TW201814739A - 鐵氧體組合物及電子部件 - Google Patents
鐵氧體組合物及電子部件 Download PDFInfo
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- TW201814739A TW201814739A TW106132226A TW106132226A TW201814739A TW 201814739 A TW201814739 A TW 201814739A TW 106132226 A TW106132226 A TW 106132226A TW 106132226 A TW106132226 A TW 106132226A TW 201814739 A TW201814739 A TW 201814739A
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 25
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- 239000005751 Copper oxide Substances 0.000 claims abstract description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 230000035699 permeability Effects 0.000 description 60
- 230000007423 decrease Effects 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 238000010304 firing Methods 0.000 description 14
- 239000002131 composite material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000009766 low-temperature sintering Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 241000656145 Thyrsites atun Species 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000002508 compound effect Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- -1 Mn 3 O 4 Chemical class 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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Abstract
本發明提供一種初始磁導率、比電阻、頻率特性及溫度特性良好的鐵氧體組合物以及使用了上述鐵氧體組合物的電子部件。本發明為一種具有主成分和副成分的鐵氧體組合物。主成分由以Fe2O3換算為18~30摩爾%的氧化鐵、以CuO換算為4~14摩爾%的氧化銅、以ZnO換算為0~6摩爾%的氧化鋅、餘量為氧化鎳構成。相對於主成分100重量份,作為副成分,含有以SiO2換算為0.30~1.83重量份的矽化合物、以Co3O4換算為2.00~10.00重量份的鈷化合物、以Bi2O3換算為1.00~3.00重量份的鉍化合物。用以Co3O4換算的鈷化合物的含量除以以SiO2換算的矽化合物的含量所得的值為5.5~30.0。
