JP2018104210A - Dielectric ceramic composition and laminate capacitor - Google Patents
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Abstract
Description
本発明は、誘電体磁器組成物および積層コンデンサに関する。 The present invention relates to a dielectric ceramic composition and a multilayer capacitor.
積層コンデンサ用のセラミックには、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示すことが求められている。この要求の実現は、現在市場で最も用いられているＢａＴｉＯ3系の誘電体セラミックでは難しい。そこで、新たな誘電体セラミックとして、ペロブスカイトと構造が良く似ているが分極構造の違う正方晶タングステンブロンズ（ＴＴＢ）構造が検討されている。 Ceramics for multilayer capacitors are required to exhibit a high dielectric constant and resistivity even at high temperatures and to exhibit a stable dielectric constant when a DC voltage is applied. Realization of this requirement is difficult with the BaTiO 3 dielectric ceramics most used on the market today. Therefore, as a new dielectric ceramic, a tetragonal tungsten bronze (TTB) structure having a structure similar to that of perovskite but having a different polarization structure has been studied.
特許文献１には、（Ｋ1-yＮａy）Ｓｒ2Ｎｂ5Ｏ15（但し、０≦ｙ＜０．２）かつ副成分としてＮｂの２０％以下のＭｎを含む誘電体磁器組成物が開示されている。 Patent Document 1 discloses a dielectric ceramic composition containing (K 1-y Na y ) Sr 2 Nb 5 O 15 (where 0 ≦ y <0.2) and 20% or less of Nb as a subcomponent. It is disclosed.
特許文献２には、一般式｛Ａ1-x（ＲＥ）2x/3｝ｙ−Ｂ2Ｏ5+yで表され、タングステンブロンズ構造を有する化合物を有し、前記Ａは、Ｂａ、Ｃａ、ＳｒおよびＭｇからなる群から選ばれる少なくとも１つ、前記Ｂは、ＮｂおよびＴａからなる群から選ばれる少なくとも１つ、前記ＲＥは、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＬｕからなる群から選ばれる少なくとも１つであり、前記ｘおよびｙが、０＜ｘ＜１、ｙ＜１．０００の関係を満足することを特徴とし、Ｖ、Ｍｏ、Ｆｅ、Ｗ、ＭｎおよびＣｒからなる群から選ばれる少なくとも１つの酸化物をさらに有する誘電体磁器組成物が開示されている。 Patent Document 2 includes a compound represented by the general formula {A 1-x (RE) 2x / 3 } y-B 2 O 5 + y and having a tungsten bronze structure, and A represents Ba, Ca, At least one selected from the group consisting of Sr and Mg, the B is at least one selected from the group consisting of Nb and Ta, and the RE is Sc, Y, La, Ce, Pr, Nd, Sm, Eu, It is at least one selected from the group consisting of Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and x and y satisfy the relationship of 0 <x <1, y <1.000 And a dielectric ceramic composition further comprising at least one oxide selected from the group consisting of V, Mo, Fe, W, Mn and Cr.
しかしながら、特許文献１に記載の誘電体磁気組成物では、高い誘電率および高温での比較的高い抵抗率を実現できているが、強誘電性を大きくしているため、高温での誘電率変化が大きく、また直流電圧印加時の誘電率低下が大きいと考えられる。特許文献２に記載の誘電体磁気組成物では、強誘電性を抑制し、直流電圧印加時の誘電率の低下を抑えているが、高温での抵抗率が十分に高くないと考えられる。 However, although the dielectric magnetic composition described in Patent Document 1 can achieve a high dielectric constant and a relatively high resistivity at high temperature, since the ferroelectricity is increased, a change in dielectric constant at high temperature is achieved. It is considered that the dielectric constant decreases greatly when a DC voltage is applied. The dielectric magnetic composition described in Patent Document 2 suppresses ferroelectricity and suppresses a decrease in dielectric constant when a DC voltage is applied, but it is considered that the resistivity at high temperature is not sufficiently high.
以上のように、正方晶タングステンブロンズ（ＴＴＢ）構造をもつ誘電体磁気組成物の検討がなされているものの、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示す誘電体磁気組成物が実現されるに至っていない現状にある。 As described above, although a dielectric magnetic composition having a tetragonal tungsten bronze (TTB) structure has been studied, it exhibits a high dielectric constant and resistivity even at high temperatures, and has a stable dielectric constant when a DC voltage is applied. A dielectric magnetic composition showing the above has not yet been realized.
本発明はこのような事情に鑑みてなされたものであり、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示す誘電体磁気組成物、および当該誘電体磁気組成物を備えた積層コンデンサを提供することを目的とする。 The present invention has been made in view of such circumstances, and shows a dielectric magnetic composition that exhibits a high dielectric constant and resistivity even at a high temperature and exhibits a stable dielectric constant when a DC voltage is applied, and the dielectric. An object of the present invention is to provide a multilayer capacitor provided with a magnetic composition.
