JP3529495B2 - Aluminum nitride ceramic substrate and method of manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a metallized composition and an aluminum nitride ceramic substrate using the same. The ceramic substrate according to the present invention can be suitably used for electronic / semiconductor device parts such as a high density and highly integrated circuit substrate, an IC package and a transistor package.

[0002]

2. Description of the Related Art In recent years, the amount of heat generated from semiconductors has increased with the increase in density and integration of semiconductors. Therefore, attention has been paid to AlN (theoretical thermal conductivity of 320 W / m · K) as a material having a higher thermal conductivity than Al ₂ O ₃ ceramics having a low thermal conductivity of about 20 W / m · K.

However, since Y ₂ O ₃ used as a sintering aid for AlN ceramics does not become a glass forming component, it reacts with the oxide layer on the surface of AlN powder to form alumina Al.
_{Even if a 2} O ₃ -yttria Y ₂ O ₃ based compound is produced, it is difficult to penetrate into the W layer side. Therefore, even if the W metallized layer was formed on the AlN surface, the metallized strength varied and the airtightness was poor.

In order to improve this, various proposals have been made to add the same component as aluminum nitride ceramics to W paste (Japanese Patent Laid-Open No. 61-291480).
JP-A-62-197372, JP-A-2-8326
2, JP-A-4-31367, JP-A-4-83783.
And JP-A-5-191039).

[0005]

However, the proposals disclosed in the '480 and' 372 publications focus only on the metallization strength, and like the electrical characteristics and the bondability with other members, It has not been examined from a comprehensive point of view when it is used in the above fields of use. Therefore, even if the metallization strength is high, the electric resistance of the W layer is too high to be sufficient as a circuit board, or the warpage occurs after sintering so that the IC chip cannot be joined or the airtightness is poor. It had been.

Further, in the '262 publication, although the warp of the substrate after sintering is tentatively measured, the relation between this and the solution means is not clarified. Therefore, it is unclear how to eliminate the warp. The '367 publication only discloses a means for limiting the space occupancy rate and the average particle diameter of the tungsten W particles as a means for preventing the cracks of the conductive vias, and has not been studied from the above comprehensive viewpoint. In the '783 and' 039 publications, the warpage of the substrate after sintering is not examined at all.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems and to firmly adhere a W layer having a low electric resistance to aluminum nitride ceramics without deformation of the ceramics, which is excellent in airtightness, and electronic / semiconductor equipment. An object is to provide an aluminum nitride ceramics substrate that can be expected to be used in the field.

[0008]

The first means for achieving the object is 100 parts by weight of tungsten W having an average particle size of more than 0.6 μm and less than 3.0 μm, and aluminum nitride A
lN powder and alumina _Al 2 _{O 3} - yttria _Y 2 _{O 3}
One or more of the mixtures (hereinafter referred to as "additives") 4
And a metallized composition, characterized in that
To produce a ceramic substrate using
In the filtrate.

Here, the addition form of the inclusions other than W includes AlN alone, Al ₂ O ₃ -Y ₂ O ₃ binary mixture, and Al.
Any _{well-N-Al 2 O 3 -Y 2} O 3 ternary mixtures may be the 4 to 40 parts by weight in total amount. However, Al ₂ O ₃
And Y ₂ O ₃ are mixed, the ratio is 3Y ₂ after firing.
O ₃ · 5Al ₂ O _{3 crystals, Y 2 O 3 · Al 2} O 3 crystals or 2Y ₂
It is preferable to determine it to be an Al ₂ O ₃ —Y ₂ O ₃ compound such as O ₃ · Al ₂ O ₃ crystal.

Similarly, the second means is that in which the conductive via is formed in the aluminum nitride AlN sintered body containing the yttrium Y component, the conductive via has an average grain size of
Tungsten W10 of more than 0.6 μm and less than 3.0 μm
0 parts by weight, aluminum nitride AlN and alumina Al
₂ O ₃ -Yttria Y ₂ O ₃ based compound 1 or more 4
In an aluminum nitride ceramics substrate characterized by comprising at least 40 parts by weight, and a metallized layer further formed on the aluminum nitride AlN sintered body, the metallized layer has an average particle size of 0.
100 parts by weight of tungsten W of more than 6 μm and less than 3.0 μm , aluminum nitride AlN and alumina Al ₂ O
_{A 3} -yttria Y ₂ O ₃ -based compound comprises one or more and 4 parts by weight or more and 20 parts by weight or less of the aluminum nitride ceramics substrate.

