US20160138180A1 - Method for fabrication of anisotropic conductive member and method for fabrication of anisotropic conductive bonding package - Google Patents

Method for fabrication of anisotropic conductive member and method for fabrication of anisotropic conductive bonding package Download PDF

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US20160138180A1
US20160138180A1 US15/003,154 US201615003154A US2016138180A1 US 20160138180 A1 US20160138180 A1 US 20160138180A1 US 201615003154 A US201615003154 A US 201615003154A US 2016138180 A1 US2016138180 A1 US 2016138180A1
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anisotropic conductive
conductive member
fabrication
residual stress
stress relaxation
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Yusuke KOZAWA
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical 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
    • C25D1/00—Electroforming
    • C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • 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
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • 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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • 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
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to a method for fabrication of an anisotropic conductive member and a method for fabrication of an anisotropic conductive bonding package.
  • anisotropic conductive members since electrical connection between an electronic component such as a semiconductor element and a circuit board can be obtained simply by inserting an anisotropic conductive member between the electronic component and the circuit board and pressing the assembly, those anisotropic conductive members are widely used as electrical connection members for connecting electronic components such as semiconductor elements, or as inspection connectors for inspecting the functions of electronic components such as semiconductor elements.
  • JP2008-270158A discloses “an anisotropic conductive member in which plural conductive paths composed of conductive members are provided in an insulating matrix such that the plural conductive paths penetrate through the insulating matrix in the thickness direction of the insulating matrix in a state of being insulated from each other, and one end of each of the conductive paths is exposed at one of the surfaces of the insulating matrix, while the other end of each of the conductive paths is exposed at the other surface of the insulating matrix, the density of the conductive paths is 2,000,000 paths/mm 2 or more, and the insulating matrix is a structure formed from an anodic oxide film of an aluminum substrate having micropores.”
  • JP2011-202194A discloses “a method for fabricating a metal-filled microstructure (anisotropic conductive member), the method including a step of filling through-holes with a metal by an electrolytic plating treatment such that the virtual filling ratio of the metal (conductive paths) in the through-holes (micropores) is larger than 100%; and a step of removing, by a polishing treatment, the metal deposited on the surface of an insulating matrix by the electrolytic plating treatment, characterized in that the electrolytic plating treatment is carried out such that the difference between the average crystal grain diameter of the metal filling the interior of the through-holes and the average crystal grain diameter of the metal deposited on the surface of the insulating matrix becomes 20 nm or less.
  • the anisotropic conductive member of JP2008-270158A in regard to the production process, for example, when plural conductive paths are provided so as to penetrate through the insulating matrix, residual stress is accumulated in the interior, and there is a risk that as energy such as heat is added from the outside, the insulating matrix may become damaged. For this reason, for example, when a wiring for connecting an electronic component to the anisotropic conductive member is formed, there is a problem that damage (for example, cracking) occurs due to the heat applied at the time of wiring formation, and a decrease in the yield of packaged products is caused thereby.
  • damage for example, cracking
  • JP2011-202194A production of an anisotropic conductive member is carried out such that residual stress does not occur to a large extent.
  • the inventors of the present invention conducted a thorough investigation in order to achieve the object described above, and as a result, the inventors found that the damage of the insulating matrix is suppressed when a treatment of relaxing the residual stress is applied after conductive paths have been formed, thus completing the invention.
  • the invention provides a method for fabrication of an anisotropic conductive member and a method for fabrication of an anisotropic conductive bonding package with the following configurations.
  • a method for fabrication of an anisotropic conductive member including a residual stress relaxation step of obtaining an anisotropic conductive member that has been subjected to a treatment for relaxing residual stress, after fabricating an anisotropic conductive member having plural conductive paths, in which plural micropores of an insulating matrix formed from an anodic oxide film are filled with a conductive member.
  • a method for fabrication of an anisotropic conductive bonding package including a connection unit forming step of applying a conductive material on an anisotropic conductive member obtained by the method for fabrication of an anisotropic conductive member according to any one of (1) to (9), and thereby obtaining an anisotropic conductive bonding package having a connection unit connected to at least one of plural conductive paths.
  • a method for fabrication of an anisotropic conductive member which can suppress the damage of an insulating matrix, and a method for fabrication of an anisotropic conductive bonding package can be provided.
