JP2003277852A - Copper metallized composition and ceramic wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper metallized composition with which the adhesive strength between a copper wiring layer and a ceramic insulation layer such as glass ceramic is improved, the warpage of the wiring board is suppressed, and which has excellent solder wettability, and to provide a ceramic wiring board obtained by using the composition. <P>SOLUTION: The copper metallized composition is obtained by incorporating glass components in 0.5 to 8 pts.mass, and a compound oxide essentially consisting of Mg, Zn and Ti in 0.05 to 3 pts.mass to 100 pts.mass of copper powder. Further, an ilmenite phase and a spinel phase are formed in the compound oxide, and B<SB>2</SB>O<SB>3</SB>is contained in 0.01 to 10 pts.mass to 100 pts.mass of the compound oxide. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper metallization composition and a ceramic wiring board using the same, and more particularly to a copper metallization composition and a ceramic wiring board suitable for cofiring with ceramic porcelain powder.

[0002]

2. Description of the Related Art In recent years, wiring boards have been required to have high frequency circuit compatibility, high density, and high speed, and have a lower dielectric constant and a lower wiring layer resistance than alumina-based ceramic insulating layers. A ceramic wiring substrate that can be fired at a low temperature, such as a glass ceramic that can be used, is receiving more attention.

As a ceramic wiring substrate, there is known a substrate in which a wiring layer mainly made of a low resistance metal such as copper, gold or silver is applied to an insulating substrate made of an insulating layer such as glass ceramics. As a copper metallizing composition used for such a wiring board, for example, the one disclosed in Japanese Patent Laid-Open No. 3-46706 is known. The copper metallization composition disclosed in this publication includes copper powder, ZnO, B ₂ O ₃ , and Si.
It is a mixture of O ₂ and a glass powder of PbO, and by using a copper metallizing composition having such a composition, the sintering of the copper powder can be promoted.
It is described that a high adhesive strength can be obtained even by firing at a temperature of 00 ° C. or lower.

[0004]

However, in the copper metallizing composition disclosed in the above publication, since the glass powder contained in the copper metallizing composition has a low softening property, the sinterability of the copper powder is improved. However, warpage occurs in the wiring board or separation of the copper component and the glass component occurs,
The glass component contained in the conductor paste floats on the surface of the copper wiring layer, and as a result, the adhesive strength between the copper wiring layer and the glass ceramic insulating layer is reduced, and terminals etc. are connected by soldering. At that time, there was a problem that solder wettability was lowered.

Therefore, the present invention provides a copper metallized composition which improves the adhesive strength between a copper wiring layer and a ceramic insulating layer such as a glass ceramic porcelain, suppresses the warp of a wiring board, and has excellent solder wettability. An object is to provide a ceramic wiring board.

[0006]

The copper metallizing composition of the present invention is a composite containing 0.5 to 8 parts by mass of a glass component, and Mg, Zn, and Ti as the main components with respect to 100 parts by mass of copper powder. It is characterized by containing 0.05 to 3 parts by mass of an oxide.

According to such a structure, the copper metallization composition approaches the firing shrinkage behavior of the glass ceramic insulating layer, as compared with the case where a conductor paste containing ZnO powder as the main component in the copper powder is used. Therefore, the warp of the ceramic wiring board can be reduced.

Further, by containing the above composite oxide together with the glass component, this composite oxide has high wettability with respect to both the copper component and the ceramic insulating layer. It is possible to increase the adhesive strength between the copper component and the glass component, and further suppress the separation of the copper component and the glass component, so that the glass floating on the surface of the copper wiring layer can be suppressed and the solder wettability can be improved.

In the above copper metallized composition, the composition of the composite oxide is Zn: Mg: Ti = 0.about.0.1.
It is preferably 95: 0.05 to 0.9: 0.1 to 1.1. By setting the composition of the composite oxide in such a range, since an ilmenite phase, a spinel phase, or a mixed phase thereof is formed in the composite oxide, the temperature around the firing temperature of the ceramic wiring substrate of the present invention In, the excessive softening of this composite oxide can be suppressed. Therefore, the composite oxide can be present in the copper metallized composition uniformly, and the sinterability of the copper metallized composition can be enhanced.

