WO2009022438A1 - Electrode and method for manufacturing the same, lead wiring using the electrode and method for connecting the same, and related electronic components and electronic equipment - Google Patents

Electrode and method for manufacturing the same, lead wiring using the electrode and method for connecting the same, and related electronic components and electronic equipment Download PDF

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Publication number
WO2009022438A1
WO2009022438A1 PCT/JP2007/066326 JP2007066326W WO2009022438A1 WO 2009022438 A1 WO2009022438 A1 WO 2009022438A1 JP 2007066326 W JP2007066326 W JP 2007066326W WO 2009022438 A1 WO2009022438 A1 WO 2009022438A1
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Prior art keywords
conductive fine
organic coating
wiring
fine particles
electrode
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PCT/JP2007/066326
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French (fr)
Inventor
Kazufumi Ogawa
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Kazufumi Ogawa
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Priority to PCT/JP2007/066326 priority Critical patent/WO2009022438A1/en
Publication of WO2009022438A1 publication Critical patent/WO2009022438A1/en

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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/102Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by bonding of conductive powder, i.e. metallic powder
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10Bump connectors ; Manufacturing methods related thereto
    • H01L24/11Manufacturing methods
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10Bump connectors ; Manufacturing methods related thereto
    • H01L24/12Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10Bump connectors; Manufacturing methods related thereto
    • H01L2224/12Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001Core members of the bump connector
    • H01L2224/13099Material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/482Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
    • H01L23/4827Materials
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    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/85Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
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    • H01L2924/00014Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
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    • H01L2924/01Chemical elements
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    • H01L2924/01029Copper [Cu]
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    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01Chemical elements
    • H01L2924/01082Lead [Pb]
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203Fillers and particles
    • H05K2201/0242Shape of an individual particle
    • H05K2201/0257Nanoparticles
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12Using specific substances
    • H05K2203/122Organic non-polymeric compounds, e.g. oil, wax, thiol

Definitions

  • the present invention is related to an electrode used for electronic equipment, electronic devices, or printed boards, and the method for manufacturing the same, and a lead wiring using the electrode and the method for connecting the same.
  • it relates to an electrode using a monostratal film of conductive fine particles or a laminated body of conductive fine particles comprising conductive fine particles that are given either thermal reactivity or light reactivity, or otherwise radical reactivity or ionic reactivity, to the surface, and the method for manufacturing the same.
  • It also relates to a lead wiring using the electrode and the method for connecting the same, and related electronic components and electronic equipment.
  • conductive fine particle includes fine metal particles made of gold, silver, copper, and nickel, or silver-plated precious metal, copper, and nickel. In addition, it also includes fine metal oxide particles, such as ITO and SnO 2 .
  • the present invention aims to provide an electrode using a film coating (a patterned monostratal conductive fine particle film) with an even thickness at the particle size level by selectively arranging conductive fine particles only in one layer on the surface of the end of any wiring, or an electrode using a film coating (a patterned laminated body of conductive fine particle films) by selectively accumulating two or more layers of films of conductive fine particles arranged only in one layer, wherein conductive fine particles are used without losing the original function of the conductive fine particles while giving a new function, and the method for manufacturing the same.
  • the present invention also aims to provide a lead wiring using the electrode and the method for connecting the same.
  • the first aspect of this invention is an electrode, wherein a selectively formed monostratal conductive fine particle film is covalently bound to the surface of the end of the wiring or the end of the lead wire via a first organic coating selectively formed on the surface of the end of the wiring or the end of the lead wire and a second organic coating formed on the surface of the conductive fine particles.
  • the second aspect of this invention is the electrode of the first aspect of this invention, wherein the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particles are different from each other.
  • the third aspect of this invention is the electrode of the first aspect of this invention, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
  • the fourth aspect of this invention is the electrode of the first and the second aspects of this invention, wherein the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particles comprise a monomolecular film.
  • the fifth aspect of this invention is a method for manufacturing an electrode comprising a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent
  • the sixth aspect of this invention is the method for manufacturing an electrode in the fifth aspect of this invention comprising a process of forming the first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alk
  • the seventh aspect of this invention is the method for manufacturing an electrode in the fifth aspect of this invention, wherein the first reactive organic coating comprises an epoxy group, and the second reactive organic coating comprises an imino group.
  • the eighth aspect of this invention is the method for manufacturing an electrode in the sixth aspect of this invention, wherein the first reactive monomolecular film comprises an epoxy group, and the second reactive monomolecular film comprises an imino group.
  • the ninth aspect of this invention is an electrode, wherein the conductive fine particles selectively accumulated in layers on the surface of the end of the wiring or the surface of the end of a lead wire are covalently bound to each other between layers via the organic coating formed on the surface of the conductive fine particles.
  • the tenth aspect of this invention is the electrode of the ninth aspect of this invention, wherein the organic coatings formed on the surface of the conductive fine particles comprise two types, and the conductive fine particles with the formation of the first organic coating and the conductive fine particles with the formation of the second organic coating are alternately laminated.
  • the eleventh aspect of this invention is the electrode of the tenth aspect of this invention, wherein the first organic coating and the second organic coating react with each other to form a covalent bond.
  • the twelfth aspect of this invention is the electrode of the ninth aspect of this invention, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
  • the thirteenth aspect of this invention is a method for manufacturing an electrode comprising a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting at least the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the first conductive fine particle by dispersing the first conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent
  • the fourteenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein the first reactive organic coating and the third reactive organic coating are made of the same materials.
  • the fifteenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein after the process of forming the second patterned monostratal conductive fine particle film, repetitively performing the process of forming the first patterned monostratal conductive fine particle film and the process of forming the second patterned monostratal conductive fine particle film in the same way.
  • the sixteenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein after the process of forming the first, second, and third reactive organic coatings, the surfaces of the base material or conductive fine particles are cleaned with an organic solvent to form the first, second, and third reactive monomolecular films that are covalently bound with the surface of the base material or conductive fine particles, respectively.
  • the seventeenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein the first and the third reactive organic coatings comprise an epoxy group, and the second reactive organic coating comprises an imino group.
  • the eighteenth aspect of this invention is the method for manufacturing an electrode in the fifth and the thirteenth aspects of this invention, wherein a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst.
  • the nineteenth aspect of this invention is the method for manufacturing an electrode in the fifth and the thirteenth aspects of this invention, wherein at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst for use.
  • at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst for use.
  • the twentieth aspect of this invention is a lead wiring, wherein the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first organic coating formed on the surface of the end of the wiring, a second organic coating formed on the surface of the conductive fine particles, and a third organic coating formed on the surface of the lead wire.
  • the twenty-first aspect of this invention is a lead wiring, wherein the conductive fine particles are formed in one layer or in multiple layers.
  • the twenty-second aspect of this invention is the lead wiring of the twentieth aspect of this invention, wherein the first organic coating and the third organic coating are covalently bound to each other directly or indirectly via the second organic coating formed on the surface of the conductive fine particles.
  • the twenty-third aspect of this invention is the lead wiring of the twenty-first aspect of this invention, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
  • the twenty-fourth aspect of this invention is the lead wiring of the twentieth, twenty-first, twenty-second, and twenty-third aspects of this invention, wherein the first organic coating, the second organic coating, and the third organic coating comprise a monomolecular film.
  • the twenty-fifth aspect of this invention is a method for connecting a lead wiring comprising a process of forming a first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming a third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of
  • the twenty-sixth aspect of this invention is the method for connecting a lead wiring in the twenty-fifth aspect of this invention, wherein the layer of the conductive fine particles is formed in multiple layers.
  • the twenty-seventh aspect of this invention is the method for connecting a lead wiring in the twenty-fifth aspect of this invention, wherein the conductive fine particles covered by the second and the fourth reactive organic coatings, respectively, are contacted to the top surface of the end of the wiring and the end of the lead wire on which the patterned first and third reactive organic coatings are formed to selectively react with each other, forming a layer of the conductive fine particles covered by the second and the fourth reactive organic coatings on the respective top surfaces.
  • the twenty-eighth aspect of this invention is the method for connecting a lead wiring in the twenty-seventh aspect of this invention, wherein the second and the fourth reactive organic coatings comprise a functional group that reacts with each other.
  • the twenty-ninth aspect of this invention is an electronic component using the electrode of the first through fourth aspects of this invention, inclusive, the electrode of the ninth through twelfth aspects of this invention, inclusive, and the lead wiring of the twentieth through twenty-fourth aspects of this invention, inclusive.
  • the thirtieth aspect of this invention is electronic equipment using the electrode of the first through fourth aspects of this invention, inclusive, the electrode of the ninth through twelfth aspects of this invention, inclusive, and the lead wiring of the twentieth through twenty-fourth aspects of this invention, inclusive.
