JPS5867095A - Method of producing ceramic circuit board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a ceramic wiring board for wiring on the surface of a seven-dimensional substrate.

Conventional techniques for wiring ceramic substrates include thin film methods,
There are thick film method, direct knot method, etc.

In the thin film method, metal is vapor-deposited on a ceramic substrate and then wired by etching. This method had the following drawbacks.

(1) Poor mass production; (1) The bonding strength between the ceramic and the vapor-deposited metal is low.

Therefore, in terms of both cost and performance, the application has been limited to semiconductors with collar-sized substrates, and has not been applied to centimeter-sized ceramic substrates.

The thick film method is a method of wiring a ceramic substrate by printing and firing a paste made of noble metal particles. This method had the following drawbacks.

0 Since wiring is done by printing method, the conductor width is 1507a.
If the conductor is n or more, it cannot be made fine; OV) The conductor is thin, resulting in poor electrical conductivity as a conductor, and high current cannot be applied; M The conductor is made of noble metals such as silver or palladium. Therefore, the cost is high.

The direct bonding method, as shown in the special bulletin No. 1d52-57914, is a method in which metallic steel with an oxidized steel surface is placed on a ceramic substrate, and the surface is inert and contains oxygen. Although this method has the advantage of providing a large bonding strength due to the amount of ceramic, porcelain, and copper, it has the following drawbacks.

(As shown in Figure 1 of VO, in order to use the metal steel of the hatch part 12 as a conductor pattern on the ceramic plate 11, it is necessary to punch out the metal steel in the shape of a conductor pattern and place it on the ceramic plate. , it was not possible to refine the pattern.Furthermore, it was not possible to form an independent pattern surrounded by patterns.

(vl) The entire surface of the metal steel placed on the ceramic plate is not bonded to the ceramic plate, but a non-bonded area is created, resulting in a bulge in the metal steel, so the yield rate is low. Rarely.

A common drawback of the prior art is that it is not possible to equally form three-dimensional wiring on the plane and side surfaces of a static substrate.

The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art.
Manufacture of ceramic wiring boards that can be wired to ceramic substrates with good mass production, high yield, high bonding strength, electrical conductivity, fine turn formation, and simultaneous wiring on the flat and side surfaces of ceramic substrates. We are here to provide you with a method.

The method for manufacturing a ceramic wiring board of the present invention includes a first ceramic wiring board made of a noble metal that forms a solid solution with steel on the surface of a ceramic substrate.
A second layer of chemically oxidized steel plating containing oxidized No. 1 steel and oxidized No. 2 steel as main components is provided on top of the second layer to form a base, and the base is made of an inert material containing oxygen. 50 in gas
Heat the second layer to a temperature of 0 to 1085°C to form a ceramic copper substrate using conductive metal steel; selectively cover unnecessary portions of the ceramic steel substrate with a resist; Selectively plate the required parts of a ceramic or steel substrate covered with a resist; remove the resist, and the parts that were under the resist are removed, but because they are not covered with the resist -) The 9° part must be machined and chipped to the extent that it will not be removed. In the above, it is preferable that the first layer is made of metallic palladium, which is formed by immersing the first layer in a treatment solution consisting of divalent ζ radical, hydrogen, and hydrochloric acid as essential components. The above-mentioned second layer is made of divalent ions,
Tartaric acid as a complexing agent for the 2-terminal ion is tartaric acid'
The two were immersed in a 5# chemical copper oxide solution containing as essential components an alkali metal salt, formaldehyde as a reducing agent for the 2-side end ion, and a complexing agent that forms a regular tetrahedral complex with the 1-gradation ion. It is preferable that chemical oxidation steel plating be formed. According to *Nimei's manufacturing method of ceramic wiring board, mass production is possible,
It has a high yield, high bonding strength, good thermal conductivity, and enables the formation of fine patterns, and enables simultaneous wiring on the plane and sides of the ceramic substrate.

The present invention will be described in more detail with reference to the illustrated vertical cross-sectional views 5 to 5 in FIG. 2.

Ceramic substrate 10 shown in Table 2 WJK: As shown in -, a first layer 2 of noble metal forming a solid solution with copper is provided.

in addition,! As shown in FIG. 1, a second layer 3t of chemical copper oxide plating containing copper oxide 1 steel and cupric oxide as a main component is provided to form a base.

The above-mentioned substrate is heated in an inert gas containing oxygen, and the second layer is reduced by heating to electrically conductive metal steel 51K, and the ceramic and metal steel 31 are firmly bonded to each other, as shown in the figure. Ceramic steel substrate. When this ceramic steel substrate is heated in an inert gas, the first layer of noble metal, which forms a complete solid solution with the steel, diffuses into the steel, and the ceramic and the second layer of oxidized steel are substantially dissolved. I don't want to come into contact with you,
The oxidized steel is heated and reduced to metallic steel, and the ceramic surface and metallic steel are strongly bonded together by oxidation and related ceramics.

Using the thus obtained ceramic and copper substrates (thickness of copper: several PIII) as starting materials, they can be processed into various applications desired by the user, as described below.