In the above-mentioned copper metallized composition, it is desirable that an ilmenite phase and a spinel phase are formed in the composite oxide. Since both phases of the ilmenite phase and the spinel phase are mixed in the composite oxide, The wettability to both the copper component and the ceramic porcelain is increased at the same time, so that the adhesive strength between the copper wiring layer and the ceramic porcelain can be further increased.

In the above copper metallized composition, B ₂ O ₃ is added in an amount of 0.01 to 1 with respect to 100 parts by mass of the main component composed of Zn, Mg and Ti in the composite oxide.
It is desirable to include 0 parts by mass. B in the complex oxide
By containing ₂ O ₃ , it becomes easier to take in the glass component contained together in the copper metallization composition, and the wettability with the copper component and the ceramic insulating layer can be further improved. The strength can be further increased.

The ceramic wiring substrate of the present invention is a composite oxide containing an ilmenite phase and / or a spinel phase in the interface region between the copper wiring layer and the ceramic porcelain obtained by co-firing the ceramic porcelain powder and the copper metallized composition. It is characterized in that an object is formed.

As described above, when the crystal phase contained in the composite oxide is an ilmenite phase, a spinel phase, or a mixed phase thereof, softening of the composite oxide can be suppressed. It is possible to prevent the diffusion to the ceramic insulating layer, and therefore, it is possible to increase the adhesive strength between the copper wiring layer and the ceramic insulating layer, and it is possible to reduce the amount of glass powder in the copper metallization composition. It is possible to suppress the floating of the glass.

In the above-mentioned ceramic wiring board, it is desirable that the area occupancy rate of glass is 50% or less with respect to the total surface area of the copper wiring layer. By setting the area occupancy of the glass protruding on the surface of the copper wiring layer to 50% or less, it is possible to prevent the plating film formed on the surface of the copper wiring layer from being chipped.
The wettability and adhesiveness with solder can be improved. That is, since the glass component is suppressed from being raised to the surface of the copper wiring layer, the adhesive strength between the copper wiring layer itself and the copper wiring layer and the ceramic insulating layer can be improved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The copper metallized composition of the present invention and the ceramic wiring board using the same will be described in detail below.

In the copper metallization composition of the present invention, the copper powder may be a copper powder and / or a copper oxide powder reduced to copper by heat treatment in a reducing atmosphere. The copper powder has an average particle size of 1 to 5 μm, particularly 1.5 to 3 μm, and further 2 to 2.5 μm, and in particular, spherical copper powder is used to prevent a decrease in adhesive strength due to oversintering. In addition, it becomes possible to form a fine copper wiring layer.

According to the present invention, it is important that the glass component is contained in an amount of 0.5 to 8 parts by mass with respect to 100 parts by mass of the copper component. When co-firing with the ceramic insulating layer, the effect of the copper metallizing composition as a sintering aid is enhanced, the sinterability of the copper metallizing composition itself can be enhanced, and the adhesive strength with the ceramic insulating layer can be improved.

When the amount of the glass component is less than 0.5 part by mass, the effect as a sintering aid becomes small, the insufficient sintering tends to occur, and the adhesive strength is lowered. on the other hand,
When the amount of the glass component is more than 8 parts by mass, the sinterability of the copper metallized composition itself is increased due to the softening property of the glass component, but the difference in firing shrinkage with the ceramic insulating layer becomes large, so that the warpage is caused. growing. Moreover, the glass floats on the surface of the copper wiring layer more frequently. Glass component is copper component 10
Particularly, 2 to 5 parts by mass of the glass component is preferable with respect to 0 parts by mass.

As the glass component used in the present invention, at least one of borosilicate glass, zinc borosilicate glass, lithium silicate glass, PbO glass, and BaO glass is used. It may be crystallized glass in which a crystal phase is precipitated by crystal quality or firing. Further, the average particle size of these glass powders as the raw materials is 1 to 3 because the glass particles can be uniformly dispersed.
The thickness is preferably μm, and more preferably 1.5 to 2 μm.

