JPH01209783A - Ceramic circuit substrate and manufacture thereof - Google Patents

Abstract

PURPOSE:To form fine wirings having excellent various characteristics, such as heat resistance, heat resistance cycle, etc., by employing at least one type of Mo and W and at least one type of Co and Ni as ceramic for a circuit substrate and forming a circuit with alloy containing P as a conductor in response to its necessity. CONSTITUTION:As ceramic for a circuit substrate, alumina ceramic, magnesia ceramic and alumina-magnesia ceramic are employed. The ceramics for the substrate are degreased, pickled, treated by a roughening bath containing hydroxide alkaline salt and organic acid salt, pickled, treated by a sensitizer bath containing tin salt and inorganic acid, and treated by an activator bath containing palladium salt and inorganic acid. Thereafter, at least one type selected from a group consisting of B, P, Co, Fe, Ni, Cu, Mo, Pd, Ag, Sn, W, Re and Pt is electrolessly plated on the surface of the ceramics, and an alloy containing at least one of Mo and W and at least one of Co and Ni and an alloy containing P are electrolessly plated.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a ceramic wiring board that has high heat resistance, high heat cycle resistance, high corrosion resistance, and allows fine wiring.

The wiring board of the present invention can be used, for example, as a wiring board for aerospace and space applications, precision instruments, power supplies, amplifiers, switching devices, semiconductor packages, ceramic sensors, and the like.

BACKGROUND ART Ceramic wiring boards have particularly good high frequency characteristics and heat dissipation characteristics, so they are not only used as hybrid boards but also widely used in wireless communication equipment, amplifiers, and the like. However, with the progress and sophistication of electronic equipment in recent years, the performance and reliability required of ceramic wiring boards are becoming even more sophisticated. That is, wiring boards with excellent heat resistance and corrosion resistance that can be used in somewhat special environments, ceramic wiring boards with fine wiring with conductor width and conductor spacing of 100 μm or less, and wiring boards that combine the characteristics of both. is requested.

Conventional ceramic wiring boards include, for example, 1) W;
Wiring board made by co-sintering powder such as Mo-based alloy, 2) Ag
Wiring board paste-printed with alloy, Cu, etc., 3) Cu
Wiring boards that are plated, 4) wiring boards that are sputtered with Au, Cr, etc. are used. however,
Both wiring boards have the following drawbacks and are undesirable. In other words, although the wiring board 1) has good heat resistance, since the conductor is sintered metal with a glass component as a binder,
Since the conductor resistance is relatively high and etching processing is not possible, it is difficult to form fine wiring with conductor width and conductor spacing of 100 μm or less. Furthermore, since the surface of metal powder oxidizes in air at high temperatures, the conductor resistance of the sintered metal increases significantly, making it difficult to use it continuously for about 100 hours at temperatures above 400°C. Furthermore, since the entire board is fired, it is difficult to guarantee the dimensional accuracy of the wiring board. Furthermore, when plating is applied to the above-mentioned conductor, there is also a drawback that the defective rate is high. Although the wiring board 2) is the most widely used, it has poor heat resistance and corrosion resistance, and is manufactured by paste printing, making it difficult to form fine wiring with a conductor width and conductor spacing of 100 μm or less. Further, there are other problems such as insufficient high frequency characteristics, high cost, and easy migration. According to the Cu plating method (3), a wiring board having fine wiring with a conductor width and conductor spacing of 100 μm or less can be obtained, but the wiring board has poor heat resistance and corrosion resistance. Therefore, even if fine wiring can be drawn, the wiring may deteriorate over time, and there is also concern that the wiring may be damaged due to the difference in thermal expansion coefficient between copper and ceramics. The wiring board 4) is used for thin film ceramic wiring boards, but it has low productivity and is expensive.

Furthermore, it is difficult to thicken the film to allow large current to flow.

Means for Solving the Problems The inventors of the present invention have conducted extensive research in order to eliminate the drawbacks of conventional ceramic wiring boards manufactured by various metallizing methods as described above. As a result, when forming a circuit using a ceramic for wiring boards as a conductor, an alloy containing a small amount of Mo and W (both 1 type, at least 1 type of Co and Ni, and P as necessary), the conductor width The present invention was completed based on the discovery that fine wiring with a conductor spacing of 100 μm or less can be formed extremely easily, and that the resulting wiring board has excellent properties such as heat resistance, heat cycle resistance, corrosion resistance, and electrical properties. did.

That is, the present invention provides: (1) A ceramic for a wiring board selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics;

and at least one of W and at least one of Co and Ni
A ceramic wiring board equipped with a circuit made of an alloy containing seeds, and (1) a ceramic for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics;

The present invention provides a ceramic wiring board including a circuit made of an alloy containing at least one of Co and W, at least one of Co and Ni, and P, and a method for manufacturing the same.

In the present invention, alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are used as ceramics for wiring boards (hereinafter referred to as ceramic substrates). Known alumina ceramics can be used; for example, 40 to 99
．． 99% alumina (A1220s), mullite (3
A9203・5iO2), ordinary porcelain (AQ20s・
5i02) etc. can be preferably used. Also known as magnesia ceramics can be used, among which, for example, magnesia (MgO), forsterite (2MgO・5i02), steatite (MgO-S
i 02 ) etc. can be particularly preferably used. Alumina
For magnesia-based ceramics, the ratio of alumina and magnesia is 0.5:99°95 to 99.95:0.5.
Any of these can be used, but among them, for example, Kogelai) (2MgOΦ2AQ203 @58
i02) etc. can be particularly preferably used. The shape of the ceramic substrate is not limited to a plate-like shape, and may be any shape such as a rectangle, a cylinder, or a sphere.

