JP2678512B2 - Metallizing composition - Google Patents
Metallizing compositionInfo
- Publication number
- JP2678512B2 JP2678512B2 JP1339155A JP33915589A JP2678512B2 JP 2678512 B2 JP2678512 B2 JP 2678512B2 JP 1339155 A JP1339155 A JP 1339155A JP 33915589 A JP33915589 A JP 33915589A JP 2678512 B2 JP2678512 B2 JP 2678512B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- metal layer
- sintered body
- metallized metal
- based sintered
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はセラミック体にメタライズ金属層を形成する
ためのメタライズ用組成物に関し、より詳細にはアルミ
ナ（Al2O3）含有量が92.0重量％以上のアルミナ質焼結
体にメタライズ金属層を形成するためのメタライズ用組
成物に関するものである。TECHNICAL FIELD The present invention relates to a metallizing composition for forming a metallized metal layer on a ceramic body, and more specifically, it has an alumina (Al 2 O 3 ) content of 92.0% by weight. % Or more of the alumina-based sintered body, the present invention relates to a metallizing composition for forming a metallized metal layer.
（従来の技術） 従来、アルミナ質焼結体は電気絶縁性、化学的安定性
等の特性に優れていることから半導体素子を収容する半
導体素子収納用パッケージや回路配線を有する回路基板
等の電子部品に多用されており、アルミナ質焼結体の表
面には回路配線導体として使用されるメタライズ金属層
が被着接合されている。(Prior Art) Conventionally, an alumina-based sintered body is excellent in characteristics such as electrical insulation and chemical stability, so that electronic devices such as a semiconductor element housing package for housing a semiconductor element and a circuit board having circuit wiring are provided. A metallized metal layer, which is widely used for parts and is used as a circuit wiring conductor, is adhered to the surface of an alumina-based sintered body.
かかるアルミナ質焼結体表面のメタライズ金属層は通
常、タングステン（Ｗ）、モリブデン（Mo）等の高融点
金属粉末に有機溶剤、溶媒を添加してペースト状と成し
たものを未焼成アルミナ質成形体表面にスクリーン印刷
等により被着させ、しかる後、前記未焼成アルミナ質成
形体を還元雰囲気中、約1500℃の温度で焼成し、アルミ
ナ質焼結体のアルミナ結晶間に介在するガラス成分の一
部を高融点金属の金属粒子間に移行させ、アルミナ結晶
と高融点金属とをガラス成分を介し接合させることによ
ってアルミナ質焼結体の表面に被着接合される。The metallized metal layer on the surface of the alumina-based sintered body is usually a non-fired alumina-based molded product obtained by adding an organic solvent or solvent to a refractory metal powder such as tungsten (W) or molybdenum (Mo) to form a paste. The surface of the body is adhered by screen printing or the like, and thereafter, the unfired alumina-based compact is fired at a temperature of about 1500 ° C. in a reducing atmosphere, and the glass component of the intercalation between the alumina crystals of the alumina-based sintered body is A part of the particles are transferred between metal particles of a refractory metal, and the alumina crystal and the refractory metal are bonded via a glass component to be adhered and bonded to the surface of the alumina-based sintered body.
（発明が解決しようとする課題） しかし乍ら、この従来のタングステン（Ｗ）、モリブ
デン（Mo）等、高融点金属を使用したメタライズ金属層
はアルミナ質焼結体のアルミナ（Al2O3）含有量が90.0
重量％以下であればアルミナ質焼結体のアルミナ結晶間
に介在するガラス成分の量が多く、該ガラス成分の高融
点金属粒子間への移行もスムーズとしてメタライズ金属
層をアルミナ質焼結体に強固に接合させることができる
ものの、アルミナ質焼結体のアルミナ（Al2O3）含有量
が92.0重量％を超えた場合、アルミナ結晶間に介在する
ガラス成分の量が少なくなり、該ガラス成分の高融点金
属粒子間への移行も悪くなってメタライズ金属層をアル
ミナ質焼結体に強固に被着接合させることができないと
いう欠点を有していた。(Problems to be Solved by the Invention) However, this conventional metallized metal layer using a high melting point metal such as tungsten (W) or molybdenum (Mo) is made of alumina (Al 2 O 3 ) which is an alumina sintered body. Content 90.0
If it is less than 10% by weight, the amount of the glass component interposed between the alumina crystals of the alumina-based sintered body is large, and the transition of the glass component between the high-melting metal particles is smooth, so that the metallized metal layer is formed on the alumina-based sintered body. Although it can be strongly bonded, when the alumina (Al 2 O 3 ) content of the alumina-based sintered body exceeds 92.0% by weight, the amount of glass components interposed between alumina crystals decreases, and the glass components Transfer between the high melting point metal particles is also deteriorated, and the metallized metal layer cannot be firmly adhered and bonded to the alumina sintered body.
