JP3152089B2 - Manufacturing method of ceramic wiring board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a ceramic wiring board used as, for example, an electronic component, and more particularly to a method of manufacturing a ceramic wiring board formed by electroless copper plating to form a conductor layer.

[0002]

2. Description of the Related Art Conventionally, when a conductor layer is formed by electroless copper plating on the surface of a ceramic substrate, a chemical etching method such as immersing the ceramic substrate in a high-temperature solution such as hydrofluoric acid, phosphoric acid, sodium hydroxide, or the like is used. Generally, the surface of the ceramic substrate is roughened by a method, so that the adhesion between the conductor layer and the ceramic substrate is secured by the so-called anchor effect.

However, since roughening the surface of the ceramic substrate has a problem of deteriorating high-frequency characteristics, a method of manufacturing a ceramic wiring board capable of forming a strongly adhered conductor layer on the surface of a ceramic substrate as smooth as possible. The development of is desired. Therefore, as a method of forming a conductor layer having excellent adhesion without roughening, various studies have been made on pretreatment of electroless copper plating, formation of an underlayer, and the like, for example, Japanese Patent Publication No. 63-4336. And Japanese Patent Publication No. 4-82043 and Japanese Patent Publication No. 3-69191.

Japanese Patent Publication No. 63-4336 discloses Cu, Z
A paste containing at least one component of a compound of n, Cd, Pb or Bi is applied to a ceramic substrate, and thereafter,
In a non-oxidizing atmosphere, heat treatment is performed at a temperature within the range of 350 to 900 ° C., and Cu, Zn, Cd, Pb, Bi
And then subjecting the surface of the metal or alloy metal to at least one of Pd or Pt in a solution containing at least one ion of Pd or Pt in a solution containing at least one ion of Pd or Pt. And a method of manufacturing a ceramic electronic component in which a nickel, cobalt or copper metal electrode is formed by electroless plating. However, in this case, a heat treatment in a non-oxidizing atmosphere is required, and therefore, there is a problem that a manufacturing apparatus and a manufacturing process are complicated, and further, by a substitution process of substituting at least one of Pd and Pt, It is estimated that the adhesion between the underlayer and the ceramic substrate is impaired,
As seen from the example of JP-B-63-4336, the maximum tensile strength is 2.75 kg / 5φ area (0.53
kg / 4 mm ² ), and in recent years, further improvement in adhesion has been demanded.

Japanese Patent Publication No. 4-82043 discloses that a metal thin film is formed on a ceramic surface by an electroless plating method.
Heat treatment at 200 ° C. to form a chemical bond between the ceramic and the metal thin film, then chemically remove the metal thin film, and then metallize the ceramic surface by electroless plating Is described. However, in the case of this method, the adhesion tends to largely depend on the thickness of the formed metal thin film, and there is a problem that it is difficult to obtain a stable adhesion.

In Japanese Patent Publication No. 3-69191, an alumina substrate is subjected to electroless copper plating.
A method is described in which a heat treatment is performed in an oxidizing atmosphere at a temperature of 200 ° C., a treatment is performed in a reducing atmosphere at a temperature of 200 to 900 ° C., an electroless copper plating is performed, and then an electrolytic copper plating is performed. However, in this method, since the treatment is performed in a reducing atmosphere, the production apparatus and the production process are complicated, and the reduction treatment is performed at a high temperature of 200 to 900 ° C .; It is presumed that the wettability of the surface becomes low, but there was a problem that the adhesion between the base layer after the reduction treatment and the electroless copper plating film formed thereon was insufficient.

[0007]

In view of the above circumstances,
The present invention is a method for manufacturing a ceramic wiring board in which a conductor layer is formed by performing electroless copper plating, and does not require a special atmosphere such as a reducing atmosphere, and has not been subjected to a roughening treatment, and has a smooth surface. It is an object of the present invention to develop a method for manufacturing a ceramic wiring board which can form a conductor layer having a stable and strong adhesion on a surface of a ceramic substrate.

[0008]

According to a first aspect of the present invention, there is provided a method of manufacturing a ceramic wiring board, comprising forming an underlayer containing bismuth and copper on a surface of a ceramic substrate, and then forming the underlayer in an oxidizing atmosphere. And then heat-treated at 600 to 1100 ° C., then immersed in a reducing solution for reduction treatment, and then subjected to electroless copper plating.