  • FIG. 1 is a simplified diagram illustrating an example of a suitable embodiment of an anisotropic conductive member, of which FIG. 1(A) is a front view diagram, while FIG. 1(B) is a cross-sectional diagram viewed from the cutting plane line Ib-Ib of FIG. 1(A) .
  • FIG. 2 is an explanatory diagram for a method of calculating the degree of ordering of micropores.
  • FIG. 3 is a cross-sectional diagram illustrating an example of the method for fabrication of an anisotropic conductive member of the invention.
  • FIG. 4 is a cross-sectional diagram illustrating an anisotropic conductive member that has been subjected to an electrodeposition treatment.
  • FIG. 5 is a diagram illustrating an example of an anisotropic conductive bonding package.
  • the anisotropic conductive member used in the residual stress relaxation step is an anisotropic conductive member having plural conductive paths, in which plural micropores of an insulating matrix formed from an anodic oxide film are filled with a conductive member.
  • FIG. 1 is a simplified diagram illustrating an example of a suitable embodiment of an anisotropic conductive member, of which FIG. 1(A) is a front view diagram, while FIG. 1(B) is a cross-sectional diagram viewed from the cutting plane line Ib-Ib of FIG. 1(A) .
  • the anisotropic conductive member 1 includes an insulating matrix 2 and plural conductive paths 3 composed of a conductive member.
  • the insulating matrix 2 has plural micropores 4 that penetrate therethrough in the thickness direction Z, and plural conductive paths 3 are filled in these plural micropores 4 .
  • the plural conductive paths 3 are provided in the plural micropores 4 at least from one surface to the other surface of the insulating matrix 2 ; however, as illustrated in FIG. 1(B) , it is preferable that the conductive paths are provided in the micropores 4 in a state such that one end of each of the conductive paths 3 protrudes from one surface 2 a of the insulating matrix 2 , while the other end of each of the conductive paths 3 protrudes from the other surface 2 b of the insulating matrix 2 . That is, it is preferable that the two ends of each of the conductive paths 3 have protrusions 3 a and 3 b , respectively, which protrude from the main surfaces 2 a and 2 b of the insulating matrix.
  • the insulating matrix constituting the anisotropic conductive member is a structure formed from an anodic oxide film of an aluminum substrate having micropores, and functions so as to maintain the insulating properties in the planar direction.
  • the thickness of the insulating matrix (total thicknesses of the part represented by Reference Numeral 6 in FIG. 1(B) ) is preferably in the range of 1 ⁇ m to 1,000 ⁇ m, more preferably in the range of 5 pin to 500 ⁇ m, and even more preferably in the range of 10 ⁇ m to 300 ⁇ m.
  • the thickness of the insulating matrix is 1 ⁇ m or more, handling of the insulating matrix is achieved satisfactorily, and when the thickness of the insulating matrix is 1,000 ⁇ m or less, residual stress can be easily relaxed in the method for fabrication of an anisotropic conductive member that will be described below.
  • the degree of ordering defined by the following Formula (i) for the micropores is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more.
  • A represents the total number of micropores in the measurement area.
  • B represents the number of micropores in the measurement area for one particular micropore, in which, when a circle that is inscribed to the edge of another micropore and has the smallest radius is drawn so as to be centered on the center of the particular micropore, the circle includes the centers of six micropores other than the particular micropore.
  • FIG. 2 is an explanatory diagram for a method of calculating the degree of ordering of micropores. Formula (1) above will be explained more specifically using FIG. 2 .
  • the micropore 101 illustrated in FIG. 2(A) when a circle 103 that is inscribed to the edge of another micropore and has the smallest radius (inscribed to a micropore 102 ) is drawn so as to be centered on the center of the micropore 101 , the circle 103 includes the centers of six micropores other than the micropore 101 . Therefore, the micropore 101 is included in B.
  • the micropore 104 illustrated in FIG. 2(B) when a circle 106 that is inscribed to the edge of another micropore and has the smallest radius (inscribed to a micropore 105 ) is drawn so as to be centered on the center of the micropore 104 , the circle 106 includes the centers of five micropores other than the micropore 104 . Therefore, the micropore 104 is not included in B.
  • the micropore 107 illustrated in FIG. 2(B) when a circle 109 that is inscribed to the edge of another micropore and has the smallest radius (inscribed to a micropore 108 ) is drawn so as to be centered on the center of the micropore 107 , the circle 109 includes the centers of seven micropores other than the micropore 107 . Therefore, the micropore 107 is not included in B.
