JP3813917B2 - Dielectric porcelain composition and electronic component using the same - Google Patents

Description

表中「＊」は本発明の範囲外であることを示す。
【００３６】
【表２】

【００３７】
【表３】

表中「＊」は本発明の範囲外であることを示す。
【００３８】
その後、得られた混合粉末を振動ミル中に投入し、一次粉砕（３時間）を行った後、大気雰囲気において昇温速度２００℃／時間で８００℃まで昇温させて２時間仮焼を行い、降温速度２００℃／時間で降温させて仮焼粉末を得た。得られた仮焼粉末に有機バインダー（約５ｇ）と水（約２００ｇ）とを加え、ボールミルに投入し、直径２０ｍｍのアルミナボールを用いて、ミルの回転数９０ｒｐｍで二次粉砕（２４時間）を行った。その後、得られた二次粉砕粉末を、真空凍結乾燥（圧力；約５３Ｐａ、凍結温度；−４０〜−２０℃、乾燥温度；４０〜５０℃、時間；２０時間）により造粒して造粒粉末を得た。得られた造粒粉末を金型に投入し、１００ＭＰａで加圧して、直径１９ｍｍ、高さ１０ｍｍの円柱状の未焼成成形体を得た。
【００３９】
次いで、得られた未焼成成形体を大気雰囲気において昇温速度５０℃／時間で５００℃まで昇温させて３時間保持することで脱脂を行った。その後、引き続いて、昇温速度１００℃／時間で表１、表２及び表３に示す各焼成温度まで昇温させて２時間保持することで焼成を行い、次いで、降温速度１００℃／時間で降温させ、本発明の誘電体磁器組成物からなる誘電体磁器及び比較例の誘電体磁器組成物からなる誘電体磁器を得た。
その後、得られた各誘電体磁器を直径１６ｍｍ、高さ８ｍｍの円柱状となるように研磨し、次いで、超音波洗浄を行い、その後、１００℃で４時間保持して乾燥させ、本発明の誘電体磁器組成物からなる誘電特性測定用の誘電体磁器（実験例３〜１７、１９〜３４、３６〜３９及び４１〜４６）及び比較例の誘電体磁器組成物からなる誘電特性測定用の誘電体磁器（実験例１、２、１８、３５及び４０）を得た。
【００４０】
（２）Ａｇ拡散域測定用の電子部品の製造
上記（１）と同様な成分粉末を用い、同様な方法により仮焼粉末を得た。得られた仮焼粉末にトルエンと分散剤とを所定量加え、上記（１）と同様にして二次粉砕を行った。その後、トルエン中にアクリル系バインダと可塑剤であるジオクチルフタレートとを４時間以上撹拌して溶解させた樹脂溶液を、得られた二次粉砕粉末に加え、粉砕時間を４時間とした以外は上記二次粉砕と同様にして混合してスラリーを得た。得られたスラリーを２００メッシュのフィルタを通過させることで、スラリー中の異物等を除去した。その後、更にトルエンを加えて３Ｐａ・ｓとなるように粘度を調整し、次いで、脱泡を行った。このようにして得られたスラリーをドクターブレード方式のキャスティング装置に投入して、厚さ１００〜３００μｍのシート状に成形した。その後、縦６ｃｍ、横５ｃｍに切り出して未焼成成形体を得た。
【００４１】
得られたシート状の未焼成成形体３枚を圧着積層し、その表面の□２ｍｍの領域に、Ａｇをペースト全体の９０質量％含有する導電層用ペーストをスクリーン印刷した。その後、更に、印刷された導電層用ペーストを覆うように３枚のシート状の未焼成成形体を圧着積層した。次いで、得られた未焼成積層体を熱圧着機を用いて２０ＭＰａで加圧して圧着した。
その後、得られた未焼成積層体を上記（１）と同様にして、脱脂を行い、引き続いて焼成を行い、本発明の誘電体磁器組成物からなる誘電体磁器と同時焼成された導電層とを備える電子部品（実験例３〜１７、１９〜３４、３６〜３９及び４１〜４６）、及び、比較例の誘電体磁器組成物からなる誘電体磁器と同時焼成された導電層とを備える電子部品（実験例１、２、１８、３５及び４０）を得た。尚、これらの電子部品は分かり易さのために上記（１）における実験例Ｎｏと同じ番号を用いて各表に表した。
【００４２】
（３）誘電特性及び焼結密度の測定
上記（１）で得られた誘電特性測定用の誘電体磁器を用い、平行導体板型誘電体円柱共振器法（ＴＥ_０１１モード）により表１、表２及び表３に示す共振周波数ｆ_０におけるε_ｒ、Ｑｕ及びτ_ｆを測定した。この結果を表１、表２及び表３に示す。尚、τ_ｆは２５〜８０℃の温度領域で測定し、下記式▲１▼に従って算出した。式▲１▼におけるｆ_２５は２５℃における共振周波数を表し、ｆ_８０は８０℃における共振周波数を表し、ΔＴは８０℃と２５℃との差である５５℃を表す。
τ_ｆ＝（ｆ_８０−ｆ_２５）／（ｆ_２５×ΔＴ） ・・・・▲１▼
また、アルキメデス法により焼成後の密度を測定し、表１、表２及び表３に焼結密度として併記した。
【００４３】
（４）Ａｇ拡散域の測定（図９参照）
上記（２）で得られた電子部品１（実験例１〜４６）を樹脂１１に封入し、誘電体磁器１２の内部に形成した導体層１３が表出するように積層方向に研磨を行った。その後、導体層１３が表出している面を積層方向にＸ線プローブマイクロアナライザ（以下、単に「ＥＰＭＡ」という。日本電子データダム社製、型式「ＪＸＡ−８８００Ｍ」）を用いてＡｇについて線分析を行った。この線分析においては、真空条件下で、波長分散型Ｘ線分光器（ＷＤＳ）を用い、照射電流を０．２５ｎＡとし、加速電圧を２０ｋＶとした。
【００４４】
この結果において、ＡｇのＸ線強度が９以上として測定された領域から導体層１３を除いた領域をＡｇの拡散が認められるＡｇ拡散域１４とした。この基準に従い導体層１３からＡｇ拡散域１４を通過して導体層１３から遠ざかる一方向へ観察したＡｇ拡散域１４の長さを測定し（図９における太い矢印１６のように）、「Ａｇ拡散域」として表１、表２及び表３に併記した。尚、各図中１５は測定した領域である。
【００４５】
（５）ＥＰＭＡによる元素マップの作成
上記（４）と同じＥＰＭＡを用い、同じ測定条件により、実験例５の電子部品の各元素について各々元素マップを作成した。このとき測定範囲は□２００μｍとし、測定時間は１点につき３０ｍ秒とし、画素の大きさは０．５μｍとし、画素数は３００×３００とした。得られた各元素マップを、図２〜９に示した。図２はＢｉに関し、図３はＮｂに関し、図４はＴａに関し、図５はＶに関し、図６はＣｕに関し、図７はＭｎに関し、図８はＡｇに関する元素マップである。
【００４６】
（７）評価
以下、上記（３）〜上記（５）までに得られた測定結果に基づき説明する。
▲１▼α及びβに関して
実験例１〜１１より、表１に示すＣｕの配合量であるβとＡｇ拡散域との相関を図１に示した。この図１から分かるように、Ｃｕは僅かな含有により極めて効果的にＡｇの拡散を抑制していることが分かる。即ち、Ｃｕを含有しない場合は実験例１（比較例）に示すようにＡｇ拡散域が１８０μｍと非常に大きい。一方、実験例３（実施例）に示すように僅か０．１質量部の配合によりＡｇ拡散域は６８μｍと小さくなり、Ａｇ拡散域が３７．８％にまで縮小されていることが分かる。更に、実験例６（実施例）に示すように僅か０．３質量部の配合であればＡｇ拡散域は２４μｍであり、Ａｇ拡散域はＣｕを含有しない場合に比べて１３．３％にまで縮小されていることが分かる。
【００４７】
この効果は、Ｖ_２Ｏ_５の配合量であるαとの関係においてβ／α≧０．８７５を満たすことが必要であることが実験例１（比較例）及び実験例２（比較例）の結果より分かる。一方、Ｃｕは過度に含有されると、実験例１８（比較例）に示すようにＱｕが２００以下と小さくなる場合がある。このため、ＣｕＯの配合量であるβは１７．１４質量部よりも小さくする必要がある。
【００４８】
Ａｇ拡散域の大きさは、Ｃｕの含有量βのみにより決定されるのではなく、Ｖの含有量αとＣｕの含有量βとの相関によっても影響を受けることが、例えば、実験例３（実施例）と実験例１１（実施例）とから読みとれる。即ち、実験例３ではＣｕＯの配合量が０．１質量部である場合にＡｇ拡散域が６８μｍである。これに対して、実験例１１ではＣｕＯの配合量が０．０８６質量部と実験例３に比べて少ないにも関わらず、Ａｇ拡散域は２５μｍである。即ち、実験例３に比べて、実験例１１の方がＣｕの含有量が少ないにも関わらず、Ａｇ拡散域は小さい。これは実験例３に比べて実験例１１における方がＶの含有量が少ないためであると考えられる。
【００４９】
更に、このＶに関して、Ｖ_２Ｏ_５の配合量であるαが本発明の範囲を超えると、実験例１８（比較例）に示すようにＱｕが２００以下と小さくなる場合がある。このため、Ｖ_２Ｏ_５の配合量は６．００質量部よりも小さくする必要がある。
【００５０】
▲２▼γに関して
表２における実験例２６〜２９はＭｎを含有しないものであり、実験例３０〜３４はＭｎを含有しないものであり、各々焼成温度を８５０〜９５０℃の間で変化させた結果である。実験例２６〜２９及び実験例３０〜３４の間の変化は下記の通りである。
実験例２６〜２９
ε_ｒ ４５．０〜４５．６の間で０．６変動
Ｑｕ ８９２〜９０１の間で１１変動
τ_ｆ −９．９〜−１０．５ｐｐｍ／℃の間で０．６ｐｐｍ／℃変動
実験例３０〜３４
ε_ｒ ３８．３〜４２．１の間で３．８変動
Ｑｕ ７４５〜８９０の間で１４５変動
τ_ｆ −１２．３〜−１９．８ｐｐｍ／℃の間で７．５ｐｐｍ／℃変動
【００５１】
