JP2002128581A - Copper-metallized composition, ceramic wiring substrate using the same and method of fabrication - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper-metallized composition that enables to calcine simultaneously with a mixed ceramic (BAS ceramic) material containing BaO, Al2O3 and SiO2 and is utilized usefully to obtain a conductor film having a high adhesive strength to a ceramic body including the BAS ceramic material. SOLUTION: The copper-metallized composition is comprised of adding a particle of total 0.5 to 30.0 wt.%, whose average particle size is of 0.1 to 10.0 μm and which is composed of a transition metal belonging to a quaternary A family and/or a quintuple A family and/or a transition-metal oxide belonging to the same according to a periodic law table, to a main component comprising a mixture of Cu, CuO and Cu-CuO, a mixture of Cu-Cu2O or a mixture of CuO- Cu2O.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper metallized composition, a ceramic wiring board using the same, and a method for producing the same, and particularly to BaO, Al ₂ O _3.
The present invention relates to a copper metallized composition advantageously used for forming a conductive film on a substrate made of a mixed ceramic (BAS ceramic) containing SiO ₂ and SiO ₂ , a ceramic wiring board using the same, and a method of manufacturing the same.

[0002]

2. Description of the Related Art A ceramic wiring board has various electronic components mounted thereon and is used for wiring these electronic components. More specifically, a package component for housing a semiconductor element such as an IC or an LSI. And hybrid integrated circuit devices on which a plurality of types of electronic components are mounted. As a base material for a ceramic wiring board, alumina is often used because of its excellent properties such as electrical insulation and chemical stability.

In such a ceramic wiring board,
As higher frequencies and higher densities have progressed, lower dielectric constants have been required for substrates, and wiring conductors have
Lower wiring resistance has been required.

[0004] Therefore, as a material for the substrate, a mixed ceramic (BAS ceramic) containing BaO, Al ₂ O ₃ and SiO ₂ instead of alumina has attracted attention.
Further, in order to realize a low wiring resistance, it is preferable to use, for example, copper (Cu), gold (Au) or silver (Ag) as a material for the wiring conductor.
In particular, it is more preferable to use copper.

[0005] There are two types of ceramic wiring boards, one having a single-layer structure and the other having a multi-layer structure. In manufacturing a ceramic wiring board having a multilayer structure using BAS ceramic as a base material, a BAS ceramic raw material powder is generally used. And a slurry obtained by mixing an organic binder and a solvent are formed into a sheet by applying a sheet forming method such as a doctor blade method, and the obtained ceramic green sheet is, if necessary, a via hole conductor. After forming a through hole for filling a conductive paste into the through hole or forming a conductive film having a predetermined pattern by applying a thick film forming method such as a screen printing method, a plurality of ceramic greens are formed. The binder is removed by laminating the sheets, pressing and heating the resulting green ceramic compact having the laminated structure Then, it is made to baking.

In the above-described method for manufacturing a ceramic wiring board, when copper is used as a material of a via-hole conductor or a conductive film, as described above, the conductive paste for forming these contains a copper metallized composition. In. For such copper metallized compositions, 1000
The main component is Cu, which can be fired at a low temperature of
O, the CuO mixture or CuO-Cu ₂ O mixture, B
Add i ₂ O ₃ , add Bi ₂ O ₃ , MoO ₃ and C
Copper metallized compositions to which r ₂ O ₃ has been added are disclosed, for example, in JP-A-4-83781 and JP-A-5-4884.
No., published in Japanese Unexamined Patent Publication No.

[0007]

When an electronic component such as a filter is mounted on a ceramic wiring board having a ceramic base made of the above-described BAS ceramic, for example, it is formed on the outer surface of the ceramic wiring board. After applying nickel plating and gold plating to the conductor film,
Such electronic components are mounted using solder.

[0008] However, the conductor film obtained by the above-mentioned copper metallized composition is porous.

Therefore, when nickel plating or gold plating is performed, these treatment liquids penetrate the conductive film in the acid treatment with a hydrochloric acid solution or a sulfuric acid solution or the alkali treatment with ammonia or the like as a pretreatment for plating, and the BAS ceramic is removed from the BAS ceramic. To the interface between the ceramic substrate and the conductive film. As a result, although the Cu and residual CuO in the conductor film are trace amounts, they dissolve in this treatment solution, and in particular, the dissolution of Cu and residual CuO at the interface between the ceramic substrate and the conductor film causes the ceramic substrate and the conductor film to dissolve. There is a case where a fatal problem of extremely lowering the adhesive strength between the two may be encountered.

