JP6152481B2 - 導電性酸化物焼結体、導電用部材、ガスセンサ、圧電素子、及び、圧電素子の製造方法 - Google Patents
導電性酸化物焼結体、導電用部材、ガスセンサ、圧電素子、及び、圧電素子の製造方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000010304 firing Methods 0.000 claims description 81
- 239000000919 ceramic Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
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- 238000000034 method Methods 0.000 claims description 11
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- 239000004020 conductor Substances 0.000 claims description 7
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000002585 base Substances 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 7
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- 239000010955 niobium Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
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- 238000005520 cutting process Methods 0.000 description 4
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- 239000011777 magnesium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
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- 239000002002 slurry Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
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- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical compound [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004121 SrRuO Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Description
0.474≦a≦0.512、
0.050≦b≦0.350、
0<c<0.250、
0.050≦d≦0.350
を満たすことを特徴とする導電性酸化物焼結体。
この導電性酸化物焼結体によれば、100S/cm以上の室温導電率を達成しつつ、焼成温度を約1100℃から約1500℃の範囲で選択可能となる。
この構成によれば、室温導電率がより高い導電性酸化物焼結体を得ることができる。
0.487≦a≦0.506、
0.050≦b≦0.250、
0<c<0.250、
0.200≦d≦0.275
を満たすものとしても良い。
この構成によれば、400S/cm以上の室温導電率を達成しつつ、焼成温度を約1100℃から約1500℃の範囲で選択可能となる。更に、最適な焼成温度を選択すれば、1200S/cm以上の室温導電率を達成可能である。
本発明の一実施形態としての導電性酸化物焼結体は、以下の組成式を満たすペロブスカイト型酸化物結晶構造を有する結晶相を含む酸化物焼結体である。
REaCobCucNidOx …(1)
ここで、REは希土類元素を表し、a+b+c+d=1、1.25≦x≦1.75である。また、係数a,b,c,dは以下の関係を満たす。
0.474≦a≦0.512 …(2a)
0.050≦b≦0.350 …(2b)
0<c<0.250 …(2c)
0.050≦d≦0.350 …(2d)
0.487≦a≦0.506 …(3a)
0.050≦b≦0.250 …(3b)
0<c<0.250 …(3c)