In the present invention, at least one of Mo and W, Co and N are used as conductors for forming a circuit on a ceramic substrate.
An alloy containing at least one type of i and optionally P (hereinafter collectively referred to as Mo/W-Co/Ni-based alloy) is used. As described later, the alloy is adhered to the ceramic substrate as an alloy plating film by a plating method. Conventionally, Mo/W-Co/Ni alloy plating film was
Although it is used as an abrasion-resistant film, a release film for glass molds, and an acid-resistant film, it has never been used as a conductive material for ceramic wiring boards.

The content of each metal in the Mo/W-Co/Ni-based alloy is not particularly limited and may be selected as appropriate.
Usually, when P is included, at least one of Mo and W is 0.
Approximately 5 to 40% by weight, at least one of Co and Ni60
~99% by weight and the remainder P, if it does not contain P,
The content may be about 0.5 to 75% by weight of at least one of Mo and W, and about 25 to 99.5% by weight of at least one of Co and Ni.

The Mo/W-Co/Ni alloy has excellent heat resistance, corrosion resistance, and electrical properties, and has a coefficient of thermal expansion very close to that of the ceramic substrate.

The manufacturing process of the ceramic wiring board of the present invention is usually (1
) a step of subjecting the ceramic substrate to a specific pretreatment (referred to as a pretreatment step); (2) a step of applying M o on the ceramic substrate;
/W-Co/Ni A process of forming a plating film of an i-based alloy (referred to as a plating process) and (3) a process of forming a circuit on a ceramic substrate by performing resist formation, etching, etc. (referred to as a circuit formation process) Contains. Each step will be explained below.

(1) Pretreatment process The pretreatment process includes the following steps) to V).

■) First, the ceramic substrate is degreased and washed with water.

Any known method can be used as the degreasing method, and examples thereof include ultrasonic solvent degreasing, ultrasonic immersion alkaline degreasing, neutral degreasing, acid degreasing, vapor degreasing, and the like.

(2) Next, after washing with a dilute acid method and water using a conventional method, it is treated by immersing it in a roughening treatment bath having the following composition, and then washed with water. The treatment is usually about 80 to 130°C, preferably 90 to 110°C.
Preferably 10 minutes to 200 hours at a temperature of
It will be completed in about 100 minutes to 100 hours.

(Roughening treatment bath) Alkaline hydroxide salt: about 50 to 1200 g/12, preferably about 50 to 1100 g/Q Organic acid salt: about 5 to 500 g/Q, preferably about 25 to 500 g/Q As the above alkali hydroxide salt can use one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and magnesium hydroxide. As the organic acid salt, one or more selected from the group consisting of sodium salts, potassium salts, and ammonium salts of organic acids can be used. Examples of organic acids include dicarboxylic acids such as adipic acid, itaconic acid, iminodiacetic acid, succinic acid, oxalic acid, fumaric acid, maleic acid, and malonic acid; tricarboxylic acids such as citric acid and nitrilotriacetic acid; ethylenediaminetetraacetic acid; and glycols. Tetracarboxylic acids such as etherdiaminetetraacetic acid and cyclohexanediaminetetraacetic acid, pentacarboxylic acids such as diethylenetriaminepentaacetic acid, hexacarboxylic acids such as triethylenetetraminehexaacetic acid, hydroxyl acids such as ascorbic acid, gluconic acid, tartaric acid, hydroxylethylethylenediamine Examples include hydroxycarboxylic acids such as triacetic acid and malic acid, and aminocarboxylic acids such as aspartic acid and glutamic acid.

(2) Next, it is treated (pickled) by immersing it in a bath containing about 3 to 500 g/Q of inorganic acid, and then washed with water. As the inorganic acid, one or more selected from the group consisting of hydrochloric acid, perchloric acid, hydrofluoric acid, nitric acid, birophosphoric acid, hydrofluoric acid, borofluoric acid, polyphosphoric acid, sulfuric acid, and phosphoric acid can be used. The treatment is completed in about 5 seconds to 10 minutes at a temperature of about 5 to 50°C.

■) Treated by immersing in a sensitizer bath with the following composition,
Wash with water. The treatment is completed in about 5 seconds to 1 hour, preferably about 10 seconds to 10 minutes, at a temperature of about 5 to 95°C, preferably about 5 to 50°C.

(Sensitizer bath) Tin salt about 1 to 100 g/Q, preferably 5 to 5
Inorganic acid about 0g/Q 1 to 500g/12, preferably 5 to
About 50 g/Q As the tin salt, tin chloride and/or tin fluoride can be used. As the inorganic acid, hydrochloric acid and/or hydrofluoric acid can be used.

■) Treat by immersing in an activator bath with the following composition,
Wash with water. The treatment is completed at a temperature of about 5 to 95°C, preferably about 5 to 50°C, for about 5 seconds to 1 hour, preferably about 10 seconds to 10 minutes.

