JP2002234781A - Copper-metallized composition, ceramic wiring board using the composition and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper-metallized composition which is burnable simultaneously with a mixed ceramics material containing BaO, Al2O3 and SiO2, and is advantageously used for the purpose of obtaining a conductor film having high adhesive strength with a ceramic board containing the above ceramic material. SOLUTION: The copper-metallized composition contains the main component consisting of Cu, CuO, Cu2O, a Cu-CuO mixture, a Cu-Cu2O mixture or a CuO- Cu2O mixture. The composition further contains an additional component consisting of metallic niobium, metallic tantalum, niobium oxide or tantalum oxide by 0.5 to 30.0 wt.% in inorganic components.

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.
TECHNICAL FIELD The present invention relates to a copper metallized composition advantageously used for forming a conductive film on a substrate made of a mixed 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, a mixed ceramic containing BaO, Al ₂ O ₃ and SiO ₂ has attracted attention as a material for the substrate instead of alumina. Further, in order to realize low wiring resistance, it is preferable to use, for example, copper (Cu), gold (Au) or silver (Ag) as a material for the wiring conductor, and in particular, use copper in terms of cost. Is more preferred.

There are two types of ceramic wiring boards, one having a single-layer structure and the other having a multi-layer structure.
Al ₂ O ₃ and when using a mixed ceramic comprising SiO ₂ to produce a ceramic wiring board having a multilayer structure generally, BaO, and a solvent mixed ceramic raw material powder and an organic binder containing Al ₂ O ₃ and SiO ₂ The slurry obtained by mixing is formed into a sheet by applying a sheet forming method such as a doctor blade method, and the obtained ceramic green sheet is provided with a through-hole for a via-hole conductor, if necessary, After filling the through hole with a conductive paste or forming a conductive film having a predetermined pattern using the conductive paste by applying a thick film forming method such as a screen printing method, a plurality of ceramic green sheets are formed. The binder is removed by laminating, pressing and heating the resulting green ceramic compact having the laminated structure, and then Firing is taking place.

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. In the above-described firing step, a method of sintering the ceramic molded body and the conductive paste at a temperature of 1000 ° C. or lower in a reducing atmosphere is applied.

Further, at least a part of the conductor film located on the outer surface of the ceramic wiring board is used as a connection pad for connection to another electronic component. In this case, after a metal thin film made of, for example, nickel and gold is formed on the conductor film by plating or the like,
Other electronic components are connected by soldering, or a solder film or a solder bump is previously formed on a metal thin film, and the other electronic components are connected by melting the solder. .

However, since the bonding strength between such a conductor film and the ceramic substrate is relatively low, such as when soldering, when forming a solder film or solder bump, or when re-melting the solder film or solder bump, etc. In a proper heating step, the conductor film may be easily peeled off from the ceramic substrate due to a stress caused by a difference in thermal expansion coefficient between the conductor film and the ceramic substrate.

In order to solve this problem, for example, Japanese Patent Application Laid-Open No. Hei 6-204656 discloses that an interface between a ceramic substrate and a conductor film contains a metal component in the ceramic substrate and a metal component in the conductor film. A technique has been proposed in which a metal layer bonded to both of the conductor films is formed to increase the adhesive strength between the ceramic substrate and the conductor film.

[0010] For example, Japanese Patent Application Laid-Open No. 4-369575 proposes a technique for increasing the adhesive strength between a copper conductor film and a glass ceramic substrate by adding a metal such as aluminum to a conductive paste containing copper. Have been.

In Japanese Patent Application Laid-Open No. Hei 8-181441, for example, the conductor film has a two-layer structure, and the first layer on the side of the glass ceramic base contains copper as a main component, in order to enhance the adhesion to the glass ceramic. A paste obtained by adding an inorganic substance such as alumina, mullite, and titanium to a green sheet is printed on the green sheet, and a second layer on the paste is made of a paste containing copper as a main component and not containing the inorganic substance on the first layer. A technique has been proposed in which the adhesive layer is formed by printing on the substrate, thereby improving the adhesiveness with the glass ceramic and the adhesiveness with the metal plating layer and the brazing agent.