  • the gist of the present invention manufactures and provides an electrode in which a selectively formed monostratal conductive fine particle film is covalently bound to the surface of the end of the wiring or the end of the lead wire via a first organic coating selectively formed on the surface of the end of the wiring or the end of the lead wire and a second organic coating formed on the surface of the conductive fine particles through a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first reactive
  • a process of forming the first reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane
  • the first reactive organic coating or monomolecular film comprises an epoxy group and the second reactive organic coating comprises an imino group, it is advantageous for generating a strong covalent bond.
  • the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particle comprise a functional group that reacts with each other for a covalent bond, it is advantageous for improving the strength of the electrode. Furthermore, it is advantageous for increasing the stability of the electrode, if the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group.
  • the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particle comprise a monomolecular film, it is advantageous for creating an electrode that is excellent in conductivity.
  • the gist of the present invention also manufactures and provides an electrode in which the conductive fine particles selectively accumulated in layers on the surface of the end of the wiring or the surface of the end of a lead wire are covalently bound to each other between layers via the organic coating formed on the surface of the conductive fine particles through: a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting at least the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the first
  • the first reactive organic coating and the third reactive organic coating are made of the same substance, it is advantageous for reducing the production cost of the electrode.
  • the process of forming the second patterned monostratal conductive fine particle film if repetitively performing the process of forming the first patterned monostratal conductive fine particle film and the process of forming the second patterned monostratal conductive fine particle film in the same way, a larger protrusion can be formed for the electrode; thus it is advantageous for connecting an external lead wire. Furthermore, after the process of forming the first, second, and third reactive organic coatings, if the surface of the base material or conductive fine particles are cleaned with an organic solvent to form the first, second, and third reactive monomolecular films that are covalently bound to the surface of the base material or conductive fine particles, respectively, it is advantageous for increasing the conductivity of the electrode.
  • first and the third reactive organic coatings comprise an epoxy group and the second reactive organic coating comprises an imino group, it is advantageous for manufacturing an electrode with a high stability. If a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst, it is advantageous for improving the efficiency of the creation of the organic coatings.
  • At least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst, it is advantageous for improving the efficiency of the creation of the organic coatings.
  • the organic coatings formed on the surface of the conductive fine particles are prepared in two types, and the conductive fine particles with the formation of the first organic coating and the conductive fine particles with the formation of the second organic coating are alternately laminated. Furthermore, it is advantageous for improving the strength of the electrode, if the first organic coating and the second organic coating react with each other to form a covalent bond, such as an N-C bond formed by a reaction between an epoxy group and an imino group.
  • the gist of the present invention also manufactures and provides a lead wiring in which the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first organic coating formed on the surface of the end of the wiring, a second organic coating formed on the surface of the conductive fine particles, and a third organic coating formed on the surface of the lead wire through: a process of forming the first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the lead
  • the layer of the conductive fine particles is formed in multiple layers, it is advantageous for eliminating steps on the substrate.
  • it is advantageous for connecting the wiring and the lead wire if the conductive fine particles covered by the second and the fourth reactive organic coatings, respectively, are contacted to the top surface of the end of the wiring and the end of the lead wire on which the patterned first and third reactive organic coatings are formed to selectively react with each other to form a layer of the conductive fine particles covered by the second and the fourth reactive organic coatings on the respective top surfaces, and these second and fourth reactive organic coatings comprise a functional group that reacts with each other.
  • the conductive fine particles are formed in one layer or in multiple layers, a highly reliable lead wiring can be obtained. Furthermore, it is advantageous for forming a highly reliable lead wiring, if the first organic coating and the third organic coating form an N-C covalent bond with each other by a reaction of an epoxy group and an imino group, directly or indirectly, via the second organic coating formed on the surface of the conductive fine particles.
  • the first organic coating, the second organic coating, and the third organic coating comprise a monomolecular film, it is advantageous for forming a lead wiring with a low contact resistance.
  • the present invention has the particular effect of providing an electrode using a film coating with an even thickness at the particle size level by selectively arranging conductive fine particles only in one layer on the end of the wiring on the surface of any circuit substrate or the surface of the end of a lead wiring, or an electrode using a film coating by selectively accumulating two or more layers of films of conductive fine particles arranged only in one layer, wherein the conductive fine particles are used without losing the original function of the conductive fine particles while giving a new function; and providing the method for manufacturing the same at a low cost.
  • the present invention also has the particular effect of providing a lead wiring with a high density using the electrode and the method for connecting the lead wiring at a low cost.
  • FIG. 1 contains conceptual diagrams of the first example of the present invention, which diagrams expand the reaction of the surface of the end of the wiring to the molecular level.
  • Fig. 1A shows the surface before the reaction.
  • Fig. 1B shows the surface after a monomolecular film containing an epoxy group is formed.
  • Fig. 1C shows the surface after a monomolecular film containing an amino group is formed.
  • Fig. 2 contains conceptual diagrams of the second example of the present invention, which diagrams expand the reaction of the surface of the conductive fine silver particle to the molecular level.
  • Fig. 2A shows the surface of the conductive fine silver particle before the reaction.
  • Fig. 2B shows the surface after a monomolecular film containing an epoxy group is formed.
  • Fig. 2C shows the surface after a monomolecular film containing an amino group is formed.
  • Fig. 3 contains conceptual diagrams of the third and fourth examples of the present invention, which diagrams expand the reaction of the surface of the end of the wiring to the molecular level.
  • Fig. 3A shows the surface of the end of the wiring on which a patterned monostratal conductive fine silver particle film is formed as an electrode.
  • Fig. 3B shows the surface of the end of the wiring on which two layers of the patterned monostratal conductive fine silver particle films are formed as an electrode.
  • Fig. 4 contains conceptual diagrams of the fifth example of the present invention, which diagrams enlarge the connection part of the end of the wiring of an electronic device and a lead wire via the electrode.
  • the present invention is to manufacture and provide a lead wiring in which the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first reactive organic coating formed on the surface of the end of the wiring, a second reactive organic coating formed on the surface of the conductive fine particles, and a third reactive organic coating formed on the surface of the lead wire through: a process of forming the first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the
  • the present invention works to easily manufacture a highly reliable lead wiring with a low contact resistance at a low cost, by using an electrode comprising the end of the wiring covered by a reactive organic coating, the lead wire covered by a reactive organic coating, and the conductive fine particles covered by a reactive organic coating.
  • an electronic device 2 on which wiring 1 was formed was prepared and dried thoroughly.
  • an agent containing a reactive functional group (e.g., epoxy group) at the functional site and an alkoxysilyl group at the other end for example, the agent shown in the following chemical formula [Formula 1] was measured at 99 w/t %, and as a silanol condensation catalyst, for example, dibutyltin diacetylacetonate was measured at 1 w/t %, respectively, and these were dissolved into a silicone solvent (e.g., hexamethyldisiloxane solvent) to prepare a chemical adsorption liquid so that it had a concentration of about 1 w/t % (preferably the concentration of the chemical adsorption agent is about 0.5% to 3%).
  • a silicone solvent e.g., hexamethyldisiloxane solvent
  • the electronic device 2 was immersed in this adsorption liquid and reacted in a normal atmosphere (45% relative humidity) for two hours.
  • a chemical adsorption monomolecular film 4 containing epoxy groups that forms a chemical bond with the surface of the wiring 1 throughout the surface was formed at a thickness of about 1 nm because of the bonding formation shown in the following chemical formula [Formula 2] by a dealcoholization reaction (in this case, de-CH 3 OH) between the Si(OCH 3 ) group of the foregoing chemical adsorption agent and the foregoing hydroxyl groups under the presence of the silanol condensation catalyst.
  • a dealcoholization reaction in this case, de-CH 3 OH
  • a chlorinated solvent such as Tricren [trichloroethylene]
  • Tricren trichloroethylene
  • an electronic device 5 which was covered by the chemical adsorption monomolecular film containing a reactive functional group (e.g., epoxy group) over the surface, was manufactured, respectively.
  • an excimer laser and a mask were used to selectively irradiate to the unwanted part of the surface of the end of the foregoing wiring and to remove the foregoing reactive monomolecular film by ablation, except for the end of the wiring 1' (shown in Fig. 1C), or the ring of the epoxy group was opened to be deactivated (shown in Fig. 1D).
  • wirings 7 and T on which the surface of the electronic device 5 was selectively covered by patterned coatings 6 and 6' containing the epoxy group were manufactured.
  • a cationic polymerization initiator e.g., IRGACURE 250 made by Chiba Specialty Chemicals K. K.
  • MEK a cationic polymerization initiator
  • an anhydrous fine silver particle 11 with the size of about 100 nm was prepared and dried thoroughly.