According to a second aspect of the present invention, there is provided a method of manufacturing a ceramic wiring board according to the first aspect, wherein the method of forming the underlayer containing bismuth and copper comprises the steps of: The method is characterized in that the material is formed by coating a material containing

According to a third aspect of the present invention, in the method for manufacturing a ceramic wiring board according to the first aspect, the method of forming the underlayer containing bismuth and copper comprises the step of forming a copper-containing layer on the surface of the ceramic substrate. And then forming a bismuth-containing layer on the copper-containing layer.

According to a fourth aspect of the present invention, in the method for manufacturing a ceramic wiring board according to the first aspect, the method of forming the underlayer containing bismuth and copper comprises the step of forming a bismuth-containing layer on the surface of the ceramic substrate. And then forming a copper-containing layer on the bismuth-containing layer.

According to a fifth aspect of the present invention, there is provided a method of manufacturing a ceramic wiring board according to any one of the first to fourth aspects, wherein the base layer containing bismuth and copper is formed of copper. It is characterized in that the component is metallic copper powder treated with an ethylenediamine-based chelating agent.

According to a sixth aspect of the present invention, there is provided a method of manufacturing a ceramic wiring board according to any one of the first to fourth aspects, wherein the copper for forming an underlayer containing bismuth and copper is provided. The component is a metal copper powder precipitated from an electroless plating solution containing an ethylenediamine-based chelating agent.

Hereinafter, the present invention will be described in detail. Examples of the material of the ceramic substrate used in the present invention include, for example, oxide-based ceramics such as alumina, zirconia, cordierite, and barium titanate; nitride-based ceramics such as aluminum nitride and silicon nitride; and carbide-based materials such as silicon carbide. And the like are not particularly limited.

An underlayer containing bismuth and copper is formed on the surface of the above-mentioned ceramic substrate. The following three methods can be used for forming the underlayer. A method capable of forming an underlayer containing bismuth and copper is used. There is no particular limitation if it exists. For example, a method of coating a material containing both bismuth and copper metal components such as a mixed resinate paste obtained by mixing a bismuth resinate paste and a copper resinate paste to form a layer in which bismuth and copper are mixed in a single step. A method for forming an underlayer containing bismuth and copper by forming a copper-containing layer and then forming a bismuth-containing layer on the copper-containing layer. A method of forming an underlayer containing bismuth and copper by forming a bismuth-containing layer and then forming a copper-containing layer on the bismuth-containing layer.

The means for forming a copper-containing layer, a bismuth-containing layer, and a layer in which bismuth and copper are mixed for forming a base layer containing bismuth and copper are not particularly limited. , A sputtering method, a metal paste method, an organic metal resinate (or a paste thereof) method, or the like. In the case of a method in which the copper-containing layer and the bismuth-containing layer are independently formed as in the methods (1) and (2), the copper-containing layer is formed only on a portion to be a circuit pattern, and the bismuth-containing layer is formed on the entire surface of the ceramic substrate. If formed, when heat treatment and reduction treatment are sequentially performed in a subsequent step, bismuth oxide alone (partially metal bismuth is present) is formed in portions other than the circuit pattern portion. Since the electroless copper plating does not precipitate on this bismuth oxide alone, and the bismuth oxide alone can be quickly etched with an acid, only the bismuth-containing layer is formed to function as a plating resist for electroless copper plating. Can be fulfilled.

The thicknesses of the copper-containing layer, the bismuth-containing layer, and the layer in which bismuth and copper are mixed for forming the underlayer containing bismuth and copper are not particularly limited. However, when the copper-containing layer is formed on the surface of the ceramic substrate as described above, and then the bismuth-containing layer is formed on the copper-containing layer, the thickness of the copper-containing layer is 0.05 to 3.0.
The range of μm is preferable in order for the finally obtained conductor layer to have a stable adhesion.

When a bismuth resinate paste is used, the bismuth content in the bismuth resinate paste is preferably 10% by weight or more. If the bismuth content is less than 10% by weight, the adhesion of the finally obtained conductor layer to the ceramic substrate is undesirably reduced.