(Activator bath) Palladium salt 0.05 to 10 g/(2 degrees, preferably 0.05 to 1.0 g/Q) Inorganic acid 0.05 to 500 g/Q, preferably 0.
The palladium salt is selected from the group consisting of palladium chloride, ammonium palladium chloride, sodium palladium chloride, potassium palladium chloride, palladium acetate, palladium cyanide, palladium bromide, palladium nitrate, and tetraammine palladium chloride. One type or two or more types can be used.

As the inorganic acid, hydrochloric acid and/or hydrofluoric acid can be used.

Mo/W-Co/Ni was prepared according to the conventional method without performing the pretreatment steps I) to V) above on the ceramic substrate.
When plating a ceramic base alloy, the adhesion between the surface of the ceramic substrate and the alloy plating film is very weak, and it cannot be used as a ceramic wiring board. The reasons for this are: a) The ceramic surface is a very dense and smooth aggregate of oxide and glass, so it does not form a compound with the metal, and it is also an anchor that hooks and joins the metal and ceramic. o) The plating film of the Mo/W-Co/Ni alloy has a large internal stress, and therefore there is a large force that tends to peel it off from the ceramic surface. c) Mo/W -When plating a Co/Ni alloy, a particularly large amount of hydrogen gas is generated compared to when plating other metals, and this hydrogen gas is occluded in the alloy plating film and at the interface between the metal and ceramics. Generating gas pressure and damaging the adhesion between the alloy film and the ceramic surface;
2) Mo/W-Co/Ni alloy plating has poor reduction efficiency and requires long periods of plating, which may result in the effects of (i) and (c) remaining for a long time.

The ceramic substrate subjected to the above pretreatment is subjected to the following plating process and circuit forming process.

(2) Plating process Examples of plating methods include the following methods (1) to (2).

■) The pretreated ceramic substrate is coated with Mo/W-Co
/Immerse in an electroless plating bath of Ni-based alloy and perform electroless plating. Electroless plating is completed in about 5 minutes to 5 hours at a temperature of about 50 to 110°C. With this electroless plating,
A plating film containing at least one of Mo and W, at least one of Co and Ni, and P is formed. Mo/W
Specific examples of electroless plating baths for -Co/Ni alloys are listed below.

Electroless Co-Mo alloy plating bath Cobalt salt 2-200g/Q Molybdate 2-200g/12 Complexing agent 2-1
50g/(2 reducing agent 1-100g/(2
pH adjuster 0-50g0-5O7-12 Temperature 50-100℃ Electroless Co-W alloy plating bath Cobalt salt 2-200g/Q Tungstate 2-200g/9 Complexing agent 2-20
0g/12 reducing agent 1-100 g/Qp
H regulator 0-50g/Q pH7-12 Temperature 50-100°C Electroless Co-Mo-W alloy plating bath Cobalt salt 2-200g/9 Molybdate 2-200g/9 Tungstate 2-20
0g/9 complexing agent 2-200g/9 reducing agent 1-100g/Q pH adjuster
0-50g/Q pH7-12 Temperature 50-100°C Electroless Ni-Mo alloy plating bath Nickel salt 2-200g/9 Molybdate 2-200g/Q Complexing agent 2-20
0g/Q reducing agent 1-100g/9 pH adjuster 0-50g/G! pH 3-12 Temperature 50-100°C Electroless Ni-W alloy plating bath Nickel salt 2-200g/Q Tungstate 2-200g/9 Complexing agent 2-20
0g/9 Reducing agent 1-100g/Q pH adjuster 0-50g/12pH3-12 Temperature 50-100°C Electroless Ni-Mo-W alloy plating bath Nickel salt 2-200g/Q Molybdate 2-200 g/Q Tungstate 2
-200g/Q complexing agent 2-200g
/ Q reducing agent 1-100g/12 pH adjuster 0-! 50g/QH3-12 Temperature 50-100℃ Electroless Co-Ni-Mo alloy bath Cobalt salt 2-200g/Q Nickel salt
2-200g/9 molybdate 2-20
0g/Q complexing agent 2-200g/9 reducing agent 1-100g/9pH adjustment agent
0-50g/Q pH3-12 Temperature 50-100℃ Electroless Co-N1-W alloy plating bath Cobalt salt 2-200g/Q Nickel salt
2-200g/9 tungstate 2-20
0g/Q complexing agent 2-200g/9 reducing agent 1-100g/99H regulator
0-50g/Q pH3-12 Temperature 50-100℃ Electroless Co-Ni-Mo-W alloy plating bath Cobalt salt
2-200g/9 nickel salt 2-20
0g/12 molybdate 2-200g/12 tungstate 2-200g/Q complexing agent
2-200g/Q reducing agent 1-100
g/Q pH adjuster 0-50g/9 pH3-12 Temperature 50-100°C In the above bath, as the cobalt salt, one or more selected from cobalt sulfate, cobalt chloride, and cobalt ammonium sulfate can be used. . As the nickel salt, one or more selected from nickel sulfate, nickel chloride, nickel ammonium sulfate, and nickel potassium sulfate can be used. As the molybdate, one or more selected from sodium molybdate, potassium molybdate, and ammonium molybdate can be used. As the tungstate salt, one or more selected from sodium tungstate, potassium tungstate, and ammonium tungstate can be used. As the complexing agent, one or more selected from sodium salts, potassium salts, ammonium salts of organic acids or inorganic acids, and amines can be used. Examples of the organic acids include adipic acid, ascorbic acid, aspartic acid, alanine, itaconic acid, aminodiacetic acid,
Examples include formic acid, citric acid, glycolic acid, glycine, gluconic acid, glutamic acid, succinic acid, acetic acid, tartaric acid, lactic acid, pyrophosphoric acid, fumaric acid, propionic acid, maleic acid, malonic acid, malic acid, and the like. Examples of amines include ethylenediamine, jetanolamine, diethylenetriamine, triethanolamine, and monoethanolamine. Examples of the inorganic acid salt include pyrophosphoric acid. Examples of the reducing agent include sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, ammonium hypophosphite, cobalt hypophosphite, nickel hypophosphite, dimethylamine borane, etc. Can be done. Examples of pH adjusters include sodium hydroxide,
Examples include potassium hydroxide and aqueous ammonia.