Further, according to the present invention, it is important that the complex oxide containing Zn, Mg and Ti as the main components is contained in a proportion of 0.05 to 3 parts by mass with respect to 100 parts by mass of the copper component. is there. By adding this complex oxide,
It is possible to suppress the diffusion of the glass component contained together in the copper metallized composition to enhance the sinterability between the copper metallized composition and the ceramic insulating layer and to suppress the warpage.

When the amount of the complex oxide is less than 0.05 parts by mass, the sinterability between the copper metallization composition and the ceramic insulating layer is lowered and the adhesive strength is lowered. On the other hand, when the amount of the composite oxide is more than 3 parts by mass, the sintering of the copper component is hindered, so that the warpage becomes large and the adhesive strength becomes low.

Further, it has high wettability with respect to both the copper component in the copper metallized composition and the ceramic insulating layer,
In particular, since the adhesive strength between the copper wiring layer and the glass ceramic insulating layer can be further increased, Z is particularly preferable.
The composite oxide containing n, Mg, and Ti as the main components is 0.
It is desirable to contain 1 to 1 part by mass.

Further, it is desirable that an ilmenite phase and / or a spinel phase be formed in the composite oxide. When the complex oxide constituting the copper metallized composition has such a crystal phase, excessive softening can be suppressed at the firing temperature of the copper metallized composition and the ceramic insulating layer, and the copper component and the ceramic insulating layer are homogeneous. Can form wetting. In particular, it is more desirable that the ilmenite phase and the spinel phase coexist in the composite oxide because the adhesive strength of the copper wiring layer is increased.

Further, the complex oxide of the present invention is not limited to the crystal phase of these stoichiometric compositions, and for example, M
As long as it is composed of metal oxides of g, Zn and Ti, it does not have to have a stoichiometric composition such as an ilmenite phase or a spinel phase.

In the composite oxide, Zn, M
Addition of 0.01 to 10 parts by mass of B ₂ O ₃ to 100 parts by mass of the main component composed of g and Ti further enhances the adhesiveness between the copper metallization composition and the ceramic insulating layer. be able to. Particularly, the amount of B ₂ O ₃ is more preferably 2 to 5 parts by mass.

Further, the element ratio of Zn, Mg, and Ti in the composite oxide is a molar ratio of Zn: Mg: Ti = 0.1 when the above ilmenite phase and spinel phase are formed.
˜0.95: 0.05 to 0.9: 0.9 to 1.1 is desirable, and when only an ilmenite phase is formed, the molar ratio of Zn: Mg: Ti is 0.1 to 0. 8: 0.2
˜0.9: 0.9 to 1.1, and when forming only a spinel phase, it is desirable that Zn: Mg: Ti = 0.8: 0.2: 0.1.

The average particle size of the composite oxide powder is preferably 1 to 5 μm for the purpose of improving the homodispersibility in the copper metallized composition and enhancing the wettability, and particularly 1.5 to More preferably, it is 2.5 μm.

The composite oxide in the present invention is Zn
O, MgO, and TiO ₂ , or a mixture obtained by adding B ₂ O ₃ to the above in the above proportions was calcined at 700 to 1300 ° C. and then pulverized, and the average particle diameter was 1 to 5 μm.
It is desirable that it is m. This is more homogeneous than the case where each component is added as each oxide powder alone, so that the adhesive strength between the ceramic insulating layer and the copper wiring layer is increased,
Variation in adhesive strength can be suppressed. The heat-treated complex oxide is preferably a crystalline compound containing the crystalline phase as described above.

In the copper metallized composition of the present invention, in addition to the above, other inorganic substances can be added in an amount of 0.05 to 1 part by mass based on 100 parts by mass of the copper component. Examples of other inorganic substances include alumina, silica, mullite, forsterite, petalite, nepheline, lithium silicate, carnegia night, garnite, and zirconia. Of these, alumina is particularly desirable.