In the present invention, after forming an underlayer containing bismuth and copper on the surface of the ceramic substrate, heat treatment is performed to oxidize bismuth and copper. By this heat treatment step, bismuth oxide is diffused, so that copper oxide is generated on the surface of the underlayer containing bismuth and copper. This heat treatment is performed at 600 to 1100 ° C. in an oxidizing atmosphere such as the air.
It is important to carry out at a temperature of less than 600 ° C. If the temperature is lower than 600 ° C., the adhesion of the finally obtained conductor layer to the smooth ceramic substrate surface becomes insufficient. In the next electroless copper plating step, the copper component acting as a catalyst for the electroless copper plating does not remain on the outermost surface of the ceramic substrate, so that the adhesion is also insufficient.

In the present invention, the ceramic substrate after the above heat treatment is immersed in a reducing solution to perform a reduction treatment. By this step, the copper oxide present on the surface of the underlayer containing bismuth and copper is reduced to metallic copper. This metallic copper serves as a catalyst nucleus in the subsequent electroless copper plating step, and desired electroless copper plating can be performed. The reducing solution is not particularly limited as long as it can reduce copper oxide, and examples thereof include a borohydride solution, a hypophosphite solution, and a dimethylamine borane solution. The temperature of the reducing solution is not particularly limited, but it is preferable to perform the reduction at a temperature higher than room temperature in order to shorten the time of the reduction treatment.

Next, a conductor layer is formed by performing electroless copper plating on the ceramic substrate that has been subjected to the above-described reduction treatment. If necessary, a metal layer may be further formed thereon by a method such as electroplating to form a conductor layer. The method of electroless copper plating is not particularly limited.

Further, in the present invention, the copper component forming the underlayer containing bismuth and copper is a metal copper powder treated with an ethylenediamine-based chelating agent or an electroless plating solution containing an ethylenediamine-based chelating agent. It is preferable that the metal copper powder be precipitated from further increases the adhesion of the conductor layer finally obtained. The ethylenediamine-based chelating agent in the present invention refers to an ethylenediamine-based chemical substance capable of forming a copper chelate compound. The ethylenediamine-based chelating agent is not particularly limited, but ethylenediaminetetraacetic acid (hereinafter, referred to as EDTA) Abbreviated), ethylenediamine-based chelate reagents such as ethylenediaminediacetate, and ethylenediamine-based chelate compounds such as disodium ethylenediaminetetraacetate. The method of treating with an ethylenediamine-based chelating agent is not particularly limited, but examples thereof include immersion, coating, and spraying.

[0023]

In the method for manufacturing a ceramic wiring board according to the present invention, an underlayer containing bismuth and copper is formed on the surface of a ceramic substrate, and then heat-treated at 600 to 1100 ° C. in an oxidizing atmosphere. An oxide of bismuth and copper is formed. Bismuth oxide has good wettability to the ceramic substrate and diffuses to act as an adhesive to the ceramic substrate. In addition, since bismuth oxide and copper oxide form a compound, the adhesion between them becomes strong. Furthermore, since the diffusion rate of bismuth oxide to the ceramic substrate side is higher than that of copper oxide, even if the layer containing bismuth and copper is formed by any of the above-mentioned methods, the bismuth and heat-treated A copper oxide layer appears on the surface of the copper-containing base layer.

In the present invention, after the heat treatment, the substrate is immersed in a reducing solution, subjected to a reduction treatment, and then subjected to electroless copper plating. Therefore, the copper oxide layer which appears on the surface of the underlayer after the heat treatment is formed. Is converted to metallic copper by the reduction treatment. This metallic copper acts as a plating catalyst in the next step of electroless copper plating. In addition, the fact that the diffusion rate of bismuth oxide is higher than that of copper oxide acts to reduce the degree to which the thickness variation of the underlayer affects the adhesion, and a stable adhesion can be obtained.

And, as in the above methods and,
When the copper-containing layer and the bismuth-containing layer are formed independently, the bismuth-containing layer is formed on the entire surface of the ceramic substrate,
If the copper-containing layer is formed only in the portion that becomes the circuit pattern, the portion in which only the bismuth-containing layer is formed does not deposit electroless copper plating, and thus functions as a plating resist for electroless copper plating. be able to.