Additionally, additives such as boric acid, ammonium chloride, ammonium sulfate, etc. are added to the bath, usually at a concentration of 500 gIQ.
It may be added to a certain extent, preferably up to about 400 g/Q.

(2) In the present invention, B, P%Fe, Co, Ni, Cu, and Mo are added to the pretreated ceramic substrate.

A metal or an alloy of two or more selected from the group consisting of Pd, Ag, Sn, W, Re, and Pt (M.

/W-Co/Ni-based alloy) may be electrolessly plated, and then a Mo/W-Co/Ni-based alloy may be further electroplated. Electroless plating has a pH of about 3 to 12 and a temperature of 30
This is carried out at about 110° C. for about 10 seconds to about 5 hours. As an electroless plating bath, Mo/W-Co/N
For the i-based alloy, those exemplified above can be used, and for other metals or alloys, known ones can be used. Electroplating of Mo/W-Co/Ni-based alloys is performed at a temperature of about 40 to 110°C and a current density of 0.5 to 2O.
It is carried out for about 10 minutes to 10 hours at A/D Go level. By electroplating, an alloy film containing at least one of Mo and W and at least one of Co and Ni is formed.

Specific examples of electroplating baths for Mo/W-Co/Ni alloys are listed below.

Electric Co-Mo alloy plating bath Cobalt salt 5-350g/Q Molybdate 5-350g/9 Complexing agent 0-40
0g/QpHn adjuster 0-100g/Qp)1
2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electric Co-W
Alloy plating bath Cobalt salt 5-350g/(2 Tungstate 5-350g/9 Complexing agent 0-4
00g/QpHFi conditioner 0-100g#19
H2-11 Temperature 40-100°C Current density 0.5-20A/dm2 Electric Co-M
o-W alloy plating bath Cobalt salt 5-350g/Q Molybdate 5-350g/(2 Tungstate 5-3
50g/9 Complexing agent 0-400g/QpH
Adjustment agent 0-100g/9pH2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electrical Ni-M
o Alloy plating bath Nickel salt 5-350g/Q Molybdate 5-350g/Q Complexing agent 0-40
0g/QpH adjuster 0-100g/9H2-
11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electric Ni
-W alloy plating bath Nickel salt 5-350g/Q Tungstate 5-350g/Q Complexing agent 0-40
0g/QpH adjuster 0-100g/(2pH
2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electric Ni-M
o-W alloy plating bath Nickel salt 5-350g/Q Molybdate 5-350g/9 Tungstate 5-35
0g/Q complexing agent 0-400g/QpHF
J preparation 0-100g/9pH2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electrical Ni-C
o-Mo alloy plating bath nickel salt 5-350g/Q cobalt salt
5-350g/9 Molybdate 5-35
0g/Q complexing agent 0-400g/Q pH adjuster 0-100g/12pH2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electrical N1-C
o-W alloy plating bath nickel salt 5-350g/Q cobalt salt
5-350g/12 tungstate 5-3
50g/Q complexing agent 0-400g/QpH
Adjustment agent 0-100g/12pH2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 Electrical Ni-C
o-Mo-W alloy plating bath nickel salt 5-350g/Q cobalt salt
5-350g/(2 molybdate 5-3
50g/Q tungstate 5-350g/Q complexing agent 0-400g/(2pH adjuster
0-100g/12pH2-11 Temperature 40-100℃ Current density 0.5-20A/dm2 In the above electroplating bath, cobalt salt, nickel salt, molybdate, tungstate, complexing agent, pH adjuster, and addition. As the agent, any of those exemplified for electroless plating baths can be used.

(2) In the present invention, after the ceramic substrate has been treated up to step (2) of the above pretreatment, washed with water and dried, A(7% 5t1Tis Vs Cr5Fe%Co,
Ni, CuSZr, Nb, Mo, PdSAg, 5nST
A metal or an alloy of two or more selected from a, W, Pt, and Au is formed on the surface of the substrate, and Mo/W-Co/Ni
Electroless plating or electroplating of the alloy may be performed.

By the above methods ① to ②, Mo is applied to the surface of the ceramic substrate.
/W-Co/Ni-based alloy plating film can be firmly adhered. The heat of the plating film is not particularly limited and can be selected as appropriate, but it is usually about 5 to 100 μm.

In addition, after forming an electroless plating film on the surface of the ceramic substrate or forming a metal film by vapor deposition, sputtering, or ion plating, M
When forming an o/W-Co/Ni alloy plating film, the Mo/W-Co/Ni alloy plating film is preferably thicker than the electroless plating film or metal film.