  • an agent containing a reactive functional group e.g., epoxy group or imino group
  • an alkoxysilyl group at the other end for example the agent shown in the above chemical formula [Formula 1] or [Formula 3]
  • a silanol condensation catalyst for example, dibutyltin diacetylacetonate or acetic acid (a type of organic acid) was measured at 1 w/t %, respectively.
  • a silicone solvent e.g., a mixed solvent with 50% hexamethyldisiloxane and 50% dimethylformamide
  • a chemical adsorption liquid so that it had a concentration of about 1 w/t % (preferably the concentration of the chemical adsorption agent is about 0.5% to 3%).
  • the anhydrous fine silver particles 11 were mixed and stirred in this adsorption liquid and reacted in a normal atmosphere (45% relative humidity) for two hours.
  • a normal atmosphere 45% relative humidity
  • a chemical adsorption monomolecular film 13 containing epoxy groups or a chemical adsorption film 14 containing amino groups, which forms a chemical bond with the surface of the conductive fine silver particles throughout the surface was formed at a thickness of about 1 nm because of the bonding formation shown in the above chemical formula [Formula 2] or the following chemical formula [Formula 4] by a dealcoholization reaction (in this case, de-CH 3 OH) between the Si(OCH 3 ) group of the foregoing chemical adsorption agent and the foregoing hydroxyl groups under the presence of the silanol condensation catalyst or an acetic acid, a type of organic acid (shown in Figs. 2B and 2C).
  • a dealcoholization reaction in this case, de-CH 3 OH
  • an adsorption agent containing an amino group When using an adsorption agent containing an amino group, it was better to use an organic acid, such as acetic acid, since the tintype catalyst produced a deposition.
  • the amino group contains an imino group, substances such as pyrrole derivatives and imidazole derivatives other than the amino group also contain the imino group.
  • a ketimine derivative when a ketimine derivative was used, the amino group was easily introduced by hydrolysis after the coating formation.
  • Tricren [trichloroethylene] or N-methylpyrrolidinon was added to the mixture and stirred for cleaning, and thus, a fine silver particle 15, which was covered by the chemical adsorption monomolecular film (the second reactive organic coating) containing a reactive functional group (e.g., epoxy group) over the surface, or a fine silver particle 16, which was covered by the chemical adsorption monomolecular film (this is also the second reactive organic coating) containing the amino group, was manufactured, respectively.
  • the chemical adsorption monomolecular film the second reactive organic coating
  • a reactive functional group e.g., epoxy group
  • the material of the fine particle is made of Au, although it does not have a hydroxyl group on the surface, when an agent in which the SiCU group or Si(OCH 3 ) 3 at the terminal position was replaced with the SH group or a triazinethiol group was used as a chemical adsorption agent (e.g., H 2 N(CH 2 )D-SH (where n is a whole number)), or in particular, when H 2 N(CH2)n-SH was used, a fine gold particle with a formation of a monomolecular film containing an amino group via S was manufactured.
  • a chemical adsorption agent e.g., H 2 N(CH 2 )D-SH (where n is a whole number)
  • H 2 N(CH2)n-SH a fine gold particle with a formation of a monomolecular film containing an amino group via S was manufactured.
  • an agent having the SH group and a methoxysilyl group at the respective terminal positions e.g., HS(CH 2 ) m Si(OCH 3 ) 3 (where m is a whole number)
  • HS(CH 2 ) 3 Si(OCH 3 ) 3 a fine gold particle with a formation of a monomolecular film containing a reactive methoxysilyl group on the surface via S was manufactured.
  • the material of the fine particle is made of Au
  • an agent in which the Si(OCH 3 ) 3 at the terminal position was replaced with the SH group or a triazinethiol group e.g., H 2 N(CH 2 ) H -SH, or H 2 N(CH 2 J 2 -SH
  • a fine gold particle with a formation of a monomolecular film containing the same reactive amino group via S was manufactured.
  • the conductive fine silver particles were covered by an insulated organic thin film, its film thickness was extremely thin so that the conductivity was ensured to be as good as that of aluminum. Particularly when the organic thin film was a monomolecular film, the conductivity as good as that of silver was obtained. Particularly, the electrode in which the epoxy group and the amino group were added to each other to bind and solidify the fine silver particles obtained the conductivity of 0.1 x 10 6 Siemens. [Example 4]
  • the epoxy group on the surface of the fine silver particles contacting the amino group was added at the section where the fine silver particles covered by the chemical adsorption monomolecular film containing the amino group were formed into a single layer in a pattern by a reaction as shown in the above formula [Formula 5] to selectively bind and solidify the fine silver particles covered by the chemical adsorption monomolecular film with the amino group and the fine silver particles covered by the chemical adsorption monomolecular film with the epoxy group via the two monomolecular films on the surface of the end of the wiring.
  • a lead wire that has the end of the lead wire covered by a monomolecular film (the third reactive organic coating) containing an amino group produced in the same way as Example 1 may be used.
  • An electrode covered by multiple layers of organic coatings having a reactive functional group may be reformed at the end of the lead wire in the same way as Example 4. Furthermore, when the electronic device was covered only by a reactive monomolecular film and the electrode covered by an organic coating having a reactive functional group was formed in the same way as Example 3, the same result could be obtained.
  • the (CH 2 OCH) group represents a functional group shown in the following formula [Formula 6] and the (CH 2 CHOCH(CH 2 ) 2 )CH group represents a functional group shown in the following formula [Formula 7].
  • [Formula 6] O CH 2 -CH -
  • Examples 1 and 2 for the silanol condensation catalyst, groups of carboxylic acid metal salt, carboxylic acid ester metal salt, carboxylic acid metal salt polymer, carboxylic acid metal salt chelate, titanic acid ester, and titanic acid ester chelate are available.
  • stannous acetic acid dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoic acid, lead naphthenate, cobalt naphthenate, iron 2-ethylhexanoate, dioctyltin bis-octylthioglycolate ester, dioctyltin maleate ester, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bis-acetylacetate, dioctyltin bis-acetyl laurate, tetrabutyltitanate, tetranonyltitanate, and bis(acetylacetonyl) diprop
  • anhydrous organochlorine solvent for the film forming liquid, anhydrous organochlorine solvent, hydrocarbon solvent, fluorocarbon solvent, silicone solvent, or a mixture of these were available as a solvent. If trying to increase the particle concentration by evaporating the solvent without cleaning, the boiling point of the solvent is preferably between 50 and 250 degrees Celsius.
  • chlorosilane non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, n-paraff ⁇ n, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, and dimethylformamide can be used.
  • the adsorption agent is an alkoxysilane type and the organic coating is formed by evaporating the solvent
  • an alcohol solvent such as methanol, ethanol, propanol, or a mixture of these, could be used in addition to the above listed solvents.
  • the fluorocarbon solvent can be a chlorofluorocarbon solvent, Fluorinert (a product manufactured by 3M Company), and Aflude (a product manufactured by Asahi Glass Co., Ltd.). These may be used as just one solvent in a patterned single layer, or two or more kinds may be mixed if the combination blends well.
  • an organochlorine solvent such as chloroform, may be added.
  • the silanol condensation catalyst was mixed with a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkylalkoxysilane compound (although the ratio can vary from 1 :9 to 9:1 , it is normally preferable to be around 1:1), the processing time was even several times faster (to about one-half hour), so that the time for film formation was reduced to a fraction.
  • a dibutyltin oxide which is a silanol catalyst
  • H3 from Japan Epoxy Resins Co., Ltd.
  • the available ketimine compounds are not particularly limited and include the following examples: 2,5,8-triaza-1 ,8-nonadien 3,11 -dimethyl-4,7, 10-triaza-3, 10-tridecadien 2,10-dimethyl-3,6,9-triaza-2,9-undecadien 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadien
  • organic acids there are also no particular limitations to the organic acids available; however, for example, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid showed almost the same effect.

Abstract

The present invention relates to an electrode in which a selectively formed monostratal conductive fine particle film is covalently bound to the surface of the end of the wiring or the end of the lead wire via a first organic coating selectively formed on the surface of the end of the wiring or the end of the lead wire and a second organic coating formed on the surface of the conductive fine particles, and also the electrode in which these organic coatings are different from each other.

Description

DESCRIPTION
ELECTRODE AND METHOD FOR MANUFACTURING THE SAME, LEAD WIRING USING THE ELECTRODEAND METHOD FOR CONNECTING THE SAME1 AND RELATED ELECTRONIC COMPONENTS AND ELECTRONIC EQUIPMENT
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention is related to an electrode used for electronic equipment, electronic devices, or printed boards, and the method for manufacturing the same, and a lead wiring using the electrode and the method for connecting the same. In particular, it relates to an electrode using a monostratal film of conductive fine particles or a laminated body of conductive fine particles comprising conductive fine particles that are given either thermal reactivity or light reactivity, or otherwise radical reactivity or ionic reactivity, to the surface, and the method for manufacturing the same. It also relates to a lead wiring using the electrode and the method for connecting the same, and related electronic components and electronic equipment.
