JP2020155589A - Magnetic material, and laminated chip component - Google Patents
Magnetic material, and laminated chip component Download PDFInfo
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- 239000000696 magnetic material Substances 0.000 title claims abstract description 57
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910002637 Pr6O11 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 239000010949 copper Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 9
- 230000035699 permeability Effects 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910007541 Zn O Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- -1 Pr 6 O 11 Inorganic materials 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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Abstract
Description
本発明は磁性材料、および積層チップ部品に関する。 The present invention relates to magnetic materials and laminated chip components.
積層インダクタなどの積層チップ部品には、電気絶縁性の磁性層と、電極パターンが形成された電極層とが層状に積層された構造を有するものがある。この種の積層チップ部品は、厚膜技術を用いて磁性層となるペースト状の磁性材料からなるシート上に電極層となる電極パターンが形成されたものを順次積層して得た積層体を焼成し、その焼成によって得られた焼結体の表面に外部電極用ペーストを形成することで製造される。 Some laminated chip components such as a laminated inductor have a structure in which an electrically insulating magnetic layer and an electrode layer on which an electrode pattern is formed are laminated in a layered manner. This type of laminated chip component is obtained by firing a laminate obtained by sequentially laminating an electrode pattern to be an electrode layer on a sheet made of a paste-like magnetic material to be a magnetic layer using thick film technology. Then, it is produced by forming a paste for an external electrode on the surface of the sintered body obtained by the firing.
電極パターンを形成する導電体には、融点が９６２℃のＡｇ（銀）を用いるのが一般的である。そのため、磁性層には、以下の特許文献１に記載の磁性材料のように、低温での焼成が可能なＮｉ系フェライト（Ｎｉ−Ｚｎ系、Ｎｉ−Ｚｎ−Ｃｕ系など）を主成分とした磁性材料が用いられる。なお、以下の特許文献２には、本発明に関連する技術として、高周波領域でもコアロス（損失）が少ない磁性材料について記載されている。 As the conductor forming the electrode pattern, Ag (silver) having a melting point of 962 ° C. is generally used. Therefore, the magnetic layer is mainly composed of Ni-based ferrite (Ni-Zn-based, Ni-Zn-Cu-based, etc.) that can be fired at a low temperature, like the magnetic material described in Patent Document 1 below. Magnetic materials are used. The following Patent Document 2 describes a magnetic material having a small core loss (loss) even in a high frequency region as a technique related to the present invention.
電子機器を構成する電子部品には、より高い周波数で動作することが求められている。したがって、積層インダクタなどの積層チップ部品の磁性層には、高周波領域でもコアロスが低い磁性材料を用いる必要がある。例えば、周知のスネーク（Ｓｎｏｅｋ）の限界を考慮しながら磁性材料の高周波領域でのコアロスを低減させるために、磁性材料中のＦｅ（鉄）の量を少なくして、透磁率μを小さくすることが考えられる。そして、上記特許文献２に記載の磁性材料では、高周波領域におけるコアロスを低くするためにＣｏＯが添加されている。 Electronic components that make up electronic devices are required to operate at higher frequencies. Therefore, it is necessary to use a magnetic material having a low core loss even in a high frequency region for the magnetic layer of a laminated chip component such as a laminated inductor. For example, in order to reduce the core loss in the high frequency region of the magnetic material while considering the limit of the well-known Snoke, the amount of Fe (iron) in the magnetic material is reduced to reduce the magnetic permeability μ. Can be considered. Then, in the magnetic material described in Patent Document 2, CoO is added in order to reduce the core loss in the high frequency region.
しかし、磁性材料は、ＣｏＯを添加すると焼結性が悪化し、積層チップ部品の導体パターンに使用されているＡｇの融点以下で焼成することが困難となる。そして、特許文献２に記載の磁性材料では１０００℃〜１１３０℃の温度で焼成することで焼結体にしている。 However, when CoO is added to the magnetic material, the sinterability deteriorates, and it becomes difficult to fire the magnetic material below the melting point of Ag used in the conductor pattern of the laminated chip component. The magnetic material described in Patent Document 2 is fired at a temperature of 1000 ° C. to 1130 ° C. to form a sintered body.
そこで本発明は、低温焼成が可能であるとともに、高周波領域でのコアロス特性に優れた磁性材料、およびその磁性材料を用いた積層チップ部品を提供することを目的としている。 Therefore, an object of the present invention is to provide a magnetic material capable of low-temperature firing and having excellent core loss characteristics in a high frequency region, and a laminated chip component using the magnetic material.