  • the width between the conductive paths (part represented by Reference Numeral 7 in FIG. 1(B) ) in the insulating matrix is preferably 10 nm or more, and more preferably 20 nm to 200 nm.
  • the insulating matrix can function sufficiently as an insulating barrier wall.
  • the insulating matrix can be produced by, for example, anodizing an aluminum substrate, and making the micropores generated by anodization to penetrate through the aluminum substrate.
  • alumina that is used as the material of the anodic oxide film of aluminum has an electrical resistivity of about 10 14 ⁇ cm, similarly to the insulating matrices (for example, a thermoplastic elastomer) that constitute conventionally known anisotropic conductive films and the like.
  • the conductive paths that constitute the anisotropic conductive member are formed from a conductive member, and function as conductive paths that conduct electricity in the thickness direction of the insulating matrix.
  • the conductive member is not particularly limited as long as it is a material having an electrical resistivity of 10 3 ⁇ cm or less, and as specific examples thereof, gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and indium-doped tin oxide (ITO) may be mentioned as suitable examples.
  • end faces only the surfaces of the faces of the conductive paths exposed at or protruding from both surfaces of the insulating matrix (hereinafter, also referred to as “end faces”) are formed of gold.
  • the conductive paths have a pillar shape, and the diameter of the entirety of a conductive path (part represented by Reference Numeral 8 in FIG. 1(B) ) is preferably in the range of 5 nm to 500 nm, more preferably in the range of 20 nm to 400 nm, even more preferably in the range of 40 nm to 200 nm, and particularly preferably in the range of 50 nm to 100 nm.
  • the anisotropic conductive member can be used more suitably as an electrical connection member or an inspection connector for electronic components.
  • the thickness of the insulating matrix is 500 nm or less, residual stress can be easily relaxed in the residual stress relaxation step that will be described below.
  • the length of the center line of the conductive path with respect to the thickness of the insulating matrix is preferably 1.0 to 1.2, and more preferably 1.0 to 1.05.
  • the anisotropic conductive member can be used more suitably as an inspection connector or an electrical connection member for electronic components.
  • the height of the protrusions is preferably 10 nm to 100 nm, and more preferably 10 nm to 50 nm.
  • the height of the bumps is in this range, joinability of the anisotropic conductive member to an electrode (pad) part of an electronic component is enhanced.
  • the conductive paths exist in a state of being mutually insulated by the insulating matrix, and the density of the conductive paths is 2,000,000 paths/mm 2 or more, preferably 10,000,000 paths/mm 2 or more, more preferably 50,000,000 paths/mm 2 or more and even more preferably 100,000,000 paths/mm 2 or more.
  • the anisotropic conductive member can still be used as an inspection connector, an electrical connection member or the like for electronic components such as semiconductor elements, even at the present time when high integration has been further advanced.
  • the distance between the respective centers of adjacent conductive paths is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and even more preferably 50 nm to 140 nm.
  • the pitch is in this range, a balance between the diameter of a conductive path and the width between conductive paths (thickness of the insulating barrier wall) can be easily achieved.
  • the thickness of the insulating matrix is preferably 1 ⁇ m to 1,000 ⁇ m, and the diameter of the conductive path is preferably 5 nm to 500 nm.
  • the method for fabrication of an anisotropic conductive member of the invention is a method for fabrication of an anisotropic conductive member, the method including a residual stress relaxation step of fabricating the aforementioned anisotropic conductive member having plural conductive paths in which plural micropores of an insulating matrix formed from an anodic oxide film are filled with a conductive member, and then obtaining an anisotropic conductive member that has been subjected to a treatment for relaxing residual stress.
  • the method for fabrication of an anisotropic conductive member of the invention includes an anodization treatment step of anodizing an aluminum substrate; after the anodization treatment step, a penetration treatment step of making plural fine pores generated by the anodization to penetrate through the aluminum substrate, and thereby obtaining an insulating matrix having plural micropores; after the penetration treatment step, a conductive path forming step of filling the interior of the plural micropores in the insulating matrix thus obtained, with a conductive member, and forming plural conductive paths; and after the conductive path forming step, a residual stress relaxation step of obtaining an anisotropic conductive member that has been subjected to a treatment for relaxing residual stress.