In the present invention, conductive fine particle includes fine metal particles made of gold, silver, copper, and nickel, or silver-plated precious metal, copper, and nickel. In addition, it also includes fine metal oxide particles, such as ITO and SnO2.
Description of Related Art
Conventional bump electrodes used for electronic equipment, electronic devices, and printed boards and the method for manufacturing the same, and a lead wiring using the bump electrode and the method for connecting the same, are known to include the method of applying a conductive paste to the end of the wiring by printing to bond an external lead wire, or the method of transferring a preformed bump on another substrate to the end of the wiring to bond an external lead wire via the foregoing bump. [Patent document 1] Japanese Patent Laid-Open No. 2002-016169
As electronic devices and printed boards become finer and denser, the printing of a silver paste or the bump method become insufficient in terms of the density growth.
In order to make the wirings finer on electronic devices and printed boards, it is necessary to form the electrode protrusion at the end of the wiring with an even thickness; however, there was no concept of manufacturing a film coating with an even thickness at the particle size level by accumulating each monolayer comprising conductive fine particles.
The present invention aims to provide an electrode using a film coating (a patterned monostratal conductive fine particle film) with an even thickness at the particle size level by selectively arranging conductive fine particles only in one layer on the surface of the end of any wiring, or an electrode using a film coating (a patterned laminated body of conductive fine particle films) by selectively accumulating two or more layers of films of conductive fine particles arranged only in one layer, wherein conductive fine particles are used without losing the original function of the conductive fine particles while giving a new function, and the method for manufacturing the same. The present invention also aims to provide a lead wiring using the electrode and the method for connecting the same.
SUMMARY OF THE INVENTION
In order to solve the above described problems, the first aspect of this invention, which is presented, is an electrode, wherein a selectively formed monostratal conductive fine particle film is covalently bound to the surface of the end of the wiring or the end of the lead wire via a first organic coating selectively formed on the surface of the end of the wiring or the end of the lead wire and a second organic coating formed on the surface of the conductive fine particles. The second aspect of this invention is the electrode of the first aspect of this invention, wherein the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particles are different from each other.
The third aspect of this invention is the electrode of the first aspect of this invention, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
The fourth aspect of this invention is the electrode of the first and the second aspects of this invention, wherein the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particles comprise a monomolecular film. The fifth aspect of this invention is a method for manufacturing an electrode comprising a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the first reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other; and a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating.
The sixth aspect of this invention is the method for manufacturing an electrode in the fifth aspect of this invention comprising a process of forming the first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; and a process that follows of forming first and second reactive monomolecular films that are covalently bound to the surfaces of the end part and the conductive fine particles, respectively, by cleaning the surfaces of the end part and the conductive fine particles with an organic solvent.
The seventh aspect of this invention is the method for manufacturing an electrode in the fifth aspect of this invention, wherein the first reactive organic coating comprises an epoxy group, and the second reactive organic coating comprises an imino group.
The eighth aspect of this invention is the method for manufacturing an electrode in the sixth aspect of this invention, wherein the first reactive monomolecular film comprises an epoxy group, and the second reactive monomolecular film comprises an imino group.
The ninth aspect of this invention is an electrode, wherein the conductive fine particles selectively accumulated in layers on the surface of the end of the wiring or the surface of the end of a lead wire are covalently bound to each other between layers via the organic coating formed on the surface of the conductive fine particles.
The tenth aspect of this invention is the electrode of the ninth aspect of this invention, wherein the organic coatings formed on the surface of the conductive fine particles comprise two types, and the conductive fine particles with the formation of the first organic coating and the conductive fine particles with the formation of the second organic coating are alternately laminated.
The eleventh aspect of this invention is the electrode of the tenth aspect of this invention, wherein the first organic coating and the second organic coating react with each other to form a covalent bond.
The twelfth aspect of this invention is the electrode of the ninth aspect of this invention, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
The thirteenth aspect of this invention is a method for manufacturing an electrode comprising a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting at least the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the first conductive fine particle by dispersing the first conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the surface of the end of the lead wire on which the first reactive organic coating is formed contact the first conductive fine particles covered by the second reactive organic coating to react with each other; a process of cleaning and removing redundant first conductive fine particles covered by the second reactive organic coating to selectively form a first patterned monostratal conductive fine particle film; a process of forming a third reactive organic coating on the surface of the second conductive fine particle by dispersing the second conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the surface of the end of the lead wire on which the first patterned monostratal conductive fine particle film covered by the second reactive organic coating is formed contact the second conductive fine particles covered by the third reactive organic coating to react with each other; and a process of cleaning and removing redundant second conductive fine particles covered by the third reactive organic coating to selectively form a second patterned monostratal conductive fine particle film.
The fourteenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein the first reactive organic coating and the third reactive organic coating are made of the same materials.
The fifteenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein after the process of forming the second patterned monostratal conductive fine particle film, repetitively performing the process of forming the first patterned monostratal conductive fine particle film and the process of forming the second patterned monostratal conductive fine particle film in the same way.
The sixteenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein after the process of forming the first, second, and third reactive organic coatings, the surfaces of the base material or conductive fine particles are cleaned with an organic solvent to form the first, second, and third reactive monomolecular films that are covalently bound with the surface of the base material or conductive fine particles, respectively. The seventeenth aspect of this invention is the method for manufacturing an electrode in the thirteenth aspect of this invention, wherein the first and the third reactive organic coatings comprise an epoxy group, and the second reactive organic coating comprises an imino group.
The eighteenth aspect of this invention is the method for manufacturing an electrode in the fifth and the thirteenth aspects of this invention, wherein a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst.
The nineteenth aspect of this invention is the method for manufacturing an electrode in the fifth and the thirteenth aspects of this invention, wherein at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst for use.
The twentieth aspect of this invention is a lead wiring, wherein the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first organic coating formed on the surface of the end of the wiring, a second organic coating formed on the surface of the conductive fine particles, and a third organic coating formed on the surface of the lead wire.
The twenty-first aspect of this invention is a lead wiring, wherein the conductive fine particles are formed in one layer or in multiple layers.
The twenty-second aspect of this invention is the lead wiring of the twentieth aspect of this invention, wherein the first organic coating and the third organic coating are covalently bound to each other directly or indirectly via the second organic coating formed on the surface of the conductive fine particles.
The twenty-third aspect of this invention is the lead wiring of the twenty-first aspect of this invention, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
The twenty-fourth aspect of this invention is the lead wiring of the twentieth, twenty-first, twenty-second, and twenty-third aspects of this invention, wherein the first organic coating, the second organic coating, and the third organic coating comprise a monomolecular film. The twenty-fifth aspect of this invention is a method for connecting a lead wiring comprising a process of forming a first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming a third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first or third reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the patterned first or third reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other; a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating to form a layer of conductive fine particles covered by the 24th reactive organic coating; and a process of clamping the end of the foregoing wiring and the end of the lead wire to connect with each other via the layer of conductive fine particles.
The twenty-sixth aspect of this invention is the method for connecting a lead wiring in the twenty-fifth aspect of this invention, wherein the layer of the conductive fine particles is formed in multiple layers.
The twenty-seventh aspect of this invention is the method for connecting a lead wiring in the twenty-fifth aspect of this invention, wherein the conductive fine particles covered by the second and the fourth reactive organic coatings, respectively, are contacted to the top surface of the end of the wiring and the end of the lead wire on which the patterned first and third reactive organic coatings are formed to selectively react with each other, forming a layer of the conductive fine particles covered by the second and the fourth reactive organic coatings on the respective top surfaces.
The twenty-eighth aspect of this invention is the method for connecting a lead wiring in the twenty-seventh aspect of this invention, wherein the second and the fourth reactive organic coatings comprise a functional group that reacts with each other.
The twenty-ninth aspect of this invention is an electronic component using the electrode of the first through fourth aspects of this invention, inclusive, the electrode of the ninth through twelfth aspects of this invention, inclusive, and the lead wiring of the twentieth through twenty-fourth aspects of this invention, inclusive. The thirtieth aspect of this invention is electronic equipment using the electrode of the first through fourth aspects of this invention, inclusive, the electrode of the ninth through twelfth aspects of this invention, inclusive, and the lead wiring of the twentieth through twenty-fourth aspects of this invention, inclusive.