The nickel plating bath and the gold plating bath are
Since the solution is an acid-based or alkali-based solution, the permeation of these solutions causes corrosion of the conductor film to proceed, and the adhesive strength is reduced to about 0.5 kg / 2 mm square. As a result, the stress exerted by the plating film causes There is also a problem that the conductor film is easily peeled off.

Furthermore, when an electronic component is to be mounted on a nickel-plated and gold-plated conductive film by using solder, there is a problem that the conductive film is easily peeled off due to the heat shrinkage stress of the solder.

Japanese Patent Application Laid-Open No. 10-95686 discloses a copper metallized composition for a conductor film which can be co-fired with a base material made of glass ceramic and can give a high adhesive strength to the base. The main components such as
A copper metallized composition containing a metal such as i, Mo, Fe, Co and an oxide such as NiO is described.

However, when the copper metallized composition disclosed herein is used, these Ni, Mo, Fe, C
Metals such as o dissolve together with copper in a treatment solution for acid treatment or alkali treatment as a pretreatment for plating,
The adhesive strength after plating is less than 2 kg / 2 mm square, and for example, when an electronic component is mounted using solder, a fatal problem that a conductor film is peeled off may be caused.

Therefore, an object of the present invention is to provide, for example, a BA
A copper metallized composition that can be co-fired with a ceramic substrate made of S-ceramic, exhibits high adhesive strength to the ceramic substrate, and can form a conductive film having excellent corrosion resistance especially to an acid-based plating bath And a ceramic wiring board using the same, and a method for manufacturing the same.

[0015]

SUMMARY OF THE INVENTION The present invention is first directed to a copper metallized composition. The copper metallized composition according to the present invention has an average particle size of 0.1 to 10.0 μm with respect to a main component containing Cu, and has a transition of Group IVA and / or VA according to the periodic table of elements. Metal and / or
Alternatively, the transition metal oxide particles in a total amount of 0.5 to 3
It is characterized by adding 0.0% by weight.

The main component described above is preferably C
u, CuO, Cu-CuO mixture, Cu-Cu ₂ O mixture, and at least one selected from CuO-Cu ₂ O mixture is used.

Further, Nb is particularly preferably used as the transition metal, and Nb ₂ O ₅ is particularly preferably used as the transition metal oxide.

The copper metallized composition according to the present invention contains 8
It is preferably directed to an application which is co-fired with a mixed ceramic (BAS ceramic) material containing BaO, Al ₂ O ₃ and SiO ₂ at a temperature of 00 to 1000 ° C.

The present invention is also directed to a method for manufacturing a ceramic wiring board. This manufacturing method includes a step of preparing a copper metallized composition as described above, a step of preparing a green ceramic molded body containing a BAS ceramic material, and applying the copper metallized composition onto the green ceramic molded body. And a step of firing the green ceramic compact together with the copper metallized composition at a temperature of 800 to 1000 ° C. in a reducing atmosphere.

The present invention is further directed to a ceramic wiring board obtained by the above-described manufacturing method. The ceramic wiring board includes a ceramic substrate obtained from a raw ceramic molded body, a conductor film obtained from a copper metallized composition, and a glass layer formed along an interface between the ceramic substrate and the conductor film. Features.

In the above-mentioned glass layer, the above-mentioned IVA No.
Group and / or group VA transition metals and / or transition metal oxides thereof, wherein the particles of these transition metals and transition metal oxides have an area ratio on the cross section of the glass layer of 20 to 80%. It is preferable to contain in the range.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to manufacture a ceramic wiring board according to one embodiment of the present invention, the following steps are performed.

First, in order to obtain a ceramic base provided on a ceramic wiring board, for example, a mixture of barium oxide, silicon oxide, alumina, calcium oxide and boron oxide, a binder made of polyvinyl butyral,
A slurry is prepared by mixing a plasticizer composed of di-n-butyl phthalate and a solvent composed of toluene and isopropylene alcohol. Next, the slurry is formed into a sheet on an organic film by a doctor blade method, and dried to obtain a ceramic green sheet.

