JP2000138428A - Wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wiring board which is provided with a metallized wiring layer composed of a low-resistance metal on the surface of an insulating substrate made of a glass ceramic, and can prevent the occurrence of such a phenomenon that the metallized wiring layer swells due to the insufficient removal of residues resulting from an organic binder or solvent. SOLUTION: In a wiring board in which a metallized wiring layer 3 is formed on at least the surface of an insulating substrate 1 composed of a sintered glass ceramic body, a layer containing molybdenum as an oxidizing agent at a rate of 1-3 wt.% in terms of molybdenum oxide (MoO3) and having a thickness of >=8 μm is provided on at least the surface of the substrate 1. In addition, the insulating substrate 1 is formed to show a white color, to contain a transition metal other than molybdenum at a rate of 0.05-10 wt.% in terms of its oxide, and to be colored.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wiring board having a metallized wiring layer.

[0002]

2. Description of the Related Art Conventionally, a ceramic wiring board has a structure in which a metallized wiring layer is provided on the surface or inside of an insulating substrate made of ceramics. As a typical example using this wiring board, a semiconductor element housing package for housing a semiconductor element, especially a semiconductor integrated circuit element such as an LSI (large-scale integrated circuit element) is generally made of an electrical material such as alumina ceramics. An insulating substrate made of an insulating material and having a semiconductor element mounted on its upper surface, and a plurality of metallized wiring layers made of a high melting point metal powder such as tungsten and molybdenum are formed from the upper surface to the lower surface of the insulating substrate,
It is electrically connected to connection pads on the lower surface of the insulating substrate.
Then, an appropriate connection terminal is attached to the connection pad. The semiconductor element mounted on the upper surface of the insulating substrate has a structure hermetically sealed by a lid.

In general, as the degree of integration of a semiconductor device increases, the number of electrodes formed on the semiconductor device also increases. As a result, the number of terminals in a semiconductor storage package also increases. However, as the number of electrodes increases, there is a limit in increasing the size of the package itself. Therefore, as more miniaturization is required, it is necessary to increase the density of terminals in the package.

Conventionally, as a structure for increasing the terminal density in a package, a structure using a metal pin as a connection terminal has been mainly used, but a structure using a ball-shaped solder has recently been proposed. Have been. In particular, it is said that the highest density is possible when a ball-shaped terminal is used.

Further, as an insulating substrate in a package for housing a semiconductor element, a metallized wiring layer can be formed of a low-resistance metal such as Cu or Ag instead of the alumina ceramics or the like. An insulating material made of a sintered body such as a glass-ceramic has been proposed.

[0006]

The use of glass ceramics as an insulating substrate is useful in that Cu or Ag, which is a low-resistance conductor, can be formed as a metallized wiring layer. However, when co-firing is performed using Cu. Has C
Since the melting point of u is 1083 ° C., the firing temperature is 1000
It is limited to below ° C. Further, since Cu is a metal which is very easily oxidized, the firing must be performed in a non-oxidizing atmosphere or a controlled oxidizing atmosphere.

[0007] The glass ceramic substrate is generally 30 to 1
It is composed of 00% by weight of glass and 0 to 70% by weight of a filler. Particularly, glass easily adsorbs organic substances on its surface, and is difficult to desorb organic substances up to a high temperature range.
In the firing atmosphere, it was difficult to quickly remove the residue of the organic binder. Therefore, there is a problem that the time required for the binder removal treatment and the baking is extremely long in order to completely remove the residue of the binder, and the productivity is significantly reduced.

[0008] Further, it is difficult to completely remove the residue even after a long-time degreasing treatment by a method such as vacuum degreasing. As a result, the residue may cause the vicinity of the insulating substrate surface or the insulating substrate. There was a tendency that bleeding occurred between the metallized wiring layer and the metallized wiring layer, and that the color tone became dull compared with the case of firing in air.