上記の目的を達成するため、誘電体磁気組成物の一態様は、一般式Ａ3（Ｂ１）（Ｂ２）4Ｏ15で表される正方晶タングステンブロンズ構造を有する主成分を含有する誘電体磁器組成物であって、Ａは、ＢｉおよびＢａを含み、Ｂ１およびＢ２は、ＺｒおよびＮｂを含み、Ｂ１およびＢ２の合計を１００ｍｏｌ％とした場合、Ｂｉの含有量が４．９５ｍｏｌ％以上５０．５０ｍｏｌ％未満であり、Ｂａの含有量が１０．１ｍｏｌ％より大きく５４．４５ｍｏｌ％以下であり、Ｂ１およびＢ２に対するＡの比率は０．５９４以上０．６０６未満であり、全体を１００ｍｏｌ％とした場合、Ｚｒの含有量が１０ｍｏｌ％より大きく７０ｍｏｌ％未満であり、Ｎｂの含有量が１０ｍｏｌ％より大きく８０ｍｏｌ％未満である。 In order to achieve the above object, one embodiment of a dielectric magnetic composition is a dielectric ceramic containing a main component having a tetragonal tungsten bronze structure represented by the general formula A 3 (B1) (B2) 4 O 15 In the composition, A contains Bi and Ba, B1 and B2 contain Zr and Nb, and the total content of B1 and B2 is 100 mol%, the Bi content is 4.95 mol% or more and 50. It is less than 50 mol%, the Ba content is more than 10.1 mol% and less than or equal to 54.45 mol%, the ratio of A to B1 and B2 is 0.594 or more and less than 0.606, and the whole is 100 mol% In this case, the Zr content is greater than 10 mol% and less than 70 mol%, and the Nb content is greater than 10 mol% and less than 80 mol%.
また、上記の目的を達成するため、積層コンデンサの一態様は、上述した誘電体磁気組成物を備えるものである。 In order to achieve the above object, one aspect of the multilayer capacitor includes the above-described dielectric magnetic composition.
本発明によれば、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示す誘電体磁気組成物、および当該誘電体磁気組成物を備えた積層コンデンサを提供できる。 According to the present invention, a dielectric magnetic composition that exhibits a high dielectric constant and resistivity even at a high temperature and exhibits a stable dielectric constant when a DC voltage is applied, and a multilayer capacitor provided with the dielectric magnetic composition are provided. it can.
（誘電体磁気組成物）
本実施形態に係る誘電体磁気組成物は、正方晶タングステンブロンズ構造を有する主成分（ＡおよびＢ）を含有する誘電体磁器組成物である。正方晶タングステンブロンズ構造は一般式Ａ3（Ｂ１）（Ｂ２）4Ｏ15で表されるが、Ｂ１およびＢ２に対するＡの比率（Ａ／（Ｂ１＋Ｂ２））が必ずしも０．６である必要はなく、比率は０．５９４以上０．６０６未満であればよい。
(Dielectric magnetic composition)
The dielectric magnetic composition according to this embodiment is a dielectric ceramic composition containing main components (A and B) having a tetragonal tungsten bronze structure. The tetragonal tungsten bronze structure is represented by the general formula A 3 (B1) (B2) 4 O 15 , but the ratio of A to B1 and B2 (A / (B1 + B2)) is not necessarily 0.6, The ratio may be 0.594 or more and less than 0.606.
Ａは、ＢｉおよびＢａを含む。すなわち、正方晶タングステンブロンズ構造におけるＡサイト成分が、ＢｉおよびＢａを含む。本実施形態では、Ｂ１およびＢ２の合計を１００ｍｏｌ％とした場合、Ｂｉの含有量が４．９５ｍｏｌ％以上５０．５０ｍｏｌ％未満であり、Ｂａの含有量が１０．１ｍｏｌ％より大きく５４．４５ｍｏｌ％以下である。なお、Ａサイト成分は、ＢｉおよびＢａ以外の元素を含んでいてもよく、例えば、ＣａやＬａを含んでいてもよい。 A includes Bi and Ba. That is, the A site component in the tetragonal tungsten bronze structure contains Bi and Ba. In this embodiment, when the sum of B1 and B2 is 100 mol%, the Bi content is 4.95 mol% or more and less than 50.50 mol%, and the Ba content is greater than 10.1 mol% and 54.45 mol%. It is as follows. The A site component may contain elements other than Bi and Ba, and may contain, for example, Ca and La.
