing poor bonding with the surface shape of the semiconductor element or semiconductor wafer to be connected. Is more preferable.
Here, "solid at room temperature" means a solid at 25 ° C., for example, a substance having a melting point higher than 25 ° C.
　硬化剤としては、具体的には、例えば、ジアミノジフェニルメタン、ジアミノジフェニルスルホンのような芳香族アミン、脂肪族アミン、４－メチルイミダゾール等のイミダゾール誘導体、ジシアンジアミド、テトラメチルグアニジン、チオ尿素付加アミン、メチルヘキサヒドロフタル酸無水物等のカルボン酸無水物、カルボン酸ヒドラジド、カルボン酸アミド、ポリフェノール化合物、ノボラック樹脂、ポリメルカプタン等が挙げられ、これらの硬化剤から、２５℃で液体のものを適宜選択して用いることができる。なお、硬化剤は１種単独で用いてもよく、２種以上を併用してもよい。 Specific examples of the curing agent include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives such as 4-methylimidazole, dicyandiamide, tetramethylguanidine, thiourea-added amines, and methyl. Examples thereof include carboxylic acid anhydrides such as hexahydrophthalic anhydride, carboxylic acid hydrazide, carboxylic acid amides, polyphenol compounds, novolak resins, and polymercaptans. From these curing agents, liquid ones at 25 ° C. are appropriately selected. Can be used. The curing agent may be used alone or in combination of two or more.
　樹脂層には、その特性を損なわない範囲内で、広く一般に半導体パッケージの樹脂絶縁膜に添加されている分散剤、緩衝剤、粘度調整剤等の種々の添加剤を含有させてもよい。 The resin layer may contain various additives such as a dispersant, a buffer, and a viscosity regulator, which are generally added to the resin insulating film of a semiconductor package, as long as the characteristics are not impaired.
　＜形状＞
　金属充填微細構造体３２の導通路２０を保護する理由から、樹脂層の厚みは、導通路２０の突出部２０ａ、２０ｂの高さより大きく、１μｍ～５μｍであることが好ましい。 <Shape>
For the reason of protecting the conduction path 20 of the metal-filled microstructure 32, the thickness of the resin layer is preferably larger than the height of the protrusions 20a and 20b of the conduction path 20 and is 1 μm to 5 μm.
　次に、保持工程について説明する。
　［保持工程］
　図３７は本発明の実施形態の保持工程に用いられる容器の一例を示す模式的斜視図であり、図３８は本発明の実施形態の保持工程の収納容器の一例を示す模式的断面図である。
　保持工程において、保持とは、静置した状態、及び静置した状態に限らず、搬送等の移動することも含まれる。 Next, the holding process will be described.
[Holding process]
FIG. 37 is a schematic perspective view showing an example of a container used in the holding step of the embodiment of the present invention, and FIG. 38 is a schematic cross-sectional view showing an example of a storage container of the holding step of the embodiment of the present invention. ..
In the holding step, holding is not limited to a stationary state and a stationary state, but also includes movement such as transportation.
　上述のように保持工程は、充填工程により構造体１８（図５参照）の複数の貫通孔１７（細孔）に金属を充填して得られた金属充填部材２１（図６参照）を、相対湿度１０～３０％の環境に２４時間以上さらす工程のことである。上述の保持工程により、貫通孔（細孔）を有する酸化膜（陽極酸化膜１６）において、安定した絶縁抵抗が得られる。相対湿度が４０％を超えると、絶縁抵抗が変動し、安定した絶縁抵抗が得られない。
　一方、相対湿度を１０％未満に維持するには専用設備が必要になる等、湿度の管理が難しい。
　また、保持時間についても、２４時間未満では、絶縁抵抗が変動し、安定した絶縁抵抗が得られない。 As described above, in the holding step, the metal filling member 21 (see FIG. 6) obtained by filling the plurality of through holes 17 (pores) of the structure 18 (see FIG. 5) with metal by the filling step is relative to each other. It is a process of exposing to an environment with a humidity of 10 to 30% for 24 hours or more. By the above-mentioned holding step, stable insulation resistance can be obtained in the oxide film (anodic oxide film 16) having through holes (pores). If the relative humidity exceeds 40%, the insulation resistance fluctuates and stable insulation resistance cannot be obtained.
On the other hand, it is difficult to control the humidity because a dedicated facility is required to maintain the relative humidity below 10%.
Further, regarding the holding time, if it is less than 24 hours, the insulation resistance fluctuates and stable insulation resistance cannot be obtained.
　保持工程では、金属充填部材２１を相対湿度１０～３０％の環境に２４時間以上にさらすことであれば、保管場所等は特に限定されるものではない。例えば、保持工程において、金属充填部材２１は、図３７に示す容器４０に収納されて保管される。容器４０は、容器本体４２と蓋４４とを有する。容器４０では、蓋４４で容器本体４２の開口４２ａが閉塞され、容器本体４２が密閉される。
　また、保持工程における温度は、２５℃以上であればよく、４０℃～５０℃であることが好ましい、 In the holding step, the storage location and the like are not particularly limited as long as the metal filling member 21 is exposed to an environment having a relative humidity of 10 to 30% for 24 hours or more. For example, in the holding step, the metal filling member 21 is stored and stored in the container 40 shown in FIG. 37. The container 40 has a container body 42 and a lid 44. In the container 40, the opening 42a of the container body 42 is closed by the lid 44, and the container body 42 is sealed.
The temperature in the holding step may be 25 ° C. or higher, preferably 40 ° C. to 50 ° C.
　容器内部４２ｂには、例えば、図示はしないが棚が設けられており、複数の金属充填部材２１が、棚に１つずつ離間して収納される。金属充填部材２１が接触して積層されると、金属充填部材２１が振動等により、金属充填部材２１同士が擦れた際に金属充填部材２１が損傷する虞があるため、金属充填部材２１は上述のように離間して収納することが好ましい。１つずつ離間して収納することができれば、棚に限定されるものではなく、棚に代えてスペーサでもよい。
　なお、金属充填部材２１は、上述のように矩形状であり、容器４０としては、矩形状の基板を収納する各種の容器を用いることができる。
　金属充填部材２１が一般的な半導体ウエハの形状と同じく、円形状である場合、容器４０としては、半導体ウエハを収納する各種の容器を用いることができる。容器４０としては、半導体ウエハの搬送容を用いることができ、例えば、フロントオープニングアンファインドポッド（ＦＯＵＰ）及びフロントオープニングシッピングボックス（ＦＯＳＢ）等を用いることができる。 For example, a shelf (not shown) is provided inside the container 42b, and a plurality of metal filling members 21 are housed in the shelves one by one. If the metal filling members 21 are in contact with each other and laminated, the metal filling members 21 may be damaged when the metal filling members 21 rub against each other due to vibration or the like. Therefore, the metal filling member 21 is described above. It is preferable to store them separately as in. As long as they can be stored one by one, the shelves are not limited to the shelves, and spacers may be used instead of the shelves.
The metal filling member 21 has a rectangular shape as described above, and as the container 40, various containers for accommodating the rectangular substrate can be used.