Accordingly, the present invention provides a wiring board having an insulating substrate made of glass ceramic and having a metallized wiring layer made of a low-resistance metal on its surface, capable of co-firing with the metallized wiring layer and having an organic binder or solvent. It is an object of the present invention to provide a wiring board that can easily remove the residue caused by the residue and has no defect caused by the residue.

[0010]

Means for Solving the Problems The present inventors have studied the above problems and found that molybdenum is deposited on at least the surface of the insulating substrate in an amount of 0.01 (MoO ₃ ) in terms of oxide (MoO ₃ ).
It has been found that by providing a layer containing at a ratio of ３3% by weight with a thickness of 8 μm or more, it is possible to quickly remove organic residues caused by an organic binder or a solvent, and have reached the present invention.

That is, a wiring board according to the present invention is a wiring board formed by applying a metallized wiring layer to at least the surface of an insulating substrate made of a glass ceramic sintered body. It is characterized in that a white Mo-containing layer containing molybdenum at a ratio of 0.01 to 3% by weight in terms of oxide (MoO ₃ ) is provided with a thickness of 8 μm or more.

Another wiring board according to the present invention is a wiring board comprising a metallized wiring layer formed on at least the surface of an insulating substrate made of a glass ceramic sintered body.
Molybdenum is used as an oxidizing agent on at least the surface of the insulating substrate in an amount of 0.01 to 3% by weight in terms of oxide (MoO ₃ );
It is characterized in that a molybdenum content containing a transition metal other than molybdenum at a ratio of 0.05 to 10% by weight in terms of oxide as a colorant is provided in a thickness of 8 μm or more.

[0013]

According to the present invention, molybdenum is converted to oxide (MoO) on at least the surface of an insulating substrate in a wiring board having a metallized wiring layer made of a low-resistance metal such as Cu.
₃ ) By containing 0.01 to 3% by weight, the carbonaceous residue adhering to the glass surface due to the organic binder and the solvent due to the oxidizing action of the Mo component can be efficiently and rapidly removed. .

In the case of manufacturing a wiring board having an insulating substrate made of glass ceramic, an organic binder is added to the glass ceramic composition in order to form it into a predetermined product shape, and a slurry is formed into a sheet. In such a case, an organic solvent is used.

These organic components are firmly bound to the surface of the glass during the grinding or mixing of the glass, and the solvent is removed.
Even after the binder removal process, a part of the binder remains on the glass surface, and the residue generated in the binder removal process also adheres to the glass surface. In general,
The firing process of the glass ceramics includes a process of thermally decomposing the binder, a process of removing residues caused by the binder and the solvent, and a process of sintering the inorganic components.

The thermal decomposition of the binder is completed at about 400 ° C., and a residue is generated. The sintering of the inorganic component depends on the composition of the composition, but generally starts sintering in a temperature range of 750 ° C. to 900 ° C. and ends by about 1000 ° C.

That is, the thermal decomposition of the binder is completed 40
0 ° C to 750 ° C, 900 even when firing start temperature is high
It is necessary to remove the residue in the temperature range up to ° C. 750
If the residue remains in the temperature range above ℃ or 900 ℃,
The sintered body has a gray color. In addition, when the residue is vaporized by desorption or oxidation, when baked simultaneously with the metallized wiring layer, blisters are generated at the interface with the metallized wiring layer formed on the surface. In order to avoid such a blistering phenomenon of the metallized wiring layer, it is necessary to completely remove the residue in a temperature range of 900 ° C. or lower, preferably 750 ° C. or lower.

However, since Cu is a metal which is very easily oxidized, the firing atmosphere must be a non-oxidizing atmosphere in which Cu is not oxidized or an atmosphere controlled so as not to oxidize Cu. However, it is difficult to quickly remove the residue in an atmosphere where it is not oxidized.

Therefore, the present inventors have studied and as a result, laminated at least the green sheet containing MoO ₃ or MoO ₂ on at least the surface of the green sheet containing the organic binder or the solvent of the insulating substrate, or added MoO ₃ or MoO ₂ to the insulating sheet. MoO ₃ or MoO ₂ acts as an oxidizing agent by applying a ceramic paste to be contained and printing and applying a metallized wiring layer paste on the surface thereof, and efficiently removes residues quickly at a temperature of 900 ° C. or less. be able to.