As a further explanation for the above described invention, the gist of the present invention manufactures and provides an electrode in which a selectively formed monostratal conductive fine particle film is covalently bound to the surface of the end of the wiring or the end of the lead wire via a first organic coating selectively formed on the surface of the end of the wiring or the end of the lead wire and a second organic coating formed on the surface of the conductive fine particles through a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the first reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other; and a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating.
In so doing, it is advantageous for improving the conductivity of the electrode, if performing: a process of forming the first reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; and a process that follows of forming first and second reactive monomolecular films that are covalently bound to the surfaces of the end part and the conductive fine particles, respectively, by cleaning the surfaces of the end part and the conductive fine particles with an organic solvent.
In addition, if the first reactive organic coating or monomolecular film comprises an epoxy group and the second reactive organic coating comprises an imino group, it is advantageous for generating a strong covalent bond.
In so doing, if the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particle comprise a functional group that reacts with each other for a covalent bond, it is advantageous for improving the strength of the electrode. Furthermore, it is advantageous for increasing the stability of the electrode, if the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group.
In so doing, if the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particle comprise a monomolecular film, it is advantageous for creating an electrode that is excellent in conductivity. Besides, the gist of the present invention also manufactures and provides an electrode in which the conductive fine particles selectively accumulated in layers on the surface of the end of the wiring or the surface of the end of a lead wire are covalently bound to each other between layers via the organic coating formed on the surface of the conductive fine particles through: a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting at least the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the first conductive fine particle by dispersing the first conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the surface of the end of the lead wire on which the first reactive organic coating is formed contact the first conductive fine particles covered by the second reactive organic coating to react with each other; a process of cleaning and removing redundant first conductive fine particles covered by the second reactive organic coating to selectively form a first patterned monostratal conductive fine particle film; a process of forming a third reactive organic coating on the surface of the second conductive fine particle by dispersing the second conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the surface of the end of the lead wire on which the first patterned monostratal conductive fine particle film covered by the second reactive organic coating is formed contact the second conductive fine particles covered by the third reactive organic coating to react with each other; and a process of cleaning and removing redundant second conductive fine particles covered by the third reactive organic coating to selectively form a second patterned monostratal conductive fine particle film.
In so doing, if the first reactive organic coating and the third reactive organic coating are made of the same substance, it is advantageous for reducing the production cost of the electrode.
In addition, after the process of forming the second patterned monostratal conductive fine particle film, if repetitively performing the process of forming the first patterned monostratal conductive fine particle film and the process of forming the second patterned monostratal conductive fine particle film in the same way, a larger protrusion can be formed for the electrode; thus it is advantageous for connecting an external lead wire. Furthermore, after the process of forming the first, second, and third reactive organic coatings, if the surface of the base material or conductive fine particles are cleaned with an organic solvent to form the first, second, and third reactive monomolecular films that are covalently bound to the surface of the base material or conductive fine particles, respectively, it is advantageous for increasing the conductivity of the electrode.
Furthermore, if the first and the third reactive organic coatings comprise an epoxy group and the second reactive organic coating comprises an imino group, it is advantageous for manufacturing an electrode with a high stability. If a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst, it is advantageous for improving the efficiency of the creation of the organic coatings. If at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst, it is advantageous for improving the efficiency of the creation of the organic coatings.
In so doing, it is advantageous for controlling the height of the electrode, if the organic coatings formed on the surface of the conductive fine particles are prepared in two types, and the conductive fine particles with the formation of the first organic coating and the conductive fine particles with the formation of the second organic coating are alternately laminated. Furthermore, it is advantageous for improving the strength of the electrode, if the first organic coating and the second organic coating react with each other to form a covalent bond, such as an N-C bond formed by a reaction between an epoxy group and an imino group.
Furthermore, the gist of the present invention also manufactures and provides a lead wiring in which the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first organic coating formed on the surface of the end of the wiring, a second organic coating formed on the surface of the conductive fine particles, and a third organic coating formed on the surface of the lead wire through: a process of forming the first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first or the third reactive organic coating into a prescribed pattern; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the patterned first or the third reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other, a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating to form an electrode comprising a layer of the conductive fine particles covered by the second reactive organic coating; and a process of clamping the end of the foregoing wiring and the end of the lead wire to connect with each other by binding the electrode comprising the layer of the conductive fine particles. In so doing, if the layer of the conductive fine particles is formed in multiple layers, it is advantageous for eliminating steps on the substrate. In addition, it is advantageous for connecting the wiring and the lead wire, if the conductive fine particles covered by the second and the fourth reactive organic coatings, respectively, are contacted to the top surface of the end of the wiring and the end of the lead wire on which the patterned first and third reactive organic coatings are formed to selectively react with each other to form a layer of the conductive fine particles covered by the second and the fourth reactive organic coatings on the respective top surfaces, and these second and fourth reactive organic coatings comprise a functional group that reacts with each other.
If the conductive fine particles are formed in one layer or in multiple layers, a highly reliable lead wiring can be obtained. Furthermore, it is advantageous for forming a highly reliable lead wiring, if the first organic coating and the third organic coating form an N-C covalent bond with each other by a reaction of an epoxy group and an imino group, directly or indirectly, via the second organic coating formed on the surface of the conductive fine particles.
Furthermore, if the first organic coating, the second organic coating, and the third organic coating comprise a monomolecular film, it is advantageous for forming a lead wiring with a low contact resistance.
As described above, the present invention has the particular effect of providing an electrode using a film coating with an even thickness at the particle size level by selectively arranging conductive fine particles only in one layer on the end of the wiring on the surface of any circuit substrate or the surface of the end of a lead wiring, or an electrode using a film coating by selectively accumulating two or more layers of films of conductive fine particles arranged only in one layer, wherein the conductive fine particles are used without losing the original function of the conductive fine particles while giving a new function; and providing the method for manufacturing the same at a low cost. The present invention also has the particular effect of providing a lead wiring with a high density using the electrode and the method for connecting the lead wiring at a low cost.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 contains conceptual diagrams of the first example of the present invention, which diagrams expand the reaction of the surface of the end of the wiring to the molecular level. Fig. 1A shows the surface before the reaction. Fig. 1B shows the surface after a monomolecular film containing an epoxy group is formed. Fig. 1C shows the surface after a monomolecular film containing an amino group is formed.
Fig. 2 contains conceptual diagrams of the second example of the present invention, which diagrams expand the reaction of the surface of the conductive fine silver particle to the molecular level. Fig. 2A shows the surface of the conductive fine silver particle before the reaction. Fig. 2B shows the surface after a monomolecular film containing an epoxy group is formed. Fig. 2C shows the surface after a monomolecular film containing an amino group is formed.
Fig. 3 contains conceptual diagrams of the third and fourth examples of the present invention, which diagrams expand the reaction of the surface of the end of the wiring to the molecular level. Fig. 3A shows the surface of the end of the wiring on which a patterned monostratal conductive fine silver particle film is formed as an electrode. Fig. 3B shows the surface of the end of the wiring on which two layers of the patterned monostratal conductive fine silver particle films are formed as an electrode.
Fig. 4 contains conceptual diagrams of the fifth example of the present invention, which diagrams enlarge the connection part of the end of the wiring of an electronic device and a lead wire via the electrode.
DETAILED DESCRIPTION
The present invention is to manufacture and provide a lead wiring in which the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first reactive organic coating formed on the surface of the end of the wiring, a second reactive organic coating formed on the surface of the conductive fine particles, and a third reactive organic coating formed on the surface of the lead wire through: a process of forming the first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the foregoing first or the third reactive organic coating into a prescribed pattern; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the patterned first or the third reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other; a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating to form an electrode comprising a layer of the conductive fine particles covered by the second reactive organic coating; and a process of clamping the end of the foregoing wiring and the end of the lead wire to connect with each other by binding the electrode comprising the foregoing layer of the conductive fine particles.
Therefore, the present invention works to easily manufacture a highly reliable lead wiring with a low contact resistance at a low cost, by using an electrode comprising the end of the wiring covered by a reactive organic coating, the lead wire covered by a reactive organic coating, and the conductive fine particles covered by a reactive organic coating.