Ｂ１およびＢ２は、ＺｒおよびＮｂを含み、選択的にさらにＴｉおよびＴａの少なくとも１つを含んでいてもよい。すなわち、正方晶タングステンブロンズ構造におけるＢ１およびＢ２サイトがＺｒおよびＮｂで構成されており、場合によってその一部がＴｉおよびＴａのいずれかにより構成されている。さらに、誘電体磁気組成物全体を１００ｍｏｌ％とした場合、Ｚｒの含有量が１０ｍｏｌ％より大きく７０ｍｏｌ％未満であり、Ｎｂの含有量が１０ｍｏｌ％より大きく８０ｍｏｌ％未満に設定されている。また、Ｂ１およびＢ２がＴｉまたはＴａをさらに含む場合には、誘電体磁気組成物全体を１００ｍｏｌ％とした場合、Ｔｉの含有量が２０ｍｏｌ％未満であり、Ｔａの含有量が６０ｍｏｌ％未満に設定されている。 B1 and B2 contain Zr and Nb, and may optionally further contain at least one of Ti and Ta. That is, the B1 and B2 sites in the tetragonal tungsten bronze structure are composed of Zr and Nb, and in some cases, a part thereof is composed of either Ti or Ta. Furthermore, when the entire dielectric magnetic composition is 100 mol%, the Zr content is set to be greater than 10 mol% and less than 70 mol%, and the Nb content is set to be greater than 10 mol% and less than 80 mol%. Further, when B1 and B2 further contain Ti or Ta, the content of Ti is set to less than 20 mol% and the content of Ta is set to less than 60 mol% when the entire dielectric magnetic composition is 100 mol%. Has been.
本実施形態に係る誘電体磁気組成物は、正方晶タングステンブロンズ構造を有する主成分（ＡおよびＢ）以外の副成分を含んでいてもよい。副成分は、例えば、Ｍｎ、Ｃｕ、Ｖ、Ｆｅ、ＣｏおよびＳｉから選択される少なくとも１つであり、好ましくは、ＭｎまたはＳｉから選択される少なくとも１つである。例えば、本実施形態では、Ｂ１およびＢ２の合計を１００ｍｏｌ％とした場合、副成分の合計含有量は５．０ｍｏｌ％未満であり、好ましくは３．０ｍｏｌ％未満である。 The dielectric magnetic composition according to the present embodiment may contain subcomponents other than the main components (A and B) having a tetragonal tungsten bronze structure. The subcomponent is, for example, at least one selected from Mn, Cu, V, Fe, Co, and Si, and preferably at least one selected from Mn or Si. For example, in this embodiment, when the sum total of B1 and B2 is 100 mol%, the total content of subcomponents is less than 5.0 mol%, preferably less than 3.0 mol%.
本実施形態では、正方晶タングステンブロンズ構造を構成する主成分Ａ、Ｂ１、Ｂ２と、それ以外の副成分は主として上述した成分からなるものであるが、アルカリ金属、遷移金属、Ｃｌ、Ｓ、Ｐ等を微量含有していてもよい。 In this embodiment, the main components A, B1, B2 constituting the tetragonal tungsten bronze structure and the other subcomponents are mainly composed of the above-described components, but alkali metals, transition metals, Cl, S, P Etc. may be contained in trace amounts.
本実施形態に係る誘電体磁気組成物によれば、一般式Ａ3（Ｂ１）（Ｂ２）4Ｏ15で表される正方晶タングステンブロンズ構造を有する主成分を含有し、Ａは、一定量のＢｉおよびＢａを含み、Ｂ１およびＢ２は、一定量のＺｒおよびＮｂを含むことにより、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示す効果を奏することができる。本実施形態によれば、ＡサイトのイオンとしてＢｉを一定量用いて、Ｂサイトのイオンによるナノ分極領域を強化することにより、ペロブスカイト構造では設計しにくい、分極特性を発揮できるものと考えられる。またＺｒとＮｂによるネットワークが高い抵抗率を維持すると考えられる。なお、Ｂｉが多すぎるとＢサイトの分極状態に影響を及ぼし、十分な効果が得られない。 The dielectric magnetic composition according to the present embodiment contains a main component having a tetragonal tungsten bronze structure represented by the general formula A 3 (B1) (B2) 4 O 15 , and A is a certain amount Bi and Ba are included, and B1 and B2 contain a certain amount of Zr and Nb, thereby exhibiting a high dielectric constant and resistivity even at a high temperature and exhibiting a stable dielectric constant when a DC voltage is applied. Can do. According to the present embodiment, it is considered that by using a certain amount of Bi as the A site ion and strengthening the nanopolarization region by the B site ion, it is possible to exhibit polarization characteristics that are difficult to design in the perovskite structure. Moreover, it is thought that the network by Zr and Nb maintains a high resistivity. In addition, when there is too much Bi, it will affect the polarization state of a B site, and sufficient effect will not be acquired.