Further, in the present invention, the copper component forming the underlayer containing bismuth and copper is precipitated from metallic copper powder treated with an ethylenediamine-based chelating agent or from an electroless plating solution containing an ethylenediamine-based chelating agent. Is that the copper chelate compound is formed on the surface of the metal copper powder, so that the copper oxide when heat-treated at 600 to 1100 ° C. in an oxidizing atmosphere is unlikely to become complete CuO As a result, the copper oxide layer can be easily changed to metallic copper in the next reduction treatment. Therefore, the metallic copper obtained by the reduction treatment reliably acts as a plating catalyst in the next step of electroless copper plating, and can form a firm bond with the copper film to be formed. Can be improved.

[0027]

EXAMPLES Specific examples of the present invention and comparative examples are shown below.

(1) Examples in which an underlayer is formed by coating using a material containing both metal components of bismuth (hereinafter abbreviated as Bi) and copper (Examples 1 to 5) A Bi resinate paste (manufactured by NE Chemcat, # 8365, Bi content 20
%) And 8 parts by weight of a copper resinate paste (manufactured by NE Chemcat Co., Ltd., # 29-B, Cu content 6%) were mixed to form a circuit pattern, and then a circuit pattern was formed. Drying was performed at 125 ° C. for 10 minutes to form an underlayer in which Bi and copper were mixed.
Thereafter, the substrate is heat-treated at 850 ° C. for 1 hour in the air, and then an aqueous solution of sodium borohydride (p
H12.5) for 5 minutes to perform a reduction treatment.

The substrate after the reduction treatment was subjected to electroless copper plating, and a copper plating film having a thickness of 10 μm was formed on the circuit pattern to form a conductor layer, thereby obtaining a ceramic wiring board. The adhesive strength between the ceramic substrate and the conductor layer in the obtained ceramic wiring board was measured. As shown in FIG. 1, the adhesion of the conductor layer was measured using a test piece in which a 0.7 mmφ tin-plated copper wire 4 was joined to a 2 mm square conductor layer 2 formed on a ceramic substrate 1 by solder 3 as shown in FIG. I did it. The arrows in FIG. 1 indicate the tensile direction in the tensile test.
Table 1 shows the measurement results of the obtained adhesion. From the results in Table 1, it can be seen that in Examples 1 to 5, good adhesion was obtained.

[0030]

[Table 1]

(2) Examples in which a copper-containing layer is formed, and then a Bi-containing layer is formed on the copper-containing layer, and an underlayer is formed (Examples 6 to 15). After nucleation having a Pd component was performed on various ceramic substrate surfaces shown in Table 2 without electroplating, electroless copper plating was performed, and a copper-containing layer (metal copper film) having a thickness shown in Table 2 was applied to the entire surface of the ceramic substrate surface. Formed. Then
The copper-containing layer was processed by an etching method so that the copper-containing layer was left only in a portion to be a circuit pattern, and the copper-containing layer was patterned. After that, Bi resinate paste (N.
# 8365, Bi content 20, manufactured by E-Chemcat
%) Is applied to the entire surface of the substrate by a screen printing method,
A drying treatment was performed at 125 ° C. for 10 minutes to form a Bi-containing layer. In this way, a substrate was obtained in which the underlayer containing Bi and copper was formed in the circuit pattern portion, and only the Bi-containing layer (containing no Cu) was formed in portions other than the circuit pattern portion.

Thereafter, the substrate was heat-treated at 850 ° C. for 1 hour in the air, and then immersed in an aqueous solution of sodium borohydride (pH 12.5) at 80 ° C. for 5 minutes to perform a reduction treatment. The substrate after the reduction treatment was subjected to electroless copper plating, and a copper plating film having a thickness of 10 μm was formed on the circuit pattern to form a conductor layer. Since the portion other than the circuit pattern portion is covered with a single body of Bi oxide generated by the heat treatment (the Bi oxide is not reduced in the reduction treatment), deposition of electroless copper plating on the portion is recognized. However, it was confirmed that the portion where only the Bi-containing layer was formed functions as a plating resist for electroless copper plating.

Next, the single layer of Bi oxide formed at locations other than the circuit pattern portion was quick-etched with an acid solution to obtain a ceramic wiring board. The adhesion of the conductor layer in the obtained ceramic wiring board was measured by the same method as in Examples 1 to 5, and the obtained measurement results are shown in Table 2. From the results in Table 2, it can be seen that in Examples 6 to 15, good adhesion was obtained.