A suitable method for producing this ceramic substrate is to fill and print the metallization composition on the through holes and the surface of the sintered precursor of aluminum nitride having the through holes,
In the method of simultaneously sintering a sintering precursor and a metallized composition, the metallized composition has an average particle size of 0.6.
100 parts by weight of tungsten W having a size of more than 3.0 μm and less than 3.0 μm, aluminum nitride AlN powder and alumina Al ₂
O ₃ -, characterized in that it comprises a yttria Y ₂ O ₃ 1 or more 4 or more parts by weight of the mixture.

In this manufacturing method, the metallized composition to be filled in the through holes preferably has an average particle size of tungsten W of 1.0 μm or more and 2.5 μm or less,
Its metallizing composition of aluminum nitride AlN and alumina _Al 2 _{O 3} - content of at least one of yttria _Y 2 _{O 3} based mixture is less than 40 parts by weight.

The metallized composition to be printed on the surface preferably has an average particle size of tungsten W of 1.0 μm or more and 2.0 μm or less. Aluminum nitride AlN and alumina Al ₂ O in the metallized composition are preferable . _Three
- content of at least one of yttria Y ₂ O ₃ based mixture is less than 20 parts by weight.

[0014]

When a metal sheet containing aluminum nitride AlN containing yttria Y ₂ O ₃ as a sintering aid component is filled with and / or printed with the above metallization composition and co-fired,
The liquid phase component generated from the oxide layer of AlN powder in the green sheet and Y ₂ O ₃ easily penetrates into the metallized composition. Therefore, the adhesive strength between the conductive via and the metallized layer and the substrate is increased, and the airtightness of the conductive via and the metallized layer is improved.

However, when the amount of the additive in the metallized composition is less than 4 parts by weight, its action is poor, and on the other hand,
If it is filled in the through-holes by more than 40 parts by weight and if printed on the surface by more than 20 parts by weight, the electric resistance becomes too high and it is not suitable for a circuit. The upper limit of the additive content is higher when it is filled in the through holes than when it is printed on the surface, because the latter has a larger cross-sectional area and a shorter wiring length. This is because the contribution of P to the electric resistance is small.

Incidentally, most of the additives become alumina Al ₂ O ₃ -yttria Y ₂ O ₃ type compounds after sintering, but the above liquid phase components permeate from the green sheet during firing. The content of Al ₂ O ₃ —Y ₂ O ₃ based compound after sintering is
A little higher than the amount of its constituents added.

When the average particle size of the tungsten W powder is 0.6 μm or less, the amount of shrinkage of the metallized composition during firing becomes larger than that of the green sheet. It is recessed more than the surface, and when the metallization composition is applied to the planar wiring, the entire substrate warps toward the metallization layer side. On the other hand, when the average particle size of W powder is 3.0 μm or more, the firing shrinkage amount of both is reversed, the end face of the conductive via protrudes from the substrate surface, the entire substrate warps toward the ceramic side, and the metallization strength and airtightness Since the properties are also deteriorated, the average particle size is limited as described above. The preferable range of the average particle diameter is 1.0 μm to 2.5 μm for filling the through holes and 1.0 μm to 2.0 μm for surface printing. The former has a higher upper limit of the average particle size, which is preferable in the case of a metallized composition filled in through-holes because the shrinkage amount in the thickness direction of the substrate is smaller than that in the planar direction. This is because the influence on the warp of the substrate and the unevenness of the conductive via is less than that of.

[0018]

【Example】

-Example 1-Here, an example is shown in which the metallized composition of the present invention is applied to a conductive via of a substrate, that is, wiring in the thickness direction.

AlN powder (average particle size 1.2 μm) 100
In parts by weight, Y ₂ O ₃ powder (average particle size 1.4
μm), 0.5 parts by weight of TiO ₂ powder (average particle size 0.7 μm) as a colorant, and polyvinyl butyral (PVB) as an organic binder and dibutyl phthalate (as a plasticizer). DBP) was added and mixed with a solvent to form a slurry, which was then tape-formed with a doctor blade device to prepare an AlN green sheet having a thickness of 0.6 mm (hereinafter, simply referred to as “green sheet”). Separately, W powder was mixed with predetermined additives and ethyl cellulose as an organic binder in a solvent to prepare a W paste (metallized composition).