この結果から、Ｍｎを含有することによりＡｇ拡散域に影響を与えることなく、誘電特性に対する焼成温度の影響を極めて効果的に抑制できることが分かる。即ち、ε_ｒの変化量は最大８４％抑制され、Ｑｕの変化量は最大９２％抑制され、τ_ｆの変化量は最大９２％抑制されている。Ｍｎを含有しなくとも本発明の組成を有することにより優れた誘電特性が発揮される。しかし、製造時には焼成温度により誘電特性が変化し易く、所望の誘電特性を有する誘電体磁器を安定的に得難い場合もある。しかし、Ｍｎを含有することにより、焼成温度による影響は大幅に抑制でき、安定して優れた誘電特性を得ることが可能となることが分かる。
【００５２】
但し、実験例１９〜２５より、Ｍｎの含有量γが大きくなるに従いＱｕが小さくなる傾向があることが分かる。特にγが２．０質量部（実験例２４）から３．０質量部（実験例２５）に変化するとＱｕは５２３から３９８へ変化するが、２．０質量部であっても、３．０質量部であってもＭｎを含有する効果は十分に発揮される。このためγは３．０未満に抑えることでＱｕの低下を効果的に抑制できることが分かる。
【００５３】
▲３▼ｘ、ｙ及びｚに関して、
表３における、実験例４０より、ｘの値が本発明の範囲を超えると（ｘ＝０．６０）Ｑｕが２３１と小さくなっていることが分かる。同様に、実験例３５より、ｙ及びｚが本発明の範囲を超えると（ｙ＝０．５４、ｚ＝０．０６）Ｑｕが２５０と小さくなっていることが分かる。
これに対して、本発明（０．４３≦ｘ≦０．５７、０＜ｙ≦０．５２、０．０１≦ｚ≦０．５７）である実験例３６〜３９及び実験例４１〜４６より、ε_rは４１．９〜５０．４の間で、Ｑｕは８５６〜９０３の間で、τ_ｆは−５３．９〜−４ｐｐｍ／℃の間で、各々の誘電特性を幅広く制御でき得ることが分かる。また、Ａｇ拡散域は２４〜２５μｍの間で安定させることができる。
【００５４】
▲４▼元素マップの結果に関して
図２及び図３より、誘電体磁器中に含まれるＢｉ及びＮｂは導体層側へ拡散していないことが分かる。これに対して、図４〜図６より、誘電体磁器中に含まれるＴａ、Ｖ及びＣｕは導体層側へ拡散していることが分かる。また、図７より、Ｍｎも僅かではあるが導体層側へ拡散していることが認められる。一方、図８より、導体層を構成するＡｇは誘電体磁器側へ僅かに拡散しているが、そのＡｇ拡散域は２５μｍと非常に小さく実使用上問題の無い程度に抑えられていることが分かる。
これらの元素マップ及び上記図１より、Ｔａ及びＶを含有する誘電体磁器において、Ｃｕが含有され、このＣｕが導体層側へ拡散を生じることにより、その理由は定かではないが、逆に導体層を構成するＡｇが誘電体磁器側へ拡散することを極めて効果的に抑制できることが分かる。
【図面の簡単な説明】
【図１】ＣｕＯの配合量とＡｇ拡散域との相関を示すグラフである。
【図２】本発明品である実験例５のＢｉに関するＥＰＭＡによる元素マップである。
【図３】本発明品である実験例５のＮｂに関するＥＰＭＡによる元素マップである。
【図４】本発明品である実験例５のＴａに関するＥＰＭＡによる元素マップである。
【図５】本発明品である実験例５のＶに関するＥＰＭＡによる元素マップである。
【図６】本発明品である実験例５のＣｕに関するＥＰＭＡによる元素マップである。
【図７】本発明品である実験例５のＭｎに関するＥＰＭＡによる元素マップである。
【図８】本発明品である実験例５のＡｇに関するＥＰＭＡによる元素マップである。
【図９】Ａｇ拡散域の測定及び元素マップの作成に関する説明図である。
【符号の説明】
１；電子部品、１１；樹脂、１２；誘電体磁器組成物（誘電体磁器）、１３；導体層、１４；Ａｇ拡散域、１５；測定領域。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dielectric ceramic composition. More specifically, it is a dielectric ceramic composition having a novel composition, which has various dielectric properties such as a relative dielectric constant, a no-load quality factor, and a temperature coefficient of resonance frequency in a well-balanced manner, and can be obtained by simultaneous firing with a conductor layer. The present invention relates to a dielectric ceramic composition that hardly causes diffusion (migration) of components constituting a layer, and an electronic component using the same.
[0002]
The dielectric ceramic composition of the present invention is suitable as various electronic components used in the microwave band and the millimeter wave band. The various electronic components include individual components such as LC devices, resonators, couplers, duplexers, diplexers, diodes, and ceramic capacitors, general-purpose substrates, and functional substrates in which various functional components are embedded (such as LTCC multilayer devices). Board, MPU, SAW, and other packages, modules including at least one of these individual parts, boards, and packages. In addition, the electronic component of the present invention is a mobile communication device, mobile communication base station device, satellite communication device, satellite communication base station device, satellite broadcast device that uses radio waves in various microwave bands and / or millimeter wave bands. It can be used for wireless LAN devices, Bluetooth (registered trademark) devices, and the like.
[0003]
[Prior art]
In general, a dielectric ceramic used in a high frequency band is required to have a large relative dielectric constant, a small dielectric loss, and a small absolute value of a temperature coefficient of a resonance frequency. In addition, simultaneous firing without trouble with metals with low melting points such as silver, silver alloys, copper and copper alloys
It is hoped that it can be done. Examples of the dielectric ceramic composition constituting such a dielectric ceramic include Patent Documents 1 to 4 listed below.
[0004]
[Patent Document 1]
Japanese Patent Laid-Open No. 5-74224
[Patent Document 2]
Japanese Patent Laid-Open No. 5-74224
[Patent Document 3]
JP-A-7-187873
[Patent Document 4]
Japanese Patent Laid-Open No. 7-277824
[0005]
[Problems to be solved by the invention]
