JP3420426B2 - Copper metallized composition and glass-ceramic wiring board using the same - Google Patents
Copper metallized composition and glass-ceramic wiring board using the sameInfo
- Publication number
- JP3420426B2 JP3420426B2 JP10713696A JP10713696A JP3420426B2 JP 3420426 B2 JP3420426 B2 JP 3420426B2 JP 10713696 A JP10713696 A JP 10713696A JP 10713696 A JP10713696 A JP 10713696A JP 3420426 B2 JP3420426 B2 JP 3420426B2
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- Japan
- Prior art keywords
- glass
- copper
- weight
- parts
- glass ceramic
- Prior art date
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- Parts Printed On Printed Circuit Boards (AREA)
- Glass Compositions (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Conductive Materials (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラスセラミック
磁器と同時焼成が可能な銅メタライズ組成物と、該銅メ
タライズ組成物を用いてガラスセラミック磁器と同時焼
成し、ガラスセラミック磁器の絶縁基体に銅（Ｃｕ）か
ら成る配線層を形成した、誘電率が低く、低抵抗の導体
を有する各種回路基板や高周波用多層配線基板等に好適
なガラスセラミック配線基板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper metallization composition which can be co-fired with a glass ceramic porcelain, and a glass ceramic porcelain which is co-fired with the copper metallized composition to form copper on an insulating substrate of the glass ceramic porcelain. The present invention relates to a glass-ceramic wiring board having a wiring layer made of (Cu), which is suitable for various circuit boards having low-dielectric constant and low-resistance conductors, high-frequency multilayer wiring boards, and the like.
【０００２】[0002]
【従来の技術】従来より、アルミナ質セラミックスは、
電気絶縁性や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、半導体素子の他に各種電子部品を搭載した混成集積
回路装置等の各種配線基板用絶縁基体として多用されて
いる。2. Description of the Related Art Conventionally, alumina ceramics have been
Because of its excellent properties such as electrical insulation and chemical stability, it is used for semiconductor element housing packages that house semiconductor elements, and for various wiring boards such as hybrid integrated circuit devices that mount various electronic components in addition to semiconductor elements. It is often used as an insulating substrate.
【０００３】近年、高周波化及び高密度化が進むＩＣや
ＬＳＩ等の半導体素子を搭載する配線基板には、前記ア
ルミナ質セラミックスから成る絶縁基体より更に低い誘
電率とより低い配線抵抗が要求されるようになり、該要
求に適用できる絶縁基体としてガラスセラミックスが、
また該ガラスセラミックスと同時焼成できる焼成温度が
低い低抵抗の導体として、例えば銅（Ｃｕ）、金（Ａ
ｕ）、銀（Ａｇ）で配線層を形成することが注目され、
高周波化及び高密度化が進む通信分野で使用する配線基
板として前記ガラスセラミックスから成る絶縁基体と低
抵抗導体とを組合せたガラスセラミック配線基板の開発
がなされており、とりわけ前記低抵抗導体としてＣｕに
よる配線化が鋭意進められている。In recent years, wiring boards on which semiconductor elements such as ICs and LSIs, which are becoming higher in frequency and higher in density, are mounted are required to have a lower dielectric constant and a lower wiring resistance than the insulating base made of alumina ceramics. As a result, glass ceramics can be
In addition, examples of low-resistance conductors having a low firing temperature that can be fired simultaneously with the glass ceramics include copper (Cu) and gold (A).
u), forming a wiring layer with silver (Ag) has attracted attention,
A glass ceramic wiring board in which an insulating substrate made of the glass ceramics and a low-resistance conductor are combined has been developed as a wiring board used in the field of communication in which high frequencies and high densities are advanced, and in particular, Cu is used as the low-resistance conductor. Wiring is being enthusiastically pursued.
【０００４】係るガラスセラミック配線基板は、一般に
はガラスセラミック原料粉末と有機バインダー、溶媒か
ら成る泥漿をドクターブレード法等のシート成形方法で
成形し、得られたガラスセラミックグリーンシートにス
ルーホールを形成し、該スルーホールに銅メタライズ組
成物を含む銅ペーストを充填し、次に、前記グリーンシ
ート上に銅ペーストを用いて所定の配線パターンを印刷
形成した後、位置合わせして複数枚加圧積層し、該積層
体を加熱してバインダーの除去及びガラスセラミックグ
リーンシートと銅メタライズ組成物とを同時焼成するこ
とにより作製されていた。Such a glass-ceramic wiring board is generally formed by molding a glass-ceramic raw material powder, an organic binder, and a solvent by a sheet forming method such as a doctor blade method, and forming a through hole in the obtained glass-ceramic green sheet. Filling the through-holes with a copper paste containing a copper metallizing composition, then printing-forming a predetermined wiring pattern on the green sheet using the copper paste, aligning and stacking a plurality of pressure-bonded sheets. It was prepared by heating the laminate to remove the binder and co-firing the glass ceramic green sheet and the copper metallization composition.
【０００５】前述のようにガラスセラミック磁器と同時
焼成可能な銅メタライズ組成物としては、銅メタライズ
組成物中にガラス粉末を含有するものが多く提案されて
おり、その一例として７００℃以上の温度で溶融するガ
ラス粉末を５〜２４体積％の割合で銅粉末と混合するこ
とが特開平５−２４３７００号公報等に提案されてい
る。As described above, as a copper metallizing composition which can be co-fired with a glass ceramic porcelain, many which contain glass powder in the copper metallizing composition have been proposed, and one example thereof is at a temperature of 700 ° C. or higher. It has been proposed in JP-A-5-243700 and the like to mix molten glass powder with copper powder in a proportion of 5 to 24% by volume.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、前記銅
メタライズ組成物をガラスセラミックグリーンシート上
に印刷して同時焼成した場合、ガラス粉末の混合割合が
５体積％でも該ガラス粉末が焼成後の銅配線層表面に浮
いて残存し易く、後工程の半田濡れ性が悪いという課題
があった。However, when the copper metallized composition is printed on a glass ceramic green sheet and co-fired, the copper wiring after firing the glass powder is 5% by volume even if the glass powder is fired. There is a problem that the layer easily floats and remains on the surface of the layer, and has poor solder wettability in a subsequent process.
