WO2021176847A1 - Procédé de fabrication d'une microstructure remplie de métal - Google Patents

Procédé de fabrication d'une microstructure remplie de métal 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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Prior art keywords
metal
oxide film
anodic oxide
filled
filled microstructure
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PCT/JP2021/000672
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English (en)
Japanese (ja)
Inventor
堀田　吉則
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富士フイルム株式会社
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Priority to CN202180017274.XA priority Critical patent/CN115210410A/zh
Priority to JP2022505007A priority patent/JP7336584B2/ja
Publication of WO2021176847A1 publication Critical patent/WO2021176847A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une microstructure remplie de métal qui présente une excellente stabilité au transport et empêche la détérioration des performances d'isolation. Le procédé de fabrication d'une microstructure remplie de métal comprend : une étape de formation dans laquelle un film d'oxyde comprenant une pluralité de micropores est formé dans une région de formation entourée par une partie de cadre disposée sur le bord externe d'un élément de métal de valve, pour obtenir ainsi une structure comprenant l'élément de métal de valve et le film d'oxyde; une étape de remplissage dans laquelle la structure est remplie d'un métal dans la pluralité de micropores du film d'oxyde; et une étape de maintien dans laquelle un élément rempli de métal obtenu dans l'étape de remplissage par remplissage de la structure avec un métal dans la pluralité de micropores du film d'oxyde est laissé pendant au moins 24 heures dans un environnement ayant une humidité relative de 10 à 30 %. La pluralité de micropores a un diamètre moyen inférieur ou égal à 1 µm.
PCT/JP2021/000672 2020-03-06 2021-01-12 Procédé de fabrication d'une microstructure remplie de métal WO2021176847A1 (fr)

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Cited By (1)

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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010033939A (ja) * 2008-07-30 2010-02-12 Murata Mfg Co Ltd イオン伝導膜、イオン伝導膜の製造方法、燃料電池および水素センサ
WO2015029881A1 (fr) * 2013-08-30 2015-03-05 富士フイルム株式会社 Procédé de fabrication d'une microstructure remplie de métal
WO2016009649A1 (fr) * 2014-07-18 2016-01-21 株式会社Uacj Matériau à base d'aluminium traité en surface et son procédé de fabrication ainsi que ledit matériau à base d'aluminium traité en surface/matériau collé à une couche de résine
WO2018037805A1 (fr) * 2016-08-24 2018-03-01 富士フイルム株式会社 Procédé de stockage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010033939A (ja) * 2008-07-30 2010-02-12 Murata Mfg Co Ltd イオン伝導膜、イオン伝導膜の製造方法、燃料電池および水素センサ
WO2015029881A1 (fr) * 2013-08-30 2015-03-05 富士フイルム株式会社 Procédé de fabrication d'une microstructure remplie de métal
WO2016009649A1 (fr) * 2014-07-18 2016-01-21 株式会社Uacj Matériau à base d'aluminium traité en surface et son procédé de fabrication ainsi que ledit matériau à base d'aluminium traité en surface/matériau collé à une couche de résine
WO2018037805A1 (fr) * 2016-08-24 2018-03-01 富士フイルム株式会社 Procédé de stockage

Cited By (2)

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

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JP7336584B2 (ja) 2023-08-31

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