  • the surface on which an anodic oxide film is provided by the anodization treatment step that will be described below preferably has an aluminum purity of 99.5% by mass or higher, more preferably 99.9% by mass or higher, and even more preferably 99.99% by mass or higher.
  • the aluminum purity is in the aforementioned range, sufficient regularity of the micropore arrangement is obtained.
  • the surface of the aluminum substrate on which the anodization treatment step that will be described below is carried out is subjected to a degreasing treatment and a mirror surface finishing treatment in advance.
  • the anodization step is a step of subjecting the aforementioned aluminum substrate to an anodization treatment, and thereby forming an oxide coating film having micropores on the surface of the aluminum substrate.
  • the anodization treatment according to the fabrication method of the invention can be carried out using a conventionally known method; however, from the viewpoint of increasing the regularity of the fine pore arrangement and more reliably securing the insulating properties of the conductive part in the planar direction, it is preferable to use a self-ordering method or a constant voltage treatment.
  • the penetration treatment step is a step of making plural fine pores generated by the anodization to penetrate the aluminum substrate, and thereby obtaining an insulating matrix having plural micropores, after the anodization treatment step.
  • the penetration treatment step include a method of dissolving an aluminum substrate after the anodization treatment step, and removing the bottom of the anodic oxide film; and a method of cutting the aluminum substrate and the anodic oxide film in the vicinity of the aluminum substrate, after the anodization treatment step.
  • JP2008-270158A for the penetration treatment step, for example, methods similar to the respective methods described in paragraphs “0110” to “0121” and [FIG. 3] and [FIG. 4] of JP2008-270158A may be used.
  • the metal to be filled is similar to the metal explained above in connection with the anisotropic conductive member.
  • an insulating matrix having plural micropores is obtained after the penetration treatment step; however, strictly speaking, the inner circumferential surfaces of these plural micropores are not extended in parallel to the thickness direction of the insulating matrix, and for example, the inner circumferential surface has a slightly non-uniform shape, such as a shape which is inclined slightly inward along the direction from one surface side toward the other surface side of the insulating matrix. Therefore, when conductive paths are formed inside the plural micropores by the conductive path forming step described above, the force generated between the inner circumferential surfaces of the plural microporcs and the outer circumferential surfaces of the conductive paths becomes non-uniform depending on the position.
  • the residual stress occurring due to this conductive path forming step is to be relaxed by the residual stress relaxation step that will be described below.
  • the fabrication method includes a surface smoothing treatment step of smothing the front surface and the back surface by a chemical mechanical polishing treatment or the like, after the conductive path forming step described above.
  • CMP Chemical Mechanical Polishing
  • CMP slurries such as PLANERLITE-7000 manufactured by Fujimi, Incoporated., GPX HSC800 manufactured by Hitachi Chemical Co., Ltd., and CL-1000 manufactured by Asahi Glass (Seimi Chemical) Co., Ltd., can be used.
  • the fabrication method of the invention in a case in which the conductive path forming step or the CMP treatment has been applied, it is preferable that the fabrication method includes a trimming treatment step after the surface smoothing treatment step.
  • the trimming treatment step is a step in which, when the conductive path forming step or the CMP treatment has been applied, only the insulating matrix at the surface of the anisotropic conductive member is partially removed, and the conductive paths are caused to protrude, after the surface smoothing treatment step.
  • the trimming treatment can be carried out by bringing the insulating matrix into contact with the aqueous acid solution or aqueous alkali solution used at the time of removing the bottom of the anodic oxide film described above, for example, by a dipping method and a spraying method.
  • the trimming treatment it is preferable to use phosphoric acid for which the dissolution rate can be easily managed.
  • the insulating matrix 2 having plural conductive paths 3 illustrated in FIG. 3(C) is obtained.
  • the aforementioned residual stress relaxation step is a step of applying a treatment for relaxing residual stress and thereby obtaining the anisotropic conductive member described above, after the conductive path forming step.
  • the treatment for relaxing residual stress refers to a treatment for reducing the residual stress of the insulating matrix down to 200 MPa or less.
  • the residual stress relaxation step it is preferable to relax residual stress by applying a treatment for dispersing the force generated between the inner circumferential surfaces of the plural micropores and the outer circumferential surfaces of the plural conductive paths.