In the slurry for obtaining the above-mentioned ceramic green sheet, a specific inorganic compound or glass is added to the slurry for the purpose of accelerating sintering, controlling shrinkage behavior, improving strength and controlling electric characteristics, or insulating the ceramic substrate. A metal may be added as long as the properties are not impaired, and an antistatic agent and a tackifier may be further added. Also, for the above-mentioned binder, plasticizer and solvent,
Other than those exemplified above may be used.

Next, a wiring conductor such as a conductor film having a desired pattern or a via-hole conductor is formed on each of the ceramic green sheets produced as described above.

In forming a wiring conductor such as a conductor film or a via-hole conductor located inside a green body formed of a plurality of green sheets, a conductive material containing copper powder having an average particle size of 0.5 to 4.0 μm as a main component is used. A conductive paste is used. In particular, for forming a conductive film, the conductive paste is printed.

As the conductive paste used here, in addition to copper, a paste containing aluminum, nickel, silver, gold or palladium or an alloy containing at least one of these metals may be used. For the purpose of controlling the temperature characteristics, improving the printability, and improving the bonding strength, a specific resin, an inorganic substance, glass, or the like may be added, or a surface treatment with these may be performed.

For the conductive film formed on the outer surface of the laminate of a plurality of green sheets, a conductive paste containing the copper metallized composition according to the present invention is used.

That is, the average particle size is 0.1 to 10.0 μm.
m, preferably 0.5 to 4.0 μm Cu, CuO,
While having Cu ₂ O, a Cu—CuO mixture, a Cu—Cu ₂ O mixture, or a CuO—Cu ₂ O mixture as a main component, as an additive, the average particle diameter is 0.1 to 10.0 μm, and the period of the element is A Group IVA transition metal according to the table, ie at least one of Ti, Zr and Hf;
And / or Group VA transition metals, ie, V, Nb
And / or Ta and / or the transition metal oxide, ie, TiO ₂ , ZrO ₂ , H
A conductive paste containing a copper metallized composition to which at least one kind of particles of fO ₂ , V ₂ O ₅ , Nb ₂ O ₅ and Ta ₂ O ₅ is added in a total amount of 0.5 to 30.0% by weight. It is used and printed to form a desired pattern.

The conductive paste containing the above-mentioned copper metallized composition is an organic paste obtained by mixing at least one of Cu powder, CuO powder and Cu ₂ O powder with an organic vehicle comprising an organic binder and a solvent. It can be obtained by adding a predetermined amount of vehicle, stirring and kneading with a stirring grinder and / or a three-roll mill.

The Cu powder, CuO powder and Cu ₂ O powder used here have no coarse powder or extremely agglomerated powder, and have a maximum coarse particle diameter of 5% after forming the conductive paste.
It is preferable that the thickness be 0 μm or less.

As the binder contained in the organic vehicle, any one can be used. For example, ethyl cellulose, acrylic resin, polyvinyl butyral, methacrylic resin and the like can be used. Further, any solvent can be used, and for example, terpineol, butyl carbitol, butyl carbitol acetate, alcohols and the like can be used.

[0033] If necessary, a dispersant, a plasticizer and an activator may be added to the conductive paste.

The viscosity of the conductive paste is preferably adjusted to 50 to 700 Pa · s ⁻¹ in consideration of printability.

Next, as described above, a plurality of green sheets on which wiring conductors such as conductor films and via-hole conductors are formed are laminated. At this time, the conductive film is formed by a conductive paste containing a copper metallization composition in which a transition metal of Group IVA and / or Group VA and / or particles of the transition metal oxide are added to a main component containing Cu. Are formed so as to form the outermost layer. Then, the stacked green sheets have a temperature of 80 ° C. and a pressure of 200 kg / cm.
Pressing is performed under the conditions of ² , whereby a green ceramic molded body having a laminated structure is obtained.

Next, this green ceramic molded body is
In a reducing atmosphere having an oxygen concentration of 0.1 to 30 ppm, for example, in a nitrogen atmosphere, firing is performed at a temperature of 800 to 1000 ° C., for example, 980 ° C. for a holding time of one hour.

Next, the fired conductor film is treated with an acid solution such as hydrochloric acid or sulfuric acid of an appropriate concentration or an alkali solution such as ammonia, so that a nickel film and a gold film having a predetermined thickness are respectively deposited. Is subjected to nickel plating and gold plating.

