JPH02101131A - Metallizing composition on the surface of ceramics and metallizing method - Google Patents

Metallizing composition on the surface of ceramics and metallizing method

Info

Publication number
JPH02101131A
JPH02101131A JP63251574A JP25157488A JPH02101131A JP H02101131 A JPH02101131 A JP H02101131A JP 63251574 A JP63251574 A JP 63251574A JP 25157488 A JP25157488 A JP 25157488A JP H02101131 A JPH02101131 A JP H02101131A
Authority
JP
Japan
Prior art keywords
metallizing
ceramics
composition
aluminum nitride
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP63251574A
Other languages
Japanese (ja)
Inventor
Toshiaki Sakaida
敏昭 坂井田
Tadashi Ariga
正 有賀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP63251574A priority Critical patent/JPH02101131A/en
Publication of JPH02101131A publication Critical patent/JPH02101131A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092Dispersed materials, e.g. conductive pastes or inks
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/24Reinforcing the conductive pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal

Abstract

PURPOSE:To metallize the surface of AlN ceramics with a composition having excellent adhesive properties and strength by coating the surface with alloy powder constituted of Ti, Co, Zr, V, Nb, Ta, Mn, Ag, W and Cu and baking it. CONSTITUTION:The surface of AlN ceramics is coated with the alloy powder or mixed powder of a metallizing compsn. contg., by weight, 2 to 40% Ti and 1 to 20% Co, furthermore contg. one or more kinds among 1 to 10% Zr, 1 to 10% V, 1 to 10% Nb, 1 to 10% Ta, 1 to 10% Mn, 1 to 40% Ag and 1 to 10% W and the balance substantial Cu. The above coating is executed by converting the above powder into paste in the use of an organic solvent such as terpineol. The surface to be coated is dried and is thereafter baked at 800 to 1300 deg.C in a nonoxidizing atmosphere such as H2 and Ar. In this way, the metallizing compsn. having excellent adhesive properties with AlN and having sufficient practical strength can be formed on the surface of the ceramics.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は窒化アルミニウム系セラミックスの表面金属化
技術に係り、より詳細には、窒化アルミニウム表面に電
子回路等を形成するための下地層としてのメタライズ層
を形成するのに用いる金属化組成物並びに金属化方法に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to surface metallization technology for aluminum nitride ceramics, and more specifically, the present invention relates to surface metallization technology for aluminum nitride-based ceramics, and more specifically, for use as a base layer for forming electronic circuits, etc. on the surface of aluminum nitride. The present invention relates to metallization compositions and metallization methods used to form metallized layers.

(従来の技術及び解決しようとする課題)電子部品用の
セラミックス基板は、表面に下地層としてメタライズ層
を形成し、その上にニッケルメッキをし、銅タブで電子
回路を形成して作成される。
(Prior art and problems to be solved) Ceramic substrates for electronic components are created by forming a metallized layer on the surface as a base layer, plating nickel on top of it, and forming an electronic circuit with a copper tab. .

従来、このようなセラミックス基板材料としてはアルミ
ナ等の酸化物が主流であったが、特に電子部品のセラミ
ックス基板材料は、素子の高密度化に伴い発生する熱の
放散が極めて重要になり、高熱伝導性を有する窒化アル
ミニウムが期待されている。
Conventionally, oxides such as alumina have been the mainstream materials for such ceramic substrates, but especially for ceramic substrate materials for electronic components, the dissipation of heat generated as the density of elements increases has become extremely important. Aluminum nitride is expected to have conductivity.

アルミナを基板材料として表面をメタライズ化する方法
としては、例えば、次の■〜■のような方法がある。
Examples of methods for metallizing the surface using alumina as a substrate material include the following methods (1) to (4).

■ モリブデン−マンガンペース1〜をアルミナ基板に
印刷し、湿潤水素中或いは湿潤水素と窒素との混合ガス
中にて1350〜1450℃で焼成する方法。
(2) A method in which molybdenum-manganese pastes 1 to 1 are printed on an alumina substrate and fired at 1350 to 1450°C in wet hydrogen or a mixed gas of wet hydrogen and nitrogen.