However, in each of the above-mentioned documents, no examination is made regarding the composition of the conductor layer and the dielectric ceramic formed on or inside the dielectric ceramic.
INDUSTRIAL APPLICABILITY The present invention provides a novel dielectric material that can be fired at a low temperature, can obtain a dielectric ceramic having a large relative dielectric constant in a high frequency band, a small dielectric loss, and a small absolute value of a temperature coefficient of a resonance frequency. An object is to provide a porcelain composition. It is another object of the present invention to provide a dielectric porcelain composition in which diffusion of components constituting the conductor layer is hardly observed on the dielectric porcelain side even when co-firing with the conductor layer is performed. It is another object of the present invention to provide an electronic component exhibiting excellent dielectric characteristics, comprising a dielectric ceramic made of such a dielectric ceramic composition.
[0006]
[Means for Solving the Problems]
The present inventors have obtained a dielectric ceramic composition exhibiting excellent dielectric properties disclosed in Patent Document 3 and Patent Document 4 so far. This dielectric ceramic composition is made of BiNbO disclosed in Patent Document 1 and Patent Document 2. ₄ The system composition further contains both Ta (tantalum) and V (vanadium). This dielectric ceramic has solved the problem that it is difficult to stably control the temperature coefficient of the resonance frequency of the dielectric ceramic to a desired value, and has made it possible to obtain various excellent dielectric characteristics.
[0007]
However, in order to provide a conductor layer on the surface or inside of this dielectric ceramic, when the conductor layer and an unsintered molded body to be the dielectric ceramic are co-fired, the components constituting the conductor layer (particularly Ag) It has been found that there is a case where the electric characteristics which are supposed to be able to be exhibited are not sufficiently exhibited due to diffusion in the dielectric ceramic. Further, when examined in more detail, it was discovered that Ta and V contained in the dielectric ceramic were diffused into the conductor layer (see FIGS. 4 and 5). However, it is not normally considered that a component having a high melting point such as Ta (such as tantalum oxide at the time of manufacture) diffuses into the conductor layer by low-temperature firing. To confirm this, this diffusion is not observed in Nb, which is very similar in nature to Ta (see FIG. 3). From these facts, it is considered that the phenomenon that the component constituting the conductor layer diffuses to the dielectric ceramic side is a peculiar phenomenon that occurs in the dielectric ceramic containing Ta and V simultaneously.
[0008]
In consideration of these facts, the present inventors studied suppression of diffusion of components constituting the conductor layer into the dielectric ceramic. As a result, it was found that this diffusion can be suppressed surprisingly effectively when Cu is added (see FIGS. 1 and 8), and the present invention has been completed. That is:
[0009]
In the dielectric ceramic composition of the present invention, 0.43 ≦ x ≦ 0.57, 0 ≦ y ≦ 0. 0 when the molar ratio of Bi is x, the molar ratio of Nb is y, and the molar ratio of Ta is z. 52, 0.01 ≦ z ≦ 0.57, and Bi, Nb and Ta are contained so as to satisfy x + y + z = 1, and Bi is further ₂ O ₃ , Nb to Nb ₂ O ₅ , Ta to Ta ₂ O ₅ Assuming that the total content of Bi, Nb and Ta converted as 100 parts by mass, V is V ₂ O ₅ It is characterized by containing α parts by mass in terms of Cu, Cu being contained by β parts by mass in terms of CuO, and satisfying α ≦ 5, β ≦ 14, and β / α ≧ 0.875. Further, when the total content of Bi, Nb and Ta is 100 parts by mass, Mn is MnO. ₂ It can be contained in an amount of 3.5 parts by mass or less.