Next, after an appropriate flux is applied on the conductor film, solder is applied so as to cover the conductor film by a dipping method or the like.

FIG. 1 is an enlarged sectional view showing a part of the ceramic wiring board 1 obtained as described above. FIG. 1 shows a ceramic substrate 2 obtained from a green ceramic compact and a conductor film 3 obtained from a copper metallized composition.
Is shown schematically in an enlarged manner.

As shown in FIG. 1, a part of the glass component 4 in the BAS ceramic contained in the ceramic substrate 2 penetrates between the Cu particles 5 contained in the conductor film 3 to form a penetrated glass portion. At the same time, a glass layer 7 is formed along the interface between the ceramic substrate 2 and the conductor film 3.

More specifically, the transition metal and / or transition metal oxide contained in the conductor film 3
By reacting with the glass component in the BAS ceramic contained in the above, the fluidity of this glass component is increased. As a result, as shown in FIG. 1, the glass component 4 penetrates between the Cu particles 5 so as to form the infiltrated glass portion 6, and simultaneously the Cu and the transition metal and / or the transition metal oxide in the conductor film 3 The transition metal and / or the transition metal oxide diffuses into the glass component 4 based on the difference in the degree of diffusion between them.

As described above, the anchor effect is exhibited by the trace amount of the glass component 4 constituting the infiltrated glass portion 6 and the glass layer 7, and as a result, the conductor film 3 is made of ceramic with the glass component 4 interposed therebetween. Strongly adheres to the substrate 2. In particular, since the transition metal and / or the transition metal oxide is diffused in the glass layer 7, Cu contained in the conductor film 3 contains BA contained in the ceramic substrate 2.
Diffusion into the S-ceramic is advantageously suppressed.

When plating is performed, the area exposed to a solution for acid treatment or alkali treatment as a pre-treatment, or an acid or alkali solution constituting a plating bath is limited by the penetration glass part. 6 and the glass component 4 constituting the glass layer 7, the influence of the solution on the conductor film 3 is reduced, and the corrosion resistance of the conductor film 3 can be greatly improved.

As a result, the adhesive strength of the conductor film 3 is maintained at, for example, 2 kg / 2 mm square or more even after plating, and the conductor film 3 is peeled off by a stress exerted from the plating film, or is mounted using solder. In the process,
The conductor film 3 can be prevented from peeling off due to the heat shrinkage stress of the solder.

When at least one of the transition metal and / or transition metal oxide as an additive in the above-mentioned copper metallized composition has an average particle size of less than 0.1 μm, aggregation of the additives proceeds, and Separates in copper metallized compositions. As a result, the reaction with the glass component in the BAS ceramic does not proceed, so that an anchor effect cannot be obtained and an improvement in adhesive strength cannot be expected.

On the other hand, when the average particle size of the transition metal and / or the transition metal oxide is larger than 10.0 μm, BA
In the reaction with the glass component in the S ceramic, these additives do not diffuse into the glass, but the main component Cu diffuses into the glass. As a result, the transition as the additive on the surface of the conductive film 3 occurs. Since a metal and / or a transition metal oxide is deposited, the plating property is reduced.

The content of at least one of the transition metals and / or transition metal oxides is 0.5% in total.
When the content is less than the weight percentage, the reaction between the glass component in the BAS ceramic and the copper metallized composition is excessively promoted, and as a result, diffusion of copper and / or copper oxide as a main component into the BAS ceramic is promoted. Therefore, after the acid or alkali treatment at the time of plating, the diffused copper and / or copper oxide dissolves, and the adhesive strength of the conductor film 3 is reduced.

On the other hand, when the content of the transition metal and / or the transition metal oxide exceeds 30.0% by weight, the glass component in the BAS ceramic excessively penetrates into the copper metallized composition, and The transition metal oxide precipitates on the surface of the conductor film 3, so that the solder wettability and the plating ability of the conductor film 3 are reduced.

From the above, the average particle diameter of the transition metal and / or transition metal oxide particles added to the copper metallized composition is 0.1 to 10.0 μm.
And the amount added is 0.5-30.0% by weight.

As described above, the transition metal and / or the transition metal oxide is diffused in the glass layer 7, and the content of the transition metal and the transition metal oxide is determined on the cross section of the glass layer 7. 20-80% in area ratio of
That is, it is preferable that the transition metal and the transition metal oxide are contained in a range of 20 to 80% in area ratio on the cross section of the glass layer 7.