As the oxidizing agent, CuO and the like are known in addition to MoO ₃ and MoO ₂ . These are all 400
Although it functions as an oxidizing agent from a temperature range of 400 ° C. or less, the added oxidizing agent is consumed for oxidation of the organic binder because the thermal decomposition of the organic binder is not completed in a temperature range of 400 ° C. or less, In a temperature range of 400 ° C. or higher where the residue is generated, a part or all of the part loses the function as an oxidizing agent, and a sufficient effect cannot be expected.

Therefore, a substance that is stable at a temperature of 400 ° C. or less and functions as an oxidizing agent in a temperature range of 400 ° C. or more and 900 ° C. or less, or a substance that is generated even if it functions as an oxidizing agent in a temperature range of 400 ° C. or less. It is necessary to use a material that can function as an oxidizing agent in a temperature range of 400 ° C. or more and 900 ° C. or less, but MoO ₃ and MoO ₂
Satisfies these conditions, and by including them on the surface of an insulating substrate made of glass ceramics, it becomes possible to quickly remove residues caused by organic binders and solvents, and the blistering phenomenon of the surface metallized wiring layer In addition, poor color tone and the like of the insulating substrate can be effectively suppressed.

Further, according to the wiring board of the present invention, although the addition system of Mo alone as the transition metal exhibits white, the transition metal other than Mo as a coloring agent is contained therein. A colored wiring board having the above-described Mo effect can be manufactured.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the accompanying drawings showing an embodiment. FIG. 1 shows an example of a wiring board of the present invention, which has a basic structure of a so-called wiring board in which a metallized wiring layer is provided on the surface or inside of an insulating substrate. 1 is a schematic cross-sectional view showing one embodiment of a package for housing a semiconductor element and its mounting structure as a typical example, wherein A is a package for housing a semiconductor element, and B is an external circuit board.

A package A for housing a semiconductor element is composed of an insulating substrate 1, a lid 2, a metallized wiring layer 3, connection terminals 4, and a semiconductor element 5 housed inside the package. A container 6 for hermetically containing the semiconductor element 5 therein is formed. That is, the semiconductor substrate 5 is placed and accommodated on the upper surface of the insulating substrate 1.
Is bonded and fixed to the insulating substrate 1 via an adhesive such as glass or resin.

A plurality of metallized wiring layers 3 are formed on the insulating substrate 1 from the periphery where the semiconductor element 5 is mounted to the lower surface, and a large number of connection pads 4a are formed on the lower surface of the insulating substrate 1. Are provided, and are electrically connected to the metallized wiring layer 3. On the surface of the connection pad 4a, a protruding terminal 4b made of a brazing material such as solder (tin-lead alloy) is attached as a connection terminal to the external circuit board B.

The method of mounting the projecting terminal 4b is as follows.
There are a method of arranging a spherical or columnar brazing material on the connection pad 4a and a method of printing the brazing material on the connection pad by a screen printing method.

The metallized wiring layer 3 electrically connected to the connection pad 4a is electrically connected to each electrode of the semiconductor element 5 via a bonding wire, so that the electrode of the semiconductor element is connected to the connection pad. 4a.

On the other hand, in the external circuit board B, the wiring conductor 8 is formed on the surface of the insulator 7. The insulator 7 is, specifically, 40 to 4 such as a glass-epoxy composite material.
It is made of an insulating material having a linear thermal expansion coefficient at 00 ° C. of 12 to 16 ppm / ° C. In addition, the wiring conductor 8 is usually made of Cu, in view of the consistency of the linear thermal expansion coefficient with the insulator and the good electrical conductivity.
It is made of a metal conductor such as Au, Al, Ni, and Pb-Sn.