[0012]

[0007] However, the technique disclosed in JP-A-6-204656 can enhance the adhesion between the conductive film and the BaO-Al ₂ O ₃ -SiO ₂ mixture of ceramic substrates containing copper It is not applicable to make it happen.

Further, the technique described in Japanese Patent Application Laid-Open No. Hei 4-369575 discloses a technique in which a conductive film containing copper and BaO-Al ₂ O ₃ -S
Although it can be applied to increase the adhesive strength to a substrate made of iO ₂ mixed ceramic, it has a serious problem that metal plating on a conductor film becomes difficult. This is because an inorganic substance such as aluminum added to the conductive paste containing copper has low adhesion to the plating film, and such an inorganic substance is exposed on the surface of the conductive film.

In the technique described in Japanese Patent Application Laid-Open No. 8-181441, it is necessary to print the first layer and the second layer one by one in order to form a conductor film having a two-layer structure. Poor pattern formation accuracy due to paste bleeding,
In addition to the problem that it is not possible to cope with the miniaturization of components, there is a problem that the overlay precision must be increased for overlay printing, and the production yield decreases.

It is an object of the present invention to provide a copper metallized composition which can solve the above-mentioned problems, a ceramic wiring board using the same, and a method of manufacturing the same.

[0016]

According to the present invention, first, in order to form a conductive film on a ceramic base containing a ceramic component, the conductive film is applied on a green ceramic molded body to be a ceramic base, and is applied at a temperature of 1000 ° C. or lower. Aimed to provide a copper metallized composition intended for use simultaneously with green ceramic molded bodies at a temperature, and in order to solve the above-mentioned technical problems, this copper metallized composition is, as an inorganic component, While containing a main component containing Cu,
It is characterized in that it contains an additive component that partially crystallizes by reacting with the ceramic component.

The above-mentioned main component is preferably C
_{u, CuO, Cu 2 O,} Cu-CuO mixtures, Cu-C
u ₂ O mixture, and is to include at least one selected from CuO-Cu ₂ O mixture, additional components, the corrosion potential is -2.0 to + 2.0 V, at a pH range of 2 to 10 non It contains at least one kind of metal which becomes active and / or at least one kind of metal oxide, and the content of the additive component is 0.5 to 30.0% by weight in the inorganic component.
Is to be.

In the present invention, more specifically, at least one selected from the group consisting of niobium metal, tantalum metal, niobium oxide and tantalum oxide is used as the additive component.

Further, the ceramic component contained in the green ceramic molded article fired simultaneously with the copper metallized composition according to the present invention preferably contains a mixed ceramic material containing BaO, Al ₂ O ₃ and SiO ₂ .

The present invention also relates to a ceramic wiring board.
Directed to manufacturing methods. This manufacturing method is as described above.
A step of preparing a copper metallized composition, BaO, Al
_TwoO _ThreeAnd SiO_TwoIncluding mixed ceramic materials
First, a process of preparing a raw ceramic molded body and a copper metalla
Of applying the composition to a green ceramic molded body
And the raw ceramic compact together with the copper metallized composition
In a reducing atmosphere at a temperature of 1000 ° C or less
And a step of performing

The present invention is also directed to a ceramic wiring board obtained by the above-described manufacturing method.
This ceramic wiring board includes a ceramic substrate obtained from a raw ceramic molded body, and a conductor film obtained from a copper metallized composition, and the vicinity of the interface between the ceramic substrate and the conductor film is included in the copper metallized composition. It is characterized in that a crystallized glass layer made of glass crystallized by reacting the added component to be reacted with the ceramic component contained in the raw ceramic molded body.

The above-mentioned crystallized glass layer is 0.1 to 1 from the interface between the ceramic substrate and the conductor film on the ceramic substrate side.
Preferably, it is formed with a thickness of 5.0 μm.

The present invention is further directed to a ceramic wiring board irrespective of whether it is obtained by the above-described manufacturing method. The ceramic wiring board includes a ceramic base and a conductive film formed on the ceramic base, and near the interface between the ceramic base and the conductive film, components included in the ceramic base and components included in the conductive film are provided. It is characterized in that a crystallized glass layer made of glass crystallized by the reaction is formed.

