JPH073377A - Metallizing composition - Google Patents

Abstract

PURPOSE:To produce a metallizing composition capable of joining a metallizing part and a ceramic body with a high strength by mixing 1 kind among W, W boride, W carbide, Mo, Mo boride and Mo carbide and aluminum oxynitride in a specified ratio. CONSTITUTION:A metallizing composition consisting of 50-99.99wt.% of at least one kind among W, W boride, W carbide, Mo, Mo boride and Mo carbide and 0.01-50wt.% of aluminum oxynitride and further contg., as required, 0.001-5wt.% (expressed in terms of carbon) of a carbonaceous material or an org. binder is prepared. The aluminum oxynitride is produced from a composition contg. about 3-90mol% of AlN and about 97-10mol% of Al2O3, and carbon black, etc., is used as the carbonaceous material and a phenolic resin, etc., as the org. binder. Consequently, a metallizing composition capable of forming a ceramic body to which a metallizing part is firmly attached is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel metallized composition suitable for a new ceramic body, especially for an aluminum nitride ceramic body, and more particularly to a metallized composition for providing a ceramic body in which a metallized portion is extremely strongly bonded. It relates to a composition.

[0002]

2. Description of the Related Art In recent years, the power consumption of devices such as microprocessors and ECL gate arrays has increased with the increase in speed and miniaturization of semiconductor devices, and the ceramic body on which these devices are mounted has a conventional alumina (Al ₂ The transition from O ₃ ) ceramic bodies to aluminum nitride (AlN) ceramic bodies has begun.

Metallization is usually applied to the surface of the AlN ceramic body in order to join metal pins and leads used for forming or mounting an electric circuit or to join an element to the ceramic body. To be done.

Conventionally, when applying this metallization,
Metallized compositions containing W, Mo, Ta, Mn, Ti and the like as main components have been developed and used.

For example, Japanese Examined Patent Publication Nos. 3-69873 and 3-69874 respectively disclose Mo, W and Ta.
Sintered by metallization using a metallized composition comprising at least one component selected from the group consisting of B, Al, IVa group elements and rare earth elements The body (substrate) is obtained. In Japanese Patent Publication No. 2836/1990, 100 parts by weight of one or more selected from W, Mo and borides and carbides thereof, and Al.N.
A having a metallized structure on the surface, which comprises a first layer consisting of 1 to 50 parts by weight and a second layer consisting of one or more selected from W, Mo and borides and carbides thereof.
A substrate made of IN is shown.

[0006]

However, when the above-mentioned conventional technique is adopted, the bonding strength between the metallized portion and the AlN ceramic body is 4 to 5 kg / mm ² at most. As mentioned, technically unsatisfactory results are obtained. For example, co-fired multilayer P
In the case of a GA package, a Kovar metal pin having a diameter of 0.45 mm is generally used, and the metallized portion for joining the metal pin is generally in the form of a circular pad having a diameter of 1.6 mm. In order for the mounted package to be used with high reliability, breakage at the joint between the AlN ceramic body and the metallized portion is not preferable in the vertical tensile test of the metal pin, and the metal pin itself breaks ( There is a strong demand for the fracture mode of the metal pin itself. To meet this demand,
It is strongly desired to develop a metallized composition that can realize higher bonding strength between the AlN ceramic body and the metallized portion. Since the tensile strength of Kovar, which is the material of the metal pin, is about 55 to 60 kg / mm ² , a total load of 10 kg or more is applied to the joint between the circular pad metallized portion and the AlN base material. Also, it is desired that peeling of the joint does not occur. To meet this demand, Al
About joining N-made base material and metallized part, 5kg / mm
It is necessary to achieve a bond strength of ² or more. However, it was not possible to obtain a bond between the AlN ceramic body having the above-mentioned bonding strength and the metallized portion by using any of the conventional metallized compositions. This is A
Although the IN ceramic body has high heat dissipation,
This was one of the major factors that prevented the application of the AlN ceramic body as a member for electronic parts.