In order to mount the semiconductor element housing package A on the external circuit board B, the projecting terminals 4b attached to the connection pads 4a on the lower surface of the insulating substrate 1 of the package A are connected to the wiring conductors 8 of the external circuit board B. By placing on top and then heating at a temperature of about 250-400 ° C.
The protruding terminal 4b itself made of a brazing material such as solder is melted, and is mounted on the external circuit board B by joining the protruding terminal 4b to the wiring conductor 8. At this time, it is preferable that a brazing material is formed on the surface of the wiring conductor 8 so as to be easily connected to the terminal 4b by the brazing material.

(Material of Insulating Substrate) According to the present invention, the insulating substrate 1 in the package for housing a semiconductor element is made of glass ceramic. As glass ceramics, crystalline glass or amorphous glass is 20 to 80% by volume, and ceramic filler is 80%.
Desirably, the ratio is about 20% by volume.

Further, the deformation point of the glass used is 400 ° C.
It is also necessary that the temperature is from 800 to 800C, especially from 400 to 650C. This is because when a mixture of crystalline glass and a filler is formed into a sheet, a molding binder such as an organic resin is added, and the binder is efficiently removed, and metallization is performed simultaneously with the insulating substrate. It is necessary to match the firing conditions.

If the yield point is lower than 400 ° C., sintering of the glass starts at a low temperature.
Sintering temperature of 600 to 800 ° C. cannot be simultaneously fired, and the densification of the molded body starts at a low temperature, so that the binder cannot be decomposed and volatilized, and the binder component remains to affect the properties. It is because of the result. On the other hand, if the yield point is higher than 800 ° C., sintering becomes difficult unless the amount of crystalline glass is increased, so that a large amount of expensive crystalline glass is required, which increases the cost of the sintered body.

It is desirable that Pb is not substantially contained in the glass. This is because Pb is toxic and requires special equipment and control for preventing poisoning during the manufacturing process, so that sintered bodies cannot be manufactured at low cost. Considering the case where Pb is inevitably mixed as an impurity, the amount of Pb is desirably 0.05% by weight or less.

On the other hand, it is desirable that the amount of the filler component is appropriately adjusted according to the yield point of the glass. That is, when the yield point of the glass is as low as 400 ° C. to 650 ° C., the sinterability at low temperatures is increased, so that the content of the filler can be relatively large as 50 to 80% by volume. On the other hand, when the yield point of the glass is as high as 650 ° C. to 800 ° C., the sinterability is deteriorated, so that the content of the filler is desirably relatively low, ie, 20 to 50% by volume.

The glass used in the present invention has a shrinkage initiation temperature of 700.degree.
If the temperature is higher than ℃, the metallized wiring layer and the like cannot be provided. However, by mixing the filler at a ratio of 20 to 80% by volume, a liquid phase for liquid phase sintering of the filler component can be formed at an appropriate temperature in the firing process. In addition, since the shrinkage start temperature of the entire molded body can be raised, the co-firing condition with the metallized wiring layer can be matched by the type of metallization used by adjusting the content of the filler.

In order to reduce raw material costs, it is preferable to reduce the content of expensive glass. For example,
When the metallized wiring layer is made of Cu, since the metallization is fired at 600 to 1000 ° C., the simultaneous firing is performed at a deformation point of the glass of 400 to 650 ° C. and a filler content of 50 to 80 ° C. It is preferably volume%.

As the glass used in the present invention, borosilicate glass, zinc borosilicate glass, lithium silicate glass, PbO glass, BaO glass and the like are used.

As the ceramic filler, Al is used.
₂ O ₃ , SiO ₂ , mullite, forsterite, petalite, nepheline, lithium silicate, carnegie knight, garnite, zirconia and the like are used.

The mixture of the glass and the filler is formed into a sheet by a desired forming means, for example, a doctor blade, a rolling method, a die press, etc., after adding an appropriate forming organic resin binder. Then, it is fired.

In firing, first, the binder component blended for molding is removed. The removal of the binder is performed in an air atmosphere at about 700 ° C., but when Cu is used as the wiring conductor, the removal is performed in a nitrogen atmosphere containing steam at 100 to 700 ° C. At this time, the shrinkage start temperature of the molded body is preferably about 700 to 850 ° C. If the shrinkage start temperature is lower than this, it becomes difficult to remove the binder. It is necessary to control the yield point as described above.