【０００７】また、同時焼成する際、前記銅メタライズ
組成物とガラスセラミック磁器との焼結開始温度が異な
ると焼成過程での収縮のズレから、更に焼結終了温度が
相違して銅メタライズ組成物が先に緻密化するとガラス
セラミック磁器の収縮が抑制され、その結果、焼成後の
絶縁基体には大きな反りやうねり等の変形が発生すると
いう課題があり、例えば、縦５０ｍｍ、横２０ｍｍ、厚
さ１ｍｍの寸法形状を有するガラスセラミック磁器の片
面のみに銅メタライズ層を形成した場合、その変形量が
０．５ｍｍを越えるものであった。Further, when the copper metallized composition and the glass ceramic porcelain are different in sintering start temperature during simultaneous firing, the difference in shrinkage in the firing process causes further difference in sintering end temperature, resulting in different copper metallization composition. However, if it is densified first, the shrinkage of the glass-ceramic porcelain is suppressed, and as a result, there is a problem that a large deformation such as warpage or waviness occurs in the insulating substrate after firing. When the copper metallized layer was formed only on one surface of the glass ceramic porcelain having a dimension of 1 mm, the amount of deformation thereof exceeded 0.5 mm.
【０００８】その上、同時焼成後の銅配線層とガラスセ
ラミック磁器との界面における接着強度が、例えば、２
ｍｍ角の銅配線層に半田接合したリード線を接合面に対
して垂直に引っ張って評価するとその剥離荷重は３Ｋｇ
程度と低く、未だ充分とは言えず、更に接着強度の向上
及び安定化が必要であるという課題があった。Moreover, the adhesive strength at the interface between the copper wiring layer and the glass ceramic porcelain after co-firing is, for example, 2
When a lead wire soldered to a square mm copper wiring layer is pulled vertically to the bonding surface and evaluated, the peeling load is 3 kg.
The level is low and not sufficient, and there is a problem that the adhesive strength needs to be further improved and stabilized.
【０００９】[0009]
【発明の目的】本発明は前記課題に鑑みなされたもの
で、銅配線層とガラスセラミック磁器とを同時焼成する
ことができ、後工程の半田濡れ性等を阻害せず、かつガ
ラスセラミック磁器から成る絶縁基体の反りやうねり等
の変形を効果的に防止することができ、銅配線層とガラ
スセラミック磁器との界面の接着強度が高く、安定した
接着強度が得られる銅メタライズ組成物と、該銅メタラ
イズ組成物を用いて同時焼成し、ガラスセラミック磁器
の絶縁基体にＣｕから成る配線層を形成した、誘電率が
低く、低抵抗の導体を有する各種回路基板や高周波用多
層配線基板等に好適なガラスセラミック配線基板を提供
することを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and a copper wiring layer and a glass ceramic porcelain can be co-fired, which does not impair solder wettability and the like in a subsequent step, A copper metallized composition capable of effectively preventing warping, undulation, or other deformation of the insulating substrate, having high adhesive strength at the interface between the copper wiring layer and the glass ceramic porcelain, and having stable adhesive strength, Suitable for various circuit boards with low dielectric constant and low resistance conductors, high-frequency multilayer wiring boards, etc., in which a wiring layer made of Cu is formed on an insulating substrate of a glass ceramic porcelain by simultaneous firing using a copper metallized composition. An object of the present invention is to provide a simple glass-ceramic wiring board.
【００１０】[0010]
【課題を解決するための手段】本発明者等は、前記課題
を解決するための方法について検討した結果、銅メタラ
イズ組成物中にガラスセラミック磁器中のガラス成分の
粘性を低下させることができる金属酸化物を添加すると
ともに、Ｃｕの焼結を遅らせることのできる無機物を同
時添加することにより、ガラスセラミック磁器と銅配線
層との接着強度を高く維持しながら、同時焼成後の銅配
線層への半田濡れ性が改善でき、絶縁基体の反り等の変
形も低減できることを知見したものである。DISCLOSURE OF THE INVENTION As a result of studies on the method for solving the above problems, the present inventors have found that a metal capable of reducing the viscosity of the glass component in the glass ceramic porcelain in the copper metallized composition. By simultaneously adding an oxide and an inorganic substance that can delay the sintering of Cu, while maintaining high adhesive strength between the glass ceramic porcelain and the copper wiring layer, the copper wiring layer after co-firing It has been found that the solder wettability can be improved and the deformation such as the warp of the insulating substrate can be reduced.
【００１１】即ち、本発明の銅メタライズ組成物は、８
００〜１１００℃でガラスセラミック磁器と同時焼成可
能なＣｕを主成分とする銅メタライズ組成物であり、該
組成物中に、前記ガラスセラミック磁器中のガラス成分
の粘性を同時焼成時に低下させることができる金属酸化
物として、アルカリ金属、アルカリ土類金属、及びＢの
内の少なくとも１種の酸化物を前記Ｃｕ１００重量部に
対して０．１〜５．０重量部と、該Ｃｕの焼結を遅らせ
ることができる無機物を０．１〜５．０重量部の割合で
含有することを特徴とするものである。That is, the copper metallization composition of the present invention is 8
A copper metallized composition containing Cu as a main component, which can be co-fired with a glass ceramic porcelain at 00 to 1100 ° C., and in which the viscosity of the glass component in the glass ceramic porcelain can be reduced during co-firing. As a metal oxide that can be formed, at least one oxide selected from alkali metal, alkaline earth metal, and B is added to 0.1 to 5.0 parts by weight with respect to 100 parts by weight of Cu, and the Cu is sintered. It is characterized by containing 0.1 to 5.0 parts by weight of an inorganic substance that can be delayed.