Description
本發明涉及一種適於積層型電感器等的製造的鐵氧體組合物、以及具有由該組合物構成的鐵氧體燒結體的電子部件。
近年來,DC-DC轉換器在向小型化、高頻化發展,以數十MHz~數百MHz左右的頻率驅動的DC-DC轉換器也出現。作為適用於小型化、高頻化後的DC-DC轉換器的電感器,要求即使在高頻區域下也能夠作為電感器工作的頻率特性、以及即使施加大電流、工作也幾乎沒有變化的直流疊加特性。
作為適用於DC-DC轉換器的電感器所使用的鐵氧體組合物,以往提出了添加有鈷的NiCuZn鐵氧體。正在探討藉由對NiCuZn鐵氧體進行鈷添加而提高磁異向性、提高磁導率的頻率特性的方法。
但是,以往已知添加有鈷的NiCuZn鐵氧體與未添加鈷的NiCuZn鐵氧體相比,有燒結性降低、溫度特性變差的傾向。作為克服上述的鈷添加的缺點的方法,提出了以下所示的方法。
專利文獻1中,藉由在NiCuZn鐵氧體中與鈷化合物一起添加氧化鉍等鉍化合物而克服燒結性降低。進一步,藉 由添加鋯化合物而改善溫度特性。
專利文獻2中,藉由在NiCuZn鐵氧體中添加Co3O4、SiO2、Bi2O3,得到高的Q值、良好的溫度特性和高的抗應力特性。
專利文獻3中,藉由使NiCuZn鐵氧體中的Fe2O3量和ZnO量比較少,進而藉由添加CoO而得到頻率特性優異的鐵氧體組合物。
但是,專利文獻1的實施例中,雖然顯示初始磁導率μi的值,但是,沒有記載保持磁導率的值至何種程度的高頻率。根據Snoek極限,一般而言,初始磁導率μi的值越低,越保持磁導率的值至高的頻率。但是,在添加有添加物的情況下,在Snoek極限以上保持磁導率至高頻率,相反,在Snoek極限以下的低頻率磁導率降低。因此,初始磁導率μi成為頻率特性的標準,但作為頻率特性的評價基準,根據不足。因此,在專利文獻1的實施例中,頻率特性不清楚。
此外,Snoek極限藉由以下的式(1)表示。此外,fr為旋轉磁化共振頻率,μi為初始磁導率,γ為回轉磁常數(gyromagnetic constant),Ms為飽和磁化。
fr(μi-1)=|γ|×(Ms/3π)......式(1)
另外,專利文獻1中,關於添加有氧化鋯的情況下的磁導率的溫度變化,示出了20℃下的初始磁導率和85℃下的初始磁導率之比。但是,在專利文獻1的實施例所示的20℃下的初始磁導率和85℃下的初始磁導率之比中最小的為1.45倍。其結果,對於抑制初始磁導率相對於溫度變化的變化 的效果過大。
另外,在專利文獻2中,沒有顯示初始磁導率的值,頻率特性不清楚。在專利文獻3中,溫度特性不清楚。進一步,專利文獻1~3中,直流疊加特性均不清楚。
由以上可知,並不清楚專利文獻1~3的NiCuZn鐵氧體是否頻率特性、直流疊加特性以及溫度特性全部都優異。
[專利文獻1]日本特開2000-252112號公報
[專利文獻2]日本特開2006-206347號公報
[專利文獻3]日本特開2008-300548號公報
本發明是鑒於這樣的實際情況而完成的,其目的在於,提供一種初始磁導率、比電阻、頻率特性及溫度特性良好的鐵氧體組合物、以及使用了上述鐵氧體組合物的電子部件。