[0034]

[Table 2]

(3) Examples in which a Bi-containing layer is formed and then a copper-containing layer is formed on the Bi-containing layer to form an underlayer (Examples 16 to 25). For each of the ceramic substrates shown in Table 3, a Bi resinate paste (N.
# 8365, Bi content 20, manufactured by E-Chemcat
%) Was dried by screen printing, or after a nucleus having a Pd component was applied to the surface of the ceramic substrate, and electroless Bi plating was applied to form a Bi-containing layer on the entire surface of the ceramic substrate surface. The method for forming the Bi-containing layer in each example was as shown in Table 3.

Next, a copper resinate paste (manufactured by NE Chemcat, # 29-B, Cu content 6%)
Is printed and dried to form a copper-containing layer only on the portion that will become a circuit pattern, a base layer containing Bi and copper is formed on the circuit pattern portion, and a Bi-containing layer is formed on the non-circuit pattern portion. A substrate on which a layer (containing no copper) was formed was obtained.

Thereafter, the substrate was heat-treated at 850 ° C. for 1 hour in the air, and then immersed in an aqueous solution of sodium borohydride (pH 12.5) at 80 ° C. for 5 minutes to perform a reduction treatment. The substrate after the reduction treatment was subjected to electroless copper plating, and a copper plating film having a thickness of 10 μm was formed on the circuit pattern to form a conductor layer. Since the portion other than the circuit pattern portion is covered with a single body of Bi oxide generated by the heat treatment (the Bi oxide is not reduced in the reduction treatment), deposition of electroless copper plating on the portion is recognized. However, it was confirmed that the portion where only the Bi-containing layer was formed functions as a plating resist for electroless copper plating.

Next, the single layer of Bi oxide formed at locations other than the circuit pattern portion was quick-etched with an acid solution to obtain a ceramic wiring board. The adhesion of the conductor layer in the obtained ceramic wiring board was measured in the same manner as in Examples 1 to 5, and the obtained measurement results are shown in Table 3. From the results in Table 3, it can be seen that in Examples 16 to 25, good adhesion was obtained.

[0039]

[Table 3]

(4) In the manufacturing conditions of the seventh embodiment,
Examples in which Bi content in Bi resinate was changed (Examples 26 to 29) By adjusting the amount of the viscosity adjusting resin in Bi resinate, the Bi content in Bi resinate was adjusted to the amount shown in Table 4. Example 7 (the Bi content in the used Bi resinate was 2%) except that the used Bi resinate was used.
0%) to obtain a ceramic wiring board. The adhesion of the conductor layer in the obtained ceramic wiring board was measured by the same method as in Examples 1 to 5 described above, and the obtained measurement results including the values of Example 7 are shown in Table 4. Show. Table 4
It can be seen from the results that better adhesion can be obtained if the Bi content in the Bi resinate is 10% or more.

[0041]

[Table 4]

(5) Examples and Comparative Examples (Examples 30 to 33 and Comparative Examples 1 to 3) in which the heat treatment temperature and the heat treatment time in the manufacturing conditions of Example 16 were changed. A ceramic wiring board was obtained in the same manner as in Example 16 (heat treatment temperature of 850 ° C.) except that the heat treatment temperature and the heat treatment time for the heat treatment were changed to the conditions shown in Table 5. The adhesion of the conductor layer in the obtained ceramic wiring board was measured in the same manner as in Examples 1 to 5 above, and the obtained measurement results are shown in Table 5 including the values of Example 16. Show.

From the results shown in Table 5, the heat treatment temperature was from 600 to 1
It can be seen that good adhesion can be obtained in the range of 100 ° C. In the present invention, it is desirable to set an appropriate heat treatment time for each heat treatment temperature to be set.

[0044]

[Table 5]

(6) Example in which metallic copper powder treated with an ethylenediamine-based chelating agent is used as a copper component for forming a base layer containing Bi and copper (Examples 34 and 35) , An alkaline saturated aqueous solution of disodium ethylenediaminetetraacetate (abbreviated as EDTA.2Na) was prepared, and a metal copper powder having an average particle size of 1 μm was prepared using the EDTA
After immersion in a 2Na solution, stirring, filtration, and drying, a metal copper powder treated with an ethylenediamine-based chelating agent was prepared. Subsequently, 1.05 parts by weight of the treated metal copper powder and Bi resinate paste (N.
# 8365, Bi content 20, manufactured by E-Chemcat
%) And 2 parts by weight to prepare a mixed paste. Then, a ceramic wiring board was obtained in the same manner as in Example 1 except that this mixed paste was used instead of the mixed resinate paste in Example 1. The adhesion of the conductor layer in the obtained ceramic wiring board was measured by the same method as in the above-described Examples 1 to 5, and the obtained measurement result was measured.
It is shown in Table 6 .