上記目的を達成するための本発明の一態様は、Ｆｅ２Ｏ３換算でｘｍｏｌ％のＦｅ、ＺｎＯ換算でｙｍｏｌ％のＺｎ、ＣｕＯ換算でｚｍｏｌ％のＣｕ、およびＮｉＯ換算で（１００−ｘ−ｙ−ｚ）ｍｏｌ％のＮｉを含む主成分に、副成分として、前記主成分に対してａｗｔ％のＣｏＯ、ｂｗｔ％のＢｉ２Ｏ３、ｃｗｔ％のＳｉＯ２、ｄｗｔ％のＡｌ２Ｏ３、およびｅｗｔ％のＰｒ６Ｏ１１が添加されてなり、
４０≦ｘ≦４５、０≦ｙ≦１０、５≦ｚ≦１５、
０＜ａ≦０．３、０＜ｂ≦１．０、０＜ｃ≦０．２、０＜ｄ＜０．４、０＜ｅ＜０．１
であることを特徴とする磁性材料としている。０＜ｅ≦０．０５である磁性材料とすればより好ましい。
One aspect of the present invention for achieving the above object is xmol% Fe in Fe 2 O 3 conversion, y mol% Zn in ZnO conversion, zmol% Cu in CuO conversion, and (100-x-) in NiO conversion. yz) Mol% of Ni-containing main component, as sub-components, awt% CoO, bwt% Bi 2 O 3 , cwt% SiO 2 , dwt% Al 2 O 3 with respect to the main component. , And weight% of Pr 6 O 11 added.
40 ≦ x ≦ 45, 0 ≦ y ≦ 10, 5 ≦ z ≦ 15,
0 <a ≦ 0.3, 0 <b ≦ 1.0, 0 <c ≦ 0.2, 0 <d <0.4, 0 <e <0.1
It is a magnetic material characterized by being. It is more preferable to use a magnetic material in which 0 <e ≦ 0.05.
本発明のその他の態様は、前記磁性材料からなる焼結体で形成される電気絶縁性の磁性層と、導電体からなる電極パターンが形成された電極層とが層状に積層されてなる積層チップ部品であって、前記導電体が銀であることを特徴としている。 Another aspect of the present invention is a laminated chip in which an electrically insulating magnetic layer formed of a sintered body made of the magnetic material and an electrode layer formed of an electrode pattern made of a conductor are laminated in layers. It is a component and is characterized in that the conductor is silver.
本発明によれば、低温焼成が可能であるとともに、高周波領域でのコアロス特性に優れた磁性材料、およびその磁性材料を用いた積層チップ部品が提供される。なお、その他の効果については以下の記載で明らかにする。 According to the present invention, there is provided a magnetic material capable of low-temperature firing and excellent core loss characteristics in a high frequency region, and a laminated chip component using the magnetic material. Other effects will be clarified in the following description.
＝＝＝本発明の実施例に想到する過程＝＝＝
磁性材料には、主成分となるフェライトに、副成分として、焼結性や特定の特性を向上させるための添加剤が添加されてなる。主成分として、Ｆｅ２Ｏ３、ＮｉＯ、ＣｕＯ、およびＺｎＯを含むＮｉ系フェライトでは、高周波領域でのコアロスを低減させるために、磁性材料中のＦｅの量をＦｅ２Ｏ３換算で４０〜４５ｍｏｌ％程度としている。それによって、磁性材料の透磁率μが小さくなり、鉄損が低減する。また、焼結性を向上させるＣｕＯは、銅損によるコアロスの劣化を抑制するために、５〜１５ｍｏｌ％程度としている。
=== Process of arriving at the embodiment of the present invention ===
In the magnetic material, an additive for improving sinterability and specific properties is added as a sub-component to ferrite as a main component. In Ni-based ferrite containing Fe 2 O 3 , NiO, CuO, and ZnO as the main components, the amount of Fe in the magnetic material is 40 to 45 mol in terms of Fe 2 O 3 in order to reduce core loss in the high frequency region. It is about%. As a result, the magnetic permeability μ of the magnetic material is reduced, and the iron loss is reduced. Further, CuO for improving sinterability is set to about 5 to 15 mol% in order to suppress deterioration of core loss due to copper loss.
なお、透磁率μは、磁性材料中のＺｎを少なくすることでも低減させることができる。しかし、透磁率μを過度に低下させれば、磁性材料が、本来の磁性体として機能しなくなるため、一般的には、磁性材料中にＺｎＯ換算で１０ｍｏｌ％以下のＺｎを含ませている。磁性材料中にＺｎを全く含ませない場合もある。なお、透磁率μは、１ＭＨｚでの比透磁率μ’でμ’≦１００であればよい。下限については、普通、μ’≒２０であれば問題はない。 The magnetic permeability μ can also be reduced by reducing the amount of Zn in the magnetic material. However, if the magnetic permeability μ is excessively lowered, the magnetic material does not function as the original magnetic material. Therefore, in general, the magnetic material contains Zn of 10 mol% or less in terms of ZnO. In some cases, Zn is not contained in the magnetic material at all. The magnetic permeability μ may be μ'≦ 100 at a specific magnetic permeability μ ′ at 1 MHz. As for the lower limit, there is usually no problem if μ'≈20.
