WO2009022437A1

WO2009022437A1 - Wiring and method for manufacturing the same and electronic components and related electronic equipment

Info

Publication number: WO2009022437A1
Application number: PCT/JP2007/066315
Authority: WO
Inventors: Kazufumi Ogawa
Original assignee: Kazufumi Ogawa
Priority date: 2007-08-16
Filing date: 2007-08-16
Publication date: 2009-02-19

Abstract

The present invention relates to wiring using a patterned monostratal conductive fine particle film in which the selectively formed monostratal conductive fine particle film is covalently bound to the surface of the base material via a first organic coating selectively formed on the surface of the base material and a second organic coating formed on the surface of the conductive fine particles, and further the wiring comprises the foregoing organic coatings that are different from each other.

Description

DESCRIPTION

WIRING AND METHOD FOR MANUFACTURING THE SAMEAND ELECTRONIC

COMPONENTS AND RELATED ELECTRONIC EQUIPMENT

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention is related to a conductor wiring and the method for manufacturing the same, which is used for electronic devices and printed boards. In particular, it relates to a conductor wiring using a monostratal film of conductive fine particles or a laminated body of conductive fine particles comprising conductive fine particles, which 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 and also relates to electronic components and related 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 includes fine metal oxide particles such as ITO and SnO₂. Electronic component includes semiconductor integrated circuits and printed boards. Electronic equipment includes equipment that uses a semiconductor integrated circuit or printed board.

Description of Related Art

Conventional conductor wiring used for electronic devices and printed boards and the method for manufacturing the same are known to include a method of forming the wiring by printing a conductive paste or a method of forming the wiring by selectively removing the metal layer on the surface of a metal laminated substrate with photolithographic etching. For example, the following patent is acknowledged. [Patent document 1] Japanese Patent Laid-Open No. 2002-124518 However, printing and photolithography are insufficient to handle the finer and higher density design of electronic devices and printed boards.

In order to make the wiring finer on electronic devices and printed boards, it is necessary to form the conductive fine particles into a film with a uniform film thickness on the boards. However, there was no concept of manufacturing a film coating with an even thickness at the particle size level by accumulating each monolayer comprising those conductive fine particles. The present invention aims to provide wiring 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 any base material, or wiring 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 electronic devices and related electronic equipment.

SUMMARY OF THE INVENTION

In order to solve the above described problems, the first aspect of this invention, which is presented as wiring using a patterned monostratal conductive fine particle film, wherein the selectively formed monostratal conductive fine particle film is covalently bound to the surface of the base material via a first organic coating selectively formed on the surface of the foregoing base material and a second organic coating formed on the surface of the foregoing conductive fine particles.

The second aspect of this invention is the wiring of the foregoing first aspect of this invention using a patterned monostratal conductive fine particle film, wherein the first organic coating formed on the surface of the base material 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 wiring of the foregoing first aspect of this invention using a patterned monostratal conductive fine particle film, 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 wiring of the foregoing first and second aspects of this invention using a patterned monostratal conductive fine particle film, wherein the first organic coating formed on the surface of the base material 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 wiring using a monostratal conductive fine particle film comprising a process of forming a first reactive organic coating on the surface of the base material by contacting the surface of the foregoing base material 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 base material 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 film to react with the alkoxysilane compound; a process of having the surface of the base material 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 wiring of the foregoing fifth aspect of this invention using a patterned monostratal conductive fine particle film comprising a process of forming the first reactive organic coating on the surface of the base material by contacting the surface of the base material 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 base material 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 film to react with the alkoxysilane compound; and followed by a process of forming first and second reactive monomolecular films, which are covalently bound to the surfaces of the base material and conductive fine particles, respectively, by cleaning the surfaces of the base material and conductive fine particles with an organic solvent.