Then, the above green sheet was punched out to form 40 through-holes arranged in 4 rows and 10 columns, each having a diameter of 0.25 mm, and filled with W paste. Two sheets of this green sheet are piled up, cut into a predetermined shape, and moistened with N ₂
/ H ₂ After degreasing at 800 ℃ in N ₂ atmosphere,
An aluminum nitride ceramics substrate was manufactured by firing at 00 ° C.

The obtained substrate had a size of 40 × 20 × 1 ^t mm, and the diameter of the conductive via was 0.20 mm. Table 1 shows the results of measuring the flatness, airtightness and volume resistance of this substrate under the following conditions.

[Evaluation of Flatness] The measuring needle of the surface roughness meter is set to 0.6 mm / sec in the plane direction of the substrate. Run at the speed of
The vertical displacement of the measuring needle when passing through the conductive via is measured, and the average value of n = 5 is 10 to 15 (excluding 10) μm is □, 5 to 10 (excluding 5) μm is ○, −5 ~ 5 (5,-
5 (including 5) is ◎, -10 to -5 (excluding -5) μm
Is indicated by ●, and −15 through −10 (excluding −10) μm is indicated by ■.

[Evaluation of airtightness] W on the surface of the green sheet
Screen-printing with a paste in a cross pattern of a predetermined size, and stacking a green sheet having a hole of 5 mm in diameter at its center so that the pattern intersection is at the center,
It was cut into an 8 mm square. Then, by firing under the above firing conditions, a ceramics laminated substrate was manufactured. The cross pattern has a width of 0.2 mm and a thickness of 20.
It had a size of μm. As shown in FIG. 2, silicon rubber S was applied to the laminated substrate 6 and applied to a helium He leak detector device, and helium gas was blown from the outside while keeping one main surface side of the substrate in vacuum. Helium gas leakage of 10 ^-9 atm · cc / sec or less is ○, 10 ⁻⁷ to 10 ⁻⁸ atm · cc / sec is △, 10 ⁻⁶ atm
・ Table 1 shows x as cc / sec or more.

[Evaluation of Volume Resistance] Ten conductive vias formed by filling the inside of the through hole with the metallized composition were arbitrarily selected, and the electrical resistance between both end faces was measured to determine the diameter and length of the conductive vias. From this, the volume resistance was calculated and the average value was displayed.

[0025]

[Table 1] As can be seen in Table 1, sample N belonging to the scope of the invention
o. 3 to 8, 10, 11, 16 to 21, 23, 24 are
The flatness, airtightness and volume resistance were all excellent. On the other hand, the sample No. Since Nos. 1 and 14 have a fine W average particle size of 0.6 μm, the metallized composition filled in the through holes shrinks more than the green sheet,
As a result, it is considered that the end face of the conductive via is depressed more than the substrate surface. Sample No. Nos. 2 and 15 are considered to be inferior in airtightness because the amount of the inorganic additive other than W contained in the metallized composition was as small as 2 parts by weight, so that the penetration of the liquid phase component from the ceramic side was insufficient. To be Sample No. On the contrary, in Nos. 9 and 22, the volume resistance became too high because the addition amount was excessive. Sample No. 12,
Nos. 13, 25, and 26 are Nos. Contrary to 1, the average W particle size was too large, 3 μm and 4 μm, respectively, so that the metallized composition filled in the through holes did not shrink as much as the green sheet, and the conductive vias relatively protruded from the substrate surface. It is considered to be a thing.

-Comparative Example 1-For comparison, CaO was used in place of Y ₂ O ₃ as a sintering aid contained in the green sheet, and AlN and Al ₂ O ₃ were used as additives in the metallized composition. A ceramics substrate was manufactured under the same conditions as in Example 1 except that 4 parts by weight of CaO was used in place of -Y ₂ O ₃ and W average particle size was 1.0 μm.

When the flatness, airtightness and volume resistance were evaluated in the same manner as in Example 1, the flatness was ◯, the airtightness was x, and the volume resistance was 23 μΩ · cm. It is considered that the airtightness was poor because the liquid phase component did not penetrate into the conductive via side because CaO was volatilized during firing.

Example 2-Here, an example is shown in which the metallized composition of the present invention is applied to a metallized layer of a substrate, that is, wiring in a plane direction. A green sheet and W paste having the same shape and quality as those produced in Example 1 were prepared. Then, the following evaluation was performed using the above green sheet and W paste.