いずれにしても、高周波領域での使用が想定される積層チップ部品の磁性層にＮｉ系フェライトを主成分とした磁性材料を用いる場合、その磁性材料には、高周波領域でのコアロスが小さいこと（高周波特性）と、１０００℃以下での焼結性（低温焼結性）が求められている。 In any case, when a magnetic material containing Ni-based ferrite as the main component is used for the magnetic layer of the laminated chip component that is expected to be used in the high frequency region, the magnetic material has a small core loss in the high frequency region ( High frequency characteristics) and sinterability at 1000 ° C or lower (low temperature sinterability) are required.
高周波特性については、上述したように、主成分にＣｏＯを添加することで向上させることができる。しかし、ＣｏＯの添加量が多いと、磁性材料の焼結性が悪化する。そこで、Ｎｉ系フェライトにＣｏＯが添加されてなる磁性材料において、低温焼結性を得るために焼結助剤であるＢｉ２Ｏ３を添加することがある。しかし、Ｂｉ２Ｏ３を添加すると、磁性材料の結晶が大きくなり、渦電流損失が増大したり、非磁性材料の含有量が相対的に増大したりすることにより、高周波領域でのコアロスが大きくなる。 As described above, the high frequency characteristics can be improved by adding CoO to the main component. However, if the amount of CoO added is large, the sinterability of the magnetic material deteriorates. Therefore, in a magnetic material in which CoO is added to Ni-based ferrite, Bi 2 O 3 which is a sintering aid may be added in order to obtain low-temperature sinterability. However, when Bi 2 O 3 is added, the crystals of the magnetic material become large, the eddy current loss increases, and the content of the non-magnetic material increases relatively, so that the core loss in the high frequency region becomes large. Become.
そこで、Ｂｉ２Ｏ３に起因する異常結晶成長の増加による渦電流損失や、高周波特性の悪化を抑制するために、ＳｉＯ２、Ａｌ２Ｏ３を添加することが考えられる。ＳｉＯ２、Ａｌ２Ｏは、その一部が磁性体中でガラス化されて磁性材料の焼結性を改善させる。また、ガラスの絶縁性によって抵抗が大きくなり高周波特性が改善する。しかし、その一方で、ＳｉＯ２やＡｌ２Ｏ３は、透磁率μを低下させる原因となる。 Therefore, it is conceivable to add SiO 2 and Al 2 O 3 in order to suppress the eddy current loss due to the increase in abnormal crystal growth caused by Bi 2 O 3 and the deterioration of high frequency characteristics. A part of SiO 2 and Al 2 O is vitrified in the magnetic material to improve the sinterability of the magnetic material. In addition, the insulating property of the glass increases the resistance and improves the high frequency characteristics. However, on the other hand, SiO 2 and Al 2 O 3 cause a decrease in magnetic permeability μ.
このように、低温焼成が可能で、高周波領域でのコアロスが小さな磁性材料を得るという目的を達成するために、主成分の組成を鉄損や銅損を考慮して調整するとともに、その主成分にＣｏＯ、Ｂｉ２Ｏ３、さらにはＳｉＯ２、Ａｌ２Ｏ３を添加したとしても、互いに特性を相殺させる要素が複雑に存在することになり、上記の目的を達成することが難しくなる。 In this way, in order to achieve the purpose of obtaining a magnetic material that can be fired at low temperature and has a small core loss in the high frequency region, the composition of the main component is adjusted in consideration of iron loss and copper loss, and the main component is adjusted. Even if CoO, Bi 2 O 3 , and further SiO 2 and Al 2 O 3 are added to the mixture, there are complicated elements that cancel each other's characteristics, and it becomes difficult to achieve the above object.