本実施形態に係る誘電体磁気組成物は、種々の電子部品や車載部品として使用される積層コンデンサに好適に使用することができる。 The dielectric magnetic composition according to the present embodiment can be suitably used for multilayer capacitors used as various electronic components and in-vehicle components.
（積層コンデンサ）
図１は、本実施形態に係る誘電体磁気組成物を備える積層コンデンサの概略断面図である。
本実施形態の積層コンデンサ１は、例えば図１に示すように、複数層（本実施形態では５層）の誘電体セラミック層２およびこれらの誘電体セラミック層２間にそれぞれ配置された複数の第１、第２内部電極３Ａ、３Ｂを有する積層体と、これらの内部電極３Ａ、３Ｂに電気的に接続され且つ積層体の両端に形成された第１、第２外部電極４Ａ、４Ｂとを備えている。この誘電体セラミック層２として、上述した本実施形態に係る誘電体磁気組成物が用いられる。
(Multilayer capacitor)
FIG. 1 is a schematic cross-sectional view of a multilayer capacitor including a dielectric magnetic composition according to this embodiment.
For example, as shown in FIG. 1, the multilayer capacitor 1 of the present embodiment includes a plurality of layers (five layers in the present embodiment) of dielectric ceramic layers 2 and a plurality of first ceramic layers disposed between the dielectric ceramic layers 2. 1 and a multilayer body having second internal electrodes 3A and 3B, and first and second external electrodes 4A and 4B electrically connected to the internal electrodes 3A and 3B and formed at both ends of the multilayer body. ing. As the dielectric ceramic layer 2, the above-described dielectric magnetic composition according to the present embodiment is used.
第１内部電極３Ａは、図１に示すように、誘電体セラミック層２の一端（同図の左端）から他端（右端）の近傍まで延び、第２内部電極３Ｂは誘電体セラミック層２の右端から左端の近傍まで延びている。第１、第２内部電極３Ａ、３Ｂは導電性材料によって形成されている。この導電性材料としては、例えば、Ｐｔ等の金属を主成分とするものを好ましく用いることができる。また、内部電極の構造欠陥を防止するために、導電性材料にセラミック粉末を少量添加しても良い。 As shown in FIG. 1, the first internal electrode 3 </ b> A extends from one end (left end in the figure) of the dielectric ceramic layer 2 to the vicinity of the other end (right end), and the second internal electrode 3 </ b> B extends from the dielectric ceramic layer 2. It extends from the right end to the vicinity of the left end. The first and second internal electrodes 3A and 3B are made of a conductive material. As this conductive material, for example, a material mainly containing a metal such as Pt can be preferably used. In order to prevent structural defects in the internal electrode, a small amount of ceramic powder may be added to the conductive material.
また、第１外部電極４Ａは、図１に示すように、積層体内の第１内部電極３Ａに電気的に接続され、第２外部電極４Ｂは積層体内の第２内部電極３Ｂに電気的に接続されている。第１、第２外部電極４Ａ、４Ｂは、従来公知のＡｇ、Ｃｕ等の種々の導電性材料によって形成することができる。また、第１、第２外部電極４Ａ、４Ｂの形成手段は、従来公知の各手段を適宜採用することができる。例えば、ガラスフリットを含有したＡｇペーストを塗布して焼き付ける方法がある。また、この上にＮｉ−Ｓｎメッキを施しても良い。 Further, as shown in FIG. 1, the first external electrode 4A is electrically connected to the first internal electrode 3A in the multilayer body, and the second external electrode 4B is electrically connected to the second internal electrode 3B in the multilayer body. Has been. The first and second external electrodes 4A and 4B can be formed of various conductive materials such as conventionally known Ag and Cu. Moreover, conventionally well-known each means can be employ | adopted suitably for the formation means of 1st, 2nd external electrode 4A, 4B. For example, there is a method of applying and baking an Ag paste containing glass frit. Further, Ni—Sn plating may be applied thereon.
本実施形態によれば、積層コンデンサの誘電体セラミック層として上述した組成の誘電体磁気組成物を用いることにより、高い電界強度や高温下において使用される場合であっても容量の低下を抑制できる積層コンデンサを提供できる。 According to this embodiment, by using the dielectric magnetic composition having the above-described composition as the dielectric ceramic layer of the multilayer capacitor, it is possible to suppress a decrease in capacitance even when used at a high electric field strength or at a high temperature. A multilayer capacitor can be provided.