【００１２】とりわけ、前記ガラスセラミック磁器中の
ガラス成分としてはＳｉＯ2 、Ａｌ2 Ｏ3 、アルカリ土
類金属の酸化物及びＢ2 Ｏ3 を含有するとともに、前記
金属酸化物がＣａＯであり、かつ前記無機物がＡｌ2 Ｏ
3 、ＳｉＯ2 、ＺｒＯ2 の内の少なくとも１種であるこ
とがより望ましいものである。In particular, the glass component in the glass ceramic porcelain contains SiO 2 , Al 2 O 3 , an oxide of an alkaline earth metal and B 2 O 3, and the metal oxide is CaO, and The inorganic substance is Al 2 O
More preferably, it is at least one of 3 , SiO 2 , and ZrO 2 .
【００１３】また、本発明のガラスセラミック配線基板
は、ガラスセラミック磁器中のガラス成分の粘度を低下
させることができる金属酸化物として、アルカリ金属、
アルカリ土類金属、及びＢの少なくとも１種の酸化物を
Ｃｕ１００重量部に対して０．１〜５．０重量部と、前
記Ｃｕの焼結を遅らせることができる無機物を０．１〜
５．０重量部含有した銅メタライズ組成物を、窒素雰囲
気中、８００〜１１００℃の温度でガラスセラミック磁
器と同時焼成して形成した銅配線層を有することを特徴
とするものである。The glass-ceramic wiring board of the present invention has an alkali metal as a metal oxide capable of reducing the viscosity of the glass component in the glass-ceramic porcelain.
0.1 to 5.0 parts by weight of an alkaline earth metal and at least one oxide of B with respect to 100 parts by weight of Cu, and 0.1 to 0.1 parts by weight of an inorganic substance that can delay the sintering of Cu.
The present invention is characterized by having a copper wiring layer formed by co-firing a copper metallization composition containing 5.0 parts by weight in a nitrogen atmosphere at a temperature of 800 to 1100 ° C. with a glass ceramic porcelain.
【００１４】更に、前記ガラスセラミック配線基板は、
ガラスセラミック磁器中のガラス成分が、少なくともＳ
ｉＯ2 、Ａｌ2 Ｏ3 、アルカリ土類金属の酸化物及びＢ
2 Ｏ3 を含有するとともに、前記金属酸化物がＣａＯで
あり、かつ前記無機物がＡｌ2 Ｏ3 、ＳｉＯ2 、ＺｒＯ
2 の内の少なくとも１種であることがより望ましいもの
である。Further, the glass ceramic wiring board is
If the glass component in the glass-ceramic porcelain is at least S
iO 2 , Al 2 O 3 , oxides of alkaline earth metals and B
2 O 3 is contained, the metal oxide is CaO, and the inorganic substance is Al 2 O 3 , SiO 2 , ZrO.
More preferably, it is at least one of the two .
【００１５】[0015]
【作用】本発明によれば、銅メタライズ組成物が、ガラ
スセラミック磁器中のガラス成分と反応し、該ガラス成
分の粘性を低下させ得る金属酸化物、即ち、アルカリ金
属、アルカリ土類金属、及びＢの内の少なくとも１種の
酸化物を含有し、更にＣｕの焼結を遅らせ得る無機物も
含有することから、８００〜１１００℃の温度で同時焼
成してもガラス成分が銅配線層表面に浮いて残存するこ
となく、しかも銅メタライズ組成物の収縮開始温度がガ
ラスセラミック磁器の収縮開始温度に近づき、ガラスセ
ラミック磁器中のガラス成分が前記無機物と反応して粘
性が低下し、銅メタライズ組成物中のＣｕ粒子の隙間へ
浸透し、その結果、銅配線層の接着強度が向上するとと
もに、前記無機物によりＣｕの焼結の開始が遅らせられ
て焼成後の絶縁基体の反りやうねり等の変形が極めて小
さいガラスセラミック配線基板を得ることができる。According to the present invention, the copper metallizing composition reacts with the glass component in the glass-ceramic porcelain to reduce the viscosity of the glass component, that is, alkali metal, alkaline earth metal, and Since it contains at least one oxide of B and also contains an inorganic substance that can delay the sintering of Cu, the glass component floats on the surface of the copper wiring layer even when co-firing at a temperature of 800 to 1100 ° C. Without remaining, and the contraction start temperature of the copper metallized composition approaches the contraction start temperature of the glass ceramic porcelain, the glass component in the glass ceramic porcelain reacts with the inorganic substance to reduce the viscosity, Of Cu particles permeate into the interstices of Cu particles, and as a result, the adhesive strength of the copper wiring layer is improved, and the start of sintering of Cu is delayed by the inorganic substance, so that the insulating group after firing is It can be modified, such as warping or undulation to obtain a very small glass ceramic wiring board.
【００１６】[0016]
【発明の実施の形態】以下、本発明の銅メタライズ組成
物及びそれを用いたガラスセラミック配線基板について
詳述する。BEST MODE FOR CARRYING OUT THE INVENTION The copper metallization composition of the present invention and the glass ceramic wiring board using the same will be described in detail below.
【００１７】本発明の銅メタライズ組成物とは、Ｃｕを
主成分とし、該Ｃｕ以外に同時焼成時にガラスセラミッ
ク磁器中のガラス成分と反応してガラス成分の粘性を低
下させることができる金属酸化物と、前記Ｃｕの焼結を
遅らせることができる無機物を含有させたものであり、
前記金属酸化物は、Ｃｕ１００重量部に対してアルカリ
金属、アルカリ土類金属、及びＢの少なくとも１種の酸
化物を０．１〜５．０重量部とするもので、かつ前記無
機物は、Ｃｕ１００重量部に対して０．１〜５．０重量
部とするものである。The copper metallization composition of the present invention is a metal oxide containing Cu as a main component and capable of reducing the viscosity of the glass component by reacting with the glass component in the glass-ceramic porcelain during co-firing, in addition to Cu. And an inorganic material that can delay the sintering of the Cu,
The metal oxide is 0.1 to 5.0 parts by weight of at least one oxide of an alkali metal, an alkaline earth metal, and B with respect to 100 parts by weight of Cu, and the inorganic material is Cu100. The amount is 0.1 to 5.0 parts by weight with respect to parts by weight.
