CN108249915B - 电介质组合物及电子部件 - Google Patents
电介质组合物及电子部件 Download PDFInfo
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- CN108249915B CN108249915B CN201611235524.4A CN201611235524A CN108249915B CN 108249915 B CN108249915 B CN 108249915B CN 201611235524 A CN201611235524 A CN 201611235524A CN 108249915 B CN108249915 B CN 108249915B
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 25
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 20
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 16
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 7
- 238000010587 phase diagram Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 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 claims description 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 27
- 239000003990 capacitor Substances 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 230000005684 electric field Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000484 niobium oxide Inorganic materials 0.000 description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
一种电介质组合物，其含有钛酸钡、钛酸锶、氧化钛及氧化铋。将钛酸钡的含量以BaTiO3换算设为a摩尔％、将钛酸锶的含量以SrTiO3换算设为b摩尔％、将氧化钛及氧化铋的含量以Bi2Ti3O9换算设为c摩尔％，a+b+c＝100。其特征为，a、b及c为在三元系相图上被下述点A、点B、点C及点D这4点包围的范围内的值。点A：(a，b，c)＝(52.1，40.0，7.9)点B：(a，b，c)＝(86.5，5.6，7.9)点C：(a，b，c)＝(91.0，5.6，3.4)点D：(a，b，c)＝(56.6，40.0，3.4)。
Description
技术领域
本发明涉及电介质组合物及电子部件。
背景技术
近几年，伴随着急速推进的电气设备的高性能化，电气电路的小型化、复杂化也进一步急速地推进。因此，对电子部件也要求更进一步的小型化、高性能化。即，正在寻求相对介电常数高且低损失，为了在高电压下使用而交流破坏电压高，另外，温度特性也良好的电介质组合物及电子部件。
为了应对所述要求，在对比文件1中记载有PbTiO3－SrTiO3－Bi2Ti3O9系的电介质组合物。但是，因为该电介质组合物含铅，所以从环境负荷的观点考虑存在问题。
专利文献1：特开2003－163132号公报
发明内容
本发明的目的在于提供一种虽然实质上未使用铅，但是相对介电常数及交流破坏电压良好，在常温下的介电损耗小的电介质组合物、及由该电介质组合物构成的电子部件。
用于解决课题的方案
为实现所述的目的，本发明的电介质组合物含有钛酸钡、钛酸锶、氧化钛及氧化铋，其特征在于，
在将钛酸钡的含量以BaTiO3换算设为a摩尔％、将钛酸锶的含量以SrTiO3换算设为b摩尔％、将氧化钛及氧化铋的含量以Bi2Ti3O9换算设为c摩尔％，且设为a+b+c＝100的情况下，