[0007]

As a result of repeated studies in view of the above-mentioned circumstances, the present inventor has found that W, W boride, W carbide,
When a metallized composition containing at least one component selected from the group consisting of Mo, boride of Mo and carbide of Mo and aluminum oxynitride (Aluminum Oxinitride) in a specific ratio is used, a ceramic body, particularly A
It was found that the 1N ceramic body and the metallized portion can be joined with extremely high joining strength, and the present invention has been completed.

That is, the present invention provides 50 to 99.99% by weight of at least one component selected from the group consisting of W, W boride, W carbide, Mo, Mo boride and Mo carbide. It is a metallized composition comprising 0.01 to 50% by weight of aluminum oxynitride. In addition, another invention is
50 to 99.99% by weight of at least one component selected from the group consisting of W, W boride, W carbide, Mo, Mo boride and Mo carbide, and aluminum oxynitride 0.01 to 50% by weight. % Is a ceramic body in which a metallized portion of 100% is joined. In still another aspect of the present invention, at least one component 50-9 selected from the group consisting of W, W boride, W carbide, Mo, Mo boride and Mo carbide.
9.989% by weight, aluminum oxynitride 0.01 to 50
Weight% and carbonaceous material or organic binder 0.001
It is a metallized composition consisting of ˜5 wt% (converted to carbon amount).

The metallized composition of the present invention is selected from the group consisting of W, W boride, W carbide, Mo, Mo boride and Mo carbide (hereinafter referred to as "W / Mo group"). At least one component and a component containing aluminum oxynitride (hereinafter referred to as "metallized composition I"), and at least one component selected from the W / Mo group, a component containing aluminum oxynitride and carbon (Hereinafter referred to as "metallized composition II").

As the aluminum oxynitride in the present invention, known aluminum oxynitride can be used without limitation. This aluminum oxynitride usually has a crystalline phase. The crystal phase includes a single phase composed of one kind of crystal phase and a mixed phase composed of two or more kinds of crystal phases. As the crystal phase of aluminum oxynitride, δ phase, φ ′ (ξ) pseudo spinel phase, γ spinel phase, 12H phase, 21R phase, 27R
Examples include phases. It is preferable to use, as the aluminum oxynitride, one that does not contain the AlN phase and the Al ₂ O ₃ phase at all, because the bonding strength between the metallized portion and the AlN ceramic body can be dramatically increased. Among the aluminum oxynitrides that do not contain the AlN phase and the Al ₂ O ₃ phase at all, those that consist of only the crystal phase that does not contain the glass phase are preferable because their melting points exceed 2000 ° C. When aluminum oxynitride having a melting point of more than 2000 ° C. is used, when the ceramic material is simultaneously sintered during metallization, that is, when so-called co-sintering is performed, the liquid resulting from the metallized composition is obtained at the temperature of the co-sintering. Preferred because no phase forms.

As the method for producing aluminum oxynitride used in the present invention, known production methods can be adopted without limitation. Illustrating the manufacturing method, AlN and A
A method of heating a composition containing 1 ₂ O ₃ to 1600 ° C. or higher or melting it to 2100 ° C. or higher, a composition containing Al ₂ O ₃ and Al or carbon in an atmosphere containing nitrogen (even in the air). Heated up to 1600 ° C or higher or 210
Examples thereof include a method of melting at 0 ° C or higher.

[0012] To produce the aluminum nitride containing no completely Preferably the AlN phase and Al ₂ O ₃ phase which is using in the present invention, the content of AlN in the raw material composition comprising AlN and Al ₂ O ₃ 3 to 90 mol%,
The content ratio of Al ₂ O ₃ is set to 97 to 10 mol%. The type of crystal phase that constitutes aluminum oxynitride is usually determined by the proportions of AlN and Al ₂ O ₃ in the raw material composition. The relationship between the composition of the raw materials and the crystal phase constituting the obtained aluminum oxynitride is as shown in Table 1 below.