Although examples are hereinafter used to describe the details of the present invention, these examples shall not be construed as being limiting of the present invention. According to the present invention, in order to produce the electrode using a patterned monostratal conductive fine particle film or the electrode using a patterned laminated body of conductive fine particle films, fine particles made of silver, copper, nickel, or silver-plated precious metal, copper, and nickel are available. Fine silver particles are used to explain the representative example. [Example 1]
First, an electronic device 2 on which wiring 1 was formed was prepared and dried thoroughly. Next, as a chemical adsorption agent, an agent containing a reactive functional group (e.g., epoxy group) at the functional site and an alkoxysilyl group at the other end, for example, the agent shown in the following chemical formula [Formula 1], was measured at 99 w/t %, and as a silanol condensation catalyst, for example, dibutyltin diacetylacetonate was measured at 1 w/t %, respectively, and these were dissolved into a silicone solvent (e.g., hexamethyldisiloxane solvent) to prepare a chemical adsorption liquid so that it had a concentration of about 1 w/t % (preferably the concentration of the chemical adsorption agent is about 0.5% to 3%). [Formula 1]
/°\ OCH3
CH2-CHCH2O(CH2)SSi -OCH3
OCH3
Then, the electronic device 2 was immersed in this adsorption liquid and reacted in a normal atmosphere (45% relative humidity) for two hours. In this case, since the surface of the electronic device 2 contains many hydroxyl groups 3 (shown in Fig. 1A), a chemical adsorption monomolecular film 4 containing epoxy groups that forms a chemical bond with the surface of the wiring 1 throughout the surface was formed at a thickness of about 1 nm because of the bonding formation shown in the following chemical formula [Formula 2] by a dealcoholization reaction (in this case, de-CH3OH) between the Si(OCH3) group of the foregoing chemical adsorption agent and the foregoing hydroxyl groups under the presence of the silanol condensation catalyst. [Formula 2] O O—
CH2-CHCH2O(CH2J3Si -O- o—
Then, a chlorinated solvent, such as Tricren [trichloroethylene], was used for cleaning, and thus, an electronic device 5, which was covered by the chemical adsorption monomolecular film containing a reactive functional group (e.g., epoxy group) over the surface, was manufactured, respectively. (Shown in Fig. 1B)
When it was taken out into the atmosphere without cleaning, the reactivity was almost the same; however, the solvent evaporated, and the chemical adsorption agent left behind on the surface of the electronic device 2 reacted at the surface with the moisture in the atmosphere, and an electronic device 5 on which an extremely thin reactive polymer coating was then formed from the foregoing chemical adsorption agent on the surface was obtained.
Next, an excimer laser and a mask were used to selectively irradiate to the unwanted part of the surface of the end of the foregoing wiring and to remove the foregoing reactive monomolecular film by ablation, except for the end of the wiring 1' (shown in Fig. 1C), or the ring of the epoxy group was opened to be deactivated (shown in Fig. 1D). Thus, wirings 7 and T on which the surface of the electronic device 5 was selectively covered by patterned coatings 6 and 6' containing the epoxy group were manufactured.
As an alternative method regarding the surface of the foregoing coating, a cationic polymerization initiator (e.g., IRGACURE 250 made by Chiba Specialty Chemicals K. K.) was diluted with MEK and quantitatively applied to the surface of the epoxy coating and then selectively exposed to a far-ultraviolet radiation. This process also allowed to selectively perform a ring-opening polymerization of the epoxy group for deactivation in a pattern. [Example 2]
In the same way as Example 1 , first an anhydrous fine silver particle 11 with the size of about 100 nm was prepared and dried thoroughly. Next, as a chemical adsorption agent, an agent containing a reactive functional group (e.g., epoxy group or imino group) at the functional site and an alkoxysilyl group at the other end, for example the agent shown in the above chemical formula [Formula 1] or [Formula 3], was measured at 99 w/t %, and as a silanol condensation catalyst, for example, dibutyltin diacetylacetonate or acetic acid (a type of organic acid) was measured at 1 w/t %, respectively. These were dissolved into a silicone solvent (e.g., a mixed solvent with 50% hexamethyldisiloxane and 50% dimethylformamide) to prepare a chemical adsorption liquid so that it had a concentration of about 1 w/t % (preferably the concentration of the chemical adsorption agent is about 0.5% to 3%). [Formula 3]
OCH3
H2N(CH2)3Si — OCH3 OCH3
The anhydrous fine silver particles 11 were mixed and stirred in this adsorption liquid and reacted in a normal atmosphere (45% relative humidity) for two hours. In this case, since the surface of the anhydrous fine silver particle contains many hydroxyl groups 12 (shown in Fig. 2A), a chemical adsorption monomolecular film 13 containing epoxy groups or a chemical adsorption film 14 containing amino groups, which forms a chemical bond with the surface of the conductive fine silver particles throughout the surface, was formed at a thickness of about 1 nm because of the bonding formation shown in the above chemical formula [Formula 2] or the following chemical formula [Formula 4] by a dealcoholization reaction (in this case, de-CH3OH) between the Si(OCH3) group of the foregoing chemical adsorption agent and the foregoing hydroxyl groups under the presence of the silanol condensation catalyst or an acetic acid, a type of organic acid (shown in Figs. 2B and 2C). [Formula 4]
O—
H2N(CH2J3Si - O — O—
When using an adsorption agent containing an amino group, it was better to use an organic acid, such as acetic acid, since the tintype catalyst produced a deposition. Although the amino group contains an imino group, substances such as pyrrole derivatives and imidazole derivatives other than the amino group also contain the imino group. Furthermore, when a ketimine derivative was used, the amino group was easily introduced by hydrolysis after the coating formation. Then Tricren [trichloroethylene] or N-methylpyrrolidinon was added to the mixture and stirred for cleaning, and thus, a fine silver particle 15, which was covered by the chemical adsorption monomolecular film (the second reactive organic coating) containing a reactive functional group (e.g., epoxy group) over the surface, or a fine silver particle 16, which was covered by the chemical adsorption monomolecular film (this is also the second reactive organic coating) containing the amino group, was manufactured, respectively.
In addition, in the case that the material of the fine particle is made of Au, although it does not have a hydroxyl group on the surface, when an agent in which the SiCU group or Si(OCH3)3 at the terminal position was replaced with the SH group or a triazinethiol group was used as a chemical adsorption agent (e.g., H2N(CH2)D-SH (where n is a whole number)), or in particular, when H2N(CH2)n-SH was used, a fine gold particle with a formation of a monomolecular film containing an amino group via S was manufactured. On the other hand, when an agent having the SH group and a methoxysilyl group at the respective terminal positions was used (e.g., HS(CH2)mSi(OCH3)3 (where m is a whole number)), or in particular, when HS(CH2)3Si(OCH3)3 was used, a fine gold particle with a formation of a monomolecular film containing a reactive methoxysilyl group on the surface via S was manufactured.
Since this coating is extremely thin with a film thickness at the nanometer level, the particle diameter was not impaired.
On the other hand, when it was taken out into the atmosphere without cleaning, the reactivity was almost the same; however, the solvent evaporated and the chemical adsorption agent left behind on the surface of the particle reacted at the surface with the moisture in the atmosphere, and a conductive fine silver particle on which an extremely thin reactive polymer coating was then formed from the foregoing chemical adsorption agent on the surface was obtained.
Since this method uses a dealcoholization reaction, it is applicable to both organic and inorganic conductive fine particles, and is capable of wide application.
In addition, in the case that the material of the fine particle is made of Au, when an agent in which the Si(OCH3)3 at the terminal position was replaced with the SH group or a triazinethiol group was used (e.g., H2N(CH2)H-SH, or H2N(CH2J2-SH), a fine gold particle with a formation of a monomolecular film containing the same reactive amino group via S was manufactured. On the other hand, when an agent having the SH group and a methoxysilyl group at the respective terminal positions was used (e.g., HS(CH2)3Si(OCH3)3), a fine gold particle with a formation of a monomolecular film containing the methoxysilyl group on the surface via S was manufactured. [Example 3]
Next, when fine silver particles, which were covered by a chemical adsorption monomolecular film (the second reactive organic coating) containing the amino group, were dispersed in alcohol to apply to the electronic device 22 selectively covered by a chemical adsorption monomolecular film 21 (the first reactive organic coating) containing the foregoing epoxy group and were heated at 200 degrees Celsius, the amino group on the surface of the fine silver particles contacting the epoxy group on the surface of the end of the wiring was added by a reaction as shown in the following formula [Formula 5] to selectively bind the fine silver particles and the end of the wiring via the two monomolecular films. (When the alcohol was evaporated while applying ultrasound, the evenness of the film thickness of the coating was allowed to improve.) [Formula 5]
O
/ \
-(CH2)CH-CH2 + H2NCH2
— ► - (CH2)CHCH2 -NHCH2 - OH Then again, the surface of the end of the wiring was cleaned with alcohol, and the fine silver particles covered by the chemical adsorption monomolecular film, containing the redundant unreacted amino group were cleaned and removed; thus, an electrode 22 comprising a patterned monostratal conductive fine silver particle film 24 was formed with an even thickness at the particle size level, while the fine silver particles 23, which were covered by the chemical adsorption monomolecular film with the amino group covalently bound to the surface of the electronic device 22, were selectively arranged only in one layer. (Shown in Fig. 3A)
Although the conductive fine silver particles were covered by an insulated organic thin film, its film thickness was extremely thin so that the conductivity was ensured to be as good as that of aluminum. Particularly when the organic thin film was a monomolecular film, the conductivity as good as that of silver was obtained. Particularly, the electrode in which the epoxy group and the amino group were added to each other to bind and solidify the fine silver particles obtained the conductivity of 0.1 x 106 Siemens. [Example 4]
In addition, if the film thickness of the conductive fine silver particle film at the electrode part needs to be thicker, subsequent to Example 3, the fine silver particles 25, which were covered by a chemical adsorption monomolecular film containing the epoxy group, were dispersed in alcohol to apply to the surface of the end of the wiring on which the electrode 24 comprising the patterned monostratal conductive fine silver particle film was formed with an even thickness at the particle size level, while the fine silver particles covered by the chemical adsorption monomolecular film containing the covalently bound amino group were arranged only in one layer, and then heated to 200 degrees Celsius. As a result, the epoxy group on the surface of the fine silver particles contacting the amino group was added at the section where the fine silver particles covered by the chemical adsorption monomolecular film containing the amino group were formed into a single layer in a pattern by a reaction as shown in the above formula [Formula 5] to selectively bind and solidify the fine silver particles covered by the chemical adsorption monomolecular film with the amino group and the fine silver particles covered by the chemical adsorption monomolecular film with the epoxy group via the two monomolecular films on the surface of the end of the wiring.