The calcination is performed in an oxidizing atmosphere at 850 ° C. to 1050 ° C., whereby the relative density is increased to 90% or more. If the firing temperature at this time is lower than 850 ° C., densification cannot be achieved, and if it exceeds 1050 ° C., the metallized layer is melted by simultaneous firing with the metallized wiring layer. However, when Cu is used as the wiring conductor, 85
It is performed in a non-oxidizing atmosphere at 0 to 1050 ° C.

In the glass ceramic sintered body thus produced, a crystal phase generated from crystalline glass, a crystal phase generated by a reaction between glass and filler, or a crystal generated by decomposition of a filler component is contained. Equality exists,
A glass phase exists at the grain boundaries of these crystal phases.

In order to manufacture a wiring board having a metallized wiring layer made of at least one of Cu, Ag, Ni, Pd, and Au as the wiring board using the above-mentioned glass ceramic as an insulating board, the insulating board must be manufactured. An appropriate organic binder, a plasticizer, and a solvent are added to and mixed with the raw material powder composed of glass and filler as described above to form a slurry, and the slurry is subjected to a doctor blade method or a calendar roll method. To produce a green sheet (raw sheet). Then, as a metallized wiring layer and connection pads, a metal paste obtained by adding and mixing an organic binder, a plasticizer, and a solvent to an appropriate metal powder among the above metals is printed in a predetermined pattern on the green sheet by a well-known screen printing method. Apply. Also, in some cases,
An appropriate punching process is performed on the green sheet to form a through hole, and this hole is filled with a metallizing paste. Then, a plurality of these green sheets are laminated.

At this time, MoO ₃ or MnO ₂ is added to MnO ₂ in at least the uppermost surface and the lowermost surface of the insulating substrate.
₃ 0.01-3 wt% in terms of, in particular 0.05 to 2 wt%
The green sheets obtained by forming the mixed powder added in the ratio of 1 into a sheet shape are laminated. Alternatively, a paste of the mixed powder is applied.

After that, the laminate on which the Mo-containing layer is formed is subjected to a binder removal treatment at 700 to 850 ° C. in a nitrogen atmosphere, and then fired at 850 to 1050 ° C. in a nitrogen atmosphere to produce a wiring substrate. it can.

In the wiring board of the present invention, the amount of the Mo component is limited to the above-mentioned amount.
The blistering phenomenon and the change in color tone of the surface metallized wiring layer cannot be prevented. If the content exceeds 3% by weight, color unevenness occurs on the surface of the insulating substrate, and the dielectric loss of the substrate increases. Is 50 × 1 at a measurement frequency of 1 MHz.
Since it is higher than 0 ^-4, it may not be suitable for some uses of the wiring board.

It is important that the thickness of the layer containing Mo is 8 μm or more, particularly 10 μm or more in the final product. The thickness of the layer containing molybdenum is 8
This is because even when the thickness is less than μm, the blistering phenomenon of the surface metallized wiring layer cannot be prevented.

As a method of forming the Mo-containing layer,
In addition to the method of laminating or coating the layer containing Mo as described above on the upper and lower surfaces of the laminate for an insulating substrate not containing Mo, the same applies when Mo is contained in the above ratio with respect to the entire insulating substrate. The effect can be obtained.

The wiring board according to the present invention basically has an M
The o component does not act as a coloring component and exhibits substantially white. However, in order to color the wiring board, a transition metal other than molybdenum, for example, Cr, Co, Fe, N
At least one selected from the group consisting of i and V can be contained at a ratio of 0.05 to 10% by weight, particularly 0.1 to 2% by weight in terms of oxide. For example, Cr such as Cr ₂ O ₃
It is also possible to color green by adding the compound. Further, by adding Co, it can be colored blue. When the amount of the coloring component is less than 0.05% by weight, coloring is insufficient, and when the amount exceeds 10% by weight, sintering is inhibited.