The reason why the Mo/W-Co/Ni-based alloy was firmly ruptured on the surface of the ceramic substrate by the methods ① to ① above is that ① the organic acid salt contained in the roughening treatment bath (2) Insoluble particles react with the glassy St and form a soluble complex salt, and also chelate the glassy modified cations of ceramics, resulting in extremely roughened glassy surfaces; and (3) insoluble particles. It is conceivable that the glassy grain boundaries of alumina and magnesia are hollowed out, forming concave portions and forming a good plating base.

(3) Circuit formation process Circuit formation can be carried out, for example, by an etching method.

That is, on the Mo/W-Co/Ni alloy plating film, a positive image resist is formed using a photosensitive resin according to a conventional method,
Then, etching and film removal may be performed. Etching is
Using an etching bath having the following composition, the etching process is completed at a temperature of about 5 to 120 DEG C., preferably about 20 to 100 DEG C., for about 5 seconds to 10 minutes, preferably about 5 seconds to 5 minutes. Membrane removal can be done by a conventional method.

(Etching bath) Fluoric acid about 5 to 500 g/Q, preferably 10 to
About 500 g/Q Inorganic acid About 50 to 1000 g/Q, preferably 5
About 0 to 500 g/Q The fluoric acid is one or two selected from the group consisting of hydrofluoric acid, hydrofluoroboric acid, and hydrofluorosilicic acid.
More than one species can be used. As the inorganic acid, one or more selected from the group consisting of hydrochloric acid, perchloric acid, nitric acid, sulfuric acid, and phosphoric acid can be used. The above etching bath contains 60
0g/(Upper limit is about 2, preferably 10 to 500g
An organic acid of about /Q may be added. As an organic acid,
From adipic acid, ascorbic acid, aspartic acid, itaconic acid, iminodiacetic acid, citric acid, gluconic acid, glutamic acid, chloroacetic acid, succinic acid, acetic acid, tartaric acid, nitrilotriaacetic acid, fumaric acid, maleic acid, malonic acid and malic acid. One or more selected from the group consisting of:

In the present invention, a Mo/W-Co/Ni-based alloy circuit can also be formed on a ceramic substrate by a method other than the etching method described above, such as an additive method or a semi-additive method.

According to the additive method, the above (1) is added to the ceramic substrate.
) After performing the pretreatment, washing with water and drying, a negative image resist is formed on the substrate using a photosensitive resin according to a conventional method, and then plated according to the method (2) or (2), and then a conventional method. Just remove the membrane according to the law. Known baths can be used for membrane removal, such as baths containing sodium hydroxide.

Further, according to the semi-additive method, a circuit is formed in the following manner. That is, the above (2) is applied to the ceramic substrate.
) Mo according to the method of ■ or ■.

/W-Co/Ni alloy film or other metal or alloy film is formed, a negative image resist is formed using a photosensitive resin according to a conventional method, and M o /W-Co/Ni is formed.
The system alloy may be electroplated, etched if necessary, then film removed, and finally unnecessary metal portions may be dissolved and removed and washed with water. Known metal removal baths can be used; for example, an alkaline hydroxide solution is used for AQ and SL, and a mixed acid solution of hydrofluoric acid and nitric acid is used for Ti1V, ZrSNbSMo, Ta, W, and Re. , hydrochloric acid solution etc. for Cr, Fe, Co, Ni%CuSPd.

For Ag and Sn, use nitric acid solution etc. For Pt, use aqua regia etc.
An alkaline cyanide solution or the like can be used for u.

In this way, the ceramic wiring board of the present invention can be obtained. In the wiring board of the present invention, the wiring may be provided on the entire surface of the ceramic substrate (or the wiring may be provided on the negative part).

Effects of the Invention According to the present invention, it has excellent properties such as heat resistance, heat cycle resistance, corrosion resistance, and electrical properties, and the conductor width and conductor spacing are 100%.
A ceramic wiring board with fine wiring of micrometers or less can be manufactured extremely easily and at low cost.

EXAMPLES Below, reference examples, working examples, and comparative examples are given to make the present invention even clearer.

Reference example 1 The above various Mo/W-C (.

8 using a Ni-based alloy electroplating bath (pH approximately 9.0)
Electroplating is performed at a current density of 5 A/dm2 at a temperature of 0°C to deposit an alloy film containing at least one of Mo and W and at least one of Co and NL with a thickness of about 100 μm, and then the copper plate is melted. did.

A polyimide film on which Pd was sputtered and deposited was immersed in an electroless plating bath (pH 9,0) of the various Mo/W-Co/Ni alloys mentioned above at 90°C for 60 minutes, and a thickness of An alloy film of about 100 μm containing at least one of Mo and W, at least one of Co and Ni, and P was deposited, and the film was then peeled off.

The thermal expansion coefficient and volume resistance of the obtained Mo/W-Co/Ni alloy film were measured. Thermal expansion coefficient is 0 to 6
The coefficient of linear expansion of the alloy film in the direction of the plated surface at 00°C was precisely measured and calculated using a working transformer. The volume resistance is
Precise measurements were made using a Whetstone bridge. The results are shown in Table 1.

Table 1 From Table 1, the coefficient of thermal expansion of the Mo/W-Co/Ni alloy is that of the ceramic substrate (85-99.95% alumina: 6.6-8.0XIO-8, ordinary porcelain: 9, 0X
IO-8, Magnesia: 10-13X10-6, Forsterite = 10-12X10-'', Steatite: 6
．． 9 to 7.8 x 1O-8).