The seventh aspect of this invention is the method for manufacturing wiring of the foregoing fifth aspect of this invention using a patterned monostratal conductive fine particle film, 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 wiring of the foregoing sixth aspect of this invention using a patterned monostratal conductive fine particle film, 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 wiring using a patterned laminated body of conductive fine particle films, wherein the conductive fine particles selectively accumulated in layers on the surface of the base material 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 wiring of the foregoing ninth aspect of this invention using a patterned laminated body of conductive fine particle films, 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 wiring of the tenth aspect of this invention using a patterned laminated body of conductive fine particle films, 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 wiring of the foregoing ninth aspect of this invention using a patterned laminated body of conductive fine particle films, 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 wiring using a patterned laminated body of conductive fine particle films comprising a process of forming a first reactive organic coating on the surface of the base material by contacting at least the surface of the base material 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 base material 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 the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle film to react with the alkoxysilane compound; a process of having the surface of the base material 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 the third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle film to react with the alkoxysilane compound; a process of having the surface of the base material 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 wiring of the foregoing thirteenth aspect of this invention using a patterned laminated body of conductive fine particle films, wherein the first reactive organic coating and the third reactive organic coating are made of the same. The fifteenth aspect of this invention is the method for manufacturing wiring in the foregoing thirteenth aspect of this invention using a patterned laminated body of conductive fine particle films with a multilayered structure, 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 wiring in the thirteenth aspect of this invention using a patterned laminated body of conductive fine particle films, wherein after the process of forming the first to third reactive organic coatings, the surfaces of the base material or conductive fine particles are cleaned with an organic solvent to form the first to third reactive monomolecular films, which 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 wiring of the foregoing thirteenth aspect of this invention using a patterned laminated body of conductive fine particle films, 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 wiring in the foregoing fifth or thirteenth aspect of this invention using a patterned monostratal conductive fine particle film or a patterned laminated body of conductive fine particle films, 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 wiring in the foregoing fifth or thirteenth aspects of this invention using a patterned monostratal conductive fine particle film or a patterned laminated body of conductive fine particle films, 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 an electronic component, wherein the wiring of the foregoing first through seventh aspects of this invention, inclusive, and the wirings of the ninth through twelfth aspects of this invention, inclusive, is used.

The twenty-first aspect of this invention is electronic equipment, wherein the wiring of the foregoing first through seventh aspects of this invention, inclusive, and the wiring of the ninth through twelfth aspects of this invention, inclusive, is used. The gist of the present invention is further described hereinafter. The gist of the present invention provides wiring using a patterned monostratal conductive fine particle film, wherein the selectively formed monostratal conductive fine particle film is covalently bound to the surface of the base material via a first organic coating selectively formed on the surface of the base material 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 base material by contacting the surface of the base material 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 base material 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 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 film to react with the alkoxysilane compound; a process of having the surface of the base material 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 controlling the film thickness of the patterned monostratal conductive fine particle film, if performing a process of forming the first reactive organic coating on the surface of the base material by contacting the surface of the base material 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 base material 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 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 film to react with the alkoxysilane compound; and followed by a process of forming the first and second reactive monomolecular films, which are covalently bound to the surfaces of the base material and conductive fine particles, respectively, by cleaning the surfaces of the base material and conductive fine particles with an organic solvent.

Furthermore, if the first reactive organic coating comprises an epoxy group and the second reactive organic coating comprises an imino group, it is advantageous for manufacturing wiring to use a patterned monostratal conductive fine particle film that is covalently bound to the surface of the base material.

In addition, if the first reactive monomolecular film comprises an epoxy group and the second reactive monomolecular film comprises an imino group, it is advantageous for manufacturing wiring to use a patterned monostratal conductive fine particle film that is covalently bound to the surface of the base material.

Furthermore, 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 reducing the time for film formation. In addition, 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 further reducing the time for film formation.

Moreover, if the first organic coating formed on the surface of the conductive fine particle and the second organic coating formed on the surface of the base material are different from each other, it is advantageous for binding only one layer of the patterned monostratal conductive fine particle film to the surface of the base material.

In addition, it is advantageous for providing wiring to use a patterned monostratal conductive fine particle film with an excellent bonding strength to the base material, if the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.