[0013]

[Table 1]

When a composition comprising Al ₂ O ₃ and AlN having a composition not shown in the right column of Table 1 above is used as a raw material, aluminum oxynitride consisting of a mixed phase is obtained. . For example, when a composition composed of 40 to 80 mol% of AlN and 60 to 20 mol% of Al ₂ O ₃ is used as a raw material, aluminum oxynitride composed of a γ spinel phase and a 12H phase is obtained. Also, AlN80-
When a composition consisting of 83 mol% and Al ₂ O _{3 20 to} 17 mol% is used, aluminum oxynitride consisting of 12H phase and 21R phase is obtained.

Then, in order to confirm that the produced aluminum oxynitride does not contain AlN, Al ₂ O ₃ , Al, carbon and the like which are the raw materials, the usual X-ray diffraction is carried out.
By this X-ray contact, it is possible to know whether or not the reaction for producing aluminum oxynitride is completed.

It is preferable that the metallized composition of the present invention contains a carbonaceous substance or an organic binder because the bonding strength between the metallized portion and the ceramic body is further increased.
Examples of carbonaceous substances that can be used in the present invention include carbon black and graphite. Examples of the organic binder that can be used in the present invention include phenol resin, polyacrylonitrile, ethyl cellulose,
Acrylic polymers such as nitrified cotton, cellulose nitrate, polymethylmethacrylate, polybutylmethacrylate, polyethylacrylate, polyvinyl butyral,
Polyvinyl acetate, cellulose acetate, methyl cellulose,
Carboxymethyl cellulose, polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, sodium alginate, polyacrylamide and the like. The organic binder is more preferably used because it also functions as a binder for the metallized composition. This organic binder is preferably dissolved in a solvent such as α-terpineol, butyl carbitol, toluene, butyl acetate, acetone, ethanol, methanol, dibutyl phthalate, dioctyl phthalate, and dinonyl phthalate before use. This solvent is highly volatile and does not contribute to the improvement of the bonding strength between the metallized portion and the ceramic body, unlike the above-mentioned carbonaceous substance or organic binder. The amount of the solvent used is not particularly limited, but is usually 1 to 40 parts by weight per 100 parts by weight of the total amount of the aluminum oxynitride and at least one component selected from the W / Mo group.

The content ratio of each component in the metallized composition of the present invention is as follows. That is, in the metallized composition I, 50 to 99.99% by weight of at least one component selected from the W / Mo group and 0.01 to 50% by weight of aluminum oxynitride. On the other hand, in the metallized composition II, at least one component selected from the W / Mo group is 50 to 99.989% by weight, aluminum oxynitride is 0.01 to 50% by weight, a carbonaceous substance or an organic binder. Is 0.01 to 5% by weight in terms of carbon amount
Is. The conversion of the amount of carbon as used herein means conversion based on the amount of carbon content in the carbonaceous material or the organic binder.

As a method of using the metallized composition of the present invention, a known method of using the metallized composition can be adopted without limitation. For example, a method in which the metallized composition is formed by molding ceramic material powder, a method of fixing the metallized composition on a ceramic body or the like, and sintering the method may be used. Examples of the ceramic material powder include Al ₂ O ₃ powder and AlN powder. Further, examples of the ceramic body include an alumina ceramic body and an aluminum nitride ceramic body.

As described above, when the metallized composition is fixed to a molded ceramic material powder, a ceramic body, or the like, the fixing position is not limited to the outer surface of the molded material, the ceramic body, or the like. It may be inside, and in that case, the metallized portion can be an internal pattern, a through hole, or the like.