為了實現上述目的,本發明所涉及的鐵氧體組合物為具有主成分和副成分的鐵氧體組合物,其特徵在於,所述主成分由以Fe2O3換算為18~30摩爾%的氧化鐵、以CuO換算為4~14摩爾%的氧化銅、以ZnO換算為0~6摩爾%的氧化鋅、餘量為氧化鎳所構成,相對於上述主成分100重量份,作為上述副成分,含有以SiO2換算為0.30~1.83重量份的矽化合物、以Co3O4換算為2.00~10.00重量份的鈷化合物、以Bi2O3換算為1.00~3.00重量份的鉍化合物,用以Co3O4換算後的上述鈷化合物的含量除以以SiO2換算的上述矽化合物的含量所得的 值為5.5~30.0。
本發明的鐵氧體組合物藉由將構成主成分的氧化物的含量設為上述的範圍,進一步作為副成分在上述的範圍內含有矽化合物、鈷化合物以及鉍化合物,從而燒結後的初始磁導率μi、比電阻ρ、頻率特性以及初始磁導率μi的溫度特性良好。
認為可得到這種效果的理由是藉由將主成分設為規定範圍、進一步將各成分的含量設為特定的範圍所得到的複合的效果。
本發明的電子部件具有由上述的鐵氧體組合物構成的鐵氧體燒結體。
此外,由本發明的鐵氧體組合物構成的鐵氧體燒結體佳用於積層型電感器、積層型L-C濾波器、積層型共模濾波器、利用其他的積層方法的複合電子部件等。例如在LC複合電子部件、NFC線圈、積層型阻抗元件、積層型變壓器中也適合使用本發明的鐵氧體組合物。
1‧‧‧積層型電感器
2‧‧‧元件
3‧‧‧端子電極
4‧‧‧積層體
5‧‧‧線圈導體
5a、5b‧‧‧引出電極
10‧‧‧LC複合電子部件
12‧‧‧電感器部
14‧‧‧電容器部
[圖1]圖1是本發明的一個實施方式的積層型電感器的剖面圖。
[圖2]圖2是本發明的一個實施方式的LC複合電子部件的剖面圖。
[圖3]圖3是NiCuZn鐵氧體中的磁導率的頻率特性的示意圖。
以下,基於附圖所示的實施方式說明本發明。
如圖1所示,本發明的一個實施方式的積層型電感器1具有元件2和端子電極3。元件2藉由經由鐵氧體層4而3維且螺旋狀地形成有線圈導體5的生坯積層體進行燒成而得到。鐵氧體層4由本發明的一個實施方式的鐵氧體組合物構成。藉由在元件2的兩端形成端子電極3,並且經由引出電極5a、5b與端子電極3接續從而得到積層型電感器1。對元件2的形狀沒有特別限制,通常設為長方體狀。另外,對其尺寸也沒有特別限制,根據用途設為適當的尺寸即可。
作為線圈導體5及引出電極5a、5b的材質,沒有特別限定,可使用Ag、Cu、Au、Al、Pd、Pd/Ag合金等。此外,也可以添加Ti化合物、Zr化合物、Si化合物等。
本實施方式的鐵氧體組合物為Ni-Cu系鐵氧體或Ni-Cu-Zn系鐵氧體,作為主成分,可以含有氧化鐵、氧化銅及氧化鎳,進一步可以含有氧化鋅。
主成分100摩爾%中,氧化鐵的含量以Fe2O3換算為18.0~30.0摩爾%。無論氧化鐵的含量過多還是過少,都存在燒結性變差、特別是低溫燒結時的燒結密度降低的傾向。另外,在氧化鐵過少的情況下,存在初始磁導率μi降低的傾向。在氧化鐵過多的情況下,存在頻率特性變差、後述的μ”上升頻率降低的傾向。進而,存在初始磁導率μi的溫度特性也變差的傾向。
主成分100摩爾%中,氧化銅的含量以CuO換算 為4~14摩爾%。氧化銅的含量過少時,存在燒結性變差、特別是低溫燒結時的燒結密度降低的傾向。其結果,存在比電阻ρ及初始磁導率μi的溫度特性變差的傾向。其過多時,存在初始磁導率μi降低的傾向。
主成分100摩爾%中,氧化鋅的含量以ZnO換算為0~6.0摩爾%。即,可以含有氧化鋅作為主成分,也可以不含有。此外,存在氧化鋅的含量越多、初始磁導率越上升的傾向,初始磁導率越升高,越適於電感器。但是,氧化鋅的含量過多時,存在居禮溫度及μ”上升頻率降低的傾向。
主成分的餘量由氧化鎳構成。