When the content is less than 20%, the transition metal and / or the transition metal oxide is deposited on the surface of the conductor film 3, so that the plating property is extremely deteriorated.
If the content exceeds 80%, the difference in the coefficient of thermal expansion between the conductor film 3 and the glass layer 7 increases, causing cracks and peeling of the conductor film 3 in some cases.

From the viewpoint of more reliably preventing warpage and undulation of the ceramic substrate 2, the above-mentioned content is more preferably 40 to 60%.

Preferably, the transition metal is Nb and the transition metal oxide is Nb ₂ O ₅ . This is because these Nb and Nb ₂ O ₅ have good wettability with the glass in the BAS ceramic, and therefore, in the conductor film 3, copper is more easily segregated in the surface layer and the glass component is more easily segregated in the lower layer. As a result, the plating ability to the conductor film 3 becomes better, and the ceramic substrate 2 of the conductor film 3 is formed.
Can be increased so as to ensure that the adhesive strength with respect to 2 kg / 2 mm square exceeds 2 kg / 2 mm square.

[0054]

EXPERIMENTAL EXAMPLES Hereinafter, experimental examples conducted to evaluate the characteristics of the copper metallized composition according to the present invention will be described. In this experimental example, a ceramic wiring board in which a conductor film obtained from a copper metallized composition was formed on a ceramic substrate containing a BAS ceramic.

Table 1 shows the main components of the copper metallized composition, various compositions of transition metals and transition metal oxides, and the compositions of the ceramic substrates used in this experimental example.

[0056]

[Table 1]

Referring to Table 1, when a type of BAS ceramic is used as the material of the ceramic substrate, a mixture of barium oxide, silicon oxide, alumina, calcium oxide and boron oxide, a binder made of polyvinyl butyral, A slurry was prepared by adding and mixing a plasticizer composed of di-n-butyl phthalate and a solvent composed of toluene and isopropylene alcohol, and forming the slurry into a sheet on an organic film by a doctor blade method. Then, drying was performed to produce a ceramic green sheet having a thickness of 125 μm.

On the other hand, when a kind of glass ceramic is used as the material of the ceramic substrate, the method disclosed in
As described in U.S. Pat.
° C, 74% by weight of SiO ₂ , 14% by weight of LiO ₂ , 4% by weight of Al ₂ O ₃ , ₂ % by weight of P ₂ O ₅ , K
₂ % by weight of ₂ O, 2% by weight of ZnO and 2% by weight of Na ₂ O
% By weight of a raw material powder obtained by mixing lithium silicate glass having a composition containing each and forsterite as a filler component, a binder made of an acrylic resin, a plasticizer made of dibutyl phthalate, and a solvent made of toluene and isopropyl alcohol. A slurry was prepared by adding and mixing, and the slurry was formed into a sheet on an organic film by a doctor blade method, and then dried to prepare a glass ceramic green sheet having a thickness of 125 μm.

On the other hand, in order to prepare a conductive paste containing a copper metallizing composition, main components, transition metals and transition metal oxides having various compositions as shown in Table 1 were prepared.

Table 2 and Table 1 are appropriately selected from these main components, transition metals and transition metal oxides.
As shown in FIG. 2, these main components, transition metals and transition metal oxides are weighed so as to have various contents, and an acrylic resin as an organic binder and terpineol as a solvent are added thereto and kneaded. Then, a conductive paste containing the copper metallized composition was produced.

Here, the amount of the organic binder in the conductive paste was 10% by weight based on the main component. The transition metals and transition metal oxides used had average particle diameters as shown in Tables 2 to 12, and the main components used had an average particle diameter of 3 μm.

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

[0068]

[Table 8]

[0069]

[Table 9]

[0070]

[Table 10]

[0071]

[Table 11]

[0072]

[Table 12]

Next, as shown in Tables 2 to 12, a conductive sheet containing the above-described copper metallized composition is formed on a green sheet to be a ceramic substrate containing the above-described type of BAS ceramic or the type of glass ceramic. Plane size after firing is 2 mm using conductive paste
□, a conductive film is formed so as to have a thickness of about 15 μm, and while the green sheet on which the conductive film is formed is the outermost layer, seven green sheets on which the conductive film is not formed are laminated while being pressed, A green ceramic compact was obtained.