  • the force generated between the inner circumferential surfaces of plural micropores and the outer circumferential surfaces of the conductive paths can be dispersed by baking the insulating matrix having plural conductive paths.
  • baking is performed at 50° C. to 600° C., more preferably at 100° C. to 550° C., and even more preferably at 150° C. to 400° C.
  • the baking temperature is 50° C. or higher, residual stress can be decreased, and when the baking temperature is 600° C. or lower, normal parts being largely deformed by excessive heating can be suppressed.
  • the insulating matrix is baked while a load is applied on at least any one of one surface and the other surface of the insulating substrate.
  • the load is applied onto at least any one of one surface and the other surface of the insulating matrix at a pressure of 50 g/cm 2 to 2,000 g/cm 2 , from the viewpoints of handleability, adhesiveness to the insulating matrix at the time of load application, and durability of the insulating matrix.
  • the baking temperature it is preferable that baking is performed at 50° C. to 600° C., more preferably at 100° C. to 550° C., and even more preferably at 150° C. to 400° C., similarly to the case of the baking temperature described above.
  • the residual stress is preferable to decrease the residual stress to 180 MPa or less, and more preferably to 165 MPa or less, by baking the insulating matrix while applying a load to at least any one of one surface and the other surface of the insulating matrix.
  • a load is applied to a flat-shaped pressing unit 20 against one surface 2 a of the insulating matrix 2 having plural conductive paths 3 obtained by the trimming step described above. At this time, it is preferable to add a load until the strain of the insulating matrix 2 generated by residual stress is completely restored.
  • the baking in the residual stress relaxation step can be performed in air, in a vacuum, in a nitrogen atmosphere, in an argon atmosphere, or the like, and particularly, from the viewpoint of preventing the metal that constitutes the conductive paths from being oxidized and gaining high resistance, it is preferable to perform baking in a vacuum, in a nitrogen atmosphere, or in an argon atmosphere.
  • a treatment of dispersing the force generated between the inner circumferential surfaces of the plural micropores and the outer circumferential surfaces of the plural conductive paths by applying ultrasonic vibration while immersing the insulating matrix in a liquid may also be carried out.
  • the liquid in which the insulating matrix having plural conductive paths is immersed for example, water, an aqueous solution, or a liquid organic compound is used, and it is preferable to use a liquid organic compound such as isopropyl alcohol (IPA) or methyl ethyl ketone (MEK).
  • IPA isopropyl alcohol
  • MEK methyl ethyl ketone
  • the ultrasonic vibration at a frequency of 20 kHz to 100 kHz.
  • the ultrasonic vibration is applied at 20 kHz or more, the residual stress can be decreased to a large extent, and when the ultrasonic vibration is applied at 100 kHz or less, normal parts and the like being damaged due to excess vibration can be suppressed.
  • the ultrasonic vibration for 10 minutes or longer, more preferably for 100 minutes or longer, and even more preferably for 150 minutes or longer.
  • the ultrasonic vibration is applied for 10 minutes or longer, the residual stress can be decreased to a large extent.
  • anisotropic conductive member having relaxed residual stress is obtained.
  • This anisotropic conductive member has the same configuration as that explained in connection with the anisotropic conductive member described above.
  • the fabrication method of the invention may be a fabrication method including, instead of the trimming treatment step or after the trimming treatment step, an electrodeposition treatment step of further precipitating the same or different conductive metal only on the surfaces of the conductive paths 3 illustrated in FIG. 3(B) ( FIG. 4 ).
  • an electrodeposition treatment is a treatment including an electroless plating treatment which utilizes the difference of the electronegativities of different kinds of metals.
  • an electroless plating treatment is a step of immersing an object in an electroless plating treatment liquid (for example, a liquid obtained by appropriately mixing a reducing agent treatment liquid having a pH of 6 to 13 with a noble metal-containing treatment liquid having a pH of 1 to 9).
  • an electroless plating treatment liquid for example, a liquid obtained by appropriately mixing a reducing agent treatment liquid having a pH of 6 to 13 with a noble metal-containing treatment liquid having a pH of 1 to 9).
  • the trimming treatment and the electrodeposition treatment are applied immediately before the use of the anisotropic conductive member.
  • these treatments are applied immediately before use, it is preferable because the metal of the conductive paths that constitute the bump parts is not oxidized until immediately before use.