When the metal filling member 21 has a circular shape similar to the shape of a general semiconductor wafer, various containers for accommodating the semiconductor wafer can be used as the container 40. As the container 40, a transfer capacity of a semiconductor wafer can be used, and for example, a front opening unfinded pod (FOUP), a front opening shipping box (FOSB), and the like can be used.
　保持工程では、例えば、図３８に示すように、収納容器５０と、収納容器５０の内部５０ａの温度及び湿度を調整する調整部５２を用いる。
　収納容器５０には、内部５０ａの温度及び湿度の変化を記録するセンサ５３が設けられており、センサ５３からの温度の情報及び湿度の情報に基づいて、調整部５２が、少なくとも収納容器５０の内部５０ａの湿度を調整する。調整部５２による収納容器５０の内部５０ａの温度及び湿度の調整には、例えば、センサ５３からの温度の情報及び湿度の情報に基づくフィードバック制御が用いられる。 In the holding step, for example, as shown in FIG. 38, a storage container 50 and an adjusting unit 52 that adjusts the temperature and humidity of the inside 50a of the storage container 50 are used.
The storage container 50 is provided with a sensor 53 that records changes in the temperature and humidity of the inside 50a, and the adjusting unit 52 is at least the storage container 50 based on the temperature information and the humidity information from the sensor 53. Adjust the humidity inside 50a. For the adjustment of the temperature and humidity inside the storage container 50 by the adjusting unit 52, for example, feedback control based on the temperature information and the humidity information from the sensor 53 is used.
　調整部５２は、例えば、湿度を調整することができれば、特に限定されるものではない。公知の空調機器が利用可能である。また、調整部５２は収納容器５０と一体でも、別体でもよい。
　保持工程では、相対湿度１０～３０％の環境に２４時間以上さらせばよいため、調整部５２は少なくとも温度を調整できる機能を有していればよく、収納容器５０の内部５０ａを換気するファンでもよい。
　なお、湿度に関しては、吸湿剤を収納容器５０の内部５０ａに設けることで調整するようにしてもよく、吸湿剤を容器４０内に設け、調整部５２では温度だけ調整するようにしてもよい。
　センサ５３は、保管期間中、温度及び湿度を計測することができれば、特に限定されるものではないが、温度情報及び湿度情報が時刻と一緒に時系列で記録できるもの、すなわち、時間履歴で記録できることが好ましい。また、センサ５３は有線式でも無線式でもよい。 The adjusting unit 52 is not particularly limited as long as the humidity can be adjusted, for example. Known air conditioning equipment is available. Further, the adjusting unit 52 may be integrated with the storage container 50 or may be a separate body.
In the holding process, the environment may be exposed to an environment with a relative humidity of 10 to 30% for 24 hours or more. Therefore, the adjusting unit 52 only needs to have a function of adjusting the temperature, and even a fan that ventilates the inside 50a of the storage container 50. good.
The humidity may be adjusted by providing a hygroscopic agent inside the storage container 50 50a, or the hygroscopic agent may be provided in the container 40 and only the temperature may be adjusted by the adjusting unit 52.
The sensor 53 is not particularly limited as long as it can measure the temperature and humidity during the storage period, but the temperature information and the humidity information can be recorded in time series together with the time, that is, it is recorded in the time history. It is preferable to be able to do it. Further, the sensor 53 may be a wired type or a wireless type.
　保持工程では、収納容器５０の内部５０ａに複数の容器４０を収納し、収納した状態で、調整部５２を動作させて、収納容器５０の内部５０ａにある容器４０の金属充填部材２１の相対湿度を１０～４０％に保持する。 In the holding step, a plurality of containers 40 are stored in the inner 50a of the storage container 50, and the adjusting unit 52 is operated in the stored state to operate the relative humidity of the metal filling member 21 of the container 40 in the inner 50a of the storage container 50. Is held at 10-40%.
　また、調整部５２により、収納容器５０の内部５０ａについて、温度２５℃における絶対湿度５０％以下の水分量（ｇ／ｃｍ３）の環境となるように調整することが好ましい。なお、温度２５℃における絶対湿度５０％以下の水分量（ｇ／ｃｍ３）は、１１．５２（ｇ／ｃｍ３）である。収納容器５０の内部５０ａの湿度を下げることにより、収納容器５０の内部５０ａの水分量を少なくできる。
　この場合、例えば、温度と湿度及び絶対湿度との関係を調整部５２に記憶させておき、センサ５３からの温度の情報と湿度の情報に基づき、収納容器５０の内部５０ａの水分量を求める。求めた水分量に基づき、調整部５２で温度と湿度を調整するようにしてもよい。
　収納容器５０の内部５０ａの上述の水分量は、上述のように吸湿剤を用いて調整することができる。 Further, it is preferable that the adjusting unit 52 adjusts the inside 50a of the storage container 50 so that the environment has a water content (g / cm 3 ) of 50% or less in absolute humidity at a temperature of 25 ° C. The amount of water (g / cm 3 ) having an absolute humidity of 50% or less at a temperature of 25 ° C. is 11.52 (g / cm 3 ). By lowering the humidity of the inside 50a of the storage container 50, the amount of water inside the storage container 50 can be reduced.
In this case, for example, the relationship between the temperature, the humidity, and the absolute humidity is stored in the adjusting unit 52, and the water content in the inside 50a of the storage container 50 is obtained based on the temperature information and the humidity information from the sensor 53. The temperature and humidity may be adjusted by the adjusting unit 52 based on the obtained water content.
The above-mentioned water content in the inside 50a of the storage container 50 can be adjusted by using a hygroscopic agent as described above.
　また、大気圧よりも圧力が低い減圧下で金属充填部材２１を保管することも好ましい。これにより、収納容器５０の内部５０ａの絶対湿度が低くなる。このことから、金属充填部材２１の絶縁抵抗の変動を抑制でき、ひいては金属充填微細構造体の性能劣化を抑制することができる。また、上述のように減圧下で金属充填部材２１を保管することで、導通路２０の突出部２０ａ、２０ｂの酸化等も抑制することができ、これにより、金属充填部材２１の接合対象、例えば、半導体素子及び半導体ウエハとの接合強度の向上、及び接合対象との接合抵抗の低減の効果を得ることができる。 It is also preferable to store the metal filling member 21 under a reduced pressure lower than the atmospheric pressure. As a result, the absolute humidity inside the storage container 50 50a is lowered. From this, it is possible to suppress fluctuations in the insulation resistance of the metal filling member 21, and thus it is possible to suppress deterioration in the performance of the metal filling microstructure. Further, by storing the metal filling member 21 under reduced pressure as described above, oxidation of the protruding portions 20a and 20b of the conduction path 20 can be suppressed, whereby the metal filling member 21 can be joined, for example. , The effect of improving the bonding strength between the semiconductor element and the semiconductor wafer and reducing the bonding resistance with the bonding target can be obtained.