In order to mold the ceramic material powder as described above, it is preferable to add a binder component to the powder. As the binder, an organic binder containing carbon is preferable because the bonding strength between the metallized portion and the ceramic body is further improved. As an example of the organic binder preferably used, a phenol resin,
Acrylic polymers such as polyacrylonitrile, ethyl cellulose, nitrified cotton, cellulose nitrate, polymethylmethacrylate, polybutylmethacrylate, polyethylacrylate, polyvinyl butyral, polyvinyl acetate, cellulose acetate, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone , Sodium alginate, polyacrylamide and the like. This organic binder is α-terpineol, butyl carbitol, toluene, butyl acetate,
It is preferably dissolved in a solvent such as acetone, ethanol, methanol, dibutyl phthalate, dioctyl phthalate or dinonyl phthalate before use. Further, the ceramic material powder contains MgO, Ca as a sintering aid.
Group IIa metal compounds such as O and SrO, SiO ₂ , Y ₂ O ₃ ,
_{Er 2 O 3, Yb 2 O} 3, Ho 2 O 3, Dy 2 O 3, Gd rare earth element compound such as _{2 O 3, WO 3, MoO} 3, TiO 2, V 2 O
One or two or more blackening or coloring compounds such as ₅ , Nb ₂ O ₅ , Co ₃ O ₄ , NiO, MnO ₂ and Cr ₂ O ₃ can be used. The amount of the sintering aid used is usually 0.00 with respect to the total amount of the ceramic material powder and the sintering aid.
It is determined within the range of 1 to 25% by weight. Furthermore, a plurality of ceramic material powder compacts or ceramic bodies on which the metallized composition is fixed can be laminated when they are subjected to sintering.

When a binder is mixed with the ceramic material powder, before firing after fixing the metallizing composition,
Debinding is usually performed. Then, the sintering for obtaining the ceramic body to which the metallized portion is bonded is usually performed at 1500 to 2000 ° C. in a non-oxidizing atmosphere containing nitrogen.

When the metallizing composition of the present invention described above is used, it comprises 50 to 99.99% by weight of at least one component selected from the W / Mo group and 0.01 to 50% by weight of aluminum oxynitride. It is possible to obtain a ceramic body in which the metallized portions are joined. Examples of the ceramic body to which the metallized portion is joined include an alumina ceramic body and an aluminum nitride ceramic body. Among these, the one in which the metallized portion is joined to the aluminum nitride ceramic body is preferable because the joining strength is extremely high.

[0023]

When the metallized composition of the present invention is used, the reason why the metallized portion and the ceramic body, especially the AlN ceramic body can be bonded with high strength is not clear. However, the present inventors presume as follows. There is.

(1) The coefficient of thermal expansion of aluminum oxynitride is 5.23 × 10 ^-6 ° C ^-1 (value at room temperature to 200 ° C) (Source: Ceramic Engineering &
Science Proceedings (Ceramic Engineerin
g and Science Proceedings) Volume 3, Nos. 1-2 (Jan.
~ Feb.) 1982 67-76), 5.91 x 10
^-6 and 7.59 × 10 ^-6 ° C ^-1 (Source: Research Report No. 32, Institute for Inorganic Materials, 1982, pp. 12-15), each component of the W / Mo group, namely W, The thermal expansion coefficients of W boride, W carbide, Mo, Mo boride and Mo carbide are approximated, and between the aluminum oxynitride inside the metallized portion and each component of the W / Mo group. The cracks due to the thermal expansion mismatch of are less likely to occur.

(2) As a chemical property of aluminum oxynitride, it has a property of easily reacting with a ceramic body component, particularly AlN to form a wide range of Al—O—N polymorphic compounds. The reaction between the aluminum oxynitride and the ceramic body component such as AlN occurs at the bonding interface between the ceramic body, particularly the AlN ceramic body and the metallized portion, and as a result, the bond strength is improved. This can be indirectly explained by the fact that when the metallized composition of the present invention is used, the insulating component is not significantly observed on the surface of the metallized portion bonded to the ceramic body. On the contrary,
For example, when a metallized composition containing W and AlN as main components is used, a large amount of AlN component swelling is observed by SEM observation and EPMA analysis on the surface of the metallized portion bonded to the ceramic body. This phenomenon is considered to occur because the ceramic body and AlN existing in W do not react well.

[0026]

When the metallized composition of the present invention is used, the metallized portion and the ceramic body can be bonded with high strength. In particular, a ceramic body obtained by using the metallized composition of the present invention and having a metallized portion bonded thereto, particularly an AlN ceramic body, is extremely reliable and useful because the metallized portion and the ceramic body can be bonded with high strength. It is a thing. In addition, when the metallized composition of the present invention is used, the insulating component, for example, the AlN component that emerges when the metallized composition containing W and AlN as the main components is used does not come out. The metallized composition of the present invention can be preferably used for forming a circuit pattern of an electronic component because it has good adhesion and does not easily cause blistering during heat treatment.