[0024]

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 substrate 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, and di-n-butyl phthalate Is mixed with a solvent composed of toluene and isopropylene alcohol to prepare a slurry. 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, and 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.

Further, as 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, that is,
As an inorganic component, while containing a main component containing Cu, and reacting with the ceramic component contained in the green sheet described above, a part thereof is crystallized. A paste is used, and by printing this, the conductor film is formed in a desired pattern.

In a more specific embodiment, the average particle size is 0.1.
5 to 4.0 μm Cu, CuO, Cu ₂ O, Cu—Cu
O mixture, Cu-Cu ₂ O mixture, or CuO-Cu
While the main component ₂ O mixture, as an additive component, niobium metal, tantalum metal, at least one selected from the group consisting of niobium oxide and tantalum oxide, in the inorganic component, from 0.5 to 39.0 wt% The conductive paste containing the copper metallized composition added with the content of is used.

The above-mentioned additive has a corrosion potential of -2.0.
It contains at least one kind of metal and / or at least one kind of metal oxide that is passivated at a range of +2.0 V and a pH of 2 to 10.

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.

Further, a dispersing agent, a plasticizer and an activator may be added to the conductive paste as needed.

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, a conductive paste containing a copper metallized composition containing a main component containing Cu and containing an additive component that partially crystallizes by reacting with a ceramic component contained in the green sheet is used. The green sheets having the film formed thereon are laminated so as to form the outermost layer. And
The laminated green sheets are pressed under the conditions of a temperature of 80 ° C. and a pressure of 200 kg / cm ² , thereby obtaining a green ceramic molded body having a laminated structure.

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 1000 ° C. or lower, for example, 980 ° C., for a holding time of 1 hour.

Next, nickel plating and gold plating are performed on the baked conductor film according to a well-known plating method so that a nickel film and a gold film having a predetermined thickness are respectively deposited. More specifically, it is immersed in a nickel plating bath having a pH of 2 to 5 and a temperature of 80 to 95 ° C. for 1 hour, and subsequently has a pH of 7 to 8 and a temperature of 80 to 9
Immerse in a gold plating bath set at 5 ° C. for 30 minutes.

As described above, niobium metal and metal tantalum, as well as niobium oxide and tantalum oxide, which are added components of the copper metallization composition contained in the conductive paste, have a corrosion potential of −2.0 to +2.0 V and a pH of −2.0 to +2.0 V. 2-1
Since it is a metal and a metal oxide that are passivated in the range of 0, they do not corrode to the plating bath as described above, and therefore do not cause deterioration of the adhesive strength due to dissolution for the plating process. .

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 crystallized glass layer 4 is formed near the interface between the ceramic substrate 2 and the conductor film 3.

More specifically, an additive component such as niobium metal, tantalum metal, niobium oxide and / or tantalum oxide contained in the conductor film 3 is added to the outside of the main component particles containing Cu due to a difference in specific gravity during firing. move, reacts with _{BaO-Al 2 O 3 -SiO 2} Ba and Si, such as glass components in the mixed ceramic contained in the ceramic base _{2, Ba a Nb b Si c} O d, Ba a Ta b Si c O d
A crystallized glass having a composition such as (a, b, c, and d is a positive arbitrary number) is generated, thereby forming a crystallized glass layer 4.

As a result, the stress 5 generated by the difference in the coefficient of thermal expansion between the ceramic substrate 2 and the conductive film 3 (a typical method is indicated by an arrow) is dispersed and relaxed by the crystallized glass layer 4. Therefore, even if heat treatment such as soldering is applied, a strong bonding state between the ceramic base 2 and the conductive film 3 can be ensured, and cracks and the like can be hardly generated. For this bonding, for example,
Adhesive strength of 20 N / 2 mm square or more can be obtained, and therefore, peeling can be suppressed.