■ Ag/Pd、Au及びCuの金属微粉末をガラス・
フリットや有機バインダー等と混合し、ペースト化した
ものをアルミナ基板に印刷し、焼成する方法。
■ Fine metal powders of Ag/Pd, Au and Cu are mixed into glass and
A method of mixing frit, organic binder, etc., making a paste, printing it on an alumina substrate, and firing it.

■ アルミナ基板に銅板を置き、加圧しながら加熱する
方法。
■ A method of placing a copper plate on an alumina substrate and heating it while applying pressure.

しかし乍ら、これらの方法は、そのまま窒化アルミニウ
ムを基板材料とする場合には適用できない。すなわち、
アルミナ基板は酸化物であるので、これを利用した接着
機構によって十分な密着強度が得られるが、窒化アルミ
ニウムは非酸化物セラミックスであるため、密着強度が
十分発揮される接合層が形成されないためである。
However, these methods cannot be applied when aluminum nitride is used as the substrate material. That is,
Since the alumina substrate is an oxide, sufficient adhesion strength can be obtained by an adhesion mechanism using this, but since aluminum nitride is a non-oxide ceramic, a bonding layer that provides sufficient adhesion strength cannot be formed. be.

したがって、窒化アルミニウム基板のメタライズ品で表
面に高信頼度の実用的な高い接合強度を有する金属化面
を備えたものは、未だ実用化されていないのが現状であ
る。
Therefore, at present, a metallized aluminum nitride substrate having a metallized surface with high reliability and high bonding strength for practical use has not yet been put into practical use.

本発明は、か)る状況のもとでなされたものであって、
窒化アルミニウムと密着性に優れ、充分な実用強度を具
備し得る新規なメタライズ技術を提供することを目的と
するものである。
The present invention was made under the above circumstances, and
The purpose of this invention is to provide a new metallization technology that has excellent adhesion to aluminum nitride and has sufficient strength for practical use.

(課題を解決するための手段) 前述の問題点に鑑みて、本発明者らは、’Cu−Ti−
Co系金属組成物がアルミナ基板のメタライズ組成物と
して好ましいことを既に提案した。
(Means for Solving the Problems) In view of the above-mentioned problems, the present inventors have developed 'Cu-Ti-
It has already been suggested that Co-based metal compositions are preferred as metallization compositions for alumina substrates.

しかし、この金属組成物を窒化アルミニウム基板のメタ
ライズ化に適用を試みたところ1通常より密着強度は発
現されるものの、アルミナ基板に対するよりも密着強度
が低い結果が得られた。
However, when this metal composition was applied to metallize an aluminum nitride substrate, it was found that although the adhesion strength was higher than usual, the adhesion strength was lower than that for an alumina substrate.

そこで、本発明者は、このように密着強度がアルミナよ
り低い原因は、上記組成物の窒化アルミニウムに対する
濡れ性が必ずしも十分でないためと推定し、前記Cu−
Ti−Co系に更に各種の金属を添加し、濡れ性の改善
を試みた。
Therefore, the present inventor presumed that the reason for the adhesion strength being lower than that of alumina was that the wettability of the above composition to aluminum nitride was not necessarily sufficient, and the above-mentioned Cu-
Various metals were further added to the Ti-Co system in an attempt to improve wettability.

その結果、添加金属として、ジルコニウム、バナジウム
、ニオビウム、タンタル、マンガン、銀、タングステン
等を存在させるならば、密着強度が改善されることを見
い出し、またか)る金属組成物の金属化方法を見い出し
、ここに本発明をなしたものである。
As a result, they discovered that the adhesion strength was improved if zirconium, vanadium, niobium, tantalum, manganese, silver, tungsten, etc. were present as additive metals, and also discovered a method for metallizing the metal composition. , this is where the present invention is made.

すなわち、本発明は、Tiを2〜40%及びCoを1〜
20%含み、更に、Zr:1〜10%、■=1〜10%
、Nb:1〜10%、Ta: 1〜’1.0%、Mn:
 1〜10%、Ag:1〜40%及びW:1〜10%の
うちの1種又は2種以上を含み、残部が実質的にCuよ
りなることを特徴とするセラミックス表面の金属化組成
物を要旨とするものである。
That is, the present invention contains 2 to 40% of Ti and 1 to 40% of Co.
Contains 20%, further Zr: 1-10%, ■=1-10%
, Nb: 1-10%, Ta: 1-'1.0%, Mn:
1 to 10%, Ag: 1 to 40%, and W: 1 to 10%, and the remainder is substantially Cu. The main points are as follows.