【００１８】本発明において、前記金属酸化物として
は、例えば、Ｎａ2 Ｏ、Ｋ2 Ｏ等のアルカリ金属の酸化
物、ＣａＯ、ＢａＯ、ＳｒＯ等のアルカリ土類金属の酸
化物や、Ｂ2 Ｏ3 等が挙げられるが、ガラスセラミック
磁器中のガラス成分の組成に応じて適宜選択することが
必要であるが、ガラスセラミック磁器中のガラス成分が
ＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 −アルカリ土類金属酸
化物系ガラス、特に結晶性ガラスである場合、銅メタラ
イズ組成物中に金属酸化物として特にＣａＯ成分を添加
することにより、前記ガラス成分の粘性を効果的に低下
させ、かつ該ガラス成分をＣｕ粒子間に浸透させること
ができる。In the present invention, examples of the metal oxide include alkali metal oxides such as Na 2 O and K 2 O, alkaline earth metal oxides such as CaO, BaO and SrO, and B 2 O. 3 and the like, it is necessary to appropriately select according to the composition of the glass component in the glass ceramic porcelain, but the glass component in the glass ceramic porcelain is SiO 2 —Al 2 O 3 —B 2 O 3 — In the case of an alkaline earth metal oxide glass, particularly a crystalline glass, by adding a CaO component as a metal oxide in the copper metallization composition, the viscosity of the glass component is effectively reduced, and The glass component can be infiltrated between the Cu particles.
【００１９】また、前記金属酸化物の含有量がＣｕ１０
０重量部に対して０．１重量部未満になると、ガラスセ
ラミック磁器中のガラス成分を銅メタライズ組成物中に
浸透させる効果が小さく接着強度が低下し、５．０重量
部を越えるとガラスセラミック磁器中のガラス成分が過
度に銅メタライズ組成物中に浸透し、銅配線層表面に析
出して銅配線層の半田濡れ性やメッキ処理性が劣化する
上、接着強度も低下する傾向を示す。The content of the metal oxide is Cu10.
If it is less than 0.1 parts by weight with respect to 0 parts by weight, the effect of permeating the glass component in the glass ceramic porcelain into the copper metallized composition is small and the adhesive strength is lowered, and if it exceeds 5.0 parts by weight, the glass ceramic is exceeded. The glass component in the porcelain excessively penetrates into the copper metallized composition and is deposited on the surface of the copper wiring layer to deteriorate the solder wettability and the plating processability of the copper wiring layer, and also tends to lower the adhesive strength.
【００２０】従って、前記金属酸化物の含有量は０．１
〜５．０重量部に特定され、特に０．５〜３．０重量部
が望ましい。Therefore, the content of the metal oxide is 0.1.
To 5.0 parts by weight, particularly 0.5 to 3.0 parts by weight is desirable.
【００２１】また、前記金属酸化物は、炭酸塩や硝酸
塩、酢酸塩等の化合物の他、それらの複合酸化物を用い
ることも可能である。As the metal oxide, it is possible to use compounds such as carbonates, nitrates and acetates, as well as complex oxides thereof.
【００２２】一方、前記Ｃｕの焼結を遅くし得る無機物
としては、Ａｌ2 Ｏ3 、ＳｉＯ2 、ＺｒＯ2 、ムライト
（３Ａｌ2 Ｏ3 ・２ＳｉＯ2 ）、コージェライト（２Ｍ
ｇＯ・２Ａｌ2 Ｏ3 ・５ＳｉＯ2 ）等が挙げられるが、
銅メタライズ組成物が前記ガラス成分の浸透により早く
焼結してしまうのを防ぎ、かつガラス成分と添加した無
機物とによりガラスセラミック磁器と銅配線層との界面
で強固に接着すると言う点ではＡｌ2 Ｏ3 、ＳｉＯ2 、
ＺｒＯ2 の少なくとも１種が好適である。On the other hand, as the inorganic substances that can delay the sintering of Cu, Al 2 O 3 , SiO 2 , ZrO 2 , mullite (3Al 2 O 3 .2SiO 2 ), cordierite (2M
gO.2Al 2 O 3 .5SiO 2 ), etc.
Al 2 in terms of preventing the copper metallization composition from prematurely sintering due to the permeation of the glass component and firmly adhering at the interface between the glass ceramic porcelain and the copper wiring layer by the glass component and the added inorganic substance. O 3 , SiO 2 ,
At least one ZrO 2 is suitable.
【００２３】前記無機物の含有量が、Ｃｕ１００重量部
に対して０．１重量部未満の場合、前記Ｃｕの焼結を遅
らせる効果が小さく、絶縁基体に反り等の変形が大とな
り、５．０重量部を越えると、得られた銅配線層が緻密
化せず、それはとりもなおさず収縮量の減少となること
から、ガラスセラミック磁器と銅配線層との接着強度が
低下するとともに、反りが大となる。When the content of the inorganic material is less than 0.1 parts by weight with respect to 100 parts by weight of Cu, the effect of delaying the sintering of Cu is small, and the deformation such as warpage of the insulating substrate becomes large. If the weight part is exceeded, the obtained copper wiring layer will not be densified, and the amount of shrinkage will be reduced in any case.Therefore, the adhesive strength between the glass ceramic porcelain and the copper wiring layer will decrease, and the warp will also occur. It becomes big.
【００２４】従って、その含有量は０．１〜５．０重量
部に特定され、より好ましくは０．５〜３．０重量部と
なる。Therefore, the content is specified to be 0.1 to 5.0 parts by weight, and more preferably 0.5 to 3.0 parts by weight.