If the content of the additional component in the above-mentioned copper metallized composition is less than 0.5% by weight in the inorganic component, the glass component in the BaO—Al ₂ O ₃ —SiO ₂ mixed ceramic and the copper metallized The reaction with the composition is excessively promoted. As a result, the diffusion of Cu, CuO and / or Cu ₂ O into the BaO—Al ₂ O ₃ —SiO ₂ mixed ceramic is excessively promoted, and the acid or At the time of the alkali treatment, the diffused Cu, CuO and / or Cu ₂ O are dissolved, so that the adhesive strength is reduced.

On the other hand, when the content of the additional component in the copper metallized composition exceeds 30.0% by weight in the inorganic component, the glass component in the BaO—Al ₂ O ₃ —SiO ₂ mixed ceramic becomes excessively copper. It penetrates into the metallized composition, and the added component precipitates on the surface of the conductor film 3,
The solder wettability and plating ability of the conductor film 3 are reduced.

From the above, it is preferable that the added amount of the additive component of the copper metallized composition is 0.5 to 30.0% by weight.

The crystallized glass layer 4 is formed on the ceramic substrate 2 side from the interface between the ceramic substrate 2 and the conductive film 3 as shown in FIG.
It is preferably in the range of 5.0 μm.

The thickness of the crystallized glass layer 4 is 0.1 μm.
When the thickness is less than 15.0 m, the additive component is exposed on the surface of the conductive film 3, so that the plating property and the solder wettability deteriorate. On the other hand, when the thickness exceeds 15.0 μm, the crystallized glass layer 4 and the ceramic This is because the periphery of the conductor film 3 may be deformed due to the difference in thermal expansion coefficient between the ceramic substrate 2 and the ceramic substrate 2 in an extreme case. In order to more reliably prevent warpage and undulation of the ceramic base 2, the above-mentioned thickness is 0.1 to 1
More preferably, it is 0.0 μm.

[0051]

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, the ceramic substrate on which includes a BaO-Al ₂ O ₃ -SiO ₂ mixed ceramic or glass ceramic, to form a conductive film obtained from a copper metallizing composition, to produce a ceramic circuit board.

Table 1 shows various compositions of the main component and the additional component of the copper metallized composition used in this experimental example, and the composition of the ceramic substrate.

[0053]

[Table 1]

Referring to Table 1, when a type of BaO—Al ₂ O ₃ —SiO ₂ mixed ceramic is used as the material of the ceramic substrate, a mixture of barium oxide, silicon oxide, alumina, calcium oxide and boron oxide is used. A binder made of polyvinyl butyral, and di-n
A slurry is prepared by adding and mixing a plasticizer composed of butyl phthalate and a solvent composed of toluene and isopropylene alcohol, forming the slurry into a sheet on an organic film by a doctor blade method, and then drying the slurry. Thus, a ceramic green sheet having a thickness of 125 μm was produced.

On the other hand, when a kind of glass ceramic is used as the material of the ceramic base, Japanese Patent Application Laid-Open No.
As described in Example 1 of No. 81441, 63 parts by weight of a borosilicate glass powder having an average particle diameter of 3 μm, 37 parts by weight of mullite powder having an average particle diameter of 3 μm, and 20 parts by weight of a methacrylic acid-based binder, Trichlorethylene 124
Parts by weight, 32 parts by weight of tetrachloroethylene, and 44 parts by weight of n-butyl alcohol were wet-mixed with a ball mill for 24 hours to prepare a slurry, and the slurry was formed into a sheet on an organic film by a doctor blade method. It was molded and then dried to produce a 125 μm thick ceramic green sheet.

On the other hand, in order to prepare a conductive paste containing a copper metallized composition, a main component having an average particle size of 3 μm and various additional components having various compositions as shown in Table 1 were prepared.

Then, as shown in Tables 2 and 3, these components are appropriately selected from the main components and the added components, and the added components are shown in Tables 2 and 3 with respect to the total of the main components and the added components. To obtain such various contents, each of these main components and additional components is weighed, and an acrylic resin as an organic binder and terpineol as a solvent are added thereto, kneaded, and a conductive material including a copper metallized composition is added. A paste was prepared. Here, the amount of the organic binder in the conductive paste was 10% by weight based on the main component.