It is also found that the volume resistivity of the above alloy is sufficiently low to be used as a conductor for ceramic wiring boards.

Example 1 90% alumina was immersed in monochloroethane for 10 minutes at room temperature for solvent degreasing, and then dried. This was immersed in a bath containing 50 g/Q of sodium hydroxide, 30 g/Q of sodium silicate, 7 g/Q of sodium phosphate, and 10 g/Q of sodium oleate at 50°C for alkaline degreasing, and then washed with water. , immersed in a sulfuric acid aqueous solution (100 g/Q), pickled at room temperature for 2 minutes, and washed with water. Next, sodium hydroxide 200g/Q, sodium citrate 200g
IQ and ethylenediaminetetraacetic acid disodium 20
It was immersed in a roughening treatment bath containing 0 g/Q at 100° C. for 72 hours for roughening treatment, washed with water, pickled with the above sulfuric acid aqueous solution (for 2 minutes at room temperature), and washed with water. This ceramic substrate was immersed in a sensitizer bath containing 25 g/Q of tin fluoride and 50 g/Q of hydrofluoric acid at room temperature for 2 minutes, washed with water, and then treated with 0.5 g/Q of palladium chloride and 1 g/Q of hydrochloric acid. After being immersed in an activator bath containing 50 g of hydrofluoric acid at room temperature for 2 minutes and washed with water, it was immersed in an electroless plating bath (pH 9) having the following composition for 60 minutes at 90°C for electroless plating (approximately 10 μm). was applied, washed with water and dried.

Cobalt sulfate 35gIQ Sodium molybdate 45g/Q Sodium citrate
85g/Q sodium hypophosphite l O
g/Q ammonium chloride 50g/Q (85.0~99.99% Co-M applied to alumina)
o Form a resist (0MR85, manufactured by Tokyo Ohka Kogyo ■) on the alloy plating film to form the desired circuit pattern,
Dry. Then exposed to ultraviolet light through negative film (
50mJ/co+2) and developed with OMR developer.
Dry with R rinse solution and add 100 g of hydrofluoric acid/9. Etch by immersing in an etching bath containing 400 g of nitric acid and 200 g of citric acid for 2 minutes at room temperature, washing with water,
The film was removed using an OMR stripping solution and dried to obtain a ceramic wiring board of the present invention.

Examples 2 to 18 The ceramic substrate and the electroless plating bath were changed as shown in Table 3 below, and the alkaline degreasing time of Examples 10 to 18 was changed to 2 minutes and the roughening treatment time to 1 hour). 1
A ceramic wiring board of the present invention was obtained in the same manner as described above.

Table 2 Table 2 (continued) Table 2 (continued) Table 2 (continued) Table 2 (continued) Examples 19 to 54 In Example 1, electroless plating (pH 9, 90°C, 10
minutes) and after washing with water, further electroplating 5A/di2
A ceramic wiring board of the present invention was obtained in the same manner as in Example 1, except that the temperature was 80° C., pH 8, 60 minutes, a titanium-platinum electrode was used as an anode, the film thickness was 25 μm), water washing and drying. In Examples 28 to 36 and 46 to 54, the alkaline degreasing time was 2 minutes, and the roughening treatment time was 1 hour. The ceramic substrates, electroless plating baths, and electroplating baths used in each example are shown in Table 3 below.

Examples 55 to 72 The same operations as in Example 1 were performed until treatment with an activator bath, washing with water, and drying (In Examples 64 to 72, the alkaline degreasing time was 2 minutes, and the roughening treatment time was 1 minute. time). Next, a resist [A
LPHO10105O.

[manufactured by Nippon Gosei Kagaku ■] was exposed to ultraviolet rays through a negative film (100 mJ/am2), developed by immersing it in a sodium carbonate aqueous solution (10 g/Q) for 2 minutes at 30°C, and washed with water. Electroless plating was carried out in an electroless plating bath having the composition described above at pH 6, 90°C for 60 minutes (film thickness: 15 μm), and then washed with water. Further, the film was removed by immersing it in an aqueous sodium hydroxide solution at 50° C. for 2 minutes, followed by washing with water and drying to obtain a ceramic wiring board of the present invention.

Table 4 Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Examples 73 to 90 Acid treatment and water washing after roughening treatment were carried out After performing the same operation as in Example 1 (in Examples 64 to 70, the alkaline degreasing time was 2 minutes and the roughening treatment time was 1 hour), and then dried. Next, gold is deposited by vapor deposition, sputtering or ion plating or Example 73.78.79.83
~85 and 89... Vapor deposition, Examples 74.75.77.
80, 82, 87 and 88...sputtering, Examples 76, 81, 86 and 90... ion plating), and then a resist (0MR85, manufactured by Tokyo Ohka Kogyo ■) to form the desired circuit pattern. Form, dry and expose to UV light through a negative film at 50 mJ.
/cm2), developed with OMR developer, dried with OMR rinse solution, and electroplated in an electroplating bath with the composition shown in Table 5 below at 5A/dm2, pH 8, 80'C, 60 minutes, film thickness 15 μm. ), washed with water, removed with OMR stripping solution, washed with water, and soaked in potassium cyanide aqueous solution (100 g/Q) at 50°C.
The substrate was immersed in water for 10 minutes to dissolve the gold in unnecessary parts, and washed with water to obtain a ceramic wiring board of the present invention.