　上述の減圧下は、例えば、収納容器５０の内部５０ａの空気を排気することにより実現することができ、例えば、調整部５２にロータリーポンプ等の真空ポンプを設けて、更に収納容器５０の内部５０ａの圧力を計測する圧力計又は圧力センサを設けることで実現される。圧力計及び圧力センサとしては、大気圧よりも低い圧力を測定することができるものであれば特に限定されるものではなく、一般的な真空容器に圧力の計測に用いられるものを適宜利用可能である。
　上述の減圧下とは、圧力が０．０１～０．１Ｐａ程度のことをいう。
　また、収納容器５０の内部５０ａに複数設ける構成としたが、これに限定されるものではなく１つでもよい。 The above-mentioned depressurization can be realized by, for example, exhausting the air inside the storage container 50. For example, a vacuum pump such as a rotary pump is provided in the adjusting unit 52, and the inside 50a of the storage container 50 is further provided. It is realized by providing a pressure gauge or a pressure sensor that measures the pressure of. The pressure gauge and the pressure sensor are not particularly limited as long as they can measure the pressure lower than the atmospheric pressure, and those used for measuring the pressure in a general vacuum vessel can be appropriately used. be.
The above-mentioned pressure reduction means that the pressure is about 0.01 to 0.1 Pa.
Further, although a plurality of configurations are provided inside 50a of the storage container 50, the present invention is not limited to this, and one may be used.
　このようにして、金属充填部材２１を保管することができ、収納容器５０に保管された状態で、金属充填部材２１を移送することができる。これにより、保管状態を管理して移送先まで移送することができる。 In this way, the metal filling member 21 can be stored, and the metal filling member 21 can be transferred while being stored in the storage container 50. As a result, the storage state can be managed and the transfer can be performed to the transfer destination.
　容器４０は、収納容器５０に限定されるものではなく、例えば、図３９に示すように収納袋５４に収納してもよい。収納袋５４は、例えば、ガスバリア性を有するフィルムで構成される。ガスバリア性を有するフィルムとは、例えば、水蒸気透過性の低いもののことであり、電子部品の包装に用いられる公知のフィルム、又は有機ＥＬ（Electro Luminescence）、電子ペーパーもしくは太陽電池等に用いられるガスバリアフィルムを用いることができる。
　ガスバリア性は、水蒸気透過性により評価され、水蒸気透過性はモコン法等で測定される。 The container 40 is not limited to the storage container 50, and may be stored in the storage bag 54 as shown in FIG. 39, for example. The storage bag 54 is made of, for example, a film having a gas barrier property. A film having gas barrier properties is, for example, a film having low water vapor permeability, which is a known film used for packaging electronic parts, or a gas barrier film used for organic EL (Electro Luminescence), electronic paper, solar cells, and the like. Can be used.
The gas barrier property is evaluated by the water vapor permeability, and the water vapor permeability is measured by the Mocon method or the like.
　容器４０を収納袋５４に収納した場合、収納袋５４は水蒸気透過性が低く、内部の湿度を外部から調整することが難しくなるため、収納袋５４の内部に吸湿剤５５を設けることが好ましい。吸湿剤５５の量については、使用する収納袋５４の水蒸気透過性、ならびに容器４０の大きさ、及び保管期間等に応じて、予め求めておき、予め求めた量の吸湿剤５５を収納袋５４の内部に設ける。収納袋５４に収納された容器４０を、収納容器５０の内部５０ａに配置して上述のように保管する。この場合、調整部５２で収納容器５０の内部５０ａの温度が調整され、金属充填部材２１の相対温度が１０～４０％とされて、金属充填部材２１が保管される。容器４０を収納袋５４に収納した場合でも、上述のように収納容器５０の内部５０ａを大気圧よりも圧力が低い圧力とし、減圧下で金属充填部材２１を保管することもできる。 When the container 40 is stored in the storage bag 54, the storage bag 54 has low water vapor permeability and it is difficult to adjust the internal humidity from the outside. Therefore, it is preferable to provide the hygroscopic agent 55 inside the storage bag 54. The amount of the hygroscopic agent 55 is determined in advance according to the water vapor permeability of the storage bag 54 to be used, the size of the container 40, the storage period, and the like, and the pre-determined amount of the hygroscopic agent 55 is stored in the storage bag 54. Provided inside. The container 40 stored in the storage bag 54 is arranged inside 50a of the storage container 50 and stored as described above. In this case, the temperature of the inside 50a of the storage container 50 is adjusted by the adjusting unit 52, the relative temperature of the metal filling member 21 is set to 10 to 40%, and the metal filling member 21 is stored. Even when the container 40 is stored in the storage bag 54, the metal filling member 21 can be stored under reduced pressure by setting the pressure inside 50a of the storage container 50 to be lower than the atmospheric pressure as described above.
　また、図４０に示すように、容器４０に上述の調整部５２とセンサ５３を設けてもよい。この場合でも、上述の収納容器５０の内部５０ａに容器４０を配置した場合と同様に、金属充填部材２１を保管することができる。上述のように収納容器５０の内部５０ａを大気圧よりも圧力が低い圧力とし、減圧下で金属充填部材２１を保管することもできる。 Further, as shown in FIG. 40, the container 40 may be provided with the above-mentioned adjusting unit 52 and the sensor 53. Even in this case, the metal filling member 21 can be stored in the same manner as when the container 40 is arranged inside 50a of the storage container 50 described above. As described above, the pressure inside 50a of the storage container 50 is set to a pressure lower than the atmospheric pressure, and the metal filling member 21 can be stored under reduced pressure.
　図３９に示すように、収納袋５４を用いる場合、図３７に示す容器４０は必ずしも必要なく、例えば、図４１に示すように、金属充填部材２１の金属層１９上にスペーサ５６を配置して、複数の金属充填部材２１を積層し、収納袋５４に収納してもよい。この場合も、相対温度を１０～４０％とするために、図３９に示すように収納袋５４の内部に吸湿剤５５を配置することが好ましい。
　スペーサ５６としては、紙、樹脂フィルム等を用いることができる。なお、スペーサ５６としては、金属充填部材２１の少なくとも金属層１９を覆うものであればよい。 As shown in FIG. 39, when the storage bag 54 is used, the container 40 shown in FIG. 37 is not always necessary. For example, as shown in FIG. 41, the spacer 56 is arranged on the metal layer 19 of the metal filling member 21. , A plurality of metal filling members 21 may be laminated and stored in the storage bag 54. Also in this case, in order to set the relative temperature to 10 to 40%, it is preferable to dispose the hygroscopic agent 55 inside the storage bag 54 as shown in FIG. 39.
As the spacer 56, paper, a resin film, or the like can be used. The spacer 56 may be any one that covers at least the metal layer 19 of the metal filling member 21.
　本発明は、基本的に以上のように構成されるものである。以上、本発明の金属充填微細構造体の製造方法について詳細に説明したが、本発明は上述の実施形態に限定されず、本発明の主旨を逸脱しない範囲において、種々の改良又は変更をしてもよいのはもちろんである。 The present invention is basically configured as described above. Although the method for producing the metal-filled microstructure of the present invention has been described in detail above, the present invention is not limited to the above-described embodiment, and various improvements or changes have been made without departing from the gist of the present invention. Of course, it is also good.