First, as shown in Figure 2, use a conductor pattern and a thin resist 4.
As a method for selectively covering the material, for example, a printable paste made by adding a filler and a solvent to a non-conducting resin or a rosin-conducting maleic acid resin is printed in a non-conductive pattern and cured. can be used. Alternatively, a photoresist that is hardened by exposure to light may be used. The method to be used depends on how dense a conductor pattern is required. . The former is inexpensive but can form a conductor pattern of 150 μm or more, while the latter is expensive but can form a conductor pattern of 150 μm or less. In other words, the essential characteristics of the resist material are as long as it can withstand the plating process described below.

Next, as shown in FIG. 5, drowsiness cutting 5 is performed through the conductor pattern K1 which is not covered with the lurgist to thicken only the conductor pattern and make the conductor pattern a good electrical conductor. This plating #5 is generally electrolytic copper plating, but solder, secondary, gel, gold, silver, etc. plating may also be used, if the characteristics desired by the user are satisfied. , it is a cost issue.

The thickness of the electroplating may satisfy the electrical conductivity required for a conductor. Since the thickness of a device mounted with a general semiconductor is several volts, a thickness of 10 volts is sufficient.

If it is equipped with a power element of 10,000'V class, an electric power element of 10 to 500 V can be used.

Next, as shown in 5, the resist 4 described above in 1 is peeled off. In this case, the method may be selected depending on the characteristics of the resist used. For example, a highly alkaline aqueous solution can be used for a printed resist, and an organic solvent such as isopropyl alcohol can be used for a photoresist.

Next, as shown at Vc1, the non-conductor pattern portion is removed.The non-conductor pattern portion 6.59 under the resist 4 is not electrically plated, that is, it is made of metal with a thickness of about 100 ml. However, the anti-μ conductor pattern is electroplated and is thicker than sand. There is no need to explain that if a ceramic steel substrate having such a structure is completely etched and etched, the thin non-conductive pattern portion will be preferentially etched away. The etching solution used is t-
Any conventional etching solution may be used as long as it has the property of dissolving it, such as hydrogen peroxide, ferric chloride, fs2 iron chloride, chlorous acid, permanganic acid, or chromic acid based etching solution.

The present invention will be explained in more detail below with reference to embodiments.

Example 1 In this example, a ceramic substrate having a purity of 96% was used. First, it was subjected to the same alkaline degreasing treatment as described below and a pretreatment of neutralization treatment. ,
The process according to the present invention is applied to the order of (c), 2)-7, ---(ν) below and wired.
Needless to say, if necessary, treatments such as washing and drying are necessary.
.

(B) Alkaline degreasing treatment Alkaline degreasing liquid composition Sodium hydroxide ・-LOO/-・Amount condition: 870°C, 5 minutes cleaning (deposition) Neutralization treatment (pretreatment) Neutralization liquid composition; 12 Normalized hydrochloric acid...150-water
...Amount condition that makes the whole t1j! Incubation, washing for 1 minute G/1 Plating nucleation treatment (first layer formation) Plating nucleation liquid composition = Sisypre Co., Ltd., USA, ChikaraCryst 404 Conditions:! (For warm and S minute immersion) Ihi Gaku plating place! ! (Second layer formation) Chemical plating liquid composition: 0uSOn ・5HtO=501 0 Tsusiel salt ・-1501MaOH・
-1>1! 57% formalin for t-<40
・-10d-5@I-dipyridyl ...100 drops of water
...Quantity conditions where the whole is 11: 40℃, 1.5
h (5 voices) (e) Heat treatment in nitrogen containing 20 ppm oxygen at 800°C, after 30 minutes % 1050", 2CI min (f)
Resist formation process Resist composition: Tokyo Ohkasha 0MR83 Condition 2 After completing the above step (E), the substrate is degreased and pickled, then resist ink is applied (3μ), exposure: 2 minutes ()) 1-step plating Treatment electroplating solution composition: Birophosphate steel -901 Potassium birophosphate ...350/Brightener
・-5wJ Polyrin Shun ・
・・Quantity of water to adjust the pH to a6
...quantity condition that makes the whole 11! 5 AIIp /
si/, 50 minutes ()9) (to) Registration stripping treatment Registration stripping agent composition: Tokyo Ohkasha Susilita A-502 Conditions! 90°C, 2 minutes (!J) Processing and processing Etching treatment solution composition: jJE 112 iron-4ap 12N hydrochloric acid -50d water
-・Quantity condition that makes the whole 11! 50
'', 1 minute By the above process, we were able to form a fine pattern with a conductor pattern width of more than 50 mm.There was no copper bulge in the turn, and sufficient bonding strength < 500 m)
However, we were able to form a fine pattern with extremely high bonding strength that was impossible with conventional technology. In addition, the 9#-nucleation solution in the (c) step is PL-8n-Oj
Metallic palladium is dispersed as a colloid in a l-based aqueous solution9, and when a ceramic substrate is immersed, it becomes a ceramic substrate! The first layer is formed by depositing RWJ#/clk.