[0058]

[Table 2]

[0059]

[Table 3]

Next, as also shown in Tables 2 and 3, a conductive sheet containing the above-described copper metallized composition was placed on a green sheet to be a ceramic substrate containing the above-mentioned kind of BAS ceramic or kind 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, the 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 4 and 5 show the evaluation results of the ceramic wiring substrates as these samples.

[0063]

[Table 4]

[0064]

[Table 5]

In Tables 2 and 3, and Tables 4 and 5, those marked with an asterisk (*) are samples corresponding to comparative examples outside the scope of the preferred embodiment of the present invention.

In Tables 4 and 5, "crystallized glass layer thickness" means that a ceramic wiring substrate as a sample is cut in a direction perpendicular to the main surface of the conductor film so as to cross the conductor film. The thickness of the crystallized glass layer existing at the interface between the glass substrate and the ceramic substrate was measured by using a scanning electron microscope.

Regarding the “adhesive strength”, a 5.0 μm thick nickel plating on a 2 mm square conductor film and a 0.5 μm thick gold plating thereon were applied, and then a C
Solder the u-type lead wire,
The maximum (peak) load when the conductor film was peeled from the ceramic substrate together with the lead wire by pulling the conductor film in the direction perpendicular to the main surface of the conductor film at a tensile speed of / min was evaluated.

The “plating property” is determined by visually observing the state of formation of a plating film when the above-described plating is performed, and determining the quality of the plating film.

“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 judgment made by integrating the various evaluation results as described above.

First, BaO-
Referring to Tables 2 and 4 showing samples using the Al ₂ O ₃ —SiO ₂ mixed ceramic, the content of the additional component in the copper metallized composition is less than 0.5% by weight,
In Samples 1 to 3 in which the “crystallized glass layer thickness” is less than 0.1, the “adhesion strength” is less than 20 N / 2 mm □.

On the other hand, in Sample 12 in which the content of the additional component in the copper metallized composition exceeds 30.0% by weight or the “crystallized glass layer thickness” exceeds 15.0 μm, the “plating property” and “solder” Wettability "is getting worse.

Next, referring to Tables 3 and 5 showing samples using a glass ceramic in the ceramic substrate, the glass component covers the surface of the copper metallized composition or the copper metallized composition Sample 2 in which the content of the additional component in the copper metallized composition is less than 0.5% by weight because it sinks into the ceramic.
In any of the samples 28 to 48 except for the samples 5 to 27,
"Plating property" and "solder wettability" are poor, most of them cannot be evaluated, and samples 25 to 27 in which the content of the additive component in the copper metallized composition is less than 0.5% by weight, Although evaluation was possible, "adhesive strength"
Is less than 5 N / 2 mm □.

On the other hand, as shown in Tables 2 and 4,
Samples 4-1 within the scope of the preferred embodiment of the invention
According to Nos. 1 and 13 to 24, "plating property" and "solder wettability" are all good, and "adhesive strength"
Is 20 N / 2 mm □ or more, which can provide comprehensively satisfactory characteristics.

In the experimental examples described above, niobium oxide and tantalum oxide were used as additional components contained in the copper metallizing composition. However, even when niobium metal and tantalum metal were used, substantially the same It has been confirmed that results can be obtained.

[0076]

As described above, according to the present invention, a copper metallized composition contains a main component containing Cu as an inorganic component and reacts with a ceramic component to partially crystallize. When the copper metallized composition is applied on a green ceramic molded body and fired simultaneously with the green ceramic molded body at a temperature of 1000 ° C. or less, the raw ceramic molded body In the vicinity of the interface between the ceramic substrate obtained from the above and the conductor film obtained from the copper metallized composition, a crystallized layer generated by the above-mentioned crystallization is formed.

Therefore, the stress generated due to the difference in the coefficient of thermal expansion between the ceramic substrate and the conductor film can be dispersed and reduced by the crystallized layer. A strong adhesive state can be secured with the conductive film.