Then again, the surface of the end of the wiring was cleaned with alcohol, and the fine silver particles covered by the chemical adsorption monomolecular film containing the redundant unreacted epoxy group were cleaned and removed; thus, an electrode 26 comprising a patterned monostratal conductive fine silver particle film with the two-layer structure was formed with an even thickness at the particle size level, while the second layer of the fine silver particles covalently bound to the surface of the end of the wiring was arranged only in one layer. (Fig. 3B) Similarly, when the fine silver particles covered by the chemical adsorption monomolecular film containing the amino group and the fine silver particles covered by the chemical adsorption monomolecular film containing the epoxy group were alternately laminated, an electrode with a controlled height comprising an accumulated coating of conductive fine silver particles with a multilayered structure was manufactured. [Example 5]
The electrode of the electronic device 22 in which the silver fine particles on the top surface of the electrode produced in the same way as Example 4 were covered by a monomolecular film containing an amino group, and the end of a lead wire 27 covered by a monomolecular film (the third reactive organic coating) containing an epoxy group produced in the same way as Example 1 were positioned and clamped together, and both were heated at 200 degrees Celsius. As a result, the amino group on the surface of the fine silver particles was added to the contacting epoxy group by the reaction shown in the above formula [Formula 5] to cause a chemical reaction for the conductivity between the silver fine particles covered by the chemical adsorption monomolecular film containing the amino group on the subsurface of the electrode and the lead wire 28 covered by the chemical adsorption monomolecular film containing the epoxy group, forming a lead wiring 29. (Fig. 4)
In the case of an electronic device in which the fine silver particles on the top surface of the electrode are covered by a monomolecular film (the second reactive organic coating) containing an epoxy group, a lead wire that has the end of the lead wire covered by a monomolecular film (the third reactive organic coating) containing an amino group produced in the same way as Example 1 may be used.
An electrode covered by multiple layers of organic coatings having a reactive functional group may be reformed at the end of the lead wire in the same way as Example 4. Furthermore, when the electronic device was covered only by a reactive monomolecular film and the electrode covered by an organic coating having a reactive functional group was formed in the same way as Example 3, the same result could be obtained.
Moreover, when these electrodes were used to connect lead wires for semiconductor devices or printed boards, a significantly higher reliability of the electrical connection could be achieved compared to those of electronic devices with the conventional ultrasonic welding. The electronic equipment with these connections significantly reduced the rate of failure occurrence in reliability tests.
Although the above Examples 1 and 2 used the substance shown in [Formula 1] or [Formula 3] as a chemical adsorption agent containing a reactive group, the following substances (1) through (16), inclusive, other than those described above, could also be used.
(1) (CH2OCH)CH2θ(CH2)7Si(OCH3)3
(2) (CH2OCH)CH2θ(CH2)iiSi(OCH3)3
(3) (CH2CHOCH(CH2)2)CH(CH2)2Si(OCH3)3 (4) (CH2CHOCH(CH2)2)CH(CH2)4Si(OCH3)3
(5) (CH2CHOCH(CH2)2)CH(CH2)6Si(OCH3)3
(6) (CH2OCH)CH2O (CH2J7Si(OC2Hs)3
(7) (CH2OCH)CH2O (CH2)I1Si(OC2Hg)3
(8) (CH2CHOCH(CH2)2)CH(CH2)2Si(OC2H5)3 (9) (CH2CHOCH(CH2)2)CH(CH2)4Si(OC2H5)3
(10) (CH2CHOCH(CH2)2)CH(CH2)6Si(OC2H5)3
(11) H2N(CH2)SSi(OCHs)3
(12) H2N(CH2)7Si(OCH3)3
(13) H2N(CH2)9Si(OCH3)3 (14) H2N(CH2)SSi(OC2Hs)3
(15) H2N(CHz)7Si(OC2Hs)3
(16) H2N(CH2)SSi(OC2Hs)3
Hereinabove, the (CH2OCH) group represents a functional group shown in the following formula [Formula 6] and the (CH2CHOCH(CH2)2)CH group represents a functional group shown in the following formula [Formula 7]. [Formula 6] O CH2-CH -
[Formula 7]
0 CH-CH2
\ / \
CH CH
\ /
CH2 -CH2
In Examples 1 and 2, for the silanol condensation catalyst, groups of carboxylic acid metal salt, carboxylic acid ester metal salt, carboxylic acid metal salt polymer, carboxylic acid metal salt chelate, titanic acid ester, and titanic acid ester chelate are available. More specifically, stannous acetic acid, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoic acid, lead naphthenate, cobalt naphthenate, iron 2-ethylhexanoate, dioctyltin bis-octylthioglycolate ester, dioctyltin maleate ester, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bis-acetylacetate, dioctyltin bis-acetyl laurate, tetrabutyltitanate, tetranonyltitanate, and bis(acetylacetonyl) dipropyl titanate could be used.
For the film forming liquid, anhydrous organochlorine solvent, hydrocarbon solvent, fluorocarbon solvent, silicone solvent, or a mixture of these were available as a solvent. If trying to increase the particle concentration by evaporating the solvent without cleaning, the boiling point of the solvent is preferably between 50 and 250 degrees Celsius.
More precisely, chlorosilane non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, n-paraffιn, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, and dimethylformamide can be used.
In addition, if the adsorption agent is an alkoxysilane type and the organic coating is formed by evaporating the solvent, an alcohol solvent, such as methanol, ethanol, propanol, or a mixture of these, could be used in addition to the above listed solvents.
In addition, the fluorocarbon solvent can be a chlorofluorocarbon solvent, Fluorinert (a product manufactured by 3M Company), and Aflude (a product manufactured by Asahi Glass Co., Ltd.). These may be used as just one solvent in a patterned single layer, or two or more kinds may be mixed if the combination blends well. In addition, an organochlorine solvent, such as chloroform, may be added.
On the other hand, when a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound was used instead of the silanol condensation catalyst, the processing time was reduced to about 1/2 to 2/3 at the same concentration.
Moreover, when the silanol condensation catalyst was mixed with a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkylalkoxysilane compound (although the ratio can vary from 1 :9 to 9:1 , it is normally preferable to be around 1:1), the processing time was even several times faster (to about one-half hour), so that the time for film formation was reduced to a fraction. For example, when a dibutyltin oxide, which is a silanol catalyst, was replaced with H3 (from Japan Epoxy Resins Co., Ltd.), a ketimine compound, and the other conditions remained the same, we obtained almost the same results, except that the reaction time was reduced to about one hour.
Moreover, when the silanol catalyst was replaced with a mixture of H3 (from Japan Epoxy Resins Co., Ltd.), a ketimine compound, and dibutyltin bis-acetylacetonate, a silanol catalyst (mixing ratio of 1 :1), and the other conditions remained the same, we obtained almost the same results, except that the reaction time was reduced to about one-half hour.