（実施例）
以下、本発明を実施例および比較例によってさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
(Example)
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
（試料の作製）
試料１−１９は、ＢａＣＯ3、ＣａＣＯ3、Ｌａ2Ｏ3、ＺｒＯ2、ＴｉＯ2、Ｎｂ2Ｏ5、Ｔａ2Ｏ5を準備して、表１の主成分に示した組成になるように秤量した後、ボールミルにより混合し、９００℃−１０００℃にて大気中で仮焼を行うことで、正方晶タングステンブロンズ構造（ＴＴＢ）を有する仮焼粉を合成した。なお、各元素の酸化物もしくは炭酸塩を原料として使用したが、各元素の他の化合物を用いても同様の効果が得られる。また、共沈法、水熱法、蓚酸法等の他の合成方法で作製しても構わない。
(Sample preparation)
Sample 1-19 is prepared with BaCO 3 , CaCO 3 , La 2 O 3 , ZrO 2 , TiO 2 , Nb 2 O 5 , and Ta 2 O 5 so as to have the composition shown in the main components in Table 1. After weighing, the mixture was mixed by a ball mill and calcined in the atmosphere at 900 ° C. to 1000 ° C. to synthesize calcined powder having a tetragonal tungsten bronze structure (TTB). In addition, although the oxide or carbonate of each element was used as a raw material, the same effect is acquired even if it uses the other compound of each element. Moreover, you may produce by other synthesis methods, such as a coprecipitation method, a hydrothermal method, and an oxalic acid method.
また、副成分としてＭｎの酸化物の粉末、ＳｉＯ2の粉末を準備し、Ｚｒ＋Ｔｉ＋Ｎｂ＋Ｔａの合計１００ｍｏｌ部に対する各添加元素が表１の副成分に示したモル部になるよう、秤量し、ボールミルにより水中にて上記仮焼粉と混合、乾燥することで誘電体原料を得た。 Also, Mn oxide powder and SiO 2 powder were prepared as subcomponents, and weighed so that each additive element was in the molar parts shown in subcomponents in Table 1 with respect to a total of 100 mol parts of Zr + Ti + Nb + Ta. A dielectric material was obtained by mixing with the calcined powder and drying.
この原料粉末に、ポリビニルブチラール系バインダー、可塑剤およびエタノールなどの有機溶媒を加えて、ボールミルにより湿式混合し、セラミックスラリーを作製した。このセラミックスラリーをドクターブレード法により、焼成後の誘電体素子厚が２０μｍになるように、シート成形し、矩形のグリーンシートを得た。次に、上記セラミックグリーンシート上に、Ｐｔを導電成分として含む導電性ペーストをスクリーン印刷し、内部電極を構成するための導電ペースト層を形成した。 An organic solvent such as polyvinyl butyral binder, plasticizer, and ethanol was added to the raw material powder, and wet mixed by a ball mill to prepare a ceramic slurry. This ceramic slurry was formed into a sheet by a doctor blade method so that the dielectric element thickness after firing was 20 μm, and a rectangular green sheet was obtained. Next, a conductive paste containing Pt as a conductive component was screen-printed on the ceramic green sheet to form a conductive paste layer for constituting an internal electrode.
導電ペースト層が形成されたセラミックグリーンシートを導電ペーストの引き出されている側が互い違いになるように複数枚積層し、積層体を得た。この積層体を、２５０℃−３００℃にて大気中で加熱し、バインダーを燃焼させた。この脱脂後の積層体を、大気中にて１２００℃−１３５０℃で１２０分間保持することで緻密なセラミック積層体を得た。この積層体を溶解し、ＩＣＰ（Inductively Coupled Plasma）分析をしたところ、内部電極成分のＰｔを除いて、表１に示すような組成であった。またこの積層体のＸＲＤ（X-Ray Diffraction）構造解析を行ったところ、主成分がＴＴＢ構造を有することが明らかになった。 A plurality of ceramic green sheets on which the conductive paste layer was formed were laminated so that the sides from which the conductive paste was drawn out were staggered to obtain a laminate. This laminated body was heated in air | atmosphere at 250 to 300 degreeC, and the binder was burned. The degreased laminate was held at 1200 ° C. to 1350 ° C. for 120 minutes in the air to obtain a dense ceramic laminate. When this laminate was dissolved and ICP (Inductively Coupled Plasma) analysis was performed, the composition was as shown in Table 1 except for Pt as an internal electrode component. Further, when an XRD (X-Ray Diffraction) structural analysis of the laminate was performed, it was found that the main component has a TTB structure.
続いて、得られた焼結体の端面にＡｇ電極を焼き付けて測定試料（積層コンデンサ）とした。 Subsequently, an Ag electrode was baked on the end face of the obtained sintered body to obtain a measurement sample (multilayer capacitor).