　以下に実施例を挙げて本発明の特徴を更に具体的に説明する。以下の実施例に示す材料、試薬、物質量とその割合、及び、操作等は本発明の趣旨から逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下の実施例に限定されるものではない。
　本実施例では、実施例１～実施例９及び比較例１～比較例３の金属充填部材を作製した。実施例１～実施例９及び比較例１～比較例３の金属充填部材について搬送性を評価した。実施例１～実施例９及び比較例１～比較例３の金属充填部材について、異方導電性を確保した後に絶縁抵抗を評価した。以下、搬送性及び絶縁抵抗の各評価項目について説明する。 The features of the present invention will be described in more detail with reference to Examples below. The materials, reagents, amounts of substances and their ratios, operations, etc. 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.
In this example, the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3 were produced. The transportability of the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3 was evaluated. The insulation resistance of the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3 was evaluated after ensuring anisotropic conductivity. Hereinafter, each evaluation item of transportability and insulation resistance will be described.
搬送性の評価について説明する。
　＜搬送性の評価＞
　金属充填部材を用い、以下に示すようにして搬送性を評価した。
　搬送性については、ＪＩＳ　Ｚ０２００：２０１３包装貨物－性能試験方法の一般通則にのっとり、ＪＩＳ　Ｚ０２３２：２００４の包装貨物－振動試験方法に記載のランダム振動試験においてレベル１を想定し、輸送振動試験及び跳ね上がり振動試験を実施して評価した。
　包装形態は、塩化ビニル製のケース（１５５ｍｍ×１５５ｍｍ×３５ｍｍ、スチロール角型ケース１９型　アズワン株式会社製）に、各金属充填部材を合紙を挟みながら１０枚積層して封入した。厚み１ｃｍの発泡スチロール製の緩衝材を積層した金属充填部材の上下に配置した。ケースに蓋をし、ケース毎にラミネートパックして供試材とした。合紙には、ＡＰクリーンペーパーII　Ａ４ピンク（７２ｇ／ｍ２）を用いた。 The evaluation of transportability will be described.
<Evaluation of transportability>
Using a metal filling member, the transportability was evaluated as shown below.
Regarding transportability, in accordance with the general rules of JIS Z0200: 2013 packaged cargo-performance test method, level 1 is assumed in the random vibration test described in JIS Z0232: 2004 packaged cargo-vibration test method, and transport vibration test and jump-up A vibration test was performed and evaluated.
As for the packaging form, 10 sheets of each metal filling member were laminated and sealed in a vinyl chloride case (155 mm × 155 mm × 35 mm, styrene square case 19 type manufactured by AS ONE Corporation) with a slip sheet sandwiched between them. It was arranged above and below the metal filling member in which a cushioning material made of styrofoam having a thickness of 1 cm was laminated. The case was covered, and each case was laminated and packed as a test material. AP Clean Paper II A4 Pink (72 g / m 2 ) was used as the interleaving paper.
　搬送性の試験における温湿度条件は、ＪＩＳ　Ｚ　０２０３：２０００の表１（前処置の温湿度条件）のＧ（＋２３℃，湿度５０％ＲＨ（相対湿度））に準拠し、供試材に対して、１８０分間のランダム振動試験を行い、続けて同じ供試材を３０分間跳ね上がり試験に供した。
　上述の試験後、ケースから取り出した金属充填部材を、目視により確認し、金属充填部において、複数枚搬送したもののうち、評価のレベルが最も悪かったものの結果を全体の評価とした。
　以下の評価基準により、金属充填部へのダメージを評価した。搬送性の評価結果を下記表１に示す。 The temperature and humidity conditions in the transportability test are based on G (+ 23 ° C, humidity 50% RH (relative humidity)) in Table 1 (pretreatment temperature and humidity conditions) of JIS Z 0203: 2000, and are used for the test material. Then, a random vibration test was performed for 180 minutes, and then the same test material was subjected to a flip-up test for 30 minutes.
After the above-mentioned test, the metal filling member taken out from the case was visually confirmed, and the result of the one having the worst evaluation level among the multiple pieces transported in the metal filling part was taken as the overall evaluation.
Damage to the metal filling part was evaluated according to the following evaluation criteria. The evaluation results of transportability are shown in Table 1 below.
　評価基準
　金属充填部材において、金属充填部である金属層に傷がない場合をＡとした。
　金属充填部材において、金属充填部である金属層に傷があっても陽極酸化膜に到達していない場合をＢとした。
　金属充填部材において、金属充填部である金属層に傷があり、かつ陽極酸化膜に到達している場合をＣとした。 Evaluation Criteria In the metal filling member, the case where the metal layer, which is the metal filling portion, is not scratched was designated as A.
In the metal filling member, the case where the metal layer, which is the metal filling portion, was scratched but did not reach the anodic oxide film was defined as B.
In the metal filling member, the case where the metal layer which is the metal filling portion is scratched and reaches the anodic oxide film is designated as C.
　絶縁抵抗の評価について説明する。
　＜絶縁抵抗の評価＞
　製造した金属充填部材について、金属層を除去した後、バルブ金属部材を構成するアルミニウム基板を除去して、陽極酸化膜単体とした。次に、陽極酸化膜の表面を、化学的機械的研磨（ＣＭＰ）により研磨して平滑化した。これにより異方導電性を確保した。この状態で、陽極酸化膜の表面上において、２０ｍｍ離して端子を設置した際に、絶縁抵抗計を用いて、抵抗値を測定した。
　なお、金属充填部材が異方導電性を確保するまでの工程については、後に詳細に説明する。
　抵抗値の数値に基づき、下記評価基準にて絶縁抵抗を評価した。絶縁抵抗の評価結果を下記表１に示す。
　評価基準
　Ａ：抵抗Ｒ＞１０ＭΩ
　Ｂ：１０ＭΩ≧抵抗Ｒ＞１ＭΩ
　Ｃ：１ＭΩ≧抵抗Ｒ＞１０ｋΩ
　Ｄ：１０ｋΩ≧抵抗Ｒ＞１ｋΩ
　Ｅ：１ｋΩ≧抵抗Ｒ The evaluation of insulation resistance will be described.
<Evaluation of insulation resistance>
With respect to the manufactured metal filling member, after removing the metal layer, the aluminum substrate constituting the valve metal member was removed to form a simple anodic oxide film. The surface of the anodic oxide film was then polished and smoothed by chemical mechanical polishing (CMP). This ensured anisotropic conductivity. In this state, when the terminals were installed 20 mm apart on the surface of the anodic oxide film, the resistance value was measured using an insulation resistance tester.
The process of ensuring the anisotropic conductivity of the metal filling member will be described in detail later.
The insulation resistance was evaluated according to the following evaluation criteria based on the numerical value of the resistance value. The evaluation results of insulation resistance are shown in Table 1 below.
Evaluation Criteria A: Resistance R> 10MΩ
B: 10MΩ ≥ resistance R> 1MΩ
C: 1MΩ ≥ resistance R> 10kΩ
D: 10kΩ ≥ resistance R> 1kΩ
E: 1kΩ ≧ resistance R
　以下、実施例１～実施例９及び比較例１～比較例３について説明する。 Hereinafter, Examples 1 to 9 and Comparative Examples 1 to 3 will be described.