また、本発明方法は、前記金属化組成物の合金粉末或い
は混合粉末を窒化アルミニウム系セラミックスの表面に
塗布した後、非酸化性雰囲気中で焼付けることを特徴と
するセラミックス表面の金属化方法を要旨とするもので
ある。
The method of the present invention also provides a method for metallizing a ceramic surface, which comprises applying an alloy powder or a mixed powder of the metallizing composition to the surface of an aluminum nitride ceramic, and then baking it in a non-oxidizing atmosphere. This is a summary.

以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.

前述の如く、本発明の金属化組成物は、Ti−Go−(
Zr、V、Nb、Ta、Mn、Ag及びWのうちの1種
又は2種以上)−Cu系であるが、これら添加金属であ
るZr、V、Nb、’I’a、Mn、 Ag及びWは少
量でも濡れ性を著しく向、ヒさせるので、溶融初期の段
階で金属化組成物が表面張力によって塗布パターンより
も縮少してしまうのを防げる作用があり、また、溶融時
に窒化アルミニウム系セラミックスの表面層に拡散侵入
して、接合層を作る作用がある。そのためには少なくと
も1%以上の添加が必要である。しかし、過剰な反応が
生じると、接合層をかえって脆化させるので、それぞれ
10%以下(但し、Agは40%以下)が好ましい。
As mentioned above, the metallization composition of the present invention comprises Ti-Go-(
One or more of Zr, V, Nb, Ta, Mn, Ag, and W) -Cu system, but these additive metals Zr, V, Nb, 'I'a, Mn, Ag and Even in a small amount, W significantly improves and reduces wettability, so it has the effect of preventing the metallized composition from shrinking more than the coating pattern due to surface tension in the initial stage of melting. It has the effect of diffusing into the surface layer and creating a bonding layer. For this purpose, it is necessary to add at least 1% or more. However, if an excessive reaction occurs, the bonding layer will become brittle, so it is preferable that each content is 10% or less (however, Ag is 40% or less).

したがって、Zr:1〜10%、V:1〜10%、Nb
:1〜10%、Ta1l−10%、Mn:1〜10%、
Ag:1〜40%及びW:1ん10%のうちの1種又は
2種以上を添加する。これらのうち特にZrが効果的で
ある。
Therefore, Zr: 1-10%, V: 1-10%, Nb
: 1-10%, Ta1l-10%, Mn: 1-10%,
One or more of Ag: 1-40% and W: 1-10% are added. Among these, Zr is particularly effective.

Tiは、2%未満では接合層が不十分で密着強度が得ら
れず、また40%を超えると反応が進みすぎて脆くなる
ので、2〜40%の範囲とする。
If Ti is less than 2%, the bonding layer will be insufficient and adhesion strength will not be obtained, and if it exceeds 40%, the reaction will proceed too much and it will become brittle, so it is set in the range of 2 to 40%.

好ましい範囲は20〜40%である。The preferred range is 20-40%.

CoもTiと同様の理由から、1〜20%の範囲とする
。好ましい範囲は1〜10%である。
For the same reason as Ti, the content of Co is also in the range of 1 to 20%. The preferred range is 1-10%.

主成分のCuは、窒化アルミニウムとの親和力はないが
、導電性を持たせるのに必要である。
Cu, the main component, has no affinity with aluminum nitride, but is necessary to provide conductivity.

次に、上記金属化組成物を使用して窒化アルミニウム表
面をメタライズ化する方法について説明する。
Next, a method of metallizing an aluminum nitride surface using the above metallization composition will be described.