[0050]

Example 1 As crystalline glass, (1) 73% SiO _{2 by} weight ratio
_{-8% Li 2 O-13%} CaO-4% Al 2 O 3 -2%
K ₂ O (Pb content 50 ppm or less, yield point 540 ° C)
Was prepared, and quartz (SiO ₂ ) was used as a filler component for the glass as shown in Table 1;
Glass: quartz was weighed so as to have a volume ratio of 45:55, and was further appropriately blended using Cr ₂ O ₃ as a coloring agent. An acrylic resin was added to this mixture as an organic binder, and after further pulverization using toluene as a solvent, a tape having a thickness of 250 μm was prepared by a doctor blade method, a via hole was formed in the tape, and a Cu paste was filled in the hole. At the same time, a Cu metallized paste was printed in a wiring pattern by a screen printing method. Then, the tape was laminated and pressed to produce a laminated mother body.

Further, in addition to the above glass ceramic composition as an insulating substrate surface composition, a molybdenum source M
Table 1 using oO ₃ and MnO ₂ and further using Cr ₂ O ₃
Were weighed and mixed so as to obtain the composition shown in Table 1. After pulverizing this mixture, an acrylic resin is added as an organic binder, toluene is used as a solvent, and a plasticizer is further added and mixed to form a paste, and the uppermost layer and the lowermost layer of the laminated matrix have a predetermined thickness. And apply and dry,
A metallized paste was screen-printed on the surface.
The amount of Cr ₂ O ₃ in the laminated mother body was set to be the same as the insulating substrate surface composition shown in Table 1.

The obtained laminate was treated with N ₂ + H ₂ O at 700 ° C.
950-9 in a nitrogen atmosphere
It was baked at 80 ° C. to produce a wiring board.

Next, swelling near the substrate surface, swelling of the surface metallized wiring layer, and color tone and color unevenness of the insulating substrate were observed using a binocular microscope of 40 times magnification with respect to the wiring substrate obtained as described above. Was observed. Also,
Processing the insulating substrate to a diameter of 60 mm and a thickness of 2 mm
The dielectric loss was determined by the method of C2141. The measurement was performed using an LCR meter (YHP4284A), and 1 MH
The measurement was performed at 25 ° C. under the conditions of z and 1.0 Vrsm. Table 1
Shows these results.

[0054]

[Table 1]

As is clear from Table 1, samples Nos. 1 and 8
When the amount of molybdenum is less than 0.01% by weight in terms of oxide as in the above, the blistering phenomenon was observed at the interface with the metallized wiring layer on the surface of the insulating substrate, and the color tone was lower than that obtained by firing in an oxidizing atmosphere. It had a dull color.

On the other hand, molybdenum is converted to oxide in 0.01
Sample No. 2 to 6, 9 to 1 containing -3% by weight
No swelling phenomenon or poor color tone at the interface between the insulating substrate and the surface metallized wiring layer was found in any of the samples Nos. 3 and 15 to 27 even when different Mo sources were used.

However, when molybdenum is contained in excess of 3% by weight in terms of oxide (MoO ₃ ) as in Samples Nos. 7 and 14, color unevenness occurs on the surface of the insulating substrate and dielectric loss of the substrate is high. became.

As shown in Sample Nos. 15 to 26, Cr
Was added, the compound was colored green, but if the amount was less than 0.05% by weight in terms of oxide, the coloring was insufficient, and as shown in Sample No. 27,
If the content of r exceeds 10% by weight in terms of oxide, sintering was insufficient and the relative density was lowered.

Example 2 A wiring board was prepared and manufactured in exactly the same manner as in Example 1 except that the thickness of the Mo-containing layer was changed as shown in Table 2 in Samples Nos. 15 and 18 of Example 1. The same evaluation as in Example 1 was performed.