そこで上記欠点を解消するために高融点金属粉末から
なるペーストを被着させた未焼成アルミナ成形体を約16
00℃の高温で焼成し、アルミナ質焼結体のアルミナ結晶
間に介在するガラス成分の高融点金属粒子間への移行を
促進することが考えられる。Therefore, in order to eliminate the above-mentioned drawbacks, about 16 unfired alumina compacts coated with a paste made of refractory metal powder are applied.
It is considered that the firing is performed at a high temperature of 00 ° C. to promote the transfer of the glass component existing between the alumina crystals of the alumina-based sintered body between the refractory metal particles.
しかし乍ら、高融点金属粉末からなるペーストを高温
で焼成した場合、高融点金属粉末はその粒子間の反応が
大きく進み、粒成長が進み過ぎて、所謂、オーバーシン
ター状態となってしまい、その結果、高融点金属粒子間
の空隙が広いものとなり、毛管現象による空隙内へのア
ルミナ質焼結体のアルミナ結晶間に介在するガラス成分
の移行が不充分となって依然としてメタライズ金属層を
アルミナ質焼結体に強固に被着接合させることができな
いという欠点を有していた。However, when the paste composed of the high melting point metal powder is fired at a high temperature, the reaction between the particles of the high melting point metal powder proceeds greatly, and the grain growth proceeds too much, resulting in a so-called oversintering state. As a result, the gap between the high-melting metal particles becomes wide, and the transition of the glass component interposed between the alumina crystals of the alumina-based sintered body into the gap due to the capillary phenomenon becomes insufficient, so that the metallized metal layer is still formed of alumina. It has a disadvantage that it cannot be firmly adhered and bonded to a sintered body.
（発明の目的） 本発明者等は上記欠点に鑑み種々の実験の結果、メタ
ライズ用組成物としてタングステン（Ｗ）、モリブデン
（Mo）にレニウム（Re）を所定量含有させておくとアル
ミナ（Al2O3）含有量が92.0重量％以上のアルミナ質焼
結体表面にメタライズ金属層を高温で焼成して被着接合
させる際、レニウム（Re）がタングステン（Ｗ）、モリ
ブデン（Mo）の粒子間反応を抑制し、タングステン
（Ｗ）、モリブデン（Mo）の粒子間に微細な空隙を数多
く残存させて毛管現象による空隙内へのガラス成分の移
行を容易となし、これによってメタライズ金属層をアル
ミナ質焼結体表面に極めて強固に被着接合させ得ること
を知見した。(Object of the Invention) As a result of various experiments in view of the above-mentioned drawbacks, the present inventors have found that when a predetermined amount of rhenium (Re) is added to tungsten (W) and molybdenum (Mo) as a metallizing composition, alumina (Al 2 O 3 ) When particles of rhenium (Re) are tungsten (W) and molybdenum (Mo) when a metallized metal layer is burned at a high temperature on the surface of an alumina-based sintered body having a content of 92.0% by weight or more and adhered and bonded. Reaction is suppressed, and many fine voids remain between the particles of tungsten (W) and molybdenum (Mo), facilitating the migration of the glass component into the voids due to the capillary phenomenon, thereby making the metallized metal layer alumina. It has been found that it is possible to adhere and bond to the surface of a high quality sintered body extremely firmly.