【００２５】次に、銅メタライズ組成物中のＣｕは、平
均粒径が２〜８μｍ（ＢＥＴ法による比表面積が０．１
〜１．０ｍ2 ／ｇ）、好ましくは平均粒径が３〜７μｍ
（比表面積が０．２〜０．５ｍ2 ／ｇ）の球状銅粉末を
用いるのが好ましい。Next, Cu in the copper metallization composition has an average particle size of 2 to 8 μm (specific surface area of 0.1 according to BET method).
˜1.0 m 2 / g), preferably an average particle size of 3 to 7 μm
It is preferable to use spherical copper powder (having a specific surface area of 0.2 to 0.5 m 2 / g).
【００２６】また、前記銅メタライズ組成物を用いて銅
ペーストを調製する場合、該メタライズ組成物に添加さ
れるビヒクル中のバインダーには、窒素雰囲気中での熱
分解性に優れたメタクリル酸樹脂、具体的には、メタク
リル酸イソブチル、メタクリル酸ノルマルブチル等を用
いるのが望ましく、前記ビヒクルの溶剤には、ブチルカ
ルビトールアセテート、ジブチルフタレート、αテルピ
ネオール等が好適であり、前記銅ペーストは、例えば銅
粉末１００重量部にバインダーを２〜６重量部と溶媒を
添加混合して調製される。When a copper paste is prepared using the copper metallizing composition, the binder in the vehicle added to the metallizing composition includes a methacrylic acid resin having excellent thermal decomposability in a nitrogen atmosphere, Specifically, it is desirable to use isobutyl methacrylate, normal butyl methacrylate, or the like.The solvent of the vehicle is preferably butyl carbitol acetate, dibutyl phthalate, α-terpineol, or the like, and the copper paste is, for example, copper. It is prepared by adding 2 to 6 parts by weight of a binder and 100 parts by weight of powder and mixing them with a solvent.
【００２７】また、本発明で用いられるガラスセラミッ
ク磁器組成物としては、ガラス成分とセラミックフィラ
ー成分から成るものを用い、ガラス成分としては周知の
ガラスを用いることができるが、特に焼成時に結晶化す
る結晶性ガラスが望ましく、該結晶性ガラスからの結晶
相の析出により強度を向上でき、この結果、銅配線層の
接着強度も向上させることができる。The glass-ceramic porcelain composition used in the present invention may be composed of a glass component and a ceramic filler component, and known glass may be used as the glass component. Crystalline glass is desirable, and the strength can be improved by the precipitation of the crystal phase from the crystalline glass, and as a result, the adhesive strength of the copper wiring layer can also be improved.
【００２８】一方、セラミックフィラー成分としては、
ジルコン酸カルシウム、チタン酸カルシウム、チタン酸
ストロンチウム、チタン酸バリウム、アルミナ、ムライ
ト、フォルステライト、ジルコニア、スピネル等を用い
ることができる。On the other hand, as the ceramic filler component,
Calcium zirconate, calcium titanate, strontium titanate, barium titanate, alumina, mullite, forsterite, zirconia, spinel and the like can be used.
【００２９】次に、絶縁基体としては、例えばＳｉＯ2
−Ａｌ2 Ｏ3 −Ｂ2 Ｏ3 −ＭｇＯ−ＺｎＯ系結晶性ガラ
スとセラミックフィラーから成る原料粉末に窒素雰囲気
下での熱分解性に優れたメタクリル酸イソブチル等のア
クリル系樹脂の有機バインダーを、固形分で前記原料粉
末に対して８〜２０重量％と、フタル酸エステル等の可
塑剤及びトルエン等の溶媒を添加して調製した泥漿を周
知のシート成形法でグリーンシートを成形する。Next, as the insulating substrate, for example, SiO 2 is used.
-Al 2 O 3 -B 2 O 3 -MgO-ZnO-based crystalline powder and a raw material powder consisting of a ceramic filler with an organic binder of an acrylic resin such as isobutyl methacrylate having excellent thermal decomposability in a nitrogen atmosphere, A slurry prepared by adding a plasticizer such as phthalic acid ester and a solvent such as toluene in a solid content of 8 to 20% by weight to the raw material powder is molded into a green sheet by a known sheet molding method.
【００３０】得られたグリーンシート表面の所定位置に
前述のような銅メタライズ組成物を含有するペーストを
印刷して導体パターンを形成した後、該シートを位置合
わせして複数枚加圧積層する。A paste containing the above-mentioned copper metallization composition is printed at a predetermined position on the surface of the obtained green sheet to form a conductor pattern, and then the sheets are aligned and laminated under pressure.
【００３１】その後、前記積層体を３００〜５００℃の
水蒸気を含んだ窒素雰囲気中で熱処理してグリーンシー
ト及び銅ペースト中のバインダーや可塑剤、溶媒を分解
除去し、次いで温度を７００〜８００℃に上げてグリー
ンシート及び銅ペースト中の残留炭素を除去する。Thereafter, the laminate is heat-treated in a nitrogen atmosphere containing steam at 300 to 500 ° C. to decompose and remove the binder, plasticizer and solvent in the green sheet and the copper paste, and then the temperature is 700 to 800 ° C. To remove residual carbon in the green sheet and copper paste.
【００３２】この時、処理温度が７００℃より低いと残
留する炭素を効率良く除去できず、焼成後の絶縁基体中
に炭素が残留し、８００℃より高いと焼成収縮による絶
縁基体の緻密化が急激に進行し、絶縁基体内部に未分解
の炭素が残留し、絶縁基体の色調不良や絶縁不良が発生
する。At this time, if the treatment temperature is lower than 700 ° C., the residual carbon cannot be removed efficiently, and the carbon remains in the insulating substrate after firing, and if it is higher than 800 ° C., the insulating substrate is densified by firing shrinkage. It rapidly progresses and undecomposed carbon remains inside the insulating substrate, resulting in poor color tone and poor insulation of the insulating substrate.
【００３３】その後、乾燥窒素雰囲気中、８００〜１１
００℃、より望ましくは９００〜１０５０℃の温度でガ
ラスセラミック磁器と銅メタライズ組成物とを同時焼成
することにより、本発明の銅配線層を有するガラスセラ
ミック配線基板を形成することができる。Then, in a dry nitrogen atmosphere, 800 to 11
The glass ceramic wiring board having the copper wiring layer of the present invention can be formed by co-firing the glass ceramic porcelain and the copper metallized composition at a temperature of 00 ° C., more preferably 900 to 1050 ° C.