0.200≦d≦0.275 …(3d)
係数a,b,c,dがこれらの関係を満足すれば、400S/cm以上の室温導電率を達成しつつ、焼成温度を約1100℃から約1500℃の範囲で選択可能となる。更に、最適な焼成温度を選択すれば、1200S/cm以上の室温導電率を達成可能である。
図1は、本発明の一実施形態における導電性酸化物焼結体の製造方法を示すフローチャートである。工程T110では、導電性酸化物焼結体の原料粉末を秤量した後、湿式混合して乾燥することにより、原料粉末混合物を調整する。原料粉末としては、例えば、REOH3又はRE2O3、Co3O4、CuO及びNiOを用いることができる。工程T120では、この原料粉末混合物を大気雰囲気下、700〜1200℃で1〜5時間仮焼して仮焼粉末を作成する。工程T130では、この仮焼粉末に適量の有機バインダを加え、これを分散溶媒(例えばエタノール)と共に樹脂ポットに投入し、ジルコニア玉石を用いて湿式混合粉砕してスラリーを得る。工程T130では、得られたスラリーを80℃で2時間ほど乾燥し、さらに、250μmメッシュの篩を通して造粒し、造粒粉末を得る。工程T140では、得られた造粒粉末をプレス機によって成形する。工程T150では、大気雰囲気下、工程T120における仮焼温度よりも高い焼成温度(1000〜1550℃、好ましくは約1100〜1500℃)で1〜5時間焼成することによって導電性酸化物焼結を得る。焼成の後には、必要に応じて導電性酸化物焼結体の平面を研磨してもよい。
図4は、実施例及び比較例としての複数のサンプルの組成及び特性を示している。ここでは、サンプルS01〜S19は実施例であり、サンプルS31〜S37は比較例である。各サンプルの酸化物焼結体は、図1で説明した製造方法に従ってそれぞれ作成し、最後に平面研磨を行って、3.0mm×3.0mm×15mmの直方体状のサンプルを得た。なお、工程T110では、図4に示す組成に従って原料を秤量・混合した。希土類元素REは、サンプルS01〜S16,S19,S31〜S37ではLaとし、サンプルS17ではPr、サンプルS18ではNdとした。
各サンプルについて、直流4端子法により導電率を測定した。測定に用いる電極及び電極線にはPtを用いた。また導電率測定は、電圧・電流発生器(エーディーシー社製のモニタ6242型)を用いた。
各サンプルに対し、JIS-R-1634に基づき焼結性を評価した。具体的には、まずサンプルの乾燥重量W1と飽水重量W3を測定し、以下の式(4)を用いて吸水率を算出した。
吸水率(%)=(W3−W1)/W1×100 …(4)
そして、以下の基準で焼結性を評価した。
×:吸水率が0.10wt%を超えた場合
△:吸水率が0.05wt%以上0.10wt%以下の場合
○:吸水率が0.05wt%未満の場合
なお、吸水率の評価結果が、△又は○であれば、酸化物焼結体が緻密な組織を有するような良好な焼結性を示し、当該焼結体を導電体として用いることに実用上問題はない。
導電性酸化物焼結体と基材との密着試験は以下のように行った。まず、平板状に加工した焼結済みのYSZ(イットリア安定化ジルコニア)基材を準備した。また、図4に示す各組成の酸化物の仮焼粉末を、エタノール等の溶媒に溶解してスラリーとし、そのスラリーを、YSZ基材に塗布し、乾燥した後、1100℃で焼成することにより、密着試験用サンプルを作製した。この密着試験用サンプルに対し、表面界面切削分析(SAICAS)法を用いて、導電性酸化物焼結体とYSZ基材の界面の剥離強度を測定した。剥離強度の測定装置は、ダイプラ・ウィンテス社製DN−100S型SAICASを用いた。切削刃には刃幅:w=2.0mm、すくい角20°、逃げ角10°の焼結BN(ボラゾン)製切削刃を用いた。剥離強度試験の条件は、剪断角度は45°、押圧荷重を0.5N、バランス加重0.5Nとし、定速度モード(垂直速度0.4μm/sec、水平速度8μm/sec)にて切削を行い、水平、垂直力を記録した。得られた水平力FHと刃幅wから以下の式(5)を用いて、剥離強度Pを算出した。
P[kN/m]=FH[kN]/w[m] …(5)
そして、以下の基準で剥離強度を評価した。
×:Pが0.1kN/m未満の場合
△:Pが0.1kN/m以上 1.0kN/m未満の場合
○:Pが1.0kN/m以上の場合
<B定数の測定方法>
上記<導電率の測定>で説明した方法で測定した25℃と900℃の導電率から、下記(6)式に従ってB定数(K)を算出した。
B定数=ln(ρ1/ρ2)/(1/T1−1/T2) …(6)
ρ1=1/σ1
ρ2=1/σ2
ρ1:絶対温度T1(K)における抵抗率(Ωcm)
ρ2:絶対温度T2(K)における抵抗率(Ωcm)
σ1:絶対温度T1(K)における導電率(S/cm)
σ2:絶対温度T2(K)における導電率(S/cm)