（実施例１）
　実施例１の金属充填部材について説明する。
　［金属充填部材］
　＜アルミニウム基板＞
　純度９９．９９９質量％のアルミニウム基板を用いた。アルミニウム基板の厚みを１２０μｍとした。
　アルミニウム基板については、１５ｃｍ四方のサイズにトリミングした上で、周囲に５ｍｍ幅のフレームができるように高粘着テープを貼り付けた。フレーム内部の陽極酸化膜１６部分のサイズが１４ｃｍ四方となるようにした。高粘着テープには、日東電工ＣＳシステム株式会社製ダンプロン（登録商標）テープＮｏ．３７５（幅２５ｍｍ×長さ５０ｍ）を用いた。 (Example 1)
The metal filling member of Example 1 will be described.
[Metal filling member]
<Aluminum substrate>
An aluminum substrate having a purity of 99.999% by mass was used. The thickness of the aluminum substrate was 120 μm.
The aluminum substrate was trimmed to a size of 15 cm square, and a high-adhesive tape was attached so that a frame having a width of 5 mm could be formed around the aluminum substrate. The size of the 16 parts of the anodic oxide film inside the frame was adjusted to be 14 cm square. For high adhesive tape, Nitto Denko CS System Co., Ltd. Dumplon (registered trademark) tape No. 375 (width 25 mm × length 50 m) was used.
　＜電解研磨処理＞
　上述のアルミニウム基板に対して、以下組成の電解研磨液を用いて、電圧１０Ｖ、液温度６５℃、液流速３．０ｍ／分の条件で、電解研磨処理を施した。なお、電解処理の処理面積は０．１２ｍ２とした。
　陰極はカーボン電極とし、電源は、ＧＰ０１１０－３０Ｒ（株式会社高砂製作所社製）を用いた。また、電解液の流速は渦式フローモニターＦＬＭ２２－１０ＰＣＷ（アズワン株式会社製）を用いて計測した。
　（電解研磨液組成）
　・８５質量％リン酸（和光純薬社製試薬）　　６６０ｍＬ
　・純水　　１６０ｍＬ
　・硫酸　　１５０ｍＬ
　・エチレングリコール　　３０ｍＬ <Electropolishing treatment>
The above-mentioned aluminum substrate was subjected to an electrolytic polishing treatment using an electrolytic polishing liquid having the following composition under the conditions of a voltage of 10 V, a liquid temperature of 65 ° C., and a liquid flow velocity of 3.0 m / min. The treated area of the electrolytic treatment was 0.12 m 2 .
The cathode was a carbon electrode, and the power supply 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).
(Electropolishing liquid composition)
・ 85% by mass phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 660 mL
・ Pure water 160mL
・ Sulfuric acid 150mL
・ Ethylene glycol 30 mL
　＜陽極酸化処理工程＞
　次いで、電解研磨処理後のアルミニウム基板に、特開２００７－２０４８０２号公報に記載の手順にしたがって自己規則化法による陽極酸化処理を施した。
　電解研磨処理後のアルミニウム基板に、０．５０ｍｏｌ／Ｌシュウ酸の電解液で、電圧４５Ｖ、液温度１６℃、液流速３．０ｍ／分の条件で、１時間のプレ陽極酸化処理を施した。
　その後、プレ陽極酸化処理後のアルミニウム基板を、０．６ｍｏｌ／Ｌリン酸水溶液（液温：４０℃）に０．５時間浸漬させる脱膜処理を施した。
　その後、０．５０ｍｏｌ／Ｌシュウ酸の電解液で、電圧４５Ｖ、液温度１６℃、液流速３．０ｍ／分の条件で、再度陽極酸化処理を施し、アルミニウム基板の表面を部分的に陽極酸化させて、厚み５０μｍの陽極酸化膜を形成した。
　これにより、外縁に５ｍｍ幅のフレーム部を備えるアルミニウム基板と、アルミニウム基板のフレーム部内に設けられた陽極酸化膜とを有する構造体を得た。
　なお、プレ陽極酸化処理及び再陽極酸化処理は、いずれもアルミニウム基板を高粘着テープでマスキングした状態で行った。また、プレ陽極酸化処理及び再陽極酸化処理は、いずれも陰極はチタン電極とし、電源にはＰＡＭ３２０－１２(菊水電子工業株式会社製)を用いた。また、冷却装置にはＮｅｏＣｏｏｌ ＢＤ３６（ヤマト科学株式会社製）、かくはん加温装置にはペアスターラー ＰＳ－１００（ＥＹＥＬＡ東京理化器械株式会社製）を用いた。更に、電解液の流速は渦式フローモニターＦＬＭ２２－１０ＰＣＷ（アズワン株式会社製）を用いて計測した。 <Anodizing process>
Next, the aluminum substrate after the electrolytic polishing treatment was anodized 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 a pre-anodizing treatment for 1 hour with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 45 V, a liquid temperature of 16 ° C., and a liquid flow velocity of 3.0 m / min. ..
Then, the pre-anodized aluminum substrate was subjected to a film removal treatment by immersing it in a 0.6 mol / L phosphoric acid aqueous solution (liquid temperature: 40 ° C.) for 0.5 hours.
Then, anodizing treatment was performed again with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 45 V, a liquid temperature of 16 ° C., and a liquid flow velocity of 3.0 m / min to partially anodize the surface of the aluminum substrate. To form an anodized film having a thickness of 50 μm.
As a result, a structure having an aluminum substrate having a frame portion having a width of 5 mm on the outer edge and an anodic oxide film provided in the frame portion of the aluminum substrate was obtained.
Both the pre-anodizing treatment and the re-anodizing treatment were performed with the aluminum substrate masked with a high-adhesive tape. In both the pre-anodizing treatment and the re-anodizing treatment, the cathode was a titanium electrode and PAM320-12 (manufactured by Kikusui Electronics Co., Ltd.) was used as the power source. A NeoCool BD36 (manufactured by Yamato Scientific Co., Ltd.) was used as the cooling device, and a pair stirrer PS-100 (manufactured by EYELA Tokyo Rika Kikai Co., Ltd.) was used as the stirring and heating device. Further, the flow velocity of the electrolytic solution was measured using a vortex type flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
　＜バリア層除去工程＞
　次いで、上述の陽極酸化処理と同様の処理液及び処理条件で、電圧を４０Ｖから０Ｖまで連続的に電圧降下速度０．２Ｖ／ｓｅｃで降下させながら電解処理（電解除去処理）を施した。電解処理には、直流電源として、ＰＫ４５－９（モデル名、松定プレシジョン株式会社製)を用いた。
　陽極酸化処理後の基材は流水で十分に洗浄した後、低温の風で数分以内に乾燥させた。陽極酸化処理した基板はイオン交換水（５０℃）及び界面活性剤を含む溶液（４５℃）に交互に３分ずつ浸漬した後、イオン交換水をかけ流した後、ウェットな状態でバリア層除去処理に供した。なお、界面活性剤を含む溶液には、ロームアンドハース社製前処理液「NeutraClean68」をイオン交換水と１：４の割合で希釈した液を用いた。
　温度２５℃に保持した過飽和状態の金属亜鉛を含む水酸化ナトリウム溶液に２分間浸漬させるエッチング処理（バリア層除去処理）を実施し、その後、水洗することにより、陽極酸化膜の底部にあるバリア層を除去しマイクロポアを介して露出したアルミニウム基板表面に亜鉛の導電層を形成した。金属亜鉛を含む水酸化ナトリウム溶液には、水酸化ナトリウム水溶液（ＮａＯＨ＝５２ｇ／Ｌ）には、酸化亜鉛を２０００ｐｐｍ溶解させた溶液を用いた。 <Barrier layer removal process>
Then, under the same treatment liquid and treatment conditions as the above-mentioned anodizing treatment, electrolytic treatment (electrolytic removal treatment) was performed while continuously lowering the voltage from 40 V to 0 V at a voltage drop rate of 0.2 V / sec. PK45-9 (model name, manufactured by Matsusada Precision Co., Ltd.) was used as a DC power source for the electrolytic treatment.