所述a、b及c在三元系相图上为被下述点A、点B、点C及点D这4点包围的范围内的值。
点A：(a，b，c)＝(52.1，40.0，7.9)
点B：(a，b，c)＝(86.5，5.6，7.9)
点C：(a，b，c)＝(91.0，5.6，3.4)
点D：(a，b，c)＝(56.6，40.0，3.4)
另外，本发明的电介质组合物更优选，含有钛酸钡、钛酸锶、氧化钛及氧化铋，
在将钛酸钡的含量以BaTiO3换算设为a摩尔％、将钛酸锶的含量以SrTiO3换算设为b摩尔％、将氧化钛及氧化铋的含量以Bi2Ti3O9换算设为c摩尔％，且设为a+b+c＝100的情况下，
所述a、b及c为在三元系相图上被下述点A′、点B、点C及点D′这4点包围的范围内的值。
点A′：(a，b，c)＝(64.1，28.0，7.9)
点B：(a，b，c)＝(86.5，5.6，7.9)
点C：(a，b，c)＝(91.0，5.6，3.4)
点D′：(a，b，c)＝(70.8，25.8，3.4)
本发明的电介质组合物通过设定所述的特定的组成及含量，虽然实质上不使用铅，但是，能够良好设定相对介电常数及交流破坏电压，能够减小常温的介电损耗。
本发明的电介质组合物优选在将所述氧化钛及所述氧化铋的含量合计以Bi2Ti3O9换算设为100重量％的情况下，以钛酸铋形式存在的所述氧化钛及所述氧化铋为80重量％以上。
本发明的电介质组合物，优选在设定为
第一副成分，其由含有锰的化合物及含有钴的化合物中的任一种以上构成，
第二副成分，其由含有铌的化合物构成，
第三副成分，其由含有锆的化合物、含有锡的化合物及含锌的化合物中的任一种以上构成，
第四副成分，其由含钇的化合物、含镧的化合物、含铈的化合物、含钕的化合物、含钐的化合物及含镝的化合物中的任一种以上构成的情况下，
含有所述自第一副成分至第四副成分中至少一种。
另外，优选在将钛酸钡、钛酸锶、氧化钛及氧化铋的含量的合计设为100重量％的情况下，
所述第一副成分即含有锰的化合物的含量以MnCO3换算为0.8重量％以下(包括0)，且含有钴的化合物的含量以Co3O4换算为1.7重量％以下(包括0)，
所述第二副成分即含有铌的化合物的含量以Nb2O5换算为1.3重量％以下(包括0)，
在将所述第三副成分中所含的各成分的含量分别进行ZrO2换算、SnO2换算、ZnO换算的情况下，所述第三副成分含量的合计为5.5重量％以下(包括0)，且，
在将所述第四副成分中所含的各成分的含量分别进行Y2O3换算、La2O3换算、CeO2换算、Nd2O3换算、Sm2O3换算、Dy2O3换算的情况下，所述第四副成分的含量的合计为1.0重量％以下(包括0)。
本发明的电介质组合物优选含有所述第一副成分至所述第四副成分的全部。
本发明的电介质组合物，优选所述第三副成分的含量为所述第一副成分至所述第四副成分的含量的合计的24～85％。
本发明的电介质组合物，优选所述第三副成分和所述第四副成分的含量合计为所述第一副成分至所述第四副成分的含量合计的40～90％。
本发明的电子部件，其由所述的电介质组合物构成。
附图说明
图1是本发明的实施方式的单板电容器的剖面图；
图2是本实施方式的主成分的组成的三元系相图。
具体实施方式
以下，基于附图说明本发明的具体实施方式。
对本实施方式的由电介质组合物构成的电子部件的种类没有特别的限制，但是，例如，列举图1所示的单板电容器1。
图1所示的单板电容器1具有本实施方式的电介质组合物10。在电介质组合物10的两面经由电极14a、14b分别固定有端子12a、12b，并用遍及其周围整个面用合成树脂16被覆。
本实施方式的电介质组合物以特定范围内的含量含有钛酸钡、钛酸锶、氧化钛及氧化铋。以下，有时将钛酸钡、钛酸锶、氧化钛及氧化铋称为主成分。
具体而言，在将钛酸钡的含量以BaTiO3换算设为a摩尔％、将钛酸锶的含量以SrTiO3换算设为b摩尔％、将氧化钛及氧化铋的含量以Bi2Ti3O9换算设为c摩尔％，且设为a+b+c＝100的情况下，
以上述a、b及c成为在三元系相图上为被下述点A、点B、点C及点D这4点包围的范围内的值的方式含有各成分。
点A：(a，b，c)＝(52.1，40.0，7.9)
点B：(a，b，c)＝(86.5，5.6，7.9)