[Evaluation of Metallization Strength] W paste was screen-printed on the surface of the green sheet to form 20 predetermined pads in 4 rows × 5 columns = 800 ° C. in a humidified N ₂ / H ₂ atmosphere. After removing the resin, under a N ₂ atmosphere 17
It was fired at 50 to 1850 ° C., and subsequently electroless Ni plating with a thickness of 1.0 μm was applied on the pad. The pad is
2.5 mm in diameter and 20 μm in thickness, 2.5
They were arranged at a pitch of 4 mm. Next, the shaft diameter is 0.45
mm, head diameter 0.70 mm, nail head pin 7
Bonding was performed with a 2Ag-28Cu eutectic brazing material. The joint structure is shown in FIG. In the figure, a bonded body 1 is a ceramic substrate 2,
The pad 3 includes a metallized layer and a Ni plating layer, a nail head pin 4, and a brazing material 5.

The ceramic substrate 2 of the bonded body 1 is fixed,
The nail head pin 4 was pulled in the direction perpendicular to the ceramic substrate 2 and the metallization strength was measured. Metalization strength is 5kg / mm ^{2 in} 5 samples (100 pads)
The pads below were regarded as defective, and the defective rate was calculated and shown in Table 2. When the metallizing strength is 5 kg / mm ² or more, the nail head pin 4 is cut off, so the metallizing strength is 5 k.
The g / mm ² was used as a criterion for pass / fail.

[Evaluation of Airtightness] Silicone rubber was applied to the substrate and placed on a helium He leak detector as in Example 1, and helium gas was blown from the outside while the hole side of the laminated substrate 6 was kept in vacuum. Evaluation was made in the same manner as in Example 1 and shown in Table 2.

[Evaluation of Volume Resistance] Three strip patterns having a predetermined size were screen-printed in parallel on the surface of the green sheet by using W paste and baked under the above baking conditions. The band pattern has a width of 0.2 mm, a length of 50 mm, and a thickness of 20 μ.
It was the size of m. The electrical resistances at both ends of each strip pattern were measured, the volume resistance was calculated from the dimensions of the strip pattern, and the average value of three strips is shown in Table 2.

[Evaluation of Warp] After the W paste was screen-printed on the entire main surface of the green sheet, it was cut into a disk shape,
Firing was performed under the above firing conditions. The thickness of the W layer after firing is 2
At 0 μm, the disc diameter was 25 mm. And
The amount of warpage of this disk was measured. As shown in FIG. 3, the warp amount d when the disc is warped to the metallization layer 7 side is a positive value,
The amount of warpage d when warping on the side of the ceramics 8 is a negative value, and the one whose absolute value is less than 300 μm is ◯, 300 to
Table 2 shows Δ in the range of 600 μm and x in the range of 600 μm or more.

[0034]

[Table 2] As can be seen in the table, sample N belonging to the scope of the invention
o. 3-6,8,13-16,18 were excellent in all of metallization strength, airtightness, volume resistance, and the amount of curvature. Regarding the volume resistance, the relationship with the added amount of the additive is shown in FIG. It is clear from FIG. 4 that the volume resistance rapidly increases when the added amount exceeds 20 parts by weight. The relationship between the amount of warp and the W average particle diameter is shown in FIG. From Figure 5 W
When the average particle size is in the range of 1.0 to 2.0 μm, the shrinkage amounts of the metallized layer and the ceramic substrate are the same,
It is clear that there is little warpage.

On the other hand, sample No. 1,11 is W
Since the average particle size was small, the amount of warpage was excessive in the positive direction. Sample No. It is considered that Nos. 2 and 12 were inferior in airtightness because the amount of the additive was small and the amount of the liquid phase component permeating from the green sheet was small. Sample No. 7,17
However, the volume resistance was too high because the additive amount was excessive. Sample No. In Nos. 9, 10, 19, and 20, the W average particle size was large, and thus the warpage amount was excessive in the negative direction. Also,
Sample No. No. 21 has no additive added, and sample N
o. No. 22 was inferior in all properties because the additive was TiN that did not form a liquid phase.

Incidentally, when the metallized layer was analyzed by XRD, the sample No. 4 and No. No. 15 had alumina Al in the metallized layer as shown in FIGS. 6 and 7, respectively.
₂ O ₃ -Yttria Y ₂ O ₃ based compounds were confirmed, and it was found that they had permeated, while sample No. 21 and No. 21. In No. 22, no such compound was confirmed as shown in FIGS. 8 and 9. Therefore, it is clear that the difference in the above various properties is due to the presence or absence of penetration of such a compound.