The base material after the anodizing treatment was thoroughly washed with running water and then dried with low-temperature air within a few minutes. The anodicated substrate is immersed in ion-exchanged water (50 ° C.) and a solution containing a surfactant (45 ° C.) alternately for 3 minutes each, then poured with ion-exchanged water, and then the barrier layer is removed in a wet state. It was used for processing. As the solution containing the surfactant, a solution prepared by diluting the pretreatment solution "NeutraClean 68" manufactured by Roam & Haas with ion-exchanged water at a ratio of 1: 4 was used.
An etching treatment (barrier layer removal treatment) is performed in which the mixture is immersed in a sodium hydroxide solution containing supersaturated metallic zinc maintained at a temperature of 25 ° C. for 2 minutes, and then washed with water to obtain a barrier layer at the bottom of the anodized film. A conductive layer of zinc was formed on the surface of the aluminum substrate exposed through the micropores. As the sodium hydroxide solution containing metallic zinc, a solution prepared by dissolving 2000 ppm of zinc oxide in the sodium hydroxide aqueous solution (NaOH = 52 g / L) was used.
　ここで、バリア層除去工程後の陽極酸化膜に存在するマイクロポア（細孔）の平均直径は６０ｎｍであった。なお、平均直径は、ＦＥ－ＳＥＭ（Field emission - Scanning Electron Microscope）により表面写真（倍率５００００倍）を撮影し、５０点測定した平均値として算出した。
　また、バリア層除去工程後の陽極酸化膜の平均厚みは４０μｍであった。すなわち、酸化膜の平均厚みは４０μｍであった。なお、陽極酸化膜の平均厚みは、陽極酸化膜を厚み方向に対してＦＩＢ（Focused Ion Beam）で切削加工し、その断面をＦＥ－ＳＥＭにより表面写真（倍率５００００倍）を撮影し、１０点測定した平均値として算出した。
　陽極酸化膜に存在するマイクロポアの密度は、約１億個／ｍｍ2であった。なお、マイクロポアの密度は、特開２００８－２７０１５８号公報の［０１６８］及び［０１６９］段落に記載された方法で測定し、算出した。
　また、陽極酸化膜に存在するマイクロポアの規則化度は、９２％であった。なお、規則化度は、ＦＥ－ＳＥＭにより表面写真（倍率２００００倍）を撮影し、特開２００８－２７０１５８号公報の［００２４］～［００２７］段落に記載された方法で測定し、算出した。 Here, the average diameter of the micropores (pores) present in the anodic oxide film after the barrier layer removing step was 60 nm. The average diameter was calculated as an average value measured at 50 points by taking a surface photograph (magnification: 50,000 times) with an FE-SEM (Field emission-Scanning Electron Microscope).
The average thickness of the anodic oxide film after the barrier layer removing step was 40 μm. That is, the average thickness of the oxide film was 40 μm. The average thickness of the anodic oxide film is 10 points after cutting the anodic oxide film with FIB (Focused Ion Beam) in the thickness direction and taking a surface photograph (magnification 50,000 times) of the cross section with FE-SEM. It was calculated as the measured average value.
The density of micropores present in the anodic oxide film was about 100 million pieces / mm 2 . The density of micropores was measured and calculated by the method described in paragraphs [0168] and [0169] of JP-A-2008-270158.
The degree of regularization of the micropores present in the anodic oxide film was 92%. The degree of regularization was calculated by taking a surface photograph (magnification of 20000 times) with an FE-SEM and measuring by the method described in paragraphs [0024] to [0027] of JP-A-2008-270158.
　＜金属充填工程＞
　次いで、アルミニウム基板を陰極にし、銅を正極にして電解めっき処理を施した。
　具体的には、以下に示す組成の銅めっき液を使用し、定電流電解を施すことにより、マイクロポアの内部に銅が充填され、かつフレーム部上にも銅で構成された金属層が形成された金属充填部材を得た。フレーム部上の金属層の厚みδ（図６参照）は５０μｍであった。
　ここで、定電流電解は、電源にＰＡＳ２０－３６(菊水電子工業株式会社製)を用い、ノベル株式会社製のめっき装置を用い、北斗電工株式会社製の電源（ＨＺ－３０００）を用い、めっき液中でサイクリックボルタンメトリを行って析出電位を確認した後に、以下に示す条件で処理を施した。
　（銅めっき液組成及び条件）
　・硫酸銅１００ｇ／Ｌ
　・硫酸１ｇ／Ｌ
　・塩酸１５ｇ／Ｌ
　・ＳＰＳ（３，３´－ジチオビス（１－プロパンスルホン酸）二ナトリウム）８．５ｐｐｍ
　・ＰＥＧ（ポリエチレングリコール）５ｐｐｍ
　・温度３０℃
　・電流密度１０Ａ／ｄｍ2 <Metal filling process>
Next, the aluminum substrate was used as a cathode and copper was used as a positive electrode for electrolytic plating.
Specifically, by using a copper plating solution having the composition shown below and performing constant current electrolysis, copper is filled inside the micropores, and a metal layer made of copper is also formed on the frame portion. A metal-filled member was obtained. The thickness δ of the metal layer on the frame portion (see FIG. 6) was 50 μm.
Here, for constant current electrolysis, PAS20-36 (manufactured by Kikusui Denshi Kogyo Co., Ltd.) is used as the power source, a plating apparatus manufactured by Novell Co., Ltd. is used, and a power source (HZ-3000) manufactured by Hokuto Denko Co., Ltd. is used for plating. After cyclic voltammetry was performed in the liquid to confirm the precipitation potential, the treatment was performed under the conditions shown below.