上記のようにして得られた積層コンデンサの外形寸法は、幅１．６ｍｍ、長さ３．２ｍｍ、厚さ０．６２ｍｍであり、内部電極間に介在する誘電体セラミック層の厚みは２０μｍ、内部電極厚みは１μｍであった。また、有効誘電体セラミック層の総数は２０であり、一層当たりの対向電極面積は２．５ｍｍ2であった。 The outer dimensions of the multilayer capacitor obtained as described above are 1.6 mm in width, 3.2 mm in length, and 0.62 mm in thickness, and the thickness of the dielectric ceramic layer interposed between the internal electrodes is 20 μm. The electrode thickness was 1 μm. The total number of effective dielectric ceramic layers was 20, and the counter electrode area per layer was 2.5 mm 2 .
（試料の評価）
このようにして得られた積層コンデンサの静電容量を室温および１５０℃にて、ＬＣＲメーターを用いて測定（１ＫＨｚ、１Ｖ）し、比誘電率を算出した。またＤＣ印加時の比誘電率は、DC電圧を試料に印加した状態で測定を行うために、外部電圧バイアスフィクスチャを用いて３００Ｖを印加して、ＬＣＲメーターを用いて測定（１ＫＨｚ、１Ｖ）し、比誘電率を算出した。また温度１５０℃にて、２００ＶのＤＣ電圧を印加して、微小電流計をもちいて漏れ電流の測定をし、抵抗率を算出した。それぞれの電気特性は２０個の試験を行い、平均値を求めた。比誘電率が３５０以下である試料、ＤＣ印加時の比誘電率の変化率が１５％以上のもの、高温での誘電率の変化率が２０％以上のもの、高温での抵抗率（Ωｍ）がｌｏｇで７．５以下のものを不良と判定し、規格外とした。
(Sample evaluation)
The capacitance of the multilayer capacitor thus obtained was measured (1 KHz, 1 V) using an LCR meter at room temperature and 150 ° C., and the relative dielectric constant was calculated. In addition, the relative dielectric constant when DC is applied is measured using an LCR meter (1 KHz, 1 V) by applying 300 V using an external voltage bias fixture in order to perform measurement with a DC voltage applied to the sample. The relative dielectric constant was calculated. Further, at a temperature of 150 ° C., a DC voltage of 200 V was applied, the leakage current was measured using a microammeter, and the resistivity was calculated. For each electrical characteristic, 20 tests were performed, and an average value was obtained. Samples with a relative dielectric constant of 350 or less, those with a dielectric constant change rate of 15% or more when DC is applied, those with a dielectric constant change rate of 20% or more at high temperature, resistivity at high temperature (Ωm) A log of 7.5 or less was determined to be defective, and was out of specification.
実施例にて作製した試料１−１９の積層コンデンサの測定結果を表２に示す。なお、表１、２において、※印を付した試料は、本実施形態で説明した好ましい含有量の範囲外のものである。 Table 2 shows the measurement results of the multilayer capacitor of Sample 1-19 produced in the example. In Tables 1 and 2, samples marked with * are out of the preferable content range described in the present embodiment.
表２に示すように、※印を付していない試料は、本実施形態に係る誘電体磁器組成物に該当するものであり、高温でのＤＣ印加時に高い誘電特性（誘電率および高温の抵抗率）を得ることができた。
試料１のように、Ｂｉを含まない組成では、ＤＣ電圧印加時や高温での誘電率の変化が著しく規格外となった。また、試料６のようにＢｉ量が多すぎる場合も、ＴＴＢ構造を維持するためＺｒの比率を上げる必要があり、十分な誘電率の値が得られず規格外となった。
試料７，８のようにイオン半径の近いＣａやＬａのみを用いた場合では、ＤＣ電圧印加なしでの誘電率低下が見られるのみで、ＤＣ電圧印加時や高温の誘電率の変化に優位な値は得られなかった。
試料１１のように、Ｔｉ量の多い組成では高温での抵抗率低下が著しく規格外となった。また、試料１４のようにＴａ置換量が多い場合は、ＤＣ印加なしの誘電率低下が著しく規格外となった。
試料１５，１６のように副成分としてＭｎやＳｉが含まれていても効果を妨げるものではなかった。
試料１７のように、Ｂｉを所定の範囲内で含んでいればＢａでなくＣａなどの元素が用いられていても効果を妨げるものではなかった。
試料１８，１９に示すようにＡ／（Ｂ１＋Ｂ２）にあたる含有元素の比率はＴＴＢ構造を保てる範囲で変わっても優位な特性に問題はない。
As shown in Table 2, the samples not marked with * correspond to the dielectric ceramic composition according to this embodiment, and have high dielectric properties (dielectric constant and high-temperature resistance) when DC is applied at a high temperature. Rate).
As in Sample 1, in the composition not containing Bi, the change in the dielectric constant at the time of applying the DC voltage or at a high temperature was remarkably out of specification. Further, when the amount of Bi was too large as in Sample 6, it was necessary to increase the ratio of Zr in order to maintain the TTB structure, and a sufficient dielectric constant value was not obtained, which was out of specification.