Next, this green ceramic molded body was heated at a temperature
80 ° C and pressure 200kg / cm ^TwoPress under the conditions
After that, in a reducing atmosphere having an oxygen concentration of 10 ppm
At a temperature of 980 ° C. and a holding time of 1 hour,
Sintered at the same time as the conductive film, thereby
A mixed wiring substrate was obtained.

Tables 13 to 23 show the evaluation results of the ceramic wiring boards as these samples.

[0076]

[Table 13]

[0077]

[Table 14]

[0078]

[Table 15]

[0079]

[Table 16]

[0080]

[Table 17]

[0081]

[Table 18]

[0082]

[Table 19]

[0083]

[Table 20]

[0084]

[Table 21]

[0085]

[Table 22]

[0086]

[Table 23]

In Tables 2 to 12 and 13 to 23, those marked with * are the samples corresponding to comparative examples outside the scope of the present invention.

In Tables 13 to 23, the “metal particle occupancy ratio in the glass layer” refers to the value obtained by cutting a ceramic wiring substrate as a sample in a direction perpendicular to the main surface of the conductive film so as to cross the conductive film. The thickness of the glass layer existing at the interface between the conductive film and the ceramic substrate is measured using a scanning electron microscope, and a wavelength dispersive X-ray microanalyzer (E
The occupancy of the transition metal and the transition metal oxide is quantitatively analyzed by mapping using PMA), and the area ratio of the region where the transition metal and the transition metal oxide are diffused in a predetermined range of the glass layer is obtained. .

Regarding the “adhesive strength”, a Cu-based lead wire was soldered to the surface of the conductive film, and this lead wire was
The maximum (peak) load when the conductive film was peeled from the ceramic substrate together with the lead wire at a pulling speed of m / min in a direction perpendicular to the main surface of the conductive film was evaluated. In addition, “after plating” has a thickness of 5.0 μm on the conductive film.
The "adhesion strength" after nickel plating and gold plating having a thickness of 0.5 μm thereon was evaluated. "Before plating" means "adhesion strength" before such plating. Was evaluated.

“Solder wettability” is determined by visually observing the solder wettability after plating as described above and determining whether the solder wettability is good or not.

"Judgment" indicates the result of the judgment made by integrating the various evaluation results as described above.

As can be seen from Tables 2 to 12 and 13 to 23, the content of the transition metal and / or the transition metal oxide in the copper metallized composition was 0.5%.
In the sample having less than 20% by weight and the “metal particle occupation ratio in the glass layer” being less than 20%, the “adhesion strength” after “plating” is less than 2 kg / 2 mm □, or the “solder wettability” is low. It's getting worse.

On the other hand, the content of the transition metal and / or the transition metal oxide in the copper metallized composition exceeds 30.0% by weight, and the “metal particle occupation ratio in the glass layer” is 8%.
If the sample exceeds 0% and the “adhesion strength” of “after plating” is 2 kg / 2 mm □ or more, the “solder wettability” is poor.

Further, in the sample in which the average particle size of the transition metal or transition metal oxide in the copper metallized composition is less than 0.1 μm, the “adhesive strength” of “after plating” is 2 kg / 2 m.
It is less than m □ or the “solder wettability” is poor.

On the other hand, a sample in which the average particle size of the transition metal or transition metal oxide in the copper metallized composition exceeds 10.0 μm, and the “adhesive strength” of “after plating” is 2 k
In the case of g / mm □ or more, the “solder wettability” is poor.

When the ceramic base is made of glass ceramic as in samples 367 to 403, the glass component covers the surface of the conductor film, or Cu particles contained in the conductor film In any case, the “adhesive strength” of “after plating” is less than 2 kg / 2 mm □, and the “solder wettability” is poor.

On the other hand, according to the samples within the scope of the present invention, the “adhesive strength” of each of “before plating” and “after plating” is 2 kg / 2 mm □ or more, and the “solder wettability” Is also good, and a totally satisfactory characteristic can be given.