(Copper plating solution composition and conditions)
・ Copper sulfate 100g / L
・ Sulfuric acid 1g / L
・ Hydrochloric acid 15g / L
SPS (3,3'-dithiobis (1-propanesulfonic acid) disodium) 8.5 ppm
・ PEG (polyethylene glycol) 5 ppm
・ Temperature 30 ℃
・ Current density 10A / dm 2
　上述の絶縁抵抗の評価のために、製造した金属充填部材を１０枚積層して、塩化ビニール製のケースに収納して蓋をした状態で、低湿度型低温恒温恒湿器（ＰＤＬ－４Ｊ（型式）　エスペック株式会社製）内に保管した。低湿度型低温恒温恒湿器内を温度４０℃、相対湿度が２０％の環境にし、２５時間さらした後、以下の工程を実施した。
　＜金属層除去工程＞
　金属充填部材に対して、粘着テープを用いて金属層を除去した。粘着テープには、ダンプロンテープ　No.375　(日東電工株式会社製)を用いた。
　＜基板除去工程＞
　次いで、２０質量％塩化水銀水溶液（昇汞）に２０℃、３時間浸漬させることによりアルミニウム基板を溶解して除去することにより、陽極酸化膜単体とした。 In order to evaluate the above-mentioned insulation resistance, a low-humidity low-temperature constant temperature and humidity controller (PDL-4J (PDL-4J)) with 10 manufactured metal filling members laminated, stored in a vinyl chloride case and covered with a lid. Model) Stored in ESPEC CO., LTD.). The inside of the low humidity type low temperature constant temperature and humidity chamber was brought into an environment with a temperature of 40 ° C. and a relative humidity of 20%, and after exposure for 25 hours, the following steps were carried out.
<Metal layer removal process>
The metal layer was removed from the metal filling member using an adhesive tape. Dumplon tape No. 375 (manufactured by Nitto Denko KK) was used as the adhesive tape.
<Substrate removal process>
Then, the aluminum substrate was dissolved and removed by immersing it in a 20 mass% mercury chloride aqueous solution (rise) at 20 ° C. for 3 hours to obtain an anodized film as a simple substance.
　＜平滑化工程＞
　次いで、陽極酸化膜の表面に、ＣＭＰ（Chemical Mechanical Polishing）処理を施し、表面を研磨することにより、表面を平滑化した。平滑化工程により、異方導電性が確保される。この状態で、上述の絶縁抵抗を測定した。
　平滑化工程では、ＭＡＴ社製研磨装置（ＢＣ－１５ＣＮ（商品名））を用いて、陽極酸化膜の表面を、アルミナを含む研磨剤（ＷＡ＃８０００（ＦＦ）ケメット・ジャパン株式会社製を純水で４倍に希釈した液）で一次研磨を行い、シリカを含む研磨剤（Ｓ－Ａ１－１－０　ケメット・ジャパン株式会社製）で二次研磨を行い、研磨後の仕上がりの算術平均粗さ（ＪＩＳ　Ｂ０６０１：２００１）を０．００５μｍとした。 <Smoothing process>
Next, the surface of the anodic oxide film was subjected to CMP (Chemical Mechanical Polishing) treatment, and the surface was polished to smooth the surface. The smoothing step ensures anisotropic conductivity. In this state, the above-mentioned insulation resistance was measured.
In the smoothing process, a polishing device (BC-15CN (trade name)) manufactured by MAT was used to polish the surface of the anodized film with an abrasive containing alumina (WA # 8000 (FF) made by Chemet Japan Co., Ltd.). Primary polishing is performed with a solution diluted 4-fold with water), secondary polishing is performed with an abrasive containing silica (manufactured by SA1-1-0 Chemet Japan Co., Ltd.), and the arithmetic average coarseness of the finished product after polishing is performed. (JIS B0601: 2001) was set to 0.005 μm.
（実施例２）
　実施例２は、実施例１に比して、保持時間が３０時間である点が異なる以外は、実施例１と同じとした。
（実施例３）
　実施例３は、実施例１に比して、保持時間が４０時間である点が異なる以外は、実施例１と同じとした。
（実施例４）
　実施例４は、実施例２に比して、フレーム部の幅が３ｍｍである点が異なる以外は、実施例１と同じとした。実施例４では、周囲に３ｍｍ幅のフレームができるように高粘着テープを貼り付けた。
（実施例５）
　実施例５は、実施例３に比して、フレーム部の厚みが２４０μｍである点が異なる以外は、実施例１と同じとした。実施例５では、厚み２４０μｍのアルミニウム基板を用いた。 (Example 2)
Example 2 was the same as that of Example 1 except that the holding time was 30 hours as compared with Example 1.
(Example 3)
Example 3 was the same as that of Example 1 except that the holding time was 40 hours as compared with Example 1.
(Example 4)
Example 4 was the same as that of Example 1 except that the width of the frame portion was 3 mm as compared with Example 2. In Example 4, a high-adhesive tape was attached so that a frame having a width of 3 mm could be formed around the frame.
(Example 5)
Example 5 was the same as that of Example 1 except that the thickness of the frame portion was 240 μm as compared with Example 3. In Example 5, an aluminum substrate having a thickness of 240 μm was used.
（実施例６）
　実施例６は、実施例２に比して、相対湿度が１０％である点が異なる以外は、実施例１と同じとした。
（実施例７）
　実施例７は、実施例３に比して、相対湿度が３０％である点が異なる以外は、実施例１と同じとした。
（実施例８）
　実施例８は、実施例３に比して、平均直径が４０ｎｍである点が異なる以外は、実施例１と同じとした。実施例８は、陽極酸化処理を１５％硫酸水溶液中で２５Ｖの電圧で液温を３℃に設定して実施して、平均直径を４０ｎｍとした。
（実施例９）
　実施例９は、実施例３に比して、平均直径が２００ｎｍである点が異なる以外は、実施例１と同じとした。実施例９は、陽極酸化処理を０．１Ｍリン酸水溶液で１９５Ｖの電圧で液温を３℃に設定して実施して、平均直径を２００ｎｍとした。 (Example 6)
Example 6 was the same as Example 1 except that the relative humidity was 10% as compared with Example 2.
(Example 7)
Example 7 was the same as Example 1 except that the relative humidity was 30% as compared with Example 3.
(Example 8)
Example 8 was the same as that of Example 1 except that the average diameter was 40 nm as compared with Example 3. In Example 8, the anodizing treatment was carried out in a 15% aqueous sulfuric acid solution at a voltage of 25 V at a liquid temperature of 3 ° C., and the average diameter was 40 nm.
(Example 9)
Example 9 was the same as Example 1 except that the average diameter was 200 nm as compared with Example 3. In Example 9, the anodizing treatment was carried out with a 0.1 M aqueous phosphoric acid solution at a voltage of 195 V and the liquid temperature was set to 3 ° C., and the average diameter was set to 200 nm.
（比較例１）
　比較例１は、実施例１に比して、保持時間が２０時間である点が異なる以外は、実施例１と同じとした。
（比較例２）
　比較例２は、実施例１に比して、フレーム部がない構成とした点が異なる以外は、実施例１と同じとした。比較例２では、バルブ金属部材の表面全域に陽極酸化膜を形成して、金属充填部材を作製した。
（比較例３）
　比較例３は、実施例１に比して、相対湿度が４０％である点が異なる以外は、実施例１と同じとした。 (Comparative Example 1)
Comparative Example 1 was the same as that of Example 1 except that the holding time was 20 hours as compared with Example 1.
(Comparative Example 2)
Comparative Example 2 was the same as that of Example 1 except that the configuration without the frame portion was different from that of Example 1. In Comparative Example 2, an anodic oxide film was formed over the entire surface of the valve metal member to prepare a metal-filled member.