点C：(a，b，c)＝(91.0，5.6，3.4)
点D：(a，b，c)＝(56.6，40.0，3.4)
另外，更优选以成为上述a、b及c在三元系相图上成为被下述点A′、点B、点C及点D′这4点包围的范围内的值的方式含有各成分。
点A′：(a，b，c)＝(64.1，28.0，7.9)
点B：(a，b，c)＝(86.5，5.6，7.9)
点C：(a，b，c)＝(91.0，5.6，3.4)
点D′：(a，b，c)＝(70.8，25.8，3.4)
将表示上述各点的位置的三元系相图示于图2。
本实施方式的电介质组合物中，各主成分的组成为被点A、点B、点C及点D这4点包围的范围内，由此，即使实质上不使用铅也可以使相对介电常数及交流破坏电压良好，能够减小常温下的介电损耗。在各主成分的组成为被点A′、点B、点C及点D′这4点包围的范围内的情况下，相对介电常数、温度特性及介电损耗的整体的均衡具有变得更良好的倾向。在各主成分的组成为被点A′、点B、点C及点D′这4点包围的范围内的情况下，尤其是具有在高温下的介电损耗变小的倾向。在本申请中，所谓“常温”是指大概25℃上下，更详细地说是指20～30℃程度的温度。所谓“高温”是指大概125℃上下，更详细地说是指100～150℃程度的温度。
此外，在本实施方式的电介质组合物中，所谓实质上不使用铅，具体而言，是指在电介质组合物整体设为100重量％的情况下，铅的含量为0.001重量％以下的情况。在本实施方式的电介质组合物中，通过实质上不使用铅，能够减小环境负荷。
氧化钛及氧化铋也可以分别存在于电介质组合物中，但是，优选作为钛酸铋(Bi2Ti3O9)存在。由于作为钛酸铋存在氧化钛及氧化铋，从而能够进一步提高交流破坏电压及温度特性，能够使介电损耗降低。
在电介质组合物中分别存在氧化钛及氧化铋，但是，是否作为钛酸铋存在可以通过XRD、EPMA、TEM－EDS等观察电介质组合物的内部构造来确认。具体而言，从XRD的衍射波峰来鉴定各相，或通过观察Ba、Sr、Bi、Ti映像来看重合程度而能够判别各相。另外，在将电介质组合物中的氧化钛及氧化铋的含量以Bi2Ti3O9换算设为100重量％的情况下，优选作为钛酸铋存在的氧化钛及氧化铋的比例为80重量％以上。
本实施方式的电介质组合物优选含有作为第一副成分的含有锰的化合物及含有钴的化合物的任一种以上。通过含有第一副成分，能够使温度特性良好。
上述含锰的化合物的含量优选在将主成分整体设为100重量％的情况下，以MnCO3换算为0.8重量％以下，更优选0.5～0.8重量％。通过在上述范围内含有含锰的化合物，能够使相对介电常数及交流破坏电压良好，能够减小介电损耗，同时能够提高温度特性。
上述含钴的化合物的含量在将主成分整体设为100重量％的情况下，以Co3O4换算优选为1.7重量％以下，更优选0.5～1.7重量％。通过在上述的范围内含有含钴的化合物，能够使相对介电常数及AC击穿电场良好，能够减小介电损耗，同时能够提高温度特性。
本实施方式的电介质组合物优选含有作为第二副成分的含铌的化合物。通过含有第二副成分，能够使温度特性良好，能够减小介电损耗。
上述含铌的化合物的含量在将主成分整体设为100重量％的情况下，以Nb2O5换算优选为1.3重量％以下，更优选为0.5～1.3重量％。通过在上述范围内含有含铌的化合物，能够使相对介电常数、交流破坏电压良好，能够减小介电损耗，同时能够提高温度特性。
本实施方式的电介质组合物优选含有作为第三副成分的含锆的化合物、含锡的化合物及含锌的化合物中任一种以上。通过含有第三副成分，能够使温度特性良好，能够减小介电损耗。
在将上述各成分的含量分别进行了ZrO2换算、SnO2换算、ZnO换算的情况下，优选第三副成分的含量合计为5.5重量％以下，更优选0.5～5.5重量％。通过在上述的范围内含有第三副成分，能够使相对介电常数及交流破坏电压良好，能够减小介电损耗，同时能够提高温度特性。
本实施方式的电介质组合物优选含有作为第四副成分的含钇的化合物、含镧的化合物、含铈的化合物、含钕的化合物、含钐的化合物及含镝的化合物中任一种以上。通过含有第四副成分，能够使温度特性良好，能够减小介电损耗。