[0027]

EXAMPLES Examples will be shown below for specifically explaining the present invention, but the present invention is not limited to the examples.

Example 1 First, four types of aluminum oxynitride were prepared by the following methods (1) to (4).

(Method 1) 39 mol% of AlN powder having an average particle size of 1.2 μm and 61 mol% of α-Al ₂ O ₃ powder having an average particle size of 0.7 μm were thoroughly mixed and heated to 1700 ° C. in an N ₂ atmosphere. After the reaction, the mixture was crushed in a mortar to obtain a fine powder of aluminum oxynitride having an average particle size of 1.8 μm and composed of a γ spinel single phase.

(Method 2) α-Al having an average particle size of 0.5 μm
₂ O ₃ powder 95% by weight, ash content 0.06%, average particle size 0.4
After thoroughly mixing 5% by weight of carbon black powder of μm, N ₂
After heating and reacting at 1750 ° C. in an atmosphere, the mixture was lightly loosened in a mortar to obtain a fine powder of aluminum oxynitride composed of a γ spinel single phase and having an average particle diameter of 1.1 μm. The nitrogen content of this powder was 4.6% by weight, and it is recognized that the composition of the powder subjected to the heating reaction corresponds to the composition of AlN 28 mol% -Al ₂ O ₃ 72 mol%.

(Method 3) α-Al ₂ having an average particle size of 90 μm
95% by weight of O _{3 and} 5% by weight of high-purity Al powder of 200 mesh were mixed, and then 215 in the atmosphere in a carbon electrode arc furnace
This mixture was melted at 0 ° C., slowly cooled, coarsely ground the molten mass, then finely ground with an iron ball mill, and iron removed with HCl to obtain an average particle size of 1.
A single aluminum oxynitride fine powder having a δ phase of 2 μm was obtained.
The nitrogen content of this powder was 0.71% by weight, and the composition of the powder used for melting was AlN 5 mol% -Al ₂ O ₃ 95.
It is recognized that it corresponds to a composition of mol%.

(Method 4) 86 mol% of AlN powder having an average particle size of 1.2 μm and 14 mol% of α-Al ₂ O ₃ powder having an average particle size of 0.7 μm were sufficiently mixed, and the crucible made of W foil was put in an N ₂ atmosphere. The mixture was heated to 2100 ° C. in the flask, and the crucible was dropped on the bottom of the furnace.
A fine powder of aluminum oxynitride consisting of m "21R + 27R" mixed phase was obtained.

Next, the following tests were carried out using the obtained four kinds of aluminum oxynitrides.

An aluminum nitride green sheet was prepared using the AlN powder and inorganic oxide shown in Table 2 as raw materials. Separately from this, at least one component selected from the W / Mo group has the components shown in Table 2 and the aluminum oxynitride has the crystal phase shown in Table 2 and has an average particle size of 0.5.
.About.5 .mu.m, as a solvent, (a) .alpha.-terpineol: dibutylphthalate (weight ratio) = 1: 1 solvent (test Nos. 1 to 11, 11 to 13, 16 to 18, 21, 2
3 to 29), (b) α-terpineol: dioctyl tartrate: butyl carbitol (weight ratio) = 1: 1: 1 solvent (test No. 7 to 10, 15, 20, 22), (c) dibutyl phthalate : Butyl carbitol (weight ratio) =
A 2: 1 solvent (Test Nos. 4 to 6, 14, and 19) was used to prepare pastes for metallization.
Then, the content ratio of aluminum oxynitride in the mixture composed of at least one component selected from the W / Mo group and aluminum oxynitride was as shown in Table 2. Further, the amount of the solvent used is the total amount of the at least one component selected from the W / Mo group and aluminum oxynitride used 10
The amount of (a) solvent was 12 parts by weight, the amount of solvent (b) was 20 parts by weight, and the amount of solvent (c) was 25 parts by weight per 0 parts by weight.