The average particle size of the inorganic material is preferably 0.1 to 3 μm, and more preferably 0.5 to 1 μm, because it can be dispersed uniformly.

Next, a ceramic wiring board using the copper metallizing composition of the present invention will be described with reference to the drawings. FIG. 1 shows the structure of a ceramic wiring board according to an embodiment of the present invention, which is a multilayer wiring board having a plurality of copper wiring layers.

As shown in FIG. 1, a ceramic wiring board 1
Includes a ceramic insulating substrate 2 and a copper wiring layer 3.

The ceramic insulating substrate 2 is composed of a laminated body in which a plurality of ceramic insulating layers 2a ... 2d are laminated, and a copper wiring layer 3 having a thickness of 5 to 30 μm is provided on each layer and on the surface of the ceramic insulating substrate 2. Has been formed.
Further, in the ceramic insulating substrate 2, the diameter of the ceramic insulating layers 2a ... 2d penetrating in the thickness direction is 50 to 20.
The via-hole conductor 4 having a thickness of about 0 μm is formed.

The ceramic insulating substrate 2 is 800-110.
It is made of a material that can be fired at a low temperature of 0 ° C., for example, a glass material containing at least SiO ₂ or a glass ceramic porcelain powder made of a composite material of a glass material containing SiO ₂ and an inorganic filler. Specifically, this glass material is composed of a plurality of metal oxide components, amorphous after firing, or by firing, cordierite, mullite, anorthite, Sergian, spinel, garnite, willemite, dolomite, lithium. A crystallized glass that precipitates crystals of silicate or its substituted derivative is desirable.

As the glass material, a well-known glass material can be used. In particular, crystalline glass that crystallizes during firing is desirable, and mechanical strength can be improved by precipitation of a crystalline phase from this crystalline glass. As a result, the adhesive strength of the copper wiring layer can also be improved. Examples of the glass component used here include SiO ₂ —Al ₂ O ₃ —MgO
A preferred -CaO based crystallized glass material, Li ₂ O in addition to glass materials of this system, K ₂ O, alkali metal oxides such as Na ₂ O, CaO, alkaline earth metal oxides such as MgO, Al Borosilicate glass containing one or more selected from ₂ O ₃ , P ₂ O ₅ , ZnO, B ₂ O ₃ and PbO,
BaO type glass, sodium soda glass, etc. are mentioned.

As the inorganic filler constituting the ceramic insulating substrate 2, at least one selected from the group consisting of calcium zirconate, calcium titanate, strontium titanate, barium titanate, alumina, mullite, forsterite, zirconia, spinel and the like. Can be used.

The ratio of the glass material to the inorganic filler is preferably 30 to 70% by mass of the glass material and 70 to 30% by mass of the inorganic filler.

Other materials that can be fired at low temperature include
A composition obtained by mixing SiO ₂ , an alkaline earth metal oxide, and the like in a desired composition without using the above glass may be used.

The ceramic insulating substrate 2 according to the present invention is
Coefficient of thermal expansion from 0 to 400 ° C is 7 to 18 × 10^-6/ ° C
Is preferred. Thermal expansion of ceramic insulating substrate 2
Number is 7 × 10^-6Below / ° C, ceramic insulating substrate 2
Mounted by applying thermal stress to the solder joint between the board and the printed wiring board
There is a problem that reliability decreases, and conversely 18 × 10 ^-6
/ C is exceeded, ceramic insulating substrate 2 and silicon chip
Thermal stress is applied to the solder joint part with and mounting reliability deteriorates.
There is a problem.

The copper wiring layer 3 on the surface of the ceramic wiring board 1 is used as a pad for mounting various electronic components 5 such as a silicon chip, as a conductor film for shielding, and as a terminal electrode for connecting to an external circuit. The
Various electronic components 5 are bonded to the copper wiring layer 3 via a conductive bonding agent 6 such as solder.

The occupying area ratio of glass with respect to the total surface area of the copper wiring layer 3 on the surface is preferably 50% or less in order to improve the formation of the plated film and enhance the solder wettability.