在将上述各成分的含量分别进行了Y2O3换算、La2O3换算、CeO2换算、Nd2O3换算、Sm2O3换算、Dy2O3换算的情况下，优选第四副成分的含量合计为1.0重量％以下，更优选为0.10～1.0质量％以下。通过在上述范围内含有第四副成分，能够使相对介电常数及交流破坏电压良好，能够减小介电损耗，同时能够提高温度特性。
本实施方式的电介质组合物优选含有自上述第一副成分至第四副成分中任意一种以上，更优选含有上述第一副成分至第四副成分的全部。通过含有上述第一副成分至第四副成分的全部，够减小介电损耗，能够使温度特性良好。在含有上述第一副成分至第四副成分的全部的情况下，尤其是能够显著地减小在高温的介电损耗。
另外，在含有上述第一副成分至第四副成分的全部的情况下，第一副成分的含量优选为，含锰的化合物的含量以MnCO3换算为0.8重量％以下，含钴的化合物的含量以Co3O4换算为1.7重量％以下。第二副成分的含量优选为1.3重量％以下。第三副成分的含量优选合计为5.5重量％以下。第四副成分的含量优选合计为1.0重量％以下。
另外，在含有上述第一副成分至第四副成分的全部的情况下，优选第三副成分的含量为第一副成分至第四副成分的含量合计的24～85％。在该情况下，在常温下的介电损耗变得更小，温度特性提高。
另外，优选第三副成分的含量为第一副成分至第四副成分的含量的合计24～85％，且，上述第三副成分和上述第四副成分的含量的合计为上述第一副成分至上述第四副成分的含量的合计的40～90％。在该情况下，在常温下的介电损耗变得更小，温度特性提高。
以下，对本实施方式的电介质组合物及电子部件的制造方法进行说明，但是，电介质组合物及电子部件的制造方法不限于下述方法。
首先，准备本实施方式的电介质组合物的原料粉末。作为原料粉末，准备各成分的化合物、或通过烧制而成为各成分的化合物的粉末。在各成分中，对于钛酸钡(BaTiO3)及钛酸锶(SrTiO3)，优选在准备原料的时刻准备钛酸钡粉末及钛酸锶粉末。另外，对于氧化钛及氧化铋，也可以分别准备在烧制后成为氧化钛的化合物的粉末及在烧制后成为氧化铋的化合物的粉末，但是，优选准备钛酸铋(Bi2Ti3O9)粉末。将最后成为氧化钛及氧化铋的原料粉末整体以Bi2Ti3O9换算设为100重量％，将钛酸铋粉末的比例设为80重量％以上，由此，即使在最后获得的电介质组合物中也能够将钛酸铋的比例设为80重量％以上。
对于第一副成分至第四副成分，除各元素的氧化物之外，可以准备在烧制后可成为各元素的氧化物的化合物，例如碳酸盐、硝酸盐、硫酸盐等。
接着，混合各成分的原料粉末而得到混合粉末。混合方法没有特别限制，可以使用通常所用的方法，例如干式混合、湿式混合等。
接着，对上述混合粉末造粒，在造粒后根据需要进行整粒，获得颗粒粉末。造粒方法没有特别限制。例如，有在上述混合粉末中添加PVA(聚乙烯醇)水溶液的造粒方法。另外，整粒方法也没有特别限定。例如，为了去除粗大的造粒粉末也可以进行筛选。
接着，对颗粒粉末成形，获得由电介质组合物构成的成形体。对成形方法没有特别限制，可以使用通常应用的方法。例如可以使用加压成形。对加压时的压力没有特别限制。例如可以设为200～600MPa。
接着，通过烧制所得到的成形体，获得由电介质组合物构成的烧结体。对烧制条件没有特别限制。烧制温度可以设为1200～1350℃。对烧制气氛也没有特别限制。例如，可以设为空气中、氮气气氛中、或使用了氮气及氢气的还原气氛中，但是，也可以在除此之外的其它的气氛中。
另外，使一对电极与所得到的烧结体接合。一对电极与例如所得到的烧结体的相对的两个面进行接合。
另外，对使电极与所得到的烧结体接合的方法没有特别限制。例如，对所得到的烧结体涂装电极膏，在700～900℃进行烧粘，由此，可以使电极与所得到的烧结体接合。
进而，经由电极连接端子。对经由电极连接端子的方法没有特别限制。而且，以使端子的一部分露出的方式遍及电介质组合物的周围整个面进行树脂被覆。对被覆方法及进行被覆的树脂的种类没有特别限制。
这样，能够获得图1所示的单板型电容器。该单板型电容器使用本实施方式的电介质组合物，由此，能够在非常高的电压下应用。
此外，在上述的说明中，将本实施方式的电子部件作为图1所示的单板型电容器对其制造方法进行了说明，但是，本发明的电容器不限于单板型电容器，也可以是叠层型电容器等除了单板型电容器以外的电容器。对叠层型电容器等制造方法没有特别限制，可以使用已知的制造方法。另外，对本发明的电容器的用途没有特别限制，但是，作为高频用电容器及高电压用电容器可以合适地应用。