上記金属化組成物は、合金粉末として或いは各成分の混
合粉末として使用することができ、いずれの場合も粉末
をペースト状にして窒化アルミニウム表面にスクリーン
印刷などの方法で塗布し、乾燥する。ペース1〜とする
場合には、前記粉末を有機溶媒中に分散させペースト状
にする。有機溶媒としてはテレピネオール、ブチルカル
ピトール、テキサノール、ブチルカルピトールアセテー
トなどを使用することができ、また粉末の量は60〜9
0%とするのが適当である。なお、有機溶媒の外に界面
活性剤を少量添加してもよい。
The above metallization composition can be used as an alloy powder or as a mixed powder of each component, and in either case, the powder is made into a paste and applied to the surface of aluminum nitride by a method such as screen printing, and then dried. In the case of pastes 1 and above, the powder is dispersed in an organic solvent to form a paste. As the organic solvent, terpineol, butylcarpitol, texanol, butylcarpitol acetate, etc. can be used, and the amount of powder is 60 to 9
It is appropriate to set it to 0%. Note that a small amount of surfactant may be added in addition to the organic solvent.

次いで、乾燥後、非酸化性雰囲気中で焼付ける。Then, after drying, it is baked in a non-oxidizing atmosphere.

水素雰囲気或いはアルゴン等の不活性雰囲気中で約1時
間加熱するのが望ましい。加熱温度は800〜1300
℃の範囲であり、好ましくは900〜1200’Cであ
る。
It is preferable to heat for about 1 hour in a hydrogen atmosphere or an inert atmosphere such as argon. Heating temperature is 800-1300
℃ range, preferably 900-1200'C.

次に本発明の実施例を示す。Next, examples of the present invention will be shown.

(実施例) いずれも360メツシユ(44μl11)以下の粉末で
あるスポンジチタン粉末、コバルト粉末、銅粉末、ジル
コニラ11粉末を第1表に示す割合(tit%)で配合
した。
(Example) Sponge titanium powder, cobalt powder, copper powder, and zirconia 11 powder, all powders of 360 mesh (44 μl 11) or less, were blended in the proportions (tit%) shown in Table 1.

次いで、ペースト状のメタライズ用金属材料にするため
に、次の割合で配合し、3本ロールミルで混練してペー
ストとした。
Next, in order to make a paste-like metal material for metallization, the following proportions were blended and kneaded in a three-roll mill to make a paste.

上記混合微粉末:100g エチルセルロース:18g テキサノール=20g そして、上記ペース1〜を用い、厚さ0.635mmの
窒化アルミニウム基板にスクリーン印刷により2mm口
のパターンを印刷し、1.05℃で30分間乾燥した。
The above mixed fine powder: 100g Ethyl cellulose: 18g Texanol = 20g Then, using the above pastes 1 to 2, a pattern with a 2mm opening was printed by screen printing on an aluminum nitride substrate with a thickness of 0.635mm, and dried at 1.05°C for 30 minutes. did.

乾燥後、厚膜焼成炉を使用し、アルゴン雰囲気中、]、
 OOO″Cで0.6Ks時間焼成し、炉冷した。
After drying, use a thick film firing furnace in an argon atmosphere.
It was fired at OOO''C for 0.6Ks and cooled in the furnace.

なお、比較のため、アルミナ基板についても同様の方法
で評価した。
For comparison, an alumina substrate was also evaluated using the same method.

次に、このメタライズ基板の金属化層部に無電解ニッケ
ルメッキを施し、0.6mmφのスズメツキ銅線を2m
m口メタライズパッドに半田付けした後、第1図に示す
要領にてL型引張りによるピル強度を測定した。測定結
果を第1表に併記する。
Next, electroless nickel plating is applied to the metallized layer of this metallized substrate, and 2 m of tinned copper wire with a diameter of 0.6 mm is applied.
After soldering to the m-hole metallized pad, the pill strength was measured by L-shaped tension as shown in FIG. The measurement results are also listed in Table 1.

第1表より明らかなように、Cu−Ti−Co系金属化
組成物を用いた場合(比較例Nα]4、No ]5)に
は、アルミナ基板に対しては所要の強度が得られるもの
の、窒化アルミニウムに対しては強度が低い。これに対
し、本発明例のように更にZr、■、Nb、Ta、Mn
等を適量添加した場合は、窒化アルミニウム基板に対し
て十分な実用強度が得られることがわかる。
As is clear from Table 1, when using the Cu-Ti-Co metallization composition (Comparative Examples Nα]4, No.]5), the required strength can be obtained for the alumina substrate. , its strength is low compared to aluminum nitride. On the other hand, as in the example of the present invention, Zr, ■, Nb, Ta, Mn
It can be seen that sufficient practical strength can be obtained for aluminum nitride substrates when an appropriate amount of the same is added.