[0098]

As described above, according to the copper metallized composition of the present invention, the average particle diameter is 0.1 to 10.0 μm with respect to the main component containing Cu, and the group IVA and / or Alternatively, since it is obtained by adding a total of 0.5 to 30.0% by weight of particles of a transition metal of Group VA and / or the transition metal oxide, in a reducing atmosphere,
When co-fired with the BAS ceramic material at a temperature of 800 to 1000 ° C., the above-described transition metal and / or transition metal oxide reacts with the glass component in the BAS to increase the fluidity of the glass component, and increase the transition between Cu and the transition metal. Based on the difference in the degree of diffusion from the metal and / or the transition metal oxide, the appropriate amount of the glass component penetrates between the Cu particles while the transition metal and / or the transition metal oxide diffuses into the glass component.

As a result, the conductor film formed of the copper metallized composition is firmly adhered to the ceramic substrate containing the BAS ceramic with the glass layer composed of the above-mentioned glass component interposed therebetween. Since the transition metal and / or the transition metal oxide is diffused therein, the diffusion of Cu in the conductor film to the ceramic base is suppressed. For this reason, the transition metal and / or the transition metal oxide acts to enhance the adhesion between the conductor film and the ceramic substrate, and significantly improves the corrosion resistance to the plating treatment. The adhesion strength before plating is substantially maintained even after plating, and peeling of the conductor film due to the heat shrinkage stress of the solder in the mounting step using the solder can be suppressed.

In the wiring board according to the present invention,
If the transition metal and the transition metal oxide in the glass layer formed along the interface between the ceramic substrate and the conductor film are contained in the area ratio on the cross section of the glass layer in the range of 20 to 80%. In addition, the plating ability of the conductive film can be kept good, and the occurrence of cracks due to the difference in thermal expansion coefficient between the conductive film and the glass layer, and further, the peeling of the conductive film can be suppressed.

[Brief description of the drawings]

FIG. 1 is an enlarged cross-sectional view schematically illustrating an interface between a ceramic substrate 2 and a conductive film 3 in a ceramic wiring board 1 according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ceramic wiring board 2 Ceramic base 3 Conductive film 4 Glass component 5 Cu particle 6 Permeation glass part 7 Glass layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/12 336 H01B 3/12 336 H01L 23/12 H05K 3/12 610G 23/14 3/38 B H05K 3/12 610 H01L 23/12 D 3/38 23/14 M (72) Inventor Daisuke Yoshida 2-26-10 Tenjin, Nagaokakyo-shi, Kyoto F-term in Murata Manufacturing Co., Ltd. (Reference) 5E343 AA24 BB22 BB24 BB59 BB72 DD32 ER38 GG02 GG20 5G301 AA08 AA27 AD10 DA02 DA06 DA23 DD01 5G303 AA05 AB06 CA03 CB01 CB03 CB30

Claims (7)

[Claims] 1. A transition metal of Group IVA and / or VA according to the periodic table of elements, having an average particle size of 0.1 to 10.0 μm with respect to a main component containing Cu.
Alternatively, the transition metal oxide particles in a total amount of 0.5 to 3
A copper metallized composition to which 0.0% by weight was added. 2. The main component is Cu, CuO, Cu—C.
uO mixture Cu-Cu ₂ O mixture, and CuO-C
containing at least one selected from the u ₂ O mixture, copper metallizing composition according to claim 1. 3. The transition metal according to claim 1, wherein the transition metal is Nb,
Group oxide is Nb_TwoO _FiveThe method according to claim 1, wherein
Wiring board. 4. At a temperature of 800 to 1000 ° C., BaO,
It is directed to Al ₂ O ₃ and mixed ceramic material comprising SiO ₂ and cofired the applications, the copper metallizing composition according to any one of claims 1 to 3. 5. A step of preparing the copper metallized composition according to claim 1, and a step of preparing a green ceramic molded body containing a mixed ceramic material containing BaO, Al ₂ O ₃ and SiO _2. Performing the step of applying the copper metallized composition on the green ceramic molded body; and firing the green ceramic molded body together with the copper metallized composition at a temperature of 800 to 1000 ° C. in a reducing atmosphere. And a method for manufacturing a ceramic wiring board. 6. A ceramic substrate obtained from the green ceramic molded body, a conductor film obtained from the copper metallized composition, and the ceramic obtained by the manufacturing method according to claim 5. A ceramic wiring board, comprising: a glass layer formed along an interface between a base and the conductive film. 7. The glass layer contains particles of the Group IVA and / or Group VA transition metal and the transition metal oxide in an area ratio of 20% on the cross section of the glass layer.
The ceramic wiring board according to claim 6, wherein the content is in a range of from about 80%.