  • An anisotropic conductive bonding package fabricated by the method for fabrication of an anisotropic conductive bonding package of the invention is a package having the anisotropic conductive member described above, and a connection unit formed from a conductive material, which is electrically connected to at least one of the plural conductive paths.
  • FIG. 5(A) is a schematic perspective view diagram illustrating an example of a suitable embodiment of a multi-chip module 11 which utilizes an anisotropic conductive bonding package 10 .
  • FIG. 5(B) is a diagram illustrating an anisotropic conductive bonding package 10 picked out from the multi-chip module 11 of FIG. 5(A) .
  • the multi-chip module 11 of FIG. 5(A) is a device mounted on a circuit board and intended for achieving electric connection, and includes a base (chip) substrate 12 , two IC chips 13 , and an interposer 14 connected to the anisotropic conductive bonding package 10 .
  • the chip substrate 12 is composed of a printed wiring board, and an electrode, which is not shown in the diagram, in the printed wiring board is electrically connected to the IC chips 13 by a wiring which is not shown in the diagram.
  • the anisotropic conductive bonding package 10 is disposed on the chip substrate 12 , and the ends of the conductive paths 3 exposed at one surface 2 a of the insulating matrix 2 of the anisotropic conductive member 1 are connected to a flat-shaped electrode 15 a (connection unit), while the other ends of the conductive paths 3 exposed at the other surface 2 b of the insulating matrix 2 are connected to a flat-shaped electrode 15 b (connection unit).
  • the electrode 15 a is connected to an internal wiring inside the interposer 14
  • the electrode 15 b is connected to the IC chips 13 via a wiring, which is not shown in the diagram, of the chip substrate 12 .
  • the electrode 15 a and the electrode 15 b can be easily connected in the thickness direction via the anisotropic conductive member 1 , and the interposer 14 and the like can be disposed by lamination.
  • the anisotropic conductive bonding package 10 may have a multilayer structure in which connection units formed from a conductive material and anisotropic conductive members are alternately laminated in the thickness direction, and thereby, heat dissipation performance can be enhanced, and reliability of the device can be enhanced.
  • the method for fabrication of an anisotropic conductive bonding package of the invention is a method for fabrication of an anisotropic conductive bonding package, which includes a connection unit forming step of applying a conductive material on an anisotropic conductive member obtainable by the fabrication method described above, and thereby obtaining an anisotropic conductive bonding package having a connection unit connected to at least one of the plural conductive paths.
  • any one kind of material or two or more kinds of materials selected from gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), ITO, molybdenum (Mo), iron (Fe), palladium (Pd), beryllium (Be), and rhenium (Re) can be used.
  • the bonding mode is not particularly limited; however, from the viewpoint of having high conduction reliability at the time of bonding, compressive bonding is preferable, and heated compressive bonding is more preferable. Furthermore, ultrasonic bonding is also preferable.
  • connection unit is, for example, an electrode
  • the electrode may be any electrode formed on any member.
  • the electrode is preferably an electrode which is bonded to one surface and the other surface of the anisotropic conductive member described above, and is further connected to an internal wiring inside the interposer.
  • the interposer is also referred to as a conversion board or a re-wiring board, and the arrangement of the electrodes can be arbitrarily designed depending on the arrangement of an external electrode connected to the surface of the interposer via an internal wiring inside the substrate.
  • the members of the interposer other than electrodes can be produced from inorganic compounds such as a silicon wafer or a GaN substrate; and various plastics such as a glass fiber-impregnated epoxy resin and a polyimide resin.
  • the interposer may be bonded to one surface of the anisotropic conductive bonding package described above; however, it is preferable that the interposer is bonded as two layers such as an upper layer and a lower layer, sandwiching the anisotropic conductive bonding package as an intermediate layer.
  • a high-purity aluminum substrate (manufactured by Sumitomo Light Metal Industries, Ltd., purity: 99.99% by mass, thickness: 0.4 mm) was cut to an area which measured 10 cm on each of four sides so that the aluminum substrate could be anodization treated, and the cut 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 25 V, a liquid temperature of 65° C., and a liquid flow rate of 3.0 m/min.