In Example 35, sodium borohydride was added to an electroless copper plating solution containing EDTA,
The electroless copper plating solution was decomposed to deposit metallic copper powder. Next, 1.05 parts by weight of the obtained metallic copper powder and Bi
Resinate paste (manufactured by NE Chemcat, Inc.
# 8365, Bi content 20%) and 2 parts by weight to prepare a mixed paste. Then, a ceramic wiring board was obtained in the same manner as in Example 1 except that this mixed paste was used instead of the mixed resinate paste in Example 1. The adhesion of the conductor layer in the obtained ceramic wiring board was measured in the same manner as in Examples 1 to 5 above, and the obtained measurement results are shown in Table 6.

From the results in Table 6, it can be seen from Examples 34 and 3 that
5, it can be seen that even better adhesion was obtained than in Example 1.

[0048]

[Table 6]

[0049]

In the method for manufacturing a ceramic wiring board according to the first and second aspects of the present invention, an underlayer containing Bi and Cu is formed on the surface of a ceramic substrate, and then a temperature of 600 to 1100 ° C. in an oxidizing atmosphere. Heat treatment, then immersion in a reducing solution for reduction treatment, and then electroless copper plating.Therefore, there is no need for a special atmosphere such as a reducing atmosphere. A conductor layer having a stable and strong adhesion can be formed on the surface.

In the method for manufacturing a ceramic wiring board according to the third and fourth aspects of the present invention, since the copper-containing layer and the Bi-containing layer are formed independently, the Bi serving as a plating resist is formed.
Since it is possible to provide a portion where only the containing layer is formed,
In addition to the above effects, an effect of increasing the degree of freedom in process design is also achieved.

According to the method for manufacturing a ceramic wiring board according to the fifth and sixth aspects of the present invention, the copper component forming the underlayer is made of metal copper powder or an ethylenediamine-based chelating agent treated with an ethylenediamine-based chelating agent. Since the metal copper powder is precipitated from the contained electroless plating solution, a conductor layer having a stronger adhesion can be formed in addition to the above-described effects.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a method for measuring the adhesion between a ceramic substrate and a conductor layer.

[Description of Signs] 1 ceramic substrate 2 conductor layer 3 solder 4 tin-plated copper wire

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-55094 (JP, A) JP-A-61-1086 (JP, A) JP-A-61-66305 (JP, A) JP-A-3-3 101291 (JP, A) JP-A-3-136293 (JP, A) JP-A-3-175689 (JP, A) WO 93/7736 (WO, A1) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) H05K 3/18 H05K 3/38

Claims (6)

(57) [Claims] An underlayer containing bismuth and copper is formed on the surface of a ceramic substrate, and then heat-treated at 600 to 1100 ° C. in an oxidizing atmosphere, and then immersed in a reducing solution. A method for producing a ceramic wiring board, which comprises subjecting a ceramic wiring board to reduction treatment and then electroless copper plating. 2. The method of forming an underlayer containing bismuth and copper is a method of coating a material containing both metal components of bismuth and copper on a surface of a ceramic substrate. A method for producing a ceramic wiring board according to claim 1. 3. The method of forming an underlayer containing bismuth and copper is a method of forming a copper-containing layer on the surface of a ceramic substrate and then forming a bismuth-containing layer on the copper-containing layer. The method for producing a ceramic wiring board according to claim 1, wherein: 4. The method of forming an underlayer containing bismuth and copper is a method of forming a bismuth-containing layer on a surface of a ceramic substrate, and then forming a copper-containing layer on the bismuth-containing layer. The method for producing a ceramic wiring board according to claim 1, wherein: 5. The copper component forming the underlayer containing bismuth and copper is metallic copper powder treated with an ethylenediamine-based chelating agent. 3. The method for producing a ceramic wiring board according to item 1. 6. A metal copper powder precipitated from an electroless plating solution containing an ethylenediamine-based chelating agent, wherein a copper component forming an underlayer containing bismuth and copper is a metal copper powder. The method for producing a ceramic wiring board according to any one of the above.