JP5013239B2 - High strength low temperature fired ceramic composition and multilayer electronic component using the same - Google Patents
High strength low temperature fired ceramic composition and multilayer electronic component using the same Download PDFInfo
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Description
本発明は、積層回路基板用の高強度低温焼成セラミック組成物に関し、特に機械的強度が高く、銀、金、銅等の低融点金属からなる電極との同時焼成が可能な高強度低温焼成セラミック組成物、及びその製造方法、並びにこれを用いた主に携帯電話等に使用する積層電子部品に関する。 The present invention relates to a high-strength low-temperature fired ceramic composition for a multilayer circuit board, and in particular, a high-strength low-temperature fired ceramic that has high mechanical strength and can be fired simultaneously with an electrode made of a low-melting-point metal such as silver, gold, or copper. The present invention relates to a composition, a production method thereof, and a laminated electronic component mainly used for a mobile phone or the like using the composition.
従来からＩＣ等の半導体素子や各種電子部品を搭載し、内層回路を配したセラミック積層回路基板が知られている。このような積層回路基板には、これまで放熱性、電気的特性、機械的強度等が総合的に優れたアルミナ基板が用いられて来た。アルミナ基板は焼成温度が１３００〜１６００℃と高いため、電極材料にはＷ，Ｍｏ等の高融点金属が使用されている。しかし、これらの電極材料は電気抵抗率が高く、携帯電話等の数百ＭＨｚを超える高周波回路では信号の伝送損失の増大を招く問題があった。
携帯電話等の移動体通信分野においては、特に、信号の伝送損失が小さいことが求められている。このため、Ｗ，Ｍｏ等の高融点金属の代わりに、電気抵抗率の小さい銀、金、銅等の電極材料が用いられるようになり、またセラミック積層回路基板には、前記電極材料と同時焼成が可能なガラスセラミックスや、低温焼成セラミック組成物が多く使用されるようになった（特許文献１）。
2. Description of the Related Art Conventionally, there has been known a ceramic laminated circuit board on which a semiconductor element such as an IC and various electronic components are mounted and an inner layer circuit is arranged. For such a laminated circuit board, an alumina board having excellent heat dissipation, electrical characteristics, mechanical strength and the like has been used so far. Since the firing temperature of the alumina substrate is as high as 1300 to 1600 ° C., a high melting point metal such as W or Mo is used as the electrode material. However, these electrode materials have high electrical resistivity, and there has been a problem in that signal transmission loss increases in a high-frequency circuit exceeding several hundred MHz such as a cellular phone.
In the field of mobile communication such as cellular phones, it is particularly required that signal transmission loss be small. For this reason, instead of refractory metals such as W and Mo, electrode materials such as silver, gold, and copper having a low electrical resistivity have been used, and ceramic laminated circuit boards are simultaneously fired with the electrode materials. Many glass ceramics and low-temperature fired ceramic compositions that can be used have been used (Patent Document 1).
しかしながら、前記積層回路基板は、アルミナ基板に比べて機械的強度が著しく劣っていた。例えばアルミナ基板の抗折強度は４００ＭＰａ程度であるが、前記積層回路基板の抗折強度は２００ＭＰａ程度である。従来の携帯電話等では積層回路基板の抗折強度が１５０ＭＰａ以上あれば実用的に十分であったが、携帯電話等に用いる電子部品の薄型化にともない、その中に用いられる積層回路基板も１ｍｍ以下にまで薄型化している。このように携帯電話等に用いる積層回路基板には、例えば、実装基板のねじれや曲がり等の変形や、落下時の衝撃に対して、クラックや破損が生じないような高強度が求められ、従来のセラミック積層回路基板では機械的強度が不十分となる場合があった。
本発明者らは、低温焼成セラミック組成物からなる積層回路基板の機械的強度を向上させるために、前記特許文献１に開示された低温焼成セラミック組成物を基にして、種々の検討を行った。その内、低温焼成セラミック組成物を構成する結晶相に着目し、焼成温度を変えて析出する結晶相を変えた試験片を作成して機械的強度を評価したところ、組織中に六方晶結晶を有するものが、他の結晶相のみで構成されるものより、相対的に高強度であることを知見した。
しかしながら、六方晶結晶を析出させるためには焼成温度を下げることが必要となり、ＡｇやＣｕとの同時同時焼成が困難となる場合があった。
従って本発明の目的は、低融点金属との同時焼成が可能であり、クラックや破損が生じにくい回路基板を形成し得る高強度の低温焼成セラミック組成物を提供することである。
本発明のさらにもう一つの目的は、かかる低温焼成セラミック組成物からなる誘電体層を有する積層電子部品を提供することである。
In order to improve the mechanical strength of a multilayer circuit board made of a low-temperature fired ceramic composition, the present inventors have made various studies based on the low-temperature fired ceramic composition disclosed in
However, in order to precipitate hexagonal crystals, it is necessary to lower the firing temperature, and simultaneous firing with Ag or Cu may be difficult.
Accordingly, an object of the present invention is to provide a high-strength, low-temperature fired ceramic composition that can form a circuit board that can be fired simultaneously with a low-melting-point metal and is less susceptible to cracks and breakage.
Still another object of the present invention is to provide a multilayer electronic component having a dielectric layer made of such a low-temperature fired ceramic composition.
第１の発明は、高強度低温焼成セラミック基板用のセラミック組成物であって、少なくとも主成分としてＡｌ、Ｓｉ、Ｓｒ、Ｂａを含み、Ａｌ ２ Ｏ ３ 、ＳｉＯ ２ 、ＳｒＣＯ ３ 、ＢａＣＯ ３ と、Ｂｉ ２ Ｏ ３ とを混合して仮焼し、Ａｌ２Ｏ３結晶を有するガラス粉末とした仮焼粉とし、前記仮焼粉より得られた成形体を、前記仮焼の温度よりも高温であり８２５℃〜９２０℃の温度で焼成して、組織中に六方晶Ａｌ２Ｏ３結晶とともに六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８ を形成するセラミック組成物である。
組織中に六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８ 、ＢａＡｌ２Ｓｉ２Ｏ８少なくとも一種を有する場合、組成物の抗折強度は３００ＭＰａ以上となるが、組織中に六方晶を有さず、ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８結晶が単斜晶および斜方晶であると、強度は１５０ＭＰａ程度に低下してしまう。六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８と単斜晶、斜方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８とで、機械的強度に著しい差がある理由は明らかではないが、主結晶相であるＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８結晶がＡｌ２Ｏ３結晶と同じ六方晶系として存在することにより、両結晶相の結び付きが強化され、機械的強度が高まるためであると考えられる。
低温焼成セラミック組成物を六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８の少なくとも一種とＡｌ２Ｏ３結晶が混在する組織とすることにより、電子部品に用いるのに必要な比誘電率、１．５ＴＨｚを超える実用的なｆＱ等の誘電特性を確保しながら、機械的強度を向上することが出来る。
A first invention is a ceramic composition for a high-strength, low-temperature fired ceramic substrate, comprising at least Al, Si, Sr, Ba as main components, Al 2 O 3 , SiO 2 , SrCO 3 , BaCO 3 , Bi 2 O 3 is mixed and calcined to obtain a calcined powder made of glass powder having Al 2 O 3 crystals, and a molded body obtained from the calcined powder is heated at a temperature higher than the calcining temperature. There was fired at a temperature of 825 ℃ ~920 ℃, hexagonal with hexagonal Al 2 O 3 crystals in tissues crystal SrAl 2 Si 2 O 8, a (Sr, Ba) Al 2 Si2O 8,
When the structure has at least one kind of hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O 8 , the bending strength of the composition is 300 MPa or more. If the SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 crystals are monoclinic and orthorhombic, the strength is 150 MPa. It will drop to the extent. Hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O 8 and monoclinic, orthorhombic SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si The reason why there is a significant difference in mechanical strength between 2 O 8 and BaAl 2 Si 2 O 8 is not clear, but SrAl 2 Si 2 O 8 and (Sr, Ba) Al 2 Si 2 O which are main crystal phases 8 and the presence of BaAl 2 Si 2 O 8 crystal as the same hexagonal system as Al 2 O 3 crystal is considered to strengthen the bond between both crystal phases and increase the mechanical strength.
By making the low-temperature fired ceramic composition a structure in which at least one of hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 and Al 2 O 3 crystals are mixed. The mechanical strength can be improved while ensuring the relative dielectric constant necessary for use in electronic parts and practical dielectric properties such as practical fQ exceeding 1.5 THz.
第１の発明のおいては、更に単斜晶及び斜方晶のＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８を有していても良い。さらに前記六方晶Ａｌ２Ｏ３結晶粒の平均結晶粒径を１μｍ以下とするのも好ましい。
第１の発明のセラミック組成物においては、１０〜６０質量％（Ａｌ ２ Ｏ ３ 換算）のＡｌと、２５〜６０質量％（ＳｉＯ ２ 換算）のＳｉと、７．５〜５０質量％（ＳｒＯ換算）のＳｒと、３．０〜５０質量％（ＢａＯ換算）のＢａとを主成分とし、前記主成分１００質量％に対して、０．１〜１０質量％（Ｂｉ ２ Ｏ ３ 換算）のＢｉと、０．１〜５質量％（ＣｏＯ換算）のＣｏからなる群から選ばれた少なくとも１種と、０．０１〜５質量％（ＣｕＯ換算）のＣｕと、０．０１〜５質量％（ＭｎＯ ２ 換算）のＭｎと、０．０１〜５質量％のＡｇと、０．０１〜２質量％（ＺｒＯ ２ 換算）のＺｒとからなる群から選ばれた少なくとも１種とを、副成分として含有するのが好ましい。
副成分として、更に２０質量％以下（ＴｉＯ ２ 換算）のＴｉや０．１〜５質量％（Ｂ ２ Ｏ ３ 換算）のＢを含むのも好ましい。
In the first invention, monoclinic and orthorhombic SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 may be further included. . Furthermore, it is also preferable that the average crystal grain size of the hexagonal Al 2 O 3 crystal grains is 1 μm or less.
In the ceramic composition of the first invention, the Al of 10 to 60 wt% (Al 2 O 3 basis), and Si 25-60 wt% (SiO 2 basis) of from 7.5 to 50 mass% ( SrO equivalent) and 3.0-50 mass% (BaO equivalent) Ba are the main components, and 0.1-10 mass% (Bi 2 O 3 equivalent) with respect to 100 mass% of the main ingredient. Bi, at least one selected from the group consisting of 0.1 to 5 mass% (CoO equivalent) Co, 0.01 to 5 mass% (CuO equivalent) Cu, and 0.01 to 5 mass % (MnO 2 equivalent) of Mn, 0.01 to 5% by mass of Ag, and 0.01 to 2 % by mass (ZrO 2 equivalent) of Zr. It is preferable to contain as a component.
It is preferable to further contain 20% by mass or less (in terms of TiO 2 ) Ti and 0.1 to 5% by mass (in terms of B 2 O 3 ) as subcomponents .
第２の発明は、第１の発明の高強度低温焼成セラミック組成物で構成され、積層体として構成された成形体と、前記積層体に形成された低融点金属からなる導体パターンとを同時焼成した積層電子部品である。第２の発明の積層電子部品においては、前記低融点金属が銀、銅、金又はこれらの合金とするのが好ましい。前記導体パターンはインダクタンス素子及び／又はキャパシタンス素子を構成する。さらに、前記積層電子部品にインダクタンス素子、キャパシタンス素子、スイッチング素子及びフィルタ素子からなる群から選ばれた少なくとも１つを実装するのも好ましい。 2nd invention is comprised by the high intensity | strength low-temperature baking ceramic composition of 1st invention, and simultaneously bakes the molded object comprised as a laminated body, and the conductor pattern which consists of a low melting-point metal formed in the said laminated body. a laminated electronic components. In the laminated electronic component of the second invention, the low melting point metal is preferably silver, copper, gold or an alloy thereof. The conductor pattern constitutes an inductance element and / or a capacitance element. Furthermore, it is preferable that at least one selected from the group consisting of an inductance element, a capacitance element, a switching element and a filter element is mounted on the multilayer electronic component.
本発明の低温焼成セラミック組成物は、組織中に六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８の少なくとも一種を有するので、高強度で実用的な誘電特性を有し、かつ１０００℃以下の低温での焼成が可能である。そのため、銀、金、銅等の低融点電極材料との同時焼成が可能である。また本発明の高強度低温焼成セラミック組成物は、誘電率、ｆＱ等の誘電特性に優れているのみならず、従来より向上した機械的強度を有するので、積層回路基板とするときに低融点金属との同時焼成が可能であり、またクラックや破損が生じにくい。そのため、本発明の高強度低温焼成セラミック組成物を用いた積層電子部品は、優れた電気的特性及び機械的強度を有する。 The low-temperature fired ceramic composition of the present invention has at least one of hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 in the structure. It has practical dielectric properties and can be fired at a low temperature of 1000 ° C. or lower. Therefore, simultaneous firing with a low melting point electrode material such as silver, gold, or copper is possible. The high-strength low-temperature fired ceramic composition of the present invention not only has excellent dielectric properties such as dielectric constant and fQ, but also has improved mechanical strength as compared with the conventional low-melting point metal when used as a laminated circuit board. Can be fired at the same time, and cracks and breakage are less likely to occur. Therefore, the multilayer electronic component using the high-strength low-temperature fired ceramic composition of the present invention has excellent electrical characteristics and mechanical strength.
本発明の高強度低温焼成セラミック組成物の主成分は、Ａｌ，Ｓｉ、Ｓｒ、Ｂａを含み、１０５０℃以下、好ましくは１０００℃以下の温度で焼成し、組織中に少なくとも六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８の少なくとも一種及びＡｌ２Ｏ３結晶粒を有する。Ｂａを添加することで、六方晶結晶が析出する温度を上昇させることが出来るので、このような低温焼成セラミック組成物からなる誘電体層上に高導電率を有する低融点金属（銀、銅、金又はこれらの合金）からなる内部電極を形成し、積層後に焼成することにより一体化すると、機械的強度に優れ、高いＱ値により極めて損失の小さい高周波電子部品を形成することができる。このため、誘電体共振器、フィルタ、積層インダクタ又は積層コンデンサ、及びこれらを複合化した高周波積層基板等に応用して、機械的強度、マイクロ波特性に優れ、低損失な回路デバイスが得られる。 The main component of the high-strength low-temperature fired ceramic composition of the present invention contains Al, Si, Sr, and Ba, fired at a temperature of 1050 ° C. or lower, preferably 1000 ° C. or lower, and at least hexagonal SrAl 2 Si 2 in the structure. It has at least one of O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O 8 and Al 2 O 3 crystal grains. By adding Ba, the temperature at which the hexagonal crystal is precipitated can be increased. Therefore, a low-melting-point metal (silver, copper, etc.) having high conductivity on the dielectric layer made of such a low-temperature fired ceramic composition. When an internal electrode made of gold or an alloy thereof is formed and integrated by firing after lamination, a high-frequency electronic component having excellent mechanical strength and extremely low loss can be formed with a high Q value. For this reason, it can be applied to dielectric resonators, filters, multilayer inductors or multilayer capacitors, and high-frequency multilayer substrates obtained by combining these, and a circuit device having excellent mechanical strength and microwave characteristics and low loss can be obtained. .
ＡｌはＡｌ２Ｏ３換算で１０〜６０質量％とするのが好ましく、ＳｉはＳｉＯ２換算で２５〜６０質量％とするのが好ましく、ＳｒはＳｒＯ換算で７．５〜５０質量％とするのが好ましく、ＢａはＢａＯ換算で３．０〜５０質量％とするのが好ましい。これらの金属の含有量がこれらの範囲外であると、１０００℃以下の低温焼成では十分な焼成密度が得られないために、低温焼成セラミック組成物は多孔質となり、吸湿等により良好な特性が得られない。 Al is preferably 10 to 60% by mass in terms of Al 2 O 3 , Si is preferably 25 to 60% by mass in terms of SiO 2 , and Sr is 7.5 to 50% by mass in terms of SrO. It is preferable that Ba is 3.0 to 50% by mass in terms of BaO. If the content of these metals is outside these ranges, sufficient firing density cannot be obtained by firing at a low temperature of 1000 ° C. or lower, so that the low-temperature fired ceramic composition becomes porous and has good characteristics due to moisture absorption and the like. I can't get it.
また、この低温焼成セラミック組成物に更に、副成分として、Ｂｉ、Ｃｏからなる群から選ばれた少なくとも１種、及びＣｕ、Ｍｎ、Ａｇ及びＺｒからなる群から選ばれた少なくとも１種を含有させるのが好ましい。またＢ、Ｔｉを含有させるのも好ましい。
これらの金属の添加量は、特に断りがない限り、主成分の合計１００質量％に対して、酸化物換算値で示す。これらの金属は酸化物又は炭酸塩の状態で添加するのが好ましい。
Further, the low-temperature fired ceramic composition further contains at least one selected from the group consisting of Bi and Co and at least one selected from the group consisting of Cu, Mn, Ag and Zr as subcomponents. Is preferred. It is also preferable to contain B and Ti.
Unless otherwise specified, the addition amount of these metals is shown as an oxide conversion value with respect to a total of 100% by mass of the main components. These metals are preferably added in the form of oxides or carbonates.
Ｂｉ、Ｃｏは、仮焼工程においてＡｌ２Ｏ３以外の成分がガラス化する際、得られるガラスの軟化点を低下させる作用を有するので、より低温での焼成を可能にし、１０００℃以下の焼成温度でもＱ値の高い誘電特性を有する低温焼成セラミックを得ることを可能にする。ここで低温での焼成を可能にするとは、ガラス相が低融点化することであり、六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８の結晶化を高める効果がある。 Bi and Co have the effect of lowering the softening point of the resulting glass when components other than Al 2 O 3 are vitrified in the calcination step, thus enabling firing at a lower temperature and firing at 1000 ° C. or less. This makes it possible to obtain a low-temperature fired ceramic having a dielectric property having a high Q value even at a temperature. Here, to enable firing at a low temperature is to lower the melting point of the glass phase, and hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O 8. This has the effect of increasing the crystallization.
Ｂｉは、Ｂｉ２Ｏ３換算で０．１〜１０質量％とするのが好ましい。Ｂｉが１０質量％より多いと、Ｑ値が小さくなる。Ｂｉのより好ましい添加量は５質量％以下である。またＢｉの添加量が０．１質量％より少ないと、焼成温度の低下効果が不十分である。Ｂｉのより好ましい添加量は０．２質量％以上である。 Bi is preferably 0.1 to 10% by mass in terms of Bi 2 O 3 . When Bi is more than 10% by mass, the Q value becomes small. A more preferable addition amount of Bi is 5% by mass or less. On the other hand, if the amount of Bi added is less than 0.1% by mass, the effect of lowering the firing temperature is insufficient. A more preferable addition amount of Bi is 0.2% by mass or more.
Ｃｏは、ＣｏＯ換算で０．１〜５質量％とするのが好ましい。Ｃｏが０．１質量％未満の場合、焼成温度の低下効果が不十分であり、９００℃以下の焼成で緻密な低温焼成セラミック組成物を得ることが困難である。またＣｏが５質量％を超えると、低温焼成セラミック組成物の結晶化温度が１０００℃超となり、１０００℃以下で誘電損失が大きくなり過ぎ、実用性が無くなる。 Co is preferably 0.1 to 5% by mass in terms of CoO. When Co is less than 0.1% by mass, the effect of lowering the firing temperature is insufficient, and it is difficult to obtain a dense low-temperature fired ceramic composition by firing at 900 ° C. or lower. On the other hand, when Co exceeds 5 mass%, the crystallization temperature of the low-temperature fired ceramic composition exceeds 1000 ° C., and the dielectric loss becomes too large at 1000 ° C. or less, so that the practicality is lost.
Ｃｕ，Ｍｎ，Ａｇ，Ｂ及びＺｒは、主に焼成工程において誘電体セラミック組成物の結晶化を促進する作用があり、１０５０℃以下での低温焼成を達成するために添加する。 Cu, Mn, Ag, B and Zr mainly act to promote crystallization of the dielectric ceramic composition in the firing step, and are added to achieve low temperature firing at 1050 ° C. or lower.
Ｃｕは、ＣｕＯ換算で０．０１〜５質量％とするのが好ましい。Ｃｕが０．０１質量％未満の場合、その添加効果は小さく、９００℃以下での焼成でＱ値の高い低温焼成セラミック組成物を得ることが困難である。またＣｕが５質量％を超えると、低温焼成性が損なわれる。 Cu is preferably 0.01 to 5% by mass in terms of CuO. When Cu is less than 0.01% by mass, the effect of addition is small, and it is difficult to obtain a low-temperature fired ceramic composition having a high Q value by firing at 900 ° C. or lower. Moreover, when Cu exceeds 5 mass%, low-temperature baking property will be impaired.
Ｍｎは、ＭｎＯ２換算で０．０１〜５質量％とするのが好ましい。Ｍｎが０．０１質量％未満の場合、その添加効果は小さく、９００℃以下での焼成でＱ値の高い低温焼成セラミック組成物を得ることが困難である。またＭｎが５質量％を超えると、低温焼成性が損なわれる。 Mn is preferably 0.01 to 5% by mass in terms of MnO 2 . When Mn is less than 0.01% by mass, the effect of addition is small and it is difficult to obtain a low-temperature fired ceramic composition having a high Q value by firing at 900 ° C. or lower. On the other hand, if Mn exceeds 5% by mass, the low-temperature calcinability is impaired.
Ａｇは、０．０１〜５質量％とするのが好ましい。Ａｇが５質量％を超えると、誘電損失が大きくなり過ぎ、実用性がない。Ａｇのより好ましい添加量は２質量％以下である。 Ag is preferably 0.01 to 5% by mass. When Ag exceeds 5% by mass, the dielectric loss becomes too large, which is not practical. A more preferable addition amount of Ag is 2% by mass or less.
ＺｒはＺｒＯ２換算で０．０１〜２質量％とするのが好ましい。Ｚｒが０．０１質量％未満では、低温焼成セラミックの機械的強度の向上効果が不十分であり、また２質量％を超えると、ｆＱが低下する。ＺｒＯ２添加による機械的強度の向上効果をより期待するためには、０．３質量％〜１．５質量％とするのがより好ましい。
Ｔｉは低温焼成セラミックの共振周波数の温度係数τｆを増加させる作用を有する。Ｔｉは、ＴｉＯ ２ 換算で０〜２０質量％とするのが好ましい。Ｔｉの含有量が増加するとともに低温焼成セラミックの共振周波数の温度係数は増大する。低温焼成セラミックの共振周波数の温度係数τｆが−２０〜−４０ｐｐｍ／℃程度のマイナス側にある場合、Ｔｉの含有量を多くしてτｆを０ｐｐｍ／℃に容易に調整することができる。しかしながら、Ｔｉの添加量がＴｉＯ ２ 換算で２０質量％より多いと、１０００℃以下の低温焼成では十分な焼成密度が得られないために、低温焼成セラミックが多孔質となり、吸湿等により良好な特性が得られない。
Ｂは０．５〜５質量％とするのが好ましい。Ｂを添加する事により、添加しないものに比べて六方晶ＳｒＡｌ ２ Ｓｉ ２ Ｏ ８ 、（Ｓｒ、Ｂａ）Ａｌ ２ Ｓｉ ２ Ｏ ８ 、ＢａＡｌ ２ Ｓｉ ２ Ｏ ８ の少なくとも一種が析出する温度域が広域化する。Ｂを５質量％以上にするとバインダーのポリビニルブチラールと反応してゲル化し、シート成形性が悪くなる。また、０．５質量％以下にすると誘電特性が劣化し、ｆＱが低下する。
Zr is preferably 0.01 to 2 % by mass in terms of ZrO 2 . If Zr is less than 0.01% by mass, the effect of improving the mechanical strength of the low-temperature fired ceramic is insufficient, and if it exceeds 2% by mass, fQ decreases. In order to further expect the effect of improving the mechanical strength due to the addition of ZrO 2, the content is more preferably 0.3% by mass to 1.5% by mass.
Ti has the effect of increasing the temperature coefficient τf of the resonance frequency of the low-temperature fired ceramic. Ti is preferably 0 to 20% by mass in terms of TiO 2 . As the Ti content increases, the temperature coefficient of the resonance frequency of the low-temperature fired ceramic increases. When the temperature coefficient τf of the resonance frequency of the low-temperature fired ceramic is on the minus side of about −20 to −40 ppm / ° C., the content of Ti can be increased and τf can be easily adjusted to 0 ppm / ° C. However, if the addition amount of Ti is more than 20% by mass in terms of TiO 2 , sufficient firing density cannot be obtained by low-temperature firing at 1000 ° C. or lower, so that the low-temperature fired ceramic becomes porous and has better characteristics due to moisture absorption and the like. Cannot be obtained.
B is preferably 0.5 to 5% by mass. By adding B, the temperature range in which at least one of hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 precipitates is wider than that in which B is not added. Turn into. When B is 5% by mass or more, it reacts with the binder polyvinyl butyral to form a gel, resulting in poor sheet formability. On the other hand, when the content is 0.5% by mass or less, the dielectric characteristics are deteriorated and the fQ is lowered.
不可避的不純物としては、例えばＹ，Ｆｅ，Ｃａ，Ｇａ，Ｃｒ等が挙げられる。不可避的不純物の含有量は、低温焼成セラミック組成物の特性を劣化させない範囲内としなければならない。
このような方法により得られる本発明の低温焼成セラミック組成物は、さらに６〜９程度の比誘電率ε、及び実用的な３０００ＧＨｚ（３ＴＨｚ）以上のｆＱ（ｆは共振周波数）を有するのが好ましい。
Inevitable impurities include, for example, Y, Fe, Ca, Ga, Cr and the like. The content of inevitable impurities must be within a range that does not deteriorate the properties of the low-temperature fired ceramic composition.
The low-temperature fired ceramic composition of the present invention obtained by such a method preferably further has a relative dielectric constant ε of about 6 to 9 and a practical fQ of 3000 GHz (3 THz) or higher (f is a resonance frequency). .
本発明の積層電子部品は、上記低温焼成セラミック組成物からなる各誘電体層に低融点金属（銀、銅、金又はこれらの合金）からなる導体パターンを形成し、得られた導体パターンを有する誘電体層を複数積層することにより得られる。導体パターン自体は公知のもので良く、例えばインダクタンス素子及び／又はキャパシタンス素子を構成する。積層電子部品には、インダクタンス素子、キャパシタンス素子、スイッチング素子及びフィルタ素子の少なくとも１つを実装しても良い。積層電子部品の層構成自体は公知のもので良い。
本発明を以下の実施例によりさらに詳細に説明するが、本発明はそれらに限定されるものではない。
The multilayer electronic component of the present invention has a conductor pattern obtained by forming a conductor pattern made of a low melting point metal (silver, copper, gold or an alloy thereof) on each dielectric layer made of the low-temperature fired ceramic composition. It is obtained by laminating a plurality of dielectric layers. The conductor pattern itself may be a known one, and constitutes, for example, an inductance element and / or a capacitance element. At least one of an inductance element, a capacitance element, a switching element, and a filter element may be mounted on the multilayer electronic component. The layer structure itself of the laminated electronic component may be a known one.
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
Ａｌ２Ｏ３粉末，ＳｉＯ２粉末，ＳｒＣＯ３粉末，ＢａＣＯ３粉末，ＴｉＯ２粉末，Ｂｉ２Ｏ３粉末，ＣｕＯ粉末，ＭｎＯ２粉末，Ｈ３ＢＯ３粉末をポリエチレン製のボールミルポットに投入し、酸化ジルコニウム製のボールと純水を投入して、２０時間湿式混合を行った。得られたスラリーを加熱乾燥した後、ライカイ機で解砕した。得られた混合粉末をアルミナ製のるつぼに入れて、７７５℃で２時間仮焼して、Ａｌ２Ｏ３結晶を含有するホウケイ酸塩系ガラス粉末とした。仮焼粉の組成は、酸化物換算で、３８．６質量％のＡｌ２Ｏ３、２７．８質量％のＳｉＯ２、１１．０質量％のＳｒＯ、１４．９質量％のＢａＣＯ３、３．１質量％のＴｉＯ２、１．９質量％のＢｉ２Ｏ３、０．２質量％のＣｕＯ、２．１質量％のＢ２Ｏ３及び０．４質量％のＭｎＯ２であった。
この仮焼粉を上記ボールミルで４０時間湿式粉砕した後、乾燥した。得られた乾燥仮焼粉の一部を純水と一緒にボールミルに投入し、平均粒径１．０μｍに粉砕した。得られた粉砕粉を含有するスラリーに、ポリビニルアルコール（ＰＶＡ）を粉砕粉１００質量％に対して１．５質量％の割合で添加した後、スプレードライヤーで造粒・乾燥し、平均粒径が約０．１ｍｍの顆粒状の造粒粉を得た。
この造粒粉を２００Ｍｐａの圧力で加圧成形し円柱状成形体を得た。この成形体を大気中で室温から８００〜１０００℃の温度まで２００℃／ｈｒの速度で加熱し、前記温度に２時間保持して焼成した後、室温まで２００℃／ｈｒの速度で冷却した。
得られた焼成体の比誘電率εを円柱共振器により８〜１５ＧＨｚの共振周波数で求めた。また上記と同様に作製した３８ｍｍ×１２ｍｍ×１ｍｍの試験片に対して、支点間距離を３０ｍｍとし、荷重速度を０．５ｍｍ／ｍｉｎそして３点曲げ試験（ＪＩＳ Ｃ２１４１）を行い、試験片が破壊したときの最大荷重から曲げ強さ（抗折強度）を求めた。
その結果、六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８少なくとも一種が析出する温度域が８２５℃〜９２０℃であり、前記温度域では７．２〜７．５の比誘電率及び１５〜１７ＴＨｚのｆＱと優れた誘電特性を示し、抗折強度は約３００ＭＰａ以上得られた。
Al 2 O 3 powder, SiO 2 powder, SrCO 3 powder, BaCO 3 powder, TiO 2 powder, Bi 2 O 3 powder, CuO powder, MnO 2 powder, H 3 BO 3 powder are put into a polyethylene ball mill pot, Zirconium oxide balls and pure water were added and wet mixing was performed for 20 hours. The obtained slurry was heat-dried and then crushed with a raikai machine. The obtained mixed powder was put into an alumina crucible and calcined at 775 ° C. for 2 hours to obtain a borosilicate glass powder containing Al 2 O 3 crystals. The composition of the calcined powder is 38.6 mass% Al 2 O 3 , 27.8 mass% SiO 2 , 11.0 mass% SrO, 14.9 mass% BaCO 3 , 3 in terms of oxide. 0.1% by weight TiO 2 , 1.9% by weight Bi 2 O 3 , 0.2% by weight CuO, 2.1% by weight B 2 O 3 and 0.4% by weight MnO 2 .
The calcined powder was wet pulverized for 40 hours by the ball mill and then dried. A part of the obtained dried calcined powder was put into a ball mill together with pure water and pulverized to an average particle size of 1.0 μm . After adding polyvinyl alcohol (PVA) to the slurry containing the pulverized powder at a ratio of 1.5% by mass with respect to 100% by mass of the pulverized powder, granulation and drying are performed with a spray dryer. A granulated granulated powder of about 0.1 mm was obtained.
This granulated powder was pressure-molded at a pressure of 200 MPa to obtain a cylindrical molded body. The molded body was heated in the atmosphere from room temperature to a temperature of 800 to 1000 ° C. at a rate of 200 ° C./hr, held at the temperature for 2 hours and fired, and then cooled to room temperature at a rate of 200 ° C./hr.
The relative dielectric constant ε of the obtained fired body was determined at a resonance frequency of 8 to 15 GHz using a cylindrical resonator. In addition, a 38 mm × 12 mm × 1 mm test piece produced in the same manner as described above was subjected to a three-point bending test (JIS C2141) with a distance between fulcrums of 30 mm, a load speed of 0.5 mm / min, and the test piece was destroyed. The bending strength (bending strength) was determined from the maximum load at the time.
As a result, the temperature range in which at least one hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 is precipitated is 825 ° C. to 920 ° C., A dielectric constant of 7.2 to 7.5 and fQ of 15 to 17 THz were exhibited and excellent dielectric properties were exhibited, and a bending strength of about 300 MPa or more was obtained.
Ｂを含まない以外は、実施例１と同様の手順で仮焼粉を得た。仮焼粉の組成は、酸化物換算で、３９．４質量％のＡｌ２Ｏ３、２８．４質量％のＳｉＯ２、１１．２質量％のＳｒＯ、１５．２質量％のＢａＣＯ３、３．２質量％のＴｉＯ２、２．０質量％のＢｉ２Ｏ３、０．２質量％のＣｕＯ及び０．４質量％のＭｎＯ２であった。
この仮焼粉を実施例１と同様の手順で造粒、成形し、８００〜１０００℃の温度で焼成して、誘電特性、抗折強度を評価した。その結果、８．０〜８．３の誘電率及び０．２５〜１１ＴＨｚのｆＱであり、六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８ 、ＢａＡｌ２Ｓｉ２Ｏ８少なくとも一種が析出する温度域は８７５℃〜約９００℃であった。
A calcined powder was obtained in the same procedure as in Example 1 except that B was not included. The composition of the calcined powder is 39.4% by mass of Al 2 O 3 , 28.4% by mass of SiO 2 , 11.2% by mass of SrO, 15.2% by mass of BaCO 3 , 3 in terms of oxide. 2% by weight TiO 2 , 2.0% by weight Bi 2 O 3 , 0.2% by weight CuO and 0.4% by weight MnO 2 .
This calcined powder was granulated and molded in the same procedure as in Example 1, and baked at a temperature of 800 to 1000 ° C. to evaluate dielectric properties and bending strength. As a result, the dielectric constant was 8.0 to 8.3 and the fQ was 0.25 to 11 THz, and hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O. 8 The temperature range in which at least one kind precipitated was 875 ° C. to about 900 ° C.
Ｂａを含まない以外は、実施例１と同様の手順で作成して得られた焼成体について、誘電特性、抗折強度を評価した。この場合には、六方晶ＳｒＡｌ２Ｓｉ２Ｏ８が析出するが、その析出温度は約８２５℃〜約８５０℃であり、低融点金属とともに焼結するには十分な焼成温度ではなかった。約８．０〜８．２の誘電率及びｆＱが約２ＧＨｚの誘電特性を示し、抗折強度は、４００ＭＰａであった。 Dielectric characteristics and bending strength were evaluated for the fired bodies obtained by the same procedure as in Example 1 except that Ba was not included. In this case, hexagonal SrAl 2 Si 2 O 8 is precipitated, but the precipitation temperature is about 825 ° C. to about 850 ° C., which is not a sufficient firing temperature for sintering together with the low melting point metal. The dielectric constant was about 8.0 to 8.2 and the dielectric property was about 2 GHz, and the bending strength was 400 MPa.
本発明の高強度低温焼成セラミック組成物を用いた積層電子部品の一例として、携帯電話の高周波回路部に用いるダイオードスイッチ（アンテナ側回路、受信側回路及び送信側回路の接続を切り替える）を以下の通り作製した。
まず、実施例１と同様にして、質量基準で３８．６質量％のＡｌ２Ｏ３、２７．8質量％のＳｉＯ２、１１．０質量％のＳｒＯ、１４．９質量％のＢａＣＯ３、３．1質量％のＴｉＯ２、１．９質量％のＢｉ２Ｏ３、０．2質量％のＣｕＯ、２．1質量％のＢ２Ｏ３及び０．4質量％のＭｎＯ２からなる仮焼粉を作製した。
この仮焼粉をエタノール及びブタノールの混合溶媒に分散させて、ボールミルで平均粒径１．０μｍまで粉砕した。得られたスラリーに、バインダーとしてポリビニルブチラール及び可塑剤としてブチルフタリルブチルグリコレートを、仮焼粉１００質量％に対してそれぞれ１５質量％及び７．５質量％の割合で分散させ、シート成形用のスラリーとした。減圧下で脱泡及び溶媒の部分的な蒸発を行ってこのスラリーの粘度を約１００００ＭＰａ・ｓにした後、ドクターブレードでシート成形し、約８０μｍの乾燥厚さを有する長尺のセラミックグリーンシートを得た。後工程のハンドリングのため、このセラミックグリーンシートを所定の大きさに裁断した。
複数枚のセラミックグリーンシートの表面に銀ペーストで伝送線路（インダクタンス素子）を構成する配線パターンＬ１−１，Ｌ１−２，Ｌ２−１，Ｌ２−２、グランド電極パターンＧＮＤ、及びスイッチング素子を実装するためのＡｇペーストを用いて電極パターンを印刷した（図１参照）。
セラミックグリーンシートには、各層間の配線パターンの接続手段として銀ペーストを充填したビアホールが形成されている。導電パターンを印刷した各セラミックグリーンシートを位置合わせし、高精度に積層した後圧着した。圧着条件は、１４ＭＰａの圧力、８５℃の温度、及び１０分の保持時間であった。
As an example of a multilayer electronic component using the high-strength low-temperature fired ceramic composition of the present invention, a diode switch (switching the connection between the antenna side circuit, the reception side circuit, and the transmission side circuit) used in a high-frequency circuit unit of a cellular phone is as follows: As prepared.
First, in the same manner as in Example 1, 38.6% by mass of Al 2 O 3 , 27.8% by mass of SiO 2 , 11.0% by mass of SrO, 14.9% by mass of BaCO 3 , 3.1 mass% of TiO 2, 1.9
The calcined powder was dispersed in a mixed solvent of ethanol and butanol and pulverized to a mean particle size of 1.0 μm with a ball mill. In the obtained slurry, polyvinyl butyral as a binder and butylphthalyl butyl glycolate as a plasticizer are dispersed in a ratio of 15% by mass and 7.5% by mass, respectively, with respect to 100% by mass of the calcined powder. Slurry. After defoaming and partial evaporation of the solvent under reduced pressure, the viscosity of the slurry was adjusted to about 10,000 MPa · s, and then a sheet was formed with a doctor blade, and a long ceramic green sheet having a dry thickness of about 80 μm was formed. Obtained. This ceramic green sheet was cut into a predetermined size for subsequent processing.
A wiring pattern L1-1, L1-2, L2-1, L2-2, a ground electrode pattern GND, and a switching element constituting a transmission line (inductance element) are mounted on the surface of a plurality of ceramic green sheets with silver paste. An electrode pattern was printed using an Ag paste for the purpose (see FIG. 1).
In the ceramic green sheet, via holes filled with silver paste are formed as means for connecting wiring patterns between the layers. Each ceramic green sheet on which the conductive pattern was printed was aligned, laminated with high accuracy, and then crimped. The pressure bonding conditions were a pressure of 14 MPa, a temperature of 85 ° C., and a holding time of 10 minutes.
得られた積層体をチップサイズに切断した後、焼成セッターに載置し、連続炉で脱バインダー及び焼成を行い、４．５ｍｍ×３．２ｍｍ×１．０ｍｍの焼成体を得た。焼成は大気雰囲気中８７５℃で２時間保持することにより行った。
焼成体のセラミック部分を粉砕してＸ線回折の測定をしたところ、組織中に六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８が、単斜晶および斜方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８、Ａｌ２Ｏ３結晶、ＴｉＯ２結晶、及びホウケイ酸塩系結晶が確認された。
焼成体から内部の配線パターンが露出している側面部分に、Ａｇを主成分とする外部電極用ペーストを塗布して８００℃で焼き付けた後、銀表面にニッケル及びスズを電解めっきし、端子電極ＧＮＤ，ＴＸ，ＲＸ，ＶＣ１，ＶＣ２とした。これらの端子電極のうち端子電極ＧＮＤ，ＴＸ，ＲＸ，ＶＣ１はスイッチング素子を実装するための電極パターンと電気的に接続させた。
このようにして得られた積層回路基板の実装電極パターンに、スイッチング素子としてダイオードＤ１，Ｄ２を実装し、図２に示す積層電子部品１を作製した。積層電子部品１は図３に示す等価回路の破線部を構成する。
The obtained laminate was cut into chip sizes, placed on a firing setter, debindered and fired in a continuous furnace, to obtain a fired body of 4.5 mm × 3.2 mm × 1.0 mm. Firing was performed by holding at 875 ° C. for 2 hours in an air atmosphere.
When the X-ray diffraction was measured by crushing the ceramic part of the fired body, hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O 8 were found in the structure. Monoclinic and orthorhombic SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , BaAl 2 Si 2 O 8 , Al 2 O 3 crystals, TiO 2 crystals, and borosilicate crystals confirmed.
After the external electrode paste mainly composed of Ag is applied to the side surface portion where the internal wiring pattern is exposed from the fired body and baked at 800 ° C., nickel and tin are electroplated on the silver surface, and the terminal electrode It was set as GND, TX, RX, VC1, VC2. Among these terminal electrodes, terminal electrodes GND, TX, RX, and VC1 were electrically connected to an electrode pattern for mounting a switching element.
Diodes D1 and D2 were mounted as switching elements on the mounting electrode pattern of the multilayer circuit board obtained as described above, and the multilayer
本実施例では、インダクタンス素子を電極パターンで構成したが、チップインダクタやコイル等を実装しても良い。また直流成分を遮断するコンデンサ素子を、電極パターンで回路基板に構成したり、チップコンデンサとして回路基板上に実装したりしても良い。ダイオードスイッチにローパスフィルタやバンドパスフィルタ等のフィルタ素子が接続されることが多いが、上記フィルタ素子をＳＡＷフィルタで構成し、これを回路基板に実装しても良い。またインダクタンス素子及びキャパシタンス素子からなるフィルタ素子を、回路基板上に電極パターンで形成したり、チップ部品として回路基板上に実装しても良い。
端子電極ＶＣ１，ＶＣ２に直流電源を接続し、ダイオードＤ１，Ｄ２をＯＮ，ＯＦＦさせて、端子電極ＡＮＴ−ＲＸ間、及び端子電極ＡＮＴ−ＴＸ間に高周波信号を通過させたところ、信号の伝送損失（挿入損失）が少なく、積層電子部品１は優れた電気的特性を有することが確認された。
積層回路基板の端子電極を試験用プリント基板にはんだ付けし、プリント基板を撓ませたり捻じったりして、端子の剥離や積層回路基板のクラック発生に対する抵抗力を評価したところ、従来のものと比べて著しく向上していることが分かった。
本実施例から、本発明の低温焼成セラミック組成物とＡｇ等の低融点金属は同時焼成が可能であるので、本発明の低温焼成セラミック組成物からなる誘電体層に低融点金属の導体パターンを形成すれば、電気的特性及び機械的強度に優れた積層電子部品が得られることが分かる。
In this embodiment, the inductance element is configured by an electrode pattern, but a chip inductor, a coil, or the like may be mounted. Further, the capacitor element that cuts off the direct current component may be configured on the circuit board with an electrode pattern, or may be mounted on the circuit board as a chip capacitor. In many cases, a filter element such as a low-pass filter or a band-pass filter is connected to the diode switch. However, the filter element may be formed of a SAW filter and mounted on a circuit board. Further, a filter element including an inductance element and a capacitance element may be formed on the circuit board with an electrode pattern, or may be mounted on the circuit board as a chip component.
When a DC power source is connected to the terminal electrodes VC1 and VC2, the diodes D1 and D2 are turned ON and OFF, and a high frequency signal is passed between the terminal electrodes ANT-RX and between the terminal electrodes ANT-TX, the signal transmission loss (Insertion loss) was small, and it was confirmed that the multilayer
Soldering the terminal electrode of the multilayer circuit board to the test printed circuit board and bending or twisting the printed circuit board to evaluate the resistance against peeling of the terminal and cracking of the multilayer circuit board. It was found that it was significantly improved.
Since the low-temperature fired ceramic composition of the present invention and a low-melting-point metal such as Ag can be fired simultaneously from this example, the conductor layer of the low-melting-point metal is formed on the dielectric layer made of the low-temperature fired ceramic composition of the present invention. If formed, it can be seen that a laminated electronic component having excellent electrical characteristics and mechanical strength can be obtained.
本発明の低温焼成セラミック組成物は、組織中に六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８の少なくとも一種を有するので、高強度で実用的な誘電特性を有し、かつ１０００℃以下の低温での焼成が可能である。そのため、銀、金、銅等の低融点電極材料との同時焼成が可能である。また本発明の高強度低温焼成セラミック組成物は、誘電率、ｆＱ等の誘電特性に優れているのみならず、従来より向上した機械的強度を有するので、積層回路基板とするときに低融点金属との同時焼成が可能であり、またクラックや破損が生じにくい。そのため、本発明の高強度低温焼成セラミック組成物を用いた積層電子部品は、優れた電気的特性及び機械的強度を有する。 The low-temperature fired ceramic composition of the present invention has at least one of hexagonal SrAl 2 Si 2 O 8 , (Sr, Ba) Al 2 Si 2 O 8 , and BaAl 2 Si 2 O 8 in the structure. It has practical dielectric properties and can be fired at a low temperature of 1000 ° C. or lower. Therefore, simultaneous firing with a low melting point electrode material such as silver, gold, or copper is possible. The high-strength low-temperature fired ceramic composition of the present invention not only has excellent dielectric properties such as dielectric constant and fQ, but also has improved mechanical strength as compared with the conventional low-melting point metal when used as a laminated circuit board. Can be fired at the same time, and cracks and breakage are less likely to occur. Therefore, the multilayer electronic component using the high-strength low-temperature fired ceramic composition of the present invention has excellent electrical characteristics and mechanical strength.
Claims (2)
少なくとも主成分としてＡｌ、Ｓｉ、Ｓｒ、Ｂａを含み、
Ａｌ ２ Ｏ ３ 、ＳｉＯ ２ 、ＳｒＣＯ ３ 、ＢａＣＯ ３ と、Ｂｉ ２ Ｏ ３ とを混合して仮焼し、Ａｌ２Ｏ３結晶を有するガラス粉末とした仮焼粉とし、前記仮焼粉より得られた成形体を、前記仮焼の温度よりも高温であり８２５℃〜９２０℃の温度で焼成して、
組織中に六方晶Ａｌ２Ｏ３結晶とともに六方晶ＳｒＡｌ２Ｓｉ２Ｏ８、（Ｓｒ、Ｂａ）Ａｌ２Ｓｉ２Ｏ８、ＢａＡｌ２Ｓｉ２Ｏ８ を形成することを特徴とするセラミック組成物。 A ceramic composition for a high-strength low-temperature fired ceramic substrate,
Including at least Al, Si, Sr, and Ba as main components,
And Al 2 O 3, SiO 2, SrCO 3, BaCO 3, by mixing a Bi 2 O 3 was calcined, the calcined powder was glass powder with Al 2 O 3 crystals, obtained from the calcined powder The obtained molded body is fired at a temperature of 825 ° C. to 920 ° C. that is higher than the temperature of the calcination,
Hexagonal with hexagonal Al 2 O 3 crystals in tissues crystal SrAl 2 Si 2 O 8, ( Sr, Ba) Al 2 Si2O 8, BaAl ceramic composition characterized by forming a 2 Si 2 O 8.
積層体として構成された成形体と、前記積層体に形成された低融点金属からなる導体パターンとを同時焼成し、前記低融点金属が銀、銅、金又はこれらの合金であることを特徴とする積層電子部品。 A ceramic composition according to claim 1,
A compact formed as a laminate and a conductor pattern made of a low melting point metal formed in the laminate are simultaneously fired, and the low melting point metal is silver, copper, gold or an alloy thereof, Laminated electronic components.
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