本発明は上記知見に基づき、アルミナ（Al2O3）の含
有量が92.0重量％以上のアルミナ質焼結体に、該アルミ
ナ質焼結体との接合強度が4.0Kg/mm2以上であるメタラ
イズ金属層を形成することができるメタライズ用組成物
を提供することをその目的とするものである。The present invention is based on the above findings, in the alumina sintered body having an alumina (Al 2 O 3 ) content of 92.0% by weight or more, the bonding strength with the alumina sintered body is 4.0 Kg / mm 2 or more. It is an object of the present invention to provide a metallizing composition capable of forming a metallized metal layer.
（課題を解決するための手段） 本発明のメタライズ用組成物は、タングステン、モリ
ブデンの少なくとも１種にレニウムを0.5乃至30.0重量
％含有させて成り、メタライズ金属層をアルミナ含有量
が92.0重量％以上のアルミナ質焼結体に4.0Kg/mm2以上
の接合強度で接合することができることを特徴とするも
のである。(Means for Solving the Problems) The metallizing composition of the present invention comprises at least one of tungsten and molybdenum containing 0.5 to 30.0 wt% rhenium, and the metallized metal layer has an alumina content of 92.0 wt% or more. It is characterized in that it can be bonded to the alumina-based sintered body of (4) with a bonding strength of 4.0 kg / mm 2 or more.
本発明のメタライズ用組成物において含有されるレニ
ウム（Re）はタングステン（Ｗ）もしくはモリブデン
（Mo）の粒子間反応を抑制するための成分であり、その
含有量が0.5重量％未満であると所望する前記性質は付
与されず、また30.0重量％を超えるとレニウム（Re）が
タングステン（Ｗ）、モリブデン（Mo）と金属間化合物
を生成し、メタライズ金属層の電気抵抗が大きなものに
なってしまう。そのためレニウム（Re）はその含有量が
0.5乃至30.0重量％の範囲に特定される。The rhenium (Re) contained in the metallizing composition of the present invention is a component for suppressing the interparticle reaction of tungsten (W) or molybdenum (Mo), and the content thereof is preferably less than 0.5% by weight. If the above-mentioned properties are not given, and if it exceeds 30.0% by weight, rhenium (Re) forms an intermetallic compound with tungsten (W) and molybdenum (Mo), and the electric resistance of the metallized metal layer becomes large. . Therefore, the content of rhenium (Re) is
It is specified in the range of 0.5 to 30.0% by weight.
尚、レニウム（Re）の含有量を1.0乃至5.0重量％の範
囲としておくとアルミナ質焼結体とメタライズ金属層の
接合強度が6.0Kg/mm2以上となり、且つメタライズ金属
層の電気抵抗を小さなものとなすことができることから
レニウム（Re）の含有量は1.0乃至5.0重量％の範囲とし
ておくことが好ましい。When the content of rhenium (Re) is set in the range of 1.0 to 5.0% by weight, the bonding strength between the alumina sintered body and the metallized metal layer becomes 6.0 Kg / mm 2 or more, and the electric resistance of the metallized metal layer is small. The content of rhenium (Re) is preferably in the range of 1.0 to 5.0% by weight because it can be obtained.
（実施例） 次に本発明を実施例に基づいて説明する。(Examples) Next, the present invention will be described based on examples.
まず出発原料として粒径１乃至５μｍのタングステン
（Ｗ）、モリブデン（Mo）及びレニウム（Re）を下表に
示す値となるように秤量し、これに有機溶剤、溶媒を添
加するとともに混練機で10時間混練し、メタライズ用ペ
ースト試料を得る。First, as starting materials, tungsten (W), molybdenum (Mo), and rhenium (Re) having a particle size of 1 to 5 μm are weighed so as to have the values shown in the table below, and an organic solvent and a solvent are added thereto, and a kneader is used. Knead for 10 hours to obtain a paste sample for metallization.