In addition, if the first organic coating formed on the surface of the conductive fine particle and the second organic coating formed on the surface of the base material comprise a monomolecular film, it is advantageous for improving the evenness of the film thickness. The gist of the present invention provides wiring using a patterned laminated body of conductive fine particle films, wherein the conductive fine particles selectively accumulated in layers on the surface of the base material 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 base material by contacting at least the surface of the base material 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 base material 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 film to react with the alkoxysilane compound; a process of having the surface of the base material 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 film to react with the alkoxysilane compound; a process of having the surface of the base material 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 selectively 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 simplifying the method for manufacturing the patterned laminated body of conductive fine particle films. In addition, the wiring can easily be manufactured using a patterned laminated body of conductive fine particle films with a multilayered structure, 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 after the process of forming the second patterned monostratal conductive fine particle film.

Furthermore, after the process of forming the first to 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 to third reactive monomolecular films, which are covalently bound to the surface of the base material or conductive fine particles, respectively, it is advantageous for making the film thickness of the patterned laminated body of conductive fine particle films uniform.

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 wiring to use a patterned laminated body of conductive fine particle films that are covalently bound between layers by a reaction between the epoxy group and imino group. Furthermore, 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 reducing the time for film formation.

In addition, 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 further reducing the time for film formation.

In so doing, it is advantageous for simplifying the process of manufacturing the wiring to use a patterned laminated body of conductive fine particle films with a multilayered structure, 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.

In addition, if the first organic coating and the second organic coating react to form a covalent bond, it is advantageous for providing wiring to use a patterned laminated body of conductive fine particle films with an excellent bonding strength.

In addition, it is advantageous for providing wiring to use a patterned laminated body of conductive fine particle films excellent in terms of strength, if the covalent bond is an N-C bond formed by a reaction between an epoxy group and an imino group.

As described above, the present invention allows the manufacture of wiring using a film coating (a patterned monostratal conductive fine particle film) with an even thickness at the particle size level by arranging conductive fine particles only in one layer on the surface of any base material, or wiring using a film coating (a patterned laminated body of conductive fine particle films) by 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 conductivity of each conductive fine particle. Therefore, the present invention has the particular effect of providing wiring excellent in controlling the evenness of the film thickness on the surface of a single base material, and the present invention has the particular effect of providing electronic components and related electronic equipment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 contains conceptual diagrams of the first example of the present invention, which expand the reaction of the surface of the glass substrate 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 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 expand the reaction of the surface of the glass substrate to the molecular level. FIG. 3A shows the surface of the substrate on which a patterned monostratal conductive fine silver particle film is formed as wiring. FIG. 3B shows the surface of the substrate on which two layers of the patterned monostratal conductive fine silver particle films are formed as wiring.

DETAILED DESCRIPTION

The present invention provides wiring using a patterned laminated body of conductive fine particle films, wherein the conductive fine particles accumulated in layers on the surface of the base material 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 base material by contacting at least the surface of the base material 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 base material 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 film to react with the alkoxysilane compound; a process of having the surface of the base material on which the first reactive organic coating is formed contact the first conductive fine particles covered by the second reactive organic coating to selectively react with each other; a process of cleaning and removing redundant first conductive fine particles covered by the second reactive organic coating to 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 film to react with the alkoxysilane compound; a process of having the surface of the base material 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 selectively react with each other; and a process of cleaning and removing redundant second conductive fine particles covered by the third reactive organic coating to form a second patterned monostratal conductive fine particle film.

Therefore, the present invention works to provide wiring 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 any base material, or wiring 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 while both wirings are excellent in controlling and maintaining a uniform film thickness on the surface of a single base material by using two types of conductive fine particles covered by two types of coatings without losing the original function of the conductive fine particles. The present invention also works to simplify the manufacture of the wiring while reducing costs. Although examples are hereinafter used to describe the details of the present invention, these examples shall not be construed as limiting the present invention.