Table 5 Table 5 (Continued) Table 5 (Continued) Table 5 (Continued) Examples 91 to 108 In Example 1, after electroless plating and water washing, further electroless plating was performed at pH 9, 90°C, 60°C. minute, film thickness diameter approx. 20
A ceramic wiring board of the present invention was obtained in the same manner as in Example 1 except for washing with water and drying. Furthermore, Example 100
~108 alkaline degreasing time is 2 minutes, roughening treatment time is 1
It was time. The ceramic substrates, electroless plating baths, and electroplating baths used in each example are shown in Table 6 below.

Examples 109 to 144 In Example 1, electroless plating (pH 9, 90°C, 10
After washing with water and drying, a resist (0MR85, manufactured by Tokyo Ohka Kogyo ■) was formed on it to form the desired circuit pattern, dried, and exposed to ultraviolet light through a positive film (50 mJ/cm2), OMR. Developed with a developer, dried with an OMR rinse solution, and electroplated in an electroplating bath with the composition shown in Table 7 below at 5A/di2, pH 8.80.
°C for 60 minutes (film thickness: 15 μm), washed with water, removed with OMR stripping solution, washed with water, and immersed in the etching bath of Example 1 at room temperature for 10 seconds to dissolve the electroless plating on unnecessary parts. The ceramic wiring board of the present invention was obtained by washing with water. Furthermore, Example 1
The alkaline degreasing time for Nos. 18 to 126 and 136 to 144 was 2 minutes, and the roughening treatment time was 1 hour. The ceramic substrates, electroless plating baths, and electroplating baths used in each example are shown in Table 7 below.

Examples 145 to 162 After performing the same operations as in Example 1 until acid treatment and water washing after roughening treatment (in Examples 154 to 162, alkaline degreasing time was 2 minutes and roughening treatment time was 1 hour). )
, dried. Next, nickel was deposited by vapor deposition, sputtering or ion plating. Example 149.15
2.159 and 162... Vapor deposition, Example 145.14
8.151.153.155.156.158 and 16
1... Sputtering, Example 146.147.15
0.154.157 and 160...ion plating), then electroplating in an electroplating bath with the composition shown in Table 8 below at 5 A/da2, pH 8, 80°C, 60 minutes, film thickness 15 μm), and washing with water. A resist (0MR85, manufactured by Tokyo Ohka Kogyo ■) was formed on it to form the desired circuit pattern, dried, exposed to ultraviolet light through a negative film at 50 mJ/cm2), and developed with an OMR developer. , dried with an OMR rinse solution, etched by immersing it in the etching bath of Example 1 at room temperature for 2 minutes, removing the film with an OMR stripping solution, and washing with water to obtain a ceramic wiring board of the present invention.

Table 8 Table 8 (Continued) Table 8 (Continued) Table 8 (Continued) Continuous use temperature (℃), heat cycle resistance, corrosion resistance, and conductor width ( The conductor spacing (μm) was investigated.

[Continuous use temperature (℃)]

It was conducted in accordance with the firing furnace continuity test. That is, the applied voltage was 100 V, and the maximum temperature ('C'') that could withstand continuous use for 100 hours in an air atmosphere was determined.

[Heat cycle resistance]

According to JIS C5030, one cycle was held at -40603 minutes, held at room temperature for 3 minutes, and held at 200°C for 3 minutes, and the test was repeated 5 times.

O: No change ×: Poor conductivity and poor insulation occur [Corrosion Resistance] According to JIS C5028, a test was conducted by spraying a 5% aqueous solution of sodium chloride at 35° C. for 100 hours.

○...No change ×...Conductor failure and insulation failure occur [Conductor width (μ
m) and conductor spacing (μm)) were measured using an electron microscope.

The results are shown in Table 9.

Table 9 Table 9 (continued) Table 9 (continued) Table 9 (continued) Table 9 (continued) Comparative Example 1 (Metal powder simultaneous sintering method) W paste with the following composition was printed on an alumina green sheet. This was simultaneously sintered at 1350° C. in an inert atmosphere to obtain a wiring board.

・W paste tungsten fine powder (particle size 1 μm) 92.0% by weight Ethyl cellulose 1.0% by weight Polyvinyl butyral 1.0% by weight Diethylene glycol
3.0% by weight Mono-n-butylethyl acetate 3.0% by weight Comparative Example 2 (Ag-based alloy paste method) Ag-Pd paste (20P d-Ag) having the following composition was printed on 96% alumina ceramics, and this in the air 9
A wiring board was obtained by firing at 00°C.

Ag-Pd paste (20Pd-Ag) Ag-Pd
Fine powder (particle size 2μm) 79.0% by weight Bismuth oxide 9.0% by weight Silicon oxide
4.0% ethyl cellulose
3.0% by weight Butyl carpitol acetate 6.0% by weight Comparative example 3 (Cu plating method) Electroless copper plating was applied to 96% alumina ceramics, and after further electrolytic copper plating was applied, wiring was formed by a photographic method,
A wiring board was obtained.

Comparative Example 4 (Chromium sputtering method) Chromium was sputtered onto 99.5% alumina ceramics, and wiring was further formed by a photographic method to obtain a wiring board.