In the case of using only Ca or La having a close ionic radius as in Samples 7 and 8, only a decrease in the dielectric constant is observed without application of a DC voltage, which is superior to changes in the dielectric constant at the time of application of a DC voltage. No value was obtained.
Like the sample 11, in the composition with a large amount of Ti, the decrease in resistivity at a high temperature was remarkably out of specification. Further, when the amount of Ta substitution was large as in Sample 14, the decrease in dielectric constant without DC application was markedly out of specification.
Even if Mn and Si were contained as subcomponents as in Samples 15 and 16, the effect was not hindered.
If Bi was included in a predetermined range as in Sample 17, the effect was not hindered even when an element such as Ca was used instead of Ba.
As shown in Samples 18 and 19, there is no problem in the superior characteristics even if the ratio of the contained element corresponding to A / (B1 + B2) changes within a range in which the TTB structure can be maintained.
以上、本発明の例示的な実施形態および実施例について説明した。 The exemplary embodiments and examples of the present invention have been described above.
本実施形態に係る誘電体磁気組成物は、一般式Ａ3（Ｂ１）（Ｂ２）4Ｏ15で表される正方晶タングステンブロンズ構造を有する主成分を含有する誘電体磁器組成物であって、Ａは、ＢｉおよびＢａを含み、Ｂ１およびＢ２は、ＺｒおよびＮｂを含み、Ｂ１およびＢ２の合計を１００ｍｏｌ％とした場合、Ｂｉの含有量が４．９５ｍｏｌ％以上５０．５０ｍｏｌ％未満であり、Ｂａの含有量が１０．１ｍｏｌ％より大きく５４．４５ｍｏｌ％以下であり、Ｂ１およびＢ２に対するＡの比率は０．５９４以上０．６０６未満であり、全体を１００ｍｏｌ％とした場合、Ｚｒの含有量が１０ｍｏｌ％より大きく７０ｍｏｌ％未満であり、Ｎｂの含有量が１０ｍｏｌ％より大きく８０ｍｏｌ％未満である。これにより、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示す誘電体磁気組成物を実現できる。 The dielectric magnetic composition according to the present embodiment is a dielectric ceramic composition containing a main component having a tetragonal tungsten bronze structure represented by a general formula A 3 (B1) (B2) 4 O 15 , A contains Bi and Ba, B1 and B2 contain Zr and Nb, and the total content of B1 and B2 is 100 mol%, the Bi content is 4.95 mol% or more and less than 50.50 mol%, When the Ba content is greater than 10.1 mol% and less than or equal to 54.45 mol%, the ratio of A to B1 and B2 is 0.594 or more and less than 0.606, and the total content is 100 mol%, the Zr content Is greater than 10 mol% and less than 70 mol%, and the Nb content is greater than 10 mol% and less than 80 mol%. Thereby, it is possible to realize a dielectric magnetic composition that exhibits a high dielectric constant and resistivity even at a high temperature and exhibits a stable dielectric constant when a DC voltage is applied.
また、Ｂ１およびＢ２は、ＴｉまたはＴａをさらに含んでいてもよく、この場合、全体を１００ｍｏｌ％とした場合、Ｔｉの含有量が２０ｍｏｌ％未満であり、Ｔａの含有量が６０ｍｏｌ％未満である。この場合であっても、高温時においても高い誘電率および抵抗率を示し、直流電圧印加時において安定した誘電率を示す誘電体磁気組成物を実現できる。 B1 and B2 may further contain Ti or Ta. In this case, when the whole is 100 mol%, the Ti content is less than 20 mol% and the Ta content is less than 60 mol%. . Even in this case, it is possible to realize a dielectric magnetic composition that exhibits a high dielectric constant and resistivity even at a high temperature and exhibits a stable dielectric constant when a DC voltage is applied.
また、本実施形態に係る積層コンデンサは、上記した誘電体磁気組成物を備えることにより、高い電界強度や高温下において使用される場合であっても容量の低下を抑制できる積層コンデンサを提供できる。 In addition, the multilayer capacitor according to the present embodiment can provide a multilayer capacitor that can suppress a decrease in capacitance even when used in a high electric field strength or at a high temperature by including the above-described dielectric magnetic composition.