T1=298.15(K)
T2=1143.15(K)
図8は、本発明の他の実施形態としての圧電素子を示す斜視図である。この圧電素子200は、円板状の圧電磁器300の上面と下面に電極301,302が取り付けられた構成を有している。電極301,302は、上述した導電性酸化物焼結体によって形成される。なお、圧電素子としては、これ以外の種々の形状や構成の圧電素子を形成可能である。
(KaNabLicCd)e(DfEg)Oh …(7)
ここで、元素CはCa(カルシウム),Sr(ストロンチウム),Ba(バリウム),Rb(ルビジウム)の一種以上、元素DはNb(ニオブ),Ta(タンタル),Ti(チタン),Zr(ジルコニウム)のうちの少なくともNb又はTaを含む一種以上、元素EはMg(マグネシウム),Al(アルミニウム),Sc(スカンジウム),Mn(マンガン),Fe(鉄),Co(コバルト),Ni(ニッケル),Zn(亜鉛),Ga(ガリウム),Y(イットリウム)の一種以上であり、a+b+c+d=1、eは任意、f+g=1、hはペロブスカイトを構成する任意の値であり、典型的には2.9≦h≦3.1である。
(KaNabLicCad1Bad2)e(Nbf1Tif2Zrf3)Oh …(8)
ここで、a+b+c+d1+d2=1、eは任意、f1+f2+f3=1、hはペロブスカイトを構成する任意の値である。
(a)Mg(マグネシウム),Ni(ニッケル),Co(コバルト),Fe(鉄),Mn(マンガン),Cr(クロム),Zr(ジルコニウム),Ti(チタン),Ag(銀),Zn(亜鉛),Sc(スカンジウム),Bi(ビスマス)から選ばれた金属元素からなる単一金属酸化物
(b)M−Ti−O系スピネル化合物(元素Mは1〜5価の金属)
(c)A2B6O13系化合物(元素Aは1価の金属、元素Bは2〜6価の金属)
(d)A3B5O15系化合物(元素Aは1〜2価の金属、元素Bは2〜5価の金属)
(e)A−Ti−B−O系化合物(元素Aはアルカリ金属、元素BはNbとTaのうちの少なくとも1種)
なお、副相は存在しなくても良いが、副相が存在する場合には、副相の含有割合の合計値は、無鉛圧電磁器組成物の全体に対して5体積%以下とすることが好ましい。
0.494≦a≦0.506 …(9a)
0.050≦b≦0.250 …(9b)
0.100≦c≦0.200 …(9c)
0.200≦d≦0.270 …(9d)
なお、この発明は上記の実施例や実施形態に限られるものではなく、その要旨を逸脱しない範囲において種々の態様において実施することが可能である。
110…基材
120…外部電極
130…空気参照電極(導電体層)
200…圧電素子
300…圧電磁器
301,302…電極
Claims (7)
- 組成式:REaCobCucNidOx(但し、REは希土類元素を表し、a+b+c+d=1、1.25≦x≦1.75)で表されるペロブスカイト型酸化物結晶構造を有する結晶相を含み、前記a,b,c,dが、
0.474≦a≦0.512、
0.050≦b≦0.350、
0<c<0.250、
0.050≦d≦0.350
を満たすことを特徴とする導電性酸化物焼結体。 - 請求項1に記載の導電性酸化物焼結体であって、
前記希土類元素REは、Laであることを特徴とする導電性酸化物焼結体。 - 請求項2に記載の導電性酸化物焼結体であって、
前記a,b,c,dが、
0.487≦a≦0.506、
0.050≦b≦0.250、
0<c<0.250、
0.200≦d≦0.275
を満たすことを特徴とする導電性酸化物焼結体。 - 導電用部材であって、
セラミックス製の基材と、
前記基材の表面に、請求項1〜3のいずれか一項に記載の導電性酸化物焼結体で形成された導電体層と、
を備えることを特徴とする導電用部材。 - 請求項1〜3のいずれかに記載の導電性酸化物焼結体で形成された電極を備えることを特徴とするガスセンサ。
- 圧電磁器組成物で形成された圧電磁器と、
前記圧電磁器の表面に、請求項1〜3のいずれかに記載の導電性酸化物焼結体で形成された電極と、
を備えることを特徴とする圧電素子。 - 請求項6記載の圧電素子を製造する製造方法であって、
前記圧電磁器組成物で形成された未焼結成形体を作製する工程と、
前記未焼結成形体を第1の焼成温度で焼成することによって前記圧電磁器を得る第1焼成工程と、
前記圧電磁器の表面に、前記導電性酸化物焼結体を形成するための導電性酸化物ペーストを塗布する工程と、
前記導電性酸化物ペーストが塗布された前記圧電磁器を、前記第1の焼成温度よりも低い第2の焼成温度で焼成する第2焼成工程と、
を備えることを特徴とする圧電素子の製造方法。
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