【００３４】[0034]
【実施例】以下、本発明の銅メタライズ組成物及びそれ
を用いたガラスセラミック配線基板について、実施例に
基づき具体的に詳述する。EXAMPLES The copper metallization composition of the present invention and the glass-ceramic wiring board using the same will be specifically described below based on examples.
【００３５】先ず、平均粒径が５．０μｍの球状銅粉末
１００重量部に対して、金属酸化物と無機物をそれぞれ
表１及び表２に示す割合で秤量し、それに有機バインダ
ーとしてメタクリル酸イソブチルと、溶媒としてブチル
カルビトールアセテート及びジブチルフタレートの混合
溶液を添加して混練し、ペースト状の銅メタライズ用試
料を作製した。First, with respect to 100 parts by weight of spherical copper powder having an average particle size of 5.0 μm, metal oxides and inorganic substances were weighed in the ratios shown in Tables 1 and 2, respectively, and isobutyl methacrylate was used as an organic binder. A mixed solution of butyl carbitol acetate and dibutyl phthalate was added as a solvent and kneaded to prepare a paste-like sample for copper metallization.
【００３６】尚、前記銅メタライズ用試料中の有機バイ
ンダー量は、球状銅粉末１００重量部に対して３重量部
とした。The amount of organic binder in the copper metallizing sample was 3 parts by weight with respect to 100 parts by weight of spherical copper powder.
【００３７】また、表１及び表２に示す銅メタライズ組
成物の金属酸化物及び無機物、ガラスセラミック磁器の
ガラス成分及びフィラー成分の種類の詳細は、表３に記
載した通りである。The details of the types of metal oxides and inorganic materials of the copper metallized compositions, glass components and filler components of the glass ceramic porcelain shown in Tables 1 and 2 are as described in Table 3.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【００４０】[0040]
【表３】 [Table 3]
【００４１】一方、絶縁基体用のガラスセラミック成形
体は、ＳｉＯ2 ４４重量％、Ａｌ2Ｏ3 ２８重量％、Ｍ
ｇＯ１１重量％、ＺｎＯ８重量％、Ｂ2 Ｏ3 ９重量％の
組成を有する結晶性ガラス粉末６０重量％と、セラミッ
クフィラーとして、ジルコン酸カルシウム２０重量％、
チタン酸ストロンチウム１６重量％、アルミナ４重量％
から成るガラスセラミック原料粉末１００重量部に対し
て、有機バインダーとしてメタクリル酸イソブチル樹脂
を固形分で１４重量部、可塑剤としてフタル酸ジブチル
を７重量部添加し、それにトルエンを溶媒として添加し
てボールミルにより４０時間混合して調製した泥漿を、
ドクターブレード法により厚さ０．３ｍｍのグリーンシ
ートに成形した。On the other hand, the glass-ceramic molded body for the insulating substrate is composed of 44% by weight of SiO 2 , 28% by weight of Al 2 O 3 , and M.
60% by weight of crystalline glass powder having a composition of 11% by weight of gO, 8% by weight of ZnO and 9% by weight of B 2 O 3, and 20% by weight of calcium zirconate as a ceramic filler,
16% by weight strontium titanate, 4% by weight alumina
To 100 parts by weight of the glass-ceramic raw material powder consisting of, 14 parts by weight of isobutyl methacrylate resin as an organic binder and 7 parts by weight of dibutyl phthalate as a plasticizer were added, and toluene was added as a solvent to the ball mill. The slurry prepared by mixing for 40 hours with
A green sheet having a thickness of 0.3 mm was formed by the doctor blade method.
【００４２】かくして得られたペースト状の銅メタライ
ズ用試料を用いて、前記ガラスセラミックグリーンシー
ト上に焼成後の形状が縦２ｍｍ、横２ｍｍ（２ｍｍ
角）、厚さ１５μｍとなる銅配線層用パターンを形成
し、これを最上層として銅配線層用パターンを形成して
いないグリーンシート６枚を加圧積層したものと、焼成
後の形状が縦５０ｍｍ、横２０ｍｍ、厚さ１５μｍとな
る銅配線層用パターンを作成し、これを最上層として銅
配線層用パターンを形成していないグリーンシートを焼
成後の全体の厚さが１ｍｍとなるように加圧積層し、パ
ターンにそって切断した２種類を準備した。Using the paste-like sample for copper metallization thus obtained, the shape after firing on the glass ceramic green sheet was 2 mm in length and 2 mm in width (2 mm).
Square), a copper wiring layer pattern having a thickness of 15 μm is formed, and six green sheets on which the copper wiring layer pattern is not formed are used as the uppermost layer, and the green shape after firing is vertical. A copper wiring layer pattern having a thickness of 50 mm, a width of 20 mm, and a thickness of 15 μm is formed, and the green sheet on which the copper wiring layer pattern is not formed is used as the uppermost layer so that the total thickness after firing is 1 mm. Two types were prepared by pressure lamination and cutting along a pattern.
【００４３】次いで、ガラスセラミック成形体及び銅メ
タライズ用試料中の有機バインダー等の有機成分を分解
除去するために、水蒸気を含んだ窒素雰囲気中、７５０
℃の温度で３時間保持する熱処理を行って残留炭素量を
２００ｐｐｍ以下に低減した後、雰囲気を乾燥窒素に切
り替え、９００℃に昇温して１時間保持する焼成を行
い、銅配線層を有する評価用のガラスセラミック配線基
板を得た。Then, in order to decompose and remove organic components such as the organic binder in the glass ceramic compact and the sample for copper metallization, 750 in a nitrogen atmosphere containing water vapor.