本實施方式的鐵氧體組合物除上述的主成分之外,含有矽化合物、鈷化合物及鉍化合物作為副成分。此外,作為各化合物的種類,除氧化物之外,只要是在燒成後會成為氧化物的化合物,就沒有特別限定。
相對於主成分100重量份,矽化合物的含量以SiO2換算為0.30~1.83重量份。如果在特定的範圍內含有矽化合物時,鐵氧體組合物的溫度特性提高。矽化合物的含量過少時,存在初始磁導率μi的溫度特性降低的傾向。其過多時,存在燒結性變差、特別是低溫燒結時的燒結密度降低的傾向。進而,存在初始磁導率μi及比電阻ρ降低的傾向。
對藉由矽化合物的添加而提高溫度特性的理由進行說明。氧化矽等矽化合物與NiCuZn鐵氧體顆粒相比,線膨脹係數小。即,在NiCuZn鐵氧體中添加矽化合物而形成鐵氧體組合物的情況下,所添加的矽化合物對NiCuZn鐵氧體預先 施加應力。本發明人等認為,藉由矽化合物的存在而產生的應力存在,因此藉由溫度變化而產生的應力的影響得以緩和,溫度特性提高。
相對於主成分100重量份,鉍化合物的含量以Bi2O3換算為1.00~3.00重量份。前述的矽化合物及後述的鈷化合物具有使燒結性降低的效果。與此相對,鉍化合物可以提高燒結性,並且能夠在900℃以下的溫度下進行燒成。鉍化合物的含量過少時,存在燒結性變差、特別是低溫燒結時的燒結密度降低的傾向。進而,存在伴隨燒結性的變差、比電阻ρ也降低的傾向。鉍化合物的含量過多時,存在比電阻ρ降低的傾向。
相對於主成分100重量份,鈷化合物的含量以Co3O4換算為2.00~10.00重量份。在特定的範圍內含有鈷化合物時,頻率特性提高,μ”上升頻率提高。進而,直流疊加特性也提高。即,直流電流疊加時的感應係數降低變小。鈷化合物的含量過少時,存在頻率特性變差、μ”上升頻率降低的傾向。進而,存在比電阻ρ也降低的傾向。其過多時,存在燒結性變差,特別是低溫燒結時的燒結密度降低的傾向。其結果,存在初始磁導率μi也降低的傾向。進而,存在初始磁導率μi的溫度特性變差的傾向。
進而,在本實施方式的鐵氧體組合物中,按重量基準計以Co3O4換算的鈷化合物的含量除以按重量基準計以SiO2換算的矽化合物的含量所得的值(以下,記為Co/Si)為5.5~30.0。
上述的Co/Si的限定顯示鈷化合物的含量的允許 範圍根據矽化合物的含量而增減。即使鈷化合物的含量為10.0重量份以下,由於矽化合物的添加量也少,因此,在Co/Si超過30.0的情況下,存在初始磁導率μi的溫度特性變差的傾向。另外,即使鈷化合物的含量為2.0重量份以上,在Co/Si低於5.5的情況下,也存在比電阻ρ及初始磁導率μi降低的傾向。進而,與具有同等磁導率的試樣相比,頻率特性降低,μ”上升頻率降低。
在本實施方式的鐵氧體組合物中,除主成分的組成範圍被控制在上述的範圍之外,還作為副成分,全部在本發明的範圍內含有上述的矽化合物、鉍化合物及鈷化合物。其結果,可以使燒結溫度降低,作為一體燒成的內部導體,例如可以使用Ag等比較的低熔點的金屬。進而,藉由低溫燒成而得到的鐵氧體燒結體,其初始磁導率高,頻率特性良好,比電阻ρ高,直流疊加特性良好,溫度特性良好。特別是藉由鈷化合物和矽化合物的相互作用從而μ”上升頻率及初始磁導率μi的溫度特性變得良好。
此外,矽化合物、鉍化合物及鈷化合物中,在任一個不含有一個以上的情況、或者含量為本發明的範圍外的情況下,不能充分地得到上述的效果。即,認為上述的效果是在同時含有特定量的矽化合物、鉍化合物及鈷化合物的情況下首次得到的複合的效果。
另外,本實施方式的鐵氧體組合物在上述副成分之外,可以進一步在不阻礙本發明的效果的範圍內含有Mn3O4等錳氧化物、氧化鋯、氧化錫、氧化鎂、玻璃化合物等附加的 成分。這些附加的成分的含量沒有特別限定,例如為0.05~10重量%左右。