According to the present invention, the copper wiring layer 3 on the surface and inside of the ceramic wiring substrate 1 and the via-hole conductor 4 are insulated from the insulating substrate 2 by the above-mentioned copper metallizing composition.
It is formed by co-firing with.

Although not shown, if necessary,
On the surface of the ceramic wiring substrate 1, a thick film resistor film such as tantalum silicide or molybdenum silicide, a wiring protective film, or the like may be further formed.

Next, a method for producing the ceramic wiring board 1 of the present invention will be described.

First, for example, SiO ₂ --Al ₂ O ₃ --Mg
A glass-ceramic composition is prepared by mixing 50 to 90% by mass of an O-CaO-based crystallized glass material and 10 to 50% by mass of an alumina-based filler, and 10 parts of an organic binder are added to 100 parts by mass of the mixture. ~ 12 parts by mass is added, and further a plasticizer such as phthalic acid ester and a solvent such as toluene are added to prepare a slurry. After that, a green sheet is obtained by an appropriate forming means such as a doctor blade method, a rolling method or a pressing method.

Next, a diameter of 100 to 20 is applied to this green sheet by laser, microdrilling, punching or the like.
A 0 μm through hole is formed, and the same conductor paste as that for the copper wiring layer 3 is filled in the through hole.

Then, a pattern is printed on the surface of this green sheet by screen printing using the above-mentioned conductor paste containing the copper metallizing composition of the present invention to form a wiring pattern. As the copper component which is the main component of the conductor paste, the above-mentioned copper powder having a predetermined particle diameter, or one containing a part of copper oxide is used. Note that copper oxide is substantially reduced to copper simple substance by firing in a reducing atmosphere.

The conductor paste contains an organic binder such as an acrylic resin, α-terpineol, and an inorganic component such as the above-mentioned copper component, glass component, complex oxide, and if necessary, an inorganic substance such as Al ₂ O ₃ . It is prepared by homogeneously mixing an organic solvent such as dibutyl phthalate or butyl carbitol using a stir mixer.

It is desirable to mix the organic binder in an amount of 1 to 10 parts by mass and the organic solvent component in an amount of 5 to 30 parts by mass with respect to 100 parts by mass of the inorganic component.

After that, the wiring pattern and the via-hole conductor 4
The green sheets on which are formed are laminated and pressure-bonded to form a laminated body.

Next, this laminated body is heat-treated in a nitrogen atmosphere containing water vapor at 300 to 500 ° C., and the temperature is further raised to 700 ° C. or higher to decompose the organic components contained in the green sheet and the conductor paste. After removing 800
By co-firing in a nitrogen atmosphere at ˜1100 ° C., the ceramic wiring board 1 including the copper wiring layer 3 and the via-hole conductor 4 can be manufactured.

The copper wiring layer 3 constituting the ceramic wiring substrate 1 of the present invention and the ceramic insulating substrate 2 made of the ceramic insulating layer are made to have similar firing shrinkage behaviors, the adhesive strength between them is enhanced, and the copper wiring layer 3 is provided. The firing temperature is more preferably 900 to 1050 ° C. for the reason that the glass float is suppressed.

The ceramic wiring board 1 of the present invention is not limited to the ceramic wiring board 1 as described above, and wiring is performed on the single-layer green sheet constituting the ceramic insulating layer with the same conductor paste as above. It also includes a ceramic wiring substrate 1 on which a pattern is printed and cofired.

Even if the structure of the ceramic wiring board 1 is a multi-layer structure, only the internal copper wiring layer 3 is baked at the same time as the laminated body, and the wiring layer on the surface is coated with a known copper thick film composition. It is also possible to print and print to form.

[0055]

EXAMPLES Hereinafter, the copper metallized composition of the present invention and the ceramic wiring board using the same will be described in detail based on examples.