According to the present invention, in order to produce the wiring using a patterned monostratal conductive fine particle film or the wiring 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. First, fine silver particles are used to explain the representative example. [Example 1]

First, a glass substrate 1 as a base material for the wiring formation 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 to be 99 w/t % and as a silanol condensation catalyst, for example, dibutyltin diacetylacetonate was measured to be 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]

CH₃

Then the glass substrate 1 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 glass substrate 1 contains many hydroxyl groups 2 (shown in FIG. 1A), a chemical adsorption monomolecular film 3 containing epoxy groups, which forms a chemical bond with the surface of the glass substrate 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 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 (in this case, Tricren [Trichloroethylene]) or N-methylpyrrolidinon was used for cleaning, and thus the glass substrate 4 covered by the chemical adsorption monomolecular film (the first reactive organic coating) containing a reactive functional group, for example, epoxy group over the surface was manufactured, respectively. (Shown in FIG. 1B)

Since this coating is extremely thin at a film thickness of the nanometer level, the transparency of the glass substrate 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 glass substrate reacted at the surface with the moisture in the atmosphere, and a glass substrate 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 the unwanted part of the surface of the foregoing glass substrate and to remove the foregoing reactive monomolecular film by ablation (shown in FIG. 1C), or the ring of the epoxy group was opened to be deactivated. (Shown in FIG. 1D) Thus, substrates 6 and 6¹, on which the surfaces of the glass substrates were selectively covered by patterned coatings 5 and 5' containing the epoxy group, were manufactured.

As an alternative method, to the surface of the foregoing coating, a cationic polymerization initiator (e.g. IRGACURE 250 made by Chiba Specialty Chemicals K. K.) was diluted with methyl ethyl ketone (MEK) and applied to the surface of the epoxy coating, and then selectively exposed to a far-ultraviolet radiation. This process also allowed the selective 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 as a conductive fine particle with a 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 the following chemical formula [Formula 3], was measured at 99 w/t % and as a silanol condensation catalyst, for example, 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)SSi -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 about 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 monomolecular film 14 containing amino groups (the second reactive organic coating), 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 Si(OCH₃) group of the foregoing chemical adsorption agent and the foregoing hydroxyl groups under the presence of acetic acid, a type of organic acid (shown in FIGs. 2B and 2C). [Formula 4]

O—

H₂N(CH₂)SSi - 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 a chlorinated solvent (in this case, Tricren) 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 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 containing the amino group, was manufactured, respectively.

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. 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 SiCb 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)_H-SH (where n is a whole number)), or in particular, when H₂N(CH₂)_H-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 method uses a dealcoholization reaction, it is applicable to both organic and inorganic conductive fine silver particles and is capable of wide application. [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 a glass substrate 22, selectively covered by a chemical adsorption monomolecular film 21 (the first reactive organic coating) containing the foregoing epoxy group, and were heated to about 100 degrees Celsius; the amino group on the surface of the fine silver particles contacting the epoxy group on the surface of the glass substrate was added by a reaction as shown in the following formula [Formula 5] to selectively bind the fine silver particles and the glass substrate 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 substrate 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 wiring 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 glass substrate 22, were selectively arranged only in one layer. (Shown in FIG. 3A)

Since the thickness of the patterned monostratal conductive fine silver particle film made of the fine silver particles is about 100 nm with excellent evenness, any color interference could not be observed at all.

Although the conductive fine silver particles were covered by an insulating organic thin film, the film thickness was extremely thin so that conductivity was 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. [Example 4]

In addition, if the film thickness of the conductive fine silver particle film needs to be thicker in order to increase the current capacity, 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 glass substrate 22, on which the patterned monostratal conductive fine silver particle film 24 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 100 degrees Celsius. As a result, the epoxy group on the surface of the fine silver particles, contacting the amino group, was added to 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 glass substrate.

Then again, the surface of the substrate 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 a patterned monostratal conductive fine silver particle film with the two-layer structure 26 was formed with an even thickness at the particle size level, while the second layer of the fine silver particles covalently bound to the glass substrate 7 was arranged only in one layer (shown in FIG. 3B).