Then, the prepared metallizing paste was applied to the surface of the aluminum nitride green sheet in a circular shape having a diameter of 1.95 mm by a screen printing method. A hole having a diameter of 0.3 mm was made in the aluminum nitride green sheet, and the hole was filled with a metallizing paste.

Next, after laminating the aluminum nitride green sheets coated and filled with the metallizing paste, the binder is removed, and then the aluminum nitride green sheets are fired to obtain an aluminum nitride sintered body having a metallized portion bonded to the surface and inside. Obtained.

The joining strength of the aluminum nitride sintered body joined to the metallized portion was measured. The procedure was as described below.

Ni was formed on the surface of the aluminum nitride sintered body to which the metallized portion (after firing: circular shape having a diameter of 1.6 mm) was joined.
The plating is applied to 3 μm, and the Ni plating has a diameter of 0.7
mm Kovar lines were joined. This joining was performed using a brazing filler metal composed of 72 wt% Ag-28 wt% Cu and 840
It was carried out by heating at ℃ for 5 minutes. Then this Kov
The ar line was pulled perpendicular to the joint surface at a rate of 0.2 mm / sec until the fracture occurred at the joint between the AlN sintered body and the metallized portion, and the joint strength was measured. Further, cross-sectional microscopic observation of the joint interface between the metallized portion inside the sintered body and the AlN sintered body revealed no abnormality. In addition, test Nos. 1, 11, 16, 23, 2 in Table 2
The metallized portion bonded to the aluminum nitride sintered body of No. 5 was analyzed for the phase constitution by X-ray diffraction of minute portions. The metallized portion was composed of only W and γ spinel type aluminum oxynitride, Peak ratio between lines (W: (110), aluminum oxynitride: (31
From 1)), it was found that the composition ratio of the starting composition was almost maintained.

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

Example 2 In Example 1, in preparing the paste for metallization, in addition to at least one component selected from the W / Mo group, aluminum oxynitride and a solvent, an organic binder or carbon black was further added. An aluminum nitride sintered body having a metallized portion bonded to the surface and inside was obtained in the same manner as in Example 1 except that it was used (Test No. 32).
In addition, A was used as the inorganic compound of the green sheet material used.
1N 95% by weight and Y ₂ O ₃ 5% by weight, W /
W as the component selected from the Mo group, 5.0% by weight of the γ-spinel phase produced by the above method 1 as aluminum oxynitride, the solvent of (a) above as a solvent, and (a) ethyl cellulose as an organic binder: Nitrified cotton (weight ratio)
= 1: 1 organic binder, (b) an organic binder consisting only of ethylcellulose or (c) an organic binder consisting only of nitrified cotton, carbon black having an average particle size of 0.4
5 μm fine powder was used respectively. The amount of the organic binder used is 1.6 parts by weight in the case of the organic binder (a) per 100 parts by weight of the total amount of at least one component selected from the W / Mo group and aluminum oxynitride,
In the case of (b) the organic binder, 0.8 parts by weight, and in the case of (c) the organic binder, 2.5 parts by weight. In addition, the modes of use of the organic binder and carbon black, and the amount of carbon resulting from both components are as shown in Table 4.

With respect to the obtained aluminum nitride sintered body having the metallized portion bonded to the surface and inside thereof, the bonding strength between the AlN sintered body and the metallized portion was measured, and the metallization inside the sintered body was carried out in the same manner as in Example 1. Section microscopic observation of the joint interface between the metal part and the AlN sintered body was performed. The measurement results of the bonding strength are shown in Table 3. No abnormalities were observed as a result of cross-sectional microscopic observation.

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

Example 3 In Example 2, Mo was used as a component selected from the W / Mo group, aluminum oxynitride was composed of the δ phase produced by the above method 3, and the solvent (c) was used as the solvent. Except for the above, an aluminum nitride sintered body having a metallized portion bonded to the surface and inside was obtained in the same manner as in Example 2 (Test No. 39). The use modes of the organic binder and carbon black, and the amount of carbon derived from both components are as shown in Table 5.