In this example, it was confirmed by xlli diffraction that the chemical precipitates in step (i)) were mainly composed of cuprous oxide and secondary oxidized steel.

Example λ Example 1 except that the chemical plating treatment was performed as follows.
．． Make sure that the processing process is exactly the same as in case 0.

ni) Chemical grinding wheel 1! (Second layer formation) Chemical plating solution composition: 0uBOa ・5H! O・"50P mouth, Vel salt...1501Naoa
"・Amount of bait 1'!h, O 37% -HoA'"Ysy
-”1 (JdO-Phenane F Lorin
...30 meters: 40m+, 1.5h (5%
”) Chemical plating according to the process in this example)
Example 1. As in the case of , the plating precipitates are mainly composed of cuprous oxide and cupric oxide according to X-ray diffraction.
It was a black film.

In Example II, as in Example 1.0, the bonding strength was high and a fine pattern was formed.

In addition, as a complexing agent to form a regular tetrahedral complex of Ou+,
Nine nitrogen-containing heterocyclic compounds such as cuproine, neocuproine, and pacproine other than -, -'-dipyridyl, 0-ph, and nandroline described above were used, and the results were exactly the same as those described above. .

A wet ceramic substrate (green sheet) on which tungsten conductors were wired was used as the ceramic substrate for the implementation side.

Example 1. By using the same process as above, it is possible to form a fine conductor pattern of 100 wires, and it is possible to form a fine pattern with high bonding strength for the circuit connected to the tungsten conductor on the ceramic and fitting surface.

Example 4゜Example 1. (c) Nome 5# nucleation process ring engineering at
All of the following except t were set as Example 1°0 and 9.

5# Nucleation liquid composition: Mu sacrificial OAs ・-111P ethanol ・-Total amount to be t-200d Condition 8Wi temperature After soaking for 3 minutes, drying Even if a nucleation liquid with the above composition is used, Example 1. obtained similar results.

Furthermore, as a result of various studies, we found that P, which forms a total solid solution with steel,
(It has been found that L, Au, Pt, etc. are effective for forming plated nuclei in the present invention.

Although the present invention has been described in detail above, the ceramic substrate to which it is applied may be one containing Aj*Oi as a main component.

As described above, according to the present invention, three-dimensional wiring on the plane and side surfaces of a ceramic substrate, which was impossible with the conventional technology, can be easily mass-produced because the conductor does not bulge.
The high yield rate is due to the formation of a fine conductive pattern with drowsy conductivity.

[Brief explanation of drawings]

FIG. 1 shows the conventional technology on the Setumik. To form a conductor, punch the copper foil into the shape of the conductor. FIG. 9 is a plan view showing nine configurations. b M2 figures - to - are of the ceramic substrate of the present invention. Wiring process St-Illustrated vertical cross-sectional views 'C' shown sequentially. 1.-Ceramic substrate; 2.-Precious metal; 3.-Chemical oxidation steel plating: 3'...Metal steel; 4.-Resist;5.
・Electroplating. Daishioiri Benkanshi Susuki 1) Ri Agoo 1 Prisoner 2 Procedural amendment (method) Indication of case 1982 Patent Application No. 165769 Amendment person 2, +(・'5101 Hayashi Shikiikagami Hitachi production Representative Name: 3 1) Masato Katsu Shigeyo

Claims (1)

[Scope of Claims] (1) A first layer consisting of a noble metal forming a solid solution with steel is provided on the surface of a ceramic substrate, and furthermore, oxidized #11 steel and oxidized #2 steel are provided as main components. A second layer of chemically oxidized steel plating containing the metal is applied to the substrate, and the substrate is heated to a temperature of 50 to 1085'' in an inert gas containing oxygen to coat the second layer of conductive metal steel. a first step of forming a ceramic-copper substrate as a ceramic-copper substrate; a second step of selectively covering unnecessary portions of the ceramic-copper substrate with a cyst;
The selection, selection-Cera covered with IC resist 1. A third step of selectively plating only the necessary parts of the Ku steel substrate;
1I4 step of removing the resist; and a 5th step of etching so that the portions under the resist are removed but the portions plated in II3 are not removed. Kura's characteristic feature is the production method for wiring boards. +2) @The first layer made of precious metal is divalent palladium. 2. The method for manufacturing a ceramic wiring board according to claim 1C, wherein the ceramic wiring board is made of metallic palladium which is formed by immersing the ceramic wiring board in a treatment solution containing silica and hydrochloric acid as essential components. (3) The second layer of armpit chemical oxidized steel plating is 2
Tartaric acid or an alkali metal salt of tartaric acid as a complexing agent for the two-tone ion and two-tone ion, formaldehyde as a reducing agent for the two-tone ion, and a complexing agent that forms a regular tetrahedral complex with the one-side end ion are required. A chemical oxidized steel plating is formed by immersing the steel in a chemical oxidized steel plating solution containing the chemical oxidized steel plating as a component.
A method for manufacturing a ceramic wiring board as described in Section 1.