[以下余白] (発明の効果) 以上説明したように、本発明によれば、金属化組成物と
してCu−Ti−Co系に更に適量のZr、V、Nb、
Ta、Mn、Ag及びWのうちの1種又は2種以上を添
加した組成とすることにより、窒化アルミニウム基板へ
の濡れ性を改善したので、アルミナ基板と同等の実用的
な密着強度を有する緻密なメタライズ層を形成させるこ
とができる。したがって、高熱伝導性を有する窒化アル
ミニウム基板の実用化を可能にする効果は大きい。
[Blank below] (Effects of the Invention) As explained above, according to the present invention, appropriate amounts of Zr, V, Nb,
By adding one or more of Ta, Mn, Ag, and W to the composition, the wettability to aluminum nitride substrates has been improved, resulting in a dense film with practical adhesion strength equivalent to that of alumina substrates. A metallized layer can be formed. Therefore, the effect of enabling the practical use of aluminum nitride substrates having high thermal conductivity is significant.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図はL型引張りによりビール強度を測定する要領を
説明する図である。 1 ・セラミックス基板、2・・・メタライズ部、3・
・・ニッケルメッキ、4・・・Cu線、5・・・ハンダ
。 特許出願人  昭和電工株式会社
FIG. 1 is a diagram illustrating the procedure for measuring beer strength by L-shaped tension. 1. Ceramic substrate, 2.. Metallized part, 3.
...Nickel plating, 4...Cu wire, 5...Solder. Patent applicant Showa Denko Co., Ltd.

Claims (2)

【特許請求の範囲】[Claims] (1)重量%で(以下、同じ)、Tiを2〜40%及び
Coを1〜20%含み、更に、Zr:1〜10%、V:
1〜10%、Nb:1〜10%、Ta:1〜10%、M
n:1〜10%、Ag:1〜40%及びW:1〜10%
のうちの1種又は2種以上を含み、残部が実質的にCu
よりなることを特徴とするセラミックス表面の金属化組
成物。
(1) Contains 2 to 40% Ti and 1 to 20% Co by weight% (the same applies hereinafter), furthermore, Zr: 1 to 10%, V:
1-10%, Nb: 1-10%, Ta: 1-10%, M
n: 1-10%, Ag: 1-40% and W: 1-10%
The remainder is substantially Cu.
A metallized composition for a ceramic surface, characterized by comprising:
(2)請求項1に記載の金属化組成物の合金粉末或いは
混合粉末を窒化アルミニウム系セラミックスの表面に塗
布した後、非酸化性雰囲気中で焼付けることを特徴とす
るセラミックス表面の金属化方法。
(2) A method for metallizing a ceramic surface, which comprises applying an alloy powder or a mixed powder of the metallizing composition according to claim 1 to the surface of an aluminum nitride ceramic, and then baking it in a non-oxidizing atmosphere. .
JP63251574A 1988-10-05 1988-10-05 Metallizing composition on the surface of ceramics and metallizing method Pending JPH02101131A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63251574A JPH02101131A (en) 1988-10-05 1988-10-05 Metallizing composition on the surface of ceramics and metallizing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63251574A JPH02101131A (en) 1988-10-05 1988-10-05 Metallizing composition on the surface of ceramics and metallizing method

Publications (1)

Publication Number Publication Date
JPH02101131A true JPH02101131A (en) 1990-04-12

Family

ID=17224841

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH02101131A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0618309A1 (en) * 1992-10-21 1994-10-05 Tokin Corporation Metal powder composition for metallization and metallized substrate
EP0640039A1 (en) * 1992-05-12 1995-03-01 The Carborundum Company Thin film metallization and brazing of aluminum nitride

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0640039A1 (en) * 1992-05-12 1995-03-01 The Carborundum Company Thin film metallization and brazing of aluminum nitride
EP0640039A4 (en) * 1992-05-12 1995-04-19 Carborundum Co Thin film metallization and brazing of aluminum nitride.
EP0618309A1 (en) * 1992-10-21 1994-10-05 Tokin Corporation Metal powder composition for metallization and metallized substrate
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