  • a carbon electrode was used as a negative electrode, and GP0110-30R (manufactured by Takasago, Ltd.) was used as a power supply. Furthermore, the flow rate of the liquid electrolyte was measured using a vortex flow monitor, FLM22-10PCW (manufactured by As One Corporation.).
  • the aluminum substrate that had been electrolytic polishing-treated was subjected to an anodization treatment based on a self-ordering method according to the procedure described in JP2007-204802A.
  • the aluminum substrate that had been electrolytic polishing-treated was subjected to a preliminary anodization treatment for five hours using a 0.50 mol/L liquid electrolyte of oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 15° C., and a liquid flow rate of 3.0 m/min.
  • the aluminum substrate that had been preliminary anodization-treated was subjected to a film-removing treatment of immersing the aluminum substrate in a mixed aqueous solution of 0.2 mol/L anhydrous chromic acid and 0.6 mol/L phosphoric acid (liquid temperature: 50° C.) for 12 hours.
  • the aluminum substrate was subjected to a re-anodization treatment for 10 hours using a 0.50 mol/L liquid electrolyte of oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 15° C., and a liquid flow rate of 3.0 m/min, and thus an oxide coating film having a film thickness of 80 ⁇ m was obtained.
  • both the preliminary anodization treatment and the re-anodization treatment were carried out using a stainless steel electrode as a negative electrode, and GP0110-30R (manufactured by Takasago, Ltd.) as a power supply. Furthermore, NcoCool BD36 (manufactured by Yamato Scientific Co., Ltd.) was used as a cooling apparatus, and PAIRSTIRRER PS-100 (manufactured by Eyela Tokyo Rikakikai Co., Ltd.) was used as a stirring and heating apparatus. Also, the flow rate of the liquid electrolyte was measured using a vortex flow monitor, FLM22-10PCW (manufactured by As One Corporation.).
  • the aluminum substrate was dissolved in a 20 mass % aqueous solution of mercury chloride (mercuric chloride) by immersing the aluminum substrate in the aqueous solution at 20° C. for three hours, and the bottom of the anodic oxide film was removed by immersing the aluminum substrate in 5 mass % phosphoric acid at 30° C. for 30 minutes.
  • mercury chloride mercuric chloride
  • the structure obtained as described above was subjected to a heating treatment at a temperature of 400° C. for one hour.
  • the structure was subjected to a treatment for forming an electrode film on one surface of the oxide coating film after the heating treatment.
  • a 0.7 g/L aqueous solution of chloroauric acid was applied on one surface and dried at a rate of 140° C./min, and a baking treatment was carried out at a rate of 500° C./hour.
  • a gold plating core was produced.
  • the structure was subjected to an immersion treatment at 50° C./hour using PRECIOUSFAB ACG2000 base liquid/reducing liquid (manufactured by Electroplating Engineers of Japan, Ltd.) as an electroless plating liquid, and thus a poreless electrode film was formed.
  • PRECIOUSFAB ACG2000 base liquid/reducing liquid manufactured by Electroplating Engineers of Japan, Ltd.
  • a copper electrode was closely adhered to the surface on which the electrode film had been formed, and the structure was subjected to an electrolytic plating treatment using the copper electrode as a negative electrode and platinum as a positive electrode.
  • the constant-voltage pulse electrolysis was performed using a plating apparatus manufactured by Yamamoto-MS Co., Ltd., using a power supply (HZ-3000) manufactured by Hokuto Denko Corp., by performing cyclic voltammetry in a plating liquid to check the precipitation potential, and then setting the potential on the coating film side to ⁇ 2 V. Furthermore, the pulse waveform of the constant-voltage pulse electrolysis was a square waveform. Specifically, an electrolysis treatment with a cycle of 60 seconds for one electrolysis time was carried out five times so that the total treatment time of electrolysis would be 300 seconds, while a resting time of 40 seconds was provided between each electrolysis treatment cycle.
  • the electrode film formed on the oxide coating film was removed by polishing the structure having a film thickness of 80 pun, up to 15 ⁇ m each from both surfaces, and the front surface and the back surface of the oxide coating film were smoothed.
  • a structure having a film thickness of 50 ⁇ m was obtained.
  • PLANERLITE-7000 manufactured by Fujimi, Incorporated. was used as the CMP slurry.
  • the surface of the structure was observed by FE-SEM, and the surface had a form in which the filling metal partially overflowed from the surface of the oxide coating film.