After performing a heat treatment at a temperature of ℃ for 3 hours to reduce the amount of residual carbon to 200 ppm or less, switch the atmosphere to dry nitrogen, raise the temperature to 900 ℃, and perform a baking for 1 hour to perform baking with a copper wiring layer. A glass ceramic wiring board for evaluation was obtained.
【００４４】かくして得られた評価用のガラスセラミッ
ク配線基板を用いて、２ｍｍ角の銅配線層に厚さ２．５
μｍのＮｉメッキを行い、その上に厚さ０．１μｍのＡ
ｕメッキをした後、該メッキ被覆層上にＣｕ系のリード
線を銅配線層表面と平行に半田接合し、その時の半田濡
れ部を目視検査して半田濡れ性の良否を、また、前記リ
ード線を銅配線層表面に対して垂直方向に曲げ、該リー
ド線を１０ｍｍ／ｍｉｎ．の引っ張り速度で垂直方向に
引っ張り、リード線が剥離した時の荷重を銅配線層の接
着強度として評価した。Using the glass-ceramic wiring board for evaluation thus obtained, a copper wiring layer of 2 mm square was formed to a thickness of 2.5.
Ni plating of μm is applied, and A of 0.1 μm thickness is applied
After u-plating, a Cu-based lead wire is soldered on the plated coating layer in parallel with the surface of the copper wiring layer, and the solder wetted portion at that time is visually inspected to determine whether the solder wettability is good or not. The wire is bent perpendicularly to the surface of the copper wiring layer, and the lead wire is bent at 10 mm / min. The load when the lead wire was peeled off was evaluated as the adhesive strength of the copper wiring layer.
【００４５】また、ガラスセラミック配線基板の反り
は、縦５０ｍｍ、横２０ｍｍの銅配線層部分の変形量を
計測し、該変形値を相対反りとして評価した。The warp of the glass-ceramic wiring board was evaluated by measuring the amount of deformation of a copper wiring layer portion having a length of 50 mm and a width of 20 mm and evaluating the deformation value as a relative warp.
【００４６】[0046]
【表４】 [Table 4]
【００４７】[0047]
【表５】 [Table 5]
【００４８】表４及び表５から明らかなように、銅メタ
ライズ組成物に含有される金属酸化物の量が０．１重量
部未満の試料番号１、３８、５２では、半田濡れ性も良
好であり相対反りも小さいものの、接着強度が２．３ｋ
ｇ／２ｍｍ角以下と弱く、逆に５．０重量部を越える試
料番号８、４３、５７は、相対反りは小さいものの、半
田濡れ性が悪く、簡単にリード線が剥がれてしまい接着
強度測定ができなかった。As is clear from Tables 4 and 5, Sample Nos. 1, 38 and 52 in which the amount of metal oxide contained in the copper metallized composition was less than 0.1 part by weight showed good solder wettability. Although the relative warp is small, the adhesive strength is 2.3k
Sample Nos. 8, 43 and 57, which are weaker than g / 2 mm square and more than 5.0 parts by weight, have small relative warpage, but poor solder wettability and lead wires are easily peeled off to measure adhesive strength. could not.
【００４９】また、銅メタライズ組成物に含有される無
機物の量が０．１重量部未満の試料番号９、１６、３
２、４４では、相対反りが０．５４ｍｍ以上と大であ
り、５．０重量部を越える試料番号１５、２１、３５、
４７は相対反りが０．５８ｍｍ以上と大きく、接着強度
は１．５ｋｇ／２ｍｍ角以下と極めて弱くなっている。Further, sample numbers 9, 16, and 3 in which the amount of the inorganic substance contained in the copper metallized composition was less than 0.1 part by weight.
In Nos. 2 and 44, the relative warpage is as large as 0.54 mm or more, and the sample numbers 15, 21, 35, which exceed 5.0 parts by weight,
No. 47 has a large relative warp of 0.58 mm or more and an adhesive strength of 1.5 kg / 2 mm square or less, which is extremely weak.
【００５０】それらに対して、本発明ではいずれも半田
濡れ性が良好で接着強度も３．１ｋｇ／２ｍｍ角以上と
高く、相対反りも０．４６ｍｍ以下と小さくなってい
る。On the other hand, in the present invention, the solder wettability is good, the adhesive strength is as high as 3.1 kg / 2 mm square or more, and the relative warp is as small as 0.46 mm or less.
【００５１】[0051]
【発明の効果】以上、詳述したように、本発明の銅メタ
ライズ組成物及びそれを用いたガラスセラミック配線基
板は、銅メタライズ組成物が、ガラスセラミック磁器中
のガラス成分と反応し、該ガラス成分の粘性を低下させ
得る金属酸化物、即ち、アルカリ金属、アルカリ土類金
属、及びＢの内の少なくとも１種の酸化物を含有し、更
にＣｕの焼結を遅らせ得る無機物も含有することから、
銅メタライズ組成物の収縮開始温度がガラスセラミック
磁器の収縮開始温度に近づき、８００〜１１００℃の温
度で同時焼成してもガラス成分が銅配線層表面に浮いて
残存することがなく、しかもガラスセラミックスが液相
を生成する温度で、銅メタライズ組成物もほぼ同時に液
相を生成し、両者の収縮も同時に開始されて最終的に絶
縁基体の反りやうねり等の変形が極めて小さくなると共
に、ガラスセラミック磁器中のガラス成分が銅粒子間に
浸透し、その結果、銅配線層の接着強度を高く維持した
ガラスセラミック配線基板を得ることができる。As described above in detail, in the copper metallized composition of the present invention and the glass ceramic wiring board using the same, the copper metallized composition reacts with the glass component in the glass ceramic porcelain, Since it contains a metal oxide that can reduce the viscosity of the component, that is, at least one oxide of alkali metal, alkaline earth metal, and B, and also contains an inorganic substance that can delay the sintering of Cu. ,
The shrinkage start temperature of the copper metallized composition approaches the shrinkage start temperature of the glass ceramic porcelain, and even if co-firing at a temperature of 800 to 1100 ° C., the glass component does not float and remain on the surface of the copper wiring layer, and the glass ceramics At the temperature at which the liquid phase is formed, the copper metallization composition also forms the liquid phase almost at the same time, and the contraction of both is started at the same time, and finally the deformation such as warpage or waviness of the insulating substrate becomes extremely small, and the glass ceramic The glass component in the porcelain penetrates between the copper particles, and as a result, it is possible to obtain a glass ceramic wiring board in which the adhesive strength of the copper wiring layer is maintained high.