そこで、全く新規な添加剤として、希土類を用いることを考えた。そして、特定の希土類に限って特性を特異的に改善できることを知見した。そして、本発明者は、このような知見に基づいて鋭意研究を重ねた結果、本発明の実施例に係る磁性材料を得ることができた。
＝＝＝実施例＝＝＝
本発明の実施例に係る磁性材料は、Ｆｅ、Ｃｕ、Ｚｎを所定の割合（ｍｏｌ％）で含むとともに残部がＮｉとなるＮｉ系フェライトを主成分としつつ、副成分として、Ｃｏ、Ｂｉ、ＳｉＯ２、Ａｌ２Ｏ３が含まれているともに、ＳｉＯ２、Ａｌ２Ｏ３を添加することによるμの低下を補完するためにＰｒ６Ｏ１１が適量添加されている。それによって、実施例に係る磁性材料は、低温での焼成が可能で、かつ高周波領域におけるコアロス特性の劣化が抑制されたものとなっている。
＜サンプルの作製手順＞
本発明の実施例に係る磁性材料の特性を評価するために、主成分の組成、副成分となる添加剤の種類や添加量が異なる各種磁性材料をサンプルとして作製した。図１に、サンプルの作製手順を示した。まず主成分であるＮｉ系フェライトの原料となるＦｅ２Ｏ３、ＺｎＯ、ＣｕＯ、ＮｉＯを秤量、混合する（ｓ１）。秤量に際しては、基準となる主成分の組成を、Ｆｅ２Ｏ３を４１ｍｏｌ％、ＺｎＯを２ｍｏｌ％、ＮｉＯを４８ｍｏｌ％、ＣｕＯを９ｍｏｌ％とし、サンプルに応じてＦｅ２Ｏ３、ＺｎＯ、ＣｕＯ、ＮｉＯのそれぞれの割合を調整した。
Therefore, we considered using rare earths as a completely new additive. Then, it was found that the characteristics can be specifically improved only for specific rare earths. Then, as a result of repeated diligent research based on such findings, the present inventor was able to obtain a magnetic material according to an embodiment of the present invention.
=== Example ===
The magnetic material according to the embodiment of the present invention contains Ni-based ferrite containing Fe, Cu, and Zn in a predetermined ratio (mol%) and the balance being Ni, and has Co, Bi, and SiO as subcomponents. 2. Al 2 O 3 is contained, and an appropriate amount of Pr 6 O 11 is added to compensate for the decrease in μ due to the addition of SiO 2 and Al 2 O 3 . As a result, the magnetic material according to the embodiment can be fired at a low temperature, and deterioration of core loss characteristics in a high frequency region is suppressed.
<Sample preparation procedure>
In order to evaluate the characteristics of the magnetic material according to the examples of the present invention, various magnetic materials having different compositions of main components, types of additives as sub-components, and addition amounts were prepared as samples. FIG. 1 shows a sample preparation procedure. First, Fe 2 O 3 , ZnO, CuO, and NiO, which are raw materials for Ni-based ferrite, which is the main component, are weighed and mixed (s1). When weighing, the composition of the main component as a reference is 41 mol% for Fe 2 O 3 , 2 mol% for Zn O, 48 mol% for Ni O, and 9 mol% for Cu O, and Fe 2 O 3 , ZnO, CuO, depending on the sample. The respective proportions of NiO were adjusted.
そして、秤量した主成分の原料を、ボールミルなどを用いて混合した。なお、以下の記載において、主成分に含まれるＦｅ、Ｎｉ、Ｚｎ、およびＣｕの各元素の割合（ｍｏｌ％）が示されている場合、Ｆｅ、Ｎｉ、Ｚｎ、およびＣｕの割合は、それぞれ、Ｆｅ２Ｏ３、ＮｉＯ、ＺｎＯ、およびＣｕＯで換算しているものとする。 Then, the weighed raw materials of the main components were mixed using a ball mill or the like. In the following description, when the ratio (mol%) of each element of Fe, Ni, Zn, and Cu contained in the main component is shown, the ratio of Fe, Ni, Zn, and Cu is shown, respectively. It is assumed that the conversion is performed with Fe 2 O 3 , NiO, ZnO, and CuO.
次に、上記主成分の原料の混合物を７５０℃で仮焼成した（ｓ２）。さらに、仮焼成によって得られた粉体をボールミルにて平均粒子径が０．５μｍになるまで粉砕し（ｓ３）、その粉砕後の粉体に対し、副成分となる各種添加剤を添加した（ｓ４）。ここでは、サンプルに応じ、ＣｏＯ、Ｂｉ２Ｏ３、ＳｉＯ２、Ａｌ２Ｏ３、Ｐｒ６Ｏ１１、Ｌａ２Ｏ３、ＢｅＯを添加した。 Next, the mixture of the raw materials of the main components was calcined at 750 ° C. (s2). Further, the powder obtained by calcination was pulverized with a ball mill until the average particle size became 0.5 μm (s3), and various additives as subcomponents were added to the pulverized powder (s3). s4). Here, CoO, Bi 2 O 3 , SiO 2 , Al 2 O 3 , Pr 6 O 11 , La 2 O 3 , and BeO were added according to the sample.
