JP5039039B2 - 誘電体磁器およびコンデンサ - Google Patents
誘電体磁器およびコンデンサ Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims description 29
- 229910052573 porcelain Inorganic materials 0.000 title description 6
- 239000013078 crystal Substances 0.000 claims description 126
- 239000002245 particle Substances 0.000 claims description 83
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 79
- 239000000919 ceramic Substances 0.000 claims description 71
- 239000011777 magnesium Substances 0.000 claims description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- 229910002113 barium titanate Inorganic materials 0.000 claims description 26
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052788 barium Inorganic materials 0.000 claims description 18
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004020 conductor Substances 0.000 claims description 15
- 238000002441 X-ray diffraction Methods 0.000 claims description 14
- 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
- 238000010030 laminating Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 description 32
- 239000000843 powder Substances 0.000 description 16
- 230000007704 transition Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 7
- 230000005621 ferroelectricity Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
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- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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Description
前記誘電体磁器を構成するバリウム1モルに対して、前記マグネシウムをMgO換算で0.02〜0.04モル、前記希土類元素(RE)をRE2O3換算で0.01〜0.03モル含み、さらにマンガンをMnO換算で0〜0.01モル含み、かつ前記結晶粒子の平均粒径が115〜145nmであることが望ましい。
本発明のコンデンサは、誘電体層と導体層とを交互に積層した積層体を含むものであって、前記誘電体層が、上記の誘電体磁器からなることを特徴とする。
チタン酸バリウム(BaTiO3)に対して、添加物(マグネシウム、希土類元素、マンガン)を表1に示す組み合わせで添加して焼成し、誘電体磁器を作製した(表1中の試料No.1〜30)。具体的には、まず、予め合成した平均粒径100nm(試料No.2は200nm)のBaTiO3粉末のバリウム1モル部に対して、表1に示す量の添加物を加え、混合粉末を調製した。次に、この混合粉末を温度1050℃、2時間にて仮焼し、仮焼粉末を得た。
作製した誘電体磁器であるこれらの試料について、組成分析を行った。試料の組成分析は、ICP分析もしくは原子吸光分析により行った。具体的には、まず、得られた誘電体磁器を硼酸と炭酸ナトリウムと混合し溶融させたものを塩酸に溶解させて、原子吸光分析により誘電体磁器に含まれる元素の定性分析を行った。次いで、特定した各元素について標準液を希釈したものを標準試料として、ICP発光分光分析にかけて定量化した。また、各元素の価数を周期表に示される価数として酸素量を求めた。その結果、得られた試料の組成は、表1に示す組成に相違ないものであった。
誘電体磁器の結晶粒子の平均粒径は、まず、得られた誘電体磁器の破断面を研磨した後、走査型電子顕微鏡を用いて内部組織の写真を撮る。次いで、その写真に映し出されている結晶粒子の輪郭から画像処理にて各粒子の面積を求め、同じ面積をもつ円に置き換えたときの直径を算出した。そして、このようにして直径を求めた結晶粒子約100個の平均値を求めた。
結晶粒子1の中心部1cにおける希土類元素の濃度C1/2、および、結晶粒子1における中心部1cと表面との中間1dにおける希土類元素の濃度C1/4は、断面を研磨し、FIB加工した誘電体磁器に対して元素分析機器(EDS)を付設した透過電子顕微鏡装置(TEM)を用いて測定した。
結晶構造、すなわち結晶相の同定は、X線回折(2θ=40〜50°、Cu−Kα)を用いて行った。このとき、X線回折パターンにおける(002)面および(200)面の回折ピークの分離が明確に見られないもの(図4(a)に相当)を立方晶系とした。また、(002)面および(200)面の回折ピークの分離が明確に現れているもの(図4(b)に相当)を正方晶系とした。
LCRメーターHP4284Aを用いて周波数1.0kHz、入力信号レベル1.0Vにて静電容量および誘電損失を測定し、試料の直径と厚みおよび導体膜の面積から25℃における比誘電率C25を算出した。また、比誘電率の変化率を−55〜125℃の範囲で測定した。
Claims (3)
- チタン酸バリウムを主成分とし、マグネシウムおよび希土類元素を含む結晶粒子により構成される誘電体磁器であって、前記誘電体磁器を構成するバリウム1モルに対して、マグネシウムをMgO換算で0.02〜0.064モル、希土類元素(RE)をRE2O3換算で0.01〜0.06モル含み、
前記結晶粒子の中心部における希土類元素の濃度をC 1/2 、前記結晶粒子における中心部と表面との中間における希土類元素の濃度をC 1/4 としたときに、比(C 1/2 /C 1/4 )が0.75〜1であるとともに、
X線回折において、2θ=44.5〜45.5°の回折角間に1つのピークのみを有し、前記結晶粒子の結晶構造が立方晶系であり、かつ前記結晶粒子の平均粒径が100〜145nmであることを特徴とする誘電体磁器。 - 前記誘電体磁器を構成するバリウム1モルに対して、前記マグネシウムをMgO換算で0.02〜0.04モル、前記希土類元素(RE)をRE2O3換算で0.01〜0.03モル含み、さらにマンガンをMnO換算で0〜0.01モル含み、かつ前記結晶粒子の平均粒径が115〜145nmである請求項1に記載の誘電体磁器。
- 誘電体層と導体層とを交互に積層した積層体を含むコンデンサであって、前記誘電体層が、請求項1または2に記載の誘電体磁器からなることを特徴とするコンデンサ。
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JP5025570B2 (ja) * | 2008-04-24 | 2012-09-12 | 京セラ株式会社 | 積層セラミックコンデンサ |
JP5067401B2 (ja) * | 2009-06-30 | 2012-11-07 | 株式会社村田製作所 | 誘電体セラミックおよびその製造方法ならびに積層セラミックコンデンサ |
US8263515B2 (en) | 2009-08-29 | 2012-09-11 | Fatih Dogan | Nanostructured dielectric materials for high energy density multi layer ceramic capacitors |
US8181134B2 (en) | 2009-10-16 | 2012-05-15 | International Business Machines Corporation | Techniques for performing conditional sequential equivalence checking of an integrated circuit logic design |
KR20130042578A (ko) | 2010-09-17 | 2013-04-26 | 가부시키가이샤 무라타 세이사쿠쇼 | 유전체 세라믹, 적층 세라믹 콘덴서, 및 이들의 제조방법 |
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JP6026883B2 (ja) * | 2012-12-27 | 2016-11-16 | 京セラ株式会社 | 圧電部品 |
WO2015016268A1 (ja) * | 2013-07-30 | 2015-02-05 | 京セラ株式会社 | 誘電体フィルム、フィルムコンデンサ、および電気装置 |
US10395828B2 (en) * | 2015-10-28 | 2019-08-27 | Kyocera Corporation | Capacitor |
JP6933326B2 (ja) * | 2017-03-08 | 2021-09-08 | 太陽誘電株式会社 | 積層セラミックコンデンサ及びその製造方法 |
US20220013288A1 (en) * | 2018-11-13 | 2022-01-13 | Jonathan E. Spanier | Nanocrystalline high-k low-leakage thin films |
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