[0060]

[Table 2]

As is clear from Table 2, Sample No. 28,
When the thickness of the molybdenum-containing layer was smaller than 8 μm as in No. 32, the blistering phenomenon was observed at the interface between the surface metallized wiring layer and the insulating substrate. On the other hand, sample Nos. 29 to 3
1, the thickness of the molybdenum-containing layer is 8 μm.
In all cases, no blistering phenomenon was observed near the surface of the insulating substrate and at the interface between the surface metallized wiring layer and the insulating substrate.

Example 3 As crystalline glass, (2) 75% SiO _{2 by} weight ratio
-10% Li ₂ O-10% CaO-5% MgO (Pb content 50 ppm or less, yield point 700 ° C.), (3) 74%
SiO ₂ -14% Li ₂ O-2% P ₂ O ₅ -2% K ₂ O
2% ZnO-2% Na ₂ O (Pb content 50 ppm or less, yield point 480 ° C.) Two kinds of glass were prepared,
As shown in Table 3, using alumina as a filler, glass: alumina = 55: 45 or 45:45.
55 at a volume ratio, and Cr ₂ as a colorant.
O ₃ , MnO ₂ or MnO ₃ is added as an oxidizing agent, an acrylic resin is added as an organic binder to the mixture, and after pulverization using toluene as a solvent,
A tape having a thickness of 250 μm was prepared by a doctor blade method, a via hole was formed in the tape, and Cu was inserted in the hole.
While filling the paste, a Cu metallized paste was printed in a wiring pattern by a screen printing method. Then, the tape was laminated and pressed to produce a laminated body.

The obtained laminate was heated at 700 ° C. with N ₂ + H ₂ O
After removing the binder in the substrate, the substrate was baked at 950 ° C. in a nitrogen atmosphere to produce a wiring board having a thickness of 2.0 mm. Then, the same evaluation as in Example 1 was performed on the obtained wiring board.

[0064]

[Table 3]

As is clear from Table 3, even when different glass types are used, MnO ₃ or MnO ₂
In the same manner as in Example 1, no blistering phenomenon was observed at the interface between the insulating substrate and the surface metallized wiring layer, and a uniform color tone was obtained.

[0066]

As described in detail above, according to the wiring board of the present invention, molybdenum is present at a specific ratio on at least the surface of the insulating substrate to simultaneously fire the wiring board having the metallized wiring layer. In this case, it is possible to prevent the blistering phenomenon at the interface between the insulating substrate and the surface metallized wiring layer, and to produce a wiring substrate having a uniform color tone without color unevenness. It can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a package for housing a semiconductor element and an example of a mounting structure thereof as an example of a wiring board of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Insulating substrate 2 ... Lid 3 ... Metallized wiring layer 4a ... Connection pad 4b ... Protruding terminal 5 ... Semiconductor element 6 ... Container 7 ... Insulator 8 ... · Wiring conductor A: Package for storing semiconductor elements B: External circuit board

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsuya Kimura 1-4-4 Yamashita-cho, Kokubu-shi, Kagoshima Inside Kyocera Research Institute (72) Inventor Ken-ichi Nagae 1-4-4 Yamashita-cho, Kokubu-shi, Kagoshima Kyocera Corporation (72) Inventor Yoji Kokubo 1-4-4 Yamashita-cho, Kokubu City, Kagoshima Prefecture Inside Kyocera Research Institute

Claims (2)

[Claims] 1. A wiring board comprising a metallized wiring layer formed on at least a surface of an insulating substrate made of a glass ceramic sintered body, wherein molybdenum as an oxidizing agent is converted into oxide (MoO) on at least the surface of the insulating substrate. ₃ )
A white Mo-containing layer containing at a rate of 0.01 to 3% by weight in a thickness of 8 μm or more. 2. A wiring board comprising a metallized wiring layer formed on at least the surface of an insulating substrate made of a glass ceramic sintered body, wherein molybdenum as an oxidizing agent is converted into oxide (MoO) on at least the surface of the insulating substrate. ₃ )
And a molybdenum content containing a transition metal other than molybdenum as a coloring agent in a ratio of 0.05 to 10% by weight in terms of an oxide in a thickness of 8 μm or more. Wiring board.