次に、仮焼成後の主成分の原料に副成分が添加された粉体材料にＰＶＡ水溶液などのバインダーを加えて適宜な大きさの粒子径となるように造粒する（ｓ５）。そして、その造粒物を所定の形状に成形する。ここでは、外径１５ｍｍ、内径１０ｍｍ、厚さ２ｍｍのリング状に成形した（ｓ６）。そして、そのリング状の成形体をＡｇの融点以下である９００℃の温度で５時間焼成し（ｓ７）、サンプルとなるリングコアを得た。
＜特性評価方法＞
上記の手順によって作製したサンプルについて、各種磁気特性を周知のＢＨアナライザを用いて測定した。ここでは、磁気特性として、周波数１ＭＨｚにおける比透磁率μ’、飽和磁束密度Ｂｍ（ｍＴ）、サンプルを４０００Ａ／ｍの磁界強度で磁化させた際の残留磁界強度（以下、保磁力とも言う）Ｈｃ（Ａ／ｍ）、共振周波数ｆｒ（ＭＨｚ）および、コアロスＰｃｖ（ｋＷ／ｍ３）を測定した。コアロスＰｃｖを測定する際には、各サンプルを所定の巻線数（例えば巻線数３）のトロイダルリングコアの状態にした。そして、測定時の最大磁気飽和密度Ｂｍを２０ｍＴとし、１ＭＨｚの周波数にてコアロスＰｃｖを測定した。なお、高周波領域での使用を想定した積層インダクタの磁性層を構成する磁性材料では、特に、低いコアロスＰｃｖと高い共振周波数とが求められている。ここでは、コアロスＰｃｖ＜３０００で、かつ共振周波数ｆｒ≧５０ＭＨｚを目標とした。
＜主成分の組成＞
まず、主成分の最適な組成を求めるために、副成分の種類と添加量が同じで、主成分の組成が異なるサンプルの特性を評価した。添加した副成分はＣｏＯとＢｉ２Ｏ３であり、ＣｏＯを主成分に対して０．２ｗｔ％添加し、Ｂｉ２Ｏ３を主成分に対して０．７ｗｔ％添加した。
Next, a binder such as a PVA aqueous solution is added to a powder material in which an auxiliary component is added to the raw material of the main component after calcination, and the particles are granulated so as to have a particle size of an appropriate size (s5). Then, the granulated product is molded into a predetermined shape. Here, it was formed into a ring shape having an outer diameter of 15 mm, an inner diameter of 10 mm, and a thickness of 2 mm (s6). Then, the ring-shaped molded product was calcined at a temperature of 900 ° C., which is equal to or lower than the melting point of Ag, for 5 hours (s7) to obtain a ring core as a sample.
<Characteristic evaluation method>
Various magnetic properties of the sample prepared by the above procedure were measured using a well-known BH analyzer. Here, the magnetic characteristics include relative permeability μ'at a frequency of 1 MHz, saturation magnetic flux density Bm (mT), and residual magnetic field strength (hereinafter, also referred to as coercive force) Hc when the sample is magnetized with a magnetic field strength of 4000 A / m. (A / m), resonance frequency fr (MHz), and core loss Pcv (kW / m 3 ) were measured. When measuring the core loss Pcv , each sample was placed in the state of a toroidal ring core having a predetermined number of windings (for example, 3 windings). Then, the maximum magnetic saturation density Bm at the time of measurement was set to 20 mT, and the core loss Pcv was measured at a frequency of 1 MHz. In addition, in the magnetic material constituting the magnetic layer of the laminated inductor that is supposed to be used in the high frequency region, a low core loss Pcv and a high resonance frequency are particularly required. Here, the target is core loss P cv <3000 and resonance frequency fr ≧ 50 MHz.
<Composition of principal components>
First, in order to obtain the optimum composition of the main component, the characteristics of samples having the same type and amount of sub-component but different composition of the main component were evaluated. The added sub-ingredients were CoO and Bi 2 O 3 , 0.2 wt% of CoO was added to the main component, and 0.7 wt% of Bi 2 O 3 was added to the main component.
以下の表１に、主成分の組成が異なるサンプルの作製条件と磁気特性とを示した。 Table 1 below shows the preparation conditions and magnetic properties of samples with different principal component compositions.
表１に示したように、Ｆｅの割合が３９ｍｏｌ％のサンプル２では、コアロスＰｃｖがサンプル１に対して劣化しており、Ｆｅの割合が４６ｍｏｌ％のサンプル３では、共振周波数ｆｒが低下している。したがって、コアロスＰｃｖを低減させるために、主成分中のＦｅの割合を４０ｍｏｌ％以上４５ｍｏｌ％以下にすることが、妥当であることが確認できた。 As shown in Table 1, Sample 2 ratio of 39 mol% of Fe, and deteriorated core loss P cv is relative to Sample 1, Sample 3 ratio of 46 mol% of Fe, the resonance frequency fr is reduced ing. Therefore, in order to reduce the core loss P cv, the proportion of Fe in the main component to be below 40 mol% or more 45 mol%, it was confirmed that reasonable.