【实施例】
以下，进一步基于详细的实施例对本发明进行说明，但是，本发明不限于这些实施例。
(实施例1)
作为原料粉末，准备钛酸钡粉末、钛酸锶粉末、钛酸铋粉末、及通过烧制而成为上述第一副成分～第四副成分的粉末，进行秤量以获得最终如表1～表3所记载的实施例及比较例组成的烧结体。此外，表1的BT表示钛酸钡(BaTiO3)，ST表示钛酸锶(SrTiO3)，BiTi表示钛酸铋(Bi2Ti3O9)。另外，在试样序号1a中，代替钛酸铋粉末而使用了氧化钛粉末及氧化铋粉末。
在表1中，在主成分的组成为被点A、点B、点C、点D这4点包围的范围内的情况下，将ABCD栏设为○，在主成分的组成为被点A、点B、点C、点D这4点包围的范围外的情况下，将ABCD栏设为×。进而，在主成分的组成为被点A′、点B、点C、点D′这4点包围的范围内的情况下，将A′BCD′栏设为○，在主成分的组成为被点A′、点B、点C、点D′这4点包围的范围外的情况下，将A′BCD′栏设为×。
在将各原料粉末混合之后，使用球磨机，以平均粒径成为0.5～3μm左右的方式进行了微粉碎。对微粉碎的粉末进行脱水干燥之后，相对于原料粉末100重量份添加10重量份的聚乙烯醇，进行造粒及整粒，制成了颗粒粉末。
对上述颗粒粉末以300MPa压力进行成形，制成直径16.5mm、厚度0.65mm圆板状的成形体。
将上述成形体在空气中，在1200～1300℃下烧制4小时，获得圆板状的瓷器原材料。用荧光X射线分析确认到所得到的瓷器原材料的组成成为表1所示的组成。接着，在上述瓷器原材料的两面涂装Ag电极膏，在Air气氛中，在800℃下进行15分钟烧制，获得电极直径12mm的电容器样品。磁器电容器样品为了全部进行以下所示的评价而制造了必要的数量。
而且，对所得到的电容器样品评价了AC击穿电场、相对介电常数、品质因数、静电容量温度特性、可靠性(高温负荷后的静电容量变化率)。以下，对评价方法进行说明。
AC击穿电场AC－Eb(KV/mm)的测定以下述的方法进行。对所得到的电容器样品的两端付与交流电场。使交流电场的大小以200V/s的速度上升，用交流耐压测定机观察泄漏电流的变化。将泄漏电流成为50mA时的电场设为AC击穿电场AC－Eb。可以说AC－Eb越高，交流破坏电压越高，对于交流电压的耐压性越优异。在本实施例中，将AC－Eb≧5.0KV/mm设定为良好。
相对介电常数(εs)根据相对于圆板状的电容器样品，在温度25℃、频率数1KHz、输入信号电平(测定电压)1.0Vrms的条件下使用LCR仪表测定的静电容量算出。在本实施例中，将εs≧1250设为良好，将εs≧1500设为更好。
就基准温度25℃下的介电损耗(tanδ)而言，相对于电容器样品，用LCR仪表在频率数1KHz、输入信号电平(测定电压)1.0Vrms的条件下测定。在本实施例中，基准温度25℃下的介电损耗(tanδ)将0.70％以下设定为良好。进而，测定了基准温度125℃下的介电损耗(tanδ)。基准温度125℃下的介电损耗(tanδ)的测定条件除了测定温度以外，与上述基准温度25℃下的介电损耗(tanδ)的测定条件同样。在本实施例中，基准温度125℃下的介电损耗(tanδ)将0.80％以下设为良好。但是，即使基准温度125℃下的介电损耗(tanδ)不是良好，也能够实现本申请发明的目的。
温度特性TC(％)的测定方法如下。首先，使温度在－25℃～+85℃范围变化来测定了各温度的静电容量。静电容量使用LCR仪表在频率数1kHz、输入信号电平1Vrms的条件下进行测定。而且，在将基准温度+25℃下的静电容量设为C25、将T(℃)的静电容量设为CT的情况下，根据下式测定在各温度的TC。
TC(％)＝{(CT－C25)/C25}×102
在本实施例中，在－25℃～+85℃范围内总是将成为－40≦TC≦+22的情况设定为良好。在本实施例中，就在－25℃及+85℃下TC为上述范围内的电容器样品而言，即使在－25℃～+85℃范围内之外的温度，TC也在上述的范围内。因此，在表1～表3中记载了在－25℃及+85℃下的TC。但是，在－25℃～+85℃范围内，即使总是不在－40≦TC≦+22的范围内，也能够实现上述本发明的目的。