An electronic component of the present invention includes a dielectric ceramic made of the dielectric ceramic composition of the present invention, and a conductor layer formed on at least one of the surface and the inside of the dielectric ceramic, It is characterized by being fired at the same time as the dielectric ceramic.
[0010]
【The invention's effect】
According to the dielectric ceramic composition of the present invention, it is possible to obtain excellent dielectric characteristics having a large relative dielectric constant in a high frequency band, a small dielectric loss, and a small absolute value of a temperature coefficient of a resonance frequency. In addition, since a metal having a low melting point such as silver, a silver alloy, copper, or a copper alloy can be simultaneously fired as a conductor layer, the degree of freedom in designing electronic components is high. Furthermore, stable baking can be performed by containing a predetermined ratio of Mn. Moreover, according to the electronic component of the present invention, even when the conductor layer formed by simultaneous firing is provided on the surface and / or inside, the component constituting the conductor layer hardly diffuses to the dielectric ceramic side. Can exhibit excellent dielectric properties.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the dielectric ceramic composition and electronic component of the present invention will be described in detail.
The dielectric ceramic composition of the present invention contains at least four elements other than Nb among Bi, Nb, Ta, V and Cu. This dielectric ceramic composition is usually Bi (NbTa) O. ₄ , BiNbO ₄ , BiTaO ₄ , BiVO ₄ And Cu ₅ V ₂ O ₁₀ In particular, Bi (NbTa) O ₄ Is the main crystal phase.
[0012]
The above “Bi” contains Bi, Nb, and Ta (however, Nb may not be contained) in a molar ratio between three elements “x” in the range of 0.43 ≦ x ≦ 0.57. This x is preferably 0.44 ≦ x ≦ 0.56, more preferably 0.45 ≦ x ≦ 0.55, and particularly preferably 0.46 ≦ x ≦ 0.54. . When x is less than 0.43 or more than 0.57, the no-load quality factor (hereinafter simply referred to as “Qu”) tends to decrease (for example, Qu <300). Further, the relative dielectric constant (hereinafter simply referred to as “ε _r ") Also tends to be smaller (for example, ε _r <40).
[0013]
The “Nb” is contained in a molar ratio between the three elements “y” in the range of y ≦ 0.52, or not contained, as in the case of Bi. This y is preferably 0.1 ≦ y ≦ 0.52, more preferably 0.2 ≦ y ≦ 0.51, and particularly preferably 0.3 ≦ y ≦ 0.50. . This Nb content causes ε _r Furthermore, the temperature coefficient of the resonance frequency (hereinafter simply referred to as “τ _f )) Can be made smaller. However, when y exceeds 0.52, Qu tends to decrease (for example, Qu <300).
[0014]
As in the case of Bi, the “Ta” is contained so that the molar ratio between the three elements is “z” in the range of 0.01 ≦ z ≦ 0.57. This z is preferably 0.01 ≦ z ≦ 0.55, more preferably 0.01 ≦ z ≦ 0.50, and particularly preferably 0.01 ≦ z ≦ 0.40. . When z is less than 0.01, the sintered density tends to decrease (for example, 7.00 g / cm ³ Less than). In 0.01 ≦ z ≦ 0.042, Qu tends to be small (for example, Qu <300) when y <0.38 at the same time. Therefore, it is preferable that y ≧ 0.38 in the range of 0.01 ≦ z ≦ 0.042. On the other hand, when z exceeds 0.50, Bi decreases in conjunction with it, and Qu tends to decrease (for example, Qu <300).
[0015]
The above “V” represents Bi contained in the dielectric ceramic composition of the present invention as Bi. ₂ O ₃ , Nb to Nb ₂ O ₅ (Nb may not be contained), Ta to Ta ₂ O ₅ When the total content of Bi, Nb and Ta converted to oxides is 100 parts by mass, V ₂ O ₅ In the above-mentioned “α” which is the content in terms of oxide, α ≦ 5. α is preferably 0.02 ≦ α ≦ 4.00, more preferably 0.02 ≦ α ≦ 2.00, and particularly preferably 0.02 ≦ α ≦ 1.00.
By containing V, the firing temperature when obtaining the dielectric ceramic composition of the present invention can be effectively lowered. That is, various dielectric properties can be maintained within a preferable range even when firing at a low temperature. However, when α exceeds 5, Qu tends to decrease (for example, Qu <300).
[0016]
The “Cu” is contained in the range of β ≦ 14 in the “β”, which is a content converted to an oxide in terms of CuO, when the total content similar to that in V is 100 parts by mass. This β can be obtained when β ≧ 0.05 (usually β ≦ 10) and β ≧ 0.1 when the purpose is only to suppress the diffusion of the conductor layer as will be described later. (Usually β ≦ 10) is preferable, β ≧ 0.15 (usually β ≦ 10) is more preferable, and β ≧ 0.2 (usually β ≦ 10) is particularly preferable. .
[0017]
Furthermore, in addition to suppressing the diffusion of the conductor layer, in the case of simultaneously obtaining excellent Qu, 0.05 ≦ β ≦ 2.00 (Qu can be made 700 or more). Is preferable, 0.12 ≦ β ≦ 1.6 (Qu can be set to 730 or more), more preferably 0.12 ≦ β ≦ 1.1 (Qu can be set to 780 or more). It is particularly preferred that
[0018]
When the electronic component of the present invention is obtained by containing Cu, it is possible to extremely effectively suppress the components constituting the conductor layer in contact with the dielectric ceramic from diffusing to the dielectric ceramic side (see FIG. 1). . Even if the Cu content is very small, the above suppression can be achieved very effectively. Furthermore, this Cu has an effect of improving Qu by containing it in a certain range. However, when β exceeds 14, Qu tends to be small (in some cases, Qu <300).