また、Ｚｎの割合が１１ｍｏｌ％のサンプル３では、コアロスＰｃｖが悪化していることから、Ｚｎの割合は１０ｍｏｌ％以下であることが必要となる。なお、上述したように主成分中にＺｎは必ずしも含まれていなくてもよいことから、主成分中のＺｎの割合は、０ｍｏｌ％以上１０ｍｏｌ％以下にすればよい。 Further, in the sample 3 having a Zn ratio of 11 mol%, the core loss Pcv is deteriorated, so that the Zn ratio needs to be 10 mol% or less. Since Zn does not necessarily have to be contained in the main component as described above, the ratio of Zn in the main component may be 0 mol% or more and 10 mol% or less.
サンプル４、５は、サンプル１に対し、Ｃｕの量が増減されており、主成分中のＣｕの割合が４ｍｏｌ％のサンプル４、および１６ｍｏｌ％のサンプル５では、ともにサンプル１に対してコアロスＰｃｖが悪化している。したがって、主成分中のＣｕの割合は、５ｍｏｌ％以上１５ｍｏｌ％以下であることが望ましい。
＜ＣｏＯ、Ｂｉ２Ｏ３の添加量＞
上述したように、磁性材料において、ＣｏＯは、焼結性が確保されていれば、添加量が多いほど、高周波特性を向上させる。しかし、添加量が多すぎると焼結性が悪化する。焼結性が悪化すれば、結局、コアロスＰｃｖも増大することになる。また、Ｂｉ２Ｏ３は、多く添加するほど焼結性を向上させる一方で、添加量が多すぎるとコアロスを増大させる。そこで、ＣｏＯとＢｉ２Ｏ３の添加量の上限を調べるために、表１に示したサンプル１の磁性材料に対し、ＣｏＯ、あるいはＢｉ２Ｏ３の添加量を変えたサンプルを作製した。
In Samples 4 and 5, the amount of Cu was increased or decreased with respect to Sample 1, and in Sample 4 in which the ratio of Cu in the principal component was 4 mol% and in Sample 5 in which the ratio of Cu was 16 mol%, the core loss P was P with respect to Sample 1. The cv is getting worse. Therefore, it is desirable that the ratio of Cu in the main component is 5 mol% or more and 15 mol% or less.
<Addition amount of CoO and Bi 2 O 3 >
As described above, in the magnetic material, if the sinterability is ensured, the larger the amount of CoO added, the better the high frequency characteristics. However, if the amount added is too large, the sinterability deteriorates. If sinterability is deteriorated, eventually will be the core loss P cv also increases. Further, while Bi 2 O 3 improves the sinterability as it is added in a large amount, the core loss increases when the amount added is too large. Therefore, in order to investigate the upper limit of the addition amount of CoO and Bi 2 O 3 , a sample in which the addition amount of CoO or Bi 2 O 3 was changed with respect to the magnetic material of sample 1 shown in Table 1 was prepared.
表２に、ＣｏＯ、あるいはＢｉ２Ｏ３の添加量を変えたサンプルの特性を示した。 Table 2 shows the characteristics of the samples in which the amount of CoO or Bi 2 O 3 added was changed.
＜ＳｉＯ２、Ａｌ２Ｏ３の添加量＞
上述したように、ＳｉＯ２、Ａｌ２Ｏ３は、磁性材料の焼結性を向上させる。しかし、多量に添加すれば、磁気特性を悪化させるため、ＳｉＯ２、Ａｌ２Ｏ３の最適添加量を求める必要がある。そこで、基準となるサンプル１の磁性材料に対し、ＳｉＯ２とＡｌ２Ｏ３を添加した各種サンプルを作製した。
<Addition amount of SiO 2 and Al 2 O 3 >
As described above, SiO 2 and Al 2 O 3 improve the sinterability of the magnetic material. However, if a large amount is added, the magnetic characteristics are deteriorated. Therefore, it is necessary to obtain the optimum addition amount of SiO 2 and Al 2 O 3 . Therefore, various samples were prepared by adding SiO 2 and Al 2 O 3 to the magnetic material of the reference sample 1.
表３に、ＳｉＯ２とＡｌ２Ｏ３の添加量が異なる各種サンプルの特性を示した。 Table 3 shows the characteristics of various samples in which the addition amounts of SiO 2 and Al 2 O 3 are different.