【表1】
*为比较例
在表1中，记载了不含第一副成分～第四副成分的全部的实施例及比较例。根据表1，具有本发明的范围内的组成的实施例即ABCD栏为○的实施例，相对介电常数εs、AC击穿电场AC－Eb及25℃下的介电损耗tanδ均良好。
另外，添加了钛酸铋的试样序号1b与除分别添加了氧化钛和氧化铋这一点以外其它与试样序号1b为同一组成的试样序号1a相比，介电损耗tanδ及温度特性TC良好。
另外，在主成分的组成为被点A′、点B、点C、点D′这4点包围的范围内的值的情况下，在－25℃～+85℃范围内总是满足－33≦TC≦+22，且125℃下的介电损耗tanδ总是为良好等，与被点A′、点B、点C、点D′这4点包围的范围外的值的情况相比，存在具有优异的特性的倾向。此外，在－25℃～+85℃范围内总是满足－33≦TC≦+22的情况下，必然满足Z5T的温度特性。
与之相对，不具有本发明的范围内的组成的比较例，相对介电常数εs、AC击穿电场AC－Eb及25℃下的介电损耗tanδ中的任意一个以上均恶化。
【表2】
在表2中，记载了主成分的组成与试样序号1b同样而使副成分的含量变化的实施例。
根据表2的试样序号1b、51～54，以MnCO3换算含有0.8重量％以下氧化锰的试样序号51～53与不含氧化锰的试样序号1b相比，温度特性及125℃下的介电损耗优异。特别是含有氧化锰0.5～0.8重量％的试样序号52、53与含有氧化锰0.1重量％的试样序号51相比，温度特性更优异。另外，试样序号51～53与含有1.0重量％氧化锰的试样序号54相比，相对介电常数及25℃下的介电损耗优异。
根据表2的试样序号1b、55～57、59，以Co3O4换算含有1.7重量％以下的氧化钴的试样序号55～57与不含氧化钴的试样序号1b相比，温度特性及125℃下的介电损耗优异。特别是含有氧化钴0.5～1.7重量％的试样序号56、57与含有氧化锰0.1重量％的试样序号55相比，温度特性更优异。另外，试样序号55～57与含有氧化钴1.8重量％的试样序号59相比，相对介电常数及25℃下的介电损耗优异。
根据表2的试样序号1b、58，两种氧化锰和氧化钴均含有的试样序号58与都不含有氧化锰和氧化钴的试样序号1b相比，温度特性优异。
根据表2的试样序号1b、60～64，含有氧化铌1.3重量％以下的试样序号60～63与不含有氧化铌的试样序号1b相比，高温下的温度特性及125℃下的介电损耗优异。尤其是，特别是含有氧化铌0.5～1.3重量％的试样序号62、63与含有氧化铌不足0.5质量％的试样序号60、61相比，温度特性优异。另外，试样序号60～63与含有氧化铌1.4重量％的试样序号64相比，相对介电常数优异。
根据表2的试样序号1b、65～75，含有第三副成分5.5重量％以下的试样序号65～74与不含第三副成分的试样序号1b相比，高温的温度特性优异。尤其是，含有第三副成分0.5～5.5重量％的试样序号66、67、69、72～74与含有第三副成分不足0.5质量％的试样序号65、68、70、71相比，温度特性优异。另外，试样序号65～74与含有第三副成分6.0重量％的试样序号75相比，相对介电常数及25℃下的介电损耗优异。
根据表2的试样序号1b、76～95，含有第四副成分1.0重量％以下的试样序号76～94与不含第四副成分的试样序号1b相比，温度特性优异。尤其是，含有第四副成分0.1～1.0重量％的试样与含有第四副成分不足0.1重量％的试样相比，温度特性优异。另外，试样序号76～94与含有第四副成分1.2重量％的试样序号95相比，相对介电常数及25℃下的介电损耗优异。
作为第三副成分含有氧化锡0.1重量％，另外，含有第一副成分或者第四副成分的试样序号96～104与不含第一副成分～第四副成分的试样序号1b相比，AC击穿电场及温度特性优异。
【表3】
在表3中，记载了主成分的组成与试样序号1b同样、并含有第一副成分～第四副成分的全部的实施例(试样序号105～120)。另外，表3中记载的试样全部是第一副成分为含锰的化合物、第二副成分为含铌的化合物、第三副成分为含锡的化合物。关于第四副成分，试样序号105～112为含钐的化合物，试样序号113～120为含镝的化合物。