尚、試料番号1,2,13,14,25,26は本発明品と比較する
ための比較試料であり、従来一般に使用されているメタ
ライズ用ペーストである。Sample Nos. 1, 2, 13, 14, 25 and 26 are comparative samples for comparison with the products of the present invention, which are commonly used metallizing pastes.
かくして得られたメタライズ用ペースト試料を使用し
てアルミナ（Al2O3）の含有量が90.0重量％、92.0重量
％、95.0重量％である未焼成アルミナ質成形体の夫々の
外表面に長さ10.0mm、幅0.5mm、厚さ20μｍのバターン2
0個を0.3mmの間隔をおいてスクリーン印刷法により印刷
し、次ぎにこれを還元雰囲気（窒素−水素雰囲気）中、
1550℃もしくは1600℃の温度で焼成しアルミナ質焼結体
の表面にメタライズ金属層を被着接合させる。そして次
ぎにメタライズ金属層の電気抵抗を抵抗測定機で測定
し、その平均値を各メタライズ金属層の電気抵抗値とし
て求めた。Using the metallizing paste sample thus obtained, the length of the alumina (Al 2 O 3 ) content on the outer surface of each of the unfired alumina-based compacts was 90.0%, 92.0% and 95.0% by weight. Pattern 2 with 10.0 mm, width 0.5 mm and thickness 20 μm 2
0 pieces are printed by a screen printing method at intervals of 0.3 mm, then, in a reducing atmosphere (nitrogen-hydrogen atmosphere),
It is fired at a temperature of 1550 ° C or 1600 ° C to adhere and bond a metallized metal layer to the surface of the alumina-based sintered body. Then, the electric resistance of the metallized metal layer was measured by a resistance measuring instrument, and the average value was determined as the electric resistance value of each metallized metal layer.
また、上記各アルミナ質焼結体の表面に1.5mm角のメ
タライズ金属層を被着形成し、これに1.0mm角、長さ40.
0mmの42Alloy（Fe−Ni合金）から成る金属柱の一端面を
銀ロウ（Ag:72％、Cu:28％）を介してロウ付けし、しか
る後、金属板のロウ付け部と反対の端を垂直方向に引っ
張り、メタライズ金属層がアルミナ質焼結体から剥がれ
た際の引っ張り強度を調べ、その平均値をメタライズ金
属層の接合強度として算出した。Also, a 1.5 mm square metallized metal layer was formed on the surface of each of the alumina sintered bodies, and a 1.0 mm square, 40.
One end surface of a 0 mm 42 Alloy (Fe-Ni alloy) metal column was brazed with silver brazing (Ag: 72%, Cu: 28%), and then the end opposite the brazing part of the metal plate. Was pulled in the vertical direction, the tensile strength when the metallized metal layer was peeled from the alumina-based sintered body was examined, and the average value was calculated as the bonding strength of the metallized metal layer.
尚、前記メタライズ金属層に金属板をロウ付けする際
には、メタライズ金属層の外表面に厚さ1.5μｍのNiメ
ッキ層を被着させておいた。When the metal plate was brazed to the metallized metal layer, a Ni plating layer having a thickness of 1.5 μm was deposited on the outer surface of the metallized metal layer.
上記の結果を第１表に示す。 The results are shown in Table 1.