  • the structure that had been CMP-treated was immersed in a phosphoric acid solution, the anodic oxide film was selectively dissolved therein, and thereby pillars of the filling metal filling the micropores were caused to protrude.
  • a structure was obtained.
  • the phosphoric acid solution the same liquid as that used for the penetration treatment was used, and the treatment time was set to 5 minutes.
  • the structure that had been trimming-treated was subjected to baking for 45 minutes at a temperature of 210° C. while a load of 50 g/cm 2 was added thereto in an open-air environment, and thus an anisotropic conductive member was obtained.
  • the anisotropic conductive member obtained after the residual stress relaxation step was subjected to a thermal compression test using a thermal compression apparatus (manufactured by Kitagawa Seiki Co., Ltd., HVHC-PRESS, cylinder area: 201 cm 2 ). Copper was used as a conductive material, and thermal compression was carried out under the conditions of a compression temperature of 240° C., a compression pressure per unit area of the electrode of 50 MPa or less, and a compression time of one minute. Thereby, an anisotropic conductive bonding package was fabricated.
  • Anisotropic conductive members and anisotropic conductive bonding packages were fabricated in the same manner as in Example 1, except that the baking temperature and the baking atmosphere were modified according to Table 1.
  • An anisotropic conductive member was fabricated in the same manner as in Example 1, except that the conductive path forming step was carried out by the method described below. Furthermore, an anisotropic conductive bonding package was fabricated in the same manner as in Example 1, except that the conductive material used in the packaging step was changed to nickel.
  • Anisotropic conductive members and anisotropic conductive bonding packages were fabricated in the same manner as in Example 17, except that the baking temperature and the baking atmosphere were changed according to Table 1.
  • Anisotropic conductive members were fabricated in the same manner as in Example 1, except that the residual stress relaxation step was carried out by the method described below.
  • Anisotropic conductive members and anisotropic conductive bonding packages were fabricated by applying, after the trimming treatment, ultrasonic vibration at a frequency of about 20 kHz to 100 kHz in an isopropyl alcohol (IPA) solution for 150 minutes, 100 minutes, and 10 minutes, respectively.
  • IPA isopropyl alcohol
  • Anisotropic conductive members and anisotropic conductive bonding packages were fabricated in the same manner as in Example 17, except that the residual stress relaxation step was carried out by the method described below.
  • Anisotropic conductive members were fabricated by applying, after the trimming treatment, ultrasonic vibration at a frequency of about 20 kHz to 100 kHz in an isopropyl alcohol (IPA) solution for 150 minutes, 100 minutes, and 10 minutes, respectively.
  • IPA isopropyl alcohol
  • An anisotropic conductive member and an anisotropic conductive bonding package were fabricated in the same manner as in Example 13, except that baking was carried out without applying a load in the residual stress relaxation step.
  • An anisotropic conductive member and an anisotropic conductive bonding package were fabricated in the same manner as in Example 16, except that baking was carried out without applying a load in the residual stress relaxation step.
  • An anisotropic conductive member and an anisotropic conductive bonding package were fabricated in the same manner as in Example 21, except that baking was carried out without applying a load in the residual stress relaxation step.
  • An anisotropic conductive member and an anisotropic conductive bonding package were fabricated in the same manner as in Example 24, except that baking was carried out without applying a load in the residual stress relaxation step.
  • An anisotropic conductive member and an anisotropic conductive bonding package were fabricated in the same manner as in Example 1, except that the residual stress relaxation step was excluded.
  • An anisotropic conductive member and an anisotropic conductive bonding package were fabricated in the same manner as in Example 17, except that the residual stress relaxation step was excluded.
  • the residual stress was calculated by the 2 ⁇ sin 2 ⁇ method using an X-ray diffraction apparatus (XRD, manufactured by Bruker BioSpin K.K., D8 Discover with GADDS). Measurement was made under the conditions of voltage/current of 45 kV/110 mA, CrK ⁇ line for the X-ray wavelength, and an X-ray irradiation diameter of 500 ⁇ m, and using Cu (311) surface or Ni (311) surface as the evaluation crystal plane.
  • XRD X-ray diffraction apparatus
  • the residual stress decreased down to 180 MPa or less independently of the metal species of the conductive path, and it was found that relaxation of the residual stress is not disrupted even if any metal between copper and nickel is used in the conductive path.

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