[0037] - For Comparative Example 2 Comparative, as a sintering aid contained in the green sheet, using the CaO in place of the Y ₂ O _3, as additives for metallizing composition, AlN and Al ₂ O ₃ A ceramic substrate was manufactured under the same conditions as in Example 2 except that 4 parts by weight of CaO was used instead of —Y ₂ O ₃ .

When the metallization strength, airtightness, volume resistance and warpage were evaluated in the same manner as in Example 2, the metallization strength had a defective rate of 12%, the airtightness was ×, and the volume resistance was 22 μΩ.
cm, the warp was x.

Example 3 In Example 1, the additive of the W paste is aluminum nitride AlN alone or alumina Al ₂ O ₃ -yttria Y ₂ O ₃ binary mixture, but here, aluminum nitride AlN is used. And alumina Al ₂ O ₃ -Yttria Y ₂ O ₃
Mixing ratio of 1: 1 and was _{AlN-Al 2 O 3 -Y 2} O 3 ternary mixtures, in the same manner as in Example 1, the metallization composition of the present invention to the wiring of the conductive via or thickness direction of the substrate The applied example is shown.

A green sheet and W paste having the same shape and quality as those produced in Example 1 were prepared except that the additives were changed. Then, in the same manner as in Example 1, 40 × 20
It has a size of × 1 ^t mm and the diameter of the conductive via is 0.20 m.
m ceramic substrate was obtained. Table 3 shows the results of measuring the flatness, airtightness and volume resistance of this substrate under the following conditions.

[Evaluation of Flatness] Similar to Example 1, the vertical displacement of the measuring needle when passing through the conductive via was measured and evaluated in the same manner as in Example 1 and shown in Table 3.

[Evaluation of Airtightness] Similar to Example 1, silicon rubber was applied to the substrate, the substrate was placed on a helium He leak detector, and helium gas was blown from the outside while the hole side of the laminated substrate 6 was kept in vacuum. Evaluation was made in the same manner as in Example 1 and shown in Table 3.

[Evaluation of Volume Resistance] The electric resistance between both end faces was measured in the same manner as in Example 1, the volume resistance was calculated from the diameter and length of the conductive via, and the average value is shown in Table 3.

[0044]

[Table 3] As can be seen in Table 3, sample N belonging to the scope of the invention
o. Nos. 30 to 35, 37, and 38 were excellent in flatness, airtightness, and volume resistance. On the other hand, the sample No. In No. 28, the W average particle size is as small as 0.6 μm, so it is considered that the metallized composition filled in the through-holes shrinks more than the green sheet, and as a result, the end face of the conductive via is depressed more than the substrate surface. To be Sample N
o. In No. 29, since the addition amount of the inorganic additive other than W contained in the metallized composition was as small as 2 parts by weight, it is considered that the penetration of the liquid phase component from the ceramic side was insufficient and the airtightness was poor. Sample No. On the contrary, in No. 36, the volume resistance was too high because the added amount was excessive. Sample No. Nos. 39 and 40 are Nos. W contrary to 28
Since the average particle sizes were too large, 3 μm and 4 μm, respectively, it is considered that the metallized composition filled in the through holes did not shrink as much as the green sheet, and the conductive vias relatively protruded from the substrate surface.

Example 4-In Example 2, the additive of the W paste is aluminum nitride AlN alone or alumina Al ₂ O ₃ -yttria Y ₂ O ₃ binary mixture, but here, aluminum nitride AlN is used. And alumina Al ₂ O ₃ -Yttria Y ₂ O ₃
Related 1, and was _{AlN-Al 2 O 3 -Y 2} O 3 ternary mixtures, as in Example 2, the wiring metallization composition metallized layer or planar direction of the substrate of the present invention: the mixing ratio of the 1 Here is an example.

A green sheet and W paste having the same shape and quality as those produced in Example 1 were prepared except that the additives were changed. Then, the following evaluation was performed using the above green sheet and W paste.

[Evaluation of Metallization Strength] As in Example 2, the ceramic substrate 2 of the bonded body 1 was fixed, and the nail head pins 4 were pulled in the direction perpendicular to the ceramic substrate 2 and evaluated in the same manner as in Example 2. The results are shown in Table 4.

[Evaluation of Airtightness] In the same manner as in Example 1, silicon rubber was applied to the substrate, the substrate was placed on a helium He leak detector, and helium gas was blown from the outside while the hole side of the laminated substrate 6 was kept in vacuum. Evaluation was made in the same manner as in Example 1 and shown in Table 4.