なお、以上説明した各実施形態は、本発明の理解を容易にするためのものであり、本発明を限定して解釈するためのものではない。本発明は、その趣旨を逸脱することなく、変更／改良され得るととともに、本発明にはその等価物も含まれる。即ち、各実施形態に当業者が適宜設計変更を加えたものも、本発明の特徴を備えている限り、本発明の範囲に包含される。例えば、各実施形態が備える各要素及びその配置、材料、条件、形状、サイズなどは、例示したものに限定されるわけではなく適宜変更することができる。さらに、図面の寸法比率は図示の比率に限られるものではない。また、各実施形態は例示であり、異なる実施形態で示した構成の部分的な置換又は組み合わせが可能であることは言うまでもなく、これらも本発明の特徴を含む限り本発明の範囲に包含される。 Each embodiment described above is for facilitating the understanding of the present invention, and is not intended to limit the present invention. The present invention can be changed / improved without departing from the spirit thereof, and the present invention includes equivalents thereof. In other words, those obtained by appropriately modifying the design of each embodiment by those skilled in the art are also included in the scope of the present invention as long as they include the features of the present invention. For example, each element included in each embodiment and its arrangement, material, condition, shape, size, and the like are not limited to those illustrated, and can be changed as appropriate. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. Each embodiment is an exemplification, and it is needless to say that a partial replacement or combination of configurations shown in different embodiments is possible, and these are also included in the scope of the present invention as long as they include the features of the present invention. .
１…積層コンデンサ
２…誘電体セラミック層
３Ａ、３Ｂ…内部電極
４Ａ、４Ｂ…外部電極
DESCRIPTION OF SYMBOLS 1 ... Multilayer capacitor 2 ... Dielectric ceramic layer 3A, 3B ... Internal electrode 4A, 4B ... External electrode
Claims (3)
Ａは、ＢｉおよびＢａを含み、
Ｂ１およびＢ２は、ＺｒおよびＮｂを含み、
Ｂ１およびＢ２の合計を１００ｍｏｌ％とした場合、Ｂｉの含有量が４．９５ｍｏｌ％以上５０．５０ｍｏｌ％未満であり、Ｂａの含有量が１０．１ｍｏｌ％より大きく５４．４５ｍｏｌ％以下であり、
Ｂ１およびＢ２に対するＡの比率は０．５９４以上０．６０６未満であり、
全体を１００ｍｏｌ％とした場合、Ｚｒの含有量が１０ｍｏｌ％より大きく７０ｍｏｌ％未満であり、Ｎｂの含有量が１０ｍｏｌ％より大きく８０ｍｏｌ％未満である、
誘電体磁器組成物。 A dielectric ceramic composition containing a main component having a tetragonal tungsten bronze structure represented by the general formula A 3 (B1) (B2) 4 O 15 ,
A includes Bi and Ba,
B1 and B2 include Zr and Nb,
When the total of B1 and B2 is 100 mol%, the Bi content is 4.95 mol% or more and less than 50.50 mol%, the Ba content is greater than 10.1 mol% and less than or equal to 54.45 mol%,
The ratio of A to B1 and B2 is 0.594 or more and less than 0.606,
When the total is 100 mol%, the Zr content is greater than 10 mol% and less than 70 mol%, and the Nb content is greater than 10 mol% and less than 80 mol%.
Dielectric ceramic composition.
全体を１００ｍｏｌ％とした場合、Ｔｉの含有量が２０ｍｏｌ％未満であり、Ｔａの含有量が６０ｍｏｌ％未満である、
請求項１記載の誘電体磁気組成物。 B1 and B2 further contain Ti or Ta,
When the whole is 100 mol%, the Ti content is less than 20 mol%, and the Ta content is less than 60 mol%.
The dielectric magnetic composition according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020043299A (en) * | 2018-09-13 | 2020-03-19 | Tdk株式会社 | Dielectric composition and electronic component |
| JP2020126895A (en) * | 2019-02-01 | 2020-08-20 | Tdk株式会社 | Multilayer electronic component |
| JP2020152622A (en) * | 2019-03-22 | 2020-09-24 | Tdk株式会社 | Dielectric composition and electronic components |
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2016
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Cited By (8)
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| JP2020043299A (en) * | 2018-09-13 | 2020-03-19 | Tdk株式会社 | Dielectric composition and electronic component |
| JP7099212B2 (en) | 2018-09-13 | 2022-07-12 | Tdk株式会社 | Dielectric compositions and electronic components |
| JP2020126895A (en) * | 2019-02-01 | 2020-08-20 | Tdk株式会社 | Multilayer electronic component |
| JP7151520B2 (en) | 2019-02-01 | 2022-10-12 | Tdk株式会社 | multilayer electronic components |
| JP2020152622A (en) * | 2019-03-22 | 2020-09-24 | Tdk株式会社 | Dielectric composition and electronic components |
| CN111718195A (en) * | 2019-03-22 | 2020-09-29 | Tdk株式会社 | Dielectric composition and electronic component |
| CN111718195B (en) * | 2019-03-22 | 2022-07-05 | Tdk株式会社 | Dielectric composition and electronic component |
| JP7168914B2 (en) | 2019-03-22 | 2022-11-10 | Tdk株式会社 | Dielectric compositions and electronic components |
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