[0019]
Furthermore, α representing the V content and β representing the Cu content satisfy the relationship β / α ≧ 0.875. That β / α is 0.875 or more means that the contents of V and Cu contained are converted into molar units, and the molar content of V is M _V And the molar content of Cu is M _Cu Where M is the molar ratio thereof. _Cu / M _V Is M _Cu / M _V It represents that ≧ 2. Β / α is 0.875 ≦ β / α ≦ 69 (2 ≦ M _Cu / M _V ≦ 158), preferably 1.4 ≦ β / α ≦ 60 (3.2 ≦ M _Cu / M _V ≦ 137), more preferably 1.6 ≦ β / α ≦ 35 (3.66 ≦ M) _Cu / M _V ≦ 80), more preferably 1.8 ≦ β / α ≦ 20 (4.11 ≦ M _Cu / M _V It is particularly preferred that ≦ 45.7).
[0020]
When β / α is less than 0.875, even when α ≦ 4 and β ≦ 12 are satisfied, components constituting the conductor layer diffuse to the dielectric ceramic side when the electronic component of the present invention is manufactured. This may not be sufficiently suppressed. More specifically, when the diffusion region is measured by a measurement method described later, for example, the Ag diffusion region (hereinafter simply referred to as “Ag diffusion region”) may exceed 100 μm. On the other hand, even if β / α exceeds 80, the components constituting the conductor layer can be prevented from diffusing to the dielectric ceramic side, but Qu tends to decrease (in some cases, Qu <300). is there.
[0021]
Although the above “Mn” may or may not be contained, when the dielectric ceramic composition of the present invention or the electronic component of the present invention is produced by containing Mn, the size of the Ag diffusion region is reduced. The influence of the firing temperature on the dielectric properties can be extremely effectively suppressed without affecting the dielectric properties. Therefore, excellent dielectric ceramics and electronic components can be stably obtained by containing Mn.
This Mn is MnO when the same total content as in V and Cu is 100 parts by mass. ₂ If the content in terms of oxide is γ parts by mass, it is preferably contained in the range of γ ≦ 3.5. γ is more preferably 0.01 ≦ γ ≦ 3.5, still more preferably 0.02 ≦ γ ≦ 2.5, and particularly preferably 0.05 ≦ γ ≦ 1.5. preferable. When γ exceeds 3.5, Qu tends to be small (in some cases, Qu <300).
[0022]
According to the dielectric ceramic comprising the dielectric ceramic composition of the present invention, the resonant frequency is about 4 GHz and the parallel conductor plate type dielectric cylindrical resonator method (TE) described later is used. ₀₁₁ ) When measured by mode) _r Can be set to 42 to 52, more preferably 43 to 51, and particularly 43.5 to 50.5. Similarly, Qu can be 400 to 910, further 500 to 905, and particularly 600 to 900. Furthermore, τ _f Can be −50 to 0 ppm / ° C., more preferably −40 to −2 ppm / ° C., and particularly preferably −30 to −3 ppm / ° C. The ranges of these dielectric characteristics can be combined with each other.
[0023]
Further, when a conductor layer containing 70% by mass or more of Ag was formed on a dielectric ceramic made of the dielectric ceramic composition of the present invention by co-firing, it was determined by the method described later in the dielectric ceramic comprising the obtained conductor layer. The Ag diffusion zone can be as follows. That is, by setting β to 0.05 or more, the Ag diffusion region can be made 80 μm or less (usually 18 μm or more). Furthermore, by setting β to 0.10 or more, the Ag diffusion region can be made 70 μm or less. In particular, by setting β to 0.15 or more, the Ag diffusion region can be made 40 μm or less. In particular, by setting β to 0.2 or more, the Ag diffusion region can be set to 25 μm or less.
[0024]
Furthermore, by setting β / α to 1.00 or more, the Ag diffusion region can be made 80 μm or less (usually 18 μm or more). Further, by setting β / α to 1.4 or more, the Ag diffusion region can be made 70 μm or less. Particularly, by setting β / α to 1.8 or more, the Ag diffusion region can be made 40 μm or less. In particular, by setting β / α to be 2.8 or more, the Ag diffusion region can be made 25 μm or less.
[0025]
The “electronic component” includes a conductor layer that is co-fired on at least one of the surface of the dielectric ceramic and the interior of the dielectric ceramic. This electronic component may be an active component or a passive component. In other words, even if it is not possible to exhibit dielectric characteristics by itself unless it is connected to another circuit at the time of use, the electronic component according to the present invention may or may not be equipped with other circuits necessary for the performance. included. For example, an antenna switch module or the like can be given as an electronic component having other circuits at the same time, and a coupler, a capacitor, and the like that are installed as a part of the circuit and cannot exhibit dielectric properties by themselves are also the electronic components referred to in the present invention.
The “dielectric ceramic” is made of the dielectric ceramic composition of the present invention. However, the electronic component of the present invention may include a dielectric ceramic made of a dielectric ceramic composition having a composition different from that of the dielectric ceramic composition of the present invention, in addition to the above dielectric ceramic.
[0026]
The “conductor layer” is a layer that is formed on the surface or inside of the dielectric ceramic and exhibits conductivity. Although this electroconductivity is not specifically limited, Usually, it is about 3-5 microhm * cm at normal temperature. The components constituting such a conductor layer are not particularly limited, but one or more of Ag, Cu, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, Au, etc. Can be mentioned. Among these conductor layers, particularly when the conductor layer is composed only of Ag or the conductor layer composed of two or more types including Ag, the diffusion of the conductive component to the dielectric ceramic side is extremely effectively suppressed. Can do. Furthermore, in the present invention, Ag is prevented from diffusing to the dielectric porcelain side even when a conductor layer containing 70 mass% or more (including 100 mass%) of Ag is included in the entire conductor layer. .
[0027]
Whether these conductor layers are fired simultaneously with respect to the dielectric ceramics at the time of manufacture depends on whether the dielectric ceramics obtained by simultaneous firing and the dielectric ceramics obtained by performing secondary firing are used. Judgment can be made using the following three differences (1) to (3). That is, the product obtained by co-firing grows larger than (1), (2) has a large electric resistance, and (3) many porcelain components are diffused in the conductor layer. The conductor layer formed in the dielectric ceramic is usually fired at the same time.
[0028]
Although the method for obtaining the dielectric ceramic composition of the present invention is not particularly limited, for example, it can be obtained as follows.
That is, a mixed powder preparation step of obtaining a mixed powder by mixing component powders so as to satisfy the relationship of x, y, z, α, β and β / α, and further γ, A calcining step of calcining the mixed powder obtained in the mixed powder preparing step at 850 ° C. or less, and a granulated powder preparing step of granulating the calcined powder obtained in the calcining step to obtain a granulated powder A molding step of molding the granulated powder obtained in the granulated powder preparation step to obtain a green molded body, and the green molded body at a temperature exceeding the calcination temperature and 800 to 1100 ° C. A firing step of firing at a temperature in the range can be obtained by a method provided in this order.