首先，含有第一副成分～第四副成分的全部的试样序号105～120与不含有副成分的试样序号1b相比，AC击穿电场、温度特性、尤其是125℃下的介电损耗优异。特别是，125℃下的介电损耗与表1及表2中记载的其它的实施例相比也显著优异。
在上述第三副成分的含量为上述第一副成分至上述第四副成分的含量的合计24～85％的情况下(试样序号106、107、109～112、114、115、117～120)，与不是24～85％的情况(试样序号105、108、113、116)相比，温度特性及25℃下的介电损耗更优异。
上述第三副成分的含量为上述第一副成分至上述第四副成分的含量的合计24～85％，且，在上述第三副成分和上述第四副成分的含量的合计为上述第一副成分至上述第四副成分的含量的合计40～90％的情况下(试样序号110、111、118、119)，与除此之外的情况相比，温度特性及25℃下的介电损耗更优异。
Claims (7)
1.一种电介质组合物，其特征在于，
含有钛酸钡、钛酸锶、氧化钛及氧化铋作为主成分，
在将钛酸钡的含量以BaTiO3换算设为a摩尔％、将钛酸锶的含量以SrTiO3换算设为b摩尔％、将氧化钛及氧化铋的含量以Bi2Ti3O9换算设为c摩尔％，且设为a+b+c＝100的情况下，
所述a、b及c在三元系相图上为被下述点A、点B、点C及点D这4点包围的范围内的值，
点A：(a，b，c)＝(52.1，40.0，7.9)
点B：(a，b，c)＝(86.5，5.6，7.9)
点C：(a，b，c)＝(91.0，5.6，3.4)
点D：(a，b，c)＝(56.6，40.0，3.4)，
在设定第一副成分、第二副成分、第三副成分以及第四副成分的情况下，含有所述第一副成分至所述第四副成分的全部，
所述第一副成分由含有锰的化合物及含有钴的化合物中的任一种以上构成，
所述第二副成分由含有铌的化合物构成，
所述第三副成分由含有锆的化合物、含有锡的化合物及含有锌的化合物中的任一种以上构成，
所述第四副成分由含有钇的化合物、含有镧的化合物、含有铈的化合物、含有钕的化合物、含有钐的化合物及含有镝的化合物中的任一种以上构成。
2.根据权利要求1所述的电介质组合物，其中，
所述a、b及c在三元系相图上为被下述点A′、点B、点C及点D′这4点包围的范围内的值，
点A′：(a，b，c)＝(64.1，28.0，7.9)
点B：(a，b，c)＝(86.5，5.6，7.9)
点C：(a，b，c)＝(91.0，5.6，3.4)
点D′：(a，b，c)＝(70.8，25.8，3.4)。
3.根据权利要求1或2所述的电介质组合物，其中，
在将所述氧化钛及所述氧化铋的含量的合计以Bi2Ti3O9换算设为100重量％的情况下，以钛酸铋的形式存在的所述氧化钛及所述氧化铋为80重量％以上。
4.根据权利要求1或2所述的电介质组合物，其中，
在将钛酸钡、钛酸锶、氧化钛及氧化铋的含量的合计设为100重量％的情况下，
作为所述第一副成分的含有锰的化合物的含量以MnCO3换算为0.8重量％以下，且含有钴的化合物的含量以Co3O4换算为1.7重量％以下，
作为所述第二副成分的含有铌的化合物的含量以Nb2O5换算为1.3重量％以下，
在将所述第三副成分中所含的各成分的含量分别进行ZrO2换算、SnO2换算、ZnO换算的情况下，所述第三副成分的含量的合计为5.5重量％以下，且，
在将所述第四副成分中所含的各成分的含量分别进行Y2O3换算、La2O3换算、CeO2换算、Nd2O3换算、Sm2O3换算、Dy2O3换算的情况下，所述第四副成分的含量的合计为1.0重量％以下。
5.根据权利要求4所述的电介质组合物，其中，
所述第三副成分的含量为所述第一副成分至所述第四副成分的含量合计的24～85％，其中，所述第三副成分的含量以及所述第一副成分至所述第四副成分的含量的单位为重量％。
6.根据权利要求5所述的电介质组合物，其中，
所述第三副成分和所述第四副成分的含量合计为所述第一副成分至所述第四副成分的含量合计的40～90％，其中，所述第三副成分和所述第四副成分的含量以及所述第一副成分至所述第四副成分的含量的单位为重量％。
7.一种电子部件，其由权利要求1～6中任一项所述的电介质组合物构成。
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