Therefore, the above results clearly indicated that the ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound are more active than the silanol condensation catalyst. Moreover, the activity was further enhanced when the silanol condensation catalyst was mixed with one selected from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound. The available ketimine compounds are not particularly limited and include the following examples: 2,5,8-triaza-1 ,8-nonadien 3,11 -dimethyl-4,7, 10-triaza-3, 10-tridecadien 2,10-dimethyl-3,6,9-triaza-2,9-undecadien 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadien
2,4, 15, 17-tetramethyl-5,8, 11 , 14-tetraaza-4, 14-octadecadien 2,4,20,22-tetramethyl-5, 12, 19-triaza-4, 19-trieicosadien
There are also no particular limitations to the organic acids available; however, for example, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid showed almost the same effect.
In the above Examples 1 through 5, inclusive, an electronic device and fine silver particles were used for the explanation; however, the present invention is applicable to electronic devices, such as semiconductor devices or printed boards, that comprise an electronic circuit.

Claims

1. An electrode, wherein a selectively formed monostratal conductive fine particle film is covalently bound to the surface of the end of the wiring or the end of the lead wire via a first organic coating selectively formed on the surface of the end of the wiring or the end of the lead wire and a second organic coating formed on the surface of the conductive fine particles.
2. The electrode as claimed in Claim 1 , wherein the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particles are different from each other.
3. The electrode as claimed in Claim 1 , wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
4. The electrode as claimed in Claim 1 or 2, wherein the first organic coating formed on the surface of the end of the wiring or the surface of the end of the lead wire and the second organic coating formed on the surface of the conductive fine particles comprise a monomolecular film.
5. A method for manufacturing an electrode comprising: a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming said first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the first reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other; and a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating.
6. The method for manufacturing an electrode as claimed in Claim 5 comprising: a process of forming the first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming the second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; and a process that follows of forming first and second reactive monomolecular films that are covalently bound to the surfaces of the end part and the conductive fine particles, respectively, by cleaning the surfaces of the end part and the conductive fine particles with an organic solvent.
7. The method for manufacturing an electrode as claimed in Claim 5, wherein the first reactive organic coating comprises an epoxy group, and the second reactive organic coating comprises an imino group.
8. The method for manufacturing an electrode as claimed in Claim 6, wherein the first reactive monomolecular film comprises an epoxy group, and the second reactive monomolecular film comprises an imino group.
9. An electrode, wherein the conductive fine particles selectively accumulated in layers on the surface of the end of the wiring or the surface of the end of a lead wire are covalently bound to each other between layers via the organic coating formed on the surface of the conductive fine particles.
10. The electrode as claimed in Claim 9, wherein the organic coatings formed on the surface of the conductive fine particles comprise two types, and the conductive fine particles with the formation of the first organic coating and the conductive fine particles with the formation of the second organic coating are alternately laminated.
11. The electrode as claimed in Claim 10, wherein the first organic coating and the second organic coating react with each other to form a covalent bond.
12. The electrode as claimed in Claim 9, wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
13. A method for manufacturing an electrode comprising: a process of forming a first reactive organic coating on the surface of the end of the wiring or the surface of the end of a lead wire by contacting at least the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming said first reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the first conductive fine particle by dispersing the first conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the surface of the end of the lead wire on which the first reactive organic coating is formed contact the first conductive fine particles covered by the second reactive organic coating to react with each other; a process of cleaning and removing redundant first conductive fine particles covered by the second reactive organic coating to selectively form a first patterned monostratal conductive fine particle film; a process of forming a third reactive organic coating on the surface of the second conductive fine particle by dispersing the second conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the surface of the end of the lead wire on which the first patterned monostratal conductive fine particle film covered by the second reactive organic coating is formed contact the second conductive fine particles covered by the third reactive organic coating to react with each other; and a process of cleaning and removing redundant second conductive fine particles covered by the third reactive organic coating to selectively form a second patterned monostratal conductive fine particle film.
14. The method for manufacturing an electrode as claimed in Claim 13, wherein the first reactive organic coating and the third reactive organic coating are made of the same materials.
15. The method for manufacturing an electrode as claimed in Claim 13, wherein after the process of forming the second patterned monostratal conductive fine particle film, repetitively performing the process of forming the first patterned monostratal conductive fine particle film and the process of forming the second patterned monostratal conductive fine particle film in the same way.
16. The method for manufacturing an electrode as claimed in Claim 13, wherein after the process of forming the first, second, and third reactive organic coatings, the surfaces of the base material or conductive fine particles are cleaned with an organic solvent to form the first, second, and third reactive monomolecular films which are covalently bound with the surface of the base material or conductive fine particles, respectively.
17. The method for manufacturing an electrode as claimed in Claim 13, wherein the first and the third reactive organic coatings comprise an epoxy group, and the second reactive organic coating comprises an imino group.
18. The method for manufacturing an electrode as claimed in Claim 5 or 13, wherein a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst.
19. The method for manufacturing an electrode as claimed in Claim 5 or 13, wherein at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst.
20. A lead wiring, wherein the end of the wiring on a circuit substrate and the lead wire are connected to each other via a first organic coating formed on the surface of the end of the wiring, a second organic coating formed on the surface of the conductive fine particles, and a third organic coating formed on the surface of the lead wire.
21. A lead wiring, wherein the conductive fine particles are formed in one layer or in multiple layers.
22. The lead wiring as claimed in Claim 20, wherein the first organic coating and the third organic coating are covalently bound to each other directly or indirectly via the second organic coating formed on the surface of the conductive fine particles.
23. The lead wiring as claimed in Claim 21 , wherein the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.
24. The lead wiring as claimed in any of Claims 20, 21 , 22, and 23, wherein the first organic coating, the second organic coating, and the third organic coating comprise a monomolecular film.
25. A method for connecting a lead wiring comprising: a process of forming a first reactive organic coating on the surface of the end of the wiring by contacting the surface of the end of the wiring or the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming a third reactive organic coating on the surface of the end of the wiring or the surface of the end of the lead wire by contacting the surface of the end of the lead wire to an alkoxysilane compound among a chemical adsorption liquid produced from a mixture of at least the third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the end of the wiring or the surface of the end of the lead wire to react with the alkoxysilane compound; a process of forming said first or third reactive organic coating into a prescribed pattern; a process of forming a second reactive organic coating on the surface of the conductive fine particle by dispersing the conductive fine particles among a chemical adsorption liquid produced from a mixture of at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle to react with the alkoxysilane compound; a process of having the surface of the end of the wiring or the end of the lead wire on which the patterned first or third reactive organic coating is formed contact the conductive fine particles covered by the second reactive organic coating to selectively react with each other; a process of cleaning and removing redundant conductive fine particles covered by the second reactive organic coating to form a layer of conductive fine particles covered by the 24th reactive organic coating; and a process of clamping the end of said wiring and the end of said lead wire to connect with each other via the layer of conductive fine particles.
26. The method for connecting a lead wiring as claimed in Claim 25, wherein the layers of the conductive fine particles are formed in multiple layers.
27. The method for connecting a lead wiring as claimed in Claim 25, wherein the conductive fine particles covered by the second and the fourth reactive organic coatings, respectively, are contacted to the top surface of the end of the wiring and the end of the lead wire on which the patterned first and third reactive organic coatings are formed to selectively react with each other, forming a layer of the conductive fine particles covered by the second and the fourth reactive organic coatings on the respective top surfaces.
28. The method for connecting a lead wiring as claimed in Claim 27, wherein the second and the fourth reactive organic coatings comprise a functional group that reacts with each other.
29. An electronic component, wherein the electrode of Claims 1 , inclusive, the electrode of Claims 9 through 12, inclusive, and the lead wiring of Claims 20, inclusive, are used.
30. Electronic equipment, wherein the electrode of Claims 1 , inclusive, the electrode of Claims 9 through 12, inclusive, and the lead wiring of Claims 20, inclusive, are used.
PCT/JP2007/066326 2007-08-16 2007-08-16 Electrode and method for manufacturing the same, lead wiring using the electrode and method for connecting the same, and related electronic components and electronic equipment WO2009022438A1 (en)

Priority Applications (1)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05297401A (en) * 1992-02-17 1993-11-12 Mitsubishi Electric Corp Method for connecting circuit board
JP2007173518A (en) * 2005-12-22 2007-07-05 Kagawa Univ Optical sensor and manufacturing method thereof
JP2007220884A (en) * 2006-02-16 2007-08-30 Kagawa Univ Electrode and its manufacturing method, lead wiring using the same and its connecting method, and electronic parts and electronic apparatus using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05297401A (en) * 1992-02-17 1993-11-12 Mitsubishi Electric Corp Method for connecting circuit board
JP2007173518A (en) * 2005-12-22 2007-07-05 Kagawa Univ Optical sensor and manufacturing method thereof
JP2007220884A (en) * 2006-02-16 2007-08-30 Kagawa Univ Electrode and its manufacturing method, lead wiring using the same and its connecting method, and electronic parts and electronic apparatus using the same

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