(Comparative Example 3)
Comparative Example 3 was the same as that of Example 1 except that the relative humidity was 40% as compared with Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１～実施例９は、比較例１～比較例３に比して、搬送性及び絶縁抵抗について良好な結果が得られた。
　比較例１は、保持時間が短く、絶縁抵抗の結果が悪かった。比較例３は、フレーム部がなく、搬送性の結果が悪かった。比較例５は、相対湿度が高く、絶縁抵抗の結果が悪かった。 As shown in Table 1, in Examples 1 to 9, better results were obtained in terms of transportability and insulation resistance as compared with Comparative Examples 1 to 3.
In Comparative Example 1, the holding time was short and the result of insulation resistance was poor. In Comparative Example 3, there was no frame portion, and the result of transportability was poor. In Comparative Example 5, the relative humidity was high and the result of insulation resistance was poor.
　１１、１５　バルブ金属部材
　１１ａ、１５ａ、１６ａ、２６ａ、６１ａ　表面
　１１ｂ、１６ｅ　外縁
　１１ｃ、１５ｃ　領域
　１１ｅ　底部
　１２、１３、１４　マスク
　１３ａ　開口
　１５ｂ　外縁
　１５ｄ　フレーム部
　１５ｅ　底部
　１６　陽極酸化膜
　１６ｂ　裏面
　１７　貫通孔
　１８　構造体
　１９　金属層
　２０　導通路
　２０ａ、２０ｂ　突出部
　２１　金属充填部材
　２２　樹脂基材
　２４　支持体
　２６　樹脂層
　２７　剥離層
　２８　支持層
　２９　剥離剤
　３０　両面粘着剤
　３１　支持部材
　３２　金属充填微細構造体
　４０　容器
　４２　容器本体
　４２ａ　開口
　４２ｂ　容器内部
　４４　蓋
　５０　収納容器
　５０ａ　内部
　５２　調整部
　５３　センサ
　５４　収納袋
　５５　吸湿剤
　５６　スペーサ
　６０　電極体
　６１　絶縁支持体
　６２　導電層
　６３　レジスト層
　Ｄｔ　厚み方向
　ｈ　厚み
　ＨＡ　厚み
　ｐ　中心間距離
　Ｑ　領域
　ｘ　方向
　δ　厚み 11,15 Valve metal members 11a, 15a, 16a, 26a, 61a Surface 11b, 16e Outer edge 11c, 15c Area 11e Bottom 12, 13, 14 Mask 13a Opening 15b Outer edge 15d Frame 15e Bottom 16 Anodized film 16b Back surface 17 Through hole 18 Structure 19 Metal layer 20 Conduction path 20a, 20b Projection 21 Metal filling member 22 Resin base material 24 Support 26 Resin layer 27 Peeling layer 28 Supporting layer 29 Peeling agent 30 Double-sided adhesive 31 Supporting member 32 Metal-filled microstructure 40 Container 42 Container body 42a Opening 42b Inside the container 44 Lid 50 Storage container 50a Inside 52 Adjusting part 53 Sensor 54 Storage bag 55 Moisturizer 56 Spacer 60 Electrode body 61 Insulation support 62 Conductive layer 63 Resist layer Dt Thickness direction h Thickness HA Thickness p Center-to-center distance Q region x direction δ Thickness

Claims (9)

  1. 　バルブ金属部材の外縁に配置されたフレーム部により囲まれる形成領域に、複数の細孔を有する酸化膜を形成することにより、前記バルブ金属部材と前記酸化膜とを有する構造体を得る形成工程と、
    　前記構造体に対して、前記酸化膜の前記複数の細孔に金属を充填する充填工程と、
    　前記充填工程により、前記構造体に対して、前記酸化膜の前記複数の細孔に金属を充填して得られた金属充填部材を、相対湿度１０～３０％の環境に２４時間以上さらす保持工程とを有し、
    　前記複数の細孔は、平均直径が１μｍ以下である、金属充填微細構造体の製造方法。     A forming step of obtaining a structure having the valve metal member and the oxide film by forming an oxide film having a plurality of pores in a forming region surrounded by a frame portion arranged on the outer edge of the valve metal member. ,
    A filling step of filling the plurality of pores of the oxide film with a metal in the structure,
    A holding step of exposing the structure to a metal-filled member obtained by filling the plurality of pores of the oxide film with metal in an environment having a relative humidity of 10 to 30% for 24 hours or more. And have
    A method for producing a metal-filled microstructure in which the plurality of pores have an average diameter of 1 μm or less.
  2. 　前記バルブ金属部材は、アルミニウムで構成されている、請求項１に記載の金属充填微細構造体の製造方法。 The method for manufacturing a metal-filled microstructure according to claim 1, wherein the valve metal member is made of aluminum.
  3. 　前記酸化膜は、陽極酸化膜である、請求項１又は２に記載の金属充填微細構造体の製造方法。 The method for producing a metal-filled microstructure according to claim 1 or 2, wherein the oxide film is an anodic oxide film.
  4. 　前記陽極酸化膜は、Ａｌ２Ｏ３膜である、請求項３に記載の金属充填微細構造体の製造方法。 The method for producing a metal-filled microstructure according to claim 3 , wherein the anodic oxide film is an Al 2 O 3 film.
  5. 　前記充填工程において、前記酸化膜の前記複数の細孔に充填する金属は、銅である、請求項１～４のいずれか１項に記載の金属充填微細構造体の製造方法。 The method for producing a metal-filled microstructure according to any one of claims 1 to 4, wherein in the filling step, the metal to be filled in the plurality of pores of the oxide film is copper.
  6. 　前記充填工程は、前記構造体の表面に金属層を形成することにより、前記金属を前記複数の前記細孔に充填する工程であり、
    　前記充填工程は、前記金属層を前記フレーム部上に厚み１００μｍ以下に形成する、請求項１～５のいずれか１項に記載の金属充填微細構造体の製造方法。     The filling step is a step of filling the plurality of pores with the metal by forming a metal layer on the surface of the structure.
    The method for producing a metal-filled microstructure according to any one of claims 1 to 5, wherein the filling step forms the metal layer on the frame portion with a thickness of 100 μm or less.
  7. 　前記保持工程の後、前記構造体の前記表面に形成された前記金属層を除去する金属層除去工程を有する、請求項６に記載の金属充填微細構造体の製造方法。 The method for producing a metal-filled microstructure according to claim 6, further comprising a metal layer removing step of removing the metal layer formed on the surface of the structure after the holding step.
  8. 　前記金属層除去工程の後、前記酸化膜の前記表面を平滑化する表面平滑化処理工程を有する、請求項７に記載の金属充填微細構造体の製造方法。 The method for producing a metal-filled microstructure according to claim 7, further comprising a surface smoothing treatment step of smoothing the surface of the oxide film after the metal layer removing step.
  9. 　前記表面平滑化処理工程の平滑化は、化学的機械的研磨、ドライエッチング又は研削を用いる請求項８に記載の金属充填微細構造体の製造方法。 The method for producing a metal-filled microstructure according to claim 8, wherein the smoothing of the surface smoothing treatment step uses chemical mechanical polishing, dry etching, or grinding.
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