進而,在本實施方式的鐵氧體組合物中,可含有不可避免的雜質元素的氧化物。
具體而言,作為不可避免的雜質元素,可列舉C、S、Cl、As、Se、Br、Te、I、或Ii、Na、Mg、Al、Ca、Ga、Ge、Sr、Cd、In、Sb、Ba、Pb等的典型金屬元素、或Sc、Ti、V、Cr、Y、Nb、Mo、Pd、Ag、Hf、Ta等過渡金屬元素。另外,不可避免的雜質元素的氧化物可以在鐵氧體組合物中含有0.05重量%以下左右。
本實施方式的鐵氧體組合物具有鐵氧體顆粒和存在於相鄰的結晶顆粒間的結晶界面。結晶顆粒的平均結晶粒徑較佳為0.2~1.5μm。
下面,針對本發明的鐵氧體組合物的頻率特性進行說明。
本發明的鐵氧體組合物的頻率特性表示是否可以保持磁導率至高頻率。
為了對本發明的鐵氧體組合物的頻率特性進行說明,對一般的NiCuZn鐵氧體,將以頻率為橫軸、以複數磁導率的實部μ’和虛部μ”為縱軸時的示意圖示於圖3。
在低頻率區域,即使使頻率變化,μ’也大致為一定,μ”在0附近且大致為一定。在使頻率上升並設為特定的頻率以上時,μ”顯示從0上升的行為。本申請中,將成為μ”>0.1的頻率設為μ”上升頻率。
在μ”上升頻率以上的頻率的區域,Q值降低,作為電感器使用變得困難。因此,就本發明的鐵氧體組合物而言,μ”上升頻率越高,可以作為電感器使用的頻率的上限越升高。就本發明的鐵氧體組合物而言,μ”上升頻率越高,頻率特性越良好。以下,有時將μ”上升頻率記為f。
接下來,對本實施方式的鐵氧體組合物的製造方法的一例進行說明。首先,以成為規定的組成比的方式稱量並混合起始原料(主成分的原料及副成分的原料),得到原料混合物。作為混合的方法,例如可列舉使用球磨機進行的濕式混合、或使用乾式混合機進行的乾式混合。此外,較佳為使用平均粒徑為0.05~1.0μm的起始原料。
作為主成分的原料,可以使用氧化鐵(α-Fe2O3)、氧化銅(CuO)、氧化鎳(NiO)、根據需要的氧化鋅(ZnO)、或複合氧化物等。進而,此外,可以使用藉由燒成而成為上述的氧化物或複合氧化物的各種化合物等。作為藉由燒成而成為上述的氧化物的物質,可列舉例如:金屬單質、碳酸鹽、草酸鹽、硝酸鹽、氫氧化物、鹵化物、有機金屬化合物等。
作為副成分的原料,可以使用氧化矽、氧化鉍及氧化鈷。對成為副成分的原料的氧化物沒有特別限定,可以使用複合氧化物等。進而,此外,可以使用藉由燒成而成為上述的氧化物或複合氧化物的各種化合物等。作為藉由燒成而成為上述的氧化物的物質,可列舉例如:金屬單質、碳酸鹽、草酸鹽、硝酸鹽、氫氧化物、鹵化物、有機金屬化合物等。
此外,作為氧化鈷的一個實施方式的Co3O4由於 容易保管或處理,在空氣中價數穩定,因此,佳作為氧化鈷的原料。
接著,進行原料混合物的煅燒,得到煅燒材料。煅燒是為了引起原料的熱分解、成分的均質化、鐵氧體的生成、由燒結導致的超微粉的消失和晶粒成長為適當的顆粒尺寸,並將原料混合物變換為適於後工序的形態而進行。這樣的煅燒較佳在500~900℃的溫度下通常進行2~15小時左右。煅燒通常在大氣(空氣)中進行,但也可以在比大氣中氧分壓低的氣氛下進行。此外,主成分的原料和副成分的原料的混合可以在煅燒之前進行,也可以在煅燒後進行。
接下來,進行煅燒材料的粉碎,得到粉碎材料。粉碎是為了粉碎煅燒材料的凝集而製成具有適當的燒結性的粉體而進行。在煅燒材料形成大的塊體時,在進行粗粉碎後,使用球磨機或超微磨碎機等進行濕式粉碎。濕式粉碎較佳進行至粉碎材料的平均粒徑成為0.1~1.0μm左右。