[0029]
As the component powder, at least one of Bi oxide powder and compound powder heated to become Bi oxide, at least one of Nb oxide powder and compound powder heated to become Nb oxide, At least one of Ta oxide powder and compound powder heated to become Ta oxide, at least one of V oxide powder and compound powder heated to become V oxide, Cu oxide powder and heating Examples thereof include at least one of compound powders that are converted to Cu oxide, Mn oxide powder, and at least one of compound powders that are heated to become Mn oxide. Examples of each compound powder include carbonates, nitrates and hydroxides containing the above-described elements.
In addition, for example, BiTaO ₄ Compound powder and BiNbO ₄ -Based compound powder and Bi (NbTa) O satisfying the above x, y and z in advance ₄ Powders containing two or more necessary components such as system compound powders can also be used.
[0030]
Moreover, in the said calcination process, it heats with the calcination temperature of 600-850 (preferably 700-800 degreeC) normally. If the calcination temperature is less than 600 ° C., for example, the purpose of performing calcination, in which the reaction is allowed to proceed to some extent to suppress the shrinkage during the main firing and the shrinkage rate is easily controlled, may not be sufficiently achieved. On the other hand, when it exceeds 850 ° C., the calcined powder becomes hard, and it may be difficult to control the particle size in the step of pulverizing the calcined product and further granulating it.
[0031]
Although the particle diameter of the granulated powder granulated in the said granulation process is not specifically limited, It is preferable that the maximum particle diameter of the obtained granulated powder is 8 micrometers or less. If the maximum particle size of the granulated powder exceeds 8 μm, homogeneous growth of the crystal phase during firing may be hindered, and sufficient dielectric properties may be difficult to obtain. Further, the average particle size of the granulated powder is preferably 0.8 to 1.2 μm (particularly 0.9 to 1.1 μm).
[0032]
In the molding step, the pressure to be applied is not particularly limited, but the molding is preferably performed by applying a pressure of 100 MPa or more. When the pressure is less than 100 MPa, densification of the green body to be obtained becomes insufficient, and the shape may not be sufficiently retained during firing.
In the firing step, the firing temperature is preferably 800 to 1100 ° C, more preferably 820 to 1000 ° C, particularly 840 to 970 ° C, and particularly 850 to 950 ° C. it can. That is, the dielectric ceramic composition of the present invention can be obtained by firing at a low temperature. If the firing temperature is less than 800 ° C., it may not be able to be sufficiently sintered. If the firing temperature exceeds 1100 ° C., an undesired crystal phase is likely to grow, and it is difficult to obtain sufficient dielectric properties. In some cases, it is not preferable.
[0033]
In addition to the above steps, necessary steps can be provided. That is, for example, a degreasing process. Usually, since a green compact contains a binder, a degreasing step for degreasing the binder can be provided. This degreasing step is performed before the firing step, and the firing step can be continued as it is.
[0034]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
(1) Manufacture of dielectric porcelain for dielectric property measurement
Bi ₂ O ₃ Powder (purity: 98.9%), Nb ₂ O ₅ Powder (purity: 99.9%), Ta ₂ O ₅ Powder (purity; 99.9%), V ₂ O ₅ Powder (purity; 99.5%), CuO powder (purity; 99.9%) and MnO ₂ Using powder (purity: 96.0%) as a component powder, x, y, z, α, β, β / α, and γ shown in Experimental Examples 1 to 46 in Table 1, Table 2, and Table 3, respectively. A predetermined amount (the total amount of the mixed powder was 200 g in any of the experimental examples) was weighed and mixed to obtain a mixed powder.
[0035]
[Table 1]

“*” In the table indicates that it is outside the scope of the present invention.
[0036]
[Table 2]

[0037]
[Table 3]

“*” In the table indicates that it is outside the scope of the present invention.
[0038]
Thereafter, the obtained mixed powder is put into a vibration mill and subjected to primary pulverization (3 hours), and then heated to 800 ° C. at a temperature rising rate of 200 ° C./hour in an air atmosphere and calcined for 2 hours. Then, the temperature was lowered at a temperature drop rate of 200 ° C./hour to obtain a calcined powder. An organic binder (about 5 g) and water (about 200 g) are added to the obtained calcined powder, put into a ball mill, and subjected to secondary pulverization using an alumina ball having a diameter of 20 mm at a rotation speed of the mill of 90 rpm (24 hours). Went. Thereafter, the obtained secondary pulverized powder is granulated by vacuum freeze-drying (pressure; about 53 Pa, freezing temperature; −40 to −20 ° C., drying temperature; 40 to 50 ° C., time; 20 hours). A powder was obtained. The obtained granulated powder was put into a mold and pressurized at 100 MPa to obtain a cylindrical unfired molded body having a diameter of 19 mm and a height of 10 mm.
[0039]
Next, the obtained green molded body was degreased by raising the temperature to 500 ° C. at a temperature rising rate of 50 ° C./hour and holding it for 3 hours in an air atmosphere. Then, it baked by heating up to each baking temperature shown in Table 1, Table 2, and Table 3 with a temperature increase rate of 100 degreeC / hour, and hold | maintaining for 2 hours, and then, at a temperature-fall rate of 100 degreeC / hour. The temperature was lowered to obtain a dielectric ceramic made of the dielectric ceramic composition of the present invention and a dielectric ceramic made of the dielectric ceramic composition of the comparative example.
Then, each obtained dielectric ceramic was polished so as to be a cylindrical shape having a diameter of 16 mm and a height of 8 mm, then subjected to ultrasonic cleaning, and then kept at 100 ° C. for 4 hours to be dried. Dielectric porcelain for measuring dielectric characteristics (experimental examples 3 to 17, 19 to 34, 36 to 39, and 41 to 46) made of a dielectric ceramic composition, and dielectric characteristic measurement made of a dielectric ceramic composition of a comparative example Dielectric ceramics (Experimental Examples 1, 2, 18, 35 and 40) were obtained.