＜Ｐｒ６Ｏ１１の添加量＞
本発明の実施例に係る磁性材料は、適正な組成を有するＮｉフェライトを主成分とするとともに、副成分として、ＣｏＯ、Ｂｉ２Ｏ３、ＳｉＯ２、およびＡｌ２Ｏ３が適量添加された磁性材料に対し、さらにＰｒ６Ｏ１１が適量添加されて、低温焼結性が確保されつつ、高周波領域でのコアロスＰｃｖが低減されたものである。そこで、Ｐｒ６Ｏ１１の適正な添加量を求めるために、表３に示したサンプル１６に対し、Ｐｒ６Ｏ１１を添加した各種サンプルを作製した。
<Addition amount of Pr 6 O 11 >
The magnetic material according to the embodiment of the present invention contains Ni ferrite having an appropriate composition as a main component, and has an appropriate amount of CoO, Bi 2 O 3 , SiO 2 , and Al 2 O 3 added as subcomponents. to material, is further added in an appropriate amount is Pr 6 O 11, while the low-temperature sintering property is ensured, in which core loss P cv in the high frequency region is reduced. Therefore, in order to determine the proper amount of Pr 6 O 11, to the sample 16 shown in Table 3, we were prepared various samples spiked with Pr 6 O 11.
表４に、Ｐｒ６Ｏ１１の添加量が異なる各種サンプルの特性を示した。 Table 4 shows the characteristics of various samples with different amounts of Pr 6 O 11 .
そして、Ｐｒ６Ｏ１１を添加していないサンプル１６に対し、主成分に対しＰｒ６Ｏ１１を添加したサンプル１７〜２０の特性をみると、Ｐｒ６Ｏ１１の添加量が極めて微量な０．０１ｗｔ％のサンプル１７でコアロスＰｃｖの低減が確認された。そして、サンプル１８の０．０５ｗｔ％の添加量におけるコアロスＰｃｖを極小値として、Ｐｒ６Ｏ１１の添加量が増加していくのにしたがって、コアロスＰｃｖも増加する傾向が確認できる。そして、Ｐｒ６Ｏ１１の添加量が０．２ｗｔ％のサンプル２０のコアロスＰｃｖは、基準となるサンプル１のコアロスＰｃｖ＝２７２７よりも大きかった。また、Ｐｒ６Ｏ１１の添加量が０．１ｗｔ％のサンプル１９は、コアロスＰｃｖが、サンプル１６のコアロスＰｃｖ＝２３３５よりも大きくなったものの、サンプル１のコアロスＰｃｖよりも小さかった。したがって、サンプル１７〜２０におけるコアロスＰｃｖの増減傾向を考慮すれば、Ｐｒ６Ｏ１１の添加量は、０．１ｗｔ％未満であることが望ましい。より好ましくは、Ｐｒ６Ｏ１１の添加量を０．０５ｗｔ％以下とすることである。
＜希土類、アルカリ土類金属を含む添加剤＞
ところで、Ｐｒは希土類であり、一般的に、希土類に属する元素やその化合物は物性が類似している。そこで、Ｐｒ以外の希土類としてＬａを含む化合物（例えば、Ｌａ２Ｏ３）を添加剤とした磁性材料をサンプルとして作製した。また、希土類に特性が近似する元素として、アルカリ土類金属のＢｅを含む化合物（例えば、ＢｅＯ）を添加物とした磁性材料もサンプルとして作製した。そして、各サンプルの特性を評価した。
Looking at the characteristics of the samples 17 to 20 in which Pr 6 O 11 was added to the principal component with respect to the sample 16 in which Pr 6 O 11 was not added, the amount of Pr 6 O 11 added was extremely small. reduction of core loss P cv has been confirmed in 01wt% of the sample 17. Then, with the core loss P cv at the addition amount of 0.05 wt% of the sample 18 as the minimum value, it can be confirmed that the core loss P cv tends to increase as the addition amount of Pr 6 O 11 increases. Then, the amount of Pr 6 O 11 has a core loss P cv of 0.2 wt% of the sample 20 was greater than the core loss P cv = 2727 samples 1 as a reference. Further, in the sample 19 in which the addition amount of Pr 6 O 11 was 0.1 wt%, the core loss P cv was larger than the core loss P cv = 2335 of the sample 16, but was smaller than the core loss P cv of the sample 1. Therefore, considering the tendency of increase or decrease core loss P cv in samples 17 to 20, the amount of Pr 6 O 11 is desirably less than 0.1 wt%. More preferably, the addition amount of Pr 6 O 11 is 0.05 wt% or less.