Claims (4)
ック磁器と同時焼成可能な銅を主成分とする銅メタライ
ズ組成物において、該銅メタライズ組成物中に、前記同
時焼成時にガラスセラミック磁器中のガラス成分の粘性
を低下させ得る金属酸化物として、アルカリ金属、アル
カリ土類金属、及びホウ素（Ｂ）の少なくとも１種の酸
化物を前記銅（Ｃｕ）１００重量部に対して０．１〜
５．０重量部と、前記銅（Ｃｕ）の焼結を遅らせ得る無
機物を０．１〜５．０重量部含有することを特徴とする
銅メタライズ組成物。1. A copper metallization composition containing copper as a main component, which can be co-fired with a glass ceramic porcelain at a temperature of 800 to 1100 ° C., in which the glass in the glass ceramic porcelain at the time of the co-firing is provided. As a metal oxide capable of reducing the viscosity of the component, at least one oxide of an alkali metal, an alkaline earth metal, and boron (B) is used in an amount of 0.1 to 100 parts by weight of the copper (Cu).
A copper metallization composition comprising 5.0 parts by weight and 0.1 to 5.0 parts by weight of an inorganic substance capable of delaying the sintering of the copper (Cu).
が、少なくともシリカ（ＳｉＯ2 ）、アルミナ（Ａｌ2
Ｏ3 ）、アルカリ土類金属の酸化物及び酸化ホウ素（Ｂ
2 Ｏ3 ）を含有するとともに、前記金属酸化物がカルシ
ア（ＣａＯ）であり、かつ前記無機物がアルミナ（Ａｌ
2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（Ｚｒ
Ｏ2 ）の内の少なくとも１種であることを特徴とする請
求項１記載の銅メタライズ組成物。2. The glass component in the glass ceramic porcelain is at least silica (SiO 2 ), alumina (Al 2
O 3 ), oxides of alkaline earth metals and boron oxide (B
2 O 3 ), the metal oxide is calcia (CaO), and the inorganic substance is alumina (Al).
2 O 3 ), silica (SiO 2 ), zirconia (Zr
The copper metallization composition according to claim 1, which is at least one of O 2 ).
度を低下させ得る金属酸化物として、アルカリ金属、ア
ルカリ土類金属、及びホウ素（Ｂ）の少なくとも１種の
酸化物を銅（Ｃｕ）１００重量部に対して０．１〜５．
０重量部と、前記銅（Ｃｕ）の焼結を遅らせ得る無機物
を０．１〜５．０重量部含有した銅メタライズ組成物
を、窒素雰囲気中、８００〜１１００℃の温度でガラス
セラミック磁器と同時焼成して形成した銅配線層を有す
るガラスセラミック配線基板。3. As a metal oxide capable of decreasing the viscosity of a glass component in a glass ceramic porcelain, at least one oxide of alkali metal, alkaline earth metal and boron (B) is added to 100 weight of copper (Cu). 0.1-5.
0 parts by weight and a copper metallizing composition containing 0.1 to 5.0 parts by weight of an inorganic substance capable of delaying the sintering of copper (Cu) in a nitrogen atmosphere at a temperature of 800 to 1100 ° C. and a glass ceramic porcelain. A glass-ceramic wiring board having a copper wiring layer formed by simultaneous firing.
が、少なくともシリカ（ＳｉＯ2 ）、アルミナ（Ａｌ2
Ｏ3 ）、アルカリ土類金属の酸化物及び酸化ホウ素（Ｂ
2 Ｏ3 ）を含有するとともに、前記金属酸化物がカルシ
ア（ＣａＯ）であり、かつ前記無機物がアルミナ（Ａｌ
2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（Ｚｒ
Ｏ2 ）の内の少なくとも１種であることを特徴とする請
求項３記載のガラスセラミック配線基板。4. The glass component in the glass ceramic porcelain is at least silica (SiO 2 ), alumina (Al 2
O 3 ), oxides of alkaline earth metals and boron oxide (B
2 O 3 ), the metal oxide is calcia (CaO), and the inorganic substance is alumina (Al).
2 O 3 ), silica (SiO 2 ), zirconia (Zr
The glass-ceramic wiring board according to claim 3, which is at least one of O 2 ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10713696A JP3420426B2 (en) | 1996-04-26 | 1996-04-26 | Copper metallized composition and glass-ceramic wiring board using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10713696A JP3420426B2 (en) | 1996-04-26 | 1996-04-26 | Copper metallized composition and glass-ceramic wiring board using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09295883A JPH09295883A (en) | 1997-11-18 |
| JP3420426B2 true JP3420426B2 (en) | 2003-06-23 |
Family
ID=14451428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10713696A Expired - Fee Related JP3420426B2 (en) | 1996-04-26 | 1996-04-26 | Copper metallized composition and glass-ceramic wiring board using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3420426B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3517062B2 (en) | 1996-09-20 | 2004-04-05 | 京セラ株式会社 | Copper metallized composition and glass-ceramic wiring board using the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3785903B2 (en) * | 2000-07-21 | 2006-06-14 | 株式会社村田製作所 | Multilayer substrate and manufacturing method thereof |
| US7569162B2 (en) | 2003-11-14 | 2009-08-04 | Murata Manufacturing Co., Ltd. | Electrically conductive paste and multilayer ceramic substrate |
-
1996
- 1996-04-26 JP JP10713696A patent/JP3420426B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3517062B2 (en) | 1996-09-20 | 2004-04-05 | 京セラ株式会社 | Copper metallized composition and glass-ceramic wiring board using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09295883A (en) | 1997-11-18 |
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