Similarly, when the fine silver particles covered by the chemical adsorption monomolecular film containing the amino group (e.g. the second reactive organic coating) and the fine silver particles covered by the chemical adsorption monomolecular film containing the epoxy group (e.g. the first reactive organic coating) were alternately laminated, and wiring comprising an accumulated coating of conductive fine silver particles with a multilayered structure was manufactured. The wiring in which the epoxy group and the amino group were added to each other to bind and solidify the fine silver particles formed polymer wiring with the conductivity of 0.2 x 10⁶ Siemens. 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:

(I) (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 (CHz)₇Si(OC₂Hs)₃ (7) (CH₂OCH)CH₂O (CH₂)nSi(OC₂H₅)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

(II) 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(CH2)7Si(OC₂H5)3

(16) H₂N(CH2)9Si(OC₂H₅)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, tetrabutyl titanate, tetranonyl titanate, 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. 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. More precisely, chlorosilane non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffln, n-paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, and dimethylformamide can be used.

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 half an 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 half an 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; etc.

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, glass substrate 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. Wiring using a patterned monostratal conductive fine particle film, wherein the selectively formed monostratal conductive fine particle film is covalently bound to the surface of the base material via a first organic coating selectively formed on the surface of said base material and a second organic coating formed on the surface of said conductive fine particles.

2. The wiring using a patterned monostratal conductive fine particle film as claimed in Claim 1 , wherein the first organic coating formed on the surface of the base material and the second organic coating formed on the surface of the conductive fine particles are different from each other.

3. The wiring using a patterned monostratal conductive fine particle film 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 wiring using a patterned monostratal conductive fine particle film as claimed in Claim 1 or 2, wherein the first organic coating formed on the surface of the base material and the second organic coating formed on the surface of the conductive fine particles comprise a monomolecular film.

5. A method for manufacturing wiring using a monostratal conductive fine particle film comprising: a process of forming a first reactive organic coating on the surface of the base material by contacting the surface of said base material 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 base material 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 film 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 film to react with the alkoxysilane compound; a process of having the surface of the base material 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 wiring using a patterned monostratal conductive fine particle film as claimed in Claim 5 comprising: a process of forming the first reactive organic coating on the surface of the base material by contacting the surface of the base material 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 base material 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 film to react with the alkoxysilane compound; and followed by a process of forming first and second reactive monomolecular films, which are covalently bound to the surfaces of the base material and conductive fine particles, respectively, by cleaning the surfaces of the base material and conductive fine particles with an organic solvent.

7. The method for manufacturing wiring using a patterned monostratal conductive fine particle film 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 wiring using a patterned monostratal conductive fine particle film 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. Wiring using a patterned laminated body of conductive fine particle films, wherein the conductive fine particles selectively accumulated in layers on the surface of the base material are covalently bound to each other between layers via the organic coating formed on the surface of the conductive fine particles.

10. The wiring using a patterned laminated body of conductive fine particle films 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 wiring using a patterned laminated body of conductive fine particle films 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 wiring using a patterned laminated body of conductive fine particle films 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. The method for manufacturing wiring using a patterned laminated body of conductive fine particle films comprising: a process of forming a first reactive organic coating on the surface of the base material by contacting at least the surface of the base material 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 base material 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 the second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle film to react with the alkoxysilane compound; a process of having the surface of the base material 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 the third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent in order for the surface of the conductive fine particle film to react with the alkoxysilane compound; a process of having the surface of the base material, 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 wiring using a patterned laminated body of conductive fine particle films as claimed in Claim 13, wherein the first reactive organic coating and the third reactive organic coating are made of the same.

15. The method for manufacturing wiring using a patterned laminated body of conductive fine particle films with a multilayered structure 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 wiring using a patterned laminated body of conductive fine particle films as claimed in Claim 13, wherein after the process of forming the first to third reactive organic coatings, the surfaces of the base material or conductive fine particles are cleaned with an organic solvent to form the first to 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 wiring using a patterned laminated body of conductive fine particle films 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 wiring using a patterned monostratal conductive fine particle film or a patterned laminated body of conductive fine particle films 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 wiring using a patterned monostratal conductive fine particle film or a patterned laminated body of conductive fine particle films 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 for use.

20. An electronic component, wherein the wirings of Claims 1, inclusive, and the wirings of Claims 9 through 12, inclusive, are used.

21. Electronic equipment, wherein the wirings of Claims 1 , inclusive, and the wirings of Claims 9 through 12, inclusive, are used.