（発明の効果） 上記実験結果からも判るように、従来のメタライズ用
組成物を使用したメタライズ金属層はアルミナ質焼結体
のアルミナ（Al2O3）含有量が90.0重量％であり、焼成
温度が1550℃の時には接合強度が5.8Kg/mm2と大きな値
を示し、メタライズ金属層がアルミナ質焼結体に強固に
被着接合するものの、アルミナ質焼結体のアルミナ（Al
2O3）含有量が92.0重量％を超え、焼成温度が1600℃の
時には接合強度が3.0Kg/mm2以下の値となり、メタライ
ズ金属層の接合強度が大きく低下してしまう。これに対
し、本発明のメタライズ用組成物を使用したメタライズ
金属層はアルミナ質焼結体のアルミナ（Al2O3）含有量
が92.0重量％以上、焼成温度が1600℃の高温であったと
してもメタライズ金属層の接合強度が4.0Kg/mm2以上の
値を示し、メタライズ金属層がアルミナ質焼結体に極め
て強固に被着接合していることが判る。 (Effect of the invention) As can be seen from the above experimental results, the metallized metal layer using the conventional composition for metallization has an alumina (Al 2 O 3 ) content of the alumina-based sintered body of 90.0% by weight, When the temperature is 1550 ° C, the bonding strength shows a large value of 5.8 Kg / mm 2, and although the metallized metal layer adheres strongly to the alumina-based sintered body, the alumina (Al
When the content of 2 O 3 ) exceeds 92.0% by weight and the firing temperature is 1600 ° C., the bonding strength is 3.0 Kg / mm 2 or less, and the bonding strength of the metallized metal layer is significantly reduced. On the other hand, in the metallized metal layer using the metallizing composition of the present invention, the alumina (Al 2 O 3 ) content of the alumina-based sintered body was 92.0% by weight or more, and the firing temperature was 1600 ° C. Also, the bonding strength of the metallized metal layer shows a value of 4.0 kg / mm 2 or more, which shows that the metallized metal layer is extremely strongly adhered and bonded to the alumina-based sintered body.
また、本発明のメタライズ用組成物を使用してアルミ
ナ質焼結体表面にメタライズ金属層を被着接合させた場
合、メタライズ金属層の電気抵抗は50×10-6Ω−cm以下
の小さなものであることが判る。Further, when the metallized metal layer is adhered and bonded to the surface of the alumina-based sintered body using the metallizing composition of the present invention, the electrical resistance of the metallized metal layer is as small as 50 × 10 −6 Ω-cm or less. It turns out that
また特に、レニウム（Re）の含有量が1.0乃至5.0重量
％ではメタライズ金属層の接合強度が6.0Kg/mm2以上、
電気抵抗が20×10-6Ω−cm以下となり、回路配線導体と
して使用する際、極めて有用となる。Further, particularly, when the content of rhenium (Re) is 1.0 to 5.0% by weight, the bonding strength of the metallized metal layer is 6.0 Kg / mm 2 or more,
The electric resistance is 20 × 10 -6 Ω-cm or less, which is extremely useful when used as a circuit wiring conductor.
よって本発明のメタライズ用組成物は半導体素子を収
容する半導体素子収納用パッケージや回路基板等の電子
部品において回路配線導体としてのメタライズ金属層の
形成に極めて有用である。Therefore, the metallizing composition of the present invention is extremely useful for forming a metallized metal layer as a circuit wiring conductor in an electronic component such as a semiconductor element housing package for housing a semiconductor element or a circuit board.
Claims (1)
種にレニウムを0.5乃至30.0重量％含有させて成り、メ
タライズ金属層をアルミナ含有量が92.0重量％以上のア
ルミナ質焼結体に4.0Kg/mm2以上の接合強度で接合する
ことができるメタライズ用組成物。1. At least one of tungsten and molybdenum.
For metallization, which contains 0.5 to 30.0% by weight of rhenium as a seed, and can bond a metallized metal layer to an alumina-based sintered body with an alumina content of 92.0% by weight or more with a bonding strength of 4.0 kg / mm 2 or more. Composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339155A JP2678512B2 (en) | 1989-12-26 | 1989-12-26 | Metallizing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339155A JP2678512B2 (en) | 1989-12-26 | 1989-12-26 | Metallizing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03197376A JPH03197376A (en) | 1991-08-28 |
| JP2678512B2 true JP2678512B2 (en) | 1997-11-17 |
Family
ID=18324762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1339155A Expired - Fee Related JP2678512B2 (en) | 1989-12-26 | 1989-12-26 | Metallizing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2678512B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2975491B2 (en) * | 1992-12-24 | 1999-11-10 | 京セラ株式会社 | Chip resistor |
-
1989
- 1989-12-26 JP JP1339155A patent/JP2678512B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03197376A (en) | 1991-08-28 |
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