使用所得到的粉碎材料,製造本實施方式的積層型電感器。對製造該積層型電感器的方法沒有限制,以下使用片材法。
首先,將得到的粉碎材料與溶劑或黏合劑等添加劑一起進行漿料化,製作膏體。而且,使用該膏體形成生坯片材。接著,將所形成的生坯片材加工成規定的形狀,經過脫黏合劑工序、燒成工序,可得到本實施方式的積層型電感器。燒成在線圈導體5及引出電極5a、5b的熔點以下的溫度下進行。例如,線圈導體5及引出電極5a、5b為Ag(熔點962℃)時, 較佳在850~920℃的溫度下進行。就燒成時間而言,通常進行1~5小時左右。另外,燒成可以在大氣(空氣)中進行,也可以在比大氣中氧分壓低的氣氛下進行。這樣得到的積層型電感器由本實施方式的鐵氧體組合物構成。
以上,對本發明的實施方式進行了說明,但本發明並不受這樣的實施方式的任何限定,顯然可以在不脫離本發明的主旨的範圍內以各種方式實施。例如,作為圖2所示的LC複合電子部件10中的鐵氧體層4,可以使用本發明的鐵氧體組合物。此外,圖2中,符號12所示的部分為電感器部,符號14所示的部分為電容器部。
以下,進一步基於詳細的實施例說明本發明,但本發明並不限定於這些實施例。
首先,作為主成分的原料,準備了Fe2O3、NiO、CuO、ZnO。作為副成分的原料,準備了SiO2、Bi2O3、Co3O4。
接下來,以作為燒結體成為表1~表4所記載的組成的方式稱量了所準備的主成分之後,用球磨機進行濕式混合16小時從而得到原料混合物。
接著,將得到的原料混合物進行乾燥之後,在空氣中在500℃~900℃下進行煅燒而製成煅燒粉。將煅燒粉及副成分的原料粉末用鋼鐵製球磨機進行濕式粉碎72小時從而得到粉碎粉。
接下來,將該粉碎粉進行乾燥之後,在粉碎粉100重量份中添加作為黏合劑的6wt%濃度的聚乙烯醇水溶液10.0 重量份進行造粒而製成顆粒。將該顆粒進行加壓成形,以成為成形密度3.20Mg/m3的方式得到了圓環形狀(尺寸=外徑13mm×內徑6mm×高度3mm)的成形體、及盤形狀(尺寸=外徑12mm×高度2mm)的成形體。
接著,將這些各成形體在空氣中、在作為Ag的熔點(962℃)以下的900℃下燒成2小時,從而得到作為燒結體的圓環磁芯樣品。進一步對樣品進行了以下的特性評價。將試驗結果示於表1~表4。此外,表1~表4中記載的各成分的含量分別為以Fe2O3、NiO、CuO、ZnO、SiO2、Co3O4、Bi2O3換算的值。
初始磁導率μi
對圓環磁芯樣品捲繞銅線10圈,使用阻抗分析儀(Agilent Technologies公司制的4991A)測定初始磁導率μi。作為測定條件,設為測定頻率1MHz、測定溫度25℃。在本實施例中,將初始磁導率μi為1.5以上的情況設為良好。
頻率特性(μ”上升頻率)
對測定了初始磁導率μi的圓環磁芯樣品,一邊使測定頻率從1MHz增加,一邊測定μ”。將μ”超過0.1時的頻率設為μ”上升頻率。將μ”上升頻率f為600MHz以上的情況設為頻率特性良好。
比電阻ρ
在盤樣品的兩面塗敷In-Ga電極,測定直流電阻值,求出比電阻ρ(單位:Ω‧m)。測定使用IR計(HEWLETT PACKARD公司製造的4329A)來進行。在本實施例中,將比電阻ρ為 106Ω‧m以上的情況設為良好。
初始磁導率μi的溫度特性
以室溫25℃為基準,求出25℃~125℃時的初始磁導率μi的變化率。在本實施例中,將μi的變化率為±30%以內的情況設為良好。
表1的試樣為將Co及Si以外的全部的組成在本發明的範圍內設為相同,在以0.33、0.36或0.40重量份固定了Si的含量的基礎上,僅使Co的含量變化的試樣。