[0050]

[Table 10]

With respect to the obtained aluminum nitride sintered body having the metallized portion bonded to the surface and inside thereof, the bonding strength between the AlN sintered body and the metallized portion was measured and the metallization inside the sintered body was carried out in the same manner as in Example 1. Section microscopic observation of the joint interface between the metal part and the AlN sintered body was performed. The measurement results of the bonding strength are shown in Table 3. No abnormalities were observed as a result of cross-sectional microscopic observation.

Example 4 In Example 2, 95% by weight of AlN, 4.8% by weight of Y ₂ O ₃ and MoO were used as the inorganic compounds of the green sheet raw material.
₂ An aluminum nitride sintered body having a metallized portion bonded to the surface and the inside was obtained in the same manner as in Example 2 except that 0.2% by weight was used and the solvent (b) was used as the solvent (test No. 48). The use modes of the organic binder and carbon black, and the amount of carbon resulting from both components are as shown in Table 6.

[0053]

[Table 11]

With respect to the obtained aluminum nitride sintered body having the metallized portion bonded to the surface and the inside thereof, the bonding strength between the AlN sintered body and the metallized portion was measured and the metallization inside the sintered body was carried out in the same manner as in Example 1. Section microscopic observation of the joint interface between the metal part and the AlN sintered body was performed. The measurement results of the bonding strength are shown in Table 3. No abnormalities were observed as a result of cross-sectional microscopic observation.

Example 5 In Example 2, an inorganic compound as a green sheet raw material,
Example 2 except that at least one component selected from the W / Mo group, aluminum oxynitride, was replaced as shown in Table 3.
In the same manner as described above, an aluminum nitride sintered body having a metallized portion bonded to the surface and inside thereof was obtained (Test Nos. 30 and 3).
1, 33-38, 40-47, 49 and 50).

With respect to the obtained aluminum nitride sintered body having the metallized portion bonded to the surface and inside thereof, as in Example 1, the measurement of the bonding strength between the AlN sintered body and the metallized portion and the metallization inside the sintered body were carried out. Section microscopic observation of the joint interface between the metal part and the AlN sintered body was performed. The measurement results of the bonding strength are shown in Table 3. No abnormalities were observed as a result of cross-sectional microscopic observation.

Comparative Example 1 In Example 1, instead of aluminum oxynitride which is a constituent of the metallized composition, Al as shown in Table 7 was used.
An aluminum nitride sintered body in which the metallized portions were joined was prepared in the same manner as in Example 1 except that fine powders of N, Al ₂ O ₃ , Y ₂ O ₃ , SiO ₂ or Er ₂ O ₃ were used.
Table 7 shows the green sheet materials used and the components selected from the W / Mo group. With respect to the obtained sintered body to which the metallized portion was joined, the joint strength was measured and the cross section of the joint interface was observed under a microscope in the same manner as in Example 1. The measurement results of the bonding strength are shown in Table 7. In addition, the test No.
In Nos. 51, 53, 56, 57 and 58, blistering occurred on the metallized surface when heated to 450 ° C. after Ni plating.

[0058]

[Table 12]

Claims (3)

[Claims] 1. A boride of W, W, a carbide of W, Mo, M
A metallized composition comprising 50 to 99.99% by weight of at least one component selected from the group consisting of boride of o and carbide of Mo and 0.01 to 50% by weight of aluminum oxynitride. 2. A boride of W, W, a carbide of W, Mo, M
A ceramic body in which a metallized portion composed of 50 to 99.99% by weight of at least one component selected from the group consisting of boride of o and carbide of Mo and 0.01 to 50% by weight of aluminum oxynitride is bonded. 3. A boride of W, W, a carbide of W, Mo, M
50 to 99.989% by weight of at least one component selected from the group consisting of boride of o and carbide of Mo, 0.01 to 50% by weight of aluminum oxynitride, and a carbonaceous substance or organic binder 0.001 to 5 Weight% (converted into carbon amount)
A metallized composition comprising: