JP4632534B2 - Dielectric porcelain and manufacturing method thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、マイクロ波、ミリ波等の高周波領域において、５〜９０の範囲の誘電率と高いＱ値及び従来のガラスセラミックスと同等の低い収縮開始温度を有する誘電体磁器に関するものであり、例えば、マイクロ波やミリ波などの高周波領域において使用される種々の共振器用材料やＭＩＣ用誘電体基板材料、誘電体導波路用材料や積層型セラミックコンデンサ等に好適に用いることができる誘電体磁器及びその製造方法に関する。
【０００２】
【従来技術】
従来、誘電体磁器は、マイクロ波やミリ波等の高周波領域において、誘電体共振器、ＭＩＣ用誘電体基板や導波路等に広く利用されている。そして、近年においては、携帯電話をはじめとする移動体通信等の発達および普及に伴い、電子回路基板や電子部品の材料として、誘電体セラミックスの需要が増大しつつある。
【０００３】
電子回路基板や電子部品において、誘電体セラミックスと内部導体を同時焼成するに際しては、従来の誘電体セラミックスの焼成温度が１１００℃以上という高温であったため、導体材料としては、比較的高融点であるＰｔ、Ｐｄ、Ｗ、Ｍｏ等が使用されていた。これら高融点の導体材料は導通抵抗が大きいため、従来の電子回路基板において、共振回路やインダクタンスのＱ値が小さくなってしまい、導体線路の伝送損失が大きくなる等の問題があった。
【０００４】
そこで、この問題点を解決するために、導通抵抗の小さいＡｇ、Ｃｕ等と同時焼成可能な低温焼成の誘電体セラミックスが提案されている。例えば、特開平８−２０８３３０号公報に開示された誘電体磁器は、ＭｇＯ、ＣａＯ、ＴｉＯ2とＢ2Ｏ3、Ｌｉ2ＣＯ3からなるものであり、９００〜１０５０℃の比較的低温でＡｇ、Ｃｕ等の内部導体と同時に焼成でき、誘電体磁器の比誘電率εｒが１８以上、測定周波数７ＧＨｚでのＱ値が２０００以上の優れた特性を有し、高周波電子部品の小型化と多機能化を実現できるものであった。
【０００５】
【発明が解決しようとする課題】
しかしながら、特開平８−２０８３３０号公報に記載された誘電体磁器は、焼結温度がまだ高く、さらに焼結における収縮開始温度が８４５〜９６０℃と高温であるため、収縮開始温度が低温であるＡｇやＣｕを主成分とする導体材料との収縮挙動のマッチングが悪く、焼成された基板が反る、歪む等の問題があった。
【０００６】
また、この誘電体磁器は、共振回路やインダクタンスのＱ値を向上させるために、４０００以上が要求されており、Ｑ値が十分ではないという問題があった。
【０００７】
従って、本発明は、導体材料と同時焼成しても反りや歪みが無く、Ｑ値の高い誘電体磁器及びその製造方法を実現することを目的とする。
【０００８】
【課題を解決するための手段】
本発明は、Ｓｉ、Ｂ及びＬｉを含むガラス相により同時焼成が可能な焼成温度を達成するとともに、ガラス相を結晶化させ、Ｌｉ２ＴｉＳｉＯ ５ 結晶相を形成することにより、Ｑ値を改善できるという知見に基づく。
【０００９】
即ち、本発明の誘電体磁器は、主結晶である第１の結晶相としてのＭｇ ２ ＳｉＯ ４ を構成する原料粉末と、ＭｇＴｉＯ ３ 、ＣａＴｉＯ ３ 及びＢａＴｉ ４ Ｏ ９ のうち少なくとも１種を構成する原料粉末と、Ｌｉ及びＳｉを含有する焼結助剤とを混合し、焼成してなる誘電体磁器であって、Ｍｇ２ＳｉＯ ４ からなる第１の結晶相と、Ｌｉ２ＴｉＳｉＯ ５ からなる第２の結晶相とを含むとともに、測定周波数２ＧＨｚでのＱ値が４０００以上であることを特徴とするものである。
【００１０】
さらに、Ｘ線回折において回折角２θ＝３４〜３５°にピークを有する（Ｍｇ，Ｔｉ）２（ＢＯ３）Ｏで表される結晶相をさらに含むことが好ましい。これにより、更に高Ｑ値化することができる。
【００１１】
また、本発明の誘電体磁器の製造方法は、第１の結晶相としてのＭｇ ２ ＳｉＯ ４ を構成する原料粉末と、ＭｇＴｉＯ３、ＣａＴｉＯ ３ 及びＢａＴｉ４Ｏ９のうち少なくとも１種を構成する原料粉末との合量１００重量部に対して、Ｂ２Ｏ３を３〜２０重量部、Ｌｉ２ＣＯ３を１〜１０重量部、ＳｉＯ２を１〜３０重量部の割合で含む成形体を、８７０〜９２０℃で焼成し、Ｍｇ ２ ＳｉＯ ４ からなる第１の結晶相を有する誘電体磁器中に、Ｌｉ２ＴｉＳｉＯ ５ からなる第２の結晶相を析出させることを特徴とし、これにより、低温焼成が可能となるため、Ａｇ、Ｃｕを主成分とする導体と同時焼成しても、反りや歪み等を防止できる。
【００１２】
特に、第１の結晶相としてのＭｇ ２ ＳｉＯ ４ を構成する原料粉末と、ＭｇＴｉＯ３、ＣａＴｉＯ ３ 及びＢａＴｉ４Ｏ９のうち少なくとも１種を構成する原料粉末との合量１００重量部に対して、さらにアルカリ土類元素酸化物を１〜５重量部、酸化マンガンを０．１〜１５重量部含有することが好ましい。これにより、焼成温度を低温化、かつ安定化ができる。
【００１３】
また、前記焼成を、２時間以上行うこと、又は前記焼成の後に、７００〜９００℃で熱処理することが好ましい。これにより、前記第２結晶相をより析出しやすくできる。
【００１４】
【発明の実施の形態】
本発明の誘電体磁器は、Ｍｇ２ＳｉＯ ４ からなる第１の結晶相とともに、Ｌｉ２ＴｉＳｉＯ ５ からなる第２の結晶相を含有することが重要である。第１の結晶相が主結晶相として存在し、第２の結晶相と組み合わせることにより、比誘電率を５〜９０、測定周波数２ＧＨｚでのＱ値を４０００以上にすることができる。なお、この誘電体磁器には、ＭｇＴｉＯ ３ 、ＣａＴｉＯ ３ 、ＢａＴｉ ４ Ｏ ９ 、Ｍｇ ２ ＴｉＯ ４ 、Ｍｇ ２ Ｂ ２ Ｏ ５ の結晶相が含有されていてもなんら差し支えない。
【００１５】
また、後述するように、ガラス成分を調整し、製造方法を制御することによって、焼成温度を８７０〜９２０℃とすることが可能となり、さらに特性を改善できる。従って、基板や電子部品において、Ａｇ、Ｃｕを主成分とする導体と同時焼成した場合でも、反りや歪み等の発生を抑制することができ、かつ高機能な高周波回路部品の設計が可能となる。
【００１６】
また、本発明によれば、さらに（Ｍｇ，Ｔｉ）2（ＢＯ3）Ｏが含有されていることが好ましい。この結晶は、磁器に含まれることにより、Ｑ値を高める効果があり、その結果、２ＧＨｚでのＱ値を更に高めることができる。
【００１７】
なお、この結晶相は、Ｘ線回折により同定されるもので、ＪＣＰＤＳの１９−０７７５に示される結晶である。そして、少なくともメインピークである（２０１）面のピーク（面間隔２．５９Å）がＣｕをＸ線源に用いた場合に、３４〜３５°に認められるものである。
【００１８】
上記のように構成された本発明の誘電体磁器は、比誘電率が５〜９０、測定周波数２ＧＨｚでのＱ値が４０００以上になり、また、焼成温度も８７０〜９２０℃と、ＡｇやＣｕを主成分とする導体との同時焼成が可能な温度範囲に設定できる。従って、同時焼成でも反りや歪み等の発生を抑制することができる。
【００１９】
次に、本発明の誘電体磁器を製造する方法について、以下に説明する。
【００２０】
まず、原料粉末を用意する。第１の結晶相のために、Ｍｇ ２ ＳｉＯ ４ の組成を含む原料粉末と、ＭｇＴｉＯ３、ＣａＴｉＯ ３ 及びＢａＴｉ４Ｏ９のうち少なくとも1種の組成を含む原料粉末とを準備する。例えば、各金属元素、ＭｇＯ、ＳｉＯ ２ 、ＴｉＯ２、ＣａＯ、ＢａＯ等の酸化物、及びＭｇ ２ ＳｉＯ ４ 、ＭｇＴｉＯ３、ＣａＴｉＯ３ 、ＢａＴｉ４Ｏ９の複合酸化物等の粉末を用いることができる。
【００２１】
ここで、第１の結晶相との組み合わせとしては、ＭｇＴｉＯ３−Ｍｇ２ＳｉＯ４、ＣａＴｉＯ ３ −Ｍｇ ２ ＳｉＯ ４ 、ＭｇＴｉＯ３−ＣａＴｉＯ３−Ｍｇ２ＳｉＯ ４ 等がある。
【００２２】
本発明によれば、助剤成分として、Ｂ、Ｌｉ及びＳｉからなるガラス成分を用いることが必要である。即ち、ＭｇＴｉＯ3、ＣａＴｉＯ3、Ｍｇ2ＳｉＯ4及びＢａＴｉ4Ｏ9のうち少なくとも１種を構成する原料粉末１００重量部に対して、Ｂ2Ｏ3を３〜２０重量部、Ｌｉ2ＣＯ3を１〜１０重量部、ＳｉＯ2を０〜３０重量部の割合で含有することが重要である。
【００２３】
Ｂを第１の結晶相１００重量部に対してＢ2Ｏ3換算で３〜２０重量部含有したのは、Ｂ2Ｏ3の含有量が３重量部未満の場合には１１００℃でも焼結せず、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に２０重量部を越える場合には、焼結体中のガラス相の割合が増加して、Ｑ値が低下するからである。
【００２４】
従って、特に、焼結性を維持し、高いＱ値を得るという観点から、Ｂの含有量はＢ2Ｏ3換算で５〜１５重量部が望ましい。なお、添加する際の硼素源である硼素含有化合物としては、Ｂ2Ｏ3の他に、金属硼素、コレマイト、ＣａＢ2Ｏ4、ホウケイ酸ガラス、ホウケイ酸アルカリガラス、ホウケイ酸アルカリ土類ガラス等がある。
【００２５】
また、ＬｉをＬｉ2ＣＯ3換算で１〜１０重量部添加したのは、添加量が１重量部未満の場合には１１００℃でも焼結せず、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に１０重量部を越える場合には、Ｑ値が低下するからである。従って、焼結性と誘電体磁器のＱ値の観点から、特に４〜９重量部が望ましい。
【００２６】
さらに、ＳｉをＳｉＯ2換算で０〜３０重量部添加したのは、３０重量部を越えると、誘電体磁器中のガラス相の割合が増加してＱ値が低下するからである。誘電体磁器のＱ値の観点からは、ＳｉＯ2は０〜１０重量部が望ましい。
【００２７】
また、さらに焼結助剤として、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢａＯ等のアルカリ土類元素酸化物粉末及びＭｎＯ2粉末を加えることが好ましい。
【００２８】
即ち、第１の結晶相としてのＭｇ ２ ＳｉＯ ４ を構成する原料粉末と、ＭｇＴｉＯ３、ＣａＴｉＯ ３ 及びＢａＴｉ４Ｏ９のうち少なくとも１種を構成する原料粉末との合量１００重量部に対して、さらにアルカリ土類元素のうち少なくとも１種を酸化物換算で１〜５重量部含むことが好ましい。これにより、焼成温度をさらに低下でき、かつ誘電体磁器のＱ値を高める効果がある。とりわけ、焼結性とＱ値の点でアルカリ土類元素の含有量は、酸化物換算で１．５〜３．５重量部が好ましい。なお、アルカリ土類元素酸化物とは、周期律表２ａ族元素の酸化物であり、ＭｇＯ、ＣａＯ、ＳｒＯ及びＢａＯ等を例示できる。
【００２９】
さらに、ＭｎをＭｎＯ2換算で０．１〜１５重量部含むことが好ましい。このＭｎも、焼結性を高め、Ｑ値を高める効果があり、特に、３〜９重量部が望ましい。
【００３０】
なお、上記の元素以外であっても、Ｑ値が高く維持され、同時焼成をしたときに、基板に反りや歪みが発生しない範囲であれば、含有していても差し支えない。
【００３１】
これらの原料粉末を含む混合粉末を作製する。例えば、原料粉末を上記組成となるように秤量して、ＺｒＯ2ボールにより粉砕混合し、粉砕粒径が２．０μｍ以下となった粉末を６５０〜８５０℃で仮焼した後、再度ＺｒＯ2ボールにより粉砕粒径が２．５μｍ以下になるまで粉砕混合し、混合粉末を作製する。
【００３２】
得られた粉末は、各種の公知の成形方法、例えばプレス法、ドクターブレード法、射出成形法、テープ成形等により任意の形状に成形する。これらの方法の中で、ドクターブレード法、及びテープ成形が積層体形成のために特に好ましい。
【００３３】
得られた成形体は、大気中または酸素雰囲気中または窒素雰囲気等の非酸化性雰囲気において８７０〜９２０℃で焼成することにより得られる。特に、第２結晶相を析出させるため、焼成時間を２時間以上、特に３時間以上、さらには４時間以上とすることが好ましい。また、焼成時間を例えば０．５〜２時間で行った後、焼成後に５００〜９００℃、特に６５０〜８００℃で後処理を行って、ガラス相の結晶化を促進しても同様の効果が得られる。
【００３４】
従って、本発明によれば、焼結助剤成分として加えられた酸化物は、焼成時に第１の結晶相のために加えられた原料粉末と反応し、第２の結晶相であるＬｉ２ＴｉＳｉＯ ５ を形成することができる。
【００３５】
なお、原料粉末は、焼成により酸化物を生成する水酸化物、炭酸塩、硝酸塩等の金属塩を用いても良い。また、本発明の誘電体磁器中には、不可避不純物として、Ａｌ、Ｆｅ、Ｈｆ、Ｓｎ等が含まれることもあるが、特性及び焼結性に影響が無ければ差し支えない。
【００３６】
【実施例】
原料として純度９９％以上の、ＭｇＴｉＯ3、ＣａＴｉＯ3、Ｍｇ2ＳｉＯ4、ＢａＴｉ4Ｏ9粉末、およびＢ2Ｏ3、Ｌｉ2ＣＯ3、ＳｉＯ2、アルカリ土類元素酸化物（ＭｇＯ、ＣａＯ、ＢａＯ）、ＭｎＯ2粉末を含むガラスフリットを、表１に示す割合となるように秤量し、純水を媒体とし、ＺｒＯ2ボールを用いたボールミルにて２０時間湿式混合し、粉砕粒径を２．０μｍ以下とした。
【００３７】
次に、この混合物を乾燥して脱水し、８００℃で１時間仮焼した。この仮焼物を、粉砕粒径が１．４μｍ以下になるように粉砕し、誘電特性評価用の試料として直径６０ｍｍ高さ２ｍｍの円柱状に１００ＭＰａの圧力でプレス成形し、表１に示す焼成条件で焼成し、直径５０ｍｍ、高さ１ｍｍの円柱状の試料を得た。次いで、所望により、８５０℃で２時間の熱処理を行った。
【００３８】
誘電特性の評価は、上記の試料を用いて誘電体円柱共振器法にて周波数２ＧＨｚにおける比誘電率とＱ値を測定した。なお、表１の試料Ｎｏ．１４〜１７、２１は参考例である。
【００３９】
【表１】
本発明の試料Ｎｏ．１〜５、７〜１３、１８〜２０は、比誘電率が５．８〜９０、Ｑ値が４０００以上の優れた誘電特性を有し、９２０℃以下で同時焼結が可能で反りや歪みが見られなかった。
【００４１】
一方、第２の結晶相がなく、本発明の範囲外の試料Ｎｏ．６は、Ｑ値が２９００であった。
【００４２】
【発明の効果】
本発明は、Ｍｇ２ＳｉＯ ４ からなる第１の結晶相に対して、Ｌｉ２ＴｉＳｉＯ５ からなる第２の結晶相を含有させることにより、比誘電率を５〜９０、測定周波数２ＧＨｚでのＱ値を４０００以上にすることができるとともに、Ｓｉ、Ｂ及びＬｉの酸化物を含有させることにより、８７０〜９２０℃の温度でＡｇやＣｕ等の導体金属との同時焼成を行っても、基板の反りや歪みが抑制でき、高周波領域において高いＱ値を有するため、電子部品や基板の高性能化が実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dielectric ceramic having a dielectric constant in the range of 5 to 90, a high Q value, and a low shrinkage starting temperature equivalent to that of conventional glass ceramics in a high frequency region such as a microwave and a millimeter wave. Dielectric ceramics that can be suitably used for various resonator materials used in high frequency regions such as microwaves and millimeter waves, dielectric substrate materials for MICs, dielectric waveguide materials, multilayer ceramic capacitors, etc. It relates to the manufacturing method.
[0002]
[Prior art]
Conventionally, dielectric ceramics are widely used for dielectric resonators, dielectric substrates for MICs, waveguides, and the like in a high frequency region such as microwaves and millimeter waves. In recent years, with the development and spread of mobile communications such as mobile phones, the demand for dielectric ceramics as materials for electronic circuit boards and electronic components is increasing.
[0003]
In the simultaneous firing of dielectric ceramics and internal conductors in electronic circuit boards and electronic parts, the firing temperature of conventional dielectric ceramics is as high as 1100 ° C. or higher, so the conductor material has a relatively high melting point. Pt, Pd, W, Mo, etc. were used. Since these high melting point conductor materials have a large conduction resistance, the conventional electronic circuit board has a problem that the Q value of the resonance circuit and the inductance is reduced, and the transmission loss of the conductor line is increased.
[0004]
In order to solve this problem, low-temperature fired dielectric ceramics that can be fired simultaneously with Ag, Cu, etc. having a low conduction resistance have been proposed. For example, the dielectric ceramic disclosed in Japanese Patent Laid-Open No. 8-208330 is made of MgO, CaO, TiO 2 and B 2 O 3 , Li 2 CO 3 , and is made of Ag at a relatively low temperature of 900 to 1050 ° C. It can be fired at the same time as an internal conductor such as Cu, and has excellent characteristics such as a dielectric ceramic having a relative dielectric constant εr of 18 or more and a Q value of 2000 or more at a measurement frequency of 7 GHz. Can be realized.
[0005]
[Problems to be solved by the invention]
However, the dielectric ceramic described in JP-A-8-208330 has a high sintering temperature, and the shrinkage start temperature in sintering is as high as 845 to 960 ° C., so the shrinkage start temperature is low. Matching of the shrinkage behavior with the conductor material containing Ag or Cu as a main component is poor, and there is a problem that the fired substrate is warped or distorted.
[0006]
Further, the dielectric ceramic is required to have a value of 4000 or more in order to improve the Q value of the resonance circuit and the inductance, and there is a problem that the Q value is not sufficient.
[0007]
Accordingly, an object of the present invention is to realize a dielectric ceramic having a high Q value without warping or distortion even when fired simultaneously with a conductor material, and a method for manufacturing the same.
[0008]
[Means for Solving the Problems]
The present invention, Si, as well as achieving a sintering temperature can be simultaneously fired glass phase containing B and Li, glass phase is crystallized by forming a L i 2 TiSiO 5 binding phase, the Q value Based on the knowledge that it can be improved.
[0009]
That is, the dielectric ceramic of the present invention constitutes at least one of the raw material powder constituting Mg 2 SiO 4 as the first crystal phase which is the main crystal, and MgTiO 3 , CaTiO 3 and BaTi 4 O 9. and the raw material powder and a sintering aid containing Li and Si are mixed, a dielectric ceramic obtained by firing a Ranaru first crystalline phase or Mg 2 SiO 4, or L i 2 TiSiO 5 together and a Ranaru second crystal phase, Q value at a measuring frequency of 2GHz is Ru Oh characterized in that at more than 4,000.
[0010]
Furthermore, it is preferable to further include a crystal phase represented by (Mg, Ti) 2 (BO 3 ) O having a peak at a diffraction angle 2θ = 34 to 35 ° in X-ray diffraction . As a result, the Q value can be further increased.
[0011]
Further, the production method of the dielectric ceramic of the present invention constitutes a raw material powder constituting the Mg 2 SiO 4 as a first crystal phase, the MgTiO 3, CaTiO 3 及 beauty BaTi 4 at least one of O 9 relative to the total amount 100 parts by weight of the raw material powder, B 2 O 3 3 to 20 parts by weight, 1 to 10 parts by weight of Li 2 CO 3, the molded body containing SiO 2 in a proportion of 1 - 30 parts by weight and then calcined at 870 to 920 ° C., in the dielectric ceramic having a first crystal phase comprising a Mg 2 SiO 4, characterized in that to precipitate Li 2 TiSiO 5 or Ranaru second crystal phase, thereby Since low-temperature firing is possible, warping, distortion, and the like can be prevented even when co-firing with a conductor mainly composed of Ag and Cu.
[0012]
In particular, a raw material powder constituting the Mg 2 SiO 4 as a first crystal phase, relative to the total amount 100 parts by weight of the raw material powder constituting at least one of MgTiO 3, CaTiO 3 及 beauty BaTi 4 O 9 Further, it is preferable to contain 1 to 5 parts by weight of alkaline earth element oxide and 0.1 to 15 parts by weight of manganese oxide. Thereby, the firing temperature can be lowered and stabilized.
[0013]
Moreover, it is preferable to perform the said baking for 2 hours or more, or to heat-process at 700-900 degreeC after the said baking. Thereby, the second crystal phase can be more easily precipitated.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The dielectric ceramic of the present invention, as well as M g 2 SiO 4 or Ranaru first crystal phase, it is important to contain L i 2 TiSiO 5 or Ranaru second crystal phase. When the first crystal phase exists as the main crystal phase and is combined with the second crystal phase, the relative dielectric constant can be 5 to 90, and the Q value at a measurement frequency of 2 GHz can be 4000 or more. Incidentally, this dielectric ceramic, MgTiO 3, CaTiO 3, BaTi 4 O 9, Mg 2 TiO 4, Mg 2 B 2 O 5 crystalline phase no problem any be contained.
[0015]
In addition, as described later, by adjusting the glass component and controlling the production method, the firing temperature can be set to 870 to 920 ° C., and the characteristics can be further improved. Therefore, even when a substrate or an electronic component is fired at the same time as a conductor containing Ag and Cu as main components, it is possible to suppress the occurrence of warpage and distortion and to design a high-performance high-frequency circuit component. .
[0016]
Further, according to the present invention, it is preferable that (Mg, Ti) 2 (BO 3 ) O is further contained. This crystal has the effect of increasing the Q value by being included in the porcelain, and as a result, the Q value at 2 GHz can be further increased.
[0017]
This crystal phase is identified by X-ray diffraction and is a crystal shown in JCPDS 19-0775. Then, at least the peak of the (201) plane (plane spacing of 2.59 mm), which is the main peak, is observed at 34 to 35 ° when Cu is used for the X-ray source.
[0018]
The dielectric ceramic of the present invention configured as described above has a relative dielectric constant of 5 to 90, a Q value of 4000 or more at a measurement frequency of 2 GHz, and a firing temperature of 870 to 920 ° C., such as Ag and Cu. Can be set to a temperature range in which co-firing with a conductor containing as a main component is possible. Accordingly, the occurrence of warpage or distortion can be suppressed even in simultaneous firing.
[0019]
Next, a method for manufacturing the dielectric ceramic according to the present invention will be described below.
[0020]
First, raw material powder is prepared. For the first crystal phase, prepared a raw material powder containing a composition of Mg 2 SiO 4, and a raw material powder containing at least one composition of the MgTiO 3, CaTiO 3 及 beauty BaTi 4 O 9. For example, powders such as various metal elements, oxides such as MgO, SiO 2 , TiO 2 , CaO, and Ba 2 O , and composite oxides of Mg 2 SiO 4 , MgTiO 3 , CaTiO 3 , and BaTi 4 O 9 are used. Can do.
[0021]
Here, the combination of the first crystal phase, M gTiO 3 -Mg 2 SiO 4 , CaTiO 3 -Mg 2 SiO 4, MgTiO 3 -CaTiO 3 is -Mg 2 SiO 4 and the like.
[0022]
According to the present invention, it is necessary to use a glass component composed of B, Li and Si as an auxiliary component. That is, 3 to 20 parts by weight of B 2 O 3 and 3 to 20 parts by weight of Li 2 CO 3 with respect to 100 parts by weight of raw material powder constituting at least one of MgTiO 3 , CaTiO 3 , Mg 2 SiO 4 and BaTi 4 O 9. It is important to contain 1 to 10 parts by weight and SiO 2 in a proportion of 0 to 30 parts by weight.
[0023]
The reason why B is contained in an amount of 3 to 20 parts by weight in terms of B 2 O 3 with respect to 100 parts by weight of the first crystal phase is that sintering is performed even at 1100 ° C. when the content of B 2 O 3 is less than 3 parts by weight. Without simultaneous firing with a conductor mainly composed of Ag or Cu, conversely, when it exceeds 20 parts by weight, the ratio of the glass phase in the sintered body increases and the Q value decreases. It is.
[0024]
Therefore, in particular, from the viewpoint of maintaining sinterability and obtaining a high Q value, the content of B is preferably 5 to 15 parts by weight in terms of B 2 O 3 . The boron-containing compound which is a boron source at the time of addition includes, in addition to B 2 O 3 , metallic boron, collimite, CaB 2 O 4 , borosilicate glass, borosilicate alkali glass, borosilicate alkaline earth glass, etc. There is.
[0025]
In addition, 1 to 10 parts by weight of Li in terms of Li 2 CO 3 was added when the added amount was less than 1 part by weight, and sintering was not performed even at 1100 ° C., and at the same time as the conductor mainly composed of Ag or Cu. This is because when the firing becomes impossible and the amount exceeds 10 parts by weight, the Q value decreases. Accordingly, 4 to 9 parts by weight is particularly desirable from the viewpoint of sinterability and the Q value of the dielectric ceramic.
[0026]
Further, the reason why Si is added in an amount of 0 to 30 parts by weight in terms of SiO 2 is that when the amount exceeds 30 parts by weight, the ratio of the glass phase in the dielectric ceramic increases and the Q value decreases. From the viewpoint of the Q value of the dielectric ceramic, 0 to 10 parts by weight of SiO 2 is desirable.
[0027]
Further, it is preferable to add alkaline earth element oxide powders such as MgO, CaO, SrO and BaO and MnO 2 powder as sintering aids.
[0028]
That is, a raw material powder constituting the Mg 2 SiO 4 as a first crystal phase, relative to the total amount 100 parts by weight of the raw material powder constituting at least one of MgTiO 3, CaTiO 3 及 beauty BaTi 4 O 9 In addition, it is preferable that 1 to 5 parts by weight of at least one alkaline earth element in terms of oxide is included. As a result, the firing temperature can be further lowered and the Q value of the dielectric ceramic can be increased. In particular, the alkaline earth element content in terms of sinterability and Q value is preferably 1.5 to 3.5 parts by weight in terms of oxide. The alkaline earth element oxide is an oxide of group 2a element of the periodic table, and examples thereof include MgO, CaO, SrO, and BaO.
[0029]
Furthermore, it is preferable to contain 0.1 to 15 parts by weight of Mn in terms of MnO 2 . This Mn also has the effect of increasing the sinterability and increasing the Q value, and 3 to 9 parts by weight is particularly desirable.
[0030]
Note that elements other than the above elements may be contained as long as the Q value is maintained high and co-firing does not cause warping or distortion of the substrate.
[0031]
A mixed powder containing these raw material powders is prepared. For example, the raw material powder was weighed so that the composition, after mixing pulverized by ZrO 2 balls were calcined powder pulverized particle diameter became 2.0μm or less at 650 to 850 ° C., again ZrO 2 balls The mixture is pulverized and mixed until the pulverized particle size becomes 2.5 μm or less to produce a mixed powder.
[0032]
The obtained powder is molded into an arbitrary shape by various known molding methods, for example, a press method, a doctor blade method, an injection molding method, a tape molding and the like. Among these methods, the doctor blade method and tape molding are particularly preferable for forming a laminate.
[0033]
The obtained molded body is obtained by firing at 870 to 920 ° C. in a non-oxidizing atmosphere such as air, oxygen atmosphere or nitrogen atmosphere. In particular, in order to precipitate the second crystal phase, the firing time is preferably 2 hours or more, particularly 3 hours or more, and more preferably 4 hours or more. Moreover, after performing baking time for 0.5 to 2 hours, for example, even if it post-processes at 500-900 degreeC after baking, especially 650-800 degreeC, and the crystallization of a glass phase is accelerated | stimulated, the same effect is obtained. can get.
[0034]
Therefore, according to the present invention, oxides added as sintering aid components, the first to react with the raw material powder was added to the crystalline phase during firing, Ru second crystal phase Der L i it is possible to form the 2 TiSiO 5.
[0035]
Note that the raw material powder may be a metal salt such as a hydroxide, carbonate, or nitrate that generates an oxide by firing. In addition, the dielectric ceramic of the present invention may contain Al, Fe, Hf, Sn, etc. as inevitable impurities, but there is no problem as long as the characteristics and sinterability are not affected.
[0036]
【Example】
MgTiO 3 , CaTiO 3 , Mg 2 SiO 4 , BaTi 4 O 9 powder, and B 2 O 3 , Li 2 CO 3 , SiO 2 , alkaline earth element oxides (MgO, CaO, BaO), a glass frit containing MnO 2 powder was weighed so as to have the ratio shown in Table 1, and wet-mixed for 20 hours in a ball mill using ZrO 2 balls using pure water as a medium, and the pulverized particle size was 2 0.0 μm or less.
[0037]
Next, this mixture was dried and dehydrated, and calcined at 800 ° C. for 1 hour. This calcined product was pulverized so that the pulverized particle size was 1.4 μm or less, and was press-molded at a pressure of 100 MPa into a cylindrical shape having a diameter of 60 mm and a height of 2 mm as a sample for dielectric property evaluation. And a cylindrical sample having a diameter of 50 mm and a height of 1 mm was obtained. Then, if desired, heat treatment was performed at 850 ° C. for 2 hours.
[0038]
For the evaluation of dielectric characteristics, the relative permittivity and Q value at a frequency of 2 GHz were measured by the dielectric cylindrical resonator method using the above sample. In Table 1, sample No. Reference numerals 14 to 17 and 21 are reference examples.
[0039]
[Table 1]
Sample No. of the present invention. 1-5, 7-13 , 18-20 have excellent dielectric properties with a relative dielectric constant of 5.8-90 and a Q value of 4000 or more, and can be simultaneously sintered at 920 ° C. or lower, warping and distortion Was not seen.
[0041]
On the other hand, there is no second crystal phase, and sample No. 6 had a Q value of 2900.
[0042]
【The invention's effect】
The present invention is, with respect to M g 2 SiO 4 or Ranaru first crystal phase, by containing the second crystalline phase consisting of L i 2 TiSiO 5, the relative dielectric constant of 5 to 90, measurement frequency 2GHz In addition, the Q value at 4000 can be 4000 or more, and by containing oxides of Si, B and Li, even when co-firing with a conductor metal such as Ag or Cu at a temperature of 870 to 920 ° C. Since the warpage and distortion of the substrate can be suppressed and the Q value is high in the high frequency region, high performance of the electronic component and the substrate can be realized.
Claims (6)
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| JP3860687B2 (en) * | 1999-10-29 | 2006-12-20 | 京セラ株式会社 | Dielectric porcelain and laminate |
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| CN106904960B (en) * | 2017-03-14 | 2020-01-14 | 电子科技大学 | Mg2SiO4-Li2TiO3Composite system LTCC material and preparation method thereof |
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