First, SiO ₂ 50% by mass-Al ₂ O ₃ 5.
A mixture of 60 parts by mass of crystalline glass powder having a composition of 5% by mass-MgO 18.5% by mass-26% by mass CaO and 40% by mass of glass ceramic raw material powder, which is an inorganic filler, and 40 parts by mass of alumina having an average particle diameter of 2 μm, is prepared. Then, to 100 parts by mass of this mixture, 14 parts by mass of isobutyl methacrylate resin as an organic binder and 7 parts by mass of dibutyl phthalate as a plasticizer were added as an organic binder, and toluene was mixed for 40 hours by a ball mill as a slurry to form a slurry. Was adjusted.

Next, the obtained slurry was formed into a green sheet having a thickness of 0.3 mm by the doctor blade method. Via holes were formed in this green sheet by using punching.

Next, the copper metallization compositions shown in Table 1 were prepared. The addition amount of the complex oxide and the glass component is the addition amount with respect to 100 parts by mass of the copper powder. The amount of B ₂ O ₃ added is the amount added with respect to 100 parts by mass of the composite oxide.
In this case, 100 parts by mass of copper powder was used as A
0.1 part by mass of 1 ₂ O ₃ was added. The average particle size of the copper powder constituting the copper metallized composition is about 2 μm, the average particle size of the composite oxide is about 2 μm, and Al ₂ used as an inorganic substance is used.
The average particle size of O ₃ was about 0.5 μm, and aluminoborosilicate glass having an average particle size of about 1.5 μm was used as the glass powder. The crystal phase of the complex oxide contained in the copper metallized composition was identified by X-ray diffraction.

Next, 4 parts by mass of isobutyl methacrylate as an organic binder was added to this copper metallized composition,
Further, a mixed solution of butyl carbitol acetate and dibutyl phthalate was added as a plasticizer and a solvent and mixed by using a stirring mixer to prepare a conductor paste.

Next, the conductor paste was printed on the via holes formed in the green sheet and the surface thereof to form via hole conductors and wiring patterns.

Next, a plurality of green sheets having via-hole conductors and wiring patterns formed thereon were laminated and pressed to produce a molded body.

Next, the molded body is heated to a temperature of 300 to 500 ° C. to remove the binder, and further heat-treated at 750 ° C. for 1 hour in a nitrogen atmosphere containing water vapor to remove residual carbon in the molded body. After reducing to less than 200ppm,
Firing at 00 ° C. × 1 h was performed to obtain a ceramic wiring board on which a copper wiring layer and a via hole conductor were formed. The obtained glass-ceramic wiring board has external dimensions of approximately 15 mm x 1
5mm x 1mm, surface area is 10mm x 10mm
Thus, a metallized pattern having a thickness of 10 μm was formed.

The warp was measured diagonally on the upper surface side of the metallized pattern of this ceramic wiring board using a surface roughness meter. The amount of warpage was the amount of deformation per 10 mm.

Next, this ceramic wiring board was plated with Ni and Au as metal components, and the copper wiring layer provided with this plating film was observed with a metallurgical microscope. Was evaluated.

Further, a sample for evaluating the adhesive strength of the copper wiring layer was prepared. This sample has a shape of 2 mm after firing
A pattern of 2 mm (2 mm □) is separately prepared, three green sheets are pressure-laminated using this as the uppermost layer, and after firing, Ni-Au plating is applied, and then 2 mm □.
Lead wires were joined to the pattern in parallel with the surface of the copper wiring layer by soldering. To evaluate the adhesive strength, a lead wire was bent in a direction perpendicular to the surface of the copper wiring layer, and a peel test was performed under the condition of 10 mm / min.

On the other hand, as a comparative example, ZnO, MgO, and TiO ₂ were added alone to the copper powder, not as a composite oxide, in addition to the composition outside the composition range of the copper metallized composition of the present invention. In that case, a copper metallized composition was prepared, and the same evaluation as the copper metallized composition of the present invention was performed.

[0067]

[Table 1]

[0068]

[Table 2]

As is clear from the results shown in Tables 1 and 2, 0.5 parts of the glass component was added to 100 parts by mass of the copper powder.
.About.8 parts by mass, and 0.05 to 3 parts by mass of the composite oxide containing Mg, Zn, and Ti as the main components. 2 to
6, 9 to 12, and 14 to 23, the adhesive strength of the copper wiring layer was 31 MPa or more, and the warpage of the ceramic wiring board was 50 μ.
When it was m or less, the area occupancy of the glass was 50% or less, and the solder wettability was good.