<Additives containing rare earth and alkaline earth metals>
By the way, Pr is a rare earth element, and in general, elements belonging to rare earth elements and their compounds have similar physical properties. Therefore, a magnetic material containing a compound containing La as a rare earth other than Pr (for example, La 2 O 3 ) as an additive was prepared as a sample. Further, as an element whose characteristics are similar to those of rare earths, a magnetic material containing a compound containing Be of an alkaline earth metal (for example, BeO) as an additive was also prepared as a sample. Then, the characteristics of each sample were evaluated.
以下の表５に、Ｐｒ、Ｌａ、Ｂｅの酸化物を添加物としたサンプルの特性を示した。 Table 5 below shows the characteristics of the sample containing the oxides of Pr, La, and Be as additives.
以上より実施例に係る磁性材料は、主成分となるＮｉフェライトに副成分としてＣｏＯ、Ｂｉ２Ｏ３、ＳｉＯ２、Ａｌ２Ｏ３、およびＰｒ６Ｏ１１が添加されてなる。そして、主成分中のＦｅ、Ｚｎ、Ｃｕ、Ｎｉの割合が、それぞれ、４０ｍｏｌ％以上４５ｍｏｌ％以下、０ｍｏｌ％以上１０ｍｏｌ％以下、５ｍｏｌ％以上１５ｍｏｌ％以下、残部がＮｉであり、かつ、ＣｏＯ、Ｂｉ２Ｏ３、ＳｉＯ２、Ａｌ２Ｏ３、およびＰｒ６Ｏ１１の主成分に対する添加量ａ、ｂ、ｃ、ｄ、およびｅが、それぞれ０ｗｔ％＜ａ≦０．４ｗｔ％、０ｗｔ％＜ｂ≦０．４ｗｔ％、０ｗｔ％＜ｃ≦０．２ｗｔ％、０ｗｔ％＜ｄ≦０．４ｗｔ％、および０ｗｔ％＜ｅ＜０．１ｗｔ％となるものである。そして、より好ましくは、０ｗｔ％＜ｅ≦０．０５ｗｔ％となるものである。 From the above, the magnetic material according to the embodiment is obtained by adding CoO, Bi 2 O 3 , SiO 2 , Al 2 O 3 , and Pr 6 O 11 as subcomponents to Ni ferrite as the main component. The proportions of Fe, Zn, Cu, and Ni in the main components are 40 mol% or more and 45 mol% or less, 0 mol% or more and 10 mol% or less, 5 mol% or more and 15 mol% or less, and the balance is Ni and CoO. The amounts of a, b, c, d, and e added to the main components of Bi 2 O 3 , SiO 2 , Al 2 O 3 , and Pr 6 O 11 are 0 wt% <a ≤ 0.4 wt% and 0 wt% <, respectively. b ≦ 0.4 wt%, 0 wt% <c ≦ 0.2 wt%, 0 wt% <d ≦ 0.4 wt%, and 0 wt% <e <0.1 wt%. Then, more preferably, 0 wt% <e ≦ 0.05 wt%.
ｓ１ 主成分原料秤量・混合工程、ｓ２ 仮焼成工程、ｓ３ 粉砕工程、
ｓ４ 副成分添加工程、ｓ５ 造粒工程、ｓ６ 成形工程、ｓ７ 焼成工程
s1 Principal component raw material weighing / mixing process, s2 Temporary firing process, s3 Grinding process,
s4 sub-component addition process, s5 granulation process, s6 molding process, s7 firing process
Claims (3)
４０≦ｘ≦４５、０≦ｙ≦１０、５≦ｚ≦１５、
０＜ａ≦０．３、０＜ｂ≦１．０、０＜ｃ≦０．２、０＜ｄ＜０．４、０＜ｅ＜０．１
であることを特徴とする磁性材料。 Fe 2 O 3 equivalent x mol% Fe, ZnO equivalent ymol% Zn, CuO equivalent zmol% Cu, and NiO equivalent (100-x-yz) mol% Ni as the main component. As subcomponents, awt% of CoO, bwt% of Bi 2 O 3 , cwt% of SiO 2 , dwt% of Al 2 O 3 and ewt% of Pr 6 O 11 are added to the main component. ,
40 ≦ x ≦ 45, 0 ≦ y ≦ 10, 5 ≦ z ≦ 15,
0 <a ≦ 0.3, 0 <b ≦ 1.0, 0 <c ≦ 0.2, 0 <d <0.4, 0 <e <0.1
A magnetic material characterized by being.
前記導電体は銀である
ことを特徴とする積層チップ部品。 A laminated chip component in which an electrically insulating magnetic layer formed of a sintered body made of the magnetic material according to claim 1 or 2 and an electrode layer having an electrode pattern made of a conductor are laminated in layers. And
A laminated chip component characterized in that the conductor is silver.
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