In the above-mentioned copper metallized composition, Cu, CuO, Cu ₂ O, a Cu—CuO mixture, a Cu—Cu ₂ O mixture, and a CuO—Cu ₂ O
At least one selected from a mixture is used, and as an additional component, a corrosion potential is −2.0 to +2.0 V, and a pH is 2-1.
At least one kind of metal and / or at least one kind of metal oxide that is passivated in the range of 0, more specifically, at least one kind selected from the group consisting of niobium metal, tantalum metal, niobium oxide and tantalum oxide Using the seeds, the content of the additive component in the inorganic component was 0.5
When the content is set to 30.0% by weight, a decrease in the adhesive strength of the conductor film due to an acid or alkali treatment in the plating step can be reliably prevented, and a decrease in solder wettability and plating ability of the conductor film can be surely achieved. Can be prevented.

When the ceramic component contained in the ceramic substrate is a mixed ceramic material containing BaO, Al ₂ O ₃ and SiO ₂ , a crystallized glass layer is formed as the above-mentioned crystallized layer. The crystallized glass layer reliably acts to disperse and relieve the stress as described above, so that the adhesive strength between the ceramic substrate and the conductive film can be reliably maintained at a high level.

Further, in the ceramic wiring board according to the present invention, the above-mentioned crystallized glass layer may be 0.1 to 15.
When the conductive film is formed to have a thickness of 0 μm, it is possible to reliably prevent the plating property and solder wettability of the conductive film from deteriorating and the periphery of the conductive film from being deformed.

[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 Crystallized glass layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4E351 AA07 BB01 BB24 BB31 CC12 CC22 CC31 CC35 DD04 DD14 DD21 DD31 DD33 DD58 EE02 EE03 EE27 GG02 5E343 AA24 BB24 BB53 BB59 BB77 DD02 ER33 ER38 ER39 GG01 A30A08 AB08

Claims (9)

[Claims] 1. A method for forming a conductive film on a ceramic substrate containing a ceramic component, the method comprising applying the conductive film on a raw ceramic molded body to be the ceramic substrate, at a temperature of 1000 ° C. or less. A copper metallized composition intended for use at the same time as firing, which contains a main component containing Cu as an inorganic component, and reacts with the ceramic component to form an additional component that partially crystallizes. A copper metallized composition to be contained. 2. The method according to claim 1, wherein the main component is Cu, CuO, Cu.
_At least one selected from the group consisting of ₂ O, Cu—CuO mixture, Cu—Cu ₂ O mixture, and CuO—Cu ₂ O mixture;
The additive component has a corrosion potential of −2.0 to +2.0 V, p
H contains at least one kind of metal and / or at least one kind of metal oxide that is passivated in the range of 2 to 10, and the content of the additional component is as follows:
The copper metallized composition according to claim 1, which is 0.5 to 30.0% by weight. 3. The copper metallized composition according to claim 2, wherein the additive component is at least one selected from the group consisting of niobium metal, tantalum metal, niobium oxide and tantalum oxide. 4. The ceramic component comprises BaO, Al ₂
A mixed ceramic material comprising O ₃ and SiO ₂ ,
The copper metallized composition according to claim 1. 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 in a reducing atmosphere at a temperature of 1000 ° C. or less. A method for manufacturing a ceramic wiring board, comprising: 6. A method according to claim 5, comprising a ceramic substrate obtained from the green ceramic molded body, and a conductive film obtained from the copper metallized composition. The vicinity of the interface between the ceramic base and the conductor film is made of glass crystallized by reacting the additive component contained in the copper metallized composition with the ceramic component contained in the green ceramic molded body. A crystallized glass layer is formed,
Ceramic wiring board. 7. The crystallized glass layer is formed with a thickness of 0.1 to 15.0 μm on the ceramic substrate side from an interface between the ceramic substrate and the conductor film.
The ceramic wiring board according to claim 6. 8. A ceramic substrate, and a conductor film formed on the ceramic substrate, and a component contained in the ceramic substrate and a component contained in the conductor film near an interface between the ceramic substrate and the conductor film. A ceramic wiring board in which a crystallized glass layer made of glass crystallized by reacting with a component to be formed is formed. 9. The crystallized glass layer is formed with a thickness of 0.1 to 15.0 μm on the ceramic substrate side from an interface between the ceramic substrate and the conductor film.
A ceramic wiring board according to claim 8.