[0040]
(2) Manufacture of electronic parts for Ag diffusion region measurement
Using the same component powder as in (1) above, a calcined powder was obtained by the same method. Predetermined amounts of toluene and a dispersant were added to the obtained calcined powder, and secondary pulverization was performed in the same manner as in (1) above. Thereafter, a resin solution obtained by stirring and dissolving an acrylic binder and dioctyl phthalate as a plasticizer in toluene for 4 hours or more was added to the obtained secondary pulverized powder, and the pulverization time was changed to 4 hours. A slurry was obtained by mixing in the same manner as in the secondary pulverization. By passing the obtained slurry through a 200-mesh filter, foreign matters and the like in the slurry were removed. Thereafter, toluene was further added to adjust the viscosity to 3 Pa · s, and then defoaming was performed. The slurry thus obtained was put into a doctor blade type casting apparatus and formed into a sheet having a thickness of 100 to 300 μm. Then, it cut out to 6 cm long and 5 cm wide, and obtained the unbaking molded object.
[0041]
Three sheet-like green compacts thus obtained were pressure-bonded and laminated, and a conductive layer paste containing 90% by mass of Ag based on the total paste was screen-printed on the surface of the square of 2 mm. Thereafter, three sheet-like green molded bodies were further pressure-bonded and laminated so as to cover the printed conductive layer paste. Next, the obtained unfired laminate was pressed and pressure-bonded at 20 MPa using a thermocompression bonding machine.
Thereafter, the obtained unfired laminate is degreased in the same manner as in the above (1), subsequently fired, and a conductive layer co-fired with a dielectric ceramic made of the dielectric ceramic composition of the present invention; An electronic component (Experimental Examples 3-17, 19-34, 36-39 and 41-46), and an electronic component comprising a dielectric ceramic comprising a dielectric ceramic composition of a comparative example and a co-fired conductive layer Parts (Experimental Examples 1, 2, 18, 35 and 40) were obtained. These electronic components are shown in the respective tables using the same numbers as the experimental example No. in the above (1) for easy understanding.
[0042]
(3) Measurement of dielectric properties and sintered density
Using the dielectric porcelain for dielectric property measurement obtained in (1) above, the parallel conductor plate type dielectric cylindrical resonator method (TE ₀₁₁ Mode), the resonance frequencies f shown in Table 1, Table 2, and Table 3. ₀ Ε at _r , Qu and τ _f Was measured. The results are shown in Table 1, Table 2 and Table 3. Τ _f Was measured in the temperature range of 25-80 ° C. and calculated according to the following formula (1). F in Formula (1) ₂₅ Represents the resonance frequency at 25 ° C. and f ₈₀ Represents the resonance frequency at 80 ° C., and ΔT represents 55 ° C., which is the difference between 80 ° C. and 25 ° C.
τ _f = (F ₈₀ -F ₂₅ ) / (F ₂₅ × ΔT) ・ ・ ・ ・ ▲ 1 ▼
Moreover, the density after baking was measured by the Archimedes method, and it described together as sintered density in Table 1, Table 2, and Table 3.
[0043]
(4) Measurement of Ag diffusion region (see Fig. 9)
The electronic component 1 obtained in the above (2) (Experimental Examples 1 to 46) was sealed in the resin 11 and polished in the stacking direction so that the conductor layer 13 formed inside the dielectric ceramic 12 was exposed. . Thereafter, the surface on which the conductor layer 13 is exposed is subjected to a line analysis with respect to Ag using an X-ray probe microanalyzer (hereinafter simply referred to as “EPMA”; model “JXA-8800M” manufactured by JEOL Data Dam Co., Ltd.). Went. In this line analysis, a wavelength dispersive X-ray spectrometer (WDS) was used under vacuum conditions, the irradiation current was 0.25 nA, and the acceleration voltage was 20 kV.
[0044]
In this result, a region obtained by removing the conductor layer 13 from a region measured with an Ag X-ray intensity of 9 or more was defined as an Ag diffusion region 14 in which Ag diffusion was observed. In accordance with this standard, the length of the Ag diffusion region 14 observed in one direction passing through the Ag diffusion region 14 from the conductor layer 13 and moving away from the conductor layer 13 is measured (as indicated by the thick arrow 16 in FIG. 9). Table 1, Table 2 and Table 3 are also shown as “range”. In each figure, 15 is a measured area.
[0045]
(5) Creation of element maps using EPMA
Using the same EPMA as in (4) above, an element map was created for each element of the electronic component of Experimental Example 5 under the same measurement conditions. At this time, the measurement range was □ 200 μm, the measurement time was 30 milliseconds per point, the pixel size was 0.5 μm, and the number of pixels was 300 × 300. The obtained element maps are shown in FIGS. 2 relates to Bi, FIG. 3 relates to Nb, FIG. 4 relates to Ta, FIG. 5 relates to V, FIG. 6 relates to Cu, FIG. 7 relates to Mn, and FIG.
[0046]
(7) Evaluation
Hereinafter, description will be made based on the measurement results obtained up to (3) to (5).
(1) Regarding α and β
From Experimental Examples 1 to 11, the correlation between β, which is the compounding amount of Cu shown in Table 1, and the Ag diffusion region is shown in FIG. As can be seen from FIG. 1, it can be seen that Cu is very effectively suppressed from diffusing Ag due to its slight content. That is, when Cu is not contained, the Ag diffusion region is as large as 180 μm as shown in Experimental Example 1 (Comparative Example). On the other hand, as shown in Experimental Example 3 (Example), it can be seen that the Ag diffusion region is reduced to 68 μm and the Ag diffusion region is reduced to 37.8% by blending only 0.1 part by mass. Furthermore, as shown in Experimental Example 6 (Example), the Ag diffusion region is 24 μm with only 0.3 parts by mass, and the Ag diffusion region is up to 13.3% compared to the case where Cu is not contained. You can see that it has been reduced.
[0047]
This effect is ₂ O ₅ It can be seen from the results of Experimental Example 1 (Comparative Example) and Experimental Example 2 (Comparative Example) that it is necessary to satisfy β / α ≧ 0.875 in relation to α, which is the blending amount of. On the other hand, if Cu is excessively contained, Qu may be as small as 200 or less as shown in Experimental Example 18 (Comparative Example). For this reason, it is necessary to make (beta) which is the compounding quantity of CuO smaller than 17.14 mass parts.
[0048]
The size of the Ag diffusion region is not only determined by the Cu content β, but is also influenced by the correlation between the V content α and the Cu content β. Example) and Experimental Example 11 (Example). That is, in Experimental Example 3, when the compounding amount of CuO is 0.1 part by mass, the Ag diffusion region is 68 μm. On the other hand, in Experimental Example 11, although the compounding amount of CuO is 0.086 parts by mass, which is smaller than that of Experimental Example 3, the Ag diffusion region is 25 μm. That is, compared with Experimental Example 3, although the Experimental Example 11 has a smaller Cu content, the Ag diffusion region is smaller. This is presumably because the content of V is lower in Experimental Example 11 than in Experimental Example 3.