由表1可知:在全部的主成分及副成分的組成為本發明的範圍內的情況下,初始磁導率μi、比電阻ρ、頻率特性以及初始磁導率μi的溫度特性變得良好。
與此相對,對於作為副成分的Co的含量過少的試 樣1、11及21而言,頻率特性或比電阻ρ不佳。而Co的含量為本發明的範圍內但Co/Si過小的試樣22,也是比電阻ρ不佳。
另外,就Co的含量過多的試樣7、17及27而言,初始磁導率μi的溫度特性不佳。針對試樣27而言,初始磁導率μi也不佳。進一步,Co的含量為本發明的範圍內但Co/Si過大的試樣6,也是初始磁導率μi的溫度特性不佳。
表2的試樣為將Co及Si以外的全部的組成在本發明的範圍內設為相同,在以2.00、4.80、9.00或10.00重量份固定了Co的含量的基礎上,僅使Si的含量變化的試樣。
由表2可知:在全部的主成分及副成分的組成為本發明的範圍內的情況下,初始磁導率μi、比電阻ρ、頻率特 性及初始磁導率μi的溫度特性變得良好。
與此相對,就作為副成分的Si的含量過少的試樣31、36、41及46而言,初始磁導率μi的溫度特性不佳。另外,Si的含量為本發明的範圍內但Co/Si過大的試樣47,也是初始磁導率μi的溫度特性不佳。
另外,就Si的含量過多的試樣50而言,初始磁導率μi及比電阻ρ不佳。進而,Si的含量為本發明的範圍內,但Co/Si過小的試樣22、40及45,比電阻ρ不佳。就試樣40及45而言,初始磁導率μi也不佳。
表3的試樣為從試樣12使主成分的含量變化的試樣。
由表3可知:在全部的主成分及副成分的組成為 本發明的範圍內的情況下,初始磁導率μi、比電阻ρ、頻率特性及初始磁導率μi的溫度特性變得良好。
與此相對,就主成分的含量為本發明的範圍外的比較例而言,比電阻ρ、頻率特性、初始磁導率μi的溫度特性及/或初始磁導率μi成為不佳的值。
表4的試樣91~95為將Bi以外的組成設為與試樣12相同,僅使Bi的含量變化的試樣。另外,關於表4的試樣12及91~95,為了確認燒結性,也進行了相對密度的測定。
就相對密度的測定而言,對成形為盤形而得到的燒結體,由燒成後的燒結體的尺寸及重量算出燒結體密度,將相對於理論密度的燒結體密度作為相對密度來計算。在本實施例中,將相對密度為95%以上設為良好。
由表4可知:在全部的主成分及副成分的組成為本發明的範圍內的情況下,初始磁導率μi、比電阻ρ、相對密度(燒結性)、頻率特性及初始磁導率μi的溫度特性變得良好。
與此相對,就Bi的含量過少的試樣91而言,相對密度變低。即,試樣91燒結性極度降低。其結果,初始磁導率μi及比電阻ρ成為了不佳的值。另外,就Bi的含量過多 的試樣95而言,比電阻ρ變差。
Claims (2)
- 一種鐵氧體組合物,其特徵在於,該鐵氧體組合物具有主成分和副成分,所述主成分由以Fe 2O 3換算為18~30摩爾%的氧化鐵、以CuO換算為4~14摩爾%的氧化銅、以ZnO換算為0~6摩爾%的氧化鋅、餘量為氧化鎳構成,相對於所述主成分100重量份,作為所述副成分,含有以SiO 2換算為0.30~1.83重量份的矽化合物、以Co 3O 4換算為2.00~10.00重量份的鈷化合物、以Bi 2O 3換算為1.00~3.00重量份的鉍化合物,用以Co 3O 4換算的所述鈷化合物的含量除以以SiO 2換算的所述矽化合物的含量所得的值為5.5~30.0。
- 一種電子部件,其具有由如申請專利範圍第1項所述的鐵氧體組合物構成的鐵氧體燒結體。
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