The wiring board of the present invention obtained in Example 1 and the conventional wiring board obtained in Comparative Examples 1 to 4 were subjected to various performance tests shown below. The results are shown in Table 7.

- Wiring board dimensional accuracy (%) Calculated by precisely measuring the error between the manufactured wiring board dimensions and the design dimensions using an XY table.

- Conductor thickness distribution (%) Calculated by precisely measuring the thickness distribution of the conductor formed on the ceramic substrate using a cross-sectional observation method.

The smaller the value, the more uniform the thickness.

- Misbond rate (%) Continuous bonding was performed on the manufactured wiring board using an automatic bonding machine, the bonding strength of the conductor was measured, and the misbond rate was calculated.

・Plating property Judgment was made according to the following criteria.

O...Can be plated very well.

Δ: It may be difficult to plate.

×...Only special items can be plated.

・Solderability Judgment was made according to the following criteria.

○... Can be soldered normally using flux.

Δ...Soldering may be difficult.

×・・・Direct soldering is not possible.

In addition, continuous use temperature (℃), corrosion resistance, volume resistance of conductor (μ
Ωcm), the thermal expansion coefficient of the conductor (10-8/°C), and the inside and conductor spacing (μm) were determined in the same manner as above.

Note 1)...Only electroless nickel plating is possible.

2)...Only a special Ag-based alloy paste can be plated.

3)...The plating process becomes complicated.

From Table 7, it can be seen that the wiring board of the present invention is significantly superior in various performances as compared to the conventional wiring board.

(that's all)

Claims (8)

[Claims] (1) A circuit made of an alloy containing at least one of Mo and W and at least one of Co and Ni is added to a wiring board ceramic selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics. Equipped with ceramic wiring board. (2) Claim in which the alloy contains P together with at least one of Mo and W and at least one of Co and Ni.
1) Ceramic wiring board. (3) Ceramics for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are degreased, pickled, and treated with a roughening treatment bath containing an alkali hydroxide salt and an organic acid salt. , pickled, treated with a sensitizer bath containing tin salts and inorganic acids, and treated with an activator bath containing palladium salts and inorganic acids, the ceramic surface was coated with B, P, Co, Fe, Ni, Cu. , Mo, Pd, Ag
, Sn, W, Re, and Pt are electrolessly plated, and then an alloy containing at least one of Mo and W and at least one of Co and Ni is electroplated. Alternatively, an alloy containing at least one of Mo and W, at least one of Co and Ni, and P is electrolessly plated, and a resist is further formed on the plating film, and the film is etched and removed. The method for manufacturing a ceramic substrate according to claim (1) or (2). (4) Ceramics for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are degreased, pickled, and treated with a roughening treatment bath containing an alkali hydroxide salt and an organic acid salt. , After pickling, Al,
Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zr
, Nb, Mo, Pd, Ag, Sn, Ta, W, Pt and Au, a resist is formed on the metal film, and Mo and W The method for producing a ceramic substrate according to claim (1), characterized in that an alloy containing at least one of Co and Ni is electroplated, and the film is removed and unnecessary portions of the metal film are removed. . (5) Ceramics for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are degreased, pickled, and treated with a roughening treatment bath containing an alkali hydroxide salt and an organic acid salt. , After pickling, B, P, F are added to the surface of the ceramic.
e, Co, Ni, Cu, Mo, Pd, Sn, Ag, W,
Electrolessly plating one or more metals selected from the group consisting of Re and Pt, forming a resist on the metal film, and further at least one of Mo and W and at least one of Co and Ni. Claim (1) characterized in that an alloy containing the above metal film is electroplated, and the film is removed and unnecessary portions of the metal film are removed.
A method for manufacturing ceramic substrates. (6) Ceramics for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are degreased, pickled, and treated with a roughening treatment bath containing an alkali hydroxide salt and an organic acid salt. , After pickling, Al,
Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zr
, Nb, Mo, Pd, Ag, Sn, Ta, W, Pt and Au, and then at least one of Mo and W and Co and N.
Claim (1), characterized in that an alloy containing at least one type of i is electroplated, a resist is further formed on the plating film, and an unnecessary portion of the metal film is removed by etching and removing the film. A method for manufacturing ceramic substrates. (7) Ceramics for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are degreased, pickled, and treated with a roughening treatment bath containing an alkali hydroxide salt and an organic acid salt. , pickling, treatment with a sensitizer bath containing a tin salt and an inorganic acid, and treatment with an activator bath containing a palladium salt and an inorganic acid, the ceramic surface is coated with at least one of Mo and W, Co and 3. The method of manufacturing a ceramic substrate according to claim 2, further comprising electrolessly plating an alloy containing at least one type of Ni and P, and further forming a resist on the plating film, and then etching and removing the film. (8) Ceramics for wiring boards selected from alumina ceramics, magnesia ceramics, and alumina-magnesia ceramics are degreased, pickled, and treated with a roughening treatment bath containing an alkali hydroxide salt and an organic acid salt. , pickling, treatment with a sensitizer bath containing a tin salt and an inorganic acid, and treatment with an activator bath containing a palladium salt and an inorganic acid, a resist is formed on the ceramic surface, and at least Mo and W are added to the surface of the ceramic. 1 type,
Claim (2) characterized in that an alloy containing at least one of Co and/or Ni and P is electrolessly plated and then film removed.
) manufacturing method for ceramic substrates.