[0049]
Furthermore, regarding this V, V ₂ O ₅ If α exceeds the range of the present invention, Qu may be as small as 200 or less as shown in Experimental Example 18 (Comparative Example). For this reason, V ₂ O ₅ The blending amount of must be smaller than 6.00 parts by mass.
[0050]
(2) Regarding γ
Experimental Examples 26 to 29 in Table 2 do not contain Mn, Experimental Examples 30 to 34 do not contain Mn, and are the results of changing the firing temperature between 850 and 950 ° C., respectively. Changes between Experimental Examples 26 to 29 and Experimental Examples 30 to 34 are as follows.
Experimental Examples 26-29
ε _r 0.6 variation between 45.0 and 45.6
11 fluctuations between Qu 892-901
τ _f 0.6ppm / ° C variation between -9.9 to -10.5ppm / ° C
Experimental examples 30 to 34
ε _r 3.8 variation between 38.3 and 42.1
145 fluctuations between Qu 745-890
τ _f 7.5 ppm / ° C. fluctuation between −12.3 and −19.8 ppm / ° C.
[0051]
From this result, it can be seen that the inclusion of Mn can extremely effectively suppress the influence of the firing temperature on the dielectric properties without affecting the Ag diffusion region. That is, ε _r Is suppressed by a maximum of 84%, Qu is suppressed by a maximum of 92%, and τ _f The amount of change is suppressed up to 92%. Even if it does not contain Mn, excellent dielectric properties are exhibited by having the composition of the present invention. However, the dielectric characteristics are likely to change depending on the firing temperature during manufacture, and it may be difficult to stably obtain a dielectric ceramic having desired dielectric characteristics. However, it can be seen that by containing Mn, the influence of the firing temperature can be greatly suppressed, and excellent dielectric properties can be obtained stably.
[0052]
However, it can be seen from Experimental Examples 19 to 25 that Qu tends to decrease as the Mn content γ increases. In particular, when γ changes from 2.0 parts by mass (Experimental Example 24) to 3.0 parts by mass (Experimental Example 25), Qu changes from 523 to 398. Even if it is a mass part, the effect containing Mn is fully exhibited. For this reason, it turns out that the fall of Qu can be suppressed effectively by suppressing (gamma) to less than 3.0.
[0053]
(3) Regarding x, y and z
From Experimental Example 40 in Table 3, it can be seen that when the value of x exceeds the range of the present invention (x = 0.60), Qu becomes as small as 231. Similarly, it can be seen from Experimental Example 35 that when y and z exceed the range of the present invention (y = 0.54, z = 0.06), Qu is as small as 250.
On the other hand, from Experimental Examples 36 to 39 and Experimental Examples 41 to 46 according to the present invention (0.43 ≦ x ≦ 0.57, 0 <y ≦ 0.52, 0.01 ≦ z ≦ 0.57). , Ε _r Is between 41.9 and 50.4, Qu is between 856 and 903, and τ _f It can be seen that each of the dielectric properties can be widely controlled between −53.9 and −4 ppm / ° C. The Ag diffusion region can be stabilized between 24 and 25 μm.
[0054]
(4) Regarding element map results
2 and 3, it can be seen that Bi and Nb contained in the dielectric ceramic are not diffused to the conductor layer side. On the other hand, it can be seen from FIGS. 4 to 6 that Ta, V, and Cu contained in the dielectric ceramic are diffused toward the conductor layer. Further, it can be seen from FIG. 7 that Mn is also diffused to the conductor layer side although it is slight. On the other hand, from FIG. 8, Ag constituting the conductor layer is slightly diffused to the dielectric ceramic side, but the Ag diffusion area is as small as 25 μm and is suppressed to such a level that there is no problem in practical use. I understand.
From these element maps and FIG. 1 above, in the dielectric porcelain containing Ta and V, Cu is contained, and this Cu causes diffusion to the conductor layer side. It can be seen that Ag constituting the layer can be extremely effectively suppressed from diffusing to the dielectric ceramic side.
[Brief description of the drawings]
FIG. 1 is a graph showing the correlation between the compounding amount of CuO and an Ag diffusion region.
FIG. 2 is an element map by EPMA regarding Bi of Experimental Example 5 which is a product of the present invention.
FIG. 3 is an element map by EPMA regarding Nb of Experimental Example 5 which is a product of the present invention.
FIG. 4 is an element map by EPMA regarding Ta of Experimental Example 5 which is a product of the present invention.
FIG. 5 is an element map by EPMA regarding V of Experimental Example 5 which is a product of the present invention.
FIG. 6 is an element map by EPMA regarding Cu of Experimental Example 5 which is a product of the present invention.
FIG. 7 is an element map by EPMA regarding Mn of Experimental Example 5 which is a product of the present invention.
FIG. 8 is an element map by EPMA regarding Ag of Experimental Example 5 which is a product of the present invention.
FIG. 9 is an explanatory diagram regarding measurement of an Ag diffusion region and creation of an element map.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1; Electronic component, 11; Resin, 12; Dielectric ceramic composition (dielectric ceramic), 13; Conductor layer, 14; Ag diffusion area, 15;

Claims (3)

When the molar ratio of Bi is x, the molar ratio of Nb is y, and the molar ratio of Ta is z, 0.43 ≦ x ≦ 0.57, 0 ≦ y ≦ 0.52, 0.01 ≦ z ≦ 0. Bi, Nb, and Ta are contained so as to satisfy 57 and x + y + z = 1, and Bi, Nb, and Ta are converted into Bi as Bi ₂ O ₃ , Nb as Nb ₂ O ₅ , and Ta as Ta ₂ O ₅ , respectively. When the total content is 100 parts by mass, V is converted to V ₂ O ₅ to contain α part by mass, Cu is converted to CuO to contain β part by mass, α ≦ 5, β ≦ 14, And a dielectric ceramic composition satisfying β / α ≧ 0.875. The dielectric ceramic composition according to claim 1, wherein Mn is contained in an amount of 3.5 parts by mass or less in terms of MnO ₂ when the total content of Bi, Nb, and Ta is 100 parts by mass. A dielectric ceramic comprising the dielectric ceramic composition according to claim 1 and a conductor layer formed on at least one of a surface and an inside of the dielectric ceramic, wherein the conductor layer is the dielectric An electronic component that is fired simultaneously with porcelain.

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