Further, a sample N in which both the ilmenite phase and the spinel phase coexist as crystal phases in the composite oxide
o. In Nos. 2 to 6, 9 to 12, and 14 to 21, the adhesive strength of the copper wiring layer was improved to 34 MPa or more.

Further, in Sample No. 10 containing 0.01 to 10 parts by mass of B ₂ O ₃ with respect to 100 parts by mass of the composite oxide. 1
In Nos. 4 to 20, the adhesive strength of the copper wiring layer was further improved to 43 MPa or more.

On the other hand, the sample No. in which the amount of glass component and the amount of complex oxide contained in the copper metallized composition were out of the range of the present invention. In Nos. 1, 7, 8, and 13, the adhesive strength is reduced to 29 MPa or less, or the warp of the ceramic wiring board is 55 μm.
There were some things that became bigger than the above.

Further, instead of the complex oxide, ZnO, M
Sample No. _{1 in} which gO and TiO ₂ were not calcined but were added individually. In No. 24, since the glass powder has a low softening property, the copper component and the glass component are separated from each other, and the glass component contained in the conductor paste floats on the surface of the copper wiring layer. 80% glass area occupancy
And the solder wettability deteriorates, and the adhesive strength between the copper wiring layer and the glass ceramic insulating layer is 14 MPa.
It dropped to below. In addition, the warp of the glass ceramic wiring board was increased to 140 μm.

[0074]

As described above in detail, according to the present invention, in the copper metallizing composition co-fired with the ceramic insulating layer, in this composition, in addition to the glass component with respect to the copper powder, Mg, By containing the composite oxide containing Zn and Ti as the main components, the composite oxide has high wettability with respect to both the copper component and the glass ceramic porcelain powder, thus suppressing glass float. The solder wettability can be improved, and the adhesive strength between the copper wiring layer and the glass ceramic porcelain can be increased.

Further, the copper metallization composition can be brought close to the firing shrinkage behavior of the glass-ceramic porcelain, so that the warpage of the ceramic wiring board can be reduced.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a ceramic wiring board of the present invention.

[Explanation of symbols]

1 Ceramic wiring board 2 insulating substrate 3 Copper wiring layer 4 Via hole conductor 5 electronic components

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4E351 AA07 BB01 BB31 CC12 DD04                       DD08 DD31 EE02 EE08 EE27                       GG01 GG02 GG03 GG15                 5E346 AA02 AA12 AA15 AA22 AA32                       CC16 CC32 DD02 DD13 DD34                       DD45 EE21 EE24 GG04 GG06                       GG08 HH11 HH13 HH31

Claims (6)

[Claims] 1. A glass component is contained in an amount of 0.5 to 8 parts by mass and a complex oxide containing Zn, Mg, and Ti as main components in an amount of 0.05 to 3 parts by mass with respect to 100 parts by mass of copper powder. A copper metallization composition comprising: 2. The composition of the composite oxide is a molar ratio of Zn: M.
g: Ti = 0.1 to 0.95: 0.05 to 0.9: 0.
The copper metallization composition according to claim 1, wherein the composition is 1 to 1.1. 3. The copper metallized composition according to claim 1, wherein an ilmenite phase and a spinel phase crystal phase are formed in the composite oxide. 4. Zn, Mg, and Ti in a composite oxide
With respect to the main component of 100 parts by weight consists, B ₂ O ₃ is copper metallization composition according to any one of claims 1 to 3, characterized in that contained 0.01 to 10 parts by weight. 5. A composite oxide containing an ilmenite phase and / or a spinel phase is formed in an interface region between a copper wiring layer and a ceramic porcelain obtained by co-firing ceramic porcelain powder and a copper metallized composition. A ceramic wiring board characterized by the above. 6. The ceramic wiring substrate according to claim 5, wherein the glass has an area occupancy of 50% or less with respect to the total surface area of the copper wiring layer after firing.