[Evaluation of Volume Resistance] The electric resistances at both ends of each strip pattern were measured in the same manner as in Example 2, the volume resistance was calculated from the dimensions of the strip pattern, and the average value of three is shown in Table 4. [Evaluation of Warp] The amount of warp of the disk was measured in the same manner as in Example 2, and evaluated in the same manner as in Example 2 and shown in Table 4.

[0050]

[Table 4] As can be seen in the table, sample N belonging to the scope of the invention
o. Nos. 25 to 28 and 30 were excellent in all of metallization strength, airtightness, volume resistance and warpage.

On the other hand, sample No. In No. 23, since the W average particle size was small, the amount of warpage was excessive in the positive direction. Sample No. It is considered that since No. 24 had a small amount of additive, the amount of liquid phase component permeated from the green sheet was small, resulting in poor airtightness. Sample No. In No. 29, since the amount of the additive was excessive, the volume resistance became too high. Sample No.
In Nos. 31 and 32, the W average particle size was large, and thus the warpage amount was excessive in the negative direction.

[0052]

As described above, when the metallized composition of the present invention is applied as a metallized layer and a conductive via of an aluminum nitride ceramic substrate, it has high adhesive strength with ceramics, excellent airtightness, no firing deformation, and electrical resistance. Electronic / semiconductor components with low resistance can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a method of evaluating metallization strength.

FIG. 2 is a diagram illustrating an airtightness evaluation method.

FIG. 3 is a diagram illustrating a method of evaluating a warp amount.

FIG. 4 is a graph in which the relationship between the volume resistance and the additive amount is plotted.

FIG. 5 is a graph in which the relationship between the amount of warp and the average particle diameter of W is plotted.

6 is a sample No. 2 of Example 2. FIG. 4 is a chart showing the result of XRD of No. 4.

7 is a sample No. 2 of Example 2. FIG. It is a chart figure which shows the result of XRD of 15.

8 is a sample No. 3 of Example 2. FIG. It is a chart figure which shows the result of XRD of 21.

9 is a sample No. 3 of Example 2. FIG. It is a chart figure which shows the result of XRD of 22.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-83782 (JP, A) JP-A-4-83783 (JP, A) JP-A-5-191039 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C04B 41/80-41/91

Claims (3)

(57) [Claims] 1. An aluminum nitride AlN sintered body containing a yttrium Y component, wherein conductive vias are formed, wherein the conductive vias have an average particle size of more than 0.6 μm.
Nitride comprising 100 parts by weight of tungsten W of less than 3.0 μm and one or more of aluminum nitride AlN and alumina Al ₂ O ₃ -yttria Y ₂ O ₃ -based compound in an amount of 4 parts by weight or more and 40 parts by weight or less. Aluminum ceramic substrate. 2. An aluminum nitride AlN sintered body containing a yttrium Y component, wherein conductive vias and a metallized layer are formed, wherein the conductive vias have an average grain size.
Tungsten W10 of more than 0.6 μm and less than 3.0 μm
0 parts by weight, aluminum nitride AlN and alumina Al
₂ O ₃ -Yttria Y ₂ O ₃ based compound 1 or more 4
100 parts by weight of Tungsten W having an average particle size of more than 0.6 μm and less than 3.0 μm and aluminum nitride AlN and alumina Al ₂ O ₃ −. An aluminum nitride ceramic substrate comprising at least one type of yttria Y ₂ O ₃ -based compound and at least 4 parts by weight and at most 20 parts by weight. 3. A method of filling a metallizing composition into a through hole of a sintering precursor of aluminum nitride having a through hole, printing the metallizing composition on the surface, and simultaneously sintering the sintering precursor and the metallizing composition. In the metallized composition of the through hole, the average particle size exceeds 0.6 μm and 3.0 μm.
With less than 100 parts by weight of tungsten W, aluminum nitride AlN powder and alumina Al ₂ O ₃ -yttria Y _2.
Tungsten W10 containing 1 to 4 parts by weight and 40 parts by weight or less of the O ₃ mixture, wherein the metallized composition on the surface has an average particle size of more than 0.6 μm and less than 3.0 μm.
0 parts by weight and one or more of aluminum nitride AlN powder and alumina Al ₂ O ₃ -yttria Y ₂ O ₃ mixture, and 4 parts by weight or more and 20 parts by weight or less are included. .